Page # 3 Chemical Kinetics

CHEMICAL KINETICS Page # 3
CHEMICAL KINETICS
This branch of chemistry deals with the study of rates of chemical reactions and the mechanism by
which they occur. While studying reaction, one deals with :
(a) how fast (or slow) the reactants get converted into products
(b) the steps or paths through which the products are formed (reaction mechanism)
A B
t=0 a 0
t = t1 a – x1 x1
t = t2 a – x2 x2
t = t3 a – x3 x3
- - - - - - - - - - - - - - - - - -
- - - - - - - - - - - - - - - - - -
t = teq a–x x
O < t < teq 

→ CHEMICAL KINETICS
teq ≤ t < ∞ 
→ CHEMICAL EQUILIBRIUM
RATE OF A REACTION
In general, for a reaction : A → B, the behaviour of the concentration of the reactant and product, as
the reaction proceeds is shown graphically
[A]0
C1 – ∆ [ A ] –(C 2 – C 1 )
rav = =
∆t ( t 2 – t1 )
Concentration of A
∆[ A]
C2
∆t
d(A)
– d[ A ]
rinst = = slope
dt
dt
t1 t2 t
time
From the graph, it is clear that the concentration of the reactant decreases and that of the product
increases as the reaction proceeds and the rate of the change of the concentration of the reactant as
well as that of the product is also changing.
Rate of a reaction can, now, be defined in two ways :
Average Rate of reaction (rav) given by :
∆[ A ] ∆[B]
rav = – =
∆t ∆t
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Page # 4 CHEMICAL KINETICS
d[B ] [B]
rinst. = = slope
dt
Concentration of B
d[B]
C2 dt
∆[B]
C1 ∆[B] (c 2 – c1)
rav = =
∆t ( t 2 – t1 )
∆t
t1 t2 t
time
where ∆[A] and ∆[B] represents the change in the concentrations of 'A' and 'B' respectively over a time
interval ∆t
The average rate of the reaction between a time interval (tf – ti = ∆t) can be determined from the
above graph by locating the concentration of 'A' of 'B' on this graph at the time instants tf and ti as
shown.
If [A]f and [A]i are the concentrations of the reactant 'A' at the time instants tf and ti then :
 [ A ]f – [ A ]i 
rav = –  
 tf – ti 
Similarly from the plot of 'B' as a function of 't', we have :
 [B] – [B]i 
rav =  f 
 tf – ti 
Note :
The above expression for rav is equivalent to the slope of the line joining the points ( tf , [A]f ) and
( ti , [A]i) or ( tf , [B]f ) and ( ti , [B]i) as shown.
Instantaneous Rate of reaction (rinst.) can be calculated from rav
in the limit ∆t → 0 and is represented as :
d[ A ] d[B]
rinst. = – =
dt dt
Note : The above expression for rinst. is equivalent to the slope of the tangent from the plot of the
concentration of 'A' or 'B' at any time instant 't'.
The rate of the reaction (rinst. or rav) is always calculated as a positive quantity.
The rate of the change of the concentration of the reactant will be a negative quantity since its
concentration is decreasing with time.
The rate of the change of the concentration of the product will be a positive quantity since its
concentration is increasing with time.
The magnitude of the rates of the change of the concentration of reactants and products will be
equal in this case, as one mole of 'A' gives one mole of 'B' in the above reaction.
The rate of a reaction at any temperature depends on the concentration of the reactants and
sometimes on the concentration of some foreign substances (e.g a catalyst being used in the reaction
as well. The representation of this dependence of the rate of the reaction on the concentrations is
known as rate law and this rate law is determined experimentally.)
The above expression for rinst is called as differential rate law.
In general for a reaction :
mA + nB → pC + qD
The rate of reaction can be expressed as follows :

1 d[ A ] 1 d[B] 1 d[C] 1 d[D]
Rate = – = – =+ = +
m dt n dt p dt q dt
Problem 1 :
T h e r a t e o f f o r m a t i o n → NO(g) + Br2(g) is found to be 1.6 × 10–
o f N O ( g ) i n t h e r e a c t i o n N O B r ( g )
4
M/s. Find the rate of overall reaction and rate of consumption of NOBr.
d[NO]
We have : = 1.6 × 10–4 M/s.
dt
First write a balanced chemical equation. 2NOBr(g) → 2NO(g) + Br2(g)
1 d[NOBr ] 1 d[NO] 1 d[Br2 ]
Now, Rate of overall reaction = – = + = = 0.8 × 10–4 M/s
2 dt 2 dt 1 dt
d[NOBr ]
Rate of consumption of NOBr = – = + 1.6 × 10–4 M/s
dt
LAW OF MASS ACTION
aA+bB cC+d D
Rate α [A]a [B]b
Rate = K [A]a [B]b
Law of mass action states that the rate of reaction is directaly proportional to the concentration of
reacting species raised to the power of stoichiometric coefficients. But this is valid only for elementary
reactions.
ORDER OF A REACTION
By performing a reaction in actual in laboratory and carefully examining it, it is possible to express the
rate law as the product of concentrations of reactants each raised to some power. For example
consider the reaction :
P + 2Q → R
The differential rate law is written as :
d[P] 1 d[Q]
Rate = – = –
dt 2 dt
Also, Rate can be expressed as Rate = k[P]m[Q]n
where k is called as rate constant or velocity constant or specific reaction rate.
k is a characteristic of a reaction at a given temperature. It changing only when the temperature
changes.
The powers m and n are integers or fractions. m is called as order of reaction with respect to P and n
is called
as order of reaction with respect to Q.
The overall order of reaction = m + n
Note :
The values of m and n are calculated from the experimental data obtained for a reaction and the
powers m and n are not related to the stoichiometric coefficients of the reactants
Why difference in experimental rate equation & theoretical rate equation

N2 + 2O2 
→ N2O4
Theoretical rate = k [N2]1 [O2]2 ; order = 1 + 2 = 3
N2 + 1/2 O2 
→ N2O (fast)
N2O + 1/2 O2 
→ 2NO (fast)
2 NO + O2 
→ N2O4 (Slow) (Rate determine step)
rate = K [NO]2 [O2]1 ; Order = 2 + 1 = 3
NOTE :
(1) Order can be fractional
(2) Order can be zero.
(3) Order can be negative with respect to any one quantity but can not be negative for whole
reaction.
aA+ bB cC+dD
rate = k [A]a [B]b 
→ Theoretical Rate equation
rate = k [A]m [B]n 
→ Experimental Rate equation
Case (I) :
a=m , b=n
Elementary reaction
Single step reaction
Case (II) :
(i) a=m ; b ≠n
or (ii) a ≠m ; b=n
or (iii) a ≠ m ; b ≠ n
Complex reaction
multiple step reaction
Units of k :
In general, the rate law for a nth order reaction can be taken as :
dc dc
= –kc n [Note : rinst = – = kcn ]
dt dt
where k : rate constant; c : concentration and n : order of reaction
dc / dt
⇒ k=
cn
⇒ Units of k ≡ (mol/L)1–n (time)–1
For a 'zero' order reaction (n = 0) :
Units of k = (mol/L)1 (time)–1
⇒ Units are : mol/L/sec
For a first order reaction (n = 1) :
Units of k ≡ (time)–1
⇒ Units are : sec–1, min–1, hrs–1 etc.
For a second order reaction (n = 2) :
Units of k ≡ (mol/L)–1 (time)–1
⇒ Units are : L/mol/sec.
Problem 2 :
The rate constant for a given reaction is k = 3 × 10–5 s–1 atm–1. Express it in units of L mol–1 sec–
1
.
Try to express concentration of 1 atm into mol/L using gas law (PV = nRT)
PV = nRT ⇒ P = cRT (c : concentration in mol/L)
Substitute R = 0.0821 L–atm/mol/K ;
T = 273 K ; P = 1 atm
⇒ c = 0.04462 mol/L
3 × 10 –5
⇒ k= = 6.73 × 10–4 L/mol/s.
0.04462
Problem 3 :
From the rate laws for the reactions given below, determine the order with respect to each
species and the overall order :
(i) 2HCrO4– + 6I– + 14H+ → 2Cr3+ + 3I2 + 8H2O
Rate = k[HCrO4–] [I–]2 [H+]2
(ii) H2O2 + 2I– + 2H+ → I2 + 2H2O
Rate = k[H2O2] [I–]
(i) The order of the reaction with respect to [HCrO4–] is 1; with respect to [I–] is 2 and with respect to
[H+] is 2. The overall order of the reaction is 1 + 2 + 2 = 5
(ii) The order of the reaction with respect to [H2O2] is 1 and with respect to [I–] is 1. The overall order
of the reaction is 1 + 1= 2.
Note : In (i) stoichiometric coefficient of I– is 6 whereas the power coefficient (n) in the rate law is 2.
Reaction (i) may not take place in a single step. It may not be possible for all the 22 molecules to
be in a state to collide with each other simultaneously. Such a reaction is called a complex
reaction.
A complex reaction takes place in a series of a number of elementary reactions.
MOLECULARITY
As already discussed, the order of a reaction is an experimental concept. The theoretical aspect of
chemical kinetics is molecularity.
A complex chemical reaction is understood in terms of various indirect steps called elementary processes.
The study of a reaction in terms of elementary processes is called as reaction mechanism. Now various
elementary steps occur at different rates. The slowest elementary process in the reaction
mechanism is called as rate determining step.
Molecularity is defined as the number of ions or molecules or atoms taking part in an elementary
process of the reaction mechanism.
In the rate determining step, when one molecule takes part, it is said to be a unimolecular reaction ;
two molecules take part, it is said to be a bimolecular reaction; three molecules take part, it is said to
be a termolecular reaction.
Unimolecular : Bimolecular :
1. Cyclopropane → propene 1. NO(g) + O3 (g) → NO2(g) + O2(g)
2. O3(g) → O2(g) + O(g) 2. 2HI(g) → H2(g) + I2(g)
1
3. N2O5(g) → N2O4(g) + O (g) Termolecular :
2 2
1. 2NO(g) + O2(g) → 2NO2 (g)
Note : For a reaction : A → B in the rate law : rate = k[A]m [B]n
Neither the order of reaction (m + n) nor the molecularity of a reaction can be predicted from
stoichiometric coefficient of a balanced reaction. The order of reaction is always to be determined
e xp eri m ental l y and
molecularity is determined theoretically after studying the reaction mechanism. However as a theoretical
idea sometime, we can have an approximate order of reaction equal to molecularity (i.e., the number of
molecules taking part in slowest elementary for complex reactions).
Order of a reaction can be fraction also. For example consider the following reaction :
(i) H2(g) + Br2(g) → 2 HBr (g)
rate = k[H2] [Br2]1/2 (determined experimentally)
1 3
order of reaction = 1 + =
2 2
(ii) CH3CHO(g) → CH4(g) + CO(g)
rate = k[CH3CHO]3/2 (determined experimentally)
3
order of reaction =
2
Also note that sum of stoichiometric coefficient (1 + 1 = 2) is not equal to the order of reaction.
TYPES OF REACTION BASED ON KINETICS
(1) ZERO ORDER REACTION;

