Chemical)Kinetics

Chemical kinetics concerns how rates of chemical

reactions are measured, how they can be predicted,
and how reaction- rate data are used to deduce
probable reaction mechanisms.
 1403)Effect)of)Concentration)on)Reaction)
Rates:)))The)Rate)Law
One of the goals in a chemical kinetics study is to derive an equation that can be used to
predict the relationship between the rate of reaction and the concentrations of reactants.
Such an experimentally determined equation is called a rate law, or rate equation.

a A + b B …. → g G + h H ….

rate of reaction = k[A]m[B]n ….

Rate constant = k
! The larger the value of k, the faster a reaction goes.

Overall order of reaction = m + n + ….

General effect of doubling the initial concentration of a
particular reactant (with other reactant concentrations
held constant).

• Zero order in the reactant—there is no effect on the initial rate of

reaction.
• First order in the reactant—the initial rate of reaction doubles.
If a reaction is first order in one of the reactants, doubling the initial
concentration of that reactant causes the initial rate of reaction to
double.
• Second order in the reactant—the initial rate of reaction
quadruples.
• Third order in the reactant—the initial rate of reaction increases
eightfold.
 1404)Zero0Order)Reactions
An overall zero-order reaction has a rate law in which the sum
of the exponents, m + n…, is equal to 0.
An example for a single reactant A decomposes
to products;
A → products
Rrxn = k [A]0

(0 - [A]0) [A]0
k = - slope Rrxn = k = =
(tf – 0) tf

[k] = mol L-1 s-1

FIGURE'14*3
A)zero0order)reaction:))A)))))))))products
Integrated Rate Law; expresses'the'concentration'
of'a'reactant'as'a'function'of'time.'

-Δ[A] Move to the -d[A]

= k infinitesimal
= k
Δt dt
And integrate from 0 to time t

[A]t t

-! d[A] = ! k dt
[A]0 0

-[A]t + [A]0 = kt

[A]t = - kt + [A]0
 H 2O21aq2 ¡ H 2O1l2 + O21g2
1
14*5'First*Order'Reactions 2
An overall first-order
The rate ofreaction
reactionhasdepends
a rate lawoninthe
which the sum of the
concentration of Hexpo-
2O 2 raised to
nents, m + npower,
+ …., isthat
equal
is, to 1.
H2O2(aq) → H2O(l) + ½ O2(g) rate of reaction = k3H 2O24
It is easy to establish that reaction (14.3) is first order by the metho
d[H
tial 2O2but
rates, ] there are also other ways of recognizing a first-order rea
= - k[H O ] 2 2 [k] = s-1
dt
An Integrated Rate Law for a First-Order Reaction
An'Integrated'rate'Law'for'a'First*Order'Reaction
Let us begin our discussion of first-order reactions as we did zero-ord
tions, by examining
[A]
a hypothetical reaction
t
d[H2O2 ]
t

! ! k¡
= -A dt products
[A]0 [H2O2] 0
for which the rate law is
[A]t ¢3A4
ln = -kt rate of reaction
ln[A] = -
t = -kt + ln[A]
= k3A4
[A]0 ¢t 0
We can obtain the integrated rate law for this first-order reaction by a
the calculus technique of integration to equation (14.12). The resul
derivation (shown in Are You Wondering 14-4) is
EXAMPLE 14-5 Using the Integrated Rate Law for a First-Order Reaction

H 2O 21aq2, initially at a concentration of 2.32 M, is allowed to decompose. What will 3H 2O24 be at t = 1200s?
Use k = 7.30 * 10-4 s -1 for this first-order decomposition.
Analyze
We have values for three of the four quantities in equation (14.13):

3H 2O240 = 2.32 M 3H 2O24t = ?

k = 7.30 * 10-4 s -1 t = 1200 s

We need to solve for the fourth quantity.

Solve
We substitute into the expression

ln3H 2O24t = - kt + ln3H 2O240

= - 17.30 * 10-4 s -1 * 1200 s2 + ln 2.32

3H 2O24t = e -0.034 = 0.967 M

= - 0.876 + 0.842 = -0.034

Assess
This calculated value agrees well with the experimentally determined value of 0.98 M, shown below.

