Date Performed: August 12, 2009

Quantitative Determination of Copper Concentration in Aqueous Solution by Iodometric Titration

C.L.N. Macapagal Department of Chemical Engineering, College of Engineering University of the Philippines, Diliman, Quezon City Philippines
Submitted August 20, 2009

RESULTS AND DISCUSSION There are two types of redox titrations involving iodine: 1) Iodimitry, and 2) Iodometry. In Iodimitry, a reducing agent (analyte) is directly titrated with Iodine (I2) to produce Iodide (I-) In Iodometry an oxidizing reagent (analyte) is added to excess I- to produce I2, which is then titrated with standard thiosulfate solution. Iodometry is further subdivided into two categories a) Direct Method wherein a standard I- solution is used as oxidizing agent; and b) Indirect Method wherein oxidizing agents are made to react with an acidic solution of soluble iodide, liberating an equivalent amount of I2 which is then titrated with a strong reducing agent. Iodimitry is not often used as a method because it requires reducing agents which can be quantitatively oxidized at equivalence point, thus limiting the analytes it can react with. The experiment involves the determination of Copper Concentration in an unknown sample using Iodometric titration. 2Cu2+ + 4I- 2CuI + I2 (1)

near the equivalence point to displace the Triiodide from CuI, and thus making the endpoint sharper. Early addition of KSCN may repress the formation of CuI. The iodometric process is dependent on pH. Iodine reacts with water, as shown by the following equation I2 + H2O H+ + I- + HIO Basic solutions pushes the equilibrium to the right causing an unstable Iodine concentration. For this reason, iodine titrations are performed at neutral or acidic solutions. However, strongly acidic solutions because it makes iodide susceptible to air oxidation. It is important to precipitate Cu(II) ions using ammonia and redissolving it using acetic acid because it allows the removal of impurities but at the same time creates a buffer so that appreciable amounts of iodide will not be lost. Steps must be taken to preserve the ideal concentration of a standard thiosulfate solution. The standard thiosulfate solution was prepared by dissolving Na2S2O35H2O crystals in boiled distilled water. Dissolved CO2 present in distilled water must be evaporated by boiling because it makes the solution acidic and promotes the disproportionation of S2O32-, as described by the following equation, S2O32- + H+ HSO3- + S(s) Thus lowering the apparent concentration of thiosulfate in solution. Iodide in acidic solution may be oxidized by air, as shown by the equation below, 4I- + 4H+ + O2 2I2 + 2H2O Thus it is important to titrate immediately after addition of KI to avoid the loss of material. Metal ions, such as copper, catalyze air oxidation, as shown by the following equations, 2Cu2+ + 2S2O32- 2Cu+ + S4O622Cu+ + O2 + 2H+ 2Cu2+ + H2O

Iodide is added in excess to the sample to precipitate CuI completely, producing Iodine in the process. I2 + I- I3(2)

Iodine then forms Triiodide complex (soluble in aqueous solution) by reacting with excess Iodide ions. 2S2O3-2 + I3- S4O62- + 3I(3)

Triiodide is then titrated with standard Thiosulfate solution, producing tetrathionate and Iodide. The endpoint is not sharp due to adsorption of Triiodide to Cuprous Iodide, the precipitate in (1). CuI: I3- + SCN- CuI:SCN- + I3Thiocyanate salt, KSCN, is added to the solution During storage, chloroform may be added to the

standard thiosulfate solution to impede bacterial action that decomposes thiosulfate. The bacteria that decomposes thiosulfate was found to be less active in pH 9 or 10. Addition of Sodium Carbonate maintains the pH in an optimum range for a relatively stable solution. The solution must also be stored in the dark because light accelerates the hydrolysis of iodine, causing the decomposition of HI, as shown by the following equation, 2HIO 2H+ + 2I- + O2 Starch solution was used as the indicator. It forms a deep blue color when reacted with iodine, formed on the surface of the colloid particles when iodine is adsorbed and is discharged when the iodine reduces to iodide. Starch should not be added until just immediately prior to endpoint (iodine color is begins to fade), because it is adsorbed on the surface of the precipitate which delays the color change. In cases wherein the use of starch solution may not be suitable, the use of redox indicators (exhibits distinct color changes during oxidation and reduction) and extraction method is employed. Extraction method involves the use non-miscible organic liquids such as toluene. Iodine is more soluble in organic solvents, thus a more intense color is formed in the aqueous layer (due to a higher concentration of iodine) and the heavier organic liquid deposits at the bottom. The endpoint is signaled by the disappearance of iodine color in the bottom layer. The method is more sensitive than starch method, but requires more time and more rigorous because the solution must be allowed to stand every after addition of a reagent. Table I shows the reported values for Copper Concentration in aqueous solution expressed in parts per million.

Table II. Copper Concentration [Cu2+] present in unknown sample

Trial Molarity, mol/L Parts Per Million, mg/L 0.0738 4690 0.0770 4900 0.0981 6240 The copper concentration in Trial 3 was relatively large compared to that of Trials 1 and 2. If the mean were computed by disregarding Trial 3, the mean would be equal to 0.0754 M, which is approximately 10% lesser than the actual mean. The difference was made evident when [Cu2+] was expressed in parts per million. The relatively large range, relative standard deviation and confidence limits may be attributed to the large deviation of the Trial 3. Possible sources of error may be 1) air oxidation of iodide from iodine due to too slow titration, thus lowering the normality of thiosulfate solution, 2) loss of iodine due to volatilization, thus increasing normality of thiosulfate solution, 3) difficult in endpoint determination that may lead to over titration, and thus increase Copper concentration and 4) incorrect pH due to use of too much ammonia (less iodine concentration) or over acidification (less iodide concentration). REFERENCES [1] [2] Pierce, W.C. Quantitative Analysis. Wiley, New York, 1948. Skoog, D.A. et.al. Fundamentals of Analytical Chemistry Eighth Edition. Thomson Learning Asia, Singapore, 2004.

1 2 3

Table I. Reported Values of Copper Concentration [Cu2+] in ppm Mean 5270 Range 1544 Relative Standard deviation 159 ppt Confidence Limits 5270 2083

[3] Willard, H. and Fulman, N.H. Elementary Quantitative Analysis: Theory and Practice. D. Van Nostrand The mean [Cu2+] using three trials was 5270 ppm. Company, New York, 1940. The range is equal to 1544 ppm. The relative standard deviation has a large value equal to 159 ppt. The confidence limits at 95% confidence level is equal to 5270 2083. It can be noted that the reported values for precision are relatively large, as supported by Table II showing the Copper Concentration present in the unknown sample.