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Chapter 1

FUNDAMENTALS ON CHEMICAL REACTION ENGINEERING


AND KINETICS

Learning Outcomes
Define basic concepts in chemical reaction engineering and kinetics
Differentiate different types of reaction.
Identify the factors to be considered in reaction rates when solving problems
related to chemical reaction engineering and kinetics.
Derive an expression relating the parameters in the operation and control on
different types of chemical reaction.
Calculate and solve problems related to chemical reaction engineering and
kinetics by determining either the time of operation, concentration after certain
time of operation, or specific rate constant depending on what is given in the
problem.
Determine the order of reaction by evaluation on the unit of specific rate constant
and observing dimensional consistency.

1. INTRODUCTION

Raw materials from another chemical process or purchased externally must usually be purified to
a suitable composition for the reactor to handle. After leaving the reactor, the unconverted
reactants, any solvents, and all byproducts must be separated from the desired product before it is
sold or used as a reactant in another chemical process.

Chemical Process

Figure 1. Flow process of a chemical plant.

1.1. Definition

A. Chemical Reaction Engineering

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. It is the syntheses of thermodynamics, chemical kinetics, fluid mechanics, heat
transfer, mass transfer and economics with the aim of properly designing a chemical reactor.
2

B. Chemical Kinetics

Chemical kinetics is defined as the study of the factors that deals with the explanation by which a
chemical reaction proceeds.

C. Chemical Kinetics and Reactor Design

It is the selection of a reaction system that operates in the safest and most efficient manner. E.G.,
use of wetlands to remove toxic chemicals from rivers, increasing the octane number of gasoline,
production of antifreeze starting from ethane, manufacture of computer chips, application of
enzyme kinetics to improve an artificial kidney.

D. Reactor Design

Chemical reactor is the heart of any chemical process.


It is expected to know the changes that will occur and the speed of the reaction.

Topics

1. rate at which chemical reaction takes place


2. mechanisms of reaction
3. rate-limiting steps that control the reaction process

Subjects considered:

1. Thermodynamics
a. liberation and absorption of heat
b. magnitude of that heat
aA rR + sS H ; positive, endothermic
negative, exothermic
free energy @ equilibrium:
F =
where: K = equilibrium constant
F = standard free energy
2. Chemical kinetics:
Study of the factors that influence the rate of reaction and the explanation for the rate of reaction

Sizing of chemical reactors to achieve production goals:

1. behavior of materials within reactors, chemically or physically.


2. know how the data from chemical reactors should be recorded, processed and interpreted.

Homogenous reaction: Reaction takes place in one phase


Heterogeneous reaction: Reaction takes place in more than one phase

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Catalyst: Hinders or accelerates the reaction process while being modified relatively slow if at all

1.2. Factors That Influence the Rate of Chemical Reaction


Nature of the reactant
Temperature
Pressure
Concentration or composition of the reactant
Catalyst

Homogeneous Reaction
Temperature
Pressure
Composition

Heterogeneous Reaction
Mass Transfer Rate
Heat Transfer Rate

If the reaction involves a number of steps in series, it is the slowest step of the series that exerts
the greatest influence and can be said to control.

Chemical Species. Refers to any chemical compound or element with a given identity
determined by the kind, number and configuration of that species atoms.

Chemical Reaction. Takes place when a detectable number of molecules of one or more species
have lost their identity and assumed a new form by a change in the kind or number of atoms in
the compound and/or by a change in structure or configuration of these atoms.

1.3. 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 factors
Specifying operating conditions, methods of control and auxiliary equipment.

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1.4. Classification of Chemical Reactions

A. According to Mechanism

1. Reversible Chemical Reaction

a. A Product

b. A + B C+D

2. Irreversible Chemical Reaction

a. A Product

b. A + B C+D

3. Simultaneous Chemical Reaction


a. A + B Product
b. A + C R
c.
P
A
R
The reactions given from 1 to 3 are simultaneous reactions with respect to A.

4. Consecutive Chemical Reaction

a. A + B C+D P+R

Reaction a can be written also as

b. A+ B C+D

c. C+D P+R

Reactions b and c are consecutive reactions with respect to C and D.

B. According to Number of Rate Equation

Single Reaction: when a single stoichiometric equation and single rate equation are chosen to
represent the progress of the reaction.

