LECTURE NOTES

in

CHEMICAL REACTION ENGINEERING

Engr Nilo T. Aldon ChE 009692
College of Engineering
Colegio San Agustin-Bacolod
November 12, 2012

1
1.1

Introduction
Chemical Kinetics ___ the study of the rate of reaction and mechanism by which one chemical
species is converted to another.
Analyzing the influence of different reaction conditions on the reaction rate gives information about
the reaction mechanism and the transition state of a chemical reaction.
In 1864, Peter Waage, a Norwegian pioneered the development of chemical kinetics by formulating
the law of mass action (the speed of a chemical reaction is proportional to the quantity of the reacting
substances.)
Focal Points Of Chemical Kinetics
1.

Rate of reaction
Kinetics deals with the experimental determination of reaction rates from which a rate law and
reaction rate constant are derived. Essential rate laws exist for zero order reactions (for which reaction
rates are independent of initial concentration), first order reactions, and second order reactions, and can
be derived for others through calculus. In consecutive reactions the rate-determining step often determines
the kinetics. In consecutive first order reactions, a steady state approximation can simplify the rate law.
The activation energy for a reaction is experimentally determined through the Arrhenius equation and the
Eyring equation. The main factors that influence the reaction rate include: the physical state of the
reactants, the concentrations of the reactants, the temperature at which the reaction occurs, and whether
or not any catalysts are present in the reaction.
2.

Mechanisms
In chemistry, a reaction mechanism is the step by step sequence of elementary reactions by
which overall chemical change occurs.
Although only the net chemical change is directly observable for most chemical reactions,
experiments can often be designed that suggest the possible sequence of steps in a reaction mechanism.
An overall description of how a reaction occurs. A mechanism describes in detail exactly what
takes place at each stage of a chemical transformation. It describes the transition state and which bonds
are broken and in what order, which bonds are formed and in what order, and what the relative rates of the
steps are. A complete mechanism must also account for all reactants used, the function of a catalyst,
stereochemistry, all products formed and the amount each.

Principal Function of Reaction Kinetics from Chemical Engineers Point of View

Establishing the chemical reaction mechanism

Collecting experimental data
Correlating rate data by mathematical equation
Designing suitable reactors
Specifying operating conditions, methods of control and auxiliary equipment.

1.2 Chemical reaction engineering _is the branch of engineering that is concerned with the exploitation of
chemical reactions on a commercial scale for purposes other than the production of power.

Fundamentals of Chemical Kinetics

nilotaldon12/21/2015

Page

1 /40

2.1 Classification of Reaction:

2.1.1

Mechanism (Elementary or non-elementary)

1. Irreversible
A B
2. Reversible

Reversible Reactions_is one which results in the formation of an equilibrium mixture. The
concept of a reversible reaction was introduced by Berthollet (1803) after he had observed the formation of
sodium carbonate crystals at the edge of a salt lake.
2NaCl + CaCO3 Na2CO3 + CaCl2
He recognized this as the reverse of the familiar reaction
Na2CO3 + CaCl2 2NaCl + CaCO3

3. Simultaneous

2.1.2
2.1.3

2.1.4

A B
A C
A BC

4. Consecutive
5. Autocatalytic
A+ B B + B
6. Homogenous Catalyzed
A+ C R + C
Phases
5. Homogeneous
6. Heterogeneous
Operating Conditions
7. Isothermal @ constant volume
8. Isothermal @ constant pressure
9. Adiabatic
10. Non-adiabatic and non-isothermal
Molecularity
11. Unimolecular
A B

Example is the decomposition of ozone :

O3 O 2 O

2.1.5
2.1.6

2.1.7

12. Bimolecular
A BP
H O2 OH O
13. Trimolecular or Termolecular
A BC P
A 2B P
3A P
2 NO O2 2 NO 2
Order
14. Integral (1st, 2nd, 3rd)
15. Fractional or Zero
System
16. Batch
17. Flow
18. Semi-batch or semi-flow
Equipment
19. Stirred tank (single or multistage)
20. Tubular (single or multiple)
21. Packed bed (fixed bed, moving bed, fluidized bed-dense phase/dilute phase)

nilotaldon12/21/2015

Page

2 /40

2.1.8
2.1.9

2.2

Catalyst
22. Catalyzed
23. Uncatalyzed
Heat evolved
24. Exothermic
25. Endothermic

Rate of reaction

r
A

___ the number of units of mass of some participating reactants which

is transformed into a product per unit time and per unit volume.

1 dN A

V dt

The negative sign denotes the

disappearance of reactant A .
A positive sign on the other hand
denotes formation of a product .

2.2.1 Basic Factors Affecting The Rate of Reaction :

a. Nature of the Reactants
The terms active and inactive are used in describing the nature of reactants. For instance, we say
that sodium is a very active metal which reacts violently with water. The activity of elements are
predicted by the use of the periodic table. An example of which is the activity series of metals which
ranks potassium as the most active. When covalent bond formation takes place between the molecules
and when large molecules are formed, the reactions tend to be very slow.
b. Frequency and efficiency of collisions of the reactant particles.
It follows that any factor (physical state, composition, temperature, pressure, area of exposure,
catalysts, etc) which affects the frequency and efficiency of collisions of the reactant particles will
necessarily alter the speed of reaction.
1. Physical State
Physical state (solid, liquid, or gas) of a reactant is also an important factor of the rate of
change. When reactants are in the same phase, as in aqueous solution, thermal motion brings them
into contact. However, when they are in different phases, the reaction is limited to the interface
between the reactants. Reaction can only occur at their area of contact, in the case of a liquid and a
gas, at the surface of the liquid. Vigorous shaking and stirring may be needed to bring the reaction to
completion. This means that the more finely divided a solid or liquid reactant, the greater its surface
area per unit volume, and the more contact it makes with the other reactant, thus the faster the
reaction. To make an analogy, for example, when you start a fire, first you use wood chips and small
branches - you don't start with big logs right away. In organic chemistry On water reactions are the
exception to the rule that homogeneous reactions take place faster than heterogeneous reactions.
2. Concentration or composition of the reactant(s)
Concentration plays an important role in reactions. According to the collision theory of chemical
reactions, this is due to the fact that molecules must collide in order to react together. As the
concentration of the reactants increases, the frequency of the molecules colliding increases, striking
each other faster by being in closer contact at any given point in time. Imagine two reactants being in
a closed container. All the molecules contained within are colliding constantly. By increasing the
amount of one or more of the reactants you cause these collisions to happen more often, increasing
the reaction rate.
Law of Mass Action _states that the rate of chemical reaction is at each instant proportional to the
concentration of the reactant with each raised to a power equal to their coefficient or the actual
number of molecules participating in the reaction. This law can be interpreted by several complex
mechanisms but it can simply be explained as follows: when two or more molecules react, it must
come close to one another or must collide. Therefore, it is expected that the rate of reaction increases
if the molecules are crowded closely together, i.e., the concentration is high.
3. Temperature
nilotaldon12/21/2015

Page

3 /40

Temperature usually has a major effect on the speed of a reaction. Molecules at a higher
temperature have more thermal energy. When reactants (reactant + reactant product) in a chemical
reaction are heated, the more energetic atoms or molecules have a greater probability to collide with
one another. Thus, more collisions occur at a higher temperature, making a product in a chemical
reaction. More importantly however, is the fact that at higher temperatures molecules have more
vibrational energy, that is, atoms are vibrating much more violently, so raising the temperature not
only increases the number of collisions but also collisions that can result in rearrangement of atoms
within the reactant molecules. For example, a refrigerator slows down the speed of the rate of
reaction since it cools the molecules. On the other hand, an oven gives heat (energy) to the molecules
which in turn speeds up the rate of reaction, cooking the food faster.
Chemical kinetics can also be determined using a Temperature Jump. This involves using a sharp
rise in temperature and observing the relaxation rate of an equilibrium process.
The kinetic energy of particles follows the Maxwell-Boltzmann distribution. An increase in
temperature not only increases the average speed of the reactant particles and the number of
collisions, but also the fraction of particles having kinetic energy higher than the activation energy.
Thus, the effective collision frequency increases.
4. Pressure
By increasing the pressure, you decrease the volume between molecules and will increase the
number of collisions between reactants, increasing the rate of reaction. This is because the activity of
a gas is directly proportional to the partial pressure of the gas. This is similar to the effect of
increasing the concentration of a solution.
5. Catalysts
A catalyst is a substance that accelerates the rate of a chemical reaction but remains
chemically unchanged afterwards. The catalyst increases rate reaction by providing a different
reaction mechanism to occur with a lower activation energy.
In autocatalysis a reaction product is itself a catalyst for that reaction leading to positive
feedback. Proteins that act as catalysts in biochemical reactions are called enzymes. MichaelisMenten kinetics describe the rate of enzyme mediated reactions.
In certain organic molecules specific substituents can have an influence on reaction rate in
neighboring group participation.
Agitating or mixing a solution will also accelerate the rate of a chemical reaction, as this
gives the particles greater kinetic energy, increasing the number of collisions between reactants and
therefore the possibility of successful collisions.

