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dC B
For overall reaction: rB k1 C A k 2 C B (89)
dt
dC C dC B
rC k 2C B k1C A0 e k1t k 2 C B
dt dt
dC A dC B
rA k1C A k 2 C B k1C A0 e k1t
dt dt
C A dC t
C A0 C A 0 kdt
A
IF e k 2t
C
ln A k1t
C A0
dC B
e k 2t e k 2t k 2 C B k1C A0 e ( k2 k1 )t
dt
C A C A0 e k1t
dt
d k 2t
e C B k1C A0 e ( k 2 k1 ) t
e k2t C B
1
k 2 k1
k1C A0 e ( k 2 k1 )t M
At t = 0; CB = CB0
kC
C B 0 1 A0 M
k 2 k1
CB
k 2 k1
k1C A0 k1t
e e k2t C B 0 e k2t (90)
kC
M C B 0 1 A0 if CBO = 0
k 2 k1
k1C A0 e ( k 2 k1 ) t
e CB
k 2t kC
C B 0 1 A0 CB
k 2 k1
k1C A0 k1t
e e k 2t (91)
( k 2 k1 ) ( k 2 k1 )
dC C
rC k 2C B
dt
C B 0 C B CC
C B C B 0 CC
dC C
dt
k kC
k 2 C B 2 1 A0 e k1t e k 2t
k1 k 2
CC
e
t
k 2 k1 C A 0
dCC
k1t
e k 2t dt
CC 0
k1 k 2 0
CC
k 2 k1C A0 k1t
k1 k 2
e
e k 2t C C 0 (92)
dC A dC A
0; 0 k1C A0 e k1t
dt dt
e k1t 0 k1t ln 0
ln 0
t max (93)
k1
dC B k1C A0 k1t
0; CB (e e k 2 t )
dt k 2 k1
dC B kC
1 A0 (k1e k1t k 2 e k 2t ) 0
dt k 2 k1
k 2 e k2t k1e k1t
ln kk12
t max (94)
k 2 k1
dC C k 2 k 1C A 0
0; CC ( k1e k1t k 2 e k 2t ) 0
dt k 2 k1
ln kk12
t max (95)
k 2 k1
dC A dC B dC C
rA k 1C A k 2 C A rB k1C A rC k 2C A
dt dt dt
CA
dC A t dC B
C A0
CA
(k1 k 2 )dt
0 dt
k1C A0 e ( k1 k 2 )t
k 2 C A0
CC e ( k1 k 2 )t
( k1 k 2 )
CA k 1C A 0
ln (k1 k 2 )t CB e ( k1 k 2 )t
C A0 ( k1 k 2 )
C A C A0 e ( k1 k2 ) t (96-98)
A
k1
B
B
k2
A
dC A
rA k1C A k 2 C A (102)
dt
C A0 C B 0 C A C B CA
k 2 CT 0
k1 k 2
1 e ( k1 k 2 ) t C A0 e ( k1 k2 )t (103)
C B C A0 C B 0 C A
C B CT 0 C A
dC A
At equilibrium: 0 Conversion: XA = amount of A converted (%)
dt
C A0 C A
k 1C A k 2 C B XA 100 (102)
C A0
C Aeq k2
k eq (103)
C B eq k1
A
k1
B A B
k2
BB
dC A
rA k 1C A k 2 C A C B
dt
(104)
Material Balance:
C A0 C A C B C B C A0 C A
dC A
k1C A k 2 C A (C A0 C A ) (105)
dt
A
k1
B A C
k2
BC
dC A
rA k 1C A k 2 C A C C
dt
(106)
Material Balance:
C A0 C C 0 C A C C C B
dC A
k1C A k 2 C A C C 0 (107)
dt
dC A
I. In terms of concentration: r A k C A C Ap C Bq (Eqtn A) - 108
dt
dC A
II. In terms of partial pressure: rA k PA PAp PBq (Eqtn B) - 109
dt
Equate Eqtn B to E:
PAp PBq
k PA PAp PBq k C A (113)
( RT ) p q
Let p + q = n
kCA
k PA (114)
( RT ) n
III. In terms of mole fraction
dN A
rA k N A N Ap N Bq (Eqtn F) - 115
dt
PA PB NA P
NA ; NB ; CA A
V RT
p q
P P
rA k C A C C k C A A B
p
A
q
B
RT RT
p q
P P
k N A N Ap N Bq k C A A B
RT RT
p q p q
P P P P
k N A A B kCA A B
RT RT
kNA kCA
pq (116)
( RT ) p q
pq n
k N A kCA let p + q = n k N A kCA (117-118)
RT RT
PROBLEM SOLVING
1. The initial rate of a second order reaction is 5.7 x 10 -7 gmole/L-s and the initial
concentration of the reactants is both 0.2 gmole/L. What is the specific reaction rate expressed
in units of hours-cu.ft./lbmole. Find kp and kN at 300C and 1 atm. Express the rate in terms of
other variables.
