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Chemical Kinetics: Recap of Early Classes
Chemical Kinetics: Recap of Early Classes
CHAPTER
4
KINETICS
Recap of Early Classes
Chemical Kinetics helps us to understand how chemical reactions occur. In this chapter we
will study the rate of chemical reaction, mechanism of the reaction and factors controlling the rate
of reaction.
1.0 INTRODUCTION
In the thermodynamics, we have studied whether a reaction will take place or not and if it does then upto what
extent. In this chapter (chemical kinetics) we will study about how fast a chemical reaction takes place and what
are the different factors affecting this rate of chemical reaction. How to optimise the conditions as to maximise
the output in optimum time. The last part of chapter will be dealing with the mechanism of a chemical reaction
and catalysis.
The rate of change of concentration with time of different chemical species taking part in a chemical reaction is
known as rate of reaction of that species.
c mol / lit.
Rate = = = mol lit–1 time–1 = mol dm–3 time–1
t sec
Rate is always defined in such a manner so that it is always a positive quantity.
For a reaction R P
3.1 Average rate
SL AL
[R]0
c1 rav = =
t (t2– t1)
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c2 –d[R]
rinst = = – slope
dt
t1 t2 t time
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d[H 2 ]
Rate of decomposition of H2 = -
dt
d[NH 3 ]
Rate of formation of NH3 =
dt
These rates are not all equal. Therefore by convention the rate of a reaction is defined as
d[N 2 ] 1 d[H 2 ] 1 d[NH 3 ]
Rate of reaction = - = - =
dt 3 dt 2 dt
Note : Rate of reaction value is dependent on the stoichiometric coefficients used in the reaction while rate of
any species will be a fixed value under given conditions.
Illustration 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
103 × [R]/mol L–1 160 80 40 10 2.5
Solution. We can determine the difference in concentration over different intervals of time and thus determine
the rate by dividing D[R] by Dt.
Illustration 2. For each reaction below, express the rates of change of [product] and [reactant] in the correct
relationship to each other.
(a) 2O3(g) ® 3O2(g) (b) 2HOF(g) ® 2HF(g) + O2(g)
1 d[O 3 ] 1 d[O 2 ] 1 d[HOF] 1 d[HF] d[O 2 ]
Solution. (a) – =+ (b) – =+ =+
2 dt 3 dt 2 dt 2 dt dt
Illustration 3. In a catalytic experiment involving the Haber's process, N2 + 3H2 ® 2NH3, the rate of
reaction was measured as rate = = 2 x 10-4 M.s-1. If there were no side reactions, express
the rate of reaction in terms of (a) N2 (b) H2?
d[N2 ] -1 d[H2 ] 1 d[NH3 ]
Solution. Rate of Reaction = – = =+
dt 3 dt 2 dt
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d[N2 ] d[H2 ]
(a) 2 × 10–4 = – (b) 2 × 10-4 × 3 = – = 6 × 10-4 MS-1.
dt dt
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Chemical Kinetics
(a) Effect of concentration : We know 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.
(b) Effect of temperature : Will be discussed later.
(f) Effect of dielectric constant of the medium : More is the dielectric constant of the medium greater
will be the rate of ionic reactions.
(i) Effect of electrical & Magnetic field : Electric and magnetic fields are rate determining factors if a
reaction involves polar species.
The representation of rate of reaction in terms of the concentration of the reactants is called the rate law.
It can only be established by experiments.
Generally rate law expressions are not simple and these may differ for the same reaction on conditions under
which the reaction is being carried out.
But for large number of reactions starting with pure reactants we can obtain simple rate laws. For these reactions:
Rate µ (conc.)order
Rate = K (conc.)order This is the differential rate equation or rate expression.
Where K = Rate constant = specific reaction rate = rate of reaction when concentration is unity
unit of K = (conc)1– order time–1
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Note : Order of a reaction can be ‘zero’ or any whole number, it can be a fractional number and it can even be
negative with respect to a particular reactant. But overall order is not found to be negative for any reaction till
observed.
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Examples showing different values of order of reactions :
Reaction Rate law Order
The reaction (ii) does not take place in one single step. It is almost impossible for all the 12 molecules of the
reactants to be in a state of encounter simultaneously. Such a reaction is called complex reaction and takes
places in a sequence of a number of elementary reactions. For an elementary reaction the sum of stoichiometric
coefficients = order of the reactions. But for complex reactions order is to be experimentally calculated.
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.
k
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3. It is derived from RDS in the mechanism of reaction. 3. It is derived from rate expression.
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Chemical Kinetics
Illustration 4. In the first step of the Ostwald process for synthesis of nitric acid, ammonia is converted into nitric
oxide by the high-temperature reaction :
4NH3 (g) + 5O2(g) 4NO(g) + 6H2O(g)
(a) How is the rate of consumption of O2 related to the rate of consumption of NH3 ?
(b) How are the rates of formation of NO and H2O related to the rate of consumption of NH3 ?
d[O 2 ] 5 d[NH 3 ] d[NO] d[NH 3 ] d[H 2O] 3 d[NH 3 ]
Solution (a) – =– (b) =– and =–
dt 4 dt dt dt dt 2 dt
4NH3 (g) + 5O2 (g) 4NO (g) + 6H2O (g)
d[O 2 ] 5 d[NH 3 ]
– =–
dt 4 dt
d[O 2 ]
= 36 gram/ min = 1.125 mole/min
dt
Illustration 6. For the reactions of I, II and III order, k1 = k2 = k3 when concentrations are expressed in mol litre 1.
What will be the relation in k'1, k'2, k'3, if concentrations are expressed in mol/mL?
Solution k'1 = k'2 × 10–3 = k'3 × 10–6
r = k [A]n k = r. [A]–n Assume r = x mole–1 sec–1
k1 = sec –1
k'1 = sec–1
k2 = mole–1 Lit sec–1 k'2 = 103 x mole–1 ml sec–1
k3 = mole lit sec
–2 2 –1
k'3 = 106 x mole–2 ml–2 sec–1
Value of k'1 = [Value of k'2] × 10 = [Value of k'3] × 10–6
–3
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Illustration 7. The following data are for the reaction A + B products:
conc. A conc. B Initial Rate
(M) (M) (mol L 1 s 1)
0.1 0.1 4.0 x 10 4
0.2 0.2 1.6 x 10 3
0.5 0.1 2.0 x 10 3
0.5 0.5 1.0 x 10 2
(i) What is the order with respect to A and B for the reaction?
(ii) Calculate the rate constant.
(iii) Determine the reaction rate when the concentrations of A and B are 0.20 M and 0.35 M,
respectively.
Ans. (i) rate = [A] [B] (ii) k = 4 x 10 2M 1s 1 (iii) rate = 2.8 x 10 3M·s 1
x x
r1 a1 4 10 –4 0.1
Solution. (i) 0 = K [A]x [B]Y r3 = =
a3 20 10 –4 0.5
x Y Y
1 1 r3 b3 2 10–3 0.1
= = x=1 r4 = =
5 5 b4 10 10 –3 0.3
Y
1 1
= = y=1
5 5
(i) Rate = K [A] [B]
(ii) 4 × 10–4 = K [0.1] [0.1] k = 4 × 10–2 n–1 sec–1
(iii) r = 4 × 10–2 (0.2) (0.35) = 2.8 × 10–3
2. For the reaction N2 + 3H2 2NH3 the rate of change of concentration for hydrogen is – 0.3 × 10 –4 Ms–1.
The rate of change of concentration of ammonia is :
(A) – 0.2 × 10–4 (B) 0.2 × 10–4 (C) 0.1 × 10–4 (D) 0.3 × 10–4
3. If the concentration of the reactants in the elementary reaction 2A + B C + D is increased by three folds, the
rate of the reaction will be increased by-
(A) 27 times (B) 9 times (C) 64 times (D) 01 times
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4. The rate of change in concentration of C in the reaction 2A + B 2C + 3D was reported as 1.0 mol litre–1
sec . Calculate the reaction rate :
–1
(A) 0.05 mole litre–1 sec–1 (B) 0.01 mol litre–1 sec–1
(C) 0.5 mol litre–1 sec–1 (D) None of these
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Chemical Kinetics
7. For the reaction, 2A + B ® Products, the following initial rates were obtained at various initial concentrations
[A] [B] Rate (mol L–1 sec–1)
0.1 M 0.2 M 0.46
0.2 M 0.2 M 1.84
0.2 M 0.1 M 0.92
The rate law for the reaction is :
(A) Rate = k [A]2 [B]0 (B) Rate = k [A] [B] (C) Rate = k [A]2 [B] (D) Rate = k [A] [B]2
8. The following kinetic data are provided for a reaction between A and B :
Concentration of A(M) Concentration of B(M) Rate of reaction (M min–1)
0.50 0.02 1.15 × 10–4
0.50 0.04 2.30 × 10–4
0.01 1.00 2.30 × 10–6
0.02 1.00 0.92 × 10–5
Then value of the rate constant for the above reaction is equal to :
(A) 1.15 × 10–4 dm3/mol min (B) 2.30 × 10–4 dm6/mol2 min
–2 6
(C) 2.30 × 10 dm /mol min 2 (D) 1.15 × 10–2 dm3/mol min
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Unit of K is same as that of Rate = mol lit–1 sec–1.
C0
Time for completion =
k
C0 C0 C0
t1/2 (half life period) at t1/2 , Ct = , so kt1/2 = t1/2 =
2 2 2k
t1/2 C0
Interval formula :
2.303 C 2.303 C
k= log 0 Ct = C0 e
–kt
k= log 1
t Ct (t2–t1) C2
Graphical Representation
2.303 2.303
t= log Ct + log C0
k R
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Chemical Kinetics
First order growth reaction
For bacteria multiplication or virus growth use following concept
Consider a growth reaction
Time Population (or colony)
0 a
t (a + x)
dx dx
= k (a + x) or = kdt
dt (a x)
on integration
loge (a + x) = kt + C at t=0;x=0 C = loge a
a 2.303 a
kt = – loge =– log10 (a x)
(a x) t
2.303 a+ x
k= log10
t a
Generation time :
At t = generation time , x = a
0.693
t=
K
Examples of 1st order reactions :
(i) Decomposition of azoisopropane
CH 3 CH3
CH – N = N – CH (g) N2(g) + C6H14 (g)
CH3 CH3
(ii) (g)
Conversion of N–chloro acetanilide into p–chloroacetanilide
•• HCl
Cl – N – C – CH3 H — N – C – CH3
||
O O
Cl
1
(iii) H2O2 H2O + O (g)
2 2
(iv) NH4 NO2 2H2O + N2 (g)
(v) Radioactive decay
All radioactive decays are always first order kinetics.
226 222
Ra Rn + 2He4
88 86
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Illustration 8. The rate of a certain reaction depends on concentration according to the equation:
dC K 1C
.
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
Solution. (a) = 1 K C = 1
dt 2
K2
C
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1
if C is very-very high then being small may be neglected.
C
dC K1
= constant, i.e., zero order reaction.
dt K2
(b) If C is very-very low 1 + K2C K
dC K 1C K1
= × concentration
dt K K
i.e., I order reaction.
t 0.75
Illustration 9. Calculate t for a 1st order reaction :
0.50
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Chemical Kinetics
Illustration 11. Hydrolysis of methyl acetate in aqueous solution has been studied by titrating the liberated
acetic acid against sodium hydroxide. The concentration of the ester at different times is given
below :
t/min 0 30 60 90
c/M 0.8500 0.8004 0.7538 0.7096.
Show that it follows a pseudo first order reaction as the concentration of H2O remains nearly
constant (55.5 M) during the course of the reaction. What is the value of k in the equation?
rate = k [CH3COOCH3] [H2O]
Solution. For pseudo first order reaction, the reaction should be first order with respect to the ester when
[H2O] = constant. From the above data we note
ln (c 0 / c )
t c k[H 2O] = min–1
t
0 0.8500 –
30 0.8004 2.004 × 10 –3
60 0.7538 2.002 × 10 –3
90 0.7096 2.005 × 10 –3
It can be seen that k [H2O] is constant and equal to 2.004 × 10 –3 min–1 and hence it is pseudo
first order reaction. We can now determine k from
k [H2O] = 2.004 × 10–3 min–1
k [55.5 M] = 2.004 × 10–3 min–1
k = 3.614 × 10–5 M –1 min–1
It has the units of a second order reaction.
