CHEMISTRY LECTURE NOTES

COURSE : VIJAY (JR)

(LECTURE No. 1 TO 11)

TOPIC : CHEMICAL KINETICS &

RADIOACTIVITY

[1]
DATE : 30-07-12 (Monday)
NOTE : Respected Faculty Member of R-Phase complete the Chemical Kinetics (before
reshuffling) according to the following lecture plan.
(Collect the New lecture notes of R-Phase From SMDD).
Note : Dependence of Rate of Reaction On temperature & Radioactivity will be discussed after reshuffling.

Week : (30-07-12 to 04-08-12)

Total Lecture in this week (3-Physical)

LECTURE = 1
Rate of reaction, Relation Between the Rate of Reactions of Different Species Taking Part in a Chemical
Reaction, Factors affecting rate of chemical reaction,

LECTURE = 2
Order of reaction,Molecularity, Zero Order Reaction,

LECTURE = 3
1st Order reaction, 2nd Order reaction, nth Order reaction,
.
Week : (06-08-12 to 11-08-12)
Total Lecture in this week (3-Physical)
LECTURE = 4
Examples of psuedo first order reactions, Experimental methods to calculate order/rate law of reaction,

LECTURE = 5
Monitoring of the Progress of Reaction, Reactions in gaseous phase & solution phase,

LECTURE = 6
Total optical rotation method.

Week : (13-08-12 to 18-08-12)

Total Lecture in this week (3-Physical)

LECTURE = 7

Complicaitons in 1st order reaction, Parrallel 1st order reaction, Reversible 1st Order reaction.

LECTURE = 8
Sequential 1st Order reaction.

LECTURE = 9

Complete the discussion, Ex-1 (Part-I : Upto section F), Ex-1 (Part -II : Q.No. 4 to 9),
Ex-2 (Upto Q.No. 22 ), ALP (Upto Q.No. 20).

[2]
CONTENTS OF CHAPTER :
Section (A) : Rate of chemical reaction and Dependence of Rate : Basic

Section (B) : Integrated rate law : Zero and First Order Reaction

Section (C) : Integrated Rate law : Second Order & Pseudo first order reaction

Section (D) : Experimental Method to calculate order and rate law of reaction and Methods to Monitor the
progress of Reaction

Section (E) : Method to monitor the progress of Reaction

Section (F) : Complication in 1st Order Reaction

Section (G) : Temperature dependence of rate

Section (H) : Catalyst dependence of rate and type of Reaction and Determination of rate law and order
with the help of given mechanism

Section (I) : Radio Activity

LECTURE # 1

RATE OF REACTION ( VELOCITY OF REACTION)

The rate of change of concetration of any species taking part in a chemical reaction with time is known as
rate of reaction of that species
c
Rate = = molarity /sec. = atm/sec = mm of Hg/sec.
t

TYPES OF RATE

For the reaction R  P

total change in conc. c
1. Average rate = total time taken =
t
“Rate is always defined in such a manner so that it always comes out to be +ve”
 [Re ac tan ts] [products ] (c 2  c 1 )
Rate = = = t t
t t 2 1
Where C1 and C2 are the concentrations of reactants at times t1 and t2.

2. INSTANTANEOUS RATE
Lim c dc
Rinst = = (slope of concetration time graph)
t  0  t dt

[P]
[Reactant]

[Product]

c1
c2
slope of tangent

t
t1 t2

[3]
  dc  d [R] d [P]
Rinst =  dt  =– =
 t  t dt dt

3. INITIAL RATE OF REACTION

Rin = slope at t = 0
 dc 
=  dt 
 t  0

Ex-1. From the concentrations of R at different times given below, calculate the average rate of the reaction:
RP during different intervals of time.
t/s 0 5 10 20 30
3
10 × [R]/mol L –1
160 80 40 10 2.5
Sol. We can determine the difference in concentration over different intervals of time and thus determine the rate
by dividing [R] by t.

[R]1  10 3 [R] 2  10 3 t2 t1 rav  10 3  [R 2  R1 ]  103

1 1 1 1 =
mol L mol L s s mol L s [ t 2  t1 ]
160 80 5 0 16
80 40 10 5 8
40 10 20 10 3
10 2.5 30 20 0.75

Relation Between the Rate of Reactions of Different Species Taking Part in a Chemical Reaction
We very well know that the rate of reaction of all the species taking part in a chemical reaction are not equal
as evident from their stochiometric coefficients. The following example will make it clear

Ex. N2 + 3H2  2NH3

 d[N2 ]
rate of reacton of N2 =
dt
 d[H2 ]
rate of reaction of H2 =
dt
d[NH3 ]
rate of reaction of NH3 =
dt
 From above we can have the following relation between the rate of reactions of different species
 d[N2 ]  1 d[H2 ] 1 d[NH3 ]
= =
dt 3 dt 2 dt
The value of above expressions is also written as rate of the given reaction.

[4]
** Remember that “Rate of Reaction” phrase has no meaning if a balanced equation is not given. Hence
rate of reaction phrase is always used with a balanced chemical equation,
And for balanced chemical equation as given below,
aA + bB  cC + dD
rate of reaction means
1 d [ A ] 1 d[B] 1 d[C] 1 d[D]
Rate of reaction = =– =+ =+
a dt b dt c dt d dt
This can further be understood from the following example
Ex. Rate of reaction is 10–2 M sec–1 when a particular amount of N2 is mixed with some amount of H2 in a
container of fixed vol. at particular temprature. Find out rate of consumption of hydrogen at this inst.
Sol. The question is meaningless, as reaction( the rate of which is given to us) is not specified
So if someone writes the reaction as
N2 + 3 H2  2 NH3
Then according to him the
Rate of reaction of Hydrogen = 3 times rate of reaction
1 dH 2 dN 2 1 dNH3
Rate =   
3 dt dt 2 dt
RH2 = 3 × 102 M sec–1
But if someone writes the reaction as
5N2 + 15 H2  10NH3
Then according to him the rate of reaction of hydrogen will be = 15 times rate of reaction
RH2 = 15 × 10–2
see here if the coefficient of H2 is changed than rate is also changed but this can not be true for a reaction
taking place in a container at particular conditions

ONLY FOR FACULTIES :

The rate of reaction in the question should either be specified in terms of any particular reactant or product or
rate of reaction should be given with respect to a balanced chemical equation.For example the language of
the question should be like

Rate of reaction is 10–2 Msec–1 according to reaction

N2 + 3H2  2NH3 when a particular amount of N2 is mixed..............

OR

Rate of reaction of N2 is 10–2 Msec–1 when a particular amount of N2 is mixed........................

The above concept should be very clear in the minds of students as well of the faculties.

Ex. Rate of reaction N2 + 3H2  2NH3 is 10–3 Msec–1. then find

(a) rate of reaction of N2 [Ans. = 10-3 M/s]
(b) rate of reaction
2N2 + 6H2  4NH3 [Ans. = 0.5 × 10-3 M/s]
(c) Rate of reaction of NH3 [Ans. = 2 × 10–3 M/s]
(d) Rate of reaction of N2 according to the reaction given in part (b) of the question and using the calculated rate
of the reaction. [Ans. = 10-3 M/s]

 From above example it is clear that the rate of reaction is dependent on the stoichiometry of the reaction but
the rate of reaction of any species always remains the same under the specified conditions of the question
whatever be the stoichiometry of the reaction.

[5]
Factors affecting rate of chemical reaction :
1. Concentration 2. Temperature 3. Nature of reactants and products
4. Catalyst 5. pH of the solution 6. Dielectric constant of the medium.
7. Radiations/light 8. Pressure 9. Electrical and magnetic field.
The first four factors generally affect rate of almost all reactions while other factors are specific to some
reactions only.
1. Effect of concentration : We known from law of mass action that Rate is
proportional to concentration of reactants. “ So rate of reaction decreases
with passage of time, since concentration of reactants decreases.

2. Effect of temperature : Will be discussed later.

3. Effect of nature of reactants and Products :
(a) Physical state of reactants :
Gaseous state > Liquid state > Solid state
Decreasing order of rate of reaction.
because collisions in homogeneous system are more effective than heterogenous system.
(b) Physical size of reactants : As we decreases the particle size rate of reaction increases since surface
area increases.
(c) Chemical nature of reactants :
 If more bonds are to be broken, the rate of reaction will be slow.
 Similarly bond strength is more, rate of reaction will be slow.
4. Effect of Catalyst :
 Presence of positive catalyst lower down the activation energy hence increases the rate of reaction.
 Presence of negative catalyst increases activation energy hence decreases the rate of reaction.
5. Effect of pH of solution :
3
Eg. Fe(CN)64–  ( Tl )

 [Fe(CN)6]3–
This reaction takes place with appreciable rate in acidic medium, but does not take place in basic medium.
6. Effect of dielectric constant of the medium : More is the dielectric constant of the medium greater will be
the rate of ionic reactions.
7. Effect of radiations/light : Radiation are useful for photochemical reaction.
8. Effect of pressure : Pressure is important factor for gaseous reaction.
9. Effect of electrical & Magnetic field : Electric and magnetic fields are rate determining factors if a reaction
involves polar species.

