CHEE3003 2012 Weeks06-07 Lecture Slides Solutions

1
Key concepts from this section

1. What is a solution
2. Partial and Integral molar properties
3. Chemical potential of ideal gas in solution
4. Chemical potential of condensed phases
(liquids, solids) in solution
5. Thermodynamic activity
6. Complex reactions with solutions, conditions for
spontaneous reactions
Thermodynamics of Solutions
(Lectures Week 6, 2012)
2
Key concept
1. What is a solution
3
The logical development of ideas means that we have concentrated on single
component (or pseudo-single component) phases to bed down many
thermodynamic principles. Unfortunately (or fortunately) real life phases
always consist of more than one component, i.e. they are multi-component
systems.
A solution refers to any type of phase (gas, liquid or solid) that
contains more than one chemical species of variable concentration such that
the species cannot be physically distinguished or separated. Importantly, this
is distinct from a mixture which is less well defined. You can have a mixture
of any two things (e.g. apples and oranges, male and female) but you can only
have a solution of chemical species in a single phase.
Mixtures
Solution of
water and
KMnO
4
is in fact
K
+
+ MnO
4
-
Air: gas
solution
Metal Alloy:
Solid solution
4
Dissolution of Oxygen in water is essential for fish / aquatic life
O
2
(gas, air) O
2
( aqueous)
change from gaseous to aqueous solution
Low solubility of O
2
in water is a problem for systems requiring oxygen
Examples of Solutions
It is important to know effects of various
factors on the dissolution of Oxygen in water
Temperature
Pressure
Composition of water how other elements
effect the solubility of O in water?
Will river water have the same solubility of O
as ocean water?
Water
Air:
21 vol % O
2
O
2
(aq)
dissolved
in water
5
Dissolution of CO
2
in water
CO
2
(gas) CO
2
(aqueous)
Applications:
CO
2
sequestration in deep saline waters (high pressure)- temporary
solution to global warming and use of carbon as a fuel
* Carbonated drinks
Deep Water
It is important to know effect of Temperature
and Pressure on maximum solubility of CO
2
in water
Earths surface
CO
2
P
6
Osmosis diffusion of
solvent (e.g. water)
across semipermiable
membrane from area of
high to area of low
solvent concentration
7
Solubility product
maximum solubility
Salts precipitate out of the Dead Sea
as water vaporises
8
Dissolution of Hydrogen in metals
H
2
(gas) 2 H (solution in metal)
Gas species H
2
break down and dissolve in the metal phase as atoms
Applications:
Hydrogen storage some alloys can dissolve significant concentrations of H
Defects during casting of some alloys for example, in humid, wet
environment H is absorbed in molten aluminium. Then, on solidification, H
is rejected by solids producing gas bubbles in castings, forming defects and
affecting mechanical properties in the final product
Alloy H (solution)
It is important to know effects of
Temperature, Pressure and alloy composition
on solubility of Hydrogen
H
2
(gas)
9
1) Gas: Air solution of O
2
, N
2
, ...
2) Liquid: Gas in liquid:
Oxygen in water
Carbonated water
Liquid in Liquid
Alcoholic drinks
Petroleum solutions of hydrocarbons
Solid in Liquid
Sugar in water
Salt in water, Ocean water
3) Solid: Gas in Solid
Hydrogen in metal (H
2
storage)
Liquid in Solid
Mercury in gold (amalgam)
Hexane in paraffin wax
Solid in Solid
Hydrocarbon based Polymers with plasticizers
Metal alloys, Steel Fe-C, bronze Cu-Sn
SUMMARY: Examples of different states (gas, liquid, solid)
in pure and in solution
10
DEMO 1 formation of a solution
The question in focus how to predict
chemical behaviour of species in solution?
DEMO 2 partitioning of solute A between two immiscible liquids B and C
CuSO
4
solution
in H
2
O
0%A
solution
in C
50%A
solution
in B
?%A
solution
in C
?%A
solution
in B
Mineral Turps (~C
10
H
16
)+
Extractant (ACORGA M5774-
Salicylaldoxime: C
7
H
7
NO
2
)
CuSO
4
(30g/L) Aqueos Solution
CuSO
4
CuSO
4
11
In the following slides several examples are given
where knowledge on the behaviour of solutes and
solvents in solutions is important to predict the
outcomes of the processes.
chemical behaviour of species in solution?
12
50%A
solution
in B
50%A
solution
in C
A? A?
30%A
solution
in B
50%A
solution
in B
B A
Example of different chemical behaviour of species in solutions
S
e
p
a
r
a
t
i
o
n
i
s

r
e
m
o
v
e
d
S
e
p
a
r
a
t
i
o
n
i
s

r
e
m
o
v
e
d
Case 1) The same solvent and solute,
two separated solutions initially with
different concentrations of A. .
In this case the answer is clear - after
separation is removed A will diffuse
from right to left, and B will diffuse
from left to right compartments before
the same concentration of A in both
compartments is reached
Question what is the direction of diffusion after separation
between two separate compartments is removed?
Case 2) Two different solvents B and
C are immiscible liquids with the
same concentration of A initially
separated.
This case is not obvious the same
solute A but different solvents, so -
different chemical environments
additional information on chemical
behaviour of A in solvents B and C is
needed to answer the question.
1)
2)
13
Example - phenol in water.
Phenol is present in different processes such
as production of paints, polymers, oil
refineries and coal.
It is soluble in water up to 8 g/l but is toxic to
marine life in ppm concentrations.
One option for cleaning water from phenol
before it is discharged from a process into
environment is to contact the stream with
Methyl Isobutyl Ketone (MIBK) since phenol
is far more soluble in MIBK leaving very
little phenol in water.
Liquid liquid separation is used to clean water
before discharge into environment?
ARD Extractor used for
removal of phenol from
water
14
30%A
solution
in B
50%A
solution
in B
A
50%A
solution
in B
50%A
solution
in C
A?
3)
4)
gas
gas
Question what is the direction of mass transfer of volatile
solute A after two solutions are placed in closed compartment?
Case 3) The same solvent B and solute A, two
separated solutions initially with different
concentrations of solute A.
In this case the answer is clear - A will move
from right to left solution before the same
concentration of A is reached in both volumes
(similar to Case 1 above).
Case 4) Two different solvents B and C with
the same concentration of solute A.
In this case the answer again is not obvious
additional information on chemical
behaviour of solute A in solvents B and C is
needed to answer the question
(similar to Case 2 above).
?
Closed container
Closed container
15
5)
6)
30%A
solution
in B
50%A
solution
in B
Solid
D
A + D ? A + D ?
Solid
D
50%A
solution
in B
50%A
solution
in C
A + D ? A + D ?
Solid
D
Solid
D
Question if reaction A+D can proceed only at certain concentration
of A will A in solution react with D?
Case 5) The same solvent B and
solute A, two solutions with
different concentrations of A.
In this case the answer is clear
that the reaction A+D will proceed
ahead for higher concentration of
A
Case 6) Two different solvents B
and C with the same
concentration of solute A.
In this case the answer is not
obvious additional information
on the chemical behaviour of
solute A in solvents B and C is
needed.
16
DEMO Ethanol and water change volume in solution
Properties of chemical species in solution are different from
pure properties
At a given T and P a property of a chemical species in
solution depends on
- solvent
- concentration
E
t
h
a
n
o
l
W
a
t
e
r
W
+
E
t
h
s
o
l
u
t
i
o
n
17
Consider the Following...
A local barman attempts to make 70 ml of his Rocket
Fuel Special by adding 50 ml of pure ethanol to 20 ml
of pure water:
a) What would happen?
b) What would the final volume of the drink be?
c) What is the ethanol fraction in the vapour of the
drink?
18
Answer
a) The two liquids mix spontaneously to form a liquid solution.
b) The final volume of the drink is 67 ml!
c) The mole fraction of ethanol in the liquid is 0.43 but the mole
fraction in the vapour is less than this!
??

67 ml Solution of
ethanol and water
20 ml Pure water 50 ml Pure ethanol
19
Lessons
1. Dont argue with the barman (let alone the bouncer), they do
not understand thermodynamics.
2. The volume difference depends on the ratio of ethanol to
water.
3. It does not matter if we added ethanol to water or vice-versa,
the result would be the same. It is a state property.
4. If you have a very sensitive nose, you may be able to measure
the vapour pressure / fugacity of the ethanol in your drink.
5. Do not drink anything that has 71 v/v% alcohol and stop
asking the barman for their recommendation.
20
A Gap to Fill...
1. How do we describe chemical phenomena in
solutions?
2. How do we predict whether a reaction will occur
spontaneously when some/all of the reactants and
products are in solution and no longer in pure state
(remember we have only considered pure
substances at 1 bar) so far in this course?
This example provokes two important
questions:
21
Key concept
2. Partial and Integral
molar properties
22
INTRODUCING TERMINOLOGY:
State Property Y can be:
- Intensive or - Extensive
- Ideal Y* or - Real Y
- Molar Partial - property of a component i in the solution
- Molar Integral Y - property of the solution
- Molar mixing property change of a property due to the mixing of
pure component into solution, including
- Integral molar mixing
- Partial molar mixing
i
Y
23
Solution Properties
1) For a pure component, the extensive state property of the
system is a function of three variables (using V as an example):
( (( ( ) )) )
, , V V T P N = == =
2) The intensive, molar properties of a pure component are
defined by any two other intensive variables:
( (( ( ) )) )
, etc. V V T P = == =
3) For a solution, containing m different chemical components,
extensive properties then become a function of the number of
moles of each species as well as two other variables (i.e. we need
m + 2 independent variables to define the system):
( (( ( ) )) ) ( (( ( ) )) )
1 2 3
, , , , , ....., , ......, , ,
where is the set of amounts for all species
i m
V V T P N N N N N V T P N
N m

= = = = = = = =

24
Partial Molar Property
The final term in the equation above is the sum of partial molar volumes.
A partial molar property (using volume as a general example) is defined as:
j j m
m
P N T N m
T P N T P N
P N T N
V V V V
dV dT dP dN dN
T P N N
V V V
dV dT dP
T P
1
1
, , 1
, , , ,
, ,
can then be written a The total differential of a property in soluti s:
.
on
....

= + + + + = + + + + = + + + + = + + + +

= + + = + + = + + = + +

j i
m
i
i
i
T P N
dN
N
i
1
, ,
The condition here is that the amounts of all other components except are kept constant

= == =

j i
m
i i
i
P N
P N
N
i
T
i
T
V V
dV dT dP VdN
T P
V
V
N
, ,
1
,
3
,
(m /mol), the overbar denotes a partial molar property

= == =

= + + = + + = + + = + +

= == =

Partial Molar Property definition:
- increment in that property when 1 mole of a component is added to a large
amount of a solution so that the bulk composition of the solution stays constant.
25
Partial Molar Properties
Take careful note of the properties of a partial molar volume:
j i
i
i
T P N
V
V
N

= == =

, ,
Always write N
i
never x
i
Always at
constant T and P
Amounts of all
other species
kept constant
Partial Property of
component i in
solution
Differential of
system property
You can have a partial molar quantity of any extensive variable:
, , , , , ,
etc
j i j i j i
i i i
i i i
T P N T P N T P N
H S G
H S G
N N N

= = = = = = = = = = = =

26
Partial Molar and Integral Molar Properties
The total number of moles in the system, N, is defined as:
( (( ( ) )) )
j i
m
i
i
i
i
T P N
N
V
V
N
N
NV
V
N
1
, ,
- Integra
Any extensive property can be converted to an intensive molar property:
e.g.
Knowing this, we can also write a partial molar property a
l Molar Pr
s
per y
:
o t

= == =
= == =

= == =

= == =

j i
i
i i
i
T P N
i
N V
V x i
x N
N N
, ,
Note that , where is the mole fraction of
since changes when changes.

= = = =

27
Integral Molar Property
Since the partial molar volume is the volume occupied by each mole of each
species, the total volume is given by:
m
i
m
i i
i
m
i
i
i
m
i i
i
i
i
V NV
N V
V V
N N
V x V x
1
1
1 1
The average molar volume of the solution can be calculated as:
- Integral m
Integral molar property = Patial m
olar
olar
volu
prop
me

Again this ca
e ty
be
r
n
= == =
= == =
= == =
= == =
= == =
= = = = = = = =
= == =

m m m
i i i i i i
i i i
H x H S x S G x G
1 1 1
extended to any variable:
etc
= = = = = = = = = = = =
= = = = = = = = = = = =

The average molar property of a solution is also called an integral molar
property of the solution.
28
Example: Partial Molar Volume
An example of determining the partial volume shows the addition of a small
amount of water into a water-ethanol solution:
- the change in volume of the solution is divided by the small amount
of water added to give the partial volume of water at the specified T, P and
amounts of water and ethanol in solution (ref. Koretsky
1
).
29
Example: Partial and Integral Molar Volume
The experimental
results show that the
partial molar volume
can be a complex
function of the
composition of the
solution (ref
Atkins
2
).
Depending on the
mole fraction of
water and ethanol,
the molecules pack
differently and
occupy different
volumes.
30
10
15
20
25
30
35
40
45
50
55
60
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Volume Fraction of Ethanol (C2H5OH) [cm3pure/cm3pure]
M
o
l
a
r

V
o
l
u
m
e

[
c
m
3

m
o
l
-
1
]
-0.035
-0.03
-0.025
-0.02
-0.015
-0.01
-0.005
0
V

m
i
x

[
c
m
3
/
c
m
3

o
f

p
u
r
e
]
Water Part.Vol . Ethanol Part.Vol .
Int.mol .Vol . Rel ati ve Vol .Change due to mi xi ng
Example: Partial and Integral Molar Volume

mix
V
Refer to DEMO
60vol% Eth
+ 40vol% W
ethanol
V
water
V
solution
V
solution mix
V
31
Question: Why partial pure property? What changed?
The Partial Property of a species (e.g. water) in the solution (e.g.
with ethanol) is different due to the interatomic / intermolecular
interactions with surrounding atoms / molecules (e.g. of ethanol).
A similar statement is true to for the ethanol.
Pure Water H
2
O
H
2
O H
2
O H
2
O H
2
O H
2
O
H
2
O
H
2
O
Solution of Water H
2
O
and Ethanol Eth
Eth
Eth
Eth
Eth
Eth
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
Eth Eth
Eth
H
2
O H
2
O
Eth Eth
Eth
Eth
H
2
O
H
2
O H
2
O H
2
O H
2
O
H
2
O H
2
O H
2
O H
2
O
H
2
O H
2
O H
2
O H
2
O
H
2
O H
2
O H
2
O H
2
O H
2
O
H
2
O
32
INTRODUCING TERMINOLOGY:
State Property Y can be:
- Intensive or - Extensive
- Ideal Y* or - Real Y
- Molar Partial - property of a component i in the solution
- Molar Integral - property of the solution
- Molar mixing property change of a property due to the mixing of
pure component into solution, including
- Integral molar mixing
- Partial molar mixing
i
Y
m
i
i
i
Y x Y
1 = == =
= == =

