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3 0 | Chemical Kinetics

Solved Examples

can be expressed as

Example 1: The half-life period of a first-order reaction d[N2O5 ]

is 30 min. Calulate the specific reaction rate of the (i) – = k1[N2O5]

dt

reaction. What fraction of the reactant remains after 70

d[NO2 ]

min? (ii) = k2[N2O5]

dt

0.6932 0.6932

Sol: k1 = = = 0.0231 min–1. d[O2 ]

t1 30 (iii) = k3[N2O5]

dt

2

Concentration after (a – x) x

1 d[N2O5 ] 1 d[NO2 ] d[O2 ]

70 min − = = = k N2O5

2 dt 4 dt dt

∴ Fraction of the reaction remained unreacted

d[N2O5 ]

(a − x) 2.303 a ∴– = 2k[N2O5] = k1[N2O5]

= Now, k1 = log or 0.0231 dt

a . t a−x d[NO2 ]

2.303 a = 4k[N2O5] = k2[N2O5]

= log dt

70 a−x

d[O2 ]

a 0.0231 × 70 = k [N2O5] = k3[N2O5]

log = = 0.7021 dt

a−x 2.303

a k1 = 2k

Taking antilog, we get = 5.036 k k

a−x ∴ k 2 = 4k or k = 1 = 2 = k

k = k 2 4

a−x 1 3

∴ = ≈ 0.2

a 5.036

or 2k1 = k2 = 4k3.

when the concentration of both reactants is doubled Example 4: The reaction 2N2O5 → 4NO2 + O2 forms

the rate increased by a factor of 8, but when only the NO2 at the rate of 0.0072 mol L-1s-1 after a certain time.

concentration of Cl2 concentration is doubled, the rate

(a) What is the rate of change of [O2] at this time?

doubles. What is the order of the reaction with respect

to NO and Cl2? (b) What is the rate of change of [N2O5] at this time?

(c) What is the rate of reaction at this time ?

Sol: Rate = k [NO]m [Cl2]n

Let the concentrations of NO and Cl2 be x and y, Sol: The rate of the reaction is expressed as

respectively.

1 d[N2O5 ] 1 d[NO2 ] d[O2 ]

rate = – = + = +

R1 = kxm yn and, R2 = k (2x)m (2y)n 2 dt 4 dt dt

R2 and given that

∴ = 2m + n = 8 = 23. (given)

R1

d[NO2 ]

∴ m + n = 3 Again, R3 = k(x)m (2y)n =0.0072 molL-1s-1.

dt

R3

= k xmyn. 2n. ∴ = 2n = 2 (given) (a) Rate of appearance of

R1

∴ n = 1; m = 3 – 1 = 2. 1

O2 = × rate of appearance of NO2

4

Chem i str y | 18.31

= × = × 0.0072 = 0.0018 mole/L/s. at zero time is only for HCl. Thus we have

dt 4 dt 4

1 Time(min) : 0 20 119 ∞

(b) Rate of disappearance of N2O5 = × rate of

appearance of NO2 2 Vol. of alkali

(mL)used

d[N2O5 ] 1 d[NO2 ] 1 : 19.24 20.73 26.6 42.03

– = × = × 0.0072 against

dt 2 dt 2

CH3COOH

= – 0.0036 mole /L/s.

−19.24 −19.24 −19.24 −19.24

1 d[NO2 ]

(c) Rate of reaction = × = 0= 1.49 = 7.36 = 22.79

4 dt (x) (x) (a)

1

= × 0.0072 = 0.0018 (mole/L)s-1.

4 For t – 20;

k1= log =0.0033 min–1

O3 (g) + NO (g) → NO2 (g) + O2 (g) is 9.6 kJ/mol. Prepare 20 22.79 – 1.49

an activation energy plot it ∆H° for this reaction is -200 For t = 119 ;

kJ/mole. What is the energy of activation for the reverse 2.303 22.79

reaction? k 1= log =0.0032 min–1

119 22.79 – 7.36

Sol: Energy of activation for reverse reaction The constancy of k1 shows that the reaction is of first

= 9.6 + 200 kJ = 209.6 kJ. order.

k k

[Cr[H 2 O] 4 Cl 2 ] + (aq) → [Cr(H 2 O) 5 Cl 2 ] 2+ (aq)

1 2→

9.6kJ

E [Cr(H2O)6]3+(aq)

k1 = 1.76 × 10–3 s–1 and k2 = 5.8 × 10–5 s–1 for the initial

Energy

Calculate the value of t at which the concentration of

[Cr(H2O)5Cl2]2+ is maximum.

Reaction coordinate

2.303(logk1 – logk 2 )

Sol: We have, t =

Example 6: 1 mL of methyl acetate was added to 20 mL k1 – k 2

of 0.5 N HCl and 2mL of the mixture was withdrawn from

time tc during the progress of hydrolysis of the ester and 2.303(log1.76 × 10−3 – log5.8 × 10−5 )

= = 2005 seconds.

titrated with a solution of alkali. The amount of alkali 1.76 × 10 −3 − 5.8 × 10 −5

needed for titration at various intervals is given below:

Time: 0 20 119 ∞ (min) Example. 8: The complexation of Fe2+ with the chelating

agent dipyridyl has been studied kinetically in both

Alkali used: 19.24 20.73 26.6 42.03 (mL)

forward and reverse directions.

Establish that the reaction is of first order. Fe2+ + 3 dipy → Fe (dipy)32+

HCl

CH3COOCH3 + H2O

[H]

→ CH3COOH + CH3OH (reverse) = (1.22 × 10–4 [Fe (dipy)32+ ].

Ini.Conc. a Find the stability constant for the complex.

Conc. after t (a-x) x

Sol: At dynamic equilibrium, Rate of formation of

HCl acts as a catalyst. The alkali used against HCl is

complex = Rate of its decomposition

subtracted from the total alkali used (given in the data)

to get the volume of alkali used only against CH3COOH. (1.45 × 1013) [Fe2+][dipy]3 = (1.22 × 10–4 [Fe (dipy)32+ ]

1 8 . 3 2 | Chemical Kinetics

[Fe(dipy)32+ ] 1.45 × 1013

ka = = = 1.19 × 1017. (b) ln K = 14.34 – [(1.25 × 104)/500]

[Fe2+ ][dipy]3 1.22 × 10−4

(∵ T = 500 K)

parallel first order rearrangements. At 730 K, the first 0.693

order rate constant for the formation of cyclohexene (c) K = (for first order)

256 × 60

was measured as 1.26 × 10–4 sec-1, and for the formation

of methyl cyclopentane the rate constant was 3.8 × 0.693 1.25 × 10 4

∴ log = 14.34 –

10–5sec–1. What is the percentage distribution of the 256 × 60 T

rearrangement products? ∴ T = 513 K

Sol:

Example 2: The specific reaction rate of a first-order

k1

Cyclohexene reaction is 0.02 sec–1. The initial concentration of the

Bicyclohexane reactant is 2 molL–1. Calculate (a) initial rate, and (b) rate

after 60 sec.

k2 Methylcyclopentane

Sol: For a first-order reaction:

k1

Percentage of cyclohexene = × 100 Rate of a reaction = k × molar concentration of the

k1 + k 2

1.26 × 10 −4 reactant.

= × 100 = 77%

1.26 × 10−4 + 3.8 × 10−5 (a) ∴ Initial rate = k × initial concentration

2.303

(b) Concentration of the reactant after 60 sec k =

Example 10: A first-order reaction has a specific 2 60

reaction rate of 10–2 sec–1. How much time will it take log = 0.02.

concentration after 60 s

for 10 g of its reactant to be reduced to 2.5 g?

∴ Concentration of the reactant after 60 sec = 0.60 M.

Sol: Rate constant, k = 10–2 sec–1

∴ Rate after 60 sec = k × concentration of the reactant

Initial reactant conc. [A]0= 10 g after 60 sec.

Final reactant conc. [A]t = 2.5 g = 0.02 × 0.60 = 0.012 molL–1sec–1

Time required, t = ?

Example 3: The rate constant is numerically the same

For a first-order reaction.

for first, second and third order reaction, the unit of

t = 2.303 × 102log 4s = 230.3 × 0.6020s = 138.6s. concentration being in moles per litre. Which reaction

should be the fastest and is this true for all ranges of

concentrations ?

JEE Advanced/Boards

Sol: Suppose R1, R2 and R3 are the rates of reactions of

Example 1: The rate constant of a reaction is given by: ln first, second and third order, respectively, and k is the

K(sec–1) = 14.34 – (1.25 × 104)/T. Calculate (a) the energy rate constant, which is the same for the three reactions,

of activation and (b) the rate constant at 500 K. (c) At ∴ R1 = k[A]1 ; R2 = k[A]2 ; R3 = k[A]3

what temperature will its half-life period be 256 min?

[A] being the concentration of the reactant A in moles

Sol: Given: per litre.

(a) Comparing equations (i) and (ii), [A] > 1, R1< R2 < R3.

Example 4: For a reaction at 800°C

Chem i str y | 18.33

2NO + 2H2 → N2 + 2H2O, the following data were At ∞ time, i.e. when the reaction is complete, the whole

obtained: of C6H5N2Cl converts into N2. Hence volume of N2 at ∞

time corresponds to the initial concentration ‘a’ while

[NO]×10–4 mole/L [H2]×10–3 mole/L d[NO]/dt×10–4

volumes of N2 at different time intervals correspond to x

mole/L min

as shown above. substituting the given data in equation

(i) 1.5 7.0 4.4

of first-order reaction, we get the following results.

(ii) 1.5 3.5 2.2

(iii) 1.5 2.0 0.24 For t = 20 min

What is the order of this reaction with respect to NO 2.303 162

k1 = log = 0.0032 min–1

and H2 ? 20 162 − 10

For t = 50 min,

Sol: From the data (i) and (ii), we see that when the

concentration of H2 is halved, the rate is also halved at 2.303 162

k1 = log = 0.0033 min–1

constant concentration of NO. Hence the reaction is of 50 162 − 25

first order with respect to H2 Let us now consider the For t = 70 min,

data (ii) and (iii) to determine the order with respect to

2.303 162

NO as [H2] is constant. k1 = log = 0.0032 min–1

70 162 − 33

The rate law of the above reaction is

The consistency of k1 shows that the decomposition of

1 d[NO] C6H5N2Cl is a first-order reaction.

rate = – × = k[NO]m[H2]1

2 dt

Example 6: From the following reaction scheme, write

where, m is the order with respect to NO

the rate law for the disappearance of A, B and C.

d[NO] k

Or – = 2k[NO]m[H2] (1) A + B →C + D

1

dt k

(2) C + D

2→A + B

Substituting data (ii) and (iii), we get k

(3) B + C →E + D

3

2.2 × 10 = 2k(1.5 × 10 )m. (2 × 10 )

–4 –4 –3

...(i)

0.24 × 10–4 = 2k(0.5 × 10–4)m. (2 × 10–3) …(ii) Sol.: The reaction A is removed in step 1 and produced

in step 2

Dividing (i) by (ii),

d[A]

2.2 (1.5 × 10−4 )m 220 ∴– = k1[A] [B] – k2[C][D] Similarly

= = 3m or = 3m dt

0.24 (0.5 × 10−4 )m 24

d[B]

– = k1[A][B] + k3[B][C] – k2[C][D] and

Taking log, log 220 – log 24 = m log 3 dt

2.4324 – 1.3802 = m × 0.4771 d[C]

– = k2[C][D] + k3[B][C] – k1[A][B].

dt

0.9622

Or 0.9622 = 0.4771 m or m = = 2.

0.4771

Example 7: At a certain temperature, the half change

Hence the reaction is of second and first order with period for the catalytic decomposition of ammonia

respect to NO and H, respectively. were found as follows:

Pressure (Pascals): 6667 13333 26666

Example 5: From the following data for the de-

composition of diazobenzene chloride, show that the Half life period in hours: 3.52 1.92 1.0

reaction is of first order Calculate the order of reaction.

Time 20 50 70 ∞ (min) n−1

(t1/2 )1 a

Vol.of N2 10 25 33 162 (mL) Sol: = 2

(t1/2 )2 a1

Sol: C6H5N2Cl → C6H5Cl + N2

where, n is order of reaction

Initial concentration a n−1

3.52 13333

From the given data, =

After time t (a – x) x 1.92 6667

(a ∝ initial pressure) = (2)n –1

1 8 . 3 4 | Chemical Kinetics

log = (n – 1) log 2 = 0.3010 × (n – 1) (i) are 2.79 × 10–3 min–1 at 237°C and 12.0 kcal mol–1

1.92

respectively. These values for reaction (ii) are 1.52 × 10–4

0.2632 = 0.3010 × (n – 1) ; n = 1.87 ≈ 2 min–1 at 237°C and 24.5 kcal mol–1 respectively. Find out

Similar calculations are made between first and third the temperature at which equimolar quantities of H2O,

observations, n comes equal to 1.908 (≈ 2). CO, CO2 and H2 are formed (R = 2 cal).

Thus, the reaction is of second order. −Ea /RT

Sol: For reaction (a) K1 = A1e

Example 8: The optical rotation of can sugar in 0.5 N 12×103

–

acid at 25°C at various time intervals are given below: or 2.79 × 10–3 = A1e RT ……(i)

−Ea /RT

Time (min): 0 1435 11360 ∞ For reaction (b): K2 = A2e

24.5×103

Rotation(°): 34.50° 31.10° 13.98° – 10.77° –

1.52 × 10–4 = A2e RT …(ii)

Show that the reaction is of first order.

Sol: 2.79 × 10−3 2.79 × 10−3

By equation (i) A1 = =

Lactic acid –

12×103 7.8 × 10−6

C12H22O11

→ C6H12O6 + C6H12O6 e 2×510

By equation (ii) A2 = =

rotatory rotatory 24.5×103 − 11

– 3.7 × 10

Since in this reaction dextro form clianges to laevo

e 2×510

= 4.11 ×106

form, the optical rotation decreases with the progress

of the reaction. Thus change in rotation is proportional If rate constants of two reactions are same, the reactions

to the amount of sugar remaind after different time will give equimolar mixture of products. Let these be

intervals. We now have, same at temperature T, i.e.

−Ea /RT −Ea /RT

Time 0 1435 11360 ∞ A1e 1 = A2e 2

(min)

Ea −Ea [24.5 −12.0]×103

2 1 A2 A2

Change in 34.50 – 31.10 – 13.98 – – 10.77– ∴ e RT = or e RT =

rotation(°) (–10.77) (–10.77) (-10.77) (–10.77) A1 A1

= 45.27 =41.87 =24.75 =0 4.11 × 106

(a – x)

= = 1.15 × 104

(a) (a – x) 3.58 × 102

Substituting the data in equation, 103 12.5 × 103

Or 9.35 \T =

× 12.5 = = 668 K

for t = 1435 min RT 9.35 × 2

2.303 45.27 ∴ T = 668 K = 395°C

k1 = log = 5.442 × 10–5

1435 41.87

and for t = 1136 min Example 10: For the reversible reaction in equilibrium:

k

2.303 45.27

A ←

1

→ B. The values of K and K are 2 × 10–3 mol L–1

k1 = log = 5.311 × 10–5 k

1 2

1435 41.87 2

sec–1 and 3 × 10–3 mol L–1 sec–1 respectively. If we add 0.5

The values of k are fairly constant and so the reaction mol of B in the equilibrium mixture, initially containing

is of first order . 2 mol of A. Calculate the time taken for concentration

of B to become equal to 3/4 of the concentration of A

Example 9: The catalytic decomposition of formic acid at initial equilibrium. The volume of mixture is 1 L and

may take place in two ways: remains constant.

(i) HCOOH → H2O + CO 1

→ B

k

Sol: A ←

k

(ii) HCOOH → H2 + CO2 2

t=0 2 mol L –1

0

Chem i str y | 18.35

K1 = 2 × 10–3 mole L–1 sec–1 (zero order)

at t = 0, X = 0 ∴ C = – 2.303 log 0.66

K2 = 3 × 10 –3sec–1 (Ist order)

0.66

dX ∴ K2 . t = 2.303 log

= K1[A]0 – K2[B]1 0.66 – X

dt

2.303 0.66

dX ∴t= log = 89.24 sec

At equilibrium =0 3 × 10−3 0.66 – 0.155

dt

(a) Partial pressure becomes half of initial in every 100

K1 2 × 10−3

∴ 0=K1–K2[X]eq ; \[X]eq = = min, therefore, order = 1.

K2 3 × 10−3

800

= 0.66 mol L–1 = Kc (b) k × 100 = ln

400

A ←→B

k × 100 =ln 2

Initial eq. 1.34 0.66 ⇒ k = 6.93 × 10–3 min–1

Moles added 1.34 0.66+0.5= 1.16 (c) For 75% reaction; time required

At eq. at time t (1.34 +X) (1.16 –X) = 2 × half-life = 200 min

(The reaction will obey back ward direction on addition (d) 2X(g) → 3Y(g) + 2Z(g)

of B) 3

800 – x x

3 3 2

∵ [B] = [A]eq = × 1.34 = 1.005 3

4 4 Total pressure = 800 + x

2

(1.16 – X) = 1.005; ∴ X = 0.155 Also 800 – x = 700 ⇒ x = 100

3

⇒ Total pressure = 800 + × 100 = 950 mm

dX 2

Now, = K1 – K2[X] = 0.66K2 –K2 X

dt

dX

= K2[0.66 – X] ; ∴ = K2 . dt

(0.66 – X)

JEE Main/Boards

T according to the equation

Q.1 A solution of A is mixed with an equal volume of 2P(g) → 4Q(g) + R(g) + S(l)

a solution of B containing the same number of moles,

is the first order reaction. After 30 minutes from the

and the reaction A + B → C occurs. At the end of 1h,

start of decomposition in a closed vessel the total

A is 75% reacted. How much of A will be left unreacted

pressure developed is found to be 317 mm Hg and

at the end of 2h if the reaction is (a) first order in A and

after a long period of time the total pressure observed

zero order in B; (b) first order in both A and B; and (c)

to be 617 mm Hg. Calculate the total pressure of the

zero order in both A and B?

vessel after 75 minute, if volume of liquid S is supposed

to be negligible ,also calculate the tiny fraction t1/8.

Q.2 The reaction CH3–CH2–NO2+ OH– → CH3–CH–NO2-

+H2O obeys the rate law for pseudo first order kinetic Given: Vapor pressure of S () at temperature T = 32.5

in the presence of a large excess of hydroxide ion . If mm Hg.

1% of nitro ethane undergoes reaction in half minute

when the reaction concentration is 0.002 M, What is the Q.4 A certain reactant Bn+ is getting converted to

pseudo first order rate constant? B(n + 4)+ in solution. The rate constant of this reaction is

measured by titrating a volume of the solution with a

1 8 . 3 6 | Chemical Kinetics

reducing reagent which only reacts with Bn+ and B(n+4)+. Q.11 Two reactions

In this process, it converts Bn+ to B(n – 2)+ and B(n +4)+ to

(i) A → products

B(n – 1)+. At t = 0 the volume of the reagent consumed is

25 ml and at t = 10 min, the volume used up is 32 ml. (ii) B → products,

Calculate the rate constant of the conversion of Bn+ to follow first order kinetics. The rate of the reaction (i)

B(n + 4)+ assuming it to be a first order reaction. is doubled when the temperature is raised from 300

K to 310 K. The half-life for this reaction at 310 K is 30

Q.5 Decomposition of H2O2 is a first order reaction. A minutes. At the same temperature B decomposes twice

solution of H2O2 labelled as 20 volumes was left open as fast as A. If the energy of activation for the reaction

due to this, some H2O2 decomposed. To determine is half of that of reaction, calculate the rate constant of

the new volume strength after 6 hours 10 mL of this the reaction (ii) at 300 K

solution was diluted to 100 mL .10mL of this diluted

solution was titrated against 25mL of 0.025 M KMnO4 Q.12 A certain organic compound A decomposes by

solution under acidic conditions. Calculate the rate two parallel first order mechanism

constant for decomposition of H2O2.

k1 B

Q.6 A metal slowly forms an oxide film which completely A

protects the metal when the film thickness is 3.956 k2 C

thousand times of an inch. If the film thickness is 1.281

thou. in 6 weeks, how much longer will it be before it If k1: k2 = 1: 9 and k1 = 1.3 × 10–5s–1.

is 2.481 thou.? The rate of film formation follows first Calculate the concentration ratio of C to A, if an

order kinetics. experiment is started with only A and allowed to run

for one hour.

Q.7 An optically active compound A upon acid catalyzed

k

hydrolysis yield two optically active compound B and C +

Q.13 The reaction cis – Cr(en)2 (OH)2 ←

1

→ trans–

by pseudo first order kinetics. The observed rotation of k 2

the mixture after 20 min was 5° while after completion Cr(en)2 (OH)+ is first order in both directions. At 25°C

of the reaction it was – 20°. If optical rotation per mole 2

of A, B & C are 60°,40° & – 80°. Calculate half-life of the the equilibrium constant is 0.16 and the rate constant

reaction. k1 is 3.3 × 10–4 s–1. In an experiment starting with the

pure cis form, how long would it take for half the

Q.8 A vessel contains dimethyl ether at a pressure of equilibrium amount of the Trans isomer to be formed?

0.4atm. Dimethyl ether decomposes as CH3OCH3(g)

→ CH4(g) + CO(g) + H2(g). The rate constant of Q.14 For a reversible first-order reaction

k1

k1

decomposition is 4.78 × 10–3 min–1. Calculate the ratio k2

of initial rate of diffusion to rate of diffusion after 4.5 = 10–2 s–1 and [B]eq /[A]eq = 4. If [A]0 = 0.01 mole L–1 and

hours of initiation of decomposition. [B]0 = 0, what will be the concentration of B after 30 s?

