Third component

Figure A2.5.30. Left-hand side Eight hypothetical phase diagrams (A through H) for ternary mixtures of d-and /-enantiomers with an optically inactive third component. Note the syimnetry about a line corresponding to a racemic mixture. Right-hand side Four T, x diagrams ((a) tlirough (d)) for pseudobinary mixtures of a racemic mixture of enantiomers with an optically inactive third component. Reproduced from [37] 1984 Phase Transitions and Critical Phenomena ed C Domb and J Lebowitz, vol 9, eh 2, Knobler C M and Scott R L Multicritical points in fluid mixtures. Experimental studies pp 213-14, (Copyright 1984) by pennission of the publisher Academic Press.

Poly(ethyl methacrylate) (PEMA) yields truly compatible blends with poly(vinyl acetate) up to 20% PEMA concentration (133). Synergistic improvement in material properties was observed. Poly(ethylene oxide) forms compatible homogeneous blends with poly(vinyl acetate) (134). The T of the blends and the crystaUizabiUty of the PEO depend on the composition. The miscibility window of poly(vinyl acetate) and its copolymers with alkyl acrylates can be broadened through the incorporation of acryUc acid as a third component (135). A description of compatible and incompatible blends of poly(vinyl acetate) and other copolymers has been compiled (136). Blends of poly(vinyl acetate) copolymers with urethanes can provide improved heat resistance to the product providing reduced creep rates in adhesives used for vinyl laminating (137). 

The equihbrium shown in equation 3 normally ties far to the left. Usually the water formed is removed by azeotropic distillation with excess alcohol or a suitable azeotroping solvent such as benzene, toluene, or various petroleum distillate fractions. The procedure used depends on the specific ester desired. Preparation of methyl borate and ethyl borate is compHcated by the formation of low boiling azeotropes (Table 1) which are the lowest boiling constituents in these systems. Consequently, the ester—alcohol azeotrope must be prepared and then separated in another step. Some of the methods that have been used to separate methyl borate from the azeotrope are extraction with sulfuric acid and distillation of the enriched phase (18), treatment with calcium chloride or lithium chloride (19,20), washing with a hydrocarbon and distillation (21), fractional distillation at 709 kPa (7 atmospheres) (22), and addition of a third component that will form a low boiling methanol azeotrope (23). 

Nitroanthraquinone is prepared from anthraquinone by nitration in sulfuric acid (11), or in organic solvent (12). Nitration in nitric acid is dangerous. The mixture of anthraquinone and nitric acid forms a Sprengel mixture (13,14) which may detonate. However, detonation can be prevented by a dding an inert third component such as sulfuric acid. Experimental results of the steel-tube detonation tests for the anthraquinone—HNO2—H2SO4 system have been pubUshed (13). 

Once the composition of each equiHbrium phase is known, infinite dilution activity coefficients for a third component ia each phase can then be calculated. The octanol—water partition coefficient is directly proportional to the ratio of the infinite dilution activity coefficients for a third component distributed between the water-rich and octanol-rich phases (5,24). The primary drawback to the activity coefficient approach to estimation is the difficulty of the calculations involved, particularly when the activity coefficient model is complex. 

Medium Boiling Esters. Esterificatioa of ethyl and propyl alcohols, ethylene glycol, and glycerol with various acids, eg, chloro- or bromoacetic, or pymvic, by the use of a third component such as bensene, toluene, hexane, cyclohexane, or carbon tetrachloride to remove the water produced is quite common. Bensene has been used as a co-solvent ia the preparatioa of methyl pymvate from pymvic acid (101). The preparatioa of ethyl lactate is described as an example of the general procedure (102). A mixture of 1 mol 80% lactic acid and 2.3 mol 95% ethyl alcohol is added to a volume of benzene equal to half that of the alcohol (ca 43 mL), and the resulting mixture is refluxed for several hours. When distilled, the overhead condensate separates iato layers. The lower layer is extracted to recover the benzene and alcohol, and the water is discarded. The upper layer is returned to the column for reflux. After all the water is removed from the reaction mixture, the excess of alcohol and benzene is removed by distillation, and the ester is fractionated to isolate the pure ester. 

As mentioned previously, ternaiy mixtures can be represented by 125 different residue curve maps or distillation region diagrams. However, feasible distillation sequences using the first approach can be developed for breaking homogeneous binaiy azeotropes by the addition of a third component only for those more restricted systems that do not have a distillation boundaiy connected to the azeotrope and for which one of the original components is a node. For example, from... 

The efficiencies which may be obtained can consequently be calculated by simple stoichiometry from the equilibrium data. In the ease of countercurrent-packed columns, the solute can theoretically be completely extracted, but equilibrium is not always reached because of the poorer contact between the phases. The rate of solute transfer between phases governs the operation, and the analytical treatment of the performance of such equipment follows closely the methods employed for gas absorption. In the ease of two immiscible liquids, the equilibrium concentrations of a third component in each of the two phases are ordinarily related as follows ... 

As mentioned earlier the ease or difficulty of separating two products depends on the difference in their vapor pressures or volatilities. There are situations in the refining industry in which it is desirable to recover a single valuable compound in high purity from a mixture with other hydrocarbons which have boiling points so close to the more valuable product that separation by conventional distillation is a practical impossibility. Two techniques which may be applied to these situations are azeotropic distillation and extractive distillation. Both methods depend upon the addition to the system of a third component which increases the relative volatility of the constituents to be separated. 

Although not strictly part of a model chemistry, there is a third component to every Gaussian calculation involving how electron spin is handled whether it is performed using an open shell model or a closed shell model the two options are also referred to as unrestricted and restricted calculations, respectively. For closed shell molecules, having an even number of electrons divided into pairs of opposite spin, a spin restricted model is the default. In other words, closed shell calculations use doubly occupied orbitals, each containing two electrons of opposite spin. 

The treatment of blends as a two phase system opened up an interesting field of modifying the composite properties by the use of a (third component within the interface boundaries, which is termed as compatibilizers [1]. Such modifications are still being extended to the formation of microgel out of the interaction between the two blend partners having a reactive for functionalities. This type of interchain crosslinking does not require any compatibilizer to enhance the blend properties and also allows the blends to be reprocessed by further addition of a curative to achieve still further improved properties [3,4]. Such interchain crosslinking is believed to reduce the viscoelastic mismatch between the blend partners and, thus, facilitates smooth extrusion [5,6]. 

Evidently nature can no longer be seen as matter and energy alone. Nor can all her secrets be unlocked with the keys of chemistry and physics, brilliantly successful as these two branches of science have been in our century. A third component is needed for any explanation of the world that claims to be complete. To the powerful theories and physics must be added a late arrival a theory of information. Nature must be interpreted as matter, energy and information. ... 

Figure 2 is a multivariate plot of some multivariate data. We have plotted the component concentrations of several samples. Each sample contains a different combination of concentrations of 3 components. For each sample, the concentration of the first component is plotted along the x-axis, the concentration of the second component is plotted along the y-axis, and the concentration of the third component is plotted along the z-axis. The concentration of each component will vary from some minimum value to some maximum value. In this example, we have arbitrarily used zero as the minimum value for each component concentration and unity for the maximum value. In the real world, each component could have a different minimum value and a different maximum value than all of the other components. Also, the minimum value need not be zero and the maximum value need not be unity. 

A. Effect of Third Component on Critical Solution Temperature. 195... 

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