CHE 326

CHEMICAL
REACTION
ENGINEERING I
FIRST OF THREE
COURSES

Chemical Reaction
Engineering
field that studies
1. the MECHANISMS and RATES of chemical
reactions and
2. the DESIGN of the reactors in which they take
place
RATES: HOW FAST REACTION OCCURS
MECHANISMS: proposed series of steps by which
reaction is assumed to occur at molecular level
DESIGN :TYPE , SIZE and REACTION CONDITIONS
IN THE REACTOR

Chemical Reaction
Engineering
is at the heart of virtually every
chemical process.
Reactor may be small but it is crucial
to the economics of the process
It separates the chemical engineer
from other engineers.
Process Industries Draw Heavily
on Chemical Reaction Engineering

mical Reactor and TYPICAL CHEMICAL PRO

Physical treatment
step

chemical treatment
step

Physical treatment
step

RAW
MAT

RECYLE

TYPICAL CHEMICAL PROCESS

Physical treatment steps: UNIT

OPERATIONS
Heating
Cooling
washing
Distillation
Filtration
Drying

PRODUCTS

MANY CHEMICAL
UBIQUITOUS REACTIONS

OUR BODIES
ENVIRONMENT-decomposition of organics
OZONE LAYER DEPLETION
SMOG
POWER GENERATION
CORROSION
INDUSTRIAL PRODUCTS
DOMESTIC PRODUCTS

**NO

WORLD WITHOUT CHEMICAL REACTIONS

Chemical reaction as a
multidisciplinary subject

identification of straight lines

intercepts and slopes

ommon integrals

REACTION?
How do you know a reaction has
occurred?
A chemical species is said to have
reacted when it has lost its chemical
identity-i.e. transformed into
another substance
The identity of a chemical species is
determined by
the kind,
number, and

EXAMPLES OF CHEMICAL REACTION

1. Decomposition

2. COMBINATION

3. ISOMERIZATION

Definition of Rate of Reaction

The reaction rate is the rate at which a species loses
its chemical identity per unit volume.
The rate of reaction (mol/dm3/s) of a species i can be
expressed as either
*the rate of consumption or Disappearance of i : -ri
or as
*the rate of formation or production (Generation) of
i : ri
negative sign indicates the amount or concentration of
the reactant i decreases because it is used up during
the
reaction
** for non homogeneous reactions other
definitions prevail

Reaction Rate for a solid catalyzed

heterogeneous reactions
For a catalytic reaction, we refer to
-rA',
which is the rate of disappearance of
species A on a per mass of catalyst
basis.
(mol/gcat/s)
NOTE: dCA/dt is not the rate of reaction

Rate of Reaction
is a function of the following parameters:
1. Concentration of reacting species
2. Temperature of reacting species
3. Pressure( gas phase reactants/ products)
4. the type of catalyst (if any)
Rate of Reaction is independent of the
type of reaction system (batch, plug flow
reactor, etc.)
. rj is an algebraic equation, not a
differential equation

Reaction Rate

EXAMPLE: AB

If Species B is being formed at a rate of 0.2

moles per decimeter cubed per second, ie
rB = 0.2 mole/dm3/s
Then A is disappearing at the same rate:
-rA= 0.2 mole/dm3/s
Why?
The rate of formation (generation of A) is
rA= -0.2 mole/dm3/s

Classification of reactions
very different ways . For our purpose a broad classification is used

HOMOGENEOUS reactions
I.gas-gas
II.liquid-liquid
.HETEROGENEOUS reactions
I. Gas-solid
II.Gas-liquid
III.Gas-solid-liquid
IV. liquid-liquid
Another classification

. CATALYTIC REACTIONS AND

. NON-CATALYTIC REACTIONS

Kinetics of homogeneous reactions

THE RATE LAW
in general, different reactants react
and products are formed at different
rates,
hence the rate of reaction/formation is
always stated with respect to a
specific reactant or the rate of
formation of a specific product.
The rate of reaction thus refers to the
rate at which the reactant is consumed

THE RATE of reaction

For many reaction systems, the rate of disappearance
of A is/can be mathematically decomposed into two
terms:
-rA = k(T)x f(Ci))
where
f (Ci ) is a function of the concentration of the reactants
This relationship between the concentration of
the reacting species and the rate of reaction is termed
the rate law.
k is the specific rate constant of the reaction.
It is most sensitive to the temperature of the reaction.
The most commonly used and experimentally tested
relation between the specific rate constant and

The Rate Law.

For many reaction systems, the rate of disappearance
of A is/can be mathematically decomposed into two
terms:
-rA = k(T)x f(Ci))
where
f (Ci ) is a function of the concentration of the
reactants
This relationship between the concentration of
the reacting species and the rate of reaction is termed
the rate law.

k is the specific rate constant of the reaction

k is the specific rate constant of the reaction.

It is most sensitive to the temperature of the
reaction.
The most commonly used and experimentally
tested relation between the specific rate constant
and temperature is the Arrhenius equation
Remember that rate constant is constant only at
a given temperature. It changes with
temperature

Arrhenius equation/law
k=k0e-Ea/RT
where
Ea =activation [energy/mol]
T =absolute temperature of the reaction i.e. K;R 0
R is the universal gas constant.
The units of Ea and R must be consistent. If E a is in
kJ/mol then R must have units of kJ/mol-K
k0 =the frequency or pre-exponential" or "entropy
factor
Equation is most useful relationship between the
specific rate constant and the temperature of
reaction

 Lnk = Lnk0 Ea/RT

Carrying Out The Reaction at Different T
and Calculating The Specific Rate Constant
at Each Temperature:

Data For Activation Energy Calculation

T

T1

T2

T3

T4

k1

k2

k3

k4

Lnk

lnk1

lnk2

lnk3

lnk4

1/T

1/T1

1/T2

1/T3

1/T4

Arrhenius plot: ln k versus

1/T
*
Ln
k

slope=Ea/R

1/T

Rate law [f(Ci )] and Order Of Reaction

aA + bB + cC
dD

For many reactions the dependence of the concentration on rate of reaction

is of the form

f(Ci )=CA CB CC

where
is the order of reaction with respect to the reactant A

is the order of reaction with respect to the reactant B

is the order of reaction with respect to the reactant C

n= + +
n= the overall order of reaction=the sum of the orders of reaction with
respect to each of the reactants
The order of reaction with respect to A reactant is the power to which the
concentration is raised in the rate law expression.
In the above expression, A, B and C are reactants
That is f(Ci ) is the product of the concentration of the reactants each raised
to a power which is the order of reaction

