GENERAL CHEMISTRY 2

Topic 4 – Chemical Kinetics (Part 3)

 Objectives
Students should be able to:
• Determine the rate at time intervals (instantaneous rate)
• Construct rate equations
• Explain the term ‘order of a reaction’ with respect to a reactant and rate constant
• Deduce the order of reaction from graphical data
• Interpret concentration against rate graphs for zero, first and second order
reactions
• Interpret concentration against time graphs for zero, first and second order
reactions
 Reminder
• In any chemical reaction, as the reaction proceeds, the amount of reactants
decreases, whereas the amount of products increases. One has to understand
that the rate of the overall reaction depends on the rate at which reactants are
consumed or the rate at which the products are formed.
• If a graph is plotted between the concentration of reactants and products and
time, rate of formation of products and rate of disappearance of reactants can
be easily calculated from the slope of curves for products and reactants. The
overall rate of the reaction may or may not be equal to the rate of formations
and disappearances.
• Reaction rates generally decrease with time as reactant concentrations
decrease.
 Experimental measurement of reaction
rates
Take for example: The decomposition reaction of hydrogen iodide at 508oC.
2HI(g) → H2(g) + I2(g)
(purple)
• We can study any reactant or products since the rate of decrease of HI and the rates of
production of H2 and I2 are all related.
• It’s easiest to monitor I2 because it is the only colored substance.
• We can use a spectrophotomer to monitor the change in color intensity of the reaction
chamber and relate it back to the concentration of I2.
• If the concentration of I2 is known, then we can relate it to the concentration of HI.
 Table of Experimental Data
Time (s) Concentration of HI (M)
0 0.1000
50 0.0716
100 0.0558
150 0.0457
200 0.0387
250 0.0336
300 0.0296
350 0.0265

The easiest way to see the behavior of the reaction is to plot the data graphically
Graph of Experimental Data
Graph of Experimental Data
aA + bB → cC + dD
Using tangents to determine rate at time intervals

At 0 sec, the rate of

decrease in HI
is 0.00077 M/s.
Using tangents to determine rate at time intervals

At 100 sec, the rate of

decrease of HI
is 0.00025 M/s.

The rate of decrease of HI

is faster at the
beginning of the
reaction.
 Reaction rate laws
• Rate laws describe the progress of the reaction; they are mathematical expressions
which describe the relationship between reactant rates and reactant concentrations.
In general, if the reaction is:
𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
We can write the following expression: 𝑟𝑎𝑡𝑒 = 𝑘[𝐴]m [𝐵]n
Where:
𝑘 is a proportionality constant called rate constant (its value is fixed for a fixed set of
conditions, specially temperature).
 Reaction rate laws
• 𝑚 and 𝑛 are known as orders of reaction. As it can be seen from the above
expression, these orders of reaction indicate the degree or extent to which the
reaction rate depends on the concentration of each reactant.
• We can say the following about these orders of reaction:
1. In general, they are not equal to the coefficients from the balanced equation.
Remember: they are determined experimentally (unless a reaction is what we call an
elementary reaction, but they are the exception).
2. Each reactant has its own (independent) order of reaction.
3. Orders of reaction are often times a positive number, but they can also be zero, a
fraction and in some instances a negative number.
4. The overall reaction order is calculated by simply adding the individual orders (𝑚 +
𝑛).
 Reaction rate laws
• From the graph we see there is relationship between the concentration of the reactants and the rate
of the reaction, this gives rise to the rate law/equation.
• The rate law/equation is a mathematical equation which relates rate to the concentrations of
reactants.
• For a general reaction,
a X + b Y → products
where ‘a’ and ‘b’ are the coefficients in the balanced chemical equation, X and Y are the reactants.

Rate α [X ]m[Y]n
Rate = k [X ]m[Y]n (This is called the rate law/equation)
The rate of a reaction is directly proportional to the product of the concentration of reactants each
raised to some power.
• k, m, and n are numbers that are determined experimentally!!
 The rate constant, k
Rate = k [X ]m[Y]n
• The bigger the rate constant, k, the faster the reaction.
•k is temperature dependent.
•k is reaction dependent.
•k has units (not the same for all reactions)
 Reaction rate laws
• From the graph we see there is relationship between the concentration of the reactants and the rate of
the reaction, this gives rise to the rate law/equation.
• The rate law/equation is a mathematical equation which relates rate to the concentrations of reactants.
• For a general reaction,
a X + b Y → products
where ‘a’ and ‘b’ are the coefficients in the balanced chemical equation, X and Y are the reactants.
Rate α [X ]m[Y]n
Rate = k [X ]m[Y]n (This is called the rate law/equation)
The rate of a reaction is directly proportional to the product of the concentration of reactants each raised
to some power.
• k, m, and n are numbers that are determined experimentally!!
• it is not possible to predict the rate law from the overall balanced chemical reaction; rate laws must be
determined experimentally
 Differential and Integrated Rate Laws

Differential rate laws express the rate of reaction as a function of a change

in the concentration of one or more reactants over a particular period of time.
They are used to describe what is happening at the molecular level during a
reaction.
These rate laws help us determine the overall mechanism of reaction (or
process) by which the reactants turn into products. E.g.:
 Differential and Integrated Rate Laws

