Ramallah Friends School

Chemistry - 11 IB
Unit Six – Kinetics SL

Rates of chemical reaction:

The rate of a chemical reaction can be defined as:
The decrease in the concentration of a reactant per unit of time OR the increase in the concentration of a
product per unit of time.

• The average rate of reaction over any time period can be determined as follows:

Rate = (1)

Rate = (2)

Unit of rate = mol dm - 3 s – 1

(concentration . Time-1)

The negative sign in equation (1) means that the concentration of the reactants decreases with time. The
positive sign in equation (2) means that the concentration of the products is increasing with time.

Rate of reaction usually decreases with time as the reactants are used up.

The change in the concentration of any reactant or any product is used in the above equations. The rates of
disappearance of the various reactants and the rates of formation of the various products are not all equal. The
rate at which the reactants are consumed and the rate at which the products are formed depend on the
stoichiometry of the reaction.

◘ H2 is disappearing 3 times faster than N2 because 3 moles H2 disappear with 1 mole N2. NH3 is appearing twice
as fast as the rate at which N2 disappears because 2 moles NH3 form when 1 mole N2 disappears.

N2 + 3H2  2NH3

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◘ The rate of formation of H2O = 2 X rate of formation of N2 because 2 moles H2O form with 1 mole N2.

2NO (g) + 2H2 (g)  N2 (g) + 2H2O (g)

Example: For the reaction

2HNO3 (aq) + CaCO3 (s)  Ca(NO3)2 (aq) + H2O (l) + CO2 (g)

What is the rate of formation of CO2 If HNO3 reacts at a rate of 2 X 10-3 mol cm-3 s-1?
The rate of formation of CO2 = X 2 X 10-3 = 1 X 10-3 mol cm-3 s-1 since HNO3 disappears twice as fast as the
rate at which CO2 appears since 1 mole CO2 forms when 2 moles HNO3 reacts.

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Example: The average rate of disappearance (mol dm – 3 s – 1) of HCl in the following equation:

Mg (s) + 2HCl (aq)  MgCl2 (aq) + H2 (g)

a) What is the average rate of disappearance of HCl if the concentration is decreased from 1 to 0.4 mol dm -3
within the first two minutes and half?

Rate = = = 0.004 mol dm – 3 s - 1

b) What is the average rate of disappearance of HCl if the concentration is decreased from 0.4 to 0.3 mol dm -3
in the period between 2.5 minutes and 6 minutes?

Rate = = 0.00048 mol dm – 3 s - 1

c) What is the average rate of appearance of MgCl2 if the concentration increased from 0 to 0.12 mol dm-3 within
the first two and half minutes?

Rate = = = 0.0008 mol dm – 3 s - 1

• Note that the measurement of the rate in the above examples provides an average rate using the net change in
concentration in the stated period of time.

Instantaneous rate of reaction:

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The rate of the reaction at a particular time can be determined by drawing a tangent to the curve at time t and
then calculating the gradient of the tangent which is equal to the rate.

Slope at time t = gradient = = Rate of reaction

The initial rate of a chemical reaction:

Draw a tangent to the curve at t = 0. The gradient of the tangent is equal to the initial rate of the chemical
reaction.

Slope at (t = 0) = gradient = = Rate of reaction

Activation energy (Ea): the minimum energy that colliding molecules need in order to have successful collisions
leading to a reaction.

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Collision theory:

The main features of the collision theory:

1- According to this theory molecules must collide in order to react.

2- The colliding molecules must collide with sufficient energy if a collision is to be productive ( the colliding
molecules must have energy ≥ Ea).
3- The colliding molecules must collide with an appropriate collision geometry (correct orientation) so the
reactive particles come into contact with each other and the collisions become productive and effective.
4- Not all molecules have energy ≥ Ea and for that not all collisions lead to a reaction.

There are three characteristic properties of reactant particles which affect the rate of reaction as
described by the collision theory:

a- Frequency of collisions
b- Kinetic energy of reactants (Number of particles with E ≥ Ea)
c- Appropriate collision geometry or orientation

Factors affecting rate of chemical reaction:

1- The concentration of reactants:

a) When the concentration of reactants increases, the number of particles increases and hence the
frequency of collisions per unit of time. The number of successful collisions per unit of time increases. More
products are produced per unit of time. Rate increases.

