Barium

“ In pharmacy, &c., chiefly to prepare barium salts. In chemistry, to separate certain metallic oxides when occurring together in solutions. In the arts, as a base for certain delicate colours, as an ingredient in plate-glass, in the manufacture of beet sugar, &c. It is not used in medicine. It is extremely poisonous.
Barium, Bisulphide. This substance may be obtained as a fine yellow-coloured product by shaking a solution of barium chloride with a mixture of ammonium sulphide and carbon disulphide. It is insoluble in alcohol, soluble in water, and rapidly dissolved by slightly acidulated water. ”

“ Commercial chloride of barium thus purified is probably the most convenient source of the other compounds of barium when required pure. Thus pure carbonate of baryta may be prepared from it by precipitation with carbonate of ammonia, or with carbonate of soda, which is free from silica, sulphuric acid and phosphoric acid.15
14 It may be that leaden pans are used for the evaporation or cry­stal­li­za­tion of the commercial chloride of barium, which would sufficiently account for the presence of lead in the product. ”

“ Barium occurs chiefly in the form of barytes or heavy spar, BaSO4, and witherite, BaCO3, and to a less extent in baryto-calcite, baryto-celestine, and various complex silicates. The metal is difficult to isolate, and until recently it may be doubted whether the pure metal had been obtained. Sir H. Davy tried to electrolyse baryta, but was unsuccessful; later attempts were made by him using barium chloride in the presence of mercury. In this way he obtained an amalgam, from which on distilling off the mercury the barium was obtained as a silver white residue. ”

“ After the administration per os, much of the barium must be carried off in the diarrheal stools. A number of deaths in horses have been attributed to the use of this agent. No doubt the presence of sulphates, etc., derived from the food would render the barium insoluble in the gastro-intestinal tract, and this would explain the lack of poisonous action in certain of the cases in which large doses of barium proved harmless.
Husard and Biron administered daily doses of 8 grams of barium chlorid to one horse, and the same amount of barium carbonate to a second horse, for several days. ”

“ Especially remarkable are the experiments of A. Debierne, which have been conducted in a similar manner with actinium, and by which it was proved that it is easy to make active the compounds of barium so that they scarcely differ from those of radium, except that they do not give a radium spectrum. The active barium is said to stand between barium and radium, its anhydrous chloride is self-luminous like that of radium, and may equally well, by fractional crystallization, be separated in a more active and a less active portion. ”

“ Hillebrand [182] has called attention to the fact that the igneous rocks of the Rocky Mountains showed a higher percentage of barium than rock from other portions of the United States, so that under these conditions one might expect the presence of barium in plants growing in this region. A sample of Aragallus lamberti and one of Astragalus mollissimus were sent to the Bureau of Chemistry for spectroscopic examination for various elements and they reported traces of barium in each. ”

“ The metallic base of these salts is barium. It is a white, malleable, and fusible metal, readily oxidizing in air, and decomposing water at common temperature. The pure baryta, oxide of barium, is used for the production of peroxide of hydrogen, which is much recommended as a medicinal reagent, and employed in the arts for bleaching animal tissue, and converting brown into blond hair. The oxide, or caustic baryta, rivals, in caustic properties, potash, soda, and ammonia. ”

“ Barytes, or Heavy Spar
The mineral known as heavy spar occurs in very large quantities and in numerous localities. It forms rhombic crystals, which are very often extremely well developed and form flat plates of considerable size. A remarkable peculiarity of this mineral is its high specific gravity, which is due to the barium content. It is found native in all colours, white being the most common.
Chemically, heavy spar is barium sulphate, BaSO4. It can be used as a pigment per se, but only when prepared artificially, the trade name for the product being permanent white, or blanc fixe. ”

“ Generally induced radio-activity obtained in this way scarcely lessens with lapse of time, but it does not as a rule withstand many successive chemical changes of the active body.
79M. Debierne made active barium by placing it in solution with actinium. This barium remains active after several chemical reactions, its activity being therefore a somewhat stable atomic property. Active barium chloride fractionates like barium-radium chloride, the more active portions being the least soluble in water and dilute hydrochloric acid. ”