LECTURE # 2
EFFECT OF CONCENTRATION (Rate law of any chemical reaction)

(1) Effect of concentration :

The rate of reactions is find to be dependent on concentration is a very complicated manner and this dependence
also changes with the progress of reactions. But in topic we are going to study the simplest kind of depenedance
of rate on concentration of different species.
For most of the reactions in starting of the reaction the rate of reaction is found to be
rate  (conc.)order
or r = k (conc.) order (This type of expression is called Rate Law)

Where, k = Rate constant or specific reaction rate or velocity constant

= rate of reaction when concentration of species in rate law expression is unity (1 M)
k is dependent only on tamprature for a given reactions always given stoichiometry of reation
(k is not dependent on concentration).

[6]
(2) Unit of K :
Rate  conc  1
K= order
 .
(conc )  time  (conc )order
= (conc)1–order time–1
so if concentration is in mole/litre = molarity(M)
Then if order = 0 (zero order reactions)
unit of K = (conc)1 time–1
= M sec–1
if order = 1 (first order reactions)
unit of K = (conc)0 time–1 = sec–1
if order = 2 (second order reaction)
unit of K = (conc)–1 time–1 = M–1 sec–1 = L mole–1 sec–1.
if order = 3/2, unit of K = (conc)–1/2 time–1 = L1/2 mole–1/2 sec–1
ORDER : is the sum of the exponents of all the concentration terms appearing in the rate law
expression
For example, for a reaction
A + B C + D
Experimentally if rate law comes out to be, Rate = k [A]x [B]y [C]z [D]r
Then
x = order of reaction w.r.t A,
y = order of reaction w.r.t. B
z = order of reaction w.r.t. C
r = order of reaction w.r.t. D
x + y + z + r = net order of reactions
The value of x, y, z and r can be zero, can be fractional, can be positive, can be negative , can be
integral
Experimentally for most of the reactions the net order is found to be positive always.
Remember that order is always experimentally calculated.

The following are some examples illustrating the different values of order and different rate law expressions

Ex. 1. 2N2O5 (g)  4NO2 + O2(g)

r = k [N2O5]1

2. 5Br – + BrO3– + H+  3Br2 + 3H2O

R = K [ Br– ] [BrO3– ] [ H2O]

3. NO2 + CO  NO + CO2

R = K [ NO2 ] [CO]o

4. 2O3  3O2

Rate = K [O3]2 [O2]-1

h
5. H2 + Cl2  HCl
R = k [ H2]º [Cl2]º

6. CH3CHO  CH4+ CO

R = k [CH3CHO]3/2

NO
7. 2SO2 + O2   2SO3
R = k [O2] [NO]2

8. H2 + Br2  2HBr

k 1[H2 ]1. [Br2 ]1 / 2

r= Rate constant & order are not defined
1  K 2 [HBr ] /[Br2 ]

9. H2 +2  2H

R = K [H2] [ 2]

[7]
 From all these it must be very clear that there is no relation between the stochiometry of the reaction
and order of the reaction, order is always experimentally calculated, the stochiometry of the reaction is in
the hand of the student balancing a reaction but the order is always fixed.
Also remember that there the meaning of rate of a reaction and rate constnat of a reaction changes with
changing in the stoichiometry of reaction, but rate of reaction of a particular reactant will always have the
same value.
Ex. If rate of reaction (hypothetical)
A + 2B  3C + D
is given by rate1 = K1 [A]2 [B]1 and if reaction is written as
2A + 4B  6C + 2D
its rate is given by expression rate2 = K2 [A]x [B]y (under similar conditions) then find value of K2 (in terms of
K1) and x & y.
Sol. A + 2B  3C + D
dA 1 dB 1 dC dD
rate1 = K1 [A]2 [B]1 =    
dt 2 dt 3 dt dt

2A + 4B  6C + 2D
1 dA 1 dB 1 dC 1 dD
rate2 = K2 [A]x [B]y =    
2 dt 4 dt 6 dt 2 dt

dA
from Ist reaction  = K1 [A]2 [B]1
dt

dA
from IInd reaction  = 2K2 [A]x [B]y
dt

K1
by comparision x = 2, y = 1 and K2 = Ans.
2
 Only for Simple/Elementary/Single Step Reactions it is found that order is equal to the stoichiometry, but
which reaction is going to be simple can not be decided by looking at the stoichiometry of the reaction , it is
always experimentall decided by the mechanism of the reaction.
For example the following three reaction look similar but their rate laws are totally different.

h
1. H2 + Cl2  HCl
R = k [ H2]º [Cl2]º

2. H2 + Br2  2HBr

k 1[H2 ]1. [Br2 ]1 / 2

r=
1  K 2 [HBr ] /[Br2 ]

3. H2 +2  2H

R = k [H2] [ 2]

dC K 1C
Ex. The rate of a certain reaction depends on concentration according to the equation : 
dt 1  K 2C .
What will be the order of reaction, when concentration (C) is :
(a) very-very high, (b) very-very low.

 dC K 1C K1
Sol. (a) = = 1
dt 1  K 2C  K2
C

1
if C is very-very high then being small may be neglected.
C

[8]
  dC K 1

 dt K 2 = constant, i.e., zero order reaction.
(b) If C is very-very low 1 + K2C  K

K 
  dC K 1C =  1  × concentration
dt

K  K 

i.e.,  order reaction.

Molecularity and Order :

The number of molecules that react in an elementary step is the molecularity of the elementary reaction.
Molecularity is defined only for the elementary reactions and not for complex reactions. No elementary
reactions involving more than three molecules are known, because of very low probability of near-simultaneous
collision of more than three molecules.
The rate law for the elementary reaction
aA + bB  products rate = k[A]a[B]b, where a + b = 1, 2 or 3.
For an elementary reaction, the orders in the rate law equal the coefficients of the reactants.

While, the order is defined for complex as well as elementary reactions and is always experimentally calculated
by the mechanism of the reaction, usually by the slowest step of the mechanism known as rate determining
step of the reaction.

[9]
 ZERO ORDER REACTION
A  products
t=0 a – rate = k [A]0 = k
Find the concentration of A at time t, the time taken for completion of the reaction, time taken for half
completion.
A  products
t=0 a = C0
t=t (a – x) = Ct

d[ A ]
Rate = – = k [A]º = k differential rate law
dt
 [A] = a–x [A] = Ct
d(a  x ) dC t
=k =k
dt dt
dx
=k
dt
x t Ct t

 dx =  kdt  dC t = –k  dt
o o Co o

Ct – Co = kt

x = kt Ct = Co – kt integrated rate law

x is consumed Ct is concentration remaining after time t

concentration
Ct = a – kt

GRAPHICAL REPRSENTION :
Ct
x Co r
slope = – K
K K
=
pe
slo
C0 t
t t
K
 Calculate time taken for completion of reactionn.
Ct = C0 – kt
when reacation is completed Ct = 0 ,
Co
to =
K
 Calculate half life of reacton t1/2
C0
= C0 – kt
2
C0
when t = t1/2  Ct =
2

C0
t1/2 = or t1/2  C0
2k

Examples of zero order reactions :

Generally decomposition of gases on metal surfaces at high concentrations follow zero order kinetics.

[10]
 Ni
2PH3 (g)  2 P + 3 H2 Rate = K [PH3]º
Au
2H (g) 
 H2 + 2
Pt
2NH3(g)  N2 + 3H2
hv
H2 + Cl2   2 HCl Rate = R [H2]º [Cl2]º

Ex. Let decomposition of Cl2O7 (g) into ClO2 (g) & O2 (g) be a zero order rxn. If at a particular time
d[Cl2O 7 ]
= 50 mm of Hg /sec. for the decomposition reaction having initial pressure of Cl2O7 = 600 mm
dt
3
of Hg. (Cl2O7  2ClO2 + O)
2 2

(a) Calculate rate of production of O2 at t = 2sec

(b) Calculate t1/2 for rxn. of Cl2O7
3
Ans. (a) Cl2O7  2ClO2 + O
2 2
d
 [Cl2O7] = K [Cl2O7]0
dt
d
 [Cl2O7] = K = 50
dt

d[O 2 ] 3 d[Cl2O 7 ] 3
= = × 50 = 75 mm.
dt 2 dt 2
a
(b) t1/2 =
2K

600
t1/2 = = 6 sec.
2  50
LECTURE # 3
st ORDER REACTION
A  products
t=0 a = C0
t=t a – x = Ct
Rate = k [A]
d[A]
– = k [A]
dt
[A] = a – x [A] = Ct
d(a  x ) dC t
=k(a–x) – k[A]
dt dt

x t
Ct t
dx dc t
dt
 a  x = k  dt 
Co
ct = – k 
o o o

x
 Co 
–ln [(a  x )]0 = kt ln  C  = kt
 t

 a 
ln   = kt Ct = Coe–kt
ax
a
= ekt ln Ct = lnCo – kt
ax
x = a(1 – e–kt)