(For gases, when the pressure is increased by decreasing the volume then the concentration increases
and hence the frequency of collisions per unit of time increases and the number of successful collisions per unit
of increases. More products are produced per unit of time. The rate of the reaction increases).

b) As time proceeds, the concentration of reactants decreases. The frequency of collisions per unit of time
decreases. The number of successful collisions per unit of time decreases. Less products are produced per unit
of time. Rate decreases and the reaction slows down.

◘ The rate of a chemical reaction can be obtained at any time from a graph of concentration of a certain reactant
on the y – axis against time on the x – axis. A graph of concentration of certain product against time can be
drawn also. This is shown in the following graphs.

Explanation of the above graphs:

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a) The curve is steepest at the start and the measured gradient (rate) will be the highest. This means the
reaction is going quickly because at start there will be the greatest concentration of reacting particles, the
greatest frequency of collisions per unit time, the greatest number of successful collisions per unit time, the
greatest amount of product produced per unit of time and the greatest rate and slope.

b) As time proceeds the curve becomes less steep because as time proceeds the concentration of reacting
particles decreases, the frequency of collisions per unit time decreases, the number of successful collisions per
unit time decreases, the amount of product produced per unit of time decreases, the rate decreases and the
measured gradient (rate) will be lower and this means the reaction is going slower. The slope of the curve
decreases with time.

c) When the curve has gone completely flat this means that the measured gradient (rate) will be equal to zero
because the limiting reagent is used up and the reaction is complete. So, no further formation of products.

So it can be seen that rate of the reaction decreases as time proceeds.

Example: The following graph shows the volume of CO2 gas produced against time when excess
calcium carbonate is added to 50 cm3 of 2.0 mol dm-3 HCl.

a- Draw a line on the curve above when 50 cm3 of 1.0 mol dm-3 HCl is used. Give your reasoning.
b- Draw a line on the curve above when 100 cm3 of 1.0 mol dm-3 HCl is used. Give your reasoning.

a) The curve (curve I) becomes horizontal at half the original height. Since HCl is the limiting reagent and
half the original amount of HCl is used then the volume of CO 2 will be half the original amount. The curve
becomes less steep and the reaction needs more time to finish because the concentration of HCl decreased and
as a result the frequency of collisions per unit time decreases, the number of successful collisions per unit time
decreases, the amount of product produced per unit time decreases and the rate decreases.

b) The curve (curve II) has the same height as the original. The same volume of CO2 will be produced
because the same amount of HCl is used. The curve becomes less steep and the reaction needs more time to
finish because the concentration of HCl decreased and as a result the frequency of collisions per unit time
decreases, the number of successful collisions per unit time decreases, the amount of product produced per unit
time decreases and the rate decreases.

2- The temperature of the reaction:

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Increasing the temperature of the reacting molecules will increase their energy and hence there will be more
particles with energy ≥ Ea. The frequency of collisions increases per unit of time increases. The number of
successful collisions per unit of time increases. More products are produced per unit of time. Rate increases.

• Note that:
• The increase in the energy of the molecules is more important and has a larger effect on the rate of the
reaction than the increase in the number of collisions.
• Endothermic reactions are more affected by temperature increase than exothermic reactions, since E a of
endothermic reactions is larger.
• In general, the rates of many reactions are doubled by 10 oC rise in temperature.
• It is important to note that a small increase in temperature has a much greater effect on the rate of
reaction than a small increase in concentration. (IB Question)

Because:
An increase in concentration will increase the frequency of collisions per unit of time only while,
An increase in temperature will:

1) Increase the frequency of collisions per unit of time and

2) Increase the number of molecules with energy ≥ Ea.

Description of the kinetic theory in terms of the movement of particles whose average kinetic energy is
proportional to temperature in Kelvin.

Maxwell – Boltzman distribution curve:

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In a gas or a liquid, molecules are in constant motion. Because they continually collide with each other, there is a
wide range of different molecular speeds. Some are moving very fast and others much slower. The faster they
move the more kinetic energy they possess. The distribution of kinetic energies is shown by a Maxwell –
Boltzman curve. The following graph shows the Maxwell – Boltzman distribution curve for a fixed amount of gas
at two different temperatures where T2 is larger than T1.

