Chemical Kinetics

Outline:
Introduction- what is chemical kinetics

Factors affecting chemical kinetics

Reaction Rates and How rates are measured.

Rate Laws How the rate depends on amounts of reactants.

Integrated Rate Laws.

Half-life

Arrhenius Equation

Introduction
A chemical reaction is the conversion of one or more
substance(s) to an entirely different substance. The speed
at which the reaction occurs may be slow like the rusting
of iron or degradation of plastics in the environment, this
is extremely slow or even the photosynthesis process in
plants; the speed of some other reactions may be very fast
like neutralization reaction of a strong base like sodium
hydroxide and strong acid like HCl, burning of paper, or
the combustion of cooking gas, which is a mixture of hydrocarbons.

Chemical Kinetics is the study of the speed at which the reaction occurs which is called reaction
rates; that is, how fast a given reaction does proceeds and the factors that affect the speed of the
reaction. The study of rate yields information on the mechanism by which a reaction occurs at
molecular level. The mechanism of a reaction gives a detailed process by which chemical
substances are transformed into other substances. The reactions themselves may involve the
interactions of atoms, molecules, ions, electrons, and free radicals, and they may take place in
gases, liquids, or solids—or at interfaces between any of these.

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The study of the detailed processes of reaction mechanisms is important for many reasons,
including the help it gives in understanding and controlling chemical reactions. Many reactions of
great commercial importance can proceed by more than one reaction path; knowledge of the
reaction mechanisms involved may make it possible to choose reaction conditions favouring one
path over another, thereby giving maximum amounts of desired products and minimum amounts
of undesired products. Furthermore, on the basis of reaction mechanisms, it is sometimes possible
to find correlations between systems not otherwise obviously related.

Chemical kinetics crosses over into many other areas of science and engineering. Rates of
metabolic reaction and the progress of reactions involved in growth and bone regeneration are
studied by biologists. Automobile engineers want to decrease the rate of rusting of car bodies,
while agricultural scientists study the chemical reactions involved in spoilage and decay of foods
(see van Kessel, et al. 358). The speed of any activity (e.g., running, reading, cooking) involves
quantifying how much is accomplished in a specific amount of time. We can quantify, or measure,
the speed of a chemical reaction (also known as its reaction rate)

Factors affecting the rates of reaction

According to collision theory, for a chemical reaction to occur, the reactant molecules must collide
with each other, and in a particular orientation and with sufficient energy. Reactants must come
together to react. The more readily reactant molecules collide with one another, the more rapidly
they react. Experimentally, it has been observed that the main factors that affect this rate of
collision are:

1. Nature of reactants
2. Temperature
3. Pressure/concentration
4. Presence/absence of a catalyst or inhibitor.

Nature of the reactants:

By nature of the reactants, we refer to the physical nature of the reactant, be it solid, liquid, gaseous,
powdery form..e.t.c…. the form that presents a greater surface area tends to make the reaction
proceed faster. A large log placed in a fire will burn relatively slowly. If the same mass of wood
were added to the fire in the form of small twigs, they would burn much more quickly. This is
because the twigs provide a greater surface are than the log does. An increase in the surface area

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of a reactant increases the rate of a reaction. Surface area is larger when a given amount of a solid
is present as smaller particles. A powdered reactant has a greater surface area than the same
reactant as a solid chunk. In order to increase the surface area of a substance, it may be ground into
smaller particles or dissolved into a liquid. In solution, the dissolved particles are separated from
each other and will react more quickly with other reactants.

Reactions may broadly be classified as homogeneous, involving either all gases or all liquids, or
as heterogeneous, in which reactants are in different phases. Under heterogeneous conditions, a
reaction is limited by the area of contact of the reactants. Thus, heterogeneous reactions that
involve solids tend to proceed more rapidly if the surface area of the solid is increased. For
example, a medicine in the form of a fine powder dissolves in the stomach and enters the blood
more quickly than the same medicine in the form of a tablet.

Concentrations and Pressure

Since the rate of a reaction is dependent on the frequency of collisions between the reactants, when
more particles are present in a given amount of space, a greater number of collisions will naturally
occur between those particles. Therefore, increasing the concentration of one or more of the
reactants will generally increase the reaction rate. For example, steel wool burns only slowly in
air, which contains 20% 𝑂 , but bursts into flame in pure oxygen. Thus, as reactant concentration
increases, the frequency with which the reactant molecules collide increases, leading to increased
rates.

For reactions involving gases, pressure is a measure of the concentration of gases. When the
pressure of a gas is increased, its particles are forced closer together, decreasing the amount of
empty space between them. Therefore, an increase in the pressure of a gas is also an increase in
the concentration of the gas. For gaseous reactions, an increase in pressure increases the rate of
reaction for the same reasons as described above for an increase in concentration.

Reaction temperature.
Reaction rates generally increase as temperature is increased. Food can spoil quickly when left on
the kitchen counter. However, the lower temperature inside of a refrigerator slows that process so
that the same food remains fresh for days. This is because increase in temperature leads to an
increase in the speed or reactant particles which leads to more collision and thus an increase in the
velocity of reaction. Gas burners, hot plates, and ovens are often used in the laboratory to increase

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the speed of reactions that proceed slowly at ordinary temperatures. For many chemical processes,
reaction rates are approximately doubled when the temperature is raised by 10 °C.

The presence of a catalyst.

A catalyst is a substance that affects the rate of a chemical reaction, but is not consumed by the
reaction; hence a catalyst can be recovered chemically unchanged at the end of the reaction it has
been used to speed up. Catalysts affect the kinds of collisions (and therefore alters the reaction
mechanism) that lead to reaction. The presence of a catalyst can increase or decrease the rate of a
particular reaction, for example, hydrogen peroxide, used as a disinfectant for scrapes and cuts,
naturally decomposes to produce water and oxygen gas, but the reaction is very slow. A bottle of
hydrogen peroxide will last for several years before it needs to be replaced. However, the addition
of just a small amount of manganese (IV) oxide to hydrogen peroxide will cause it to decompose
completely in just a matter of minutes

Catalysts are extremely important parts of many chemical reactions. Enzymes in our body act as
nature's catalysts, allowing important biochemical reactions to occur at reasonable rates. Chemical
companies constantly search for new and better catalysts to make reactions go faster and thus make
the company more profitable.

A substance that slows down a chemical reaction is called an inhibitor. In active research,
corrosion inhibitors are introduced into the corrosion-active medium in order to protect metals.

