College of Science

Determination of Chloride Ion Concentration by Titration (Volhards Method)

Safety
Lab coats, safety glasses and enclosed footwear must be worn at all times in the laboratory. Silver nitrate solution causes staining of skin and fabric (chemical burns). Any spills should be rinsed with water immediately. Concentrated nitric acid is very corrosive: take great care using the 6molL-1 solution. neutral or basic, Mohrs method or the gravimetric method should be used. The method is illustrated below by using the procedure to determine the concentration of chloride (from sodium chloride) in cheese.

Equipment Needed
boiling chips 500 mL volumetric flask 10 mL and 100 mL measuring cylinders

Introduction

conical flasks This method uses a back titration with potassium thiocyanate to determine the concentration of chloride Bunsen burner, tripod and gauze ions in a solution. Before the titration an excess volume burette and stand of a silver nitrate solution is added to the solution 50 mL pipette (if possible) containing chloride ions, forming a precipitate of silver chloride. The term excess is used as the moles of silver Introduction nitrate added are known to exceed the moles of sodium This method uses a back titration with potassium chloride present in the thiocyanateso determine the concentration of chloride sample to that all the chloride ions in a solution. Before the titration an excess volume Burette containing ions present will react. of a silver nitrate solution is added to the solution potassium thiocyanate

Determination of Chloride Ion Concentration by Titration (Volhards Method)

Ag+(aq) + Cl(aq)The term excess is used as the moles of silver chloride. AgCl(s)
The indicator Fe3+ (ferric ion) is theninadded and that all the chloride chloride present the sample so the ions present will react. solution is titrated with the potassium thiocyanate Ag+(aq) + as the AgCl(s) solution. The titrate remains pale yellow Cl(aq) excess The indicator the thiocyanate ions (unreacted) silver ions react withFe3+ (ferric ion) is then added and the solution is titrated with to form a silver thiocyanate precipitate. the potassium thiocyanate

containing chloride ions, forming a precipitate of silver

solution

nitrate added are known to exceed the moles of sodium

Ag

+ (aq)

solution. The titrate remains pale yellow as the excess (unreacted) silver ions react with SCNa(aq) AgSCN(s) the thiocyanate ions to form silver thiocyanate precipitate.

Once all the silver ions have reacted, the slightest (s) Ag+(aq) + SCN(aq) AgSCN 3+ excess of thiocyanate reacts with Feions have reacted, the slightest Once all the silver to form a dark red excess of thiocyanate reacts with Fe3+ to form a dark red complex.
Fe (aq) + SCN (aq) Fe3+(aq) + SCN(aq) [FeSCN]2+(aq) [FeSCN]
3+

complex.

2+ (aq)

The concentration of chloride ionstitration findings of the moles of silver subtracting the is determined by ions that reacted the moles of silver subtracting the titration findings ofwith the thiocyanate from the total moles of silver nitrate added to the solution. ions that reacted with the thiocyanate from the total This method is used when the pH of the solution after moles of silver nitrate added tohas been prepared is acidic. If the pH is the sample the solution.
neutral or This method is used when thebasic,of used.method or theafter below pH Mohrs The method isgravimetric the solution, illustrated method should be the sample has been prepared, is acidic.to determine the concentration by using the procedure If the pH is of chloride (from sodium chloride) in cheese.

