Triple vapor

At a given temperature and pressure, a pure compound can exist in one, two or three states. The compound exists at three different states at the triple point and at two different states along the curves of vaporization, freezing and sublimation. Refer to Figure 4.6. 

Triple point temperature K Heat of fusion kJ/lc Heat of vaporization kJ/kg Liquid conductivity atr, W / (m-K) Liquid conductivity AtT W/(m-I0 Temperature Ti K Temperature h K... 

Triple point temperature Heat of fusion Heat of vaporization Liquid conductivity at r, Liquid conductivity at Temperature Tx Temperature Tz... 

Molecular dynamics and density functional theory studies (see Section IX-2) of the Lennard-Jones 6-12 system determine the interfacial tension for the solid-liquid and solid-vapor interfaces [47-49]. The dimensionless interfacial tension ya /kT, where a is the Lennard-Jones molecular size, increases from about 0.83 for the solid-liquid interface to 2.38 for the solid-vapor at the triple point [49], reflecting the large energy associated with a solid-vapor interface. 

Referring to Fig. XVII-17, use handbook data to calculate the vapor pressure of O2 ordinary liquid at the melting point of the 6 phase. Comment on the result. Locate the 2D S-L-V triple point. 

Table 5.27 Compressibility of Water Table 5.28 Mass of Water Vapor In Saturated Air Table 5.29 Van der Waals Constants for Gases Table 5.30 Triple Points of Various M aterlals 5.9.1 Some Physical Chemistry Equations for Gases...

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. ... 

Molten Salt Distillation. Hafnium tetrachloride is slightly more volatile than zirconium tetrachloride, but a separation process based on this volatility difference is impractical at atmospheric pressures because only soHd and vapor phases exist. The triple point for these systems is at about 2.7 MPa (400 psia) and 400°C so that separation of the Hquids by distillation would necessarily require a massive pressurized system (13). 

Hydration. Water adds to the triple bond to yield acetaldehyde via the formation of the unstable enol (see Acetaldehyde). The reaction has been carried out on a commercial scale using a solution process with HgS04/H2S04 catalyst (27,28). The vapor-phase reaction has been reported at... 

Tables 2,3, and 4 outline many of the physical and thermodynamic properties ofpara- and normal hydrogen in the sohd, hquid, and gaseous states, respectively. Extensive tabulations of all the thermodynamic and transport properties hsted in these tables from the triple point to 3000 K and at 0.01—100 MPa (1—14,500 psi) are available (5,39). Additional properties, including accommodation coefficients, thermal diffusivity, virial coefficients, index of refraction, Joule-Thorns on coefficients, Prandti numbers, vapor pressures, infrared absorption, and heat transfer and thermal transpiration parameters are also available (5,40). Thermodynamic properties for hydrogen at 300—20,000 K and 10 Pa to 10.4 MPa (lO " -103 atm) (41) and transport properties at 1,000—30,000 K and 0.1—3.0 MPa (1—30 atm) (42) have been compiled. Enthalpy—entropy tabulations for hydrogen over the range 3—100,000 K and 0.001—101.3 MPa (0.01—1000 atm) have been made (43). Many physical properties for the other isotopes of hydrogen (deuterium and tritium) have also been compiled (44).

In addition to H2, D2, and molecular tritium [100028-17-8] the following isotopic mixtures exist HD [13983-20-5] HT [14885-60-0] and DT [14885-61-1]. Table 5 Hsts the vapor pressures of normal H2, D2, and T2 at the respective boiling points and triple points. As the molecular weight of the isotope increases, the triple point and boiling point temperatures also increase. Other physical constants also differ for the heavy isotopes. A 98% ortho—25/q deuterium mixture (the low temperature form) has the following critical properties = 1.650 MPa(16.28 atm), = 38.26 K, 17 = 60.3 cm/mol3... 

Fig. 2. A water triple-point ceU. A, handle B, water vapor C, Hquid vapor, D, soHd water (ice mande) and E, thermometer weU.

VP = vapor pressure point CVGT, constant volume gas thermometer point TP, triple point MP, melting point FP, freezing point. Note MP and FP at 101.325 Pa (1 atm) ambient pressure. 

Static Pressure Synthesis. Diamond can form direcdy from graphite at pressures of about 13 GPa (130 kbar) and higher at temperatures of about 3300—4300 K (7). No catalyst is needed. The transformation is carried out in a static high pressure apparatus in which the sample is heated by the discharge current from a capacitor. Diamond forms in a few milliseconds and is recovered in the form of polycrystalline lumps. From this work, and studies of graphite vaporization/melting, the triple point of diamond, graphite, and molten carbon is estimated to He at 13 GPa and 5000 K (Fig. 1)... 

Young s modulus, N/m heat of vaporization, kj /mol sublimation point, K triple point, K... 

Properties of Light and Heavy Hydrogen. Vapor pressures from the triple point to the critical point for hydrogen, deuterium, tritium, and the various diatomic combinations are Hsted in Table 1 (15). Data are presented for the equiUbrium and normal states. The equiUbrium state for these substances is the low temperature ortho—para composition existing at 20.39 K, the normal boiling point of normal hydrogen. The normal state is the high (above 200 K) temperature ortho—para composition, which remains essentially constant. 

Table 1. Vapor Pressures and Triple and Critical Points of Hydrogen Isotopes ...

Equations of State. Equations of state having adjustable parameters are often used to model the pressure—volume—temperature (PVT) behavior of pure fluids and mixtures (1,2). Equations that are cubic in specific volume, such as a van der Waals equation having two adjustable parameters, are the mathematically simplest forms capable of representing the two real volume roots associated with phase equiUbrium, or the three roots (vapor, Hquid, sohd) characteristic of the triple point. 

Vapor pressure is the most important of the basic thermodynamic properties affec ting liquids and vapors. The vapor pressure is the pressure exerted by a pure component at equilibrium at any temperature when both liquid and vapor phases exist and thus extends from a minimum at the triple point temperature to a maximum at the critical temperature, the critical pressure. This section briefly reviews methods for both correlating vapor pressure data and for predicting vapor pressure of pure compounds. Except at very high total pressures (above about 10 MPa), there is no effect of total pressure on vapor pressure. If such an effect is present, a correction, the Poynting correction, can be applied. The pressure exerted above a solid-vapor mixture may also be called vapor pressure but is normallv only available as experimental data for common compounds that sublime. 

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