PHYSICAL CHEMISTRY II

MODULE 1: RATES OF REACTION

Reactions are taken place everywhere around us…..imagine the millions of reactions which
are currently taken place inside your body as you read this sentence. The rate at which
these reactions takes place depends on several factors and the study of the rate of reaction
is known as kinetics. Interestingly, the word ‘kinetic’ meaning ‘moving’ comes from the same
root word as cinema.

LEARNING OBJECTIVES:
1. Define the following terms:
 rate of reaction
 rate equation
 rate constant
 order of reaction
 half-life of a reaction
2. Explain how to calculate the reaction rate graphically
3. Understand how to calculate the initial rate of reaction by using a tangent line at
the start of the curve
4. Construct rate equations of the form: Rate = k [A]n [B]m and understand how to
derive rate equations from experimental data
5. Discuss how to obtain the units of the rate constant from different reactions
6. Understand the three ways that are used to determine the order of a reaction
which includes:
 plotting a graph of reaction rate against concentration of reactant
 plotting a graph of concentration of reactant against time
 calculating and interpreting successive half-lives from graphs of
concentration against time
7. Understand how to calculate the rate constant from initial concentration, initial
rates and half-life data
8. Explain how to calculate the overall order of a reaction when given experimental
data
9. Discuss how to determine the order of a reactant from initial rates data
10. Understand the term ‘rate determining step’ and deduce possible reaction
mechanisms for multi-step reactions
11. Explain how to predict order of reaction from a given reaction mechanism
12. Understand the following terms:
 collision theory
 activation energy
 Boltzmann distribution curve
 catalysis
13. Explain how the following affect the rate of a chemical reaction:
 concentration (in terms of collision frequency)
 temperature (in terms of both the Boltzmann distribution and collision
frequency)
 catalysts (in terms of changing a reaction’s mechanism, lowering the
activation energy and the Boltzmann distribution)
14. Describe the terms homogenous catalysis and heterogeneous catalysis and provide
examples of each
15. Discuss how enzymes act as catalysts and their role in industrial and biological
processes
 1. DEFINITIONS:

Rate of reaction is a measure of the rate at which reactants are used up

(decrease) or the rate at which products are formed (increase). The units of rate
are moldm–3 s–1.

The rate of reaction can be expressed as:

Rate of reaction = change in concentration (or amount) of reactants or products

Time taken for this change

Rate equation is an equation showing the relationship between the concentrations

of reactants which affect the rate of reaction and the rate constant.

The general form of the rate equation is:

Rate = k[A]m[B]n, where:

 k is the rate constant

 [A] and [B] are the concentrations of those
Reactants that affect the rate of reaction
 m is the order of the reaction with respect to A
 n is the order of reaction with respect to B.

Rate constant is the proportionality constant in the rate equation.

The order with respect to a particular reactant is the power to which its
concentration is raised in the rate expression. The overall order is the sum of the
orders with respect to each reactant.

The half-life of a reaction is the time taken for the concentration of a reactant to
decrease to half of its initial value.
This is a link to a video which will help you understand rate of reaction, how it can be measured and
calculated:

https://youtu.be/NhdtqnEfa9w
 2. CALCULATING THE RATE OF A REACTION GRAPHICALLY

In many reactions, the reaction rate changes as the reaction begins. The equation
graphs below show the progress between reactants A and C.

A+C B Therefore as A reacts with C, its concentration decreases and

the concentration of the product B increases.

Graph #1 Graph #2

THESE ARE THE FOLLOWING STEPS WHICH ARE INVOLVED IN

CALCULATING THE RATE OF REACTION at particular time on A GRAPH:

1. Select a point on the line corresponding to a particular time

2. Draw a straight line at this point so that the two angles look the same
3. Extend he tangent line to meet the axes of the graph
4. Calculate the gradient of the graph. This is the rate of reaction.

In the graph below, the rate at 0 seconds (the rate at the start – the initial
rate) is -0.019 mol dm-3 s-1. The rate after 40 seconds is -0.0048 mol dm-3
s-1. The negative sign shows that the rate is decreasing with time.
QUESTIONS????
1. Why should we have a long tangent line, extending as far as the axes?

Answer: If the tangent line is too short then there will be a larger degree of error in
the gradient calculation stemming from reading the values.

2. Why are the two values (the first at zero seconds and the other at forty
seconds of rates are not the same?

Answer: Most reactions start faster and slow down due to there being less reactant
particles as time goes on and so less frequent successful collisions between reactant
particles. Therefore, the initial rate of the reaction takes quicker as oppose to the
rate of the reaction at 40s
 3. INITIAL RATES
The initial rate of reaction is calculated by drawing a tangent line at the start of
the curve (at time = zero) as shown in the two graphs below. Then extending the
tangent line as far as possible and finally calculating the gradient of the graph.

PRACTICE QUESTIONS

1. Convert the following rates into the units of moldm–3 s–1:

• 0.254g of I2 consumed in 1.00h in a reaction mixture of volume 1dm3 (Ar [I]
= 127)
• 0.0440g ethyl ethanoate formed in 1.00min from a reaction mixture of
volume 400cm3. (Mr [CH3COOC2H5 ] = 88.0)
 2. Magnesium reacts with hydrochloric acid to form hydrogen gas. The
data below shows how the hydrochloric acid concentration varied with
time.
Time (s) 0 10 20 30 40 50 60 70 80
[HCl] (mol dm-3) 1.00 0.51 0.25 0.16 0.13 0.11 0.09 0.08 0.06

• Plot a graph of acid concentration against time.