A product
Rate = K [A]o = k
A+B product
Rate = K [A] [B]° or K [A]1 [B]–1
o
Example :
(1) Photochemical Reactions, Photosynthesis
(2) CH4 + Cl2 
hυ
→
Cl – Cl 
→ Cl •
CH4 + Cl • 
→ CH3Cl + H •
All reactions occuring by free radical mechanism.
(2) FIRST ORDER REACTION :
A product
Rate = K [A]1
A+B product
Rate = K [A] [B]–1
2
Example :
(1) Radioactive disintegration.
(2) PCl5(g) 
→ PCl3(g) + Cl2(g)
Gaseous phase decomposition
(3) H2O2 → H2O + ½O2
(4) NH4NO2 → N2 + 2H2O
(3) SECOND ORDER REACTION :

2A product
Rate = K [A]2
A+B product
Rate = K [A] [B]1 1
Example :
(1) Alkaline hydrolysis of esters.
(2) Self Canizzaro’s reactions,
(4) nth ORDER REACTION :

nA product
Rate = K [A]n
Zero Order Reactions :
The rate law for zero order reactions (n = 0) is written as :

A product
t=o a = [A]o o
t=t a – x = [A] x
d [A]
Rate of reaction = – .............(1)
dt
Rate of reaction = k [A]o .............(2)
From equation (1) and (2)
d [A]
– = k [A]°
dt
d [A]
– =k
dt
[A] t
– ∫ [A] o
d [A] = k ∫ dt
o
[A]o – [A] = kt
[A] o – [A] x
k= =
t t
Half life (t 1/2) :
Time in which half of initial amount is left.
[A]o 
→ [A]o/2
t=o t = t1/2
[A]o – [A]o /2
k=
t 1/2
[A] o
t1/2 =
2k
Thus, for a Zero order reaction, half life is directly proportional to initial concentration of the reactant.
Clearly, zero order reactions are those, whose rates are not affected by change in concentrations of
reactants (i.e., independent of concentration). The rates of such reactions only depend upon
temperature. Most of photochemical reactions are zero order reactions. Other examples are :
decomposition of HI over the surface of gold and NH3 over tungsten.
Equation (i) can be rearranged and integrated to get the variation of the concentration of the
reactants as a function of time.
A0
t1/ 2
Slope = –k
A
t A0
From the above expression, it is clear that if we plot A as a function of time (t) then it will be a
straight line with a negative slope = – k and Y - Intercept of A0
FIRST ORDER REACTION
A product
t=o [A]o
t=t [A]
d [A]
Rate of reaction = – ...........(1)
dt
Rate of reaction = k [A]1 ...........(2)
From equation (1) & (2)
d [A]
– = k [A]
dt
[A] t
– ∫
[A] o
d[A]/[A] = k ∫ dt o
ln [A]o/[A] = kt
2.303 [A]o
k = log
t [A]
Half life (t1/2) :

t1/ 2
t = t1/2 [A] = [A]o/2
2.303 [A]o 2.303

k= log = log 2
t 1/2 [A]o /2 t1/ 2
A
2.303
t1/ 2 = log10 2
k
0.693 loge 2
t1/ 2 = t 1/ 2 =
k k
Average life :
[ A ]o
Kt = ln [A]
[A]o = [A] e Kt
[A] = [A]o e–kt

[ A ]o
[A] = where , n = number of half lifes.
2n
t=0 [A]0
[ A] 0 t1/2
2
t = t1/2 [ A] 0
2
[ A] 0 2 t1/2
[ A] 0 4
t = 2t1/2
4
[ A] 0 3 t1/2
t = 3t1/2 [ A] 0
8
8
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
[A]o [A]o [A]o
t 1/2 + 2 t 1/2 + 3t1/2 + - - - - - -
tav = 2 4 8
[ A]o
1 2 3 4 
tav =  + 2 + 3 + 4 + - - - - - - -  t 1/2
2 2 2 2 
0.693
tav = 1.44 t1/2 here t 1/2 =
k
1.44 × 0.693
tav =
K
1
⇒ tav =
K
Features of a First Order Reaction :

1. A first order reaction must follow above form of rate law for all time instants.
This means if we are given value of A0 and values of x at different time instants [i.e.(A0 – x) as value
of reactants after t], the values of k can be calculated for different time instants by using the above
first order law.
If the reaction for which the data were given is a first order reaction, then all values of k will
approximately equal to each other.
2. The time for half reaction for a first order reaction is independent of initial concentration of
reactants.
3. The concentration of reactants in a first order reaction decreases exponentially with time (see figure)
[A = A0e–kt from (ii)] A0
Note that plot of log10 A vs t is linear. It is important to note that
A
equation of this straight line is of the form :
t
y = mx + C. Comparing it with Ist order rate law as follows :

A0
kt = 2.303 log10
A log10A0
⇒ log10 A =  − k t + log10 A 0 is the equation of line. Slope =

−k
 2.303  log10 A 2.303
 −k 
Note that slope of the line   and Y-intercept (OA) = log10A0
2.303  t
Rate constant of a first order reaction can also be calculated by measuring the concentration
of the reactants at two time instants (if the initial concentration is not known).
If A1 and A2 are the reactant's concentrations at two time instants 't1' and 't2' respectively, then we
have :
A0
2.303log10 = kt1 ...(iii)
A1
A0
and 2.303log10 = kt 2 ... (iv)
A2
Subtracting (iv) from (iii), we get :
A1
2.303log10 = k( t1 − t 2 ) Thus, k can be evaluated.
A2
The molecularity of acidic hydrolysis of sucrose and esters is 2, whereas their order is 1. In both the
reactions water is in excess so that its concentration remains constant throughout the reaction.
The rate of reaction therefore depends only on the concentration of sucrose and ester in two
reactions respectively. So the reactions in which the molecularity is 2 or 3 but they conform to the
first order kinetics are known as pseudo first order reactions OR pseudo unimolecular reactions.
C12H22O11 + H2O + H+ → C6H12O6(glucose) + C6H12O6(fructose)
CH3COOC2H5(ester) + H2O + H+ → CH3COOH + C2H5OH
(In both the reactions, H+ ion acts as a catalyst)
Problem : 4
For a reaction 2NO(g) + 2H2(g) → N2(g) + 2H2O (g) ; the following data were obtained.
[NO] (mol/L) [H2](mol/L) Rate (mol/L/s)
1. 5 × 10 –3
2.5 × 10 –3
3 × 10–5
2. 15 × 10 –3
2.5 × 10 –3
9 × 10–5
3. 15 × 10 –3
10 × 10 –3
3.6 × 10–4
(a) Calculate the order of reaction.
(b) Find the rate constant.
(c) Find the initial rate if [NO] = [H2] = 8.0 × 10–3 M
Assuming rate law can be expressed as follows :
rate = k[NO]x [H2]y
By analysing the data :
From observation 1 and 2, we see that [H2] is constant and when [NO] is tripled, the rate is also
tripled.
⇒ rate (r) ∝ [NO] ⇒ x=1
From observations 2 and 3, we see that [NO] is constant; when [H2] is increased four times, the rate
also increases four times :
rate ∝ [H2] ⇒ y=1
⇒ r = k [NO] [H2O]
⇒ The order of reaction w.r.t No and H2 is 1 and the overall order of reaction is 1 + 1 = 2.
Initial rate = k[NO][H2] = 2.4 × (8 × 10–3)2 = 1.536 × 10–4 mol/L/s.
Problem : 5
The rate of change of concentration of C in the reaction 2A + B → 2C + 3D was reported as 1.0 mol
litre–1 sec–1. Calculate the reaction rate as well as rate of change of concentration of A, B and D.
Sol. We have,
1 d[ A ] d[B] 1 d[C] 1 d[D]
– = – = = = rate of reaction
2 dt dt 2 dt 3 dt
d[C]
∴ = 1.0 mol litre–1 sec–1
dt
d[ A] d[C]
∴ – = = 1.0 mol L–1sec–1
dt dt
d[B] 1 d[C] 1
– = = = 0.5 mol L–1 sec–1
dt 2 dt 2
d[D] 3 d[C] 3
= = × 1 = 1.5 mol L–1 sec–1
dt 2 dt 2
Also,
1 d[C]
∵ Rate =
2 dt
1
∴ Rate = × 1 = 0.5 mol L–1 sec–1
2
Problem : 6
For the reaction A + B → C, the following data were obtained. In the first experiment, when the
initial concentrations of both A and B are 0.1 M, the observed initial rate of formation of C is 1 ×
10–4 mol litre–1 minute–1. In the second experiment when the initial concentrations of A and B
are 0.1 M and 0.3 M, the initial rate is 9.0 × 10–4 mol litre–1 minute–1.
(a) Write rate law for this reaction
(b) Calculate the value of specific rate constant for this reaction.
Sol. Let Rate = K[A]m[B]n
(a) r1 = 1 × 10–4 = K[0.1]m [0.1]m ...(1)
r2 = 9 × 10–4 = K[0.1]m[0.3]n ...(2)
r3 = 2.7 × 10–3 = K[0.3]m[0.3]m ...(3)
By Eqs. (1) and (2),
n
r1 1 × 10 –4  1 
= = 
r2 9 × 10 –4  3 
∴ n=2
By Eqs. (2) and (3),
m
r2 9 × 10 –4  1
= =  m= 1
r3 27 × 10 –4  3
∴ Rate = K[A]1[B]2
(b) Also by Eq. (1), 1 × 10–4 = K[0.1]1 [0.1]2
K = 10–1 = 0.1 L2 mol–2 min–1
Problem : 7
The chemical reaction between K2C2O4 and HgCl2 is ;
2HgCl2 + K2C2O4 → 2KCl + 2CO2 + Hg2Cl2
The weights of Hg2Cl2 precipitated from different solutions in given time were taken and
expressed as following :
Time (minutes) HgCl2 (M) K 2C2O 4 (M) Hg2Cl2 formed (M)