Q.9 At room temperature (20°C) orange juice gets Q.15 For the system A ( g) → B ( g) , ∆H for the forward

spoilt in about 64 hours. In a refrigerator at 3°C juice reaction is –33kJ/mol (Note. ∆H = ∆E in this case).

can be stored three times as long before it gets spoilt.

Estimate (a) the activation energy of the reaction that Show that equilibrium constant

causes the spoiling of juice (b) How long should it take [B]

K= = 5.572 × 105 at 300 K. If the activation energies

for juice to get spoilt at 40°C? [A]

Er and Eb are in the ratio 20: 31. Calculate Er and Eb at this

Q.10 A first order reaction, A → B, requires activation temperature .Assume that the pre-exponential factor is

energy of 70 kJ mol–1.When a 20% solution of A was the same for the forward and backward reactions

kept at 25°C for 20 minutes, 25% decomposition took

place. What will be the percent decomposition in the Q.16 The complex [Co(NH3)5F]2+ reacts with water

same time in a 30% solution maintained at 40°C ? according to the equation

Assume that activation energy remains constant in this

range of temperature. [Co(NH3)5F]2+ + H2O → [Co(NH3)5(H2O)]3+ + F–

Chem i str y | 18.37

The rate of the reaction = rate const. x[complex]a x[H+]b. The initial pressure in a container of capacity V litres is

The reaction is acid catalysed i.e. [H+] does not change 1 atm. Pressure at time t = 10 sec is 1.4 atm and after

during the reaction. infinite time it becomes 1.5 atmosphere. Find the rate

constant k1 and k2 for the appropriate reaction.

Thus rate = k[Complex]a where k’ = k[H+]b calculate ‘a’

and ‘b’ given the following data at 25°C.

Q.21 A first order reaction takes 69.3 minutes for 50%

[Complex]M [H+ ]M T1/2hr T3/ 4hr completion. How much time will be needed for 80%

0.1 0.01 1 2 completion?

Q.22 The specific rate constant for a reaction increases

k

by a factor 4 of the temperature is changed from 27°C

Q.17 For the two parallel reactions A → B and

1

to 47°C. Find the activation energy for the reaction

k

2

A → C , show that the activation energy E’ for the

disappearance of A is given in terms of activation Q.23 The reaction 2A+ B + C → D + 2 E is of first order

k E + k 2E2 with respect to A and of second order with respect to B

energies E1 and E2 for the two paths by E’ = 1 1 and is of zero order with respect to C

k1 + k 2

(i) Write down the rate law for the reaction

Q.18 For the mechanism

(ii) What will be the effect of doubling concentration of

k

A + B ←

1 k3

→ C ; C →D

A, B and C.

k

2

(a) Derive the rate law using the steady-state Q.24 A first order reaction is 50% completed in 30 min

approximation to eliminate the concentration of C. at 27°C and in 10 minutes at 47°C. Calculate the rate

(b) Assuming that k3 << k2, express the pre-exponential constant at 27°C and the energy- of activation of the

factor A and Ea for the apparent second order rate reaction in kJ per mole

constant in terms of A1, A2 and A3 and Ea , Ea and Ea

1 2 3

for the three steps. Q.25 The optical rotation of sucrose in 0.5 M HCl at 35°

C at different time intervals are given below. Show that

Q.19 The reaction of formation of phosgene from CO the reaction follows first order kinetics

and Cl2 is CO + Cl2 → COCl2 Time (min) 0 10 20 30 40 ∞

The proposed mechanism is Rotation +32.4 +28.8 +25.5 +22.4 +19.6 –11.1

k1 (degrees)

(i) Cl2 ← →

2Cl (fast equilibrium)

k −1

k

(ii) Cl + CO ←

2 →

COCl (fast equilibrium) Q.26 t1/2 of a reaction is halved as the initial concentration

k −2

of the reaction is doubled, find out the order of the

(iii) COCl + Cl2

k3

→ COCl2 +Cl (slow)

reaction.

Show that the above mechanism leads to the following Q.27 The rate constant of a reaction is 1.5 × 10–7 sec–1

d[COCl2 ] at 50°C and 4.5 × 10–7 sec–1 at 100°C. Evaluate the

rate law = K[CO][Cl2]3/2.

dt Arrhenius parameters A and Ea.

1/2

k k Q.28 A substance reacts according to the law of first

Where K = k 3 ⋅ 2 1 .

k − 2k −1 order reaction the velocity constant of the reaction is

1.0 × 10–2 sec–1. If initial conc. of the substance is 1.0 M

Q.20 For the following first order gaseous reaction (a) Find out the initial rate

k1 (b) Find out the rate after 1 min.

2B(g

A(g)

Q.29 What will be initial rate of a reaction if its rate

k2

C(g) constant is 10–3 min–1 and concentration of reactant is

0.2 mol dm–3. How much of reactant will be converted

into products in 200 minutes.

1 8 . 3 8 | Chemical Kinetics

Q.30 A first order reaction is 20% complete in 10 Q.5 t1/4 can be taken as the time taken for the

minutes. Calculate concentration of a reactant to drop to 3/4 of its value.

If the rate constant for a first order reaction is k, the t3/4

(a) Specific rate constant of the reaction and

can be written as

(b) Time taken for the reaction to go to 75 % completion

(A) 0.69/k (B) 0.75/k (C) 0.10/k (D) 0.29/k

respect to the concentration of carbon monoxide. If

Single Correct Choice Type the concentration of carbon monoxide is doubled, with

everything else kept the same, the rate of reaction will

Q.1 For the reaction A + B → C; starting with different

initial concentration of A and B, initial rate of reaction (A) Double (B) Remain unchanged

were determined graphically in four experiments.

(C) Triple (D) Increase by a factor of 4

S. No. [A]0/M (Initial [B]0/M (Initial rate/ (M sec )

–1

1 1.6×10–3 5×10–2 10–3

A + 3B → P ∆H = –2x kJ/mole of A

2 3.2×10–3 5×10–2 4×10–3

3 1.6×10–3 10–1 2×10–3 and M → 2Q + R ∆H = –x kJ/mole of M

4 3.2×10–3 10–1 8×10–3 If these reactions are carried simultaneously in a

reactor such that temperature is not changing. If rate of

Rate law for reaction from above data is

disappearance of B is y M sec–1 then rate of formation

(A) r = k[A]2W2 (B) r = k[A]2[B] (in M sec–1) of Q is:

(C) r = k[ A] [B]2 (D) r = k[A][B] 2 3 4 3

(A) y (B) y (C) y (D) y

3 2 3 4

Q.2 The rate law for a reaction between the substances

A and B is given by rate = k [A]n [B]m On doubling the Q.8 Gaseous reaction A → B + C follows first order

concentration of A and halving the concentration of kinetics. Concentration of A changes from 1M to 0.25

B, the ratio of the new rate to the earlier rate of the M in 138.6 minutes. Find the rate of reaction when

reaction will be as concentration of A is 0.1 M.

(A) 2(n – m) (B) 1/2m + n (C) (m + n) (D) (n – m) (A) 2 × 10–3M min–1 (B) 10–3M min–1

(C) 10–4M min–1 (D) 5 × 10–4M min–1

Q.3 In a first order reaction, the concentration of the

reactant, decreases from 0.8 to 0.4 M in 15 minutes. The

time taken for the concentration to change from 0.1 M Q.9 The initial rate of zero-order reaction of the

to 0.025 M is gaseous reaction A(g) → 2B(g) is 10–2 M min–1. If the

initial concentration of A is 0.1M. What would be the

(A) 30 minutes (B) 15 minutes concentration of B after 60 sec?

(C) 7.5 minutes (D) 60 minutes

(A) 0.09 M (B) 0.01 M

Q.4 The rate equation for the reaction (C) 0.02 M (D) 0.002 M

Q.10 Consider the following first order competing

statement in relation to this reaction is

reactions:

(A) Unit of k must be s–1 k k

X → A + B and Y

1 → C + D if 50% of the reaction

2

(B) t1/2 is a constant of X was completed when 96% of the reaction of Y was

(C) Rate of formation of C is twice the rate of completed the ratio of their rate constants (k2/k1) is

disappearance of A (A) 4.06 (B) 0.215 (3) 1.1 (D) 4.65

(D) Value of k is independent of the initial concentration

of A and B

Chem i str y | 18.39

Q.11 At certain temperature, the half-life period for Q.16 The reaction A (g) → B(g) + 2C (g) is a first order

the thermal decomposition of a gaseous substance reaction with rate constant 3.465 × 10–6s–1.Starting with

depends on the initial partial pressure of the substance 0.1 mole of A in 2 litre vessel, find the concentration of

as follows A after 200 sec, when the reaction is allowed to take

place at constant pressure and temperature

P(mm Hg) 500 250

t1/2(in min) 235 950 (A) 0.05 M (B) 0.025 M

[Given log(23.5) = 1.37; log (95)= 1.97; log 2 = 0.30]

Q.17 In respect of the equation k = A exp (– Ea / RT),

(A) 1 (B) 2 (C) 2.5 (D) 3 which one of the following statements is correct?

(A) R is Rydberg’s constant

Q.12 Consider the reaction: A → B + C

(B) k is equilibrium constant

Initial concentration of A is 1M. 20 minutes time is

required for completion of 20% reaction. (C) A is adsorption factor

d[B] (D) Ea is the energy of activation

If =k[A], then half life (t1/2) is

dt

(A) 55.44 min (B) 50 min Q.18 Rate of a reaction can be expressed by Arrhenius

(C) 62.13 min (D) None of these equation as k = Ae–E/RT In this equation, E represents

(A) The fraction of molecules with energy greater than

Q.13 If decomposition reaction A(g) → B (g) follows the activation energy of the reaction

first order kinetics then the graph of rate of formation (B) The energy above which all the colliding molecules

(R) of B against time t will be will react

(A) R (B) R (C) The energy below which colliding molecules will not

react

(D) The total energy of the reacting molecules at a

temperature T.

t t

(C) R (D) R

Q.19 The rate constant, the activation energy and

the Arrhenius parameter (A) of a chemical reaction at

25°C are 3.0 × 10–4 s–1, 104.4 kJmol–1 and 6.0 × 104 S–1

t

respectively. The value of the rare constant at T → ∞

t

(A) 2.0 × 10–18s–1 (B) 6.0 × 1014s–1

(C) Infinity (D) 3.6 × 1030s–1

Q.14 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 Q.20 A first order reaction is 50% completed in 20

then rate constant for the backward reaction at this minutes at 27°C and in 5 min at 47°C. The energy of

temperature is activation of the reaction is

(A) 1.50 × 104L mol–1 s–1 (B) 1.5 × 1011L mol–1 s–1 (A) 43.85kJ/mol (B) 55.14kJ/mol

(C) 1.5 × 1010L mol–1 s–1 (D) 1.5 × 10–11L mol–1 s–1 (C) 11.97kJ/mol (D) 6.65kJ/mol

Q.15 Reaction A + B → C + D follows following rate law: Q.21 For the first order reaction A → B + C, carried out

rate = k[A]1/2[B]1/2. Starting with initial conc. of 1 M of A at 27°C if 3.8 × 10–16 % of the reaction molecules exists

and B each, what is the time taken for concentration of in the activated state, the Ea(activation energy) of the

A to become 0.25 M. reaction is [log 3.8 = 0.58]

Given: k = 2.303 × 10–3 sec–1 (A) 12 kJ/mole (B) 831.4kJ/mole

(A) 300sec. (B) 600 sec. (C) 900 sec. (D) 1200 sec. (C) 100 kJ/mole (D) 88.57kJ/mole

1 8 . 4 0 | Chemical Kinetics

Q.22 In a reaction carried out at 400 K , 0.0001% of the Q.6 The half-life period of a first order chemical reaction

total number of collisions are effective. The energy of is 6.93 minutes. The time required for the completion of

activation of the reaction is 99% of the chemical reaction will be (log 2 = 0.301)

(2009)

(A) Zero (B) 7.37k cal/mol

(A) 230.3 minutes (B) 23.03 minutes

(C) 9.212 k cal/mol (D) 11.05k cal/mol

(C) 46.06 minutes (D) 460.6 minutes

Previous Years’ Questions Q.7 A reaction involving two different reactants (2005)

Q.1 For a reaction A → 2B, rate of disappearance

2 (B) Can never be a unimolecular reaction

of ‘A’ is related to the rate of appearance of B’ by the

(C) Can never be a bimolecular reaction

expression (2008)

(D) Can never be a first order reaction

d[A] 1 d[B] d[A] d[B]

(A) – = (B) – =

dt 4 dt dt dt

Q.8 A reaction was found to be second order with

d[A] d[B] d[A] 1 d[B] respect to the concentration of carbon monoxide. If

(C) – =4 (D) – =

dt dt dt 2 dt the concentration of carbon monoxide is doubled with

everything else kept the same, the rate of reaction will

Q.2 The rate of a chemical reaction doubles for every (2006)

10° C rise of temperature. If the temperature is raised (A) Remain unchanged (B) Triple

by 50° C, the rate of the reaction increases by about (C) Increase by a factor of 4 (D) Double

(2011)

(A) 10 times (B) 24 times Q.9 For the reaction A + 2B → C, rate is given by R = [A]

[B]2 then the order of the reaction is (2002)

(C) 32 times (D) 64 times

(A) 3 (B) 6 (C) 5 (D) 7

Q.3 In a first order reaction the concentration of

reactant decreases from 800 mol/dm3 to 50 mol/dm3 Q.10The following mechanism has been proposed for

in 2 × 102 sec. The rate constant of reaction in sec–1 is the reaction of NO with Br2 to from NOBr: NO(g) +

(2003)

Br2 (g) ← → NOBr (g) NOBr (g) + NO(g) → 2NOBr

2 2

(A) 2 × 104 (B) 3.45 × 10–5 (g) If the second step is the rate determining step, the

order of the reaction with respect to NO(g) is (2006)

(C) 1.386 × 10–2 (D) 2 ×10–4

(A) 1 (B) 0 (C) 3 (D) 2

Q.4 Consider the reaction, 2 A + B → Products When

concentration of B alone was doubled, the half-life did Q.11 Consider the reaction Cl2(aq) + H2S(aq) → S(s) + 2H+(aq)

not change. When the concentration of A alone was + 2Cl–(aq) The rate equation for this reaction is rate =

doubled, the rate increased by two times. The unit of

k[Cl2][H2S] Which of these mechanisms is/are consistent

rate constant for this reaction is (2007)

with this rate equation

(A) L mol–1 s–1 (B) No unit

A. Cl2 + H2S → H+ +Cl– + Cl– + HS– (slow)

(C) mol L s

–1 –1

(D) s–1

Cl++ HS– → H+ + Cl– + S (fast)

Q.5 The rate constant for the reaction,

B. H2S ←→ H+ + HS– (fast equilibrium)

2N2O5 → 4NO2 + O2 is 3 ×10–5 sec–1. If the rate is Cl2 + HS– → 2Cl– + H+ + S (slow) (2010)

2.40 × 10–5mol litre–1 sec–1.

Then the concentration of N2O5 (in mol litre–1) is(2001) (A) A only (B) B only

(A) 1.4 (B) 1.2 (C) 0.04 (D) 0 (C) Both A and B (D) Neither A nor B

Chem i str y | 18.41

Q.12 The time for half life period of a certain reaction Q.18 The time for half-life period of a certain reaction A

A → Products is 1 hour. When the initial concentration → products is 1 hour. When the initial Concentration

of the reactant ‘A’ is 2.0 mol L–1, how much time does it of the reactant ‘A’, is 2.0 mol/L, how much time does

take for its concentration to come for 0.50 to 0.25 mol it take for its concentration to come from 0.50 to

L–1 if it is a zero order reaction (2010) 0.25 mol/L if it is a zero order reaction? (2010)

(A) 1 h (B) 4h (C) 0.5h (D) 0.25 h (A) 4 h (B) 0.5 h (C) 0.25 h (D) 1 h

Q.13 The energies of activation for forward and reverse Q.19 Consider the reaction: Cl2(aq) + H2S(aq) →

reactions for A2 + B2 → 2AB are 180kJ mol–1 and S(s) + 2H+(aq) + 2Cl– (aq) The rate equation for this

200kJ mol–1 respectively. The presence of catalyst lowers reaction is rate = k [Cl2] [H2S]

the activation energy of both (forward and reverse)

Which of these mechanisms is/are consistent with this

reactions by 100 kJ mol–1. The enthalpy change of the

rate equation? (2010)

reaction (A2 + B2 → 2AB) in the presence of catalyst will

be (in kJ mol–1) (2007) (A) Cl2 + H2 → H+ + Cl– + Cl+ + HS–(slow)

(A) 300 (B) -120 (C) 280 (D)- 20 Cl+ + HS– → H+ + Cl– + S (fast)

(B) H2S ⇔ H+ + HS– (fast equilibrium)

Q.14 Consider an endothermic reaction X → Y with

Cl2 + HS– → 2Cl– + H+ + S (slow)

the activation energies Eb and Ef for the backward and

forward reactions, respectively, in general (2005) (A) B only (B) Both A and B

(A) Eb < Ef (C) Neither A nor B (D) A only

(B) Eb >Ef

Q.20 The rate of a chemical reaction doubles for every

(C) Eb =Ef 10oC rise of temperature. If the temperature is raised by

(D) There is no definite relation between Eb and Ef 50oC, the rate of the reaction increases by about:

(2011)

Q.15 If ‘I’ is the intensity of absorbed light and C is the (A) 24 times (B) 32 times

concentration of AB for the photochemical process

(C) 64 times (D) 10 times

AB + hυ → AB*, the rate of formation of AB* is directly

proportional to (2001)

Q.21 For a first order reaction, (A) → products, the

(A) C (B) I (C) I2 (D) C.I concentration of A changes from 0.1 M to 0.025 M in 40

minutes. The rate of reaction when the concentration of

1

Q.16 For a reaction A → 2B , rate of disappearance A is 0.01 M is: (2012)

2

of ‘A’ is related to the rate of appearance of ‘B’ by the (A) 1.73 x 10–5 M/ min (B) 3.47 x 10–4 M/min

expression (2008)

(C) 3.47 x 10–5 M/min (D) 1.73 x 10–4 M/min

d[A] 1 d[B] d[A] 1 d[B]

(A) − = (B) − =

dt 2 dt dt 4 dt Q.22 The rate of a reaction doubles when its temperature

d[A] d[B] d[A] d[B] changes from 300 K to 310 K. Activation energy of

(C) − = (D) − 4

= such a reaction will be : (R = 8.314 JK-1 mol-1 and log

dt dt dt dt

2 = 0.301) (2013)

Q.17 The half-life period of a first order chemical (A) 53.6 kJ mol-1 (B) 48.6 kJ mol-1

reaction is 6.93 minutes. The time required for the (C) 58.5 kJ mol-1 (D) 60.5 kJ mol-1

completion of 99% of the chemical reaction will be

(log 2 = 0.301) (2009)

Q.23 . For the non-stoichiometry reaction 2A + B → C

(A) 230.3 minutes (B) 23.03 minutes + D, the following kinetic data were obtained in three

(C) 46.06 minutes (D) 460.6 minutes separate experiments, all at 298 K. (2014)

1 8 . 4 2 | Chemical Kinetics

Initial Initial Initial rate of Q.24 Decomposition of H2O2 follows a first order

Concentration (A) Concentration (A) formation (C) reaction. In fifty minutes the concentration of

(mol L-1s-1) H2O2 decreases from 0.5 to 0.125 M in one such

decomposition. When the concentration of H2O2

0.1 M 0.1 M 1.2 × 10-3

reaches 0.05 M, the rate of formation of O2 will be:

0.1 M 0.2 M 1.2 × 10-3 (2016)

0.2 M 0.1 M 2.4 × 10-3

(A) 6.93 × 10–4 mol min–1 (B) 2.66 L min–1at STP

The rate law for the formation of C is

(C) 1.34 × 10–2 mol min–1 (D) 6.93 × 10–2 mol min–1

dC dC

(A) = k[A][B] (B) = k[A]2 [B]

dt dt

dC dC

(C) = k[A][B]2 (D) = k[A]

dt dt

JEE Advanced/Boards

hydrogenation that the pressure of hydrogen gas

Q.1 Ammonia and oxygen reacts at higher temperatures decreases from 2 atmosphere to 1.1 atmosphere in 75

as 4NH3(g) + 5O2(g)→ 4NO(g) + 6H2O(g) minutes. Calculate the rate of reaction (in M sec–1) and

rate of reaction in term of pressure.

In an experiment, the concentration of NO increases by

1.08 × 10–2 mol litre–1 in 3 seconds. Calculate

Q.6 For the elementary reaction 2A + B2 → 2AB.

(i) Rate of reaction (ii) Rate of disappearance of Calculate how much the rate of reaction will change if

ammonia (iii) Rate of formation of water the volume of the vessel is reduced to one third of its

original volume?

Q.2 In the following reaction 2H2O2 → 2H2O + O rate of

formation of O2 is 3.6 M min–1 Q.7 For the reaction 3BrO– → BrO–3 +2Br– in an alkaline

(i) What is rate of formation of H2O? aqueous solution the value of the second order

(in BrO–) rate constant at 80°C in the rate law for

(ii) What is rate of disappearance of H2O2?

∆[BrO − ]

– was found to be 0.056L mol–1 s–1. What is the

∆t

Q.3 In a catalytic experiment involving the Haber rate constant when the rate law is written for

process N2 + 3H2 → 2NH3, the rate of reaction was

∆[BrO3− ] ∆[Br − ]

measured as (a) (b) ?

