Lecture - 3

Interpretation of batch reactor data

Determination rate equation and constants
Determination rate equation is a two step process
• First, the conc. Dependency is found at fix temp
• Then temp dependence of rate constant is found, to get complete
rate equation
Equipment used in kinetic study
Equipment by which empirical information obtained can be divided in
two category
• Batch reactor
• Flow reactor
Batch reactor
Batch reactor is container which hold the reaction material during the
reaction
Determination of extent of reaction is done many ways
1. By following the conc of given components
2. By following the change in physical property of the fluid like electric
conductivity or refractive index
3. By following change in total pressure of a constant volume system
4. By following the change in volume of a constant pressure system
Batch reactor
• Batch reactor is operated at constant volume isothermally because it
is easy to interprets results from such run
• This is used whenever possible to obtain kinetics of homogeneous rxn
Flow reactor
• Flow reactor usually used to study the kinetic of heterogeneous rxn
• Heterogeneous rxn we will study in next course
Procedure to analyze kinetic data
There are two method to analyze kinetic data
• Integral
• differential
Integral method
• In the integral method, we guess a particular form of equation
• After appropriate integration and mathematical manipulation, predict
that the plot certain conc function versus time which should yield
straight line
• When data are plotted, if a reasonable straight line fit is obtained,
then the rate equation said to be good fit to the data
 1. Set a hypothesis as to the mathematical formonofthethe
If the rate law depends reactionofrate
concentration more than one
component, and it is not possible to use the method of one component
1. Set afunction.
hypothesisIn aasconstant volume
to the mathematicalsystem,
being in excess, aformtheofrate
linearized theequation
least reaction
squares for
method thebe used. The
rate
can

Integral method
disappearance of reactant A system,
is of regression
purpose analysis is to determine a functional relationship
function. In a constant volume the rate equation
between the dependent variable for rate)
(e.g., the reaction theand the various
disappearance of reactant A independent
is variables (e.g., the concentrations).
dC A
(− rA ) = − dt = k f (C A ) (3-225)
dC A
(− rA ) = − dt = k f (C A ) (3-225)
2. Separate the variables and integrate Equation 3-225 to give
2. Separate the variables and integrate Equation 3-225 to give
CA t
dC A
CA − ∫dC f (C A ) =t k ∫ dt (3-226)
− ∫ C AO A = k ∫ dt 0
C
f
AO
( C A ) 0
(3-226)

Figure 3-18. Test of reaction rate data using the integral method.
Integral method
Zero order, 𝛼=0
9/15/2020 First order, 𝛼=1 Second order,
Chapter 5 Summary Notes 𝛼=2
Integral method
If data do not fit to If
thethe data
straight linedo
fornot
𝛼=0,fall on2 as
1 and a straight line for α=
shown for 𝛼=2

then stop guessing the reaction order and proceed either with
differential methodthen
analysis
we or should
regressionstop
analysis
guessing reaction orders
analysis or to regression.
Differential method
• In the differential method analysis we test the fit of the rate
expression to the data directly
 k and the concentration dependence of the rate equation f(C

Differential method 1. Set a hypothesis as 170to the form

Modeling of the
of Chemical concentration
Kinetics

of the rate function f(Ci). This can be of the form

and Reactor Design d

170 Modeling of Chemical Kinetics and Reactor Design

dC A
(− rA ) = − dt = k f (C i )
From the exp. Data of conc. Vs time, determine
2. From the
the experimental data of concentration versus tim
reaction rate at various times mine the reaction rate at various times.
Draw smooth curve through these 3. data
Draw a smooth curve through these data.
Determine slope (rate) of this curve at selected value
4. Determine of of this curve at selected value
the slope
conc. concentration. The slopes are the rates of reaction
Calculate f(Ci) for each compositioncompositions.
Prepare a plot of reaction rate (-dCA/dt) vs f(Ci).
5. Calculate f(CIfi)the
for each composition.
plot is linear and passes through 6.
origin, the rate
Prepare a ploteq.of reaction rate (–dCA/dt) versus f(Ci). I
consistent with data, otherwise another eq. should
is linear be
and passes through the origin, the rate eq
tested. consistent with the data, otherwise another equation s
tested. Figure 3-17 shows a schematic of the differentia
g the natural log of
2. Differential Method (p. 224-232)

Differential method
ethod (p. 224-232)
Taking the natural log of
The reaction order can be found from
topa l

Consider
g of order
eaction take
can be found from a ln-ln plot of: log :

The reaction order can be found from a ln-ln plot of:

an be found from a ln-ln plot of:

From the intercept
get the rate constant

ds for finding the slope of log-log and semi-log graph papers may be found at
Advantage and disadvantage of each method
• The integral method is easy to use and is recommended when testing
specific mechanisms, or relatively simple rate expressions, or when
the data are so scattered that we cannot reliably find the derivatives
needed in the differential method.
• The differential method is useful in more complicated situations but
requires more accurate or larger amounts of data.
• The integral method can only test this or that particular mechanism
or rate form; the differential method can be used to develop or build
up a rate equation to fit the data.
• it is suggested that integral analysis be attempted first, and, if not
successful, that the differential method be tried.
 Consider a mole balance on a constant volume batch reactor repre-
sented by

Linear regression −
dC A
dt
= kC aA C Bb (3-227)
172 Modeling of Chemical Kinetics and Reactor Design
Using the method of initial rates gives
If the rate law depends on the conc.a mole
Consider of more than
balance onone component,
a constant it is reactor
volume batch
not possible to use the
⎛ method
sented byof one component being excess
dC A⎞
− = ( − rA )O = kC AO C BO
a b
(3-228)
⎝ dt ⎠ O
dC
− A = kC aA C Bb (3
dt
Taking the logarithms of both sides of Equation 3-228 gives

Using
dC A ⎞ the method of initial rates gives
⎛
ln − = ln k + a ln C AO + b ln C BO
⎝ ⎠ (3-229)
dt
⎛ − dC A ⎞ = − r
⎝ represented
This can be dt ⎠ O
( A ) = kC
in theO form
a
AO C b
BO (3

C0 + C1the
Y = Taking X1 +logarithms
C2 X2 (3-230)
of both sides of Equation 3-228 gives

where Y = ln (–dC
dCA/dt), CO = ln k, X1 = ln CAO, X2 = ln CBO, C1 = a,
 NONLINEAR ANALYSIS
Another method for determining rate law parameters is t
a searchAnother
for those parameter
method valuesratethat
for determining law minimize
parameters the
is to su
em
Nonlinearsquared analysis
difference
a search of measured
for those reaction
parameter values thatrate and the
minimize thecalcula
sum o
squared
tion rate. In difference
performingof measured reaction rate
N experiments, the and the calculated
parameter value
tion rate.
determined In performing
(e.g., E , C , N ,experiments,
C and C ) the minimize
that parameter values
the qua c
Search for those parameters valuesathatOminimize1 sum2 of squared
determined (e.g., Ea, CO, C1, and C2) that minimize the quantit
difference of measured and calculated reaction2 rate
s 2
σ 2 =σ 2 = s = ∑
2
N
(Nrim − ric ) 2
( rim − ric )
=∑ (3
N–K N – Ki =1 i =N − K −1
1 N − K −1

2 σ2 = variance
where σ = variance
where
2 s 2 = Σ (rim – r2ic)2
s = Σ (rim – ric)
N = number of runs
N = number of runs
K = number of parameters to be determined
K =r number
= of parameters
measured reaction ratetoforberundetermined
i
im
rim =ricmeasured reaction
= calculated reactionrate
rate for
for run
run ii
ric = calculated reaction rate for run i
Nonlinear least squares curve fitting using the Microsoft Sol
 to obtain For concentration-time data, the measured parameter P ha
Nonlinear analysis
the combined mole balance equation and rate law
to obtain

Lets consider , integrate:

We now guess k and alpha and calculate each CACi at the times shown in the abov
We now guess k and alpha and calculate each C
then compare it with the measured concentration by taking the difference and squ
Guess the valuetoofobtain
𝛼 and k, calculate CA,then compare it with the measured concentratio
calculate difference with
We then sum
measured up squaring
value, the differences
it for all theWe
data
thenpoints.
sum up the differences for all the data

We now guess k and alpha and calculate

We continue to guess k each CACi
and alpha atwe
until the
findtit
We continue tothen compare
guess it with
k and alpha untilthe measured
we(actually
find the concentration
wevalues
let the of alpha find
computer by
andthese taking
k which m
values.
(actually we let the computer find these values.)
 We then sum up the differences for all the data points.

Nonlinear analysis
Continue to guess the value of k and
We continue 𝛼 until
to guess k and we
alphafind
until the value
we find of k ofand
the values alpha and k wh
(actually we let the computer find these values.)
𝛼 for which S^2 is minimum
Unit of rate constant K
116 Modeling of Chemical Kinetics and Reactor Design
Consider reaction A à Products, The rate eq. and K are:
1. Zero order (n = 0; k = moles/m3-sec)

(–rA) = kC0A (3-18)

2. First order (n = 1; k = 1/sec)

(–rA) = kCA (3-19)

3. Second order (n = 2; k = m3/moles-sec)

(–rA) = kCA2 (3-20)

4. Third order (n = 3; k = (m3/moles)2•sec–1)

(–rA) = kCA3 (3-21)

 availability of surface sites.

