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7 - Chemical Kinetics

Chemical kinetics is the branch of chemistry concerned with the speeds or rates at
which chemical reactions occur. The number of factors determining how fast
reactants are transformed into products is small. Analyzing these factors yields
information that helps understand the pathway through which reactants are
transformed into products. This knowledge can then be used to predict how a
change in a physical condition will alter the speed of a chemical reaction.

7.1 Rate of a reaction


The rate of a reaction is the speed by which the reactants are transformed into
products. The rate can be expressed as the rate of the consumption of the reactants
or as the rate of the formation of the products.
Let us consider the following hypothetical reaction: aA + bB cC + dD.

The rates of consumption of A and B are respectively =


The rates of formation of C and D are respectively: =

As the change in the reactants is negative, a (-) sign is added to get a positive rate.
From stoichiometry we know that for every a moles of A consumed there will also
be consumed b moles of B and will be produced c moles of C and d moles of D.
Ratereaction =

Consequently the relation is:

In a constant volume V the (change) number of moles can be expressed in terms of


concentration, thus: =
Ratereaction =

[]

[]

[]

[]

=
=

[]

[]

[]

[]

For gases and solutes rates are preferably expressed in terms of concentration. For
gases reaction rates can also be expressed in terms of partial pressures.
Determining the (changes in) concentrations can be difficult, especially after the
reaction has been going on for a while. This is why the (changes in) concentrations
are usually determined through indirect changes such as: pressure (for gases),
color, electric conductivity, pH, density, formation of a precipitation etc.
The rates discussed so far are actually average rates during a time interval t. By
means of calculus we can also determine instant rate (e.g. Ratei A=d[A]/dt).

7.2 Collision Theory


7.2.1 Introduction to Collision Theory
It is clear that the primary requirement for a chemical reaction to occur is collision
(contact) between reactant particles. It is known that such collisions are quite
frequent, for example in gaseous state in NK there are nearly 1030 collisions per
liter per second, however should all this collisions result in a chemical reaction it
would be completed in a fraction of a second. We know that this is not the case,
thus a simple collision between particles is a necessary yet not a sufficient
condition to result in a chemical reaction.
To look into the subject further lets consider the following single step reaction:
N2O (g) + NO (g) N2 (g) + NO2 (g)

Obviously we must consider only the collisions between the particles that yield our
products as the other collisions will not contribute to the formation of our products.
For a collision to result in a reaction the following conditions must be satisfied:
1. At the moment of collision the particles must be properly oriented.
2. The particles must have sufficient Ek to break the reactants chemical bonds.
The necessity to satisfy both these conditions instantaneously means only few of
the total collisions result in a chemical reaction.
Collisions which result in a chemical reaction are called effective collisions.
Collisions which satisfy the first condition. The probability of two molecules to
have a proper orientation during a random collision is dependent only on the
molecular geometry of the molecules thus is dependent only on the nature of the
reactants (molecules). This means that for a given type of molecules the probability
of a collision to satisfy the first condition is a constant for every random collision.
Consequently the probability of a random collision satisfying the second condition
to satisfy the first condition as well is a constant. Thus, the number of collisions
that satisfy both conditions is directly proportional to the number of collisions that
satisfy the second condition.

7.2.2 Transition State Theory: The Activation Energy


When two particles collide, they combine in a system. They lose some of their
speed and thus they lose some of their Ek. This energy is transformed into chemical
potential energy of the new formed system. This increase in the Ep destabilizes the
reactants chemical bonds (recall the chemical bond theories, esp. MO Theory). If
this increase in Ep is not sufficient (i.e. the reactants bonds do not break) the
system will then separate into the reactant particles. The energy that increased the
potential energy is now transformed back into Ek of the reactant particles.
If, however, this Ep exceeds a certain threshold it will cause the breakage of the
reactants bonds and then the formation of new product bonds thus resulting in a
chemical reaction. Every reaction (collision) has a characteristic Ep threshold. The
unstable form having max Ep is called an activated complex or a transition state.
The difference between the Ep of the activated complex and the initial Ep of the
reactants is called energy of activation (Ea). Its clear that this extra energy is
actually the part of Ek that was transformed into Ep thus the energy of activation
can also be defined as the minimum Ek
required to have an effective collision.
When the complex is separated into the
new formed products a part of the
chemical energy is transformed back into
Ek of the particles of products. As we can
see from the graph of Ep in the right, Ea
forms an energetic barrier between the
reactants and the products. If we
consider the reverse reaction the activation energy would be the difference between
Ep of the activated complex and the initial Ep of the products which is called Ea
reverse. From this (from the graph as well) we notice that the difference between
the energies of the products and reactants is same as the difference between the
activation energies of the forward and the reverse reaction. Thus: H = Ea f - Ea r .