∆t ∆t

∆[NH3 ]

Rate = = 2 × 10 mol L s .

–4 –1 –1

∆t Q.8 Dinitropentoxide decomposes as follows:

If there were no side reactions, what was the rate of 1

N2O5(g) → 2NO2(g) + O2(g)

reaction expressed in terms of (a) N2, (b) H2? 2

Given that – d [N2O5]/dt = k1[N2O5]

Q.4 The reaction 2A + B + C → D + E is found to be d[NO2]/dt = k2[N2O5] ; d[O2]/dt = k3[N2O5]

first order in A second order in B and zero order in C. (1)

What is the relation between k1, k2 and k3?

Give the rate law for the reaction in the form of

differential equation.

Q.9 Suppose that the Sun consist entirely of hydrogen

(ii) What is the effect in rate of increasing concentrations atom and releases the energy by the nuclear reaction.

of A, B, and C two times?

Chem i str y | 18.43

411 H →2 He with 26 MeV of energy released. If the

1.5 × 10–3 sec–1. How long will 5.0 g of this reactant take

total output power of the Sun is assumed to remain to reduce to 1.25 g?

constant at 3.9 × 1026 W find the time it will take to burn

all the hydrogen. Take the mass of the Sun as 1.7 × 1030 kg.

Q.20 A drug is known to be ineffective after it has

decomposed 30%. The original concentration of a

Q.10 The reaction A(g) + 2B(g) → C(g) + D(g) is an sample was 500 units/ml. When analyzed 20 months

elementary process. In an experiment, the initial partial later, the concentration was found to be 420units/ml.

pressure of A & B are PA = 0.6 and PB = 0.8 atm. Calculate Assuming that decomposition is of first order, what will

the ratio of rate of reaction relative to initial rate when be the expiry time of the drug?

PC becomes 0.2 atm.

Q.11 In the given reaction, A → B rate constant is 1.2 × bath. The inactivation process was found to be first

10–2 M s–1. What is concentration of B after 10 and 20 order in virus concentration. At the beginning of the

min, if we start with 10 M of A. experiment 2.0% of the virus was found to be inactivated

per minute. Evaluate k for inactivation process.

Q.12 For the following data for the zero order reaction

A → products. Calculate the value of k. Q.22 If a reaction A → Products, the concentrations of

Time(min) [A] reactant A are C0, aC0, a2C0, a3C0 .........after time interval

0, t, 2t, 3t,........... where a is a constant. Given 0 < a < 1.

0.0 0.10 M Show that the reaction is of first order. Also calculate

1.0 0.09 M the relation between k,a and t.

2.0 0.08 M

Q.23 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.

Q.13 The rate constant for a zero order reaction is

What % of SO2Cl2 is decomposed on heating this gas

2 × 10–2 mol/L sec–1, if the concentration of the reactant

for 90 min?

after 25 sec is 0.25 M, calculate the initial concentration.

Q.14 A drop of solution (volume 0.10 ml) contains

follow first order kinetics are taken in such a way that

6 × 10–6 mole of H+, if the rate constant of disappearance

initially [A]= 4 [B]. Calculate the time after which the

of H+ is 1 × 107 mole liter–1 sec–1. How long would it take

concentration of both the substance will be equal.

for H+ in drop to disappear?

Q.15 A certain substance A is mixed with an equimolar

quantity of substance B. At the end of an hour A is 75% 2NO + H2 → N2 + H2O

reacted Calculate the time when A is 10% unreacted. Changes with the concentration of NO and H2 are

(Given: order of reaction is zero)

[NO] in M [H2] in M

1 d[NO]

− in M sec–1

Q.16 A first order reaction is 75% completed in 72 min. 2 dt

How much time will it take for (i) 50% completion

(i) 1.5×10–4 4 × 10–3 4.4 × 10–4

(ii) 87.5% completion.

(ii) 1.5×10–4 2 × 10–3 2.2 × 10–4

Q.17 A first order reaction is 20% complete in 10 min. (iii) 3.0×10–4 2 × 10–3 8.8 × 10–4

Calculate (i) the specific rate constant. (ii) the time taken

for the reactions to go to 75% completion. (a) What is the order of this reaction?

(b) What is the rate equation for the reaction?

Q.18 Show that in case of unimolecular reaction, the (c) What is the rate when

time required for 99.9% of the reaction to take place in

ten times that required for half of the reaction. [H2] = 1.5 × 1–3 M and [NO] = 1.1 × 1–3M?

1 8 . 4 4 | Chemical Kinetics

Q.26 The data below are for the reaction if NO and Cl2 Q.32 A → B + C

to form NOCl at 295 K

Time 0 t

Concentration of Concentration Initial Rate

Volume of reagent V1 V2

Cl2 [M] of NO (M s–1)

The reagent reacts with A, B and C. Find k.

0.05 0.05 1×10–3

0.15 0.05 3×10–3

[Assuming n-factor of A B & C are same]

Q.33 A → 2B + 3C

(a) What is the order w. r.t. NO and Cl2 in the reaction.

Time t ∞

(b) Write the rate expression

Volume of reagent V2 V3

(c) Calculate the rate constant

The reagent reacts with A, B and C.

(d) D

etermine the reaction rate when concentration of

Cl2 and NO are 0.2 M & 0.4 M respectively. Find k. [Assuming n-factor of A B & C are same]

°C and at an initial pressure of 200 mm is 50% complete

Time t ∞

in 53 minutes and 73% complete in 100 minutes

Rotation of Glucose & Fructose r1 r∞

(i) What is the order of the reaction?

(ii) Calculate the velocity constant Find k.

(iii) How much of H2O will decompose in 100 min. at the

3

same temperature but at initial pressure of 600 mm? Q.35 The reaction AsH3(g) → As(s) + H (g) was

2 2

followed at constant volume at 310°C by measuring

Q.28 The pressure of a gas decomposing at the surface the gas pressure at intervals. Show from the following

of a solid catalyst has been measured at different times figures that reaction is of first order.

and the results are given below

Time (in hrs) 0 5 7.5 10

t (sec) 0 100 200 300

Total pressure (in min) 758 827 856 882

Pa(Pascal) 4×103 3.5×103 3×103 2.5×103

Determine the order of reaction, its rate constant. Q.36 The thermal decomposition of dimethyl ether as

measured by finding the increase in pressure of the

Q.29 The half -life period of decomposition of a reaction.

compound is 50 minutes. If the initial concentration is (CH3)2O(g) → CH4(g)+H2(g)+CO(g) at 500°C is as follow:

halved, the half life period is reduced to 25 minutes.

What is the order of reaction? Time (sec.) 390 1195 3155 ∞

Q.30 In this case we have A → B + C (mm Hg)

Time t ∞ The initial pressure of ether was 312 mm Hg. Write the

rate equation for this reaction and determine the rate

Total pressure of A + B +C P2 P3

constant.

Find k.

Q.37 From the following data show that decomposition

Q.31 A → B + C of H2O2 in aqueous media is first order.

Total pressure of ( B +C) P2 P3 Volume (in c.c. of KMnO4) 22.8 13.3 8.25

Find k.

Chem i str y | 18.45

Q.38 The following data were obtained in experiment Q.43 The reaction A(aq) → B (aq) + C (aq) is monitored

on inversion of cane sugar by measuring optical rotation of reaction mixture

as different time interval .The species A, B and C are

Time 0 60 120 1805 360 ∞

optically active with specific rotations 20°, 30° and – 40°

(minute)

respectively. Starting with pure A if the value of optical

Angle of +13.1 +11.6 +10.2 +9.0 +5.87 –3.8 rotation was found to be 2.5° after 6.93 minutes and

rotation optical rotation was –5° after infinite time. Find the rate

(degree) constant for first order conversion of A into B and C.

would you expect a zero reading in polarimeter? Q.44 For a reaction k1 y

x

Q.39 At 100°C the gaseous reaction A → 2B + C was k2 zt

observed to be of first order. On starting with pure

A it is found that at the end of 10 minutes the total [x]t

Calculate value of ratio, at any given instant.

pressure of system is 176 mm Hg and after a long time [y] + [z]

270 mm Hg. From these data find (a) initial pressure

of A (b) the pressure of A at the end of 10 minutes B

k1

(c) the specific rate of reaction(d) the half-life period of Q.45 A

the reaction?

k2 C

[C]

Q.40 The decomposition of N2O5 according to the k1 = x hr–1; k1: k2 = 1: 10. Calculate after one hour

[A]

equation 2N2O5 (g) → 4 NO2(g) + O2(g) is a first order

reaction. After 30 min, from start of decomposition in a from the start of the reaction. Assuming only A was

closed vessel the total pressure developed is found to present in the beginning.

be 284.5 mm Hg. On complete decomposition, the total

pressure is 584.5 mm Hg. Calculate the rate constant of

Q.46 How much time would be required for B to reach

the reaction. k

maximum concentration for the reaction A →B

1

k

Q.41 A definite volume of H2O2 undergoing spontaneous

2

→ C.

decomposition required 22.8 c.c. of standard ln2 ln2

Given k1 = k =

permanganate solution for titration. After 10 and 20 4 2 2

minutes respectively the volumes of permanganate

required were 13.8 and 8.25 c.c. Q.47 For first order parallel reaction k1 and k2 are 8 and

(a) Find order of reaction. How may the result be 2 min–1 respectively at 300 K. If the activation energies

explained? for the formation of B and C are respectively 20 and

28.314 kJ/ mol respectively find the temperature at

(b) Calculate the time required for the decomposition

which B and C will be obtained in molar ratio of 2:1.

to be half completed.

k1 B

(c) Calculate the fraction of H2O2 decomposed after

A

25 minutes.

k2 C

Q.42 Hydrogen peroxide solution was stored in a mild [Given: ln4 = 1.4]

steel vessel. It was found, however, that the hydrogen

peroxide decomposed on the wall of the vessel Q.48 In gaseous reactions important for understanding

(a first order reaction) .An experiment with 100 ml of a the upper atmosphere, H2O and O react bimolecularly

solution gave 10.31 ml oxygen (corrected to 1 atm & to form two OH radicals. ∆H for This reaction is 72 kJ

273 K) after 5.1 days. Find how long the peroxide can at 500 K and Ea = 77 kJ mol–1, then calculate Ea for the

be stored before the loss of 20.00 ml oxygen occurs bimolecular recombination of 2OH radicals to form

(per 100 ml solution) under similar storage conditions H2O and O at 500 K.

if complete decomposition of the H2O2sample gave

46.34 mL oxygen.

1 8 . 4 6 | Chemical Kinetics

Q.49 The energy of activation of a first order reaction Q.58 Deduce rate law expressions for the conversion of

is 104.5 kJ mole–1 and pre - exponential factor (A) is H2 and I2 to HI at 400°C corresponding to each of the

5 × 1011 sec–1. At what temperature, will the reaction following mechanisms:

have a half-life of 1 minute?

(a) H2 + I2 → 2HI (one step)

by a factor of 4. If the temperature is changed from 27°C 2I + H2 → 2HI (slow)

to 47°C. Find the activation energy for the reaction.

(c) I2 → 2I

Q.51 The energy of activation and specific rate I + H2 → IH2

constant for a first order reaction at 25°C are 100 kJ/

IH2 + I → 2HI (slow)

mole and 3.46 × 10–3 sec–1 respectively. Determine the

temperature at which half life of the reaction is 2 hours. (d) Can the observed rate law expression

rate = k[H2][I2] distinguish among these mechanisms?

Q.52 A catalyst lowers the activation energy for a

certain reaction from 75 kJ to 25 kJ mol–1. What will be (e) If it is known that ultraviolet light causes the reaction

the effect on the rate of reaction at 25°C after things of H2 and I2 to proceed at 200°C with the same rate law

being equal? expression, which of these mechanisms becomes most

improbable?

Q.53 Given that the temperature coefficient for the

saponification of ethyl acetate by NaOH is 1.75.

Calculate activation energy for the saponification of

Exercise 2

ethyl acetate.

Single Correct Choice Type

Q.1 The rate of a reaction is expressed in different ways

decomposition of H2O2 is 360 min. The energy of

as follows:

activation of the reaction is 200 kJ mol–1. Calculate the

time required for 75% decomposition at 450°C. 1 d[C] 1 d[D] 1 d[A] d[B]

+ =– = + =–

2 dt 3 dt 4 dt dt

Q.55 The reaction 2NO + Br2 → 2NOBr, is supposed to The reaction is:

follow the following mechanism

fast

(A) 4A + B → 2C + 3D

(i) NO + Br2

NOBr2

(B) B + 3D → 4A + 2C

slow

(ii) NOBr2 + NO → 2NOBr

(C) A + B → C + D

Suggest the rate law expression.

(D) B + D → A +C

Q.2 For the reaction system

following mechanism has been suggested 2NO → N2O2

equilibrium constant K1 (fast) 2NO (g) + O2 (g) → 2NO2(g) volume is suddenly

k2 reduced to half of its value by increasing the pressure

N2O2 + H2

→ N2O + H2O (slow)

k

on it. If the reaction is first order with respect to O2 and

N2O + H2 → H2 + H2O (fast)

3

second order with respect to NO the reaction rate will

Establish the rate law for given reaction. (A) Increase to four times of its initial value

(B) Diminish to one-fourth of its initial value

Q.57 Reaction between NO and O2 to form NO2 is

2NO + O2 → 2NO2 follows the following mechanism (C) Diminish to one-eight of its initial value

NO + NO N2O2 (in rapid equilibrium)

1

k −1

→ 2NO2 (slow)

k2

reactions for A2 + B2

2AB are 180 kJ mol–1 and

1 d[NO2 ] 200 kJmol respectively. The presence of catalyst lower

–1

Show that the rate of reaction is given by

= K [NO]2[O2] 2 dt the activation energy of both (forward and reverse)

Chem i str y | 18.47

reactions by 100 kJ mol–1. The magnitude of enthalpy Q.7 For the first order decomposition of SO2Cl2(g).

change of the reaction (A2 + B2 → 2AB) in the presence

SO2Cl2(g) → SO2(g) + Cl2(g) a graph of log (a0 – x) vs t is

of catalyst will be (in kJ mol–1).

shown in figure. What is the rate constant (sec–1)?

(A) 300 (B) 120 (C) 20 (D) –20

Time (min)

(0, 0) 2 4 6 8 10

Q.4 Which graph represents zero order reaction

-1

log(a0 - x)

[A(g) → B(g)]

-2

(A) (B)

d[B] -3

[B]

dt

t t

(C) 7.7 × 10–3 (D) 1.15 × 10–2

(C) (D)

Q.8 Decomposition of H2O2 is a first order reaction.

t1/2 t1/4

A solution of H2O2 labelled as “16.8 V” was left open

due to this, some H2O2 decomposed. To determine the

[A]0 [A]0 new volume strength after 2.303 hours. 20 mL of this

solution was diluted to 100 mL. 25 mL of this diluted

Q.5 Consider the reaction A → B, graph between solution was titrated against 37.5 mL of 0.02 M KMnO4

half-life (t1/2) and initial concentration (a) of the reaction is solution under acidic conditions [Given: STP is 1 atm

and 273 K].

The rate constant (in hr–1) for decomposition of H2O2 is:

t1/2 (A) 0.15 (B) 0.30 (C) 0.60 (D) 1.3

two experiments starting with two different initial

d[A] concentration of A is given in the following graph. The

Hence graph between – and time will be

dt reaction is represented as A (aq) → B(aq).

What is the rate of reaction (M/min) when concentration

(A) (B)

of A in aqueous solution was 1.8 M?

d[A] d[A]

dt dt

Concentration (M)

1.5

t

1.2

1

(C) (D)

0.8 Experiment-1

d[A] d[A] 0.6 Experiment-2

dt dt 5 10 15 20

time (min)

t t (A) 0.08 M min–1 (B) 0.036 M min–1

Q.6 The reactions of higher order are rare because (C) 0.13 M min–1 (D) 1 M min–1

Q.10 The following mechanism has been proposed for

energy

the exothermic catalyzed complex reaction.

(B) Many body collisions have a very low probability fast k k

A+B

IAB → AB+I

1 2→ P+A

(C)Many body collisions are not energetically favoured

If k1 is much smaller than k2. The most suitable

(D) Many body collisions can take place only in the qualitative plot of potential energy (PE.) versus reaction

gaseous phase. coordinate for the above reaction.

1 8 . 4 8 | Chemical Kinetics

(A)

(1) (2) (3) (4)

(A) ∆E for Ea for ∆Eoverall Ea for

P.E.

A+B A+P

IAB (B) Ea for ∆E for Ea for ∆Eoverall

AB+I

E+S→ES E+S→ES ES→EP for S®P

reaction coordinate

(B) (C) Ea for Ea for ∆Eoverall ∆E for

ES→EP EP→E+P for S®P EP→E+P

(D) Ea for Ea for Ea for ∆Eoverall

E+S→ES ES→EP EP→E+P for S®P

P.E.

AB+I A+P

A+B

IAB (E) ∆E for ∆Eoverall ∆E for Eafor

E+S→ES for S®P EP→E+P EP→E+P

reaction coordinate

(C)

Multiple Correct Choice Type

P.E.

A+B AB+I

A+P

polluting gases from thermal power plant but at the

IAB

same time it is decomposing & following first order

reaction coordinate kinetics with half-life of 100 days.

Based on above information select the true statement (s).

(D)

(A) Concentration of SO3 in Kota is 1.25 × 10–5 M

(Assume SO3 present in air reaches steady state)

P. E.

IAB A+P (assuming all SO3 to be dissolved in it) & resulting

reaction coordinate solution is titrated against 1 N NaOH solution, 15 ml is

required to reach end point

Q.11 The following mechanism has been proposed for

(C) An industry is manufacturing H2SO4 at the rate of

the reaction of NO with Br2 to form NOBr

980 kg per day with the use of SO3 in air it should use

NO(g) + Br2(g)

NOBr2(g)

8 × 105 litre air/day

NOBr2(g) + NO(g) → 2NOBr(g) (D) If SO3 emission is stopped then after 1000 days its

concentrations will reduce to ≈ 1.2 × 10–3 M.

If the second step is the rate determining step, the

order of the reaction with respect to NO(g) is

Q.14 For the reaction A → B. The rate law expression is

(A) 2 (B) 1 (C) 0 (D) 3

d[A]

– = k[A]1/2. If initial concentration of [A] is [A]0, then

dt

Q.12 Choose the correct set of indentifications.

2

(A) The integrated rate expression is k= (A1/2 − A1/2 )

t 0

Potential energy

K

(4) (C) The half-life period t1/2 =

(1)

(2) (3)

2[A]1/2

0

(D) The time taken for 75% completion of reaction

reaction coordinate

[A]0

t3/4 =

k

t1/2

a

Chem i str y | 18.49

2

k1=6.93 x 10 min

-1

B Q.19 Which of the following is/are correct statement?

Q.15 Consider the reaction, A (A) Stoichiometry of a reaction tells about the order of

C the elementary reaction.

k2=13.85 x 10 min-1

(B) For a zero-order reaction, rate and the rate constant

A, B and C all are optically active compound. If optical are identical

rotation per unit concentration of A, B and C are 60°, (C) A zero-order reaction is controlled by factors other

–72°, 42° and initial concentration of A is 2 M then than concentration of reactants.

select write statements(s).

(D) A zero-order reaction is always elementary reaction

(A) Solution will be optically active and dextro after

very long time

Assertion Reasoning Type

(B) Solution will be optically active and laevo after very

long time (A) S

tatement-I is true, statement-II is true and

statement-II is correct explanation for statement-I

(C) Half life of reaction is 15 min

(B) Statement-I is true, statement-II is true and

(D) After 75% conversion of A in to B and C angle of statement-II is NOT the correct explanation for

rotation of solution will be 36° statement-I

(C) Statement-I is true, statement-II is false.

Q.16 Which of the following statement is incorrect?

(D) Statement-I is false, statement-II is true.

(A) The order of reaction is the sum of powers of all the

concentration terms in the rate equation.

Q.20 Statement-I: A fractional order reaction must be

(B) The order of reaction with respect to one reactant

a complex reaction.

is the ratio of the change of logarithm of the rate of

the reaction to the change in the logarithm of the Statement-II: Fractional order of RDS equals to overall

concentration of the particular reactant, keeping the order of a complex reaction.

concentrations of all other reactants constant.

Q.21 Statement-I: Temperature coefficient of a one

(C) Orders of reactions cannot be fractional.

step reaction may be negative

(D) The order of a reaction can only be determined

Statement-II: The rate of reaction having negative

from the stoichiometric equation for the reaction.

order with respect to a reactant decreases with the

increase in concentration of the reactant.

Q.17 Select incorrect statement(s)

(A) Unit of pre-exponential factor (A) for second order Q.22 Statement-I: The overall rate of a reversible

reaction is mol L–1 s–1 reaction may decrease with the increase in temperature.

(B) A zero-order reaction must be a complex reaction Statement-II: When the activation energy of forward

reaction is less than that of backward reaction, then the

(C) Molecularity is defined only for RDS in a complex increase in the rate of backward reaction is more than

reaction that of forward reaction on increasing the temperature

(D) Decay constant (λ) of radioactive substance is

affected by temperature Q.23 Statement-I: In a reversible endothermic reaction

Ea of forward reaction is higher than that of backward

E reaction.

1

Q.18 In a consecutive reaction system A → B

E Statement-II: The threshold energy of forward reaction

→ 2 C when E1 is much greater than E2, the yield of is more than that of backward reaction.

