Thermogravimetric measurements of liquid vapor pressure

A method was developed using thermo-gravimetric analysis (TGA) to determine the vapor pressure of volatile liquids. This is achieved by measuring the rate of evaporation (mass loss) of a pure liquid contained within a cylindrical pan. The influence of factors like sample geometry and vapor diffusion on evaporation rate are discussed. The measurement can be performed across a wide range of temperature yielding reasonable results up to 10 kPa. This approach may be useful as a rapid and automatable method for measuring the volatility of flavor and fragrance raw materials.     

相变储能化合物CH_3COONa·3H_2O的热分解行为

通过对CH3COONa·3H2O进行热重(TG)及差示扫描量热法(DSC)测试,分析了其热分解行为,并从热力学的角度对其脱水过程进行了讨论。结果表明,CH3COONa·3H2O的脱水过程可分为两个阶段,先失液态水形成CH3COONa溶液,再从溶液中脱出气态水,并且在加热过程中一直伴随着结晶水的蒸发逸出。用硅油覆盖的方法能很好地抑制低温时由于蒸汽压差异引起的CH3COONa·3H2O结晶水的不断蒸发逸出问题。     

CRTA for the thermoanalytical screening of volatile compounds

Quasi-equilibrium thermogravimetry (variant of CRTA) is utilized as a thermoanalytical screening method for volatile compounds, standard Q-derivatograph sample holders (platelike holder, open crucible, crucible with lid, and conical holder) were calibrated against the partial pressures of metal β-diketonate vapor (in sublimation and evaporation processes) in the range 0.0006–0.11 atm. The mathematical relationship between the vapor partial pressure, the holder construction, the vapor molecular mass, and the mutual diffusion coefficient of the gas was derived and considered. It is possible to obtain a roughp-T relationship for volatile compounds by using stabilized temperatures of sublimation (evaporation) processes in four pressure-calibrated sample holders.     

Raman thermometry measurements of free evaporation from liquid water droplets

Recent theoretical and experimental studies of evaporation have suggested that on average, molecules in the higher-energy tail of the Boltzmann distribution are more readily transferred into the vapor during evaporation. To test these conclusions, the evaporative cooling rates of a droplet train of liquid water injected into vacuum have been studied via Raman thermometry. The resulting cooling rates are fit to an evaporative cooling model based on Knudsen's maximum rate of evaporation, in which we explicitly account for surface cooling. We have determined that the value of the evaporation coefficient (gamma(e)) of liquid water is 0.62 +/- 0.09, confirming that a rate-limiting barrier impedes the evaporation rate. Such insight will facilitate the formulation of a microscopic mechanism for the evaporation of liquid water.     

相变储能化合物CH3COONa·3H2O的热分解行为

通过对CH₃COONa·3H₂O进行热重(TG)及差示扫描量热法(DSC)测试,分析了其热分解行为,并从热力学的角度对其脱水过程进行了讨论。结果表明,CH₃COONa·3H₂O的脱水过程可分为两个阶段,先失液态水形成CH₃COONa溶液,再从溶液中脱出气态水,并且在加热过程中一直伴随着结晶水的蒸发逸出。用硅油覆盖的方法能很好地抑制低温时由于蒸汽压差异引起的CH₃COONa·3H₂O结晶水的不断蒸发逸出问题。     

Solvent Trapping during Large Volume Injection with an Early Vapor Exit. Part 3: The Main Cause of Volatile Component Loss during Partially Concurrent Evaporation

When 0.53 mm i.d. uncoated precolumns connected to a solvent vapor exit are used for sample introduction with partially concurrent solvent evaporation, substantial losses of volatile solutes are often observed. They were found to be the consequence of solute accumulation at the front end of the flooded zone, which in turn is the result of a strong pressure drop over the flooded zone owing to the formation of plugs of sample liquid. The pressure drop causes significant solvent evaporation at the front, which enriches the solute material there and causes its loss. The use of 0.32 mm i.d. restrictions between the uncoated precolumn and the vapor exit greatly reduced this problem.     