If the rate of the reaction is independent of the

Determining the order of reaction
the reacting substance A, then the amount dCA by wh
tion of A decreases in any given unit of time dt is co
the course of the reaction. The rate equation
Reaction for a
Rate Expre
Zero order reaction: The rate of a chemical
batch system reaction is of adensity)
(i.e., constant Zero order if express
can be
it is independent of of the participating substancesis CAf, integrating Equation 3-
time t2 the concentration
dC A
(− rA ) = − dt = k
these limits gives:

C Af t2
The negative sign indicates that the component A
− ∫ dC A = k ∫ dt
the system, and k is the velocity constant with the u
C AO t1
sec. Assuming that at time t1 the concentration of

−(C Af − C AO ) = k( t 2 − t1 )

k=
( C AO − C Af )
( t 2 − t1 )
 k=
( C AO − C Af ) AO
may include arbitrary constants resulting from various l
(3-24)
( t 2 − t1 )
118 Modeling of Chemical Kinetics and Reactor Design
such as diffusion constants and a fixed intensity of ab
Zero order reaction In terms of the fractional conversion XA
If t1 = 0, Equation 3-24 reduces
CAOXA =tokt

If t1 = 0; CAf = CAO – kt2 (3-25)

Because CA cannot be negative, the following is ob
Plotting CA vs t gives straight line; where CA0 is intercept and k is slope
In terms ofPlotting theconversion:
fractional concentration (C ) versus time t givesC a straight line,
C AO −AC A = C AO X A = kt for t < AO
118
where CAO is the intercept and k is the slope. The velocity
Modeling of Chemical Kinetics and Reactor Design k constant k
may include arbitrary constants resulting from various limiting factors
This means that the conversion is proportional to tim
such as diffusion constants and a fixed intensity of absorbed light.
shows plots of the zero order rate equations. Examples
In terms of the fractional conversion
reactions XA of radiation within the vat for
are the intensity
reactions or the surface available in certain solid catalyzed
CAOXA = kt (3-26)
FIRST ORDER REACTIONS
Because CA cannot be negative, the following is obtained
Consider the reaction A ⎯⎯k → B . The rate of a first
is proportional
C to the first power of the concentratio
AO Figure 3-4. Zero order reaction.
 ⎡ C Af ⎤
− ln ⎢the
or any other factor that may affect the reaction, ⎥ = k( tdC
C Aamount 2 − 1)
A tthat
First order reaction ⎢⎣C AO ⎥⎦dt depends only
undergoes a chemical change in the short time interval
on the amount of component A present at that instant. The rate for a
first order reaction for a constant volume batch system (i.e., constant
A à productsdensity) can be expressed as: − ln CRate
Reaction [
Af − C ]
AO = k t 2119
Expression − t1 ( )
− dC A
(−Rearranging
rA ) = =and
kC Aintegrating Equation 3-28Cbetween the limits
(3-28)gives
dt − ln Af
C AO
= k t −t(2 1 )
C Af t2
dC A
− ∫ CA
= k ∫ dt (3-29)
C AO t
1 At t1 = 0 and t2 = t. Therefore

⎡ C Af ⎤ C Af
− ln ⎢ C A ⎥ = k( t 2 − t1 ) − ln = kt (3-30)
⎢⎣C AO ⎥⎦ C AO

− ln [C Af − C AO ] = k( t 2 − t1 ) The fractional conversion

(3-31) XA
the fraction of the reactant conve
 first order kinetics or pseudo-first order kinetics over certain
X A =of the
the fraction AO A
reactant converted C AOinto product or
of experimental conditions. Examples are the cracking(3-34) of butane
N AO
For a constant density system, pyrolysis thereactions,
volumetheVdecomposition
remains constant of nitrogen pentoxide (
N AO − N A The
and fractional conversion
disintegrationXof A for a given
nuclei.reactan
First order reaction
the radioactive unstable Instead
X A =For a constant density velocity system, the
constant, volumequantity V
a reactant remains
referred as constant
to(3-34)the half-life t1/2 is
N AO
N N ( 1 − Xthe ) fraction of the converted into product o
= reaction. = C AO (1 − X A )
C A =ZeroA order
Figure 3-4. AO A used. The half-life is the time required for the
(3-35)
concentration
V V reactant to drop to one-half of its initial value. Substitution
For a constant N A densityN AO (system, )
1 − X Aappropriate
the Nvolume − N AV remains
AO numerical values into Equation 3-33 gives
constant
In terms of fractional
C A = conversion
= X A = C AO (1 − X A ) (3-35)
r any other factor that may Differentiating Equation
affectVthe reaction, V the 3-35
amount givesN A 0.693
dC that
1. AO
ndergoes a chemical 120 theNshort(1of
changeNinModeling time
− X )
Chemical
interval k=
dtKinetics
depends = Reactor Design
ln 2 and
only
n the amount of component
V
–CAO
C A =Differentiating
dCAAA =presentAO dX
at
V
that
A
A Equation = C
instant. (1
AO 3-35
For −
The
a
t1 2
X )
rate
constant for
t1 2
a
A gives density system, the (3-36)
(3-35)volume V rem
irst order reaction for a120constant
Rearranging volume
Modeling of batch
and Chemical system
integrating (i.e.,
Kinetics constant
and
Equation Reactor Design
3-37givesbetween the limits t =
ensity) can be expressed dC Substituting
as: = –C dX Equation 3-36 into Equation 3-28
0, XA =A 0 andEquation
Differentiating AO t = tAf and 3-35Xgives
A =NXAf gives N ( 1 − X ) (3-36)
− dC A
Rearranging and integrating
dX C A
Equation
= A
= 3-37 between=the
AO A
C AO (
limits
1 − X A)
t =
(− rA ) = dt = kCdC 0,
A => =
X A
–C
=
A
AX Af dt AO
0
= k
Substituting
dX(
and1 −
A
tX =
A )
t and
Equation
f
tf
X = X
A 3-36Af V gives
into (3-28)
Equation V 3-28 gives (3-37)
(3-36)
dX A
X Af
Substituting ∫ dX(1A− X A ) = k ∫dt
= kt dt Differentiating Equation 3-35 gives
dXEquationf 3-36 into Equation 3-28 gives
0 ∫ (1 −=XkA(1) − X∫A0)
A
(3-37)
0 dt 0 dCA = –CAOdXA
dX A
= k(1 − X A ) (3-37)
dt− −lnln(11−−X
X Af ) ==ktkt f (3-38) (3-38)
( Af ) f
Substituting Equation 3-36 into Equation 3-28 giv
 described by the following mechanism and set of
reacting species.−Case − dC A − dC B
(− rA ) = dt = dt B =(kC − rA )C=
dC A 1 − dCFrom stoichiometry: = = kC A C B
A B dt dt (3-40)
CaseSecond
1 order reaction
Consider (Case-1)
the reaction A+B⎯ k
⎯→ products . The rate
A
equation
The amount of A and B that have C reacted
constant volume
Amount batch
at time system
t = 0 (i.e.,
The amount of A and Bk that have reacted at any time t can constant density) is: AO be
Consider the reaction A + described
B
Amount ⎯ ⎯ →
at by the
products
time t = t . following
The rate mechanism
equation for and
a
C set
described by the followingFrom mechanism and
stoichiometry:
set of equations. A
constantFrom
volume batch system −
Amounts
dC(i.e.,−
that have
constant
dC reacted
density) is: CAO – CA
(− rA ) =
stoichiometry: A
dt
= B
dt
= kC A C B
A
(
− dC A − dC B CAmount A B
(− rAmount
A ) = = The
atdttime t =dt0
= kC
amount B
A B
=
Cof C ABO –
at time
and (C
B = 0 – CA )
t AO
that
Amount at time t = t AO C
have reacted at (3-40)
any time
C
CAO
BOCA
t ca
Amount at timedescribed
t = t byAmounts
the following mechanism
CA
that have reacted
and set of equations.
CCAO
B – CA
Amounts that From
have reacted Substituting Equation
stoichiometry: C – C 3-41 into EquationC – C 3-4
The amount of A and B that have reactedAOat any A time t can BO be B
integrating between the limits Agives B
described by the following mechanism and set
CB = CBO – (CAO – CA) of equations.
FromCstoichiometry:
B = C BO – (CAO – C A)
Amount at timeC At = 0 CAO t (3-41)C
Amount at time t = t − dCEquation CA C
∫
Amounts that have
Substituting
C [
reacted
C −
A
A
( AO the3-40,
C − C CAO – CA ∫
]
=
3-41 kintodt
B
) rearranging
Equation
CBO
3
Substituting Equation Cintegrating
3-41 BObetween
A into Equation limits
A gives
0 and
Amount at time t = 0 AO CAO CBO
 ⎧⎪ A dC A
dC ⎫⎪
⎧⎪CA C
⎧ AC A ⎫
q = −–1/(CBO –CAO)⎨ A∫ ∫
AA
−
dC − dC ⎪ ⎪ ⎬A
⎨ ∫
(
( C
[
−
− C AO ) A
∫ C ( A (3-46)
C BO −⎩C AO ) C A C (C BO − C AO ) (C BO − C AO ) + C A ⎪C − C⎭
⎪ BO [ dC
C BO − C AO ) (−C⎨BO − C⎬AO ) + C A ⎪
∫ ]( ]
)
C C
⎪ AO AO
Second C
Substituting
limits gives
order reaction (Case-1)
⎩ AO p and q into EquationAO3-43 and integrating between the ⎪
⎩ AO
C ⎭ BO AO C A
t
t = k ∫ dt (3-47)
−⎨ ∫ 0
∫
⎧⎪ = k dt dC
CA
0
CA
dC A ⎫⎪ t
= k ∫ dt
(3-47)
A
− ∫ [ ] ⎬
⎪⎩C AO (C BO − C AO ) C A C AO (C BO − C AO ) (C BO − C AO ) + C A ⎪⎭ 0
1 ⎧⎪ C ⎡⎧⎪ (C BO − C AO ) + C A ⎫⎪⎤ ⎫⎪
AO
+ ln ⎬⎥ ⎬ = kt
t 1 ( ⎧⎪ C
Cln
ln
⎨ ⎡⎧ ( −
C AO+) ⎪ln ⎢ C A BO ⎢⎣⎪⎩AO
−AO ⎪ C ⎢⎨ ) + C ⎫
C ( ⎪ ⎤ ⎫⎪
kt ) ⎪⎭⎥⎦ ⎪⎭(3-48) ⎧
C BO −AC AO⎥ + =C AO
(3-48)
= k ∫ dt ⎨ BO ⎩ ⎨ ⎬ ⎬(3-47)
(C − C AO ) ⎪⎩ C A
0 BO ⎢⎣⎪⎩ (C BO − C AO + C AO ) ⎪⎭⎥⎦ ⎪⎭ 1 ⎪ C AO
⎨ln
⎧⎪⎛ C AO ⎞ ⎡ (C BO − C AO ) + C A ⎤ ⎫⎪ (C BO − C AO ) ⎪⎩ C A
⎧⎪ C ln ⎨⎜ ⎟⎡⎧⎪⎢ (C BO − C AO ) + C A ⎫⎪⎥⎤⎬⎫⎪ = k (C BO − C AO ) t (3-49)
⎪⎛ C AO⎨⎞ln⎡ (C⎪⎩BO
1⎧ AO ⎝C+−BO ⎠⎢⎨⎣ ) + C A ⎤C⎪A
C AO ⎫ ⎪⎭⎬ = kt
=+ kC(AO ⎥ −⎪ C AO ) t
ln ⎬⎦ (3-48)
(C BOln−⎨C⎜⎝ C
AO ) ⎪ ⎟ ⎢ CA ⎢
⎣ ⎪
⎩ ( C BO − C⎥AO⎬ )
C BO ⎪
⎭ ⎥
⎦
(3-49)
⎪⎩ BO⎩⎠ ⎣ ⎭
CA ⎦ ⎪⎭ ⎧ (
⎪⎛ C AO ⎞ ⎡ C BO − C A
ln ⎨⎜ ⎟⎢
⎧⎪⎛ C AO ⎞ ⎡ (C BO − C AO ) + C A ⎤ ⎫⎪ ⎩⎝ C BO ⎠ ⎣
⎪ CA
 − dC A
(− rA ) = dt
= kC 2A = kC 2AO (1 − X A )
2
(3-50)

