CHEMICAL KINETICS:-(Gr.

kinesis = movement) The branch of science which deals with

the rate of chemical reactions and thefactors which influence the rates of reactions and the
mechanism by which the reaction proceed.
RATE OF CHEMICAL REACTION:- The change in any one of the reactants or products per
unit time. R →P
decrease in concentration of Reactants
Rate of reaction = time taken
−∆𝑅 −∆𝑃
Rate of reaction = or
∆𝑡 ∆𝑡
Here, ∆R = [R]2─ [R]1
∆t = t2─ t1
∆P = [P]2─ [P]1
∆Rgives the decrease in conc., ∆P gives increse in conc., ∆t, change time, in case of reactants's
conc. - ve (minus) sign is used,
e.g. PCl5(g) → PC3(g) + Cl2(g),
∆[𝑃𝐶𝑙5 ] ∆[𝑃𝐶𝑙3 ] ∆[𝐶𝑙2 ]
Rate = ─ = =
∆𝑡 ∆𝑡 ∆𝑡

REACTIONS INVOLVING DIFFERENT STOICHIOMETRIC COEFFICIENIS OF REACTANTS

AND PRODUCTS: -
A(1mol) + B (1 mol) → 2C (2 mol)

2 Rate of disappearance of A = 2 Rate of disappearance of B

= Rate of appearance of C Rate of reaction
∆𝐴 ∆𝐵 1 ∆𝐶
Rate of reaction = ─ ∆𝑡 = ─ ∆𝑡 =2 × ∆𝑡
e.g. 2N2O5(g) → 4NO2(g) + O2(g),
1 ∆[𝑁2 𝑂5 ] 1 ∆[𝑁𝑂2 ] ∆[𝑂2 ]
Rate of reaction= ─ 2 = ─4 =
∆𝑡 ∆𝑡 ∆𝑡
AVERAGE RATE AND INSTANTANEOUS RATE :
Change in concentration ∆𝑥
Average rate of reactions = = ∆𝑡
Time interval
It is not used because rate of reaction depend upon conc., which is not constant.
𝑑[𝑅] 𝑑[𝑃] 𝑑𝑥
Instaneous rate of reaction rinst =─ = = 𝑑𝑡
𝑑𝑡 𝑑𝑡

General reaction, aA + bB ⇋ 𝑐C + dD
1 𝑑[𝐴] 1 𝑑[𝐵] 1 𝑑[𝐶] 1 𝑑[𝐷]
Rate of reaction = ─ = ─ = =
𝑎 𝑑𝑡 𝑏 𝑑𝑡 𝑐 𝑑𝑡 𝑑 𝑑𝑡

e. g. H2(g) + I2(g)⇋ 2 HI(g)

1
 EXPERIMENTAL MEASUREMENT OF REACTION RATE :-
e.g. 2N2O5(g) ⇋ 2N2O4(g) + O2(g),
concentrations time data at 318K for the decomposition of N2O5
t 0 10 20 30 40 50 60 70 80
[N2O5]
(molL-1) 1.72×10─2 1.13×10─2 0.84×10─2 0.62×10─2 0.46×10─2 0.35×10─2 0.26×10─2 0.19×10─2 0.14×10─2

If 𝑥1 and 𝑥2 are the concentrations in the time interval between 𝑡1 , 𝑡2

∆[𝑥] 𝑥2 − 𝑥1
Average rate of reaction = ─ =
∆𝑡 𝑡2 − 𝑡1

[4.1] For the reaction R—>P, the concentration of reactant changes from 0.03 M to
0.02 M in 25 minutes. Calculate the average rate of reaction using units of time
both in minutes and seconds.
(Ans.)[R1] = 0.03M [R2] = 0.02M, t2 = 25 min.
𝑅 𝑅 (0.02−0.03)
Average rate of reaction = ─ 𝑡2 − 𝑡 1 = ─ = 4×10─4Ms─1
2− 1 25 𝑚𝑖𝑛.