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Illustration 12. Compounds A and B react with a common reagent with first order kinetics in both cases. If 99% of
A must react before 1% of B has reacted. What is the minimum ratio for their respective rate
2
constants ? (Given 2 - log 99 = 458)
Ans. 458
Solution. The fraction of A and B remaining at any time t, are
[A]t
(fA)t = [ A ]
0
[B] t
and (fB)t = [B]
0
\ ln (fA)t = – kA t
and ln (fB)t = – kB t
kA ln ( f A ) t ln (0.01)
\ kB = ln ( fB ) t = ln (0.99) = 458.
Illustration 13. Surface catalysed reactions that are inhibited by the products obey the rate equation (in some cases)
dx K (a - x )
= where a is the initial concentration of the reactant and K and b are constants.
dt 1 + bx
Integrate this equation. Derive an expression for t1/2 . x is the concentration of products at any time
t and the reaction is
A ¾¾® B.
dx (1 + bx )
Solution. (a - x ) = Kdt
[1 - b (a - x ) + ab]
dx (a - x )
= Kdt
1 + ab
ò dx (a - x) - ò dx × b = K ò dt
– (1 + ab) ln (a – x) – bx = Kt – (1 + ab) ln a
a
Kt = (1 + ab) ln (a - x ) – bx
a
at t = t1/2 x=
2
a b×a ba
K1/2 = (1 + ab) ln - = (1 + ab) ln 2 – = ln 2 + ab ln 2 – ba × 0.5
a 2 2
a-
2
l n 2 + ab ( l n 2 - 0 . 5 )
t1/2 = Ans.
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Illustration 14. A 1mL sample of a bacterial culture at 370C is taken, and diluted to 10 L. A 1mL sample of the
diluted culture is spread on a culture plate. Ten minutes later, another 1mL sample taken from the
original culture diluted and spread in the same way. The two plates are incubated for 24 hours. The
first sample exhibits 48 colonies of bacteria, the second 72 colonies. If we assume that each colony
originates with a single bacterium, what is the generation time (time required for doubling the
population).
Ans. 17min. (approx.)
1 æ a + x1 ö
Solution. t1 = ln ç ÷
k è a ø
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Chemical Kinetics
1 æ a + x2 ö
t2 = ln ç ÷
k è a ø
1 æç a + x 2 ö÷
(t2 – t1) = ln ç ÷
k è a + x1 ø
1 æ a + x2 ö
k = t – t ln çç a + x ÷÷
2 1 è 1ø
1 æ 72 ö
k= ln ç ÷
10 è 48 ø
1 æ3ö
k= ln ç ÷
10 è 2 ø
æ ln 3 – ln 2 ö
k= ç 10
÷
è ø
ln 2 æ ln 3 – ln 2 ö
ç ÷
( t1/ 2 ) = è 10 ø
0.30 0.18
( t1/ 2 ) = 10
30 ´ 10
t1/2 = = 17 minutes (Approx.)
18
1
3. The half life period of a chemical reaction is given by : t 1 µ
2
a n-1
The order of the reaction is :
(A) n (B) n – 1 (C) n + 1 (D) None of these
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4. In a second order reaction 20% of a substance is dissociated in 40 minutes. The time taken by the 80% of its
dissociation is
(A) 160 minutes (B) 640 minutes (C) 200 minute (D) 320 minute
5. The half life period of a first order reaction is 100 seconds. Its rate constant is :
(A) 0.693 sec–1 (B) 6.93 × 10–3 sec–1 (C) 6.93 × 10–2 sec–1 (D) None of these
6. 75% of a first order reaction was completed in 32 minutes. When was 50% of the reaction completed.
(A) 24 minutes (B) 8 minutes (C) 16 minutes (D) 4 minutes
7. The half life period of a first order reaction is 15 minute. How much reaction will be completed in 30 min.
(A) 75% (B) 80% (C) 95% (D) 100%
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8. 99% at a first order reaction was completed in 32 min. When will 99.9% of the reaction complete.
(A) 48 min (B) 46 min (C) 50 min (D) 45 min
9. t0.5 = constant, confirms the first order of the reaction as one a 2 t0.5 = constant confirms that the reaction is of
(A) Zero order (B) First order (C) Second order (D) Third order
a
r01 [A 0 ]1
r02 [A 0 ]2
t1 / 2 1
n 1
(R 0' )2
n 1
t1/' 2 2
(R 0 )1
Illustration 15. The rate of decomposition of N2O5 in CCl4 solution has been studied at 318 K and the following
results have been obtained :
t/min 0 135 342 683 1693
c/M 2.08 1.91 1.67 1.35 0.57
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Find the order of the reaction and calculate its rate constant. What is the half-life period?
Solution. It can be shown that these data will not satisfy the integrated rate law of zero order. We now try
ln (c 0 / c )
integrated first order equation i.e., k=
t
ln (c 0 / c )
t/min c/M k= min–1
t
0 2.08 6.32 × 10–4
135 1.91 6.30 × 10–4
339 1.68 6.32 × 10–4
683 1.35 6.32 × 10–4
1680 0.72 6.31 × 10–4
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Chemical Kinetics
It can be seen that the value of k is almost constant for all the experimental results and hence it is first order
reaction with k = 6.31 × 10–4 min–1 .
0.69
t1/2 = = 1.094 × 103 min–1
6.31 10 4 min 1
Graphical method : Alternatively, if we draw a graph between ln c against t, we obtain a straight line with slope
= – k.
Illustration 16. In the reduction of nitric gas with hydrogen, the reaction was found to be 50% complete in 210
seconds when the initial pressure of the mixture was 200 mm. In a second experiment the time of
half reaction was 140 seconds when the initial pressure was 300 mm. Calculate the total order of the
reaction.
1
Solution. For a nth order reaction (n 1), t1/2
c n0 1
n 1
210 300
= n=2
140 200
n 1 n 1
nP0 Pt
a p0 & a–x PA =
n 1
2.303 P0 (n 1)
k= log nP P
t 0 t
Final total pressure after infinite time = Pf = nP0
Formula is not applicable when n = 1, the value of n can be fractional also.
Do not remember the formula but derive it for each question.
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Illustration 18. The following data are obtained for the hydrolysis of benzene diazonium chloride.
C6H5N2Cl(aq) + H2O( ) C6H5OH(aq) + HCl(aq) + N2(g)
Time (minutes) 0 2 8 16 30 50
Pressures (P) of N2 0 1.6 6.2 11.2 15.5 24.4 34.0
at constant vol.
(arbitrary units)
Calculate the rate constant, assuming first order kinetics.
34 34 34 34 34
[ n = 0.0482, n = 0.2013, n = 0.3996, n = 0.6086, n = 1.2646]
32 .4 27 .8 22 .8 18.5 9.6
2 .303 P – Po
k= log Here PO = 0
t P – Pt
(i) By measuring the volume of product formed we can monitor the progress of reactions.
(ii) By titration method : By measuring the volume of titrating agent we can monitor amount of reactant
remaining or amount of product formed at any time. It is the titre value . Here the milliequivalent or
millimoles are calculated using valence factors.
Illustration 19. Study of a reaction whose progress is monitored by measuring the volume of a escaping gas.
NH4NO2 (s) 2H2O ( ) + N2 (g)
Solution. Let, Vt be the volume of N2 collected at time ‘t’
V = be the volume of N2, collected at the end of the reaction.
a V and x Vt
(a – x) V – Vt
2.303 V
k= log
t V Vt
Illustration 20. From the following data show that the decomposition of hydrogen peroxide in aqueous solution is a
first - order reaction. What is the value of the rate constant?
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Time in minutes 0 10 20 30 40
Volume V in mL 25 20 15.7 12.5 9.6
where V is the number of ml of potassium permagnate required to react with a definite volume of
hydrogen peroxide solution.
Solution. The equation for a first order reaction is 2H2O2 2H2O ( ) + O2 (g)
the volume of KMnO4 used, evidently corresponds to the undecomposed hydrogen peroxide.
Hence the volume of KMnO4 used, at zero time corresponds to the initial concentration a and the
volume used after time t, corresponds to (a – x) at that time. Inserting these values in the above
equation, we get
2 .303 25
When t = 10 min. k1 = log = 0.022318 min–1 = 0.000372 s–1
10 20 .0
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Chemical Kinetics
2 .303 25
when t = 20 min. k1 = log = 0.023265 min–1 = 0.000387 s–1
20 15.7
2 .303 25
when t = 30 min. k1 = log = 0.02311 min–1 = 0.000385 s–1
30 12.5
2 .303 25
when t = 40 min. k1 = log = 0.023932 min–1 = 0.0003983 s–1
40 9.6
The constancy of k, shows that the decomposition of H2O2 in aqueous solution is a first order
reaction. The average value of the rate constant is 0.0003879 s –1 .
HCl
The above reaction is first order reaction and its progress is monitored by iodometric titration in
which liberated iodine is titrated against a standard solution of Hypo using starch as indicator. Given
that in this reaction KI does not react with the product (p–chloro acetanilide).
Calculate the rate constant of the reaction. Given that volume of hypo consumed at t = 0 is V0 and
at time ‘t’, Vt
Solution. Let, V0 = volume of hypo consumed at t = 0
Similarly Vt = volume of hypo consumed at t = ‘t’
a V0 { K reacts with the reactant only}
a – x Vt
2.303 V0
k= log
t Vt
The progress of this reaction is monitored or determined by titrating the reaction mixture at different
time intervals against a standard solution of NaOH using phenolphthalein as indicator. Find out rate
constant of the reaction in terms of volume of NaOH consumed at t = 0, V 0 , at t = , V & at time
t, Vt .
Solution. Let,V0 = vol. of NaOH used at t = 0 [this is exclusively for HCl.]
Vt = vol. of NaOH used at ‘t’
V = vol. of NaOH used at t =
a V – V0
a – x V – Vt
x Vt – V0
V V0
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2 .303
a V – V0 ; k= log V Vt
t
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Illustration 23. Study of hydrolysis of sucrose progress of this reaction is monitored with the help of polarimeter
because a solution of sucrose is dextrorotatory and on hydrolysis, the mixture of glucose as fructose
obtained becomes laevorotatory. That’s why this reaction is also known as inversion of cane sugar.
H
C12H22O11 + H2O C6H12O6 + C6H12O6
excess glucose fructose
Sp. rotation +66.5º +52.7º –92.4º
Let the readings in the polarimeter are
t = 0 , 0 ; t = ‘t’, t and at t =
Then calculate rate constant ‘k’ in terms of these readings.
Solution. The principle of the experiment is that change in the rotation is directly proportional to the amount
of sugar hydrolysed.
a – 0; a–x – t
2 .303 0
k= log
t t
In early days the effect of temperature on reaction rate was expressed in terms of temperature coefficient
which was defined as the ratio of rate of reaction at two different temperature differing by 10ºC (usually these
temperatures were taken as 25ºC and 35ºC)
K t 10
T.C. = Kt 2 to 3 ( for most of the reactions)
Note. For some reactions temperature coefficient is also found to be less than unity. For example
2NO + O2 2NO2 rate of reaction decreases on increasing temperature.
k 40 º C
Illustration 24. For a reaction T.C. = 2, Calculate for this reaction.
k 25 º C
t 15 3
k2
Solution. ( T .C .) 10 (2) 10 ( 2) 2 8
k1
Note. But the method of temperature coefficient was not exact and to explain the effect of temperature
on reaction rate new theory was evolved
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Chemical Kinetics
Orientation barrier : Energy alone does not determine the effectiveness of the collision. The reacting molecules
must collide in proper direction to make collision effective. Following diagrams can explain importance of
suitable direction for collision.
A A
A A
A A
B B
B B B B
Reactants
Transition Product
state
(iii) Collision to be effective the colliding molecules must possess some certain minimum energy called threshold
energy of the reaction.
(iv) Reactant molecules having energy equal or greater than the threshold are called active molecules and
those having energy less than the threshold are called passive molecules.
(v) At a given temperature there exists a dynamic equilibrium between active and passive molecules. The
process of transformation from passive to active molecules being endothermic, increase of temperature
increases the number of active molecules and hence the reaction.
Passive molecules Active molecules, H = +ve
(vi) Concept of energy of activation (Ea)
• The extra amount of energy which the reactant molecules (having energy less than the threshold) must
acquire so that their mutual collision may lead to the breaking of bond(s) and hence the energy is known
as energy of activation of the reaction. It is denoted by the symbol E a. Thus,
Ea = Threshold energy – Actual average energy
Ea is expressed in kcals mole–1 or kJ mole–1.
• The essence of Arrhenius Theory of reaction rate is that there exists an energy barrier in the reaction path
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between reactant(s) and product(s) and for reaction to occur the reactant molecules must climb over the
top of the barrier which they do by collision. The existence of energy barrier and concept of Ea can be
understood from the following diagram.
