802 C he m i ca l K i net i cs I

In Eq. (32.7c) we chose to write the volume in cubic metres and the concentration in
moljm 3 • In these equations we could equally well choose to use litres for the volume unit
and moljL for the concentration unit. All that is required is that the two be in conformable
units ; that is, the product of concentration times volume must equal the amount of sub­
stance. For the remainder of this chapter we will use concentrations in moljL, which is the
customary unit.

• EXAMPLE 32 . 1 The rate of decomposition of acetaldehyde can be studied by

measuring the pressure in a system at constant volume and temperature. Express the

-
rate of reaction in terms of the rate of change of the pressure. The overall reaction is
CH 3 CHO(g) CH 4 (g) + CO(g)
with mole numbers

Then

The initial pressure, p O = n OR T/V ; then p = p o + (R T/V)� ; and we obtain

1 1
dp R T d� d� dp
or
dt V dt V dt R T dt.·
Alternatively, we can use Eq. (32.7a). We see that : op/o n i = R T/V for all i ; then Eq.

_-
(32.7a) becomes
dp
dt
_- (Vi RT
V +
V2 V
RT
+
) -_
R T d�
V 3 V dt
fl.vR T
V
_- ( - 1 + 1 + 1) R T d�
V dt
R T d�
V dt '

32.3 RATE LAWS

The rate of reaction will be a function of temperature, pressure, and the concentrations of
the various species in the reaction, Ci ' and may depend on the concentrations, cx , of
species such as catalysts or inhibitors that may not appear in the overall reaction. Further­
more, if the reaction occurs homogeneously (that is, exclusively within a single phase), the
rate is proportional to the volume of the phase, V. If the reaction occurs on an active sur­
face the rate is proportional to the area of the active surface, A. Thus, in a very general way
we can write the rate of reaction as the sum of the rates of the homogeneous and surface
reaction :
(32.8)

wheref(T, p, Ci ' cJ and F(T, p, C j , cJ are functions to be determined from the experimental
data. Equation (32.8) is the rate law for the reaction.
Reactions are classified kinetically as homogeneous or heterogeneous. A homo­
geneous reaction occurs entirely in one phase ; a heterogeneous reaction occurs, at least in
part, in more than one phase. A common type of heterogeneous reaction has a rate which
 R ate laws 803

depends on the area of a surface that is exposed to the reaction mixture. This surface may
be the interior wall of the reaction vessel or it may be the surface of a solid catalyst. At some
stage in any kinetic study it is necessary to find out if the reaction is influenced by the walls
of the vessel. If the vessel is made of glass, it is usually packed with glass wool or beads or
many fine glass tubes so as to increase the exposed area. Any effect on the rate of the reac­
tion is noted. If the reaction is strictly homogeneous, the rate will not be affected by packing
the vessel in this way. In this chapter the discussion will be restricted almost entirely to
homogeneous reactions.
For homogeneous reactions, the second term on the right-hand side of Eq. (32.8) is
negligible and we have
d�
= Vf(T, p, Ci , cx) · (32.9a)
dt
In this situation it is convenient to deal with the rate of the reaction per unit volume,
(1/V) (d�/dt). In view of Eq. (32.8), the rate per unit volume becomes
d(�/V)
-----;[t = f(T, p, Ci , cx), (32.9b)

which is the rate law for a homogeneous reaction.

Dividing Eq. (32.5) by the volume, we obtain
1 d� 1 dn i
V dt v; V dt '
- -

If the volume does not change with time, this equation takes the form
d(�/V) dCi
1
(32. 10)
dt V i dt '

in which Ci is the conc'::ntration of the ith species ; Ci = n/V.

In many cases, the rate law has the simple form

�t
d( V)
= kc'A C� C t . . · , (32. 1 1)

in which CA , CB , CC , . . . , denote the concentrations of the participating species, and k, rx, j3 ,

and l' are constants. The constant k is the rate constant of the reaction, or the specific rate
of the reaction, since k is the rate if all the concentrations are unity. In general the rate
constant depends on temperature and pressure. The constant rx is the reaction order with
respect to A, j3 is the reaction order with respect to B, and l' is the reaction order with
respect to C. The overall reaction order is the sum : rx + j3 + 1'.
The order of the reaction governs the mathematical form of the rate law and therefore
the variation in concentration of all the species with time. The order of the reaction with
respect to the various species must be discovered from experiment. The experimental
determination of the order of the reaction with respect to the various substances taking
part is one of the first objectives of a kinetic investigation. It cannot be emphasized too
strongly that the order of the reaction with respect to a given substance has no relation
whatsoever to the stoichiometric coefficient of that substance in the chemical equation. For
example, in the chemical equation above, the coefficient ofN z O 5 is 2. We cannot infer from
this that the reaction is second order with respect to N z0 5 . (Elementary reactions­
reactions that take place in a single act -are excepted from this statement.)
804 C hemical K i n et i cs I

