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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
1.1. Definition
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.
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
Topics
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
Catalyst: Hinders or accelerates the reaction process while being modified relatively slow if at all
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.
A. According to Mechanism
a. A Product
b. A + B C+D
a. A Product
b. A + B C+D
a. A + B C+D P+R
b. A+ B C+D
c. C+D P+R
Single Reaction: when a single stoichiometric equation and single rate equation are chosen to
represent the progress of the reaction.
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.
C. According to Molecularity
A P
O3 O + O2
A+B P
2B P
Example:
H + O2 OH + O
O + H2 OH + H
A+B+C P
2B + B P
3A P
Example:
2NO + O2 2NO2
D. Types
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
H. According to Equipment
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
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:
A k
P
aA + bB + cC+... k
dD + eE +... (2)
From the given chemical reaction the rate expression of A is given as:
r
A C C aAC Bb c
C (3)
r
C C CaA C bB c
C (5)
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.
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
Based on unit volume of reactor, if different from the rate based on unit volume of fluid,
Based on unit interfacial surface in two fluid systems or based on unit surface of solid in gas-
solid systems,
dN i
ri = (13)
Vdt
dNi
= change in the number of moles of any substance
dt at anytime
V = volume of the reactor
dN i
dCi = (15)
V
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.
The stoichiometric equation is a chemical equation which expresses an overall chemical reaction
in terms of the simplest ratio of reactant and product molecules.
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
+ dC R
rR = = k R CaA CBb (20)
dt
+dCS
rS = = k SCaA CBb (21)
dt
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
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.
CH 3COOC 2 H 5 H 2O
HCl CH 3COOH + C 2 H 5OH
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.
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.
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
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.
Mechanism
A A*
A* P
Reactants (intermediates)*
(intermediates)* + Reactant (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
Kinetically, the system is at equilibrium if the net rate of change of the forward and backward
elementary reactions is zero.
A+ B R+S
rR , forward rR ,backward 0
rforward = rbackward
k1CACB = k2CRCS (28)
k1 C R CS
= (29)
k 2 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.
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.
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.
Example:
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
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
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
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
a
rA kp A p Bb ... p Dd (44)
2 A k1 2 R
Same as A k1 R
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)
A2 + B2 2AB
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.
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.
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.
a. Non chain reactions. Intermediate is formed in the first reaction and then disappears as it
reacts further to give the product.
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.
Samples of mechanisms:
H2 + Br2 2HBr
k1 H 2 Br2 2
1
Solution:
_k1
Br2 2Br
_k2
2Br Br2
_k3
Br + H2 HBr + H
HBr + H _k4 Br + H2
_k5
H + Br2 HBr + Br
HBr + Br _k6 H + Br2
A + B AB (67)
A + enzyme (A enzyme)* (68)
(Aenzyme)* + B AB + enzyme (69)
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.
Or 2A A* + A (74)
A* R + S (75)
H2 + I2 2HI
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.
2 A B k 3C Trimolecular reaction
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)
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