CHEMICAL KINETICS

For 2nd year chemistry students

2023
Prof. Dr. Sahar A. El-Molla

Books:
Chemical Kinetics by Kaith J. Laidler.
 Thermodynamics vs. Kinetics
Thermodynamics:
Is the reaction feasible? (G = − ve?)
Which product is stable? (at equilibrium)

Ea
Kinetics: G
How fast (rate) is the chemical process!
Mechanism of reaction! (any intermediate!)
 Thermodynamics vs. Kinetics

For the above transformation

Thermodynamics favors the process (G: -ve )
Kinetics makes this reaction nearly impossible
(Requires a very high pressure and temperature over long time)
 HOW THE REACTION OCCURS?
IN ONE STEP OR MORE
ONE OF THEM DETERMINES ITS
RATE
types of chemical reactions
Slow Fast
4Fe+3O2+2H2O→2Fe2O3∙2H2O Combustion of magnesium in oxygen
2Mg+O2→2MgO
Rusting
 Chemical Reaction Timescale of Reaction
Combustion Very fast
The reaction of magnesium with
Fast
water
Rusting of iron Slow

Chemical weathering of rocks Very slow

Example 1: Choosing Which Chemical Reaction is Likely to Occur on a Certain Timescale

The chemical timeline gives examples of different chemical reactions that take place over a
range of timescales. Which of the following reactions is likely to occur at point X?

A.Cooking food
B.The reaction of iron and hydrochloric acid
C.Striking a match
D.The reaction of alkali metals with water
E.The chemical weathering of rocks
Answer
X corresponds to a reaction that occurs on a very slow timescale. While the diagram
provides no details on exactly how slow, we can deduce that the reaction is slower
than the rusting of iron. cooking food is unlikely to be slower than the rusting of iron.
Iron reacts quickly with hydrochloric acid, the striking of a match initiates a very fast
chemical reaction to produce a flame, and the dropping of alkali metals in water
produces a vigorous and explosive reaction.The chemical weathering of rocks is a
slow process taking place over years, and therefore the correct answer is option E.
Kinetics (Ancient Greek: "kinesis", movement or to move)

Chemical kinetics also known as Reaction kinetics is the

study of rate of chemical processes.
Rate of a Reaction
Rate is defined as r = change in concentration (C)
time (t)
the rate of formation intermediate or product or loss of reactant or any species –

Observing the change in concentrations of reactants and products is a way

of following the process of a reaction. Let’s consider the following chemical
reaction :A+B→C During the chemical reaction, the concentrations
of A and B will decrease as they react with each other. the concentration
of C will increase as it is being produced during the reaction.
 The graph below shows how the concentrations of A and C change during the
reaction. The horizontal axis shows the time, usually given in units of seconds.
The vertical axis represents the concentrations of A and C, usually given in units
of moles per litre.

The concentration –time curve

The point at which the concentrations of the reactant and product do not change tells us
that the reaction is complete. From the graph above, the concentration of the
product C reaches its maximum value at 50 seconds. At this time, the concentration of
reactant A is zero and therefore has been used up.
For the reaction:2H2O2 → H2O+O2 How long does this reaction take to reach
completion?

the maximum value of concentration that the oxygen gas reaches is 1.00 mole per litre .
at 90 seconds
The speed at which a chemical reaction takes place is known as the rate of reaction.
Usually, the rate of reaction describes how some variable changes over a certain rate
of time. This could be a change in volume or mass per second or per minute.
However, a common measurement for the rate of reaction is the change in
concentration over time.

Definition: Rate of Reaction

The rate of reaction measures how reactant or product concentrations change
per unit of time.

