Chapter 6

Thermodynamics
 ↑

Thermodynamics Study of heat changes associated with chemical reactions.

System - It is the part under observation

Surroundings - It is the part other than system

Boundary - It is the separation between the system and

surroundings. It can be real or imaginary.

System + Surrounding = Universe

Types of Systems (ability to exchange energy and matter with the surroundings)

1. Open system:
System can exchange both energy and matter.
Eg : Hot water taken in an open vessel.

2. Closed system:
It can exchange only energy and not matter.
Eg : Hot water taken in a closed vessel.

3. Isolated system:
It cannot exchange both energy and matter.
Eg : Hot water taken in a thermo flask.
Chapter 6

Thermodynamics
Intensive / Extensive Properties
6 & 8 & & ·
& &
8 8 & &
& &
⑨ &
⑱ ⑧
· &
⑨ ⑤ & &
&
G &
& &
8
&
& & & &
* &
⑧
&
8 %
·
· &
09
D &
8 &
⑤ & D ⑱
·
⑱ &
· & & 3
&
 Extensive Properties Intensive Properties
Depend on the amount of Independent of the amount of
matter present in the system matter present in the system
Volume (V) Temperature
Mass (m) Pressure
Internal energy (U) Density
Enthalpy (H) Refractive index
Entropy (S) Molar heat capacity
Gibb’s energy (G) Viscosity
Heat capacity Surface tension
Ratio of 2 extensive property is an intensive property

Intensive
X Mass - Ext
-

Density Volume Ext

=

T
F F
Chapter 6

Thermodynamics
State functions and Path functions
 ⑮

E
work
heat

⑭
 State functions and Path functions

State functions : A function or a property that depends only

on the initial and final state of a system and
not on the path followed.

Eg : T, P, V, U, H, S, G etc

Path functions : These are properties which depend on the path

followed also.

Eg : Heat (q) and Work (w)

Chapter 6

Thermodynamics
First law of thermodynamics
Internal Energy
It is the energy possessed by a body.
It is the sum of different types of molecular energies like
translational kinetic energy, rotational kinetic energy,
vibrational kinetic energy, electronic energy, nuclear energy etc.

The unit of internal energy is kJ/mol.

The internal energy of a system can change in mainly by two ways:

1. By the transfer of heat

2. By doing work
First law of thermodynamics
It states that energy can neither be created nor be destroyed.

Or, the total energy in the universe is always a constant.

Or, the total energy of an isolated system is always a constant.

Fde
Mathematically ; We

ΔU = q + w We
-
P GV
.

If there is only expansion work, the above equation becomes,

ΔU = q – PΔV
Heat absorbed by the system + ve
q =

-ve
Heat released by the system q =

-ve
Work is done by the system w =

ve
w=
Work is done on the system
-
Work

For irreversible process, (wexp) = -

POV

For reversible process, (wexp) = -

2 303
.

nrFlo
Free expansion
Expansion of a gas into vacuum (Pext = 0) is called free expansion.

No work is done during free expansion of an ideal gas whether the

process is reversible or irreversible.
Chapter 6

Thermodynamics
Thermodynamic processes
 Thermodynamic processes

1. Isothermal process: DT 0 ; XV = 0
=

It is a process that occurs at constant temperature.

2. Isobaric process: Up
= 0

It is a process that occurs at constant Pressure

3. Isochoric process: NV 0 =

It is a process that occurs at constant volume.

4. Adiabatic process: q 0=

It is a process that occurs at constant heat energy.

Here no heat enters into or leaves from the system.

5. Cyclic process:
It is a process that takes place in a cyclic manner.
Here the system undergoes a series of changes and
finally returns to its initial state.

For such a process ΔU=0 and ΔH = 0

Enthalpy (H)
It is the total heat content of a system.

It is the sum of internal energy and pressure-volume energy of a system.

It is a state function and an extensive property.

H = U + PV

ΔH = ΔU + PΔV

ΔH = ΔU + ΔnRT Δn = nP - nR
Measurement of ∆U and ∆H - Calorimetry

Energy changes associated with chemical or physical processes by an

experimental technique called calorimetry.

In calorimetry, the process is carried out in a vessel called

calorimeter, which is immersed in a known volume of a liquid.

ΔU is measured in a bomb calorimeter.

Chapter 6

Thermodynamics
Relation between Cp and Cv
Heat capacity
It is the amount of heat required to raise the temperature of a body
through 1⁰C or 1K.