“ The contents of the stomach are coloured with litmus, and barium carbonate added until the fluid is no longer acid (as shown by the disappearance of the red colour) ; then the contents are evaporated to dryness in a platinum dish, and ignited at a dull red heat; complete burning to an ash is not necessary. After cooling, the burnt mass is repeatedly exhausted with boiling water and filtered; the chloride of barium is precipitated from the filtrate by means of dilute sulphuric acid; the barium sulphate filtered off, washed, dried, and, after ignition, weighed ”

“ A. N. Guntz (Comptes rendus, 1901, 133, p. 872) electrolyses a saturated solution of barium chloride using a mercury cathode and obtains a 3% barium amalgam; this amalgam is transferred to an iron boat in a wide porcelain tube and the tube slowly heated electrically, a good yield of pure barium being obtained at about 1000° C. The metal when freshly cut possesses a silver white lustre, is a little harder than lead, and is extremely easily oxidized on exposure; it is soluble in liquid ammonia, and readily attacks both water and alcohol. ”

“ The amount of barium found in various species of loco plants will no doubt vary, and perhaps the pharmacological test on rabbits as the writer has used it may have to be modified for such plants, so that at present the wisest plan to test these plants is to determine their barium content and also make the physiological test, as has been proposed, and if the barium content runs low, say below 0.11 per cent of the ash, in plants yielding from 12 to 18 per cent of ash, then to increase the number of feedings on the rabbit. ”

“ The baryta is mixed with a portion of hydrate of calcium or of magnesium, and the mixture being placed in an appropriate earthen tube heated to dull redness, is oxidised by passing a current of dry atmospheric air over it. As soon as the oxidation is complete, the tube is connected with the gas-holder, and a jet of steam allowed to act upon it; this reconverts the peroxide of barium into hydrate of barium, the excess of oxygen being given off and collected in the gas-holder. ”

“ The decomposition of the ammonium salt by the hydrated oxide of barium gives the barium salt, BaS2O84H2O, which is soluble to the extent of 52·2 parts in 100 parts of water at 0°. The crystals do not deliquesce in the air and decompose in the course of several days; they decompose most rapidly in perfectly dry air. Solutions of the pure salt decompose slowly at the ordinary temperature; on boiling barium sulphate is gradually precipitated, oxygen being liberated simultaneously. ”

“ From a concentrated solution of either nitrate or chloride of barium, precipitated with a rather strong solution of pure potassa, or of pure soda, perfectly free from carbonic acid.
2. A strong solution of sulphide of barium is boiled with successive portions of black oxide of copper, until it ceases to give a black precipitate with a salt of lead; the liquid, after filtration, yields crystals of the hydrate on cooling. ”

“ Witherite is readily altered to barium sulphate by the action of water containing calcium sulphate in solution, and crystals are therefore frequently encrusted with barytes. It is the chief source of barium salts, and is mined in considerable amounts in Northumberland. It is used for the preparation of rat poison, in the manufacture of glass and porcelain, and formerly for refining sugar. ”

“ The precipitate carries down the active body.
(4) Precipitation of insoluble sulphates. If barium sulphate, for example, is precipitated in the solution containing the active body, the barium carries down the active matter. The thorium and actinium are freed from the barium by conversion of the sulphate into the chloride and precipitation by ammonia.
In this way Debierne has obtained a substance comparable in activity with radium. The separation, which is difficult and laborious, has not yet been carried far enough to bring out any new lines in the spectrum. ”

“ Fractions 2, 3, and 4 were treated in an exactly similar way, the barium salts obtained and the weight and percentage of barium sulphate being shown in the following table:—
Calculating the fractions 1 and 2 as mixtures of barium butyrate and acetate, and fractions 3 and 4 as mixtures of barium acetate and formate, we may summarise the results thus:—
or as free acids:—
Proceeding now to (3) non-volatile bodies, we find these to consist of (1) acids, and (2) soluble carbohydrates. For examination, the remaining 4 litres of experimental drench were evaporated down to 1 litre and filtered ”