Given:
RA = 5.7x10-7 gmole / L –s 2A → Products
CA = 0.2 gmole/ L
2NO + O2 → 2NO2
Is assumed to be taking place at constant volume. The initial concentrations of NO and O 2 are
2 lbmoles and 1 lbmole respectively. No NO2 present initially. Derive the rate reactions in
terms of the total pressure (π) of the system.
A
k1
B
k2
C
R
k1
F , k1 0.4m 3 / mole min R
k2
A, k 2 2.0 / min
OBJECTIVES:
To know how temperature affects the rate of reaction through understanding of the
three theorems proposed.
To apply the theorems in solving for kinetics reaction rate constant.
ri f 1 (Temperatur e) f 2 (composition)
k f 2 (composition)
A. Arrhenius Equation
EA
k ko e RT (120)
where:
k = rate constant;
ko = Arrhenius constant, frequency factor, or pre-exponential factor;
EA = Arrhenius Energy of Activation, Cal / g-mol,
R = Universal constant, 1.987 Cal/g-mol K; and
T = Absolute temperature, K.
gives a good empirical description of the temperature dependence of the rate constant of an
elementary reaction. Both EA 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.
k1 ko e RT1
Apply the natural logarithm to both sides of the equation and simplify
EA
ln k1 ln ko e RT1
EA
ln k1 ln ko ln e RT1
E
ln k1 ln ko A
RT1
ln k2 ln ko e RT2
EA
ln k2 ln ko ln e RT2
EA
ln ko ln k2 (122)
RT2
Simplifying further will give us Equation 36 which is the working equation if there two
sets of rate constant (k) and temperature (T) are given.
E E
ln k2 ln k1 A A
RT1 RT2
k2 E A �1 1 �
ln � �
k1 R �T1 T2 �
k E �T T �
ln 2 A �2 1 � (124)
k1 R �T1T2 �
2. When more than two sets of rate constant (k) and temperature (T) are available:
EA
k ko e RT (125)
Applying the natural logarithm to both sides of Equation 37 and simplifying will give
E
ln k ln ko A (126)
RT
EA
Equation 38 is an equation of a straight line where ln ko and are the intercept and the
R
slope of the line, respectively. The natural logarithm of k ( ln k ) is plotted against the
�1 �
reciprocal of temperature � �in Figure 1.
�T �
ln
k
Figure 2. ln k vs. 1/T
( ln k )( ( ) ) ( )( (ln k )( ))
1 2
T
1
T
1
T
y int ercept ln k 0 (128)
n ( ) ( )
2
1 2 1
T T
The fact that k goes to zero as T goes to zero tells us that there must be an energy barrier that
the reaction has to cross. When two molecules encounter, if they are to react they usually need
to meet with sufficient kinetic energy to allow their chemical bonds to be redistributed to form
products. If we follow the total energy of the two molecules as their reaction proceeds, the
energy reaches a maximum at the transition state, where the old bonds are half broken and the
new bonds are half made. The energy profile thus has a barrier to reaction: the height of this is
the activation energy EA.
The number of molecules that meet to form the transition state is the molecularity of the
reaction. The reaction profile shows the exergicity of the reaction (energy released on
formation of products, ΔE). Clearly the activation energy for the reverse reaction is E A + ΔE.
Catalysis involves providing a reaction pathway which has a smaller energy barrier to reaction
EA, and hence gives a faster reaction. Reactions with high activation energies are very
temperature sensitive; reaction with low activation energies are relatively temperature
insensitive. A given reaction is much more temperature-sensitive at low temperature that at
high temperature. From the Arrhenius law the frequency factor ko does not affect the
temperature sensitivity of a reaction.
Transition State
EA
Reactants
E
Products
For all but reactions involving two bare atoms, the relative orientations of the species that
meet in the transition state is important. For the simple reaction H + H2 � H2 + H, the lowest
energy reaction pathway goes through a linear transition state in which the partial bonds are of
o o
equal length at 0.95 A ( the normal bond length is 0.74 A ).
