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KJ2050 Analytical Chemistry 2012

Experiment 3: Preparation and Standardization of a Sodium Thiosulfate solution

Chan Ao Bang Osborne

Table of Contents
1. Introduction ..................................................................................................................... 3
1.1 Objective of experiment .................................................................................................................... 3

2. Theory ................................................................................................................................ 3 3. Experimental Procedure ............................................................................................. 5


3.1 Standardization of Sodium Thiosulfate solution against Potassium Iodate ................ 5 3.2 Determination of Copper in an unknown sample .................................................................. 6

4. Experimental Results.................................................................................................... 6 5. Experimental Discussion ............................................................................................. 7 6. Conclusion ........................................................................................................................ 9 7. Literature ....................................................................................................................... 10 8. Appendix ........................................................................................................................ 11

Norwegian University of Science and Tech KJ2050 Analytical Chemistry Experiment 2

Experiment 3: Preparation and Standardization of a Sodium Thiosulfate solution


1. Introduction
1.1 Objective of experiment To prepare a solution of sodium thiosulfate and standardize it against potassium iodate. The sodium thiosulfate solution is to be used in the determination of the content of copper in an unknown sample thereafter by using the Iodometric titration method.

2. Theory
Iodine solutions are a weak oxidizing agents, which are usually used to determine the concentration or the content of strong reducing compounds in a solution. Equation 1.1 shows the half-reaction for the reduction of iodine and the small electrode potential value indicates that the reverse reaction takes place readily. I3 - 2e- 3I- E0 = 0.536 V --------------------------------------(1.1) Iodine (I2) is not very soluble in water, and hence is frequently added to potassium iodide (KI) in moderate concentrations to produce I3-. This reaction is as per in equation (1.2). I2 (s) + I- I3 --------------------------------------(1.2) This reaction shows that the addition of KI will cause more I2 to be dissolved, but since I2 dissolves slowly in CI, only a small amount of I2 was added to a small amount of concentrated HCI. It should also be noted that iodine is oxidized by air through the reaction equation as shown in equation (1.2.1). 4I-+ O2 + 4 H+ 2I2 + 2 H2O --------------------------------------(1.2.1) Sodium thiosulfate (Na2S2O3) dissociates into thiosulfate ions (S2O3-), which after titration with IO3-, is oxidized to a tetrathionation (S4O62-) according to equation (1.3). 2S2O3- + 2 e- S4O62- --------------------------------------(1.3) By first adding KI in excess to a solution with a known concentration of I2, triodide ions (I3-) are released. By titrating against Na2S2O3, the concentration of Na2S2O3 can then be determined. Equation (1.4) shows the reaction equation of determining the concentration of S2O3-, while equation (1.5) shows the reaction equation for determining the amount of copper (Cu) in the unknown sample. IO3- + 6 S2O3- + 6 H+ I- + H2O + S4O62--------------------------------------- (1.4) 2 Cu2+ + 2S2O3- + I- 2CuI + S4O62- --------------------------------------(1.5) 3

Norwegian University of Science and Tech KJ2050 Analytical Chemistry Experiment 2

Starch solutions are usually added for titration experiments involving iodine to improve the color change while determining equivalence point. When starch is added to a solution containing iodine, the solution forms a deep blue coloration as the starch absorbs the iodine. In iodometric titrations, where iodine solution is titrated against S2O3- as an indirect oxidant, the starch is added just before the end point of the titration. This is because starch is irreversibly degraded in solutions with high concentrations of iodine. By iodometric titrations, where S2O3- titrated directly with iodine, starch is added from the start of titration. When I2 forms IO- in alkaline environments, the acid is added to keep the pH below titration.1 The concentration of a substance is given by equation (1.6) n = V c --------------------------------------(1.6) where c is the concentration, n is moles and V is the volume. n = m Mr --------------------------------------(1.7) where m is mass and Mr is the molar mass of the substance. These equations provide, in combination with equations and the molar ratio of equations, the following expression for the concentration of thiosulfate and copper, respectively, equation (1.8) and the equation (1.9). CNa2S2O3 V S2O32- = 6 CKIO3 V IO3- --------------------------------------(1.8) CCu2+ VCu2+ = CNa2S2O3 VS2O32- --------------------------------------(1.9) where C is the concentration, and V is the volume. One alternative analytical method to determine the copper content in a sample is by electrogravimetry.3 As described in James J. Lingane experiment, the alloy sample was weighed into a covered beaker and dissolved in a warm mixture of hydrochloric and nitric acid. The solution was then boiled gently for 1 minute to remove oxides of nitrogen and chlorine. Subsequently, sodium tartrate dehydrate was added and the solution was diluted to about 200 cc. and treated with hydroxylamine hydrochloride (1 g) as an anodic depolarizer. The solution was then electrolyzed for 60 minutes, with a cathode potential of -0.36 V vs. the saturated calomel electrode. The electrolysis was stopped by lowering the beaker away from the electrodes without disconnecting the circuit. The cathode was then washed quickly with water, dipped into two baths of pure acetone and dried for 3 minutes in an oven at 70 C. Subsequently, the cathode was first cooled to room temperature and then weighed, and the amount of copper deposited was calculated from the difference between initial and final mass of the cathode. Another alternative method to determine copper content is by photometric determination4. The sample (0.500 g) was dissolved in hydrobromic acid (25 mL, 48 %) and diluted to 100 mL in a volumetric flask. An aliquot containing 0.04 to 0.20 mg. of copper was transferred to a separatory funnel and diluted to 50 ml. 4 Norwegian University of Science and Tech KJ2050 Analytical Chemistry Experiment 2

