38

Experiment #2. Preparation and Analysis of Potassium trioxalato ferrate (III) trihydrate

Preparation & Analysis of potassium trioxalato ferrate (III) trihydrate K3[Fe(C2O4)3]3H2O

Step One: Preparation of Ferrous Oxalate
Weigh the vial containing the sample of ferrous ammonium sulfate, (NH4)2SO4FeSO46H2O. Transfer the ferrous ammonium sulfate to a beaker containing 25 mL of warm water acidified with 1 mL dilute 3M H2SO4. Dry the vial and weigh the empty vial. Record the mass of ferrous ammonium sulfate used. To this solution add 25 mL of oxalic acid solution (5 g/50 mL). Cautiously heat the solution to boiling on a hot plate, continuously stirring the solution to avoid bumping. Remove and then allow the precipitate to settle. Decant and discard the clear supernatant liquid (avoid loss of precipitate). Stir the remaining precipitate with 25 mL of hot water, the solubility of FeC2O42H2O is .022 g/100 mL in cold water and .026 g/100 mL in hot water. Decant and discard the wash liquid. Add 25 mL of hot water to the precipitate and stir, then filter by suction using a small Bchner funnel and wash the precipitate thoroughly with small portions (10-20 mL) of hot water. Finally rinse with 20 mL of acetone. Weigh the final product.

Step Two: Preparation of K3[Fe(C2O4)3]3H2O

Suspend the washed and dried ferrous oxalate in 30 mL of warm solution containing 3.5 g of potassium oxalate (K2C2O4H2O). Place this solution in an ice bath and add slowly with continuous stirring 7-10 mL of 30% H2O2 in very small portions, then heat the mixture to boiling and dissolve the precipitate by adding in one portion 7 mL of a solution of oxalic acid (containing 2.5 g/25 mL). A further 3 mL is then added drop by drop using an eye dropper (an excess of oxalic acid is to be avoided). The liquid should be near the boiling point while these additions are being made. 6FeC2O4 + 3H2O2 + 6K2C2O4 2Fe(OH)3 + 3H2C2O4 + 3K2C2O4 4K3[Fe(C2O4)3] + 2Fe(OH)3 2K3[Fe(C2O4)3] + 6H2O

30% H2O2 is a strong oxidizer, a corrosive irritant to skin, eyes, mucous membranes and should be handled with care. 18M H2SO4 sulfuric acid is a strong acid, corrosive irritant and contact will result in rapid destruction of tissues, causing severe burns.

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Experiment #2. Preparation and Analysis of Potassium trioxalato ferrate (III) trihydrate

Filter through a Bchner funnel. Transfer the hot solution to a clean beaker and while still hot, add to the filtrate 15 mL of 95% ethanol and redissolve any precipitated crystals by gently heating. Then store the solution in a dark cupboard for crystallization. After crystallization has occurred, filter with suction and wash the product on the filter paper with 20 mL of an equi-volume mixture of ethanol and water and finally with 20 mL of acetone. Draw air through the precipitate for several minutes. Weigh the dry crystals. K3[Fe(C2O4)3] 3H2O is highly photosensitive. The bright green crystals on exposure soon become covered with a yellow powder of ferrous oxalate. 2K3[Fe(C2O4)3]3H2O 2FeC2O42H2O + 2CO2 + 3K2C2O4 + 2H2O

Oxidation - Reduction Titration

Potassium permanganate (KMnO4) is commonly used as an oxidizing agent and can be reduced in different ways, depending on the H+ concentration of the reaction mixture. In neutral or basic solutions a mixture of products may result, chiefly solid MnO2 and green manganate ion, MnO42. In acid solution, however, the reduction goes by one course only, the half-reaction being: MnO4 (aq) + 8H+ (aq) + 5e Mn2+ (aq) + 4H2O (l)

Part A

Preparation of a 0.02 M KMnO4 Solution

Handle solid KMnO4 and the solution carefully, for if either gets on clothes or skin, it will be reduced to MnO2 leaving brown spots. Traces of MnO2 initially present in the permanganate are formed by the reaction of permanganate with residual organic impurities (reducing material) in the water will catalyze the reduction of MnO4 . Weigh out approximately 1.2 - 1.40 g of potassium permanganate and add it to approximately 350 mL of boiled distilled water in a 600 mL beaker. Stir the solution well to dissolve all the crystals. Cover the solution with a watch glass and keep the solution near the boiling point for 20 minutes. Allow the solution to cool slightly, then filter the solution through a non-reducing filter (glass wool) placed in the neck of a short stemmed funnel. The KMnO4 solution can be stored in a plastic bottle. Be sure the bottle is labelled with your name, lab number, semester and year.

