4.3.APPENDIX

6.What kind of parameters can be calculated using the Arrhenius equation?

7.Define the concept of activation energy and the energy barrier.

8.What is the activated complex in catalytic reactions?

9.From what stages consist of heterogeneous catalytic reactions?

10.Features of diffusion processes.

11.Features of catalytic reactions?

12.Mechanisms of catalytic reactions.

13.What is adsorption?

14.The main types of adsorption, give a brief description of them.

15.Explain the role of adsorption in heterogeneous catalytic reactions.

16.The basic of Langmuir’s theory.

17.Why use Langmuir equation?

18.What is the degree of surface filling by the adsorbate? What data is needed to calculate it?

19.What determines the activity of the solid catalyst?

20.Name the basic theories of heterogeneous catalysis. What is the difference between them?

4.5REFERENCES

1.Peter Atkins, Julio de Paula, Atkins’ Physical Chemistry 9th ed., [English] OUP Oxford, 2009, 1008 p.

2.R.J. Silbey, R.A. Alberty, M.G. Bawendi. Physical Chemistry. 4th ed., [English] John Wiley and Sons, 2004, 960 p.

3.Thomas Engel, Philip Reid, Physical Chemistry. 2nd ed., [English]

Prentice Hall, 2009, 1088 p.

4.K.S. Krasnov et al., Physical chemistry. V.2. Electrochemistry. Chemical kinetics and catalysis. Textbook for universities in 2 volumes. Ed. K.S. Krasnov. 3rd ed., Moscow: Vysshaya Shkola, 2001, 319 p. [In Russian]

5.G.A. Golikov, Guide to Physical Chemistry. Tutorial for chemicaltechnological special universities. Moscow: Vysshaya Shkola, 1988, 383 p. [In Russian]

6.S.M. Kochergin et al., Brief course of physical chemistry. A textbook

for high schools. Ed. S.N. Kondratieff. 2nd ed., Moscow: Vysshaya Shkola, 1978, 312 p. [In Russian]

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7.N.N. Mushkambarov, Physical and Colloid Chemistry. A Textbook for medical schools. 3rd ed., Moscow: Medical Information Agency Ltd., 2008, 295 p. [In Russian]

8.S.V. El'tsov, N.A. Vodolazkaya, Physical and Colloid Chemistry. Textbook. Kharkov, 2005, 239 p. [In Russian]

9.L.V. Senicheva, V.A. Yargaeva, Physical chemistry: chemical equilibrium. A tutorial. Khabarovsk: Pacific. Reg. University Press, 2008,

83 p. [In Russian]

10.I.A. Semiohin, Physical chemistry. Textbook. Moscow State University Press, 2001, 272 p. [In Russian]

11.B.P. Nikolsky et al., Physical chemistry. Theoretical and practical guide. A textbook for high schools. Ed. B.P. Nikolsky, 2nd ed., Leningrad: Khimiya, 1987, 880 p. [In Russian]

12.A.N. Alexandrov et al., Practical works on Physical Chemistry. Ed. V.V. Budanov, N.K. Vorobyov. 5th ed., Moscow: Khimiya, 1986, 352 p. [In Russian]

13.E.A. Vaitulevich et al., Laboratory practical works in physical chemistry. Ed. I.A. Kurzina, Tomsk State Arhit.-builds. University Press, 2008, 72 p. [In Russian]

14.S.I. Levchenkov, Physical and Colloid Chemistry. Summary of lectures. Part 2. Khim. kinetics and catalysis. Rostov-on-Don, 2004, 27 p. [In Russian]

15.T.V. Lapova et al., Physical chemistry. Chemical kinetics and equilibrium. Electrochemistry. Tutorial. Ed. T.V. Lapova. Tomsk State

Arhit.-builds. University Press, 2009, 104 p. [In Russian]

16.E.I. Mingulina et al., The general chemistry course. The textbook for the students of the Energy Special Universities. Ed. N.V. Korovin. 2nd ed., Moscow: Vysshaya Shkola, 1990, 446 p. [In Russian]

17.A.G. Stromberg, D.P. Semchenko, Physical chemistry. A textbook

for Chem. Specials. Universities, Ed. A.G. Stromberg. 4th ed., Moscow: Vysshaya Shkola, 2001, 527 p. [In Russian]

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5. INDIVIDUAL ASSIGNMENTS.

