Kinetic studies on the formation of nitrosamines I

Formation of dimethylnitrosamine in aqueous solution of perchloric acid
  • J. M. Cachaza
  • J. Casado
  • A. Castro
  • M. A. López Quintela
Original Papers

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]02[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.

Key words

Dimethylnitrosamine formation in aqueous perchloric solution Nitrosation of dimethylamine in aqueous perchloric-solution Kinetic and mechanisms of the nitrosation of dimethylamine 

Kinetische Untersuchungen über die Bildung von Nitrosaminen I

Entstehung von Dimethylnitrosamin in wäßriger Perchlorsäurelösung

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]02, [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.

Schlüsselwörter

Dimethylnitrosamin Bildung in wäßriger Perchlorsäurelösung Nitrosierung von Dimethylamin in wäßriger Perchlorsäurelösung Kinetik und Mechanismus der Nitrosierung von Dimethylamin 

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Copyright information

© Springer-Verlag 1978

Authors and Affiliations

  • J. M. Cachaza
    • 1
  • J. Casado
    • 1
  • A. Castro
    • 1
  • M. A. López Quintela
    • 1
  1. 1.Dpto. de Química FísicaInstituto de Investigaciones Químicas, C.S.I.C., Universidad de SantiagoE-Santiago de CompostelaEspaña

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