Chapter 3:

Rate Laws and

Stoichiometry

Objectives
After completing this chapter, students are be
able to:
Define rate law, reaction order and activation
energy
Set up stoichiometry table for batch and flow
system

Rate law
Activation Energy
Reaction Order

Rate Law
For a reaction given below:
aA + bB cC + dD

rA
rB rC rD

a b c
d
Example:
2NO + O2 2NO2

rNO rO2 rNO2

2 1
2

Rate Law
The rate law will give -rA = [kA(T)][fn(CA,CB,)]
Rate law gives the relationship between the reaction rate
and concentration.
k= specific reaction rate determined by Arrhenius equation

k Ae

E
RT

where
E = activation energy
R = universal gas constant
T = temperature
A = frequency factor
* k and A units depends on overall
reaction order

Reaction Rate Constant

At temperature T0,

k (T0 ) Ae

At temperature T, k (T ) Ae

E
RT0

E
RT

Taking the ratio to obtain,

Energy

k (T ) k (T0 )e

A+B

E 1 1

R T0 T

Activation Energy: defined as

the energy that must be
overcome in order for a
chemical reaction to occur.

E
C

Reaction Coordinate

Reaction Rate Constant

k

k = A exp(-E/RT)
T
lnk

ln( k) = ln A - (E/R) x 1/T

T

Slope = -E/R

1/T

Rxn1: High E

lnk

k with higher E is more sensitive to

temperature than those with low E
Rxn 2: Low E
1/T

POLYMATH Results
07-20-2009
Linear Regression Report
Model: lnk = a0 + a1*K
Variable
a0
a1

Value

95% confidence

38.923319
-1.461E+04

0.9924566
320.53961

General
Regression including free parameter
Number of observations = 5
Statistics
R^2 =
R^2adj =
Rmsd =
Variance =

0.9998574
0.9998099
0.0051949
2.249E-04

Reaction Order
Rate law is a behavior of a reaction.
Consider the following reaction:
aA + bB cC + dD
The rate law may be written as Power Law Model:

rA kCA C B
where k = specific reaction rate
= order with respect to A
= order with respect to B
+ = overall order

Reaction Order
In the previous example, i.e., aA + bB cC + dD
The rate law was written as:
(-rA) = k CACB
Elementary Rate Law
if the Stoichiometry
coefficients are the same
as the individual reaction
order of each species.
H2 +I2 2HI
(rHI) = k CH2 CI2

Non-elementary Rate
Law
CO+CI2COCI
r kC C 3 / 22
CO

CO

CI 2

This rxn is 1st order

with respect to CO,
3/2 order with
respect to CI2 and 5/2
order overall.

Reaction Order
Overall reaction order can be determined by the unit of k
Reaction Order

Rate Law

k unit

Zero

-rA=kA

mol/dm3.s

One

-rA=kACA

s-1

Two

-rA=kACA2

(dm)3/mol.s

Three

-rA=kACA3

(dm3/mol)2.s

Self Test : Rate Law

1) What is the reaction rate law for the reaction
A+ BC if the reaction is elementary? What is rB? What
is rC ?

rA kCAC B1/ 2
rA
rB

1 1/ 2
1
k
rB rA C AC B1/ 2
2
2
rA
rC

1
1
rC rA kCAC B1/ 2

2) Calculate the rates of A, B, and C in a CSTR where the

concentrations are CA = 1.5 mol/dm3, CB = 9 mol/dm3 and kA =
2 (dm3/mol)(1/2)(1/s).

dm

2
mol

rA

mol
rA 9
dm 3s
mol
rB 4.5
dm 3s
mol
rC 9
dm 3s

1/ 2

1
s

mol mol
1
.
5
9
3

dm dm 3

1/ 2

Reversible Reaction
Rate law for reversible reaction must
Satisfy thermodynamic relationships at equilibrium and
Reduce to the irreversible rate law when the
concentration of one or more of the reaction products
is zero
General reaction
aA + bB cC + dD
c
d
CCe
C De
thermodynamic equilibrium relationship K C a b
C AeC Be

