CLASS-XI

CHEMISTRY CLASS NOTES-1

CHAPTERS

I. CHEMICAL BONDING
II. THERMODYNAMICS
III. CHEMICAL EQUILIBRIUM
IV. IONIC EQUILIBRIUM
 CHEMICAL BONDING
I NT RO DU CT IO N

(a) It is well known fact that except for inert gases, no other element exists as independent atoms under
ordinary condition.

(b) Most of the elements exist as molecules which are cluster of atoms. How do atoms combine to form
molecules and why do atoms form bonds? Such doubts will be discussed in this chapter.

(c) A molecule will only be formed if it is more stable and has a lower energy, than the individual atoms.

Chemical Bond :

(a) A force that acts between two or more atoms to hold them together as a stable molecule.

(b) It is union of two or more atoms involving redistribution of e– among them.

(c) This process accompanied by decrease in energy.

(d) Decrease in energy  Strength of the bond.

(e) Therefore molecules are more stable than atoms.

CAUSE OF CHEMICAL COMBINATION

1. Tendenc y to acquire mi nimum energy :

(a) When two atoms approaches to each other-

Nucleus of one atom attracts the electron of another atom.

(b) Two nuclei and electron of both the atoms repells each other.
Potential Energy diagram
(c) If net result is attraction, the total energy of the system (molecule) decreases and a chemical bond forms.

(d) So Attraction  1/energy  Stability.

(e) Bond formation is an exothermic process

2. Octet rule

Octet rule was given by Lewis & Kossel

Atoms Combines to complete an octet of electrons in their outer most orbit. Complete orbital represents to get most
stable state. Hence all atoms have a tendency to acquire octet (s2p6) configuration in their outermost orbit.

The octet may be complete in following manner:

Complete transfer of electrons from one atom to another.

Ex. NaCl, CaCl2 & MgO etc. (Ionic Bond)

Sharing of electrons between atoms.

(a) Sharing of equal number of electron between two atoms.

Ex. Cl2, N2, O2 etc., (Covalent bond)

(b) Sharing of electron pair given by only one atom

Ex. [NH3  H+] & NH3  BF3 (Co-ordinate Bond)

 EXCEPTIONS OF OCTET RULE
1. Tra nsit ion metal ions
Cr 3+ Mn 2+ Fe 2+
[Ar]3d 3 [Ar]3d 5 [Ar]3d 6
[2, 8, 11] [2, 8, 13] [2, 8, 14]
2. Pseudo inert gas configuration [s 2 p 6 d 10 ]
Zn 2+ Cd 2+
[Ar]3d 10 [Kr]4d 10
3. Contraction of octet (incomplete octet)
Be F2 B
——
F
— 3
Al Cl3 B
—— —
Cl3 F
×
|
..
(4e) (6e) (6e) (6e)
B
. ×F (6 Electrons)

|
|
×
4. Expansion of Octet (due to empty d-orbitals) F

PCl 5 SF 6 ClF3 ICI5 IF7 F F

    
F S F
(10e) (12e) (10e) (12e) (14e)
5. Odd electron species F F
(12e)
Ex. NO, NO2, ClO2 etc.

O
N , N O
O
6. Compounds of Noble gases
Noble gases which have already completed their octets (or douplet in case of He.) should not form compounds.
However, their compouinds like XeF2, XeF6 & KrF2 etc., have been actually prepared.
CL ASSIFICATION OF BONDS

A T T R A C T IV E F O R C E S

STRONG BOND WEAK INTERACTION

Ionic Covalent Co-ordinate Metallic Hydrogen Vander waal's

bond bond bond bond bond Interaction
COVALENT BOND
(a) A covalent bond is formed by the mutual sharing of electrons between two atoms of electrolnegativity
elements to complete their octet.(Except H which completes its duplet)
× ×
H  H H – H









×






×
  ×  O= O

  ××  N N
× ×








× ×



H2 molecule O O N N
(b) The shared pair of electrons should have opposite spins, and are localised between two atoms
concerned.
 (c) Shairing of electrons may occurs in three ways –
No. of electrons shared Bonded Electron pair Bond.
between two atoms
2 1 Single bond (–)
4 2 Double bond (=)
6 3 Triple bond ()
Ex. 
H –– N –– H {Three single bonds (not triple bond}

H
N  N Triple bond. (not three single bond) O = O (Double bond) H – O – H (Two single bonds.)

CO-ORDINATE BOND

(a) It is a covalent bond in which the shared electron pair come from one atom is called coordinate bond.
(b) Necessary conditions for the formation of co-ordinate bond are -
(i) Octet of donor atom should be complete and should have atleast one lone pair of electron.
(ii) Acceptor atom should have a defficiency of at least one pair of electron.
(c) Atom which provide electron pair for shairing is called donor.
(d) Other atom which accepts electron pair is called acceptor. That is why it is called donor-acceptor or
dative bond.
H F
 
H–N: + B–F  NH3 BF3
 
H F
BF3 is electron defficient compound.
H3N  NH
 3

Metal co-ordinate compounds - [Cu(NH 3) 4] +2  Cu+2

H3N  NH
 3
+
H

Ex. NH4+ ; H3N + H+ H – N –H

(Lowry-Bronsted acid) H
(e– acceptor)

H H






+
H3O ; O + H +
 O  H+
H H

N2O ; N  N O

 Note : Compounds in which Ionic, covalent and co-ordinate bonds are present, are as follows -
NH4Cl, CuSO4.5H2O, K4[Fe(CN)6], KNC, KNO3, etc.
 WAVE MECHANICAL CONCEPT OF CO-VALENT BONDING –

(a) One orbital can accomodate at the most 2 electrons with opposite spins
(b) Half filled orbital or unpaired electron orbital accepts one electron from another atom, to complete its orbital.
(c) Tendency to complete orbital or to pair the electron is an condition of covalent bond.
Completion of octet is not the essential condition of covalent bond.
(d) If the outermost orbit has empty orbitals then covalent bonds are formed in excited state.
Variable valenc y i n covalent bonds :
(i) Variable valencies are shown by those elements which have empty orbitals in outermost shell.
(ii) Lone pair electrons get excited in the subshell of the same shell to form the maximum number of
unpaired electrons. Maximum covalency is shown in excited state.
(iii) The energy required for excitation of electrons is called promotion energy.
(iv) Promotion rule – Excitation of electrons in the same orbit.
Ex.
(I) Phosphorus  Ground state

Covalency 3 (PCl3)

3s 3p
Phosphorus  Excited state

Covalency – 5 (PCl5)

3s 3p 3d
(II) Sulphur  Ground state.

3s 3p 3d Covalency - 2 (SF2)
Sulphur  Excited state

Ist excited state  Covalency - 4 (SF4)

3s 3p 3d

2nd excited state  Covalency - 6 (SF6)

3s 3p 3d So variable covalency of S is 2, 4, & 6.

(III) Iodine has three lone pair of electrons

(Ground state) 

5s 5p 5d
So it shows three excited states – Maximum number of unpaired electrons = 7
Variable Valencies are 1, 3, 5, 7
To explain the formation of covalent bond two theories based on quantum mechanics have been proposed.
 Valence bond theory (VBT)  Molecular orbital theory (MOT)

 VALENCE BOND THEORY (VBT)

(A) Overlapping theory (B) Hybridisation theory
(A) OVERLAPPING THEORY :
(1) It was presented by Heitler & London to explain how a covalent bond is formed.
(2) The main points of theory are –
(a) To form a covalent bond overlapping occurs between half filled valence shell orbitals of the two atoms.
(b) Resulting bond acquires a pair of electrons with opposite spins to get stability.
(c) Orbitals come closer to each other from the direction in which there is maximum overlapping
(d) So covalent bond has directional character.
(e) Extent of overlapping  strength of chemical bond.
(f) Extent of overlapping depends on two factors.
(i) Nature of orbitals – p, d and f are directional orbitals  more overlapping
s-orbital  non directional – less overlapping
(ii) Nature of overlapping –
Co-axial overlapping - extent of overlapping more.
Collateral overlapping - extent of overlapping less
Order of strength of Co - axial overlapping – p - p > s - p > s - s

• • • • • •
p-p p–s s–s

(g) As the value of n increases, bond strength decreases.

1s - 2p > 2s - 2p > 3s - 3p

(h) If n is same 2p - 2p > 2s - 2p > 2s - 2s

(i) Electron which is already paired in valency shell can enter into bond formation, if they can be unpaired
first and shifted to vacant orbitals of slightly higher energy of the same energy shell.
(j) This point can explain the trivalency of boron, tetravalency of carbon, pentavalency of phosphorus etc.
(k) Three types of bonds are fomed on account of overlapping.
(1) Sigma () bond (2) Pi () bond (3) delta () bond
1. Sigma () bond :
When orbitals overlaps along their inter nuclear axis, -bond is formed Ex. The bond formed by overlapping of
s - s, s - p, p - p (axial), sp3 – s, sp2 – s, sp3 – sp3, sp3 – sp2 & sp – sp atomic orbitals.

Sigma bond

 +   

S – S overlapping
 -bond

p-p co-axial overlapping

2. Pi () bond : When two p-orbitals along the lateral axis (side way), -bond is formed.

Difference between sigma and pi-bond

Sigma-bond Pi-bond

1. A -bond is formed by the axial overlapping A -bond is formed by the side ways overlapping
of atomic orbitals. of orbitals.
2. -bond formation involves overlapping of s-s, It involves overlapping of p-p orbitals.
s-p and p-p orbitals.
3. -bond is stronger because of larger extent of -bond is relatively weaker because of smaller
overlapping extent of overlapping.
4. The molecular orbital is symmetrical about The molecular orbital is discontinuous and consists
internuclear axis and electron cloud is present on two electron clouds below and above the internuclear
this axis axis
5. Free rotation exists around a -bond. Free rotation does not exist around -bonds.
6 A sigma bond may exist either alone or A -bond is always present along with a sigma-bond
or along with -bonds.
7. Hybridised orbitals or unhybridised orbitals are Hybridised orbitals are never involved in -bond.
involved in -bond.

3. Dalta()-bond: It is special type of lateral overlapping in which all four lobs of d-orbital are overlap laterally
with other smilar d-orbital produce delta()-bond.

–
+
–

+ +
–
+ z
–

dx2–y2 dx2–y2
(B) HYBRIDISATION THEORY
(a) It is introduced by pauling and slater, to explain equivalent nature of covalent bonds in a molecule.
Consider an example of Be compound :-
If it is formed without hybridisation then -
p-s p–p
Cl —— Be ———— Cl
both the Be–Cl bonds should have different parameters and p–p bond strength > s–p bond strength.
Practically bond strength and distance of both the Be–Cl bonds are same.
This problem may overcome if hybridisation of s and p-orbital occurs.
(b) Definition : Mixing of different shapes and approximate equal energy atomic orbitals, and redistribution
of energy to form new orbitals, of same shape & same energy. These new orbitals are called hybrid
orbitals. and the phenomenon is called hybridisation.
Now after considering s–p hybridisation in BeCl2
p–sp sp–p
Cl ——— Be ———— Cl
bond strength of both the bonds will be equal.
Characteristic of Hybridisation :
(a) Hybridisation is a mixing of orbitals and not electrons. Therefore in hybridisation full filled, half filled and
empty orbitals may take part.
(b) Number of the hybrid orbitals formed is always be equivalent to number of atomic orbital which have
taken part in the process of hybridisation.
(c) Each hybrid orbital having two lobes, one is larger and other is smaller. Bond will be formed from large lobe.
(d) The number of hybrid orbitals on central atom of a molecule or ion = number of  bonds + lone pair of
electron.
(e) One element can represent many hybridisation state depending on experimental conditions
E x . C showing sp, sp2 and sp3 hybridisation in its compounds.
(f) Hybrid orbitals are differentiated as sp, sp2, sp3 etc.
(g) The directional properties in hybrid orbital is more than atomic orbitals. Therefore hybrid orbitals form
stronger sigma bond. The directional property of different hybrid orbitals will be in following order.
sp < sp2 < sp3 < sp3d < sp3d2 < sp3d3
(h) Hybridize orbitals show oxial overlapping & form  bond

TYPES OF HYBRIDISATION :
1. sp hybridisation :
(a) In this hybridisation one s– & one p– orbital of an atom are mixed to give two new hybrid orbitals which
are equivalent in shape & energy known as sp hybrid orbitals.
(b) These two sp hybrid orbitals are arrange in straight line & at bond angle 180°.
(c) s-character 50%
2s 2p
Be (ground state)

2s 2p

Be (excited state)
sp hybridisation

Be atom share two electrons sp sp

with F in BeF2,

F F
2. sp 2 Hybridisation :
(a) In this hybridisation one s & two p orbitals are mixed to give three new sp2 hybrid orbitals which all are in
same shape & equivalent energies.
(b) These three sp2 hybrid orbitals are at angle of 120° & giving trigonal planar shape.
(c) s-character 33.33% in each orbital.
2s 2p

B (ground state)

B (excited state)
sp2 hybrid orbitals
2 2 2
sp sp sp
B atom share 3 electrons

with 3 F atoms in BF3

F F F
3. sp 3 Hybridisation :
(a) In this hybridisation one s orbital & three p orbitals of an atom of a molecule or ion, are mixed to give four
new hybrid orbitals called as sp3 hybrid orbitals.
(b) The angle between these four hybrid orbitals will be 109° 28'
2s 2p
C (ground state)

C (excited state)
sp3 hybridisation

C atom share sp3 sp3 sp3 sp3

four electrons with H H H H

4 hydrogen atoms

(c) The shape obtained from these hybrid orbitals would be tetrahedron.
4. sp 3 d Hybridisation :
(a) In this hybridisation one s orbital, three p orbitals and one d orbital are mixed to give five new hybrid
orbitals which are equivalent in shape and energy called as sp3d hybrid orbitals.
(b) Out of these five hybrid orbitals, three hybrid orbitals are at 120° angle and two hybrid orbitals are
perpendicular to the plane of three hybrid orbitals that is trigonal planar, the shape of molecule becomes is
trigonal bipyramidal.
For example, PCl5 showing sp3d hybridisation

3s 3p 3d
P (ground state)
 3s 3p 3d Cl

P* (excited state)
Cl P Cl
sp3d hybridisation
3 3 3 3 3
Cl
sp dsp dsp dsp dsp d
P atom share five e with Cl
Cl Cl Cl Cl Cl Cl
Structure of PCl5
(c) In this hybridisation dz2 orbital is hybridised with s and p orbitals.
In this way five sp3d hybrid orbitals form five sigma bond with five Cl atoms and give a molecule of PCl5,
shape of this molecule is trigonal bipyramidal.
Axial two P–Cl bonds are longer than equatorial three P–Cl bond due to repulsion
between 3 equitorial b.p. of e– and 2 axial b.p. of e–
5. sp 3 d 2 Hybridisation :
(a) In this hybridisation, one s-orbital, three p-orbitals & two d-orbitals are mixed to give six new hybrid
orbitals known as sp3d2 hybrid orbitals.
(b) The shape of molecule obtained from above six hybrid orbitals will be symmetrical octahedral.
(c) The angle between all hybrid orbitals will be 90°.
Ex. SF6, AlF6–3, PF6–, ICl5, XeF4, XeOF4, ICl4–,
(d) Two 'd' orbital participates in the hybridisation are dx2–y2 and dz2.
3s 3p 3d
SF6 S (ground state)

3s 3p 3d
S (IInd excited state)

sp3d2 hybridisation

3 2 3 2
sp3d2 sp3d2 sp3d2 sp3d2 sp d sp d

S (after hybridisation) share 6e– with 6 F atoms

F F F F F F

6. sp 3 d 3 Hybridisation :
(a) In this hybridisation, one s-orbital, three p-orbitals & three d-orbitals are mixed to give seven new hybrid
orbitals known as sp3d3 hybrid orbitals.

(b) In this hybridisation d-orbitals used are dxy, d x2  y 2 & d z 2 orbitals.

