- 60 DETERMINATION OF SOLUBLE CHLORIDE: THE VOLHARD TITRATION

Introduction In this experiment, the chloride content in a sample composed of NaCl and KCl will be determined. The experiment will give you experience in a variety of important techniques, including quantitative transfer, and digestion, filtering, and washing of precipitates. The Volhard titration is an example of a back titration. In back titrations, a known quantity of reagent is added in excess of that required to completely react with the analyte. The remaining reagent is then subsequently titrated. The difference between the total amount of reagent added, and that remaining after reaction with the analyte, is proportional to the number of moles of analyte in the sample.

Theory With the exception of fluoride ion, all of the halides (Cl!, I!, and Br!) as well as the pseudohalides (OCN!, SCN!, and CN!) form insoluble precipitates with Ag+. This reaction has been used for the analysis of all of the above ions. Analyses based on reaction with Ag+ are called argentometric analyses. There are a number of argentometric procedures available for the determination of chloride. Direct titration with Ag+ and potentiometric determination of the endpoint is one of the most frequently employed, but this requires the use of a millivoltmeter, and potentiometric titrations can be tedious and time consuming. Several methods have been devised for visual determination of the endpoint. Of these, the Mohr, the Fajans, and the Volhard titration are the most popular. In the Mohr titration, a small amount of CrO42- is added to the solution containing the chloride to be analyzed. Ag+, most frequently originating as AgNO3, is then added from a buret. The Ag+ reacts first with the Cl! in solution to form a white precipitate according to: Ag+ + Cl! = AgCl(s) Ksp = 1.8 " 10!10

When all of the Cl! has reacted, further addition of Ag+ will result in the formation of the red AgCrO4 precipitate, indicating the endpoint. Ag+ + CrO4! = AgCrO4(s) The Fajans titration relies on the fact that colloidal AgCl particles will have Cl! ions adsorbed on their surface in the presence of excess chloride, and Ag+ ions adsorbed when Ag+ is present in excess. If Cl! is titrated with Ag+, the small colloidal particles bear a net negative charge prior to the endpoint, and a net positive charge immediately past the

- 61 endpoint. In the Fajans titration, a small quantity of an anionic dye, usually dichlorofluoroscein, is added to solution. Immediately past the endpoint, the AgCl particles bear net positive charge, and the anionic dye can now adsorb on top of the adsorbed Ag+ ions. The interaction between adsorbed dichlorofluoroscein and adsorbed Ag+ causes the dichlorofluoroscein to change from a yellow-green colour to pink. The first appearance of pink therefore marks the endpoint. Dichlorofluoroscein is an example of an adsorption indicator. In the Volhard titration, an excess of Ag+ is added to the sample. The excess Ag+ is then titrated with a standard solution of SCN! (thiocyanate). Thiocyanate also forms an insoluble complex with Ag+, according to: Ag+ + SCN! = AgSCN(s) Ksp = 1.1 " 10!12

A small quantity of Fe3+ ion is added to the solution as an indicator. After the thiocyanate has removed all the Ag+ from solution, the first excess reacts with Fe3+ to form the red ferrithiocyanate complex. Fe3+ + SCN! = FeSCN2+ The first appearance of red marks the endpoint. In comparing the Ksps of silver chloride and silver thiocyanate it is apparent that silver thiocyanate is in fact less soluble than silver chloride. If titration of the excess silver was carried out in the presence of silver chloride precipitate, the thiocyanate would therefore react with the AgCl particles according to: AgCl + SCN! = AgSCN + Cl! This reaction must be prevented for the endpoint to be meaningful. A common method of circumventing this problem in the past was to add a small quantity of nitrobenzene to solution. The nitrobenzene coated the colloidal silver chloride particles, preventing them from reacting with thiocyanate. However, since nitrobenzene is extremely carcinogenic, this practice is normally discouraged. A safer and environmentally more friendly procedure, and the approach we will use, is to simply remove the solid AgCl from solution by filtration, and titrate the excess Ag+ in the filtrate. While removing the AgCl precipitate seems a simple solution to the problem in concept, it is considerably less so in practice. To begin with, the colloidal particles formed when silver ion is added to chloride solutions are too small to be conveniently removed by filtering. In the second place, they have a very high surface area on which a significant number of silver ions will be adsorbed. These silver ions would be lost along with the silver chloride, contributing to a large error in the amount of excess silver determined in the subsequent titration. To solve the problem of filterability, it is necessary to bring about coagulation of the colloidal precipitate. Coagulation refers to the coalescing of very small particles into larger

