A Text-book of Assaying: For the Use of Those Connected with Mines Part 60

FOOTNOTES:

[101] BaCl_{2} + Na_{2}SO_{4} = BaSO_{4} + 2NaCl.

[102] Se + KCy = KCySe.

CHAPTER XVII.

a.r.s.eNIC, PHOSPHORUS, NITROGEN.

a.r.s.eNIC.

The chief source of the a.r.s.enic of commerce is a.r.s.enical pyrites, or mispickel, which contains about 45 per cent. of a.r.s.enic (As). a.r.s.enic also occurs as a const.i.tuent of several comparatively rare minerals; and, as an impurity, it is very widely distributed. White a.r.s.enic is an oxide of a.r.s.enic, and is obtained by roasting a.r.s.enical ores, and refining the material (crude a.r.s.enic), which condenses in the flues.

a.r.s.enic itself is volatile, and many of its compounds have the same property. It forms two well-defined series of salts, corresponding to the oxides: a.r.s.enious oxide (As_{2}O_{3}), and a.r.s.enic oxide (As_{2}O_{5}). These combine with bases to form a.r.s.enites and a.r.s.enates respectively. Boiling with nitric acid converts the lower into the higher oxide; and powerful reducing-agents, such as cuprous chloride, have the opposite effect.

a.r.s.enic may be detected by dissolving the substance in hydrochloric acid, or in aqua regia (avoiding an excess of nitric acid), and adding a little of this solution to the contents of a small flask in which hydrogen is being made by the action of zinc and hydrochloric acid. The ignited jet of hydrogen a.s.sumes a blue colour if a.r.s.enic is present, and a cold porcelain dish held in the flame (fig. 67) becomes coated with a dark deposit of metallic a.r.s.enic. Antimony produces a similar effect, but is distinguished by the insolubility of its deposit in a cold solution of bleaching-powder.

[Ill.u.s.tration FIG. 67.]

a.r.s.enites are distinguished by the volatility of the chloride; by decolorising a solution of permanganate of pota.s.sium, and by immediately giving a yellow precipitate with sulphuretted hydrogen. a.r.s.enates are distinguished (after converting into soda salts by boiling with carbonate of soda and neutralising) by giving with nitrate of silver a red precipitate, and with "magnesia mixture" a white crystalline one.

~Dry a.s.say.~--There is no dry a.s.say which is trustworthy. The following method is sometimes used to find the proportion of a.r.s.enious oxide in "crude a.r.s.enic":--Weigh up 5 grams of the dried sample, and place them in a clean dry test-tube about 6 inches long. Tie a small filter-paper over the mouth of the tube, so as to prevent air-currents. Heat the tube cautiously so as to sublime off the white a.r.s.enic into the upper part of the tube. Cut off the bottom of the test-tube by wetting whilst hot.

Sc.r.a.pe out the a.r.s.enic and weigh it. The weight gives an approximate idea of the quant.i.ty, and the colour of the quality, of the white a.r.s.enic obtainable from the sample. Some workers (sellers) weigh the residue, and determine the white a.r.s.enic by difference. In determining the percentage of moisture in these samples, the substance is dried on a water-bath or in a water-oven.

WET METHODS.

~Solution.~--Where, as in crude a.r.s.enic, the substance is a.r.s.enious oxide (As_{2}O_{3}) mixed with impurities, the a.r.s.enic is best got into solution by warming with caustic soda, and neutralising the excess with hydrochloric acid; it will be present as sodium a.r.s.enite. Metals and alloys are acted on by means of nitric acid; or the a.r.s.enic may be at the same time dissolved and separated by distilling with a strongly-acid solution of ferric chloride, in the way described under _Volumetric Methods_.

With minerals, mattes, &c., solution is thus effected:--The finely-powdered substance is mixed (in a large platinum or porcelain crucible) with from six to ten times its weight of a mixture of equal parts of carbonate of soda and nitre. The ma.s.s is then heated gradually to fusion, and kept for a few minutes in that state. When cold, it is extracted with warm water, and filtered from the insoluble residue. The solution, acidified with nitric acid and boiled, contains the a.r.s.enic as sodium a.r.s.enate. With mispickel, and those substances which easily give off a.r.s.enic on heating, the substance is first treated with nitric acid, evaporated to dryness, and then the residue is treated in the way just described.

