An Introductory Course of Quantitative Chemical Analysis Part 5

Refill the burettes and repeat the t.i.tration. From the records of calibration already obtained, correct the burette readings and make corrections for temperature, if necessary. Obtain the ratio of the sodium hydroxide solution to that of hydrochloric acid by dividing the number of cubic centimeters of acid used by the number of cubic centimeters of alkali required for neutralization. The check results of the two t.i.trations should not vary by more than two parts in one thousand (Note 2). If the variation in results is greater than this, refill the burettes and repeat the t.i.tration until satisfactory values are obtained. Use a new page in the notebook for each t.i.tration.

Inaccurate values should not be erased or discarded. They should be retained and marked "correct" or "incorrect," as indicated by the final outcome of the t.i.trations. This custom should be rigidly followed in all a.n.a.lytical work.

[Note 1: The end-point should be chosen exactly at the point of change; any darker tint is unsatisfactory, since it is impossible to carry shades of color in the memory and to duplicate them from day to day.]

[Note 2: While variation of two parts in one thousand in the values obtained by an inexperienced a.n.a.lyst is not excessive, the idea must be carefully avoided that this is a standard for accurate work to be !generally applied!. In many cases, after experience is gained, the allowable error is less than this proportion. In a few cases a larger variation is permissible, but these are rare and can only be recognized by an experienced a.n.a.lyst. It is essential that the beginner should acquire at least the degree of accuracy indicated if he is to become a successful a.n.a.lyst.]

STANDARDIZATION OF HYDROCHLORIC ACID

SELECTION AND PREPARATION OF STANDARD

The selection of the best substance to be used as a standard for acid solutions has been the subject of much controversy. The work of Lunge (!Ztschr. angew. Chem.! (1904), 8, 231), Ferguson (!J. Soc. Chem.

Ind.! (1905), 24, 784), and others, seems to indicate that the best standard is sodium carbonate prepared from sodium bicarbonate by heating the latter at temperature between 270 and 300C. The bicarbonate is easily prepared in a pure state, and at the temperatures named the decomposition takes place according to the equation

2HNaCO_{3} --> Na_{2}CO_{3} + H_{2}O + CO_{2}

and without loss of any carbon dioxide from the sodium carbonate, such as may occur at higher temperatures. The process is carried out as described below.

PROCEDURE.--Place in a porcelain crucible about 6 grams (roughly weighed) of the purest sodium bicarbonate obtainable. Rest the crucible upon a triangle of iron or copper wire so placed within a large crucible that there is an open air s.p.a.ce of about three eighths of an inch between them. The larger crucible may be of iron, nickel or porcelain, as may be most convenient. Insert the bulb of a thermometer reading to 350C. in the bicarbonate, supporting it with a clamp so that the bulb does not rest on the bottom of the crucible. Heat the outside crucible, using a rather small flame, and raise the temperature of the bicarbonate fairly rapidly to 270C. Then regulate the heat in such a way that the temperature rises !slowly! to 300C.

in the course of a half-hour. The bicarbonate should be frequently stirred with a clean, dry, gla.s.s rod, and after stirring, should be heaped up around the bulb of the thermometer in such a way as to cover it. This will require attention during most of the heating, as the temperature should not be permitted to rise above 310C. for any length of time. At the end of the half-hour remove the thermometer and transfer the porcelain crucible, which now contains sodium carbonate, to a desiccator. When it is cold, transfer the carbonate to a stoppered weighing tube or weighing-bottle.

STANDARDIZATION

PROCEDURE.--Clean carefully the outside of a weighing-tube, or weighing-bottle, containing the pure sodium carbonate, taking care to handle it as little as possible after wiping. Weigh the tube accurately to 0.0001 gram, and record the weight in the notebook. Hold the tube over the top of a beaker (200-300 cc.) and cautiously remove the stopper, making sure that no particles fall from it or from the tube elsewhere than in the beaker. Pour out from the tube a portion of the carbonate, replace the stopper and determine approximately how much has been removed. Continue this procedure until 1.00 to 1.10 grams has been taken from the tube. Then weigh the tube accurately and record the weight under the first weight in the notebook.

The difference in the two weights is the weight of the carbonate transferred to the beaker. Proceed in the same way to transfer a second portion of the carbonate from the tube to another beaker of about the same size as the first. The beakers should be labeled and plainly marked to correspond with the entries in the notebook.

