Thermodynamics

Thermodynamics is concerned with the energy changes in physical and

chemical transformation

Limitation of thermodynamics

• It deals only with the properties of macroscopic system and is not

concerned with properties of microscopic system

• It deals only with initial and final state and not on path followed to
reach that state.
Lift staircase pipe
Thermodynamics
Thermodynamics is concerned with the energy changes in physical and
chemical transformation

Limitation of thermodynamics

• It deals only with the properties of macroscopic system and is not

concerned with properties of microscopic system

• It deals only with initial and final state and not on path followed to
reach that state.

• It gives no information regarding the rates at which physical and

chemical process occur.
System Boundary
Surrounding
Basic definitions

SYSTEM:
A portion of the universe chosen to study the thermodynamic properties

SURROUNDING:
All other parts of the universe outside the system where the observations
are made.

BOUNDARY:
Real or imaginary line separating the system from the surrounding.
Types of system

• 1.OPEN SYSTEM

• 2. CLOSED SYSTEM

• 3. ISOLATED SYSTEM
1.OPEN SYSTEM
3.ISOLATED SYSTEM
Water vapor
(Gas)

Heat matter
(Energy) Water
(Liquid)
matter

2.CLOSED SYSTEM
Heat
(Energy)

Water vapor
Heat (Gas) matter
(Energy)
Water
(Liquid)
PROPERTIES OF SYSTEM

• EXTENSIVE PROPERTY

• INTENSIVE PROPERTY
Extensive property Intensive property

Amount Mass Amount Boiling point

50kg
1000C

100kg 1000C

150kg 1000C
PROPERTIES OF SYSTEM
• EXTENSIVE PROPERTY
Any property which depends on the amount of matter present in the
system.
E.g. mass, volume, energy etc.

• INTENSIVE PROPERTY
Any property which is independent of the amount of matter present in the
system.
E.g. refractive index, boiling point, density etc.
state
variables
Certain amount of a gas is enclosed in a
cylinder fitted with a movable piston.

Suppose,
the pressure of the gas is 1 bar (P1),
volume is 1 dm3 (V1) and temperature is
300 K (T1) in the beginning. This initial state
of the system is fully defined by specifying
the values of these properties. Such
properties defining the state of a system, are
state variables.
State Functions :
The property which depends on the state of a system and independent of a path
followed to attain it, is called the state function

Path Functions :
The properties which depend on the path are called path functions.
For example, work (W) and heat (Q).

Lift Staircase Pipe

Thermodynamic equilibrium

• A system is said to be in thermodynamic equilibrium when its state

variables do not vary wit time.

Process: A transition from one state to another is called a process.

Process:
A transition from one state to another is called a process.

• Types of process
• 1. Isothermal process
• 2. Adiabatic process
• 3. Isochoric process
• 4. Isobaric process
• 5. Reversible process
1. Isothermal process :
Temperature of the system remains constant during the transformation
T = constant
∆𝐓 = 𝟎

2. Adiabetic process :
Heat of the system remains constant during the transformation
H = constant
∆𝐇 = 𝟎

3. Isochoric process :
Volume of the system remains constant during the transformation
V = constant
∆𝐕 = 𝟎
3. Isobaric process :
Pressure of the system remains constant during the transformation
P = constant
∆𝐏 = 𝟎
5. Reversible process:
A process conducted in such a way so that at every stage the driving force is
infinitesimally greater than the opposing force and which can be reversed by
a slight change of the opposing force is reversible process.

• Features of reversible process

• i. The driving and opposing forces differ by an infinitesimal amount.