2.2.2 Factors Affecting the Rate of Homogeneous Reactions :

1. Composition
rA= f (temperature, pressure, composition)
2. Temperature
3. Pressure
These variables are interdependent in that the pressure is fixed, given the temperature and composition of the
phase. This we may write without loss of generality.

rA= f (temperature, composition)

2.2.3 Factors Affecting Heterogeneous Reactions :
1. Mass transfer factors (e.g. diffusion characteristics of fluid phases)
2. Contact patterns of phases ( each phase may be in one of two ideal flow patterns i.e. plug or back-mix
flow. There are a number of possible combinations of contacting patterns)
3. Fluid dynamic factors (e.g. mass velocity, degree of turbulence, etc)
4. Interfacial surface area
5. Geometry of the reaction vessels
6. Chemical kinetic factors (i.e. activation energy, concentration of reactants, etc)
7. Temperature and pressure
Some of these factors are not completely independent and may interact with each other.
nilotaldon12/21/2015

Page

4 /40

2.3
2.3.1

Mathematical Expression of Rate of Chemical Reaction

Stoichiometry:
1. Stoichiometry may suggest whether we have a single reaction or not.
2. Stoichiometry can suggest whether a single reaction is elementary or not because no elementary
reactions with molecularity greater than three have been observed.
The stoichiometric equation is a chemical equation which expresses an overall chemical reaction
in terms of the simplest ratio of reactant and product molecules.
Consider the irreversible elementary reaction

aA + bB rR + sS

The stoichiometric relationship of this given chemical reaction is

-rA
a
rA

-rB
b

=
=

- dC A
dt

rR
r

rS =
k A CaA C Bb
a

rS
s

= k A CaA CBb
rB =

rR

+ dC R
dt
+dCS
dt

k Ca C b
= B A B
b

- dCB
dt

= k BCaA C Bb

= k R CaA CBb
= k SCaA CBb
k R CaA C Bb
=
r

k SCaA CBb
=
s

From the preceding equations the values of the specific rate constants k B, kR and kS are solved as a function of k A
thus,

k A CaA C Bb
a

kR =

k BCaA CBb
kB =
;
=

b
r
s
k A ; kS = k A
a
a

b
kA
a

Kinetically, the system is at equilibrium if the net rate of change of the forward and backward
elementary reactions is zero.
Consider the elementary reversible reaction
k1
A+ B
R+S
k2
The rate of formation of R by the forward reaction is:

Rate of Formation of R : rR k1C A C B

And the rate of disappearance by the reverse reaction is

Rate of Disappearance of R : - rR k 2 C R C S

At equilibrium the net rate of formation of R is zero, then

nilotaldon12/21/2015

Page

5 /40

rforward =rbackward = 0

rforward = rbackward
k1CACB = k2CRCS
k1 C R C S
=
k 2 CA CB

Since for this reaction kC is defined as

kC =

C R CS
CA CB

at equilibrium we have
kC =

k1
k2

C Re CSe
C Ae CBe

kC, which is equal to k1/k2, is a constant independent of concentration. C Ae, CBe, CRe, and CSe are
equilibrium concentrations with respect to A, B, R, and S, respectively. Thus, the equation for k c is very
specific only for equilibrium condition.
The rate of chemical reaction is dependent on temperature, pressure, and concentration. In particular,
an important relationship is expressed by the Law of Mass Action. The Law of Mass Action states that the
rate of chemical reaction is at each instant proportional to the concentration of the reactant with each
raised to a power equal to their coefficient or the actual number of molecules participating in the reaction.
This law can be interpreted by several complex mechanisms but it can simply be explained as follows:
when two or more molecules react, it must come close to one another or must collide. Therefore, it is
expected that the rate of reaction increases if the molecules are crowded closely together, i.e., the
concentration is high.
The statement of the Law of Mass Action is translated into its mathematical expression using the
following defined notations:
ri = rate of reaction of any substance i
i = any substance in the reaction
Ci = concentration of any substance i in the reaction.
Suppose the reaction is represented by
A k P
Applying the principle of the Law of Mass Action

rA

CA

The preceding equation is the mathematical expression of the Law of Mass Action.
Given an irreversible chemical reaction

aA + bB + cC+...

where:

dD + eE +...

A, B, C = are the reactants participating in the chemical reaction;

D, E = are the products formed during chemical reaction;
a, b, c, d and e are the number of molecules of each substance involved in
the chemical reaction, then

From the given chemical reaction the rate expression of A is given as:

rA C A a C B b C C c
nilotaldon12/21/2015

Page

6 /40

 rA kC A a C B b C C c
Also:

rB

b
a
b
c
kC A C B CC
a

c
a
b
c
kC A C B C C
a
Consider the rate of change of component i involved in the chemical reaction. If the rate of
change in the number of moles of this component is dNi/dt, the rate in the various areas of kinetics is
defined as follows

rC

Based on a unit volume of reacting fluid,

dN i
Change in No. of moles of any substance i
=
Vf dt
unit volume of fluid time
Based on unit volume of reactor, if different from the rate based on unit volume of fluid,
dN i
Chnage in the No. of moles of any substance i
ri =
=
Vr dt
Unit volume of reactor time
Based on unit interfacial surface in two fluid systems or based on unit surface of solid in gas-solid systems ,
ri

ri

dNi
Sdt

Change in the No. of moles of any substance i

Unit surface area time

Based on unit mass of solid in fluid-solid systems,

ri

dN i
=
Ws dt

Change in

the No. of moles of any substance i

unit mass of solid time

2.3.2 Molecularity and Order of Reaction

The molecularity and order of an elementary reaction is the number of molecules involved in the rate
determining step of a reaction. Molecularity of reactions has been found to be one, two, and occasionally
three. Molecularity refers only to an elementary reaction and can only be whole numbers.
Example:
Consider the irreversible elementary reaction

aA + bB + cC +.. product
where a, b, and c are stoichiometric coefficients. We call the power to which the concentration
raised the order of reaction.

rA kC A pCBq CC r
nilotaldon12/21/2015

Page

7 /40

are

When the stoichiometric equation truly represents the mechanism of the reaction, the order and
molecularity both are n = a + b + c and individually p = a, q = b, r = c

Thus, the reaction is

ath order with respect to A
bth order with respect to B
cth order with respect to C
nth order over all
n = a + b + c + .
Example:
1.
2.
3.
4.

A P
A+ B
P
2A + B
P
A+ B+ C P

(n=1)
(n=2)
(n=3)
(n=3)

Rates of disappearance of reactants or formation of products are related to A by the stoichiometric coefficients:

rA rB rC
a

2.3.3 Rate Constant k :

For Equation : aA product (s)
The rate of disappearance of reactant A:

rA k

rA k

nA

V
nA

1
unit time

unit mass

unit volume

unit volume n 1
unit mass n 1 time

unit mass
unit volume time

for zero-order

1
time

for 1st-order

unit volume
unit mass time

unit volume 2
unit mass 2 time

unit of k for an nth order chemical reaction.

for 2nd-order
for 3rd-order

The reaction rate constant could also be expressed in terms of pressure ( ) and mole fraction (NA):
If we let

CA

nilotaldon12/21/2015

PA N A

RT
RT

Page

8 /40

(-rA) = kc (CA)n = kp (PA)n

n

rA
PA
kc
k
CA n p CA n

k P RT

NA
kN
CA n

RT

kN

Rate and Order Questions

1.

A reaction has the stoichiometric equation

2A R S

What is the order of reaction?

Answer: The reaction is elementary, irreversible, second order
2.

Given the reaction

1
O2 N 2O5
2
What is the relation between the rates of formation and disappearance of three components of the reaction?
Answer:
2 NO2

rNO k NO2 2 O2 0.5

2

rO 14 k NO2 2 O2 0.5 14 rNO

2

rN O 12 k NO2 2 O2 0.5 12 rNO

2

3.

A reaction with a stoichiometric equation

1
A B R
2

Has the following rate expression: rA 2 A 0.5 B

What is the rate expression for this reaction if the stoichiometric equation is written as
Answer: rA 2 A B

4.

A 2 B 2 R 2S

For the elementary reaction: 2A+B 2S

CAo= 8 mols/liter, CBo= 6 mols/liter, CSo= 2mols/liter
a. What is the order of reaction with respect to A?
b. What is the over-all order of reaction?
c. What is the limiting reactant?
d. If 75% of the limiting reactant is reacted after 5 minutes, what will be the values of C A, CB,,and CS ?
e. What is (-r A)?
f. What is (r B)?
g. What is (r S)?
SOLUTION:
a. Second-order
b. Third-order
c. A is the limiting reactant. 2 mols of A will react with 1 mol of B, hence, 8 mols A will react with
only 4 mols B.
8 0.75 3 mol
2 mol
8 mol ANSWER:
C 8 0.75 2
d. C 8 1 0.75
; C 6

;
A

nilotaldon12/21/2015

liter

liter

Page

liter

9 /40

dC A
12k mol
2
ANSWER:
kC A2CB k 2 3
dt
literminute
r
6 kmol
ANSWER:
f. rB A
2 literminute

e.

rA

12k mol
liter min ute

g. rs rA

5.

