CHEM20024 Lecture Notes 11 - Free Energy and Equilibrium

FREE ENERGY AND EQUILIBRIUM
Chemical Thermodynamics (E)

Chemistry and Energy Relations
Lecture Notes 11
Chemistry for Engineers
GIBBS FREE ENERGY (G) – the maximum net energy at constant T and P available
for doing useful work available from a process
𝐺 = 𝐻 − 𝑇𝑆
At constant temperature process,
∆𝐺 = ∆𝐻 − 𝑇∆𝑆
At standard conditions,
∆𝐺° = ∆𝐻° − 𝑇∆𝑆°
For reactions,
∆𝐺 = 𝐺𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝐺𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
Calculation of Free Energy Changes
𝐺2 𝑃2
𝑑𝐺 = 𝑉𝑑𝑃
𝐺1 𝑃1
For ideal gases,

𝑃2
∆𝐺 = 𝑛𝑅𝑇 𝑙𝑛
𝑃1
For solids and liquids,
∆𝐺 = 𝑉 𝑃2 − 𝑃1
Gibbs Free Criteria on Spontaneity
1. If ΔG < 0 , the reaction is spontaneous in the forward reaction

2. IIf ΔG = 0, reaction is at equilibrium
3. If ΔG > 0, the reaction in the forward direction is nonspontaneous (work must
be done to make it occur) but the reverse reaction is spontaneous.
In any spontaneous process carried out, at constant temperature and pressure,

the free energy always decreases.
Gibbs Free Energy and Temperature

SAMPLE PROBLEM 01:

SAMPLE PROBLEM 02:
ANS: -9.921 kJ
SAMPLE PROBLEM 03:
Two moles of an ideal gas are compressed isothermally and reversibly at 100°C
from a pressure of 10 to 25 atm. Find the value of ∆G.
ANS: 1359 cal

SAMPLE PROBLEM 04:

Standard Free Energies of Formation
∆𝐺° = 𝑛∆𝐺𝑓°𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝑛∆𝐺𝑓°𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

SAMPLE PROBLEM 05:
Calculate ∆H°, ∆S° and ∆G° at 298K for the reaction below. Show that ∆G° = ∆H° -
T∆S°. Is the process spontaneous or not spontaneous?
ANS: ∆H° = -166 kJ; ∆S° = 1.38 J/K; ∆G° = -166 kJ

PHYSICAL EQUILIBRIA INVOLVING PURE SUBSTANCES
CLAPEYRON EQUATION: relates the change in temperature which must accompany a change in
pressure occurring in a system containing two phases of a pure substance in equilibrium
𝑑𝑃 ∆𝐻
=
𝑑𝑇 𝑇∆𝑉
𝑷𝟐 − 𝑷𝟏 ∆𝑯
=
𝑻𝟐 − 𝑻𝟏 𝑻∆𝑽
If ∆H/∆V are constant,
∆𝐻 𝑇2
𝑃2 − 𝑃1 = 𝑙𝑛
∆𝑉 𝑇1
SAMPLE PROBLEM 06:
At 273.15K the molar enthalpy of fusion of water ΔHfusion is 6 x 103 J/mol and the
corresponding volume change is –1.6 x 10-6 m3/mol. Estimate the melting point
of ice at a pressure of 150 atmospheres.
ANS: 272.07K
VAPOR PRESSURES OF LIQUIDS
CLAUSIS-CLAPEYRON EQUATION: expresses the variation of vapor pressure with temperature
𝑑 𝐼𝑛𝑃 ∆𝐻𝑣
=
𝑑𝑇 𝑅𝑇 2
∆𝐻𝑣 𝑑𝑇
𝑙𝑛𝑃 = +𝐶
𝑅 𝑇2
∆𝐻𝑣 1
𝑙𝑛𝑃 = − +𝐶
𝑅 𝑇
∆𝐻𝑣 1
𝑙𝑜𝑔10 𝑃 = − +𝐶
2.303𝑅 𝑇
𝑷𝟐 ∆𝑯𝒗 𝑻𝟐 − 𝑻𝟏
𝒍𝒐𝒈𝟏𝟎 =
𝑷𝟏 𝟐. 𝟑𝟎𝟑𝑹 𝑻𝟏 𝑻𝟐
Where R=1.987 cal/mol-K = 8.314 J/mol-K

SAMPLE PROBLEM 07:
At 373.6K and 372.6K the vapor pressures of H2O(l) are 1.018 and 0.982 atm,
respectively. What is the heat of vaporization of water?
ANS: 552 cal/g

TROUTON’S 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 88𝐽
= 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ~
𝑇𝑏 𝑚𝑜𝑙 − 𝐾
𝑃2 ∆𝐻𝑣 𝑇𝑏 1 1
𝑙𝑛 = −
𝑃1 𝑅 𝑇1 𝑇2
Tb is the normal boiling point if a liquid which is defined as the temperature at which
the vapor pressure of the liquid equals 760 mmHg pressure or 1 atm.
Boiling point of a liquid is defined as the temperature at which the vapor pressure of
the liquid becomes equal to the external pressure acting upon the surface of the liquid.
SAMPLE PROBLEM 08:
The normal boiling point of C6H5Br is 156.15°C. Using Trouton’s rule, find the
vapor pressure at 100°C.
Ans: 155 mmHg

SAMPLE PROBLEM 09:
ANS: 79°C
FREE ENERGY UNDER NON-STANDARD CONDITIONS
∆𝐺 = ∆𝐺° + 𝑅𝑇 𝑙𝑛𝑄
At equilibrium Q = K; ∆G = 0
∆𝐺° = −𝑅𝑇 𝑙𝑛𝐾

• REACTION QUOTIENT, Q, is a number obtained by substituting reactant and

product concentrations or partial pressures at any point during a reaction into
an equilibrium-constant expression.
𝑎𝐴 + 𝑏𝐵 ↔ 𝑐𝐶 + 𝑑𝐷
𝑐 𝑑
𝐶 𝐷
𝑄= 𝑎 𝑏
𝐴 𝐵
Q = K only if the system is in equilibrium.