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From the figure above it can be concluded that the minimum activation energy of any exothermic reaction will
be zero while minimum activation energy for any endothermic reaction will be equal to H.
Greater the height of energy barrier, greater will be the energy of activation and more slower will be the reaction
at a given temperature.
Rate of any chemical reaction = Collision frequency × fraction of the total number of effective collision
= Collision frequency × fraction of the total number of collision in which
K.E. of the colliding molecules equals to Ea or exceeds over it.
Collision frequency is the number of collisions per unit volume per unit time. It is denoted by the symbol Z. Z is
directly proportional to T . By 10ºC rise in temperature, so it is the fraction of the total number of effective
collision that increases markedly resulting into marked increase in the reaction rate.
From maxwellian distribution it is found that fraction of molecules having excess energy greater than threshold
energy lead to the formation of product.
Fraction of T2
molecule T1 T2 > T1
Ea
rate e Ea / RT
dependence of rate on temperature is due to dependence of k on temperature.
k e E a / RT
k Ae Ea / RT (Arrhenius equation)
A is pre exponential factor / frequency factor representing collisions taking place with proper orientation.
A and Ea are independent of temperature generally.
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Reversible Reactions
E af / RT
kf = Af e
E ab / RT
kb = Ab e
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Chemical Kinetics
Eaf / RT
kf Af e Af
(E af Eab ) / RT
Keq = k = Eab / RT = Ab e
b Ab e
H Af
n Keq = – + n A
RT b
Illustration 25. Explain on the basis of temprature coeff. of rate const. that equilibrium of endothermic reaction
shifts in forward direction on increasing temprature while equilibriums of exothermic shift back.
K eq1 H 1 1
n =
K eq 2 R T1 T2
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.
Catalyst are generally foreign substances but sometimes one of the product may act as a catalyst and such
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catalyst is called “auto catalyst” and the phenomenon is called auto catalysis.
Examples of catalysis
(a) Thermal decomposition of KCIO3 is found to be accelerated by the presence of MnO2. Here MnO2 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.
(b) In the permanganate titration of oxalic acid initially there is slow discharge of the colour of permanganate
solution but afterwards the discharge of the colour become faster. This is due to the formation of MnSO 4
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
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14.1 General characteristics of catalyst
AL
(i) A catalyst does not initiate the reaction. It simply fastens it.
(ii) Only a small amount of catalyst can catalyse the reaction.
(iii) 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 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.
Reaction Coordinate
Potential energy
Ea Ea
Reactants Reactants
Products Products
Illustration 26. The pyrolysis of an organic ester follows a first order process and its rate constant can be
42075
expressed as ln k = 78.09 –
T
where k is given in the min–1. Calculate the time required for 25 percent reaction to complete at
227°C.
42075
Solution. ln k = 78.09 – = – 6.06
500
6.06
log k = – = – 2.63 ; k = 2.344 × 10–3 min –1
2.303
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Chemical Kinetics
2.303 a 2.303
when x = 0.25 ; k = log 0.75 a t 1/4 = 3 log 1.333 = 123.06 min
t 1/ 4 2.344 10
Illustration 27. From the following data for the reaction between A and B.
–3 –1
[A] [B] Initial rate (mole dm min )
–3 –3
(mole dm ) (mole dm )
300 k 320 k
(i) 2.5 × 10
–4
3.0 × 10
–5
5.0 × 10
–4 2.0 × 10–3
–4 –5 –3
(ii) 5.0 × 10 6.0 × 10 4.0 × 10
–3 –5 –2
(iii) 1.0 × 10 6.0 × 10 1.6 × 10
Calculate the following
(i) The order w.r.t. A and w.r.t. B (ii) The rate constant at 300 K
(iii) The energy of activation (iv) The pre-exponential factor
[e –22.18 = 2.3283 × 10–10 , ln2 = 0.693]
Ans. (i) 2, 1 (ii) 2.67 × 108 mol–2 litre2 sec–1
(iii) 55.13 kJ mol–1 (iv) 1.147 × 1018 mol–2 litre2 sec–1
Solution. (i) r = K [A]x [B]Y
From (2 & 3) equation
x
5 10 – 4
x 2
4 10 –3 1 1
= = = x= 2
10 10– 4 16 10 – 3 2 2
From 1 & 2
x y x y
2.5 10 – 4 3 10 – 5 5 10–4 1 1 1
–4 –5 = –4 = = 23 y=1
5 10 6 10 40 10 2 2
5 10 –4 50 108
K300 = –8 –5 = K300 = 2.67 × 108 Mole–2 Lit2 sec–1
6.25 10 3 10 6.25 3
K2 Ea 1
–
1 2 10 –3
(iii) log K1 = 2.303 R T1 T2 K320 =
6.25 10 – 8 3 10 – 5
200 10 8
= = 10.67 × 10+8
6.25 3
Ea
K = A e– Ea = 55.13 kJ/mole
RT
55.32 103
2.67 × 108 = A e– = A e– 22.18
8.314 300
2.67 × 108 = A × 2.3283 × 10–10 ,
2.67 108
A= = 1.147 × 1018
2.3283 10–10
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3. The activation energies for forward and backward reactions are Ef and Eb respectively. If the reaction is
exothermic then :
(A) Ef > Eb (B) Ef < Eb
(C) Ef = Eb (D) There is no relation between Ef and Eb directly
1 1
4. The slope of the line for the graph of log k versus for the reaction, N2O5 2NO2 + O is – 5000. Calculate
T 2 2
the energy of activation of the reaction - (kJ K –1 mol—1)
(A) 95.7 (B) 9.57 (C) 957 (D) None
5. For a reaction, the rate constant is expressed as, k = A.e –40000/T . The energy of the activation is :
(A) 40000 cal (B) 88000 cal (C) 80000 cal (D) 8000 cal
6. A B KA = 1015 e–2000/T
C D KC = 1014 e–1000/T
Temperature TK at which (KA = KC) is :
(A) 1000 K (B) 2000 K (C) (2000 / 2.303) K (D) (1000 / 2.303) K
7. For the first order reaction A B + C, carried out at 27°C if 3.8 × 10–16 % of the reactant molecules exists
in the activated state, the Ea (activation energy) of the reaction is :
(A) 12 kJ/mol (B) 831.4 kJ/mol (C) 100 kJ/mol (D) 88.57 kJ/mol
AL
(i) These reaction take place in single step without formation of any intermediate
T.S.
P.E. Ep
Er
Reaction coordinates
(ii) 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
186
Chemical Kinetics
(i) Reaction which proceed in more than two steps. or having some mechanism. ( sequence of elementary
reaction in which any complex reaction procceds)
T.S.
E intermediate
Reaction coordinates
(ii) For complex reaction each step of mechanism will be having its own molecularity but molecularity of net
complex reaction will not be defined.
(iii) Order of complex reaction can be zero fractions whole no, even negative w.r.t. some species.
(iv) 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.
(v) Rate law of a reaction is always written in terms of conc. of reactant, products or catalysts but never in
terms of conc. of intermediates.
The mechanism of any complex reaction is always written in terms of elementary steps, so molecularity
of each of these steps will be defined but net molecularity of complex reaction has no meaning.
The mechanism of most of the reaction will be calculated or predicted by using mainly the following
approximations.
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 mechanism.
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Illustration 29. Calculate rate law
2O3 3O2
k1
O3 O2 + O (fast eq. step)
k2
(intermediate)
O + O3 k3 2O2 (slow)
Solution. From R.D.S., rate = k3 [O3] [ O]
According to equilibrium step.
k1 [O 2 ][O]
Keq. = =
k2 [O 3 ]
k 1 [O3 ]
[O] = k [O ]
2 2
k 1 [O3 ]
Rate = k3 [O3] [O] = k3 [O3] k [O ] .
2 2
k 1 k 3 [O 3 ] 2
Rate =
k 2 [O 2 ]
Steady state
Time
d [int ermediate ]
At steady state =0
dt
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O2 + O k2 O3
O3 + O k3 2O2
1 d[O 3 ] 1 d[O 2 ]
Solution. rate = =
2 dt 3 dt
188
Chemical Kinetics
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
k1[O 3 ]
[O] = k [O ] k [O ]
2 2 3 3
d[O 3 ] k 2 [O 2 ] k1[O 3 ] k1 k 3 [O 3 ]2
= – k1 [O3] + –
dt k 2 [O 2 ] k 3 [O 3 ] k 2 [O 2 ] k 3 [O 3 ]
k1k 2 [O 2 ] [O 3 ] – k1k 3 [O 3 ] 2
= – k1 [O3] +
k 2 [O 2 ] k 3 [O 3 ]
– 2k1 k 3 [O3 ] 2
=
k 2 [O 2 ] k 3 [O 3 ]
–1 d k1 k 3 [O 3 ] 2
[O3 ] =
2 dt k 2 [O 2 ] k 3 [O 3 ]
1 d
Rate = – [O3]
2 dt
k1 k 3 [O 3 ]2
So, Rate (r) =
k 2 [O 2 ] k 3 [O 3 ]
if 3rd step is RDS then k1>> k3
k2 >> k3
k1 k 3 [O 3 ]2
r=
k 2 [O 2 ] k 3 [O 3 ]
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d[H2NO 2 ]
Solution. = k1 [H+][HNO2] – k2 [H2NO2+] – k3 [H2 NO2+] [Br–] = 0
dt
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[H ]]HNO 2 ]
[H2NO2+] = k1
k2 k 3 [Br – ]
d d
rate = [C 6H5NH2 ] = [HNO 2 ]
dt dt
d
[C6H5NH2 ] = k [ONBr ] [C H NH ]
dt 4 6 5 2
d
[NOBr ] = – k4 [C6H5NH2][NOBr ] + k3 [Br–] [H2NO2+] = 0
dt
k 3 [Br – ][H2NO 2 ]
[NOBr] =
k 4 [C6H5NH2 ]
k 4 k 3 [Br – ][H2NO 2 ]
r = [C 6H5NH2 ]
k 4 [C 6H5NH2 ]
Illustration 32. Drive a rate law for the reaction H2 (para) H2 (ortho) with the help of following mechanism.
k1
Ans. Rate = k3 3/2
k 2 [H2 (para)]
k1
Rate = k3 3/2
k 2 [H2 (para)]
190
Chemical Kinetics
The reactant A follows two different paths to form B and C as shown below :
C
A
B
Conc.
d[A]
Rate = – = k1[A] + k2[A] = k[A] [As, (k1 + k2) = k]
dt
[A]0 [B] k1
ln [A] = (k1 + k2) t ; [C] k2
t
k1[A0 ] k 2[A 0 ] k 2t
[A] = [A0] e–kt; [B] = (1 e k1t
) ; [C] = k k (1 e )
k1 k 2 1 2
k1 k2
% yield of B = × 100 ; % yield of C = k k 2 × 100
k1 k2 1
(ii) Consecutive Reaction : Frequently a product of one reaction becomes a reactant in a subsequent
reaction. This is true in multistep reaction mechanisms. We shall consider only the simple case of two
consective irreversible first-order reactions : A B with rate constant k1, and B C with rate contant k2:
k k
A 1
B 2
C
where for simplicity we have assumed stoichiometric coefficients of unity. Since the reactions were assumed
to be first-order, Thus
d [B] d [B] d [B]
= + = k1[A] – k2[B]
dt dt 1 dt 2
We have
d [A ] d [B] d [C]
= – k1[A], = k1[A] – k2 [B], = k2[B]
dt dt dt
Let only A be present in the system at t = 0 :
[A]0 0, [B]0 = 0, [C]0 = 0
[A] = [A]0 e –k1t
d [B]
and solving = k1[A]0 e –k1t – k2[B] gives
dt
k 1[ A ] 0 k t k t
[B] = k e 1 e 2
2 k1
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To find [C], we use conservation of matter. The total number of moles present is constant with time, so
[A] + [B] + [C] = [A]0.
k2 k t k1 k t
Hence [C] = [A]0 k e 1 e 2
2 k1 k 2 k1
Figure shows plots [A], [B], and [C] for two values of k 2/k1.Note of maximum in the intermediate species [B].
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JEE-Chemistr y
Conc.
1 [A]
Conc.
