Chemical Kinetics

Chemical reactions

Reaction Mechanisms
Chemical kinetics
is the study and discussion of chemical
reactions with respect to reaction rates, effect of various
variables, re-arrangement of atoms, formation of
intermediates etc..

There are many topics to be discussed, and each of these topics

is a tool for the study of chemical reactions
The study of motion is called kinetics, from Greek
kinesis, meaning movement.
If Chemistry is making new substances out of old substances (i.e.,
chemical reactions), then there are two basic questions that must
be answered:

1. Does the reaction want to go? This is the subject of

chemical thermodynamics.
2. If the reaction wants to go, how fast will it go? This is the
subject of chemical kinetics
 Chemical kinetics studies two things:

1) the rate at which a chemical reaction takes place.

2) the factors which affect the speed of the reaction.

•Molecules or atoms of reactants must collide with
each other in chemical reactions.
•The molecules must have sufficient energy
(discussed in terms of activation energy) to initiate
the reaction.
•In some cases, the orientation of the molecules
during the collision must also be considered
Reaction Rates
Chemical reaction rates are the rates of change in concentrations
or amounts of either reactants or products.

Thermodynamics and kinetics are two factors that affect

reaction rates. The study of energy gained or released in
chemical reactions is called thermodynamics
 Factors Influence Reaction Rates

1.Nature of Reactants

Acid-base reactions, formation of salts, and

exchange of ions are fast reactions. Reactions in
which large molecules are formed or break apart are
usually slow. Reactions breaking strong covalent
bonds are also slow.
2.Temperature

Usually, the higher the temperature, the faster the

reaction.The temperature effect is discussed in terms of
activation energy.
 Concentration Effect

The dependences of reaction rates on concentrations are called

rate laws. Rate laws are expressions of rates in terms of
concentrations of reactants. Keep in mind that rate laws can be in
differential forms or integrated forms. They are called
differential rate laws and integrated rate laws. The following is a
brief summary of topics regarding rate laws
 Reaction Mechanisms

The detailed explanation at the molecular level how a reaction

proceeds is called reaction mechanism. The explanation is
given in some elementary steps. Devising reaction mechanisms
requires a broad understanding of properties of reactants and
products.
Chemical reactions go through many steps before bonds are
broken and new ones are formed. Everything that a chemical
reaction goes through to break these bonds and form new ones is
called the reaction mechanism
However, we can mix hydrogen gas and oxygen gas together in a
bulb or other container, even in their correct stoichiometric
proportions, and they will stay there for centuries, perhaps even
forever, without reacting.

If we drop in a catalyst - say a tiny piece of platinum - or introduce

a spark, or even illuminate the mixture with sufficiently high
frequency uv light, or compress and heat the mixture, the mixture
will explode.
The problem is not that the reactants do not want to form the
products, they do, but they cannot find a "pathway" to get from
reactants to products.
Molecularity, which tells us the number of molecules involved in an
elementary reaction step.

Sequence of elementary reaction steps together form what is called

a mechanism. A reaction mechanism is a detailed (theoretical)
description of how we think the chemical reaction proceeds. That is,
it describes our thought about which molecule collides with which
other molecule to form an intermediate product, which may go on to
react with some other species, and so on, to produce the overall
reaction. The elementary reaction steps must be balanced (as do all
chemical reactions)
 E+ = Electrophile
Nuc: = Nucleophile

General Mechanism: The first step requires a powerful

electrophile to attract the pi bond electrons, which then forms a
carbocation. A nucleophile quickly adds to the carbocation to
form the monosubstituted product
The Rate Determining Step--Formation of the carbocation
 Rate Laws

A rate law is an equation that tells us how fast the reaction proceeds
and how the reaction rate depends on the concentrations of the
chemical species involved
1. First Order Reactions
In a first order reaction the rate is proportional to the
concentration of one of the reactants.

2. Second Order Reactions

In a second order reaction the rate is proportional to concentration
squared
In this rate law, the rate at which NO & O2 disappear
is proportional to their concentrations and k is a
proportional constant
nH2N -- R -- NH2 + nHOOC -R' - COOH

H--- (--NH -R - NHCO - R' - CO-)n -OH + (2n-1)H2O

Acetic acid will react with ethanol to produce ethyl acetate