Rate laws or rate equations are mathematical expressions that describe the

relationship between the rate of a chemical reaction and the concentration of its
reactants. In general, a rate law (or differential rate law, as it is sometimes called)
takes this form:

rate=k[A]m[B]n[C]p…rate=k[A]m[B]n[C]p…

in which [A], [B], and [C] represent the molar concentrations of reactants, and k is
the rate constant, which is specific for a particular reaction at a particular
temperature. The exponents m, n, and p are usually positive integers (although it is
possible for them to be fractions or negative numbers). The rate constant k and the
exponents m, n, and p must be determined experimentally by observing how the rate
of a reaction changes as the concentrations of the reactants are changed. The rate
constant k is independent of the concentration of A, B, or C, but it does vary with
temperature and surface area.

The exponents in a rate law describe the effects of the reactant concentrations on the
reaction rate and define the reaction order. Consider a reaction for which the rate law
is:

rate=k[A]m[B]nrate=k[A]m[B]n

If the exponent m is 1, the reaction is first order with respect to A. If m is 2, the

reaction is second order with respect to A. If n is 1, the reaction is first order in B.
If n is 2, the reaction is second order in B. If m or n is zero, the reaction is zero order
in A or B, respectively, and the rate of the reaction is not affected by the concentration
of that reactant. The overall reaction order is the sum of the orders with respect to
each reactant. If m = 1 and n = 1, the overall order of the reaction is second order
(m + n = 1 + 1 = 2).

The rate law:

rate=k[H2O2]rate=k[H2O2]

describes a reaction that is first order in hydrogen peroxide and first order overall. The
rate law:

rate=k[C4H6]2rate=k[C4H6]2
describes a reaction that is second order in C4H6 and second order overall. The rate
law:

rate=k[H+][OH−]rate=k[H+][OH−]

describes a reaction that is first order in H+, first order in OH−, and second order
overall.

Example 1

Writing Rate Laws from Reaction Orders

An experiment shows that the reaction of nitrogen dioxide with carbon monoxide:

NO2(g)+CO(g)⟶NO(g)+CO2(g)NO2(g)+CO(g)⟶NO(g)+CO2(g)

is second order in NO2 and zero order in CO at 100 °C. What is the rate law for the
reaction?

Solution
The reaction will have the form:

rate=k[NO2]m[CO]n

The reaction is second order in NO2; thus m = 2. The reaction is zero order in CO;
thus n = 0. The rate law is:

rate=k[NO2]2[CO]0=k[NO2]2

Remember that a number raised to the zero power is equal to 1, thus [CO]0 = 1, which
is why we can simply drop the concentration of CO from the rate equation: the rate of
reaction is solely dependent on the concentration of NO2. When we consider rate
mechanisms later in this chapter, we will explain how a reactant’s concentration can
have no effect on a reaction despite being involved in the reaction.

Check Your Learning

The rate law for the reaction:

H2(g)+2NO(g)⟶N2O(g)+H2O(g)H2(g)+2NO(g)⟶N2O(g)+H2O(g)

has been determined to be rate = k[NO]2[H2]. What are the orders with respect to each
reactant, and what is the overall order of the reaction?
order in NO = 2; order in H2 = 1; overall order = 3

Check Your Learning

In a transesterification reaction, a triglyceride reacts with an alcohol to form an ester
and glycerol. Many students learn about the reaction between methanol (CH3OH) and
ethyl acetate (CH3CH2OCOCH3) as a sample reaction before studying the chemical
reactions that produce biodiesel:

CH3OH+CH3CH2OCOCH3⟶CH3OCOCH3+CH3CH2OHCH3OH+CH3CH2OCOCH
3⟶CH3OCOCH3+CH3CH2OH

The rate law for the reaction between methanol and ethyl acetate is, under certain
conditions, determined to be:

rate=k[CH3OH]rate=k[CH3OH]

What is the order of reaction with respect to methanol and ethyl acetate, and what is
the overall order of reaction?

order in CH3OH = 1; order in CH3CH2OCOCH3 = 0; overall order = 1

It is sometimes helpful to use a more explicit algebraic method, often referred to as

the method of initial rates, to determine the orders in rate laws. To use this method,
we select two sets of rate data that differ in the concentration of only one reactant and
set up a ratio of the two rates and the two rate laws. After canceling terms that are
equal, we are left with an equation that contains only one unknown, the coefficient of
the concentration that varies. We then solve this equation for the coefficient.

