Chapter 1

Chemical Equilibrium-Part I

Dr. Farhana Aziz

Faculty of Chemical & Energy Engineering
Universiti Teknologi Malaysia, 81310 UTM
Johor, Johor Bahru, Malaysia
 Topic Outcomes
Week Topic Topic Outcomes
1-3 Chemical equilibrium It is expected that students are
able to:

Introduction to Physical Interpret the spontaneity of a

Chemistry gas mixture.
The Gibbs energy & Helmholtz
energy Calculate the Gibbs energy and
the equilibrium partial pressure
The Gibbs energy of a gas in a of mixing for ideal gases.
mixture

The thermodynamic equilibrium

constant, Kp for a mixture of
ideal gases

The dependence of eq on to T
&P 2
 Scope of Lecture

Introduction to Physical Chemistry

The Gibbs Energy and Helmholtz energy

The Gibbs Energy of a Gas in a Mixture

Thermodynamic of Equilibrium Constant

The Dependence of eq on T and P

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 Intro to Phy. Chem.
Physical chemistry: is the study of macroscopic, atomic,
subatomic, and particulate phenomena in chemical systems
in terms of laws and concepts of physics.
Two different ways to 'look' at things
Macroscopic vs. Microscopic

When you hear the word "rust"

Rust on a surface Rust at the molecular level

Macroscopic viewpoint studies

large-scale properties of matter without Microscopic viewpoint based on
explicit use of the molecule concept. the concept of molecules.
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 Areas of Physical
4 Branches
Chemistry

Quantum
Thermo.
Chemistry

Molecules, e & nuclei - Interrelationships

not obey classical Various equil. propert.
mechanics. in equil. propert.
Their motions
Governed by the laws Kinetics
of quantum mechanics.
Statistical
Mechanics
Rate processes
Uses relevant portions
Molecular macro. Thermodynamics
Quantum chemistry
Statistical

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 Thermodynamics

Describes the behavior of matter & the

transformation between different forms of energy
on macroscopic scale, or the human scale and
larger

DOES NOT refer to structure & behavior at

microscopic level

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 Example: Thermodynamics
1 mol of gaseous water at a sufficiently low density.

MACROSCOPIC SCALE: describes 2 of 3 macroscopic

variables of pressure, volume and temperature.

IF MICROSOPIC LEVEL: dimensions of molecules and water is

dipolar triatomic molecule, H2O, with bond angle of 104.5

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 Thermodynamics
Solid
Liquid
Gas
State
Heating
Cooling
System

Water in bottle Processes

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 Thermodynamics Systems
An important concept in thermodynamics thermodynamic systems

Interacts and exchanges energy with the area around it

transformation of energy

Surrounding Everything outside the system

Universe A region of universe that we

System direct our attention to

Wall separates a system

Boundary from its surroundings

System & surroundings can be described by 1/more system variables

i.e: P, T, conc. 9
 1st Law of
Thermodynamics
Statement of Energy Balance / Conservation:

Energy in = Energy out

Heat in = Heat out

dq c v dT pdV U q w

Heating
Sensible heating Work Done
Change in
Latent heating Expansion
Internal Energy
Evaporational cooling Compression
Radiational heating
Radiational cooling

Says nothing about the direction of energy transfer

Says nothing about the efficiency of energy transfer
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 1st Law of
Thermodynamics
Example 1: Calculate the work involved in expanding
20 L of an ideal gas to a final volume of 80 L against a
constant external pressure of 25 bar.

Example 2: The temperature for a system contain an

ideal gas (Cv=20.8 Jmol-1K-1) was increased from 27oC
to 50oC. How much energy has been increased.