[11]
 2.303  a 
K= log  
t ax

Ct x Rate
Co a In (C0/Ct) kCO
slo
pe
= –k

t t t t

dC t
r = – d , r = kCt = k C0e– kt
t
rate exponantially decreases
 Calculate time for taken for completion of rxn.
Ans. since rate exponantially decreases it will take infinite time for completion
t = T100% , Ct = 0 or x = a so T100%  

Calculate time for taken for half (fifty percent) completion of rxn.

ln 2 0.693
t = T50% = t1/2 = =  t1/2 not dependent on initial conc.
k k

 100 
Time taken for x% completion, kTx% = ln  
 100  x 

1 ax
For bacterial first order growth reaction k= In  
t  a 

1 a  x1
For time interval (if reading at t = 0 is not given) in first order k = t  t In a  x
2 1 2

Time taken for any % completion in a Ist order reaction is not dependent on initial concentrations taken, While
in zero order reaction time taken for equal amount to react is equal.
Zero Ist order

10 sec 10 sec

90 90

10 sec 10 sec 10% completion will require equal time

80 81

10 sec 10 sec

70 72.9

10 sec 10 sec

60 65.61

[12]
 T1/2 of Ist order reactions is constant, so the concentration remaining after n half lives
C0
Cn =
2n
 Examples of first order reactions
1. 2N2O5 (g)  4NO2 + O2(g)
r = k [N2O5]1

2. NO2 + CO  NO + CO2

R = K [ NO2 ] [CO]o

3. Radioactive decays
4. The decomposition of Cl2O7 at 400 K in gaseous phase to Cl2 and O2 is of  order reaction
5. Decomposition of H2O2 is a first order reaction
6. NH4NO2 (aq.)  N2 (g) + 2 H2O (l)

Ex. If t = Time taken for 25% completion then

Time 1st order concentration remaining zero order concentration remaining

0 C0 C0
3C0 3C0
t
4 4
2
3 9 1
2t   C0  C0 C0
4 16 2

3
3 1
3t   C0 C0
4 4

4
3
4t   C0 0
4

n
3
nt  
4

Ex. If t = T25% (time taken for 25% completion) in time t, 25% of reactant will get reacted and 75% will remain
Time t=0 t 2t 3t 4t 5t .............

Conc. remaining C0 3/4C0 (3/4)2C0 (3/4).3C0 (3/4)4C0 (3/4)5C0.............

t 0.75
Ex. Calculat t for a 1st order reaction
0.50

2.303 C0 2.303 C0 t3 / 4 log 4 2 log 2

Sol. k= t log 1  t log C 0  t1/ 2 = log 2 = log 2 = 2
3/4 1/ 2
C0
4 2
t 0.5
Ex. Calculat t for a 1st order reaction
0.25

 C 
2.303 log  0 
t 0.5  C2 / 2  log 2
Sol. t 0.25 = = log 4 / 3
 
 C 
0
2.303 log  
 3C 0 
 
 4 

[13]
Ex. A & B are two different chemical species undergoing 1st order decomposition with half lives equal to 0.231 &
Ct (A )
0.3465 sec respectively. If the initial conc. of A & B are in the ratio 3 : 2. Calculate C (B) after theree half
t
lives of ‘A’.
Sol. t = 0.231 × 3 = 0.693 sec
n2 0.693 0.693
kA= t = =3 kB = =2
1/ 2 0.231 0.3465
Ct = C0e–kt
Ct (A ) 3 0.693 3 1 3
e
 C t (B) = 2 =  =
2 2 4
Ans.

Ex. If for a Ist order reaction

Tx%  700 
T25% = 2 then find x  x =  16 
 

nd ORDER REACTION

],

1. A  products Rate = k [A]2

t=0 a = Co
d [ A ]
= k [A]2 differential rate law
dt
d [ A ] d(a  x )
2 = Kdt = ( a – x)2
[A] dt
Ct
t
d [A]
  = Kdt

C0 [ A ]2
o
x x
l Ct dx
[A] C0
= kt or  (a  x )2 =  kdt
0
0
1 1 1 1

C t C o = kt
 = kt
ax a
1 1
C t = kt + C 0
Above two are the integrated rate laws
1
Ct pe
slo C0 – Ct
k
1 Ct
C0
slope = KC0
t
1 1
Ct C0 = kt


C0  Ct
Ct C0 = kt
 C0  Ct 
  = [kC ]t
 Ct  0

y = mx

a Co
At t = t1/2 X= and Ct =
2 2

1 1 1
t1/2 = kC  ka ; t1/2  C
0 0

[14]
 nth ORDER REACTION
A  products Rate = k [A]n
t=0 a = Co
d [ A ]
= k [A]n differential rate law
dt
1 t
 .dC t  k.dt
 (Ct )n 0
1  1 1 
  
n  1  (Ct )n1 (C0 )n1  = kt
 

2n1  1
t1/ 2 
(n  1)k(C0 )n1
Results :
So far we have
for zero order T1/2  C01
for Ist order T1/2  C00
for 2nd order T1/2  C0–1
‘ ‘
‘ ‘
‘ ‘
‘ ‘
So far nth order T1/2  (C0)1–n
This can be proved as follows.
Ex. For three reaction, first one is zero order, second reaction is first order and the third reaction is of second
order. The initial concentrations for all thses reactions are 100 and the time taken for the concentration to
decrease to 50% of the initial value for all three reactions is found to be equal as shown below.
Then Calculate the times taken for the successive decrements to 50% of the valuesas shown ...
Zero st  ND
Co 100 100 100

10sec 10sec 10sec

50 50 50

25 25 25

12.5 12.5 12.5

6.25 6.25 6.25

3.125 3.125 3.125

Total time taken for 20 sec infinite infinite

the completion of
reactions

[15]
 LECTURE # 4
Case : For the reaction
A + B product, if Rate = k[A][B] then find the integrated rate law and half lives of A and B
t =0 a b
Sol. A + B product
t=0 a b
t a– x b–x

d [ A ] d(a  x )
= k [A] [B]  = kdt
dt (a  x )(b  x )

dx
= kdt After doing partial fraction
(a  x )(b  x )

1  dx dx   1   (b  x ) x 
   = k dt    ln   = kt
a b b x a x  ab  (a  x ) 0 
 

x
(b  x ) 1  a(b  x ) 
ln = – kt (a–b)  kt = ln  
(a  x ) 0 ba  b(a  x ) 
CASE : if b >> a then b – a  b,
b–x  b

1  a   a 
kt = ln    (kb) t = ln  .
b ax ax

 a 
k’t = ln   k’= pseudo 1st order rate constant
ax
 Examples of psuedo first order reactions
1. hydrolysis of esters is a pseudo first order reaction
CH3COOC2H5 + H2O  CH3COOH + C2H5OH

rate = k [ester ][H2O]  k’ [ester] {H2O is solvent}

ln 2
t1/2 =
k'

2. hydrolysis of sucrose is a pseudo first order reaction

C12 H22 O6 + H2O  C6 H12 O6 + C6 H12 O6

 A + B product,
t =0 a b
If the rate law is , rate = k [A] [B], then if b >> a,
dA dB
rate = = = k [A] [B]
dt dt

dA
= (kb) [A] = k’ [A]
dt
 If the rate law would have been, rate = k [A] [B]3, and b >> a, then
k’ = kb3

[16]
 EXPERIMENTAL METHODS TO CALCULATE ORDER/ RATE LAW OF REACTION
(a) INITIAL RATE LAW METHOD
aA + bB + cC  products
rate = k [A]x [B]y [C]z

Initial concentrations r0 (initial rate )

[A] [B] [C]
Exp.1 a1 b1 c1 r1
Exp.2 a2 b1 c1 r2
Exp.3 a1 b2 c1 r3
Exp.4 a1 b1 c2 r4
r1 = k a1x b1y c1z
x
r1  a1  log(r1 / r2 )
r2 = k a2x b1y c1z  =    x = log(a / a )
r2  a2  1 2