ANSWER:

The specific reaction rate of a first-order reaction is 2.5 x10 -7/s and the initial concentration is 0.1gmol/lit.
What is the initial rate expressed in terms of seconds, liters gmols.
SOLUTION:
dC A
2.5 x10 7 0.1gmol 2.5 x10 8 gmol
kC A
x

dt
s
lit
lit

6.

ANSWER:

The initial rate of a second-order reaction is 5.0x10 -7 gmol/lit-s when CA is 0.2 gmol/lit. What is the specific
reaction rate expressed in units of second, liter, gmol.
SOLUTION:
dnA
5.0 x10 7 gmol
0.2 gmol
kC A 2
k

Vdt
lit s
lit

5
1.25 x10 lit
ANSWER:
k
( gmol )( s)

( rA )

7.

The third-order gas-phase reaction 2NO+O 2 2NO2 has a specific reaction rate of kC=2.65 x104 lit2/
(gmol)2(s) at 30oC. Find kP and kN.
SOLUTION:
kC
lit 2
ANSWER: 1.7239
4

2
.
65
x
10
a. k P
n
2
2
3
3
(lit )( gmol ) 2 ( s) 2 ( atm) 2
( RT )
( gmol ) ( s ) (0.08205) (303k )

b. k N k C

2.65 x 10

RT

lit

gmol s
2

atm

0.08205 lit atm 303

8.

ANSWER:

1.7239
(lit )( gmol ) 2 ( s ) 2
The third-order gas-phase reaction 2NO + O2 2NO2 has a specific reaction rate at 30 oC and 1 atm. Find
kp and kn.
Solution;

L2
g.mol 2 .s

k c 2.65 x10 4
Solution:
n

kp

kc

RT n

nilotaldon12/21/2015

RT
kn

k c RT k p

2.65 x10 4 L2

g.mol 2 .sAnswer

0.08206 L.atm
303 K

g .mol.K

1.7239

Page

g mol
L . atm 3 .s

10 /40

gmol
g .mol
3
kn n k p 1 atm 1.7239
1.7239
L. atm 3 .s
L.s

9.

Answer

Ex. At a given temperature the following data were taken:

CH3CHO (g) CH4 (g) + CO (g)
A
B
C
Initial Pressure, A(Torr)
Experiment Number
1
300
2
200
a. Write the equation
b. Find the order of reaction
SOLUTION:

r d
dt

kPAn ; r1 kPAn1 ;

r2 kPAn2 :

kPAn1

r1

r2 kPAn2

Initial Rate of Increase in Total

pressure (Torr)
0.61
0.27

P
A1

PA2

r1
0.61
log
r2
0.27 2
n

300
PA
log
log 1
200
PA2
log

a. r = kPA2
b. 2nd-order reaction

2.4

Answer:

Mechanism __ is the sequence of individual chemical events whose over-all result

produce

the observed reaction.

__ the sequence of steps that takes place to complete a chemical change.
In most instances the postulated mechanism is a theory devised to explain the end results observed by
experiments. Like other theories, mechanisms are subject to change over the years as new data is uncovered or as
new concepts regarding chemical interactions are developed.
The mechanism of an overall chemical reaction consists of a series of elementary reactions, which together
bring about the overall reaction summarized in the stoichiometric equation.

A reaction mechanism is a set of steps at the molecular level. Each step involves combinations or rearrangements of individual molecular species. The steps in combination describe the path or route that
reactant molecules follow to reach the product molecules. The result of all steps is to produce the overall
balanced stoichiometric chemical equation for reactants producing products.
Page
11 /40
nilotaldon12/21/2015

2.4.1 Steps Followed in Establishing Reaction Mechanism :

1. Postulate a simple mechanism with a corresponding stoichiometry.

2. If the stoichiometry appears to indicate the reaction to be one-step and elementary, proceed to acquire
kinetic data and analyze them according to the integral method.
3. For non-elementary reactions, assume that the overall reaction consists of several elementary reaction
steps with formation of intermediate compounds.
4. Formulate a rate expression for each of the elementary steps and sum up the individual rate
expressions to describe the overall rate.
5. If the resulting rate expression agrees with experimental kinetic data, the assumed mechanism is
acceptable. Otherwise, continue to assume alternative mechanisms, and repeat step 4 until a desired
degree of agreement is obtained.
6. Frequently, it may be simpler to use a purely empirical approach to correlate the data.

2.5

Elementary and Non-Elementary Reactions

2.5.1 Elementary Reactions __ any such reaction in which the rate equation suggested by stoichiometric
equation represents the actual mode of action and occurs in a single step .
Ex. A 2B 2S P

rA rP KC A C B2
rB rS 2 KC A C B2

2.5.2

Non-elementary Reactions __ are those where there is no direct correspondence between

stoichiometric equation and the rate expression and occurs in two or more series of reactions.
Ex.

A 2B 2S P
rA rP KC A C B2
If

rA rP KC B2

or

the reaction is non-elementary.

Two Types of Non-Elementary Reaction Mechanism

1. Non-chain reaction mechanism
Reactants

(intermediates)*

(intermediates)*
Example:

Products

B*

B*

Mechanism

nilotaldon12/21/2015

Page

12 /40

2. Chain Reaction Mechanism

Reactants (intermediates)*
(intermediates)* + Reactant (Another intermediates)* + Product
(another intermediates)*
Example:
1. A + B S + P

Product

Mechanism
A I*
I* + B R* + S
R* P
2. 2A + B

P + 2R

Mechanism
A+B

AB*

AB* + A

S* + 2R

S*

Example: Present mechanisms consistent with experimentally found rate equation for the following reaction:

rA2

2A2B=2AB + A2 ;

1500 [ A2 B ] 2
[ AB ] 20[ A2 B]

SOLUTION:

A2 B A* AB
A* A2 B A2 AB
rA2 k 3 [ A* ][ A2 B] k 4[ [ A2 ][ AB ]
rA* k1[ A2 B ] k 2 [ A* ][ AB ] k3[ A* ][ A2 B ] k 4 [ A2 ][ AB ] 0
A*

k [ A B ] k 4 [ A2 ][ AB ]
k1[ A2 B ] k 4 [ A2 ][ AB ]
; rA2 k3[ A2 B ] 1 2
k 4 [ A2 ][ AB ]
k 2 [ AB ] k3[ A2 B ]
k 2 [ AB ] k3[ A2 B ]

k1 k 3 [ A2 B ] 2 k k 4 [ A2 ][ AB] 2
2

k 2 [ AB] k 3 [ A2 B]

Assume k4=0

rA

k1k3

k1 k 3 [ A2 B] 2

k 2 [ AB ] k 3 [ A2 B]

1
multiply by

k2
k2

[ A2 B]2

1500[ A2 B]2
k2

k3
[ AB]
[ A B ] [ AB] 20[ A2 B]
k2 2
Therefore, the mechanism will be:
nilotaldon12/21/2015

Page

13 /40

A2 B A* AB

ANSWER:

A A2 B A2 AB
*

k3

2.6. Effect of Temperature on Rate of Reaction:

2.6.1 Arrhenius Equation:
The Arrhenius equation is a simple, but remarkably accurate, formula for the temperature dependence of
a chemical reaction rate, more correctly, of a rate coefficient, as this coefficient includes all magnitudes that
affect reaction rate except for concentration. The equation was first proposed by the Dutch chemist Jacobus
Hendricus vant Hoff in 1884; five years later in 1889, the Swedish chemist Svante Arrhenius provided a
physical justification and interpretation for it. Nowadays it is best seen as an empirical relationship. In short,
the Arrhenius equation is an expression that shows the dependence of the rate constant k of chemical
reactions on the temperature T (in Kelvin) and activation energy Ea, as shown below:
where A is the pre-exponential factor or simply the prefactor and R is the gas constant. The units of the
pre-exponential factor are identical to those of the rate constant and will vary depending on the order of the
reaction. If the reaction is first order it has the units s -1, and for that reason it is often called the frequency
factor or attempt frequency of the reaction. When the activation energy is given in molecular units, instead of
molar units, e.g. joules per molecule instead of joules per mol, the Boltzmann constant is used instead of the
gas constant.
It can be seen that either increasing the temperature or decreasing the activation energy (for example
through the use of catalysts) will result in an increase in rate of reaction.

Where:
k = reaction rate constant

k A e RT

E = activation energy, cal/gmol

A = frequency factor
T = absolute temperature, K
Ho = standard-state enthalpy change, cal/gmol
R = 1.987 cal/gmol.K

k
e RT
A

k
E

A
RT
E
ln k
ln A
RT
Equation of a straight line: y = mx + b
where: y = lnk
m = slope = -E/R
x = 1/T
b = ln A
ln

k2
k1

E 1 1 EA
RT
Rg T2 k T1k o e

ln
Equation
The Arrhenius

Slope=-E/R
lnk2
Lnk1
1/T2

1/T1

gives a good empirical description of the temperature dependence of

the rate constant of an elementary reaction. Both E A and ko are independent of temperature. This expression fits
experimental data well over wide temperature ranges and is strongly suggested from various standpoints as being a
reasonable first approximation of the true temperature dependency.
1.

