Chemical Kinetics

• The area of chemistry that concerns reaction rates is

called chemical kinetics.
• One of the main goals of chemical kinetics is to
understand the steps by which a reaction takes place.
This series of steps is called the reaction
mechanism.
• Understanding the mechanism allows us to find ways
to facilitate the reaction and save money and
reactants.
• Knowing the rate law for a reaction is important
mainly because we can usually infer the individual
steps involved in the reaction from the specific form
of the rate law.
12.1 Reaction Rates:
Chemical kinetics deals with the speed at which
changes in reactants or products occur.
The speed, or rate, of a process is defined as the
change in each quantity over a specific period.
For chemical reactions, the quantity that changes are
the amount or concentration of a reactant or product.
So, the reaction rate of a chemical reaction is defined as
the change in concentration of a reactant or product per
unit time.
Reaction Rate:
• For the reactant A to change from A1 at t1 to A2 at
t2, the reaction rate is represented as follows:
[𝐴2]−[𝐴1] 𝛥[𝐴]
• 𝑜𝑟 figure (1)
𝑡2 −𝑡1 𝛥𝑡
• [A] means
concentration
of A in mol/L.
• the symbol Δ
indicates a
change in each
quantity.
 • A is the reactant or product being considered.
• The reaction rate (meaningfully) must be positive.
Dealing with the reactants, the concentration
decreases so R is negative. In this case, we only add a
to the rule, yielding a positive R.

Example:
• For the following reaction
• To calculate the average
rate at which the concentration of NO2 changes over
the first 50 seconds of the reaction using the data
given in the table:

figure (2)

• But we can deal easily with values of any of the

products (NO or O2) without the negative sign,
approaching the same R value.
 • Notice from the table how R is not constant although
the same reaction.
• The value of the rate at a particular time (the
instantaneous rate) can be obtained by computing the
slope of a line tangent to the curve at that point.
• Notice the line tangent drawn at t =100 seconds in
figure (2). The slope of this line gives the rate as
follows:

figure (3)

• Also notice that for the following reaction

• The coefficients of NO
and NO2 are the same, so they yield the same R. But
since O2 has half the coefficient of any of them, it
will have ½ R. figure (4)

OR
12.2 Rate Laws: An Introduction:
Reversible reactions:
• Chemical reactions are reversible. In our discussion
of the decomposition of nitrogen dioxide, we have so
far considered only the forward reaction, as shown
here:
• However, the reverse reaction also can occur. As NO
and O2 accumulate, they can react to re-form NO2:

• When gaseous NO2 is placed in an otherwise empty

container, initially the dominant reaction is

• and the change in the concentration of NO2

(Δ[NO2]) depends only on the forward reaction.
However, after a period, enough products accumulate
so that the reverse reaction becomes important. Now
D[NO2] depends on the difference in the rates of the
forward and reverse reactions. This complication can
be avoided if we study the rate of a reaction under
conditions where the reverse reaction makes only a
negligible contribution. Typically, this means that we
must study a reaction at a point soon after the
 reactants are mixed before the products have had
time to build up to significant levels.
• If we choose conditions where the reverse reaction
can be neglected, the reaction rate will depend only
on the concentrations of the reactants. For the
decomposition of nitrogen dioxide, we can write
The Rate Law
• The proportionality constant k, called the rate
constant, and n, called the order of the reactant,
must both be determined by experiment. The order of
a reactant can be an integer (including zero) or a
fraction.
Notes:
1- The concentrations of the products do not appear in the
rate law because the reaction rate is being studied under
conditions where the reverse reaction does not contribute
to the overall rate.
2- The value of the exponent n must be determined by
experiment; it cannot be written from the balanced
equation.

3-
• A rate law that expresses how the rate depends on
concentration is technically called the differential
rate law, but it is often simply called the rate law.
• A second kind of rate law, the integrated rate law,
also will be important in our study of kinetics. The
integrated rate law expresses how the concentrations
depend on time.
12.3 Determining the Form of the Rate Law:
Determining the differential rate law for a specific
reaction
• Firstly, determine the reactants from the balanced
equation.
• Secondly, you need to find the order of those
reactions. We will use the initial rates for this case to
calculate the order.
• Consider the reaction:
• The general form of the rate law for this reaction is:

• We can determine the values of n and m by observing

how the initial rate depends on the initial
concentrations of NH4+ and NO2-

• See the table.

