COLLEGE OF ENGINEERING

CENTRAL PHILIPPINE UNIVERSITY

ILOILO CITY, PHILIPPINES
Tel. Nos. (033) 3291971 (to 79) Local 1085
Fax No. (033) 3203004
Email: chem._engg@cpu.edu.ph

MODULE 4
FREE ENERGY and EQUILIBRIUM
 If a certain system is away from equilibrium, it will experience changes.
Once equilibrium is reached or has been reached, the tendency to change also
disappears.
No work can be obtained from a system in equilibrium but a system on its
way to equilibrium can still yield useful work.
A system undergoing change can perform maximum work only when the
change is carried out reversibly.
If the process is not completely reversible, the amount of work obtainable
is always below the maximum.
The difference between maximum work and obtainable work appears as
heat.

When the process is carried out reversibly, the process has initial and final states;
- if the properties in the initial state is used, then initial maximum work is
obtained
- if the properties in the final state is used, then final maximum work is
obtained
- the difference between them represents the highest possible quantity of
energy that can be utilized as a result of the process
To evaluate this, we use free energy functions A and G.
where A – Helmholtz free energy

𝑨 = 𝑬 − 𝑻𝑺 → eq. 1
E, T, S are state functions and so is, A
Since the system passes from one state to another,

∆𝑨 = 𝑨𝟐 − 𝑨𝟏
∆𝑨 = ∆𝑬 − 𝑻∆𝑺, @ 𝑻 = 𝒌 → eq. 2
𝒒𝒓
But ∆𝑺 = , and the 1st Law gives 𝒒𝒓 − 𝑾 = ∆𝑬
𝑻
 ∆𝑨 = 𝒒𝒓 − 𝑾 − 𝒒𝒓 = −𝒘𝒎 → eq. 3
Equation 3 tells us that @ T=k, the 𝒘𝒎 obtained by a system is accomplished by a
decreased in A of the system. Reason why A is sometimes called as maximum
work content of a system.
For any pure substance, A, is most conveniently expressed in terms of T and V as
the independent variables, A = f (T, V)

Using partial fractions

𝜕𝐴 𝜕𝐴
𝑑𝐴 = ( ) 𝑑𝑇 + ( ) 𝑑𝑉 → eq. 4
𝜕𝑇 𝑉 𝜕𝑇 𝑇
Differentiate eq.1 completely
𝑑𝐴 = 𝑑𝐸 − 𝑆𝑑𝑇 − 𝑇𝑑𝑆
𝑑𝐴 = 𝑑𝐸 − 𝑆𝑑𝑇 − 𝑑𝑞𝑟
But,
𝑇𝑑𝑆 = 𝑑𝑞𝑟
𝑇∆𝑆 = 𝑞𝑟
and
𝑑𝑞𝑟 = 𝑑𝐸 + 𝑃𝑑𝑉
𝐻 = 𝐸 + 𝑃𝑉

𝑑𝐴 = 𝑑𝐸 − 𝑆𝑑𝑇 − 𝑑𝐸 − 𝑃𝑑𝑉
𝑑𝐴 = −𝑆𝑑𝑇 − 𝑃𝑑𝑉 → eq. 5
Compare eq.4 and eq.5
𝜕𝐴
( ) = −𝑆 → eq. 6
𝜕𝑇 𝑉
 𝜕𝐴
( ) = −𝑃 → eq. 7
𝜕𝑉 𝑇
Note: eq.5 shows the dependence of A for a pure substance in both T and V
𝐴
Differentiate = 𝑤𝑅𝑇, T @ V = k
𝑇

𝐴
𝜕( ) −𝐸
[ 𝑇 ] = 2 → eq. 8
𝜕𝑇 𝑇
𝑉

We can use eq.8 as an alternative equation for variation of A with T

aA + bB + …. = cC + dD + ….
where:

∆𝐴 = ∑ 𝐴′𝑠(𝑝𝑟𝑜𝑑𝑢𝑐𝑡) − ∑ 𝐴′𝑠(𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡)