60 0.0418 0.404 0.0032
65 0.0836 0.404 0.0068
120 0.0836 0.202 0.0031
Let the rate law be written as : r = k[HgCl2]x [K2C2O4]y

0.0032
1. = k[0.0418]x [0.404]y
60
0.0068
2. = k[0.0836]x[0.404]y
65
0.0031
3. = k[0.0836]x [0.202]y
120
Solving the above equations, we get :
x = 1 and y = 2 ⇒ order of reaction w.r.t x = 1 and y = 2 and overall order is 3.
Problem : 8
The reaction given below, involving the gases is observed to be first order with rate constant
7.48 × 10–3 sec–1. Calculate the time required for the total pressure in a system containing A at
an initial pressure of 0.1 atm to rise to 0.145 atm also find the total pressure after 100 sec.
2A(g) → 4B(g) + C(g)
Sol. 2A(g) → 4B(g) + C(g)
initial P0 0 0
at time t P0 – P′ 2P′ P′/2
3P'
Ptotal = P0 – P′ + 2P′ + P′/2 = P0 +
2
2
P′ = (0.145 – 0.1) = 0.03 atm
3
2.303 P0
k= log
2t P0 – P'
2.303  0.1 
t= log 
7.48 × 10 – 3 × 2  0.07 
t = 23.84 sec
2.303  0.1 
Also, k = log 

2t  P0 – P' 
2.303  0.1 
7.48 × 10–3 = log 
2 × 100  0.1 – P' 
0.1/0.1 – P′ = 5
P′ = 0.08
3
Ptotal = 0.1 + (0.080) ~
– 0.22 atm.
2
Problem : 9
The net rate of reaction of the change :
[Cu(NH3)4]2+ + H2O [Cu(NH3)3H2O]2+ + NH3 is,
dx
= 2.0 × 10 – 4 [Cu(NH3)4]2+ – 3.0 × 105 [Cu(NH3)3H2O]2+ [NH3]
dt
calculate :
(i) rate expression for forward and backward reactions.

(ii) the ratio of rate constant for forward and backward reactions.
(iii) the direction of reaction in which the above reaction will be more predominant.
Sol. (i) Rate of forward reaction = 2.0 × 10–4 [Cu(NH3)4]2+ [H2O]
Rate of backward reaction = 3.0 × 105 [Cu(NH3)3H2O]2+ [NH3]
(ii) Also, Kf = 2.0 × 10–4
Kb = 3.0 × 105
Kf 2.0 × 10 –4
∴ = = 6.6 × 10–10
Kb 3.0 × 10 5
(iii) More predominant reaction is backward reaction.
Problem : 10
The rate law for the decomposition of gaseous N2O5,
1
N2O5(g) → 2NO2(g) + O (g)
2 2
is observed to be
d[N2 O 5 ]
r= – = k[N2O5]
dt
A reaction mechanism which has been suggested to be consistent with this rate law is
k
N2O5(g) NO2(g) + NO3(g) (fast equilibrium)
k1
NO 2 (g) + NO 3 (g)  → NO2(g) + NO(g) + O2(g) (slow)
NO(g) + NO3(g)  k2
→ 2NO2(g) (fast)
Show that the mechanism is consistent with the observed rate law.
Since the slow step is the rate determining step, hence
r = k1[NO2] [NO3] ...(1)
and from the fast equilibrium step,
[NO 2 ][NO 3 ]
K=
[N2 O 5 ]
Thus, [NO2] [NO3] = K[N2O5] ...(ii)
Using (ii) in (i), we get :
r = k1K[N2O5] = k[N2O5] where k = k1K
This shows that the mechanism is consistent with the observed rate law.
Problem : 11
The half life of first order decomposition of nitramide is 2.1 hour at 15°C.
NH2NO2(aq) → N2O(g) + H2O (l)
If 6.2 gm of NH2NO2 is allowed to decompose, find :
(a) time taken for nitramide to decompose 99%;
(b) volume of dry N2O gas produced at this point at STP.
Sol. (a) Using first order kinetics, we have :
A0
kt = 2.303 log10
A
0.693 100
⇒ × t = 2.303 log ⇒ t = 13.96 hours
21
. 100 – 99
(b) 6.2 gm of NH2NO2 ≡ 0.1 mol

and 1 mole NH2NO2 ≡ 1 mole of N2O
As 99% of NH2NO2 is decomposed
⇒ 0.099 mol of NH2NO2 is decomposed
0.099 mol of N2O are produced ≡ 22.4 × 0.099 = 2.217 L of N2O at STP.
Second Order kinetics
Case I :
A product
t=o [A]o
t = t [A]t
d [A]
Rate of reaction = – .............(1)
dt
Rate of reaction = k [A]2 .............(2)
d [A]
– = K [A]2
dt
[A] d[ A ] t
– ∫ [A]o [A] 2
= k ∫ dt
o
1 1
– = Kt
[A] [A]o
1/[A] – 1 /[A]o
K=
t
[A o ]
Half-life (t1/2) : [A]t =
2
K = 2/[A]o – 1/[A]o
1
t1/2 = k [A]
o
In this half life is inversely proportional to initial concentration
Case (II):
A+B product
t=o a b
t=t a–x b–x
d [A]
Rate of reaction = – ............(1)
dt
Rate of reaction = k [A] [B] ............(2)
d [A]
– = k [ A ] [B]
dt
dx
= k (a – x) (b – x)
dt
x dx t
∫ o (a – x) (b – x)
= k ∫ dt
o
x dx x dx t
∫ o (b – a) (a – x)
+ ∫ o (a – b) (b – x)
= k dt
o ∫
(–1)  a – x  (– 1) b – x 
ln  + ln   = kt
(b – a)  a  (a – b)  b 
a b
ln – ln = k (b – a) t
a– x b–x
1   a b – x 
k = t (b – a)  ln  a – x × b 
  
1 a (b – x)
k = ln
t (b – a) b (a – x)
nTH ORDER KINETICS
A product
d [A]
rate = – ................(1)
dt
rate = k [A]n ................(2)
d [A]
⇒ – = k[A]n
dt
[A]t
d [A] t
⇒ – ∫
[A]o
[A]n ∫
= k dt
o
[A]
1  1 
⇒   = kt
(n – 1)  [A]n –1  [ A ]
o
1  1 1 
⇒  n –1
–  = kt
(n – 1)  [A] t [A]o n –1 
1  1 1 
⇒ k=  n –1
– 
(n – 1) t  [A] t [A] o n –1 
[ A ]o
Half-life (t1/2) : at t = t1/2 , [A]t =
2
1  2n –1 1 
⇒ k = (n – 1) t  n –1
– 
1/2  [A]o [A]o n –1 
2n –1 – 1 1
⇒ t 1/2 = n –1 ⇒ t 1/ 2 α
(n – 1) K [A] o [A] o n –1
Problem : 12
For the non-equilibrium process, A + B → Products, the rate is first order w.r.t A and second
order w.r.t. B. If 1.0 mole each of A and B are introduced into a 1 litre vessel and the initial rate
were 1.0 × 10–2 mol/litre-sec, calculate the rate when half of the reactants have been used.
Sol. Rate = K[A] [B]2
∴ 10–2 = K[1] [1]2
or K = 10–2 litre2 mol–2 sec–1
Now ratell = 10–2 × 0.5 × (0.5)2
or New rate = 1.2 × 10–3 mol/L-sec
Problem : 13
The reaction A + OH– → Products, obeys rate law expression as,
–d[A]
= k[A][OH – ]
dt
If initial concentrations of [A] and [OH –] are 0.002 M and 0.3 M respectively and if it takes 30
sec for 1% A to react at 25°C, calculate the rate constant for the reactions.
Sol. A + OH– → Products
t=0 0.002 0.3
 0.002 × 1  0.002 × 1
t = 30 0.002 – 100  0.3 – 100 
   
