A kinetic expression is derived to explain how interfaces alter bulk chemical equilibria and accelerate reactions in micro-compartments. This description, aided by the development of a stochastic model, quantitatively predicts previous experimental observations of accelerated imine synthesis in micron-sized emulsions. The expression accounts for how reactant concentration and compartment size together lead to accelerated reaction rates under micro-confinement. These rates do not depend solely on concentration, but rather the fraction of total molecules in the compartment that are at the interface. Although there are ∼10⁷ to 10¹³ solute molecules in a typical micro-compartment, a kind of “stochasticity” appears when compartment size and reagent concentration yield nearly equal numbers of bulk and interfacial molecules. Although this is distinct from the stochasticity produced by nano-confinement, these results show how interfaces can govern chemical transformations in larger atmospheric, geologic and biological compartments.

中文翻译：

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界面如何加速微隔室内反应的动力学描述

得出动力学表达式来解释界面如何改变整体化学平衡并加速微隔室内的反应。该描述借助随机模型的发展，定量预测了微米级乳液中亚胺合成加速的先前实验观察。该表达式说明了在微约束下反应物浓度和隔室大小如何共同导致加速的反应速率。这些速率不仅取决于浓度，还取决于界面中总分子的比例。虽然有〜10 ⁷至10 ¹³在典型的微隔室中，溶质分子会在隔室大小和试剂浓度产生几乎相等数量的大分子和界面分子时出现“随机性”。尽管这与纳米约束产生的随机性不同，但这些结果表明界面如何控制更大的大气，地质和生物区室中的化学转化。