7.3 Reaction Mechanism


The equation of a chemical reaction shows only the stoichiometric relation
between the reactants and the products. It does not show the pathway through
witch the reactants are transformed into products. This far we have discussed only

the case when a collision between two particles results in a chemical reaction. We
know, however, that reactions may have 3, 4 or even more reacting particles.
According to the collision theory the rate of the reaction is determined by the
number of effective collisions. From physics, we know that the probability (and
thus the number) of three particles colliding instantaneously is small and when we
add the requirements of having a proper orientation and having sufficient energy
during the collision, the number of effective collisions would be very small. Using
the same reasoning the number of effective collisions between 4 or more molecules
would be extremely small.
On the contrary, experimental results show that the rates of such reactions vary,
with some actually having very high rates. This fact leads to the proposition that
some reactions do not occur through a single collision between all the reactants but
through a series of collisions between two (or 3) particles.
The series of collisions (steps) that leads to product formation is called a reaction
mechanism. Each of the steps of the mechanism is called an elementary reaction.
The products of a step (collision) may be the reactants of another step (collision) of
the mechanism. This proposition is supported by experimental findings of chemical
species that are formed in one of the steps and consumed in another step of the
reaction mechanism but do not appear at the overall balanced chemical equation (if
the reaction would occur through a single step there would be no such species).
Chemical species that are formed and consumed within the reaction mechanism but
do not appear at the overall chemical equation are called reaction intermediates.
Reactions which occur through a single collision between the reactants are called
single step reactions. A single step or elementary reaction passes through a single
transition state and does not involve the formation of any intermediate species. The
discussion over single step reaction holds even for the single steps (collisions or
elementary reactions) of a reaction mechanism.

7.4 The number of effective collisions


We know that the rate of a single step reaction is determined by the number of
effective collisions per unit time. Let us find what this number depends on.
7.4.1 Collisions which satisfy the second condition. For a collision to satisfy this
condition, the sum of the kinetic energies of the colliding molecules must exceed
the Ea. Lets now look at the energetic requirements of particular molecules to

satisfy this condition. In a random collision lets consider the first colliding
molecule having a random kinetic
energy of Ek1 or higher. The two prior
statements imply that for the collision to
satisfy the condition the second colliding
molecule must have a kinetic energy of
Ek2 (such that Ek1 + Ek2 = Ea) or higher.
From the Maxwell-Boltzmann
Distribution of kinetic energies we know that the probability (P(1)) of a random
molecule having a kinetic energy of Ek1 or higher is dependant only on the
temperature (T). Symmetrically the probability (P(2)) of a molecule having a kinetic
energy of Ek2 or higher is dependant only on the temperature (T). Consequently the
probability (P(E)) of a collision to be of two such molecules is P(E)= P(1)* P(2) and is
obviously dependant only on the temperature. As a result, at a constant temperature
the probability of a collision to satisfy the second condition is a constant thus the
number of collisions satisfying the second condition is proportional only to T.Nr.C.
In conclusion, for a given type of molecules, at a constant temperature (T) the
number of collisions satisfying both conditions and thus the number of effective
collisions is directly proportional to the T.Nr.C.
7.4.2 The total number of collisions. From physics, the total number of molecular
collisions (1-2) per second (T.Nr.C) is equal to the product of the number of
molecules (type 1) N1 and the frequency of collisions per molecule f1-2, which is
the inverse of the time period between two consecutive collisions, thus its equal to
the ratio of mean translational molecular speed (<v1>) and the mean free path ().
. . . = 1 12 = 1

<1 >
12

= 1 < 1 >

< >2 2
<1 >

=< > 2 1 2 .