Which of the following statements best defines the rate of a chemical reaction?
A.The measure of change in the concentration of reactants or products per unit of time
B.The difference in mass between the reactants and the products
C.The final concentration of the products following a chemical reaction
D.The speed at which particles need to move in order to successfully collide
E.The time at which the concentrations of products and reactants are equal
 Project 1

By measuring the time taken for the solution to turn colorless, or the time
taken for the copper hydroxide to appear, the rate of the reaction can be
measured.
 Factors affecting reaction rate

The rate of reaction can be affected by many factors. Changing these

factors can either increase or decrease the rate of reaction. Some of
the factors that affect the rate of reaction include
•nature of reactants,
•surface area,
•concentration,
•temperature,
•catalysts.
•radiation
It is important to note that changing these factors does not change the
final concentration of products made. However, changing these factors
will change the time taken for these final concentrations to be reached.
 1-Nature of active species

The nature of reactants refers to whether the reactant is an ionic or covalent

molecule. ionic reactants are much faster than covalently bonded reactants.
Ionic reactants can decompose into ions, which can react quickly. Covalent
molecules require breaking the old bonds and forming news bonds to undergo a
chemical reaction, and this takes longer time than the reaction between ions.
NaCl+AgNO3 → AgCl+NaNO3 fast
2CO+O2 → CO2 slow

ex2
NaOH + HCl → NaCl + H2O
The ionic compounds make the reaction easier

N2 + 3H2 → 2NH3
The covalent compounds make the reaction so difficult
 2-Surface area (particle size of solid reactant

Consider the reaction between two reactants A and B. In the images below, A is
shown by the purple circles, and B is shown by the green circles.
In the image below, A is a large, solid lump. Here, the surface area of A is low.
Initially, the molecules of B can only react with the outer particles of A. Once the
outer particles of A have reacted, the inner particles will be exposed

However, if a lump of A with the same mass is cut into smaller pieces, then the
surface area will have increased. The image below shows how more particles
of A are now available to react with molecules of B.As a result, the rate of reaction
will increase.
 The surface area of A can be increased further by cutting it into even smaller
pieces, as shown in the image below. Now, an even larger number of particles
of A are available to react with B. The rate of reaction will increase again and be the
fastest of all three experiments.

In Heterogeneous reaction the reaction occurs only at the surface boundary between
reacting phases. When particle size of the solid decreases the rate of reaction increases,
because of increasing the surface area of solid surface (catalyst).
Reaction between Mg and any acid has hydrogen ions
 Project 2
The effect of surface area on the rate of reaction can be demonstrated using the
reaction of iron with hydrochloric acid. two conical flasks are filled with the same
concentration of hydrochloric acid. An iron ribbon is put into one of the conical
flasks and iron filings are put into the other. Both reactions occur at the same
temperature. The gas syringe is used to measure how much hydrogen gas is
produced as the iron filings or iron ribbon reacts with the hydrochloric acid.

Fe(s)+2HCl(aq) → FeCl2(aq)+H(g)
 the volume of gas can be measured over 5-second intervals and the data
can be plotted on a graph. The graph below shows the results of the two
experiments.

the final amount of gas produced in each reaction is the same. However, this amount
of gas is produced faster when the conical flask contains iron filings. Therefore, the
rate of reaction is fastest in the reaction with iron filings. The iron filings have a much
greater surface area than the iron ribbon. Usually, the greater the surface area, the
faster the rate of reaction.
 •3-Concentration of reactants

Fe + H2O → Fe2O3
•Rusting iron increases in humidity (water vapor) in rainy season than dry air.
particles to react, they must first collide. In addition, the particles must have a
certain amount of energy when they collide. Any factor that can increase the
frequency of collisions, or the energy of the particles, will likely increase the
rate of reaction.

An increase in the number of particles will result in an increase in the number of

collisions. A greater number of collisions causes an increase in the rate of reaction.

Why is the combustion of aluminum in air slower than in pure oxygen?

A.The temperature of oxygen in air is greater than in pure oxygen.
B.The temperature of pure oxygen is greater than air.
C.The concentration of oxygen in air is less than in pure oxygen.
D.The concentration of oxygen in air is greater than in pure oxygen.
Project 3
shows the effect of concentration on the rate of reaction is the reaction of magnesium
with hydrochloric acid. In this experiment, one conical flask contains dilute
hydrochloric acid and a different flask contains concentrated hydrochloric acid. Into
each conical flask is placed an identical piece of magnesium of the same size and mass.
The chemical equation for the reaction between magnesium and hydrochloric acid is
Mg(s)+2HCl(aq)→MgCl2(aq)+H(g) Therefore, by measuring the volume of hydrogen gas
produced over time, any change in the rate of reaction can be determined. The setup
of this experiment is shown in the image below:
The graph shows that a greater volume of hydrogen gas is produced over a
short period of time when concentrated hydrochloric acid is used. This shows
that the rate of reaction increases as the concentration increases. As the
concentration of hydrochloric acid increases, the number of acid particles
present increases. As a result, there is a greater number of collisions between
the acid and the magnesium particles, and so, there is an increase in the rate of
reaction.
 •4- Temperature

