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Lecture 9:
Chemical Kinetics
Spring 2015

Course lecturer :
Jasmin utkovi
20th May 2015

Contents

1.
2.
3.
4.
5.
6.

International University of Sarajevo

Factors that affect the chemical kinetics

Reaction rates and rate laws
Methods of Determining Reaction Orders
Half-Lives and Radioactive Decay Kinetics
The Collision Model of Chemical Kinetics
Catalysis

1. Factors That Affect

Reaction Rates

Chemical kinetics
Study of reaction rates, or the changes in the concentrations of
reactants and products with time
By studying kinetics, insights are gained into how to control
reaction conditions to achieve a desired outcome

Chemical kinetics of a reaction depend on

various factors
1. Reactant concentrations
2. Temperature
3. Physical states and surface areas of reactants
4. Solvent and catalyst properties

Concentration Effects

Two substances cannot react with each other unless their

constituent particles come into contact; if there is no
contact, the rate of reaction will be zero.

The more reactant particles that collide per unit time, the
more often a reaction between them can occur.

The rate of reaction usually increases as the

concentration of the reactants increases.

Example

Temperature Effects
Increasing the temperature of a
system increases the average
kinetic energy of its constituent
particles.

As the average kinetic energy

increases, the particles move

faster, so they collide more
frequently per unit time and
possess greater energy when
they collide, causing increases in
the rate of the reaction.

Rate of all reactions increases

with increasing temperature and

decreases with decreasing
temperature.

Homogenous VS
Heterogeneous solutions

REMINDER !!

Homogeneous Mixtures
are composed of two or more components that are equally
(uniformly) distributed throughout the system, examples: Salt
dissolved in water, Soapy water, Hydrochloric acid & water, Alcohol
& water, Sugar dissolved in water,

Heterogeneous Mixtures
are composed of two or more components that are unequally (not
uniformly) distributed though out the system, examples: Sand &
water (liquid & solid), Oil & water (immiscible liquids), Table salt
crystals & sugar crystals (solids & solids),

Phase and Surface Area Effects

If reactants are uniformly dispersed in a single homogeneous

solution, the number of collisions per unit time depends on
concentration and temperature.

If the reaction is heterogeneous, the

reactants are in two different phases,

and collisions between the reactants can
occur only at interfaces between phases;
therefore, the number of collisions between
the reactants per unit time is reduced, as
is the reaction rate.

Solvent Effects
The nature of the solvent can affect the reaction rates of
solute particles.

Solvent viscosity is also important in determining

reaction rates.
1. In highly viscous solvents, dissolved particles diffuse much more
slowly than in less viscous solvents and collide less frequently per
unit time.
2. Rates of most reactions decrease rapidly with increasing solvent
viscosity.

Viscosity .REMINDER!!!
The viscosity of a fluid is a measure of its resistance on
gradual deformation by shear stress or tensile stress.

Catalyst Effects

Catalyst is a substance that participates in a chemical

reaction and increases the rate of the reaction without
undergoing a net chemical change itself.

Catalysts are highly selective and often determine the

product of a reaction by accelerating only one of several
possible reactions that could occur.

2. Reaction Rates
The rate of a reaction is the speed at which a
reaction happens.
If a reaction has a low rate, that means
the molecules combine at a slower speed than a reaction
with a high rate.
Some reactions take hundreds, maybe even thousands, of
years while others can happen in less than one second.

Reaction Rates cont.

Expressed as the concentration of reactant consumed or the

concentration of product formed per unit time
A+2B 3C
Units are moles per liter per unit time (M/s, M/min or M/h)
To measure reaction rates
1. initiate the reaction;
2. measure the concentration of the reactant or product at
different times as the reaction progresses;
3. plot the concentration as a function of time on a graph;
4. calculate the change in the concentration per unit time.

Reaction Rates cont.

There is another big idea for rates of reaction called collision
theory.

The collision theory says that as more collisions in a system occur,

there will be more combinations of molecules bouncing into each
other.

If there are a higher number of collisions in a system, more

combinations of molecules can occur. The reaction will go faster and
the rate of that reaction will be higher.

Concentration
More substance in a system, greater chance that
molecules will collide and speed up the rate of the reaction

less of something, there will be fewer collisions and the

reaction will probably happen at a slower speed.
Sometimes when you are in a chemistry lab, you will add
one solution to another. When you want the rate of reaction
to be slower, you will add only a few drops at a time instead
of the entire beaker.!!!

Temperature
Raising the temperature of a system, the molecules
bounce around a lot more because they have
more energy.
Bouncing results in collision and collision in
combinations. When you lower the temperature, the
molecules are slower and collide less.

That temperature drop lowers the rate of the reaction.

Back to the chemistry lab! Sometimes you will mix
solutions in ice so that the temperature of the system
stays cold and the rate of reaction is slower.

Pressure:
Pressure affects the rate of reaction, especially when you
look at gases.

When you increase the pressure, the molecules have

less space in which they can move. That
greater density of molecules increases the number of
collisions.

When you decrease the pressure, molecules don't hit

each other as often. The lower pressure decreases the
rate of reaction.

Interaction of all factors

Reaction Rates cont.

The change in the concentration of either the reactant or the
product over a period of time.

For a simple reaction ( A B),

rate = [B] = [A]

t
t
Square brackets indicate concentration; and means change in.
Concentration of A decreases with time; and the concentration of B
increases with time.

