CHE 315

Dr. Sanni S.E

• 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
•at the heart of virtually every chemical
process.
•Reactor may be small but crucial to the
economics of the process
•It separates the chemical engineer from
other engineers.
•Process Industries Draw Heavily on
Chemical Reaction Engineering
Chemical Reactor and TYPICAL CHEMICAL PROCESS
Physical treatment step chemical treatment step Physical treatment step

PRODUCTS
RAW

MAT
RECYLE

TYPICAL CHEMICAL PROCESS

Physical treatment steps: UNIT OPERATIONS

Heating
Cooling
 washing
Distillation
Filtration
Drying
crystallization
 MANY CHEMICAL REACTIONS
• UBIQUITOUS
• OUR BODIES
 ENVIRONMENT-decomposition of organics
 OZONE LAYER DEPLETION
 SMOG
 POWER GENERATION
• CORROSION
• INDUSTRIAL PRODUCTS
• DOMESTIC PRODUCTS
• **NO WORLD WITHOUT CHEMICAL REACTIONS
• **No condition is permanent
 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 of species’ atoms –H,N, Ca
• number of species’ atoms-H2O, H2O2 and
• configuration of species’ atoms -isomers
 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
 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; 0R
• R is the universal gas constant.
• The units of Ea and R must be consistent. If Ea is in kJ/mol
then R must have units of kJ/mol-K
• k0 =the frequency or pre-exponential" or "entropy factor
• Ea/R=Activation temperature
• 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

k 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 k0

slope=-Ea/R
Ln k
Higher Ea

Lower Ea

1/T
 Least square method of obtaining Ea and k0
• Linearizing Arrhenius equation:
•  yields a straight line equation :
• where - - -1

• Multiplying eqn.1 by x

• - - -2
• Summing all the n data points as given in the eqn.1

• - - -4

• Summing all the n data points as given in the eq.2

•
• - - -6
 Summing all the n data points as given in the equations 1 and 2:

Expt. # x = 1/T y = k x2 xy
1 x1 y1 (x1)2 x1 y1
2 x2 y2 (x2)2 x2 y2
--- --- --- --- ---
n xn yn (xn)2 xn yn
Σ Σ xi Σ yi Σ (xi)2 Σ xi y i
 Least square method
• Eqn4/n: - - -5

• Eqn.6/ : - - -7

• Eqn.6- Eqn.7:

• Hence:

•
 Activation energy: implications
• The smaller the activation energy of a reaction, the
lower is the sensitivity of the reaction to
temperature change
• The higher the activation energy of a reaction, the
greater is the sensitivity of the reaction to
temperature change
• The higher the Ea , the slower the rate will be.
• Endothermic reactions have higher Ea and hence are
slower than exothermic ones
• The effect of a rise in temperature is more on the
rate of an endothermic reaction than on an
exothermic one because of the value of the Ea
 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 )=CAα CBβ CCγ
• where
• α is the order of reaction with respect to the reactant A
•  
• β is the order of reaction with respect to the reactant B
•  

• γ is the order of reaction with respect to the reactant C

•  
• n= α +β +γ
• 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
 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: -rA =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 in the balanced equation
• It must be emphasized that the orders
of reaction are determined
experimentally
• cannot predict the rate law for a
chemical reaction from the balanced
 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 ;
• N2O5 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 one-step

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
• This is the rate-limiting 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 C NO CH2
2

• 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
dominated by the rate law for the slowest
step in the reaction.
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 input of energy.
• The activated complex can not be isolated;
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) CH3COO(aq) +CH3OH(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)
• In the acid hydrolyses of esters H3O+(aq) is removed, and
• the pH increases with time, with a corresponding change in EMF.
 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 α 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 α 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
 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 consumed is
also given by
• NB0 – NB= NB0 XB
• But the quantities that react are related by the coefficients
 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, ξ , is defined as

