UNIT III CHEMICAL KINETICS

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 log k2/k1 = Ea/2.303R [1/T1 – 1/T2] COLLISION THEORY

A+B PRODUCTS
PSEUDO FIRST ORDER REACTION ARRHENIUS EQUATION
RATE = ZAB e-Ea/RT
RATE = k[CH3COOC2H5] K = A e –Ea/RT

MOLECULARITY OF A
ORDER OF REACTION CHEMICAL KINETCS REACTION

UNIMOLECULAR NH4NO2 N2 +2H2O

ORDER UNITS OF INTEGRATED RATE
RATE OF CHEMICAL REACTION BIMOLECULAR 2HI H2 +I2
RATE CONSTANT
CONSTANT TRIMOLECULAR 2NO +O2 2NO2
0 Mol L-1 s-1 K = [R]0 – [R]/t
1 s-1 K = 2.303/t log[R]0/[R] INSTANTANEOUS AVERAGE RATE
2 Mol-1 L s-1 K = [1/[R] -1/[R]0]/t RATE OF OF REACTION
REACTION
FIRST ORDER K = 2.303/t log [pi/(2pi – pt)] rav = ∆P/∆t
GAS PHASE rinst = -d[R]/dt
REACTION
HALF LIFE OF A REACTION

ZERO ORDER REACTION t1/2 = [R]0/2k

FIRST ORDER REACTION t1/2 = 0.693/k

Chemical Kinetics the branch of chemistry, which deals with the study of reaction rates and their
mechanisms.

Rate of a Chemical Reaction: the rate of a reaction can be 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.
(ii) The rate of increase in concentration of any one of the products.
Consider a hypothetical reaction, R ---> P
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.
Rate of disappearance of R = Decrease in concentration of R / Time taken = - R/t (1)
Rate of appearance of P = Increase in concentration of P /Time taken = P/t (2)
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.
Equations (1) and (2) given above represent the average rate of a reaction, rav.
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Average rate depends upon the change in concentration of reactants or products and the time taken for that
change to occur. (Ref. ncert Fig. 4.1)

Units of rate of a reaction: The units will be mol L-1s–1.

In gaseous reactions, the units of the rate equation will be atm s–1.

Factors affecting rate of reaction: The important factors are:

1. Concentration of the reacting species.
2. Temperature of the system.
3. Nature of reactant and products.
4. Presence of a catalyst.
5. Surface area.
6. Exposure to radiation.

Rate Law and Rate Constant:

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 Rate ∝ [A]x [B]y
Where exponents x and y may or may not be equal to the stoichiometric coefficients (a & b) of the
reactants. Above equation can also be written as
Rate = k [A]x [B]y
-d[R] /dt = k[A] x [B]y
This form of equation is known as differential rate equation, where k is a proportionality constant called
rate constant.
The equation, Rate = k [A]x [B]y which relates the rate of a reaction to concentration of reactants is called
rate law or rate expression.
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.
For example:
2NO (g) + O2 (g) ----> 2NO2 (g)
Rate = k [NO]2 [O2]
-d[R] /dt = k [NO]2 [O2]
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Order of reaction:
Rate = k [A]x [B]y
x and y indicate the rate is to the change in concentration of A and B.
Sum of these exponents, i.e., x + y in above equation gives the overall order of a reaction. whereas x and y
represent the order with respect to the reactants A and B respectively.
Order of reaction is defined as the sum of powers of the concentration of the reactants in the rate law
expression is called the order of that chemical reaction.
Order of a reaction can be 0, 1, 2, 3 and even a fraction.
A zero-order reaction means that the rate of reaction is independent of the concentration of reactants. Units of
rate constant:
Zero order rate of reaction: mol L-1 s-1
First order rate of reaction: s-1
Second order rate of reaction: L mol-1 s-1

Molecularity of a reaction: The number of reacting species (atoms, ions or molecules) taking part in an
elementary reaction, which must collide simultaneously in order to bring about a chemical reaction is called
molecularity of a reaction.
For examples:
NH4NO2 -----> N2 + 2H2O Unimolecular reaction
2HI (g) ----> H2 (g) + I2 (g) Bimolecular reaction
2NO (g) + O2 (g) -----> 2NO2 (g) Trimolecular reaction

Important points of distinction between order and molecularity

S.No. Order Molecularity
1 Order is the sum of powers of the Molecularity is the number of reacting
concentration terms in the rate law species undergoing simultaneous collision
expression. in the elementary or simple reaction.
2 Order of a reaction is determined Molecularity is a theoretical concept.
experimentally.
3 Order of a reaction can be zero. Molecularity of a reaction cannot be zero.