Rate Laws cont..

Reaction orders
For a reaction with the general equation
aA + bB cC + dD,

the experimentally determined rate law has the form

rate = k[A]m [B]n.
The proportionality constant, k, is called the rate constant.
1. Value is characteristic of the reaction and reaction conditions
2. A given reaction has a particular value of the rate constant
under a given set of conditions, such as temperature, pressure, and
solvent

Orders of Reaction
summary
In a zero order reaction the rate=k since anything to the
power of 0 is 1. Therefore the rate of reaction does not
change over time and the [A] (for example) changes
linearly.
In a first order reaction, the rate and concentration are
proportional. This means that if the concentration is
doubled, the rate will double.
And finally, in a second order reaction, if the concentration
is doubled, the rate will increase by a factor of 4 (22). The
speed at which the [A] changes

Zero-Order Reactions

A zero-order reaction is a reaction that proceeds at a rate that is

independent of reactant concentration.
Typically with increasing or decreasing reactants concentrations will not
affecting the observed reaction. This means that the rate of the reaction
is equal to the rate constant, k, of that reaction.

One can write their rate in a form such that the exponent of the reactant
in the rate law is 0
rate = [A] = k [reactant]0 = k(1) = k
t

First-Order Reactions
Reaction rate is directly proportional to the concentration of one of the
reactants- depends linearly only on one reactant concentration.
Have the general form A products
Differential rate for a first-order reaction is
rate = [A] = k[A]
t
If the concentration of A is doubled, the rate of the reaction
doubles; if the concentration of A is increased by a factor of 10,
the rate increases by a factor of 10
Units of a first-order rate constant are inverse seconds, s 1
First-order reactions are very common

Second-Order Reactions
Two kinds of second-order reaction
1. The simplest kind of second-order reaction is one whose rate is
proportional to the square of the concentration of the reactant and
has the form 2A products.
Differential rate law is rate = [A] = k[A]2
2t

Doubling the concentration of A quadruples the rate of the

reaction
Units of rate constant is M1s1 or L/mols

Second-Order Reactions
2. The second kind has a rate that is proportional to the product
of the concentrations of two reactants and has the form A + B
products.
Reaction is first order in A and first order in B
Differential rate law for the reaction is
rate = [A] = [B] = k[A] [B]
t
t
Reaction is first order both in A and in B and has an overall
reaction order of 2

Half-Lives
Another approach to describe reaction rates is based on
the time required for the concentration of a reactant to
decrease to one-half its initial value.

The period of time is called the half-life of the reaction,

written as t .

The half-life of a reaction is the time required for the

reactant concentration to decrease from [A]0 to [A]0 /2.

If two reactions have the same order, the faster reaction

will have a shorter half-life and the slower reaction will
have a longer half-life.

Radioactive Decay Rates

Radioactivity, or radioactive decay, is the emission of a

particle or a photon, that results from the spontaneous
decomposition of the unstable nucleus of an atom.

The rate of radioactive decay is an intrinsic property of

each radioactive isotope, independent of the chemical
and physical form of the radioactive isotope.

Radioactive Decay Rates

Because radioactive decay is a first-order
process, the time required for half of the nuclei
in any sample of a radioactive isotope to decay
is a constant, called the half-life of the isotope
Isotopes with a short half-life decay more
rapidly, undergoing a greater number of
radioactive decays per unit time than do
isotopes with a long half-life

Radioisotope Dating
Techniques
Using the half-lives of isotopes, one can estimate the
ages of geological and archaeological artifacts.
Techniques that have been developed for this application
are known as radioisotope dating techniques.
Radiometric or radioactive dating is a technique used to
date materials such as rocks or carbon, usually based on
a comparison between the observed abundance of a
naturally occurring radioactive isotope and its decay
products, using known decay rates.

Activation Energy

A minimum energy (activation energy, Ea) is required

for a collision between molecules to result in a chemical
reaction.

Reacting molecules must have enough energy to

overcome electrostatic repulsion and a minimum
amount of energy to break chemical bonds so that new
ones may be formed.

Catalysis
Substances that increase the rate of a chemical
reaction without being consumed in the process
A catalyst does not appear in the overall
stoichiometry of the reaction it catalyzes, but it must
appear in at least one of the elementary steps in the
mechanism for the catalyzed reaction
Catalyzed pathway has a lower Ea (activation
energy )
Because of its lower Ea, the rate of a catalyzed

Catalysis
A catalyst decreases the height of the energy barrier, and its
presence increases the rates of both the forward and the reverse
reactions by the same amount

There are three major classes of catalysts

1. Heterogeneous catalysts
2. Homogeneous catalysts
3. Enzymes

Enzymes

Enzymes are catalysts that occur naturally in living

organisms and are almost all protein molecules
A reactant in an enzyme-catalyzed reaction is called a
substrate.
Enzymes can increase reaction rates by enormous
factors and tend to be very specific, typically producing
only a single product in quantitative yield.

Enzymes

Enzymes are expensive, and often cease functioning at

temperatures higher than 37C, and have limited stability
in solution.
Enzyme inhibitors cause a decrease in the rate of an
enzyme-catalyzed reaction by binding to a specific
portion of an enzyme and thus slowing or preventing a
reaction from occurring.

Readings

First ,follow the slides and get more info

from the Book
Homework 4 topic (submit by 20th May):
How we determine the age of dinosaurs ?
Write one page essay.