Other forms of the Rate Laws

-rA =k1CA/( k2+k3CA2)

For such, one talks of order of reaction and rate constant only
in limiting cases when the expression can be simplified

ELEMENTARY AND NON-ELEMENTARY

REACTIONS
rate law- inadequate theoretical knowledge
**determined experimentally
In some cases, the order of reaction with respect to a
reactant corresponds to the stoichiometric coefficient
of the reactant in the reaction equation.
When this happens we say the reaction is
elementary.
If for the reaction with the stoichiometric equation:
A + 2B
Products, the rate law is: -r A =k CA CB2
we say the reaction is elementary.
Otherwise the reaction is non-elementary

Reaction Mechanisms
The mechanism of a reaction is the series of
elementary steps by which the reaction is
assumed to occur at the molecular level.
It is proposed to give the detailed explanation
at the molecular level on how a reaction
proceeds.
When searching for a mechanism:
Steps are Proposed
Rate equations are derived and
Tested with data

Elementary Reaction

A reaction is said to be
elementary when the orders of
reaction correspond to the
stoichiometric coefficients of the
reactants n the balanced
equation
It must be emphasized that the
orders of reaction are
determined experimentally

Molecularity of a reaction

Some reactions occur in a single step-e.g.

ClNO2(g) + NO(g)

NO2(g) + ClNO(g)

Other reactions occur by a series of individual steps. for

example, decomposition of N2O5 ;
N2O 5
NO2 + O2
by a three-step mechanism.
The steps in a reaction are classified in terms of
molecularity, i.e. the number of molecules
consumed in a step.
When a single molecule is consumed, the step is called
unimolecular.
When two molecules are consumed, it is bimolecular.

Molecularity of elementary reaction steps

A reaction occurring in a three-steps is the

decomposition of N2O5 : N2O5
NO2 + O2
Each step is described by its molecularity
Step 1:
N2O5
NO2 + NO3 unimolecular step
Step 2:
NO2 + NO3
NO2 + NO + O2 bimolecular
step
Step 3:
NO + NO3
2 NO2 bimolecular step

Molecularity & ORDER

The Molecularity of a reaction, or a step
within a reaction, describes what happens
on the molecular level
The order of a reaction describes what
happens on the macroscopic scale.
We determine the order of a reaction by
watching the products of a reaction
appear or the reactants disappear.
The molecularity of the reaction is
something we deduce to explain these
experimental results.

collision theory model of chemical reactions:

explains the observed rate laws for both onestep and multi-step reactions.
model assumes that the rate of any step in a
reaction depends on the frequency of
collisions between the particles involved in
that step.
This is the basis for understanding the
implications of the collision theory model for
simple, one-step reactions, such as the
following.
ClNO2(g) + NO(g)
NO2(g) + ClNO(g)

collision theory model of chemical

reactions2
The kinetic molecular theory assumes
that the number of collisions per
second in a gas depends on the
number of particles per liter.
The rate at which NO2 and ClNO are
formed in this reaction should
therefore be directly proportional to
the concentrations of both ClNO2 and
NO.
Rate = k(ClNO2)(NO)

collision theory model of chemical reactions3

model suggests that the rate of any step in a

reaction is proportional to the concentrations of the
reagents consumed in that step.
The rate law for a one-step reaction should therefore
agree with the stoichiometry of the reaction.
The following reaction, for example, occurs in a
single step.
CH3Br(aq) + OH-(aq)
CH3OH(aq) + Br-(aq)
Because the reaction occurs in a single step, which
involves collisions between the two reactants, the
rate of this reaction is proportional to the
concentration of both reactants.
Rate = k(CH3Br)(OH-)

collision theory model: multistep chemical reactions4

Not all reactions occur in a single step.

The following reaction occurs in three
steps,
(CH3)3CBr(aq) + OH-(aq) (CH3)3COH(aq)
+ Br-(aq)
some of the steps are fast
Some of the steps are very slow
Since the steps are in series, the
overall rate is determined by the rate
of the slowest step

collision theory model: multistep chemical reactions5

step1
(CH3)3CBr
(CH3)3C+ + Br:Slow step
step2
(CH3)3C+ + H2O
(CH3)3COH2+ :Fast step
step3
(CH3)3COH2+ + OH(CH3)3COH + H3O :Fast step
The overall rate of reaction is therefore more or less
equal to the rate of the first step.
The first step is therefore called the rate-limiting
step in this reaction because it literally limits the
rate at which the products of the reaction can be
formed.

collision theory model: multistep

reactions6
Because only one reagent is involved in
the rate-limiting step, the overall rate of
reaction is proportional to the concentration
of only this reagent: Rate = k((CH3)3CBr)
The rate law for this reaction therefore
differs from what we would predict from the
stoichiometry of the reaction.
Although the reaction consumes both
(CH3)3CBr and OH-, the rate of the reaction
is only proportional to the concentration of
(CH3)3CBr.

H2(g) + Cl2(g) ---> 2 HCl(g) is made up of 4 elementary steps.

Cl2 2Cl.

Cl. + H2

HCl + H.

H. + Cl2

HCl + Cl.

Cl. + Cl.