Second order reaction (Case-1)

Figure 3-6. Test for the reaction A + B → products.

 Case 2
Case 2 − dC
CA t Reaction Rate Express
124 Case ∫Kinetics
124 2Modeling
involves a∫Chemical
system
= ofkReactor with a and
Kinetics single reactant.
Reactor DesignIn this case,
Second order reaction (Case-2)
Modeling of Chemical A and dt Design
C 2 (3-5
Case 2 involves a system rate at Cany
with instant
A
a single
AO is0 proportional
reactant. X A to the square of the concentra
In this case,
= kC AO t the
of A.Rearranging
Rearranging Equation 3-50
Theand Equation
integrating
reaction 3-50(1and
between
mechanism is A )2A
− Xthe limits k yields
integrating
⎯ ⎯ between
→ products the limits
. The rate expyie
ate at any instant is proportional to the square of the concentration
f A. The reaction mechanism sion isfor2ACaA ⎯constant volume
⎯k → products batch
. The rate
Figure system
3-7 expres- (i.e.,
gives plots constant
of Equations 3-54 density) i
and 3-58, resp
k
CA CA Consider the second order reaction 2A + B ⎯ ⎯ → products
t
− dC Avolume batch system
ion for a constant ⎡ 1 ⎤ t
− dC=Akt(i.e., constant first density) is to both A and B, and therefore sec
124 ∫ Modeling ∫ ∫ ∫
order with respect
= k dt ⎢ ⎥ = k dt
of Chemical C AC−⎦2AdC
Kinetics and Reactor Design 2 (3-51) (3-5
(3-5
(−CrAAO)C=AO dt = 0kC A = kC AO (1 − X A )
2 overall. The rate equation is:
C
ForCconstantAvolume and
0
⎣ A 2 2
(3-
AO
−Rearranging
dC A
density
( A ) dt
− r = = kC Equation
2
A = kC AO (1 − X A ) 2
2 3-50 and integrating between the limits (3-50)
yields
CA CA
1 1
⎡ 1− dC
CA
⎤ A t ⎡ 1 ⎤ − = kt (3-5
⎢∫ ⎥ = kt= k ∫ dt ==> ⎢ C A⎥ = ktC AO (3-51)
C C 2
⎣ CA ⎦ (3-52) (3-5
C⎣AO A ⎦ A 0
C AO
orC AO
CA
⎡ 11 ⎤− 1 = kt 11 11
− = =+ kt
⎢C ⎥ = kt ==>
C AC A CCAO (3-53) (3-5
(3-5
⎣ CAA ⎦ C AO AO (3-52)
C AO
 CA C AO
C AO dX A
= kC AO (1 − X A ) = 1 + kt
2
2 1 (3-55)
In terms
dt of the fractional conversion, X , Equation 3-50 becomes
Second order reaction (Case-2)
A
C A C AO
Rearranging
C AO dX A Equation 3-55 2 and integrating gives
= kC 2AO (1 − XIn
A ) terms of the fractional conversion, XA, Equation
(3-55)
dt
In terms ofX fractional conversion
A t
dX A Equation 3-55
∫ (1 − X )2 = kC AO ∫ dtC AOand
Rearranging dX Aintegrating
2 gives 2
= kC AO (1 − X A ) (3-56)
0 A 0 dt
XA t
dX A
∫ (1 − X 3-56
Equation
)
kC AO ∫ dt
2 = yields Rearranging Equation 3-55 and (3-56)
integrating gives
0 A 0

XA
⎡ 1 3-56⎤ yields
Equation XA
dX A
t
⎥ = kC AO t
0
⎢
⎣ (1 − XA ) ⎦ ∫ (1 − X )2 = kC AO ∫ dt Rate Expression
Reaction (3-57) 125
XA 0 A 0
⎡ 1 ⎤
⎢ XA ⎥ = kC AO t (3-57)
0⎣
(1 − X3-57
Equation A )= gives
⎦ kC AO t Equation 3-56 yields
(
1− X A)
(3-58)
 Boundary
IRREVERSIBLE(− conditions
rA ) = =are:
kC Aat t = 0, CA = CAO and t = t, CA = CA.(3-73
REACTIONS
dt EQUATIONS
EMPIRICAL
Integrating − dC A RATE
Equation n 3-73 between the OF TheTHE
limits value
gives nth
of nORDERmust be found by tr
( − rA ) =
The rate equation for irreversible = kC A
reactions for a constant 1− n volume
fractional 1conversion,
(3-73)
dt
Boundary conditions are: at t C = 0, − CC −n
= =
C ( 1)ktXtA,=the
n −and t,
rate equa
C A = CA
Nth order reaction
batch system (i.e., constant density) is A A AO AO
C
IRREVERSIBLE REACTIONS
Boundary
A
− Integrating
dC conditions
t Equation
are: at t 3-73= 0, Cbetween
A = CAO and the tlimits
= t, CA gives
= C A.
dX A
A ∫ rate ∫ ( valueA ) a of ( )
− dCIntegrating
A
=
Equation dt 3-73 between the limitsThe gives− r = C = kC
n mustvolume n
beAOfound 1 − X Aby
n
tria
(− rA ) = dt The C
= kC A n nequation
CA C 0 for irreversible reactions
fractional
for constant
AO
(3-73) dt
conversion, XA, the rate equat
(3-74)
batch system
Irreversible, forA constant
AO
C
(i.e.,
A
t− dC
constant
volume
t density)
batch systemis
Boundary conditions
− dC A
∫ C−AndC are:∫ = ∫atdt
C t n
A
=
= ∫ dt
0, C A = C AO and t = Boundary
t, C A = C A
conditions are: at t =(3-74
. (3-74)
0, X
A dX
Integrating Equation( ⎧AC) A dt⎫
− C
rAO =
−3-73
n + 1
C AO A
C =
between
A0
kC A
n the
0
limits gives ( − r A )
Rearranging = C AO
andA integrating
dt
= kC n
(3-73)
AO (1 − X A )
Equationn 3
−⎨ ⎬ = kt (3-75)
− n +
t ⎩ − n +1 ⎭ C1 C XA t
CA
⎧ C A ⎫conditions A
− n +1 C Aare: at t = 0,130 dX A t of
− dC A Boundary − ⎧ CAO
= ⎫ C = C Modeling
Boundary∫ and ==t,Chemical
conditions kCCAO =dtCAat
∫
n −1are: . t = 0, an
Kinetics XA
∫ C An Integrating
= ∫ ⎩ − n + 1Equation
dt⎨ ==> ⎬
−⎭ ⎨
− n
A
+
kt
1
= kt
⎬3-73 between
A
the Rearranging
limits
AO
1300 gives (1(3-74) A ) integrating
−Modeling
Xand
n A
(3-75)
of Chemical (3-75
Kinetics
Equation an
3-7
C AO 0 ⎩
C AO
⎭C AO 0
1
(
CA 1
− )
{ 1− n
C A t − C AO = kt 1− n
} ⎧ (1X − X A )
⎨ ⎧ −
− n +1 X A
−
⎫n +1 X A
⎬ ⎫ = kC n −(3-76)
1
AOn −t1
⎫ ∫( n − 1)n{A A=1∫ dt AO 1}− n
n − 1
dC 1− n
− 1− n
=
A (1dX X ) t
C C kt ⎨1 − n A =⎭0kC(3-76) n −1 = kC AO t
C A
⎬AO
⎩ ∫ ∫
− n +1
⎧ CA A
−⎨
⎩ − n + 1
⎬
⎭C AOC AO
= ktCA
( n − 0 1 )
{ C A − C AO }
1− n
= kt
0
⎩(1 − X 1 −
(3-75)
A )nn ⎭0
0
dt
(3-74) (3-76
CC1A1A−−nn −− CC1AO ( n(−n1−)kt1)kt
1−−n n
AO= = n −1n −1 (3-77)
1 C (1 − X(1A−) X A )− 1 −=1kC
1− n 1− n (3-77)
= kC
AO (
AO
1(−1 −nn)t)t
{C A −− C AO } =CktA =− ktC1AO− n = (n − 1)kt
− n +1
1− n ⎧ C1A− n ⎫ 1− n
A
(3-76) (3-77
⎨ ⎬ (3-75)
 and the radioactive disintegration of unstable nu
velocity constant, a quantity referred to as the h
First order reaction used. half life
The half-life is the time required for the c
reactant to drop to one-half of its initial value.
appropriate numerical values into Equation 3-33 g
The half-life is the time required for the concentration to drop to one-
half of its initial value
1. 0.693
k= ln 2 =
t1 2 t1 2
Half life of first order reaction is independent of the concentration of
the reactant. This basis can be used test whether reaction obey the first
obey first order kinetics by measuring the half life at various initial
concentration of the reactant
 weOverall
of may write
zero-order reactions so thatReactions
this other factor is included Overall Order
ac-of Irreve
Order of Irreversible from the Half-Life t,,. and properly
Sometimes, for
the irreversible reaction
counted for.
the irreversible reaction

