Q1 |
From the rate expression for the following reactions, determine their order of reaction and the dimensions of the rate constants.
(i) 3 NO(g) → N2O(g) Rate = k[NO]2
(ii) H2O2 (aq) + 3 I - (aq) + 2 H+→ 2 H2O (l) + I3- Rate = k[H2O2][I - ]
(iii) CH3CHO(g) → CH4(g) + CO(g) Rate = k [CH3CHO]3/2
(iv) C2H5Cl(g) → C2H4(g) + HCl(g) Rate = k [C2H5Cl] |
Ans: |
(i) Given rate = k [NO]2
Therefore, order of the reaction = 2
Dimension of k = Rate / [NO]2
= mol L-1 s-1 / (mol L-1)2
= mol L-1 s-1 / mol2 L-2
= L mol-1 s-1
(ii) Given rate = k [H2O2][I - ]
Therefore, order of the reaction = 2
Dimension of k = Rate / [H2O2][I - ]
= mol L-1 s-1 / (mol L-1) (mol L-1)
= L mol-1 s-1
(iii) Given rate =k [CH3CHO]3/2
Therefore, order of reaction = 3/2
Dimension of k = Rate / [CH3CHO]3/2
= mol L-1 s-1 / (mol L-1)3/2
= mol L-1 s-1 / mol3/2 L-3/2
= L½ mol-½ s-1
(iv) Given rate = k [C2H5Cl]
Therefore,order of the reaction = 1
Dimension of k = Rate / [C2H5Cl]
= mol L-1 s-1 / mol L-1
= s-1 |
|
Q2 |
For the reaction:
2A + B → A2B
the rate = k[A][B]2with k= 2.0 x 10-6mol-2L2s-1. Calculate the initial rate of the reaction when [A] = 0.1 mol L-1, [B] = 0.2 mol L-1. Calculate the rate of reaction after [A] is reduced to 0.06 mol L-1. |
Ans: |
The initial rate of the reaction is
Rate = k [A][B]2
= (2.0 × 10 - 6mol - 2L2s - 1) (0.1 mol L - 1) (0.2 mol L - 1)2
= 8.0 × 10 - 9mol - 2L2s - 1
When [A] is reduced from 0.1 mol L - 1to 0.06 mol - 1, the concentration of A reacted = (0.1 - 0.06) mol L - 1 = 0.04 mol L - 1
Therefore, concentration of B reacted= 1/2 x 0.04 mol L-1 = 0.02 mol L - 1
Then, concentration of B available, [B] = (0.2 - 0.02) mol L - 1
= 0.18 mol L - 1
After [A] is reduced to 0.06 mol L - 1, the rate of the reaction is given by,
Rate = k [A][B]2
= (2.0 × 10 - 6mol - 2L2s - 1) (0.06 mol L - 1) (0.18 mol L - 1)2
= 3.89 mol L - 1s - 1 |
|
Q3 |
The decomposition of NH3on platinum surface is zero order reaction. What are the rates of production of N2and H2if k = 2.5 x 10-4mol-1L s-1? |
Ans: |
The decomposition of NH3on platinum surface is represented by the following equation.
= 7.5 × 10 - 4mol L - 1s - 1 |
|
Q4 |
The decomposition of dimethyl ether leads to the formation of CH4, H2and CO and the reaction rate is given by
Rate = k [CH3OCH3]3/2
The rate of reaction is followed by increase in pressure in a closed vessel, so the rate can also be expressed in terms of the partial pressure of dimethyl ether, i.e.,
Rate = k (PCH3OCH3)3/2
If the pressure is measured in bar andtime in minutes, then what are the units of rate and rate constants? |
Ans: |
If pressure is measured in bar and time in minutes, then
Unit of rate = bar min - 1
Rate = k (PCH3OCH3)3/2
⇒ k = Rate / (PCH3OCH3)3/2
Therefore, unit of rate constants (k) = bar min-1 / bar3/2
= bar-½ min - 1 |
|
Q5 |
Mention the factors that affect the rate of a chemical reaction. |
Ans: |
The factors that affect the rate of a reaction areas follows.