(c) These seven sp3d3 orbitals are configurated in pentagonal bipyramidal shape.
(d) Five bond angles are of 72° & ten bond angles of 90°.
(e) The following examples showing sp3d3 hybridisation –IF7 & XeF6.
F F

F F
I

F F
F
 VALENCE SHELL ELECTRON PAIR REPUL SION THEORY (VSEPR)
(a) Molecules having covalent bond have definite geometry as covalent bonding has directional characteristics. A
simple theory was given for the molecular shape of the covalent molecules by Gillespie and Nyholm in 1957.
(b) This theory predicts the shape of the molecule by considering the most stable configuration of the bond
angles in the molecule. This theory states
(i) Electron pairs in the valence shell of the central atom of a molecule, whether bonding or lone pairs are
regarded as occupying localised orbitals. These orbitals arange themselves in so as to minimize the
mutual electronic repulsions.
(ii) The magnitude of the different types of electronic repulsions follows the order given below:
lone pair-lone pair > lone pair - bonded pair > bonded pair - bonded pair
(iii) The electronic repulsion between two pairs of electrons will be minimum if they are as far apart as possible.
(iv) The actual shape of the molecules containing lone pairs is a little distorted from the basic shape as in the
NH 3 and H 2O molecules, the bond angles are not 109º28' but 107º and 104.5º respectively due to
presence of one lone pair in NH3 and two lone pairs in H2O.

Number of Molecule Electronic Bonding Non-bonding Molecular Example

electron pairs type geometry pair pair (E) geometry

2 AB 2 


 2 0 B A B BeF 2,BeCl 2
Linear Linear





O C O etc






 B



 

F

A
3 AB 3   3 0 B B B
 






   
Trigonal planar Trigonal planar

F 
F 

 



N



AB2 Trigonal planar 2 1 


B B O O ,SO2, O3







Bent

 B
H
A
4 AB 4
  4 0 B B C
 B H H
H
Tetrahedral Tetrahedral

 

A 
N
B B H H
AB 3 E Tetrahedral 3 1 B
H
Trigonal pyramidal

 

A 
O



B


AB 2 E 2 Tetrahedral 2 2 H
B
H
Bent
 B

 B

 A B

 B
5 AB5  5 0 PCl5
 B
Trigonal bipyramidal
Trigonal bipyramidal

B



A B
AB4E Trigonal bipyramidal 4 1 B SF4
B
See saw

B



A B
AB3E2 Trigonal bipyramidal 3 2 ClF 3


B
T-shaped

B



A 

AB2E3 Trigonal bipyramidal 2 3 XeF 2


B
Linear
B

  B B
  A
  B B
6 AB 6   6 0 SF 6
 B
Octahedral
Octahedral

B B
A
AB 5 E Octahedral 5 1 B B BrF 5
 

Square pyramidal

 

B B
A
B B
AB 4 E 2 Octahedral 4 2  
XeF 4
Square planar

Determination of hybridisation state :

Method (I)
Count the following pair of e– arround the central atom :
(a) Count all pure  bonded electron pairs (or  bonds)
(b) Count all lone pair of electron

(c) Count all coordinate bond.

(d) Count all negative charge.

Method (II)
To predict hybridisation following formulae may be used :

1
No. of hybrid orbital = [Total number of valence e– in the central atom + total number of
2
monovalent atoms – charge on cation + charge on anion]

1
Ex. NH 4 2
[ 5+ 4 – 1] = 4 sp3 hybridisation.

1
SF4 [6 + 4] = 5 sp3d hybridisation.
2
1
SO 2
4 2
[ 6 + 2] = 4 sp3 hybridisation.

( 'O' is divalent so add only charge on anion)

1
NO 3 [5 + 1] = 3 sp2 hybridisation.
2
If such type of e– pairs are –
two – sp hybridisation
three – sp 2 hybridisation
four – sp 3 hybridisation
five – sp 3 d hybridisation
six – sp 3 d 2 hybridisation
seven – sp 3 d 3 hybridisation

BOND LENGTH

(i) The internuclear distance between the two single covalently bonded atoms is called bond length or bond
distance.
(ii) If the electronegativities of both the atoms are equal, then the bond length is equal to the sum of the
covalent radii of two bonded atoms. dA – A = rA + rA
(ii) If the electronegativities of two bonded atoms differ, then the bond length is smaller than the sum of their
covalent radii. dA – B < rA + rB
Factors affecting bond length
(i) Size of atoms:
HI > HBr > HCl > HF
H2Te > H2Se > H2S > H2O
(ii) Hybridization state of the bonded atoms: If the s-character in hybridization state of the bonded
atoms increases, the C–H bond distance decreases.
Ex. In C – C single bond.
sp3 – sp3 single bond length = 1.54 Å sp3 – sp2 single bond length = 1.52 Å
sp2 – sp2 single bond length = 1.51 Å sp3 – sp single bond length = 1.46 Å
sp2 – sp single bond length = 1.45 Å sp – sp single bond length = 1.37 Å
Bond length decreases in the order sp3 – sp3 > sp2 – sp2 > sp – sp
(iii) Resonance or delocalisation of electrons of the bond: Bond length between atoms are changed if
a molecule shows resonance.
BOND ANGLE
The angle between two bonds is known as bond angle.
Factors affecting bond angle
(i) Hybridisation state of central atom: Compounds having different hybridisation have diferent bond angle.
Ex. BeH 2 BH 3 CH 4
Hybridisation sp sp 2 sp 3
Bond angle 180º 120º 109º28'
(ii) Lone pair of electron: If compounds have same hybridisation states then bond angle depends on lone
pair of electron.
Ex. CH 4 NH 3 H2 O
Hybridisation sp 3 sp 3 sp 3
Lone pair e– zero one two
Bond angle 109º28' 107º 105º
The different in bond angle is explained on the basis of following repulaion sequence
The repulsion between
lone pair-lone pair > lone pair - bonded pair > bonded pair - bonded pair
(iii) Electronegativity: When compounds having same hybridisation state of central atom and some number
of lone pair of electrons, then bond angle depends on electronegativity.
Bond angle  electronegativity
Ex. H2O > H2S
NH3 > PH3
E.N. of oxygen is more than sulphur therefore the bond angle in H2O will be more than H2S.
(iv) Size of terminal atoms: When size of terminal stoms increases, bond angle increases.
Ex. OF2 < Cl2O < Br2O
PF3 < PCl3 < PBr3

BOND ENERGY

(i) The amount of energy required to break one mole of the bond and separate the bonded atoms in the
gaseous state is known as the bond energy of that particular bond.
(ii) B.E. is expressed in KJ mol–1 (in SI units) or in Kcal mol–1.
Factors afecting bond energy
(a) Electronegativity difference of the bonded atoms : As the EN difference of the bonded atoms
increases the bond energy increases because the ionic nature of the bond increases.
Ex. Bond strength of hydrogen halides decreases in the order
H – F > H – Cl > H – Br > H – I
(b) Bond Order Bond energy  Bond order, therefore the increasing order of bond energy is
C–C<C=C<CC
(c) Hybridisation state of the bonded atoms : Bond energy  s-character
Ex. –C – H < –C = H < – C  H
sp3 sp2 sp
(d) Atomic size of bonded atoms : Atoms with small atomic radii form stronger bonds because the extent
of overlapping of atomic orbitals is more
Ex. B.E. of halogens is of the order
Cl – Cl > Br – Br > I – I
because their atomic sizes are in the order Cl < Br < I.
(e) Extent of overlapping of atomic orbitals: A larger extent of overlapping of component atomic
orbitals imparts great strength to the bond.
(f) Repulsion between the lone pairs of electrons of bonded atoms:
1
Bond energy 
No. of lone pair of electron on the bonded atoms
Ex. the bond energies of the following single bonds having zero, one, two and three lone pair of electrons
are in the order.
     
C – C > N– N> O– O > F – F









DIPOLE MOMENTS & MOLECULAR POLARITY

(a) The degree of polarity of covalent bond is given by the dipole moment (µ), which is the product of either
charge (e) and the distance (d) between them. µ = d × e. 'e' is the order of magnitude of the electronic
charge, i.e., about 10–10 esu and d is the distance between the atomic centres, i.e., about 10–8 cm.
(b) Hence dipole moments may be expected to have value around 10 –10 × 10 –8 = 10 –18 esu-cm. It is
however, general particle to express dipole moments in Debye units (D), 1 D = 10–18 esu-cm.

 –
A B
Electronegativity of A < Electronegativity of B

If the charge is in SI units (Coulumbs) and d in metre, µ will be coulumb-metre (cm) unit.
1D = 3.336 × 10–30 cm
(c) Any covalent bond which has a certain degree of polarity will have a coresponding dipole moment,
though it does not follow that compound containing such bonds will have dipole moment,for the polarity
of the molecule as a hole is the vector sum of the individual bond moment.

µresultant = µ12  µ22  2µ1 µ2 cos 

(i) For example, CO2 is a linear molecule, O = C = O, so that the dipole moments of the two C = O bonds
cancel out.
(ii) The C  Cl bond has a definite polarity and a definite dipole moment but carbon tetrachloride has zero
dipole moment becaue it is a tetrahedral molecule, and the resultant of the 4C – Cl bond moments is
zero.
(iii) On the contrary CH3Cl, CH2Cl2 and CHCl3 have definite dipole moments.
(Order of dipole moment CH3Cl > CHCl3 > CH2Cl2 > CCl4 = CH4)
Application of Dipole Moment Measurements
Dipole mement is a measure of the electrical dissymmetry (polarity) in the molecule and so its measurement
provides valuable information concerning the shape of molecules. Conversely, when the symmetry of the molecules
is known, dipole moment could be estimated fairly.
1. Inorganic substances:
(a) Monoatomic molecules such as He, Ne, etc., have zero dipole moment becaue they are symmetrical.
(b) Diatomic molecules such as H2, Cl2 and N2 have no dipole moment; so these molecules are symmetrical.
(c) Triatomic molecules some of these molecules possess zero dipole moment so they have a symmetrical
linear structure, Ex. CO2, CS2, HgCl2. Others like water and sulphur dioxide have definite dipole moments.
They are said to have angular or bent structures. (V-shaped)
O S
O= C= O S= C= S Cl – Hg – Cl
H H O O
1.84 D 1.63 D 0D 0D 0D
(d) Tetratomic molecules some molecules like BCl3 have zero dipole moment. They are said to possess a flat
2
and symmetrical (triangular) structure; other example are BF3, BBr3, CO 3 , and NO 3

Cl

µ= 0
B

Cl Cl
(e) PCl3, AsCl3, NH3, PH3, AsH3, H3O+ have apreciable dipole moment. They possess trigonal pyramidal structure.

P

Cl Cl Cl
2. Organic substances
(a) Mathane and CCl4 have zero dipole moment. So thay posess symmetrical tetrahedral structures with C
atom at the centre of the tetrahedron.
H

C
H H
H
Methane
(b) Benzene has zero dipole moment. All the 6C and 6H atoms are assumed to be in the same plane
(symmetrical hexagonal structure).
H
H H

H H
H
(c) Measurement of dipole moments will enable us to detect cis-and trans isomers of organic compounds (you
will learn about cis-trans or geometrical isomerism later in the organic chemistry).
The trans-isomer, which is symmetrical, has zero dipole moment while the cis-isomer has a definite dipole moment.
H H H Br
C C C C
Br Br Br H
cis-dibromoethylene (µ = 1.4D) trans-dibromoethylene (µ = 0)
 (d) The dipole moments of the aromatic compounds present a very good illustration of dipole moment. We
know that when substituted benzene is treated with reagent different products (namely ortho, meta and
para products) are formed. The dipole moments of these products are different since the orientation of
the groups is different. Let us take an example to clarify it. Let us take three isomers. o-nitrophenol,
m-nitrophenol and p-nitrophenol. We also have three other isomers, o-aminophenol, m-aminophenol and
p-aminophenol. We want to arrange these isomers in the order of their dipole moments.
X X X
Y

Y
Ortho Meta Para
In those cases where X = Y, the para isomer becomes symmetrical and have zero dipole moment. In
order to find their dipole moment, we need to know about the nature of the groups linked to the benzene
ring. In nitro phenols, one group (OH) is electron pushing and the other (NO2) is electron withdrawing
while in aminophenols, both the groups (OH and NH2) attached are electron pushing. So, depending on
the nature of the groups attached, the isomers have different dipole moment. Then calculation of dipole
moment follows as:
Case (i) : When X and Y both are electron pushing or electron withdrawing.
Let the bond dipole of C–X bond is represented by µ1 and that of C–Y bond by µ2. Now let us assume that
the electgron pushing groups have +ve bond moment and the electron withdrawing groups have –ve
bond moment. The net dipole moment is the resultant of two bond dipoles at different orientations.

1
µortho = µ12  µ22  2µ1 µ2 cos 60 o = µ12  µ22  2µ1 µ2 ·
2

 µo = µ12  µ22  µ1 µ2

µmeta = µ12  µ22  2µ1 µ2 cos120 o

 µm = µ12  µ22  µ1 µ2

µpara = µ12  µ22  2µ1 µ2 cos180 o = µ12  µ22  2µ1 µ2

 µp = µ1 – µ2
From the above expressions of µo, µm and µp, it is clear that when both X and Y are of the same nature
i.e., both are electron withdrawing or both are electron pushing the para product has the least dipole
moment and ortho product has the highest dipole moment. When X = Y, µ1 = µ2, thus µp would be zero.
Case (ii) : When X is electron pushing and Y is electron withdrawing or vice versa.
Let the bond moment of C–X dipole is µ1 and that of C–Y dipole is µ2.

µo = µ12  (  µ2 ) 2  2µ1 (  µ2 ) cos 60 o = µ12  µ22  µ1 µ2

= (µ1  µ2 ) 2  3µ1 µ2

µ meta = µ12  (  µ2 )2  2µ1 (  µ2 ) cos120 o = µ12  µ22  µ1 µ2

= (µ1  µ2 ) 2  µ1 µ2

µ para = µ12  (  µ2 )2  2µ1 (  µ2 ) cos180 o = µ12  µ22  2µ1 µ2 = µ1 + µ2

Looking at the expressions of µo, µm and µp, it is clear that the para isomer has the highest dipole
moment and ortho has the least.
3. Dipole moment and percentage ionic character
The measured dipole moment of a substance may be used to calculate the percentage ionic character of a
covalent bond in simple molecules.
1 unit charge = Magnitude of electronic charge = 4.8 × 10–10 e.s.u.
1 D = 1 × 10–18 e.s.u × cm.
Observed dipole moment
 % ionic character = × 100
Theoritical dipole m oment
Theoritical dipole moment is confined when we assume that the bond is 100% ionic and it is broken into ions
while observed dipole moment is with respect to fractional charges on the atoms of the bond.
ELECTROVALENT OR IONIC BOND
(a) The chemical bond formed between two or more atoms as a result of the complete transfer of one or
more electons from one atom to another is called Ionic or electrovalent bond.
(b) Electro possitive atom loses electron (group IA to IIIA)
(c) Electro negative atom gains electron (group VA to VIIA)
(d) Electrostatic force of attraction between cation and anion is called ionic bond or electrovalent bond.
(e) Total number of electron lose or gained is called electrovalency.
Ex.

(i) Mg + O  Mg+2 + O–2

2, 8, 2 2, 6
2e–

electrovalency of Mg = 2
electrovalency of O = 2

+2 –
(ii) Ca + Cl  Ca + 2Cl
2,8,8,2 2,8,7
One e–

Cl
2,8,7
One e–

electrovalency of Ca = 2
electrovalency of Cl = 1
–2
(iii) Ca + O  Ca+2 + O

2e–

electrovalency of Ca = 2
electrovalency of O = 2
(f) The force of attraction is equal in all direction so ionic bond is non-directional.
(g) A definite three dimensional structure is formed called crystal lattice.
(h) Ionic compound do not have molecular formula. It has only empirical formula.
Ex. NaCl is empirical formula of sodium chloride
FORM ATION OF IONIC COMPOUND - BORN HA BER CYCLE
(a) When elements react to form compounds, G (the free energy of formation) is negative. For a reaction
to proceed spontaneously, the free energy of the products must to lower than that of the reactants.
(b) Usually the energy changes are measured as enthalpy values H, and G is related to H by the equation
G = H – TS
In many cases ethalpy values are used instead of free energy values, and the two are almost the same if
the term TS is small. At room temperature T is almost 300 K, so G and H are similar when the
change in entropy S is very small. Entropy changes are large when three is a change in physical state,
Ex. solid to liquid, or liquid to gas, but otherwise entropy changes are usually small.
(c) A whole series of energy changes is involved when one starts from the elements and finishes with an ionic
crystal. These changes are shown in the Born-Haber cycle.
Formation of NaCl (s) involves

1 Hf
Na(s) + Cl  NaCl(s)
2 2(g)
S D
2
Na(g) Cl(g) –U
I.P. –e– – EGE + e–
Na+(g) Cl–(g)

D
thus S + I.P. + – EGE – U = Hf
2
here S = heat of sublimation of Na(s)
I.P. = ionisation potential of Na(g)
D = bond dissociation energy of Cl2
EGE = electron gain enthalpy of Cl(g)
U = lattice energy
Hf = enthalpy heat of formation of NaCl(s)
If lattice is MgX2(s) then
S + (IP1 + IP2) + D – 2EGE – U = Hf
where (IP1 + IP2) = total ionisation energy to form Mg2+(g) from Mg(g).

