CHEMICAL KINETICS

Chemical reactions require varying lengths of time for completion,depending on the characteristics
of the reactants and productsand the conditions under which the reaction is run.Many reactions are
over in a fraction of a second, whereas others cantake much longer. If you add barium ion to an
aqueous solution ofsulfate ion, a precipitate of barium sulfate forms almost immediately. The
reason for studying reaction rates, the speed at which the reaction occurs, is to understandhow
chemical reactions occur. By noting how the rate of a reaction isaffected by changing conditions,
you can sometimes learn the details ofwhat is happening at the molecular level.

Chemical kineticsis the study of reaction rates, how reaction rates change under
varyingconditions, and what molecular events occur during the overall reaction. In the first part of
this topic, we will look at reaction rates and the variables that affect them.What variables affect
reaction rates? The rate of any given reaction may be affected by thefollowing factors:

1. Concentrations of reactants. Often the rate of reaction increases when the concentrationof
a reactant is increased. A piece of steel wool burns with some difficultyin air (20% O2) but
bursts into a dazzling white flame in pure oxygen. Therate of burning increases with the
concentration of O2. In some reactions, however,the rate is unaffected by the concentration
of a particular reactant, as longas it is present at some concentration.
2. Concentration of catalyst. A catalyst is a substance that increases the rate of reaction
without being consumed in the overall reaction. Because the catalyst is not consumed by
the reaction, it does not appear in the balanced chemical equation (although its presence
may be indicated by writing its formula over the arrow). A solution of pure hydrogen
peroxide, H2O2, is stable, but when hydrobromicacid, HBr(aq), is added, H2O2 decomposes
rapidly into H2O and O2


Here HBr acts as a catalyst to speed decomposition.

3. Temperature at which the reaction occurs.Usually reactions speed up when

thetemperature increases. It takes less time to boil an egg at sea level than on amountaintop,
where water boils at a lower temperature. Reactions during cookinggo faster at higher
temperature.
 4. Surface area of a solid reactant or catalyst. If a reaction involves a solid with a gas or
liquid, the surface area of the solid affects the reaction rate. Because the reaction occurs at
the surface of the solid, the rate increases with increasing surface area. A wood fire burns
faster if the logs are chopped into smaller pieces. Similarly, the surface area of a solid
catalyst is important to the rate of reaction.The greater the surface area per unit volume,
the faster the reaction.
Reactions in the gasphase and in liquid solution, factors 1 to 3 are important.

Definition of Reaction Rate

The rate of a reaction is the amount of product formed or the amount of reactant usedup per unit
of time. So that a rate calculation does not depend on the total quantityof reaction mixture used,
you express the rate for a unit volume of the mixture. Therefore,the reaction rate is the increase
in molar concentration of product of a reactionper unit time or the decrease in molar
concentration of reactant per unit time. Theusual unit of reaction rate is moles per liter per second,
mol/(L.s).Consider the gas-phase reaction:

The rate for this reaction could be found by observing the increase in molar concentrationof O 2
produced. You denote the molar concentration of a substance by enclosingits formula in square
brackets. Thus, [O2] is the molar concentrationof O2. In a given time interval,Δt, the molar
concentration of oxygen,[O2], in the reaction vessel increases by the amount Δ[O2]. Thesymbol

Δ(capital Greek delta) means“change in”; you obtain thechange by subtracting the initial value

from the final value. The rateof the reaction is given by:

This equation gives the average rate over the time interval Δt. Ifthe time interval is very short, the
equation gives the instantaneousrate, that is, the rate at a particular instant of time. The
instantaneousrate is also the value of Δ[O2]/Δtfor the tangent at a giveninstant (the straight line
that just touches the curve of concentrationversus time at a given point). See figure below:
The figure above shows the increase in concentration of O2 during the decompositionof N2O5. It
shows the calculation of average rates at two positions on the curve. Forexample, when the time
changes from 600 s to 1200 s (Δt= 600 s), the O2 concentrationincreases by 0.0015 mol/L (=Δ[O2]).
Therefore, the average rate =Δ[O2]/Δt= (0.0015 mol/L)/600 s =2.5X106 mol/(L.s). Later, during
the time intervalfrom 4200 s to 4800 s, the average rate is 5X107 mol/(L.s). Note that the
ratedecreases as the reaction proceeds.

