CHAPTER-3

Chemical Kinetics

The branch of chemistry that deals with the study of rate of Rean, factors
affecting it, mechanism of Rean and their aspects.

Very fast Rean =Ionie Rean

Moderate Rean
x r__________ y P
1 △ [R ]
rR ¿− x △ t

1 △ [ P]
rp ¿ y △ t

→ N2 + 3H2 → 2NH3

△ [N 2] −1 △ [ H 2 ] 1 △ [NH 3]
rav = = =
△t 3 △t 2 △t

→ 2H2 + O2 → 2H2O

△ [H 2] △ [O 2]
rH2 = =
△t △t

Q-1. Find the rate of formation of H 2O if rate of disappearance of H 2 is 2.5 ×

10-3 mol/L-1 t-1
→ 2H2 + O2 → 2H2O

−△ [ H 2 ]
Ans. 2H2 = =2.5 × 103
△t

△ [ H 2O ] −1 △ [ H 2 ] 1 △ [ H 2 O]
2H2O = → r= =¿
△t 2 △t 2 △t

r = 2.5×103
 −1 △ [ H 2 ] −△ [ O 2 ]
r= =
2 △t △t

1 △ [ O2 ]
×2.5 × 103 ¿
2 △t

−△ [ O 2 ]
= 1.25 × 103 ¿
△t

Q-2. Find the rate of disappearance of NH3 on Iron surface if its initial coven is
2 M and after 10 min, it remains 1M. also, find rate of appearance of H 2
in second and hour and min.

An 2H3 → N2 +3H2

−△ [ NH 3 ] −[ 1−2 ] 1
rNH3 = = = =0.1 M min-1
△t 10 10

−1 △ [ NH 3 ] 1 △ [ H 2 ]
rav = =
2 △t 3 △t

3 △ [ H 2]
= 2 × 0.1 = =0.15 M min-1
△t

Rh = 0.15 × 60 Mn-1
0.15
rsec = 60
Ms-1

 Instantaneous rate of rean

For reactant

−d ( R )
Tan Q = rinst = slope = -ve =
dt

p1
p2

R1 R2
R1 > R 2
For Product

Coven of P2
 P1 slope = +ve = rinst

t1 t2 t
P2 > P 1

Coven

for equm.

 Factors affecting rate of rean

Concentration
aA + bB = cC + dD
r α coven of A and B
r α [A]a
r α[A]a [B]b
Law of mass action
r= k[A]x [B]y
x = a, x ≠ a y = b, y ≠ b
 x and y are order of rean w.r.t A and B respectfully
 x and y can be calculated experimentally
 overall order of rean (n) = x+y
 order may be fraction, integer, 0

r
 K= [ A ] x [ B ] y =¿it is ratio of rean when coven of reactant
is unity or 1M

K= Mt-1 = M1 t-1 = Mt-1 = M1-x t-1

Mx, My Mx+y Mx

Q-3. Find the unit of rate comtt. For 1st order rean .

K=M1-1 t-1 = t-1

 Graphs:- [r]
y = mx+c
y = y-axis
m = slope
x = x- axis
c = intercept

For zero order [R]

r = k[R]0 = k
on comparing y= mx+c
k = [Ro]-[R] = kt = [Ro]-[R] [R]
t
[R] = [Ro]-kt
[Ro] x

on comparing with mx+c

 First order rean r
r = k[R] + o
y = mx + c
x

K = 2.303 log [Ro]

t [R] [R]

log [Ro] = kt , k = 2.303 log [Ro]

[R] 2.303 t [R]

kt = 2.303 log [Ro]

[R]
Ro/R _K__
2.303 -kt = log [Ro]
2.303 [R]

mx = y

-kt = log [R]

2.303 [Ro]
t

y
 log R t
Ro
-2k/2.303

t = 2.303 log Ro
R R

kt= 2.303 (log Ro-log R)

kt = log Ro – log R log Ro

2.303

log R = log Ro – kt__ log R -k/2.303

2.303

log R = log Ro + (- k ) t
2.303
y = c + mx

→ First order rean never completes

 Hay life of a reaction

The time taken to reduce to the coven of reactant to its hay life, RY2, R50%

t = t50%, initial coven = Ro, final coven = Ro- Ro = Ro

2 2

 Zero order

t= [Ro] –[R] = t ½ = [Ro] – Ro/2 = Ro

k k 2k

→ Hay life of a zero order rean depends on initial coven of reactant

 First order

t = 2.303 log Ro = t ½ = 2.303 log Ro = t ½ = 2.303 log Ro

k R k Ro/2 k Ro/2

t ½ = 0.693 = k = 0693
k t½
 Hay life of 1 order rean is independent of any coven term.
st