Ozone in the upper atmosphere is depleted when it reacts with nitrogen oxides. The
rates of the reactions of nitrogen oxides with ozone are important factors in deciding
how significant these reactions are in the formation of the ozone hole over
Antarctica (Figure 1). One such reaction is the combination of nitric oxide, NO, with
ozone, O3:

Over the past several years, the atmospheric ozone concentration over Antarctica
has decreased during the winter. This map shows the decreased concentration as a
purple area. (credit: modification of work by NASA)
 NO(g)+O3(g)⟶NO2(g)+O2(g)NO(g)+O3(g)⟶NO2(g)+O2(g)

This reaction has been studied in the laboratory, and the following rate data were
determined at 25 °C.

Trial [NO] (mol/L) [O3] (mol/L) Δ[NO2]Δt(mol\;L−1s−1)Δ[NO2]Δt(mol\;L−1s−1)

1 1.00 × 10−6 3.00 × 10−6 6.60 × 10−5

2 1.00 × 10−6 6.00 × 10−6 1.32 × 10−4

3 1.00 × 10−6 9.00 × 10−6 1.98 × 10−4

4 2.00 × 10−6 9.00 × 10−6 3.96 × 10−4

5 3.00 × 10−6 9.00 × 10−6 5.94 × 10−4

Table 3.

Determine the rate law and the rate constant for the reaction at 25 °C.

Solution
The rate law will have the form:

rate=k[NO]m[O3]nrate=k[NO]m[O3]n

We can determine the values of m, n, and k from the experimental data using the
following three-part process:

1. Determine the value of m from the data in which [NO] varies and [O3] is
constant. In the last three experiments, [NO] varies while [O3] remains
constant. When [NO] doubles from trial 3 to 4, the rate doubles, and when
[NO] triples from trial 3 to 5, the rate also triples. Thus, the rate is also directly
proportional to [NO], and m in the rate law is equal to 1.
2. Determine the value of n from data in which [O3] varies and [NO] is
constant. In the first three experiments, [NO] is constant and [O3] varies. The
reaction rate changes in direct proportion to the change in [O3]. When [O3]
doubles from trial 1 to 2, the rate doubles; when [O3] triples from trial 1 to 3,
the rate increases also triples. Thus, the rate is directly proportional to [O3],
and n is equal to 1.The rate law is thus:
 rate=k[NO]1[O3]1=k[NO][O3]rate=k[NO]1[O3]1=k[NO][O3]

3. Determine the value of k from one set of concentrations and the corresponding
rate.

krate[NO][O3]6.60×10−5mol\;L−1s−1(1.00×10−6mol\;L−1)(3.00×10−6mol\;L−1)2.20×107L\;mol−1s−1krat
e[NO][O3]6.60×10−5mol\;L−1s−1(1.00×10−6mol\;L−1)(3.00×10−6mol\;L−1)2.2
0×107L\;mol−1s−1

The large value of k tells us that this is a fast reaction that could play an
important role in ozone depletion if [NO] is large enough.

Check Your Learning

Acetaldehyde decomposes when heated to yield methane and carbon monoxide
according to the equation:

CH3CHO(g)⟶CH4(g)+CO(g)CH3CHO(g)⟶CH4(g)+CO(g)

Determine the rate law and the rate constant for the reaction from the following
experimental data:

Trial [CH3CHO] (mol/L) −Δ[CH3CHO]Δt(mol\;L−1s−1)−Δ[CH3CHO]Δt(mol\;L−1s−1)

1 1.75 × 10−3 2.06 × 10−11

2 3.50 × 10−3 8.24 × 10−11

3 7.00 × 10−3 3.30 × 10−10

Table 4.