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 1st Law of
Thermodynamics
Work w - pdV

Example 1: Calculate the work involved in expanding

20 L of an ideal gas to a final volume of 80 L against a
constant external pressure of 25 bar.

Internal Energy U c v dT
Example 2: The temperature for a system contain an
ideal gas (Cv=20.8 Jmol-1K-1) was increased from 27oC
to 50oC. How much energy has been increased.
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 2nd Law of
Thermodynamics
The Second Law of Thermodynamics determines whether a given
process can naturally occur
Preferred direction of energy transfer
Fraction of heat that can be converted into work

Often called the Supreme Law of Nature

Application of the second law reveals that there are three types of
thermodynamics processes that can occur without external forcing:

Natural (or Irreversible)

Impossible
Reversible

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 Chemical Equilibrium

How fast we get the product How much we get the product

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 ACTIVITY

In a chemical reaction, chemical equilibrium is the state in which both

reactants and products are present in concentrations which have no further
tendency to change with time. Usually, this state results when the forward
reaction proceeds at the same rate as the reverse reaction. Products is
higher than reactants

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 Definition
Conditions for Equilibrium
The equilibrium state can only be
reached if the chemical reaction takes
place in a closed system. Otherwise,
some of the products may escape,
leading to the absence of a reverse
reaction

Reaction equilibrium:
Is equilibrium with respect to
conversion of 1 set of
chemical species to another
set.
Phase equilibrium:
Is equilibrium with respect to
transport of matter between
phases of the system without
conversion of 1 species to
another.
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 Types of Equilibrium

Equilibria in Mechanics:
Mechanical equilibrium
No unbalanced forces act on the system
System undergoes no acceleration
No turbulence

Material equilibrium stable unstable metastable

No net chemical rxns occur,

No net transfer of matter Equilibria in Thermodynamics:
Conc. of the chemical species const. in time.

H2O (water) H2 + O2
Thermal equilibrium 25C 25C
1 bar 1 bar
No change in the properties of the system or
surroundings when they are separated by a
thermally conducting wall. stable metastable

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 Example: Equilibrium

Phase equilibrium:
Involves the same chemical species present in different phases

E.g.: C6H12O6 (s) C6H12O6 (aq)

Reaction Equilibrium:
Involves different chemical species, which may or may not be
present in the same phase.

E.g.: CaCO3 (s) CaO (s) + CO2 (g)

N2 (g) + 3H2 (g) 2NH3 (g)

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 Entropy & Equilibrium
Consider an isolated system that is not at material equilibrium;

The spontaneous chemical rxn / transport / matter btw phases

in this system are irreversible processes that increase the
entropy (S).

The processes continue until the S is maximized once the

S is maximized, further processes can only decrease S,
thus violate 2nd Law.

Criteria for equilibrium in an isolated system is the maximization

of the systems entropy, S.
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 Closed System
(in material equilibrium)
Ordinarily not isolated
Can exchange heat and work with its surroundings.

By considering the system itself plus the surroundings with

which it interacts to constitute an isolated system

Then, the CONDITION FOR MATERIAL EQUILIBRIUM in the

system is maximization of the total entropy of the system plus
its surroundings:

S syst S surr a maximum at equilibrium

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 Reaction Equilibrium
1. Rxn that involve gases
E.g.: Chemicals put in container of fixed V,
System is allowed to reach equilib. at const. T &
V in a const.-T bath.
2. Rxn in liquid solutions
E.g.: The system is usually held at atm P
Allowed to reach equilib. at constant T & P.

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 Scope of Lecture

Introduction to Physical Chemistry

Chemical Equilibrium

The Gibbs Energy and Helmholtz energy

The Gibbs Energy of a Gas in a Mixture
Thermodynamic of Equilibrium Constant
The Dependence of eq on T and P

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 New State of
Functions
Previously: the direction for an arbitrary process is predicted
by S + Ssurr > 0.

This part: Spontaneity is discussed in context of the approach to

equilibrium of a reactive mixture of gas.

A spontaneous process is the time-evolution of a system in

which it releases free energy (usually as heat) and moves to a
lower, more thermodynamically stable energy state

2 new state functions are introduced that express spontaneity in

terms of the properties of the system only.

Note: surr, surroundings 29

 Reactant Product
Criterion for determining if the reaction mixture will evolve toward
reactants or products:

Systems at const. V & T Systems at const. P & T

Kp derived
Predict equilibrium conc.
Note: P, pressure; V, volume; T, temperature; Kp, equilibrium const. 30
 The Helmholtz Energy
The Helmholtz free energy is a thermodynamic potential that measures
the useful work obtainable from a closed thermodynamic system at a
constant T & V.

