The dependence of low-energy electron attachment to CF3Br on electron and vibrational energy

In a joint experimental and theoretical effort, we have studied dissociative electron attachment (DEA) to the CF3Br molecule at electron energies below 2 eV. Using two variants of the laser photoelectron attachment method with a thermal gas target (T(G) = 300 K), we measured the energy dependent yield for Br- formation over the range E = 3-1200 meV with resolutions of about 3 meV (E < 200 meV) and 35 meV. At the onsets for excitation of one and two quanta for the C-Br stretching mode nu3, downward cusps are detected. With reference to the recommended thermal (300 K) attachment rate coefficient k(A)(CF3Br) = 1.4 x 10(-8) cm3 s(-1), absolute cross sections have been determined for Br- formation. In addition, we studied Br- and (CF3Br)Br- formations with a seeded supersonic target beam (10% CF3Br in helium carrier gas, with a stagnation pressure of 1-4 bars and nozzle temperatures of 300 and 600 K) and found prominent structure in the anion yields due to cluster formation. Using the microwave pulse radiolysis swarm technique, allowing for controlled variation of the electron temperature by microwave heating, we studied the dependence of the absolute DEA rate coefficient on the mean electron energy E over the range of 0.04-2 eV at gas temperatures T(G) ranging from 173 to 600 K. For comparison with the experimental results, semiempirical resonance R-matrix calculations have been carried out. The input for the theory includes the known energetic and structural parameters of the neutral molecule and its anion; the parameters of the resonant anion curves are chosen with reference to the known thermal rate coefficient for the DEA process. For the gas temperature T(G) = 300 K, good overall agreement of the theoretical DEA cross section with the experimental results is observed; moreover, rate coefficients for Br- formation due to Rydberg electron transfer, calculated with both the experimental and the theoretical DEA cross sections, are found to agree with the previously reported absolute experimental values. At T(G) = 300 K, satisfactory agreement is also found between the calculated and experimental attachment rate coefficients for mean electron energies E = 0.04-2 eV. The strong increase of the measured rate coefficients with rising gas temperature, however, could be only partially recovered by the R-matrix results. The differences may result from the influence of thermal excitations of other vibrational modes not included in the theory.     

Molecular dynamics simulations of laser-induced incandescence of soot using an extended ReaxFF reactive force field

Laser-induced incandescence (LII) of soot has developed into a popular method for making in situ measurements of soot volume fraction and primary particle sizes. However, there is still a lack of understanding regarding the generation and interpretation of the cooling signals. To model heat transfer from the heated soot particles to the surrounding gas, knowledge of the collision-based cooling as well as reactive events, including oxidation (exothermic) and evaporation (endothermic) is essential. We have simulated LII of soot using the ReaxFF reactive force field for hydrocarbon combustion. Soot was modeled as a stack of four graphene sheets linked together using sp(3) hybridized carbon atoms. To calculate the thermal accommodation coefficient of various gases with soot, graphene sheets of diameter 40 ? were used to create a soot particle containing 2691 atoms, and these simulations were carried out using the ReaxFF version incorporated into the Amsterdam Density Functional program. The reactive force field enables us to simulate the effects of conduction, evaporation, and oxidation of the soot particle on the cooling signal. Simulations were carried out for both reactive and nonreactive gas species at various pressures, and the subsequent cooling signals of soot were compared and analyzed. To correctly model N(2)-soot interactions, optimization of N-N and N-C-H force field parameters against DFT and experimental values was performed and is described in this paper. Subsequently, simulations were performed in order to find the thermal accommodation coefficients of soot with various monatomic and polyatomic gas molecules like He, Ne, Ar, N(2), CO(2), and CH(4). For all these species we find good agreement between our ReaxFF results and previously published accommodation coefficients. We thus believe that Molecular Dynamics using the ReaxFF reactive force field is a promising approach to simulate the physical and chemical aspects of soot LII.     