The activation energy rises steeply for other directions of approach of the H atom. This is a
simple example of the very general steric effect for species to react, they not only need to
have sufficient energy to overcome the activation energy barrier, but they also need to collide
in the right orientation. The simple graph of energy against reaction coordinate conceals the
true complexity of reactions, since even for collinear H + H 2 reaction the energy is a function
of two variables (the two H…H separations). In general the potential energy of reacting
species can be described as a surface in n dimensions; for H + H 2 this can be shown as a
contour map.
The explanation of the Arrhenius Law is now clearer. The pre-exponential factor ko is
determined by the frequency with which collisions with the right orientation happen (ko is
numerically equal to the number of collisions per second with the right orientation for reactant
EA
concentrations of 1 mol dm-3). The exponential term e RT is the fraction of those collision
which have energies (for motion along the line of centers) greater than or equal to E A; the
exponential character is a consequence of the Boltzmann distribution, which describes the
way that energy is distributed amongst randomly moving particles at thermal equilibrium. The
T dependence of the collision frequency is usually masked by the exponential term in the
Arrhenius equation.
A
k1
R, R
k2
A, H r (129)
d (ln K ) H r
By Van’t Hoff equation: (130)
dt RT 2
Where: K K G R / A k1 / k 2
d ( ln k1 ) d (ln k 2 ) H r
(131)
dT dT RT 2
d (ln k1 ) E d (ln k 2 ) E
12 and 22 (132)
dT RT dT RT
E1 E 2 H r (133)
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.
ECT
k ko' T e RT (134)
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).
The collision theory states that the number of molecules formed per unit time per unit volume,
which is the rate, is equal to the number of collisions multiplied by a factor f.
M MB
z 2AB C A C B 8RT A (136)
M AM B
M A M B 12
rA f 2AB C A C B (8RT ) (137)
M AM B
k0e E /( RT )
C A C B f C A C B 8RT
2
AB
M AM B
f e E /( RT )
1
M MB
2
k0 2
AB
8RT A
M AM B
1
M MB
2
k 8R A T 2 e E /( RT )
2 1
AB (138)
M AM B
k T 2 e E /( RT )
1
(139)
4kT N2 4kT 2
Z AA A2 n A2 A2 CA (140)
MA 10 6 MA
= number of collisions of A with A/ (sec-cc)
2
B 1 1
Z AB A n A n B 8kT
2 MA MB
2
B N 2 1 1
A 6
8kT C A C B (141)
2 10 MA MB
The more energetic and violent collisions between molecules lead to reaction, or more
specifically, only those collisions that involve energies in excess of a given minimum energy
E lead to reaction. From the Maxwell distribution law of molecular energies the fraction of all
bimolecular collisions that involve energies in excess of this minimum energy is given
approximately by
e-E/(RT)
k2 E
ln ln ko' CT
T2 RT2
k2 E
ln ko' ln CT (144)
T2 RT2
Equating Equations 53 and 54
k2 E k E
ln CT ln 1 CT
T2 RT2 T1 RT1
k2 k E E
ln ln 1
T2 T1 RT1 RT2
�k2 �
�T � �
ln � 2 � E �T2 T1 �
�
� k1 � R �T1T2 �
�T �
� 1 �
�k2 T1 � ECT � T2 T1 �
ln �
�k �
� � � (145)
�1 T2 � R �T2T1 �
Equation 55 is used to determine the activation energy (ECT) if two sets of rate constants (k)
and temperature (T) are given.
E
k CT
ko' e RT
T
Applying natural logarithm to both sides of the equation, then simplify will result into an
equation of a straight line.
k E
ln ln ko' CT
T RT
k 1
The plot of ln vs T is shown in Figure 5.
T
�k �
ln � �
�T �
1/T
Chemical Reaction Engineering and Kinetics Compiled by Mary Rose F. Persincula
Revision 1: 2011
40
�k �
Figure 5. Plot of ln � �as a function of (1/T) for the determination of
�T �
activation energy (ECT) and constant (ko’).
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 given Equation 56.
E ACT
k k o Te
" RT (146)
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).
Reactants combining to form unstable intermediates called activated complexes which then
decomposes spontaneously into products. It assumes in addition that an equilibrium exists
between reactants and activated complex at all times and that the rate of decomposition of
complex is the same for all reactants and is given by kT/h where k is the Boltzmann constant
and h = 6.63 x 10-27 erg-sec is the Planck constant.
