Chemical Kinetics

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General Chemistry II: Chemical Kinetics 1

Diana, Michael John Jose


April 01, 2023

Chapter Outline importance when the yield or rate of


1. Chemical Reaction Rates a reaction needs to be controlled.
2. Factors Affecting Reaction The study of chemical kinetics
Rates concerns the second and third
3. Rate Laws questions—that is, the rate at which
4. Integrated Rate Laws a reaction yields products, and the
5. Collision Theory molecular-scale means by which a
6. Catalysis reaction occurs. In this chapter, we
will examine the factors that
influence the rates of chemical
reactions, the mechanisms by which
reactions proceed, and the
quantitative techniques used to
determine and describe the rate at
which reactions occur.

1. Chemical Reaction Rates

By the end of this section, you will


Figure 1 An agama lizard basks in be able to:
the sun. As its body warms, the • Define chemical reaction rate
chemical reactions of its metabolism • Derive rate expressions from
speed the balanced equation for a
up. given chemical reaction
Introduction • Calculate reaction rates from
experimental data.
The lizard in the photograph is
not simply enjoying the sunshine or A rate is a measure of how some
working on its tan. The heat from property varies with time. Speed is
the sun’s rays is critical to the a familiar rate that expresses the
lizard’s survival. A warm lizard can distance traveled by an object in a
move faster than a cold one because given amount of time. Wage is a rate
the chemical reactions that allow that represents the amount of money
its muscles to move occur more earned by a person working for a
rapidly at higher temperatures. In given amount of time. Likewise, the
the absence of warmth, the lizard is rate of a chemical reaction is a
an easy meal for predators. measure of how much reactant is
consumed, or how much product is
From baking a cake to produced, by the reaction in each
determining the useful lifespan of amount of time.
a bridge, rates of chemical
reactions play important roles in The rate of reaction is the change
our understanding of processes that in the amount of a reactant or
involve chemical changes. When product per unit time. Reaction
planning to run a chemical reaction, rates are therefore determined by
we should ask at least two measuring the time dependence of
questions. The first is: “Will the some property that can be related to
reaction produce the desired reactant or product amounts. Rates
products in useful quantities?” The of reactions that consume or produce
second question is: “How rapidly gaseous substances, for example, are
will the reaction occur?” A reaction conveniently determined by
that takes 50 years to produce a measuring changes in volume or
product is about as useful as one pressure. For reactions involving
that never gives a product at all. one or more colored substances,
A third question is often asked when rates may be monitored via
investigating reactions in greater measurements of light absorption.
detail: “What specific molecular- For reactions involving aqueous
level processes take place as the electrolytes, rates may be measured
reaction occurs?” Knowing the answer via changes in a solution’s
to this question is of practical conductivity.

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General Chemistry II: Chemical Kinetics 2
Diana, Michael John Jose
April 01, 2023

For reactants and products in To obtain the tabulated results


solution, their relative amounts for this decomposition, the
(concentrations) are conveniently concentration of hydrogen peroxide
used for purposes of expressing was measured every 6 hours over the
reaction rates. If we measure the course of a day at a constant
concentration of hydrogen peroxide, temperature of 40 °C. Reaction rates
H2O2, in an aqueous solution, we were computed for each time interval
find that it changes slowly over by dividing the change in
time as the H2O2 decomposes, concentration by the corresponding
according to the equation: time increment, as shown here for
the first 6-hour period:
2H2 O2(aq) ⟶ 2H2 O(l) + O2(g)
The rate at which the hydrogen
peroxide decomposes can be expressed
in terms of the rate of change of
its concentration, as shown here: Notice that the reaction rates
vary with time, decreasing as the
reaction proceeds. Results for the
last 6-hour period yield a reaction
rate of:

This mathematical representation of This behavior indicates the


the change in species concentration reaction continually slows with
over time is the rate expression for time. Using the concentrations at
the reaction. The brackets indicate the beginning and end of a time
molar concentrations, and the symbol period over which the reaction rate
delta (Δ) indicates “change in.” is changing results in the
Thus, [H2 O2]t1 represents the molar calculation of an average rate for
concentration of hydrogen peroxide the reaction over this time
at some time t1; likewise, [H2 O2]t2 interval. At any specific time, the
represents the molar concentration rate at which a reaction is
of hydrogen peroxide at a later time proceeding is known as its
t2; and Δ[H2O2] represents the instantaneous rate. The
change in molar concentration of instantaneous rate of a reaction at
hydrogen peroxide during the time “time zero,” when the reaction
interval Δt (that is, t2 − t1). commences, is its initial rate.
Since the reactant concentration Consider the analogy of a car
decreases as the reaction proceeds, slowing down as it approaches a stop
Δ[H2O2] is a negative quantity; we
sign. The vehicle’s initial rate—
place a negative sign in front of analogous to the beginning of a
the expression because reaction chemical reaction—would be the
rates are, by convention, positive speedometer reading at the moment
quantities. Figure 2 provides an
the driver begins pressing the
example of data collected brakes (t0). A few moments later,
during the decomposition of H2O2. the instantaneous rate at a specific
moment—call it t1—would be somewhat
slower, as indicated by the
speedometer reading at that point in
time. As time passes, the
instantaneous rate will continue to
fall until it reaches zero, when the
car (or reaction) stops. Unlike
instantaneous speed, the car’s
average speed is not indicated by
Figure 2 The rate of decomposition the speedometer; but it can be
of H2O2 in an aqueous solution calculated as the ratio of the
decreases as the concentration of distance traveled to the time
H2O2 decreases. required to bring the vehicle

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General Chemistry II: Chemical Kinetics 3
Diana, Michael John Jose
April 01, 2023

to a complete stop (Δt). Like the state, temperature,


decelerating car, the average rate concentration, and catalysis
of a chemical reaction will fall on reaction rates
somewhere between its initial and
final rates. The rates at which reactants
are consumed and products are formed
The instantaneous rate of a during chemical reactions vary
reaction may be determined one of greatly. We can identify five
two ways. If experimental conditions factors that affect the rates of
permit the measurement of chemical reactions: the chemical
concentration changes over very nature of the reacting substances,
short time intervals, then average the state of subdivision (one large
rates computed as described earlier lump versus many small particles) of
provide reasonably good the reactants, the temperature of
approximations of instantaneous the reactants, the concentration of
rates. Alternatively, a graphical the reactants, and the presence of
procedure may be used that, in a catalyst.
effect, yields the results that
would be obtained if short time The Chemical Nature of the
interval measurements were Reacting Substances
possible. If we plot the
concentration of hydrogen peroxide The rate of a reaction depends
against time, the instantaneous rate on the nature of the participating
of decomposition of H2O2 at any time substances. Reactions that appear
t is given by the slope of a straight similar may have different rates
line that is tangent to the curve at under the same conditions, depending
that time (Figure 3). We can use on the identity of the reactants.
calculus to evaluating the slopes of For example, when small pieces of
such tangent lines, but the the metals iron and sodium are
procedure for doing so is beyond the exposed to air, the sodium reacts
scope of this chapter. completely with air overnight,
whereas the iron is barely affected.
The active metals calcium and sodium
both react with water to form
hydrogen gas and a base. Yet calcium
reacts at a moderate rate, whereas
sodium reacts so rapidly that the
reaction is almost explosive.

The State of Subdivision of the


Reactants

Figure 3 This graph shows a plot of Except for substances in the gaseous
concentration versus time for a state or in solution, reactions
1.000 M solution of H2O2. The rate occur at the boundary, or interface,
at any instant is equal to the between two phases. Hence, the rate
opposite of the slope of a line of a reaction between two phases
tangential to this curve at that depends to a great extent on the
time. Tangents are shown at t = 0 h surface contact between them. A
(“initial rate”) and at t = 10 h finely divided solid has more
(“instantaneous rate” at that surface area available for reaction
particular time). than does one large piece of the
same substance. Thus a liquid will
2. Factors Affecting Reactions Rate react more rapidly with a finely
divided solid than with a large
By the end of this section, you piece of the same solid. For
will be able to: example, large pieces of iron react
slowly with acids; finely divided
iron reacts much more rapidly
• Describe the effects of
(Figure 4). Large pieces of wood
chemical nature, physical
smolder, smaller pieces burn

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General Chemistry II: Chemical Kinetics 4
Diana, Michael John Jose
April 01, 2023

rapidly, and saw dust burns CaCO3(s) + H2SO3(aq) ⟶ CaSO3(aq) +


explosively. CO2(g) + H2O(l)

In a polluted atmosphere where


the concentration of sulfur dioxide
is high, calcium carbonate
deteriorates more rapidly than in
less polluted air. Similarly,
phosphorus burns much more rapidly
in an atmosphere of pure oxygen than
Figure 4 (a) Iron powder reacts in air, which is only about 20%
rapidly with dilute hydrochloric oxygen.
acid and produces bubbles of
hydrogen gas because the powder has
a large total surface area: 2Fe(s)
+ 6HCl(aq) ⟶ 2FeCl3(aq) + 3H2(g).
(b) An iron nail reacts more slowly.

