Rock-salt

Salt mining is a large-scale specialized activity. Few chlorine producers mine salt or have much control over the process. Section 7.1.2 therefore gives only a brief review of the subject of mechanical mining of rock salt. Solar salt production, on the other hand, is closely tied to chlorine plants in some parts of the world. A fuller description of its production seems appropriate and appears in Section 7.1.3. 

While the natural salts predominate in the NaCl market, the chlor-alkali industry also uses quantities of processed and byproduct NaCl. Several techniques, discussed in Section 7.1.5, are used to upgrade both rock and solar salts in order to reduce the cost of on-site treatment. In other cases, byproduct brines are available from chlorine consumers. These usually result from the neutralization of HCl produced in phosgenation or chlorination processes (Section 7.1.4). 

KCl is much less plentiful than NaCl. Its molar concentration in seawater is only one fiftieth that of NaCl. It is obtained chiefly from mineral deposits and again is not so widespread as NaCl. Much of the KCl, moreover, exists in mixed ores such as sylvinite, a combination of NaCl and KCl. KCl is discussed separately in Section 7.1.6. 

Any chlor-alkali producer whose operation is based on the solid raw material will find it necessary to store salt. Section 7.1.7 addresses this topic. 

Most rock salt mining involves undercutting of a deposit, drilling, and blasting. Usually, mining advances by undercutting the salt to a distance of about 5 m from the 

In the following sections, we will look in some more detail at the symmetry systems of two fundamentally important crystals, rock salt and diamond, following their descriptions by Shubnikov and Koptsik [9-19]. The descriptions that will be given are far from complete. They are intended to give some flavor for the characterization of these two highly symmetrical structures rather than to be a rigorous treatment. 

Two very simple descriptions of the rock salt crystal structure are also given. According to one, the sodium and chloride ions occupy positions with point-group symmetry m3m forming a checkered pattern in the Fm3m space group. According to the other description, the structure consists of two cubic sublattices in parallel orientation, one of sodium ions and the other of chloride ions. 

Fm3m by replacing the symmetry planes m by glide-reflection planes d with the latter displaced i along the cube edges. 

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A rather different method from the preceding is that based on the rate of dissolving of a soluble material. At any given temperature, one expects the initial dissolving rate to be proportional to the surface area, and an experimental verification of this expectation has been made in the case of rock salt (see Refs. 26,27). Here, both forward and reverse rates are important, and the rate expressions are... 

Tolbert S H and Aiivisatos A P 1994 Size dependence of a first order solid-solid phase transition the wurtzite to rock salt transformation in CdSe nanocrystais Science 265 373... 

Rock salt Rutile Caesium chloride Fluorite... 

The stmcture of Pmssian Blue and its analogues consists of a three-dimensional polymeric network of Fe —CN—Fe linkages. Single-crystal x-ray and neutron diffraction studies of insoluble Pmssian Blue estabUsh that the stmcture is based on a rock salt-like face-centered cubic (fee) arrangement with Fe centers occupying one type of site and [Fe(CN)3] units randomly occupying three-quarters of the complementary sites (5). The cyanides bridge the two types of sites. The vacant [Fe(CN)3] sites are occupied by some of the water molecules. Other waters are zeoHtic, ie, interstitial, and occupy the centers of octants of the unit cell. The stmcture contains three different iron coordination environments, Fe C, Fe N, and Fe N4(H20), in a 3 1 3 ratio. 

Transuranic Waste. Transuranic wastes (TRU) contain significant amounts (>3,700 Bq/g (100 nCi/g)) of plutonium. These wastes have accumulated from nuclear weapons production at sites such as Rocky Flats, Colorado. Experimental test of TRU disposal is planned for the Waste Isolation Pilot Plant (WIPP) site near Carlsbad, New Mexico. The geologic medium is rock salt, which has the abiUty to flow under pressure around waste containers, thus sealing them from water. Studies center on the stabiUty of stmctures and effects of small amounts of water within the repository. 

Sodium is not found ia the free state ia nature because of its high chemical reactivity. It occurs naturally as a component of many complex minerals and of such simple ones as sodium chloride, sodium carbonate, sodium sulfate, sodium borate, and sodium nitrate. Soluble sodium salts are found ia seawater, mineral spriags, and salt lakes. Principal U.S. commercial deposits of sodium salts are the Great Salt Lake Seades Lake and the rock salt beds of the Gulf Coast, Virginia, New York, and Michigan (see Chemicals frombrine). Sodium-23 is the only naturally occurring isotope. The six artificial radioisotopes (qv) are Hsted ia Table 1 (see Sodium compounds). 