Similarly the values of y, z and k can also be calculated

Ex. The initial rate of reaction
A + 5B + 6C = 3L + 3M
has been determined by measuring the rate of disappearance of A under the following conditions :
Expert - [A] 0 [B] 0 [C]0 Initial rate
Ment No. M M M M/min–1
1. 0.02 0.02 0.02 2.08 × 10–3
2. 0.01 0.02 0.02 1.04 × 10–3
3. 0.02 0.04 0.02 4.16 × 10–3
4. 0.02 0.02 0.04 8.32 × 10–3
Determine the order of reaction with respect to each reactant and overall order of the reaction. What is
the constant? Calculate the initial rate of the reaction when the concentration of all the reactants is
0.01M. And also calculate the initial rate of change in concentration of B and L.
Sol. In experiments  and , initial concentrations of B and C remain unchanged and hence from the rate
expression
r = k [A0]a [B0]b [C0]c = k 0 [A]0a ,
(r0 )1 2.08  10 3 [ A 0 ]1a 0.02a
We get (r ) = = a =
0 2 1.04  10 3 [ A 0 ]2 0.01a
or 2 = (2)a and a = 1
Similarly
(r0 )3 4.16  10 3 [B 0 ]b3 0.04b
(r0 )1 = 2.08  10 3 = [B 0 ]1b = 0.02b
2 = (2)b or b = 1
(r0 ) 4 8.32  10 3 [C 0 ]c4 0.04 c
and = = =
(r0 )1 2.08  10 3 [C 0 ]1c 0.02 c
or 4 = (2)c and c = 2
Thereforrs, the order of the reaction with respect to A, B and C rae 1, 1 and 2 respectively and the overall
order of the reaction = 1 + 1 + 2 = 4.
r r
k= a b c =
[ A 0 ] [B 0 ] [C 0 ] [ A 0 ][B 0 ][C 0 ] 2

we can put the values from the set ,

2.08  10 3 M min 1
k= = 1.3 × 104 M–2 min–1
16  10 8 M3
rate of reaction when [A0] = [B0] = [C0] = 0.01 M
r = k [A0] [B0] [C0]2 = 1.3 × 104 M–2 min–1 [0.01 M] [0.01 M] [0.01 M]2 = 1.3 × 10–4 M min–1
1 d [B] 1 d [L ]
r= = = 1.3 × 10–4 M min–1
5 dt 3 dt

[17]
 d [B]
– = 5 × 1.3 × 10–4 M min–1 = 6.5 × 10–4 M min–1
dt
d [L ]
= 3 × 1.3 × 10–4 M min–1 = 3.9 × 10–4 M min–1
dt

(b) METHOD OF HALF LIVES

For a nth order reaction, we have
t1/2  (co)1-n
The above result can be applied for the following type of reactions.
(i) A  product
(ii) 2A + 3B  product
2a 3a
Where the initial concentrations are in the stoichiometric ratios
rate = k[A]x [B]y
n=x+y
t1/2  ( Co )1–n. {where Co can be initial concentrations [A] or [B] or [A] + [B]}

 Only two readings are sufficient, but more readings are collected as to insure that the
experimental errors can be minimised, ideally we should take the average value of n ,
calculated from different runs.

Ex. Reduction of NO with H2 takes place as

2NO + 2H2  N2 + 2H2O
if equimolar mixture of NO & H2 is taken at initial total pressure of 350 mm of Hg, total pressure reduces to
half its value after 121sec. while if initial total pressure would have been 275 mm it reducess to half after 196
sec. calculate order of reaction.
1n
121  350 
Sol.   Ans. n = 3
196  275 
Note that the value of n is total order, not the order with respect to any one particular species.

(c) USING INTEGRATED RATE LAWS/GRAPHICAL METHOD (Hit and Trial Method)
This method is specially suitable for the following type of reactions.
A  products
The following data is collected for the above reaction
t=0 t1 t2 t3
Co C1 C2 C3
check for which order of reaction, the above data is best fitted in the integrated rate law of that particular
order of reaction.
c 0  c1
For zero order : Calculate kusing given data k= t1
c0  c2
k= t2
and so on..... if all the values of k comes out to be equal, then reaction will be of zero order. If not, then
check for the first order

1  c0 
For Ist order : k = t ln  c 
1  1

1  c0 
k = t in  c 
2  2
and calculate k using the other data also....if all the values of k comes out to be equal, then the reaction
will be of first order, if not then check for the second order.
In this way, we can check the order of reaction.

[18]
 LECTURE # 5
MONITORING OF THE PROGRESS OF REACTION
1. Gaseous phase reactions
(a) Pressure measurement
Concept : Pressure of gas  no. of mole of gas (V, T = constant)
(b) Volume measurement
Concept : Volume of gas  no. of mole of gas (P, T = constant)

The pressure or volume of system is under the specified conditions is directly proportional to the number of
gaseous moles. This method is applicable only if there is some change in the number of gaseous moles
during the chemical reaction.
So, method is applicable of reactions like
An(g)  nA(g) [one mole of gas is decompositing into n-moles.]
for ex.
N2O4(g)  2NO2(g) n = 2 (n > 1)
2NH3(g)  N2(g) + 3H2(g) n=2
2Cl2O7(g)  4ClO2(g) + 3O2(g) n = 7/2 = 3.5
or A(s)  B(g) + 2C (g)
or A(aq)  2B(g) + C(g)
1
for ex. H2O2(aq)  H2O() + O (g)
2 2
NH4NO2(aq)  N2(g) + 2H2O()

* Remember pressure or volume measurement is only because of gaseous moles, not because of
solid or liquid species moles.
The data collected wil be in the following form
Time t=0 t1 t2 ............ 
Pressure P0 P1 P2 ............ P
or
Volume V0 V1 V2 ............ V
We have to relate the above data with the concentration of remaining reactant.
For example : For reaction (symbolic)

Ex. An (g)  nA(g)

(p0 – x ) nx Pg
t=0 t1 t2 .... t h
p0 p1 p2 ... npo height
pt = po – x + nx  total press at time t. different
 pt  po 
x=  
 n 1 
ct  po – x
p t  po np o  p t
ct  {po – }; ct 
n 1 n 1

1  p o (n  1) 
For Ist order K= ln  np  p 
t  o t 

Now see again :

1  P  P0 
nP0 = P So, k= ln  
t  P  Pt 


[19]
 This formula is more convinient to remember and more accurate. But how, lest’s see.
An (g)  nA (g) (some inert gas is also present)
PAn
PAn – x nx P0 = PAn + Pinert
0 nPAn Pt = PAn – x + nx + Pinert
P = nPAn + Pinert
Now P – P0 = PAn (n – 1)
P – Pt = (n – 1) (PAn – x)

1 PAn 1 P  P0
So k= ln P  x = ln P  P
t An t  t

So there is no effect of impurity or inert gas in this formula

But in previous formula effect of inert gas is explained as.

1 (PAn  Pinert )(n  1) 1 (PAn  Pinert )(n  1)

k  ln = ln
t n(PAn  Pinert )  [PAn  x  nx  Pinert ] t [PAn  Pinert  x ](n  1)
Similarly in volume measurement
1  V  V0 
k  ln  

t  V  Vt 
For NH4NO2(aq)  2H2O () + N2(g)

1  V 
k  ln 
 V0 for gas = 0
t  V  Vt 

Ex. The decomposition of NH3(g) on platinum surface is Ist order reaction. and the progress of reaction is monitred
by measuring the pressure inside the fixed volume container. (Assume initially only NH3 is present. The data
collected is :
Time t=0 t = 20 min
Total pressure 100 mm of Hg t = 125 mm of Hg
Calculate half life of decomposition of NH3. Given that log 2 = 0.30 and log 3 = 0.48]
Sol.
Note : At high concentration  zero order
At low concentration  first order
2NH3(g)  N2(g) + 3H2(g)
t=0 100 0 0
t (100 – x) x/2 3x/2 = (100+x)

3 x 100
 0 100/2 = 200
2

1  100  n2 n2

K = 20 min ln   =
t1/ 2  T1/2 = (20 min) n4 / 3
 75 

 0.30  100
So, T1/2 = (20 min)  0.12  = min.
  3

Ex. Progress of decomposition (Ist order)

NH4NO2(aq)  2H2O () + N2(g)
is followed by total pressure measurement the data collected is :
Time t=0 t = 20 min 
Total pressure 50 mm of Hg 80 mm of Hg 90 mm of Hg
Calculate half life of above decomposition.

[20]
Sol. NH4NO2(aq)  2H2O () + N2(g)
t=0 a 0 0
t (a–x) - x
 0 - a
So, a  (90 – 50) = 40
x  (80 – 50) = 30
(a – x)  10

1  40  n2
So, K = n   =
T1 / 2 So, T1/2 = 10 min
20 min  10 
Ex. For the decomposition of azoisopropane at 270ºC it was found that at t = 0, the total pressure was
33.15 mm of Hg and after 3 minutes the total pressure was found to be 46.3 mm of Hg. Calculate the value
of ‘k’ for this reaction [(CH3)2 CH N = N CH(CH3)2  N2 + C6H14].

