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Kinetic studies on the formation of nitrosamines I

Formation of dimethylnitrosamine in aqueous solution of perchloric acid

Kinetische Untersuchungen über die Bildung von Nitrosaminen I

Entstehung von Dimethylnitrosamin in wäßriger Perchlorsäurelösung

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Summary

The kinetics of nitrosation of dimethylamine (DMA) in aqueous perchloric acid solution haves been studied using a differential spectrophotometric technique. The rate law is Initial rate=e[DMA]0 [nitrite] 20 [H+]/(f+[H+])2 where [DMA]0 and [nitrite]0 represent initial stoichiometric concentrations. At 310.0 K and μ=2.0 M, e=(2.2±0.2)×10−5 M−1 s−1 and f=(1.28±0.02) ×10−3M. The associated activation energy is 56±3kJ mol−1. A clear inhibition of the nitrosation rate by ionic strength has been observed in which only the kinetic parameter (f) has an effective change. It is concluded that under the experimental conditions of this work only the dinitrogen trioxid is the effective carrier for the nitrosation.

Zusammenfassung

Die Kinetik der Nitrosierung von Dimethylamin (DMA) wurde in Perchlorsäurelösung durch eine differential-spectrophotometrische Technik untersucht. Die folgende kinetische Gleichung wurde festgestellt: Anfangsgeschwindigkeit=e[DMA]0 [Nitrit] 20 , [H+]/(f+[H+])2 wobei [DMA]0 und [Nitrit]0 die stoichiometrischen Ausgangskonzentrationen bedeuten. Bei 310,0 K und μ=2,0 M wurden folgende kinetischen Parameterwerte e=(2,2±0,2)×10−5 M−1 s−1 und f=(1,28±0,02)× 10−3M ermittelt. Auch wurde die Aktivierungsenergie des Prozesses zu E*=56±3 kJ mol−1 festgestellt. Eine klare Verringerung der Nitrosierungsgeschwindigkeit mit der lonenstärke wurde infolge der Veränderung des kinetischen Parameters (f) beobachtet. Unter den hier gewählten Reaktionsbedingungen ist zu schließen, daß das Distickstofftrioxid das einzige nitrosierende Agens ist.

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References

  • Bunton,C.A., Stedman,G.: Mechanism of the azide-nitrite reaction. III. Reaction in [18O] water. J. Chem. Soc. 1959, 3466–3474

  • Cachaza,J.M., Casado,J., Castro,A., López Quintela,M. A.: Kinetics of oxidation of nitrite by hypochlorite ions in aqueous basic solution. Can. J. Chem. 54, 3401–3406 (1976)

    Google Scholar 

  • Deming,W.E.: Statistical adjustement of data. New York: John Willey & Sons, Inc., (1943)

    Google Scholar 

  • Druckrey,H., Preussmann,R., Ivankovic,S.: Organtrope cancerogene Wirkungen bei 65 verschiedenen N-Nitroso-Verbindungen an BD-Ratten. Z. Krebsforsch. 69, 103–201 (1967)

    Google Scholar 

  • Fan,T.Y., Tannenbaum,S.R.: Factors influencing the rate of formation of nitroso-morpholine from morpholine and nitrite: Acceleration by thiocyanate and other anions. J. Agr. Food Chem. 21, 237–240 (1973)

    Google Scholar 

  • Friedman,M.A.: Nitrosation of sarcosine. Chemical kinetics and gastric assay. Bull. Environ. Contam. Toxicol. 8, 375–382 (1972)

    Google Scholar 

  • Goldfield,S.M., Quandt,R.E.: Some tests for homoscedasticity. J. Am. Statist. Assoc. 60, 539–547 (1965)

    Google Scholar 

  • Hildrum,K.I., Williams,J.L., Scanlan,R.A.: Effect of sodium chloride concentration on the nitrosation of proline at different pH levels. J. Agr. Food Chem. 23, 439–442 (1975)

    Google Scholar 

  • Hughes,E.D., Ingold,C.K., Ridd,J.H.: Nitrosation, Diazotization, and Deamination. Part I and subsequent papers. J. Chem. Soc. 1958, 58–89

  • Kalatzis,E., Ridd,J.H.: Nitrosation, Diazotization and Deamination. XII. The kinetics of N-nitrosation of N-methylaniline. J. Chem. Soc. (B), 1966, 529–533

  • Kawamura,T., Sakai,K., Miyazawa,F., Wada,H., Ito,Y., Tanimura,A.: Nitrosamines in foods. IV. Distribution of secondary amines in foods. J. Food Hyg. Soc. Japan 12, 192–197 (1971a)