Answer:

rate=k[CH3CHO]2rate=k[CH3CHO]2 with k = 6.73 × 10−6 L/mol/s

Example 3

Determining Rate Laws from Initial Rates

Using the initial rates method and the experimental data, determine the rate law and
the value of the rate constant for this reaction:
 2NO(g)+Cl2(g)⟶2NOCl(g)2NO(g)+Cl2(g)⟶2NOCl(g)

Trial [NO] (mol/L) [Cl2] (mol/L) −Δ[NO]Δt(mol\;L−1s−1)−Δ[NO]Δt(mol\;L−1s−1)

1 0.10 0.10 0.00300

2 0.10 0.15 0.00450

3 0.15 0.10 0.00675

Table 5.

Solution
The rate law for this reaction will have the form:

rate=k[NO]m[Cl2]nrate=k[NO]m[Cl2]n

As in Example 2, we can approach this problem in a stepwise fashion, determining the

values of m and n from the experimental data and then using these values to determine
the value of k. In this example, however, we will use a different approach to determine
the values of m and n:

1. Determine the value of m from the data in which [NO] varies and [Cl2] is
constant. We can write the ratios with the subscripts x and y to indicate data
from two different trials:

ratexratey=k[NO]mx[Cl2]nxk[NO]my[Cl2]nyratexratey=k[NO]xm[Cl2]xnk[NO]ym[Cl2]yn

Using the third trial and the first trial, in which [Cl2] does not vary, gives:

rate3rate1=0.006750.00300=k(0.15)m(0.10)nk(0.10)m(0.10)nrate3rate1=0.006750.00300=k(0.15
)m(0.10)nk(0.10)m(0.10)n

After canceling equivalent terms in the numerator and denominator, we are left
with:

0.006750.00300=(0.15)m(0.10)m0.006750.00300=(0.15)m(0.10)m

which simplifies to:

 2.25=(1.5)m2.25=(1.5)m

We can use natural logs to determine the value of the exponent m:

ln(2.25)mln(1.5)ln(2.25)ln(1.5)m2mln(2.25)mln(1.5)ln(2.25)ln(1.5)m2m

We can confirm the result easily, since:

1.52=2.251.52=2.25

2. Determine the value of n from data in which [Cl2] varies and [NO] is constant.

rate2rate1=0.004500.00300=k(0.10)m(0.15)nk(0.10)m(0.10)nrate2rate1=0.004500.00300=k(0.10
)m(0.15)nk(0.10)m(0.10)n

Cancelation gives:

0.00450.0030=(0.15)n(0.10)n0.00450.0030=(0.15)n(0.10)n

which simplifies to:

1.5=(1.5)n1.5=(1.5)n

Thus n must be 1, and the form of the rate law is:

Rate=k[NO]m[Cl2]n=k[NO]2[Cl2]Rate=k[NO]m[Cl2]n=k[NO]2[Cl2]

3. Determine the numerical value of the rate constant k with appropriate

units. The units for the rate of a reaction are mol/L/s. The units for k are
whatever is needed so that substituting into the rate law expression affords
the appropriate units for the rate. In this example, the concentration units are
mol3/L3. The units for k should be mol−2 L2/s so that the rate is in terms of
mol/L/s.

To determine the value of k once the rate law expression has been solved,
simply plug in values from the first experimental trial and solve for k:

0.00300mol\;L−1s−1k(0.10mol\;L−1)2(0.10mol\;L−1)1k3.0mol−2L2s−10.00300mol
\;L−1s−1k(0.10mol\;L−1)2(0.10mol\;L−1)1k3.0mol−2L2s−1
Check Your Learning
Use the provided initial rate data to derive the rate law for the reaction whose equation
is:

OCl−(aq)+I−(aq)⟶OI−(aq)+Cl−(aq)OCl−(aq)+I−(aq)⟶OI−(aq)+Cl−(aq)

Trial [OCl−] (mol/L) [I−] (mol/L) Initial Rate (mol/L/s)

1 0.0040 0.0020 0.00184

2 0.0020 0.0040 0.00092

3 0.0020 0.0020 0.00046

Table 6.