∆𝐴 = (𝑐𝐴𝑐 + 𝑑𝐴𝐷 + ⋯ ) − (𝑎𝐴𝐴 + 𝑏𝐴𝐵 + ⋯ ) → eq. 9

where:
𝐴𝐴 = Helmholtz free energy of specie A per mole of substance
𝐴𝐵 , 𝐴𝐶 , 𝐴𝐷 = Helmholtz free energy of species B, C, and D per mole of
substance
If A = E – TS is substituted
∆𝐴 = (𝐸𝑝 − 𝐸𝑟 ) − 𝑇(𝑆𝑝 − 𝑆𝑟 )
∆𝐴 = ∆𝐸 − 𝑇∆𝑆 → eq. 10
Applying partial fractions to eq.9
𝜕∆𝐴 𝜕𝐴𝐶 𝜕𝐴𝐷 𝜕𝐴𝐴 𝜕𝐴𝐵
[ ] = [𝑐 ( ) +𝑑( ) + ⋯ ] − [𝑎 ( ) +𝑏( ) + ⋯]
𝜕𝑇 𝑉 𝜕𝑇 𝑉 𝜕𝑇 𝑉 𝜕𝑇 𝑉 𝜕𝑇 𝑉
Using eq.6
𝜕∆𝐴
[ ] = [−𝑐𝑆𝐶 − 𝑑𝑆𝐷 − ⋯ ] − [−𝑎𝑆𝐴 − 𝑏𝑆𝐵 − ⋯ ] = −∆𝑆 → eq. 11
𝜕𝑇 𝑉
Insert eq.11 in eq.10:
𝜕∆𝐴
∆𝐴 = ∆𝐸 + 𝑇 ( )
𝜕𝑇 𝑉
Use eq.8 for variation of ∆𝐴 with T, just place Δ before A and E
∆𝐴
𝜕(
[ 𝑇 )] = −∆𝐸 → eq. 12
𝜕𝑇 𝑇2
𝑉

G ― Gibbs free energy ― represents the net available energy @ a given T and P
𝐺 = 𝐻 − 𝑇𝑆 → eq. 13
Given 2 states of a system
∆𝐺 = 𝐺2 − 𝐺1
∆𝐺 = (𝐻2 − 𝑇2 𝑆2 ) − (𝐻1 − 𝑇1 𝑆1 )
∆𝐺 = ∆𝐻 − 𝑇∆𝑆 → eq. 14 (if T=k)
𝐺 = 𝐴 + 𝑃𝑉
∆𝐺 = ∆𝐴 + 𝑃∆𝑉 → eq. 15 (@ P=k)
Insert eq.2 in eq.15
∆𝐺 = ∆𝐸 − 𝑇∆𝑆 + 𝑃∆𝑉
∆𝐺 = ∆𝐸 + 𝑃∆𝑉 − 𝑇∆𝑆
If P and T vary,
∆𝐺 = ∆𝐸 + 𝑃2 𝑉2 − 𝑃1 𝑉1 − (𝑇2 𝑆2 − 𝑇1 𝑆1 )
∆𝐺 = ∆𝐻 − ∆𝑇𝑆
@T=k 𝑇∆𝑆 = 𝑞𝑟
@P=k ∆𝐻 = ∆𝐸 + 𝑃∆𝑉
Substitute to eq.14
∆𝐺 = ∆𝐸 + 𝑃∆𝑉 − 𝑞𝑟
 ∆𝐺 = −(𝑞𝑟 − ∆𝐸 − 𝑃∆𝑉)
From the 1st Law
𝑞𝑟 − ∆𝐸 = 𝑤𝑚
∆𝐺 = −(𝑤𝑚 − 𝑃∆𝑉) → eq. 16
Eq.16 simply shows that -ΔG represents the maximum net energy @ P = k and T=k
available for doing useful work like the enthalpy, G, is most conveniently
expressed in terms of T and P as the independent variables.
𝐺 = 𝑓(𝑇, 𝑃)
𝜕𝐺 𝜕𝐺
𝑑𝐺 = ( ) 𝑑𝑇 + ( ) 𝑑𝑃 → eq. 17
𝜕𝑇 𝑃 𝜕𝑃 𝑇
Differentiate G = H – TS completely
𝑑𝐺 = 𝑑𝐻 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 → eq. 18
but TdS = dE + PdV
H = E + PV
dH = dE + PdV +VdP
substitute to eq.18
𝑑𝐺 = 𝑑𝐸 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆
𝑑𝐺 = 𝑑𝐸 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 − (𝑑𝐸 + 𝑃𝑑𝑉) − 𝑆𝑑𝑇
𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇
or
𝑑𝐺 = −𝑆𝑑𝑇 + 𝑉𝑑𝑃 → eq. 19
Compare eq.17 and eq.19
𝜕𝐺
( ) = −𝑆 → eq. 20
𝜕𝑇 𝑃
𝜕𝐺
( ) = 𝑉 → eq. 21
𝜕𝑃 𝑇
Differentiate
𝐺
= 𝑤𝑅𝑇, 𝑇 @ 𝑃 = 𝑘
𝑇
𝐺 𝜕𝐺
𝜕( ) 𝑇( ) −𝐺
𝜕𝑇 𝑃
[ 𝑇 ] =
𝜕𝑇 𝑇2
𝑃

