Gravimetric Determination of Chloride as AgCl

(Experiment 3) The chloride ion content in a solid unknown can be analyzed by dissolving the sample in dilute nitric acid, followed by precipitation with silver ion to form insoluble AgCl. A heating/cooling process known as digestion is used to enhance the production of easilyfiltered AgCl particles. The precipitate is collected by vacuum filtration, dried, and weighed.

UNKNOWN The unknown provided will be a powdery solid containing a mixture of soluble chloride salts. The objective is to determine the chloride composition (i.e., mass percent Cl) of the sample.

REAGENTS Prepare 500 mL of ~ 0.1 M HNO3 by diluting the stock solution (5 M) provided. Prepare 100 mL of ~ 0.2 M AgNO3 (169.87 g/mole). Silver salts are expensive! Please do not make more solution than you need and do not waste it! Verify your calculated mass of AgNO3 with the TA before weighing it. 1 M HCl will be provided.

PROCEDURE 1. Dry the unknown sample for 1.5-2 hours at 160 C. It is a good idea to mark it not only with your name but also some indication that this is the chloride sample. Cool in desiccator. 2. Weigh accurately by difference three 0.20-0.25 g samples of the unknown into clean, dry weighing bottles. For each sample, quantitatively transfer the weighed amount to a 250-mL beaker using about 100 mL of 0.1 M nitric acid (HNO3). 3. Precipitate silver chloride by adding 25 mL of 0.2 M silver nitrate to each solution. Digest (heat) at just below the boiling point for about one hour until the supernatant solution is clear. Add a few more drops of silver nitrate solution to the supernatant to check for complete precipitation of AgCl.

4. Weigh three clean and dry medium porosity fritted glass crucibles (prepared as in the gravimetric Ca experiment). Set up the 500-mL side-arm flask for vacuum filtration. Clean the rubber crucible holder where the crucible will make contact. For each sample, first decant the supernatant through the weighed filtering crucible. Rinse the precipitate still in the beaker with a solution of 0.1 M nitric acid. Decant the rinse through the crucible. Repeat the rinse at least twice. Use a rubber policeman to dislodge any particles that may be adhering to the beaker. Filter the AgCl through the weighed medium porosity fritted glass crucible. Wash the precipitate with 0.1 M nitric acid to remove any excess silver nitrate (check by adding a few drops of 1 M HCl to the filtrate). 5. Dry the precipitate, first at 105 C for 1-2 hours, then dry the sample to a constant weight at 160 C for 30 minutes (the precipitate may turn purple but this will not significantly change the weight). Cool the precipitate in the desiccator and weigh. 6. Calculate the weight percent of chloride in each sample, the average, and the standard deviation.

NOTES 1. When diluting acids (as in preparing the 0.1 M HNO3) always add acid to water! Handle the concentrated acids very carefully! Before lab, calculate how much 5 M HNO3 is required to prepare the required 500 mL of 0.1 M HNO 3. Check your result with the TA. 2. Likewise, check your calculated amount of solid AgNO3 with the TA before you weigh it and prepare the required 100 mL of 0.2 M AgNO3 solution. 3. Be sure to use DI water when preparing the AgNO3 solution because tap water contains significant amounts of chloride ion. Generally, use DI water in preparing all solutions in this course. 4. Aqueous AgNO3 will turn your skin black because of the reduction of the silver ion by ascorbic acid (Vitamin C). Although this discoloration is harmless, it is a good idea to minimize the amount of contact of AgNO3 with your skin. (i.e., If your technique is sloppy, you'll have visible marks to prove it!) The black splotches will not wash off but will gradually fade away in a few days. 5. Any surplus AgNO3 solution and solid AgCl residue must be disposed of in a designated waste container, not down the sink drain!