Vapor pressure salt solutions

Fig. 17.7. Two experimental techniques for measuring stoichiometric ion activity coefficients in hydrothermal solutions, (a) Determination by measuring difference in vapor pressures between solutions of known total salt concentration and pure water, (b) Isopiestic measurement in which sample solutions containing known weights of salts are equilibrated with a standard solution for which activity coefficients have been independently measured. In a sealed system water activity is everywhere the same at equilibrium measured salt concentrations in each sample container give the desired activity coefficients from the known activity of water in the standard salt solution.

The value of is determined-independently, from measurements of electromotive force, freezing point, or vapor pressure, in solutions of the pure salt. 

Chemical reactions in the liquid phase are either reversible or irreversible. Typical reversible reactions are involved in the absorption of H2S into ethanolamines, or the absorption of CO2 into alkali carbonate solutions. These reversible reactions permit the resultant solution to be regenerated so that the solute can be recovered in a concentrated form. Some irreversible reactions are the absorption of NH3 into dilute acids and the absorption of CO2 into alkaline hydroxides. The solute in such absorptions is so tightly bound in the reaction product that there is no appreciable vapor pressure of solute above the liquid phase. Under these conditions, regeneration of the solute is not possible, and the reacting component in the liquid is consumed. The purpose of such a reactant is to increase the solubility of the solute in the liquid phase and/or reduce the liquid-film resistance to mass transfer. Much theoretical work has been conducted since the 1950s to study diffusion and reaction in the liquid phase [19]. To calculate the effect of the rate of chemical reaction on the mass transfer requires the prediction of physical/chemical constants of salt solutions, such as equilibrium constants, reaction velocities, solubilities, and diffusion coefficients. Often, these constants must be available at elevated temperatures and/or pressures. 

In addition to the carbon monoxide vapor pressure, the vapor pressures of other solution components are of interest in assisting the calculation of possible losses and heat requirements. Copper-ammonium carbonate solutions have an appreciably higher vapor pressure than solutions of the formate or salts of stronger acids because of the relatively high decomposition pressure of ammonium carbonate. The total vapor pressures of a number of solutions have been measured by Zhavoronkov and Reshchikov (1933) and Zhavoronkov and Chagunava (1940). 

A saturated aqueous solution in contact with an excess of a definite solid phase at a given temperature will maintain constant humidity in an enclosed space. Table 11.4 gives a number of salts suitable for this purpose. The aqueous tension (vapor pressure, in millimeters of Hg) of a solution at a given temperature is found by multiplying the decimal fraction of the humidity by the aqueous tension at 100 percent humidity for the specific temperature. For example, the aqueous tension of a saturated solution of NaCl at 20°C is 0.757 X 17.54 = 13.28 mmHg and at 80°C it is 0.764 X 355.1 = 271.3 mmHg. 

Anionic polymerization of vinyl monomers can be effected with a variety of organometaUic compounds alkyllithium compounds are the most useful class (1,33—35). A variety of simple alkyllithium compounds are available commercially. Most simple alkyllithium compounds are soluble in hydrocarbon solvents such as hexane and cyclohexane and they can be prepared by reaction of the corresponding alkyl chlorides with lithium metal. Methyllithium [917-54-4] and phenyllithium [591-51-5] are available in diethyl ether and cyclohexane—ether solutions, respectively, because they are not soluble in hydrocarbon solvents vinyllithium [917-57-7] and allyllithium [3052-45-7] are also insoluble in hydrocarbon solutions and can only be prepared in ether solutions (38,39). Hydrocarbon-soluble alkyllithium initiators are used directiy to initiate polymerization of styrene and diene monomers quantitatively one unique aspect of hthium-based initiators in hydrocarbon solution is that elastomeric polydienes with high 1,4-microstmcture are obtained (1,24,33—37). Certain alkyllithium compounds can be purified by recrystallization (ethyllithium), sublimation (ethyllithium, /-butyUithium [594-19-4] isopropyllithium [2417-93-8] or distillation (j -butyUithium) (40,41). Unfortunately, / -butyUithium is noncrystaUine and too high boiling to be purified by distiUation (38). Since methyllithium and phenyllithium are crystalline soUds which are insoluble in hydrocarbon solution, they can be precipitated into these solutions and then redissolved in appropriate polar solvents (42,43). OrganometaUic compounds of other alkaU metals are insoluble in hydrocarbon solution and possess negligible vapor pressures as expected for salt-like compounds. 

The high solubility of the salt and resultant low water vapor pressure (58) of its aqueous solutions ate usehil ia absorption air conditioning (qv) systems. Lithium bromide absorption air conditioning technology efficiencies can surpass that of reciprocal technology usiag fluorochlorocarbon refrigerants. 

Lithium Iodide. Lithium iodide [10377-51 -2/, Lil, is the most difficult lithium halide to prepare and has few appHcations. Aqueous solutions of the salt can be prepared by carehil neutralization of hydroiodic acid with lithium carbonate or lithium hydroxide. Concentration of the aqueous solution leads successively to the trihydrate [7790-22-9] dihydrate [17023-25-5] and monohydrate [17023-24 ] which melt congmendy at 75, 79, and 130°C, respectively. The anhydrous salt can be obtained by carehil removal of water under vacuum, but because of the strong tendency to oxidize and eliminate iodine which occurs on heating the salt ia air, it is often prepared from reactions of lithium metal or lithium hydride with iodine ia organic solvents. The salt is extremely soluble ia water (62.6 wt % at 25°C) (59) and the solutions have extremely low vapor pressures (60). Lithium iodide is used as an electrolyte ia selected lithium battery appHcations, where it is formed in situ from reaction of lithium metal with iodine. It can also be a component of low melting molten salts and as a catalyst ia aldol condensations. 

