Chemical Kinetics Exercise 04
Question:
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]/molL-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)
Answer:
(i) Plot [N2O5] against t.
(ii) Find the half-life period for the reaction.
Half-life period = t1/2 = 2400 s
(iii) Draw a graph between log[N2O5] and t.
(iv) What is the rate law?
Rate law = -d[N2O5]/dt = k[N2O5]
(v) Calculate the rate constant.
k = -(1/[N2O5])*(d[N2O5]/dt)
k = -(0.35-1.63)/(3200-0)
k = -0.004375 mol L-1 s-1
(vi) Calculate the half-life period from k and compare it with (ii).
Half-life period = ln(2)/k
Half-life period = ln(2)/(-0.004375)
Half-life period = 1580.7 s
The calculated half-life period (1580.7 s) is close to the measured half-life period (2400 s).
Question:
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?
Answer:
Step 1: Write down the rate equation for a first order reaction.
Rate = -k[A]
Step 2: Substitute the given rate constant into the rate equation.
Rate = -60 s-1[A]
Step 3: Calculate the time it will take for the concentration of the reactant to be reduced to 1/16th of its initial value.
Time = ln(1/16)/(-60 s-1)
Time = 8.86 s
Question:
A reaction is second order with respect to a reaction. How is the rate of reaction affected if the concentration of the reactant is : (a) doubled, (b) reduced to 1/2?
Answer:
A. (a) The rate of reaction will be doubled. B. (b) The rate of reaction will be reduced to 1/4.
Question:
From the rate expression for the following reactions, determine their order of reaction and the dimensions of the rate constants. (i) 2NO(g)→N2O(g); Rate=k[NO]2 (ii) H22O2(aq)+3I-(aq)+2H^+→2H22O(I)+3I; Rate=k[H22O2][I-] (iii) CH3CHO(g)→CH4(g)+CO(g); Rate=k[CH3CHO]3/2 (iv) C2H5Cl(g)→C2H4(g)+HCl(g); Rate=k[C2H5Cl]
Answer:
(i) Order of reaction: 2 Dimensions of rate constant: M/s
(ii) Order of reaction: 2 Dimensions of rate constant: M-1 s-1
(iii) Order of reaction: 3/2 Dimensions of rate constant: M-3/2 s-1
(iv) Order of reaction: 1 Dimensions of rate constant: s-1
Question:
Calculate the half life of a first order reaction from their rate constants given below: (a) 200s-1; (b) 2 min-1; (c) 4year-1.
Answer:
Step 1: Understand the definition of a half-life. The half-life of a reaction is the time it takes for the reactant concentration to decrease by half.
Step 2: Calculate the half-life for each rate constant given.
(a) For a rate constant of 200s-1, the half-life is 0.5 seconds.
(b) For a rate constant of 2 min-1, the half-life is 30 seconds.
(c) For a rate constant of 4year-1, the half-life is 182.5 days.
Question:
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/molL-1 0.20 0.20 0.40 B/molL-1 0.30 0.10 0.05 r0/molL-1s-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?
Answer:
- Calculate the rate of reaction for each set of initial concentrations of A and B.
- Calculate the change in rate of reaction for each set of initial concentrations of A and B.
- Calculate the change in concentration of A and B for each set of initial concentrations.
- Calculate the ratio of the change in rate of reaction to the change in concentration of A and B for each set of initial concentrations.
- Compare the ratios for each set of initial concentrations and determine the order of the reaction with respect to A and B.
Question:
The rate constant for the first order decomposition of H2O2 is given by the following equation: logk=14.34−1.25×104K/T Calculate Ea for this reaction and at what temperature will its half-period be 256 minutes?