0.800

0.400 Test)for)a)first0order)reaction:))Decomposition)of)H2O2(aq)

Decomposition of H2O21aq2
FIGURE 14-4
*

Test for a first-order reaction:

0.000
2]
on of reactant consumed, as is done
Half-Life, t
uired for one-half of a½reactant to be

That is, at t = t1>2,3A4t = 23A40. At

amount ofthereactant
time taken forconcentra-
or its one-half of a reactant to be consumed.
1

For the half-life of a first-order reaction, use the integrated

Eq; [A]t
- ln 2 = - k * t1>2 ln = -kt
[A]0

½[A]0
0.693 ln = -kt½
(14.14)
[A]0
k

- ln 2 = -kt½
r reactions. We will derive half-life
we encounter them. ln 2 0.693
t½ = 14-2, =
reaction described in Section k k

49 * 102 s = 949 s
14*6'Second*Order'Reactions
An overall second-order reaction has a rate law with the sum of
the exponents, m + n…, equal to 2.
Rate law where sum of exponents m + n +… = 2
A → products

d[A]
= -k[A]2 [k] = M-1 s-1 = L mol-1 s-1
dt
[A]t
d[A] t

! = - ! k dt
[A]0 [A]2 0

1 1
= kt +
[A]t [A]0
The reciprocal of the concentration, 1/[A], is plotted against time. As
the reaction proceeds, [A] decreases and 1/[A] increases in a linear
fashion. So, the slope of the line is (+) and is the rate constant k.

A)straight0line)plot)for)the)second)order)reaction)A)))))))))))products
 14-7 Reaction Kinetics: A Summary 621

TABLE 14.5 Reaction Kinetics: A Summary for the Hypothetical Reaction A ¡ Products

Rate Lawa
3A40
Order Integrated Rate Equation Straight Line k = Units of k Half-Life

0 rate = k 3A4t = - akt + 3A40 3A4 v. time - slope mol L-1 s-1
2 ak
1 rate = k3A4 ln3A4t = - akt + ln3A40 ln3A4 v. time - slope s -1 0.693
ak

3A4t 3A40 3A4

1 1 1 1
2 rate = k3A42 = akt + v. time slope L mol -1 s -1 ak3A40

= -a b
arate 1 ¢3A4
a ¢t

3. To determine the order of a reaction, use one of the following methods.

Use the method of initial rates if the experimental data are given in the
form of reaction rates at different initial concentrations.
Find the graph of rate data that yields a straight line (Table 14.5).
Test for the constancy of the half-life (good only for first-order).
Substitute rate data into integrated rate laws to find the one that gives a
constant value of k.
4. To find the rate constant k for a reaction, use one of the following methods.
Obtain k from the slope of a straight-line graph.
Substitute concentration time data into the appropriate integrated rate law.
Obtain k from the half-life of the reaction (good only for a first-order
 14*9'Effect'of'Temperature'on'Reaction'Rates

In 1889, Svante Arrhenius demonstrated that the rate constants

of many chemical reactions vary with temperature in
accordance with the expression;

Arrhenius Eq; k = Ae-Ea/RT

ln k = -Ea 1 + lnA
R T
This equation indicates that a rate constant increases as the
temperature increases and as the activation energy decreases.
 -Ea 1
k= Ae-Ea/RT ln k = + ln A
R T

-Ea 1 1
ln k2– ln k1 = + ln A - -Ea - ln A
R T2 R T1

k2 -Ea 1 1
ln = -
k1 R T2 T1
 FIGURE 14-12
Temperature dependence of the rate constant k for the reaction

N2O5 1in CCl42 ¡ N2O4 1in CCl42 * O 1g2

1
2 2
Data are plotted as follows, for the representative point in black.

t = 25 °C = 298 K
1>T = 1>298 = 0.00336 = 3.36 * 10-3 K-1
k = 3.46 * 10-5 s-1 ; ln k = ln 3.46 * 10-5 = - 10.272 -Ea
= -1.2"104 K
slope of line = -Ea>R = - 1.2 * 10 K
To evaluate Ea ,
4
R
Ea = 8.3145 J mol-1 K-1 * 1.2 * 104 K
= 1.0 * 105 J>mol = 1.0 * 102 kJ>mol -Ea = 1.0"102 kJ mol-1
(A more precise plot y ields a value of Ea = 106 kJ>mol. The arrow points to data
referred to in Example 14-9.)

*To see that this expression is dimensionally correct, note that on the right side the units in
the numerator are J mol -1 (for Ea ) and K -1 (for the quantity in parentheses) and that in the
denominator the units are J mol -1 K -1 (for R). Cancellation yields a dimensionless quantity on
the right, to match the dimensionless logarithmic term on the left.

Temperature)dependence)of)the)rate)constant)k)for)a)reaction