EQUILIBRIUM is the state wherein the rate at which the reactants disappear to
form products is exactly equal to the rate at which the products interact to
reform the reacting substances.5
CLASSIFICATIONS OF CHEMICAL EQUILIBRIA
1. Homogeneous equilibrium is one established in a system in which only one

phase occurs.
2. Heterogeneous equilibrium is one established in a system in which more
than a single phase appears.
THE THERMODYNAMIC EQUILIBRIUM CONSTANT, Ka
𝑎𝐶𝑐 𝑎𝐷𝑑 … . .
𝐾𝑎 =
𝑎𝐴𝑎 𝑎𝐵𝑏 … . .
∆𝐺 ° = −𝑅𝑇 𝑙𝑛𝐾𝑎
*In writing the expression of the equilibrium constant, the activities of the
products must always be placed in the numerator.
Kp and Kc for Gaseous Reactions
Kp is the equilibrium constant of a reaction expressed in pressure
𝑃𝐶𝑐 𝑃𝐷𝑑 … . .
𝐾𝑝 =
𝑃𝐴𝑎 𝑃𝐵𝑏 … . .
Kc is the concentration equilibrium constant
𝐶𝐶𝑐 𝐶𝐷𝑑 … . .
𝐾𝐶 =
𝐶𝐴𝑎 𝐶𝐵𝑏 … . .
∆𝑛𝑔
𝐾𝑃 = 𝐾𝐶 𝑅𝑇
SAMPLE PROBLEM 10:
ANS: -1299.5 kJ; -1235.1 kJ

SAMPLE PROBLEM 11:
ANS: -5.40 kJ; - 0.30 kJ

SAMPLE PROBLEM 12:
ANS: 6.0 x10-39 atm; 1.6 x10-4 atm

REFERENCES
Brown, T.L., Lemay Jr., H.E., Bursten, B.E., Murphy, C.J., and Woodward, P.M. (2012)
Chemistry: The Central Science, 12th Ed., USA: Pearson Education, Inc.
Brown, L.S. and Holme, T.A. (2011) Chemistry for Engineering Students, 2nd Edition,
USA, Brooks/Cole, Cengage Learning
Chang, R. (2010) Chemistry, 10th Ed., New York, McGraw Hill
5Maron, S.H and Lando, J.B. (1974) Fundamentals of Physical Chemistry. Macmillan
Publishing Co. Inc. New York, USA
Smith, J.M., Van Ness, H.C., Abbot, M.M. (1996) Introduction to Chemical Engineering
Thermodynamics, 5th Ed., McGraw Hill International Editions, Chemical Engineering
Series, Singapore

CHEM20024 Lecture Notes 11 - Free Energy and Equilibrium

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FREE ENERGY AND EQUILIBRIUM

Chemical Thermodynamics (E)

Calculation of Free Energy Changes

For ideal gases,

Gibbs Free Criteria on Spontaneity

1. If ΔG < 0 , the reaction is spontaneous in the forward reaction

In any spontaneous process carried out, at constant temperature and pressure,

Gibbs Free Energy and Temperature

SAMPLE PROBLEM 01:

SAMPLE PROBLEM 02:

SAMPLE PROBLEM 03:

ANS: 1359 cal

SAMPLE PROBLEM 04:

Standard Free Energies of Formation

∆𝐺° = 𝑛∆𝐺𝑓°𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝑛∆𝐺𝑓°𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

SAMPLE PROBLEM 05:

ANS: ∆H° = -166 kJ; ∆S° = 1.38 J/K; ∆G° = -166 kJ

PHYSICAL EQUILIBRIA INVOLVING PURE SUBSTANCES

If ∆H/∆V are constant,

SAMPLE PROBLEM 06:

Where R=1.987 cal/mol-K = 8.314 J/mol-K

SAMPLE PROBLEM 07:

ANS: 552 cal/g

SAMPLE PROBLEM 08:

Ans: 155 mmHg

SAMPLE PROBLEM 09:

FREE ENERGY UNDER NON-STANDARD CONDITIONS

∆𝐺° = −𝑅𝑇 𝑙𝑛𝐾

• REACTION QUOTIENT, Q, is a number obtained by substituting reactant and

Q = K only if the system is in equilibrium.

CLASSIFICATIONS OF CHEMICAL EQUILIBRIA

1. Homogeneous equilibrium is one established in a system in which only one

THE THERMODYNAMIC EQUILIBRIUM CONSTANT, Ka

Kp and Kc for Gaseous Reactions

Kp is the equilibrium constant of a reaction expressed in pressure

Kc is the concentration equilibrium constant

SAMPLE PROBLEM 10:

ANS: -1299.5 kJ; -1235.1 kJ

SAMPLE PROBLEM 11:

ANS: -5.40 kJ; - 0.30 kJ

SAMPLE PROBLEM 12:

ANS: 6.0 x10-39 atm; 1.6 x10-4 atm

Chang, R. (2010) Chemistry, 10th Ed., New York, McGraw Hill

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