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Multiple Reactions: When more than one stoichiometric equation is used to represent the
observed changes, more than one kinetic expression is needed to follow the changes in
composition of all components of the reaction.

a. Consecutive or Series Reactions


b. Parallel, Competing, or Side Reactions
c. Mixed Reactions
A+BR
R+BS

C. According to Molecularity

1. Unimolecular Chemical Reaction


In a unimolecular reaction a single molecule reacts,

A P

Example: the decomposition of ozone

O3 O + O2

2. Bimolecular Chemical reaction


In a bimolecular reaction two molecules collide and react,

A+B P

2B P
Example:
H + O2 OH + O

O + H2 OH + H

3. Trimolecular or Termolecular Chemical Reaction

A+B+C P

2B + B P

3A P

Example:
2NO + O2 2NO2

2NO + Cl2 2NOCl

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D. Types

1. Decomposition: molecule is breakdown into smaller molecules, atoms or atom fragments.


2. Combination: molecules added or combined to another molecule or atom.
3. Isomerization: although the molecule neither adds other molecule to itself nor breaks into
smaller molecules, change in configuration.

E. According to Order of Chemical Reaction

1. Integral Order
a. 1st Order Reaction
b. 2nd Order Reaction
c. 3rd Order Reaction
2. Fractional or Zero Order Reaction

F. According to Phases

1. Homogeneous Chemical Reaction


2. Heterogeneous Chemical Reaction

G. According to Operating Conditions

1. Isothermal Chemical Reaction


2. Non-isothermal Chemical Reaction
3. Isobaric Chemical Reaction
4. Adiabatic Chemical Reaction
5. Isochoric Chemical Reaction
6 Non-isochoric Chemical Reaction

H. According to Equipment

1. Backmix Reactor or Constant Stirred Tank Reactor (CSTR)


2. Plug-Flow Reactor or Continuous Flow Reactor
3. Reactors filled with solid particles
a. Fixed Bed Chemical Reactor
b. Moving Bed Chemical Reactor
c. Fluidized Bed Chemical Reactor

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Table 1. Classification of chemical reaction useful in reactor design

Noncatalytic Catalytic
Homogeneous Most gas phase reactions Most liquid-phase reactions
Fast reactions such as Reactions in colloidal systems
Heterogeneous burning of a flame
Burning of coal Ammonia synthesis
Roasting of ores Oxidation of ammonia to produce
Attack of solids by acids nitric acid
Gas-liquid absorption with Catalytic cracking of petroleum
reaction hydrocarbons
Methanol synthesis

1.5. Rate of Chemical Reaction

The rate of chemical reaction is an intensive quantity and 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


r
A C A (1)

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Equation 1 is the mathematical expression of the Law of Mass Action.


Given an irreversible chemical reaction


aA + bB + cC+... k
dD + eE +... (2)

where: 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:

r
A C C aAC Bb c
C (3)

Similarly the rates of Band C are:


r
B C CaA C bB c
C ; and (4)

r
C C CaA C bB c
C (5)

To remove the proportionality sign, introduce a proportionality constant k thus, Equations 3, 4


and 5 can be written as:

rA =k A CaA C Bb CCc (6)


a b c
rB =k BC C C A B C (7)
a b c
rC =k C C C C A B C (8)

where the exponents a, b, and c, and kA, kB, and kC are the orders and the specific rate constants
of the reaction with respect to A, B and C, respectively. Orders a, b, and c are not necessarily the
same as the stoichiometry a, b, and c. Orders may be zero, 1, 2, 3 or even fractional, e.g., . The
overall order of the reaction is the sum of the individual orders, here a+b+c.

Mole Balance: Accounting of materials leaving and entering the system and or remaining inside
the reaction system volume.

1.6. Another Definition of Reaction Rates

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

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Based on a unit volume of reacting fluid,

dN i Change in No. of moles of any substance i


ri = = (9)
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 = = (10)
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,

dNi Change in the No. of moles of any substance i


ri = - (11)
Sdt Unit surface area time

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

dN i Change in the No. of moles of any substance i


ri = = (12)
Ws dt unitmass of solid time

In general, we can express the reaction rate as

dN i
ri = (13)
Vdt

Where: Ni = moles of any substance i

dNi
= change in the number of moles of any substance
dt at anytime
V = volume of the reactor

Expressing the rate in terms of concentration


Ni
Ci = (14)
V
Differentiating with respect to Ni at constant volume

dN i
dCi = (15)
V

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Substitution of Equation 15 to 9 yields


dCi
ri = (16)
dt
Sign Convention
rate is (+) if substance i is a product
(-) if substance i is a reactant

Example

1. A + B
k1
P+R
dC
rA = - A = k1CA CB
dt
dC
rB =- B =k BCA CB
dt
dCP
rP =+ =k P CA CB
dt
dCA
rR =+ = k R CA CB
dt

where k1, kB, kP and kR are specific rate constants with respect to A, B, P and R, respectively.