33
Key concept
3. Chemical potential
of ideal gas in solution
34
chemical behaviour of species in solution
For example - refer to DEMO
partitioning of solute A between two immiscible liquids B and C
- the question is how much A will be in the final equilibrium state?
Pure C
(0%A )
50%A
solution
in B
?%A
solution
in C
?%A
solution
in B
Initial State Final State
35
Recall from Section 5
Three Criteria of Equilibrium
j i
i i
i
T P N
G
G J mol chemical potential
N
partial molar Gibbs Free Energy

= = = = = = = =

, ,
[ / ]
-
Chemical Potential
Thermal Equilibrium
Mechanical Equilibrium
Chemical Equilibrium
i i
T T
P P
G G

= == =
= == =
= == =
36
RECALL: MASTER EQUATION
dG = VdP SdT
describes the direction of change in a system as a function of two important
practical variables: temperature, T, and pressure, P.
INSERT
for additional study
PRELIMINARIES: EFFECT OF TEMPERATURE
dG = VdP-SdT
1) At P = const: dG = -SdT
and (dG/dT)
P
= -S or (d G/dT)
P
= - S
2) G = H-T S so G/T = H/T- S so d( G/T) / d(1/T) = H
2
1
2 2
2
1
1 1
T
P
1 2
P
*
P P
P * 2
P
P P
1
dG VdP SdT; at T=const: dG=VdP and (dG/dP) V
for a change from P to P G VdP
for 1 mol of ideal gas (V =RT/P)
P RT
G V dP ( )dP =RT[ln P ] RT ln( )
P P

= = = = = = = =
= == =
= = = = = = = = = = = =

PRELIMINARIES: EFFECT OF PRESSURE:
37
Chemical Potential of Pure Ideal Gas
j i
i
i
T ,P ,N
Actual State
i
Standard State
Actual State
i
Standard S
i
tate
0
G
Partial Molar Gibbs free energy
dG
Difference d
Standard partial Gibb

G
(chemical potential) G
G

s
N

+ ++ +

= = = = = = = =

0
i
free energy G
To derive Partial Molar Gibbs Free Energy (Chemical Potential) of ideal
gas at pressure P:
1. Reference Standard State is introduced, and
2. Difference between the values at Standard State and actual state at
pressure P is calculated
3. The Partial Molar Gibbs Free Energy (Chemical Potential) equals to
(Standard) + (Difference) :
38
at pressure P
0
i i i
0 0
i
Chemical potential (Partial Molar Gibbs
1. Pure gas at P 1atm is frequently selected a
Free Energy) of pure ideal gas is

s Standard State for gas: G ,
t
G G RT ln
hen
P ,

P in

= = + = = + = = + = = +
= == =
0 0
0
P P
0
i i i i
0
P P
0
2. Integration from Standard State (pure P )
to actual state at p
atm, and P
ressure P for an ideal gas
RT P
gives dG = dP , so that G G RT l
P
t
P
1a m
n = = + = = + = = + = = +
= == =

39
at pressure P
0
P
0
0
i i
i
i
P
0
i
For Pure Standard State
Standard partial Gibbs free energy
(P =1atm) dG RT ln P
( P in atm

(chemical potential) G G RT ln P
)

G

= = = =
= + = + = + = +

= == =

Partial Molar Gibbs Free Energy (Chemical Potential) of ideal gas
at pressure P equal to (Value at Standard State) + (Difference) :
40
Chemical Potential of Real Gas and fugacity
i
0 i i
i i i
0
P 0
i i
0
i
Fugacity f (T, P, x') is introduced to retain simplicity of expressions
f ( T, P, x') f
(T,P,x')= G ( T, P, x') G RT ln with lim 1
P f
f is the value of fugacity of gas in The Standard State
is

= + = = + = = + = = + =

( (( ( ) )) )
0
i
0
i i i i i
commonly selected to be pure ideal gas at 1 atm and f 1
then (T,P)= G ( T, P ) G RT ln f for f in atm
is a measure of a chemical potential
in the form of ' adjusted
F
pressure
ugacity
.'

= == =
= + = + = + = +
41
Chemical Potential of Real Gas and fugacity
( (( ( ) )) )
0
i i i i
For moderate pressures f/P 1 ,
and (T,P)= G ( T, P ) G RT ln P

= + = + = + = +
42
Total pressure and partial pressures P
i
of
Several Gases in Solution behaving ideally
- Daltons law
N
A
mols of ideal gas A - in a container with volume V
will produce pressure P
A
=N
A
RT/V
If we add N
B
mols of ideal gas B into the same container with
volume V it will produce additional pressure P
B
=N
B
RT/V
What is the total pressure?
Daltons Law: The total pressure exerted by a solution of
gases behaving ideally is the sum of the pressures exerted by
the individual gases occupying the same volume
P
total
=P
A
+P
B
=(N
A
+N
B
)RT/V ; P
A
=x
A
P
total
and P
B
=x
B
P
total
43
Total pressure and partial pressures P
i
of
Several Gases in Solution behaving ideally
P
total
0
P
A
=
xA
*
P
t
o
t
a
l
1.0
Mol Fraction, x
A
P
r
e
s
s
u
r
e
P
B =
x
B *
P
t
o
t
a
l
Daltons Law: P
total
= P
A
+P
B
= (N
A
+N
B
)RT/V
44
Chemical Potential of Ideal Gas
with partial pressure P
i
in solution
For the Pure Standard State:
at partial pressure P
i
in solution equals to
(Molar Gibbs free energy in Standard State pure gas at 1 atm)
+ (Difference between pure gas at 1 atmand at partial pressure P
i
) :
0
P
0
0
i i
i
i
P
0
i i
i
For Pure Standard State (
P =1atm) dG RT ln P

(

(chemical poten
Standard
tial) G G R
partial
P in
Gibbs
T ln
fr
P
ee energy G
atm)

= = = =
= = = = = = = =

+ ++ +

45
Pure gas i
at 1 atm
Chemical Potential of Ideal Gas
with partial pressure P
i
in solution
0
i
G
For the Pure Standard State:
at partial pressure P
i
in solution equals to
(Molar Gibbs free energy in Standard State pure gas at 1 atm)
+ (Difference between pure gas at 1 atmand at partial pressure P
i
) :
Gas i in the solution
0
P
i i
P
dG RT ln P = == =

0
i i
i
G G RT ln P = + = + = + = +
46
Solution made of N
A
mols of A and N
B
mols of B
with total pressure P = P
A
+P
B
Calculating Integral Molar
Gibbs Free Energy of Ideal Gas Solution
A
B
Let's calculate the change of Gibbs Free Energy of the system
due to the formation of an ideal gas solution
from N mols of pure A at pressure P and
N mols of pure B at pressure P
(initially not in solution) at a given T
N
A
mols of pure A at P
where P
i
=x
i
*P
total
is Partial Pressure of component i
x
i
mol fraction of component i
x
i
= N
i
/ N
total
= N
i
/ (N
A
+N
B
)
P
i
= x
i
*P
total
, i=A or B
N
B
mols of pure B at P
INSERT INSERT
47
0
i i
0 0
A B A B
Total A B A B
0
A
Total to
A
tal A B
B
1) Initial State: N mols of pure A at P and N mols of pure B at P
(not in solution) at a given T G G RT ln P
G N * G + N * G N ( G RT ln P ) +N ( G RT ln P )
G G / N x ( G

RT ln P )

x
= + = + = + = +
= = + + = = + + = = + + = = + +
= = + + = = + + = = + + = = + +
0
B
0 0 0 0
A B A B
A B A B A B
A B
( G RT ln P )
x G x G ( x x )RT ln P x G x G RT ln P
(note x x 1)
+ = + = + = + =
= + + + = + + = + + + = + + = + + + = + + = + + + = + +
+ = + = + = + =
N
A
mols of pure A at P N
B
mols of pure B at P
INSERT INSERT
48
( (( ( ) )) ) ( (( ( ) )) )
0 0
A B A B
A B A A B B
0 0
A B
total A A B B Total
0 0
A B
A A B B
A B
G N G N G N G RT ln P N G RT ln P ,
G G / N ( N ( G RT ln P ) N ( G RT ln P
2 ) Final State: Solution of N and N mols of A and B at
) )/N
x ( G RT l
P
n P ) x ( G RT ln P ) (substi
and
t

ute P
T
= + = + + + = + = + + + = + = + + + = + = + + +
= = + + + = = = + + + = = = + + + = = = + + + =
= + + + = = + + + = = + + + = = + + + =
i i
0 0
A B
A A A B B B
0 0
A B
A B A A A B B B
0 0
A B
A B A A B B
A B
x P )
x G x RT ln( x P ) x G x RT ln( x P )
x G x G x RT ln x x RT ln P x RT ln x x RT ln P
x G x G x RT ln x x RT ln x RT ln P
(note that x x =1)
= == =
= + + + = = + + + = = + + + = = + + + =
= + + + + + = = + + + + + = = + + + + + = = + + + + + =
= + + + + = + + + + = + + + + = + + + +
+ ++ +
Solution made of N
A
mols of A and N
B
mols of B
A
+P
B
INSERT INSERT
49
0
A
0
A B
B
A B
A
B
G x G x G
1) In
R
itial State: N mols of pure A at P and N mols o
T ln P
f pure B at P
(not in solution) at a given T
2) Final State: Solution of N and N mols of A

= + + = + + = + + = + +
0 0
A B
A B A A B B
A A B B
G x G x G RT ln P x RT ln x x RT ln x
Note that the term x RT ln x x RT ln x - difference between
G for separate pure gas and G for solutio
and B a
n - is a
t P and
lways neg ve
T
ati
= + + + + = + + + + = + + + + = + + + +
+ ++ +
Solution made of N
A
mols of A and N
B
mols of B
A
+P
B
N
A
mols of pure A at P N
B
mols of pure B at P
INSERT INSERT
50
A B
total A A B B
0 0
A A B B
A B
M
i
1) for solution of N mols of A and N mols of B at temperature T
for P 1atm, P = x , P = x
Partial Gibbs Free Energies G G RT ln x and G G RT ln x
for ideal gas: G
= == =
= + = + = + = + = + = + = + = +
= == =
i
total
m
0 0
i A B
i A A B B solution
i 1
RT ln x
___________________________________________________________
2) It can be shown (see Insert above) that Integral Gibbs Free Energy (P =1 atm)
G x G x ( G RT ln x ) x ( G RT ln x ) =
= == =
= = + + + = = + + + = = + + + = = + + +

0 0
A B
A B A A B B
x G x G x RT ln x x RT ln x
___________________________________________________________
3) Gibbs free energy change due to formation of solution from pure ideal ga
= + + + = + + + = + + + = + + +
0 0
A B
Mixing A B A A B B solution
ses
(Integral molar Gibbs Free Energy of Mixing):
G G ( x G x G ) = x RT ln x x RT ln x 0 = + + = + + = + + = + +
Integral Molar Gibbs Free Energy of Ideal Gas Solution
51
Pure A Pure B
0 mol fraction of B x
B
6 66 6 1
between x
B
=0 and x
B
=1 (A and B solution)
T=const
0
A
G
0 0
A B
A B A A B B Solution
Total
G ( x G x G ) x RT ln x x RT ln x
at P =1atm
= + + + = + + + = + + + = + + +
total
0 0
A B
A B
Two separate pure gases at P = 1atm
x G x G + ++ +
0
B
G
Mix
A A B B
G
x RT ln x x RT ln x
= == =
+ ++ +
Integral Molar Gibbs Free Energy
of Ideal Gas Solution
52
Ideal Gas Solution
0 0
A B
Mixing A B solution
A A B B
G G ( x G x G )
x RT ln x x RT ln x
= + = + = + = +
= + = + = + = +
Pure A Pure B

M
i
x
i
n
g
G
T=const
Mix
Negative values of G indicate that
1. the solution of ideal gases is more stable
than separate pure A and pure B, and
2. the formation of solution of ideal gases

is spontaneous
0 mol fraction of B x
B
6 66 6 1
between x
B
=0 and x
B
=1 (A and B solution)
mix
A B
G - change due to formation of solution of ideal gases
N and N mols of A and B at total P = 1 atm and T

06 66 6
53
DEMO formation of solution
Ideal Gas Solution
O
2
+N
2 CO
2
+H
2
O+N
2
O
2
+N
2
Spontaneous
diffusion of O
2
54
Key concept
4. Chemical potential
of condensed phases (liquids, solids)
in solution
55
Equilibrium Partial Pressure over condensed phase
H
2
O
Pure water Liquid
Water- Ethanol
Solution
Gas Equilibrium
partial pressure
P
H2O
< P
0
H2O
P
H2O
depends on x
H2O
:
higher x
H2O
- higher P
H2O
Eth Eth
Eth
Eth
Eth
Gas
P
H2O
= P
0
H2O
P
0
H2O
= saturation
vapor pressure
- standard state
H
2
O H
2
O H
2
O H
2
O
H
2
O H
2
O H
2
O H
2
O
H
2
O H
2
O H
2
O H
2
O H
2
O
H
2
O H
2
O H
2
O H
2
O H
2
O
H
2
O
H
2
O H
2
O
H
2
O
H
2
O H
2
O
H
2
O
Questions:
What is the steam
(H
2
O) partial
pressure above the
water- ethanol
solution compared to
the H
2
O partial
pressure above pure
water?
Is it proportional to
the H
2
O
concentration?
56
Equilibrium Partial Pressure over condensed phase
A A
A
A
A
A
A
A
A
A
Pure Liquid A
A
A
A
A
Liquid Solution
A in B
Gas
Partial pressure
above solution:
P
A
< P
0
A
P
A
~ x
A
mol fraction
B B
B
B
B A
A A A A A
Gas
P
A
= P
0
A
P
0
A
= saturation
vapor pressure
- Standard state
Note
for low
pressures
f P
P will further
be used
in place of
fugacity f

Saturation P
0
i
is a measure of chemical interactions if i in a solution
57
Relationship between partial pressure P
A
and
solution concentration in an ideal solution
EXAMPLE at T = const
Mol fraction A
P
A
,

(
a
t
m
)
0
1.0
0
I
d
e
a
l

S
o
l
u
t
i
o
n
(
R
a
o
u
l
t
s
l
a
w
)
If A-A interactions . .. . A-B (the same),
then Partial pressure P
A
is proportional to the concentration
of A in the solution
such behaviour is called Ideal or Raoultian
A A
A
A
A
A
A
A
A
B B
B
P
0
A
P
0
A
- saturation vapour pressure
58
A
and
solution concentration in a non-ideal system
Mol fraction A
P
A
,