2.303  P0 (n  1)  2.303 33.15 ( 2  1)

Sol. k= log  nP  Pt   k= log = 0.1684 min–1
t  0  3 2  33.15  46.3

2. REACTIONS IN SOLUTION PHASE

The progress of reactions in monitred by measuring any property of solution which varies with the concentration
of reactant/produce or with the progress of reaction. Progress can be measured by measuring.
1. The volume of titrant consumed with a fixed volume of reaction mixture etc.
2. Total optical rotation of solution of reactant or product or both are optically active.
3. Total electrical conductance of solution of reactant or product or both are ionic species.
4. Other properties of solution which is directly proportional to the concontration.
(i) Titration method : Reaction must involve some species which can take part in titration.
The data collected will be in the form
time duration t=0 t1 t2 t
vol. of reagent consumed v0 v1 v2 v
() Only one reactant reacts with titrating Agent
Ex. H2O2()  H2O() + 1/2O2(g)
t=0 a 0 0
t a–x x x/2
t=  0 a a/2

For titration.
Mili eq. of H2O2 = Mili eq. of KMnO4
[M2 × 10]n2 = [M1 × V0] × n1
 M1 n1 V0 
M2 =  n 10 
 2 
molarity  v0
a  v0
a – x  vt

1  v0 
k= ln  v 

t  t 

[21]
 MAY ALSO EXPLAIN THIS CONCEPT BY THE EXAMPLE GIVEN BELOW :
Ex. Conversion of N-Chloroacetanide to parachloroacetanilide is 1st order only. It is given to us that the reactant
only can react with I– ions to convert these into the I2.
& 2 produced can be measured by hypo titration.
time duration t=0 t1 t2 t3
Vol. of hypo consumed Vo V1 V2 V3 find k

Excess of KI

N-chloro hypo soln.

Sample
Bi-chloro

a  Vo
a – x  Vt

1  Vo 
k= ln  V 

t  t 
() Only product reacts :
A  B + C only B reacts with reagent, [take same amount of sample otherwise proportionality
constant will change]
t=0 a 0 0
t=t a-x x x
if initial amount of B = b0
b0+ a  v 
b0  v0
b0 + x  vt
x  vt – v0
a  (v  – v0) 1st order w.r.t. reactant
a–x (v  – vt)

1  v  v0 
k= ln  v  v 

t   t 

(III) If more than one compound is reacting even the catalyst.

D ( y moles )
Ex. A     B + C v.f. of A:B:C:D
moles a 1:2:3:Z suppose
a-x x x given t=0 t=t 
0 a a volume of titrant v = v0 vt v

equivalent of A + equivalent of B + equivalent of C + equivalent of D = equivalent of titrant

at t = 0 a × 1 + 0 + 0 + y×z = M1v0 × v.f.
a + yz  v0 ....... (1)
at t = t a –x + 2x + 3x + y×z  vt ....... (2)
at t =  0 + 2a + 3a + y×z  v ....... (3)
Geak v – v0  4a
and v – vt  4(a-x)

1 v   v0
so k = t n v  v
 t

[22]
Ex. Acid catalyzed hydrdysis of esters & CH3COOC2H5 + H2O  HCl
 CH3COOH + C2H5OH
progress of this reactions measured by titrating reaction mixture with NaOH
time t=0 t1 t2
NaOH consumed Vo V1 V2
st
For this 1 order rxn. calculate k.
Sol. CH3COOC2H5 + H2O  H3CCOOH + C2H5OH
a 0 0
(a -x) x do not consider
0 a
catalyst  [HCl]  V0 (HCl is a catalyst in this reaction)
[HCl] + x  Vt
[HCl] + a  V 

1  V  Vo 
K= ln  V  V 

t  t 

If progress is monitored by measuring total optical rotation produced by solution.

LECTURE # 6
TOTAL OPTICAL ROTATION METHOD

Ex. HYDROLYSIS OF CANE SUGAR / INVERSION OF CANE SUGER

C12H22O11 + H2O  C6H12C6 + C6H12O6
Sucrose dextrotatory glucose dextrotatory fructose laevorotatory
1 = 66.5º 2 = 52.7º 3 = – 92.4º
Progress of reaction is monitored by measuring angle by which plain polarised light is rotated
t=o t1 t2 t
o 1 2 
C12H22O11  glucose + fructose
t=0 a 0 0
t=t a–x x x
t = 0 a a
concentration
O = a 1  = length of solution
t =  (a – x) 1 + x 2 – x 3
  a2 – a3
o
1 - =
a


2 – 3 =
a

 o (a  x ) x 
t = +
a a

x  t  o
at = oa – ox + x  =  
a  o

a    o 1    o
=    K= ln   
ax  t t  t

[23]
Case-I Only reactant is optically active
A*  2B + 3C
t=0 a 0 0
t (a – x) 2x 3x
 0 2a 3a

data collected
Time t=0 t1 t2 t3 ............... 
Angle by which light is rotated Q0 Q1 Q2 Q3 ...............Q
Since, rotation produced by species is Q =   c
 - specific rotational angle of species.
 - length of solution
C - concentration for a Ist order reaction (as Q 0 here)
1  Q0 
So K = n  Q 

t  t 
Case-II If some species is present which is not taking part in reaction but is optically active or a optically active
catalyst is present whose concentration remains constant during progress of reaction.
D*
A*   2B + 3C
In this case Q 0
= angle by which light is rotated by D.
So, a  (Q0 – Q9)
(a – x)  (Qt – Q0)

1  Q   Q0 
So K = n  Q  Q 

t   t 

Case-III If only products are optically active

A *
  2B* + 3C
t=0 a 0 0
t (a – x) 2x 3x
 0 2a 3a
If D is present then Q0  0 = angle by which light is rotated by D.
Now 2a  (Q – Q0)
2x  (Qt – Q0)
So 2(a – x)  (Q – Qt)

1  Q   Q0 
So K= ln  
t  Q Q 
  t 

Case-IV If reactants, products and catalyst all are optically active.

A*  2B* + 3C*

t=0 a 0 0
t (a – x) 2x 3x
 0 2a 3a
Q0 = 1a
Qt = 1(a – x) + 2 (2x) + 3 (3x)
Q = 0 + 2 (2a) + 3 (3a)
1 - constant of proportionality for A = A
2 = B
3 = C Similarly

[24]
 From
Qt = 1 (a – x) + 2(2x) + 3 (3x)

Q0 Q
= (a – x) + x
a a
So, a(Qt – Q0) = x (Q – Q0)

x  Qt  Q  1  Q   Q0 
=  Q  Q 
  So K = ln  Q  Q 

a   0  t   t 
YOU CAN DIRECTLY QUOTE THE RESULT IN THE CLASS, IF IT APPEARS BEYOND THE LEVEL OF
THE STUDENTS.
ao V  Vo
(1) Total property given irrespective of valency factors optical rotation a  x = V  V
o t
ao V  Vo
(2). Total property of only products is given a o  x = V  Vt
eg. Only products read with reagent
ao  Vo 
(3) If only reactant’s property given =  
ao  x V 
 t 

LECTURE # 7
COMPLICATIONS IN 1ST ORDER REACTION

PARRALLEL 1st ORDER REACTION

K1 B
A x

a -x -y K2
C
y
t=0 [A] = a [B] = [C] = 0
Calculate effective t1/2 for [A] & [B], [C] & [B] / [C]
d [B] d [ C]
Sol. = K1 [A] = K2 [A]
dt dt

d[ A ] d[B] d[C]

= +
dt dt dt

d[ A ]
= (K1 + K2 ) [A] = Keff [A]
dt
Keff = K1 + K2
ln 2 ln 2 ln 2
Teff = T1 + T2 (where T represent half life)

1 1 1
` Teff = T1 + T2 (remember)

 (K 1  K 2 ) t
Now, [A]t = a e K eff t = a e
d [B]
= K1 [A]
dt

d [B]
= K1a e (K 1  K 2 )t
dt

[25]
  k 1a 
[B] =  k  k  ( 1  e (K 1  K 2 )t )
 1 2 
similarly
K2 a
[C] = K  K ( 1  e (K 1  K 2 )t )
1 2

[B] K1
= K (remember)
[C] 2

Keff = k1 + k2

THE RESULTS OF REVERSIBLE REACTIONS WILL NOT BE TAUGHT IN PHYSICS SO WE HAVE TO

DEAL WITH THIS SECTION IN THE CLASS.

REVERSIBLE 1ST ORDER REACATION ( both forward and backward )

kf
A B
Kb
t=0 a 0
t=t a –x x
t = teq. a – xeq. xeq.

xeq. = eq conc. of product

d[A] d [B]
= = 0 At eq. ( At equilibrium conc. is not changed)
dt dt

d[A]
= –Kf [A] + Kb[B]
dt

d [B]
= – Kb [B] + Kf [A]
dt

d(a  x )
= – Kf (a – x) + Kbx
dt

dx
– = – Kf a + (Kf+ Kb )x
dt
x t
dx
 K f a  (K f  K b )x =  dt
0 0

ln[K f a  (K f  K b )x]0x
 =t
K f  Kb

1   ln  K f a  (K f  K b )x]    t
  
 K f  Kb   Kfa 
  

1  Kfa 
 ln   =t
K f  Kb  
 K f a  (k f  k b )x ] 

Kfa
( k f  k b ) t
x = K K
f b
1  e  (remember)

[26]
 Kf [B] eq. x eq.
Keq. = K = [ A ] = (a  x )
b eq. eq.

K f  Kb a
Kf = x
eq.

x = xeq. 1  e (K f  K b )t
  (t   , x  xeq.)

1  x eq. 
 
