Lesson 12.

3 The Integrated Rate Law

Suggested Reading
 Zumdahl Chapter 12 Sections 12.4 & 12.5

Essential Question
 What is the integrated rate law and how is it different from the
differential rate law?

Learning Objectives:
 Analyze data from rate experiments.
 Determine rate laws and rate constants.
 Calculate the half-life of a first or second order reaction.

Introduction
The rate laws we have looked at so far express rate as a function of reactant
concentration. These types of rate laws are known as differential rates,
although they are usually just referred to as the rate law. The integrated rate
law, which is based on the differential rate, gives a mathematical expression
of how a reactant concentration changes over a period of time. Thus, the
integrated rate law can be used to predict concentrations at different times.
Using the integrated rate law we can answer questions such as "How long
does it take for this reaction to be 50% complete?" Also, as you will see in lab,
plotting concentration vs. time data provides an alternative to the initial rate
method of determining rate laws (I suggest you pay close attention to this part
of the lesson, as this will be one of the more complex labs we do). Calculus is
used to transform the differential rate law into the integrated rate law, but
since we will only work with the final equation the derivations will not be
shown.

Concentration-Time Equations
The Integrated First-Order Rate Law
Let us first look at the first-order law. Let A be a substance that reacts to give
products according to the equation
aA → products
where a is the stoichiometric coefficient of reactant A. Suppose that this
reaction has a first-order rate law

Using calculus, you get the following equation, which is called the integrated
first-order rate law.

where [A]t is the concentration of reactant A at time t, and [A]0 is the initial
concentration. The ratio of [A]t / [A]0 is fraction of reactant remaining at time t.
Lets look at an example of how to use this equation.

Example: Using the concentration-time equation for a first-order reaction

The decomposition of N2O5 to NO2 and O2 is first order with a rate constant of
4.80 x 10-4/s at 45 ∘C.

a) If the initial concentration is 1.65 x 10-2 M, what is the concentration after

825 s?
b) How long would it take for the initial concentration to decrease to 1.00 x 10-
2
M?
Solution:
a) This is basically plug and chug type work. Substituting gives

To solve for [N2O5], you take the antilogarithm of both sides (10x key). This
removes the log from the left and gives antilog(-0.172), or 10-0.172 on the right,
which equals 0.673.

b) You substitute into the concentration-time equation and solve.

The Integrated Second-Order Rate Law

Again, consider the reaction

aA → products
but suppose it has the second order rate law

Like before, using calculus, you obtain the following relationship between
concentration and time for second order reactions.

This equation is applied in the same way as shown in the example for the
integrated first-order rate law, but is used when the reaction is second order.

Half-Life Reaction
As a reaction proceeds, the concentration of a reactant decreases, because it
is being consumed. The half-life, t1/2, of a reaction is the time it takes for the
reactant concentration to decrease to one-half of its initial value. The concept
of half-life is used to characterize a radioactive nucleus, whose decay is a
first-order process. Carbon dating is a well known example.
For the general first-order rate law

the half-life is related to the rate constant, but is independent of the

concentration of A. The equation derived from calculus is

This is the equation for half-life for first-order reactions. For second order
reactions the equation is

In second-order reactions, the half-life does depend on the initial

concentration and becomes larger as time goes on.

Example: Half-life of a first order reaction

Sulfuryl chloride, SO2Cl2, is a colorless, corrosive liquid whose vapor

decomposes in a first-order reaction to sulfur dioxide and
chlorine, SO2Cl2(g) → SO2(g) + Cl2(g). At 320 deg C, the rate constant is 2.20 x 10^-5/s.

a) What is the half-life of the SO2Cl2 vapor at this temperature?

b) How long will it take for 50% of the SO2Cl2 to decompose? How long for 75%?

Solution:

a)
b) The half-life is the time required for 50% of the vapor to decompose. From
above we see this is 3.15 x 104 s or 8.75 hours. After another half-life, one
half of the remaining vapor decomposes. The total decomposed at this point is
75%. The time required for two half-lives is 2 x 8.75 hours = 17.5 hours.

Graphing Kinetic Data

In the previous lesson you saw that the order of a reaction can be determined
by comparing initial rates for several experiments in which different initial
concentrations are used (initial-rate method). It is also possible to determine
the order of a reaction by graphing the data for a particular experiment. The
experimental data are plotted in several different ways, first assuming a first-
order reaction, then a second-order, and so on. The order is determined from
the graph that best fits the data, which is the one with the straightest line.
Lets take a closer look. You have learned that each reaction order has its
own, differential rate law, integrated rate law, and half-life equation. Similarly,
each reaction order has its own plot. The table 12.6 on page 548 of your
textbook shows the relationships.

What this means is that for zero-order reactions, the plot of [A] vs t gives a
straight line. For first-order reactions the plot of log [A] vs t gives a straight
line, and for second-order reactions it is the plot of 1/[A] vs t. Thus, for a set of
experimental data, you can determine the reaction order by creating these
three plots. If your plot of [A] vs t give a straight line, your reaction is zero-
order. If your plot of log [A] vs t results in a straight line your reaction is first-
order, and if 1/[A] vs t is a straight line it is second order. Of the three plots,
only one should result in a straight line. Get the picture? The textbooks tend to
complicate this topic, so be careful.

In order to apply this in the lab, you must collect concentration versus time
data. There are several methods, but we will use spectrophotometry. You will
learn more about this method next semester. It is super fun!

Below are typical experimental results for a zero-order reaction:

A first-order reaction:

A second-order reaction

This work can be time consuming, but it is not hard. Unless, of course
something goes wrong and none of your graphs results in a straight line! Take
careful measurements!

HOMEWORK: Practice exercises 14.9, 14.10

Book questions page 278 questions 1, 3-6, 16 & 18