𝑅 𝑅 (0.02−0.03)
Average rate of reaction = ─ 𝑡2 − 𝑡 1 = ─ = 6.67×10─6 Ms─1
2− 1 25×60 𝑠.

[Intext 4.2] In a reaction 2A —> Products, the concentration of A decreases from

0.5 moll-1 to 0.4 molL-1 in 10 minutes. Calculate the rate during this time interval.
(Ans.)[R1] = 0.5 moll-1 [R2] = 0.4 molL-1, t2 = 10 min.
1 𝑅2 − 𝑅1 (0.5−0.4)
Average rate of reaction = ─ 2 =─ = 5×10─3 molL─1min─1
𝑡2 − 𝑡1 10 𝑚𝑖𝑛.

FACTORS INFLUENCING RATES OF CHEMICAL REACTIONS:-

[1] CONCENTRATION OF THE REACTANTS: -
The rate of reaction isproportional to the concentration of the reactants. e.g. directly a
piece of wood burns slowly in air (if 20% oxygen) but burns rapidly in pure oxygen (
100% pure).
[2] T'EMPERATURE OF THE SYSTEM:-
an increase in the temp. increase the rate of almost all chemical reactions.
A decrease in temp. increase the rate.
[3] NATURE OF REACTANTS AND THE PRODUCTS :-
A chemicalreaction involves the breaking of old bonds and formation of new bonds.
e.g. 2NO + O2—>2NO2 (fast)
2CO +O2—>2CO2 (slow) .

2
[4] PRESENCE OF CATALYSTS:-
Catalyst is a substance which influences the rate of a reaction without undergoing any
chemical changes itself. e.g. mixture of H2 and O2 does not react in room temp., but in a
presence of finely divided platinum, rate of reaction become quite vigorous.
[5] SURFACE AREA :- The larger the surface area of reactants,the faster is rate of
reaction. e.g. a piece of log of wood burns slowly but when cut into pieces, it burns
rapidly.
[6] EXPOSURE OF RADIATION:- Increases the rate of reaction.
𝐿𝑖𝑔ℎ𝑡
e.g. H2 + Cl2→ 2HCl
DEPENDENCE OF REACTION RATES ON CONCENTRATION :-
RATE LAW EXPRESSION:-
(i) in the begining of the reaction(when time =0), only reactants are present so that
increasing concentration of product is zero.
(ii) The change in concentration of the various species takes place rapidly in the
begining but very slowly as the reaction approaches the final stage.
LAW OF MASS ACTION :-

At a given temperature the rate of a chemical reaction is directly proportional to the

product of the molar concentration of the reactants.
The molar conc. of the reactant is also called active mass.

3
A + B —>2AB
Rate =k [A] [B ], where [A] and [B] are the molar concentration of reactants, ‘k’ is a rate
constant.
RATE CONSTANT:-
Rate of the reaction when the molar conc.of each of the reactants is unity. It is also
called specific reaction rateconstant.

CHARACTERISTICS OF RATE CONSTANT:-

(I) It is measurethe rate of reaction. Larger the value of'k', faster is the reaction.
(II) Different reactions have different values of k.
(III) It changes with temp.

DIFFERENCE BETWEEN RATE OF REACTION AND REACTION RATE

CONSTANT:
RATE OF REACTION REACTION RATE CONSTANT
(1) It is the proportionally constant in the rate law
(1) It is the speed with which reactants are and is defined as the rate of reaction, when the
converted into products. It is measured as the concentration of the reactants is unity.
rate of reactants decrease in conc. or increase in
conc. of products.
(2) It depends upon the initial concentration of (2) It is independent of the initial concentration of
the reactants. reactants.
(3) Its unity are always molL-1time-1
(3) Its unity depends upon the order of reaction.

RATE LAW EXPRESSION:- to express the rate of reaction as afunction of the

concentration of the reactants.
e.g. 2NO2(g) + F2(g)—> 2 NO2F (Nitryl fluoride)
Rate = k [NO2] [F2]
a general reaction: aA + bB + cC—>Products
Rate = k [A]p[B]q [C]r A,B,C are reactants, a,b, c are stoichio- metric coefficients
p,q,rare power of constant conc. of reactants. which may or may not be equal to
stoichiometric coefficients.