FACTORS FAVOURING IONIC BONDING

(a) Ionisation energy :
Amount of energy required to remove an electron from the outermost orbit of an isolated gaseous atom
to form the +ve ion or cation. (energy absorbed)
Lesser Ionization energy  Greater tendency to form cation.

Ex. Na + > Mg +2 > Al +3 

+ + + + +
 Cation formation tendency
Cs > Rb > K > Na > Li 
(b) Electron affinity :
Amount of energy released when an electron is added to an isolated gaseous atom to form
–ve ion (anion) energy released.
Higher electron affinity  Greater tendency to form anion
Ex. Cl– > F– > Br– > I–
F– > O–2 > N–3
(c) Lattice energy - (Energy released)
The energy released in the formation of 1g mole electrovalent compound from isolated gaseous ions is called
lattice energy (U) of that compound.
Higher lattice energy  Greater will be the stability or strength of ionic compound.
Factors affecting lattice energy :
(i) Magnitude of charge  U  z+ z– (Ionic charge)
Lattice energy  Magnitude of charge
NaCl MaCl 2 AlCl 3
Na+ Mg +2 Al +3

– Lattice energy increases
– Size of cation decreases.
1
(ii) Size of Cation :- Lattice energy 
r  r


LiCl NaCl KCl RbCl CsCl


– Size of cation increasing
– Size of anion is constant
– Lattice energy decreases.

PROPERTIES OF IONIC COMPOUND

(a) Physical state – Ionic compounds are hard, crystalline and brittle due to strong electrostatic force of attraction.
Brittleness  {Same charged ions comes nearer. So they repell each other}

+ + + + + +

+ + + +
+ + +
+ + +
+ +
+ +

Attraction Repulsion
(b) Isomorphism : Different ionic compounds, having same configuration/geometry of ions are isomorphs
of each other and phenomenon is known as isomorphism
Ex. NaF, MgO, ZnSO4 · 7H2O, FeSO4 · 7H2O. All alums M2'SO · M2"(SO4)3 · 24H2O.
(c) Boiling point and melting point –
Ionic compounds have high boiling point and melting point due to strong electrostatic force of attraction
among oppositely charged ions.
(d) Conductivity – It depends on ionic mobility.
(i) In solid state - No free ions - Bad conductor of electricity.
(ii) In fused state or aqueous solution Due to free ions - Good conductor of electricity.
Conductivity order Solid state < fused state < Aqueous solution
(e) Solubility – Highly soluble in water (Polar solvents) Ex. NaCl in water
(i) The Na+ ions get associates with - vely charged 'O' of water
(ii) And Cl– ions associates with +vely charged 'H' of water.

+
H
– –
Na+ = O +
Cl–
H

(iii) Thus charge on Na+ and Cl– decreases and electrostatic force of attraction also decreases which leads
to produce free ion.
(iv) The energy released due to interaction between solvent and solute is called solvation energy. If water is
used as solvent it is called hydration energy.
(v) For an ionic compound to be soluble in water – Hydration energy > Lattice energy

1
Lattice energy 
So lub ility

Hydration energy  Solubility.

1 1
Hydration energy (H)   { r+ & r– are radius of cation and anion}
r r

1 1
(vi) Hydration energy mainly depends on the cation radius because the value of is negligible in comparision to 
r r
(vii) Down the group both the lattice energy & hydration energy decreases, if decrease in lattice energy is
greater than hydration energy, solubility increases down the group and vice versa.
FACTOR AFFECTING SOLUBILITY :
(a) Dielectric constant of solvent –
The capacity of solvent to neutralise the charge of ionic compounds is called Dielectric constant. It is
represented by 
(i) Water has maximum dielectric constant ( = 80)
(CH3OH  = 35) , (Acetone  = 21)
(C2H5OH  = 27) , (Ether  = 4.1)
(Benzene  = 2.3)
H2O > CH3OH > CH3CH2OH > CH3COCH3 > CH3OCH3 > C6H6
(ii) Ionic compounds are more soluble in the solvents, having high dielectric constant.
(iii) H2SO4 and H2O2 have high dielectric constant but these are not a good solvent due to oxidising nature.
(b) Size of ion :
(i) Keeping size of cation constant, the lattice energy decreases with the increase of anionic radius.
Hence order of solubility of LiX in water is LiF < LiCl < LiBr < LiI

1
As solubility 
lattice energy
(ii) In LiI covalent nature is more according to Fajan's rule but HE > LE therefore LiI is more soluble in water.

(iii) Keeping size of anion constant, the hydration energy decreases with the increase of cationic radius.
Hence order of solubility of MSO4 will be – BeSO4 > MgSO4 > CaSO4 > SrSO4 > BaSO4 ( Exception of
Fajan's rule)

(iv) If size of cation and anion is very large, solubility decreases from top to bottom.

(v) Solubility decreases in a period (as ionic nature decreases and covalent nature increases)

NaCl > MgCl2 > AlCl3

TR ANSITION FROM IONIC TO COVALENT BOND – FAJANS' RULE

(a) Just as a covalent bond may have partial ionic character an ionic bond may also show a certain degree of
covalent character. When two oppositely charged ions aproach each other closely, the cation would
attract the electrons in the outer shell of the anion and simultaneously repel its nucles. This produces
distortion or polarization of the anion, which is accompanied by some sharing of electrons between the
ions, i.e., the bond acquires a certain covalent character. The formation of a covalent bond between two
ions may be illustrated with reference to formation of Agl.

Ag+ Ag+ I– Ag+ ... I–

I–

distorted ion covalent character in ionic bond

separate ions
(b) FACTORS INFLUENCING ION – DEFORMATION OR INCREASING COVALENT CHAR ACTER

(i) Large charge on the ions:

The greater the charge on the cation, the more strongly will it attract the electrons of the anion. For
example, Al 3+ can distort Cl – ion more than Na + ion. So aluminium chloride is a covalent compound
whereas NaCl, AlF3, AgF are ionic.

(ii) Small cation and large anion:

For a small cation, the electrostatic force with which its nucleus will attract the anion will be more.
Moreover a large anion cannot hold the electrons in its outermost shell, especially when they are attracted
by a neighbouring cation. Hence there will be increased covalent charcter with a small cation and a large
anion, as in AgI.

(i i i ) Cation with a pseudo-inert gas type of electronic configuration:

A cation with a 18 electron in outermost shell such as Ag+ ([Kr] 4d10) polarizes anions more strongly than
a cation with a 8 electron arrangement as in K+. The 'd' electrons in Ag+ do not screen the nuclear charge
as effectively as the 's' and 'p' electron shell in K+. Thus AgI is more covalent than KI, although Ag+ and
K+ ions are nearly of the same size. Cuprous and mercurous salts are covalent.

The above statements regarding the factors, which influence covalent character, are called Fajans' rules.
It can thus be seen easily that there is nothing like a purely ionic compound or a purely covalent compound.

Polarisation power of a cation is usually called ionic potential or charge density.

Ch arge on cation
Ionic potential  (phi) =
Size of cation
APPLICATION OF THE CONCEPT OF POLARISATION :

(a) To determine covalent and ionic character of molecule : -

Covalent character

Ionic character

From left (larger size) to right (smaller size) in a period  increases so covalent character increases.

Na +, Mg++ A l +++ Si ++++



- charge increases

- size decreases  increases

- Covalent character increases with particular anion

From top to bottom in a group  decreases so covalent, character decreases.

Li +

Na+ - Size increases (charge is fix)

K+ -  decreases

Rb+ - Hence covalent character decreases with particular anion

Cs +

(b) To determine nature of oxide : -

 < 2.2 (Basic oxides)

 = 2.2 to 3.2 (Amphoteric oxides)

Neutral oxides doesn't react with acid & base eg. H2O, CO etc.

Amphoteric oxides (Al2O3 etc.) reacts with acid & base

 > 3.2 (Acidic oxide)

Ex. Li2O, Na2O, K2O, Rb2O, Cs2O



–  decreases
– Basic character increases

(c) To determi ne conduct iv it y of metal halide s (MX)

If  < 2.2 MX - ionic nature

If  > 2.2 MX - covalent nature
(d) Formation of complex compounds :-

Smaller the cation, more will be the tendency of forming complex compounds.

High value of  shows tendency of forming complex compounds.

If  is low  No or less tendency of forming complex compounds.

 s-block metals (larger size) doesn't have the tendency to form complex compounds.

Exceptions - Li, Be, Mg (small size)

 d-block metals have the tendency to form complex compounds (small in size, high charge).

1
(e) To determine thermal stability of metal carbonates : stability  (Covalent nature)

–––––––––––

O
– 
M+2 O— C MO + CO2

O–

More smaller the size of metal cation, its polarisation capacity increases - strength of M—O bond increases
and C—O bond decreases. So thermal stability of carbonates decreases.


CO3–2 
O–2 + CO2

From top to bottom thermal stability of carbonates increases (as size of cation increases)

(Ionic character increases or covalent character decreases)

BeCO3
MgCO3 – size of cation increases
CaCO3 –  decreases (covalent character decreases)
SrCO3 – Thermal stability increases
BaCO3

(f) To explain colour of compounds : -

More the covalent character, more will be the colour intensity.

Colour density    (Covalent character)

Ex. AgCl AgBr AgI

(White) (Light yellow (Dark yellow)

SnO 2 SnS 2

(White) (Yellow)

(g) To explai n diagonal relat ionship :-

Since the value of  for Be2+ is almost of the same order as that of diagonally situated Al3+. Hence have
many similar properties. Similarly value of  for Li+ is equal to Mg+2 , so have diagonal relationship.
MOLECUL AR ORBITAL THEORY (MOT):
Given by hund & Mulican
(a) Two atomic orbital come nearer & then overlap each other to form two molecular orbitals (MO)
(b) Combination of two atomic orbital (AO) forms two molecular, orbital (MO):

ABMO (antibonding molecular orbital)

AO + AO
BMO (bonding molecular orbital)

(c) Both orbitals can be filled by electrons according to Auffbau principle.

(d) Energy of BMO < Energy of ABMO.
(e) Order of energy in molecular orbitals of di-atomic molecules.
(i) From H2 to N2:
1s < *1s < 2s < *2s < 2pz = 2py < 2px <  *2pz =  *2py <  *2px
For N 2 molecule

^ pz

 
     
2p 2p

Increasing energy in N 2 molecule

pz
 
  px   py


  2s

 
2s 2s


2s
  1s

 
1s 1s


1s
(ii) For O2 & F2:
1s < *1s ; < 2s < *2s < 2px < 2pz = 2py <  *2pz =  *2py <  *2px
For O 2 molecule

 pz
^
  Bond order = ½ (8–4) = 2
 

p x p y
    
2p 2p
* Having two unpaired  
electrons so paramagnetic  p x  py

pz
Increasing energy

  2s

 
2s 2s

2s

  1s

 
1s 1s

1s

    = antibonding molecular orbital

  = bonding molecular orbital

Nb  Na
Bond order =
2

Nb = No. of electron in bonding MO's

Na = No. of electron in antibonding MO's
(g) If bond order = 0, it means species does not exist.
(h) Bond order of 1, 2 & 3 corresponds to a single bond, double & triple bond respectively.
(i) Bond order  stability of molecule  bond length 
(j) If the molecule has one or more unpaired electron, it will be paramagnetic, while if all the electrons are
paired it will be diamagnetic.
Ex. H2 = Configuration : (1s)2  * (1s)0

Nb  Na 2 0
Bond order = = = 1, Hence H – H (dimagnetic)
2 2
 MO Electronic Configuration of Some Molecules

Molecule Total no. MO configuration Bond order Magnetic

or ion of electrons behaviour

H2 2 (  s)2 1 Diamagnetic
H2+ 1 ( 1s)1 0.5 Paramagnetic
H2 3 ( 1s)2, ( * 1s)1 0.5 Paramagnetic
He 2 4 ( 1s)2, ( * 1s)2 0 Diamagnetic
N2 14 KK ( 2s)2, ( * 2s)2 , 3 Diamagnetic
( 2py)2=( 2pz)2, ( 2px)2
O2 16 KK ( 2s)2, ( * 2s)2 ( 2px)2, 2 Diamagnetic
( 2py)2=( 2pz)2 ( * 2py)1 ( * 2pz)1
O2+ 15 Remove one electron from 2.5 Paramagnetic
 * 2pz from O2
O 2 2+ 14 Same as that of N2 3 Diamagnetic
O2 17 KK ( 2s)2, ( * 2s)2 ( 2px)2, 1.5 Paramagnetic
( 2py)2,( 2pz)2
( *2py)2,( *2pz)1
O22– 18 KK ( 2s)2, ( * 2s)2 ( 2px)2 1 Diamagnetic
( 2py )2,( 2pz)2
( *2py)2,( *2pz)2
F2 18 Same as above 1 Diamagnetic
Ne 2 20 18 as above and ( * 2px)2 0 Diamagnetic
CO 14 Same as in N2 3 Diamagnetic
NO 15 Same as in O2 + 2.5 Paramagnetic
NO+ 14 Same as in N2 3 Diamagnetic
NO 2+ 13 KK( 2s)2 ( * 2s)2 ( 2px)2 2.5 Paramagnetic
( 2py)1,( 2pz)1
NO – 16 Same as in O2 2 Paramagnetic
CN 13 Same as in NO2+ 2.5 Paramagnetic
–
CN 14 Same as in N2 3 Diamagnetic

HYDROGEN BOND
(a) An atom of hydrogen linked covalently to a strongly electronegative atom can estabilish an extra weak
attachment to another electronegative atom in the same or different molecules. This attachment is called
a hydrogen bond.
(b) To distinguish from a normal covalent bond, a hydrogen bond is represented by a broken line,
e.g. X – H ... Y where X and Y are two electronegative atoms. The strength of hydrogen bond is quite low
about 2-10 kcalmol–1 or 8.4-42 kJmol–1.
(c) Conditions of hydrogen bonding:
(i) The molecule must contain a highly electronegative atom linked to H-atom. (If E.N.  polarity of bond )
(ii) The size of the electronegative atom should be small.(size  electrostatic atraction )
Ex.