- Each curve does not go to zero because there is no upper limit to molecular speeds.
- The maximum on the curve, A1 and B1, represents the kinetic energy possessed by the largest fraction of
particles. It is called the most probable kinetic energy.
- The average kinetic energy, A2 and B2, occurs at a higher value than the most probable kinetic energy because
the curve is not symmetrical.

Explanation Maxwell – Boltzman distribution curve:

a) At a higher temperature, T2, the area under the curve does not change as the total number of particles
remains constant. At T2 more particles have a very high velocity resulting in an increase in the average kinetic
energy, which leads to a broadening of the curve.

b) There will be more particles with energy ≥ E a. The frequency of collisions increases per unit of time increases.
The number of successful collisions per unit of time increases. More products are produced per unit of time.
Rate increases.

3- Surface area of a solid substance:

In a solid substance only the particles on the surface can come into contact with a surrounding reactant.

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The effect of increasing surface area:
If the size of the particles is decreased or if the solid is in powdered form then the surface area increases and the
number of colliding particles increases, the frequency of collisions per unit time increases. The number of
successful collisions per unit of time increases. More products are produced per unit of time. The rate increases.

• Powdered CaCO3 (Limestone) reacts faster than marble chips (lumps or large crystals) of CaCO 3(s) with
HCl(aq).

4- Catalysts:

Catalysts are defined as substances that increase the rate of a chemical reaction without themselves being
chemically changed at the end of the reaction.

The effect of adding a catalyst:

Catalysts work essentially by bringing the reactive parts of the reactant particles into close contact with each
other. This provides an alternative pathway for the reaction with a lower activation energy (Ea). There will be
more reactant particles with E ≥ Ea. The frequency of collisions per unit time increases. The number of
successful collisions per unit of time increases. More products are produced per unit of time. So, the rate of
reaction increases. (The catalyst has no effect on (H) or the yield of products of reaction and it is not consumed
at the end of reaction).

Maxwell – Boltzman distribution curve in the presence of catalyst:

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The following graph shows the Maxwell – Boltzman distribution curve for the reacting molecules when a catalyst
is used.

◘ The effect of a catalyst on the rate of a chemical reaction is shown in the following two potential energy
profiles or enthalpy level diagrams:

Exothermic Reaction: Endothermic Reaction:

Example: When dilute hydrochloric acid is added to a solution of sodium thiosulfate, a reaction will take place.

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 Na2S2O3 (aq) + 2HCl → 2 NaCl (aq) + H2O (l) + SO2 (g) + S (s)

a) State and explain what will happen to the rate of reaction if the volume of the same concentration of HCl is
increased

If the volume of the same concentration of HCl is increased then the rate of the reaction will decrease because
the extra volume of HCl will decrease the sodium thiosulfate concentration. So, the frequency of collisions, the
number of successful collisions will decrease and the amount of product produced per unit time will decrease.

b- State and explain what will happen to the rate of reaction If the solution of sodium thiosulfate is made from a
fine powder instead of from crystals.

If the solution of sodium thiosulfate is made from a fine powder instead of from crystals then the rate of the
reaction will not be affected because the concentration of the sodium thiosulfate solution is not affected by the
size of the solid.

Example: The following graph shows the volume of CO2 gas produced against time when excess
calcium carbonate is added to 50 cm3 of 2.0 mol dm-3 HCl.
What will happen to the volume of CO 2 produced when more lumps of calcium carbonate are added?.
Give your reasoning.

The same volume of carbon dioxide will be produced and the curve will not change because the calcium
carbonate was already in excess. The curve will be same as the original.

Note: Increasing the temperature, adding a catalyst or using the same mass of powdered calcium carbonate will
not affect the volume of carbon dioxide produced because the quantities of reactants will not change. Only the
curve becomes steeper and the reaction finishes earlier.
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It is important to say that the nature of reactants has an effect on rates of chemical reactions. Some
reactants by nature react fast. Others react slowly.

Reasons for a reaction being slow at room temperature:

1- The activation energy of the reaction is high and as a result not enough molecules have E ≥ Ea
2- Incorrect collision geometry
3- Infrequent collisions or the frequency of collisions is low.

Ways of increasing the rate of reaction between gases C and D:

1- Increase the temperature of the reaction

2- Add a catalyst
3- Increase the concentration of C or D
4- Increase the total pressure by decreasing the volume of the container.

