JEE Chemistry Practice Book Overview
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MASTER INDEX
VOLUME 1:
Structure of an Atom
Periodic Properties
Chemical Bonding
Mole & Equivalent concept
VOLUME 2:
Redox Reactions
General Organic Chemistry
Hydrocarbons
Thermodynamics and Thermochemistry
VOLUME 3:
Chemical Equilibrium
Ionic Equilibrium
p-Block (group 13 and 14)
VOLUME 4:
Gaseous State
Hydrogen
s- Block
Environmental Chemistry
TABLE OF CONTENTS
REDOX REACTIONS
Theory ............................................................................................................................................................................................... 7
Exercise - 1 : Basic Objective Questions........................................................................................................................... 22
Exercise - 2 : Previous Year JEE MAIN Questions ....................................................................................................... 26
Exercise - 3 : Advanced Objective Questions ............................................................................................................ 30
Exercise - 4 : Previous Year JEE Advanced Questions ........................................................................................... 35
Answer Key ..................................................................................................................................................................................... 229
GENERAL ORGANIC CHEMISTRY
Theory ............................................................................................................................................................................................... 40
Exercise - 1 : Basic Objective Questions........................................................................................................................... 73
Exercise - 2 : Previous Year JEE MAIN Questions ....................................................................................................... 84
Exercise - 3 : Advanced Objective Questions ............................................................................................................ 93
Exercise - 4 : Previous Year JEE Advanced Questions ........................................................................................... 102
Answer Key ..................................................................................................................................................................................... 231
HYDROCARBONS
Theory ............................................................................................................................................................................................... 106
Exercise - 1 : Basic Objective Questions........................................................................................................................... 144
Exercise - 2 : Previous Year JEE MAIN Questions ....................................................................................................... 154
Exercise - 3 : Advanced Objective Questions ............................................................................................................ 167
Exercise - 4 : Previous Year JEE Advanced Questions ........................................................................................... 177
Answer Key ..................................................................................................................................................................................... 233
THERMODINAMICS & THERMOCHEMISTRY
Theory ............................................................................................................................................................................................... 182
Exercise - 1 : Basic Objective Questions........................................................................................................................... 199
Exercise - 2 : Previous Year JEE MAIN Questions ....................................................................................................... 208
Exercise - 3 : Advanced Objective Questions ............................................................................................................ 214
Exercise - 4 : Previous Year JEE Advanced Questions ........................................................................................... 221
Answer Key ..................................................................................................................................................................................... 235
REDOX REACTIONS
Chapter 05 7
REDOX REACTIONS
1. OXIDATION & REDUCTION
Let us do a comparative study of oxidation and reduction
Oxidation Reduction
1. Addition of Oxygen e.g. 2Mg + O2 2MgO 1. Removal of Oxygen e.g. CuO + C Cu + CO
2. Removal of Hydrogen e.g. H2S + Cl2 2HCl + S 2. Addition of Hydrogen e.g. S + H2 H2S
2+ 3+ – 3+ – 2+
3. Increase in positive charge e.g. Fe Fe + e 3. Decrease in positive charge e.g. Fe + e Fe
4. Increase in oxidation number 4. Decrease in oxidation number
(+2) (+4) (+7) (+2)
– 2+
e.g. SnCl2 SnCl4 e.g. MnO4 Mn
2+ 4+ – 3+ – 2+
5. Removal of electron e.g. Sn Sn + 2e 5. Addition of electron e.g. Fe + e Fe
2. OXIDATION NUMBER In case of
It is an imaginary or apparent charge developed over atom of an (i) peroxide (e.g. H2O2, Na2O2) is –1,
element when it goes from its elemental free state to combined
(ii) super oxide (e.g. KO2) is –1/2
state in molecules.
(iii) ozonide (e.g. KO3) is –1/3
It is calculated on basis of an arbitrary set of rules.
(iv) in OF2 is +2 & in O2F2 is +1
It is a relative charge in a particular bonded state.
In order to keep track of electron-shifts in chemical reactions Hydrogen Atom
involving formation of compounds, a more practical method of In general, H atom has oxidation number equal to +1. But in
using oxidation number has been developed. metallic hydrides (e.g. NaH, KH) it is –1.
In this method, it is always assumed that there is a complete Halogen Atom
transfer of electron from a less electronegative atom to a more
In general, all halogen atoms (Cl, Br, I) have oxidation number
electronegative atom.
equal to –1.
2.1 Rules Governing Oxidation Number
But if halogen atom is attached with a more electronegative
The following rules are helpful in calculating oxidation number atom than halogen atom, then it will show positive oxidation
of the elements in their different compounds. it is to be numbers.
remembered that the basis of these rule is the electronegativity
5 5 7 5
of the element. e.g. K ClO3 , HIO3 , HClO 4 , KBrO3
Fluorine Atom Metals
Fluorine is most electronegative atom (known). It always has (a) Alkali metal (Li, Na, K, Rb, .........) always have oxidation number
oxidation number equal to –1 in all its compounds +1
Oxygen Atom (b) Alkaline earth metal (Be, Mg, Ca ......) always have oxidation
In general and as well as in its oxides, oxygen atom has number +2.
oxidation number equal to –2. (c) Aluminium always has +3 oxidation number
SCAN CODE
Redox Reactions
REDOX REACTIONS 8
NOTE 4. CALCULATION OF INDIVIDUAL OXIDATION
Metal may have negative or zero oxidation number NUMBER
Oxidation number of an element in free state or in allotropic It is important to note that to calculate individual oxidation number
forms is always zero of the element in its compound one should know the structure of
0 0 0 0 the compound and use the following guidelines.
e.g. O 2 , S8 , P 4 , O3
Formula :
Sum of the oxidation numbers of atoms of all elements in a Oxidation Number = Number of electrons in the valence shell -
molecule is zero. Number of electrons taken up after bonding
Sum of the oxidation numbers of atoms of all elements in an Guidelines : It is based on electronegativity of elements.
ion is equal to the charge on the ion. 1. If there is a bond between similar type of atom and each atom
If the group number of an element in modern periodic table is has same type of hybridisation, then bonded pair electrons
n, then its oxidation number may vary from are equally shared by each element.
Example
(n – 10) to (n – 18) (but it is mainly applicable for p-block
elements) Calculate oxidation number of each Cl-atom in Cl2 molecule
e.g. N-atom belongs to 15th group in the periodic table,
therefore as per rule, its oxidation number may vary from
3 2 3 4 5
–3 to +5 NH3 , NO, N 2 O3 , NO2 , N 2 O5
I. Number of electrons in the valence shell = 7
The maximum possible oxidation number of any element in a Number of electrons taken up after bonding = 7.
compound is never more than the number of electrons in oxidation number = 7 – 7 = 0.
valence shell. (but it is mainly applicable for p-block elements) II. similarly, oxidation number = 7 – 7 = 0
3. CALCULATION OF AVERAGE OXIDATION NUMBER 2. If there is a bond between different type of atoms :
Example e.g. A – B (if B is more electronegative than A)
Calculate oxidation number of underlined element : Then after bonding, bonded pair of electrons are counted
with B-atom
(a) Na 2 S2 O3 (b) Na 2 S4 O6 Example
Sol. Calculate oxidation number of each atom in HCl molecule
(a) Let oxidation number of S-atom is x. Now work
accordingly with the rules given before.
(+1) × 2 + (x) × 2 + (–2) × 3 = 0 Structure :
x =+2
(b) Let oxidation number of S-atom is x NOTE
(+1) × 2 + (x) × 4 + (–2) × 6 = 0 Electron of H-atom is now counted with Cl-atom, because Cl-
x = + 2.5 atom is more electronegative than H-atom
It is important to note here that Na2S2O3 have two S- H : Number of electrons in the valence shell = 1
atoms and there are four S-atom in Na2S4O6. However Number of electrons taken up after bonding = 0
none of the sulphur atoms in both the compounds Oxidation number of H = 1 – 0 = + 1
have +2 or + 2.5 oxidation number, it is the average of
oxidation number, which reside on each sulphur atom. Cl : Number of electrons in the valence shell = 7
Therefore, we should work to calculate the individual Number of electrons taken up after bonding = 8
oxidation number of each sulphur atom in these Oxidation number of Cl = 7 – 8 = –1
compounds.
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Redox Reactions
REDOX REACTIONS 9
Example From the structure, it is evident that in CrO5 there are two peroxide
linkages and one double bond. The contribution of each peroxide
Calculate individual oxidation number of each S-atom in
linkage is –2. Let the oxidation number of Cr is x.
Na 2S 2 O 3 (sodium thiosulphate) with the help of its
x + (–2) 2 + (–2) = 0 or x = 6
structure.
Oxidation number of Cr = +6
Sol.
Structure :
The structure of H2SO5 is
From the structure, it is evident that in H2SO5, there is one peroxide
linkage, two sulphur-oxygen double bonds and one OH group.
Let the oxidation number of S = x.
(+1) + (–2) + x + (–2) 2+ (–2) + 1 = 0
or x + 2 – 8 or x – 6 = 0 or x = 6
Oxidation number of S in H2SO5 is + 6
NOTE
3
I (central S-atom) is sp hybridised (25% s-character) and II
5. PARADOX OF FRACTIONAL OXIDATION NUMBER
2
(terminal S-atom) is sp hybridised (33% s-character). Therefore, Fractional oxidation number is the average of oxidation state of all
terminal sulphur atom is more electronegative than central atoms of element under examination and the structural parameters
sulphur atom. Now, the shared pair of electrons are counted reveal that the atoms of element for whom fractional oxidation
with terminal S-atom. state is realised a actually present in different oxidation states.
I, S-atom : Number of electrons in the valence shell = 6 Structure of the species C3O2, Br3O8 and S4 O 62 reveal the
Number of electrons left after bonding = 0 following bonding situations :
Oxidation number of central S-atom = 6 – 0 = +6 The element marked with asterisk (*) in each species is
exhibiting different oxidation number from rest of the atoms of
II, S-atom : Number of electrons in the valence shell = 6
the same element in each of the species. This reveals that in
Number of electrons left after bonding = 8 C3O2, two carbon atoms are present in +2 oxidation state each
Oxidation number of terminal S-atom = 6 – 8 = – 2 whereas the third one is present in zero oxidation state and
Now, you can also calculate Average Oxidation number of the average is +4/3. However, the realistic picture is +2 for two
terminal carbons and zero for the middle carbon.
6 (2)
S 2 (as we have calculated before) 2 2
2 0
O C C* C O
4.1 Miscellaneous Examples
Structure of C3O2 (Carbon suboxide)
In order to determine the exact or individual oxidation number we
need to take help from the structures of the molecules. Some special Likewise in Br3O8, each of the two terminal bromine atoms are
cases are discussed as follows : present in +6 oxidation state and the middle bromine* is present
in +4 oxidation state. Once again the average, that is different
from reality, is + 16/3.
The structure of CrO5 is
SCAN CODE
Redox Reactions
REDOX REACTIONS 10
In the same fashion, in the species S4 O62 , average oxidation or which undergoes gain of electrons in a redox reaction are
termed as oxidants.
number of S is + 2.5, whereas the reality being + 5, 0*, 0* and
+5 oxidation number respectively for respective sulphur atoms. e.g. KMnO4, K2Cr2O7, HNO3, conc. H2SO4 etc are powerful
oxidising agents.
Reducing Agent or Reductant
Reducing agents are those compounds which can reduce other
and oxidise itself during the chemical reaction. Those reagents
in which for an element, oxidation number increases or which
In general, the conclusion is that the idea of fractional oxidation undergoes loss of electrons in a redox reaction are termed as
state should be taken with care and the reality is revealed by the reductants.
structures only.
e.g. KI, Na2S2O3 etc are the powerful reducing agents.
6. OXIDISING AND REDUCING AGENT NOTE
Oxidising Agent or Oxidant There are some compounds also which can work both as
oxidising agent and reducing agent
Oxidising agents are those compounds which can oxidise
others and reduce itself during the chemical reaction. Those e.g. H 2 O 2 , NO 2
reagents in which for an element, oxidation number decreases
How to Identify whether a particular substance is an Oxidising or a Reducing Agent
Example: HNO3 Example: Lithium
Example: Sulphur
SCAN CODE
Redox Reactions
REDOX REACTIONS 11
List of Some Important Disproportionation Reactions
7. REDOX REACTION
1. H 2 O 2
H 2O O 2
A reaction in which oxidation and reduction simultaneously
take place is called a redox reaction. In all redox reactions, the –
2. X2 + OH (dil.)
– –
X + XO (X = Cl, Br, I)
total increase in oxidation number must be equal to the total
– –
decrease in oxidation number. 3. X2 + OH (conc.)
X + XO3
e.g.
F2 does not undergo disproportionation as it is the most
2 5
electronegative element.
10FeSO 4 2KMnO 4 8H 2SO 4
–
3 2 F2 + NaOH (dil.)
F + OF2
5Fe 2 (SO 4 )3 2MnSO 4 K 2SO 4 8H 2 O
7.1 Disproportionation Reaction F O 2
F2 NaOH (conc.)
A redox reaction in which same element present in a particular
4. (CN) 2 OH
CN OCN
compound in a definite oxidation state is oxidized as well as reduced
simultaneously is a disproportionation reaction.
5. P4 OH
PH 3 H 2 PO 2
Disproportionation reactions are a special type of redox reactions.
One of the reactants in a disproportionation reaction always 6. S8 OH
S2 S2O 32
contains an element that can exist in at least three oxidation states. The
element in the form of reacting substance is in the intermediate oxidation 7. MnO 24
MnO 4 MnO 2
state and both higher and lower oxidation states of that element are
formed in the reaction. For Example 8. NH 2 OH
N 2O NH 3
1 2 0
2H 2 O 2 (aq) 2H 2 O ( l ) O 2 (g) NH 2 OH
N 2 NH 3
0 9. Oxyacids of Phosphorus (+1, +3 oxidation number)
S8 (s) 12OH (aq)
2 2 H 3PO 2
PH 3 H 3 PO3
4S 2 (aq) 2 S 2 O 32 (aq) 6H 2 O (l )
1
H 3PO 3
PH 3 H 3 PO 4
0 1
Cl 2 (g) 2OH (aq)
Cl O (aq) Cl (aq) H 2 O(l )
10. Oxyacids of Chlorine (Halogens) (+1, +3, +5 Oxidation number)
Consider the Following Reations
ClO
Cl ClO 2
(a) 2KClO3
2KCl + 3O2
ClO 2
Cl ClO3
KClO3 plays a role of oxidant and reductant both. Here, Cl
present in KClO3 is reduced and O present in KClO3 is ClO3
Cl ClO4
oxidized. Since same element is not oxidized and reduced, so
it is not a disproportionation reaction, although it looks like 11. HNO2
NO + HNO3
one.
Reverse of disproportionation is called Comproportionation.
3 3 0
(b) N H 3 N O2 N 2 2H 2 O In some of the disproportionation reactions, by changing the
medium (from acidic to basic or reverse), the reaction goes in
Nirogen in this compound has -3 and +3 oxidation number,
backward direction and can be taken as an example of
which is not a definite value. So it is not a disporportionation
Comproportionation reaction.
reaction. It is an example of comproportionation reaction,
which is a class of redox reaction in which an element from 1 5 0
two different oxidation state gets converted into a single I I O3 H
I2 H 2 O
oxidation state.
5 7 1
(c) 4KClO 3
3KClO 4 KCl
It is a case of disproportionation reaction and Cl atom is
disproportionating.
SCAN CODE
Redox Reactions
REDOX REACTIONS 12
8. BALANCING OF REDOX REACTIONS Step III :
Now identify the oxidation/reduction occuring in the
All balanced equations must satisfy two criteria. reaction
1. Atom balance (Mass Balance) :
There should be the same number of atoms of each kind on
reactant and product side.
2. Charge Balance :
The sum of actual charges on both sides of the equation must
Step IV :
be equal.
Spilt the Ionic reaction in two half, one for oxidation and
There are two methods for balancing the redox equations
other for reduction.
1. Oxidation – number change method
2. Ion electron method or half cell method
Since First method is not very much fruitful for the balancing
Step V :
of redox reactions, students are advised to use second method
(Ion electron method) to balance the redox reactions Balance the atom other than oxygen and hydrogen atom
in both half reactions
8. 1 Ion Electron Method
By this method redox equations are balanced in two different
medium.
(a) Acidic medium (b) Basic medium Fe & Mn atoms are balanced on both side.
Balancing in Acidic Medium Step VI :
+
Students are adviced to follow the following steps to balance the Now balance O & H atom by H2O & H respectively by the
redox reactions by ion electron method in acidic medium following way : For one excess oxygen atom, add one H2O
+
Example on the other side and two H on the same side.
Balance the following redox reaction :
Fe 2
Fe3 (no oxygen atom)............... (i)
FeSO4 + KMnO4 + H2SO4
Fe2(SO4)3 + MnSO4 +
8H MnO 4
Mn 2 4H 2 O ................ (ii)
H2O + K2SO4
Sol. Step VII :
Step-I : Equation (i) & (ii) are balanced atomwise. Now balance
both equations chargewise. To balance the charge, add
Assign the oxidation number to each element present in
electrons to the electrically positive side.
the reaction
oxidation
2 6 2 1 7 2 1 6 2 Fe 2 Fe3 e ........ (1)
Fe SO 4 K MnO 4 H 2 SO 4
3 6 2 2 6 2 1 2
5e 8H MnO 4
Reduction
Mn 2 4H 2 O ......... (2)
Fe 2 (SO 4 )3 Mn SO 4 H 2 O
Step II : Step VIII :
Now convert the reaction in Ionic form by eliminating the The number of electrons gained and lost in each half-
elements or species, which are not undergoing either reaction are equalised by multiplying both the half reactions
oxidation or reduction. with a suitable factor and finally the half reactions are
7
added to give the overall balanced reaction.
Fe 2 Mn O 4
Fe3 Mn 2 Here, we multiply equation (1) by 5 and (2) by 1 and add
them :
SCAN CODE
Redox Reactions
REDOX REACTIONS 13
Fe 2
Fe3 e ..........(1) 5 4OH CrO2 CrO42 2H2O ........ ii
Now see equation (i) and (ii) in which O and H atoms are
–
balanced by OH and H2O
(Here, at his stage, you will get balanced redox reaction in Now from step VIII
Ionic form)
2e H 2 O ClO Cl 2OH .......(i) 3
Step IX : 2
4OH CrO CrO 2H 2 O 3e
.......(ii) 2
2 4
Now convert the ionic reaction into molecular form by Adding : 3ClO 2CrO 2OH 3Cl 2CrO 42 H 2 O
2
adding the elements or species, which are removed in step
(2). 9. CONCEPT OF EQUIVALENTS
Now, by some manipulation, you will get :
9.1 Equivalent Mass of Element
or
Number of parts by mass of an element which reacts or displaces
5 FeSO 4 KMnO 4 4H 2SO 4
from a compound 1.008 parts by mass of hydrogen, 8 parts by
5 1 mass of oxygen and 35.5 parts by mass of chlorine, is known as
Fe 2 (SO 4 )3 MnSO 4 4H 2 O K 2SO 4
2 2 the equivalent weight of the element.
10FeSO 4 2KMnO 4 8H 2SO 4
e.g. 2Mg + O2
2MgO
5 Fe 2 (SO 4 )3 2MnSO 4 8H 2 O K 2SO 4 .
48g 32g
Balancing in Basic Medium
12g 8g
In this case, except step VI, all the steps are same. We can
understand it by the following Example 32g of O2 reacts with 48 g of Mg
Example 48 8
8 g of O2 = 12g
Balance the following redox reaction in basic medium : 32
ClO CrO 2 OH
Cl CrO 42 H 2O Equivalent weight of Mg = 12
Sol. By using upto step V, we will get : Similarly, Zn + H2SO4
ZnSO4 + H2
65.5 g 32.75
65.5
Equivalent weight of Zn = 32.75g
2
Now, students are advised to follow step VI to balance ‘O’
and ‘H’ atom. 3
Al Cl 2
AlCl3
2
2H ClO
Cl H 2O | 2H 2O CrO 2 4H CrO 42
3
Now, since we are balancing in basic medium, therefore 27 g 71 g
– 2
add as many as OH on both side of equation as there are
+
H ions in the equation. 111.5 g chlorine reacts with 27 g of Al.
2OH 2H ClO Cl H 2 O 2OH 27 35.5
35.59 chlorine reacts with 9.0 g of Al
111.5
Finally you will get
27
H 2 O ClO Cl 2OH ........ i Equivalent weight of aluminium = 9.0
3
4OH 2H2O CrO2 CrO42 4H 4OH As we can see from the above examples that equivalent weight is
the ratio of atomic weight and a factor (say n-factor or valency
Finally you will get
factor) which is in above three cases is their respective valencies.
SCAN CODE
Redox Reactions
REDOX REACTIONS 14
Equivalent Weight (E) : Example
In general, Eq. wt. (E) = 2NaOH H 2 SO 4
Na 2 SO 4 2H 2 O
Atomic weight or molecular weight Mol. wt. M
Base Acid
valency factor (v.f ) n factor x
Sol. Valency factor of base = 1
+
mass of species Here, two molecule of NaOH replaced 2H ion from the
Number of Equivalents = eq. wt. of that species H2SO4. Therefore, each molecule of NaOH replaced only
+
one H ion of acid, so v.f. = 1.
For a solution, Number of equivalents = N1V1, where N is the –
normality and V is the volume in litres v. f. for acid is the number of OH replaced from the
base by each molecule of acid
Equivalent mass is a pure number which, when expressed in
gram, is called gram equivalent mass. Example
The equivalent mass of substance may have different values NaOH H 2SO 4
NaHSO 4 H 2 O
under different conditions.
Base Acid
There is no hard and fast rule that equivalent weight will be Sol. Valency factor of acid = 1
always less than the molecular mass. –
Here, one of molecule of H2SO4 replaced one OH from
9.2 Valency Factor Calculation
NaOH. Therefore, valency factor for H2SO4 is one
For Elements :
Mol. wt
Valency factor = valency of the element. Eq. wt. of H2SO4 =
1
For Acids :
+ Salts :
Valency factor = number of replaceable H ions per acid
(a) ln Non-Reacting Condition
molecule
Example Valency factor = Total number of positive charge or negative
charge present in the compound.
NaOH, KOH
Example
Sol. v.f. 1 1
Na2 CO3 Fe2 (SO4)3 FeSO4.7H2O
M M
Eq. wt. Sol. v.f. = 2 2×3=6 2
1 1
M M M
Bases may be defined as the substances in which OH group Eq. wt.
2 6 2
is/are directly attached with group I elements (Li, Na, K, Rb,
Cs), group II elements (Be, Mg, Ca, Ba) or group III elements (b) In Reacting Condition
(Al, Ga, ln, Tl), transition metals, non-metallic cations like Example
PH , NH etc.
4 4
Na 2 CO 3 HCl
NaHCO3 NaCl
Acid - Base Reaction : Base Acid
In case of acid base reaction, the valence factor is the actual Sol. It is an acid base reaction, therefore valency factor for
+ –
number of H or OH replaced in the reaction. The acid or base Na2CO3 is one while in non-reacting condition, it will be
+ –
may contain more number of replaceble H or OH than two.
actually replaced in reaction. (c) Equivalent Weight of Oxidising / Reducing Agents in a Redox
+
v. f. for base is the number of H ion from the acid replaced by Reaction
each molecule of the base In case of redox change, v.f. = Total change in oxidation number
per molecule.
SCAN CODE
Redox Reactions
REDOX REACTIONS 15
Example 11. LAW OF EQUIVALENCE
2
KMnO 4 H 2 O 2
Mn O2 The law states that one equivalent of an element combine with
Sol. Mn in KMnO4 is going from +7 to +2, so change in oxidation one equivalent of the other. In a chemical reaction, equivalents
number per molecule of KMnO4 is 5. So the valency factor and milli equivalents of reactants react in equal amount to give
same number of equivalents or milli equivalents of products
M separately.
of KMnO4 is 5 and equivalent weight is .
5 Accordingly
10. NORMALITY (i) aA + bB mM + nN
meq of A = meq of B = meq of M = m.eq. of N
Normality of a solution is defined as the number of equivalents of
solute present in one litre (1000 mL) solution. (ii) In a compound MxNy
Let V mL of a solution is prepared by dissolving W g of solute of meq of MxNy = meq of M = meq of N
equivalent weight E in water. Example
W Find the number of moles of KMnO4 needed to oxidise
Number of equivalents of solute =
E one mole Cu2S in acidic medium.
The reaction is
W
VmL of solution contain equivalents of solute
E 2 2
Mn Cu SO 2
KMnO4 + Cu2S
W 1000 Sol. From law of equivalence,
1000 mL solution will contain equivalents of
EV equivalents of Cu2S = equivalents of KMnO4
solute.
moles of Cu2S × v.f. = moles of KMnO4 × v.f.
W 1000 1 × 8 = moles of KMnO4 × 5 moles of KMnO4 = 8/5
Normality (N) =
EV
( v.f. of Cu2S = 2 (2 – 1) + 1 (4 – (–2)) = 8 and v.f. of
Normality (N) = Molarity × Valency factor KMnO4 = 1 (7 – 2) = 5)
N × V (in mL) = M × V (in mL) × n Example
or The number of moles of oxalate ions oxidized by one mole
milliequivalents = millimoles × n of MnO 4 ion in acidic medium are :
Example 5 2
(a) (b)
Calculate the normality of a solution containing 15.8 g of 2 5
KMnO4 in 50 mL acidic solution. 3 5
(c) (d)
5 3
W 1000
Sol : Normality (N) =
EV MnO 4 C 2 O 42 Mn 2 2CO 2
Sol. 7 3 2 4
Here W = 15.8 g, V = 50 mL
molar mass of KMnO 4 Equivalents of C 2 O 42 = equivalents of MnO 4
E 158/ 5 31.6
Valency factor x (mole) × 2 = 1 × 5
So, normality = 10 N ( v.f. of C 2 O 24 2 (4 3) 2
Example
and v.f. of MnO 4 = 1 (7 – 2) = 5.
Calculate the normality of a solution containing 50 mL of 5
M solution of K2Cr2O7 in acidic medium. 5
x mole of C 2 O 42 ions.
Sol : Normality = Molarity × valency factor = 5 × 6 = 30 N 2
SCAN CODE
Redox Reactions
REDOX REACTIONS 16
Example 12 TITRATIONS
How many millilitres of 0.02 M KMnO4 solution would be
Titration is procedure for determining the concentration of a
required to exactly titrate 25 mL of 0.2 M Fe(NO3)2 solution
solution by allowing a carefully measured volume to react with a
in acidic medium ?
standard solution of another substance, whose concentration is
Sol. Method -1 : Mole Concept Method known.
2+
Starting with 25 mL of 0.2 M Fe , we can write : Standard Solution - It is a solution whose concentration is known
2+ and is taken in burette. It is also called Titrant.
Millimoles of Fe = 25 × 0.2 ........ (1)
There are two type of titrants :
and in volume V (in milliliters) of the KMnO4,
Primary Titrants/Standard - These reagents can be accurately
Millimoles of MnO 4 = V (0.02) ........... (2) weighed and their solutions are not to be standardised before
The balanced reaction is : use.
Ex : Oxalic acid, K2Cr2O7, AgNO3, CuSO4, ferrous ammonium
MnO 4 5Fe 2 8H
Mn 2 5Fe3 4H 2 O
sulphate, hypo etc.
This requires that at the equivalent point,
Secondardy Titrants/Standard : These reagents cannot be
m.moles of MnO 4 m.moles of Fe 2 accurately weighed and their solutions are to be standardised
1 5 before use.
V(0.02) (25) (0.2) Ex : NaOH, KOH, HCl, H2SO4, I2, KMnO4, etc.
(from (1) & (2))
1 5
Titrate : Solution consisting of substance to be estimated,
V = 50 mL. generally taken in a beaker.
Method -2 : Equivalent Method Equivalence Point : It is the point when number of equivalents of
At the equivalence point, titrant added becomes equal to number of equivalents of titrate.
milliequivalents of MnO 4 = milliequivalents of Fe
2+ At Equivalence Point :
n1V1M1 = n2V2M2
M1 × vf1 × V1 = M2 × vf2 × V2
Indicator : An auxiliary substance added for physical detection of
0.02 × 5 × V1 = 0.2 × 1 × 25 completion of titration at equivalence point. It generally show
colour change on completion of titration.
( MnO 4 Mn 2 ; v.f . 5, Fe 2 Fe3 ; v.f . 1)
Types of Titrations :
V1 50 mL.
Acid-base titrations (to be studied in Ionic equilibrium)
Redox Titrations
SCAN CODE
Redox Reactions
REDOX REACTIONS 17
12. 1 Some Common Redox Titrations
M
12.1.1 Permanganate Titrations 5e Mn 7
Mn 2 E KMnO4
5
KMnO4 is generally used as oxidising agent in acidic medium,
Indicator : KMnO4 acts as self indicator.
generally provided by dilute H2SO4.
Example
KMnO4 works as self indicator persistent pink color is
Write the balanced reaction of titration of KMnO4 Vs
indication of end point.
2+ ferrous ammonium sulphate in presence of H2SO4.
Mainly used for estimation of Fe , oxalic acid, oxalates, H2O2
Sol. Reaction :
etc.
2KMnO 4 10 [FeSO 4 (NH 4 ) 2 SO 4 .6H 2 O] 8H 2SO 4
Example
Write the balanced reaction of titration of KMnO4 Vs oxalic
acid in presence of H2SO4. 5Fe 2 (SO 4 )3 10(NH 4 ) 2 SO 4 K 2SO 4 2MnSO 4 68H 2O
Sol. Reaction :
M
2KMnO 4 3H 2SO 4 5H 2 C 2 O 4
Fe3 e E FeSO4
Redox Changes : Fe2
1
K 2 SO 4 2MnSO 4 8H 2 O 10CO 2
M
M Mn 7 5e
Mn 2 E KMnO4
5
2C4 2e E H2C2O4
Redox Changes 2C3
2
Indicator : KMnO4 acts as self indicator.
Redox Titrations : (Excluding lodometric/Iodimetric titrations)
Estimation By titrating Reactions Relation *between
of with OA and RA
2+
Fe MnO 4 Fe 2 Fe3 e 5Fe 2 MnO 4
2+
MnO 4 8H 5e Mn 2 4H 2 O Eq. wt. of Fe = M/1
2+
Fe Cr2 O 72 Fe 2 Fe3 e 6Fe 2 Cr2 O 72
Cr2 O 72 14H 6e 2Cr 3 7H 2 O Eq. wt. of Cr2O 72 M / 6
C 2 O 42 MnO 4 C 2 O 24 2CO 2 2e 5C 2 O 42 2MnO 4
MnO 4 8H 5e Mn 2 4H 2 O Eq. wt.of C 2O 42 M / 2
H2 O 2 MnO 4 H 2 O 2 2H O 2 2e 5H 2 O 2 2MnO 4
MnO 4 8H 5e Mn 2 4H 2 O Eq. wt. of H2O2 = M/2
As 2 O 3 MnO 4 As 2 O3 5H 2 O 2AsO34 10H 4e Eq. wt of As2O3 = M/4
MnO 4 8H 5e Mn 2 4H 2 O
AsO 33 BrO3 AsO 33 H 2 O AsO 34 2H 2e Eq. wt. of AsO 33 M / 2
BrO 3 6H 6e Br 3H 2 O Eq. wt. of BrO3 = M/6
SCAN CODE
Redox Reactions
REDOX REACTIONS 18
13. HYDROGEN PEROXIDE (H2O2) To obtain 11.2 litre O2 at STP, at least 34 g H2O2 must be
decomposed.
H2O2 can behave both like oxidising and reducing agent in both
the mediums (acidic and basic). 34
For 20 L O2, we should decompose atleast 20 g H 2O 2
11.2
34
1L solution of H2O2 contains 20 g H 2O 2
11.2
34 20
1L solution of H2O2 contains equivalents of H2O2
11.2 17
Oxidising Agent : (H2O2 H2O)
M 34
(E H2O2 17)
(a) Acidic Medium : 2e 2H H 2 O 2
2H 2 O 2 2
v.f = 2 34 20 20
Nomality of H2O2 =
11.2 17 5.6
(b) Basic Medium : 2e H 2 O 2
2OH
v.f = 2 Volume strength of H 2O 2
Normality of H2O2 (N) =
5.6
Reducing Agent : (H2O2 O2)
N H 2O2 N H 2 O2
O 2 2H 2e
(a) Acidic Medium : H 2 O 2 M H 2O2
v.f . 2
v.f = 2
(b) Basic Medium : Volume strength of H 2O 2
Molarity of H2O2 (M) =
11.2
2OH H 2O 2
O 2 2H 2O 2e
Strength (in g/L) : Denoted by S
v.f = 2
Strength = Molarity × Mol. wt = Molarity × 34
NOTE
Strength = Normality × Eq. weight = Normality × 17
Valency factor of H2O2 is always equal to 2.
Example
Volume Strength of H2O2 : Strength of H2O2 is represented as
20 mL of H2O2 after acidification with dilute H2SO4 required
10V, 20V, 30V etc.
N
20VH 2 O 2 means one litre of this sample of H 2 O 2 on 30 mL of KMnO 4 for complete oxidation. Final the
12
decomposition gives 20L of O2 gas of STP.
strength of H2O2 solution. [Molar mass of H2O2 = 34]
Decomposition of H2O2 is given as :
Sol. meq. of KMnO4 = meq. of H2O2
H2O2 1
H 2O O2 1
2 30 20 N
12
1
1 mole × 22.4 L O2 at STP 30 1
2 N N
12 20 8
= 34g = 11.2 L O2 at STP
1
strength = N × equivalent mass = 17 2.12 g / L.
8
SCAN CODE
Redox Reactions
REDOX REACTIONS 19
14. HARDNESS OF WATER 14.1 Measurement of Hardness
Hardness is measured in terms of ppm (parts per million) of CaCO3
Temporary Hardness - due to bicarbonates of Ca & Mg.
or equivalent to it.
(a) Boiling : Soluble salts converts to insoluble salt during boiling
which forms ppt and can easily removed by filtration. mass of CaCO3
Hardness in ppm = Total mass of solution 10
6
Mg HCO3 2
Boil
Mg OH 2 2CO2
Example
Mg(OH)2 is precipitated because of high solubility product of
Mg(OH)2 as compared to that of MgCO3 0.00012% MgSO4 and 0.000111% CaCl2 is present in ater.
What is the measured hardness of water and millimoles
Ca HCO3 2
Boil
CaCO3 CO 2 H 2 O of washing soda required to purify water 1000 L water ?
Filtrate is soft water. Sol. Basis of calculation = 100 g hard water
(b) Clark’s method (calcium hydroxide/lime water method) : 0.00012
MgSO4 = 0.00012g mole
120
Ca HCO3 2 Ca OH 2 calculated amount
0.000111
2CaCO 3 2H 2 O CaCl2 = 0.000111g mole
111
Mg HCO3 2 2Ca OH 2 calculated amount equivalent moles of CaCO3 =
2CaCO3 Mg OH 2 2H 2 O 0.00012 0.000111
mole
120 111
Permanent Hardness - due to chlorides & sulphates of Ca & Mg.
There are some method by which we can soften the water sample. mass of CaCO3 =
(a) Addition of washing soda (sodium carbonate) : It 0.00012 0.000111 4
reacts with chloride and sulphate of Mg2+ and Ca2+ to 100 2 10 g
120 111
precipitate out as MgCO3 and CaCO3.
Hardness (in terms of ppm of CaCO3) =
MCl2 Na 2 CO3 MCO3 2 NaCl M Mg / Ca
2 104
106 2 ppm
MSO 4 Na 2 CO3 MCO3 Na 2SO4 M Mg / Ca 100
Parts Per Million (ppm) CaCl 2 Na 2 CO3
CaCO 3 2NaCl
When the solute is present in very less amount, then this
MgSO 4 Na 2 CO 3
MgCO3 Na 2SO 4
concentration term is used. It is defined as the number of parts of
the solute present in every 1 million parts of the solution. ppm can Required Na2CO3 for 100g of water =
both be in terms of mass or in terms of moles. If nothing has been
specified, we take ppm to be in terms of mass. Hence, a 100 ppm 0.00012 0.000111
mole
solution means that 100 g of solute is present in every 1000000g 120 111
of solution. –6
= 2 × 10 mole
mass of A Required Na2CO3 for 1000 litre water =
ppm A 106 mass fraction 106
Total mass
2 106 2
106 mole ( d 1g / mL)
100 100
20
mole 20 m mole
1000
SCAN CODE
Redox Reactions
REDOX REACTIONS 20
o +
15. ELECTROCHEMICAL CELL A negative E means that the H / H2 couple.
o
A positive E means that the redox couple is a weaker reducing
It is a device which converts chemcial energy produced in an +
agent than the H / H2 couple.
indriect redoc reaction into electrical energy.
The electrode potential is termed as oxidation potential if the
Redox couple is defined as a combination of the oxidised and
electrode loses electrons and is called the reduction potential if
reduced froms of the same substance taking part in an oxidation
the electrode gains electrons.
or reduction half reaction.
16.1 Electromotive Series
A list of oxidising agents, arranged in decreasing order of their
strength is called the activity or electromotive or electrochemical
series.
Representation of an electrochemcial cell
Zn | Zn 2 C1 || Cu 2 C2 | Cu
2
At anode : Zn s Zn aq 2e
2
At cathode : Cu aq 2e Cu s
15.1 Important Generalisation
Oxidation occurs at the anode while reduction occurs at the
cathode.
Anode acts as the negative pole while cathode acts as the positve
pole.
Electrons flow from anode to cathode in the external circuit while
current flows from cathode to anode.
Chemcial energy of the redox reaction occuring in the galvic cell is
converted into electrical energy.
16.2 Application
16. ELECTRODE POTENTIAL
To compare the relative strength of oxidising and reducing agents.
The tendency of an electrode to lose or gain electrons. Comparison of reactivity of metals.
-1
If the concetration of electrolytes is taken as unity (1 mol L ) or if To predict whether a metal willl liberate hydrogen from the aqueous
any gas appears in the electrode reaction, it is taken at 1 atm solution of acids or not.
presure and temoerature is taken as 298 K, then the electrode
o
potentials is called standard electrode potential (E )
o
By convertion, the standrad electrode potential (E ) of hydrogen
electrode is 0.00 volt.
SCAN CODE
Redox Reactions
REDOX REACTIONS 21
SUMMARY
Oxidation is a process which involves loss of electrons or Decomposition reaction
increase in oxidation number.
2KClO3 2KCl 3O 2
Reduction is a process which involves gain of electrons or
decrease in oxidation number. Displacement reaction
Oxidation agent is a substance which accepts one or more CuSO 4 Zn Cu ZnSO 4
electrons or its oxidation number decreases.
Sn 2HCl SnCl 2 H 2
Reducing agent is a substance which loses one or more
electrons or its oxidation number increases. Br2 2I 2Br I 2
Oxidation and Reduction always occur side by side. Disporpotionation reactions
Oxidation Number : The reactions in which the oxidation number of an element
Oxidation numnber is the charge which an atom appears to both increases and decreases.
have when all other atoms ar removed from it as ions.
e.g., 2H 2 O 2 2H 2 O O 2
For elementary state, O.N is zero.
In this case the oxidation number of O decreases from -1 to -2
e.g., He(O.N. = 0), H2 (O.N. = 0), Sn (O.N. = 0)
(in H2O) and increases from -1 to 0 (in O2)
Oxidation number of hydrogen is +1 except in hydrides NaH,
Cl 2 2OH OCl Cl H 2 O
LiH, CaH2 (-1).
=
Oxidation number of oxygen is always -2 except in peroxides, O.N. of Cl increases from 0 to +1 (in OCl ) and decreases from
=
H2O, N2O2 (-1) 0 to -1 (in Cl ).
in superpxodes KO2 (-1/2) 3ClO ClO 3 2Cl is also a disproportionation reaction
= =
in OF2 (+2) because O.N. of Cl increase from +1 (in ClO ) to +5 (in ClO3 )
=
O2F2 (+1) and decrease from +1 to -1 (in Cl ).
Oxidation and reduction reactions can be balanced by
Combination reaction
oxidation number method and half reaction method.
2Mg O 2 2MgO
SCAN CODE
Redox Reactions
REDOX REACTIONS 22
EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS
Concept of Oxidation and Reduction Oxidation Number
1. Which of the following behaves as both oxidising and 7. The oxidation stae of osmium (Os) in OsO4 is
reducing agents? (a) + 7 (b) + 5
(a) H2SO4 (b) SO2 (c) + 4 (d) + 8
(c) H2S (d) HNO3 8. Oxidation number of nitrogen in (NH4)2SO4 is
2. The compound that can work both as an oxidising as well as (a) – 1/3 (b) – 1
a reducing agent is : (c) + 1 (d) – 3
(a) KMnO4 (b) H2O2 9. The oxidation number of Phosphorus in Mg2P2O7 is :
(c) Fe2(SO4)3 (d) K2Cr2O7 (a) + 3 (b) + 2
3. Which of the following is not a redox reaction? (c) + 5 (d) – 3
(a) CaCO3 CaO + CO2 10. In which of the following compounds, nitrogen has an
(b) O2 + 2H2 2H2O oxidation state of – 1?
(c) Na + H2O Na OH + 1/2 H2 (a) N2O (b) NO2 –
(d) MnCl3 MnCl2 + 1/2 Cl2 (c) NH2OH (d) N2H4
4. Which substance serves as reducing agents in the following 11. A metal ion M 3+
loses 3 electrons, its oxidation number will
reaction? be :
14H+ + Cr2O72– + 3Ni 2Cr3+ + 7 H2O + 3Ni2+ (a) + 3 (b) + 6
(a) H2O (b) Ni (c) 0 (d) – 3
(c) H+ (d) Cr2O72– 12. In which of the following reactions is there a change in the
oxidation number of nitrogen atom?
5. Which of the following reactions depicts the oxidising
property of SO2? (a) 2 NO2 N2O4
(b) NH3 + H2O NH4+ + OH–
(a) SO2 + H2O
H2SO3
(c) N2O5 + H2O 2HNO3
(b) 2H2S + SO2
3S + 2H2O (d) None of these
(c) Cl2 + SO2
SO2Cl2 13. When SO2 is passed through an acidified solution of
potassium dichromate the oxidation state of S changes from:
(d) 2MnO4– + 5SO2 + 2H2O
5SO42– + 2Mn2+ + 4H + (a) + 4 to 0 (b) + 4 to + 2
6. Nitric oxide acts as a reducing agent in the reaction (c) + 4 to + 6 (d) + 6 to + 4
(a) 4NH3 + 5O2
4NO + 6H2O 14. Oxidation state of nitrogen is correctly given for
Compound Oxidation state
(b) 2NO + 3I2 + 4H2O
2NO3– + 6I– + 8H +
(a) [Co(NH3)5 Cl]Cl2 0
(c) 2NO + H2SO3
N2O + H2SO4 (b) NH2OH +1
(d) 2NO + H2S
N2O + S + H2O (c) (N2H5)2SO4 +2
(d) Mg3N2 – 3
REDOX REACTIONS 23
15. The oxidation state of chromium in Cr(CO)6 is : 22. For the redox reaction,
(a) 0 (b) + 2 MnO4– + C2O42– + H + Mn2 + + CO2 + H2O the correct
(c) – 2 (d) + 6 coefficients of the reactants for the balanced reaction are:
16. In which of the following pairs, there is greatest difference MnO4– C 2O 4 2 – H+
in the oxidation number of the underlined elements? (a) 2 5 16
(a) NO2 and N2O4 (b) P2O5 and P4O10 (b) 16 5 2
(c) N2O and NO (d) SO2 and SO3 (c) 5 16 2
17. In which of the compounds does manganese exhibit highest (d) 2 16 5
oxidation number? 23. What is the coefficient of oxalate ion in the following
(a) MnO2 (b) Mn3O4 reaction?
(c) K2MnO4 (d) MnSO4 MnO4– + C2O42– + H +
Mn2 + + CO2 + H2O
18. Which of the following elements has least oxidation number? (a) 4 (b) 2
(a) Ni(CN)4 (b) Ni(CO)4 (c) 3 (d) 5
(c) Fe2O3 (d) SF6 24. In the equation
19. The oxidation number of sulphur in S8, S2F2, H2S respectively NO 2 H 2 O
NO3 2H ne
are :
n stands for
(a) 0, + 1 and –2 (b) + 2, + 1 and –2
(a) 1 (b) 2
(c) 0, + 1 and + 2 (d) –2, + 1 and – 2
(c) 3 (d) 4
Types & Balancing of Redox Reactions
25. For the redox reaction MnO4 C2 O42 H
20. In which of the following reactions, there is no change in
valency?
Mn 2 CO2 H 2 O, The correct stoichiometric
(a) 4KClO3
3KClO4 + KCl
coefficients of MnO4 , C2 O42 and H are respectively:
(b) SO2 + 2H2S
2H2O + 3S
(a) 2,5,16 (b) 16,5,2
(c) BaO2 + H2SO4
BaSO4 + H2O2 (c) 5,16,2 (d) 2,16,5
(d) 2BaO + O2
2BaO2 26. In the chemical reaction, K 2 Cr2 O7 XH 2SO 4 YSO 2
21. Which of the following is a disproportionation reaction ?
K 2SO4 Cr2 SO4 3 ZH 2 O, X, Y and Z are
(a) Cu 2 O 2H
Cu Cu 2 H 2 O
(a) 1,3,1 (b) 4,1,4
(b) 2CrO 24 2H
Cr2 O 72 H 2 O (c) 3,2,3 (d) 2,1,2
27. In the chemical reaction,
(c) CaCO 3 2H
Ca 2 H 2 O CO 2
K2Cr2O7 + xH2SO4 + ySO2
K2SO4 + Cr2(SO4)3 + zH2O
2
2CrO24 H 2 O
(d) Cr2 O7 2 O H
x, y and z are
(a) 1, 3, 1 (b) 4, 1, 4
(c) 3, 2, 3 (d) 2, 1, 2
28. In the balanced chemical reaction
IO3 aI bH
cH 2 O dI 2
a, b, c and d respectively, correspond to
(a) 5, 6, 3, 3 (b) 5, 3, 6, 3
(c) 3, 5, 3, 6 (d) 5, 6, 5, 5
REDOX REACTIONS 24
29. How many moles of MnO 4 ion will react with 1 mol of ferrous 34. The standard reduction potentials at 298 K are given against
oxalate in acidic medium ? each of the following half cell reactions :
1 2
I. E Zn 2 |Zn 0.76 V
II. E Cr3 |Cr 0.74 V
(a) (b)
5 5
3 5 III. E H |H 2 0.00 V IV. E Fe3 |Fe2
0.77 V
(c) (d)
5 3
Based on the above data, state which of the following is the
Redox Reactions and Electrode Processes strongest reducing agent ?
30. Which of the following statement is correct for a galvanic (a) Zn (b) Cr
cell ?
(c) H2 (d) Fe
(a) Reduction occurs at cathode
Equivalent Concept
(b) Oxidation occurs at anode
(c) Electrons flow from anode to cathode 35. In the reaction VO Fe2 O3 FeO V2 O5 the eq. wt. of
(d) All the statements are correct V2O5 is equal to its
31. The correct order of reactivity of K, Mg, Zn and Cu with (a) mol. wt. (b) mol. wt./8
water according to the electrochemical series is (c) mol. wt./6 (d) none of these
(a) K > Mg > Zn > Cu (b) Mg > Zn > Cu > K 36. The eq. wt. of K2CrO4 as an oxidising agent in acid medium
(c) K > Zn > Mg > Cu (d) Cu > Zn > Mg > K is
32. Consider the following standard reduction potentials: 2 mol. wt.
(a) mol. wt./2 (b)
3
Ca; E o 2.76 V
Ca 2 2e
mol. wt. mol. wt.
Pb; E o 0.13 V
Pb 2 2e (c) (d)
3 6
Cu; E o 0.34 V
Cu 2 2e 37. In the conversion NH2OH N2O, the equivalent weight
2 of NH2OH will be :
Hg; E o 0.80 V
Hg 2 2e
(a)M/4 (b)M/2
2
Pt 2e Pt; E o 1.20 V
(c)M/5 (d)M/1
Which of the following metals is the strongest reducing (M = molecular weight of NH2OH)
agent? 38. The mass of oxalic acid crystals (H2C2O4.2H2O) required to
(a) Ca (b) Pb prepare 50 mL of a 0.2 N solution is :
(c) Cu (d) Hg (a) 4.5 g (b) 6.3 g
33. Consider the following electrodes potentials: (c) 0.63 g (d) 0.45 g
39. M is molecular weight of KMnO4.. The equivalent weight of
(a) V 2 2e V; E o 1.18V
KMnO4 when it is converted into K2MnO4 is :
(b) Cu 2 e Cu ; E o 0.15V (a) M (b) M/3
(c) M/5 (d) M/7
(c) 2H 2e H 2 ; E o 0.00V 40. The equivalent mass of oxidising agent in the following
reaction is
(d) Mg 2 2e Mg; Eo 2.37 V SO2 + 2H2S 3S + 2H2O
Based on the above data, state which of the following is (a) 32 (b) 64
the strongest reducing agent ? (c) 16 (d) 8
REDOX REACTIONS 25
41. In the following reaction : 47. Volume V1 mL of 0.1M K2Cr2O7 is needed for complete
oxidation of 0.678 g N2H4 in acidic medium. The volume of
NO3 As 2S3 H 2 O
AsO 4 3 NO SO 42 H 0.3 M KMnO4 needed for same oxidation in acidic medium
the equivalent weight of As2S3 (with molecular weight M) will be :
is: (a) 2/5 V1 (b) 5/2 V1
3M M (c) 113 V1 (d) Can not be determined
(a) (b)
28 4 48. 80 mL of KMnO4 solution reacts with 3.4 g of Na2 C2O4.2H2O
M M in acidic medium. The molarity of the KMnO4 solution is
(c) (d)
24 28 (a) 0.5 M (b) 0.1 M
42. Equivalent weight of H3PO2 (molecular weight = M) when it (c) 5 M (d) 1 M
disproportionates into PH3 and H3PO3 is
49. What weight of NaHSO3 is required to react with 100 mL of
M solution containing 0.33 g of NaIO3 according to the
(a) M (b)
2 following reaction
M 3M IO3 HSO 3
I SO 42
(c) (d)
4 4
(a) 0.52 g (b) 5.2 g
43. Equivalent weight of MnO 4 in acidic, neutral and basic
(c) 1.04 g (d) 10.4 g
media are in ratio of :
50. What volume of 0.05 M K2Cr2O7 in acidic medium is needed
(a) 3 : 5 : 15 (b) 5 : 3 : 1 for complete oxidation of 200 mL of 0.6 M FeC2O4 solution?
(c) 5 : 1 : 13 (d) 3 : 15 : 5 (a) 1.2 mL (b) 1.2 L
44. K2CrO4 oxidises KI in the presence of HCl to I 2. The (c) 120 mL (d) 800 mL
equivalent weight of the K2CrO4 is
51. KI reacts with H2SO4 producing I2 and H2S. The volume of
Mw 2 0.2 M H2SO4 required to produce 0.1 mol of H2S is
(a) (b) Mw (a) 4 L (b) 2.5 L
2 3
(c) 3.8 L (d) 5 L
Mw Mw Volume Strength of Hydrogen Peroxide
(c) (d)
3 6
52. 34 g of H2O2 is present in 1120 mL of solution. This solution
45. The equivalent weight of MnSO4 is half its molecular weight is called
when it is converted to (a) 10 vol solution (b) 20 vol solution
(a) Mn2O3 (b) MnO2 (c) 34 vol solution (d) 32 vol solution
53. A 5.0 mL solution of H2O2 liberates 1.27 g of iodine from an
(c) MnO 4 (d) MnO 4 2
acidified KI solution. The percentage strength of H2O2 is
Redox Titrations (a) 11.2 (b) 5.6
46. If equal volumes of 0.1 M KMnO4 and 0.1 M K2Cr2O7 (c) 1.7 (d) 3.4
solutions are allowed to oxidise Fe2+ to Fe3+ in acidic medium, 54. The volume strength of 1.5 N H2O2 solution is
then Fe2+ will be oxidised :
(a) 4.8 (b) 8.4
(a) More by KMnO4 (b) More by K2Cr2O7
(c) 3.0 (d) 8.0
(c) Equal in both cases (d) Cannot be determined.
REDOX REACTIONS 26
EXERCISE - 2 : PREVIOUS YEAR JEE MAIN QUESTIONS
1. The oxidation states of nitrogen in NO, NO2, N2O and NO3 (c) MnO 2 , ClO 2 , Cl 2 and Mn 3
are in the order of : (18-03-2021 Shift - 2)
(d) ClO 4 , MnO 4 , ClO 2 and F2
(a) NO NO 2 NO N 2 O
3
7. The exact volumes of 1 M NaOH solution required to
(b) N 2 O NO 2 NO NO 3 neutralise 50 mL of 1 M H3PO3 solution and 100 mL of 2 M
H3PO2 solution, respectively, are : (16-03-2021 Shift - 2)
(c) NO NO 2 N 2 O NO 3 (a) 100 mL and 100 mL (b) 100 mL and 50 mL
(d) NO 2 NO 3 NO N 2 O (c) 100 mL and 200 mL (d) 50 mL and 50 mL
8. The reaction of sulphur in alkaline medium is given below :
2. The species given below that does NOT show
2 2
disproportionation reaction is : (20-07-2021 Shift - 1) S8(s) aOHaq bS(aq) cS(aq) cS2 O3(aq) dH 2 O(l)
(a) BrO 4 (b) BrO- The values of ‘a’ is _______. (Integer answer)
(24-02-2021 Shift-1)
(c) BrO 2 (d) BrO3
9. In basic medium CrO24 oxidises S2 O 32 to form SO 24 and
3. The correct order of following 3d metal oxides, according to
their oxidation number is : (25-07-2021 Shift - 1) itself changes into Cr(OH)4. The volume of 0.154 M CrO 24
(A) CrO3 (B) Fe2O3 (C) MnO2 (D) V2O5 (E) Cu2O
required to react with 40 mL of 0.25 M S2 O 32 is _____ mL.
(a) (D) > (A) > (B) > (C) > (E)
(Rounded-off to the nearest integer)(25-02-2021 Shift-1)
(b) (A) > (C) > (D) > (B) > (E)
10. 0.4 g mixture of NaOH, Na2CO3 and some inert impurities
(c) (A) > (D) > (C) > (B) > (E)
N
(d) (C) > (A) > (D) > (E) > (B) was first titrated with HCl using phenolphthalein as an
10
4. Identify the process in which change in the oxidation state
indicator, 17.5 mL of HCl was required at the end point. After
is five : (25-07-2021 Shift - 2)
this methyl orange was added and titrated. 1.5 mL of same
2 3 2
(a) Cr2 O 7 2Cr (b) MnO Mn4 HCl was required for the next end point.The
weight percentage of Na2CO3 in the mixture is _______.
(c) CrO 24 Cr 3 (d) C 2 O 24 2CO 2 (Rounded-off to the nearest integer)(25-02-2021 Shift-1)
5. The oxidation states of ‘P’ in H4P2O7, H4P2O5 and H4P2O6 11. Consider titration of NaOH solution versus 1.25 M oxalic
respectively, are : (10-01-2019 Shift - 2) acid solution. At the end point following burette readings
(a) 7, 5 and 6 (b) 5, 4 and 3 were obtained.
(c) 5, 3 and 4 (d) 6, 4 and 5 (i) 4.5 mL (ii) 4.5 mL
6. In which one of the following sets all species show (iii) 4.4 mL (iv) 4.4 mL (v) 4.4 mL
disproportionation reaction? (31-08-2021 Shift - 2) If the volume of oxalic acid taken was 10.0 mL then the
molarity of the NaOH solution is _______ M. (Rounded-
(a) ClO 2 , F2 , MnO 4 and Cr2 O 72
off the nearest integer) (25-02-2021 Shift - 1)
(b) Cr2 O 72 , MnO 4 , ClO 2 and Cl 2
REDOX REACTIONS 27
12. Consider the following reaction 16. 10.0 mL of Na2CO3 solution is titrated 0.2 M HCl solution.
The following titre values wer obtained in 5 readings : 4.8
MnO 4 8H 5e Mn 2 4H 2 O, E o 1.51V
mL, 4.9 mL, 5.0 mL, 5.0 mL and 5.0 mL.
The quantity of electricity required in Faraday to reduce Based on these readings, and convention of titrimetric
five moles of MnO 4 is _____ . (26-02-2021 Shift - 1) estimation the concentration of Na2CO3 solution is ....... mM.
