Carbonates in limestone

Earths land reservoirs play an important role in long-term carbon storage. In fact, they store carbon for very long periods of time. The carbon in limestone, for example, may remain in a land reservoir for thousands of years. The carbon in a fossil fuel may be stored for millions of years. 

As you saw in the last section, the calcium carbonate in limestone can be converted into calcium oxide (lime) and carbon dioxide. At normal temperatures, this reaction is so slow that most limestone formations remain unreacted for thousands of years. Why, then, does it take place rapidly at 1200 °C Similarly, why does the combustion of gasoline take place more quickly when the fuel air mixture in a cylinder of your car is compressed into a smaller volume by a moving piston How does your car s catalytic converter speed the conversion of NO( g ) into N2(j ) and 02 g) Now that we know more about the requirements for reaction, we can proceed to answer questions such as these. 

Although it constimtes only about 0.09 percent by mass of Earth s crust, carbon is an essential element of living matter. It is found free in the form of diamond and graphite (see Figure 8.17), and it is also a component of natural gas, petroleum, and coal. (Coal is a natural dark-brown to black solid used as a fuel it is formed from fossilized plants and consists of amorphous carbon with various organic and some inorganic compounds.) Carbon combines with oxygen to form carbon dioxide in the atmosphere and occurs as carbonate in limestone and chalk. 

In a similar vein, mean seawater temperatures can be estimated from the ratio of 0 to 0 in limestone. The latter rock is composed of calcium carbonate, laid down from shells of countless small sea creatures as they die and fall to the bottom of the ocean. The ratio of the oxygen isotopes locked up as carbon dioxide varies with the temperature of sea water. Any organisms building shells will fix the ratio in the calcium carbonate of their shells. As the limestone deposits form, the layers represent a chronological description of the mean sea temperature. To assess mean sea temperatures from thousands or millions of years ago, it is necessary only to measure accurately the ratio and use a precalibrated graph that relates temperatures to isotope ratios in sea water. 

Chemical-grade limestone is a pure type of high calcium or dolomitic limestone used by the chemical-process industry or where exacting chemical requirements ate necessary. It contains a minimum of 95% total carbonate. In a few areas of the United States this minimum may be extended to 97 or 98%. 

At about the same time that the Birkeland-Eyde process was developed, the Frank-Caro cyanamide process was commercialized (14). In this process limestone is heated to produce lime, which then reacts with carbon in a highly energy-demanding reaction to give calcium carbide. Reaction with N2 gives calcium cyanamide [150-62-7] which hydrolyzes to ammonia and calcium carbonate (see Cyanamides). 

Carbonates and Sulfates Carbonates include limestone, cal-cite, marble, marls, chalk, dolomite, and magnesite the most important sulfates are barite, celestite, anhydrite, and gypsum these are used as fillers in paint, paper, and rubber. (Gypsum and anhydrite are discussed below as part of the cement, lime, and gypsum industries.)... 

Notes. (1) For practice in this determination, the student may employ calcium carbonate or Limestone, 15e (Analysed Samples for Students) from the Bureau of Analysed Samples. 

The CuS is then smelted, a process in which metal ions are reduced by heating the ore with a reducing agent such as carbon (in the form of coke). At the same time, the sulfur is oxidized to S02 by blowing compressed air through the mixture of ore, limestone, and sand ... 

The limestone deposits that decorate Carlsbad and other caverns are the result of the solubility equilibrium of calcium carbonate in groundwater, as described in Chapter 16 ... 

Figure 7.1 Cave formations are caused when rainwater and carbon dioxide mix and form a weak carbonic acid, which then dissolves the calcium carbonate of limestone beneath the earth, allowing for cave formation. The photo shows stalactites and stalagmites and other formations at Luray Caverns in Virginia.

Leblanc wrestled with the problem for five years between 1784 and 1789. Then finally, somehow, someway, he stumbled on the solution. Ancient ironmakers had used carbon in the form of charcoal when hot, the carbon is highly reactive and wrests the oxygen from iron oxide ores. As Leblanc heated his sodium sulfate with charcoal, he added a key new ingredient—common limestone (chalk)—as his source of C03. Almost miraculously, the transformation took place ... 

This technology shows benefits for carbon capture. Limestone is cheap and widely available, and there is a potential for process integration, which can lead to low energy penalties, i.e., heat released from carbonisation can be utilised in a steam cycle or the heat used in the calciner reactor can be recovered in the carbonation process. 

The action of carbonic acid on limestone produces a calcium bicarbonate solution that is exceedingly soluble in water. (For comparison, at 20°C the solubility of calcium carbonate in water is only 0.0145 g per liter while the solubility of calcium bicarbonate is 166 g per literJ ) Magnesium ions from dolomite are also released into aqueous solution according to the same mechanism. The weathering of gypsum, calcium sulfate, also releases calcium ions into natural water supplies. 

Zinc is the 24th most abundant element in the earth s crust. The Zn concentration in the lithosphere is 50-70 mg/kg (Vinogradoc, 1959 Adriano, 2001). Basic igneous rocks contain higher Zn (70-130 mg/kg) than metamorphic and sedimentary rocks (80 mg/kg). Carbonate and limestones contain low Zn (16-20 mg/kg) (Aubert and Pinta, 1977). The total Zn concentration in the soils of the world ranges from 10 to 300 mg/kg (Swaine, 1955), with average concentrations from 50 to 100 mg/kg (Aubert and Pinta, 1977). Arid and semi-arid soils vary from trace levels (subdesert soils) to 900 mg/kg (saline alkali soils) (Aubert and Pinta, 1977). The average Zn concentration in the arid and semi-arid soils of the U.S. (62.9 mg/kg) is... 

Table 8.8 Compositions of superficial and deep waters of the Sarcidano region (Sardinia, Italy) equilibriated with Mesozoic dolomite limestones (Bertorino et ah, 1981). Values in mEq/1. C-j- total inorganic carbon in mmol/1.

The next major raw material for which we discuss the derived chemicals is calcium carbonate, common limestone. It is the source of some carbon dioxide, but, more importantly, it is used to make lime (calcium oxide) and slaked lime (calcium hydroxide). Limestone, together with salt and ammonia, are the ingredients for the Solvay manufacture of sodium carbonate, soda ash. Soda ash is also mined directly from trona ore. The Solvay process manufactures calcium chloride as an important by-product. Soda ash in turn is combined with sand to produce sodium silicates to complete the chemicals in the top 50 that are derived from limestone. Since lime is the highest-ranking derivative of limestone in terms of total amount produced, we discuss it first. Refer to Fig. 2.1, Chapter 2, Section 1, for a diagram of limestone derivatives. 

Mining wastes and overburden. Estonian kukersite oil shales occur in limestone strata (Schmidt 1858, 1881), yielding a carbonate-rich spoil with significant potential for acid neutralisation. Other oil shales, for example, the siliceous Estonian Dictyo-nema shales, which contain only traces of carbonate compared with the kukersites, are associated with sulphides, such as pyrite, and may thus generate acidic leachate due to pyrite oxidation (Puura Pihlak 1998 Puura et al. 1999). 

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