Heterogeneous reactions of solid nickel(II) complexes,V |
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| Authors: | E. Jóna V. Jesenák T. šramko J. GaŽo |
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| Affiliation: | 1. Department of Inorganic Chemistry, Slovak Technical University, Bratislava, Czechoslovakia
2. Department of Chemical Technology of Silicates, Slovak Technical University, Bratislava, Czechoslovakia
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| Abstract: | The kinetics of the thermal decomposition of solid complexes of the type Ni(NCS)2L2 (L=pyridine,β-picoline and quinoline), of pseudooctahedral configuration, were studied by using isothermal methods, on the basis of losses of weight, in the temperature range 90–191?. The most suitable reaction order for all the complexes under investigation was found to ben=2/3, i.e. the total decomposition rate is determined by the chemical process proper. The calculated values ofE a(in kcal · mole?1) decrease in the following order: Ni(NCS)2py2 (29.4)>Ni(NCS)2(β-pic)2 (27.6)>Ni(NCS)2Q2 (24.3). With increasing volume of the ligand L the reaction rate also increases, and this suggests that the reaction proceeds by dissociative activation. For all the investigated complexes it was found that δH>E A; this may be explained by a several-step mechanism and the complex Ni(NCS)2L is then considered an intermediate. |
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