(Round off to the Nearest Integer). (18-03-2021 Shift - 2)
13. Dichromate ion is treated with base, the oxidation number
of Cr in the product formed is (26-02-2021 Shift - 1) 17. When 10 mL of an aqueous solution of Fe2+ ion was titrated
in the presence of dil. H2SO4 using diphenylamine indicator,
14. 2MnO 4 bC 2 O 24 cH xMn 2 yCO 2 zH 2 O
15 mL of 0.02 M solution of K2Cr2O7 was required to get the
If the above equation is balanced with integer coefficients, end point. The molarity of the solution containing Fe2+ ions
the value of c is ________. (Round off to the Nearest is x × 10-2 M. The value of x is _________. (Nearest Integer)
Integer) (16-03-2021 Shift-1) (25-07-2021 Shift - 1)
15. 15 mL of aqueous solution of Fe2+ in acidic medium 18. 10.0 mL of 0.05 M KMnO4 solution was consumd in a titration
completely reacted with 20 mL of 0.03 M aqueous Cr2 O 72 . with 10.0 mL of given oxalic acid dihydrate solution. The
strength of given oxalic acid solution is ...... × 10-2 g/L. (Round
The molarity of the Fe solution is ....... × 10 M. (Round
2+ -2
off to the narest integer) (25-07-2021 Shift - 1)
off to the Nearest Integer) (17-03-2021 Shift-1)
19. When 10 mL of an aqueous solution of KMnO4 was titrated
in acidic medium, equal volume of 0.1 M of an aqueous
solution of ferrous sulphate was required for complete
discharge of colour. The strength of KMnO4 in grams per
litre is _______× 10-2. (Nearest integer)
[Atomic mass of K = 39, Mn = 55, O = 16]
(27-08-2021 Shift - 1)
REDOX REACTIONS 28
20. Which one of the following is an example of 25. In neutral or faintly alkaline medium, KMnO4 being a
disproportionation reaction? (JEE Main 2022) powerful oxidant can oxidize, thiosulphate almost
(a) 3MnO42– + 4H+ → 2MnO4– + MnO2 + 2H2O quantitatively, to sulphate. In this reaction overall
(b) MnO4– + 4H+ + 4e– → MnO2 + 2H2O change in oxidation state of manganese will be :
(c) 10I– + 2MnO4– + 16H+ → 2Mn2+ + 8H2O + 5I2 (JEE Main 2022)
(d) 8MnO4– + 3S2O32– + H2O → 8MnO2 + 6SO42– + (a) 5 (b) 1
2OH– (c) 0 (d) 3
21. Which of the given reactions is not an example of 26. A 2.0 g sample containing MnO2 is treated with HCl
disproportionation reaction? (JEE Main 2022) liberating Cl2. The Cl2 gas is passed into a solution of
(a) 2H2O2 → 2H2O + O2 KI and 60.0 mL of 0.1 M Na2S2O3 is required to titrate
(b) 2NO2 + H2O → HNO3 + HNO2 the liberated iodine. The percentage of MnO2 in the
(c) MnO
+ 4H+ + 3e– → MnO2 + 2H2O sample is ____. (Nearest integer)
4
[Atomic masses (in u) Mn = 55; Cl = 35.5: O = 16, I =
2
(d) 3MnO 4 + 4H+ → 2MnO4– + MnO2 + 2H2O 127, Na = 23, K = 39, S = 32] (JEE Main 2022)
22. Which of the following has least tendency to liberate 27. 0.01 M KMnO4 solution was added to 20.0 mL of 0.05
H2 from mineral acids? (JEE Main 2022) M Mohr's salt solution through a burette. The initial
(a) Cu (b) Mn reading of 50 mL burette is zero. The volume of
(c) Ni (d) Zn KMnO4 solution left in the burette after the end point
23. For kinetic study of the reaction of iodide ion with is ____ ml. (nearest integer) (JEE Main 2022)
H2O2 at room temperature: 28. 20 mL of 0.02 M hypo solution is used for the titration
(A) Always use freshly prepared starch solution. of 10 mL of copper sulphate solution, in the presence
(B) Always keep the concentration of sodium of excess of KI using starch as an indicator. The
thiosulphate solution less than that of KI solution. molarity of Cu2+ is found to be _____ × 10–2 M
(C) Record the time immediately after the appearance [nearest integer]
of blue colour. Given: 2Cu2+ + 4I– → Cu2I2 + I2
(D) Record the time immediately before the I2 + 2S2O32– → 2I– + S4O62– (JEE Main 2022)
appearance of blue colour. 29. 20 mL of 0.02 M K2Cr2O7 solution is used for the
(E) Always keep the concentration of sodium titration of 10 mL of Fe2+ solution in the acidic
thiosulphate solution more than that of KI medium.
solution. The molarity of Fe2+ solution is ______ × 10–2 M.
Choose the correct answer from the options given (Nearest Integer) (JEE Main 2022)
below: (JEE Main 2022) 30. In the titration of KMnO4 and oxalic acid in acidic
(a) (A), (B), (C) only medium, the change in oxidation number of carbon at
(b) (A), (D), (E) only the end point is_____ (JEE Main 2022)
(c) (D), (E) only 31. On reaction with stronger oxidizing agent like KIO4,
(d) (A), (B), (E) only hydrogen peroxide oxidizes with the evolution of O2.
24. Given below are two statements : One is labelled The oxidation number of I in KIO4 changes to ______.
as Assertion A and the other is labelled as Reason R (JEE Main 2022)
Assertion A: Permanganate titrations are not 32. Which one amongst the following are good oxidizing
performed in presence of hydrochloric acid. agents?
Reason R: Chlorine is formed as a consequence of A. Sm 2
oxidation of hydrochloric acid. B. Ce2
In the light of the above statements, choose
C. Ce4
the correct answer from the options given below
(JEE Main 2022) D. Tb4
(a) Both A and R are true and R is the correct Choose the most appropriate answer from the options
explanation of A given below : (JEE Main 2023)
(b) Both A and R are true but R is NOT the correct (a) C only (b) D only
explanation of A (c) A and B only (d) C and D only
(c) A is true but R is false
(d) A is false but R is true
REDOX REACTIONS 29
33. An indicator ‘X’ is used for studying the effect of 38. A metal chloride contains 55.0% of chlorine by
variation in concentration of iodide on the rate of weight. 100 mL vapours of the metal chloride at STP
reaction of iodide ion with H 2 O2 at room temp. The weight 0.57 g. The molecular formula of the metal
indicator ‘X’ forms blue colored complex with chloride is
compound ‘A’ present in the solution. The indicator (Given: Atomic mass of chlorine is 35.5u)
‘X’ and compound ‘A’ respectively are (JEE Main 2023)
(JEE Main 2023) (a) MCl (b) MCl2
(a) Starch and iodine (c) MCl3 (d) MCl4
(b) Methyl orange and H 2 O2 39. Zinc reacts with hydrochloric acid to give hydrogen
(c) Starch and H 2 O2 and zinc chloride. The volume of hydrogen gas
(d) Methyl orange and iodine produced at STP from the reaction of 11.5 g of zinc
with excess HCl is ______ L (Nearest integer)
34. When Cu 2 ion is treated with KI, a white precipitate,
(Given: Molar mass of Zn is 65.4 g mol –1 and Molar
X appears in solution. The solution is titrated with
sodium thiosulphate, the compound Y is formed. X volume of H 2 at STP = 22.7L) (JEE Main 2023)
and Y respectively are (JEE Main 2023) 40. In ammonium – Phosphomolybdate, the oxidation
(a) X Cu2 I 2 , Y Na2 S 4 O5 state of Mo is + _____ (JEE Main 2023)
(b) X Cu2 I 2 , Y Na2 S4 O6 41. The sum of oxidation state of the metals in
(c) X CuI 2 , Y Na2 S4 O3 Fe CO 5 , VO2 and WO3 is _____
(d) X CuI 2 , Y Na2 S 4 O6 (JEE Main 2023)
42. In alkaline medium, the reduction of permanganate
35. During the reaction of permanganate with
anion involves a gain of _____ electrons.
thiosulphate, the change in oxidation of manganese
(JEE Main 2023)
occurs by value of 3. Identify which of the below
43. In Chromyl chloride, the oxidation state of chromium
medium will favour the reaction. (JEE Main 2023)
is (+) ______ (JEE Main 2023)
(a) aqueous acidic
44. The total change in the oxidation state of manganese
(b) aqueous neutral
involved in the reaction of KMnO4 and potassium
(c) both aqueous acidic and neutral
(d) both aqueous acidic and faintly alkaline iodide in the acidic medium is ______
36. 2 IO3 – xI – 12 H 6 I 2 6 H 2 O (JEE Main 2023)
45. 20 mL of calcium hydroxide was consumed when it
What is the value of x ? (JEE Main 2023)
was reacted with 10 mL of unknown solution of
(a) 12 (b) 6
H 2 SO4 . Also 20 mL standard solution of 0.5 M HCl
(c) 10 (d) 2
37. Given below are two statements: containing 2 drops of phenolphthalein was titrated
Statement I: In redox titration, the indicators used are with calcium hydroxide, the mixture showed pink
sensitive to change in pH of the solution. colour when burette displayed the value of 35.5 mL
Statement II: In acid-base titration, the indicators whereas the burette showed 25.5 mL initially. The
used are sensitive to change in oxidation potential. concentration of H 2 SO4 is ___________ M. (Nearest
In the light of the above statements, choose the most integer) (JEE Main 2023)
appropriate answer from the options given below. 46. KMnO4 is titrated with ferrous ammonium sulphate
(JEE Main 2023) hexahydrate in presence of dilute H 2 SO4 . Number of
(a) Statement I is incorrect but Statement II is correct
water molecules produced for 2 molecules of KMnO4
(b) Both Statement I and Statement II are incorrect
(c) Statement I is correct but Statement II is incorrect is ______ (JEE Main 2023)
(d) Both Statement I and Statement II are correct 47. See the following chemical reaction:
Cr2 O72 XH 6 Fe 2 YCr 3 6 Fe 3 ZH 2 O
The sum of X, Y and Z is ___. (JEE Main 2023)
REDOX REACTIONS 30
EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS
Objective Questions I [Only One Correct Option] (d) none of the above
8. A bottle of H2O2 is labelled as 10 vol H2O2. 112 mL of this
1. In the reaction, 2FeCl3 + H2S
2FeCl2 + 2HCl + S solution of H2O2 is titrated against 0.04 M acidified solution
(a) FeCl3 acts as an oxidizing agent of KMnO4. The volume of KMnO4 in litre is
(b) Both H2S and FeCl3 are oxidized (a) 1 L (b) 2 L
(c) FeCl3 is oxidised while H2S is reduced (c) 3 L (d) 4 L
(d) H2S acts as an oxidizing agent 9. Which of the following is a redox reaction?
2. When KMnO4 reacts with acidified FeSO4 (a) H2SO4 with NaOH
(a) Only FeSO4 is oxidised (b) In atmosphere, O3 from O2 by lightning
(b) Only KMnO4 is oxidised (c) Nitrogen oxides from nitrogen and oxygen by lightning
(c) FeSO4 is oxidised and KMnO4 is reduced (d) Evaporation of H2O
(d) None of the above 10. Phosphorus has the oxidation state of + 3 in
3. The oxidation number of cobalt in K3[Co(NO2)6] is (a) Phosphorous acid
(a) 0 (b) + 4 (b) Orthophosphoric
(c) + 3 (d) + 6 (c) Hypophosphorous acid
4. For the redox reaction, (d) Metaphosphoric acid
MnO 4 C2 O42 H Mn 2 CO 2 H 2 O 11. In a chemical reaction
the correct coefficients of the reactions for the balanced K2Cr2O7 xH2SO4 ySO2 K2SO4 Cr2 (SO4 )3 zH2O ;
reaction are respectively MnO4 , C2 O4 , H : the value of x, y and z respectively are:
(a) x = 1, y = 3, z = 1 (b) x = 4, y = 1, z = 4
(a) 2, 5, 16 (b) 16, 3, 12
(c) x = 3, y = 2, z = 1 (d) x = 2, y = 2, z = 1
(c) 15, 16, 12 (d) 2, 16, 5
12. 1 mole of equimolar mixture of ferric oxalate and ferrous
5. In the reaction between SO2 and O3 , the equivalent weight
oxalate will require x mole of KMnO4 in acidic medium for
of ozone is :
complete oxidation, x is:
(a) The same as its molecular weight
(a) 0.5 mole (b) 0.9 mole
(b) Half the molecular weight
(c) 1.2 mole (d) 4.5 mole
(c) One – third of the molecular weight
13. 20 mL of 0.2 M NaOH (aq) solution is mixed with 35 mL of 0.1
(d) One – fourth of the molecular weight M NaOH (aq) solution and the resultant solution is diluted
6. In the reaction, 8Al 3Fe3O 4 4Al 2 O3 9Fe , the number to 100 mL. 40 mL of this diluted solution reacted with 10%
impure sample of oxalic acid (H2C2O4). The weight of impure
of electrons transferred from reductant to oxidant is:
sample is:
(a) 8 (b) 4
(a) 0.15 gram (b) 0.135 gram
(c) 7 (d) 24
(c) 0.59 gram (d) None of these
2 o
7. If Sn 2e Sn; E 0.14 V 14. 32 g of a sample of FeSO4.7H2O were dissolved in dilute
sulphuric acid and water and its volume was made up to 1
Sn 4 2e Sn 2 ; E o 0.13 V then: litre, 25 mL of this solution required 20 mL of 0.02 M KMnO4
(a) Sn2+ will disproportionates to Sn4+and Sn solution for complete oxidation. Calculate the weight % of
FeSO4.7H2O in the sample.
(b) Sn2+ is stable and it will not disproportionate
(a) 34.75 (b) 69.5
(c) Sn4+ is easily reduced to Sn
(c) 89.5 (d) None of these
REDOX REACTIONS 31
15. 125 mL of 63% (w/v) H2C2O4 . 2H2O solution is made to react Objective Questions II
with 125 mL of a 40% (w/v) NaOH solution. The resulting
solution is : (ignoring hydrolysis of ions)
[One or more than one correct option]
21. Which of the following can act both as an oxidising as well
(a) Neutral (b) Acidic
as reducing agent :
(c) Strongly acidic (d) Alkaline
(a) HNO2 (b) H2O2
16. An element A in a compound ABD has oxidation number – (c) H2S (d) SO2
n. It is oxidised by Cr2O72– in acidic medium. In the experiment,
22. In an electrochemical cell, a salt bridge is used:
1.68 × 10–3 moles of K2Cr2O7 were used for 3.36 × 10–3 moles
of ABD. The new oxidation number of A after oxidation is : (a) to avoid mechanical contact of electrolyte solution in
cathodic and anodic half-cell
(a) 3 (b) 3 – n
(b) to maintain electrical neutrality in the cell
(c) n –3 (d) + n
(c) to avoid liquid junction potential
17. Which of the following solutions will exactly oxidize 25 mL (d) to mix the solution of anodic and cathodic half-cell
of an acid solution of 0.1 M iron (II) oxalate :
23. Which of the following reactions do not involve oxidation
(a) 10 mL of 0.25 M KMnO4 or reduction:
(b) 25 mL of 0.2 M KMnO4 (a) 2 Rb + 2H2O
2 RbOH + H2
(c) 25 mL of 0.6 M KMnO4
(b) 2CuI2
2 CuI + I2
(d) 15 mL of 0.1 M KMnO4
(c) NH4Cl + NaOH
NaCl + NH3 + H2 O
18. In the reaction of sodium thiosulphate with I2 in aqueous
(d) 4 KCN + Fe(CN)2 K4[Fe(CN)6]
medium the equivalent weight of sodium thiosulphate is
24. When Cl2 reacts with aqeous NaOH in cold condition then
equal to:
oxidation number of chlorine changes from 0 to:
(a) molar mass of sodium thiosulphate
(a) -1 (b) +1
(b) the average molar masses of Na2S2O3 and I2
(c) -2 (d) +2
(c) half the molar masss of sodium thiosulphate 25. In the reaction
(d) twice of molar mass of sodium thiosulphate
I 2 C2H5OH OH CHI3 HCOO H 2O I
19. Based on the following information arrange four metals A, which of the following statements is/are correct?
B, C and D in order of decreasing ability to act as reducing
(a) The coefficients of OH and I in the given in balanced
agents:
equation are, respectively, 6 and 5.
(I) Only A, B and C react with 1 M HCl to give H2 (g)
(b) The coefficients of OH and I in the given balanced
(II) When C is added to solutions of the other metal ions, equation are, respectively, 5 and 6.
metallic B and D are formed (c) C 2 H 5 OH is oxidised to CHI3 and HCOO
(III) Metal C does not reduce A . n+
(d) The number of electrons in the conversion of C 2 H 5 OH
(a) C > A > B > D (b) C > A > D > B to CHI3 and HCOO is 8.
(c) A > C > D > B (d) A > C > B > D 26. When a equimolar mixture of Cu2S and CuS is titrated with
20. A mixture of FeO and Fe2O3 is completely reacted with 100 Ba(MnO4)2 in acidic medium, the final product’s contains
mL of 0.25 M acidified KMnO4 solution. The resultant Cu2+, SO2 and Mn2+. If the mol. wt. of Cu2S, CuS and
solution was then titrated with Zn dust which converted Ba(MnO4)2 are M1, M2 and M3 respectively then:
Fe3+ of the solution of Fe2+. The Fe2+ required 1000 mL of M1
(a) eq. wt. of Cu2S is
0.10 M K2Cr2O7 solution. Find out the weight % Fe2O3 in the 8
mixture. M2
(a) 80.85 (b) 19.15 (b) eq. wt. of CuS is
6
(c) 50 (d) 89.41 M3
(c) eq. wt. of Ba(MnO4)2 is
5
(d) Cu2S and CuS both have same equivalents in mixture
REDOX REACTIONS 32
27. Identify the correct statements with reference to the given Numerical Value Type Questions
reaction, P4 3OH H 2 O PH3 3H 2 PO2 32. In the reaction : Na2S2O3 + 4Cl2 + 5H2O Na2SO4 +
(a) Phosphorus is undergoing reduction only H2SO4 + 8HCl, the equivalent weight of Na2S2O3 will be : (M
(b) Phosphorus is undergoing oxidation only = molecular weight of Na2S2O3)
(c) Phosphorus is undergoing oxidation as well as reduction. 33. It requires 40 mL of 1 M Ce4 + to titrate 20 mL of 1M Sn2+ to
Sn4+. What is the oxidation state of the Cerium in the
(d) Hydrogen is undergoing neither oxidation nor reduction
product?
28. 25 mL of 0.5 M H2O2 solution is added to 50 mL of 0.2 M
KMnO4 in acid solution. Which of the following statements 34. Oxidation number of chlorine in NOClO4 is ...............
is false : 35. In the redox reaction,
(a) 0.010 mole of oxygen gas is liberated. xNO3 y As 2S3 zH 2 O AsO 43 NO SO 4 2 H
(b) 0.005 mole of KMnO4 is left. x
What is the value of ?
(c) 0.030 g of oxygen gas is evolved. z
(d) 0.0025 mole H2O2 does not react with KMnO4. 36. A volume of 12.5 mL of 0.05 M SeO2 reacts with 25mL of
0.1M CrSO4 which is oxidised to Cr3+. To what oxidation
29. In the following reaction : Cr(OH)3 + OH– + IO3– CrO42– +
state was the selenium converted by the reaction?
H 2O + I –
(a) IO3 – is oxidising agent 37. 20 mL of H2O2 after acidification with dilute H2SO4 required
30 mL of N/12 KMnO4 for complete oxidation. The strength
(b) Cr(OH)3 is oxidised
of H2O2 solution is in g/L : [Molar mass of H2O2 = 34]
(c) 6e– are being taken per iodine atom
38. A sample of 28 mL of H2O2 (aq) solution required 10 mL of
(d) None of these 0.1 KMnO4 (aq) solution for complete reaction in acidic
30. 500 mL of a 0.05 M Mohr salt solution required the same medium. What is the volume strength of H2O2?
volume of permanganate solution for complete oxidation. Assertion Reason
Which of the followings is (are) true regarding the above
redox reaction? (A) If both Assertion and Reason are correct and
(a) The molarity of KMnO4 must be 0.01 M if the medium is Reason is the correct explanation of Assertion.
acidic (B) If both Assertion and Reason are true but
(b) The molarity of KMnO4 must be 1 M if the medium is Reason is not the correct explanation of
basic. Assertion.
(c) The medium has no role to play in redox reaction.
(C) If Assertion is true but Reason is false.
(d) In the above reaction Fe(II) is oxidized to Fe(III)
irrespective of medium. (D) If Assertion is false but Reason is true.
39. Assertion (A) : KO2 is superoxide.
31. Given that, E Ni2 / Ni – 0.25V, E°Cu 2 /Cu 0.34V
Reason (R) : Oxidation state of oxygen of KO2 is – 2.
o o (a) A (b) B
E Ag 2 / Ag
0.80 V, E Zn 2 / Zn
0.76 V
(c) C (d) D
Which of the following redox processes will not take place
in specified direction? 40. Assertion (A) : MnO2 can act as an oxidizing agent as well
as reducing agent.
(a) Ni 2 (aq) Cu (s) Ni (s) Cu 2 (aq)
Reason (R) : Oxidation state of Mn lies between highest
2 and lowest oxidation state.
(b) Cu(s) 2Ag (aq) Cu (aq) 2Ag(s)
(a) A (b) B
2
(c) Cu (s) 2H (aq) Cu (aq) H 2 (g) (c) C (d) D
(d) Zn(s) 2H (aq) Zn 2 (aq) H 2 (g)
REDOX REACTIONS 33
41. Assertion (A) : F2 does not undergo disproportionation 45. Match the reaction in column 1 with the coefficients x and y
reactions. given in column II.
Reason (R) : Fluorine shows only 0 and – 1 oxidation states. Column - I Column - II
(a) A (b) B (Reaction) (The coefficients
of x and y are)
(c) C (d) D
(A) xCu yHNO3 Cu(NO3 ) 2 (p) 2 and 6
42. Assertion (A) : White phosphorous reacts with aqueous
caustic soda to form PH 3 and NaH 2 PO 2 . It is NO NO 2 H 2 O
disproportionation reaction. (B) xKI yBaCrO 4
H
(q) 6 and 2
Reason (R) : In the reaction of disproportionation, same I 2 CrCl3
substance is oxidised as well as reduced simultaneously. (C) xAs S yNO (r) 3 and 28
2 3 3
3 2
(a) A (b) B AsO4 NO SO4
(c) C (d) D (D) 4P 3OH 3H O (s) 1 and 3
2
xPH 3 yH 2 PO 2
43. Assertion (A) : If 1.50 mol of KMnO4 is required for oxidation
in acidic medium, 2.50 mol of KMnO4 would be required for (E) xKI yH 2SO 4 (t) 8 and 5
same oxidation but in basic medium. I 2 H 2S K 2SO 4
Reason (R) : In acidic medium, oxidation state of Mn changes 46. Column - I Column - II
from +7 to +2, while is basic medium , it changes from +7 to Molecular weight
(A) Eq. wt. (p) When CrI3 oxidises
+4. 33
(a) A (b) B into Cr2 O7 2 and IO4
(c) C (d) D Molecular weight
(B) Eq. wt. (q) When Fe(SCN)2
Match the following 27
Each questions has two columns. Four options are oxidises into Fe3+,
given representing matching elements from SO42 , CO32 ,
Column-I and Column-II. and NO3
44. Column - I Column - II Molecular weight
(C) Eq. wt. (r) When NH4SCN
(Redox reaction) (molar ratio of reducing to 28
oxidising agent) oxidizes into
(A) CIO Fe(OH)2 (p) 3 : 2 SO42 , CO32 and
Cl Fe(OH)3 NO3
(B) Cr2 O7 2 FeC2 O 4 (q) 2 : 1 Molecular weight
(D) Eq. wt. (s) When As2S3
Cr 3 CO 2 Fe3 24
(C) H 2 O 2 Cr(OH)3 (r) 1 : 3 oxidises into AsO3
CrO 4 2 H 2 O
and SO42
(D) N 2 H 4 Cu(OH) 2 (s) 2 : 3
47. Column - I Column - II
N 2 O Cu
3M
(E) MnO 4 C2 O 4 2 (A) P2 H 4 PH3 P4 H 2 (p) E
MnO 2 CO 2 4
(q) E 3M
(B) I 2 I IO3
5
(C) MnO 4 Mn 2 H 2 O (r) E 15M
26
Mn 3 O 4 H
5M
(D) H3PO2 PH3 H3 PO3 (s) E
6
REDOX REACTIONS 34
Paragraph type questions Example 2
Use the following passage, solve Q.48 to Q.50 FeC 2O 4 Fe3 2CO 2
Passage Total no. of moles of e– lost by 1 mole of FeC2O4
The valency of carbon is generally 4, but its oxidation state =1+1×2 3
may be -4, -2, 0, 2, -1 etc. In the compounds containing C, H
and O, the oxidation number of C is calculated as n-factor of FeC2O4 = 3
51. n-factor of Ba(MnO4)2 in acidic medium is
2n O n H
Oxidation number of C = (a) 2 (b) 6
nC
(c) 10 (d) None of these
where nO, nH, nC are the number of oxygen, hydrogen, and 52. For the reaction,
carbon atoms, respectively.
H 3 PO 2 NaOH NaH 2 PO 2 H 2 O
What is the equivalent weight of H3PO2? (mol. wt. is M)
48. In which of the following compounds is the oxidation state (a) M (b) M/2
of C a fraction? (c) M/3 (d) None of these
(a) CO (b) CO2 53. For the reaction, Fe0.95 O (molar mass: M) Fe2O3. What is
the eq. wt. of Fe0.95 O ?
(c) Carbon suboxide (d) All
49. In which of the following compounds the oxidation state of M M
(a) (b)
C is 2? 0.85 0.95
(a) Ketenes (b) Alkenes M
(c) (d) None of these
(c) Allenes (d) Carbenes 0.8075
Use the following passage, solve Q.54 to Q.55
50. In which of the following compounds is the oxidation state
of C highest? Passage
(a) HCOOH (b) HCHO The next two questions deal with an experiment. An unknown
(c) CH3OH (d) CH4 metal ‘X’ is found to react spontaneously with 1.0M solution
of CuSO4 plating out Cu(s). X does not react with a solution
Use the following passage, solve Q.51 to Q.53 of 1.0M Zn(NO3)2. The half-reactions for these metals are:
Passage X 2 (aq) 2e
X(s)
Molecular weight / Atomic weight Cu 2 (aq) 2e
Cu
Equivalent weight =
n factor Zn 2 (aq) 2e
Zn
n-factor is very important in redox as well as non-redox 54. What is the correct order for listing the metals according to
reactions. With the help of n-factor we can predicts the decreasing strength as reducing agent ?
molar ratio of the reactant species taking part in reactions.
(a) X, Cu, Zn (b) Cu, Zn, X
The reciprocal of n-factor’s ratio of the reactants is the molar
ratio of the reactants. (c) Cu, X, Zn (d) Zn, X, Cu
In general n-factor of acid/base is number of moles of 55. Another metal Y displaces Cu2+ from its aqueous solution
H+/OH– furnished per mole of acid/base. n-factor of a but can’t displace Zn2+ from its aqueous solution. Which of
reactant is no. of moles of electrons lost or gained per mole the following statements regarding X and Y is correct?
of reactant. (a) X is stronger reducing agent than Y
Example 1 (b) X is weaker reducing agent than Y
(c) Both X and Y are weaker reducing agents than Cu
1. In acidic medium : KMnO 4 (n 5) Mn 2
(d) X can be either stronger or weaker reducing agent than
2
2. In neutral medium : KMnO 4 (n 3) Mn Y.
3. In basic medium : KMnO 4 (n 1) Mn 6
REDOX REACTIONS 35
EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTIONS
(a) 0, +1 and -2 (b) +2, +1 and -2
Objective Questions I [Only one correct option]
(c) 0, +1 and +2 (d) -2, +1 and -2
1. The equivalent weight of MnSO4 is half of its molecular
weight when it converts to (1988) 8. Among the following, the species in which the oxidation
number of an element is +6 (2000)
(a) Mn2O3 (b) MnO2
(a) MnO 4 (b) Cr(CN) 36
(c) MnO 4 (d) MnO 24
2. The volume strength of 1.5 N H2O2 is (1990) (c) NiF62 (d) CrO2Cl2
(a) 4.8 (b) 8.4 9. An aqueous solution of 6.3 g oxalic acid dihydrate is made
(c) 3.0 (d) 8.0 up to 250 mL. The volume of 0.1 N NaOH required to
completely neutralize 10 mL of this solution is (2000)
3. For the redox reaction
(a) 40 mL (b) 20 mL
MnO 4 C 2 O 24 H Mn 2 CO 2 H 2 O
(c) 10 mL (d) 4 mL
The correct coefficients of the reactants for the balanced
10. The reaction, 3ClO(aq)
ClO 3 (aq) 2Cl(aq) is an
reaction are
example of (2001)
MnO 4 C2 O 42 H+ (1992)
(a) oxidation reaction
(a) 2 5 16
(b) reduction reaction
(b) 16 5 2
(c) disproportionate reaction
(c) 5 16 2
(d) decomposition reaction
(d) 2 16 5
11. In the standardization of Na 2S 2O 3 and K 2Cr 2 O 7 by
4. The number of moles of KMnO4 that will be needed to iodometry, the equivalent weight of K2Cr2O7 is (2000)
react with one mole of sulphite ion in acidic solution
(a) (molecular weight)/2
(1997)
(b) (molecular weight)/6
2 3
(a) (b) (c) (molecular weight)/3
5 5
(d) same as molecular weight
4
(c) (d) 1 12. Consider a titration of potassium dichromate solution with
5
acidified Mohr’s salt solution using diphenylamine as
5. The number of moles of KMnO4 that will be needed to
indicator. The number of moles of Mohr’s salt required per
react completely with one mole of ferrous oxalate in acidic
mole of dichromate is (2007)
medium is (1997)
(a) 3 (b) 4
2 3
(a) (b) (c) 5 (d) 6
5 5
13. Which ordering of compounds is according to the
4 decreasing order of the oxidation state of nitrogen ?
(c) (d) 1
5
(2012)
6. The normality of 0.3 M phosphorus acid (H3PO3) is
(a) HNO3, NO, NH4Cl, N2
(a) 0.1 (b) 0.9 (1999) (b) HNO3, NO, N2, NH4Cl
(c) 0.3 (d) 0.6 (c) HNO3, NH4Cl, NO, N2
7. The oxidation number of sulphur in S 8 , S 2 F 2 , H 2 S (d) NO, HNO3, NH4Cl, N2
respectively, are (1999)
REDOX REACTIONS 36
14. The reaction of white phosphorus with aqueous NaOH Fill in the Blank
gives phosphine along with another phosphorus
18. The compound YBa 2 Cu 3 O 7 , which shows super
containing compound. The reaction type; the oxidation
conductivity, has copper in oxidation state..................
states of phosphorus in phosphine and the other product
Assume that the rare earth element yttrium is in its usual +3
are respectively (2013)
oxidation state. (1994)
(a) redox reaction; –3 and – 5
Numerical Value Type Questions
(b) redox reaction; 3 and + 5
19. A student performs a titration with different burettes and
(c) disproportionation reaction; –3 and +5
finds titre values of 25.2 mL, 25.25 mL, and 25.0 mL. number
(d) disproportionation reaction; –3 and + 3 of significant figures in the average titre value is (2010)
15. For the reaction : (2016) 20. Among the following, the number of elements showing only
one non-zero oxidation state is O, Cl, F, N, P, Sn, Tl, Na, Ti
(2010)
The correct statement(s) in the balanced equation is/are: 21. The difference in the oxidation numbers of the two types of
sulphur atoms in Na2S4O6 is (2011)
(a) Stoichiometric coefficient of HSO4– is 6.
Subjective Type Questions
(b) Iodide is oxidized
22. The density of a 3 M sodium thiosulphate solution
(c) Sulphur is reduced (Na2S2O3) is 1.25 g per mL. Calculate (i) the percentage by
(d) H2O is one of the products. weight of sodium thiosulphate (ii) the mole fraction of
16. The order of the oxidation state of the phosphorus atom in sodium thiosulphate and (iii) the molalities of Na+ and
H 3 PO 2 , H 3 PO 4 , H 3 PO3 , and H 4 P2 O 6 is (2017) S2 O 32 ions. (1983)
23. 4.08 g of a mixture of BaO and unknown carbonate MCO3
(a) H 3 PO3 H 3 PO 2 H 3 PO 4 H 4 P2 O6
was heated strongly. The residue weighed 3.64 g. This was
(b) H 3 PO 4 H 3 PO 2 H 3 PO3 H 4 P2 O6 dissolved in 100 mL of 1 N HCl. The excess acid required 16
mL of 2.5 N NaOH solution for complete neutralization.
(c) H 3 PO 4 H 4 P2 O6 H 3 PO3 H 3 PO 2 Identify the metal M. (1983)
24. 2.68 × 10–3 moles of a solution containing an ion An+ require
(d) H 3 PO 2 H 3 PO3 H 4 P2 O6 H 3 PO 4
1.61 × 10–3 moles of MnO4– for the oxidation of An+ to AO3 in
Assertion Reason acidic medium. What is the value of n? (1984)
(a) Assertion is true; Reason is true; Reason is the 25. A sample of hydrazine sulphate (N2H6SO4) was dissolved
correct explanation of Assertion. in 100 mL of water, 10 mL of this solution was reacted with
excess of ferric chloride solution and warmed to complete
(b) Assertion is true; Reason is true; Reason is not
the reaction. Ferrous ion formed was estimated and it,
the correct explanation of Assertion. required 20 mL of M/50 potassium permanganate solution.
(c) Assertion is true; Reason is false. Estimate the amount of hydrazine sulphate in one litre of
the solution (1984)
(d) Assertion is false; Reason is true.
Reaction:
17. Assertion (A): In the titration of Na2CO3 with HCl using
methyl orange indicator, the volume required at the 4Fe3 N 2 H 4 N 2 4Fe 2 4H
equivalence point is twice that of the acid required using MnO4 5Fe2 8H Mn2 5Fe3 4H2O
phenolphthalein indicator.
26. 5 mL of 8 N nitric acid, 4.8 mL of 5 N hydrochloric acid and
Reason(R) : Two moles of HCl are required for the complete a certain volume of 17 M sulphuric acid are mixed together
neutralization of one mole of Na2CO3. (1991) and made up to 2 L. 30 mL of this acid mixture exactly
(a) A (b) B neutralise 42.9 mL of sodium carbonate solution containing
(c) C (d) D one gram of Na2CO3.10H2O in 100 mL of water. Calculate the
amount in gram of the sulphate ions in solution. (1985)
REDOX REACTIONS 37
27. An equal volume of a reducing agent is titrated separately 33. One gram of commercial AgNO3 is dissolved in 50 mL of
with 1M KMnO4 in acid, neutral and alkaline medium. The water. It is treated with 50 mL of a KI solution. The silver
volumes of KMnO4 required are 20 mL in acid, 33.3 mL in iodide thus precipitated is filtered off. Excess of KI in the
neutral and 100 mL in alkaline media. Find out the oxidation filtrate is titrated with (M/10) KIO3 solution in presence of 6
state of mangnese in each reduction product. Give the M HCl till all I– ions are converted into ICl. It requires 50 mL
balanced equations for all the three half reaction. Find out of (M/10) KIO3 solution. 20 mL of the same stock solution
the volume of 1M K2Cr2O7 consumed, if the same volume of of KI requires 30 mL of (M/10) KIO3 under similar conditions.
the reducing agent is titrated in acid medium. (1989) Calculate the percentage of AgNO3 in the sample.
28. An organic compound X on analysis gives 24.24 per cent Reaction :
carbon and 4.04 per cent hydrogen. Further, sodium extract
of 1.0 g of X gives 2.90 g of silver chloride with acidified KIO 3 2KI 6HCl 3ICl 3KCl 3H 2 O (1992)
silver nitrate solution. The compound X may be represented 34. A 5.0 cm3 solution of H2O liberates 0.508 g of iodine from an
by two isomeric structures Y and Z. Y on treatment with acidified KI solution. Calculate the strength of H2O 2
aqueous potassium hydroxide solution gives a dihydroxy solution in terms of volume strength at STP (1995)
compound while Z on similar treatment gives ethanal. Find 35. A 20.0 cm3 mixture of CO, CH4 and He gases is exploded by
out the molecular formula of X and gives the structure of Y an electric discharge at room temperature with excess of
and Z. (1989) oxygen. The volume contraction is found to be 13.0 cm3. A
29. A mixture of H2C2O4 (oxalic acid) and NaHC2O4 weighing further contraction of 14.0 cm3 occurs when the residual
2.02 g was dissolved in water and the solution made up to gas is treated with KOH solution. Find out the composition
one litre. Ten millilitres of the solution required 3.0 mL of 0.1 of the gaseous mixture in terms of volume percentage.
N sodium hydroxide solution for complete neutralization. (1995)
In another experiment, 10.0 mL of the same solution, in hot
36. A 3.00 g sample containing Fe3O4, Fe2O3 and an inert impure
dilute sulphuric acid medium, required 4.0 mL of 0.1 N
substance, is treated with excess of KI solution in presence
potassium permanganate solution for complete reaction.
of dilute H2SO4. The entire iron is converted into Fe2+ along
Calculate the amount of H2C2O4 and NaHC2O4 in the mixture.
with liberation of idoine. The resulting solution is diluted
(1990)
to 100 mL. A 20 mL of the dilute solution requires 11.0 mL of
30. A solution of 0.2 g of a compound containing Cu2+ and
0.5 M Na2S2O3 solution to reduce the iodine present. A 50
C2 O 42 ions on titration with 0.02 M KMnO4 in presence of mL of the dilute solution, after complete extraction of the
H2SO4 consumes 22.6 mL of the oxidant. The resultant iodine required 12.80 mL of 0.25 M KMnO4 solution in
solution is neutralized with Na2CO3 , acidified with dilute dilute H2SO4 medium for the oxidation of Fe2+. Calculate the
acetic acid and treated with excess KI. The liberated iodine percentage of Fe2O3 and Fe3O4 in the original sample.
requires 11.3 mL of 0.05 M Na2S2O3 solution for complete (1996)
reduction. Find out the mole ratio of Cu2+ to C2 O 42 in the 37. To a 25 mL H2O2 solution, excess of acidified solution of
potassium iodide was added. The iodine liberated required
compound. Write down the balanced redox reactions
20 mL of 0.3 N sodium thiosulphate solution. Calculate the
involved in the above titrations. (1991)
volume strength of H2O2 solution. (1997)
31. A 1.0 g sample of Fe2O3 solid of 55.2% purity is dissolved in
acid and reduced by heating the solution with zinc dust. 38. An aqueous solution containing 0.10 g KIO3 (formula weight
The resultant solution is cooled and made up to 100.0 mL. = 214.0) was treated with an excess of KI solution. The
An aliquot of 25.0 mL of this solution requires for titration. solution was acidified with HCl. The liberated I2 consumed
Calculate the number of electrons taken up by the oxidant 45.0 mL of thiosulphate solution decolourise the blue starch-
in the reaction of the above titration. iodine complex.Calculate the molarity of the sodium
(1991) thiosulphate solution. (1998)
32. A 2.0 g sample of a mixture containing sodium carbonate, 39. How many millilitres of 0.5 M H2SO4 are needed to dissolve
sodium bicarbonate and sodium sulphate is gently heated 0.5 g of copper (II) carbonate ? (1999)
till the evolution of CO2 gases. The volume of CO2 at 750
mm Hg pressure and at 298 K is measured to be 123.9 mL. A
1.5 g of the same sample requires 150 mL of (M/10) HCl for
complete neutralization. Calculate the percentage
composition of the components of the mixture. (1992)
REDOX REACTIONS 38
40. Hydrogen peroxide solution (20 mL) reacts quantitatively 44. 5.00 mL of 0.10 M oxalic acid solution taken in a conical
with a solution of KMnO4 (20 mL) acidified with dilute flask is titrated NaOH from a burette using phenolphthalein
H2SO4.The same volume of the KMnO4 solution is just indicator. The volume of NaOH required for the appearance
decolourised by 10 mL of MnSO4 in neutral medium of permament faint pink colour is tabulated below for five
simultaneously forming a dark brown precipitate of hydrated experiments. What is the concentration, in molarity, of the
MnO2. The brown precipitate is dissolved in 10 mL of 0.2 M NaOH solution? (2020)
sodium oxalate under boiling condition in the presence of
dilute H2SO4. Write the balanced equation involved in the
reactions and calculate the molarity of H2O2. (2001)
41. Calculate the amount of calcium oxide required when it
reacts with 852 g of P4O10. (2005)
42. To measure the quantity of MnCl2 dissolved in an aqueous
45. In the chemical reaction between stoichiometric quantities
solution, it was completely converted to KMnO4 using
of KMnO 4 and Kl in weakly basic solution, what is the
thereaction.
number of moles of I 2 released for 4 moles of
MnCl2 K 2 S 2 O8 H 2O KMnO4 H 2 SO4 HCl
KMnO 4 consumed? (2020)
(equation not balanced).
Few drops of concentrated HCl were added to this solution 46. The treatment of an aqueous solution of 3.74 g of Cu(NO3)2
and gently warmed. Further, oxalic acid (225 mg) was added with excess KI results in a brown solution along with the
in portions till the colour of the permanganate ion formation of a precipitate. Passing H2S through this brown
disappeared. The quantity of MnCl2 (in mg) present in the solution gives another precipitate X. The amount of X (in
initial solution is_______. (2018) g) is ________.
43. The amount of water produced (in g) in the oxidation of 1 [Given: Atomic mass of H = 1, N = 14, O = 16, S = 32, K = 39,
Cu = 63, I = 127] (2022)
mole of rhombic sulphur by conc. HNO3 to a compound
with the highest oxidation state of sulphur is______(Given
data: molar mass of water = 18g mol-1) (2019)
Find Answer Key and Detailed Solutions at the end of this book
REDOX REACTIONS
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GENERAL ORGANIC CHEMISTRY
Chapter 06 40
GENERAL ORGANIC CHEMISTRY
1. INTRODUCTION TO CARBON General Organic Chemistry is the detailed study of the basic
AND ITS COMPOUNDS concepts and factors that govern the progress and outcome of
reactions.
In 1807, Berzelius proposed the term ‘Organic Chemistry’ for the 1.1 Tetravalence of Carbon
study of compounds derived from natural sources. This was based The tetravalency of carbon is its ability to form bonds with other
on the theory of vitalism which said that all living systems atoms by sharing its valence electrons. A carbon atom forms four
possessed a ‘vital force’ which was absent in non-living systems. covalent bonds hence carbon is said to be tetravalent, where tetra
Compounds derived from living natural sources (organic) were means ‘four.’
thought to be fundamentally different from inorganic compounds.
Covalent bond can be or bond.
Shape of and bond
The vital force could be philosophically thought as the mysterious
force God instilled in the living systems. In 1823, Friedrich Wohler Single bond All single bonds are bonds
joined Berzelius as his student. In 1828, Wohler made a discovery
Double bond 1 + 1 bond
which changed the definition of organic chemistry. Wohler
conducted the following experiment. Triple bond 1 + 2 bond
Wohler successfully synthesized an organic compound starting
In the above given example tetravalence of each carbon is 4.
from an inorganic compound. Following this, many others
synthesized organic compounds starting from inorganic 1.2 Catenation
compounds. Thus, the theory of vitalism and the definition of Catenation refers to the property of self – linking of atoms of an
organic chemistry lost its meaning. But what was common in all element. It depends upon bond energy, size and bond length
the above compounds synthesized was the presence of carbon. between the atoms of the same element. Thus, the element capable
Carbon shows a special property catenation. Carbon can connect of forming stronger and shorter self – linking bonds will have the
with other carbon atoms to form long chains and rings (self- best catenation property.
catenation) and can connect with atoms of many other elements (a) Carbon is known to be the element in which the catenation
in the periodic table (cross-catenation). Because of this reason, occurs most readily.
carbon can form a wide variety of compounds. Therefore, the
(b) It forms covalent bonds to form longer chains and structures
modern definition of organic chemistry is the study of carbon
with other carbon atoms. This is the main reason behind the
compounds. Probably, the vital force can be explained by the
occurrence of a vast number of organic compounds in nature.
fact that most of the life-giving and life-sustaining functions are
performed by carbon compounds, for example, the human tissues Commonly Occuring Forms of Carbon
and skin are formed by proteins, respiration is possible due to The commonly occuring forms of carbon are
haemoglobin, the information in our genes is carried out in the (a) Diamond (b) Graphite (c) Carbides
form of DNA/RNA etc.
(d) Fullerenes (e) Charcoal
SCAN CODE
General Organic Chemistry
GENERAL ORGANIC CHEMISTRY 41
NOTE 2. STRUCTURAL REPRESENTATION OF
3
Diamond - Each C is sp . Tetrahedral solid. ORGANIC COMPUONDS
2
Graphite - Each C is sp . Layered solid with weak van der Waal’s Several kinds of formulae are used by organic chemists to represent
forces between layers. organic compounds
Calcium Carbide - Each C is sp. 2.1 Complete Formula
2
Fullerene - Each C is sp . Complete formulas are lewis structures which shows all bond pair
1.3 Hybridization of electrons as a dash (–). Lone pair of electrons are shown as a
pair of dots.
Hybridisation is a process in which two or more atomic orbitals
of comparable energy of the valence-shell of an atom (central
H H
atom of the molecule or ion) either in its ground state or in its | |
excited state mix together and give rise to the formation of new Example: H C| C| H
degenerate orbitals which are called hybrid orbitals. H H
(a) Applications of Hybridization
2.2 Condensed Formula
Hybridization %s-character Condensed formulas are written without showing all the individual
3 bonds. Each central atom is shown together with the atoms that
Sp 25.0
are bonded to it.
Sp2 33.3
Example:- CH3–CH3
Sp 50.0
2.3 Line-Angle Formula or Bond Line Formula
These are also called skeletal structures or a stick figure. Line-
(i) Size of Hybrid Orbitals angle formulas are often used for cyclic compounds and occasionally
As % s-character increases, size of hybrid orbital decreases. for non-cyclic ones. Bonds are represented by lines, and carbon
Therefore atoms are assumed to be present where two lines meet or a line
3 2 begins or ends. Hydrogens are generally implicit in these drawings.
Size of Hybrid Orbital : sp > sp > sp
(ii) Electronegativity of Hybrid Orbitals Example:- Butane
As % s-character increases, electronegativity of hybrid orbital
increases. Therefore In cyclic compounds, the bond-line formulas used
2 3
EN of Hybrid Orbital : sp > sp > sp
1.4 Homologous Series
A homologous series (Greek homos = “the same as”) is a family
of compounds in which each member differs from the next by one
methylene (CH2) group. The members of the homologous series
are called homologues. Example:
(a) Alkanes CnH2n + 2
(b) Alkenes CnH2n
(c) Alkynes CnH2n – 2
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General Organic Chemistry
GENERAL ORGANIC CHEMISTRY 42
2.4 Tetrahedral Representation 4. CLASSIFICATION OF ORGANIC COMPOUNDS
This is generally the three-dimensional (3-D) representation of
molecules. Dashed Wedge ( ) or solid wedge ( ) are used to 4.1 Hydrocarbons
indicate bonds projecting behind the plane (away from the
observer) and out of the plane (towards the observer) respectively. The hydrocarbons & their derivatives are organic compounds.
Bonds lying in the plane of paper are depicted by using a normal
line (—).
3.DEGREE OF CARBON
It is defined as the number of carbons attached to carbon under
observation. (Free vacancies indicates hydrogen atom).
4.2 Functional Group
The functional group may be defined as an atom or group of atoms
Methyl joined in a specific manner which is responsible for the
characteristic chemical properties of the organic compounds. The
examples are hydroxyl group (–OH), amino group (–NH 2)
aldehyde group (–CHO) and carboxylic acid group (–COOH) etc.
1° (Primary)
5. DEGREE OF UNSATURATION
2° (Secondary) DU of a compound is equal to the number of moles of H2 that
must be supplied to convert it into an open chain saturated
compound.
Calculation of DU:
Case I: When structure is given
3° (Tertiary)
DU = Number of bonds + number of rings
Case II: If molecular formula given, then
H X A
DU = (C + 1) –
2
4° (Quaternary
Where C number of atoms of C
H number of atoms of H
X number of monovalent atoms
A number of trivalent atoms
Number of ‘O’ & ‘S’ are neglected
SCAN CODE
General Organic Chemistry
GENERAL ORGANIC CHEMISTRY 43
Example NOTE
All negatively charged species are nucleophilic but all positively
charged species need not be electrophilic
For example
Solution:
In the given compound 1 ring +2 double bonds are present
that means DU = 1 + 2 = 3.
Example
C2 H 7 N
7. NOMENCLATURE OF ORGANIC COMPOUNDS
Solution: 7.1 Common Name of Organic Compounds
DU 2 1
7 0 1 Common names for hydrocarbon derivatives
2
33 0
6. REACTING SPECIES
Reacting species are attacking reagents, which attack on substrate
and form product. Attacking reagents are electrophile and
nucleophile
Reagent
(a) Electrophile/Electrophilic Reagent
Electrophiles are electron deficient species and attacks at electron
rich site. These are also electron loving species. Here R, R’, R” represent alkyl group
Types: Example
CH3 CH 2 NH CH 3 Ethyl methyl amine
1. Cationic N O 2 , N O,C H 3 , C l, B r etc.
CH 3 CH 2 C CH 3 Ethyl methyl ketone
||
2. Neutral BF3 , AlCl3 , ZnCl 2 ,SO 3 etc.
O
(b) Nucleophile/Nucleophilic Reagent Alkyl Group:
Nucleophiles are electron rich speices and attack electron deficient When a hydrogen is removed from alkane (saturated
site that is these are nucleus loving species hydrocarbon) then alkyl group is formed.
Types: A bond is vacant on alkyl group on which any functional group
may come.
1. Anionic : OH,
N H 2 ,: C H 3 , C l etc.
Alkane
H
Alkyl
2. Neutral H 2 O :, N H 3 , R O
H, R O R, R N H 2 etc.
Cn H 2n 2 C n H 2n 1
Groups
3. Bonded C C C C Atom or a group of atoms which possess any ‘free valency’ are
called as groups. If their are two structure of same molecular
formula then some prefix (n iso, neo) are used two differentiate
4. Ambident: : C N, O
N O: them.
Nitrite ion
SCAN CODE
General Organic Chemistry
GENERAL ORGANIC CHEMISTRY 44
o
I. Normal group: There should be one 4 carbon and atleast three methyl group
o
(a) It is represented by ‘n’. on 4 carbon.
(b) Groups having no branch (Straight chain). Common Names of the Functional Group
(c) Free bond will come either on Ist carbon atom or on last Functional Suffix
carbon atom. group
O -ic Acid
n - butyl CH 3 CH 2 CH 2 CH 2 ||
C OH
n - propy CH 3 CH 2 CH 2 O O -ic anhydride
|| ||
II. Iso group: C O C
When one methyl group is attached to the second last carbon of O -ate
the straight carbon chain is named as iso group. ||
C O R
Example O -amide
||
CH 3 C NH 2
|
CH 3 C O -yl halide
| ||
H C X
Isopropyl O -aldehyde
||
C H
Secondary Group: C N -o-nitrile
The carbon having free valency attached to two carbon is called N C -o-isonitrile
secondary carbon.
Prefix:
Example
1. Carbon Form
CH 3 CH CH 2 CH 3 2. Carbon Acet
|
3. Carbon Propion
secondary butyl
4. Carbon Butyr
Tertiary Group: 5. Carbon
The carbon having free valency attached to three other carbon.
Example
CH 3
|
CH 3 C CH 3
|
Tertiary butyl
Neo Group: 3 C + (=) double bond = Acryl-
When two methyl groups on second last carbon of a straight 4 C + double bond = Croton
carbon chain is attached to other four carbon atom group is
named as neo group.
Example
C
|
CCC Neo pentyl
|
C
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Example No. of Name Structure Substituent
CH 3 CH 2 CH 2 C H C-Atoms Name
||
O 1 Methane CH4 Methyl
Butyric Aldehyde 2 Ethane CH3CH3 Ethyl
3 Propane CH3CH2CH3 Propyl
CH 3 CH CH C OH
|| 4 Butane CH3(CH2)2CH3 Butyl
O
5 Pentane CH3(CH2)3CH3 Pentyl
Crotonic Acid
6 Hexane CH3(CH2)4CH3 Hexyl
7.2 IUPAC Nomenclature
In 1949, an organization was set up to formulate the rules for 7 Heptane CH3(CH2)5CH3 Heptyl
naming organic compounds. This organization is IUPAC - 8 Octane CH3(CH2)6CH3 Octyl
International Union for Pure and Applied Chemistry. Prior to this,
9 Nonane CH3(CH2)7CH3 Nonyl
the organic compounds were known by their trivial/common names
which generally indicated their source. For example, formic acid 10 Decane CH3(CH2)8CH3 Decyl
gets its name from formica (Latin, red ants) and acetic acid gets 11 Undecane CH3(CH2)9CH3
its name from acetum (Latin, vinegar). Important: Systematic
12 Dodecane CH3(CH2)10CH3
nomenclature is required in order to have unambigous names for
all compounds 13 Tridecane CH3(CH2)11CH3
IUPAC name Template 14 Tetradecane CH3(CH2)12CH3
15 Pentadecane CH3(CH2)13CH3
20 Eicosane CH3(CH2)18CH3
Compound roots represent the number of carbon atoms.
(ii) Naming of Saturated Branched Chain Hydrocarbons
o
2 prefix – They are substituent or position of locant
o
1 prefix – Cyclic
Word root – Number of C atoms
o
1 suffix – Saturated or unsaturated
o
2 suffix – Main functional group Rule-1
(a) Naming of Saturated Hydrocarbons (Alkane) Determine the longest carbon chain in the molecule (parent
chain).
(i) Naming of Saturated Unbranched Hydrocarbons
Example
Template : Alk + ane
I.
Longest chain = 8
II.
Longest chain = 9
(II) is the correct chain selection.
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Rule-2 Rule-4
Assign numbers to each carbon of the parent chain. Numbering is Determine the correct name for each branch for example, alkyl
done to identify the parent alkane (compound root) and to locate groups such as methyl, ethyl, etc. Attach the name of the branches
the positions of the carbon atoms at which branching takes place. alphabetically along with their positions to the parent chain as
The numbering is done in such a way that the branched atoms prefix. Separate numbers from letters with hyphens.
get the lowest possible number. Example
Example
I.
6-Ethyl-2-methylnonane
If two substituents are in equivalent positions, the lower number
is given to the one coming first in the alphabetical listing.
II. Example
I. CORRECT
2, 6-CORRECT
If there is a tie for the first branch, then go to the second and so on
until a difference is observed.
Example
II. INCORRECT
I. 2, 4, 5-INCORRECT
II. 2, 3, 5-CORRECT Rule-5
When two or more branches are identical, use prefixes di-, tri-,
tetra-, etc. Numbers are separated with commas and prefixes are
Rule-3 ignored while determining alphabetical order.
Lowest set of locant rule: The number given to the side chain is Example
locant. While numbering the parnet chain, lowest set of locants
rule needs to be followed. According to this rule, that set of locants
will be considered which has got a lower number at the first point
of difference.
I 2, 2, 3, 6,8 Correct
II 2, 2, 4, 4,5 Incorrect
First point of
difference
Example
This is an incorrect selection as lowest number rule is violated.
Rule-6
If there happen to be two chains of equal length, then that chain is
selected which contains more number of side chains
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Example 7.2.2 Naming of Unsaturated Hydrocarbon (Alkene/Alkyne)
Unsaturation Index Suffix
CC -ene
CC -yne
I.
(i) Naming of Unbranched Unsaturated Hydrocarbons
INCORRECT (3 side chains) Template
Alk + n + ene (n is the location of double bond)
Alk + n + yne (n is the location of triple bond)
Example
II.
CORRECT (4 side chains)
2,3,5-Trimethyl-4-propyloctane
Rule-1
(iii) Naming of Complex Alkyl Groups
Numbering of Carbon Chain
For systematic names, the carbon atom of the branch that
attaches to the parent chain is given number one. If unsaturated bond is present in the molecule at the terminal
carbon, then numbering done from the side of unsaturated carbon.
Example
4 3 2 1
Example
C H3 C H C H2 C H 1 2 3 4
| | C H 2 C H C H 2 C H 3 But-1-ene
CH 3 CH 3 1 2 3 4
1,3Dimethylbutyl C H C C H 2 C H 3 But-1-yne
Rule-2
The name of such branched chain alkyl group is placed in
parenthesis while naming the compound If unsaturated bonds like double bond and triple bond are present
In alphabetical order, the prefixes iso- and neo- are at terminal carbon, then numbering always done from double
considered to be the part of the fundamental name of alkyl bonded terminal carbon.
group. The prefixes sec- and tert- are not considered to be (Double bond preferred over triple bond when both bonds are at
the part of the fundamental name. same position)
The use of iso and related common prefixes for naming alkyl Example
groups is also allowed by the IUPAC nomenclature as long
1 2 3 4
as these are not further substituted. C H2 C H C C H But 1 en 3 yne
Rule-3
If unsaturated bonds like double bond or triple bond is present at
terminal carbon, then numbering is done from either way.
Example
1 2 3 4
I. C H 2 C H C H C H2 But 1,3 diene
1 2 3 4
CH CH 3 2 II. C H 2 C C C H But-1,3-diyne
1 2 3 4| 5 6 7 8 9 10
C H 3 C H 2 C H 2 CH C H C H 2 C H 2 C H 2 C H 2 C H 3
|
CH 3 CH CH 2 CH 3
5 sec Butyl 4 isopropyldecane
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Rule-4
If triple bond is present at terminal carbon and double bond is
located at any carbon except other terminal carbon. Then
numbering is done from triple bond.
Example 3 - Ethenyl hepta - 1, 6 - diene
1 2 3 4 5
C H C C H C H C H 3 Pent 3 en 1 yne
7.2.3 Naming of Alicyclic Hydrocarbons
Rule-5 Template
If double bond is present at terminal carbon and triple bond is
present at any other position except other terminal carbon, then
numbering is done from double bonded terminal carbon.
Example
1 2 3 4 5
C H 2 C H C C C H 3 Pent 1 en 3 yne
Naming of Branched Unsaturated Hydrocarbon
Rule-1
Select that chain which contains maximum number of double and
triple bonds.
Rule:
Rule-2
A ring is treated as a substituent only when the number of carbon
If two chains are competing for selection as the chain with
atoms are less in the ring than in the chain.
maximum number of unsaturated bonds, then the choice goes to
Example:
(a) The one with the greatest number of carbon atoms.
(b) The number of carbon atoms being equal, the one containing
maximum number of double bonds.
CH 2 CH
CH 2 CH CH 2
CH C
Example
3 2 1
C H 2 C H C H2 7.2.4 Nomenclature of Organic Compounds Containing
| 4 5 6
CH 3 CH 2 CH 2 CH 2 C C H C H 3 Functional Group
4 Butylhexa 1 4 diene Type I
A functional group is an atom or a group of atoms which
characterizes the chemical reactivity of a molecule.
Alkoxy, nitro,nitroso and halogen groups are treated as
substituents
3 - Ethynyl penta - 1, 4 - diene
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Alkoxy, nitro and halogen groups are always treated as substituents Example
Group Substituent name
OR alkoxy 2-Methoxypentane
X halo Example
NO2 nitro
NO nitroso
2-Bromo-3-nitroso pentane
Type II
The longest chain of atoms containing the functional group is numbered in such a way that the carbon to which functional group is
attached is assigned the lowest number. In case of polyfunctional compounds, one of the functional groups is chosen as the principal
functional group and the compound is named treating other functional groups as substituents.
Class Formula Prefix Suffix
Acid Halide COX Halocarbonyl – carbonyl halide
(C)OX – – oyl halide
Alcohols OH Hydroxy – ol
Aldehydes CHO Formyl – carbaldehyde
(C)HO Oxo – al
Amides CONH2 Carbamoyl – carboxamide
(C)ONH2 – – amide
Amines NH2 Amino – amine
Carboxylates Carboxylato – carboxylate
– – oate
Carboxylic Acid COOH Carboxy– – carboxylic acid
(C)OOH – – oic acid
Esters of COOR Alkoxy carbonyl Alkyl .. carboxylate
Carboxylic Acid (C)OOR – Alkyl ... oate
Ketones Oxo– – one
cyanides (Nitriles) Cyano – carbonitrile
– – nitrile
Salts of Carboxylic – Cation ... carboxylate
Acids – Cation ... oate
Sulphonic Acids Sulfo– – sulfonic acid
Thiols SH Mercapto – thiol
Order of Decreasing Priority for Functional Groups
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Points to Remember Example
(a) The –R, –C6H5, halogens, nitro and alkoxy groups are
always treated as substituents.