• ξ = (Ni – Ni0)/ υi
• where
• Ni0 = number of moles of i into reactor (t=0)
Ni = number of moles of i out of reactor (t = t)
• υi =stoichiometric coefficient of i
• Ni = Ni0 + υi ξ
• ξ (mol/s) is same for all species, must be positive
• a dummy variable that reflects how far each reaction
proceeds.
 *
• υi is positive for a product
• υi 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 the reaction
mixture
 Stoichiometric Table at XA for constant volume batch
reactor
Compon Initial Change due Moles Concentration
ent charge [2] to reaction, remaining, Ni [4] Ci [5]
[1] [3]
A NA0= NA0θA -NA0XA NA0θA -NA0XA NA0 (θA -XA)/ V
= NA0 (θA -XA) = CA0 (θA -XA)

B NB0= NA0θB -NA0XA(b/a) NA0θB-NA0XA(b/a) NA0 [θB-XA(b/a)]/ V

= NA0 [θB-XA(b/a)] = CA0 [θB-XA(b/a)]

C NC0= NA0θC NA0XA(c/a) NA0θC+ NA0XA(c/a) NA0 [θC+XA(c/a)]/ V

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

D ND0= NA0θD NA0XA(d/a) NA0θD+ NA0XA(d/a) NA0 [θD+XA(d/a)]/V

= NA0 [θD+XA(d/a)] = CA0 [θD+XA(d/a)]

I NI0= NA0θI 0 = NA0θI =NA0θI /V

Total
N0=NA0(θA + θB + θC + θD + θI) 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 θi0.
• The definition of θi0, 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.
• Θi = Ni0/ NA0 ;ΘA = NA0/ NA0 =1 ; ΘB = NB0/ NA0
•
• ΘC = NC0/ NA0 ;ΘD = ND0/ NA0 ; ΘI = 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 N A0XA,
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
= NA0θB-NA0XA(b/a)= NA0 [θB-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
=NA0θD+ NA0XA(d/a) = NA0 [θD+XA(d/a)]

Note that θD =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. Ci = 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 CA)
Compo Initial Change due Moles Concentration
nent charge [2] to reaction, [3] remaining, Ni [4] Ci [5]
[1]

A NA0= NA0θA -( NA0- NA) NA0θA -( NA0- NA)= NA NA/V

=CA
B NB0= NA0θB -( NA0- NA) (b/a) NA0θB-( NA0- NA)(b/a) [NA0(θB - b/a)+ b/a NA]/V
=NA0(θB - b/a)+ b/a NA CB= CA0(θB-b/a)+ (b/a) CA
= 2.0(1-0.5)+ (0.5) CA
= 1.0+ (0.5) CA
D ND0= NA0θD ( NA0- NA) (d/a) NA0θD+( NA0- NA)(d/a) [ NA0(θD +d/a)-(d/a)NA]/V
= NA0(θD +d/a)-(c/a)NA CD=CA0(θD +d/a)-(d/a)CA]
=2(0+1.5)-(1.5)CA]
=3-1.5CA
I NI0= NA0θI 0 NA0θI NA0θI/V
CI= 2.0(0.05)=0.10
Total N0=NA0(1 + 1 + 0 + 0.05) Nt=NA0(1 + 1 + 0 +0.05) +( NA0- NA)(1.5+0-0.5-1)
=2.05 NA0 = 2.05 NA0+( NA0- NA) )(1.5+0-0.5-1)
2.05x200=410 =2.05 NA0 +0=2.05x200=410
Stoichiometric Table for constant volume batch
reactor (in terms of a product D i.e. CD)
Compo Initial Change due Moles Concentration
nent charge [2] to reaction, [3] remaining, Ni [4] Ci [5]
[1]
A NA0= NA0θA -( ND-ND0)(a/d) NA0 -(ND-ND0)(a/d) [NA0 -( ND-ND0)(a/d)]/V
=CA0 -(CD-CD0)(a/d)

B NB0= NA0θB -( ND-ND0)(b/d) NB0-(ND-ND0)(b/d) [NB0-( ND-ND0)(b/d)]/V

CB= CB0-(CD-CD0)(b/d)