ORDER OF REACTION:- The sum of the powers to which the concentration terms are
raised in the rate law equation to express the observed rate of the reaction.
aA + bB + cC —>Products
∆[𝒙]
Rate= ─ = k [A]p [B]q [C]r
∆𝒕
order of reaction (n) = p + q + r,
when n=1, the reaction is first order.

4
N2O5(g)—>2NO2(g) + 1/2O2(g)
Rate=k [N2O5 ] First order reaction

2NO2(g) —>2NO (g) + O2(g)

Rate=k [NO2]2 Second order reaction

2NO (g) + O2(g) —>2NO2

Rate=k [NO]2[O2] Third order reaction

H2(g) + Br2(g)—>2HBr(g)
Rate=k [H2][Br2]1/2 Fractional order reaction

𝑷𝒕.
2NH3(g) 𝟏𝟏𝟑𝟎> N2(g) + 3H2(g)
Rate=k [NH3]0 Zero order reaction

Zero order reaction is independent of the conc. of reactants.

UNITS OF REACTION RATE CONSTANTS:-

UNITS IN GASEOUS
REACTION SOLUTION
REACTANTS
ZERO ORDER molL-1s-1 atms-1
FIRST ORDER s-1 s-1
SECOND
Lmol-1s-1 atm-1s-1
ORDER
THIRD ORDER L2mol-2s-1 atm-2s-1
nth ORDER (molL-1)1-ns-1 (atm)1-ns-1

𝑐𝑜𝑛𝑐. 𝑚𝑜𝑙𝐿−1
Rate = = = molL-1s -1
𝑡𝑖𝑚𝑒 𝑠
Rate = [R]0 for zero order reaction.
𝑚𝑜𝑙𝐿−1
=k
𝑠
k = molL-1s -1
[4.1] From the rate expression their order of reaction and the dimensions of the
rate constants for the following reactions.
(i) 3NO(g) —>N2O(g) + NO2(g) Rate = k [NO]2
(Ans.) with rate law expression,
no. of order = 2
overall order = 2

5
 𝑚𝑜𝑙𝐿−1
Dimensions of rate constant = = k(molL-1)2
𝑠
or k = mol-1Ls -1

(II) H2O2(aq) + 3𝐈 − (aq) + 2H+ → 2 H2O(l) + 𝐈𝟑− Rate = k [H2O2][𝐈 − ]

(Ans.) order w.r.t. H2O2 = 1

order w.r.t. I − = 1
overall order = 1+1=2
𝑚𝑜𝑙𝐿−1
Dimensions of rate constant = = k(molL-1)2
𝑠
or k = mol-1Ls -1

(III) CH3CHO(g) →CH4(g) + CO2(g) Rate = k [CH3CHO]3/2

(Ans.)order w.r.t. CH3CHO = 3/2
overall order = 3/2
𝑚𝑜𝑙𝐿−1
Dimensions of rate constant = = k(molL-1)3/2
𝑠
or k = mol-1/2L1/2s-1

(IV) C2H5Cl(g) → C2H4(g) + HCI(g) Rate = k [C2H5Cl]

(Ans.)order w.r.t. C2H5Cl = 1
overall order = 3/2
𝑚𝑜𝑙𝐿−1
Dimensions of rate constant = = k(molL-1)1
𝑠
or k = s-1

[Intext 4.3] For a reaction, A+B→ Product, the rate is given byr= k [A] 1/2 [B]2
What is the order of the reaction?
(Ans) order = 2 + 0.5 = 2.5 (Fractional order reaction)

[Intext 4.4] The conversions of molecules ‘X’ to ‘Y’ follows second order kinetics.
If concentrations of ‘X’ is increased three times how will it affect rate of formation
of ‘Y’?
(Ans.)X (reactants) → Y (product)
Case I
Rate = k [X]2 or kX2...(i)
Case II
X is increased three times, then X= 3X
Rate = k [3X]2 = k 9X2… (ii)
divided e.q. (II) by eq. (I)

