Probing the interaction of amorphous solid water on a hydrophobic surface: dewetting and crystallization kinetics of ASW on carbon tetrachloride

Desorption of carbon tetrachloride from beneath an amorphous solid water (ASW) overlayer is explored utilizing a combination of temperature programmed desorption and infrared spectroscopy. Otherwise inaccessible information about the dewetting and crystallization of ASW is revealed by monitoring des...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2011-11, Vol.13 (44), p.19848-19855
Main Authors: May, R. Alan, Smith, R. Scott, Kay, Bruce D
Format: Article
Language:English
Subjects:
ADSORPTION
CARBON TETRACHLORIDE
Chemistry
CRYSTALLIZATION
DEPOSITION
DESORPTION
Dewetting
Environmental Molecular Sciences Laboratory
Exact sciences and technology
Fracture mechanics
General and physical chemistry
Graphene
Infrared spectroscopy
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
KINETICS
MONITORING
REFLECTION
SPECTROSCOPY
Surface physical chemistry
WATER
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Summary:Desorption of carbon tetrachloride from beneath an amorphous solid water (ASW) overlayer is explored utilizing a combination of temperature programmed desorption and infrared spectroscopy. Otherwise inaccessible information about the dewetting and crystallization of ASW is revealed by monitoring desorption of the CCl 4 underlayer. The desorption maximum of CCl 4 on graphene occurs at ∼140 K. When ASW wets the CCl 4 no desorption below 140 K is observed. However, the mobility of the water molecules increases with ASW deposition temperature, leading to a thermodynamically driven dewetting of water from the hydrophobic CCl 4 surface. This dewetting exposes some CCl 4 to the ambient environment, allowing unhindered desorption of CCl 4 below 140 K. When ASW completely covers the underlayer, desorption of CCl 4 is delayed until crystallization induced cracking of the ASW overlayer opens an escape path to the surface. The subsequent rapid episodic release of CCl 4 is termed a "molecular volcano". Reflection absorption infrared spectroscopy (RAIRS) measurements indicate that the onset and duration of the molecular volcano is directly controlled by the ASW crystallization kinetics. Amorphous solid water (ASW) prevents desorption of CCl 4 until crystallization induced cracking leads to eruption of the "Molecular Volcano".
ISSN:1463-9076
1463-9084
DOI:10.1039/c1cp21855g