When only two sets of k and T are given

For a given k1 and T1 the equation becomes

k1 ko e

EA
RT1

Apply the natural logarithm to both sides of the equation and simplify
EA
EA
E
ln ko A
RT1
ln k1 ln ko e
ln ko ln e RT1
RT1
Solving for lnko will give
nilotaldon12/21/2015

ln ko ln k1

EA
RT1
Page

14 /40

Similarly for k2 and T2, Equation 1 becomes

EA

EA

ln k2 ln ko e RT2 ln ko ln e RT2
E
ln ko ln k2 A
RT2
Equating the two equations:

ln k1

EA
E
ln k2 A
RT1
RT2

Simplifying further :
ln k2 ln k1
ln

ln

EA
E
A
RT1 RT2

k2 E A 1 1

k1
R T1 T2

ln k

k2 E A T2 T1

k1
R T1T2

1/T

2. When more than two sets of rate constant (k) and temperature (T) are available:

EA

k ko e RT

Applying the natural logarithm to both sides of Equation and simplifying will give
EA
E
ln k ln ko A
is an equation of a straight line where ln ko and
are the intercept and the slope of
RT
R
the line, respectively. The natural logarithm of k

2.6.2 Collision Theory:

ln k is plotted against the reciprocal of temperature

1
.
T

RT

k T Ae

For a chemical reaction to proceed, molecules must have effective collisions. The two requirements for an
effective collisions are;
a.The molecules must be suitably reactive and must have enough energy,
b. The molecules must be arranged in a proper position.
Collision theory, was proposed by Max Trautz and William Lewis in 1916 that qualitatively explains how
chemical reactions occur and why reaction rates differ for different reactions. It assumes that for a reaction to
occur the reactant particles must collide, but only a certain fraction of the total collisions, the effective collisions,
cause the transformation of reactant molecules into products. This is due to the fact that only a fraction of the
molecules have sufficient energy and the right orientation at the moment of impact to break the existing bonds and
form new bonds. The minimal amount of energy needed so that the molecule is transformed is called activation
energy. Collision theory is closely related to chemical kinetics.
Collision theory views the rate to be governed by the number of energetic collisions between reactants.
What happens to the unstable intermediate is of no concern. It is simply assumed that this intermediate breaks
down rapidly enough into products so as not to influence the rate of the over-all process.

k ko

Ec
e RT

Where: k is the specific rate constant, ko is the collision theory constant, T is the temperature (K), R is the
universal constant (1.987 cal/g-mol K), and ECT is the collision theory activation energy (cal/g-mol).
nilotaldon12/21/2015

Page

15 /40

1. When only two sets of k and T are available

For a given k1 and T1 equation becomes
k1
ko' e
T1
ln

k1
T1

ln ko'

ln ko' ln

ln ko' ln
ln

Equating

ln

k
E
CT
T1 RT1

E
k2
CT
T2 RT2

k2
E
k
E
CT ln 1 CT
T2 RT2
T1 RT1

k2
k
E
E
ln 1

T2
T1 RT1 RT2

ln

E
RT1

k2
E
ln ko' CT
RT2
T2

ln

Similarly for k2 and T2

ECT
RT1

k2

T2
E T2 T1 ; ln k2 T1 ECT T2 T1

k1 R T1T2
R T2T1
k1 T2

T1

The preceding equation is used to determine the activation energy (ECT) if two sets of rate constants (k) and
temperature (T) are given.
2. When more than two sets of k and T are given the equation can be rearranged as shown below

k ko' T e
k
ko' e
T

ECT
RT

ECT
RT

Applying natural logarithm to both sides of the equation, then simplify will result into an equation of a straight
line.

k
E
ln ko' CT
RT
T

ln

The plot of ln

k
1
vs T is
T

ln

1/T

Plot of

ln

k
as a function of (1/T) for the determination of activation energy (ECT) and constant (ko).
T

nilotaldon12/21/2015

Page

16 /40

2.6.3 Transition-State Theory:

k TAe

E
RT

Activated Complex or Transition State Theory:

Henry Eyring, an American chemist, postulated an alternative to collision theory. He
hypothesized that an intermediate species called an activated complex forms during collision. This intermediate
species exist very briefly. It dissociates to form either the product (if reaction occurs) or the original reactants
(if reaction does not occur)
Most reactions proceed in many steps called elementary processes. The combined effect of all the
elementary processes gives the overall reaction. The slow step determines the rate of the chemical reaction and
is called the determining step. The observed rate of the overall reaction is the equivalent to the rate of the slow
reaction.Transition-state theory views the reaction rate to be governed by the rate of decomposition of
intermediate. The rate of formation of intermediate is assumed to be so rapid that it is present in equilibrium
concentrations at all times. The governing equation is

k k o Te
"

E ACT
RT

where, k is the specific rate constant, ko is the activated complex theory constant, T is the temperature (K), R
is the universal constant (1.987 cal/g-mol K), and EACT is the activation energy (cal/g-mol).
1. When two sets of k and T are given
For k1 and T1

k1 k T e
"
o 1

k1
ko"e
T1
nilotaldon12/21/2015

E ACT
RT1

E ACT
RT1

Page

17 /40

 k
ln 1 ln ko" ln e
T1

E ACT
RT1

k1
E ACT

RT1
T1

ln ko" ln

k2
E ACT

RT2
T2

similarly for k2 and T2

ln ko" ln

Equating

ln

k 2

k1

T1

T2

E ACT T2 T1

T 2T1
R

2. When more than 2 sets of k and T are available

E ACT
k
ko" e RT
T
E ACT
k
ln ln ko'' e RT
T
k

E ACT
k
"
ln ko
RT
T

ln

ln
1
k
vs is
T
T

The Plot ln
Plot of

1/T
k
as a function of (1/T) for the determination of activation energy (EACT) and constant (ko).
T

ln

2.6.4 General Equation:

2.6.5 Vant Hoff Equation:

k T m Ae

E
RT

d ln k
H o

dT
Rg T 2

Example:

1. If a first-order reaction has an activation energy (E) of 25,000 cal/gmol and in the equation
k=Ae-E/RT, A=5x1012/s. At what temperature will the reaction has a half-life of 1-minute?
SOLUTION:
25 , 000
E
1
12
RT
k 1 ln 2
ln 2 0.01155 Ae 5 x 10 e RT
60s
t2

ANSWER:

T 373.28 K

2.7.

EQUILIBRIUM
The system is in the state of equilibrium if the following characteristics are observed:
1. It is a closed system ( the amount of matter in the system does not change)
2. There is no change in the properties of the system as time passes.
3. Two processes, which are opposite in direction, simultaneously take place at the same rate.
4. The ratio of the product of the molar concentration of the substances formed to the product of the
molar concentration of the reactants is constant.

2.7.1 Factors that Affect Chemical Equilibrium:

nilotaldon12/21/2015

Page

18 /40

1. Temperature
2. Pressure
3. Composition
For Equilibrium: Pressure may be fixed given the temperature and composition of the phase, (due to
the interdependency of P and T )
Therefore: r = f ( T, C ) . This assumption could also be applied to non-equilibrium systems in the
absence of better supposition (theory).

2.7.2 Le Chateliers Principle:

If a stress (disturbance or change) is applied to a system in a state of equilibrium, the system will shift in
such a way to neutralize the effect of the stress.

Ex. In the decomposition of CaCO 3 =CO2 + CaO, the removal of CO 2 gas will trigger the system in a
state of equilibrium to produce more CO2 in order to offset the reduction in pressure.

The tendency of a reaction, whether physical or chemical, is determined by a balance between these two
factors:
1. The tendency toward a state of minimum energy, or low enthalpy; and
2. Tendency toward a state of maximum disorder, or high entropy.
If we represent the change in the heat content of a system as H, the change in entropy as S, and
absolute temperature as T, an equation which is helpful in predicting reaction tendency is ;

G = H - (T) (S). (free-energy change)

In spontaneous reactions, G is negative; in systems in equilibrium , G is zero.

2.7.3 Hesss Law : The total change in enthalpy of a system is dependent on the temperature, pressure, state
of aggregation, and state of combination at the beginning and at the end; it is independent of the number
of intermediate reactions

Design of Homogenous Batch Reactors

3.1

Constant-Volume Reactions:
Irreversible Reactions
dC
a
rA Order A k C AA B
a. Zero
dt
-(CA - CAo )=Kt
b. First- Order

ln

aA

bB

dC B b
kC A
dt
a
CA = CAo Kt

rB

CA
kt
C Ao

c. Second Order
Type 1

C A C Ao e kt

2A B

1
1

kt
C A C Ao
Type 2

C Bo

CA

C Ao
1 ktC Ao

A+ B R

C C
1
ln B Ao kt
C Ao C Bo C A

d. Third Order
nilotaldon12/21/2015

Page

19 /40

Type I

1
CA2

3A B

1
C Ao 2

Type II

CA

2kt

2C Bo C Ao C Ao C A
C Ao C A

2C

Ao

1 2ktC
2

Ao

2A + B R

Type III

C Ao

C A C Bo 2C Bo C Ao 2 kt
ln

C Ao C B
2

A + 2B R

C Bo C Bo C B
C C
2
ln B Ao 2C A C Bo kt
C Bo C B
C Bo C A
o

Type IV

A+ B + C R

3.2
a.