On the other hand, integrated rate laws express the reaction rate as a function
of the initial concentration and a measured (actual) concentration of one or
more reactants after a specific amount of time (t) has passed.
They are used to determine the rate constant and the reaction order from
experimental data. E.g. (when 𝑛 = 1):

Where [𝐴]0 is the initial concentration of the reactant and [𝐴] is the
concentration after a time 𝑡 has passed.
 The orders of reaction
Rate = k [X ]m[Y]n
•m represents the order of the reaction with respect to X
•n represents the order of the reaction with respect to Y
• The overall order of the reaction = m + n
• The order of the reaction with respect to a particular reactant is the power to
which the concentration of that reactant is raised in the rate equation (NOTE
it is not equal to the stoichiometry of the reactant)
 The orders of reaction
• The values of m and n can be 0, 1, 2, 3 or rarely higher.
• When the values of m on n are zero we can ignore the concentration term as
anything to a power zero = 1
Example: Rate = k[H2][NO]2
• In this example the reaction is:
• 1st order with respect to H2 (doubling concentration of H2 doubles the rate)
• 2ndorder with respect to NO (doubling concentration of NO quadruples the
rate).
•1 + 2 = 3 (third order overall)
 The orders of reaction
• The values of m and n can be 0, 1, 2, 3 or rarely higher.
• When the values of m on n are zero we can ignore the concentration term as
anything to a power zero = 1
Example: Rate = k[H2][NO]2
• In this example the reaction is:
• 1st order with respect to H2 (doubling concentration of H2 doubles the rate)
• 2ndorder with respect to NO (doubling concentration of NO quadruples the
rate).
•1 + 2 = 3 (third order overall)
 Practice Question
What is the order with respect to each of the reactants in the rate equation? Give the
overall order of the reaction.

1. Rate = k[NO]2[O2] : [NO]=2, [O2]=1, overall order = 2 + 1 = 3

2. Rate = k[N2O5] : [N2O5] = 1, overall order = 1

3. Rate = k[O3][Cl] : [O3] = 1, [Cl] = 1, overall order = 1 + 1 = 2

 Methods of deducing orders of reaction
• Graphically using the initial rates method (concentration vs
rate graphs)
• Graphically using concentration vs time graphs
• Visual inspection from experimental data
 Deducing the order of a reaction
graphically using the initial rates method
What is the initial rates method?
• Thismethod involves calculating the rate of the reaction, due to a
reactant, by drawing a tangent to the curve at the initial concentration.
• Thisprocedure is repeated for different concentrations of the same
reactant.
• A graph of concentration vs. rate is then drawn and used to determine the
order of the rxn.
NB. All other reactant concentrations and temperature are kept constant.
An example of the initial rates method employed in the decomposition rxn of H 2O2
Concentration vs. rate graphs for
different orders
 Deducing order of reaction graphically using
concentration vs. time graphs (Integrated rate laws)
In order to determine the rate law for a reaction from a set of data consisting
of concentration (or the values of some function of concentration) versus
time, three graphs need to be made.
• For a zero order reaction, the graph of [A] versus time will be linear
• For a first order reaction, the graph of ln [A] versus time will be linear
• For a second order reaction, the graph of 1/[A] versus time will be linear.
Therefore, we see that the integrated rate law for each common type of
reaction (zeroth, first, or second order in a single reactant) can be plotted as
a straight line.
For a zero order reaction
For a 1st order reaction
For a 2nd order reaction
Practice Question #1
NO2 decomposes to give NO and
O2.
• What is the order with respect to
[NO2]?

• What is the rate law for the

decomposition of NO2 ?
 Practice Question #2

N2O5 decomposes to give NO2 and O2.

What is the order with respect to N2O5?
What is the rate law for the decomposition of N 2O5?
 Practice Question #2
N2O5 decomposes to give NO2 and O2.
What is the order with respect to N2O5?
What is the rate law for the decomposition of N2O5?

The plot of ln[N2O5] versus t gives a straight line, whereas the plots of [N2O5] versus t does not. This means
that the decomposition of N2O5 is first order in [N2O5].

The rate law for the reaction is therefore

rate = k[N2O5]
 Practice Question #3

What is the order with

respect to sucrose?
 Worked Example
In the reaction, A + B  X + Y, the
concentration of A was found to vary as
shown in the table. It was later found that
the order with respect to B was zero.
• Plot a graph of [A] vs time
• From your graph, determine the
instantaneous rate at 60s
• Plot a graph of ln [A] vs time
• Deduce from your graphs, the order with
respect to A.
• From your graph determine the value for the
rate constant
Worked Example cont’d
Worked Example cont’d
 Homework
Given the following information, determine the order of the reaction and the
value of k, the reaction constant.

Concentration (M) Time (s)

1.0 10
0.50 20
0.33 30

Hint: Start by making graphs of concentration vs. time (zeroth order), natural log of concentration vs. time
(first order), and one over concentration vs. time (second order), then determine which graph results in a
straight line.