Pour over the carbonate in each beaker about 80 cc. of water, stir until solution is complete, and add two drops of methyl orange solution. Fill the burettes with the standard acid and alkali solutions, noting the initial readings of the burettes and temperature of the solutions. Run in acid from the burette, stirring and avoiding loss by effervescence, until the solution has become pink. Wash down the sides of the beaker with a !little! water from a wash-bottle, and then run in alkali from the other burette until the pink is replaced by yellow; then finish the t.i.tration as described on page 37. Note the readings of the burettes after the proper interval, and record them in the notebook. Repeat the procedure, using the second portion of sodium carbonate. Apply the necessary calibration corrections to the volumes of the solutions used, and correct for temperature if necessary.

From the data obtained, calculate the volume of the hydrochloric acid solution which is equivalent to the volume of sodium hydroxide solution used in this t.i.tration. Subtract this volume from the volume of hydrochloric acid. The difference represents the volume of acid used to react with the sodium carbonate. Divide the weight of sodium carbonate by this volume in cubic centimeters, thus obtaining the weight of sodium carbonate equivalent to each cubic centimeter of the acid.

From this weight it is possible to calculate the corresponding weight of HCl in each cubic centimeter of the acid, and in turn the relation of the acid to the normal.

If, however, it is recalled that normal solutions are equivalent to each other, it will be seen that the same result may be more readily reached by dividing the weight in grams of sodium carbonate per cubic centimeter just found by t.i.tration by the weight which would be contained in the same volume of a normal solution of sodium carbonate.

A normal solution of sodium carbonate contains 53.0 grams per liter, or 0.0530 gram per cc. (see page 29). The relation of the acid solution to the normal is, therefore, calculated by dividing the weight of the carbonate to which each cubic centimeter of the acid is equivalent by 0.0530. The standardization must be repeated until the values obtained agree within, at most, two parts in one thousand.

When the standard of the acid solution has been determined, calculate, from the known ratio of the two solutions, the relation of the sodium hydroxide solution to a normal solution (Notes 1 and 2).

[Note 1: In the foregoing procedure the acid solution is standardized and the alkali solution referred to this standard by calculation. It is equally possible, if preferred, to standardize the alkali solution.

The standards in a common use for this purpose are purified oxalic acid (H_{2}C_{2}O_{4}.2H_{2}O), pota.s.sium acid oxalate (KHC_{2}O_{4}.H_{2}O or KHC_{2}O_{4}), pota.s.sium tetroxalate (KHC_{2}O_{4}.H_{2}C_{2}O_{4}.2H_{2}O), or pota.s.sium acid tartrate (KHC_{4}O_{6}), with the use of a suitable indicator. The oxalic acid and the oxalates should be specially prepared to insure purity, the main difficulty lying in the preservation of the water of crystallization.

It should be noted that the acid oxalate and the acid tartrate each contain one hydrogen atom replaceable by a base, while the tetroxalate contains three such atoms and the oxalic acid two. Each of the two salts first named behave, therefore, as mon.o.basic acids, and the tetroxalate as a tribasic acid.]

[Note 2: It is also possible to standardize a hydrochloric acid solution by precipitating the chloride ions as silver chloride and weighing the precipitate, as prescribed under the a.n.a.lysis of sodium chloride to be described later. Sulphuric acid solutions may be standardized by precipitation of the sulphate ions as barium sulphate and weighing the ignited precipitate, but the results are not above criticism on account of the difficulty in obtaining large precipitates of barium sulphate which are uncontaminated by inclosures or are not reduced on ignition.]

DETERMINATION OF THE TOTAL ALKALINE STRENGTH OF SODA ASH

Soda ash is crude sodium carbonate. If made by the ammonia process it may contain also sodium chloride, sulphate, and hydroxide; when made by the Le Blanc process it may contain sodium sulphide, silicate, and aluminate, and other impurities. Some of these, notably the hydroxide, combine with acids and contribute to the total alkaline strength, but it is customary to calculate this strength in terms of sodium carbonate; i.e., as though no other alkali were present.

PROCEDURE.--In order to secure a sample which shall represent the average value of the ash, it is well to take at least 5 grams. As this is too large a quant.i.ty for convenient t.i.tration, an aliquot portion of the solution is measured off, representing one fifth of the entire quant.i.ty. This is accomplished as follows: Weigh out on an a.n.a.lytical balance two samples of soda ash of about 5 grams each into beakers of about 500 cc. capacity. (The weighings need be made to centigrams only.) Dissolve the ash in 75 cc. of water, warming gently, and filter off the insoluble residue; wash the filter by filling it at least three times with distilled water, and allowing it to drain, adding the washings to the main filtrate. Cool the filtrate to approximately the standard temperature of the laboratory, and transfer it to a 250 cc.

measuring flask, washing out the beaker thoroughly. Add distilled water of laboratory temperature until the lowest point of the meniscus is level with the graduation on the neck of the flask and remove any drops of water that may be on the neck above the graduation by means of a strip of filter paper; make the solution thoroughly uniform by pouring it out into a dry beaker and back into the flask several times. Measure off 50 cc. of the solution in a measuring flask, or pipette, either of which before use should, unless they are dry on the inside, be rinsed out with at least two small portions of the soda ash solution to displace any water.