figure (5)
• In Experiments 1 and 2, where the initial
concentration of NH4+ remains the same but the initial
concentration of NO2- doubles, the observed initial
rate also doubles.
• We have shown that the values of n and m are both 1
and the rate law is
• The overall reaction order is the sum of n and m. For
this reaction, n + m=2. The reaction is second order
overall.
• The value of the rate constant k can now be
calculated using the results of any of the experiments
shown in the table. Using data from experiment 1:
12.4 The Integrated Rate Law:
The integrated rate law:
• The rate law expressed rate as a function of
concentration. The Integrated law expresses it as a
function of time.
• If the reaction is of the first, second, or zeroth order,
it differs accordingly.
• For integrated Frist Order
Law: aA→product

• For Frist Order reaction, a plot of Ln[A] versus t

always gives a straight line of the form y = mx+b
(m=> slope b=> y-intercept)
• where y=ln[A], x=t, m= -k,
b=ln[A]0
• If the plot ln[A] verses t is
not a straight line, the reaction is not first order in A.
• The expression also can appear as:
• Half-life of a reactant (t½) is the
time required for a reactant to reach half its original
concentration.
• For FIRST ORDER reaction when t=t½

• For integrated Second Order Rate Law:

aA→product

• From the rate law: Doubling the conc of [A]

quadruples the reaction rate.
• For integrated SOCEND ORDER reactions, a plot
1
of [ ] versus t will always
𝐴
produce a straight line with a
slope equal to K.
 • When time of the 2nd order reaction reaches t½
the concentration is half its initial:

• For integrated Zero Order Rate Law:

aA→product and [𝐴]0 = 1
• For a zero-order reaction, the rate is constant. It does
not change with concentration as it does for first-
order or second-order reactions.

• In this case a plot of [A] versus t gives a straight line

of slope -k
• For integrated Zero Order
Rate Law: aA→product and
[A]0 = 1
[A]0
When t= t½, [A]=
2
Summary for half-reactions integrated rate laws
12.5 Reaction Mechanism:
Reaction mechanism is a series of steps each one of these
steps called elementary step.
Elementary step means:
a reaction whose rate law can be written from its
molecularity.
Molecularity is defined as:
the number of species that must collide to produce the
reaction indicated by that step, and table (1) shows
examples of molecularity and its rat law.

Table (1)

A reaction involving one molecule is called a

unimolecular step. Reactions involving the collision of
two and three species are termed bimolecular and
termolecular, respectively.
Reaction mechanism shows exactly what happen inside
the reaction, shows the species that are formed and
consumed during the reaction sequence.
For example,
the reaction between nitrogen dioxide and carbon
monoxide, which has balanced equation:
NO2(g) + CO1g2 NO(g) + CO2(g)
The rate law of this reaction is: Rate = k(NO2)2
And the reaction mechanism is:
k1
NO2(g) + NO2(g) NO3(g) + NO(g)
(elementary step1)
k2
NO3(g) + CO(g) NO2(g) + CO2(g)
(elementary step2)
The intermediate in this reaction is NO3.
The intermediate means the species that nether reactants
or products but is formed and consumed during the
reaction.
k1 and k2 are the rate constants of the individual reactions.
There are two important requirements that must be
achieved by reaction mechanism:
1. The sum of the elementary steps must give the overall
balanced equation for the reaction.
for example,

2. The mechanism must agree with the experimentally

determined rate law.
This requirement indicates that there is an elementary
slow step, which when this step ends the reaction ends
too. The rate of this elementary slow step must be the
same rate of the reaction, so, the slow elementary step is
called rate-determining step.
For example,
The elementary step1 of the reaction above is a slow
(rate-determining step), as the step ends the reaction will
end too, so, when we get the rate of the step by using
molecularity (k(NO2)2) will be the same rate of the
reaction (k(NO2)2).
12.6 A Model of Chemical Kinetics:
There is a new model called collision model, this model
is built around the central idea that molecules must collide
to react.
There are two ways to increase collision of the
reactants:
1- by increase the concentration of the reactants.
2- by raising the temperature of the reaction.
chemical reactions speed up when the temperature is
increased.
The kinetic molecular theory of gases predicts that an
increase in temperature raises molecular velocities and so
increases the frequency of collisions between molecules.
This idea agrees with the observation that reaction rates
are greater at higher temperatures.

