Zero-Order Processes

D[A]t
reaction rate = - = k (constant)
Dt
So… [A]t = -kt + [A]0
• This equation has the general form for a straight line, y=mx+b, so
a plot of [A]t vs. t is a straight line with slope (-k) and intercept [A]0.

(slope= −k)

[A]t

Time (s)
First-Order Processes
For 1st order reactions: ln[A]t = −kt + ln[A]0
where [A]t = concentration of [A] after some time, t
k= reaction rate constant in units of s-1
t= time in seconds
[A]o = initial concentration of A

• This equation has the general form for a straight line, y=mx+b, so
a plot of ln[A]t vs. t is a straight line with slope (-k) and intercept
ln[A]0.

(slope= −k)
ln[A]t

Time (s)
 Half-Life
• Half-life is the time taken for the concentration of a
reactant to drop to half its original value.
• Substitute into integrated rate laws: t½ is the time taken
for [A] to reach ½[A]0
Half-Life - 1st order
For a first-order process, set [A]t=0.5 [A]0 in
integrated rate equation:
What is the half-life of N2O5 if it decomposes with a rate
constant of 5.7 x 10-4 s-1?

t½ = Ln 2 = 0.693
= 1200 s = 20 minutes
k -4
5.7 x 10 s -1
Example 36.3

Example Problem 36.3

The decomposition of N2O5 is an important process in tropospheric
chemistry. The half-life for the first order decomposition of this
compound is 2.05×104 s. How long will it take for a sample of N2O5 to
decay to 60% of its initial value?

Solution

ln 2 ln 2 −5 -1
k= = = 3 . 38  10 s
t1/ 2 2.05 10 s
4

N 2O5  = N 2O5 0 e −kt

N 2O5  = 0.6N 2O5 0 = N 2O5 0 e −(3.3810 )
−5
s -1 t

0 .6 = e ( )
− 3.3810−5 s -1 t

ln 0.6
t=− −5 -1
= 1 . 51  10 4
s
3.38 10 s
 Second-Order Processes
For 2nd order reactions: 1/[A]t = kt + 1/[A]0
where [A]t = concentration of [A] after some time, t
k= reaction rate constant in units of M-1s-1
t= time in seconds
[A]o = initial concentration of A

• This equation has the general form for a straight line, y=mx+b, so
a plot of l/[A]t vs. t is a straight line with slope (k) and intercept of
1/[A]0.

(slope= k)
1/[A]t

Time (s)
At high temperatures, nitrogen dioxide decomposes to nitric oxide and oxygen.
2NO2(g)−→Δ2NO(g)+O2(g)
Experimental data for the reaction at 300°C and four initial concentrations of NO2 are listed in the
following table:

Experiment [NO2]0 (M) Initial Rate (M/s)

1 0.015 1.22 × 10−4
2 0.010 5.40 × 10−5
3 0.0080 3.46 × 10−5
4 0.0050 1.35 × 10−5
Determine the reaction order and the rate constant.
Given: balanced chemical equation, initial concentrations, and initial rates
Asked for: reaction order and rate constant
Strategy:
From the experiments, compare the changes in the initial reaction rates with the corresponding changes in the
initial concentrations. Determine whether the changes are characteristic of zeroth-, first-, or second-order
reactions.
Determine the appropriate rate law. Using this rate law and data from any experiment, solve for the rate
constant (k).
Solution
A We can determine the reaction order with respect to nitrogen dioxide by comparing the changes in
NO2 concentrations with the corresponding reaction rates. Comparing Experiments 2 and 4, for example, shows
that doubling the concentration quadruples the reaction rate [(5.40 × 10−5) ÷ (1.35 × 10−5) = 4.0], which means
that the reaction rate is proportional to [NO2]2. Similarly, comparing Experiments 1 and 4 shows that tripling the
concentration increases the reaction rate by a factor of 9, again indicating that the reaction rate is proportional
to [NO2]2. This behavior is characteristic of a second-order reaction.
B We have rate = k[NO2]2. We can calculate the rate constant (k) using data from any experiment in the table.
Selecting Experiment 2, for example, gives the following:
 rate=k[NO2]2
5.40×10−5 M/s=k(0.010M)
0.54M−1⋅s−1=k
Nth Order Reaction