Physical Chemistry 2

Lecture 1. Gibbs and Helmholtz

energies
Prepared by:
Niño B. Felices
 MATERIAL EQUILIBRIUM
• Temperature of the system is constant –
thermal equilibrium
• Pressure of the system is constant –
mechanical equilibrium
• In each phase, number of moles of each
species remain constant with time
 Systems in material equilibrium
(1) Reaction equilibrium – rate of forward
reaction equal to rate of reverse reaction
aA + bB ⇌ cC + dD
defined by an equilibrium constant:
𝐶𝑐 𝐷𝑑
𝐾=
𝐴𝑎 𝐵𝑏
 Systems in material equilibrium
(2) Phase equilibrium
Rate of transport of species i between two
phases are equal
Defined by equilibrium ratio:
𝑦𝑖
𝐾𝑖 =
𝑥𝑖
 Material equilibrium in a isolated system

Goal: Derive thermodynamic relations for

systems in material equilibrium

Consider an isolated system not in material

equilibrium:
By the 2nd law of thermodynamics, the entropy
of an isolated system can never decrease over
time and constant if only if all processes are
reversible
Material equilibrium in an isolated system

• Processes occurring: (1) mass transport

between phases and (2) spontaneous
reactions

• System entropy will continue increasing until

all these processes become reversible wherein
the system’s entropy is maximized.

• At material equilibrium Ssystem is maximized

Material equilibrium in closed systems
• For closed systems, there is an exchange of
heat & work with surroundings
• At material equilibrium, Ssystem + Ssurr is
maximized.
 Material equilibrium in a closed system

• Consider closed system not in material

equilibrium but in thermal & mechanical
equilibrium:
𝑑𝑞𝑠𝑢𝑟𝑟 = −𝑑𝑞𝑠𝑦𝑠
dqsys  infinitesimal heat flow associated with
phase changes or chemical reactions
• For an irreversible process
𝑑𝑆𝑢𝑛𝑖𝑣 = 𝑑𝑆𝑠𝑦𝑠 + 𝑑𝑆𝑠𝑢𝑟𝑟 > 0
 Material equilibrium in a closed system