H H H H

H — N ····· H — N ····· H — N ····· H — N

H H H H

+ – + – + – + – + –
H — O ····· H — O ····· H — O, H — F ····· H — F

+ + +
H H H

(d) Strength of H-bond :

H .............. F bond dissociation energy = 41.8 kJ mol–1
H .............. O bond dissociation energy = 29.3 kJ mol–1
H .............. N bond dissociation energy = 12.6 kJ mol–1
(e) Effect of H-bond
(i) It causes the association of many molecules.
(ii) Due to hydrogen bond molecules are associated and show high moleculer weight.
(iii) M.P. & B.P. of the molecules increases
(iv) Viscosity & surface tension of the molecules increases.
(v) The compounds which can form H-bond with the covalent molecules are soluble in such
solvents.
Examples : Alcohol & Ammonia are water soluble.
Type of H-bonding :
(a) Intermolecular (b) Intramolecular
(a) Intermolecular H-bond:
(i) This type of H-bonding takes place between two moleules. Ex. ROH, H2O, R - OH & H2O

R R H H R H R
| | | | | | |
O – H ... O – H, O – H ... O – H, O – H ... O – H ... O – H

(ii) In such compounds molecular wt., M.P, & B.P. are high.
(iii) Extent of H-bonding  viscosity & density .
(b) Intramolecular Bond:
(i) It is the H-bonding in the same molecule of a compound. The bonding also known as chelation.
(ii) Solubility in water, M.P. & B.P. of these compounds decreases.
(iii) The value of acid strength of acid depends on the relative stability of the acid and its canjugated base
if the interamolecular H-bonding stablises the conjugate base then, the acid strength increase and if
the conjugate acid is stabilised in this way then the acid strength decreased.
H-bond has serious consequences on the physical properties. These are –
(i) H2O is liquid at room temperature whereas H2S is gas at room temperature although H2S has greater
molecular weight.
(ii) Ice is lighter than water, although it solid because in ice H2O molecules are extending their H-bonds to full
length and six water molecules produce a cage like structure which is porous in nature leading to smaller
mass and larger volume, thus lowering the density.
(iii) Alcohols have higher boling points than corresponding alkanes and there of the same moleculear mass.
This can be explained by the intermolecular H-bonds existing among the R-OH molecules whereas ethers
and hydrocarbon are not capable to have such strong intermolecular forces. thus they have lower boling
points.
H2O > R-OH > R-OH  Exceptional
H2S < R-SH < R-S-R  Normal
H-bond increases
H2O > R-OH > R-O-R

B.P. increases
R-O-R  no H-bond
H2O  H-bonds
R-OH  H-bond.
(iv) Alcohol and water are miscible in any proportion due to formation of H-bonds.
(v) Ammonia is excessively soluble in water whereas other gases are partially soluble. This is due to the
tremendous capacity of NH3 molecule to generate 4-H-bonds.
NH3 > RNH2 > R2NH
(vi) Solubility order of different amines and ammonia in water follows the order NH3 > RNH2 > R2NH. This
can be explained by the capacity of these elements to form H-bonds.
(vii) KHF2 exists whereas KHCl2, KHBr2, KHI2 do not because KHF2 is constituted by 2 ions
–
i.e. K+ & HF2

– + – –
[ F ... H – F ] [Cl ... H – Cl]
exist does not exist
KHF2 is a red orange coloured solid.
(viii) o-nitro phenol is steam volatile and less H 2O soluble than its coresponding para isomer because in
o-nitro phenol, intra molecular H-bond exists which reduces the capacity of the molecule to produce
intermolecular H-bonds with other molecules like water. This brings interamolecular forces among the o-
nitrophenol molecules resulting into high volatility.
(ix) Acetic acid has a molecular weight of 60 in benzene and it shows a very high boiling points. This is due to
dimerization of molecule.

O – H ... O
CH3 – C C CH3
O ... H O
(x) Salicylic acid has very high acidity due to chelation of salicylate ion through the H-bond
–
O ··· H
C O

(xi) Chelation means to grab atoms in vicinity as much as possible.

(xii) Maleic acid has greater acidity than furmaric acid. This can also be explained by chelation of monomaleate
anion which has a H-bond between carboxylate anion adn the unionized carboxylic acid.
O

H— C O–

H— C OH

O
(xiii) Normally when 2 hydroxyl groups are present on the same carbon atom i.e. gem diols are unstable, but
"chloralhydrate" is a stable molecule due to formation of H-bond.
Cl ..... H — O

Cl C— C— H

Cl ..... H — O
O O
(xiv)
CH3 – C – CH2 – C – CH3

In the above compound, (acetyl acetone) enol form is stable because of the intramolecular H-bond.

H
O O

C C
CH3 CH3
CH

VANDER WALL'S FORCES

(a) These are the weakest type of inter molecular forces that exist among the molecules which being significant
change in physical properties.
(b) These are non-directional, non-valence cohesive forces. These attractive forces being played between
the two molecules are independent of the presence of other molecules.
(c) Solid, liquid or gaseous states of many molecules are explained on the basis of inter molecular forces
other than covalent, ionic or metallic bonds. Although inert gases do not form any type of bond but may
exist in liquid and solid states. This shows that the atoms of inert gases are attracted by each other
through some type of inter molecular forces. These intermolecular forces are called Vander Walls forces
and may be of the following types:
(d) Ion-dipole attraction : Polar molecules are atracted by ions. The negative pole is attracted by cation
and positive pole attracted by the anion. This type of attraction is called ion dipole attraction, ion-dipole
attraction is abserved generally in the process of solvation when sodium chloride (Na+ Cl–) is dissolved in
water because negative poles of water aggregate around Na+ ions and positive poles around Cl– ions.

H
+
Na ······ O
H
(e) Dipole-dipole attraction : The force of attraction between the oppositely charged poles of two polar
molecules (for example : H2O, H–F, NH3 etc.) is called dipole-dipole attraction. This type of attraction is
weaker than the ion-dipole attraction.
O
H–Cl
··
·· ·· H H

···
O

···
O
H H
H H
(f) Ion-induced dipole attraction : When non polar molecules come in contact with ions, its electron cloud
gets polarised and the oppositely charged end of it is attracted by the ion. For example attraction
between Na + and Cl 2 molecule.

– +
Na+ + Cl – Cl  Na+ ........ Cl – Cl

(g) Dipole-induced dipole attraction : This type of cohesive forces occurs in a mixture of polar and non
polar molecules. The former induce polarity in non polar molecules by disturbing their electron system.
for example force of attraction between Cl2 and H2O.

O H
+ Cl – Cl  O ........ + –
Cl – Cl
H H H

(h) Induced-Induced dipole : The weak intermolecular forces operating in similar non polar gaseous
molecules are called London forces. These forces are very weak in nature and exists only at low
temperature. For example weak intermolecular forces in F2, Cl2, N2, molecules and in nobal gasses.

+ +

– –
+ +
 Class-XI

THERMODYNAMICS AND THERMOCHEMISTRY

THERMODYNAMICS:-
 It is the branch of science which deals with the study of quantitative relationship between heat &
other forms of energy. It is based on two generalizations viz. the 1st law and the 2nd law of
thermodynamics which are based on human experience.
 It helps to predict the maximum efficiency of various types of heat engines and maximum work
obtained from a given fuel.
 It helps to predict the feasibility of a physical or chemical process under a given set of conditions.
 It helps to predict the extent to which a reaction would take place before the attachment of
equilibrium.
 Laws of thermodynamics helps to deduce important generalizations of physical chemistry like
Raoult’s law of lowering of vapor pressure, expression for elevation in boiling point, depression in
freezing point, Nernst distribution law, phase rule and law of chemical equilibrium.
 Though thermodynamics helps in various ways to study a chemical reaction but it gives no idea
about the rate and mechanism of a reaction and the laws of thermodynamics are applicable only to
matter in bulk and not to individual atoms.
BASIC TERMINOLOGY:-
1. System-:
 It is defined as any specified portion of the matter under study which is separated from the rest
of the universe by a bounding surface.
 It may consist of one or more substances.
 If a system is uniform throughout in all respects and consists of only one phase then it is known
as a homogeneous system, e.g. a pure solid or a liquid.
 If a system is not uniform throughout and consists of more than one phase it is known as a
heterogeneous system, e.g. a system consisting of two immiscible liquids.
2. Surrounding:-
 The rest of the universe which might be in a position to exchange energy and matter with the
system is called the surroundings.
 For example :-If a test tube containing a gas under examination is immersed in a water bath then
the gas is the system, the water bath is the surrounding and the test tube is the boundary.
3. Types of System:-
 Depending upon the interaction between the system and surroundings there are three different
types of systems.
 Open system: - A system which can exchange matter as well as energy with its surrounding is
said to be an open system e.g. evaporation of water placed in an open breaker. fig….(1a)
 Closed system: - A system which can exchange energy but not the matter with the surrounding
is known as a closed system e.g. evaporation of water placed in a closed breaker. fig….(1b)
 Isolated system:-A system which can neither exchange matter nor energy with the surrounding
is known as an isolated system e.g. evaporation of water placed in a closed and insulated vessel.
fig….(1c)
4. Properties of a system:-
 The properties associated with macroscopic systems (systems consisting of large number of
molecules, atoms or ions) are known as macroscopic properties and these are of two types.
 The properties that depend upon the amount of substance or substances present in the system are
known as extensive properties e.g. mass, volume, internal energy, enthalpy, entropy and heat
capacities etc.
 The properties that does not depend upon the amount of substance present in the system are
known as intensive properties e.g. pressure, temperature, density, refractive index, M.P, B.P,
viscosity, surface tension, specific heat, molar properties etc.
5. State of System:-
 When macroscopic properties of a system have definite values, the system is said to be in a
definite state. Whenever there is change in any one of the macroscopic properties, the system is
said to be changed into a different state.
 The state of a system is fixed by its macroscopic properties.
6. State Variables:-
 The measurable properties of a system which completely define the state of a system are called
as state variables e.g. pressure (P), temperature (T) and volume (V) etc.
 The variables (P and T) which must be necessarily specified to define the state of a system are
designated as independent state variables while the state variable (V) which depends on the
value of P and T, is called as dependent state variable.
7. State functions & path functions:-
 State function is a property of a system that is uniquely determined by the present state of system
which depends only upon the state of the system and not how its state is achieved, e.g. internal
energy, enthalpy etc.
 The letter  is used to indicate change in state function in a thermodynamic process, e.g.  V=
Vfinal – Vinitial. While path functions are the property of a system which depends upon how the
state is achieved, e.g. heat & work.
8. Thermodynamic equilibrium -:
 A system in which the macroscopic properties do not undergo any change with time is said to be
in thermodynamic equilibrium. In fact the tem thermodynamic equilibrium implies the existence
of three kinds of equilibrium. Which are-:
 Thermal equilibrium:- A system is said to be in thermal equilibrium if there is no flow of heat
from one portion of the system to another. This is possible if the temperature remains the same
throughout in all parts of the system.
 Mechanical equilibrium:- A system is said to be in mechanical equilibrium if no mechanical
works is done by one part of the system on another part of the system. This is possible if the
pressure remains the same throughout in all parts of the system.
 Chemical equilibrium: - A system is said to be in chemical equilibrium if the composition in
the various phases of the system remains the same throughout.
9. Processes & their types:-
 The operation by which a system changes from one state to another is called a process.
 A process carried out infinitesimally slowly so that the driving force is only infinitesimally
greater than the opposing force is called a reversible process while a process which does not take
place infinitesimally slowly, is said to be an irreversible process or spontaneous process.
 A reversible process can’t be realised in practice because it would require infinite time for its
completion. In fact these are imaginary and theoretical.
 A process is said to be isothermal if the temperature of the system remains constant during each
stage of the process. i,e dT=0
 A process is said to be adiabatic if no heat enters to or leaves from the system during each step
of the process. i.e dQ=0
 A process is said to be isobaric if the pressure of the system remains constant during each step of
the process. i.e dP=0
 A process is said to be isochoric if the volume of the system remains constant during each step
of the process. i.e dV=0
 When a system after completing a series of changes returns to its original state, it is said to be a
cyclic process.
10. Nature of heat and works:-
 Whenever a system changes from one state to another it is accompanied by change in energy.
Thus change in energy may appear in the form of heat, work, light etc.
 According to James Joule, there is a definite relationship between mechanical work done
‘ W ’and heat produced ‘ H . ’ i.e. W  H or W  JH where ‘ J ’ is known as Mechanical
equivalent of heat.
 If work is done by the system on the surroundings and energy of the system is decreased, it is
taken to be negative, ‘-W’.
 If work is done on the system by the surroundings and energy of the system is increased, it is
taken to be positive, ‘+W’.
 Energy manifests itself not only in the form of mechanical work but also as heat energy,
electrical energy and chemical energy.
  The energy is composed of two factors, an intensity factor and a capacity factor and the product
of these two factors give the energy. For example heat energy is measured by the product of
temperature (intensity factor) and the heat capacity (capacity factor) of the system concerned.
 Heat & work are not state functions but are path functions
11. INTERNAL ENERGY (U):-
 Every substance is associated with a definite amount of energy which depends upon its chemical
nature as well as upon its temperature, pressure and volume. This energy is known as internal
energy. In fact it is the total energy stored in a system.
 The exact magnitude of this energy is not known because the chemical nature includes such
indeterminate factors as the translational, rotational and vibrational movements of the molecules, the
manner in which the molecules are put together, the nature of the individual atom etc. However if a
system changes from one state to the other then we can determine the change in internal energy.
 Internal energy of a substance or a system is a definite quantity and is a state function.
 Suppose one system having internal energy U A undergoes a chemical change giving rise to another
chemical system having internal energy U B then the change in internal energy is given by-:
U  U B  U A ---------------- (1)
 If U R is the internal energy of the reactants and U P is the internal energy of the products then the
change in internal energy is given by U  U P  U R --------------- (2)
12.FIRST LAW OF THERMODYNAMICS: -
 As a result of a number of experimental observations, Helmholtz, Clausius and Kelvin generated a
law of nature known as principles of the conservation of energy or the first law of thermodynamics.
It can be stated in different ways as follows.
 Energy can neither be created nor be destroyed during any physical or chemical change. It can
convert one form to other form only.
 The total energy of an isolated system remains constant. In other way it is impossible to construct a
perpetual motion machine. i.e. a machine which can produce energy without expenditure of energy.
 There is exact equivalence of heat & mechanical work. Mathematically, If a system with internal
energy U 1 , volume V1 and pressure P absorbs heat energy Q .The absorbed energy will be utilised
in two ways:
(1) To increase the internal energy from U 1 to U 2
(2) to do some work i.e. to change the volume from V1 to V2
 Q  (U 2  U 1 )  W  U  W ------------------ (3)
Or ∆U=Q-W
 If a system with internal energy U 1 , volume V1 and pressure P liberates heat energy Q and work
‘W’ is done on the system. Then Q  (U 2  U 1 )  W   U  W ------------------ (3)
Or ∆U=Q+W

13.Internal energy and the first law: -

 Suppose a system changes from state A to sate B by following path-I accompanying a change of
energy equal to U . Now suppose that the same change of state is brought about by another path
 say path-II and the change of energy is U 1 Suppose U  U 1 ,then by coupling of these two
processes the system would return to its initial state and at the same time a surplus of energy equal
to U  U 1 would became available. By repeating the same cycle over and over again, energy
would be generated continuously hence a perpetual machine would be possible. This is
contradiction to first law. Hence U 1  U .Thus energy change accompanying a process is a
function only of the initial and the final state.

 If a reaction is taking place at constant temperature and constant volume then w  0 and hence the
first law U  q  w becomes U  qV , where qV is the heat absorbed at constant volume.
 U  U P  U R  qV = heat of reaction at constant volume.
 Thus internal energy is the heat of reaction at constant volume and at a given temperature provided
the quantities of the products and the reactants being the same as represented by the chemical
equation.
14.Heat content or enthalpy of a system (H):
 Enthalpy of a system is the heat content at constant pressure. In fact it is the total energy stored in a
system at constant pressure. It is denoted by ‘H’ and is given by-:
H  U  PV ------------ (5)
 The enthalpy of a system is an extensive property. It is a state function and has a definite value. The
absolute value of enthalpy can not be determined but the change in enthalpy can be which is of real
importance. If a system with enthalpy H1 changes to another state with enthalpy H2,
then H  H 2  H 1 . For a chemical reaction, H  H P  H R where H P and H R are the enthalpies
of product and reactants respectively. If q p is the heat absorbed at constant pressure,
then H  HP  HR  qp .
 Suppose a system with internal energy U 1 , enthalpy H 1 , volume V1 and number of moles n1 with
a constant pressure P changes to another state having internal energy U2, enthalpy H 2 , Volume
V2 and number of moles n2 , Then-: H 1 = U 1 + P V1 , H 2 = U2 + P V2
 H  H 2  H 1 =( U2 + P V2 )–( U 1 + P V1 )= U 2  U 1  P(V2  V1 )  H  U  PV ………….(6)
From ideal gas equation:-
PV  nRT
 PV2  PV1  ( n2  n1 ) RT
 PV  ng RT
  H  U  ng RT ---------------- (7)
15. Measurement of ∆U and ∆H-:
 In a chemical reaction, heat evolved or absorbed in measured by carrying out the reaction in an
apparatus called calorimeter. The principle is based on the fact that the heat given out in equal to the
heat taken in,
If Q = Amount of heat of reaction taken out
W = Water equivalent of the calorimeter
m = Mass of liquid taken the calorimeter
S = Specific heat
T1 = Initial temperature and
T2 = Final temperature
Q = (W + m) × S × (T2 – T1)
 The common types of calorimeter used for the measurement are
i. Water calorimeter
ii. Bomb calorimeter
16. Heat capacity and specific heat
 Heat Capacity of a system is the amount of heat required to raise the temperature of the system
through 1°C.
 Let (q) cal. of heat is absorbed by (m) mass of a substance and temperature is raised from T1 to T2,
then,
m = mass of substance
q = amount of heat required
T1 = initial temperature
T2 = final temperature
q q
Then C = C=
m(T2  T1 ) mT
q
If m = 1 gm, C = , where C = Specific hear or specific heat capacity.
T
q
If m = 1 mole, C = , where C = molar heat capacity
T
So, specific heat capacity is the amount of heat required to raise the temperature of 1 gm of
substance through 1°C.
Again “Molar heat capacity is the amount of heat required to raise the temperature of 1 mole of
substance through 1°C.