1.7. Stoichiometric Relationship of Chemical Reaction

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 -rB rR rS
= = = (17)
a b r s

- dC A
rA = = k A CaA CBb (18)
dt
- dCB
rB = = k BCaA C Bb (19)
dt

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+ dC R
rR = = k R CaA CBb (20)
dt
+dCS
rS = = k SCaA CBb (21)
dt

Substitution of Equations 18, 19, 20 and 21 into Equation 17 results to

k A CaA C Bb k BCaA C Bb k R CaA C Bb k SCaA CBb


= = = (22)
a b r s

From Equation 22 the values of the specific rate constants KB, KR and KS are solved as a function
of KA thus,
k A CaA C Bb k BCaA CBb b
= ; kB = kA (23)
a b a
It follows also that
r s
k R = k A ; kS = k A (24)
a a

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. Only
a small number of molecules can be involved in the reactive single collision which constitutes an
elementary reaction. The number of molecules involved in the collision defines the molecularity
of the elementary reaction. The probability of more than three molecules meeting in a reactive
collision is negligible under normal circumstances. In other words, the rate is a measure of how
many moles of the stoichiometric reaction equation happen per unit time.

Experimental measurements of reaction rates have to be performed at constant temperature, for


example in a thermostat bath, because reaction rates vary strongly with temperature. Slow
reactions, with timescales of minutes, can use sampling, measuring the concentration by taking
samples at regular time interval. Reactions at high temperature can be stopped by quenching,
cooling the sample until reaction rate is negligible.

Example: H 2 + I
2
k
2 HI

The reaction is allowed to proceed in a sealed quartz ampoule at 700 K for a given time and the
ampoule is then rapidly cooled to room temperature. The extent of the reaction can be found by
absorbing the HI and I2 in alkaline solution measuring the volume of H2 remaining and titrating
the HI and I2.

Reaction in solution can sometimes be quenched by dilution of the sample, or by addition of a


reagent which stops the reaction. Thus diluting a sample from the acid-catalyzed hydrolysis of
ethyl acetate stops the reaction by reducing the acid concentration.

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CH 3COOC 2 H 5 H 2O
HCl CH 3COOH + C 2 H 5OH

Modern analytical methods often allow direct measurement of concentrations in reaction


mixtures. Faster reaction with timescales of less than a minute, typically use continuous
measurement of some physical property as a function of time.

Examples of properties and the corresponding measurement device:

1. Pressure change of a gas reaction (manometer)


Ethylene oxide decomposition C 2 H 4 O CH 4 + CO

2. Volume change of a liquid reaction (dilatometer)


Acid hydrolysis of acetal
CH 3CH OC2 H 5 2 + H 2O
HCl CH 3CHO + 2C 2 H 5OH

3. Gas evolution from a liquid reaction (gas burette)


Hydrogen peroxide decomposition 2H 2 O 2 2H 2 O+O 2

4. Electrical conductivity of a liquid reaction (conductivity cell)


Hydrolysis of tertiary butyl iodide (tBuI)
tBuI + OH- tBuOH + I- (tBu indicates (CH3)3C)

5. Thermal conductivity of a gas reaction (katharometer)


Hydrogen isotope exchange: H2 + D2 2HD

6. Optical rotation of a liquid reaction (polarimeter)


Hydrolysis of sucrose
C12H22O11 + H2O C6H12O6 (glucose) + C6H12O6 (fructose)

7. Optical absorption of a gas or liquid reaction (spectrophotometer / spectrometer)


H2 + Br2 2 HBr

Many different physical properties can be used: the only requirements are that there be a direct
relationship between the property and the extent of reaction and that the measurement of the
property be sufficiently fast.

1.8. Elementary and Non-Elementary Reactions

A. Elementary Reaction

Elementary reaction is one in which the order of reaction corresponds to the stoichiometry of the
chemical reaction and occurs only in a single step.