Where <vr> is the mean relative molecular speed, N2 is the number of molecules
(type 2), d is the sum of the kinetic radii of the considered molecules (d=r1+r2) and
V is the volume. For a constant volume (V), the term (N1N2/V) is proportional to
the product of the concentrations of the considered molecules ([1][2]).
In gas mixtures, the effect of the intermolecular forces on translational molecular
speeds is insignificant thus the mean relative speed takes the form <vr >=

8RT
M12

where R is the universal gas constant (8.31*103), T is the temperature and M12 is

the reduced molar mass (M12-1=M1-1 + M2-1). Substituting in the equation we get:
. . = (8) (

d2
M12

) (T)(

N1 N2
V

). The term (

d2
M12

) is determined by the

nature of the reactants. The term (8) is a constant. The term T is determined
by the temperature (T). Thus for given types of reactants, at a constant volume (V)
and temperature (T), T.Nr.C in gas mixtures is proportional to the product of the
concentrations of the reacting molecules ([1][2]).
In solids, the intermolecular forces are strong enough to trap molecules in potential
wells. Molecules can only oscillate around their equilibrium points, consequently
in solids the mean relative molecular speed is virtually zero. This is the reason why
reactions, where all (two or more) reactants are solids, are not common.
In liquid mixtures (solutions), the effect of intermolecular forces cannot be
neglected. Translational molecular speeds are determined by the combination of
the thermal speeds and the tension of the intermolecular forces, which is depended
on the nature of the reactants, temperature (T) and outer pressure (p0). Thus for a
given type of reactants, at a constant temperature (T) and outer pressure (p0) the
mean relative molecular speed is a constant. Consequently, in liquid mixtures
(solutions) for given types of reactants at a constant temperature and outer pressure
T.Nr.C is proportional to the product of the concentrations of the molecules [1][2].
For reactions occurring between solutes, in a liquid solute, the nature of the
reactants must include the nature of the solute as well.
In conclusion, the T.Nr.C. of a homogenous mixture, for given types of reactants,
at a constant temperature (and outer pressure p0 for liquids), is proportional to the
product of the concentration of the reactants ([1][2]).
7.4.3 The Interacting Area.
Many reactions occur through an interacting area. Usually, such reactions occur
when the reactants are in different states (gas-solid, gas-liquid, and liquid-solid).
To derive the T.Nr.C at an interacting area, we use of the concept of pressure at a
molecular level, which is the result of molecular collisions at the area of contact.
In gas-solid and gas-liquid interacting areas pressure is a result of gas molecules
colliding with the condensed surface. As the strength of intermolecular forces at
gases can be neglected, the sum of the changes in momentum of gas particles
colliding with the surface results in gas pressure. =

2< >

Where pA is the partial pressure of the gas (type A), Fx is the force perpendicular to

the interacting area A, px is the sum of the change in momentum of the gas
molecules (Nx) colliding with the interacting area at a time interval t, m is the
molecular mass (m= M/Na=MkB/R) and <vx> is the mean molecular speed
perpendicular to the interacting area. Since the number of gas molecules is great, it
can be approximated <vx>=< v > /3 . From gas law pA=[A]RT (pA~[A]T). Its
clear that the ratio (Nx/t) is . . =

[]

2< >

= 2

38
3

3 3 []
42

Consequently, for a given type of reactants, at a constant temperature, T.Nr.C. at


gas-solid or gas-liquid interacting areas is proportional to the interacting area (A)
and to the concentration of the gas ([A]). In high pressures, changes in pA ([A]) no
longer significantly change the number of effective collisions (and thus the rate of
the reaction), as the interacting area can be considered saturated.
In the liquid-solid interacting area, pressure is the result of liquid molecules
colliding with the solid surface. In liquids, the strength of intermolecular forces
cannot be neglected, thus when a molecule collides with the solid surface the
change in its momentum is due to the intermolecular forces and the force exerted
by the solid (the pressure).Thus the pressure and consequently the T.Nr.C. are:
=

( )

(2< >)

; . . =

2< >

= (

3
)
2<>

Where U is the effect (tension) of the intermolecular forces. For given types of
reactants, at a constant temperature (T) and pressure (p), the term p/(2m<v>-U)
can be considered to be a constant. Consequently, for given types of reactants, at a
constant temperature and pressure, T.Nr.C. at a liquid-solid interacting area is
proportional to the interacting area (A).
In conclusion, the T.Nr.C. at an interacting area, for given types of reactants, at a
constant temperature (pressure p for liquids), is proportional to the interacting area
and to the concentration of the gas (for gas-solid or gas-liquid reactions).

