CH321 Thermodynamics &

Phase Equilibria

Lecture # 31-33

GIK Institute of Engineering Sciences and Technology

Faculty of Chemical Engineering
Fall Semester 2014
Dr Khurram Imran Khan

Multireaction: Alternate Criterion of

Equilibrium for Computer Program
The criterion is based on that at equilibrium the total
Gibbs energy of the system has its minimum
value.
The total Gibbs energy of a single phase system:

G
t

T ,P

g n1 , n2 , n3 ,...., nN

We will find the set of {ni} which minimizes Gt for

specified T and P, subject to constraints of material
balance.
The standard solution of this method is based on the
Method of Lagranges undetermined multipliers
On next slides the method is described for Gas-Phase
Reactions.

Constraini
ng
Equations

n a

i ik

k 1, 2,...., w

Ak

Number of
atoms of the
kth element
present in
each molecule

Total Number of atomic masses of the kth element

n a

i ik

k 1, 2,...., w

Ak 0

Total number of
elements
comprising the
system

2 Lagrange Multiplier

Summed over k

n a

i ik

Ak 0

n a
k

i ik

Ak 0

k 1, 2,...., w

New function formed, identical to Gt and

incorporates the constraints of material
balance.

F G k
t

n a

i ik

Ak

4Criterion of the equilibrium

F
G
t

n
i T , P , n j

T , P ,n j

i k aik 0
k

k aik 0
k

i 1, 2,...., N

i 1, 2,...., N

i Gio RT ln fi / fi o

i Gio RT ln fi / Pi o

G G
o
i

o
fi

fi yii P

i G RT ln yii P / Pi
o
i

Gio RT ln yii P / Pi o k aik 0

k

na

w- material balance equations

N-Equilibrium equations

i ik

Ak

i 1, 2,..., N

k 1, 2,...., w

Example 13.14
Calculate the equilibrium composition at 1000 K and 1
bar of a gas phase system containing the species CH4,
H2O, CO, CO2 and H2. In the initial unreacted state there
are present
mole
CH-14 and
3 omole
O. J mol -1
G o 219
720of
J mol
, G
of
192H2420
fCH 4

f H 2O

G ofCO 200 240 J mol-1 , G ofCO 395 790 J mol -1

2

n a

i ik

k 1, 2,...., w

Ak

Gio RT ln yii P / Pi o k aik 0

k

i 1, 2,..., N

Element k
Carbon

Oxygen

Hydrogen

Ak = no. of atomic masses of k in the system

AC = 2
Species i

AO = 3

AH = 14

aik = no. of atoms of k per molecule of i

CH4

aCH4,C = 1

aCH4,O = 0

aCH4,H = 4

H 2O

aH2O,C

aH2O,O

aH2O,H

CO

aCO,C

aCO,O

aCO,H

CO2

aCO2,C

aCO2,O

aCO2,H

aH2,C

aH2,O

aH2,H

H2

Fuel Cells
Acid electrolyte

H 2 2H 2e
1
2

Reaction at Anode

H 2 12 O 2 H 2 O g
Overall Reaction

O 2 2e 2H H 2O g Reaction at Cathode

Alkaline electrolyte

Reaction at Anode

H 2 2OH 2H O g 2e
1
2

O 2 2e H2O g 2OH

H 2 12 O 2 H 2 O g
Overall Reaction

Reaction at Cathode

Proton-Exchange Membrane

n from: http://energydesignresources.com/resources/e-news/e-news-90-fuel-cells

Nafion
Sulfonated
Tetrafluoroethyl
ene
Ionomer

(PANI-F)
Polyaniline
Fibers
with Pt
nanoparticles

n from: http://www.rsc.org/Publishing/ChemTech/Volume/2008/06/spray_electrode

Fuel Cell Operation

For steady-state flow
process, the energy
balance

H Q Welect

Q T S

Electrical Work of
a reversible Cell

H T S Welect

Welect H T S G

For each molecule of

hydrogen consumed, 2
electrons pass to the
external circuit

Q H G
q 2 N A e coulomb

F eN(Faradays
constan
A

q 2F , F Faraday's constant 96 485 coulomb mol

Welect 2F E joule

Welect G
E

2F
2F

Calculations example of above

formulas of Hydrogen/Oxygen
fuel cell at 25oC and 1 bar with
assumption of Ideal gas (Pure H2, O2
as gases and H2O vapour.
Calculations example of above
formulas of Hydrogen/Air fuel
cell at 25oC
and 1 bar with
assumption of Ideal gas (Pure H2, air
as gases
ig and
ig H2O vapour.

Hint Gi Gi RT ln yi

(volt)

k
n
a
h
T
!
u
o
y