Determine the rate law expression and the value of the rate constant k with appropriate
units for this reaction.

Answer:

rate2rate3=0.000920.00046=k(0.0020)x(0.0040)yk(0.0020)x(0.0020)yrate2rate3=0.000920.00046=k(0.002
0)x(0.0040)yk(0.0020)x(0.0020)y

2.00 = 2.00y

y=1

rate1rate2=0.001840.00092=k(0.0040)x(0.0020)yk(0.0020)x(0.0040)yrate1rate2=0.001840.00092=k(0.004
0)x(0.0020)yk(0.0020)x(0.0040)y

2.002x2y2.002x214.002xx22.002x2y2.002x214.002xx2

Substituting the concentration data from trial 1 and solving for k yields:

ratek[OCl−]2[I−]10.00184k(0.0040)2(0.0020)1k5.75×104mol−2L2s−1
 REACTION ORDER AND RATE CONSTANT UNITS

In some of our examples, the reaction orders in the rate law happen to be the same as
the coefficients in the chemical equation for the reaction. This is merely a coincidence
and very often not the case.

Rate laws may exhibit fractional orders for some reactants, and negative reaction
orders are sometimes observed when an increase in the concentration of one reactant
causes a decrease in reaction rate. A few examples illustrating these points are
provided:

NO 2+ CO NO+CO2 rate=k[NO2]2

CH3CHO CH4+CO rate=k[CH3CHO]2

2N2O5 2NO2+O2 rate=k[N2O5]

2NO2+F2 2NO2F rate=k[NO2][F2]

2NO2Cl 2NO2+Cl2 rate=k[NO2Cl]

It is important to note that rate laws are determined by experiment only and are not
reliably predicted by reaction stoichiometry.

Reaction orders also play a role in determining the units for the rate constant k.
In Example 2, a second-order reaction, we found the units for k to
be L\;mol−4s−1L\;mol−4s−1, whereas in Example 3, a third order reaction, we found
the units for k to be mol−2 L2/s. More generally speaking, the units for the rate constant
for a reaction of
order (m+n)(m+n) are mol1−(m+n)L(m+n)−1s−1mol1−(m+n)L(m+n)−1s−1.Table
7 summarizes the rate constant units for common reaction orders.
Reaction

Units of k

Order

(m+n)(m+n) mol1−(m+n)L(m+n)−1s−1

ZERO mol/L/s

First s−1

Second L/mol/s

Third mol−2 L2 s−1

Table 7. Rate Constants for Common Reaction Orders

Note that the units in the table can also be expressed in terms of molarity (M) instead
of mol/L. Also, units of time other than the second (such as minutes, hours, days) may
be used, depending on the situation.
 COLLISION THEORY

We should not be surprised that atoms, molecules, or ions must collide before they
can react with each other. Atoms must be close together to form chemical bonds. This
simple premise is the basis for a very powerful theory that explains many observations
regarding chemical kinetics, including factors affecting reaction rates.

Collision theory is based on the following postulates:

1. The rate of a reaction is proportional to the rate of reactant collisions:

reaction\;rate∝#collisions\time

2. The reacting species must collide in an orientation that allows contact between
the atoms that will become bonded together in the product.
3. The collision must occur with adequate energy to permit mutual penetration of
the reacting species’ valence shells so that the electrons can rearrange and form
new bonds (and new chemical species).