C NC0= NA0θC ( ND-ND0)(c/d) NC0+(ND-ND0)(c/d) [NC0+( ND-ND0)(c/d)] /V

CC= CC0 + (CD-CD0)(c/d)

D ND0= NA0θD ( ND-ND0) ND ND /V

= CD

I NI0= NA0θI 0 NA0θI NA0θI/V

CI= CA0θI
 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;
• if the rate is affected by [product] then the use of integrated rate
expressions can give completely misleading conclusions.
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: A B
 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 i
  k f (C i )
dt
• 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]= kCAα

• ln(-dCA/dt)= lnk + α ln CA

• Hence a plot of ln(-dCA/dt) versus ln CA should give

a straight line of slope α

• No trial and error is involved here. The value of the

order is obtained from the plot
Differential Method: obtaining
order ln(-dCA/dt)= lnk + α ln CA
*

ln (-dCA/dt)
slope= α

intercept= lnk
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 CA 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
the 3-point formula for data of equal time
 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 a function of time
dC A     
-  kC A C B  kC A C B0  kC A
dt
•By now reacting under conditions of excess
reactant A, the concentration versus time data of
component B is obtained.
dCA     
- 
 kCA CB  kCA0 C B  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 (t1/2), 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=kτ
• 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. t  1
1/ 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 order of the reaction.
1 n 1 n
C (0.5  1)
A0
 t1/ 2
( n  1)k

• Taking logs of both sides

1 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
• Intercept = (n  1)k
• 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) Slope =1-n

(0.51 n  1)
int ercept 
(n  1)k ln(CA0)
 different slope signs depending on the order
of reaction
• *

Orders of reaction < 1

lnt1/2
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 CAα CBβ
• If B is the reactant in excess,
• A is the ‘isolated’ reactant
• CA changes while CB remains virtually constant
during the reaction.
• Hence
• – rA= -dCA/dt =(k CBβ )CAα=(k CB0β )CAα = k' Caα
• *

ln(-rA)

ln(CA0)
 Method of excess.3
• k' is a pseudo-α-order rate constant.
• The reaction is a pseudo- α -order reaction,
because it behaves as if it were α -order
although it is not really α-order.
• It is α-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 20-fold

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 at
preferably the same temperature but using different
initial concentrations of reactants.
 METHOD OF INITIAL RATES:

• The rate law for reversible

reaction :A+B=C+D has the general
form
–
• A r = -dC A /dt =k C A
α
C B
β
-k’C C
a
C D
b

• At t=0, and with no products in the initial

charge, CC0=0; CD0=0;
• -rA=-rA0
• – r = -dC /dt =k C α
C β
series of runs with the same CB0 but
different CA0, and measuring the rate [-rA0
• ln(– rA0)=ln(k. CB0β)+ α lnCA0

ln(– rA0)

slope=α

ln(k. CB0β)

ln(–CA0)
 Runs with same CA0 but different CB0 and measuring -
rA0
• ln(– rA0)=ln(k. CA0 α)+ β lnCB0

ln(– rA0)
slope= β

ln(k. CA0α)
 Least–square method
• The least–square 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 CA are the variables measured
experimentally
 Least–square method2
• the plot of vs. ln CA 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.
• The data for each run i can be written in the
form;
 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 α and k by the least square methods
Run Xi Yi xiyi xi2
CAi (-rAj) =lnCA =ln(-rA)
1
CA1 (-rA1) lnCA1 ln(-rA1) lnCA1*ln(-rA1) (lnCA1)2
2
CA2 (-rA2) lnCA2 ln(-rA2) lnCA2*ln(-rA2) (lnCA2)2
3
CA3 (-rA1) lnCA3 ln(-rA3) lnCA3*ln(-rA3) (lnCA3)2
4
CA4 (-rA4) lnCA4 ln(-rA4) lnCA4*ln(-rA4) (lnCA4)2
n
Can (-rAn) lnCAn ln(-rAn) lnCAn*ln(-rAn) (lnCAn)2
summations

