Interfacial supercooling and the precipitation of hydrohalite in frozen NaCl solutions as seen by X-ray absorption spectroscopy

Laboratory experiments are presented on the phase change at the surface of sodium chloride–water mixtures at temperatures between 259 and 241 K. Chloride is a ubiquitous component of polar coastal surface snow. The chloride embedded in snow is involved in reactions that modify the chemical composition of snow as well as ultimately impact the budget of trace gases and the oxidative capacity of the overlying atmosphere. Multiphase reactions at the snow–air interface have been of particular interest in atmospheric science. Undoubtedly, chemical reactions proceed faster in liquids than in solids; but it is currently unclear when such phase changes occur at the interface of snow with air. In the experiments reported here, a high selectivity to the upper few nanometres of the frozen solution–air interface is achieved by using electron yield near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy. We find that sodium chloride at the interface of frozen solutions, which mimic sea-salt deposits in snow, remains as supercooled liquid down to 241 K. At this temperature, hydrohalite exclusively precipitates and anhydrous sodium chloride is not detected. In this work, we present the first NEXAFS spectrum of hydrohalite. The hydrohalite is found to be stable while increasing the temperature towards the eutectic temperature of 252 K. Taken together, this study reveals no differences in the phase changes of sodium chloride at the interface as compared to the bulk. That sodium chloride remains liquid at the interface upon cooling down to 241 K, which spans the most common temperature range in Arctic marine environments, has consequences for interfacial chemistry involving chlorine as well as for any other reactant for which the sodium chloride provides a liquid reservoir at the interface of environmental snow. Implications for the role of surface snow in atmospheric chemistry are discussed.

Supercooled liquid sodium chloride solution on ice and snow surfaces

<p>Laboratory experiments are presented on the phase change at the surface of sodium chloride – water mixtures at temperatures between 259 K and 240 K. Chloride is a ubiquitous component of polar coastal surface snow. The chloride embedded in snow is involved in reactions that modify the chemical composition of snow as well as ultimately impact the budget of trace gases and the oxidative capacity of the overlying atmosphere.  Multiphase reactions at the snow – air interface have found particular interest in atmospheric science. Undoubtedly, chemical reactions proceed faster in liquids than in solids; but it is currently unclear when such phase changes occur at the interface of snow with air.</p><p>In the experiments reported here, a high selectivity to the upper few nanometres of the frozen solution – air interface is achieved by using electron yield near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. We find that sodium chloride at the interface of frozen solutions, which mimic sea-salt deposits in snow, remain as supercooled liquid down to 240 K, which is about 10 K lower than the freezing temperature of sodium chloride solutions. Below this temperature, hydrohalite exclusively precipitates, anhydrous sodium chloride is not detected. In this work, we present the first NEXAFS spectrum of hydrohalite. The hydrohalite is found to be stable while increasing the temperature towards the eutectic temperature of 253 K.</p><p> </p><p>Taken together, this study reveals no differences in the phase changes of sodium chloride at the interface as compared to the bulk. That sodium chloride remains liquid at the interface upon cooling down to 240 K, which spans the most common temperature range in Polar marine environments, has consequences for interfacial chemistry involving chlorine as well as for any other reactant for which the sodium chloride provides a liquid reservoir at the interface of environmental snow. Implications for the role of surface snow on atmospheric chemistry are discussed. </p>

Breaking inversion symmetry by protonation: experimental and theoretical NEXAFS study of the diazyniumion, N2H+

As an example of symmetry breaking in NEXAFS spectra of protonated species we present a high resolution NEXAFS spectrum of protonated dinitrogen, the diazynium ion N2H+. By ab-initio calculations we...

Interfacial supercooling and the precipitation of hydrohalite in frozen NaCl solutions by X-ray absorption spectroscopy

Laboratory experiments are presented on the phase change at the surface of sodium chloride – water mixtures at temperatures between 259 K and 240 K. Chloride is a ubiquitous component of polar coastal surface snow. The chloride embedded in snow is involved in reactions that modify the chemical composition of snow as well as ultimately impact the budget of trace gases and the oxidative capacity of the overlying atmosphere. Multiphase reactions at the snow – air interface have found particular interest in atmospheric science. Undoubtedly, chemical reactions proceed faster in liquids than in solids; but it is currently unclear when such phase changes occur at the interface of snow with air. In the experiments reported here, a high selectivity to the upper few nanometres of the frozen solution – air interface is achieved by using electron yield near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. We find that sodium chloride at the interface of frozen solutions, which mimic sea-salt deposits in snow, remain as supercooled liquid down to 240 K. Below this temperature, hydrohalite exclusively precipitates, anhydrous sodium chloride is not detected. In this work, we present the first NEXAFS spectrum of hydrohalite. The hydrohalite is found to be stable while increasing the temperature towards the eutectic temperature of 253 K. Taken together, this study reveals no differences in the phase changes of sodium chloride at the interface as compared to the bulk. That sodium chloride remains liquid at the interface upon cooling down to 240 K, which spans the most common temperature range in Polar marine environments, has consequences for interfacial chemistry involving chlorine as well as for any other reactant for which the sodium chloride provides a liquid reservoir at the interface of environmental snow. Implications for the role of surface snow on atmospheric chemistry are discussed.