(i) Concentration of reactants (pressure in case of gases)
(ii) Temperature
(iii) Presence of a catalyst |
|
Q6 |
A reaction is second order with respect to a reactant. How is the rate of reaction affected if the concentration of the reactant is
(i) doubled
(ii) reduced to half? |
Ans: |
Let the concentration of the reactant be [A] = a
Rate of reaction, R = k [A]2 = ka2
(i) If the concentration of the reactant is doubled, i.e. [A] = 2a, then the rate of the reaction would be
R = k(2a)2
= 4ka2
= 4 R
Therefore, the rate of the reaction would increase by 4 times.
(ii) If the concentration of the reactant is reduced to half, i.e. [A] = 1/2 a, then the rate of the reaction would be
R = k(1/2a)2
= 1/4 Ka2
= 1/4 R |
|
Q7 |
What is the effect of temperature on the rate constant of a reaction? How can this temperature effect on rate constant be represented quantitatively? |
Ans: |
The rate constant is nearly doubled with a rise in temperature by 10° for a chemical reaction.
The temperature effect on the rate constant can be represented quantitatively by Arrhenius equation,
K = Ae -Ea / RT
where, kis the rate constant,
A is the Arrhenius factor or the frequency factor,
R is the gas constant,
T is the temperature, and
Ea is the energy of activation for the reaction |
|
Q8 |
In a pseudo first order hydrolysis of ester in water, the following results were obtained:
t/s |
0 |
30 |
60 |
90 |
[Ester]mol L - 1
|
0.55 |
0.31 |
0.17 |
0.085 |
(i) Calculate the average rate of reaction between the time interval 30 to 60 seconds.
(ii) Calculate the pseudo first order rate constant for the hydrolysis of ester. |
Ans: |
(i) Average rate of reaction between the time interval, 30 to 60 seconds, = d[ester] / dt
= (0.31-0.17) / (60-30)
= 0.14 / 30
= 4.67 × 10 - 3mol L - 1s - 1
(ii) For a pseudo first order reaction,
k = 2.303/ t log [R]º / [R]
For t= 30 s, k1 = 2.303/ 30 log 0.55 / 0.31
= 1.911 × 10 - 2s - 1
For t = 60 s, k2 = 2.303/ 60 log 0.55 / 0.17
= 1.957 × 10 - 2s - 1
For t= 90 s, k3 = 2.303/ 90 log 0.55 / 0.085
= 2.075 × 10 - 2s - 1
Then, average rate constant, k = k1 + k2+ k3 / 3
= 1.911 × 10 - 2 + 1.957 × 10 - 2 + 2.075 × 10 - 2 / 3
= 1.981 x 10-2 s - 1 |
|
Q9 |
A reaction is first order in A and second order in B.
(i) Write the differential rate equation.
(ii) How is the rate affected on increasing the concentration of B three times?
(iii) How is the rate affected when the concentrations of both A and B are doubled? |
Ans: |
|
|
Q10 |
In a reaction between A and B, the initial rate of reaction (r0) was measured for different initial concentrations of A and B as given below:
A/ mol L - 1
|
0.20 |
0.20 |
0.40 |
B/ mol L - 1
|
0.30 |
0.10 |
0.05 |
r0/ mol L - 1 s - 1
|
5.07 × 10 - 5
|
5.07 × 10 - 5
|
1.43 × 10 - 4
|
What is the order of the reaction with respect to A and B? |
Ans: |
Let the order of the reaction with respect to A be xand with respect to B be y.
