Surface Transformations and Water Uptake on Liquid and Solid Butanol near the Melting Temperature

Water interactions with organic surfaces are of central importance in biological systems and many Earth system processes. Here we describe experimental studies of water collisions and uptake kinetics on liquid and solid butanol from 160 to 200 K. Hyperthermal D2O molecules (0.32 eV) undergo efficient trapping on both solid and liquid butanol, and only a minor fraction scatters inelastically after an 80% loss of kinetic energy to surface modes. Trapped molecules either desorb within a few ms, or are taken up by the butanol phase during longer times. The water uptake and surface residence time increase with temperature above 180 K indicating melting of the butanol surface 4.5 K below the bulk melting temperature. Water uptake changes gradually across the melting point and trapped molecules are rapidly lost by diffusion into the liquid above 190 K. This indicates that liquid butanol maintains a surface phase with limited water permeability up to 5.5 K above the melting point. These surface observations are indicative of an incremental change from solid to liquid butanol over a range of 10 K straddling the bulk melting temperature, in contrast to the behavior of bulk butanol and previously studied materials.Comment: 28 pages, 4 figures + introduction figur

Photocatalytic oxidation of gaseous benzene, toluene and xylene under UV and visible irradiation over Mn-doped TiO2 nanoparticles

The photocatalytic oxidation of gaseous benzene, toluene and xylene (BTX) over un-doped, 0.1 and 1 wt% Mn-TiO2 nanoparticles under ultraviolet and visible irradiation was studied in atmosphere of synthetic air or inert gas. The photocatalytic decomposition efficiency and the oxidation products were determined using a Static Photochemical Reactor coupled with FTIR spectroscopy. BTX underwent efficient decomposition over Mn-TiO2 photocatalysts under UV irradiation, more with oxygen presence and less without oxygen. More important toluene and xylene went substantial decomposition over 0.1 mol% Mn-TiO2 under visible irradiation with oxygen presence. The main final oxidation products in the UV photocatalysis of BTX were CO2, CO and H2O, with CO2 and CO yields 4 and 2 respectively. The conversion percentage of benzene, toluene, and xylene to CO2 were 63.6%, 56.4%, 51.8%, and to CO 29%, 26.5%, 23.2%, respectively. In the visible photocatalysis of toluene and xylene the yields of CO were insignificant. Formation of carbon containing deposits on TiO2 surfaces was observed after extensive UV photocatalysis of toluene and xylene, and such by-products surface coverage may reduce the photocatalytic activity of TiO2 samples. Some aspects of the photocatalytic mechanism were examined. Keywords: Mn-doped TiO2, Visible, Light photocatalysis, Photodegradation of benzene, Toluene, Xylene, Indoors air pollutio

Collision dynamics and uptake of water on alcohol-covered ice

Molecular scattering experiments are used to investigate water interactions with methanol and n-butanol covered ice between 155 K and 200 K. The inelastically scattered and desorbed products of an incident molecular beam are measured and analyzed to illuminate molecular scale processes. The residence time and uptake coefficients of water impinging on alcohol-covered ice are calculated. The surfactant molecules are observed to affect water transport to and from the ice surface in a manner that is related to the number of carbon atoms they contain. Butanol films on ice are observed to reduce water uptake by 20 %, whereas methanol monolayers pose no significant barrier to water transport. Water colliding with methanol covered ice rapidly permeates the alcohol layer, but on butanol water molecules have mean surface lifetimes of less than or similar to 0.6 ms, enabling some molecules to thermally desorb before reaching the water ice underlying the butanol. These observations are put into the context of cloud and atmospheric scale processes, where such surfactant layers may affect a range of aerosol processes, and thus have implications for cloud evolution, the global water cycle, and long term climate

Collision dynamics and uptake of water on alcohol-covered ice

Molecular scattering experiments are used to investigate water interactions with methanol and n-butanol covered ice between 155 K and 200 K. The inelastically scattered and desorbed products of an incident molecular beam are measured and analyzed to illuminate molecular scale processes. The residence time and uptake coefficients of water impinging on alcohol-covered ice are calculated. The surfactant molecules are observed to affect water transport to and from the ice surface in a manner that is related to the number of carbon atoms they contain. Butanol films on ice are observed to reduce water uptake by 20 %, whereas methanol monolayers pose no significant barrier to water transport. Water colliding with methanol covered ice rapidly permeates the alcohol layer, but on butanol water molecules have mean surface lifetimes of less than or similar to 0.6 ms, enabling some molecules to thermally desorb before reaching the water ice underlying the butanol. These observations are put into the context of cloud and atmospheric scale processes, where such surfactant layers may affect a range of aerosol processes, and thus have implications for cloud evolution, the global water cycle, and long term climate