Tropospheric multiphase chemistry of 2,5- and 2,6-dimethylphenols: determination of the mass accommodation coefficients and the Henry's law constants

The uptake of 2,5-dimethylphenol and 2,6-dimethylphenol on aqueous surfaces was measured between 279 and 293 K, using the wetted-wall flow tube technique coupled with UV absorption spectroscopic detection. For both compounds, the uptake coefficients gamma were found to be independent of the KOH scavenger concentration in the range of 0.01 to 1 M (pH > pK(a)) and of the liquid-gas contact times. In addition, the uptake coefficients and the derived mass accommodation coefficients alpha show a negative temperature dependence in the investigated temperature range. The mass accommodation coefficients decrease from 1.1 x 10(-3) to 1.1 x 10(-4), and from 5.4 x 10(-4) to 6.4 x 10(-5) for 2,5-dimethylphenol and 2,6-dimethylphenol, respectively. These results are used to discuss the incorporation of these species into the liquid using the nucleation theory. Henry's law constants (HLC) of both compounds were directly measured using a dynamic equilibrium system based on the water/air equilibrium at the interface within the length of a microporous tube. The measurements were conducted over the range 278-293 K in both deionized water and 35 g L(-1) solution of NaCl. At 293 K and in pure water, HLC were found to be equal to (in units of M atm(-1)): 2,5-dimethylphenol, HLC = (1270 +/- 240); 2,6-dimethylphenol, HLC = (250 +/- 80). All of the values for HLC in 35 g L(-1) salt solution were 5-55% lower than the corresponding values in deionized water, depending on the compound and the temperature. These data (mass accommodation coefficients and Henry's law constants) were then used to estimate the partitioning of these phenolic compounds between gaseous and aqueous phases and the corresponding atmospheric lifetimes under clear sky (tau(gas)) and cloudy conditions (tau(multiphase)) have then been derived. The calculated multiphase lifetimes (in units of hours) are lower than those in gas phase at a cumulus temperature of 283 K (in parentheses): 2,5-dimethylphenol, 2.2 (3.5); 2,6-dimethylphenol, 3.8 (4.2).     

Onsager heat of transport for water vapour at the surface of water and ice: thermal accommodation coefficients for water vapour on a stainless-steel surface

The Onsager heat of transport Q* has been measured for water vapour at the surface of water, supercooled water, and ice, over the temperature range -8 to +10 degrees C. For liquid water, Q* is constant at -24.7 +/- 3.6 kJ mol(-1) (two standard deviations) over the pressure range 4-9.5 Torr. Provided the ice is suitably aged, the |Q*| values are very similar for water and ice, a result which is consistent with the presence of a liquid-like layer at the surface of ice. The values are slightly larger for ice, in proportion to the ratio of the heat of sublimation of ice to the heat of vaporization of the liquid. Departures from linearity of plots of P against DeltaT are attributed to temperature jumps at the surface of the dry upper plate. Hence jump coefficients and thermal accommodation coefficients have been derived as a function of temperature for collisions of water molecules with type-304 stainless steel.     

Molecular dynamics simulations of atmospheric oxidants at the air-water interface: solvation and accommodation of OH and O3

A comparative study of OH, O3, and H2O equilibrium aqueous solvation and gas-phase accommodation on liquid water at 300 K is performed using a combination of ab initio calculations and molecular dynamics simulations. Polarizable force fields are developed for the interaction potential of OH and O3 with water. The free energy profiles for transfer of OH and O3 from the gas phase to the bulk liquid exhibit a pronounced minimum at the surface, but no barrier to solvation in the bulk liquid. The calculated surface excess of each oxidant is comparable to calculated and experimental values for short chain, aliphatic alcohols. Driving forces for the surface activity are discussed in terms of the radial distribution functions and dipole orientation distributions for each molecule in the bulk liquid and at the surface. Simulations of OH, O3, and H2O impinging on liquid water with a thermal impact velocity are used to calculate thermal accommodation (S) and mass accommodation (alpha) coefficients. The values of S for OH, O3, and H2O are 0.95, 0.90, and 0.99, respectively. The approaching molecules are accelerated toward the liquid surface when they are approximately 5 angstroms above it. The molecules that reach thermal equilibrium with the surface do so within 2 ps of striking the surface, while those that do not scatter into the gas phase with excess translational kinetic energy in the direction perpendicular to the surface. The time constants for absorption and desorption range from approximately 35 to 140 ps, and the values of alpha for OH, O3, and H2O are 0.83, 0.047, and 0.99, respectively. The results are consistent with previous formulations of gas-phase accommodation from simulations, in which the process occurs by rapid thermal and structural equilibration followed by diffusion on the free energy profile. The implications of these results with respect to atmospheric chemistry are discussed.     