Therefore,
= 1.496
= 1.5 (approximately)
Hence, the order of the reaction with respect to A is 1.5 and with respect to B is zero. |
|
Q11 |
The following results have been obtained during the kinetic studies of the reaction: 2A + B → C + D
Experiment |
A/ mol L - 1
|
B/ mol L - 1
|
Initial rate of formation of D/mol L - 1 min - 1
|
I |
0.1 |
0.1 |
6.0 × 10 - 3
|
II |
0.3 |
0.2 |
7.2 × 10 - 2
|
III |
0.3 |
0.4 |
2.88 × 10 - 1
|
IV |
0.4 |
0.1 |
2.40 × 10 - 2
|
Determine the rate law and the rate constant for the reaction. |
Ans: |
|
|
Q12 |
The reaction between A and B is first order with respect to A and zero order with respect to B. Fill in the blanks in the following table:
Experiment |
A/ mol L - 1
|
B/ mol L - 1
|
Initial rate/mol L - 1 min - 1
|
I |
0.1 |
0.1 |
2.0 × 10 - 2
|
II |
-- |
0.2 |
4.0 × 10 - 2
|
III |
0.4 |
0.4 |
-- |
IV |
-- |
0.2 |
2.0 × 10 - 2
|
|
Ans: |
The given reaction is of the first order with respect to A and of zero order with respect to B.
Therefore, the rate of the reaction is given by,
Rate = k [A]1[B]0
⇒ Rate = k [A]
From experiment I, we obtain
2.0 x 10-2mol L-1min-1= k (0.1 mol L-1)
⇒ k = 0.2 min-1
From experiment II, we obtain
4.0 x 10-2mol L-1min-1= 0.2 min-1[A]
⇒ [A] = 0.2 mol L-1
From experiment III, we obtain
Rate = 0.2 min-1 x 0.4 mol L-1
= 0.08 mol L-1min-1
From experiment IV, we obtain
2.0 x 10-2mol L-1min-1= 0.2 min-1[A]
⇒ [A] = 0.1 mol L-1 |
|
Q13 |
Calculate the half-life of a first order reaction from their rate constants given below:
(i) 200 s-1
(ii) 2 min-1
(iii) 4 years-1 |
Ans: |
(i) Half life, t½ = 0.693 / k
= 0.693 / 200 s-1
= 3.47 ×10 -3 s (approximately)
(ii) Half life, t½ = 0.693 / k
= 0.693 / 2 min-1
= 0.35 min (approximately)
(iii) Half life,t½ = 0.693 / k
= 0.693 / 4 years-1
= 0.173 years (approximately) |
|
Q14 |
The half-life for radioactive decay of 14C is 5730 years. An archaeological artifact containing wood had only 80% of the 14C found in a living tree. Estimate the age of the sample. |
Ans: |
Here,
K = 0.693 / t½
= 0.693 / 5730 years-1
It is known that,
= 1845 years (approximately)
Hence, the age of the sample is 1845 years. |
|
Q15 |
The experimental data for decomposition of N2O5
[2N2O5 → 4NO2 + O2]
in gas phase at 318K are given below:
t/s |
0 |
400 |
800 |
1200 |
1600 |
2000 |
2400 |
2800 |
3200 |
102 × [N2O5] mol L-1 |
1.63 |
1.36 |
1.14 |
0.93 |
0.78 |
0.64 |
0.53 |
0.43 |
0.35 |
(i) Plot [N2O5] against t.
(ii) Find the half-life period for the reaction.
(iii) Draw a graph between log[N2O5] and t.
(iv) What is the rate law ?
(v) Calculate the rate constant.
(vi) Calculate the half-life period from k and compare it with (ii). |
Ans: |
(i)
(ii) Time corresponding to the concentration, 1630x102 / 2 mol L-1 = 81.5 mol L-1 is the half life. From the graph, the half life is obtained as 1450 s.
(iii)
t/s |
102 × [N2O5] mol L-1 |
Log [N2O5] |
0 |
1.63 |
-1.79 |
400 |
1.36 |
-1.87 |
800 |
1.14 |
-1.94 |
1200 |
0.93 |
-2.03 |
1600 |
0.78 |
-2.11 |
2000 |
0.64 |
-2.19 |
2400 |
0.53 |
-2.28 |
2800 |
0.43 |
-2.37 |
3200 |
0.35 |
-2.46 |
(iv) The given reaction is of the first order as the plot, log[N2O5] v/s t, is a straight line. Therefore, the rate law of the reaction is
Rate = k [N2O5]
(v) From the plot, log[N2O5]
v/s t, we obtain
Slope = -2.46 -(1.79) / 3200-0
= -0.67 / 3200
Again, slope of the line of the plot log[N2O5] v/s t is given by
- k / 2.303
.Therefore, we obtain,
- k / 2.303 = - 0.67 / 3200
⇒ k = 4.82 x 10-4 s-1
(vi) half life is given by,
t½ = 0.693 / k
= 0.639 / 4.82x10-4 s
=1.438 x 103 s
Or we can say
1438 S
Which is very near to what we obtain from graph.
|
|
Q16 |
The rate constant for a first order reaction is 60 s-1. How much time will it take to reduce the initial concentration of the reactant to its 1/16th value? |
Ans: |
|
|
Q17 |
During nuclear explosion, one of the products is 90Sr with half-life of 28.1 years. If 1μg of 90Sr was absorbed in the bones of a newly born baby instead of calcium, how much of it will remain after 10 years and 60 years if it is not lost metabolically. |
Ans: |
Therefore, 0.7814 μg of 90Sr will remain after 10 years.
Again,
Therefore, 0.2278 μg of 90Sr will remain after 60 Years |
|
Q18 |
For a first order reaction, show that time required for 99% completion is twice the time required for the completion of 90% of reaction. |
Ans: |
For a first order reaction, the time required for 99% completionis
t1 = 2.303/k Log 100/100-99
= 2.303/k Log 100
= 2x 2.303/k
For a first order reaction, the time required for 90% completion is
t2 = 2.303/k Log 100/100-90
= 2.303/k Log 10
= 2.303/k
Therefore, t1 = 2t2
Hence, the time required for 99% completion of a first order reaction is twice the time required for the completion of 90% of the reaction. |
|
Q19 |
A first order reaction takes 40 min for 30% decomposition. Calculate t1/2. |
Ans: |
For a first order reaction,
t = 2.303/k Log [R] º / [R]
k = 2.303/40min Log 100 / 100-30
= 2.303/40min Log 10 / 7
= 8.918 x 10-3 min-1
Therefore, t1/2 of the decomposition reaction is
t1/2 = 0.693/k
= 0.693 / 8.918 x 10-3 min
= 77.7 min (approximately) |
|
Q20 |
For the decomposition of azoisopropane to hexane and nitrogen at 543 K, the following data are obtained.
t (sec) |
P(mm of Hg) |
0 |
35.0 |
360 |
54.0 |
720 |
63.0 |
Calculate the rate constant |
Ans: |
The decomposition of azoisopropane to hexane and nitrogen at 543 K is represented by the following equation.
After time, t, total pressure, Pt = (Pº - p) + p + p
⇒ Pt = (Pº + p)
⇒ p = Pt - Pº
therefore, Pº - p = Pº - Pt - Pº
= 2 Pº - Pt
For a first order reaction,
k = 2.303/t Log Pº / Pº - p
= 2.303/t Log Pº / 2 Pº - Pt
When t = 360 s, k = 2.303 / 360s log 35.0 / 2x35.0 - 54.0
= 2.175 × 10 - 3 s - 1
When t = 720 s, k = 2.303 / 720s log 35.0 / 2x35.0 - 63.0
= 2.235 × 10 - 3 s - 1
Hence, the average value of rate constant is
k = (2.175 × 10 - 3 + 2.235 × 10 - 3 ) / 2 s - 1
= 2.21 × 10 - 3 s - 1 |
|
Q21 |
The following data were obtained during the first order thermal decomposition of SO2Cl2at a constant volume.
SO2Cl2(g) → SO2(g) + Cl2(g)
Experiment |
Time/s - 1
|
Total pressure/atm |
1 |
0 |
0.5 |
2 |
100 |
0.6 |
Calculate the rate of the reaction when total pressure is 0.65 atm. |
Ans: |
The thermal decomposition of SO2Cl2at a constant volume is represented by the following equation.