When the a.r.s.enic is present as a.r.s.enite or a.r.s.enide, distillation with an acid solution of ferric chloride will give the whole of the a.r.s.enic in the distillate free from any metal except, perhaps, tin as stannic chloride. With a.r.s.enates, dissolve the substance in acid and then add an excess of soda. Pa.s.s sulphuretted hydrogen into the solution; warm, and filter. Acidulate the filtrate, and pa.s.s sulphuretted hydrogen. Decant off the liquid through a filter, and digest the precipitate with ammonic carbonate; filter, and re-precipitate with hydrochloric acid and sulphuretted hydrogen. Allow to stand in a warm place, and filter off the yellow sulphide of a.r.s.enic. Wash it into a beaker, clean the filter-paper (if necessary) with a drop or two of dilute ammonia; evaporate with 10 c.c. of dilute nitric acid to a small bulk; dilute; and filter off the globules of sulphur. The filtrate contains the a.r.s.enic as a.r.s.enic acid.

GRAVIMETRIC METHOD.

Having got the a.r.s.enic into solution as a.r.s.enic acid, and in a volume not much exceeding 50 c.c., add about 20 c.c. of dilute ammonia and 20 c.c. of "magnesia mixture." Stir with a gla.s.s rod, and allow to settle overnight. Filter, and wash with dilute ammonia, avoiding the use of large quant.i.ties of wash water. Dry, transfer the precipitate to a Berlin crucible, and clean the filter-paper thoroughly. Burn this paper carefully and completely; and add the ash to the contents of the crucible, together with 4 or 5 drops of nitric acid. Evaporate with a Bunsen burner, and slowly ignite, finis.h.i.+ng off with the blow-pipe or m.u.f.fle. Cool, and weigh. The ignited precipitate is pyra.r.s.enate of magnesia (Mg_{2}As_{2}O_{7}), and contains 48.4 per cent. of a.r.s.enic (As).

Instead of igniting the precipitate with nitric acid, it may be collected on a weighed filter-paper, dried at 100 C., and weighed as ammonic-magnesic a.r.s.enate (2AmMgAsO_{4}.H_{2}O), which contains 39.5 per cent. of a.r.s.enic. The results in this case are likely to be a little higher. The drying is very tedious, and is likely to leave behind more water than is allowed for in the formula. In a series of determinations in which the a.r.s.enic was weighed in both forms, the results were:--

Ammonic-magnesic a.r.s.enic Magnesium Pyra.r.s.enate a.r.s.enic a.r.s.enate in grams. in grams. in grams. in grams.

0.0080 0.0032 0.0065 0.0031 0.0400 0.0158 0.0330 0.0160 0.0799 0.0316 0.0633 0.0306 0.1600 0.0632 0.1287 0.0623 0.4000 0.1580 0.3205 0.1551 0.7990 0.3156 0.6435 0.3114

VOLUMETRIC METHODS.

There are two methods: one for determining the a.r.s.enic in the lower, and the other in the higher state of oxidation. In the first-mentioned method this is done by t.i.trating with a standard solution of iodine; and in the latter with a solution of uranium acetate. Where the a.r.s.enic already exists as a.r.s.enious oxide, or where it is most conveniently separated by distillation as a.r.s.enious chloride, the iodine method should be used; but when the a.r.s.enic is separated as ammonic-magnesic a.r.s.enate or as sulphide, the uranium acetate t.i.tration should be adopted.

IODINE PROCESS.

This is based on the fact that sodium a.r.s.enite in a solution containing an excess of bicarbonate of soda is indirectly oxidised by iodine to sodium a.r.s.enate,[103] and that an excess of iodine may be recognised by the blue colour it strikes with starch. The process is divided into two parts--(1) the preparation of the solution, and (2) the t.i.tration.

~Preparation of the Solution.~--For substances like crude a.r.s.enic, in which the a.r.s.enic is present as a.r.s.enious oxide, the method is as follows:--Take a portion which shall contain from 0.25 to 0.5 gram of the oxide, place in a beaker, and cover with 10 c.c. of sodic hydrate solution; warm till dissolved, put a small piece of litmus paper in the solution, and render acid with dilute hydrochloric acid. Add 2 grams of bicarbonate of soda in solution, filter (if necessary), and dilute to 100 c.c. The solution is now ready for t.i.trating.

[Ill.u.s.tration: FIG. 68.]

Where the a.r.s.enic has to be separated as a.r.s.enious chloride, the process is as follows:[104]--Weigh up 1 gram of the finely-powdered ore (metals should be hammered out into a thin foil or be used as filings), and place in a 16-ounce flask provided with a well-fitting cork, and connected with a ~U~-tube, as shown in the drawing (fig. 68). The ~U~-tube should contain 2 or 3 c.c. of water, and is cooled by being placed in a jar or large beaker of cold water. The water used for cooling should be renewed for each a.s.say.

Pour on the a.s.say in the flask 50 c.c. of a "ferric chloride mixture,"

made by dissolving 600 grams of calcium chloride and 300 grams of ferric chloride in 600 c.c. of hydrochloric acid, and making up to 1 litre with water.