17. Types of Heat Capacity

It can be of two types:
1. Molar Heat Capacity at constant pressure (CP) :
 q dH
CP =  CP =  dH = CPdT and for n mole dH = nCPdT
t dT
2. Molar Heat at constant volume (CV)
q dV
CV =  CV =  dV = CVdT and for n mole dV = nCVdT
t dT
Here dH = Heat change at constant pressure
dV = Heat change at constant volume
R
Note : CP – CV = , where CV, CP = specific heat capacity at constant volume and pressure
M
respectively, M = molecular mass of the substance
Relation between CP and CV
We Know, H = U + PV
But PV = RT
Differentiate with respect to,
dH dV dT dH du dH du
 R   R    R  CP – CV = R, i.e., (CP > CV)
dT dT dT dT dT dT dT
18. Thermochemical Reaction :
 The reactions which takes place with the evolution and absorption of heat energy are called thermo
chemical reactions. These are of two kinds.
i. Exothermic reactions : Exothermic reactions are the chemical reactions where heat energy is
released out of the system. It can be represented as :
A + B  C + D + Q Kcal
OR
A + B  C + D ; H = –Q Kcal.
By plotting a graph of path of Reaction (Vs) Energy
ii. Endothermic Reactions : Endothermic reactions are the thermo chemical reactions where heat
energy is absorbed by the system. It can be represented by :
A + B  C + D – Q Kcal
OR
A + B  C + D ; H = +Q Kcal
By plotting a graph of path of Reaction (Vs) Energy
Exothermic products are more stable than endothermic products.
19. Enthalpy of Reaction / Heat of Reaction
 The total amount of heat energy evolved / absorbed when the no. of moles of reactant completely
reacts to give the product as given in the balanced chemical equation is known as heat of reaction or
enthalpy of reaction.
 In other words, it’s the difference between the enthalpies of product and reactant species when the
reactant completely reacts as per the given balanced chemical reaction. The enthalpy of reaction is
given by :
HR = HP – HR
 The different types of heat of reactions are according to the type of reactions. These are :
i. Enthalpy of Formation (Hf) : It is defined as the enthalpy change in one mole of a substance
is formed from its constituent elements in the standard date.
e.g. 2H2(gas) + O2(gas)  2H2O(liq.)
 Here, H = –572 KJ
572
 Enthalpy formation of H2O = = –286 KJ/mol.
2
 The enthalpy change in 1 mole of substance which is formed from its element in their standard state
at 1 atm. and 298 K (NTP) is known as standard enthalpy of formation (Hf).
NOTE :
 Standard enthalpy of elements are 0 (zero).
 H° of a reaction is known as standard enthalpy of a reaction. In terms of standard enthalpy of
formation. It is given by : H° = Hf°(product) – Hf°(reactant)
 In order to calculate the (Hf°), 1 mole of the product is written in the right hand side.
ii. Enthalpy of Combustion (HC) : It is the total enthalpy change when 1 mole of substance
undergoes complete combustion.
e.g. :- C(solid) + O2(gas)  CO2(gas) H = –393.5 KJ/mol.
Heat of combustion of carbon (HC) = –393.5 KJ/mol
NOTE :
 Enthalpy of combustion is always –ve.
 The energy released when 1 gm of a fuel or food is burnt is known as its fuel value / calorific value.
 Among the fuels, (H) has the highest fuel value.
 For calculating the enthalpy of reaction from enthalpy of combustion :
Hreaction = HC(reactant) – HC(product)
iii. Enthalpy of neutralization : It is defined as the change in enthalpy when 1 gm equivalent of an
acid is neutralized by base or vice-versa in dilute solution.
e.g. :- NaOH(aq.) + HCl(aq.)  NaCl(aq.) + H2O H = –57.1 KJ
NOTE :
 Heat of neutralization of strong acid and strong base or vice-versa is always equal to –57.1 KJ/–13.7
Kcal.
 Heat of neutralization of (weak acid + strong base) or (strong acid + weak base) or (weak acid +
weak base) is always less than –57.1 KJ.
 The heat of neutralization of a weak acid or weak base is equal to the difference between the heat of
neutralization of strong acid and strong base and heat of ionization of weak acid/base, i.e., –57.1 KJ
– ionization enthalpy of weak acid/base.
H weak acid + strong base  57.1 – Heat of ionization of weak acid/base
weak acid + weak base
strong acid + weak base

iv. Enthalpy of Ionization : It is the heat change when 1 mole of a gaseous atom is converted into
monovalent (+ve) ion.
e.g. :- Sodium gas gives Na+(gas) + e–
 Na  Na+(g) + e– H 495 KJ/mol.
v. Enthalpy of Fusion (Hfus) : It is the change in enthalpy when 1 mole of a solid substance is
converted into liquid at its melting point.
H2O(solid)  H2O(liq.) H = +6.02 KJ
It is always +ve.
Hfus = Total heat of fusion per gm. × mol. mass
 vi. Enthalpy of Vapourization (Hv) : It is the total heat change when one mole of liquid is
converted into vapours at its boiling point.
H2O(liq.)  H2O(gas) H = +43.93 KJ
It is always +ve.
vii. Enthalpy of Sublimation (Hsub) : It is the enthalpy change when one mole of a solid
substance changes directly into its vapour at a temperature below its melting point.
e.g. :- I2(solid)  I2(gas) H = +62.31 KJ
It is always +ve.
It’s the sum of enthalpy of fusion and enthalpy of vapourization.
 H°sub = H°fus + H°v
20. HESS’S LAW OF CONSTANT HEAT SUMMATION:
 It states that the enthalpy change during a chemical reaction remains the same whether the reaction
takes place in one step or in several steps.
 The enthalpy change of a chemical reaction is independent of the path followed.
 Consider a system changes from A to B with an enthalpy change of H. Let the same process is
carried out through 3 steps.
H1
A  C
H 2
C  D
H3
D  B
H
and A  B
According to Hess’ law, H = H1 + H2 + H3
Let H > (H1 + H2 + H3)
 Let A changes to B, the heat evolved is H. If B will be converted to A (H1 + H2 + H3) of
energy will be absorbed.
 As H > (H1 + H2 + H3), in doing a cycle an amount of H – (H1 + H2 + H3) surplus
energy will be available. On repeating the cycle again and again a large amount of energy will be
available which means a system will work without nothing, i.e., a perpetual motion machine can be
constructed which is against of 1st law of thermodynamics.
 Hence H > (H1 + H2 + H3) is not true. So,
H = H1 + H2 + H3
Application:
Hess’ law can be applied to determine:
i. Heat of formation
ii. Heat of combustion
iii. Heat of transition
iv. Heat of various reactions.
21. Enthalpy Change and Bond Energy:
The average amount of energy required to break one mole of a particular gaseous types of bonds in a
molecule to set free atoms or radicals is called bond energy.
OR
It is the amount of energy released when 1 mole of a particular bond is formed from the respective
atoms or reactants.
The heat of reaction from bond energy data can be calculated as :
Heat of reaction = Total bond energy of reactants – Total bond energy of products
 H = BER – BEP
nd
22. 2 Law of Thermodynamics:-
 The 2nd law of thermodynamics can be summarised by two statements:-
 Kelvin’s Statement:- It is impossible for a cyclic process to take heat from a cold resource and
convert it into work without at the same time transferring heat from a hot to a cold resource.
 Clausius Statement:-It is impossible to construct a machine which converts heat by a cyclic process
from one reservoir at a lower temperature to another at a higher temperature unless work is done
on the machine by an external agency.
 The well known cyclic process is the Carnot’s cycle and the efficiency of a heat engine which is
operating like Carnot’s engine in a reversible manner is given by:-
q q T T
  2 1  2 1 --------------------- (8)
q2 T2
 Thermodynamic reversible processes are very slow i.e. it is not possible to carry out a process
infinitesimally slowly. Hence efficiency of heat engine is always less than one and No heat engine
has yet been constructed which has an efficiency equal to unity.
23. The concept of entropy :-(S)
 Entropy is the measure of degree of randomness or disorderness of a system. It is a definite quantity
and is a state function. The absolute value of entropy can not be determined. However the change
in entropy can be determined from the final & initial state of the system. If S i and S f are the
entropy of the system at initial and final state of the system respectively, the change in entropy is
given by: -
S  Sf - Si ----------------------------- (9)
From Carnot’s cycle
q 2  q1 T2  T1 q T q q
  1  1  1  1 Or 1  2
q2 T2 q2 T2 T1 T2
 For a reversible process
q nev
= Constant ----------------------- (10)
T
q q
The term nev is known as the entropy ( S ) of the system i.e. S  nev ---------------------- (11)
T T
 From equation (11), S  q nev , thus with increase in temperature the entropy of the system
increases.
 If entropy of the system increases S becomes positive, on the other hand if the entropy of the
system decreases S becomes negative.
 The entropy of the universe tends to increase.
24. Standard entropy:
 Entropy of one mole of a substance in pure state at one atmospheric pressure and 250C is termed as
standard entropy of that substance and is denoted as S 0 . When in a reaction each reactant and
products involved are in their standard state, the entropy change is said to be standard entropy
change. This is denoted by S 0
S 0   S 0 products   S 0 reac tan ts --------------- (12)
Entropy change in reversible & irreversible or spontaneous process:
 Consider an isothermal expansion of an ideal gas at constant temperature into vacuum which will be
a spontaneous process. Here Since there is no opposing force, the work done w will be zero and also
V  0 as temperature is constant. Hence from the 1st law q  0 i.e. no heat is absorbed or
evolved in the process. In other words no heat is supplied or removed from the surrounding,
thus S surr  0 .
 But in the process volume of the gas increases, say from V1 to V2 at constant T .
V 
 Hence entropy of the system increases and is given by: - S  R In  2  as V2  V1 , thus
 V1 
there is change in entropy of the system and surrounding considered together increases. Therefore
for spontaneous process: S sys  S surr  0 ------------------ (13)
 Now if the expansion is carried out reversibly, the gas will do some external work.
q
 Consequently an equivalent amount of heat rev will be obtained by the system and the same
T
amount will be lost by the surrounding.
q q
 S sys  S surr  re v - re v  0 --------------------------------- (14)
T T
 Combining equation (13) & (! 4)
S sys  S surr  0 ----------------------- (15)
 In a reversible process the entropy of the system and the surroundings taken together remains
constant while in an irreversible process the entropy of the system and surrounding taken together
increase.
 Since all process in nature occur spontaneously it follows that entropy of the universe increase
continuously which is one of the statement of 2nd law also.
25. Free energy: - [Gibbs free energy ( G )]
 The Gibbs free energy is given by G  H  TS ------------ (18) where G is the Gibbs free energy, H
is the enthalpy, S is the entropy and T is the absolute temperature. If a system changes
from G1 , H 1 , T , S1 to G 2 , H 2 , T , S 2 , then
G  G2  G1  ( H 2  TS 2 )  ( H 1  TS1 )  H 2  TS 2  H 1  TS 1  ( H 2  H 1 )  T ( S 2  S1 )
 G  H  TS --------------------------------------- (19)
We have H  U  PU , TS  q rev
 G  U  pV  q rev  q rev  Wmax  pV  q rev  Wmax  pV
----------------- (20)
Or  G  Wmax  pV
 Wmax  pV , Is called as the net work done. From equation (20), it is clear that decrease in free
energy gives the net work done at constant temperature & pressure.
Variation of free energy with temperature and pressure: -
We know, G  H  TS
H  U  PV
 G  U  PV  TS
but Differentiating equation from first law of thermodynamics -:
dG  dU  PdV  VdP  TdS  SdT....................(21)
dq  dU  PdV
For a reversible process, dU  PdVin equation (21)
dq
Putting the value of dS   TdS  dq  dU  PdV
T
At constant pressure dP  0
 dG  TdS  VdP  TdS  SdT  VdP  SdT …(22)
 dG = –SdT

Gibb’s free energy and equilibrium-:

Consider a general reaction. A + B  C + D
Gibbs free energy for the above reaction at equilibrium, G = 0
We know that G = G° + RT lnK …(1)
Where G° = Standard free energy change i.e., when all reactants and products are at their standard
states of unit activity or concentration.
K = Thermodynamic equilibrium constant
So at equilibrium,
0 = G° + RT lnK …(2)
 G° = –RT lnK
= –2.303 RT log K …(3)
We also know that,
G° = H° – TS° …(4)
So, G° = H° – TS° = –RT lnK …(5)
Case I
In case of endothermic reaction, H is large and +ve. In such a case the value of K will be much smaller
than 1 and reaction is unlikely to form more product.
Case II
In case of exothermic reaction, H is large and –ve. G° is likely to be large and –ve. K will be much
larger than 1, the reaction is likely to form more product.
Since G also depends upon S, the value of K also gets affected depending on whether S in
+ve or –ve.
Equation (5) may be used to estimate G° from measurement of H° and S°. K can than be
calculated.
26. Criteria for feasibility of a process: -
Theromdynamic Term Sign Process
+ve Non-spontaneous
H –ve Spontaneous
0 Equilibrium
+ve Spontaneous
S –ve Non-spontaneous
0 Equilibrium
+ve Non-spontaneous
G –ve Spontaneous
0 Equilibrium
+ve Non-spontaneous
U –ve Spontaneous
0 Equilibrium
Gibb’s Hemlholtz equation and spontaneity
H S G Process
–ve +ve –ve Spontaneous (at all temperature)
–ve(low temp.) Spontaneous
–ve –ve
+ve (high temp.) Non-spontaneous
–ve(high temp.) Spontaneous
+ve +ve
+ve (low temp.) Non-spontaneous
+ve –ve +ve Non-spontaneous (at all temperature)
27. Third law of Thermodynamics
At absolute zero of temperature the products and reactions in solid state have same value of entropies.
So S tends to approach zero at 0K. On analogy with zero value of heat capacity at absolute zero, the
entropy value of all pure solids at 0K approach zero.
i.e. limS  0
T 0

This statement has led to following definition of third law of thermodynamics.