4. We can see the importance of the two physical factors noted in postulates 2 and
3, the orientation and energy of collisions, when we consider the reaction of
carbon monoxide with oxygen:
5. 2CO(g)+O2(g)⟶2CO2(g)2CO(g)+O2(g)⟶2CO2(g)
6. Carbon monoxide is a pollutant produced by the combustion of hydrocarbon
fuels. To reduce this pollutant, automobiles have catalytic converters that use a
catalyst to carry out this reaction. It is also a side reaction of the combustion of
gunpowder that results in muzzle flash for many firearms. If carbon monoxide
and oxygen are present in sufficient quantity, the reaction is spontaneous at
high temperature and pressure.
7. The first step in the gas-phase reaction between carbon monoxide and oxygen
is a collision between the two molecules:
8.CO(g)+O2(g)⟶CO2(g)+O(g)CO(g)+O2(g)⟶CO2(g)+O(g)
9.Although there are many different possible orientations the
two molecules can have relative to each other, consider the two presented
in Figure 1. In the first case, the oxygen side of the carbon monoxide molecule
collides with the oxygen molecule. In the second case, the carbon side of the
carbon monoxide molecule collides with the oxygen molecule. The second case
is clearly more likely to result in the formation of carbon dioxide, which has a
central carbon atom bonded to two oxygen atoms (O=C=O). This is a rather
simple example of how important the orientation of the collision is in terms of
creating the desired product of the reaction.
Figure 1. Illustrated are two collisions that might take place between carbon monoxide and
oxygen molecules. The orientation of the colliding molecules partially determines whether a
reaction between the two molecules will occur.

If the collision does take place with the correct orientation, there is still no guarantee
that the reaction will proceed to form carbon dioxide. Every reaction requires a certain
amount of activation energy for it to proceed in the forward direction, yielding an
appropriate activated complex along the way. As Figure 2 demonstrates, even a
collision with the correct orientation can fail to form the reaction product. In the study
of reaction mechanisms, each of these three arrangements of atoms is called a
proposed activated complex or transition state.
Figure 2. Possible transition states (activated complexes) for carbon monoxide
reacting with oxygen to form carbon dioxide. Solid lines represent covalent bonds,
while dotted lines represent unstable orbital overlaps that may, or may not, become
covalent bonds as product is formed. In the first two examples in this figure, the O=O
double bond is not impacted; therefore, carbon dioxide cannot form. The third
proposed transition state will result in the formation of carbon dioxide if the third
“extra” oxygen atom separates from the rest of the molecule.

In most circumstances, it is impossible to isolate or identify a transition state or

activated complex. In the reaction between carbon monoxide and oxygen to form
carbon dioxide, activated complexes have only been observed spectroscopically in
systems that utilize a heterogeneous catalyst. The gas-phase reaction occurs too
rapidly to isolate any such chemical compound.

Collision theory explains why most reaction rates increase as concentrations increase.
With an increase in the concentration of any reacting substance, the chances for
collisions between molecules are increased because there are more molecules per unit
of volume. More collisions mean a faster reaction rate, assuming the energy of the
collisions is adequate.

ACTIVATION ENERGY AND THE ARRHENIUS EQUATION

The minimum energy necessary to form a product during a collision between reactants
is called the activation energy (Ea). The kinetic energy of reactant molecules plays an
important role in a reaction because the energy necessary to form a product is
provided by a collision of a reactant molecule with another reactant molecule. (In
single-reactant reactions, activation energy may be provided by a collision of the
reactant molecule with the wall of the reaction vessel or with molecules of an inert
contaminant.) If the activation energy is much larger than the average kinetic energy
of the molecules, the reaction will occur slowly: Only a few fast-moving molecules
will have enough energy to react. If the activation energy is much smaller than the
average kinetic energy of the molecules, the fraction of molecules possessing the
necessary kinetic energy will be large; most collisions between molecules will result
in reaction, and the reaction will occur rapidly.

