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QUANTITATIVE DETERMINATION OF OXALATE BY PERMANGANATE TITRATION

Borras, A.E.L. Department of Food Science and Nutrition, College of Home Economics Date Due: 01 February 2013 Date Submitted: 01 February 2013 In this experiment, permanganate titration using Potassium Permanganate (KMnO4) in acidic medium was used to determine the concentration of oxalate in the sample. KMnO4 is a good oxidizing agent of different inorganic and organic substances. Under different conditions, KMnO4 reduces as follows: Acidic: MnO4- + 8H+ + 5e- Mn2+ + 4H2O (1) Basic: MnO4- + e- MnO42(2) Neutral: MnO4- + 2H2O + 3e- MnO2 + 4OH- (3) KMnO4 in titration reduces errors brought about by the use of chemical indicators since excess permanganate can already determine the endpoint of titration. In this case, Permanganate serves as a self-indicator, which under acidic conditions, becomes pale pink by the presence of Mn2+. In addition, Mn2+ serves as auto catalyst, which is directly proportional to the speed of the reaction, causing an increase in the speed with an increase in the concentration of Mn2+. The reaction of permanganate with oxalate involves an oxidation-reduction reaction (RedOx) with half reactions (HR) given by: Reduction HR: MnO4- + 8H+ + 5e- Mn2+ + 4H2O Oxidation HR: C2O42- 2CO2 + 2e(4) Overall: 2MnO4- + 16H+ + 5C2O42 2Mn2+ + 8H2O + 10CO2 (5) During the experiment, solution of KMnO4 was prepared as it will be used as the titrant in the experiment. Preparation of KMnO4 should be done with outmost caution by covering the buret and flasks used with aluminum foil since it can easily be decomposed by the presence of MnO2 as well as exposure to sunlight. As much as possible also, the contact with skin of KMnO4 was avoided as it can oxidize the skin causing irritation and discoloration of the skin. If then the solution will be stored for future use, it should be boiled to further remove other reducing substances present and may contaminate the solution. The prepared solution was standardized using a primary standard in the form of Na2C2O4 that has high purity, stability and it being nonhygroscopic. In the analysis of the sample, the analyte solution was acidified using 3 M H2SO4. The solution was then heated until 70C and was immediately titrated with the prepared KMnO4 solution. Heating is important since the reaction of the analyte and the titrant is slow at room temperature. Immediate titration was performed to continue the rate of the reaction with respect to its initial rate, and Mn2+ being an autocatalyst, will add to the fastness of the reaction. It should be noted that H2SO4 was used to acidify the analyte and not HCl. The highly oxidative property of the titrant will oxidize the Chlorine ions (Cl-) into Chloride (Cl2) and thus may contaminate the sample. A blank sample was done during the analysis of the sample. A blank sample is a sample that includes all substances and chemicals needed in the experiment except the analyte, in this case, the oxalate. The blank sample increases the accuracy of the experiment by allowing interferences such as contamination from substances oxidized in the sample as well as difference in the endpoint not detected right away from the original sample. Table 1 shows the results obtained during the analysis of the oxalate sample, which has already been corrected, with volume of the blank sample equal to 0.3mL.

Table 1. Sample Analysis 1 Sample weight, g Vnet Vblank, mL 0.1316 3.5 2 0.1011 10.9 3 0.1029 3.8

