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Chapter 4: Chemical


Chemical Kinetics
The area of chemistry concerned with the speeds, or rates at which a
chemical reaction occurs
Kinetic = movement/ change
Reaction rate is the change of concentration of a reactant or a
product with time (M/s)
Reactants [A] products [B]
The reactants are consumed while products are formed
Rate = -[A]

Rate = [B]

The rate of reaction A B, represented as the decrease of A molecules

with time and as the increase of B molecules with time

In aqueous solution, molecular bromine reacts with formic acid (HCOOH) as follows:

Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)
Measuring the change (decrease) in bromine concentration at some initial time and then at some
final time enables us to determine the average rate of the reaction during that interval
Average rate = - [Br2]
= - [Br2]final [Br2]initial
tfinal - tinitial

The instantaneous rates of the reaction between molecular bromine and formic
acid at t = 100 s. 200 s and 300 s are given by the slopes of the tangents at these

From the graph, we can conclude that the rate of reaction is directly proportional to Br2
concentration, rate = k[Br2], where k is known as the rate constant (a constant of proportionality
between the reaction rate and the reaction of reactant)
Rearranging the equation, we get k = rate, where k is in 1/s or s-1

Reaction Rates & Stoichiometry

As in ozone (O3) depletion for instance, 2O3 3O2
Thus the rate of this reaction, can be given by the rate at which ozone decomposes, Rate = [O3]
Average Rate: Two concentrations are measured at times separated by a finite difference, and the slope of the
line between them gives the rate

Instantaneous Rate: The rate at a single moment, and it is given by the slope of a line tangent to the curve
defined by the change in concentration versus time

Rate Law and the Concentration Dependence of Rates

Differential rate law: Rate = k[X]m[Y]n, where k= rate constant, [X] and [Y] represent the reactant
concentrations and m and n are either integers or half integers
m and n are referred to as the order of a reaction. For example, if m = 1, the reaction is first order
with respect to reactant X
When a rate law depends on more than one reactant concentration, we can distinguish between
the overall order of the reaction and the order with respect to individual reactants.
For example, Rate = k[A]2[B]
overall order is 3

The order with respect to A is 2 and with respect to B is 1. The

Determination of the Rate Law

Rate = k[A]n
If n = 0, doubling the concentration of A does not change the rate at
all. Because any quantity raised to the 0 power is 1
If n = 1, doubling the concentration of A doubles the rate
If n = 2, doubling the concentration of A increases the rate by a factor
of 4 (because 22 = 4)


The decomposition of N2O5:

2N2O5(g) 4NO2(g) + O2(g)

Consider the following data for the kinetics of this reaction. Determine the rate law and rate
constant for this reaction of these experiments.

Initial [N2O5] (mol L-1]

Initial Rate of Reaction (mol

L-1 s-1)

3.0 x 10-3

9.0 x 10-7

9.0 x 10-3

2.7 x 10-6

From the data, the initial concentration triples from the first to the second exp:

3(3.0 x 10-3) = 9.0 x 10-3 mol L-1

And the rate also triples:
3(9.0 x 10-7) = 2.7 x 10-6 mol L-1s-1
Because tripling the concentration triples the rate, the reaction must be first order with respect to N2O5,
Rate = k[N2O5]
Using Exp #1 from the table,
9.0 x 10-7 mol L-1 s-1 = k(3.0 x 10-3 mol L-1)

Therefore, k = 3.0 x 10-4 s-1

Integrated Rate Laws: Zero- Order Integrated Rate Law

The simplest rate law, Rate = k[A]0 = k

The rate of reaction will not change as the reactants are consumed. The integrated rate law for
this type of kinetics is given by [A]t = [A]0 kt
Rearrange this equation slightly and compare to the equation for a straight line with the form

y = mx + b

[A]t = -kt + [A]0

Integrated Rate Laws: First- Order Integrated Rate Law

For first- order reaction of some reactant, A, the integrated rate law is given by the equations,
ln [A]t = -kt


[A]t = [A]0e-kt

[A]0 represents the initial concentration of the reactant at time t = 0. With these equations, if
we know the rate constant and the initial concentration, we can predict the concentration
at any subsequent time.