Kf + Kb = ln  x  x  (remember)
t  eq. 
 Kf 
Where Xeq = a ×  K  K  a
 f b

Kf  a 2 a/3
Xeq = K  K .
f b a/3
Kf
if K = 2
b

Ex. Calculate tavg.

tavg. = sum of life time of all molecule /total number of molecule
A  products
t=0 N0
t = eq. N = N0e-Kt
dN = –KN0e–Kt dt
t. dN = sum of lifetimes of molecules with lifetimes = Kt N0e–Kt

Kt
 Kt N0 e dt
1
0
Total sum = =
N0 K

LECTURE # 8
SEQUENTIAL 1ST ORDER REACTION
K1 K2
A  B 
 C all first order equation
t=0 a 0 0
t a–x y z

Calculate [A]t , [B]t & [C]t

Sol. For  A
d [ A ]
= r1 = K1 [A]
dt
d [ A ]
= K1 dt
[A]
k 1t
 [A]t = [A]0 e
k 1t
a – x = ae
k 1t
 x = a(1 – e )
For  B
r2 = K2 [B]
dy
= K1ae–kt – K2y
dt

[27]
 dy
+ K2y = K1ae-kt
dt
dy + K2ydt = K1 ae-kt dt
k 1t k 2 t
e k 2 t dy + K2 y e k 2 t = K 1ae .e dt
t t
k t ( k 2 k 1 ) t
 d(K 2 ye 2 ) =  K1ae dt
0 0

 K 1a 
K2y ek 2 t =  K  K  e (k 2 k 1 )t + y
 2 1

At t = 0 y=0
 K 1a 
y = –  K  K 
 2 1

K 1a
 y = K  K { e  k1t – e  k 2 t } (remember)
2 1

Calculate time at which concentration of B will be maximum

dy
=0
dt
–K1 e k 1t + K2 e k 2 t = 0

K 1 k1t
e
e k 2 t = K
2

K1 k 2 t
e
e k1 t = K
2

K1
K1t = ln K + K2t
2

1 K1
 tmax. = K  K  ln K (remember)
1 2 2

 ln K1 – ln K 2 
 
 K1 – K 2 

K2 K2
K  K – K K  K – K
[B]max = a ×  2  1 2 = [A0]  2  1 2
 K1   K1 
CASE- K1 >> K2
K1 K2
A   B 
 C
a

a–x x

k 1 t
 [A] = a e (conc. is minimum)

 [B] = a e k 2 t

 [C] = a ( 1  e k 2 t )
 K1t >> K2 t

[28]
  Kp > K2
 K1t << – K2 t
 e k 1 t << e k 2 t

K 1a
y = K (  e k 1 t ) = a e k 2 t = [B]
1

effective half life is t1/2 for B.

CASE  : K2 >> K1
[B]t  0
k 1 t
 [A] = a e

 [C] = a ( 1  e k 1 t )
K1 K1  K1 
k t
y = K ae 1 = K [A]   0 
2 2  K2 

Conc
a [C]

[B] [A]
t

CASE  : If in sequential equation, k1 = k2 = k

y = Ka e–Kt

z = a(1– e–Kt) – K at e–Kt

k1 k2
Ex. In the case of first order consecutive reactions A   B 
 C (Product), one may show that the
concentration of B is given by

k 1C0A
k 1t k
CB =
(k 2  k 1) e  e  2t .

The usual assumptions are CA = CA0 at t = 0 while CB = CC = 0 at t = 0. Show that CB has its maximum

 2.303   k2 
value at time t =  k  k  log   .
 2 1  k1 

dCB k 1CA k 2 t
Sol. =
(k 2  k 1) k 2 e   k 1e k1t 
dt

equating this zero k 2 e k 2 t  k 1 e k 1 t

k2  k2   2.303   k2 
  t =  k  k  log  k 
 k = e(k 2 k 1 ) t n  k  = (k 2 – k 1) t 
1  1  2 1  1

[29]
 Part-II (Discuss after reshuffling)
LECTURE # 9
DEPENDENCE OF RATE OF REACTION ON TEMPRATURE
 earlier experent it was observed that on increasing temp. by 10ºC rate of reaction becomes double or triple.
Temp. coefficient ( T.C.) is the ratio of rate of reaction or rate constant of reaction at two temp. differing by
10ºC (generally 35º & 25 ºC )
R T 10 º C K T 10 ºC
T.C. = RT = KT

R 35 ºC
=R
25 º C
T.C. is generaly between 2 to 3.
RT + T = RT(TC)T/10

Ex. If Tempeture cofficient = 2 then

Calculate rate of reaction at 60ºC if at 20ºC it is R
R 60ºC = 16R
RT + T = RT(TC)T/10

Ex. If rate = R, at’ 20ºC calculate rate at 45ºC if Tempeture cofficient = 2

R’ = R (2)2.5
R’ = 4 2 R

Ex. Two  orderreactions 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. Let the rate of reaction for  at 25°C be R1 and the rate of reaction for  at 25°C be R2
Also, R1 = R2
Rate of reaction
 At 25°C R1 R2
35°C 2R1 3R2
2
45°C (2) R1 (3)2 R2
3
55°C (2) R1 (3)3 R2
65°C (2)4 R1 (3)4 R2
5
75°C (2) R1 (3)5 R2
rate of reaction for  (3 ) 5 R 2
 At 75°C =
rate of reaction for  ( 2 ) 5 R1
(  R1 = R2 ) = 7.5937

ARRHENIUS / TRANSITION STATE THEORY

1. According to this theory during a chemical reaction there will be collision between different reactant molecules
2. During these collisions, the existing bonds of reactant molecules will be broken and new bonds of product
molecules will be formed
3. All random collisions will not lead into the product formation only those collision which are taking place in
proper orientation and with sufficient amount of energy will lead into the product formation. These collisions
are also called effective collisions.
4. During effective collisions there can be considered formation of a hypothetical species known as activated.
Complex or transition state in which the reactant bonds are not yet completely broken and products bonds
are not yet completely formed
T.S.  can’t be Isolated  very high energy, very unstable, it can’t be experimentally studied.
ELEMENTARY / SINGLE STEP / SIMPLE RXN.
 Which takes place in one stop without formation of any intermediate (can be isolated and shielded)
AB + A  A2 + B

[30]
 A B A improper orientation

B A A proper orientation form the product

B A A

T. S. B A A

B + A A

=
O
Ex. NO2 + NO2 N2 O 4
N–N

=
O
O
O O
N N Proper orientation.
O O

ENERGY PROTILE / ENERGY LEAEC POAGPAIN

Er = avg. energy of reactant

EP = avg. energy of product molecules
EP < Er or EP < Er
EP > Er endothermic
EP < Er exothermic
H = ( EP – Er ) = enthalpy change
Ethreshold = min. energy of reactant molecules so they can lead to the transition or product formation.
Ea = activation energy (it is excess energy of reactant molecules w.r.t. avg energy level so that these can
lead into product formation)
Eaf = activation of forward rxn.
Eab = activation of for backward.
H = Eaf – Eab
Ethreshold = Eaf + Er = Eb + Ep
From maxwellian distribution it is found that fraction of molecules having excess energy greater the threshold
energy lead to the formation of product.
k  Ae E aRT
r = K [conc.]order
dependence of r on temp is due to dependence of k on temp.

K  e Ea / RT
K  Ae Ea / RT [Arrhenius equation]

[31]
 A is pre exponontial factor / frequency factor representing collisions taking place with proper orientation.
A and Ea are independent of temp. generally.
Ea = min K. E. colliding molecules must have to reach transtion state
Ethreshold= min. total energy to reach transtion state

fraction
of
molecules
T2 T2 > T1
T1

e E a / RT  represents fraction of molecules K.E. having energy greater Ea

rate  e E a / RT
Ea
lnk = ln A –
RT

InA
Ea
slope = –
R
Ea  O
InK

1/T
 T  ,K  A

REVERSIBLE REACTIONS

kf = Af e E af / RT
kb = Ab e E ab / RT

Kf A f e Eaf / RT
Keq = K =
b A b e Eab / RT

 Af 
=  A  e (E af E ab ) / RT
 b

H  Af 
ln Keq = – + ln  A 
RT  b

In Keq In Keq

endothermic 1/T exothermic

1/T

At temp T1 rate const. = K1

T2 rate const. = K2
Ea
lnK1 = lnA – RT
1

[32]
 Ea
lnK2 = lnA – RT
2

K2 Ea  1  1 
ln K =   (remember)
1 R  T1 T2 

Ex. Two st order rxns. are initially having equal rate at a particular temprature. Temprature of both the reaction is
increased by same amount. Calculate rate of which reaction will increase by greater amount ( reaction with
low Ea or high Ea)

 K2  Ea  1  1 
ln  K  =   .....(i)
 1 R  T1 T2 

 K2'  Ea '  1  1 
ln  K  =   .....(ii)
 1 R  T1 T2 ' 

Equation (i) – (ii).