Order
wethe
Overall
If mayof reaction
write
Order of Irreversible
reactants from
Reactions
are present half
from thelife
Half-Life
in their stoichiometric ratios,t,,.theySometimes,
will remainfor
at
the that
irreversible reaction the reaction. Thus, for reactants A and we
ratio throughout B at
mayany time
write
If we
the reactants
CB/CA
may = Pla, are
write and present in their stoichiometric ratios, they will remain at
we may write
Consider
that ratio throughout the reaction. Thus, for reactants A and B at any time
CB/CA= Pla, and we may write
we may If thewrite
reactants are present in their stoichiometric ratios, they will remain at
that ratio throughout the reaction. Thus, for reactants A and IfB the at reactants
any time are pre
If the reactants are present in their stoichiometric ratio, they will
that ratio throughout t
If CB/CA = Pla, and
the reactants are we may write
present in their stoichiometric ratios, they will remain atand we m
remain at that ratio through out the reaction, at any time CB/CA = Pla,
that ratio throughout the reaction. Thus, for reactants A and B at any time
CB/CA= Pla, and we may write
If the reactants are present in their stoichiometric ratios, they will remain at
that ratio throughout the reaction. Thus, for reactants A and B at any time
CB/CA= Pla, and we may write
Integrating for n # 1 gives

Integrating for n # 1 gives

 ⎨ ⎬ (3-75)
⎩ − n + 1 ⎭C AO
(n1
t = 2 − 1{C
−1
)
1−
− nn
C1AO −n
− C1AO } (3-87)
Order of reaction from half life
t1 2 = k( n − 1) A
(3-90)
1 k(1n− −
n ) 1− n
1
{C − C } = kt
( n −
The1) A
half-life is AO
defined as the time required for the concentration(3-76)
Similarly,
Chemical Kinetics and132
Reactor the time
Design
Modeling requiredKinetics
of Chemical for theand
concentration to fall to 1/p of
Reactor Design
to drop to half of its initial value, that is, at t = t1/2, CA = 1/2CAO.
Half life isitsthe time
initial
From required
value
Equation 3-86,to conc. to drop half its initial value
gives
Reaction Rate Expression 1
or
C1A− n − nC 1− n
=1−( nn − 1)kt (3-77)
n −n
− C1AO } t1 p
(
(2= C1 AO ) ) −AOC AO(3-87)
−1p
−1AO
− − nC 1− n
11
= kt1 2 ( n − 1) (3-88)
t=
Thek(value
{
k( n −C11A)− n − C1AO −n
}
n − 1) of n must be found by trial-and-error. In terms
(3-91)
(3-87)
of the
defined as the time required (
fractional
its initial value, that is,Taking
2 −1for
at t = the
the
n
1) C1AO
− concentration
• 2conversion,
t1/2, natural
CA = 1/2C
−n
=X ktA1 ,2 (the
logarithm
) equation is
n − 1rate
of both sides of Equation 3-90
(3-89)
gives >1
The half-life is definedAO. as the time required for the concentration
86, <1
to drop to(2half
11)C
n −1 of its 1− n initial value, that is, at t = t1/2, CA = 1/2C AO.
n −−
C AO = kt1 2 ( n − 1)
1− n From (
ln t = ln
− r11AEquation ( 2 dX −
k( n −dt1)
A)AO
22) = C AO 3-86,= kC AO (1 −AO
1 + (1 −
(3-88)
nn ) ln C
X −
A )
ln (
n k − ln n − 1
) (3-92) (3-78)
(3-90)

−n
O = kt1 2 ( n − 1) 2(−1
Similarly,
C
Boundary
⎧
ln t1 2 = ln ⎨
AO )
1− nn −1 1− n
the
− 1 ⎫(3-89)
−time
2conditions
C AO⎬
=required
kt
are:
1 2 ( n −
+ (1 − n ) ln C
atfor
1 )
t =the concentration to fall to 1/p
0, X A = 0, and t = t, X
(3-93) A
of
(3-88)
=half-life
XAexperimen
.
its initial value
Rearranging⎩ kand ( n −gives
)⎭
1integrating
AO
Figure
Equation
3-9. Overall
3-78
each at different
order of
initialbetween
reaction from
the
concentration of
a series of
limits gives
reactant.

(2 −1 • 2 n −n −11) C1AO− n1−=n kt1 2 (n − 1)

1− n
AO (3-89)
Method of half life
Half life method requires data from several experiments, each at
different initial concentration

The method shows that fraction conversion at given time

raises with increased concentration for order > 1,
drops with increased concentration for order < 1
and independent of the initial concentration for order = 1
 (− rA ) = A
= kPARALLEL
dtPARALLEL ( kREACTIONS
1 + k 2 ) CA
1C A + k 2 C A =REACTIONS
(i.e., constant density) are (3-95)
dt
kk1 k 2k
PARALLEL
Consider dC
Consider REACTIONS
elementary
elementary reactions
reactions A
A ⎯⎯⎯⎯ 1→→ B
B and
and AA ⎯
⎯ ⎯ ⎯ →
2
→ CC. .The
The
− dC
rate(equations
B ) = dC Bfor
Parallel reactions
k k
Consider
rate (
+ relementary
equations for= these
B
+ rB ) = dt = k1C A
k1Creactions
these ( − rA ) for
A reactions
reactions A
= ⎯
for aa⎯
dt
1A →= B
constant and+ k 2A
k1Cvolume
constant volume
A
⎯
Cbatch
A =⎯
batch (2
k→ kC2.) CThe
+(3-96)
system
1 system
(3-96) A
rate equations for
(i.e., constant
(i.e., constant dtthese k 1reactions
density)
density) are
are
mentary reactions A ⎯⎯→ B and A ⎯⎯→ C . The for a constant
k2 volume batch system
(i.e., constant density)
dC are
or these (((−++rrArCC)))==−dC
reactions for
−dC
dC C a
=
constant
A= k 2 C A
+ ( volumedCbatch
+ r =) (= +
B
)= k C
system (3-97)
ensity) are( − rA ) = dtdt = =2 k11ACAA + k22 CAA = ( k11 +dtk22 ) CAA
CA k C k C k k C
k C B 1 A (3-95)
(3-97)
(3-95)
dt
− dC A dt
(− rA ) =Rearranging
Rearranging
dt
= kand
dC B
+ k 2 C A Equation
C Aintegrating
1and integrating (
=Equation
k1 + k3-95) Cbetween
23-95 Abetween the the
limitslimits
with with
the (3-95)
the
dC=CC , C = C , C = C , gives:
( +
boundary ) = = (dtk1 =+kk11C
dC
+(k+ r2BBC) A= conditions
= k1C A boundary r B =
conditions k atAtime t (=+0,
2 )AC A
C at time t =rCC) A= =A CAO=,AO
0, C k B2 C=BA(3-95)
C CBO, BO (3-96)
CC = CCCO, gives:
CO (3-96)
dt dt
dC
(+ rB ) =(−+ rdt
C AB tt
C A
=AkAC1=C A k + k dtRearranging and integrating Equation 3-95
dC
dC (3-96)
( =
dC
+ rCC∫))= CCdt
dC = =
= k
k(
C ∫∫( 21 1 A 2 )2
k C
C+ k )
dt (3-97)
(3-98) (3-98)
(3-97)
between
= k1C A CAO
C AO AA
dt 00
2 A boundary conditions at(3-96) time t = 0, CA = CAO, CB = CBO
Rearranging
dC CC and integrating Equation 3-95 between the limits with the
( Cboundary
+ r )boundary
= Rearranging
− ln
C = k C
((
and
conditions
== k + +k
integrating
) t)
Equation
CA 3-95
t
AA 2 A at time t = 0, CdC= C , C = C , C = C , gives:
between
= 0, CA = C=AO(,kC1B+=k 2C)BO
the limits with the
(3-97)
k 2CA
ln
dt CCconditions
AO
AO
k11 at k t
2 2 time t −
∫ A A
CA 0
AO
∫ B
dt , CC = CCO
BO

