Strontium and in Barium

FIGURE 14.19 The elements of Croup 2 (a) beryllium (b) magnesium (c) calcium id) strontium and (c) barium. The four central elements of the group (magnesium through barium) were discovered bv I lumphry Davy in a single year (1 808). The two outer elements were discovered later beryllium in 1828 (by Friedrich Wohler) and radium (which is not shown here) in 1898 (by Pierre and Marie Curie). 

Hydroxo salt is the term used for a group of complexes where the central atom of the complex anion is a metal to which hydroxyl ions are bound as ligands. The niunber of these ions depends on the normal coordination number of the metal. The cation of a hydroxo salt is usually an alkali metal, particularly sodium, or the alkaline earth metals barium, strontium and, in some cases, calciiun. Heavy-metal salts can be prepared from a few hydroxo anions via a double decomposition reaction. 

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. 

Calcium, strontium and barium produce characteristic flame colours like the Group 1 cations (calcium, orange strontium, red barium, green) and flame photometry can be used for their estimation. All give insoluble carbonates in neutral solution. 

OtherAlkaline-Parth Hydrides. Strontium and barium hydrides resemble calcium hydride in properties and reactivity. They have no significant commercial apphcations. 

Sa.lts Salting out metal chlorides from aqueous solutions by the common ion effect upon addition of HCl is utilized in many practical apphcations. Typical data for ferrous chloride [13478-10-9] FeCl2, potassium chloride [7447-40-7] KCl, and NaCl are shown in Table 9. The properties of the FeCl2-HCL-H2 0 system are important to the steel-pickling industry (see Metal SURFACE TREATMENTS Steel). Other metal chlorides that are salted out by the addition of hydrogen chloride to aqueous solutions include those of magnesium, strontium, and barium. 

At room temperature, sulfur unites readily with copper, silver, and mercury and vigorously with sodium, potassium, calcium, strontium, and barium to form sulfides. Iron, chromium, tungsten, nickel, and cobalt react much less readily. In a finely divided state, zinc, tin, iron, and aluminum react with sulfur on heating (19). 

Barium titanate thin films can be deposited on various substances by treating with an aqueous solution containing barium salts and an alkanolamine-modifted titanate such as TYZOR TE (151). In a similar fashion, reaction of a tetraalkyl titanate with an alkah metal hydroxide, such as potassium hydroxide, gives oxyalkoxide derivatives (KTi O(OR) ), which can be further processed to give alkali metal titanate powders, films, and fibers (152—155). The fibers can be used as adsorbents for radioactive metals such as cesium, strontium, and uranium (156). 

Barium [7440-39-3] Ba, is a member of Group 2 (IIA) of the periodic table where it Hes between strontium and radium. Along with calcium and strontium, barium is classed as an alkaline earth metal, and is the densest of the three. Barium metal does not occur free in nature however, its compounds occur in small but widely distributed amounts in the earth s cmst, especially in igneous rocks, sandstone, and shale. The principal barium minerals are barytes [13462-86-7] (barium sulfate) and witherite [14941-39-0] (barium carbonate) which is also known as heavy spar. The latter mineral can be readily decomposed via calcination to form barium oxide [1304-28-5] BaO, which is the ore used commercially for the preparation of barium metal. 

Barium is a member of the aLkaline-earth group of elements in Group 2 (IIA) of the period table. Calcium [7440-70-2], Ca, strontium [7440-24-6], Sr, and barium form a closely aUied series in which the chemical and physical properties of the elements and thek compounds vary systematically with increa sing size, the ionic and electropositive nature being greatest for barium (see Calcium AND CALCIUM ALLOYS Calcium compounds Strontium and STRONTIUM compounds). As size increases, hydration tendencies of the crystalline salts increase solubiUties of sulfates, nitrates, chlorides, etc, decrease (except duorides) solubiUties of haUdes in ethanol decrease thermal stabiUties of carbonates, nitrates, and peroxides increase and the rates of reaction of the metals with hydrogen increase. 

The classical analytical method of deterruination of barium ion is gravimetric, by precipitating and weighing insoluble barium sulfate. Barium chromate, which is more insoluble than strontium chromate in a slightly acidic solution, gives a fairly good separation of the two elements. 

Alkaline-earth metals are often deterruined volumetricaHy by complexometric titration at pH 10, using Eriochrome Black T as indicator. The most suitable complexing titrant for barium ion is a solution of diethylenetriaminepentaacetic acid (DTPA). Other alkaline earths, if present, are simultaneously titrated, and in the favored analytical procedure calcium and strontium are deterruined separately by atomic absorption spectrophotometry, and their values subtracted from the total to obtain the barium value. 

Historically, materials based on doped barium titanate were used to achieve dielectric constants as high as 2,000 to 10,000. The high dielectric constants result from ionic polarization and the stress enhancement of k associated with the fine-grain size of the material. The specific dielectric properties are obtained through compositional modifications, ie, the inclusion of various additives at different doping levels. For example, additions of strontium titanate to barium titanate shift the Curie point, the temperature at which the ferroelectric to paraelectric phase transition occurs and the maximum dielectric constant is typically observed, to lower temperature as shown in Figure 1 (2). 

The chemical identities of the fission products determine their subsequent redistribution, those elements which are in the gaseous state at the temperature of the operation migrating to the cooler exterior of the fuel rods, and die less voltile elements undergoing incorporation in the fuel rod in solid solution. Thus caesium and iodine migrate to the gas fill which sunounds the fuel rod, and elements such as the rare earths and zirconium are accommodated in solid solution in UO2 without significant migration along the fuel rod radius. Strontium and barium oxidize to form separate islands which can be seen under the microscope. 

Resoles are usually those phenolics made under alkaline conditions with an excess of aldehyde. The name denotes a phenol alcohol, which is the dominant species in most resoles. The most common catalyst is sodium hydroxide, though lithium, potassium, magnesium, calcium, strontium, and barium hydroxides or oxides are also frequently used. Amine catalysis is also common. Occasionally, a Lewis acid salt, such as zinc acetate or tin chloride will be used to achieve some special property. Due to inclusion of excess aldehyde, resoles are capable of curing without addition of methylene donors. Although cure accelerators are available, it is common to cure resoles by application of heat alone. 

Experimentally we find that strontium and barium hydroxides are indeed strong bases. All of the alkaline earth hydroxides dissolve readily in acidic solutions, showing that they are all bases to some extent ... 

The sparingly soluble sulphates (e.g. those of barium, strontium, and lead) also exhibit increased solubility in acids as a consequence of the weakness of the second-stage ionisation of sulphuric acid (K2 = 1.2 x 10 2 mol L1) ... 

Both carbonates decompose to their oxides with the evolution of carbon dioxide. The decomposition temperature for calcium carbonate is in the temperature range 650-850 °C, whilst strontium carbonate decomposes between 950 and 1150°C. Hence the amount of calcium and strontium present in a mixture may be calculated from the weight losses due to the evolution of carbon dioxide at the lower and higher temperature ranges respectively. This method could be extended to the analysis of a three-component mixture, as barium carbonate is reported to decompose at an even higher temperature ( 1300 °C) than strontium carbonate. 

In 1817 Dobereiner found that if certain elements were combined with oxygen in binary compounds, a numerical relationship could be discerned among the equivalent weights of these compounds. Thus when oxides of calcium, strontium, and barium were considered, the equivalent weight of strontium oxide was approximately the mean of those of calcium oxide and barium oxide. The three elements in question, strontium, calcium, and barium were said to form a triad. 

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