    Google Scholar 

  • Kawamura,T., Sakai,K., Miyazawa,F., Wada,H., Ito,Y., Tanimura,A.: Nitrosamines in foods. IV. Distribution of secondary amines in foods. J. Food Hyg. Soc. Japan 12, 394–398 (1971b)

    Google Scholar 

  • Lijinsky,W., Epstein,S. S.: Nitrosamines as environmental carcinogens. Nature 225, 21–23 (1970)

    Google Scholar 

  • Magee,P.N., Barnes,J.N.: Carcinogenic nitroso compounds. Advan. Cancer Res. 10, 163–246 (1967)

    Google Scholar 

  • Masui,M., Nakahara,H., Ohmori,H., Sayo,H.: Kinetic studies on the formation of dimethylnitrosamine. Chem. Pharm. Bull. 22, 1846–1849 (1974)

    Google Scholar 

  • Mirvish,S.S.: Kinetics of dimethylamine nitrosation in relation to nitrosamine carcinogenesis. J. Nat. Cancer Inst. 44, 633–639 (1970)

    Google Scholar 

  • Perrin,D.D.: Dissotiation constants of organic bases in aqueous solution. London: Butterworths (1965)

    Google Scholar 

  • Raja,K., Kann,J., Tauts,O., Kask,K.: Studyng the formation of nitrosamines. Tr. Tallin. Politkh. Inst. 367, 101–107 (1974)

    Google Scholar 

  • Ridd,J.H.: Nitrosation, diazotization and deamination. Quart. Rev. 15, 418–441 (1961)

    Google Scholar 

  • Sander,J., Schweinsberg,F., Menz,H.P.: Untersuchungen über die Entstehung cancerogener Nitrosamine im Magen. Z. Physiol. Chem. 349, 1691–1697 (1968)

    Google Scholar 

  • Stedman,G.: Mechanism of the azide-nitrite reaction. I and II. J. Chem. Soc. 1959, 2943–2954

  • Stedman,G.: Mechanism of the azide-nitrite reaction. IV. J. Chem. Soc. 1960, 1702–1709

  • Taylor,T.W.J., Price, L.S.: The action of nitrous acid on amino-compounds III. Dimethylamine, n-propylamine, and glycine ethyl ester. J. Chem. Soc. 1929, 2025–2059

  • Tummavuori,J., Lumme,P.: Protolysis of nitrous acid in aqueous sodium nitrate and sodium nitrite solutions at different temperatures. Acta Chem. Scand. 22, 2003–2011 (1968)

    Google Scholar 

  • Turney,T.A., Wright,G.A.: Nitrous acid and nitrosation. Chem. Rev. 59, 497–513 (1959)

    Google Scholar 

  • Wishnok,J.S., Archer,M.C.: Structure-activity relations in nitrosamine carcinogenesis. Brit. J. Cancer 33, 307–311 (1976)

    Google Scholar 

  • Wogan,G.N., Tannenbaum,S.R.: Environmental N-nitroso compounds. Implications for public health. Toxicol. Appl. Pharmacol. 31, 375–383 (1975)

    Google Scholar 

  • Wolff,I.A., Wasserman,A.E.: Nitrates, nitrites and nitrosamines. Science 177, 15–19 (1972)

    Google Scholar 

  • Yamada,T., Yamamoto,M., Tanimura,A.: Studies on the formation of nitrosamines I. Kinetical studies on the nitrosation of piperidine and morpholine. J. Food Hyg. Soc. Japan 15, 201–205 (1974)

    Google Scholar 

  • Ziebarth,D.: Untersuchungen über die Nitrosierung sekundärer Amine in Puffergemischen und in menschlichen Magensaft. Arch. Geschwulstforsch. 43, 42–51 (1974)

    Google Scholar 

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Authors and Affiliations

  1. Dpto. de Química Física, Instituto de Investigaciones Químicas, C.S.I.C., Universidad de Santiago, E-Santiago de Compostela, España

    J. M. Cachaza, J. Casado, A. Castro & M. A. López Quintela

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  1. J. M. Cachaza
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  2. J. Casado
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  3. A. Castro
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  4. M. A. López Quintela
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Cachaza, J.M., Casado, J., Castro, A. et al. Kinetic studies on the formation of nitrosamines I. Z. Krebsforsch. 91, 279–290 (1978). https://doi.org/10.1007/BF00312290

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  • DOI: https://doi.org/10.1007/BF00312290

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