If q amount of heat is required to raise the temperature of a body

through ΔT,
then heat capacity, C = q /ΔT H
[p
=

heat capacity at constant volume, Cv = Du

Ev =

heat capacity at constant pressure, Cp -

Relation between Cp and Cv
c
=
CH = Ou + PAV
E CUT Du
RA/T
=

C = CDX +
DH
= CUT
=

Cu + R
Cp =

nRT
PV =

R
Cp-Cv =

For Imok ; n= 1

- PV = RT

POV = ROT
Chapter 6

Thermodynamics
Hess’s Law of Constant Heat Summation
 Hess’s Law of Constant Heat Summation
The law states that the total enthalpy change for a physical
or chemical process is the same whether the reaction taking
place in a single step or in several steps.

Att D
Be
DH2
Orl CH ,
= + Whe + OHs
Born-Haber Cycle

b
Born-Haber Cycle
Q)

Using these data, calculate the enthalpy of reaction for

N₂O₄ (g) + 3CO(g) N₂O(g) + 3CO₂(g)

OrH =
CH N20 + 3x+
H(O2) -

(SHNOn + 3x & fHCO)

= (8) + 3x
-

393) -
(9 . 7 + 3x
-

110)
= (81 -

1179) -

(9 . 7 -
330)
1098 -- 320 3 -1098 + 320 3
.

=
=
.

-
=

17 TK1/mo .
Q)

S + = G H(02 + 2x* H20] (HCH0H

H -
+ s
G

Ex 0)
2x 286) (H(zH +

(
-

(26 =
393 +

-
726 = 7 393- 572) -
OfH CHOH

Of CHOH = -965 + 726

39k5/me
=
Chapter 6

Thermodynamics
Spontaneous / non-spontaneous Process
Spontaneous Process
It is a process that takes place without the help of any external agency.
All natural processes are spontaneous.

Eg: flow of water from high level to low level.

flow of heat from hot body to cold body.

Non-spontaneous Process
A process that takes place with the help of an external agency is
called non-spontaneous process.

Eg: flow of water from low level to high level.

Entropy (s)
It is a measure of degree of disorderness or randomness of a system.

It is an extensive property and state function.

If S1 is the initial entropy of a system and S2 is its final value,

then the change in entropy , ΔS = S2 –S1

When temperature increases entropy also increases.

+ ve
NS = S-S ,↓ -

gab liquid
Entropy and spontaneity
During a spontaneous process, disorderness of the system increases.

Thus entropy increases and hence ΔS becomes positive.

The total entropy change for the system and surroundings is given by

ΔStotal = ΔSsyst. + ΔSsurr.

For, spontaneous process ; ΔStotal >0

equilibrium ; ΔStotal = 0
non-spontaneous ; ΔStotal < 0
 Second Law of Thermodynamics
It can be stated as the entropy of the universe always
increases during every spontaneous process.

For spontaneous process ; ΔStotal >0

ΔStotal = ΔSsyst. + ΔSsurr.

Third law of Thermodynamics
It states that the entropy of any perfectly crystalline substance is zero
at absolute zero of temperature.
Gibb’s energy (G)
It is the maximum amount of available energy that can be
converted to useful work.

It is an extensive property and a state function.

W
Du =
E +

The unit of Gibb’s energy is kJ/mol.

w=
-
Por

It is given by the equation, G = H – TS + POV

CH Du
=

ΔG = ΔH - TΔS UG =CH-TOS
Gibb’s energy and Spontaneity
For a spontaneous process, energy of the system is decreases.

is , For spontaneous process ; ΔG <0

equilibrium ; ΔG = 0
non-spontaneous ; ΔG > 0
Conditions for ΔG to be negative ΔG = ΔH - TΔS

1) ΔH = -ve, ΔS = +ve o always-ve ; sportams .

Norsporter
2) ΔH = +ve, ΔS = -ve
the
o always ;

when TOS > DH

3) ΔH = +ve, ΔS = +ve spontanews
when &H > TOS
4) ΔH = -ve, ΔS = -ve sportances ,
Q) Enthalpy and entropy changes of a reaction are 40.63 kJ/mol
and 108.8 J/K/mol. Predict the feasibility of the reaction at 27⁰C.

WH = 40 63. k]/mo
US = 108 .

81/k/mol = O . 1088 K1/mo

T = 27 + 273k =
o
Gistre
OG = DH-TOS since
40 63-300x0
. Loss
reactions
ontar
.

= 40 63 . - 32 .
64 This
DG = + 7 99. ky/me nore
 CHAPTER 07

EQUILIBRIUM
A+B C+D

A+B C+D
Equilibrium
Equilibrium is a state in which the rates of forward
and backward reactions are equal.

Equilibrium is dynamic in nature.

i.e. at equilibrium the reaction does not stop.
Physical equilibrium

Equilibrium involving physical process is called physical equilibrium.

