Ethanol-water equilibria

The operating reflux ratio is usually 1.5 to 10 times the minimum. By using the ethanol-water equilibrium curve for 101.3-kPa (1-atm) pressure shown in Fig. 13-123 out extending the line to a convenient point... 

McCabe-Thiele calculations are easiest to do on spreadsheets if the y versus x VLE data are expressed in an equation. The form y = f(x) is most convenient for flash distillation and for distillation columns (see Chapter 4) if stepping off stages from the bottom of the column up. The form x = g(y) is most convenient for distillation columns if stepping off stages from the top down. Built-in functions in Excel will determine polynomials that fit the data, aldiough the fit will usually not be perfect. This will be illustrated for fitting the ethanol-water equilibrium data in Table 2-1 in the form y = f (x ). (Note An additional data point Xg = 0.5079, = 0.6564 was added to the numbers in the table.) Enter the data in the... 

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,... 

A typical apphcatiou of a simple batch still might be distillation of an ethanol-water mixture at 101.3 kPa (1 atm). The initial charge is 100 mol of ethanol at 18 mole percent, aud the mixture must be reduced to a maximum ethanol concentration in the stiU of 6 mole percent. By using equilibrium data interpolated from Table 13-1,... 

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. 

Example 5.3 Predict the degrees of freedom for (a) pure liquid water and solid ice in equilibrium (b) pure liquid water, solid ice, and water vapor in equilibrium, and (c) solid ice in equilibrium with a liquid mixture of (ethanol + water). 

When the neutral macrocycles [64] were dissolved in solvents other than water, equilibria between the neutral forms and betaine structures were also found. In ethanol, the equilibrium between a phenol and a betainic... 

Equilibrium data for the system ethanol-water, at 760 mmHg, mol fractions... 

Pervaporation. Pervaporation differs from the other membrane processes described so far in that the phase-state on one side of the membrane is different from that on the other side. The term pervaporation is a combination of the words permselective and evaporation. The feed to the membrane module is a mixture (e.g. ethanol-water mixture) at a pressure high enough to maintain it in the liquid phase. The liquid mixture is contacted with a dense membrane. The other side of the membrane is maintained at a pressure at or below the dew point of the permeate, thus maintaining it in the vapor phase. The permeate side is often held under vacuum conditions. Pervaporation is potentially useful when separating mixtures that form azeotropes (e.g. ethanol-water mixture). One of the ways to change the vapor-liquid equilibrium to overcome azeotropic behavior is to place a membrane between the vapor and liquid phases. Temperatures are restricted to below 100°C, and as with other liquid membrane processes, feed pretreatment and membrane cleaning are necessary. 

Vapor-Liquid Equilibrium in the Ethanol-Water System Saturated with Chloride Salts... 

The present work studies the vapor-liquid equilibrium of the ethanol-water system saturated with copper(II) chloride, strontium chloride, and nickel(II) chloride. 

From experimental data for the ethanol-water system without salt, obtained at 700 and 760 mmHg, it can be seen that within this pressure range the effects of pressure on the equilibrium data are small enough to be within the experimental scatter. In fact, in previous works (8,11,12,13,18,19,23,24,27) there seems to be no clear difference between the equilibrium data at 700 and at 760 mmHg. Errors obtained in the determination of liquid and vapor compositions are approximately 0.05 wt % for the systems without salt. For salt-saturated systems, the same error prevails for the vapor phase, while the error is between 0.1 and 0.2 wt % for liquid phase compositions. The error for the boiling temperature is less than 0.1 °C for the systems without salt, but for saturated solutions the error is much greater from 0.2°C for nonconcentrated solutions to 3°C or more for highly concentrated solutions. 

