Title: Raman Spectroscopy of Isotopic Water Diffusion in Ultraviscous, Glassy, and Gel States in Aerosol by Use of Optical Tweezers

Abstract

The formation of ultraviscous, glassy, and amorphous gel states in aqueous aerosol following the loss of water results in nonequilibrium dynamics due to the extended time scales for diffusive mixing. Existing techniques for measuring water diffusion by isotopic exchange are limited by contact of samples with the substrate, and methods applied to infer diffusion coefficients from mass transport in levitated droplets requires analysis by complex coupled differential equations to derive diffusion coefficients. Here, we present a new technique that combines contactless levitation with aerosol optical tweezers with isotopic exchange (D₂O/H₂O) to measure the water diffusion coefficient over a broad range (D_w ≈ 10^-12-10^-17 m²s^-1) in viscous organic liquids (citric acid, sucrose, and shikimic acid) and inorganic gels (magnesium sulfate, MgSO₄). For the organic liquids in binary and ternary mixtures, D_w depends on relative humidity and follows a simple compositional Vignes relationship. In MgSO₄ droplets, water diffusivity decreases sharply with water activity and is consistent with predictions from percolation theory. These measurements show that, by combining micrometer-sized particle levitation (a contactless measurement with rapid mixing times) with an established probe of water diffusion, D_w can be simply and directly quantified for amorphous and glassy states that are inaccessible to existing methods.

Authors:

Davies, James F. ^[1]; Wilson, Kevin R. ^[1]

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+ Show Author Affiliations

1. Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Chemical Sciences Division

Publication Date:

Mon Jan 11 00:00:00 EST 2016

Research Org.:

Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

OSTI Identifier:

1454451

Grant/Contract Number:  

AC02-05CH11231

Resource Type:

Accepted Manuscript

Journal Name:

Analytical Chemistry

Additional Journal Information:

Journal Volume: 88; Journal Issue: 4; Related Information: © 2016 American Chemical Society.; Journal ID: ISSN 0003-2700

Publisher:

American Chemical Society (ACS)

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY