Abstract
The possibilities of using direct calorimetric measurements for the determination of kinetic parameters of processes are discussed in terms of the choice of an appropriate method of reproduction of the course of changes in the heat power generated in time, i.e. thermokinetics. Such methods are presented and it is concluded that many of these methods permit reproduction of the thermokinetics in the same way as if the experimental thermal curve were obtained in a calorimetric system characterized by a time constant 100–200 times as large as that for the thermal inertia of this calorimetric system.
Zusammenfassung
Die Möglichkeiten zur Benutzung direkter kalorimetrischer Messungen zur Bestimmung kinetischer Parameter von Prozessen werden hinsichtlich der Wahl geeigneter Methoden zur Reproduzierung des Verlaufs der Änderungen der Wärmekraft mit der Zeit, d.h. zur Reproduzierung der Thermokinetik diskutiert. Solche Methoden werden angeführt und es wird die Schlussfolgerung gezogen, dass viele dieser Methoden die Reproduzierung der Thermokinetik auf gleiche Weise wie in den Fällen erlauben, in denen die thermische Kurve mit einem kalorimetrischen System erhalten wird, dessen Zeitkonstante um 100–200mal grösser als die des diskutierten Systems ist.
Резюме
Возможности использ ования прямых калориметрических и змерений обсуждены в плане выбора соотве тствующего метода воспроизводимости х ода изменения выделя ющегося тепла во времени т. е. те рмокинетики. Предста влены эти методы и сделан вы вод, что многие из этих методо в позволяют воспроиз вести термокинетику тем же самым путем, как если бы экспериме нтальные термически е кривые были получены в калор иметрической системе, характеризу ющейся постоянной вр емени в 100–200 раз выше по сравнению с термической инерци онностью такой калориметрической с истемы.
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References
J. Duclaux, Comp. Rend. Acad. des Sci., 146 (1908) 120.
J. Polaczek, Calorimetry Application for Study of Reaction in Liquid Phase, II. National Conference on Calorimetry and Thermal Analysis, Zakopane, 1976, Poland.
W. Świetosławski, Microcalorimetry, Reinhold Publishing Co., New York, 1946.
P. D. Garn, Thermoanalytical Methods of Investigation, Academic Press, New York, 1965.
W. W. Wendlandt, J. Chem. Educ., 38 (1961) 371.
P. C. Gravelle, Annual Meeting of the Franch Association of Calorimetry and Thermal Analysis, ICAT 80, Barcelona, Spain, June 1980.
F. D. Rossini, Experimental Thermochemistry, Measurement of Heats of Reaction, Interscience Publishers Inc., New York, 1959.
W. Frankvoort, Thermochim. Acta, 20 (1977) 279.
S. Bretsznajder and R. Marcinkowski, Bull. Acad. Polon. Sci., Sér. Sci. Chim., 13 (1965) 171.
C. E. Bawn, C. Fitsimmons, A. Ledwith, J. Penfold, D. C. Sherrington and J. A. Weightman, Polymer, (London), 12 (1971) 119.
R. H. Biddulph and P. H. Plesh, J. Chem. Soc., 1960, 3913.
J. H. Beard, P. H. Plesh and P. P. Rutherford, J. Chem. Soc., 1964, 2560.
R. H. Biddulph, P. H. Plesh and P. P. Rutherford, J. Chem. Soc., 1965, 275.
V. S. Lebiediev, V. Yu. Sharikov, V. N. Demin, V. A. Sokolov, E. A. Vasilieva and V. D. Valgin, Plast. Massy, 1969 (4), 62.
F. J. W. Roughton, Proc. Royal Soc., A 126 (1930) 470.
J. B. Bateman and F. J. W. Roughton, Biochem. J., 29 (1935) 2662.
J. B. Bateman and F. J. W. Roughton, Biochem. J., 29 (1925) 2630.
J. C. Kernohan and F. J. W. Roughton, J. Physiol. (London), 197 (1968) 345.
J. R. Chipperfield, Proc. Royal Soc., B 164 (1966) 401.
J. S. Naworski and P. Harriot, Ind. Eng. Chem. Fund., 8 (1969) 397.
B. Balko, R. L. Berger and W. Friant, Anal. Chem., 41 (1969) 1506.
R. L. Berger and L. Ch. Stoddart, Rev. Sci. Instr., 36 (1965) 78.
R. L. Berger, J. M. Peterson and E. Budge, Rev. Sci. Instr., 36 (1965) 93.
L. C. Stoddart and R. L. Berger, Rev. Sci. Instr., 36 (1965) 85.
R. L. Berger and N. Davids, Rev. Sci. Instr., 36 (1965) 88.
R. L. Berger, B. Balko, W. O. Brocherdt and W. S. Friant, Rev. Sci. Instr., 39 (1968) 486.
R. L. Berger, B. Balko and H. Chapman, Rev. Sci. Instr., 39 (1968) 493.
W. J. Evans, E. J. Courtney and W. B. Carney, Anal. Chem., 40 (1968) 262.
C. Kitzinger and T. H. Benzinger, Meth. Biochem. Anal., 8 (1966) 309.
J. de Jong and L. Marquenie, Instr. Prakt., 16 (1962) 45.
N. Tenoutasse, Rev. Mat. Constr., 28 (1970) 655.
G. J. Berezin, Zaw. Laboratoria, 25 (1959) 484.
E. Pelda and M. Kamiński, Patent, P. 160 899 UP PRL.
J. C. Reggiani, G. Cudey and J. Bernard, Journées de Calorimétrie et. d'A. T. D., Mulhouse, 1971.
J. A. Forrester, Cement Techn., 1 (1970) 95.
P. Monk and I. Wadsö, Acta Chem. Scand., 23 (1969) 29.
E. J. Prosen and J. C. Colbert, NBS Special Publication 400, August 1977.
L. D. Hansen and R. M. Hart, J. Elektrochem. Soc., 125 (1978) 842.
H. A. Schaft, Special Report NBS Special Publication, 6, 1979.
P. C. Gravelle, Thermokinetics measurements in adsorption and heterogenous catalysis studies, II. National Conference on Calorimetry and Thermal Analysis, Zakopane, 1976, Poland.
H. D. Brown, Biochemical Microcalorimetry. Academic Press, London, 1969.
R. Alegre, La calorimétrie de ciments, CERILH, Paris, 1961.
M. Kamiński and W. Zielenkiewicz, Cem. Concr. Res., 12 (1982) 549.
S. W. Benson, Thermochemical kinetics, J. Wiley and Sons, Inc., New York, London, Sidney, 1968.
W. Świetostawski and J. Salcewicz, Roczniki Chem., 121 (1934) 621.
E. Calvet and H. Prat, Microcalorimétrie, Paris, 1956.
G. Laville, Compt. Rend. Acad. Sci., 240 (1955) 1060.
E. Calvet and F. M. Camia, J. Chem. Phys., 55 (1958) 818.
F. M. Camia, Traité de thermocinétique impulsionelle, Dunod, Paris, 1967.
M. Łaźniewski, Bull. Acad. Polon. Sci., Sér. Sci. Chim., Géol. Géogr., 7 (1959) 157; ibid., 7 (1959) 163.
M. Łaźniewski, Roczniki Chem., 30 (1973) 999.
W. Zielenkiewicz, Analysis of thermal effects in nonisothermal-nonadiabatic calorimeters, PWN, Warszawa, 1966 (in Polish).
W. Zielenkiewicz, Bull. Acad. Polon. Sci., Sér. Sci. Chim. 14 (1966) 586, 593, 676, 683.
E. Margas, A. Zielenkiewicz and W. Zielenkiewicz, Bull. Acad. Polon. Sci., Sér. Sci. Chim., 18 (1970) 271, 297.
E. Margas and W. Zielenkiewicz, Bull. Acad. Polon. Sci., Sér. Sci. Chim., 16 (1966) 101, 133; ibid., 21 (1973) 247, 251; ibid., 26 (1978) 503; ibid., 28 (1980) 89.
W. Zielenkiewicz and A. Tabaka, Bull. Acad. Polon. Sci., Sér. Sci. Chim., 28 (1980) 727; ibid., 29 (1981) 41, 51, 61.
J. Gutenbaum, E. Utzig, J. Wiśniewski and W. Zielenkiewicz, Bull. Acad. Polon. Sci. Sér. Sci. Chim., 24 (1976) 193.
J. Gutenbaum, E. Utzig, J. Wisniewski and W. Zielenkiewicz, IV. Conférence Internationale de Thermodynamique Chimique, Montpellier, 9 (1975) 144.