Fingerprints of sp1 Hybridized C in the Near-Edge X-ray Absorption Spectra of Surface-Grown Materials

Carbon structures comprising sp 1 chains (e.g., polyynes or cumulenes) can be synthesized by exploiting on-surface chemistry and molecular self-assembly of organic precursors, opening to the use of the full experimental and theoretical surface-science toolbox for their characterization. In particular, polarized near-edge X-ray absorption fine structure (NEXAFS) can be used to determine molecular adsorption angles and is here also suggested as a probe to discriminate sp 1 /sp 2 character in the structures. We present an ab initio study of the polarized NEXAFS spectrum of model and real sp 1 /sp 2 materials. Calculations are performed within density functional theory with plane waves and pseudopotentials, and spectra are computed by core-excited C potentials. We evaluate the dichroism in the spectrum for ideal carbynes and highlight the main differences relative to typical sp 2 systems. We then consider a mixed polymer alternating sp 1 C 4 units with sp 2 biphenyl groups, recently synthesized on Au(111), as well as other linear structures and two-dimensional networks, pointing out a spectral line shape specifically due to the the presence of linear C chains. Our study suggests that the measurements of polarized NEXAFS spectra could be used to distinctly fingerprint the presence of sp 1 hybridization in surface-grown C structures.

Self-association of organic solutes in solution: a NEXAFS study of aqueous imidazole

N K-edge near-edge X-ray absorption fine-structure (NEXAFS) spectra of imidazole in concentrated aqueous solutions have been acquired. The NEXAFS spectra of the solution species differ significantly from those of imidazole monomers in the gas phase and in the solid state of imidazole, demonstrating the strong sensitivity of NEXAFS to the local chemical and structural environment. In a concentration range from 0.5 to 8.2 mol L−1 the NEXAFS spectrum of aqueous imidazole does not change strongly, confirming previous suggestions that imidazole self-associates are already present at concentrations more dilute than the range investigated here. We show that various types of electronic structure calculations (Gaussian, StoBe, CASTEP) provide a consistent and complete interpretation of all features in the gas phase and solid state spectra based on ground state electronic structure. This suggests that such computational modelling of experimental NEXAFS will permit an incisive analysis of the molecular interactions of organic solutes in solutions. It is confirmed that microhydrated clusters with a single imidazole molecule are poor models of imidazole in aqueous solution. Our analysis indicates that models including both a hydrogen-bonded network of hydrate molecules, and imidazole–imidazole interactions, are necessary to explain the electronic structure evident in the NEXAFS spectra.

SURFACE PHOTODEGRADATION OF POLY(VINYLIDENE FLUORIDE) BY INNER-SHELL EXCITATION

Poly(vinylidene fluoride) (PVDF, –( CH 2– CF 2)n–) shows the effective H + desorption induced by the irradiation of photon corresponding to the transition from carbon ( C ) 1s to σ( C – H )*. In order to clarify the effect of the C – H bond scission by the irradiation, near-edge X-ray absorption fine structure (NEXAFS) spectra and the kinetic energy (Ek) distribution of desorbed ion were observed. By the irradiation of photon near C 1s region, a new peak appears in the C 1s NEXAFS spectra at photon energy of 285 eV, which is about 3 eV lower than that of the lowest peak in the NEXAFS spectrum of the pristine PVDF film. The appearance of the lowest NEXAFS peak of irradiated PVDF film is assigned to the transition to π*. It indicates that the irradiation of photons near C 1s region introduces carbon–carbon double bonds into the backbone chain of PVDF. At early stage of X-ray exposure the yield of desorbed ion with low Ek (~ 2 eV) decreases rapidly. The ion with low Ek is assigned to H + desorbed from the sp3-hybrid state, which is characteristics of the pristine PVDF. It indicates that formation of double bonds in PVDF backbone chain makes the number of sp3-hybrid state decrease. This variation occurs by irradiation of photons corresponding to the transition from C 1s to σ( C – H )* more rapidly than that to the transition to σ( C – F )*.