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    This document provides a tutorial on chemical kinetics, including rates of reaction, rate laws, reaction orders, factors affecting reaction rates, and reaction mechanisms. Some key points covered include: - The rate of appearance of chlorite ion is equal to the initial rate of disappearance of chlorine dioxide under the specified conditions. - Collision theory states that molecules must collide with sufficient energy for a reaction to occur. - Reaction orders and rate laws can be determined from experimental data on initial reaction rates under varying conditions. - Reaction mechanisms involve elementary steps that may include intermediates or catalysts to explain an overall reaction.

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    This document provides a tutorial on chemical kinetics, including rates of reaction, rate laws, reaction orders, factors affecting reaction rates, and reaction mechanisms. Some key points covered include: - The rate of appearance of chlorite ion is equal to the initial rate of disappearance of chlorine dioxide under the specified conditions. - Collision theory states that molecules must collide with sufficient energy for a reaction to occur. - Reaction orders and rate laws can be determined from experimental data on initial reaction rates under varying conditions. - Reaction mechanisms involve elementary steps that may include intermediates or catalysts to explain an overall reaction.

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    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
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    234 views6 pages

    Chm271 - Tutorial 5 - Chemical Kinetics

    Uploaded by

    fiefy zmr
    This document provides a tutorial on chemical kinetics, including rates of reaction, rate laws, reaction orders, factors affecting reaction rates, and reaction mechanisms. Some key points covered include: - The rate of appearance of chlorite ion is equal to the initial rate of disappearance of chlorine dioxide under the specified conditions. - Collision theory states that molecules must collide with sufficient energy for a reaction to occur. - Reaction orders and rate laws can be determined from experimental data on initial reaction rates under varying conditions. - Reaction mechanisms involve elementary steps that may include intermediates or catalysts to explain an overall reaction.

    Copyright:

    © All Rights Reserved
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    of 6

    TUTORIAL 5 CHM271 PRINCIPLES OF PHYSICAL CHEMISTRY

    CHEMICAL KINETICS
    A. Rates of Reaction

    1. Chlorine dioxide reacts in basic water to form chlorite and chlorate according to the
    following chemical equation:

    2ClO2(aq) + 2OH–(aq) → ClO2–(aq) + ClO3–(aq) + H2O(l)

    Under a certain set of conditions, the initial rate of disappearance of chlorine dioxide
    was determined to be 2.30 x 10–1 M/s. Determine the initial rate of appearance of
    chlorite ion under the same conditions.

    2. For the following reaction, dP(C6H14)/dt was found to be –6.2 x 10–3 atm/s.

    C6H14(g) → C6H6(g) + 4H2(g)

    Determine dP(H2)/dt for this reaction at the same time.

    3. The thermal decomposition of phosphine (PH3) into phosphorus and molecular


    hydrogen is a first-order reaction. The half-life of the reaction is 35.0 s at 680°C.

    4 PH3 (g)  P4(g) + 6 H2(g)

    a) Write the expression relating the rate of formation of P 4 to the disappearance of


    PH3.
    b) Write the rate expression relating the consumption of PH3 to the formation of H2.

    4. For the reaction, 2 N2O5(g)  4 NO2(g) + O2(g), the rate of formation of NO2(g) is
    4.0 x 10-3 mol L-1s-1.

    a) Calculate the rate of disappearance of N2O5(g).


    b) Calculate the rate of appearance of O2(g).

    1
    TUTORIAL 5 CHM271 PRINCIPLES OF PHYSICAL CHEMISTRY

    B. Factors Affecting Rates of Reaction

    1. Indicate the factors which increase the rate of a reaction.

    2. Describe the ideas of collision theory.

    3. For the following exothermic reaction, the rate law at 298 K is rate = k [H2] [I2].

    H2(g) + I2(g) → 2HI(g)

    Predict the effect of each of the following changes on the initial rate of the reaction:
    a. Addition of hydrogen gas at constant temperature and volume
    b. Increase in volume of the reaction vessel at constant temperature
    c. Addition of a catalyst
    d. Increase in temperature

    C. Rate Law and Order of Reaction

    1. Consider the zero-order reaction:


    A → products

    a) Write the rate law for the reaction.


    b) What are the units for this rate law constant?
    c) Plot the graph of the rate of reaction versus [A].

    2. Consider the reaction below. The reaction order in N2O2 is zero order. The
    order with respect to Br2 is second order.

    N2O2 + Br2  2NOBr

    a) Write the rate law for the reaction.


    b) Predict the change in rate if [N2O2] is tripled.
    c) Predict the change in rate if [Br2] is doubled.
    d) Predict the change in rate if [NOBr] is tripled.

    2
    TUTORIAL 5 CHM271 PRINCIPLES OF PHYSICAL CHEMISTRY

    3. Hydrogen iodide decomposes to give a mixture of hydrogen and iodine:

    2 HI(g) H2(g) + I2(g)

    Use the following data to determine whether the decomposition of HI in the gas phase
    is first order or second order in hydrogen iodide.