Cl 2

Reaction Mechanism A
eg. 2 NO(g) + 2 H2(g) ----> N2(g) + 2 H2O(g)
This appears to be a 4 particle reaction as
written. Impossible!! Hence cant be a single step
reaction
Actual reaction mechanism is :
step #1: 2 NO + H2 ----> N2 + H2O2
slow since it involves a rare three particle
collision.
This is the slowest and therefore is the step
that determines the rate of all the other
steps.
step #2: H2 + H2O2 ------> 2 H2O fast reaction
Overall rate is therefore given by

Reaction Mechanism B
-r NO =k CNO2 CH2
Termolecular reaction steps
require three molecules coming
together at the same time
They are rare because three-body
collisions in the gas phase are rare
4 particle reactions are
therefore virtually
Impossible!!

general rules to explain rate laws

1. The rate of any step in a reaction is

directly proportional to the
concentrations of the reagents
consumed in that step.
2. The overall rate law for a reaction is
determined by the sequence of
elementary steps, or the
mechanism, by which the
reactants are converted into the
products of the reaction.
3. The overall rate law for a reaction is

Activation Energy and the Activated

Complex
Activation Energy is the energy that
must be reached by 2 colliding molecules
before a reaction can take place
From Collision Theory the rate of a
reaction depends on two factors.
1) The number of collision per unit time
between the reacting species.
2) The fraction of these collisions that are
successful in producing a mew molecule.
For a reaction to occur, molecules must
collide not only with sufficient energy
but also with the proper orientation

Activation Energy and the

Activated Complex2
The reactants can get to the point of
highest potential energy (the
"activated complex" or "transition
state" -) only if they initially have
sufficient kinetic energy to turn into
the potential energy of the activated
complex.
activated complex is that
arrangement of reactants which can
proceed to products without further

Activation Energy and the

Activated Complex2

Relationship Between the Activation

Energies of Opposing Reactions

Slow reactions have high activation

energies.
Fast reactions have relatively low
activation energies.
An endothermic reaction always has a
greater activation energy and a slower
rate than the opposing exothermic reaction.
An increase in the temperature affects
the rate of the endothermic reaction
more than that of the exothermic reaction.

Obtaining the rate law: by

1.Monitoring the levels of
reactants or products as the
reaction progresses-i.e. as a
function of time of reaction
2.Testing for the rate law which is
consistent with the measured
kinetic data
3.Equipment used are batch or
flow reactors

Chemical kinetics or reaction

kinetics
the study of rates of chemical processes.
includes
investigations of how different experimental
conditions can influence the speed of a
chemical reaction and yield information
about the reaction's mechanism and
transition states,
as well as the construction of mathematical
models that can describe the characteristics
of a chemical reaction

Obtaining the kinetic data:

batch reactor types

Vessel containing reaction contents as reaction

progresses
Batch reactor: constant
volume
Usually stirred to ensure
uniform
composition in whole vessel

Batch reactor:
variable volume

Flow reactors

Typical Features Of A Batch Reactor

Probes for monitoring temperature, Pressure,
pH, other concentration parameters
Connection to a condenser
Connection to atmosphere if relief valve
ruptures
Jacketed for heating/ cooling reactor contents
*coils for cooling/heating reactor contents
Perforated coils for sparging
*Sampling points
Sight glass to observe reactor contents
Charging points
Discharge points

Kinetic Data

Direct measurement of concentration

Direct measurement of pressure-for gas
phase reactions
Measurement of parameters which are
related to concentration of species
-pH of solutions
- conductance of solutions
-absorbance of solutions
-colours of solutions
-etc

Kinetic Data: Chemical Methods

These are mainly titration methods and
they can be highly accurate.
They are generally reserved for simple
reactions in solution where either only the
reactant or the product concentrations are
being monitored.
Here sampling errors and speed of analysis
are crucial.
Chemical methods have been largely
superseded by modern black box techniques,
though, in certain types of solution reaction,
they can still be very useful.

Physical Methods:1

These use a physical property

dependent on concentration and must
be calibrated
much more convenient than chemical
methods.
In situ measurement can often be made
in, and analysis is often very rapid.
Automatic recording gives a continuous
trace.
It is vital to make measurements faster
than reaction is occurring.

Physical methods:2
pH and EMF methods
1. using a glass electrode sensitive to H3O+
. Reactions which occur with change in H3O+ or a
change in [OH-] to be followed with ease.
. A pH meter measures pH directly, and
. a millivoltmeter measures EMFs directly, and these are
related to H3O+
E.g.In CH3COOCH3(aq) +OH-(aq)
+CH3OH(aq)

CH3COO(aq)

. OH-(aq) is removed, [H3O+] will increase and the pH will

decrease with time, with a corresponding change in
EMF and
In CH3COOCH2CH3(aq) + H3O+ aq)
CH3COOH(aq)
+CH3CH2OH(aq)

Kinetic Data: Pressure Changes In

Gas Phase Reactions For
Constant-Volume Batch Reactors

for gas phase reactions which

occur with an overall change in
the number of molecules and
consequently show a change in
total pressure with time.
Ideal gas law pV = nRT and
P n :if V and T are constant

Kinetic Data: Volume Changes In

Gas Phase Reactions For
Constant-Pressure Batch Reactors

for reactions which occur with an

overall change in the number of
molecules in the gas phase and
consequently show a change in
volume with time.
PV = nRT
P n :if V and T are constant

Kinetic Data:
Conductance Methods

useful when studying reactions involving

ions.
1. (CH3)3CCl(aq) +H2O(l) (CH3)3COH(aq) +
H+(aq)
+Cl-(aq)
. Ions are produced, and the
conductance rises with time.
2. NH+4(aq) + OCN-(aq)
CO(NH2)2(aq)
. Ions are removed, and the
conductance decreases with time

Other Analytical methods

include
Chromatographic,
mass spectrometric
spectrophotometer
and spectroscopic methods
**Some methods will be
explained in subsequent
questions

Describing The Progress of a Chemical

Reaction:
Fractional Conversion 1

The Progress of a Chemical Reaction is often

expressed in terms of the fractional
conversion, Xi, of the reactant i.
The fractional conversion of a reactant A (
XA ) is defined as
XA =[moles of A consumed or transformed
into products after reaction time, t] /[moles
of A fed to the reactor].
For a batch reactor, the fractional conversion
of the reactant A is expressed as
XA =(NA0 - NA)/ NA0

Fractional Conversion 2
NA0 =Moles of A charged into the reactor initially
(t=0)
NA =Moles of A left in the reactor after reaction
time, t
It follows that the moles of A that has been
transformed into products or consumed after
reaction time, t is

NA0 - NA= NA0 XA

The fractional conversion can be used to relate
the quantities of all the reactants that
participate in the reaction at any time of the
reaction
In terms of the reactant B, the amount of B

Fractional Conversion3
of the stoichiometric equation: aA + bB
cC + dD
[Moles of A reacted]/[Moles of B reacted]
[NA0 XA ]/ [NB0 XB ]=a/b
In general, the fractional conversion of a
reactant A is different from that of
another reactant B
The fractional conversion of a reactant A
increases with reaction time
At complete conversion, the fractional
conversion of the limiting reactant is 1

The Extent of Reaction (or sometimes the degree of

advancement).