(3-97)
C CO , gives:
(3-99) (3-99)
C AO
 for the case when CBO =CCO = 0 and k1 > k2 are reviewed in Chapter 5.
An example
Reaction
An example
Rate ofparallel
of parallelreactions
reactionsinvolves
Expression involvesthe
135 thetwo
twomodes
modesofofdecom-
decom-
position of
position of an
an alcohol:
alcohol:
Reaction Rate Expression 135
= Parallel reactions
rB dC B k1
=
rC dC C r k 2dC
CC22HH55OH
OH == CC2HH4 ++ HH2OO
Reaction Rate(3-101) 2 4
Expression
2
135
(3-104)
(3-104)
k C H OH = CH CHO + H (3-105)
B
= B= 1 C22H55OH = CH33CHO + H22
(3-101) (3-105)
rC dC C k 2
Integrating
r Equation
dC k3-101 between the limits yields
B
= B
= 1
(3-101)
rIntegrating
C dC C Equation
k2 3-101 between the limits yields
C B − C BO k1
= (3-102)
C C − C COC B −k 2C BOk1
Integrating= Equation 3-101 between the limits yields(3-102)
C C − C CO k2
C B − C BO
k1 = k1 k1
or C B −CC BO = CC − C CO (3-103) (3-102)
C − C CO
k 2 k 2 kk1 2 k1
or C B − C BO = k C C − k C CO (3-103)
2 2
Therefore, the slope of the linear plot CB versus CC gives the ratio
k1/k2. Knowing k1 + the
Therefore, k2 slope
and
k1 kof
1/kthe
2, the values
kFigure
linear
Figure 3-10.
plot
3-10. ofBconstants
C
Rate
Rate k1 andfor
versus
constants C kCtwo
for can
gives
2two be
the
competing
competing ratio
elementaryfirst
elementary firstorder
orderreactions.
reactions.
determined
k1or as C −
shown C
/k2. Knowing
B in =
Figure −
3-10. 1
BOk 1 + k2 Cand k 1/kC2,CO
C Concentration
the valuesprofiles
of k1 and of com-
k2 can be (3-103)
ponents A, B, and Casin shown k 2 systemkusing
a batch
determined in Figure 23-10. the differential profiles
Concentration Equations of com-
 ⎛ dC A ⎞ reaction can be expressedk as
(− rA ) = − ⎝rates
A
reaction
catalyzed
dt ⎠ 1
= ka1Cconstant
for A A HOMOGENEOUS
+ C
volume⎯ ⎯ 2
→
batchP + C CATALY
(3-114)
(catalyzed)
system (i.e., constan
density) are:
k1
HOMOGENEOUS CATAL
A ⎯⎯→ P (uncatalyzed) (3-112)
Homogeneous catalyzed reactions⎛ dC A ⎞
A catalyzed reaction can be expresse
where C and P represent the catalyst an
(− rAA) =+−C⎝⎯dt⎛ dC
2 ⎠A⎞
= k C C A catalyzed
reaction rates reaction
for a can
constant be expres
volume
(3-115) b
(− rA ) = − ⎯→2P + C= k1(catalyzed)
k
⎝ dt ⎠ 1
2 A C
C A density)
k 1 are:
A ⎯⎯→ P (uncatalyzed)
(3-113)
(3-114
k1
A catalyzed reaction
where
can
C
bePexpressed
and represent the
A ⎯⎯and
as catalyst → Pproduct (uncatalyzed)
respectively. The
The overall rate of disappearance of reactant dC A
⎛ A system is:
⎞ = k C(i.e., constant
reaction rates ⎛ dC A ⎞ for a constant ( − r
volume
A + C A⎯⎯→ ) =k 2−batch
P + C (catalyzed)
(dC− rA ) = −are: ⎝ ⎠ 1 A
= k 2 C A C C A + C ⎯⎯ k 2 dt 1 (3-115
density) ⎝ ⎠
dtk C2 C → P + C (catalyzed)
−
C- Catalyst P- Product
A
= k C
1 A + 2 A C (3-116)
dt where C and PdCrepresent the catalyst a
⎛ dC A⎞ ⎛ PA ⎞represent
The (− roverall
A ) = − ⎝ rate⎠ of= disappearance
k1Creaction
A ( Arates
where − r ) of ⎝reactant
C = and
− for
dt
a
⎠2 A kis:
2 C A Cthe
=constant C catalyst
volume
(3-114)
dt 1
The catalyst concentration remains
reaction
density) are:rates for aandconstant
unchanged integrating
volum
Equation dC3-116 with the boundary conditions:
density) are: t = 0, CA = CAO and
t = t, −CA− r= C
A
=Ak1⎛CdC + ⎞k 2 C A C C The overall rate of disappearance(3-116 of re
( dtA ) = − ⎝ dt ⎠ = k 2C A CC
A A
⎛ dC A ⎞ (3-115)
2 (− rA )dC= A− ⎝ dt ⎛ dC⎠A ⎞= k1C A
CA
The dC catalyst t
concentration remains(
− − rA ) ==−k C +1k C= Ck1C A
1⎝unchanged
Adt ⎠2 A Cand integratin
− ∫ C A3-116
Equation
The overall
A
= (
∫ with
rate
k 1 + kof C
2the )
disappearance
dt dt of reactant A 1 is:
C boundary conditions: t = 0, C (3-117)
A = CAO an
t =Ct,AO CdCA = C A
0
The catalyst⎛ dC A ⎞concentration remains
 dC A
CA (− rAt) =−
dt
= kC A C B (3-120)
dC A
− ∫ = ∫ (Ak1is +consumed,
When k 2 C C )then
dt the total moles ofCA and B remain (3-117)
Homogeneous
C catalyzed reactions
AO
C A unchanged − ln = ( k1 + k 2 C C ) t = Kt
at any time t and can be expressed as COA= CA + CB =
CAO + 0CBO = constant. Then the rate equation becomes
C AO
dC A
(− rA ) = − = kC A (C O − C A ) (3-121)
dt
CA
− ln = ( k1 + k 2 C C ) t = Kt where K = k1 + k2CC. (3-118)
C AO

where K = k1 + k2CC.

A series of experiments are performed with varying catalyst concentrations Cc, K vs Cc plotted
Figure 3-11. Rate constants for a homogeneous catalyzed reaction from a
series of experiments with different catalyst concentrations.
slope of the straight line is K2 and intercept is k1
ions acts as a catalyst, and is expressed by This type of reaction occursk when one of t
+ ⎯⎯ k
→
AUTOCATALYTIC
+ A + Band ⎯⎯is→expressed
B+ B REACT
k
reactions
A B acts as Ba catalyst,
B by
+B ⎯ ⎯→ B + B (3-119)
Autocatalytic reactions This
The rate
A + B is: ⎯
type of reaction
k equation
⎯acts
→ Bas
The
for rate equation
occurs
a constant when
volumeone
+ Ba catalyst, and is expressed b
for ao
batch
reactions
e rate equation for a constant volume batch system
dC A
kC(A−
dC
One
dC A of the products act as catalyst
The ( − rrate
A+B ⎯ A ) =equation
−k
⎯→dtB + B
A
=for AB ) = − volume
aCrconstant
dt
= kC batch
ACB
rA ) = − = kC A C B (3-120)
dt dC
When A is consumed, total moles ( −When
The
r A ) = −
A
rate is
equation= kCfor
Aconsumed,
C Bathen
When
A A the total
is consumed,
constant volumemoles bat
hen A is consumed, then the total moles of unchanged
A and B remain atdtany time t and can
unchanged at be
any expressed
time t aa
anged atofanyA+Btime
remain
t andconstant CAO=+ CCBO+ =C
can be expressed as C constant.
dC = C Then
+ C the =rate equationTh
constant. be
+ CBO = constant. Then the rate equation becomes
O(
When − rA )A =is− consumed,
A B A
= kC A C
AO then
B
BO the total Reaction
dt time t and can be expressed a
moles
unchanged at dC any
( − r ) =
+ Rearranging
CAO When −
CABO A= is
A
= kC A ((Then
constant. C
− r
O −) C
= −
the
A ) dC A
rate (
= kC Amole
equation C bO
dC A dt Equation
consumed, A 3-121
then and
the integrating
total
rA ) = − = kC A (C O − C A ) unchanged(3-121) at any time t and can be expressed
dt
dt C AC dC=A constant. Then
C(AO
− rA ) = −BO
+ =
dCkC ( C −t
C )
the rate equation
∫ C A (CO − C A ) = ∫ kdt
A O A
− dt A

C AO dC A 0
(− rA ) = − dt = kC A (CO − C A )
Converting the left side of Equation 3-122 in
 p = q density) are:

dC A
1 (− rA ) = − = k1C A (3-127)
p=⎧
q =C A
dC A ⎫
CA t dt
⎪ CO ⎪
Autocatalytic reactions
−⎨ ∫
⎪ C
1 dC A
O C A
+ ∫
C
1
O ( C O − C A ) ⎬ = k ∫ dt
⎪
( − r )
B net = −
dC B
= k 2 C(3-124)
B − k1C A (3-128)
⎩C AO
Integrating EquationC AO
3-122 between the ⎭ limits
0 gives
dt

dC C
(+ rC ) = dt
= k 2CB (3-129)

⎧⎪ ⎧C
⎪ A1 1 dCC AA C1A 1⎛ C OdC − CAA ⎞⎫⎪⎫⎪ t
− ⎨− ⎨∫ ln −+
∫ ln ⎜ ⎟⎬⎬ = kt
k ∫ dt
O C (C A )⎪
⎪ C C C ⎝ C − C
OO − C ⎠ ⎪ (3-124)
⎪⎩C⎩AO OC O CAO
A C AO O
AO
⎭⎭ 0

⎧
⎪ C ⎛ C − C ⎞ ⎫
⎪ C B ⎞C⎫BO
⎧⎪ln 1⎨ AOC O 1 A ⎛ − CA ⎪
C=O ln = C O kt
−⎨ ⎪ C ln ⎜⎟⎠ ⎬
lnA ⎜⎝AC O− − C AO ⎪ =
C A ⎟C⎬AOkt (3-125)
⎩ ⎭
⎪⎩ C O C AO C O ⎝ C O − C AO ⎠ ⎪⎭

The fractional conversion, XA, and the initial reaction ratio, θB =

Some ⎧⎪ C AO, ⎛yields
CBOproduct
/C BCmust
O − Cbe
⎫⎪
A ⎞present C BforCreaction to proceed
= BO
=
AO Figure 3-12. Autocatalytic reaction.
ln ⎨ ⎜ ⎟⎬ ln C kt (3-125)
Starting⎪with
C small
⎝ C −concentration
C ⎠ ⎪ C ofC B, rate raises
O as B formed
⎩ A O AO ⎭ A AO
When A used up, rate drops to Zero
The fractional conversion, XA, and the initial reaction ratio, θB =
 and from stoichiometry CAOConst – CA. = C−B = CC. ⎛ k2 ⎞
the originFrom as IRREVERSIBLE
shown in Figure
rate 3-12.
equations
REACTIONS
Equation 3-127, the concentration forC( k
ofBtA a
2 IN− k
constant
⎛ )
1SERIES
k
is=obtained ⎞ ⎜
⎝ k volume
−
⎟
by⎠ integration
k batch dC system (i.e., c
(
2 1
CA
dC
density) are:A = − kC AOdt ⎝ k 2 ⎠
max
⎜
1
⎟ − r ) = − A
= k1C A
∫ 1∫
A
dt (
Irreversible reaction in series
IRREVERSIBLE
Consider
dC A a first order
= − k1for
REACTIONS
reaction
Therefore,
C A a constant volume
C AO
dt
in series
dC
IN asSERIES
Equation 0A ⎯
This shows
k
⎯→ Bbecomes
3-139 1

