Alkali metal hydroxides, MeOH

There are a few works devoted to the quantitative investigation of hydroxide ion dissociation in high-temperature ionic melts. Zambonin 

Oxygen electrodes in ionic melts. Oxide ion donors 

Wrench showed that hydroxide ions did not undergo decomposition according to equation (1.2.4) in the molten KCl-LiCl eutectic mixture at 400 °C [318]. This is probably connected with strong fixation of water by this melt, and may be explained by the extremely high hygroscopicity of LiCl [179]. The elevation of the melt temperature to 500 °C results in complete decomposition of hydroxide ions and removal of water from the melt, as is confirmed by both polarographic [319, 320] and potentiometric [232] measurements. 

Combes et al. reported investigations of the equilibrium constant of reaction (1.2.4) in the molten KCl-NaCl equimolar mixture [119, 180, 240], The experimental routine consists in addition of a weight of O2- donor to the melt afterwards the equilibrium e.m.f. of the cell with the indicator oxygen electrode (NilNiOlZr02) is measured and the e.m.f. values are determined at partial pressures of water vapour from 0.0013 to 0.011 atm. The calculations of the equilibrium constant of reaction (1.2.4), performed using the obtained e.m.f. values, show that in the temperature range 737-817 °C the dependence of the pK of the equilibrium (1.2.4) upon the inverse temperature is expressed by the following equation  

Since the stoichiometry of the dissociation process was beyond doubt, there were no examinations over a wide range of oxide-ion concentrations. 

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Kinetics of the transformations of the N-F class of fluorinating agents in water, acetonitrile, alcohols, and aqueous solutions of alkali metal hydroxides have been studied.159 Other kinetic studies include die reactions of triphenylphosphine with 3-methoxy- or 3-acctoxy-4,4,5,5-tetrasubstitutcd-1,2-dioxolanes,160 the reactions of 2-amino-5-chlorobenzophenone witii HC1 in MeOH-H20 (die aspect of nucleophilic aliphatic substitution lies in certain products arising from attack of AH2 on CH3OH there are six products in all, and rate constants are evaluated for die formation of each of them),161 and the hydrolysis of derivatives of diazidophenyhnethane.162... 

Ni5(CO)9] . However, the existence of these anions is not certain. The reaction of [Ni(CO)4] with amalgams in THF or with the alkali metal hydroxides in MeOH gives [Ni5(CO)i2] and [Ni6(CO)i2] - In solution these anions exist in equilibrium ... 

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