PAWAN WAGH ACADEMY

Notes
Topic – Chemical Thermodynamics

 Introduction-

Solid ⇋ Liquid ⇋ Water

Ice water vapour

Energy
Changes

 Thermodynamics
It is phenomenon, which is concerned with the energy changes in
physical and chemical transformations.

 System
A part of universe thermodynamics investigation is called as the
System.

 Surroundings
The all other parts of the universe, outside the system, are called as
Surroundings.

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 Types of system
(On the basis of exchange of energy and
matter)

Isolated system
Closed System
Open System A system that does
A system that
A system which not exchange energy
exchanges energy and
exchanges both as well as matter is
not the matter with
energy and matter called as isolated
the surroundings, is
with surroundings is system
called as a closed
called as open system system Ex. A hot coffee is
Ex. Hot coffee placed placed in thermos
Ex. A cup container
in cup in a room flask
hot coffee is covered
with saucer

Properties of System
(On the basis of dependence on amount
of matter)

Extensive Property Intensive property

A property which depends A property which is
on the amount of matter, independent of the amount
present in a system is called of matter, present in a
as Extensive Property system, is called as intensive
property
Ex. Mass, volume, Internal
energy, heat capacity, number of Ex. Pressure, temperature
moles. surface tension, Viscosity Melting
point, Boiling point, specific heat

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 Functions

State Function Path function

The property which depends The property which depend
on the state of a system and on the path are called as
independent of a bath Path function
followed to attain it, is
Ex. Work (W) and heat (Q)
called as State function
Ex. S E H V A G
S:- Entropy
E:- Internal energy
H:- Enthalpy
V:- Volume
A:- Helmholtz free energy
G :- Gibbs free energy

Equilibrium

Thermodynamics Non –thermodynamic

Equilibrium equilibrium
A system is said to be in A system is said to be in
thermodynamics equilibrium non-thermodynamics
if state function do not vary equilibrium, it state function
with time vary with time

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 Process
A transition from one equilibrium state to another is called as Process

Isobaric Process Isochoric

Isothermal
process Pressure Adiabatic Reversible
The process in
Process Process
which the The process in
The process in
pressure of which the The process in The process in
which
system remains volume of which there is which, at every
temperature of
constant during system remains no exchange of stage, the
system remains
the constant during heat between driving force
constant during
transformation the system and due to pressure
the
is called as transformation surrounding is (P) is
transformation
Isobaric is called as called as infinitesimally
is called
process Isochoric Adiabatic greater than the
Isothermal
process Process Process opposing force
P=constant
due to external
T =constant ∆P=O V=constant Q=O
pressure (Pext)
∆T=O (P=Pressure) ∆V=O (Q=heat) and which can
be sight change
∆U=O (V=Volume)
of opposing
Where force is called
as Reversible
(T,U=constant Process
Internal energy
temperature)

 Features of Reversible Process:-

a. The driving force and opposing force differ by an infinitesimal
amount
b. The process can be reversed by an infinitesimal change in condition
c. A reversible process infinity slowly and takes place in infinite
number of steps
d. At the end of every step of the process, the system attains
mechanical equilibrium with surroundings

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 Nature of

Work Heat
W=Force x displacement The form of energy, by
W = f x d ……….(1) which the system exchanges
energy with its
It is also realized that surroundings is called as
W = P x V ……......(2) heat
force f
So now, P = pressure= =
Area A

A = Area = d2
d = displacement
V = Volume = d3
So,
f f
PxV= xV= x d3 = fxd = W
A d2

So, W=PxV

 Sign convention of work and heat:-

-W → Work done by the system

+W → Work done on the system
+Q → Heat is absorbed by the system
-Q → Heat is released by the system

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 Expression for pressure – volume (pv) work
Consider a certain amount of gas at constant pressure P, which is
enclosed in a cylinder fitted with frictionless, rigid, movable piston
of Area A, as shown in fig. It is allowed to undergo expansion as…

Let
Force =f = - Pext x A .....(1)
W=fxd ……(2)

So, substituting value of f in eq n (2)

We get, W = - Pext x A x d ………………(3)

A x d = ∆V = change in volume ………………..(4)

Put eqn (4) in eqn (3)

W = - Pext x ∆V
W = - Pext x (V2 – V1)