Thermal waves scattering by a subsurface sphere in a semi-infinite exponentially graded material using non-Fourier's model

In this study, the multiple scattering of thermal waves and temperature distribution resulting from a subsurface sphere in a semi-infinite exponentially graded material are investigated, and the analytical expression of the temperature at the surface of the graded material is obtained. Non-Fourier heat conduction equation is applied to solve the temperature at the surface, and the image method is used to satisfy the semi-infinite boundary condition of graded material. The thermal wave fields are expressed using wave function expansion method, and the expanded mode coefficients are determined by satisfying the boundary condition of the sphere. According to the wave equation of heat conduction, a general solution of scattered thermal waves is presented for the first time. The temperature distribution and phase difference at the surface of the semi-infinite material with different parameters are graphically presented. Analyses show that the hyperbolic heat conduction equation cannot be regarded as a continuation of the parabolic heat conduction equation at very short time scale. The effects of the incident wave number, the structural and physical parameters on the distribution of temperature and phase difference in the semi-infinite material are also examined.     

温度和压力对六氟二酐型聚酰亚胺的透气性能的影响

本文研究了温度和压力对五种六氟二酐（６ＦＤＡ）型聚酰亚胺膜对Ｈ_２、ＣＯ_２、Ｏ_２、Ｎ_２和ＣＨ_４五种气体透过性能的影响．在３０－１００℃区间，五种聚酰亚胺的透气系数与温度的关系均符合Ａｒｒｈｅｎｉｕｓ关系式；在０．３－１．２ＭＰａ区间，压力对透气系数的影响很小．６ＦＤＡ－４，４＇－二氨基二苯酮（ＤＡＢＰ）和６ＦＤＡ－３，３＇－二甲基二苯甲烷二胺（ＤＭＭＤＡ）在１００℃仍然具有较大的透气选择系数，是比较好的气体分离膜材料．     

Thermal diffusion behavior of nonionic surfactants in water

We studied the thermal diffusion behavior of hexaethylene glycol monododecyl ether (C12E6) in water by means of thermal diffusion forced Rayleigh scattering (TDFRS) and determined Soret coefficients, thermal diffusion coefficients, and diffusion constants at different temperatures and concentrations. At low surfactant concentrations, the measured Soret coefficient is positive, which implies that surfactant micelles move toward the cold region in a temperature gradient. For C12E6/water at a high surfactant concentration of w1 = 90 wt % and a temperature of T = 25 degrees C, however, a negative Soret coefficient S(T) was observed. Because the concentration part of the TDFRS diffraction signal for binary systems is expected to consist of a single mode, we were surprised to find a second, slow mode for C12E6/water system in a certain temperature and concentration range. To clarify the origin of this second mode, we investigated also, tetraethylene glycol monohexyl ether (C6E4), tetraethylene glycol monooctyl ether (C8E4), pentaethylene glycol monododecyl ether (C12E5), and octaethylene glycol monohexadecyl ether (C16E8) and compared the results with the previous results for octaethylene glycol monodecyl ether (C10E8). Except for C6E4 and C10E8, a second slow mode was observed in all systems usually for state points close to the phase boundary. The diffusion coefficient and Soret coefficient derived from the fast mode can be identified as the typical mutual diffusion and Soret coefficients of the micellar solutions and compare well with the independently determined diffusion coefficients in a dynamic light scattering experiment. Experiments with added salt show that the slow mode is suppressed by the addition of w(NaCl) = 0.02 mol/L sodium chloride. This suggests that the slow mode is related to the small amount of absorbing ionic dye, less than 10(-5) by weight, which is added in TDFRS experiments to create a temperature grating. The origin of the slow mode of the TDFRS signal will be tentatively interpreted in terms of a ternary mixture of neutral micelles, dye-charged micelles, and water.     