• The surroundings is in thermodynamic

equilibrium throughout the process:
𝑑𝑞𝑠𝑢𝑟𝑟 𝑑𝑞𝑠𝑦𝑠
𝑑𝑆𝑠𝑢𝑟𝑟 = =−
𝑇 𝑇
• The system, however is not in thermodynamic
equilibrium and the processes involved in the
system are irreversible
𝑑𝑞𝑠𝑦𝑠
𝑑𝑆𝑠𝑦𝑠 >
𝑇
Material equilibrium in closed systems
• At material equilibrium, any infinitesimal
process is reversible. Thus
𝑑𝑞𝑟𝑒𝑣
𝑑𝑆𝑠𝑦𝑠 =
𝑇
• For a closed system:
𝑑𝑞
𝑑𝑆 ≥
𝑇
𝑇𝑑𝑆 ≥ 𝑑𝑞
Material equilibrium in closed systems
• Recall: 𝑑𝑈 = 𝑑𝑞 + 𝑑𝑤
𝑇𝑑𝑆 ≥ 𝑑𝑞
𝑇𝑑𝑆 ≥ 𝑑𝑈 − 𝑑𝑤
𝑑𝑈 ≤ 𝑇𝑑𝑆 + 𝑑𝑤
If only PV work 𝑑𝑤 = −𝑃𝑑𝑉
𝑑𝑈 ≤ 𝑇𝑑𝑆 − 𝑝𝑑𝑉
For a closed system in material equilibrium w/
PV work only:
dU = TdS − PdV
Material equilibrium in closed systems
dU = TdS + PdV
• This is called a fundamental property relation
for internal energy.
Note: This is not limited to reversible process
though derived for such.
It is applicable for any process in a closed system
that results to a differential change from one
equilibrium state to another.
 Helmholtz free energy
Consider const. T and V systems
𝑑𝑈 ≤ 𝑇𝑑𝑆 − 𝑃𝑑𝑉
𝑑𝑈 ≤ 𝑇𝑑𝑆 + 𝑆𝑑𝑇 − 𝑆𝑑𝑇 − 𝑃𝑑𝑉
𝑑𝑈 ≤ 𝑑 𝑇𝑆 − 𝑆𝑑𝑇 − 𝑃𝑑𝑉
𝑑 𝑈 − 𝑇𝑆 ≤ −𝑆𝑑𝑇 − 𝑃𝑑𝑉
At constant T and V, dT = 0 and dV = 0.
𝑑 𝑈 − 𝑇𝑆 ≤ 0
A = U – TS where A is the Helmholtz free
energy.
 Helmholtz free energy
At constant T and V, dT = 0 and dV = 0.
𝑑𝐴 ≤ 0
At constant T and V, A continually decrease until
material equilibrium is achieved wherein:
𝑑𝐴 = 0
 Helmholtz free energy
𝑑 𝑈 − 𝑇𝑆 ≤ −𝑆𝑑𝑇 − 𝑃𝑑𝑉
𝑑𝐴 ≤ −𝑆𝑑𝑇 − 𝑃𝑑𝑉
For a closed system in material equilibrium:
𝑑𝐴 = −𝑆𝑑𝑇 − 𝑃𝑑𝑉
This is the fundamental property relation for
Helmholtz free energy.
 Gibbs free energy
• Consider const. T and P systems
𝑑𝑈 ≤ 𝑇𝑑𝑆 + 𝑆𝑑𝑇 − 𝑆𝑑𝑇 − 𝑃𝑑𝑉 + 𝑉𝑑𝑃 − 𝑉𝑑𝑃
𝑑𝑈 ≤ 𝑑 𝑇𝑆 − 𝑆𝑑𝑇 − 𝑑 𝑃𝑉 + 𝑉𝑑𝑃
𝑑 𝑈 + 𝑃𝑉 − 𝑇𝑆 ≤ −𝑆𝑑𝑇 + 𝑉𝑑𝑃
𝑑 𝐻 − 𝑇𝑆 ≤ −𝑆𝑑𝑇 + 𝑉𝑑𝑃
G = H – TS where G is the Gibbs free energy
 Gibbs free energy
• For const. T and P, dT = 0 and dP = 0
𝑑𝐺 ≤ 0
At material equilibrium:
𝑑𝐺 = 0
G continually decreases at constant P and T until
material equilibrium is reached.
 Gibbs free energy
𝑑 𝐻 − 𝑇𝑆 ≤ −𝑆𝑑𝑇 + 𝑉𝑑𝑃
𝑑𝐺 ≤ −𝑆𝑑𝑇 + 𝑉𝑑𝑃
For a closed system in material equilibrium:
𝑑𝐺 = −𝑆𝑑𝑇 + 𝑉𝑑𝑃
This is the fundamental property relationship
for Gibbs energy.
 𝑑𝑈 ≤ 𝑇𝑑𝑆 − 𝑃𝑑𝑉 + 𝑉𝑑𝑃 − 𝑉𝑑𝑃
𝑑𝑈 ≤ TdS − d PV + VdP
𝑑 𝑈 + 𝑃𝑉 ≤ 𝑇𝑑𝑆 + 𝑉𝑑𝑃
𝑑𝐻 ≤ 𝑇𝑑𝑆 + 𝑉𝑑𝑃
For a closed system in material equilibrium:
𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃
This is the fundamental property relation for
enthalpy
Conditions for Material Equilibrium
• dA = 0 (const. T and V)
• dG = 0 (const. T and P)
 Maximum work
𝑑𝑈 ≤ 𝑇𝑑𝑆 + 𝑑𝑤
𝑑𝑤 ≥ 𝑑𝑈 − 𝑇𝑑𝑆
The maximum energy that can be obtained from
the system as work.
𝑑𝑤𝑚𝑎𝑥 = 𝑑𝑈 − 𝑇𝑑𝑆
At const. T, dT = 0.
𝑑𝐴 = 𝑑 𝑈 − 𝑇𝑆 = 𝑑𝑈 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇
Therefore:
𝑑𝑤𝑚𝑎𝑥 = 𝑑𝐴
 Maximum work
• For a closed system at const. T, the maximum
energy available for doing work is A.
 Maximum non-expansion work
𝐺 = 𝐻 − 𝑇𝑆
𝑑𝐺 = 𝑑𝐻 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇
𝑑𝐺 = 𝑑𝑞 + 𝑑𝑤 + 𝑑 𝑃𝑉 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇
For constant T, dT = 0.
𝑑𝐺 = 𝑑𝑞 + 𝑑𝑤 + 𝑑 𝑃𝑉 − 𝑇𝑑𝑆
For reversible work: 𝑑𝑤 = 𝑑𝑤𝑟𝑒𝑣
For reversible isothermal process:
𝑑𝑞 = 𝑑𝑞𝑟𝑒𝑣 = 𝑇𝑑𝑆
 Maximum non-expansion work
𝑑𝐺 = 𝑇𝑑𝑆 + 𝑑𝑤𝑟𝑒𝑣 + 𝑑 𝑃𝑉 − 𝑇𝑑𝑆
Reversible work includes expansion work and
non-expansion work (electrical, etc.)
𝑑𝑤𝑟𝑒𝑣 = −𝑃𝑑𝑉 + 𝑑𝑤𝑎𝑑𝑑
𝑑𝐺 = −𝑃𝑑𝑉 + 𝑑𝑤𝑎𝑑𝑑 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃
At constant pressure, dP = 0:
𝑑𝐺 = 𝑑𝑤𝑎𝑑𝑑
 Maximum non-expansion work
• For a closed system at const. T and P, the
maximum energy available for doing non-
expansion work is equal to G.
 Spontaneity
• When a process is spontaneous
𝑑𝑆𝑢𝑛𝑖𝑣 > 0
For a closed system in mechanical and thermal
equilibrium but undergoes irreversible processes at
const. T and P
𝑞𝑠𝑢𝑟𝑟 𝑞𝑠𝑦𝑠
Δ𝑆𝑠𝑢𝑟𝑟 = =
𝑇 𝑇
If P is constant, 𝑞𝑠𝑦𝑠 = Δ𝐻𝑠𝑦𝑠 .
−Δ𝐻𝑠𝑦𝑠
Δ𝑆𝑠𝑢𝑟𝑟 =
𝑇
 Spontaneity
Δ𝐻𝑠𝑦𝑠
Δ𝑆𝑢𝑛𝑖𝑣 = − + Δ𝐻𝑠𝑦𝑠
𝑇
Δ𝐻𝑠𝑦𝑠 − 𝑇Δ𝑆𝑠𝑦𝑠
Δ𝑆𝑢𝑛𝑖𝑣 = −
𝑇
−ΔGsys
ΔSuniv =
T
Thus, when
ΔGsys > 0 (process is spontaneous)
ΔGsys < 0 (process is non-spontaneous)
 Fundamental Property Relations
• Also called Gibbs equations:
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃
𝑑𝐴 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇
𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇
 Euler’s Reciprocity Equation
• Given total differential of F
𝜕𝐹 𝜕𝐹
𝑑𝐹 = 𝑑𝑥 + 𝑑𝑦
𝜕𝑥 𝑦 𝜕𝑦 𝑥
𝑑𝐹 = 𝑀𝑑𝑥 + 𝑁𝑑𝑌
where
𝜕𝐹 𝜕𝐹
𝑀= and 𝑁 =
𝜕𝑥 𝑦 𝜕𝑦 𝑥
 Euler’s Reciprocity Equation
𝜕𝑀 𝜕2 𝐹 𝜕𝑁 𝜕2 𝐹
= and =
𝜕𝑦 𝑥 𝜕𝑦𝜕𝑥 𝜕𝑥 𝑦 𝜕𝑥𝜕𝑦