B increase with

(A) Increase in temperature Q.24 Statement-I: The time of completion of reaction

of type A → product

(B) Decreases in temperature

(order < 1) may be determined.

(C) Increase in initial concentration of A

Statement-II: Reactions with order ≥ 1 are either too

(D) Decrease in initial concentration of A slow or too fast and hence the time of completion

cannot be determined

1 8 . 5 0 | Chemical Kinetics

Q.25 Statement-I: A catalyst provides an alternative Q.30 What will be the concentration of A at time t, if

path to the reaction in which conversion of reaction n1 = 1 and n2 = 2 ?

into products takes place quickly e−kt

(A) [A0] .e–kt (B) [A0 ]

Statement-II: The catalyst forms an activated complex 2 − e−kt

of lower potential energy with the reactants by which

e−kt

more number of molecules are able to cross the barrier (C) [A0 ] (D) [A0](1 – 2 . e–kt)

per unit of time. 1 − e−kt

Paragraph 3

Comprehension Type

For the reaction sequential reaction

Paragraph 1 k k

k1 B A → B

1 2→ C

For a hypothetical elementary reaction A

the concentration of A, B & C at anytime ‘t’ is given by

k2 C

k1 1 k1 [A]0 −k1t −k 2t

where = . Initially only 2 moles of A is present. [A]1 = [A]0e–kt ; [B]1 = [e −e ]

k2 2 (k 2 – k1 )

[C]1 = [A0] – ([A]1 + [B]1)

Q.26 The total number of moles of A, B & C at the end

of 50% reaction are Q.31 The time at which concentration of B is maximum is

(A) 2 (B) 3 (C) 4 (D) 5 k1 k

1

(A) (B) ln 1

k 2 − k1 k 2 − k1 k 2

Q.27 Number of moles of B are

(A) 2 (B) 1 (C) 0.666 (D) 0.33 1 k k2

(C) ln 1 (D)

k1 − k 2 k 2 k 2 − k1

Paragraph 2

The gaseous reaction: n1 A(g) → n2B (g) is first order Q.32 Select the correct option if k1 = 1000s–1 and

with respect to A. The true rate constant of reaction is k2 = 20s–1.

k. The reaction is studied at a constant pressure and

temperature. Initially, the moles of A were ‘a’ and no B (A) [C]1 (B) [C]1

were present.

Conc.

Conc.

[B]1

[A]1 [B]1 [A]1

Q.28 How many moles of A are present at time, t? time time

−n1kt

(A) a ⋅ e-kt (B) a ⋅ e

(C) [C]1 (D) [C]1

−n2kt −n2kt

(C) a ⋅ e (D) a(1 − e )

Conc.

Conc.

[B]1

Q.29 If the initial volume of system were v 0° then the [B]1 [A]1 [A]1

volume of system after time t will be time time

n1 v 0

(A)

n2 Paragraph 4

(B) reaction involving many steps. These steps involve

n1

electron transfer reactions. A particular type of oxidation

n involve overall first order kinetics with respect to fraction

n −n kt

(C) v 0 2 + 1 − 2 ⋅ e 1 of unoxidised metal (1 – ƒ) surface thickness relative to

n1 n1 maximum thickness (T) of oxidised surface, when metal

surface is exposed to air for considerable period of time

n n −n kt

(D) v 0 2 + 2 – 1 ⋅ e 2 Rate law: = k(1 – ƒ), where f = x/T,

n1 n1

Chem i str y | 18.51

0 t

time ‘t' and Q.37 For the reaction of type A(g) → 2B(g)

T = thickness of oxide film at Column I contains four entries and column II contains

t=∞ four entries. Entry of column I are to be matched with

A graph of ln( 1 – ƒ) vs t is

-3 only one entry of column II

shown inthe adjacent figure. In(1-)

Column I Column II

Q.33 The time taken for thickness to grow 50% of T is

(p)

d[B] −d[A]

(A) 23.1 hrs (B) 46.2hrs (A) vs

dt dt

(C) 100 hrs (D) 92.4 hrs for first order

(A) [1 – e–3t/200] (B) e–3t/200–1

(B) [A] vs t for first (q)

(C) e–3t/200 (D) e3t/200

order

Paragraph 5

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) (C) [B] vs t for first (r)

order

At t = 0 a 0 0

At time t a-x x x

dx

The rate of reaction is govern by the expression

dt

= k(a – x) and integrated rate equation for a given

reaction is represented as (D) [A] vs t for zero (s)

a order

1

k= ln a − x where a = initial concentration and

t

(a – x) = concentration of A after time t.

order reaction .If 75% of X is decomposed in 100 min.

How long will it take for 90% of the compound to Q.38 Column-I and column-II. Entry of column-I are

decompose? Given: log 2 = 0.30 to be matched with one or more than one entries of

(A) 190 min (B) 176.66 min column-II and vice versa.

(C) 166.66 min (D) 156.66 min Column-I (Graphs Column-II (Co-ordinates)

reaction A → Products)

(A) (p) ln [A] (y-axis), t(x-axis)

Q.36 Consider a reaction A(g) 3B(g) + 2C(g) with

(order = 1)

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 298 K 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

1 8 . 5 2 | Chemical Kinetics

(B) (q) t1/2(y-axis), [A0] (x-axis)

about order of reaction? (2005)

(order = 1)

(A) Order of reaction is determined experimentally

(B) Order of reaction is equal to sum of the power of

concentration terms in differential rate law

(C) It is not affected with stoichiometric coefficient of

(C) (r) r(y-axis), t(x-axis)(order > 0) the reactants

(D) Order cannot be fractional

(k) with temperature (T) are given below. The plot that

follows Arrhenius equation is (2010)

(A) (B)

(D) (s) r(y-axis), t(x-axis)(order = 0)

(t) t 1/2(y-axis), [A0] (x-axis) (order K K

> 1)

1 T T

(u) (y-axis), t(x-axis)

[A] (C) (D)

(order = 2)

K K

(v) r (y-axis), [A](x-axis)(order = 1)

Comprehension (Q.6), (Q. 7), (Q.8)

Q.1 The rate constant of a reaction depends on(1981) Carbon-14 is used to determine the age of organic

(A) Temperature material. The procedure is based on the formation of

14

C by neutron capture in the upper atmosphere.

(B) Initial concentration of the reactants

14

14

(C) Time of reaction 7 N +0 n1 →6 C +1 p1

(D) Extent of reaction 14

C is absorbed by living organisms during

photosynthesis. The 14C content is constant in living

Q.2 A catalyst is a substance which (1983) organism once the plant or animal dies, the uptake

(A) Increases the equilibrium concentration of the of carbon dioxide by it ceases and the level of 14C in

product the dead being, falls due to the decay which C–14

14

14

(B) Changes the equilibrium constant of the reaction undergoes 6 C →7 N + β–

(C) Shortens the time to reach equilibrium The half-life period of 14C is 5770 yr.

(D) Supplies energy to the reaction The decay constant (λ) can be calculated by using the

following formula

Q.3 If I is the intensity of absorbed light and C is the 0.693

λ=

concentration of AB for the photochemical process. t1/2

AB + hv → AB*, the rate of formation of AB* is directly The comparison of the β– activity of the dead matter

proportional to (2001) with that of the carbon still in circulation enables

measurement of the period of the isolation of the

(A) C (B) I (C) I2 (D) C.I

material from the living cycle. The method however,

ceases to be accurate over periods longer than 30,000

yr. The proportion of 14C to 12C in living matter is

1: 1012. (2006)

Chem i str y | 18.53

Q.6 Which of the following option is correct? Q.11 A first order gas reaction has A’ = 1.5 × 10–6 per

second at 200° C. If the reaction is allowed to run for 10

(A) In living organisms, circulation of 14C from

h, what percentage of the initial concentration would

atmosphere is high so the carbon content is

have change in the product? What is the half-life of this

constant in organism

reaction? (1987)

(B) Carbon dating can be used to find out the age of

earth crust and rocks

Q.12 An experiment requires minimum beta activity

(C) Radioactive absorption due to cosmic radiation is produced at the rate of 346 beta particles per minute.

equal to the rate of radioactive decay, hence the The half-life period of 42Mo99 which is a beta emitter is

carbon content remains constant in living organisms 66.6 h. Find the minimum amount of 42Mo99 required to

carry out the experiment in 6.909 h. (1989)

(D) Carbon dating cannot be used to determine

concentration of 14C in dead beings.

Q.13 The gas phase decomposition of dimethyl ether

follows first order kinetics

Q.7 What should be the age of fossil for meaningful

determination of its age? CH3–O–CH3(g) → CH4(g)+ H2(g)+CO(g)

(A) 6 yr The reaction is carried out in a constant volume

container at 500°C and has a half-life of 14.5 min.

(B) 6000 yr

Initially only dimethyl ether is present at a pressure of

(C) 60,000 yr 0.40 atm. What is the total pressure of the system after

(D) It can be used to calculate any age 12 min? Assume ideal gas behaviour. (1993)

Q.8 A nuclear explosion has taken place leading to Q.14 (a) The rate constant of a reaction is 1.5 × 107 s–1 at

increase in concentration of C14 in nearby areas. C14 50° C and 4.5 × 107 s–1 at 100°C. Evaluate the Arrhenius

concentration is C1 in nearby areas and C2 in areas far parameters A and Ea. (1998)

1

away. If the age of the fossil is determined to be T1 and (b) For the reaction, N2O5 (g) → 2NO2 (g) + O2 (g)

T2 at the places respectively then 2

calculate the mole fraction N2O5(g) decomposed at a

(A) The age of fossil will increase at the place where constant volume and temperature, if the initial pressure

1 C is 600 mm Hg and the pressure at any time is 960 mm

explosion has taken place and T1 – T2 = ln 1

λ C2 Hg. Assume ideal gas behaviour.

(B) The age of fossil will decrease at the place where

1 C Q.15 2X(g) → 3Y(g) + 2Z(g)

explosion has taken place and T1 – T2 = ln 1

λ C2

Time (in min) 0 100 200

(C) The age of fossil will be determined to be the same

Partial pressure of X (in mm of Hg) 800 400 200

T1 C1

(D) =

T2 C2 Assuming ideal gas condition. Calculate (2005)

(A) Order of reaction

Q.9 The concentration of R in the reaction

(B) Rate constant

R → P was measured as a function of time and the

(C) Time taken for 75% completion of reaction.

following data obtained:

(D) Total pressure when px = 700 mm

[R] (molar) 1.0 0.75 0.40 0.10

t (min) 0.0 0.05 0.12 0.18 Q.16 Consider a reaction aG + bH → Products.

When concentration of both the reactants G and H is

The order of the reaction is (2010)

doubled, the rate increases by eight times. However,

when concentration of G is doubled keeping the

Q.10 Radioactive decay is a first order process. Radioactive concentration of H fixed, the rate is doubled. The

carbon in wood sample decays with a half-life of 5770 yr. overall order of the reaction is (2007)

What is the rate constant (in yr–1) for the decay? What

fraction would remain after 11540 yr? (1984) (A) 0 (B) 1 (C) 2 (D) 3

1 8 . 5 4 | Chemical Kinetics

concentration of 1.386 mol dm-3 of a substance [Q]0

becomes half in 40 seconds and 20 seconds through [Q]

first order and zero order kinetics, respectively. Ratio 1

k1

of the rate constants for first order (k1) and zero

k0

order (k0) of the reactions is (2008) Time

(A) 0.5 mol-1 dm3 (B) 1.0 mol dm-3 (A) 2 (B) 3 (C) 0 (D) 1

(C) 1.5 mol dm-3 (D) 2.0 mol-1 dm3

Q.20 For the elementary reaction M → N, the rate

of disappearance of M increases by a factor of 8 upon

Q.18 An organic compound undergoes first-order

doubling the concentration of M. The order of the

decomposition. The time taken for its decomposition

reaction with respect to M is (2014)

to 1/8 and 1/10 of its initial concentration are t1/8 and

[t ] (A) 4 (B) 3 (C) 2 (D) 1

t1/10 respectively. What is the value of 1/8 × 10? (take

[t1/10 ]

log102=0.3) (2013) Q.21 According to the Arrhenius equation, (2015)

(A) A high activation energy usually implies a fast

Q.19 In the reaction, P + Q → R + S the time reaction

taken for 75% reaction of P is twice the time taken for (B) Rate constant increases with increase in temperature.

50% reaction of P. The concentration of Q varies with This is due to a greater number of collisions whose

reaction time as shown in the figure. The overall order energy exceeds the activation energy

of the reaction is (2013)

(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.

Exercise 1 Exercise 1

Q.1 Q.4 Q.7 Q.9 Q.7 Q.9 Q.20 Q.36

Exercise 2 Exercise 2

Q.2 Q.10 Q.16 Q.8 Q.12 Q.28 Q.29

Q.33 Q.34 Q.37

Previous Years’ Questions

Q.9 Q.14 Q.15

Q.12 Q.15

Chem i str y | 18.55

Answer Key

Q.18 (a) =

dt k 2 + k3

Exercise 1 A1 A3

(b) Ea = Ea1 + Ea3 – Ea2 A =

Q.1 (a) 6.25 ; (b) 14.3; (c) 0 % A2

Q.2 2 × 10–2 min–1 Q.20 0.0805

Q.5 k = 0.022 hr–1 Q.23 Rate = K(A][13]2 rate will became 8 times

Q.9 (a) 43.46 kJ mol–1 (b) 20.47 hour Q.25 It is first order kinetics with

A = 5.42 × 1010

Q.15 Er=6 × 104 J; Eb = 9.3 × 104 J (b) = 5.495 × 10–3 mol–1 l–1 s–1

E1k1 + E2k 2 Q.30 k = 0.02231 min–1 t = 62.07 min

Q.17 E=

k1 + k 2

Exercise 2

Q.7 C Q.8 B Q.9 C Q.10 D Q.11 D Q.12 C

Q.13 C Q.14 D Q.15 B Q.16 A Q.17 D Q.18 C

Q.19 B Q.20 B Q.21 C Q.22 D

Q.1 A Q.2 C Q.3 C Q.4 A Q.5 D Q.6 C

Q.7 B Q.8 C Q.9 A Q.10 D Q.11 A Q.12 D

Q.13 D Q.14 A Q.15 B Q.16 B Q.17 C Q.18 C

Q.19 D Q.20 B Q.21 B Q.22 A Q.23 D Q.24 A

1 8 . 5 6 | Chemical Kinetics

Exercise 1

(c) 8.85 ×10–3 M sec–1

1 d[NO]

Q.1 (i) r= = 9 × 10–4 mol litre–1 sec–1 Q.26 (a) Order w.r.t. NO = 2 and w.r.t. Cl2 = 1,

4 dt

(b) r = K[NO]2[Cl2],

(ii) 36 × 10–4 mol litre–1 sec–1

(c) K = 8 L2 mol–2s–1,

(iii) 54 × 10–4 mol litre–1 sec–1

(d) Rate = 0.256 mole L–1 s–1

Q.2 (i) 7.2 mol litre min ,

–1 –1

(ii) 7.2 mol litre–1 min–1

(ii) k = 1.308 × 10–2 min–1

Q.3 (a) 1 × 10–4 mol L–1 s–1, (iii) 73%

(b) 3 × 10 mol L s

–4 –1 –1

Q.4 (i) = k [A][B]2

dt

Q.29 Zero order

(ii) Rate increases by 8 times

1 P3

Q.5 7.23 × 10–6 Ms–1, 0.012 atm min–1 Q.30 k = ln

t 2(P3 − P2 )

Q.6 Rate increases by 27 times

1 P3

Q.31 k = ln

Q.7 (a) 0.019 mol L s ,

–1 –1 t (P3 − P2 )

Q.32 k = ln

t (2V1 − V2 )

Q.8 2k1= k2 = 4k3

1 4V3

Q.33 k = ln

Q.9 2.72 × 10 sec

18

t 5(V3 − V2 )

Q.10 1/6 1 r

Q.34 k = ln ∞

t (r∞ − r1 )

Q.11 (i) 7.2 M, (ii) 10 M

Q.35 First order

Q.12 K= 0.01 M min –1

Q.36 (i) r = K[(CH3)2O]2 0.000428 sec–1

Q.13 0.75 M Q.37 First order

Q.14 6 × 10–9 sec Q.38 966 min

(b) 47 mm,

Q.16 (i) 36 min (ii) 108 min

(c) 6.49 × 10–2 per minutes,

Q.17 (i) 0.0223 min , (ii) 62.17 min

–1

(d) 10.677 min.

Q.19 924.362 sec Q.40 k1 =2.605 × 10–3 min–1

(b) 13.75 minutes,

Q.21 3.3 × 10–4 s–1

(c) 0.716 0.180 atm, 47.69 sec

2.303 1

Q.22 k = log

t a Q.42 11.45 days

Q.23 11.2% Q.43 0.1 min–1

Chem i str y | 18.57

1 Q.51 306 K

Q.44

e

(K1 +K2 )

t −1 Q.52 Rate of reaction increases 5.81 × 108 times

Q.45 = (e – 1)

[A] 11 Q.54 t=20.4 minutes 56. 2000 K

Q.46 t = 4 min Q.55 r = K’ [NO]2 [Br2]

Q.47 0379.75 K Q.56 k = k'2

Q.48 5 kJ mol–1 Q.57 r = K[NO]2 [H2], where K=k2 × K1/k-1

Q.49 349.1 K Q.58 (d) No, (e) mechanism (a) is incorrect

Q.50 55.33 kJ mole –1

Exercise 2

Q.19 A, B, C

Comprehension Type

Q.37 A → s; B → r; C → p; D → q Q.38 A → p; B → q, s; C → r, t; D → v

Q.15 (a) 1 (b) 693x10-3 min-1 (c) 200 min (d) 950 mm Q.16 D

1 8 . 5 8 | Chemical Kinetics

Solutions

JEE Main/Boards 3

⇒k=

[A0 ]

Exercise 1

Now, at time t = 2 hours,

Sol 1: (a) A + B → C −1 1 3 −6

+ = –2 × =

We have, first order in A and 0 order in B. [A] [A0 ] [A0 ] [A0 ]

−d[A] −d[A] 1 7 [A] 1

Rate = = k[A] 1[B] 0 = = – k[A] ⇒ = ⇒ =

dt dt [A] [A0 ] [A0 ] 7

For first order reaction, we know

100

A left is % or 14. 3 %

[A] = [A0] e–kt 7

We have, at t = 1 hour

(c) If the reaction is 0 order

75% of A reacted

d[A]

1 Rate = =k

[A] = A0 – 0. 75; A = A0 dt

4 [A] t

1 ⇒ ∫ d[A] = ∫ k dt

[A ] = [A0] e–kt ⇒ k = ln 4

4 0 [A0 ] 0

[A] 1

= e–2×ln 4 = ⇒ [A] = [A0]-kt

[A0 ] 16

Now, at time t = 1 hour

[A] = 6. 25 % of A0 [A0 ]

[A] =

∴6. 25% of A will be left unreacted. 4

[A0 ]

– [A0] = –k

(b) Here, reaction is first order in both A and B 4

3

d[A] ⇒k= [A ]

∴Rate = = k[A] [B] 4 0

dt

We see that, if t or [A] = 0

Since the initial concentration of A and B is the same

and they have the same coefficient, their concentration [A0 ] 4

t= = hours < 2 hours

will remain same at any time. k 3

−d[A] The reactions will be finished before 2 hours and 6 % of

= k[A] 2 A will be left after 2 hours.

dt

[A] t −

d[A]

⇒ ∫ = ∫ −kdt Sol 2: CH3CH2NO2 + OH– → CH3 CHNO2 + H2O

2

[A0 ] [A] 0 (A)

Since this is a first order reaction

1 1 [A] = [A0] e–kt

⇒− + = –k(t – 0) = kt

[A] [A0 ] 1

Now, we have at time t = minute,

2

[A0 ]

At time t = 1 hour, [A] = [A] = 0. 99[A0]

4

4 1 (1 % of nitroethane reacted)

∴− + = –k

[A0 ] [A0 ] ∴0. 99[A0] = [A0] e–k. 1/2

Chem i str y | 18.59

⇒ P0 – 2x = 158. 22

⇒ −k = loge(0. 99)

2 233.8 − 158.22

−k ⇒x= = 37. 78

⇒ = 0. 01 min. 2

2

Now, total pressure at t = 75 min

⇒ k = 0. 02 min–1

Pt = P0 + 3x + 32. 5

k = 2 × 10–2 min–1

= 233. 8 + (3 × 37. 78) + 32. 5

as the liquid begins to form, pressure due to liquid will

7

Time fraction, t7/8 is time at which th of reaction gets

always be equal to 32. 5 mm Hg. Now, let initial pressure 8

P

of P(g) be P0 mm Hg, then according to stoichiometry completed, ie. P∆ = 0

8

P0 2.303

2P(g) → 4Q(g) + R(g) + S() Using rate law, = P0e –kt ⇒ t = log 8

8 R

at time t = 399. 96 min.

t = 0 min P0 0 0 0

Sol 4: We have, the reaction as,

t = 30 min P0 – 2x 4x x 32. 5

Bn+ → B(n-2)+ + 4e

t = ∞ 0 2P0 P0 32. 5

At time t = 0 V0 0

2

Now, we are given, Pt = 317 mm Hg at t=30 min. total time

∴P0 – 2x + 4x + x + 32. 5 = 317 t = 10 min V0 – x x

⇒ P0 + 3x = 284. 5 …….(i) Now, for titration we have

At time, t = ∞ (very long time), Pt = 617 mm Hg Bn+ + 2e → B(n–2)+

P0 From this, we see that for volume V0 of Bn+, 2V volume

∴2P0 + + 32. 5 = 617

2 of titrant is used.