with deionized water. Hydroxylamine hydrochloride (5 mL, 10%) and sodium citrate (10 mL) was then added to the solution and the pH adjusted to between 4 and 6, before addition of neocuproine solution (10 mL). The solution was shook to mix thoroughly and extracted with chloroform (10 mL) for 30 seconds. Subsequently, the chloroform layer was transferred to a volumetric flask and the stem of the funnel was rinsed with two portions of chloroform (1 mL). The extraction was then repeated with additional chloroform (8 mL). The extracted solution was diluted to volume with ethyl alcohol and the absorbance at 454 mF was determined. Iodometric titration can also be used to determine other substances apart from copper such as colbalt5 and trace amount of chlorate ions6. The experimental procedure in the iodometric determination of cobalt is similar to copper, differing only in the preparation of the sample containing cobalt for titration with standard sodium thiosulfate solution. The sample was dissolved in sulfuric acid solution and sufficient sodium bicarbonate was then added to neutralize the acid. Subsequently, hydrogen peroxide (5 ml, 30 %) was added to the solution to oxidize the cobalt completely. The solution was heated to decompose the hydrogen peroxide and then left to cool to room temperature before addition of potassium iodide (5 g), followed by titration with sodium thiosulfate. For the experimental described for the determination of trace amount of chlorate ions, potassium chlorate was dissolved and recrystallized from distilled water. Sodium thiosulfate was used as the titrant and was standardized against primary standard potassium iodate solution.

3. Experimental Procedure
3.1 Standardization of Potassium Iodate Sodium Thiosulfate solution against

Na2S2O3.5H2O (25.1971 g, 0.1015 mols) was weighed and dissolved in adequate amounts of freshly cooled boiled-water. The solution was then transferred to a clean, ground-glass-stoppered storage bottle, and diluted with water up to the mark. KIO3 (1.3341 g, 0.0062 mols) was weighed and dissolved in minimal amount of distilled water in a clean beaker. The solution was then transferred to a 500 mL volumetric flask and diluted up to the calibration mark with distilled water. The mixture was mixed thoroughly. An aliquot of KIO3 (50 mL) was transferred into a Erlenmeyer flask. Solid KI (3.0030 g) was added to the solution, and the flask was swirled to dissolve the solid. Then, hydrochloric acid was added (6 M, 2 mL) to the solution, and titration with Na2S2O3 solution was done immediately. The titration was continued until the yellow triiodide color is just barely visible. Then starch indicator (5 mL) was added, afterwhich sodium thiosulfate solution was added dropwise until the dark blue starch-iodine color disappears2. The titration was repeated three times to obtain three separate parallels. The average of the three results was calculated and recorded. 5

Norwegian University of Science and Tech KJ2050 Analytical Chemistry Experiment 2

3.2 Determination of copper content in an unknown sample The unknown sample (50 mL), which contains Cu(NO3)2, was transferred into a 250 mL beaker. Concentrated H2SO4 (10 mL) was added dropwise to the solution under gentle stirring. The solution was boiled gently until white vapors of SO3 were observed. Under gentle stirring, pure water (20 mL) was added slowly. Then, concentrated NH3 was added slowly to the solution until a deep blue colouration of the solution was observed. H2SO4 (3 M) was then added slowly until the blue colouration disappears, and another 1 mL of H2SO4 (3 M) was added. The solution was cooled, and solid KI (4 g) was added to the solution, then the mixture was gently stirred until complete dissolution of the salt. It was then titrated immediately against the standard Na2S2O3 solution as prepared in Section 3.1. Solid KSCN (2 g) was added just before the end point in order to get a sharper color change.2

4. Experimental Results
For this experiment, Unknown Sample 52 was used. The concentration of weighed sodium thiosulfate (Na2S2O3.5H2O, 25.1971 g, 0.1015 M) was determined using equation (1.8). Table 4.11 shows results from the titration where the concentration of Na2S2O3 was determined using potassium iodate (KIO3-).

