A simultaneous correlation of vapour pressures and thermal data: application to 1-alkanols

R∪žička, K. and Majer, V., 1986. A simultaneous correlation of vapour pressures and thermal data: application to 1-alkanols. Fluid Phase Equilibria, 28: 253-264Possibilities of simultaneous correlation of vapour pressures and thermal data (enthalpy of vaporization and difference between heat capacity of idea gas and liquid) are investigated. This approach permits a reliable evaluation of vapour pressures and/or enthalpies of vaporization far below the normal boiling point and can serve also as a consistency test of experimental data. A simple procedure using smoothed input data is proposed which can be implemented in a software of the data bank of thermodynamic properties. The method is demonstrated on a group of eight 1-alkanols.     

Determining the vapour pressures of plant volatiles from gas chromatographic retention data

The frequently used vapour pressure versus Kováts retention index relationship has been evaluated in terms of its universal applicability, highlighting the problems associated with predicting the vapour pressures of structurally divergent organic compounds from experimentally measured isothermal Kováts retention indices. Two models differing in approximations adopted to express the activity coefficient ratio have been evaluated using 32 plant volatiles of different structural types as a test set. The validity of these models was established by checking their ability to reproduce 22 vapour pressures known from independent measurements. Results of the comparison demonstrated that (i) the original model, based on the assumption of equal activity coefficients for the test and reference substances, led, as expected, to a poor correlation (r2 = 89.1% only), with significantly deviating polar compounds and (ii) the model showed significant improvement after incorporating a new empirical term related to vaporization entropy and boiling point. The addition of this term allowed more than 99% of the vapour pressure variance to be accounted for. The proposed model compares favourably with existing correlations, while having an added advantage of providing a convenient tool for vapour pressure determination of chemically divergent chemicals.     

Measurement of enthalpies of vaporization of volatile heterocyclic compounds by DSC

An experimental procedure is proposed for direct measurement of the heat involved in the vaporization of volatile heterocyclic compounds. This technique consists on the vaporization of the liquid substance by a sudden decrease of the pressure then, the direct register of heat flow as function of time by differential scanning calorimetry. This procedure allows quantifying the enthalpy of vaporization of compounds such as tetrahydropyran, 2-methoxy-tetrahydropyran, N-morpholine and N-methyl-morpholine. Enthalpies of vaporization were measured in isothermal mode at T=298.15 K and then compared with results from the literature, which currently are obtained by vapour pressure measurements.     

Physical properties of hexafluoroacetone

The vapour pressure of hexafluoroacetone has been determined from 58°C to the critical point. The critical temperature and pressure were also measured. Densities of the liquid and saturated vapour were determined between - 50°C and the critical point. Using this information the rectilinear diameter line and the heats of vaporization have been determined.     

Thermal analysis study on vaporization of some analgesics. Acetanilide and derivatives

The thermal behaviour of acetanilide (Ac) and two of its analogues, namely the para-ethoxyacetanilide (p-Eto Ac) and the para-bromoacetanilide (p-Br Ac), which are used as analgesics in the pharmaceutical industry was studied with a simultaneous TG/DSC unit. The examined analgesics showed two endothermic DSC peaks due to melting and vaporization. By combining the experimental TG data with the corresponding reference vapour pressure data obtained with the Antoine equation the plot of P versus v was derived. From the slope of this equation the constant k-value was determined for Ac. Then, using the same k-value the vapour pressures of p-Eto Ac and p-Br Ac were determined in the same temperature range. The vaporization enthalpies for all the studied compounds were obtained from different methods and a very good agreement was found. Vaporization follows a zero-order kinetics. The activation energy of vaporization (E_vap) was calculated from the dynamic TG experiments, using the Arrhenius equation.     

Universal behavior of the enthalpy of vaporization: an empirical equation

Values of the enthalpy of vaporization from the critical to the triple point are correlated by an empirical equation. The equation contains parameters which characterize each substance: the critical and triple point temperatures and the enthalpy of vaporization at the triple point, and for all substances the same universal critical ratio. This work suggests that a wide class of fluids with the exception of quantal liquids shows an universal behavior along the coexistence curve.     

Vapour pressures and heat capacity measurements on the C7–C9 secondary aliphatic alcohols

Molar enthalpies of vaporization of secondary C₇–C₉ alkanols were obtained from the temperature dependence of the vapour pressure measured by the transpiration method. The measured data sets were checked for internal consistency successfully. A large number of the primary experimental results on temperature dependences of vapour pressures of secondary alcohols have been collected from the literature and have been treated uniform in order to derive their vaporization enthalpies at the reference temperature 298.15 K. This collection, together with our experimental results, have helped to ascertain the database for branched aliphatic alcohols.     