The definition of Reaction rates

The Reaction Rate for a given chemical reaction is the measure of the change in concentration of
the reactants or the change in concentration of the products per unit time. Mathematically

𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 ∆[𝑋]

= (0.1)
𝑡𝑖𝑚𝑒 𝑒𝑙𝑎𝑝𝑠𝑒𝑑 ∆𝑡
Thus, the rate of reaction can be determined by measuring the disappearance of a reactant or the
appearance of a product over time. Consider the decomposition of gaseous dinitrogen pentoxide

2𝑁 𝑂 (𝑔) → 4𝑁𝑂 (𝑔) + 𝑂 (𝑔) (0.2)

The rate for this reaction can be determined by measuring the increase in the molar concentration
of 𝑁𝑂 or 𝑂 ,or decrease in the concentration of 𝑁 𝑂 . Using the 𝑂 as an example, suppose that
[𝑂 ] is the initial molar concentration at initial time 𝑡 and [𝑂 ] is the final molar concentration
at final time 𝑡 . Then change in molar concentration is

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 [𝑂 ] − [𝑂 ] = ∆[𝑂 ] (0.3)
and the time required for the change is

𝑡 − 𝑡 = ∆𝑡
(0.4)
The rate of reaction can be written as

[𝑂 ] − [𝑂 ]
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑂 = (0.5)
𝑡 −𝑡
∆[𝑂 ]
= (0.6)
∆𝑡
The decrease in the molar concentration of nitrogen pentoxide can equally be observed. The rate
of the reaction will therefore be

[𝑁 𝑂 ]
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑑𝑒𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛 𝑜𝑓𝑁 𝑂 = − (0.7)
∆𝑡
Note the negative sign which represent the negative change in molar concentration of the reactant
i.e. its concentration decreases with time. Thus it is expected that the concentration of the reactant
will decrease over time and that of the products will increase. Experimentally the rate of a reaction
is plotted as a graph of concentration vs time as shown. Graphically, this is represented in the
picture below, Figure 0.1. as seen the concentration of the reactant decreases with time while the
concentration of the product increases.

Figure 0.1: graphical representation of the change in concentration with time as a reaction progresses
Unit of the rate of reaction.
The rate of reaction is a measure of the change in concentration of reactants or products over time.
The reaction rate has the units of concentration divided by time. Concentration is usually expressed
in 𝑚𝑜𝑙/𝐿 or simply 𝑀, but time may be given in any convenient unit second (𝑠), minutes (𝑚𝑖𝑛),
hour (ℎ), days (𝑑) or possibly years. Therefore, the units of reaction rates may be

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𝑚𝑜𝑙. 𝐿 . 𝑠 i.e mole per litre per second or 𝑚𝑜𝑙. 𝐿 . 𝑚𝑖𝑛 i.e. mole per litre per minute and so
on

Reaction Rates and Stoichiometric Relationships

Consider again the decomposition of dinitrogen pentoxide equation 0.2. From the equation, two
moles of 𝑁 𝑂 are required to produce one mole of 𝑂 . In other words, the rate of decomposition
of 𝑁 𝑂 is twice as fast as the rate of formation of 𝑂 . If we wish to equate the two rate expressions,
then we must divide the rate of decomposition of 𝑁 𝑂 by 2 i.e.

1 [𝑁 𝑂 ] ∆[𝑂 ]
− = (0.8)
2 ∆𝑡 ∆𝑡
A similar argument shows that

∆[𝑂 ] 1 [𝑁𝑂 ]
= (0.9)
∆𝑡 4 ∆𝑡
In general, for the reaction

𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷 (0.10)
The rate of reaction is

1 ∆[𝐴] 1 ∆[𝐵] 1 ∆[𝐶] 1 ∆[𝐷]

𝑟𝑎𝑡𝑒 = − =− = = (0.11)
𝑎 ∆𝑡 𝑏 ∆𝑡 𝑐 ∆𝑡 𝑑 ∆𝑡

Example 0.1 How might the rate of reaction of the following equation be expressed
𝑯𝟐 (𝒈) + 𝑰𝟐 (𝒈) → 𝟐𝑯𝑰(𝒈)
Solution 0.1 Using the stoichiometry of the balanced equation, the rate of the reaction
is given as
∆[𝑯𝟐 ] ∆[𝑰𝟐 ] 𝟏 ∆[𝑯𝑰]
𝒓𝒂𝒕𝒆 = − = =
∆𝒕 ∆𝒕 𝟐 ∆𝒕

Example 0.2 At some time, it was observed that in the reaction

𝟐𝑵𝟐 𝑶𝟓 (𝒈) → 𝟒𝑵𝑶𝟐 (𝒈) + 𝑶𝟐 (𝒈)
The rate of formation of 𝑵𝑶𝟐 was 𝟎. 𝟎𝟎𝟕𝟐 𝒎𝒐𝒍. 𝑳 𝟏 . 𝒔 𝟏

∆[𝑶𝟐 ]
a) What is the rate of change of [𝑶𝟐 ], in 𝒎𝒐𝒍. 𝑳 𝟏 . 𝒔 𝟏
at this
∆𝒕

time?

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 ∆[𝑵𝟐 𝑶𝟓 ]
b) What is the rate of change of [𝑵𝟐 𝑶𝟓 ], in 𝒎𝒐𝒍. 𝑳 𝟏 . 𝒔 𝟏
at
∆𝒕

this time?
c) What is the rate of reaction at this time?
Solution 0.2 (a) from the balanced equation, we have
∆[𝑶𝟐 ] 𝟏 [𝑵𝑶𝟐 ]
=
∆𝒕 𝟒 ∆𝒕
Rate of change of [𝑶𝟐 ] is
∆[𝑶𝟐 ] 𝟏
= × 𝟎. 𝟎𝟎𝟕𝟐 𝒎𝒐𝒍. 𝑳 𝟏 . 𝒔 𝟏 𝒐𝒇 𝑵𝑶𝟐
∆𝒕 𝟒
= 𝟎. 𝟎𝟎𝟏𝟖𝒎𝒐𝒍/𝑳 𝒐𝒇 𝒐𝟐
(b) The balanced equation shows that 2 mole of 𝑵𝟐 𝑶𝟓 is consumed for
every 4 mole of 𝑵𝑶𝟐 that is formed, we have
𝟏 [𝑵𝟐 𝑶𝟓 ] 𝟏 [𝑵𝑶𝟐 ]
− =
𝟐 ∆𝒕 𝟒 ∆𝒕
The rate of change of [𝑵𝟐 𝑶𝟓 ] is
[𝑵𝟐 𝑶𝟓 ] 𝟐 [𝑵𝑶𝟐 ]
=− ×
∆𝒕 𝟒 ∆𝒕
𝟐
= − × 𝟎. 𝟎𝟎𝟕𝟐 𝒎𝒐𝒍. 𝑳 𝟏 . 𝒔 𝟏 𝒐𝒇 𝑵𝑶𝟐
𝟒
= −𝟎. 𝟎𝟎𝟑𝟔𝒎𝒐𝒍/𝑳 𝒐𝒇 [𝑵𝟐 𝑶𝟓 ]
(c ) Rate of reaction can be calculated from the rate of decrease of any
reactant conc or the rate of increase of any product conc.
𝟏 ∆[𝑵𝟐 𝑶𝟓 ]
Rate of reaction =− =
𝟐 ∆𝒕
𝟏
− [−𝟎. 𝟎𝟎𝟑𝟔 𝒎𝒐𝒍. 𝑳 𝟏 . 𝒔 𝟏 𝒐𝒇 [𝑵𝟐 𝑶𝟓 ]]
𝟐

= 𝟎. 𝟎𝟎𝟏𝟖 𝒎𝒐𝒍. 𝑳 𝟏 . 𝒔 𝟏

Alternatively, it can be obtained from 𝑵𝑶𝟐

𝟏 ∆[𝑵𝑶𝟐 ] 𝟏 𝟎.𝟎𝟎𝟕𝟐 𝒎𝒐𝒍 𝒐𝒇 𝑵𝑶𝟐
Rate of reaction = = ×
𝟒 ∆𝒕 𝟒 𝑳 .𝑺

= 𝟎. 𝟎𝟎𝟏𝟖 𝒎𝒐𝒍. 𝑳 𝟏 . 𝒔 𝟏

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Types of Rates
Rate can be measured at the beginning of the reaction, at any point in time while the reaction is in
progress or over an interval of time. At the beginning of the reaction, it is called the initial rate, at
any point in time, this is called instantaneous rate. If over a period of time, this is called the
average rate.