The extent of, , is defined as

= (Ni Ni0)/ i
where
Ni0 = number of moles of i into reactor (t=0)
Ni = number of moles of i out of reactor (t = t)
i =stoichiometric coefficient of i
Ni = Ni0 + i
(mol/s) is same for all species, must be
positive
a dummy variable that reflects how far each
reaction proceeds.

*
i is positive for a product
i is negative for a reactant
. If there is more than one reaction
going on, there will be an extent
term for each reaction. So for i
components and j reactions:

Relating the concentrations of species in the

reaction mixture: Stoichiometric Table

Lets consider components of a reaction

system, including inerts-I-that have been
charged to the reactor.
All quantities are written in terms of
one(A) of the components of the reaction
system.
Amounts and concentrations of species
change as the reaction progresses
balance of the reacting system is carried
out when the fractional conversion of the
chosen reactant, A, is XA

Stoichiometric Table
Useful in relating the relationship
between the *Concentrations of
various species in the reaction
mixture with time
*enables easy representation of the
rate law in terms of a single variable
*enables easy calculation of the
partial pressures of various species
for gas phase reactions
*enables easy calculation of the
mole fractions of various species in

Stoichiometric Table at XA for constant

volume
batch reactor
Compon Initial
Change due Moles
Concentration
ent
[1]
A

charge [2]

remaining, Ni [4]

Ci [5]

NA0= NA0A

to reaction,
[3]
-NA0XA

NA0A -NA0XA
= NA0 (A -XA)

NA0 (A -XA)/ V
= CA0 (A -XA)

NB0= NA0B

-NA0XA(b/a)

NA0B-NA0XA(b/a)
= NA0 [B-XA(b/a)]

NA0 [B-XA(b/a)]/ V
= CA0 [B-XA(b/a)]

NC0= NA0C

NA0XA(c/a)

NA0C+ NA0XA(c/a) NA0 [C+XA(c/a)]/ V

= NA0 [C +XA(c/a)] = CA0 [C+XA(c/a)]

ND0= NA0D

NA0XA(d/a)

NA0D+ NA0XA(d/a) NA0 [D+XA(d/a)]/V

= NA0 [D+XA(d/a)] = CA0 [D+XA(d/a)]

NI0= NA0I

= NA0I

=NA0I /V

Total
N0=NA0(A + B + C + D + I) N=N0 + NA0 XA [(d/a)+ (c/a)-(b/a)-1]

Stoichiometric Table3
Column 1 lists the various components of the
reaction system- reactants, products and inerts
(I)
Column 2 lists the amount of the various
components initially charged to the reactor, all
amounts expressed in terms of NA0 and i0.
The definition of i0, listed at the bottom of Table
2.1 makes this simplification possible. This
column is calculated from the composition of
the initial charge to the reactor.
i = Ni0/ NA0 ;A = NA0/ NA0 =1 ; B = NB0/ NA0

C = NC0/ NA0 ;D = ND0/ NA0 ; I = NI0/ NA0

Column 3 lists the changes in the amounts of each

component due to chemical reaction when the
fractional conversion of A is XA.
These changes are negative for a reactant because it
is consumed during the reaction.
For a product the changes are positive.
The quantities are based on the stoichiometric
equation. From the stoichiometry,
[Amount of B reacted]/[amount of A reacted] =b/a
If the change in A (amount of A reacted) is NA0XA,
Then
[The amount of B reacted] =(b/a) x [amount of A
reacted] =(b/a) NA0XA.

 Column 4 is simply the summation of columns 2

and 3. Hence the amount of B remaining at
fractional conversion of A of XA
=amount present initially + change in B
= NA0B-NA0XA(b/a)= NA0 [B-XA(b/a)]
For product D, the amount remaining when the
fractional conversion of A is XA
=amount of D present initially + change in D
=NA0D+ NA0XA(d/a) = NA0 [D+XA(d/a)]
Note that D =0 if there is no D in the reaction
mixture initially

Stoichiometric Table
Column 5 gives the concentration of components at X A.
This is obtained by simply dividing the moles remaining by the
volume of the reaction mixture, which in this case is
assumed to be constant -i.e. C i = Ni / V.
The moles remaining is obtained from column 4.

Note that in a similar manner, the table can be expressed in

terms of any reactant or product .
Usually it is the limiting reactant that is used for reactants
A product may be monitored instead of a reactant because it
may be easier or more accurate to do so.
Hence the importance of being able to express the rate of
reaction in terms of any component in the mixture

Stoichiometric Table for constant volume batch reactor (in terms of C A)

Compo Initial
Change due
nent charge [2] to reaction, [3]
[1]

Moles
remaining, Ni [4]

Concentration
Ci [5]

NA0= NA0A -( NA0- NA)

NA0A -( NA0- NA)= NA

NA/V
=CA

NB0= NA0B -( NA0- NA) (b/a) NA0B-( NA0- NA)(b/a)

=NA0(B - b/a)+ b/a NA

[NA0(B - b/a)+ b/a NA]/V

CB= CA0(B-b/a)+ (b/a) CA
= 2.0(1-0.5)+ (0.5) CA
= 1.0+ (0.5) CA

ND0= NA0D ( NA0- NA) (d/a)

NA0D+( NA0- NA)(d/a)

= NA0(D +d/a)-(c/a)NA

[ NA0(D +d/a)-(d/a)NA]/V
CD=CA0(D +d/a)-(d/a)CA]
=2(0+1.5)-(1.5)CA]
=3-1.5CA

NI0= NA0I 0

NA0I

NA0I/V
CI= 2.0(0.05)=0.10

Total

N0=NA0(1 + 1 + 0 + 0.05)
=2.05 NA0
2.05x200=410

Nt=NA0(1 + 1 + 0 +0.05) +( NA0- NA)(1.5+0-0.5-1)

= 2.05 NA0+( NA0- NA) )(1.5+0-0.5-1)
=2.05 NA0 +0=2.05x200=410

Stoichiometric Table for constant

volume batch reactor (in terms of
a Change
product
CD)
Compo Initial
due
MolesD i.e.Concentration
nent
[1]

charge [2]

to reaction, [3]

remaining, Ni [4]

