YTTRIA.
Yttria is found in gadolinite and some other rare minerals. It is precipitated along with the other earths by ammonia. It is distinguished by the insolubility of its hydrate in potash, by the insolubility of its oxalate in oxalic acid, and by not being precipitated by hyposulphite of soda or pota.s.sium sulphate. Further, it is precipitated by potash in the presence of tartaric acid as an insoluble tartrate. This reaction distinguishes the members of the yttria group from most of the other earths. The other members of the group closely resemble it, and amongst them are erbia, terbia, ytterbia, scandia, &c.
BERYLLIA.
The oxide of beryllium, BeO (also known as glucina), occurs in nature mainly as silicate. Beryl, the green transparent variety of which is the emerald, is the best known of these. It is a silicate of alumina and beryllia.[91] Some other minerals in which it occurs are phenakite, euclase, and chrysoberyl.
In the ordinary course of a.n.a.lysis, beryllia will be precipitated with alumina, &c., by ammonic hydrate. It is distinguished by the solubility of its hydrate in ammonic carbonate, by not being precipitated by boiling with sodium hyposulphite, and by not being precipitated by ammonic sulphide from an ammonic carbonate solution.
The a.n.a.lysis of silicates containing beryllia is thus effected. The finely powdered substance is fused with twice its weight of pota.s.sium carbonate; and the "melt" is extracted with water, and evaporated with a slight excess of sulphuric acid to render the silica insoluble. Treat with water, filter, and evaporate the filtrate until a crust is formed.
Potash alum crystallises out. The liquor is poured off into a warm strong solution of ammonium carbonate. Ferric hydrate and alumina will be precipitated. They are filtered off, re-dissolved, and again precipitated in ammonic carbonate solution; the combined filtrates are boiled for some time, and acidified slightly with hydrochloric acid. The carbon dioxide is boiled off, and the beryllia is then precipitated as hydrate with ammonia. The hydrate is washed with hot water, dried, ignited, and weighed as beryllia, BeO.
Beryllia has a specific gravity of 3.08. It is white, infusible, and insoluble in water. After ignition, it is insoluble in acids, except sulphuric, but is rendered soluble by fusion with alkalies.
Beryllia, in a solution of carbonate of ammonia, is precipitated as carbonate on boiling in proportion as the carbonate of ammonia is volatilised. The hydrate is dissolved by a boiling solution of ammonic chloride, ammonia being evolved.
THE ALKALINE EARTHS.
LIME.
Lime is an oxide of calcium, CaO. It occurs abundantly in nature, but only in a state of combination. The carbonate (CaCO_{3}), found as limestone, chalk, and other rocks, and as the minerals calcite and arragonite, is the most commonly occurring compound. The hydrated sulphate, gypsum (CaSO_{4}.2H_{2}O), is common, and is used in making "plaster of Paris." Anhydrite (CaSO_{4}) also occurs in rock ma.s.ses, and is often a.s.sociated with rock salt. Phosphate of lime, in the forms of apat.i.te, phosphorite, coprolite, &c., is largely mined. Lime is a component of most natural silicates. Calcium also occurs, combined with fluorine, in the mineral fluor (CaF_{2}). In most of these the acid is the important part of the mineral; it is only the carbonate which is used as a source of lime.
Lime, in addition to its use in mortars and cements, is valuable as a flux in metallurgical operations, and as a base in chemical work on a large scale. A mixture of lime and magnesia is used in the manufacture of basic fire-bricks.
Carbonate of lime on ignition, especially when in contact with reducing substances, loses carbonic acid, and becomes lime. This is known as "quicklime"; on treatment with water it becomes hot, expands, and falls to a powder of "slaked lime" or calcium hydrate (CaH_{2}O_{2}). The hydrate is slightly soluble in water (0.1368 gram in 100 c.c.), forming an alkaline solution known as lime-water. Calcium hydrate is more generally used suspended in water as "milk of lime."
As a flux it is used either as limestone or as quicklime. Silica forms with lime a compound, calcium silicate, which is not very fusible; but when alumina and other oxides are present, as in clays and in most rocky substances, the addition of lime gives a very fusible slag.
~Detection.~--Calcium is detected by the reddish colour which its salts impart to the flame. It is best to moisten with hydrochloric acid (or, in the case of some silicates, to treat with ammonium fluoride) before bringing the substance into the flame. When seen through a spectroscope, it shows a large number of lines, of which a green and an orange are most intense and characteristic. Calcium is detected in solution (after removal of the metals by treatment with sulphuretted hydrogen and ammonium sulphide) by boiling with ammonium oxalate and ammonia. The lime is completely thrown down as a white precipitate. Lime is distinguished from the other alkaline earths by forming a sulphate insoluble in dilute alcohol, but completely soluble in a boiling solution of ammonium sulphate.
