[Note 1: Iodine solutions react with water to form hydriodic acid under the influence of the sunlight, and even at low room temperatures the iodine tends to volatilize from solution. They should, therefore, be protected from light and heat. Iodine solutions are not stable for long periods under the best of conditions. They cannot be used in burettes with rubber tips, since they attack the rubber.]
[Note 2: Sodium thiosulphate (Na_{2}S_{2}O_{3}.5H_{2}O) is rarely wholly pure as sold commercially, but may be purified by recrystallization. The carbon dioxide absorbed from the air by distilled water decomposes the salt, with the separation of sulphur.
Boiled water which has been cooled out of contact with the air should be used in preparing solutions.]
INDICATOR SOLUTION
The starch solution for use as an indicator must be freshly prepared.
A soluble starch is obtainable which serves well, and a solution of 0.5 gram of this starch in 25 cc. of boiling water is sufficient. The solution should be filtered while hot and is ready for use when cold.
If soluble starch is not at hand, potato starch may be used. Mix about 1 gram with 5 cc. of cold water to a smooth paste, pour 150 cc. of !boiling! water over it, warm for a moment on the hot plate, and put it aside to settle. Decant the supernatant liquid through a filter and use the clear filtrate; 5 cc. of this solution are needed for a t.i.tration.
The solution of potato starch is less stable than the soluble starch.
The solid particles of the starch, if not removed by filtration, become so colored by the iodine that they are not readily decolorized by the thiosulphate (Note 1).
[Note 1: The blue color which results when free iodine and starch are brought together is probably not due to the formation of a true chemical compound. It is regarded as a "solid solution" of iodine in starch. Although it is unstable, and easily destroyed by heat, it serves as an indicator for the presence of free iodine of remarkable sensitiveness, and makes the iodometric processes the most satisfactory of any in the field of volumetric a.n.a.lysis.]
COMPARISON OF IODINE AND THIOSULPHATE SOLUTIONS
PROCEDURE.--Place the solutions in burettes (the iodine in a gla.s.s-stoppered burette), observing the usual precautions. Run out 40 cc. of the thiosulphate solution into a beaker, dilute with 150 cc. of water, add 1 cc. to 2 cc. of the soluble starch solution, and t.i.trate with the iodine to the appearance of the blue of the iodo-starch.
Repeat until the ratio of the two solutions is established, remembering all necessary corrections for burettes and for temperature changes.
STANDARDIZATION OF SOLUTIONS
Commercial iodine is usually not sufficiently pure to permit of its use as a standard for thiosulphate solutions or the direct preparation of a standard solution of iodine. It is likely to contain, beside moisture, some iodine chloride, if chlorine was used to liberate the iodine when it was prepared. It may be purified by sublimation after mixing it with a little pota.s.sium iodide, which reacts with the iodine chloride, forming pota.s.sium chloride and setting free the iodine. The sublimed iodine is then dried by placing it in a closed container over concentrated sulphuric acid. It may then be weighed in a stoppered weighing-tube and dissolved in a solution of pota.s.sium iodide in a stoppered flask to prevent loss of iodine by volatilization. About 18 grams of the iodide and twelve grams of iodine per liter are required for an approximately tenth-normal solution.
An iodine solution made from commercial iodine may also be standardized against a.r.s.enious oxide (As_{4}O_{6}). This substance also usually requires purification by sublimation before use.
The substances usually employed for the standardization of a thiosulphate solution are pota.s.sium bromate and metallic copper. The former is obtainable in pure condition or may be easily purified by re-crystallization. Copper wire of high grade is sufficiently pure to serve as a standard. Both pota.s.sium bromate and cupric salts in solution will liberate iodine from an iodide, which is then t.i.trated with the thiosulphate solution.
The reactions involved are the following:
(a) KBrO_{3} + 6KI + 3H_{2}SO_{4} --> KBr + 3I_{2} + 3K_{2}SO_{4} + 3H_{2}O,
(b) 3Cu + 8HNO_{3} --> 3Cu(NO_{3})_{2} + 2NO + 4H_{2}O, 2Cu(NO_{3})_{2} + 4KI --> 2CuI + 4KNO_{3} + I_{2}.