NA0= NA0A

-( ND-ND0)(a/d)

NA0 -(ND-ND0)(a/d) [NA0 -( ND-ND0)(a/d)]/V

=CA0 -(CD-CD0)(a/d)

NB0= NA0B

-( ND-ND0)(b/d)

NB0-(ND-ND0)(b/d)

[NB0-( ND-ND0)(b/d)]/V
CB= CB0-(CD-CD0)(b/d)

NC0= NA0C

( ND-ND0)(c/d)

NC0+(ND-ND0)(c/d)

[NC0+( ND-ND0)(c/d)] /V
CC= CC0 + (CD-CD0)(c/d)

ND0= NA0D

( ND-ND0)

ND

ND /V
= CD

NI0= NA0I

NA0I

NA0I/V
CI= CA0I

Ci [5]

Stoichiometric Table:
last comments

It is easy to set up
May be in terms of the fractional conversion
of any reactant
In terms of the concentration of any reactant
in the reaction mixture or
In terms of the concentration of any product
in the reaction mixture
It is easy
Learn to set it up very fast
Very necessary because mathematical
manipulation generates errors and this must
be minimised

Analysis Of Kinetic Data

Different methods can be used to analyse the
collected data. They include the following :

1.Integral Method
2.Differential Method
3.Method of initial rates
4.Method of half-lives
5.Method of isolation or excess
6.Least square analysis Method
Use any that is fast convenient and sufficiently
accurate

1.Integral Method
Involves the following steps:
1. Assume order(s) of reaction and hence rate
law
2. Integrate the differential form of the rate law
3. Make the appropriate linear plot based on the
integrated equation
4. If the linear plot is consistent with the
expected straight line, then the assumed
order is correct
5. Otherwise the process is repeated with
another order of reaction
6. Hence important to know linear plots for 0, 1,
2 and 3 orders of reaction

Main Features of Integrated Rate Equations

Confirms a suspected order if the relevant plot is

linear;
a quick, easy and accurate way to determine k once
the order is known;
can be used to calculate the concentration at any time,
or the time taken for the concentration to drop by a
given amount;
But
if the reaction is NOT followed over a long enough
extent, the graphs will appear to be linear for all orders

to distinguish between orders of reaction it is vital to

follow to at least 60 per cent of the reaction
less than 60 per cent conversion is possible with very
accurate data;

Integral Method: zero order(single Rt:

A
Pdt.)constant-volume batch reactor

Integral Method: 1st order wrt a single

reactant, A, constant-volume batch
reactor
First order reaction:

The first order rate law

is a very important rate law:
radioactive decay and many chemical
reactions follow this rate law
some of the language of kinetics comes
from this law.

This form is called an "exponential
decay."
This form appears in many places in
nature.
it gives rise to a concept called "half-life."

Integral Method: 2nd order wrt a single

reactant, A, constant-volume batch reactor

2A

products

nth order reaction: nA

products

If the order for type of reaction is not known,

one can assume directly an nth order reaction
instead of testing for orders of 0, 1 and 2
successively.
For an nth order reaction (constant density
reaction mixture) : -rA=-dCA/dt =k CAn

n tested by trial and error

Units of the rate constant, k

Differential Method Of
Analysis
dC

dt

k f (C i )

makes use of the differential form of the

rate law:
Concentration vs. time data is differentiated
numerically or graphically in order to obtain
values of [-dCA/dt ].
method is most easily applicable when the
rate is dependent on the concentration of
only one component.
If the rate depends on more than one
component, the method is easily adapted
by combining it with the method of excess.

Differential method: rate depends on

the concentration of a single reactant
rate law is of the form:-rA = [dCA/dt]= kCA
ln(-dCA/dt)= lnk + ln CA
Hence a plot of ln(-dCA/dt) versus ln
CA should give a straight line of slope

Differential Method:
obtaining order ln(dCA/dt)= lnk + ln CA
*

ln (dCA/dt)

intercept=
lnk

slope=

ln CA

Obtaining (-dCA/dt):
Any mathematically convenient and
accurate method of obtaining the
slope
measuring the slope of the tangent to the
CA vs t. plot at various points as shown in
fit a polynomial of sufficient accuracy to
the CA vs. t plot :
CA(t)=a0 + a1t + a2t2 + a3t3+ a4t4
Microsoft Excel can be easily used for this.
Differentiating equation with respect to t
yields
dCA(t)/dt= a1 + 2a2t + 3a3t2+ 4a4t3

slope of the tangent to the C A vs t. plot

slope of the tangent to the C A vs t.

plot at different points

Differential method of
analysis

By choosing the appropriate times

and reading from the CA vs t plot or
calculating CA from eq., one can
obtain the (-dCA/dt) vs t

other methods of obtaining dC(t)/dt

include:
plotting CA/t versus t and using the
method of equal area to obtain dCA/dt
Use of the differentiation formula such as

Differential method: rate

depends on the concentration
of more than one reactant

Applied by combining with the method of

excess.
If the reactant B is in large excess then
and
the
concentration
of
A
is
monitored
as
dC A

kC A of
C B time
kC A C B0 kC A
a- function

dt

By now reacting under conditions of excess

reactant A, the concentration versus time data of
component B is obtained.
dCA

kCA CB kCA0 CB k CB
dt

Method of half-life:
Half-life period or the half-life

of a decaying material is the time it takes for the

amount of decaying material to be reduced to
half.
The half-life is characteristic of the decaying
(originally radioactive) materials.
The half life of a limiting reactant (t 1/2), is the
time required for the concentration of the
reactant to be reduced to half of its original value.
The time it takes for the concentration to half its
value.
The dependence of the half-life on concentration
reflects the way in which the rate of reaction
depends on concentration.

