Chemical Kinetics

1. Chemical reaction : - Fast ionic NaOH + HCl ---> NaCl + H2 Rate cannot be calculated
Slow Rusting of iron
(reversible) Moderate rate reaction
2. For chemical reaction aA + bB cC + dD
Average Rate r= = mol L
-1
S
-1

for A ------> B r = [ -ve sign for decrease in concentration ]
3. Reaction life time: - Time to complete 98% reaction.
4. Instantaneous rate: - Rate at given instant of time is called instantaneous rate and found
graphically. Represented by slope of graph.






For Reactant For Product
5. Homogeneous Reaction : - Reactant and catalyst in same phase.
SO2(g) + O2(g) ---[NO]-----> SO3(g)
6. Heterogenous Reaction : - Reaction and catalyst in different phase.
SO2(g) + O2(g) -------V2O5(s)-----> SO3
7. Effective collision : - Collision of reactant molecules which bring chemical change
8. Threshold energy: - Minimum energy to bring chemical change.
9. Activation Energy (Ea) : - Minimum energy to be supplied externally to start a reaction.
Ea = Eth - ER
ER Energy required to form intermediate [ activated complex]
10. Law of mass action : - r = k [A]
a
[B]
b
[a, b are coefficient in balanced chemical reaction].
11. Rate law expression : - Rate of chemical reaction determined experimentally i.e dependence of
rate on concentration of reaction raised to power determined experimentally.
r = K [A]
x
[B]
y

x = order of reaction with respect to [A] x, y may or may not be
y= order of reaction with respect to [B] equal to stoichiometric
x + y = overall order of reaction coefficient
12. Rate constant :- If [A] = [B] = 1mol L
-1
r = K i.e rate constant is equal to rate of reaction
when conc. of reactants = 1mol L
-1

13. Unit of rate constant : - K = r/[R]
n
= mol L
-1
S
-1
/ [mol L
-1
]
n

for zero order = mol L
-1
S
-1

for I order = S
-1
S
-1
always comes
for II order = mil L S
-1

14. Zero order reaction :- Rate does not depend on conc. of reactant.
H2 + Cl2 ---hv---> 2HCl
15. Negative order reaction : - Rate decreases on increasing conc.
2O3 ----> 3O2
16. Fraction order reaction : - H2 + Br2 ------> 2HBr r = k [H2] [Br]
1/2

17. Molecularity: - No of [R] collide simultaneously to bring chemical change in elementary
reaction is called molecularity.
Uni molecular NH4NO2 ----> N2 + 2H2O
Bi molecular 2HI --------> H2 + I2
18. Complex reaction: - Reaction which has molecularity more than 2 and proceed through more
than one step. Slowest step is rate determination step.
e.g. 2NO2 + F2 ---> 2NO2F
Rate law given r = K [NO2] [F2]
Mechanism NO2 + F2 ----slow----> NO2F + F Given, NO2 + F2 ----slow----> NO2F + F
NO2 + F ------fast----> NO2F NO2 + F ------fast----> NO2F
2NO2 + F2 ------> 2NO2F
r = K [NO2] [F2]
19. Integrated rate equation: - Equation give relation b/w rate constant, time and conc. of [R]
calculated by integration is called integrated rate equation.
r = K [A]
n
equate for zero order K = ([R]o [R])/t , t

= [R]o/2K
r = - dA/dt & integrate, const. = c for Ist order K = (2.303/t)log[R]o/[R]t
at t = 0 [R] = [R]o t

= 0.693/K, not depend on conc. of R




20.
Graph b/w ln[R] and t Graph b/w log [R]0/[R]





21. Pseudo first order reaction : - Chemical reaction has two [R] but rate depend on only one [R],
since other is in excess is called pseudo first order reaction.
e.g. CH3COOC2H5 + H2O ----H+------> CH3COOH + C2H5OH
r = K
I
[CH3COOC2H5] [H2O] = K [CH3COOC2H5] i.e K = K
I
[H2O]
22. Half life of a n
th
order reaction : -
t

1/ [R]0
n-1
Therefore, for zero order t

[R]0
n-1

for first order t

independent of conc.
for second order t

1/[R]o
23. Arrhenius Equation : - Give relation b/w rate constant and temp.
On increasing temperature by 10
0
[10K] rate constant becomes double.
K = A . e
-Ea/RT

lnK = lnA (Ea/RT) lne , where ln = loge
lnK = lnA (Ea/RT) / logK = logA Ea/2.303RT
logK2/K1 = Ea/2.303R[1/T1 1/T2]


24. Effect of catalyst : -
(i) Lower Ea by providing alternate path
(ii) Do not change Kc since rf = rb
(iii) Do not change G
(iv) Work for only spontaneous reaction

25. Fraction of molecule having E equal to or greater than Ea
x = e
-Ea/RT
/ ln x = -Ea/RT / log x = -Ea/2.303RT
26. Collision theory for reaction rate : -
(i) A reaction occur on proper collision of two molecules if posses E >= Ea i.e if they have no
proper orientation reaction not take place.
e.g. CH3Br + OH- ------> CH3OH + Br
-

(ii) If improper orientation




(iii) According to collision theory expression for rate of a reaction
r = PZABe
-Eo/RT
, P = Probability of orientation factor ZAB = frequency factor
Ea = activation energy, R = 8.314 , T = temperature