Σ Σ Σ Σ
lnCAi ln(-rAi) lnCAi *ln(-rAi) (lnCAi)2
 Least square method
•The two simultaneous equations 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

i x1i x2i yi x1i2 x1i x2i x1iyi x2i2 yi x2i

n
 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 + εAXA
 εA=( NT-N0)/ N0 =yA0 ∆n /a At XA =1

• εA =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 + εAXA)
• Assuming negligible change in compressibility
factors within the range of operation,
• V= V0 (P0 /P) (T/T0) (1 + εAXA)
• In a constant pressure (P0=P) isothermal (T=T0) batch
reactor the relationship simplifies to
• V= V0 (1 + εAXA)
 VARIABLE VOLUME BATCH REACTOR: XA and CA
• XA =(V- V0 )/ εAV0

• dXA/dt= [1/εAV0]dV/dt

• CA= NA/V =NA0(1 –XA)/V0 (1 + εAXA)

• CA= CA0(1 -XA)/(1 + εAXA)

VARIABLE VOLUME BATCH REACTOR: -rA
• -rA=(-1/V)(dNA/dt)
• = (-1/ V0 (1 + εAXA)(dNA0 (1 –XA)/dt)
• = (-1/ V0 (1 + εAXA)(-NA0dXA)/dt)
• =[CA0/ (1 + εAXA)] [dXA/dt]
• -rA =[CA0/εAV][dV/dt]=[CA0/εA][d(lnV)/dt]

• For zero order:

• -rA = [CA0/εA][d(lnV)/dt]=k
• [d(lnV)]=[εA/CA0]k dt Integrating

• ln(V/V0)=[kεA/CA0] t
Variable volume, constant pressure, isothermal batch reactor:
Zero order reaction

εA > 0

ln(V/V0)

εA < 0
VARIABLE VOLUME BATCH REACTOR: -rA
• For first order: -rA = [CA0/εA][d(lnV)/dt]=kCA
• Substituting for CA
• [CA0/εA][d(lnV)/dt]=k CA0(1 -XA)/(1 + εAXA)
• Simplifying
• [dV/V)/dt]=k εA(1 -XA)V0/V
• dV =kεA[(1 -(V- V0 )/εAV0)]V0 dt
• dV= k[εAV0-(V-V0)]=k[(1+εA)V0–V]dt Integrating
• -ln[(1+εA)V0–V]/[(1+εA)V0–V0]=kt
• -ln[V0+V0εA–V]/[εAV0]=-ln[V0εA–ΔV]/[εAV0]=kt
• -ln[1–ΔV/εAV0]=kt ; ΔV=V-V0
Variable volume, constant pressure, isothermal batch reactor:
first order reaction

-ln[1–ΔV/εAV0]

t
 Q & A
• Nitric acid is made commercially from nitric oxide. Nitric oxide is
produced by the gas-phase oxidation of ammonia.
• 4NH3 + 5O2 4NO + 6H2O
• The feed consists of 15 mol% ammonia in air at 8.2 atm and 227°C.
• 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 for C1 and C2 above.
Assume the reaction is first order in both reactants
 Total pressure in constant volume batch reactors: gas
phase reactions
component initial charge change due to moles remaining in terms of
Ni0 reaction at NA total moles
Ni
A NA0θA -( NA0-NA) NA0θA-( NA0-NA)

= NA0θ-(NT-N0) (a/Δn)
B NA0θB -( NA0-NA) (b/a) NA0θB -( NA0-NA)(b/a)

=NA0θB -(NT-N0)(b/Δn)
C NA0θC ( NA0-NA) (c/a) NA0θC +( NA0-NA) (c/a)

=NA0θC+(NT-N0)(c/Δn)
D NA0θD ( NA0-NA) (d/a) NA0θD +( NA0-NA) (d/a)

=NA0θD +(NT-N0)(d/Δn)
I NA0θI 0 NA0θI
• Total moles initially
• N0=NA0 (θA +θB + θC +θD +θI ) - - - 3.1
• Total moles remaining
• NT =NA0 (θA +θB + θC +θD +θI )-( 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)(Δn/a)