1 [A] 0
2 0 2
[C]
[B]
0 0
0 0.5 1 1.5 0 2 4 6
k1 t k1 t
(a) (b)
d [ A] d[A] d [ A]
= + dt = – kf [A] + kb [C] = kb[C]0 + kb[A]0 – (kf + kb) [A]
dt dt f b
In the limit as t , the system reaches equilibrium, the concentration of each species is constant, and
d [ A] d [ A]
is 0. Let [A]eq be the equilibrium concentration of A. Setting = 0 and [A] = [A]eq , we get
dt dt
kb[C]0 + kb[A]0 = (kf + kb) [A]eq
d [ A]
Now = (kf + kb) [A]eq – [A]. Using the identity f (x + s) –1 dx = In (x + s) to integrate this equation,
dt
[ A ] [ A ]eq ( k f k b )t
we get In = (kf + kb)t or [A] – [A]eq = ([ A ]0 [ A ])e
[ A ]0 [ A] eq
A C
[A]/[A]0 kf/kb = 2
0.8
0.6
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0.4
[C]/[A]0
0.2
0
0 31 4 52
jt
1Concentrations versus time for the reversible first-order reaction A C with forward and reverse rate
constants kf and kb plotted for the case
kf/kb = 2. As t , [C]/[A] 2, which is the equilibrium constant for the reaction.
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Chemical Kinetics
Illustration 33. A follows parallel path, first order reaction giving B and C as
k1
B
5A
k2
2C
2.303 0.25
2 × 10–5 = log
t [A]t
[A]t = 0.1744 M
[A]decomposed = [A]0 – [A]t = 0.25 – 0.1744 = 0.0756 M
6
k2 2 5 10 2
Fraction of C formed = × [A]decomped × = 5 × 0.0756 × = 7.56 × 10–3 M
(k1 k 2 ) 5 2 10 5
(5 moles of A are used to give 2 moles of C)
5. For the reaction, A + B C + D. The variation of the concentration of the products is given by the curve :
Y
Z
Conc.
W
X
Time
7. A gaseous compound A reacts by three independent first order processes (as shown
in figure) with rate constant 2 × 10–3, 3 × 10–3 and 1.93 × 10–3 sec–1 for products B, C and D respectively.
If initially pure A was taken in a closed container with P = 8 atm, then the partial pressure of B (in atm) after
100 sec from start of experiment :
k1 B(g)
k2
A(g) C(g)
k3
D(g)
(A) 0.288 (B) 0.577 (C) 1.154 (D) none of these
18.0 RADIOACTIVITY
AL
The spontaneous emission of particles, electromagnetic radiation or both by unstable nuclei, is known as
radioactivity.
PROPERTIES OF , -PARTICLES AND -RAYS.
Properties Alpha beta Gamma
1. Nature Fast moving He Fast moving High energy
nuclei electrons
2. Representation 2
He4 or –1
e0 or –1 0
or 00
3. Charge 2 unit (+ve) 1 unit (–ve) no charge
4. Velocity 1/10 of light 33% to 90% of Same as light
light waves
5. Relative penetrating 1 or (0.01 mm of 100 or (0.1 cm 10000 or (8 cm lead
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Chemical Kinetics
Kinetics of nuclear distintegration
dN
Radioactive decay is a first order process. Hence = N or N = N0 e t
dt
where N = number of radioactive nuclei at any time t ;
N0= number of radioactive nuclei at t = 0 ;
= decay constant.
dN
Activity activity (A) = = N
dt
S.I. units :
Disintegration per second (symbol s 1 or dps). 1 dps = 1 Bq (Becquerel)
Other units:
1Ci (Curie) = 3.7 × 1010dps.
1 Rd (Rutherford) = 106 dps
Specific activity = dps / gm
Half life (t½) The time taken by half the nuclei (originally present) to decay. t ½ = 0.693/
1
Note : After n half lives have passed, activity is reduced to of its initial value.
2n
1 t1/ 2
Tavg = = = 1.44 t1/2
0.693
Application of Nuclear disintegration :
(i) Carbon dating (ii) Rock dating
210
Illustration 34. 84
Po decays with emission of -particle to 206
82
Pb with a half-life period of 138.4 days. If 1g of 210
84
Po
is placed in a sealed tube, how much helium will be accumulated in 69.2 days ? Express the answer
in cm3 at STP.
210
Solution. Po 206
84 82
Po + 24He
Amount of 21084
Po left after 69.2 days can be calculated by applying
N = N0 (1/2)n
69.2 1
n = t/t1/2 =
138.2 2
1/ 2
1
N=1× = 0.702 g
2
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18.1 Carbon Dating
AL
The cosmic ray generates neutrons in the atmosphere which bombards the nucleus of atmospheric nitrogen to
form radioactive 14C hence 14C in the atmosphere has been remaining constant over thousands of years. In living
materials, the ratio of 14C to 12C remains relatively constant. When the tissue in an animal or plant dies, assimilation
of radioactive 14C ceased to continue. Therefore, in the dead tissue the ratio of 14C to 12C would decrease depending
on the age of the tissue.
14
7
N + 10n 14
6
C + 11p
14 14
6
C 7
N + –10e
A sample of dead tissue is burnt to give carbon dioxide and the carbon dioxide is analysed for the ratio of 14C
to 12C. From this data, age of dead tissue (plant or animal) can be determined.
2.303×t1/2 A0
Age = log
0.693 A
n
1 t
A0 = Original activity A = Final activity. Also, N = N0 where n = t
2 1/ 2
It is based on the kinetics of radioactive decay. It is assumed that no lead was originally present in the sample
and whole of it came from uranium.
Initial no. of mole (N0) = [U] + [Pb]
Final no. of mole (N) = [U]
N0 [U] [Pb] [Pb] 2.303 N0
=1+ ; t= log
N [U] [U] N
Illustration 35. A sample of uranium mineral was found to contain 206Pb and 238U in the ratio of 0.008 : 1. Estimate
the age of the mineral (half-life of 238U is 4.51 × 109 years).
206
2.303 Pb
Solution. t= log 1 238
U
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206
2.303 Pb
t= t1/ 2 × log 1 238 Ratio by mass 206
Pb : 238
U = 0.008 : 1
0.693 U
0.008 1
Ratio by moles 206Pb : 238U = : = 0.0092
206 238
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Chemical Kinetics
AL
It is a nuclear reaction in which heavy nucleus splits into lighter nuclei of comparable masses with release of
large amount of energy by bombardment with suitable sub-atomic particles, i.e.
140 93 1
Ba + 36Kr + 30n
56
1
0
n + 235
92
U Xe144 + 38Sr 90 + 20n1
54
144 90 1
Cs + 37Rb + 20n
55
If the neutrons from each nuclear fission are absorbed by other 92U235 nuclei, these nuclei split and release even
more neutrons. Thus, a chain reaction can occur. A nuclear chain reaction is a self sustaining series of nuclear
fissions caused by the previous neutrons released from the previous nuclear reactions.
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JEE-Chemistr y
0 n1 235
92 U
1
56 Ba140 +0 1n 235
92 U 0 n 235
92 U
n 1 235
U
1
0n + 235
92 U
+01n 92 U235 0 92
It is a nuclear reaction in which two lighter nuclei are fused together to form a heavier nuclei. To achieve this,
colliding nuclei must posses enough kinetic energy to overcome the initial force of repulsion between the positively
charged core. At very high temperature of the order of 106 to 107 K, the nuclei may have the sufficient energy
to overcome the repulsive forces and fuse. Such reactions are therefore also known as thermonuclear reactions.
2
1H + 13H ¾¾® 42 He + 10 n + 17.8MeV 2
1H + 12H ¾¾® 42 He + 24.9 MeV
1
1H + 13H ¾¾® 42 He + 20.0 MeV 7 1
3 Li + 1H ¾¾® 42 He + 17.7 MeV
Radioactivity
1. A piece of wood from an archeological source shows a C-14 activity which is 60% of the activity found today.
Calculate the age of the sample ( t 1 for 14
6C = 5770 years) :
2
(A) 3515 years (B) 300 years (C) 4253 years (D) 4000 years
2. A radioactive isotope x with half life of 1.37 × 109 years decays to y which is stable. A sample of rock from
the moon was found to contain both the elements x and y in the ratio 1 : 7. What is the age of the rocks :
(A) 1.96 × 108 years (B) 3.85 × 109 years (C) 4.11 × 109 years (D) 3.06 × 109 years
a-b (a - b) b-a (a - b)
(A) a = , b=d+ -c (B) a = , b=d+ -c
4 2 4 2
b-a (a + b) b+a (a + b)
(C) a = , b=d+ +c (D) a = , b=d+ +c
4 2 4 2
4. What is the a-activity in disintegration per minute 1 g sample of 226Ra. (t1/2 = 1620 year)
(A) 1.08 × 106 events/min (B) 2.16 × 1012 events/min
6
(C) 1.28 × 10 events/min (D) 1.08 × 1010 events/min
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5. The half life of the nuclide Rn220 in 54.5 sec. What mass of radon is equivalent to 1 millicurie.
(A) 1.06 × 10–15 kg (B) 1.06 × 1015 kg (C) 2.06 × 1010 kg (D) 2.06 × 10–10 kg
210
6. 84Po decays with a to 206
82Pb with a half life of 138.4 days. If 1.0 g of Po
210
is placed in a closed tube, what
volume of helium will be accumulated in 69.2 days at STP.
(A) 22.4 ml (B) 11.2 ml (C) 31.2 ml (D) 48.2 ml
218
7. 84Po (t1/2 = 3.05 min) decay to 82Pb214 (t1/2 = 2.68 min) by a-emission, while Pb214 is a b-emitter. In an
experiment starting with 1 g atom of pure Po218, how much time would be required for the number of nuclei of
214
82Pb to reach maximum.
(A) 3.15 min (B) 4.12 min (C) 5.15 min (D) 5.30 min
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Chemical Kinetics
dx
=k
dt
2.303 a 0.693 0.693 1.382
First order reaction k1 = log 10 time–1 t 1= t 3 =2× =
t (a–x) 2
K1 4
k1 k1
2.303 b(a-x) 1 3
Second order reaction k 2= log Mole–1litre time–1 t1 t 3=
t(a-b) a(b-x) 2
k 2a 4
k 2a
dx
=k(a-x)2
dt
x×(2a-x) 3
Third order reaction k 3= Litre2mole–2time–1 t 1= --
t2a 2 (a-x)2 2
2k 3a 2
dx
=k(a-x)3
dt
Examples of reactions of 1st order and their formula for rate constants
2.303 V
(i) 2N2O5 4NO2 + O2 ; k = log V V
t t
where V = volume of O2 gas collected at infinite time
Vt = volume of O2 gas collected at time t
2.303 V
(ii) NH4NO2 2H2O + N2 ; k = log V V
t t
where V and Vt are volumes of N2 gas collected after infinity time and after time t respectively.
1 2.303 VD
(iii) H2O2 H2O + O2 ; k = log V
2 t t
where V0 and Vt are the volumes of KMnO4 solution used for titrating a definite volume of the
reaction mixture at t = 0 and at time t respectively.
2.303 V V0
k= log V Vt
t
where V0, Vt and V are the volume of NaOH solution used for titration mixture at zero time,
after time t and after infinity respectively.
H
(v) C12H22O11 + H2O C6H12O6 + C6H12O6
Glucose Fructose
2.303 (r0 r )
k= log (r r )
t t
where r0, rt and r are the polarimetric reading at zero time, after time t and after infinity respectively.
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k1
B
d[A]
A Rate = – [dt] = k1 [A] + k2 [A] = [k1 + k2] [A]
k2
C
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Chemical Kinetics
Illustration 2.
The reaction CO(g) + NO2(g) CO2 + NO is second order in NO2 and zero order in CO at temperatures less
than 500K.
(a) Write the rate expression for the reaction.
(b) How will the reaction rate change if the NO2 concentration is halved?
Solution.
d d
(a) [CO] = (NO2) = K [NO2]2 Order is zero w.r.t. CO but Conc will Still change
dt dt
(b) Rate of Rxn = K[NO2 ]2 of Conc of NO2 Half The Rate becomes One fourth
Illustration 5.
For a reaction A + 3B Product, Rate = {– d[A] / dt} = k [A] 2 [B] , the expression for the rate of reaction in
terms of change in the concentration of B; {– d[B] / dt} will be :
(A) k[A]2 [B] (B) k [A]2 [3B] (C) 3k [A2] [B] (D) (1/3) k [A2] [B]
Ans. [C]
Solution.
For the given reaction
d[ A ] 1 d[B] d[B]
= = K[A]2[B] Then = 3K[A]2[B]
dt 3 dt dt
Illustration 3.
For the reaction 2N2O5 (g) 4NO2 (g) + O2 (g) the concentration of NO2 increases
by 2.4× 10–2 Mol lit–1 in 6 seconds. Calculate the rate of appearance of NO2 and the rate of disappearance
of N2O5 -
(A) 4 × 10–3 mol lit –1 sec –1, 2 × 10–3 mol lit –1 sec –1
(B) 2 × 10–3 mol lit –1 sec –1, 4 × 10–3 mol lit –1 sec –1
(C) 3 × 10 –3 mol lit –1 sec –1, 3 × 10–3 mol lit –1 sec –1
(D) None of these
Ans. [A]
Solution.