that(i.e.,
k
⎯⎯→ C . The
2

/C(3-130)
C B maxconstant
rate equations batch system AO dependsdC only on k1 an
density)
dt
are:
( − rA ) = − bek =evaluated
dt
A
k1C A kfrom C Reaction Rate
B max /C ( Expression
rB )at
−AO t= −. B 141
= k 2CB −
der a first order reaction in serieslnaskAA C
t
⎯
= ⎯ −
1
k →
k
From C t B ⎯
e ( k⎯2 →
2−
stoichiometry:
k )
1 C . The
t
k C
net max
dt
uations for a dC CA
The
constant initial t C
conditions
volume e
C
batch
B
2
AO =
aresystem
at time
1 AO
1
t−=k 0, constant
(i.e., CA = C − 1 AO
and CB = 0, CC
k k A0− k
∫
are: ( − rAC ) ==−dt0. From
A
dC =A − k ∫ dt
(
= k1Cstoichiometry:
1
− r ) = −
dC B
A =
⎯
k 12
⎯
k →C B −
1 k
⎯ k⎯ 2
→
C C
2
(3-127)
1
(3-131)dC C
(+ rC ) = dt = k 2C B
AO dt 0 A B net
Therefore, dt
2 B 1 A
and
− k 1t A B A C B
dC A C A dC C A = dC C AO e (
=− ( −=rBln
k)1CAmount
A= − = at−
B ktime
= 1kt Ct =−0k( +Cr ) = C Amount = k C atkCtime
− t t = 0 (3-127) 0
(3-128)
− k t CAO 0 0
dt C AO dt
net 2 B 1 CA
dt k1Amount
C AO 2 e Bat time t = tk C
1AO e 2
CA C
Amount at time t = t CThe =
B variation in concentration C A − 1 AO C
of B is Bobtained by substituti C C
Amounts that have reacted concentrationkof 2 −A CkAO1 – CEquation
from A
k 2 −3-132
k1 CBinto Equation C3-128: C
Therefore,
dC( +BrC ) = dC C = k 2 C B and from stiochiometry, (CAO – CA) = (CB + CC). Th
(3-129)
= − = k 2 C −
dt from
B k 1 C A ThedC final concentration
– C ) – C . The of (3-128)
B is:
concentration of C in terms of CAO
net and
dt C A = C AO e − k 1 t stoichiometry BC
+ k
AO C
2 B
– C
=Ak C =
A1 AO B
BC e − k 1=t C .
C (3-132) (
dt
From Equation 3-127, the concentration of A is obtained by integration
k1C AO C − k1t ⎧ − k 2 t
dC C The variation in concentration B =
CEquation
k
of B
− k
is e
3-133 is C(
obtained − e
= ⎨a1 −firstby ) ⎛ k1 ⎞the− k1t
− ksubstituting
e order
1 t
− ⎜ linear ⎟ (edifferential
−e −k2t
⎝ k 2 − k1 ⎠ factor is IF⎪⎭ = e∫Pd
)
⎫
⎬equat
= =concentration
k C dC of A from Equation the form 23-132 dy/dx 1 Cinto
+AOPyEquation=⎪⎩ Q. The 3-128:
(3-129) integrating
 k2
t max ( k22 − k1 ) = ln k
k
( k tC AO ( k 2 − k
− k 1 ) t max k
− k11)t = ln e ( k−2k−2 kt 1 ) t max =k1 2
{ + k 2ke1 }
k dC
= 1 =max
2
e 2
B
− k e (3-146)
k (3-144)Rate Expression
Irreversible reaction in series Reaction
1
dt 2k −k 11
k
1
The maximum concentration of B occurs at
kk21 andTok2obtain
Theofmaximum thethe
concentration maximum ofkconcentration
B occurs at ofcon- B, differentiate Eq
t max ( k 2 − k1 ) = ln
The values
3-143
govern
with t (
respect
k − k
location
to ) =
time
ln
and maximum
2t, which gives
Forcentration
maximum of concentration
k1 this occurs
B, and of B at⎛ kdC
max 2
2
B /dt = 0,
⎞ 1
k 1
t = tmax. Equation
3-144 becomes: ln ⎜ ⎟
⎛ kdC ⎞ k C ⎝ k1 ⎠
The maximum concentration
2
ln
0 =⎜
− k 1t ⎝ 1 ⎠
k
2
dt
B
= of
t⎟ max =1 B AO
Thekmaximum
k −− k
{
occurs
k
2 −
t
−
k 1
k 1eat− k 1t
+ k}
concentration
2 e −k2t
of B occurs at (
k1 Ct AO e = k1 k 2 C AO2e 21 (3-1
0=− max +
⎛ k 22 − ⎞ k1 k 2 −Atk1tk 2 − k1
ln⎜ ⎟ The max values of k⎛1kand 2 ⎞ k2 govern the location and maximum
⎝ k1 ⎠ ln⎜ ⎟
t max 2= centration of B, and ⎝ k1 this
⎠ occurs at dC B /dt = 0, t = t max. Eq
(3-147)
kAt − t1 1 k1k3-144
k t − k t
2− t t max k=2 = k e − t max k 1
k1 C AO 2e− kmax = 2 C AO ekbecomes:
e max
2 k 2 1− k1 (3-145)
k 2 − k1 k 2 − k1
Substituting for − k 1t in Equation 3-147 gives
At tmax k 2e − t k
= k1At − t
ek1t C AO e 1k − e (3-1
max 2 2 max 1 k t
k1 k 2 C AO e − k 2 t
0 = − max +
k C B maxk−2k −t k1 1 kk2 t− k1
−( t max
k 2 − k 1 ) t max
=
{ }
2 k
k 2ee k2
= k1e k − t max
Substituting 1
for =−1t max
in Equation − (3-148)
−(3-146)
max − k gives
2 3-147 k 2 t max
= − k 2 t max
e k e
k 2 e ( k 2 k−2 k=1 )k1e 2− t max k1 1e e
1 C AO
−k t 2 − k 1t −k2t
 Taking the natural logarithm gives
144 C Modeling of⎛ Chemical ⎞Kinetics ⎛ ⎞and Reactor Design
C B max C B⎛ k ⎛ ⎞ k⎛ kln2 ⎞⎞ max
B ⎛ k ⎞ k k
ln max 2 2 2 = −
ln=C ⎜ − = ⎛⎜ −⎟ ln⎜ ⎟⎞⎟Cln⎜⎛ ⎟⎞ ⎜⎝ k − k ⎟⎠ ⎜⎝ k(3-151)
2
ln 2
⎟
Irreversible reaction in series
C AO B⎝max k 2 − k⎝1 ⎠ k k
C
ln AO = ⎜ − 2 1 ⎟ ln⎜ 1 ⎟
⎝−2kk ⎠⎠ AO⎝ k
Substituting
1 k 2 ⎠Equation 2 3-1471 into 1 ⎠Equation
(3-151)
3-149 gives
(3-151)
C AO ⎝ 2 k − k 1⎠ ⎝ 1⎠
k
k2/(k 2 – kk21/(k
Treating Treating ) as an Treating
exponent /(k
k2and – k k 1⎤) as the
removing an exponent
natural and removing
2 – k 1) as an exponent ⎡ ln ( 2 1and
2k ) removing the natural
logarithmlogarithm
gives logarithm
C gives
− k 2 ⎢ ⎥
Treatinggivesk2/(k 2 – k 1) maxB as an= eexponent⎢⎣ 2 1 and
k − k ⎥⎦ removing the natural
logarithm gives C AO
⎛ k2 ⎞
⎛ k2 ⎞ ⎛ k2 ⎞ ⎜ ⎟
C
C B max ⎛CkB1 ⎞ ⎜⎝ k 2 −⎛kk1 ⎟⎠ ⎞ ⎛⎜⎝ k 2k− kTaking
⎟ B max ⎛ k ⎞ ⎝ k 2 − k 1⎠
2 1⎞
⎠ the= ⎜ natural
1
⎟ logarithm gives
= ⎜ ⎟ = ⎜ ⎟⎜
max 1
⎟ C AO ⎝ k ⎠ (3-152) (3-152)
C AO C ⎝C ⎠ ⎛⎝ k12 ⎞⎠ ⎝ k 2 − k1 ⎠
kB2AO 2
max
=⎜ ⎟ (3-152)
C AO ⎝ k 2 ⎠ C B max ⎛ k2 ⎞ ⎛ k2 ⎞
lnThis shows = that
⎜ − C B max⎟/ClnAO
⎜ depends
⎟ only on k1 and k2
Thisshows
This show that
Thisthat C that C/C depends
depends
/CAO only
only ⎝ onon kK1 and
and kk2k2;
⎝1, and ⎠ kt2 , can
shows B max AOB max C
be evaluatedAO dependsfrom C1−Bkmax
k 2only 1on
⎠/C
AO
k1at
max
and
. k2 can
be evaluated
k2 can from
calculated
beThis
evaluated
showsC Bfrom
from
that /C CC
AO at t
/C max . at
at t
depends . only on k and k 2, and k2 can
max From
BBmax
max AO
AOstoichiometry:
max 1
From be
stoichiometry:
From
evaluatedstoichiometry:
from C BTreating
/C AO kat2/(k
tmax .
max 2 – k 1 ) as an exponent and removing th
From stoichiometry: logarithm k 1gives k 2
k1 k 12 k2 A ⎯⎯→ B ⎯⎯→ C
A ⎯⎯→ A B ⎯⎯→ B C ⎯⎯→ C
k k
 Reaction
be evaluated from C BRate /CExpression
AO at tmax.
141
k1 k2 IRREVERSIBLE REACTIONS IN SERIES
From stoichiometry:
max
A ⎯⎯→ B ⎯⎯→ C
The initial conditions are at time t = 0, CA =kCA0 and kCB = 0, CC
Irreversible reaction in series
Consider a first order reaction
= 0. From stoichiometry:
A
inA
k1
series
⎯⎯
B
→ as
B ⎯⎯A
k2
→⎯
C⎯
C
1
→ B ⎯⎯ 2
→ C . The
rate equations for a constant
Amount at time t = 0 C
volume0 batch system
0
(i.e., constant
A B
CBA B C
AO
Amountdensity)
at time t = are:
t CA CC
Amount at time t = 0 Amount at
0 CAOtime t = 0 CAO 0 0
Amount at time t = t CA CB
Amount at time t = t CA CB CC
dC
A
− r (B )
and from stiochiometry,
= −
Amounts (Chave
A
that AO – reacted
= k C
CA) = (CB + CC146
). CThat is, Cof Chemical
AO – CA C
Modeling = (CAOKinetics
A concentration1 ofAC in terms of C , k , and k are:
– C ) – C . The dt
CB
AO stiochiometry,
1 2
and Reactor CC
Design
(3-127)
and from (CAO – CA) = (CB + CC). That
and from stoichiometry CAO –– CCA) –=CC
B. The
= Cconcentration
. of C in terms of CAO, k
A B C
CC ⎧ ⎛ ⎞ ⎫
= ⎨1 − e −From dCkB1 ⎟ (3-127,
− ⎜Equation e − k1t − the )⎬
e − k 2concentration of A is obtained by integration
(−⎪⎩ rB )net = −⎝ kdt− k=⎠k 2C B − k1C A⎪⎭
k 1t t
C AO CC ⎧ ⎛ k1 ⎞ − k1t (3-128) ⎫
dC A
2 1
C AO
= ⎨1 − e
⎪⎩
− k 1t
−⎜ (
⎟ e
⎝ k 2 − k1 ⎠
−e −k2t
⎬
⎪⎭
)
⎧ k1 = −−k 2kt 1C A k 2 − k 1t ⎫
(3-130)
= ⎨1 + dt e − e ⎬ (3-153)
dC
⎩+ r k=2 − k 2 − k1 ⎧ k1 k2 − k 1t ⎫
( C )k1C
CA dtdC
= k 2CB
t
⎭ = ⎨1 +
⎩ k 2 − k 1
e −k2t
−
k 2 − k 1
e (3-129)
⎬
⎭
∫ A
= − k1 ∫ dt (3-131)
 (− rA ) = −Reaction
dt
A
CA
= k1Rate
A − k 2CB
Expression 147B
Amount at time t = 0 C
A AO B CBO
dC
Amount at time t = t k 1 CA CB
First ( )
order reversible
− rAAmount
= − at Atime
Amounts
the reaction A [
Consider reaction
that= have
tk= C
dttime t = t
Amount at
− k 2From
0 reacted
1 A CB stoichiometry:
CCAO – C
C B . The rate C equa
Reaction
AO
CBO
(3-155)
CB – CB
A Rate Expression
A B
Amounts that have reacted C k 2– C C – C
volume batch
dC A
system is: A AO A B BO