Thermal stability enhancement of polyurethanes by surface treatment

Both oxidation and methoxymethylation of the surfaces of a series of MDI (methylene diphenyl isocyanate) and TDI (toluene diisocyanate) polyether and polyester soft segment 1–4 butanediol polyurethanes result in increased thermal stability as measured by TG. Explosive loss of mass above the hard segment melting temperature suggests that the diffusion of the dissociated diisocyanate moiety is hindered at lower temperatures. Thus suppression of the depolycondensation reaction by chemical blockage of the surface may result in a material with an increased service life at use temperatures as thermal stability of a polyurethane may depend upon the low diffusivity of its diisocyanate comonomer. The effect of vacuum, oxygen and water vapor on the kinetics of mass-loss of several of the polyurethanes is presented. In celebration of the 60^th birthday of Dr. Andrew K. Galwey     

Effects of the polarizability and packing density of transparent oxide films on water vapor permeation

The tin oxide and silicon oxide films have been deposited on polycarbonate substrates as gas barrier films, using a thermal evaporation and ion beam assisted deposition process. The oxide films deposited by ion beam assisted deposition show a much lower water vapor transmission rate than those by thermal evaporation. The tin oxide films show a similar water vapor transmission rate to the silicon oxide films in thermal evaporation but a lower water vapor transmission rate in IBAD. These results are related to the fact that the permeation of water vapor with a large dipole moment is affected by the chemistry of oxides and the packing density of the oxide films. The permeation mechanism of water vapor through the oxide films is discussed in terms of the chemical interaction with water vapor and the microstructure of the oxide films. The chemical interaction of water vapor with oxide films has been investigated by the refractive index from ellipsometry and the OH group peak from X-ray photoelectron spectroscopy, and the microstructure of the composite oxide films was characterized using atomic force microscopy and a transmission electron microscope. The activation energy for water vapor permeation through the oxide films has also been measured in relation to the permeation mechanism of water vapor. The diffusivity of water vapor for the tin oxide films has been calculated from the time lag plot, and its implications are discussed.     

Thermal Efficiency of Solar Steam Generation Approaching 100 % through Capillary Water Transport

Solar‐driven interfacial water evaporation yield is severely limited by the low efficiency of solar thermal energy. Herein, the injection control technique (ICT) achieves a capillary water state in rGO foam and effectively adjusts the water motion mode therein. Forming an appropriate amount of capillary water in the 3D graphene foam can greatly increase the vapor escape channel, by ensuring that the micrometer‐sized pore channels do not become completely blocked by water and by exposing as much evaporation area as possible while preventing solar heat from being used to heat excess water. The rate of solar steam generation can reach up to 2.40 kg m^?2 h^?1 under solar illumination of 1 kW m^?2, among the best values reported. In addition, solar thermal efficiency approaching 100 % is achieved. This work enhances solar water‐evaporation performance and promotes the application of solar‐driven evaporation systems made of carbon‐based materials.     

Assessment of systematic errors in measurement of vapor pressures by thermogravimetric analysis

The present study explores the application of the diffusion limited evaporation theory to the estimation of vapor pressure from TG experimental data. A simplified method was developed to calculate the apparent values of the vapor pressure of pure substances from TG data, based on isothermal TG runs with crucibles having different surface areas available for evaporation. Antoine parameters are estimated through a numerical procedure based on a non-linear least square algorithm. The procedure also evaluates the substance diffusivity in nitrogen. The methodology developed might be used for a preliminary screening of the vapor pressure of pure compounds, due to the limited amounts of sample that are necessary and to the limited time frame required for the experimental runs. However, the estimation of diffusivity and vapor pressures values by the TG technique is possible with limited accuracy. Possible sources of error were thoroughly investigated and discussed.     