Because the amounts of products and reactants are related by stoichiometry, anysubstance in the
reaction can be used to express the rate of reaction. In the case ofthe decomposition of N2O5 to
NO2 and O2, we gave the rate in terms of the rate offormation of oxygen, Δ[O2]/Δt. However, you
can also express it in terms of the rateof decomposition of N2O5.

Note the negative sign. It always occurs in a rate expression for a reactant in orderto indicate a
decrease in concentration and to give a positive value for the rate. Thus,because [N2O5] decreases,
Δ[N2O5] is negative and Δ[N2O5]/Δtis positive.The rate of decomposition of N2O5 and the rate of
formation of oxygen are easilyrelated. Two moles of N2O5 decompose for each mole of oxygen
formed, so therate of decomposition of N2O5 is twice the rate of formation of oxygen. To equatethe
rates, you must divide the rate of decomposition of N2O5 by 2 (its coefficient inthe balanced
chemical equation).

Rate of formation of O2 = 1/2 (rate of decomposition of N2O5)

Dependence of Rate on Concentration

Experimentally, it has been found that a reaction rate depends on the concentrationsof certain
reactants as well as the concentration of catalyst, if there is one. The rate of this reaction is observed
to be proportional to the concentration of the reactant.

2NO2(g) + F2(g) 2NO2F(g)

When the concentration of reactants is doubled, the rate doubles.When the concentration of
nitrogen dioxide is doubled, the rate doubles.The rate is also proportional to the concentration of
fluorine; doubling the concentrationof fluorine also doubles the rate.

A rate law is an equation that relates the rate of a reaction to the concentrationsof reactants (and
catalyst) raised to various powers. The following equation is therate law for the foregoing reaction:

Rate = k[NO2][F2]

Note that in this rate law both reactant concentrations have an exponent of 1. Here k, called the
rate constant, is proportionality constant in the relationship between rateand concentrations. It
has a fixed value at any given temperature, but it varies withtemperature. Whereas the units of rate
are usually given as mol/(L.s), the units of kdepend on the form of the rate law. For the previous
rate law,

K= Rate /[NO2][F2]

As a more general example, consider the reaction of substances A and B to giveD and E, according
to the balanced equation:

aA+bB dD+eE
You could write the rate law in the form:

Rate =k[A]m[B]n

The exponentsm, and nare frequently, but not always, integers. They must be
determinedexperimentally and they cannot be obtained simply by looking at the balancedequation.
For example, note that the exponents in the equation Rate =k[NO2][F2] haveno relationship to the
coefficients in the balanced equation 2NO2+ F2 → 2NO2F.Once you know the rate law for a
reaction and have found the value of the rateconstant, you can calculate the rate of a reaction for
any values of reactant concentrations.

Reaction Order
You can classify a reaction by its orders. The reaction order with respect to a givenreactant
species equals the exponent of the concentration of that species in the ratelaw, as determined
experimentally. For the reaction of NO2 with F2 to give NO2F, thereaction is first order with respect
to the NO2 because the exponent of [NO2] in therate law is 1. Similarly, the reaction is first order
with respect to F2.The overall order of a reaction equals the sum of the orders of the reactant
speciesin the rate law.Therefore, the reaction is second order overall.

Nitrogen monoxide, NO, reacts with hydrogen according to the equation:

2NO(g) + 2H2(g) N2 + 2H2O(g)

The experimentally determined rate law is: Rate =k[NO]2[H2]. Thus, the reaction is secondorder
in NO, first order in H2, and third order overall.

Acetone, CH3COCH3, reacts with iodine in acidic solution.