The photodissociation of ozone by ultraviolet light in the upper atmosphere is a first- order reaction with a rate
constant of 1.0 x 10-5 s-1 at 10 km above the planets surface.
O3 + hv O + O2
Consider a laboratory exp in which a vessel of ozone is exposed to UV radiation at an intensity chosen to mimic
the conditions at that altitude. If the initial O3 concentration is 5.0 mM, what will the concentration be after 1.0

1.0 day x 1 x



x 1 = 8.6 x 104 s

[O3] = [O3]0e-kt
= 5.0 mM (e-(1.0 x 10-5)(8.6 x 104))
= 2.1 mM

Graph of [O3] vs Time

Graph of ln[O3] vs Time

Integrated Rate Laws: Second- Order Integrated Rate Law

For second- order reactions, the consumption of reactant X, the integrated law is


1 = kt

where, [X]t is the concentration of X at time t and [X]0 is the initial concentration
Second- order reaction is a reaction whose rate depends on the concentration of one reactant
raised to the second power or on the concentrations of two different reactants, each raised to the
first power.

Half- Life
The half- life of a reactant is the time it takes for its concentration to fall to one- half its original
value. Although this quantity can be defined for any reaction, it is particularly meaningful for firstorder reactions

Taken from first- order reaction, t = ln

By the definition of half- life, when t = t1/2 = [A]0/2, so


t1/2 = ln



t1/2 = ln 2 =


Half- life of a first- order reaction is independent of the initial concentration of the reactant. Thus,
it takes the same time for the concentration of the reactant to decrease from 1.0 M to 0.50 M,
say as it does for a decrease in concentration from 0.10 M to 0.050 M

A plot of [A]t vs time for the first- order reaction A products. The half- life of the reaction is 1 min. After the
elapse of each half- life, the concentration of A is halved

The rate constant, k, for the thermal decomposition of ozone in the dark at 25C is just
3 x 10-26 s-1. What is the half life of ozone under these conditions?

From the units of the rate constant, this is a first- order reaction.
t1/2 = 0.693 = 0.693

3 x 10-26 s-1

2 x 1025 s

Summary of the Kinetics of Zero- Order, First- Order, and Second- Order

Temperature & Kinetics (The Collision Theory of Chemical Kinetics)

Chemical reactions occur as a result of collisions between reacting molecules. In terms of the
collision theory of chemical kinetics, it expected that the rate of a reaction to be directly
proportional to the number of molecular collisions per second

Any molecule in motion possesses kinetic energy; the faster it moves, the greater the kinetic
energy. But a fast- moving molecule will not break up into fragments on its own. To react, it must
collide with another molecule. When molecules collide, part of their kinetic energy is converted
to vibrational energy.
If the initial kinetic energies are large, then the colliding molecules will vibrate so strongly as to
break some of the chemical bonds. This bond fracture is the first step toward product formation.
If the initial kinetic energies are small, the molecules will merely bounce off each other intact.
There is some minimum collision energy below which no reaction occurs. Lacking this energy, the
molecules remain intact and no change results from the collision

Temperature & Kinetics (The Collision Theory of Chemical Kinetics)

In order to react, the colliding molecules must have a total kinetic energy equal to or greater than
the activation energy (Ea), which is the minimum amount of energy required to initiate a chemical
When molecules collide, they form an activated complex (transition state), a temporary species
formed by the reactant molecules as a result of the collision before they form the product
A + B AB C + D
AB denotes an activated complex formed by the collision between A and B. AB is a highly
unstable species with a high potential energy.
If the products are more stable than the reactants, the reaction will be accompanied by a
release of heat (EXOTHERMIC). If the products are less stable than the reactants, the heat will
be absorbed by the reacting mixture from the surroundings (ENDOTHERMIC)

a) Exothermic process
b) Endothermic process

The Arrhenius Equation

The dependence of the rate constant of a reaction on temperature can be expressed by the
following equation, known as Arrhenius equation:


ln k = ln A Ea

Ea is the activation energy of the reaction (in kJ/mol), R is the gas constant (8.314 J/K.mol). The
quantity A represents the collision frequency and is called the frequency factor

Chemical Reaction Stoichiometry

Stoichiometry is the theory of the proportions in which chemical species combine with one
The stoichiometric equation of a chemical reaction is a statement of the relative number of
molecules or moles of reactants and products that participate in the reaction