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Nurture\Che\Unit-08\Chemical Kinetics
1 [N2O5 ] 1 [NO2 ]
Rate of reaction, – =
2 t 4 t
Since, NO2 is the product, therefore, its concentration when t = 0 is zero.
Rate of appearance of NO2 i.e.
2
[NO2 ] 2 . 4 10
= = 4 × 10–3 mol lit–1 sec–1
t 6
1 [NO2 ]
Thus, rate of reaction =
4 t
3
4 10
= mol lit –1 sec –1 = 1 × 10–3 mol lit –1 sec –1
4
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Illustration 4.
For the chemical reaction 3O2 — 2O3, the rate of formation of O3 is 0.04 mole lit–1 sec–1. Determine
the rate of disappearance of O2 -
(A) 0.04 mol lit –1 sec –1 (B) 0.08 mol lit –1 sec –1
(C) 0.10 mol lit –1 sec –1 (D) 0.06 mol lit –1 sec –1
Ans. [D]
Solution.
d [O3 ]
= 0.04 mol lit–1 sec —1
dt
We know, Rate
1 d [O2 ] 1 d [O3 ]
= – =
3 dt 2 dt
d [O2 ] 3 d [O3 ] 3
– = × = × 0.04 = 0.06 mol lit–1 sec–1.
dt 2 dt 2
Illustration 5.
For the reaction
2N2O5(g) — 4NO2 (g) + O2(g), the concentration of NO2 increases by 2.4 × 10–2 Mol lit.–1 in 6 second.
What will be the rate of appearance of NO2 and the rate of disappearance of N 2O5
(A) 2 × 10 –3 mol lit. –1 sec –1 , 4 × 10–3 mol lit.–1 sec –1
(B) 4 × 10 –3 mol lit. –1 sec –1 , 2 × 10–3 mol lit.–1 sec –1
(C) 2 × 10 –3 mol lit. –1 sec –1 , 2 × 10–3 mol lit.–1 sec –1
(D) None of these
Ans. [B]
Solution.
1 [N2O5 ] 1 [NO2 ]
Rate of reaction = – =
2 t 4 t
Since NO2 is the product, therefore, its concentration when t = 0 is zero.
Rate of appearance of NO2 i.e.
[NO2 ] 2 .4 10 2
=
t 6
= 4 × 10–3 mol lit.–1 sec–1
1 [NO2 ]
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4 10 3
= mol lit.–1 sec –1
4
= 1 × 10–3 mol lit –1 sec –1.
[N2O5 ]
Rate of disappearance of N2O5 i.e. = 2 × Rate of reaction
t
= 2 × 1 × 10–3 mol lit. –1 sec –1
= 2 × 10–3 mol lit.–1 sec–1.
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Chemical Kinetics
Illustration 6.
Following reaction was carried out at 300 K. 2SO2(g) + O2 (g) —— 2SO3(g)
How is the rate of formation of SO3 related to the rate of disappearance of O2
[O 2 ] 1 [SO3 ] [O 2 ] [SO3 ]
(A) – = + (B) – =
t 2 t t t
[O 2 ] 1 [SO3 ]
(C)– = – (D) None of these
t 2 t
Ans. [A]
Solution.
Rate of reaction
1 [SO2 ] [O 2 ] 1 [SO3 ]
= – = – = +
2 t t 2 t
Therefore, rate of disappearance of O2 is related to rate of formation of SO3 as -
[O 2 ] 1 [SO3 ]
– = +
t 2 t
Illustration 7.
For the reaction 2NO (g) + H2(g) — N2O (g) + H2O (g), at 900 K. following data are observed.
=
0.005 k [0.075]m [0.4]n
or 4 = [2]m m = 2
Divide equation (i) by (iii)
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2 1
Rate law, r = k [PNO2 ] [PH2 ]
Order of reaction = 2 + 1 = 3
Illustration 8.
A study of chemical kinetics of the reaction A + B Products, gave the following data at 25ºC.
Experiment [A] [B] d [Products]dt
1 1.0 0.15 4.20 × 10–6
2 2.0 0.15 8.40 × 10–6
3 1.0 0.20 5.60 × 10–6
Calculate the rate law -
(A) K [A] (B) K [B] (C) K [A] [B] (D) None of these
Ans. [C]
Solution.
Doubling the concentration of A increases the rate by two times. Raising the concentrating of B by 4/
3 times increases the rate of B by 4/3 times. Thus the reaction is of first order with respect to both A
and B. So rate law = K [A] [B].
Illustration 9.
In the reaction of NO by H2 it was observed that equimolecular mixture of gases at 500 mm was half
changed in 100 seconds. In another experiment with an initial pressure of 250 mm, the reactions was
half completed in 200 seconds. Calculate the order of reaction-
(A) 1 (B) 2 (C) 3 (D) 4
Ans. [B]
Solution.
Since, t1 / 2
1
, So
t1 LM a OP
2
n 1
LM p OP
2
n 1
an 1 t2 = Na Q
1
=
Np Q
1
Illustration 10.
For a reaction 3A products, it is found that the rate of reaction doubles, if concentration of A is
increased four times, calculate order of reaction
(A) 1 (B) 1/2 (C) 2 (D) 3
Ans. [B]
Solution.
Rate = k [Reactant]n
if [Reactant] = a ; rate = r1
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Illustration 11.
A first order reaction was started with a decimolar solution of the reactant. After 8 minutes and 20
seconds, its concentration was found to be M/100. Determine the rate constant of the reaction
(A) 4.6 × 10–3 sec –1 (B) 16.6 × 10–3 sec –1
(C) 24.6 × 10–3 sec –1 (D) 40.6 × 10–3 sec –1
Ans. [A]
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Chemical Kinetics
Solution.
Here a = 0.1 M
M
a – x = = 0.01 M
100
t = 8 minutes 20 seconds
= 500 seconds
Substituting the values in the first order reaction.
2 . 303 a
K = log
t a x
2 . 303 0 .1
= log 0 . 01
500
2 . 303
= log 10
500
4 . 606
= × 1
1000
= 4.6 × 10–3 sec–1
Illustration 12.
The first order rate constant for the decomposition of N2O5 is 6.2 × 10–4 second–1. What will be the
half life period in second for this decomposition.
(A) 1117.74 seconds (B) 117.74 seconds (C) 1177.74 seconds (D) None
Ans. [A]
Solution.
We know that for a first order reaction,
0 . 693
t1/2 =
K
0 . 693
t1/2 = 6 2 10 4
.
= 1117.74 seconds
Illustration 13.
In a first order reaction A Products, the ratio of a and (a – x) was found to be 8 after 60 minutes.
Calculate the rate of the reaction in moles of A reacted per minute, If its concentration is 0.1 mole litre–1-
(A) 5.566 × 10–3 mole litre–1 min–1 (B) 3.466 × 10–3 mole litre min
–3 –1 –1
(C) 4.366 × 10 mole litre min (D) 3.466 × 10–3 mole litre–1 min–1
Ans. [D]
Solution.
2.303 a 2.303
K= log = log 8
t a x 60
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Illustration 14.
A second order reaction with two reactants is started with 0.1 m concentration of each reactant. It is 20%
complete in 500 seconds. How much time it take to go 60% completion
(A) 5000 seconds (B) 3000 seconds (C) 2000 seconds (D) 4000 seconds
Ans. [B]
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JEE-Chemistr y
Solution.
1 x
K2 = × .
t a(a x)
Since a = 0.1 so for 20% completion x would be 20% of initial concentration.
i.e. a = 0.1
20 1 0.02 1
x = × 0.1 = 0.02 K2 = × 01
. (01
. 0.02) =
100 500 200
For 60% completion,
60
x = × 0.1 = 0.06
100
1 0 . 06 1 1 0 . 06
K2 = × 0 .1 (0 .1 0 . 06) or = × 0 .1 (0 .1 0 . 06) or t = 3000 sec.
t 200 t
Illustration 15.
The formation in water of d potassium chromo oxalate from its l form is reversible reaction which is first order
in both directions, the racemate being the equilibrium product. A polarimeter experiment at 22 0C showed that,
after 506 sec, 12 mole % of the l isomer was converted to the d form. Find the rate constant for the forward
and the reverse reactions.
Ans. Kf = kb = 2.71 x 10- 4 sec -1
Solution.
– potassium chromo - oxalate d potassium chromo oxalate
t=0 a 0
t=teq. (a – xeq.) xeq.
Kf x eq.
Keq. = K = a – x eq.
b
a
As xeq. = ; Kf = Kb
2
2 .303 x eq.
(Kf + Kb) = log x – x
t eq.
2 .303 0.5a
2Kf = log 0.5a – 0 .12a
560
2Kf = 5.42 × 10–4
Kf = Kb = 2.71 × 10–4
Illustration 16.
The values of rate constant for the decomposition of N2O5,
1
N2O5 N2O4 + O
2 2
are 3.50 x 10—5 and 5 x 10—3 at 27ºC and 67ºC, respectively. Calculate the energy of activation -
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Nurture\Che\Unit-08\Chemical Kinetics
k2 Ea T2 T1
R = 2 × 10–3 kcal mol–1 k–1 log k = x T1T2
1 2.303 xR
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Chemical Kinetics
3 340 300
5 10 E a
2.303 log 5 = 340 x 300
3.5 10 R
Ea = 25 kcal/Mole
Illustration 17.
The reaction
A+B products
is first order with respect to both A and B has a rate constant of 6.0 mol–1 sec–1. at 27°C. Calculate the initial
rate of the reaction at 47°C when equal volumes of A and B of concentration 0.02 moles litre –1 in each are
mixed. The activation energy of the energy of the reaction is 42 kJ mol –1 .
Solution.
Reaction A + B Product
K2 E 1 1
We know log K1 = T1 T2
2.303R
K2 E T2 T1
log K1 = T1T2
2.303R
K2
log = .4577
6
K2
= anti log (.4577)
6
K2 = 2.863 × 6 = 17.178
Rate at 47oC will be
The Rate2 = 17.178 × [0.01] × [0.01]
Rate2 = 17.178 × 10-4 = 1.7178 × 10-3
Illustration 18.
In Arrhenius`s equation for a certain Reaction, the value of A and E (activation energy) are 6 × 10 13 s-1 and
98.6 kJ mol-1 respectively. If the reaction is of first order, at what temperature will its half-life period be 20
minutes ?
Solution.
k = Ae-E/RT
E
In k = In A –
RT
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Nurture\Che\Unit-08\Chemical Kinetics
E
2.303 log k = 2.303 log A –
RT
E
or log k = log A – . ...(i)
2.303RT
Given that A = 6 × 10 s , E = 98.6 kJ mol-1
13 -1
t1/2 = 20 × 60 s.
0.6932 0.6932 -1
For first-order reaction k = t1/ 2 = 1200 s
Thus (i) becomes,
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JEE-Chemistr y
0.6932 98.6
log = log (6 × 1013) - 3 [R = 8.314 × 10-3 kJ/K/mol]
1200 2.303 8.314 10 T
T = 302.26 K.
Illustration 19.
For a gaseous reaction A products, the half-life of the first order decomposition at 400 K is 150 minutes
and the energy of activation is 65.0 kJ mole –1. What fraction of molecules of A at 400 K have sufficient energy
to give the products ?
Solution.
K
= e–Ea/RT = 3.13 × 10-6. = Fraction of Molecule Having Sufficient Energy
A
Illustration 20.
The following data is for the decomposition of ammonium nitrite in aqueous solution.
2.303 35.05
From Ist data K = log = 1.96 × 10–2 sec–1
10 (35.05 6.25 )
2.303 35.05
IInd data K= log = 1.96 × 10–2 sec–1
15 (35.05 9)
2.303 35 .05
IIIrd data K= log = 1.96 × 10–2 sec–1
20 (35.05 11.40 )
From these relation the value of K are same the Rxm will be First order
Illustration 21.
D
A B+C
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Time 0 t
Volume of reagent V1 V2 V3
208
Chemical Kinetics
after t = 0 reagent react with B.C.D.
2a a (V3 - V1)
( V3 - V1 )
aa
2
2x a (V2 - V1)
2(a - x) a (V3 - V1 - V2 + V1)
( V3 - V2 )
(a - x) a
2
1 ( V3 - V1 )
Then K = ln ( V - V )
t 3 2
Illustration 22.
k1 k2
In the case of first order consecutive reactions A ¾¾ ® B ¾¾
¾® C (Product), one may show that the
concentration of B is given by
k1C0A k k
CB = é e - t - e - t ùû .