𝐺
𝜕( ) −(𝐺 + 𝑇𝑆)
[ 𝑇 ] =
𝜕𝑇 𝑇2
𝑃

𝐺
𝜕( ) 𝐻
[ 𝑇 ] = − 2 → eq. 22
𝜕𝑇 𝑇
𝑃

Note: Use eq.23 as an alternative expression of the dependency of G or T

ΔG for Reactions
For any reaction: ΔG = Gp – Gr
where:
Gp = sum total of the free energies of all the products
Gr = sum total of the free energies of all the reactants
∆𝐺 = (𝐻𝑝 − 𝑇𝑆𝑝 ) − (𝐻𝑟 − 𝑇𝑆𝑟 )

∆𝐺 = (𝐻𝑝 − 𝐻𝑟 ) − 𝑇(𝑆𝑝 − 𝑆𝑟 )
∆𝐺 = ∆𝐻 − 𝑇∆𝑆 → eq. 23
The free energy change in general, is a function of T and P
∆𝐺 = 𝑓(𝑇, 𝑃)
𝜕∆𝐺 𝜕∆𝐺
𝑑(∆𝐺) = [ ] 𝑑𝑇 + [ ] 𝑑𝑃
𝜕𝑇 𝑃 𝜕𝑃 𝑇
 𝜕∆𝐺
[ ] is similar in eq.17 but G was replaced by ΔG
𝜕𝑇 𝑃

If we differentiate eq.23, wRT, T @ P = k

𝜕(∆𝐺) 𝜕(∆𝐻) 𝜕(∆𝑆)
[ ] =[ ] −𝑇[ ] − ∆𝑆 → eq. 24
𝜕𝑇 𝑃 𝜕𝑇 𝑃 𝜕𝑇 𝑃
𝜕(∆𝐺) ∆𝐶𝑝
[ ] = ∆𝐶𝑝 − 𝑇 ( ) − ∆𝑆
𝜕𝑇 𝑃 𝑇
𝜕(∆𝐺)
[ ] = −∆𝑆 → eq. 25
𝜕𝑇 𝑃
The 2nd derivative in eq.17
𝜕(∆𝐺) 𝜕𝐺𝑝 𝜕𝐺𝑟
[ ] =[ ] −[ ] → eq. 26
𝜕𝑃 𝑇 𝜕𝑃 𝑇 𝜕𝑃 𝑇
Use eq.21:
𝜕(∆𝐺)
[ ] = 𝑉𝑃 − 𝑉𝑟 = ∆𝑉 → eq. 27
𝜕𝑃 𝑇
Introduce eq.25 and eq.27 in eq.17
𝑑(∆𝐺) = −∆𝑆𝑑𝑇 + ∆𝑉𝑑𝑃 → eq. 28
where:
−∆𝑆𝑑𝑇 = gives the effect on ΔG of ΔT @ P = k
∆𝑉𝑑𝑃 = shows the effect of ΔP @ T = k
Substitute eq.25 in eq.23
𝜕∆𝐺
∆𝐺 = ∆𝐻 + 𝑇 ( ) → eq. 29
𝜕𝑇 𝑃
An alternative equation for variation of ∆𝐺 with 𝑇 is given in eq.22 but we replace
𝐺𝑟 by ∆𝐺 and 𝐻 by ∆𝐻
∆𝐺
𝜕( )
[ 𝑇 ] = − ∆𝐻 → eq. 30
𝜕𝑇 𝑇2
𝑃
Properties and Significance of ΔG
There are 3 possible conditions that ΔG of a process at T = k and P = k may
be calculated.

If a process proceeds as follows

A+B→C+D ΔG = (―) negative
This means that when the deriving tendency of a reaction is from left to right,
energy is emitted in the reaction, sign of ΔG is (―) negative.
A minus sign for ΔG denotes that the reaction tends to proceed simultaneously.
If it proceeds from the right to the left
A+B←C+D ΔG = (+) positive
A positive sign for ΔG denotes that the reaction is not spontaneous.
If it proceeds like this
A+B↔C+D ΔG = 0
This denotes that the system is in equilibrium, there is no tendency to proceed in
either direction. No work can be done by the system.

