CHEMICAL KINETICS Rate law

completes
equal
in
single step .

to stoichiometric coefficients of reactions

. Elementary reaction ,

molecularity is
equal to its order
.

Average rate of Reaction

L Rate of Reaction -3 ↑
Instantaneous Rate of Reaction
Reactions
>
-
-AC
Rate Change in conc or .

pressure Elementary
Rate =
(Reactant)
=

d[R]
At

↓
-

Time taken Rate =

(Reactant)
dt
-
AC Unit moll"time" atm time Maximum value of
Rate (Product) or
molecularity
=
=

At &[P] Note
Note =
Rate of Reaction can never be-ve Rate = (Product)
Zero order reactions be
Molecularity -
>
or order is 3
.
dt can never
elementary
For
elementary reactions Fractional order is not possible .

/ I
.

Rate law unit of rate constant ~

(k)
CONC -

[P]
L
AA + 6B >
-

Product Zero order First order

1 -"
Time
Rate < [A] [B]
[R]
n =
0
=
(01) n = 1 can be an
integer (1 2003) but it cannot complex reaction
molecularity of each
step
C >
,
--- -
L 3
of mechanism is defined
KIA] "[B] time K sect be zero or
negative or Fractional.
separately.
Rate
(11) 'sec
=
K
(atm)' -"Time
= V
=

K =

K Rate constant reaction rate Reactant Product

specific
>
or
-
=

order of reaction root A

>
x =

Overall NXNS : A + 2B > Products complex

-
-

N2 + 3Hz - >
2NH3
y
=
order of reaction cost B completed in Multi
step
Step 1 : A + 2B - C fast

Rate dIN2] d[H2T + d[NH3] Differential Rate Law Overall order # Order of Reaction Overall rate of on is controlled
by slowest step which is
Ccty .
=
-
= =
=
-

Step 2 :C >
-

Products slow
called Rate
dt dt 2dt
Determining Step (RDS)

Xb
3

NITESH DEVNANI
↑ -
Note
Rate of + d[NH3]
appearance
=

Rate of
disappearance - dIN2] d[H2] Reactions
complex
= I
-

(Product) dt
order is an experimental quantity
(Reactant) dt dt
Order of on
may be zero
,
He ,
-
> Rxn intermediate

In rate rate of depends reactants

-
ve or fractional . expression ,
oxn on conc of

of slowest step which must be free from intermediate

.

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 CHEMICAL KINETICS
K T + 10
to 3
(Ealf (Ea)f 2
=
AH = -

M =

KT
(Ealf Activation
energy forward
=

enk
InA-E
=

energy backward
(Ealf =
Activation .

Ape-t
Ea log
N

Rate Law
Integrated At enk

(
Threshold energy
=

↑ Ef
=
=
+

L - completion time (t100 % At

I In a
At =
Ao-k+
At
↑
=
0
Zero order reactions (n = 0)
Rate
<
= K
-

coefficient (M)
Initial t Temperature
=A
Ao

I
conc.

y
=
100 %

Condition
Energy ↓
I 1)
At =
Conc. left after time 't

First order reaction (n

K Rate constant A H
Ep-ER
= =
=

- "c =
logA

I I
1H = + Ve AH = -

Ve
n logk
Half life / + ) Half life =
+,200 50 % -
C = Ao
Endothermic Exothermic
m

.
2 303R

At
A At
12 as
K
tV
=
M = -
= =

.
released
Energy absorbed Energy 4

4 &

-1/2 Ep >
ER Ep < ER
=
t
Y
Independent of Ao .

a)entr =Eli i
> Activated complex >
Activated complex
N N

N
(Ealf N
n(Ea)f N
a
(Ea)t N

Total number of collisions (Ea)f

per second in unit Energy
L
V

-
N

Energy ER ET
First order Zero order ET -AH
volume
frequency
AH
is called collision
w

. -
V

ER

t =An e t
= y Rxnprogress
V
C 7 < >
Rxn
V
progress Y

-Y2d A -1/2 d As Collision theory A =

Arrhenius constant

>
- Ea =
Activation
energy
↓ - t
N
a
t
//2
-
For reaction to there must be collisions Universal constant
/2 a occur
Ae-Ea/RT R
gas
=

K Arrehinus
equation
.

< 4
4 >
molecules. Temperature (Kelvin)
in between
reacting T
A A =

-
small fraction of collisions are
capable to convert TY K4 Rate ↑

A
= =

NITESH DEVNANI
↑ reactants into products called effective collisions
.

Catalyst
Half Life substance which alter rate of Maxwell Distribution curve
can on without

I Pseudo first order reactions

having any change in
composition
Increased
Elementarybimolecular of the reactant
-

Second order reactions in which one

Fraction T T + 10 Fraction
nth order reaction is in excess
. These reactions to be of with inhibitor
of molecular
A- appear without
catalyst

.
t /2 <

2nd order butFollow ast order kinetics

.
~
with
catalyst
Al-M
.

-1/2 <
Ep Emer
Rate = K. [A]' >
-
Order = 1
" AR

E gY

Aftera half life

A
=

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