Reversible Reaction
Example:
2C6H6

k-B
C12H10 + H2 ;
kB

2B D + H2

Rate of deformation of benzene

-rB, forward = kBCB2
Rate of formation of benzene
rB, reverse = k-BCDCH2
Thus,
rB,net = rB, forward + rB, reverse
rB, net = -kBCB2 + k-BCDCH2

concentration
equilibrium
constant

- rB, net = kB(CB2 (CDCH2)/KC) Kc = kB/k-B

Problem 3.7
The rule of thumb that the rate of reaction doubles for a
10 C increase in temperature occurs only at a specific
temperature for a given activation energy. Develop a
relationship between the temperature and activation
energy for which the rule of thumbs holds. Neglect any
variation of concentration with temperature.
Determine the activation energy and frequency factor
from the following
K (min-1)

0.001

0.050

T(C)

60.0

100.0

Stoichiometry

Useful Definitions
Reaction:

1. Parameter

b
a

c
a

d
a

N i 0 Ci 0
y

i0
N A0 C A0 y A0

2. Net mole change for the reaction

d c b
1
a a a

3. Relationship between and initial mole fraction of A

Change in total number of moles when complete conversion of A is attained

Total number of moles of all species fed to the reactor

N AO
y A0
NTO

N X N A0
NT
T0
1 X
N TO
NT 0

Batch System
Reaction:

A B C D

Stoichiometric Table for a Batch System

Species

Symbol

Initial

Change

Remaining

NAO

-NAOX

NA=NAO(1-X)

NBO=NAOB

-b/a NAOX

NB=NAOB-b/a NAOX

NCO=NAOC

c/a NAOX

NC=NAOC+c/a NAOX

NDO=NAOD

d/a NAOX

ND=NAOD +d/a NAOX

Inert

NIO=NAOI

NI=NAOI

NTO

NT=NTO + NAOX

Concentrations

Constant Volume
Batch System

With a condition that reaction occurred in liquid form or gas

phase that occurred in rigid (e.g. steel) batch reactor, V=Vo
N A N AO (1 X )

C AO (1 X )
V
VO
b
N AO ( B X )
N
b
a
CB B
C AO ( B X )
V
VO
a
CA

Stoichiometric Table for a Constant Volume Batch System

Remaining

Concentrations

.......

NA=NAO(1-X)

CA=CAO(1-X)

.......

NB=NAOB-b/a NAOX

CB=CAO((B-b/a*X)

NC=NAOC+c/a NAOX

CC=CAO(C+c/a*X)

.......

ND=NAOD +d/a NAOX

CD=CAO(D +d/a*X)

.......

NI=NAOI

CI=CAOI

N =N

+ N X

BOMB CALORIMETER
An apparatus for measuring the heat generated by a chemical
reaction, change of state, or formation of a solution.

Self Test:
Write the rate law for the elementary liquid phase reaction;

3 A 2 B 4C
solely in terms of conversion(-rA as a function of X). The feed
to the batch reactor is equal molar A and B with CA0 = 2
mol/dm3 and kA= 0.01 (dm3/mol)41/s.
a) What is the rate law?
b) What is the concentration of A and B?
a)

rA kCA C B

b) Liquid phase,V=V0 (no volume change)

CA

CB
B

N AO (1 X )
NA
NA

C AO (1 X )
V
VO
VO
NB
NB

V
VO

N AO ( B
VO

b
X)
b
a
C AO ( B
X)
a

N BO

1
N AO

Species A is the limiting reactant because the feed is equimolar in A and B.