Calculation of Free Energy Changes

𝜕𝐺
( ) =𝑉
𝜕𝑃 𝑇
Integrate
𝐺2 𝑃2
∫ 𝑑𝐺 = ∫ 𝑉𝑑𝑃 → eq. 31
𝐺1 𝑃1

Note:
ΔH < 0, ΔS > 0 ― reaction will be spontaneous
 ΔG < 0, @ any T
𝑃2
∆𝐺 = 𝐺2 − 𝐺1 = ∫ 𝑉𝑑𝑃
𝑃1

Note:
ΔH > 0, ΔS < 0 ― reaction will be not spontaneous
ΔG > 0, @ any T
To evaluate the integral V must be expressed in terms of P
For n moles of ideal gas
𝑛𝑅𝑇
𝑉=
𝑃
𝑃2
𝑛𝑅𝑇 𝑃2
∆𝐺 = ∫ 𝑑𝑃 = 𝑛𝑅𝑇𝑙𝑛
𝑃1 𝑃 𝑃1

Note:
The real gases, either V or P obtained from equations can be substituted in
eq.31.
If we try to look on p.331 ― it taught us, as to what integration to use for solids,
gases, and liquids.
As solids and liquids are only slightly compressible, then V can be considered as
constant.
𝑃2
∆𝐺 = ∫ 𝑉𝑑𝑃 = 𝑉(𝑃2 − 𝑃1 ) → eq. 32
𝑃1

For appreciable pressure changes, use eq.32

Sample Problem:
Given:
𝐶𝐻4(𝑔) + 2𝐻2 𝑂(𝑔) → 𝐶𝑂2(𝑔) + 4𝐻2(𝑔)
Req’d: ΔS1000°C, ΔH
Sol’n:
Use Table 9-2
° ° °
1st: ∆𝐺298𝐾 = ∆𝐺𝑝𝑟𝑜𝑑𝑢𝑐𝑡 − ∆𝐺𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡
°
∆𝐺298𝐾 = −94,258 − [2(−54,635) − 12,140]
°
∆𝐺298𝐾 = 27,152 𝑐𝑎𝑙
2nd: ∆𝐻𝑇 = ∆𝐻𝑂 + ∆𝐻𝑃 − ∆𝐻𝑟 → 𝑒𝑞. 1

Start with
a. Use Table 7-2
°
∆𝐻298 = ∆𝐻𝑂 + ∆𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡 − ∆𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡
°
where: ∆𝐻298 = ∆𝐻𝑝° − ∆𝐻𝑟°
°
∆𝐻298 = −94,051 − [−17,889 + 2(−57,798)]
°
∆𝐻298 = 39,434 𝑐𝑎𝑙
b. Use Table 7-7
298
∆𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡 = ∑ 𝑛 ∫ 𝐶𝑝° 𝑑𝑇
0

𝐶𝑝𝐶𝑂2 : 5.166 + 15.177𝑥10−3 𝑇 − 95.78𝑥10−7 𝑇 2 + 2.260𝑥10−9 𝑇 3

4𝐶𝑝𝐻2 : 4[6.62 + 0.81𝑥10−3 𝑇] = 26.48 + 3.24𝑥10−3 𝑇
298
∆𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡 = ∫ (36.65 + 5.22𝑥10−3 𝑇 − 158,000𝑇 −2 )𝑑𝑇
0

∆𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡 = 𝐴
c. Use Table 7-7
298
∆𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 = ∑ 𝑛 ∫ 𝐶𝑝° 𝑑𝑇
0

𝐶𝑝𝐶𝐻4(𝑔) : 3.422 + 17.845𝑥10−3 𝑇 − 41.65𝑥10−7 𝑇 2

 2𝐶𝑝𝐻2 𝑂(𝑔) : 2[7.219 + 2.374𝑥10−3 𝑇 + 2.67𝑥10−7 𝑇 2 ]
= 14.438 + 4.748𝑥10−3 𝑇 + 5.34𝑥10−7 𝑇 2
298
∆𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 = ∫ (17.981 + 0.22964𝑇 − 4.3𝑥10−6 𝑇 2 )𝑑𝑇
0

∆𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 = 𝐵
d. Then solve for ΔHo
∆𝐻𝑂 = 39,434 − 𝐴 + 𝐵 → 𝑒𝑞. 2
e. Then substitute eq. 2 in eq. 1
𝑇 𝑇
°
∆𝐻𝑇 = ∆𝐻𝑂 + ∑ 𝑛 ∫ 𝐶𝑝 𝑑𝑇 − ∑ 𝑛 ∫ 𝐶𝑝° 𝑑𝑇
𝑝𝑟𝑜𝑑𝑢𝑐𝑡 298 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 298