E.g. melting of ice, evaporation of water

H₂O(s) H₂O(l) ⑳
Hope H20(g)
Chemical Equilibrium
Equilibrium associated with chemical reactions is called
chemical equilibrium.

At equilibrium, the concentrations of reactants and products

are constant.

N₂ + 3H₂ 2NH₃
Law of Chemical Equilibrium Equilibrium Constant

It states that at constant temperature, the ratio of

concentration of the products to that of the reactants, in
which each concentration terms is raised to a power which is
equal to the stoichiometric coefficients in the balanced
chemical equation, has a constant value.

T
For a general reversible reaction:

aA + bB cC + dD k=
-
For the reaction :

H₂+ I₂ 2HI

=
For the reaction :

N₂ + 3H₂ 2NH₃
For the reaction :

2HI H₂+ I₂ =
KT
-

k=
k = 1
-
k
Equilibrium constant for gaseous reactions
For a reaction involving gases, the concentration terms are
replaced by partial pressures.

Share
H₂ (g)+ I₂ (g) 2HI (g)

↑
 aA + bB = c + dD
Relation between Kc and Kp PV = nRT

=
P
ART
=

Kp P = Conc
. RT

Pa [A](R)
=
=

K
PB [B(RT)
=

a) (a+ b)
(RT)(x Pi [c] (R+Y
=

kp k,
=

on PE[D] Cra
CRT)
= k, (c+ d) (a+b)
-
= on

= on
 on
CRT)
=
k,

①
gunkp
Homogeneous and heterogeneous equilibria
An equilibrium reaction in which all the reactants and products are
in the same phase is called homogeneous equilibrium.

Eg : H₂ (g)+ I₂ (g) 2HI (g)

Equilibrium reaction in which the reactants and products are

in different phases is called heterogeneous equilibrium.

Eg : H₂O(s) H₂O(l)
Characteristics of Equilibrium constant K
1. Equilibrium constant is applicable only when the concentrations of
the reactants and products have attained their equilibrium state.

2. The value of equilibrium constant is independent of the initial

concentrations of reactants and products.

3. The value of equilibrium constant depends on temperature.

4. The equilibrium constant for the reverse reaction is the reciprocal

of that of the forward reaction. k =
5. If for the reaction A B, the value of equilibrium constant is K,
n
then for the reaction nA nB, its value is K .
 Applications of equilibrium constant

1. Prediction of the extent of a reaction k

,
=
Greater the value of equilibrium constant,
greater will be the concentration of products.

a) If Kc is very large, the reaction proceeds nearly to completion

b) If Kc is very small, the reaction proceeds rarely.

2. Prediction of the direction of the reaction
By knowing the values of Kc and Qc, we can predict
the direction of a reaction.

Q at a e

If Qc > Kc, the reaction will proceed in the direction of reactants

(reverse direction).

If Qc < Kc, the reaction will proceed in the direction of products

(forward direction).

If Qc = Kc, the reaction mixture is at equilibrium.

3. Calculation of equilibrium concentrations
By knowing the value of equilibrium constant, we can calculate
the equilibrium concentrations of reactants and products.
Relationship between Kc and Gibbs energy (G)

ΔG⁰ = – RT lnKc

ΔG⁰ = – 2.303RT logKc

EQUILIBRIUM
Factors affecting equilibrium
Le Chatlier’s Principle
whenever there is a change in concentration,
pressure or temperature of a system at equilibrium,
the system will try to readjust in such a way so as to
cancel the effect of that change.
1. Effect of concentration change
An increase in concentration of reactants
increases the rate of forward reaction and,

An increase in concentration of products

increase the rate of backward reaction rate

N₂ + 3H₂ 2NH₃
2. Effect of temperature change
Increase in temperature favours endothermic process and
decrease in temperature favours exothermic process.

EXO
N₂ + 3H₂ 2NH₃ ΔH=-92.38kJ/mol
ENDO

o Temp
↓
farm Forward Rule

zook
3. Effect of pressure change
Pressure has its role only in gaseous reactions.

In general an increase in pressure favours the reaction in which

number of moles decreases and vice versa.

N₂ + 3H₂ 2NH₃
-
(g) (9) e
Kress format

0+②
de
⑪more
4. Effect of catalyst
In an equilibrium reaction, a catalyst increases the rate of both
forward and backward reactions simultaneously and helps to
attain the equilibrium faster.
It does not affect the equilibrium.

Haber process for the manufacture of ammonia, iron (Fe).

In contact process for the manufacture of sulphuric acid, V₂O₅

EQUILIBRIUM
Electrolytes and non-electrolytes
Electrolytes
Electrolytes are substances which conduct electricity in molten
state or in solution state.