• ( NA0-NA)= (NT-N0)(a/Δn)
 At constant temperature and volume
Pi=NiRT/V or Ni=Pi V/RT
component Ni Pi=NiRT/V
A NA0 -(NT-N0)a/Δn PA= PA0 - (PT-P0)a/Δn
B NA0θB -( NT-N0)(b/Δn) PB= PA0θB - (PT-P0)b/Δn
C NA0θC +( NT-N0)(c/Δn) PC= PA0θC + (PT-P0)c/Δn
D NA0θD +( NT-N0)(d/Δn) PD= PA0θD + (PT-P0)d/Δn

NA=NA0-(NT-N0)a/Δn PAV/RT=PA0V/RT- (PT-P0)Va/ΔnRT PA=PA0- (PT-P0)a/Δn

NB=NA0θB -( NT-N0)b/Δn PBV/RT=PA0θBV/RT- (PT-P0)Vb/ΔnRT PB=PA0θB- (PT-P0)b/Δn

NC =NA0θC +( NT-N0)(c/Δn PCV/RT=PA0θCV/RT+ (PT-P0)Vc/ΔnRT PC=PA0θC+ (PT-P0)c/Δn

ND =NA0θD +( NT-N0)(d/Δn PDV/RT=PA0θDV/RT+ (PT-P0)Vd/ΔnRT PD=PA0θD+ (PT-P0)d/Δn

NI =NA0θI PIV/RT=PA0θIV/RT PI=PA0θI

 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

• 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
 A D
• 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: A D

• 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
CD
25 8
-rA=forward reaction
7
20
6

mole/L
mole/L.min

k1=3/min; k1'=1.0
5 k1 =3/min; k1 '=1.0/min
15
4
CA
3
10
2
rA=reverse reaction
1
5
0
0 0.5 1 1.5 2 2.5
0 t, min
0 0.20.40.60.8 1 1.21.41.61.8 2
t,min
 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
A NA0 -(NA0- NA) NA CA
D 0 (NA0- NA) NA0- NA CA0- CA
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 k1. 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=k1/k1’, the two constants of the reversible reaction
can be found
Consecutive/Series First Order irreversible A k1
B k2 C

• 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
B k2 C

CH4 +Cl2 CH3Cl +Cl2 CH2Cl2 +Cl2 CHCl3 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
10 CA CA

CC
9
9
CC
8
8
7
7
6 k1=1.0/ 6
k1=1.0/min;
min; k2=10.0/min
mole/L

mole/L
5 k2=2.0/min 5

4 4

3 3

2 CB 2 CB

1 1

0 0
0 0.5 1 1.5 2 2.5 3 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5

t,min t,min
CATALYSIS
Introduction to catalysis
Science and technology of catalysis is of great significance in our daily lives
including the four major sectors of the world economy (petroleum and
energy production, chemicals and polymer production, food industry and
pollution control, involve catalytic processes).
Catalysts are used to produce fuels (gasoline, diesel, heating oil, fuel oil etc.), plastics, synthetic
rubbers, fabrics, cosmetics, clean energy from renewable energy sources, such as hydrogen for
fuel cells and transportation fuels from non-edible biomass are also catalyst dependent
processes.

Automobile emission: catalysts are used to reduce emissions of CO, NOx and hydrocarbons
from mobile vehicles.

Catalysts are also used in the production of the polymers including . The pharmaceutical
industry uses catalysts for production of drugs that are used to save lives and improve the
health of people.

Catalysts are also widely used in food processing. More than 90 % of industrial processes
actually use catalysts in one form or the other. Owing to expanding need of mankind,
production in all sectors is increasing at a fast rate and catalysis science and technology has a
major contribution in this.

Thrusts are being given in the areas of catalyst upgrading to new and more efficient catalysts.
Increasing catalyst life is another area of importance to maximize catalyst efficiency.