0.020M. In this case, it can be said that the titrant prepared is too concentrated that is why only a smaller volume was needed for the reaction to occur and end. REFERENCES: Chemistry 221 Laboratory: Quantitative Analysis. Adapted from J Chem. Ed. 1992. http://kinardf.people.cofc.edu/221LabCHEM/C HEM221L%20Permanganimetric %20Determination%20of%20Iron.htm. Accessed 29 January 2013. Dulski, Thomas R. A Manual for the Chemical Analysis of Metals. Ann Harbor, MI. March 1996. http://books.google.com.ph/books? id=ViOMjoLKB1gC&pg=PA150&lpg=PA150 &dq=titration+with+a+selfindicator+and+its+advantages&source=bl&ots= gru1eH9HrE&sig=2YBCXQYqqpLcdYKA3peLeZmxm8&hl=fil&sa=X&ei=ZhAKUZeeL M2iigfQhoCwBw&sqi=2&ved=0CIABEOgBM Ag#v=onepage&q=titration%20with%20a %20self-indicator%20and%20its %20advantages&f=false. Accessed 30 January 2013. Jain, Manisha. Redox Titration. University of Delhi, Delhi India. http://eduframe.net/andc/chemistry/Che01/Redo x%20Titrations%20only%20-%20Final.htm#1. Accessed 30 January 2013. Potassium Permanganate. http://www.epa.gov/ogwdw/mdbp/pdf/alter/chap t_5.pdf. Accessed 30 January 2013.

It can be observed that the volume of the titrant is not consistent concerning the other samples. Sample 2, with the lowest sample weight, had the highest volume needed to reach the endpoint without overtitrating the sample. Table 2 Reported Values Trial 1 2 3 Ave. Molarit y 0.1120 0.0276 0.0806 0.0734 Normality 0.2240 0.0552 0.1612 0.1468 Titer % Na2C2O4

The molarity of the titrant used in each sample was higher than the prepared solution. The standardized solution was 0.020 M KMnO4, however, the lowest value for the molarity obtained was 0.0276M with highest of 0.1120M and average of 0.0734M. By obtaining these kinds of values will affect the percentage of Na2C2O4 by actually exceeding 100%. This error in the data can be attributed to the indeterminate or determinate errors during the whole experiment. It may be possible that the substances still present in the buret decomposed the titrant used despite washing the buret. Misreading the actual volume used because of the dark color of the titrant and cover of the buret could also be one reason; however, it is quite improbable to happen since the aluminum foil covering the buret is removed occasionally for accurate reading. It can be said that the error in the data cause the experiment to be quite a failure since a large difference in the expected molarity was obtained due to some errors. Even in the standardization of the permanganate, a larger volume of the titrant is needed to get a closer molarity to

CHEMISTRY 221 LABORATORY? QUANTITATIVE ANALYSIS


EXPERIMENT: PERMANGANIMETRIC DETERMINATION OF IRON IN IRON OXIDE Adapted from J. Chem. Ed., 1992, 69, 935.
THEORY:

Potassium permanganate has been widely used as an oxidizing agent for over 100 years. It is a reagent that is readily available, inexpensive, and requires no indicator unless very dilute solutions are used. One drop of 0.1 N permanganate imparts a perceptible pink color to the volume of solution normally used in a titration. This color is used to indicate excess of the reagent. Permanganate undergoes a variety of chemical reactions, since manganese can exist in oxidation states of +2, +3, +4, +6, and +7. The most common reaction encountered in the introductory laboratory is the one that takes place in very acidic solutions, 0.1 M or greater: MnO4- + 8 H+ + 5 eMn+2 + 4 H2O E?= +1.51 V Special precautions must be taken in the preparation of permanganate solutions. Manganese dioxide catalyzes the decomposition of permanganate solutions. Traces of MnO2 initially present in the permanganate, or formed by the reaction of permanganate with traces of reducing agents in the water, leads to decomposition. Directions usually call for dissolving the crystals, heating to destroy reducible substances, and filtering through asbestos or sintered glass (non-reducing filters) to remove MnO2. The solution is then standardized, and if kept in the dark and not acidified, its concentration will not change appreciably over a period of several months.
Standardization of Permanganate Solutions: Sodium Oxalate