 K2  T
ln  K '  = ( Ea – Ea,)
 2  R

if Ea > Ea,
K2 > K2’
or
E a / RT
K = Ae

dk  EaA   1 
 2 E a / RT
RT  T  A e
=
dt

1 dK Ea
temprature coeff.of rate constant. =
K dt RT 2

K
K . T = fractional change / unit temp. rise

Ex. Explain on the basis of temprature coeffof rate const. that equlibrium of endothermic rxn.will shift in forward
direction on increasing temprature while equlibrium of exothermic shifts back.

 K eq 
 1  H  1  1 
ln  K =  
 eq 2 
 R  T1 T2 

Ex. H = Eaf – Eab > 0 endothermic

Eaf > Eab
on increasing temp. Kf   more than Kb 
Eaf > Eab
reaction will shift in forward direction.

Ex. For the reaction CO(g) + Cl2 (g)  COCl2 (g) under the same concentration conditions of the reactants,
the rate of the reaction at 250°C is 1500 times as fast as the same reaction at 150°C. Calculate the
activation energy of the reaction. If the frequency factor is 2.0 × 1010 M–1 sec –1, calculate the rate
constant of the reaction at 150°C.

[33]
 k2 E  T2  T1 
Sol. log k = 2.303 R  T T 
1  1 2 

E 100
log 1500 = 
2.303  2 523  423

3.1761  2.303  2  523  423

E= = 32.36 kcal mol–1
100

E 32360
log k = log A – 2.303 RT = log (2.0 × 1010) – = 10.301 – 16.609 = – 6.308
2.303  2  423
k = 4.92 × 10–7 litres mol–1 sec –1

LECTURE # 10
Catalyst and catalysis
A catalyst is a substance, which increases the rate of a reaction without itself being consumed at the end of
the reaction, and the phenomenon is called catalysis. There are some catalysts which decrease the rate of
reaction and such catalysts are called negative catalyst. Catalyst are generally foreign substances but
sometimes one of the product may act as a catalyst and such catalyst is called “auto catalyst” and the
phenomena is called auto catalysis.
Thermal decomposition of KCIO3 is found to be accelerated by the presence of MnO2. Here MnO2 (foregin
substance) acts as a catalysts.
2KClO3 + [MnO2] 2KCl + 3O2  + [MnO2]
MnO2 can be received in the same composition and mass at the end of the reaction.
In the permanganate titration of oxalic acid in the beginning there is slow discharge of the colour of
permanganate solution but after sometime the discharge of the colour become faster. This is due to the
formation of MnSO4 during the reaction which acts as a catalyst for the same reaction. Thus, MnSO4 is an
“auto catalyst” for this reaction. This is an example of auto catalyst.
2KMnO4 + 3H2SO4 + 5H2C2O2 K2SO4 + 8H2O + 10CO2

General characteristics of catalyst

1. A catalyst does not initiate the reaction. It simply fastens it.
2. Only a small amount of catalyst can catalyse the reaction.
3. A catalyst does not alter the position of equilibrium i.e. magnitude of equilibrium constant and hence Gº.
It simply lowers the time needed to attain equilibrium. This means if a reversible reaction in absence of
catalyst completes to go to the extent of 75% till attainment of equilibrium, and this state of equilibrium is
attained in 20 minutes then in presence of a catalyst also the reaction will go to 75% of completion before the
attainment of equilibrium but the time needed for this will be less than 20 minutes.
4. A catalyst drives the reaction through a different route for which energy barrier is of shortest height and hence
Ea is of lower magnitude. That is, the function of the catalyst is to lower down the activation.
Ea = Energy of activation in absence of catalyst.
E’a = Energy of activation in presence of catalyst.
Ea – E’a = lowering of activation energy by catalyst.

[34]
 P.E. Ea
E'a
HR

HP
Products

Reaction Coordinate
If k and kcat be the rate constant of a reaction at a given temperature T, and Ea and E’a are the activation
energies of the reaction in absence and presence of catalyst, respectively, the
k cat Ae E 'a / RT
 = Ae (E a E'a ) / RT
k Ae Ea / RT
k cat
Since Ea – E’a is positive so kcat > k. the ratio gives the number of times the rate of reaction will increase
k
by the use of catalyst at a give temperature
The rate of recation in the presence of catalyst at any temperature T1 may be made equal to the rate of
reaction in absence of catalyst but for this sake we will have to raise the temperature. Let this temperature
be T2 this
E'a E a

e E'a / RT1  e E a / RT2 or T1 T2
Ex. The Ea of a reaction in presence of a catalyst is 4.15 kJ mol–1 and in absence of a catalyst is 8.3 kJ mol–1.
1
What is slope of the plot of l nk vs in the absence of catalyst
T
(A) + 1 (B) –1 (C) + 1000 (D*) –1000
Ea 1
Sol. Now In k = In A – ×
R T

Ea  8.3  10 3
 Slope = – = = 1000
R 8 .3

Ex. The elementary reaction A + B  products has k = 2 × 10–5 M–1 S–1 at a temperature of 27°C. Several
experimental runs are carried out using stoichiometric proportion. The reaction has a temperature coefficient
value of 2.0. At what temperature should the reaction be carried out if inspite of halving the concentrations,
n 6
the rate of reaction is desired to be 50% higher than a previous run. (Given n 2 = 2.585).

Sol. r2 = k2 [A]21 [B]21 for a certain run

r1 = k1 [A]11 [B]11 for a previous run
dividing, we get
r2 k 2 [ A ]2 [B] 2
r1 = k 1 [ A ]1 [B]1
Substituting the given information

[35]
  t 2 27 
  1 1
1.5 = 2 10  × ×
2 2
t 2  27
t 2  27 t 2  27 n 6
 6= 2 10  l n2 = l n 6  = n 2
10 10

t 2  27
 = 2.585  t2 = 52.85°C
10
~
 53°C

MECHANISM OF REACTION
Reactions can be divided into
(a) Elementary / simple / single step
(b) Complex / multi-step

ELEMENTARY REACTION
1. These reaction take place in single step without formation of any intermediate

T.S.

Ep

Er

2. For elementary reaction we can define molecularity of the reaction which is equal to no of molecules which
make transition state or activated complex because of collisions in proper orientation and with sufficient
energy
3. molecularity will always be a natural no
1 = unimolecular one molecule gets excited (like radioectivity)
2.= bimolecular
3 = trimolecular
4 Molecularly  3 because the probabilty of simaltaneous collision between 4 or more molecules in proper
orientation is very low

5. For elementary reaction there is only single step and hence it is going to be rate determining step so order
of an elementary reaction is its molecularity
Order of elementary reaction w.r.t. reactant = stoichiometric co-efficient of the reactant
H2 +  2 2H Simple reaction
rate = k [H2] [2]
2H2 + 22 4H ( not elementary )
reaction obtained by multiplying an elementary reaction with some no will not be of elementary nature
H2 + Cl2 2HCl
order = 0

COMPLEX REACTION
1. Reaction which proceed in more than two steps. or having some mechanism. ( sequence of elementary
reaction in which any complex reaction procceds)

[36]
 E T.S.

intermediate

2. For complex reaction each step of mechanism will be having its own molecularity but molecularity of net
complex reaction will not be defined.
3. Order of complex reaction can be zero fractions whole no, even negative w.r.t. some species.
4. Order of reaction or rate law of reaction is calculated with the help of mechanism of the reaction generally
using Rate determine step (R.D.S) if given.
5. Rate law of a reaction is always written in terms of conc. of reactant, products or catalysts but never in terms
of conc. of interimediates.
CALCULATION OF RATE LAW/ OREDER
(A) MECHANISM IN WHICH RDS GIVEN
(i) If RDS involves only reactant, product or catalyst on reactant side
rate law of RDS = rate law of reaction
Ex. Calculate order and rate law of reaction
2NO2 + F2 2NO2F with help of mechanism

K1
NO2 + F2 
  NO2F + F (slow )
molecularity = 2 for both
 : NO2 + F  K2
 NO2F (fast )
According to RDS
Rate = K1 [NO2] [F2]
Ex. Calculate rate law
3ClO–  ClO3– + 2Cl–
K1
2ClO–   ClO2– + Cl– (slow)
ClO2– + ClO–  K2
 ClO3 + Cl (fast )
– –

Rate = K1[ClO– ]2

(ii) RDS is having intermediade on reactant side

To calculate order, we have to specify [ intermediate] in expression of rate law in terms of conc. of
[R], [P] or catalyst with the help of same equilibrium step given in mech.
Ex. 2O3  3O2
k1
O3 O2 + O (fast eq. step)
k2
(intermediate)
k3
O + O3    2O2 (slow)

From R.D.S.
rate = k3 [O3] [ O]
According to equilibrium step.
K1 [O 2 ][O]
Keq. = K = [O ]
2 3

[37]
  K1 [O3 ] 
[O] =  K [O ] 
 2 2 
Rate = K3 [O3] [O].
 K1 [O3 ] 
= K3 [O3]  K [O ]  .
 2 2 

K 1 K 3 [O 3 ] 2
Rate = K
2 [O 2 ]