(b) If more than one functional group of same type is present,
its number is indicated by adding di-, tri- etc.
(c) When C is marked in parenthesis, the carbon of the
2-hydroxy-4-oxo pentanoic acid
functional group is counted as part of the parent chain
and the numbering will always begin from this carbon and Secondary suffix is oic acid hence rest functional group treated
its position need not be marked in the name. as substituent.
NOTE Example
Double bond and triple bond are not true functional groups.
IUPAC Rule of Compounds with Multifunctional Groups
1. Longest possible ‘C’ chain with functional group and having 5,7-dioxo-6-hydroxyoct-3-en-1-nitrile
maximum number of multiple bonds is selected as parent ‘C’ C N Here nitrile is secondary suffix
chain.
Example
Example
2-Propyl-but-3-enoic acid
2. Numbering starts from the side of functional group given below Here Amide is secondary suffix.
is the priority order for numbering. Example
Functional group > Multiple bonds > Substituents
Here Ester is secondary suffix (main functional group)
3. ‘e’ of primary suffix is dropped if secondary suffix starts from
a vowel. The pattern of ester naming is Alkyl Alkanoate
Example
3 - Ethyl pent - 3 - enal
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Example It is anhydride nomenclature of anhydride is done on the basis of
the carboxylic acid from which it is obtained.
when both alkyl group is same pattern is Alkanoic anhydride.
When both alkyl group is different pattern is alkanoic
alkanoic’anhydride
Example
(I)
Here ketone is secondary suffix.
pattern is alk + one N,2-dibromobutanamine
Example
(II)
2-bromo-N-chlorobutanamine
The substituents on nitrogen atom is written as N-<substituent
5-ethyl-3-hydroxy-4-mercaptohept-5-ynoyl chloride
name>. Here, N (italic) indicates the position of substituent.
Acyl halide is secondary suffix.
Pattern is alkan + oyl chloride NOTE
Conditions when carbon of carbon containing functional
group not count in parent chain
Case 1: When theses functional group directly attached with a
cyclic system.
Example
Cyclohexane carboxylic acid
Here suffix carboxylic acid is used not oic acid.
Case 2: When more then two carbon containing functional
group directly attached with a parent chain.
4-carbamoyl-8-fluoro-3-methoxydecanoic acid
Here, carboxylic acid is secondary suffix
Pattern alkan + oic acid
Example
Here, suffix of aldehyde is changed.
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7.3 Nomenclature of Benzene Derivatives With respect to substituent X, we define three positions on the
benzene ring as shown in the figure. Ortho, meta, para positions
are used for writing common names of disubstituted benzenes.
The positions are also abbreviated as o-, m-, p-.
(I)
(II)
(III)
7.3.2 Benzene as substituent-Phenyl Group
When C6H5– group is treated as substituent, it’s called phenyl
group.
Important:
(a) A saturated chain containing benzene ring is named as
derivative of the larger structural unit.
(b) If the chain is unsaturated, the compound is always named as
a derivative of that chain.
7.3.1 Ortho, Meta and Para Positions Example
1-Phenyl butane
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The bond breaking is shown by a full-headed arrow. A full headed
arrow shows the movement of a pair of electrons. In organic
chemistry, the movement of electrons is always shown by curved
arrows - half-headed or full-headed arrows.
9. ELECTRONIC DISPLACEMENT EFFECT
2-methyl-1-phenylpropene
2-Phenyl heptane
There is another special group in which C6H5– is present.
10. INDUCTIVE EFFECT
When two unlike atoms form covalent bond, the electron-pair
8. COVALENT BOND FISSION forming the sigma bond is never shared equally between the two
atoms but is shifted slightly towards the more electronegative
In organic chemistry, the bond that is important for the study of
species.
reactions is covalent bond. We, therefore, study ways in which a
covalent bond can be broken. 10.1 Characterstics of Inductive Effect
(a) Homolytic Fission (b) Heterolytic Fission
8.1 Homolytic Fission or Homolytic Cleavage
In this kind of bond breaking, each atom separates with one
electron, leading to the formation of highly reactive species known
as radicals (or free radicals).
The bond breaking is shown by two half-headed or fish-hook
arrows. A half-headed arrow shows the movement of one electron. There are broadly three types of groups/atoms that may be attached
Radicals are neutral and are odd electron species. to carbon as illustrated. Although C is more electronegative than
H, the electronegativity difference is small and the bond is
8.2 Heterolytic Fission or Heterolytic Cleavage
generally consider non-polar.
In this type of covalent bond breaking, the shared pair of electrons
Nature of Inductive Effect
are transferred to the more electronegative part. Therefore, this
fission leads to the formation of a cation and an anion (ion- Inductive effect is a permanent effect and can be directly
pair). correlated to its dipole moment. It is a weak effect as the
shifting of electrons takes place only through sigma bonds.
Effect of branched carbon chain
An illustration has been marked for operation of inductive
effect which is self-explanatory.
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10.2 Applications of Inductive Effect
Effect on Acidic/Basic Strength
EWG increases acidic strength and decreases basic strength.
ERG decreases acidic strength and increases basic strength.
Strength of Carboxylic Acids
Acid strength is measured by the position of equilibrium
More the number of , lesser the effect
of ionisation in water.
Electron Donating and Electron withdrawing Groups
Inductive effect may be due to single atom or a group of HA H A
acid anion
atoms. Relative inductive effects are measured with
reference to hydrogen. Those which donate electrons to
H A
carbon chain are called electron-donating groups (EDG) or Ka
(Ka = acid ionisation constant)
or electron-releasing groups (ERG) and are said to exert HA
+I effect. Those which withdraw electrons from carbon
chain are called electron-withdrawing groups (EWG) and 1
are said to exert –I effect. or, acid strength H K a pK
a
NOTE
(here pKa = -logKa)
+I. effect of alkyl groups: 3° > 2° > 1° > CH3–
In general, greater is the number of carbons in an alkyl group, or Acid strength concentration of [H+]
greater is its +I effect. or Acid strength stability of acid anion
For problem-solving, we take electronegativity of sp-
Thus strength of acid is the function of stability of acid anion.
3
hybridized carbon to be more than sp hybridized
nitrogen. Stability of acid anion Presence of electron withdrawing
Series of +I and –I groups in order of their strength
1
–I Series (EWG) group -I group I group
acidic strength Presence of electron withdrawing group
1
I group
+I Series (ERG) Example
Compare the acidic strength :
(I) (II)
(III)
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Solution a base strengthening effect.
An alkyl group is donating only if no other EWG is present on it. Thus, strength of base +I power of group present on
Therefore, groups like –CH2Cl and –CH2F become electron
withdrawing groups. 1
NH 2 K b
pKb
Order of Acidic Strength : III > II > I
Effect of Distance Whereas, a group producing -I effect [-Cl, -NO2] tends to
decrease electron density over N-atom in amines, thereby
If the ERG/EWG moves away, the inductive effect diminishes.
producing a base weakening effect.
Example Thus, strength of base
(a) Compare the acidic strength of : 1
Kb
(I) I power of group present on -NH 2
(II)
The order in gaseous phase is :
3° > 2° > 1° > NH3
To determine the basic strength of amines in aqueous phase.
(III) We have to consider inductive effect, solvation effect and
steric hinderance. The order of basic strength is therefore
experimental in aqueous state as we can’t give priority to
(IV) stability provided by any one factor. Two results are
important for aqueous phase :
(a) (CH3)2NH > CH3NH2 > (CH3)3N > NH3
Solution:
i.e. 2° > 1° > 3° > NH3 (R = CH3)
(a) (I) (b) (C2H5)2NH > (C2H5)3N > C2H5NH2 > NH3
i.e. 2° > 3° > 1° > NH3 (R = C2H5)
11. RESONANCE
(II) Molecules are generally represented by simple Lewis structures
but some molecules can not be represented by just one Lewis
structure. This led to the discovery of resonance. Resonance refers
to the delocalization of electrons (generally -electrons).
(III) 11.1 Conjugated Systems
When a molecule or ion cannot be represented by single Lewis
dot structure and more than one structure are needed to represent
all properties of the molecule, these structures are known as
resonating structure and combined structure of all resonating
(IV)
structure is known as resonance hybrid and this phenomenon is
known as resonance.
Resonating structure have the same arrangement of atomic
Order of acidic strength : II > III > IV > I nuclei but differ in distribution of electrons, (only electron
delocalised)
Basicity of Amines
Basicity is defined as the tendency to donate an electron
Resonating structure are hypothetical and actual structure is
a resonance hybrid.
pair for sharing. The differnece in the base strength in various
amines can be explained on the basis of +I - effect. Resonance generally occurs when there is a conjugation of
-bonds (alternate double - single-double bond
The groups producing +I effects (alkyl groups) tends to arrangement)
intensify electron density over N in amines thereby producing
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(1) Pi( ) Alternate (6) Lone Pair and Positive Charge on Adjacent Atoms
Example Example
Benzene
11.2 Rules for Validity of Lewis Structures
Example Rule-1
Second period elements should not violate the octate rule while
drawing resonating structures
Rule-2
Position of atoms in all resonating structures must be the same.
Only the electrons move.
Rule-3
All the resonating structures must have the same number of paired
and unpaired electrons, i.e. sum of bond pairs and lone pairs must
be constant.
Rule-4
(2) Alternate Positive Charge All the atoms participating in resonance in a molecule must be
coplanar. This is required for the effective overlap of
Example
p orbitals and the delocalization of electrons.
For example, buta-1,3-diene.
Rule-5
Net charge should be conserved in all resonating structures.
(3) Alternate Negative Charge CH 2 CH CH CH 2 C H 2 CH CH C H 2
Net charge = 0 Net charge = 0
Example
Both structures have same net charge so both are resonance forms.
11.3 Criteria for Major/Minor Contributors
Resonance forms can be compared using the following criteria in
(4) alternate Odd Electron the following order :
Example 1. Complete octet (a neutral molecule is always more stable
in which its octet is complete).
2. More number of bonds more will be stability.
(5) alternate Lone Pair 3. Negative charge on more electronegative atom is stable.
This case is similar to ‘pi alternate negative charge’ as lone 4. Charge separation.
pair and negative charge are treated similarly. (a) Similar charges - Keep them as FAR as possible to
Example minimize repulsion and instability.
(b) Opposite charges - Keep them as NEAR as possible to
maximize attraction and stability.
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Example 11.4 Resonance Energy
Which of the following structures is more stable? The energy difference between most stable resonating structure
and resonance hybrid is known as resonance energy.
It’s the experimental value which is calculated by heat of
hydrogenation (HOH)
Higher the value of resonance energy, greater is the resonance
Solution: stabilization.
II is more stable as all the octets are complete. Resonance Energy of Benzene:
Example
Which of the following is more stable in the following pairs
(a) The resonance energy of benzene is calculated from the heat of
hydrogenation as given below:
(b)
Solution:
(a) In II, all octets are complete. Therefore, II is more stable.
but experimental value for benzene is 51 kJ, so,
(b) I and II are tied on octets and number of bonds but negative
charge is more stable on more electronegative atom. Hence, Resonance energy = Calculated value – Experimental value
II is more stable. = 87 - 51
Example = 36 Kcal.
Give the order of stability of following resonating structures Resonance Energy Comparison
(I) 1. Consider better resonance or equivalent resonating
structures, molecules having equivalent resonating structures
(II) must have more resonance energy, than non-equivalent
resonaing structures.
(III)
(IV)
(V)
2. Aromatic compound have more resonance energy that non-
Solution: aromatic compound.
In (I), there are maximum number of pi bonds. Therefore, it 3. In case or large conjugation, more will be the Resonance
is most stable. In (II) and (V), the number of pi bonds is equal energy.
but charge separation is greater in (V). Therefore, (II) is more
stable than (V). In (III) and (IV), there is maximum charge
separation but (III) is highly unstable due to electrostatic 4. Resonance energy will be more, when -bond, lone pair
repulsion. Hence, the order of stability is : conjugation is present than , -conjugation
I > II > V > IV > III
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12. MESOMERIC EFFECT 12.2 Applications of Mesomeric Effect
The permanent polarization, due to a group conjugated with a 12.2.1 Effect on Acidic Strength of Carboxylic Acids
bond or a set of alternate bonds, is transmitted through the and Phenols
electrons of the system-resulting in a different distribution of The resonating structure of carboxylic acid leads to charge-separated
electrons in the unsaturated chain. structure which is less stable than the carboxylate ion in which
This kind of electron redistribution in unsaturated compounds charge is delocalized. Therefore, carboxylic acid readily loses proton
conjugated with electron-releasing or electron-withdrawing ( H ) to form a carboxylate ion.
groups (or atoms) is called Mesomeric Effect or Resonance
Effect. This effect is permanent and is indicated by the dipole
moment.
12.1 Electron-Releasing and Electron-Withdrawing Groups
Electron-Releasing Groups (+R or +M effect)
The common thing about all the groups listed is that the atom
connected with the conjugated system has a lone pair to donate.
Therefore, a generic representation can be
Electron-Withdrawing Groups (–R or –M effect)
The common thing about all the groups listed is that the
atom connected with the conjugated system has a bond Similarly, in phenol, resonance leads to charge separation which
with another more electronegative atom which withdraws increases the rate of ionization and forms phenoxide ion which is
the electrons or directly has a positive charge on them. stabilized by charge delocalization.
Therefore, a generic representation can be
(ENZ > ENY)
Dual Behaviour
Groups such as are both electron-releasing and
electron-withdrawing as illustrated.
Example
As electron releasing group
As electron withdrawing group
Which behaviour dominates and which is used in a particular
context will be discussed later in Electrophilic Aromatic
Substitution later.
NOTE
Resonance Effect does NOT depend upon distance unlike
Order of acidic strength
inductive effect.
RSO3H > RCOOH > PhOH > CH3OH > H2O >
ROH > HCCH > NH3 > CH4
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12.2.2 Effect on Reactivity of Carboxylic Acid Derivatives
A typical nucleophilic reaction is represented as :
The stronger is the bond between C and Z, the difficult it is for a
nucleophile to break a bond and therefore, lower reactivity.
Reactivity order of carboxylic acid derivatives towards
nucleophilic acyl substitution is :
Acyl Chloride > Acid Anhydride > Ester > Amide
12.2.3 Effect of ERG/EWG on Acidic/Basic Strength
EWG increases the acidic strength and decreases the basic strength.
ERG decreases the acidic strength and increases the basic strength.
Example
Arrange the following in the order of decreasing acidic
13. AROMATICITY
strength :
It is defined as a property of the conjugated cycloalkenes which
enhances the stability of a molecule due to the delocalization of
electrons.
13.1 Aromatic Compounds (Huckel’s rule)
2
Planarity (2-D) [sp carbon]
–
Solution: Conjugated system (delocalization of e in ring)
Cyclic system
–
Presence (4n + 2) e in the ring. Where, (n = 0, 1, 2, 3...)
The order of acidic strength is: II > V > I > III > IV
In the previous example, let’s also discuss the stability of phenoxide
ions corresponding to (II) and (IV).
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13.2 Anti -Aromatic compounds The hybrid formed by these resonating structures better known as
hyperconjugating structures
Cyclic
Planar
Conjugated System
–
4n e should present in the ring where (n = 1, 2, 3...)
Now, greater the number of -H, greater the number of
hyperconjugating structures and more is the electron donation of
alkyl group to bond.
The order of electron-donation of alkyl groups based on
hyperconjugation is :
13.3 Non-Aromatic compounds
Compound which are neither aromatic nor antiaromatic.
Methyl > 1° > 2° > 3°
NOTE
Stability order of compounds: More is the number of -H, more is the bond delocalized.
Aromatic > Non aromatic > Anti-Aromatic This implies that more will be the stability of alkene and less
will be the heat of hydrogenation and more is the no-bond
14. HYPERCONJUGATION resonance energy.
14.3 Applications of Hyperconjugation
Hyperconjugation is the ability of the bond electrons of an
bond to undergo conjugation with the adjacent electrons. 14.3.1 Stability of Alkenes
It is also known as Baker-Nathan Effect, No-Bond Resonance More is the number of -hydrogen, more is the number of
and - Effect. hyperconjugating structure and therefore more stability and greater
14.1 -Carbon and -Hydrogen no bond resonance.
Example
Which alkene is more stable?
Solution :
-Carbon is the carbon attached to a functional group such as
. The hydrogen attached to -carbon is called -hydrogen.
For an bond to be eligible for hyperconjugation, C
3
must be sp hybridized.
14.2 Mechanism of Electron Donation in Hyperconjugation
I is more stable than II.
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14.3.2 Acidic Character of Alkenes 14.3.5 Heat of combustion (HOC)
Hyperconjugation weakens the C-H bond in hyperconjugation It is the energy liberated during complete combustion of organic
compuond.
hybrid (partial single bond) and therefore H can be lost easily.
HOC comparison
HOC No. of carbon-atoms
14.3.3 Stability of Carbocations
1
HOC
Stability of hydrocarbon
The positive charge on C is delocalized over H to give stability
to the carbocation. More is the number of H, more is the stability
of carbocations.
15. ELECTROMERIC EFFECT
Electromeric effect is observed only in the presence of a reagent
and is therefore, a temporary effect. When a reagent approaches a
molecule, the multiple bond such as or is polarized
by the complete transfer of electrons.
14.3.4 Heat of hydrogenation (HOH)
R CH CH 2 H 2 R CH 2 CH 3 H When
the multiple bond is between two unlike atoms, the shift of
(a) Heat evolved when 1 mole of any unsaturated electrons takes place towards more electronegative atom.
hydrocarbon is hydrogenated is called heat of
hydrogenation H If alkene is more reactive towards
hydrogen then it will evolve more H .
1 1 16. APPLICATION OF ELECTRONIC EFFECTS
So, H stability of alkene number of -H
16.1 Comparison of inductive, hyperconjugation and
(b) H number of bonds
Resonance Effects
(c) It is exothermic process (energy release)
Examples of HOH order Inductive Effect is a - interaction and acts through strong
(i) CH 2 CH CH 2 CH 3 CH 3 CH CH CH 3 sigma bonds.
(ii) CH 2 CH CH 2 CH3 CH 2 CH CH CH 2 Resonance/Mesomeric Effect is a - interaction and acts
| through weak pi bonds.
CH 3
Hyperconjugation is a - interaction and acts through a strong sigma
and a weak pi bond.
(iii)
Therefore, the order of importance is
Resonance > Hyperconjugation > Inductive
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16.2 Steric Inhibition of Resonance (SIR) 16.3 Steric Inhibition of Protonation (SIP)
When both the ortho positions of a bulky functional group are
occupied by bulky substituents, all the three groups are out of
plane of the benzene ring.
Example
Mark the order of basic strength : Expected Order : o > p > m > PhNH2
Actual Order* : p > m > PhNH2 > o
17. REACTIVE INTERMEDIATES
17.1 Carbocation
17.1.1 Definition
Solution Carbocation is the intermediate of carbon containing positive
In (II) and (III), the lone pair of N is in conjugation with the charge. It has six electrons in the valence shell.
benzene ring and is not available for donation. (II) is less 17.1.2 Geometry and Hybridization
basic than (III) due to –I and –M of –NO2 group. It may seem
2
that (I) is least basic due to presence of 2 –NO2 groups but – Hybridization of C = sp
NO2 and –N(CH3)2 are all bulky groups. This is a case of Geometry of C = Trigonal Planar
steric inhibition of resonance due to which the lone pair of N
is not in conjugation and is readily available for electron
donation. Hence, the order of basic strength is :
(I) > (III) > (II)
Example
Mark the order of bond lengths in the given molecule.
17.1.3 Classification of Carbocations
This classification will also be used for carbanions and carbon
free radicals and will be studied only in this section.
Methyl Carbocation
1° Primary Carbocation
Solution :
–I, –NO2 are bulky groups and is case of steric inhibition of 2° Secondary Carbocation
resonance. Therefore, the –NO2 groups ortho to –I are out
of conjugation while the –NO2 group para to –I will be in 3° Tertiary Carbocation
conjugation with the benzene ring. Therefore, bonds ‘a’ and
‘b’ will always have single bond character while ‘c’ has
double bond character. Therefore :
c<a=b
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Example
Rank the stability of carbocations in each case
(a)
Solution :
(a)
17.1.4 Stability of Carbocations
There are three factors contributing to the stability of carbocations:
(a) Inductive Effect
(b) Hyperconjugation
(c) Resonance
Order of stability
Order of stability : III > I > II
17.1.5 Formation of Carbocations
Ionization of Carbon-Leaving Group Bond
In this method :
(a) Bond between carbon and leaving group ionizes.
(b) Leaving group accepts the pair of electrons that were shared
in the covalent bond.
Rate of formation of carbocation depends on :
(a) The stability of carbocation formed.
(b) The nature of the leaving group. Weaker the base better
the leaving group. This is because weaker leaving group
implies a stable compound and its formation will therefore
be favoured.
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Addition of Proton to a bond Step-3: Deprotonation
Rate of carbocation formation depends on :
(a) Stability of carbocation formed.
(b) Strength of the electrophile.
17.1.6 Reactions of Carbocations
There are three important reactions of carbocations :
(a) Capture a Nucleophile
(b) Loss a proton to form a bond.
(c) Rearrangement When carbocation deprotonation can lead to more than one product,
1. Capture a Nucleophile all products are formed and the most stable product is the major
product.
2. Loose a proton to form a bond 3. Carbocation Rearrangement
A carbocation can become more stable by rearrangement. Bonding
Form the products from the following reaction : electrons of carbocation may shift between adjacent atoms to form
more stable carbocation. There are two kinds of shifts that take
place in order to gain stability.
(a) Hydride Shift (b) Alkyl Shift
Solution :
Step-1 : Protonation
Step-2 : Formation of Carbocation
In the above example, both hydride and methyl shifts are possible
leading to more stable carbocation but only that shift is preferred
which leads to more stable carbocation. In this example, hydride
shift will take place.
The shift takes place in the form of .
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Cyclic Rearrangement/Ring Expension 17.2 Carbanions
Ring expension will take place only when positive charge is 17.2.1 Definition
on carbon adjacent to the ring.
Carbanion is the intermediate of carbon containing negative charge.
Example It has eight electrons in the valence shell.
Draw the products of the following reaction :
17.2.2 Geometry and Hybridization
3
Hybridization of carboanion is sp .
Solution Geometry : Trigonal Pyramidal
Carbanion and ammonia are isoelectronic species having same
structure
17.2.3 Stability
ERG will increase the electron density at carbon and will make it
Even though the hydride shift leads to more stable carbocation, unstable. EWG will decrease the electro density at carbon and
ring expansion is preferred. will make it stable.
Order of Stability
Example
Give the order of stability of :
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Solution: 17.3.3 Stability
As s-character increases, electronegativity of C increases ERG increase stability while EWG decrease stability.
and therefore negative charge will become more stable.
Therefore, order of stability is :
III > II > I
17.2.4 Formation of Carbanion
There are two methods for the formation of carbanion :
(A) Partial formation via Grignard Reagent 17.3.4 Formation of Carbon Free Radical
(B) Formation from Carbonyl Compounds Carbon Free Radicals are formed by homolytic cleavage of bonds.
They are formed :
17.3 Carbon free radical (a) at high temperature in the gas phase
17.3.1 Definition (b) in non-polar solvents
Carbon Free Radical is the intermediate of carbon having an odd (c) by ultraviolet light
electron. It is neutral and has seven electrons in the valence shell. (d) by addition of other radicals
It is highly reactive as it requires only one electron to complete its
17.3.5 Reactions of Carbon Free Radical
octet and therefore, is short-lived. The most common reactions in which free radical is involved are
(a) Halogenation of alkanes.
17.3.2 Geometry and Hybridization (b) Addition of HBr in the presence of peroxides to alkenes. (Anti-
Markonikov Rule)
(c) -Halogenation of alkenes.
(d) Wurtz Reaction
(e) Decarboxylation reaction
18. ISOMERISM IN ORGANIC CHEMISTRY
The hybridization of carbon free radical was proposed after In organic chemistry, a number of organic compounds having
experimental verification of structure of different radicals. It was different physical and chemical properties can be represented by
• 2
proposed that when ERG are placed on C , it has sp hybridization the same molecular formula. The property by virtue of which
3
and when EWG are placed on C•, it has sp hybridization. organic compounds possessing different physical and chemical
properties and having the same molecular formula is known as
Molecule Hybridization Location of
odd electron isomerism and the different compounds are known as isomers.
CH 3 sp 2 P Since the isomers are constituted of the same number of atoms, so
CF3 sp3 sp3 it is clear that the difference in their properties must be due to the
difference in the relative arrangement of the atoms within the
molecules.
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Molecular Formula Functional Groups
C n H 2n 2 Alkane
C n H 2n Alkene, Cycloalkane
C n H 2n 2 Alkyne, Cycloalkene,
Diene (Cumulated,
Conjugated, Isolated)
C n H 2n 2 O Alcohols, Ethers
19. STRUCTURAL ISOMERISM Cn H 2n O Aldehydes, Ketones,
If the isomers have the same molecular formula but they differ in Cyclic Ether (Epoxide,
the relative arrangement of atoms, it is called structural isomerism. Oxirane,), Unsaturated
In structural isomers, the structural formula of the isomers differ Alcohol
whereas the molecular formula remains same. This type of Cn H 2n O 2 Acid, Ester, Hydroxy
isomerism is further divided into various types. aldehyde and Hydroxy
19.1 Chain or Nuclear Isomerism Ketone
This type of isomerism arises due to the difference in the structure Example
of carbon chain. The difference may be in the length of the carbon
chain or in the size of the carbon ring. (i)
Example
n–Butane and isobutane are chain isomers. (ii) C3H6O exhibits the following functional isomers.
CH3–CH2–CH2–CH3
n–butane isobutane
19.2 Positional Isomerism
This isomerism arises due to the difference in position of either
substituent or functional group in the same carbon chain.
Example
(i) CH3–CH2–CH=CH2 CH3–CH = CH–CH3 19.4 Tautomerism
But–1–ene But–2–ene This is a special type of functional isomerism where functional
(ii) C6H4(NO2)2 exhibits following three positional isomers. isomers exist in equilibrium with each other. Such isomers are called
tautomers.
The necessary condition for this type of isomerism is the presence
of –hydrogen to the carbonyl group (a hydrogen on a carbon
adjacent to carbon of functional group).
A very common form of tautomerism is that between a
carbonyl compound containing -hydrogen and its enol
19.3 Functional Isomerism form. This type of isomerism is also known as keto–enol
These isomers have same molecular formula but they differ only isomerism.
in the presence of different functional groups.
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In general, the keto form is more stable than the enol form Same atoms or groups on same carbon atoms. So geometrical
but in some cases the enol form is more stable. isomerism is not possible.
19.5 Metamerism
It is caused by the attachment of different alkyl groups to a polyvalent
atom or group (an atom having more than one valency). A metamer
can be obtained by shifting one or more CH2 group from one side of
the polyvalent functional group to the other side. Metamerism is found Cis-Trans Isomerism
to occur in amines, ethers, ketones, esters, etc. Geometrical Isomerism in
Example
Cis isomers are isomers in which two similar atoms lie on the
C4H10O exhibits three metamers. same side of a double bond in the molecule. On the other hand,
trans isomers feature molecules with two similar atoms placed on
opposite sides of a double bond.
Example
Calculation of Geometrical Isomers
Case 1:
n
20. STEREO ISOMERISM If both the ends are differnet 2 when n is number of stereogenic
area of bond which can show G.I.
In this type of isomerism, the compounds possessing same
molecular formula differ in their properties due to the difference Case 2:
in the arrangement in space of their atoms or groups in the If both the ends are same
molecule.
2 n 1 2p 1
20.1 Geometrical Isomerism
If n = even ; P = n/2
It is the type of isomerism in which the compounds possessing same
molecular formula differ in their properties due to the difference in n 1
If n = odd; P
their geometry that is, due to the difference in the direction of 2
attachment of same atoms or groups in their molecule. It is not
20.2 Conformational Isomerism
shown by single bonded compounds like (C – C) due to free rotation.
A form of stereoisomerism in which the isomers can be
It is shown by C = C, C = N, N = N and cycloalkanes.
interconverted just by rotations about formally single bonds
Conditions for exhibiting Geometrical Isomerism (Generally Alkanes).
(a) There must be restricted rotation in the molecule. Any two arrangements of atoms in a molecule that differ
by rotation about single bonds can be referred to as
different conformations and this phenomenon is
called conformational isomerism. Such spatial arrangement
of carbon, hydrogen atoms which can be converted into
(b) Groups attached to the doubly bonded carbon or nitrogen must be one another by rotation around a C-C single bond is called
different. Lone pair is also considered as a different group. confirmation or conformer or rotamer.
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NOTE
In all the conformations, the bond angles and the bond lengths
remain the same.
Eclipsed and the staggered conformations can be represented
by Sawhorse and Newman projections.
20.2.2 Sawhorse Projection
In this projection, the molecule is viewed along the
molecular axis. Also know as side view of molecule.
Rotation around a C-C single bond is not completely
free. It is hindered by a small energy barrier of 1-20 kJ Bond between two C-C represented by a longer straight
line.
mol–1 due to weak repulsive interaction between the
adjacent bonds. The rotational energy barrier is known as Upper end of the line is slightly tilted towards right- or
left-hand side. The front carbon is shown at the lower end
conformational energy. It is the potential energy differ-
of the line, whereas the rear carbon is shown at the upper
ence between most stable conformation and least stable
end
conformation.
If the energy barrier is low (1-20 kJ mol–1), there is free The front carbon is shown at the lower end of the line,
whereas the rear carbon is shown at the upper end.
rotation (energy available at room temperature) and a
sample of the compound exists as a rapidly equilibrating In ethane each carbon has three hydrogen atoms hence H
atoms represented by three lines. The lines are inclined at
mixture of multiple conformers.
an angle of 120° to each other.
20.2.1 Conformation of Ethane Sawhorse projections of eclipsed and staggered conformations
Ethane molecule (C2H6) contains a C– C single bond with each of ethane are:
carbon atom attached to three hydrogen atoms, keep one carbon
atom stationary, and rotate the other carbon atom around the C-C
axis.
This rotation results into infinite number of spatial arrangements
of hydrogen atoms attached to one carbon atom with respect to
the hydrogen atoms attached to the other carbon atom. These
different arrangements are known as conformational
isomers or conformers.
However, there are two extreme cases, Staggered and Eclipsed
confirmation. 20.2.3 Newmann Projection
Staggered conformation: Type of confirmation in which The molecule is viewed at the C–C bond head on. It is also
hydrogens are as far apart as possible. The dihedral angle known as front view of molecule.
between the bonds at each atom of carbon-carbon bond is The carbon atom nearer to the eye is represented by a point.
60o, 180o, 300o. Three hydrogen atoms attached to the front carbon atom
Eclipsed conformation: Type of conformation in which are shown by three lines drawn at an angle of 120° to each
hydrogen atoms attached to two carbons are as closed to- other.
gether as possible. The atoms bonded to carbons at each The rear carbon atom (the carbon atom away from the eye)
end of carbon-carbon bond are directly opposite to one is represented by a circle and the three hydrogen atoms are
another and the dihedral angle between them is 0o, 120o,
shown attached to it by the shorter lines drawn at an angle
240o.
of 120° to each other.
Any other intermediate conformation is called a skew
conformation.
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Newman projections of eclipsed and staggered conformations of
ethane are:
From above the conformations of ethane, the staggered form has
the least torsional strain and the eclipsed form, the maximum
torsional strain.
Hence stability order of ethane is:
Eclipsed > Skew > Staggered
20.2.5 Conformation of n-Butane
20.2.4 Relative stability of conformations
More the energy less will be the stability of conformer, the repul-
sive interaction between the electron clouds, which affects sta-
bility of a conformation, is called torsional strain, Pitzer strain or
Eclipsing strain.
Magnitude of torsional strain depends upon the angle of rotation
about C–C bond. This angle is also called dihedral angle or tor-
sional angle.
20.2.6 Case of Intramolecular Hydrogen Bonding
Dihedral angle is the angle between C - X and C - Y in X - C - C
- Y when it is visualised along C - C bond. In case of G-CH2-CH2-OH, where G = -OH, -NH2, -F, -NR2, -
NO2, -COOH, -CHO the Gauche form is more stable than the anti
form due to intramolecular hydrogen bonding.
Example. 2-Fluoroethanol
Energy of confirmations of ethane is
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Stability order: Gauche form > Anti form > Partially eclipsed >
Fully eclipsed.
Newman projection of Ethylene Glycol
The most stable conformation of ethylene glycol is gauche, due
to the high stabilization induced by intramolecular hydrogen
bonding interaction.
Energy Profile of Conformations of Butane
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SUMMARY
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EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS
Introduction to Carbon and Its Compounds 3. The hybridization of carbon atoms in C—C single bond of
H—C C — CH CH2 is :
1. In which of the following molecules, all atoms are coplanar? (a) sp – sp
3 3
(b) sp2 – sp3
(c) sp – sp
3
(d) sp – sp2
4. Hybridized carbon atom used in the formation of the
compound CH3 — CH CH — CH2 — CH3 are :
(a) (a) sp and sp 3
(b) sp and sp2
(c) only sp (d) sp2 and sp3
5. In the hydrocarbon,
The state of hybridization of carbons 1,3,5 are in the
(b) following sequence :
(a) sp, sp2, sp3 (b) sp3, sp2, sp
(c) sp2, sp, sp3 (d) sp, sp3, sp2
(c) 6. Which of the following statements is true about hybridization ?
(a) Hybrid orbitals frequently undergo linear overlaps
making sigma bonds.
(b) Hybrid orbitals frequently undergo lateral overlaps making
-bonds. In other words, there are several compounds in
(d)
which -bonds are formed using hybrid orbitals.
(c) Hybrid orbitals are molecular orbitals.
(d) A hybrid orbital bigger in size makes shorter bond.
2. In which of the following molecules, all atoms are not coplanar ? 7.
C1—C2 bond of this molecule is formed by
(a) (a) sp3–sp2 overlap (b) sp2–sp3 overlap
(c) sp–sp2 overlap (d) sp2–sp2 overlap
8. In which of the following compounds, C has used sp2 orbital
in making C—O bond ?
(b)
(a) (b)
(c)
(c) (d)
9. In which of the following hybridization, bond angle is
the highest
(a) sp3 (b) sp2
(d)
(c) sp (d) sp 3d
GENERAL ORGANIC CHEMISTRY 74
10. 18. The IUPAC name of neopentane is
In this molecule (allene) (a) 2-methylbutane (b) 2, 2-dimethylpropane
(a) all three C-atoms are sp2-hybridized (c) 2-methylpropane (d) 2,2-dimethylbutane
(b) both terminal C-atoms are sp2-hybridized while central 19. The IUPAC name of CH3COCH (CH3)2 is
C-atom is sp-hybridized (a) isopropylmethyl ketone
(c) both terminal C-atoms are sp-hybridized while central C- (b) 2-methyl-3-butanone
atom is sp2-hybridized
(c) 4-methylisopropyl ketone
(d) none of these
(d) 3-methyl-2-butanone
11. Underlined carbon is sp 3 hybridised in
20. The correct IUPAC nomenclature for the following alcohol
(a) (b)
is :
(c) (d)
Reacting Species
12. Which of the following species is a nucleophile ?
(a) 2-ethyl-2-butanol
(a) H2O (b) H3O
(b) 3-methyl-3-pentanol
(c) both (a) and (b) (d) none of these
(c) 3-ethyl-3-methyl-3-pentanol
13. Which of the following species is a nucleophile ?
(d) 1, 1-diethylanol
(a) CH3O (b) CH3OH
21. The IUPAC name of the compound
(c) both (a) and (b) (d) none of these (CH3)2 CH – CH = CH – CHOH – CH3 is :
14. Which of the following species is an electrophile ? (a) 5-methylhex-3-en-2-ol
(a) H (b) H (b) 2-methylhex-3-en-5-ol
(c) both (a) and (b) (d) none of these (c) 2-hydroxy-5-methyl-3-hexene
IUPAC System of Nomenclature (d) 5-hydroxy-2-methyl-3-hexene
15. Which one of the following does not have sp 2 hybridised 22. The IUPAC name of the compound
carbon ?
(a) Acetone (b) Acetic acid is
(c) Acetonitrile (d) Acetamide
16. The suffixes for alcohols, aldehyes and ketones according (a) 3, 3-dimethyl-1-hydroxy cyclohexane
to IUPAC system are respectively : (b) 1, 1-dimethyl-3-hydroxy cyclohexane
(c) 3, 3-dimethyl-1-cyclohexanol
(a) -alc, -ald, -ket (b) -ol, -al, -ket
(d) 1, 1-dimethyl-3-cyclohexanol
(c) -ol, -al, -one (d) -coh, -ald, -one 23. The IUPAC name of the following compound is :
17. The correct decreasing order of priority for the functional
groups of organic compounds in the IUPAC system of
nomenclature is
(a) 2, 5, 6-trimethylheptane
(a) —COOH, —SO3H, —CONH2, — CHO (b) 1,3-isopropyl-3-methylpropane
(b) —SO3H, —COOH, —CONH2, —CHO (c) 2, 6, 3-trimethylheptane
(c) —CHO, —COOH, —SO3H, —CONH2 (d) 2,3,6-trimethylheptane
(d) —CONH2, —CHO, — SO3H,—COOH
GENERAL ORGANIC CHEMISTRY 75
24. Name of the compound given below is : 29. The IUPAC name of CH3CH2C(Br) CHCl is :
(a) 4-chloro-3-bromo but-3-ene
(b) 2-bromo-1-chloro butane
(c) 2-bromo-1-chloro but-1-ene
(d) 2-bromo-2-ethyl-3-chloro propene
30. The IUPAC name of is :
(a) 2,3-diethylheptane (b) 3-methyl-4-ethyloctane (a) 3-propylpent-1-ene (b) 3-ethylpent-1-ene
(c) 5-ethyl-6-methyloctane (d) 4-ethyl-3-methyloctane (c) 4-ethylhex-1-ene (d) 3-ethylhex-1-ene
31. The IUPAC name of CH3 C CCH CH3 2 is:
25. The IUPAC name of is (a) 4-methyl-2-pentyne
(b) 4,4 -dimethyl-2-pentyne
(a) 1, 1-diethyl-2, 2-dimethylpentane
(b) 4, 4-dimethyl-5, 5-diethylpentane (c) methyl isopropyl acetylene
(c) 5, 5-diethyl-4, 4-dimethylpentane (d) 4,4,4-trimethyl-1-butene
(d) 3-ethyl-4, 4-dimethylheptane 32. The IUPAC name of
26. The correct IUPAC name of the following compound :
is :
(a) 2,2-diethyl pentanoic acid
is (b) 2,4-dimethyl hexanoic acid
(c) 2-methyl-4-ethyl pentanoic acid
(a) 4 – methyl – 3 – ethylhexane (d) 4-ethyl-2-methyl pentanoic acid
(b) 3 – ethyl – 4 – methylhexane 33. The IUPAC name of the compound
(c) 3, 4 – ethylmethylhexane
(d) 4 – ethyl – 3 – methylhexane
27. The IUPAC name of CH3C(CH3)2 CH2CH CH2 is :
is :
(a) 2,2-dimethyl-4-pentene
(a) 3-ethyl-4-methylhex-5-en-2-ol
(b) 4,4-dimethyl-1-pentene (b) 3-ethyl-4-ethylhex-1-en-5-ol
(c) 1,1,1-trimethyl-3-butene (c) 3-ethyl-2-hydroxy-4-methylhex-5-ene
(d) 2-chloro-4,4-dimethylhexane (d) none of the above
28. The name of according to IUPAC 34. Which of the following compounds has incorrect IUPAC
nomenclature ?
nomenclature system is :
(a) 2,3-dibromo-1,4-dichlorobutene-2 (a) (b)
(b) 1,4-dichloro-2,3-dibromobutene-2
(c) dichlorobromobutene
(c) (d)
(d) dichlorobromobutane
GENERAL ORGANIC CHEMISTRY 76
Introduction of Reaction Intermediates Inductive Effect
35. Due to the presence of an unpaired electron, free radicals 38. Inductive effect of —CH3 group operates in
are
(a) cations (b) anions
(c) chemically inactive (d) chemically reactive (a) (b)
36. For the reactions
(I) (c) (d) all of these
39. In the following benzyl/allyl system
(II)
(R is alkyl group)
(III) decreasing order of inductive effect is
(a)
(b)
(IV)
(c)
(d)
The correct decreasing order of enthalpies of reaction for 40. Inductive effect of Cl atom operates in
producing carbocation is (a)
(b)
(a) H1o H o2 H 3o H 4o
(b) H o4 H1o H o2 H 3o
(c)
(c) H 3o H 2o H1o H 4o
(d) all of these
(d) H o2 H1o H o4 H 3o
41.
37. The order of reactivity of the following alcohols towards
conc. HCl is : Which of these groups has –I effect ?
(a) I (b) II
(I)
(c) III (d) all of these
42. Inductive effect of a —CH3 group operates
(II) (III) (a) (b)
(a) I > II > III (b) I > III > II
(c) (d) both (b) and (c)
(c) III > II > I (d) III > I > II
GENERAL ORGANIC CHEMISTRY 77
Resonance (c) II > III > I (d) II > I > III
43. Among these compounds, which one has shortest C—Cl 49. Among these canonical structures of pyridine, the correct
bond ? order of stability is
(a) I (b) II
(c) III (d) IV
44. Heat of hydrogenation of cyclohexene is –28.6 kcal/mol and
that of benzene is –49.8 kcal/mol. Then resonance energy of
benzene will be
(a) 46 kcal/mol (b) 39 kcal/mol
(c) 36 kcal/mol (d) 30 kcal/mol
45. Resonance structure of a molecules should have
(a) Identical arrangement of atoms
(b) Nearly the same energy content
(c) The same number of paired electrons
(d) All the above
46. In the anion, HCOO – the two carbon-oxygen bonds are
found to be of equal length. What is the reason for it ?
(a) Electronic orbits of carbon atom are hybridised
(b) The bond is weaker than the bond
(c) The anion, HCOO has two equivalent resonating
–
structures
(a) ( I = V) > (II = IV) > III
(d) The anion is obtained by removal of a proton from
the acid molecule (b) (II = IV) > (I = V) > III
47. Which of the following statements is true about this molecule ? (c) (I = V) > III > (II = IV)
(d) III > (II = IV) > (I = V)
50. The most stable canonical structure among these is
(a) C1—C2 and C3—C4 bonds are of same length
(b) C1—C2 bond is shorter than C3—C4 bond
(c) C1—C2 bond is longer than C3—C4 bond
(d) Cannot be predicted
48. The correct order of stability among these canonical
structures is (a) I (b) II
(c) III (d) all are equally stable
(a) I > III > II (b) III > I > II
GENERAL ORGANIC CHEMISTRY 78
51. The stability order of these canonical structures is 54. In which of the following molecule the resonance effect is
not present for lone pair or charge ?
(a)
(b)
(c)
(a) I > II > III (b) III > I > II (d)
(c) I > III > II (d) II > III > I
52. Which of the following is most stable ? 55. The most unlikely representation of resonance structure of
p–nitrophenoxide ion is :
(a) (b)
(a) I (b) II (c) (d)
(c) III (d) IV
Resonance or Mesomeric Effect and Concept of
56. Number of electrons present in naphthalene is
Aromaticity
(a) 4 (b) 6
53. Which one of the following substituents at para-position
is most effective in stabilizing the phenoxide (c) 10 (d) 14
ions ?
(a) –OCH3 (b) –CH2OH
(c) –CH3 (d) –COCH3
GENERAL ORGANIC CHEMISTRY 79
Hyperconjugation 61. Which of the following orders is correct for no-bond-
resonance energy of these radicals ?
57. Which of the following orbital diagrams represents the case
of hyperconjugation ?
(a)
(a) I > II > III (b) III > II > I
(c) I > III > II (d) II > I > III
62. Which of the following represents the case of
hyperconjugation ?
(a) (b)
(b)
(c) (d) both (b) and (c)
(c) both (a) and (b)
(d) none of these
58. How many hyperconjugable H-atoms does this molecule has ?
63. Hyperconjugation occurs in
(a)
(a) 0 (b) 2
(c) 3 (d) 4 (b)
59. Hyperconjugation occurs in
(a) CH CH2 (b) CH CH CH3
3 3
(c)
(c) CH CH2 CH2 (d) all of these
3
(d) All of these
60. Which of the following orders is correct for no-bond-
resonance energy of these radicals ?
(a) I > II > III (b) III > II > I
(c) III > I > II (d) II > III > I
GENERAL ORGANIC CHEMISTRY 80
67.
64.
Which of the following orders is correct for the stability of
these carbanions ?
Canonical structures due to hyperconjugation in this (a) I > II > III (b) III > II > I
molecule can be written as
(a) (b) (c) II > I > III (d) I II III
68.
Which of the following orders is correct for the stability of
these carbanions ?
(a) I > II > III (b) III > II > I
(c) II > III > I (d) II > I > III
(c) both (a) and (b) (d) none of these
Applications of Electronic Effects 69.
65. Among the following acids which has the lowest pK a (I) (II) (III)
value? Which of the following orders is correct for the stability of
(a) CH3CH2COOH (b) (CH3)2CH—COOH these carbanions ?
(c) HCOOH (d) CH3COOH (a) I > II > III (b) III > II > I
66. In which of the following molecules, –NO2 group is not (c) II > I > III (d) III > I > II
coplanar with phenyl ring ?
70. Which of the following carbocation is least stable ?
(a) (b) (a) (b) CH CH2
(c) CH 2 CH CH2 (d)
(c) (d)
GENERAL ORGANIC CHEMISTRY 81
71. What is the correct order of stability of the given cations: (c) D < A < B < C (d) A < D < C < B
75.
Which of the following orders is correct for the stability of
these carbanions ?
(a) I > II > III (b) III > II > I
(c) III > I > II (d) II > I > III
76. The increasing order of stability of the following free
radicals is
(a) III > II > IV > I (b) I > II > III > IV (a) CH 3 CH CH 3 C C6 H 5 CH C6 H 5 C
2 3 2 3
(c) III > I > II > IV (d) IV > II > III > I
(b) C6 H 5 C C 6 H 5 CH CH 3 C CH 3 CH
72. Which of the following statements is correct about methyl 3 2 3 2
group ? (c) C6 H 5 CH C6 H 5 C CH 3 C CH 3 CH
2 3 3 2
(a) It stabilizes both carbocation and free radical equally
(d) CH 3 CH CH 3 C C6 H 5 C C 6 H 5 CH
(b) it stabilizes a free radical more than a carbocation 2 3 3 2
(c) it stabilizes a carbocation more than a free radical Structural Isomerism
(d) none of these 77.
73. The order of stability of the following carbocations
CH 2 CH C H 2 ;CH 3 CH 2 C H 2 ;
I II
(a) III > II > I (b) II > III > I Among these, chain isomers are
(c) I > II > III (d) III > I > II (a) I and II (b) I and III
74. The correct order of increasing acid strength of the (c) II and III (d) all of these
compounds
(A) CH3CO2H (B) MeOCH2CO2H
(C) CF3CO2H (D) is
(a) B < D < A < C (b) D < A < C < B
GENERAL ORGANIC CHEMISTRY 82
81.
78.
OH
Among these functional isomers are
(a) I and II (b) I and III
(c) II and III (d) Both (a) and (c)
Among these, I is the chain isomer of
(a) II only (b) III only 82. Isomers are the compounds having the
(c) both (d) none of these (a) same molecular formula but different physical and/or
79. chemical properties.
(b) same structural formula but different molecular formulae
(c) same chemical properties and physical properties
(d) same physical properties but different chemical properties.
Among these III is the chain isomer of 83.
(a) I only (b) II only
(c) both I and II (d) none of these
80.
Among these, positional isomers are
(a) I and II (b) I and III
(c) II and III (d) all of these
84. The compound C4H10O can show
(a) metamerism (b) positional isomerism
(c) functional isomerism (d) all types
85. The number of structural isomers for C6H14 is:
Which among these are tautomers ?
(a) 4 (b) 5
(a) I and II (b) I and III
(c) 6 (d) 3
(c) II and III (d) None of these
GENERAL ORGANIC CHEMISTRY 83
Geometrical Isomerism 91. Which of the following can exist as cis and trans isomers ?
86. (a) (b)
(c) (d)
92. Which is a pair of geometrial isomers ?
Which among these are stereo-isomers ?
(a) I and II (b) I and III
(a) I and II (b) I and III
(c) II and III (d) all of these
87. Geometrical isomerism will be exhibited by (c) II and IV (d) III and IV
(a) Pent–1–ene 93. Which of the following will exhibit geometrical isomerism ?
(b) 3–Methylbut–1–ene (a) 1–Phenylbut–2–ene
(c) Pent–2–ene (b) 3–Phenylbut–1–ene
(d) All of these compounds (c) 2–Phenylbut–1–ene
88. The simplest alkene which is capable of exhibiting (d) 1, 1–Diphenylprop–1–ene
geometrical isomerism has 94. Which of the following compounds can show geometrical
(a) 3 carbon atoms (b) 5 carbon atoms isomerism ?
(c) 6 carbon atoms (d) 4 carbon atoms (a) Vinyl chloride (b) 1, 1–Dichloroethene
89. Which of the following compounds can exhibit geometrical (c) 1, 2–Dichloroethene (d) Trichloroethene
isomerism ? 95. Which of the following pair of structures represent
(a) Hex–1–ene (b) 2–Methylpent–2–ene geometrical isomers of each other?
(c) 3–Methylpent–1–ene (d) Hex–2–ene
90. Which one of the following compound will show geometrical (a)
isomerism ?
(a) (b)
(b)
(c) (d)
(c)
(d)
GENERAL ORGANIC CHEMISTRY 84
EXERCISE - 2 : PREVIOUS YEAR JEE MAIN QUESTIONS
1. Which one of the following compounds is non-aromatic? Choose the correct answer from the following options
(2021-02-24/Shift-2) (a) (A) and (B) only
(b) (B) and (C) only
(c) (A), (B) and (C) only
(a) (b) (d) (B), (C) and (D) only
5. Compound with molecular formula C3H6O can show:
(2021-03-18/ Shift - 1)
(c) (d) (a) Both positional isomerism and metamerism
(b) Metamerism
2. The correct order of acid character of the following (c) Functional group isomerism
compounds is: (2021-02-25/Shift-2) (d) Positional isomerism
6. In the following molecule,
Hybridisation of Carbon a, b and c respectively are:
(a) IV > III > II > I (b) II > III > IV > I
(2021-03-18/Shift-2)
(c) III > II > I > IV (d) I > II > III > IV
(a) sp , sp, sp
3
(b) sp , sp, sp2
3
1 2 3 4
3. In C H 2 C C H C H3 molecule, the hybridization of (c) sp3, sp2, sp (d) sp3, sp2, sp2
carbon 1, 2, 3 and 4 respectively, are:
(2021-02-25/Shift-2) 7. Which of the following is an aromatic compound?
(a) sp2, sp, sp2, sp3 (2021-03-17/Shift - 1)
(b) sp3, sp, sp3, sp3
(c) sp2, sp3, sp2, sp3
(a) (b)
(d) sp2, sp2, sp2, sp3
4. Among the following, the aromatic compounds are:
(c) (d)
(2021-03-16/Shift - 1)
GENERAL ORGANIC CHEMISTRY 85
8. Which of the following compounds does not exhibit 11. Given below are two statements:
resonance? (2021-07-22/Shift - 2) Statement I: Hyperconjugation is a permanent effect.
(a) CH 3CH 2 OCH CH 2 Statement II: Hyperconjugation in ethyl cation involves
CH 3 C H 2 the overlapping of Csp2 H1s bond with
(b) empty 2p orbital of other carbon.
Choose the correct option: (2021-07-27/Shift - 2)
(c) CH3CH 2 CH 2 CONH 2 (a) Both statement I and statement II are false
(b) Statement I is incorrect, but statement II is true
(d) CH 3CH 2 CH CHCH 2 NH 2
(c) Statement I is correct, but statement II is false
(d) Both Statement I and statement II are true
9. Which one among the following resonating structures is
least stable? (2021-07-25/Shift - 1)
12. Staggered and eclipsed conformers of ethane are:
(2021-07-27/Shift-1)
(a) Polymers
(a)
(b) Rotamers
(c) Enantiomers
(d) Mirror images
(b)
13.
(c)
The correct order of stability of given carbocation is:
(2021-07-27/Shift - 1)
(a) A > C > B > D (b) D > B > C > A
(c) D > B > A > C (d) C > A > D > B
(d)
10. Which among the following is the strongest acid?
14.
(2021-07-25/Shift - 2)
(a) CH3CH 2 CH 2 CH3 (b) Among the given species the resonance stabilised
carbocations are: (2021-07-20/Shift - 1)
(a) (C) and (D) only
(b) (A), (B) and (D) only
(c) (d)
(c) (A) and (B) only
(d) (A), (B) and (C) only
GENERAL ORGANIC CHEMISTRY 86
15. Which one of the following pairs of isomers is an example 16. Arrange the following conformational isomers of n-
of metamerism? (2021-07-20/Shift - 2) butane in order of their increasing potential energy:
(a)
(2021-08-31/Shift - 2)
(a) II < III < IV < I (b) I < IV < III < II
(b) (c) II < IV < III < I (d) I < III < IV < II
17. The total number of C–C sigma bond/s in mesityl oxide
C6 H10 O is ............... (Round off to the Nearest Integer).
(2021-03-17/Shift - 2)
(c) 18. The number of acyclic structural isomers (including
geometrical isomers) for pentene are______.
(2021-07-22/Shift - 2)
(d)
19. The number of sigma bonds in
is ________.
(2021-07-25/Shift-1)
20. The dihedral angle in staggered form of Newman
projection of 1, 1, 1-Trichloro ethane is......... degree.
(Round off to the nearest integer) (2021-07-27/Shift - 1)
GENERAL ORGANIC CHEMISTRY 87
21. Arrange the following carbocations in decreasing order
of stability. (JEE Main 2022)
(a) (b)
(c) (d)
25. Which will have the highest enol content?
(JEE Main 2022)
(a) B > A > C (b) A > B > C
(c) C > B > A (d) C > A > B
22. In the following structures, which one is having
staggered conformation with maximum dihedral
angle? (JEE Main 2022)
(a) (b)
(a)
(c) (d)
26. Which of the following is most stable?
(JEE Main 2022)
(b)
(a) (b)
(c) (d)
27. Which of the following structures are aromatic in
nature? (JEE Main 2022)
(c)
(a) A, B, C and D
(b) Only A and B
(d)
(c) Only A and C
23. The IUPAC name of ethylidene chloride is: (d) Only B, C and D
(JEE Main 2022) 28. The correct IUPAC name of the following compound
(a) 1-Chloroethene is (JEE Main 2022)
(b) 1-Chloroethyne
(c) 1,2-Dichloroethane
(d) 1,1-Dichloroethane
•
24. C7 H 5O2 2
hv
X 2 C6 H 5 2CO2
(a) 4-methyl-2-nitro-5-oxohept-3-enal
Consider the above reaction and identify the (b) 4-methyl-5-oxo-2-nitrohept-3-enal
intermediate ‘X’ (JEE Main 2022) (c) 4-methyl-6-nitro-3-oxohept-4-enal
(d) 6-formyl-4-methyl-2-nitrohex-3-enal
GENERAL ORGANIC CHEMISTRY 88
29. Which of the following carbocations is most stable? 33. The correct decreasing order of priority of functional
(JEE Main 2022) groups in naming an organic compound as per IUPAC
system of nomenclature is : (JEE Main 2022)
(a) –COOH > –CONH2 > –COCl > –CHO
(b) –SO3H > –COCl > –CONH2 > –CN
(a)
(c)
(d) –COOH > –COOR > –CONH2 > –COCl
(b) 34. Which of the following is not an example of benzenoid
compound ? (JEE Main 2022)
(c)
(a) (b)
(d)
30. Arrange the following in decreasing acidic strength.
(JEE Main 2022)
(c) (d)
35. Given below are two statements. One is labelled as
Assertion A and the other is labelled as Reason R.
Assertion A: [6] Annulene. [8] Annulene and cis –
(a) A > B > C > D (b) B > A > C > D [10] Annulene, are respectively aromatic, not-aromatic
(c) D > C > A > B (d) D > C > B > A and aromatic.
31. Which of the following compounds is not aromatic?
(JEE Main 2022)
[6] Annulene
(a) (b)
[8] Annulene
(c) (d)
32. The correct stability order of the following diazonium Cis-[10] Annulene
salt is (JEE Main 2022)
Reason R: Planarity is one of the requirements of
aromatic systems.
In the light of the above statements, choose the most
appropriate answer from the options given below.
(JEE Main 2022)
(a) Both A and R are correct and R is the correct
explanation of A.
(b) Both A and R are correct but R is NOT the correct
(a) (A) > (B) > (C) > (D)
(b) (A) > (C) > (D) > (B) explanation of A.
(c) (C) > (A) > (D) > (B) (c) A is correct but R is not correct.
(d) (C) > (D) > (B) > (A)
(d) A is not correct but R is correct.
GENERAL ORGANIC CHEMISTRY 89
36. Which among the following is the strongest Bronsted In the light of the above statement, choose the most
base ? (JEE Main 2022) appropriate answer from the options given below.
(a) Both Statement I and Statement II are correct
(b) Both Statement I and Statement II are incorrect.
(c) Statement I is correct but Statement II is incorrect.
(d) Statement I is incorrect but Statement II is correct.
39. Match List-I with List-II.
List-I List-II
(a) (b)
(A)
(I) Spiro compound
(B)
(II) Aromatic compound
(c) (d)
(C)
37. Correct structure of -methylcyclohexane (III) Non-planar
Heterocyclic
carbaldehyde is : (JEE Main 2022)
compound
(D)
(IV) Bicyclo compound
(a)
Choose the correct answer from the options given
below: (JEE Main 2022)
(a) (A) – (II), (B) – (I), (C) – (IV), (D) – (III)
(b) (b) (A) – (IV), (B) – (III), (C) – (I), (D) – (II)
(c) (A) – (III), (B) – (IV), (C) – (I), (D) – (II)
(d) (A) – (IV), (B) – (III), (C) – (II), (D) – (I)
40. Number of electrophillic centres in the given
(c)
compound is_____. (JEE Main 2022)
(d)
38. Given below are two statements. (JEE Main 2022)
41. Total number of possible stereoisomers of dimethyl
cyclopentane is _____. (JEE Main 2022)
Statement I: The compound is optically 42. Observe structures of the following compounds
active.