After time, t, total pressure,Pt = (Pº - p) + p + p
⇒ Pt = (Pº + p)
⇒ p = Pt - Pº
therefore, Pº - p = Pº - Pt - Pº
= 2 Pº - Pt
For a first order reaction,
k = 2.303/t Log Pº / Pº - p
= 2.303/t Log Pº / 2 Pº - Pt
When t= 100 s,
k = 2.303 / 100s log 0.5 / 2x0.5 - 0.6
= 2.231 × 10 - 3s - 1
When Pt= 0.65 atm,
P0+ p= 0.65
⇒ p= 0.65 - P0
= 0.65 - 0.5
= 0.15 atm
Therefore, when the total pressure is 0.65 atm, pressure of SOCl2 is
pSOCL2 = P0 - p
= 0.5 - 0.15
= 0.35 atm
Therefore, the rate of equation, when total pressure is 0.65 atm, is given by,
Rate = k(pSOCL2)
= (2.23 × 10 - 3s - 1) (0.35 atm)
= 7.8 × 10 - 4atm s - 1 |
|
Q22 |
The rate constant for the decomposition of N2O5 at various temperatures is given below:
T/°C
|
0 |
20 |
40 |
60 |
80 |
105 X K /S-1
|
0.0787 |
1.70 |
25.7 |
178 |
2140 |
Draw a graph between ln k and 1/T and calculate the values of A and Ea.
Predict the rate constant at 30 º and 50 ºC.
|
Ans: |
From the given data, we obtain
T/°C |
0 |
20 |
40 |
60 |
80 |
T/K
|
273 |
293 |
313 |
333 |
353 |
1/T / k-1 |
3.66×10 - 3
|
3.41×10 - 3
|
3.19×10 - 3
|
3.0×10 - 3
|
2.83 ×10 - 3
|
105 X K /S-1 |
0.0787 |
1.70 |
25.7 |
178 |
2140 |
In k |
-7.147 |
-4.075 |
-1.359 |
-0.577 |
3.063 |
Slope of the line,
In k= - 2.8
Therefore, k = 6.08x10-2s-1
Again when T = 50 + 273K = 323K,
1/T = 3.1 x 10-3 K
In k = - 0.5
Therefore, k = 0.607 s-1
|
|
Q23 |
The rate constant for the decomposition of hydrocarbons is 2.418 x 10-5 s-1 at 546 K. If the energy of activation is 179.9 kJ/mol, what will be the value of pre-exponential factor. |
Ans: |
k= 2.418 × 10-5 s-1
T= 546 K
Ea= 179.9 kJ mol - 1 = 179.9 × 103J mol - 1
According to the Arrhenius equation,
= (0.3835 - 5) + 17.2082
= 12.5917
Therefore, A = antilog (12.5917)
= 3.9 × 1012 s - 1(approximately) |
|
Q24 |
Consider a certain reaction A → Products with k = 2.0 x 10-2 s-1. Calculate the concentration of A remaining after 100 s if the initial concentration of A is 1.0 mol L-1. |
Ans: |
k= 2.0 × 110-2 s-1
T= 100 s
[A]o= 1.0 moL - 1
Since the unit of kis s - 1, the given reaction is a first order reaction.
