Irreversible unimolecular-type first-order reaction A Products

dC A rA = = kC A dt
t dC A = k dt CA C 0 CA
A0

CA ln = kt CA
0

For convenience let

xA =
Fractional conversion

NA NA
0

NA

NA CA = = NA V
0

1 xA = C A (1 x A ) V
0
0

CA = CA CA x A dC A = 0 C A dx A
0

dC A = C A dx A
0

Substitute dCA and CA into the rate equation

C A dx A
0

dt

= k (C A C A x A )
0 0

dx A = k(1 x A ) dt
xA t dx A = k dt 0 1 xA 0

ln(1 x A ) = kt

What if

dC A .6 0 .4 = kC0 A CB dt

Can we treat it like in the example?

Irreversible bimolecular-type second-order reaction A + B Products

dC A dCB rA = = = kC A CB dt dt

A and B have reacted equally C A x A = CB xB

0 0

Then
dx A rA = C A = k(C A C A x A )(CB C A x A ) dt
0 0 0 0 0

Let M =

CB CA

dx A rA = C A = kC2 A (1 x A )(M x A ) dt
0 0

xA

t dx A = CA k dt 0 (1 x A )(M x A ) 0
0

CBC A M xA 1 xB CB ln = ln = ln = ln 1 xA M(1 x A ) CB C A MCA

0 0

= C A (M 1)kt = (CB C A )kt, M 1

0 0 0

Overall order of irreversible reactions from half-life ( t )

1 2

Consider the irreversible reaction

A + B + L Products dC A b C rA = = kCa A B dt CB = At any time CA Therefore dC A a +b +L rA = = kC A CA L = k L Ca A dt
b b

dC A = kCn A dt

Integrating for n 1
n 1n C1 C )t A A = k (n 1
0

k L = k

Defining the half-life as the time needed for the reduction of concentration of reactant for one-half of the original value then we get
2n1 1 1n CA t = k(n 1)
1 2 0

Irreversible reactions in parallel

Irreversible reactions in series

First-order reversible reactions

Second-order reversible reactions

Differential method of analysis of data Guess the rate equation Find (1/V)(dN/dt) Plot of the data
Rate equation is satisfied by the data.

Good fit

Unfit

General procedure 1. Hypothesize a mechanism.

dC A rA = = f (k, C) dt dC A rA = = kf (C) dt

2. Plot concentration vs. time from experimental data 3. Draw a smooth curve through the data. 4. Determine the slope at each concentration.

Nonlinear-curve fitting can be used

5. Evaluate f(C) for each concentration

If we obtain straight line through the origin, our mechanism is consistent to the data. If not hypothesize another one.

Variable-volume batch reactor

1 dNi 1 d(Ci V ) = ri = V dt V dt 1 VdCi + CidV ri = V dt dCi Ci dV + ri = dt V dt

Let V = V0 (1 + A x A ) A = fractional change in volume

= Vx
A=

Linear change of volume with concentration!

Vx
A=

A=

Vx

No conversion

Complete conversion

NA = NA (1 x A )
0

Therefore
NA NA (1 x A ) (1 x A ) CA = = = CA V V0 (1 + A x A ) (1 + A x A )
0 0

Thus
CA 1 xA = CA 1 + A x A
0

or
CA 1 CA xA = ACA 1+ CA
0 0

Substitute V and NA into the rate equation

1 dNA rA = V dt NA d(1 x A ) 1 rA = V0 (1 + A x A ) dt
0

or
dx A rA = (1 + A x A ) dt
0

CA

If A = 0
dx A rA = C A dt
0

Constant-volume

Integral method of analysis The analysis requires again the integration of the rate expression to be tested. For T, P = constant
C A dx A 1 dNA rA = = V dt 1 + A x A dt
0

CA

xA
0

t dx A = dt = t 0 (1 + A x A )( rA ) 0

We need to know the exact form of rA in order to integrate this equation

Differential method of analysis The procedure is the same as for constantvolume batch reactor analysis except that we must replace
dC A dC A d ln V by + CA dt dt dt dx A or 1 + A x A dt
0

CA

Zero-order reactions For homogeneous zero-order reaction (-rA f(C))

1 dNA rA = V dt dx A rA = =k 1 + A x A dt
0

CA

with V = V0 (1 + A x A ) and C A we obtain

xA
0

t dx A = dt 0 (1 + A x A )( rA ) 0

CA

xA
0

CA CA dx A V = ln(1 + A x A ) = ln = kt A A V0 0 (1 + A x A )
0 0

First-order reactions For unimolecular-type first-order reaction, P = const

1 dNA rA = = kC A V dt

Substitute xA and -rA

CA CA xA = C 1+ A A CA 1
0 0

rA =

dx A (1 + A x A ) dt
0

CA

dx A kC A (1 x A ) rA = = 1 + A x A dt 1+ A x A CA
0 0

xA

V dx A = ln(1 x A ) = ln1 = kt 0 1 xA A V0

Second-order reactions For bimolecular-type second-order reaction 2A Products or A + B Products, C A = CB

0 0

The rate is
rA = kC2 A

Substitute xA and -rA

C 1 A CA xA = C 1+ A A CA
0 0

rA =

dx A (1 + A x A ) dt
0

CA

dx A rA = = kC2 A 1 + A x A dt
0

CA

1 xA 1+ A x A

xA

1+ A xA (1 + A )x A dx A = + A ln(1 x A ) = kC A t 2 1 xA 0 (1 x A )
0

nth-order reactions
1 xA rA = kC = kC 1+ A x A
n A n A0 n

From
CA
xA
0

t dx A = dt = t 0 (1 + A x A )( rA ) 0

We obtain
xA

(1 + A x A )n1 n1 dx A = CA kt n (1 x A ) 0
0