The total number of structures/compounds which
posses asymmetric carbon atoms is ____.
(JEE Main 2022)
Statement II: is mirror image of 43. The number of chiral alcohol(s) with molecular
above compound A. formula C4H10O is_____. (JEE Main 2022)
GENERAL ORGANIC CHEMISTRY 90
44. The number of sp3 hybridised carbons in an acyclic
neutral compound with molecular formula C4H5N is :
(JEE Main 2022)
45. Optical activity of an enantiomeric mixture is +12.6°
and the specific rotation of (+) isomer is +30°. The
optical purity is____% (JEE Main 2022)
46. The number of stereoisomers formed in a reaction of (c)
(±) Ph(C=O) C(OH)(CN)Ph with HCN is_____.
(JEE Main 2022)
47. Increasing order of stability of the resonance structure
is:
(d)
50. Match List I with List II.
List I(Isomeric pairs) List II(Type of Isomers)
A. Propanamine and N-
I. Metamers
Methylethanamine
B. Hexan-2-one and
II. Positional isomers
Hexan-3-one
C. Ethanamide and
III. Functional isomers
Hydroxyethanimine
D. o-nitrophenol and p-
IV. Tautomers
nitrophenol
Choose the correct answer from the options given
(JEE Main 2023)
(a) C, D, B, A (b) C, A, B, D below :- (JEE Main 2023)
(c) D, C, A, B (d) D, C, B, A (a) A-III, B-IV, C-I, D-II
48. Which will undergo deprotonation most readily in
(b) A-IV, B-III, C-I, D-II
basic medium?
(c) A-II, B-III, C-I, D-IV
(d) A-III, B-I, C-IV, D-II
51. What is the correct order of acidity of the protons
(JEE Main 2023)
(a) a only (b) c only marked A–D in the given compounds ?
(c) Both a and c (d) b only
49. Which of the following conformations will be the most
stable ? (JEE Main 2023)
(JEE Main 2023)
(a) HC > HD > HB > HA
(a)
(b) HC > HD > HA > HB
(c) HD > HC > HB > HA
(d) HC > HA > HD > HB
(b)
GENERAL ORGANIC CHEMISTRY 91
52. The most stable carbocation for the following is: 56. The decreasing order of hydride affinity for following
(JEE Main 2023) carbocations is:
(a) (b)
(c) (d)
53. The strongest acid from the following is
(JEE Main 2023)
Choose the correct answer from the options given
below: (JEE Main 2023)
(a) C, A, D, B (b) A, C, B, D
(c) A, C, D, B (d) C, A, B, D
(a) (b) 57. Correct statements for the given reaction are:
(c) (d)
54. The descending order of acidity for the following A. Compound ‘B’ is aromatic
carboxylic acid is- B. The completion of above reaction is very slow
A. CH3COOH C. ‘A’ shows tautomerism
B. F3C—COOH D. The bond lengths of C-C in compound B are found
C. ClCH2—COOH to be same
D. FCH2—COOH Choose the correct answer from the options given
E. BrCH2—COOH below: (JEE Main 2023)
Choose the correct answer from the options given (a) B, C and D only (b) A, B and C only
below: (JEE Main 2023) (c) A, C and D only (d) A, B and D only
(a) E > D > B > A > C 58. Among the following compounds, the one which
(b) B > D > C > E > A shows highest dipole moment is (JEE Main 2023)
(c) B > C > D > E > A
(d) D > B > A > E > C
55. The correct IUPAC nomenclature for the following (a)
compound is:
(b)
(JEE Main 2023) (c)
(a) 5-Formyl -2-methylhexanoic acid
(b) 2-Formyl -5-methylhexan-6-oic acid
(c) 5-Methyl-2-oxohexan-6-oic acid (d)
(d) 2-Methyl-5-oxohexanoic acid
GENERAL ORGANIC CHEMISTRY 92
59. Given below are two statements : 61.
Statement I: Tropolone is an aromatic compound and
has 8π electrons.
Statement II: π electrons of >C = O group in
tropolone is involved in aromaticity.
In the light of the above statements, choose the correct
The number of hyperconjugation structures involved to
answer from the options given below:
stabilize carbocation formed in the above reaction is
(JEE Main 2023)
______. (JEE Main 2023)
(a) Statement I is true but Statement II is false
(b) Both Statement I and Statement II are true
(c) Both Statement I and Statement II are false
(d) Statement I is false but Statement II is true
60. Given below are two statements, one is labelled as
Assertion A and the other is labelled as Reason R.
Assertion A: Order of acidic nature of the following
compounds is A > B > C.
Reason R: Fluoro is a stronger electron withdrawing
group than Chloro group.
In the light of the above statements, choose the correct
answer from the options given below:
(JEE Main 2023)
(a) A is false but R is true
(b) A is true but R is false
(c) Both A and R are correct, but R is NOT the correct
explanation of A
(d) Both A and R are correct, and R is the correct
explanation of A
GENERAL ORGANIC CHEMISTRY 93
EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS
Objective Questions I [Only one correct option] 6. Which of these groups has –I effect ?
1. Which of the following alkenes will exhibit geometrical
isomerism ?
(a) CH3–CH2–CH2–CH = CH2 (a) I (b) II
(b) CH3–CH2–CH = CH–CH3 (c) III (d) all of these
(c) CH3–CH2–CH = CH–CH2–CH3 7. Which of these groups has +I effect ?
(d) both (b) and (c) CH 3 CH CH 2 C CH
I II III
2. Aniline is weaker base than ethyl amine. This is due to
(a) I (b) II
(a) – I effect of NH2 in aniline
(c) III (d) all of these
(b) – R effect of NH2 in aniline
8. Which of the following alkyl benzenes has maximum elec-
(c) + I effect of NH2 in aniline tron density?
(d) + R effect of NH2 in aniline
3. Which of the following is strongest acid ?
(a) (b)
(a) HCOOH (b) CH3COOH
(c) (d)
(c) (b)
4. Which of the following orders is correct for the basic-
strength of these 1º, 2º and 3º amines in gas phase ? 9. Consider the following structures
(I) CH3NH2 (II) (CH3)2NH (III) (CH3)3N (I) CH 2 C H (II) CH 3 C H 2
(a) I > II > III (b) III > II > I
(III) CH 2 CH C H 2 (IV) C 6 H 5 C H C 6 H 5
(c) II > I > III (d) II > III > I
The correct sequence of these carbocations in the
5. Which of the following orders is correct for the basic-
decreasing order of their stability is
strength of these amines in polar solvents (e.g., –H2O) ?
(a) IV, III, II, I (b) I, II, III, IV
(I) CH3NH2 (II) (CH3)2NH
(c) IV, II, III, I (d) I, III, II,
(III) (CH3)N
(a) I > II > III (b) III > II > I
(c) II > I > III (d) II > III > I
GENERAL ORGANIC CHEMISTRY 94
10. Which of the following no-bond-canonical structures is (c) both (a) and (b)
correct for this radical ?
(d) none of these
12. The total number of contributing structures showing
hyperconjugation (involving C–H bonds) for the
following carbocation is:
(a) 4 (b) 5
(a)
(c) 6 (d) 7
13. Which statement explains why the element carbon forms
so many compounds with different shape?
(a) Carbon atoms combine readily with oxygen.
(b) Carbon atoms have very high electronegativity.
(c) Carbon readily forms ionic bonds with other carbon
atoms.
(b)
(d) Carbon readily forms covalent bonds with other
carbon atoms.
14. The reaction
represents
(c) (a) nucleophilic substitution
(b) electrophilic addition
(c) electrophilic substitution
(d) elimination reaction
(d) none of these
15. The hybridization of carbon in diamond, graphite and
11. Regarrangement in this carbocation will produce
acetylene are respectively:
(a) sp3, sp, sp2 (b) sp, sp2, sp3
(c) sp3, sp2, sp (d) sp2, sp3, sp
16. CH2=CH–CH=CH–CH=CH–CH3
How many geometrical isomers of this compound are
(a) possible ?
(a) 2 (b) 3
(c) 4 (d) 8
(b)
GENERAL ORGANIC CHEMISTRY 95
17. CH3–CH2–CH=CH–CH=CH–CH3
How many geometrical isomers of this compound are
possible ?
(a) 2 (b) 3 (b)
(c) 4 (d) 8
18. Arrange following compounds in decreasing order of basicity.
(c)
(a) IV > I > III > II (b) III > I > IV > II
(c) II > I > III > IV (d) I > II > III > IV
19. Which of the following orders is correct for the basic- (d)
strength of these compounds ?
21. Correct order of basicity of various nitrogen in
I.
II.
III. CH3 NH 3
(a) I > II > III (b) III > II > I
(a) 1 > 2 > 3 (b) 2 > 1 > 3
(c) I > III > II (d) II > I > III
(c) 2 > 3 > 1 (d) 3 > 2 > 1
20. Which is the major product of the following reaction ?
22. Which of the following orders is correct for the basic-strength
of these anilines ?
(a) I > II > III (b) III > II > I
(a)
(c) II > I > III (d) I > III > II
GENERAL ORGANIC CHEMISTRY 96
23. Which of the following is the most stabilized carbocation? 26. What is the decreasing order of stability (most stable
least stable) of the following carbocations ?
(a)
(b)
(a) 3 >2 > 1 > 4 > 5 (b) 3 > 2 >5 > 4 >1
(c) 1 4 2 5 3 (d) 3 1 4 2 5
(c) 27. Which of the following carbocation is most stable ?
(a) (b)
(d)
24. Which carbocation is the most stabilized ?
(c) (d)
(a) (b) 28. Relative stabilities of the following carbocation will be in
order :
(c) (d)
25. Which of the following options is the correct order of relative
stabilities of cations as written below (most stable first) ?
(I)
(a) I < II < III < IV (b) IV < III < II < I
(c) IV < II < III < I (d) II < IV < III < I
(II)
29. What is the decreasing order of strength of the bases ?
OH , NH 2 , H – C C and CH 3 CH 2
(III)
(a) CH 3 CH 2 NH 2 H C C OH
(a) I > II > III (b) II > III > I (b) H C C CH 3 CH 2 NH 2 OH
(c) III > I > II (d) I > III > II (c) OH NH 2 H C C CH 3 CH 2
(d) NH 2 H C C OH CH 3 CH 2
GENERAL ORGANIC CHEMISTRY 97
30. Which of the following orders is correct for the stability of 34. The three carbanions follows which order of stability
these carbanions ?
(a) I > II > III (b) III > II > I
(c) II > III > I (d) II > I > III (a) I > II > III (b) I > III > II
31. Which of the following is least stable? (c) II > I > III (d) II > III > I
35. The correct arrangement of the relative stability of the three
carbocation is :
(a) I > II > III (b) III > II > I
(a) I (b) II
(c) III (d) None (c) I > III > II (d) III > I > II
32. Arrange the following in decreasing order of stability. 36. Which of the following is most likely to undergo a favourable
hydride shift ?
(a) (b)
(a) I > II > III (b) I > III > II (c) (d)
(c) II > I > III (d) II > III > I
33. The correct order of stability of the three isomeric carbanions is: 37. Which of the following orders is correct for the stability of
these carbocations ?
(a) I > II < III (b) I > III > II
(c) II > I > III (d) II > III > I
(a) I > II > III (b) III > II > I
(c) II > III > I (d) III > I > II
GENERAL ORGANIC CHEMISTRY 98
38. Which of the following orders is correct for the stability of 41. Which of the following is least stable?
these carbocations ?
(a)
(b)
(a) I > II > III (b) III > II > I
(c) II > I > III (d) II > III > I (c)
39. Rearrangement in this carbocation will
produce (d)
(a)
42. Which of the following ring compounds obeys Huckel’s
(b) rule?
(a) C 4 H 41 (b) C 4 H 41
(c) both (a) and (b)
(c) C 4 H 42 (d) C4 H 4
(d) none of these
43. The correct acidity order of the following is
40. Which of the following is correctly named?
(a)
(a) (III) > (IV) > (II) > (I) (b) (IV) > (III) > (I) > (II)
(c) (III) > (II) > (I) > (IV) (d) (II) > (III) > (IV) > (I)
(b)
44. How many open chain structural isomers of compound with
molecular formulaC6H12 show geometrical isomerism ?
(a) 2 (b) 3
(c) 4 (d) 5
Objection Question II
(c)
[One or more than one correct option]
45. Br has low reactivity in CH 2 CH Br because
(a) the C Br bond has a partial double bond character
(d) (b) of the +M effect of bromine
(c) Br is electronegative
(d) None of the above
GENERAL ORGANIC CHEMISTRY 99
46. Which of the following have larger C—O bond length than 49. Which statements among following are correct ?
O (a) Hydration effect stabilize dimethyl ammonium ion more
||
C—O bond length of CH 3 C CH 3 ? than trimethyl ammonium ion
(b) is more basic than
(a) (b)
(c) basicity order
(d) Phenol is more acidic than CH3OH
(c) (d)
Assertion Reason
(A) If both Assertion and Reason are correct and
47. Which of the statements are incorrect about the following Reason is the correct explanation of Assertion
compound ? (B) If both Assertion and Reason are true but
Reason is not the correct explanation of
Assertion.
(C) If Assertion is true but Reason is false.
(D) If Assertion is false but Reason is true.
50. Assertion (A) : The C C distance is longer than C = C
distance
(a) All three C—N bonds are of same length
Reason (R) : Both C atoms in alkenes are sp2 hybridized.
(b) C1 — N and C3 — N bonds are of same length but shorter
than C5 — N bond (a) A (b) B
(c) C1 — N and C5 — N bonds are of same length but (c) C (d) D
longer than C3 — N bond
51. Assertion (A) : Tropylium cation is more stable than
(d) C1 — N and C3 — N bonds are of different length but CH3 3 C
both are longer than C5 — N bond
Reason (R) : It is stabilized by both resonance effect and
48. Which of the following alkenes are more stable than inductive effect.
(a) A (b) B
(c) C (d) D
52. Assertion (A) : p-nitrophenol is a stronger acid than
o-nitrophenol.
Reason (R) : Intramolecular hydrogen bonding make the
(a) (b) o-isomer weaker acid than p-isomer.
(a) A (b) B
(c) C (d) D
53. Assertion (A) : The acetate ion is a weaker base than the
ethoxide ion.
(c) (d)
Reason (R) : In carboxylic acids, the carbonyl group is
polarized and so the carbon of the carbonyl group bears a
GENERAL ORGANIC CHEMISTRY 100
partial +ve charge. 60. Assertion (A) : Tertiary carbocations are generally formed
more easily than primary carbocations.
(a) A (b) B
Reason (R) : Hyperconjugation as well as inductive effect
(c) C (d) D due to additional alkyl groups stabilize tertiary carbocations.
(a) A (b) B
54. Assertion (A) : The carbocation CF3 CH2 is less stable
(c) C (d) D
than CF3 . Match the Following
Each question has two columns. Four options are
Reason (R) : In case of CF3 CH2, CF3 is strong electron
withdrawing, therefore increases +ve charge whereas in given representing matching of elements from
CF3 , lone pair of ‘F’ overlap with vacant p-orbital of carbon
Column-I and Column- II.
reducing +ve charge by p - p bonding or back bonding. 61. Match the Column I and II (Matrix)
(a) A (b) B Column - I Column - II
(c) C (d) D (A) — NO2 (P) –M effect
–
55. Assertion (A) : The two structures, (B) — O (Q) +M effect
(C) — O — CH3 (R) +I effect
CH3 – CH2 – CH2 – C CH and CH 3 CH C CH
| (D) C N (S) –I effect
CH3 62. Match the Column I and II (Matrix)
are chain isomers. Column - I Column - II
Reason (R) : The chain isomers differ in the chain of carbon
(A) CH 3 C H CH 3 (P) Pyramidal structure
atoms.
(a) A (b) B (B) C H 3 (Q) Planar geometry
(c) C (d) D
(C) CH 3 C H CH 3 (R) Electrophile
56. Assertion (A) : CHCl = CHBr exhibits geometrical isomerism.
Reason (R) : Presence of C = C is the condition for a (D) Singlet carbene (S) Nucleophile
compound to exhibit geometrical isomerism.
(a) A (b) B
Paragraph Type Questions
(c) C (d) D Use the following passage, solve Q. 63 to Q. 65
57. Assertion (A) : Ethylene is more reactive than ethane. Passage
Reason (R) : Ethylene possess bond. Hyperconjugation is no bond resonance. It involves
(a) A (b) B electrons of C—H bond. Greater the number of C — H bonds (-
(c) C (d) D hydrogen atoms w.r.t. double bond) more will be hyperconjugative
58. Assertion (A) : Conjugated dienes are more stable than non- structures, more will be stability. Heats of hydrogenation of
conjugated dienes. alkenes are affected by hyperconjugative effects. Greater the
Reason (R) : 1,4-Pentadiene is a non-conjugated diene. hyperconjugative structures, lower will be the heat of
(a) A (b) B hydrogenation.
(c) C (d) D 63. Which of the following has highest heat of hydrogenation?
59. Assertion (A) : All carbon atoms in 1,3-butadiene are sp2
hybridized. (a) CH 2 CH 2 (b) But-l-ene
Reason (R) : 1,3-Butadiene is a conjugated diene. (c) Isobutylene (d) Tetramethyl ethylene
(a) A (b) B 64. Which of the following has highest heat of combustion ?
(c) C (d) D
(a) Isobutylene (b) But-l-ene
(c) Tetramethyl ethylene (d) But-2-ene
GENERAL ORGANIC CHEMISTRY 101
65. Which of the following is incorrect hyperconjugative 66. Which of the following alkenes is most stabilized?
structure?
(a) (b)
(c) (d)
(a) (b)
67. Which of the following cations is hyperconjugation
destabilized?
(a) (b)
(c) (d)
Use the following passage, solve Q. 66 to Q. 67 (c) (d)
Passage
When (C—H) electrons are in conjugation to pi bond, this
Subjective Type Questions
conjugation is known as hyperconjugation : For any
compound to show hyperconjugation 68. In acidic medium, ................ behaves as the strongest base.
2
(i) Compound should have one sp -hybridised carbon. (nitrobenzene, aniline, phenol)
2 3
(ii) -carbon with respect to sp should be sp 69. Arrange the following in the order of their increasing basicity.
(iii) -carbon should contain at least one hydrogen atom. p-toluidine, N, N-dimethyl-p-toluidine, p-nitroaniline, aniline.
No. of -carbon stability of cation and alkene. 70. Give reasons for the following in one or two sen
tences. The central carbon-carbon bond in 1, 3-
butadiene is shorter than that of n-butane.
GENERAL ORGANIC CHEMISTRY 102
EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTION
Objective Questions I [Only one correct option] 8. Arrange in order of increasing acidic strength (2004)
1. Which of the following, has the most acidic hydrogen ?
(2000)
(a) 3-hexanone (b) 2, 4-hexanedione
(c) 2, 5-hexanedione (d) 2, 3-hexanedione
(a) X > Z > Y (b) Z < X > Y
2. Among the following, the strongest base is (2000)
(c) X > Y > Z (d) Z > X > Y
(a) C6H5NH2 (b) p-NO2C6H4NH2
9. Which of the following resonating structures of 1-methoxy-
(c) m-NO2— C6H4NH2 (d) C6H5CH2NH2 1, 3-butadiene is least stable ? (2005)
3. The correct order of basicities of the following compounds
is (2001) (a) C H 2 CH CH CH O CH 3
(b) CH 2 CH C H CH O CH 3
(c) C H2 C H CH CH O CH3
(a) 2 > 1 > 3 > 4 (b) 1 > 3 > 2 > 4
(d) CH 2 CH C H C H O CH 3
(c) 3 > 1 > 2 > 4 (d) 1 > 2 > 3 > 4
4. Which of the following hydrocarbons has the lowest dipole 10. Which of the following is obtained when 4-methylbenzene
moment ? (2002) sulphonic acid is hydrolysed with excess of sodium
acetate ? (2005)
(a) cis-2-butene (b) 2-butyne
(c) 1-butyne (d)
(a)
5. Identify the correct order of boiling points of the following
compounds
(1) CH3CH2CH2CH2OH (2) CH3CH2CH2CHO
(3) CH3CH2CH2COOH (2002) (b)
(a) 1 > 2 > 3 (b) 3 > 1 > 2
(c) 1 > 3 > 2 (d) 3 > 2 > 1
6. Which of the following acids has the smallest dissociation
constant ? (2002) (c)
(a) CH3CHFCOOH (b) FCH2CH2COOH
(c) BrCH2CH2COOH (d) CH3CHBrCOOH
7. Which of the following represents the given mode of (d)
hybridisation sp 2 – sp 2 – sp – sp from left to right ?
(2003)
(a) H2C = CH – C N (b) HC C – C CH
(c) H2C = C = C = CH2 (d)
GENERAL ORGANIC CHEMISTRY 103
11. Among the following, the least stable resonance structure is 15. The correct stability order of the following resonance
(2007) structure is
(a)
(2009)
(b)
(a) (I) > (II) > (IV) > (III) (b) (I) > (III) > (II) > (IV)
(c) (II) > (I) > (III) > (IV) (d) (III) > (I) > (IV) > (II)
16. Among the following compounds, the most acidic is
(c) (2011)
(a) p-nitrophenol (b) p-hydroxybenzoic acid
(c) o-hydroxybenzoic acid (d) p-toluic acid
17. Which of the following compounds will show highest dipole
(d) moment (2018)
12. The correct stability order for the following species is
(2008)
(a) I (b) II
(c) III (d) IV
Objective Questions II
(a) (II) > (IV) > (I) > (III) (b) (I) > (II) > (III) > (IV) [One or more than one correct option]
(c) (II) > (I) > (IV) > (III) (d) (I) > (III) > (II) > (IV) 18. Amongst the given options, the compounds in which alll
13. Hyperconjugation involves overlap of the following orbitals the atoms are in one plane in all the possible conformations
(2008) (if any), is (are) (2011)
(a) - (b) -
(c) p-p (d) - (a)
14. In the following carbocation ; H/CH3 that is most likely to
migrate to the positively charged carbon is (2009)
(b)
(c)
(d)
(a) CH3 at C-4 (b) H at C-4
(c) CH3 at C-2 (d) H at C-2
GENERAL ORGANIC CHEMISTRY 104
19. The compound in which C uses its sp3-hybrid orbitals for Match the Following
bond formation is (2000)
Each question has two columns. Four options are
(a) HCOOH (b) (H2N)2 CO given representing matching of elements from
(c) (CH3)3 COH (d) CH3CHO
Column-I and Column-II.
20. The IUPAC name(s) of the following compound is (are)
22. Match the following with their Ka values (2003)
Column - I Column - II
(2017)
Benzoic acid 4.2 × 10–5
(a) 4-methylchlorobenzene p-nitrobenzoic acid 3.3 × 10–5
(b) 4-chlorotoluene p-chlorobenzoic acid 6.4 × 10–5
(c) 1-chloro-4-methylbenzene p-methylbenzoic acid 36.2 × 10–5
(d) 1-methyl-4-chlorobenzene
p-methoxybenzoic acid 10.2 × 10–5
Numerical Value Type Question
Subjective Type Questions
21. Among the following, the number of aromatic compound(s)
23. Give reasons for the following
is ? (2017)
is more basic than HC C . (2000)
24. Draw the resonating structures of .
(2003)
25. Which of the following is more acidic and why ? (2004)
Find Answer Key and Detailed Solutions at the end of this book
GENERAL ORGANIC CHEMISTRY
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HYDROCARBONS
Chapter 07 106
HYDROCARBONS
1. INTRODUCTION OF HYDROCARBON 2.2 Structure of Alkanes
Alkane is saturated hydrocarbon for representing a five carbon
Compounds containing carbon and hydrogen are hydrocarbons. alkane following ways can be used:
They are of following types :
Molecular formula (M. F): C5H12
1. Saturated Hydrocarbons (Alkanes)
Condensed structural formula (CSF):
2. Unsaturated Hydrocarbons (Alkenes, Alkynes)
H 3 C CH 2 CH 2 CH 2 CH 3
3. Aromatic Hydrocarbons
Expanded structural formula (ESF):
Bond line Notation (BLN):
2.3 Nomenclature and Isomerism in Alkanes
Common names are given in parenthesis
1. H 3 C CH 2 CH 2 CH 2 CH 3
Pentane (n-pentane)
2. ALKANES H 3 C CH CH 2 CH 3
|
CH3
2.1 Introduction to Alkanes
2-methylbutane (Isopentane)
Branched and unbranched aliphatic saturated
hydrocarbons are called member of alkane. The structural Isomerism
formula of alkane have only single bonds or all bonds Alkane show only chain and position isomerism.
in alkane is only bonds. Example
Alkanes are less reactive and does not reacts with chemical
Isomer of hexane
reagants such as dil. and conc. HCl, dil. and conc. H2SO4,
dil. and conc. HNO3, Caustic soda, acidic & basic K2Cr2O7, 1. H 3 C CH 2 CH 2 CH 2 CH 2 CH 3
KMnO4 etc. Therefore alkanes are also called as paraffins.
(Parum=little, affins = reactivity). 2. H3CCHCH2 CH2CH3
|
CH3
3. H 3 C CH 2 CH CH 2 CH 3
|
CH3
1 is chain isomer of both 2 and 3, while 2, 3 are position
isomers
SCAN CODE
Hydrocarbons
HYDROCARBONS 107
2.4 Methods of Preparations From Alkyl Halide (By Wurtz reaction)
2.4.1 From Alkenes and Alkynes (Sabatier and Sandrens A solution of alkyl halide in ether on heating with sodium
Reaction) or (By Hydrogenation of Alkenes and Alkynes) gives alkane.
Alkanes, are obtained by the catalytic hydrogenation of alkenes
R X 2Na X R
Dry
ether
R R 2NaX
and alkynes.
(a) Two moles of alkyl halide treated with Na in presence
R—CH CH—R + H2
Catalyst
R—CH2—CH2—R of dry ether. If ether is wet then we obtain alcohol.
Alkene Alkane
R—C C—R + 2H2 CH 3 Cl 2Na Cl CH 3
dry ether
CH 3 CH 3 2NaCl
Catalyst
R—CH2—CH2—R
Alkyne (b) Methane cannot be prepared by this method. The alkane
Catalyst : produced is higher and symmetrical i.e. it contains
double the number of carbon atoms present in the alkyl
(a) Pd/Pt at ordinary temp. and pressure
halide taken.
(b) Ni, 200–300° C (sabatier)
(c) Two different alkyl halides, on wurtz reaction give all
(c) Raney Nickel at room temp. possible alkanes.
(d) Methane can not be prepared by this method (From (d) The seperation of mixture in to individual members is not
unsaturated hydrocarbon). easy because their B.P. are near to each other and thus
wurtz reaction is not suitable for the synthesis of alkanes
Ni / Pt
eg : H C C H 2H 2 CH 3 CH 3 containing odd number of carbon atom.
2.4.2 From Alkyl Halides (e) This reaction generally fails with tertiary alkyl halide.
From Alkyl Halides (By reduction) Mechanism:
2[ H ]
Two mechanism have been proposed for this reaction.
R—X R—H + HX
( Nascent Hydrogen ) (i) Ionic Mechanism:
Catalyst: 2Na 2e
2Na
(a) Zn + HCl
(b) Zn + CH3 COOH
(c) Zn—Cu couple in C2H5OH
(d) Red P + HI
(e) Al + Hg + ethanol
2[H]
eg : CH3 Cl CH 4 HCl
Zn / HCl 2Na 2X
2NaX
Mechanism: Example
2C 2 H 5 I 2Na
C 2 H 5 C 2 H 5 2NaI
n bu tane
(ii) Free radical mechanism:
Na e
Na
(a) Alkyl halides can also be reduced to alkane by H2/Pd
or LiAlH4 or H2/Ni.
(b) Reduction is due to the electron transfer from the metal R R R — R
to the substrate R—X Na X
NaX
(c) If any alkyl halide is asked, the H-atom of any carbon atom
Product
of given alkane is removed by halogen atom.
SCAN CODE
Hydrocarbons
HYDROCARBONS 108
Free radicals also undergo disproportionation i.e. one 2RCOONa + 2H2O
Electrolysis
radical gains hydrogen at the expense of the other which
loss hydrogen. R — R + 2CO2 + 2NaOH + H 2
At Anode At Cathode
Electrolysis of Sodium propionate solution give n-butane,
ethylene, ethane and ethyl propionate as follows-
This explains the presence of ethylene and ethane in the 2C 2 H 5 - COONa
electro.
C 2 H 5 - C 2 H 5 + 2CO 2
butane obtained by Wurtz reaction. + 2NaOH + H 2
From Alkyl Halide (By Frankland Reagent) Mechanism:
If Zn is used in place of Na, the reaction is named as
electrolysis
Frankland reaction. C2H5COONa C H —COO- + Na+
2 5
R—X + 2Zn +RX
R2Zn + ZnX 2 (Ionization)
Frankland reagent At Anode
R2Zn + R—X C2H5—COO-
e
C2H5— COO
R—R + RZnX
From Alkyl Halide (By Corey-House Synthesis)
This method is suitable for the preparation of
unsymmetrical alkanes i.e. those of type R—R'
(a) RX + Li RLi + LiX C2 H 5 + C2 H 5
C2H5—C2H5
Product
(b) 2RLi + CuX R2CuLi + LiX
(c) R2CuLi + R ' X R—R' + RCu + LiX
(1 or2 )
NOTE An ester is also formed.
In Corey-house reaction symmetrical and unsymmetrical
alkane both can be formed. C2H5— CO O + C H 5
C2H5 —COOC2H5
2
2.4.3 From Carboxylic Acid (minor products)
At cathode
From Carboxylic Acid (By decarboxylation)
Saturated monocarboxylic acid salt of sodium or potassium Na+ + e-
Na
on dry distillation with soda lime give alkane.
Na + H2O
NaOH + 1
2 H2
HCOONa + NaOH (CaO) H 2 +Na 2 CO3
(a) Methane can not be prepared by this method.
CH 3COONa + NaOH + CaO
CH 4 + Na 2CO 3
(b) Electrolysis of an acid salt gives symmetrical alkane,
(a) The process of elimination of Carbon dioxide from however in case of a mixture of carboxylic acid salts, all
carboxylic acid is called decarboxylation. probable alkanes are formed.
(b) Replacement of -COOH by hydrogen is known as
Electrolysis
decarboxylation. R'COOK + R"COOK (R'—R" + R'—R' +
The alkane formed always contains one carbon atom less R"—R") +2CO2 + H2 +2KOH
than the original acid. (c) Presence of alkyl groups in - position decrease the
From Carboxylic Acid (By Kolbe's process) yield of alkanes.
Alkanes are formed on electrolysis of concentrated (d) True aromatic acids do not undergo Kolbe's electrolytic
aqueous solution of sodium or potassium salt of saturated reaction.
monocarboxylic acids.
SCAN CODE
Hydrocarbons
HYDROCARBONS 109
(e) Free radical mechanism has been suggested for Kolbe CH 4, CH 3—CH 3, isobutane and neopentane are not
reaction. obtained from Ketones because these alkane do not
(f) At anode alkane (major) and CO2 gas is formed while at contain CH2 group.
cathode NaOH and H2 gas is formed. From Carbonyl Compounds (By Wolff Kishner reaction)
(g) The concentration of NaOH in solution is increased with
C O + NH2NH2
C Glycol / KOH
N.NH2
CH2 + N2
time so pH of solution is also increased.
2.4.4 From Reduction with Red P + HI Hydrazine Hydrazone
The reduction of the alcohol, carbonyl compound and carboxylic 2.4.6 From Grignard Reagent
acid in presence of red P and HI gives corresponding alkane. Formation of alkanes with same number of C atoms
With same number of C-atoms as G.R. react with compound
R—OH +2HI
Re d P
150 C
R—H+H2O+ I2
containing active hydrogen alkanes is obtained.
R—CHO + 4HI RCH3+H2O + 2I2
Re d P R Mg X H O H
R H Mg(OH) X
1 50 C
R Mg X R O H
R H Mg(OR) X
R Mg X R NH H
R H Mg(NHR) X
This reaction is used to determine the number of active H-
RCOOH + 6HI
Re d P
R—CH3+2H2O + 3I2 atoms in the compound this is known as Zerewitnoff's method.
150 C
Grignard Reagent react with alkyl halide to give higher alkanes
In the above reaction I2 is formed which acts as reducing agent
and may reduce alkane and form alkyl halide. So red P is added RMgX + R'—X
R—R' + MgX2
in the reaction to remove I2 formed in the reaction. 2.4.7 From Metal Carbide (By Hydrolysis)
R—CH3 + I 2 R—CH2—I + HI Only CH 4 can be obtained by the hydrolysis of Be or Al
carbides
2P + 3I2
2PI3
Al4 C3 12H 2 O 4Al(OH)3 3CH 4
2.4.5 From Carbonyl Compounds
From Carbonyl Compounds (By Clemmensen's method): Be 2 C 4H 2 O
2Be(OH) 2 CH 4
Carbonyl compounds (Preferably ketones) may also be
reduced with Zinc amalgam and concentrated HCl
(Zn—Hg/HCl), this reaction is called Clemmensen
reduction.
SCAN CODE
Hydrocarbons
HYDROCARBONS 110
Preparation of Alkane
SCAN CODE
Hydrocarbons
HYDROCARBONS 111
2.5 Physical Properties of Alkanes predominantly non-polar in nature.
2.5.1 Physical State 2.5.5 Density
The first four members (C1 to C4) are gases ; the next thirteen The densities of alkanes increase with increasing molecular
members, (C5 to C17) are liquids while the higher members are weight but become constant at about
waxy solids. 0.8 g cm–3. This means that all alkanes are lighter than water.
2.5.2 Boiling Points 2.6 Chemical Reactions of Alkanes
The boiling points of n-alkanes increase regularly with the Alkanes undergo free radical substitution reaction, these
increase in the number of carbon atoms. reactions include three steps.
(i) Chain initiation
(ii) Chain propagation.
(iii) Chain termination
2.6.1 Halogenation
Halogenation of an alkane is carried out by treating it with a
suitable halogen in presence of ultraviolet light or by heating the
/
reaction mixture to 250 400C.
The order of reactivity of different halogens in these reaction is
Reactivity of X2 : F2 > Cl2 > Br2 > I2
UV Light or temp
Among the isomeric alkanes, the branched chain isomers have R – H + X2
250 - 400C
R – X + HX
relatively low boiling points as compared to their corresponding
straight chain isomers. Greater the branching of the chain, lower Mechanism:
is the boiling point. This is due to the fact that branching of the (i) Chain initiation
It is an endothermic step.
chain makes the molecule more compact and brings it close to a
sphere, so the magnitude of vander wall forces decreases. UV or temp.
X2
250 400C
2X
2.5.3 Melting Point
It is evident that the increase in melting point is relatively more (ii) Chain propagation
in moving from an alkane having odd number of carbon atoms to
the higher alkane with even no. of ‘C’ while it is relatively less in X R H
R HX
moving from an alkane with even number of carbon atoms to the
higher alkane. R X X
R X X
(iii) Chain termination
It is always exothermic
X X
X2
R R
R R
R X
R X
With F2 alkanes react so vigorously that even in the dark and at
room temperature, reactant is diluted with an Inert gas. Iodination
is reversible reaction, since HI formed as a by product and it is a
strong reducing agent and reduces alkyl iodide back to alkane.
Hence iodination can be done only in presence of strong
2.5.4 Solubility oxidising agent like HIO3, HNO3 or HgO.
In keeping with the popular rule “like dissolves like” hydrocarbons
R – H + I2 R – I + HI
are insoluble in polar solvent like water because they are
5HI + HIO3 3H2O + 3I2
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Hydrocarbons
HYDROCARBONS 112
CH 3 CH 2 CH CH 3 + CH3 CH2 CH2 CH2 Cl
2HI + HgO I2 + H2O + Hg |
Cl
2HI + 2HNO3 I2 + 2H2O + NO2 72% 28%
Formation of alkyl free radical is rate determining step.
Reactivity of H : 3°H > 2°H > 1° H Cl
CH 3 CH CH 3 CH 3 CH CH 2 Cl
2
(c) light, 25C
When equimolar amount of methane and Cl2 is taken, a mixture of | |
four possible products are formed, but when we take excess of CH 3 CH 3
CH4 then yield of CH3Cl will be high. 64%
CH 4
Cl2
CH 3 Cl
Cl2
CH 2 Cl 2
Cl2
CHCl3
Cl2
CCl 4 CH 3
h
h
h h
|
HCl HCl HCl HCl
+ CH 3 C CH 3
|
One chlorine molecule cleaves to form two chlorine radicals, by a Cl
photon of light. Each chlorine atom starts a chain reaction and 36%
on an average each chain contains 5000 repetitions of the chain
propagating cycle so about 10,000 molecules of CH3Cl are formed
Br
2
by one photon of light. (d) CH3 – CH2 – CH3 CH 3 CH 2 CH 2 Br
heat, 127C
In a chain reaction following reagents are involved - 3%
(i) Initiators: They initiate the chain reaction, Initiators are
peroxide (R2O2), etc. + CH 3 CH CH 3
|
h •
Br
R – O – O – R RO
or 97%
h •
R C O O C R R C O Br
or 2
|| || || (e) CH 3 CH CH 3 CH 3 CH CH 2 Br
| heat, 127 C |
O O O
CH 3 CH 3
(ii) Inhibitors: A substance that slows down or stops the trace
reaction is known as inhibitors
For example O2 is a good inhibitor CH 3
|
• • • + CH 3 C Br
R + O2 R O O + R R – O – O – R |
All reactive alkyl free radicals are consumed so reaction CH 3
stops for a period of time. over 99%
Halogenation of Higher Alkane Relative amounts of the various isomers differ remarkably
Cl2 depending upon the halogen used. From the above reaction, it is
(a) CH3 – CH2 – CH3 CH 3 CH CH 3 + observed that chlorination gives mixture in which no isomer
light, 25C |
Cl greatly dominates while, in bromination gives a mixture in which
55% one isomer dominates greatly (97% – 99%),
CH3 CH2 CH 2 Cl Factors Affecting the Relative Yields
Factors determining the relative yields of the isomeric products.
45%
(i) Probability factor: Depends on the other number of each
Cl2
type of H atom in the molecule.
(b) CH3 – CH2 – CH2 – CH3
light, 25C
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HYDROCARBONS 113
(ii) Reactivity of Hydrogen: The order of reactivity is 3° > 2° 2.6.5 Aromatisation
> 1°. The relative rate per hydrogen atom is found to be Alkanes containing 6 or more number of C atoms are oxidised
(dehydrogenate & cyclised) in presence of oxidising agent at
Primary Secondary Tertiary
1 : 3.8 : 5 For chlorination at 25oC higher temparature and form benzene or its derivatives.
1 : 82 : 1600 For bromination at 127oC
(iii) Reactivity vs Selectivity Principle :
The more reactive is halogen less selective it will be, so the
more reactive chlorine free radical is less selective and more
influenced by the probability factor and the less reactive
bromine free radical is more selective and less influenced
by the probability factors.
2.6.2 Sulphonation
Lower alkanes are not easily sulphonated but hexane & higher
members are sulphonated on heating with oleum (conc. H2SO4 +
SO3) at 400°C
400 C
C6H14 + H2SO4
C6H13SO3H + H2O
2.6.3 Isomerisation
Alkanes undergo isomerisation n-Alkanes on heating in the
presence of anhydrous aluminum chloride and hydrogen chloride
gas isomerise to branched chain alkanes.
Anhyd. AlCl3 / HCl
CH3CH2CH2CH3 CH 3 CH CH 3
300C |
CH 3
Isobutane
CH 3
|
AlCl3 / HCl
CH3 – (CH2)3 – CH3
300C
CH3 C CH 3
|
CH 3
Neopentane
2.6.4 Alkylation
2.6.6 Pyrolysis / Cracking
Higher branched alkanes are formed when isoalkane add to
400 500ºC
isoalkene in presence of Conc. H2SO4 CH3 – CH2 – CH3
in absence of air CH3CH3 + CH3CH = CH2 +
CH2 = CH2+ CH4 + H2
Higher alkanes are heated in absence of air so these compounds
break down into smaller alkanes which are better fuels. Mixture
of products contains all lower alkanes, alkenes & hydrogens.
2.6.7 Controlled Oxidation
Alkanes on heating with a regulated supply of dioxygen or air at
high pressure and in the presence of suitable catalysts give a
variety of oxidation products.
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Hydrocarbons
HYDROCARBONS 114
(i) 2CH 4 O 2
cu /523K /100atm
2CH 3 OH CH4 < C2H6 < C3H8
Methanol
Isomers: Branched isomer has lower heat of combustion.More
(ii) CH 4 O 2
Mo 2 O3
HCHO H 2 O branched alkane has more no. of primary C – H bonds.
Methanal
(therefore it has more bond energy).
CH3 COO 2 Mn
(iii) 2CH 3 CH 3 3O 2
2CH 3 COOH 2H 2 O
Ethanoic acid
(iv) Ordinarily alkanes resist oxidation but alkanes having
tertiary H atom can be oxidized to corresponding alcohols
by potassium permanganate.
CH 3 3 CH
KMnO 4
Oxidation
CH 3 3 COH
2 Methylpropane 2 Methylpropan-2-ol
Cyclo-alkanes : More strained ring has higher heat of combustion
2.6.8 Combustion
per – CH2 – unit.
Alkane an complete combustion yield CO2 and H2O.
> > >
3n 1 combustion
CnH2n+2 + O nCO2 + (n + 1)
2 2 (Hcomb. per ‘CH2’ unit)
H2O ( ΔH combustion = -ve) Octane Number
It is a scale used to measure the fuel efficiency when the fuel
exothermic reaction burns during combustion, more branched alkanes have lower
knocking (cracking sound), so are better fuels. On commercial
y y scale iso-octane has been alotted a rating i.e. octane no. of
combustion
CxHy + x O2 xCO2 + HO Isooctane is 100 & n-heptane is - ‘0’
4 2 2
CH3
combustion |
C5H12 + 8O2 5CO2 + 6H2O H 3 C C CH 2 CH CH 3 Octane number = 100
| |
Points to remember for H of combustion : CH3 CH3
Homologues: Higher homologues have higher heat of H 3C CH 2 CH 2 CH 2 CH 2 CH 3 Octane number = 0
combustion.
If the octane no. of a fuel is 80, it means that the efficiency of the
fuel is equivalent to the efficiency of mixture of 80% isoctane and
20% n-heptane.
Chemical properties of Ethane
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HYDROCARBONS 115
3. ALKENES Relative Stabilities of Alkenes
3.1 Introduction of Alkenes > >
These are acylic unsaturated hydrocarbons with carbon–carbon
double bonds. They form homologous series with general
R H
formula CnH2n Alkenes are also called as olefins, a term derived C=C > >
from olefiant gas, meaning "oil forming". Alkenes are among the R H
most important industrial compounds and many alkenes are also
found in plants and animals. Ethylene is the largest–volume R R
industrial organic compound, used to make polyethylene and a C=C > >
H H
variety of other industrial and consumer chemicals. Alkenes
polymerise to give many important polymers.
Structure and Bonding
(a) Alkenes are unsaturated hydrocarbons having at least one
Another way of measuring the stability of an alkene is the
double bond.
determination of its heat of hydrogenation or the heat of
(b) In Ethene C = C bond length is 1.34 Å
combustion. ( H = – ve)
(c) Its bond energy is 146 kcal.mol-1
(d) The hybridization of (C = C) alkenic carbon is sp2 1
H (– ve sign indicates the exothermic nature of
stability
(e) The e cloud is present above and below the plane of
reaction)
bonded skeleton.
Heat of Combustion of Alkenes:
(f) Compounds may exist as conjugated polyenes or as
Heat of
cumulated polyenes or as isolated polyenes
Alkene combustion
1.34A kJ / mol
117.2° 1-Butene 2719
1.10A
(b)
Isobutene 2703
121.2°
(a) cis-2-Butene 2712
trans-2-Butene 2707
All four butenes may be compared,
since all give the same products on
combustion viz. 4CO2 + 4H2O.
3.3 Nomenclature and Isomerism
Nomenclature
For alkene IUPAC template is Alk + n + ene
But - 2 - ene
3.2 Stability of Alkenes
Studies of numerous alkenes reveal, pattern of stabilities that
related to the number of alkyl groups attached to the carbon
atoms of the double bond. The greater the number of attached
alkyl groups (i.e., the highly substituted the carbon atoms of the
double bond), the greater is the alkene’s stability. This order of
stabilities can be given in general terms as follows.
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HYDROCARBONS 116
Isomerism General Reaction
Alkenes show both structural isomerism and geometrical
isomerism
But-1-ene and But-2-ene are position isomers.
Alkene shows geometrical isomerism because of restricted Example
rotation it is of two types Na / NH ( )
CH3 – CH2 – C C – CH2 – CH3
3
(a) in which two identical atoms or groups lie on the same side
of the double bond is called cis isomer.
(b) in which identical atoms or groups lie on the opposite sides
of the double bond is called trans isomer.
NOTE
This process of reduction is not eligible when terminal
alkynes are taken.(R–C CH) because terminal alkynes
form sodium salt with Na metal.
3.4 Methods of Preparation CH3 – C CH + Na / NH3
3.4.1 From Alkynes: By Catalytic Hydrogenation of Alkynes in CH3 – C C¯ Na+ + 1/2 H2
Presence of Poisoned Catalyst 3.4.2 From Vicinal Dihalides
(A Syn Addition of Hydrogen takes place giving cis alkynes) There are two types of dihalides namely gem (or geminal)
Lindlar’s catalyst: Metallic palladium deposited on calcium dihalides in which the two halogen atoms are attached to the
carbonate conditioned with lead acetate and quinoline. same carbon atom and vicinal dihalides in which the two halogen
Example atoms are attached to the adjacent carbon atoms. When vicinal
dihalides are heated with Zn metal in presence of NaI in acetone
or Zn in C2H5OH or Zn in CH3COOH, corresponding alkenes are
formed. This reaction is a dehalogenation process.
General Reaction
Example
Example
NaI
CH3 – CHBr – CHBr – CH3
Acetone
CH – CH = CH – CH
3 3
3.4.3. From Alkyl Halides
When alkyl halide is heated with alc.KOH hydrogen halide is
eliminated giving corresponding alkene. This is called as
dehydrohalogenation
Example
CH3
Birch Reduction |
(Anti Addition of Hydrogen take place giving trans-Alkenes) CH 3 C Br alc.KOH
Heat
|
It follows free radical path CH3
CH 3 C CH 2 KBr H 2 O
|
CH3
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HYDROCARBONS 117
Here – H is eliminated by base hence called elimination (iv) Al2O3 / 350°C undergo loss of water molecule and form
following Saytzeff rule alkenes
i.e. (Highly substituted alkene is major product). It also General Reaction
involves an anti elimination of HX.
RCH 2 CH 2 OH
P2 O5 or conc. H 2SO 4 or Al2 O3
R CH CH 2 H 2 O
Example
Example
Minor Major
3.4.4 By Dehydration of Alcohols
3.4.5 By Kolbe's Electrolytic Synthesis
Alcohols when heated in presence of following reagents undergo
loss of water molecule and form alkenes. The elimination is
elimination.
(i) H2SO4 / 160°C
(ii) H3PO4 /
(iii) P2O5 /
Preparation of Alkene
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HYDROCARBONS 118
3.5 Physical Properties of Alkenes
S. No. Physical Homologous Series Isomers
Properties
1. Physical state C1 – C3 gases –
C4 – C20 liquids
> C20: solids
2. Dipole moment () – Cis > Trans
3. Polar – Cis > Trans (for Cab = Cab type of alkens)
4. Melting point Increases with Molecular Weight Trans > Cis
(Due to more packing capacity)
5. Boiling point Increase with Molecular Weight Cis > Trans
# Branching decreases boiling point C
|
C–C = C < C – C = C – C
Polarity increases, boinling point
6. Solubility Practically insoluble in water but Cis > Trans
fairly soluble in non-polar solvents Polar increases, solubility in polar
like benzene petroleum ether, etc. solvents increases
7. Stability – Trans > Cis (Cis isomers has more
Vander Waals repulsion)
3.6 Chemical Properties of Alkenes (c) The reactivity order of alkenes has been written in terms
Alkenes are more reactive than alkane because - of heat of hydrogenation of alkene, more is the heat of
hydrogenation (H = –ve), more is the reactivity, the
(a) The electrons of double bond are located much far
reactivity of alkene is however also related to
from the carbon nuclei and are thus less firmly bound
to them. (i) Steric hinderence
(b) bond is weaker than bond and more easily (ii) Hyperconjugation
broken. (iii) Heat of Combustion.
The reactivity order for alkenes -
Alkene Heat of combustion Heat of hydrogenation
CH2 CH2 > R—CH CH2 > R2C CH2 RCH CHR (kJ/mol) (kcal/mol)
> R2C CHR > R2C CR2 1-Butene 2719 30.3
(Trans < Cis) Isobutene 2703 27.2
Cis-2-butene 2712 28.6
Trans-2-butene 2707 27.6
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HYDROCARBONS 119
Alkene undergo electrophilic addition reactions, under
Step II: The nucleophile (: Nu – ) released in the slow
special conditions alkenes undergo for radical addition
step combines with the carbocation to give the
reaction
desired addition product in the fast step.
3.6.1 Addition Reaction
Example of Electrophilic Addition Reaction
Alkene react with H2 in presence of Ni/Pd to give alkanes.
(a) Addition of Halogen
This reaction is called as catalytic Hydrogenation.
It is a electrophilic addition reaction.
(i) Addition of H2 :
Ni,Pt or Pd
R—CH=CH2+H2
R—CH2—CH3+ Heat
NOTE
Reaction is exothermic NOTE
More the stable alkene less will be the heat of The reaction is quite fast with Cl2, relatively slow
hydrogenation and less will be the reactivity with Br2 and is very slow with I2
towards H2.
Addition of F 2 is exothermic reaction so it is
The process is used to obtain vegetable (saturated difficult to control.
fats) ghee from hydrogenation of oil.
The addition of Br2 on alkenes provides a useful
(ii) Electrophilic Addition Reactions : test for unsaturation in molecule.The brown
Because of the presence of >C = C< bond in colour of the bromine being rapidly discharged.
molecules, alkenes generally take part in the addition Thus decolarization of 5% Br 2 in CCl 4 by a
reactions. compound suggest unsaturation in it. Colourless
dibromo compound is formed.
I2 reacts slowly with alkenes to form Vicinal di-
iodides which are unstable and eliminated I 2
molecule very readily to give original alkene due
From mechanism point of view, the addition in alkenes to large size of Iodine they overlap.
is generally electrophilic in nature which means that
CH3—CH CH2 + I2 CH3 CH CH2
attacking reagent which carries the initial attack is an
electrophile (E+). This is quite expected also as there I I
is high electron density in the double bond. The Unstable
mechanism proceeds in two steps. Mechanism:
Step I: The –electron cloud of the double bond It is interesting to note that product which is mainly
causes the polarisation of the attacking molecule (E– formed as a result of addition is trans in nature whereas
Nu) which cleaves to release the electrophile ( E ) for the cis isomer is obtained in relatively smaller proportions.
the attack. The double bond simultaneously undergoes Since carbocation intermediate is planar (sp 2 hybridised),
electromeric effect and the attack by the electrophile is both cis and trans addition products must be formed
accomplished in slow step (also called rate determining almost in equal proportions. The trans product can be
step) to form a carbocation intermediate. justified in case a cyclic ion is formed by the initial
electrophile attack.
The attack of Br– ion on the cyclic ion takes place from
the side opposite to side where bromine atom is present in
order to minimise steric hindrance.
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HYDROCARBONS 120
Markovnikoff's Rule
(a) First Rule : When molecule of a HX add up on
unsymmetrical unsaturated hydrocarbon, the halogen
atom goes to the unsaturated carbon atom bearing
Example lesser number of hydrogen atoms.
X
aq.NaCl
CH 2 CH 2 + Br 2 Products, what are |
Ethylene
CH3 CH CH 2 HX CH3 C H C H 2
|
H
the products?
Mechanism:
It is electrophilic addition and is illustrated by the action of
HCl to propene.
Sol.
Primary carbocation (CH3—CH2— CH 2 ) is formed but only
in very small proportion since it is less stable than the
Similarly
secondary carbocation. Markownikoff's rule can also be
stated as:
The electrophilic addition to unsymmetrical alkenes always
occurs through the formation of a more stable carbocation
intermediate.
(b) Second Rule : In the addition of HX to vinyl halide
and analogous compounds, the halogen attaches itself
to the carbon atom, on which the halogen atom is
(b) Addition of Hydrogen Halides already present.
X CH2 CH—Cl+HCl
| CH 3 CH Cl
R—CH CH—R + HX
R CH C H R |
2 Cl
X Ethylidene chloride
|
R—CH CH2 + HX
R C H CH Mechanism:
3
NOTE
The order of reactivity of hydrogen halide is
HI > HBr > HCl > HF
Their addition is an example of electrophilic
addition.
Addition on alkene proceeds via the formation of In vinyl chloride two effects operate simultaneously in
more stable carbonium ion. opposite direction-
Addition of HX on unsymmetrical alkenes (i) Inductive effect – electron attracting (-I) effect of
(R—CH=CH2) takes place according to chlorine.
Markownikoff's rule.
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HYDROCARBONS 121
(ii) Resonance effect – electron pair releasing (+R) effect (ii) Chain propagation
of chlorine.
The resonance effect is much more than the -I
effect of Chlorine at the time of attack. This creates
centres of +ve and –ve charges. All polar reagents
of the general structure Y+Z- (such as H+ — X-,
H+ — OH-, H+ — SO3H-, X+ — OH-) add on
unsymmetrical unsaturated compound in accordance
with Markownikoff's rules. Such additions are called
normal Markownikoff's rule, where as additions in
the opposite manner are reffered to as abnormal or
antimarkownikoff's additions.
Anti Markovnikoff's rule or Peroxide Effect or (iii) Chain termination :
Kharasch Rule:
R R
R—R
(i) In the presence of peroxides the addition of HBr on
unsaturated unsymmetrical compound takes place R Br
R—Br
against/opposite to Markownikoff's rule. This is called
Br Br
Br—Br
peroxide effect and is due to the difference in the
mechanism of the addition. NOTE
(ii) In the normal Markownikoff's addition the mechanism HCl and HI do not give antimarkownikoff products in
is ionic. the presence of peroxides.
(iii) In the presence of peroxide the addition of HBr takes Reasons are
place via free radicals.
(a) The H—Cl bond is stronger than H—Br. So Cl free
radical is not formed.
(b) The H-I bond is weaker than H—Br bond. It is
broken by the alkoxy free radicals obtained from
peroxides, but the addition of iodine atom on alkene
is endothermic as compared to Br atom therefore
iodine atoms so formed combine with each other to
yield iodine.
(c) Addition of Hypohalous acid (or X2/H2O, or HOX) : It
Mechanism: is a electrophilic addition and follows Markownikoff's
(i) Chain initiation - rule.
(a) R—O—O—R
2RO•
(b) HBr + RO•
ROH + Br•
In the fast step, there is competition between Cl- ion
and H2O molecule to act as nucleophile but H2O is a
better nucleophile.
Reactivity order is HOCl > HOBr > HOI
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HYDROCARBONS 122
(d) Addition of H2SO4: Alkene react with conc. H2SO4 to
produce alkyl hydrogen sulphate. Which gives
alcohols on hydrolyses.This reaction used to seprate
alkene from a mixture of alkane and alkene.
BH3 does not exist or stable as monomer so a solvent
THF (tetra hydro furane) is used.
NOTE BHR2 also can be taken.
Ethyl hydrogen sulphate give ethylene when heated
430-440K while ethanol is obtained on boiling it with CH3 C H C H 2 BHR 2 CH3 CH 2 CH 2 BR 2
water. Example
(e) Addition of Water (Hydration of Alkenes) : Propene
and higher alkenes react with water in the presence of
acid to form alcohol. This reaction is known as the
hydration reaction . Intermediate in this reaction is
carbocation, so rearrangement will take place.
+
H
(i) CH3 - CH = CH2 + H2O CH3 - CH - CH3
OH
Propane Propan-2-ol
(g) Oxymercuration – Demercuration: Mercuric acetate in
(ii) tetrahydro furan (THF) is treated with an alkene.The
addition product on reduction with sodium Boro
hydride in aqueous NaOH solution gives alcohol. It
follows the markownikoff's rule.
Mechanism
CH3 - CH = CH2 CH 3 CH CH 3
|
OH
(i) (AcO)2 Hg/H2O (Mercuric acetate) or (CH3COO)2
Hg/H2O
(ii) NaBH4/NaOH
Mechanism :
(f) Hydroboration Oxidation
It obeys markownikoff's rule. Diborane readily reacts
with alkenes giving trialkyl boranes. The reaction is
called hydroboration.
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Hydrocarbons
HYDROCARBONS 123
NOTE
Intermediate is cyclic cation so their is no
rearrangement.
3.6.2 Oxidation Reaction
Alkenes are easily oxidised by oxidising agents. Oxidising
agents attack on double bond and product formed during
oxidation depends on oxidising agents.
(a) Ozonolysis: (A test for unsaturation in molecule)
(i) The addition of ozone on the double bonds and
subsequent a reductive hydrolysis of the ozonide
formed is termed as ozonolysis.
(ii) When ozone is passed through an alkene in an inert
solvent, it adds across the double bond to form an
ozonide. Ozonides are explosive compound they are
not isolated.
Reductive Ozonolysis
(h) Hydroformylation or Oxo Reaction: Alkenes react with Products of reductive ozonolysis are aldehydes and/or
Carbon monoxide and hydrogen at 100 – 150°C ketones
temperature and high pressure (200 atm) in the
Hydrolysis with Zn metal
presence of Cobalt catalyst to produce an aldehyde.It
does not follows markownikoff's rule. Oxidative Ozonolysis
The net reaction is the addition of a H–atom to one Products of oxidtive ozonolysis are carboxylic and/or
of the Olefinic bond and a formyl (–CHO) group to ketones
the other, thereby forming aldehydes Hydrolysis without Zn metal
In Place of Zn, dimethyl sulphur can also be used.
In reductive ozonolysis, We add zinc which reduces H2O2
to H 2O and thus H2O2 is not present to oxidised any
aldehyde formed. While without Zn metal, H2O2 formed
would oxidise aldehydes to carboxylic acids but ketones
are not oxidized.