Initial rate
In the initial rate the change in concentration of a reactant or product as a function of time is
measured within minutes (or seconds) the reaction starts. The initial rate is used to derive the rate
law for the reaction. A rate law is a mathematical equation that shows the dependence of reaction
rate to the molar concentrations of reactants at constant temperature. (vide infra)

Instantaneous rate
The instantaneous rate is calculated from the slope of a tangent drawn at any points on the graph
of concentrations versus time. The slope of tangent taken at the initial point of the graph is
assumed to be equal to its initial rate.

Figure 0.2: showing different instantaneous rates (From Chemistry central science brown et al)

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Average rate
The average rate of reaction is obtained by dividing the change in concentration of a reactant or
product that occurs over a longer period of time by the time interval that the change occurs. For
example, consider the following reaction at 300oC:

2𝑁𝑂 (𝑔) → 2𝑁𝑂(𝑔) + 𝑂 (𝑔) (0.12)

If in the first 150 seconds, the concentration of 𝑁𝑂 has decreased from 0.0100 𝑚𝑜𝑙/𝐿 to
0.0055 𝑚𝑜𝑙/𝐿, thus, the average rate for the disappearance of 𝑁𝑂 for first 150 𝑠 under this
condition is,

∆[𝑁𝑂 ] ( 0.0055 − 0.0100)𝑚𝑜𝑙. 𝐿 0.0045𝑚𝑜𝑙. 𝐿

− =− = = 3.0 × 10 𝑚𝑜𝑙. 𝐿 𝑠
∆𝑡 150 𝑠 150𝑠

If in the next 150 seconds the concentration of NO2 decreases from 0.0055 𝑚𝑜𝑙/𝐿 to
0.0038 𝑚𝑜𝑙/𝐿 . Then, the average rate during the second 150 𝑠 period is

∆[𝑁𝑂 ] ( 0.0038 − 0.0055)𝑚𝑜𝑙. 𝐿 0.0017𝑚𝑜𝑙. 𝐿

− =− = = 1.1 × 10 𝑚𝑜𝑙. 𝐿 𝑠
∆𝑡 150 𝑠 150𝑠

The average rate is the mean of several instantaneous rates taken over a period of time.

Note that instantaneous rates of a reaction decreases as time progresses as the concentrations of
reactants decrease. Then the average rate taken over a longer period would have a smaller value
compared to those taken over a shorter period after the reaction begins.

A typical set of data for the reaction of N2O5 is presented below

Table 0.1: The experimental data give the conc of N2O5 measured at the beginning of the reaction (t=0) and then at a number
of time intervals during the course of the reaction
T(s) Conc. N2O5 Average reaction rate in Instantenous reaction
of mol/L each time interval (mol/Ls rate at t (mol/Ls)
0 2.33 1.14 x 10-3 1.42 x 10-3
184 2.07 1.19 x 10-3 1.27 x 10-3
319 1-91 1.11 x 10-3 1.17 x 10-3
529 1.68 0.97 x 10-3 1.02 x 10-3
-3
867 1.35 0.76 x 10 0.83 x 10-3
Note that the Reaction Rate decreases as the reaction proceeds.

Rate law
The rate law is an expression which shows how the reaction rate is related to concentration of
reactants (and in some cases the catalyst). It is also called a rate equation. At a fixed temperature

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 the rate of a given reaction depends on concentration of reactants. The exact relation between
concentration and rate is determined by measuring the reaction rate with different initial reactant
concentrations. By a study of numerous reactions, it is shown that the rate of a reaction is directly
proportional to the reactant concentrations, each concentration being raised to some power.
For a reaction

𝑎𝐴 + 𝑏𝐵 → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 (0.13)
The rate law generally has the form

𝑟𝑎𝑡𝑒 = 𝑘[𝐴] [𝐵] (0.14)

where, 𝑘 is called the rate constant, it is a proportionality constant which is experimentally
determined. It is temperature dependent and it’s value and unit are obtained from the rate law. The
indices 𝑚 and 𝑛 are small whole numbers called the order of reaction. They are also experimentally
determined. The rate law is determined from experimental data. The rate law for some reactions
are given in Table 0.2. An obvious note is that the powers of concentration in the rate law are
usually different from coefficient of the respective reactant in the equation. Therefore, the rate law
for a reaction must be determined by experiment cannot be written by merely looking at the
equation with a background of our knowledge of Law of mass action. However, for some
elementary reactions the powers in the rate law may correspond to coefficient in the chemical
equation.

Table 0.2
Reaction Observed Rate law
1 𝑁𝐻 (𝑎𝑞) + 𝑁𝑂 (𝑎𝑞) → 𝑁 (𝑔) + 2𝐻 𝑂(𝑙) 𝑟𝑎𝑡𝑒 = 𝑘[𝑁𝐻 ][𝑁𝑂 ]
2 2𝑁 𝑂 (𝑔) → 4𝑁𝑂 (𝑔) + 𝑂 (𝑔) 𝑟𝑎𝑡𝑒 = 𝑘[𝑁 𝑂 ]
3 𝐻 (𝑔) + 𝐼 (𝑔) → 2𝐻𝐼 𝑟𝑎𝑡𝑒 = 𝑘[𝐻 ][𝐼 ]
4 2𝐻 (𝑔) + 2𝑁𝑂(𝑔) → 𝑁 (𝑔) + 2𝐻 𝑂(𝑙) 𝑟𝑎𝑡𝑒 = 𝑘[𝐻 ][𝑁𝑂]
5 𝐶𝐻𝐶𝑙 (𝑔) + 𝐶𝑙 (𝑔) → 𝐶𝐶𝑙 (𝑔) + 𝐻𝐶𝑙(𝑔)
𝑟𝑎𝑡𝑒 = 𝑘[𝐶𝐻𝐶𝑙 ][𝐶𝑙 ]
6 𝑁𝑂 (𝑔) + 𝐶𝑂(𝑔) → 𝑁𝑂(𝑔) + 𝐶𝑂 (𝑔) 𝑟𝑎𝑡𝑒 = 𝑘[𝑁𝑂 ]
7 𝑟𝑎𝑡𝑒 = 𝑘[𝐶𝐻 𝐶𝑂𝐶𝐻 ][𝐻 ]
𝐶𝐻 𝐶𝑂𝐶𝐻 (𝑎𝑞) + 𝐼 (𝑎𝑞) 𝐶𝐻 𝐶𝑂𝐶𝐻 𝐼(𝑎𝑞)
+ 𝐻𝐼(𝑎𝑞)