Using K = 2.303 log10 b( a – x)

t(a – b) a(b – x)
 0.002 × 1
0.3 × 0.002 –
2.303  100 
K= log10  0.002 × 1
30 × ( 0.002 – 0.3) 0.0020.3 –
 100 
K = 1.12 × 10–3 L mol–1 sec–1
Problem : 14
A certain reaction A + B → products ; is first order w.r.t. each reactant with k = 5.0 × 10–3 M–1s–
1
. Calculate the concentration of A remaining after 100s if the initial concentration of A was 0.1
M and that of B was 6.0 M. State any approximation made in obtaining your result.
Sol. A + B → products
Given : Rate = k[A][B] (2nd Order reaction)
Now, since [B] >> [A], [B] can be assumed to remain constant throughout the reaction. Thus, the rate
law for the reaction, becomes :
Rate ≈ k0[A] where k0 = k[B] = 5.0 × 10–3 × 6.0 s–1 = 3.0 × 10–2 s–1
Thus, the reaction is now of first order.
A0
Using, 2.303 log10 = k0t
A
0. 1
⇒ 2.303 log10 = k 0t = 3
A
0.1
⇒ log e =3 [∴ logex = 2.303 log10x]
A
0.1
⇒ A= 3
= 5 × 10 – 3 M
e
ANALYSIS OF SOME IMPORTANT FIRST-ORDER REACTIONS
Decomposition of Hydrogen peroxide (H2O2)
H2O2(g) → H2O(g) + ½O2(g)

The rate of this first order reaction is measured by titrating a fixed volume of H2O2 (undecomposed)
against a standard solution of KMnO4. Here KMnO4 acts as oxidising agent and H2O2 as reducing agent.
The volumes of KMnO4 used for H2O2 after regular intervals of time are as follows.
Time instants t=0 t1 t2 t3 t4 t5
Vol. of KMnO4 V0 V1 V2 V3 V4 V5
Volume of KMnO4 at t = 0 corresponds to volume of H2O2 initially present.
⇒ A0 ∝ V0
Volume of KMnO4 at time instants t1, t2, t3, .................... corresponds to volume of H2O2 remaining
a f t e r
t1, t2, t3, .................
⇒ A ∝ Vt
Now it being a first order reaction, follows first order kinetics, so
V0
k t = 2.303 log10 V
t
Now using the above expression, if we calculate the values of k for different time intervals t1, t2,
........... (for actual numerical data), the values of k should be same if the reaction follows first order
kinetics.
Decomposition of ammonium nitrite (NH4NO2)
and benzene diazonium chloride (C6H5N = NCl)

NH4NO2(g) → 2 H2O(g) + N2(g)
C6H5 – N = N – Cl(g) → C6H5 – Cl(g) + N2(g)
The rate of both the reaction is studied (measured) in similar manner. The volume of nitrogen (N2) is
collected after a regular interval of time as follows :
Tim e instants t = 0 t1 t2 t3 t4 t
Vol. of N 2 0 V1 V2 V3 V4 V∞
At t = 0, clearly the volume of N2 = 0

Time instant t = ∞ means the end of a reaction i.e., when whole of NH4NO2 or C6H5 – N = N – Cl is
decomposed.
⇒ A t t = ∞, V∞ corresponds to the initial volume of NH4NO2 or C6H5 – N = N – Cl
(Note that the ratio of stoichiometric coefficient for both N2 : NH4NO2 or N2 : C6H5N = NCl is 1 : 1)
⇒ A0 ∝ V∞
A t t = t1, t2, t3................ the volume of N2 corresponds to concentration of product formed i.e., equal
to x.
⇒ x ∝ Vt
⇒ A0 – x ∝ V∞ – Vt
V∞
⇒ k t = 2.303 log10 V – V
∞ t
Hydrolysis of Esters (CH3COOC2H5)

CH3COOC2H5 (ester) + H2O + HCl(H+) → CH3COOH + C2H5OH
The reaction rate is measured by titrating the acid (CH3COOH) produced against a standard alkali
solution. Note that when a test sample is prepared from the reacting mixture, there are two acids :
one is minral acid H+ (HCl or any other) and second is CH3COOH produced. So volume of alkali used
gives titration value for both acids. The data is collected in the following manner.
Time instants t=0 t1 t2 t3 t4 t∞
Vol. of NaOH V0 V1 V2 V3 V4 V∞
At t = 0, V0 is the volume NaOH used to neutralise the mineral acid present (H+) being used as catalyst.
(At t = 0, no CH3COOH is yet produced)
At t = ∞ (i.e., at the end of hydrolysis), V∞, is the volume of NaOH used to neutralise whole of CH3COOH
plus vol. of HCl present At t = ∞, volume of CH3COOH corresponds to volume of ester taken initially
⇒ A0 ∝ V∞ – V0 (as V0 ≡ vol. of HCl)
At t = t1, t2, t3............ V1, V2, V3, ................corresponds to vol. of HCl plus vol. of CH3COOH being
produced.
⇒ x ∝ Vt – V0
⇒ A0 – x ∝ (V∞ – V0) – (Vt – V0)
⇒ A0 – x ∝ V∞ – Vt
V∞ – V0
⇒ k t = 2.303 log10
V∞ – Vt
Inversion of Cane Sugar (C12H22O11)
C12H22O11 + H2O + H+ → C6H12O6(glucose) + C6H12O6 (fructose)
The rate is measured by measuring the change in the angle of rotation (optical activity) by a polarimeter.
Sucrose is dextro-rotatory, glucose is dextro-rotatory and fructose is leavo-rotatory. The change
produced in rotatory power in time t gives a measure of x, the quantity of sucrose decomposed in that
time. The total change in the rotatory power produced at the end of the reaction gives the measure of
A0, the initial concentration of sucrose.
If r0, r1 and r∞ represent rotations at the start of reaction, after time t and at the end of reaction
respectively,
then
⇒ A0 ∝ r0 – r∞ and x ∝ r0 – rt
⇒ A0 – x ∝ rt – r∞
r0 – r∞
⇒ k t = 2.303 log10 r – r
t ∞
DECOMPOSITION OF AsH3(g)
In first-order reactions involving gases, sometime measuring the pressure of the reaction mixture is
very good method for measuring reaction rates.
For example consider decomposition of arsine gas (AsH3)
3
AsH3(g) → As(s) + H2 ( g)
2
The rate of reaction is measured as the increase in pressure of the reaction mixture. Note that there is
an increase in number of moles of the gaseous products to the right, so as the reaction proceeds,
there will be an increase in pressure of contents (P ∝ n).
Let the initial pressure of AsH3(g) is P0, if x is the decrease in pressure of AsH3(g) after time t.
AsH3(g) → As(s) + H2(g)
A0 ≡ initial pressure P0 0 0
3
A ≡ partial pressures P0 – x 0 x
2
Arsenic is solid, so P(AS) = 0
After time t, let Pt be the total pressure, then

3
Pt = P(AsH3) + P(H2) = (P0 – x) + x
2
1
⇒ Pt = P0 + x ⇒ x = 2(Pt – P0)
2
Now A0 ∝ P0
and A ∝ P0 – x ≡ P0 – 2 (Pt – P0) ≡ 3P0 – 2Pt
P0
⇒ k t = 2.303 log10 3P – 2P
0 t
On similar pattern, please try to write the expression for Ist order rate law for following first-order
reactions. (in terms of P0 and Pt)
1
1. N2O(g) → N2(g) + O (g)
2 2
2. (CH3)3C – O – O – C(CH3)(g) → 2(CH3)2C = O(g) + C2H6(g)
Problem : 15
Dimethyl ether decomposes according to the following reaction :
CH3 – O – CH3(g) → CH4(g) + CO(g) + H2(g)
At a certain temperature, when ether was heated in a closed vessel, the increase in pressure with time
was noted down.
Time (min) 0 10 20 30
Pressure (mm Hg) 420 522 602 678
(i) Show that the reaction is first order.

