Of sublimation

S = Heat of sublimation of sodium D = Dissociation energy of chlorine / = Ionization energy of sodium = Electron affinity of chlorine Uq = Lattice energy of sodium chloride AHf = Heat of formation of sodium chloride. 

We have seen that in a metal the atoms are close-packed, i.e. each metal atom is surrounded by a large number of similar atoms (often 12, or 8). The heat required to break up 1 mole of a metal into its constituent atoms is the heat of atomisation or heat of sublimation. Values of this enthalpy vary between about 80 and 800 kJ. for metals in their standard states these values indicate that the bonds between metal atoms can vary from weak to very strong. There is a rough proportionality between the m.p. of a metal and its heat of atomisation. so that the m.p. gives an approximate measure of bond strength. 

For an example of sublimation, see the preparation of anthra-quinone, p. 259 for semi-micro sublimation, see p. 69. 

The term distillation is applied to vaporisation and subsequent condensation according to (i) it should also be applied to (ii) since it is really the liquid which is converted into vapour and is first formed by condensation. Strictly speaking, the term sublimation should be applied to changes according to (iii). However, in practice, a substance when heated may first melt and then boil, but on cooling it may pass directly from the vapour to the solid the process is then also called sublimation. Indeed the mode of vaporisation, whether directly from solid to vapour or through the intermediate formation of a liquid, is of secondary importance it is the direct conversion of vapour to solid which is really the outstanding feature of sublimation in the laboratory. 

The theory of sublimation, t.e. the direct conversion from the vapour to the sohd state without the intermediate formation of the liquid state, has been discussed in Section 1,19. The number of compounds which can be purified by sublimation under normal pressure is comparatively small (these include naphthalene, anthracene, benzoic acid, hexachloroethane, camphor, and the quinones). The process does, in general, yield products of high purity, but considerable loss of product may occur. 

To a first approximation, the enthalpy of sublimation ISHs at constant temperature is ... 

Fig. 2.25 The differential heat of adsorption of argon on carbon blacks at 78 K, before and after graphitizalion.. Spheron O, Graphon. , and El denote molar heat of sublimation and of evaporation respectively.

When the sample is a solid, a separation of the analyte and interferent by sublimation may be possible. The sample is heated at a temperature and pressure below its triple point where the solid vaporizes without passing through the liquid state. The vapor is then condensed to recover the purified solid. A good example of the use of sublimation is in the isolation of amino acids from fossil mohusk shells and deep-sea sediments. ... 

Cera.micA.bla.tors, Several types of subliming or melting ceramic ablators have been used or considered for use in dielectric appHcations particularly with quartz or boron nitride [10043-11 -5] fiber reinforcements to form a nonconductive char. Fused siHca is available in both nonporous (optically transparent) and porous (sHp cast) forms. Ford Aerospace manufactures a 3D siHca-fiber-reinforced composite densified with coUoidal siHca (37). The material, designated AS-3DX, demonstrates improved mechanical toughness compared to monolithic ceramics. Other dielectric ceramic composites have been used with performance improvements over monolithic ceramics (see COMPOSITE MATERIALS, CERAMIC MATRIX). 

The thermal protection system of the space shutde is composed mainly of subliming or melting ablators that are used below their fusion or vaporization reaction temperatures (42). In addition to the carbon-carbon systems discussed above, a flexible reusable surface insulation composed of Nomex felt substrate, a Du Pont polyamide fiber material, is used on a large portion of the upper surface. High and low temperature reusable surface insulation composed of siHca-based low density tiles are used on the bottom surface of the vehicle, which sees a more severe reentry heating environment than does the upper surface of the vehicle (43). 

Most of the water is sublimated from the frozen mass by heating the product under reduced pressure. The operating conditions must be such that the product remains in a soHd state while sublimation is taking place. The completion of sublimation can be observed by an increase in product temperature. This increase occurs when the energy being introduced is no longer consumed by the latent heat of sublimation, but is absorbed by the product instead. 

Consequently, the development of chain length of the polymer is restricted and the average molecular weight tends to be low. PhthaUc anhydride has a tendency to sublime. Its heat of sublimation is 598 J /g (143 cal/g), and the heat of vaporization is 365 J/g (87.2 cal/g). Therefore, care must be taken to prevent its loss (see later discussions on Production Processes). 

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