32.4 F I R ST- O R D E R R EACTI O N S

Consider a simple decomposition reaction of the type
A --------> Products.
Since substance A is the only reactant, we choose to balance the equation with the coef­
ficient of A equal to unity. Suppose that the reaction is first-order with respect to A and
that the rate does not depend on the concentrations of any products ; then the rate law,
Eq. (32. 1 1), becomes
d(�/V) =
dt kc (32. 12)

where c is the concentration of A.

To integrate this equation we must either express c as a function of �/V or �/V as a
function of c. In either case, we obtain the relation by dividing Eq. (32.2) by V,

c = Co - � ' (32. 1 3)
V
and then differentiate with respect to time :
dc d(�/V)
dt .
(32. 14)
dt
Using this value for d(�/V)ldt in Eq. (32.12), we find that
dc
- dt = kc. (32. 1 5)

By rearranging we can separate the variables,

dc =
k dt,
c -
-

and integrate from t = 0 when c= Co to t; then

Ic
Co
dc =
c - 0
- k dt,It
or
c
In - = - kt, (32. 16)
Co
which can also be written
(32. 1 7)
Thus for a first-order decomposition, the concentration of A decreases exponentially
with time. After measuring c as a function of time we can test whether the reaction is first
order in A by plotting In (clco) versus t. According to Eq. (32.16) this plot should be a
straight line if the reaction is first order in A. If we find that our experimental points lie on
a straight line we conclude that the reaction is first order in A. The slope of this line is

equal to - k.
The half-life, T, of the reaction is the time required for the concentration of A to reach
one-half of its initial value. Therefore, when t = T, C = !co . Putting these values into
 R a d i oactive D ecay 805

Eq. (32. 1 6), we obtain In t = - h , so that

1n 2 0.693
1: = T = -k-· (32. 1 8)

One way to evaluate the rate constant of a reaction is to determine the half-life for various
initial concentrations of the reactant A. If the half-life is independent of the initial con­
centration, then the reaction is first order, and the rate constant is calculated using Eq.
(32. 1 8). It is only for first-order reactions that the half-life is independent of the initial
concentration.
The decomposition of N 2 0 5 is an example of a first-order reaction. The stoichiometry
is represented by

and the rate law is

dCN20S = k
- --a;- CN20S ·

At 25 °C the rate constant is 3.38 x 10- 5 S - 1 . Note the absence of any relation between
the order of the reaction and the stoichiometric coefficient of N 2 0 5 in the chemical equa­
tion .
• EXAMPLE 32.2 Calculate the half-life for N 2 0 5 at 25 °C and the fraction
decomposed after 8 hours ; k= 3.38 X 10 - 5 S - 1 .
0.693 0.693
1: = -k- = 3.38 10 5 = 20 500 s. x S 1

Mter 8 hours the fraction remaining is given by Eq. (32. 1 7) ; since

8 hr = 8 hr (60 min/hr) (60 s/min) = 28 800 s, we have
-=- e - kt e � 3 . 3 8 x 1 0 - S s - 1 ( 2 8 8 0 0 s)
= = 0.378. e 3
Co
= = - O.97

Therefore the fraction decomposed is 1 .000 - 0.378 = 0.622

32.4.1 R a d i oact i ve D ecay

The radioactive decay of an unstable nucleus is an important example of a process that
follows a first-order rate law. Choosing CU 6 4 as an example, we have the transformation

1: = 12.8 hr.
The emission of a p-particle occurs with the formation of a stable isotope of zinc. The
pro bability of this occurrence in the time interval dt is simply proportional to dt . Therefore
dN = A dt (32. 19)
--N '
where - dN is the number of copper nuclei that disintegrate in the interval dt. Equation
(32. 1 9) is a first-order law, and can be integrated to the form
(32.20)
No being the number of CU 6 4 nuclei present at t = 0, N the number at any time t. The