At absolute zero of temperature the entropy of every substance may become zero and it does
become zero in case of a perfectly crystalline solid.
In a crystalline solid the molecules, ions or atoms constituting the solid acquire definite positions in
the crystal lattice. The arrangement has lowest energy. There is zero disorder and hence associated with
zero value of entropy.
 CLASS-XI SUBJECT-CHEMISTRY
TEST YOUR UNDERSTANDING (CHEMICAL THERMODYNAMICS)

TYPE-I (MULTIPLE CHOICE QUESTIONS)

1. A system that can transfer neither matter nor energy to and from its surroundings is called
(a) A closed system (b) An isolated system
(c) An open system (d) A homogeneous system
2. A thermos flask is an example of
(a) Isolated system (b) Closed system
(c) Open system (d) none of these
3. A closed system is one which cannot transfer matter but transfer.
(a) Heat (b) work
(c) Radiations (d) all of these
4. A gas contained in a cylinder filled with a piston constitutes
(a) An open system
(b) A heterogeneous system
(c) A closed system
(d) An isolated system
5. A system that can transfer both energy and matter to and from its surroundings is called
(a) An isolated system (b) A closed system
(c) An open system
(d) A heterogeneous system
6. A system in which no thermal energy passes into or out of the system is called
(a) Adiabatic system (b) an open system
(c) A reversible system (d) a closed system
7. Which out of the following is not an intensive property?
(a) Pressure (b) concentration
(c) Density (d) volume
8. Which following is not an extensive property?
(a) Mass (b) volume
(c) Density (d) internal energy
9. Which of the following sets of properties constitute intensive properties?
(a) Temperature, pressure and volume (b) mass, density and volume
(c) Density, pressure and temperature (d) internal energy, density and pressure
10. The work done in the reversible expansion of a gas from the initial state A to final state B is
(a) Maximum (b) minimum
(c) Equal to zero (d) equal to infinity
11. The first law of thermodynamics is
(a) The total energy of an isolated system remains constant though it may change from one form to
another
(b) Total energy of a system and surroundings remains constant
(c) Whenever energy of one type disappears, equivalent amount of another type is produced
(d) All of the above
12. The mathematical relation for the first law of thermodynamics is
(a) ∆U = q - w
(b) ∆ U = 0 for a cyclic process
(c) ∆U = q for an isochoric process (d) all of these
13. For an adiabatic process, according to first law of thermodynamics,
(a) ∆U = -w (b) ∆U= w
(c) ∆U = q - w (d) none of these
14. Which of the following properties is not a function of state?
(a) Concentration (b) internal energy
 (c) Enthalpy (d) entropy
15. The change in enthalpy of a system is measured by measuring
(a) Heat of the process at constant volume
(b) Heat of the process at constant temperature
(c) Heat of the process at constant pressure
(d) None of these
16. The amount of heat required to raise the temperature of one mole of the substance by 1 K is called
(a) Heat capacity (b) Molar heat capacity
(c) Molar heat (d) Molar capacity
17. Heat capacity at constant volume is the change in
(a) Internal energy with temperature at constant volume
(b) Internal energy with temperature at constant pressure
(c) Enthalpy with temperature at constant volume
(d) Enthalpy with temperature at constant pressure
The heat capacity at constant pressure is related to heat capacity at constant volume by the relation
(a) Cv-R = Cp (a) Cp = Cv
(c) Cp-Cv = R (d) None of these
18. The phenomenon of lowering of temperature when a gas is made to expand adiabatically from a region of high
pressure into a region of low pressure is known as
(a) First law of thermodynamics (b) Second law of thermodynamics
(c) Le Chatlier's principle (d) Joule Thomson effect
19. Which of the following is not correct?
(a) H = E + PV (b) H-E=PV
(c) H-E-PV=0 (d) H=E-PV
20. When the total energy change in an isothermal cycle is zero, it represents
(a) A reversible cycle (b) an adiabatic change
(c) A thermodynamic equilibrium (d) an irreversible cycle
21. The change in enthalpy that takes place when one mole of the compound is formed from its elements is called
(a) Heat of formation of compound (b) heat of synthesis
(c) Heat of combustion (d) standard heat of formation
22. By convention, the standard heat of formation of all elements is assumed to be
(a) Zero (b) negative
(c) Positive (d) infinity
23. The change in enthalpy of a system when one mole of the substance is completely burnt in excess of oxygen is
called
(a) Heat of reaction (b) heat of formation '\
(c) Heat of oxidation (d) heat of combustion
24. The heat of neutralisation of a strong acid and a strong base is always
(a) Zero (b) constant
(c) Positive (d) changing
25. The heat change (or enthalpy change) when one mole of a solid substance is converted into the liquid state at
its_______is called heat of fusion.
(a) boiling point
(b) Melting point
(c) freezing point
(d) None of these
26. The change in enthalpy which occurs when one mole of an element changes from one allotropic form to another
is called.
(a) Heat of allotropy (b) Heat of transition
(c) Heat of transformation (d) Heat of fusion
27. In a chemical process, the amount of total heat change is same no matter by which method the change is brought
about. This is statement of
(a) Law of thermo chemistry (b) Hess's law
(c) Thermodynamic law (d) law of heat of reaction
28. The average amount of energy required to break all bonds of a particular type in one mole of the substance is
called
(a) heat of reaction
(b) bond energy
(c) heat of bond formation
(d) heat of transition
29. The heat of neutralization of an acid A with a base B is 13.7 kcal. Which of the following is true
(a) A is weak and B is also weak (b) A is strong and B is weak
(C) A is weak nd B is strong (d) A is strong and B is also strong
30. The heat of neutralization of one mole of H2SO4 with sodium hydroxide will be
(a) -13.7 kcal (b) -27.4 kcal
(c) +27.4 kcal (d) -6.85 kcal
Answer, (b)
31. The apparatus used to measure heat changes during chemical reactions is called
(a) polarimeter (b) colorimeter
(c) Calorimeter (d) none of these
32. Hess's law is used to determine
(a) Heat of formation of substances which are otherwise difficult to measure
(b) Heat of transition
(c) Heats of various other reactions like dimerization
(d) all of the above
33. Considering entropy as parameter in the following reaction at 298K: X (g) + Y (g) = XY (l)
(a) ∆S is negative
(b) ∆S is positive
(c) ∆S is zeo
(d) ∆S can not be predicted
34. If ∆G for a reaction is negative, the change is
(a) Spontaneous
(b) Reversible
(c) Irreversible
(d) Non-spontaneous
35. The enthalpies of all elements in their standard state are:
(a) One
(b) Different for all
(c) Zero
(d) Less than zero
36. The unit of entropy is
(a) JK-1mol-1
(b) KJ-1mol-1
(c) JK-1mol
(d) KJmol-1
37. Which of the following condition is correct for a spontaneous reaction?
(a) ∆G is negative
(b) ∆G is positive
(c) ∆G is zero
(d) None of the above
38. The enthalpy of combustion is always
(a) –Ve
(b) +ve
(c) Zero
(d) Same for all substance
39. The correct relation between ∆G, ∆H,∆S is
(a) ∆H = ∆G-T ∆S
(b) ∆H = ∆G+T ∆S
(c) ∆H =- ∆G-T ∆S
(d) ∆H = ∆G X T ∆S
40. Which of the following is true for a reaction to proceed spontaneously?
(a) Both ∆H and ∆S are positive
(b) Both ∆H and ∆S are negative
(c) ∆H is positive but ∆S is negative
(d) None of the above
41. In which of the following change there is an increase in entropy?
(a) SO2(g)+1/2O2(g)SO3(g)
(b) Ice Water
(c) Both (a) and (b)
(d) None of the above
42. A reaction A+BC+D+q, is found to have a positive entropy change. The reaction will be
(a) Possible at high temperature
(b) Possible only at low temperature
(c) Not Possible at any temperature
(d) Possible at any temperature
43. Heat of neutralization of a strong acid and a weak base is
(a) 13.7 kcal
(b) Greater than 13.7 kcal
(c) Less than 13.7 kcal
(d) None of the above
44. A spontaneous change is one in which the system suffers
(a) An increase in internal energy
(b) A lowering of entropy
(c) A lowering of free energy
(d) No energy change.
45. For which reaction from the following, S will be maximum?
(a) Ca (s) + ½ O2 (g)  CaO (s)
(b) CaCO3 (s)  CaO (s) + CO2 (g)
(c) C (s) + O2 (g)  CO2 (g)
(d) N2 (g) + O2 (g)  2 NO (g)
46. Heat of transition is the heat evolved or absorbed when a substance is converted from
(a) solid to liquid
(b) solid to vapour
(c) liquid to vapour
(d) one allotropic form to another allotropic form.
47. A solution of 500 ml. Of 0.2 M KOH and 500 ml of 0.2 M HCI is mixed and stirred; the rise in temperature is
T1. The experiment is repeated using 250 ml each of solution, the temperature rise is T2. Which of the
following is true?
(a) T1 = T2 (b) T1 = 2T2
(c) T1 = 4T2 (d) T1 = 9T2
48. The occurrence of reaction is impossible if
(a) H is +ve; S is also +ve
(b) H is - ve; S is also – ve
(c) H is - ve; S is +ve
(d) H is +ve; S is – ve
49. A mixture of 2 moles of carbon monixide and one mole of oxygen in a closed vessel is ignited to get carbon
dioxide. If H is the enthalpy change and E is the change in internal energy.
(a) H > E (b) H < E
(c) H = E (d) not definite.
TYPE-2 (VERY SHORT TYPE QUESTION)
(Each question carries 1 mark)
1. Define bond energy.
2. Write the equation for free energy change of a reversible gaseous reaction at equilibrium.
3. Explain endothermic reaction with an example
4. What is the value of entropy change at equilibrium condition?
5. Write Gibbs Helmholtz equation.
6. For an exothermic process ∆H is -------------
7. When water changes in to water vapour its entropy ---------------
8. Arrange the following in the increasing order of entropy
Water vapour, liquid water and ice
9. Write the equation relating entropy change, free energy change and enthalpy change.
10.How does free energy change indicates the equilibrium condition and spontaneity of a process?
11.The relation between free energy change and electrical energy is---------------
12.The relation between standard free energy change and equilibrium constant is---------------
13.The relation between enthalpy of sublimation, enthalpy of fusion and enthalpy of vapourisation is---------------.
14.What is the criterion for spontaneity in terms of free energy?
15.In which type of reaction reactants have less energy as compared to product?
16.Under which condition ∆H =∆U?
17.The dissociation energy of CH4 is 360 Kcal. What is the bond energy of C-H bond?
18.What is the free energy change of a reaction at 270C with an enthalpy change of 5 Kcalmol-1 and entropy change
of 15 e.u?
19.Calculate the entropy of vaporization for a liquid boiling at 300K having enthalpy of vaporization 27.0 KJmol-1.
20.What is calorific value of food or fuel?
TYPE-3 (SHORT TYPE QUESTION)
(Each question carries 2/3 marks)
1. Bond energy of F2 and Cl2 are 36.6 and 58.0 Kcal per mole respectvely. If heat liberated in the reaction F2 +
Cl22ClF is 26.6 Kcals calculate the bond energy of Cl-F bond.
2. Calculate the C-C bond energy from the following data
(i) 2C(graphite) + 3H2(g) C2H6(g), ∆H=-84.67KJ
(ii) C(graphite)  C(g) ∆H =-710.7KJ
(iii) H2(g)2H(g), ∆H=-435.9KJ
(iv) C-H bond energy is 416KJ
3. Given that the average bond energies of C-C, C=C, C-H and H-H are respectively 80.5, 145, 98.2 and 103 Kcal
mol-1, calculate the enthalpy of the reaction per mole.
4. The dissociation energy of methane and ethane are 360 and 620 Kcal/mole. What is the bond energy of C-C
bond?
5. State Hess’s law.
6. When ice melts into water entropy increases. Explain.
7. Entropy of the universe is increasing. Explain.
8. Global warming is one of the causes of increase in entropy of the universe. Comment.
9. Show that internal energy is a state function.
10. Define enthalpy of formation.
11. What is the equilibrium constant K for the following reaction?
2NOCl(g)2NO(g)+Cl2(g) , ∆H0=77.2 KJmol-1, ∆S0=122JK-1 at 400K.
12. For the equilibrium PCl5(g)PCl3(g) + Cl2(g) at 298K, K=1.8X10-7. What is ∆G0for the reaction?
13. Calculate the enthalpy of formation of methane. Given
a) C(graphite)  O2(g)  CO2(g) , H  393.5kj
b) 2H2(g)  O2(g)  2H2O(1) , H  571.8kj
c) CH4(g)  2O2(g)  CO2(g)  2H2O(1) , H  890.3kj TYPE-4 (LONG ANSWER TYPE QUESTIONS)
(Each question carries 5 marks)
1. State and explain Hess’s law. Write its applications
Calculate the heat of formation of benzene Given that the standard heat of combustion of benzene is 3266KJ and
standard heat of formation of CO2 (g) and H2O (l) are -393.1 KJ and -286KJ respectively.
2. Define the terms enthalpy, entropy and free energy change. Derive Gibb’s Helmholtz equation in terms of G &H.
 CHEMICAL EQUILIBRIUM
1. Irreversible and Reversible Reactions:
 “A chemical reaction is said to be irreversible if the products formed have no tendency to react
with each other to give the original reactants”.
 This is due to the reason that in such reactions generally one or more of the products separates
out as insoluble or volatile species, which serves as sink and makes the reaction
unidirectional.
 Ex: - NaOH +HCl  NaCl +H2O, AgNO3 (aq)+ NaCl (aq)  AgCl (S)+ NaNO3 (aq)
 “A chemical reaction is said to be reversible if the products formed react with each other to
give the original reactants again”.
 Ex: - PCl5(g)  PCl3(g) + Cl2(g)
CaCO3(s)  CaO(s) + CO2(g)
2HI(g)  H2(g) + I2(g)
 Irreversible reactions proceed in one direction (foreword direction) only whereas reversible
reaction proceeds in both directions (forward as well as backward).
 Irreversible reactions always proceed towards completion.
 Irreversible reactions have no tendency to attain a state of equilibrium but reversible reactions
possess such tendency.
2. Physical equilibrium:
 The equilibrium established in physical process like evaporation, condensation, fusion,
sublimation, dissolution is called physical equilibrium. There are 3 types of physical
equilibrium.
i. S  L equilibrium
This is the equilibrium state between melting process of solid  liquid (forward reaction)
and freezing of liquid  solid (backward)
S o lid       
m e lt in g / f u s io n
 L i q u i d
fre e z in g

In such a state : a) rate of fusion = rate of freezing

b) both the solid and liquid co-exist at equilibrium at a particular
temperature called melting point or freezing point.
ii. L  G equilibrium
It is the equilibrium state between evaporation state between gas and condensation of
vapour to liquid.
 
vapourisation
Liquid   Gas
condensation

In such a state : a) rate of evaporation = rate of condensation

b) both liquid and gas co-exist at equilibrium at a particular
temperature.
iii. S  G equilibrium
It is the equilibrium state between sublimation of solid gas directly and condensation of
gas  solid directly.

 Gas
sublimation
Solid  In such a state : rate of sublimation = rate of condensation
condensation

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Note :
 Equilibrium involving gases can be established only in a closed system. The concentration of
various substances at equilibrium become constant at a given temperature.
 The intermediate values of K (103 - 10–3) shows that concentration of products and reactants
are comparable.
3. Chemical equilibrium:
 “The state of a system, where it’s observable properties like pressure, concentration, density,
colour etc. do not undergo any noticeable change is known as the equilibrium state and
equilibrium refers to chemical systems in known as chemical equilibrium”. The characteristics
of chemical equilibrium are as follows.
i. Equilibrium state is achieved only if the reaction is carried out in a closed vessel.
ii. Chemical equilibrium at a given temperature is characterised by constancy of certain
observable properties like pressure, concentration, colour, density etc.
iii. Chemical equilibrium is dynamic in nature i.e. at the point of equilibrium the reaction
doesn’t come to a stop but the rate of forward reaction is equal to the rate of backward
reaction.
iv. Chemical equilibrium can be approached from either side.
v. When equilibrium is attained at a given temperature, each reactant and each product has a
fixed concentration i.e. the composition of the reaction mixture remains constant.
vi. A catalyst can hasten the approach of equilibrium but doesn’t alter the state of equilibrium.
vii. At the state of equilibrium the free energy change G is zero.

4. Law of mass action: -

 It states that – “The rate at which a substance reacts is directly proportional to its active mass
and the rate of a chemical reaction is directly proportional to the product of the active masses
of the reacting species”.
Consider a reaction: - A + B + C + ……………  Products
Then rate at which A reacts  [A]
Rate at which B reacts  [B]
Rate of the reaction, r  [A] [B] [C] ……
[Active mass means molar concentration i.e. moles / liter (n/V) which have certain value for
liquids and gases but for solids it is always taken as unity]. Active mass of ‘A’ can be denoted
as [A] or CA
5. Law of chemical equilibrium: -
Kf
 Let us consider a general reaction: - aA  bB  lL  mM , ÷÷here A, B are the reactants with
Kb

stochiomertric coefficients a, b respectively and L, M are the products with stochiomertric

coefficients l, m respectively.
 According to Law of mass action, the rate of reaction is proportional to the active mass of each
reacting species raised to their power equal to their stochiomertric coefficients in the reaction.
 Hence for the above reaction -:
The rate of forward reaction, Rf =Kf [A] a [B] b
The rate of backward reaction, Rb= Kb [L] l [M] m
Where Kf and Kb are the rate constants for the forward and backward reactions respectively
and [A], [B] and [L], [M] are the molar concentration of the reactants and products respectively.
 At equilibrium the rate of forward and backward reactions are equal. I.e. Kf [A] a [B] b = Kb [L] l
[M] m
Kf [L]l [M]m (C )l (C ) m
  Kc  a b
orK c  L a M b …………(1)
Kb [A] [B] (CA ) (C B )
 Equation (1) is known as law of chemical equilibrium. Thus “ For a reversible chemical
reaction the ratio of product of the active masses of the products formed to that of the
reactants, each raised to the power equal to their stochiomertric coefficients is constant at a
constant temperature and is known as the equilibrium constant”.
 When partial pressure is involved (for gaseous reactions), the equilibrium constant can be
(PL ) l (PM ) m
expressed as: – K P  ...............(2)
(PA ) a (PB ) b
Where KP is the equilibrium constant for the reaction in terms of partial pressure. P L, PM, PA, PB
are partial pressure of L, M, A, and B respectively.
 When mole fraction is involved then the equilibrium constant can be expressed as: –
(X L )l (X M ) m
KX  .................(3)
(X A ) a (X B ) b
Where KX is the equilibrium constant for the reaction in terms of mole fraction. XL, XM, XA,
XB are mole fraction of L, M, A, and B respectively.
6. Relationship between Kp, Kc and Kx: -
i. Relation between Kp and Kc: -
Kf
Let us consider a general reaction: - aA  bB  lL  mM
Kb

Where A, B are the reactants with stochiomertric coefficients a, b respectively and L, M are
the products with stochiomertric coefficients l, m respectively.
When partial pressure is involved (for gaseous reaction), the equilibrium constant can be
(p )l (p ) m
expressed as: – K P  L a M b
(p A ) (p B )
ni n
For an ideal gaseous mixture -: PiV  ni RT  Pi  RT  Ci RT ,WhereCi  i is the molar
V V
th
concentration of the i component in the mixture of total volume V.

