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QUANTITATIVE DETERMINATION OF COPPER CONCENTRATION IN AQUEOUS SOLUTION BY IODOMETRIC TITRATION
DEPARTMENT OF CHEMICAL ENGINEERING, COLLEGE OF ENGINEERING UNIVERSITY OF THE PHILIPPINES, DILIMAN QUEZON CITY, PHILIPPINES RECEIVED AUGUST 31, 2011
The objective of the experiment was to determine the copper concentration in an aqueous solution using a redox titration called iodometry. A standard Copper solution was made using 15.62g of pure Copper sulfate pentahydrate. A working standard of Copper solution was then prepared. A thiosulfate solution was then standardized and used as a titrant. A 50ml Copper solution sample was obtained and three 10ml aliquots were taken. The aliquots were then titrated with the standardized thiosulfate solution and the initial and final volumes were recorded. The concentration of Cu(II) ions were then calculated. Means 0.161 M and 10230 ppm, ranges 0.036 and 2288, and confidence limits 0.16M ± 0.05M and 10000 ppm ± 3000 ppm were obtained (molarity and ppm respectively). The calculated RSD’s 124.068 ppth and 124.883 ppth show that bad precision was obtained.
INTRODUCTION There are two types of redox reactions involving the substance Iodine, Iodimetry and Iodometry. Iodimetric titration involves a direct titration of a reducing analyte with Iodine. In Iodimetry, there is only one reaction present in the titration process.  ( ( ) )
Iodine has a low solubility in water and it is volatile. Because of its volatility, amounts of Iodine can be lost in the solution. In excess Iodide, the Iodine reacts with Iodide to form a triiodide complex. Reaction  allows one to obtain useful concentrations of Iodine in aqueous solution. Reaction  lowers the free concentration of I2 and the solution is stable enough to titrate. Thus, it is beneficial to have excess iodide in the solution.  The triiodide solution is then titrated with a standardized Thiosulfate solution, a reducing agent. The Thiosulfate solution reduces the I3back to Iodide.  Drops of freshly prepared starch solution are added to indicate the endpoint, as I2 (I3- in aqueous solutions) bonds with the starch forming a blue-black complex. Titration is
However, there are only few reducing agents strong enough to reduce Iodine. Because of this, there are only few titrations that involve iodimetry. In an Iodometric titration, an oxidizing analyte is made to react with Iodide to produce Iodine.  ( ) ( )
continued until the blue-black color disappears. The blue-black color, however, may reappear because of the oxidation of the excess I- with the air. The volume of the standardized Thiosulfate used is measured, and if all the required calculations go smoothly, one can accurately calculate the concentration of the copper present in the aqueous solution. RESULTS AND DISCUSSION In this experiment, the analyte is copper (in the form of CuSO4•5H2O), which is strong enough to oxidize Iodide ions to Iodine. 1:1 (v/v) NH3 was then added dropwise to precipitate out the Cu(II) ions. It is important not to add the NH3 in excess because [Cu(NH3)4]2+ interferes with the reduction of Cu2+ and changes the pH of the solution, which also interferes (slows) with the reaction. To prevent this, 1-2 drops of Glacial acetic acid was added to counter the pH change caused by the added NH3 and to dissolve the precipitate formed. I-„s (in the form of KI) were then added in excess to ensure that all of the Cu2+‟s in the solution would be reduced. After the addition if KI, it is important that the solution must be titrated immediately because the excess I- can be oxidized by the air and this leads to a positive error. The oxidation of Iodide by Cupric ions is shown below: 
the decomposition of Thiosulfate ions to Sulfur. It is also important to add some solid Na2CO3 in the solution. Na2CO3 raises the pH slightly that prevents bacteria from growing (that may metabolize the Thiosulfate ions) if the solution is left to stand for a period. To indicate the endpoint of the titration, drops of starch solution must be added. It is important that the starch solution is freshly prepared so that it has not yet decomposed slowly and its sensitivity (its ability to bond with I2) has not yet decreased. It is also important to delay the addition of starch until almost all of the I2 (I3- in aqueous solutions, refer to reaction ) is reduced to I- because the disappearance of the blue-black will be gradual. In addition, the presence of the excess of I- (the product of reaction ) increases the sensitivity of the starch indicator. That is also the reason why KI was added in excess. However, the precipitate formed in reaction , CuI(s), adsorbs I2 (I3- in aqueous solutions) which causes a dull endpoint (the color change near the equivalence point is gradual, i.e. the endpoint has already been reached but the color change is undetected). This can be prevented by adding CNS-, for CNS- displaces the adsorbed I2, shown below:  The addition of CNS- makes the endpoint sharper because I2 is now available for bonding with the starch indicator. The disappearance of the blue-black color must last for at least 30 seconds or the titration has not reached the endpoint yet. The disappearance is always temporary as the excess I- will react with O2 in the air leading to the production of I2, which will be detected by the starch and hence the blueblack color will reappear. The reaction is shown below: 
The reaction proceeds rapidly in slightly acidic to neutral solutions. The reaction proceeds very slowly in strongly basic or acidic solutions. The I2 produced will then react with the excess Ito form I3- shown in . KI is also added to ensure that the iodine (low solubility in water) produced by  will react with the excess I- to form I3-. The I3- is then titrated with the standardized Thiosulfate solution. The reaction is shown in . In the preparation of the standard Thiosulfate, it is important to boil the distilled water that will be used to dissolve the Thiosulfate. Even distilled water that was left standing for a period may have dissolved enough CO2 that can lower the pH sufficiently leading to
Table I. Standardization of Sodium Thiosulfate Solution Trial # 1 2 3 Net volume of Thiosulfate (mL) 15.3 4.6 10.7
As one can see, the data gathered is very inconsistent. The large differences on the titrant used can be explained by many factors. One of the factors is color change detection. Since the data from this experiment came from the whole class (i.e. each trial is done by a different person), the ability to detect slight color changes varies from person to person (e.g. their definition of light brown/ tan or any other color differ), thus their “endpoint” also varies, which results to these large differences in the titrant used. Another factor is the solution preparation. Since these data came from different groups and each group has to prepare their own “working standard” of Cu(II) solution, there is a large chance that the prepared solutions really did differ in their molarities (some groups may have committed errors during the solution preparation while others did not). Table II. Sample Analysis Trial # 1 2 3 Net volume of Thiosulfate (mL) 24.0 23.6 29.35
There are many sources of error in the experiment. A source of error is CuI(s) (a product of reaction ) forms a weak complex with I2. If this happens, there will be less I2‟s that would be available to react with Thiosulfate and hence, a negative error would be obtained. This can be prevented by adding SCN- ions just before the titration has reached its endpoint. Another source of error is I2 is volatile and some amounts of I2 may evaporate before titration resulting into a negative error. This can be prevented by adding excess I- because I2, together with I-, forms I3-, a more stable complex. Also, one can perform Iodometric titration using cold solutions so that the evaporation is minimized. Another source of error is in acidic solutions, the excess I- can be easily oxidized in to I2 resulting in a positive error. Titrating the solution immediately with the standard Thiosulfate solution can prevent such unnecessary oxidation. Another source of error is adding a large amount of excess NH3. Even though the NH3 can be neutralized by adding Glacial acetic acid, the NH4CH3COO formed may interfere with reaction , resulting in a negative error. This can be prevented by adding NH3 dropwise and one should observe if the solution changes for every each drop added. CONCLUSIONS AND RECOMMENDATIONS Although the data was very inconsistent, the method is successful in determining the concentration of cupric ions in an aqueous solution. The procedure for this experiment can be made better. The lab manual states, “After the addition of KI, the solution must be titrated until the brown color almost disappears”. This statement needs a revision because if the brown color almost disappears, the solution is already overtitrated with Thiosulfate ions. Other sources indicate that one must stop the titration if the color of the solution turns light brown/tan (completely different from almost disappeared) to add the starch indicator. With more trials, the RSD and Confidence limit interval would become much smaller and one can find a more precise value of the concentration of Cu2+ ions in the sample.