Where
f = force
W = work done
Pext = external pressure
V1 = Initial volume
V2 = Final volume
A = Area
d = displacement

W = - Pext (V2 – V1)

During expansion During compression

Volume increase volume decrease
So V2 > V1 So V1> V2

W = -ve W = +ve

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 Free expansion:-
1. The expansion against zero opposing force, is called as free
expansion
2. Free expansion, occur in vaccum
Pext = 0
So, W = - Pext∗ ∆V
W=0

 Work unit conversion

1 dm3.bar = 100 J

 Expression for the maximum work:-

Consider n moles of an ideal gas enclosed in a cylinder fitted with
frictionless movable rigid piston.
The piston is allowed to expand isothermally and reversibly from
initial volume V1 to final volume V2 at temperature T.
At every step, the Pext is made infinitesimally smaller than pressure
(P) of gas.

dw = Pext x dv
dw = -P x dv
Integrating both sides
𝑊2 𝑉2
∫𝑊1 𝑑𝑤= - ∫𝑉1 𝑃. 𝑑𝑣 (1)

As PV = nRT
𝑛𝑅𝑡
So P = (2)
𝑉
 Substituting the value of P from eqn (2) into eqn (1)
𝑉2 𝑛𝑅𝑇
Wmax = - ∫𝑉1 . dv
𝑉

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 𝑉2 1
= - nRT .∫𝑉1 . dv
𝑉

= -nRT ln[𝑉]𝑉2
𝑉1

= -nRT( In[V2]-In[V1] )

𝑉2
Wmax= -nRT In ( ) (a)
𝑉1

1
dx = In x
𝑥

In x = 2.303 x log x

𝑚
In m-In n = In ( )
𝑛

So

V2
Wmax = -2.303nRT log10 ( ) ……..(b)
V1

According to Boyle’s Law,

V2 P1
=
V1 P2

so P1
Wmax = -2.303nRT Log10 ( ) ……. (c)
P2

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 Internal Energy :-
The definite amount of energy stored in a substance is called as
internal energy

Change in
Internal energy = ∆U = (U2 – U1) of a system

Where U2 = Internal energy of final state

U1 = Internal energy of Initial state

 First law of thermodynamics:-

Statement:-
1. Energy of the universe remains constant
2. The total internal energy of an isolated system is constant
3. Energy can be neither be created nor be destroyed, but can be
converted from one from to another.

 Formation of 1st Law of thermodynamics

∆U = Q+W or du = dQ+ dW

Where ∆U = change in internal energy of the system

Q = Heat supplied to the system
W = Amount of work done

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 First law of thermodynamics for various process

Isothermal Adiabatic Isochoric Isobaric

process Process process
process
Temp=constant
Q=0 V = volume
U = internal ∆V ≠ 0
∆U =Q+W =constant
energy =constant
So ∆V = 0 ∆U = Qp - Pext x ∆𝑉
∆U = 0 ∆U =O+W
∆U = W As , Qp = ∆U+Pext x ∆V
So ∆U = Q+W
O = Q+W W = Pext x ∆V Where
Q = -W W = -Pext x 0 Qp =∆H
W = -Q W=0
And
∆U = Q + W

∆U = Q + 0
∆U = Q

 Enthalpy So ∆U = Qv
Enthalpy of a system is the sum of internal energy of a system and
pv work
H = U + PV
H = U1 + P1V and H2 = U2 + P2 V2
∆H = H2-H1
∆H= (U2 – P2 V2) – (U1 + P1 V1) as p = constant
= (U2 – U1) + (P2V2 – P1 V1) so P1 = P2 = P
= (U2 – U1) + (PV2 – PV1)
= (U2 –U1) + P(V2 – V1) as (U2 – U1) = ∆U
∆H= ∆U + P ∆V …….(1) (V2 – V1) =∆V

As Qp = ∆U + P∆V ……..(2)

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 So from (1) & (2)
∆H = Qp

The change in enthalpy of a system is equal to heat transferred

from is at constant pressure.