5P0 at time t = 0, volume of titrant used = 25 mL

⇒ = 584. 5

2

⇒ 2V0 = 25 mL

⇒ P0 = 233. 8 mm Hg

⇒ V0 =12. 5 mL

Putting this in (i), we get,

For titration of B(n–1)+, we have

3x = 284. 5 – 233. 8

B(n+4)+ + 5e → B(n–1)-

⇒ x = 16. 9

i.e. for volume V of Bn+ + B(n+4), 5V volume of titrant is

Now, since this is first order reaction, we have used.

at t = 30 min a = 233.8 x = 16.9 ∴ At time t = 10 min,

2.303 P 2.303 233.8 Volume of titrant used = 32 mL

k= log 0 = log

t Pp 30 233.8 − (2 × 16.9) ⇒ 2(V0 – x) + 5x = 32

⇒ k = 5.2 × 10–3 min–1

⇒ 2V0 + 3x = 32

Now, at t = 75 min, we have

⇒3x = 32 – 25

2.303 P

k= log 0 7

t Pp ⇒x=

3

⇒ Pt = P0 × 10–kt/2. 303 Now, since this is a first order reaction, rate law is

–5.2×10 –3 ×75 2.303 V 2.303 12.5

= 233. 8 × 10 2.303 k= log 0 = log

t V n+ 10 12.5 − x

B

Pt = 158. 22 m Hg

1 8 . 6 0 | Chemical Kinetics

= log ; k = 0. 0207 min–1 k= log

10 7 6 3.956 – 1.281

12.5 −

3 k = 0. 065

Sol 5: We have initially, volume strength = 20 2.481

Now, when, τ = inch, we have

According to reaction 1000

2.303 3.956

1 0. 065= log

H2O2 → H2O + O t 3.956 – 2.481

2 2

1 2.303

1 mole (34g) of H2O2 gives moles of O2 i. e. 11. 21 ⇒t= × 0.49

at STP 2 0.065

t = 15. 13 weeks

Now, volume strength is the volume of O2 given by unit

volume of H2O2 t = 15. 13 weeks

Let normality of H2O2 = N longer = 9. 13 weeks

weight

Then, N = Sol 7: We have,

Eq. weight

H +

⇒ Weight = 17 N (equivalent weight = 17) A →B + C

H +

11.2 × 17N A →B + C

\ 17 N g of H2O2 gives of O2

34 At t = 0 x 0 0

11.2 × 17N At t = ∞ 0 x x

Volume strength = = 5. 6 N

34

We know optical rotation of B and C are 40º and –80º

Now, initially volume strength = 20 respectively at completion,

20

⇒ N0 = = 3. 75 N total optical rotation

5.6

⇒ 40x – 80x = -10

At time, t = 6 hours, let normality be N.

⇒ x = 0. 5

Since, 10 mL of solution be diluted to 100 mL,

Now, optical rotation at t = 0

N.10

Now normality = = 0. 1 N

100 ⇒ 60 × 0. 5 = 30º

Now, since this is first order reaction, according to rate Using first order rate law,

law, as N is proportional to number of moles of H2O2 2.303 θ − θ∞

k= log 0

2.303 N t θt − θ∞

k= log 0 = 2.303 log 3.57 ; k = 0. 022 hr–1

t N 6 3.125 q0 = initial optical rotation

or t1/2 = = +

k 2.303 θ0 − θ∞

2.303 τ log

k= log max θt − θ∞

6 τmax − τ

Putting values

Where, tmax = maximum thickness of oxide film

(at t → ∞) 0.693 20

t1/2 = +

τ = thickness at time t 2.303 (30 − 1 − 20)

log

(5 − 1 − 20)

We are given

since θ = 5º

3.956

tmax = inch 0.3 × 20

1000 at t = 20 min =

log2

1.281 t1/2 = 20 min

τ= inch, at t = 6 weeks

1000

Chem i str y | 18.61

Sol 8: Since, volume and temperature is constant, we +(log3 × 2.303 × 8.314 × 293 × 276)

∴ EA =

take P ∝ n 17

CH3OCH3(g)→CH4(g)+CO(g)+H2(g) EA = 43. 46 kJ/mol

at (b) When T2 = (273 + 40) K = 313K,

t=0 0. 4 0 0 0 k2 43.460 1 1

We have, log = −

t = 4.5hr. 0. 4–x x x x k1 303 × 8.314 293 313

We are given k = 4. 78 × 10 , since unit is –3 ⇒ k2 = 3312 k1

Further, as k ∝

t

PA = P0e–kt

t2 k1 6.4

= 0.4 × e(–4. 78 × 10

–3 × 4. 5 × 60)

∴ = ⇒ t2 =

t1 k2 3.12

⇒ PA = 0.11 t2 = 20. 47 hours

0. 4 – x = 0. 11

⇒ x = 0. 29 Sol 10: We have, according to Arrhenius equation

log = −

k1 2.303R t1 t2

(P0 − x)MCH + x.MCH + MCO + x + M0 + xMH

3OCH3 Here,

= 4 2

P+x+x+x+x

EA = 70 ks mol–1

0.11 × 46 × 0.29 × 16 + 0.29 × 28 + 0.29 × 2

= = 18. 77 t1 = (273 + 25) K = 298 K

0.11 + 0.29 + 0.29 + 0.29

t2 = (273 + 40) K = 313 K

at t = 0, molecular mass

Putting values

M1 = MCH = 46 k2

3OCH3 70000 1 1

log = −

Pt = 0. 4 – x + 3x = 0. 4 × 2x = 0. 98 k1 2.303 × 8.314 298 313

According to Graham’s law ⇒ k2 = 3. 87 k1

P Now, equation

Rate of diffusion ∝

M A→B

D0 P0 M2 18.77 0.4 According to rate law

= = ×

Dt Pt M1 46 0.98

[A] = [A0] e–kt

D0 At T = 298 K, k = k1, … t = 20 min,

= 0. 26

Dt 3[A0 ]

[A] =

4

Sol 9: (a) According to Arrhenius equation, we have

3 −k .20

∴ = e 1

k2 EA 1 1 4

log = −

k1 2.303 T1 T2 ⇒ k1 = 0. 014 min–1

Here, we have ∴ k2 = 3. 87 k1 = 0. 055 min–1

T1 = (273 + 20)K = 293 K Now, at T = 313 K, t = 20 min,

T2 = (273 + 3)K = 276 K k = 0. 055 min–1

k1 [A] = [A0] e–0. 055 × 20

k2 =

3

Putting values [A] = 0. 3279 [A0]

∴ 67. 21 % of A got decomposed.

1 EA 1 1

log = −

3 2.303 × 8.314 293 276

1 8 . 6 2 | Chemical Kinetics

We have, = k2[A]

k2 EA 1 1 dt

log = −

k1 2.303R T1 T2 d[C] −(k +k )t

⇒ = k2[A0] e 1 2

dt

For, A → products

[C] t

If k at 310 K is taken to be k −(k1 +k 2 )t

⇒ ∫ d[C] = k 2 [A0 ]∫ e dt

k 0 0

Then, k at 300 K is

2 k 2 [A0 ] −(k1 +k 2 )t

[C] = (1 − e )

Putting this in equation, we get k1 + k 2

EA 1 1 k [A ](1 − e 1 2 )

−(k +k )t

log 2 = − [C]

2.303 × 8.314 300 310 = 2 0

[A] −(k +k )t

(k1 + k 2 ).[A0 ]e 1 2

log2 × 2.303 × 8.314 × 310 × 300

⇒ EA = k2 (k1 +k 2 )t

10 = (e − 1)

k1 + k 2

EA = 53. 67 kJ/mol

Now we are also given at T = 310 K, Now, we have k1 = 1. 3 × 10–5 s–1,

∴ k at 310 K = = 0. 0231 min–1

t1/2 Putting values,

At 310 K, for (ii) B → products [C] 9 1.3×10−4 ×3600

= (e − 1)

k = 211 for (i) [A] 10

= 0. 537

[A]

Further, for (ii)

(EA ) f k

EA = = 26. 802 k J/mol Sol 13: As Cis-(en)2(OH)2+

k b

2

trans-Cr(en)2(OH)2+

Therefore, using Arrhenius equation, we get

We have,

k 268.02 1 1 kf

log = −

0.0769 2.303 × 8.314 310 300 Eq. constant = = 0. 16

kb

k = 0. 0327 min–1

and kf = k1 = 3. 3 × 10–1 s–1

kt

Sol 12: We are given, ⇒ kb = = 2. 0625 × 10–4 s–1

0.16

k1 B

Now using formula for eq. reactions.

A

xeq

k2 C ln = (kf + kb) t

xeq .x

Here, xeq

We have to find t for which x =

k1 1 q

= , k = 1. 3 × 10–5 s–1

k2 9 x

eq

Now, both are first order reactions ln = (3. 3 × 10–4 + 2. 0625 × 10–3)t

xeq

d[A] xeq −

∴ = –(k1 + k2)[A] 2

dt

ln 2

⇒ [A] = [A0] e

−(k1 +k 2 )t ⇒t= s

2.3925 × 10−5

Now, for A → C,

t = 289. 71 s ⇒ t = 4. 83 min

Chem i str y | 18.63

1 k

Sol 14: We have, A B

k 2

k1 [B]eq

Energy →

Also, we know, keq = = Ef Eb

k2 [A]eq

k1

⇒ = 4, k1 = 10–2 s–1

k2 A B ∆H

⇒ k2 = = 2. 5 × 10–3 s–1

4 We see that

Now at eq. , [A] = [A0] – xeq

Eb = Ef + |∆H|

[B] = xeq

20Eb

⇒ But Ef =

xeq 31

Then, =4

− xeq

[A]e 20Eb 11Eb

∴Eb = + 33 ⇒ = 33

We are given [A] 0 = 0. 01 mole L–1 31 31

⇒ Eb = 63 kJ/mol

xeq

=1 Ef = Eb – 33

0.01 xeq

5xeq = 0 + 60. 07 Ef = 30 kJ/mol

xeq = 0. 008 mole L–1

Now, using equilibrium first order formula, Sol 16: We have rate k′[complex] a, k′ = k[H+] b

xeq Let’s assume that this is Pseudo first order reaction, that is

ln = (k1 + k2)t a=1

xeq − x

0.693

Then, we have t1/2 = ,

At t = 30 s, k′

1.386

0.008 t3/4 =

ln = (12. 5 × 10 ) × 30 = – 0. 375

–3 k′

0.008 − x

We note that, here t3/4 = 2. t1/2

x = 0. 0025 mole L–1

which is true for given data also

B(g)

A(g)

0.693 0.693 0.693

t1/2 = 1 = = ⇒ (0. 01)b =

k′ + b

k[H ] k

For forward reaction, we have

∆H = ∆E = –33 kJ/mol When [H+] = 0. 02

0.693 1.386

We know, (0. 02)b = =

k.t1/2 k

−∆Hº

ln k = (since ∆S ≈ 0) These both will be satisfied for b = 1.

RT

with T = 300 K, ∆H = 33 kJ/mol ∴ Taking a = b = 1, all the given data can be verified

and there are no contradictions

we get, k = 5. 57 × 105

∴a=b=1

Now, we are given

Ef 20 k

= Sol 17: A

1

→B

Eb 31

2k

Now, we have for this transformation A →C

−d[A]

We have, k for disappearance of A, = (k1 + k2)t

dt

∴ k = k1 + k2

1 8 . 6 4 | Chemical Kinetics

−E1 −E2

−E

Rate, R = k3[COCl] [Cl2]

Ae RT = A1e RT + A2e RT

(∵ (iii) is slowest step (RDS))

A = Pre exponential constant Also, from equilibrium of (ii),

1 k2 [COCl]

Differentiating with respect to , we get =

T k −2 [CO][Cl]

−E −E −E

−AE RT −A1E1 RT1 −A2E2 RT2

e = e + e And from equilibrium of (i),

R R R

k1 [Cl]2

⇒ Ek = E1k1 + E2k2 =

k −1 [Cl2 ]

E1k1 + E2k 2 k

1/2

⇒E= [Cl] = 1 ([Cl2 ])1/2

k

k −1

E1k1 + E2k 2

⇒E= Putting these values back in rate formula,

k1 + k 2

we get

1

+

Sol 18: (a) We have, k2 k 2

Rate = k 3 [CO] 1 ([Cl2 ])1/2 [Cl]

k

k −2 k −1

1

A + B

C

k 2

k1 d[COCl2 ] k 2 k1

C

→ D = k3 [CO][Cl2 ]3/2 = k[CO] [Cl2] 3/2

dt k −2 k −1

Since second step is RDS,

1/2

Rate = k3[C] k 2 k1

k = k3 .

d[C] k −2 k 2

Also, = –k3[C] + k2[A] [B] – k2[C]

dt

d[C] k [A][B] k1

Now, at steady state, = 0 ⇒ [C] = 1 2B(g)

dt k3 + k 2

Sol 20: A(g)

k1k 3 [A][B] k2

∴ Rate = C(g)

k3 + k 2

We have,

(b) If k2 >> k3, then k2 + k3 ~

_ k2

−d[A]

Rate = = –(k1 + k2)[A]

k1k 3 dt

Then, Rate = [A] [B]

k2 [A] = [A]0 e–kt ; k = k1 + k2

Using Arrhenius equation, 1 d[B]

Further, Rate = = k1[A]

−EA 2 dt

k = A e RT

Putting value of [A] and integrating

Ea Ea

1 3 −(Ea +Ea −Ea )

A1 e RT A3 e RT 1 3 2 2k1 [A1 ]

A1 A3

k= = e RT [B] = (1 − e−kt )

Ea

2 A2 k1 + k 2

A2 e RT k 2 [A]0

−Ea Similarly, [C] = (1 − e−kt )

Comparing with k = Ae RT k1 + k 2

A=

A2 At t → ∞, Pt = 1. 5 atm

Ea = Ea + Ea − Ea Putting values and taking t = ∞, we get

1 3 2

Chem i str y | 18.65

+ = 1. 5

k1 + k 2 k1 + k 2 (i) Since, this is first order w. r. t. A, second order w. r. t.

B, and 0 order w. r. t. C.

⇒ 2k1 + k2 = 1. 5 k1 + 1. 5k2

Rate law = k[A] [B]2[C]0

k

⇒ k1 = k2 = Rate,R = k[A] [B]2

2

Now, taken at t = 10s, Pt = 1. 4 atm (ii) Now rate, R′ = k[2A] [2B]2 = 8k[A] [B]2 = 8k

k[A]0 ∴ Rate becomes 8 times

∴ [A]0e–k. 10 = (1 − e−k.10 )

k

k[A]0 Sol 24: We know, for first order reaction

(1 − e−k.10 ) = 1. 7

2k 2.303 [A]

k= log 0

[A]0 = 1, 30 [A]t

1 e−10k At T = 27ºC = 300 K, at t = 30 min, 50% of reaction gets

∴ e–10R + 1 – e–10R + – = 1. 4

2 2 completed, i. e. [A] t = 0. 5[A]0

⇒ e–10R = 0. 2 2.303

k= log2

⇒ k = 0. 16 30

k = 0. 0231 min–1 = 3.85 × 10–4 s–1

k

⇒ k 1 = k2 = = 0. 08

2 At T = 47ºC=320 K, time taken for 50% completion is

10 min.

Sol 21: For 50% completion, time taken 2.303

∴k= log2

0.693 10

t1/2 =

k k = 0. 0693 min–1 = 11.55 × 10–4 s–1

0.693 Now, by Arrhenius equation

⇒k= = 0. 01 min–1

69.3

k2 EA 1 1

Now, for 80%, [A] = 0. 2[A0] ln = −

k1 2.303 T1 T2

Using [A] = [A]0e–RT ⇒ 0. 2 = e–RT

ln5 At T = 300 K, k = 0. 0231 min–1

⇒t=

0.01 T = 320 K, k = 0. 0693 min–1

t = 161 min Putting values

0.0693 EA 1 1

Sol 22: We have, from Arrhenius equation, log = −

0.0231 2.303 × 8.314 300 320

k2 Ea 1 1

log = − EA = 43. 78 kJ/mol

k1 2.303R T1 T2

k2

Now, = 4, T1 = 27ºC = 300 K Sol 25: Firstly, we assume that reaction is first order and

k1

see if the data is consistent.

T2 = 47ºC = 320 K

For first order reaction, we have

Putting values, we find 2.303 θ − θ∞

k= log 0

EA 1 1 t θt − θ∞

log 4 = −

2.303 × 8.314 300 320 At time, t = 10 min,

⇒ EA = k= log

20 t 28.8 − ( −11.1)

EA = 55. 33 kJ mol–1 k = 8. 14 × 10–3 min–1

At time, t = 20 min

1 8 . 6 6 | Chemical Kinetics

k= log

t 25.5 − ( −11) (i) Initial rate = k[A] 0

k = 8. 64 × 10–3 min–1 = 1. 8 × 10–2 × 0. 1

At time, t = 30 min = 1 × 10–3 mol sec–1 L–1

2.303 32.4 − (11.1) (ii) After 60 sec (1 min),

k= log = 8. 70 × 10–3 min–1

t 22.4 − ( −11) Rate = k[A] 1

At t = 40 min, = k[A]0 e–k×60

2.303 32.4 − (11.1) = 5. 495 × 10–3 mol sec–1 L–1

k= log = 8. 71 × 10–3 min–1

40 19.6 − ( −11.1)

We see that all values of k are pretty close to each other, Sol 29: Since, unit of rate constant is min–1, it is first

order reaction.

∴ The reaction is first order.

Initial rate = k [A]0 = 10–3 × 0. 2 = 2×10–4 mol min–1 dm–3

1 After 200 minutes,

Sol 26: We know, for nth order reaction t1/2 ∝

[A]n0−1 −3 ×200

[A] = [A] 0 e−10 = 0. 8187[A] 0

Here as [A]0 is doubled, t1/2 gets halved,

∴ 18. 12 % of reactant converted into product.

1

∴ t1/2 ∝

[A]0

Sol 30: (i) At time, t = 10 min, [A] = 0. 8 [A]0

Or n – 1 = 1

∴ 0. 8[A]0 = [A]0 e–10k

⇒n=2

⇒ k = 0. 022 min–1

Hence, second order reaction.

(ii) When 75% reaction is completed,

Sol 27: We have, by Arrhenius equation 1

[A] = [A]0,

4

k2 Ea 1 1

log = − 1

k1 2.303k T1 T2 ∴ [A]0 = [A]0 e–0. 022t

4

Now, given data, ⇒ t = 63. 01 min.

at t = 50ºC = 323 K,

k = 1. 5 × 10+7 sec–1.

Exercise 2

at T = 100ºC = 373 K,

k = 4. 5 × 107 sec–1 Sol 1: (B) From the table, we see that when (A) is

doubled, rate get becomes 4 times, keeping (B) constant

Filling the data,

∴ Rate ∝ (A) 2

Ea

1 1

log 3 = − Also, when (B) is doubled, keeping (A) doubled.

2.303 × 8.314 323 373

−Ea Rate becomes 2 times

Ea = A e RT ∴ Rate ∝ (B)

∴ Rate = k(A)2 (B)

Ea = 2. 2 × 107 J mol–1

−Ea

Now,k = A e RT Sol 2: (A) Rate, ri = k(A) n[B] m

m

+Ea B k 2n

⇒ A = ke RT rf = k[2A] n = [A] n [B] m

2.2×107

2

2 m

7e 8.214 ×323 rf

= 1. 5 × 10 = 2(n – m)

ri

A = 5. 42 × 1010 s–1

Chem i str y | 18.67

Now, for 0. 1 M to 0. 025 M, = 0. 01 × 0. 1 M min–1

t = 2 × t1/2 = 30 min = 10–3 M min–1

t t

(0. 1

1/2

→ 0. 5

1/2

→ 0. 025)

Sol 9: (C) For zero order reaction, rate is always

constant.

Sol 4: (D) Only statement (D) is correct as k is constant

at a given temperature. i. e. rate = 10–2 M min–1

(A) and (B) are correct for first order reaction. (C) is A(g) → 2B(g)

wrong as t=0 0. 1

d[C] 1 d[A] d[A] t=1 0. 1–x 2x

= − not 2

dt 2 dt dt

1 d[B]

= 10–2

2 dt

Sol 5: (D) For a first order reaction,

[B] = 0. 02 t

[A] = [A]0e–kt

At t = 60 sec = 1 minute

3

When, [A] = [A]0 , t = t3/4

4 [B] = 0.02 M

3 −k.t

⇒ = e 3/ 4

4 Sol 10: (D) Let time be t

0.29 Then, for X →A + B

1 k

⇒ t3/4 =

k

50% reaction gets completed at time t

Sol 6: (D) rate ∝ [O] 2 1 −k t

⇒ [X]0 = [X]0 e 1

2

∴ When [(O)] is doubled, rate becomes 4 times.

ln2

k1 =

t

Sol 7: (C) A + 3B → P

k

For Y

2→C + D

∆H = -2x kJ/mole of A …(i)

96 % of reaction gets completed at time t.