Answer:
Step 1: Calculate Ea: Ea = -1.25 x 104K/ln(k)
Step 2: Calculate the rate constant (k): k = e^(14.34 - 1.25 x 104K/T)
Step 3: Calculate the temperature (T): T = 1.25 x 104K/ (14.34 - ln(k))
Step 4: Calculate the half-period (t1/2): t1/2 = (ln(2))/k
Step 5: Substitute the value of k into the equation for t1/2: t1/2 = (ln(2))/e^(14.34 - 1.25 x 104K/T)
Step 6: Solve for T: T = 1.25 x 104K/ (14.34 - ln(2/t1/2))
Step 7: Substitute the value of t1/2 (256 minutes): T = 1.25 x 104K/ (14.34 - ln(2/256))
Step 8: Calculate the temperature: T = 897.9 K
Question:
The rate constant for the decomposition of hydrocarbons is 2.418×10-5s-1 at 546 K. If the energy of activation is 179.9 kJ/mol, what will be the value of pre-exponential factor?
Answer:
Answer:
Step 1: Calculate the Arrhenius equation which is given by k = Ae(-Ea/RT).
Step 2: Substitute the given values in the equation to calculate the pre-exponential factor (A).
A = 2.418 × 10-5 × e(179.9 × 103/8.314 × 546)
Step 3: Calculate the value of pre-exponential factor (A).
A = 1.30 × 10^13 s-1
Question:
For the decomposition of azo-isopropane to hexane and nitrogen at 543K, the following data are obtained. t(sec) P(mm of Hg) 0 35.0 360 54.0 720 63.0 Calculate the rate constant.
Answer:
- Calculate the pressure change for each time interval:
Time interval 0-360 sec: ΔP = 54.0 - 35.0 = 19.0 mm of Hg Time interval 360-720 sec: ΔP = 63.0 - 54.0 = 9.0 mm of Hg
- Calculate the rate constant:
k = ΔP/Δt
For the first time interval:
k = 19.0/360 = 0.0527 mm of Hg/sec
For the second time interval:
k = 9.0/360 = 0.0250 mm of Hg/sec
The average rate constant is (0.0527 + 0.0250)/2 = 0.0388 mm of Hg/sec.
Question:
For a first order reaction, show that time required for 99% completion is twice the time required for the completion of 90% of reaction.
Answer:
Step 1: Let the time required for completion of 90% of reaction be ’t'.
Step 2: According to the definition of a first order reaction, the rate of reaction is directly proportional to the concentration of the reactant.
Step 3: Therefore, the rate of reaction at 90% completion (t) will be half the rate of reaction at 99% completion (2t).
Step 4: Since the rate of reaction is directly proportional to the time taken for completion, the time required for 99% completion will be twice the time required for 90% completion (2t).
Question:
The time required for 10% completion of a first order reaction at 298K is equal to that required for its 25% completion at 308K. If the value of A is 4×1010s-1. Calculate k at 318K and Ea.
Answer:
Step 1: Calculate the rate constant (k) at 298K. k = A * e(-Ea/RT) k = 4×1010s-1 * e(-Ea/8.314*298)
Step 2: Calculate the rate constant (k) at 308K. k = 4×1010s-1 * e(-Ea/8.314*308)
Step 3: Calculate the ratio of the rate constants at 298K and 308K. k298/k308 = (4×1010s-1 * e(-Ea/8.314298)) / (4×1010s-1 * e^(-Ea/8.314308))
Step 4: Calculate the ratio of the time required for 10% completion of a first order reaction at 298K and 25% completion of the same reaction at 308K. Time298/Time308 = 0.1/0.25
Step 5: Equate the ratio of the rate constants and the ratio of the times required for completion. (4×1010s-1 * e^(-Ea/8.314298)) / (4×1010s-1 * e(-Ea/8.314308)) = 0.1/0.25
Step 6: Solve for Ea. Ea = -8.314 * ln(0.4)
Step 7: Calculate the rate constant (k) at 318K. k = 4×1010s-1 * e(-Ea/8.314*318)
Step 8: Calculate the activation energy (Ea) at 318K. Ea = -8.314 * ln(k/4×1010s-1)
Question:
The following results have been obtained during the kinetic studies of the reaction: 2A+B→C+D Experiment [A]/molL-1 [B]/molL-1 Initial rate of formation of D/molL-1min-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.
Answer:
-
Calculate the initial rate of reaction for each experiment using the equation: rate = (change in concentration of product/change in time).
-
Plot the initial rate of reaction (y-axis) against the concentration of reactant A (x-axis).