Page| 3
 Hence p L  C L RT , p M  C M RT , p A  C A RT , p B  C B RT
( p L ) l ( p M ) m C L RT  C M RT  C  C 
l m l m

KP  =  L a M b RT l  m a b   K c ( RT ) n
a
( p A ) ( pB ) b
C A RT  C B RT  C A  C B 
a b

Kp  Kc RT  .......... .......... .(4)

n

Where ∆n=(l+m)-(a+b)= (no of moles of gaseous products) – (no of moles of gaseous

reactants), R = universal gas constant, T = Absolute temperature.
Case – 1 -: If ∆n = 0 then Kp= Kc. e.g. H2 (g) + I2 (g)  2HI(g).
Case – 2 -: If ∆n >0 then Kp>Kc. e.g. PCl5 (g)  PCl3 (g + Cl2 (g).
Case – 3 -: If ∆n <0 then Kp < Kc. e.g. N2 (g) + 3H2(g)  2NH3 (g).
ii. Relationship between Kp & Kx –:
( PL )l ( PM ) m
From equation (2) we have, K P 
( PA ) a ( PB )b
But partial pressure of a particular component= Total pressure X mole fraction of that
component. I.e. p I  PX I  p L  PX L , p M  PX M , p A  PX A , p B  PX B
Putting the values in the expression for Kp-:
( PL ) l ( PM ) m PX L l PX M m  X L l  X M m P l  m  a  b   Kx ( P )  n
Kp  = 
( PA ) a ( PB ) b PX A a PX B b  X A a  X B b
 Kp  KxPn ..............(5)
iii. Relation between Kc &Kx -: From equation (4) and (5), we have
n
 RT 
Kc RT  = Kx ( P ) n  Kx  Kc  Kc V 
n n

 P 
 Kx  Kc(V )n ............(6)

7. Characteristics of equilibrium constant: -

i. It is a numerical value, which is constant at a given temperature for a particular reaction, and
changes with change in temperature.
ii. The value of K is independent of initial concentration of reactants, presence of catalyst, change
of pressure, Volume, presence of inert material, direction from which equilibrium is reached
and the nature and number of steps in the reaction as long as stochiomertric is not changed.
iii. Equilibrium constant for backward reaction is the reciprocal of equilibrium constant for the
forward reaction. I.e. K backward = 1/K forward. E.g. PCl5 (g)  PCl3 (g) + Cl2 (g)
iv. K forward = [PCl3] [Cl2] / [PCl5], K backward = [Pcl5] / [PCl3][Cl2]
v. If a reaction is multiplied by a factor m than the new equilibrium constant becomes
NO 2 
K1 = (K) m. E.g. NO (g) + ½ O2 (g)  NO2 (g), K  1
[ NO][O2 ] 2

2NO + O2  2NO2 (multiplied by 2) K 1 

NO2 2 K1 = K2
NO2 O2 

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 vi. If a reaction is divided by a factor n than the new equilibrium constant becomes -: K1 =n K .

E.g. N2 + 3H2  2NH3, K 

NH 3 2
[ N 2 ][ H 2 ]3
1 3
N 2  H 2  NH 3 (Divided by 2), K1  NH 3   K1  K
2 2 1 3
N 2 2 H 2 2
vii. If a reaction is taking place in several steps than the equilibrium constant for overall reaction is
equal to multiplication of equilibrium constants of all the steps. E.g.
 - - 2- 2- 3-
H 3 PO 4 
K1
H  H 2 PO 4 , H 2 PO 4 
K2
H   HPO 4 , HPO 4 
K3
H   PO 4
3H   PO 4
3-
H 3 PO 4 
K

- 2- 3- 3-
[H  ] [H 2 PO 4 ] [H  ][HPO 4 ] [H  ][PO 4 ] [H  ]3 [PO 4 ]
K1  , K2  -
, K 3  2-
, K 
[H 3 PO 4 ] [H 2 PO 4 ] [HPO 4 ] H 3 PO 4
- 2- 3- 3-
[H  ] [H 2 PO 4 ] [H  ][HPO 4 ] [H  ][PO 4 ] [H  ]3 [PO 4 ]
K 1 .K 2 .K 3  X -
X 2-
 K
[H 3 PO 4 ] [H 2 PO 4 ] [HPO 4 ] H 3 PO 4
 K  K1 .K 2 .K 3

viii. For a reaction A + B  C + D, K = Kf / Kb, where K is the equilibrium constant, Kf and Kb are
rate constant for the forward and backward reactions respectively. Thus if the forward reaction
in exothermic than the value of K decreases with increase in temperature and increases with
decrease in temperature.
ix. In case of heterogeneous equilibrium for expressing equilibrium constant, concentration of a
pure solid or liquid is taken as unity and the concentration of a pure solvent is taken as
constant.
x. The value of K is always greater than zero. If K is very large, the reaction proceeds towards
completion. If k = 1 concentration of reactants and products are nearly at equilibrium, while if
K is very small hardly any products are formed.
xi. Greater the value of equilibrium constant of a reaction greater will be the stability of the
products and instability of the reactants.

Kf
xii. For a reaction aA  bB  lL  mM at any state other than the equilibrium state,
L l M m Q
Kb Aa B b
is called the reaction quotient.
8. Types of chemical equilibrium: -
 There are two kinds of chemical equilibrium which are Homogeneous equilibrium, where all
the reactants and products are in the same phase and heterogeneous equilibrium where
reactants and products are in two or more different phases.
H2 (g) +I2 (g)2HI(g) (homogeneous)
NH4HS(s)NH3(g)+H2S(g) (Heterogeneous)

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9. Factors altering state of equilibrium: (The lechatlier’s principle)
 It states that – “when a system in equilibrium is subjected to any change in concentration,
pressure or temperature, the equilibrium shifts in such a direction so as to undo or cancel the
effect of stress. The various effects are discussed as follows -:
i. Effect of change of concentration: -
 According to this principle, if a small amount of reactants are added at equilibrium,
then the equilibrium will shift towards the product side after partially using the
reactants. Consider a reaction between N2 and H2 to give NH3 in a closed vessel as per
the reaction
N2 + 3H2  2NH3, H =negative
 According to Lechatlier’s principle, for the above reaction with increase in
concentration of N2 or H2, more NH3 will be formed while more N2 or H2 will be
formed if Concentration of NH3 is increased.Thus-
Increase in concentration of any of the reactant 
shift the equilibrium
 Forward direction
Decrease in concentration of any of the reactant 
shift the equilibrium
 Backward direction
ii. Effect of change of temperature: -
 According to this principle, if the temperature of the system is increased at equilibrium,
then the equilibrium will shift in the direction where heat is absorbed that is towards
endothermic side. On the other hand a decrease in temperature will shift the equilibrium
in a direction where heat is evolved, that is towards exothermic side. Consider the
reaction - N2 + 3H2  2NH3, H = negative
 According to Lechatlier’s principle, for the above reaction with decrease in temperature
more NH3 will be formed, as the forward reaction is exothermic and with increase in
temperature more of N2 and H2 will form.Thus-
Increase in temperature 
shift the equilibrium
 Endothermic side
Decrease in temperature 
shift the equilibrium
 Exothermic side
iii. Effect of change of pressure: -
 According to this principle increase in pressure at equilibrium will shift the equilibrium
towards less number of moles as with increase in pressure the number of moles
increases. On the other hand decrease in pressure at equilibrium will shift the
equilibrium towards large number of moles as with decrease in pressure the number of
moles decreases. Consider the reaction - N2 + 3H2  2NH3, H = negative
 According to Lechatlier’s principle, for the above reaction increase in pressure
produces more NH3. Thus-
Increase in Pressure 
shift the equilibrium
 Less number of mole side
Decrease in Pressure 
shift the equilibrium
 Large number of mole side
iv. Effect of addition of inert gas: -
 Addition of inert gas has no effect on equilibrium at constant volume whatever may be
the value of ng

Page| 6
  Addition of inert gas has no effect on equilibrium at constant pressure if ng = 0, but if
ng  O then addition of inert gas at constant pressure shifts the equilibrium towards
large number of moles. I.e. if np>nr  equilibrium will shift to forward direction
 If np<nr  equilibrium will shift to backward direction.
10. Applications of Lechatlier’s principle: -
(a) Lechatlier’s Principle applied for some common processes: -
i. Haber’s Process: -
N2 + 3H2  2NH3(q), H = -Ve
Forward reaction is favored by –
i. High concentration of N2 and H2
ii. Low temperature
iii. High pressure.
ii. Birkland & Eyde Process: -
N2 + O2  2NO, H = +Ve
Forward reaction is favored by –
i. High concentration N2 and O2
ii. High temperature
iii. Pressure has no effect since ng = 0
iii. Contact process: -
2SO2 + O2  2SO3, H = -Ve
Forward reaction is favored by –
i. High concentration SO2 and O2
ii. Low temperature
iii. High pressure
iv. Decomposition of nitrogen tetroxide-
N2O4  2NO2, H = +Ve
Forward reaction is favored by –
i. High temperature
ii. Low pressure
iii. Excess of N2O4.
(b) Lechatlier’s principle and physical equilibrium:
1. Solid  Liquid, H = +Ve
Increase in temperature  shifts the equilibrium towards right.
Decrease in temperature  shifts the equilibrium towards Left.
If on melting volume decreases, e.g. ice  water

Page| 7
 Large volume less volume
Increase in pressure  shifts the equilibrium towards right.
Decrease in Pressure  shifts the equilibrium towards Left
If on melting volume increases, e.g. S(s) S (l), H = +Ve, then
Increase in pressure  shifts the equilibrium towards Left
Decrease in Pressure  shifts the equilibrium towards right
[Because Increase in pressure lowers the melting point of ice where as raises the melting point of
sulphur]
2. Liquid  Vapour, H = +Ve
Increase in temperature  shifts the equilibrium towards Right
Decrease in temperature  shifts the equilibrium towards Left
Increase in pressure  shifts the equilibrium towards Left
Decrease in Pressure  shifts the equilibrium towards Right
[Because Increase in pressure raises the B.P of liquid (principle of pressure cooker)]
3. Effect of temperature on solubility: -
 If dissolution of solute is accompanied by absorption of heat then it is favoured by
increase in temperature, and if it is accompanied by evaluation of heat than it is
favoured by decrease in temperature.
4. Effect of pressure on solubility of gases: -
 Solubility of a gas on a liquid increases, with increase in pressure due to decrease in
volume.
(c) Lichatlier’s principle applied to living systems: -
i. Transport of oxygen by hemoglobin in blood: -
Hb(s) + O2 (g)  HbO2(s)
ii. Removal of CO2 from tissue by blood: -
CO2 (g) + H2O (l)  H2CO3 (aq)  H+ (aq) + HCO3– (aq)
iii. Sweet substances cause tooth decay: -
Ca5 (PO4) 3OH (s)  5Ca2+ (aq)+3PO43 –(aq) + OH – (aq)

Page| 8
 IONIC EQUILIBRIUM
1. Concepts of acids and bases:
 Different concepts have been put forward by different investigation to characterize acid and
base, but the following of the 3 modern concepts of acids and bases :
1) Arrhenius concept
2) Bronsted-Lowry concept
3) Lewis concept
1) Arrhenius Concept
According to this,
 Acids are those substances which furnish H+ ions when dissolved in water.
e.g., HCl(g) + (aq.)  H+(aq) + Cl–(aq.)
HNO3(l) + (aq.)  H+(aq.) + NO3–(aq.)
H2SO4(l) + (aq.)  2H+(aq.) + SO42– (aq.)
CH3COOH(l) + (aq.)  CH3COO–(aq.) + H+(aq.)
 Bases are those substances, which can OH– ion when dissolved in water
e.g., NaOH(s) + (aq.)  Na+(aq.) + OH–(aq.)
NH4OH(l) + (aq.)  NH4+(aq.) + OH–(aq.)
 Neutralization of acid and base is based on the key reaction between H+ ion and OH– ion to
form H2O molecule.
H+(aq.) + OH–(aq.)  H2O(l)
Limitations :
 According to Arrhenius, an acid release H+ ion in aqueous medium, but H+ is a proton which
cannot exist independently. It receives 2e–s from H2O and exists as hydrated P+ or oxonium ion
or hydroxynium ion (H3O+).
..
H   H — O— H  H 3 O  (hydroxonium ion)
..

 It fails to explain the acidic and basic properties of substances in solvents rather than water.
 It fails to explain the acidic character of substances like CO2, SO2 etc which do not contain H2.
 It fails to explain the neutralization reaction in absence of water.
2) Bronsted-Lowry Concept (P+ transfer theory)
According to this,
 An acid is a substance(molecule/ion), which can donate a proton to any other substance and a
base is a substance which can accept a proton from any other substance.
e.g.,

 In the above example, HCl donate a proton to H2O. Thus HCl is an acid. H2O accept the
proton, thus H2O is a base.
e.g.,

 Neutralization of an acid and base is simply the transfer of proton between an acid and a base.