M → 2Q + R

∴ 0. 04[Y] 0 = [Y]

−k 2 t

e

∆H = -x kJ/mole of M …(ii) 0

ln25

We see that, if these reactions are carried simultaneously k2 =

t

energy released from (i) and energy absorbed is (ii)

counter each other further, ∆H = 2OH, rate of second k2 ln25

= = 4. 65

reaction will be double of that of (i) k1 ln2

−1 d[B] y

Now, rate of first reaction= = Sol 11: (D) We know, for nth order reaction

3 dt 3

1

2y 1 d[Q] d[Q] 4 ∝

Rate of second reaction= = ⇒ = y P0n−1

3 2 dt dt 3 n−1

(t1/2 )2 P0

⇒ = 1

Sol 8: (B) We have t = 138. 6 min for (t1/2 )1 P0

2

1M → 0. 25 M Putting values,

2 × 0.693

i.e., 2t1/2 = 138. 6 = 950 500

n−1

k =

t t 235 250

(1

1/2

→ 0. 5

1/2

→ 0. 25)

log 4.04

⇒ k = 0. 01 ⇒n–1= = 2; ⇒ n = 3

log2

When [A] = 0. 1,

1 8 . 6 8 | Chemical Kinetics

Sol 12: (C) We have first order reaction Sol 16: (A) We have for first order,

k= log 0

t [A]t 0.1

(A)0 = mol L–1 = 0. 05 mol L–1

at t = 20 min, (A) t = 0.8(A)0 2

k = 3. 465 × 10–6 s–1, t = 200 s

(Since 20% reaction completed)

−6 ×200

(A) = 0. 05 e−3.465×10

2.303 5

⇒k= log ≈ 0. 05 M

20 4

k = 1. 11 × 10–2 min–1

Sol 17: (D) R is universal gas constant

0.693

t1/2 = = 62. 13 minutes k is rate constant

k

A is pre exponential factor

Sol 13: (C) Rate = k(A) = k(A) 0e–kt

Ea is activation energy

It follows an exponential decay.

Sol 18: (C) This is the correct definition.

Sol 14: (D) A(g) → 2B(g)

−E0 /RT

100 2 Sol 19 (B) k = A e ;As T → ∞,

2 −E0 /RT

B V 10 4 1 k = A = 6 × 1014 s–1(∵ e → 1)

We have, keq = = = . = 108

[A] 10

−5

10 −5 10

V Sol 20: (B) We have, from Arrhenius equation

k 1.5 × 10 −3 k2 EA 1 1

108 = f = log = −

kb kb k1 2.303R T1 T2

⇒ kb = 1. 5 × 10–11 L mol–1 s–1 Here, at T1 = 27ºC = 300 K

k1 = min–1

20

t=0 1 1 0 0

t=1 1-x 1–x x x At T2 = 47ºC = 320 K

We have, 0.693

k2 = min–1

−d[A] 5

Rate = = k(A) 1/2(B) 1/2

dt Putting these values,

−d[A] EA 1 1

⇒ = k(1 – x)1/2 (1 – x)1/2 log 4 = −

dt 2.303 × 8.314 300 320

−d[A] ⇒EA = 55. 14 kJ/mol

⇒ = k(1 – x)

dt

This can be written as, Sol 21: (C) We have, 27ºC = 300 K, 3. 8 × 10–16 of

−d[A] reactant molecules exist in the activated region.

= k(A)

dt i. e, N = 3. 8 × 10–16 N0

N

2 n2 2 × 2.303log2 N0

t= =

k 2.303 × 10−3 3.8 × 10−16 N0

t = 600 s

Ea = 100 kJ/mol

Chem i str y | 18.69

Sol 22: (D) Since, at 400 K, 0. 0001% (10–4%) of collisions 0.693 2.303 100

are effective only 10–4% of molecules have their energy = log

t1/2 t 100 – 99

above activation energy.

N0 0.693 2.303 × 2

Ea = 2. 303 RT log =

N 6.93 t

N0

= 2. 303 × 8. 314 × 400 log So, t = 46.06 min.

10−6 N0

= 45. 944 k J/mol = 11. 05 k cal/mol Sol 7: (B) Because two molecules are taking part in

elementary reaction.

dx

∝ [CO]2 so on doubling the

dt

1 d[A] 1 d[B] d[A] 1 d[B] concentration of CO, the rate of reaction will increase

Sol 1: (A) A → 2B ; – 2 = ;– = by 4 times.

2 dt 2 dt dt 4 dt

Rate at 50°C T

Sol 2: (C) = (2) 1 = (2)10 = 25 = 32 times

Rate atT1 °C

Sol 10: (D) The differential rate law for,

NO + Br2 → NOBr2 would be

2.303 a

Sol 3: (C) k = log10 ;

t a−x dc

– =k[NOBr2][NO]

dt

t = 2 × 102, a = 800, a – x = 50 [NOBr2 ]

We have, Kc =

2.303 800 2.303 [NO][Br2 ]

k= log10 = log10 16

2 × 10 2 50 2 × 102 Provided the first reaction attains equilibrium rapidly.

dc

2.303 4 2.303 ∴– = k × kc × [NO]2[Br2] = k[NO]2[Br2]

= log10 2 = × 4 × 0.301 = 1.38 × 10 s

–2 –1

dt

2 × 102 2 × 102

∴The order of the reaction with respect to NO(g) is 2.

When conc. of B is doubled, the half-life did not Rate = k[Cl2][H2S] (By slow step)

change, hence reaction is of first order w.r.t. B. When

concentration of A is doubled, reaction rate is doubled, For B

hence reaction is of first order w.r.t. A, Rate = k[Cl2][HS–]

Hence, over all order of reaction is 1 +1 = 2

[H+ ][HS − ]

keq =

So, unit of rate constant mol lit s . –1 –1

[H2S]

(According to equilibrium)

Sol 5: (D) Rate= k(N2O5)

k eq [H2S]

hence 2.4 × 10–5 Rate = k[Cl2]

[H+ ]

= 3.0 × 10 (N2O5) or (N2O5)

–5

Rate = k.keq[Cl2]

[H+ ]

Sol 6 (C) In first order reaction for x% completion

a

Sol 12: (D) t1/2 = (for zero order reaction)

2.303 100 2k 0

k= log

t 100 – x% a 2

k0 = = =1

2 × t1/2 2 × 1

1 8 . 7 0 | Chemical Kinetics

A0 – [A]t 0.50 – 0.25 Sol 19: (D) Rate equation is to be derived w.r.t slow

k0 = ⇒ k0 = =1

t t Step ∴ from mechanism (A)

t = 0.25 hr. Rate = k[Cl2] [H2S]

Sol 13: (D) So, ∆HReaction = Ef – Eb = 80 – 100 = –20. Sol 20: (B)

Temperature coefficient µ =2;

Sol 14: (A) For endothermic reaction ∆H = +ve ∆T

k

Then from equation ∆H = EaF.R – EaB.R ; EB.R < EF.R . µ 10 =2 ;

k1

50

k2

Sol 15: (B) In photochemical reaction, the rate of µ 10 = 25 = 32 =

k1

formation of product is directly proportional to the

intensity of absorbed light. Therefore 32k1 = k2

Sol 21: (B) k = log ;

1 40 0.025

A → 2B 0.693

2 k=

20

d[A] d[B]

− =

+ 0.693

dt 2dt For a F.O.R., rate = × 10−2 = 3.47 × 10−4 M / min.

20

d[A] 1 d[B]

− =

dt 4 dt

K −Ea 1 1

Sol 22: (A)

= log 2 −

Sol 17: (C) K1 2.030R T2 T1

K2

0.6932 0.6932 = 2;=

T2 310K T1 300K

=

=

λ = min−1 K1

t1/2 6.93

−E 1 1

[A ] ⇒ log2

= −

2.303 2.303 × 8.134 310 300

Also t= log

λ [A]

=⇒ Ea 53598.6

= J / mol 53.6 KJ / mol

[A ] = initial concentration (amount)

[A] = final concentration (amount)

Sol 23: (D)

2.303 × 6.93 100

∴ t= log = 46.06 minutes

0.6932 1 −1 d[A] d[B] d[C] d[D]

Rate of Reaction = =

− = =

2 dt dt dt dt

Sol 18: (C) Let rate of Reaction = k(A)x(B)y

x d[C]

For a zero order reaction k = …. (i) Or, = k[A]x [B]y

t dt

Where x = amount decomposed Now from table,

k = zero order rate constant 1.2 × 10–3 = k [0.1]x[0.1]y .....(i)

for a zero order reaction 1.2 × 10–3 = k [0.1]x[0.2]y .....(ii)

[A]0 2.4 × 10–3 = k [0.2]x[0.1]y .....(iii)

k= …. (ii)

2t1/2

Dividing equation (i) by (ii)

Since [A0]=2M, t1/2 = 1hr; k=1 1.2 × 10−3 k[0.1]x [0.1]y

⇒ =

∴ from equation (i) 1.2 × 10−3 k[0.1]x [0.2]y

0.25 y

=t = 0.25 hr 1

1 ⇒ 1=

2

Chem i str y | 18.71

⇒ y=0 +1.08

= × 10 −2 = 3. 6 × 10–3 mol L–1

3

Now dividing equation (i) by (iii)

d[H2O] 6 d[NO]

−3 x y (iii) =

1.2 × 10 k[0.1] [0.1] dt 4 dt

⇒ =

−3

1.2 × 10 k[0.2]x [0.1]y 3 1.08 × 10 −2

= × = 5. 4 × 10–3 mol L–1

1 y 2 3

1 1

⇒ =

2 2 Sol 2: (a) 2H2O2 → 2H2O + O2

⇒ xx==

1 −1 d[H2O2 ] −1 d[H2O] d[O2 ]

We know, = =

2 dt 2 dt dt

d[C]

Hence = k[A]1 [B]0

dt d[H2O] d[O2 ]

=2 = 2 × 3. 6 M min–1

dt dt

Sol 24: (A) In 50 minutes, concentration of H2O2 d[H2O]

= 7. 2 M min–1

1 dt

becomes of initial.

4

−d[H2O2 ] 2 d[H2O] −d[H2O2 ]

⇒ 2 × t1/2 = 50 minutes (b) = = = 7. 2 M min–1

dt 2 dt dt

⇒ t1/2 =

25 minutes

Sol 3: N2 + 3H2 → 2NH3

0.693

⇒ K= per minutes

25 d[N2 ] −1 d[H2 ] 1 d[NH3 ]

(a) = =

0.693 dt 3 dt 2 dt

rH = × 0.05 = 1.386 × 10−3

2O2 25 −d[N2 ] 1 d[NH3 ]

=

dt 2 dt

2H2O2 → 2H2O + O2

1

= × 2 × 10–4 mol L–1s–1 = 10–4 mol L–1 s–1

1 2

rO = ×r

2 2 H2O2 −d[H2 ] 3 d[NH3 ]

(b) = ×

dt 2 dt

rO

= 0.693 × 10−3

2 3

= ×2 × 10–4 mol L–1 s–1 = 3 × 10–4 mol L–1 s–1

6.93 × 10−4 mol / minute × litre

rO = 2

2

JEE Advanced/Boards and 0 order w. r. t. C.

dx

= k [A] 1[B] 2[C] 0, k = [D]t

Exercise 1 dt

dx

⇒ = k[A] [B] 2

Sol 1: 4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g) dt

−1 d[NH3 ] −1 d[O2 ] (ii) If [A], [B], [C] are all doubled.

Rate of reaction = = =

4 dt 5 dt rf = k[2A] [2B] 2 = 8k[A] [B] 2 = 8r

1 d[NO] 1 d[H2O] Rate becomes 8 times

=

4 dt 6 dt

1 d[NO] 1 1.08 × 10−2 Sol 5: We have, by ideal gas equation

(i) Rate of reaction = =

4 dt 4 3 n

PV = nRT ⇒ P = RT

= 9 × 10–4 mol L–1 V

P = CRT

−d[NH3 ]

(ii) = +4 d[NO] P

dt 4 dt C=

RT

1 8 . 7 2 | Chemical Kinetics

∆C 1 ∆P k2

Rate of reaction = = ⇒ k1 = = 2k3 ⇒ 2k1 = k2 = 4k3

∆t RT ∆T 2

We have, R = 0. 0921 L atm/mol. k

1 4

T = 27ºC = 300 K Sol 9: 4 1 H → 2 He ; ∆H = 2. 6 MeV

1 0.9 NA

Rate of reaction = × Ms–1 H= = 26 × 106 × 1. 6 × 10–14 J = 6. 26 × 1011 J

0.0921 × 300 75 × 60 4

= 7. 23 × 10–6 Ms–1 Power output of sun = 3. 9×1026 W = 3. 9 × 1026 J/s

Rate of reaction in terms of pressure i.e. it radiates 3. 9 × 1026 J in one second.

∆P 0.9 Number of moles of H required per second

= = atm min–1 = 0.012 atm min–1

∆t 75

3.9 × 1026

= = 6. 23 × 1014

6.26 × 1011

Sol 6: 2A + B2 → 2AB

1.7 × 1030

Since, this is an elementary reaction, Total moles of H on sun = = 1. 7 × 1033

10 −3

rate, ri = k[A] 2[B2] 1.7 × 1033

Time taken = = 2. 72 × 1018 s

If volume of vessel reduced to one-third, [A] and [B2] 6.23 × 1014

becomes 3 times each.

∴ rf = k[3A] 2[3B2] = 27k (A) 2[B2] = 27ri Sol 10: A(g) + 2B(g) → C(g) + D(g)

t 0. 6–x 0. 8–2x x x

Sol 7: 3BrO → BrO3 + 2Br

– -

Since this is elementary reaction

We have, Rate, r = k(B) 2(A)

−1 ∆[BrO] ∆[BrO3− ] Now,ri = k(0. 6)(0. 8)2 = 0. 381 k

Rate = =

3 ∆t ∆t

WhenPi = x – 0. 2 atm

1 ∆[Br] −∆[BrO − ]

= = k[BrO–] +2= = 3k[BrO–] 2 PA = 0. 6 – x = 0. 4 atm

2 ∆t ∆t

We have, 3k = 0.056 PB = 0. 8 – 2x = 0. 8 – 0. 4 = 0. 4 atm

rf 0.064 1

∆[BrO3− ] = =

(a) = k[BrO–] 2 = 0. 0186[BrO–] 2

∆t ri 0.384 6

Hence rate constant = 0. 0186 L mol–1s–1

Sol 11: A → B

∆[Br − ]

(b) = 2k[BrO–] 2 = 0. 037[BrO–] 2 k = 1. 2 × 10–2 Ms–1

∆t

Rate constant = 0. 037 Lmol–1s–1 Since unit of rate constant is Ms–1, it is zero order

reaction

1

Sol 8: We have, N2O5(g) → 2NO2(g) + O2(g) Rate law [B] = kt

2

−d[N2O5 ] 1 d[NO ] At t = 10 min

⇒ = 2

dt 2 dt [B] = 1. 2 × 10–2 × 10 × 60 M

1 d[O2 ] [B] = 7. 2 M

= = +k[N2O5]

1 dt

At t = 20 min

2

k

Hence, k1 = k, k2 = 2k, k3 = [B] = 1. 2 × 10–2 × 20 × 60 M = 14. 4 M

2

Chem i str y | 18.73

But, [A] 0 = 10 M and [B] cannot be greater than [A0] [A]0. When A is 10% unreacted,

∴ [B] = 14.4 M implies that reaction has reached 1

[A] = [A ]

completion, i. e. 10 0

1

[B] max = 10 M ∴ [A]0 = [A]0 – kt

10

[B] = 10 M

9 3

⇒ [A] 0 = [A]0t

Sol 12: For zero order reaction, 10 4

[A] = [A]0 – kt ⇒ t = 1. 2 hr

At t = 0, [A] = [A]0 = 0. 1 M

At t = 1 min, [A] = 0. 09 M Sol 16: (i) We know, for first order reaction

0. 09 = 0.1 – k [A] = [A]0e–kt

⇒ k = 0. 01 M min–1 k=

1 [A]0

ln

t [A]

At t = 2 min, [A] = 0. 1 – 0. 01 × 2

1

At t = 72 min, 75% reaction completed, i. e. [A] = [A]0

= 0. 08 M, which is the value given. 4

1

∴ k = 0.01 M min–1 ∴k = ln 4 = 0. 019 min–1

72

When reaction is 50% complete,

Sol 13: For zero order reaction

ln2

[A] = [A]0 – kt t = t1/2 = = 36 min

k

We are given,

(ii) When reaction is 87. 5% complete, [A] = 0. 125[A]0,

k = 2 × 10–2 mol L–1sec–1

1 1

∴t= ln

and at t = 25 sec, (A) = 0. 25 M k 0.125

[A]0 = [A] + kt t = 108 min

= 0. 25 + 2 × 10–2 × 25 = 0. 75 M

Sol 17: We have, for first order reaction

Sol 14: It is a zero order reaction (∵ unit of rate constant 1 [A]0

k= ln

is M sec–1) t [A]t

6 × 10−6 (i) At t = 10 min, reaction is 20% complete, i. e. [A] = 0.

[H+]0 = = 6 × 10–2 M

0.1 × 10−3 8[A]0

k = 107 mol L–1 sec–1 1 [A]0

k= ln

[H+ ]

10 0.8[A]0

Time taken to disappear =

k k = 0. 0223 min–1

6 × 10 −2

= sec = 6 × 10 sec

–9

1

Sol 15: Since it is a zero order reaction [A] = [A]0

4

[A] = [A]0 – kt

1 [A]0 1 [A]0

1 t= ln = ln

When t = 1 hour, [A] = [A]0 k [A]t 0.0223 1

4 .[A]0

4

(∵ 75% reacted) t = 62. 17 min.

1

∴ [A]0 = [A]0 – k Sol 18: Order will be equal to 1.

4

3 1 [A]0

⇒ k = [A]0 M hr–1 t= ln

4 k [A]t

1 8 . 7 4 | Chemical Kinetics

[A]t = 10–3 [A] 0 k = 3. 3 × 10–4 sec–1.

1 [A]0 3 6.909

t1 = ln = ln10 =

k 10−3 [A] k k Sol 22: If we assume the reaction to be of first order,

0

[A]0 then, let [A]t = α and [A]0 = C0.

When reaction is 50% completed, [A]t =

2 a = C0e–kt

1 [A]0 ln2 0.693

∴t2 = ln = = At time

k 0.5[A]0 k k

t = 0, α = C0

We see that t2 ≈ 10t1

t = t, α = C0e–k = aC0, a = e–k

t = 2t, α = C0e–2k = a2C0, a = e–k

Sol 19: We have, first order reaction

t = 3t, α = C0e–3k = a3C0, a = e–k

N = N0e–kt

Therefore, taking the reaction to be of first order, we

here, k = 1. 5 × 10–3 sec–1

found the concentration of A to be of the form given in

N ∝ 1. 25 (wt. ∝ molar) question. Therefore, the reaction is of first order.

N∝5

−1.5×10−3 t Sol 23: For first order reaction,

∴1. 25 = 5e

1 5 [SO2Cl2] = [SO2Cl2]0 e–kt

⇒t= ln

1.5 × 10−3 1.25 k = 2. 2 × 10–5 sec–1,

t = 924. 3625 t = 90 min = 5400 sec

[SO2Cl2 ] −5400×2.2×10−5

∴ = e = 0. 888

Sol 20: We have, [SO2Cl2 ]0

[N]0 = 500 11. 2 % of [SO2Cl2] decomposed.

At t = 20 months, [N]t = 420,

ln2

Using first order to rate law, Sol 24: For A, k1 = ln2 =

t1/2 5

1 [N]0 Initial concentration = a0

k= ln

t [N]t Let [A]t = a

ln2

The drug will be ineffective (will expire) when it has For B, k2 = ln2 =

t1/2 1.5

decomposed 30%, i. e. [N] = 0. 7 [N] 0.

Initial concentration

1 [N]0 1 [N]0

∴ t = log = log [A]0 a0

t [N]t 8.717 × 10−3 0.7[N]0 [B]0 = =

4 4

t ≈ 41 months [B]4 = b

a0 −k 2 t

Sol 21: For first order reaction Then, b = e

4

1 [A]0

k = log When a = b,

t [A]t

a0 −k 2 t

We are given, 2% of virus gets inactivated every minute a0 e−k1t = e

4

at the beginning, i. e. , at t = 1 min, [A]t = 0. 98[A]0

4= e 1 2

(k −k )t

1 [A]0

k = log ln 4

1 0.98[A]0 ⇒t=

k1 − k 2

Chem i str y | 18.75

= = = ∴k= = = 0. 013 min–1

ln2 ln2 1 1 10 t 53

− ln2 −

5 15 5 15 (i) We see that both values of k are same, this is first

order reaction.

t = 15 min.

[N2O] −2 ×100

(ii) = e–kt = e−1.3×10 = 0. 27

Sol 25: From the data, we observe that, when [H2] [N2O]0

is halved, keeping [NO] constant, reaction rate gets

Thus 73% of N2O will decompose.

halved. So, order w. r. t H2 is 1.

When [NO] is doubled, keeping [H2] constant, reaction Sol 28: As in previous question, we assume order = 0

rate becomes 4 times so, order w. r. t. NO is 2. and calculate k at different time.