From and the concentration

stoichiometry: of B is
( − rA ) = − = Amount
k1C A −atk 2time
and the concentration of B is
dt
CB t = 0 C (3- AO

CB = (CAO – CA)Amount + C
Amounts
at time t = t
A
BO that have reacted B
CA
(3-15
CAO – CA
CB = (C – CA) + CBO (3-156)
Amount at From
time t =stoichiometry:
AO
0
Substituting Equation 3-156 into AO C C
Equation 3-155, rearranging
BO an
Amount at time t = t and the CA
concentration of3-155, CB
B is rearranging
integrating
Substitutingbetween
Equation the3-156
limits gives:
into Equation and
Amounts that have reacted CAO – CA A CB – CBO B
integrating between the limits gives:
AmountC A at time t = 0
CB = (CAO – CA) + tCCBO CB
AO
and theAmount time t =oft B isdC A
concentration
∫
C A at −
− (
dC
{
A − C ) + CEquation
Substituting ∫
t = dtCA
3-156} (3-15
into Equation
CB
3-1
∫
Amounts
C AO
CB = (CC AO
− k
that C
have k
reactedC
k1C A) −+k 2C{(Cintegrating
1 A 2 AO A BO
− C A ) + between
= ∫ C
dt – C
C BO } 0the limits gives: (3-156)
AO
0 A C
(3-157)B –
AO – C A BO AO
and the C A concentration of B is t
Substituting Equation 3-156
dC C Ainto Equation 3-155,
dC rearranging and t
∫ = ∫ dt A
CA
integrating− −between
A t

CB∫C=AO(C ( k +the
k )limits
C
1 – 2 C AA − k ∫
dC A gives:
( −
C −
) + C −kC1C A BO C =)
− k 2∫{(C
dt
= ∫ dt
0 AO − C A ) + C BO } (3-158)
(3-15
(3-
C AO
(
k + AO
1 2 )
k C − k CC2 BOAO
A 2 ( AOAO BO ) 0
0

CA t
 −C⎨ln ⎢That is: ⎥
−
1
ln [C A − α ]C⎪
⎩AO ⎣= t
A ( 1 2)
k + k ⎦ (3-162)
k1 + k 2 (3-165)
1
[ ]
CA t
− C AA − α ) − ln (C AO
ln (dC −dtα ) = t
− ∫ = ∫ (3-163)
First order reversible reaction
That is: ⎡ k C
− ln ⎢ C1AOAO
k + +
( k11 + k222) CAOA − k 22( AO
k k C − k
( k1Equation
+ k2 )
C + k
AO − C BO2 ) BO0 ⎪
C ⎤ ⎫
⎥ ⎬ = ( k 1 + k 2 )t
(3-158)

⎣ Substituting 3-160 into⎦ ⎪ ⎭Equation 3-163 gives

−
1
[
ln (C A − α ) − ln (C AO1 − α )C A= t ] dC A (3-163) = dt
t
k1 + k 2 − ∫
( ⎧ )⎛C AO C k −2 (C AOk−2 C BO )C⎞ − C ∫ (3-159)

Substituting Equation 3-160 into

{ [
k + k
− ln ( k11−+⎪⎨kln22 )⎜C
⎪⎩ Equation
⎝
⎛
CAA −−kA 2 (C⎜AO − C BO
3-163 2
⎞
⎟ () ⎟AO
⎝kk1 1++kgives
k2 ⎠ ⎠ ] BO )
0

(3-166)
⎧⎪ ⎛
− where
k 2 (C AO − C BO ) ⎞ ⎛
}
ln [ k1C AO + k 2 C BO ] = ( k1 + k 2 )t
k 2 (C AO − C BO ) ⎞ ⎫⎪
(3-164)
− ⎨ ln ⎜ C A − ⎟ − ln ⎜ C AO −
⎛ ⎞ ⎟ ⎬ = ( k 1 + k 2 )t
⎪⎩ ⎝ kor1 + k 2 α =⎠ k 2⎝ k1 + k 2 ⎠ ⎪⎭
⎜ ⎟ (C AO − C BO ) (3-160)
⎝ k1 + k 2 ⎠
(3-164)
⎛ k 2 (C AO − C⎧BO ) ⎞ ⎫⎪
⎞( k⎡1 +Equation ⎫ Equation 3-159 becomes
− ln ⎜ C AO −
+ ⎪
⎛
⎜
k ⎟ +⎪1⎟ C( kA1−+(kC2AO
1 ⎬ =
⎧
Substituting k 2 ) t )C A−−CkBO
3-160 C)AO
into
⎪ + k 2 C BO ⎤
⎝ k k 2 ⎝ k⎠ − ⎪ 2
1
⎪ 2⎭ ⎨⎪ln⎠ ⎢ ( ⎪) ⎥
− ln ⎨ ⎩ ⎣C A k 1 + k 2 ⎬ = ( k1 + k 2⎦)t (3-167)
1 ⎛ k dC ⎞ t (3-165)
⎪− ⎪
⎧⎪ ⎡ ( k1 + k 2 )C A − k 2 C AO ⎪⎩ +k1k+⎝C ⎜
1
∫C AO + C A
BO ⎟= ∫ dt
kk2⎡2Ck ⎤CC A +− kαC⎠ 0− k ⎪C + k C ⎤ ⎫ ⎪
(3-161)
2⎭ AO
−2 lnBO ⎥ ⎬ = ( k 1 + k 2 )t
1 AO 2 AO 2 BO
− ⎨ln ⎢ ⎢ AO ⎥
⎪⎩ ⎣ ( k1 + k 2 ) ⎣ ⎦ ( k1 + k 2 ) ⎦ ⎪⎭
(3-165)
⎡k C +k C −k C +k C ⎤⎫
 Reaction Rate Expression
− ln ⎨
( ) (
C Ae + 1 • C A − C AO − C Bo ⎫⎪
⎧⎪ C Be149 )
Reaction
⎬ Reaction RateR
Reaction Rate ⎪⎩ Expression(
(C Be C Ae ) • C AO
149+ C BO ) ⎪⎭
First order reversible reaction
At equilibrium with concentrations of A and B as C , C , respectively,
Ae Be
then k C = k C . Since dC /dt = 0 at equilibrium At equilibrium with concentrations of A and B as C
1 Ae 2 Be A
At equilibrium with concentrations of A and At B
equilibrium
versus
as Ctime , C with
t gives
, concentrations
a straight
respectively, line with theofslope
A and(k1 +Bk2as
).Ae
then k C Ae = Be kC
then kslope
C and= the
k 2CBe. . Since
Since
equilibrium dC
dC A/dt
constant K, =
/dt 0andat
k1 = 0 equilibrium
kat
2 can be de
equilib
thenk1 k1CAeCAt
Be equilibrium
= k C
2 Be . Since dC A /dt = 0 at 1
equilibrium Ae
1 Ae 3-14 shows
Figure 2 Be a plot of the reversible
A first order reacti
=K= (3-168)
k2 C Ae
k1 C Be
k1 C Be k = KC
= Be
= K = Equation 3-168 into Equation 3-167 gives
Substituting 1
=
k 2K = C Ae (3-168)
k2 C Ae k C 2 Ae
⎧ ⎛ C ⎞ ⎫ Substituting Equation 3-168 into Equation 3-167
Substituting
⎪⎜
Be
+ 1⎟ Equation
• C A − (C AO3-168
− C BO ) ⎪into Equation 3-167 gives
⎪ ⎝ C Ae ⎠ ⎪ Substituting Equation 3-168 into Equation 3-
− ln ⎨ ⎬ = ( k 1 + k 2 )t (3-169)
⎪ ⎛ C Be ⎞ ⎪ ⎧ ⎛ C Be ⎞ ⎫
⎪⎧ ⎛ C⎝Be
⎩⎪ ⎜
⎜
C
• C
⎞ AO + C BO
(
⎟
⎠ ⎪
+ 1⎟ • C A − C AO − C BO ⎪
⎭ )
⎫ ⎪⎜ (
+ 1⎟ • C A − C AO − C BO ⎪ )
Ae
⎪⎝ C ⎠ ⎪
−⎧ln⎛ ⎨C BeAe ⎞ =⎫ ( k1 + k 2 )t
− ln ⎨
⎪ ⎝ C Ae ⎠ ⎪
⎬ = ( k1 +⎪ k⎜ ⎪2 )t + ⎛C (
1⎟Be• C(3-169)
A − C AO ⎞− C BO⎪ ⎪
⎬ )
A plot of ⎛ C Be ⎞ ⎪ ⎝ ⎪C Ae ⎜ ⎠ • C AO + C BO ⎟ ⎪
⎪
⎜ • C AO + C BO ⎟ ⎪ − ln ⎨ ⎩ ⎝ C Ae ⎠ ⎪
⎭ ⎬ = ( k1 + k
⎪ ⎝ C Ae ⎠ ⎪ ⎛ C Be ⎞
⎧⎪ (C Be C Ae + 1) • C A − (C AO − C Bo ) ⎫⎪ ⎭
⎩ ⎪ • C + C ⎪
− ln ⎨ From slope (k1+k2) and equilibrium ⎪ K, k1 and k2 can
⎜ Figure 3-14. be calculated
BO ⎟reversible reaction.
AO First order
⎪
⎬ ⎝C ⎠
General reversible reaction
Integration of rate equation is difficult for order > 1 or 2
152 Modeling of Chemical Kinetics and Reactor Design
Differential method of analysis is used to search the form of rate eq.
152 Modeling of Chemical Kinetics and Reactor Design
For example, lets assume below eq. dCfits the data CA
( A)
− r = − A
= k
dC Adt
1
(1 C+ kA2C A ) (3-177)
(− rA ) = − = k1
(1 + k 2ofC AEquation
dt reciprocals
Taking the ) 3-177 gives
(3-17