C Ao
1
C
1
C

ln Bo
ln Co kt
C Ao CCo C Ao CBo C A CBo CCo CBo C Ao CB CCo C Ao CCo CBo CC
Complex Constant-Volume Reactions
ln

A k1 B

Side or Simultaneous Reactions

A k2 C

C A C Ao e k1 k2 t

k 1 C Ao

1 e - k1 k 2 t

C B C Bo

k k
2
1

CB
CC

tC B max

k1C Ao k1 t
e k2t
e

k 2 k1

1
k k C k C
t
ln 2 1 Ao 2 Ao
k 2 k1 k 2 k 1 C A k 2C Ao

k1

k2

k k 2 k1
C BMax C Ao 1
k2
k1
C Bequib
C Ao e k1t
k2

C Ao
k t
k t
k2 k1 k1e 2 k 2e 1

k2 k1

nilotaldon12/21/2015

k2

k1

ln
k k
2 1

kt

Reversible Reaction

k1
k
CC 1 CCo
k2
k2

A k B k C

Consecutive Reactions

C A C Ao e

c.

1 e - k1 k 2 t

k k
2
1

b.

C B C Bo

k 2 C Ao

CC CCo

rB dC B k1 C B C Bo

rC dCC k 2 CC CCo

k2

Page

20 /40

1
C C Ae
ln Ao
k 2 k1 C A C Ae

d.

A k R
AC k R C

Homogeneous Catalyzed Reactions

Ln

e.

CA

CA

Ln 1 x A k1 k 2C c t k observed t
A R R R
k

Autocatalytic Reactions

Ln

C Ao Co C A

C A Co C Ao

Ln

C Ao CR
C ACRo

Co kt C Ao C Ro kt

Where : Co C A C R C Ao C R o Constant

3.2 Variable Volume Reactions:

dn A
n
k A
Vdt
V
a.

Zero-Order

C Ao
ln1 A x A kt
A
b. First Order

V
ln 1
AV o

c.

ln1 x A kt

Second-Order

1 A x ln1 x kC t
A
A
1 x A A A
o

d. Third-Order

1 2 x x
21 x
2

Where:

2
A

2 x

A
2
2
A ln1 xA kCAo t
1 x A

x A fractional conversion
A fractional cahnge in volume

Vx A 1 Vx A 0
VxA 0

Sample Problems:
1. For the reaction A + B S, equal volumes of 1 molar A and 2 molar B are mixed and allowed to react
for 1 hr which half of A had been reacted. If the reaction is 1 st-order with respect to A and 1st-order with
respect to B, how much time in hours is required for 75% of A to react?
nilotaldon12/21/2015

Page

21 /40

a. 2.714
b. 2.26
c. 4.351
Initial concentration of A and B after mixing:
11 0.5; C 21 1
C Ao
Bo
2
2

d. 6.732

For sec ond-order reaction

1
C C
t
Ln B Ao ; C A C Ao 1 x A 0.51 0.5 0.25
k C Bo C Ao
C BoC A
C Bo 1 0.5 0.50 0.75

0.75 0.5 0.8109

1
C C
1
Ln B Ao
Ln
1 0.25
t C Bo C Ao
C BoC A 1 1 0.5

C A C Ao 1 x A 0.51 0.75 0.125

C Bo 1 0.5 0.75 0.625

2.

0.625 0.5 2.26 h

1
C C
1
Ln B Ao
Ln
1 0.125
k C Bo C Ao
C BoC A . 0.8109 1-0.5

The reaction A +B S is of second-order and k at 0oC is 39.1 liter/(mole)(minute). An aqueous

solution is made of 0.004 molar A and 0.005 molar B. How long will it take for 90% of A to react?
a. 30 minutes
b. 26 minutes
c. 50 minutes
d.
20
minutes

For second - order reaction

C A C Ao 1 x A 0.004 1 0.9 0.0004
C B 0.005 0.004 0.90 0.0014
t

C C
0.0014 0.004 26.33 minutes
1
1
Ln B Ao
Ln
k C Bo C Ao C Bo C A 39.1 0.005 0.004 0.005 0.0004

3. The reaction 2A 2R + S takes place isothermally in a constant-volume experimental reactor. Starting

with a mixture of 80% A and 20% inserts, the initial pressure of 10 atm increases by 25% in 8
minutes. What conversion is attained?
a. 37.5%
b. 62.5%
c. 35.5%
d. 64.5%
2A I 2R S
i
8
2 0
0
- x'A

x 'A

f 10 0.5 x 'A 12.5;

PA 8 5 3 :

xA

0.5 x 'A
x A' 5
PAo PA 8 3

6.52%
PAo
8

4. If the same feed in the preceding problem is introduced in an isothermal variable-volume batch reactor,
what is the time required for the same conversion?
a. 9.3 minutes
b. 8.5 minutes
c. 6.5 minutes
d. 10.5 minutes
@ constant-volume
nilotaldon12/21/2015

Page

22 /40

1 1
1
k

t C A C Ao

1 1 1 0.02604

8 3 8

Variable Volume:

A
t

3.3.

V x A 1 V x A 0
Vx A 0

3 2
0.8 0.4;
2

1 0.4 0.625

1 1 A x A
1
A Ln1 x A t
0.4 Ln1 0.625 9.32 mi

0.02604 8 1 0.625
kPAo 1 x A

REACTOR DESIGN

3.3.1 Material Balance:

Reactant
Leaves

fCA dt
Reactant
Enters

REACTOR

oCAo dt
(-rA)Vdt

Reactant
Disappears
by reaction

Reactant
Accumulates
d (VCA)

Types of Reactors
1. Single Batch Reactors (Continuously-Stirred Tanks)
nilotaldon12/21/2015

Page

23 /40

a. Feed is introduced before the start of reaction and product is drawn out after reaction is
b.
c.
d.

completed or terminated.
No feed is introduced and no product is drawn out during reaction time
Concentration of reactants and products varies as a function of time
Concentration of reactants and products is uniform throughout the reactor volume

2. Back-Mix Reactors (Continuously-Stirred Tanks, steady-state)

a. Feed is introduced simultaneously as product is drawn out
b. The volumetric feed rate is equal to the product draw-out rate
c. Reactor volume and reactant concentration remain constant and do not vary as function of time.
d. Concentration of reactants and products is uniform throughout the reactor volume.
3. Plug-Flow or Tubular Reactors
a. Feed is introduced simultaneously as product is drawn out
b. Concentration of the reactants and products varies as a function of location or length of the
reactor

c. The concentration of the reactants and products at the specific length of the reactor does not vary
as function of time

d. The volumetric feed rate may not necessarily be equal to the volumetric product draw-out rate.

REACTOR COMPARISON
1. When fluid density is constant

t batch k t batch v k t plugflow plugflow

t batch k t plugflow

2. For all conditions

3. For Batch

t ts

4. For Back-Mix

t 1 A x A

Where:

= space time or cycle time; the time required to process one reactor volume
t = holding time or reaction time (batch and plug-low)

t = holding time, mean residence time (for back-mix)

ts = shutdown time; time required for loading and unloading of reactants and products
respectively, cleaning etc. Applicable for batch reactors
s= space velocity; volume of entering feed at a specified conditions per unit time per void
volume of reactor.
=1/

3.3.2 Single Batch Reactors (Continuously-Stirred Tanks)

In a batch reactor, neither the reactants nor the products flow into or leave the system when the
reaction is carried out. They are either the constant-volume or constant-pressure reactors. The operation of a
batch reactor is unsteady-state. Although the composition throughout the reactor is uniform at a given instant,
Reactant
it changes with time.
disappears
Material Balance
by reaction
(-rA)V dt

nilotaldon12/21/2015

Page

24 /40

BATCH
REACTOR
Reactant
Accumulates
d (VCA)

0 = (-rA)V dt + d (VCA)

dt

d VC A
V rA

where: (-rA) = kCAn

dC A

rA

Holding or Reaction time, t_ retention time of reactants inside the reactor volume
Constant Volume
a.

Zero-Order

t
b.

C Ao C A

C Ao 1 x A
k

First-order

CA
1
1
Ln o
Ln1 x A
k
CA
k

c.