(
a
t
m
)
0
1.0 0
I
d
e
a
l

S
o
l
u
t
i
o
n
P
o
s
i
t
i
v
e

d
e
v
i
a
t
i
o
n

-
R
e
a
l

S
o
l
u
t
i
o
n
A A
A
A
A
A
A
A
A
B B
B
P
0
A
P
0
A
If A-B interactions are weaker than A-A,
A
is higher
than over an ideal solution
Saturation P
0
i
59
A
and
Mol fraction A
P
A
,

(
a
t
m
)
0
1.0
0
I
d
e
a
l

S
o
l
u
t
i
o
n
N
e
g
a
t
i
v
e

d
e
v
i
a
t
i
o
n

-
R
e
a
l

S
o
l
u
t
i
o
n
A A
A
A
A
A
A
A
A
B B
B
P
0
A
P
0
A
If A-B interactions are stronger than A-A,
A
is lower
than over an ideal solution
Saturation P
0
i
60
Chemical potential of components in condensed
(liquid or solid) solution phases
0

is frequently used:
component "i" (stable as gas at 298.15K and 1 atm)
Pure Standard
G
State - ideal gas at
aseo
P 1at
s
m
u
Recall: Pure Standard State
= == =
0
i i i i i

(stable as liquid at 298.15K and 1 atm)

L
- Chemical potential of pure ideal gas "i" is

component "i"
Pure Sta
iquid
nd
G G RT lnP [ P in atm] = = + = = + = = + = = +
0
i
0
i
(stable as solid at 298.15K and 1 atm)
ard State - pure liquid G
component "i"

Soli
Pure Standard State - pure solid G
d

Chemical potential of condensed component "i"

"i" in solution
i i , pure solution
Pure "i"
0 0
i i i i
dG G G G G

= == = = = + + = = + + = = + + = = + +

Sol
i
Std
i
0
i
ch
G
ange
d
G
G

61
A,Solution
Liquid Solution
A in B: G
A,Pure
A,Pure
Pure Liquid A
G G = == =
i , pure solution
0
i i i
G
Calculating Chemical potential of condensed component "i"
in solution G G

= = + = = + = = + = = +
A, pure A in solution
G

- the Gibbs Free Energy change
between pure species A and A in sol n
G
utio

62
G
2
Equilibrium
Saturated
Gas,
P
A,pureA
=P
0
A
G
3
G
1
A,Solution
Liquid Solution
A in B: G
A,Pure
A,Pure
Pure Liquid A
G G = == =
0
1
2
3
A, pure A,solution A,solution A, pure
1 2 3
Since G is a State Property (not dependent on the path)
to calculate G of change (pure A) (A in solution)
we may follow the path 0 1 2 3, so th
G G
a
G G
t
G G

= = + = = + = = + = = +

+ ++ +

Equilibrium
Saturated
Gas,
P
A,sol
and P
B,sol
A,Solution, gas
G A,Solution, gas
G
i , pure solution
0
i i i
G
in solution G G

= = + = = + = = + = = +
G

63
G
2
Gas, P
A,pureA
G
3
=0
Gas, P
A,sol
, P
B,sol
G
1
=0
A,Solution
Liquid Solution
A in B: G
A,Pure
A,Pure
Pure Liquid A
G G = == =
A,liquid A, gas A,liquid A, gas
1 3
2
For any liquid A in equilibrium with species A in the gas phase
G G G 0, then G 0 and G 0,
then G G G G

= = = = = = = = = = = = = = = =
= = = = = = = =
0
1
2
3
A,Solution, gas
G
A,Solution, gas
G
i , pure solution
0
i i i
G
in solution G G

= = + = = + = = + = = +
G

64
Solution Solution
A A 2
Pure Pure
A above solution A above pure
i i
A abo
from dG=VdP-SdT :
G VdP ( RT / P )dP
RT ln( f / f )
for low pressures when gas behaves ideally and f P
RT ln( P
= = = = = = = = = = = =
= == =
= == =
= == =

ve solution A above pure
1 2 3
A, pure A,solution
A,s
/ P )
Gibbs free energy change
between A in pure and A in solution
G G G G G G
G RT ln( P

= = + + = = = + + = = = + + = = = + + =
= == =
olution A, pure
/ P )
i , pure solution
0
i i i
G
in solution G G

= = + = = + = = + = = +
65
A,solution A, pure
A,solution A, pure
A,solution A, pure
Rearranging: G G G
RT ln( P / P )
G G RT ln( P / P )
if pure is selected as Standard Stat

= = = =
= == =
= + = + = + = +
0
0
A A, pure
A A, pure A A
0
0
A,solution A
A,solution A
0
0
A,solution A
A,solution A
Chemical Potential
e,
then G G and P P (if A ideal and f P )
G G RT ln( P / P )
in general form G G RT ln( f / f )

= = = = = = = = = = = =
= + = + = + = +
= + = + = + = +
i , pure solution
0
i i i
G
in solution G G

= = + = = + = = + = = +
66
Gas, P
A,pureA
G
3
=0
Gas, P
A,sol
, P
B,sol
G
1
=0
0
A
A,Solution A
0
A
Liquid Solution A in B
P
G G RT ln( )
P
= + = + = + = +
0
A,Pure A
A,Pure
Pure Liquid A
G G G = = = = = = = =
i , pure solution
0
i i i
G
SUMMARY: Calculating Chemical potential of condensed component "i"
in solution G G

= = + = = + = = + = = +
0
0
A A, pure
A A, pure
0
0
A,solution A
A,solution A
0
A,solution A
Chemical Potential
- G of 1 mol of A in solution = Partial Molar Free Energy
-
Pure Standard State, G G and P P
G G RT ln( P / P ) -
RT ln( P / P )
= = = = = = = =
= + = + = + = +
correction term
A
A, pure A,solution
0
A
P
G RT ln( )
P

= == =
Solution
2
Pure
Sol .
A
A
0
Pure
A A
G VdP
P RT
( )dP RT ln( )
P P
= = = = = = = =
= == =

A,Solution, gas
G
A,Solution, gas
G
67
Key concept
5. Thermodynamic activity
68
i
i
0
i i
i i
i
i
i i
Definition :
This leads to a simplified equation for partial Gibbs Free Energy:
G G RT lna
For the special case when the gas is
f
a Activity of component
ideal, f P and f P on
"i
e can
"
f
= == =
= + = + = + = +
= = = = = = = =

i i
i i i
i i
i
use:
P
G G RT ln
P
Fugacity f (T,P,x') is a function of concentration of component in soluti
a
o
P
P
n

= + = + = + = +

= == =

Activity of a component in solution
69
ACTIVITY AS A FUNCTION OF
CONCENTRATION
The activity of a species (or effective
concentration) is commonly expressed as as
function of concentration:
a
A
=
A
x
A
where
A
is the activity coefficient of A in a solution
of a given composition, and
x
A
is the molar fraction of A in the solution.
70
Pure Standard State is often used: .
For gaseous components - Pure Standard State is 1 atm pure gas,
i.e. a
A
= P
A
/1atm,
where P
A
= the partial pressure of the gas species A in atm.
.
For a component in condensed phases (in solid or liquid solution),
the pure element or compound is taken as the Pure Standard State,
and a
A
=
A
x
A
relative to the pure component
Note activity a is dimensionless value as it is always relative to the
standard state
0 0
A A A A
A
A
0
A
A
Also, , for the special case when A gas above pure A and solution
behave as ideal (P
P
a
=f and P =f )
where P - equilibrium p a
P
arti
= == =
0
A
l pressure of A above solution
and P - equilibrium partial pressure of A above pure A
in the corresponding state (liquid or solid)
71
0
A,sol
A,solution A
0
A
0
A,solution A, pure
A A
A
A
For pure component standard state
P
G G RT ln( )
P
G G RT lna
this is a general equation valid for solids, liquids and gases
G - refers to only part of solution

= + = + = + = +
= + = + = + = +

Partial Molar Gibbs Free Energy
Chemical Potential

72
0 0 0
1 2
T T T
P
T T T 0 0
1 2 2 1 T
T 298.15
P P 298.15
298.15 298.15 298.15
T T 0 0
1 P P
T 298.15
298.15 298.15
at temperature T G H TS ; for C A BT CT
B
H H C dT; C dT ( A BT CT )dT [ AT T CT ]
2
C C
S S dT; dT ( AT B CT
T T

= = + + = = + + = = + + = = + +
= + = + + = + = + = + + = + = + = + + = + = + = + + = +
= + = + + = + = + + = + = + + = + = + +

T
3 2 T
298.15
298.15
0
A,solution A, pure
A A
C
)dT [ Aln( T ) BT T ]
2
For pure component standard state
G G RT lna

= + = + = + = +
= + = + = + = +

Chemical
Potential
as a function
of
temperature
INSERT INSERT
73
A
and
Mol fraction A
P
A
,

(
a
t
m
)
0
1.0
0
I
d
e
a
l

S
o
l
u
t
i
o
n
P
o
s
i
t
i
v
e

d
e
v
i
a
t
i
o
n

-
R
e
a
l

S
o
l
u
t
i
o
n
A A
A
A
A
A
A
A
A
B B
B
A
0
A
A A
Dividing P - equilibrium Partial Pressure of A above solution -
by P - equilibrium Partial Pressure of A above pure A (solid or liquid respectively)
we can obtain "normalised" Partial Pressure P /P
0
given in the next slide
P
0
A
P
0
A
74
Normalised partial pressure = activity
as a function of concentration a
A
=
A
x
A
A
= 1 - ideal behaviour
A
> 1 - positive deviation from ideality.
1.0
A
c
t
i
v
i
t
y

a
A
=

P
A
/

P
0
p
u
r
e
A
,
s
a
t
1.0
0
I
d
e
a
l

A
-
B

=

A
-
A

(

A
=
1
)
(
R
a
o
u
l
t
s
l
a
w
)
+
v
e
d
e
v
i
a
t
i
o
n

f
r
o
m

i
d
e
a
l
A
-
B

w
e
a
k
e
r

t
h
a
n

A
-
A

(
A
>
1
)
Mol Fraction, x
A
A
A
A
A
Liquid Solution
A in B
Gas
P
A
< P
0
A
P
A
~ x
A
mol fraction
B B
B
B
B A
A
0
A A
A
A
A
A
75
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 0.2 0.4 0.6 0.8 1
x,Ethanol
P
(
E
t
h
a
n
o
l
)
/
P
,
V
a
p
(
E
t
h
a
n
o
l
)
Ideal 2 constant Marg Exp Data
Example - Water Ethanol
- important solution for biofuels - as the result of any fermentation
reaction will contain water and ethanol.
A major cost in biofuel production is the separation of ethanol from
water
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 0.2 0.4 0.6 0.8 1
x, H2O
P
(
H
2
O
)
/
P
v
a
p
(
H
2
O
)
Ideal 2 constant Marg Exp Data
76
1.0
A
c
t
i
v
i
t
y

a
A
=

P
A
/

P
0
p
u
r
e
A
,
s
a
t
1.0
0
I
d
e
a
l

A
-
B

=

A
-
A

(

A
=
1
)
(
R
a
o
u
l
t
s
l
a
w
)
-
v
e
d
e
v
i
a
t
i
o
n

f
r
o
m

i
d
e
a
l
A
-
B

s
t
r
o
n
g
e
r

t
h
a
n

A
-
A

(

A
<
1
)
Mol Fraction, x
A
A
A
A
A
Liquid Solution
A in B
Gas
P
A
< P
0
A
P
A
~ x
A
mol fraction
B B
B
B
B A
A
0
Normalised partial pressure = activity
as a function of concentration a
A
=
A
x
A
A
= 1 - ideal behaviour
A
< 1 - negative deviation from ideality.
A A
A
A
A
A
77
Feature of activity function vs concentration:
Activity in dilute solutions - Henrys Law
a
A
= h
A
x
A
dilute concentrations always exists such that have h
A
=const (
0
A
)
A A
A
Liquid Solution
A in B
Gas
P
A
< P
0
A
P
A
~ x
A
mol fraction
B B
B
B
B B B B
A
c
t
i
v
i
t
y
,

a
A
=

P
A
/

P
0
p
u
r
e
A
,
s
a
t
1.0
0
ideal
-ve
deviation
from
ideal
1.0
Mol Fraction, x
A
h
A
0
H
e
n
r
y
s
L
a
w
78
Feature of activity function vs concentration:
Activity in dilute solutions - Henrys Law
a
A
= h
A
x
A
dilute concentrations always exists such that have h
A
=const (
0
A
)
A A
A
Liquid Solution
A in B
Gas
P
A
< P
0
A
P
A
~ x
A
mol fraction
B B
B
B
B B B B
A
c
t
i
v
i
t
y
,

a
A
=

P
A
/

P
0
p
u
r
e
A
,
s
a
t
1.0
0
ideal
+ve deviation
from ideal
1.0
Mol Fraction, x
A
h
A
0
H
e
n
r
y
s

L
a
w
79
Description of measurement of Vapour pressure
Alloy (Au-Cu) sample sheet is placed on a hot plate in a vacuum
chamber and heated up to desired temperature. After the system has
been stablised, a molybdem plate is inserted into the vacuum chamber
above the sample and the gaseous metal deposits onto the Mo plate. The
amount of deposition and time are then used to calculate the vapour
pressure of the metal.
Vapour Pressure & Activity Au-Cu alloy [Hall, 1951]
T = 1052
o
C
Au in Cu
(mol
fraction)
Log(P
Au
)
[atm]
P
Au
[atm] a
Au

Au

0 0.00E+00
0.050 -12.6 2.51E-13
0.125 -11.85 1.41E-12
0.250 -11.5 3.16E-12
0.500 -11.23 5.89E-12
0.750 -10.92 1.20E-11
1.000 -10.71 1.95E-11

Example vapour pressure and activity
Au Au
pure in solution
1) ??? what is at x = 0.5 ?
2) what is G of reaction Au Au ?