H+
CH3COCH3(aq) + I2(aq) CH3COCH2I(aq) + HI(aq)

The experimentally determined rate law is: Rate =k[CH3COCH3][H+]. The reaction is first order
in acetone. It is zero order in iodine; that is, the ratelaw contains the factor [I2]0= 1. Therefore, the
rate does not depend on theconcentration of I2, as long as some concentration of I2 is present. Note
that thereaction is first order in the catalyst, H+. Thus, the overall order is 2.
Although reaction orders frequently have whole-number values (particularly 1 or 2),they can also
be fractional. Zero and negative orders are also possible.

Determining the Rate Law

The experimental determination of the rate law for a reaction requires that you findthe order of the
reaction with respect to each reactant and any catalyst. The initialratemethod is a simple way to
obtain reaction orders. It consists of doing a series ofexperiments in which the initial, or starting,
concentrations of reactants are varied.Then the initial rates are compared, from which the reaction
orders can be deduced.

Initial N2O5 Concentration Initial Rate of Disappearance of N2O5

Experiment 1: 1.0 x 10-2 mol/L 4.8 x 10-6 mol/(L.s)

Experiment 2: 2.0 x 10-2 mol/L 9.6 x 10-6 mol/(L.s)

In Experiment 2, the initial concentrationof N2O5 is twice that in Experiment 1. You then note the
initial rate of disappearanceof N2O5 in each case.

The rate law for this reaction will have the concentration of reactant raised to apower m.

Rate = k[N2O5]m

The value of m (the reaction order) must be determined from the experimental data.Note that when
the N2O5 concentration is doubled, you get a new rate, Rate’, givenby the following equation:

Rate’= k(2[N2O5])m= 2mk[N2O5]m

This rate is 2mtimes the original rate.You can now see how the rate is affected when the
concentration is doubled forvarious choices of m. Suppose m = 2. You get 2m= 22= 4. That is, when
the initialconcentration is doubled, the rate is multiplied by 4. Suppose you divide the initial rate
of reaction of N2O5 from Experiment 2 by theinitial rate from Experiment 1.

9.6 x 10-6 mol/(L.s) /4.8 x 10-6 mol/(L.s) = 2.0

You see that when the N2O5 concentration is doubled, the rate is doubled. This correspondsto the
case m = 1. The rate law must have the form: Rate = k[N2O5]
You can determine the value of the rate constant k by substituting values of therate and N2O5
concentrations from any of the experiments into the rate law.

Worked Example:

Iodide ion is oxidized in acidic solution to triiodide ion, I3-, by hydrogen peroxide.

H2O2(aq) + 3I-(aq) + 2H+(aq) I3-(aq) + 2H2O(l )

A series of four experiments was run at different concentrations, and the initial rates of I3-formation
were determined. From these data,

a. Obtain the reaction orders withrespect to H2O2, I-, and H+ and then
b. Find the rate constant.

Problem Strategy:
a. In order to know the reaction orders of the reactants, you need toknow the rate law.
Using the reactants in the chemical equation, you assume the rate lawhas the following
form:

Rate =k[H2O2]m[I-]n[H+]p

You can determine each of the reaction orders (exponentsm, n, and p) by choosing
experimentsin which all concentrations of reactants except one are held constant.
Solving foreach exponent will require comparing different experiments. Once you
know the reactionorders, you will know the rate law.

Comparing Experiment 1 and Experiment 2, you see that when the

H2O2concentration is doubled (with other concentrations constant), the rate is
doubled. Fromthe table of effect on rate of doubling the initial concentration of
reactant, you see that m = 1. The reaction is first order in H2O2.To solve a problem
such as this in a general way, you approach it algebraically. Youwrite the rate law
for two experiments. (The subscripts denote the experiments.)