Figure 3 shows the energy relationships for the general reaction of a molecule
of A with a molecule of B to form molecules of C and D:

A+B⟶C+DA+B⟶C+D
The figure shows that the energy of the transition state is higher than that of the
reactants A and B by an amount equal to Ea, the activation energy. Thus, the sum of
the kinetic energies of A and B must be equal to or greater than Ea to reach the
transition state. After the transition state has been reached, and as C and D begin to
form, the system loses energy until its total energy is lower than that of the initial
mixture. This lost energy is transferred to other molecules, giving them enough energy
to reach the transition state. The forward reaction (that between molecules A and B)
therefore tends to take place readily once the reaction has started. In Figure 3,
ΔH represents the difference in enthalpy between the reactants (A and B) and the
products (C and D). The sum of Ea and ΔH represents the activation energy for the
reverse reaction:

C+D⟶A+B

Figure 3. This graph shows the potential energy relationships for the reaction A + B⟶C + D.
The dashed portion of the curve represents the energy of the system with a molecule of A and a
molecule of B present, and the solid portion the energy of the system with a molecule of C and a
molecule of D present. The activation energy for the forward reaction is represented by Ea. The
activation energy for the reverse reaction is greater than that for the forward reaction by an
amount equal to ΔH. The curve’s peak is represented the transition state.

We can use the Arrhenius equation to relate the activation energy and the rate
constant, k, of a given reaction:

k=Ae−Ea/RTk=Ae−Ea/RT

In this equation, R is the ideal gas constant, which has a value 8.314 J/mol/K, T is
temperature on the Kelvin scale, Ea is the activation energy in joules per mole, e is the
constant 2.7183, and A is a constant called the frequency factor, which is related to
the frequency of collisions and the orientation of the reacting molecules.

Both postulates of the collision theory of reaction rates are accommodated in the
Arrhenius equation. The frequency factor A is related to the rate at which collisions
having the correct orientation occur. The exponential term, e−Ea/RTe−Ea/RT, is related
to the fraction of collisions providing adequate energy to overcome the activation
barrier of the reaction.

At one extreme, the system does not contain enough energy for collisions to overcome
the activation barrier. In such cases, no reaction occurs. At the other extreme, the
system has so much energy that every collision with the correct orientation can
overcome the activation barrier, causing the reaction to proceed. In such cases, the
reaction is nearly instantaneous.

The Arrhenius equation describes quantitatively much of what we have already

discussed about reaction rates. For two reactions at the same temperature, the reaction
with the higher activation energy has the lower rate constant and the slower rate. The
larger value of Ea results in a smaller value for e−Ea/RTe−Ea/RT, reflecting the smaller
fraction of molecules with enough energy to react. Alternatively, the reaction with the
smaller Ea has a larger fraction of molecules with enough energy to react. This will be
reflected as a larger value of e−Ea/RTe−Ea/RT, a larger rate constant, and a faster rate
for the reaction. An increase in temperature has the same effect as a decrease in
activation energy. A larger fraction of molecules has the necessary energy to react
(Figure 4), as indicated by an increase in the value of e−Ea/RTe−Ea/RT. The rate
constant is also directly proportional to the frequency factor, A. Hence a change in
conditions or reactants that increases the number of collisions with a favorable
orientation for reaction results in an increase in A and, consequently, an increase in k.
Figure 4. (a) As the activation energy of a reaction decreases, the number of
molecules with at least this much energy increases, as shown by the shaded areas.
(b) At a higher temperature, T2, more molecules have kinetic energies greater
than Ea, as shown by the yellow shaded area.

A convenient approach to determining Ea for a reaction involves the measurement

of k at different temperatures and using of an alternate version of the Arrhenius
equation that takes the form of linear equation:

Ink (−EaR) (1\T) + ln A

Y mx + b

Thus, a plot of ln k versus 1\T 1\T gives a straight line with the slope –Ea\R−Ea
from which Ea may be determined. The intercept gives the value of ln A.

Example 1

Determination of Ea
The variation of the rate constant with temperature for the decomposition of HI(g) to
H2(g) and I2(g) is given here. What is the activation energy for the reaction?