Second-Order

1 1
1
1

k C A C A kC A
o

d.

xA

1 xA

Third-Order

1
2k

2
1
1
1 2x A x A

2
2
2
2
C A 2kC A 1 x A
C A
o

Variable -Volume Reactors

a. Zero-Order

nilotaldon12/21/2015

Page

25 /40

CA

Ln1 A x A

Ak

b. First Order

1
1
V
Ln1 x A Ln 1

k
k
AVo

c. Second-Order

1 1 A x A
A Ln1 x A

kC A 1 x A

d. Third-Order

1 1 A 2 x A x A
2 A xA
2
t
A
A Ln1 x A
2
2
1 x A
kC A
21 x A

Note: For Batch, Space Time or cycle Time,

t ts

where:

ts= shutdown time

3.3.3 Back-Mix Reactors (Continuously-Stirred Tanks, steady-state)

Material Balance

Reactant
Enters

Reactant
Leaves

oCAo dt

fCAodt

BACK-MIX
REACTOR

Reactant
Disappears
by Reaction

(-rA)Vdt

oC Ao dt f C Adt rA V dt
nilotaldon12/21/2015

Page

26 /40

@ steady-state: o = f ; = CA, V are constant

o (CAo-CA)dt = (-rA)Vdt
V
C C A C Ao x A
Ao

rA
rA
o
For single reactor

rA C A

C A _ equation of a straight line

o

C Ao
y - intercept

(-rA)
For reactors in series:

rA

C An

C An 1

CAn

Back-Mix Constant Volume: (Steady-State)

1. Zero-Order

r k
A

CA CA
o

CA xA

C A C Ao k

For Reactors in Series:

CA CA
n

n 1

2. First-Order

r kC
A

C Ao C A
kC A

xA
k 1 x A

CA
1

C Ao 1 k
For Uniform Volume Reactors in series:

C An

C Ao
1 k n

3. Second-Order

nilotaldon12/21/2015

Page

27 /40

 r kC
A

2
A

CA CA

kC A

xA

kC A 1 x A

CA

1 4 k C A o
2k

For Reactors in series:

C An

1 1 4k C An 1
2k n

4. Third-Order

r kC
A

3
A

CA CA
o

kC3A

xA

kC 2Ao

1 x A 3

Back-Mix Variable Volume: (Steady-State)

General Equation:

CA CA
o

rA

1 x A 1 A x A
kC nAo1 1 x A n

Space Time,
10.

Mean Holding Time, t

Zero-Order

CA CA
o

CA x A
o

CA CA
o

k 1 A x A

CA x A
o

k 1 A x A

11.First-Order

12.

1 x A 1 A x A
k 1 x A

1 x
k 1 x
A

Second-Order

1 x A 1 A x A
kC A
1 x A 2
o

13.

1 x 1 x
1 x
kC
A

Ao

Third-Order

nilotaldon12/21/2015

Page

28 /40

1 x 1 A x A
2 A
kC Ao 1 x A 3

Note: a. When density is constant or A = 0,

1
kC 2A o

x 1 x
1 x
A

t 1 A x A

b. When density varies with conversion,

10.5.4 For Back-Mix Reactors, (Unsteady State)

oCAo dt = fCAdt + (-rA)Vdt + VdCA + CAdV

Where: V = Vo + (o-f)t

10.6. Plug-Flow or Tubular Reactors

10.6.1 Material Balance

dV

oCAo

xA

FAo

(-rA)dV

FA

Reactant

Enters

Reactant
Disappears
by Reaction

oCAf

FA + dFA

FAf

Reactant

xA + dxA
xA

Leaves

Material Balance for Incremental Volume:

FA F A dF A rA dV

dF A rA dV

FA FAo 1 x A
dFA FAo dx A

but:

and

Substituting values:

FAo dx A rA dV

1
FA

dV

also :

dx A

(r

FA o C A
o

nilotaldon12/21/2015

Page

29 /40

V
o

C Ao

dx A

(r

A)

General equation:

CA

dX A
A)

(r

1
n 1
kC A

(1 A x A ) n
dx A
(1 x A ) n

10.6.2 Space Time and Holding Time

Space Time,

Holding Time, t

1. Zero-Order

CA CA
o

CA xA

C Ao
k A

Ln 1 A x A

2. First-Order

1
1
A xA
1 A ln
1 x A
k

3. Second-Order

kC A

2 A 1 A ln1 x A A x A
2

1 x

1 x

1
Ln 1 x A
k

1 1 A x A
A Ln1 x A

kC A 1 x A

4. Third-Order

2
2
3
2
6 A 3 A x A
1 2x A x A 1 3 A 6 A 2 A
2
3
2
3 A ln1 x A A x A

2
1 x A
kC Ao
21 x A

nilotaldon12/21/2015

Page

30 /40

2
2
2

2 A A x A
1 1 A 2 x A x A
2

t 2

Ln
1

x
A
A
1 x A
kC Ao
21 x A 2

Sample Problems:
1.

The reaction 2A 2R + S takes place isothermally in a constant-volume experimental reactor. Starting with
a mixture of 80% A and 20% inert, the initial pressure of 10 atm increases by 25% in 8 minutes. What
conversion is attained?
2A I 2R S
initial
8
2
0
0

xA
x A 0.5x A
final
8 x A 2 x A 0.5x A 1.25 10
x' A 5 PAo PA
PA 8 5 3 atm
Answer
P PA
5
%conversion Ao

x100% 62.5%
PAo
8

2.

If the same feed in the preceding problem is introduced in an isothermal variable-volume batch reactor, what
is the time required for the same conversion?
Solving for k

: 2nd order constant volume reactor

1
1
1 1

kt = k 8
C A C Ao
3 8
k 0.026

for 2nd order variable volume reactor

1 A x ln1 x kC t
A
Ao
1 x A A A

Solving for fractional change in volume : A

A=

VxA =1 -VxA =0
Vx A =0

nilotaldon12/21/2015

3-2
0.8=0.4
2

Page

31 /40

Substituting values:
1+ A

1-x

xA + Aln 1-xA =kC Aot

1 0.4

1 0.625

0.625 0.4ln 1 0.625 0.026 8 t

t 9.3 minutes

3.

Answer

For a gas reaction 2A R+2S taking isothermally in a constant volume reactor. Starting with 3 atm A and 1
atm inerts, the pressure rises to 4.5 atm in 60 minutes. What space time, space velocity and holding time is
required to effect this conversion in a) plug flow b) back-mix reactor.
I
+ 2A R + 2S
initial
1
3

-xA
xA 2xA
Final = =1+3 -xA+ xA+ 2xA=4.5
xA= 1.0
PA = PAo - xA
= 3-1= 2
Fractional conversion
=

P P
Ao

Aa

1
33.33 %
3

nd

For 2 -order constant volume reactor:

1
1

PA
PA

kt

60

1 1
1

Answer
2
3
360

a. For 2nd-order variable volume plug-flow reactor:

kC A

2 A 1 A ln1 x A A x A
2

1 x

1 x

32 3

0.375
2 4

1 0.375 2 0.333
68.77 minutes
360
2 0.3751 0.375 ln 1 0.333 0.375 2 0.333
Answer
1 0.333
3

1 1 A x A
A Ln1 x A

kC A 1 x A

360 1 0.375 0.333

0.375 Ln1 0.333 Answer
64.15 minutes

1 0.333
3

b. for back-mix
2
1 xA 1 A xA
360 0.333 1 (0.375) (0.333)

113.66 min utes

2
2

kC Ao

1 xA

nilotaldon12/21/2015

1 0.333

Page

Answer

32 /40

1 (0.375)(0.333)

1 xA 1 x A A
3600.333

2
2
kC Ao 1 x A
3
1 0.333

101.66 min utes

Answer

or:
t

4.

1 A x A

113.66

1 (0.375)(0.33)

101.66Answer
minutes

The isothermal irreversible aqueous phase A+B E @ 100oF obeys rE=KCACB; k=15ft3/lbmol.h. Using a
1000ft3 stirred tank reactor with aqueous feed of 2000 ft 3/h, solve for the active concentration of E if the
inlet concentration of A and B are both 0.25 lbmol/ft 3.
Solution:
V
1000 ft 3

0.5h
2000 ft 3 / h

For 2nd-order Back-mix reactor:

CA

1 1 4kC Ao
2k

C Ao C A
kC A 2

1 1 415 0.5 0.25

0.1277
215Answer
0.5

C E C Ao C A 0.25 0.1277 0.1233 lbmol / ft 3

5.