(i) Alkenylation (Addition of Alkene) In presence of
H2SO4 or H3PO4 at 80°C dimerisation of isobutylene
take place gives two isomer of octene.
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HYDROCARBONS 124
Example (b) Hydroxylation
Oxidation of carbon-carbon double bond to
is known as hydroxylation.
Oxidation by Baeyer's Reagent
(A test for unsaturation) : Alkenes on passing through
dilute alkaline 1% cold KMnO4 (i.e., Baeyer's reagent)
decolourise the pink colour of KMnO4 and gives brown
ppt MnO2 and glycol.
(iii) Ozonolysis of alkenes helps in locating the position of
double bond in an alkene. It can be achieved by
joining together the carbon atoms of the two carbonyl
compounds formed as the products of ozonolysis with
double bond.
Example
By peracid:
Example
H H
1 2 3 4
H C O + O C CH2 CH3 CH2 CH CH2 CH3
(c) Epoxidation
Methanal Propanal But-1-ene
Alkenes reacts with oxygen in the presence of Ag
It may be noted that reaction with bromine water or
catalyst at 250°–400° C to form epoxide.
Baeyer's reagent detects the presence of double bond
(or unsaturation) in an alkene while ozonolysis helps in
locating the position of the double bond.
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HYDROCARBONS 125
(ii)
(d) Oxidation by Strong Oxidising Agent (Oxidative
Cleavage) : The alkenes themselves are readily
oxidised to acid or ketone by means of acid
Prilezhaev Reaction : When an alkene is treated with permanganate or acid dichromate. If HCOOH is formed,
perbenzoic acid, an epoxide is formed. Such an it further oxidized to CO2 and H2O. Keep it in mind
epoxidation is known as Prilezhaev reactions. that no further oxidation of ketones will takes place.
CH2 CH2+4[O]
2HCOOH
2[O ]
2CO2 + H2O
CH3CH CH2
5 [O ]
CH3COOH+CO2+H2O
4 [O ]
CH3CH CHCH3 2CH3COOH
Syn
Cis symmetrical
addition
Meso compound
Alkene
(e) Oxidation with Retention of Carbon-Carbon Bond -
Anti
Cis symmetrical
addition
Racemic Mixture (Wacker's Process) :
Alkene
PdCl
Syn
Trans symmetrical Racemic Mixture CH2 CH2+H2O2
CuC l
2
CH3CHO
addition 2
Alkene
Trans symmetrical Anti
Meso compound (f) Combustion Reaction : Alkene on combustion gives
addition
Alkene CO2 and H2O
Syn addition on alkene H 2 , 3n
CnH2n + O
nCO2 + nH2O
Baeyer 's reagent, OsO 4 / H 2 O 2 2
Anti addition on alkene X 2 , 3n
One mole of alkene requires moles of O2 for
HOX, R COOOH / H 2 O, Ag 2 O / H 2 O 2
complete combustion.
Example 3.6.3 Substitution Reaction (Allylic Substitution)
When alkenes are treated with Cl 2 or Br 2 at high
temp., one of their allylic hydrogen is replaced by
halogen atom. Allylic position is the carbon adjacent
to one of the unsaturated carbon atoms.It is free
(i)
radical substitution.
0
CH3—CH = CH2 + Cl2
50 0 C
ClCH2—CH = CH2 + HCl
Allyl chloride
(3-Chloro-1-propene)
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N-Bromosuccinimide (NBS) is an important reagent 3.6.4 Polymerization
used for allylic bromination and benzylic substitution. (i) The process of formation of macro molecules by the
addition of simple unsaturated molecules is known
as polymerization
(ii) The macro molecule formed is a polymer and simple
molecules from which polymer is formed is called
monomer.
(iii) Molecular weight of polymer is simple multiple of
monomer.
(iv) Addition polymerization can also be carried out by
ionic mechanism by using Ziegler - Natta Catalysts
(R3Al + TiCl4)
3.6.5 Isomerization
Alkene on heating to 500° to 700 °C or on heating in
presence of catalyst [AlCl 3 or Al 2 (SO 4 ) 3 ] undergo
isomerisation.
Substitution reaction is not given by ethene. Catalyst
CH3CH2—CH CH2 CH3—CH CH—CH3
Example 1–Butene 2–Butene
CH3 CH3 C CH 2
CH2 Br |
(i) NBS
CH3
Isobutylene
(ii) NBS
Br
H . Br
CH3 CH3 CH3
3° more stable
3.6.6 Laboratory Test of Alkene
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Chemical reactions of Alkenes
4. ALKYNES (b) Alkynes are also called acetylenes because they are
derivatives of acetylene
4.1 Introduction of Alkynes (c) In alkyne C C bond length is 1.20 Å
Unsaturated Hydrocarbon characterised by a presence of (d) Its bond energy is 192 kcal mol–1
CC (e) The hybridization of carbon atoms having triple bond
Form homologous series with general formula CnH2n-2 and each ( C C ) in alkynes is sp.
homologue of alkyne has 4H atoms less than the corresponding
(f) Overlapping of these sp hybrid orbitals with each other and
alkane.
with the hydrogen orbitals gives the sigma bond framework
4.2 Structure and Bonding in Alkynes which is linear (180°) structure.
(a) Alkynes are hydrocarbons that contain carbon-carbon triple
bond.
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(g) Two p bonds result form overlap of the two remaining (b) Due to stability of vinyl halide by resonance there is partial
unhybridized p orbitals on each carbon atom. These orbitals double bond in which elimination does not take place by
overlap at right angles (90°) to each other, forming one p alc. KOH so stronger base NaNH2 is used.
bond with electron density above and below the C-C sigma
bond, and the other with electron density in front and in (c) Basic strength : NH 2 is stronger base then RO
back of the sigma bond. This result in a cylindrical p electron
(d) Trans elimination takes place in forming of alkynes.
cloud around s bonded structure.
(e) From Vicinal Dihalides
1.20Å 1.06Å
180° H H H
| | |
alc.KOH
R C C H
HX
R C C H
| |
H H H–C–C–H X X
NaNH
HX
2
R C CH
NOTE
Any type of stereoisomerism does not arise in acetylenic NOTE
bond due to linearity of C C bond. Elimination of Vic. dihalides gives also alkadiene (1, 2
4.3 Nomenclature and Isomerism and 1, 3 alkadienes) but the major product is alkyne.
Nomenclature Non terminal gem dihalide gives 2-Alkyne in presence
of alc. KOH while gives 1-alkyne in presence of NaNH2.
In common system, alkynes are named as derivatives of acetylene
In IUPAC system, they are named as derivatives of the 4.4.2 Dehalogenation of Tetrahaloalkane
corresponding alkanes replacing ‘ane’ by the suffix ‘yne’. By heating 1, 1, 2, 2 - tetra halo alkane with Zn dust.
Structure Common name IUPAC name X X
| |
H C CH Acetylene Ethyne 2Zn
R C C H R C CH 2ZnX 2
CH 3 CH 2 C CH Ethylacetylene But 1 yne | |
X X
Isomerism
4.4.3 From Kolbe's Electrolysis
Alkyne shows generally position isomerism
By the electrolysis of aqueous solution of sodium or potassium
CH 3 C C CH 3 But 1 yne fumarate or maleate, acetylene is formed at anode.
CH 3 CH 2 C CH But 2 yne
4.4 General Methods of Preparation + H2
4.4.1 By Dehydrohalogenation
4.4.4 Preparation of Higher Alkynes by Grignard Reagent
(a) From Gem dihalides: Dehydrohalogenating agents are :
By this method lower alkyne is converted in to higher alkyne
NaNH2 (Sodamide) or Alc. KOH or ROH + RONa.
Example
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CaC2 + 2H2O
CH CH + Ca(OH)2
Ca+2 + C C + 2H+ + 2OH–
CH CH + Ca(OH)2
4.4.6 Berthelot's Process
Acetylene is synthesized by striking an electric arc between
carbon electrodes in presence of hydrogen.
1200 C
2C + H2 CH CH
4.4.7 From Haloform [CHI3, CHCl3]
Pure acetylene is obtained when iodoform or chloroform is heated
4.4.5 From Metal Carbide [ Laboratory Method] with Silver powder
Acetylene is prepared in the laboratory by the action of water on
calcium carbide.
Preparation Methods of Alkynes
4.5 Physical Properties doubly bonded carbon atoms and the electrophile is formed.
Since the bond energies of the bond broken and the new s
Solubility
bond formed are not much different therefore electrophilic
Alkynes are relatively nonopolar (w.r.t. alkyl halides and substitution reaction are not accompnied by large energy changes.
alcohols) and nearly insoluble in water (but they are more On the other hand in electrophilic addition reactions one weak p-
polar than alkenes and alkanes). They are quite soluble in bond (251 KJ mol –1) is broken and two strong bonds
most organic solvents, (acetone, ether, emthylene chloride, (2 × 347 = 694 KJ mol–1) are formed. The overall reaction is
chloroform and alcohols). accompnied by a release of about 694-251 = 443 KJ mol–1 of energy.
Physical state and Boiling point In other words electrophilic addition reactions are energetically
Acetylene, propyne, and butyne are gases at room more favourable than electrophilic substitution reactions Thus
temperature, just like the corresponding alkanes and the typical reactions of alkynes are electrophilic addition reaction
alkenes. In fact, the boiling points of alkynes are nearly the and not the electrophilic substitution reactions.
same as those of alkanes and alkenes with same number of 4.6.1 Catalytic Hydrogenation
carbon atoms. Reduction to Alkenes
4.6 Chemical Reactions of Alkynes (a) By Lindlar's Reagent : Hydrogenation of an alkyne can be
Due to presence of weak p electrons in alkyne, it will go for stopped at the alkene stage by using a “poisioned”
electrophilic reaction. In electrophilic substitution reaction, one (partially deactivated) catalyst made by treating a good
bond is broken and a new - bond between one of the
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catalyst with a compound that makes the catalyst less ef- General Reaction:
fective. Lindlar’s catalyst is a poisioned Pd catalyst, com-
posed of powdered barium sulfate coated with Pd, poisoned
with quinoline.
Example
Common Reagents :
(i) + X2 (ii) + HOX
(iii) + HX (iv) + H2O/H+
(b) By Birch Reduction
(a) Hydration of Alkynes
General Reaction
(i) Mercuric ion Catalyzed Hydration :
Alkynes undergo acid–catalyzed addition of water across
the triple bond in the presence of mercuric ion as a catalyst.
A mixture of mercuric sulfate in aqueous sulfuric acid is
Example commonly used as the reagent.
General Reaction
(c) By Hydroboration Reduction Example
Example
(ii) Hydroboration Oxidation of Alkynes :
4.6.2 Electrophilic Addition to Alkynes Alkynes react with BH3 or B2H6 + THF to give trivinyl bo-
rane which upon subsequent treatment with alkaline H2O2,
Many of the reactions of alkynes are similar to the corresponding
gives alcohols corresponding to anti-markovnikov's addi-
reactions of alkenes. Like the pi bond of an alkene, the pi bonds
tion of H2O to alkynes, which on tautomerisation give cor-
of an alkyne are electron-rich, and they readily undergo addition
responding aldehydes or ketone. Terminal alkynes give al-
reaction. The bond energy of the alkyne triple bond is about 226
dehyde whereas internal alkynes give ketone.
kJ (54 kcal) more than the bond energy of an alkene double bond.
Since sigma bonds are generally stronger than pi bonds, the (b) Addition of Hydrogen Halides (+HX)
reaction is usually exothermic. Alkynes have two pi bonds, so Markownikoff’s Rule:
upto two molecules can add across the triple bond. We must When reagent (asymmetrical HX, H2O) adds to asymmetrical
consider the possibility of a double addition whenever a reagent alkene eg, propene isobutene etc. the addition occurs such
adds across the triple bond of an alkyne. Some conditions may that the nucleophile attaches itself to the carbon atom of
allow the reaction to stop after a single addition, while other
conditions give double addition.
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the alkene bearing the least number of hydrogen, or (c) Addition of Halogen (Halogenation)
electrophile adds to the sp2 carbon that is bonded with the
Alkyne + 2X2 Tetrahalide
greater number of hydrogen.
General Reaction
Alkyne + 2HX Geminal Dihalides
Hydrogen halides add across the triple bond of an alkyne
in much the same way they add across the alkene double
bond. The initial product is a vinyl halide. When a hydrogen
halide adds to a terminal alkyne, the product has the
orientation predicted by Markownikoff’s rule. A second
molecule of HX can add, usually with the same orientation
as the first.
Example
Nature of Addition: Anti in both step
NOTE
(d) Addition of HOX
Markownikoff’s Addition in both steps.
If two moles of HX are added the final product is Alkynes + HOX ' - dihaloketone + -
Gemdihalide. haloketone
Example
Electrophilic addition to terminal alkyne is regioselective.
Example
HCl
C H 3 C H 2 C C H
1 B utyne
Cl
|
CH 3 CH 2 C CH 3
HCl |
Cl
2, 2 Dichlorobutane
Example
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NOTE
Two molecules of HOX can be added, the end product is
Dihaloketone.
The intermediate product is an enol which gives a minor
product haloketone.
4.6.3 Polymerisation
(a) Linear Polymerisation :
Dimerisation : When two molecules of acetylene passed
through a solution of Cu2Cl2 and NH4Cl a vinyl
acetylene is obtained.
Cu Cl
2HC C—H
NH 4 Cl CH2
2 2
CH—C C—H
mono vinyl acetylene
4.6.4 Isomerisation
When vinyl acetylene react with HCl then chloroprene is
obtained. (a) When 1-alkyne is treated with alcoholic KOH 2-alkyne is
formed.
CH 2 CH C C H
HCl
CH 2 CH C CH 2
| R CH 2 C CH
Alco.KOH
R C C CH 3
Cl 1 alkyne 2 alkyne
2- chloro-1,3-butadiene [chloroprene]
(b) When 2-alkyne is treated with sodamide then it is converted
Polymerisation
Neoprene (Synthetic rubber) into 1-alkyne.
Trimerisation: 3 molecules of acetylene.
CH 3 C C CH 3
NaNH 2
NH 3
CH 3 CH 2 C CH
Cu2 Cl2
3CH CH
NH 4 Cl CH2 CH—C C—CH CH2
H2 O
NaOH
CH 3 CH 2 C CH
Divinyl acetylene 4.6.5 Laboratory test of Terminal Alkynes (Acidic nature)
(b) Cyclic Polymerisation : When alkyne is passed through When triple bond comes at the end of a carbon chain.
red hot metallic tube, cyclic polymerisation takes place with The alkyne is called a terminal alkyne.
the formation of aromatic compound
acetylenic hydrogen
H - C C - CH2CH3
1-Butyne, a terminal alkyne
(i) Decolourization of Br2 in CCl4 solution.
(ii) Decolourisation of 1% alkaline KMnO4 solution.
(iii) 1- alkynes give white ppt. with ammonical AgNO3 and red
ppt with ammonical cuprous chloride solution.
NOTE
(i) and (ii) tests are used for determination of unsaturation
(i.e, presence of double or triple bond in any compound)
(iii) Test is used for distinguish between alkenes and
1-alkynes or 1-alkyne and 2-alkyne.
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4.6.6 Laboratory Test for Alkynes
Chemical Properties of Alkynes
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5. BENZENE 5.2 Aromaticity (Huckel Rule)
Criteria for Aromaticity
5.1 Introduction of Benzene
The main essentials for aromaticity are :
Benzene is aromatic hydrocarbon. It undergo electrophilic sub-
stitution reactions. 1. Delocalisation, The molecule should contain a cyclic cloud
Kekule (1865) proposed following structure the basis of the struc- of delocalized n electrons above and below the plane of the
ture of cyclohexane. molecule,
So benzene is found to be resonance hybrid of two Kekule 2. Planarity. For the delocalisation of p-electrons the ring
structures. must be planar to allow cyclic overlap of -orbitals.
Therefore, for a molecule to be aromatic, the ring must be
planar.
3. (4n + 2) electrons. For aromaticity, the -electron cloud
must contain a total of (4n + 2) electrons where n is an
integer equal to 0,1, 2, 3........... This is also known as Huckel
rule. In a nutshell for aromaticity, the molecule must be
planar, cyclic system having delocalized (4n + 2) electrons.
This is known as Huckel rule.
Thus, according to Huckel rule, the aromatic compounds
have delocalised electron cloud of electrons of 2 or 6
or 10 or 14 electrons.
5.3 Preparation Methods of Benzene
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5.4 Physical Properties The five electrophilic aromatic substitutions that we shall study
(i) Benzene and its homologues containing upto eight carbon in this package. All of these reactions involve the attack on the
atoms are colourless liquids while the higher one are solids benzene ring by an electron-deficient species – (by an
with characteristics smell. electrophile). Later we shall learn what the electrophile is in each
instance.
(ii) Aromatic hydrocarbons are immisible with water but are Electrophilic Aromatic Substitution Reactions
soluble in organic solvents.
(iii) They are inflammable and burn with sooty flame.
(iv) The melting and boiling points of aromatic hydrocarbons
increase with increasing molecular mass. This is due
to increase in magnitude of van der Waal's forces of
attraction with increase in molecular size. Amongst isomeric
arenes, (i.e., o-, m- and p- xylenes), the p-isomer has the
highest melting point because it is most symmetrical.
(v) They are toxic and carcinogenic in nature.
5.5 Chemical Properties
Arenes are expected to be quite reactive due to the presence of
double bonds. However, benezne is quite stable and does not
undergo common addition reactions undergone by alkenes.
Electrophilic Aromatic Substitution Reactions
Aromatic hydrocarbons are generally known as arenes. An aryl
group is one derived from an arene by removal of a hydrogen
atom and its symbol is Ar –. Thus, arenes are designated ArH
just as alkanes are designated RH.
The most characteristic reactions of benzenoid arenes are the
substitution reactions that occur when they react with
electrophilic reagents. These reactions are of the general type
shown below. Mehcanism for Electrophilic Aromatic Substitution
The most widely accepted mechanism for aromatic electrophilic
ArH + E+
Ar – E + H+ or
substitution reaction is the two step mechanism.
(i) complex formation
(ii) Loss of proton from the complex
The electrophiles are either a positive ion (E+) or some other
electron-deficient species with a large partial positive charge.
For example, benzene can be brominated when it reacts with
bromine in the presence of FeBr3. Bromine and FeBr3 reacts to
produce positive bromonium ions, Br + . These positive
bromonium ions act as electrophiles and attack the benzene ring
replacing one of the hydrogen atoms in a reaction that is called
an electrophilic aromatic substitution (EAS).
Electrophilic aromatic substitutions allow the direct introduction
of a wide variety of groups into an aromatic ring and because of
this they provide synthetic routes to many important compounds.
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Of the following two steps,
Step 1: The formation of the arenium ion, is the rate-determining
step in electrophilic aromatic substitution.
Step 2: The loss of a proton, occurs rapidly relative to step 1
and has no effect on the overall rate of reaction.
TS I
TS II
Energy
complex
Substrate
(b) Halogenation of Benzene
Product
Progress of the reaction
Energy profile of an aromatic electrophilic substitution without
formation of complex. The evidence for the two step mechanism
are
(i) Detection and isolation of complex: A large number of
complexes as intermediate has been detected, some of them
have also been isolated.
(ii) Displacement of an H (or D) atom of C6H6 (or C6D6) by a
nitronium ion NO2+ (formed by the action of concentrated Benzene does not react with bromine or chlorine unless a
H2SO4 on concentrated HNO3) is an aromatic electrophile Lewis acid is present in the mixture, (as a consequence,
substitution reaction. If the C – H bond breaking benzene does not decolorize a solution of bromine in carbon
is the r/d, step, then the reaction will exhibit a primary tetrachloride). When Lewis acids are present, however,
kinetic isotope effect. By contrast C6H6 and C6D6 are found benzene reacts readily with bromine or chlorine, and the
to undergo nitration at essentially the same rate, thus C – H reactions give bromobenzene and chlorobenzene in good
bond breaking cannot be involved in the r/d step, that yields.
means complex formation is the r/d step. The Lewis acids most commonly used to effect chlorination
(a) Nitration of Benzene and bromination reactions are FeCl3, FeBr3, and AlCl3 all in
Benzene reacts slowly with hot concentrated nitric acid to the anhydrous form. Ferric chloride and ferric bromide are
yield nitrobenzene. The reaction is much faster if it is carried usually generated in the reaction mixture by adding iron to
out by heating benzene with a mixture of concentrated nitric it. The iron then reacts with halogen to produce the ferric
acid and concentrated sulphuric acid. halide :
2Fe + 3X2
2FeX3
⊕
The mechanism for aromatic bromination is as follows:
Step 1 :
Concentrated sulphuric acid increases the rate of the
reaction by increasing the concentration of the electrophile
–– the nitronium ion (NO2+).
Formation of Electrophile
In step 1 nitric acid acts as a base and accepts a proton
from the stronger acid, sulfuric acid.
In step 2 the protonated nitric acid dissociates and produces
a electrophile nitronium ion.
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Step 2 : I
HNO 3
+ I2
Kinetic isotope effects have not been observed for
chlorination and rarely for bromination, but iodination
shows kinetic isotope effect.
(c) Sulphonation of Benzene
Benzene reacts with fuming sulphuric acid at room
temperature to produce benzenesulfonic acid. Fuming
sulphuric acid is sulphuric acid that contains added sulphur
Step 3:
trioxide (SO3). Sulphonation also takes place in concentrated
sulphuric acid alone, but more slowly.
O
O
O S H
25 C O
+ O S
conc . H2SO 4
O
Suffer trioxide Benzenesulfonic acid
In either reaction the electrophile appears to be sulphur
trioxide. In concentrated sulphuric acid, sulphur trioxide is
produced in the following equilibrium in which H2SO4 acts
as both an acid and a base.
The mechanism of the chlorination of benzene in the Step 1: 2H2SO4 SO3 + H3O+ + HSO4-
presence of ferric chloride is analogous to the one for When sulphur trioxide reacts with benzene the following steps
bromination. Ferric chloride serves the same purpose in occur.
aromatic chlorinations as ferric bromide does in aromatic
All of the steps are equilibria, including step 1 in which sulphur
brominations. It assists in the generation and transfer of a
trioxide is formed from sulphuric acid. This means that the overall
positive halonium ion. The rate of reaction is often of the
reaction is an equilibrium as well. In concentrated sulphuric acid,
form, Rate = K [Ar – H] [X2I2] [Lewis acid]
the overall equilibrium is the sum of steps 1 - 4.
Hypo-halous acids (HO – X) in presence of strong acid also
Step 2:
become a very powerful halogenating agent.
HO X H+ H 2O X H 2O X
Fluorine reacts so rapidly with benzene that aromatic
fluorination requires special conditions and special types
of apparatus. Even then, it is difficult to limit the reaction to
monofluorination. Fluorobenzene can be made, however,
by an indirect method.
Iodine, on the other hand, is so unreactive that a special
technique has to be used to effect direct iodination; the
reaction has to be carried out in the presence of an oxidizing
agent such as nitric acid.
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Step 3: an arenium ion. The arenium ion (step 3) then loses a proton
to generate isopropylbenzene.
When R –– X is a primary halide, a simple carbocation
probably does not form. Rather, the aluminum chloride forms
a complex with the alkyl halide and this complex acts as the
Step 4: electrophile. The complex is one in which the carbon -
halogen bond is nearly broken –– and one in which the
carbon atom has a considerable positive charge.
RCH2 —— Cl : AlCl3
SO3H
Even though this complex is not a simple carbocation, it
+ H2SO4 + H2O acts as if it were and it transfers a positive alkyl groups to
the aromatic ring. These complexes are so carbocation like
that they also undergo typical carbocation rearrangements.
In fuming sulphuric acid, step 1 is unimportant because the
dissolved sulphur trioxide reacts directly. Friedel - Crafts alkylations are not restricted to the use of
alkyl halides and aluminum chloride. Many other pairs of
Because all of the steps are equilibria, the position of
reagents that form carbocations (or carbocation like species)
equilibrium can be influenced by the conditions we employ.
may be used as well. These possibilities include the use of
If we want to Sulphonate benzene we use concentrated
a mixture of an alkene and an acid.
sulphuric acid (or better fuming sulphuric acid). Under these
conditions the position of equilibrium lies appreciably to CH(CH3)2
0 C
the right and we obtain benzenesulphonic acid in good + CH3CH = CH2
C
yield.
On the other hand, we may want to remove a sulphonic
acid group from a benzene ring. To do this we employ dilute + 0 C
sulphuric acid and usually pass steam through the mixture. C
Under these conditions with a high concentration of water
the equilibrium lies appreciably to the left and A mixture of an alcohol and an acid may also be used
desulphonation occurs. The equilibrium is shifted even
further to the left with volatile aromatic compounds because
the aromatic compound distills with the steam.
+
Like iodination, sulphonation exhibits a kinetic isotopic
effect.
(d) Friedel - Crafts Alkylation
In 1877 a French chemist, Charles Friedel, and his American There are several important limitations of the Friedel - Crafts
collaborator James M. Crafts, discovered new methods for reaction.
the preparation of alkylbenzenes (ArR) and acylbenzenes
(e) Friedel - Crafts Acylation
(ArCOR). These reactions are now called the Friedel - Crafts
alkylation and acylation reactions. O
||
R The R C group is called an acyl group, and a reaction
AlCl3
+ R X + HX whereby an acyl group is introduced into a compound is
called an acylation reaction. Two common acyl groups are
The mechanism for the reaction (shown in following steps the acetyl group and the benzoyl group.
with isopropyl chloride as R –– X) starts with the formation
of a carbocation (step 1). The carbocation then acts as an
electrophile (step 2) and attacks the benzene ring to form
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O C
CH3C
Acetyl group Benzoyl group
The remaining steps in the Friedel - Crafts acylation of benzene
The Friedel - Crafts acylation reaction is an effective means are the following:
of introducing an acyl group into an aromatic ring. The
reaction is often carried out by treating the aromatic
compound with an acyl halide. Unless the aromatic
compound is one that is highly reactive, the reaction
requires the addition of at least one equivalent of a Lewis
acid (such as AlCl3) as well. The product of the reaction is
an aryl ketone.
O
O C
AlCl3
CH3
+ H3C C
excess benzene
80 C
Cl
acetyl chloride Acetophenon (methyl
phenyl ketone
Acyl chlorides, also called acid chlorides, are easily prepared
by treating carboxylic acids with thionyl chloride (SOCl2)
or phosphorus pentachloride (PCl5).
O O
H3C C + SOCl 2
80 C
H3C + SO 2 + HCl In the last step aluminum chloride (a Lewis acid) forms a complex
OH Thionyl chloride Cl
with the ketone (a Lewis base). After the reaction is over, treating
acetic acid acetyl chloride the complex with water liberates the ketone.
O
H3C R
O
+ PCl5 + POCl3 + HCl C O AlCl3 + 3H2 O C O + Al(OH)3 + 3HCl
OH Cl
Phosphorus
benzoic acid pentachloride benzoyl chloride H3C H5C6
Friedel - Crafts acylations can also be carried out using Several important synthetic applications of the Friedel - Crafts
carboxylic acid anhydrides. For example: reaction are later in the package.
O (i) Nature of Alkyl Groups
H3C C If the alkyl group is simple CH3- or CH3CH2-, then a complex
O AlCl3 between alkyl halide and Lewis acid is the electrophile as
+ excess benzene
shown in second mechanism. But because of the relative
H3C C
stability of s - and t- carbonium ions, the adducts with s-
O and t- alkyl halides ionise and it is now the carbonium ion
acetic anhydride that is predominantly the active species. e.g.
O
Me3C+ + AlCl 4
Me3C-Cl + AlCl3
C O
CH3
+ H3C (ii) Nature of Lewis Acid as Catalyst
The order of effectiveness of Lewis acid catalysts has been
OH
Acetophenone
shown to be AlCl3 > FeCl3 > BF3 > TiCl3 > ZnCl2 > SnCl4
The action of Me3CCH2Cl/AlCl3 on benzene is found to
In most Friedel - Crafts acylations the electrophile appears yield almost completely the rearranged product,
to be an acylium ion formed from an acyl halide in the PhCMe2CH2Me, which can be explained on the basis of the
following way:
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initial electrophilic complex being polarized enough to For Example
allow the rearrangement of [Me3 CCH 2 ] Cl Phenolic (-OH) group increases the electron density in
the benzene ring due to its strong +R effect.
AlCl3 to the more stable [Me 2 CCH 2 Me]
Cl AlCl3 . By contrast Me3CCH2Cl/FeCl3 on
benzene is found to yield almost completely the
unrearranged product, Me3CCH2Ph. This is due to the fact
that the complex with the weaker Lewis acid, FeCl3, is not
now polarized enough to allow the rearrangement.
(iii) Temperature
Not only nature of the alkyl group, but also temperature
determines the nature of electrophile. e.g. n-alkyl group
can be introduced to a fair extent without rearrangement at
low temperatures, because ionisation of the adduct is
retarded. But at higher temperatures, carbonium ion is
formed which rearranges and the product is rearranged alkyl
benzene. Thus n-propylchloride n-propyl chloride gives
isopropyl benzene as major product. In the same way,
isobutyl chloride gives t-butyl benzene. Other examples of ortho and para directing groups are
–NH2, –NHR, –NHCOCH3, –OCH3, –CH3, –C2H5, X
(X = F, Cl, Br, I) etc.
Halogens are o-, p- directing but these are mild
deactivating groups.
(b) Meta Directing Groups:
Decrease electron density at ortho and para positions
as a result incoming group prefer attack at meta
position.
For example :
Nitro (-NO2) group reduces the electron density in the
benzene ring due to its strong -R and -I effects.
5.6 Directive Influence
On EAS of substituted benzene, the attacking position of
incoming group depends on nature of existing substitutent.
Two types of behaviour are observed :
(a) Ortho and para directing groups
(b) Meta directing group Other examples of meta directing groups are
(a) Ortho and Para Directing Groups : –NO2, –CN, –CHO, –COR, –COOH, –COOR, –SO3H,
etc.
Increased electron density at ortho and para positions
results in incoming group prefering to attack at ortho
and para positions.
SCAN CODE
Hydrocarbons
HYDROCARBONS 141
Effect of Substituents on Electrophilic Aromatic Substitution
Strong Activating Moderately Deactivating
N H 2 , NHR, NR 2 C N
SO3 H
O H, O : CO 2 H, CO 2 R
CHO, COR
Moderately Activating
Strongly Deactivating
NHCOCH 3 , NHCOR
NO 2
OCH 3 , OR
NR 3
Weakly Activating CF3 , CCl3
CH 3 , C 2 H 5 , R CH 2 X
C6 H 5
Weakly Deactivating
O
||
F :, Cl : Br :, I :, CHX 2 , NO, S OH
C H CH W
Chemical Reactions of Benzene
SCAN CODE
Hydrocarbons
HYDROCARBONS 142
SUMMARY
SCAN CODE
Hydrocarbons
HYDROCARBONS 143
SCAN CODE
Hydrocarbons
HYDROCARBONS 144
EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS
Preparation and Chemical Properties of Alkanes 5. Br will abstract which of the hydrogen most readily..
1. Alkyl halides react with dialkyl copper reagents to give
(a) alkenyl halides (b) alkanes
(c) alkyl copper halides (d) alkenes
2. Which of the following compounds can be best prepared
by Wurtz-reaction ?
(a) Iso-butane (b) n-butane
(a) a (b) b
(c) n-pentane (d) Iso-pentane
(c) c (d) d
3. Select the structure of the major product formed in the
reaction 6. On mixing a certain alkane with chlorine and irradiating it
with ultraviolet light, it forms only one monochloroalkane.
This alkane could be
(a) propane (b) pentane
(c) isopentane (d) neopentane
7. The major product obtained in the photo catalysed
bromination of 2-methylbutane is:
(a) 1-bromo-2-methylbutane
(b) 1-bromo-3-methylbutane
(a) (b)
(c) 2-bromo-2-methylbutane
(d) 2-bromo-3-methylbutane
8. Below reaction is an example of :
(c) (d)
(a) isomerization (b) polymerization
4. To maximise the yield of monochloro product in the
above reaction ? (c) cracking (d) de-hydrogenation
9. In the chain propagation steps in the free-radical
(A) + Cl2 monochloro product
chlorination of methane. which of the following is not
(a) Cl2 must be added in excess possible step:
(b) Reactant (A) must be added in excess (1)
(c) Reaction must be carried out in dark (2)
(d) Reaction must be carried out with equimolar mixture
(3)
of Cl2 and A
(4)
(5)
(a) 2, 3, 5 (b) 1, 3, 6
(c) 2, 4 (d) 2, 3, 4
HYDROCARBONS 145
10. Of the five isomeric hexanes, the isomer which can give two Chemical Properties of Alkenes
monochlorinated compounds, is
16. Arrange the above in the decreasing order of reactivity
(a) 2-methylpentane (b) 2,2-dimethylbutane towards HBr :
(c) 2,3-dimethylbutane (d) n-hexane
Preparation of Alkenes
11.
Conc.H 2 SO4
Major product :
(a) (b)
(c) (d) None of these
12. Which of the following is the major product when 1- (a) a > b > c (b) b > a > c
butanol is heated with concentrated H2SO4 ? (c) b > c > a (d) a > c > b
(a) 1-butene (b) Cis-2-butene 17. Choose the correct major product for the reaction below
(c) Trans-2-butene (d) All of the above
13. The gas liberated by the electrolysis of dipotassium
succinate solution is:
(a) Ethane (b) Ethyne
(c) Propene (d) Ethene
(a)
14. Elimination of bromine from 2-bromobutane results in the
formation of
(a) predominantly 2-butyne
(b) predominantly 1-butene
(b)
(c) predominantly 2-butene
(d) equimolar mixture of 1 and 2-butene
15. Trans-2-phenyl-1-bromocyclopentane on reaction with (c)
alcoholic KOH produces
(a) 4-phenylcyclopentene (b) 2-phenylcyclopentene (d)
(c) 1-phenylcyclopentene (d) 3-phenylcyclopentene
18. Alkene + H2O Alcohol
Which of the following statements about this reaction is
correct ?
(a) It is Markovnikov addition of water to alkene.
(b) It involves carbonium ion rearrangement, if possible.
(c) both of these
(d) none of these
HYDROCARBONS 146
19. H3C CH = CH2 + HCl
Peroxide
Product, the intermediate 22. In the following sequence of reactions
of reaction is : O H O
CH3CH CHCH3
3
A
Zn B.
2
(a) (b)
The compound B is
(c) (d) (a) CH3CH2CHO (b) CH3COCH3
20. In case of addition of HX to an alkene, Markovnikov (c) CH3CH2COCH3 (d) CH3CHO
originally stated that 23. Ozonolysis of an organic compound given formaldehyde
(a) the H atom adds to the carbon atom of the double bond as one of the products. This confirms the presence of
that already has greater number of H atoms and halide (a) two ethylenic double bonds
ion adds to the carbon atom of the double bond that has (b) a vinyl group
fewer number of H atoms.
(c) an iso-propyl group
(b) the H atom adds to the carbon atom of the double bond
that has fewer number of H atoms and halide ion adds to (d) an acetylenic triple bond
the carbon atom of the double bond that has greater
number of H atom.
(c) both of these depending upon situation
24. reagent used for the reaction :
(d) none of these
21. Identify the product of the reaction when molecule
undergoes ozonolysis
(a) LiAlH4 (b) H2/Ni
(c) NaBH4 (d) H2, Pd — BaSO4
25. Butene-1 may be converted to butane by reaction with
(a) Zn-HCl (b) Sn-HCl
(c) Zn-Hg (d) Pd/H2
26. Consider the addition of HBr to 3,3-Dimethyl-1-butene
shown below. What is the best mechanistic explanation for
(I) (II) the formation of the observed product ?
(III) (IV)
(a) Protonation of the alkene followed by a hydride shift
and addition of bromide to the carbocation
(b) Double bond shift in the alkene following by the
(V) protonation and addition of bromide to the
carbocation
(a) I is only product (b) I and III (c) Addition of bromide to the alkene followed by a
double bond shift and protonation
(c) I and IV (d) II and IV
(d) Protonation of the alkene followed by a methyl shift
and addition of bromide to the carbocation
HYDROCARBONS 147
32. Give the major product of the following reaction
3,3-dimethyl-1-butene + HCl Major
27. (a) 2-chloro-3,3-dimethyl butane
(b) 2-chloro-2,3-dimethyl butane
(c) 1,2-dichloro-3,3-dimethylbutane
(d) 1-chloro-3,3-dimethylbutane
33. Major product :
(a) (b)
(c) (d) (a) (b)
28. Reaction of one molecule of HBr with one molecule of
1,3-butadiene at 40ºC gives predominantly
(a) 1-bromo-2-butene under kinetically controlled conditions
(b) 3-bromobutene under thermoynamically controlled (c) (d)
conditions
(c) 1-bromo-2-butene under thermodynamically controlled
conitions
(d) 3-bromobutene under kinetically controlled conditions
29. On catalytic reduction with H2/Pt how many alkenes will 34.
give n-butane ?
(a) 1 (b) 2
(c) 3 (d) 4
(a) (b)
30. HBr reacts with CH2 = CH – OCH3 under anhydrous
conditions at room temperature to give
(a) CH3CHO and CH3Br
(b) BrCH2CHO and CH3OH
(c) (d) none of these
(c) BrCH2 – CH2 – OCH3
(d) H3C – CHBr – OCH3
31. HCl
peroxide
(A)
EtONa
(Z)(major)
Identify (Z) in the above sequence of reactions :
(a) (b)
(c) (d)
HYDROCARBONS 148
35. Which compound will yield 5-keto-2-methyl hexanal upon 38. An organic compound C4H6 on ozonolysis give HCHO,
treatment with O3 ? CO2, CH3CHO. Compound will be :
(a) (b)
(a) (b) (c) (d)
39. Which of the following compound does not evolve CO2
gas, when undergo oxidative ozonolysis ?
(c) (d)
(a) (b)
36. Compound (X)
(c) (d)
40. One mole of a symmetrical alkene on ozonolysis gives two
Find the structure of (X). moles of an aldehyde having a molecular mass of 44 u. The
alkene is
(a) propene (b) 1-butene
(a) (b) (c) 2-butene (d) ethene
(c) (d)
41.
37. Ozonolysis of the following compound will produce;
is : Compound (A) is :
(a) (b)
(a)
(c) (d)
(b)
(c)
(d)
HYDROCARBONS 149
Preparation of Alkynes Chemical Properties of Alkynes
42. Identify the major product 45. The treatment of CH3MgX with CH3C C – H produces
(a) CH3 – CH = CH2 (b) CH3C C – CH3
(c) (d) CH4
46. The hydrocarbon which can react with sodium in liquid
(a) (b) ammonia to yield ionic compounds is
(a) CH3CH2CH2C CCH2CH2CH3
(b) CH3CH2C CH
(c) (d) (c) CH3CH = CHCH3
(d) CH3CH2C CCH2CH3
47. Predict the product of the reaction 1-butyne with 2
equivalents of HCl
43.
(a) (b)
(c) (d)
P should be
48. The reagent needed for converting is:
(a)
(b)
(a) LiAlH4 (b) Cat. Hydrogenation
(c) H2/Lindlar Cat. (d) Li/NH3
(c) 49. Choose the reagent to carry out the reaction.
(d)
(a) H2 + Lindlar catalyst (b) Li + NH3
44. The major organic compound formed by the reaction of
(c) Conc. H2SO4 (d) H2O + H+
1,1,1-trichloroethane with silver powder is
(a) acetylene (b) ethene
(c) 2-butyne (d) 2-butene
HYDROCARBONS 150
50. Rank the following compounds with respect to increasing 55. Acetylene does not react with
acidity
(a) Na (b) ammoniacal AgNO3
(1) 1-butene (2) butane
(c) HCl (d) NaOH
(3) 1-butyne (4) NH3 56. Which is the most suitable reagent among the following to
(a) 4 < 3 < 1 < 2 (b) 2 < 1 < 4 < 3 distinguish compound (3) from the others ?
(c) 2 < 1 < 3 < 4 (d) 3 < 1 < 2 < 4 (1) (2)
51. Which alkyne gives 3-ethylhexane on catalytic (3) (4)
hydrogenation ?
(a) Bromine in carbon tetrachloride
(b) Bromine in acetic acid solution
(c) Alk. KMnO4
(a) (b) (d) Ammonical silver nitrate
Preparation of Aromatic Hydrocarbons
57. The ‘middle oil’ fraction of coal–tar distillation contains
(c) (d) All of these
(a) benzene (b) naphthalene
(c) anthracene (d) xylene
58. Catalytic dehydrogenation of n–heptane in the presence of
52. Acetylene reacts with hypochlorous acid to form
Cr2O3/Al2O3 at 750 K gives
(a) Cl2CHCHO (b) ClCH2COOH
(a) iso–heptane (b) 1–heptane
(c) CH3COCl (d) ClCH2CHO
(c) toluene (d) 2,3–dimethyl pentene–1
53. 59.
Product (B) of the reaction is :
(a) Toluene (b) Ethyl-benzene
(c) Benzene (d) Butyne
Product (C) is 60. On heating a mixture of sodium benzoate and sodalime, the
following is obtained
(a) toluene (b) phenol
(a) (b) (c) benzene (d) benzoic acid
Chemical Properties of Aromatic Hydrocarbons
61. In desulphonation of benzene sulphonic acid, on treatment
with steam, electrophile is
(c) (d)
(a) H (b) SO3
Test of Alkynes (c) H2O (d) none of these
54. Which of the following reacts with Tollen’s reagent giving 62. The product of following reaction is C6H6 + Cl2
white precipitate ?
(a) C6H5Cl (b) ortho C6H4Cl2
(a) 2-pentene (b) 2-pentyne
(c) C6H6Cl6 (d) para C6H4Cl2
(c) 1-butyne (d) 1-butanol
HYDROCARBONS 151
63. In electrophilic aromatic substitution reaction, a phenyl 68. In the given reaction, what is the product ?
substituent on the aromatic ring is
(a) a deactivator and m–director
(b) a deactivator and o, p–director
(c) an activator and m–director
(d) an activator and o, p–director Product + HCl
64. In electrophilic aromatic substitution reactions, a–N=O
substituent on the aromatic ring is
(a) a deactivator and m–director
(b) a deactivator and o, p–director (a) (b)
(c) an activator and m–director
(d) an activator and o, p–director
65. Which of the following is not the activating group ?
(a) (b)
(c) (d)
(c) (d) – F
66. Which of the following compounds will not undergo Friedel–
Craft acylation when treated with CH3CH2COCl, AlCl3 ?
(a) Toluene (b) p–Xylene
69.
(c) Chlorobenzene (d) Benzophenone
67. The compound X is :
Compound X, is :
(a) (b)
(a)
(b)
(c) (d) none of these
70. The reaction of toluene with Cl2 in presence of FeCl3 gives
(c)
predominantly
(d) all are correct (a) benzoyl chloride (b) benzyl chloride
(c) o - and p - chlorotoluene (d) m-chlorotoluene
HYDROCARBONS 152
71. Presence of a nitro group in a benzene ring
75. (B)
(a) activates the ring towards electrophilic substitution
(b) renders the ring basic Product (B) in this reaction is
(c) deactivates the ring towards nucleophilic substitution
(d) deactivates the ring towards electrophilic substitution (a)
72. Which of the following will be obtained by the bromination
of ethylbenzene in presence of light ?
(b)
(a) (b)
(c)
(c) (d)
(d)
73. Arrange the following in decreasing order of reactivity
towards EAS (electrophilic aromatic substitution)
76.
Suitable
product of this reaction is
(a) a > b > c (b) c > b > a
(c) a > c > b (d) c > a > b
74. Consider the following statements (a) (b)
I: Hyperconjugation helps in increasing electron-density
at ortho and para-sites in case of alkyl groups.
II: Electron-donating groups are activators and ortho and
para-directors because they stabilise the arenium cations.
III: Electron-withdrawing groups are activators and are
meta-directors because they stabilise the arenium cations.
(c) (d)
IV:Halogens are activators and ortho and para-directors.
Select correct statements
(a) I, II (b) I, II, III
(c) II, III, IV (d) I, IV 77. Which of the following compounds will undergo bromination
most rapidly using Br2, FeBr3 ?
(a) p–methylacetanilide (b) bromobenzene
(c) acetanilide (d) benzenesulphonic acid
HYDROCARBONS 153
78. The major product obtained on the monobromination (with 80. Which of the following is the major product from
Br2/FeBr3) of the following compound A is bromination of meta-nitrobenzene sulphonic acid ?
OCH3
CH3
(A)
OCH3
OCH3
(a) (b)
Br
(a) (b)
CH3
CH3
Br
OCH3 OCH3
(c) (d)
Br
(c) (d)
Br CH3 CH3
79. Consider the following compound
The relative reactivity towards halonium ion is such that :
(a) I > II > III (b) II > I > III
(c) II > III > I (d) III > I > II
HYDROCARBONS 154
EXERCISE - 2 : PREVIOUS YEAR JEE MAIN QUESTIONS
1. What is the major product formed by HI on reaction with
(a) (b)
(2021-02-24/Shift - 1)
(c) (d)
4. The major product of the following reaction is:
(a)
(2021-02-25/Shift-2)
(b)
(a) (b)
(c)
(c) (d)
(d)
5. The correct sequence of reagents used in the preparation
of 4-bromo-2-nitroethyl benzene from benzene is:
2. Which of the following reagent is used for the following (2021-02-25/Shift - 2)
reaction? (2021-02-24/Shift - 1) (a) CH3COCl/AlCl3, Zn-Hg/HCl, Br2 /AlBr3, HNO3/H2SO4
?
(b) HNO3/H2SO4, Br2 /AlBr3, CH3COCl/AlCl3, Zn-Hg/HCl
CH3 CH 2 CH3 CH 3CH 2 CHO
(c) Br2 /AlBr3, CH3COCl/AlCl3, HNO3/H2SO4, Zn-Hg/HCl
(a) Copper at high temperature and pressure (d) CH3COCl/AlCl3, Br2 /AlBr3, HNO3/H2SO4, Zn-Hg/HCl
(b) Molybdenum oxide 6. For the given reaction:
(c) Manganese acetate
(d) Potassium permanganate
3. Identify A in the given chemical reaction. What is 'A'? (2021-02-25/Shift - 2)
(a) CH3CH2CH2NH2 (b)
(2021-02-25/Shift-1) (c) (d)
HYDROCARBONS 155
7. For the given reaction: (2021-02-26/Shift-1) (2021-03-16/Shift - 1)
(a)
What is ' A'?
(a) (b) (b)
(c) (d) (c)
8. Consider the below reaction, the major product among
the following is: (2021-02-26/Shift-2)
(d)
10. Which of the following is Lindlar catalyst?
(2021-03-16/Shift - 1)
(a) Zinc chloride and HCl
(b) Partially deactivated palladised charcoal
(a) (b) (c) Cold dilute solution of KMnO4
(d) Sodium and Liquid NH4
11.
(c) (d)
(2021-03-17/Shift - 1)
9. The products “A” and “B” formed in above reactions are:
(a) (b)
(c) (d)
HYDROCARBONS 156
12. Given below are two statements: (2021-03-17/Shift - 2) 15. Metallic sodium does not react normally with:
Statement I: 2-methylbutane on oxidation with KMnO4 (2021-07-20/Shift-2)
gives 2-methylbutan-2-ol.
(a) Gaseous ammonia (b) But-2-yne
Statement II: n-alkanes can be easily oxidised to
(c) Ethyne (d) Tert-butyl alcohol
corresponding alcohols with KMnO4.
16. Benzene on nitration gives nitrobenzene in presence of
Choose the correct option:
HNO3 and H2SO4 mixture, where: (2021-07-20/Shift - 2)
(a) Both statement I and statement II are incorrect
(a) Both H2SO4 and HNO3 act as a bases
(b) Both statement I and statement II are correct
(c) Statement I is incorrect but statement II is correct (b) HNO3 acts as an acid and H2SO4 acts as a base
(d) Statement I is correct but statement II is incorrect (c) Both H2SO4 and HNO3 act as an acids
13. Match List-I with List-II: (d) HNO3 acts as a base and H2SO4 acts as an acid.
List-I List-II 17. An organic compound ‘A’ C4H8 on treatment with KMnO4/
(Chemicals) (Use Preparation/Constituent) H+ yields compound ‘B’C3H6O. Compound ‘A’ also yields
(A) Alcoholic (i) electrodes in batteries compound ‘B’ on ozonolysis. Compound ‘A’ is:
potassium hydroxide (2021-07-25/Shift-1)
(B) Pd/BaSO4 (ii) obtained by
addition reaction (a) 2-Methylpropene
(C) BHC (Benzene (iii) used for (b) 1-Methylcyclopropane
hexachloride) -elimination reaction (c) But-2-ene
(D) Polyacetylene (iv) Lindlar’s Catalyst
(d) Cyclobutane
Choose the most appropriate match:
18. Presence of which reagent will affect the reversibility of
(2021-03-18/Shift - 1)
the following reaction, and change it to an irreversible
(a) (A) – (iii), (B) – (iv), (C) – (ii), (D) – (i) reaction: (2021-07-27/Shift - 1)
(b) (A) – (iii), (B) – (i), (C) – (iv), (D) – (ii)
hv
CH 4 I 2
CH 3 I HI
(c) (A) – (ii), (B) – (iv), (C) – (i), (D) – (iii) Reversible
(d) (A) – (ii), (B) – (i), (C) – (iv), (D) – (iii) (a) HOCl (b) dilute HNO3
14. Choose the correct statement regarding the formation of (c) Liquid NH3 (d) Concentrated HIO3
carbocations A and B given:
19.
Consider the above reaction and identify the Product B:
(2021-07-27/Shift - 1)
(2021-03-17/Shift - 2)
(a) Carbocation B is more stable and formed relatively (a) (b)
at faster rate
(b) Carbocation A is more stable and formed relatively
at faster rate
(c) Carbocation B is more stable and formed relatively (c) (d)
at slow a rate
(d) Carbocation A is more stable and formed relatively
at slow rate.
HYDROCARBONS 157
20. (a)
(b)
For above chemical reactions, identify the correct
statement from the following: (2021-07-20/Shift - 1) (c)
(a) Both compound ‘A’ and compound ‘B’ are
dicarboxylic acids
(b) Both compound ‘A’ and compound ‘B’ are diols
(d)
(c) Compound ‘A’ is diol and compound ‘B’ is
dicarboxylic acid
(d) Compound ‘A’ is dicarboxylic acid and compound 23. Identify correct A, B and C in the reaction sequence
‘B’ is diol. given below: (2021-08-31/Shift-2)
21. The major product formed in the following reaction is:
(2021-08-26/Shift-1)
(a)
(b)
(a) (b)
(c)
(c) (d)
(d)
22. The structures of A and B formed in the following
reaction are: [Ph = – C6H5]. (2021-08-31/Shift - 2)
HYDROCARBONS 158
24. The major product formed in the following reaction is: 25. Given below are two statements: one is labelled as
Assertion (A) and the other is labelled as Reason (R).
Assertion (A): Treatment of bromine water with
propene yields 1-bromopropan-2-ol.
Reason (R): Attack of water on bromonium ion follows
Markovnikov rule and results in 1- bromopropan-2-ol.
(2021-08-31/Shift - 1) In the light of the above statements, choose the most
appropriate answer from the options given below :
(a) (2021-08-31/Shift - 1)
(a) Both (A) and (R) are true but (R) is NOT the correct
explanation of (A)
(b) (A) is false but (R) is true.
(c) Both (A) and (R) are true and (R) is the correct
(b) explanation of (A)
(d) (A) is true but (R) is false.
26. Experimentally reducing a functional group cannot be
done by which one of the following reagents:
(c)
(2021-09-1/Shift - 2)
(a) Pt-C/H2 (b) Na/H2
(c) Pd-C/H2 (d) Zn/H2O
27. Consider the following chemical reaction.
(d)
1) Red hot Fe tube, 873K
CH CH
2)CO,HCl,AlCl
Product
3
The number of sp2 hybridized carbon atom(s) present in
the product is ______. (2021-02-24/Shift - 1)
28. A chloro compound "A".
(i) forms aldehydes on ozonolysis followed by the
hydrolysis.
(ii) when vaporized completely 1.53 g of A, gives 448 mL
of vapour at STP.
The number of carbon atoms in a molecule of compound
A is _______. (2021-08-26/Shift - 2)
HYDROCARBONS 159
29. Given below are two statements.
Statement I: The presence of weaker π-bonds make
alkenes less stable than alkanes.
Statement II: The strength of the double bond is (c)
greater than that of carbon-carbon single bond.
In the light of the above statements, choose the correct
answer from the options given below.
(JEE Main 2022)
(a) Both Statement I and Statement II are correct. (d)
32. Among the following, the major product of the given
(b) Both Statement I and Statement II are incorrect.
chemical reaction is (JEE Main 2022)
(c) Statement I is correct but Statement II is incorrect.
(d) Statement I is incorrect but Statement II is correct.
30. In the given reaction sequence, the major product ‘C’
is: (JEE Main 2022)
C8 H10
HNO3
H 2 SO4
A
Br2
B
alcoholic
KOH
C
(a)
(a)
(b) (b)
(c)
(c)
(d)
(d)
31. The product formed in the following reaction.
33. The major product formed in the following reaction, is
(JEE Main 2022) (JEE Main 2022)
(a) (a)
(b)
(b) (c)
(d)
HYDROCARBONS 160
34. The major product in. the following reaction
(JEE Main 2022)
(d)
37. Product A of following sequence of reactions is
(a)
(JEE Main 2022)
(b)
(c)
(a) (b)
(d)
35. Halogenation of which one of the following will yield
m-substituted product with respect to methyl group as
a major product? (JEE Main 2022)
(c) (d)
38. ‘A’ and ‘B’ respectively are:
3
1 O
A
2 Zn - H 2 O Ethane-1,2-dicarbaldehyde +
(a) (b) Glyoxal/Oxaldehyde
3
1 O
B
2 Zn - H 2 O 5-oxohexanal (JEE Main 2022)
(a) 1-methylcyclohex-1,3-diene & cyclopentene.
(b) Cyclohex-1,3-diene & cyclopentene
(c) 1-methylcyclohex-1,4-diene & 1-methylcyclopent-
(c) (d) 1-ene
36. What will be the major product of following sequence (d) Cyclohex-1,3-diene & 1-methylcyclopent-1-ene
of reactions? (JEE Main 2022) 39. The major product (P) in the reaction
i n BuLi,n C H Cl (JEE Main 2022)
n Bu
ii Lindlar cat,H2
5 11
(a)
(a)
(b)
(b)
(c) (c)
(d)
HYDROCARBONS 161
40. Two isomers ‘A’ and ‘B’ with molecular formula
C4H8 give different products on oxidation with
KMnO4 in acidic medium. Isomer ‘A’ on reaction with
KMnO4/H+ results in effervescence of a gas and gives
ketone. The compound ‘A’ is (JEE Main 2022) (b)
(a) But-1-ene
(b) cis-But-2-ene
(c) trans-But-2-ene (c)
(d) 2-methyl propene
41. (d)
The stable carbocation formed in the above reaction is 44. The major product of the following reaction is
(JEE Main 2022) (JEE Main 2022)
(a) CH 3CH 2 C H 2 (b) CH 3 C H 2
(c) CH 3 C H CH 3 (d)
42. A compound 'A' on reaction with 'X' and 'Y’ produces
the same major product but different by product 'a' and
'b'. Oxidation of 'a’ gives a substance produced by (a)
ants.
(b)
‘X’ and ‘Y’ respectively are : (JEE Main 2022)
(a) KMnO4/H+ and dil. KMnO4, 273 K
(b) KMnO4,(dilute), 273 K and KMnO4/H+
(c) KMnO4/H+ and O3, H2O/Zn (c)
(d) O3, H2O/Zn and KMnO4/H+
43. Major product of the following reaction is
(JEE Main 2022)
(d)
(a)
HYDROCARBONS 162
45. Major product ‘B’ of the following reaction sequence B. bromobenzene
is: (JEE Main 2022) C. mesitylene
D. nitrobenzene
E. benzene
Choose the correct answer from the options given
below (JEE Main 2022)
(a) C < D < E < A < B
(b) D < B < E < A < C
(c) D < C < E < A < B
(a) (d) C < D < E < B < A
48. Which among the following pairs of the structures will
give different products on ozonolysis?
(Consider the double bonds in the structures are rigid
and not delocalized.) (JEE Main 2022)
(b)
(c) (a)
(d)
46. The major product in the given reaction is (b)
(JEE Main 2022)
(c)
(a)
(d)
49. The major product ‘A’ of the following given reaction
has _____ sp2 hybridized carbon atoms
(b)
(JEE Main 2022)
50. The total number of monobromo derivatives formed
by the alkanes with molecular formula C5H12 is
(c) (excluding stereo isomers)____ (JEE Main 2022)
51. In the presence of sunlight, benzene reacts with Cl2 to
give product, X. The number of hydrogens in X is
_____ (JEE Main 2022)
52. A 100 mL solution of CH3CH2MgBr on treatment with
(d)
methanol produces 2.24 mL of a gas at STP. The
47. Arrange the following in increasing order of reactivity
weight of gas produced is _______ mg. [nearest
towards nitration
integer] (JEE Main 2022)
A. p-xylene
HYDROCARBONS 163
53. In the following given reaction 'A' is 55. The one giving maximum number of isomeric alkenes
on dehydrohalogenation reaction is (excluding
rearrangement) (JEE Main 2023)
(a) 1-Bromo-2-methylbutane
(b) 2-Bromopropane
(c) 2-Bromopentane
(d) 2-Bromo-3,3-dimethylpentane
(JEE Main 2023) 56. The major products ‘A’ and ‘B’, respectively, are
(a) (JEE Main 2023)
(a)
(b)
(b)
(c)
(c)
(d)
54. Find out the major products from the following (d)
reaction. (JEE Main 2023) 57. Choose the correct set of reagents for the following
conversion
trans ( Ph CH CH – CH 3 ) cis ( Ph CH CH – CH 3 )
(JEE Main 2023)
(a) Br2 , alc KOH , NaNH 2 , Na ( Liq NH 3 )
(b) Br2 , alc KOH , NaNH 2 , H 2 Lindlar Catalyst
(c) Br2 , aq KOH , NaNH 2 , H 2 Lindlar Catalyst
(a)
(d) Br2 , aq KOH , NaNH 2 , Na ( Liq NH 3 )
58. A hydrocarbon ‘X’ with formula C6 H 8 uses two
(b) moles of H 2 on catalytic hydrogenation of its one
mole. On ozonolysis, ‘X’ yields two moles of methane
dicarbaldehyde. The hydrocarbon ‘X’ is :
(c) (JEE Main 2023)
(a) hexa-1, 3, 5-triene
(b) 1-methylcyclopenta-1, 4-diene
(c) cyclohexa-1, 3-diene
(d) (d) cyclohexa-1, 4-diene
HYDROCARBONS 164
59. When a hydrocarbon A undergoes complete 63. The major product ‘P’ formed in the given reaction is:
combustion it requires 11 equivalents of oxygen and
produces 4 equivalents of water. What is the molecular
formula of A? (JEE Main 2023)
(a) C9 H8 (b) C11 H 4
(c) C5 H 8 (d) C11 H 8 (JEE Main 2023)
60. Decreasing order of dehydration of the following
alcohols is
(a)
(JEE Main 2023)
(a) a > d > b > c (b) b > d > c > a
(c) b > a > d > c (d) d > b > c > a
61. But-2-yne is reacted separately with one mole of
Hydrogen as shown below:
B Na
CH 3 C C CH 3
Pd / C
A (b)
liq . NH 3 H2
Identify the incorrect statements from the options
given below:
A. A is more soluble than B.
B. The boiling point & melting point of A are higher
and lower than B respectively.