    Initial Instantaneous
    Initial (HI) (M)
    Rate of Reaction (M/s)
    Trial 1 1.0 x 10-2 4.0 x 10-6
    Trial 2 2.0 x 10-2 1.6 x 10-5
    Trial 3 3.0 x 10-2 3.6 x 10-5

    4. The reaction 2 NO(g) + 2 H2(g)  N2(g) + 2 H2O(g) is found experimentally to be


    second order in NO(g) and first-order in H2(g).

    a) Write the rate law for the reaction.


    b) What is the overall order of the reaction?
    c) What are the units for the rate constant k?
    d) If [NO] is doubled (while keeping [H2] constant), by what factor will the reaction rate
    increase?
    e) If [H2] is doubled (while keeping [NO] constant), by what factor will the reaction
    rate increase?

    5. The following set of data was obtained by the method of initial rates for the reaction:

    2 HgCl2 (aq) + C2O42- (aq)  2 Cl- (aq) + 2 CO2 (g) + Hg2Cl2 (s)

    What is the rate law for the reaction?

    Trial [HgCl2],M [C2O42-], M Rate, M/s


    1 0.10 0.10 1.3 x 10-7
    2 0.10 0.20 5.2 x 10-7
    3 0.20 0.20 1.0 x 10-6

    3
    TUTORIAL 5 CHM271 PRINCIPLES OF PHYSICAL CHEMISTRY

    6. The reaction, 2 NO(g) + 2 H2(g) → N2(g) + 2 H2O(g), was studied at 904oC, and the
    data are given below.

    Reactant Concentration(mol/L) Rate of Appearance


    [NO] [H2] of N2 (mol/Ls)
    0.420 0.122 0.136
    0.210 0.122 0.0339
    0.210 0.244 0.0678
    0.105 0.488 0.0339

    a) Determine the order of the reaction w/r each reactant


    b) Write the rate law for the reaction
    c) Calculate the rate constant for the reaction at 904oC.
    d) Find the rate of appearance of N2 at the instant when [NO]= 0.350 M and
    [H2] = 0.205 M

    7. Acetaldehyde, CH3CHO, decomposes by second-order kinetics with a rate constant of


    0.334 M-1s-1 at 500°C. Calculate the amount of time it would take for 80% of the
    acetaldehyde to decompose in a sample that has an initial concentration of 0.00750 M.

    8. A first-order reaction has a rate constant of 3.00 x 10–3 s–1. Find the time required for
    the reaction to be 75.0% complete?

    9. It takes 42.0 min for the concentration of a reactant in a first-order reaction to drop from
    0.45 M to 0.32 M at 25°C. How long will it take for the reaction to be 90% complete?

    10. The isomerization of cyclopropane to form propene is a first-order reaction.

    At 760 K, 15% of a sample of cyclopropane changes to propene in 6.8 minutes.


    Compute the half-life of cyclopropane at 760 K.

    4
    TUTORIAL 5 CHM271 PRINCIPLES OF PHYSICAL CHEMISTRY

    D.Relation between Rate and Temperature

    1. Calculate the activation energy, in kJ/mol, for the redox reaction.

    Temp (°C) k (1/M·s)


    2 3.12 x 103
    27 27.0 x 103

    2. Determine the slope of an Arrhenius plot for the following reaction.

    2NOCl → 2NO + Cl2

    Temperature (K) k (L/mol·s)


    400 6.6 x 10–4
    500 2.9 x10–1
    600 16.3

    3. The activation energy for the reaction CH3CO → CH3 + CO is 71 kJ/mol. How many
    times greater is the rate constant for this reaction at 170°C than at 150°C?

    5
    TUTORIAL 5 CHM271 PRINCIPLES OF PHYSICAL CHEMISTRY

    E. Reaction Mechanism

    1. Explain the meaning of each of the following:


    a) an elementary step
    b) the molecularity of a reaction
    c) the mechanism of a reaction

    2. Identify the molecularity for the following elementary steps.


    a) NO(g) + O3(g) → NO2(g) + O2(g)
    b) CO2(g) → CO(g) + O(g)
    c) 2Cl(g) + N2(g) → Cl2(g) + N2(g)
    d) F2(g) + NO2(g) → F(g) + NO2F(g)
    e) N2O2 + Br2 → 2NOBr
    f) SO2Cl2 → SO2 + Cl2
    1.
    3. Nitrogen monoxide reacts with hydrogen with the following reaction mechanism.
    2NO + H2 → N2 + H2O2 (slow)
    H2O2 + H2 → H2O (fast)

    a) Write the overall equation for the reaction.


    b) Predict the rate law for the reaction.
    i.
    4. The rate law for decomposition of N2O5 is rate = k[N2O5]. Based on the proposed
    mechanism, derive the rate law that agrees with the experimental rate law.
    N2O5 ⇌ NO2 + NO3 (fast)
    NO2 + NO3→ NO + NO2 + O2 (slow)
    NO3 + NO → NO2 (fast)

    5. Sulfur dioxide is oxidized to sulfur trioxide in the following sequence of reactions:


    2 SO2 (g) + 2 NO2 (g) → 2 SO3 (g) + 2 NO(g)
    2 NO (g) + O2 (g) → 2 NO2 (g)

    a) Write the chemical equation for the overall reaction.


    b) Identify any molecule that acts as a catalyst or intermediate in this reaction.
    c)
    6. Distinguish between homogeneous catalysis and heterogeneous catalysis. Give an
    example of industrial processes that utilize heterogeneous catalysis.

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