The concentration of chloride ions is determined by

Conical flask

Cheese extract solution

Equipment Needed
boiling chips

Solutions Needed Concentrated nitric acid Solutions Needed (see safety notes): (6 mol L-1)
1 Silver nitrate nitric acid (see safety notes): (6 dry 5 ) Concentratedsolution: (0.1 mol L ). If possible,mol L-1g of AgNO for 2 hours at 100C and allow to cool. Accurately Silver 3about 4.25 g of solidmol L1). and dissolve it ing of weighnitrate solution: (0.1 AgNO3 If possible, dry 5 AgNO3 for 2 hours at 100C and allow flask. Store the 250 mL of distilled water in a conical to cool. Accurately weigh about 4.25 g of solid AgNO3 and dissolve it in 250 solution in a brown bottle. mL of distilled water in a conical flask. Store1the solution Potassium thiocyanate solution: (0.1 mol L ). Weigh in a brown bottle. 2.43 g of solid KSCN and dissolve it in 250 mL of Potassium thiocyanate solution: (0.1 mol L1). Weigh distilled water in a volumetric flask. 2.43 g of solid KSCN and dissolve it in 250 mL of distilled Potassium permanganate solution: (5%) Add 1.5 g water in a volumetric flask. KMnO4 to 30 mL of distilled water. Potassium permanganate solution: (saturated) Add 8g Ferric ammonium sulfate solution: (5%) Add 1.5 g KMnO4 to 30 )mL of distilledmL of distilled water and of NH Fe(SO .12H2O to 20 water.

and addition of 5 mL of potassium permanganate should be continued, checking each time until there 4. Cool the solution and filter it. Wash the solid is a satisfactory level of digestion. residue with a few mL of distilled water. 4. Cool the solution and filter it. Wash the solid residue 5. with a few mL of distilled 500 mL in a volumetric Make the filtrate up to water. flask. 5. Make the filtrate up to 500 mL in a volumetric flask.

add a few drops of concentrated nitric acid (see safety Ferric ammonium sulfate solution: (saturated) Add 8 g notes). of NH4Fe(SO4)2.12H2O to 20 mL of distilled water and add a few drops of concentrated nitric acid.

42

Method Method Sample Preparation

The salt Preparation Sample sodium chloride is added during the manufacture of chloride cheese. during the The salt sodium cheddar is addedIn this method, the cheese is digested cheese. In this method, manufacture of cheddarto release this salt to obtain the concentration of chloride ions. To carry out this the cheese is digested to release this salt to obtain digestion, the cheese is reacted with carry out and the concentration of chloride ions. Tonitric acidthis potassium permanganate. The with nitric acid and digestion, the cheese is reacted chloride ions are then free to form a precipitate The the added silver then potassium permanganate. with chloride ions are ions. 1. Cut or grate precipitate with the pieces and free to form a the cheese into fine added silver ions. accurately weigh about 6 g into a 500 mL conical 1. Cut or grate the cheese into fine pieces and flask. accurately weigh about 6 g into a 500 mL conical flask. 2. Precisely add 50 mL of 0.1 mol L1 silver nitrate 2. solution (byadd 50 mL possible), 20 mL ofnitrate Precisely pipette if of 0.1 mol L1 silver solution (by pipette if possible), 20 mL of concentrated concentrated nitric acid, (very carefully see nitric acid, (very carefully distilled water and100 mL safety notes), 100 mL of see safety notes), a few of distilledchips, and heat the solution to and heat the boiling water and a few boiling chips, boiling in a solution to boiling. fumehood. 3. AsAs the solution boils addmL ofof 5% potassium 3. the solution boils add 5 5 mL 5% potassium permanganate solution. This addition willwill cause a permanganate solution. This addition cause a very smelly reaction and should be done in fumehood. Keep very smelly reaction so done in the a fumehood. Keep boiling until the purple colour disappears, then boiling until the purple colour disappears, then add add another 5 mL of potassium permanganate solution. another 5 mL of potassium permanganate solution. Continue this process until 30 30 mL potassium Continue this process until mL of of potassium permanganate solution has been added and thethe permanganate solution has been added and cheese particles areare completely digested (or close cheese particles completely digested (or as as close as as possible). To find out when digestioncomplete, possible). To find out when digestion is is complete, remove the flask from heat and allow it to stand for for a remove the flask from heat and allow it to stand a few moments. Undigested cheese particles willwill float few moments. Undigested cheese particles float upon the surface of thethe clear liquid, while the white upon the surface of clear liquid, while the white precipitate of silver chloride willwill sinkthethe bottom. If precipitate of silver chloride sink to to bottom. If there is still too much undigested cheese, thethe boiling there is still too much undigested cheese, boiling and addition of 5 mL of potassium permanganate should be continued, checking each time until there is a satisfactory level of digestion.