C. A is more polar than B because dipole moment of A (c)
is zero.
D. Br2 adds easily to B than A. (JEE Main 2023)
(a) B and C only (b) B, C and D only
(c) A, C and D only (d) C and D only
62. ‘X’ is (JEE Main 2023)
(d)
64. Arrange the following compounds in increasing order
of rate of aromatic electrophilic substitution reaction
(JEE Main 2023)
(a) (b)
(a) b, c, a, d (b) d, b, c, a
(c) c, a, b, d (d) d, b, a, c
(c) (d)
HYDROCARBONS 165
65. The major product formed in the following reaction is
(c)
Choose the correct answer from the options given
below: (JEE Main 2023) (d)
(a)
3i O
68. 2 hexene
ii H 2 O Pr oducts
(b) The two products formed in above reaction are –
(JEE Main 2023)
(a) Butanal and acetaldehyde
(b) Butanal and acetic acid
(c) (c) Butanoic acid and acetic acid
(d) Butanoic acid and acetaldehyde
69. The product formed in the following multistep reaction
is:
2 6 2 2
i B H , ii H O , NaOH
CH 3 CH CH 2
iii PCC , iv CH 3 MgBr
(d)
(JEE Main 2023)
(a) CH 3 CH 2 CH 2 CH 2 OH
66. Compound ‘B’ is
(b)
(JEE Main 2023) (c)
(d)
70. Decreasing order of reactivity towards electrophilic
(a) (b)
substitution for the following compound is
(c) (d)
(JEE Main 2023)
(a) e > d > a > b > c (b) d > a > e > c > b
67.
Product [X] formed in the above reaction is: (c) a > d > e > b > c (d) c > b > a > d > e
(JEE Main 2023)
(a) H 3 C CH 2 CH CH 2
(b) H 3 C CH CH CH 3
HYDROCARBONS 166
71. The major product formed in the Friedel-Craft In the above reaction, left hand side and right hand
acylation of chlorobenzene is (JEE Main 2023) side rings are named as 'A' and 'B' respectively. They
undergo ring expansion. The correct statement for this
process is: (JEE Main 2023)
(a) Finally both rings will become five membered
each.
(b) Only A will become 6 membered.
(c) Finally both rings will become six membered each.
(a)
(d) Ring expansion can go upto seven membered rings
74. The major product for the following reaction is:
(JEE Main 2023)
(b)
(a)
(b)
(c)
(c)
(d)
(d)
72. In the following reaction ‘X’ is
CH 3 CH 2 4 CH 3
Anhy . AlCl3
HCl
'X ' 75. Maximum number of isomeric monochloro derivatives
major product
(JEE Main 2023) which can be obtained from 2,2,5,5-tetramethylhexane
by chlorination is _________ (JEE Main 2023)
(a) CH 3 CH 2 4 CH 2 Cl
76. 17 mg of a hydrocarbon M .F .C10 H16 takes
up 8.40mL of the H 2 gas measured at 0C and
760mm of Hg. Ozonolysis of the same hydrocarbon
yields
(b) The number of double bond/s present in the
hydrocarbon is _______. (JEE Main 2023)
(c) Cl CH 2 CH 2 4 CH 2 Cl
77. Number of bromo derivatives obtained on treating
ethane with excess of Br2 in diffused sunlight is
______ (JEE Main 2023)
78. Molar mass of the hydrocarbon (X) which on
(d)
ozonolysis consumes one mole of O3 per mole of (X)
and gives one mole each of ethanal and propanone is
_______ g mol –1 (Molar mass of
73. C :12 g mol –1 , H :1 g mol –1 ) (JEE Main 2023)
HYDROCARBONS 167
EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS
Objective Questions I [Only one correct option] 5. Nitration of benzene is possible by which of the following
1. Choose the major product of reaction reagents ?
(a) Conc. HNO3/Conc. H2SO4
(b) R NO2/H
(c) both (a) and (b)
(d) none of these
6. The compound which has one isopropyl group, is
(a) 2, 2, 3, 3-tetramethyl pentane
(b) 2, 2-dimethyl pentane
(c) 2, 2, 3- trimethyl pentane
(a) I (b) II (d) 2-methyl pentane
(c) III (d) IV
7. Which of the following statements is correct ?
2. What will be formed in the following Kolbe’s electrolys
is? (I) Melting point of alkane increases with increase of
C atoms and with increase in branching.
(II) Boiling point of alkane increases with increase of
C atoms but with decrease in branching.
(a) 2-butene (b) 1-butyne (III) Cycloalkanes have lower boiling point than normal
(c) 2-butyne (d) Both b and c alkane with same number of C atoms.
3. The boiling point of trans-dichloroethene is 48 degress (IV) Alkenes have lower boiling point than same number
Celsius. Which number best approximates the boiling of C atoms in alkanes.
point of cis-dichloroethene ?
(a) (I), (II) (b) (I), (II), (III)
(a) 36 degrees Celsius (b) 42 degrees Celsius
(c) 48 degrees Celsius (d) 54 degrees Celsius (c) (III), (IV) (d) (IV)
4. What is the major product in the reaction ? 8. The bond dissociation energy of the C—H bond for the
compound
(a)
decreases in the order :
(a) P > Q > R > S (b) S > R > Q > P
(b)
(c) S > P > Q > R (d) Q > P > S > R
9. Which of the following is incorrect regarding combustion
of alkanes ?
(c) (a) It is always an exothermic process
(b) It proceeds through a free radical mechanism
(c) It can be controlled to an intermediate stage
(d) (d )2-methyl butane will lib erate less heat than
n-pentane.
HYDROCARBONS 168
10. Propyne and propene can be distinguished by 15. Which of the following cannot be used to prepare cumene
(a) conc. H2SO4 (b) Br2in CCl4 from benzene ?
(c) dil. KMnO4 (d) AgNO3 in ammonia (a)
11. Which of the following would not form upon electrolysis (b) CH3––CH2––CH2––Cl, AlCl3
of aqueous solution of potassium propanoate ?
(c)
(a) Butane (b) Ethyl ethanoate
(c) Ethyl propanoate (d) Ethene
(d) CH3––CH2––CH2––OH, BF3
12.
3Cl2
Br2 , Fe Zn
Major product is 16. or light HCl Product
(a) The main product is
(a) (b)
(b)
(c) Both (a) and (b) in same amount
(d) None of the above
13. Which of the following alkenes is most reactive towards (c) (d)
electrophilic addition reaction ?
(a) H2C = CH2 (b) CH3 – CH = CH2 17. In which of the following the incorrect place for electrophilic
substitution has been indicated ?
(c) (d) H2C = CH – CH2– CH3
14. Which molecule will give following dicarboxylic acid (a)
upon treatment with acidic solution of KMnO4 ?
(b)
(c)
(a) (b)
(d)
(c) (d)
HYDROCARBONS 169
18. An electrophile, E attacks the benzene ring to generate
the intermediate –complex. of the following, which
–complex is of lowest energy ?
NO2 (b)
H
(a) (b) E
(c)
H E
NO2 NO2
H
(c) E (d) H
E (d)
19. The sulphonic acid group is often readily replaced by a
nitro group e.g.,
21. Which will undergo Friedal-Craft alkylation reaction ?
OH
CH2CH3 COOH OH
O2N NO2
SO3H
HNO3
NO2
NO
OH
O2N NO2
1 2 3 4
(a) 1 and 3 (b) 2 and 4
(c) 1 and 2 (d) 1, 2 and 4
NO2 Objection Question II
(Picric Acid)
[One or more than one correct option]
This is because
22. Halogens are deactivating yet ortho, para directing in
(a) –SO3H group is a better leaving group than –NO2 group
electrophilic aromatic substitution. Which statements do
in electrophilic substitution
not explain this ?
(b) –NO2 group is a better leaving group than –SO3H group
(a) A combination of inductive electron withdrawal and
in electrophilic substitutions
resonance electron release.
(c) This is a nucleophilic substitution.
(b) Inductive electron withdrawal with no resonance
(d) both (b) and (c) effect.
(c) A combination of inductive electron release and
20. resonance electron withdrawal.
(d) A combination of inductive electron release and
Which of the following is the correct structure of the organic resonance electron release
product of the above reaction ?
(a)
HYDROCARBONS 170
23. Choose the correct comparisons : 28. Predict the products of following reactions :
(a)
(b) > (a) A is Ph – CH2 – CH2 – CH2 – CH3
(b) B is Ph – CH = CH – CH = CH 2
(c) A is Ph – CH = CH – CH = CH2
(c) (d) B is Ph – CH2 – CH2 – CH = CH2
(Reactivity towards HBr) 29. :
(a) A is
(d)
(b) A is
24. Which of the fo llo wing re actions a re correctly
represented? (R is a alkyl group)
(c) B is
(a) R – CH = CH2 + HCl
(b) R – CH = CH2 + HI R – CH 2 – CH2 – I
(d) B is
(c) R – CH = CH2 + HBr R – CH2 – CH2 – Br
30. Which of the following is/are deactivating groups towards
electrophilic aromatic substitution ?
(a) – Cl (b) – NO2
(d) R – CH = CH2 + HI
25. Which of the following will produce a visible change (c) – CCl3 (d) Cl
with 1-butyne and can be used to differentiate it from 2-
butyne ? 31. Which of the following are deactivating but ortho, para
+
(a) Ag(NH3)2 (b) Cu(NH3)2+ directing during electrophilic aromatic substitution
+ reaction ?
(c) KMnO4/H (d) Br2
26. Which of the following reactions are not feasible ?
(a)
(a) (b)
(b)
(c)
(d)
27. Which of the following will react with 1-butyne ?
(c) (d)
(a) AgNO3 + NH4OH (b) Cu2Cl2 + NH4OH
(c) Na (d) KMnO4/
HYDROCARBONS 171
32. Isopropyl benzene can be obtained by : 36. In this reaction which ring will be reduced, by
hydrogenation.
(a)
(b)
(c)
37. Identify number of substituents those are deactivating
but ortho and para directing.
(d)
33. Which of the statements are correct for alkyne with
molecular formula C6H10? (Only structural isomers)
(a) It shows 7 structural isomers.
(b) It shows 4 terminal and 3 internal alkynes.
(c) It shows 3 terminal and 4 internal alkynes.
(d) Only Internal alkynes are acidic in nature
34. In which of the followings, reactant and product are
correctly matched ? 38. Examine the structural formulas shown below and find
out how many compounds undergo electrophilic nitration
(a) more rapidly than flouro benzene.
(b)
(c) , ,
(d)
Numerical Value Type Questions
35. How many mono chlorinated products may be obtained ,
when the alkane shown below is heated in the presence
of Cl 2
HYDROCARBONS 172
39. Examine the structural formulas shown below and find 41. Examine the structural formulas shown below and find
out how many compounds will show oxidation reaction out how many compounds can not, give Friedel Craft
with acidic KMnO 4. reaction.
,
, ,
, , , Assertion Reason
(A) If both Assertion and Reason are correct and
40. Each of the compounds shown below has two aromatic Reason is the correct explanation of Assertion
ring, labled as A and Identify number of compounds in (B) If both Assertion and Reason are true but
which ring B is more active than ring A for electrophilic
aromatic substitution reaction.
Reason is not the correct explanation of
Assertion.
(C) If Assertion is true but Reason is false.
(D) If Assertion is false but Reason is true.
42. Assertion (A) : Addition of HBr in presence of a peroxide
(ROOR) to propene gives 2-bromo propane.
Reason (R) : Reaction involves a bromine free radical.
(a) A (b) B
(c) C (d) D
43. Assertion (A) : 1-butyne forms white precipitate with
ammoniacal silver nitrate solution while 2-butyne does
not.
Reason (R) : 1-butyne has acidic hydrogen.
(a) A (b) B
(c) C (d) D
44. Assertion (A) : Among isomeric alkanes, branching increase
the boiling points.
Reason (R) : Branching lowers the intermolecular van der
Waal’s force of attraction.
(a) A (b) B
,
(c) C (d) D
HYDROCARBONS 173
45. Assertion (A) : Addition of HCl to 3-methyl-1-butene gives 51. Assertion (A) : Toluene undergoes nitration much more
2-chloro-2-methyl butane as the major product. readily than benzene.
Reason (R) : Rearrangement of carbocation to more stable Reason (R) : It is due to electron releasing nature of –CH3
carbocation leads to formation of major product. group which increases electron density on benzene and
(a) A (b) B electrophilic substitution reaction like nitration becomes
faster.
(c) C (d) D
(a) A (b) B
46. Assertion (A) : A mixture of alkene and alkane can be
separated by passing the mixture through a cold, (c) C (d) D
concentrated sulphuric acid solution. Match the Following
Reason (R) : Alkene is absorbed in the solution while
alkane passes unreacted. Each question has two columns. Four options are
(a) A (b) B given representing matching of elements from
(c) C (d) D Column-I and Column- II.
47. Assertion (A) : Alkenes usually undergo electrophilic 52.
addition reaction at carbon-carbon double bond.
Reason (R) : Electrophilic addition at double bond
produces carbocation intermediate.
(a) A (b) B
(c) C (d) D
48. Assertion (A) : Propyne is more reactive than propene
towards electrophilic addition of HBr.
Reason (R) : Propyne has greater electron density
available for electrophile due to two pi-bonds.
(a) A (b) B
(c) C (d) D
49. Assertion (A) : Hydrogenation of an alkene is always an
exothermic process. 53.
Reason (R) : Alkane has lower potential energy than an
alkene.
(a) A (b) B
(c) C (d) D
50. Assertion (A) : Benzene does not decolourise alkaline
KMnO4.
Reason (R) : Benzene is stabilized by resonance and -
electrons are delocalized.
(a) A (b) B
(c) C (d) D
HYDROCARBONS 174
Paragraph Type Questions OCH3 OCH3
Use the following passage, solve Q. 54 to Q. 56 (c) H (d)
+ +
Passage
E
H E
Aromatic compounds can easily show electrophilic substitution
reactions due to the presence of pie electron clouds above and Use the following passage, solve Q. 57 to Q. 59
below the plane of aromatic ring. This ring can be easily attached Passage
by electrophiles due to high electro density. The mechanism of
these reaction is common in general which can be given as follows: Directing nature of substituted aromatic compound is decided
by stability of -complex or arenium ion. If -complex is
stabilise at o-and p-position by attack of electrophile then the
group is o-and p-directing but if -complex is stabilise at m-
position then group will be meta directing
H
k2
RX E RX E +H
fast
54. In which of the following compounds the rate of electrophilic
substitution (Halogenation) is fastest ?
(a) (b)
NH
O On the basis of above explanation find out correct answers of
following questions.
(c) (d) 57. Which of the following is m-directing ?
NH
N
H
(a) (b)
55. Which of the following resonance structures is not a
contributor to the cyclo hexa dienyl cation intermediate in
the halogenation of benzene ?
H X H X
(c) (d)
(a) (b)
58. Which of the following is not o-and p-directing ?
X H X
H
(c) H (d)
(a) (b)
56. Which of the following -complexes generated by the attack
of an electrophile of benzene ring has lowest energy ?
OCOCH3 NO2
(a) + (b) + (c) (d)
H E H E
HYDROCARBONS 175
59. Which of the following is o- and p-directing ?
(c)
(a) (b)
(d) No reaction
61. Major product formation take place at which position in
this reaction :
(c) (d)
(a) 3 (b) 1
Use the following passage, solve Q. 60 to Q. 62 (c) 6 (d) 4
Passage 62. Find out major product of following reaction :
If aromatic ring is substituted by more than groups then
electrophilic aromatic substitution reaction take place
according to more activating group. Types of group
which donate electron in aromatic ring known as
activating groups.
60.
(a) (b)
Find out correct product of reaction.
(a)
(c) (d)
(b)
HYDROCARBONS 176
Use the following passage, solve Q. 63 to Q. 65
Passage (a)
A benzene ring deactivated by strong and moderate
electron withdrawing group that is, any meta directing
group, is not electron rich enough to undergo Friedel-
Crafts reactions. (b)
(c)
Friedel-Crafts reaction also do not occur with NH2 group
as it react with AlCl3 and produce deactivating group.
(d)
65. Which of the following sequence of reaction is correct
for the synthesis of product
X (No reaction)
63. Which of the following compounds undergo Friedel-
Crafts alkylation reaction ?
(a)
(a) (b)
(b)
(c) (d)
(c)
64. Which of the following cannot be starting material for
this compound (d) All are incorrect
HYDROCARBONS 177
EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTIONS
Objective Questions [Only one correct option] 7. 2-hexyne gives trans-2 hexene on treatment with (2004)
1. Which one of the following alkenes will react fastest with (a) Li/NH3 (b) Pd/BaSO4
H2 under cataltic hydrogenation condition? (2000) (c) LiAlH4 (d) Pt/H2
8. 1-bromo-3-chlorocyclobutane when treated with two
(a) (b) equivalents of Na, in the presence of ether which of the
following will be formed? (2005)
(c) (d)
(a) (b)
2. The reaction of propene with HOCl proceeds via the (c) (d)
addition of (2001)
+ + 9. Cyclohexene is best prepared from cyclohexanol by which
(a) H in the first step (b) Cl in the first step
– + –
of the following? (2005)
(c) OH in the first step (d) Cl and OH single step
(a) conc. H3PO4 (b) conc. HCl/ZnCl2
3. In the presence of peroxide, hydrogen chloride and
(c) conc. HCl (d) conc. HBr
hydrogen iodide do not give anti-Markownikoff’s addition
to alkenes because (2001) 10. Identify the product.
(a) both are highly ionic (2006)
(b) one is oxidising and the other is reducing (a) (b)
(c) one of the steps is endothermic in both the cases
(d) all the steps are exothermic in both the cases
4. Identify a reagent from the following list which can easily
(c) (d)
distinguish between 1-butyne and 2-bytyne. (2002)
(a) bromine, CCl4 (b) H2, Lindlar catalyst
11. The reagent(s) for the following conversion,
(c) dilute H2SO4, HgSO4 (d) ammoniacal CuCl 2
solution
is/are
5. Consider the following reaction
(2007)
(a) alcoholic KOH
(b) alcoholic KOH followed by NaNH2
Identify the structure of the major product X (2002) (c) aqueous KOH followed by NaNH2
(a) (b) (d) Zn/CH3OH
12. The synthesis of 3-octyne is achieved by adding a
bromoalkane into a mixture of sodium amide and an alkyne.
The bromoalkane and alkyne respectively are (2010)
(c) (d)
(a) BrCH CH CH CH CH and CH CH C CH
2 2 2 2 3 3 2
(b) BrCH 2 CH 2 CH 3 and CH 3 CH 2 CH 2 C CH
6. 2-phenyl propene on acidic hydration, gives (2004)
(c) BrCH 2 CH 2 CH 2 CH 2 CH 3 and CH 3 C CH
(a) 2-phenyl-2-propanol (b) 2-phenyl-1-propanol
(d) BrCH 2 CH 2 CH 2 CH 3 and CH 3CH 2 C CH
(c) 3-phenyl-1-propanol (d) 1-phenyl-2-propanol
HYDROCARBONS 178
Numerical Value Type Question 17. Assertion (A) : 1-butene on reaction with HBr in the
presence of a peroxide produces 1-bromobutane.
13. The total number of cyclic isomers possible for a
hydrocarbon with the molecular formula C4H6 is (2010) Reason (R) : It involves the formation of a primary radical.
14. The number of isomeric tetraenes (NOT containing sp- (2000)
hybridized carbon atoms) that can be formed from the (a) A (b) B
following reaction sequence is ________. (c) C (d) D
18. Assertion (A) : Dimethyl sulphide is commonly used for
the reduction of an alkene to get the carbonyl compound.
Reason (R) : It reduces the ozonide giving water soluble
dimethyl sulphoxide and excess of it evaporates. (2001)
(a) A (b) B
(2022)
(c) C (d) D
15. The number of –CH2 (methylene) groups in the product
formed from the following reaction sequence is ________.
Paragraph Type Questions
Use the following passage to solve Q. 16 and Q. 17
Passage
An acyclic hydrocarbon P, having molecular formula C6H10,
gave acetone as the only organic product through the
following sequence of reactions, in which Q is an
(2022) intermediate organic compound.
16. The total number of chiral molecules formed from one
molecule of P on complete ozonolysis (O3, Zn/H2O) is
________.
(2022) 19. The structure of compound P is (2011)
(a)
(b)
Assertion Reason
(A) If both Assertion and Reason are correct and (c)
Reason is the correct explanation of
Assertion
(B) If both Assertion and Reason are true but
(d)
Reason is not the correct explanation of
Assertion.
(C) If Assertion is true but Reason is false.
(D) If Assertion is false but Reason is true.
HYDROCARBONS 179
20. The structure of the compound Q is (2011)
(c) (d)
(a)
22. The correct statement with respect to product Y is
(2014)
(a) It gives a positive Tollens test and is a functional
(b) isomer of X.
(b) It gives a positive Tollens test and is a geometrical
isomer of X.
(c) It gives a positive iodoform test and is a functional
(c) isomer of X.
(d) It gives a positive iodoform test and is a geometrical
isomer of X.
Subjective Type Question
(d)
23. Identify X, Y and Z in the following synthetic scheme and
Use the following passage to solve Q. 18 and Q. 19 write their structures. (2002)
Passage
Schemes 1 and 2 describe sequential transformation of alkynes
M and N. Consider only the major products formed in each
step for both the schemes.
24. Considering the following reaction sequence, the
correct statement(s) is(are)
(a) Compounds P and Q are carboxylic acids.
(b) Compound S decolorizes bromine water.
21. The product X is (2011) (c) Compounds P and S react with hydroxylamine to
give the corresponding oximes.
(d) Compound R reacts with dialkylcadmium to give the
corresponding tertiary alcohol.
(a) (b)
(2022)
HYDROCARBONS 180
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HYDROCARBONS
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THERMODYNAMICS
AND
THERMOCHEMISTRY
Chapter 08 182
THERMODYNAMICS AND THERMOCHEMISTRY
1. INTRODUCTION 2.2.2 Closed System
It is the study of flow of energy. It encompasses the study of flow In a closed system, there is no exchange of matter, but exchange
of heat as well as mass. of energy is possible between system and the surroundings. The
presence of reactants in a closed vessel made of conducting
The law of thermodynamics deals energy changes of macroscopic
material. i.e., Copper or steel, is an example of a closed system.
systems involving a large number of molecules rather than
microscopic systems containing a few molecules.
Thermodynamics is not concerned about how and at what rate
these energy transformations are carried out, but is based on
initial and final states of a system undergoing the changes.
2. THERMODYNAMIC TERMS
2.1 System and The Surroundings
A system in the thermodynamics refers to that part of universe in
which observations are made and remaining universe constitutes
the surroundings. The surroundings include everything other
than the system. System and the surroundings together constitute
the universe. Closed system
The Universe = The System + The Surrounding
2.2.3 Isolated System
2.2 Types of System
In an isolated system, there is no exchange of energy or matter
2.2.1 Open System between the system and the surroundings. The presence of
reactants in a thermos flask or any other closed insulated vessel
In an open system, there is exchange of energy and matter between
is an example of an isolated system.
system and surroundings. The presence of reactants in an open
beaker is an example of an open system.
Here the boundary is an imaginary surface enclosing the beaker
and reactants.
Isolated system
Open system
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2.3 State of a System
In thermodynamics, state of the system defined by state functions
and state variables.
2.3.1 State Functions
These physical quantities whose value depend only upon the
status of the the system and does not depend upon the path by
which this state has been attained are said to be state function. In
other words, if the physical quantity depends only upon the initial Extensive and intensive properties
state and final state of the system independent of the path by
2.5 Thermodynamic Processes
which this change had been brought upon is known as a state
function. Some common state functions are pressure (p), volume Let us consider a system having P1V1 and T1 state functions if T1
(V), temperature (T), internal energy (U), enthalpy (H), entropy is chaged to T2 then the resulting system is characterized by state
(S), etc. functions P1V1 and T2 and the process of changing state is called
thermodynamic process. A thermodynamic process can be defined
2.3.2 State Variables as a process having change in state of system. These are of
If any of P, V or T is changed, it act as state variable and the other following types:
which depends on first one are state functions. 2.5.1 Isothermal Process
2.3.3 Path Functions The thermodynamic process in which temperature remains
constant throughout is called isothermal process.
Functions, which are associated with the path they carried
through, are called path functions. Values of path functions varies 2.5.2 Adiabatic Process
if the followed path is different. The common path funtions are
The thermodynamic process in which heat exchange between
heat and work.
system and surrounding is not possible.
2.4 Extensive and Intensive Properties 2.5.3 Isobaric Process
In thermodynamics, a distinction is made between extensive The thermodynamic process occurrring at constant pressure is
properties and intensive properties. An extensive property is a called isobaric process.
property whose value depends on the quantity or size of matter
2.5.4 Isochoric Process
present in the system. For example, mass, volume, internal energy,
enthalpy, heat capacity, etc. are extensive properties. The thermodynamic process occurring at constant volume is called
isochoric process.
Those properties which do not depend on the quantity or size of
matter present are known as intensive properties. For example 2.5.5 Cyclic Process
temperature, density, pressure etc. are intensive properties. The therymodynamic process having same initial and final state
is called cyclic process.
Example
2.6 Thermodynamic Equilibrium
A container having the volume V, contains water at temperature
25ºC . If we put a partition exactly in the middle, each part will have A system is said to be under thermodynamic equilibrium when
a volume V/2, but the temperature will remain same, i.e, 25ºC. none of the state variables are changing and it satisfies the three
equilibriums.
2.6.1 Mechanical Equilibrium
There is no mechanical motion and the pressure and the volume
of the system are not changing.
2.6.2 Thermal Equilibrium
There is no flow of heat and the temperature and the system does
not change with time.
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2.6.3 Chemical Equilibrium
If any chemical reaction is taking place in the system then the rate
of forward reaction is equal to the rate of backward reaction which
means that the overall moles of the system is constant.
3. ZEROTH LAW OF THERMODYNAMICS
This statement just says that, if body 'A' is in thermal equilibrium
with body 'B' and body 'B' is in thermal equilibrium with body 'C'
then body 'A' will also be in thermal equilibrium with body 'C' and
all three will be in thermal equilibrium with each other. Adiabatic system
Let us call the initial state of the system as state A and its
temperature as TA. Let the internal energy of the system in state A
be called UA. We can change the state of the system in two different
ways.
First way: We do some mechanical work, say 1 kJ, by rotating a
set of small paddles and thereby churning water. Let the new
state be called B state and its temperature, as TB . It is found that
TB > TA and the change in temperature, T = TB –TA. Let the
internal energy of the system in state B be UB and the change in
Zeroth law of thermodynamics internal energy, U =UB – UA.
4. INTERNAL ENERGY Second way: We now do an equal amount (i.e., 1 kJ) electrical
A thermodynamic system containing some quantitiy of matter is work with the help of an immersion rod and note down the
itself associated with a certain quantity of energy. It is the sum temperature change. We find that the change in temperature is
of all different types of energies associated with atoms and same as in the earlier case, say, TB – TA.
molecules such as electronic energy (Ee), nuclear energy (En), In fact, the experiments in the above manner were done by J. P.
chemical bond energy (Ec), potential energy (Ep) and kinetic energy Joule between 1840–50 and he was able to show that a given
(Ek). This total energy of a system always implies internal energy amount of work done on the system, no matter how it was done
represented by the symbol ‘U’. Thus (irrespective of path) produced the same change of state, as
U = Ee + En + Ec + Ep + Ek measured by the change in the temperature of the system.
The change in internal energy can be brought about whenever So, the adiabatic work, wad required to bring about a change of
heat is absorbed or realeased by the system, work is done on or state is equal to the difference between the value of U in one state
by the system or matter enters or leaves the system. and that in another state, U i.e.,
U = U2 – U1 = wad
5. CONCEPT OF HEAT AND WORK
Therefore, internal energy, U, of the system is a state function.
5.1 Thermodynamic Work
By conventions of IUPAC in chemical thermodynamics. The
Let us first examine a change in internal energy by doing work. positive sign expresses that wad is positive when work is done on
We take a system containing some quantity of water in a thermo the system and the internal energy of system increases. Similarly,
flask or in an insulated beaker. if the work is done by the system, wad will be negative because
Let us bring the change in the internal energy of the system by internal energy of the system decreases.
doing some work on it.
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5.2 Heat Now the final internal enerygy U2 is given by
We can also change the internal energy of a system by transfer of U2 = U 1 + q + w
heat from the surroundings to the system or vice-versa without or U2 – U1 = q + w
expenditure of work. This exchange of energy, which is a result of
temperature difference is called heat, q. Let us consider bringing or U = q + w
about the same change in temperature by transfer of heat through i.e., change in internal energy = Heat absorbed + Work done on
thermally conducting walls instead of adiabatic walls. the system
For a given change in state, q and w can vary depending on how
the change is carried out. However q + w = U will depend only
on initial and final state. It will be independent of the way the
change is carried out. If there is no transfer of energy as heat of
energy as heat or as work (isolated system) i.e., if w = 0 and q = 0,
then U = 0.
The equation, U = q + w is a mathematical statement of the first
law of thermodynamics which states that, “Energy can neither
be created nor be destroyed although it may be changed from one
form to another”.
From this statement it follows that total energy of the universe,
i.e., system and surroundings taken together is always constant
Non-adiabatic system
during any physical or chemical process.
We take water at temperature, TA in a container having thermally
conducting walls, it in a huge heat reservoir at temperature, TB.The 7. CONCEPT OF REVERSIBILITY
heat absorbed by the system (water), q can be measured in terms
of temperature difference , TB – TA. In this case change in internal A process whose direction can be changed by an infinitesimal
energy, change to the system or surroundings and which can be reversed
by retracing the original path and the system is restored to the
U= q, when no work is done at constant volume. By conventions initial state. The driving force of a reversible process is very-very
of IUPAC in chemical thermodynamics. The q is positive, when small and such a process is extremely slow. For a process to be
heat is transferred from the surroundings to the system and the reversible there must not be any dissipative forces and also the
internal energy of the system increases and q is negative when system should be in a Quasi Static State.
heat is transferred from system to the surroundings resulting in
decrease of the internal energy of the system. 7.1 Quasi Static State
A quasi static state means that the system seems to be static at all
6. FIRST LAW OF THERMODYNAMICS
intervals of time but actually is not. The motion is so slow that it
Let us consider the general case in which a change of state is is almost impossible to detect the motion and the system seems
brought about both by doing work nad transfer of heat. The to be in equilibrium with the surroundings at all instants of time.
change in internal energy for this case can be written as
7.2 Irrversible Process
U=q+w
Processes other than reversible processes are known as
Lets simplify it through a diagrammatic representation of system irreversible process as these processes do not meet the
undergoing changes. requirements of reversibilty. So it can be defined as “When a
process goes from initial to final state in a single step and can not
be carried out in the reverse order, it is said to be an irreversible
process”.
First law of thermodynamics
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Difference between Reversible Process and Irreversible Process
S.NO. Reversible Process Irreversible process
1. It takes place in infinite number of It takes place in single step
number of infinitesimally small steps and
it would take infinite time to occur
2. It is imaginary as it assumes the presence It is real and can be performed actually
of, frictionless and weightless piston
3. It is in the state of equilibrium at all the It is an equilibrium state only at the
stages of operation initial and final stages of the
operation
4. All changes are reversed when the After the occurring of the process
process is carried out in reversible changes do not return to the initial
direction state by themselves
5. It is extremely slow. It proceeds at measureable speed.
6. Work done by a reversible process is Work done in irreversible process is
greater than the corresponding smaller than the corresponding
irreversible process reversible process.
8. EXPANSION WORK
First of all, let us concentrate on the nature of work a system can
do. We will consider only pressure-volume work.
For understanding pressure-volume work, let us consider a
cylinder which contains one mole of an ideal gas fitted with a
frictionless piston. Total volume of the gas is Vi and pressure of
the gas inside is p. If external pressure is pex which is greater than
p, piston is moved inward till the pressure inside becomes equal
to pex. Let this change be achieved in a single step and the final
volume be Vf. During this compression, suppose piston moves a
distance, l and is cross-sectional area of the piston is A.
then, volume change A V Vf Vi
force
We also know, pressure
area Work done on an ideal gas in a cylinder when it is compressed
Therefore, force on the piston = pex . A by a constant external pressure
If w is the work done on the system by movement of the piston The negative sign of this expression is required to obtain
then conventional sign for w, which will be positive. It indicates that in
case of compression work is done on the system. Here (Vf – Vi)
w = force × distance pex .A. will be negative and negative multiplied by negative will be
= pex . (– V) = – pex V = – pex (Vf – Vi) positive. Hence the sign obtained for the work will be positive.
If the pressure is not constant at every stage of compression, but
changes in number of finite steps, work done on the gas will be
summed over all the steps and will be equal to - p V
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Now, the pressure of the gas (pin which we can write as p now) can
be expressed in terms of its volume through gas equation. For n
mol of an ideal gas i.e., pV = nRT.
nRT
p
V
Therefore, at constant temperature (isothermal process),
Vf
dV V
w rev nRT nRT ln f
Vi
V Vi
P-V plot when pressure is not constant and changes in finite
steps Vf
If the pressure is not constant but changes during the process w rev 2.303nRT log
Vi
such that it is always infinitesimally greater than the pressure of
the gas, then, at each stage of compression, the volume decreases Work in Cyclic Process
by an infinitesimal amount, dV. In such a case we can calculate the
work done on the gas by the relation A cyclic process is one which comes back to its initial state. The
graph of a cyclic process is always a closed graph. For a cyclic
Vf
process, Unet = 0 and qnet = – wnet.
w p ex dV
Vi Isothermal Free Expansion of an Ideal Gas
Here, pex at each stage is equal to (Pin + dp) in case of compression. For isothermal (T = constant) expansion of an ideal gas into
In an expansion process under similar conditions, the external vacuum ; w = 0 since pex = 0. Also, Joule determined experimentally
pressure is always less than the pressure of the system i.e., pex = that q = 0; therefore, U = 0
(pin– dp). In general case we can write, pex = (pin + dp). Such
processes are called reversible processes. Equation, U = q + w can be expressed for isothermal irreversible
and reversible changes as follows:
1. For isothermal irreversible change
q = – w = pex (Vf –Vi )
2. For isothermal reversible change
Vf
q w nRT ln
Vi
Vf
2.303nRT log
Vi
3. For adiabatic change, q = 0, U = wad
P-V plot when pressure is not constant and changes in infinite
steps 8.1 Work Done in Various Types of Thermodynamic Processes
Vf Vf 8.1.1 Isothermal Process
w p ex dV p in dp dV
These processes are the ones in which the temperature is constant
Vi Vi
throughout the process.
Since dp × dV is very small we can write U = 0; H = 0
Vf
w pin dV V P1
w 2.303nRT log 2 2.303nRT log
Vi
V1 P2
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8.1.2 Adiabatic Process 9.1.1 Molar Heat Capacity at Constant Pressure
These processes are the ones in which the heat exchanged with The molar heat capacity of a system at constant pressure (Cp) is
the surroundings is zero. Such processes are generally defined the amount of heat needed to raise the temperature of one mole
by the equations: gas by 1K. at constant pressure.
TV–1 = constant, TP1– = constant, PV = constant. qp
Cp
q=0 w = U nT
P V P V nRT 9.1.2 Molar Heat Capacity at Constant Volume
U nC V T 2 2 1 1
1 1 The molar heat capacity of a system at constant volume (CV) is
the amount of heat needed to raise the temperature of one mole
H = nCPT gas by 1K. at constant volume.
8.1.3 Isochoric Process
qv
Cv
These processes are the ones in which the volume remains nT
constant. Since the change in volume is zero therefore we can say
Heat Capacities of Different Types of Gases
that
Types of gas Cv Cp = Cp/Cv
w=0 Monoatomic 3R/2 5R/2 5/3 = 1.67
U = nCVT = qV Diatomic 5R/2 7R/2 7/5 = 1.4
8.1.4 Isobaric Process Non-linear Polyatomic 3R 4R 4/3 = 1.34
These are the processes in which the pressure remains constant 9.1.3 Relation between Cp and CV
(dp = 0) We know that : H = nCpT and U = nCVT
w = – PV = – nRT for 1 mole (n = 1) of an ideal gas
H = nCPT H = U + PV U + RT
NOTE Putting H = CpT and U = CVT
All these processes are happening on a system containing an CpT = CVT + RT
ideal gas therefore we can apply PV = nRT at any stage that we Cp = CV + R
find suitable.
9.2 Polytropic Process
9. HEAT CAPACITY OF A SYSTEM
It is a generalized form of any thermodynamic process which has
The heat capacity (C) of the system is the amount of heat needed
a form PVn = constant where n is a real number. For an isothermal
to raise the temperature of the system by 1K.
process n = 1 and for an adiabatic process n = . The heat capacity
q of a polytropic process can be calculated using the first law of
C thermodynamics and comes out to be :
T
9.1 Molar Heat Capacity R
C CV
The molar heat capacity of a system (CM) is the amount of heat n 1
needed to raise the temperature of one mole gas by 1K.
10. GRAPH TRANSFORMATION
q
CM
nT When a thermodynamic process is plotted in terms of two state
variable it can be transformed into a graph involving the other
state variable by doing the following
1. Identify the type of curve given, whether it is P-V, V-T or P-T
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graph. 11. ENTHALPY (H)
2. Then, Identify every step of the process According to the first law of thermodynamics
3. Then one by one convert every step into the required graph U q p pV at constant pressure, where qp is heat absorbed
bearing in mind critical points like, an expansion process will
by the system and pV represent expansion work done by the
remain an expansion process and so on.
system.
4. A cyclic process should remain cyclic whichever graph we Let us represent the initial state by subscript 1 and final state by
make. subscript 2. We can rewrite the equation as:
U2 – U1 = qp – p (V2 – V1)
On rearranging, we get
qp = (U2 + pV2) – (U1 + pV1)
Now we can define another thermodynamic function, the enthalpy
as: H = U + pV
so, equation becomes
P-V and P-T graphs of cyclic process
qp = H2 – H1 = H
NOTE
From the given P–V graph. Hence, H U pV
Process 12 is isothermal expansion; 23 adiabatic expansion; It is important to note that when heat is absorbed by the system
34 isothermal compression & 41 adiabatic compression. at constant pressure, we are actually measuring changes in the
enthalpy.
Graphical representation of various thermodynamic processes
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Remember H = qp, heat absorbed by the system at constant
pressure.
H is negative for exothermic reactions and H is positive for
endothermic reactions.
Let us consider a reaction involving gases. If VA is the total volume
of the gaseous reactants, VB is the total volume of the gaseous
products, nA is the number of moles of gaseous reactants and nB
is the number of moles of gaseous products, all at constant
pressure and temperature, then using the ideal gas law, we write,
pVA n A RT
and pVB n B RT
Thus, pVB – pVA = nBRT – nART = (nB –nA)RT
or p (VB – VA) = (nB – nA) RT Bomb calorimeter
or p V = ngRT
T Here, a steel vessel (the bomb) is immersed in a water bath to
ensure that no heat is lost to the surroundings. A combustible
Here, ng refers to the number of moles of gaseous products substance is burnt in pure dioxygen supplied in the steel bomb.
minus the number of moles of gaseous reactants. Heat evolved during the reaction is transferred to the water around
the bomb and its temperature is monitored. Since the bomb
This gives the relation, H = U n g RT calorimeter is sealed, its volume does not change. Under these
conditions, no work is done as the reaction is carried out at
12. CALORIMETRY: MEASUREMENT OF U AND H constant volume in the bomb calorimeter. Temperature change of
the calorimeter produced by the completed reaction is then
We can measure energy changes associated with chemical or converted to q V, by using the known heat capacity of the
physical processes by an experimental technique called calorimetry. calorimeter.
In calorimetry, the process is carried out in a vessel called
calorimeter, which is immersed in a known volume of a liquid. 12.2 H Measurements
Knowing the heat capacity of the liquid in which calorimeter is Measurement of heat change at constant pressure (generally
immersed and the heat capacity of calorimeter, it is possible to under atmospheric pressure) can be done in a calorimeter shown
determine the heat evolved in the process by measuring in the figure below.
temperature changes. Measurements are made under two different
conditions:
i) at constant volume, qV
ii) at constant pressure, qp
12.1 U Measurements
For chemical reactions, heat absorbed at constant volume, is
measured in a bomb calorimeter.
Coffee cup calorimeter
We know that H = q p (at constant p) and, therefore, heat
absorbed or evolved, qp at constant pressure is also called the
heat of reaction or enthalpy of reaction, H .
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In an exothermic reaction, heat is evolved, and system loses heat With partition we can pick the molecules of gas with surety that it
to the surroundings. Therefore, qp will be negative and H will is from gas A or gas B. But, if we were to pick up molecules from
also be negative. Similarly in an endothermic reaction, heat is container when partition is removed, we are not sure whether the
absorbed, qp is positive and H will be positive. molecules picked are of gas A or gas B. We say that the system
has become less predictable or more chaotic.
13. NEED FOR SECOND LAW At this point, we introduce another thermodynamic function,
entropy denoted as S. The above mentioned disorder is the
13.1 Spontaneous Process
manifestation of entropy. S is independent of path. For a given
A spontaneous process is one which happens on its own. Example, substance, the crystalline solid state is the state of lowest entropy
heat always flows spontaneously from higher temperature to lower (most ordered), The gaseous state is state of highest entropy.
temperature.
Whenever heat is added to the system, it increases molecular
The first law talks about the conservation of energy in a process motions causing increased randomness in the system. Thus heat
but does not speak of the feasibility of a process. It does not tell (q) has randomising influence on the system. Therefore S is
whether a process will happen on its own i.e. whether the process related with q and T for a reversible reaction as :
is spontaneous or not.
qrev
According to first law any process where energy remains S
T
conserved is feasible, but this is not true for all processes. Hence,
The total entropy change (Stotal) for the system and surroundings
we need some other basis for feasibility of a process.
of a spontaneous process is given by
13.2 Entropy and Spontaneity
Stotal = Ssystem + Ssurr > 0
Let us consider diffusion of two gases into each other in a closed
When a system is in equilibrium, the entropy is maximum, and the
container which is isolated from the surroundings as shown in
change in entropy, S = 0.
fig. (a) and (b).
We can say that entropy for a spontaneous process increases till
The two gases, say, gas A and gas B are represented by blue dots
it reaches maximum and at equilibrium the change in entropy is
and pink dots respectively and separated by a movable partition
zero. Since entropy is a state property, we can calculate the change
fig. (a) When the partition is withdrawn the gases begin to diffuse
in entropy of a reversible process by.
into each other and after a period of time, diffusion will be complete
fig (b). q sys,rev
S
T
We find that both for reversible and irreversible expansion for an
ideal gas, under isothermal conditions, U = 0, but Stotal i.e.,
Ssys + Ssurr is not zero for irreversible process. Thus, U does
not discriminate between reversible and irreversible process,
whereas S does.
13.3 Entropy change in Thermodynamic Processes
The entropy changes in a thermodynamic process can be
mathematically calculated by the equation:
T V2
S nCV n 2 nRn
T1 V1
This expression can be simplified for the four processes studied
earlier as :
V2
Diffusion of two gases For Isothermal Process: S nRn V
1
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T2 constant i.e. STotal = 0
For Isochoric Process: S nCV n T
1
15. GIBBS FREE ENERGY AND SPONTANEITY
T2
For Isobaric Process: S nCP n T We have seen that for a system, it is the total entropy change,
1 Stotal which decides the spontaneity of the process. It is clear
from the discussion in previous sections that neither decrease in
For Adiabatic Process: S 0 q rev 0
enthalpy nor increase in entropy alone can determine the direction
of spontaneous change.
13.4 Entropy Change During Phase Transition
For this purpose, we define a new thermodynamic function the
Entropy of Fusion Gibbs energy or Gibbs function, G, as
G = H – TS
H fusion
Sfusion Sliquid Ssolid Gibbs function, G is an extensive property and a state function.
Tf
The change in Gibbs energy for the system, Gsys can be written
Entropy of Vapourisation as
H vapour G sys H sys TSsys Ssys T
Svapour Svapour Sliquid
Tbp
At constant temperature, T = 0
Entropy of Sublimation
G sys H sys T Ssys
H sub
Ssub Svapour Ssolid
Tsub Usually the subscript ‘system’ is dropped and we simply write
this equation as
Important points to Remember:
1. Entropy of a system remains constant in a reversible adiabatic G H T S
process. Therefore, it is also known as isoentropic process. This equation is known as the Gibbs equation, one of the most
2. Entropy of an ideal gas will always increase in isothermal important equations in chemistry. Here, we have considered both
expansion. terms together for spontaneity: energy (in terms of H) and
entropy (S, a measure of disorder) as indicated earlier.
3. In a reversible adiabatic process the entropy of both system Dimensionally if we analyse, we find that G has units of energy
and surroundings remains the same and there is no overall because, both H and the TS are energy terms, since TS = (K)
change in entropy as well. (J/K) = J.
SSystem = SSurroundings = STotal = 0 Now let us consider how G is related to reaction spontaneity.
4. In a reversible isothermal expansion the entropy of We know,
surroundings will always decrease to balance the increase in
system’s entropy to make the overall entropy constant. Stotal Ssys Ssurr
5. In free expansion the entropy of the system always increases If the system is in thermal equilibrium with the surrounding, then
and that of surrounding remains constant. Free expansion is the temperature of the surrounding is same as that of the system.
both isothermal and adiabatic and is irreversible. Also, increase in enthalpy of the surrounding is equal to decrease
in the enthalpy of the system.
14. SECOND LAW OF THEROMODYNAMICS
Therefore, entropy change of surroundings,
“The entropy of an isolated system/Universe tends to increase.”
or H surr H sys
“In a spontaneous process the entropy of the universe increases.” Ssurr
T T
STotal SSystem SSurrounding 0
(for a sponataneous change)
Thus, in a reversible process the entropy of the Universe remains
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temperature is lowered, the entropy decreases.
H sys
Stotal Ssys The absolute entropy of a perfectly crystalline substance at
T
absolute zero temperature is zero.
Rearranging the above equation: This is called third law of thermodynamics. This is so because
there is perfect order in a crystal at absolute zero. The statement
TStotal TSsys H sys
is confined to pure crystalline solids because theoretical
For spontaneous process, Stotal > 0 , so arguments and practical evidences have shown that entropy of
solutions and super cooled liquids is not zero at 0 K. The
TSsys H sys 0 importance of the third law lies in the fact that it permits the
calculation of absolute values of entropy of pure substance from
H sys TSsys 0 thermal data alone.
Using equation , the above equation can be written as q rev
For a pure substance, this can be done by summing
T
–G > 0
increments from 0 K to 298 K.
GH – TS < 0
Hsys is the enthalpy change of a reaction, TSsys is the energy 17. THERMOCHEMICAL EQUATIONS
which is not available to do useful work. So G is the net energy A chemical equation which gives us all the information like energy
available to do useful work and is thus a measure of the ‘free changes associated with a chemical reaction and phases of various
energy’. For this reason, it is also known as the free energy of the reactants and products is called thermochemical equation.
reaction.
For a chemical reaction, HReaction = HProducts – HReactants
G gives a criteria for spontaneity at constant pressure and
temperature. The change in enthalpy during a chemical reaction occurs due to
breaking and making of bonds.
(i) If G is negative (< 0), the process is spontaneous.
Also, H = U + ngRT.
(ii) If G is positive (> 0), the process is non spontaneous.
All reactions can be categorized into one of the following two
Effect of Temperature on Spontaneity categories :
fHº fSº fGº Description 17.1 Endothermic Reactions
– + – Spontaneous at all temperatures These are chemical reactions which absorb energy.
+ – + Nonspontaneous at all tempertures
(H = positive)
– – + (at high T) Nonspontaneous at high temeprature
– – – (at low T) Spontaneous at low temperature
+ + + (at low T) Non-spontaneous at low temperature
+ + – (at high T) Spontaneous at high temperature
16. THIRD LAW OF THERMODYNAMICS
Molecules of a substance may move in a straight line in any
direction, they may spin like a top and the bonds in the molecules
may stretch and compress. These motions of the molecule are Fig. 10.17: Enthalpy diagram for endothermic reactions
called translational, rotational and vibrational motion respectively. CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (g)
When temperature of the system rises, these motions become
more vigarous and entropy increases. On the other hand when H = – 890 kJ/mol
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17.2 Exothermic Reactions gaseous state at a constant temperature and standard pressure
(1 bar).
These are chemical reactions which release energy.
For example: Solid CO2 or ‘dry ice’ sublimes at 195 K
H = negative)
CO 2 s CO 2 g ; sub H 25.2kJmol –1
Naphthalene sublimes slowly and for this sub H 73.0kJmol 1
18. ENTHALPIES OF REACTIONS
Enthalpy change can be calculated for all reactions and is
sometimes called the Heat of Reaction. Let’s take a look at various
types of reactions and enthalpy changes associated with them :
Enthalpy diagram for exothermic reaction H oRe action H oPr oduct H oReactants
18.1 Enthalpy of Formation
17.3 Enthalpy Change During Phase Transformation
It is the heat absorbed or released when one mole of a compound
17.3.1 Enthalpy of fusion (Symbol fusHº)
is formed from its constituent elements under their standard
The heat change (or enthalpy change) that is accompanied when elemental forms. The enthalpy for formation of the following
one mole of a solid substance undergoes melting in standard substances is taken to be zero under 1 bar pressure and 298 K.
state is called standard enthalpy of fusion or molar enthalpy of
Hfo (O2, g) = 0; Hfo (S, Rhombic) = 0
fusion, fus H Hfo (C, graphite) = 0; Hfo (P, white) = 0
For example, ice requires heat for melting. Normally this melting Hfo (Br2, l) = 0; Hfo (H2, g) = 0
takes place at constant pressure, i.e., atmospheric pressure and
during the phase transition, temperature remains constant (273K). 18.2 Enthalpy of Combustion
It is the heat released when one mole of a substance undergoes
H 2 O s H 2 O l ; fus H 6.00kJmol1 combustion in presence of oxygen.
If process is reversed, an equal amount of heat is given off to the CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (g) H = – 890 kJ/mol
surroundings. 18.3 Enthalpy of Neutralization
17.3.2 Enthalpy of vaporization (Symbol vapHº) It is the heat released or absorbed when one equivalent of an acid
undergoes neutralisation with one equivalent of a base. e.g.
The enthalpy change (or heat change) when one mole of liquid at
H+ (aq) + OH– (aq) H2O (l ) H = – 57.3 kJ/mol
constant temperature and under pressure (1 bar) undergoes
vaporization is called standard enthalpy of vaporization or molar 18.4 Enthalpy of Solution
enthalpy of vaporization, vap H . It is the heat released or absorbed when 1 mole of a compound is
dissolved in excess of a solvent (water).
For example, water requires heat for evaporation, at constant
MgSO4 (s) + H2O (excess) Mg2+ (aq) + SO42– (aq)
temperature of its boiling point Tb and at constant pressure
HoSol = – 91.211 kJ/mol
H 2 O l H 2 O g ; vap H 40.79kJmol
1
18.5 Enthalpy of Hydration
17.3.3 Enthalpy of sublimation (Symbol subHº) It is the energy released or absorbed when 1 mole of anhydrous
or partially hydrated salt undergoes hydration by the addition of
Sublimation is the process when a solid changes directly into water of crystallisation. e.g.
gaseous state without changing into liquid state. The change in CuSO4(s) + 5H2O(l) CuSO4. 5H2O(s) Hhyd = –78.9 kJ/mol
state occurs at a temperature below its melting point. In this case
the enthalpy of sublimation is defined as the change in enthalpy
when one mole of a solid substance is directly converted into the
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18.6 Lattice Enthalpy
The lattice enthalpy of an ionic compound is the enthalpy change
which occurs when one mole of an ionic compound dissociates
into its ions in gaseous state. It is denoted by lattice H Resonating structures of benzene
For example: The difference of 151 kJ gives the resonance energy of benzene.
NaCl s Na
g Cl g ;
lattice H 788kJ mol 1
19. HESS LAW
Relationship of solH,latticeH and hydH “If a reaction takes place in several steps then its standard reaction
sol H lattice H hyd H enthalpy is the sum of the standard enthalpies of the intermediate
reactions into which the overall reaction may be divided at the
18.7 Bond Dissociation Enthalpy same temperature”. This is called the Hess law of constant heat
summation
The energy needed to break the bonds of one mole molecules is
called the bond dissociation Enthalpy of the substance. It is defined
per mol of molecule.
e.g. Bond dissociation enthalpy of H2 is 436 kJ/mol
H 2 (g) 2H(g) H 436 kJ / mole
18.8 Heat of Atomization
It is defined as the energy required to convert any substance to
gaseous atoms. This is defined per mol of the gaseous atoms. For Representation of Hess law
example heat of atomisation of H will be 218 kJ/mol atoms. 19.1 Born Haber Cycle
The entire thermodynamics process of formation of an ionic crystal
H 2 (g) 2H(g) H 436 kJ / mole lattice is called Born Haber cycle. An ionic compound is formed
from its constituents through a series of steps involving
For diatomic molecules bond dissociation energy and heat of conversion of atoms/molecules into gaseous phase for ion
atomization are same. formation, ionisation and electron gain to form ions and then the
reaction of gaseous ions to form solid lattice
18.9 Resonance Energy
Generally there is a good agreement between the enthalpies of
formation as calculated from bond energies and those determined
experimentally. However, if a compound exhibits resonance, there
is a considerable difference between the two values. This difference
gives a measure of the resonance energy of the compound. As an
example, we may consider the dissociation of benzene:
C 6 H 6 (g) 6C(g) 6H(g)
Assuming that benzene ring consists of three single and three
double bonds (Kekule’s structure), the calcualted dissociation
energy comes out to be 5384.1 kJ as illustrated below:
H g 3( H C C ) 3( H C C ) 6( H C H )
3 347.3 3 615.0 6 416.2 5384.1 kJ mol1
The experimental value is known to be 5535.1 kJ mol-1. Evidently,
the actual energy required for the dissociation of benzene is 151
kJ more than the calcualted value. This clearly show that the
acutal structure of benzene is more stable than the Kekule structure
by 151 kJ. The actual structure of benzene is known to be the
resonance hybrid of the two Kekule structures.
Born Haber Cycle of NaCl
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20. KIRCHHOFF EQUATION 21. GIBBS ENERGY CHANGE AND EQUILIBRIUM
The enthalpy of any process, whether physical or chemical, varies Gibbs energy for a reaction in which all reactants and products
with temperature. The influence of temperature can be worked are in standard state, r G is related to the equilibrium constant
out as follows: of the reaction as follows:
H reaction H products H reactants 0 r G RT ln K
Differentiating with respect to temperature, keeping pressure Or r G RT ln K
constant, we have
Or r G 2.303RT log K
dH dH product dH reactant
C P product CP reactant We also know that
dT P dT P dT P
r G r H T r S RT ln K
If C P = Sum of heat capacities of products – Sum of heat
For strongly endothermic reactions, K is smaller while for
capacities of reactants, then
exothermic reactions, K is much larger than 1.
d H CP dT
This equation is called the Kirchhoff equation. It states that the
variation of H of a reaction as temperature at constant pressure
is equal to C P of the system.
The temperature-dependence of enthalpy of reaction at constant
volume is given by
d U CV dT
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SUMMARY
System: A part of universe which is under investigation. Enthalpy (H): It is sum of internal energy and pressure-
volume energy of the system at a particular temperature and
Surroundings: The rest of the universe which is not a part
pressure. It is also called heat content (H = U + PV).
of the system.
Enthalpy change ( ΔH ): It is the measure of heat change
State of the system: The conditions of existence of a system
when its macroscopic properties have definite values. taking place during the process at constant temperature and
constant pressure.
State functions: The thermodynamic quantities which
depend only on the initial and final state of the system. q p H
Energy is exchanged between the system and the Enthalpy H and internal energy change (U) are related as
surroundings as heat if they are at different temperatures.
H U PV
The properties of the system whose value is independent
of the amount of substance are called intensive properties, H U n g RT
e.g., temperature, pressure, viscosity, surface tension,
dielectric, specific heat capacity.
Where n g Gaseous moles of products – Gaseous moles
The properties of the system whose value depends upon of reactants
the amount of substance present in the system are called
extensive properties. e.g., mass, volume, surface area,
energy, enthalpy, entropy, free energy, heat capacity.
Θ
Enthalpy of reaction Δr H : The enthalpy change
accompanying a chemical reaction when the number of moles
Work is also a mode of transference of energy between
of reactants react to give the products as given by the
system and the surroundings. Work done by the system on
balanced chemical equation.
the surroundings is given by PV.
Internal energy (U): The energy associated with the system
Θ
Standard enthalpy of formation Δf H : The enthalpy
at a particular conditions of temperature and pressure. change accompanying the formation of one mole of the
Internal energy change ( ΔU ): It is a measure of heat change compound from its element at standard conditions and all
occurring during the process at constant temperature and the substances being in their standard states.
constant volume.
As a convention, the f H of every element is assumed to
q v U be zero.
First law of thermodynamics: It states that the energy of
the universe always remains constant during chemical and
Θ
Enthalpy of combustion Δc H : The amount of heat
physical changes. Mathematically. change when 1 mole of the substance is completely burnt in
U q w excess of oxygen or air. c H is always negative.
Internal energy of an ideal gas depends only on temperature.