 Relationship between ∆H and ∆U for chemical

reactions
∆H= ∆U + P∆V
∆H= ∆U + P(V2 – V1) ……. (PV1 =n1RT)
∆H= ∆U + PV2 – PV1
∆H= ∆U + (n2RT – n1RT) …….. (PV1 =n1RT)

∆H= ∆U + (n2 – n1) RT

∆H= ∆U + ∆ng RT

 Work done in a chemical Reaction :-

The work done by system at constant temp and pressure is given
below as

W= Pext x ∆V where, Pext = - P

W = -P x ∆V
= -P (V2 – V1) Ideal Gas Equation
W= -PV2 + PV1 PV1 = n1RT
W= -n2RT + n1RT PV2 = n2RT
W= -(n2-n2)RT ∆ng= n2-n1

So W= -∆ng RT

n1>n2 n! = n2 n2>n1

∆ng= -ve no’s of moles of ∆ng= +ve

reactant = no’s of W<O or W= -ve
W>O or W= +ve
moles product
Work is done on the Work is done by the
system no PV work is done system
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  Enthalpy of physical transformations

Enthalpy of Enthalpy for atomic/

Phase transition molecular change

Enthalpy of
fusion Enthalpy of Enthalpy of
vaporization sublimation
(∆fusH)
(∆vapH) (∆subH)

Enthalpy of
Enthalpy of Enthalpy of solution
Ionization atomization (∆solH)
(∆ionH) (∆atomH)

I) Enthalpy of phase transition :-

The enthalpy change, that occurs where one phase of a substance is
converted into another at constant temperature and pressure without
change in chemical composition, is called as Enthalpy of phase
transition.

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a) Enthalpy for fusion(∆fusH) :-
The enthalpy change that occurs, where one mole of a solid is
converted into liquid, at constant temperature and pressure, is called
as Enthalpy of fusion
Fusion
H2O(s) H2O(l)

b)Enthalpy of vaporization (∆vapH) :-

The enthalpy change that occurs, where one mole of a liquid is

converted into gas (vapors) at constant temperature and pressure,
is called as enthalpy of vapourization.

Vaporization
H2O(l) H2O(g)

c) Enthalpy of sublimation (∆subH) :-

The enthalpy change that occurs, when one mole of solid is directly
converted into vapour at constant temperature and pressure, is
called as enthalpy of sublimation
Sublimation
H2O(s H2O(g)

 Relation

∆Hsub = ∆H fus + ∆H vap

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II) Enthalpy for atomic/molecular change

1) Enthalpy of ionization (∆ionH):-

The enthalpy change that occurs during the removal of an electron
from one mole of gaseous atom, is called as Enthalpy of ionization

Na Na1+ + e-
Ionization

2) Electron gain enthalpy (∆egH):-

The enthalpy change that occurs, when one mole of gas-phase atom
of an element accept electron to form gaseous anion, is called as
electron gain enthalpy

Cl(g) + e- Cl (g)
-

3) Enthalpy of atomization(∆atomH):-
The enthalpy change that occurs, when one mole of gaseous substance
undergoes dissociation into, is called as enthalpy of Atomization

Atomization
Cl2(g) Cl(g) + Cl (g)
molecule atom atom

4) Enthalpy of solution(∆SolH):-
The enthalpy change, that occurs when one mole of a substance is
dissolved in specified amount of solvent, is called as enthalpy of
solution

NaCl(s) + aq NaCl(aq)
Solvent Solution

 Relation: ∆solH = ∆ LH + ∆hydH

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 Where
∆solH = Enthalpy of solution

∆ LH = Enthalpy Lattice enthalpy

∆hydH = Enthalpy of hydration

5) Enthalpy of Chemical Reaction (∆rH)

The difference between the sum of enthalpies of products and that
of reactants in the balanced chemical equation of reaction is called
as enthalpy of chemical Reaction
Consider
a A+ b B cC + dD

∆ϒH = ∑ H Products - ∑ H Reactants

H = (c Hc + dHD) – (aHA + bHb)

Enthalpy of chemical Reaction (conditions)

1) If ∑H Products > ∑ H Reactants

2) If ∑H Reactants > ∑H Product
So ∆ϒH = +ve So ∆ϒH = -ve

Endothermic Reaction Exdothermic Reaction

 Thermodynamics standard state

T= Temperature = 298K (25oC)
P = Pressure = 1 bar
C = concentration = 1M

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 Standard enthalpy of reaction (∆rH)
The enthalpy change that occurs, when the reactants and products
involved in the reaction, are in standard state, is called as standard
enthalpy of reaction.