–
Ex. H+ + HNO2 + C6H5NH2  Br +
 C6H5N2 + 2H2O
interimediate
K1
H+ + HNO2 H2 NO2+ (fast) equilibrium step
K2
interimediate
K3
H2NO2+ + Br – 
 NOBr + H2O (slow)

NOBr– + C6H5NH2  K4 +
 C6H5N2 + Br + H2O (fast)
–

Sol. r = K3 [Br–] [H2NO2+]

K1 [H2NO2 ]
Keq = K = 
2 [H ][HNO2 ]

 K1 
[H2NO2+] =  K  [H+] [HNO2]
 2

K1 K 3
r = [H+] [HNO2] [Br–].
K2

(B) MECHANISMS IN WHICH RDS NOT SPECIFIED

STEADY STATE APPROXIMATION
Initially, for most of the cases only reactants are taken and hence the rate of production of intermediate is
large in comparision to its rate of consumption but after some time rate of consumption of intermediate will
become equal to its rate of production. This is known as steady state of reaction. Finally when reaction is
going to get completed, rate of consumption will become more then rate of production. But for most of the
times reaction remains at steady state. So rate law of reaction during steady state can be taken to be final
or net rate law of reaction.
Intermediate

Steady state

Time

d [intermediate ]
At steady state =0
dt
Ex. 2O3  3O2
K1
O3   O2 + O
K2
O2 + O 
 O3
K3
O3 + O  
 2O2

[38]
 1 d[O 3 ] 1 d[O 2 ]
Sol. rate = =
2 dt 3 dt

d[O 3 ]
= – K1 [O3] + K2 [O2][O] – K3 [O3] [O]
dt

d[O 2 ]
= K1 [O3] – K2 [O2] [O] + K3 [O3] [O]
dt

d [O ]
At steady state =0
dt

d[O]
= K1 [O3] – K2 [O2] [O] – K3[O3] [O] = 0
dt

K 1[O 3 ]
[O] = K [O ]  K [O ]
2 2 3 3

d[O 3 ] K 2 [O2 ] K1[O3 ] K1 K 3 [O3 ]2

= – K1 [O3] + K [O ]  K [O ] –
dt 2 2 3 3 K 2 [ O 2 ]  K 3 [ O3 ]

K1K 2 [O2 ] [O3 ] – K1K 3 [O3 ]2

= – K1 [O3] +
K 2 [O 2 ]  K 3 [O3 ]

K1K 2 [O2 ][O3 ] – K1K 3 [O3 ]2  K1K 2 [O2 ][O3 ] – K1K 3 [O3 ]2
=
K 2 [O 2 ]  K 3 [O3 ]

– 2K1 K 3 [O3 ]2
=
K 2 [ O 2 ]  K 3 [ O3 ]

 –1 d  K1 K 3 [O3 ]2
 2 dt [O3 ] =
  K 2 [ O 2 ]  K 3 [ O3 ]

1 d
Rate = – [O3]
2 dt

K1 K 3 [O3 ]2
So, Rate (r) =
K 2 [ O 2 ]  K 3 [ O3 ]

if 3rd step is RDS then K1>> K3

K2 >> K3
K 1 K 3 [O 3 ] 2
r=
K 2 [O 2 ]  K 3 [O 3 ]

Br
Ex. H+ + HNO2 + C6H5NH2  C6H5N2+ + 2H2O
H+ + HNO2 
K1
 H2NO2
+

H2NO2+  +
 H + HNO2
K2

K3
HNO2+ + Br– 
 NOBr + H2O.
K4 +
NOBr + C6H5NH2 
 C6H5N2 + H2O + Br
–


d[H2NO 2 ]
= K1 [H+][HNO2] – K2 [H2NO2+] – K3 [H2 NO2+] [Br–] = 0
dt
[H ]]HNO 2 ]
[H2NO2+] = K1
K 2  K 3 [Br – ]
d d
rate = [C 6H5NH2 ] = [HNO 2 ]
dt dt

[39]
 d
[C 6H5NH2 ] = K [ONBr ] [C H NH ]
dt 4 6 5 2

d
[NOBr ] = – K4 [C6H5NH2][NOBr ] + K3 [Br–] [H2NO2+] = 0
dt

K 3 [Br – ][H 2NO 2 ]
[NOBr] =
K 4 [C 6H5NH 2 ]

K 4 K 3 [Br – ][H2NO 2 ]

K 1 K 3 [Br – ][H ][HNO2 ]
r= [C 6H5NH2 ]  r =
K 4 [C 6H5NH2 ] K 2  K 3 [Br – ]

THE FOLLOWING DERIVATIONS WILL BE COVERED IN DETAIL IN PHYSICS SO WE CAN ONLY QUOTE
THE RESULTS AND DO TELL STUDENTS THAT ALL THESE WILL BE COVERED IN PHYSICS. THE
DERIVATIONS ARE GIVEN HERE FOR YOUR HELP AND UNDERSTANDING

LECTURE # 11
Radioactivity
* All radioactive disintegration follow Ist order kinetics.
A  B + C
Int. nuclie N0
At time t. N

*  = Not dependent on temperature.

– dN – dN
dt
= N ;  N
=   dt
N  N0e  t

1  N0  A 0 N0 n0 w 0
 ln   ;   
t  N  A N n w
n0 = initial moles ; w0 = initial weight
1  w0 
= ln  w  (w = weight of A remaining after time t)
t  

1  w0 
 ln  
w x
t  0 
Half life :
N0
t = t1/2 ; N=
2

1  N0 
= t ln  N / 2 
1/ 2  0 

ln 2
= t
1/ 2

ln 2 0.693
t1/ 2  
 

[40]
 Average life :
1
Tavg.   1.44 t1/ 2


 dN. t 1 dN
0
Tavg. = = ( = N and N = N0e–t ,  dN = – N0e–t dt)
N0  dt

Unit of activity :
* curie (Ci) = 3.7 × 1010 dps
millicurie (mCi) = 3.7 × 107 dps
microcurie (Ci) = 3.7 × 104 dps
* Rutherford (1 Rd) = 1 × 106dps

Application of radioactivity :
1. Carbon dating : (used for wooden object)
In living matter existing in nature : 6
C14 : 6
C12 = 1 : 1012
(radio active) (stable)
In upper atmosphere :

7
N14 + 0n1  6
C14 + 1p1
Ratio of radioactive carbon in dead animals / trees decreases with respect to time.
1  A0 
t= ln  A 
  
Half life of 6C14 = 5770 yrs.
A = activity of old wood piece. ; A0 = activity of fresh wood piece.
2. Age of rocks or minerals

92
U238  82
Pb206
(radioactive) (stable)

Reaction :

92
U238  82
Pb206 + x2He4 + y–1e0

z
XA  z–2
X´A – 4 + 2He4

z
YA  z+1
Y´A + –1
e0

difference of mass no. 238  206

Number of -particles = = =8
4 4
238 = 206 + 4x + 0 .....(1)
92 = 82 + 2x – y .....(2)
On solving (1) and (2),
x=8 ; y=6

92
U238  82
Pb206 + 8(2He4) + 6(–1e0)
At time t wg yg

1  w0 
t= ln  w 
  

1  w0 
t= ln  w  x 
  0 
w = w0 – x
 w0 = w + x

[41]
 1 mole or 238 g U provide 206 g of Pb
238
 g U provide 1 g Pb
206

238
 × y g U provide y g Pb
206

238 238
x= ×y ; w0 = w + ×y
206 206

92
U238  82
Pb206 + 82He4 + 6–1e–
V(in mL) collected
PV
nHe = ........ (1)
RT

1  n0 
t= ln  n 
  

w
n= ........ (2)
238

nHe
n0 = n +
8

Ex. The half  life of a radioactive isotope is 3 hours . If the initial mass of the isotope were 256 gm , the
mass of it remaining undecayed after 18 hours would be :
Ans. 4 gm
256 256
Sol. 6 = = 4.
2 64

Ex. 1 gram of 79Au198 (t1/2 = 65 hrs) decays by beta emission and produces stable mercury. How much mercury
will be present after 260 hours.
Ans. 0.9375 gram.
198  198
Sol. 79Au 80Hg + –1e0
t1/2 = 65 hr, T = 260 hr, T = t1/2 × n
260
Number of half live (n) = = 4.
65
N0 1 1
Amount left undecayed (N) = = = g
24 24 16

15
Amount decayed of Au = = 0.9375 gram.
16

dN 1
Ex. Starting from the equation for radioactive decay i.e. – = N, derive the expression, mean life = .
dt 
dN
Sol. (i) – = N . This on integration gives (with N = N0 , at t = 0) ; N = N0 e–t
dt

  
  dN
 tdN  t dt  ( N0 )e t t dt
   
t 0
dt t 0 1 1
t 0
Mean life =  
 =

=  = .  Mean life =
 
  dN ( N0 )e t dt
 dN   dt 


t 0
 t 0
dt t 0
 

[42]