6
𝑘 9 𝑋2
=9
𝑘 𝑋2
Rate of formation will become nine times.
[4.2] For the reaction: 2A + B→ A2B the rate = k [A][B]2 with
k =2.0 × 10-6 mol-2 L2s-1. Calculate the initial rate of the reaction.
when [A] = 0.1 mol L-1, [B] = 0.2 mol L-1
Calculate the rate of reaction. after [A] is reduced to 0.6 mol L-1
(Ans.) CASE-I
rate = k [A] [B] = 2.0 × 10 × [0.1 × 10 ] ×[0.2]2= 8.0x 10-9mol L-1s-1
2 -6 -6

CASE- II
when [A] reduced,
[A] reacted = initial̶ reduction = 0.1̶ 0.06 = 0.04mol L-1
Rate = k [A][B]2 = 2.0x10-6 x 0.06x(0.18)2 = 3.89X10-9Lmol-1s-1
[B] reacted= initial̶ reduction = 0.2̶ 0.02 = 0.18 mol L-1

[4.3] The decomposition of NH3 on platinum Surface is zero order regction.

What are the rates of production of N2 and H2, if k=2.5 x 10- 4 mol-1 Ls-1
(Ans.) 2NH3→N2 + 3H2
Rate (k) = 2.5 x 10- 4 mol-1 Ls-1(Zero Order)
1 𝑑[𝑁𝐻3 ] 𝑑[𝑁2 ] 3 𝑑[𝐻2 ]
Rate of reaction =− 2 = =1
𝑑𝑡 𝑑𝑡 𝑑𝑡
𝑑[𝑁2 ]
Rate of production = = 2.5 x 10 Ms-1 -4
𝑑𝑡
𝑑[𝐻2 ]
Rate of production of H2 = = 3.0 x 2.5x 10- 4Ms-1
𝑑𝑡
= 7.5 x 10- 4Ms-1
[4.4] The decomposition of dimethyl ether leads to the formation of CH 4, H2and CO and the
reaction rate is given by Rate = k [CH3OCH3] 3/2. The rate of reaction is followed by increase in
pressure in a closed vessel, so therate can also be expressed in terms of partial pressure of
dimethyl ether, i.e, Rate = k [p CH3OCH3] 3/2.
If the pressure is measured in bar and time in minutes, then what are the units of rate and
rate constants?
bar
(Ans.) Rate = 𝑚𝑖𝑛bar = barmin-1 ,

Rate = k (p CH3OCH3)3/2
barmin-1= k(bar)3/2
𝑏𝑎𝑟𝑚𝑖𝑛 −1
k= = 𝑏𝑎𝑟 −1/2 min-1
(𝑏𝑎𝑟)3/2

[4.5] Mention the factors that effect the rate of chemical reaction.
(Ans.) surface area, temp. of system, conc. of reactants, catalyst etc.