Page| 9
 HCl + NH3  NH4+ + Cl– NH4Cl
Note :
a) When an acid looses a proton, the residual part have a tendency to accept a proton. So it acts as a
base. This pair of acid and base is differ by a proton are said to form a conjugate acid base pair.
Acid  H+ + conjugate base

Base + H+  conjugate acid

Limitations :
 It fails to explain the acidic character of AlCl3, FeCl3, BF3 etc.
 It fails to explain the reaction between acidic oxides and basic oxides.
3) Lewis Theory :
According to Lewis,
 An acid is defined as any substance that accepts at least a pair of e–s.
e.g., i. Species which contain e– deficient atoms : AlCl3, FeCl3, BF3, FeCl2, ZnCl2, SO3
etc.
ii. All cations : Ca2+, Fe3+ etc.
iii. Molecules which can accommodate more e– in vacant d-orbitals : SiCl 4, SiF4
etc.
iv. Molecules having multiple bonds between atoms of different : CO2, SO2 etc.
 Lewis acids are e– acceptors.
 A base is defined as a substance which can donate a pair of e–s.
e.g. : i) Molecules having one or more lone pair of e–s :
ii) all anions : OH–, Cl–, CH3COO–, SO42–, CN–, Br– etc.
 Lewis bases are e– donors.
 Whenever an acid and base react, a co-ordinate bond is formed.
Limitations :
 It fails to explain the strength of acids and bases.
 Dative bonds are always not formed when acid and base reacts.
Acid-base reactions are fast for the formation of dative bond is a slow process.
2. Ionisation of electrolytes -:
 When an electrolyte is dissolved in water, it splits up into charged particles called ions. The
ions formed have a tendency to reunite to form unionised electrolyte. As a result equilibrium is
established called ionic equilibrium between the ions formed and the unionised electrolyte.
e.g., AB  A++ B-.
 Thus “ionic equilibrium is defined as the dynamic equilibrium established between the ions
and unionised molecules of weak electrolyte in solution”.
 Some electrolytes ionise almost completely when dissolved in water and are known as strong
electrolytes. e.g., HCl, NaOH, NaCl. While some electrolytes ionise to small extent when
dissolved in water and are known as weak electrolytes. e.g., CH3COOH, NH 4OH.
 The fraction of total number of molecules of an electrolyte, which splits up in to ions, is called
degree of ionisation (). Thus -:

P a g e | 10
 number of molecules of electrolyte which splits up in to ions
Degree of ionisation ()=
Total number of molecules of electrolyte
3. Ostwald’s dilution law-:
 Consider a weak electrolyte (AB) is dissolved in water .Its ionisation can be shown as –:
AB  A++ B-
 Let initial concentration of undissociated ‘AB’ =C moles/ litre, and degree of dissociation
at equilibrium =, then the ionisation can be represented as
Initial conc. C moll-1 0 0
AB  A+ + B-
Equi.Conc. C (1-) C C
[ A  ][ B  ] C .C C 2 2 C 2
Applying law of chemical equilibrium -: K     . Since  is
[ AB] C (1   ) C (1   ) 1  
very small for weak electrolytes 1- can be taken as 1.
K 1
 K = C 2      ............(14) .
C C
 If one mole of the electrolyte is dissolved in V litre of the solution, then  V . Where K is
known as dissociation or ionisation constant and the equation (14) is the mathematical form of
Ostwald’s dilution law. Hence Ostwald’s dilution law for weak electrolytes can be stated as -: “The
degree of ionisation is inversely proportional to the square root of the molar concentration or
directly proportional to the square root of the volume (in litres) containing one mole of electrolyte
at a given temperature”.
 For binary acids (HA) with dissociation constant (Ka), Ostwald’s dilution law can be written as –:
Initial conc. C moll-1 0 0

HA  H++A-
Equi.Conc. C (1-) C C
[ H  ][ A  ] C .C C 2 2 C 2
Applying law of chemical equilibrium -: K a     . Since  is
[ HA] C (1   ) C (1   ) 1  
very small for weak electrolytes 1- can be taken as 1.
Ka Ka
 K a = C 2    , [ H  ]  C  C  K a C ……….(15)
C C
 For binary bases (BOH); with dissociation constant (Kb), Ostwald’s dilution law can be written as
–: Initial conc. C moll-1 0 0

BOH  B++ OH-

Equi.Conc. C (1-) C C
[ B ][OH ] C .C
 
C 2 2 C 2
Applying law of chemical equilibrium -: K a     . Since 
[ BOH ] C (1   ) C (1   ) 1  
is very small for weak electrolytes 1- can be taken as 1.
Kb Kb
 K b = C 2    , [OH  ]  C  C  K b C …….(16)
C C
4. Relative strength of acids and bases-:

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 For two acids having dissociation constants Ka1 and Ka2 and degree of dissociation 1and
1 K a1  K b1
2,  similarly for two bases, 1 
2 K a2 2 K b2
Since degree of dissociation is a measure of strength of acids and bases, hence-
Strength of acid HA1 K a1 Strength of base BOH1 K b1
 ,similarly  ............(17)
Strength of acid HA 2 Ka2 Strength of base BOH 2 K b2
5. Ionisation of polybasic acid strength-:
Acids having more than one ionisable proton per molecule are known as polybasic acids.
e.g., H2C2O4 (oxalic acid), H2SO4 (Sulphuric acid), H3PO4 (Phosphoric acid)
 For a diabasic acid H2X the ionization reactions are represented as :

i. H2X (aq)  H+(aq) + HX–(aq)

ii. HX–(aq)  H+(aq) + X2–(aq)
Equilibrium constant for (i) is.
[H  ][HX  ]
K1 =
[H 2 X]
Equilibrium constant for (ii) is
[H  ][HX 2  ]
K2 =
[HX  ]
Where K1 and K2 are called 1st 2nd ionization constant of the acid H2X. The values of ionization
constants for some polybasic acids are given in the following table.
Ionisation Constant of some Polybasic Acid (298 K)
Acid K1 K2 K3
Oxalic acid 5.9 × 10–2 6.4 × 10–5 -
Ascorbic acid 7.4 × 10–4 1.6 × 10–12 -
Sulphuric acid Very large 1.2 × 10–2 -
Carbonic acid 4.3 × 10–7 5.6 × 10–11 4.0 × 10–7
Phosphoric acid 7.5 × 10–3 6.2 × 10–8 4.2 × 10–13
The value of K2, K3 are smaller than K1 in case of polybasic acids. This is because it is
increasingly difficult to remove positively charged proton from negative ion due to electrostatic forces.
6. Ionic product of water-:
 Pure water is a weak electrolyte and is feebly ionised. The ionisation of water can be
represented as-: H2O  H+ + OH –
[H  ] [OH - ]
 Applying law of chemical equilibrium-: K C 
[H 2 O]
Since H2O undergo feebly ionisation, concentration of undissociated H2O is taken as
constant.
 K C X k  [H  ] [OH - ] or K W  [H  ] [OH - ]........( 18)
Where, Kw is the ionic product of water
 The value of Kw at 25oC is found to be 1 x 10 –14 mol2 l–2

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 For pure water [H+] = [OH-]= 1X 10 14 = 1 x 10 –7 moll–1
 If [H+] = [OH-] = 10 –7, the solution is neutral
 If [H+] >10 –7 or [OH-] < 10 –7, the solution is acidic.
 If [H+] < 10 –7 or [OH-] > 10 –7 the solution is basic.
 The value of Kw increases with increase in temperature.

7. The pH scale-:
 The pH scale was introduced by Surensen and is a more convenient method to determine
acidic character. It is defined as the negative logarithm of H+ ion concentration. pH =
+ -
- log [H ],Similarly pOH=-Log [OH ].

We have KW=[H+][OH-]-Log KW= -Log [H+][OH-] or pKw=pH+pOH

 For a weak acid -:

1
[ H  ]  K a C  pH  p K a C   log K a  log CorpH  1 pK a  log C.....(19)
2 2
 For a weak base-:

1
[OH  ]  K b C  pOH  p K b C   log K b  log CorpOH  1 pK b  log C.....(20)
2 2
[H+] 100 10-1 10-2 10-3 10-4 10-5 10-6 10-7 10-8 10-9 10-10 10-11 10-12 10-13 10-14

pH 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Acidic Character Basic character
Neutral
5. Common ion effect: -

“The suppression of dissociation of a week acid or weak base by the addition of a strong
electrolyte containing its own ions is known as common ion effect”.
 E.g., CH3COOH  CH3COO - + H+, if at equilibrium small amount of CH3COONa is
added, the dissociation of CH3COOH will be suppress.
6. Solubility product: -
 Substances like BaSO4, AgCl etc., which dissolves in water to an extremely small extent,
are known as sparingly soluble salts. The equilibrium between the ions and the undissolved
particles for the sparingly soluble salts AgCl can be represented as -: AgCl  Ag+ + Cl–.
[Ag  ][Cl - ]
 Applying law of chemical equilibrium -: K
[AgCl]


 K[AgCl] [Ag ][Cl ]
-
,
But [AgCl] can be taken as constant
 Kk  [Ag ][Cl- ] or Ksp  [Ag ][Cl- ] .
Where, Ksp = solubility product. Thus “solubility product of a salt at a given temperature can
be defined as the product of molar concentration of the ions (formed in the saturated solution at a

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 given temperature) raised to the power equal to the number of times each ion occurs in the
equation for solubility equilibrium”.
 If solubility of a sparingly soluble salt Ax By is S moles /litre, then

Ax By  x AY+ + Y BX-
S moles x S Moles YS Moles
Y+ x-
[A ] =XS, [B ] = YS
Ksp = [Ay+] x [B x-] y = (XS) X (YS) Y = XX. SX. YY. SY= XX. YY. SX+Y
Ksp= XXYYSX+y………..(21)
 Solubility product is constant for a given electrolyte at a given temperature, while changing
the concentration can vary ionic product.
 If KW = KSP the Solution is just saturated and no precipitate takes place.
 If Kw > Ksp, the solution is super saturated and precipitate takes place.
 If Kw < KSP, the solution is unsaturated and more solute can dissolve.
7. Application of common ion effect & solubility product: -
1. Purification of NaCl –:
NaCl  Na+ + Cl –, HCl  H+ + Cl –
With increase in concentration of Cl– the Kw for [Na+] [Cl –] becomes more than KSP
hence NaCl precipitate out.
2. Salting out of soap-:
C17H35 COONa  Na+ + C17H35COO –
NaCl  Na+ + Cl –
Due to common ion effect of Na+, the value of Kw exceeds KSP and Soap is precipitate out.
3. In qualitative analysis-:

The group cations are preferentially precipitated due to the combined application of
common ion effect and solubility product.
8. Buffer solutions: -
 A solution whose PH almost remains constant even when a few drops of an acid or base are
added to it is known as a buffer solution. In other words a buffer solution is a system which
maintains it’s hydrogen (or hydroxyl) ion concentration at an approximately constant level,
which does not change by adding water or small amounts of any acids or base to it. e.g., a
mixture of CH3COOH and CH3 COONa, blood, urine etc.
 The property of a solution by virtue of which it tends to resist the change in PH is known as
buffer action, and the number of moles of acids or bases added to one litre of the buffer
solution so as to change it’s pH by one unit is known as it’s buffer capacity.

Number of moles of teh acid or bases added to one liture of the buffer n
Buffer Capacity  
Change in pH pH
9. Types of buffer and mechanism of buffer action: -
 Strong acids and bases seldom form buffers, as they are completely ionised. In general buffer
solutions contain either a weak acid in presence of rather high concentration of salt of its

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 conjugate base or a weak base in presence of rather high concentration of salt of its conjugate
acid. Thus there are two main types of buffers, namely acidic buffers and basic buffers.
a. Acidic buffer: -
 An acidic buffer is an equilmolar mixture of a weak acid and its salt with strong base. For
example a mixture containing one mole at CH3 COOH and one mole of CH3 COONa
 In the above buffer, there will be large concentration of Na+ ions, CH3COO - ions and
undissociated CH3COOH molecules.
(i) Suppose a few drops of HCl are added to the buffer solution. Most of the H + ions from
HCl will combine with the CH3COO– ions (from CH3COONa in buffer) to form feebly
dissociated CH3COOH molecules, hence negligible change in PH occurs.
CH3 COONa  CH3COO - +Na+
CH3COO -(From buffer) + H+ (From acid)CH3COOH
(ii) Suppose a few drops of NaOH are added to the said buffer. The OH – (from NaOH)
are neutralized by the H+ ions of buffer to from feebly ionised water molecules. Hence
negligible change in PH occurs.
H+(From CH3COOH) +OH – (From base)  H2O
Again according to lechatlier’s principle, the above reaction results in the greater
dissociation of CH3COOH to restore the original concentration of H+ ions in solution.
 PH of acidic buffer: -
 Consider a buffer of a weak acid HA and it’s salt with strange base, BA. The weak acid
ionises as; HA  H+ + A –
Applying law of chemical equilibrium:
[H  ][A - ] K a [HA]
Ka  or [H  ]  ………….(23)
[HA] [A - ]
The salt can be ionised as; BA  B ++ A –
As the salt AB is completely ionised, the concentration of A–, ions from AB salt is too
large to be compared with A– ions from weak acid, HA.
Thus [HA] is the initial concentration of the weak acid as it is only feebly ionized and
[A –] is the initial concentration of the salt, AB as it is completely ionised.
[Acid]
 From equation (20) [H+]= K a
[Salt]
 [Acid]
Or – log [H+] = - log Ka 
 [Salt]
[Acid]
Or pH = - logK a - log
[Salt]
[Salt]
Or pH = - logK a  log ....................(24)
[Acid]
The equation (24) is known as Henderson’s equation to calculate the pH of an acidic
buffer.
b. Basic buffer:
 A basic buffer is an equimolar mixture of weak base and it’s salt with strong acid. For
example, a mixture containing 1 mole of NH4OH and one mole of MH4Cl.In the said

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 buffer there will be a large concentration of NH4+ ions, Cl – ions and NH4OH
molecules.
i. Suppose a few drops of HCl are added to the buffer. The H+ ions of HCl
combine with OH – ions of NH4OH to form feebly ionised water. Thus no change in
pH occurs. NH4OH  NH4 + + OH –
H+ (From acid) + OH –(From buffer)  H2O
According to Lechatlier’s principle, the above reaction results in the greater
dissociation of NH4OH to restore the original concentration of OH – ions.
ii. Suppose a few drops of NaOH are added to the buffer. Here OH– ions from NaOH.
Combine with NH4+ ions of NH4Cl to form weakly ionised NH4OH molecules.
Hence, no appreciable change in pH value occurs. NH4Cl  NH4++ Cl-
+ –
NH4 (From buffer) +OH (From base) NH4OH
 pH of basic buffer: -
 Consider a buffer of weak base BOH and its salt with strong acid (BA). The weak
base can be represented as
BOH  B + + OH –
Applying law of chemical equilibrium.
[B  ] [OH - ] K b [BOH]
Kb  or [OH - ]  ...............(25)
[BOH] [B  ]
 The salt can be represented as -: BA  B+ + A –
 As BA is completely ionised, the concentration of B+ ions from BA salt is too large
to be compared with B+ ions from weak base BOH. Thus [BOH] is the initial
concentration of the weak base as it is only feebly ionised and [B+] is the initial
concentration of the salt, BA as it in completely ionised.
[Base ]
 From equation (25), [OH - ]  K b
[Salt]
 [Base ] 
Or – log [OH-] = - log K b 
 [Salt] 
[Base ]
Or pOH  - log K b - log
[Salt]
[Salt]
Or pOH = pK b  log …….…(26)
[Base ]
Equation (26) is the Henderson’s equation to calculate the pOH of a basic buffer.
10. Hydrolysis of salts:
 The reaction of an anion or cation with water accompanied by cleavage of (OH-bond)/(–OH) is called
hydrolysis.

e.g. AB + H2O
A– + H–O–H  HA + OH– (anionic hydrolysis)
B– + H–O–H  BOH + H+ (cationic hydrolysis)
 When a salt is dissolved in water, it produces corresponding acids and bases, from which it is produced.

Salt + Water  Acid + Bases

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 Thus hydrolysis is the reversible process of neutralization.
a) Hydrolysis of different salts :
i. Salt of strong acid – weak base
Consider a salt NH4Cl of the strong acid HCl and weak base NH4OH undergo
hydrolysis as follows :
(H+) and (Cl–) exist as such they form a strong electrolyte. On the other hand, the
ammonium ion (NH4+) can accept (OH–) ion from water. These consumption decreases
the OH– ion, hence the equilibrium will shift towards right so (H+) ion concentration
increases. Thus the solution becomes acidic :
i. NH4OH  NH4+ + OH–
ii. NH4+ + H2O  NH4OH + H+
iii. H2O  H+ + OH–
ii. Salt of Weak acid and Strong Base
Consider a salt CH3COONa of weak acid CH3COOH and strong base NaOH.
CH3COONa  CH3COO– + Na+
H2O  H+ + OH–
Result :- CH3COOH + Na+ + OH–
The Na+ and OH– exists as such they form a strong electrolyte. In other hand
CH3COO– combine with H+ to form CH3COOH. This consumption of H+ ion shifts the
equilibrium towards right and more OH– will be formed. As a result the concentration
of OH– ion will increase. Thus the resulting solution will be basic and PH > 7.
iii. Salt of strong acid and strong base :
Consider a salt NaCl of strong acid HCl and strong base NaOH.
NaCl  Na+ + Cl–
H2O  H+ + OH–
Result : Na+ + Cl– + H2O
Since HCl is a strong acid, its conjugate base Cl– formed is very weak base, hence Cl–
is unable to accept a proton from an acid, particularly H2O, i.e., Cl– does not hydrolyse.
Cl– + H2O  HCl + OH–
Similar case happens for Na+. So the resulting solution becomes neutral, i.e., pH = 7.
iv. Salt of Weak acid and weak base :
Consider a salt CH3COONH4 of weak acid CH3COOH and weak base NH4OH.
CH3COONH4  CH3COO– + NH4+
H2O  H+ + OH–
Result : CH3COOH + NH4OH
Here CH3COOH and NH4OH are weak electrolytes Both of them associate to same
extent, hence, the resulting solution is neutral i.e., pH = 7.

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