Order of a reaction
It is the (sum of the) powers/exponents of the concentration terms in the rate equation (law). The
order of a reaction, also called rate order, is determined by the number of atoms or molecule whose
concentration change during the reaction. The order of a reaction is important in that it enables us

10
to classify specific chemical reactions easily and efficiently. It also quickly allows us to understand
numerous factors within the reaction including the rate law, units of the rate constant, half life, and
much more. Reaction order can be calculated from the rate law by adding the exponential values
of the reactants in the rate law. The reaction order with respect to a given reactant species equals
the exponent of the concentration of that species in the rate law, as determined experimentally. For
example, consider the rate law

𝑟𝑎𝑡𝑒 = 𝑘[𝐴] [𝐵] … (0.15)

𝑚 is the order of reaction with respect to 𝐴 and 𝑛 is the order of reaction with respect to 𝐵.The
overall order of a reaction equals the sum of the orders of the reactant species in the rate law. Thus
the overall order of the reaction is

𝑚+𝑛 (0.16)
The reaction order is generally whole number but in some cases we have fractional numbers

Table 0.3
Reaction Observed Rate law m n Overall
order
1 𝑁𝐻 (𝑎𝑞) + 𝑁𝑂 (𝑎𝑞) 𝑟𝑎𝑡𝑒 1 1 2
→ 𝑁 (𝑔) + 2𝐻 𝑂(𝑙) = 𝑘[𝑁𝐻 ][𝑁𝑂 ]
2 2𝑁 𝑂 (𝑔) → 4𝑁𝑂 (𝑔) + 𝑂 (𝑔) 𝑟𝑎𝑡𝑒 = 𝑘[𝑁 𝑂 ] 1 1
3 𝐻 (𝑔) + 𝐼 (𝑔) → 2𝐻𝐼 𝑟𝑎𝑡𝑒 = 𝑘[𝐻 ][𝐼 ] 1 1 2
4 2𝐻 (𝑔) + 2𝑁𝑂(𝑔) → 𝑁 (𝑔) + 2𝐻 𝑂(𝑙) 𝑟𝑎𝑡𝑒 = 𝑘[𝐻 ][𝑁𝑂] 1 2 3
5 𝐶𝐻𝐶𝑙 (𝑔) + 𝐶𝑙 (𝑔) 𝑟𝑎𝑡𝑒 1 1 3
→ 𝐶𝐶𝑙 (𝑔) + 𝐻𝐶𝑙(𝑔) 2 2
= 𝑘[𝐶𝐻𝐶𝑙 ][𝐶𝑙 ]
6 𝑁𝑂 (𝑔) + 𝐶𝑂(𝑔) → 𝑁𝑂(𝑔) + 𝐶𝑂 (𝑔) 𝑟𝑎𝑡𝑒 = 𝑘[𝑁𝑂 ] 1 0 1
7 𝐶𝐻 𝐶𝑂𝐶𝐻 (𝑎𝑞) 𝑟𝑎𝑡𝑒 1
= 𝑘[𝐶𝐻 𝐶𝑂𝐶𝐻 ][𝐻 ]
+ 𝐼 (𝑎𝑞) 𝐶𝐻 𝐶𝑂𝐶𝐻 𝐼(𝑎𝑞) + 𝐻𝐼(𝑎𝑞)

A reactant whose concentration does not affect the reaction rate is not included in the rate equation
(law) and the concentration of such a reactant has the power 0. Thus [A] 0 = 1. An example is seen
in 6th reaction given in table 0.2 where the order of reaction with respect to CO is zero. Changing
the concentration of such specie does not affect the rate of the reaction. According to the law of
mass action, the rate of a chemical reaction at a constant temperature depends only on the
concentrations of the substances that influence the rate. The substances that influence the rate of
reaction are usually one or more of the reactants, but can occasionally include products. Catalysts,

11
which do not appear in the balanced overall chemical equation, can also influence reaction rate.
The rate law is experimentally determined and can be used to predict the relationship between the
rate of a reaction and the concentrations of reactants.

Classification of reaction based on order of a reaction

Reactions may be classified according to the order. If in the rate law

𝑟𝑎𝑡𝑒 = 𝑘[𝐴] [𝐵] (0.17)

 m + n = 1, It is first order reaction
 m + n = 2, It is second order reaction
 m + n = 3, It is third order reaction

Zero Order Reaction

A zero order reaction is one whose rate is independent of concentration. For example, in the
reaction

𝑁𝑂 (𝑔) + 𝐶𝑂(𝑔) → 𝑁𝑂(𝑔) + 𝐶𝑂 (𝑔) (0.18)

At 200ºC , its rate equation is

𝑟𝑎𝑡𝑒 = 𝑘[𝑁𝑂 ] (0.19)

Hence the rate does not depend on [CO], so this is not included in the rate law and the power of
[CO] is understood to be zero. The reaction is zeroth order with respect to CO. The reaction is
second order with respect to [NO2]. The overall reaction order is 2 + 0 = 2. A reactant whose
concentration does not affect the reaction rate is not included in the rate equation (law).

The most common type of zero-order reaction occurs when a gas undergoes decomposition on the
surface of a solid. If the surface is completely covered by decomposing molecules, the rate of
reaction is constant because the number of reacting surface molecules is constant, so long as there
is some gas-phase substance left.

Example 0.3 The following tabulated data refer to the hypothetical reaction
𝑨 + 𝟐𝑩 → 𝑪
Expt Initial [A] Initial [B] Initial rate of
formation of C
1 1.0 x 10-2 M 1.0 x 10-2 M 1.5 x 10-6 Ms-1
2 1.0 x 10-2 M 2.0 x 10-2 M 3.0 x 10-6 Ms-1