Historical review on research of kinetics in thermal analysis and thermal endurance of electrical insulating materials

Thermal analysis techniques, such as thermogravimetry, differential thermal analysis and evolved gas analysis, have been applied to thermal endurance evaluation of electrical insulating materials of high polymers, which are used for a long time at a relatively high operating temperature. Various attempts have been made to estimate the life time of the materials at the operating temperature by thermal analysis and a calorimetric method. These are critically described in this review paper.     

Thermal transport coefficients for liquid and glassy water computed from a harmonic aqueous glass

We compute thermal transport coefficients for liquid and glassy water in terms of the vibrations of the quenched liquid. The thermal conductivity and thermal diffusivity are computed for H(2)O and D(2)O at densities from 0.93 to 1.2 g cm(-3). The computed thermal diffusivity of liquid water is in reasonable agreement with measured values and is found to increase with increasing temperature due largely to the thermal accessibility of delocalized librational modes. The influence of structure and density on the thermal conductivity of amorphous ices is investigated. The calculations reveal that density alone is unable to explain the measured thermal conductivity of amorphous ices, particularly low-density amorphous ices, for which the thermal conductivity decreases with increasing temperature near 100 K. To investigate the influence of structure on thermal transport in amorphous ices we have computed the thermal transport coefficients for low-density amorphous ices prepared in two different ways, one formed by quenching the liquid at 0.93 g cm(-3) and the other by distortion of cubic ice at the same density. The computed thermal conductivity of the latter is higher, but the structures of both forms are too disordered for the thermal conductivity to exhibit the unusual variation observed experimentally.     

Heterogeneous uptake of 8-2 fluorotelomer alcohol on liquid water and 1-octanol droplets

The heterogeneous uptake of the 8-2 fluorotelomer alcohol, F(CF2)8CH2CH2OH, on liquid water surfaces over the temperature range 256-273 K and on 1-octanol surfaces over the temperature range 264-295 K has been investigated with a droplet train flow reactor. The uptake coefficient on water droplets is zero within the error of the measurement (+/-0.01) and is independent of droplet temperature. In contrast, significant uptake onto 1-octanol is observed. Measured uptake coefficients for 1-octanol showed a negative temperature dependence, varying from 0.034 +/- 0.005 (1sigma) at 295 K to 0.103 +/- 0.009 at 264 K. The measured uptake coefficients on 1-octanol were independent of gas-liquid contact time, for typical contact times varying between 3 and 15 ms, and independent of the 8-2 fluorotelomer alcohol gas-phase concentration, indicating that the uptake coefficients are equivalent to mass accommodation coefficients. The uptake coefficients on 1-octanol were also independent of relative humidity. These results show that the uptake of FTOHs on or into the aqueous component of cloud/fog droplets or aqueous aerosol particles is not likely to be an important atmospheric sink for these compounds. In these experiments, 1-octanol was used as a model compound for organic-containing atmospheric particles. The larger uptake coefficient measured for 1-octanol surfaces indicates that FTOH partitioning to organic-containing cloud/fog droplets and aerosol particles may be an atmospheric loss mechanism.     

Transport Coefficients Of Ar—Kr Mixtures by Molecular Dynamics Computer Simulation

Abstract

Equilibrium molecular dynamics computer simulations have been used to determine the transport coefficients of model Ar—Kr mixtures, which are represented by Lennard-Jones pair potentials with Lorentz—Berthelot rules for the cross-species interactions. The component self-diffusion and mutual-diffusion coefficients are calculated from time correlation functions and mean square displacements. Time correlation functions are used to evaluate the shear and bulk viscosity, thermal conductivity and the thermal diffusion coefficient (Soret/Dufour coefficient). In the case of the thermal transport coefficients, the partial enthalpy of the two species is required at each state point to define the heat flux rigorously. We obtain this and the partial volume (and species resolved chemical potential) using particle-exchange (and particle insertion) techniques implemented in separate [NPT] simulations at the same state point.