Temperature of the Reactants

Chemical reactions typically


occur faster at higher temperatures.
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 Figure 5 Statues made from carbonate
days. We use a burner or a hot plate compounds such as limestone and
in the laboratory to increase the marble typically weather slowly over
speed of reactions that proceed time due to the actions of water,
slowly at ordinary temperatures. In and thermal expansion and
many cases, an increase in contraction. However, pollutants
temperature of only 10 °C will like sulfur dioxide can accelerate
approximately double the rate of a weathering. As the concentration of
reaction in a homogeneous system. air pollutants increases,
deterioration of limestone occurs
Concentrations of the Reactants more rapidly. (credit: James P
Fisher III)
The rates of many reactions depend
on the concentrations of the The Presence of a Catalyst
reactants. Rates usually increase Hydrogen peroxide solutions foam when
when the concentration of one or poured onto an open wound because
more of the reactants increases. For substances in the exposed tissues act
as catalysts, increasing the rate of
example, calcium carbonate (CaCO3) hydrogen peroxide’s decomposition.
deteriorates as a result of its However, in the absence of these
reaction with the pollutant sulfur catalysts (for example, in the bottle
dioxide. The rate of this reaction in the medicine cabinet) complete
depends on the amount of sulfur decomposition can take months. A
dioxide in the air (Figure 5). An catalyst is a substance that increases
acidic oxide, sulfur dioxide the rate of a chemical reaction by
combines with water vapor in the air lowering the activation energy without
to produce sulfurous acid in the itself being consumed by the reaction.
following reaction: Activation energy is the minimum amount
of energy required for a chemical
reaction to proceed in the forward
SO2(g) + H2 O(g) ⟶ H2SO3(aq) direction. A catalyst increases the
reaction rate by providing an
Calcium carbonate reacts with alternative pathway or mechanism for
sulfurous acid as follows: the reaction to follow (Figure 6).
Catalysis will be discussed in greater

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General Chemistry II: Chemical Kinetics 5
Diana, Michael John Jose
April 01, 2023

detail later in this chapter as it determined experimentally by


relates to observing how the rate of a reaction
changes as the concentrations of the
mechanisms of reactions.
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]n

Figure 6. The presence of a catalyst If the exponent m is 1, thereaction


increases the rate of a reaction by is first order with respect to A. If
lowering its activation energy. m is 2, the reaction is second order
with respect to A. If n is 1, the
3. Rate Laws reaction is first order in B. If n
is 2, the reaction is second order
By the end of this section, you in B. If m or n is zero, the reaction
will be able to: is zero order in A or B,
respectively, and the rate of the
reaction is not affected by the
• Explain the form and function
concentration of that reactant. The
of a rate law
overall reaction order is the sum of
• Use rate laws to calculate the orders with respect to each
reaction rates reactant. If m = 1 and n = 1, the
• Use rate and concentration data overall order of the reaction is
to identify reaction orders and second order (m + n = 1 + 1 = 2).
derive rate laws
The rate law:
As described in the previous rate = k[H2O2]
module, the rate of a reaction is
affected by the concentrations of describes a reaction that is first
reactants. Rate laws or rate order in hydrogen peroxide and first
equations are mathematical order overall. The rate law:
expressions that describe the
relationship between the rate of a rate = k [C4H6]2
chemical reaction and the
concentration of its reactants. In describes a reaction that is second
general, a rate law (or differential order in C4H6 and second order
rate law, as it is sometimes called) overall. The rate law:
takes this form:
rate = k[H+][OH−]
rate = k[A]m[B]n[C] p…

describes a reaction that is first


in which [A], [B], and [C] represent order in H+ , first order in OH− ,
the molar concentrations of and second order overall.
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