As the temperature increases, the particles gain energy and move faster.
The faster the particles move, the more likely they are to collide with each
other. In the diagram below, the larger the arrow, the faster the particle is
moving. At higher temperatures, the particles have more energy and so a
larger arrow.

Rate is doubly increasing with increasing temperature each 10o C.

 Project 4
The effect of temperature on the rate of reaction can easily be demonstrated, one
effervescent tablet is put into a flask that contains hot water and a second tablet is
put into a different flask that contains cold water. The tablet reacts with the water to
produce carbon dioxide gas. The experimental setup is shown below.

By measuring the volume of gas produced in each experiment, the rates of reaction can
be determined and compared.
At the higher temperature, the particles have more energy and move around
faster. This increases the number of collisions between particles and increases the
rate of reaction. A faster rate of reaction increases the volume of gas produced at
the start of the reaction, resulting in a steeper line on the graph. However, as the
mass of the tablet and volume of water remain constant, the final amount of gas
produced is the same. The higher the temperature, the greater the frequency of
collisions between molecules.
Life application
Temperature is a very important factor for controlling the rate of reactions in food.
Placing food in a cool place, such as a refrigerator or freezer, slows down the
chemical reactions that spoil food. As a result, food can be preserved and last
longer. High temperatures are often used when cooking food. The higher
temperature increases the rate of reaction and helps cook food quicker and more
thoroughly.
 •5- Catalysts
Catalysts are substances that can speed up or slow down chemical reactions. They
can do this without being used up or chemically changed as the reactants turn into
products. They have essentially the same structure and properties before and after a
chemical reaction. The following figure shows how a metal catalyst surface can
speed up a reaction by making materials join together and form product molecules.

Chemical reactants can be made to react with less energy in the presence of the righ
catalyst. The catalysts can make the chemical reactions happen more easily by
binding to the reactant molecules during the chemical reaction. The catalyst breaks
away from the reactant molecules as they turn into products. Most chemists use a
relatively small amount of catalyst material to change a reaction rate because the
same catalyst surface can be used again and again without being used up.
Which of the following best defines a catalyst?
A.A substance that provides energy to the reactants to increase the rate of reaction
B.A substance that can make any chemical reaction occur
C.A substance that increases either the concentration or the surface area of
reactants to increase the rate of reaction
D.A substance that changes the rate of reaction but is chemically unchanged by the
end of the reaction
E.A substance that increases the amount of product produced by a chemical reaction

Which of the following is not a characteristic of a catalyst?

A.It decreases the amount of energy needed for a reaction to proceed.
B.It changes the rate of reaction, but it does not affect the start or end of the
reaction.
C.A large amount of a catalyst is often required to make a reaction occur.
D.It can be bonded to the reactants during the reaction, but it is separated by the
end.
E.It does not change chemically before or after the reaction.
Enzymes are biological catalysts .Enzymes tend to be large proteins with
a complex shape. They catalyze lots of important reactions. Some
enzymes make long molecules break down into small molecules at a very
fast rate. Others make small molecules react together and form larger
molecules at a very fast rate. The following image shows how an enzyme
can rapidly break down long starch molecules into smaller sugar units.

Which of the following names is given to the class of biological catalysts?

A.Enzymes
B.Substrates
C.Minerals
D.Gametes
E.Alleles
Positive catalysts are substances that have the capacity to speed up a chemical
reaction. They can be added to a reaction mixture to make a chemical reaction
happen faster. Negative catalysts are substances that have the capacity to slow
down or retard a chemical reaction. They can be added to a reaction mixture to
make a chemical reaction happen less rapidly.

