CHEMICAL KINETICS

Lecture Notes

Chemical Kinetics
Kinetics is the study of how fast chemical reactions occur.

There are four important factors that affect rates of reactions:

1. reactant concentration
2. temperature
3. catalyst
4. surface area

Reaction Rates
Speed of a reaction is measured by the change in concentration with time.

Suppose A reacts to form B. For the reaction A  B there are two ways of measuring rate:
1. the speed at which the products appear (i.e. change in concentration of B per unit time), or
2. the speed at which the reactants disappear (i.e. the change in concentration of A per unit time).

average rate = change in concentration of B or A = [ B] = -[ A]

time required for this change t t

The units for average rate are mol/L.s or M/s.

The rate at any instant (instantaneous rate) is the slope of the tangent to the curve (r =-d[A]/dt). Instantaneous rate is
different from average rate.

Reaction Rates and Stoichiometry

In general for aA + bB cC + dD

rate = - 1 d[A] = - 1 d[B] = 1 d[C] = 1 d[D]

a dt b dt c dt d dt

Dependence of Rates on Concentration

In general, rates increase as concentrations increase.
For the reaction: NH4+(aq) + NO2-(aq) N2(g) + 2H2O(l)

we note :
as [NH4+] doubles with [NO2-] constant, the rate doubles,
as [NO2-] doubles with [NH4+] constant, the rate doubles.

We conclude, rate  [NH4+] [NO2-]

Rate law: Rate = k[NH4+] [NO2-]. The constant k is the rate constant.

Note that the rate constant k does not depend on concentration.

For a general reaction with rate law: Rate = k[reactant 1]m[reactant 2]n
we say the reaction is mth order in reactant 1 and nth order in reactant 2. The overall order of reaction is m + n.
A reaction can be zeroth order if m, n are equal to zero.
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 Note the values of the exponents (orders) have to be determined experimentally. They are not simply related to
stoichiometry.

The Change in Concentration with Time

First-Order Reactions
Goal: convert rate law into a convenient equation to give concentrations as a function of time.
Consider the hypothetical reaction: A  B

For a first order reaction, the rate doubles as the concentration of a reactant doubles. Therefore:
rate = - d[A] = k[A]
dt

ln[A]t - ln[A]0 = - kt.
Rearranging:
ln[A]t = - kt + ln [A]0 or [A]t = [A]oe-kt

A plot of ln[A]t versus t is a straight line with slope -k and intercept ln[A]0.

Half-life
 Half life is the time taken for the concentration of a reactant to drop to half its original value. That is, half life, t1/2 is
the time taken for [A]0 to reach 1/2[A]0

Mathematically:
ln [A]t = - kt
[A]0
So for t = t1/2 and [A]t = 1/2[A]0, ln 1/2[A]0 = - kt1/2.
[A]0
ln 1/2 = - kt1/2.

Therefore: t1/2 = - ln 1/2 = 0.693 .

k k

Second-Order Reactions
For a second order reaction,
Consider the hypothetical reaction: A B

Rate = - d[A] = k[A]2 .

dt

Integrating gives

1 = kt + 1 .
[A]t [A]0

 A plot of 1/[A]t versus t is a straight line with slope k and intercept 1/[A]0
 For a second order reaction, a plot of ln[A]t vs. t is not linear.
We can show that the half life is:
t1/2 = 1
k[A]0

For a reaction that is zeroth order with respect to A:

 d[A]
 k[A]0  k
dt

Integrating gives the zeroth order integrated rate law: [A]t = -kt + [A]0

Temperature and Rate

 Most reactions speed up as temperature increases. (e.g. food spoils when not refrigerated.)
 As temperature increases, the rate increases.
 Since the rate law has no temperature term in it, the rate constant must depend on temperature.

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Illustrative Examples:

1. Given the following equations and experimental data, write the correct
a. Rate Law Expression
b. Reaction Order
c. Determine k, the Specific Rate Constant (including units)

A2 + B2  2 AB

Exp # [A2] [B2] Rate

(mole L-1 s-1)
1 0.001 0.001 0.01
2 0.001 0.002 0.02
3 0.001 0.003 0.03
4 0.001 0.004 0.04
5 0.002 0.004 0.16
6 0.003 0.004 0.36

2. Use the following data to determine a) the reaction order of A and B, b) the rate constant (k), and c) the rate law
equation for the reaction that proceeds by the equation 2A + B  C.

Experiment [A] [B] Rate (M/s)

1 0.25 0.10 0.012
2 0.25 0.20 0.048
3 0.50 0.10 0.024

3. The first order rate constant for the decomposition of N2O5, 2N2O5(g)  4NO2(g) + O2(g), at 70oC is 6.82 x 10-3 s-1.
Suppose we start with 0.0250 mol of N2O5(g) in a volume of 2.0 L.
(a) How many moles of N2O5 will remain after 5.0 min?
(b) How many minutes will it take for the quantity of N2O5 to drop to 0.010 mol?
(c) What is the half-life of N2O5 at 70oC?

4. The gas-phase decomposition of NO2, 2NO2(g)  2NO(g) + O2(g), is studied at 383oC, giving the following data:

Time (s) [NO2] (M)

0.0 0.100
5.0 0.017
10.0 0.0090
15.0 0.0062
20.0 0.0047

(a) Is the reaction first order or second order with respect to the concentration of NO2?
(b) What is the value of the rate constant?