12
 3 2.0 x 10-2 M 1.0 x 10-2 M 6.0 x 10-6 Ms-1
At a specific temp.
(a) Write the rate expression for the reaction
(b) Calculate the rate constant for the reaction
Solution 0.3 From the reaction, the general expression for a rate law is
𝒓𝒂𝒕𝒆 = 𝒌[𝑨]𝒙 [𝑩]𝒚
From experiments 1 & 2, we have
𝟏. 𝟓 × 𝟏𝟎 𝟔 = 𝒌 × [𝟏. 𝟎 × 𝟏𝟎 𝟐 ]𝒙 × [𝟏. 𝟎 × 𝟏𝟎 𝟐 ]𝒚 (0.20)
𝟑. 𝟎 × 𝟏𝟎 𝟔 = 𝒌 × [𝟏. 𝟎 × 𝟏𝟎 𝟐 ]𝒙 × [𝟐. 𝟎 × 𝟏𝟎 𝟐 ]𝒚 (0.21)
Dividing equation 0.9 by 0.8 gives
𝟔
𝟑. 𝟎 × 𝟏𝟎 𝒌 × [𝟏. 𝟎 × 𝟏𝟎 𝟐 ]𝒙 × [𝟐. 𝟎 × 𝟏𝟎 𝟐 ]𝒚
𝟔
=
𝟏. 𝟓 × 𝟏𝟎 𝒌 × [𝟏. 𝟎 × 𝟏𝟎 𝟐 ]𝒙 × [𝟏. 𝟎 × 𝟏𝟎 𝟐 ]𝒚
𝟐 = 𝟐𝒚
Thus 𝒚 = 𝟏
In a similar fashion
𝟔
𝟔. 𝟎 × 𝟏𝟎 𝒌 × [𝟐. 𝟎 × 𝟏𝟎 𝟐 ]𝒙 × [𝟏. 𝟎 × 𝟏𝟎 𝟐 ]𝒚
𝟔
=
𝟏. 𝟓 × 𝟏𝟎 𝒌 × [𝟏. 𝟎 × 𝟏𝟎 𝟐 ]𝒙 × [𝟏. 𝟎 × 𝟏𝟎 𝟐 ]𝒚
𝟒 = 𝟐𝟐 = 𝟐𝒙
which yield 𝒙 = 𝟐
Thus, the rate law is 𝒓𝒂𝒕𝒆 = 𝒌[𝑨]𝟐 [𝑩]𝟏 = 𝒌[𝑨]𝟐 [𝐁]
(b) To calculate the rate constant, 𝒌, substitute any of the three sets of data
into the rate law expression
𝒓𝒂𝒕𝒆 = 𝒌[𝑨]𝟐 [𝐁]
𝒓𝒂𝒕𝒆
𝒌=
[𝑨]𝟐 [𝐁]
𝟏. 𝟓 × 𝟏𝟎 𝟔 𝑴/𝒔
=
[𝟏. 𝟎 × 𝟏𝟎 𝟐 ]𝟐 𝑴𝟐 × 𝟏. 𝟎 × 𝟏𝟎 𝟐 𝑴
= 𝟏. 𝟓𝑴 𝟐 𝒔 𝟏

Example 0.4 For the reaction:

𝑺𝟐 𝑶𝟐𝟖 (𝒂𝒒) + 𝟑𝑰 (𝒂𝒒) → 𝟐𝑺𝑶𝟐𝟒 (𝒂𝒒) + 𝑰𝟑 (𝒂𝒒)

13
 The data below were obtained.

Expt. # [S2O82-] (mol/L) [I-] (mol/L) Initial Rate,

(mol/L.s)
1 0.036 0.060 1.5 x 10-5
2 0.072 0.060 2.9 x 10-5
3 0.036 0.120 2.9 x 10-5

(a) Determine the order of the reaction with respect to each reactant and
write the rate law for the above reaction.
(b) Calculate the rate constant, k, and give its appropriate units.
(c) Calculate the reaction rate when each reactant concentration is 𝟎. 𝟐𝟎 𝑴
Solution 0.4 (a) The rate law will have the form
𝒙
𝑹𝒂𝒕𝒆 = 𝒌 𝑺𝟐 𝑶𝟐𝟖 [𝑰 ]𝒚
where x and y are rate orders.
To calculate rate order, x: we need to use the equations with varying
concentration of [S2O82-]
𝟓
𝟏. 𝟓 × 𝟏𝟎 = 𝒌 × 𝟎. 𝟎𝟑𝟔𝒙 × 𝟎. 𝟎𝟔𝒚
𝟓
𝟐. 𝟗 × 𝟏𝟎 = 𝒌 × 𝟎. 𝟎𝟕𝟐𝒙 × 𝟎. 𝟎𝟔𝒚
Dividing gives
𝟓
𝟐. 𝟗 × 𝟏𝟎 𝒌 × 𝟎. 𝟎𝟕𝟐𝒙 × 𝟎. 𝟎𝟔𝒚
=
𝟏. 𝟓 × 𝟏𝟎 𝟓 𝒌 × 𝟎. 𝟎𝟑𝟔𝒙 × 𝟎. 𝟎𝟔𝒚
~𝟐 = 𝟐𝟏 = 𝟐𝒙
𝒙=𝟏
similarly
𝟓
𝟐. 𝟗 × 𝟏𝟎 𝒌 × 𝟎. 𝟎𝟑𝟔𝒙 × 𝟎. 𝟏𝟐𝒚
=
𝟏. 𝟓 × 𝟏𝟎 𝟓 𝒌 × 𝟎. 𝟎𝟑𝟔𝒙 × 𝟎. 𝟎𝟔𝒚
~𝟐 = 𝟐𝟏 = 𝟐𝒚
𝒚=𝟏
This reaction is first order w.r.t. [S2O82-] and [I-] therefore
𝑹𝒂𝒕𝒆 = 𝒌 𝑺𝟐 𝑶𝟐𝟖 [𝑰 ]
The rate constant can be calculated as follows

14
 𝟐. 𝟗 × 𝟏𝟎 𝟓
𝒌= = 𝟔. 𝟔 × 𝟏𝟎 𝟑 𝑴 𝟏 𝒔 𝟏
𝟎. 𝟎𝟑𝟔 × 𝟎. 𝟏𝟐
If 𝑺𝟐 𝑶𝟐𝟖 = 𝟎. 𝟐𝑴,[𝑰 ] = 𝟎. 𝟐𝑴 and 𝒌 = 𝟔. 𝟔 × 𝟏𝟎 𝟑 𝑴 𝟏 𝒔 𝟏

𝒓𝒂𝒕𝒆 = 𝟔. 𝟔 × 𝟏𝟎 𝟑 𝑴 𝟏 𝒔 𝟏
× 𝟎. 𝟐𝑴 × 𝟎. 𝟐𝑴 = 𝟐. 𝟔 × 𝟏𝟎 𝟒 𝑴/𝒔
The units for a rate constant will vary as appropriate to accommodate the overall order of the
reaction. Table summarizes the rate constant units for common reaction orders.

Table 0.4: Rate Constant Units for Common Reaction Orders

Overall Reaction Order (x) Rate Constant Unit (Lx−1 mol1−x s−1)
0 (zero) mol L−1 s−1
1 (first) s−1
2 (second) L mol−1 s−1
3 (third) L2 mol−2 s−1

Types of Rate Laws and half-life

The different type of rate laws are discusses as follows

1. the differential Rate Law (rate law) – shows how the rate of a reaction depends on
concentrations. This is what we have been discussing so far
2. Integrated Rate Law – shows how the concentrations of species in the reaction depend on
time.
3. Graphical method to derive the rate law of a reaction.

They are all related to each other

Zero order reaction

If the reaction A  Products is a zero-order reaction, then the differential rate law is

∆[𝐴]
𝑟𝑎𝑡𝑒 = − =𝑘 (0.22)
∆𝑡
Rearranging gives

∆[𝐴] = −𝑘∆𝑡 (0.23)

which yields

[𝐴] − [𝐴] = −𝑘𝑡 (0.24)

This is the integrated rate law for a zero-order reaction. A plot of [𝐴] versus 𝑡 will yield a straight
line with slope = −𝑘 in a graph which represents the graphical rate law.