1 2
(k 2 - k1 ) ë
The usual assumptions are CA = CA0 at t = 0 while CB = CC = 0 at t = 0. Show that CB has its maximum value
æ 2.303 ö æ k2 ö
at time t = çç k - k ÷÷ log çç ÷÷ .
è 2 1ø è k1 ø
Solution.
dCB k1C°A
= é k e - k 2 t - k 1e - k 1t ùû
dt (k 2 - k1 ) ë 2
k2 æ k2 ö æ 2.303 ö æ k2 ö
\ = (k 2 -k 1 ) t \ln çç ÷÷ = (k – k ) t \ t = çç k - k ÷÷ log çç k ÷÷
k1 e
è k1 ø 2 1
è 2 1ø è 1ø
Illustration 23.
dN 1
Starting from the equation for radioactive decay i.e. – = lN, derive the expression, mean life = .
dt l
Solution.
dN
– = lN . This on integration gives (with N = N0 , at t = 0) ; N = N0 e–lt
dt
¥ ¥
é ¥ ù
ê
ò tdN ú ò t
dN
dt ò ( -lN0 )e -lt t dt
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ê ú dt t =0 1 1
t=0 t =0
Mean life = ê ú = = ¥ = . \ Mean life =
ê ¥
ú ¥ l l
ê
ê ò dN ú
ú
ò
dN
dt
dt ò
t =0
( -lN0 )e -lt dt
ë t=0 û t=0
Illustration 24.
The half life time for the decomposition of a substance dissolved in CCl4 is 2.5 hour at 30ºC. How much
of the substance will be left after 10 hours, if the initial weight of the substance is 160 gm
(A) 20 gm (B) 30gm (C) 40 gm (D) 10 gm
Ans. [D]
Solution.
No. of half life periods
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Total time 10
= = = 4
Time of one half life period 2.5
Now we know that the quantity left after ‘n’ half-life periods
= (1/2)n × Initial quantity
= (1/2)4 × 160
160
= = 10 gm
2 2 2 2
Illustration 25.
(a) The decomposition of HI to yield H2 and I 2 at 508°C has a half-life of 135 minutes when
PHI = 0.1 atm (initially), which comes down to one tenth of that value when the initial pressure is 1 atm.
Calculate the rate constant.
(b) In a kinetic study of the reduction of nitric oxide with hydrogen, the initial pressure of 340 mm, an
equimolar mixture of gases was reduced to half the value in 102 seconds. In another experiment, the
initial pressure of 288 mm, under the same conditions was reduced to half the value in 140 sec. Calculate
the order of the reaction.
Ans. (a) 0.074 atm–1 min–1 , (b) 3
Solution. (a) t1/2 = 135 minutes at PHI = 0.1 atm
t 1/2 = 13.5 minutes at PHI = 1 atm.
1
t1/2 PHI
a
At t = t1/2 , (a – x) =
2
1 1
k = at = = 0.074 atm–1 min–1
1/ 2 0.1 135
(b) The reaction is not first order because the t 1/2 varies with initial concentration.
1 1
For a second order reaction, t1/2 is proportional to n 1
or t1/2 is proportional to
a a
where n = 2 and a = initial concentration
t1/2 × a = constant
from the given data, 340 × 102 = 34680
288 × 140 = 40320
The products are not constant, therefore the reaction is not second order also,
( t1/ 2 )1 ( an 1)
2
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For a third order reaction = n 1 1, 2 represent the first and second data given.
( t1/ 2 )2 (a )1
n 1
102 ( 288 )n 1
288
= =
140 ( 340 )n 1
340
* * * * *
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Chemical Kinetics
ANSWERS
BEGINNER'S BOX-1
1. (D) 2. (B) 3. (A) 4. (C) 5. (B)
6. (B) 7. (C) 8. (C) 9. (C) 10. (C)
BEGINNER'S BOX-2
1. (A) 2. (A) 3. (A) 4. (B) 5. (B)
6. (C) 7. (A) 8. (A) 9. (D)
BEGINNER'S BOX-3
1. (D) 2. (C) 3. (B) 4. (A) 5. (C)
6. (D) 7. (C)
BEGINNER'S BOX-4
1. (D) 2. (A) 3. (A) 4. (C) 5. (B)
6. (B) 7. (C)
BEGINNER'S BOX-5
1. (C) 2. (C) 3. (A) 4. (B) 5. (A)
6. (C) 7. (B)
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2. In the formation of sulphur trioxide by contact process, 2SO2 + O2 2SO3, the rate of reaction was
d[O2 ]
measured as = 2.5 × 10-4 mol lit-1 sec-1. the rate of formation of SO3 will be-
dt
(A) –1.25 × 10-4 mol L–2 sec-1 (B) 50 × 10-4 mol L–1 sec–1
(C) –3.75 × 10-4 mol L–1 sec-1 (D) 5.00 × 10-4 mol L–1 sec–1
d[C]
3. Reaction A + 2B + C product, follows the rate law : = k [A]2
dt
False statement regarding the above reaction is :
(A) On doubling the conc. of B and C the rate of the reaction remains unaffected
(B) Reducing the conc. of A to half, the rate becomes one-fourth
(C) Half life period of the reaction depends upon the conc. of B
(D) Half life period of the reaction is inversely proportional to the first power conc. of A
4. In a first order reaction, the initial conc. of the reactant was M/10. After 8 minutes 20 seconds the conc.
becomes M/100. What is the rate constant ?
(A) 5 × 10–3 second–1 (B) 2.303 × 10–5 second–1
–4 –1
(C) 2.303 × 10 second (D) 4.606 × 10–3 second–1
6. Dinitrogen pentaoxide decomposes as 2N 2O5 4NO2 + O2. the rate can be given in three ways
d[N2O5 ] d[NO2 ] d[O2 ]
= k1 [N2O5], = k2 [N2O5], = k3 [N2O5]
dt dt dt
The relation between the rate constants k1, k2 and k3 is :
(A) k2 = 2k1 and k3 = 1/2 k1 (B) k1 = 2k2 and k3 = 2k1
(C) k1 = k2 = k3 (D) k1 = 2k2 = 3k3
k1
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Y
d[x]
7. For a reaction X , is equal to
t 0 a dt
t t (a x) k2
Z
(A) k1 (a – x) – k2 (a – x) (B) k2 (a – x) – k1 (a – x)
(C) k1 (a – x) + k2 (a – x) (D) –k1 (a – x) – k2 (a – x)
12. In a certain reaction 10% of the reactant decomposes in one hour, 20% in two hours, 30% in three hours and so
on. Dimension of the velocity constant (rate constant) are-
(A) Hour –1 (B) Mol litre–1hour –1
–1 –1
(C) Litre mol sec (D) Mol sec–1
14. In acidic medium the rate of reaction between (BrO 3) – and Br– ion is given by the expression
d[BrO3 ]
= k[BrO3–] [Br–] [H+]2 it means
dt
(A) Rate constant of overall reaction is 4 sec –1
(B) Rate of reaction is independent of the conc. of acid
(C) The change in pH of the solution will not affect the rate
(D) Doubling the conc. of H+ ions will increase the reaction rate by 4 times
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d[D]
15. The rate law for the reaction : 2 C + D A + E is – = k[C]2 [D]
dt
If C is present in large excess, the order of the reaction will be -
(A) Zero (B) First (C) Second (D) Third
dx
16. For a second order reaction = k(a – x)2. Its half life period is :
dt
1 0.693 a 0.693
(A) (B) (C) (D)
a. k k k ak
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JEE-Chemistr y
17. The dissociation of nitrogen pentoxide is a first order reaction. In first 24 minutes 75% of nitrogen pentaoxide is
dissociated. What amount of nitrogen pentaoxide will be left behind after one hour of start of the
reaction ?
(A) Approximately 1% (B) Approximately 2% (C) Approximately 3% (D) None
18. In the Wilhelmey equation of a first order reaction Ct = C0e–kt if the initial concentration C0 is increased m times
then
(A) The value of k will increase m times (B) The value of k will decrease m times
(C) The value of k will remains unchanged (D) None of these
19. The half-life period for a reaction at initial concentration of 0.5 and 1.0 moles litre –1 are 200 sec and 100 sec
respectively. The order of the reaction is
(A) 0 (B) 1 (C) 2 (D) 3
1
20. In Arrehenius equation if a graph is plotted between log k and , the slope of the curve will be :
T
Ea Ea E Ea
(A) – (B) – (C) a (D)
R 2.303 R R 2.303 R
21. A reaction takes place in three steps. The rate constants are k1, k2 and k3. The over all rate constant
k1k 3
k= . If (energy of activation) E1, E2 and E3 are 60, 30 and 10 kJ. The overall energy of activation is :
k2
(A) 40 (B) 30 (C) 400 (D) 60
22. The rate constant for the forward reaction A (g) 2B (g) is 1.5 × 10–3 s–1 at 100 K. If 10–5 moles of A and
100 moles of B are present in a 10 litre vessel at equilibrium then rate constant for the backward reaction at this
temperature is :
(A) 1.50 × 104 L mol–1 s–1 (B) 1.5 × 1011 L mol–1 s–1
10 –1 –1
(C) 1.5 × 10 L mol s (D) 1.5 × 10–11 L mol–1 s–1
1 1
2 2
23. Reaction A + B C + D follow's following rate law rate = k = [A] [B] . Starting with initial conc. of one
mole of A and B each, what is the time taken for amount of A of become 0.25 mole. Given
k = 2.31 × 10–3 sec–1.
(A) 300 sec. (B) 600 sec. (C) 900 sec. (D) none of these
24. The rate constant, the activation energy and the Arrhenius parameter of a chemical reaction at 25°C are
3.0× 10–4 s–1, 104.4 kJ mol–1 and 6.0 × 1014 s–1 respectively. The value of the rate constant at T is :
18 –1 14 –1 30 –1
(A) 2.0 × 10 s (B) 6.0 × 10 s (C) infinity (D) 3.6 × 10 s
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Chemical Kinetics
d[A]
2. For the reaction A B, the rate law expression is = k [A]1/2. If initial concentration of [A] is [A] 0, then
dt
2 1/ 2
(A) The integerated rate expression is k = (A 0 A1 / 2 )
t
K
(C) The half life period t 1 / 2 =
2[A ]10/ 2
[A]0
(D) The time taken for 75% completion of reaction t 3 / 4 =
k
4. For the reaction CH4 + Br2 CH3Br + HBr, the experimental data require the following rate equation:
d k1[CH4 ][Br2 ]
[CH3Br] =
dt 1 k 2 [HBr ] /[Br2 ]
Which of the following is/are true regarding this ?
(A) The reaction is a single step reaction
(B) The reaction is 2nd order in the initial stages {[HBr] 0}
(C) The reaction is 2nd order in the final stages {[Br 2] 0}
(D) The molecularity of the reaction is two.
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JEE-Chemistr y
E1 E2
6. In a consecutive reaction system A B C when E1 is much greater than E2, the yield of B
increase with
(A) increase in temperature (B) decreases in temperature
(C) increase in initial concentration of A (D) decrease in initial concentration of A
9. The polarimeter readings in a experiment to measure the rate of inversion of cane sugar (1 st order reaction) were
as follows:
Time (min.) 0 30
Rotation due to solution (degree) 30 20 –15
Identify the true statements:
[Given : log 2 = 03, log 3 = 0.48, log 7 = 0.84, (log e 10) = 2.3
(A) The half life of the reaction is 75 min
(B) The solution is optically inactive at 120 min
(C) The half life of the reaction is 60 min
(D) The solution is optically inactive at 90 min.
10. For a certain reaction A P, the half life for different initial concentration of A is mentioned below.
[A0] 0.1 0.025
t½ (s) 100 50
Which of the following option(s) is/are incorrect.
(A) The order is 1 (B) The order is 0.5
(C) For [A0] = 1M, t½ = 100 10 sec . (D) For [A0] = 1M t½ = 100 sec.
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11. For the (Set-1) :
(A) if T1 > T2, k1 > k2 always (B) if T1 > T2, k1 > k2 (for exothermic reaction)
(C) if T1 > T2, k1 < k2 (for endothermic reaction) (D) Ea1 Ea2
Comprehension-2
A reaction is said to be first order if it's rate is proportional to the concentration of reactant. Let us consider a
reaction
A(g) B(g) + C(g)
At t = 0 a 0 0
At time t a–x x x
dx
The rate of reaction is given by the expression = k(a – x) and integrated rate equation for a given reaction
dt
1 a
is represented as k = ln where a = initial concentration and (a – x) = concentration of A after
t a x
time t.