• ii. The process can be reversed by an infinitesimal change in
conditions.
• iii. A reversible process proceeds infinitely slowly and takes place in
infinite number of steps.
• iv. It’s a slow process
• v. Work done is maximum
 Expression for pressure-volume (PV) work

• Consider a certain amount of gas at

constant pressure P, constant
temperatute T and volume V1 enclosed
in a cylinder fitted with frictionless, rigid
movable piston of area A

• As the gas expands the piston moves out

a distance d and the final volume
becomes V2
w.k.t.
f = -Pext × A ……………………….(1) (where Pext is the external pressure)
From def,
W = f × d ……………………………(2)
Substitution from Eq. 1 in 2
W=f×d

W = -Pext × A × d …………………..(3)
The product of area of the piston and distance it moves is the volume change
(∆V) in the system.
∆V = A × d …………………(4)
Substituting eq. 4 in eq. 3 Where change in volume
W = - Pext ∆V ∆V = Vfinal - Vinitial
W = - Pext(V2 – V1) ∆V = V2 – V1
Work done max (rev.)

• Consider n moles of an ideal gas

at constant temp T enclosed in a
cylinder fitted with frictionless
movable rigid piston. It expands
isothermally and reversibly from
the initial volume V1 to final
volume V2. The expansion takes
place in a number of steps
illustrated in the fig.
• During each step with a gradual
removal of masses from the
piston, the gas expand slowly
and its pressure P would
decrease
• After the first step, let the volume increase by a small amount dV
• ∴ 𝐢𝐧𝐢𝐭𝐢𝐚𝐥 𝐯𝐨𝐥𝐮𝐦𝐞 = V final volume = V+dV
• Similarly ,after the first step, let the pressure decrease by a small amount dP
• ∴ 𝐢𝐧𝐢𝐭𝐢𝐚𝐥 𝐩𝐫𝐞𝐬𝐬𝐮𝐫𝐞 = 𝐏 Final pressure = P - dP
• w.k.t.
• W = -P∆V
• W = -P(Vfinal - Vinitial)
• In this case,
• dW = - (P – dP)(V + dV – V)
• dW = - (P-dP)dV
• dW = -PdV + dPdV
• dW = -PdV. ( dP.dV is so small, that it is neglected)
Wmax = ∫dW
V2

Wmax = ∫- PdV From Ideal gas Equation

V1 PV = nRT where P = Pressure
V = Volume
nRT
V2 ∴ P =
V n = no of moles
nRT
Wmax = ∫ - dV R = Universal gas constant
V T = Temperature
V1

V2
1
Wmax = - nRT
∫ V
dV

V1

V2
Wmax = - nRT [ ln(V) ]
V1
 V2
Wmax = - nRT [ ln(V) ] According to Boyle’s law
V1
P1V1 = P2V2
Wmax = - nRT ln(V2) - ln(V1)
P1 V2
=
P2 V1
Wmax = - nRT ln
( )V2
V1
Wmax = - 2.303 nRT log10
()
V2

() V2 V1
Wmax = - nRT loge
V1
P1
Wmax = - 2.303 nRT log10
P2
Wmax = - nRT 2.303 log10
()
V2
V1

Wmax = - 2.303 nRT log10

()
V2
V1
Work done in a chemical reaction
Consider a chemical reaction,
sub eq 1 from eq 2

PV2 – PV1 = n2RT – n1RT

reactants products
P(V2 – V1) = RT(n2 – n1)
(initial) (final)

From Ideal gas equation, where, P∆V = RT∆n

P = pressure
PV = nRT P∆V = ∆nRT ……….(3)
V = volume
T = temperature from work done PV type,
For reactants (initial),
R = Gas constant W = - P∆V ……….(4)
PV1 = n1RT ………….(1)
n = no of moles
substituting eq. 3 in eq. 4
For products (final)
W = - ∆nRT
PV2 = n2RT …………(2)
 W = - P∆V (PV type)

Work done Wmax=-2.303nRTlog10(V2/V1) (Reversible)

W = - ∆nRT (Chemical reaction)

 Sign conventions of W(work)
GAS

C Compression
O On the system
EXPANSION COMPRESSION P Positive

BY THE SYSTEM ON THE SYSTEM

W= -P∆𝐕 W= +P∆𝐕
Internal energy(U)
• Every substance is associated with a definite amount of energy. This
energy stored in a substance is internal energy denoted by U.
• Change in internal energy
∆U = Ufinal – Uinitial
∆U = U2 – U1

• The internal energy of a system is made up of kinetic and potential

energies of individual particles of the system.
• A transfer of energy (as heat or work) from the system would change its
internal energy.

