Integrated Rate Laws
The differential rate laws and integrated rate laws are summarized in the table below to give
you an overall view of reactions of these types.
Differential
Integrated
\
Linear plot
Half life
rate law
rate law
first
order
- d[A]/dt = k [A]
second
- d[A]/dt = k [A]2
order
[A] = [A]o exp (-k t)
ln [A] vs t
slope = - k
hl=ln(2)/k
1
1
--- - ---- = k t
[A]
[A]o
1
--- vs t
[A]
slope = k
hl=1/k[A]o
In this module, more examples are given to show applications of integrated rate laws in
problem solving.
Problem 1
The decomposition of A is first order, and [A] is monitored. The following data
are recorded:
t / min
[A]/[M]
0
1
2
4
0.100 0.0905 0.0819 0.0670
Calculate k. (What is the rate constant?)
Calculate the half life. (What is the half life?)
Calculate [A] when t = 5 min.
Calculate t when [A] = 0.0100.
(Estimate the time required for 90% of A to decompose.)
Solution
A. We can calculate k from any two data points
The integrated rate law for 1st order is
A = Ao exp (- k t)
Using the the first two points,
0.0905 = 0.100 exp (- k * 1)
- k = ln (0.0905/0.100)
= ln(0.905) = -.0998 min-1
Using the point when t = 2
0.100 = 0.0819 exp (-k * 2)
- k 2 = ln (0.0819/0.100)
= ln (0.819)
= -0.200
k = 0.100 min-1
Using the point when t = 4
0.0670 = 0.100 exp (- k * 4)
4 k = ln 1.49
= 0.400
k = 0.100 min-1
B. Two methods to evaluate half life are:
(a) half life * k = ln 2
= 0.693
half life = 0.693 / 0.1 = 6.93 min
(note the calculation of units)
(b) Calculate the time t when [A] = 0.0500
0.0500 = 0.100 exp (-0.100 t)
0.100 * t = ln (0.100/0.0500)
gives the same result.
C. When t = 5 min
[A] = 0.100 exp (-0.100 *5)
= 0.100 * 0.6065
= 0.0607
D. When [A] is reduced by 90%, we have
0.01 = 0.1 exp (-0.100 * t)
0.100 * t = ln (10)
t = 2.303/0.100 = 23.03 min
check:
[A] = 0.1 exp (-0.1 * 23.03)
= 0.010
Problem 2
The dimerization reaction of butadiene is second order:
2 C4H6(g) = C8H12(g).
The rate constant at some temperature is 0.100 /min. The initial concentration of
butadiene [B] is 1 M. Calculate the concentration of butadiene when t is 1, 2, 5,
10, 20, 30, and 70.
Solution:
In fact, many of the following values can be evaluated without using a calculator.
t/min
[B]/M
0
1
2
5
10
20
30
1.0 0.909 0.833 0.667 0.50 0.333 0.25
70.
0.125
Discussion:
From the record shown as above,
Calculate k. (What is the rate constant?)
Calculate the half life for [B] = 1.0. (What is the half life for an initial concentration
of 1.0?)
Calculate [B] when t = 40 min.
Calculate t when [B] = 0.100.
(Estimate the time required for 90% of B to polymerize.)
How does the total pressure change with time?
Getting the answers for the above is fun. Please try.
Confidence Building Questions
For the polymerization of butadiene,
2 C4H6(g) = C8H12(g),
the rate of decreasing of partial pressure of butadiene is 2 kPa/min. What is the
rate of increasing of partial pressure of (octadiene)?
1kpa/min
Discussion Consider the relationship
-d[C4H6]/dt = 2 d[C8H12]/dt
A cylinder containing pure butadiene has a pressure of 101 kPa. After 10 minutes,
the total pressure drops to 95 kPa. What is the partial of C8H12 (octadiene) formed?
2 C4H6(g) = C8H12(g).
6kpa
Discussion The drop in pressure is 101-95 = 6 kPa. Consider the reaction:
2 C4H6(g) = C8H12(g).
12 kPa
6 kPa
Since two moles of butadiene combine to give one mole octadiene, the difference in total
pressure is the partial pressure of octadiene, 12 kPa of butadiene converted to 6 kPa of
octadiene. What is the partial pressure of butadiene?
At some temperature, the total pressure of a butadiene cylinder drops from 101 kPa
to 95 kPa in 10 min. The polymerization is known to be second order. What is the rate
constant?
0.000133kpa/min
Discussion The reaction is:
2 C4H6(g) = C8H12(g).
Since the total pressure drops from 101 to 95 kPa after 10 min, the partial pressure of C4H6
goes from 101 to [101 - 2*(101-95)] = 89 kPa. Using the integrated rate law:
1/89 - 1/101 = k * 10
k =1.33e-4
What is the total pressure when the reaction is completed?
Radioactive decay always follow first order kinetics. Carbon-11 is a radioactive
isotope of carbon, and its half life is 20.3 min. What is the decay (or rate) constant?
0.0341/m
Skill Evaluate half-life according to conditions. Apply the equation,
k * half-life = ln 2
in this case.