Therefore, in an isothermal process involving ideal gas,
Θ
Enthalpy of solution Δsol H : The enthalpy change when
U 0 . one mole of a substance is dissolved in large excess of
solvent so that further dilution does not give any further
Work of expansion, w –PV . enthalpy change.
Work of expansion in vacuum. Enthalpy of hydration: It is the enthalpy change during the
hydration of 1 mole of anhydrous salt to a specific hydrate.
pext 0, w 0
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Hess law: The enthalpy change in a particular reaction is the Gibbs energy: Gibbs energy is the energy in a system that
same whether the reaction takes place in one step or in a can be converted into useful work
number of steps. G w useful
Bond enthalpy: The average amount of energy required to G H T S
break one mole of the bonds of a particular type in gaseous
For a spontaneous process G 0
molecules.
For a non - spontaneous process G 0
q rev For a process at equilibrium G 0
Entropy: S
T Relation of Gibbs energy and equilibrium constant:
r G 2.3 03R T log K
r Sº Sº (products) – Sº (reactants)
i.e., Stotal Ssys Ssurr must be positive
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EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS
Introduction of Thermodynamics 9. What is the change in internal energy when a gas contracts
from 377 mL to 177 mL under a constant pressure of 1520
1. Which of the following is not a state function ?
torr, while at the same time being cooled by removing 124
(a) Heat (b) Internal energy J heat?
(c) Enthalpy (d) Entropy (a) 40.52 J (b) –83.48 J
2. Which of the following quantities is not a state function ? (c) –248 J (d) None of these
(a) Temperature (b) Entropy 10. A given mass of gas expands from the state A to the state
(c) Enthalpy (d) Work B by three paths 1, 2 and 3 as shown in the figure. If w1, w2
and w3 respectively be the magnitudes work done by the
3. Which of the following is not an intensive property ?
gas along three paths then :
(a) Entropy (b) Pressure
(c) Temperature (d) Molar volume
4. Which of the following is a state function and also an
extensive property?
(a) Internal energy (b) Pressure
(c) Molar heat capacity (d) Temperature
(a) w1 > w2 > w3 (b) w1 < w2 < w3
5. Warming ammonium chloride with sodium hydroxide in a
(c) w1 = w2 = w3 (d) w2 < w3 < w1
test tube is an example of :
11. An ideal gas is taken around the cycle ABCA as shown in
(a) Closed system (b) Isolated system
P-V diagram
(c) Open system (d) None of these
The net work done by the gas during the cycle is equal to :
6. A tightly closed thermoflask contains some ice cubes. This
constitutes
(a) closed system (b) open system
(c) isolated system
(d) Non-thermodynamic system
Internal Energy, Concept of Heat and Work
7. A sample of gas changes from P1, V1 and T1 to P2, V2 and T2
(a) 12 P1V1 (b) 6P1V1
by one path and then back to P1, V1 and T1, U for the
process is : (c) 5P1V1 (d) P1V1
(a) Infinite (b) > 0 12. An ideal gas is taken through the cycle A B C A
as shown in fig. If the net heat supplied to the gas in cycle
(c) < 0 (d) equal to 0
is 5 J, the work done by the gas in the process C A.
8. Which of the following changes would definitely increase
the internal energy of a system?
(a) The system gains heat and performs work.
(b) The system gains heat and has work performed on it.
(c) The system loses heat and performs work.
(d) The system loses heat and has work performed on it.
(a) –5 J (b) –10 J
(c) –15 J (d) –20 J
THERMODYNAMICS AND THERMOCHEMISTRY 200
13. In a system where E = –51.0 kJ, a piston expanded against 20. A heat engine carries one mole of an ideal mono-atomic
a pext of 1.2 atm giving a change in volume of 32.0 L. What gas around the cycle as shown in figure, the amount of
was the change in heat of this system? heat added in the process AB and heat removed in the
(a) –36 kJ (b) –13 kJ process CA are:
(c) –47 kJ (d) 24 kJ
First Law of Thermodynamics
14. A system absorb 10 kJ of heat at constant volume and its
temperature rises from 27°C to 37°C. The value of U is
(a) 100 kJ (b) 10 kJ
(c) 0 (d) 1 kJ
15. As per the First Law of thermodynamics, which of the (a) qAB = 450 R and qCA = –450 R
following statement would be appropriate : (b) qAB = 450 R and qCA = –225 R
(a) Energy of the system remains constant (c) qAB = 450 R and qCA = –375 R
(b) Energy of the surroundings remains constant (d) qAB = 375 R and qCA = –450 R
(c) Entropy of the universe remains constant 21. An ideal gas receives 10 J of heat in a reversible isothermal
(d) Energy of the universe remains constant expansion. Then the magnitude of work done by the gas :
16. A sample of liquid in a thermally insulated container (a (a) would be more than 10 J
calorimeter) is stirred for 2 hr. by a mechanical linkage to a (b) 10 J
motor in the surrounding, for this process;
(c) would be less than 10 J
(a) w < 0; q = 0; U = 0 (b) w > 0; q > 0; U > 0
(d) cannot be determined
(c) w < 0; q > 0; U = 0 (d) w > 0; q = 0; U > 0
22. The maximum work obtained by an isothermal reversible
17. For a particular process q = –10 kJ and w=25 kJ. Which of expansion of 1 mole of an ideal gas at 27°C from 2.24 to
the following statements is true? 22.4 L is (R = 2 cal)
(a) Heat flows from the surroundings to the system. (a) – 1381.8 cal (b) – 600 cal
(b) The system does work on the surroundings. (c) –138.18 cal (d) – 690.9 cal
(c) E= –35 kJ 23.
o
2 mole of an ideal gas at 27 C expands isothermally and
(d) None of the above is true reversibly from a volume of 4 litres to 40 litre. The work
done (in kJ) is:
Reversible and Irreversible Work
(a) w = –28.72 kJ (b) w = –11.488 kJ
18. In an isothermal expansion of an ideal gas
(c) w = –5.736 kJ (d) w = –4.988 kJ
(a) q = 0 (b) V = 0
24. 5 mole of an ideal gas expand isothermally and irreversibly
(c) U = 0 (d) w = 0
from a pressure of 10 atm to 1 atm against a constant
19. Two moles of Helium gas undergo a reversible cyclic external pressure of 1 atm. wirr at 300 K is:
process as shown in figure. Assuming gas to be ideal.
(a) –15.921kJ (b) –11.224 kJ
What is the work for the process C to D ?
(c) –110.83 kJ (d) None of these
25. 10 mole of ideal gas expand isothermally and reversibly
from a pressure of 10 atm to 1 atm at 300 K. What is the
largest mass which can lifted through a height of 100 meter?
(a) 31842 kg (b) 58.55 kg
(c) 342.58 kg (d) None of these
(a) –800 Rn2 (b) zero
(c) +200 Rn2 (d) –600 Rn2
THERMODYNAMICS AND THERMOCHEMISTRY 201
26. Which of the following statement is true? 33. During the adiabatic expansion of an ideal gas against
(a) A thermodynamic process is defined by initial and atmospheric pressure, the internal energy will
final states. (a) Increase (b) decrease
(b) E=0 for a reversible phase change at constant T and (c) stay the same (d) Impossible to say
P. 34. One mole of an ideal gas expands reversibly and
(c) q must be zero for an isothermal process. adiabatically from a temperature of 27oC. If the work done
(d) A reversible adiabatic process is also isoentropic. during the process is 3 kJ, then final temperature of the
gas is:(CV = 20 J/K )
27. In the thermodynamic sense of the word, an irreversible
process (a) 100 K (b) 150 K
(a) does the same work (but of opposite sign) as a (c) 195 K (d) 255 K
reversible process Enthalpy of a System
(b) violates the 1st law of thermodynamics, unlike a 35. For a chemical reaction at constant P and V, H is equal to
reversible process
(a) U (b) zero
(c) involves non-ideal gases (as opposed to ideal gases
(c) U + PV (d) p/T
in a reversible process)
36. For an endothermic reaction, S is positive. The reaction
(d) exchanges the same amount of heat (but of opposite
is :
sign) as a reversible process.
(a) feasible when TS > H
Heat Capacity of a System, Adiabatic Process and
(b) feasible when H > TS
Poisson’s Ratio
(c) feasible at all temperatures
28. Molar heat capacity of water in equilibrium with ice at
constant pressure is (d) not feasible at all
(a) zero (b) 37. Which of the following conditions is not favourable for
the feasibility of a process ?
(c) 40.45 kJ K–1 mol–1 (d) 75.48 J K–1 mol–1
(a) H = –ve, TS = –ve and TS < H
29. Ice–Water mass ratio is maintained as 1 : 1 in a given
system containing water in equilibrium with ice at constant (b) H = +ve, TS = +ve and TS > H
–1 –1
pressure. If CP (ice) = CP (water) = 4.18 J mol K molar (c) H = –ve, TS = +ve and H > TS
heat capacity of such a system is (d) H = +ve, TS = +ve and H > TS
(a) Zero (b) Infinity 38. In which of the following cases, the reaction is
–1 –1 –1 –1
(c) 4.182 JK mol (d) 75.48 JK mol spontaneous at all temperatures ?
30. In an adiabatic expansion of an ideal gas (a) H > 0, S > 0 (b) H < 0, S > 0
(a) T = 0 (b) w = 0 (c) H < 0, S < 0 (d) H > 0, S < 0
(c) q = 0 (d) U = 0 39. Which of the following is true for the reaction ?
31. The temperature of the system decreases in an H2O(g) at 100°C and 1 atm pressure
H2O()
(a) Isothermal compression (b) Isothermal expansion
(a) S = 0 (b) H = TS
(c) Adiabatic compression (d) Adiabtic expansion
(c) H = U (d) H = 0
32. 1 mole of NH3 gas at 27°C is expanded in reversible adiabatic
condition to make volume 8 times ( = 1.33). Final 40. For the reaction :
temperature and work done by the gas respectively are : C s O2 g
CO 2 g
(a) 151 K, –900 cal (b) 151 K, –400 cal (a) H < U (b) H > U
(c) 250 K, 1000 cal (d) 200 K, –800 cal (c) H = U (d) H = 0
THERMODYNAMICS AND THERMOCHEMISTRY 202
41. For which of the following reactions, H is greater than (c) H is +ve, S is –ve
U ?
(a) N2(g) + 3H2(g) 2NH3(g) (d) Both H and S are –ve.
(b) CH4(g) + 2O2(g) CO2(g) + 2H2O(l) Second Law of Thermodynamics
(c) PCl5(g)
PCl3(g) + Cl2(g) 50. The statement “A heat engine always loses some of its
heat energy to the surroundings.” is an example of which
(d) HCl(aq) + NaOH(aq)
NaCl(aq) + H2O(aq)
of the following laws?
42. For the reaction,
(a) The Law of Corresponding States
PCl5 g
PCl3 g Cl 2 g
(b) The Zeroth Law of Thermodynamics
(a) H = U (b) H > U
(c) H < U (d) None of these (c) The First Law of Thermodynamics
43. (U – H) for the following equation is N2 + 3H2 2NH3. (d) The Second Law of Thermodynamics
(a) RT (b) 2 RT
51. The entropy of the universe
1
(c) -2 RT (d) RT T (a) tends towards a maximum
2
44. The difference between heats of reaction at constant (b) tends towards a minimum
pressure and constant volume for the reaction.
(c) tends to be zero
2C2H6(l) + 15O2(g)
12CO2(g) + 6H2O(l) at 25°C is
(d) remains constant
(a) –7.43 kJ (b) +3.72 kJ
(c) –3.72 kJ (d) 7.43 kJ 52. Heat cannot by self flow from a body at lower temperature
45. For the reaction : to a body at higher temperature a statement of
consequence of:
C 2 H 4 g 3O 2 g
2CO 2 g 2H 2 O
at 298 K, U = – 1415 kJ. (a) 1st law of thermodynamics
–1
If R = 0.0084 kJ K , then H is equal to (b) 2nd law of thermodynamics
(a) –1400 kJ (b) –1410 kJ
(c) conservation of momentum
(c) –1420 kJ (d) –1430 kJ
46. The difference between H and E on a molar basis for (d) conservation of mass
the combustion of methane gas at 300K (kelvin) would be : 53. When steam condenses to water at 90oC, the entropy of
(a) zero (b) –RT the system decreases. What must be true if the second
(c) –2RT (d) –3RT law of thermodynamics is to be satisfied?
47. Consider the reaction at 300 K (a) Entropy of the universe also decreases.
H2(g) + Cl2 (g)
2HCl(g); Hº = –185 kJ (b) Entropy of the surroundings also decreases.
If 2 mole of H2 completely react with 2 mole of Cl2 to form (c) Entropy of the surroundings increases to same extent
HCl. What is U° for this reaction ?
to which entropy of the system decreases.
(a) 0 (b) –185 kJ
(c) 370 kJ (d) –370 kJ (d) Increase in entropy in the surroundings is greater than
decrease in entropy of the system.
48. In an endothermic reaction
(a) H is negative
Entropy and Spontaneity
(b) Heat is given to the surroundings 54. Which of the following has highest entropy ?
(c) Enthalpy of the reactants is less than that of the (a) Mercury (b) Hydrogen
products (c) Water (d) Graphite
(d) E is negative 55. For a reversible process at equilibrium, the change in
entropy may be expressed as :
49 For the process : CO2(s)
CO2(g)
q rev
(a) Both H and S are +ve (a) S = Tqrev (b) S
T
(b) H is –ve, S is +ve H
(c) S (d) S = G
T
THERMODYNAMICS AND THERMOCHEMISTRY 203
56. Entropy is a measure of 5
64. When two mole of an ideal gas Cp,m. R heated from
(a) disorder 2
300 K to 600 K constant pressure. The change in entropy
(b) internal energy of gas (S) is :
(c) efficiency 3 3
(a) R n 2 (b) R n 2
(d) useful work done by the system 2 2
5
57. When a solid is converted directly into gaseous state, the (c) 5 R n 2 (d) R n 2
process is called sublimation. The entropy change during 2
the process is : 65. In the above question calculate Sgas if process is carried
out at constant volume :
(a) zero (b) negative
3
(c) positive (d) may be negative or zero (a) 5 R n 2 (b) R n 2
2
58. The enthalpy of vaporisation of a substance is (c) 3 R n 2 (d) – 3 R n 2
–1
8400 J mol and its boiling point is –173ºC. The entropy 66. The entropy change when two moles of ideal monoatomic
change for vaporisation is : gas is heated from 200°C to 300°C reversibly and
(a) 84 J mol K
–1 –1
(b) 21 J mol K
–1 –1 isochorically ?
3 300 5 573
R n R n
–1 –1 –1 –1
(c) 49 J mol K (d) 12 J mol K (a) (b)
2 200 2 273
59. The enthalpy of vaporisation of a compound AB at its
573 3 573
(c) 3R n (d) R n
–1
boiling point (127°C) is 6.4 kJ mol . Its entropy of
vaporisation is : 473 2 473
–1 –1
If one mole of an ideal gas Cp.m. R is expanded
(a) 2.56 kJ mol (b) 16 J mol 5
67.
–3
(c) 16 × 10 J mol
–1 3
(d) 1.6 × 10 kJ mol
–1
2
60. The entropy change for the conversion of 1 mol of –tin isothermally at 300 K until it’s volume is tripled, then
(at 13°C, 1 atm) to 1 mol of –tin (13°C, 1 atm), if enthalpy change in entropy of gas is :
–1
of transition is 2.095 kJ mol is : (a) zero (b) infinity
5
(c) R n 3
–1 –1 –1 –1
(a) 7.32 J mol K (b) 14.62 J K mol (d) R n 3
–1 –1
2
(c) 56.3 J mol K (d) 0
68. When one mole of an ideal gas is compressed to half of its
61. The following data is known about the melting of a initial volume and simultaneously heated to twice its initial
–1 –1 –1
compound AB. H = 9.2 kJ mol . S = 0.008 kJ K mol . Its temperature, the change in entropy of gas (S) is :
melting point is :
(a) Cp,m ln2 (b) Cv,m ln2
(a) 736 K (b) 1050 K
(c) R ln2 (d) (Cv,m –R) ln2
(c) 1150 K (d) 1150°C
69. Two mole of a monoatomic ideal gas is expanded
62. When potassium chloride is dissolved in water irreversibly and isothermally at T Kelvin until its volume
(a) Entropy increases is doubled and q joules of heat is absorbed from
surrounding. Stotal (J/K) (system + surrounding) is :
(b) Entropy decreases
(a) zero (b) 2 Rln2–q/T
(c) Entropy increases and then decreases
(c) 3Rln2–q/T (d) –2 Rln2 + q/T
(d) Free energy increases
70. One mole of an ideal diatomic gas (Cv = 5 cal) was
63. Which of the following processes is not accompanied by
transformed from initial 25°C and 1 L to the state when
increase of entropy ?
temperature is 100°C and volume 10 L. The entropy change
(a) dissolution of NH4Cl in water of the process can be expressed as (R = 2 calories/mol/K)
(b) burning of rocket fuel 298 373
(a) 3n 2 n10 (b) 5n 2 n10
(c) sublimation of dry ice 373 298
(d) condensing steam 373 1 373 1
(c) 7n 2 n (d) 5n 2 n
298 10 298 10
THERMODYNAMICS AND THERMOCHEMISTRY 204
71. A reaction has H = – 33 kJ and S = +58 J/K. This reaction (a) should always be negative
would be : (b) should always be positive
(a) spontaneous below a certain temperature (c) will be equal to twice the energy of combination
(b) non-spontaneous at all temperature (d) may be positive or negative
(c) spontaneous above a certain temperature 78. Which of the following pairs has heat of neutralisation
(d) spontaneous at all temperature equal to –57.1 kJ ?
72. Calculate the entropy change (J/mol K) of the given (a) HNO3,KOH (b)HCl, NH4OH
reaction. The molar entropies [J/K–mol] are given in (c) H2SO4,NH4OH (d) CH3COOH,NaOH
brackets after each substance.
79. Which of the following neutralisation reactions is most
2 Pb S(s) [91.2] + 3O2(g)[205.1]
exothermic ?
(a) HCl and NaOH
2PbO(s) [66.5] + 2SO2(g)[248.2]
(b) HCN and NaOH
(a) –113.5 (b) –168.3
(c) HCl and NH4OH
(c) +72.5 (d) –149.2
(d) CH3COOH and NH4OH
o o
73. Given rS = –266 and listed [ Som values] calculate S for
80. The enthalpy change for the reaction,
Fe3O4(s) :
H 2 O s
H 2 O is called
4Fe3 O 4 (s)[.......] O 2 (g)[205] 6Fe 2 O3 (S)[87]
(a) Enthalpy of formation
(a) +111.1 (b)
(b) Enthalpy of fusion
(c) (d) 248.25
(c) Enthalpy of vaporisation
Gibb’s Energy, Enthalpy of reactions/processes
(d) Enthalpy of transition
74. For a reaction to be spontaneous at all temperatures
81. The enthalpies of formation of N2O and NO at 298 K are 82
(a) G and H should be negative –1
and 90 kJ mol . The enthalpy of the reaction :
(b) H = G = 0
N 2 O g ½O 2 g
2NO g
(c) G and H should be positive
(d) H < G (a) –8 kJ (b) 98 kJ
75. For isothermal expansion in case of an ideal gas : (c) –74 kJ (d) 8 kJ
(a) G = S (b) G = H 82. The enthalpies of solution of anhydrous CuSO4 and
–1
CuSO4.5H2O are –15.89 and 2.80 k cal mol respectively.
(c) G = – T.S (d) None of these
The enthalpy of hydration of CuSO4 to CuSO4.5H2O is :
76. For the reaction at 300 K
(a) –18.69 kcal (b) 13.09 kcal
A(g) + B(g)
C(g) (c) –13.09 kcal (d) 18.69 kcal
U = –3.0 kcal S = –10.0 cal/K 83. Calculate the heat required to make 6.4 Kg CaC2 from CaO(s)
–1
(R 2 cal mol K )
–1 and C(s) from the reaction :
G is : CaO(s) + 3 C(s)
CaC2(s) + CO(g) given that
(a) –600 cal (b) –3600 cal
f H º CaO = –151.6 kcal, f H º CaC2 = –14.2kcal.
(c) 2400 cal (d) 3000 cal
77. The enthalpies of elements in their standard states are f H º CO = –26.4 kcal.
taken as zero. Hence the enthalpy of formation of a (a) 5624 kcal
4
(b) 1.11 × 10 kcal
compound 3
(c) 86.24 × 10 (d) 1100 kcal
THERMODYNAMICS AND THERMOCHEMISTRY 205
84. Given : (a) –297.1 kJ (b) 493.7 kJ
H2(g) + ½O2(g) H2O(g) + q1 (c) –493.7 kJ (d) 297.1 kJ
–2
H2(g) + ½O2(g) H2O (l) + q2 90. The standard heat of formation at 101.3 kNm and 298 K is
The enthalpy of vaporisation of water is equal to arbitrarily taken to be zero for :
(a) q1 + q2 (b) q1 – q2 (a) gaseous bromine atoms
(c) q2 – q1 (d) q1q2 (b) gaseous bromine molecules
(c) liquid bromine
If CH3COOH + OH
CH COO– + H O + x kJ
–
85. 3 2
(d) solid bromine.
H + OH H O + y kJ
+ –
2
The enthalpy change for the reaction : 91. The enthalpy of formation of two compounds A and B are
–84 kJ and –156 kJ respectively. Which one of the following
CH COOH CH COO– + H+ is
3 3 statements is correct ?
(a) x + y (b) x – y
(a) A and B are endothermic compounds
(c) y – x (d) x – y/2
(b) A is more stable than B
86. Which of the following reactions represents enthalpy of
(c) A is less stable than B
formation of AgCl ?
(d) Both A and B are unstable
(a) Ag aq Cl aq
AgCl s
92. When 0.5 g of sulphur is burnt to SO2 4.6 kJ of heat is
1 liberated. What is the enthalpy of formation of sulphur
(b) AgCl s
Ag s Cl2 g
dioxide ?
2
(c) Ag s AuCl s
AgCl s Au s (a) –147.2 kJ (b) +147.2 kJ
(c) +294.4 kJ (d) –294.4 kJ
1
(d) Ag s Cl2 g
AgCl s . 93.
–1
The heat of formation of Fe2O3(s) is –824.2 kJ mol . H for
2
the reaction.
87. Which of the following equations represents standard heat
of formation of methane ? 2Fe 2 O3 s
4Fe s 3O2 g is :
(a) C (diamond) + 2H2(g)
CH4(g) (a) –412.1 kJ (b) –1648.4 kJ
(b) C (graphite) + 2H2(g)
CH4(g) (c) –3296.8 kJ (d) 1648.4 kJ
(c) C (diamond) + 4H(g) 94. The H for the reaction,
CH4(g)
(d) C (graphite) + 4H(g)
CH4(g) 4S(s) + 6O2 (g)
4 SO3(g)
88. For the reaction, is –1583.2 kJ. Standard enthalpy of formation of sulphur
trioxide is :
2H 2 O g
2H 2 g O 2 g H = 571.6 KJ
(a) –3166.4 kJ (b) 3166.4 kJ
f H of water is : (c) –395.8 kJ (d) 395.8 kJ
(a) 285.8 kJ (b) –285.8 kJ 95. Calculate the heat of formation of PCl5(s) from the following
(c) 1143.2 kJ (d) –1143.2 kJ data :
89. H for the reaction, 2P(s) + 3Cl2(g) 2PCl3(l) H = –151.8 kcal
1 PCl3(l) + Cl2(g)
PCl (s) H = –32.8 kcal
SO3 g
SO 2 g O 2 g H = –98.3 kJ
5
2 (a) –108.7 kcal (b) 108.7 kcal
If the enthalpy of formation of SO3(g) is –395.4 kJ then the (c) –184.6 kcal (d) 184.6 kcal
enthalpy of formation of SO2(g) is :
THERMODYNAMICS AND THERMOCHEMISTRY 206
102. The enthalpy of neutralisation of NH4OH and HCl is :
96. If S + O2
SO2 H = –298.2 kJ –1 –1
(a) 57.1 kJ mol (b) < 57.1 kJ mol
1
SO 2 O 2
SO3 H = –98.2 kJ (c) > 57.1 kJ mol
–1
(d) zero
2 –1
103. The heat of neutralisation of NaOH and HCl is 57.3 kJ mol .
H 2SO4 H = –130.2 kJ
SO3 H 2 O
The amount of heat liberated when 0.25 mol of H2SO4 reacts
1 with 1 mole of NaOH is
H 2 O 2 H2O H = –287.3 kJ
2 (a) 57.3 kJ (b) 14.325 kJ
the enthalpy of formation of H2SO4 at 298 K will be (c) 28.65 kJ (d) 114.6 kJ
(a) –433.7 kJ (b) –650.3 kJ 104. The heat of neutralisation of strong base and strong acid
(c) +320.5 kJ (d) –813.9 kJ is 57.0 kJ. The heat released when 0.5 mol of HNO3 is
97. The enthalpies of combustion of carbon and carbon added to 0.2 mol of NaOH solution is :
–1
monoxide are –393.5 and –283.0 kJ mol respectively. The (a) 57.0 kJ (b) 11.40 kJ
enthalpy of formation of carbon monoxide is : (c) 28.5 kJ (d) 34.9 kJ
(a) –676.5 kJ (b) 110.5 kJ 105. In which of the following neutralisation reaction, the heat
(c) –110.5 kJ (d) 676.5 kJ of neutralisation will be highest ?
98. On combustion, carbon forms two oxides CO and CO2. (a) NH4OH and H2SO4 (b) HCl and NaOH
Heat of formation of CO2 is –393.5 kJ and that of CO is – (c) CH3COOH and KOH (d) CH3COOH and NH4OH
110.5 kJ. Heat of combustion of CO is :
106. The enthalpies of neutralization of a weak base AOH and
(a) –393.5 kJ (b) –504.0 kJ a strong base BOH by HCl are –12250 cal/mol and –13000
(c) –283.0 kJ (d) 2830.0 kJ cal/mol respectively. When one mole of HCl is added to a
99. Which of the following compounds will absorb maximum solution containing 1 mole of AOH and 1 mole of BOH,
the enthalpy change was –12500 cal/mol. In what ratio is
quantity of heat when dissolved in the same amount of
the acid distribution between AOH and BOH?
water. The enthalpies of solution of these compounds at
(a) 2:1 (b) 2:3
25°C in kJ/mole are given in brackets ?
–1 –1 (c) 1:2 (d) None of these
(a) P (H = –32.6 kJ mol ) (b) Q (H = –17.3 kJ mol )
–1 –1 107. In what proportion 1 M NaOH and 0.5M H2SO4 are mixed
(c) R (H = +2.56 kJ mol ) (d) S (H = +25.6 kJ mol )
so as to release maximum amount of energy and to form
100. Which of the following salts will have maximum cooling 100 mL solution ?
effect when 0.5 mole of the salt is dissolved in same amount
(a) 33 and 67 (b) 67 and 33
of water. Integral heat of solution at 298 K is given for
each salt ? (c) 40 and 60 (d) 50 and 50
(a) KNO3
–1
(H = 35.4 kJ mol ) 108. The enthalpies of combustion of rhombic sulphur and
–1
–1 monoclinic sulphur are –295.1 and –296.4 kJ mol
(b) NaCl (H = 5.35 kJ mol )
respectively. The enthalpy of allotropic transformation of
–1
(c) HBr (H = –83.3 kJ mol ) monoclinic to rhombic sulphur is :
–1
(d) KOH (H = –55.6 kJ mol ) (a) 1.3 kJ (b) –1.3 kJ
101. The enthalpy of neutralisation of HCl by NaOH is –57.1 kJ (c) –591.5 kJ (d) 0
–1
and that of HCN by NaOH is –12.1 kJ mol . The enthalpy
109. Which of the following enthalpies is always negative ?
of ionization of HCN is :
(a) Enthalpy of solution
(a) –69.2 kJ (b) –45.0 kJ
(b) Enthalpy of combustion
(c) 69.2 kJ (d) 45.0 kJ
(c) Enthalpy of sublimation
(d) Enthalpy of formation
THERMODYNAMICS AND THERMOCHEMISTRY 207
–1 –1
110. In the reaction : (a) 498 kJ mol (b) 463 kJ mol
–1 –1
CO 2 g H 2 g
CO g H 2 O g H = 2.8 kJ (c) 428 kJ mol (d) 70 kJ mol
115. Calculate the heat of the reaction
then H represents
(a) heat of formation (b) heat of reaction CH2 = CH2(g) + H2(g)
CH3CH3(g)
(c) heat of solution (c) heat of combustion given that bond energy of C – C, C = C, C – H and H – H is
111. Using the following energy values, determine the lattice 80, 145, 98 and 103 kcal.
–1 –1
energy of KF(s): (a) –28 kcal mol (b) –5.6 kcal mol
–1 –1 –1
Property Energy (kJ mol ) (c) –2.8 kcal mol (d) –56 kcal mol
Hatomization of K(s) 90 116. The enthalpy change for the following reaction is 368 kJ.
Hatomization of F2(g) 158 Calculate the average O–F bond energy.
Hf of KF(s) –567 OF2 (g) O(g) 2F(g)
IE of K(g) 419 (a) 184 kJ/mol (b) 368 kJ/mol
EA of F(g) 328 (c) 536 kJ/mol (d) 736 kJ/mol
(a) 51 kJ (b) + 827 kJ 117. The enthalpy change for the reaction,
(c) + 1145 kJ (d) + 1483 kJ C2H6(g) 2C(g) + 6H(g) is X kJ. The bond energy of C–H
112. The lattice enthalpy and hydration enthalpy of four bond is:
compounds are given below: X X
(a) (b)
Compound Lattice enthalpy Hydration enthalpy 2 3
X
(kJ/mol) (kJ/mol) (c) (d) data insufficient
6
P +780 –920 o
118. Based on the values of B.E. given, fH of N2H4(g) is:
Q +1012 –812 –1 –1
Given: N–N = 159 kJ mol ; H–H = 436 kJ mol
R +828 –878
N N = 941 kJ mol , N–H = 398 kJ mol
–1 –1
S +632 –600 –1 –1
(a) 711 kJ mol (b) 62 kJ mol
The pair of compounds which is soluble in water is –1 –1
(c) –98 kJ mol (d) –711 kJ mol
(a) P and Q (b) Q and R
119. The dissociation energy of CH4 and C2H6 are respectively
(c) R and S (d) P and R 360 and 620 kcal/mole. The bond energy of C–C is
Bond Dissociation Enthalpy (a) 260 k cal/mole (b) 180 k cal/mole
113. The standard enthalpies of formation of HCl(g), H(g) and (c) 130 k cal/mole (d) 80 k cal/mole
–1
Cl(g) are –92.2, 217.7 and 121.4 kJ mol respectively. The 120. An imaginary reaction X Y takes place in three steps
bond dissociation energy of HCl is :
X A, H = –q1; B A, H = –q2, B Y,, H = –q3
(a) +431.3 kJ (b) 236.9 kJ
If Hess’ law is applicable, then the heat of the reaction
(c) –431.3 kJ (d) 339.1 kJ (X Y) is:
114. The enthalpy changes at 25°C in successive breaking of (a) q1–q2+q3 (b) q2–q3–q1
O–H bonds of water are :
(c) q1–q2–q3 (d) q3–q2–q1
H2O(g)
H(g) + OH(g) H = 498 kJ mol–1
OH(g)
H(g) + O(g) –1
H = 428 kJ mol
the bond enthalpy of the O–H bond is :
THERMODYNAMICS AND THERMOCHEMISTRY 208
EXERCISE - 2 : PREVIOUS YEAR JEE MAINS QUESTIONS
1. During which of the following processes, does entropy Minimum temperature at which it will become
decrease? sponatneous is ________ K. (Integer)
(A) Freezing of water to ice at 0oC (2021-02-26/Shift - 1)
(B) Freezing of water to ice at - 10 C
o
5. The average S - F bond energy in kJ mol-1 of SF6 is ______.
(Rounded off to the nearest integer)
(C) N 2 (g) 3H 2 (g) 2NH 3 (g)
[Given : The values of standard enthalpy of formation of
(D) Adsorption of CO(g) on lead surface.
SF6(g), S(g) and F(g) are -1100, 275 and 80 kJ mol-1
(E) NaCl(s) Na (aq) Cl (aq) respectively.] (2021-02-26/Shift - 2)
6. At 25oC, 50 g of iron reacts with HCl to form FeCl2, The
Choose the correct answer from the options given
evolved hydrogen gas expands against a constant
below : (2021-03-17/Shift - 2)
pressure of 1 bar. The work done by the gas during this
(a) (A), (C) and (E) only expansion is (Round off to the Nearest Integer).
(b) (A), (B), (C) and (D) only [Given : R = 8.314 J mol-1 K-1. Assume, hydrogen is an
(c) (A) and (E) only ideal gas] (2021-03-16/Shift - 2)
(d) (B) and (C) only [Atomic mass of Fe is 55.85 u]
2. The reaction of cyanamide, NH2CN(s) with oxygen was 7. The standard enthalpies of formation of Al2O3 and CaO
run in a bomb calorimeter and U was found to be are -1675 kJ mol-1 and -635 kJ mol-1 resepectively
-742.24 kJ mol-1. The magnitude of H 298 for the reaction For the reaction
3CaO + 2Al 3Ca + Al2O3 the standard reaction enthalpy
3
NH 2 CN(s) O2 (g) N 2 (g) CO2 (g) H2 O(l) r H o ........kJ (2021-03-17/Shift - 1)
2
(Round off to the Nearest Integer).
is _____ kJ. (Rounded off to the nearest integer)
[Assume ideal gas and R = 8.314 J mol-1 K-1] 8. For the reaction C 2 H 6 C2 H 4 H 2 the reaction
(2021-02-25/Shift - 1) enthalpy r H ..........kJ mol-1. (Round off to the Nearest
3. Five moles of an ideal gas at 293 K is expanded isothermally Integer) . [Given : Bond enthalpies in kJ mol-1 : C - C = 347,
from an initial pressure of 2.1 MPa to 1.3 MPa against at C = C = 611; C - H = 414, H - H = 436]
constant external pressure 4.3 MPa. The heat transferred (2021-03-18/Shift - 1)
in this process is ______ kJ mol . (Rounded-off to the
-1
9. An average person needs about 10000 kJ energy per day.
nearest integer) [Use R = 8.314 J mol-1 K-1] The amount of glucose (molar mass = 180.0 g mol-1) needed
(2021-02-25/Shift - 2) to meet this energy requirement is _____ g. (nearest
4. C D
For a chemical reaction A B integer) (Use : C H(glucose) 2700 kJ mol1 )
(2021-07-20/Shift - 1)
( r H 80 kJ mol 1 ) the entropy change r S
depends on the temperature T (in K) as
r S 2T(JK 1 mol1 ).
THERMODYNAMICS AND THERMOCHEMISTRY 209
10. For a given chemical reaction A B at 300 K the free
16. For water vap H 41kJmol1 at 373 K and 1 bar pressure.
energy change is -49.4 kJ mol-1 and the enthalpy of reaction
is 51.4 kJ mol-1. The entropy change of the reaction is Assuming that water vapour is an ideal gas that occupies
_____ J K-1 mol-1. (2021-07-20/Shift - 2) a much larger volume than liquid water, the internal energy
change during evaporation of water is ____ kJ mol-1
11. If the standard molar enthalpy change for combustion of
graphite powder is 2.48 × 102 kJ mol-1, the amount of heat [Use : R = 8.3 J mol-1 K-1] (2021-08-26/Shift - 2)
generated on combustion of 1 g of graphite powder is 17. 200 mL of 0.2 M HCl is mixed with 300 mL of 0.1 M NaOH.
_____kJ. (Nearest Integer) (2021-07-22/Shift - 2) The molar heat of neturalization of this reaction is
12. At 298 K, the enthalpy of fusion of a solid (X) is 2.8 kJ mol-1 -57.1 kJ. The increase in temperature in oC of the system
and the enthalpy of vaporization of the liquid (X) is 98.2 on mixing is x × 10-2. The value of x is ______. (Nearest
KJ/mol–1. The enthalpy of sublimation of the substance integer) [Given : Specific heat of water = 4.18 J g-1 K-1
(X) in KJ mol-1 is _______ . (in nearest integer) Density of water = 1.00 g cm-3] Assume no volume change
on mixing) : (2021-08-27/Shift - 1)
(2021-07-25/Shift - 1)
18. Data given for the following reaction is as follows :
13. A system does 200 J of work and at the same time absorbs
150 J of heat. The magnitude of the change in interval FeO (s) C(graphite) Fe (s) CO (g )
energy is ________ J. (2021-07-25/Shift - 2)
14. When 400 mL of 0.2 M H2SO4 solution is mixed with 600
mL of 0.1 M NaOH solution, the increase in temperature Substance H o (kJ mol 1 ) So (J mol 1K 1 )
of the final solution is ______ × 10-2 K. (Round off to the FeO(s) -266.3 57.49
nearest integer). (2021-07-27/Shift - 2) C(graphite) 0 5.74
[Use : H (aq) + OH (aq) H2O : r H 57.1 kJ mol ]
+ - 1
Fe(s) 0 27.28
CO(g) -110.5 197.6
Specific heat of H2O = 4.18 J K-1 g-1
Density of H2O = 1.0 g cm-3
Assume no change in volume of solution on mixing.
The minimum temperature in K at which the reaction
15. For water at 100oC and 1 bar, becomes spontaneous is _______. (Integer answer)
vap H vap U ___________102 Jmol1 (2021-08-27/Shift - 2)
(Round off to the Nearest Integer. Use:R = 8.31J mol-1 K-1 19. N 2 O4 (g), when
For the reaction 2NO 2 (g)
Assume volume of H2O(l) is much smaller than volume of 1
H2O (g). Assume H2O(g) treated as an ideal gas). S 176.0JK 1 and H 57.8 kJ mol , the
(2021-07-27/Shift - 1) magnitude of G at 298 K for the reaction is ____ kJ
mol-1. (Nearest integer) (2021-09-01/Shift - 2)
THERMODYNAMICS AND THERMOCHEMISTRY 210
20. At 25°C and 1 atm pressure, the enthalpies of (b) Both A and R are correct but R is NOT the correct
combustion are as given below: explanation of A
Substance H2 C(graphite) C2H6(g) (c) A is correct but R is not correct
c H –286.0 –394.0 –1560.0 (d) A is not correct but R is correct
kJ mol1
25. C(s) + O2(g) → CO2(g) + 400 kJ
The enthalpy of formation of ethane is
(JEE Main 2022) 1
C(s) + O2(g) → CO(g) + 100 kJ
(a) +54.0 kJ mol–1 (b) –68.0 kJ mol–1 2
(c) –86.0 kJ mol–1 (d) +97.0 kJ mol–1 When coal of purity 60% is allowed to burn in
21. At 25°C and 1 atm pressure, the enthalpy of presence of insufficient oxygen, 60% of carbon is
combustion of benzene (l) and acetylene (g) are –3268 converted into 'CO' and the remaining is converted
kJ mol–1 and –1300 kJ mol–1, respectively. The change into 'CO2'.
in enthalpy for the reaction 3C2H2(g) → C6H6 (l), is The heat generated when 0.6 kg of coal is burnt is
(JEE Main 2022) ______. (JEE Main 2022)
(a) +324 kJ mol–1 (b) +632 kJ mol–1 (a) 1600 kJ (b) 3200 kJ
(c) –632 kJ mol–1 (d) –732 kJ mol–1 (c) 4400 kJ (d) 6600 kJ
22. Match List-I with List-II. 26. For complete combustion of methanol
3
List-I List-II CH 3OH l O2 g CO2 g 2 H 2 O l the
(A) Spontaneous process (I) H 0 2
(B)Process with (II) GT , P 0 amount of heat produced as measured by bomb
P 0, T 0 calorimeter is 726 kJ mol–1 at 27oC. The enthalpy of
combustion for the reaction is –x kJ mol–1, where x
(C) H reaction (III) Isothermal and isobaric
is_____. (Nearest integer)
process
(Given: R = 8.3 JK–1 mol–1) (JEE Main 2022)
(D) Exothermic Process (IV) [Bond energies of
27. A fish swimming in water body when taken out from
molecules in reactants] –
the water body is covered with a film of water of
[Bond energies of product
weight 36 g. When it is subjected to cooking at 100°C,
molecules]
then the internal energy for vaporization in kJ mol –1 is
Choose the correct answer from the options given
____. [nearest integer]
below? (JEE Main 2022)
[Assume steam to be an ideal gas. Given vap H for
(a) (A) – (III), (B) – (II), (C) – (IV), (D) – (I)
(b) (A) – (II), (B) – (III), (C) – (IV), (D) – (I) water at 373 K and 1 bar is 41.1 kJ mol –1; R = 8.31 J
(c) (A) – (II), (B) – (III), (C) – (I), (D) – (IV) K–1 mol–1] (JEE Main 2022)
(d) (A) – (II), (B) – (I), (C) – (III), (D) – (IV) 28. When 5 moles of He gas expand isothermally and
23. Which of the following relation is not correct? reversibly at 300 K from 10 litre to 20 litre, the
(JEE Main 2022) magnitude of the maximum work obtained is ______
(a) ∆H = ∆U – P∆V (b) ∆U = q + W J. [nearest integer] (Given: R = 8.3 J K–1 mol–1 and log
(c) ∆Ssys + ∆Ssurr ≥ S (d) ∆G = ∆H – T∆S 2 = 0.3010) (JEE Main 2022)
24. Given below are two statements: One is labelled 29. 4.0 L of an ideal gas is allowed to expand isothermally
as Assertion A and the other is labelled as Reason R into vacuum until the total volume is 20 L. The
Assertion A: The reduction of a metal oxide is easier
amount of heat absorbed in this expansion is _____ L
if the metal formed is in liquid state than solid state.
Reason R: The value of ∆G becomes more on atm. (JEE Main 2022)
negative side as entropy is higher in liquid state than 30. For combustion of one mole of magnesium in an open
solid state.
container at 300 K and 1 bar pressure, ∆CH⊖ = –
In the light of the above statements. Choose the most
appropriate answer from the options given below 601.70 kJ mol–1, the magnitude of change in internal
(JEE Main 2022) energy for the reaction is ____ kJ. (Nearest integer)
(a) Both A and R are correct and R is the correct (Given: R = 8.3 J K–1 mol–1) (JEE Main 2022)
explanation of A
THERMODYNAMICS AND THERMOCHEMISTRY 211
31. 17.0 g of NH3 completely vapourises at –33.42oC and 38. A gas (Molar mass = 280 g mol–1) was burnt in excess
1 bar pressure and the enthalpy change in the process O2 in a constant volume calorimeter and during
is 23.4 kJ mol–1. The enthalpy change for the combustion the temperature of calorimeter increased
vapourisation of 85 g of NH3 under the same from 298.0 K to 298.45 K. If the heat capacity of
conditions is _____ kJ. (JEE Main 2022) calorimeter is 2.5 kJ K–1 and enthalpy of combustion
32. 2.2 g of nitrous oxide (N2O) gas is cooled at a constant of gas is 9 kJ mol–1 then amount of gas burnt
pressure of 1 atm from 310 K to 270 K causing the is_______ g. (Nearest Integer) (JEE Main 2022)
compression of the gas from 217.1 mL to 167.75 mL. 39. Among the following the number of state variable is
The change in internal energy of the process, ∆U is ‘– ______.
x’ J. The value of ‘x’ is _____. [Nearest integer] Internal energy (U)
(Given: atomic mass of N = 14 g mol–1 and of Volume (V)
O = 16 g mol–1. Molar heat capacity of N2O is 100 J Heat (q)
K–1 mol–1) (JEE Main 2022) Enthalpy (H) (JEE Main 2022)
33. The enthalpy of combustion of propane, graphite and 40. When 600 mL of 0.2 M HNO3 is mixed with 400 mL
dihydrogen at 298 K are: –2220.0 kJ mol–1, – 393.5 kJ of 0.1M NaOH solution in a flask, the rise in
mol–1 and –285.8 kJ mol–1 respectively. temperature of the flask is _______ × 10–2 oC.
The magnitude enthalpy of formation of propane (Enthalpy of neutralisation = 57 kJ mol–1 and Specific
(C3H8) is………kJ mol–1. (Nearest integer) heat of water = 4.2 JK–1 g–1)
(JEE Main 2022) (Neglect heat capacity of flask) (JEE Main 2022)
34. While performing a thermodynamics experiment, a 41. Which of the following relations are correct?
student made the following observations, (A) U q pV
HCl + NaOH → NaCl + H2O ∆H = –57.3 kJ mol–1 (B) G H T S
CH3COOH + NaOH → CH3COONa + H2O qrev
∆H = –55.3 kJ mol–1. (C) S
T
The enthalpy of ionization of CH3COOH as calculated
(D) H U nRT
by the student is ______ kJ mol–1.
Choose the most appropriate answer from the options
(nearest integer) (JEE Main 2022)
given below: (JEE Main 2023)
35. 2.4 g coal is burnt in a bomb calorimeter in excess of
(a) C and D only (b) B and C only
oxygen at 298 K and 1 atm pressure. The temperature
(c) A and B only (d) B and D only
of the calorimeter rises from 298 K to 300 K. The –1
enthalpy change during the combustion of coal is –x kJ 42. The correct order of bond enthalpy ( (kJ mol ) is :
mol–1. The value of x is ______. (Nearest Integer) (JEE Main 2023)
(Given: Heat capacity of bomb calorimeter 20.0 kJ (a) Si – Si > C – C > Sn – Sn > Ge – Ge
K–1. Assume coal to be pure carbon) (b) Si – Si > C – C > Ge – Ge > Sn – Sn
(JEE Main 2022) (c) C – C > Si – Si > Sn – Sn > Ge – Ge
36. For the reaction (d) C – C > Si – Si > Ge – Ge > Sn – Sn
43. Given
H2F2(g) → H2(g) + F2(g)
(A) 2CO g O2 g 2CO2 g .. H1 x kJ mol
–1
∆U = –59.6 kJ mol–1 at 27 °C.
(B) C(graphite) O2 g CO g .. H 2 ykJ mol –1
The enthalpy change for the above reaction is (–) ___
kJ mol–1 [nearest integer] The H for the reaction
1
Given: R = 8.314 JK–1 mol–1. (JEE Main 2022) C(graphite) O2 g CO g is
2
37. The molar heat capacity for an ideal gas at constant (JEE Main 2023)
pressure is 20.785 J K–1mol–1. The change in internal 2x y x 2y
(a) (b)
energy is 5000 J upon heating it from 300K to 500K. 2 2
x 2y
The number of moles of the gas at constant volume is (c) 2 y x (d)
2
___ [Nearest integer]
(Given: R = 8.314 J K–1 mol–1) (JEE Main 2022)
THERMODYNAMICS AND THERMOCHEMISTRY 212
44. What happens when methane undergoes combustion in Given: The enthalpy of evaporation of water is
systems A and B respectively? (JEE Main 2023) 45 kJ mol –1
–1
Molar mass of C, H & O are 12. 1 and 16 g mol .
(JEE Main 2023)
48. 28.0 L of CO2 is produced on complete combustion of
16.8 L gaseous mixture of ethene and methane at
(a) 25º C and 1 atm. Heat evolved during the combustion
System A System B
process is ________ kJ.
Temperature Falls Temperature remains same
Given: HC (CH 4 ) –900 kJ mol
–1
(b)
System A System B HC (C2 H 4 ) –1400 kJ mol –1 (JEE Main 2023)
Temperature Falls Temperature rises
(c) 49. Consider the following reaction approaching
System A System B equilibrium at 27C and 1 atm pressure
Temperature Rises Temperature remains same K f 103
(d) A B C D
K r 102
System A System B
The standard Gibb’s energy change r G at 27C
Temperature remains same Temperature rises
45. For independent process at 300 K. is _____ kJmol 1
1 1
Process H / kJ mol S / J K (Nearest integer)
A –25 –80 (Given: R 8.3JK 1mol 1 andln10 2.3
B –22 40 (JEE Main 2023)
C 25 –50 50. When 2 litre of ideal gas expands isothermally into
D 22 20 vacuum to a total volume of 6 litre, the change in
The number of non-spontaneous process from the internal energy is ______ J. (Nearest integer)
following is _______. (JEE Main 2023) (JEE Main 2023)
46. One mole of an ideal monoatomic gas is subjected to 51. 1 mole of ideal gas is allowed to expand reversibly and
changes as shown in the graph. The magnitude of the adiabatically from a temperature of 27C . The work
work done (by the system or on the system) is done is 3 kJ mol –1 . The final temperature of the gas is
_______ J (nearest integer)
_____K (Nearest integer). Given Cv 20 J mol K .
–1 –1
(JEE Main 2023)
52. The enthalpy change for the conversion of
1
Cl2 g to Cl – aq is (-) _____________
2
kJ mol –1 (Nearest integer)
Given: dis H oCl2 g 240kJ mol1 ,
eg H oCl g 350kJ mol1 , hyd H oCl g 380kJ mol 1
Given: log 2 = 0.3, ln 10 = 2.3 (JEE Main 2023)
(JEE Main 2023)
47. An athlete is given 100 g of glucose (C6 H12O6 ) for
53. Enthalpies of formation of
energy. This is equivalent to 1800 kJ of energy. The CCl4 g , H 2 O g , CO2 g and HCl g are − 105,
50% of this energy gained is utilized by the athlete for
sports activities at the event. In order to avoid storage − 242, − 394 and 92 kJ mol 1 respectively. The
of energy, the weight of extra water he would need to magnitude of enthalpy of the reaction given below is
perspire is _______ g (Nearest integer) ______ kJ mol 1 (nearest integer)
Assume that there is no other way of consuming stored CCl4 g 2 H 2 O g CO2 g 4 HCl g
energy. (JEE Main 2023)
THERMODYNAMICS AND THERMOCHEMISTRY 213
54. At 25C , the enthalpy of the following processes are 59. When a 60 W electric heater is immersed in a gas for
given: 100s in a constant volume container with adiabatic
H2(g) + O2(g) → 2OH(g) ∆H0 = 78kJ mol–1 walls, the temperature of the gas rises by 5C . The
H2(g) + ½ O2(g) → H2O(g) ∆H0 = –242 kJ mol–1 heat capacity of the given gas is ______ J K–1 (Nearest
H2(g) → 2H(g) ∆H° = 436 kJ mol–1 integer) (JEE Main 2023)
½ O2(g) → O(g) ∆H° = 249 kJ mol–1 60. For complete combustion of ethene,
What would be the value of X for the following C2 H 4 g 3O2 g 2CO2 g 2 H 2 O l
reaction? _____ (Nearest integer)
the amount of heat produced as measured in bomb
H2O(g)→H(g) + OH(g) ∆H0 = X kJ mol–1
calorimeter is 1406 kJ mol–1 at 300K. The minimum
(JEE Main 2023)
value of T∆S needed to reach equilibrium is (–)
55. 0.3 g of ethane undergoes combustion at 27C in a
_______ kJ. (Nearest integer)
bomb calorimeter. The temperature of calorimeter Given: R = 8.3 J K–1 mol–1 (JEE Main 2023)
system (including the water) is found to rise by 0.5C . 61. The number of endothermic process/es from the
The heat evolved during combustion of ethane at following is _____
constant pressure is kJmol1 . A. I 2 g 2 I g
(Nearest integer)
[Given: The heat capacity of the calorimeter system is B. HCl g H g Cl g
20kJK1 , R 8.3JK 1 mol1 . C. H 2 O l H 2 O g
Assume ideal gas behaviour. D. C s O2 g CO2 g
Atomic mass of C and H are 12 and 1gmol1 E. Dissolution of ammonium chloride in water
respectively] (JEE Main 2023) (JEE Main 2023)
56. The value of log K for the reaction A B at 298 K 62. Solid fuel used in rocket is a mixture of Fe2O3 and Al
is ______. (Nearest integer) (in ratio 1 : 2). The heat evolved (kJ) per gram of the
Given: H 54.07kJ mol
1 mixture is _____ (Nearest integer)
Given,
S 10 JK 1 mol 1 Hf Al 2 O3 1700 kJ mol 1
(Take 2.303 8.314 298 5705) (JEE Main 2023)
H f Fe 2 O3 840 kJ mol 1
57. Consider the graph of Gibbs free energy G vs Extent
of reaction. The number of statement/s from the Molar mass of Fe, Al and O are 56, 27 and 16 g
following which are true with respect to points (a), (b) mol–1 respectively. (JEE Main 2023)
and (c) is ______ 63. The total number of intensive properties from the
following is ________
Volume, Molar heat capacity, Molarity, E cell,
Gibbs free energy change, Molar mass, Mole
(JEE Main 2023)
64. One mole of an ideal gas at 350 K is in a 2.0 L vessel
of thermally conducting walls, which are in contact
with the surroundings. It undergoes thermal reversible
expansion from 2.0L to 3.0 L against a constant
pressure of 4 atm. The change in entropy of the
surrounding S is _______ JK 1 (Nearest integer)
A. Reaction is spontaneous at (a) and (b) Given: R 8.314 JK 1 mol 1 (JEE Main 2023)
B. Reaction is at equilibrium at point (b) and non- 65. 30.4 kJ of heat is required to melt one mole of sodium
spontaneous at point (c) chloride and the entropy change at the melting point is
C. Reaction is spontaneous at (a) and non-spontaneous 28.4 J K–1 mol–1 at 1 atm. The melting point of sodium
at (c) chloride is ______ K (Nearest Integer)
D. Reaction is non-spontaneous at (a) and (b) (JEE Main 2023)
(JEE Main 2023) 66. A2 + B2 → 2AB. ∆Hf0 = –200 kJ mol–1
58. Consider the following data. AB. A2 and B2 are diatomic molecules. If the bond
Heat of combustion of H2(g) = –241.8 kJ mol–1 enthalpies of A2, B2 and AB are in the ratio 1:0.5:1.
Heat of combustion of C(s) = –393.5 kJ mol–1 then the bond enthalpy of A2 is ____ kJ mol–1 (Nearest
Heat of combustion of C2H5OH(l) = –1234.7 kJ mol–1 integer) (JEE Main 2023)
The heat of formation of C2H5OH(l) is (–) ________
kJ mol–1 (Nearest integer). (JEE Main 2023)
THERMODYNAMICS AND THERMOCHEMISTRY 214
EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS
Objective Questions I [Only One Correct Option] (a) 104 kcal (b) 10.4 kcal
1. An ideal gas at constant temperature and pressure (c) 1040 kcal (d) 1.04 kcal
expands, then its 8. Consider an ideal gas. When dw = 0 and dq < 0,
(a) Internal energy remains same (a) the temperature will decrease
(b) Internal energy decreases (b) the volume will increase
(c) Internal energy increases (c) the pressure will remain constant
(d) Entropy first increases and then decreases
(d) the temperature will increase
2. The internal energy of a substance
9. When heat is supplied to an ideal gas in an isothermal
(a) Increases with increase in temperature process, the
(b) Decreases with increase in temperature (a) gas will do positive work
2
(c) Can be calculated by the relation E = mc (b) gas will do negative work
(d) Remains unaffected with change in temperature (c) kinetic energy of the gas will increase
3. Which of the following is correct ? (d) gas will not obey the law of conservation of energy
CP 10. The magnitudes of enthalpy changes for irreversible
(a) CP – CV = R (b) C
V adiabatic expansion of a gas from 1L to 2L is H1 and
(c) CP > CV (d) All of these for reversible adiabatic expansion for the same expansion
4. CP for monoatomic gas is is H2. Then
(a) 5/2 R (b) 3/2 R (a) H1 > H2
(c) 7/2 R (d) R (b) H1 < H2
5. Standard molar enthalpy of formation of CO2 is equal to (c) H1 = H2, enthalpy being a state function
(a) zero (d) H1 = E1 & H2 = E2 where E1 & E2 are
(b) the standard molar enthalpy of combustion of magnitudes of change in internal energy of gas in
gaseous carbon these expansions respectively.
(c) the sum of standard enthalpies of formation of CO and 11. A liquid which is confined inside an adiabatic piston is
O2 suddenly taken from state 1 to state 2 by a single stage
process. If the piston comes to rest at point 2 as shown.
(d) the standard molar enthalpy of combustion of
Then the enthalpy change for the process will be :
carbon (graphite)
6. The mathematical expression for the standard enthalpy
of sublimation is given by
(a) Hº (sublimation) = Hº (fusion) – 2Hº
(vaporization)
(b) Hº (sublimation) = Hº (fusion) – Hº
(vaporization)
(c) Hº (sublimation) = Hº (fusion) + Hº
(vaporization)
(d) Hº (sublimation) = Hº (combustion) + Hº
(dissociation)
2 P0 V0 3P0 V0
7. Energy required to dissociate 4g of gaseous hydrogen (a) H 1 (b) H 1
into free gaseous atoms is 208 kcal at 25°C. The bond
energy of H — H bond will be (c) H = – P0 V0 (d) None of these
THERMODYNAMICS AND THERMOCHEMISTRY 215
12. A gas expands adiabatically at constant pressure such If Cv , m 21.686 103 T , then H for the process is :
–1/2
that T V . The value of (Cp,m/Cv,m) of the gas will
be : (a) 3000 J (b) 3350 J
(a) 1.30 (b) 1.50 (c) 3700 J (d) 30350 J
(c) 1.70 (d) 2 19. For an ideal gas undergoing adiabatic expansion
13. 1 mole of an ideal gas A (Cv,m = 3 R) and 2 mole of an in vaccum,
3 (a) U = 0 (b) q = 0
ideal gas B C v,m R are taken in a container and
2 (c) W = 0 (d) all the above are true
expanded reversibly and adiabatically from 1 litre to 4
litre starting from initial temperature of 320 K. E or U 20. What is the change in molar entropy of helium in the
for the process is : following process ?
