KINETICS, CHEMICAL KINETICS:

Also known as reaction kinetics is the study of rates and mechanism of chemical processes.

HOMOGENEOUS REACTIONS:
The reaction in which all reactants and products are in one phase.
HETEROGENEOUS REACTION:
Chemical reactions in which the reactants are components of
two or more phases e.g solid and gas, solid and liquid, two immiscible liquids. The reaction of metals
with acids, the electrochemical changes that occur in batteries and electrolytic cells, and the
phenomena of corrosion are part of the subject of heterogeneous reactions.

REACTION RATES:
Change in concentration of a reactant or product per unit time.
AB

t
A
-
t - t
A - A

t in time, Change
A conc, in Change
0 t
0 t

-ive shows is Because [A] decreases with time,

t
B

t - t
B - B

t in time, Change
B conc, in Change
0 t
0 t

FACTORS AFFECTING RATE:
Temperature
Nature Of The Reactants
Surface Area
Effect Of Concentration
Pressure

Temperature:
Kinetic theory says that molecules are in constant motion. The kinetic energy
and molecule velocity increase with temperature.
KE = [1/2][mv
2
]
Reactions usually require collisions between reactant molecules or atoms.
The formation of bonds requires atoms to come close to one another. New
bonds can form only if the atoms are close enough together to share
electrons. Collisions between molecules will be more violent at higher temperatures.
The higher temperatures mean higher velocities. This means there will be less time
between collisions. The frequency of collisions will increase. The increased number of
collisions and the greater violence of collisions results in more effective collisions. The
rate for the reaction increases.

Example
the use of a pressure cooker to cook foods faster.
the use of a refrigerator to store food and slow its spoilage.

Nature Of The Reactants
Rate of a reaction depends on the nature of bonding in the reactants.

State of Matter
Gases tend to react faster than solids or liquids: It takes energy to separate particles
from each other. In order to burn candle wax, the solid wax has to be melted and then
vaporized before it reacts with oxygen. Methane gas is already in the gas state so it
burns faster than wax.

fast
slow
Bond Type
Reactions involving ionic species tend to proceed faster than reactions evolving
molecular compounds.
Bond Strength
Reactions involving the breaking of weaker bonds proceed faster than reactions
involving the breaking of stronger bonds.
Number of Bonds/Molecular Size
Reactions involving the breaking of fewer bonds per reactant proceed faster than
those involving the breaking of a larger number of bonds per reactant.

Surface Area
The rate of reaction of a solid substance is related to its surface area. The rate of a
reaction increases with increase in the surface area of solid reactant. The surface of a
solid can be increased by grinding it to a fine powder. In a reaction between a solid
and an aqueous/liquid/gas species, increasing the surface area of the solid-
phase reactant increases the number of collisions per second and therefore increases the
reaction rate. E.g. The reaction between zinc and hydrochloric acid occurs within
seconds if the zinc metal is finely powdered. But the reaction will be slower when a zinc
wire is used. This is also true with the solid catalysts, which are usually employed in
finely powdered form, while carrying out a chemical reaction.

Effect Of Concentration
Rate of a reaction is directly
proportional to the concentration of reactants. Reaction rates can be increased if the
concentration of reactants is raised. An increase in concentration produces more
collisions. The chance of an effective collision goes up with the increase in
concentration.

i.e.
rate (r) cn
where, c = concentration, n = order of the reaction
or r = kcn, where k = specific rate



Pressure
The concentration of a gas is a function of the pressure on the
gas. Increasing the pressure of a gas is exactly the same as increasing its
concentration. If you have a certain number of gas molecules, you can increase the
pressure by forcing them into a smaller volume.
Under higher pressure or at a higher concentration, gas molecules collide more
frequently and react at a faster rate. Conversely, increasing the volume of a gas
decreases pressure which in turn decreases the collision frequency and thus reduces
the reaction rate. Note that solids and liquids are not affected by pressure changes.

RATE LAWS
In many reactions, the rate of reaction changes as the reaction progresses. Initially the rate of
reaction is relatively large, while at very long times the rate of reaction decreases to zero (at
which point the reaction is complete). In order to characterize the kinetic behavior of a
reaction, it is desirable to determine how the rate of reaction varies as the reaction
progresses.

A rate law is a mathematical equation that describes the relationship of the rate of a reaction
to the rate constant and the concentrations of the reactants raised to some powers.
aA + bB--------- cC + dD
Rate = k[A]
x
[B]
y

Where,
K is the rate coefficient or rate constant of the reaction.
Reaction is x
th
order in A and is y
th
order in B and reaction is (x +y)
th
order overall.

