Kinetic Study on the Synthesis of Alkali Formate from Carbon Dioxide and Hydrogen Catalyzed by Palladium(II) Chloride in an Aqueous Alkali Solution

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  • アルカリ水溶液中における塩化パラジウム(II)触媒による加圧二酸化炭素と水素からギ酸塩生成反応の速度論的研究

Description

It was foudd that palladium (II) chloride is a highly active catalyst for the synthesis of alkali formate from carbon dioxide and hydrogen in an aqueous alkali solution under pressure. For example, potassium formate, in 82.6 mol% yield, was obtained under the following condition: pressure of carbon dioxide being 40 atm, pressure of hydrogen being 106 atm, concentration of palladium(II) chloride being 1.0 g/l, concentration of potassim hydroxide in aqueous solution being 1.9 mol/l, temperature being 240deg;C, and period of reaction being 3 hrs.<BR>The effect of following variables on the rate of formation of formate was examined in view of kinetics: starting amount of catalyst, alkali concentration, partial pressure of carbon dioxide or hydrogen, and temperature. Assuming that the reaction substances involved hydrogencarbonate ion and active catalyst-hydrogen complexes, following initial rate equation has been derived:: Solubility constant of 112, Pressure of H2, M: Palladium-catalyst, V0: Initial rate. This equation reasonably agreed with experimental results.<BR>The values of the apparent rate constant k', the equilibrium constant Ks, and the overall activation energy Ea, were found to be 2.90×10-2(160deg;C) 4.97×10-2 la g-cat-2min-1(200°C), 28.4 (160°C) 13.2 ismol-i (200°C), and 7 kcal. mol-1 respectively.

Journal

  • NIPPON KAGAKU KAISHI

    NIPPON KAGAKU KAISHI 1977 (3), 302-309, 1977-03-10

    The Chemical Society of Japan

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