The viscoelasticity of the fluids is characterised by the relaxation times for bulk and shear stress relaxation. The results are for dense liquids close to the triple point temperature and density. Agreement with experiment and previous simulation is particularly good for the density of the mixtures, the shear modulus, shear viscosity, shear stress relaxation time and thermal conductivity. As for the single component noble gas fluids (simulated and experiment) there is a significant qualitative difference in the temperature and, for mixtures, composition dependence of the bulk viscosity.     

醇类的缔合作用与热压力系数

测定了甲醇、正丙醇、正丁醇和正癸醇在25-85℃温度范围的热压力系数, 并为正构醇液体建立了一个热压力系数与密度间的通式。这个通式可用来预测正构醇在各种温度下的内压值。用同形物近似法, 本文还获得了正构醇缔合作用的若干重要信息和估计其缔合度的近似方法。     

New Insights into the Thermal Expansion of Neptunium Dioxide up to 2000 K

We report for the first time the thermal expansion of NpO2 up to 2000 K and compare it to the one of UO2 and PuO2. Lattice parameters were measured as a function of temperature by in situ X-ray diffraction with neutral, reducing and oxidizing atmospheres. Data for NpO2 under neutral and reducing conditions perfectly superpose. Up to 1550 K, thermal expansion varies linearly with increasing temperature. Above, thermal expansion presents a curvature towards higher lattice parameters. No bibliographic data were available for this temperature range for comparison. As for the thermal expansion of UO2, we propose this curvature is certainly inferred by the formation of lattice defects in the oxygen sub-lattice. Expression of thermal expansion and coefficients of thermal expansion at given temperatures for NpO2, are presented.     

Heat flow in proteins: computation of thermal transport coefficients

The rate of vibrational energy transfer and thermal transport coefficients are computed for two structurally distinct proteins, green fluorescent protein (GFP) and myoglobin. The computation of thermal transport coefficients exploits the scaling of the energy diffusion coefficient with the vibrational mode frequency of a protein. Near 300 K we find that vibrational energy transfer due to anharmonicity contributes substantially to thermal transport because of the localization of many thermally accessible normal modes. The thermal diffusivity for the beta-barrel GFP is larger than that for myoglobin, particularly at low temperature due to a mean free path for vibrational energy propagation that is twice as large at low frequency. Vibrational energy transfer is also faster in GFP than in myoglobin for most vibrational modes.     

Scattering, accommodation, and trapping of HCl in collisions with a hydroxylated self-assembled monolayer

Time-of-flight molecular beam scattering techniques are used to explore the energy exchange, thermal accommodation, and residence time of HCl in collisions with an OH-terminated self-assembled monolayer. The monolayer, consisting of 16-mercapto-1-hexadecanol (HS(CH(2))(16)OH) self-assembled on gold, provides a well-characterized surface containing hydroxyl groups located at the gas-solid interface. Upon colliding with the hydroxylated surface, the gas-phase HCl is found to follow one of three pathways: direct impulsive scattering, thermal accommodation followed by prompt desorption, and temporary trapping through HO--- HCl hydrogen bond formation. For an incident energy of 85 kJ/mol, the HCl transfers the majority, >80%, of its translational energy to the surface. The extensive energy exchange facilitates thermalization, leading to very large accommodation probabilities on the surface. Under the experimental conditions used in this work, over 75% of the HCl approaches thermal equilibrium with the surface before desorption and, for a 6 kJ/mol HCl beam, nearly 100% of the molecules that recoil from the surface can be described by a thermal distribution at the temperature of the surface. For the molecules that reach thermal equilibrium with the surface prior to desorption, a significant fraction appear to form hydrogen bonds with surface hydroxyl groups. The adsorption energy, determined by measuring the HCl residence time as a function of surface temperature, is 24 +/- 2 kJ/mol.     