-
Draw a line of best fit through the points on the graph.
-
The slope of the line is equal to the rate constant, k.
-
The rate law for the reaction is rate = k[A]m[B]n, where m and n are the exponents for the reactants A and B.
-
Calculate the exponents m and n by substituting the rate constants and concentrations obtained from the experiments into the rate law.
-
The rate law and the rate constant for the reaction are: rate = k[A]m[B]n, where k = slope of the line of best fit, m = exponents for A, and n = exponents for B.
Question:
During nuclear explosion, one of the products is 90Sr with half life of 28.1 yr. 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 year and 60 year if it is not lost metabolically.
Answer:
-
Calculate the decay constant (λ): λ = 0.693 / 28.1 = 0.0247 yr-1
-
Calculate the amount of 90Sr remaining after 10 years: Amount remaining after 10 years = 1μg x (1/2)(λ x 10) = 0.732μg
-
Calculate the amount of 90Sr remaining after 60 years: Amount remaining after 60 years = 1μg x (1/2)(λ x 60) = 0.039μg
Question:
In a pseudo first order hydrolysis of ester in water the following results were obtained: ^t/s 0 30 60 90 [Ester]/M. 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.
Answer:
(i) Average rate of reaction between 30 and 60 seconds:
Rate = (Change in [Ester]/Change in time) Rate = (0.31 M - 0.17 M/ 30s - 0.00s) Rate = 0.14 M/s
(ii) Pseudo first order rate constant (k):
k = -(Change in [Ester]/Change in time)/[Ester] k = -(0.31 M - 0.17 M/30s - 0.00s)/0.31 M k = -0.14/0.31 k = 0.45 s-1
Question:
What is the effect of temperature on the rate constant of a reaction? How can this effect of temperature on rate constant be represented quantitatively?
Answer:
Answer:
-
The effect of temperature on the rate constant of a reaction is that an increase in temperature generally increases the rate constant of a reaction.
-
This effect of temperature on rate constant can be represented quantitatively by the Arrhenius equation, which states that the rate constant of a reaction is proportional to the exponential of the inverse of the absolute temperature.
Question:
The rate for the decomposition of NH3 on platinum surface is zero order. What are the rate of production of N2 and H2 if K=2.5×10-4mol litre-1s-1.
Answer:
Step 1: The rate of the decomposition of NH3 is zero order, which means that the rate of the reaction is independent of the concentration of NH3.
Step 2: The rate of production of N2 and H2 can be calculated using the rate constant K.
Step 3: The rate of production of N2 is equal to the rate constant K multiplied by the concentration of NH3.
Rate of production of N2 = K x [NH3] = 2.5 x 10-4 mol litre-1s-1 x [NH3]
Step 4: The rate of production of H2 is equal to the rate constant K multiplied by twice the concentration of NH3.
Rate of production of H2 = K x 2[NH3] = 2.5 x 10-4 mol litre-1s-1 x 2[NH3]
Question:
The decomposition of hydrocarbon follows the equation, k=(4.5×1011s−1)e−28000K/T. Calculate Ea.
Answer:
Given: k = (4.5 x 1011 s-1) e(-28000K/T)
Step 1: Rearrange the equation to solve for e(-28000K/T).
e(-28000K/T) = k/(4.5 x 1011 s-1)
Step 2: Take the natural logarithm of both sides of the equation.
ln(e(-28000K/T)) = ln(k/(4.5 x 1011 s-1))
Step 3: Simplify the equation.
-28000K/T = ln(k/(4.5 x 1011 s-1))
Step 4: Multiply both sides of the equation by T.
-28000K = T*ln(k/(4.5 x 1011 s-1))
Step 5: Divide both sides of the equation by -28000.
K = -T*ln(k/(4.5 x 1011 s-1))/28000
Step 6: Multiply both sides of the equation by -1.
Ea = T*ln(k/(4.5 x 1011 s-1))/28000
Question:
A reaction is first order in A and second order in B : (i) Write differential rate equation. (ii) How is the rate affected when the concentration of B is tripled? (iii) How is the rate affected when the concentration of both A and B is doubled?