Thermogravimetric studies on the reduction of hematite ore fines by a surrounding layer of coal or char fines: Part 2. Non-isothermal kinetic studies

A kinetic study on the non-isothermal reduction of a column of iron ore fines by a surrounding layer of char fines is the main theme of this paper. A study on isothermal reduction by coal/char fines was described in Part 1 of this communication.In the present work the degree of reaction at a given instant has been described as in Part 1, i.e., as the ratio of weight loss at that instant to the maximum possible weight loss. Reduction experiments have been carried out on three different sample sizes. Samples of ~1 g were used in a thermogravimetric set-up and continuous measurements of weight loss analysed in terms of the degree of reaction. Some fixed time reduction experiments have been carried out on large (~15 g) samples where the reduced sample was chemically analysed for the degree of reduction. In addition, a thermal analyser was used to study reduction in a thoroughly mixed ore-char system (sample size, ~30 mg).It is shown that while the reaction in a mixed system is characterized by uniform internal reduction, reduction in an unmixed system is characterized by diffusion of gases through a porous product layer, the reaction being controlled by gasification of carbon.     

Evaporation of Lennard-Jones fluids

Evaporation and condensation at a liquid/vapor interface are ubiquitous interphase mass and energy transfer phenomena that are still not well understood. We have carried out large scale molecular dynamics simulations of Lennard-Jones (LJ) fluids composed of monomers, dimers, or trimers to investigate these processes with molecular detail. For LJ monomers in contact with a vacuum, the evaporation rate is found to be very high with significant evaporative cooling and an accompanying density gradient in the liquid domain near the liquid/vapor interface. Increasing the chain length to just dimers significantly reduces the evaporation rate. We confirm that mechanical equilibrium plays a key role in determining the evaporation rate and the density and temperature profiles across the liquid/vapor interface. The velocity distributions of evaporated molecules and the evaporation and condensation coefficients are measured and compared to the predictions of an existing model based on kinetic theory of gases. Our results indicate that for both monatomic and polyatomic molecules, the evaporation and condensation coefficients are equal when systems are not far from equilibrium and smaller than one, and decrease with increasing temperature. For the same reduced temperature T/T(c), where T(c) is the critical temperature, these two coefficients are higher for LJ dimers and trimers than for monomers, in contrast to the traditional viewpoint that they are close to unity for monatomic molecules and decrease for polyatomic molecules. Furthermore, data for the two coefficients collapse onto a master curve when plotted against a translational length ratio between the liquid and vapor phase.     

Untersuchungen zur thermischen Zersetzung von Boraten

In spite of numerous investigations the literature data on the thermal decomposition of borax are contradictory. On the basis of thermal, X-ray, gas analytical and optical investigations this fact can be attributed to the complex decomposition mechanism. After the release of about 8 mole water the reaction product is an X-ray amorphous phase, having the thermal behaviour of glass. From this glass sodium diborate (Na₂O.2B₂O₃) crystallizes between 500–600? with further mass loss. Sodium diborate decomposes from about 700? incongruently yielding NaBO₂ vapor and B₂O₃ glass phase. After evaporation of NaBO₂ is completed the rate of evaporation of B₂O₃ increases considerably.     

Experimental studies of the vapor phase nucleation of refractory compounds. VI. The condensation of sodium

In this paper we discuss the condensation of sodium vapor and the formation of a sodium aerosol as it occurs in a gas evaporation condensation chamber. A one-dimensional model describing the vapor transport to the vapor/aerosol interface was employed to determine the onset supersaturation, in which we assume the observed location of the interface is coincident with a nucleation rate maximum. We then present and discuss the resulting nucleation onset supersaturation data within the context of nucleation theory based on the liquid droplet model. Nucleation results appear to be consistent with a cesium vapor-to-liquid nucleation study performed in a thermal diffusion cloud chamber.     

Water diffusion through hydrogel membranes: A novel evaporation cell free of external mass-transfer resistance