7
[4.6] A reaction is second order with respect to a reactant.
How is the rate of reaction affected if the concentration of the reactant is
(I) doubled
(II) reduced to half.
(Ans.) suppose ‘A’ and ‘B’ are reactants, conc. is one unit.
Rate = k [A] [B ] 1+1=2 (second order reaction)
(I) Concentration of the reactant is doubled.
[A] = 2, [B]=2
Rate = k [A]2[B]2, then 2+2=4 times increased.
(II) Concentration of the reactant is reduced to half.
[A] = 1/2, [B]= 1/2
Rate = k [A]1/2[B] 1/2, then 1/2 + 1/2 = 1/4 times reduced.
MOLECULARITY OF A REACTION:- The number of reacting species (molecules, atoms or ions)
which collide simultaneously to bring about a chemical reaction is called molecularity of a
reaction.
e.g. NH4NO2→N2 + 2H2O (Unimolecular reaction)
2HI →H2(g) + + I2(g) (Bimolecular reaction - because two molecules collide)
2NO(g)+ O2(g)→NO2(g) + O2(g) (Trimolecular reaction)
Type of reactions which take place through a sequence of two or more consecutive steps are
called complex reactions.
The detailed description of various steps by which reactants changes into the product is called
mechanism of the reaction.
The steps which contributeto the overall reaction are called elementary processes.
MECHANISM AND RATE LAW :- The rate of reaction which is determined by the slowest step in
the sequence. The slowest slep. is called rate determining step in the proposed mechanism.
e.g. Step I: NO2 + NO2→NO(g) + NO3(g) Slow step
step II : NO3(g) + CO(g)→CO2(g) + NO2(g) Fast step
--------------------------------------------------------------------------------------------------------------------------
NO2 + CO →CO2(g) + NO(g) Net reaction
--------------------------------------------------------------------------------------------------------------------------
Rate = k [NO2]2 because Istep is slow/rate determining step.

8
 MOLECULARITY ORDER
(1) It is the number of reacting species (1) It is the sum of powers of the
undergoing simultaneous collision in the concentration terms in the rate law
elementary or simple reaction. expression.
(2) It is applicable only for elementary
reaction. For complex reaction it has no (2) It is applicable to elementary as well as
meaning. complex reactions.
(3) It is theoretical concept. (3) It is determined experimentally.
(4) It has whole number value. (4) It has fractional values also.
(5) It can not be zero. (5) It can be zero.
(6) Molecurality of slowest step is same as (6) It is given by slowest step.
the order of reaction.

INTEGRATED RATE EXPRESSION:- It gives a relation bet ween directly measured experimental
quantities(e.g. conc. at different times). These are different for reactions of different orders.
ZERO ORDER REACTION:- When the amount of substance reacted is proportional to the time.
[𝑅𝑖𝑛𝑖𝑡𝑖𝑎𝑙 ] −[𝑅𝑓𝑖𝑛𝑎𝑙 ]
ko= 𝑡𝑖𝑚𝑒
𝑃𝑡.
2NH3(g) 1130 𝐾> N2(g) + 3H2(g)
Rate=k [NH3]0
Rate becomes constant and independent.
FIRST ORDER REACTION:- When the amount of substancereacted is proportional to the time.
2.303 [𝑅𝑖𝑛𝑖𝑡𝑖𝑎𝑙 ]
k= 𝑡𝑖𝑚𝑒 [𝑅𝑓𝑖𝑛𝑎𝑙 ]

e.g. all natural and artificial radioactive decay of unstable nuclei take place by first order
kinetics.
𝟐𝟐𝟔 𝟐𝟐𝟐 𝟒
𝟖𝟖𝑹𝒂 → 𝟖𝟔𝑹𝒂+ 𝟐𝑯𝒆

Rate = k[Ra]

9
EXPERIMENTAL DETERMINATION OF ORDER OF A REACTION:-
GRAPHICAL METHOD:- This method is used when there is only one reactant. A graph is plotted
between concentration and rate.

(a) If rate of reaction remains constant. It means the rate is independent of the conc. of
reactant.
Rate = k[R]0 = k Zero order
(b) If straight line is obtained (rate versus conc.). It means rate is directly proportional to the
conc of reactant. Rate = k[R] First order
(c) If straight line is obtained (rate v/s [R]2)
Rate = k [R]2 Second order.
(d) If straight line is obtained (rate v/s [R]3
Rate = k [R]3 Third order

[Intext 4.5] A first order reaction has a rate constant 1. 15 x 10-35s-1. How long will 5g. of this
reactant take to reduce to 3g?
[Ans]k = 1. 15 x 10-35s-1
[Rinitial] =5M
[Rfinal] =3M
time = ?
For First order reaction.
2.303 [𝑅𝑖𝑛𝑖𝑡𝑖𝑎𝑙 ] 2.303 [𝑅𝑖𝑛𝑖𝑡𝑖𝑎𝑙 ]
k= 𝑡𝑖𝑚𝑒 OR time =
[𝑅𝑓𝑖𝑛𝑎𝑙 ] 𝑘 [𝑅𝑓𝑖𝑛𝑎𝑙 ]