2
A
B
3
b
2/3

a
1
rA
rA

4
C
3
2
2
; C B C AO (1
X)
3
3

k C AO 1 X C AO (1
X )
3

2
5
3
kCAO 1 X (1
X )2
3
3

 dm

rA 0.01
mol
3

1 2mol

3
s dm

2
2
1 X (1 X )
3

2
mol
2
rA 0.321 X (1 X )

3
3
dm .s
3

Variable Volume
Batch System
Usually involve gas phase reaction, V V0.
The reactor volume may be related to initial reactor volume (V0)
and other operating parameters (P0, T0, P, and T)

V Vo

N T Po T Z
( ) ( )
N TO P To Z o

Vo (1 X )(

Po T Z
) ( )
P To Z o

For
Ideal Gas

V Vo

N T Po T
( )
N TO P To

Vo (1 X )(

Po T
)
P To

Example 3.3
Considering the stoichiometric table from
example 3.2, if the initial mixture consists
solely of sodium hydroxide at a concentration
of 10 mol/dm3 and the glyceryl stearate at a
concentration of 2 mol/dm3, what is the
concentration
of
glycerine
when
the
conversion of sodium hydroxide is
(a) 20 %
(b) 90 %

Example 3.6
The reversible gas phase decomposition of nitrogen
tetroxide, N2O4, to nitrogen dioxide, NO2,
N 2O4 2NO2

is to be carried out at constant temperature. The feed

consists of pure N2O4 at 340K and 202.6 kPa. The
concentration equilibrium constant, KC at 340K is 0.1
mol/dm3.
Calculate the equilibrium conversion of N2O4 in a
constant volume batch reactor.

FAO
FBO
FCO
FDO
FI

Flow System

FA
FB
FC
FD
FI

Consider reaction where A is a limiting reactant in a flow reactor

with the reaction,
b
c
d

Stoichiometric Table for a Flow System

Species

Initial

Change

Remaining

FAO

-FAOX

FA=FAO(1-X)

FBO=FAOB

-b/a FAOX

FB=FAOB-b/aFAOX

FCO=FAOC

c/a FAOX

FC=FAOC+c/a FAOX

FDO=FAOD

d/a FAOX

FD=FAOD +d/a FAOX

Inert

FI

FI

where i

F
FTO

iO

FAO

y
iO
y AO

FT=FTO + FAOX

Concentrations

Flow System:
Liquid Phase Reaction
v = vO

FA=FAO(1-X)
Since FA=CAv

FB=FAOB-b/aFAOX
CB=CAO(B-b/a*X)

CAv=CAOvO(1-X)
CA=CAO(1-X)
Stoichiometric Table for a constant volumetric flow rate system
Change

Remaining

Concentrations

FA=FAO(1-X)

CA=CAO(1-X)

FB=FAOB-b/aFAOX

CB=CAO(B-b/a*X)

FC=FAOC+c/a FAOX

CC=CAO(C+c/a*X)

FD=FAOD +d/a FAOX

CD=CAO(D+d/a*X)

FI

CI

FT=FTO + FAOX

Similar
with
batch
system

Flow System:
Gas Phase Reaction
In a gas phase flow system,
v v0 (1 X )

Thus,

T P0
T0 P

FA FAO (1 X ) T0 P
(1 X ) T0 P

C AO
v
vO (1 X ) T P0
(1 X ) T P0
b
b
FAO ( B X )
( B X )
F
T0 P
T0 P
a
a
CB B
C AO
v
vO (1 X ) T P0
(1 X ) T P0

CA

At constant temperature and pressure, if the rate of reaction was

P
rA kCA2C B1
C A0 A 0
RT
b
3
2
kCAO (1 X ) ( B X )
y B 0 C B 0 FB 0

a
B
r A
y A0 C A0 FA0
3

(1 X )

Stoichiometry in Extent
of Reaction Analysis
Using = XFA0, All labels in the
previous tables can be converted
into the extent of reaction
Mole balance can be attained by
using either the stoichiometry or
the extent of reaction method

The End