14. Thermal decomposition of compound X is a first order reaction. If 75% of X is decomposed in 100 min. How
long will it take for 90% of the compound to decompose?
Given : log 2 = 0.30
(A) 190 min (B) 176.66 min (C) 166.66 min (D) 156.66 min
15. Consider a reaction A(g) 3B(g) + 2C(g) with rate constant 1.386 × 10–2 min–1. Starting with
2 moles of A in 12.5 litre vessel initially, if reaction is allowed to takes place at constant pressure & at 298K then
find the concentration of B after 100 min.
(A) 0.04 M (B) 0.36 M (C) 0.09 M (D) None of these
Comprehension-3
Competing First-Order Reactions
Frequently a species can react in different ways to give a variety of products. For example, toluene can be
nitrated at the ortho, meta, or para positions, We shall consider the simplest case, that of two competing
irreversible first-order reactions :
k1 k2 D
A C and A
where the stoichiometric coefficients are taken as unity for simplicity. The rate law is
d [A ]
= – k1[A] – k2[A] = – (k1 + k2) [A] [A] = [A]0 e ( k 1 k 2 )t .
dt
d [C]
For C, we have = k1[A] = k1[A]0 e ( k 1 k 2 )t . Multiplication by dt and integration from time 0
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dt
k 1[ A ] 0 ( k1 k 2 ) t
(where [C]0 = 0) to an arbitary time t gives [C] = (1 e )
k1 k 2
d [D] k [A]
Similarly, integration of gives [D] = 2 0 (1 – e (k 1 k 2 )t )
dt k1 k 2
The sum of the rate constants k1 + k2 appears in the exponentials for both [C] and [D].
[C] k1
At any time we also have =
[D] k2
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16. A starting initially with only A Which of the following is correct at time t
(A) [A]0 = [A]t +[B]t + [C]t (B) [A]0 = [A]t + 2 [B]t + 3 [C]t
[B] t [C] t 2
(C) [A]0 = [A]t + + (D) [A]0 = [A]t +[B]t + [C]t
2 3 3
[ X] t
17. X starting with only 'X', ratio
[ Y ] t [ Z] t
1
(A) Independent of time (B)
(ekt 1)
(C) Depends upon initial concentration of X (D) [A]0 (ekt –1)
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Chemical Kinetics
2. The reaction SO2Cl2 (g) SO2 (g) + Cl2 (g) is a first order gas reaction with k = 2.2 × 10 –5 sec–1 at 320°C.
What % of SO2Cl2 is decomposed on heating this gas for 90 min.
3. Two substance A (t1/2 = 5 mins) and B (t1/2 = 15 mins) follow first order kinetics are taken in such a way that
initially [A] = 4[B]. Calculate the time (in minute) after which the concentration of both the substance will be
equal.
4. Calculate the age (in years) of a vegetarian beverage whose tritium content is only 15% of the level in living
plants. Given t1/2 for 1H3 = 12.3 years.
K1(hr–1) = 102 e
K1
A2(g) 2A(g) RT
20000
B3(g) K2
3B(g) K2(hr–1) = 103 e RT
If one mole of each A2(g) and B3(g) are taken in a 10 L evacuated flask and heated to some temperature so that
they start decomposing at the same rate, determine total pressure (in atm) in the flask after 1.0 hr.
B
6. The reaction A proceeds in 1st order parallel channels A . Suppose the half life values for the two branches
C
are 60 minutes and 90 minutes, what is the overall half-life (in minute) value?
7. H2 gas is adsorbed on the metal surface like tungsten. The order of this process is
8. In a first order reaction, the concentration of the reactant, decreases from 0.8 M to 0.4 M in 15 minutes.
The time taken (in minutes) for the concentration to change from 0.1 M to 0.025 M is
9. The half-life of a radio isotope is four hours. If the initial mass of the isotope was 200 g, the mass (in gm)
remaining after 24 hours undecayed is :
10. A certain organic compound A decomposes by two parallel first order mechanism
k1 B
A
If k1 : k2 = 1 : 9 and k1 = 1.3 × 10–5 s–1
k2
C
Calculate the concentration ratio of C to A, if experiment is started with only A and allowed to run for one hour.
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SECTION - 2 : MATRIX - MATCH QUESTIONS
11. For the reaction of type A(g) 2B(g)
Column-I contains four entries and column-II contains four entries. Entry of column-I are to be matched with
ONLY ONE ENTRY of column-II.
Column - I Column - II
d[ B] d[ A]
(A) vs for first order (p)
dt dt
(B) Rate constant of a first - order reaction is 0.0693 min–1. (q) Zero
If we start with 20 mol L–1, it is reduced to 2.5 mol L–1
in how many minutes
(C) Half - lives of first - order and zero order reactions (r) 11
are same. Ratio of rates at the start of reaction is
how many times of 0.693 Assume initial concentration to
be same for the both.
13. The polarimeter readings in an experiment to measure the rate of inversion of cane suger (1st order reaction)
were as follows
time (min) : 0 30
angle (degree) : 30 20 – 15
Then match the following. (Use : log 35 = 1.54, log 3 = 0.48, log 2 = 0.3)
Column - I Column - II
(A) The half life of the reaction (p) 120 min.
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Chemical Kinetics
1
1. For a reaction A 2B , rate of disappearance of ‘A’ is related to the rate of appearance of ‘B’ by the
2
expression [AIEEE-2008]
d A 1d B d A 1d B d A d B d A d B
(1) – = (2) – = (3) – = (4) – =4
dt 2 dt dt 4 dt dt dt dt dt
2. The half life period of a first order chemical reaction is 6.93 minutes. The time required for the completion
of 99% of the chemical reaction will be (log 2 = 0.301) :- [AIEEE-2009]
(1) 46.06 minutes (2) 460.6 minutes (3) 230.3 minutes (4) 23.03 minutes
3. The time for half life period of a certain reaction A Products is 1 hour. When the initial concentration fo
–1,
the reactant 'A' is 2.0 mol L How much time does it take for its concentration to come from 0.50 to 0.25
mol L–1 if it is a zero order reaction ? [AIEEE-2010]
(1) 1 h (2) 4 h (3) 0.5 h (4) 0.25 h
4. The rate of a chemical reaction doubles for every 10°C rise of temperature. If the temperature is raised by 50°C,
the rate of the reaction increases by about :- [AIEEE-2011]
(1) 32 times (2) 64 times (3) 10 times (4) 24 times
6. The activation energy for a reaction which doubles the rate when the temperature is raised from 298 K to 308
K is :- [AIEEE ONLINE - 2012]
(1) 29.5 kJ mol–1 (2) 39.2 kJ mol–1 (3) 52.9 kJ mol–1 (4) 59.2 kJ mol–1
7. In a chemical reaction A is converted into B. The rates of reaction, starting with initial concentration of A as
2 × 10–3 M and 1 × 10–3 M, are equal to 2.40 × 10–4 Ms–1 and 0.60 × 10–4 Ms–1 respectively. The order
of reaction with respect to reactant A will be :- [AIEEE ONLINE - 2012]
(1) 1.5 (2) 2 (3) 0 (4) 1
8. For a first order reaction, (A) products, the concentration of A changes from 0.1 M to 0.025M in 40 minutes.
The rate of reaction when the concentration of A is 0.01 M is :- [AIEEE-2012]
(1) 1.73 × 10–4 M/min (2) 1.73 × 10–5 M/min (3) 3.47 × 10–4 M/min (4) 3.47 × 10–5 M/min
9. A radioactive isotope having a half - life period of 3 days was received after 12 days. If 3g of the isotope is
left in the container, what would be the initial mass of the isotope ? [JEE MAINS - ONLINE - 2013]
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Nurture\Che\Unit-08\Chemical Kinetics
10. The half-life period of a first order reaction is 15 minutes. The amount of substance left after one hour will be:
[JEE MAINS - ONLINE - 2014]
1 1
(1) of the original amount (2) of the original amount
4 16
1 1
(3) of the original amount (4) of the original amount
32 8
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11. For the reaction
3A + 2B C + D the differential rate law can be written as [JEE MAINS - ONLINE - 2014]
1 d[A] d[C] 1 d[A] d[C]
(1) k[A]n [B]m (2) k[A]n [B]m
3 dt dt 3 dt dt
1 d[A] d[C] d[A] d[C]
(3) k[A]n [B]m (4) k[A]n [B]m
3 dt dt dt dt
12. For the non-stoichiometry reaction 2A + B C + D, the following kinetic data were obtained in three separate
experiments, all at 298 K. [JEE Mains-2014]
13. A + 2B C, the rate equation for this reaction is given as Rate = k[A][B].[JEE MAINS - ONLINE - 2015]
If the concentration of A is kept the same but that of B is doubled what will happen to the rate itself?
(1) quadrupled (2) doubled (3) halved (4) the same
14. The rate law for the reaction below is given by the expression k[A] [B]
A+B Product [JEE MAINS - ONLINE - 2016]
If the concentration of B is increased from 0.1 to 0.3 mole, keeping the value of A at 0.1 mole, the rate constant
will be :
(1) 3k (2) 9k (3) k (4) k/3
15. For the reaction, 2A + B products, when the concentrations of A and B both wrere doubled, the rate of
the reaction increased from 0.3 mol L–1s–1 to 2.4 mol L–l s–1. When the concentration of A alone is doubled,
the rate increased from 0.3 mol L–1s–1 to0.6 mol L–1s–1
Which one of the following statements is correct ? [JEE MAINS - ONLINE - 2019]
(1) Order of the reaction with respect to B is 2 (2) Order of the reaction with respect to A is 2
(3) Total order of the reaction is 4 (4) Order of the reaction with respect to B is 1
K2
6AB(g) 3A2(g) + 3B2(g) .....(2)
The relation between K1 and K2 is :
1
(1) K2 = K13 (2) K2 = K1–3 (3) K1K2 = 3 (4) K1K2 =
3
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17. The following results were obtained during kinetic studies of the reaction :
2A + B Products [JEE MAINS - ONLINE - 2019]
Experment [A] [B] Initial Rate of reaction
-1 -1
(in mol L ) (in mol L ) (in mol L–1 min–1)
19. Consider the given plots for a reaction obeying Arrhenius equation (0°C < T < 300°C) : (k and Ea are rate
constant and activation energy, respectively) [JEE MAINS - ONLINE - 2019]
k k
Ea T(°C)
I II
Choose the correct option :
(1) Both I and II are wrong (2) I is wrong but II is right
(3) Both I and II are correct (4) I is right but II is wrong
20. The reaction 2X B is a zeroth order reaction. If the initial concentration of X is 0.2 M, the half-life is 6 h.
When the initial concentration of X is 0.5 M, the time required to reach its final concentration of 0.2 M will
be :- [JEE MAINS - ONLINE - 2019]
(1) 18.0 h (2) 7.2 h (3) 9.0 h (4) 12.0 h
1
21. If a reaction follows the Arrhenius equation, the plot lnk vs gives straight line with a gradient (–y) unit.
(RT)
The energy required to activate the reactant is : [JEE MAINS - ONLINE - 2019]
(1) y unit (2) –y unit (3) yR unit (4) y/R unit
22. For a reaction, consider the plot of ln k versus 1/T given in the figure. If the rate constant of this reaction at
400 K is 10–5 s–1, then the rate constant at 500 K is : [JEE MAINS - ONLINE - 2019]
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ln k slope = –4606K
1/T
–4 –1 –4 –1
(1) 2×10 s (2) 10 s (3) 10–6 s–1 (4) 4×10–4 s–1
23. Decomposition of X exhibits a rate constant of 0.05 g/year. How many years are required for the decomposition
of 5 g of X into 2.5 g ? [JEE MAINS - ONLINE - 2019]
(1) 50 (2) 25 (3) 20 (4) 40
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24. For the reaction 2A +B C, the values of initial rate at different reactant concentrations are given in the table
below. The rate law for the reaction is : [JEE MAINS - ONLINE - 2019]
k1 k2
25. For a reaction scheme A B C , if the rate of formation of B is set to be zero then the concentration
of B is given by : [JEE MAINS - ONLINE - 2019]
k1
(1) [A] (2) (k1 + k2) [A] (3) k1k2[A] (4) (k1 – k2) [A]
k2
26. The given plots represent the variation of the concentration of a reactant R with time for two different reactions
(i) and (ii). The respective orders of the reactions are : [JEE MAINS - ONLINE - 2019]
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Chemical Kinetics
2. For a reaction A Products, a plot of log t½ versus log a0 is shown in figure. If the initial concentration of A is
represented by a0, the order of the reaction is :- [AIEEE ONLINE - 2012]
(1) Two
(2) Zero log t½ 45º
(3) One
(4) Three
log a0
3. The instantaneous rate of disappearance of MnO4 ion in the following reaction is 4.56 × 10 –3Ms–1
–
4. The rate constant of a zero order reaction is 2.0 × 10 –2 mol L–1 s–1. If the concentration of the reactant after 25
seconds is 0.5 M. What is the initial concentration ? [JEE MAINS - ONLINE - 2013]
(1) 0.5 M (2) 12.5 M (3) l.0 M (4) 1.25 M
5. The rate of reaction doubles when its temperature changes form 300 K to 310 K. Activation energy of such a
reaction will be : (R = 8.314 JK–1 mol–1 and log 2 = 0.301) [JEE Mains-2013]
(1) 53.6 kJ mol–1 (2) 48.6 kJ mol–1 (3) 58.5 kJ mol–1 (4) 60.5 kJ mol–1
d[N 2O5 ]
6. For the reaction, 2N2O5 4NO2 + O2, the rate equation can be expressed in two ways k[N 2O5 ]
dt
d[NO 2 ]
and k [N 2O5 ] [JEE MAINS - ONLINE - 2014]
dt
k and k are related as
(1) k = k (2) k = 4k (3) 2k = k (4) k = 2k
The rate coefficient (k) for a particular reactions is 1.3 x 10–4 M–1 s–1 at 100ºC, and 1.3 × 10– 3 M–1 s–1 at
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7.