2.303 [5]
time =1.15×10−3 log [3]
2.303
time = log5 – log3 (log5= 0.6989, log3= 0.4771)
1.15×10−3
2.303
time =1.15×10−3 0.6989 – 0.4771
2.303
time =1.15×10−3 × 0.2218
time = 444 s
[Exp. 4.5, 4.6 also read]

10
(4. 16] The rate constant for the first order reaction is 60s -1. How much time will it to take to
reduce the concentration of the reactant to 1/16 th value ?
(Ans.) k = 60s-1
Let [Rinitial] = x
[Rfinal] = 1/16x
2.303 [𝑅𝑖𝑛𝑖𝑡𝑖𝑎𝑙 ] 2.303 [𝑅𝑖𝑛𝑖𝑡𝑖𝑎𝑙 ]
for first order reaction k= 𝑡𝑖𝑚𝑒 OR time =
[𝑅𝑓𝑖𝑛𝑎𝑙 ] 𝑘 [𝑅𝑓𝑖𝑛𝑎𝑙 ]

2.303 [𝑥]
time = log [1/16]
60
2.303
time = log 16 (log16= 1.204)
60
2.303
time = × 1.204
60
time = 0.046 s or 4.6 × 10-2 seconds
(4.18) show that time required for 99% completion is twice the time required for the
completion of 90% reaction.
(Ans.) Let [Rinitial] = x
𝑥 × 99
For 99% completion of reaction, [R] = x- = 0.01x
100
2.303 [𝑅𝑖𝑛𝑖𝑡𝑖𝑎𝑙 ]
Time(99%) = log
𝑘 [𝑅𝑓𝑖𝑛𝑎𝑙 ]
2.303 [𝑥]
Time(99%) = log [0.01 𝑥]
𝑘
2.303
Time(99%) = log 102 (log 102 or 2 log 10=2)
𝑘
2.303 × 2
Time(99%) = …. (i)
𝑘

𝑥 × 90
For 90% completion of reaction, [R] = = 0.1x
100
2.303 [𝑅𝑖𝑛𝑖𝑡𝑖𝑎𝑙 ]
Time(90%) = log
𝑘 [𝑅𝑓𝑖𝑛𝑎𝑙 ]
2.303 [𝑥]
Time(90%) = log [0.1 𝑥]
𝑘
2.303
Time(99%) = log 101 (log 101or 1 log 10=1)
𝑘
2.303 × 1
Time(99%) = …. (ii)
𝑘
Dividing e.q. (i) by e.q. (ii)
𝑡(99%) 2.303 × 2 2.303 × 1
= ÷
𝑡(90%) 𝑘 𝑘
t99% = 2× t90%
(4.24) Consider a certain reaction A → Products with k = 2.0 × 𝟏𝟎−𝟐 𝒔−𝟏 .
Calculate the concentration of A remaining after 100s if theinitial concentration of A is 1.0
𝒎𝒐𝒍𝑳−𝟏 .
(Ans)k = 2.0 × 10−2 𝑠 −1

11
Let [Ainitial] = 1.0 × 𝑚𝑜𝑙𝐿−1
[Afinal] = ?
t2 = 100 s
2.303 [𝑅𝑖𝑛𝑖𝑡𝑖𝑎𝑙 ]
for first order reaction k= 𝑡𝑖𝑚𝑒 log [𝑅𝑓𝑖𝑛𝑎𝑙 ]

2.303 [1]
2.0 × 10−2 = log [𝐴]
100

[1] 2.0 × 10−2 × 100

log [𝐴] = = 0.868
2.303
[1]
[𝐴]
= antilog(0.868)
[1]
[𝐴]
= 7.379
1
[A] = = 0.135 M
7.379

