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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

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

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

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 )

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

Cs = CA0 (1 + ek1t + ek2t )

k1 k2 k2 k1

k

1 In ( 2k )

1

t max = =

k log mean k 2 k1

= ( ) 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

= + ( )

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

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