Integrated rate equations:

Zero order reaction: Zero order reaction means that the rate of the reaction is proportional to zero power of the
concentration of reactants.
Consider the reaction,
R -----> P
Rate = -d[R] /dt = k [R]0
Rate = -d[R] /dt = k x 1
d[R] = -k dt
Integrating both sides
[R] = -k t +I (1)
Where, I is the constant of integration
At t = 0 the concentration of reactant [R] = [R]0
Where [R]0 is the initial concentration of reactant.
[R]0 = -k x 0 + I = I, Substituting the value of I in the equation (1)

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[R] = -k t + [R]0
k ={[R]0 - [R]}/t
Variation in the concentration Vs time plot for a zero-order reaction

Example of Zero order reaction is the decomposition of gaseous ammonia.

2NH3 (g) ------> N2 (g) + 3 H2 (g)
Rate = k [NH3]0 = k
the rate of the reaction is proportional to the
First Order Reactions: The rate of the reaction is proportional to the first power of the concentration of the
reactant R.
For example:
R -----> P
Rate = -d[R] /dt = k [R]
d[R] /[R]= -k dt,
Integrating this equation and we get
ln [R] = -kt + I (1)
At t = 0, ln [R] = -k x 0 + I,
I = ln [R]0, Substituting the value of I in the equation (1)
ln [R] = -kt + ln [R]0

k = {ln [R]0 - ln [R]} /t

Remember that, (log a – log b = log(a/b)
k = (1/t) ln {[R]0/[R]}
ln {[R]/[R]0} = - kt, taking antilog both sides
[R] = [R]0 e –kt
We know that, ln a = 2.303 log a
k = (2.303/t) log {[R]0/[R]}
If we plot a graph between log [R]0/[R] Vs t, the slope is k/2.303 for first order reaction

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First order gas phase reaction: A(g) -----> B(g) + C(g)
Total pressure pt = pA + pB + pC
A(g) -----> B(g) + C(g)
At t = 0 pi atm 0 atm 0 atm
At time t (pi – x) x atm x atm
pt = (pi – x) + x + x = pi + x
x = (pt - pi)
pA = pi – x = pi - (pt - pi) = 2pi-pt
k= (2.303/t) log [pi/ pA]
k= (2.303/t) log [pi/(2pi-pt)]

Half-life of a reaction: The half-life of a reaction is the time in which the concentration of a reactant is
reduced to one half of its initial concentration. It is represented as t1/2.

For a zero-order reaction, rate constant is

k ={[R]0 - [R]}/t
At t = t1/2, [R] = [R]0 /2

k ={[R]0 - [R]0 /2}/t1/2= [R]0 /2 t1/2

t1/2 = [R]0 /2 k

For a first order reaction, rate constant is

k = (2.303/t) log {[R]0/[R]}

At t = t1/2, [R] = [R]0 /2
k = (2.303/t1/2) log {[R]0/[R]0 /2}
k = (2.303/t1/2) log 2
k = (2.303/t1/2) 0.3010

t1/2 = 0.693/ k

For zero order reaction t1/2 ∝ [R]0.

For first order reaction t1/2 is independent of [R]0.

Collision Theory of Chemical Reactions:

Collision frequency: It is defined as the number of collisions per second per unit volume of the reaction
mixture is known as collision frequency (Z).
Effective collision: The collisions in which molecules collide with proper orientation, breaking of bonds
between reacting species and formation of new bonds to form products are called as effective collisions.
Ineffective collision: The collisions in which molecules collide with improper orientation no products are
formed are called as ineffective collisions.

For example, formation of methanol from Bromoethane depends upon the orientation of reactant molecules.
The proper orientation of reactant molecules lead to bond formation whereas improper orientation makes

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them simply bounce back and no products are formed. Diagram showing molecules having proper and
improper orientation: -

Rate of reaction is proportional to

(i) the number of collisions per unit volume per second (collision frequency, Z) between the
reacting species.
(ii) the fraction of effective collisions (properly oriented and possessing sufficient energy), f:
i.e., Rate = - dx/dt = f x Z

Temperature Dependence of the Rate of a Reaction: For the effect of temperature on reaction rates is that
the rate of a reaction or rate constant becomes almost doubled for every 10° rise in temperature. Increase in
the rate of reaction with the rise in temperature is mainly due to the increase in number of effective
collisions.
The temperature dependence of the rate of a chemical reaction can be accurately explained by Arrhenius
equation.

Arrhenius equation and calculation of Activation energy:

Where A is the Arrhenius factor or the frequency factor. It is also called pre-exponential factor. It is a
constant specific to a particular reaction. R is gas constant and Ea is activation energy measured in
joules/mole (J mol –1).

Concept of Activation energy: The excess energy (over and above the average energy of the reactants)
which must be supplied to the reactants to undergo chemical reactions is called activation energy.
It is equal to the difference between the threshold energy needed for the reaction and the average kinetic
energy of all the reacting molecules. That is,
Activation energy = Threshold energy - Average kinetic energy of the reacting molecules
Ea = Ea (threshold – Ea (reactants)
Low Activation energy: Fast reactions
High Activation energy: Slow reactions

It can be understood clearly using the following simple reaction:

H2 (g) + I2 (g) 2HI (g)

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According to Arrhenius, this reaction can take place only when a molecule of hydrogen and a molecule of
iodine collide to form an unstable intermediate. The energy required to form this intermediate, called
activated complex, is known as activation energy (Ea).