 Standard enthalpy of formation (∆fH)

The enthalpy change, that occurs when one mole of a pure
compound in its standard state is formed from its elements in their
standard state, is called as standard enthalpy of formation

Formation
C(s) + 2H2 (g) CH4 (g)

 Some important points:-

1) ∆fHo(H2) = ∆fHo(Cl2) = ∆fHo (C) = ∆fHo (O2) = 0
2) ∆fHo (compound) = Ho (compound)

 Standards enthalpy of combustion(∆cH) :-

The enthalpy change that occurs, when one mole of a substance, in
standard state, is completely oxidized in a reaction, is called as
standard enthalpy of combustion

 Bond Enthalpy:-
The enthalpy change required to break particular covalent bond in
one mole of gaseous molecule to produce gaseous atoms or
radicals, is called as Bond enthalpy
HCl(g) H(g) + Cl(g)
Gaseous gaseous atom
molecules
Bond Enthalpy is given by:-
Bond Enthalpy = ∑ ∆Ho(Reactants) - ∑ ∆Ho(Products)

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 Hess’s Law of constant heat summation
It states that “The overall enthalpy change, for a reaction is
equal to the sum of enthalpy changes of individual steps in
the reaction”.

 Application of Hess’s Law :-

The Hess’s Law has been useful to calculate the enthalpy changes
for the various reactions.

 Spontaneous (Irreversible) process

The process that do not require any external influence or force for
their occurrence, is called as Spontaneous or irreversible process.

OR
The process which have natural tendency to occur in a direction,
which leads to equilibrium, is called as Spontaneous or irreversible
process

 Entropy :-
The molecular disorder or randomness of a system, is measured by
term entropy (S)

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Expression for entropy change (∆S)

𝑄𝑟𝑒𝑣
∆S =
𝑇

where
Q rev = amount of heat transferred in a reversible manner
T = Temperature in kelvin

 Second law of thermodynamics

The second law of thermodynamics states that total entropy of a
system and its surroundings increases in a spontaneous process

∆Stotal = ∆Ssystem + ∆Ssurroundings > O

 Three conditions for ∆S total

∆Stotal > 0 ∆Stotal = 0 ∆Stotal< 0

Spontaneous Process is at Non spontaneous
process equilibrium process

 Gibb’s Energy (G) where

G = H- TS G = Gibb’s energy
H = Enthalpy
also T = Temperature (Kelvin)
S = Entropy
∆G = ∆H - T∆S ∆G = change in Gibb’s energy
∆H = Enthalpy change
∆Stotal = ∆Ssystem + ∆Ssurrounding ∆S = change in entropy

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 Relation between ∆G and ∆Stotal :-
−∆𝐻
∆Ssurr= …………………(1)
𝑇

∆Ssystem = ∆S ………………(2)

∆Stotal = ∆Ssytem+ ∆Ssurrounding

∆𝐻
∆Stotal = ∆S - …………………..(3)
𝑇
So T ∆Stotal = T∆S -∆H
Also, -T∆Stotal = ∆H - T∆S…………(4)
∆G = ∆H - T∆S ………….(5)

Comparing eqn 4 & 5 ∆G = - T ∆Stotal

3 conditions

∆Stotal > 0 ∆Stotal = 0 ∆Stotal < 0

∆G < 0 ∆G = 0 ∆G>0
Spontaneous Process is at Non-spontaneous
equilibrium process

 Temperature of Equilibrium
The temperature at which, the spontaneous process changes to non-
spontaneous process, is called as temperature of equilibrium

∆𝐻
Teq = T =
∆𝑆

Where Teq = T = Temperature of equilibrium in kelvin

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 Gibb’s function and equilibrium constant
∆G = ∆G0 + RT ln Q…………….(1)

Consider,
aA + bB cC + dD

Reaction Quotient
Qc =
[𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠]
[𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠]
= ([A].[B] / [C].[D])

When all reactants and products are gases,

Qp = Pcc x PDd
PAa x PBb ……………..(3)

At equilibrium Qc = Kc
& Qp = Kp and ∆G = 0

∆G = ∆G0 + RT ln K.

At equilibrium
∆G = 0
So 0 = ∆G0 + RT lnk

∆GFor
0 gases
= -RT lnKp
∆G0 = -RT lnKc

also ln = 2.303 x log10

∆G0 = -2.303 RT log10 Kp

∆G0 = -2.303 RT log10 Kc
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