A gas decomposes @ 900oC according to the reaction: 2A(g) 2R(g) + S(g) with a rate constant of 1000
cm3/gmol.s. Solve for the time required in minutes for 80% of reactant A in a batch reactor @ 900 oC and 1
atm.
Solution:
For 2nd-order variable-volume batch reactor:
1 A x ln1 x kC t
A
Ao
1 x A A A
Solving for fractional change in volume : A

Vx A 1 Vx A 0

3 2
0.5
2

Vx A 0
x A 0.80
1000 cm3
L
1L

3
gmol.s 1000cm gmol.s
C Ao=

n Ao P T1
1
gmol
273 1
=
=

=0.01039
V T PV
273+900
L

1 22.4
1 1

Substituting known values in the equation:

1+ A x + ln 1-x =kC t
A
Ao
1-xA A A

nilotaldon12/21/2015

Page

33 /40

t=

1+0.5

1
0.8 + 0.5 ln 1-0.8 =500 s

1 0.01039 1-0.8

minutes
=8.33 minutes
60 s

= 500

Answer

11. Glossary
Activation energy_ the critical amount of energy required for a reaction to take place. The amount of energy in
excess of the average energy level which the reactants must have in order for the reaction to proceed. A
kinetic energy greater than a certain minimum,
Antimatter_ matter composed of elementary particles that are, in a special sense, mirror images of the particles
that make up ordinary matter as it is known on earth. Antiparticles have the same mass as their
corresponding particles but have opposite electric charges or other properties related to electromagnetism.
For example, the antimatter electron, or positron, has opposite electric charge and magnetic moment (a
property that determines how it behaves in a magnetic field), but is identical in all other respects to the
electron. The antimatter equivalent of the chargeless neutron, on the other hand, differs in having a
magnetic moment of opposite sign (magnetic moment is another electromagnetic property). In all of the
other parameters involved in the dynamical properties of elementary particles, such as mass, spin, and
partial decay, antiparticles are identical with their corresponding particles.The existence of antiparticles
was first proposed by the British physicist Paul Adrien Maurice Dirac, arising from his attempt to apply the
techniques of relativistic mechanics.
Catalyst_ acts by lowering the activation energy requirement of a particular reaction or shortening of the reaction
pathway. It either hastens or retards the rate of a chemical reaction without itself undergoing a permanent
change.
a. A substance that changes the rate of chemical reaction
b. A substance which changes the rate of reaction without itself undergoing a permanent chemical
change.
c. A substance which lowers the activation energy requirement of a reaction.
Chemical Kinetics ___ the study of the rate of reaction and mechanism by which one chemical species is
converted to another. chemical kinetics or reaction kinetics is the study of reaction rates in a chemical
reaction. Analyzing the influence of different reaction conditions on the reaction rate gives information
about the reaction mechanism and the transition state of a chemical reaction. In 1864, Peter Waage
Page
34 /40
nilotaldon12/21/2015

pioneered the development of chemical kinetics by formulating the law of mass action, which states that
the speed of a chemical reaction is proportional to the quantity of the reacting substances.
Chemical equation_ is a symbolic representation of a chemical reaction. The coefficients next to the symbols and
formulae of entities are the absolute values of the stoichiometric numbers. The first-ever chemical
equation was diagrammed by Jean Beguin in 1615.
Chemical reaction_ is a process that results in the interconversion of chemical substances.The substance or
substances initially involved in a chemical reaction are called reactants. Chemical reactions are usually
characterized by a chemical change, and they yield one or more products which are, in general, different
from the reactants.
Chemical reaction engineering _is the branch of engineering that is concerned with the exploitation of chemical
reactions on a commercial scale for purposes other than the production of power.
Collision theory of chemical reaction_ rate is directly proportional to the number of collisions per second
a. Only certain collisions between particles results in the formation of products
b. The molecules must have proper orientation
c. A more concentrated solution contains a greater number of particles
Collision Theory of a Chemical reaction:
For a chemical reaction to proceed, molecules must have effective collisions. The two
requirements for an effective collisions are; a.The molecules must be suitably reactive and must have
enough energy, b. The molecules must be arranged in a proper position.
a. The molecules must be suitably reactive and must have enough energy. The energy that the
molecules must possess is known as activation energy. The critical amount of energy required for a
reaction to take place. The amount of energy in excess of the average energy level which the reactants
must have in order for the reaction to proceed.
Collision theory is a theory, proposed by Max Trautz and William Lewis in 1916 that qualitatively
explains how chemical reactions occur and why reaction rates differ for different reactions. It
assumes that for a reaction to occur the reactant particles must collide, but only a certain fraction of
the total collisions, the effective collisions, cause the transformation of reactant molecules into
products. This is due to the fact that only a fraction of the molecules have sufficient energy and the
right orientation at the moment of impact to break the existing bonds and form new bonds.
Activated Complex or Transition Theory:
Henry Eyring, an American chemist, postulated an alternative to collision theory. He
hypothesized that an intermediate species called an activated complex forms during collision. This
intermediate species exist very briefly. It dissociates to form either the product (if reaction occurs) or
the original reactants (if reaction does not occur)
Most reactions proceed in many steps called elementary processes. The combined effect of all the
elementary processes gives the overall reaction. The slow step determines the rate of the chemical
reaction and is called the determining step. The observed rate of the overall reaction is the equivalent
to the rate of the slow reaction
b. The molecules must be arranged in a proper position. This affects the chance for the reaction to occur.

Dutch chemist Jacobus vant Hof won the 1901 Nobel Prize in
chemistry. vant Hoff investigated the structure of organic
compounds and came to be known as the father of chemical
kinetics.

Jacobus vant Hof

nilotaldon12/21/2015

Page

35 /40

Complex chemical reactions_ reactions where actual mechanisms are not represented by simple stoichiometric
equations. These are usually non-elementary reactions and involve more than one step to accomplish.
Elementary Particles, in physics, particles that cannot be broken down into any other particles. The term
elementary particles also is used more loosely to include some subatomic particles that are composed of
other particles. Particles that cannot be broken further are sometimes called fundamental particles to avoid
confusion. These fundamental particles provide the basic units that make up all matter and energy in the
universe.

Structure of Matter
Modern physics has revealed successively deeper layers of structure in ordinary matter. Matter is composed, on a
tiny scale, of particles called atoms. Atoms are in turn made up of minuscule nuclei surrounded by a cloud
of particles called electrons. Nuclei are composed of particles called protons and neutrons, which are
themselves made up of even smaller particles called quarks. Quarks are believed to be fundamental,
meaning that they cannot be broken up into smaller particles.
Elementary Reactions __ any such reaction in which the rate equation suggested by stoichiometric equation
represents the actual mode of action and occurs in a single step.
Equilibrium_ the system is in the state of equilibrium if the following characteristics are observed:
1. It is a closed system ( the amount of matter in the system does not change)
2. There is no change in the properties of the system as time passes.
3. Two processes, which are opposite in direction, simultaneously take place at the same rate.
For chemical equilibrium: The ratio of the product of the molar concentration of the substances formed
to the product of the molar concentration of the reactants is constant.
Equilibrium constant _ the ratio of the forward and reverse rate constant for a reversible reaction.
Fermion_ one of the two main classes of fundamental particles that make up matter and energy. Fermions play an
important role in the structure of matter. The particles that make up atoms (electrons, protons, and
neutrons) are all fermions. Fermions are named for Italian-born American physicist Enrico Fermi. In the
1920s Fermi calculated a set of rules that define the behavior of fermions.
Fractional conversion ( xA )_ the amount of the reactant converted to the desired product divided by the original
amount of reactants.
Fractional change in volume ( A)_ the resulting change in volume when all of the reactants are converted divided
by the original volume occupied by the reactants before the start of the reaction .

Vx A 1 Vx A 0
Vx

A
A =
General Theory of Relativity_ The principle of equivalence holds that forces produced by gravity are in every way
equivalent to forces produced by acceleration, so that it is theoretically impossible to distinguish between
gravitational and accelerational forces by experiment. In 1915 Einstein developed the general theory of
relativity in which he considered objects accelerated with respect to one another. He developed this theory
to explain apparent conflicts between the laws of relativity and the law of gravity. To resolve these
conflicts he developed an entirely new approach to the concept of gravity, based on the principle of
equivalence.
Holding time or reaction time (t) = (batch and plug-low); t = holding time, mean residence time (for back-mix)_
the average time required by the reactants to stay inside the rector in order to attain the desired
conversion to the desired product
Hadron, family of elementary particles. All known particles of matter and energy are classified as hadrons,
leptons, or force carriers. Scientists believe leptons and force carriers are fundamental particles, meaning
they cannot be divided into smaller particles. Hadrons, on the other hand, have an underlying structure of
smaller particles called quarks. The most common hadrons are protons and neutrons, the building blocks of
the nucleus in an atom.

nilotaldon12/21/2015

Page

36 /40

Hesss Law _ The total change in enthalpy of a system is dependent on the temperature, pressure, state of
aggregation, and state of combination at the beginning and at the end; it is independent of the number of
intermediate reactions.
Irreversible reactions_ reactions that proceed only in one direction
Law of chemical equilibrium_ the ratio of the products of the molar concentration of the substances formed to the
product of the molar concentration of the reactants is constant.
Law of Mass Action _states that the rate of chemical reaction is at each instant proportional to the concentration of
the reactant with each raised to a power equal to their coefficient or the actual number of molecules
participating in the reaction. This law can be interpreted by several complex mechanisms but it can
simply be explained as follows: when two or more molecules react, it must come close to one another or
must collide. Therefore, it is expected that the rate of reaction increases if the molecules are crowded
closely together, i.e., the concentration is high.
Le Chateliers Principle_ If a stress (disturbance or change) is applied to a system in a state of equilibrium, the
system will shift in such a way to neutralize the effect of the stress .
Lepton_ type of elementary particle, the most basic building block of matter, that does not experience the strong
force. The strong force holds particles in the nucleus of an atom together. Physicists have discovered the
following leptons: electrons, muons, tau particles, and three corresponding types of neutrino (electron
neutrinos, muon neutrinos, and tau neutrinos).
Limiting reactant_ the reactant that determines the rate of the chemical reaction. The chemical that determines
how far the reaction will go before the chemical in question gets used up, causing the reaction to stop. The
chemical of which there are fewer mols than the proportion requires is the limiting reagent.
Mechanism __ is the sequence of individual chemical events whose over-all result
produce the observed
reaction.
_ the sequence of steps that takes place to complete a chemical change.
Metabolic pathway_ is a series of chemical reactions occurring within a cell. In each pathway a principal chemical
is modified by chemical reactions. These reactions are accelerated, more accurately catalyzed, by enzymes.
Dietary minerals, vitamins and other cofactors are often needed by the enzyme to perform its task. Many
pathways are elaborate. Various metabolic pathways within each cell form that cell's metabolic network.
Pathways are needed by an organism to keep its homeostasis.
Neutrino_ very small particles with no electric charge and little or no mass. Neutrinos are elementary particles
that is, they cannot be broken into smaller particles. Neutrinos are so small that they pass right through
most material. One important kind of neutrino is created in the nuclear reactions that give the Sun its
energy. Neutrinos are members of a group of elementary particles called leptons
Non-elementary Reactions __ are those where there is no direct correspondence between stoichiometric equation
and the rate expression and occurs in two or more series of reactions.
Quantum theory_ based on the idea that energy exist in the form of tiny, discrete units called quanta.
Quarks_ Quark, smallest known building block of matter. Quarks never occur alone; they always are found in
combination with other quarks in larger particles of matter. An elementary particle with an electric charge
equal to one-third or two-thirds that of the electron. Quarks are believed to be the constituents of baryons
and mesons
Quarks and Their Properties
Name
Symbol