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Example: 1. A Product

2. A B Pr oduct

rA kC A C B
(25)

B. Non-elementary Reaction

Non-elementary reaction occurs in two or more series of reactions and there is no direct
correspondence between the stoichiometry of the reaction and the rate expression of the reaction.

H2 + Br2 2HBr

k1 H 2 Br2 4
1

Rate Expression: rHBr (26)


k 2 HBr / Br2

Nonelementary reactions are explained by assuming that what we observe as a single reaction is
in reality the over-all effect of a sequence of elementary reactions. The reason for observing only
a single reaction rather than two or more elementary reactions is that the amount of intermediates
formed is negligibly small and unmeasurable.

Two Types of Non-Elementary Reaction Mechanism

1. Non-chain reaction mechanism


Reactants (intermediates)*
(intermediates)* Products

Example: Elementary Reaction


A P

Mechanism
A A*
A* P

2. Chain Reaction Mechanism

Reactants (intermediates)*
(intermediates)* + Reactant (Another intermediates)* + Product

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(another intermediates)* Product

Example:

1. A + B P+B

Mechanism
A A*
A* + B B* + P
B* S

2. 2A + B P + 2R

Mechanism
A+B AB*

AB* + A A* + 2R

A* P

1.9. Kinetic View of an Equilibrium for Elementary Reactions

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

A+ B R+S

The rate of formation of R by the forward reaction is:

Rate of formation of R= rformation =k1C A C B (26)

and the rate of disappearance by the reverse reaction is

Rate of disappearance rR ,backward k 2 C R C S (27)

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

rR , forward rR ,backward 0

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rforward = rbackward
k1CACB = k2CRCS (28)

k1 C R CS
= (29)
k 2 CA CB

Since for this reaction kC is defined as


C R CS
kC = (30)
CA CB

at equilibrium we have
k1 CRe CSe
kC = = (31)
k2 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. At non-equilibrium
conditions, Equations 29 and 30 do not hold. Thus, Equation 31 is very specific only for
equilibrium condition.

Equilibrium viewed in three ways:


1. Thermodynamics: equilibrium is attained if for any possible change, the free energy of the
system increases.
F P ,T 0

2. Statistical mechanics: equilibrium is the state of the system consisting of the greatest number
of equally likely molecular configurations which are macroscopically indistinguishable and can
be considered to be identical and said to be in equilibrium state.

3. Kinetics: equilibrium is the rates of change of all the forward and backward elementary
reactions are equally.

1.10. Molecularity and Order of Chemical 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. Needless to say, the molecularity refers only to an elementary reaction and
can only be whole numbers.

The power to which the concentrations are raised is the order of the reaction and empirically
found through its rate of reaction.

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Example:

Consider the irreversible elementary reaction

aA + bB + sS + ... k
Product

where a, b, and s are not necessarily related to the stoichiometric coefficients. We call the power
to which the concentration are raised the order of reaction.

- dC A
rA = = k CaA C bBCSs (32)
dt
Thus, the reaction is

ath order with respect to A


bth order with respect to B
sth order with respect to S
nth order over all
n = a + b + s + .

Example:

1. A P
-dn A
rA = = k CA n = 1 (33)
Vdt

2. 2A + B P
-dn A
rA = = k C A2 C B n = 3 (34)
Vdt

1.11. Unit of Specific Rate Constant (k)

Given an nth Order Irreversible Reaction

A K P

- dC A
rA = = k C An (35)
dt
dC A moles
where: = (36)
dt (volume)(time)
n moles n
CA = (37)
volume n

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moles moles n
rA = = k (38)
volume times Volume n

solving for k
volume n-1
k = unit of k for an nth order chemical reaction.
moles n-1 time
(39)
1. For a zero order (n=0)
mole
k = (40)
volume time

2. For first order (n=1)


1
k = (41)
time

3. For second order (n=2)


volume
k = (42)
mole time
4. For third order (n=3)
volume 2
k = (43)
mole 2 time

1.12 Representation of a Reaction Rate

Using partial pressures of the components

a
rA kp A p Bb ... p Dd (44)

Bimolecular irreversible reaction with second-order rate constant k1

2 A k1 2 R

Rate expression: rA rR k1C A2 (45)

Same as A k1 R

Rate expression: rA rR k1C A (46)

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For the reaction: B + 2D k 3T


2

Rate expression: rB k 2 ' C B C D2 (47)

rD k 2 "C B C D
2

(48)

rT k2 "'CBCD
2

(49)

Stoichiometry: rB 12 rD 13 rT (50)

k2 ' 1
2
k2 " 1
3
k 2 '"
(51)

1.13 Kinetic models for nonelementary reactions

A2 + B2 2AB

A series of elementary steps:


A2 2A* (52)
A* + B2 AB + B* (53)
A* + B* AB (54)

To test the postulated scheme, check the kinetic expression predicted by it corresponds to the
experimentally found kinetic equation.

