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4 Chemical Kinetics-Notes

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73 views8 pages

4 Chemical Kinetics-Notes

Uploaded by

youlaughyoulose29
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4 .

Chemical Kinetics
Branch of chemistry, which deals with the study of reaction rates and their
mechanisms, called chemical kinetics.
Thermodynamics tells only about the feasibility of a reaction whereas
chemical kinetics tells about the rate of a reaction.
For example, thermodynamic data indicate that diamond shall convert to
graphite but in reality the conversion rate is so slow that the change is not
perceptible at all.
Kinetic studies help us to determine
i) the speed or rate of a chemical reaction
ii)To describe the conditions by which the reaction rates can be altered.
iii)The factors such as concentration, temperature, pressure and catalyst
affect the rate of a reaction.
Rate of a Chemical Reaction
Speed of a reaction or the rate of a reaction is defined as the change in
concentration of a reactant or product in unit time.

It can be expressed in terms of:


(i) the rate of decrease in concentration of any one of the reactants, or
(ii) the rate of increase in concentration of any one of the products.

Consider a reaction, R →P (assuming that the volume of the system remains constant)

One mole of the reactant R produces one mole of the product P.

If [R]1 and [P]1 are the concentrations of R and P respectively at time t1 and [R]2 and [P]2 are
their concentrations at time t2 then,
∆t = t2 – t1
∆[R] = [R]2 – [R]1
∆[P] = [P]2 – [P]1
The square brackets in the above expressions are used to express molar concentration.

Average

Average

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Since, ∆[R] is a negative quantity (as concentration of reactants is decreasing), it is multiplied with
(–1) to make the rate of the reaction a positive quantity.

Instantaneous and average rate of a reaction

Units of rate of a reaction:


Units of rate are concentration time–1.
For example, if concentration is in mol L–1 and time is in seconds then the units will be mol L –1s–1.

However, in gaseous reactions, when the concentration of gases is expressed in


terms of their partial pressures, then the units of the rate equation will be atm s–1.

For a gaseous reaction at constant temperature,


Concentration is directly proportional to the partial pressure of a species and
hence, rate can also be expressed as rate of change in partial pressure of the reactant or the
product.

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Instantaneous rate:

The rate of change of concentration of any one of the reactants or products at a given time
(or) the rate at a particular moment of time is called instantaneous rate.

037 M

0165 M

Instantaneous rate of hydrolysis of butyl chloride(C4H9Cl)

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Factors Influencing Rate of a Reaction :
The rates of chemical reaction are influenced by a number of factors. They
are:

i) Concentration of reactants ii) Temperature


iii)Presence of catalyst iv) Nature of reactants
v) Surface area vi) Exposure to radiations

Rate Law :
At a given temperature the rate of a chemical reaction is directly
proportional to the product of the molar concentrations(or Active mass) of the
reactants raised to the power their numerical coefficients.
[The molar concentrations of the reactant is also called active mass.]

Consider a reaction:
aA + bB + cC→ Products
According to Rate Law :
Reaction rate  [A]a[B]b[C]c

Reaction rate = k[A]a[B]b[C]c


Where k is known as rate constant or Velocity constant or Specific reaction
rate. [k is proportionality constant].
***The powers of concentrations of reactants in rate law expression are
experimentally determined values.
Consider a reaction
aA + bB + cC→ Products
According to Rate Law:

Reaction rate  [A]x[B]y[C]z Where x, y and z are experimentally determined values.


Reaction rate = k [A]x[B]y[C]z

Order of a Reaction:
Sum of powers raised on concentration terms in the rate expression.
(or)
Sum of powers of the concentration of the reactants in the rate law expression is
called the order of that chemical reaction.
Reaction rate = k [A]x[B]y[C]z

Therefore, Order = x+y+z

Note: Power, which may or may not be same as the stoichiometric coefficient
of the reacting species in a balanced chemical equation.

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Rate constant:
The Rate constant of a reaction at a given temperature is defined as “ Rate
of the reaction when the concentration of each of the reactants is unity” i.e., 1 mol L-1.

Difference between Reaction Rate and Rate Constant:

Sl.No. Reaction Rate Reaction Rate Constant


1 It is the speed with which reactants are It is a constant of proportionality in the rate law
converted into products. i.e, Rate of a reaction is and is equal to the rate of reaction when the
the change in the concentration of reactants per concentration of reactants is unity.
unit time.
2 It depends upon the initial concentration of the Its value is independent of the initial
reactants. concentration of reactants and depends upon the
temperature.

3 Its units are always mol L-1 time-1. The units of rate constant depend upon the
nature of the reaction and also upon the order of
reaction.

Reaction rate = k [A]a[B]b[C]c

Reaction Rate Reaction Rate Constant

Units of rate constant:

In General Units of K = [mol L-1] (1-n) S-1


Rate Law:
.

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Elementary reactions:
The reactions taking place in one step are called elementary reactions.
Complex reactions:
When a sequence of elementary reactions (called mechanism) gives us the
products, the reactions are called complex reactions.
Molecularity of a Reaction:
Molecularity is defined as the number of atoms or molecules taking part in an
elementary step leading to a chemical reaction.
Rate determining step:
Most of the chemical reactions occur by multistep reactions. In the sequence of
steps it is found that one of the steps is considerably slower than the others. The
step which has the lowest rate value among the other steps of the reaction is
called as the rate determining step (or) rate limiting step.
Consider the reaction,
2A + B C + D going by two steps like,

Here, the first step is called as the rate determining step of the reaction.

Distinction between Molecularity and Order


Molecularity Order
1 It is the number of molecules of It is the sum of powers raised on
reactants taking part in elementary step concentration terms in the rate
of a reaction. expression.
2 It is a theoretical concept. Order is determined experimentally.
3 Molecularity can neither be zero nor Order of a reaction can be zero,
fractional fractional or integer.
4 In a multistep reaction, the In a multistep reaction, order is
molecularities of all the steps are determined for the slowest step
determined. only.
5 A multistep reaction has no overall The overall order of the multistep
molecularity. Only the the steps have reaction is given by the slowest step
the molecularity. only.

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Integrated Rate Equations :

The integrated rate equations are different for the reactions of different
reaction orders. Here we are going to discuss only zero and first order chemical
reactions.

Zero Order Reactions


Zero order reactions are relatively uncommon but they occur under special
conditions.
Examples,
1. The decomposition of gaseous ammonia on a hot platinum surface is a zero order
reaction at high pressure.

Rate = k [NH3 ]0 = k

2. The thermal decomposition of HI on gold surface is another example of zero order reaction.

Consider the zero order reaction,

(Equ. 1) Where I= Integration constant

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When t = 0, R = [R]0, where [R]0 is the initial concentration of the reactant.

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