For example, 2SO2 + O2 2SO3 indicates that for every two molecules (g-moles, lb-mole) of O2
reacts to produce two molecules (g-moles, lb-moles) of SO3. A valid stoichiometric must be
The stoichiometric ratio of two molecular species participating in a reaction is the ratio of their
stoichiometric coefficients in the balanced reaction. This ratio can be used as a conversion factor
to calculate the amount of a particular reactant (or product) that was consumed (or produced),
given a quantity of another reactant of product that participated in the reaction
For 2SO2 + O2 2SO3, you can write the stoichiometric ratios

2 mol SO3 generated

1 mol O2 consumed


2 lb-moles SO2 consumed

2 lb-moles SO3 generated

Limiting and Excess Reactant, Fractional Conversion and Extent of Reaction

Two reactants, A and B are said to be present in stoichiometric proportion if the ratio (moles A
present)/(moles B present) equals the stoichiometric ratio obtained from the balanced reaction
equation. For the reactants in the reaction 2SO2 + O2 2SO3 to be present in stoichiometric
proportion, there must be 2 moles of SO2 for every mole of O2 (so that nSO2/nO2 = 2:1) present in
the feed to the reactor
If reactants are fed to a chemical reactor in stoichiometric proportion and the reaction proceeds
to completion, all of the reactants are consumed. In the above reaction, for example, if 200 mol of
SO2 and 100 mol of O2 are initially present and the reaction proceeds to completion , the SO2 and
O2 would disappear at the same instant. It follows that if you start with 100 mol of O2 and less
than 200 mol of SO2, the SO2 would run out
The reactant that would run out if a reaction proceeded to completion is called the limiting
reactant, and the other reactants are termed excess reactants. A reactant is limiting if it is present
in less than its stoichiometric proportion relative to every other reactant. If all reactants are
present in stoichiometric proportion, then no reactant is limiting.

Limiting and Excess Reactant, Fractional Conversion and Extent of Reaction

Suppose (nA)feed is the number of moles of an excess reactant, A, present in the feed to a reactor
that (nA)stoich is the stoichiometric requirement of A, or the amount needed to react completely
with the limiting reactant. Then (nA)feed (nA)stoich is the amount by which the A in the feed
exceeds the amount needed to react completely if the reaction goes to completion. The fractional
excess of the reactant is the ratio of the excess to the stoichiometric requirement:
Fractional excess of A = (nA)feed - (nA)stoich
Percentage excess of A is 100 times the fractional excess

Consider the hydrogenation of acetylene to form ethane:
C2H2 + 2H2 C2H6
and suppose that 20.0 kmol/h of acetylene and 50.0 kmol/h of hydrogen are fed to a reactor. The
stoichiometric ratio of hydrogen to acetylene is 2:1 and since the ratio of H2 to C2H2 in the feed is
2.5:1 (50:20), hydrogen is fed in a greater-than-stoichiometric proportion to acetylene. Acetylene is
therefore the limiting reactant. Since it would take 40.0 kmol H2/h to react completely with all the
acetylene fed to the reactor, (nH2)stoich = 40.0 kmol/h
Thus, fractional excess of H2 = (50.00 40.0) kmol/h
40.0 kmol/h
= 0.25 (25% excess hydrogen in the feed)

Limiting and Excess Reactant, Fractional Conversion and Extent of Reaction

Chemical reactions do not take place instantaneously and indeed often proceed rather slowly. In
such cases, it is not practical to design the reactor for complete conversion of the limiting
reactant; instead, the reactor effluent emerges with some of the limiting reactant still present
and is then usually subjected to a separation process to remove the unconverted reactant from
the product.
The separated reactant is then recycled to the reactor inlet. The fractional conversion of a
reactant is the ratio

f = moles reacted
moles fed
The fraction unreacted is accordingly 1- f. If 100 moles of a reactant are fed and 90 moles react, the
fractional conversion is 0.90 (the percentage conversion is 90%) and the fraction unreacted is 0.10.
If 20 mol/min of a reactant is fed and the percentage conversion is 80%, then (20)(0.80) = 16
mol/min has reacted and (20)(1-0.80) = 4 mol/min remains unreacted.