80
Example vapour pressure and activity
0.00E+00
2.00E-12
4.00E-12
6.00E-12
8.00E-12
1.00E-11
1.20E-11
1.40E-11
1.60E-11
1.80E-11
2.00E-11
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mol Fraction of Au
V
a
p
o
u
r

P
r
e
s
s
u
r
e

[
a
t
m
]
Au Vapour Pressure Raoult's behai vi our Pol y. (Au Vapour Pressure)
0.000
0.100
0.200
0.300
0.400
0.500
0.600
0.700
0.800
0.900
1.000
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mol Fraction of Au
A
u

A
v
t
i
v
i
t
y
0.000
0.200
0.400
0.600
0.800
1.000
A
c
t
i
v
i
t
y

C
o
e
f
f
i
c
i
e
n
t
Au acti vity Raoul ts's (i deal) l ine
Au Acti vity coeffi ci ent Pol y. (Au acti vi ty)
Vapour Pressure & Activity Au-Cu alloy [Hall, 1951]
T = 1052
o
C
Au in Cu
(mol
fraction)
Log(P
Au
)
[atm]
P
Au
[atm] a
Au

Au

0 0.00E+00 0.000
0.050 -12.6 2.51E-13 0.013 0.258
0.125 -11.85 1.41E-12 0.072 0.580
0.250 -11.5 3.16E-12 0.162 0.649
0.500 -11.23 5.89E-12 0.302 0.604
0.750 -10.92 1.20E-11 0.617 0.822
1.000 -10.71 1.95E-11 1.000 1.000

Solution
81
Example vapour pressure and activity measurement
with Knudsen Cell
INSERT INSERT
82
Example vapour pressure
and activity measurement
with Knudsen Cell
1) The Mass
Spectrometer with
Knudsen cell in high
vacuum is used to
directly measure vapour
pressures of various
species evaporated into
the chamber from the
Knudsen cell
2) Another method a quartz crystal
microbalance (QCM) is used to measure the
mass loss from the Knudsen cell into the
ultra high vacuum (UHV pressure below
1*10
-10
mbar) and therefore the equilibrium
vapor pressure within the cell Knudsen cell.
INSERT INSERT
83
Key concept
6. Complex reactions with solutions,
conditions for spontaneous reactions
84
30%A
solution
in B
50%A
solution
in B
B A
1
2
A in solution 1 A in solution 2
0 0
A A
Criteria for equilibrium
1 ) G G
2 )
3 ) G RT lna G RT lna
4 ) a a

= == =
= == =
+ = + + = + + = + + = +
= == =
=============== =============== =============== ===============
B in solution 1 B in solution 2
same for all other components
a a
================== ================== ================== ==================
= == =
Direction of reactions with solutions
- diffusion will proceed till there is no difference in
chemical potentials of individual species between phases
These arguments
apply to any
system at
equilibrium
solid, liquid, gas.
O
p
e
n
e
d

p
a
r
t
i
t
i
o
n
85
- diffusion will proceed till there is no difference in
chemical potentials of individual species between phases
DEMO partitioning of solute A between two immiscible liquids B and C
Pure C
(0%A)
50%A
solution
in B
?%A
solution
in C
?%A
solution
in B
These arguments
apply to any
system at
equilibrium
solid, liquid, gas.
0 0
A A
Criteria for equilibrium
1 ) G G
2 )
3 ) G RT lna G RT lna
4 ) a a

= == =
= == =
+ = + + = + + = + + = +
= == =
=============== =============== =============== ===============
B in solution 1 B in solution 2
same for all other components
a a
================== ================== ================== ==================
= == =
86
REACTION EQUILIBRIA
INVOLVING SOLUTIONS
Consider the general chemical reaction
occurring at constant temperature and
pressure:
bB + cC +. = mM+ nN +.
where b, c, ..m, n.. are the stoichiometric
coefficients indicating the number of moles
of the species B, C, .., M, N. respectively.
87
( (( ( ) )) ) ( (( ( ) )) )
R Re action
Pr oducts Re ac tants M N A C
R
The Gibbs Free Energy change associated with the general reaction
bB + cC + ... = mM + nN + ... G
G G G mG nG ... - bG cG ...
substituting chemical potentials G

= = + + + + = = + + + + = = + + + + = = + + + +

0
i i
i
0 0
M N
R M N
0 0
B C
B C
0 0 0 0
M N B C
G RT lna , then obtain
G m( G RT lna ) n( G RT lna ) ...
b( G RT lna ) c( G RT lna ) ...
after rearranging we obtain :
( mG nG ... bG cG ...)

= + = + = + = +
= + + + + + = + + + + + = + + + + + = + + + + +
+ + = + + = + + = + + =
+ + + + + + + + + + + + + + + +
M N B C
m n
0
M N
R R
b c
B C

RT(mlna nlna ... blna c lna ...)
a a ... products
G G RT ln
reac tants a a ...

+ + + + + + + +

= + = + = + = +

88
R
m n
o
M N
R R
b c
B C
products
reac tants
The condition for spontaneous change
for non-standard conditions
for any general reaction G 0
a a ....
G G RT ln i.e.
a a ....
term for cor
standard
conditions

< << <

= + = + = + = +

= + = + = + = +
rection term
for non-standard
conditions
89
( (( ( ) )) )
R
m n
o M N
R R
b c
B C
o
R eq
o
m n
R M N
eq
b c
B C
For the special case
when the system is at equilibrium, G 0
a a ....
0 G G RT ln
a a ....
G RT ln K
G a a .... products
K exp i.e.
RT reac tants a a ....

= == =

= = + = = = + = = = + = = = + =

= + = + = + = +

= = = = = = = =

eq
,
where K is the equilibrium constant
(usually K is used without "eq" subscript)

dG > 0
dG < 0
dG = 0
90
DEMO Reaction equilibria
CH
4
O
2
CO
2
H
2
O
N
2
C
n
H
2n+2
- paraffin
CH
4
+ 2O
2
+N
2
CO
2
+2H
2
O+N
2
o
1 2
R CO2 H2O
eq
1 2
CH4 O2
G a a
K exp
RT a a

= = = = = = = =

91
30%A
solution
in B
50%A
solution
in B
Solid
D
A + D ? A + D ?
50%A
solution
in B
50%A
solution
in C
A + D ? A + D ?
?
Will A in solution
react with D?
What is the extent
of reaction?
5)
6)
Solid
D
Solid
D
Solid
D
reaction
0
A A
A
reaction A + D ...
will proceed
if G 0
with G G RT lna

< << <
= + = + = + = +
92
Example: Consider the general chemical
reaction occurring at constant temperature and
pressure:
B(s) + cC(g) +. = mM(l) + nN(g)
if C and N are gaseous
then (for pure component standard state)
a
c
= P
C
and a
N
= P
N
m
o
M
R R
b
B
n
N
c
C
a . P
P
...
G G RTln
a ....

= + = + = + = +

93
Example: Consider the general chemical
reaction occurring at constant temperature
and pressure:
bB(s) + cC(g) +. = mM(l) + nN(g)
if B and M are pure then a
B
= 1 and a
M
= 1
n
o
N
R R
c
C
eq
P ....
G G RTln
P ....
1
1

= + = + = + = +

94
Consider the general chemical reaction
occurring at constant temperature and pressure:
bB(s) + cC(g) +. = mM(l) + nN(g)
if B and M behave ideally,
a
B
=x
B
and a
M
= x
M
n
o
m
M
b
B
N
R R
c
C
eq
P ....
G G RTln
P ..
x
x ..

= + = + = + = +

95
Example: Will PbO be reduced in CO/CO2 gas?
PbO(s)+CO(g)Pb(l)+CO
2
(g)
1) for gaseous: a
CO
= P
CO
and a
CO2
= P
CO2
.
2) if PbO and Pb are pure then a
PbO
= 1 and a
Pb
= 1
1
CO2( g
1
Pb( l ) o
R R
)
1
CO
1
PbO ( g ( s ) )
a
G G RTln
a
P
P

= + = + = + = +

1
CO2( g ) o
R R
1
CO( g )
1
1
P
G G RTln
P

= + = + = + = +

PbO(s)
Pb(l)
96
Example: PbO(s)+CO(g)Pb(l)+CO
2
(g)
3) if PbO and Pb are in solutions and behave
ideally (Raoults Law), then (for pure component
standard state)
a
PbO
=x
PbO
and a
Pb
= x
Pb
1
CO2( g ) o
R
1
Pb( l )
1
PbO( s )
R
1
CO
x
x
P
G G RTln
P

= + = + = + = +

97
The approach is true for ALL chemical reactions
m n
o
M N
R R
b c
B C
a a ....
G G RT ln
a a ....

= + = + = + = +

dG > 0
dG < 0
dG = 0
98
SUMMARY Direction of reactions with solutions
i i
j i
0
i i i
i i
i
T ,P ,N
i i
i i
0 0
i i
i i i i
>1 - positive deviation, <0-negative d
G
1 ) G chemical potentiaal; 2 ) G =G RT lna
N
f P
3 ) a , for low pressures a
f P
4 ) a x ( is function of composition)

= = + = = + = = + = = +

= = = = = = = =
= == =
i
0
A
A in sol
eviation,
=0 -ideal(Raoult's Law) - do not confuse with ideal gas
5 ) condition for equilibria:
G G (or )
G RT lna

= = = = = = = =
+ ++ +
0
A
ution 1 A in solution 2
A in soltn.1 A in soltn.1 A in soltn.2 A in soltn.2
0 0 0
i i i
i i i i i
0
i i
G RT lna
a a
x x
6 ) G RT lna G RT ln x G RT ln x RT ln
7 ) Henrian Law or h

= + = + = + = +
= == =
= == =
+ = + = + + + = + = + + + = + = + + + = + = + +
m n
o
M N
R R
b c
B C
a a ....
8 ) G G RT ln
a a ....

= + = + = + = +

99
Example: Mono-pressure nitric acid plant:
A key part of the process if the oxidation of ammonia to nitrous oxide in the
NH
3
converter:
NH
3
(g) + 1.25O
2
(g) NO(g) + 1.5H
2
O(g)
r
G
0
(1073.15) = -276,764 J/mol
Q.? Is reaction spontaneous at 800
o
C if the gas stream has the following partial
pressures?
NH
3
: 110
-6
MPa
O
2
: 0.15 MPa
NO: 0.1 MPa
H
2
O: 0.15 MPa
100
Example: Mono-pressure nitric acid plant:
A key part of the process if the oxidation of ammonia to nitrous oxide in the
NH
3
converter:
NH
3
(g) + 1.25O
2
(g) NO(g) + 1.5H
2
O(g)
r
G
0
(1073.15) = -276,764 J/mol
Q.? Is reaction spontaneous at 800
o
C if the gas stream has the following partial
pressures?
Solution:
NH
3
: 110
-6
MPa =9.910
-06
atm
O
2
: 0.15 MPa = 1.480 atm
NO: 0.1 MPa = 0.987 atm
H
2
O: 0.15 MPa = 1.480 atm
1 1.5
o
NO H2O
R R
1 1.25
NH3 O2
1 1.5
6 1.25
R
a a
G G RTln
a a
0.987 1.480
276,764 8.314* 1073.15ln -173169 J/mol
9.9 10 1.480
G <0 - reaction will proceed spontaneously

= + = = + = = + = = + =

= + = = + = = + = = + =

101
Example:
Can Mn catalyst on Al
2
O
3
substrate be used
in a process at 900
o
C and
syngas with CO/CO
2
volume ratio =10
6
?
1. Will Al
2
O
3
and Mn react?
2. Will Mn be oxidised to MnO?
3. Will Al
2
O
3
be reduced to Al?
Mn
Al
2
O
3
CO/CO
2
102
103
Example: Step 1. Will Al
2
O
3
and Mn react?
Solution:
1. Formulate reaction 3Mn+Al
2
O
3
3MnO+2Al
2. Assumptions: pure Mn, Al, Al
2
O
3
, MnO, no intermediate compounds or solutions
3. Find
R
G
0
1173K
1) Mn(s) + 0.5O
2
(g) MnO
R1
G
0
1173K
=-388900 +76.3T = -299 KJ mol
-1
2) 2Al(l) + 1.5O
2
(g) Al
2
O
3
(s)
R2
G
0
1173K
=-1682900 +323.2T = - 1303 KJ mol
-1
3) 3Mn(s)+Al
2
O
3
(s) 3MnO(s)+2Al(l) (R3) = 3*R1 R2

R3
G
0
1173K
=3*(-299)-(-1303) = +406 KJmol
-1
> 0
4. Find
R
G
1173K
since
R3
G
1173K
> 0, the reaction of reduction of Al
2
O
3
and oxidation of Mn
will not proceed, so Mn catalyst will not react with Al
2
O
3
ceramic substrate
the Al
2
O
3
can be used as ceramic substrate for Mn catalyst
(if no intermediate compounds or solutions are formed)
3 1
o
MnO Al
R3 R3
3 1
Mn Al 2O3
3 1
MnO Al
MnO Al Mn Al 2O3
3 1
Mn Al 2O3
o
1
R R
a a
G G RT ln ,
a a
a a
for pure phases a a =a a =1 , then ln 0,
a a
then G G 0 406KJmol

= + = + = + = +

= = = = = = = = = = = =

= + = + = + = + = + = + = + = +
104
Step 2. Will Mn be oxidised to MnO?
1. Formulate reaction 1) Mn(s) + CO
2
(g) MnO + CO(g)
2. Assumptions: Mn is oxidised to MnO,
pure Mn & MnO, ideal CO &CO
2
3. Find
R1
G
0
1173K
= R2+R3-R4=-118 KJ/mol
R2) Mn(s) + 0.5O
2
(g) MnO
R
G
0
1173K
= -299 kJ/mol
R3) C + 0.5O
2
CO
R
G
0
1173K
= -214 kJ/mol
R4) C+O
2
CO
2

R
G
0
1173K
= -396 kJ/mol
4. Find
R1
G
1173K
As
R1
G
1173K
>0 then Mn catalyst will not be oxidised in a process at 900
o
C
and syngas with CO/CO
2
volume ratio =10
6
.
( (( ( ) )) )
( (( ( ) )) )
1 1
o
MnO CO
R1 R1 MnO Mn
1 1
Mn CO2
o
CO CO2 R1 R1 CO CO2
6
a a
G G RT ln , assume pure phases a a =1,
a a
for P and P in atm G G RT ln P / P
117985 8.314* 1173.15* ln 10 117985 134750 16765J / mol

= + = = + = = + = = + =

= + = = + = = + = = + =
= + = + = + = + = + = + = + = + = + = + = + = +
105
Step 3. Will Al
2
O
3
be reduced to Al?
1. Formulate reaction 1) Al
2
O
3
(s)+3CO2Al(l) + 3CO
2
(g)
2.Assumptions: pure Al
2
O
3
(s) reacts to pure Al(l),
CO & CO
2
are ideal
3. Find
R2
G
0
1173K
= -R2-3R3+3R4=759KJ/mol
R2) 2Al(l) + 1.5O
2
(g)Al
2
O
3
(s)
R
G
0
1173K
= -1303 KJ/mol
R3) C + 0.5O
2
CO
R
G
0
1173K
= -214 KJ/mol
R4) C+O
2
CO
2

R
G
0
1173K
= -396 KJ/mol
4. Find
R2
G
1173K
As
R1
G
1173K
>0 then Al
2
O
3
substrate will not be reduced to Al
in a process at 900
o
C and syngas with CO/CO
2
volume ratio =10
6
.
( (( ( ) )) )
2 3
o
Al CO2
R1 R1 Al 2O3 Al
1 3
Al 2O3 CO
o
3 3
CO CO2 R1 R1 CO2 CO
6
a a
G G RT ln , assume pure phases a a =1,
a a
for P and P in atm G G RT ln P / P
759528 3* 8.314* 1173.15* ln( 10 ) 759528 404252 355276 J / mol