15
 Figure 0.3: graphical representation of rate law of a zero order reaction
First order integrated law
If the reaction A  Products is a first order reaction, then

∆[𝐴]
𝑟𝑎𝑡𝑒 = − = 𝑘[𝐴] (0.25)
∆𝑡
∆[𝐴]
= −𝑘∆𝑡 (0.26)
[𝐴]
which yields

ln[𝐴] = −𝑘𝑡 + ln[𝐴] (0.27)

Or

[𝐴]
ln= −𝑘𝑡 (0.28)
[𝐴]
And a plot of ln[𝐴] versus 𝑡 will yield a straight line with slope = −𝑘 and y-intercept = ln[𝐴]

Figure 0.4: Graphical representation of First order reaction

16
Second order integrated law
If the reaction A  Products is a second order reaction, then

∆[𝐴]
𝑟𝑎𝑡𝑒 = − = 𝑘[𝐴] (0.29)
∆𝑡
i.e.

∆[𝐴]
= −𝑘𝑡 (0.30)
[𝐴]
which yields

1 1
= 𝑘𝑡 + (0.31)
[𝐴] [𝐴]
A plot of [ ]
versus 𝑡 will yield a straight line with slope = k and y-intercept = [ ]

Figure 0.5: Graphical representation of second order reaction

Example 0.5 The hydrolysis of ethyl nitrobenzoate by aqueous sodium hydroxide was
followed at 250C by titration of the hydroxide against standard acid at different
stages in the reaction. From the given data, show that the reaction is second
order
Time (seconds) 0 95 140 222 334 805 1364
ml of acid used 10 9.3 9.0 8.5 7.9 6.1 4.8
Solution 0.5 For the second order reaction
𝟏 𝟏
= 𝒌𝒕 +
[𝑨]𝒕 [𝑨]𝟎

17
 This can be rearranged to give
[𝑨]𝟎 − [𝑨]𝒕 𝟏
𝒌= ×
[𝑨]𝟎 [𝑨]𝒕 𝒕
Given [𝑨]𝟎 = 10 ml, we can derive a table calculating 𝒌 at different times in
the reaction
Time [𝑨]𝒕 [𝑨]𝟎 − [𝑨]𝒕 𝟏 [𝑨]𝟎 − [𝑨]𝒕
𝒌= ×
𝒕 [𝑨]𝟎 [𝑨]𝒕
𝟗𝟓 9.3 0.7 1 0.7
× = 7.92 × 10
95 10 𝑥 9.3
𝟏𝟒𝟎 9.0 1.0 1 1.0
× = 7.93 × 10
140 10 𝑥 9.0
𝟐𝟐𝟐 8.5 1.5 1 1.5
× = 7.94 × 10
222 10 𝑥 8.5
𝟑𝟑𝟒 7.9 2.1 1 2.1
× = 7.95 × 10
334 10 𝑥 7.9
𝟖𝟎𝟓 6.1 3.9 1 3.9
× = 8.05 × 10
805 10 𝑥 6.1
𝟏𝟑𝟔𝟒 4.8 5.2 1 5.2
× = 7.93 × 10
1364 10 𝑥 4.8
The constancy of 𝒌 shows that the reaction under consideration is of second
order.
The alternative method
𝟏
A plot of [𝑨] versus 𝒕 will give a straight line with
𝒕

Slope = +𝒌

Example 0.6 The decomposition of NO2 at 300°C is described by the equation

𝟏
𝑵𝑶𝟐 (𝒈) → 𝑵𝑶(𝒈) + 𝑶𝟐 (𝒈)
𝟐
and the following data was obtained:
𝑇𝑖𝑚𝑒 (𝑠) [𝑁𝑂 ], 𝑀
0.0 0.01000
50.0 0.00787
100.0 0.00649
200.0 0.00481
300.0 0.00380
determine the order of the reaction using the graphical method

18
 Solution 0.6 Graphing ln [NO2] vs. t yields:
The plot is not a straight line, so the
process is not first-order in [A].
Time (s) [NO2], M ln[NO2]
0.0 0.01000 -4.610
50.0 0.00787 -4.845
100.0 0.00649 -5.038
200.0 0.00481 -5.337
300.0 0.00380 -5.573
It does not fit 𝐥𝐧[𝑨]𝒕 = −𝒌𝒕 + 𝐥𝐧[𝑨]𝟎
𝟏
We consider [𝑵𝑶
𝟐]

Time (s) [NO2], M 1/[NO2]

0.0 0.01000 100
50.0 0.00787 127
100.0 0.00649 154
200.0 0.00481 208
300.0 0.00380 263
A graph of 1/[NO2] vs. t gives this plot.
This is a straight line. Therefore, the
process is second-order in [NO2].
𝟏 𝟏
= 𝒌𝒕 +
[𝑨]𝒕 [𝑨]𝟎

Half-life
Half-life of a reaction, 𝑡 is the time required for the concentration of a reactant to drop to one half

of its initial value i.e. when

1
[𝐴] = [𝐴] (0.32)
2
Half-life is a convenient way to describe how fast a reaction occurs, especially if it is a first-order
process. A fast reaction has a short half-life. Substituting this for [𝐴] in the integrated rate equation
for any of the order gives the half-life expression for that reaction order.

For zero-order reaction at

19
 [𝐴]
[𝐴] = = 0.5[𝐴] (0.33)
2
Substituting in the integrated rate law [𝐴] − [𝐴] = −𝑘𝑡 gives

[𝐴] [𝐴]
− [𝐴] = − = −𝑘𝑡 (0.34)
2 2
i.e.

[𝑨]𝟎
𝒕𝟏 = (0.35)
𝟐 𝟐𝒌
[ ]
For first-order reaction, at 𝑡 , substituting [𝐴] = in the integrated law gives

[𝐴] 0.5[𝐴]
ln = ln = −𝑘𝑡 (0.36)
[𝐴] [𝐴]
Which is

ln 0.5 = −𝑘 𝑡 (0.37)
i.e.

ln 2 = 0.693 = 𝑘𝑡 (0.38)
For a first order process the half-life expression is

𝟎. 𝟔𝟗𝟑
𝒕𝟏 = (0.39)
𝟐 𝒌
For a first-order process, the half-life does not depend on [𝐴] .

