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Pilani Campus

CHEM F111 General Chemistry Lecture 12

Thermodynamic Potentials, Maxwell
relations, Chemical equilibrium
Thermodynamics – things
already known

• System, surroundings, universe, types of systems

• Intensive and extensive properties
• Thermal equilibrium and zeroth law, temperature
• Path functions: Work and Heat
• First law, internal energy, enthalpy, heat capacity
• Entropy and second law
• Variation of entropy with temperature and third law
• Free energy (Gibbs and Helmoltz)

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Thermodynamic potentials
Thermodynamic potentials are the scalar quantities used to represent
thermodynamic state of a system.
Useful to obtain equilibrium properties of the system.
Introduced by J.W. Gibbs and Pierre Duham in 1886.
Four commonly used thermodynamic potentials are internal energy,
enthalpy, Helmoltz energy and Gibbs energy. We will study these
potentials for one-component systems with no non-expansion work.
The approach can be easily extended to multicomponent systems.
+PV

U H
–TS

A G

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Thermodynamic potential: U

From the first law, we have

It thus follows, and

We see that the internal energy is a natural function of entropy

and volume. On the other hand, if we want to express the internal
energy as a function of temperature and volume, we get a
complicated form:

Can we find a thermodynamic potential that is a natural function

of temperature of volume?
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Legendre transform (FYI)

Consider a function y = y(x).

y(x) Let the slope of the tangent to the
function at x be w; and y-intercept be Φ.

Φ(w3) The slope is w=dy/dx

The tangents obey
Φ(w2) equations of straight line
write
Φ(w1) y = y(x)
y = wx + Φ
Thus,
Φ(w) = y – wx
The function Φ(w) is called Legendre transform of y(x). y(x) It is
equivalent to y(x),
y(x) but is a natural function of w, instead of x.
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Thermodynamic potential: A

We have,

In the context of Legendre transform, y is U; x is S and the

slope w is T. Calling the intercept (Φ) as “A”, it follows:

A is natural function of T and V:

It follows:

and

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Thermodynamic potentials:
G&H
Analogously, the dependence on T and p can be obtained
by Legendre transform of A to get
→

Thus, and

Similarly, the thermodynamic potential, H can be obtained

from Legendre transform of G:

→ and

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Maxwell relations

Obtained by James Clerk Maxwell in nineteenth century.

Derived from thermodynamic potentials – second order
mixed derivatives with respect to a mechanical variable (P
or V) and a thermal variable (T or S).
Mathematically, if

then it follows:

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Maxwell relations

From, the thermodynamic potential expressions:

dU = TdS – PdV; dH = TdS + VdP
dA = -SdT – PdV; dG = -SdT + VdP

Homework:
Derive these
it follows: relationships
yourself.

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Multicomponent systems
For a one-component system, a thermodynamic potential is
natural function of two variables (T or S, and P or V). In
case of a multicomponent system, it additionally becomes a
natural function of the number of moles of each component.

What is μj? – Chemical potential of j-th component.

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Chemical potential
Chemical potential of a component is defined as the change
in the thermodynamic potential with respect to the change
in the number of moles of that component, keeping the
other variables (number of moles of other components and
the natural variables of the thermodynamic potential)
constant.

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Chemical equilibrium
Consider a chemical reaction:

We define extent of reaction, such that the change in the

number of moles of j-th component is
Then,

For simplicity, we consider the reaction in gas-phase with

the gases dilute enough to behave ideally.
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Chemical equilibrium
Under isothermal conditions, Gibbs energy change of a pure
component would be

Where, refers to standard pressure of 1 bar.

Thus, for one mole of a pure gas, it follows:

The quantity in logarithm is pressure of gas relative to

standard pressure and is referred to as activity, a of the gas.
Pure solids and liquids have unit activity. For solute in a
solution, the activity is concentration relative to standard
concentration of 1 mol dm-3.
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Chemical equilibrium
From these definitions, the Gibbs energy change for our reaction
can be written as:

The quantity, is called reaction quotient. If the Gibbs energy

change is negative, it indicates spontaneity of forward reaction
whereas the positive Gibbs energy change indicates spontaneity of the
backward reaction.
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Chemical equilibrium
At equilibrium, the Gibbs energy change would be zero.

Thus, -

The quantity, K is called equilibrium constant. Rearranging

the above equation and expressing the Gibbs energy in terms
of enthalpy and entropy, it follows:

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Chemical equilibrium
Now, consider a small change in temperature (from T to
T'), so that the reaction enthalpy and the reaction entropy
remain almost constant. Let the equilibrium constant
change from K to K'. It then follows:

This equation is called van't Hoff equation.

Criterion for spontaneity of reactions:

< 0; ( >1)
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Spontaneity of chemical
reactions
Reaction feasible if ΔrGΘ < 0, ie., K > 1, and not so if ΔrGΘ >
0, ie., K < 1
Since ΔrGΘ = ΔrHΘ – T ΔrSΘ
If ΔrHΘ < 0 (exothermic) and ΔrSΘ > 0, then ΔrGΘ < 0 at all T
If ΔrHΘ < 0 (exothermic) and ΔrSΘ < 0, then ΔrGΘ < 0
for T < ΔrHΘ/ΔrSΘ
If ΔrHΘ > 0 (endothermic) and ΔrSΘ > 0, then ΔrGΘ < 0
for T > ΔrHΘ/ΔrSΘ
If ΔrHΘ > 0 (endothermic) and ΔrSΘ < 0, then ΔrGΘ < 0 at no
temperature

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Gibbs energy and
spontaneity

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