What name is given to a catalyst that can slow down a chemical reaction?
A.Block catalyst
B.Negative catalyst
C.Stop catalyst
D.Slow catalyst
E.Decelerating catalyst
hydrogen peroxide molecules decompose more rapidly if they are in the presence of
the right type of catalyst.

manganese dioxide (MnO2) catalyst can speed up the decomposition of hydrogen

peroxide liquid into water and oxygen gas.
Why are catalysts used in chemical reactions?
•ATo reduce the amount of waste produced
•BTo ensure the reaction is safe
•CTo increase the rate of reaction
•DTo produce more product overall
•ETo improve the purity of the products
 Project 5
Determining How a Piece of Sweet Potato Affects the Decomposition of Hydrogen
Peroxide Molecules

1.Fill two identical beakers with 300 cm3 of hydrogen peroxide liquid.
2.Cut a small piece of sweet potato and add it to one of the beakers.
3.Observe the beakers to determine which sample releases oxygen bubbles at a faster rate.

lots of (oxygen) gas bubbles are produced at the edge of the sweet potato
sample. The sweet potato acts as a positive catalyst in this experiment because it
makes the hydrogen peroxide molecules turn into product gas molecules more
rapidly. The sweet potato can speed up the decomposition of hydrogen peroxide
molecules because it contains a relatively high concentration of the oxidase
enzyme.
Energy level diagrams can be used to understand why catalysts make chemical reactions
happen more rapidly. The following image shows that a minimum amount of energy has
to be added to reactants to make them react with each other and turn into product
molecules. The catalyst changes the minimum amount of energy that needs to be added
to the reactant molecules to make them react and produce product molecules. Less
energy is needed to make the chemical reaction happen if the reaction happens in the
presence of the catalyst.

The diagram below shows the energy needed for a chemical

reaction to occur. How does a positive catalyst affect this energy?
A.It will increase it.
B.It will not affect it.
C.It will decrease it.
Life applications
Catalytic converters contain large honeycomb-like structures that are made of catalytic
metals such as platinum. These honeycomb-like structures have very high surface areas,
and the catalytic converters can react with lots of harmful gases before they are expelled
from the car engine through the car exhaust.
Most people have a plentiful supply of the lactase enzyme, which speeds up the
decomposition of lactose sugars, but some people are lactose intolerant and they usually
add lactase enzymes to milk to make it easier to digest.
Enzymes are also added to both laundry and dishwasher detergents to make them more
effective at breaking down dirt and oily residues. Catalysts are also used by chefs to
enhance the Maillard reaction and make pretzel crust a more appetizing brown color. New
catalysts are even being added to objects like windows to give them the ability to break
down dirt and clean themselves.
 •6- Radiations

2H2 + Cl2 + hu → 2HCl

ex :X-ray, U.V, I.R can affect on the rate of chemical reaction. These reactions are
called photochemical reactions.
Quiz
1-Which of the following factors does not affect the rate of a chemical reaction?
•ACatalysts
•BSurface area
•CTemperature
•DConcentration
•EColor of the reactants
2-Fill in the blanks: The ---surface area exposed to a chemical reaction, the ---rate
of the reaction.
•Alarger, faster
•Blarger, slower
•Csmaller, faster
3-Which of the following is not an ideal way to measure the rate of a chemical reaction?
•AThe time taken for a color change to occur
•BThe volume of gas produced
•CChange in mass
•DChange in concentration
•EChange in the volume of liquid

4-Food can often be made to last longer by keeping it in a refrigerator or a freezer.

Which of the following statements explains why?
•AThe cooler temperatures reduce the rate of decay of food.
•BThe plastic interior reduces the rate of decay of food.
•CThe absence of oxygen reduces the rate of decay of food.
•DThe formation of ice prevents bacteria from sticking to food.

5-Fill in the blanks: As the temperature--- ,the number of collisions between

molecules -----resulting in a ---- rate of reaction.
•Aincreases, decreases, slower
•Bdecreases, decreases, faster
•Cincreases, decreases, faster
•Ddecreases, increases, slower
•Eincreases, increases, faster
 THANKS

PROF. DR . SAHAR A. EL-MOLLA

DR. MONA ALI