Lab: Quantitative Oxidation/Reduction Titration Alexander Kazberouk Period 5/6 Chemistry AP Mrs.

Murphree

TITLE: Quantitative Oxidation/Reduction Titration PURPOSE: The purpose of the experiment was to use the permanganate ion, a strong oxidizing agent, in a titration in order to determine the concentration of a FeSO4 solution. Purple MnO4- ion from a standardized potassium permanganate solution was titrated thrice to give clear Mn2+ with an analyte of acidified FeSO4 until all the Fe2+ in the solution was oxidized to Fe3+. The color of the MnO4-/Mn2+ was used as the indicator for the titration. A balanced oxidation-reduction, the molarity/normality of the standards potassium permanganate, and the volume of potassium permanganate used allowed the determination of the concentration of the FeSO4. PROCEDURE:
1. Obtain about 100mL of potassium permanganate solution (.020M) from the stock bottle 2. Obtain about 50mL of FeSO4 solution

3. Obtain 2 burets. Rinse one with 5mL of FeSO4, discard rinsings, and fill it with FeSO4. Repeat procedure for potassium permanganate and second buret 4. Place 50mL of distilled water and add 1 drop of potassium permanganate. Observe, this will be the color standard for titration 5. Measure 10.0mL of FeSO4 into flask from buret. Add 5.00mL of 3.0M sulfuric acid to increase H+ concentration. Now titrate with potassium permanganate as titrant, reach the endpoint, read the buret, and discard the contents of the flask 6. Rinse flask and repeat titration two more times using the same volume of FeSO4 DATA & OBSERVATIONS: 1. Potassium permanganate solution = deep purple color, stains o 99.2 mL of standardized .020M taken total o no crystals visible, completely dissolved o color standard for reaction = pink/purple, not as strong as permanganate solution 2. FeSO4 solution = yellow/dirty grey murky color o 50.0 mL of FeSO4 solution of unknown concentration taken 3. Titrations = solution turns pink/purple where drop of titrant lands, but later goes back to murky yellow/grey color o After endpoint, solution is pink/purple 4. Data Table 1: Titration volumes:
H2SO4 added 5.0mL 5.1mL 4.9mL

Trial 1 2 3

FeSO4 start 14.76mL 24.60mL 34.59mL

FeSO4 stop 24.60mL 34.59mL 44.61mL

KMnO4 start 9.18mL 26.20mL 27.93mL

KMnO4 stop 26.20mL 43.65mL 45.17mL

CALCULATIONS:

Balancing: Reduction: 8H+ + MnO4- + 5e- -> Mn2+ + 4H2O Oxidation : Fe2+ -> Fe3+ + e8H+ + MnO4- + 5e- -> Mn2+ + 4H2O 5Fe2+ -> 5Fe3+ + 5eBalanced overall: 8H+(aq) +MnO4-(aq) + 5Fe2+(aq) -> 5Fe3+(aq) + Mn2+(aq) + 4H2O(l) Normality: Number of electrons transferred = number of equivalents = 5 Equivalent weight: (39.10g/mol + 54.94g/mol + 4*16.00g/mol)/5 = 31.61g/mol Normality = 5M = 5 * .020M = .100N Volumes: Trial 1: FeSO4: 24.60mL - 14.76mL = 9.84mL KMnO4: 26.20mL - 9.18mL = 17.02mL Trial 2: FeSO4: 34.59mL - 24.60mL = 9.99mL KMnO4: 43.65mL - 26.20mL = 17.45mL Trial 3: FeSO4: 44.61mL - 34.59mL = 10.02mL KMnO4: 45.17mL - 27.93mL = 17.24mL Average: FeSO4: (9.84mL + 9.99mL + 10.02mL)/3 = 9.95mL KMnO4: (17.02mL + 17.45mL + 17.24mL)/3 = 17.23mL FeSO4 normality and molarity: 17.02mL mL KMnO4 * 0.100 equivalents/1000mL KMnO4 = 1.70 * 10-3 equivalents KMnO4 1 equivalent FeSO4 = 1 equivalent KMnO4 1.70 * 10-3 equivalents KMnO4 = 1.70 * 10-3 equivalents FeSO4 1.70 * 10-3 equivalents FeSO4 / 9.84mL * 1000mL/1L = 0.173N Number of electrons transferred = number of equivalents = 1, normality = molarity Molarity FeSO4 = 0.173M 17.45mL KMnO4 * 0.100 equivalents/1000mL KMnO4 = 1.75 * 10-3 equivalents KMnO4 1 equivalent FeSO4 = 1 equivalent KMnO4 1.75 * 10-3 equivalents KMnO4 = 1.75 * 10-3 equivalents FeSO4 1.75 * 10-3 equivalents FeSO4 / 9.99mL * 1000mL/1L = 0.175N Molarity FeSO4 = 0.175M 17.24mL KMnO4 * 0.100 equivalents/1000mL KMnO4 = 1.72 * 10-3 equivalents KMnO4 1 equivalent FeSO4 = 1 equivalent KMnO4 1.72 * 10-3 equivalents KMnO4 = 1.72 * 10-3 equivalents FeSO4 1.72 * 10-3 equivalents FeSO4 / 10.02mL * 1000mL/1L = 0.172N Molarity FeSO4 = 0.172M Average molarity: (0.173M + 0.175M + 0.172M)/3 = 0.173M

