Substance, pure

Boublik, T., V. Fried, and E. Hala "The Vapor Pressure of Pure Substances," Elsevier, Amsterdam, 1973. 

Avogadro s number, L The number of particles (atoms or molecules) in one mole of any pure substance. L = 6 023 x 10. It has been determined by many methods including measurements of Brownian movement, electronic charge and the counting of a-particles. 

Clapeyron-Clausius equation A thermodynamic equation applying to any two-phase equilibrium for a pure substance. The equation states ... 

I This formula shows that if quantitative analysis in the infrared is to be possible, it is necessary to know the coefficients a( i ), therefore, either to have the pure substance, or to be able to obtain them from the literature... 

Fugacity is expressed as a function of the molar volume, the temperature, the parameters for pure substances Oj and h, and the binary interaction coefficients )... 

The calculation of vapor pressure of a pure substance consists of finding the pressure for which the fugacities of the liquid and vapor are equal. 

When the critical constants for a pure substance or the pseudocritical constants for a petroleum fraction are known, the vapor pressure for hydrocarbons and petroleum fractions can be calculated using the Lee and Kesler equations ... 

The average error is around 30%. This formula applies to pure substances and mixtures. For pure hydrocarbons, it is preferable to refer to solubility charts published by the API if good accuracy is required. 

The solid phase can be considered as a pure substance or a solid solution. 

It was made clear in Chapter II that the surface tension is a definite and accurately measurable property of the interface between two liquid phases. Moreover, its value is very rapidly established in pure substances of ordinary viscosity dynamic methods indicate that a normal surface tension is established within a millisecond and probably sooner [1], In this chapter it is thus appropriate to discuss the thermodynamic basis for surface tension and to develop equations for the surface tension of single- and multiple-component systems. We begin with thermodynamics and structure of single-component interfaces and expand our discussion to solutions in Sections III-4 and III-5. 

The principal point of interest to be discussed in this section is the manner in which the surface tension of a binary system varies with composition. The effects of other variables such as pressure and temperature are similar to those for pure substances, and the more elaborate treatment for two-component systems is not considered here. Also, the case of immiscible liquids is taken up in Section IV-2. 

Langmuir also gave needed emphasis to the importance of employing pure substances rather than the various natural oils previously used. He thus found that the limiting area (at the Pockels point) was the same for palmitic, stearic, and cerotic acids, namely, 21 per molecule. (For convenience to the reader, the common names associated with the various hydrocarbon derivatives most frequently mentioned in this chapter are given in Table IV-1.)... 

The importance of the van der Waals equation is that, unlike the ideal gas equation, it predicts a gas-liquid transition and a critical point for a pure substance. Even though this simple equation has been superseded, its... 

All standard states, both for pure substances and for components in mixtures and solutions, are defined for a pressure of exactly 1 atmosphere. However the temperature must be specified. (There is some movement towards metricating this to a pressure of 1 bar = 100 kPa = 0.986 924 atm. This would make a significant difference only for gases at J= 298 K, this would decrease a p by 32.6 J moT )... 

Nitrogen trifluoride and trichloride can both be prepared as pure substances by the action of excess halogen on ammonia, a copper catalyst being necessary for the formation of nitrogen trifluoride. 

Finally we require a case in which mechanism (lii) above dominates momentum transfer. In flow along a cylindrical tube, mechanism (i) is certainly insignificant compared with mechanism (iii) when the tube diameter is large compared with mean free path lengths, and mechanism (ii) can be eliminated completely by limiting attention to the flow of a pure substance. We then have the classical Poiseuille [13] problem, and for a tube of circular cross-section solution of the viscous flow equations gives 2... 

Ac Che limic of Knudsen screaming Che flux relacions (5.25) determine Che fluxes explicitly in terms of partial pressure gradients, but the general flux relacions (5.4) are implicic in Che fluxes and cheir solution does not have an algebraically simple explicit form for an arbitrary number of components. It is therefore important to identify the few cases in which reasonably compact explicit solutions can be obtained. For a binary mixture, simultaneous solution of the two flux equations (5.4) is straightforward, and the result is important because most experimental work on flow and diffusion in porous media has been confined to pure substances or binary mixtures. The flux vectors are found to be given by... 

Let us first consider experiments without composition gradients. These are permeability measurements, in which flow is induced by a pressure gradient Consider first the flow of pure substance 1, setting x = 1, = 0 and... 

At the outset it will be profitable to deal with an ideal solution possessing the following properties (i) there is no heat effect when the components are mixed (ii) there is no change in volume when the solution is formed from its components (iii) the vapour pressure of each component is equal to the vapour pressure of the pure substances multiplied by its mol fraction in the solution. The last-named property is merely an expression of Raoult s law, the vapour pressure of a substance is pro-... 

The theory underlying the removal of impurities by crystaUisation may be understood from the following considerations. It is assumed that the impurities are present in comparatively small proportion—usually less than 5 per cent, of the whole. Let the pure substance be denoted by A and the impurities by B, and let the proportion of the latter be assumed to be 5 per cent. In most instances the solubilities of A (SJ and of B (/Sb) are different in a particular solvent the influence of each compound upon the solubility of the other will be neglected. Two cases will arise for an3 particular solvent (i) the impurity is more soluble than the compound which is being purified (/Sg > SA and (ii) the impurity is less soluble than the compound Sg < S ). It is evident that in case (i) several recrystallisations will give a pure sample of A, and B will remain in the mother liquors. Case (ii) can be more clearly illustrated by a specific example. Let us assume that the solubility of A and 5 in a given solvent at the temperature of the laboratory (15°) are 10 g. and 3 g. per 100 ml. of solvent respectively. If 50 g. of the crude material (containing 47 5 g. of A and 2-5 g. of B) are dissolved in 100 ml. of the hot solvent and the solution allowed to cool to 15°, the mother liquor will contain 10 g. of A and 2-5 g. (i.e., the whole) of B 37-5 g. of pure crystals of A will be obtained. 

Nitrobenzene. Nitrobenzene, of analytical reagent quality, is satisfactory for most purposes. The technical product may contain dinitrobenzene and other impurities, whilst the recovered solvent may be contaminated with aniline. Most of the impurities may be removed by steam distillation after the addition of dilute sulphuric acid the nitrobenzene in the distillate is separated, dried with calcium chloride and distilled. The pure substance has b.p. 210°/760 mm. and m.p. 5 -7°. 

Sulphuryl chloride. The technical product should be fractionated, preferably in an all-glass apparatus the fraction b.p. 69-70° is collected. The pure substance has b.p. 69°/760 mm. 

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