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.

= 1 for perfectly ordered crystal. Hence = ln = 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 crosspartial 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 /, 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 energy A and Gibbs energy G

Substituting 2nd law of thermodynamics ( / in 1st law (
have

) we

At constant temperature T
or

or

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: = + nonpv

Using 2nd law: + nonpv
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.

GibbsHelmholtz equation
Gibbs free energy is defined as: = . Using =

Eliminating G from above we have:

For a change between state 1 and state 2:

,* +

we have

GibbsHelmholtz
equation

Since

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

we can write

For ideal gas: substituting = /, then:

where is the standard state pressure.

Chemical potential
Chemical potential of species i, is defined as:
It is also referred to as partial molar Gibbs energy, =

Suppose an infinitesimal amount dni of species i is

transferred from phase to phase at constant T
and P.

For the transfer to be spontaneous < 0 and hence

> . Hence a species diffuses spontaneously
from the phase where its chemical potential is higher to the
phase where its chemical potential is lower.
Also = 0 if = .

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

A thermodynamic state is defined by state variables T, P and n

If no reaction takes place in the system n is constant. So
phase
P

Corresponding
thermodynamic
potential is G.
Coexistence
curve

dP
1
dT

All along the coexistence curve for

change in T and P.

phase

Hence,

Change in entropy
for phase change

Here =? and why?

Clapeyron equation

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 i

Maxwell relation

because dG
is exact

Maxwell relation

Similarly show
Similarly

are defined.

Additive property of partial molar quantities

Since
Additive
property
of G

, hence integrating at constant T, P and i one gets:

It can also be derived from the Euler relation:

EULER RELATION is derived as follows:

(, , 1 , 2 , ) is a homogenous 1st order function of extensive parameters.
Mathematically this means,

Differentiate w.r.t.

Put =1, and one gets the Euler relation:

Note R.H.S is not

a differential

Therefore

Follows from the

definition of A, H & G

We proved

Similarly from

, then:

, 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
Stoichometric
number of species i

is +ve for products

is -ve for reactants

Extent of the reaction () is given as:

For a reaction: X+Y 2Z

(substituting as

Therefore,
At chemical equilibrium at constant T and P, G has its minimum value, i.e.

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 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 = 1 for ideal
solution)

At equilibrium:
Substituting i,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 i in

Test for spontaneity:

(Reaction is spontaneous in forward direction)

(Reaction is spontaneous in backward direction)

Reaction
enthalpy

Similarly

Reaction
entropy

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 (1 mole of) i
from its elements

Standard enthalpy of
formation of i

Standard entropy of i

sum of the standard entropies of the elements

in the formation reaction for species i.

Vant Hoff Equation

Recall Gibbs Helmholtz equation

for finite changes

K is only a
function of T

(If

ln K

Slope = rH/R

1/T

is independent of T)

K increases when T increases for endothermic

reaction
. Equilibrium shifts in
forward direction.
K decreases when T increases for exothermic
reaction
. Equilibrium shifts in
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 )?

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 A+ B , where + is the number of cations and is

the number of anions, electroneutrality requires that

is written as:

where = + + + is the chemical potential of the electrolyte.

The chemical potentials of the cation and anion are given by:

On substituting + and in we have:

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

Thus is written as

where activity of the electrolyte is written as:

The standard chemical potential of the electrolyte is the chemical potential

in a solution of unit activity on the molality scale.
Calculate , 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 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 K1mol-1 at 10 C. What is the Gibbs energy of freezing of water at
10 C?