Firmly cork up the apparatus, and boil over a small Bunsen-burner flame for fifteen or twenty minutes, but avoid evaporating to dryness.

Disconnect the flask, and pour away its contents at once to prevent breakage of the flask by their solidification. The a.r.s.enic will be condensed in the ~U~-tube, together with the greater part of the hydrochloric acid; transfer the distillate to a beaker was.h.i.+ng out the tube two or three times with water; add a small piece of litmus paper; neutralise with ammonia; render faintly _acid_ with dilute hydrochloric acid; add 2 grams of bicarbonate of soda in solution; and dilute to 250 c.c. The solution is now ready for t.i.trating.

The a.r.s.enic comes over in the early part of the distillation, as will be seen from the following experiment, made on 1 gram of copper precipitate; in which experiment the distillate was collected in separate portions at equal intervals, and the a.r.s.enic in each portion determined:--

Time Iodine Equivalent to a.r.s.enic Distilling. Required. in the Distillate.

5 minutes 12.0 c.c. 0.0450 gram 5 " 0.17 " 0.0005 "

5 " 0.0 "

5 " 0.0 "

To dryness 0.0 "

The volume of each distillate was about 5 c.c.

In this operation the metals are converted into chlorides by the action of ferric chloride, which gives up a part of its chlorine, and becomes reduced to the ferrous salt. The calcium chloride does not enter into the chemical reaction, but raises the temperature at which the solution boils, and is essential for the completion of the distillation.[105] Two experiments with material containing 3.48 per cent. of a.r.s.enic gave--(1) with ferric chloride alone, 2.74 per cent.; and (2) with the addition of calcium chloride, 3.48 per cent.

It is always necessary to make a blank determination with 1 gram of electrotype copper, to find out the amount of a.r.s.enic in the ferric chloride mixture.[106] Unfortunately, a correction is always required.

This amounts to about 0.15 per cent. of a.r.s.enic on each a.s.say, even when the mixture has been purified; and this const.i.tutes the weakness of the method, since, in some cases, the correction is as much as, or even greater than, the percentage to be determined.

The acid distillate containing the a.r.s.enious chloride may be left for an hour or so without much fear of oxidation; but it is safer to neutralise and then to add the bicarbonate of soda, as the following experiments show. Several portions of a solution, each having a bulk of 100 c.c., were exposed for varying lengths of time, and the a.r.s.enic in each determined.

_____________________________________________________________________ | | | | | | Acid Solutions. | Neutralised Solutions. | | Time Exposed. | "Iodine" a.r.s.enic Found. |"Iodine" a.r.s.enic Found. | | | Required. | Required | |_______________|___________________________|_________________________| | | | | | -- | 18.2 c.c. = 0.0136 gram | 18.1 c.c. = 0.0136 gram | | 1 hour | 18.2 " = 0.0136 " | 18.2 " = 0.0136 " | | 2 hours | 17.7 " = 0.0133 " | 18.0 " = 0.0135 " | | 4 " | 17.5 " = 0.0131 " | 18.4 " = 0.0138 " | | 5 " | 17.0 " = 0.0127 " | 18.3 " = 0.0137 " | |_______________|___________________________|_________________________|

~The t.i.tration.~--Make a _standard solution of iodine_ by weighing up in a beaker 16.933 grams of iodine and 30 grams of pota.s.sium iodide in crystals; add a few c.c. of water, and, when dissolved, dilute to 1 litre: 100 c.c. will equal 0.500 gram of a.r.s.enic.

A solution of starch similar to that used in the iodide-copper a.s.say will be required. Use 2 c.c. for each a.s.say. Variations in the quant.i.ty of starch used do not interfere; but the solution must be freshly prepared, as after seven or eight days it becomes useless.

To standardise the iodine solution, weigh up 0.3 gram of white a.r.s.enic; dissolve in caustic soda; neutralise; after acidulating, add 2 grams of bicarbonate of soda and 2 c.c. of the starch solution, and dilute to 200 c.c. with cold water. Fill a burette having a gla.s.s stop-c.o.c.k with the iodine solution, and run it into the solution of a.r.s.enic, rapidly at first, and then more cautiously, till a final drop produces a blue colour throughout the solution. Calculate the standard in the usual way.

White a.r.s.enic contains 75.76 per cent. of a.r.s.enic.

The following experiments show the effect of variation in the conditions of the t.i.tration:--

Make a solution of a.r.s.enic by dissolving 6.60 grams of white a.r.s.enic in 100 c.c. of sodic hydrate solution; render slightly acid with hydrochloric acid; add 10 grains of bicarbonate of soda, and dilute to 1 litre: 100 c.c. will contain 0.50 gram of a.r.s.enic.