Two methods for the direct standardization of the sodium thiosulphate solution are here described, and one for the direct standardization of the iodine solution.
!Method A!
PROCEDURE.--Weigh out into 500 cc. beakers two portions of about 0.150-0.175 gram of pota.s.sium bromate. Dissolve each of these in 50 cc. of water, and add 10 cc. of a pota.s.sium iodide solution containing 3 grams of the salt in that volume (Note 1). Add to the mixture 10 cc.
of dilute sulphuric acid (1 volume of sulphuric acid with 5 volumes of water), allow the solution to stand for three minutes, and dilute to 150 cc. (Note 2). Run in thiosulphate solution from a burette until the color of the liberated iodine is nearly destroyed, and then add 1 cc. or 2 cc. of starch solution, t.i.trate to the disappearance of the iodo-starch blue, and finally add iodine solution until the color is just restored. Make a blank test for the amount of thiosulphate solution required to react with the iodine liberated by the iodate which is generally present in the pota.s.sium iodide solution, and deduct this from the total volume used in the t.i.tration.
From the data obtained, calculate the relation of the thiosulphate solution to a normal solution, and subsequently calculate the similar value for the iodine solution.
[Note 1:--Pota.s.sium iodide usually contains small amounts of pota.s.sium iodate as impurity which, when the iodide is brought into an acid solution, liberates iodine, just as does the pota.s.sium bromate used as a standard. It is necessary to determine the amount of thiosulphate which reacts with the iodine thus liberated by making a "blank test"
with the iodide and acid alone. As the iodate is not always uniformly distributed throughout the iodide, it is better to make up a sufficient volume of a solution of the iodide for the purposes of the work in hand, and to make the blank test by using the same volume of the iodide solution as is added in the standardizing process. The iodide solution should contain about 3 grams of the salt in 10 cc.]
[Note 2: The color of the iodo-starch is somewhat less satisfactory in concentrated solutions of the alkali salts, notably the iodides. The dilution prescribed obviates this difficulty.]
!Method B!
PROCEDURE.--Weigh out two portions of 0.25-0.27 gram of clean copper wire into 250 cc. Erlenmeyer flasks (Note 1). Add to each 5 cc. of concentrated nitric acid (sp. gr. 1.42) and 25 cc. of water, cover, and warm until solution is complete. Add 5 cc. of bromine water and boil until the excess of bromine is expelled. Cool, and add strong ammonia (sp. gr. 0.90) drop by drop until a deep blue color indicates the presence of an excess. Boil the solution until the deep blue is replaced by a light bluish green, or a brown stain appears on the sides of the flask (Note 2). Add 10 cc. of strong acetic acid (sp.
gr. 1.04), cool under the water tap, and add a solution of pota.s.sium iodide (Note 3) containing about 3 grams of the salt, and t.i.trate with thiosulphate solution until the color of the liberated iodine is nearly destroyed. Then add 1-2 cc. of freshly prepared starch solution, and add thiosulphate solution, drop by drop, until the blue color is discharged.
From the data obtained, including the "blank test" of the iodide, calculate the relation of the thiosulphate solution to the normal.
[Note 1: While copper wire of commerce is not absolutely pure, the requirements for its use as a conductor of electricity are such that the impurities const.i.tute only a few hundredths of one per cent and are negligible for a.n.a.lytical purposes.]
[Note 2: Ammonia neutralizes the free nitric acid. It should be added in slight excess only, since the excess must be removed by boiling, which is tedious. If too much ammonia is present when acetic acid is added, the resulting ammonium acetate is hydrolyzed, and the ammonium hydroxide reacts with the iodine set free.]
[Note 3: A considerable excess of pota.s.sium iodide is necessary for the prompt liberation of iodine. While a large excess will do no harm, the cost of this reagent is so great that waste should be avoided.]
!Method C!