Eg : All acids, bases and almost all salts

Non- electrolytes
Non- electrolytes are substances which do not conduct electricity
in molten state or in solution state.

Eg : sugar, urea etc.

Strong electrolytes and weak electrolytes
Strong electrolytes
Strong electrolytes are electrolytes which dissociate almost
completely in aqueous solution.
+ -
Eg : Strong acids like HCl, HNO₃, H₂SO₄ etc. H +

H =>

Strong bases like NaOH, KOH etc.

Salts like NaCl, KCl, Na₂SO₄, K₂SO₄, KNO₃, NaNO₃ etc.

Weak electrolytes
Electrolytes which dissociate only partially in aqueous solution are
called weak electrolytes. Ht +

Eg : weak acids like CH₃COOH, HCOOH etc.,

weak bases like Mg(OH)₂, Ca(OH)₂, NH₄OH etc. and
ECHyco
some salts like CaSO₄, BaSO₄ etc. CHyCOOH
Acids, Bases and Salts

1. Arrhenius concept
Acids : Substances which give hydrogen ion (H+) in aq.solution
Bases : Substances which give hydroxyl ion (OH-) in aq.solution

2. Bronsted – Lowry concept

Acids are proton (H+) donors
Bases are (H+) acceptors.

3. Lewis concept
Acids are electron pair acceptors
Bases are electron pair donors.
Q) An example of Lewis acid among the following is:

(A) HCl 3
↑E

(B) NH₃
FB-2 ,

9
(C) H₂SO₄ ·
B
19-F (D) BF₃

F
Q) Write conjugate acid and conjugate base of the following:
(a) NH₃

(b) H₂O

Conjugate acid = NHztH

Conjugate base E
NH3-H-
acid = He0 + H
+
=- Hz0T
⑯ Conjugate
base E
=

OH
Conjugate H20 -
H =
=
The pH scale
pH is defined as the negative logarithm of the hydrogen ion
concentration in moles per litre.

pH = - log[H+]

Negative logarithm of [OH- ] ion concentration in mol/L is called pOH.

pOH = -log[OH- ]

12 + 2
ph === Neutral
pH + pOH = 14 pt = Basic

pic7 => Acidic

Q) Calculate pH of a 0.1M solution of NaOH. OH
NaOH- > Nat +

pElog IM M
[Hi 0 . IM o

[OH
pot--log [0H]
-
=

log(0 1)
·

pot + pt = 14

=
-
-1 = 1
pH = 14 - pot
-

pot = 14 -1
- =B
 Hydrolysis of Salts
Q)Out of the following, which can produce an acidic solution in water?
(CH₃COONa, NH₄Cl, CH₃COONH₄, NaCl) Nat c
He of
NHatch CH3co NHI
CHCOO Nat + OH-

creak
H
H+ ot-
At OH

who
Chycohere
NaOt Strongbose
HC) strongd neutra
?
=

Acidic
.

Basic
-
Common Ion Effect
It is the suppression of the dissociation of a weak electrolyte by the
addition of a strong electrolyte containing a common ion.
+
CHOOHCHyc00 + H

Nat
CHICOONa >
-
CH3c00 +

NHOH = NHnt + OH-

Nhat cl-
NHnCl >
- +
Buffer Solutions
Solution which resists the change in pH on dilution or with the
addition of small amount of acid or alkali is called Buffer solution.

There are two types of buffer solutions – acidic buffer and basic buffer.

Acidic buffer : mixture of a weak acid and its salt with a strong base.

CH3COOH + CHzCOONa
Basic buffer : mixture of a weak base and its salt with a strong acid.

NHOH + NHaCl
 cl-
Solubility Product Constant (Ksp) Nad- > Nat +

It is defined as the product of the molar concentration of #

ions of a sparingly soluble salt or in a saturated solution.
(s)) x(s)) =
Ksp =

a b
If S is the molar solubility, & cation anion ratio a:b, Ksp = (aS) .(bS)

Bet So (s) x
(s)) = sxs =
5
For BaSO₄ Ksp =

2+
20HMg(OH)₂ Ksp = (s) x (25) sx45= =

25
z
49,0
(s) (ss) sx275 =
.

Al(OH)₃ Ksp = x =

Alt 30H-
1 : 3
Q) Consider the equilibrium, AgCl Ag+ + Cl−
The solubility of AgCl is 1.06 x 10-⁵ mol/L at 298K.
Find out its Ksp at this temperature. a : b

S = 1 . 06 x105 1 I
:

(s) (s)) S 2
ksp
=
= x

=
( . 06 x 105)
x180
=
Thank you...
-
Madhadal