(ii) Compute the pressure of CO(g) after 25 minutes.
Sol. CH3 – O – CH3 (g) → CH4(g) + CO(g) + H2(g) (all are gases)
time CH3–O–CH3 CH4 CO H2
t=0 C 0 ≡ P0 0 0 0
t=t C t ≡ P0 – x x x x
⇒ Pt = P0 + 2x
1
⇒ x= (P – P0)
2 t
A0 P0 2P0
⇒ = =
A P0 – x 3P0 – Pt
Now find k1, k2 and k3 using the first order kinetics
2P0
k t = 2.303 log10 3P – 2P
0 t
2.303 2(420)
k1 = log10 = 0.0129 min–1
10 3( 420 ) – 522
2.303 2(420)
k2 = log10 = 0.0122 min–1
20 3(420) – 602
2.303 2( 420 )
k3 = log10 = 0.0123 min–1
30 3( 420 ) – 678
As k1 ~ k2 ~k3, the reaction is first order.
1
kaverage = (k 1 + k 2 + k 3 ) = 0.0127 min–1
3
1
PCO = x = (Pt – P0 )
2
Find P after t = 25 min using first order kinetics with k = 0.0127 min–1
2( 420)
⇒ log10 = 0.0127 × 25
3(240) – Pt
⇒ Pt = 648.46 mm ⇒ x = 114.23 mm
Problem : 16
The decomposition of N2O5 according to following reaction is first order reaction :
2N2O5(g) → 4NO2(g) + O2 (g)
After 30 min. from start of the decomposition in a closed vessel, the total pressure developed
is found to be 284.5 mm of Hg and on complete decomposition, the total pressure is 584.5 mm
of Hg. Calculate the rate constant of the reaction.
Sol. 2N2O5(g) → 4NO2(g) + O2(g)
2N2O5 4NO2 O2
P0 0 0
P0 – 2x 4x x
P0 : initial pressure ; Let Pt : pressure at 30 min and P∞ : pressure at the end of decomposition.
1
⇒ Pt = P0 + 3x ⇒ x= (P – P0)
3 t
1 5 2
and P∞ = 2P0 + P0 = P0 ⇒ P0 = P∞
2 2 5
For the first order kinetics
A0
keff t = 2.303 log10
A
A0 : initial concentration ; A : final concentration
1
P∞
A0 P0 5 A 0 3  P∞ 
= = =  
Now A P0 – 2x 1 P – 2 / 5P∞ ⇒ 
P∞ – 2 t A 5  P∞ – Pt 
5 3
1 3 584.5
⇒ keff = × 2.303 log10 × = 5.204 × 10–3 min–1
30 5 584.5 – 284.5
5.204
k for the reaction = × 10 –3 = 2.602 × 10–3 min–1
2
Problem : 17
The gas phase decomposition of N2O5 to NO2 and O2 is monitored by measurement of total
pressure. The following data are obtained.
Ptotal (atm) 0.154 0.215 0.260 0.315 0.346
Time (sec) 1 52 103 205 309
Find the average rate of disappearance of N2O5 for the time interval between each interval and
for the total time interval. [Hint : Integrated rate law is NOT to be used]
Sol. 2N2O5(g) → 4NO2(g) + O2(g)
Initial Pressure (at t = 0) P0 0 0
At equilibrium P0 – 2x 4x x
1
Now: Pt = (P0 – 2x) + 4x + x ⇒ x= (Pt – P0 )
3
1
PN2O 5 = P0 – 2x = (5P0 – 2Pt )
3
2
Thus, ∆PN2O 5 = (Pt 1 – Pt 2 ) where Pt 2 and Pt 1 are the total pressures at time instants t2 and t1 (t2 >
3
t1) respectively
∆PN2O 5
Ptotal (atm) Time (sec) = Avg. Rate of disappearance of N2O5
∆t
0.154 1 (0.154 – 0.215 )

= –1.20 × 10 –3
(52 – 1)
0.215 52
(0.215 – 0.260)
= –0.88 × 10 –3
(103 – 52)
0.260 103
(0.260 – 0.315)
= –0.54 × 10 –3
(205 – 103)
0.315 205
(0.315 – 0.346 )
= –0.30 × 10 –3
0.346 309 (309 – 205)
Problem : 18
5 ml of ethylacetate was added to a flask containing 100 ml f 0.1 N HCl placed in a thermostat
maintained at 30°C. 5 ml of the reaction mixture was withdrawn at different intervals of time
and after chilling, titrated against a standard alkali. The following data were obtained :
Tim e (m inutes) 0 75 119 183 ∞
Volum e of alk ali used in m l 9.62 12.10 1.10 14.75 21.05
Show that hydrolysis of ethyl acetate is a first order reaction.

Sol. The hydrolysis of ethyl acetate will be a first order reaction if the above data confirm to the equation.
2.303 V – V0
k1 = log ∞
t V∞ – Vt
Where V0, Vt and V∞ represent the volumes of alkali used at the commencement of the reaction, after
time t and at the end of the reaction respectively, Hence
V∞ – V0 = 21.05 – 9.62 = 11.43
Time V∞ – Vt k1
2.303 1143
.
75 min 21.05 – 12.10 = 8.95 log = 0.003259 min–1
75 8.95
2.303 1143
.
119 min 21.05 – 13.10 = 7.95 log = 0.003051 min–1
119 7.95
2.303 1143
.
183 min 21.05 – 14.75 = 6.30 log = 0.003254 min–1
183 6.30
A constant value of k shows that hydrolysis of ethyl acetate is a first order reaction.
Problem : 19
The optical rotations of sucrose in 0.5N HCl at 35°C at various time intervals are given below.
Show that the reaction is of first order :
Time (minutes) 0 10 20 30 40 ∞
Rotation (degrees) +32.4 +28.8 +25.5 +22.4 +19.6 –11.1
Sol. The inversion of sucrose will be first order reaction if the above data confirm to the equation, k1 =
2.303 r0 – r∞
log r – r
t t ∞
Where r0, rt and r∞ represent optical rotations initially, at the commencement of the reaction after time
t and at the completion of the reaction respectively
In the case a0 = r0 – r∞ = +32.4 – (–11.1) = +43.5
The value of k at different times is calculated as follows :
Time rt rt – r∞ k
2.303 43.5
10 min +28.8 39.9 log = 0.008625 min–1
10 39.9
2.303 43.5
20 min +25.5 36.6 log = 0.008625 min–1
10 36.6
2.303 43.5
30 min +22.4 33.5 log = 0.008694 min–1
30 33.5
2.303 43.5
40 min +19.6 30.7log = 0.008717 min–1
40 30.7
The constancy of k1 indicates that the inversion of sucrose is a first order reaction.
Problem : 20
The hydrolysis of ethyl acetate
CH3COOC2H5 + H2O CH3COOH + C2H5OH
in aqueous solution is first order with respect to ethyl acetate. Upon varying the pH of the
solution the first order rate constant varies as follows.
pH 3 2 1
k1 ×10–4s–1 1.1 11 110
what is the order of the reaction with respect of H+ and the value of the rate constant?
Sol. Rate = k[CH3COOC2H5]a[H+]b
[H+] is constant through out the reaction
k1 = k[H+]b
b b
 k 1   [H + ]1  .  10 –3 
11
Hence,  '  =  +  = 
 k 1   [H ] 2  11  10 –2 
b=1
k1= k[H+]
1.1 × 10–4 = k(10–3) ⇒ k = 1.1 × 10–1 dm3 mol–1 sec–1
COMPLEX (FIRST ORDER) KINETICS
K1 B K1 K1 A B
A B C
A K2
C
Parallel Kinetics Series Kinetics Reversible Kinetics
PARALLEL KINETICS
K1 B
I
A K2
II C
t = 0 [A]o
t = t [A]
Rate of change of A = [rate of change of A]I + [rate of change of A]II
d [A]
– = K1 [A] + K2 [A]
dt
dB dC
= k 1A , = k 2A
dt dt
[B] k 1
⇒ =
[C ] k 2
k1
% of B in the mix of A & B = k + k × 100
1 2
k2
% of C in the = × 100
k1 + k 2
d [A]
– = (K 1 + K 2 ) [A]
dt
2.303 [A] o 0.693

K1 + K 2 = log10 t 1/ 2 =
t [A] t K1 + K 2
GENERALIZATION
B
K1
K2
A C
Kn
Z
2.303 [A]
K1 + K 2 + - - - - - - K n = log o
t [ A ]t
0.693
t1/ 2 =
K1 + K 2 + - - - - K n
Problem : 21
An organic compound A de composes following two parallel first order mechanisms :
k1
B
k1 1
A ; k = 9 and k1 = 1.3 × 10–5 sec–1.
k2 2
C
Calculate the concentration ratio of C to A, if an experiment is allowed to start with only A for
one hour.
k1 1
Sol. =
k2 9
But k1 = 1.3 × 10–5 sec–1 ; k2 = 9 × 1.3 × 10–5 sec–1 = 117 × 10–5 sec–1
(k1 + k2) = (1.3 × 10–5) + (11.7 × 10–5) sec–1 = 13 × 10–5 sec–1 ....(1)
[B] t 1 [ C] t
Also [C] = 9 ⇒ [B]t = ...(2)
t 9
For parallel first order reaction :
d[ A ]
– = (k1 + k2) [A]
dt
[ A ]t t= t
d[ A ]
⇒ – ∫
[ A ]0
[A] ∫
= (k 1 + k 2 ) dt
t=0
[ A ]0  [ A ] t + [B] t + [C] t 
⇒ ln [ A ] = (k 1 + k 2 ) t ; ln  [ A] t
 = (k1 + k2)t
t  
 [ C] t 
 [ A] t + + [ C] t 
⇒ ln  9  = (k 1 + k 2 ) t [from eq. (2)]
 [A] t 
 