Compared to the standardization of the titrant, the data from the sample analysis are much more precise. However, the same difficulties were encountered and many trials were wasted. Concentrations (in Molarity) 0.151 M, 0.148 M, and 0.184 M were calculated from trials 1, 2, and 3 respectively. A range of 0.036, RSD of 124.068 ppth were obtained. Based on the calculated statistical parameters, the precision is not that great. The accuracy of the experiment cannot be determined yet because the actual amount the Cu2+ concentration in the sample was not disclosed.
It is also recommended that the Thiosulfate solution must be standardized using another kind of titration that does not involve iodine. This procedure is more precise than the one indicated on the lab manual. Then after the standardization, one can proceed to the copper analysis part. The procedure indicated by the lab manual for this experiment leads to many systematic errors. If one wants to determine the concentration of cupric ions in an aqueous solution, he/she may use spectrophotometry, which is faster and highly more sensitive than iodometry. This method is based on the formation of [Cu(NH3)4]2+. Unlike in iodometry, excess NH3 is added to allow the formation of the complex and using Beer‟s law and a blank solution, one can accurately determine the actual Cu2+ concentration in the aqueous solution. APPLICATIONS Determination of the amount of copper in a brass alloy sample. Determination of the %H2O2 in Agua Oxigenada bottles (antiseptic). Determination of IO3- and IO4- present in Aminophenols. Determination of Oxygen content of H2O samples.
 Kimsley, V.S.: Introductory Chemistry, 2nd Ed. Brooks/Cole Publishing Company, California. 1995  Skoog, D.A., West, D.M., Holler, F.H., Crouch, S.R.: Fundamentals of Analytical Chemistry, 8th Ed. Brooks/Cole Publishing Company, California, 2004.  Gregersen, E.: The Britannica Guide to Statistics and Probability, 1st Edition. Rosen Educational Publishing, 2010  Peter, A., Shriver: Inorganic Chemistry: Shriver and Atkins, 4th Edition. Oxford University Publishing, 2006  Kimura, M., Ikawa R., Shiota, Y., Tsukahara, K. “Kinetics and Mechanism of the Copper(II)-Catalyzed Oxidation of Iodide Ion by Chromate (VI) Ion in Aqueous Solution”. The Chemical Society of Japan, Volume 71, pp. 893897.  Christian, G.D.: Analytical Chemistry, 6th Edition. Wiley Publishing, New York, 2003. APPENDIX A. WORKING EQUATIONS ∑ ∑ √ ( )
REFERENCES  Petrucci, P.H., Herring, F.G., Madura J.D. and Bissonnette C.: General Chemistry, Principles and Modern Application, 10th Ed. Prentice Hall, New Jersey, 2010  Rosenberg, J.L., Epstein, L.M.: College Chemistry, 7th Ed. McGraw-Hill, Inc., New York, 1990  Brown, T.L., Le May Jr., H.E., Bursten, B.E.: Chemistry the Central Science, 11th Ed. Prentice Hall, New Jersey, 2010.  Mortimer, C.E.: Chemistry, 6th Wadsworth Publishing Company, 1986 Ed. √
3rd Trial: Where: is the mean; n is the number of measurements taken; s is the standard deviation; RDS is the relative standard deviation; R is the range; RR is the relative range; CL is the confidence limit (95%); [S2O32-] is the molarity of S2O32-; [Cu2+] is the molarity of Cu2+; T Cu2+ is the titer of Cu2+ in mg/ml; Ppm Cu2+ is the concentration of Cu2+ expressed in mg/L.
B. SAMPLE CALCULATIONS Standardization of S2O32-: 1st Trial: Determination of ppm Cu2+: 1st Trial: 2nd Trial:
2nd Trial: 3rd Trial:
3rd Trial: Average [S2O32-]:
̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ Determination of Cu2+ concentration: 1st Trial:
Average ppm Cu2+:
Statistical Parameters for [Cu2+]:
Relative Standard Deviation:
Standard deviation: ∑ √ ( )
Relative Standard Deviation:
The pooled standard deviation cannot be calculated because the data gathered came from the whole class (i.e. the parts of the data came from different groups).
Confidence Limit: √ √ Statistical Parameters for ppm Cu2+:
Standard Deviation: ∑ √ ( )
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