Rate laws are always determined experimentally.
Reaction order is always defined in terms of reactant (not product) concentrations.
The order of a reactant is not related to the stoichiometric coefficient of the reactant in the
balanced chemical equation.
F
2(g)+
2ClO
2(g)
------2FClO
2(g)

rate = k[F
2
][ClO
2
]
1

RATE CONSTANT
A + B -----> Products
Then rate law would be;
Rate = k[A][B]
and the reaction would
be first order in A, first order in B and second order overall. The rate constant can then be
determined from initial rate information easily:
CONCENTRATION vs. TIME
The reaction rate is the change in the concentration of
either the reactant or the product over a period of time. The concentration of A decreases
with time, while the concentration of B increases with time.
The mixture initially contains only A molecules (purple). With increasing time, the number of
A molecules decreases and more B molecules (green) are formed (top). The graph shows the
change in the number of A and B molecules in the reaction as a function of time over a 1 min
period (bottom).
Q. So what happens if the rate is independent of concentration, as in a zero order reaction?
In this case, the rate of reaction won't change as the concentration
of the substance falls over time. If the rate doesn't change, that means that the slope of the
curve doesn't change - and so you will get a straight line rather than a curve.

INSTANTANEOUS RATE OF CHANGE
The rate of change at a particular moment is called.

x
y
line tangent of slope

For a function, the instantaneous rate of change at a point is the

same as the slope of the tangent line. That is, it's the slope of a curve.


We determine an instantaneous rate at time t:
by calculating the negative of the slope of the curve of
concentration of a reactant versus time at time t.
by calculating the slope of the curve of concentration of a product versus time at time
t.

Problem:
???

INITIAL RATE (t = 0)
Instantaneous rate just after reaction is initiated

METHOD OF INITIAL RATES
The Method of Initial Rates involves measuring the rate of reaction r (reaction order) at
very short times before any significant changes in concentration occur. Suppose one is
studying a reaction with the following stoichiometry;
aA + bB Product
reactions have a rate law of the following form;
r = k [A]
a
[B]
b

The initial concentrations of A and B are known; therefore, if the initial reaction rate is
measured, the only unknowns in the rate law are the rate constant, k, and the exponents
a and b.




2 2
O 2NO 2NO
Problem:

Consider the following set of data:





The rate Law is then given as;


n
2
2
NO k
t
NO
rate

-


First, write the ratio of the rate laws for two trials.


n
2 1
n
2 2
NO k -
NO k -

1 rate
2 rate

n
1
n
2
5 -
-4
0.010 k -
0.020 k -

10 7.1
10 2.8

or
To convert n from an exponent into a coefficient, take the logarithm of both sides of the
equation.

Rate constant:


n
2
2
NO k
t
NO
rate

-




Rate 1: 7.1 x 10-5 M s-1 = -k[0.01 M]2
k = 0.71 M-1 s-1

Rate 2: 2.8 x 10-4 M s-1 = -k[0.02 M]2
k = 0.70 M-1 s-1







ORDER OF REACTIONS
aA
(g)
-----> products
rate = k(conc A)
m

The power(m) to which the concentration of A is raised in the rate expression describes
the order of the reaction.
If "m" = 0, the reaction is zero order
If "m" = 1, it is first order
If "m" = 2, it is second order
Conditions:
m = 0: zero order - rate is independent of the concentration of reactant. Doubling
concentration has no effect on rate. It is because any concentration raised to zero is
one.
m = 1: first order - rate is directly proportional to the concentration of the reactant.
Doubling the concentration increases the rate by a factor of 2.
m = 2: second order - If the rate is second order with respect to a particular
component, doubling its concentration increases the rate by a factor of 2
2
= 4, Tripling
its concentration increases the rate by a factor of 3
2
= 9 and so forth
TYPES:
Chemical reactions are often classified on the basis of kinetics as zero-order, first-order,
second-order.
Differential:
Rate dependence on concentration.
Integrated:
Concentration dependence on time.

First Order (m=1):
The Differential Form:
A first-order reaction is a reaction that proceeds at a rate that depends only on one reactant
concentration. The differential equation describing first order kinetics is:

aA -----> products
Rate=d[A]/dt
= k[A]
1
= k[A]








The Integrated Form:





































The following graphs represent concentration of reactants versus time for a first-order
reaction.

Plotting ln[A] with respect to time for a first-order reaction gives a straight line with the slope
of the line equal to -k.
Relationship Between Half-life and First-order reactions





Second Order (m=2):
A Second-order reaction is a reaction that proceeds at a rate that depends only on two
reactants concentration.
The Differential Form:
The differential equation describing first order kinetics is:
A+AP
2AP
The reaction rate for this step can be written as;


where k is a second order rate constant with units of M
-1
min
-1
or M
-1
s
-1
. Therefore, doubling the
concentration of reactant A will quadruple the rate of the reaction.