 10 [C] t 
⇒ ln 1 +  = (k 1 + k 2 ) t
 9 [ A] t 
 10 [C] t 
⇒ ln 1 + 9 [ A ]  = 13 × 10–5 × 60 × 60 = 0.468 [from eq. (1)]
 t
10 [C] t [ C] t
= 0.537
⇒ 1+ = 1.5968 ;
9 [ A] t [ A] t
(2) SERIES KINETICS
K1 K2
A  → B 
→ C
d [A]
– = K 1 [A]
dt
d [B]
= Rate at which B is produced – Rate at which B is consumed
dt
d [B]
= Rate at which A is consumed – Rate at which B is consumed
dt
d [B]
= K 1 [A] – K 2 [B]
dt
d [C]
= Rate at which C is produced
dt
= Rate at which B is consumed
d [C]
= K 2 [B]
dt
d [A]
– = K 1[A]
dt
[ A ]t = [ A ]o e –k 1t
d [B]
= K 1 [A] – K 2 [B]
dt
d [B]
+ K 2 [B] = K 1 [A]o e – k 1t
dt
dy
+ P (x) y = Qx
dx
y×e ∫ P (x) dx
∫
= Q (x). e ∫ P (x) dx dx + C
[B] e ∫ k 2dt = ∫K 1 [A]o e –k 1t e ∫ k 2dt dt + C
[B] e k 2t = k 1 [A]o ∫e
–k 1t
e k 2t dt + C
[B] e k 2 t = k 1[A]o ∫e
(k 2 – k 1)t
dt + C
e (k 2 – k 1)t
[B] e k 2 t = k 1 [A]o +C
(k 2 – k 1)
At, t = o , [B] = 0
k 1[ A ]o –k 1[ A ]o
0 = k –k +C ⇒ C=
2 1 (k 2 – k 1)
e (k 2 – k 1)t k [A]
[B]e k 2 t = k 1 [A]o – 1 o
(k 2 – k 1) (k 2 – k 1)
k 1[A] o
[B ] =
(k 2 – k 1)
[e – k 1t
– e –k 2t ]
d [C]
= k2[B]
dt
d [C]
=
k 1 k 2 [A]o
(k 2 – k 1)
[e – k 1t
– e –k 2t ]
dt
t
k 1 k 2 [ A ]o  e –k 1t e –k 2 t  k 1 k 2 [ A ]o  e –k1t e –k 2 t 1 1
[C] = k – k  –  [C] =  – – + 
2 1  – k 1 – k 2 
o
k 1 – k 2  k 1 k2 k 1 k 2 
k 1 k 2 [A] o  (e –k 1t – 1) (e –k 2 t – 1) 
[C ] =  – 
k1 – k 2  k1 k2 
Graph of [A], [B], [C] Vs t:
[B]
[A]
[A]0
t
k 
t loge  2 
 k1 
t=
(k 2 – k 1 )
[C]
k 1 [A]o
[B] = k – k e
– k 1t
[
– e –k 2t ]
2 1
[A]0
d [B]
dt
k [A]
[
= 1 o – k 1e – k 1t – (–k 2 ) e – k 2 t = 0
k 2 – k1
]
k 1 e –k1t = k 2e – k 2t t
(k 2 – k 1) t k2 [C]
e =
k1
k2 [A]0
(k 2 – k 1)t = log e
k1
log e (k 2 /k 1)
t= t
k 2 – k1
REVERSIBLE KINETICS
K1
B
rate
A
K2 rf
t = o [A]o 0 rb
t = t [A]t [B]t = [A]o – [A]t
t = teq [A]eq [B]eq t
teq
rate(f) = k1[A]
rate (b)
= k2[B]
At equilibrium, rf = rb
k1 [A] equilibrium = k2 [B] equilibrium
k1 [B] equilibrium
=
k2 [A] equilibrium
k 1 [A]o – [A] equilibrium [A]o

= =
k2 [ A ]equilibrium [A]eq – 1
k 1 + k 2 [A]o
=
k2 [A]eq
k 2 [A] o
[ A ]equilibriu m = ............ (I)
k1 + k 2
d [A]
= Rate at which A disappears
dt
+ Rate at which A is produced.
d [A] d [A]
= – k1 [A] + k2 [B] = – k1 [A] + k2 [ [A]o – [A] ]
dt dt
 k2 
= – (k1 + k2) [A] + k2 [A]o = (k1 + k2)  – [A] + k + k [A]o 
 1 2 
By substituting the value from equation (I)
[A] t d [A] t
d [A]
dt
[
= (k 1 + k 2 ) [A]eq – [A] ]⇒ ∫ [A]o [A]eq – [A]
= (k 1 + k 2 ) ∫ dt
o
[A]eq – [A]o
log e = (k 1 + k 2 ) t
[ A ]eq – [ A ]t
2.303 [A] eq – [A] o

(k 1 + k 2 ) = log 10
t [ A ]eq – [A] t
[B]t = [A]o – [A]t
Problem : 22
K1
For the reversible reaction in equilibrium : A B. The values of K1 and K2 are 2 × 10–3 mol L–
K2
1
s ec –1 an d
–3 –1
3 × 10 sec respectively. If we add 0.5 moles of B in the equilibrium mixture, initially containing
2 moles of A. Calculate the time taken for concentration of B to become equal to 3/4 of the
concentration of A initial equilibrium. The volume of mixture is 1 L and remains constant.
K1
Sol. A B
K2
t=0 2 mol litre–1 0
At eq. (2 – X) mol litre–1 X
–3
K1 = 2 × 10 mol L sec –1 –1
(zero order)
K2 = 3 × 10–3 sec–1 (Ist order)
dX
= K 1[ A ] 0 – K 2 [B]1
dt
dx
At equilibrium = 0 ∴ 0 = K1 – K2 [X]eq
dt
K 1 2 × 10 –3
∴ [X]eq = = = 0.66 mol litre–1 = K
K 2 3 × 10 –3 c
A B
Initial eq. 1.34 0.66
Moles added at eq. 1.34 0.66 + 0.5 = 1.16
Addition of B will bring backward reaction
at time t (1.34 + x) (1.16 – X)
3 3
∴ [B] = [ A ]Ieq. = × 134
. = 1005
.
4 4
(1.16 – X) = 1.005
∴ X = 0.155
dX
Now, = K 1 – K 2 [ X ] = 0.66K2 – K2X = K2 [0.66 – X]
dt
dX
∴ = K 2 . dt
(0.66 – X)
or –2.303 log (0.66 – X) = K2.t + C
at t = 0, X=0
∴ C = –2.303 log 0.66
0.66
∴ K2.t = 2.303 log
0.66 – X
2.303 0.66
∴ t= –3
log = 89.24 sec
3 × 10 0.66 – 0.155
Problem : 23 For a reversible first order reaction,

Kf
A B ; Kf = 10–2 sec–1
Kb
B eq
and A = 4 ; If A0 = 0.01 ML–1 and B0 = 0, what will be concentration of B after 30 sec ?
eq
Sol. A0 → B
0.01 0
0.01 – xeq xeq
[B]eq 10 –2 [ x] eq
= =4 =
[ A ]eq Kb 0.01 – [ x] eq
0.04
∴ Kb = 0.25 × 10–2 and xeq = = 0.008
5
2.303 [ x] eq
t = (K + K ) log [ x] – x
f b eq
2.303 0.008
30 = –2 log
125
. × 10 ( 0.008 – x)
0.008
∴ = 1455
. ∴ x = 2.50 × 10–3
0.008 – x
Ways to determine order of reaction
Initial Rate Half life method Ostwald Isolation Integrated Rat law
method method method
(1) Initial Rate Method
A+B product
rate = k [A] m
[B] n
; Order = m + n
[A] [B] rate

Experiment 1 0.1 0.1 2 × 10–3
Experiment 2 0.1 0.2 4 × 10–3
Experiment 3 0.2 0.1 32 × 10–3
Experiment (1) and Experiment (2)
2 × 10 –3 k [0.1]m [0.1]n
=
4 × 10 – 3 k [0.1]m [0.2]n
1 n
 1  1
  = 
 
2 2
n=1
Experiment (1) and Experiment (3)

2 × 10 –3 k [0.1]m [0.1]n
–3
=
32 × 10 k [0.2]m [0.1]n
4 m
 1  1
  = 
2 2
m=4
Order (m + n) = 4 + 1 = 5
(2) Half - life method
t 1/2 [A]o
1
1 hr 0.1 t1/2 α
[ A ]n –1
2 hr 0.2
–1
[t1/ 2 ]1  1 [0.1]n –1
=   =
[t1/ 2 ]2 2 [0.2]n –1
–1 n –1
 1  1
  =  
2 2
n=0
log (t1/2 ) 2 / (t1/2 )1
n = 1+
log [ A ]o1 /[ A ]o 2
(3) Ostwald Isolation method
rate = k[A]m [B]n [C]o [D]p - - - - - - - -

Experiment 1 :
[A] = In small quantity ; [B], [C], [D] - - - - - - - in excess
The rate equation reduces to
rate = k’ [A]m ⇒ r1 = k’ [A]1m
r2 = k’ [A]2m
m
r1  [A] 
=  1 
r2  [A]2 
r   [A] 
log  1  = m log  1 
 r2   [ A ]2 
log (r1/r2 )
m =
log ([ A ]1 /[ A ]2 )
Experiment 2:
[B] = In small quantity .
& [A], [C], [D] - - - - - - ⇒ in excess.
rate = k’ [B]n → repeated
Order of reaction = m + n + O + p + - - - - - - - -
(4) Integrated Rate law Method

A product
t=0 1000 M
t = 60 sec 100 M
t = 120 sec 10 M
[ A ]o – [A] t 1000 – 100 900
n=0 k= = = = 15
t 60 60
1000 – 10 990
k = =
120 120
n = 1
2.303 1000 2.303
k= log =
60 10 60
2.303 1000 2.303
k= log =
120 10 60
ACTIVATION ENERGY (Ea)
A mixture of magnesium and oxygen does not react at room temperature. But if a burning splinter is
introduced to the mixture, it burns vigorously. Similarly a mixture of methane and oxygen does not
react at room temperature, but if a burning match-stick is put in the mixture, it burns rapidly. Why it
happen like this, that some external agents has to be introduced in order to initiate the reaction ?
According to the theory of reaction rates "for a chemical reaction to take place, reactant molecules
must make collisions among themselves". Now in actual, only a fraction of collisions are responsible for
the formation of products, i.e., not all collisions are effective enough to give products. So the collisions
among reactant molecules are divided into two categories :-
Effective collisions and In-effective collisions
Effective collisions are collisions between the molecules which have energies equal to or above a
certain minimum value. This minimum energy which must be possessed by the molecules in order to
make an effective collision (i.e., to give a molecule of products) is called as threshold energy. So it is
the effective collisions which bring about the occurrence of a chemical reaction.
Ineffective collisions are the collisions between the molecules which does not posses the threshold
energy. These can not result in a chemical reaction.
Now most of the times, the molecules of reactants do not possess the threshold energy. So in order to
make effective collisions (i.e., to bring about the chemical reaction), an additional energy is needed to
be absorbed by the reactant molecules. This additional energy which is absorbed by the molecules so
that they achieve the threshold energy is called as energy of activation or simply activation energy. It
is represented as Ea.
A reaction which needs higher activation energy is slow at a given temperature.
E
E
Ea Ea
EP ER
∆H > 0 ∆H < 0
EP
ER
time
time
1
For example : NO(g) + O (g) → NO2(g) is faster at ordinary temperature whereas the following
2 2
reaction :
1
CO(g) + O 2 (g) → CO2(g) is slower at the same temperature as the value of Ea for the second reaction
2
is much higher.
Note :
The progress of the reaction can studied in a graph with energy of the reacting system. You can find
∆H and Ea from graph. (see fig on left)
Collision Theory
(1) Energy Barrier (2) Orientation Barrier
(1) Energy Barrier
A+B A–B
Endothermic Reaction Exothermic Reaction
E E
Ea
Ea
EP ER
∆H > 0 ∆H > 0
ER EP
time time
Eaf > Eab Eaf < Eab