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General Chemistry II: Chemical Kinetics 6
Diana, Michael John Jose
April 01, 2023

Sample Problem: • Define half-life and carry out


related calculations
• Identify the order of a
reaction from
concentration/time data

The rate laws we have seen thus far


relate the rate and the concentrations
of reactants. We can also determine a
second form of each rate law that
relates the concentrations of reactants
and time. These are called integrated
rate laws. We can use an integrated
rate law to determine the amount of
reactant or product present after a
period of time or to estimate the time
required for a reaction to proceed to
a certain extent. For example, an
integrated rate law is used to
determine the length of time a
radioactive material must be stored for
its radioactivity to decay to a safe
level.

Using calculus, the differential


rate law for a chemical reaction can be
integrated with respect to time to give
an equation that relates the amount of
reactant or product present in a
reaction mixture to the elapsed time of
the reaction. This process can either
be very straightforward or very
complex, depending on the complexity of
the differential rate law. For purposes
of discussion, we will focus on the
It is sometimes helpful to use resulting integrated rate laws for
a more explicit algebraic method, first-, second-, and zero-order
often referred to as the method of reactions.
initial rates, to determine the
orders in rate laws. To use this First-Order Reactions
method, we select two sets of rate
data that differ in the An equation relating the rate
concentration of only one reactant constant k to the initial
and set up a ratio of the two rates concentration [A]0 and the
and the two rate laws. After concentration [A]t present after any
canceling terms that are equal, we given time t can be derived for a
are left with an equation that first-order reaction and shown to
contains only one unknown, the be:
coefficient of the concentration
that varies. We then solve this
equation for the coefficient.
Or
4. Integrated Rate Laws

By the end of this section, you


will be able to:
Second-Order Reactions
• Explain the form and function The equations that relate the
of an integrated rate law concentrations of reactants and the
• Perform integrated rate law rate constant of second-order
calculations for zero-, first- reactions are fairly
, and second-order reactions

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General Chemistry II: Chemical Kinetics 7
Diana, Michael John Jose
April 01, 2023

complicated. We will limit ourselves


to the simplest second-order
reactions, namely, those with rates
that are dependent upon just one
reactant’s concentration and
described by the differential rate
law:
Rate = k[A]2

For these second-order


reactions, the integrated rate law
is:

where the terms in the equation have


their usual meanings as defined Figure 7. The decomposition of NH3
earlier. on a tungsten (W) surface is a zero-
order reaction, whereas on a quartz
Zero-Order Reactions (SiO2) surface, the reaction is
first order.
For zero-order reactions, the
differential rate law is: The Half-Life of a Reaction
Rate = k[A]0 = k
The half-life of a reaction (t1/2)
A zero-order reaction thus is the time required for one-half of
exhibits a constant reaction rate, a given amount of reactant to be
regardless of the concentration of consumed. In each succeeding half-
its reactants. life, half of the remaining
concentration of the reactant is
The integrated rate law for a consumed. Using the decomposition
zero-order reaction also has the of hydrogen peroxide as an example,
form of the equation of a straight we find that during the first half-
line: life (from 0.00 hours to 6.00
[A] = −kt + [A]0 hours), the concentration of H2O2
y = mx + b decreases from 1.000 M to 0.500 M.
During the second half-life (from
A plot of [A] versus t for a 6.00 hours to 12.00 hours), it
zero-order reaction is a straight decreases from 0.500 M to 0.250 M;
line with a slope of −k and an during the third half-life, it
intercept of [A]0. decreases from 0.250 M to 0.125
M. The concentration of H2O2
Figure 7 shows a plot of [NH3] versus decreases by half during each
t for the decomposition of ammonia successive period of 6.00 hours. The
on a hot tungsten wire and for the decomposition of hydrogen peroxide
decomposition of ammonia on hot is a first-order reaction, and, as
quartz (SiO2). The decomposition of can be shown, the half-life of a
NH3 on hot tungsten is zero order; first-order reaction is independent
the plot is a straight line. The of the concentration of the
decomposition of NH3 on hot quartz reactant. However, half-lives of
is not zero order (it is first reactions with other orders depend
order). From the slope of the line on the concentrations of the
for the zero-order decomposition, we reactants.
can determine the rate constant:
First-Order Reactions
slope = −k = 1.3110−6 mol/L/s
We can derive an equation for
determining the half-life of a
first-order reaction from the
alternate form of the integrated
rate law as follows:

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General Chemistry II: Chemical Kinetics 8
Diana, Michael John Jose
April 01, 2023

For a second-order reaction,


t 1/2 is inversely proportional to
the concentration of the reactant,
and the half-life increases as the
reaction proceeds because the
If we set the time t equal to concentration of reactant
the half-life, t1/2, the decreases. Consequently, we find the
corresponding concentration of A at use of the half-life concept to be
this time is equal to one-half of more complex for second-order
its initial concentration. Hence, reactions than for first-order
when t = t1/2, reactions. Unlike with first-order
reactions, the rate constant of a
second-order reaction cannot be
calculated directly from the half-
Therefore: life unless the initial
concentration is known.

Zero-Order Reactions

We can derive an equation for


Thus: calculating the half-life of a zero-
order reaction as follows:

We can see that the half-life


of a first-order reaction is
inversely proportional to the rate
constant k. A fast reaction (shorter
half-life) will have a larger k; a
slow reaction (longer half-life)
will have a smaller k.

Second-Order Reactions The half-life of a zero-order


reaction increases as the initial
We can derive the equation for concentration increases. Equations
calculating the half-life of a for both differential and integrated
second order as follows: rate laws and the corresponding
half-lives for zero-, first-, and
second-order reactions are
summarized in Table 1.

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General Chemistry II: Chemical Kinetics 9
Diana, Michael John Jose
April 01, 2023

5. Collision Theory catalytic converters that use a


catalyst to carry out this reaction.
By the end of this section, you It is also a side reaction of the
will be able to: combustion of gunpowder that results
in muzzle flash for many firearms.
• Use the postulates of collision If carbon monoxide and oxygen are
theory to explain the effects present in sufficient quantity, the
of physical state, reaction is spontaneous at high
temperature, and concentration temperature and pressure.
on reaction rates
• Define the concepts of The first step in the gas-phase
activation energy and reaction between carbon monoxide and
transition state. oxygen is a collision between the
two molecules:
We should not be surprised that
atoms, molecules, or ions must CO(g) + O2(g) ⟶ CO2(g) + O(g)
collide before they can react with
each other. Atoms Although there are many
must be close together to form different possible orientations the
chemical bonds. This simple premise two molecules can have relative to
is the basis for a very powerful each other, consider the two
theory that explains many presented in Figure 8. In the first
observations regarding chemical case, the oxygen side of the carbon
kinetics, including factors monoxide molecule collides with the
affecting reaction rates. oxygen molecule. In the second case,
the carbon side of the carbon
Collision theory is based on monoxide molecule collides with the
the following postulates: oxygen molecule. The second case is
clearly more likely to result in the
1. The rate of a reaction is formation of carbon dioxide, which
proportional to the rate of reactant has a central carbon atom bonded to
collisions: two oxygen atoms (O = C = O). This
is a rather simple example of how

2. The reacting species must collide important the orientation of the


in an orientation that allows collision is in terms of creating
contact between the atoms that will the desired product of the reaction.
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).
Figure 8 Illustrated are two
We can see the importance of collisions that might take place
the two physical factors noted in between carbon monoxide and oxygen
postulates 2 and 3, the orientation molecules. The orientation of the
and energy of collisions, when we colliding molecules partially
consider the reaction of carbon determines whether a reaction
monoxide with oxygen: between the two molecules will
occur.

If the collision does take


place with the correct orientation,
Carbon monoxide is a pollutant
there is still no guarantee that the
produced by the combustion of
reaction will proceed to form carbon
hydrocarbon fuels. To reduce this
dioxide. Every reaction requires a
pollutant, automobiles have