Ways of increasing the rate of reaction between HCl (aq) and lumps of CaCO3 (s):

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1- Increase the temperature of the reaction
2- Add a catalyst
3- Increase the concentration of HCl
4- Increase the surface area of CaCO3 by using powder CaCO3.
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Measuring reaction rate experimentally:

1- Measurement of the volume of gas produced per unit of time:

● The Flask and Syringe Method is used to record volume changes.
An example is the reaction between magnesium metal and hydrochloric acid to produce hydrogen gas.

Mg (s) + 2HCl (aq)  MgCl2 (aq) + H2 (g)

The apparatus needed is shown below:

1- The flask is connected to the scaled syringe through a tube. The setup is airtight to prevent loss of gas.
2- The acid and the metal are mixed together inside the flask and at the same time the syringe is connected to
the flask and a stop watch is started.
3- When they start to react, hydrogen gas is produced. The gas pushes its way out into the syringe; the plunger
of the syringe is forced back.
4- Readings of volume are taken every minute, using the scale marked on the side of the syringe.
5- The results can be shown graphically because a graph of volume of H 2 gas produced on the y – axis against
time on the x – axis can be used to find the rate of the reaction at any time. The graph is shown below.
6- The rate of the reaction at a particular time can be determined by drawing a tangent to the curve at time t and
then calculating the gradient of the tangent which is equal to the rate.

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Homework (1):
The following data were collected for the reaction between magnesium and hydrochloric acid.
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 Mg (s) + 2HCl (aq) → MgCl2 (aq) + H2 (g)

Time / min 0 1 2 3 4 5 6 7 8 9 10
Volume of H2 gas / cm 3 0 12 20 26 30 33 35 36.5 37.5 38 38

1) What is the initial rate?

2) What is the rate of the reaction at t = 2 min?

To find the rate of production of hydrogen at two minutes, the steps are:

a- Draw a line up to the curve from the 2 min mark.

b- Carefully draw a tangent to the curve, at the point where the line touches it.
c- The gradient of the curve at time = 2 min is the same as the gradient of this tangent.
d- To measure the gradient of the tangent, mark two points on the tangent and the

Slope= gradient = = Rate of reaction

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IB Question:

Outline an experimental procedure by which you could obtain a value for the rate of this reaction. [6]

Key Words
1) Volume of gas method:
Name of chemicals in flask: Magnesium (Mg) and sulfuric acid (H2SO4) [1]

2) Method of collection: Flask and syringe [1]

Airtight [1]
3) Measurement and processing:
Volume monitoring [1]
Timing [1]
4) Appropriate processing of data:
Plot volume-time graph and measure slope [1]
Slope = Rate of reaction

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2- Measure the mass of beaker and chemicals per unit time when a gas is evolved and lost:

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A top – pan balance is used to record the mass of beaker and chemicals.

An example is the reaction between calcium carbonate and hydrochloric acid to produce carbon dioxide gas.

CaCO3 (s) + 2HCl (aq)  CaCl2 (aq) + H2O (l) + CO2 (g)

The apparatus needed is shown below:

1-The beaker of reactants is placed on the balance. The reactants are mixed inside the beaker.
2- The same time a lid is placed over the beaker to prevent loss by splashing and a stop watch is started.
3- The setup is not airtight because the lid is loose. Because the lid is loose, the gas can bubble out from the
beaker; the beaker therefore weighs less. Record the mass of the beaker every minute.
4-The results can be shown graphically because a graph of mass of beaker on the y – axis against time on the x
– axis can be used to find the rate of the reaction at any time.
5- Also a graph of mass of CO 2 gas produced on the y – axis against time on the x – axis can be used to find the
rate of the reaction at any time. The two graphs are shown below.
6-The rate of the reaction at a particular time can be determined by drawing a tangent to the curve at time t and
then calculating the gradient of the tangent which is equal to the rate.

IB Question:
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 CaCO3 (s) + 2HNO3 (aq)  CaCl2 (aq) + H2O (l) + CO2 (g)

Outline an experimental procedure by which you could obtain a value for the rate of this reaction. [6]
Key Words:
1) Mass loss method:
Name of chemicals in beaker: Calcium carbonate (CaCO3) and nitric acid (HNO3) [1]
2) Method of collection: Top pan balance [1]
Not airtight [1]
Measurement and processing:
mass monitoring [1]
Timing [1]
3) Appropriate processing of data:
Plot mass loss in beaker -time graph and measure slope. OR
Plot mass of CO2 -time graph and measure slope. Slope = Rate of reaction
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Homework (2): The following data were collected for the reaction between calcium carbonate and
hydrochloric acid.

