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本文合成了一个新的双Schiff碱钴配合物,并研究了该配合物在吡啶溶液中的吸氧过程热力学。在4—24℃范围内,吸氧摩尔比为1:1,吸氧过程热力学参数为:△H=-26.8(±0.5)kJ/mol,△S=-89.2(±1.8)J/mol·K。在30—45℃范围内,吸氧摩尔比为2:1,吸氧过程的热力学参数为:△H=-172.6(±9.14)kJ/mol,△S=-517.3(±29.4)J/mol·K。温度超过45℃,自氧化作用变得明显,配合物中苄羟基被氧化为醛基。提出了可能的氧化反应机理。
In this paper, a new double Schiff base cobalt complex was synthesized and the thermodynamics of the oxygen absorption process of the complex in pyridine solution was studied. In the range of 4-24 ℃, the molar ratio of oxygen to oxygen is 1: 1, the thermodynamic parameters of oxygen absorption process are ΔH = -26.8 (± 0.5) kJ / mol and ΔS = -89.2 (± 1.8) J / K. In the range of 30-45 ℃, the molar ratio of oxygen to oxygen was 2: 1 and the thermodynamic parameters of oxygen absorption process were ΔH = -172.6 (± 9.14) kJ / mol and ΔS = -517.3 (± 29.4) J / mol K When the temperature exceeds 45 ° C, the self-oxidation becomes obvious, and the benzylic hydroxyl group in the complex is oxidized to the aldehyde group. Proposed a possible oxidation reaction mechanism.