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CONSTANT VOLUME BATCH REACTOR

Similarly, for any product R we can find,


In a constant-volume system the measure of reaction rate of component i becomes r
PR = CR RT = PR0 + ( 0 ) (6)
n

1 dNi d ( ) dCi Equations 5 and 6 are the desired relationships between total pressure of the
ri = = = system and the partial pressure of reacting materials.
V dt dt dt
The Conversion
or for ideal gases, where C=p/RT Suppose that NAo is the initial amount of A in the reactor at time t = 0, and that NA
is the amount present at time t. Then the conversion of A in the constant volume
1 dpi system is given by
ri =
RT dt NA0 NA = 1 CA
XA = =1
ANALYSIS OF TOTAL PRESSURE DATA OBTAINED IN A NA0 0 CA0
CONSTANT-VOLUME SYSTEM.
PA NA NA0 ax
CA = = = dCA
RT V V dXA =
CA0
NA0 a N N0
CA = INTEGRAL METHOD OF ANALYSIS OF DATA
V n V Irreversible Unimolecular-Type First-Order Reactions.
A --- PRODUCTS
Equation 5 gives the concentration or partial pressure of reactant A as a function of XA t
the total pressure n at time t, initial partial pressure of A, pAo, and initial total
dXA
= k dt or In (1 XA ) = kt
pressure of the system, .0 0 1 XA 0
a
PA = CA RT = PA0 ( 0 ) (5)
n

Irreversible Bimolecular-Type Second-Order Reactions A + 2B-------R


A + B -------- PRODUCTS (2CA0 CB0 )(CB0 CB ) CA0 CB
1 XB M XA CB CA0 CB + In = (2CA0 CB0 )2 kt M2
In = In = In = In CB0 CB CA CB0
1 XA M (1 XA ) CB0 CA MCA 1 1
2 = 8kt M=2
= CA0 (M 1)kt = (CB0 CA0 )kt M 1 CA CA0 2

Caution 1: 2A-----PRODUCTS (CA0 CB0 )(CB0 CB ) CA0 CB


1 1 1 XA + In = (CA0 CB0 )2 kt M1
CB0 CB CB0 CA
= = kt
cA CA0 CA0 1 XA
1 1
Caution 2: A + B --------- PRODUCTS 2 = 2kt M=1
CA CA0 2
CB CA0 M 2XA
In = In = CA0 (M 2)kt M2
CB0 CA M(1 XA ) Empirical Rate Equations of nth Order
When the mechanism of reaction is not known, we often attempt to fit the data with
1 1 1 XA an nth-order rate equation of the form
= = 2kt M=2
CA CA0 CA0 1 X A
CA1n CA01n = (n 1)kt n1
Irreversible Trimolecular-Type Third-Order Reactions.
Zero Order Reaction
A + B + D -------PRODUCTS

1 CA0 1 CB0 CA0


In + In CA0 CA = CA0 XA = kt for t <
(CA0 CB0 )(CA0 CD0 ) CA (CB0 CD0 )(CB0 CA0 ) CB k
1 CD0 0
+ In = kt = 0
(CD0 CA0 )(CD0 CB0 ) CD
Overall Order of Irreversible Reactions from the Half-Life t1/2, Homogeneous Catalyzed Reactions

Defining the half-life of the reaction, t1/2 , as the time needed for the CA
concentration of reactants to drop to one-half the original value, we obtain In = In (1 XA ) = (k1 + k 2 CC )t = k observed t
CA0
(0.5)1n 1 Autocatalytic Reactions
t1/2 = CA01n A reaction in which one of the products of reaction acts as a catalyst.
k (n 1)
CR
CA0 (C0 CA ) C
Fractional Life Method, R0
In = In = C0 kt = (CA0 + CR0 )kt
CA (C0 CA0 ) CA
C
F1n 1 A0
tf = C 1n
k(n 1) A0 In terms of the initial reactant ratio M = CRdCAO and fractional
conversion of A, this can be written as
M + XA
In = CA0 (M + 1)kt = (CA0 + CR0 )kt
Irreversible Reactions in Parallel M(1 XA )

CA Irreversible Reactions in Series


In = (k1 + k 2 )t CA
CA0 In = k1 t or CA = CA0 ek1t
CA0

ek1t ek2t
CR CR0 k1 CR = CA0 k1 ( + )
= k 2 k1 k1 k 2
CS CS0 k 2

k2 k1 Second-Order Reversible Reactions.


Cs = CA0 (1 + ek1t + ek2t )
k1 k2 k2 k1

The time at which the maximum concentration of R occurs is thus

k
1 In ( 2k )
1
t max = =
k log mean k 2 k1

The maximum concentration of R

CRmax k1 k2 XAe 2(XAe 1)XA 1


= ( ) k2k1 In = 2k1 ( 1)CA0 t
CA0 k2 X Ae X A X Ae
First-Order Reversible Reactions Reactions of Shifting Order
CA0
With conversions measured in terms of , this may be looked on as a pseudo first- In + k 2 (CA0 CA ) = k1 t
order irreversible reaction which on integration gives
CA

A-------R K C = K = equilibrium constant K c = k1 /k2 CA0 CA 1 k1 t


= + ( )
CA0 k k CA0
XA CA CAe M+1 In( C ) 2 2 In ( C )
In (1 ) = In = k t A A
XAe CA0 CAe M + XAe 1

( 0 ) 1

= 2 +
0 0
DIFFERENTIAL METHOD OF ANALYSIS
VARYING VOLUME BATCH REACTOR
dCA CA0 dV CA0 d (In V)
For such systems the volume is linearly related to the conversion, or with or
dt VA dt A dt
VXA1 VXA0
A = INTEGRAL METHOD OF ANALYSIS
VXA0
Zero-Order Reactions
where Ais the fractional change in volume of the system between no
conversion and complete conversion of reactant A. CA0 V
In = kt
NA = NA0 (1 XA ) A V0
First-Order Reactions
We see, then, that A accounts for both the reaction stoichiometry and
the presence of inerts. Noting that
V
In (1 ) = kt, V = V V0
CA =
NA
=
NA0 (1XA )
=CA0
1XA A V0
V V0 (1+ A XA ) 1+ A XA
Second-Order Reactions
Thus,
CA (1 + A )V V
CA 1 XA 1 C + A In (1 ) = kCA0 t
A0 V0 A V V0 A
= or XA =
CA0 1 + A XA 1 + A CA /CA0

INTERPRETATION OF
BATCH REACTOR DATA