Sodium vapor pressure, high temperature

Figure 2. Experimentai emission spectra of a high-pressure Na discharge. The tube diameter is 7.6 mm, the axis temperature 3000 K, the wall temperature 1400-1800 K, and the sodium vapor pressure 100 (a), 300 (b) and 1000 (c) torr. The spectra have not been corrected for the instrument spectral sensitivity indicated by -----. Arrows 1 and 2 indicate the classical satellites. A number of Na nonresonance lines and the K and Cs resonance lines (due to trace impurities) are indicated.

Historically, phenol was produced by the distillation of coal tar. Today, phenol is prepared by one of several synthetic methods, such as the fusion of sodium benzenesulfonate with sodium hydroxide followed by acidification the hydrolysis of chlorobenzene by dilute sodium hydroxide at high temperature and pressure to give sodium phenate, which on acidification liberates phenol (Dow process) or the catalytic vapor-phase reaction of steam and chlorobenzene at 500°C (Raschig process). 

Liquid Metals. If operating temperatures rise above 250—300°C, where many organic fluids decompose and water exerts high vapor pressure, hquid metals have found some use, eg, mercury for limited appHcation in turbines sodium, especially its low melting eutectic with 23 wt % potassium, as a hydrauhc fluid and coolant in nuclear reactors and potassium, mbidium, cesium, and gallium in some special uses. 

Bonilla, C. F., D. L. Sawhuey, and N. M. Makansi, 1962, Vapor Pressure of Alkali Metals III, Rubidium, Cesium, and Sodium-Potassium alloy up to 100 psia, Proc. 1962 High Temperature Liquid MetaI Heat Transfer Tech. Meeting, BNL-756, Brookhaven, NY. (3)... 

Very recently, Hu et al. claimed to have discovered a convenient procedure for the aerobic oxidation of primary and secondary alcohols utilizing a TEMPO based catalyst system free of any transition metal co-catalyst (21). These authors employed a mixture of TEMPO (1 mol%), sodium nitrite (4-8 mol%) and bromine (4 mol%) as an active catalyst system. The oxidation took place at temperatures between 80-100 °C and at air pressure of 4 bars. However, this process was only successful with activated alcohols. With benzyl alcohol, quantitative conversion to benzaldehyde was achieved after a 1-2 hour reaction. With non-activated aliphatic alcohols (such as 1-octanol) or cyclic alcohols (cyclohexanol), the air pressure needed to be raised to 9 bar and a 4-5 hour of reaction was necessary to reach complete conversion. Unfortunately, this new oxidation procedure also depends on the use of dichloromethane as a solvent. In addition, the elemental bromine used as a cocatalyst is rather difficult to handle on a technical scale because of its high vapor pressure, toxicity and severe corrosion problems. Other disadvantages of this system are the rather low substrate concentration in the solvent and the observed formation of bromination by-products. 

The melting point of sodium chloride is 800°C [301], At this high temperature, the chlorine gas obtained at the anode, would corrode all the cell components getting into contact with it. The sodium solubility in the molten salt is high (4.2 wt%) and so is its vapor pressure (50 kPa) [302], Therefore an electrolyte of lower melting point must be used. 

The removal of silica from a siliceous iron ore, such as the taconites found in Minnesota and Wisconsin, has been studied by Tiemann (T7, T9). Caustic concentrations from 25-500 gm/liter were used to digest the ore in a bomb at temperatures from 312 to 408°F. The leaching pressures in the bomb correspond closely to the equilibrium vapor pressures of the sodium hydroxide solutions used. A residual concentrate containing around 65% iron was obtained with —200 mesh material in 60 min of contact time. The high rate of dissolution of the silica was attributed to its occurrence in the form of microcrystalline (chalcedonic) varieties with high specific surface. The dissolution rate of pure quartz is directly proportional to the surface area and an average rate of 17 X 10 gm moles/cm sec was obtained for a 100 gm/liter NaOH solution at 312°F for the —400 mesh fraction. 

Due to its high vapor pressure at the operating temperature of the electrolysis, mercury, whose circulating tonnage represents 700 to 2400 kg/t per day of chlorine production capacity, pollutes the different gaseous streams produced (chlorine, hydrogen). Similarly, it contaminates the different liquids produced by the operation (spent brine, caustic soda, etc.). This results in substantial losses, which must be limited for economic as well as environmental reasons. Whereas small. amounts of mercury in the chlorine (0.1 to 0.2 g/t) are not detrimental to its subsequent uses, the same cannot be said of caustic soda, especially for food applications, in which it is removed by filtration (up to 15 ppb), for hydrogen, from which it is removed (up to 3 to 5 ppb) by absorption in sodium hypochlorite, adsorption on activated charcoal etc, and aqueous wastes, from which it is removed (up to 5 to 10 ppb) by precipitation, adsorption, reduction or extraction. The spent brine, which normally contains 1 to 10 ppm mercury and occasionally 1000 ppm, is usually recycled and therefore does not require treatment... 

---