Method of HALF-LIFE: ZERO ORDER

first half-life, second half-life the

third half-life etc
At half-life, t= t1/2, CA=0.5CA0
For zero order
the higher the concentration the
greater is the half-life:

Half-lives Decrease As The Concentration

Decreases:
Zero Order Reaction

half-life for a FIRST ORDER reaction:

ln (CA0/ CA )
=kt
At half-life, t= t1/2, CA=0.5CA0
ln (CA0/ 0.5CA0 ) =ln2= kt1/2

half-life is independent of the

concentration for a first order
reaction

Half-life Is Independent Of
Concentration
First Order Reaction

Any Fractional Life-time For A First

Order Reaction
The relaxation time is the time when the
concentration becomes 1/e of the
original.
At relaxation time, and CA=(1/e)CA0,
Ln[CA0 /(CA0 /e)]=ln(e)=1=k
hence
Since (1/e)CA0,= 0.3679 CA0
At the relaxation time the reaction has
gone to XA =[CA0 - 0.3679 CA0 )/CA0]=0.632
=63.2 per cent completion

relaxation time for a first order reaction

half-life for a second order reaction

1
1

kt
CA
C A0

half-life is inversely proportional

to the concentration.
1
t1 / 2

kC A0

The half-life increases as

reaction proceeds.

half-lives increase as the concentration

decreases: Second order reaction

half-life for nth order reaction:

In general the half life of a reaction
depends on the concentration of the
reactant
and the
1 n order
of the reaction.
1 n

C A0

(0.5 1)
t1/ 2
(n 1)k

Taking logs of both 1sides

n

(0.5 1)
(1 n) ln C A0 ln
ln t1/ 2
(n 1)k

half-life for nth order reaction:

Hence a log log plot of t1/2 vs. CA0

should give straight line
Slope =1-n ; or

n=1-slope

(0.51 n 1)
ln
= (n 1)k

Intercept
depends on the concentration of the
reactant
and the order of the reaction.
Taking logs of both sides

log log plot of t1/2 versus CA0

ln(t1/2
)

(0.51 n 1)
int ercept
(n 1)k

Slope =1n

ln(CA
0)

different slope signs depending on

the order of reaction
*

lnt1/2

Orders of
reaction < 1
Orders of reaction
>1

Orders of reaction
=1

ln CA0

Method of excess or Method of isolation

technique used to simplify the analysis of

complex rate expressions
The method consists of effecting runs
with all but one component in such
sufficient excess that its or their
concentration(s) remain(s) essentially
constant during the run.
By monitoring the concentration of this
isolated reactant as a function of time,
the order with respect to the isolated
reactant can be determined by any of the
techniques discussed

Method of excess or Method of isolation

the rate law for the reaction: A +B

products
rA= -dCA/dt =k CA CB
If B is the reactant in excess,
A is the isolated reactant
CA changes while CB remains
virtually constant during the
reaction.
Hence
r = -dC /dt =(k C )C =(k C )C

 *
ln(-rA)

ln(CA0)

Method of excess.3
k' is a pseudo--order rate constant.
The reaction is a pseudo- -order
reaction, because it behaves as if it
were -order although it is not
really -order.
It is -order with respect to only A.
k' is not a true constant
its value varies with the initial
concentration of B, CB0.

*
By performing a series of experiments in
which CB0 varies but is always much
larger than CA0, one obtains k' as a
function of CB0

As a general rule, a minimum of a 20fold stoichiometric excess is necessary.

A 50-fold or 100-fold stoichiometric
excess is the preferable requirement to
effectively "isolate" the effects of a
single reactant.

 *
ln(k')

ln(CB0)

METHOD OF INITIAL RATES

method uses the initial rate of reaction to
simplify the analysis of obtaining the rate
law of complex rate expressions.
This involves effecting the same reaction
at preferably the same temperature but
using different initial concentrations of
reactants.
There is more certainty about the
measurement of the initial
concentrations and any interference
about the effect of side reactions are also
avoided in this method.

METHOD OF INITIAL RATES:

Primary Problem Of Method
difficulty in accurately determining the
initial rate.
Difficult to determine the initial rate,
because as soon as the reaction begins,
the rate slows down (unless the order is
zero)
Measuring the rate as close to the start of
the experiment, measuring the rate and
extrapolation to obtain the rate at t=0
invariably entails some errors.
This involves effecting the same reaction

METHOD OF INITIAL RATES:

The rate law for reversible

reaction :A+B=C+D has the
general form

r
=
-dC
/dt
=k
C
C
-kC
A
A
A
B
C
CDb
At t=0, and with no products in
the initial charge, CC0=0;

CD0=0;

series of runs with the same CB0

but different CA0, and measuring
the rate [-rA0

ln( rA0)=ln(k. CB0 )+ lnCA0

ln( rA0)

slope=
ln(k. CB0)
ln(CA0)

Runs with same CA0 but different CB0 and

measuring -rA0
ln( rA0)=ln(k. CA0 )+ lnCB0

ln( rA0)

slope=

ln(k. CA0)

Leastsquare method
The leastsquare method can be
used to obtain the best values of the
parameters of the rate law-the
orders of reaction and the rate
constant.
For a rate law of the form:
linearizing the functional form of the
law:
and C are the variables measured

Leastsquare method2
vs. ln CA
the plot of
represents the equation of a straight
line of the form y=mx+c,
Where y=

; x= ln CA

The best values of the parameters c

and m are obtained from the least
square method.

For n experimental sets of data of a given

reaction,

one can generate the following sets of

equations by summing the data from the
runs - using the linearized forms:
Multiplying both sides of the linearized
equation by xi and summing i.e.[yixi
=mxixi + cxi]
Since the sums are easily set up, the two
equations have only two unknowns-m
and c

best values for and k by the least square methods

Run

CAi (-rAj)

Xi
=lnCA

Yi
=ln(-rA)

xiyi

xi2

CA1 (-rA1)

lnCA1

ln(-rA1)

lnCA1*ln(-rA1) (lnCA1)2

CA2 (-rA2)

lnCA2

ln(-rA2)

lnCA2*ln(-rA2) (lnCA2)2

CA3 (-rA1)

lnCA3

ln(-rA3)

lnCA3*ln(-rA3) (lnCA3)2

CA4 (-rA4)

lnCA4

ln(-rA4)

lnCA4*ln(-rA4) (lnCA4)2

Can (-rAn)

lnCAn

ln(-rAn)

lnCAn*ln(-rAn) (lnCAn)2

lnCAi

ln(-rAi)

lnCAi *ln(-rAi) (lnCAi)2

summations

Least square
The two simultaneous
equations
method
are solved for the unknowns.
These are the best values of the
parameters obtainable from the
experimental data