The salt effects of potassium bromide and a series office symmetrical tetraalkylammonium bromides on vapor-liquid equilibrium at constant pressure in various ethanol-water mixtures were determined. For these systems, the composition of the binary solvent was held constant while the dependence of the equilibrium vapor composition on salt concentration was investigated these studies were done at various fixed compositions of the mixed solvent. Good agreement with the equation of Furter and Johnson was observed for the salts exhibiting either mainly electrostrictive or mainly hydrophobic behavior however, the correlation was unsatisfactory in the case of the one salt (tetraethylammonium bromide) where these two types of solute-solvent interactions were in close competition. The transition from salting out of the ethanol to salting in, observed as the tetraalkylammonium salt series is ascended, was interpreted in terms of the solute-solvent interactions as related to physical properties of the system components, particularly solubilities and surface tensions. 

Salt concentrations were obtained by the addition of known weights of dried salt to the solvent mixture. The compositions of the condensed equilibrium vapor samples and the previously prepared ethanol-water charges to the still were determined as previously outlined. The mole fractions of the salt, ethanol, and water charged to the Othmer still were thus accurately determined by mass balance calculations. 

The data in Tables I-XVI (see Appendix for all tables) show the isobaric vapor-liquid equilibrium results at the boiling point for potassium, ammonium, tetramethylammonium, tetraethylammonium, tetra-n-propylammonium, and tetra-n-butylammonium bromides in various ethanol-water mixtures at fixed liquid composition ratios. The temperature, t, is the boiling temperature for all solutions in these tables. In all cases, the ethanol-water composition was held constant between 0.20 and 0.35 mole fraction ethanol since it is in this range that the most dramatic salt effects on vapor-liquid equilibrium in this particular system should be observed. That is, previous data (12-15,38) have demonstrated that a maximum displacement of the vapor-liquid equilibrium curve by salts frequently occurs in this region. In the results presented here, it should be noted that Equation 1 has been modified to... 

An examination of Figures 1-6 indicates that Equation 1 is valid under conditions of constant x for potassium, ammonium, and tetramethylammonium bromides in ethanol-water mixtures. All three salts show an ability to salt out ethanol from these mixtures (i.e., increase its concentration in the equilibrium vapor) which is verified by their k values shown in Table XVIII. Also, the results for tetra-n-propylammonium bromide and tetra-n-butylammonium bromide in ethanol-water mixtures reveal that Equation 1 can be used to predict the salt effects of these systems however, these two salts demonstrate a propensity to salt in ethanol (i.e., decrease its vapor concentration) in ethanol-water mixtures. On the other hand, Figures 7-9 and the data in Table XVIII reveal that Equation 1 cannot be used to correlate the salt effects of tetraethylammonium bromide in ethanol-water. For this system, a linear dependence of log aja vs. z is observed initially however, a gradual levelling off occurs at higher concentrations. 

Table I. Isobaric Vapor—Liquid Equilibrium Data for the Potassium Bromide—Ethanol—Water System at x = 0.206 0.001 (760 5 Torr)...

Table 3.4 Air-Hexadecane, Air-Water, and Hexadecane-Water Equilibrium Partitioning of Hexane, Benzene, Diethylether, and Ethanol Free Energies, Enthalpies, and Entropies of Transfer, as well as Partition Constants Expressed on a Molar Base (i.e., mol U phase 1/mol L/ phase 2)...

Azeotropic and Partially Miscible Systems. Azeotropic mixtures are those whose vapor and liquid equilibrium compositions are identical. Their x-y lines cross or touch the diagonal. Partially miscible substances form a vapor phase of constant composition over the entire range of two-phase liquid compositions usually the horizontal portion of the x-y plot intersects the diagonal, but those of a few mixtures do not, notably those of mixtures of methylethylketone and phenol with water. Separation of azeotropic mixtures sometimes can be effected in several towers at different pressures, as illustrated by Example 13.6 for ethanol-water mixtures. Partially miscible constant boiling mixtures usually can be separated with two towers and a condensate phase separator, as done in Example 13.7 for n-butanol and water. 

The substituted benzylidenemalonodialdehydes (89) are organic Lewis acids and they react with feeble nucleophiles (ethanol, water) affording162 the equilibrium mixture of... 

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