Lecture 3
Lecture 3
Lecture 3
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
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 :
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
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)
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
⎡ C Af ⎤ C Af
− ln ⎢ C A ⎥ = k( t 2 − t1 ) − ln = kt (3-30)
⎢⎣C AO ⎥⎦ C AO
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
−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.
(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 ⎠ ⎪⎭
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
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)
(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.
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
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