Types of Intermediates

1. Free radicals. Free atoms or larger fragments of stable molecules which contain one or more
unpaired electrons. The unpaired electron is designated by a dot in the chemical symbol for the
substance.
CH3, C2H5, I, H, CCl3

2. Ions and polar substances. Electrically charged atoms, molecules, or fragments of molecules.

N3-, Na+, OH-, H3O+, NH4+, CH3OH2+, I-

3. Molecules. For the reaction ARS

If the product material R is highly reactive, its mean lifetime will be very small and its
concentration in the reacting mixture can become unmeasurably small.

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4. Transition complex. The numerous collisions between reactant molecules result in a wide
distribution of energies among the individual molecules. This can result in strained bonds,
unstable forms of molecules, or unstable association of molecules which can then either
decompose to give products or by further collisions return to molecules in the normal state.

Reaction scheme involving this intermediate:

a. Non chain reactions. Intermediate is formed in the first reaction and then disappears as it
reacts further to give the product.

Reactants (Intermediates)* (55)


(Intermediates)* Products (56)

b. Chain reactions. Intermediate is formed in a first reaction, called the chain initiation step,
then reacts with the reactant to produce the product and more intermediate in the chain
propagation step, then occasionally the intermediate is consumed in the chain termination
step. In the propagation step, the intermediate is not consumed but acts simply as a catalyst
for the conversion of material.

Reactant (Intermediate)* Initiation (57)


(Intermediate)* + Reactant (Intermediate)* + Product Propagation (58)
(Intermediate)* Product Termination (59)

Samples of mechanisms:

b.1. Free radicals, chain reaction mechanism.

H2 + Br2 2HBr

k1 H 2 Br2 2
1

Experimental rate: rHBr (60)


k 2 HBr / Br2

Scheme: Br2 2Br Initiation and termination (61)


Br + H2 HBr + H Propagation (62)
H + Br2 HBr + Br Propagation (63)

Solution:
_k1
Br2 2Br
_k2
2Br Br2
_k3
Br + H2 HBr + H

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HBr + H _k4 Br + H2
_k5
H + Br2 HBr + Br
HBr + Br _k6 H + Br2

rHBr = k3[Br][H2] k4[HBr][H] + k5[H][Br2] k6[HBr][Br] (1)

rBr = 2k1[Br2] k2[Br]2 k3[Br][H2] + k4[HBr][H] +


k5[H][Br2] k6[HBr][Br] (2)
rH = k3[Br][H2] k4[HBr][H] k5[H][Br2] + k6[HBr][Br] (3)
rBr = rH = 0
rBr = 0 = 2k1[Br2] k2[Br]2
2k1[Br2] = k2[Br]2 (4)
rHBr = k4[HBr][H] + k5[H][Br2] k6[HBr][Br] k4[HBr][H] +
k5[H][Br2] k6[HBr][Br]
rHBr = 2k5[H][Br2] 2k6[HBr][Br] (5)

from equation (4): k2[Br]2 = 4k1[Br2]


[Br]2 = 4k1/k2[Br2]
[Br] = 2(k1/k2)1/2[Br]1/2 (6)

Substitute (6) to (3)


0 = k3[2(k1/k2)1/2[Br2]1/2][H2] k4[HBr][H] k5[H][Br2] +
k6[HBr][2(k1/k2)1/2[Br2]1/2

[H] = ___2(k1/k2)1/2[Br2]3/2{k3[H2] + k6[HBr]___ (7)


{k4[HBr] + k5[Br2]}

Substitute (6) and (7) to (5)

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rHBr = ___2k5(k1/k2)1/2[Br2]3/2{k3[H2] = k6[HBr]}___


k4[HBr] + k5[Br2] -4k6(k1/k2)1/2[Br2]1/2[HBr]
rHBr = 2k3k5(k1/k2)1/2[Br2]3/2[H2] + 2k5k6(k1/k2)1/2[HBr][Br2]3/2
___4k4k6(k1/k2)1/2[Br2]1/2[HBr]2 4k5k6(k1/k2)1/2[Br2]3/2[HBr]___
k4[HBr] + k5[Br2]