7.5 The Rate equation of a single step reaction


Molecularity of a single step reaction or of a step of a reaction mechanism is the
number of molecules participating in an individual reaction (collision). A single
step reaction can be unimolecular, bimolecular or termolecular if there are
respectively participating one, two or three molecules. It is highly improbable for
four (or more) molecules to collide instantaneously. When the conditions of having

proper orientation during the collision and having sufficient kinetic energy are
included, the number of such collisions is virtually zero. This is why steps
(collisions) with four or more molecules are never proposed.
7.5.1 Rate equation of Bimolecular Reactions: A + B products
Earlier we saw that the number of effective collisions (A-B), and thus the rate of
the reaction, for given reactants, at a constant temperature, is proportional to the
product of the concentration of the reactant species. Rate ~ [A][B]. This
proportionality can be converted into equality by introducing a constant k known
as the rate constant (k= Rate / ([A][B])). The value of k is determined by the nature
of the reactants and the temperature. Rate=k[A][B].
7.5.2Rate equation of Bimolecular Reactions: A + A products
The number of effective collisions (A-A), and thus the rate of the reaction, for
given reactants, at a constant temperature, is proportional to the product of the
concentration of the reactant species. Rate ~ [A][A] or Rate ~ [A]2. This
proportionality is converted into equality by a constant k. Rate = k[A]2
7.5.3 Rate equation of Unimolecular Reactions: A* products
A reaction of this type occurs when a highly energetic molecule (A*) is separated
into smaller molecules or undergoes a molecular restructuration. The rate of such a
reaction will depend only on the number of highly energetic molecules (A*), which
in a constant volume can be expressed in terms of concentration ([A *]). This
proportionality is converted into equality by a constant k. Rate = k [A *]. The rate of
the whole transformation from normal molecule A to a highly energetic molecule
A* to products is given by the speed of the mechanism discussed in section 7.7.2.
7.5.4 Rate equation of Termolecular Reactions:
Termolecular reactions, though rare, are plausible propositions of single step
reaction collision models. It can be concluded that the number of effective
collisions of such cases, for given reactants, at a constant temperature, is
proportional to the product of the concentrations of the reactants.
Type 1: A + B + C products
Rate = k [A][B][C]
Type 2: A +A + B products
Rate = k [A]2[B]
Type 3: A + A + A products
Rate = k [A]3

7.6 Factors affecting the Rate of a reaction


On the previous section, the effect of the concentration of the reactants and of the
interacting area on the reaction rate was discussed. This section deals with two
more factors affecting the rate of the reaction: the nature of the reactants and the
temperature.
7.6.1 The nature of the reactants affects reactions rates at three levels. First, one of
the terms of the T.Nr.C. equation is determined by the nature of the reactants, thus
T.Nr.C is depended on the nature of the reactants. Second, the nature of the
reactants is the only factor determining the probability of molecules to have an
appropriate orientation during a collision. Last, the energy of activation (Ea) of a
reaction is determined by the nature of the reactants. The larger the number and
strength of the chemical bonds of the reactants the larger will be the energy needed
to destabilize this chemical bonds thus the slower the reaction will proceed.
7.6.2 The effect of temperature. When the temperature is increased, the rate of the
reaction increases almost every time. This is true for both exothermic and
endothermic reactions. An increase by
100C increases the rate by 100% to 300%.
An increase in temperature increases the
T.Nr.C. but this increase alone (by 2%)
cant explain the increase in the rate of the
reaction. From the graph we notice that at
a higher temperature (T2) the number of
molecules exceeding the Ea is much greater than at a lower temperature (T1). This
is the reason why an increase in temperature greatly increases the reaction rate.
The relation between the temperature and the rate constant, and thus the rate of the
reaction, is given by the Arrhenius Equation. This relation, however, is empirical.