[ ]
For second-order reactions, substituting [𝐴] = = 0.5[𝐴] in the integrated law gives

1 1
= 𝑘𝑡 + (0.40)
0.5[𝐴] [𝐴]
2 1
= 𝑘𝑡 + (0.41)
[𝐴] [𝐴]

Rearranging

2 1
− = 𝑘𝑡 (0.42)
[𝐴] [𝐴]
This gives

𝟏
𝒕𝟏 = (0.43)
𝟐 𝒌[𝑨]𝟎

20
The half-life for second-order and other reactions depends on reactant concentrations and therefore
changes as the reaction progresses

Example 0.7 The half-life of a first-order reaction was found to be 10 min at a certain
temperature. What is its rate constant in reciprocal seconds?
Solution 0.7 From 𝒕½ =
𝟎.𝟔𝟗𝟑
;
𝒌

k = –0.693/(600 s) = 0.00115 s–1

Example 0.8 A certain first-order reaction has a half-life of 20.0 minutes.

a. Calculate the rate constant for this reaction.
b. How much time is required for this reaction to be 75% complete?
Solution 0.8 a. For a first order reaction 𝒕½ =
𝟎.𝟔𝟗𝟑
𝒌
𝟎. 𝟔𝟗𝟑 𝟎. 𝟔𝟗𝟑
𝒌= = = 𝟑. 𝟒𝟕 × 𝟏𝟎 𝟐 𝒎𝒊𝒏 𝟏
𝒕½ 𝟐𝟎

Figure 0.6: summary of the various attributes of zero, first and second order reactions

21
Collision theory model
On a molecular level, reaction rates depend on the frequency of collisions between molecules. The
greater the frequency of collisions, the higher the reaction rate. For a collision to lead to a reaction,
however, it must occur with sufficient energy to break bonds and with suitable orientation for new
bonds to form in the proper locations. The two main conditions for a collision between reacting
molecules to be productive are

- The colliding molecules must possess sufficient kinetic energy to cause a reaction
- The reacting molecules must collide with proper orientation:

There is a minimum energy necessary to cause a reaction between the colliding molecules called
activation energy, 𝐸 . Only the molecules that collide with a kinetic energy greater than 𝐸 may be
able to get over the barrier and react. The molecules colliding with kinetic energies less than 𝐸 fail
to surmount the barrier. The collisions between them are unproductive and the molecules simply
bounce off one other.

The reactant molecules must also collide with favourable orientation (relative position). The
correct orientation is that which ensure direct contact between the atoms involved in the breaking
and forming of bond. Consider the reaction

𝐶𝑙 + 𝑁𝑂𝐶𝑙 → 𝑁𝑂 + 𝐶𝑙 (0.44)
Effective collision orientation is seen only when chlorine radical comes in contact with the chlorine
end of the 𝑁𝑂𝐶𝑙, see figure below. Thus, only molecules colliding with kinetic energy greater than
activation energy 𝐸 and with correct orientation can cause reaction.

Figure 0.7: effective and ineffective collision orientation

22
Effect of Temperature on Reaction Rate
It has been observed experimentally that increase in temperature leads to a remarkable increase in
the rate of a chemical reaction and hence in rate constants. Generally, as temperature increases, so
does the reaction rate. This is because k is temperature dependent

Figure 0.8: variation of rate constant with temperature Temperature dependence of the rate constant for methyl isonitrile
conversion to acetonitrile.

Arrhenius Equation
Svante Arrhenius developed a mathematical relationship between the rate constant, 𝑘 and
activation energy, 𝐸 given as

𝑘 = 𝐴𝑒 (0.45)
where, 𝐴 is the frequency factor, a number that represents the likelihood that collisions would
occur with the proper orientation for reaction, 𝑅 is a gas constant and T is the absolute temperature

at which the reaction is taking place. The exponential factor, 𝑒 , is the fraction (< 1) of
molecules having the minimum kinetic energy for reaction. Note as 𝐸 increases, 𝑘 decreases. This
equation is called the Arrhenius equation. Taking the natural logarithm of both sides, the equation
becomes

𝐸 (0.46)
ln 𝑘 = −
𝑅𝑇 + ln 𝐴
𝐸
Thus, a plot of ln 𝑘 vs. will give a straight-line graph with slope 𝑅 and 𝐸 can be calculated;
ln 𝐴 is the intercept. The rate constant, 𝑘 is determined experimentally at several temperatures.
Alternatively, the rate constant can be determined at two different temperatures and activation
energy is calculated from 𝐸 :

𝑘 𝐸 1 1
𝑙𝑛 =− − (0.47)
𝑘 𝑅 𝑇 𝑇
23
Conversely, if 𝐸 is known, the Arrhenius equation can be used to calculate 𝑘 at a different temp.

Example 0.9 Benzene diazonium chloride decomposes in the presence of water

according to first order kinetics. If the rate constant at 25℃ is 2.8 ×
10 𝑚𝑖𝑛 , and the activation energy is 11.9 𝑘𝑐𝑎𝑙 /𝑚𝑜𝑙, find the rate
constant at 35℃.
Solution 0.9 the rate constant can be determined at a different temperature can be
calculate using a rearranged equation 0.47
𝑘𝟐 𝐸 1 1 𝐸 𝑻𝟐 − 𝑻𝟏
ln =− − =−
𝑘𝟏 𝑅 𝑇𝟏 𝑇𝟐 𝑅 𝑻𝟐 𝑻𝟏
Given that
𝑘 = 2.8 × 10 𝑚𝑖𝑛 ; 𝑇 = 𝟐𝟕𝟑 + 25℃ = 298𝐾; 𝑇 = 35℃ =
308𝐾 and 𝐸 = 11.9 𝑘𝑐𝑎𝑙 /𝑚𝑜𝑙; 𝑅 =
Substituting these values
𝑘𝟐 𝟏𝟏. 𝟗 𝟑𝟎𝟖 − 𝟐𝟗𝟖
ln =
2.8 × 10 𝟏. 𝟗𝟖𝟕 𝟑𝟎𝟖 × 𝟐𝟗𝟖
Which gives
𝑘𝟐 = 𝟓. 𝟑𝟕 × 10 𝑚𝑖𝑛

Mechanism Molecularity
Chemical reactions may be classed into two types: elementary reactions and complex reactions.
An elementary reaction is a simple reaction which occurs in a single step. An example is seen in
the rearrangement of methyl isonitrile. The isonitrile molecule must collide with another molecule
to get enough energy for rearrangement:

𝐶𝐻 𝑁𝐶 → 𝐶𝐻 𝐶𝑁 (0.48)
two different molecules must collide with enough energy and with the correct geometry:

A complex reaction is that which occurs in two or more steps and are also called multistep
reactions. For example, the reaction:

𝐵𝑟 (𝑔) + 2𝑁𝑂(𝑔) → 2𝐵𝑟𝑁𝑂(𝑔) (0.49)

Occurs via 2 elementary steps, both bimolecular:

𝐵𝑟 (𝑔) + 𝑁𝑂(𝑔) → 𝐵𝑟 𝑁𝑂(𝑔) (0.50)

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 𝐵𝑟 𝑁𝑂(𝑔) + 𝑁𝑂(𝑔) → 2𝐵𝑟𝑁𝑂(𝑔) (0.51)
Elementary steps in a multi-step mechanism must always add together to give the overall, balanced
equation (verify). note that the component Br2NO is not in overall, it is called an intermediate.

The molecularity of an elementary reaction is defined as the number of reactant molecules involved
in that elementary reaction. Molecularity is always defined for an elementary reaction.