General correlation model for some physical properties of saturated pure fluids

In this work, we use a general expression to accurately correlate the liquid density, the vaporization enthalpy, the surface tension, and the isobaric heat capacity of a saturated liquid versus temperature along the whole coexistence curve. The general expression used is the same for the four thermodynamic properties, and uses both critical and triple point values as reference. As representative examples of the use of the model, results are given for a set of 22 pure substances. We find that this general expression correlates the data with smaller or similar overall deviations when compared with other published models whose number of coefficients are the same or greater.     

The Role of Metal Vapour in Gas Metal Arc Welding and Methods of Combined Experimental and Numerical Process Analysis

Gas metal arc welding (GMAW) processes are characterized by a high number of simultaneously running physical processes. The process capability is mainly determined by the properties of a metal vapour influenced arc and the material transfer. In recent years, experimental as well as numerical methods are being used increasingly in order to understand the complex interactions between the arc and material transfer. In this paper, we discuss the influence of metal vapour on GMAW processes in spray as well as pulsed material transfer mode. With respect to the high complexity of the process, experimental and numerical methods are combined in a targeted manner in order to obtain a high level of expressive capability with moderate numerical and experimental effort. The results illustrate the high influence of the changing vaporization rate not only on the arc properties but on the arc attachment at the filler wire. It could be shown, that in many cases the metal vapour concentration in the arc region has a greater influence on the arc properties and the material transfer than different shielding gas components like oxygen, hydrogen or helium.     

Calculation of the Vapour Pressure of Organic Molecules by Means of a Group-Additivity Method and Their Resultant Gibbs Free Energy and Entropy of Vaporization at 298.15 K

The calculation of the vapour pressure of organic molecules at 298.15 K is presented using a commonly applicable computer algorithm based on the group-additivity method. The basic principle of this method rests on the complete breakdown of the molecules into their constituting atoms, further characterized by their immediate neighbour atoms. The group contributions are calculated by means of a fast Gauss–Seidel fitting algorithm using the experimental data of 2036 molecules from literature. A ten-fold cross-validation procedure has been carried out to test the applicability of this method, which confirmed excellent quality for the prediction of the vapour pressure, expressed in log(pa), with a cross-validated correlation coefficient Q² of 0.9938 and a standard deviation σ of 0.26. Based on these data, the molecules’ standard Gibbs free energy ΔG°_vap has been calculated. Furthermore, using their enthalpies of vaporization, predicted by an analogous group-additivity approach published earlier, the standard entropy of vaporization ΔS°_vap has been determined and compared with experimental data of 1129 molecules, exhibiting excellent conformance with a correlation coefficient R² of 0.9598, a standard error σ of 8.14 J/mol/K and a medium absolute deviation of 4.68%.     

Vapour pressure and enthalpy of vaporization of aliphatic poly-amines

Molar enthalpies of vaporization of aliphatic poly-amines: 1,4-dimethylpiperazine [106-58-1], 1-(2-aminoethyl)-piperazine, [140-31-8], 1-(2-aminoethyl)-4-methyl-piperazine [934-98-5], and triethylenetetramine [112-24-3] were obtained from the temperature dependence of the vapour pressure measured by the transpiration method. A large number of the primary experimental results on temperature dependences of vapour pressures of the parent compounds have been collected from the literature and have been treated uniformly in order to derive vaporization enthalpies of poly-amines at the reference temperature 298.15 K. An internal consistency check was performed on enthalpy of vaporization values for poly-amines studied in this work.     

Vapour pressure of DSC calibration substances

For a large number of DSC calibration substances the vapour pressure at room temperature or at transition temperature (whichever is the highest) is given. It is important to know the vapour pressure of substances, because a DSC measurement on a substance with a high vapour pressure requires encapsulation of the substance in a hermetically sealed crucible to prevent evaporation. Because the calibration procedure must be performed using the same type of sample pan as will be used during the actual measurements, the presented information allows one to decide which calibration substances and/or what type of sample pan should be used for calibration.This revised version was published online in November 2005 with corrections to the Cover Date.     

Vapour pressure and enthalpy of vaporization of aliphatic dialkyl carbonates

Molar enthalpies of vaporization of aliphatic alkyl carbonates: dimethyl carbonate [616-38-6], diethyl carbonate [105-58-8], di-n-propyl carbonate [623-96-1], di-n-butyl carbonate [542-52-9], and dibenzyl carbonate [3459-92-5] were obtained from the temperature dependence of the vapour pressure measured by the transpiration method. A large number of the primary experimental results on temperature dependences of vapour pressures have been collected from the literature and have been treated uniformly in order to derive vaporization enthalpies of dialkyl carbonates at the reference temperature 298.15 K. An internal consistency check was performed on enthalpy of vaporization values for dialkyl carbonates studied in this work.     