∆𝐻𝑇 = 𝑓(𝑇) → 𝑒𝑞. 3

3rd: Use eq. 30 derived equation

∆𝐺
𝜕( )
[ 𝑇 ] = − ∆𝐻
𝜕𝑇 𝑇2
𝑃

Substitute eq.3 in eq.30

∆𝐺
= ______________________ + 𝐼
𝑇
∆𝐺𝑇 = 𝑓(𝑇) → 𝑒𝑞. 4
4th: Evaluate I
Substitute T = 298
°
∆𝐺298 obtained from 1st step → 27,152 cal
5th: Use eq. 4, substitute T = 1273 K
∆𝐺 = _______________
6th: Use eq. 25 derived equation
 𝜕(∆𝐺)
[ ] = −∆𝑆
𝜕𝑇 𝑃
Differentiate eq. 4
158,000
∆𝐺 = 39,458.67 + 17.74𝑥10−3 𝑇𝑙𝑛𝑇 − 2
− 4.3𝑥10−6 𝑇 2
3𝑇
−3
1 −3
158,000 𝑇 −1
∆𝑆 = − [17.74𝑥10 ( ) + 17.74𝑥10 𝑙𝑛𝑇 − (−2) ( )( ) − 2(4.3𝑥10−6 )𝑇 + 𝐼]
𝑇 3 −1

Substitute T = 1273 K
∆𝑆 = _______________
7th: Use ΔH = TΔS + ΔG, solve for ΔH

Complete Solution:
1st: get ∆𝐻° from Table 7-2
°
∆𝐻298 = 39,434 𝑐𝑎𝑙
2nd:
298 298
° °
∆𝐻298 = ∆𝐻𝑂 + ∑ 𝑛∫ 𝐶𝑝 𝑑𝑇 − ∑ 𝑛∫ 𝐶𝑝° 𝑑𝑇
𝑝𝑟𝑜𝑑𝑢𝑐𝑡 0 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 0

∆𝐻𝑂 = __________
3rd:
𝑇 𝑇
°
∆𝐻𝑇 = ∆𝐻𝑂 + ∑ 𝑛 ∫ 𝐶𝑝 𝑑𝑇 − ∑ 𝑛 ∫ 𝐶𝑝° 𝑑𝑇 → 𝑒𝑞. 1
𝑝𝑟𝑜𝑑𝑢𝑐𝑡 0 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 0

4th:
∆𝐺
𝜕( )
[ 𝑇 ] = − ∆𝐻
𝜕𝑇 𝑇2
𝑃
 ∆𝐺
𝜕( ) −49,291.991 0.022264 0.01𝑥105
[ 𝑇 ] = − −6
+ 4.3𝑥10 −
𝜕𝑇 𝑇2 𝑇 𝑇4
𝑃

−2
0.01𝑥105
−6
= −49,291.991𝑇 − 0.022264𝑙𝑛𝑇 + 4.3𝑥10 𝑇 − +𝐼
3𝑇 3
°
5th: If we substitute the value of ∆𝐺298 = −12,140 @ 𝑇 = 298𝐾
Solve for I
0.01𝑥105
−12,140 = 49, 291.991 − 0.022264(298) ln(298) + 4.3𝑥10−6 (298)2 + + (298)I
3(298)2

I = ―206
6th:
0.01𝑥105
−6 2
∆𝐺𝑇 = 49,291.991 − 0.022264𝑇𝑙𝑛𝑇 + 4.3𝑥10 𝑇 + + 𝐼𝑇 → 𝑒𝑞. 2
3𝑇 2
7th: Solve for ΔG when T = 1000 K
0.01𝑥105
∆𝐺 = 49,291.991 − 0.022264(1000) ln(1000) + 4.3𝑥10−6 (1000)2 + − 206(1000)
3(1000)2

∆𝐺 = −156,857.5 𝑐𝑎𝑙
To obtain ΔS, differentiate eq.2
𝜕(∆𝐺) −6 )(2𝑇)
0.01𝑥105
[ ] = −∆𝑆 = −0.022264 − 0.022264𝑙𝑛𝑇 + (4.3𝑥10 + (−2)(𝑇 −1 ) + 𝐼
𝜕𝑇 𝑃 3

670
−∆𝑆 = −206.02264 − 0.022264𝑙𝑛1000 + 8.6𝑥10−6 (1000) −
1000
−∆𝑆 = −206.8
∆𝑆 = 206.8
Use ΔH = TΔS + ΔG
∆𝐻 = 1000(206.8) + (−156,857.5)
∆𝐻 = 49,942.5 𝑐𝑎𝑙
Fugacity and Activity Concepts
For ideal gases at low pressures:
𝑃2
∆𝐺 = 𝑛𝑅𝑇𝑙𝑛
𝑃1
For real gases:
𝑃2
∆𝐺 = ∫ 𝑉𝑑𝑃
𝑃1

where V must be expressed in terms of P

G.N. Lewis showed how real systems may be handled without discarding the
simple free energy equations derived for ideal systems.
This is by the use of 2 new thermodynamic quantities.
It is a known fact that each substance in a particular state has a definite tendency
to escape from its present state.
Mr. Lewis pointed out that this escaping tendency can be measured by fugacity
which is related to free energy per mole of the substance.
𝐺 = 𝑅𝑇𝑙𝑛𝑓 + 𝐵 → 1
where B is a constant dependent on a) T and b) nature of the substance
But B can’t be evaluated since the absolute values of G are not known. So, we
refer all free energy measurements for any given substance to a standard
reference point.
Let G° = free energy in the standard state
f° = fugacity in the standard state

