Equilibrium volatile

The last two columns of Tables 1 and 2 give equilibrium volatility ratios of ammonia partial pressure divided by the weight percent of ammonia in the liquid phase. The column labeled "Uncorr." gives the volatility ratio computed simply as the partial pressure of ammonia divided by the total weight percent of ammonia in solution. The second column gives a corrected volatility ratio based on the dissociation of ammonia at low concentrations and extrapolation to zero concentration of ammonia. 

Equilibrium concentrations describe the maximum possible concentration of each compound volatilized in the nosespace. Despite the fact that the process of eating takes place under dynamic conditions, many studies of volatilization of flavor compounds are conducted under closed equilibrium conditions. Theoretical equilibrium volatility is described by Raoulf s law and Henry s law for a description of these laws, refer to a basic thermodynamics text such as McMurry and Fay (1998). Raoult s law does not describe the volatility of flavors in eating systems because it is based upon the volatility of a compound in a pure state. In real systems, a flavor compound is present at a low concentration and does not interact with itself. Henry s law is followed for real solutions of nonelectrolytes at low concentrations, and is more applicable than Raoult s law because aroma compounds are almost always present at very dilute levels (i.e., ppm). Unfortunately, Henry s law does not account for interactions with the solvent, which is common with flavors in real systems. The absence of a predictive model for real flavor release necessitates the use of empirical measurements. 

C = equilibrium volatile concentration (Figure 5), M/D D = diameter of devolatilizer, L... 

The capacity of such a centrifuge varies with the solid concentration of the feed slurry, the drain rate of the mother and rinse liquors through the cake and filter screen, the amount of cake rinse required to attain the desired product purity, the time required to spin to terminal equilibrium volatile content, and the bulk density of polymer in the centrifuge basket. A centrifugal force of 1000 g may be... 

The equilibrium volatility of a species dissolved in water is characterized by its equilibrium constant for... 

Brunauer and co-workers [129, 130] found values of of 1310, 1180, and 386 ergs/cm for CaO, Ca(OH)2 and tobermorite (a calcium silicate hydrate). Jura and Garland [131] reported a value of 1040 ergs/cm for magnesium oxide. Patterson and coworkers [132] used fractionated sodium chloride particles prepared by a volatilization method to find that the surface contribution to the low-temperature heat capacity varied approximately in proportion to the area determined by gas adsorption. Questions of equilibrium arise in these and adsorption studies on finely divided surfaces as discussed in Section X-3. 

Experiments on sufficiently dilute solutions of non-electrolytes yield Henry s laM>, that the vapour pressure of a volatile solute, i.e. its partial pressure in a gas mixture in equilibrium with the solution, is directly proportional to its concentration, expressed in any units (molar concentrations, molality, mole fraction, weight fraction, etc.) because in sufficiently dilute solution these are all proportional to each other. 

Many of the reactions listed at the beginning of this section are acid catalyzed, although a number of basic catalysts are also employed. Esterifications are equilibrium reactions, and the reactions are often carried out at elevated temperatures for favorable rate and equilibrium constants and to shift the equilibrium in favor of the polymer by volatilization of the by-product molecules. An undesired feature of higher polymerization temperatures is the increased probability of side reactions such as the dehydration of the diol or the pyrolysis of the ester. Basic catalysts produce less of the undesirable side reactions. 

Three types of binary equilibrium cui ves are shown in Fig. 13-27. The y-x diagram is almost always plotted for the component that is the more volatile (denoted by the subscript 1) in the region where distillation is to take place. Cui ve A shows the most usual case, in which component 1 remains more volatile over the entire composition range. Cui ve B is typical of many systems (ethanol-water, for example) in which the component that is more volatile at lowvalues of X becomes less volatile than the other component at high values of X. The vapor and liquid compositions are identical for the homogeneous azeotrope where cui ve B crosses the 45° diagonal. A heterogeneous azeotrope is formed with two liquid phases by cui ve C,... 

It is sometimes permissible to assume constant relative volatility in order to approximate the equilibrium curve quickly. Then by applying Eq. (13-2) to components 1 and 2,... 

When it is desired to compute, with rigorous methods, actual rather than equilibrium stages, Eqs. (13-69) and (13-94) can be modified to include the Murphree vapor-phase efficiency T ij, defined by Eq. (13-29). This is particularly desirable for multistage operations involving feeds containing components of a wide range ol volatility and/or concentration, in which only a rectification (absorption) or stripping action is provided and all components are not sharply separated. In those cases, the use of a different Murphree efficiency for each component and each tray may be necessary to compute recovery accurately. 

When an equilibrium reaction occurs in a vapor-hquid system, the phase compositions depend not only on the relative volatility of the components in the mixture, but also on the consumption (and production) of species. Thus, the condition for azeotropy in a nonreactive system = x, for all i) no longer holds true in a reactive system and must be modified to include reaction stoichiometry ... 

In distillation towers, entrainment lowers the tray efficiency, and 1 pound of entrainment per 10 pounds of liquid is sometimes taken as the hmit for acceptable performance. However, the impact of entrainment on distiUation efficiency depends on the relative volatility of the component being considered. Entrainment has a minor impact on close separations when the difference between vapor and liquid concentration is smaU, but this factor can be dominant for systems where the liquid concentration is much higher than the vapor in equilibrium with it (i.e., when a component of the liquid has a very lowvolatiUty, as in an absorber). 

This term is analogous to relative volatility or its reciprocal (or to an equilibrium selectivity). Similarly, the assumption of a constant sepa-... 

An important characteristic of pervaporation that distinguishes it from distillation is that it is a rate process, not an equilibrium process. The more permeable component may be the less-volatile component. Perv oration has its greatest iitihty in the resolution of azeotropes, as an acqiinct to distillation. Selecting a membrane permeable to the minor corTiponent is important, since the membrane area required is roughly proportional to the mass of permeate. Thus pervaporation devices for the purification of the ethanol-water azeotrope (95 percent ethanol) are always based on a hydrophihc membrane. 

Toxic Volatile Ratio of Equilibrium Vapor Concentration over the Acute Substances Toxic Concentration (in ppm) is greater than 1000... 

Types of columns and packings. A slow distillation rate is necessary to ensure that equilibrium conditions operate and also that the vapour does not become superheated so that the temperature rises above the boiling point. Efficiency is improved if the column is heat insulated (either by vacuum jacketing or by lagging) and, if necessary, heated to Just below the boiling point of the most volatile component. Efficiency of separation also improves with increase in the heat of vaporisation of the liquids concerned (because fractionation depends on heat equilibration at multiple liquid-gas boundaries). Water and alcohols are more easily purified by distillation for this reason. 

The composition of the vapour in equilibrium with a miscible liquid mixture at any temperature, e.g. on heating during distillation, will be enriched by the more volatile components. The composition of the liquid phase produced on partial condensation will be enriched by the less volatile components. Such fractionation can have implications for safety in tliat tlie flammability and relative toxicity of the mixtures can change significantly. 

In distillation work for binary systems with constant relative volatility, the equilibrium between phases for a given component can be expressed by the following equation ... 

Pulmonary excretion takes place for volatile compounds. Alveolar air is at equilibrium with capillary blood. Thus, pulmonary excretion depends on the vapor pressure of the compound and its blood solubility. If blood solubility is... 

Now interpret phase X as pure solute then Cs and co become the equilibrium solubilities of the solute in solvents S and 0, respectively, and we can apply Eq. (8-58). Again the concentrations should be in the dilute range, but nonideality is not a great problem for nonelectrolytes. For volatile solutes vapor pressure measurements are suitable for this type of determination, and for electrolytes electrode potentials can be used. 

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