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General Chemistry II: Chemical Kinetics 10
Diana, Michael John Jose
April 01, 2023

certain amount of activation energy 6. Catalysis


for it to proceed in the forward
direction, yielding an appropriate By the end of this section, you
activated complex along the way. As will be able to:
Figure 9 demonstrates, even a • Explain the function of a
collision with the correct catalyst in terms of reaction
orientation can fail to form the mechanisms and potential
reaction product. In the study of energy diagrams
reaction mechanisms, each of these • List examples of catalysis in
three arrangements of atoms is natural and industrial
called a proposed activated complex processes
or transition state.
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
Figure 9 Possible transition states catalyst is regenerated in the
(activated complexes) for carbon process. Several reactions that are
monoxide reacting with oxygen to thermodynamically favorable in the
form carbon dioxide. Solid lines absence of a catalyst only occur at
represent covalent bonds, while a reasonable rate when a catalyst is
dotted lines represent unstable present. One such reaction is
orbital overlaps that may, or may catalytic hydrogenation, the
not, become covalent bonds as process by which hydrogen is added
product is formed. In the first two across an alkene C=C bond to afford
examples in this figure, the O=O the saturated alkane product. A
double bond is not impacted; comparison of the reaction
therefore, carbon dioxide cannot coordinate diagrams (also known as
form. The third proposed transition energy diagrams) for catalyzed and
state will result in the uncatalyzed alkene hydrogenation is
shown in Figure 10.

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 Figure 10 This graph compares the
compound. Collision theory explains reaction coordinates for catalyzed
why most reaction rates increase as and uncatalyzed alkene
concentrations increase. With an hydrogenation.
increase in the concentration of any
reacting substance, the chances for Catalysts function by providing an
collisions between molecules are alternate reaction mechanism that
increased because there are more has a lower activation energy than
molecules per unit of volume. More would be found in the absence of the
collisions mean a faster reaction catalyst. In some cases, the
rate, assuming the energy of the catalyzed mechanism may include
collisions is adequate. additional steps, as depicted

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General Chemistry II: Chemical Kinetics 11
Diana, Michael John Jose
April 01, 2023

in the reaction diagrams shown in earth’s ozone layer. Ozone in the


Figure 11. This lower activation upper atmosphere, which protects the
energy results in an increase in earth from ultraviolet radiation, is
rate as described by the Arrhenius formed when oxygen molecules absorb
equation. Note that a catalyst ultraviolet light and undergo the
decreases the activation energy for reaction:
both the forward and the reverse
reactions and hence accelerates both
the forward and the reverse
reactions. Consequently, the Ozone is a relatively unstable
presence of a catalyst will permit molecule that decomposes to yield
a system to reach equilibrium more diatomic oxygen by the reverse of
quickly, but it has no effect on the this equation. This decomposition
position of the equilibrium as reaction is consistent with the
reflected in the value of its following mechanism:
equilibrium constant (see the later
chapter on chemical equilibrium).

The presence of nitric oxide,


NO, influences the rate of
decomposition of ozone. Nitric oxide
acts as a catalyst in the following
mechanism:

The overall chemical change for


the catalyzed mechanism is the same
as:

Figure 11 This potential energy


The nitric oxide reacts and is
diagram shows the effect of a
regenerated in these reactions. It
catalyst on the activation energy.
is not permanently used up; thus, it
The catalyst provides a different
acts as a catalyst.
reaction path with a lower
activation energy. As shown, the
The rate of decomposition of
catalyzed pathway involves a two-
ozone is greater in the presence of
step mechanism (note the presence of
nitric oxide because of the
two transition states) and an
catalytic activity of NO. Certain
intermediate species (represented
compounds that contain chlorine also
by the valley between the two
catalyze the decomposition of ozone.
transitions states).
Heterogeneous Catalysts
Homogeneous Catalysts
A heterogeneous catalyst is a
A homogeneous catalyst is
catalyst that is present in a
present in the same phase as the
different phase (usually a solid)
reactants. It interacts with a
than the reactants. Such catalysts
reactant to form an intermediate
generally function by furnishing an
substance, which then decomposes or
active surface upon which a reaction
reacts with another reactant in one
can occur. Gas and liquid phase
or more steps to regenerate the
reactions catalyzed by
original catalyst and form product.
heterogeneous catalysts occur on the
surface of the catalyst rather than
As an important illustration of
within the gas or liquid
homogeneous catalysis, consider the
phase.

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General Chemistry II: Chemical Kinetics 12
Diana, Michael John Jose
April 01, 2023

Heterogeneous catalysis has at oxidation of ammonia to nitric acid,


least four steps: and the synthesis of methanol,
CH3OH. Heterogeneous catalysts are
1. Adsorption of the reactant onto also used in the catalytic
the surface of the catalyst converters found on most gasoline-
2. Activation of the adsorbed powered Automobiles.
reactant
3. Reaction of the adsorbed Key Equations:
reactant
4. Diffusion of the product from
the surface into the gas or
liquid phase (desorption).