Table 4.1 Volume of Na2S2O3 required to titrate against KIO3 solution in the standardization of Na2S2O3 solution Experimental Parallel 1 2 3 Average Volume of Na2S2O3 required / mL 35.10 35.30 35.20 35.20

Table 4.2. Calculation of concentration of Na2S2O3 solution before and after titration. Concentration of Na2S2O3 solution / M Before titration 0.102 After titration 0.106 Percentage deviation 4.7 % The average concentration of copper in the unknown sample was determined using equation (1.9). To determine the mass of copper, equation (1.6) and (1.7) were used. Table 4.3 shows the results for the determination of the copper content in the unknown sample. 6 Norwegian University of Science and Tech KJ2050 Analytical Chemistry Experiment 2

Table 4.3. Volume of Na2S2O3 required to titrate against unknown sample solution in the determination of the copper content in a sample Experimental Parallel 1 2 3 Average Volume of Na2S2O3 required / mL 28.50 28.30 28.40 28.40

Table 4.4. Deviation of the calculated mass of copper from theoretical value Experimental Theoretical Deviation Mass of Copper in Sample / g 0.9604 0.9623 0.2 %

5. Experimental Discussion
From Table 4.4 it was seen that the calculated content of copper in the unknown sample has a deviation of the 0.2 % of theoretical value. This is a small error, as careful considerations were taken when taking the readings of the volume required for the titrations. Also, the colour change was difficult to determine, but care was taken to ensure that when the equivalence point was nearing, the drops of sodium thiosulfate was added dropwise in small quantities. In addition, the glassware was cleaned and dried before the experiment to ensure that there were no impurities to interfere with the results of the readings. During the experiment, there are several significant errors to be expected which may have caused an inaccuracy in the results. One major source of error is the presence of nitrous acid in the solution after gentle boiling7. The presence of nitrous acid in solution will interfere by oxidizing I- to I2, which will affect the titration end point. Thus complete removal of nitrous acid by boiling should be ensured. Another major source of error may be due to the loss of solution by spattering7. Spattering may occur during the transfer of solution between apparatus or during the boiling process where droplets of solution may have spattered out. Care should be taken to ensure quantitative transfer of solution and the boiling of the solution should be gentle to lower the errors caused by spattering. Delay in the titration of the solution against standard thiosulfate solution is also another major source of error in this experiment. As I2 is highly volatile, any delay in the titration will result in a partial loss of I2, thus affecting the titration end point. This error can be minimized by titration of the sample solution immediately. There are also sources of error present in the alternative method of electrogravimetric determination of copper. A major source of error is the 7 Norwegian University of Science and Tech KJ2050 Analytical Chemistry Experiment 2

reduction of other trace metals in the sample solution, which are then deposited on the cathode. As observed in James J. Lingane experiment, only copper was deposited during the initial stages of the electrolysis. However after the deposition of copper was near completion, deposition of bismuth which was present in the sample solution suddenly commenced and proceeded to completion3. This will incur a positive error in the mass of the cathode and thus a positive error in the mass of copper calculated. Another source of error can be due to the loss of analyte deposited during the washing of the cathode after the electrolysis has ended. Partial resolution of the lead deposit during the washing3 was experienced in James J. Lingane experiment, which resulted in a low yield for lead deposited. Although copper was not stated to have undergone resolution in the experiment, minimal amount of copper can be assumed to have been rinsed away during washing. Loss of analyte may also occur due to incomplete electrolysis of the sample solution, producing a negative error in the mass of copper obtained. This error can be minimized by a monitoring a current-time curve3 to determine the appropriate time to end the electrolysis for complete deposition of the analyte. Major sources of errors that arise in photometric determination of copper may be caused by incomplete extraction, presence of excess oxidizing agent and multiple transference of solution between apparatus as described below respectively. Difficulties may arise in keeping the sample in solution, thus saturated ammonium acetate solution buffered at pH 5 with acetic acid can be added to keep the sample in solution4. However as the resulting solution is miscible with the chloroform, extraction may not be complete thus resulting in an error. In this experimental method, copper must exist in the cuprous state (Cu+)4. Thus an excess of oxidizing agent will oxidize Cu+ to Cu2+, which will affect the accuracy in the determination of the copper content. Loss of solution may occur during the multiple transference of solution from the volumetric flask to the separatory funnel. With increased number of transference, the accumulated amount of the sample lost with each transference becomes significant. In a comparison of the three methods described, photometric determination has the highest sensitivity, in the range of 0.002 to 1.00 % of copper in aluminum4. Electrogravimetry is also sensitive to copper by adjustment of the cell voltage to a constant -0.36 V, however other metals of similar cell potential may be deposited as well. Iodometric determination may be less sensitive as the pH of the solution may vary with each titration sample prepared, thus affecting the titration end point.