Therefore, k = 2.303/t Log [A]º / [A]
⇒2.0 × 110-2 s-1 = 2.303/100s Log 1.0 / [A]
⇒2.0 × 110-2 s-1 = 2.303/100s ( - Log [A] )
⇒ - Log [A] = - (2.0 x 10-2 x 100) / 2.303
⇒ [A] = antilog [- (2.0 x 10-2 x 100) / 2.303]
= 0.135 mol L - 1 (approximately)
Hence, the remaining concentration of A is 0.135 mol L - 1. |
|
Q25 |
Sucrose decomposes in acid solution into glucose and fructose according to the first order rate law, with t1/2 = 3.00 hours. What fraction of sample of sucrose remains after 8 hours? |
Ans: |
For a first order reaction,
k = 2.303/t Log [R]º / [R]
It is given that, t1/2 = 3.00 hours
Therefore, k = 0.693 / t1/2
= 0.693 / 3 h-1
= 0.231 h - 1
Then, 0.231 h - 1 = 2.303 / 8h Log [R]º / [R]
Hence, the fraction of sample of sucrose that remains after 8 hours is 0.158. |
|
Q26 |
The decomposition of hydrocarbon follows the equation
k = (4.5 x 1011 s-1) e-28000 K/T
Calculate Ea. |
Ans: |
The given equation is
k = (4.5 x 1011 s-1) e-28000 K/T (i)
Arrhenius equation is given by,
k= Ae -Ea/RT (ii)
From equation (i) and (ii), we obtain
Ea / RT = 28000K / T
⇒ Ea = R x 28000K
= 8.314 J K - 1mol - 1× 28000 K
= 232792 J mol - 1
= 232.792 kJ mol - 1 |
|
Q27 |
The rate constant for the first order decomposition of H2O2 is given by the following equation:
log k = 14.34 - 1.25 x 104 K/T
Calculate Ea for this reaction and at what temperature will its half-period be 256 minutes? |
Ans: |
Arrhenius equation is given by,
k= Ae -Ea/RT
⇒In k = In A - Ea/RT
⇒In k = Log A - Ea/RT
⇒ Log k = Log A - Ea/2.303RT (i)
The given equation is
Log k = 14.34 - 1.25 104 K/T (ii)
From equation (i) and (ii), we obtain
Ea/2.303RT = 1.25 104 K/T
⇒ Ea =1.25 × 104K × 2.303 × R
= 1.25 × 104K × 2.303 × 8.314 J K - 1mol - 1
= 239339.3 J mol - 1 (approximately)
= 239.34 kJ mol - 1
Also, when t1/2= 256 minutes,
k = 0.693 / t1/2
= 0.693 / 256
= 2.707 × 10 - 3 min - 1
= 4.51 × 10 - 5s - 1
It is also given that, log k= 14.34 - 1.25 × 104K/T
= 668.95 K
= 669 K (approximately) |
|
Q28 |
The decomposition of A into product has value of k as 4.5 x 103 s-1 at 10°C and energy of activation 60 kJ mol-1. At what temperature would k be 1.5 x 104 s-1? |
Ans: |
From Arrhenius equation, we obtain
log k2/k1 = Ea / 2.303 R (T2 - T1) / T1T2
Also, k1 = 4.5 × 103 s - 1
T1 = 273 + 10 = 283 K
k2 = 1.5 × 104 s - 1
Ea = 60 kJ mol - 1 = 6.0 × 104 J mol - 1
Then,
= 297 K = 24°C
Hence, k would be 1.5 × 104 s - 1 at 24°C. |
|
Q29 |
The time required for 10% completion of a first order reaction at 298 K is equal to that required for its 25% completion at 308 K. If the value of A is 4 x 1010 s-1. Calculate k at 318 K and Ea. |
Ans: |
For a first order reaction,
t = 2.303 / k log a / a - x
At 298 K,
t = 2.303 / k log 100 / 90
= 0.1054 / k
At 308 K,
t' = 2.303 / k' log 100 / 75
= 2.2877 / k'
According to the question,
t = t'
⇒ 0.1054 / k = 2.2877 / k'
⇒ k' / k = 2.7296
From Arrhenius equation,we obtain
To calculate k at 318 K,
It is given that, A = 4 x 1010 s-1, T = 318K
Again, from Arrhenius equation, we obtain
Therefore, k = Antilog (-1.9855)
= 1.034 x 10-2 s -1
|
|
Q30 |
The rate of a reaction quadruples when the temperature changes from 293 K to 313 K. Calculate the energy of activation of the reaction assuming that it does not change with temperature. |
Ans: |
From Arrhenius equation, we obtain
Hence, the required energy of activation is 52.86 kJ mol - 1. |
|