The Integrated Form:




This graph is useful in a variety of ways. If we only know
the concentrations at specific times for a reaction, we can attempt to create a graph similar
to the one above. If the graph yields a straight line, then the reaction in question must be
second order. In addition, with this graph we can find the slope of the line and this slope is k,
the reaction constant. The slope can be found be finding the "rise" and then dividing it by the
"run" of the line. For an example of how to find the slope, please see the example section
below. There are alternative graphs that could be drawn.
The plot of [A]t versus time would result in a straight
line if the reaction was zeroth order. It does, however, yield less information for a second
order graph. This is because both the graphs of a first or second order reaction would look
like exponential decays. The only obvious difference, as seen in the graph below, is that the
concentration of reactants approaches zero more slowly in a second-order, compared to that
in a first order reaction.
Relationship Between Half-life and Second-order reactions:
By definition, the half life of any reaction is the amount of time it takes to consume half of
the starting material. For a second-order reaction, the half-life is inversely related to the
initial concentration of the reactant (A). For a second-order reaction each half-life is twice as
long as the life span of the one before.
Consider the reaction 2A --> P
We can find an expression for the
half-life of a second order reaction by using the previously derived integrated rate equation.









This inverse relationship suggests that as the initial concentration of reactant is increased,
there is a higher probability of the two reactant molecules interacting to form product.
Consequently, the reactant will be consumed in a shorter amount of time, i.e. the reaction
will have a shorter half-life. This equation also implies that since the half-life is longer when
the concentrations are low, species decaying according to second-order kinetics may exist for
a longer amount of time if their initial concentrations are small.

Zero Order (m=0):
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 not afecting
the observed reaction. This means that the rate of the reaction is equal to the rate constant,
k, of that reaction having the units of M/sec.

The Differential Form:


where Rate is the reaction rate and k is the reaction rate coefficient. In this example, the
units of k are M/s. The units can vary with other types of reactions. For zero-order reactions,
the units of the rate contants are always M/s.

The Integrated Form:



















Graph:
[A]=kt+[A]0
is in the form y = mx+b where slope = m = -k and the y-intecercept = b
= [A]
0
Zero-order reactions are only applicable for a very narrow region of time. Therefore, the
linear graph shown is only realistic over a limited time range. If we were to extrapolate the
line of this graph downward to represent all values of time for a given reaction, it would tell
us that as time progresses, the concentration of our reactant becomes negative. We know
from general chemistry that concentrations can never be negative, which is why zero-order
reactions give us a brief window into looking at the reaction.

Relationship Between Half-life and Zero-order Reactions
The half-life is a timescale in which each half-life represents the reduction of the initial
population to 50% of its original state. We can represent the relationship by the following
equation.












COLLISION THEORY OF REACTION RATES
According to this theory, a chemical reaction takes place only by collisions between the
reacting molecules. But not all collisions are effective. Only a small fraction of the collisions
produce a reaction. The two main conditions for a collision between the reacting molecules
to be productive are :
(1) The colliding molecules must posses sufficient kinetic energy to cause a reaction.
(2) The reacting molecules must collide with proper orientation.

The molecules must collide with sufficient kinetic energy;
Let us consider a reaction
A A + B B 2A B
A chemical reaction occurs by breaking bonds between the atoms of the reacting molecules
and
forming new bonds in the product molecules. The energy for the breaking of bonds comes
from the kinetic energy possessed by the reacting molecules before the collision. Fig. shows
the energy of molecules A
2
and B
2
as the reaction A
2
+ B
2
2AB progresses.

The Fig. also shows the activation energy, E
a
, that is the minimum energy necessary to cause
a reaction between the colliding molecules. Only the molecules that collide with a kinetic
energy greater than E
a
, are able to get over the barrier and react. The molecules colliding with
kinetic energies less that E
a
fail to surmount the barrier. The collisions between them are
unproductive and the molecules simply bounce off one another.


The molecules must collide with correct orientation;
The reactant molecules must collide with favourable
orientation (relative position). The correct orientation is that which ensure direct contact
between the atoms involved in the breaking and
forming of bonds. (Fig. 20.10) From the above discussion it is clear that : Only the molecules
colliding with kinetic energy greater that Ea and with correct orientation can cause reaction.


ARRHENIUS EQUATION
We know that the kinetic energy of a gas is directly proportional to its temperature. Thus as
the temperature of a system is increased, more and more molecules will acquire necessary
energy greater that Ea to cause productive collisions. This increases the rate of the reaction.
Quantitatively this relationship between the rate a reaction proceeds and its
temperature is determined by the Arrhenius Equation.
k = A e
Ea /RT

This is called the Arrhenius equation in which A is an experimentally determined
quantity, Ea is the activation energy, R is the gas constant, and T is Kelvin
temperature.








































REACTION MECHANISM

Q3. Define the term activation energy as it is used in chemical kinetics.
A3. In chemical science, activation energy is a term introduced in 1889 by the Swedish
scientist Svante Arrhenius that is defined as the energy that must be overcome in order
for a chemical reaction to occur. Activation energy may also be defined as the minimum
energy required to start a chemical reaction. The activation energy of a reaction is usually
denoted by Ea, and given in units of kJ/ mol.