Lime compounds are for the most part soluble in water or in dilute hydrochloric acid. Calcium fluoride must be first converted into sulphate by evaporation in a platinum dish with sulphuric acid.
Insoluble silicates are opened up by fusion with "fusion mixture," as described under _Silica_.
~Separation.~--The separation of lime is effected by evaporating with hydrochloric acid, to separate silica; and by treating with sulphuretted hydrogen, to remove the second group of metals. If the substance contains much iron, the solution is next oxidised by boiling with a little nitric acid; and the iron, alumina, &c., are removed as basic acetates. The filtrate is treated with ammonia and sulphuretted hydrogen, and allowed to settle. The filtrate from this is heated to boiling, treated with a solution of ammonium oxalate in excess, boiled for five or ten minutes, allowed to settle for half an hour, and filtered. The precipitate contains all the lime as calcium oxalate.
GRAVIMETRIC DETERMINATION.
The precipitate of calcium oxalate is washed with hot water, dried, transferred to a weighed platinum crucible, and ignited at a temperature not above incipient redness. This ignition converts the oxalate into carbonate, with evolution of carbonic oxide, which burns at the mouth of the crucible with a blue flame.[92] Generally a small quant.i.ty of the carbonate is at the same time converted into lime. To reconvert it into carbonate, moisten with a few drops of ammonic carbonate solution, and dry in a water-oven. Heat gently over a Bunsen burner, cool, and weigh. The substance is calcium carbonate (CaCO_{3}), and contains 56 per cent. of lime (CaO). It is a white powder, and should show no alkaline reaction with moistened litmus-paper.
Where the precipitate is small, it is better to ignite strongly over the blowpipe, and weigh directly as lime. With larger quant.i.ties, and when many determinations have to be made, it is easier to make the determination volumetrically.
VOLUMETRIC METHODS.
These are carried out either by dissolving the oxalate at once in dilute sulphuric acid, and t.i.trating with permanganate of pota.s.sium solution; or by calcining it to a mixture of lime and carbonate, and determining its neutralising power with the standard solutions of acid and alkali.
~t.i.tration with Permanganate of Pota.s.sium Solution.~--This solution is made by dissolving 5.643 grams of the salt in water, and by diluting to 1 litre; 100 c.c. are equivalent to 0.5 gram of lime. The solution is standardised by t.i.trating a quant.i.ty of oxalic acid about equivalent to the lime present in the a.s.say; 0.5 gram of lime is equivalent to 1.125 gram of crystallised oxalic acid. The standardising may be done with iron. The standard found for iron multiplied by 0.5 gives that for lime.
The process is as follows:--The calcium oxalate (having been precipitated and washed, as in the gravimetric process) is washed through the funnel into a flask with hot dilute sulphuric acid, boiled till dissolved, diluted to 200 c.c. with water, and heated to about 80 C.
The standard solution of "permanganate" is then run in, (not too quickly, and with constant shaking) until a permanent pink tinge is produced. The c.c. used multiplied by the standard, and divided by the weight of the substance taken, will give the percentage of lime.
~Estimation of Lime by Alkalimetry.~--The methods of determining the amount of an alkali or base by means of a standard acid solution, or, conversely, of determining an acid by means of a standard alkaline solution, are so closely related that they are best considered under one head. The same standard solution is applicable for many purposes, and, consequently, it is convenient to make it of such strength that one litre of it shall equal an equivalent in grams of any of the substances to be determined. Such solutions are termed _normal_. For example, a solution of hydrochloric acid (HCl = 36.5) containing 36.5 grams of real acid per litre, would be normal and of equivalent strength to a solution containing either 17 grams of ammonia (NH_{3} = 17) or 40 grams of sodic hydrate (NaHO = 40) per litre. It will be seen in these cases that the normal solution contains the molecular weight in grams per litre; and, if solutions of these strengths be made, it will be found that they possess equal neutralising value.
If, now, a solution containing 98 grams of sulphuric acid (H_{2}SO_{4} = 98) per litre be made, it will be found to have twice the strength of the above solution, that is, 100 c.c. of the soda would only require 50 c.c. of the acid to neutralise it. The reason for this will be seen on inspecting the equations:--
NaHO + HCl = NaCl + H_{2}O.
2NaHO + H_{2}SO_{4} = Na_{2}SO_{4} + 2H_{2}O.
Acids like sulphuric acid are termed bibasic, and their equivalent is only half the molecular weight. Thus, a normal solution of sulphuric acid would contain 49 grams (98/2) of real acid per litre. Similarly, lime and most of the bases are bibasic, as may be seen from the following equations; hence their equivalent will be half the molecular weight.
2HCl + CaO = CaCl_{2} + H_{2}O.