On thermal gas slip

The distribution function of the gas molecule velocities has been determined in Couette's problem in an approximation of three velocity polynomials by the half-range expansion method. Using this function, we have calculated the isothermal heat flux in the Knudsen layer. The coefficient of the thermal gas slip was determined by means of Onsager's symmetry relations of nonequilibrium thermodynamics, the accommodation coefficient of the tangential pulse of molecules being arbitrary. The formula thus obtained coincides with the formula derived by direct method and with the experimental results obtained by Rabinovich and Derjaguin (within the limits of accuracy of the measurements).     

Measurement of the Soret and diffusion coefficients for benchmark binary mixtures by means of digital interferometry

We report on the development of the optical digital interferometry (ODI) technique for measuring diffusion and Soret coefficients. The unique feature of this method is that it traces the transient path of the system in the entire two-dimensional cross section of a cell. In this way, it is applicable not only for measurements of Soret coefficients, but also for studying diffusive transport mechanism and convection. Presently, this method is not widely used and, in our view, not because of fundamental limitations but rather due to a lack of properly developed postexperimental procedures of the raw data analysis. Thus, in this paper our attention is focused on the successive analysis of different steps: the fringe analysis, the choice of reference images, the thermal design of the cell, and multiparameter fitting procedure. Using the ODI technique, we have measured the diffusion and the Soret coefficients for three binary mixtures composed of dodecane (C(12)H(26)), isobutylbenzene, and 1,2,3,4-tetrahydronaphtalene at a mean temperature of 25(°)C and 50 wt. % in each component. These measurements were compared with their benchmark values and show an agreement within less than 3%.     

便携式气相色谱–质谱法现场测定有组织排放废气中VOCs

建立便携式气相色谱-质谱仪现场测定有组织排放废气中VOCs的方法。针对固定污染源有组织废气排放的特点,对升温程序、扫描方式、采样方式、进样体积进行了讨论优化,提出了对高、低浓度废气样品测定的解决方案,分析了气袋本底的干扰和去除方式。用所建方法对TO-14标准气体进行测定,各组分的含量在0.02~1.00μL/L范围内线性关系良好,相关系数均大于0.990,各组分检出限为0.004~0.014μL/L。测定结果的相对标准偏差为2.4%~15.3%(n=6),加标回收率为73.3%~109%。该方法检测时间短,具有良好的精密度和准确度,适用于有组织排放废气中VOCs测定。     

Molecular dynamics studies to understand the mechanism of heat accommodation in homogeneous condensing flow of carbon dioxide

Using molecular dynamics (MD), we have studied the mechanism of heat accommodation between carbon dioxide clusters and monomers for temperatures and cluster size conditions that exist in homogeneous condensing supersonic expansion plumes. The work was motivated by our meso-scale direct simulation Monte Carlo and Bhatnagar-Gross-Krook based condensation simulations where we found that the heat accommodation model plays a key role in the near-field of the nozzle expansion particularly as the degree of condensation increases [R. Kumar, Z. Li, and D. Levin, Phys. Fluids 23, 052001 (2011)]. The heat released by nucleation and condensation and the heat removed by cluster evaporation can be transferred or removed from either the kinetic or translational modes of the carbon dioxide monomers. The molecular dynamics results show that the time required for gas-cluster interactions to establish an equilibrium from an initial state of non-equilibrium is less than the time step used in meso-scale analyses [R. Kumar, Z. Li, and D. Levin, Phys. Fluids 23, 052001 (2011)]. Therefore, the good agreement obtained between the measured cluster and gas number density and gas temperature profiles with the meso-scale modeling using the second energy exchange mechanism is not fortuitous but is physically based. Our MD simulations also showed that a dynamic equilibrium is established by the gas-cluster interactions in which condensation and evaporation processes take place constantly to and from a cluster.