Hf – Hi = ∆ HR
Eaf + Hi = Eab + Hf = Ethreshold
Eaf = Eab + ∆HR
(2) Orientation Barrier
CO + H2O CO2 + H2
H C O H H
C O O O C O O
H H H
Improper orientation ⇒ no reaction.
H H H
O C O O C O O C O
H H H
Activated complex
Proper orientation ⇒ Reaction possible.
For a reactant to change into product both the barriers should be crossed simultaneously.
All those collisions which results into. product are called effective collisions.
ARRHENIUS EQUATION
Number of effective collisions = Number of collision × fraction.
K = A e–Ea/RT
Where ,
K = rate constant of reaction
A = Pre exponential factor

= Arrhenius constant
= Collision frequency
= Frequency factor.
Ea = Activation energy
R = Universal gas constant
T = Absolute temperature.
K
Fraction of molecules undergoing effective collision = e–Ea / RT =
A
Variation in Arrhenius equation
Type -1 :
5 × 10 3
log k = 2 – ; A = ? Ea = ?
T
k = Ae–Ea/RT
Ea
loge k = loge A –
RT
Ea
log k = log A –
2.303 RT
log10 A = 2 ⇒ A = 102 = 100
Ea 5 × 10 –3
= ⇒ Ea = 2.303 × R × 5 × 10–3
2.303 RT T
Type -2 : Temperature Variation :

r1 
→ K1 
→ T1
r2 
→ K2 
→ T2
r2 k
= 2
r1 k1
Ea
log k1 = log A – 2.303 RT
1
Ea
log k2 = log A – 2.303 RT
2
k2 Ea 1 1
log =  – 
k1 2.303 R  T1 T2 
Type -3 :Addition of Catalyst :
Activation Energy
Without Catalyst
Activation Energy
With Catalyst Reaction Path
Without Catalyst
Reaction Path
Without Catalyst
POTENTIAL ENERGY
Reaction
∆H
Products
REACTION COORDINATE
r1 
→ k1 
→ no catalyst 
→ Ea 
→ T
r2 
→ k1 
→ catalyst 
→ Eac 
→ T
Ea
log k1 = log A –
2.303 RT
E ac
log k2 = log A –
2.303 RT
k2 E a – E ac
log =
k1 2.303 RT
Type -4 : Both Catalyst and Temperature :
k2 1  E a E ac 
log =  – 
k1 2.303 R  T1 T2 
FACTORS AFFECTING RATE OF REACTION
(a) Catalyst : The rate of reaction increased by addition of catalyst, because catalyst lowers, the
activation energy and increased the rate of reaction
(b) Temperature : With increase in temperature the rate of reaction increases. It is generaly found
for every 10o increase in temperature. The rate constant double.
The ratio of rate constants with 10o difference in their temperature is called temperature coefficient.
K T + 10
KT = Q = Temperature coefficient of reaction ≈ 2
(c) Concentration :
Rate = A e–Ea/RT [A]m [B]n - - - - - - - - -
With increase in concentration of reactants the rate of the reaction increases because number of
collision (effective collisions) increases.
(d) Nature of Reactants :

Ionic Reactants :
3
–
Na+ Cl– Na+ NO 3–
+
NO
Ag
AgCl (fraction of second)
Covalent Reactants :
H Cl
H2 + Cl2 HCl
will take time H Cl
H Cl H Cl H Cl
H Cl H Cl H Cl
Generaly ionic reactions in aq. media are fast than the reaction involving covalent reactants.
As covalent reactants involving breaking of bond then formation of bond where as ionic reaction
involve in single step.
(e) Surface Area : Increase in surface area increases the number of collisions and hence rate increases
(f) Effect of Sun light : Some reactions exposes to sunlight also increases the rate of reaction.
Problem : 24
At 278 °C the half life period for the first order thermal decomposition of ethylene oxide is 363
min and the energy of activation of the reaction is 52,00 cal/mole. From these data estimate
the time required for ethylene oxide to be 75% decomposed at 450°C.
k 450 5200  1 1 
– = 1122
.
2  551 725 

Sol. ln k =
278
k 450 363
= 3.07 = t1/2 (at 450°C) = 118.24 min.
k 278 t1/ 2 ( at 450° C)
1 A0 1 1386
.
Now t 0.75 = k ln A / 4 = k ln 4 = k
0
1386
.
∴ t0.75 = × 118.24 = 236.48 min
0.693
Problem : 25
The activation energy of the reaction : A + B → products is 102.9 kJ/mol. At 40°C, the products
are formed at the rate of 0.133 mol/L/min. What will be rate of formation of products at 80°C?
Sol. Let the rate law be defined as

At T1 : r1 = k1[A]x[B]y
At T2 : r2 = k2[A]x [B]y
 k2 
⇒ r2 = r1  k 
 1
Using Arrhenius equation find k at 40°C.
k2 Ea  T2 – T1  k 2 102.9 × 10 3  40 
log10 k = 2.303R  T T  ⇒ log10 =  
1  1 2  k 1 2.303 × 8.31  313 × 353 
k2 k2
⇒ log10 k 1 = 1.95 ⇒ = 88.41
k1
⇒ r2 = 0.133 × 88.41 = 11.76 mol/L/min
Problem : 26
The activation energy of a non-catalysed reaction at 37°C is 200 kcal/mol and the activation
energy of the same reaction when catalysed decreases to only 6.0 kcal/mol. Calculate the
ratio of rate constants of the two reactions.
Sol. We know that :
k = A e – Ea / RT
Let k = rate constant for non-catalysed reaction and kc rate constant for catalysed reaction. Let Ea be
the activation energy for non-catalysed reaction and Eac be the energy of activation of catalysed
reaction.
1. k = A e – Ea / RT
2. k c = A e – Eα / RT
1
k (E∞ –Ea )
⇒ = e RT
kc
k 1
⇒ log10 = (Eac – Ea )
k C 2.303 RT
k 1
⇒ log10 = (6 × 10 3 – 200 × 10 3 )
k c 2.303 × 2 × 310
k k kc
⇒ log10 = –9.8 ⇒ . × 10 –10
= 156 or = 6.3 × 10 9
kc kc k
Problem : 27
A first order reaction A → B requires activation energy of 70 kJ/mol. When 20% solution of A
was kept at 25°C for 20 minutes, 25% decomposition took place. What will be the percent
decomposition in the same time in a 30% solution maintained at 40°C? Assume that the
activation energy remains constant in this range of temperature.
Sol. Note : It does not matter whether you take 20%, 30%, 40% or 70% of A.
At 25°C, 20% of A decomposes 25%
A
⇒ k t = 2.303 log10 0
A
100
⇒ k(40) = 2.303 log10 ⇒ k(at 25° C) = 0.0143 min–1
75
Using Arrhenius equation find k at 40°C.
k 40° E a  T2 – T1 
log10 =  
k 25° 2.303R  T1T2 
k 40° 70 × 10 3  40 – 25 
log10 =   ⇒ k(at 40°C) = 0.055 min–1
0.0143 2.303 × 8.31  298 × 313 
Now calculate % decomposition at 40°C using first order kinetics.
A0
kt = 2.303 log10
A
100
⇒ 0.055 × 40 = 2.303 log10
100 – x
⇒ x = 67.1 ≡ 67.1% decomposition of A at 40°C.
Problem : 28
The rate constant of a reaction is 1.5 × 107 sec–1 at 50°C and 4.5 × 107 sec–1 at 100°C. Evaluate
the Arrhenius parameters A and Ea.
K2 Ea  T2 – T1 
Sol. ∴ 2.303 log10 = R  TT 
K1  1 2 
4.5 × 10 7 Ea  373 – 323 

∴ 2.303 log10 =  
15
. × 10 7 8.314  373 × 323 
∴ Ea = 2.2 × 104 J mol–1
2.2 ×10 4
Now, K = Ae –Ea /RT ∴ 4.5 × 107 = –
8.314 × 373
Ae
∴ A = 5.42 × 1010
Problem : 29
A reaction proceeds five times more at 60°C as it does at 30°C. Estimate energy of activation.
Sol. Given, T2 = 60 + 273 = 333 K, T1 = 30 + 273 = 303 K,
R = 1.987 × 10–3 kcal
∵ r = k [ ]n (at a temperature T)
r2 K 2
∴ = (at temp. T2 and T1)
r1 K 1
r2 K2
∵ =5 ∴ K =5
r1 1
K 2 Ea [ T2 – T1]
∵ 2.303 log10 K = R T T
1 1 2
 333 – 303 
Ea
∴ 2.303 log10 5 = –3  333 × 303 
10 × 1987
.  
Ea = 10.757 kcal mol–1
Problem : 30
The rate constant of a reaction increases by 7% when its temperature is raised from 300 K to
310 K, while its equilibrium constant increases by 3%. Calculate the activation energy of the
forward and reverse reactions.
Sol. Rate constant at 300K = k
 7 
∴ Rate constant at 310 K = k + k ×  = 1.07 k
 100 
k 2 Eaf [ T2 – T1]
Thus, 2.303 log =
k1 R T2 T1
. k Eaf  310 – 300 

