• which on integration gives

[42]
• In terms of the initial reactant ratio M = CR0/CA0 and fractional conversion of A, this can be
written as

[43]
Irreversible Reactions in Series.
• We first consider consecutive unimolecular type first-
order reactions such as

• The rate equations for the three components are

[44]

[45]

[46]
• Start with a concentration CA0 of A

[47]

• To find the changing concentration of R, substitute the

concentration of A from Eq. 47 into the differential
equation governing the rate of change of R, Eq. 45;
thus
[48]

• which is a first-order linear differential equation of the

form
• By multiplying through with the integrating factor the
solution is

Applying this general procedure to the integration of Eq.

48, we find that the integrating factor is ek2t. The constant
of integration is found to be –k1CAo/(k, - k,) from the initial
conditions CR0 = 0 at t = 0, and the final expression
for the changing concentration of R is

[49]
• Noting that there is no change in total number of moles, the
stoichiometry relates the concentrations of reacting
components by

• which with Eqs. 47 and 49 gives

[50]

• Now if k2 is much larger than k1, Eq. 50 reduces to

• Now if k1 is much larger than k2, Eq. 50 reduces to

• Values of k1, and k2 also govern the location and

maximum concentration of R. This may be found by
differentiating Eq. 49 and setting dCR/dt = 0. The time at
which the maximum concentration of R occurs is thus

[51]
• The maximum concentration of R is found by combining
Eqs. 49 and 51 to give

[52]
First-Order Reversible Reactions

[53a]

• Starting with a concentration ratio M=CR0/CA0 the rate

equation is

[53b]
• Now at equilibrium dCA/dt = 0. Hence from Eq. 53 we find
the fractional conversion of A at equilibrium conditions to
be

and the equilibrium constant to be

• Combining the above three equations we obtain, in terms

of the equilibrium conversion,
• With conversions measured in terms of XAe, this may be
looked on as a pseudo first-order irreversible reaction
which on integration gives

[54]

• A plot of -In(1 - XA/XAe) vs. t, as shown in Fig. 3.13,

gives a straight line.
• The similarity between equations for the first-order
irreversible and reversible reactions can be seen by
comparing Eq. 12 with Eq. 54 or by comparing Fig. 3.1
with Fig. 3.13. Thus, the irreversible reaction is simply
the special case of the reversible reaction in which
Second-Order Reversible Reactions

• For the bimolecular-type second-order reactions

[55a]

[55b]

[55c]

[55d]
• with the restrictions that CA0= CB0 and CR0= Cso= 0, the
integrated rate equations for A and B are all identical, as
follows

[56]

A plot as shown in Fig. 3.14 can then be used to test the

adequacy of these kinetics
Reversible Reactions in General

• If Eq. 54 or 56 is not able to fit the data, then the search

for an adequate rate equation is best done by the
differential method.
Reactions of Shifting Order

• In searching for a kinetic equation it may be found that the

data are well fitted by one reaction order at high
concentrations but by another order at low concentrations.
Consider the reaction

[57]

At high CA the reaction is of zero order with

rate constant k1/k2

At low CA the reaction is of first order with

rate constant k,
• Integrating Eq. 57:

[58a]

or

[58b]

• Two ways to test this rate form are then shown in Fig.
3.16
By similar reasoning to the above we can show that the
general rate form

[59]
• Another form which can account for this shift is

[60]

Reactant A decomposes in a batch reactor

The composition of A in the reactor is measured at various

times with results shown in the following columns 1 and 2.
Find a rate equation to represent the data.
SOLUTION
• Guess First-Order Kinetics.
• Guess Second-Order Kinetics.
• Guess nth-Order Kinetics.

Let's plan to use the fractional life method with F = 80%.

Then Eq. 33b becomes

Next take logarithms


Differential Method of Analysis of Data
The procedure is as follows.
• Plot the CA vs. t data, and then by eye carefully draw a smooth curve to
represent the data. This curve most likely will not pass through all the
experimental points.

• Determine the slope of this curve at suitably selected concentration values.

These slopes dCA/dt = rA are the rates of reaction at these compositions.

• Now search for a rate expression to represent this rA vs. CA data, either by
(a) picking and testing a particular rate form, -rA = kf (CA), see Fig. 17, or
(b) testing an nth-order form : by taking logarithms of the rate
equation (see Fig. 3.18).
• With certain simpler rate equations, however, mathematical
manipulation may be able to yield an expression suitable for
graphical testing. As an example, consider a set of C, vs. t
data to which we want to fit the M-M equation

[57]

• By the differential method we can obtain -rA vs. CA.

[61]
• Alternatively, a different manipulation (multiply Eq.
61 by yields another form, also suitable
for testing, thus

[62]
Try to fit an nth-order rate equation to the concentration
vs. time data of Example 3.1.
take logarithms of both sides (see columns 3 and 4), or