QUANTITATIVE DETERMINATION OF OXALATE BY PERMANGANATE TITRATION

RESULTS AND DISCUSSION There are factors to be considered in preapring potassium permanganate (KMnO4). The solution must be free of reducing agents for the solution not to reduce rapidly. MnO2 will precipitate and will cause the solid MnO2 to catalyze the decomposition of the solution if there are traces of reducing agents in the solution. The Guyard reaction shows the instability of permanganate in the presence of Mn2+ ions. 2MnO4- + 3Mn2+ + 2H2O 5MnO2 + 4H+ (Guyard reaction)

The decomposition of KMnO4 is also brought about by light. This is the reason why use of dark reagent bottles is needed, to avoid the decomposition of the solution. This solution also undergoes decomposition with respect to time; which is why it is needed to restandardize the solution if it is to be used for a very long time. During the preparation, the solution should be kept away from dust particles, filter papers, and rubber. This shows that KMnO4 is a solution that is sensitive of the environment, and that it is carefully stored because it decomposes quickly over time. A blank solution consists of all the reagents used in the sample except the analyte. Usually in a determination, the raw response from the instrument is not used. Instead, the raw analytical response is corrected by measuring a blank. Blank titration serves as an adjustment for errors. It is needed to run a blank so as to know if any considerable volume of permanganate is necessary. A blank greater than one drop of permanganate should be subtracted from the volume used in titration. It is also necessary to insure that NaOH is free of reducing agents. Potassium permanganate is one of the most valuable oxidants for general purposes because of its self-indicating property. As long as the standard permanganate that is being added to a solution is being reduced, the color of the permanganate ion rapidly disappears. As soon as all the reducing agent has been oxidized, a single drop of the standard MnO4 solution imparts a faint pinkish or purplish tint to the solution. Using a self-indicator in titration, less reagents are used, less cost and contamination, and it produces a sharp change of color upon reaction because it initially has color already. In the presence of Mn2+ ions, the permanganate decomposes quickly. To avoid this, sources of this contaminant is needed to be removed. A way of doing this is by heating the solution before standardization, and digesting it near the boiling point before filtration. Sodium oxalate is an anhydrous solution. It can be heated to 240C without decomposition and it gives a colorless solution which is perfectly stable. The oxalate is converted into sodium carbonate by ignition, and is therefore of value also as a standard in acidimetry. This results to a faster rate of reaction because temperature is high. The purple color also readily disappears in high temperatures. It is needed to increase the rate of reaction since the initial reaction is relatively slow. Increasing it would save more time and reagents used.

An acidic medium is needed in order to carry out titrations with permanganate. Sulfuric acid, H2SO4, is the suitable acid to acidify the analyte mixture because it does not act on permanganate in dilute solutions. Hydrochloric acid, HCl, sometimes causes reduction as in the chemical reaction: 2KMnO4 + 16HCl 2KCl + 2MnCl2 + 5Cl2 + 8H2O Based on this chemical reaction, one can say that permanganate is used up in the formation of chlorine and also in the titration. To prevent loss of material, H2SO4 is used instead of HCl. In this experiment, sources of errors are present in the preparation of blank samples. Differences in experimental variables at the times at which blank, sample, and standard are measured can invalidate the calibration. Even when the basic assumption is valid, errors can still occur owing to contamination during the sampling or in the sample preparation steps. Other source of error is also in standardization. Differences in changes in volume of the solution and concentration could change the results of the experiment. A higher concentration of the analyte would give to a lesser volume resulting to a lesser amount of oxalate. This is unavoidable because of the concentrations of standards due to volatilization, decomposition, and adsorption on the container walls. In this experiment, random errors are also present and having a direct effect on the calculated composition of the sample. REFERENCES Skoog, D.A., West, D.M., Holler, J.F., Crouch, S.R. Fundamentals of Analytical Chemistry. Eighth Edition. Thomson Brooks/Cole, Canada, 2004. Hamilton, L.F., Simpson, S.G. Quantitative Chemical Analysis. Twelfth Edition. MacMillan Company, USA, 1964. Pierce, W.C., Sawyer, D.T. Quantitative Analysis. Fourth Edition. John Wiley & Sons, Inc., London, 1958. Laitinen, H.A., Harris, W.E. Chemical Analysis. Second Edition. McGraw-Hill Inc., USA, 1975. Willard, H.H., Furman, N.H. Elementary Quantitative Analysis: Theory and Practice. D. Van Nostrand Company, Inc., New York, 1940.