The energy transferred to the The energy transferred from the

system by heating it or system by cooling or by performing
performing work on it work by the system is removed from
is added to the system. the system.
First law of thermodynamics
• Energy is neither created nor destroyed and can only be
converted from one form to another.
 heat
energy

sound
energy
current

light
energy

electrical chemical
energy energy
First law of thermodynamics

• Energy is neither created nor destroyed and can only be converted

from one form to another.

• Energy of the universe remains constant

• The total internal energy of an isolated system is constant

Mathematical expression for First law of Thermodynamics

A B
Work is done on
Heat(Q)
the system (W) C

initial internal U1 + Q U1 + Q + W
energy (U1)
Final internal energy
Final internal energy = U1 + Q + W

U2 = U1 + Q + W

U2 – U1 = Q + W

Uf – Ui = Q + W

∆U = Q + W
w.k.t.
∆U = Q - P∆𝐕 W = -P∆𝐕
First law of thermodynamics cases
• ∆U = Q - P∆𝐕 ……………..(1) u ∆U = Q - P∆𝐕 …………..(1)
• Case 1) u Case 2)
• Isothermal process u Adiabetic process
• temperature remains constant
u Heat remains constant
• internal energy constant
u change in heat = 0
• change in internal energy = 0
u 𝐐=0
• ∆U = 0
u substituting Q = 0 in equation 1
substituting ∆U = 0 in equation 1 ∆U = Q - P∆𝐕 (from 1)
∆U = Q - P∆𝐕 ∆U = 0 - P∆V
0 = Q - P∆V
∆U = - P∆𝐕
Q = P∆𝐕
First law of thermodynamics cases
• ∆U = Q - P∆𝐕 ……………..(1) u ∆U = Q - P∆𝐕 …………..(1)
• Case 3) u Case 4)
• Isochoric process
u Isobaric process
• Volume remains constant
u Pressure remains constant
• change in volume = 0
u change in pressure = 0
• ∆𝐕 = 0
u ∆P = 0
• substituting ∆V = 0 in equation 1
u substituting ∆P = 0 in equation 1
∆U = Q - P∆𝐕 (from 1)
∆U = Q - P∆𝐕
∆U = Q – P(0)

∆U = Q
Enthalpy (H)

Def. : Enthalpy is the total heat content of a system.

It is the sum of internal energy of a system and the energy equivalent to PV work.
enthalpy = internal energy + work(PV) type
H= U +W
H = U + PV
Expression for change in Enthalpy (Physical process) Relationship between ∆H and ∆U for chemical reactions :
Initial enthalpy
Consider a chemical reaction,
H = U + P V ....(1)
1 1 1 1

Final enthalpy
reactants products
H = U + P V …..(2) . (initial)
2 2 2 2 (final)
subtracting eq. 2 from eq.1 From Ideal gas equation, from def of enthalpy,
H2 - H1 = U2 - U1 + PV2 - PV2 PV = nRT
∆H = ∆U + P ∆V ……….(4)
For reactants (initial),
∆ H = ∆ U + P (V2 – V1) substituting eq. 3 in eq. 4
PV1 = n1RT ………….(1)
∆H = ∆U + ∆nRT
∆H = ∆U + P ∆V For products (final)
PV2 = n2RT …………(2)
sub eq 1 from eq 2
PV2 – PV1 = n2RT – n1RT
P(V2 – V1) = RT(n2 – n1)
P∆V = RT∆n
P∆V = ∆nRT ……….(3)
 W = - Pext∆V

WMAX=-2.303nRTlog10(V2/V1)
Work done

W = - ∆nRT

First law of ∆U = Q + W
thermodynamics

∆H = ∆U + P∆V (physical)

Change in
enthalp ∆H = ∆U + ∆𝐧𝐑𝐓 (chemical)
 Enthalpies of physical transformations(process)

