Lecture 2

Stoichiometry and Chemical

Reaction Equilibria

Departemen Teknik Kimia

Universitas Indonesia

Stoichimetry, Extent of Reaction and

Conversion
Stiochiometry coefficients
a A+ b B c C + d D
A + b/a B c/a C + d/a D
= c/a + d/a b/a -1

A A + B B + CC + D D =0
A = -1, B = - b/a, C = c/a, D = d/a
I : coeff. stoichiometry
v A 0

Extent of reaction,

i i

dn1/v1 = dn2/v2 = dn3/v3 = = dni/vi = d

= (ni-ni0)/vi

Conversion, X
X = (ni0-ni)/ni0 = - (vi/nio)

Stoichiometric Equation

This describes the overall reaction but the reaction order cannot
be deduced from it.

Examples:

H2 I2

2HI

rf =
kfCH CI

and rb =
kbCHI2

2 C ( 2nd order overall)

Forward reaction is 1st order in CH 2 and
I
2
2
Reverse reaction is 2nd order in CHI

Compare the above reaction with the analogous nonelementary

reaction between H2 and Br2 .
k1
k1C H 2 C Br 1 2
2
H 2 Br2
2HBr
r

f
k 2 C HBr C Br2
k2

Chemical Reaction Equilibrium

Kinetics vs. Themodynamics

Chemical Reaction Equilibria

Equilibrium state for given T and P

Criteria :

(G)T,P = (G/)T, P=

vi i 0

(G) : Gibbs free energy change, i: the chemical potential

(G)T , P vi (Gio RT ln ai ) 0
i
c/a

- RT ln Ka = G

a
a
RT ln
aa
C

d /a

D
b/a
B

Consider the general reversible reaction:

aA bB

cC d D

Therefore:

Therefore:

rfA k fAC AaCBb

rbA kbACCc CDd

k fAC C k C C
a
A

k fA
kbB

At equilibrium rA=0

b
B

c
bA C

c
C
a
A

C C
KC
CC

rA rfA rbA 0
d
D

rfA = rbA

d
D
b
B

Thermodynamic equilibrium relationship

H RX
K (T ) K C (T1 ) exp
Thermodynamic equilibrium constantC
R

1 1

T1 T

 H RX
K C (T ) K C (T1 ) exp
R
Endothermic

1 1

T1 T
Exothermic

KC

KC

Chemical equilibrium

All reactions are reversible in principle.

The extent of reversibility depends on -G, the Gibbs
Free Energy change.

G RTInK p

Where Kp is the equilibrium constant in

terms of partial pressures.

If Kp is large, reaction is essentially irreversible, which

means that the equilibrium position lies very far to the
product side.

Equilibrium Constants
K a K K P
c/a

KC

C
C

CC
C

D
b/a

c/a

KC

d /a

K a K K P

C C
CC
C

ai = fi / fi,o= i Pi

d /a

D
b/a
B

K P KC (RT )

Impact of T, P, Inert changes

Impact of T, P, Inert changes

Temperature change

d ln K/dT = Ho(T) /RT2

H o (T ) H o C op dT
plot log K vs 1/T , slope = -(Ho/R), (see Fig EC-1.1)
Exo. Reaction (Ho negative), K decreases with increasing T
Endo. Reaction (Ho positive), K increases with increasing T

Total pressure change

Inert change

Ka=Kf/P (

Pi=yi P

KP=Ky P
b
n aAnB
c d
nC
nD

) [P/nA + nB+nC +nD + nI] c+d-a-b

Calculation Procedure
Determine (Go) or (Ho).
a A + b B c C + d D maka:
Xo = c. Xof,C + d. Xof,D a. Xof,A b. Xof,B , X : G, H
Calculate KP at T

d ln K P H o (T )
o

RT
ln
K
(
T
)

G
(T )
2
dT with HoRT
(T) = Ho(25oC) +C dT
p

Calculation Procedure
Combine
constant

equilibrium

K i ai

composition

aC .a D

a A .a B

and

Equilibrium

Express in Extent of reaction, composition or conversion

vi Ai 0

vi
noi ni
Xi

noi
noi

Solve analytically/graph or numerically

Example 3-6 The reversible gas-phase decomposition of nitrogen

tetroxide, N2O4, to nitrogen dioxide, NO2, is to be carried out at
constant temperature. The feed consists of pure N2O4 at 340 K and
202.6 kPa (2 atm). The concentration equilibrium constant, Kc, at 340
K is 0.1 mol/dm3.
A 2B

concentration equilibrium constant:

at
equilibrium !!

(a) Calculate the equilibrium conversion of N2O4 in a constantvolume batch reactor.

at
equilibrium !!

(b) Calculate the equilibrium conversion of N2O4 in a flow

reactor.
at
equilibrium !!

(c) Assuming the reaction is elementary, express the rate of

reaction solely as a function of conversion for a flow system
and for a batch system.
Elementary reaction:

A 2B

for flow system

for batch system
(d) Determine the CSTR volume necessary to achieve 80% of
the equilibrium conversion.

CSTR design equation

HW2

Scott Fogler

P3-11A
P3-15B
P3-16B