Professional Documents
Culture Documents
Chemical Kinetics
Chemical Kinetics
Chemical Kinetics
Kinetics – Background
• To understand & predict behaviour of a chemical system one must consider certain factors of
both Thermodynamics & Kinetics to analyze the feasibility of a chemical change
Thermodynamics : does a reaction takes
place ???
1. Gibbs Free Energy ΔG = (-)ve
The branch of chemistry, which deals with the study of reaction rates and their mechanisms,
called chemical kinetics.
• Kinetic studies not only help us to determine the speed or rate of a chemical reaction but also
describe the conditions by which the reaction rates can be altered.
• The factors such as concentration, temperature, pressure and catalyst affect the rate of a reaction.
Rate Of Reaction: Change in concentration (mol/L) of a reactant or product with time (s, min, hr);
Rate of Reaction =
• Concentration of Reactant A
(Black ) decreases with time time
• Concentration of Product B
(Red) increases with time The graph shows the change in
the number of A
and B molecules in the reaction
• Concentrations of A & B are
as a function of time
measured at time t1 & t2
respectively A1 , A2 & B1 , B2
Rate with respect to A
-Δ[A] Δ[B]
Rate = = ( - ve ) sign is used because the concentration of A is decreasing
Δt Δt
aA+bB→cC+dD
where a, b, c,d are stoichiometric coeffi cients in the balanced
Chemical equation & A, B , C , D are Chemical Species
Average rate depends upon the change in conc. of reactants or products and the time taken for that change to occur, rav.
The rate of reaction at a particular moment of time is called as the instantaneous rate, rins.
Rate Law or Rate Expression and Rate Constant
The expression which relates of rate of reaction to concentration of the reactants is known as rate law. It is also
called as rate equation or rate expression.
• Consider a general reaction: aA + bB → cC + dD where a, b, c and d are the stoichiometric coefficients of
reactants and products.
The rate expression for this reaction is –
Acc. to the Law Of Mass Action
Rate of reaction = k [A]x[B]y where exponents x and y may or may not be equal to the stoichiometric coefficients
(a and b) of the reactants.
Thus, rate law is the expression in which reaction rate is given in terms of molar concentration of reactants with
each term raised to some power, which may or may not be same as the stoichiometric coefficient of the reacting
species in a balanced chemical equation.
B
Order of a reaction can be 0, 1, 2, 3 and even a fraction.
Overall order of reaction(n) = x + y
Depending upon order of reaction, reactions are termed as zero, first or second order reactions.
Rate concentration 1
k = = x
[A]n time (concentration)n
k = (concentration)1-n time-1
Molecularity of a Reaction
Molecularity of a reaction is simply the number of reacting species (atoms, ions or molecules)
involving is an elementary reaction which must collide simultaneously.
Rate
[Ro ] ̶ [R] = kt
First Order Reactions
First order reaction means that the rate of the reaction is proportional to first power
of the concentration of reactants. Consider the reaction,
R→P
Rate constant unit:
𝟏
k = 𝐭ln [Ro]
[R]
Second Order Reactions Half-Life of a Reaction
The half-life of a reaction is the time in which the
−d[A]/dt=k[A] 2
concentration of a reactant is reduced to one half of its initial
concentration. It is represented as t1/2
The equation can then be rearranged:
t1/2 for a Zero Order Reactions
Half-Life of a First Order Reaction
t1/2 for a First Order Reactions Half-Life of a Second Order Reaction
Thus for a first order
reaction, half-
life period is constant, i.e.,
it is independent of
initial concentration of
the reacting species.
a a 1/a
zero first second
order order order
Examples of observed
rate laws for some
reactions follow:
r = k [ester] [H2O]
Effect of temperature on rate of chemical 2. The larger the value of Ea, the slower the rate
reaction of a reaction at a given temperature.
For a chemical reaction with rise in temperature by 10°, the
3. The larger the value of Ea, the steeper the slope
rate constant is nearly doubled
of (ln k) vs (1/T). A high activation energy
k
(T+10) /kT = 2 or 3 is called the temperature coefficient corresponds to a reaction rate that is very
sensitive to temperature.
Arrhenius equation
Slow
ClO(g) + O(g) O2(g) + Cl(g)
How catalyst change reaction rate
Catalysts
particles
Cl(g) in the destruction of O3(g)
products
k = 3.3 x
Solution
10-4 sec-1
[A]/[A]0 = fraction remaining
when
Whatt is
= tthe half-life
1/2, then fractionofremaining = 1/2
this reaction?
Therefore, ln (1/2) = - k • t1/2
0.693 = k • t1/2
So, for sugar,
= 0.693/3.3 10-4 s-1 = 2100 sec = 35 min
t1/2