J. Gutenbaum, E. Utzig, J. Wiśniewski and W. Zielenkiewicz, Application of dynamic optimization methods for the calculation of thermal effects in nonisothermal-non-adiabataic calorimeters, Papers from the I. National Conference on Calorimetry, Zakopane, 1973, Poland (in Polish).
E. Utzig and W. Zielenkiewicz, Bull. Acad. Polon. Sci., Sér. Sci. Chim., 26 (1978) 233.
W. Zielenkiewicz, J. Lipkowski and P. Starzewski, Thermochim. Acta, 49 (1981) 269.
J. Navarro, V. Torra and E. Rojas, An. Fis., 67 (1971) 367.
J. Navarro, V. Torra and E. Rojas, Thermogenèse, Colloques Internationaux du CNRS, Marseille, 1971.
J. Navarro, Thèse, Barcelona, 1972.
E. Rojas, V. Torra and J. Navarro, An. Fis., 67 (1971) 359.
J. Navarro, E. Rojas and V. Torra, Détermination d'une thermogenèse par analyse harmonique. Application à l'étude calorimétrique des amalgames, Revue Générale de Thermique, Nr. 143, November, 1973.
L. Adamowicz, J. Thermal Anal., 22 (1981) 199.
L. Adamowicz and W. Zielenkiewicz, J. Thermal Anal. (in press).
C. Brie, J. L. Petit and P. C. Gravelle, Compt. Rend. Acad. Sci., 273 (1971) 1.
C. Brie, M. Guivarch and J. L. Petit, Proc. I. Intern. Conf. on Calorimetry and Thermodynamics, Warsaw, 1969.
R. Point, J. L. Petit and P. C. Gravelle, Recherche de la thermocinétique exacte des courbes calorimétriques par filtrage numé rique inverse, Turin, 1978.
R. Point, Thèse, Nr. 327, Lyon, 1978.
E. Margas and W. Zielenkiewicz, Bull. Acad. Polon. Sci., Sér. Sci. Chim., 26 (1978) 503.
J. Hatt, E. Margas and W. Zielenkiewicz, Thermochim. Acta (in press).
Y. Thouvenin, C. Hinnen and A. Rousseau, Actes du Colloque CNRS 156, CNRS éd., Paris, 65 (1967).
J. P. Dubes, M. Barres and H. Tachoire, Compt. Rend. Acad. Sci., 283 (1976) 163.
J. P. Dubes, M. Barres and H. Tachoire, Thermochim. Acta, 19 (1977) 101.
J. P. Dubes, M. Barres, E. Boitard and H. Tachoire, Coll. Intern. de Thermocinétique, Cadarache, 1979.
S. Randzio, J. Phys. Sci. Instr., 11 (1978) 145.
S. Randzio, Coll. Intern. de Thermocinétique, Cadarache, 1979.
M. Lewandowski, Coll. Intern. de Thermocinétique, Cadarache, 1979.
R. Point, J. L. Petit and P. C. Gravelle, J. Thermal Anal., 17 (1979) 383.
M. Hattori, S. Tanaka and K. Amaya, Bull. Chem. Soc. Japan, 43 (1970) 1027.
R. E. Johnson and R. L. Biltonen, J. Am. Chem. Soc., 97 (1975) 2349.
A. E. Beezer and H. J. V. Tyrrel, Science Tools, 19 (1972) 13.
J. P. Belaich, J. C. Senez and M. Murgiel, J. Bacteriol., 95 (1968) 1750.
J. P. Belaich, M. Murgiel, A. Belaich and P. Simonpietri, Proc. First Eur. Biophys. Congr., 4 (1971) 289.
E. Cesari, P. C. Gravelle, J. Gutenbaum, J. Hatt, J. Navarro, J. L. Petit, V. Torra, E. Utzig and W. Zielenkiewicz, J. Thermal Anal., 20 (1981) 47.
E. Cesari, J. Hatt, J. Ortin, V. Torra, J. Vinals and W. Zielenkiewicz, Thermochim. Acta (to be published).
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Zielenkiewicz, W. Calorimetry for thermokinetic determinations. Journal of Thermal Analysis 29, 179–192 (1984). https://doi.org/10.1007/BF02069955
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DOI: https://doi.org/10.1007/BF02069955