3.

5 Helmholtz & Gibbs Energy

From Clausius inequality

dq
dS − ≥0
T

(a) Criteria for spontaneity 1

Heating at constant volume.
Then, in the absence of non-expansion work dqV = dU

TdS ≥ dU (constant V, no additional work)

TdS ≥ dH (constant P, no additional work)

Spontaneity 1

From Clausius inequality

dq
dS − ≥0
T
(a) Criteria for spontaneity 1
Heating at constant volume.
Then, in the absence of non-expansion work dqV = dU

TdS ≥ dU (constant V, no additional work)

At either constant internal energy (dU = 0) or constant
entropy (dS = 0), this expression becomes
dSU ,V ≥ 0 dU S ,V ≤ 0
 Spontaneity 2

(a) Criteria for spontaneity 2

When energy is transferred as heat at constant pressure.
And there is no work other than expansion work, dq p = dH

TdS ≥ dH (constant p, no additional work)

At either constant internal energy (dH = 0) or constant

entropy (dS = 0), this expression becomes
dS H , p ≥ 0 dU S , p ≤ 0

Helmholtz & Gibbs Energy

TdS ≥ dU TdS ≥ dH
dU − TdS ≤ 0 dH − TdS ≤ 0
A = U − TS G = U − TS
Helmholtz energy Gibbs energy

at constant temperature, dA = dU –TdS and dG = dH - TdS

Criteria of spontaneous change

dAT ,V ≤ 0 and dGT , P ≤ 0
 Maximum Work 1

(b) Some remarks on the Helmholtz energy

Criterion of equilibrium dAT ,V = 0

(c) Maximum work
Change in the Helmholtz function is equal to the maximum
work accompanying a process
TdS − dq ≥ 0 where, dU = dq + dw
TdS − dU + dw ≥ 0
dw ≥ dU − TdS
dwmax = dU − TdS = dA

Maximum Work 2

dWmax = dA
Wmax = ∆A with ∆A = ∆U − T∆S

Entropy of system decreased Entropy of system increased

Surrounding entropy increases Surrounding entropy decreases

Maximum Work 3

Example 3.4
 Remarks on Gibbs Energy

(b) Some remarks on the Gibbs energy

Gibbs free energy is common in chemistry than Helmholtz energy,
because we are usually more interested in change occuring at
constant pressure than at constant volume

dGT , P ≤ 0 At constant temperature and pressure, chemical

reations are spontaneous in the direction of
decreasing Gibbs energy.

ex) Spontaneous endothermic reactions

dG = dH - TdS
Increase in TdS overwhelms increase of dH

Maximum Non-expansion Work

H = U + pV
dH = dq + dw + d ( pV )
G = H − TS
dG = dH − TdS − SdT = dq + dw + d ( pV ) − TdS − SdT
when the change is isothermal (dT = 0)
dG = dq + dw + d ( pV ) − TdS
when the change is reversible (dw = dwrev and dq = dqrev = TdS )
dG = TdS + dwrev + d ( pV ) − TdS = dwrev + d ( pV )
= (− pdV + dwadd ,rev ) + pdV + Vdp
if the change occurs at const. pressure (dp = 0)
dG = dwadd ,rev Maximum non-expansion (additional) work
for a measurable change, wadd ,rev = ∆G