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

In the Fajans titration.61 endpoint. the AgCl particles bear net positive charge. Coagulation refers to the coalescing of very small particles into larger . it is considerably less so in practice. and the approach we will use. preventing them from reacting with thiocyanate. it is necessary to bring about coagulation of the colloidal precipitate. Fe3+ + SCN! = FeSCN2+ The first appearance of red marks the endpoint. this practice is normally discouraged. is to simply remove the solid AgCl from solution by filtration. A safer and environmentally more friendly procedure. In the second place. according to: Ag+ + SCN! = AgSCN(s) Ksp = 1. In comparing the Ksp’s of silver chloride and silver thiocyanate it is apparent that silver thiocyanate is in fact less soluble than silver chloride. since nitrobenzene is extremely carcinogenic. While removing the AgCl precipitate seems a simple solution to the problem in concept. they have a very high surface area on which a significant number of silver ions will be adsorbed.1 " 10!12 A small quantity of Fe3+ ion is added to the solution as an indicator. The first appearance of pink therefore marks the endpoint. a small quantity of an anionic dye. The nitrobenzene coated the colloidal silver chloride particles. If titration of the excess silver was carried out in the presence of silver chloride precipitate. the colloidal particles formed when silver ion is added to chloride solutions are too small to be conveniently removed by filtering. To begin with. the first excess reacts with Fe3+ to form the red ferrithiocyanate complex. an excess of Ag+ is added to the sample. contributing to a large error in the amount of excess silver determined in the subsequent titration. These silver ions would be lost along with the silver chloride. 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.. is added to solution. In the Volhard titration. To solve the problem of filterability. A common method of circumventing this problem in the past was to add a small quantity of nitrobenzene to solution. Dichlorofluoroscein is an example of an adsorption indicator. The interaction between adsorbed dichlorofluoroscein and adsorbed Ag+ causes the dichlorofluoroscein to change from a yellow-green colour to pink. and the anionic dye can now adsorb on top of the adsorbed Ag+ ions. and titrate the excess Ag+ in the filtrate. Immediately past the endpoint. usually dichlorofluoroscein. After the thiocyanate has removed all the Ag+ from solution. The excess Ag+ is then titrated with a standard solution of SCN! (thiocyanate). However. Thiocyanate also forms an insoluble complex with Ag+.

. at least in part. In this experiment. The distance into solution into which the electric field of the adsorbed ions extends decreases as ionic strength increases. Pipet 10 mL of 0. Transfer to a 100 mL volumetric flask and dilute to volume with deionized water. Coagulation is impeded by the fact that colloidal particles bear a net charge . by heating the solution.in this case the positive charge due to adsorbed Ag+ ions .) Preparation of Solutions 2. 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.and therefore tend to repel each other.15 M standard AgNO3 solution by accurately weighing out #2. distilled water. Standardization of KSCN Solution 4. 6 M nitric acid.54 g of AgNO3 to the nearest 0.62 and more readily filterable ones. A further advantage is that protons from the nitric acid will displace adsorbed Ag+ ions. Procedure Cleaning Sintered Glass Filtering Crucibles 1. Be careful to avoid skin contact. Contact with silver nitrate solutions results in the development of interesting black marks on the skin. Combine thirty mL of deionized water and three mL of 6 M HNO3 into each of three 250 mL conical flasks. nitric acid is added to the solutions to increase the ionic strength and facilitate coagulation. which therefore remain in the filtrate. (Caution: Solid silver nitrate is toxic and corrosive. and distilled water through the glass filtering frit under vacuum.91 g of KSCN.) Prepare 250 mL of 0. 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. This rectifies the error in the analysis that would otherwise occur. 5. Clean one or more sintered glass filtering crucibles by drawing alternate portions of concentrated ammonia.. and diluting to volume with deionized water.15 M AgNO3 into each.0375 M KSCN solution by weighing out #0. 3. allowing the particles to move into closer proximity. Prepare 100 mL of 0.1 mg. which imparts higher kinetic energy to the particles. (Note: Concentrated ammonia should be handled only in a fume hood. transferring to a 250 mL volumetric flask. The repulsive force can be overcome.

Repeat this process for the other solutions. . 7. 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.5 to 0. Wash the precipitate. Calculate and report the weight percent of chloride in your unknown sample. 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. add 1 mL of ferric ion indicator.1 M HN03 stock solution. This has been dried in an oven prior to the laboratory.15 M AgNO3 and 10 mL of your unknown solution. If it is still hot. Filter one of the solutions through a sintered glass crucible. Accurately weigh out 0.01 M HNO3 (Prepare about 200 mL from 0.63 Analysis of Unknown 6. 8..) To the vacuum flask. Dilute to volume with deionized water. Obtain an unknown from your instructor. 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. store it in a dessicator until it reaches room temperature. Into each of three 250 mL erlenmeyer flasks. and titrate with KSCN solution until the filtrate just acquires a faint light brown colour that does not disappear on swirling. the flask. and crucible holder with small portions 0. pipet 10 mL of 0. Be careful not to lose droplets in the suction arm of the flask. crucible. Calculations First calculate the concentration of the AgNO3 solution.6 g of your unknown and transfer to a 100 mL volumetric flask. 9.

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