Isothermal properties

The PC isothermal properties on the above Li-Mg-N-H system have been reported by a few groups for desorption [9, 20-22], absorption [23] and both absorption and desorption reactions [24—26], as shown in Figure 6.2 (desorption) and Figure 6.3 (absorption). However, thermodynamically accurate results have not yet been reported, because the kinetic properties are significantly worse, even around... 

Liquid Crystal Technique for Measuring Temperature, Fig. 5 Normalized standard deviation of temperatures calculated with local and global calibration curves under isothermal properties for encapsulated TLCs in liquid... 

If the coiiplin g parameter (the Bath relaxation constan t in IlyperChem), t, is loo Tight" (<0.1 ps), an isokinetic energy ensemble results rather than an isothermal (microcan on leal) ensemble. The trajectory is then neither canonical or microcan on-ical. You cannot calculate true time-dependent properties or ensemble averages for this trajectory. You can use small values of T for Ih CSC sim ii lalion s ... 

An interesting example of a large specific surface which is wholly external in nature is provided by a dispersed aerosol composed of fine particles free of cracks and fissures. As soon as the aerosol settles out, of course, its particles come into contact with one another and form aggregates but if the particles are spherical, more particularly if the material is hard, the particle-to-particle contacts will be very small in area the interparticulate junctions will then be so weak that many of them will become broken apart during mechanical handling, or be prized open by the film of adsorbate during an adsorption experiment. In favourable cases the flocculated specimen may have so open a structure that it behaves, as far as its adsorptive properties are concerned, as a completely non-porous material. Solids of this kind are of importance because of their relevance to standard adsorption isotherms (cf. Section 2.12) which play a fundamental role in procedures for the evaluation of specific surface area and pore size distribution by adsorption methods. 

The Type II isotherms obtained experimentally often display a rather long straight portion (BC in Fig. 2.9), a feature not strictly compatible with the properties of the BET equation which, as we have seen, yields a point of... 

As will be demonstrated in Chapter 4, however, the presence of micropores distorts the Type II isotherm in a sense which is reflected in a much increased value of the constant c. In such cases the value of c is no guide at all to the course of the isotherm on the external surface. Consequently the appropriate criterion for choosing the correct f-curve for a particular system is the similarity in chemical properties and not in c-values l>etween the solid under test and the reference solid. 

Furthermore, it must be remembered that highly disperse materials are, from their very nature, difficult to prepare with exactly reproducible surface properties, in respect of either the extent of the surface or the nature of the surface itself. Consequently, highly precise values of the absolute area of individual samples, even if attainable by some method as yet undeveloped, would be of little more value in practice than the BET specific surface, calculated from carefully measured isotherms. 

The subsequent literature shows the rule to be generally valid, within a few pet cent, amongst systems which give Typje IV isotherms in the typical example of Table 3.1, the data refer to adsorptives differing widely in their physical and chemical properties, yet the deviation of the saturation volume y, from the mean is within 6 per cent. 

The t and a.-methods, the nature of which was explained in Chapter 2, may be used to arrive at a value of the micropore volume. If the surface of the solid has standard properties, the t-plot (or a,-plot) corresponding to the isotherm of the nonporous powder in Fig. 4.11(a) will be a straight line passing through the origin (cf. curve (i) of Fig. 4.11(6)) and having a slope proportional to the specific surface of the powder. For the microporous powder which yields the isotherm (iii).of Fig. 4.11(a), the t-plot (or Oj-plot) will have the form of curve (iii) of Fig. 4.11(6) the linear branch of this curve will be parallel to curve (i), since it corresponds to the area of the outside of the particles which is identical with that of the nonporous parent particles. 

In describing the various mechanical properties of polymers in the last chapter, we took the attitude that we could make measurements on any time scale we chose, however long or short, and that such measurements were made in isothermal experiments. Most of the experimental results presented in Chap. 3 are representations of this sort. In that chapter we remarked several times that these figures were actually the result of reductions of data collected at different temperatures. Now let us discuss this technique our perspective, however, will be from the opposite direction taking an isothermal plot apart. 

The isothermal curves of mechanical properties in Chap. 3 are actually master curves constructed on the basis of the principles described here. Note that the manipulations are formally similar to the superpositioning of isotherms for crystallization in Fig. 4.8b, except that the objective here is to connect rather than superimpose the segments. Figure 4.17 shows a set of stress relaxation moduli measured on polystyrene of molecular weight 1.83 X 10 . These moduli were measured over a relatively narrow range of readily accessible times and over the range of temperatures shown in Fig. 4.17. We shall leave as an assignment the construction of a master curve from these data (Problem 10). 

