In sea water

The alkali metals of Group I are found chiefly as the chlorides (in the earth s crust and in sea water), and also as sulphates and carbonates. Lithium occurs as the aluminatesilicate minerals, spodimene and lepidolite. Of the Group II metals (beryllium to barium) beryllium, the rarest, occurs as the aluminatesilicate, beryl-magnesium is found as the carbonate and (with calcium) as the double carbonate dolomite-, calcium, strontium and barium all occur as carbonates, calcium carbonate being very plentiful as limestone. 

Bromides of sodium, potassium, magnesium and calcium occur in sea water (about 0.07 % bromine) but the Dead Sea contains much more (5% bromine). Salt deposits (e.g. at Stassfurt) also contain these bromides. Silver bromide, AgBr, is found in South America. 

Iodine occurs to a minute extent (less than 0.001 %) in sea water, but is found in greater concentration, combined in organic form, in certain seaweeds, in oysters and in cod livers. Crude Chile saltpetre, or caliche contains small amounts of sodium iodate, NalOj. from which iodine can be obtained (see below). Some insoluble iodides, for example liiose of silver and mercury(II), occur in Mexico. Iodine is found in the human body in the compound thyroxin in the thyroid gland deficiency of iodine in diet causes enlargement of this gland (goitre). 

Gr. iodes, violet) Discovered by Courtois in 1811, Iodine, a halogen, occurs sparingly in the form of iodides in sea water from which it is assimilated by seaweeds, in Chilean saltpeter and nitrate-bearing earth, known as caliche in brines from old sea deposits, and in brackish waters from oil and salt wells. 

Trace metals in sea water are preconcentrated either by coprecipitating with Ee(OH)3 and recovering by dissolving the precipitate or by ion exchange. The concentrations of several trace metals are determined by standard additions using graphite furnace atomic absorption spectrometry. 

The concentration of chloride in sea water can be determined by a flow injection analysis. The analysis of a set of calibration standards gives the results in the following table. 

The use of accurate isotope ratio measurement is exemplified here by a method used to determine the temperature of the Mediterranean Sea 10,000 years ago. It is known that the relative solubility of the two isotopic forms of carbon dioxide COj) in sea water depends on temperature... 

By experimentally determining the ratio of abundances of C and isotope peaks for CO2 dissolved in sea water at various temperatures, a graph can be drawn relating the solubility of CO2 compared with that of CO2 (the ratio described above). On extracting the CO2 from sediment containing the shells (calcium carbonate) of dead sea creatures by addition of acid, a ratio (R) of abundances of CO2 to CO2 can be measured. If this value is read from the graph, a temperature T is extrapolated, indicating the temperature of the sea at the time the sediment was laid down. Such experiments have shown that 10,000 years ago the temperature of the Mediterranean was much as it is now. 

One method for measuring the temperature of the sea is to measure this ratio. Of course, if you were to do it now, you would take a thermometer and not a mass spectrometer. But how do you determine the temperature of the sea as it was 10,000 years ago The answer lies with tiny sea creatures called diatoms. These have shells made from calcium carbonate, itself derived from carbon dioxide in sea water. As the diatoms die, they fall to the sea floor and build a sediment of calcium carbonate. If a sample is taken from a layer of sediment 10,000 years old, the carbon dioxide can be released by addition of acid. If this carbon dioxide is put into a suitable mass spectrometer, the ratio of carbon isotopes can be measured accurately. From this value and the graph of solubilities of isotopic forms of carbon dioxide with temperature (Figure 46.5), a temperature can be extrapolated. This is the temperature of the sea during the time the diatoms were alive. To conduct such experiments in a significant manner, it is essential that the isotope abundance ratios be measured very accurately. 

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. 

V. B. Chemo2ubov and co-workers, in Proceedings of the 1 st International Symposium on Water Desalination, Washington, D.C., Oct. 1965, p. 139. CIBA-Geigy Corp., The Application ofBelgardEU and Belgard EUN in Sea Water Evaporators, CIBA-GEIGY pamphlet DB 21. 

TABLE 28-1 b Galvanic Series in Sea Water (Approx )/ Volts vs Sat Calomel Ref Electrode... 

Many shell-and-tube condensers use copper alloy tubes, such as admiralty brasses (those containing small concentrations of arsenic, phosphorus, or antimony are called inhibited grades), aluminum brasses, and cupronickel austenitic stainless steel and titanium are also often used. Utility surface condensers have used and continue to use these alloys routinely. Titanium is gaining wider acceptance for use in sea water and severe service environments but often is rejected based on perceived economic disadvantages. 

In sea water with a pH of 8, crevice pH may fall helow 1 and chloride concentration can be many times greater than in the water. The crevice environment becomes more and more corrosive with time as acidic anions concentrate within. Areas immediately adjacent to the crevice receive ever-increasing numbers of electrons from the crevice. Hydroxyl ion formation increases just outside the crevice—locally increasing pH and decreasing attack there (Reaction 2.2). Corrosion inside the crevice becomes more severe with time due to the spontaneous concentration of acidic anion. Accelerating corrosion is referred... 

The crevice shape markedly affects corrosion. Crevices so tight that water may not enter are entirely immune to attack. In misting environments or alternately wet-diy environments, the crevice holds water and may allow continued attack even when neeu by surfaces eire dry. In sea water, the severity of attack in stainless steel crevices depends on the ratio of the crevice area to the cathodic surface area outside the crevice. If the cathodic area is large relative to crevice eirea, corrosion is promoted. 

Generai description. Galvanic corrosion refers to the preferential corrosion of the more reactive member of a two-metal pair when the metals are in electrical contact in the presence of a conductive fluid (see Chap. 16, Galvanic Corrosion ). The corrosion potential difference, the magnitude of which depends on the metal-pair combination and the nature of the fluid, drives a corrosion reaction that simultaneously causes the less-noble pair member to corrode and the more-noble pair member to become even more noble. The galvanic series for various metals in sea water is shown in Chap. 16, Table 16.1. Galvanic potentials may vary with temperature, time, flow velocity, and composition of the fluid. 

A galvanic series has been constructed that lists numerous industrial metals according to their galvanic potential in sea water. Table 16.1 is such a listing for metals often found in cooling water systems. 

Table 16.2 summarizes the probable galvanic activity of various metals in sea water. 

TABLE 16.1 Galvanic Series of Selected Metals in Sea Water ... 

Some years after Davy s death, Faraday examined the corrosion of cast iron in sea water and found that it corrodes faster near the water surface than deeper down. In 1834 he discovered the quantitative connection between corrosion weight loss and electric current. With this discovery he laid the scientific foundation of electrolysis and the principles of cathodic protection. 

USSR 76 and Brazil 37 tonnes of contained Be, which together accounted for 98% of world production. The cost of Be metal was 690/kg in 1987. By contrast, world supplies of magnesium are virtually limitless it occurs to the extent of 0.13% in sea water, and electrolytic extraction at the present annual rate, if continued for a million years, would only reduce this to 0.12%. 

Data after Fontana and Greene source International Nickel Co. t Immersed in tidal current. t Immersed in sea-water flume. 

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