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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Organic Acids Tunably Catalyze Carbonic Acid Decomposition
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Organic Acids Tunably Catalyze Carbonic Acid Decomposition

机译：有机酸可调谐地催化碳酸分解

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摘要

Density functional theory calculations predict that the gas-phase decomposition of carbonic acid, a high-energy, 1,3-hydrogen atom transfer reaction, can be catalyzed by a monocarboxylic acid or a dicarboxylic acid, including carbonic acid itself. Carboxylic acids are found to be more effective catalysts than water. Among the carboxylic acids, the monocarboxylic acids outperform the dicarboxylic ones wherein the presence of an intramolecular hydrogen bond hampers the hydrogen transfer. Further, the calculations reveal a direct correlation between the catalytic activity of a monocarboxylic acid and its pK_a, in contrast to prior assumptions about carboxylic-acid-catalyzed hydrogen-transfer reactions. The catalytic efficacy of a dicarboxylic acid, on the other hand, is significantly affected by the strength of an intramolecular hydrogen bond. Transition-state theory estimates indicate that effective rate constants for the acid-catalyzed decomposition are four orders-of-magnitude larger than those for the water-catalyzed reaction. These results offer new insights into the determinants of general acid catalysis with potentially broad implications.
机译：密度泛函理论计算预测，碳酸的气相分解是一种高能的1,3-氢原子转移反应，可通过单羧酸或二羧酸（包括碳酸本身）来催化。发现羧酸比水更有效。在羧酸中，一元羧酸优于二元羧酸，其中分子内氢键的存在阻碍了氢的转移。此外，与先前关于羧酸催化的氢转移反应的假设相反，该计算揭示了单羧酸的催化活性与其pK_a之间的直接相关性。另一方面，二羧酸的催化功效受到分子内氢键强度的显着影响。过渡态理论估计表明，酸催化分解的有效速率常数比水催化反应的有效速率常数大四个数量级。这些结果为一般酸催化的决定因素提供了新的见解，并可能具有广泛的意义。

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