PROCEDURE.--Weigh out into 500 cc. beakers two portions of 0.175-0.200 gram each of pure a.r.s.enious oxide. Dissolve each of these in 10 cc. of sodium hydroxide solution, with stirring. Dilute the solutions to 150 cc. and add dilute hydrochloric acid until the solutions contain a few drops in excess, and finally add to each a concentrated solution of 5 grams of pure sodium bicarbonate (NaHCO_{3}) in water. Cover the beakers before adding the bicarbonate, to avoid loss. Add the starch solution and t.i.trate with the iodine to the appearance of the blue of the iodo-starch, taking care not to pa.s.s the end-point by more than a few drops (Note 1).
From the corrected volume of the iodine solution used to oxidize the a.r.s.enious oxide, calculate its relation to the normal. From the ratio between the solutions, calculate the similar value for the thiosulphate solution.
[Note 1: a.r.s.enious oxide dissolves more readily in caustic alkali than in a bicarbonate solution, but the presence of caustic alkali during the t.i.tration is not admissible. It is therefore destroyed by the addition of acid, and the solution is then made neutral with the solution of bicarbonate, part of which reacts with the acid, the excess remaining in solution.
The reaction during t.i.tration is the following:
Na_{3}AsO_{3} + I_{2} + 2NaHCO_{3} --> Na_{3}AsO_{4} + 2NaI + 2CO_{2} + H_{2}O
As the reaction between sodium thiosulphate and iodine is not always free from secondary reactions in the presence of even the weakly alkaline bicarbonate, it is best to avoid the addition of any considerable excess of iodine. Should the end-point be pa.s.sed by a few drops, the thiosulphate may be used to correct it.]
DETERMINATION OF COPPER IN ORES
Copper ores vary widely in composition from the nearly pure copper minerals, such as malachite and copper sulphide, to very low grade materials which contain such impurities as silica, lead, iron, silver, sulphur, a.r.s.enic, and antimony. In nearly all varieties there will be found a siliceous residue insoluble in acids. The method here given, which is a modification of that described by A.H. Low (!J. Am. Chem.
Soc.! (1902), 24, 1082), provides for the extraction of the copper from commonly occurring ores, and for the presence of their common impurities. For practice a.n.a.lyses it is advisable to select an ore of a fair degree of purity.
PROCEDURE.-- Weigh out two portions of about 0.5 gram each of the ore (which should be ground until no grit is detected) into 250 cc.
Erlenmeyer flasks or small beakers. Add 10 cc. of concentrated nitric acid (sp. gr. 1.42) and heat very gently until the ore is decomposed and the acid evaporated nearly to dryness (Note 1). Add 5 cc. of concentrated hydrochloric acid (sp. gr. 1.2) and warm gently. Then add about 7 cc. of concentrated sulphuric acid (sp. gr. 1.84) and evaporate over a free flame until the sulphuric acid fumes freely (Note 2). It has then displaced nitric and hydrochloric acid from their compounds.
Cool the flask or beaker, add 25 cc. of water, heat the solution to boiling, and boil for two minutes. Filter to remove insoluble sulphates, silica and any silver that may have been precipitated as silver chloride, and receive the filtrate in a small beaker, washing the precipitate and filter paper with warm water until the filtrate and washings amount to 75 cc. Bend a strip of aluminium foil (5 cm. x 12 cm.) into triangular form and place it on edge in the beaker. Cover the beaker and boil the solution (being careful to avoid loss of liquid by spattering) for ten minutes, but do not evaporate to small volume.
Wash the cover gla.s.s and sides of the beaker. The copper should now be in the form of a precipitate at the bottom of the beaker or adhering loosely to the aluminium sheet. Remove the sheet, wash it carefully with hydrogen sulphide water and place it in a small beaker. Decant the solution through a filter, wash the precipitated copper twice by decantation with hydrogen sulphide water, and finally transfer the copper to the filter paper, where it is again washed thoroughly, being careful at all times to keep the precipitated copper covered with the wash water. Remove and discard the filtrate and place an Erlenmeyer flask under the funnel. Pour 15 cc. of dilute nitric acid (sp. gr.
1.20) over the aluminium foil in the beaker, thus dissolving any adhering copper. Wash the foil with hot water and remove it. Warm this nitric acid solution and pour it slowly through the filter paper, thereby dissolving the copper on the paper, receiving the acid solution in the Erlenmeyer flask. Before washing the paper, pour 5 cc.