𝐺° = 𝑅𝑇𝑙𝑛𝑓 ° + 𝐵 → 2
Subtract 2 from 1
𝑓 𝑓
𝐺 − 𝐺 ° = 𝑅𝑇𝑙𝑛 ; 𝐺 = 𝐺 °
+ 𝑅𝑇𝑙𝑛
𝑓° 𝑓°
 𝑓
where: 𝑎 =
𝑓°

𝐺 = 𝐺° + 𝑅𝑇𝑙𝑛𝑎 → 3
For a difference between 2 states
∆𝐺 = 𝐺2 − 𝐺1
∆𝐺 = (𝐺° + 𝑅𝑇𝑙𝑛𝑎2 ) − (𝐺° + 𝑅𝑇𝑙𝑛𝑎1 )
𝑎2
∆𝐺 = 𝑅𝑇𝑙𝑛
𝑎1
For n moles:
𝑎2
∆𝐺 = 𝑛𝑅𝑇𝑙𝑛
𝑎1
It is said that at the standard state of a gas f°=1
𝑓
Therefore, 𝑎 = =𝑓
𝑓°

Thus, 3 becomes G = G° + RTlnf

If gas is ideal: f = P
(Note: Any gas can be brought into an ideal state by reducing its pressure to zero)
𝑓
𝑓𝑎𝑛𝑦 𝑔𝑎𝑠 = 𝑃 𝑎𝑠 𝑃 → 0 𝑜𝑟 lim =1
𝑃→0 𝑃
𝑓
As long as the gas is ideal, the ratio remains equal to 1.
𝑃

But as the gas deviates from ideality

𝑓
𝑓 ≠ 𝑃 𝑎𝑛𝑑 ≠1
𝑃
The further the value of this ratio to 1, the greater is the non-ideality of the gas.
This ratio is now called the activity coefficient of the gas, represented by γ.

γ – gives a direct measure of the extent to which any real gas deviates from
ideality @ any given P and T.
To determine γ of gases at T, use
𝑑𝐺 = 𝑉𝑑𝑃
Since 𝐺° is constant at any T, then
𝐺 = 𝐺° + 𝑅𝑇𝑙𝑛𝑓
𝐺 − 𝐺° = 𝑅𝑇𝑙𝑛𝑓
𝑑𝐺 = 𝑅𝑇𝑑𝑙𝑛𝑓 = 𝑉𝑑𝑃
𝑉𝑑𝑃
𝑑𝑙𝑛𝑓 = → (1)
𝑅𝑇
𝑅𝑇
If we let 𝛼 = 𝑉 − → (2), then
𝑃

𝑅𝑇
𝑉= + 𝛼 → (2)
𝑃
Substitute (2) in (1)
𝑅𝑇 𝑑𝑃
𝑑𝑙𝑛𝑓 = [ + 𝛼]
𝑃 𝑅𝑇
𝑅𝑇 + 𝛼𝑃 𝑑𝑃
𝑑𝑙𝑛𝑓 = [ ]
𝑃 𝑅𝑇
𝑑𝑃 𝛼 𝑑𝑃 𝛼
𝑑𝑙𝑛𝑓 = [ + ] ; 𝑑𝑙𝑛𝑓 = 𝑑𝑙𝑛𝑃 + 𝑑𝑃
𝑃 𝑅𝑇 𝑅𝑇 𝑅𝑇
𝑓 𝛼
𝑑𝑙𝑛𝛾 𝑜𝑟 𝑑𝑙𝑛 = 𝑑𝑃 → (3)
𝑃 𝑅𝑇
Integrate (3) between limits:
P=0→P=P
γ=1→γ=γ
𝛾
1 𝑃
∫ 𝑑𝑙𝑛𝛾 = ∫ 𝛼𝑑𝑃
𝛾=1 𝑅𝑇 𝑃=0
 1 𝑃
𝑙𝑛𝛾 = ∫ 𝛼𝑑𝑃 → (4)
𝑅𝑇 0
or
𝑃
1
𝑙𝑜𝑔𝛾 = ∫ 𝛼𝑑𝑃
2.303𝑅𝑇 0
Solve 12, 13, 14, 15, 16 (BW)

