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Kinetik der Diazotierung der Chloraniline in methanolischer Chlorwasserstofflösung

Kinetics of the diazotization of the chloroanilines in methanolic hydrochloric acid solution

  • Anorganische, Struktur- und Physikalische Chemie
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Monatshefte für Chemie / Chemical Monthly Aims and scope Submit manuscript

Abstract

The kinetics of the diazotization of o-, m-, p-chloroaniline in 0.005n- to 0.4n-methanolic HCl-solution at 25, 15, 0, −10 −20, and −30°C was invertigated.

It was found that the nitrosation reaction (the same as in1)

$$C_6 H_4 ClNH_2 + NOCl \mathop \rightleftharpoons \limits^k C_6 H_4 ClNH_2 NO^ + + Cl^ - $$

is a proceeding advance-back-reaction. The decomposition of C6H4ClNH2NO+ by splitting off a proton is the rate determining step. The free activation enthalpies ΔG * for the nitrosation reaction, the activation entropies ΔS *, the activation enthalpies ΔH * and the activation energiesE a at the given temperatures are calculated.

The experimentally found and the calculated velocities are given in Tables 1–6. The equilibrium constants of the o-, m-, p-chloroanilinium ions, and nitrosyl-chloride in methanol are indicated in Table 7, diagram 1.

TheK M values (the ionic products of methanol, extrapolated at infinite dilution) together with theK A values of Table 7 give theK B values (p. 2) using the table10. The ΔG B values can be calculated using equation ΔG B = ∔RTlnK B

Fig 2 shows the linear dependance of the logarithmus of the ΔG * values from the logarithmus of theK B values.

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Literatur

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Authors and Affiliations

  1. Institut für Physikalische Chemie der Technischen Hochschule Wien, Getreidemarkt 9, A-1060, Wien, Österreich

    A. Woppmann

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  1. A. Woppmann
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Woppmann, A. Kinetik der Diazotierung der Chloraniline in methanolischer Chlorwasserstofflösung. Monatshefte für Chemie 105, 419–426 (1974). https://doi.org/10.1007/BF00907391

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  • DOI: https://doi.org/10.1007/BF00907391

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