However, it is found that the rate of reaction is much

smaller than the calculated collision frequency in a
collection of gas particles. This must mean that only a
small fraction of the collisions produces a reaction.
For example,
2BrNO(g) 2NO(g) + Br2(g)
 This reaction needs kinetic energy between the reactant
molecules, this kinetic energy produces collisions
between them. The collisions make reactant molecules
decomposed and form products in an activation energy.
In a specific high temperature,
collisions that the reaction needs
increases, makes the reaction
produced by using only small
fraction of the collisions at the
same activation energy as shown
in figure (6). figure (6)

Arrhenius postulated that the number of collisions

having an energy greater than or equal to the activation
energy is given by the expression:
Number of collisions with the activation energy= (total
number of collisions) e -Ea/RT
where Ea is the activation energy, R is the universal gas
constant, and T is the Kelvin temperature. The factor
represents the fraction of collisions with energy Ea or
greater at temperature T.
There are some collisions can produce the reaction, but
there also some cannot produce the reaction, so to collide
successfully (to rearrange to form products) there are two
requirements:
1. The collision must involve enough energy to produce
the reaction; that is, the collision energy must equal or
exceed the activation energy.
2. The relative orientation of the reactants must allow
formation of any new bonds necessary to produce
products.
Taking these factors into account, we can represent the
rate constant as
k = zpe-Ea/RT

where z is the collision frequency, p is called the steric

factor (always less than 1) and reflects the fraction of
collisions with effective orientations and represents the
fraction of collisions with sufficient energy to produce a
reaction. This expression is most often written in form:
k = Ae-Ea/RT
which is called the Arrhenius equation. In this equation, A
replaces zp and is called the frequency factor for the
reaction.
12.6 Catalysis:
Reaction can seed up by using high temperature, but
sometimes rising temperature become a bad way to seed
the reaction. For example, the biologic reactions which
occur inside the human body; these reactions do not use
temperature; but use some
specific catalysts called
enzymes. This is another
way to seed up the reaction
with a lower temperature
and lower activation energy
as figure (7) shows. figure (7)

A catalyst is a substance that speeds up a reaction

without being consumed itself.
There are some industrial prosses also involve the use of
catalysts.
For example, the production of sulfuric acid uses
vanadium(V) oxide, and the Haber process uses a mixture
of iron and iron oxide.
although a catalyst lowers the activation energy for a
reaction, it does not affect the energy difference between
products and reactants.
Because the catalyst allows the reaction to occur with a
lower activation energy, a much larger fraction of
collisions is effective at a given temperature, and the
reaction rate is increased as shown in figure (8).

figure (8)

Catalysts are classified into:

1-heterogeneous: Catalyst which exists in a different
phase, usually as a solid.
2-homogeneous: is present in the same phase as the
reacting molecules.
First heterogeneous catalysis:
Heterogeneous catalysis most often involves gaseous
reactants being adsorbed on the surface of a solid catalyst.
Typically, heterogeneous catalysis involves four steps:
1. Adsorption and activation of the reactants.
2. Migration of the adsorbed reactants on the surface.
3. Reaction of the adsorbed substances.
4. Escape, or desorption, of the products.
for example, hydrogenation.
Hydrogenation is an important industrial process used to
change unsaturated fats, occurring as oils, to saturated fats
in which the double bonds between the two carbon atoms
have been converted to single bonds through addition of
hydrogen. The reaction rate in this process can be greatly
increased by using a solid catalyst of platinum, palladium,
or nickel.
In the hydrogenation process:
1- ethylene and hydrogen adsorb on the sold surface of
the catalyst as shown in figure (9).
2- these reactants start to leave the surface not so far as
shown figure (10).
3- then the hydrogen reacts with the ethylene and convert
to methane as shown in figure (11).
4- eventually the new product escape from the catalyst
surface as shown in figure (12).
 figure (9) figure (10)

figure (11) figure (12)

Also, catalysts can be used to get out the exhaust

damage gases, by converting it to another harmless gases.
For example, converting carbon monoxide to carbon
dioxide, hydrocarbons to carbon dioxide and water, and
nitric oxide to nitrogen gas to lessen the environmental
impact of the exhaust gases. on the other hand, catalysts
can facilitate the reaction between O2 and SO2 to form
SO3 causing acid rains.
 The most effective catalytic materials are transition
metal oxides and noble metals such as palladium and
platinum.
Second homogenous catalysis:
One such example is the unusual catalytic behavior of
nitric oxide toward ozone. In the troposphere, that part of
the atmosphere closest to earth, nitric oxide catalyzes
ozone production by converting oxygen molecule to
ozone molecule. It is an important problem because ozone
is a powerful oxidizing agent that can react with other air
pollutants to form substances irritating to the eyes and
lungs and is itself very toxic.
In the upper atmosphere, nitric oxide has the opposite
effect it depletes ozone and converts it to oxygen.
Ozone which absorbs ultraviolet light, is necessary to
protect us from the harmful effects of this high energy
radiation. That is, we need O3 in the upper atmosphere to
block ultraviolet radiation from the sun but not in the
lower atmosphere, where we would have to breathe it and
its oxidation products.
The ozone layer is also threatened by Freons, a group of
stable, which produce chlorine atoms. These chlorine
atoms can act as a catalyst and decomposed ozone layer.
Obour STEM Chemistry Club

(Design committee)

Done by: Menna Walid