2HI(g)⟶H2(g)+I2(g)

T (K) k (L/mol/s)

555 3.52 × 10 −7
575 1.22 × 10 −6
645 8.59 × 10 −5
700 1.16 × 10 −3
781 3.95 × 10 −2

Figure 5 is a graph of ln k versus 1\T. To determine the slope of the line, we need two
values of ln k, which are determined from the line at two values of 1\T (one near each
end of the line is preferable). For example, the value of ln k determined from the line
when 1\T=1.25×10−31\T=1.25×10−3 is −2.593; the value
when 1\T=1.78×10−31\T=1.78×10−3 is −14.447.
Figure 5. This graph shows the linear relationship between ln k and 1/T for the reaction
2HI⟶H2 + I2 according to the Arrhenius equation.

The slope of this line is given by the following expression:

Slope Δ(ln k)\ Δ(1\T)

(−14.447)−(−2.593)\ (1.78×10−3K−1)−(1.25×10−3K−1)

−11.854\ 0.53×10−3K−1 =2.2×104K

−Ea\R

Ea=−slope×R=−(−2.2×104K×8.314J\;mol−1K−1)Ea=−slope×R=−(−2.2×104K×8.314⁢
J\;mol−1⁢K−1)
Ea=1.8×105J\;mol−1

In many situations, it is possible to obtain a reasonable estimate of the activation

energy without going through the entire process of constructing the Arrhenius plot.
The Arrhenius equation:
 CATALYSIS

We have seen that the rate of many reactions can be accelerated by catalysts. A
catalyst speeds up the rate of a reaction by lowering the activation energy; in
addition, the catalyst is regenerated in the process. Several reactions that are
thermodynamically favorable in the absence of a catalyst only occur at a reasonable
rate when a catalyst is present. One such reaction is catalytic hydrogenation, the
process by which hydrogen is added across an alkene C=C bond to afford the
saturated alkane product. A comparison of the reaction coordinate diagrams (also
known as energy diagrams) for catalyzed and uncatalyzed alkene hydrogenation is
shown in

Figure 1. This graph compares the reaction coordinates for catalyzed and uncatalyzed alkene
hydrogenation.

Catalysts function by providing an alternate reaction mechanism that has a lower

activation energy than would be found in the absence of the catalyst. In some cases,
the catalyzed mechanism may include additional steps, as depicted in the reaction
diagrams shown in Figure 2. This lower activation energy results in an increase in rate
as described by the Arrhenius equation. Note that a catalyst decreases the activation
energy for both the forward and the reverse reactions and hence accelerates both the
forward and the reverse reactions. Consequently, the presence of a catalyst will
permit a system to reach equilibrium more quickly, but it has no effect on the position
of the equilibrium as reflected in the value of its equilibrium constant (see the later
chapter on chemical equilibrium).
Figure 2. This potential energy diagram shows the effect of a catalyst on the
activation energy. The catalyst provides a different reaction path with a lower
activation energy. As shown, the catalyzed pathway involves a two-step mechanism
(note the presence of two transition states) and an intermediate species
(represented by the valley between the two transitions states).

Example 1

Using Reaction Diagrams to Compare Catalyzed Reactions

The two reaction diagrams here represent the same reaction: one without a catalyst
and one with a catalyst. Identify which diagram suggests the presence of a catalyst,
and determine the activation energy for the catalyzed reaction:
Solution

A catalyst does not affect the energy of reactant or product, so those aspects of the
diagrams can be ignored; they are, as we would expect, identical in that respect. There
is, however, a noticeable difference in the transition state, which is distinctly lower in
diagram (b) than it is in (a). This indicates the use of a catalyst in diagram (b). The
activation energy is the difference between the energy of the starting reagents and the
transition state—a maximum on the reaction coordinate diagram. The reagents are at 6
kJ and the transition state is at 20 kJ, so the activation energy can be calculated as
follows:

Ea=20kJ−6kJ=14kJ

Check Your Learning

Determine which of the two diagrams here (both for the same reaction) involves a
catalyst, and identify the activation energy for the catalyzed reaction:

Answer:

Diagram (b) is a catalyzed reaction with an activation energy of about 70 kJ.