Sodium oxalate, Na2C2O4, is a good primary standard for permanganate in acid solution. It can be obtained in a high degree of purity, is stable on drying, and is non-hygroscopic. Its reaction with permanganate is somewhat complex, and even though many investigations have been made, the exact mechanism is not clear. The reaction is slow at room temperature, and hence the solution is normally heated to about 60 ? Even at an elevated temperature the reaction starts C. slowly, but the rate increases as manganese(II) ion is formed. Manganese(II) acts as a catalyst, and the reaction is termed autocatalytic, since the catalyst is produced in the reaction itself. The equation for the reaction between oxalate and permanganate is 5 C2O4-2 + 2 MnO4- + 16 H+ 2 Mn2+ + 10 CO2 + 8 H2O For a number of years analysts employed the procedure recommended by McBride, which called for the entire titration to be carried out slowly at elevated temperature with vigorous stirring. Later, Fowler and Bright thoroughly investigated the reaction and recommended that almost all of the permanganate be added rapidly to the acidified solution at room temperature. After the reaction is complete, the solution is heated to 60 ? and the titration completed at this C temperature. This procedure eliminates any error caused by the formation of hydrogen peroxide.

a. Strongly alkaline medium MnO4 + e- MnO42Permanganate ion Manganate ion b. Neutral medium MnO4 + 2H2O + 3e-c. Acidic medium MnO4 + 8H+ + 5e Mn2+

Ered = +0.56V MnO2 + 4OHManganese dioxide ppt. Ered = +1.23V

+ 4H2O Ered = +1.51V Manganous ion

Titration of Potassium permanganate Vs Oxalic acid Potassium permanganate is not a primary standard. It is not easily obtained in perfectly pure form which is completely free from manganese dioxide. Also the aqueous solutions are not stable for long as the ordinary distilled water usually contains reducing substances (traces of organic matter, etc.) which react with permanganate resulting in precipitation of MnO2. This reaction is catalysed by light. Presence of manganese dioxide is totally undesirable as it catalyses the auto decomposition of the permanganate ion on standing: 4MnO4 + 2H2O 4MnO2 + 3O2 + 4 OH

Permanganate solution decompose in presence of manganous ions also: 2MnO4 + 3 Mn2+ + 2H2O = 5MnO2 + 4H+ The reaction is quite slow in acidic medium but attains a fast rate in neutral solutions. Thus Permanganate solution cannot be considered as a primary standard solution by simply making the calculations based on the amount of permanganate weighed and dissolved. The permanganate solutions once prepared are either left for a day or two or the freshly prepared solutions are boiled for an hour. In both the cases the resulting solution is filtered through sintered glass crucibles. The clear solutions so obtained are then standardized by titrating with a primary standard solution. Permanganate ion in the acidic medium is a very strong oxidizing agent MnO4 + 8H+ + 5epermanganate Mn2+ + 4H2O Ered = +1.51V Manganous ion

The acidity is introduced by addition of dil. H2SO4 only and no other acid. Conc. H2SO4 , Nitric acid (both conc. and dilute) cant be used as these are oxidizing agent and may interfere in the reaction of permanganate depending on the reductants strength. In the hydrochloric acid permanganate can oxidize chloride to chlorine, which can be a source of positive errors as permanganate is consumed in this reaction. (Ered Cl2/Cl-)= +1.36V) 2MnO4 + 16 H+ + 10Cl - (aq) 2Mn2+ + 5Cl2 + 8 H2O (l)

Acetic acid is too weak an acid to provide the desired acidity in the solution. Permanganate acts as self indicator. Since MnO4 is intense purple while Mn2+ is colourless, the reaction mixture at equivalence point is colourless and even a single drop of the permanganate would impart sufficient pink colour to the solution acting as self indicator. This also leads to precaution that while titrating a reducing agent with KMnO 4 , constant stirring of reaction mixture is must otherwise local reduction in acidity may lead to precipitation of MnO2 according to this reaction. The reducing agent in the titration to be discussed is oxalic acid here. The composition of it is H 2C2O4.2H2O. Inspite of being a dehydrate it is a good primary standard as its composition is unchanged during storage or weighing.

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