CHM 207.

CHEMICAL KINETICS
AJAYEOBA, T. A.
INTRODUCTION
• The study of reaction rates is also known as reaction kinetics (or chemical kinetics). Someone who
does research in reaction kinetics will make many measurements of the speed of reactions.
• The rate of a chemical reaction is the change in concentration over the change in time and is a
measurement of the "speed" at which a chemical reactions occurs and can be defined in terms in
two ways:
• The Rate of Disappearance of Reactants
𝛥[𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠]
• ` −
𝛥𝑡
• The minus sign (-) is an indication of disappearance of reactants.

And
𝛥[𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠]
• The rate of formation of products
𝛥𝑡
• This is the rate at which the products are being formed.
Introduction cont’d
• To measure the rate of a chemical reaction, we must find out the change in the numbers of particles of reactants that is disappearing or a
product that is being made. We must also record the time taken for the change to take place.
•
• For example, to measure the rate of decomposition of hydrogen peroxide in the presence of catalyst, we have
•
• 2H2O2(g) → 2H2O(l) + O2(g)
•
• There are three types of molecules in the reaction, and we could put:
•
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑜𝑓 H2O2 𝑙𝑜𝑠𝑡
• Rate of disappearance of H2O2 =
𝑡𝑖𝑚𝑒 𝑡𝑎𝑘𝑒𝑛
• Or
•
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑜𝑓 H2O 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑
• Rate of appearance of H2O =
𝑡𝑖𝑚𝑒 𝑡𝑎𝑘𝑒𝑛
•
• Or
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑜𝑓 O2 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑
• Rate of disappearance of O2 =
𝑡𝑖𝑚𝑒 𝑡𝑎𝑘𝑒𝑛
Some methods used for Measuring Rates of
reaction.
• Titrations: titrations can be used to discover the contrations of a wide
variety of different chemicals. For example, if hydrogen ions are
librated during a reaction, the course of the reaction can be followed
by titrating a sample of the reaction mixture with alkali. A method
called quenching, where a reaction is brought to an abrupt halt can
be used to bring a neutralisation reaction to a stop. Then the mixture
can be analysed to see how much of the reactants remain
•
• In some other instance, the reaction can be stopped by cooling them
rapidly e.g by plunging the reactants into ice.
Some methods used for Measuring Rates of
reaction cont’d
• 2. Colour Changes: many chemicals are are coloured, and the intensity of
their colour varies with their concentration. For example, thiosulphate
ions, S2O32- , react with hydrogen ions to produce sulphur.
•
• S2O32-(aq) + 2H+(aq) → 2S(s) + SO2(aq) + H2O(l)
• Colourless yellow colourless
•
• The progress of this reaction can be followed by measuring the intensity of
the yellow colour.
• However, colorimeter is an instrument that can be used to follow a
reaction through colour change accurately.
Some methods used for Measuring Rates of
reaction cont’d
• 3. Volume Change: volume changes when gases are given off in a reaction.
Some reactions involving liquids also show volume changes.
•
• 4. Pressure Changes: reaction between gases are often followed by
measuring changes in pressure rather than volume. (it is easier to keep the
volume of the apparatus constant and measure pressure changes).
Examples of reactions that have been followed using pressure changes are:
• 2NO(g) + O2(g) → 2NO2(g)
• 2N2O(g) + N2(g) → O2(g)
• Notice that in both cases, there is a change in the number of moles of gas.
•
Some methods used for Measuring Rates of
reaction cont’d
• 5. Conductivity Changes: solutions containing ions conduct electricity. So, if
there is increase in concentration of ions, the conductivity will increase.
And if the concentration of ions decreases, the conductivity will decrease.
Conductivity can sometimes be used to find out if there is no change in
overall number of ions. Example is the reaction between an ester such as
ethyl ethanoate, CH3COOC2H5 and hydroxide ions:
•
• CH3COOC2H5 (aq) + OH- (aq) → CH3COO- (aq) + C2H5OH(aq)
•
• Each time an ethanoate ion CH3COO- , is made, a hydroxide ion is used up.
As a consequence, there is no change in the total number of ions. However,
ethanoate ions have much smaller conductivities than hydroxide ions, so
the reaction involves a gradual decrease in conductivity.
Some methods used for Measuring Rates of
reaction cont’d
6. Rotation of plane of polarised light.
• Some molecules are able to rotate the plane of polarised light. The
amount of rotation can be measured using polarimeterr.for example,
in the reaction of sucrose with water, sucrose changes into a mixture
of glucose and fructose. This brings about a change in the amount of
rotation. The rotation can be measured at various time intervals. A
graph of angle of rotation plotted against time allows the rate of the
reaction to be determined.
Some methods used for Measuring Rates of
reaction cont’d
• 7.. Measuring the rates of very fast reactions:
• The above methods would be suitable for relatively slow reactions. If
a reaction take place in about 0.01 seconds for example, it is more
difficult to measure the rate of the reaction. We therefore need
specialised equipments to follow such reaction.
• Some methods developed to follow fast reaction include:
• Stopped flow
• Temperature Jump Method where electric spark is passed through
the reaction.
• Flash Photolysis that can measure rates of reaction that are very fast
RATE LAW.
• In general, rates of reactions increase as concentrations increase since
there are more collisions occurring between reactants.
• The rate law or rate expression gives the overall concentration
dependence of reaction.
 Rate ∝ [reactants}n 1.
• Where n is a number which states exactly how rate depends on the concentration of reactant [reactant], it is called the
order
•
• From the above,
• Rate = k[reactant]n

• K = a constant of propotionality called rate constant

•
• e.g , if n = 1, the reaction is first order, rate = k[A] , unit = s-1
• n = 2, the reaction is second order, rate = k[A]2 , unit = dm3 mol-1 s-1
𝟑
𝟑
• n = , the reaction is three-halves order, rate = 𝒌[𝑨] , 𝟐
𝟐
•
• n = 0, it is zero order, rate = k[A]0 or rate = k.
RATE LAW
• Given the Equation below,
• A + B → Product
• Rate = k[A][B];
•
• Then, the order is first order with respect to A,
• and first order with respect to B, with
• the overall reaction order is second order
• example 3:
• if, rate = k[P]2[Q]
• then , the reaction is second order in P, and First order in Q,

• overall order = 2+1 = 3.

• on the whole, Rate = k[reactant]n
• Rate = k[reactant1]m [reactant2]n
RATE LAW
• If we have reactants A, B, C.. e.t.c, the rate expression or rate
equation for the reaction will be:
• Rate = k[A]x [B]y [C]z

• The overall order of the reaction is x + y+ z.

• NOTE: A kinetic analysis aims to find the value of x, y, z and k at

constant temperature for the raection being studied.
RATE LAW
• Question 1:
• (i) rate = k[A]2 [B] [C]2 . what is the overall order?
• (ii) a reaction involve A and B, the reaction is second order in A and
zeroth order in B. write down the rate law for the reaction.
• Answer:
• (i) overall oder = 2+1+2 = 5.

• (ii) rate = k[A]2 [B]0

• Therefore: rate = k[A]2