Integrated Rate Laws

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.

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Integrated Rate Laws

[A] = [A]o exp (-k t)

Calculate k. (What is the rate constant?)

(b) Calculate the time t when [A] = 0.0500

Confidence Building Questions

For the polymerization of butadiene,

Discussion Consider the relationship

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