电弧制样-电感耦合等离子体光谱分析法直接测定合金钢中的痕量元素

本文提出了电弧制样与电感耦合等离子体(ICP)相结合光谱直接测定合金钢中痕量元素的新方法。采用高压/低电流直流电弧放电作为试样蒸发的蒸发源,由于阴极弧斑在金属表面上方作快速均匀的移动,使试样剥离形成金属气溶胶,它在载气流(Ar)的作用下引入ICP。研究了试样的蒸发行为、放电气体介质、基体组成变化的影响及ICP工作参数等。用本法测定Co、Ni、Cr、Mn、Mo、Nb、Ta、Ti、V、W和Zr的检出限为0。x至xμg/g。分析了低、高合金钢试样,结果与NBS标准值吻合。     

Analysis of phase change during pervaporation with single component permeation

Individual (single) component pervaporation study helped to address some of the basic curiosities for the process of pervaporation. Investigations were carried out to focus on the location of vaporization during single component pervaporation. A mathematical model was developed for single component permeation during pervaporation, assuming two zones inside the membrane; namely, liquid permeation and vapour permeation zones. Considering a pressure distribution across the thickness of the membrane, Kelvin equation (saturation vapour pressure gets modified inside the membrane due to permeant membrane interactions) proved to be useful in developing the model. According to the model assumptions, the sorbed liquid first transports as liquid; and as soon as it finds the region, where pressure is Kelvin pressure, it evaporates and continues to transport as vapor. Further, the developed model was found to be useful in describing the flux in terms of downstream pressure variations. Accordingly, location of vaporization was determined. It was observed that vapor phase transport dominates in the membrane at low downstream pressures. Importance of consideration for both the phases, during modeling, is discussed. Activity profile, determined across the membrane, was observed to be in agreement with the experimental observations (as per literature). The study may help to establish a fundamental framework in turn to model for binary and/or multi-component mixtures.     

Theoretical analysis of atom formation-time curves for HGA-74

A simplified mathematical analysis of atom formation was developed. For this purpose, the atomization process was considered as first order kinetics. Experimental studies were carried out. From the initial portion of experimental curves the Arrhenius-type rate constants, activation energies and frequency factors for atom formation reactions were calculated. The values obtained for activation energy could be attributed to the heat of vaporization of the test element nickel. The rate constants proportionality factors relating absorbance to the amount of metal vapour in the graphite furnace were found to be considerably dependent upon the temperature.     

An optimized molecular potential for carbon dioxide

An optimized molecular potential model for carbon dioxide is presented in this paper. Utilizing the established techniques of molecular-dynamics and histogram reweighting grand canonical Monte Carlo simulations, this model is demonstrated to show excellent predictability for thermodynamic, transport, and liquid structural properties in a wide temperature-pressure range with remarkable accuracies. The average deviations of this new model from experimental data for the saturated liquid densities, vapor densities, vapor pressures, and heats of vaporization are around 0.1%, 2.3%, 0.7%, and 1.9%, respectively. The calculated critical point is almost pinpointed by the new model. The experimental radial distribution functions ranging from 240.0 to 473.0 K are well reproduced as compared to neutron-diffraction measurements. The predicted self-diffusion coefficients are in good agreement with the nuclear-magnetic-resonance measurements. The previously published potential models for CO2 are also systematically evaluated, and our proposed new model is found to be superior to the previous models in general.     

Solubilities and vapour pressures of saturated aqueous solutions of sodium peroxydisulfate and potassium peroxydisulfate

Solubilities of sodium peroxydisulfate and potassium peroxydisulfate in water and vapour pressures of saturated solutions were determined as a function of temperature. The vapour pressures served to evaluate the water activities, osmotic coefficients and molar enthalpies of vaporization. The molar enthalpy of solution of sodium peroxydisulfate was determined calorimetrically.     

Optimization of the electrothermal vaporization conditions for inductively coupled plasma excitation spectrometry: Selective volatilization versus covolatilization approaches

A new version of the outlet port of a graphite furnace electrothermal vaporizer (upward streaming system) is described, in which the hot sample vapour is mixed with an auxiliary carrier argon stream of ambient temperature. The operation procedures using carrier volatilization of organic liquids as gas phase additives are also outlined. The selective volatilization and transport efficiency for As, Cd, Hg, Pb, Sb, Se and Zn could be increased by applying sodium thiosulfate as chemical modifier to solution samples with controlled nitric acid content. On the other hand, a near simultaneous vaporization of 16 elements using chlorination with CCl(4) vapour at 2100 degrees C could be performed for a multielement analysis. By wetting the auxiliary carrier argon stream, the linearity of the analytical curves was improved (except for chromium), when applying multielement standards. Linear analytical curves could also be obtained in the presence of alkali and alkaline earth metal matrices in multielement standards using halocarbon assisted electrothermal vaporization sample introduction.