Standard States for Solids and Liquids

As mentioned from our previous lecture @ this state, the solid or liquid has
a = 1 and G = G°

Consider the reaction aA + bB + …... = cC + dD + ……

Let aA, aB, aC, aD = activities of products and reactants
Their respective G’s/mole @ T are
𝐺𝐴 = 𝐺𝐴° + 𝑅𝑇𝑙𝑛𝑎𝐴 → {1𝑎}
𝐺𝐵 = 𝐺𝐵° + 𝑅𝑇𝑙𝑛𝑎𝐵 → {1𝑏}
𝐺𝐶 = 𝐺𝐶° + 𝑅𝑇𝑙𝑛𝑎𝐶 → {1𝑐}
𝐺𝐷 = 𝐺𝐷° + 𝑅𝑇𝑙𝑛𝑎𝐷 → {1𝑑}
where G°s with the given subscripts represent free energy @ unit
activity of the respective species
∆𝐺 = [𝑐𝐺𝐶 + 𝑑𝐺𝐷 + ⋯ ] − [𝑎𝐺𝐴 + 𝑏𝐺𝐵 + ⋯ ] → {2}
Substitute {1𝑎}, {1𝑏}, {1𝑐}, {1𝑑} in {2}
𝑎𝐶𝑐 𝑎𝐷𝑑
∆𝐺 = ∆𝐺° + 𝑅𝑇𝑙𝑛 𝑎 𝑏 → 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑖𝑠𝑜𝑡ℎ𝑒𝑟𝑚
𝑎𝐴 𝑎𝐵
Reaction Isotherm → most fundamental thermodynamic equation
 Free energy change of a reaction in terms of free energy change in the
standard state and the starting and final activities @ any T= k
Note: For any reaction, ∆𝐺° is constant @ any given T and completely
independent of P.

Let us now define ΔGf = standard free energy of formation of a compound

ΔGf = free energy which accomplished the formation of a compound @ unit
activity from the elements also @ unit activity
Note:
∆𝐺𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 is evaluated using Gf as in ∆𝐻𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 using Hf

Sample Problem:
18
(354) The standard free energy of formation of 𝐻2 𝑂(𝑙) at 25°C is – 56,690 cal. Find
the free energy of formation of 𝐻2 𝑂 at 25°C from 𝐻2 at a partial pressure of 0.01
atm and 𝑂2 at a partial pressure of 0.25 atm.
1 °
𝐻2(𝑔,1𝑎𝑡𝑚) + 𝑂2(𝑔,1𝑎𝑡𝑚) → 𝐻2 𝑂(𝑙,1𝑎𝑡𝑚) ∆𝐺25 = −56,690 𝑐𝑎𝑙 → (1)
2
Required: ΔGf of 𝐻2 𝑂 @ 25°C of 𝐻2(𝑔,0.01 𝑎𝑡𝑚) + 𝑂2(𝑔,0.25 𝑎𝑡𝑚) → 𝐻2 𝑂(𝑙,1𝑎𝑡𝑚)

Solution:
°
1st: Evaluate ∆𝐺25℃ of the reaction
𝐻2(𝑔,1𝑎𝑡𝑚) → 𝐻2(𝑔,0.01 𝑎𝑡𝑚)

°
𝑃2
∆𝐺25℃ = 𝑛𝑅𝑇𝑙𝑛 = 1(1.987)(298)𝑙𝑛10−2
𝑃1
°
∆𝐺25℃ = −2,720 𝑐𝑎𝑙 → (2)
°
2nd: Evaluate ∆𝐺25℃ of the reaction
1 1
𝑂2(𝑔,1𝑎𝑡𝑚) → 𝑂2(𝑔,0.25𝑎𝑡𝑚)
2 2
 °
1
∆𝐺25℃ = (1.987)(298)𝑙𝑛25𝑥10−2
2
°
∆𝐺25℃ = −410 𝑐𝑎𝑙 → (3)
Subtract (2) and (3) from (1)
1
𝐻2(𝑔,0.01𝑎𝑡𝑚) + 𝑂2(𝑔,0.25𝑎𝑡𝑚) → 𝐻2 𝑂(𝑙,1𝑎𝑡𝑚)
2
°
∆𝐺25℃ = −56,690 + 2,720 + 410
°
∆𝐺25℃ = −53,560 𝑐𝑎𝑙
Seatwork: 19, 23, 24