“ The examination of this fluid for barium might, however, be [Pg 68] misleading, as the large amount of proteids would unquestionably interfere with the determination of this amount of barium, unprotected by other salts and silica, so that this side of the investigation was not pursued. Control feedings with an emulsion of one-half gram each of pepsin and pancreatin proved inactive. ”

“ Experience has shown that water which contains appreciable quantities of organic matter does not give a pure white product. The presence of sulphate of lime in the water, which precipitates barium sulphate, need not be regarded, because the barium sulphate is so finely divided that it remains suspended in the liquid, and is carried down on precipitation of the enamel white by sulphuric acid. Carbonate of lime in the water causes the separation of barium carbonate; this may be avoided by slightly acidifying the barium chloride solution, thus converting the calcium carbonate into chloride. ”

“ Dissolve lactate of barium in water, precipitate the barium with dilute sulphuric acid, carefully avoiding excess, and gently evaporate to the consistence of a syrup, or until it acquires the density 1·215. Lactate of calcium may be used instead of lactate of barium, in which case a solution of oxalic acid must be employed as the precipitant. ”

“ This seems to prove that the radioactivity does not keep pace with the concentration of the barium compounds, but lags far behind. A reliable measure of the radium-amount is not furnished. Even a preparation of 3,500 activity must have consisted mainly of barium chloride, since it yielded 140 for the atomic weight which is only slightly in excess of that of barium. As to the activity of the purest radium chloride, we find no statements, but it is said that the best radium preparations have an activity of 50,000 to 100,000 times that of uranium. ”

“ The dry chloride is spontaneously luminous: its Becquerel radiation is similar to that of barium-radium chloride. M. Debierne has prepared an active barium chloride 1000 times as active as uranium. This barium, however, had not acquired all the characteristics of radium, for it showed none of the strongest radium lines in the spectroscope. Further, its activity diminished on standing, and after three weeks it had become one-third of its original value.
There is a wide field for research upon the radio-activity induced in substances in solution with active bodies. ”

“ The barium precipitate was treated with dilute hydrochloric acid and heated to boiling to decompose the barium resinate, and to liberate the free resin acid. The liberated acid was a brown resin of a thin consistency and had a characteristic odor. This acid was removed by [Pg 11] shaking out with ether. The ethereal solution was dried with anhydrous sodium sulphate, filtered, and the ether removed by distillation. The last traces of ether were removed by heating the resin acids in a vacuum oven at sixty five degrees Centigrade. ”

“ The fact that treatment of the loco-weed extract with a few drops of sulphuric acid, which will remove the barium, renders these extracts harmless, and even apparently nutritious, would suggest the theoretical antidotal treatment to be with sulphates, in the form, perhaps, of epsom salts, but perhaps alkaline bicarbonates may be present in the stomach, either due to lessened acidity of the stomach or from drinking alkaline waters, in which case the precipitation of the barium by sulphates would presumably be interfered with, and thus the treatment be rendered ineffectual. ”

“ One sample of the soil from near Hugo, Colo., from which the Aragallus lamberti was collected, was examined by the Bureau of Soils, and that Bureau reported the absence of barium and zirconium, at least of any recognizable by the chemical methods used, so that it can not be said that the barium came from any soil accidentally mixed with the ash. Traces of titanium were, however, found. Evidently the plant must collect minimal quantities of these elements from the soil and store them. ”

“ Radium rays transform barium platinocyanide into a brown, less luminous variety (an action similar to that produced by Röntgen rays, and described by M. Villard) . Uranium sulphate and potassium sulphate are similarly altered. The changed barium platinocyanide is partially regenerated by the action of light. If the radium be placed beneath a layer of barium platinocyanide spread on paper, the platinocyanide becomes luminous; if the system be kept in the dark, the platinocyanide becomes changed, and its luminosity diminishes considerably. ”