Techniques vapor pressure determination

Knudsen effusion technique and equation, vapor pressure determination. 100-101... 

Miscellaneous methods. Some other techniques, such as dielectric constant measurements , conductimetry , mass spectrometry , and electronic spectroscopy are used less frequently but can also be useful. Change in vapor pressure determined with a manometric device can be used when the reaction mixture contains a volatile compound such as ethylene oxide... 

The equilibria between clathrate and gas, and Qa, clathrate, and gas could be determined by using w-propanol as the auxiliary solvent.53 In the latter equilibrium, the composition of the clathrate is found from the amount of gas required for the conversion of a given amount of solid a-hydroquinone suspended in the propanol solution into clathrate at constant temperature and pressure. The dissociation pressure of the clathrate is given by the total pressure of the four-phase equilibrium -clathrate-solution-gas, corrected for the vapor pressure of w-propanol saturated with a-hydroquinone. Using this technique it was found that the equilibrium clathrates of hydroquinone and argon have yA = 0.34 at 25°C63 and 0.28 at 60°C.28... 

Binary (vapor + liquid) equilibria studies involve the determination of / as a function of composition. the mole fraction in the liquid phase. Of special interest is the dependence of/ on composition in the limit of infinite dilution. In the examples which follow, equilibrium vapor pressures, p,. are measured and described. These vapor pressures can be corrected to vapor fugacities using the techniques described in the previous section. As stated earlier, at the low pressures involved in most experiments, the difference between p, and / is very small, and we will ignore it unless a specific application requires a differentiation between the two. 

Vapor pressures of phases in these systems were measured by the Knudsen effusion technique. Use of mass spectrometer-target collection apparatus to perform thermodynamic studies is discussed. The prominent sublimation reactions for these phases below 2000 K was shown to involve formation of elemental plutonium vapor. Thermodynamic properties determined in this study were correlated with corresponding values obtained from theoretical predictions and from previous measurements on analogous intermetallics. 

Vapor pressures were determined by using the Knudsen effusion technique. Effusion rates through and orifice contained in each sample cell were measured as a function of temperature by use of a mass spectrometer/target collection... 

The permeation technique is another commonly employed method for determining the mutual diffusion coefficient of a polymer-penetrant system. This technique involves a diffusion apparatus with the polymer membrane placed between two chambers. At time zero, the reservoir chamber is filled with the penetrant at a constant activity while the receptor chamber is maintained at zero activity. Therefore, the upstream surface of the polymer membrane is maintained at a concentration of c f. It is noted that c f is the concentration within the polymer surface layer, and this concentration can be related to the bulk concentration or vapor pressure through a partition coefficient or solubility constant. The amount... 

Malaspina, L., Bardi, G., Gigli, R. (1974) Simultaneous determination by Knudsen-effusion microcalorimetric technique of the vapor pressure and enthalpy of vaporization of pyrene and 1,3,5-triphenylbenzene. J. Chem. Thermodyn. 6, 1053-1064. 

The enthalpies of phase transition, such as fusion (Aa,s/f), vaporization (AvapH), sublimation (Asut,//), and solution (As n//), are usually regarded as thermophysical properties, because they referto processes where no intramolecular bonds are cleaved or formed. As such, a detailed discussion of the experimental methods (or the estimation procedures) to determine them is outside the scope of the present book. Nevertheless, some of the techniques addressed in part II can be used for that purpose. For instance, differential scanning calorimetry is often applied to measure A us// and, less frequently, AmpH and AsubH. Many of the reported Asu, // data have been determined with Calvet microcalorimeters (see chapter 9) and from vapor pressure against temperature data obtained with Knudsen cells [35-38]. Reaction-solution calorimetry is the main source of AsinH values. All these auxiliary values are very important because they are frequently required to calculate gas-phase reaction enthalpies and to derive information on the strengths of chemical bonds (see chapter 5)—one of the main goals of molecular energetics. It is thus appropriate to make a brief review of the subject in this introduction. 

G. W. Thomson. Determination of Vapor Pressure. In Technique of Organic Chemistry vol. I, part 1, Physical Methods ofOrganic Chemistry (3rd. ed.) A. Weissberger, Ed. Interscience New York, 1965 chapter 9. 