A novel evaporative cell is used to measure steady-state gradient-driven diffusion rates of water through hydrogel membranes in the absence of external mass-transfer resistance. In this cell, the bottom surface of a hydrogel membrane is exposed to pure water vapor at known activity (a_w) less than unity, while a sealed liquid-water reservoir bathes the upper membrane surface. Induced by the chemical-potential gradient between the two surfaces, the water evaporation rate is monitored by the rate of weight loss of the water reservoir.Results at ambient temperature are compared with those from measured water flux through soft-contact-lens (SCL) materials and with other published experimental results. Concentration-dependent water diffusivities are obtained by interpreting measured water fluxes for 0.11 ≤ a_w ≤ 0.93 with extended Maxwell–Stefan (EMS) diffusion theory. Thermodynamic non-ideality is taken into account through Flory–Rehner polymer–solution theory. Shrinking/swelling is modeled by conservation of the total polymer mass assuming volume additivity. In spite of correction for thermodynamic non-ideality, EMS–water-diffusion coefficients increase with the water volume fraction, especially strongly for those hydrogel materials with low liquid-saturated water contents. The evaporation cell described here provides a simple robust method to establish water transport rates through soft-contact-lenses and other hydrogel membranes without the need to correct for external mass-transfer resistance.     

Change of thermal drying characteristics for dewatered sewage sludge based on anaerobic digestion

The moisture distribution and thermal drying characteristics of dewatered sludge in anaerobic digestion were investigated by a thermo-gravimetric analyzer (TG) and the isothermal kinetic characteristics during the drying were developed by an unreacted core model. The TG results showed that the bound water was partly converted to the free water with the invariant interstitial water and surface water after anaerobic digestion, which enhanced the drying performance of sludge. The time required for the complete drying of digestate was less than that of the raw sludge in the same temperature. The moisture evaporative efficiency of digestate was related to the vapor diffusion rate of the outer surface, and the drying efficiency of digested sludge cannot be enhanced by increased temperatures.     

ChemInform Abstract: A Matrix Isolation and Computational Study of Molecular Palladium Fluorides: Does PdF6 Exist?

Binary palladium fluorides from PdF to PdF₆ are investigated by matrix‐isolation methods using thermal evaporation and laser ablation to generate Pd atoms for reaction with F₂‐doped Ar and Ne matrices as well as neat F₂ matrices.     

Characterization and field emission properties of ZnMgO nanowires fabricated by thermal evaporation process

In this paper, we investigate the roles of gold catalyst using modified thermal evaporation set-up in the growth process of ZnMgO nanowires. ZnMgO nanowires are fabricated on silicon substrates using different thickness of gold catalyst. A simple horizontal double-tube system along with chemical vapor diffusion of the precursors, based on Fick’s first law, is used to grow the ZnMgO nanowires. Field emission scanning electron microscopy images show that the ZnMgO nanowires are tapered. The optical properties of the ZnMgO nanowires are characterized by room temperature photoluminescence (PL) measurements. The PL studies demonstrate that the ZnMgO nanowires grown using this method have good crystallinity with excellent optical properties and have a larger band-gap in comparison to the pure ZnO nanowires. Field emission characterization shows that the turn-on field for the nanowires grown on the thinner gold film is lower than those grown on the thicker gold film.     

A special reactor coupled with a high‐temperature mass spectrometer for the investigation of the vaporization and cracking of organometallic compounds

A special reactor coupled to a high‐temperature mass spectrometer was specifically designed for the study of vaporization and thermal cracking of organometallic precursors. This reactor has two kinds of settings. One is a single Knudsen effusion cell which enables the analysis of the composition of saturated vapors and the determination of the partial pressure of each gaseous molecule in equilibrium with its condensed phase. This cell is an evaporation/sublimation cell (operating from 243 to 473 K), which can be tightly closed – like a vacuum chamber – in order to protect organometallic compounds against moisture and atmospheric components. This cell can be independently weighed usefully to evaluate the equilibrium vapor pressures of the sample using the mass‐loss method. During experiments, the effusion aperture is externally opened for direct mass spectrometric measurements. The other setting dedicated to the study of thermal decomposition of gaseous molecules consists of a set of tandem cells: the previously described Knudsen cell and a cracking cell (operating from 293 to 973 K). Copyright © 2009 John Wiley & Sons, Ltd.     

A Study of Evaporation of Complex Oxide Systems Based on Chromium(III) Oxide

Evaporation of chromium ore and concentrates was studied using high-temperature differential mass-spectrometry. The data obtained, concerning the component vapor pressures in evaporation of complex oxide systems in the range 1700-2100 K, can be used to calculate the evaporation loss in melting and to assess the possibility of utilization of the sublimates formed.