Any one of these steps may be slow


and thus may serve as the rate
determining step. In general,
however, in the presence of the
catalyst, the overall rate of the
reaction is faster than it would be
if the reactants were in the gas or
liquid phase. Figure 12 illustrates
the steps that chemists believe to
occur in the reaction of compounds
containing a carbon–carbon double
bond with hydrogen on a nickel
catalyst. Nickel is the catalyst Summary
used in the hydrogenation of
polyunsaturated fats and oils (which 1. Chemical Reaction Rates
contain several carbon–carbon
double bonds) to produce saturated The rate of a reaction can be
fats and oils (which contain only expressed either in terms of the
carbon–carbon single bonds). decrease in the amount of a reactant
or the increase in the amount of a
product per unit time. Relations
between different rate expressions
for a given reaction are derived
directly from the stoichiometric
coefficients of the equation
representing the reaction.

2. Factors Affecting Reaction Rates


Figure 12. There are four steps in
the catalysis of the reaction C2 H4 The rate of a chemical reaction
+ H2 ⟶ C2 H6 by nickel. (a)Hydrogen is affected by several parameters.
is adsorbed on the surface, breaking Reactions involving two phases
the H–H bonds and forming Ni–H proceed more rapidly when there is
bonds. (b) Ethylene is adsorbed on greater surface area contact. If
the surface, breaking the π-bond and temperature or reactant
forming Ni–C bonds. (c) Atoms concentration is increased, the rate
diffuse across the surface and form of a given reaction generally
new C–H bonds when they collide. (d) increases as well. A catalyst can
C2H6 molecules escape from the increase the rate of a reaction by
nickel surface, since they are not providing an alternative pathway
strongly attracted to nickel. that causes the activation energy of
the reaction to decrease.
Other significant industrial
processes that involve the use of 3. Rate Laws
heterogeneous catalysts include the
preparation of sulfuric acid, the Rate laws provide a
preparation of ammonia, the mathematical description of how

General Chemistry II: DianaMJ2023 dianamj@sac.edu.ph dianamj@up.edu.ph


General Chemistry II: Chemical Kinetics 13
Diana, Michael John Jose
April 01, 2023

changes in the amount of a substance the relation between a reaction’s


affect the rate of a chemical rate constant and its activation
reaction. Rate laws are determined energy, temperature, and dependence
experimentally and cannot be on collision
predicted by reaction orientation.
stoichiometry. The order of reaction
describes how much a change in the 6. Catalysis
amount of each substance affects the
overall rate, and the overall order Catalysts affect the rate of a
of a reaction is the sum of the chemical reaction by altering its
orders for each substance present in mechanism to provide a lower
the reaction. Reaction orders are activation energy. Catalysts can be
typically first order, second order, homogenous (in the same phase as the
or zero order, but fractional and reactants) or heterogeneous (a
even negative orders are possible. different phase than the reactants).

4. Integrated Rate Laws


Reference:
Differential rate laws can be
determined by the method of initial OpenStax College, Chemistry
rates or other methods. We measure OpenStax College. 11 March
values for the initial rates of a 2015.<http://cnx.org/content/c
reaction at different ol11760/latest/>. Chapter 12;
concentrations of the reactants. page. 661-701
From these measurements, we
determine the order of the reaction
in each reactant. Integrated rate
laws are determined by integration
of the corresponding differential
rate laws. Rate constants for those
rate laws are determined from
measurements of concentration at
various times during a reaction.
The half-life of a reaction is
the time required to decrease the
amount of a given reactant by one-
half. The half-life of a zero-order
reaction decreases as the initial
concentration of the reactant in the
reaction decreases. The half-life
of a first-order reaction is
independent of concentration, and
the half-life of a second-order
reaction decreases as the
concentration increases.

5. Collision Theory

Chemical reactions require


collisions between reactant
species. These reactant collisions
must be of proper orientation and
sufficient energy in order to result
in product formation. Collision
theory provides a simple but
effective explanation for the effect
of many experimental parameters on
reaction rates. The Arrhenius
equation describes

General Chemistry II: DianaMJ2023 dianamj@sac.edu.ph dianamj@up.edu.ph

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