2HCl + MgO = MgCl_{2} + H_{2}O.
_The standard normal solution of hydrochloric acid_ is made by diluting 100 c.c. of the strong acid to one litre with water. This will be approximately normal. In order to determine its exact strength, weigh up 3 grams of recently ignited pure sodium carbonate or of the ignited bicarbonate. Transfer to a flask and dissolve in 200 c.c. of water; when dissolved, cool, tint faintly yellow with a few drops of a solution of methyl orange, and run in the standard "acid " from a burette till the yellow changes to a pink. Read off the number of c.c. used, and calculate to how much sodium carbonate 100 c.c. of the "acid" are equivalent. If the "acid" is strictly normal, this will be 5.3 grams. It will probably be equivalent to more than this. Now calculate how much strictly normal "acid" would be equivalent to the standard found. For example: suppose the standard found is 5.5 gram of sodium carbonate, then--
5.3 : 5.5 :: 100 : _x_ (where _x_ is the quant.i.ty of normal "acid" required).
_x_ = 103.8 c.c.
To get the "acid" of normal strength, we should then add 3.8 c.c. of water to each 100 c.c. of the standard solution remaining. Suppose there were left 930 c.c. of the approximate "acid," 35.3 c.c. of water must be added and mixed. It should then be checked by another t.i.tration with pure sodium carbonate.
_The standard solution of semi-normal "alkali."_ The best alkali for general purposes is ammonia, but, since it is volatile (especially in strong solutions), it is best to make it of half the usual strength, or _semi-normal_. One litre of this will contain 8.5 grams of ammonia (NH_{3}), and 100 c.c. of it will just neutralise 50 c.c. of the normal "acid." Take 100 c.c. of dilute ammonia and dilute with water to one litre. Run into a flask 50 c.c. of the standard "acid," tint with methyl orange, and run in from a burette the solution of ammonia till neutralised. Less than 100 c.c. will probably be used. Suppose 95 c.c.
were required, there should have been 100, hence there is a deficiency of five. Then, for each 95 c.c. of standard "ammonia" left, add 5 c.c.
of water, and mix well. 100 c.c. will now be equivalent to 50 c.c. of the "acid."
As an example of the application of this method, we may take the determination of lime in limestone, marble, and similar substances.
~Determination of Lime in Limestone.~--Weigh up 1 gram of the dried sample, and dissolve in 25 c.c. of normal acid, cool, dilute to 100 c.c., and t.i.trate with the semi-normal solution of alkali (using methyl-orange as an indicator). Divide the c.c. of alkali used by 2, subtract from 25, and multiply by 0.028 to find the weight of lime. This method is not applicable in the presence of other carbonates or oxides, unless the weight of these substances be afterwards determined and due correction be made.
STRONTIA.
Strontia, the oxide of strontium (SrO), occurs in nature as sulphate, in the mineral celestine (SrSO_{4}), and as carbonate in strontianite (SrCO_{3}). It is found in small quant.i.ties in limestones, chalk, &c.
Strontia is used in sugar-refining, and for the preparation of coloured lights.
~Detection.~--It is detected by the crimson colour which its compounds (when moistened with hydrochloric acid) impart to the flame. The spectrum shows a large number of lines, of which a red, an orange, and a blue are most characteristic.
It resembles lime in many of its compounds, but is distinguished by the insolubility of its sulphate in a boiling solution of ammonium sulphate, and by the insolubility of its nitrate in alcohol. From baryta, which it also resembles, it is distinguished by not yielding an insoluble chromate in an acetic acid solution, by the solubility of its chloride in alcohol, and by the fact that its sulphate is converted into carbonate on boiling with a solution formed of 3 parts of pota.s.sium carbonate and 1 of pota.s.sium sulphate.
It is got into solution in the same manner as lime. The sulphate should be fused with "fusion mixture," extracted with water, and thoroughly washed. The residue will contain the strontia as carbonate, which is readily soluble in dilute hydrochloric or nitric acid.
~Separation.~--It is separated (after removal of the silica and metals, as described under _Lime_) by adding ammonia and ammonia carbonate, and allowing to stand for some hours in a warm place. In the absence of baryta or lime it is filtered off, and weighed as strontium carbonate, which contains 70.17 per cent. of strontia. It is separated from baryta by dissolving in a little hydrochloric acid, adding ammonia in excess, and then acidifying with acetic acid, and precipitating the baryta with pota.s.sium bichromate, as described under _Baryta_. The strontia is precipitated from the filtrate by boiling for some time with a strong solution of ammonic sulphate and a little ammonia. Fifty parts of ammonic sulphate are required for each part of strontia or lime present.
The precipitate is filtered off, and washed first with a solution of ammonic sulphate, and then with alcohol. It is dried, ignited and weighed as strontium sulphate.