Sublimation pressure: defined

A solid substance in equilibrium with its vapor phase will exhibit a well-defined vapor pressure for a given temperature, which will be independent of the relative amounts of solid and vapor present. The curve representing the solid/vapor equilibrium conditions is termed a sublimation curve, which generally takes a form similar to that of a vaporization curve. Although the sublimation pressure of a solid is often exceedingly small, for many substances it can be considerable. 

An increase in the boiling point or a decrease in the freezing point of a solution containing a nonvolatile component is compared to pure solvent caused by a reduction in the vapor pressure. The reduction of the freezing point AT of a solution is T — T, as shown in Fig. 1-42 where T is the freezing point (or melting point) of the pure solvent. At Tg the vapor pressure is the same for the liquid and solid phases of the solvent. Tg is defined by the intersection A of the vapor pressure curve VC and the sublimation pressure curve SC of the solvent. If only pure solvent freezes, the freezing point T of the solution occurs at the intersection B of the vapor pressure curve of the solution VCS and the sublimation pressure curve of the solvent SC. 

A considerable amount of research has been conducted on the decomposition and deflagration of ammonium perchlorate with and without additives. The normal thermal decomposition of pure ammonium perchlorate involves, simultaneously, an endothermic dissociative sublimation of the mosaic crystals to gaseous perchloric acid and ammonia and an exothermic solid-phase decomposition of the intermosaic material. Although not much is presently known about the nature of the solid-phase reactions, investigations at subatmospheric and atmospheric pressures have provided some information on possible mechanisms. When ammonium perchlorate is heated, there are three competing reactions which can be defined (1) the low-temperature reaction, (2) the high-temperature reaction, and (3) sublimation (B9). 

Heat transfer from the shelves to the sublimation front depends on the pressure and the distance between shelf and product (Fig. 1.58). Mass transfer (g/s) increases with the pressure, but also depends on the flow resistance of the already dry product and of the packing of the bones. If the maximum tolerable Tke is defined, the drying time depends only on the two processes mentioned above. It cannot be shortened under a given geometric situation and the chosen Tke. This method of Tkt control does not require thermocouples, and does not contaminate the product. 

The phase diagram also illustrates why some substances which melt at normal pressure, will sublime at a lower pressure the line p = Pa intersects at Tg the locus OR of the points defining the solid-vapour equilibrium, i.e. at the pressure pj, the substance will sublime at the temperature T. Sometimes the opposite behaviour is observed, namely that a substance which sublimes at normal pressure will melt in a vacuum system under its own vapour pressure This is a non-equilibrium phenomenon and occurs if the substance is heated so rapidly that its vapour pressure rises above that of the triple point this happens quite frequently with aluminium bromide and with iodine. 

Arsenic does not combine directly with molecular hydrogen,9 and the element may be purified by sublimation in that gas. Hydrides, however, may be obtained by indirect methods (see pp. 79-84). Arsenic may be displaced by the gas from solutions of its salts at high temperatures and pressures. Thus arsenic separates in large well-defined crystals when a solution of sodium arsenate is subjected to the action of hydrogen at 25 atm. pressure 10 the action commences at 300° C., 15 per cent, of the arsenic being precipitated at this temperature, but it increases rapidly with rising temperature and at 350° C. 77 per cent, of the arsenic is liberated. Arsine is not produced in the reaction. 

If a substance undergoes a transformation from one physical stale to another, such as a polymorphic transition, the fusion or sublimation of a solid, or the vaporization of a liquid, the heat adsorbed hy the substance during the transformation is defined as the latent heat of transformation (transition, fusion, sublimation or vaporization). It is equal in the enthalpy change of the process, which is the difference between the enthalpy of the substance in the two states at (he temperature of the transformation. For the purpose of thcrmochemical calculations, i( is usually reported as a molar quantity with die units of calories (or kilocalories) per mule (or gram formula weight). The symbol L or AH. with a subscript i.f (or in), s. and n is commonly used and the value is usually given at the equilibrium temperature of the transformation under atmospheric pressure, or at 25 C. 

Tellurium dipropionylmethane (2 6-Dimethylcyclotelluro-pentanedione) (Formula II), obtained from the dichloride by bisulphite reduction, crystallises from methyl alcohol, benzene or aqueous ethyl alcohol as well-defined golden-yellow needles, M.pt. 151° C. with slight decomposition. Under diminished pressure it sublimes at 110° C. as slender needles, which slowly pass at this temperature into compact prisms. It readily dissolves in organic solvents, except light petroleum in water it is sparingly soluble, the solution giving no enolic reactions. 

S03 (c, a), S03 (c, / ). There are two crystalline forms of solid sulfur trioxide, the ice-like or a form which melts sharply at 16.8°, and the wool-like or / form which is stable above 16.8° but does not appear to be well defined. The vapor pressure data of Smits and Schoen-maker,1-2 yield —12.1 for the heat of sublimation of S03 (c, a), whence Qf=106.0. Berthelot,6,9 and Grau and Roth1 measured the heat of solution of S03 (c, / ) in water. Their data yield Qf=105.8 and 105.2, respectively. Grau and Roth1 showed that the heat of solution varied considerably with the sample, indicating that the wool-like or / form of sulfur trioxide may be a mixture of varying composition. 

FIGURE 10.17 The vapor pressure of a solid or liquid depends strongly on temperature. The temperature at which the vapor pressure becomes 1 atm defines the normal boiling point of a liquid and the normal sublimation point of a solid. 

Where po and pn is the partial pressures of water vapor at z=0 and z=H(f) respectively. The pressure boundary condition at the top surface of the material being dried is defined as a constant pressure inside the drying chamber, and the vapor pressure at the sublimation interface is defined as an equilibrium vapor pressure according to the temperature of the interface. 

---