Lecture – III & IV

Thermodynamics

Students are advised to go through the presentation

thoroughly and derive the equations as discussed in the class.
 Third law of thermodynamics

The entropy of each pure element or substance in a perfect crystalline form is

zero at absolute zero.

Ω = 1 for prefectly ordered crystal. Hence 𝑆 = 𝑘𝐵 ln Ω = 0

Exceptions to the third law

Imagine the mixed crystal to be formed from a pure crystal of A and a pure crystal of
B, then for the mixing process

• Impure crystal has at least the entropy of mixing at the absolute zero, its entropy
cannot be zero; such a substance does not follow the third law of thermodynamics
• Substances that are chemically pure do not fulfill the requirement that the crystal
be perfectly ordered at the absolute zero of temperature. E.g. CO and NO. In the
crystals of CO and NO, some molecules are oriented differently than others.

In the actual crystal of CO, the two ends of the molecule are oriented
randomly; it is as if two kinds of carbon monoxide were mixed, half
and half. The molar entropy of mixing would be

• Crystalline hydrogen has a residual entropy of 0.750 R = 6.23 J/K/mol at the

absolute zero of temperature. This entropy is not the result of disorder in the
crystal, but of a distribution over several quantum states.
 Internal energy U

Fundamental equation:
Combined 1st and 2nd law
of thermodynamics

Chemical work which involves

change in number of moles.

Chemical potential is a measure of potential a species has to move from one phase to
another or undergo a chemical reaction.

U is a function of S, V, {ni}, where {ni} is the set of amount of species i; and represented
by U(S, V, {ni}). The total differential of U is written as:

Ns is the number of different species in the system.

Equations of state

Maxwell Relations, obtained

by equating second cross-
partial derivatives as dU is an
exact differential.
 Thermodynamic potentials

Definitions:
Enthalpy: H = U + PV
Helmholtz Free Energy: A = U – TS
Gibbs Free Energy: G = H – TS
dH = dU + d(PV) = dU + PdV + VdP

What are the equations of state in terms of H, A and G?

What are the corresponding Maxwell relations?
Spontaneity criterions

Internal energy provides a criterion for whether a process can occur

spontaneously at constant S, V, and {ni}.

Substitute 2nd law 𝑑𝑆 ≥ đ𝑞/𝑇, in the 1st law with

This is one of the criterions for spontaneous change and equilibrium in the
system involving work and specified amounts of species. At equilibrium, U at
constant S, V, and {ni} must be at a minimum.
Similarly derive:
 Few relations in Helmholtz enery A and Gibbs energy G

Substituting 2nd law of thermodynamics (𝑑𝑆 ≥ đ𝑞/𝑇 in 1st law ( ) we

have

At constant temperature T

−𝑑 𝑈 − 𝑇𝑆 ≥ −đ𝑤 or 𝑑𝐴 𝑇 ≤ đ𝑤 or − 𝑑𝐴 𝑇 ≥ −đ𝑤

In a reversible process at constant T, the work done on the

system is equal to the increase in the Helmholtz energy

The decrease in A is an upper bound on the total work done in the surroundings
 Similarily if the 1st law is written as: 𝑑𝑈 = đ𝑞 − 𝑃𝑑𝑉 + đ𝑤nonpv

Using 2nd law: −𝑑𝑈 − 𝑃𝑑𝑉 + 𝑇𝑑𝑆 ≥ −đ𝑤nonpv

At constant T and P :

For a reversible process at constant T and P the change in Gibbs energy is equal to the
non-PV work done on the system by the surroundings. Thus, when work is done on the
system, the Gibbs energy increases, and when the system does work on the
surroundings, the Gibbs energy decreases.

The decrease in G is an upper bound on the non-PV work done on the surroundings.
 Gibbs–Helmholtz equation

𝜕𝐺
Gibbs free energy is defined as: 𝐺 = 𝐻 − 𝑇𝑆. Using 𝑆 = − we have
𝜕𝑇 𝑃,{𝑛𝑖 }

Eliminating G from above we have: Gibbs–Helmholtz

equation

For a change between state 1 and state 2:

Since

At constant T, for a single component system with no chemical reaction

we can write

For ideal gas: substituting 𝑉 = 𝑛𝑅𝑇/𝑃, then:

where 𝑃∘ is the standard state pressure.

 Chemical potential

Chemical potential of species i, 𝜇𝑖 is defined as:

It is also referred to as partial molar Gibbs energy, 𝜇𝑖 = 𝐺𝑖

Suppose an infinitesimal amount dni of species i is

transferred from phase 𝛼 to phase 𝛽 at constant T
and P.

For the transfer to be spontaneous 𝑑𝐺 < 0 and hence

𝜇𝑖 𝛼 > 𝜇𝑖 𝛽 . Hence a species diffuses spontaneously
from the phase where its chemical potential is higher to the
phase where its chemical potential is lower.

Also 𝑑𝐺 = 0 if 𝜇𝑖 𝛼 = 𝜇𝑖 𝛽 .

Thus, at equilibrium, the chemical potential of a species is the same in all of the
phases of a system.
 Clausius Clapeyron equation

Consider a one component system with phases α and β. At equilibrium

T, P and μ must be the same in two phases.

Corresponding
thermodynamic
A thermodynamic state is defined by state variables T, P and n
potential is G.
If no reaction takes place in the system n is constant. So
phase β Coexistence
curve
P 2
dP
1
dT phase α

All along the coexistence curve for

change in T and P.
Hence,
Note:

Change in entropy
Clapeyron equation for phase change

For vaporization and sublimation

Further assuming vapor as ideal gas, we have

Note H and Vg are molar

quantities.
Clausius - Clapeyron equation
 On integrating between states 1 & 2

(assuming ∆vapH is independent of T).