For k1 and T1
E ACT
k1 k T e
"
o 1
RT1
E ACT
k1
ko"e RT1
T1
E ACT
�k �
ln �1 � ln ko" ln e RT1
�T1 �
�k � E
ln ko" ln �1 � ACT (147)
�T1 � RT1
similarly for k2 and T2
�k � E ACT
ln ko" ln � 2 � (148)
�T2 � RT2
�k ��T � E T T �
�
ln �2 ��1 � ACT �2 1 � (149)
�k1 ��
T2 � R �T2T1 �
T
�k � E
ln � � ln ko" ACT (150)
�T � RT
�k � 1
The Plot ln � �vs is shown in Figure 5.
�T � T
�k �
ln � �
�T �
�k � 1/T
ln
Figure 5. Plot of � �as a function of (1/T) for the determination of
�T �
activation energy (EACT) and constant (ko”).
PROBLEMS
1. At temperature 320F and 680F the standard rate of reaction are 2.46 and 47.5 sec -1
respectively. Determine the activation energy and the frequency factor.
Given :
T1 = 320F = 492 0R 1.987 cal / gmol – K
T2 = 680F = 5280R 1.987 BTU / lbmol – 0R
K1 = 2.46 sec -1
K2 = 47.5 sec -1
Req’d : EA and ko
Sol’n : ln _k2_ = _EA_ [ _T2 – T1_]
K1 R T1T2
Ln _47.5_ = _EA_ [ _528 – 492_ ]
2.46 = 1.987 (492)(528)
__ EA = 42,449.19759 BTU / lbmol
K1 = k2 e –E / RT
-42449.19759 / [ (1.987)(492)]
1.46 = ko e
Ko = 1.7731 x 10 19 sec -1
Using Collision Theoy
k1 = ko T11/2 e-Ect/RT1
ln __k1__ = ln ko - _ECT_ . _1_
T11/2 R T1
ln __k2__ = ln ko - _ECT_ . _1_
T21/2 R T2
ln __k1 T21/2__ = - _ECT _ [ _1_ - _1_ ]
k2 T11/2 R [ T1 T2 ]
ln _k1_ + _1_ ln _T2_ = - _ECT _ [ _T2 – T1_ ]
k2 2 T1 R [ T 1 T2 ]
2. Data on the effect of temperature on the reaction between ethanol and acetic acid catalyzed
by a cation-exchange resin were obtained by Soletan and Ukete
T, deg C 30 40 50 60 70
k, L/mole-hr 0.5 1.1 2.2 4.0 6.0
Solution:
m = __n∑XY – (∑X)(∑Y)__ y-int = __∑Y∑X2 - ∑ - ∑X∑XY__
n∑X2 - (∑X)2 n∑X2 - (∑X)2
Arrhenius:
k = koe-Ea/RT
ln k = ln ko – _EA_ [_1_]
R [ T ]
= _(3.3688)(4.8158x10-5) – (15.5025x10-3)(9.841x10-3)
5(4.8158x10-5) – (15.5025x10-3)2
ko = 1.2153x109 L/mole-hr
3. Determine the activation energy and the frequency factor from the following
data:
T(deg C) 0 100
k (/min) 0.001 0.05
(a) Use Arrhenius equation
(b) Transition state theory
(c) What is the % difference between the time activation energies in (a) and (b)
(d) Calculate the value of k at 10000C using (a) and (b). What is the % difference
between the two k at this temperature?
Sample Problems
Chemical Reaction Engineering and Kinetics
Directions: Solve the problems completely. Show your solutions in a neat and organized way
on the answer sheets provided. Round off your answer to four decimal places. Your solution
will be graded according to how the problem is solved.
R B k2 = 6 min-1
M is the desired product, B and F are foul pollutants that are expensive to get rid of.
a. Derive the rate law expressions for each species. (5 points)
b. Determine the time in seconds, to achieve 90% conversion of R (XR) for a feed of 3.0
lbmol/ft3. (20 points)
2. (10 points) The time required for one-half of the reactant to disappear is called the half-life
of the reaction.
a. Find the half life of the reaction A B with k = 0.5 mol/L-min and CA0 = 15
M. (5 points)
b. Find the half life of the reaction A B with k = 1 /min and CA0 = 15 M. (5
points)
3. For the reaction, A R, assumed to be first order in both forward and backward
reactions, the initial concentrations of A and R are 3M and zero respectively. Ten minutes
after, the conversion of A is 10%. After a long time, the concentration of A is 30% of the
initial concentration. Predict the conversion of A after 20 minutes.
4. A ten minute experimental run shows that 75% of liquid reactant is converted to product by
a ½ order rate. What would be the fraction converted in a half-hour run?