In the Godrej-Lurgi process, olefins are produced by dehydration of fatty alcohols on alumina in a continuous vapor-phase process. The reaction is carried out in a specially designed isothermal multitube reactor at a temperature of approximately 300°C and a pressure of 5—10 kPa (0.05—0.10 atm). As the reaction is endothermic, temperature is maintained by circulating externally heated molten salt solution around the reactor tubes. The reaction is sensitive to temperature fluctuations and gradients, hence the need to maintain an isothermal reaction regime. 

Physical and Chemical Properties. Ammonium nitrate is a white, crystalline salt, df = 1.725, that is highly soluble in water, as shown in Table 3 (7). Although it is very hygroscopic, it does not form hydrates. This hygroscopic nature compHcates its usage in explosives, and until about 1940, was a serious impediment to its extensive use in fertilizers. The soHd salt picks up water from air when the vapor pressure of water exceeds the vapor pressure of a saturated aqueous ammonium nitrate solution (see Table 4). 

The reaction involves two electrons per thionyl chloride [7719-09-7] molecule (40). Also, one of the products, SO2, is a Hquid under the internal pressure of the cell, facihtating a more complete use of the reactant. Finally, no cosolvent is required for the solution, because thionyl chloride is a Hquid having only a modest vapor pressure at room temperature. The electrolyte salt most commonly used is lithium aluminum chloride [14024-11-4] LiAlCl. Initially, the sulfur product is also soluble in the electrolyte, but as the composition changes to a higher SO2 concentration and sulfur [7704-34-9] huA.ds up, a saturation point is reached and the sulfur precipitates. 

Beryllium Sulfate. BeiyUium sulfate tetiahydiate [7787-56-6], BeSO TH O, is produced commeicially in a highly purified state by fiactional crystallization from a berylhum sulfate solution obtained by the reaction of berylhum hydroxide and sulfuric acid. The salt is used primarily for the production of berylhum oxide powder for ceramics. Berylhum sulfate chhydrate [14215-00-0], is obtained by heating the tetrahydrate at 92°C. Anhydrous berylhum sulfate [13510-49-1] results on heating the chbydrate in air to 400°C. Decomposition to BeO starts at about 650°C, the rate is accelerated by heating up to 1450°C. At 750°C the vapor pressure of SO over BeSO is 48.7 kPa (365 mm Hg). 

Referring to Figure 8, temperature Tc is the chamber temperature and Ts is the surface temperature at the salt solution/vapor interface. The temperature of the chamber is well defined and is an experimental variable, whereas Ts must be higher than Tc due to condensation of vapor on the saturated solution surface. We can determine Ts by applying the Clausius-Clapeyron equation to the problem. Assume that the vapor pressures of the surface and chamber are equal (no pressure gradients), indicating that the temperature must be raised at the surface (to adjust the vapor pressure lowering of the saturated solution) to Pc (at Tc) = Ps (at Tc). However, there is a difference in relative humidity between the surface and the chamber, where RHC is the relative humidity in the chamber and RH0 is the relative humidity of the saturated salt solution, and we obtain... 

The basic assumption for a mass transport limited model is that diffusion of water vapor thorugh air provides the major resistance to moisture sorption on hygroscopic materials. The boundary conditions for the mass transport limited sorption model are that at the surface of the condensed film the partial pressure of water is given by the vapor pressure above a saturated solution of the salt (Ps) and at the edge of the diffusion boundary layer the vapor pressure is experimentally fixed to be Pc. The problem involves setting up a mass balance and solving the differential equation according to the boundary conditions (see Fig. 10). 

The boundary conditions for the system are (1) that at the surface of the hygroscopic material the partial pressure of water is determined by that of the saturated salt solution (Ps) and (2) that at a characteristic distance from the surface (8) the partial pressure of water vapor is given by the chamber pressure (Pc). 

The boundary conditions are that (1) at the moving boundary ( ) the solution is saturated with salt with a corresponding concentration of water (Cs) and (2) at the disk/atmosphere surface the concentration of water is governed by the equilibrium vapor pressure in the chamber to give a water concentration of C0. 

In writing the Etudes de dynamique chimique (1884), van t Hoff drew on Helmholtz s 1882 paper but especially on the work of August Horstmann, a student of Bunsen, Clausius, and H. Landolt.59 As has often been discussed, van t Hoffs was an ambitious and original synthesis of disconnected ideas and theories about opposing forces, equilibrium, active masses, work and affinity, electromotive force, and osmotic pressure. He demonstrated that the heat of reaction is not a direct measure of affinity but that the so-called work of affinity may be calculated from vapor pressures (the affinity of a salt for its water of crystallization), osmotic pressure (affinity of a solute for a solution), or electrical work in a reversible galvanic cell (which he showed to be proportional to the electromotive force). 

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