Isotherms for H2O and / -hexane adsorption at room temperature and for O2 adsorption at Hquid oxygen temperature on 13X (NaX) zeoHte and on the crystalline Si02 molecular sieve siHcaHte are are shown in Figure 8 (43). SiHcaHte adsorbs water very weaMy. Further modification of siHcaHte by fluoride incorporation provides an extremely hydrophobic adsorbent, shown in Figure 9 (44). These examples illustrate the broad range of properties of crystalline molecular sieves. 

Many of the unusual properties of the perfluorinated inert fluids are the result of the extremely low intermolecular interactions. This is manifested in, for example, the very low surface tensions of the perfluorinated materials (on the order of 9-19 mN jm. = dyn/cm) at 25°C which enables these Hquids to wet any surface including polytetrafluoroethene. Their refractive indexes are lower than those of any other organic Hquids, as are theh acoustic velocities. They have isothermal compressibilities almost twice as high as water. Densities range from 1.7 to 1.9 g/cm (l )-... 

Heat pipes are used to perform several important heat-transfer roles ia the chemical and closely aUied iadustries. Examples iaclude heat recovery, the isothermaliziag of processes, and spot cooling ia the mol ding of plastics. In its simplest form the heat pipe possesses the property of extremely high thermal conductance, often several hundred times that of metals. As a result, the heat pipe can produce nearly isothermal conditions making an almost ideal heat-transfer element. In another form the heat pipe can provide positive, rapid, and precise control of temperature under conditions that vary with respect to time. 

The heat pipe has properties of iaterest to equipmeat desigaers. Oae is the teadeacy to assume a aeady isothermal coaditioa while carrying useful quantities of thermal power. A typical heat pipe may require as Htfle as one thousandth the temperature differential needed by a copper rod to transfer a given amount of power between two poiats. Eor example, whea a heat pipe and a copper rod of the same diameter and length are heated to the same iaput temperature (ca 750°C) and allowed to dissipate the power ia the air by radiatioa and natural convection, the temperature differential along the rod is 27°C and the power flow is 75 W. The heat pipe temperature differential was less than 1°C the power was 300 W. That is, the ratio of effective thermal conductance is ca 1200 1. 

Ferritic stainless steels depend on chromium for high temperature corrosion resistance. A Cr202 scale may form on an alloy above 600°C when the chromium content is ca 13 wt % (36,37). This scale has excellent protective properties and occurs iu the form of a very thin layer containing up to 2 wt % iron. At chromium contents above 19 wt % the metal loss owiag to oxidation at 950°C is quite small. Such alloys also are quite resistant to attack by water vapor at 600°C (38). Isothermal oxidation resistance for some ferritic stainless steels has been reported after 10,000 h at 815°C (39). Grades 410 and 430, with 11.5—13.5 wt % Cr and 14—18 wt % Cr, respectively, behaved significandy better than type 409 which has a chromium content of 11 wt %. 

If a dye is used which changes its properties by illumination, eg, its shape like the a2oben2ene, the phase change temperature can be lowered. The writing process then is nearly isothermal which helps to reduce spot diameters. 

Thermodynamic Properties. The thermodynamic melting point for pure crystalline isotactic polypropylene obtained by the extrapolation of melting data for isothermally crystallized polymer is 185°C (35). Under normal thermal analysis conditions, commercial homopolymers have melting points in the range of 160—165°C. The heat of fusion of isotactic polypropylene has been reported as 88 J/g (21 cal/g) (36). The value of 165 18 J/g has been reported for a 100% crystalline sample (37). Heats of crystallization have been determined to be in the range of 87—92 J/g (38). 

Indirect methods of estimating sorption have been used when actual measurement of sorption isotherm is impossible (44). For instance, sorption coefficients have been estimated from soil organic carbon and a specific surface of soil, and from semiempidcal equations using pesticide properties. 

The isothermal vaporization of pure Hquid / represents its transition from saturated Hquid to saturated vapor at temperature T and at saturation vapor pressure The treatment of this transition is faciUtated through use of property changes of vaporization defined by equation 139 ... 

The solubilities of Li, Na, and Ca hypochlorites in H2O at 25°C ate 40, 45, and 21%, respectively. Solubility isotherms in water at 10°C have been determined for the following systems Ca(OCl)2—CaCl2, NaOCl—NaCl, and Ca(OCl)2—NaOCl (141). The densities of approximately equimolar solutions of NaOCl and NaCl ate given in several product bulletins (142). The uv absorption spectmm of C10 shows a maximum at 292 nm with a molar absorptivity of 350 cm ( 5)- Heats of formation of alkali and alkaline earth hypochlorites ate given (143). Thermodynamic properties of the hypochlorite ion ate ... 

---