= + = = + = = + = = + =

= + = = + = = + = = + =
= + = = = + = = = + = = = + = =
106
Example: What temperature and syngas composition (CO/CO
2
) ranges
are safe for Mn catalyst on Al
2
O
3
substrate be used in a process ?
1) 3Mn(s)+Al
2
O
3(s)
3MnO(s)+2Al(l)
R1
G
0
T
=...
2) Mn(s) + CO
2(g)
MnO + CO(g)
R2
G
0
T
=...
3) Al
2
O
3(s)
+3CO 2Al(l) + 3CO
2(g)

R3
G
0
T
=...
2 3
o
Al CO2
R3 R3
1 3
Al 2O3 CO
a a
G G RT ln ?
a a

= + = + = + = +

1 1
o
MnO CO
R2 R2
1 1
Mn CO2
a a
G G RT ln ?
a a

= + = + = + = +

3 1
o
MnO Al
R1 R1
3 1
Mn Al 2O3
a a
G G RT ln ?
a a

= + = + = + = +

If in addition we would need to select a ceramic material for substrate and a metal
for catalyst in addition to the question about the ranges of conditions that would
require collection of a lot of data and extensive calculations.
Further calculations are
needed to calculate
ranges of T and CO/CO
2
107
APPENDIX
EXAMPLES OF Ni OXIDATION
AT DIFFERENT CONDITIONS
108
m n
o
M N
R b c
to
B C
solid , 2 ,gas sol ,
al P
i
t
d
a a ....
bB cC ... m
Example 1: Will pure Ni oxidis
M nN ... G G RTln
a a ....
Ni 0.5O NiO
E.g., for the reac
e at 1300K and P =1 atm?
tio
1a) using C expressions
n

+ + + + = + + + + + = + + + + + = + + + + + = +

+ > + > + > + >
2
0
MO pure 2 ,gas pure F
0 0 0
0
MO M O
MeO F
0 0 0
1 2
T T T
P
T 0 0
T 298.15
P P
298.15 298.15
of metal with oxygen M 0.5O MO G
Molar Gibbs Free Energy of Formation G G G 0.5G
G H T S ; for C A BT CT
H H C dT; C dT

+ ++ +
= = = =
= = + + = = + + = = + + = = + +
= + = + = + = +

( (( ( ) )) )
2
T T
1 2 2 1 T
298.15
298.15
T T T 0 0
1 3 2 T P P
T 298.15
298.15
298.15 298.15 298.15
0 0 0
0
MO M O
F ,MeO
T 0
298.15 ,MeO
P ,MeO
298.15
B
( A BT CT )dT [ AT T CT ]
2
C C C
S S dT; dT ( AT B CT )dT [ Aln( T ) BT T ]
T T 2
G G G 0.5G
H C dT

= + + = + = + + = + = + + = + = + + = +
= + = + + = + = + = + + = + = + = + + = + = + = + + = +
= = = = = = = =
= + = + = + = +

( (( ( ) )) )
( (( ( ) )) )
2
2 2
2
T 0
P ,MeO
298.15 ,MeO
298.15
T T 0 0
P ,Me
298.15 ,Me 298.15 ,Me
P ,Me
298.15 298.15
T T 0 0
P ,O
298.15 ,O 298.15 ,O
P ,O
298.15 298.15
F
C
T* S dT
T
C
H C dT T* S dT
T
C
0.5* H C dT T* S dT
T
H

+ + + +

+ + + + + + + +

+ + = + + = + + = + + =

= == =

0 0
MeO,T MeO,T F
T* S
109
0 0 0
1 2
T T T
P
0 0 T
T 298.15
P P
298.15 298.1
t
solid ,
ota
2 ,ga
l P
s solid ,
H H C dT ; C dT
Ni 0.5
Example 1a): Will pure Ni oxidise at 1300K and P =1 atm? (using C ) Continua
O NiO
tion...

= = + + = = + + = = + + = = + +
= + = + = + = +
+ > + > + > + >

T T
1 2 2 1 T
298.15
5 298.15
0 0 T T T
1 3 2 T
P P
T 298.15
298.15
298.15 298.15 298.15
B
2
C C C
S S dT ; dT ( AT B CT )dT [ Aln( T ) BT T ]
T T 2

= + + = + = + + = + = + + = + = + + = +
= + = + + = + = + = + + = + = + = + + = + = + = + + = +

2
0 0 0
0
NiO Ni O
F ,NiO
G G G 0.5G = = = =
110
0 0 0
1 2
T T T
P
0 0 T
T 298.15
P P
298.15
solid , 2,g
total P
as solid ,
H H C dT ; C dT
Ni
Example 1a): Will pure Ni oxidise at 1300K and P =1 atm? ( 1a) using
0.5O Ni
C ) Continuat

.
O
ion ..

= = + + = = + + = = + + = = + +
= + = + = + = +
+ > + > + > + >

T T
1 2 2 1 T
298.15
298.15 298.15
0 0 T T T
1 3 2 T
P P
T 298.15
298.15
298.15 298.15 298.15
B
2
C C C
S S dT ; dT ( AT B CT )dT [ Aln( T ) BT T ]
T T 2

= + + = + = + + = + = + + = + = + + = +
= + = + + = + = + = + + = + = + = + + = + = + = + + = +

0
298 ,15 H
0
298 ,15 S
0 0 -167000 C
P
C*T
-2
0.00846 0.00753 0.00418 C
P
B*T
1
46.800 25.100 29.960 C
P
A*T
0
38.080 30.950 205.000 [J mol
-1
K
-1
]
-240600 630 0 [J mol
-1
]
NiO
solid,
Ni
solid,
O
2,gas
Value
0
1300 H
0
1300 S
0
1300 G -337051 -66286 -295209 [J mol
-1
]
115.47 75.45 252.41 [J mol
-1
K
-1
]
-186941 31805 32930 [J mol
-1
]
NiO
solid,
Ni
solid,
O
2,gas
2
0 0 0
0
1
NiO Ni O
NiO F
0
NiO F
G G G 0.5G 123161[ Jmol ]
G <0 - therefore pure Ni will oxidise at 1 atm and 1300K

= = = = = = = =
111
solid , 2 ,gas solid ,
0 0 0
NiO NiO NiO F F F
0 0
NiO
0 0
total F
iO
F
N F F
Ni 0.5O NiO
alternative way
Example 1b): Will pure Ni
G H T* S ,
where H and S are values
oxidise at 1300K and P =1 atm? (using

H

&

S )

+ > + > + > + >
= = = =
0 0
1 1 1
NiO NiO F F
approximately valid over a range of temperatures
H 235800Jmol ; S 86.2 Jmol K

= = = = = = = =
112
0 0
total
so d ,
F F
li
Example 1b): Will pure Ni oxidise at 1300K and P =1 atm? (using H & S )
Continuati
N
on
i 0.

+ ++ +
2 ,gas solid ,
0 0 0
NiO NiO NiO F F F
0 0
NiO NiO,T F F
0
1
NiO F
5O NiO
alternative way G H T* S ,
where H and S are values
approximately valid over a range of temperatures
H 235800Jmol

> > > >
= = = =
= = = =
( (( ( ) )) )
0
1 1
NiO F
0
1
NiO F
0 NiO,solid ,
NiO NiO R F 0.5
Ni ,solid , O2,gas
; S 86.2 Jmol K
at 1300K G 235800 1300* 86.2 123740 Jmol
a
G G RTln
a * P
Case

= = = =
= = = = = = = =

= + = + = + = +

======================================== ======================================== ======================================== ======================================================= =============== =============== ===============
( (( ( ) )) )
( (( ( ) )) )
total 2
NiO,solid Ni,solid O2,gas O2 2 O2
0.5
NiO R
1. Will pure Ni oxidise at 1300K and P =1 atm in pure O ?
Pure NiO a =1; Pure Ni a =1, a =P ; pure O at 1atm: P =1
at1300K G =-123740+8.314*1300*ln 1/ 1*1 = -123740 J /mol < 0
Ni will oxidise to NiO
113
solid , 2,gas solid ,
0 0 NiO,solid ,
1
NiO NiO NiO R F F 0.5
Ni ,solid , O2,gas

Ni 0.5O NiO
a
G G R
Example Case 2: Will pure Ni oxidise in ai
Tln G 123740 Jmo
r
a
?
l
* P

+ > + > + > + >

= + = = + = = + = = + =

============================= ============================= ============================= =============================
( (( ( ) )) )
( (( ( ) )) )
NiO,solid Ni,solid O2
0.5
NiO R
Pure NiO a =1; Pure Ni a =1, air P =0.21
at1300K G =-123740+8.314*1300*ln 1/ 1*0.21 = -115306 J/mol < 0

========================== ========================== ========================== ==========================
114
0 NiO,solid ,
NiO NiO R F 0.5
Ni ,solid , O2,
2 total
gas
Example Case 3: Will pure Ni oxidise
in Nitrogen gas with 1ppm O impurity at P =1 atm
Ni 0.5O NiO
a
G G RTln
a * P
?

+ > + > + > + >

= + = + = + = +

2
0
1
NiO F
NiO,solid Ni,solid
6
2 total O
R
G 123740 Jmol
Pure NiO a =1; Pure Ni a =1,
Nitrogen gas with 1ppm O impurity at P =1 atm: P =10
at1300K

= = = =

======================================== ======================================== ======================================== ======================================================= =============== =============== ===============
( (( ( ) )) )
( (( ( ) )) )
6 0.5
NiO
G =-123740+8.314*1300*ln 1/ 1*(10 ) = -49080 J/mol < 0

==================== ==================== ==================== ======================================================= =================================== =================================== ===================================
115
2
Ni,solid
solid , 2
6
2 t
,gas solid ,
R
otal O
Example: Will Ni oxidise?
Case 4: Will Ni in Cu alloy with a =0.01 oxidise at 1300K
in Nitrogen gas with
Ni 0.5O
1ppm O impurity at P =1 atm:
Ni
=
G
0
O
P 1 ?

+ > + > + > + >
( (( ( ) )) )
( (( ( ) )) )
0 0 NiO,solid ,
1
NiO NiO NiO F F
0.5
Ni ,solid , O2,gas
6 0.5
NiO R
a
G RTln G 123740 Jmol
a * P
at1300K G =-123740+8.314*1300*ln 1/ 0.01*(10 ) = +694 J/

= + = = + = = + = = + =

======================================== ======================================== ======================================== ======================================================= =============== =============== ===============
mol > 0
Ni will not oxidise to pure NiO
116
2
Ni,solid
6
2 total O
Example: Will Ni oxidise?
Case 5: Will Ni in Cu alloy with a =0.01 oxidise at 1300K
in Nitrogen gas with 1ppm O impurity at P =1 atm: P =10
in contact with MgO-NiO crucibl

0 0 NiO,solid ,
1
NiO NiO NiO R F F 0.5
Ni ,solid , O2 ,
NiO
gas
,solid
Ni 0.5O NiO
a
G G RTln G 123740 J
e having a 0.5
mo
*
?
l
a P

+ > + > + > + >

= + = = + = = + = = + =

======================================== ======================================== ======================================== =================================================== =========== =========== ===========
= == =
==== ==== ==== ====
( (( ( ) )) )
( (( ( ) )) )
6 0.5
NiO R
Ni,solid NiO
at1300K G =-123740+8.314*1300*ln 0.5/ 0.01*(10 ) = -6798 J/mol < 0
Ni from alloy (a =0.01) will oxidise to NiO in solution with MgO (a =0.5)

117
2 2
Ni,solid total
NiO,solid
Example Case 6:
What maximum O impurity in N is allowed to avoid Ni oxidation
from Cu alloy with a =0.01 oxidise at 1300K, P =1atm,
in contact with MgO-NiO crucible having a 0.5? = == =
solid , 2 ,gas solid ,
0 0 NiO,solid ,
1
R,NiO F ,NiO F ,NiO
0.5
Ni ,solid , O2,gas
NiO,solid ,
Ni ,solid
Ni 0.5O NiO
a
G G RTln G 123740 Jmol
a * P
a
a

+ > + > + > + >

= + = = + = = + = = + =

======================================== ======================================== ======================================== ======================================================= =============== =============== ===============
2
2
0 0
F ,NiO F ,NiO
NiO
O 0.5
, O2,gas Ni
2 7
O2 ,gas
G G
a
exp P exp *
* P RT RT a
at 1300K P =[exp(-123740/8.314/1300)*0.5/0.01 ] =2.84*10 atm

= = = = = = = =

2 2
0.284 ppm O in N is safe
======================================== ======================================== ======================================== ======================================================= =============== =============== ===============
118
0 0
1 1 1
NiO NiO s 2,gas s F F
2
t
g 2
o
,
tal
Example: Case 7 What minimum CO/CO ratio in gas is needed to protect
pure Ni from oxidation at 1300K
R1) Ni 0.5O NiO H 235800Jmol ; S 86.2 Jm
(P =1
ol K
R2) CO 0.5O
atm)?