Salt that is substantially free of sulfate and other impurities is the cell feed. This grade may be purchased from commercial salt suppHers or made on site by purification of cmde sea or rock salt. Dried calcium chloride or cell bath from dismanded cells is added to the bath periodically as needed to replenish calcium coproduced with the sodium. The heat required to maintain the bath ia the molten condition is suppHed by the electrolysis current. Other electrolyte compositions have been proposed ia which part or all of the calcium chloride is replaced by other salts (61—64). Such baths offer improved current efficiencies and production of cmde sodium containing relatively Htde calcium. 

Similar to processing mined rock salt, solar salt may be cmshed, screened, and kiln dried or fluidized-bed dried. Coarse solar salt is a premium product because of high purity and relatively large crystal size. It is in particular demand for use to regenerate the resin in cation-exchange water softeners... 

Salt produced in the United States varies in purity from 95% NaCl for rock salt to 99.99% NaCl for mechanically evaporated salt. Mechanically evaporated salt made using purified brine generally has the highest purity rock salt generally has the lowest. Several voluntary standards and mandatory specifications apply to salt to ensure appropriate gradation, quaUty, and purity for particular salt uses (Table 4). 

Water-soluble crystal modifiers such as yellow pmssiate of soda (YPS) (sodium ferrocyanide decahydrate) or ferric ammonium citrate may also be added to some types of salt as anticaking agents. Both are approved by the U.S. Food and Dmg Administration for use in food-grade salt. YPS and Pmssian Blue (ferric ferrocyanide), are most commonly added to rock salt used for wintertime highway deicing. Concentrations of YPS and Pmssian Blue in deicing salt vary, typically in the range of 20—100 ppm. 

Highway. Rock salt, solar salt, and in some cases in Europe, evaporated salt are used to maintain traffic safety and mobiUty during snow and ice conditions in snowbelt regions throughout the world. Sodium chloride melts ice at temperatures down to its eutectic point of —21.12°C. Most snowstorms occur when the temperature is near 0°C, where salt is very effective. More than 40% of dry salt produced in the United States is used for highway deicing. 

Titanium Monoxide. Titanium monoxide [12137-20-17, TiO, has a rock-salt stmcture but can exist with both oxygen and titanium vacancies. For stoichiometric TiO, the lattice parameter is 417 pm, but varies from ca 418 pm at 46 atom % to 4I62 pm at 54 atom % oxygen. Apparendy, stoichiometric TiO has ca 15% of the Ti and O sites vacant. At high temperatures (>900° C), these vacancies are randomly distributed at low temperatures, they become ordered. Titanium monoxide may be made by heating a stoichiometric mixture of titanium metal and titanium dioxide powders at 1600°C... 

Cadmium Sulfide. CdS [1306-23-6] is dimorphic and exists ia the sphalerite (cubic) and wurtzite (hexagonal) crystal stmctures (40). At very high pressures it may exist also as a rock-salt stmcture type. It is oxidized to the sulfate, basic sulfate, and eventually the oxide on heating ia air to 700°C, especially ia the preseace of moisture (9). 

There has been much interest in making chemicals from brine because of the low expense compared to alternative methods. Lithium, for example, had been mostly produced from spodumene ore, but now most is produced from brine. Those now producing from ore are seriously researching brine reserves and contemplating converting to brine sources before the turn of the century. Similady, solar salt has cost advantages over mined rock salt. Potassium chloride produced from brine has more than doubled from 1980 to 1990. 

Brine Preparation. Rock salt and solar salt (see Chemicals frombrine) can be used for preparing sodium chloride solution for electrolysis. These salts contain Ca, Mg, and other impurities that must be removed prior to electrolysis. Otherwise these impurities are deposited on electrodes and increase the energy requirements. The raw brine can be treated by addition of sodium carbonate and hydroxide to reduce calcium and magnesium levels to below 10 ppm. If further reduction in hardness is required, an ion-exchange resin can be used. A typical brine specification for the Huron chlorate ceU design is given in Table 6. 

Soft Materials (1) Talc, dried filter-press cakes, soapstone, waxes, aggregated salt ciystals (2) gypsum, rock salt, ciystahine salts in gener, soft coal (3) calcite, marble, soft limestone, barites, chalk, brimstone. 

Chemicals The fineness obtainable with a hammer mill on rock salt and chemicals is given in Tables 20-23 and 20-24. 

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