Dividing numerator and the denominator by [Br 2]:


rHBr = 2k3k5(k1/k2)1/2[Br2]1/2[H2] 4k4k6(k1/k2)1/2[Br2]1/2[HBr]2
____________2k5k6(k1/k2)1/2[Br2]1/2[HBr] ___________
k4[HBr] + k5[Br2]

rHBr = __[2k3k5(k1/k2)1/2 - 2k5k6(k1/k2)1/2] [Br2]1/2[H2]__


k5 + k4 [HBr]/[Br2]

Divide numerator and denominator by k4:


rHBr = __[(2k3k5/k4)(k1/k2)1/2 (2k5k6/k4)(k1/k2)1/2] [Br2]1/2[H2]__
k5 / k4 [HBr]/[Br2] (64)
whereas:
k1 = [(2k3k5/k4)(k1/k2)1/2 (2k5k6/k4)(k1/k2)1/2] (65)
k2 = k5/k4 (66)

b.2. Molecular intermediates, nonchain mechanism. General class of enzyme-catalyzed


biological reactions.

A + B AB (67)
A + enzyme (A enzyme)* (68)
(Aenzyme)* + B AB + enzyme (69)

Chemical Reaction Engineering and Kinetics Compiled by Mary Rose F. Persincula


Chapter 1: Fundamentals on Chemical Engineering Reaction and Kinetics Revision 2: 2013
22

b.3. Ionic intermediates, catalyzed nonchain mechanism. The kinetics of the acid-catalyzed
hydration of the unsaturated hydrocarbon isobutene is consistent with a multi-step
mechanism involving formation of a number of intermediates, all polar.

b.4. Transition complex, nonchain mechanism. The spontaneous decomposition of azomethane


(CH3)2N2 C2H6 + N2

The decomposition AR+S (70)


Formation of unstable reactant A + A A* + A (71)
Return to stable form by collision A* + A A + A (72)
Spontaneous decomposition of unstable reactant A* R + S (73)

Or 2A A* + A (74)
A* R + S (75)

b.5. Transition complex, nonchain reaction

H2 + I2 2HI

Chemical Reaction Engineering and Kinetics Compiled by Mary Rose F. Persincula


Chapter 1: Fundamentals on Chemical Engineering Reaction and Kinetics Revision 2: 2013
23

Testing Kinetic Models

Two problems make the search for the correct mechanism of reaction difficult.
1. Reaction may proceed by more than one mechanism, say free radical and ionic, with the
relative rates changing with the conditions of the reaction.
2. More than one mechanism can be consistent with given kinetic data.

Steps in getting the mechanism of reaction:


1. If component i takes place in more than one reaction, its net rate of change is the sum
total of the rates of change of that component in each of the elementary reactions.
2. Because the intermediates are present in such small quantities, their rates of change in the
system after a very short time can never be great; hence with negligible error these rates
are taken to be zero called steady-state approximations.

1.14. REPRESENTATION OF REACTION RATE

Consider the elementary reaction

2 A B k 3C Trimolecular reaction

k, specific reaction rate constant for third order.

1 dN A
rA kC A2 C B (76)
V dt
dC B
rB k ' C A2CB (77)
dt

dCC
rC k"C A
2
CB
dt
(78)
r r r
From stoichiometric relation: A B C (79)
2 1 3

kC A2 C B 2k ' C A2 C B (80)
k 2k ' (81)

2
kC A CB 2
3
2
k"C A CB
(82)
k 23 k " (83)

Chemical Reaction Engineering and Kinetics Compiled by Mary Rose F. Persincula


Chapter 1: Fundamentals on Chemical Engineering Reaction and Kinetics Revision 2: 2013
24

Reversible reactions: A B, A k1 B, B k 2 A
dC A1
rA1 k 1C A (84)
dt
dC A 2
rA 2 k 2C B (85)
dt

For overall reaction: Total rate of transformation of A


dC A
rA k1 C A k 2 C B (86)
dt

Chemical Reaction Engineering and Kinetics Compiled by Mary Rose F. Persincula


Chapter 1: Fundamentals on Chemical Engineering Reaction and Kinetics Revision 2: 2013

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