() +

2 1

) ln(2 )

= (

Where k is the rate constant, Ea is the energy of activation, R is the gas constant.
T is the temperature (k1 rate constant at T1 and k2 is the rate constant at T2).The
term e-E/RT represents the part of molecules exceeding the energy of activation. A is
called the frequency factor which combines the effect of collision frequency and
the probability of having an appropriate molecular orientation. By means of

logarithms we can transform the Arrhenius equation into a linear relation between
lnk and the inverse of temperature (1/T). If we know the rate constants (rates) of a
reaction at two different temperatures (T1 and T2) the value of the energy of
activation and the frequency factor A can be determined. The Arrhenius equation,
due to being empirical can only give an approximation of the rate of the reaction.

7.7 The Rate of a Reaction Mechanism


Each step of the reaction mechanism has its own transition state, energy of
activation and its rate. Since the lifetime of reaction intermediates is very short, it
can be concluded that shortly after the reaction has begun, the rate of formation of
a reaction intermediate is same as the rate of consumption of that intermediate.
Assuming that the rates of reactions vary greatly, which is generally true, the
following can be concluded:
If two steps contribute to the formation of the same product(s), almost the entire
amount of product(s) will come from the fastest step. If two steps consume the
same reactant, the reactant will be consumed almost entirely by the fastest step.
Lets consider the slowest step in a series of steps that leads to the formation of
some product. Since by definition the successive steps are significantly faster, the
products of the slowest steps will be consumed almost immediately. Similarly, due
to the previous steps being faster, there will be sufficient reactants for the slowest
step to consume from. As a result, the rate of a series of steps that leads to the
formation of some product will be same as the rate of the slowest step.
Consequently, the rate of formation of some product will be same as the slowest
step of the fastest series of steps that contributes to its formation. Since this step
determines the rate of the reaction, it is called the rate determining step.
The energy of activation of a series of steps that leads to the formation of some
product is the difference between the potential energy of the transition state having
the highest potential energy, which is usually that of the slowest step, and the
potential energy of the initial reactants. The lifetime of a reaction intermediate is
generally slower than the time required to reach thermal equilibrium. This is why
the Ea of a sequence of steps that leads to the formation of some product is
depended on the height of the highest energy barrier and not on the Eas of the
particular steps of the considered sequence.

7.7.1 The rate equation of a reaction mechanism where the first step is the slowest.
In such cases, the first step is the rate determining step, thus usually the rate of the
reaction mechanism is same as the rate of the first step. Since the energy of
activation of the first step is the highest barrier that the reactants must pass in their
path to be transformed into products, any reactants that cross this barrier, those that
successfully undergo the first step, will be quickly transformed into products, thus
the rate of the reaction mechanism is same as the rate of the first step. Generally, in
such mechanisms, the Ea of the whole reaction is same as the Ea of the first step.
The following reaction is an example of such mechanisms:
1. NO + F2 ONF +F
Rate1 = k1[NO][F2]
2. F + NO ONF
Rate2 = k2[NO][F]
2NO + F2 2ONF
Rate = -d[NO]/2dt = -d[F2]/dt = d[ONF]/2dt .
But F2 is consumed only in the first step thus: Rate = -d[F2]/dt =Rate1 = k1[NO][F2]
7.7.2 In some mechanisms, one of the steps is the reverse of one of the other steps.
In such reaction mechanisms, the intermediate products of the considered step may
continue their path to be transformed into the final products or may undergo the
reverse reaction, thus be transformed back into the products of the considered step.
The following is such an example: A D
Rate= -d[A]/dt = d[D]/dt
*
*
1) A + AA + A
2) A + A A + A
3) A* D
Rate1=k1[A]2
Rate2=k2[A][A*]
Rate3=k3[A*]
The product D is formed only step 3, thus: Rate = d[D]/dt = Rate3=k3[A*] .
The reactant A is consumed in step 1 and produced in step 2, thus:
Rate = -d[A]/dt = Rate1 Rate2 = k1[A]2 - k2[A][A*] = k3[A*] from where
[A*] = k1[A]2/(k3 + k2[A]) [A]k1/k2
thus
Rate= k3[A*]=[A]k1k3/k2
The following is another example: CH3OH(aq) + H+(aq) + Br-(aq) CH3Br(aq) + H2O
1) CH3OH + H+ CH3OH2+
Rate1=k1[CH3OH][ H+]
2) CH3OH2+ CH3OH + H+
Rate2=k2[CH3OH2+]
3) CH3OH2+ + Br- CH3Br + H2O
Rate3= k3[Br-][CH3OH2+]
Rate= -d[CH3OH]/dt = -d[H+]/dt = -d[Br-]/dt = Rate3= k3[Br-][CH3OH2+]
Rate= -d[CH3OH]/dt = Rate1 Rate2= k1[CH3OH][ H+]- k2[CH3OH2+]
[CH3OH2+]= k1[CH3OH][ H+]/(k2 + k3[Br-]) k1[CH3OH][ H+]/ k2
Bromine ions Br- are consumed only in step 3. Methanol is consumed in step 1
and produced in step 2. Rate= k3[Br-][CH3OH2+]= (k1k3/ k2)[Br-][CH3OH][ H+]