Rate = k[NO]2 [H2] At t = 0 sec, P = P0 = 4 × 103 Pa

(a) Order = 2 + 1 = 3 At t = 100 sec, P = 3. 5 × 103 Pa

(b) When, [NO] = 1. 5 × 10 M, –4

P0 − P (4 − 3.5) × 103

We have, k1 = = Pa/s

[H2] = 4 × 10–3 M, t 100

k1 = 5 Pa/s

Rate = 4. 4 × 10–4 M sec–1

At t = 200 sec, P = 2 × 103 Pa

4.4 × 10−4

∴k = (4 − 3) × 103

(1.5 × 10−4 )2 × (4 × 10−3 )2 k = k2 = = 5 Pa/s

200

When [NO] = 1. 1 × 10–3 M, At t = 300 sec, P = 2. 5 × 103 Pa

[H2] = 1. 5 × 10 M –3

(4.2.5) × 103

k3 = = 5 Pa

(c) Rate = 4. 88 × 106 × (1. 1 × 10–3)2 × (1. 5 × 10–3) 300

Rate = 8. 85 × 10–3 M sec–1 We see that k1 = k2 = k3 = 5 Pa/s is same for all. Hence

this is zero order reaction, rate constant = 5 Pa/s

Sol 26: From given data, we observe that, when [Cl2] is

tripled, rate becomes 3 times, so, order w. r. t. Cl2 is 1. Sol 29: We know, for nth order reaction

1

When [NO] is tripled, rate becomes 9 times, so, order t1/2 ∝

w. r. t [NO] is 2. [A]n0−1

Cl = 1 [A]0

at , ( t1/2 )2 = 25 min

(b) Rate = k[NO] [Cl2]

2

2

n−1

(c) When [Cl2] = 0. 05 M, [NO] = 0. 05 M, [A]0

Rate = 10–3 50 2 1

∴ = =

25 [A]0 2 −1

n

rate 10−3

k= = = 8 M–2 sec–1

2 2

[NO] [Cl2 ] (0.05) (0.05)

1

(d) If [Cl2] = 0. 2 M, [NO] = 0. 4 M, 2= ⇒ 2n–1 = 2–1

n−1

2

Rate = k[NO] 2 [Cl2] = 8 × (0. 4)2 (0. 2) n – 1 = –1

Rate = 0. 256 mol sec L –1 –1

⇒n=0

i. e. [A] = [A]0e–kt. Using this, we will calculate k at both

times. If they are same, then our assumption is correct.

At t = 53 min, 50% reaction completed, i. e. [A] = 0.

5[A]0

1 8 . 7 6 | Chemical Kinetics

Vn = V2 = =

A → B+ C N N

t=0 P0 0 0 NV2

⇒ n0 + x =

t P0 − x x x a

t→∞ 0 P0 P0 NV0 N

x= − n0 =

(V − V1 )

a a 2

We have, at time t = t1

1 n 1 n

k = ln 0 = ln 0

P1 = Pt = P0 – x + x + x t nt t n0 − x

P2 = P0 + x ⇒ x = P2 – P0 1 NV1

= ln

At time, t → ∞, t NV N

a 1 − (V2 − V1 )

Pt = P3 = 2P0 a a

P3 1 V1

⇒ P0 = k= ln

2 t 2V1 − V2

Taking first order reaction,

1 (PA )0 1 P 1 P0 Sol 33: A → 2B + 3C

k= ln = ln 0 = ln

t (PA )t t P0 − x t P0 − P2 + P0 Time, t = 0 a

1 P0 1 P3 Time, t a – x 2x 3x

k= ln = ln

t 2P0 − P2 3 2(P3 − P2 ) Time, t → ∞ 0 2a 3a

Let n-factor of A, B and C be n and normality of reagent

Sol 31: Here, we have, at time t = N then at time, t

P2 N. V2 = (a – x)n + 2xn + 3xn

PB + PC = P2 = 2x ⇒ x =

2

NV2 = n(a + 4x)

at time t → ∞, PB + P0 = P3 = 2P0

NV2

P3 a + 4x =

⇒ P0 = n

2

at time, t → ∞

1 (P ) 1 P3 1 P

k = ln A 0 = ln = ln 3 NV3 = 2a. n + 3a. n

t (PA )t t P3 P2 t P3 − P2

− ⇒ a = NV3 = 5an

2 2

NV3

a=

5n

Sol 32: A → B + C

NV2 NV3

Then 4x = –

time n 5n

t=0 n0 0 0 V3

N

x= V2 −

t n0 – x x x 4n 5

t→∞ 0 n0 n0

1 a 1 NV3

n0 − a k= ln = ln

At time, t = 0, Vr = V1 = t a−x t NV NV2 NV3

N 5n 3 − +

5n 4n 20n

NV1

⇒ n0 = V3 4V3

a 1 1

= ln = ln

(n-factor of A, B, C = a) t 5 t 5(V3 − V2 )

V3 − V + 4V3

4 2

(using NV1 = n0a)

1 4 V3

Normality of reagent = N k= ln

t 5 ( V3 − V2 )

At time, t = t,

Chem i str y | 18.77

⇒ = 856 – 758

Time t = 0 a 0 0 2

Time, t a–x x x x = 196 mm

Time t → ∞ 0 a a 1 758

k= ln

7.5 758 − 196

Let specific rotation of Glucose and Fructose be q1 and

q2 respectively k = 0. 039 hr–1

Then, at time t x

t = 10 hr, Pt = 889 = P0 +

2

xq1 + xq2 = rt

x = 2(883 – 758)

rt

x= x = 248 mm

θ1 + θ2

1 758

At time, t → ∞ k= ln

10 758 − 248

aq1 + aq2 = r∞

k = 0. 039 hr–1

r∞

a=

θ1 + θ2 Thus, all 3 values of k are approximately the same,

hence first order reaction.

2.303 a 1 a

k= log = log

t a−x t a−x Sol 36 : (CH3)2O(g)→CH4(g)+H2(g)+CO(g)

1 r∞ Time t = 0 P0 0 0 0

k= log

t r rt

(θ1 + θ2 ) ∞ − Time, t P0 – x x x x

θ1 + θ2 θ1 + θ2 t→∞ 0 P0 P0 P0

1 r∞

k= log

t r∞ − r1 Total pressure, at time t,

Pt = P0 – x + x + x + x = P0 + 2x

3

Sol 35: As H3(g) → As(s) + H2(g) Increase in pressure = (P0 + 2x) – P0 = 2x

2

t = 0P0 We will assume that this is a first order reaction and

3 check the consistency of given data.

t = 1P0 – x x

2

At t = 0, P0 = 312 mm Hg

Since, as a solid, it won’t contribute to pressure.

At t = 390 s, pressure increases;

3 x

∴ At time t, Pt = P0 – x + x = P0 + DP = 96 mm Hg = 2x

2 2

Let’s assume reaction is first order and calculate k at x = 48 mm Hg

1 P

different times, using k = ln 0 1 P 1 312

4 P0 − x ∴k= ln 0 = ln

t P0 − x 390 312 − 48

t = 0 P0 = 758 = Pt

k = 4. 28 × 10–4 s

x

t = 5 hrs , Pt = 827 = P0 +

2 At t = 1195 s, DP = 250 = 2x

x

827 = 758 + x = 125 mm Hg

2

1 312

⇒ x = 138 mm k= ln = 4. 28 × 10–4 s

1195 312 − 125

1 758

k= ln

5 758 − 138 At t = 3155 s, DP = 467 = 2x

x = 233. 5 mm Hg

k = 0. 04 hr–1

1 312

x k= ln = 4. 30 × 10–4 sec–1

t = 7. 5 hr, Pt = 856 = P0 + 3155 312 − 233.5

2

1 8 . 7 8 | Chemical Kinetics

k= log A 0 = log

Thus, we see that all 3 values of k are approximately the t (PA )+ 10 47

same. Therefore, this is a first order reaction.

k = 6. 49 × 10–2 min–1

So, rate = k[(CH3)2O], k

1 13.1 − ( −3.8)

= 4. 28 × 10–4 sec–1 k1 = 2.303log .

60 11.6 − ( −3.8)

1 = 1. 55 × 10–3 min–1

Sol 37: H2O2(g) → H2O() + O (g)

2 2

At time, t = 120 min, qt = + 10. 2º

Here, Vr ∝ [H2O2]

Assuming this is a first order reaction 2.303 (13.1) − ( −3.8)

k2 = log = 1. 57 × 10–3 min–1

120 (10.2) − ( −3.8)

2.303 [H O ] 1 V

k= log 2 2 0 = log 0

t [H2O2 ]t t Vt At time, t = 180 min, qt = +9. 0º

At time, t = 0, Vr 22. 8 cc = V0

2.303 (13.1) − ( −3.8)

k3 = log = 1. 54 × 10–3 min–1

t = 10,Vr = 13. 3 cc = Vt 180 (9.0) − ( −3.8)

2.303 22.8 At time, t = 360 min, qt = +5. 87º

k1 = log = 5. 4 × 10–2 min–1

10 13.3

2.303 (13.1) − ( −3.8)

t = 20,Vr = 8. 25 cc = Vt k4 = log = 1. 55 × 10–3 min–1

360 (5.87) − ( −3.8)

2.303 22.8

k2 = log = 5. 1 × 10–2 min–1 We see that, k1, k2, k3 and k4 are all same within

20 8.25

experiment value.

k1 and k2 are equal within experimental error.

Therefore, this is a first order reaction

Therefore, first order reaction.

0.693 0.693

Half-life = = = 10. 677 min

k 6.49 × 10−2

Sol 38: For inversion of cane sugar, assuming first order,

(i) (PA)I = 90 mm Hg

1 θ − θ∞

k= log 0 (ii) (PA)f = 47 mm Hg

t θf − θ∞

(iii) k = 6. 49 × 10–2 min–1

At time, t = 0, θ = q0 = + 13. 1

(iv) t1/2 = 10. 67 min

At time, t → ∞,θ = θ∞ = –3. 8

At time, t = 60, θ+ = 11. 6º Sol 40: 2N2O5(g)→4NO2(g)+O2(g)

time, t = 0 P0 0 0

Sol 39: A(g) → 2B(g) + C(g)

time, t = t P0 – 2x 4x x

Time, t = 0 P0 0 0

t→∞ 0 2 P0 P0

Time, t P0 – x 2x x

2

Time, t→∞ 0 2P0 P0 P0

At t → ∞, Pt = 584. 5 = 2P0 +

At, t → ∞,Pt = 3P0 = 270 mm Hg 2

5P0

P0 = 90 mm Hg = (PA) ⇒ = 584. 5

2

At, t = 10 min, Pt = P0 – x + 2x + x = P0 + 2x = 176

⇒ P0 = 233. 8 mm Hg

2x = 176 – 90

At t = 30 min,

x = 43 mm Hg

Pt = 284. 5 = P0 – 2x + 4x + x

(PA)+ = P0 – x = 90 – 43 = 47 mm Hg

⇒ P0 + 3x = 284. 5

Chem i str y | 18.79

x = 16. 9 mm Hg Vt −25 × 5.05 × 10−2

= 1. 10 = 1 – 0. 284

PN = P0 – 2x V0 2.303

2O5

We have,

1

Sol 42: H2O2 → H2O + O

−1 d[N2O5 ] 2 2

= k[N2O5]

2 dt We are given complete dissociation gives 46. 34 mL O2.

[N2O5 ]t t Also VO ∝ [H2O2]

d[N2O5 ] 2

∫ = −2k ∫ dt

[N2O5 ]0 ( VO is volume of O2 a given sample of H2O2 can give)

[N2O5 ]0 0 2

∴ [H2O2] 0 ∝ 46. 34

[N2O5 ]t

ln = –2kt Also, at t = 5.1 days, VO = 10. 31 mL

[N2O5 ]0 2

2.303 [N O ]

k= log 2 5 0

2t [N2O5 ]t 2.303 [H O ]

So, k = log 2 2 0

t [H2O2 ]t

2.303 (PN O )0

k= log 2 5 (∵ PN O ∝ [N2O5]) 2.303 46.34

2t (PN O )t 2 5

k= log

2 5

5.1 46.34 − 10.31

2.303 233.8

= log k = 4. 93 × 10–2 days–1.

2 × 30 200

When 20 mL, O2 lost,

k = 2. 605 × 10–3 min–1.

[H2O2] t ∝ (46. 34 –20. 00)

t= log

V k [H2O2 ]0 − [H2O2 ]t

2.303

k= log 0

t Vt

2.303 46.34

= log

We have,V0 = 22. 8 cc 4.93 × 10 −2 46.34 − 20

At t = 10 min, Vt = 13. 8 cc t = 11. 45 days

2.303 22.8

k1 = log = 5. 02 × 10–2 min–1 Sol 43: A(aq) → B(aq) + C(aq)

10 13.8

t = 0 n0

At t = 20 min, Vt = 8. 25 cc

t = t n0 – x x x

2.303 22.8 t →∞ 0 n0 n0

k2 = log = 2 × 10–2 min–1

20 8.25

At t → ∞,θ∞ = –5º = n0. θB + n0θC

Since, k1 ≈ k2. This is first order reaction.

We have, θA = 20º, θB = 30º,

0.693 0.693

(b) t1/2 = = = 13. 75 min θC = –40º

k 5.05 × 10−2

∴ 30n0 – 40n0 = –5

(c) At t = 25 min,

n0 = 0. 5

2.303 V At time, t = 6. 43 min.

k= log 0

25 Vt

qt = (n0 – x)θA + x(θB + θC) = 2. 5

1 8 . 8 0 | Chemical Kinetics

= (1 − e−kt ) + (1 − e−kt )

30x = 20 × 0. 5 – 2. 5 k k

30x = 7. 5 k + k2 (1 −e−kt )

[x]0 (1 − e ) = [x] 0 e

−kt

= 1

x = 0. 25 k

For first order conversion, [x]t e−kt 1

∴ = =

2.303 n [y] + [2] 1−e −kt

e

+ (k1 +k 2 )t

−1

k= log 0

t n0 − x

Sol 45: Using results of previous question

2.303 0.5

= log

6.93 0.5 − 0.25 k 2 [A]0

[C]t = (1 − e−kt ) , k = k1 + k2

k = 0. 1 min–1

k

[A]t = [A]0e–kt

Sol 44:

[C]t k2 (1 − e−kt ) 1

= = (e−kt − 1)

k1 B [A]t k1 + k 2 e −kt k1

1+

x k2

k2 C We have, k1 = x hr–1, k2 = 10 k1

= 10 × hr–1, t = 1 hr

(B = y, C = z)

[C]t 1

We have, ∴ = (e(x +10x) − 1)

[A]t 1

1+

d[x] 10

= –(k1 + k2)[x] [C]t

dt 10 11x

= (e – 1)

[A]t 11

[x]t t

d[x]

∫ = −(k1 + k 2 )∫ dt

[x]0

[x] 0 Sol 46: We have,

k k

⇒[x] t = [x]0e–kt, k = k1 + k2 A → B

1 2→ C,

Now, = k1[x] t k1 = ,k =

dt ln1 2 2

d[B] For [A]

= k1[x]0e–kt

dt d[A]

[B]t t

= –k1[A]

−kt

dt

∫ d[B] = k1[x] 0 ∫e

0 0 ⇒ [A] = [A] 0 e−k1t

−k1 [x]0 t

d[B]

[B]t = e−kt = k1[A] – k2[B]

k 0 dt

d[B]

−k1 [x]0 = k1[A] 0 e−k1t – k2[B]

[B] t = (1 − e −kt

) dt

k1 + k 2

d[B]

+ k2[B] – k1[A]0 e−k1t = 0…(i)

dt

k 2 [x]0

Similarly [C] t = (1 − e−kt ) This is a linear differential equation.

k1 + k 2

Chem i str y | 18.81

[B] t = [e −e ] k2 = 2 antilog −

k 2 − k1

2.303R 300 T

d[B]t k1

Now, at [B] max, =0 =2

dt k2

d[B]t

In (i), putting = 0, we get ((Ea )1 − (Ea )2 ) 1 1

dt 4antilog − =2

2.303R 300 T

k1[A]0 e−k1t = k2[B]

(Ea )1 .(Ea )2 1 1 1

− = log

k 2k1 [A]0 −k1t −k 2t 2.303R 300 T 2

k1[A]0 e−k1t = [e −e ]

k 2 − k1 (Ea )1 = 20 kJ/mol,

k 2e .k1e = k 2e .k 2e (Ea )2 = 2. 8314 kJ/mol

3

k1 ⇒ (28.314 − 20) × 10 1 − 1 =0. 7

= (k −k )t

e 1 2 8.314 300 T

k2

1 1

logk1 − logk 2 − = 7 × 10–4

t = 300 T

.2.303

k1 − k 2 1

= 2. 63 × 10–3

1 ln2 −4 1 T

t= ln = ln = 4

k1 − k 2 4.ln2 ln2 2 T = 379. 75 K

∴ t = 4 min.

Sol 48: H2O + O → 2OH–, Ea

1

k1 2OH– → H2O + O, Ea

B 2

Sol 47: A

Potential energy →

k2 C

E a2

[B] k1

= Ea1

[C] k2 2OH

[B] k1

We need, =2= H2O+O

[C] k2

Reaction coordinate →

Let temperature be T.

By Arrhenius equation.

Ea = Ea – ∆H = (77. 72) kJ mol–1

2 1

Ea = 5 kJ mol–1

k2 Ea 1 1 2

log = −

k1 2.303R T1 T2

Sol 49: For t1/2 = 1 min, k = 0.693

t1/2

For A

k1

→ B, k2 = k1, k1 = 8,

= 0. 693 min = 1. 155 × 10 s –1 –2

−1

Ea = 20 kJ/mol (E1), T1 = 300, T2 = T Ea A

−Ea

Now, k = A e RT

⇒T= ln

R k

k1 (Ea )1 1 1

log = − A = 5 × 1013 sec–1

8 2.303R 300 T

Ea = 104. 5 kJmol–1

(Ea )1 1 1 −1

k1 = 8 antilog − 3

T = 104.5 × 10 ln 5 × 1013

2.303R 300 T

8.134 1.155 × 10 −2

For A

k2

→ C, similarly,

T = 349. 1 K

1 8 . 8 2 | Chemical Kinetics

Sol 53: Temperature coefficient = = 1. 75

k2 Ea

1 1 k 298 k

log = −

k1 2.303R T1 T2 By Arrhenius equation

1 1

log = −

k2 k 298 k 2.303k 298 308

T2 = 47ºC = 320 K, =4

k1

log1.75 × 2.303 × 8.314 × 298 × 308

Ea 1 1 Ea =

∴ log 4 = − 10

2.303 × 8.314 300 320

= 42. 711 kJ mol–1

log 4 × 2.303 × 8.314 × 300 × 320

Ea = Ea = 10. 757 kJ mol–1

20

Ea = 55. 33 kJ/mol

Sol 54: At T1 = 380ºC = 653 K,

0.693 –1 0.693

Sol 51: For t1/2 = 2 hr, k = 0.693 = hr k1 = 0.693 = = 1. 925 × 10–3 min–1

t1/2 2 t1/2 360

= 9. 625 × 10–5 sec–1

T2 = 450º C = 723 K, k2 = k

So, we have, k1 = 3. 46 × 10–5 sec–1

Ea = 200 k J mol–1

k2 = 9. 625 × 10 sec –5 –1

By Arrhenius equation

Ea = 100 kJ mol–1

k2 Ea 1 1

T1 = 25ºC = 298 K log = −

k1 2.303R T1 T2

T2 = T

k 200 × 103 1 1

By Arrhenius equation. log = −

−3 2.303 × 8.314 653 723

1.925 × 10

k2 Ea

1 1

log = − k

k1 2.303R T1 T2 log = 1. 548

1.925 × 10 −3

9.625 × 10 −5 100 × 103 1 1 k = 6. 81 × 10–2 min–1

log = −

−5 2.303 × 8.314 298 T

3.46 × 10 2 × 0.693

Time required for 75 % reaction = 2t1/2 =

1 1 6.8 × 10−2

⇒ − = 8. 5 × 10–5 Time = 20. 4 minutes

298 T

T = 306 K Sol 55: We have,

(i) NO + Br2 NOBr2

k = A e−Ea /RT k2

k3

k2 (Ea −Ea )/RT (ii) NOBr2 + NO

→ 2NOBr

= e 1 2

k1

This is RDS

We have,

Here, we use equilibrium approach, as equilibrium is

Ea = 75 kJ mol–1 achieved fast

1

Ea = 25 kJ mol–1 Rate = k3[NOBr2] [NO]

2

T = 25ºC = 298 K For equilibrium of (i),

k2

∴ = 5. 8 × 108 k1 [NOBr2 ]

k1 =

k2 [NO][Br2 ]

Therefore, rate of reaction increases by 5. 8 × 108 times.

Chem i str y | 18.83

[NOBr2] = [NO] [Br]

k2 (ii) 2I + H2

k2

→ 2HI, RDS

k1k 3 [I]2

Hence, rate = [NO] [Br] = k[NO] [Br2]

2 2 from (i) equilibrium, k1 =

k2 [I2 ]

k1k 3 [I] 2 = k1[I2]

k=

k2 from (ii)Rate = k2[I] 2[H2]

= k2k1[I2] [H2]

Sol 56: (i) 2NO → N2O2

= k[H2] [I2] , k=k2k1

equilibrium constant = k1 (fast)

(c) (i) I2 → 2I

(ii) N2O2 + H2

k2

→ N2O + H2O

equilibrium constant = k1, fast

RDS

k3 (ii) I + H2 → HI2

(iii) N2O + H2 → N2 + H2O

k

3

→ 2HI, RDS

(iii) IH2 + I

As equilibrium step is fast, we use equilibrium approach

equilibrium constant = k2, fast

[N2O2 ]

from (i), k1 = [I]2

[NO] 2 from equilibrium (i), k1 =

[I2 ]

[N2O2] = k1[NO] 2 [I] 2 = k1[I2]

Also, from (ii), Rate = k2[N2O2] [H2] from equilibrium (ii),

= k1k2[NO] [H2] 2

[IH2 ]

k2 = [HI] 2

= k[NO] [H2] 2

[I][H2 ]

k = k 2k 3 [IH2] = k2[I] [H2]

Sol 57 (i) NO + NO N2O2 [fast] k −1

Rate = k3[IH2] [I]

(ii) N2O2 + O2

→ 2NO2 (RDS)

k2

= k3k2[I] 2[H2]

from equilibrium of (i),

= k1k2k3[I2] [H2]

k1 [N2O2 ]

= Rate = k[H2] [I2]

k −1 [NO]2

(d) No, it cannot distinguish between the three mechanisms

k1 as all the 3 molecules gives the same rate law.

