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Series or Consecutive Reactions: A 


k1
B 
k2
C
dC A
 rA    kC A (87)
dt
dC B dC B
rB1   kC A , rB 2    k2CB (88)
dt dt

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

When CB0 = 0; -CB = CC

dC C
dt
k kC

 k 2 C B  2 1 A0 e  k1t  e  k 2t
k1  k 2

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25

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

1.15. PARALLEL REACTIONS


A 
k1
B, A 
k2
C

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 )

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C A  C A0 e  ( k1  k2 ) t (96-98)

Product Distribution (Point Selectivity)


r kC k
Sp  B  1 A  1 (99)
rC k 2 C A k 2
k1
For elementary reaction: Sp  (100)
k2
r R
For non-elementary reaction: Sp  B  1 (101)
rC R2

1.16. REVERSIBLE REACTIONS

A 
k1
B
B 
k2
A

dC A
rA    k1C A  k 2 C A (102)
dt

Material Balance Final Equation:

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

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1.17. AUTOCATALYTIC REACTION

A 
k1
B A  B 
k2
BB

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

Homogeneous Catalyst Reaction:

A 
k1
B A  C 
k2
BC
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

1.18. STANDARD RATE OF REACTION FOR GASEOUS REACTIONS

Consider the reaction


aA  bB 
 Pr oducts

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

Assuming Ideal Gas Behavior:


P PB
CA  A (Eqtn C) - 110 CB  (Eqtn D) - 111
RT RT

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Substitute Eqtn C and D in A:


PAp PBq
 rA  k C A (Eqtn E) - 112
( RT ) p  q

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

Find the relation between kNA and kCA


PA = partial pressure of A at any time t
π = total pressure of system
NA = mole fraction of A
NB = mole fraction of B
PB = partial pressure of B at any time t

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
 pq  (116)
  ( RT ) p  q
 
pq n
     
k N A  kCA   let p + q = n k N A  kCA   (117-118)
 RT   RT 

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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

Req’d: kCA, kPA, kNA


Sol’n
-ra = kCACA2
KCA = _-rA_ = _-5.7 x 10-7 gmole / L – s_
CA2 (0.2 gmole / L) 2
KCA = - 1.425 x 10 -5 L / gmole – s
KCA = - 8.219 x 10 -1 ft3 / lbmole – hr

KPA = _KCA_ = ________-1.425 x10-5 L / gmole –s________


(RT)2 [(0.08205 _L - atm_) (30 + 273.15 K) ] 2
Gmole – K
KPA = - 2.3033 x 10 -8 gmole / L – atm 2- s
KPA = 2.98 x 10 -7 lbmole / ft3 – (PSI)2 – hr
KNA = KCA ( _π_)2 = (-1.425 x 10-1 L/gmole – s) [__1atm__]
RT (0.08205 _L- atm_)(30+274.15K)]2
KNA = - 2.3033 x 10-4 gmole / L – s
KNA = -298 x 10 -5 lbmole / ft3 –hr

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2. The third order reaction

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.

3. A simple coupled enzyme assay system may be represented as:

A 
k1
B 
k2
C

Determine the time dependent behavior of the concentration of species B if no B is present


initially. How long does it take to reach a steady value if k 1 = 0.833 moles/m3-s and k2 =
0.767/s? What is the steady state value? CB = 1.0866 moles/m3

4. Liquid reacts and decomposes according to the parallel reactions:

R 
k1
F , k1  0.4m 3 / mole  min R 
k2
A, k 2  2.0 / min

Aqueous feed containing R (CR0 = 40 moles/m3) is provided in a batch reactor. Calculate:


(a) mean residence time, t;
(b) CF ;
(c) CA for a conversion of 90% of R.

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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.

2. TEMPERATURE DEPENDENT TERM OF A RATE EQUATION

2.1. Effect of Temperature on the Rate of Reaction

ri  f 1 (Temperatur e)  f 2 (composition)
 k  f 2 (composition)

General form: k  k 0T m e  E /( RT ) (119)

A. Arrhenius Equation

The Arrhenius Equation (Equation 120)

 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.

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


For a given k1 and T1 Equation 31 becomes
 EA

k1  ko e RT1

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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

Solving for lnko will give Equation 33


EA
ln ko  ln k1  (121)
RT1

Similarly for k2 and T2, Equation 33 becomes


 EA

ln k2  ln ko e RT2
 EA

ln k2  ln ko  ln e RT2

EA
ln ko  ln k2  (122)
RT2

Equating Equations 33 and 34


EA E
ln k1   ln k 2  A (123)
RT1 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

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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

Using Least Mean Square Technique


1/T
E n (ln k )( 1T )  (  1T )(  ln k )
m 
n ( 1T )  (  1T )
2 (127)
R 2

(  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

B. Why Does Arrhenius Equation Have This Form

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.

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Transition State

EA
Reactants

E
Products

Figure 3. Visualization of the energies involved in the transformation of reactants to


products in an elementary reaction.

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 ).

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


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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

Figure 4. Potential Energy Surface for the Collinear Reaction H2 + H → H + H2.

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.

Temperature dependency from thermodynamics

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For the elementary reversible reactions:

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)

2.2. Collision Theory

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.