HALF LIFE PERIOD METHOD/ HALF LIFE PERIOD OF A REACTION:-

the time during which the conc. of a reactant is reduced to half of its initial concentration.
2.303 [𝑅 ]
t1/2= log [𝑅 𝑖𝑛𝑖𝑡𝑖𝑎𝑙
𝑘 ]/2
𝑓𝑖𝑛𝑎𝑙
2.303 1
t1/2 = log 1/2
𝑘
2.303
t1/2 = log 2 (log2= 0.3010)
𝑘
2.303 ×0.3010
t1/2 = 𝑘
𝟎.𝟔𝟗𝟑
t1/2 = 𝒌
[Intext 4.6] Time required to decompose SO2Cl2 to half of its initial amount is 60 minutes. If
the decomposition is a first order reaction. Calculate the rate constant of the reaction.
0.693 0.693 0.693
(Ans.) k= 𝑡 (ℎ𝑎𝑙𝑓)= 60 𝑚𝑖𝑛 = = 1.925 × 𝟏𝟎−𝟒 𝒔−𝟏
60 × 60 𝑠𝑒𝑐.
(4.13] Calculate the half-life period of a first order reaction wherethe specific rate constant is:
(a) 𝟐𝟎𝟎𝒔−𝟏
(b) 𝟐𝒎𝒊𝒏−𝟏
(c) 𝟒𝒚𝒆𝒂𝒓−𝟏
0.693 0.693
[Ans.] (a) t1/2 = = = 3.465 × 𝟏𝟎−𝟑 sec.
𝑘 200
0.693 0.693
(b) t1/2 = = = 3.465 × 𝟏𝟎−𝟏 min.
𝑘 2
0.693 0.693
(c) t1/2 = = = 1.732 × 𝟏𝟎−𝟏 year
𝑘 4

12
[4.14] The half-life period for radioactive decay of 14C is 5730 year. An archaeological artefact
contained wood had only 80% the 14C found in a living tree. Estimate the age of the sample.
(Ans.) t1/2 = 5730 year
0.693 0.693
t1/2 = or k = 𝑡(ℎ𝑎𝑙𝑓)
𝑘
0.693
= 5730 𝑦𝑒𝑎𝑟 = 1.209 × 𝟏𝟎−𝟒 𝒚𝒆𝒂𝒓−𝟏
[Rinitial] = 100
[Rfinal] = 80
2.303 [𝑅𝑖𝑛𝑖𝑡𝑖𝑎𝑙 ]
time =1.209 × 10−4 log [𝑅𝑓𝑖𝑛𝑎𝑙 ]
2.303 [100]
time =1.209 × 10−4 log [80]
2.303
time = 2log10 ─ log80 ( log 80 = 1.9030)
1.209 × 10−4
2.303
time =1.209 × 10−4 × 2 ─ 1.9030
2.303 ×0.0969
time = 1.209 × 10−4
time = 1846 year
[4.19] A first order reaction takes 40 minutes for 30% decomposition is calculate 𝒕𝟏/𝟐 .
(Ans.) Let initial conc. = x
conc. after 40 minutes = x ̶ 30% of x = 0.70X
2.303 [𝑅𝑖𝑛𝑖𝑡𝑖𝑎𝑙 ]
k= log
𝑡 [𝑅𝑓𝑖𝑛𝑎𝑙 ]
2.303 𝑥
k= log 0.70 𝑥
𝑡
2.303 100
k= log
40 70
2.303
k= × (2log10 ̶ log 70)
40
2.303
k= × (2 ̶ 1.8451 = 0.1549)
40
2.303
k= × 0.1549
40
k = 8.92 min-1
0.693 0.693
𝒕𝟏/𝟐 = = 8.92 ×10 −3 = 77.7 min
𝑘

[4.25] Sucrose decomposes in acid solution into glucose and fructose according to the first
order rate law, with t1/2 = 3.00 hours.
What fraction of sample of sucrose remains after 8 hours?
0.693 0.693
(Ans.)t1/2 = = = 0.231𝒉𝒓−𝟏
𝑘 3.0
Let initial conc. of sucrose = 1M
conc. after 8 hrs = 1 ̶ x