+ = = + = = + = = + = =
+ ++ +
0 0
1 1 1
g 2 ,g R2 R2
0 0
1 1 1
s 2,gas s gas R3 R3
0
R3
CO H 281900Jmol ; S 85.7 Jmol K
R3 R1 R2
R3 ) Ni CO NiO CO H 46100Jmol ; S 0.5 Jmol K
at 1300 K G = 46100-13

= = = = = = = =

= = = =
+ + = = + + = = + + = = + + = =
1
0 NiO,solid , CO,gas
R3 R3
Ni ,solid , CO2,gas
Ni,solid NiO,solid
0
CO,gas Ni ,
R3
R3
CO2,gas
00(-0.5)=+46750 Jmol
a * P
G G RTln
a * P
pure Ni a =1 ; pure NiO a =1
P a
G
at equilibrium G 0, then exp *
P RT

= + = + = + = +

= = = = = = = =

solid
NiO,solid
CO,gas
2
CO2,gas
a
P
46750 1
at 1300K exp * = 1.32*10
P 8.314* 1300 1

= == =

119
References:
1. Koretsky, M.D., 2004. Engineering and Chemical Thermodynamics,
John Wiley & sons Inc., Hoboken, NJ.
2. Lee, H.G., 1999. Chemical thermodynamics for metals and materials ,
Imperial College Press, London.
3. Atkins, P. & de Paula, J., 2006, Atkins' Physical Chemistry, 8th edition,
Oxford University Press, Oxford, NY.
List of DEMOS:
1. Ethanol water volume
2. Solubility product make the solution
3. Two immiscible liquid solvents and a solute
CuSO
4
partition can be affected by H
2
SO
4
4. Reaction equilibria candle in air
120
Example: 2Ag(s)+0.5O
2
(g)Ag
2
O(s)
1) for gaseous: a
O2
= P
O2
2) if Ag and Ag
2
O are pure then a
Ag
=1 and a
Ag2O
= 1
2
2
1
Ag O( s )
o
R R
2
A
0.5
O ( s ) g ) g(
a
G G RTln
P a

= + = + = + = +

2
2
1
Ag O( s )
2
A
o
R R
0.5
O ( ( g ) g s )
G
1
R ln
P 1
G T

= + = + = + = +

2
2
1
Ag O( s )
o
R R
2 0.5
Ag( s ) O ( g )
a
G G RTln
a a

= + = + = + = +

121
Example: 2Ag(s)+0.5O
2
(g)Ag
2
O(s)
3) if Ag and Ag
2
O behave ideally (Raoults Law),
a
Ag
=x
Ag
and a
Ag2O
= x
Ag2O
2
2
1
Ag O( s )
2
A
o
R R
0.5
O ( ( g ) g s )
G
x
R ln
P x
G T

= + = + = + = +

1
Lecture week 7 (2012) CHEE3003
CALCULATION AND
REPRESENTATION OF
COMPLEX EQUILIBRIA
UNDER NON-STANDARD
CONDITIONS
2
Key Concepts:
Graphical representation of complex
equilibria
- Ellingham Diagrams
- Predominance Diagrams
3
For example:
Will a catalyst oxidise in particular gas stream in a range of temperatures?
Will production gas oxidise tubes or reduce ceramic (complex oxide) filters at a
given temperature?
Can you use Fe plate with Al
2
O
3
refractory?
Can you heat PbO in Ni crucible?
Can you selectively reduce some of the metal oxides and keep others unchanged?
Which PbO, Pb
3
O
4
or PbO
2
will be stable at what T and P?
Or more general:
What range of operational conditions has to be used to achieve a certain target or to
avoid a certain reaction? E.g. temperature, total pressure, composition
!!! Graphical and computer tools are used for complex systems
Real systems are not pure, complex, multi-component, multi-phase.
A number of seemingly simple important practical questions require
extensive calculations to answer.
4
ELLINGHAM first constructed a very useful diagram
now called ELLINGHAM DIAGRAM
that shows stability of certain groups of compounds.
can assist in fast answer to a wide range of questions
are now widely used.
In the following slides we will construct several lines for
the ELLINGHAM DIAGRAM.
5
2
0
pure 2, gas pure F MO
0 0
0
MO M O
F MeO
e.g. METAL OXIDES
For the reaction of metal with oxygen M 0.5O MO G
where n is oxidation state of the metal oxide
Molar Gibbs Free Energy of Formation G G G 0.5G

+ ++ +
= = = =

2
2 2
2
0
T T 0 0
P,MeO
298.15 ,MeO 298.15 ,MeO
P,MeO
298.15 298.15
T T 0 0
P ,Me
298.15 ,Me 298.15 ,Me
P ,Me
298.15 298.15
T 0 0
P,O
298.15 ,O 298.15 ,O
P ,O
298.15 2
C
H C dT T* ( S dT )
T
C
H C dT T* ( S dT )
T
C
0.5* H C dT T* ( S dT )
T
= == =
| | | | | | | |
= + + = + + = + + = + +
| | | |
\ \ \ \
| | | | | | | |
+ + + + + + + +
| | | |
\ \ \ \
+ + + + + + + +

T
98.15
0 0 0
F F F MeO MeO MeO
0 0
F F MeO MeO
G H T* S
the values H and S for metal oxides do not change a lot with temperature
- approximate "mean" values valid over a range of temperatures are frequent

| | | | | | | |
| | | |
| | | |
\ \ \ \
= = = =

ly
tabulated and used - this is common for other groups of compounds (e.g. sulfides etc)
REPRESENTATION OF EQUILIBRIA G
F
0
vs T
6
Although C
P
of
compounds are
complex functions
of temperature, the
terms
R
H
0
and

R
S
0
do not change
significantly with T
!!!
2
0 0 0
0 0
MO M O
pure 2, gas pure F F MO MeO
e.g. METAL OXIDES 0.5M 0.5O MO G ; G G 0.5G 0.5G + = + = + = + =
m n
0 0 0 0
0 0
M N
M N B C
R R R
b c
B C
0 0 0
1 2
R R R P T T T
0
0
298.15 ,i
R T
i
REACTION EQUILIBRIA bB + cC + ... = mM + nN + ...
a a ...
G G RT ln G ( mG nG ... bG cG ...)
a a ...
At temperature T G H T S ; for C A BT CT
H i H

| | | | | | | |
= + = + + = + = + + = + = + + = + = + +
| | | |
\ \ \ \
= = + + = = + + = = + + = = + +
= == =
( (( ( ) )) )
T T 0
0 P ,i
298.15 ,i
P ,i R T
298.15 298.15
i i i
C
i C dT and S iS i dT
T
where i - stoichiometric coefficients (products "+"; reactants"-")

| | | | | | | |
+ = + + = + + = + + = +
| | | |
\ \ \ \

7
Temperature, K
G
F
0

[
k
J

m
o
l
-
1
]
4Ag(s) + O
2
(g)2Ag
2
O(s)

F
G
0
=

F
H
0
-
T

F
S
0 =
-
5
6
.
2
+
0
.
1
2
1
2

J

m
o
l
-
1 O
2
0
-60
-40
-20
20
40
0 100 200 300 400 500 600 700
1)2Ag(s) + 0.5O
2
(g)Ag
2
O(s)
F
G
0
=-28.1+0.0606T [kJ per mol Ag
2
O]
2) 4Ag(s) + O
2
(g)2Ag
2
O(s)
F
G
0
=-56.2+0.1212T [kJ per mol O
2
]
! Per mole of O
2
!

F
H
0
=-56.2kJ mol
-1
- intersection at T = 0
o
K

F
S
0
=
+0.1212
kJ mol
-1
K
-1
- slope
0 0 0
F F F MeO MeO MeO
For metal oxides G H T* S = = = =
REPRESENTATION OF EQUILIBRIA
F
G
0
vs T
Standard
conditions:
pure metal,
pure oxide
8
Temperature, K
G
F
0

[
k
J

m
o
l
-
1
]
4Ag(s) + O
2
(g)2Ag
2
O(s)

F
G
0
=

F
H
0
-
T

F
S
0 =
-
5
6
.
2
+
0
.
1
2
1
2

J

m
o
l
-
1 O
2
0
-60
-40
-20
20
40
0 100 200 300 400 500 600 700
4Ag(s) + O
2
(g)2Ag
2
O(s)
F
G
0
=-56.2+0.1212T [kJ per mol O
2
]

F
S
0
0 0 0
F F F MeO MeO MeO
For metal oxides G H T* S = = = =
F
G
0
vs T
From higher disorder -
4 moles solid+1mol gas
to low disorder
(higher order)
-2 moles of solid
entropy (measure
of disorder)
decreased S<0
So for metal oxides

F
G
0
=
F
H
0
T
F
S
0
-slopes are positive
and similar
9
2
Ag2O 0
R F'
4 1
Ag O2
0
R F' O2
R
0
F' O2
a
G G RT ln
a * P
For pure metal and pure oxide G G RT ln( 1 / P )
At equilibrium
G 0, so
G RT ln P

| | | | | | | |
= + = + = + = + | | | |
| | | |
\ \ \ \
= + = + = + = +
= == =
= == =
Temperature, K
G
F
0

[
k
J

m
o
l
-
1
]
4Ag(s) + O
2
(g)2Ag
2
O(s)
0
-60
-40
-20
20
40
0 100 200 300 400 500 600 700
4Ag(s) + O
2
(g)2Ag
2
O(s)
F
G
0
=-56.2+0.1212T [kJ per mol O
2
]
F
G
0
vs T

F
G
0
measure
of chemical
affinity
of metal
to oxygen
Decomposition T

F
G
0
>0
Ag is
stable

F
G
0
<0
AgO
2
is stable

F
G
0
=

F
H
0
-
T

F
S
0 =
-
5
6
.
2
+
0
.
1
2
1
2

k
J

m
o
l
-
1 O
2
10
F
G
0
vs T
If Gibbs Free energies of formation are presented
per 1 mol of common gaseous species O
2
, then the
relative stabilities of metal oxides can be readily
compared
e.g.
Ag
1+
: 4Ag(s) + O
2
(g) 2Ag
2
O(s)
Fe
2+
: 2Fe(s) + O
2
(g) 2FeO(s)
Al
3+
: 4/3Al(s) + O
2
(g) 2/3Al
2
O
3
(s)
Ti
4+
: 2Ti(s) + O
2
(g) TiO
2
(s)
11
Example: What temperature range is safe for Mn catalyst on Al
2
O
3
substrate to be used in a process?
1) 2Mn(s) + O
2(g)
->2MnO
R1
G
0
1173K
=2*
F
G
0
MnO
=-777800-152.6T
2) 4/3Al(l)+O
2(g)
->2/3Al
2
O
3(s)

R2
G
0
1173K
=2/3
F
G
0
Al2O3
=-1121933-215.5T Jmol
-1
3) 2Mn(s)+2/3Al
2
O
3(s)
2MnO(s)+4/3Al(l) (R3) = R1R2=344133+62.9T >0
G
o
,

k
J

m
o
l
-
1
O
2
4
/
3
A
l
(
l
)

+

O2
(
g
)

=
2
/
3
A2
O3
(
s
)
2
M
n

+

O
2
(
g
)

=

2
M
n
O
(
s
)

R
1
G
0
=
-
7
7
7
8
0
0
+
1
5
2
.
6
T
Temperature, K

R
3
G
0
=
3
/
2
(

R
1
G
o
-

R
2
G
o
)
0 K 1173 K
-500-
-1000-

R
2
G
0
=
-
1
1
2
1
9
3
3
+
2
1
5
.
5
T

J
m
o
l
-
1
Presentation of

F
G
0
per 1 mol of
oxygen enables
direct graphical
analysis of relative
stability of
different metals
and oxides
12
G
o
,

k
J

m
o
l
-
1
O
2
R
1
)

2
A

+

O
2
(
g
)

=
2
A
O
(
s
)
R
2
)

B

+

O
2
(
g
)

=

B
O
2
(
s
)
Temperature, K
T
E
R
3
G
0 =
R
2
G
o
B
O
2
-
R
1
G
o
A
O
G
0
R3
<0
BO
2
is more stable than AO
Reaction 3 will proceed
from left to right
B will reduce AO to A
G
0
R3
>0
AO is more stable than BO
2
A will reduce BO
2
to B
0
F
0
R 2
0 0
2 R1 F A
ELLINGHAM DIAGRAM RELATIVE STABILITIES OF GROUP OF COMPOUNDS G vs T
E.g. for metal oxides, series of reactions G are written for 1 mol O
R1 2A + O 2AO G 2 G
R2

= = = =
0 0
2 2 R2 F B
0 0 0 0 0
B A
F F 2 R3 R2 R1
B + O BO G G
R3=R2-R1: B+2AO BO +2A G G G G 2 G

= = = =
= = = = = = = =
R3=R2-R1
13
ELLINGHAM:
Combined Gibbs Free energies of
formation per 1 mol of common
gaseous species for similar groups of
compounds (oxides, sulphides,
chlorides etc. ).
Now called
ELLINGHAM DIAGRAMS
1) Are comprehensive sources of data
2) Present relative stability of various
compounds or species analysing
which one will be stable
3) Make analysis and calculations very
simple
4) Allows analysis of sensitivity to
process variables
!!! Use faster than computers !!!
14
ELLINGHAM DIAGRAM EXAMPLE:
? Can pure metallic Fe be kept at 1000
o
C in
contact with Cr
2
O
3
without reduction of
Cr
2
O
3
?
1) 2Fe + O
2
->2FeO

R1
G
0
1000C
=-360 kJ mol O
2
-1
2) 4/3 Cr + O
2
->2/3Cr
2
O
3

R2
G
0
1000C
=- 525 kJ mol O
2
-1
3)2/3Cr
2
O
3
+ 2Fe->2FeO+4/3Cr
(R3) = (R1)(R2)

R3
G
0
1000C
=-360-(-525)= +165 kJmol
-1
> 0
Reaction 3 will not proceed
Cr
2
O
3
is more stable at 1000
o
C
Fe can contact Cr
2
O
3
at 1000
o
C
The answer can be obtained directly from
the graph - Cr
2
O
3
line is lower than FeO
15
Example: Can other ceramic substrates (SiO
2
, TiO
2
, Cr
2
O
3
, MgO)
be used for Mn catalyst and in what range of temperatures?
Cr
2
O
3
cant
SiO
2
TiO
2
Al
2
O
3
MgO
can be used
lines are lower,
oxides are
more stable
16
Example: Which ceramic (oxide) crucible (SiO
2
, TiO
2
, Cr
2
O
3
, MgO)
can be used to melt Al?
Cr
2
O
3
SiO
2
TiO
2
cant
MgO
can be used
the line is
lower, MgO
is more stable
17
2A(s,l)+O
2
=2AO(s,l)
F
G
0
=
F
H
0
-T
F
S
0
Slope of the line changes with the change of state
S
gas
>S
liq
>S
solid
2
A
(s
)+
O
2
=
2
A
O
(s
)
2
A
(
l
)
+
O
2
=
2
A
O
(
s
)
2
A
(
l
)
+
O
2
=
2
A
O
(
s
)
2
A
(
l)
+
O
2
=
2
A
O
(
l
)
AO
AO

R
S
0

F
S
0
=2S
0
AO
-S
0
O2
-2S
0
A
18
F
G
0
vs T
Slope of the line changes at the change of state
19
F
G
0
vs T
Slope of the line changes at the change of state
20
REACTIONS AT NON STANDARD CONDITIONS IN O
2
at fixed P
O2
4Ag(s) + O
2
(g) -> 2Ag
2
O(s) Effect of P
O2
1) if Ag and Ag
2
O are pure,
then G=
F
G
0
+RTln(1/P
O2
) = (
F
H
0
-T
F
S
0
) - RTln(P
O2
)
2)
F
G
0
is negative for most of oxides and increases with temperature
3) For a given O
2
partial pressure P
O2
at P
total
=1 atm, P
O2
<1, lnP
O2
<0
then the term [ Rln(P
O2
) ]<0, then the term [-RTln(P
O2
)] is positive,
and makes more and more positive contribution to G
as temperature increases
Richardson added nomographic scale for the [-RTln(P
O2
)] term to
Ellingham diagrams
21
COMPOUNDS IN NON STANDARD CONDITIONS IN O
2
at fixed P
O2
Effect of P
O2
4Ag(s) + O
2
(g) -> 2Ag
2
O(s)
if Ag and Ag
2
O are pure, then G= G
0
+RTln(1/P
O2
) = G
0
-RTln(P
O2
)
R
T
l
n
P
O
2
P
O
2

s
c
a
l
e
[
a
t
m
]
10
-X
R
G=

F
G
0
-RTlnP
O2
1
G<0 : Ag
2
O stable at fixed P
O2
G>0 : Ag stable at fixed P
O2
G<0
Ag
2
O
stable
at T
G>0
Ag stable
at T
Temperature, K
G
F
0