 First order gaseous rean

2.303 p˚
k= log ( )
t p

2.303 p˚
t= log ( )
k p
 p= final p of reactant (depends on stoichiometry of rean)

Exe 4.6. 2N205 (g) 2N2 04 (g) + O2 (g)

t=0 pº - -

t=t (pº- px) (px) ¿)

px
pº - px + px + 2 = 0.512

px
pº + 2 = 0.512

px
2
= 0.512-0.5

px
2
= 0.012 = px = 2.024

2.303
(
k = 100 log 0.5−2.024
0.05
)
2.303
k= 100 log 0.51 - log (0.476)

k = 4.6 × 10-4 s-1

 Pseudo first order reaction

The rean which appears to be first order rean is actually of 2nd or other order.

Eg.:- Ester Hydrolysis

0 0
11 11
R - C - O - R1 + H2O H+ R - C - OH + R1 OH
S+ S-

(0.1 mo1) (10 mo1)

10-0.1=9.9 mo1 = mo1

r = k[Ester]
r = k’[Ester] [H2O]

k’[Ester] [H2O] = k [Ester]

k’ [H2O] = k

When a reactant is taken into large excess, the rate of rea n depends on coven of
other reactant and follows first order. This rean is c/a pseudo first order rean
 Tow types of reaction

On the basis of kinetics

→ (1) Elementary/ simple rean
The rean which computer in single step and this rate is determing step.
 Eg.:- SN2 rean.
Rx + KOH →ROH + KH
r = k[Rx]’ [KOH]’ (molecularity = 2)

Molecularity :- No of molecular present in the rate determing step of rean

→1,2,3

1. Complex rean :- the rean which completer in two more step is c/o complex rean.
Note :- for a complex rean, the rate determing step will be the slowest step.

A + D → C
A → Slow
B + D fast C

r α [A]
r = k[A]

Molecularity = (1)

 Temperature Dependence of rate of rean.

2) collision between reactants → ( collision theory)

A + BC → AB
Rate of collision d r α k

3) A + BC → AB
A + CB → AB ×

Only collision do not produce product but collision must be effective and
oriented to produce product.

4) Temperature , rate of collision ↑, r↑, ↑k

5) threshold energy (energy barrier) (ET)

The minm energy to which reactant must reach to form product.

Region of energy which is possessed by

maxm fraction of molecules
N
No

ET

N= no. of molecular crossing energy carrier

No = initial no. of molecular taken.
 T1=T T2= T+10

N Arva decreases
No

Energy A

With 10 unit increase in temperature increases the rate of rea n by 2 dimes’ it

is experimentally observed k α e-Ea/RT

 Arrhenius Equation

k α e-Ea/RT
k = Ae-Ea/RT [A=frequency factor]

in K = -Ea
A RT

2.303 log K = -Ea

A RT
log K = _-Ea____
A 2.303RT

log K = log
_-Ea___
2.303RT
→Ea = Energy of activation
H2 +I2=2HI

Transition state
(high energy complex)

 The energy required to convert reactant into high transition complex

(transition state)

Ea
Energy P1= intermediate

P2
n
Rea coordinate

Energy – profile diagram

△H = HP - HR
 △HP1 = HP1 - HR = +VE
△HP2 = HP2 - HR = -VE

E1 = 3240 KJ/mol → ET
E2 = 2140 KJ/mol → P1
E3 = 1000 KJ/mol → P2
ER = 1200 KJ/mol

log K = log A _-Ea___

2.303RT

T↑ , K↑

T1 → K1 → r1
T2 → K2 → r2

T2 > T 1 ⸫ K2 > K1, r2 > r1

R=8.314J = 2 col

log K2 = log A -Ea___

2.303RT2
log K1 = log A -Ea___
2.303RT1
-_ - +
______________
K1
log K 2 ¿
¿
Ea
= 2.303 ( T11 − T12 )
 Catalyst
Ea Ea1→ Ea without catalyst

Ea2 Ea2→ Ea in pressure of catalyst

R
P

fe
N2 + H2 NH3

N2 → → N2 N N N
→
H2 → → H2 H H H

A catalyst decrease the Ea and rate of rea n new takes small path and
becomes faster.
N
N2

ET2 ET1