Enthalpy of phase transition Enthalpy in atomic or molecular change

i) enthalpy of fusion i) enthalpy of ionization

ii) enthalpy of vaporization ii) enthalpy of atomization

iii) enthalpy of sublimation iii) enthalpy of solution

sublimation

fusion vaporization
solid liquid gas
Enthalpies of physical transformations ii) Enthalpy for the atomic / molecular change
1) Enthalpy of phase transition :
i. Enthalpy of ionization (∆ionH)
i. Enthalpy of fusion : (∆fusH) energy
Enthalpy change that occurs when one mole of a solid is converted into
liquid without change in temperature and pressure I mole gaseous ATOM removing an electron
e.g. H2O(S) H20(l) ∆fusH = 6 kJ/mol

ii. Enthalpy of vapourisation : (∆vapH)

ION
Enthalpy change that occurs when one mole of a liquid is converted
into gas without change in temperature at constant pressure
e.g. H2O(l) H20(g) ∆vapH = 45 kJ/mol

iii. Enthalpy of sublimation : (∆subH) ii. Enthalpy of atomization (∆atoH)

energy
Enthalpy change that occurs when one mole of a solid is directly
converted into gas without change in temperature at constant I mole gaseous SUBSTANCE dissociate
pressure
e.g. H2O(S) H20(g) ∆fusH = 51 kJ/mol
ATOM

iii) Enthalpy of solution ∆solH

Enthalpy change that occurs when 1 mole of a substance is dissolved

in specified amount of solvent.
NaCl(s) NaCl(aq) ∆solH = 4kJ/mol
Thermochemistry :
Thermochemistry deals with enthalpy changes in chemical reactions
Enthalpy of chemical reaction (∆ rH)

5A + 3B 7C + 2D
(s) (g) (l) (g)

∆H = Hfinal - Hinitial
∆H = Hproduct - Hreactant

∆H = 7HC + 2HD - 5HA + 3 HB

Thermodynamic standard state :
The standard state of a substance is the form in which the substance is present at a pressure of 1 bar
and at temperature 298 K. (250C)

H2O (solid) H2O (liquid) H2O (gas)

STANDARD STATE
Standard enthalpy of reaction (∆rH0)

The standard enthalpy of reaction is the enthalpy change

accompanying the reaction when the reactants and products
involved are in their standard states.

P = 1bar
T= 250C (298K)

Standard enthalpy of reaction(∆rH0)

Standard enthalpy of FORMATION (∆fH0)

Enthalpy change that accompanies a reaction in which
one mole of pure compound in its standard state is formed from its elements in their standard states.

C + 2H2 CH4 ∆fH0 = -75 kJ

(s) (g) (g)

Standard enthalpy of COMBUSTION (∆CH0)

Enthalpy change accompanying a reaction in which
one mole of the substance in its standard state is completely oxidised.

C+O CO2 ∆fH0 = -393 kJ

(g) 2
(g) (g)
N2 + 3H2 2NH3 N2 + 3H2 2NH3 ∆H0 = -91KJ
(g) (g) (g)
CHEMICAL REACTION THERMOCHEMICAL EQUATION

THERMOCHEMICAL EQUATION

It is the balanced chemical equation in which the enthalpy change, physical states
and the number of moles of reactants and products, have been specified

Rules to write a thermochemical equation

1. The chemical reaction should be balanced

2. The physical states of reactants and products are specified by letter, s (solid), l (liquid), g (gas) and aq. (aqueous)
3. The value and appropriate sign of enthalpy change should be written on the right hand side.

4. ∆ rH0 for the reverse reaction equals in magnitude and opposite in the sign to that of the forward reaction
5. When a reaction is multiplied or divided by a certain numerical factor, the corresponding ∆ rH0 need to be multiplied or
divided by the same.
Bond enthalpy

The enthalpy change required to break particular covalent bond in one mole of gaseous molecule to produce gaseous
atoms and/or radicals, is called bond enthalpy.