CaCO3 (s) + 2HCl (aq) → CaCl2 (aq) + H2O (l) + CO2 (g)

Time / min Mass of beaker and

reactants / g
0 130.13
1 129.98
2 129.91
3 129.85
4 129.79
5 129.74
6 129.69
7 129.66
8 129.63
9 129.61
10 129.60
11 129.60

1) What is the rate of the reaction at t = 3 min?

2) What is the initial rate?
3) What is the average rate?
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Homework (3): The following data were collected from the reaction of Homework (2).

Time / min 0 1 2 3 4 5 6 7 8 9 10 11
Mass of CO2 gas / g 0 0.15 0.22 0.28 0.34 0.39 0.44 0.47 0.50 0.52 0.53 0.53

1)What is the rate of the reaction at t = 4 min?

2) What is the initial rate?
3) What is the average rate?
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Homework (4): The following data were collected from the reaction of bromine and methanoic acid.

Br2 (aq) + HCOOH (aq) 2HBr (aq) + CO2 (g)

Time / min 0 0.5 1 1.5 2 3 4 6 8 10

[Br2] / 0.01 0.009 0.0081 0.0073 0.0066 0.0053 0.0044 0.0028 0.0020 0.0013
mol dm - 3

1) What is the rate of the reaction at t = 4 min?

2) What is the initial rate?
3) What is the average rate?
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3- Measure pH of the solution per unit time when there is a change in acidity of the solution: A pH meter
is used to record the pH of the solution. A graph of pH (y – axis) against time (x – axis) is then usually plotted.
The rate of the reaction at a particular time can be determined by drawing a tangent to the curve at time t and
then calculating the gradient of the tangent which is equal to the rate. Notice that the slope of the curve
decreases with time and so the calculated rate. An example is the change in the pH of the reaction mixture in the
following reaction.

CaCO3 (s) + 2HCl (aq) → CaCl2 (aq) + H2O (l) + CO2 (g)

The graph is shown below:

pH

4- Measure the electrical conductivity of the solution per unit time when there is a change in the ionic
concentrations of the solution: An ammeter is used to record the electrical conductivity of the solution. A
graph of electrical conductivity (y – axis) against time (x – axis) is then usually plotted. The rate of the reaction at
a particular time can be determined by drawing a tangent to the curve at time t and then calculating the gradient
of the tangent which is equal to the rate. Notice that the slope of the curve decreases with time and so the
calculated rate. An example is the reaction between NaOH and HCl to produce NaCl and H 2O. The graph is
shown below.
Electrical conductivity

5- Measure the pressure of gas produced per unit of time when there is a change in pressure: The
reaction takes place inside a closed flask. The setup is airtight to prevent loss of gas. A pressure meter is used
to record the pressure of the gas. A graph of pressure (y – axis) against time (x – axis) is then usually plotted.
The rate of the reaction at a particular time can be determined by drawing a tangent to the curve at time t and
then calculating the gradient of the tangent which is equal to the rate. Notice that the slope of the curve
decreases with time and so the calculated rate. An example is the change in the pressure in the following
reaction.

CaCO3 (s) + 2HCl (aq) → CaCl2 (aq) + H2O (l) + CO2 (g)

The graph is shown below:

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 Pressure

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6- Measure the change in light intensity per unit of time:

When a solution of hydrochloric acid, HCl (aq), is added to a solution of sodium thiosulfate, Na 2S2O3 (aq), a
yellow precipitate of sulfur is formed.

Na2S2O3 (aq) + 2HCl (aq) → 2NaCl (aq) + H2O (l) + SO2 (g) + S (s)

A series of reactions is carried out where a fixed volume of a fixed concentration of hydrochloric acid is added to
a fixed volume of sodium thiosulfate solution of different concentrations.

The time taken to form a visible precipitate of sulfur is noted. A graph of the decrease in sodium thiosulphate
concentration (vertical axis) against time to form the visible precipitate (horizontal axis) or a graph of the
decrease in light intensity (vertical axis) against time to form the visible precipitate (horizontal axis).

Concentration of Na2S2O3

Light intensity

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