Values for the parameters are determined by a least squares fit of experimental data using eq (5) for experiments such as galvanic cells measurements that measure solute activity and thus y/Yref values, and eq (6) for experiments such as vapor pressure measurements that measure solvent activity and thus (f) values. All the original data are used in a single fitting program to determine the best values for the parameters. A detailed description of the evaluation procedure has been illustrated for the system calcium chloride-water (Staples and Nuttall, 1977), and calculations deriving activity data from a variety of experimental technique measurements have also been described. 

Abstract In this chapter we discuss practical techniques and instrumentation used in experimental measurements of kinetic and equilibrium isotope effects. After describing methods to determine IE s on rate constants, brief treatments of mass spectrometry and isotope ratio mass spectrometry, NMR measurements of isotope effects, the use of radio-isotopes, techniques to determine vapor pressure and other equilibrium IE s, and IE s in small angle neutron scattering are presented. 

CAI s that were once molten (type B and compact type A) apparently crystallized under conditions where both partial pressures and total pressures were low because they exhibit marked fractionation of Mg isotopes relative to chondritic isotope ratios. But much remains to be learned from the distribution of this fractionation. Models and laboratory experiments indicate that Mg, O, and Si should fractionate to different degrees in a CAI (Davis et al. 1990 Richter et al. 2002) commensurate with the different equilibrium vapor pressures of Mg, SiO and other O-bearing species. Only now, with the advent of more precise mass spectrometry and sampling techniques, is it possible to search for these differences. Also, models prediet that there should be variations in isotope ratios with growth direction and Mg/Al content in minerals like melilite. Identification of such trends would verify the validity of the theory. Conversely, if no correlations between position, mineral composition, and Mg, Si, and O isotopic composition are found in once molten CAIs, it implies that the objects acquired their isotopic signals prior to final crystallization. Evidence of this nature could be used to determine which objects were melted more than once. 

The activity of the solvent often can be obtained by an experimental technique known as the isopiestic method [5]. With this method we compare solutions of two different nonvolatile solutes for one of which, the reference solution, the activity of the solvent has been determined previously with high precision. If both solutions are placed in an evacuated container, solvent will evaporate from the solution with higher vapor pressure and condense into the solution with lower vapor pressure until equilibrium is attained. The solute concentration for each solution then is determined by analysis. Once the molality of the reference solution is known, the activity of the solvent in the reference solution can be read from records of previous experiments with reference solutions. As the standard state of the solvent is the same for all solutes, the activity of the solvent is the same in both solutions at equUibrium. Once the activity of the solvent is known as a function of m2 for the new solution, the activity of the new solute can be calculated by the methods discussed previously in this section. 

One of the most common techniques for determining x parameters for polymer-solvent systems is the vapor pressure method.(10) In this approach, the uncrosslinked polymer is exposed to solvent vapor of known pressure, p. The polymer absorbs solvent until equilibrium is established, x is related to p and V2, the volume fraction of polymer at equilibrium, by the Flory-Huggins equation (ll)... 

The thermodynamic constants of THF polymerization have been investigated by a number of authors. A variety of experimental techniques have been utilized including determinations of conversion to polymer, combustion, heat capacities eind vapor pressure. Comparison of our results with some previously published data shows that our results are within the range of the values reported (Table 3). 

While this technique can be used for gas solubility in volatile liquids, where the vapor pressure of the liquid is determined prior to the introduction of the gas, it is uniquely suited for fhe measurement of gas solubilities in ILs because the gas phase remains pure. This is the technique used by Costa Gomez and coworkers [8-10] to measure the solubility of various gases in ILs and a schematic of the apparatus is shown in Figure 8.3. These apparatuses are frequently made entirely from glass and, therefore, are limited to low-pressure operation. Nonetheless, this makes them ideal for determining Henry s law constants. 

A technique of making known vapor concentrations of reasonably volatile liquids in a diluent gas involves the use of the vapor pressure of the liquid (30). The diluent gas is passed through successive thermostatted bubblers obtaining a mixture determined by the saturation vapor pressure. Thus for ethanol, if the bubblers were maintained at 20°C (ethanol vapor pressure at 20°C... 

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