150°C, What is the energy of activation (E A) (in kJ) for this reaction ?
(R = molar gas constant = 8.314 JK–1 mol–1) [JEE MAINS - ONLINE - 2014]
(1) 132 (2) 60 (3) 99 (4) 16
8. The reaction
2N2O5(g) 4NO2(g) + O2(g) [JEE MAINS - ONLINE - 2015]
follows first order kinetics. The pressure of a vessel containing only N 2O5 was found to increase from 50 mm Hg
to 87.5 mm Hg in 30 min. The pressure exerted by the gases after 60 min. will be (Assume temperature remains
constant) :
(1) 106.25 nm Hg (2) 116.25 nm Hg (3) 125 mm Hg (4) 150 mm Hg
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9. Decomposition of H2O2 follows a first order reaction. In fifty minutes the concentration of H2O2 decreases from
0.5 to 0.125 M in one such decomposition. When the concentration of H2O2 reaches 0.05 M, the rate of
formation of O2 will be [JEE Mains-2016]
(1) 6.93 × 10–2 mol min–1 (2) 6.93 × 10–4 mol min–1
(3) 2.66 L min–1 at STP (4) 1.34 × 10–2 mol min–1
10. The rate of a reaction A doubles on increasing the temperature from 300 to 310 K. By how much, the temperature
of reaction B should be increased from 300 K so that rate doubles if activation energy of the reeaction B is twice
to that of reaction A : [JEE MAINS - ONLINE - 2017]
(1) 2.45 K (2) 4.92 K (3) 9.84 K (4) 19.67 K
11. The rate of a reaction quadruples when the temperature changes from 300 to 310 K. The activation energy of
this reaction is: [JEE MAINS - ONLINE - 2017]
(Assume activation energy and pre-exponential factor are independent of temperature; n 2 = 0.693;
R = 8.314 J mol–1 K–1)
(1) 107.2 kJ mol–1 (2) 53.6 kJ mol–1 (3) 214.4 kJ mol–1 (4) 26.8 kJ mol–1
12. Two reactions R1 and R2 have identical pre-exponential factors. Activation energy of R1 exceeds that R2 by 10 kJ
mol–1. If k1 and k2 are rate constants for reactions R1 and R2 respectively at 300 K, then In(K2/k1) is equal to :
(R = 8.314 J mol–1 K–1) [JEE Mains-2017]
(1) 4 (2) 8 (3) 12 (4) 6
13. At 518ºC, the rate of decomposition of a sample of gaseous acetaldehyde, initially at a pressure of 363 Torr, was
1.00 Torr s–1 when 5% had reacted and 0.5 Torr s–1 when 33% had reacted. The order of the reaction is
[JEE Mains-2018]
(1) 2 (2) 3 (3) 1 (4) 0
14. A bacterial infection in an internal wound grows as N'(t) = N 0 exp(t), where the time t is in hours. A dose of
antibiotic, taken orally, needs 1 hour to reach the wound. Once it reaches there, the bacterial population goes
dN N0
down as = –5N2. What will be the plot of vs. t after 1 hour ? [JEE MAINS - ONLINE - 2019]
dt N
N0 N0 N0 N0
N N N N
(1) (2) (3) (4)
15. For the reaction of H2 with I2, the rate constant is 2.5×10–4dm3 mol–1 s–1 at 327°C and 1.0 dm3 mol–1 s–1 at
527°C. The activation energy for the reaction, in kJ mol –1 is: [JEE MAINS - ONLINE - 2019]
(R=8.314J K–1 mol–1)
(1) 72 (2) 166 (3) 150 (4) 59
16. NO2 required for a reaction is produced by the decomposition of N 2O5 in CCl4 as per the equation
2N2O5(g) 4NO2(g) + O2(g). [JEE MAINS - ONLINE - 2019]
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2. A sample of milk splits after 60 min. at 300 K and after 40 min. at 400 K when the population of lactobacillus
acidophilus in it doubles. The activa tion energy (in kJ/ mol) for this process is closest to__________.
2
(Given, R = 8.3 J mol–1 K–1, ln = 0.4, e–3 = 4.0) [JEE MAINS - ONLINE - 2020]
3
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*1. Under the same reaction conditions, initial concentration of 1.386 mol dm–3 of a substance becomes half in 40
k1
seconds and 20 seconds through first order and zero order kinetics, respectively. Ratio of the rate constants
k0
for first order (k1) and zero order (k0) of the reactions is [JEE 2008]
(A) 0.5 mol–1 dm3 (B) 1.0 mol dm–3 (C) 1.5 mol dm–3 (D) 2.0 mol–1 dm3
2. Statement-1 : The plot of atomic number (y-axis) versus number of neutrons (x-axis) for stable nuclei shows a
curvature towards x-axis from the line of 45° slope
as the atomic number is increased.
and
Statement-2 : Proton-proton electrostatic repulsions begin to overcome attractive forces involving protons and
neutrons in heavier nuclides. [JEE 2008]
(A) Statement-1 is True, Statement-2 is True ; Statement-2 is a correct explanation for Statement-1
(B) Statement-1 is True, Statement-2 is True ; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True
238 214
*3. The total number of and particles emitted in the nuclear reaction 92 U 82 Pb is. [JEE 2009]
142
4. The number of neutrons emitted when 235
92 U undergoes controlled nuclear fission to 54 Xe and 90
38 Sr is -
[JEE 2010]
5. Plots showing the variation of the rate constant (k) with temperature (T) are given below. The plot that follows
Arrhenius equation is – [JEE 2010]
k k k k
(A) (B) (C) (D)
T T T T
*6. The concentration of R in the reaction R P was measured as a function of time and the following data
is obtained :
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*8. Bombardment of aluminium by -particle leads to its artificial disintegration in two ways,
(i) and (ii) as shown. Products X, Y and Z respectively are : [JEE 2011]
27 (ii) 30
13
Al 15 P + Y
(i)
30 30
14 Si + X 14Si + Z
(A) proton, neutron, positron (B) neutron, positron, proton
(C) proton, positron, neutron (D) positron, proton, neutron
*9. The periodic table consists of 18 groups. An isotope of copper, on bombardment with protons, undergoes a
nuclear reaction yielding element X as shown below. To which group , element X belongs in the periodic table?
[JEE 2012]
63 1
29 Cu 1 H 6 10 n 211 H X
10. An organic compound undergoes first-order decomposition . The time taken for its decomposition to 1/8 and
[t 1/8 ]
1/10 of its initial concentration are t1/8 and t1/10 respectively. What is the value of 10 ?
t 1/10
(Take log102 = 0.3) [JEE 2012]
[Q]0
[Q]
Time
12. For the elementary reaction M N, the rate of disappearance of M increases by a factor of 8 upon doubling
the concentration of M. The order of the reaction with respect to M is [JEE 2014]
(A) 4 (B) 3 (C) 2 (D) 1
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Nurture\Che\Unit-08\Chemical Kinetics
*13. A closed vessel with rigid walls contains 1 mol of 238 and 1 mol of air at 298 K. Considering complete decay
92 U
of 238 to 206 the ratio of the final pressure to the initial pressure of the system at 298 K is [JEE 2015]
92 U 82 Pb ,
*14. A plot of the number of neutrons (N) against the number of protons (P) of stable nuclei exhibits upwards
deviation from linearity for atomic numberk, Z > 20. For an unstable nucleus having N/P ratio less than 1, the
possible mode(s) of decay is (are) [JEE 2016]
(A) – -decay ( emission) (B) orbital or K-electron capture
(C) neutron emission (D) -decay (positron emission)
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JEE-Chemistr y
*15. According to the Arrhenius equation, [JEE 2016]
(A) a high activation energy usually implies a fast reaction.
(B) rate constant increases with increase in temperature. This is due to a greater number of collisions whose
energy exceeds the activation energy.
(C) higher the magnitude of activation energy, stronger is the temperature dependence of the rate constant.
(D) the pre–exponential factor is a measure of the rate at which collisions occur, irrespective of their energy.
16. In a bimolecular reaction, the steric factor P was experimentally determined to be 4.5. The correct option(s)
among the following is (are) [JEE 2017]
(A) The value of frequency factor predicted by Arrhenius equation is higher than that determined experimentally
(B) The activation energy of the reaction is unaffected by the value of the steric factor
(C) Since P = 4.5, the reaction will not proceed unless an effective catalyst is used
(D) Experimentally determined value of frequency factor is higher than that predicted by Arrhenius equation
*18. For a first order reaction A(g) 2B(g) + C(g) at constant volume and 300 K, the total pressure at the beginning
(t = 0) and at time t are P0 and Pt, respectively. Initially, only A is present with concentration [A]0, and t1/3 is the
time required for the partial pressure of A to reach 1/3 rd of its initial value. The correct option(s) is (are)
(Assume that all these gases behave as ideal gases) [JEE 2018]
In(3P0 – Pt)
t1/3
(A) (B)
Time [A]0
Rate constant
In(P0 – Pt)
(C) (D)
Time [A]0
238 234
92 U 90 Th 91 Pa Z 90 Th
[JEE 2019]
x1, x2, x3 and x4 are particles/ radiation emitted by the respective isotopes. The correct option(s) is/are-
(A) Z is an isotope of uranium
(B) x2 is –
(C) x1 will deflect towards negatively charged plate
(D) x3 is -ray
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Chemical Kinetics
20. Consider the kinetic data given in the following table for the reaction A + B + C Product.
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JEE-Chemistr y
ANSWERS
EXERCISE-1
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. C B C D B A C D B C B B B D B
Que. 16 17 18 19 20 21 22 23 24 25
Ans. A C C C B A D B B B
EXERCISE-2
MULTIPLE CORRECT CHOICE QUESTIONS
1. (ABCD) 2. (ABD) 3. (ACD) 4. (BC) 5. (CD)
6. (AC) 7. (AB) 8. (AC) 9. (AB) 10. (AD)
EXERCISE-3
NUMERICAL ANSWER BASED QUESTIONS
1. (924) 2. (11.2) 3. (15) 4. (33.67) 5. (5.42)
6. (36) 7. (0) 8. (30) 9. (3.125) 10. (0.537)
EXERCISE-4(A)
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. 2 1 4 1 2 3 2 3 2 2 1 4 2 3 1
Que. 16 17 18 19 20 21 22 23 24 25 26 27
Ans. 2 2 3 4 1 1 2 1 3 2 1 2
EXERCISE-4(B)
SECTION - 1 : SINGLE CHOICE CORRECT QUESTIONS
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. 1 2 1 3 1 3 2 1 2 2 1 1 1 1 2
Que. 16 17
Ans. 4 4
SECTION - 2 : NUMERICAL ANSWER BASED TYPE QUESTIONS
JPR\COMP.251\D\Allen(IIT-JEE Wing)\2020–21\Nurture\Che\Unit-08\Chemical Kinetics
Que. 1 2
Ans. 23 3.984
EXERCISE-5
1. (A) 2. (A) 3. (8) 4. (4) 5. (A)
6. (0) 7. (ABD) 8. (A) 9. (8) 10. (9)
11. (D) 12. (B) 13. (9) 14. (BD) 15. (BCD)
16. (BD) 17. (8500) 18. (AD) 19. (ABC) 20. (6.75)
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