7.7.3 Chain Reaction Mechanisms.


A chain reaction is one where an intermediate formed in one step generates an
intermediate in a subsequent step, then that intermediate generates another
intermediate, and so on. The mechanism can be described in the following stages:
The initiation step is the step where the chain carriers are initially formed. In an
initiation step a molecule dissociates into atoms which will be the chain carriers.
Propagation steps are the steps where carriers produced in the initiation step attack
other reactant molecules each attach results in the formation of a new chain carrier.
Branching steps (optional) are steps in which the attack of a chain carrier on a
reactant molecule result in the formation of more than one chain carrier.
Retardation steps (optional) are the steps where a carrier attacks a product
molecule. The result is the formation of a reactant molecule and a new carrier thus
retardation steps do slow down the chain but they do not end it.
Termination steps are the steps where carriers combine and end the chain. Chain
reactions have complex rate expressions and usually have fractional reaction order.
The following is an example of chain reactions: H2 (g) + Br2 (g) 2HBr(g)
Initiation:
1) Br2 2Br
Propagation: 2) Br + H2 HBr + H
3) H + Br2 HBr + Br
Retardation: 4) Br + HBr Br2 + H
5) H + HBr H2 + Br
Termination: 6) Br + Br Br2
7) H + H H2
8) H + Br HBr
7.7.4 Order of the reaction is called the sum of the exponents of the concentration
terms present in the rate of the reaction expression. Clearly, the order of single step
reactions is same as their molecularity.
7.7.5 The Arrhenius equation and Reaction Mechanisms. The Arrhenius equation
holds even for reaction mechanisms (just as it holds for single step reactions).
However the values of the parameters A and Ea will be a combination of the values
of the As and the Eas of the particular steps of the reaction mechanism. For
mechanisms where the first step is the rate determining step the values of A and E a
of the reaction mechanism are same as the values of A and Ea of the first step. To
find the values of A and Ea of the reaction for other types of mechanisms we must
express the rate constant of the reaction in terms of the rate constants of the
particular steps of the reaction mechanism and then apply the Arrhenius equation
to all rate constants then solve to find the values of A and Ea of the mechanism.

7.8 Catalysis
A catalyst is a substance that alters (generally increases) the rate of a reaction
without being consumed in the reaction. The catalyst is consumed in one of the
early steps of the mechanism but is then reproduced in one of the late steps of the
mechanism. This is why even a small amount of catalyst is sufficient to catalyze a
reaction. Since the catalyst is chemically unaltered at the end of the reaction, it is
usually written above the arrow used in the equations of chemical reactions.
The catalyzed reaction has a different mechanism from that of the not catalyzed
reaction. The catalyzed path has an overall smaller energy of activation thus the
increase in the rate of the reaction. Since the catalyst does not affect the overall
stoichiometry of the reaction, it does not change the H of the reaction. This
implies that the Ea r is lowered by the same amount that the Ea f is lowered.
7.8.1 In homogenous catalysis, the catalyst is in the same physical state as the
reactants. An example of homogenous catalysis is the effect of gaseous chlorine in
the division of dinitrogen oxide. In room temperature N2O is inert, however, at
about 6000C it is divided according to the mechanism: 2N2O (g) 2N2 (g) + O2 (g)
1. N2O(g) N2 (g) + O(g)
2. O(g) + N2O(g) N2 (g) + O2 (g) Ea=240 kj/mol
The reaction can be catalyzed by traces of chlorine according to the following
2 ()

mechanism: 2N2O (g)