KINETICS OF HOMOGENEOUS PROCESSES

5.1. BASIC CONCEPTS AND LAWS OF

CHEMICAL KINETICS

Task 1

1.How do you understand the term "the rate of a chemical reaction"? What are the factors on which it depends?

2.What is the dimension of the reaction rate constant, k, for a zero-order reaction?

3.What experimental data are necessary for determining the reaction kinetic order?

4.Deduce an equation for the half-life, τ1/2, of a second-order reaction for the case when the initial concentration of reactants are equal.

5.Derive the expression for the reaction rate constant, k, of gas-phase

reactions of the general type, A → B + C, using the values of the initial (pо) and total (p) pressure in the system.

6.The volume, V, of oxygen that evolves upon decomposition of N2O5 in CCl4 in varies with time as follows:

Calculate the reaction rate constant and show using the graphical method that this is a first-order reaction.

Task 2

1.Formulate the basic postulate of chemical kinetics.

2.Write down the mathematical expression for the true rate of the reaction, А → В.

3.What methods of determination of the reaction order are related to the group of integral methods?

4.Illustrate graphically the dependence of the reaction rate constant on the concentration of reactants.

5.How to explain that the reaction,

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30C2H5OH + B10H14 → 10B(OC2H5)3 + 22H2,

is of the 2nd order but not of the 31st order? Write the kinetic equation for the given example.

6.During catalytic decay of ammonia to simple substances on the wolfram wire at Т=1100°C, the time required for decomposition of half

of all the amount of NH3 depends on the initial pressure of ammonia as follows:

Determine the order of the reaction and its kinetic constant.

Task 3

1.Explain the physical meaning of the reaction rate constant. On which parameters does it depend?

2.Can the reaction order be fractional?

3.What kind of a graphical dependence does a kinetic curve show?

4.The data on changes in the concentration of a reactant with time are obtained upon studying the reaction kinetics. Which method of determination of the reaction order is most efficient in this case?

5.An irreversible reaction of which order, first-, second-, or third-order, will proceed faster under the condition of equal initial concentrations and equal kinetic constants?

6.The kinetic constant of the reaction

is the following: k = 2.2 × 10–4 s–1. Determine the initial concentration of isobutylene, if its concentration after 3600 s from the reaction start became equal to 1.0 × 10–4 mol/L.

Task 4

1.What is called the order of a chemical reaction? For what type of reactions the order and molecularity always coincide?

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2.What methods can be used for determination of the reaction rate?

3.Specify the unit of the rate constant for the 1st order reactions.

4.Illustrate schematically kinetic curves with respect to the concentration of a starting reactant for irreversible reactions of the first and second orders in the same diagram.

5.Compare the reaction rate constants for two first-order reactions in the case, when the half-life of the first reaction is by 5 times larger than of the second one.

6.During the reaction

Cu + (NH4)2S2O8 = CuSO4 + (NH4)2SO4

the concentration of CuSO4 in different periods of time varied as follows:

The initial concentration of (NH4)S2O8 was 0.219 mol/L. Determine the order and rate constant of the reaction.

Task 5

1.What does the term "half-life of a reaction" mean? Can it be applied to secondand third-order reactions?

2.What is the difference between the order and molecularity of a chemical reaction?

3.Describe the method of equal concentrations and the isolation method for experimental determination of the reaction order.

4.Illustrate schematically the dependence graph, which can be used for determination of the rate constant of a third-order reaction at equal concentrations of starting reagents.

5.The following kinetic equation was obtained for the reaction

What is the overall reaction order? Make some assumptions about the mechanism of this chemical reaction.

6. The amount of the reacted compound in the rearrangement reaction of

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