If a flask is used, fill it to the graduation with the soda ash solution and remove any liquid from the neck above the graduation with filter paper. Empty it into a beaker, and wash out the small flask, unless it is graduated for !delivery!, using small quant.i.ties of water, which are added to the liquid in the beaker. A second 50 cc.

portion from the main solution should be measured off into a second beaker. Dilute the solutions in each beaker to 100 cc., add two drops of a solution of methyl orange (Note 1) and t.i.trate for the alkali with the standard hydrochloric acid solution, using the alkali solution to complete the t.i.tration as already prescribed.

From the volumes of acid and alkali employed, corrected for burette errors and temperature changes, and the data derived from the standardization, calculate the percentage of alkali present, a.s.suming it all to be present as sodium carbonate (Note 2).

[Note 1: The hydrochloric acid sets free carbonic acid which is unstable and breaks down into water and carbon dioxide, most of which escapes from the solution. Carbonic acid is a weak acid and, as such, does not yield a sufficient concentration of H^{+} ions to cause the indicator to change to a pink (see page 32).

The chemical changes involved may be summarized as follows:

2H^{+}, 2Cl^{-} + 2Na^{+}, CO_{3}^{--} --> 2Na^{+}, 2Cl^{-} + [H_{2}CO_{3}] --> H_{2}O + CO_{2}]

[Note 2: A determination of the alkali present as hydroxide in soda ash may be determined by precipitating the carbonate by the addition of barium chloride, removing the barium carbonate by filtration, and t.i.trating the alkali in the filtrate.

The caustic alkali may also be determined by first using phenolphthalein as an indicator, which will show by its change from pink to colorless the point at which the caustic alkali has been neutralized and the carbonate has been converted to bicarbonate, and then adding methyl orange and completing the t.i.tration. The amount of acid necessary to change the methyl orange to pink is a measure of one half of the carbonate present. The results of the double t.i.tration furnish the data necessary for the determination of the caustic alkali and of the carbonate in the sample.]

DETERMINATION OF THE ACID STRENGTH OF OXALIC ACID

PROCEDURE.--Weigh out two portions of the acid of about 1 gram each. Dissolve these in 50 cc. of warm water. Add two drops of phenolphthalein solution, and run in alkali from the burette until the solution is pink; add acid from the other burette until the pink is just destroyed, and then add 0.3 cc. (not more) in excess. Heat the solution to boiling for three minutes. If the pink returns during the boiling, discharge it with acid and again add 0.3 cc. in excess and repeat the boiling (Note 1). If the color does not then reappear, add alkali until it does, and a !drop or two! of acid in excess and boil again for one minute (Note 2). If no color reappears during this time, complete the t.i.tration in the hot solution. The end-point should be the faintest visible shade of color (or its disappearance), as the same difficulty would exist here as with methyl orange if an attempt were made to match shades of pink.

From the corrected volume of alkali required to react with the oxalic acid, calculate the percentage of the crystallized acid (H_{2}C_{2}O_{4}.2H_{2}O) in the sample (Note 3).

[Note 1: All commercial caustic soda such as that from which the standard solution was made contains some sodium carbonate. This reacts with the oxalic acid, setting free carbonic acid, which, in turn, forms sodium bicarbonate with the remaining carbonate:

H_{2}CO_{3} + Na_{2}CO_{3} --> 2HNaCO_{3}.

This compound does not hydrolyze sufficiently to furnish enough OH^{-} ions to cause phenolphthalein to remain pink; hence, the color of the indicator is discharged in cold solutions at the point at which bicarbonate is formed. If, however, the solution is heated to boiling, the bicarbonate loses carbon dioxide and water, and reverts to sodium carbonate, which causes the indicator to become again pink:

2HNaCO_{3} --> H_{2}O + CO_{2} + Na_{2}CO_{3}.

By adding successive portions of hydrochloric acid and boiling, the carbonate is ultimately all brought into reaction.

The student should make sure that the difference in behavior of the two indicators, methyl orange and phenolphthalein, is understood.]

[Note 2: Hydrochloric acid is volatilized from aqueous solutions, except such as are very dilute. If the directions in the procedure are strictly followed, no loss of acid need be feared, but the amount added in excess should not be greater than 0.3-0.4 cc.]