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 titration 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.]
[Note 3: Attention has already been called to the fact that the color changes in the different indicators occur at varying concentrations of H^{+} or OH^{-} ions. They do not indicate exact theoretical neutrality, but a particular indicator always shows its color change at a particular concentration of H^{+} or OH^{-} ions. The results of titration with a given indicator are, therefore, comparable. As a matter of fact, a small error is involved in the procedure as outlined above. The comparison of the acid and alkali solutions was made, using methyl orange as an indicator, while the titration of the oxalic acid is made with the use of phenolphthalein. For our present purposes the small error may be neglected but, if time permits, the student is recommended to standardize the alkali solution against one of the substances named in Note 1, page 41, and also to ascertain the comparative value of the acid and alkali solutions, using phenolphthalein as indicator throughout, and conducting the titrations as described above. This will insure complete accuracy.]