Norwegian University of Science and Tech KJ2050 Analytical Chemistry Experiment 2

In the determination of copper in samples such as sea water, various inferences may be present. For the electrogravimetric determination, trace amounts of metal in sea water, such as bismuth, gold, mercury and the metals of the platinum group, can interfere3 with the deposition of copper on the cathode. However, presence of relatively large amounts of tin, antimony, lead, zinc will not interfere with copper. The major interference in the iodometric determination of copper is the presence of NO3- ions which may oxidize I- to I2. However this can be effectively removed by gentle boiling of the sample solution producing fumes of SO3 gas. Thus iodometric determination may be a more suitable method for copper content determination in sea water. In the terms of sources of error, electrogravimetric method may have the least significant errors as the experimental procedure minimizes mechanical errors and no loss of analyte caused by transference of sample between apparatus is experienced as all procedures are conducted in one beaker. The method is also the least complex in terms of experimental procedures, which minimizes human error.

6. Conclusion
In this experiment, the sodium thiosulfate (Na2S2O3) was standardized using potassium iodate and by using the standardized Na2S2O3 solution, titrations were carried out for determination of copper in an unknown sample. It was then calculated that the mass of copper present in the unknown sample #52 was 0.9604 g. The experimental results deviated from the theoretical value, which is 0.9623 g, by 0.2 %, but using a higher concentration of iodine, the results could be more accurate as the color change in determining equivalence point could be more easily observed.

Norwegian University of Science and Tech KJ2050 Analytical Chemistry Experiment 2

7. Literature
1. Skoog, D.A., West, D. M., Holler J. F., Crouch S. R. (2004). Fundamentals of Analytical Chemistry. Thomson Learning. 2. Mikkelsen O. (2012). Preparation and Standardization of a sodium thiosulfate solution. Experiment 3 (Thursday 11 October 2012). NTNU: Trondheim 3. James J. Lingane, Electrogravimetric Determination of Copper in Copper-Base and Tin-Base Alloys by Controlled Potential Electrolysis, Industrial & Engineering Chemistry Analytical Edition 1945 17 (10), 640-642 4. J. W. Fulton and Jane. Hastings, Photometric Determination of Copper in Aluminum and Lead-Tin Solder with Neocuproine, Analytical Chemistry 1956 28 (2), 174-175 5. H. A. Laitinen and L. W. Burdett, Iodometric Determination of Cobalt, Analytical Chemistry 1951 23 (9), 1268-1270 6. Y. Ikeda, T. Tang, and G. Gordon, Iodometric method for determination of trace chlorate ion, Analytical Chemistry 1984 56 (1), 71-73 7. R. C. Brasted, Iodometric Codetermination of Copper and Iron, Analytical Chemistry 1952 24 (6), 1040-1041

Done and checked by:

_______________________________ Chan Ao Bang Osborne Date: 11 November 2012 10 Norwegian University of Science and Tech KJ2050 Analytical Chemistry Experiment 2

8. Appendix
Calculation of concentration of Na2S2O3 solution before titration Mr of Na2S2O3.5H2O = 248.18 Mass of Na2S2O3.5H2O = 25.1971 g n(Na2S2O3.5H2O) = 25.1971/248.18 = 0.10152752 = 0.1015 M Calculation of concentration of Na2S2O3 solution after titration Mr of KIO3 = 214.001 g/mol Mass of KIO3 = 1.3341 g Number of moles of KIO3 in aliquot = (1.3341/214.001) / 10 = 6.2341 x 10-4 moles According to the formula: CNa2s203 VS2O32- = 6 CKIO3 VIO3 CNa2s203 = 6 x 6.23408 x 10-4 / (35.20/1000) = 0.1063 M Calculation of percentage deviance of concentration of Na2S2O3 solution before and after titration Percentage deviance = (0.10626-0.101527)/0.1015 x 100 = 4.7% Calculations for mass of Copper in unknown sample Volume of unknown sample= 250 mL According to the equation: CCu2+ x VCu2+ = CNa2S2O3 x VS2O32CCu2+ = 0.1062 x (28.40/1000) / (50/1000) = 0.0604 M Number of moles of Cu in the unknown sample = 0.06356 x 250/1000 = 0.0151 mols 11

Norwegian University of Science and Tech KJ2050 Analytical Chemistry Experiment 2

Mass of Cu in the unknown sample = 0.0150891136 x 63.646 = 0.9604 g Calculation for deviation of the calculated mass of copper from theoretical value Percentage deviation = (0.9623 0.9604)/0.9623 x100% = 0.2 %

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Norwegian University of Science and Tech KJ2050 Analytical Chemistry Experiment 2

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