13
 2.303 1
k= log 1
𝑡 ̶𝑥
1 0.231 × 8
log 1 = = 0.824
̶𝑥 2.303
1
log 1 = antilog(0.824)
̶𝑥
1
log 1 = 6.345
̶𝑥
1 = 6.345 ̶ 6.345x
1 ̶ 6.345 = ̶ 6.345x
5.345 = 6.345x

5.345
x= = 0.842
6.345
conc. of sucrose left after 8 hours = 1 ̶ 0.842
= 0.158M
[4.17] During nuclear explosion, one of the product is 90Sr with half-life of 28.1 years. If 1µg of
90
Sr was absorbed in the bones of a newly born baby instead of calcium.
How much of it will remain after 10 years and 60 years if it is not lost metabolically?
0.693 0.693
[Ans.]t1/2 = = = 0.0247 𝑦𝑒𝑎𝑟 −1
𝑘 28.1
[Rinitial] of 90Sr = 1 µg
[Rfinal] after 10 years of 90Sr = x µg
2.303 [𝑅𝑖𝑛𝑖𝑡𝑖𝑎𝑙 ]
time =1.209 × 10−4 log [𝑅𝑓𝑖𝑛𝑎𝑙 ]
[𝑅𝑖𝑛𝑖𝑡𝑖𝑎𝑙 ] 𝑡 ×𝑘
log = 2.303
[𝑅𝑓𝑖𝑛𝑎𝑙 ]
1 10 ×0.0247
log =
𝑥 2.303
1
log = 0. 1072
𝑥
1
log = antilog (0.1072) antilog (0.1072) = 1.280
𝑥
1
log = 1.280
𝑥
1
x= = 0.782 µg
1.280
Conc. of 90Sr after 10 years = 0.782 µg
Let conc. of 90Srafter 60 years = yµg
2.303 [𝑅𝑖𝑛𝑖𝑡𝑖𝑎𝑙 ]
time =1.209 × 10−4 log [𝑅𝑓𝑖𝑛𝑎𝑙 ]
[𝑅𝑖𝑛𝑖𝑡𝑖𝑎𝑙 ] 𝑡 ×𝑘
log = 2.303
[𝑅𝑓𝑖𝑛𝑎𝑙 ]
1 60 ×0.0247
log 𝑦 = 2.303
1
log 𝑦 = 0.6435
1
log = antilog (0.6435) antilog (0.6435) = 4.40
𝑦

14
1
= 4.40
𝑦
1
x= = 0.228 µg
4.40
Conc. of 90Sr after 60 years = 0.228 µg
PSEUDO CHEMICAL REACTIONS :- Reactions which appear to be higher order but actually
follow lower order kinetics.
hydrolysis of cane sugar/inversion of cane sugar.
C12H22O11 + H2O → C6H12O6 + C6H12O6
(sugar) (excess) (Glucose) (Fructose)
during the reaction, water is present in large quantity that itsconcentration remains practically
unchanged. In this case molecularity is two while order is one.
Rate = k [C12H22O11]
[4.8] In a pseudo first order hydrolysis of ester in water the is following results were obtained
(i) Calculate the average rate of reaction between the time interval 30 to 60 seconds.
t/s 0 30 60 90
[Ester]/molL-1s-1 0.55 0.31 0.17 0.085

(ii) Calculate the pseudo first order rate constant for the hydrolysis of ester.
(Ans.)
[4.9] A reaction is first order in A and second order in B.
(i) Write the differential rate equation.
(Ans.) Rate = k [A][B]2
(ii) How is the rate affected on increasing the concentration ofB three times.
(Ans.) Rate = k [3B]2, increase 9 times.
(iii) How is the rate affected when the concentrations of both A and B are doubled.
(Ans.) Rate= k [2A] [2B]2, 4+2 = 6 rate becomes 6 times:
----------------

15