2N2 (g) + O2 (g)
Ea = 140 kj.mol
1) Cl2(g) 2Cl(g) 2) N2O(g) + Cl(g) N2 (g) + ClO(g) 3) 2 ClO(g) O2 (g) + Cl2 (g)
7.8.2 In heterogeneous catalysis, the catalyst, usually being a solid, is not in the
same physical state as the reactants. In this type of catalysis the reactants are
absorbed onto the catalysts surface and this is where the reaction occurs.
Absorption is called physical absorption when the reactant molecules are kept onto
the catalysts surface due to intermolecular London forces. However, heterogeneous
catalysis generally occurs through chemo-absorption, which is when reactant
molecules are kept onto the catalysts surface by bonds similar to chemical bonds.
When these bonds are formed, chemically absorbed molecules undergo changes in
their electronic configuration. Certain bonds in the structure of these molecules are
weakened and even broken. The layer of chemically absorbed molecules plays the
role of a reaction intermediate in the catalyzed reaction. The division of N2O on a
gold plate is an example of such catalysis: 2N2O (g) 2N2 (g) + O2 (g) Ea=120 kj/mol
1) N2O(g) N2O(onto Au)
2) N2O(onto Au) N2 + O(onto Au)
3) 2O(onto Au) O2 (g)
As N2O is consumed only in step 1: Rate = -d[N2O (g)]/2dt =Rate1/2=A[N2O (g)] k1/2

The rate of the reaction is proportional to the catalysts surface (A) and to the
concentration of N2O. For a constant catalyst surface, at high pressures, changes in
[N2O] no longer significantly affect the rate of the reaction thus in these conditions
the rate will be same as the rate constant thus the reaction order will be zero.
7.8.3 Catalysts generally are highly specific. In some cases, from the same
reactants, different catalysts will lead to the formation of different products.
As an example, if the reaction between carbon oxide (CO) and hydrogen (H2) is
catalyzed by nickel (Ni), the products will be a mixture of hydrocarbons. However,
if the same reaction is catalyzed by of zinc and chromium oxides (ZnO, Cr2O3), the

product will be methanol. 2 + CO 4

/2 3

2 + CO

8 Experimental Rate of a Reaction


The numerical value of the rate constant and the form of the expression of the rate
of a reaction are based on experimental results. On the previous sections, we saw
the theoretical foundations of the following conclusion:
The rate of a reaction, for given reactants, at a constant temperature, is
proportional to an expression which includes the concentrations of the reactants,
catalysts or even of the products (and if applicable, is proportional to the
interacting area).
By altering the concentration of one of the reactants, catalysts or products, whilst
keeping the rest constant, makes it possible to find how these changes in the
concentration affect the rate of the reaction. Repeating this process for each of the
participating chemical species makes it possible to know how changes in their
respective concentrations affect the rate of the reaction. The combination of these
results leads to the expression of the rate of the reaction.
The following is an example: 2NO(g) + O2 (g) 2NO2 (g)
Nr.
Concentrations
Rate
Considering the first three experiments, it
NO (mol/l) O2 (mol/l)
can be concluded that Rate ~ [O2].
1.
10-3
10-3
7*10-6
Considering the last three experiments, it
2.
10-3
2*10-3 14*10-6
can be concluded that Rate ~ [NO]2.
3.
10-3
3*10-3 24*10-6
-3
Combining the previous results, it can be
4.
2*10
3*10-3 84*10-6
5.
3*10-3
3*10-3 189*10-6
concluded that Rate = k[O2][NO]2, where
the value of the rate constant is k=7*103 (l2/s*mol2). The order of the reaction is 3.