Taking logarithm both side

The plot of ln k Vs 1/T gives a straight line.

Slope = – Ea /R and intercept = ln A.
So we can calculate Ea and A using these values.

Converting to common logarithm lnX = 2.303 log X

2.303log k = 2.303log A – Ea/RT
log k = log A – Ea/2.303 RT
Let k1 and k2 are the rate constants for the reaction at two different temperatures T1 and T2 respectively.
log k1 = log A – Ea/2.303 RT1 …(i)
log k2 = log A – Ea/2.303 RT2 …(ii)
Subtracting eq. (i) from (ii)
log k2 - log k1 = Ea/2.303 R [1/T1 – 1/T2]

Assignments:

Q1. Which of the following observations is incorrect about the order of a reaction?
(a) Order of a reaction is always a whole number
(b) The stoichiometric coefficient of the reactants doesn’t affect the order
(c) Order of reaction is the sum of power to express the rate of reaction to the concentration terms of the
reactants.
(d) Order can only be assessed experimentally
Ans. (a)
Q2. In the reaction 2A + B → A2B, if the concentration of A is doubled and that of B is halved, then the rate
of the reaction will
(a) decrease 2 times
(b) increase 4 times
(c) increase 2 times
(d) remain the same
Ans. (c)
Q3. when the rate of the reaction is equal to the rate constant, the order of the reaction is
(a) zero order
(b) first order
(c) second order
(d) third order

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Ans. (a)
Q4. A substance ‘A’ decomposes by a first-order reaction starting initially with [A] = 2.00M and after
200min, [A] becomes 0.15M. For this reaction t1/2 is
(a) 53.72 min
(b) 50.49 min
(c) 48.45 min
(d) 46.45 min
Ans. (a)
Q5. A catalyst alters, which of the following in a chemical reaction?
(a) Entropy
(b) Enthalpy
(c) Internal energy
(d) Activation energy
Ans. (d)

Q6. Express the rate of the following reaction:

5 Br- (aq) + BrO3– (aq) + 6 H+ (aq) 3 Br2 (aq) + 3 H2O (l)

Q7. For the reaction R P, the concentration of a reactant changes from 0.03M to 0.02M in 25 minutes.
Calculate the average rate of reaction using units of time both in minutes and seconds.
Ans. Average rate = 4 x 10-4 mol L-1 min-1
Rate = 6.67 x 10-6 mol L-1 s-1

Q8. Calculate the overall order of a reaction which has the rate expression:
(a) Rate = k [A]1/2 [B]3/2
(b) Rate = k [A]3/2 [B]–1
Ans. (a) Second order
(b) half order.

Q9. Identify the reaction order from each of the following rate constants.
(i) k = 2.3 × 10–5 L mol–1 s–1
(ii) k = 3 × 10–4 s–1
Ans. (i) Second order reaction
(ii) first order reaction.

Q10. For a reaction, A + B Product; the rate law is given by, r = k [A]1/2 [B]2.
What is the order of the reaction?
Ans. Order = 2.5

Q11. The initial concentration of N2O5 in the following first order reaction
N2O5 (g) 2 NO2 (g) + 1/2O2 (g) was 1.24 × 10–2 mol L–1 at 318 K. The concentration of N2O5 after
60 minutes was 0.20 × 10–2 mol L–1.
Calculate the rate constant of the reaction at 318 K.
Answer: k = 0.0304 min-1

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Q12. Show that in a first order reaction, time required for completion of 99.9% is 10 times of half-life (t1/2)
of the reaction.
t = 6.909/k
For half-life of the reaction
t1/2 = 0.693/k
t/t1/2 = 10

Q13. The rate constant for a first order reaction is 60 s–1. How much time will it take to reduce the initial
concentration of the reactant to its 1/16th value?
Ans. t = 2.303/k {log[A]0/[A]}
= 2.303/60 {log (a/a/16)}
= 0.038 log16
= 0.038 x 1.204
= 0.046 seconds

Q14. A first order reaction takes 40 min for 30% decomposition. Calculate t1/2.
Ans. k = 2.303/t {log[A]0/[A]}
= 2.303/40 {log (a/0.70a)}
= 2.303/40 {0.1549}
k = 8.92 x 10-3 min-1
t1/2 = 0.693/k
t1/2 = 0.693/8.92 x 10-3 min-1
t1/2 = 77.7 min.

Q15. The rate of the chemical reaction doubles for an increase of 10K in absolute temperature from 298K.
Calculate Ea.
Ans. log k2 - log k1 = Ea/2.303 R [1/T1 – 1/T2]
logk2/k1 = Ea/2.303 R [1/T1 – 1/T2]
log2 = (Ea/2.303 x 8.314) [1/298 – 1/308]
Ea = log2 x 2.303 x 8.314 x 298 x 308
10
Ea = 52.898 kJ

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