Reaction Molecularity
𝑪𝑯𝟑 𝑵𝑪 → 𝑪𝑯𝟑 𝑪𝑵 1
𝑩𝒓𝟐 (𝒈) + 𝑵𝑶(𝒈) → 𝑩𝒓𝟐 𝑵𝑶(𝒈) 2
𝑩𝒓𝟐 𝑵𝑶(𝒈) + 𝑵𝑶(𝒈) → 𝟐𝑩𝒓𝑵𝑶(𝒈) 2
The elementary reactions having molecularity 1,2 and 3 are called unimolecular, bimolecular and
termolecular respectively.

Rate Laws of Elementary Processes

The rate law of an elementary step or reaction is based on the molecularity of the reaction. For the
elementary reaction

𝐴 → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 (0.52)
The rate law is

𝑟𝑎𝑡𝑒 = 𝑘[𝐴] (0.53)

Similarly for the bimolecular elementary step

𝐴 + 𝐴 → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 (0.54)
Or

𝐴 + 𝐵 → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 (0.55)
The rate laws respectively are

𝑟𝑎𝑡𝑒 = 𝑘[𝐴] (0.56)

And

𝑟𝑎𝑡𝑒 = 𝑘[𝐴][𝐵] (0.57)

Thus, molecularity and order are the same for an elementary step. Elementary reaction steps with
order 3 (called ternary reactions) are rare and unlikely to occur. However, overall reactions
composed of several elementary steps can, of course, be of any (including non-integer) order

Molecularity versus Order of Reaction

Order of Reaction Molecularity of Reaction

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 1. It is the sum of powers of the 1. It is the number of reacting species
concentration terms in the rate law undergoing simultaneous collision in
expression an elementary reaction.
2. It is an experimentally determined 2.It is a theoretical concept.
value
3. It can have fractional value. 3.It is always whole number.
4. It can assume zero value. 4.It cannot have zero value.
5. Order of a reaction can change with 5.Molecularity is invariant for a
conditions such as pressure, chemical equation.
temperature and concentration.

Mechanism
A balanced chemical equation usually gives the starting point and the finishing point of a reaction,
it also shows the ratios of reactant(s) and product(s). However, it gives no information on how the
process of bond rearrangement occurs, i.e.- pathway taken. The sequence of events that describes
the actual process by which reactants become products is called the reaction mechanism. It consists
of a series of steps of individual reactions called elementary steps or elementary reactionsthat
shows probable reactions involving molecular species – including reaction intermediates. Each of
these processes is known as an elementary reaction or elementary process or steps. The sum of
these elementary steps yields the overall balanced equation for the reaction. Reaction mechanism
is derived from experimental kinetic data

Consider the hypothetical reaction

2𝐴 + 𝐵 → 𝐶 + 𝐷 (0.58)
which may involve the following elementary steps in its mechanism:

• Step-1: 𝐴 + 𝐵 → 𝑋;
• Step-2: 𝑋 + 𝐴 → 𝑌;
• Step-3: 𝑌→ 𝐶 + 𝐷

The overall reaction is 2𝐴 + 𝐵 → 𝐶 + 𝐷;The entities 𝑋 and 𝑌 are called reactive intermediates

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At temperatures below 500 𝐾, the mechanism for the reaction between 𝐶𝑂 and 𝑁𝑂 is, based on
experimental evidence, proposed to be as follows

Step 1 𝑁𝑂 + 𝑁𝑂 → 𝑁𝑂 + 𝑁𝑂 (an elementary reaction)

Step 2 𝑁𝑂 + 𝐶𝑂 → 𝑁𝑂 + 𝐶𝑂 (an elementary reaction)

Each of the above steps is an elementary reaction such that adding the two equations will give the
overall equation of reaction

𝑁𝑂 + 𝐶𝑂 → 𝑁𝑂 + 𝐶𝑂 (overall reaction)

The specie 𝑁𝑂 is neither a product or a reactant, it is an intermediate that is formed and consumed
in the course of the reaction.

Multistep mechanisms involve one or more intermediates. Intermediates are not the same as
transition states. Intermediates can be stable and can therefore sometimes be identified and even
isolated. Transition states, on the other hand, are always inherently unstable and as such can never
be isolated

In a multistep process, one of the steps will be slower than all others and the overall reaction
cannot occur faster than this slowest. This step is said to be the rate-determining step. In the above
example of the reaction between 𝐶𝑂 and 𝑁𝑂 , the rate law for this reaction is found experimentally
to be

𝑅𝑎𝑡𝑒 = 𝑘 [𝑁𝑂 ]

From the equation of reaction, it is noted that CO is necessary for this reaction to occur, but the
rate of the reaction does not depend on its concentration which led to the proposed mechanism
described below

• A proposed mechanism for this reaction is

• Step 1 𝑁𝑂 + 𝑁𝑂 → 𝑁𝑂 + 𝑁𝑂 (slow)
• Step 2 𝑁𝑂 + 𝐶𝑂 → 𝑁𝑂 + 𝐶𝑂 (fast)

As CO is not involved in the slow, rate-determining step, it does not appear in the rate law.

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 Example 0.10 The decomposition of nitrous oxide, 𝑁 𝑂, is believed to occur by a two-
step mechanism:
𝑁 𝑂(𝑔) → 𝑁 (𝑔) + 𝑂(𝑔) (𝑠𝑙𝑜𝑤)
𝑁 𝑂(𝑔) + 𝑂(𝑔) → 𝑁 (𝑔) + 𝑂 (𝑔)(𝑓𝑎𝑠𝑡)
(a) Write the equation for the overall reaction.
(b) Write the rate law for the overall reaction
Solution 0.10 (a) The overall equation is obtained by adding the two elementary
steps
𝑁 𝑂(𝑔) → 𝑁 (𝑔) + 𝑂(𝑔)
𝑁 𝑂(𝑔) + 𝑂(𝑔) → 𝑁 (𝑔) + 𝑂 (𝑔)
2𝑁 𝑂(𝑔) → 2𝑁 (𝑔) + 𝑂 (𝑔)
(b) The rate law is obtained from the slow step; Because that slow step
is a unimolecular elementary reaction, the rate law is first order:
𝑅𝑎𝑡𝑒 = 𝑘[𝑁 𝑂]

Catalysis
As earlier defined, a catalyst is a substance that changes the speed of reaction without getting
permanently damaged in the process. Catalysts increase the rate of a reaction by decreasing the
activation energy of the reaction. They do so by changing the mechanism by which the process
occurs. Most reactions in the body, the atmosphere, and the oceans occur with the help of catalysts.
Much industrial chemical research is devoted to the search for more effective catalysts for reactions
of commercial importance. Extensive research efforts also are devoted to finding means of
inhibiting or removing certain catalysts that promote undesirable reactions, such as those that
corrode metals, age our bodies, and cause tooth decay.

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 Figure 0.9:

Catalysts can be classified into two types: homogeneous and heterogeneous. A homogeneous
catalyst is any catalyst that is present in the same phase as the reactant molecules. A
heterogeneous catalyst is one that exists in a phase different from the phase of the reactant
molecules, usually as a solid in contact with either gaseous reactants or reactants in a liquid
solution.

One way a catalyst can speed up a reaction is by holding the reactants together and helping bonds
to break.

Enzymes are catalysts in biological systems. The substrate fits into the active site of the enzyme
much like a key fits into a lock.

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