Physical Chemistry for

Engineers – CE1PCE
Session 4: Free energies
Video 3

Dr Stephen David Worrall

s.worrall@aston.ac.uk
Phone: 0121 204 3179
Office: MB 136
1
Intended Learning Outcomes

After this lecture you should be able to:

1) Calculate a standard reaction Gibbs energy.

2) Combine the first and second laws of thermodynamics to obtain the

fundamental equations.

2
Standard reaction Gibbs energies

3
 Third law entropies

• Entropies reported on the basis that S(0) = 0 are called Third Law
entropies.

• A substance in its standard state at a temperature T has a standard

entropy S⦵(T).

• Similarly can define a standard reaction entropy ΔrS⦵ which is the

difference between the molar entropies of the pure separated products
and the pure separated reactants.

∆𝒓 𝑺 =
⦵
∑ ⦵
𝒗𝑺 −
𝒎 ∑ 𝒗𝑺
⦵
𝒎
𝑷 𝒓𝒐𝒅𝒖𝒄𝒕𝒔 𝑹𝒆𝒂𝒄𝒂𝒏𝒕𝒔

4
 Standard reaction Gibbs energies

• Can combine the standard entropy concept from our previous lecture,
with the standard enthalpy concept from Dr Evan’s lectures to give
standard Gibbs energy of reaction.
⦵ ⦵ ⦵
∆ 𝒓 𝑮 =∆𝒓 𝑯 − 𝑻 ∆ 𝒇 𝑺

• Like with standard reaction enthalpies it is convenient to define the

standard Gibbs energy of formation.

⦵
∆𝒇 𝑮

∆𝒓 𝑮 =
⦵
∑ ⦵
𝒗 ∆𝒇 𝑮 − ∑ 𝒗 ∆𝒇 𝑮
⦵

𝑷 𝒓𝒐𝒅𝒖𝒄𝒕𝒔 𝑹𝒆𝒂𝒄𝒂𝒏𝒕𝒔

5
The fundamental equations

6
 Combining the 1st and 2nd laws

• Combining the 1st and 2nd laws gives us an equation that allows us to
better predict the behaviour of matter than either law alone.

𝒅𝑼 =𝒅𝒒+ 𝒅𝒘 𝒅 𝒘 𝒓𝒆𝒗 =− 𝒑𝒅𝑽 𝒅 𝒒 𝒓𝒆𝒗 =𝑻𝒅𝑺

𝒅𝑼 =𝑻𝒅𝑺 − 𝒑𝒅𝑽

• As U is a state function this means that this equation applies for both
reversible and irreversible changes.

• This is the fundamental equation.

7
 Combining the 1st and 2nd laws

• Can then obtain an equation for the Gibbs energy using the
fundamental equation.

𝒅𝑮=𝒅𝑯 − 𝒅 (𝑻𝑺) 𝒅𝑯 =𝒅𝑼 + 𝒅 (𝒑𝑽 )

𝒅𝑮=𝒅𝑯 − 𝑻𝒅𝑺− 𝑺𝒅𝑻 𝒅𝑯 =𝒅𝑼 + 𝒑𝒅𝑽 +𝑽𝒅𝒑

𝒅𝑮=𝒅𝑼 +𝒑𝒅𝑽 +𝑽𝒅𝒑 −𝑻𝒅𝑺 − 𝑺𝒅𝑻

• Inserting the fundamental equation

𝒅𝑼 =𝑻𝒅𝑺 − 𝒑𝒅𝑽
𝒅𝑮=𝑻𝒅𝑺 − 𝒑𝒅𝑽 +𝒑𝒅𝑽 +𝑽𝒅𝒑 −𝑻𝒅𝑺 − 𝑺𝒅𝑻
𝒅𝑮=𝑽𝒅𝒑 − 𝑺𝒅𝑻