HCl(g) H(g) + Cl(g) ∆H(H-Cl) = 431.9 kJ

For polyatomic molecules,

∆ rH0 = Bond Enthalpy (reactant) – Bond enthalpy(product)

100 rupees

400 rupees

200 rupees 1000 rupees

200 rupees

100 rupees
Hess’s law of constant heat summation
“Overall the enthalpy change for a reaction is equal to sum of
enthalpy changes of individual steps in the reaction”.
1
C + O2 CO ∆H0 = -110 kJ
2
1
CO + O2 CO2 ∆H0 = -283 kJ
2

C + O2 CO2 ∆H0 = -393kJ

Application of Hess’s law

The Hess's law has been useful to calculate the enthalpy changes for
the reactions with their enthalpies being not known experimentally.
Entropy (S)
Entropy is defined as degree of randomness or disorder
Greater the disorder of a system larger is its entropy.

Solid liquid gas

Change in entropy

∆H J
∆S = unit =
T K
Spontaneous process :
Spontaneous processes have a natural tendency to occur and do not require any external influence
for their occurrence.

Key points of spontaneous process

1.It occurs of its own and does not require any external agency to occur.
2. It proceeds in one direction and cannot take place in the opposite direction unless the external
stimulant is present.
3. The spontaneous processes can be rapid or slow, spontaneity is not concerned with the rate
of the reaction.
4. The processes continues till equilibrium is reached. The spontaneous (natural) processes tend
to occur in a direction that leads to equilibrium.
Energy and spontaneity : Consider few spontaneous process
Consider a spontaneous chemical reaction, Melting of ICE
H2O(S) H20(l) ∆fusH = + 6 kJ/mol

Dissolution of salt in water

reactants products
water
NaCl(s) NaCl(aq) ∆solH = + 4kJ/mol

UNSTABLE STABLE

positive
ENERGY ENERGY

Change in enthalpy
∆H= Hp - Hr
Endothermic
∆H= negative Exothermic
Entropy and spontaneity
Consider few spontaneous process,

Melting of ice

H2O(S) H20(l) ∆S = +

Combustion of carbon
spontaneous
C(s) + O2(g) C02(g) ∆S = -
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+ ∆Ssurrounding > 0

i. ∆Stotal > 0, the process is spontaneous

ii. ∆Stotal < 0, the process is nonspontaneous
iiii. ∆Stotal = 0, the process is at equilibrium
Gibbs Free Energy (G)
∆ Stotal = ∆ Ssystem+ - ∆ Hsystem
G = H - TS T
Change in Gibbs Free Energy Multiplying through out by ‘-T’

∆ G = ∆ H - T ∆S - T ∆ Stotal = - T ∆ Ssystem+ - T - ∆ Hsystem

T
Relation between ∆ Stotal and ∆ G
- T ∆ Stotal = - T ∆ Ssystem+ ∆ Hsystem

∆ Stotal = ∆ Ssystem+ ∆ Ssurrounding

- T ∆ Stotal = ∆ Hsystem - T ∆ Ssystem
∆ Stotal = ∆ Ssystem+ ∆ Hsurrounding
- T ∆ Stotal = ∆G system
T
i. ∆Stotal > 0, ∆Gsystem < 0, the process is spontaneous

ii. ∆Stotal < 0, ∆Gsystem > 0, the process is non-spontaneous

iii. ∆Stotal = 0, ∆Gsystem = 0, the process is in equillibrium

Gibbs function and equilibrium constant :
Gibbs energy change for a chemical
reaction is given by At Equilibrium,
∆G = 0 and Q =K
∆G = ∆ GO + RT ln(Q)
∴ ∆G = ∆ GO + 2.303 RT log10(Q)
Consider
∴ 0 = ∆ GO + 2.303RT log10(K)
aA + bB cC + dD
c c d ∴ ∆ GO = -2.303 RT log10(K)
d
[C] [D] (PC) (PD)
Q = or Q =
[A] a [B] b (PA)a (PB) b

∆G = ∆ GO + 2.303 RT log10(Q)