- 62 and more readily filterable ones. Coagulation is impeded by the fact that colloidal particles bear a net charge - in this case the positive charge due to adsorbed Ag+ ions - and therefore tend to repel each other. The repulsive force can be overcome, at least in part, by heating the solution, which imparts higher kinetic energy to the particles. A more efficient method of minimizing the effect of the repulsive forces is to increase the ionic strength of the solution by addition of some inert electrolyte. The distance into solution into which the electric field of the adsorbed ions extends decreases as ionic strength increases, allowing the particles to move into closer proximity. In this experiment, nitric acid is added to the solutions to increase the ionic strength and facilitate coagulation. A further advantage is that protons from the nitric acid will displace adsorbed Ag+ ions, which therefore remain in the filtrate. This rectifies the error in the analysis that would otherwise occur.

Procedure Cleaning Sintered Glass Filtering Crucibles 1. Clean one or more sintered glass filtering crucibles by drawing alternate portions of concentrated ammonia, distilled water, 6 M nitric acid, and distilled water through the glass filtering frit under vacuum. (Note: Concentrated ammonia should be handled only in a fume hood.)

Preparation of Solutions 2. Prepare 100 mL of 0.15 M standard AgNO3 solution by accurately weighing out #2.54 g of AgNO3 to the nearest 0.1 mg. Transfer to a 100 mL volumetric flask and dilute to volume with deionized water. (Caution: Solid silver nitrate is toxic and corrosive. Contact with silver nitrate solutions results in the development of interesting black marks on the skin. Be careful to avoid skin contact.) Prepare 250 mL of 0.0375 M KSCN solution by weighing out #0.91 g of KSCN, transferring to a 250 mL volumetric flask, and diluting to volume with deionized water.

3.

Standardization of KSCN Solution 4. 5. Combine thirty mL of deionized water and three mL of 6 M HNO3 into each of three 250 mL conical flasks. Pipet 10 mL of 0.15 M AgNO3 into each. Add 1 mL of ferric ion indicator and titrate with KSCN solution until the supernatant acquires a faint light brown colour which does not disappear on swirling the solution.

- 63 Analysis of Unknown 6. 7. 8. Obtain an unknown from your instructor. This has been dried in an oven prior to the laboratory. If it is still hot, store it in a dessicator until it reaches room temperature. Accurately weigh out 0.5 to 0.6 g of your unknown and transfer to a 100 mL volumetric flask. Dilute to volume with deionized water. Into each of three 250 mL erlenmeyer flasks, pipet 10 mL of 0.15 M AgNO3 and 10 mL of your unknown solution. Add 10 mL of water and 3 mL of 6 M HNO3. Cover with a watchglass and heat the solutions on a hot plate or Bunsen burner until the supernatant is clear. Filter one of the solutions through a sintered glass crucible. Wash the precipitate, the flask, crucible, and crucible holder with small portions 0.01 M HNO3 (Prepare about 200 mL from 0.1 M HN03 stock solution.) To the vacuum flask, add 1 mL of ferric ion indicator, and titrate with KSCN solution until the filtrate just acquires a faint light brown colour that does not disappear on swirling. Be careful not to lose droplets in the suction arm of the flask. Repeat this process for the other solutions.

9.

Calculations First calculate the concentration of the AgNO3 solution. With this value in hand you can determine the concentration of the KSCN titrant from your titrations of AgNO3 aliquots in absence of any unknown. The volume of KSCN required to titrate the filtrate from the unknown solutions multiplied by the concentration of the KSCN solution gives the number of moles of Ag+ remaining in solution following precipitation with chloride. The difference between this value and the total number of moles of Ag+ added equals the number of moles of chloride in your unknown aliquot. Calculate and report the weight percent of chloride in your unknown sample.