• By drawing gradients, calculate the rate at 0, 10, 20 and 30 seconds.
• Explain why the rate changes during the reaction as it does.

4. RATE EQUATIONS

This is a link to a video which discusses rate equations, how to rearrange the equation
and how to determine the units for k, the rate constant:

https://youtu.be/xfu7-4GQCXk

Please review the definition of the rate equation and recall the mathematical
expression……

All rate equations must be determined experimentally, they cannot be

predicted from the stoichiometric chemical equations.

We will use the example below, to show the steps involved in formulating a rate
equation for a reaction:

2H2 (g) + 2NO(g) 2H2O(g) + N2(g)

 1. First find how the concentration of H2(g) affects the rate by varying the
concentration of H2(g), while keeping the concentration of NO(g) constant
2. The results (from experimental data) show that the rate is proportional to
the concentration of hydrogen, therefore rate = k1 [H2 ]
3. Then find how the concentration of NO(g) affects the rate by varying the
concentration of NO(g) while keeping the concentration of H2(g) constant
4. The results show that the rate is proportional to the square of the
concentration of NO (rate = k2[NO]2).
5. Combining the two rate equations we get the overall rate equation: rate =
k [H2 ][NO]2.

5. The units of Rate constant (k)

Please recall the definition for rate constant, k…………..

The image below shows the steps one must take to calculate the units of the rate
constant for a reaction. The units for rate constant vary according to the order of
the reaction. The order of the reaction is discussed on the next page.
 PRACTICE QUESTIONS

1. Write rate equations for each of the following reactions:

 cyclopropane propene
where rate is proportional to the concentration of cyclopropane

 2HI(g) H2(g) + I2(g)

where rate is proportional to the square of the hydrogen iodide concentration

2. Work out the units for the rate constant in each of the following examples:

Rate equation Rearrange to give k Working Units for k

1) EXAMPLE: rate = k k = rate k = (mol dm-3) s-1 s-1

-3
[A] [A] (mol dm )

2) rate = k [C] [H]

3) rate = k [S]2

4) rate = k [J]2 [H]

5) rate = k [T]
 6. ORDER OF A REACTION

This is a link to a video which highlights the different graphs which are associated
with rate of reaction and it further shows how order of reaction can be determined
from such data:

https://youtu.be/Gj0UFfDOfGA

Please note that, orders of reaction are not always whole numbers. A few reactions have
fractional orders. For example, the reaction:

 CH3CHO (g) CH 4 (g) + CO (g) has an overall order of 1.5. The rate
equation for this reaction is: rate = k[CH3CHO]1.5

 The first way to determine the order of a reaction:

 plotting a graph of reaction rate against concentration of reactant

Hence, a graph of reaction rate against concentration tells us whether a reaction is

zero, first, second or third order with respect to a particular reagent (or overall).
/ moldm-3 s-1

Rate =k [Reactant] 2

Rate = k

Rate = k [Reactant]

/ moldm-3
  The second way to determine the order of reaction:
 plotting a graph of concentration of reactant against time

For first- and second-order reactions, the graph is a curve. The curve for the
second-order reaction is much deeper than for a first-order reaction. It also
appears to have a relatively longer ‘tail’ as it levels off. We can also distinguish
between these two curves by determining successive half-lives of the reaction.
 The third way to determine the order of reaction:

 calculating and interpreting successive half-lives from graphs of concentration

against time

 This graph shows the half-life for cyclopropane isomerization. Below are the
calculations:
  This figure below shows the half-life for zero order, first order and second
order reactions:

The figure above shows that a zero-order reaction has successive half-lives which
decrease with time .A first-order reaction has a half-life which is constant. Second-
order reactions have successive half-lives which increase with time.

COMPULSORY READINGS FROM online TEXTBOOK

Cambridge International AS and A Level Chemistry Coursebook 2nd Edition

7. Calculate the rate constant from initial concentration,

initial rates and half-life data
 See Chapter 22, pages 334-335

8. Calculate the overall order of a reaction when given

experimental data
 See Chapter 22, pages 335-336

9. Determine the order of a reactant from initial rates

data
 See Chapter 22, pages 337-338
10. Understand the term ‘rate determining step’ and
deduce possible reaction mechanisms for multi-step
reactions
 See Chapter 22, pages 338-339
This is a link to a video which help you understand the term, “rate determining step”
https://youtu.be/AU7op2jlEdE

11. Predict order of reaction from a given reaction

mechanism
 See Chapter 22, page 340

12. Understand the following terms:

 collision theory
 activation energy
 Boltzmann distribution curve
 catalysis
 See Chapter 9, pages 141-144
This is a link to a video which focuses on the Boltzmann distribution curve:
https://youtu.be/pS9q7FNdR74

13. Factors which affect the rate of a chemical

reaction:
 concentration (in terms of collision frequency)
 temperature (in terms of both the Boltzmann
distribution and collision frequency)
 catalysts (in terms of changing a reaction’s
mechanism, lowering the activation energy and the
Boltzmann distribution)
 See Chapter 9, pages 143-145
This is a link to a video which discusses collision theory, factors affecting rate of reaction
(please focus on only temperature, concentration and catalysts) and activation energy:
https://youtu.be/mUJS0B_ERIs
14. Homogenous catalysis and heterogeneous catalysis
and examples
 See Chapter 9, page 144 AND Chapter 22, pages 340-343

This is a link to video which discusses what a catalyst is and how they work:
https://youtu.be/m_9bpZep1QM

15. Enzymes and their role in industrial and biological

processes
 See Chapter 9, page 145