Answer:
(i) Differential rate equation: d[A]/dt = -k[A][B]
(ii) When the concentration of B is tripled, the rate of the reaction will be tripled as well.
(iii) When the concentration of both A and B is doubled, the rate of the reaction will be quadrupled.
Question:
The rate constant for the decomposition of N2O5 at various temperatures is given below:
T/°C 0 20 40 60 80
105×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° and 50°C.
Answer:
-
Use the given table to plot a graph of ln k versus 1/T.
-
Use the graph to calculate the values of A and Ea.
-
Calculate the rate constant at 30°C and 50°C using the equation k = A e(-Ea/RT).
-
Substitute the values of A, Ea, R, and T into the equation to calculate the rate constants at 30°C and 50°C.
Question:
A first order reaction takes 40 min for 30% decomposition. Calculate t1/2.
Answer:
Step 1: Understand the problem.
We are being asked to calculate the half-life (t1/2) of a first order reaction that takes 40 minutes for 30% decomposition.
Step 2: Calculate the rate constant (k).
The rate constant (k) can be calculated using the following equation: k = -ln(1 - (x/100)) / t where x is the percentage of decomposition and t is the time taken for the reaction.
Plugging in the values from the problem, we get: k = -ln(1 - (30/100)) / 40 k = 0.0045 min-1
Step 3: Calculate the half-life (t1/2).
The half-life (t1/2) can be calculated using the following equation: t1/2 = ln(2) / k where k is the rate constant.
Plugging in the value for k from Step 2, we get: t1/2 = ln(2) / 0.0045 t1/2 = 154.6 min
Question:
The following data were obtained during the first order thermal decomposition of SO2Cl2 at 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.
Answer:
Step 1: Calculate the rate of the reaction when total pressure is 0.5 atm.
Rate of reaction = (0.6-0.5)/100 = 0.001 atm/s
Step 2: Calculate the rate of the reaction when total pressure is 0.65 atm.
Rate of reaction = (0.65-0.5)/100 = 0.0015 atm/s
Question:
The rate of a reaction quadruples when the temperature changes from 293K to 313K. Calculate the energy of activation of the reaction assuming that it does not change with temperature.
Answer:
-
Calculate the temperature difference between 293K and 313K: 313K - 293K = 20K
-
Calculate the ratio of the rate of the reaction at 313K to the rate of the reaction at 293K: 4:1
-
Calculate the energy of activation of the reaction: The energy of activation of the reaction is the same regardless of the temperature change.
Question:
The half-life for radioactive decay of 14°C is 5730 years. An archaeological artifact containing wood had only 80% of the 14°C found in a living tree. Estimate the age of the sample.
Answer:
-
Determine the half-life of 14°C. Answer: The half-life of 14°C is 5730 years.
-
Calculate the amount of 14°C present in a living tree. Answer: 100% of the 14°C is present in a living tree.
-
Calculate the amount of 14°C present in the archaeological artifact. Answer: 80% of the 14°C is present in the archaeological artifact.
-
Calculate the age of the sample using the half-life of 14°C. Answer: The age of the sample can be calculated by dividing the half-life of 14°C (5730 years) by the amount of 14°C present in the archaeological artifact (80%) to get the age of the sample, which is 7,163 years.
Question:
Consider a certain reaction A→ Products with, k=2.0×10-2s-1. Calculate the concentration of A remaining after 100 s, if the initial concentration of A is 1.0molL-1.
Answer:
Answer: Step 1: The rate equation for this reaction is given by: Rate = -d[A]/dt = k[A]
Step 2: To calculate the concentration of A remaining after 100 s, we need to solve the differential equation: d[A]/dt = k[A]
Step 3: We can solve this equation using the separation of variables technique: Integral of d[A]/[A] = Integral of kdt
Step 4: After integrating both sides, we get: ln[A] = kt + C
Step 5: To determine the constant C, we can use the initial condition given in the problem: At t = 0, [A] = 1.0 mol/L
Step 6: Substituting t = 0 and [A] = 1.0 mol/L in the equation, we get: ln(1.0) = k(0) + C
Step 7: Solving for C, we get: C = ln(1.0)
Step 8: Substituting C and k in the equation, we get: ln[A] = 2.0 × 10-2s-1 × 100s + ln(1.0)
Step 9: Solving for [A], we get: [A] = e(2.0 × 10-2s-1 × 100s + ln(1.0))
Step 10: Hence, the concentration of A remaining after 100 s is: [A] = e(2.0 × 10-2s-1 × 100s + ln(1.0)) = 0.3678 mol/L
Question:
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?