[N2O2] = [NO] 2

k −1

(e) Mechanism (a) becomes most improbable as it just

from (ii) involves one step and it is highly unlikely that I2 and H2 will

combine directly at 200ºC without breaking into radicals.

1 d[NO2 ] k 2k1

Rate = = k2[O2] [N2O2] = [NO] 2[O2]

2 dt k −1

1 d[NO2 ]

Exercise 2

Rate = = k[NO]2[O2] ,

2 dt Single Correct Choice Type

k 2k1

k= Sol 1: (B) We know,

k −1 1

Coefficient in rate law =

stiochiometric coefficient

Sol 58: (a) H2 + I2 → 2HI Given rate law

since, this is one step, rate = k[H2] [I2] 1 d[C] −1 d[D] +1 d[A] d[B]

+ = = = −

2 dt 3 dt 3 dt dt

(b) (i) I2 → 2I

Reaction is 3D + B → 2C + 4A

1 8 . 8 4 | Chemical Kinetics

doubled. log(a0–x) = + log a0

2.303

Now, reaction is first order w. r. t O2 and second order −kt

Slope of log (a0 – x) vs. t graph is

w. r. t N2 2.303

−k

\ Rate = k[O2] [N2] 2 Slope of given graph = –3. 3 × 10–3=

2.303

rf = k[2O2] [2N2] 2 ⇒ k = 7. 7 × 10–3

rf = k[2O2] [2N2] 2 = 8ri

Sol 8: (C) Volume strength = 5. 6 N0 = 16. 8º

Sol 3: (C) We have Now, after 2. 303 hours, let normality be N.

When 20 mL of this solution is diluted, Normality

becomes

Ef N.20 N

Energy →

Eb =

∆Η 100 5

It is diluted against 0. 02 M KMnO4.

Reaction coordinate→ Under acidic conditions, normality of KMnO4 = M × 5

∴ |∆H| = Eb – Ef = (200 – 180) kJ mol–1 = 0. 02 × 5 = 0. 1 N

N

. 25 = 0. 1 × 37. 5

5

Sol 4: (D) For zero order reaction

N = 0. 75 N

d[B]

rate, =k Now volume strength

dt

[B] = kt V = N × 5. 6 = 0. 75 × 5. 6 = 4. 2 V

Now,

[A] = [A]0 – kt

2.303 V

1 k= log 0

At time t = t3/4, [A] = [A0] t Vt

4

t = 2. 303 hours, V0 = 16. 8 V,

3[A]0

⇒t =

4k Vf = 4. 2 V

k= log

2.303 4.2

Similarly, t1/2 ∝ [A0]

k = 0. 60 hr–1

Sol 9: (A) For experiment 1,

reaction.

d[A] 1.5M

So, rate of reaction will be independent of time.

Conc.(M)→

dt

little probability for more than 3 atoms to collide

simultaneously. 10min

Time(min)→

2.303 a

Sol 7: (C) We have k = log 0

t a0 − x −∆[A] 0.55

Average rate = = = 0. 055 min–1

∆t 10

kt = 2. 303 log a0 – 2. 30 log(a0–x)

For experiment 2,

Chem i str y | 18.85

EP

1.5M

P

Energy →

0.8M

S+E

ES

5

Time(min)→

Reaction coordinate→

∆A

Average rate, r2 =

∆t This is the plot for enzyme catalysed reaction.

0.2 1 Correct option is (B).

= M min–1 = M min–1

5 25 Multiple correct choice type

r 0.55 [A]0

⇒ 1 = = 1. 375 ≈ 1. 5 = 1

r2 1 / 25 [A]0 Sol 13: (A, D) We have, emission rate of SO3

2

Hence the reaction is first order

= 6. 93 × 10–6 gm/L/day

When (A) = 1. 8 M

6.93 × 10−6

Rate, r = 1. 8 × [x]2 = mol/L/day

80

1.8

= M min–1 = 0. 072 M min–1 = 8. 6625 × 10–8 mol/L/day

25

≈ 0. 08 M min–1 For decomposition of SO3,

0.693 0.693

k= = = 6. 93 × 10–3 day–1

Sol 10: (A) Since k1 << k2 second reaction will have the t1/2 100

most activation energy

d[SO3 ]

Further, since the overall reaction is exothermic, = 8. 6625 × 10–8 – 693×10–3[SO3]

dt

therefore the final energy of products should be less

d[SO3 ]

than the reactants plot which satisfies above 2 is (A). At steady state, =0

dt

k1 8.6625 × 10−8

Sol 11: (A) NO(g) + Br2(g) NOBr2(g) ⇒ [SO3] =

k2 6.93 × 10−3

NOBr2(g) + NO(g) → 2NOBr(g)

3 k [SO3] = 1. 25 × 10–5 M

When dissolved in water (1 L),

Rate, R = –k3[NOBr2] [NO]

[SO3] = 1. 25 × 10–2 M

From equilibrium of (i),

Normality of SO3 = 2M = 2. 5 × 10–2 N

k1 [NOBr2 ]

= N1V1 = N2V2

k2 [NO][Br2 ]

2. 5 × 10–2 × 1000 = 1 × V2

k1

⇒ [NOBr2] = [NO] [Br2] V2 = 25 mL

k2

k 3k1 SO3 + H2O → H2SO2

Therefore, rate = [NO]2 [Br2 ]

k2 Rate of H2SO4 production

Order w. r. t. NO = 2 980 × 103

= 980 kg/day = mol/day = 104 mol/day

98

SO3 required = H2SO4 manufactured = 104 mol/day

1 8 . 8 6 | Chemical Kinetics

Now V = 2 [A]1/2 − 0

M 0

2

10 4 k

= = 8 × 108 L/day

1.25 × 10−5

[A]0

If SO3 emission stopped, t3/4 =

k

d[SO]3

= –6. 93 × 10–3[SO3]

dt Sol 15: (A, D) Solution will be optically active and

−6.93×10−3 t dextro after very long time

⇒ [SO3] = [SO3]0 e

−3 t After 75% conversion of A in to B and C angle of rotation

of solution will be 36°

[SO3] 0 = 1. 25 × 10–5 M

(A) is correct

\[SO3]0 ≈ 1. 2 × 10–8 M

Rate, R = k[A] m[B] n[C]0

−d[A] log R = log k + m log[A] + n log[B]

Sol 14: (A, B, D) = k(A) 1/2

dt If all concentration other than (A) are constant,

[A] t

−d[A] d(logk)

∫ = ∫ k dt Then =m

1/2

[A]0 [A] 0 d(log[A])

[A] t (C) Order of reaction can be fractional

2[A]1/2 = kt

[A]0 0

(D) Order of a reaction can only be determined

kt experimentally

(A) 1/2 = [A]1/2

0 =

2

−1 1/2 1/2) Sol 17: (A, C, D)

k= (A .A

2 0 (A) Unit of A = Unit of k ≠ mol L–1s–1

kt

A = + A0 (B) Order of an elementary must atleast be 1 (atleast 1

2 molecule should be present)

Straight line (C) Molecularity can be defined for any elementary

[A]0 reaction.

At t = t1/2, (A) =

2 (D) Decay constant (λ) of radioactive substance is

independent of temperature.

2 2k

t1/2 =

[A0 ]1/2 Sol 18: (A, C) With increase in [A]0, rate will increase,

[A0 ]1/2 − 0

2 leading to increase in yield of B. A → B has higher Ea,

1/2 which means it has lower k and thus with increase in

[A] temperature k1 will increase more than k2, resulting in

2 [A0 ]1/2 1/2

0 2([2A]0 −

2 increase in yield of B.

k

= = 0

( 2 − 1)

( 2 − 1)[A]0 k (D) A zero order reaction is always complex, rest all are

correct.

[A]0

At t = t3/4, (A) =

4

2k

\t3/4 =

[A]1/2

[A]1/2

0 −

0

2

Chem i str y | 18.87

fractional, through the overall order of a reaction can x

be fractional.

k2 C

k1 2B

A (B = y, C = z)

k2 2C We have,

[B] k 1 d[x]

We have, = 1 = = –(k1 + k2)[x]

[C] k2 2 dt

1 [x]t t

For every mole of A consumed, mole used for forming d[x]

3 ∫ = −(k1 + k 2 )∫ dt

B and rest for forming C. [x]

[x]0 0

[A]0 = 2 moles

⇒[x]t = [x]0e–kt, k = k1 + k2

At end of 50% reaction, A0 = 1 mole

1 2 d[B]

Bn = ×2×1 = moles Now, = k1[x]t

3 3 dt

2 4 d[B]

Cn = ×2×1 = moles = k1[x]0e–kt

3 3 dt

[B]t

[Since, for every mole A, 2 moles of B (or C) is produced] t

−kt

∫ d[B] = k1[x]0 ∫e

0 0

Sol 21: (D) A(aq) → B(aq) + C(aq)

−k1 [x]0 t

t=0 n0 [B]t = e−kt

k 0

t = t n0 – x x x

−k1 [x]0

t →∞ 0 n0 n0 [B]t = (1 − e−kt )

k1 + k 2

At t → ∞,θ∞ = –5º = n0.θB + n0θC

k 2 [x]0

Similarly [C]t = (1 − e−kt )

We have, θA = 20º, θB = 30º, k1 + k 2

= (1 − e−kt ) + (1 − e−kt )

n0 = 0.5 k k

k + k2 (1 −e−kt )

At time, t = 6.43 min. = 1 −kt

[x]0 (1 − e ) = [x]0 e

k

θt = (n0 – x)θA + x(θB + θC) = 2.5

[x]t e−kt 1

20n0 + x(30.40 – 20) = 2.5 ∴ = =

[y] + [2] 1−e −kt

e

+ (k1 +k 2 )t

−1

30x = 20 × 0.5 – 2.5

Sol 23: (C) Using results of previous question

30x = 7.5

x = 0.25 k 2 [A]0

[C]t = (1 − e−kt ) , k = k1 + k2

k

For first order conversion,

[A]t = [A]0e–kt

2.303 n 2.303 0.5

k= log 0 = log

t n0 − x 6.93 0.5 − 0.25 [C]t k2 (1 − e−kt ) 1

= = (e−kt − 1)

[A]t k1 + k 2 e −kt k1

k = 0.1 min–1 1+

k2

1 8 . 8 8 | Chemical Kinetics

[C]t 1 n1A(g) → n2B(g)

∴ (e(x +10x) − 1)

=

[A]t 1

1+ time 0 a 0

10

[C]t 10 11x time t a – n1x n2x

= (e – 1)

[A]t 11

−1 d[A]

\Rate = k[A] = = k[A]

n1 dt

Sol 24: (C) For reactions with order ≤ 1, time of at t

completion can be determined as those reactions gets d[A]

⇒ ∫ = −n1k ∫ dt

fully completed in specific amount of time. a

dt 0

n = –n1kt

% completion and hence time of completion cannot be a

determined. −n1kt

at = a e

Sol 29: (D) n1A(g) → n2B(g)

Without catalyst t = 0 a 0

−n1kt n2 −n1kt

t=1 ae a(1 − e )

n1

Ea Total moles present

Energy

R

−n kt n n −n kt

= a e 1 + 2 − 2 e 1

P

n1 n1

Reaction coordinate n n −n kt

= a 2 − 2 − 1 e 1

n

1 n1

With catalyst

Concentration is to remain same at time t,

∴ = 0

V V0

Ea

n n −n kt

Energy

R V0 n

⇒V = = V0 2 − 2 − 1 e 1

a0 n1 n1

P

at time t,

= V0(2 – e–kt)

2 4

Sol 26: (B) Total number of moles = 1+ + = 3 moles e−kt

3 3 nA ae−kt

(A) = = = (A)

2 V V0 (2 − e−kt )

0 2 − e−kt

Sol 27: (C) Moles of B = = 0. 666 moles.

3

Chem i str y | 18.89

k1 [A]0 −3 –1

Sol 31: (C) (B) = [e

−k1t

−e

−k 2t

] = –k = hr

k 2 − k1 200

3

d[B] k [A] −k t −k t ⇒k = hr–1

= 1 0 ( −k1e 1 + k 2e 2 ) 200

dt k 2 − k1

1

d[B] When f =

When (B) is maximum, =0 2

dt 1

d[B] = 1 – e–kt

=0 2

dt n2 0.693 × 200

−k1t −k 2t

t= = = 46. 2 hrs.

⇒ −k1e + k 2e =0 k 3

−k1t −k 2t

k1 e = k 2e Sol 34: (A) f = 1 – e–kt

k1 f = [1 – e–3t/200]

=

k2

k1 1 k Paragraph 5

(k1 – k2)t = ln ; ⇒t = ln 1

k2 k1 − k 2 k 2 3

Sol 35: (C) For t = 100 min, x = a

4

Sol 32: (C) For k1 = 1000 s–1, k2 = 20 s–1, 1 a n2

\k = ln = min–1

100 3 50

[A]t = [A]0 e–1000t a− a

4

1000 When x = 0. 9 a,

[B]t = [A] [e−1000t − e−20t ]

20 − 1000 0 1 a

k= ln

1 1000 t a − 0.9a

≈ [A]0e–20t, tmax = n

1000 − 20 20

1 50ln10 50 50

t= ln10 = = = ; = 166. 66 min

[B]t will increase till tmax and then decay exponentially k ln2 ln2 0.3

Sol 36: (B) [A]0 = = 0. 16

= [A]0 – [A0] e–1000t – [A]0e–20t 12.5

We have,

= [A]0(1 – e –1000t

–e –20t

) 1 d[B]

= k[A]

≈ [A]0(1 – e )

–20t 3 dt

A(g) → 3B(g) + 2C(g)

[C]t will approach [A]0 asymptotically.

At time 0 0. 16

At time t 0. 16–x 3x 2x

Paragraph 4

d[A]

df Also, = –k[A]

We have = k(1 – f) dt

dt

[A] = [A]0 e–kt

f f

df −2 ×100

∫1−f = ∫ k dt = 0. 16 e1.386×10

0 0

= 0. 04

f

−ln(1 − f)0f = k f

0 i. e. , 0. 16 – x = 0. 04

–ln(1 – f) = kt x = 0. 12

f = 1 – e–kt (B) = 3x = 0. 36.

1 8 . 9 0 | Chemical Kinetics

t1/2 ∝

[A0 ]n−1

We have,

decreasing graph

1 d[B] −d[A]

=

2 dt dt Matches (C).

(U) vs t(order = 2)

[A]

(B) → r

we have,

[A] = [A]0e–kt

−d[A] −k

exponential decay =

dt [A]2

(C) → p

[A] t

d[A]

(B) = 2([A]0 – [A]); = 2[A]0 (1 – e–kt) ⇒ ∫ = −k ∫ dt

[A]0 [A]2 0

Exponential graph will approach 2(A)0 asymptotically.

[A]

(D) → q −1 t

⇒ = −k t

[A]0 0

For zero order, [A0 ]

[A] = [A]0 – kt 1 1

⇒ − = –kt

Straight line with slope –k. [A]0 [A]

1 1

Sol 38: We will draw all graphs given in Column-II and ⇒ = kt +

[A] [A]0

then match them with Column-I.

Straight line with positive slope and positive intercept.

(p) ln (A) vs t (order 1)

Matches no option in Column-I.

We have, [A] = [A]0e–kt

(V)r vs [A] (order = 1)

ln[A] = ln[A]0 – kt

r = k[A]

Straight line with negative slope matches (A). Straight line with positive slope.

(q) t1/2 vs (A)0 (order = 1) Matches (D)

0.693 (A) → p

t1/2 =

k (B) → q, s

It is independent of [A]0, straight line parallel to x-axis. (C) → r, t

Matches (B)

(D) → v

(r) r vs t (order > 0)

r = k[A]n, n > 0

Previous Years’ Questions

for order > D, rate decreases with increasing t as (A)

decreases with t Sol 1: (A) The rate constant (k) of all chemical reactions

\decreasing graph (not straight line) matches (C). depends on temperature.

where, A = Pre-exponential factor,

For order, r is constant of time, graph is straight line

parallel to x-axis. Ea = Activation energy.

Sol 2: (C) A catalyst increases the rate of reaction but

by the same factor to both forward and backward

Chem i str y | 18.91

directions. Hence, a catalyst shorten the time required Sol 11: k = 1.5 × 10–6 s–1

to reach the equilibrium.

100

kt = ln

100 – x

Sol 3: (D) Rate will be directly proportional to both

concentration and intensity, i.e, rate of formation of AB 100

⇒ ln

* ∝ C. I. 100 – x

= 1.5 × 10–6 s–1 ×10 × 60 × 60s; = 0.0054

Sol 4: (D) Order of a reaction can take any real value, 100

⇒ = 1.055

i.e, negative, integer, fraction, etc. 100 – x

⇒ x =5.25% reactant is converted into product

Sol 5: (A) According to Arrhenius equation, rate

ln2 0.693

constant increases exponentially with temperature : Half-life = = = 462000 s; = 128.33 h

k = Ae–Ea /RT k 1.5 × 10 −6

Sol 6: (A) Living plants maintain an equilibrium

h is 346 particles min–1.

between the absorption of C14 (produced due to cosmic

radiation) and the rate of decay of C14 present inside ⇒ Rate = kN

the plant. This gives a constant amount of C14 per gram Rate 346 × 66.6 × 60

of carbon in a living plant. ⇒N= =

k 0.693

= 1.995 × 106 atoms

Sol 7: (B) Fossil whose age is closest to half-life of C–14

(5770 yr) will yield the most accurate age by C–14 dating. N0

⇒ kt = ln

N

N0 ln2 N

Sol 8: (A) λT =ln ⇒ × 6.909 = ln 0 = 0.0715

N 66.6 N

where N0 = Number of C14 in the living matter and

N = Number of C14 in fossil. Due to nuclear explosion, N0

⇒ = 1.074

amount of C14 in the near by area increases. This will N

increase N0 because living plants are still taking C–14

⇒ N0 = 1.074 × N = 1.074 × 1.995 × 106

from atmosphere, during photosynthesis, but N will not

change because fossil will not be doing photosynthesis. = 2.14 × 106 atoms of Mo

⇒ T (age) determined in the area where nuclear ⇒ Mass of Mo required

explosion has occurred will be greater than the same

2.14 × 106

determined in normal area. = × 99 = 3.56 × 10–16g

6.023 × 1023

C1

Also, λT1 =

ln

C Sol 13: CH3–O–CH3(g) → CH4(g)+ H2(g)+CO(g)

C

ln 2

λT2 = At 12 min :0.40 – p p p p

C

C1 Total pressure = 0.4 + 2p

⇒ T1 – T2 = ln

C2

0.40

C = Concentration of C–14 in fossil. Also k × 12 = ln

0.40 – p

ln2

Sol 9: Rate of reaction is constant with time. = × 12 = ln 0.40

14.5 0.40 – p

ln2 0.693 ⇒ p = 0.175

Sol 10: k = = yr–1 = 1.2 × 10–4 yr–1

t1/2 5770 ⇒ Total pressure = 0.4 + 2p

1 ln2 = 0.4 + 2 × 0.175

Also kt = ln = × 11540 = ln 4

f 5770

= 0.75 atm.

1

⇒f= = 0.25

4

1 8 . 9 2 | Chemical Kinetics

Sol 14: (A) ln =

k1 R T1 T2 rate ∝ [G]a [H]b

a = 1, b = 2

4.5 × 107 Ea 50

⇒ ln =

7 8.314 323 × 373 0.693 0.693

1.5 × 10 Sol 17: (A)

= k1 =

t1/2 40

⇒ Ea = 22 kJ

A0 1.386

Ea k0

= =

Also ln k = ln A – 2t1/2 2 × 20

RT

At 50°C :

k1 0.693 40 0.693

22 × 1000 = × = = 0.5 mol−1 litre

ln A = ln (1.5 × 10 ) –7

= 8.33 k0 40 1.386 1.386

8.314 × 323

⇒ A = 4.15 × 103 s–1

2.303log8 2.303 × 3log2

1 Sol=

18: t1/8 =

(b) N2O5 (g) → 2NO2 (g) + O2 (g) k k

2

p 2.303 2.303

600–p 2p =t1/10 = log10

2 k k

3 2.303 × 3log2

Total pressure = 690 = 600 + p

2 t1/8 k × 10 9

⇒ p = 240 mm =

× 10 =

t1/10 2.303

⇒ Partial pressure of N2O5(g)

k

remaining

= 600 – 240 Sol 19: (D) Overall order of reaction can be decided by

= 360 mm the data given t75% = 2t50%

360 ∴ It is a first order reaction with respect to P.

⇒ Mole-fraction = = 0.375

960

From graph [Q] is linearly decreasing with time, i.e.

order of reaction with respect to Q is zero and the rate

Sol 15: (A) Partial pressure becomes half of initial in expression is r = k [P]1[Q]0.

every 100 min, therefore, order = 1.

Hence (D) is correct.

800

(B) k × 100 = ln = ln 2 n

400 r1

1 M

Sol 20: (C) = = ⇒n= 3

⇒ k = 6.93 × 10–3 min–1 r2 8 2Mn

(C) For 75% reaction; time required

Sol 21: (B, C, D) A high activation energy usually

= 2 × half-life implies a slow reaction.

= 200 min

(D) 2X(g) → 3Y(g) + 2Z(g)

3

800–x x x

2

3

Total pressure = 800 + x

2

Also 800 – x = 700

⇒ x = 100

⇒ Total pressure

3

= 800 + × 100 = 950 mm

2

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