Least square method: complex rate forms

Linearizing
yi =
c + ax1i + ax2i
Two independent variables:
x1=lnCA and x2=lnCB
The summation of the results of all
the n runs

Least square method: complex

rate forms 2
The summation of the runs :

Multiplying both sides of the linearized

equation by x1i and summing

Multiplying both sides of the linearized

equation by x2i and summing

Sums for solving the system of

equations
x1i

x2i

yi

x1i2

x1i x2i x1iyi x2i2

yi x2i

Solving for the parameters

We now have three equations in three
unknowns, namely the desired
parameters
This method becomes particularly useful
when simplifying methods such as the
method of excess cannot be used.
It is obvious that the method can be
applied when more than three
parameters from the rate law are to be
determined

VARIABLE VOLUME BATCH

REACTORS
Variable volume batch reactors occur when there
is a change in the number of moles as the gas
-phase reaction proceeds at constant pressure.
in the gas phase reaction: CO+O2=CO2
2 moles of reactants react to give one mole of
product
a decrease in the number of moles and hence of
the volume of reaction mixture
because, the volume is proportional to the
number of moles at constant pressure and
temperature.

Equation Of State :PV=ZNRT

By applying the equation of state on the
reaction system in a batch reactor, to relate
the volume of the reaction mixture with its
number of moles.
The equation of state at any time t, after
reaction has started is
PV=ZN RT - - -1
Z=compressibility factor
NT=total number of moles of reaction mixture
At t=0, P=P0 , T=T0 ;V=V0 Z=Z0,
the equation of state becomes
P0V0=Z0N0RT0 - - -2

Eq(1) /Eq(2) and simplifying

V= V0 (P0 /P) Z/Z0) (T/T0) (NT/N0 ) - - -3

From stoichiometric table:
NT=N0 + NA0 XA [(d/a)+ (c/a)-(b/a)-1]
= N0 + NA0 XA (d+ c-b-a) /a
= N0 + NA0 XA n /a
where:
n =(d+ c-b-a)
NT/ N0= 1 + (NA0 /N0 ) XA n/a
= 1 + (yA0 n /a) XA
=1 + AXA

A=( NT-N0)/ N0 =yA0 n /a At XA =1

A =change in total number of moles on

complete reaction of A (XA =1) / total moles fed
to the reactor
Eq.3 now becomes
V= V0 (P0 /P) (Z/Z0) (T/T0) (1 + AXA)
Assuming negligible change in compressibility
factors within the range of operation,
V= V0 (P0 /P) (T/T0) (1 + AXA)
In a constant pressure (P0=P) isothermal (T=T0)
batch reactor the relationship simplifies to
V= V0 (1 + AXA)

VARIABLE VOLUME BATCH REACTOR: XA and

XA =(V- V0 )/ AV0
dXA/dt= [1/AV0]dV/dt
CA= NA/V =NA0(1 XA)/V0 (1 + AXA)
CA= CA0(1 -XA)/(1 + AXA)

CA

VARIABLE VOLUME BATCH REACTOR: -rA

-rA=(-1/V)(dNA/dt)

= (-1/ V0 (1 + AXA)(dNA0 (1 XA)/dt)

= (-1/ V0 (1 + AXA)(-NA0dXA)/dt)

=[CA0/ (1 + AXA)] [dXA/dt]

-rA =[CA0/AV][dV/dt]=[CA0/A][d(lnV)/dt]
For zero order:
-rA = [CA0/A][d(lnV)/dt]=k
[d(lnV)]=[A/CA0]k dt
Integrating
ln(V/V0)=[kA/CA0] t

Variable volume, constant pressure, isothermal

batch reactor:
Zero order reaction

A > 0

ln(V/V0)
t

A < 0

VARIABLE VOLUME BATCH REACTOR: -rA

For first order: -rA = [CA0/A][d(lnV)/dt]=kCA

Substituting for CA
[CA0/A][d(lnV)/dt]=k CA0(1 -XA)/(1 + AXA)
Simplifying
[dV/V)/dt]=k A(1 -XA)V0/V
dV =kA[(1 -(V- V0 )/AV0)]V0 dt
dV= k[AV0-(V-V0)]=k[(1+A)V0V]dt
Integrating
-ln[(1+A)V0V]/[(1+A)V0V0]=kt
-ln[V0+V0AV]/[AV0]=-ln[V0AV]/[AV0]=kt
-ln[1V/AV0]=kt ; V=V-V0

Variable volume, constant pressure, isothermal

batch reactor:
first order reaction

-ln[1
V/AV0]

Q & A
Nitric acid is made commercially from nitric oxide. Nitric
oxide is produced by the gas-phase oxidation of
ammonia.
4NO + 6H2O
4NH3 + 5O2
The feed consists of 15 mol% ammonia in air at 8.2 atm
and 227C.
What is the total entering concentration?
What is the entering concentration of ammonia?
Set up a stoichiometric table with ammonia as your
basis of calculation.
Express Ci for all species as functions of conversion for a
constant-volume batch reactor. Express PT as a function of X.
Express Pi and Ci for all species as functions of conversion for a
flow reactor.

Write the combined mole balance and rate law solely in

terms of the molar flow rates and rate law parameters

Total pressure in constant volume batch

reactors: gas phase reactions
component

initial charge
Ni0

change due to
reaction at NA

moles remaining in terms of

total moles
Ni

NA0

-( NA0-NA)

NA0-( NA0-NA)=NA
= NA0-(NT-N0) (a/n)

NA0B

-( NA0-NA) (b/a)

NA0B -( NA0-NA)(b/a)
=NA0B -(NT-N0)(b/n)

NA0C

( NA0-NA) (c/a)

NA0C +( NA0-NA) (c/a)

=NA0C+(NT-N0)(c/n)

NA0D

( NA0-NA) (d/a)

NA0D +( NA0-NA) (d/a)

=NA0D +(NT-N0)(d/n)

NA0I

NA0I

 Total moles initially

N0=NA0 (A +B + C +D +I )
- - - 3.1
Total moles remaining
NT =NA0 (A +B + C +D +I )-( NA0-NA)( NA0-NA)(b/a) +( NA0-NA)(c/a) +( NA0-NA)(d/a)
Simplifying
NT =N0+( NA0-NA)( d/a+ c/a- b/a-1)
NT=N0+( NA0-NA)( d+ c- b-a)/a
NT =N0+( NA0-NA)(n/a)
( NA0-NA)= (NT-N0)(a/n)