Application of Clapeyron Equation in Physical Equilibrium involving Solids and

Liquids
𝑑𝑃 ∆𝐻
= → 1
𝑑𝑇 𝑇∆𝑉
This equation relates the change in temperature which must accompany a change
in pressure occurring in a system containing 2 phases of a pure substance in
equilibrium.
To integrate this equation, ΔH and ΔV must be known as functions of temperature
or pressure.
If this information is not available, we express 1 in differential form
𝑃2 − 𝑃1 ∆𝐻
= → 2
𝑇2 − 𝑇1 𝑇∆𝑉
where T is taken as the average of T1 and T2
Or, if we integrate 1
𝑃2 𝑇2
𝑑𝑇
∆𝑉 ∫ 𝑑𝑃 = ∆𝐻 ∫
𝑃1 𝑇1 𝑇
∆𝐻 𝑇2
𝑃2 − 𝑃1 = 𝑙𝑛 → 3
∆𝑉 𝑇1
 where: ΔH and ΔV are taken to be constants
Equation 3 is more precise than 2 for calculations with slight changes in
temperature.

Vapor Pressure of Liquids

Define:
1. Saturated vapor pressure of the liquid
2. Heat of vaporization
∆𝐻𝑣 = 𝐻𝑣 − 𝐻𝑙
where: 𝐻𝑣 = enthalpy of vapor
𝐻𝑙 = enthalpy of liquid
For an evaporation process, ∆𝐻𝑣 is always (+) positive
For condensation process, ∆𝐻𝑣 is always (-) negative
∆𝐻𝑣 = ∆𝐸𝑣 + 𝑃∆𝑉𝑣
𝑃 = 𝑣𝑎𝑝𝑜𝑟 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒
∆𝐸𝑣 = 𝐸𝑣 − 𝐸𝑙
∆𝑉𝑣 = 𝑉𝑣 − 𝑉𝑙
For a vaporization process, 1 can be written as
𝑑𝑃 ∆𝐻𝑣
=
𝑑𝑇 𝑇(𝑉𝑔 − 𝑉𝑙 )
If the temperature is too near to the critical value, 𝑉𝑙 is negligible.
Note: Critical – point when the substance changes from liquid to vapor
𝑑𝑃 ∆𝐻𝑣 ∆𝐻𝑣 𝑃
= =
𝑑𝑇 𝑇𝑉𝑔 𝑅𝑇 2
𝑅𝑇
𝑃𝑉 = 𝑅𝑇; 𝑉=
𝑃
 1 𝑑𝑃 ∆𝐻𝑣
=
𝑃 𝑑𝑇 𝑅𝑇 2
𝑑𝑙𝑛𝑃 ∆𝐻𝑣
=
𝑑𝑇 𝑅𝑇 2
Integrating,
𝑃2
∆𝐻𝑣 𝑇2 𝑑𝑇
∫ 𝑑𝑙𝑛𝑃 = ∫
𝑃1 𝑅 𝑇1 𝑇 2
𝑃2 ∆𝐻𝑣 1 𝑇2 ∆𝐻𝑣 𝑇2 − 𝑇1
𝑙𝑛 = [− ] = [ ]
𝑃1 𝑅 𝑇 𝑇1 𝑅 𝑇1 𝑇2
𝑃2 ∆𝐻𝑣 𝑇2 − 𝑇1
𝑙𝑜𝑔 = [ ]
𝑃1 2.303𝑅 𝑇1 𝑇2

The Boiling Point of the Liquids

Normal Boiling Point
If ∆𝐻𝑣 of the liquid is not known, then its value may be
estimated from Trouton’s rule.
This rule states that the ratio of the molar heat of vaporization
of a liquid to its normal boiling point on the absolute scale is the
same constant for all liquids.
∆𝐻𝑣
= 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇𝑏
An alternative way of stating the rule is that the entropy of vaporization of
all liquids at their normal boiling point is a constant.
For ∆𝐻𝑣 in cal/mole, T in °K, the value of the constant = 21
Table 9-3 gives the value of the constant for liquids.

Sublimation Pressure of Solids

- Equilibrium vapor pressure of a solid
 - Similar to saturated vapor pressure of a liquid
For any given solid, vapor pressure is a constant at any given
temperature and the process is accompanied by an absorption of heat
called the heat of sublimation, ∆𝐻𝑠 and by a volume change
∆𝑉𝑠 = 𝑉𝑔 − 𝑉𝑠
where: 𝑉𝑠 = molar volume of the solid
If 𝑉𝑠 is negligible compared to 𝑉𝑔 and if the vapor behaves as an ideal gas,
then we can apply the Clapeyron Equation.
∆𝐻𝑣 𝑖𝑠 ∆𝐻𝑠
Temperature (T) is now the sublimation temperature. At any given
temperature, the sublimation of a solid is equivalent to the fusion of the solid and
the vaporization of the resulting solution.
∆𝐻𝑠 = ∆𝐻𝑓 + ∆𝐻𝑣