Chemistry Part II Chapter#10 (Alkyl Halides)
SHORT QUESTIONS
1. What are primary and tertiary alkyl halides? Give one example of each.
Ans: Primary alkyl halides:
The alkyl halides in which halogen atom is attached to a carbon atom which is
further attached with one carbon atom or no carbon atom are called primary alkyl
halides.
Tertiary alkyl halides:
The alkyl halides in which halogen atom is attached to a carbon atom which is
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further attached with three carbon atoms are called tertiary alkyl halides.
Examples:
Primary alkyl halide:
CH3-Br
Methyl bromide
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Tertiary alkyl halide:
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H3C C Cl
CH3
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2-Chloro-2-methylpropane
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2. How alkyl halides can be prepared by alcohols? Give two examples.
Ans: (a) Reaction of alcohols with halogen acids:
Alcohols may be converted to the corresponding alkyl halides by the
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action of halogen acid in the presence of ZnCl2, which acts as a catalyst
ZnCl2
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CH3CH2 – OH + HX CH3CH2 – X + H2O
Ethyl halide
(b) Reaction of alcohols with thionyl chloride:
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Alcohols react with thionyl chloride in pyridine as a solvent to give alkyl
chlorides. This is the best method because HCl, and SO2 gases escape
leaving behind the pure product.
Pyridine
ROH + SOCl2 R – Cl + SO2 + HCl
3. Write down reactions of ethanol with (i) PBr3 (ii) PCl5
Ans: Reactions of ethanol with phosphorus halides:
Phosphorus tribromide and Phosphorus pentachloride react with Ethanol to
produce alkyl halides as follows.
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3CH3 CH2 OH + PBr3 3CH3 CH2 Br + H3PO3
CH3 CH2 OH + PCl5 CH3 CH2 Cl + POCl3 + HCl
4. Explain the order of reactivity of alkyl halides on the basis of bond polarity.
Ans: According to this factor, greater the electronegativity difference between carbon
and halogen greater the bond polarity. Greater the polarity greater the reactivity.
So with this rule the alkyl fluorides should be the most polar and the most reactive
and alkyl iodides least polar and least reactive.
It means reactivity order must be like this;
R-F>R-Cl>R-Br>R-I
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5. What is the order of reactivity of HX with Ethene?
Ans: Ethene reacts with HX to form Ethyl halide.
CH2 = CH2 + HX CH3 CH2-X
The order of reactivity of HX is given below.
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Hl > HBr > HCl > HF
6. How the bond dissociation energy of carbon suggests that alkyl iodides should have
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maximum reactivity?
Ans: Bond energy directly depends on bond polarity. The bond dissociation energy of
C-X bond is in the order:
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C F > C Cl > C Br > C I
Greater the bond energy, stronger the bond and lesser the reactivity. With this rule
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the reactivity order must be like this;
R-I>R-Br>R-Cl>R-F
Alkyl iodides should be most reactive due to least bond energy.
7. What is Wurtz’s synthesis reaction?
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Ans: Alkyl halides react with sodium in ether (solvent) to give alkanes. This is called
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Wurtz’s synthesis. The reaction is particularly useful for preparation of
symmetrical alkanes with double number of carbon atoms as compared with that
in alkyl halide used.
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Ether
CH3 CH2 Cl + 2Na + Cl CH2 CH3 CH3 CH2 CH2 CH3 + 2NaCl
n-Butane
8. What is difference between molecularity and order of reaction?
Ans:
Molecularity Order of Reaction
Molecularity is defined as the number of Sum of exponents of conc. terms in the
molecules taking part in the rate rate expression of a chemical equation is
determining step of reaction. called order of reaction.
It is calculated through balanced chemical It is always experimentally determined.
equation
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9. How antiknocking agents are prepared?
Ans: Preparation of anti-knocking agents:
Methyl chloride and Ethyl chloride can react with sodium lead alloy to produce
anti-knocking agents, Tetramethyl lead and Tetraethyl lead respectively.
4CH3Cl + Na4Pb (CH3)4Pb + 4NaCl
Tetramethyl lead
4CH3CH2 Cl + Na4Pb (CH3CH2)4Pb + 4NaCl
Tetraethyl lead
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10. In tertiary alkyl halides, SN1 reaction takes place but not SN2 reaction. Why?
Ans In ter-alky halide, attacking neucleophile cannot reach directly at the electrophilic
center (carbon) due to steric hindrance. So attachment of attacking nucleophile and
removal of leaving group can’t occur simultaneously as occurs in S N2 reactions. As a
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result in tertiary alkyl halides nucleophilic substitution occurs in two steps i.e. S N1
mechanism occurs. In first step halogen (leaving group) is removed to reduce steric
hindrance and planar carbocation is formed. In second step attack of new nucleophile
takes place.
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11. What is the role of Carbonium ion for determining SN1 or SN2 mechanism?
Ans: Greater the stability of the carbonium ion, greater the possibility for two step
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mechanism which is SN1. These alkyl halides which can provide unstable carbonium ion
give SN2 mechanism, which is a single step reaction. Carbonium ion is stable if it is
bonded to maximum number of alkyl groups.
