Pretreating the Ore Converting Mineral to Element Converting the Mineral to Another Compound Converting the Compound to the Element Through Chemical Redox Converting the Compound to the Element Through Electrochemical Redox Converting the Mineral to Another Compound
First, the mineral is often converted to another compound,
one that has more appropriate solubility properties, is easier to reduce, or is free of a troublesome impurity. Conversion to an oxide is common because oxides can be reduced easily. Carbonates are heated to convert them to the oxide: CaCO3 (s) CaO(s) + CO2(g) Metal sulfides, such as ZnS, can be converted to oxides by roasting in air: 2 ZnS(s) + 3 O2(g) 2 ZnO(s) + 2 SO2(g) Converting the Compound to the Element Through Chemical Redox Reduction with carbon. Carbon, in the form of coke (a porous residue from incomplete combustion of coal) or charcoal, is a very common reducing agent. Heating an oxide with a reducing agent such as coke to obtain the metal is called smelting. Many metal oxides, such as zinc oxide and tin(lV) oxide, are smelted with carbon to free the metal, which may need to be condensed and solidified: ZnO(s) + C(s) Zn(g) + CO(g) SnO2s) + 2C(s) Sn(l) + 2CO(g) Several nonmetals that occur with positive oxidation states in minerals can be reduced with carbon as well. Phosphorus, for example, is produced from calcium phosphate: 2Ca3(PO4)2(s) + 10C(s) + 6SiO2(s) 6CaSiO3(s) + 10CO(g) + P4(s) (Metallic calcium is a much stronger reducing agent than carbon, so it is not formed) Reduction with hydrogen. For oxides of some metals, especially some members of Groups 6B and 7B, reduction with carbon forms metal carbides. These carbides are difficult to convert further, so other reducing agents are used. Hydrogen gas is used for less active metals, such as tungsten: WO3(s) + 3H2(g) W(s) + 3H2O(g) Reduction with an active metal. When a metal might form an undesirable hydride, its oxide is reduced by a more active metal. In the thermite reaction, aluminum powder reduces the metal oxide in a spectacular exothermic reaction to give the molten metal. The reaction for chromium is Cr2O3(s) + 2AI(s) 2Cr(l) + Al2O3(s) , Ho <<0 Oxidation with an active nonmetal. Just as chemical reduction of a mineral is used to obtain the metal, chemical oxidation of a mineral is sometimes used to obtain a nonmetal. A stronger oxidizing agent is used to remove electrons from the nonmetal anion to give the free nonmetal, as in the industrial production of iodine from concentrated brines by oxidation with chlorine gas: 2I-(aq) + Cl2(g) 2CI-(aq) + I2(s) Converting the Compound to the Element Through Electrochemical Redox
In these processes, the mineral components are converted to the
elements in an electrolytic cell. Sometimes, the pure mineral, in the form of the molten halide or oxide, is used to prevent unwanted side reactions. The cation is reduced to the metal at the cathode and the anion is oxidized to the nonmetal at the anode: BeCl2(l) Be(s) + Cl2(g) High-purity hydrogen gas is prepared by electrochemical reduction: 2H2O(l) 2H2(g) + O2(g) Specially designed cells separate the products to prevent recombination. Cost is a major factor in the use of electrolysis and an inexpensive source of electricity is essential for large-scale methods. Refining and Alloying the Element Refining (Purifying) the Element Refining is a purification procedure, often carried out by one of three common methods: - electrorefining (the impure metal acts as the anode and a sample of the pure metal acts as the cathode), - distillation (for metals with relatively low boiling points, such as zinc and mercury), and - zone refining (impurities are removed from a bar of the element by concentrating them in a thin molten zone, while the purified element recrystallizes. Alloying the Purified Element Alloying a metal with other metals (and, in some cases, nonmetals) is done to alter the metal's melting point and to enhance properties such as luster, conductivity, malleability, ductility, and strength. The manufacture of sulfuric acid Obtaining sulfur - Claus process, in which the H2S in "sour" natural gas is chemically separated and then oxidized: 2H2S(g) + 2O2(g) low temperature 1/8S8(g) + SO2(g) + 2H2O(g) 2H2S(g) + SO2(g) Fe203 catalyst 3/8S8(g) + 2H2O(g) - Frasch process, a nonchemical method that taps natural underground deposits of sulfur. A hole is drilled to the deposit and superheated water (about 160C) is pumped down two outer concentric pipes to melt the sulfur. Then, a combination of the hydrostatic pressure in the outermost pipe and the pressure of compressed air sent through a narrow inner pipe forces the sulfur to the surface. The costs of drilling, pumping, and supplying water (5 X 10 6 gallons per day) are balanced somewhat by the fact that the product is very pure (-99.7% S). From sulfur to sulfur dioxide. Once obtained, the sulfur is burned in air to form SO2: 1/8S8(s) + O2(g) SO2(g) Ho = -297 kJ Some SO2 is also obtained from the roasting of metal sulfide ores. About 90% of processed sulfur is used in making sulfur dioxide for production of the all- important sulfuric acid. From sulfur dioxide to trioxide. The contact process oxidizes SO2 with O2 to SO3: SO2(g) + 1/2O2(g) SO3(g) Ho = -99 kJ The reaction is exothermic and very slow at room temperature. The pressure effect is small and economically not worth exploiting. The concentration effects are controlled by providing an excess of O2 in the form of a 5:1 mixture of air:SO2, or about 1:1 O2:SO2. The mixture is passed over catalyst beds (contact process : V2O5 on inert silica at 400-600oC) in four stages, and the SO3 is removed at several points to favor more SO3 formation. The overall yield of SO3 is 99.5%. From sulfur trioxide to acid. Sulfur trioxide is the anhydride of sulfuric acid, so a hydration step is next. However, SO3 cannot be added to water because, at the operating temperature, it would first meet water vapor, which catalyzes its polymerization to (SO3)x, and results in a smoke of solid particles that makes poor contact with water and yields little acid. To prevent this, previously formed H2SO4 absorbs the SO3 and forms pyrosulfuric acid (or disulfuric acid, H2S2O7), which is then hydrolyzed with sufficient water: SO3(g) + H2O(l) H2SO4(l) - [Iow yield] SO3(g) + H2SO4(l) H2S2O7(l) H2S2O7(l) + H2O(l) 2H2SO4(l)