For the gaseous reaction A+B→C+D

The collision theory can be expressed as: -rA = zf (135)

Where: rA = reaction rate


z = number of collisions of A and B in cm3 of reaction mixture/sec
f = fraction of collision involving molecules with x’s activation energy

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 M  MB 
z   2AB C A C B 8RT A  (136)
 M AM B 

 AB = effective diameter of A plus B upon collision ≈ collision diameter


CA and CB = concentration of A and B; molecules/sec
R = universal gas law constant
R = kB N 0
kB = Boltzmann’s constant, 1.38 x 10-16 erg/K.
N0 = Avogadro’s Number (6.023 x 1023 molecules/gmoles)
Mi = molecular weight

M A  M B 12
 rA  f 2AB C A C B (8RT ) (137)
M AM B

In terms of rate standard rate of reaction:  rA  kC A C B

From the Arrhenius equation: k  k 0 e  E / RT


1
 MA  MB 
2

k0e  E /( RT )
C A C B  f C A C B 8RT
2
AB 
 M AM B 
f  e  E /( RT )
1
 M  MB 
2

k0   2
AB
 8RT A 
 M AM B 
1

 M  MB 
2

k   8R A  T 2 e  E /( RT )
2 1

AB (138)
 M AM B 
k  T 2 e  E /( RT )
1
(139)

Based from the kinetic theory of gases:

4kT N2 4kT 2
Z AA   A2 n A2   A2 CA (140)
MA 10 6 MA
= number of collisions of A with A/ (sec-cc)

Where: σ = diameter of a molecule, cm


M = (molecular weight)/N, mass of a molecule, gms
N = 6.023 x 1023 molecules/gm mole, Avogadro’s number
CA = concentration of A, gmoles/liter
nA = NCA/103, number of molecules of A/cc
k = R/N = 1.38 x 10-16 erg/K, Boltzmann constant

For the bimolecular collisions of unlike molecules in a mixture of A and B:

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2
  B   1 1 
Z AB   A  n A n B 8kT   
 2   MA MB 
2
  B  N 2  1 1 
 A  6
8kT   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)

 fractionof col is ons


col is onrate,  
 involvingenergies 
moles/(liter)(sec)inexces of E 
 rA  
1 dN A
V dt
 kC A C B   
1000  E /( RT )
 Z AB e
N
2
  B  N  1 1   E /( RT )
 A  3
8kT   e C AC B
 2  10 MA MB  (142)

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

For a given k1 and T1 Equation 45 becomes


 ECT
k1
 ko' e RT1
T1
k1 E
ln  ln ko' 
T1 RT1
k E
ln ko'  ln  CT (143)
T1 RT1
Similarly for k2 and T2

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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.

B. When more than two sets of k and T are given

Equation 45 can be rearrange as shown below


 ECT
k  ko' T e RT

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
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40

�k �
Figure 5. Plot of ln � �as a function of (1/T) for the determination of
�T �
activation energy (ECT) and constant (ko’).

2.3. Activated Complex Theory or Theory of Transition State

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.

A. When two sets of k and T are given

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

Equating Equations 57 and 58

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


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�k ��T � E T T �

ln �2 ��1 � ACT �2 1 � (149)
�k1 ��
T2 � R �T2T1 �

B. 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
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”).

Variables Affecting the Temperature Dependency of Reactions

1. Reactions with high activation energies are very temperature-sensitive; reactions


with low activation energies are relatively temperature-insensitive.
2. A given reaction is much more temperature-sensitive at low temperature than at
high temperature.
3. From the Arrhenius law the frequency factor k0 does not affect the temperature
sensitivity of a reaction.

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


Revision 1: 2011
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Chemical Reaction Engineering and Kinetics Compiled by Mary Rose F. Persincula


Revision 1: 2011
43

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 ]

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


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ln _k1_ = - _ECT _ [ _T2 – T1_ ]


k2 R [ T 1 T2 ]
ln _2.46_ = - __ECT__ [ _528 – 492_ ]
47.5 1.987 [ (492)(528) ]
ECT = 41,942.93347 BTU / lbmole

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

Find the activation energy and frequency factor.

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 ]

T,K 303.15 313.15 323.15 333.15 343.15


X 1/T (x103) 3.2987 3.1934 3.0945 3.0017 2.9142
Y ln k -0.6931 0.0953 0.7885 1.3863 1.7918
XY (x103) -2.2863 0.3043 2.4400 4.1613 5.2217
X2 (x105 1.0881 1.0198 0.9576 0.9010 0.8493

-6529.4334 = m = -_EA_ = _5(9.841x10-3) – (15.5025x10-3)(3.3688)_


R 5(4.8158x10-5) – (15.5025x10-3)2
EA = 12973.9836 cal/gmole-K
20.9183 = y-int = ln ko
Chemical Reaction Engineering and Kinetics Compiled by Mary Rose F. Persincula
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= _(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?

4. Calculate the activation energy for the decomposition of benzene diazonium


chloride to give chlorobenzene and nitrogen. Use the following information for the
first order reaction. (Use Arrhenius equation). Answer: E = 123 753.263 J/gmole

T(K) 313 319 323 328 333


k(s-1) 0.00043 0.00103 0.00180 0.00355 0.00717

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


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46

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.

1. (25 points) Consider the following system of liquid-phase reactions:

R M k1 = 0.01 lbmol/ft3 – min

R B k2 = 6 min-1

R F k3 = 80 ft3/ lbmol – min

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?

5. Enzyme E catalyzes the transformation of reactant A to product as follows:


enzymes
A R -rA = 200 CA CEO mol
2 + CA L-min
If we introduce enzyme (CEO = 0.001 mol/L) and reactant (CAO = 10 mol/L) into a
batch reactor and let the reaction proceed, find the time needed for the concentration
of reactant to drop to 0.025 mol/L. Note that the concentration of enzyme remains
unchanged during the reaction.

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


Revision 1: 2011