Mass1 (GeV)

Charge2 (e)

Generation

up

.002 - .005

+2/3

First

down

.003 - .009

-1/3

First

charm

1.1 - 1.4

+2/3

second

strange

.06 - .17

-1/3

second

top

163 -179

+2/3

third

bottom

4.1 - 4.4

-1/3

third

One GeV is equal to 1.78 x 10-17 kg (3.92 x 10-17 lb).

The charge 'e' is equal to the charge on one proton, or 1.602 x 10 -19

nilotaldon12/21/2015

Page

37 /40

coulombs.

Rate constant_ experimentally determined constant of proportionality between the reaction rate and the
concentrations of reactants that appear in the rate law.
Rate Law_ equation or mathematical expression showing the relationship between reactant concentrations and rate
of reaction. It has the form: rate = k [A] a[B]b[c]c
Rate of reaction ___ the number of units of mass of some participating reactants which is transformed into a
product per unit time and per unit volume.
Reactant or reagent _ a chemical substance which takes part in a chemical reaction is a substance consumed during
a chemical reaction. Solvents and catalysts, although they are involved in the reaction, are usually not
referred to as reactants.
Reaction mechanism is the step by step sequence of elementary reactions by which overall chemical change occurs.
Series of successive elementary steps by which reactants are converted to products.
Reducing agent_ substance that produces reaction in another substance.
Reduction_ removal of oxygen; combination with hydrogen; involves gain in electrons.
Resonance structures_ two or more possible Lewis structures used to describe the bonding in a molecule or ion.
Reversible Reactions_is one which results in the formation of an equilibrium mixture. The concept of a reversible
reaction was introduced by Berthollet (1803) after he had observed the formation of sodium carbonate
crystals at the edge of a salt lake.
2NaCl + CaCO3 Na2CO3 + CaCl2
He recognized this as the reverse of the familiar reaction
Na2CO3 + CaCl2 2NaCl + CaCO3
Reversible process, or reversible cycle_ in thermodynamics, is a process that can be "reversed" by means of
infinitesimal changes in some property of the system without loss or dissipation of energy. Due to these
infinitesimal changes, the system is at rest during the whole process. Since it would take an infinite
amount of time for the process to finish, perfectly reversible processes are impossible.
Shielding effect_ electrons in filled energy levels that fairly but effectively shield the outer electrons in the
outermost energy level from the effect of an equal number of protons in the nucleus.
Shutdown time ( ts)_ time required for loading and unloading of reactants and products respectively, cleaning
Single replacement reaction_ element replaces another element in a compound.
Solid_ state of matter that has a definite shape and volume.
Solubility_ measure of the amount of solute that can dissolve in a given amount of solvent at a certain temperature
Standard molar volume_ volume occupied by one mole of an ideal gas at STP=22.4 L
Stoichiometry_ calculation of quantities of reactants and products in a chemical reaction.
Sub-atomic particles_ electrons, protons and neutrons contained in an atom.
Solution_ homogeneous mixture of two or more substances.
Specific gravity_ ratio of the density of a substance to the density of water at the same temperature.
Space time() or cycle time_ the time required to process one reactor volume
Space velocity ( s)_volume of entering feed at a specified conditions per unit time per void volume of reactor. =1/
= the number of reactor volumes of feed at specified conditions which can be processed in unit time
Special Theory of Relativity_ According to Einstein, no particular object in the universe is suitable as an absolute
frame of reference that is at rest with respect to space. Any object (such as the center of the solar system)
is a suitable frame of reference, and the motion of any object can be referred to that frame. Thus, it is
equally correct to say that a train moves past the station, or that the station moves past the train. This
example is not as unreasonable as it seems at first sight, for the station is also moving, due to the motion
of the earth on its axis and its revolution around the sun. All motion is relative, according to Einstein.
None of Einstein's basic assumptions was revolutionary; Newton had previously stated absolute rest
cannot be determined from the position of bodies in our regions. Einstein stated the relative rate of
motion between any observer and any ray of light is always the same, 300,000 km/sec (186,000 mi/sec),
and thus two observers, moving relative to one another even at a speed of 160,000 km/sec (100,000
mi/sec), each measuring the velocity of the same ray of light, would both find it to be moving at 300,000
km/sec (186,000 mi/sec), and this apparently anomalous result was proved by the Michelson-Morley
experiment.
Spin _ in physics, intrinsic angular momentum of a sub-atomic particle. In particle and atomic physics, there are
two types of angular momentum: spin and orbital angular momentum. Spin is a fundamental property of
nilotaldon12/21/2015

Page

38 /40

all elementary particles, and is present even if the particle is not moving; orbital angular momentum
results from the motion of a particle. For example, an electron in an atom has orbital angular momentum,
which results from the electron's motion about the nucleus, and spin angular momentum. The total angular
momentum of a particle is a combination of spin and orbital angular momentum.
Stoichiometric equation_ is a chemical equation which expresses an overall chemical reaction in terms of the
simplest ratio of reactant and product molecules.
Sub-atomic particles_ electrons, protons and neutrons combined in an atom
Temperature_ Measure of the average kinetic energy of the molecules.
Temperature jump_ is a technique used in the study of chemical kinetics. It usually involves the discharging of a
capacitor (in the kV range) through a small volume (<ml) of a conducting solution containing the
molecule/reaction to be studied. In some versions of the apparatus used, the solution is heated instead by
the output of a pulsed laser which emits in the near infra-red. When laser heating is employed, the
solution need not be conducting. In both cases, the temperature of the solution is caused to rise by a small
amount in microseconds (or less in the case of laser heating). This allows the study of the shift in
equilibrium of reactions that equilibrate in milliseconds (or microseconds with laser temperature jump),
these changes most commonly being observed using absorption spectroscopy. Due to the small volumes
involved the temperature of the solution returns to that of its surroundings in minutes.
Termolecular reaction_ when elementary step involves the simultaneous collision of three molecules.
Ternary compounds_ contain atoms of three elements.
Theoretical yield_ calculated quantity of product in chemical reaction.
Torr_ metric unit of pressure equal to 1 mm Hg. 760 Torr = 1 atm.
Triple bond_ formed by the sharing of three pairs of electrons between atoms.
Uncertainty principle_ states that it is impossible to accurately determine the exact position and velocity of an
electron at the same time.
Unimolecular reaction_ when elementary process involves only one molecule.
Unit cell_ smallest repeating unit showing the structural characteristic of a crystal.
Universal gas constant_ (R) proportionality constant in the Ideal Gas Law, PV= nRT
Valence electrons_ outermost electrons of atoms
Valence-shell-electron-pair repulsion (VSEPR)_ theory assumes that electron pairs are arranged around the central
atom of a molecule or polyatomic ion so that there is maximum separation and minimum repulsion among
electron pairs.
Vapor pressure of the liquid_ pressure exerted by the vapor particles on the liquid at equilibrium
Viscosity_ tendency of a liquid to resist flow
Volatility_ refers to the case with which a liquid vaporizes
.
12. References:
Chemical Reaction Engineering, Octave Levenspiel
Reaction Kinetics for Chemical Engineers, Stanley M. Walas
Chemical Engineering Kinetics, J.M. Smith

13. Sample Problems

1.

Derivation of Formula Michaelis Menten equation:

ES

k1

ES k3 E P

k2

nilotaldon12/21/2015

Page

39 /40

d ES

0 k1 ET ES S k 2 ES k3 ES
dt
k1 ET S k1 ES S k 2 ES k3 ES 0

ES k1 S k2 k3 k1 ET S 0
k E S
ET S

ES 1 T
k2 k3 k1 S k2 k3 k1

ES ET S
km S

nilotaldon12/21/2015

k1

k1

ET S
km S

Michaelis Menten

equation (1)

Page

40 /40