At constant temperature and

volume
P
V=N
RT
or
N
=P
V/RT
i
i
i
i
component N
Pi=NiRT/V

A
B
C
D

NA0 -(NT-N0)a/n
NA0B -( NT-N0)(b/n)
NA0C +( NT-N0)(c/n)
NA0D +( NT-N0)(d/n)

NA0I

PA= PA0 - (PT-P0)a/n

PB= PA0B - (PT-P0)b/n
PC= PA0C + (PT-P0)c/n
PD= PA0D + (PT-P0)d/n
PI=PA0I

NA=NA0-(NT-N0)a/n

PAV/RT=PA0V/RT- (PT-P0)Va/nRT

PA=PA0- (PT-P0)a/n

NB=NA0B -( NT-N0)b/n

PBV/RT=PA0BV/RT- (PT-P0)Vb/nRT

PB=PA0B- (PT-P0)b/n

NC =NA0C +( NT-N0)(c/n

PCV/RT=PA0CV/RT+ (PT-P0)Vc/nRT

PC=PA0C+ (PT-P0)c/n

ND =NA0D +( NT-N0)(d/n

PDV/RT=PA0DV/RT+ (PT-P0)Vd/nRT

PD=PA0D+ (PT-P0)d/n

NI =NA0I

PIV/RT=PA0IV/RT

PI=PA0I

Total pressure versus time

data

Question.
The gas phase decomposition of ethylamine produces ethene and ammonia,
C2H5NH2(g)-- C2H4(g)+ NH3(g)
The following total pressures were found for the reaction at 500 0C with an initial pressure of pure ethylamine
equal to 55 mmHg.

Ptotal,mmHg: 55
:

Time,min 0 2

64
4

72 89 93

10 12

Using this and the following data, find the partial pressure of C2H5NH2 remaining at the
various times, and plot an appropriate graph showing the progress of reaction.
What will the final pressure be?
Show that the decomposition is not first order
What is the rate law of the decomposition

REVERSIBLE REACTIONS
In irreversible reactions the reactants
react until they are completely consumed
and products are formed.
In reversible reactions the products
formed do react to give back the
reactants.
Reversible reactions are thus
represented as shown, with a double
arrow:

A
D. forward reaction
The reactants, A , react to form the
product D. The reverse reaction is
represented as
A
D. reverse reaction
The products of the forward reaction D
react to form the reactants
forward and reverse reactions take
place simultaneously

rate of the forward reaction depends

on the concentration of the reactant
A
rate of the reverse reaction depends
on the concentration of the reactant
for the reverse reaction-D.
There is thus a net reaction in favour
of the faster of the reactions,
depending on the concentration of A
and D

Dynamic Equilibrium:

When the concentrations of the reactants and

products are such that the rate of the forward
reaction is equal to that of the reverse reaction then
we have attained the condition of dynamic
equilibrium.
When reactants and products are present in
significant quantities at equilibrium, the relationship
is described in terms of the equilibrium constant,
the magnitude indicates of how far right the reaction
has gone.
Irreversible reactions may thus be regarded as
reversible reactions whose equilibrium lie far to the
right-that is, the reaction mixture consists of either
reactants or products.

Equilibrium Constant
The larger the value for the equilibrium
constant the more the reaction goes to
completion.
The value for K is large when products
dominate the mixture.
The value for K is small when the
reactants dominate the mixture.
Irreversible reactions can be thought to
have an infinite equilibrium constant so
there are no reactants left

the equilibrium constant

Large K have values that are
huge, 1 x 1034
K = 1 neither reactants nor
products are favored
Small K have values that are
tiny, 4 x 10-41

First order reversible reactions:

both the forward and the reverse
reactions are first order
Common examples of first-order
reversible reactions are the gas-phase
isomerisation in various types of
hydrocarbon systems
For the forward reaction, the rate of
consumption of A is:
The reverse reaction produces A:

30

10
9

-rA =forward reaction

25

k1 =3/min; k1 '=1.0

k1 =3/min;
k1 '=1.0/min

20

rA =reverse reaction

CA

6
5
mole/L
4

mole/L.min 15

10

2
1

0
0

0 0.5 1 1.5 2
t,min

0.5

1.5

t, min

2.5

First order reversible reactions:

A
D

The net rate of consumption of A is :

Substituting for CD from the

stoichiometric table
i

Ni0

Ni

Ci

NA0

-(NA0- NA) NA

CA

(NA0- NA)

CA0- CA

NA0- NA

Separating variables leads to

Integrating leads to

Substituting limits leads to

At equilibrium,

and .

Simplifying

Dividing log term by [k1+k1] leads to

In terms of the fractional conversions

*since CA=CA0(1-XA) and CAe=CA0(1-XAe). Hence

The method of initial rates can be used to

find . At t=0,
and
This simplifies to
= k1

Hence a plot of
vs.
should give a
straight line through the origin with slope
equal to k1 .

slope=k
+k

slope=k

+k

linear plot to test for first order

reversible reaction
When combined with equilibrium constant
K=k/k, the two constants of the reversible
reaction can be found

Consecutive/Series First Order irreversible A

k1

k2

an intermediate product is formed and

it reacts further to form products-C.
substitution reactions.
In oxidation of ethanol or methanol.
the desired product is acetaldehyde.
acetaldehyde can react further to
produce carbon dioxide- a loss of the
desired acetaldehyde product:

Consecutive/Series First Order irreversible A

k1

k2

CH4 +Cl2 CH3Cl +Cl2 CH2Cl2 +Cl2 CH3Cl and

so on . This is the chlorination of methane

Consecutive reactions are quite

common in organic reactions

Assuming the reaction is elementary

as written each step is first order *
Separating variables and integrating
For component B, the net rate of
reaction is

From the stoichiometry, it follows

*

10

C
A

10

C
C

CB

8kn;=1.0/mi
1

k1=1.0/mi
n;
k2=2.0/mi
n

k2=10.0/
min

6
mole/L

mole/L

1
0
0

1
t,min

t,min