Titration Titration 1. Use a volumetric cylinder measure 100 mL of the 1. Use a volumetric cylinder toto measure 100 mL of the cheese extract solution (be(be precise as possible) and cheese extract solution as as precise as possible) pour it poura conicalconical flask. and into it into a flask. 2. Add 1 mL saturated ferric ammonium sulfate 2. Add 1 mL of of saturated ferric ammonium sulfate solution as as indicator. solution indicator. Titrate the unreacted silver ions with the mol L1 3. Titrate the unreacted silver ions with the 0.10.1 mol L1 potassium thiocyanate solution. The end point is the point is the first appearance of a dark redred colour due thethe ferric first appearance of a dark colour due to to ferric thiocyanate complex (figure 1). 1). thiocyanate complex (figure 4. Repeat the titration with 100 mL samples ofof the Repeat the titration with 100 mL samples the cheese extract solution until you obtain concordant cheese extract solution until you obtain concordant results (titres agreeing within mL). results (titres agreeing within 0.1 0.1 mL).

Figure 1 Leftformation of silver thiocyanate precipitate, makingof flask: before the titration endpoint, addition the ions leads to SCN ions leadsHere the solution also takes a faint yellow colour due solution cloudy. to formation of silver thiocyanate precipitate, making the solution cloudy. Here the solutionthe endpointa the to the colour of the cheese extract. Centre flask: at also takes all faint yellow colourbeen precipitated by of the cheese extract. of free silver ions have due to the colour SCN. The slightest excess Centre flask:dark redendpointcomplexfree silver ions have been SCN forms a at the coloured all the with the Fe3+ ions from the precipitated by SCN. The slightest excess solution a slighta ferric ammonium sulfate indicator, giving the of SCN forms orange/ red colouration. Right flask: If with the Fe3+ ions from the ferric dark red coloured complex addition of SCN is continued past the endpoint, further ferric thiocyanate complex solution a slight ammonium sulfate indicator, giving the is formed and a stronger dark red colour results. NB: The titration should be stopped is orange/red colouration. Right flask: If addition of SCNwhen the first trace of dark red endpoint, further ferric thiocyanate complex continued past the colour is observed. Using an incompletely titrated reference flask a comparison is red colour results. NB: The is formed andforstronger dark a helpful way to identify the first appearance of red colouration. titration should be stopped when the first trace of dark red colour is observed. Using an incompletely titrated reference flask for comparison is a helpful way to identify the first appearance of red colouration.

Figure 1 Left flask: before the titration endpoint, addition of SCN

Result Calculations
1. Determine the average volume of potassium thiocyanate used from your concordant titres. 2. Calculate the moles of potassium thiocyanate used. 3. Use the equation of the reaction between silver ions and thiocyanate ions

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Ag

+ (aq)

+ SCN

( aq)

AgSCN(s)

to calculate the moles of unreacted silver nitrate in 100 mL of cheese extract, and multiply the figure by five to determine the total moles of unreacted silver nitrate (the excess) in the 500 mL volumetric flask. 4. Calculate the moles of silver nitrate in the 50 mL of solution that was added during the sample preparation to the cheese. 5. Calculate the total moles of silver nitrate that reacted with the salt from the cheese by subtracting the moles of unreacted silver nitrate (the excess) from the total moles of silver nitrate added to the cheese. 6. Use the equation of the reaction between the silver ions and the chloride ions to calculate the moles of sodium chloride in the sample of cheese.

Ag+(aq) + Cl(aq) AgCl(s)

7. Calculate the concentration of sodium chloride in the cheese as grams of salt per 100 g cheese (% salt).

Additional Notes
1. Residues containing silver ions and precipitate are usually saved for later recovery of silver metal. Check this with your teacher or the laboratory supervisor. 2. A blank titration substituting sucrose (sugar) for the cheese should be carried out to see if there are any contaminating chloride ions present in the reagent solutions used. If any are found, the figure should be subtracted from the titration results. 3. For greatest accuracy it is a good idea to standardise your thiocyanate solution by titrating several samples against your standardised silver nitrate solution (once again using ferric ammonium sulfate indicator). The concentration of SCN determined by this titration should then be used in all calculations.