Vaporizing tendency

The Lockhart-Martinelli correlations, as noted earlier, were developed for estimating the pressure drops associated with two-phase flow at ambient conditions. However, because of the increased vaporization tendency of cryogenic fluids, these correlations have a tendency to underestimate the pressure drop by as much as 10-30% with low-temperature flows. 

Two additional illustrations are given in Figures 6 and 7 which show fugacity coefficients for two binary systems along the vapor-liquid saturation curve at a total pressure of 1 atm. These results are based on the chemical theory of vapor-phase imperfection and on experimental vapor-liquid equilibrium data for the binary systems. In the system formic acid (1) - acetic acid (2), <() (for y = 1) is lower than formic acid at 100.5°C has a stronger tendency to dimerize than does acetic acid at 118.2°C. Since strong dimerization occurs between all three possible pairs, (fij and not... 

There is, of course, a mass of rather direct evidence on orientation at the liquid-vapor interface, much of which is at least implicit in this chapter and in Chapter IV. The methods of statistical mechanics are applicable to the calculation of surface orientation of assymmetric molecules, usually by introducing an angular dependence to the inter-molecular potential function (see Refs. 67, 68, 77 as examples). Widom has applied a mean-held approximation to a lattice model to predict the tendency of AB molecules to adsorb and orient perpendicular to the interface between phases of AA and BB [78]. In the case of water, a molecular dynamics calculation concluded that the surface dipole density corresponded to a tendency for surface-OH groups to point toward the vapor phase [79]. 

The vapor pressure ratio measures the intrinsic tendency of component 1 to enter the vapor phase relative to component 2. Likewise, ri measures the tendency of Mi to add to Mi - relative to M2 adding to Mi-. In this sense there is a certain parallel, but it is based on Mi - as a reference radical and hence appears to be less general than the vapor pressure ratio. Note, however, that ri = l/r2 means kn/ki2 = k2i/k22- In this case the ratio of rate constants for monomer 1 relative to monomer 2 is the same regardless of the reference radical examined. This shows the parallelism to be exact. 

When an atom or molecule receives sufficient thermal energy to escape from a Hquid surface, it carries with it the heat of vaporization at the temperature at which evaporation took place. Condensation (return to the Hquid state accompanied by the release of the latent heat of vaporization) occurs upon contact with any surface that is at a temperature below the evaporation temperature. Condensation occurs preferentially at all poiats that are at temperatures below that of the evaporator, and the temperatures of the condenser areas iacrease until they approach the evaporator temperature. There is a tendency for isothermal operation and a high effective thermal conductance. The steam-heating system for a building is an example of this widely employed process. 

Lamination Inks. This class of ink is a specialized group. In addition to conforming to the constraints described for flexo and gravure inks, these inks must not interfere with the bond formed when two or more films, eg, polypropylene and polyethylene, are joined with the use of an adhesive in order to obtain a stmcture that provides resistance properties not found in a single film. Laminations are commonly used for food applications such as candy and food wrappers. Resins used to make this type of ink caimot, therefore, exhibit any tendency to retain solvent vapor after the print has dried. Residual solvent would contaminate the packaged product making the product unsalable. 

Lithium Iodide. Lithium iodide [10377-51 -2/, Lil, is the most difficult lithium halide to prepare and has few appHcations. Aqueous solutions of the salt can be prepared by carehil neutralization of hydroiodic acid with lithium carbonate or lithium hydroxide. Concentration of the aqueous solution leads successively to the trihydrate [7790-22-9] dihydrate [17023-25-5] and monohydrate [17023-24 ] which melt congmendy at 75, 79, and 130°C, respectively. The anhydrous salt can be obtained by carehil removal of water under vacuum, but because of the strong tendency to oxidize and eliminate iodine which occurs on heating the salt ia air, it is often prepared from reactions of lithium metal or lithium hydride with iodine ia organic solvents. The salt is extremely soluble ia water (62.6 wt % at 25°C) (59) and the solutions have extremely low vapor pressures (60). Lithium iodide is used as an electrolyte ia selected lithium battery appHcations, where it is formed in situ from reaction of lithium metal with iodine. It can also be a component of low melting molten salts and as a catalyst ia aldol condensations. 

Poly(alkylene glycol)s have a number of characteristics that make them desirable as lubricants. Compared to petroleum lubricants, they have lower pour points, a higher viscosity index, and a wider range of solubilities including water, compatibility with elastomers, less tendency to form tar and sludge, and lower vapor pressure (35). 