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12. What is meant by attacking nucleophile? Give examples.
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Ans: In SN reactions, the nucleophile which attacks on the electrophilic carbon of alkyl
halide from outside is called attacking nucleophile.
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Examples:
-OH-, -CN etc.
13. Reaction of Ethyl bromide with OH nucleophile is SN2. Why?
Ans: Reaction of ethyl bromide with OH is SN2 because it is a bimolecular reaction.
The rate of reaction depends upon the concentration of nucleophile as well as
substrate.
CH3 CH2 Br + OH- CH3 CH2OH + Br-
Rate =k [CH3CH2Br][OH]
Order = 2
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14. What is difference between Electrophile and Nucleophile?
Ans:
Electrophile Nucleophile
(i) It is an electron deficient species. It is electron rich species.
(ii) It always acts as Lewis acid. It always acts as Lewis base.
(iii) It may be neutral or positively It may be negatively charged or neutral
charged. with one or more lone pairs.
(iv) Examples: NO2+, SO3 Examples: Cl-, NH3
15. What are differences between SN1 and SN2 reactions?
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Ans:
SN1 SN1
(i) It is a two step mechanism. It is a single step mechanism.
(ii) First step is slow and second is fast. It has only one step and that is slow.
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(iii)It is unimolecular reaction. It is a bimolecular reaction.
(iv)It is a favored in polar solvents.
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16. Why tertiary alkyl halides follow SN1 mechanism and not SN2 mechanism? OR
During SN1 reaction, what is the significance of first step?
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Ans: SN1 mechanism involves two steps. Due to steric (space) hindrance, the attack of
nucleophile on the ɑ-carbon of substrate is not directly possible. In order to create
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space for the attack, older nucleophile means halogen needs to be removed first.
This is the reason that reaction occurs in two steps. The first step is the reversible
ionization of the alkyl halide. This step provides a carbocation as an
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intermediate. In the second step this carbocation is attacked by the nucleophile to
give the substitution product.
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In SN2 reactions, the there is no issue of steric hindrance as ɑ-carbon of primary
alkyl halide is surrounded by small groups e.g. Hydrogen atoms and attacking
nucleophile finds space to attack on carbon.
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17. What are leaving group and substrate?
Ans: Leaving Group:
Leaving group (L) is also a nucleophile. In SN reactions of alkyl halides, the
halogens are the leaving groups. It is called leaving group because it departs from
alkyl halide.
Examples:
Cl, Br, I, HSO4
Substrate Molecule:
The alkyl halide molecule on which a nucleophile attacks is called a substrate
molecule.
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18. What is difference between Elimination and substitution reactions?
Ans:
Elimination substitution
Elimination of two atoms or groups from Substitution reaction involves the
adjacent carbon atoms in the presence of breakage of C-X bond and the formation
a nucleophile or a base is called of C-Nu bond.
elimination reaction.
The product of an elimination reaction is Substitution reaction yields substitution
alkene usually. product
Example: Example:
CH3CH2X+OH− H2C=CH2+ H2O CH3-X + OH- CH3-OH + X-
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19. How do we get alkyl nitriles from Grignard’s reagent?
Ans: When ClCN is reacted with Grignard’s reagent. The alkyl group of the Grignard’s
reagent combines with CN group to give Alkyl nitrile. See example below;
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Ether
CH 3 CH2 Mg Br + Cl CN CH3 CH2 CN + Mg
Cyanogen chloride
Cl
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20. Explain the structure and reactivity of Grignard’s reagent.
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Ans: Grignard’s reagent are much reactive than most of the organic compounds. The
reactivity is due to the nature of C-Mg bond which is highly polar.
CH 3 CH 2 Mg X
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Magnesium is more electropositive than carbon and C-Mg bond though covalent
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is highly polar, giving alkyl carbon the partial negative charge. The negative charge is an
unusual character which makes the alkyl groups highly reactive towards electrophilic
centers.
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21. What is the nature of C-Mg bond in R-Mg-X?
Ans: Grignard’s reagents are very reactive organic compounds. Their reactivity is due to
C-Mg bond which is highly polar.
CH3CH2 Mg X
Magnesium is less electronegative that carbon so partial positive charge appears on
magnesium and partial negative on carbon attached to it. This –ve charge on carbon is
very unusual which makes alkyl group very reactive towards electrophiles.
22. How is carboxylic acid prepared from Grignard’s reagent?
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Ans: When Grignard’s reagent is reacted with carbon dioxide gas, we get carboxylic
acids as follows;
- - + -
_ + +
Ether H 3O
CH3 CH2 Mg Br + O = C = O O=C OMgBr O=C OH
Carbon dioxide
CH2 Br CH2
CH3 + Mg CH3
Propanoic acid
OH
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23. How Grignard reagent reacts with epoxides to form alcohol?
Ans: Grignard’s reagent reacts with epoxide in dry ether to generate primary alcohols.
_ +
Ether
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CH3 CH2 Mg Br + CH2 CH2 CH3 CH2 CH2 CH2OMgBr
O + +
H3O
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Ethylene epoxide
Br
CH3 CH2 CH2 CH2 OH + Mg
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1-Butanol
OH
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