Answer:
Step 1: Calculate the half-life of the sucrose sample, which is 3.00 hours.
Step 2: Calculate the fraction of the sample that remains after 8 hours by subtracting 8 hours from the half-life and then dividing the result by the half-life.
Fraction remaining = (3.00 - 8.00) / 3.00
Fraction remaining = -5.00 / 3.00
Fraction remaining = -1.67
Since the fraction remaining is negative, this means that all of the sucrose has decomposed after 8 hours.
Question:
Mention the factors that affect the rate of a chemical reaction.
Answer:
-
Concentration of reactants: The higher the concentration of reactants, the higher the rate of reaction.
-
Temperature: Increasing the temperature of a reaction increases the kinetic energy of the reactants, which increases the rate of reaction.
-
Presence of a catalyst: A catalyst provides an alternative pathway for the reaction to occur, which increases the rate of reaction.
-
Surface area: Increasing the surface area of the reactants increases the rate of reaction, as more particles are available for reaction.
-
Pressure: Increasing the pressure of a reaction increases the rate of reaction.
Question:
For the reaction:
2A+B→A2B, the rate =k[A][B]2 with k=2.0×10-6mol-2L2s-1.
Calculate the initial rate of the reaction when [A]=0.1molL-1,[B]=0.2 molL-1. Calculate the rate of reaction after [A] is reduced to 0.06 molL-1.
Answer:
Answer: Initial rate of reaction when [A]=0.1molL-1 and [B]=0.2molL-1: Rate = k[A][B]2 = 2.0×10-6mol-2L2s-1 × 0.1molL-1 × 0.2molL-1 = 4.0×10-8molL-1s-1
Rate of reaction after [A] is reduced to 0.06molL-1: Rate = k[A][B]2 = 2.0×10-6mol-2L2s-1 × 0.06molL-1 × 0.2molL-1 = 2.4×10-8molL-1s-1
Question:
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]/molL-1 B]/molL-1 Initial rate/ molL-1min-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
Answer:
Experiment [A]/molL-1 B]/molL-1 Initial rate/ molL-1min-1 I 0.1 0.1 2.0×10-2 II 0.2 0.2 4.0×10-2 III 0.4 0.4 4.0×10-2 IV 0.2 0.2 2.0×10-2
Question:
The decomposition of A into product has value of k as 4.5×103s-1 at 10°C and energy of activation 60 kJmol-1. At what temperature would k be 1.5×104s-1?
Answer:
-
Rearrange the given equation to isolate the variable ’temperature’: k = 4.5×103s-1 * e^(-60kJmol-1/R * (1/T - 1/T_0))
-
Substitute the given values into the equation: k = 4.5×103s-1 * e^(-60kJmol-1/R * (1/T - 1/293.15K))
-
Rearrange the equation to solve for ‘T’: T = 293.15K * (1 + (60kJmol-1/R) * ln(4.5×103s-1/1.5×104s-1))-1
-
Substitute the given values into the equation: T = 293.15K * (1 + (60kJmol-1/(8.314JK-1mol-1)) * ln(4.5×103s-1/1.5×104s-1))-1
-
Calculate the value of T: T = 293.15K * (1 + (7.235K-1) * ln(3))-1
-
Calculate the value of T: T = 293.15K * (1 + 21.705K-1)-1
-
Calculate the value of T: T = 293.15K * 0.0462
-
Calculate the value of T: T = 13.55K
Question:
The decomposition of dimethyl ether leads to the formation of CH4,H2 and 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 and time in minutes, then what are the units of rate and rate constants?
Answer:
Units of rate: bar3/2 min-1
Units of rate constant: bar3/2 min-1 mol-3/2