Partial molar quantities

Definitions:

Chemical
potential

Analogous to μi

because dG
is exact
Maxwell relation
 Similarly show Maxwell relation

Similarly are defined.

• Additive property of partial molar quantities

Since , hence integrating at constant T, P and μi one gets:

Additive
It can also be derived from the Euler relation:
property
of G

EULER RELATION is derived as follows:

U(S,V,n1,n2,…) is a homogenous 1st order function of extensive parameters.
Mathematically this means,
Differentiate w.r.t. λ

Note R.H.S is not

a differential
Put λ=1, and one gets the Euler relation:

Therefore

Follows from the

definition of A, H & G
We proved , then:

Similarly from , show

Proof of (schematic derivation)

Differentiate w.r.t. ni at constant

Multiply through out by ni

and sum over i

Similarly following additive properties can be shown:

 Free energy and chemical equilibria

In general a balanced chemical reaction is represented as

Molecular
formula

is +ve for products

Stoichometric
is -ve for reactants
number of species i

Extent of the reaction (ξ) is given as:

For a reaction: X+Y ⇋ 2Z

 (substituting the )

At chemical equilibrium at constant T and P, G has its minimum value, hence

Equilibrium condition applies to all chemical equilibria,

whether they involve gases, liquids, solids, or solution

Reaction Gibbs energy ∆rG:

Defined as the change in Gibbs energy when the extent of reaction ξ

changes by 1 mol, as specified by the balanced chemical equation, at
constant T and P.
 Chemical potential and activity

Chemical potential of the ith species is written as:

Chemical potential of ith species at standard (reference) state.

For gas reactions, standard state of reactant and products is
pure gas at 1 bar pressure in the ideal state.

Activity. (for real gas. Fugacity f is defined as )

(for ideal gas)

(for real solution. Activity coefficient fc,i=1 for ideal solution)

 At equilibrium:

Substituting μi,eq in the equilibrium condition ,

Equilibrium constant (K):

Standard reaction Gibbs energy ∆rG°

Defined as the change in Gibbs energy when reactants in their standard

state are converted to products in their standard state

Note: ∆rG° and K are functions of T only.

 Substituting μi in ,

Test for spontaneity:

(Reaction is spontaneous in forward direction)

(Reaction is spontaneous in backward direction)

Reaction Reaction
enthalpy entropy
Similarly
Equilibrium constant for gas reactions:

For ideal gases ai = Pi/P°, hence , P°= 1bar.

For an ideal gas reaction A + B ⇋ C:

For reaction in solution: X + Y ⇋ Z ,

(if the reaction involves ideal solutions)

 Free energy in chemical reactions

Standard Gibbs energy of formation

of a mole of i from its elements

Standard Gibbs energy of formation of elements in their reference states are

zero at all temperatures

∆rG° for reaction X+Y ⇋ 2Z

Standard Gibbs energy of
formation of i Standard entropy of i

Standard enthalpy of sum of the standard entropies of the elements

formation of i in the formation reaction for species i.
 Van’t Hoff Equation

Recall Gibbs Helmholtz equation K is only a

for finite changes function of T

(If is independent of T)

K increases when T increases for endothermic

Slope = −∆rH°/R reaction . Equilibrium shifts in
ln K forward direction.

K decreases when T increases for exothermic

reaction . Equilibrium shifts in
1/T backward direction.
 Reactions at an electrochemical cell

(Reduction)
(Half cell) Galvanic cell

Cathode (+)

Anode (-)
(Rxn. in this half cell takes place in rev.
direction in a galvanic cell)

Note: A reaction involving more than one phase that does not involve equilibria
of a species between phases. (heterogenous reaction)

Activities of the pure solid phases are very nearly equal to unity for moderate pressures.

How to calculate activity of electrolytes (here 𝒂𝐇𝐂𝐥 )?

Activity of electrolytes

On the molal (m) scale the activity of a solute substance is defined by

When an infinitesimal quantity of an electrolyte is added to a kilogram of solvent,
the differential change in the Gibbs energy is given by

For strong electrolyte is A𝜈+ B𝜈− , where 𝜈+ is the number of cations and 𝜈− is
the number of anions, electroneutrality requires that

𝑑𝐺 is written as:

where 𝜇 = 𝜈+ 𝜇+ + 𝜈− 𝜇− is the chemical potential of the electrolyte.

The chemical potentials of the cation and anion are given by:
 On substituting 𝜇+ and 𝜇− in 𝜇 we have:

If mean ionic molality 𝑚± and mean ionic activity coefficient 𝛾± are defined
as follows:

Thus 𝜇 is written as

where activity of the electrolyte is written as:

 The standard chemical potential 𝜇 ∘ of the electrolyte is the chemical potential
in a solution of unit activity on the molality scale.

Calculate 𝒎± , and the activity of 1-1 electrolyte like NaCl and 2-1 electolyte
like CaCl2 ?

b) Can the following conversion occur at 500 K? Take the value of Δ𝑟 𝐺 ∘ from (a).

c) Enthalpy of freezing of water at −10 °C is −5619 J mol-1 and entropy of freezing of

water is −20.54 J K−1mol-1 at −10 °C. What is the Gibbs energy of freezing of water at
−10 °C?