This gives 2 = 2m, from which you obtain m = 1. That is, doubling the H2O2
concentrationdoubles the rate.The exponentsn and p are obtained in the same way.
Comparing Experiment 1 andExperiment 3, you see that doubling the I-
concentration (with the other concentrationsconstant) doubles the rate. Therefore,
n = 1 (the reaction is first order in I-). Finally, comparingExperiment 1 and
 Experiment 4, you see that doubling the H+ concentration (holdingother
concentrations constant) has no effect on the rate. Therefore, p= 0 (the reactionis
zero order in H+). Because [H+]0 = 1, the rate law is:

Rate =k[H2O2][I-]

b. To determine the rate constant, you can take the datafrom one of the experiments and
substitute them into the rate law; the only unknown in theequation will be the rate
constant, k.

You calculate the rate constant by substituting values from any of the experiments
intothe rate law. Using Experiment 1, you obtain:

Change of Concentration with Time

A rate law tells you how the rate of a reaction depends on reactant concentrations ata particular
moment. But often you would like to have a mathematical relationshipshowing how a reactant
concentration changes over a period of time. Such an equationwould be directly comparable to the
experimental data, which are usuallyobtained as concentrations at various times. In addition to
summarizing the experimentaldata, this equation would predict concentrations for all times. Using
it, youcould answer questions such as: How long does it take for this reaction to be 50%complete?
to be 90% complete?

Using calculus, we can transform a rate law into a mathematical relationshipbetween

concentration and time called an integrated rate law. Because we will workonly with the final
equations, we need not go into the derivations here. We will lookin some depth at first-order
reactions and briefly at second-order and zero-orderreactions.
Integrated Rate Laws (Concentration—Time Equations)
First-Order Rate Law Let us first look at first-order rate laws. The decompositionof
dinitrogenpentoxide,

has the following rate law:

Using calculus, one can show that such a first-order rate law leads to the followingrelationship
between N2O5 concentration and time:

Here [N2O5]tis the concentration at time t, and [N2O5]0 is the initial concentrationof N2O5 (that is,

the concentration at t = 0). The symbol “ln” denotes the natural logarithm(base e = 2.718 . . .).This

equation enables you to calculate the concentration of N2O5 at any time, onceyou are given the
initial concentration and the rate constant. Also, you can find thetime it takes for the N 2O5
concentration to decrease to a particular value. The ratio [N2O5]t/[N2O5]0 is the fraction of reactant
remaining at time t.

Second-Order Rate Law Consider the reactionaA productsand suppose it has the
second-order rate law:

Using calculus, you can obtain the following relationship between the concentrationof A and the
time.

(second-order integrated rate law)

An example is the decomposition of nitrogen dioxide at moderately high temperatures(300°C to
400°C). 2NO2(g) 2NO(g) + O2(g)

Using the second-order integrated rate law equation, you can calculate the concentration of NO2
at any time duringits decomposition if you know the rate constant and the initial concentration.
At330°C, the rate constant for the decomposition of NO2 is 0.775 L/(mol.s). Supposethe initial
concentration is 0.0030 mol/L. What is the concentration of NO2 after645s? By substituting into
the previous equation, you get:

If you invert both sides of the equation, you find that [NO2]t= 0.0012 mol/L. Thus,after 645s, the
concentration of NO2 decreased from 0.0030 mol/L to 0.0012 mol/L.

Zero-Order ReactionsThere are instances where reactions are zero-order. An example includes
the decompositionof ethyl alcohol in the liver in the presence of the enzyme liver alcohol
dehydrogenase.Once again, consider the reaction with the general form:

aA Products,

which has a zero-order rate law of: Rate =k[A]0 or Rate =k

The relationship between concentration and time for a zero-order reaction is:

[A]t = -kt+ [A]0 (zero-order integrated rate law)

Class exercise

The decomposition of N2O5 to NO2 and O2 is first order, with a rate constant of 4.80 x10-4/s at
45°C.

