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非晶态固态水中结晶冰的成核速率。

The nucleation rate of crystalline ice in amorphous solid water.

作者信息

Safarik D J, Mullins C B

机构信息

Department of Chemical Engineering, Texas Materials Institute, University of Texas at Austin, Austin, Texas 78712-0231, USA.

出版信息

J Chem Phys. 2004 Sep 22;121(12):6003-10. doi: 10.1063/1.1779171.

Abstract

The kinetics of crystalline ice nucleation and growth in nonporous, molecular beam deposited amorphous solid water (ASW) films are investigated at temperatures near 140 K. We implement an experimental methodology and corresponding model of crystallization kinetics to decouple growth from nucleation and quantify the temperature dependence and absolute rates of both processes. Nucleation rates are found to increase from approximately 3x10(13) m(-3) s(-1) at 134 K to approximately 2x10(17) m(-3) s(-1) at 142 K, corresponding to an Arrhenius activation energy of 168 kJ/mol. Over the same temperature range, the growth velocity increases from approximately 0.4 to approximately 4 A s(-1), also exhibiting Arrhenius behavior with an activation energy of 47 kJ/mol. These nucleation rates are up to ten orders of magnitude larger than in liquid water near 235 K, while growth velocities are approximately 10(9) times smaller. Crystalline ice nucleation kinetics determined in this study differ significantly from those reported previously for porous, background vapor deposited ASW, suggesting the nucleation mechanism is dependent upon film morphology.

摘要

在接近140K的温度下,研究了非多孔、分子束沉积的非晶态固体水(ASW)薄膜中结晶冰的成核和生长动力学。我们采用了一种实验方法和相应的结晶动力学模型,以将生长与成核解耦,并量化这两个过程的温度依赖性和绝对速率。发现成核速率从134K时的约3×10¹³ m⁻³ s⁻¹增加到142K时的约2×10¹⁷ m⁻³ s⁻¹,对应于168 kJ/mol的阿仑尼乌斯活化能。在相同温度范围内,生长速度从约0.4增加到约4 Å s⁻¹,也表现出阿仑尼乌斯行为,活化能为47 kJ/mol。这些成核速率比235K附近液态水中的成核速率高出多达十个数量级,而生长速度则小约10⁹倍。本研究中确定的结晶冰成核动力学与先前报道的多孔、背景气相沉积ASW的成核动力学有显著差异,表明成核机制取决于薄膜形态。

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