107
=
2  310 × 300 
2.303 log
k
∴ Eaf = 1258.68 cal
Now, equilibrium constant at 300 K = K′
3
Equilibrium constant at 310 K = K′ + × K′ = 1.03 K′
100
K2 ∆H  T2 – T1 
Using 2.303 log K = R  T T 
1  1 2 
. K ' ∆H  310 – 300 

103
=
2  310 × 300 
2.303 log
K'
∴ ∆H = 549.89 cal
Since, ∆H = Eaf – Eba
∴ 549.89 = 1258.68 – Eba
∴ Eba = 708.79 cal
Problem : 31
At 380°C, the half life period for the first order decomposition of H2O2 is 360 min. The energy of
activation of the reaction is 200 kJ mol–1. Calculate the time required for 75% decomposition at
450°C. [IIT 1995]
Sol. K1 = 0.693/360 min–1 at 653 K and
Ea = 200 × 103 J, K2 = ? at 723 K, R = 8.314 J
∴ From 2.303 log10 (K2 / K1) = (Ea /R)[(T2 – T1)/(T1T2)]
K2 = 0.068 min–1
2.303 100
Now, t= log10 = 20.39 minute
0.068 25
Problem : 32
Two I order reactions having same reactant concentrations proceed at 25°C at the same rate.
The temperature coefficient of the rate of the first reaction is 2 and that of second reaction is 3.
Find the ratio of the rates of these reactions at 75°C
Sol. For I order reaction r1 = K[C]1
R1
∴ R = K 1 / K 2 = temperature coefficient
2
Let temperature co-efficient be a

R 35 K 35 R45 K 45
= =a = =a
R 25 K 25 R35 K 35
R45
∴ = a × a = a2
R25
R75 5
Similarly, R = a
25
For I reaction (R75)I = 25 × (R25)I
For II reaction (R75)II = 35 × (R25)II
(R75 )II 3 5
∴ = 5 = 7.9537 [∴ (R25)I = (R25)II]
(R75 )I 2
Problem : 33
For the reaction :
C2H5I + OH– → C2H5OH + I–
the rate constant was found to have a value of 5.03 × 10–2 mol–1 dm3 s–1 at 289 K and 6.71 mol–
1 dm3 s–1 at 333 K. What is the rate constant at 305 K.
Sol. k2 = 5.03 × 10–2 mol–1 dm3 s–1 at T2 = 289 K

k1 = 6.71 mol–1 dm3 s–1 at T1 = 333 K
 6.71  Ea  333 – 289 

log   =  
5.03 × 10 –2  2.303 × 8.314  333 × 289 
On solving we get, Ea = 88.914 kJ

The rate constant at 305 K may be determined from the relation :
k1 Ea  1 1
log  – 
k 2 = 2.303 R  T2 T1 
 k1  88.914  1 1 
log   =  – 
5.03 × 10 –2  2.303 × 8.314  298 305 
On solving we get, k1 = 0.35 mol–1 dm3 s–1
OBJECTIVE SOLVED PROBLEMS

Problem : 1
In gaseous reactions important for understanding of the upper atmosphere H2O and O react
bimolecularly to form two OH radicals. ∆H for this reaction is 72kJ/mol at 500 K and Ea = 77 kJ/
mol, then Ea for two bimolecular recombination of 2OH radicals to form H2O & O is
(A) 3 kJ mol–1 (B) 4 kJ mol–1
(C) 5 kJ mol–1 (D) 7 kJ mol–1
Sol. As ∆H is positive, therefore reaction is endothermic
x
This is the energy profile diagram for an endothermic reaction. E Ea
Now when the products is converted back to reactant the
energy of activation is x as shown in fig. ∆H
Evidently x = Ea – ∆H
= (77 – 72) = 5 kJ mol–1 ∴ (C) Reaction co-ordinate
Problem : 2
In a certain reaction 10% of the reactant decomposes in the first hour, 20% is second hour,
30% in third hour and so on. What are the dimensions of rate constant.
(A) hour–1 (B) mol lit–1 sec–1 (C) lit mol–1 sec–1 (D) mol sec–1
Sol. If the amount of products formed which is 10%, 20% and 30% is plotted against time i.e., 1 hr, 2 hr and
3 hr respectively, it is a straight line passing through the origin.
x
∴ it is a zero order reaction where x = kt ⇒ =k
t
∴ dimensions of k = moles lit–1 sec–1
∴ (B)
Problem : 3
Two substances A(t½ = 5 mins) and B(t½ = 15 mins) are taken is such a way that initially [A]
= 4[B]. The time after which the conentration of both will be equal is
(A) 5 min (B) 15 min
(C) 20 min (D) concentration can never be equal
Sol. t½ of A is 5 min
∴ in 15 mins it will become 1/8 of initial and t½ of B is 15 mins
∴ in 15 mins it will become ½ of initial
∴ ratio of [A] : [B] after 15 min is 4 : 1
But given [A] = 4[B]
∴ [A] = [B] after 15 min
∴ [B]
Problem : 4
The reaction A(g) + 2B(g) → C(g) + D(g) is an elementary process. In an experiment, the initial
partial pressure of A & B are PA = 0.60 and PB = 0.80 atm. When Pc = 0.2 atm the rate of reaction
relative to the initial rate is
(A) 1/48 (B) 1/24 (C) 9/16 (D) 1/6
Sol. A(g) + 2B(g) → C(g) + D(g)
t=0 0.60 0.80 0 0
t=t (0.6 – 0.2) (0.8 – 2 × 0.2) 0.2 0.2
2
(Rate)i = k[A] [B] = k[0.6][0.8] 2
(Rate)t = k[0.4] [0.4]2
Rt k[0.4]3 1
=
Ri k[0.6][0.8] 2 = 6
∴ [D]
Problem : 5
For a hypothetical reaction A + B → C + D, the rate = k[A]–1/2[B]3/2. On doubling the concentration
of A and B the rate will be
(A) 4 times (B) 2 times (C) 3 times (D) none of these
Sol. k = k[2]–1/2 3/2
[2] = k[2]3/2–1/2
= k = [2]1 = 2k
∴ [B]

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CHEMICAL KINETICS Page # 3

O < t < teq 

The rate of reaction can be expressed as follows :

LAW OF MASS ACTION

Why difference in experimental rate equation & theoretical rate equation

TYPES OF REACTION BASED ON KINETICS

(1) ZERO ORDER REACTION;

(3) SECOND ORDER REACTION :

(4) nth ORDER REACTION :

Zero Order Reactions :

The rate law for zero order reactions (n = 0) is written as :

FIRST ORDER REACTION

Half life (t1/2) :

2.303 [A]o 2.303

[A] = [A]o e–kt

Features of a First Order Reaction :

y = mx + C. Comparing it with Ist order rate law as follows :

⇒ log10 A =  − k t + log10 A 0 is the equation of line. Slope =

Time (minutes) HgCl2 (M) K 2C2O 4 (M) Hg2Cl2 formed (M)

Let the rate law be written as : r = k[HgCl2]x [K2C2O4]y

(i) rate expression for forward and backward reactions.

(b) 6.2 gm of NH2NO2 ≡ 0.1 mol

Second Order kinetics

In this half life is inversely proportional to initial concentration

nTH ORDER KINETICS

Using K = 2.303 log10 b( a – x)

ANALYSIS OF SOME IMPORTANT FIRST-ORDER REACTIONS

Decomposition of Hydrogen peroxide (H2O2)

H2O2(g) → H2O(g) + ½O2(g)

Decomposition of ammonium nitrite (NH4NO2)

and benzene diazonium chloride (C6H5N = NCl)

At t = 0, clearly the volume of N2 = 0

Hydrolysis of Esters (CH3COOC2H5)

Time instants t=0 t1 t2 t3 t4 t∞

After time t, let Pt be the total pressure, then

Pressure (mm Hg) 420 522 602 678

(i) Show that the reaction is first order.

time CH3–O–CH3 CH4 CO H2

Ptotal (atm) 0.154 0.215 0.260 0.315 0.346

Time (sec) 1 52 103 205 309

0.154 1 (0.154 – 0.215 )

Tim e (m inutes) 0 75 119 183 ∞

Volum e of alk ali used in m l 9.62 12.10 1.10 14.75 21.05

Show that hydrolysis of ethyl acetate is a first order reaction.

Rotation (degrees) +32.4 +28.8 +25.5 +22.4 +19.6 –11.1

COMPLEX (FIRST ORDER) KINETICS

2.303 [A] o 0.693

(2) SERIES KINETICS

[B] e ∫ k 2dt = ∫K 1 [A]o e –k 1t e ∫ k 2dt dt + C

Graph of [A], [B], [C] Vs t:

k 1 [A]o – [A] equilibrium [A]o

2.303 [A] eq – [A] o

Problem : 23 For a reversible first order reaction,

Ways to determine order of reaction

(1) Initial Rate Method

[A] [B] rate

Experiment (1) and Experiment (3)

(2) Half - life method

(3) Ostwald Isolation method

rate = k[A]m [B]n [C]o [D]p - - - - - - - -

(4) Integrated Rate law Method

ACTIVATION ENERGY (Ea)

(1) Energy Barrier (2) Orientation Barrier