when F is a function of x and y, the differential is

exact and it follows that
𝜕𝑀 𝜕𝑁
=
𝜕𝑦 𝑥 𝜕𝑥 𝑦
 Maxwell’s Equations
• 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
Applying Euler’s reciprocity equation
𝜕𝑇 𝜕𝑃
=−
𝜕𝑉 𝑆 𝜕𝑆 𝑉
Maxwell’s Equations
Relationship of Gibbs free energy with
pressure and volume
𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇
𝐺 1 𝐺
𝑑 = 𝑑𝐺 − 2 𝑑𝑇
𝑇 𝑇 𝑇
𝐺 𝑉𝑑𝑃 − 𝑆𝑑𝑇 𝐻 − 𝑇𝑆
𝑑 = − 2
𝑑𝑇
𝑇 𝑇 𝑇
𝐺 𝑉 𝐻
𝑑 = 𝑑𝑃 − 2 𝑑𝑇
𝑇 𝑇 𝑇
Relationship of Gibbs free energy with
pressure and volume
𝐺 𝑉 𝐻
𝑑 = 𝑑𝑃 − 2 𝑑𝑇
𝑇 𝑇 𝑇
By similarity,
𝐺
𝜕 𝑉
𝑇 =
𝜕𝑃 𝑇 𝑇

𝐺
𝜕 𝐻
𝑇 =− 2
𝜕𝑇 𝑃 𝑇
 𝐺
𝜕 𝑉
𝑇 =
𝜕𝑃 𝑇 𝑇
 𝐺
𝜕 𝐻
𝑇 =− 2
𝜕𝑇 𝑇 𝑇

- Called the Gibbs-Helmholtz equation

- This shows that if the change in enthalpy of
a system is known then corresponding
change in G with T can be determined.
 𝐺
𝜕 𝐻
𝑇 =− 2
𝜕𝑇 𝑃 𝑇
When ΔH is a weak function of temperature:
ΔG(T2 , P) ΔG T1 , P 1 1
− = ΔH −
T2 T1 T2 T1
 Problem
• The molar Gibbs free energy of a certain gas is
given by
1 2 1 3
G = RT lnP + A + BP + CP + DP
2 3
Where A, B, and C are constants.
Obtain the equation of state of the gas.