The pentahalides of phosphorus, PX, in the gas phase exhibit varying tendencies to dissociate into trihaUde and halogen. InstabiUty increases with increasing ionic radius of the halogen. The pentafluoride appears to be thermally stable. Dissociation of the pentachloride, a few percent at 100°C and 101.3 kPa (1 atm), is essentially completed at 300°C (36). The pentabromide is partially dissociated in the Hquid state and totally dissociated above ca 35°C (39). Pentaiodide does not exist. The molecules of PF and PCl in the vapor phase are trigonal bipyramids. In the crystalline state, both pentachloride and pentabromide have ionic stmctures, ie, [PClJ IPClg] and [PBr4]" PBrJ , respectively. The PX" 4 cations are tetrahedral and the PX anion is octahedral (36,37). 

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). 

A third screening smoke-type is white phosphoms [7723-14-0] (WP), P (see Phosphorus and THE phosphides), which reacts spontaneously with air and water vapor to produce a dense cloud of phosphoms pentoxide [1314-56-3]. An effective screen is obtained as the P2O5 hydrolyzes to form droplets of dilute phosphoric acid aerosol. WP produces smoke in great quantity, but it has certain disadvantages. Because WP has such a high heat of combustion, the smoke it produces from bulk-filled munitions has a tendency to rise in pillarlike mass. This behavior too often nullifies the screening effect, particularly in stiU air. Also, WP is very brittle, and the exploding munitions in which it is used break it into very small particles that bum rapidly. 

There are direct substitutions of possible interest that would not be feasible without drastic changes in the feed system or pressure. Thus if the available substitute for natural gas is, eg, a manufactured gas containing much CO, there would almost always be a mismatch of the WIs unless the fuel could be further modified by mixing with some other gaseous fuel of high volumetric heating value (propane, butane, vaporized fuel oil, etc). Moreover, if there are substantial differences in eg, as a result of the presence of considerable H2 as well as CO in the substitute gas, the variation in dame height and dashback tendency can also make the substitution unsatisfactory for some purposes, even if the WI is reproduced. Refinements and additional criteria are occasionally appHed to measure these and other effects in more complex substitution problems (10,85). 

The term in equation 42 is called a Souders-Brown capacity parameter and is based on the tendency of the upflowing vapor to entrain Hquid with it to the plate above. The term E in equation 43 is called an E-factor. and E to be meaningful the cross-sectional area to which they apply must be specified. The capacity parameter is usually based on the total column cross section minus the area blocked for vapor flow by the downcomer(s). Eor the E-factor, typical operating ranges for sieve plate columns are... 

The activity coefficient y can be defined as the escaping tendency of a component relative to Raonlt s law in vapor-liqnid eqnihbrinm (see Sec. 4 in this handbook or Null, Phase Equilibrium in Process Design, Wiley-Interscience, 1970). 

The carbon residue is a measure of the carbon compounds left in a fuel after the volatile components have vaporized. Two different carbon residue tests are used, one for light distillates, and one for heavier fuels. For the light fuels, 90% of the fuel is vaporized, and the carbon residue is found in the remaining 10%. For heavier fuels, since the carbon residue is large, 100% of the sample can be used. These tests give a rough approximation of the tendency to form carbon deposits in the combustion system. The metallic compounds present in the ash are related to the corrosion properties of the fuel. 

Volatilization — Volatilization is a physico-chemical phenomenon of particular interest to environmental managers as well as safety managers. It is the tendency of a material to transfer from a liquid phase (either pure or dissolved as in aqueous systems) to a gaseous phase (commonly air). The volatilization, or evaporation as it is more commonly called, is controlled by a number of factors, the most important of which are the vapor pressure of the material, temperature (vapor pressure increases with temperature), and air/material interfacial surface area, and the action of active mass transfer agents such as wind. 

The tendency is greatest, however, where pressures are close to atmospheric and "superheat" relative to atmosphere is least. Pipestill atmospheric towers and cat unit fractionators tend to fall in this category. Some operators consider that the likelihood is great that calculated condensation (dew) will coalesce to droplets which will gravitate (rain) when the partial pressure of condensibles at the dew point exceeds 1/3 atmosphere. With this factor and environmental protection in mind, some plants have diverted such releases into closed systems. Generally, however, this has not been of sufficient concern, and such releases have been treated as though they were all vapor. 

The liquids that are separated from the gas stream in the first separator may be flowed directly to a tank or may be stabilized in some fashion. As was discussed in Chapter 2 of Volume 1, these liquids contain a large percentage of methane and ethane, which will flash to gas in the tank. This lowers the partial pressure of all other components in the tank and increases their tendency to flash to vapors. The process of increasing the amount of intermediate (C3 to C5) and heavy (C + ) components in the liquid phase is called stabilization. In a gas field this process is called condensate stabilization and in an oil field it is called crude stabilization. 

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