Material equilib. in a system held at const. T &V (dV = 0, dT= 0)

dU TdS + dw =: equilibrium

Add & subtract S dT:

dU TdS + SdT SdT + dw

dU d(TS) SdT + dw Since d(TS) = SdT + TdS

d(U TS) SdT + dw

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 The Helmholtz Energy
Since dw = P dV
P-V work only
d(U TS) SdT PdV

At const. T & V, dT=0, dV=0

d(U TS) 0

State function Const. T & V, dT=0, dV=0, closed syst.

In therm. & mech. Equilib.,P-V work only

Helmholtz free energy

A U - TS
Note: Equality sign holds at material equilibrium
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 The Gibbs Energy
Consider for const.T & P, dw = PdV into dU TdS + dw

dU TdS + SdT SdT + PdV + VdP - VdP

dU d(TS) SdT d(PV) + VdP is a thermodynamic potential

d(U + PV TS) SdT + VdP
d(H TS) SdT VdP
d(H TS) SdT - VdP
At const. T and P, dT=0, dP=0
that measures the maximum or
reversible work that may be
performed by a thermodynamic
system at a constant
temperature and pressure
(isothermal, isobaric)

d(H TS) 0

Gibbs free energy,

G H TS U + PV TS 33
 Equilibrium State

G
Const. T, P

G decreases
Suniv increase

Equilibrium reached
Time

dAT,V 0 dGT,P 0
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 Summary

In a closed system capable of doing only P-V work,

Const. T & V material-equilibrium condition is the

minimization of the A,
Const. T & P material-equilibrium condition is the
minimization of the G.

dA = 0 at equilib., const. T, V
dG = 0 at equilib., const. T, P

Note: A, Helmholtz function ; G, Gibbs function 35

 Summary
Second law of thermodynamics:
Entropy must always increase!

Gibbs Free Energy Helmholtz Free Energy

G H T S A U T S
What G means: What A means:
G +ve : not spontaneous A +ve : not spontaneous
G=0 : at equilibrium A=0 : at equilibrium
G ve : spontaneous A ve : spontaneous

Initial & final states of system Initial & final states of system
at the same values of at the same values of
P&T V&T 36
 Work Function: A
Closed system in thermal & mechanical equilibrium

dU TS SdT dw dA SdT dw Const. T

dA dw

A w Finite isothermal process

Equality sign reversible proc.
wby can be greater or less than
U (int. energy of syst.)
wby = U + q (E.g. Carnot
cycle, U = 0 & wby>0)
w by w Work done by the system
on its surroundings
w by A Const. T, closed syst.

A carries a greater significance than being simply a signpost of

spontaneous change:
Change in the Helmholtz energy is equal to the max. expansion work the
system can do:
Expansion work: work arises
wmax A from a V change in the system 38
 Work Function: G

Form

G H TS U PV TS

G U TS PV A PV dG dA PdV VdP

dU TS SdT dw
A = U-TS (Helmholtz energy)
dA SdT dw

dG SdT dw PdV VdP

dG dw PdV const. T & P, closed syst.

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 Work Function: G
If the P-V work is done in a mechanically reversible

dw PdV dwnonP V
dG dw PdV

dG dwnonP V G w non P V w by, non P V

dG dwnonP V wby, non P V G const. T & P, closed syst.

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 Work Function: G (Cont.)
dU dq dw
Non-expansion work example:
dH dq dw dPV electrical work or chemical
transformation
dw dwrev
dq dqrev TdS

dG TdS dw dPV TdS dwrev dPV

dG dH TdS

dG PdV dwnonP V PdV VdP dwnonP V VdP

Reversible change, equality w nonP V, max G (const. T, P)

sign holds & wby,non-P-V= G

The max. non-expansion work from a process at cont. P & T is given by the
value of G 41
 Example 1

You wish to construct a fuel cell based on the oxidation of hydrocarbon fuel.
The 2 choices for a fuel are methane & octane. T constant

a. Calculate the maximum work available through the combustion of these

2 hydrocarbons, on a per mole and a per gram basis at 298.15 K and 1
bar pressure.

b. Calculate the maximum nonexpansion work that can be produced by the

fuel cell oxidation reactions.

The standard enthalpies are Hcombustions(CH4,g) = 891kJ mol1

Hcombustions(C8H8,l) = 5471 kJ mol1 , and S m =361.1 J mol1 K1. Use
tabulated values of S m in App. A for these calculations.

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