[
K
J

m
o
l
-
1
]
0
-60
-40
-20
20
40
0 100 200 300 400 500 600 700
4
A
g
(
s
)

+

O
2
(
g
)
2
A
g
2
O
(
s
)

G
0
At equilibrium
0= G=

F
G
0
-RTlnP
O2

F
G
0
=RTlnP
O2
intersection
22
ELLINGHAM DIAGRAM
Richardsons nomographic scale for RTlnP
O2
23
Superposition
of Ellingham Diagram and RTlnP
O2
2A+O
2
2AO
R
G=
R
G
0
+RTlnP
O2
e.g. at T
2
term
R
G
0
= (cd)
is compensated
by term
-RTln(P
O2
) =(cd)
at P
O2
=10
-8
atm
so that
R
G=0
and reaction
2A+O
2
2AO
is at equilibrium
at P
O2
>10
-8
or T<T
2

R
G <0 Me is oxidised
at P
O2
<10
-8
or T>T
2

R
G >0 Me is oxidised

R
G
0
R
T
l
n
P
O
2
24
? What is critical oxygen partial pressure
P
O2
in the gas to avoid Cu oxidation at
1000
o
C and 1 atm total pressure?
Cu + O
2
->Cu
2
O answer P
O2
= 10
-7
atm
25
Example: What critical CO/CO
2
ratio in the gas to avoid Cu oxidation at 1000
o
C?
0
2 2 R1
0
2 2 R2
2 2
2 2
0
Cu2O CO
R3 R3
4 2
Cu CO2
0
R1 R
R1) 4Cu(s) + O (g) 2Cu O G
R2) 2CO(g) + O (g) 2CO (g) G
R3) 4Cu(s) + 2CO (g) 2Cu O+2CO R3 = R1 - R2
a P
G G RT ln
a * P
( G

| | | | | | | |
= + = = + = = + = = + =
| | | |
\ \ \ \
= = = =
2 2
0
Cu2O CO
2
4 2
Cu CO2
2
0 0
Cu2O CO
R1 R2
4
Cu CO2
0
CO
R2
CO2
a P
G ) RT ln RT ln
a P
a P
G RT ln G 2RT ln
a P
P
The nomographic scale for the term G 2RT ln
P
is added to the El

| | | | | | | | | | | | | | | |
+ + + + + + + +
| | | | | | | |
\ \ \ \ \ \ \ \
( ( ( ( ( ( ( (
| | | | | | | | | | | | | | | |
= + = + = + = +
( ( ( ( ( ( ( (
| | | | | | | |
( ( ( ( ( ( ( (
\ \ \ \ \ \ \ \

( ( ( (
| | | | | | | |

( ( ( ( | | | |
( ( ( (
\ \ \ \

lingham diagram
26
? What is critical CO/CO
2
ratio in gas to
avoid Cu oxidation at 1000
o
C and 1 atm
total pressure?
4Cu + 2CO
2
2Cu
2
O+2CO
answer CO/CO
2
= 10
-3.5
atm
27
Example: What critical H
2
/H
2
O ratio in the gas to avoid Cu oxidation at 1000
o
C?
0
2 2 R1
0
2 2 2 R2
2 2 2
2 2
0
Cu2O H2
R3 R3
4 2
Cu H2O
0
R1 R2
R1) 4Cu(s) + O (g) 2Cu O G
R2) 2H (g) + O (g) 2H O(g) G
R3) 4Cu(s) + 2H O(g) 2Cu O+2H R3=R1 - R2
a P
G G RT ln
a * P
( G

| | | | | | | |
= + = = + = = + = = + =
| | | |
\ \ \ \
= = = =
2 2
0
Cu2O H2
4 2
Cu H2O
2
0 0
Cu2O H2
R1 R2
4
Cu H2O
0
H2
R2
H2O
a P
G ) RT ln RT ln
a P
a P
G RT ln G 2RT ln
a P
P
The nomographic scale for the term G 2RT ln
P
is added to the Ell

| | | | | | | | | | | | | | | |
+ + + + + + + +
| | | | | | | |
\ \ \ \ \ \ \ \
( ( ( ( ( ( ( (
| | | | | | | | | | | | | | | |
= + = + = + = +
( ( ( ( ( ( ( (
| | | | | | | |
( ( ( ( ( ( ( (
\ \ \ \ \ \ \ \

( ( ( (
| | | | | | | |

( ( ( ( | | | |
( ( ( (
\ \ \ \

ingham diagram
28
? What is critical H
2
/H
2
O ratio in gas to
avoid Cu oxidation at 1000
o
C and 1 atm
total pressure?
4Cu + 2H
2
O 2Cu
2
O+2H
2
answer H
2
/H
2
O = 10
-3.7
atm
29
Example:
At what temperature SiO
2
can be reduced to Si by pure carbon?
(C+O
2
2CO line on the Ellingham Diagram)
0
2 2 R1
0
2 R2
2
R1) Si(s) + O (g) SiO G
R2) 2C + O (g) 2CO(g) G
R3) SiO (s) + 2C Si+2CO(g) R3= - R1 + R2

30
? At what temperature SiO
2
can be
reduced to Si by pure carbon?
31
ELLINGHAM DIAGRAM
EXAMPLE:
? Will Ni be oxidised at 1000
o
C at 1 atm
total pressure in nitrogen gas N
2
with
1ppm O
2
impurity?
2Ni + O
2
->2NiO
RTlnP
O2
=-150 kJmolO
2
-1

F
G
0
=-240 kJmolO
2
-1

R
G =
F
G
0
-RTlnP
O2
=
= -240 (-150) =-90 kJmolO
2
-1
<0
Ni will be oxidised
(critical P
O2
is 10
-10
atm)
32

F
G
0
vs T diagram for
hydrocarbons shows
that in general low molecular
weight hydrocarbons are
thermodynamically more stable
than those of high molecular
weight
This is used in Petroleum
industry for hydrocarbon
promoting cracking reactions by
heating
e.g.
C
n+m
H
2(n+m)+2
C
n
H
2n
+ C
m
H
2m+2
33
OTHER ELLINGHAM DIAGRAMS:
Ref: Y.K.Rao, Stoichiometry and thermodynamics of metallurgical
processes, Cambridge Univ. Press. 1985,
p. 371:
Chlorides, Fluorides:- Kellogg,Trans.AIME, 1950, v188, pp.862-72;
ibid.1951, 191, pp. 137-141
Oxides, Chlorides, Fluorides:Glassner, ANL-5750, Argonne
National Laboratory, Argonne, Ill., 1957
Oxides, Halides, Carbides:- Wicks & Block,Bulletin 605, Bureau of
Mines, US Dept. of Interio, Washinton, DC, 1963
Oxides, Sulfides, Halides, Nitrides, Hydrides, Selenides, Tellurides:
Reed, MIT Press, Cambridge, Mass., 1971
34
PREDOMINANCE DIAGRAMS
We can now predict the conditiosn for a particular chemical reactions
to proceed under non-standard conditions.
Question:
What can be done if gas contains several species and a number of
alternative products can be formed?
Answer:
The graphical representation concept can be extended to include
other variables
35
Graphical representation of multiple reaction equilibria as
functions of process variables
Two gas composition / activity variables + many condensed phases
+ total pressure on one graph analysis of which one is stable
Analyse sensitivity to process variables
Map over ranges of operating conditions
More possibilities
Easy for analysis
Use of computer power
36
- graphical representation of multiple reaction equilibria as functions of process
variables
EXAMPLE: Si-C-O system forms the basis for 2 important industrial processes:
1) Production of SiC from SiO
2
using C (SiC is used in abrasive / grinding and as
heat resistant refractory material)
2) Production of Si metal from SiO
2
using C (Si is used in photovoltaic cells for
converting solar energy into electricity)
Conditions necessary to produce these different products from the same starting
materials can be evaluated using : PREDOMINANCE DIAGRAMS
Feed
SiO
2(s)
| C
(s)
| ?O
2(gas)
SiC or Si
CO
,gas
Electric Energy
High T
Molten Zone
CO
2,g
SiO
g
37
EXAMPLE: Production of SiC or Si metal from SiO
2
using C
Feed SiO
2(s)
| C
(s)
| ?O
2(gas)
SiC or Si
CO
,gas
Electric Energy
High T
Molten Zone
CO
2,g
SiO
g
SiO
2(s)
C
O
+
S
i
O
2
(
s
)
S
i
li
q
+
C
O
2
(
g
a
s
)
C
(s)
CO
2(gas)
CO
gas
C
O
2
,
g
a
s
+
C
(
s
)
2
C
O
g
a
s
Si
liq
C
(s) Si
liq
2C
s
+SiO
2(s)
Si
liq
+2CO
gas
Possible Reactions
The question :
what are
conditions
(e.g. P
O2
and a
C
at a given T)
to produce
SiC or Si
38
EXAMPLE: Si-C-O SYSTEM, Temp FIXED
------------------------------------------------------------------------
Possible condensed phases/species: SiO
2
, SiC, Si, C,
Possible gaseous species:O
2
, CO, CO
2
, SiO,
------------------------------------------------------------------------
Question: What temperature and reduction/oxidation conditions
(P
O2
, a
C
, P
CO
, P
CO2
, ) are needed to get stable Si or SiC ?
------------------------------------------------------------------------
Variables selected for diagram: log(a
C
) and log(P
O2
)
Condensed phases for analysis: SiO
2
, SiC, Si
------------------------------------------------------------------------
39
-14 -13 -12 -11
-3
-2
-1
0
l
o
g
(
a
C
)
log(P
O2
)
SiC
Si
Si SiO
2
SiC SiO
2
SiC(s)
SiO
2(l)
Si(l)
(
4
)

C
(
s
)
+
0
.
5
O
2
(
g
)
-
>
C
O
(
g
)

P
C
O
=
1
0
-
1
a
t
m
P
C
O
=
1
0
-
2
a
t
m
P
C
O
=
1

a
t
m
C(s) stable
!
!
!
!

I
n
d
u
s
t
r
i
a
l

c
o
n
d
i
t
i
o
n
s

f
o
r

S
i
C
a
t

P
t
o
t
a
l
=
1
a
t
m
PREDOMINANCE DIAGRAMS are used to select operating
conditions fuel/O
2
ratio, Temperature, P
total
, other
Example: Si-C-O system at T=2133.5K
40
PREDOMINANCE DIAGRAMS CONSTRUCTION
Procedure:
1. Fix temperature and select 2 variables describing gas composition
or activity of an element (e.g. T=2133.5K, a
C
, P
O2
)
2. Identify all possible condensed phases (e.g.Si
liq
, SiO
2,liq
, SiC
s
)
3. Write down all possible reactions between combinations of these
condensed phases with selected variables and derive equations for
critical conditions (equilibria) corresponding to these reactions
4. Assess relative stabilities of the condensed phases and identify
ranges of stabilities of the condensed phases in terms of selected 2
variables
41
EXAMPLE Si-C-O SYSTEM, T=2133.5K
l
o
g
(
a
C
)
log(P
O2
)
0
?
SiC
? SiO
2
?
Si
Aim to define operation conditions in terms of a
C
and P
O2
at a given temperature to produce Si(l) or SiC(s) from SiO
2
(l)
Reactions to consider:
Si(l) + O
2
(g) -> SiO
2
(l) (1)
Si(l) + C(s) -> SiC(s) (2)
SiC(s) + O
2
(g) -> SiO
2
(l) +C (3)
For pure Si, SiC, SiO
2
:
a
Si
= 1, a
SiC
=1, a
SiO2
=1
42
( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) )
2 , solid solid solid 2
2 2
possilbe phases are 1.pure SiO ; 2.pure Si ; 3.pure SiC ;4. C in solution and 5.gas with O
PREDOMINANCE DIAGRAMS example : Si-C-O system, T=2133.5 K
Si l + O g -> SiO l
( (( ( ) )) )
( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) )
( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) )
0
R1
0
R2
0
2 2 R3
1 G =?
Si l + C s ->SiC s 2 G =?
SiC s + O g -> SiO l +C 3 G =?
---------------------------------------------------------------------
Data taken from Fact

2
2
-1
0 0
C ,2133.5 O ,2133.5
0 0 0
Si ,2133.5 SiC ,2133.5 SiO ,2133.5
Sage using View Data in Jmol :
G =-51566.0 G =-514127.7
G =-110659.5 G =-205727.7 G =-1150491.2
--------------------------------------------
( ( ( (

( (( ( ) )) ) ( (( ( ) )) )
( (( ( ) )) )
2 2
0 0 0
0
-1
SiO ,2133.5 Si ,2133.5 O ,2133.5
R1
0 0 0
0
SiC ,2133.5 Si ,2133.5 C ,2133.5
R2
------------------------------------------
G =G -G -G =-1150491.2- -110659.5 - -514127.7 =-525704.0Jmol
G =G -G -G =-205727.7- -110659.5 - -5156

( (( ( ) )) )
( (( ( ) )) )
-1
0 0 0
-1
R3 R1 R2
6.0 =-43502.2Jmol
G = G - G =-525704.0 -43502.2 = -482201.8 Jmol
43
(note logX=lnX/2.303)
PREDOMINANCE DIAGRAMS e.g. Si-C-O system, T=2133.5 K
==================== ==================== ==================== ====================
( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) )
2
2
2
2 2
0 0
-1
2 2 R1 F SiO ,2133.5
0
SiO 0 0
R1
R1 R1 R1 O
Si O O
R1 Si l + O g -> SiO l 1 G = G =-525704.0 Jmol
a
G
1
0 G= G RT ln G RT ln log P
a P P 2.3

======================================== ======================================== ======================================== =========================================== === === ===
| | | | | | | | | | | | | | | |
| | | | | | | | = + = + = = + = + = = + = + = = + = + =
| | | | | | | |
\ \ \ \ \ \ \ \
2
2
O
O C
03RT
log P -525704.0 / ( 2.303* 8.314* 2133.5 ) 12.9
log P 12.9 does not depend on a

= = = =
= = = = = = = =
44
0
O2 R1
R1 log P G / ( 2.303RT ) 12.9 = = = = = = = =
l
o
g
(
a
C
)
log(P
O2
)
(
1
)