a. If the initial concentration is 1.65 x 10-2 mol/L, what is the concentrationafter 825s?
b. How long would it take for the concentration of N2O5 to decrease to1.00 x 10-2 mol/L from
its initial value, given in a?
Half-Life of a Reaction
As a reaction proceeds, the concentration of a reactant decreases, because it is beingconsumed.
The half-life, t1/2, of a reaction is the time it takes for the reactant concentrationto decrease to one-
half of its initial value. For a first-order reaction, such as the decomposition of dinitrogenpentoxide,
the half-lifeis independent of the initial concentration. To see this, substitute into the equation

In one half-life, the N2O5 concentration decreases by one-half, from its initial value,[N2O5]0, to the
value [N2O5]t= 1/2 [N2O5]0. After substituting, the equation becomes

The expression on the left equals ln 1/2 =-0.693. Hence,0.693 =kt1/2

t1/2 = 0.693/ k

It can be shown by reasoning similar to that given previously that the half-life ofa second-order
rate law, Rate =k[A]2, is:

t1/2= 1/k[A]0

For zero-order reactions, the half-life is dependent upon the initial concentrationof the reactant.
However, in contrast to the second-order reaction, as a zero-order reactionproceeds, each half-life
gets shorter.

t1/2= [A]0/2k
Temperature and Rate
As we noted earlier, the rate of reaction depends on temperature. This shows up inthe rate law
through the rate constant, which is found to vary with temperature. Inmost cases, the rate increases
with temperature.The rate constant and therefore the rate are more thantripled for a 10°C rise in
temperature. The change in rate constant with temperaturevaries considerably from one reaction
to another. In many cases, the rate of reactionapproximately doubles for a 10°C rise, and this is
often given as an approximate rule.

Why the rate constant depends on temperature can be explained by collision theory.Collision
theory of reaction rates is a theory that assumes that, for reaction to occur,reactant molecules
must collide with an energy greater than some minimum value andwith the proper orientation. The
minimum energy of collision required for two moleculesto react is called the activation energy,
Ea. The value of Eadepends on theparticular reaction.An increase in temperature causes an
increase in the kinetic energy of the particles. This leads to more frequent collisions and reaction
rate increases.At a higher temperature, the fraction of collisions with sufficient energy equal to or
greater than Ea increases. Reaction rate therefore increases.

Rate constants for most chemical reactions closely follow an equation of the form:

k =Ae-Ea /RT

The mathematical equation k =Ae-Ea /RT, which expresses the dependence of therate constant on
temperature, is called the Arrhenius equation, after its formulator,the Swedish chemist Svante
Arrhenius. Here eis the base of natural logarithms,2.718 . . . ; Eais the activation energy; R is the
gas constant, 8.31 J/(K.mol); and Tis the absolute temperature. The symbol A in the Arrhenius
equation, which isassumed to be a constant, is called the frequency factor. The frequency factor
isrelated to the frequency of collisions with proper orientation (pZ).

It is useful to recast Arrhenius’ equation in logarithmic form. Taking the naturallogarithm of both
sides of the Arrhenius equation gives:

lnk = lnA – Ea/RT

This shows that if you plot lnk against 1/T, you should get a straight line. The slopeof this line is -
Ea/R, from which you can obtain the activation energy Ea. The interceptis lnA. It demonstrates
that the points do lie on a straight line.

You can put the previous equation into a form that is useful for computation.First you write the
equation for two different absolute temperatures T1 and T2. Youwrite k1 for the rate constant at
temperature T1 and k2 for the rate constant attemperature T2.

lnk1= lnA – Ea/RT1and,

lnk2= lnA – Ea/RT2

You eliminate ln A by subtracting the equations:

lnk2- lnk1= (lnA- lnA) –[Ea/RT2– (-Ea/RT1)]

lnk2- lnk1=–Ea/RT2+ Ea/RT1

The decomposition of hydrogen iodide, 2HI(g) → H2(g) + I2(g), has rate constants of 9.51x10-9
L/mol·s at 500 K and 1.10x10-5 L/mol·s at 600 K. Find Ea.Then calculate the rate constant at 700
K.