CONCLUSION: The purpose of the laboratory exercise was to perform an oxidation/reducation titration between a standardized solution of potassium permanganate and an unknown iron (II) sulfate solution in order to determine the concentration of the latter. The permanganate ion in the titrant was reduced to Mn2+ and the Fe2+ in the analyte was oxidized to Fe3+. Everything was done in a solution acidified by sulfuric acid so that the MnO4- would get reduced to Mn2+ and the extra oxygen atoms could form water. From the titration data and the balanced oxidation/reduction equation the normality and molarity of the FeSO4 solution were gotten. The oxidation/reduction titration was the major part of the experiment and was performed in order to determine the molarity of the FeSO4. A deep purple and skin-staining 0.020M standardized solution of potassium permanganate was taken and used as the titrant in the titration. The analyte was prepared from a murky grey/yellow solution of unknown concentration of FeSO4 and from 3.0M sulfuric acid. The sulfuric acid was required so that an acidic environment was present with H+ ions to take on the oxygen atoms left over from the reduction of MnO4- to Mn2+. In such an acidic medium, the reaction 8H+(aq) +MnO4-(aq) + 5Fe2+(aq) -> 5Fe3+(aq) -> Mn2+(aq) + 4H2O(l) took place. The titrant, MnO4-, was the oxidizing agent and itself gained 5 electrons to get reduced to Mn2+. The extra oxygen atoms formed water with the H+ ions from the sulfuric acid. The analyte, Fe2+ was the reducing agent and got oxidized to form Fe3+. Initially in the titration, the titrant was a deep purple and the analyte was a pale murky yellow/grey color. As the MnO4- was added to the analyte, the area around the drop turned became a pink/purple color. The titration proceeded until the entire solution stayed purple pink. Initially, the purple MnO4- added to the analyte was quickly reduced to clear Mn2+ and lost its color. However, after all the Fe2+ was oxidized to Fe3+ there was no more reducing agent and thus the MnO4- stayed as MnO4- in the analyte solution. The addition of extra MnO4- after all the Fe2+ has been oxidized made the color of the solution a light purple/pink color as there was no longer

anything to convert the MnO4- to the mostly colorless (slightly pink) Mn2+. Thus, the potassium permanganate was the indicator in the reaction. It turned clear to Mn2+ while there still was Fe2+ to oxidize, but as excess permanganate was added, the solution turned purple with MnO4- having a distinctly different color. The color standard for the reaction was simulated by the addition of a drop of potassium permanganate to water to show what the potassium permanganate would look like after being added at the equivalence point of the titration. Other oxidizing agents could have been used in the titration as well. For instance, Cr2O72- would have likewise oxidized the Fe2+ and could have also acted as a self-indicator because of how it also changes color as it goes to Cr3+. Likewise, CrO42- could have been used and would have also changed color as it oxidized the Fe3+. Oxygen gas noticeably reacted with the FeSO4 solutions to oxidize the Fe2+ions. With a proper set-up that controlled exactly how much oxygen was put in, it would be possible to use oxygen gas as an oxidizing agent. Finally, H2O2 in an acidic solution could have been used as an oxidizing agent and given water. By doing the entire reaction in hydrogen peroxide and seeing how much water was made, another experiment could have been possible. Anything with a reduction potential greater than that of Fe3+ + e- -> Fe2+ could have been used as an oxidizing agent. However, the colorful changes that accompany the changes of oxidation numbers of manganese and the ease of obtaining manganese-containing compounds made it the simplest choice. Having gotten the volumes necessary for the titration, the next step calculated the molarity of the FeSO4 solution. From the balanced chemical equation, the number of the electrons reacting with MnO4-, and the molarity of the standardized KMnO4 solution, the normality of the solution was calculated to be 1.00N. For every mole of MnO4- reduced to Mn2+, 5 moles of electrons were required and thus the normality of the solution, 1.00N, was 5 times its molarity, 0.020M. However, only a single mole of electrons was gotten from the oxidation of

Fe2+ to Fe3+. Thus, there was a 5:1 stoichometric ratio between the two reagents. From the normality of KMnO4- and the volumes used in the titrations, the average normality of the FeSO4 solution was gotten to be 0.173N. That was also equal to the molarity of the solution as the oxidation of Fe2+ to Fe3+ dealt with only a single electron. Overall, it is unlikely that error played a major role in the experiment. The three values for the molarity of the FeSO4 were very close, 0.172M, 0.173M, and 0.175M and the results were precise. To determine the accuracy of the results, the actual value would be needed. Minor error can be attributed to going slightly past the equivalence point for the second titration, thus producing a higher value of 0.175M than is the actual value. A more likely source of error is the oxidation/reduction reaction between the iron sulfate and oxygen in the air. Oxygen got reduced and reacted with H+ in the analyte to form water while the Fe2+ in the FeSO4 analyte got oxidized to give Fe3+. Because the newly formed Fe3+ did not react with the potassium permanganate, less potassium permanganate was added than was needed to oxidize all the Fe2+ originally present in solution. Thus, the actual molarity of the FeSO4 solution was probably higher but the spontaneous reaction of the solution with air made it appear lower than it really was. This can be avoided by performing the reaction in a vacuum.