S
i
(
l
)
+
O
2
(
g
)
S
i
O
2
(
l
)
Si SiO
2
-14 -13 -12 -11
-3
-2
-1
0
Reaction 1 produced
line logP
O2
=-12.9 which
divides the range of
conditions into two
to the right
more oxidising
SiO
2
is stable
to the left
more reducing
Si is stable
45
==================== ==================== ==================== ====================
( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) )
0 0
-1
R2 F SiC ,2133.5
0
0 0
R2 SiC
R2 R2 R2 C
Si C C
C
R2 Si l + C s ->SiC s 2 G = G =-43502.2 Jmol
G a 1
0 G= G RT ln G RT ln log a
a a a 2.303RT
log a

======================================== ======================================== ======================================== =========================================== === === ===
| | | | | | | | | | | | | | | |
= + = + = = + = + = = + = + = = + = + =
| | | | | | | |
\ \ \ \ \ \ \ \
C O2
-43502.2 / ( 2.303* 8.314* 2133.5 ) 1.1
log a 1.1 - d

oes not dep

e

nd on P

= == =
= = = =
= = = =
46
l
o
g
(
a
C
)
log(P
O2
)
SiC
Si
-14 -13 -12 -11
-3
-2
-1
0
0
C R2
R2 log a G / ( 2.303RT ) 1.1 = = = = = = = =
(2) Si(l) + C(s) -> SiC(s)
Reaction 2 produced line log(a
C
)=-1.1
which divides the range of conditions into two
Up from the line higher a
C
SiC is stable
Down from the line
- lower a
C
-
Si is stable
47
==================== ==================== ==================== ====================
( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) )
2
2
2 2
0
-1
2 2 R3
0
SiO C 0 0
R3 C
R3 R3 R3 C O
SiC O O
C
R3 SiC s + O g -> SiO s +C 3 G = -482201.8 Jmol
a a
G a
0 G= G RT ln G RT ln log a log P
a P P 2.303RT
log a

======================================== ======================================== ======================================== =========================================== === === ===
| | | | | | | | | | | | | | | |

| | | | | | | | = + = + = + = + = + = + = + = + = + = + = + = +
| | | | | | | |
\ \ \ \ \ \ \ \
2 2
2
C O
O
C O
( 482201.8 ) / ( 2.303* 8.314* 2133.5 ) log P
log a 11.8 log P - depends on both

a and P
= + = + = + = +
= + = + = + = +
48
0
C R3 O2 O2
R3 log a G / ( 2.303RT ) log P 11.8 log P = + = + = + = + = + = + = + = +
l
o
g
(
a
C
)
log(P
O2
)
(3) SiC SiO
2
-14 -13 -12 -11
-3
-2
-1
0
(
3
)

S
i
C
(
s
)

+

O
2
(
g
)
S
i
O
2
(
l
)

+

C
(
s
)
Reaction 3
produced
line
log(a
C
)=
11.8+logP
O2
which divides
the range
of conditions
into two
Up or Left
from the line
higher a
C
and
lower P
O2
SiC is stable
Down or Right
from the line
- lower a
C
or
more oxidising-
SiO
2
is stable
49
==================== ==================== ==================== ====================
( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) )
2
2
2
2 2
0 0
-1
2 2 R1 F SiO ,2133.5
0
SiO 0 0
R1
R1 R1 R1 O
Si O O
R1 Si l + O g -> SiO l 1 G = G =-525704.0 Jmol
a
G
1
0 G= G RT ln G RT ln log P
a P P 2.3

======================================== ======================================== ======================================== =========================================== === === ===
| | | | | | | | | | | | | | | |
| | | | | | | | = + = + = = + = + = = + = + = = + = + =
| | | | | | | |
\ \ \ \ \ \ \ \
( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) )
2 2
O
0 0
-1
R2 F SiC ,2133.5
0
SiC
R2 R2
Si C
O
03RT
log P -525704.0 / ( 2.303* 8.314* 2133.5 ) 12.9
R2 Si l + C s ->SiC s 2 G = G =-43502.2 Jmol
a
0 G= G RT ln
log P 12.9
a a

= = = = = = = =
| || |
= + = + = + = +
= = = =

\ \\ \
( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) )
0
0
R2
R2 C
C
C
0
-1
2 2 R
C
3
R3
G 1
G RT ln log a
a 2.303RT
log a -43502.2 / ( 2.303* 8.314* 2133.5 ) 1.1
R3 SiC s + O g -> SiO s +C
log a 1.
3 G = -482201.8 Jm
G
1
ol
0

| | | | | | | | | | | |
= + = + = + = +
= = = =
= == =
| | | | | | | |
\ \ \ \
= = = = = = = =
= == =
2
2
2
2 2
2
0
SiO C 0 0
R3 C
R3 R3 C O
SiC O O
C O C O
a a
G a
= G RT ln G RT ln log a log P
a P P 2.303RT
log a ( -482201.8 ) / ( 2.303* 8.314* 2133.5 ) log P log a 11 .8 lo P g

| | | | | | | | | | | | | | | |

| | | | | | | | + = + = + + = + = + + = + = + + = + = +
| | | | | | | |
\ \ \ \ \ \ \ \
= + = + = + = + = + = + = + = +
50
0
O2 R1
R1 log P G / ( 2.303RT ) = = = =
0
C R3 O2
R3 log a G / ( 2.303RT ) log P = + = + = + = +
l
o
g
(
a
C
)
log(P
O2
)
SiC
Si (2)
(3) SiC SiO
2
(
1
)

S
i
(
l
)
+
O
2
(
g
)
S
i
O
2
(
l
)
(2) Si(l) + C(s) -> SiC(s)
(
3
)

S
i
C
(
s
)

+

O
2
(
g
)

S
i
O
2
(
l
)

+

C
(
s
)
(1) Si SiO
2
-14 -13 -12 -11
-3
-2
-1
0
0
C R2
R2 log a G / ( 2.303RT ) = = = =
51
0
O2 R1
R1 log P G / ( 2.303RT ) = = = =
l
o
g
(
a
C
)
log(P
O2
)
(
1
)

S
i
(
l
)
+
O
2
(
g
)
-
>
S
i
O
2
(
l
)
(
3
)

S
i
C
(
s
)

+

O
2
(
g
)

-
>

S
i
O
2
(
l
)

+

C
(
s
)
(1) Si(l)+O
2
(g)->SiO
2
(l)
(1) Si7 6 7 6 7 6 7 6SiO
2
(2) Si(l) + C(s) -> SiC(s)
-14 -13 -12 -11
-3
-2
-1
0
Reaction 1 Line divides
the range of conditions
into two:
Si is not stable to the right
SiO
2
is not stable to the left
- this eliminates
redundant parts
of the two other lines
52
-14 -13 -12 -11
-3
-2
-1
0
l
o
g
(
a
C
)
log(P
O2
)
(
1
)

S
i
(
l
)
+
O
2
(
g
)
-
>
S
i
O
2
(
l
)
(2) Si(l) + C(s) -> SiC(s)
(
3
)

S
i
C
(
s
)

+

O
2
(
g
)

-
>

S
i
O
2
(
l
)

+

C
(
s
) SiC
Si (2)
(1) Si SiO
2
(3) SiC SiO
2
Si
Reaction 2 Line divides the range
of conditions into two:
Si is not stable Up
SiC is not stable Down
- this eliminates redundant part
of another line
53
-14 -13 -12 -11
-3
-2
-1
0
l
o
g
(
a
C
)
log(P
O2
)
SiC
Si (2)
(1) Si SiO
2
(3) SiC SiO
2
Si
SiC
SiO
2
Finally, three lines derived from
Reactions 1, 2 and 3 divide the range
of conditions into three
fields of stability of SiC, Si and SiO
2
54
-14 -13 -12 -11
-3
-2
-1
0
l
o
g
(
a
C
)
log(P
O2
)
SiC
Si (2)
(1) Si SiO
2
(3) SiC SiO
2
SiC(s)
SiO
2(l)
Si(l)
C(s) stable
Oxidising
Reducing
C
a
r
b
u
r
i
s
i
n
g
D
e
c
a
r
b
u
r
i
s
i
n
g
55
-14 -13 -12 -11
-3
-2
-1
0
55
l
o
g
(
a
C
)
log(P
O2
)
SiC
Si (2)
(1) Si SiO
2
(3) SiC SiO
2
SiC(s)
SiO
2(l)
Si(l)
C(s) stable
The diagrams show the ranges of stability of
SiC, Si and SiO
2
in terms of a
C
and P
O2
.
The gas phase, however, contains a number
of other species including CO, CO
2
, SiO etc.
At these reducing conditions CO(g) is a
predominant species.
For the process run at P
total
=1atm , the P
CO
-
partial pressure of CO can only be less than
1atm. P
CO
isobars are important.
56
( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) )
CO
2
- other gaseous species PREDOMINANCE DIAGRAMS e.g. Si-C-O system, T=2133.5 K
To constract the lines with constant CO partial pressure P ,
the following reaction is analysed:
R4 C s + 0.5O g -> CO g
( (( ( ) )) )
2
2
2
2
C CO O
0
-1
R4
0
0
R4 CO
R4 R4 C CO O
0.5
C O
C CO O
4 G = -297038.3 Jmol
G P
0 G= G RT ln log a log P 0.5 log P
2.303RT a P
log a -297038.3 / ( 2.303* 8.314* 2133.5 ) log
log a 7
P 0.5 log P

.

3 log P 0.5 log P

= + = + = + = +
| | | | | | | |
| | | | = + = + = + = + = + = + = + = +
| | | |
\ \\ \

= + = + = + = +
2
2
2
CO C O
CO C O
CO C O
for P =1 log a 7.3 0 0.5 log P
for P =0.1 log a 7.3 1 0.5 log P
for P =0.01 log a 7.3 2 0.5 log P
= + = + = + = +
= = = =
= = = =
57
( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) )
2
2
C CO O
- other gaseous species PREDOMINANCE DIAGRAMS e.g. Si-C-O system, T=2133.5 K
R4 C s + 0.5O g -> CO g
log a 7.3 log P 0.5 log P = + = + = + = +
-14 -13 -12 -11
-3
-2
-1
0
l
o
g
(
a
C
)
log(P
O2
)
SiC
Si (2)
(1) Si SiO
2
(3) SiC SiO
2
SiC(s)
SiO
2(l)
Si(l)
(
4
)

C
(
s
)
+
0
.
5
O
2
(
g
)
-
>
C
O
(
g
)

P
C
O
=
1
0
-
1
a
t
m
P
C
O
=
1
0
-
2
a
t
m
P
C
O
=
1

a
t
m
C(s) stable
!
!
!
!

I
n
d
u
s
t
r
i
a
l

c
o
n
d
i
t
i
o
n
s

f
o
r

S
i
C
a
t

P
t
o
t
a
l
=
1
a
t
m
P
CO
=const lines
provide
additional
information
on gas
composition
NOTE!
Gas contains
other species.
These
diagrams
are used
to select
operating
conditions:
fuel/O
2
ratio
Temperature
P
total
other
58
-14 -13 -12 -11
-3
-2
-1
0
l
o
g
(
a
C
)
log(P
O2
)
SiC
Si (2)
(1) Si SiO
2
(3) SiC SiO
2
SiC(s)
SiO
2(l)
Si(l)
(
4
)

C
(
s
)
+
0
.
5
O
2
(
g
)
-
>
C
O
(
g
)

P
C
O
=
1
0
-
1
a
t
m
P
C
O
=
1
0
-
2
a
t
m
P
C
O
=
1

a
t
m
C(s) stable
!
!
!
!

I
n
d
u
s
t
r
i
a
l

c
o
n
d
i
t
i
o
n
s

f
o
r

S
i
C
a
t

P
t
o
t
a
l
=
1
a
t
m
Comments on PREDOMINANCE DIAGRAM for the Si-C-O system at 2133.5 K
1) Gas
solution
over
condenced
phases
2) Complex
multi-
component
equilibria
=
equilibria
of simple
subsystems
3) Crossing the SiC/SiO
2
line
along ~1atm CO isobar
will produce SiC
4) CO in equilibrium with C
has P
CO
>> 1atm
strong driving force
SiO
2(s)
C
(s)
CO
2(gas)
CO
gas
Si
liq
59
In addition to thermodynamic stability, other factors should be taken into
account. E.g. solid/solid reactions are slow- liquid phase is desirable to accelerate
reactions.
* Also, CO is
predominant
gaseous species to
remove oxygen
P
CO
should
approach 1 atm.
* Other gaseous
species (e.g. SiO)
and other phases
(e.g. SiO liquid)
should be
considered.
Gaskell Introduction to the
thermodynamics of materials, pp
420-433.
Alternative axes - more convenient for analysis
60
PREDOMINANCE DIAGRAMS- Si-C-O SYSTEM
- Other variables can also be selected for axes and
- Other variables can also be fixed. E.g.:
Construction of the
Predominance
diagram
using logP
CO
and 1/T
coordinates
at constant P
CO2
=10
-12
atm
61
PREDOMINANCE DIAGRAMS- Si-C-O SYSTEM
- Other variables
P
CO
is far less
than 1 atm
in this range
of temperatures
Si can be
produced
only at high
tempertures
62
PREDOMINANCE DIAGRAMS Example: selection of conditions for roasting of
the Cu-Fe-sulphides to form more soluble CuSO
4
and Cu oxides and insoluble Fe
oxides (rather than soluble sulphates) Ref: Biswas and Davenport.
Shaded area-
operating
conditions
at P
total
=1atm
O
2
is added
to burn S to SO
2
63
4
Shaded area-
operating
conditions
at P
total
=1atm
Higher
temperatures
favour formation
of Fe
2
O
3
64
4
Higher
temperatures
favour formation
of Fe
2
O
3
65
PREDOMINANCE DIAGRAMS Example: PbS smelting (FactSage).
P
(
to
t
a
l)=
0
.1
a
t
m
PbO(l)
PbS(l)
PbSO
4
(s
2
)
PbOPbSO4(s)
(PbO)4(PbSO4)(s)
Pb(l)
P
(t
o
ta
l)=
1
a
tm
Pb-S-O, 1200 C
'+' = 0.1 atm P(total) isobar
log
10
(P(S
2
)) (atm)
l
o
g
1
0
(
P
(
O
2
)
)

(
a
t
m
)
-10 -9 -8 -7 -6 -5 -4 -3 -2 -1 0
-14
-13
-12
-11
-10
-9
-8
-7
-6
-5
-4
-3
-2
-1
0
66
References:
Lee, H.G., 1999. Chemical thermodynamics for metals and materials , Imperial
College Press, London.
D. Gaskell, 2008. Introduction to Thermodynamics of Materials,
Taylor&Francis, USA.
Y.K.Rao, 1985. Stoichiometry and thermodynamics of metallurgical processes,
Cambridge Univ. Press.
Biswas and Davenport, Extractive Metallurgy of Copper, Pergamon

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