Taking1 the1reciprocals
+ k 2CA 1of Equation
k2 3-177 gives
= = +
(− rA ) k1C A k1C A k1 (3-178)
1 1 + k 2CA 1 k
= = + 2
1/(-ra) (− rPlotting
vs 1/CA gives straightA ) line kwith
C
1/(–r
1 AA )slope
k C
versus
1 A1/k1
1/Ck
A1 and
would intercept
give a k2/k1
straight line with the (3-17
slope
equal to 1/k 1 and an intercept of k 2/k 1. Another analysis method
involves1/(–r
Plotting multiplying each side of Equation 3-178 by k1/k2with
and solving
A) versus 1/CA would give a straight line the slo
for to
equal ) to give
(–rA1/k and an intercept of k /k . Another analysis meth
1 2 1
 Plotting 1/(–rA) versus 1/CA would give a straight li
equal to 1/k 1 and an intercept of k 2/k 1. Another a
General reversible reaction involves multiplying each side of Equation 3-178 by k
for (–rA) to give

k1 ( − rA )
(− rA ) = k − k C
2 2 A

Plotting
• Plotting (-rA) vs (-rA)/CA gives A) versus
straight(–rline (–rA)/C
with slope A gives
-1/k2 and a straight lin
intercept k1/k2 equal to –1/k2 and the intercept equal to k1/k2.

SIMULTANEOUS IRREVERSIBLE SIDE R

Consider the chemical reactions

k1
A →B
 For component C ( + r )
in =which
which the reactions are first order, the initial concentration
C
dt
C
= the
k 2 C reactions
Reaction
A Rate
of A is
are first (3-182)
Expression order,
153 the init
C
, and both the concentrations of B and C are zero. The rateAO , and both
Reaction
the
Rate
concentrations
Expression 153
of B and
equations representing the reactionsk 1 for a
em are:
Simultaneous irreversible side reaction
For component C ( C )
ations representingRearranging
the reactions
and for + a
integrating
r =
system
dC
constant
Equation
C
=
dC C dt are:
volume
k C
2 A
3-180 batch
between the (3-182) → B
A
limits gives
For component C ( + rC ) = = k 2C A (3-182)
CA t dt k 2 gives
− ∫
dC A and integrating Equation 3-180 between the limits
Rearranging
dC A= ∫ ( k1 + k 2 )dt dC ↓
(− rAC AO
or component A Rearranging ( k1 + k 2 )CEquation
) = −C Adtand =0integrating (
(3-180)
For component A − rA = −
A 3-180 between the )
limits gives A
(
(3-183)
= k1 + k 2
CA dt
−A ∫
dC A
t
t= ( k1 + k 2 )dt
C
C
dCC C
dC ∫
B ( k01 + k 2 )dt
(3-183)
or component B −( +−∫rBln
C)AO A A=
=∫=( k11C
A
= + Ak 2 )t (3-181) dC(3-184)
(3-183)
C
C AO C AO A dt 0 (
For component B + r = B = k C
B )in which
dt
1 the
A rea
Reaction
CA
− ln
The = ( kfor
solution
C AC 1 + kthe2 )t concentration of A is , and both
C AO(3-184)
− ln = ( k 1 + k 2 )t dC C
( )
AO (3-184)
C AO For component C + rC equations
= repres
= k 2C A
−( k1 + k 2 )t dt
(3-185)
C A =solution
The C AO e for the concentration of A is system are:
The solution for the concentration of A is
Substituting− (Equation
k1 + k 2 )t
Rearranging
3-185 and
into Equation integrating
3-181, Equation
rearranging and 3-180
C A = C AO−(ek1 + k 2 ) t (3-185)
integrating
C A = C AO e gives (3-185)
CA t For componen
 The solution for the concentration of A is
154 Modeling of Chemical Kinetic
dC A
For component A ( − rA ) = − −( k1 +=k 2()kt 1 + k 2 )C A (3-180)
SimultaneousC A = C AOirreversible
edt side reaction (3-185)
( k1 + k 2 ) { }
C k − ( k 1 + k 2 ) t Rat
C = B
AO 1
1 − eReaction
Substituting
dC B Equation 3-185 into Equation 3-181, rearranging and
(+ rB ) = gives= k1CFor
For component Bintegrating
dt
A component C + r =
dC C
(3-181)=k C ( Correspondingly,
C)
dt the
2 Asolution fo

CB t
dC B
154 ∫
0 C e
AO
= k1 ∫ dt Kinetics
Rearranging
− ( k 1 + k 2of) t Chemical
Modeling
0
and and
integrating
CC =
Reactor Equation
C AO k2
1− e
Design −3-180
(
( k1 + k 2 ) {
+ k 2 ) tbetw
k(3-186)
1
}
{ }
CA t
C AO k1 − ( k 1 +dC
k 2 )t
C B = rearrangement
Further
( k1 + k 2 )
1 −−e of Equation
∫ C ∫ 1 2 A
= (
3-186
k + k )
gives
dt
Concentration profiles can(3-189)
be deve
C AO A 0 Equations 3-180, 3-181, and 3-182,
CB t
1 −( k1 + k 2 )t
fourth order method at known valu
∫ dC = k
Correspondingly,
C AO 0
B 1 ∫ the solution
e + Constant
for the concentration of C (3-187)
is
CA
= ( k + k )t PSEUDO-ORDE
0
− ln 1 2
C AO
C AO k 2 −( k + k )t
Pseudo order reactions
Kinetic data becomes rapidly more complex as the reaction order increases

In cases where concentration one or more component present in the rate

eq. remain constant, these terms may be included in the rate constant

For example in catalytic reaction catalyst concentration remain constant

during the reaction

A kinetic study of a reaction can be simplified by running the reaction with

one or more of the components in large excess, so that the concentration
remain effectively constant.
 reaction with one or more of the components in large excess, so that
the concentration remains effectively constant. Mc Tigue and Sime + [2] –
Br + CH
Reaction
consider the oxidation
2 CHO
Rate + H O
Expression → CH COOH
If such
155
3of aliphatic 2aldehydes there
3 + 2H
thatisethanal +
excessively
with2Br
Pseudo order reactions
bromine in aqueous solution follows second-order
constant kinetics:
and the reaction
If there is excessively large aldehyde, its concentration
The rate equation remainsfor a constant volume b
of the reaction
kinetics. Equation 3-192 ca
nstant and the reaction can be referred to as pseudo-first order+
Br2 + CH3CHO + H2O → CH3COOH + 2H + 2BrReaction –
(3-191)
Rate Exp
netics. Equation 3-192 can be rewritten as
dC Br2 dC Br2
dC Br2
The rate equation
− of the
If there = reaction
isk 2 C
excessively
CH CHO Br −
for aCconstant =
volume batch
k C
2large aldehyde, its
1
system is
Br2 concentr
− = k1C Br2 dt 3
(3-193)
dt
dt If aldehyde in excess, its constant
concentration and the reaction
remain can be
constant, referred
reaction can to as pseu
dC Br2
− kinetics.
= k C Equation
C 3-192 can be rewritten as(3-192)
where
here
be referred to pseudo dt first order kinetics
2 CH 3 CHO Br 2

dC Br2 k1 = k 2 C CH 3CHO
k1 = k 2 C CH 3CHO − = k1C Br2 (3-194)
dt
Second
The second order
order rate rate 2 is k 2 = k1 C CH 3 CHO can
constant
constant kwhere , andbe The
be second
determined
can byorder rate co
termined by measuring
measuring 1 at known
K1 atkknown of aldehydedetermined
aldehyde concentrations.
concentration The by measuring k
e of excess reagent concentrations has important practical conse-use of excess reagent con
k1 = k 2 C CH 3CHO
ences where physical methods, such as light absorption orquences con- where physical m