(a) –240 R (b) 240 R 1 He (298 K, 1 bar) 1 He (100 K, 10 bar)
(c) 480 R (d) –960 R (a) 41.8 J K–1 mol–1 (b) 4.18 J K–1 mol–1
14. 2 mole of an ideal monoatomic gas undergoes a (c) – 41.8 J K–1 mol–1 (d) – 4.18 J K–1 mol–1
2
reversible process for which PV = C. The gas is expnaded
from initial volume of 1 L to final volume of 3L starting H
21. S holds good for
from initial temperature of 300 K. Find H for the process: T
(a) –600R (b) –1000R (a) an adiabatic process
(c) –3000R (d) None of these (b) an isothermal reversible-phase change
15. A certain gas in expanded from (lL, 10 atm) to (4L, 5 atm) (c) a process at constant pressure
against a constant external pressure of 1 atm. If the
(d) a process under any condition
initial temperature of gas is 300 K and heat capacity for
the process is 50 J/ºC, the enthalpy change during the 22. rH0 for solid-to-liquid transition for proteins A and B
process is : (Use : 1L atm 100 J) are 2.73 kcal mol–1 and 3.03 kcal mol–1. The two melting
(a) 15 kJ (b) 15.7 kJ points are 0ºC and 30ºC respectively. The entropy
changes SA and SB at two transition temperatures
(c) 14.3 kJ (d) 14.7 kJ
are related as :
16. The molar heat capacities at constant pressure (assumed
(a) SA = SB (b) SA < SB
constant with respect to temperature) for A, B and C are
in ratio of 3 : 1.5 : 2.0. The enthalpy change for the 303SA
(c) SB > SA (d) SB =
exothermic A + 2B 3C at 300 K and 310 K is H300 and 273
H310 (magnitudes) respectively then : 23. For the real gases reaction
(a) H300 > H310 2CO (g) + O2(g)
2CO2 (g) H = –560 kJ.
(b) H300 < H310
In 10 litre rigid vessel at 500 K the initial pressure is
(c) H300 = H310 70 bar and after the reaction it becomes 40 bar. The
(d) if T2 > T1 then H310 > H300 and if T2 < T1 change in internal energy is :
then H310 < H300 (a) –557 kJ (b) –530 kJ
17. The specific heat of a gas at constant volume is 0.075 cal/g. (c) –563 kJ (d) None of these
Predict the atomicity of the gas. Molar mass of gas is 24. At 5 × 105 bar pressure, density of diamond and graphite
–1
40 g mol . are 3 g/cc and 2 g/cc respectively, at certain temperature
(a) 1 (b) 2 ‘T’. Find the value of U–H for the conversion of
(c) 3 (d) None of these 1 mole of graphite to 1 mole of diamond at temperature
‘T’ :
18. 10 mole of an ideal gas is heated at constant pressure of
o
one atmosphere from 27 C to 127 C.
o (a) 100 kJ/mol (b) 50 kJ/mol
(c) – 100 kJ/mol (d) None of these
THERMODYNAMICS AND THERMOCHEMISTRY 216
25. The enthalpy of formation of NH3(g) at constant pressure 30. Given that,
and 3500C temperature is –50.0 kJ mol–1. What will be the H0f (CO2, g) = – 393.509 kJ mol–1,
enthalpy of formation of NH3(g) at constant volume at
the same temperature ? H0f (H2O, l ) = – 285.830 kJ mol–1,
(a) – 50.0 kJ mol–1 (b) – 45 kJ mol–1 H0f (C2H5OH, l) = – 277.800 kJ mol–1.
(c) – 60.4kJ mol–1 (d) – 54 kJ mol–1 Calculate the Hº (combustion) of liquid ethanol. The
26. Mg(s) + 2HCl(aq.) MgCl2(aq) + H2(g); following is the required reaction.
rH0 = – 467 kJ/mol C2H5OH (l ) + 3O2 (g) 2CO2 (g) + 3H2O (l )
MgO (s) + 2HCl (aq) MgCl2 (aq) + H2O (l ) ; (a) – 1366.82 kJ mol–1 (b) – 278.82 kJ mol–1
rH0 = – 151 kJ/mol (c) – 2264.66 kJ mol–1 (d) – 1155.78 kJ mol–1
According to the information, and given the fact that 31. The enthalpy of neutralization of a strong acid by a
for water, fH0 = – 286 kJ/mol, what is the fH0 for strong base is –57.32 kJ mol–1. The enthalpy of formation
MgO(s) ? of water is –285.84 kJ mol–1. The enthalpy of formation
of the hydroxyl ion is
(a) – 904 kJ/mol (b) – 602 kJ/mol
(a) + 228.52 kJ mol–1 (b) – 114.26 kJ mol–1
(c) – 334 kJ/mol (d) – 30 kJ/mol
(c) – 228.52 kJ mol–1 (d) + 114.26 kJ mol–1
1
27. The enthalpy of reaction CH4(g) + O (g) CH3OH(L ) 32. Heat of neutralisation of NaOH and HCl is –57.46 kJ/
2 2 equivalent. The heat of ionisation of water will be :
is negative. If enthalpy of combustion of CH4 and (a) – 57.46 kJ/mol (b) 57.46 kJ/mol
CH3OH are x and y respectively then which of the
(c) – 114.92 kJ/mol (d) 114.92 kJ/mol
following relations is correct?
33. In which case of mixing of a strong acid and strong
(a) x > y (b) x < y
base, each of 1N concentration, temperature increase is
(c) x = y (d) x y
the highest ?
28. For the allotropic change represented by the equation
C (diamond) (graphite) the enthalpy change is (a) 20 ml acid and 30 ml alkali
H = – 1.89 kJ (b) 10 ml acid and 40 ml alkali
If 6g of diamond and 6 g of graphite are separately burnt
(c) 25 ml acid and 25 ml alkali
to yield carbon dioxide, the heat, liberated in the first
case is (d) 35 ml acid and 15 ml alkali
(a) less than in the second case by 1.89 kJ
34. Heat of neutralization of a strong dibasic acid in dilute
(b) more than in the second case by 1.89 kJ
solution by NaOH is nearly
(c) less than in the second case by 11.34 kJ
(a) – 27.4 kcal/eq (b) 13.7 kcal/mol
(d) more than in the second case by 0.945 kJ
29. The enthalpy of combustion for octane (a major (c) – 13.7 kcal/eq (d) – 13.7 kcal/mol
component of gasoline) is – 47.8 kJ/g. How much energy 35. Heat released in neutralization of strong acid and strong
is released by burning 1.0 L of octane (density
0.740 g/mL) ? base is 13.4 kcal/mol. The heat released on neutralization
(a) – 35400 kJ (b) – 64600 kJ of NaOH with HCN is 2.9 kcal/mol, then H° of
(c) – 47800 kJ (d) – 57200 kJ ionization of HCN in water is
(a) 10.5 kcal (b) 16.3 kcal
(c) 9.5 kcal (d) 11.5 kcal
THERMODYNAMICS AND THERMOCHEMISTRY 217
36. Calculate the enthalpy change when 1.0 g of water is (c) rG0 is + 50.8 kJ and the reaction is driven by both
frozen at 00C ( H0f = 1.435 kcal mol–1) enthalpy and entropy.
(d) rG0 is – 50.8 kJ and the reaction is driven by both
(a) – 1.435 cal g–1 (b) – 80.0 cal g–1
enthalpy and entropy.
(c) 80.0 cal g–1 (d) – 55.6 cal g–1
41. Given fH0 (kJ/mol) S0m (J/k/mol)
37. Given are the following entropy values at 298 K and 1
atm: CCl4 (l ) – 135.4 215.4
–1 –1 –1 –1
H2 (g) = 130.6 J K mol ; Cl2 (g) = 223.0 J K mol ; CCl4 (g) – 103.0 308.7
–1 –1
HCl (g) = 186.7 J K mol What is the boiling point of carbon tetrachloride ?
The entropy change for the reaction (a) 8.25ºC (b) 74.3ºC
H2 (g) + Cl2 (g) 2HCl (g) would be (c) 92.3ºC (d) 45.8ºC
(a) +540.3 J K–1 mol–1 (b) +727 J K–1 mol–1 42. Calculate f G o for (NH4Cl, s) at 310 K.
(c) –166.9 J K–1 mol–1 (d) +19.8 J K–1 mol–1
Given : f H o (NH4Cl, s)= –314.5 kJ/mol; r C p =0
38. The free-energy change for the conversion of maleate
into fumarate is 3.0 kJ. In metabolism, this reaction is SoN2 (g) =192 JK–1 mol–1; SoH2 (g) =130.5JK–1 mol–1
coupled with the conversion fumarate to asparate,
SoCl2 (g) =233 JK–1 mol–1 SoNH4 Cl(s) = 99.5 JK–1 mol–1
0
which is exergonic by 15.5 kJ. Calculate G for the
overall reaction. (All data given at 300K)
(a) – 18.5 kJ (b) + 18.5 KJ (a) – 198.56 kJ/mol (b) –426.7 KJ/mol
(c) – 12.5 kJ (d) – 25.0 kJ (c) –202.3 KJ/mol (d) None of these
39. The G for the following reactions at 8000C are given as 43. The bond energy of H2 is 104.3 kcal/mol. It means that
S2 (s) + 2O2 (g) 2SO2 (g); G = – 544 kJ (a) 104.3 kcal heat is needed to break one bond to form two
atoms
2Zn (s) + S2 (s) 2ZnS (s) ; G = – 293 kJ
(b) 104.3 kcal is required to break 6.02 × 1023 molecules
2Zn (s) + O2 (g) 2ZnO (s); G = – 480 kJ
into 1.2406 × 1024 atoms of hydrogen
The G for the reaction
(c) 104.3 kcal is required to break 3.015 × 1023 hydrogen
2Zn S + 3O2 (g) 2ZnO (s) + 2SO2 (g) will be molecules to 6.02 × 1023 hydrogen atoms
(a) – 357 kJ (b) – 731 kJ (d) none of these
(c) – 773 kJ (d) – 229 kJ 44. Determine C–C and C–H bond enthalpy (in kJ/mol)
40. Consider the reaction below at 298 K :
Given: f H o (C2 H 6 ,g) = –85 kJ/mol
C (graphite) + 2H2 (g) CH4 (g) fHº (kJ/mol) = 74.9
f H o (C3 H8 ,g) = –104 kJ/mol
S0m (J/K/mol)
+ 5.6 + 130.7 + 186.3 sub H o (C,s) =718 kJ/mol B.E.(H H) = 436 kJ/mol
Which statement below is correct ? (a) 414, 345 (b) 345, 414
(a) rG0 is – 50.8 kJ and the reaction is driven by enthalpy (c) 287, 404.5 (d) None of these
only.
(b) rG0 is – 50.8 kJ and the reaction is driven by entropy
only.
THERMODYNAMICS AND THERMOCHEMISTRY 218
45. What is the bond enthalpy of Xe–F bond? 50. A sample containing 1.0 mol of an ideal gas is expanded
isothermally and reversily to ten time of its original
XeF4 Xe (g) F (g) F2 (g) F(g);
volume, in two separate experiments. The expansion is
r H 292 kcal / mol carried out 200 K and at 400 K, respectively. Choose the
Given: Ionization energy of Xe = 279 kcal/mol correct option.
B.E. (F–F) = 38 kcal/mol, (a) Work done at 400 K is twice the work done at
200 K.
Electron affinity of F = 85 kcal/mol
(b) Work done at 400 K is twice the work doen at
(a) 24 kcal/mol (b) 34 kcal/mol 200 K.
(c) 8.5 kcal/mol (d) None of these (c) Work done at 400 K is 20 times the work done at
46. The lattice energy of solid NaCl is 180 kcal per mol. The 200 K.
dissolution of the solid in water in the form of ions is
(d) E 0 in both cases.
endothermic to the extent of 1 kcal per mol. If the
solvation energies of Na+ and Cl– ions are in the ratio 51. The normal boiling point of a liquid ‘X’ is 400 K.
6 : 5, what is the enthalpy of hydration of sodium ion ? Which of the following statement is true about the
(a) – 85.6 kcal/mol (b) – 97.5 kcal/mol process X(l) X(g) ?
(c) 82.6 kcal/mol (d) + 100 kcal/mol (a) at 400 K and 1 atm pressure G 0
5 (b) at 400 K and 2 atm pressure G ve
47. 0.5 mole each of two ideal gases A C v,m R and B
2 (c) at 400 K and 0.1 atm pressure G ve
(Cv,m = 3R) are taken in a container and expanded (d) at 410 K and 1 atm pressure G ve
reversibly and adiabatically, during this process
temperature of gaseous mixture decreased from 350 K Numerical Value Type Questions
and 250 K. Find H (in cal/mol) for the process : 52. Assume that the human body is a heat engine. For a
(a) –100 R (b) –137.5 R food intake equivalent to 1.0 × 107 J day-1, a human
(c) –375 R (d) None of these can work for 6 h day-1 at a rate equivalent to 0.0374
HP (1 HP = 746 W). What is the efficiency of the
Objective Questions II
human body?
[One or more than one correct option] 53. Heat of neutralisation of a polybasic acid by a strong
48. Among the following, the state function(s) is/are base is -54.8 k cal mol-1. What is basicity of the acid?
(a) Internal energy 54. Find change in internal energy, when 0.5 mole of Ar
(b) Irreversible expansion work having a specific heat at constant pressure of
(c) Reversible expansion work 20.814 J g-1 deg-1 is heated from 27oC to 31oC at
(d) Molar enthalpy constant volume. (Atomic mass of Ar = 40) (give your
answer in kJ)
49. If enthalpy of hydrogenation of C6H6(l) into C6H12(l)
55. The enthalpy of neturalizaton of 0.4 M H2SO4 will be
is –205 kJ and resonance energy of C6H6(l) is –152 kJ/
how many times the enthalpy of neutralization of
0.1 M HCl?
mol then enthalpy of hydrogenation of is
Assume Hvap of C6H6(l), C6H8(l), C6H12(l) all are equal:
(a) – 535.5 kJ/mol (b) – 238 kJ/mol
(c) – 357 kJ/mol (d) – 119 kJ/mol
THERMODYNAMICS AND THERMOCHEMISTRY 219
61. Assertion (A) : Heat of neutralization of HF is more
Assertion Reason
than that of HCl by NaOH.
(A) If both Assertion and Reason are correct
Reason (R) : HCl is stronger acid than HF.
and Reason is the correct explanation of
(a) A (b) B
Assertion.
(B) If both Assertion and Reason are true but (c) C (d) D
Reason is not the correct explanation of 62. Assertion (A) : Enthalpy of neutralization of
CH3COOH by NaOH is less than that of HCl by NaOH.
Assertion.
(C) If Assertion is true but Reason is false. Reason (R) : Enthalpy of neutralization of CH3COOH
is less because of the absorption of heat in the
(D) If Assertion is false but Reason is true. ionization process.
56. Assertion (A) : The extensive properties of a single (a) A (b) B
pure substance will not only depend upon the number (c) C (d) D
of moles of the substance present but also on any
two of the three variables. 63. Assertion (A) : When a salt dissolves in water, the
temperature of solution decreases.
Reason (R) : Any extensive property if expressed as
per mole or per gram becomes an intensive property. Reason (R) : Energy equal to lattice energy is required
to ionize the salt in solution.
(a) A (b) B
(a) A (b) B
(c) C (d) D
(c) C (d) D
57. Assertion (A) : There is no change in internal energy
for an ideal gas at constant temperature. Match the following
Reason (R) : Internal energy of an ideal gas is a Each questions has two columns. Four options are
function of temperature only.
given representing matching elements from
(a) A (b) B
Column-I and Column-II. Only one of these four
(c) C (d) D
options corresponds to a correct matching for each
58. Assertion (A) : A reversible process produces more
questions.
work than the same process if it is carried out
irreversibly for the same increase in volume. 64. Match the Column-I with Column-II
Reason (R) : A reversible process is exothermic while Column - I Column - II
irreversible process is endothermic A. H 2 O(l) H 2 O(g) p. G 0
(a) A (b) B
B. C(s) O 2 (g) CO 2 (g) q. H 0
(c) C (d) D
C. H 2 O(s) H 2 O(l) r. S 0
59. Assertion (A) : Entropy change in reversible
adiabatic expansion of an ideal gas is zero. 1
D. C(s) O 2 (g) CO(g) s. H 0
Reason (R) : The increase in entropy due to volume 2
increase just componsate the decrease in entropy 65. Match the Column-I with Column-II
due to fall in temperature.
Column I Column II
(a) A (b) B
(A) O2 (p) 1.4
(c) C (d) D
60. Assertion (A) : When internal energy of reactants (B) N2 7
(q) CP R
becomes greater than that of products the energy is 2
given out to the surrounding.
(C) CO2, CH4 23
Reason (R) : All exothermic reactions take place at (r) C P R
6
constant temperature, E will be positive.
(a) A (b) B (D) 1 mol O2 + 2 mol O3 (s) 1.33
(c) C (d) D
THERMODYNAMICS AND THERMOCHEMISTRY 220
Paragraph Type Questions Use the following passage, to solve Q. 69 to Q. 70
Use the following passage, to solve Q. 66 to Q. 68 Passage
Passage Standard Gibb’s energy of reaction ( r G o ) at a certain
Observe the following graphic representation of four
temperature can be computed as r G o r H o T. r So
basic thermodynamic processes.
and the change in the value of r H o and r So for a
reaction with temperature can be computed as follow:
Isobaric
Pressure r H oT2 r H oT1 r Cop (T2 T1 )
Isochoric
Isothermal
Adiabatic T
r STo2 r STo1 r Cop ln 2
T1
r G o r H o T. r So
Volume and by r G o RT ln K eq .
66. Which of the following is true for isochoric process ? Consider the following reaction:
(a) V = 0 (b) U = q + PV CH3OH(g)
CO(g) 2H 2 (g)
(c) U = qv (d) All of these
Given: f H o (CH3OH, g) = –201 kJ/mol;
67. Which of the following is not true for isothermal process ?
f H (CO,g) = –144 kJ/mol
o
V2 o o –1 –1
(a) wexp = –2.303 nRT log V S (CH3OH, g) = 240 J/K-mol; S (H2, g) = 29 JK mol
1 o
S (CO, g) = 198 J/mol-K; Cop, m (H 2 ) =28.8 J/mol-K
P1
(b) wexp = –2.303 nRT log P Cop, m (CO) =29.4 J/mol-K; Cop, m (CH3OH) = 44 J/mol-K
2
(c) T = 0 320
and ln 0.06 , all data at 300 K
(d) T1V11 T2 V21 300
CP 69. r So at 300 K for the reaction is :
68. If the ratio 1.30 , the atomicity of gas is
CV (a) 152.6 J/K-mol (b) 181.6 J/K-mol
(a) 1 (b) 2 (c) –16 J/K-mol (d) None of these
(c) 3 (d) 4 70. r H o at 300 K for the reaction is :
(a) –87 kJ/mol (b) 87 kJ/mol
(c) –315 kJ/mol (d) –288 kJ/mol
THERMODYNAMICS AND THERMOCHEMISTRY 221
EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTIONS
Objective Questions I [Only One Correct Option] (d) not defined, because pressure is not constant
1. The difference between heats of reaction at constant 7. Which of the following reactions defines Hºf ? (2003)
pressure and constant volume for the reaction (a) C(diamond) + O2(g) CO2 (g)
2C6H6 (l ) + 15O2(g) 12CO2(g) + 6H2O (l ) 1 1
(b) H 2 (g) F2 (g) HF(g)
at 25º C in kJ is (1991) 2 2
(a) – 7.43 (b) + 3.72 (c) N2 (g) + 3H2 (g) 2NH3(g)
1
(c) – 3.72 (d) + 7.43 (d) CO(g) O 2 (g) CO 2 (g)
2
2. For an endothermic reaction, where H represents the
8. Spontaneous adsorption of a gas on solid surface is an
enthalpy of the reaction in kJ/mol, the minimum value for
exothermic process because (2004)
the energy of activation will be (1992)
(a) H increases for system (b) S increases for gas
(a) less than H (b) zero
(c) S decreases for gas (d) G increases for gas
(c) more than H (d) equal to H
9. H vap = 30 kJ/mol and S vap = 75 Jmol –1 K–1 . Find
3. The Hºf for CO2(g), CO(g) and H2O (g) are – 393.5, – 110.5
temperature of vapour, at one atmosphere. (2004)
and – 241.8 kJ mol–1 respectively. The standard enthalpy
(a) 400 K (b) 350 K
change (in kJ mol–1) for the reaction
(c) 298 K (d) 250 K
CO2 (g) + H2(g) CO(g) + H2O(g) is. (2000)
10. 2 moles of an ideal gas expanded isothermally and reversibly
(a) 524.1 (b) + 41.2
from 1 L to 10 L at 300 K. What is the enthalpy change ?
(c) – 262.5 (d) – 41.2
4. In thermodynamics, a process is called reversible when (2004)
(2001) (a) 4.98 kJ (b) 11.47 kJ
(a) surroundings and system change into each other
(c) – 11.47 kJ (d) 0 kJ
(b) there is no boundary between system and surroundings
(c) the surroundings are always in equilibrium with the 11. When one mole of monoatomic ideal gas at TK undergoes
system adiabatic change under a constant external pressure of
(d) t he s ys t em c ha ng es in to t h e s u rr o u nd i n gs 1 atm changes volume from 1 L to 2 L. The final temperature
spontaneously
in kelvin would be (2005)
5. Which of the following statements is false ? (2001)
(a) Work is a state function T 2
(a) (b) T
2 2 /3 3 0.0821
(b) Temperature is a state function
2
(c) Change in the state is completely defined when the (c) T (d) T
initial and final states are specified 3 0.0821
(d) Work appears at the boundary of the system 12. A monoatomic ideal gas undergoes a process in which the
6. One mole of a non-ideal gas undergoes a change of state ratio of p to V at any instant is constant and equals to 1.
(2.0 atm, 3.0 L, 95 K) (4.0 atm, 5.0 L, 245 K) with a change What is the molar heat capacity of the gas ? (2006)
in internal energy, E = 30.0L-atm. The change in enthalpy
(H) of the process in L-atm is (2002) 4R 3R
(a) (b)
2 2
(a) 40.0 (b) 42.10
5R
(c) 44.0 (c) (d) 0
2
THERMODYNAMICS AND THERMOCHEMISTRY 222
13. The direct conversion of A to B is difficult, hence it is f G o [C(diamond)] = 2.9 kJ mol–1
carried out by the following shown path The standard state means that the pressure should be 1
C D bar, and substance should be pure at a given temperature.
The conversion of graphite [C(graphite)] to diamond
A B [C(diamond)] reduces its volume by 2 × 10–6 m3 mol–1. If
Given S(AC) = 50 eu C(graphite) is converted to C(diamond) isothermally at
T = 298 K, the pressure at which C(graphite) is in equilibrium
S(CD) = 30 eu
with C(diamond), is
S(DB) = 20 eu [Useful information : 1 J = 1 kg m2s–2,
where eu is entropy unit, then S(AB) is (2006) 1 Pa = 1 kg m–1 s–2; 1 bar = 105 Pa] (2017)
(a) 58001 bar (b) 1450 bar
(a) + 100 eu (b) + 60 eu
(c) 14501 bar (d) 29001 bar
(c) – 100 eu (d) – 60 eu Objective Questions II
14. For the process H2O (l ) (1 bar, 273 K) H2O(g) (1 bar, 373 [One or more than one correct option]
K), the correct set of themodynamic parameters is(2007) 19. Identify the intensive quantities from the following (1993)
(a) G = 0, S = +ve (b) G = 0, S = –ve (a) enthalpy (b) temperature
(c) volume (d) refractive index
(c) G = + ve, S = 0 (d) G = – ve, S = +ve
20. The following is (are) endothermic reaction (s) (1999)
15. The value of log10 K for a reaction A B is (a) combustion of methane
(Given : rHº298K = – 54.07 kJ mol , –1 (b) decomposition of water
rSº298 K = 10 JK–1 mol–1 and R = 8.314 JK–1 mol–1; (c) dehydrogenation of ethane to ethylene
(d) conversion of graphite to diamond
2.303 × 8.314 × 298 = 5705 (2010)
(a) 5 (b) 10 21. Among the following, the state function(s) is (are) (2009)
(c) 95 (d) 100 (a) internal energy
16. For the pocess (b) irreversible expansion work
(c) reversible expansion work
H 2O H2O g (d) molar enthalpy
at T = 100°C and 1 atmosphere pressure, the correct choice 22. An ideal gas in a thermally insulated vessel at internal
is (2014) pressure=P1, volume = V1, and absolute temperature =T1
(a) Ssystem > 0 and Ssurroundings > 0 expands irreversibly against zero external pressure as
(b) Ssystem > 0 and Ssurroundings < 0 shown in the diagram. The final internal pressure, volume
and absolute temperature of the gas are P2, V2 and T2,
(c) Ssystem < 0 and Ssurroundings > 0
respectively. For this expansion, (2014)
(d) Ssystem < 0 and Ssurroundings < 0
17. One mode of an ideal gas at 300 K in thermal contact with
surroundings expands isothermally from 1.0 L to 2.0 L
against a constant pressure of 3.0 atm. In this process, the
change in entropy of surroundings (Ssurr) in JK–1 is
(1L atm = 101.3 J) (2016)
(a) 5.763 (b) 1.013
(c) –1.013 (d) –5.763
18. The standard state Gibbs free energies of formation of
C(graphite) and C(diamond) at T = 298 K are (a) q = 0 (b) T2 = T1
–1
f G [C(graphite)] = 0 kJ mol
o
(c) P2V2 = P1V1 (d) P2 V2 P1V1
THERMODYNAMICS AND THERMOCHEMISTRY 223
23. An ideal gas is expanded from (p1, V1, T1) to (p2, V2, T2) 26. In thermodynamics the P-V work done is given by
under different conditions. The correct statement(s) among
w dVPext.
the following is (are) (2017)
(a) The work done by the gas is less when it is expanded For a system undergoing a particular process, the work
done is,
reversibly from V1 to V2 under adiabatic conditions as
RT a
compared to that when expanded reversibly from V1 to V2 w dV 2 .
under isothermal conditions. V b V
(b) The change in internal energy of the gas is (i) zero, if it The equation is applicable to a (2020)
is expanded reversibly with T1 = T2, and (ii) positive, if it is (a) System that satisfies the van der Waals equation of
expanded reversibly under adiabatic conditions with state.
T 1 T 2. (b) Process that is reversible and isothermal
(c) If the expansion is carried out freely, it is simultaneously (c) Process that is reversible and adiabatic
both isothermal as well as adiabatic (d) Process that is irreverisble and at constant isothermal.
(d) The work done on the gas is maximum when it is 27. An ideal gas undergoes a reversible isothermal expansion
compressed irrversibly from (p2, V2) to (p1, V1) against from state I to stable II followed by a reversible adiabatic
constant pressure p1. expansion from state II to state III. The correct plot(s)
24. A reversible cyclic process for an ideal gas is shown below, representing the changes from state I to state III is(are)
Here, P, V, and T are pressure, volume and temperature, (p : pressure, V : volume, T : tempeature, H : enthalpy,
respectively. The thermodynamic parameters q, w, H and S : entropy) (2021)
U are heat, work, enthalpy and internal energy, respectively.
(a) (b)
(c) (d)
The correct option(s) is (are) (2018)
(a) qAC = U BC and wAB = P2 (V2 – V1)
Numerical Value Type Questions
(b) w BC P2 (V2 V1 ) and q BC H AC
28. The enthalpy for the following reactions (Hº) at 25ºC are
(c) H CA U CA and q BC H AC given below
(d) q BC H AC and H CA U CA 1 1
(i) H (g) + O2(g) OH(g) Hº = –10.06 kcal
25. Choose the reaction(s) from the following options, for which 2 2 2
the standard enthalpy of reaction is equal to the standard (ii) H2(g) 2H(g) Hº = 104.18 kcal
enthalpy of formation (2019) (iii) O2 (g) 2O(g) Hº = 118.32 kcal
1 Calculate the O — H bond energy in the hydroxyl radical.
(a) S8 (s) O 2 (g)SO 2 (g)
8 (1981)
(b) 2H 2 (g) O 2 (g) 2H 2 O(l) 29. The standard heats of formation of CCl4(g), H2O(g), CO2(g)
3 and HCl(g) at 298 K are –25.5, –57.8, – 94.1 and –22.1
(c) O 2 (g) O3 (g) kcal/mol respectively. Calculate Hº (298 K) for the reaction
2
(d) 2C(g) 3H 2 (g) C 2 H 6 (g) CCl4(g) + 2H2O(g) CO2(g) + 4HCl(g) (1982)
THERMODYNAMICS AND THERMOCHEMISTRY 224
30. The molar heats of combustion of C2H2(g), C (graphite) Compound : H2(g) CH4(g) C2H6(g) C(graphite)
and H2(g) are 310.62 kcal, 94.05 kcal and 68.32 kcal Hº (kJ/mol) : –285.8 –890.0 –1560.0 –393.0
The standard heat of formation of C3H8(g) is –103 kJ/mol.
respectively. Calculate the standard heat of formation of
C2H2(g). (1983) (1992)
38. The polymerization of ethylene to linear polyethylene is
31. Given the following standard heats of reactions
represented by the reaction,
(i) heat of formation of water = – 68.3 kcal
n [CH2 [ CH 2 – CH 2 ]n
CH2]
(ii) heat of combustion of acetylene = – 310.6 kcal
where, n has large integral value. Given that the average
(iii) heat of combustion of ethylene = – 337.2 kcal
enthalpies of bond dissociation for C C and C—C at
Calculate the heat of reaction for the hydrogenation of 298 K are + 590 and +311 kJ/mol respectively, calculate the
acetylene at constant volume (25º C). (1984) enthalpy of polymerization per mole of ethylene at 298 K.
32. The bond dissociation energies of gaseous H2, Cl2 and (1994)
HCl are 104, 58 and 103 kcal/mol respectively. Calculate the 39. From the following data, calculate the enthalpy change
enthalpy of formation of HCl gas. (1985) for the combustion of cyclopropane at 298 K. The enthalpy
33. The standard molar heat of formation of ethane, carbon of formation of CO2(g), H2O (l) and propane (g) are –393.5,
dioxide and liquid water are –21.1, –94.1, and –68.3 kcal –285.8 and 20.42 kJ mol–1 respectively. The enthalpy
respectively. Calculate the standard molar heat of of isomerization of cyclopropane to propene is
combustion of ethane. (1986) –33.0 kJ mol–1. (1998)
34. An intimate mixture of ferric oxide, Fe2O3, and aluminium, 40. Estimate the average S–F bond energy in SF6. The values
Al, is used in solid fuel rockets. Calculate the fuel value of standard enthalpy of formation of SF6(g), S(g) and F(g)
per gram and fuel value per cc of the mixture. Heats of are :
formation and densities are as follows :
– 1100, 275 and 80 kJ mol–1 respectively. (1999)
Hf (Al2O3) = – 399 kcal/mol
41. A sample of argon gas at 1 atm pressure and 27ºC expands
Hf (Fe2O3) = – 199 kcal/mol reversibly and adiabatically from 1.25 dm3 to 2.50 dm3.
Density of Fe2O3 = 5.2 g/cc, Calculate the enthalpy change in this process C Vm for
Density of Al = 2.7 g/cc (1989)
argon is 12.49 JK–1 mol–1. (2000)
35. An athlete is given 100g of glucose (C6H12O6) of energy
42. Diborane is a potential rocket fuel which undergoes
equivalent to 1560 kJ. He utilizes 50 percent of this gained
combustion according to the reaction
energy in the event. In order to avoid storage of energy in
the body, calculate the weight of water the would need to B2 H 6 (g) + 3O2 (g)
B2O3 (s) + 3H 2O(g)
perspire. The enthalpy of evaporation of water is 44 kJ/mol.
From the following data, calculate the enthalpy change for
(1989)
the combustion of diborane. (2000)
36. The standard enthalpy of combustion at 25ºC of hydrogen,
3
cyclohexene (C6H10) and cyclohexane (C6H12) are –241, 2B(s) + O2 (g) B2O3 (s), H 1273 kJ mol 1
2
– 3800 and –3920 kJ/mol respectively. Calculate the heat of
1
hydrogenation of cyclohexene. (1989) H 2 (g) + O2 (g)
H 2O(l ), H 286 kJ mol 1
2
37. Determine the enthalpy of the reaction,
H 2 O(l )
H 2O(g), H 44 kJ mol1
C3H8(g) + H2(g) C2H6(g) + CH4(g), at 25ºC, using the
2B (s) + 3H 2 (g)
B2 H6 (g), H = 36 kJ mol –1
given heat of combustion values under standard conditions.
THERMODYNAMICS AND THERMOCHEMISTRY 225
43. In a constant volume calorimeter, 3.5g of a gas with
molecular weight 28 was burnt in excess oxygen at 298.0 K.
The temperature of the calorimeter was found to increases
from 298.0 K to 298.45 K due to the combustion process.
Given that the heat capacity of the calorimeter is 2.5 kJ K–1,
the numerical value for the enthalpy of combustion of the
gas in kJ mol–1 is (2009) (U : Internal energy, S : entropy, p : pressure, V : volume,
44. The surface of copper gets tarnished by the formation of R : gas constant)
copper oxide. N2 gas was passed to prevent the oxide (Given : molar heat capacity at constant volume, CV.m of
formation during heating of copper at 1250 K. However, 5
the gas is R)
2
the N2 gas contains 1 mole % of water vapour as impurity.
47. 2 mol of Hg(g) is combusted in a fixed volume bomb
The water vapour oxidises copper as per the reaction given
below : (2018) calorimeter with excess of O2 at 298 K and 1 atm into
HgO(s). During the reaction, temperature increases from
2Cu(s) + H2O(g) Cu2O(s) + H2(g)
298.0 K to 312.8 K. If heat capacity of the bomb calorimeter
p H 2 is the minimum partial pressure of H2 (in bar) needed
and enthalpy of formation of Hg(g) are 20.00 kJK 1 and
to prevent the oxidation at 1250 K. The value of ln (p H2 ) is 61.32 kJ mol 1 at 298 K, respectively, the calculated
......... . standard molar enthalpy of formation of HgO(s) at 298 K is
(Given : total pressure = 1 bar, R (universal gas constant) X kJ mol 1 . The value of X is _______.
= 8J K mol , ln (10) = 2.3. Cu(s) and Cu2O(s) are mutually
–1 –1
immiscible. [Given: Gas constant R = 8.3 JK 1 mol 1 ] (2022)
45. Tin is obtained from cassiterite by reduction with coke.
48. One mole of an ideal monoatomic gas undergoes two
Use the data given below to determine the minimum
reversible processes ( A B and B C ) as shown in
tempeature (in K) at which the reduction of cassiterite by
the given figure.
coke would take place. (2020)
At 298 K : f H 0 (SnO 2 (s)) 581.0kJmol1 ,
f H 0 (CO 2 (g)) 394.0 kJ mol 1
S0 (SnO 2 (s)) 56.0JK 1mol 1 ,S0 (Sn(s)) 52.0 JK 1mol1
S0 (C(s)) 6.0JK 1 mol1 ,S0 (CO 2 (g)) 210.0 J K 1mol 1
Assume that the enthalpies and the entropies are
temeprature independent.
46. One mole of an ideal gas at 900 K, undergoes two reversible
processes, I followed by II, as shown below. If the work
done by the gas in the two processes are same, the value
v3
of ln v is _________. (2021)
2
THERMODYNAMICS AND THERMOCHEMISTRY 226
A B is an adiabatic process. If the total heat absorbed Subjective Type Questions
in the entire process ( A B and B C ) is RT2 ln10, 52. Following statement is true only under some specific
conditions. Write the conditions for that in not more than
the value of 2 logV3 is _____. two sentences
[Use, molar heat capacity of the gas at constant “The heat energy q, absorbed by a gas is H.” (1984)
53. In order to get maximum calorific output, a burner should
5 have an optimum fuel to oxygen ratio which corresponds
pressure, C p , m R] (2023)
2 to 3 times as much oxygen as is required theoretically for
complete combustion of the fuel. A burner which has been
Assertion Reason adjusted for methane as fuel (with x litre/hour of CH4 and
(A) If both Assertion and Reason are correct and 6x litre/hour of O2) is to be readjusted for butane, C4H10. In
Reason is the correct explanation of Assertion. order to get the same calorific output, what should be the
rate of supply of butane and oxygen ? Assume that losses
(B) If both Assertion and Reason are true but due to incomplete combustion etc., are the same for both
Reason is not the correct explanation of fuels and that the gases behave ideally. Heats of
Assertion. combustions :
(C) If Assertion is true but Reason is false. CH4 = – 809 kJ/mol, C4H10 = – 2878 kJ/mol (1993)
(D) If Assertion is false but Reason is true. 54. The standard enthalpies of formation of cyclohexane (l)
and benzene (l) at 25ºC are –156 and +49 kJ mol–1
49. Assertion (A) : The heat absorbed during the isothermal
respectively. The standard enthalpy of hydrogenation of
expansion of an ideal gas against vacuum is zero.
cyclohexene (l) at 25ºC is –119 kJ mol–1. Use these data to
Reason (R) : The volume occupied by the molecules of an
estimate the magnitude of the resonance energy of
ideal gas is zero. (2000)
benzene. (1996)
(a) A (b) B
55. Show that the reaction,
(c) C (d) D
1
50. Assertion (A) : For every chemical reaction at equilibrium CO(g) + O2 (g) CO 2 (g) at 300 K, is spontaneous
standard Gibbs’ energy of reaction is zero. 2
and exothermic, when the standard entropy change is
Reason (R) : At constant temperature and pressure,
chemical reactions are spontaneous in the direction of –0.094 kJ mol–1 K–1. The standard Gibbs’ free energies of
decreasing Gibbs’ energy. (2008) formation for CO2 and CO are –394.4 and –137.2 kJ mol–1,
(a) A (b) B respectively. (2000)
(c) C (d) D 56. When 1-pentyne (A) is treated with 4 N alcoholic KOH at
175ºC, it is converted slowly into an equilibrium mixture of
51. Assertion (A) : There is a natural asymmetry between 1.3% 1-pentyne (A), 95.2% 2-pentyne (B) and 3.5% of 1,
converting work to heat and converting heat to work. 2-pentadiene (C). The equilibrium was maintained at 175ºC.
Reason (R) : No process is possible in which the sole Calculate Gº for the following equilibria.
result is the absorption of heat from a reservoir and its A,
B G o ?
1
complete conversion into work. (2008)
C,
B G o2 ?
(a) A (b) B
(c) C (d) D From the calculated value of G1o and G o2 indicate the
order of stability of (A), (B) and (C). Write a reasonable
reaction mechanism showing all intermediates leading to
(A), (B) and (C) (2001)
THERMODYNAMICS AND THERMOCHEMISTRY 227
57. Two moles of a perfect gas undergo the following Paragraph Type Questions
processes :
Use the following passage, to solve Q. 68 to Q. 69
(a) a reversible isobaric expansion from (1.0 atm, 20.0L) to
(1.0 atm, 40.0 L) Passage
(b) a reversible isochoric change of state from (1.0 atm, The entropy versus temperature plot for phases and
40.0 L) to (0.5 atm, 40.0 L) at 1bar pressure is given.
(c) a reversible isothermal compression from (0.5 atm, 40.0L) ST and S0 are entropies of the phases at temperatures T
to (1.0 atm, 20.0 L)
and 0 K, respectively.
(i) Sketch with labels each of the processes on the same
p-V diagram.
(ii) Calculate the total work (W) and the total heat change
(Q) involved in the above processes.
(iii) What will be the values of U, H and S for the
overall process ? (2002)
3R 3R
58. CV value of He is always but CV value of H2 is at
2 2
5R
low temperature and at moderate temperature and more
2
5R
than at higher temperature. Explain in two or three
2
lines. (2003)
The transition temperature for and phase change is
59. 100 mL of a liquid contained in an isolated container at a
pressure of 1 bar. The pressure is steeply increased to 100 600 K and CP , and CP, CP. 1 J mol 1 K 1 .
bar. The volume of the liquid is decreased by 1 mL at this
constant pressure. Find the H and U. (2004) Assume CP , CP. is independently of temperature in
Fill in the Blanks
the range of 200 to 700 K. CP. and CP , are heat
60. The total energy of one mole of an ideal monatomic gas at
27ºC is ..................... cal. (1984) capacities of and phases, respectively..
61. Cp – CV for an ideal gas is .................. (1984) 68. The value of entropy change S S , (in J mol 1 K 1 ),
62. A system is said to be ............. if it can neither exchange at 300 K is ____.
matter nor energy with the surroundings. (1993)
[Use: ln 2 0.69
63. The heat content of the products is more than that of the
reactants in an ................. reaction. (1993) Given: S S 0 at 0 K] (2023)
64. When Fe(s) is dissolved in aqueous hydrochloric acid in a
closed vessel, the work done is .................. . (1997) 69. The value of enthalpy change, H H (in J mol 1 ), at
300 K is ____. (2023)
65. Enthalpy is an ............... property. (1997)
True / False
66. First law of thermodynamics is not adequate in predicting
the direction of a process. (1982)
67. Heat capacity of a diatomic gas is higher than that of a
monatomic gas. (1985)
THERMODYNAMICS AND THERMOCHEMISTRY 228
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ANSWER KEY 229
Answer Key
CHAPTER -5 REDOX REACTION
EXERCISE - 1 : EXERCISE - 2 :
BASIC OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAIN QUESTIONS
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1. (b) 2. (b) 3. (a) 4. (b) 5. (b) 1.(a) 2.(a) 3.(c) 4.(b) 5.(c)
6. (b) 7. (d) 8. (d) 9. (c) 10. (c) 6.(c) 7.(c) 8.(12.00) 9.(173.0) 10.(4.00)
11. (b) 12. (d) 13. (c) 14. (d) 15. (a) 11.(6.00) 12.(25.0) 13. (6.00) 14.(16.0) 15.(24.0)
16. (d) 17. (c) 18. (b) 19. (a) 20. (c) 16. (50.0) 17.(18.0) 18.(1575.0)19. (316.0)
21. (a) 22. (a) 23. (d) 24. (b) 25. (a) 20. (a) 21. (c) 22. (a) 23. (a) 24. (a)
25. (d) 26. 13 27. 30 28. 4 29. 24
26. (a) 27. (a) 28. (a) 29. (c) 30. (d)
30. 1 31. 5 32. (d) 33. (a) 34. (b)
31. (a) 32. (a) 33. (d) 34. (a) 35. (c)
35. (b) 36. (c) 37. (b) 38. (b) 39. (4)
36. (c) 37. (b) 38. (c) 39. (a) 40. (c) 40. (6.00) 41. (10) 42. (3.00) 43. (6)
41. (d) 42. (d) 43. (a) 44. (c) 45. (b) 44. (5) 45. (1) 46. (68) 47. (23.00)
46. (b) 47. (a) 48. (b) 49. (a) 50. (b)
51. (b) 52. (a) 53. (d) 54. (b)
ANSWER KEY 230
CHAPTER -5 REDOX REACTION
EXERCISE - 3 : EXERCISE - 4 :
ADVANCED OBJECTIVE QUESTIONS PREVIOUS YEAR JEE ADVANCED QUESTIONS
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1. (a) 2. (c) 3. (c) 4. (a) 5. (b) 1. (b) 2. (b) 3. (a) 4. (a) 5. (b)
6. (d) 7. (b) 8. (a) 9. (c) 10. (a) 6. (d) 7. (a) 8. (d) 9. (a) 10. (c)
11. (a) 12. (b) 13. (a) 14. (b) 15. (a) 11. (b) 12. (d) 13. (b) 14. (c) 15. (a,b,d)
16. (b) 17. (d) 18. (a) 19. (d) 20. (a) 16. (c) 17. (b) 18. (7/3) 19. (3.00) 20. (2.00)
21. (a,b,d) 22. (a,b,c)23. (c,d) 24. (a,b) 21. (5.00)
25. (a,c,d) 26. (a,b) 27. (c,d) 28. (a,c,d)
22. ( i 37.92;ii 0.065;iii 7.73 and 3.86 )
29. (a,b,c) 30. (a,d) 31. (a,c) 32. (M/8)
33. (+3) 34. (7.00)35. (7.00) 36. (.00) 37. (2g/L) 24. (2) 25. (6.5g/L) 26. (6.5g)
38. (1.00) 39. (c) 40. (a) 41. (a) 42. (a) 27. (16.67 mL) 29. (1.12g) 30. (1:2)
43. (a) 31. ( 1.04 1021 ) 32. (26.5%) 33. (85%) 34.
44. ( A q; B q;C r; D s; E p ) (4.48%) 35. (50%, 20%, 30%)
45. ( A p; B q; C r; D s; E t ) 36. (49.33%, 34.8%) 37. (1.33V) 38. (0.06)
39. (8.1 mL) 40. (0.1 M)
46. ( A q;B p;C s; D r ) 41.(1008 gm) 42.(126.00)
47. ( A s; B q;C r; D p )48. (c) 49. (d) 43. (288.00) 44.(0.11)
50. (a) 51. (c) 52. (a) 53. (a) 54. (d) 45.(6.00) 46. (0.32)
55. (d)
ANSWER KEY 231
Answer Key
CHAPTER -6 GENERAL ORGANIC CHEMISTRY
EXERCISE - 1 : EXERCISE - 2 :
BASIC OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAIN QUESTIONS
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1. (a) 2. (c) 3. (d) 4. (d) 5. (d) 1. (a) 2. (b) 3. (a) 4. (b) 5. (c)
6. (a) 7. (c) 8. (c) 9. (c) 10. (b) 6. (d) 7. (b) 8. (d) 9. (a) 10. (d)
11. (b) 12. (a) 13. (c) 14. (a) 15. (c) 11. (c) 12. (b) 13. (a) 14. (c) 15. (d)
16. (c) 17. (a) 18. (b) 19. (d) 20. (b) 16. (d) 17. (5.00) 18. (6.00) 19. (10.00) 20. (60.00)
21. (a) 22. (c) 23. (d) 24. (d) 25. (d) 21. (a) 22. (c) 23. (d) 24. (d) 25. (c)
26. (b) 27. (b) 28. (a) 29. (c) 30. (d) 26. (a) 27. (b) 28. (c) 29. (d) 30. (a)
31. (a) 32. (b) 33. (a) 34. (d) 35. (d) 31. (c) 32. (b) 33. (b) 34. (b) 35. (d)
36. (b) 37. (d) 38. (d) 39. (a) 40. (d) 36. (d) 37. (a) 38. (c) 39. (c) 40. 3
41. (d) 42. (d) 43. (a) 44. (c) 45. (d) 41. 6 42. 3 43. 1 44. 1 45. 42
46. 3 47. (b) 48. (a) 49. (a) 50. (d)
46. (c) 47. (b) 48. (b) 49. (a) 50. (c)
51. (b) 52. (c) 53. (c) 54. (b) 55. (d)
51. (b) 52. (d) 53. (d) 54. (b) 55. (c) 56. (d) 57. (c) 58. (d) 59. (a) 60. (c)
56. (c) 57. (a) 58. (d) 59. (d) 60. (a) 61. (7)
61. (c) 62. (b) 63. (d) 64. (a) 65. (c)
66. (c) 67. (a) 68. (b) 69. (b) 70. (b)
71. (a) 72. (c) 73. (d) 74. (c) 75. (d)
76. (a) 77. (d) 78. (a) 79. (c) 80. (d)
81. (d) 82. (a) 83. (d) 84. (d) 85. (b)
86. (c) 87. (c) 88. (d) 89. (d) 90. (b)
91. (c) 92. (c) 93. (a) 94. (c) 95. (c)
ANSWER KEY 232
CHAPTER -6 GENERAL ORGANIC CHEMISTRY
EXERCISE - 3 : EXERCISE - 4 :
ADVANCED OBJECTIVE QUESTIONS PREVIOUS YEAR JEE ADVANCED QUESTIONS
DIRECTION TO USE -
DIRECTION TO USE -
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Scan the QR code and check detailed solutions.
1. (d) 2. (d) 3. (a) 4. (b) 5. (c) 1. (b) 2. (d) 3. (b) 4. (b) 5. (b)
6. (d) 7. (a) 8. (a) 9. (a) 10. (a) 6. (c) 7. (a) 8. (a) 9. (c) 10. (c)
11. (a) 12. (c) 13. (d) 14. (b) 15. (c) 11. (a) 12. (d) 13. (b) 14. (d) 15. (b)
16. (c) 17. (c) 18. (d) 19. (c) 20. (b) 16. (c) 17. (a) 18. (b,c) 19. (c,d) 20. (b,c)
21. (b) 22. (d) 23. (d) 24. (c) 25. (a) 21. (5.00)
26. (b) 27. (c) 28. (c) 29. (a) 30. (d)
31. (b) 32. (c) 33. (d) 34. (b) 35. (d)
36. (a) 37. (a) 38. (d) 39. (b) 40. (a)
41. (a) 42. (c) 43. (c) 44. (c) 45. (a, b)
46. (a, c) 47. (a,b,c,d) 48. (a,b,c,d)
49. (a,b,d) 50. (d)
51. (c) 52. (a) 53. (b) 54. (a) 55. (a)
56. (c) 57. (a) 58. (b) 59. (b) 60. (a)
61. (A – P, S; B – Q, R; C – Q, S; D – P, S)
62. (A – Q, R; B – P, S; C – Q, R; D – Q, R)
63. (a) 64. (b) 65. (c) 66. (c) 67. (d)
ANSWER KEY 233
Answer Key
CHAPTER -7 HYDROCARBONS
EXERCISE - 1 : EXERCISE - 2 :
BASIC OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAIN QUESTIONS
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1. (b) 2. (b) 3. (b) 4. (b) 5. (a) 1. (a) 2. (b) 3. (c) 4. (b)
6. (d) 7. (c) 8. (a) 9. (c) 10. (c) 5. (a) 6. (c) 7. (d) 8. (a) 9. (b)
11. (a) 12. (c) 13. (d) 14. (c) 15. (d) 10. (b) 11. (b) 12. (d) 13. (a) 14. (a)
16. (b) 17. (d) 18. (c) 19. (c) 20. (a) 15. (b) 16. (d) 17. (a) 18. (d) 19. (b)
21. (c) 22. (d) 23. (b) 24. (b) 25. (d) 20. (d) 21. (a) 22. (a) 23. (a) 24. (b)
26. (d) 27. (c) 28. (c) 29. (c) 30. (d) 25. (c) 26. (b) 27. (7.00) 28. (3.00)
31. (b) 32. (b) 33. (c) 34. (b) 35. (b) 29. (a) 30. (b) 31. (b) 32. (a) 33. (d)
36. (a) 37. (a) 38. (b) 39. (d) 40. (c) 34. (a) 35. (c) 36. (c) 37. (d) 38. (d)
41. (b) 42. (c) 43. (b) 44. (c) 45. (d) 39. (c) 40. (d) 41. (c) 42. (d) 43. (d)
46. (b) 47. (c) 48. (d) 49. (a) 50. (b) 44. (a) 45. (b) 46. (c) 47. (b) 48. (c)
49. 2 50. 8 51. 6 52. 3 53. (d)
51. (d) 52. (a) 53. (b) 54. (c) 55. (d)
54. (a) 55. (c) 56. (a) 57. (b) 58. (d)
56. (d) 57. (b) 58. (c) 59. (c) 60. (c)
59. (a) 60. (b) 61. (d) 62. (a) 63. (d)
61. (a) 62. (c) 63. (d) 64. (b) 65. (d) 64. (d) 65. (b) 66. (d) 67. (c) 68. (c)
66. (d) 67. (b) 68. (b) 69. (c) 70. (c) 69. (d) 70. (a) 71. (a) 72. (d) 73. (c)
71. (d) 72. (d) 73. (a) 74. (a) 75. (b) 74. (b) 75. (3) 76. (3) 77. (9.00) 78. (70)
76. (b) 77. (a) 78. (b) 79. (b) 80. (b)
ANSWER KEY 234
CHAPTER -7 HYDROCARBONS
EXERCISE - 3 : EXERCISE - 4 :
ADVANCED OBJECTIVE QUESTIONS PREVIOUS YEAR JEE ADVANCED QUESTIONS
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Scan the QR code and check detailed solutions.
1. (c) 2. (c) 3. (d) 4. (d) 5. (a) 1.(a) 2.(b) 3.(c) 4.(d) 5.(b)
6. (d) 7. (a) 8. (c) 9. (d) 10. (d) 6.(a) 7.(a) 8.(d) 9.(a) 10. (a)
11. (b) 12. (b) 13. (c) 14. (d) 15. (c) 11.(b) 12.(d) 13.(5) 14.(2) 15.(0)
16. (b) 17. (b) 18. (b) 19. (a) 20. (d) 16.(2) 17.(c) 18.(a) 19.(d) 20. (b)
21. (b) 22. (b,c,d) 23. (a,b,d) 24. (a,c,d) 25. (a,b) 21.(a) 22.(c) 24. (a,c)
26. (a,cd) 27. (a,b,c,d) 28. (a,b) 29. (b,c)
30. (a,b,c,d) 31. (a,c) 32. (a,b,c) 33. (a,b)
34. (c,d) 35. (1.00) 36. (2.00) 37. (5.00) 38. (6.00)
39. (4.00)40. (5.00) 41. (6.00) 42. (d) 43. (a)
44. (d) 45. (a) 46. (a) 47. (b) 48. (d)
49. (a) 50. (a) 51. (a)
52. (a-Q, R; b-Q, R; c-P; d-P,S)
53. (a-P,S; b-P,Q,R; c-Q,R; d-P,Q,S)
54. (d) 55. (c) 56. (d) 57. (c) 58. (c)
59. (b) 60. (a) 61. (b) 62. (c) 63. (c)
64. (c) 65. (c)
ANSWER KEY 235
Answer Key
CHAPTER -8 THERMODYNAMICS AND THERMOCHEMISTRY
EXERCISE - 1 : EXERCISE - 2 :
BASIC OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAINS QUESTIONS
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1. (a) 2. (d) 3. (a) 4. (a) 5. (c) 1.(b) 2. (741.00) 3.(15.00) 4.(200.00)
6. (c) 7. (d) 8. (b) 9. (b) 10. (b) 5.(309.00) 6. (–2218.00) 7. (230.00) 8.(128.00)
11. (c) 12. (a) 13. (c) 14. (b) 15. (d) 9. (667.00) 10. (336.00) 11.(–21.00)
16. (d) 17. (d) 18. (c) 19. (a) 20. (c) 12. (101.00) 13. (–50.00) 14.(82.00)
21. (b) 22. (a) 23. (b) 24. (b) 25. (b) 15. (31.00)16. (38.00) 17.(82.00)
26. (d) 27. (c) 28. (b) 29. (b) 30. (c) 18. (964.00) 19. (–5.00)
31. (d) 32. (a) 33. (b) 34. (b) 35. (a) 20. (c) 21. (c) 22. (b) 23. (a) 24. (a)
25. (d) 26. 727 27. 38 28. 8630 29. 0
36. (a) 37. (d) 38. (b) 39. (b) 40. (c)
30. 600 31. 117 32. 195 33. 104 34. 2
41. (c) 42. (b) 43. (b) 44. (a) 45. (c) 35. 200 36. 57 37. 2 38. 35 39. 3
46. (c) 47. (d) 48. (c) 49. (a) 50. (d) 40. 54 41. (b) 42. (d) 43. (d) 44. (c)
51. (a) 52. (b) 53. (d) 54. (b) 55. (b) 45. (2) 46. (620) 47. (360) 48. (847) 49. (6)
56. (a) 57. (c) 58. (a) 59. (b) 60. (a) 50. (0) 51. (150) 52. (610) 53. (173) 54. (499)
61. (c) 62. (a) 63. (d) 64. (c) 65. (c) 55. (1006)56. (10) 57. (2) 58. (278) 59. (1200)
66. (c) 67. (d) 68. (d) 69. (b) 70. (b) 60. (1411) 61. (4) 62. (4) 63. (4) 64. (3)
71. (d) 72. (b) 73. (c) 74. (a) 75. (c) 65. (1070) 66. (800)
76. (a) 77. (d) 78. (a) 79. (a) 80. (b)
81. (b) 82. (a) 83. (b) 84. (c) 85. (c)
86. (d) 87. (b) 88. (b) 89. (a) 90. (c)
91. (c) 92. (d) 93. (d) 94. (c) 95. (a)
96. (d) 97. (c) 98. (c) 99. (d) 100. (a)
101. (d) 102. (b) 103. (c) 104. (b) 105. (b)
106. (a) 107. (d) 108. (b) 109. (b) 110. (b)
111. (b) 112. (d) 113. (a) 114. (b) 115. (a)
116. (a) 117. (d) 118. (b) 119. (d) 120. (b)
ANSWER KEY 236
CHAPTER -8 THERMODYNAMICS AND THERMOCHEMISTRY
EXERCISE - 3 : EXERCISE - 4 :
ADVANCED OBJECTIVE QUESTIONS PREVIOUS YEAR JEE ADVANCED QUESTIONS
DIRECTION TO USE - DIRECTION TO USE -
Scan the QR code and check detailed solutions. Scan the QR code and check detailed solutions.
1. (a) 2. (a) 3. (d) 4. (a) 5. (d) 1. (a) 2. (c) 3. (b) 4. (c) 5. (a)
6. (c) 7. (a) 8. (a) 9. (a) 10. (b) 6. (c) 7. (b) 8. (c) 9. (a) 10.(d)
11. (c) 12. (b) 13. (d) 14. (b) 15. (b) 11.(d) 12.(a) 13.(a) 14. (a) 15.(b)
16. (c) 17. (c) 18. (d) 19. (d) 20. (c) 16.(b) 17.(c) 18.(c) 19. (b,d)
21. (b) 22. (a) 23. (b) 24. (a) 25. (b) 20.(b,c,d) 21.(a,c,d)
26. (b) 27. (a) 28. (d) 29. (a) 30. (a)
22.(a,b,c) 23.(a,c,d)
31. (c) 32. (b) 23. (c) 34. (c) 35. (a)
24.(b, c) 25. (a, c)
36. (b) 37. (d) 38. (c) 39. (b) 40. (a)
41. (b) 42. (a) 43. (b) 44. (b) 45. (b) 26. (a, b, c) 27. (a, b, d)
46. (b) 47. (d) 48. (a, d) 49. (c,d) 50. (b, d) 28.(121.31) 29.(-41.4)
51. (a, b, c) 52. (6.00) 53. (4.00) 54. (1.00) 30.(-54.2) 31.(41.104)
55. (8.00) 56. (b) 57. (a) 58. (d) 32.(22.0) 33.(-372.0)
59. (a) 60. (c) 61. (b) 62. (a) 63. (d) 34.(3.94) 35.(319.1)
64. (A p, q, r) ; (B p, s); (C p, q, r); D (p, r,s) 36.(-121.0) 37.(-55.7)
65. (A p,q) ; (B p, q); (C s); (D r)
38.(72.0) 39.(-2091.32)
66. (d) 67. (c) 68. (c) 69. (c) 70. (a) 40.(309.16) 41.(-115.41)
42.(-2035.0) 43.(9.00)
44.(-14.6) 45. (935.00)
46. (10.00) 47.(90.39) 48.(7) 49.(b)
50.(c) 51.(b)
60.(900) 61.(R)
62.(Isolated) 63.(Exothermic rection)
64.(Zero) 65.(Extensive)
66.True 67.True 68.(0.31)
69.(300)
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