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Experiment #2. Preparation and Analysis of Potassium trioxalato ferrate (III) trihydrate

Part B

Standardization of KMnO4 Solution

2-

Note 1. The MnO4 / C2O4 reaction is slow at room temperature and hence the titration is carried out at elevated temperatures. Even at higher temperatures the reaction starts slowly, but the rate increases as Manganous (Mn2+) ion, which acts as a catalyst, is formed. Since the Mn2+ ion is a product of the reaction itself, the reaction is called "autocatalytic". Note 2. With deeply colored solutions like permanganate, it may be necessary to read the top of the meniscus since it is difficult to see the bottom of it. Weigh accurately, to the nearest tenth of a milligram, three samples each in the range .18 - .22 g of sodium oxalate (Na2C2O4) into clean 250 mL Erlenmeyer flasks. To each sample add 60 mL of water and 10 mL of 3 M (dilute) sulfuric acid. Titrate each solution as follows. Heat the contents of the Erlenmeyer flask to 80 - 90C, but not over 90C. (Do warm all trials at the same time). Rinse the thermometer with 1 to 2 mL of distilled water and remove and titrate the hot solution with the KMnO4 solution. Add several mL of KMnO4 solution slowly to initiate the reaction then larger portions may be added until the endpoint is approached. Then slow the addition of titrant to avoid overshooting the faint pink endpoint. The solution should be swirled while additions are being made. The reaction is represented by the following reactants and products in acid solution. MnO4 + C2O4
2-

+ H+

Mn2+ + CO2 + H2O

Balance the equation and calculate the molarity of your permanganate solution.

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Experiment #2. Preparation and Analysis of Potassium trioxalato ferrate (III) trihydrate

Characterization of the Green Crystals: A. % H20 in the green crystals

Weigh 0.7-1.0 g (0.0001g) of the complex salt into a pre-weighed evaporating dish. Label or mark the dish so you can identify it and place the evaporating dish and complex salt in an oven set at 110oC for approximately 45 minutes. Cool the dish and contents and weigh to the nearest 0.1 mg. Calculate the % H20 in the crystals. Use the dried crystals for part C.

B.

% of Oxalate in the green crystals using Potassium Permanganate

MnO4 + C2042- + H+ Mn2+ + CO2 + H2O

Proceed with the prepared salt complex. Weigh out 3 samples of the complex salt in the weight range of .18 - .22 g (on the analytical balance) into clean 250 mL Erlenmeyer flasks. Dissolve each sample in 60 mL H2O, 10 mL of 3 M (dilute) sulfuric acid and heat each sample to 80-90C but not over 90 and titrate with standardized potassium permanganate until the first appearance of a faint permanent pink color occurs. Calculate the percent oxalate in the complex salt.

C.

% of Iron in the green crystals

This procedure should be carried out in the fumehood until the final step. To the evaporating dish and dried crystals, add cautiously approximately 3 mL concentrated H2SO4 (sulfuric acid) and cover with a watch glass. In the fumehood, using a hotplate, gently heat the dish and contents for several minutes until the bubbling resulting from the decomposition of the oxalate ion ceases rather abruptly. Allow the evaporating dish and contents to cool in the hood. Then pour the colorless (anhydrous) ferric sulfate from the dish into an Erlenmeyer flask and rinse the watch glass. Add approximately 25 mL of distilled H2O to the Erlenmeyer flask and heat the flask and contents to boiling. The milky solution will gradually turn to a clear pale yellow solution. Then add small portions of zinc dust and continue to cautiously heat the flask until the yellow color disappears from the solution. Heat for approximately 1 minute beyond this point. The hot mixture is filtered through #1 Whatman paper into a clean flask and rinsed to achieve complete transfer. This solution is then titrated with standardized KMnO4 solution until a faint pink/orange endpoint appears. The % Fe in the green crystals can then be calculated. Use the original mass of the green crystals before they were dried in the oven.

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Experiment #2. Preparation and Analysis of Potassium trioxalato ferrate (III) trihydrate

Preparation and Analysis of Potassium trioxalato ferrate (III) trihydrate

Name: ______________________ Lab Section# : ____________ Data Sheet: 1. Step one: Preparation of Ferrous oxalate

Ferrous Ammonium Sulfate sample # ___________ Mass of Ferrous ammonium sulfatehexahydrate used Mass of 250mL beaker _________ g Instructors signature: ________________ 2. Step two: Preparation of Potassium trioxalato ferrate (III) trihydrate Mass of ferrous oxalate dihydrate used to start the reaction _________ g Mass of Potassium Tris-oxalatoferrate III trihydrate produced _______ g (Green Crystals) Part B: Standardization of the prepared KMnO4 solution Trial #1 Trial #2 Trial #3 Trial #4 ________ g

Mass Na2C2O4 & container (g)___________ ___________ ___________ ____________ Mass container (g) Mass of Na2C2O4 used(g) Initial Volume KMnO4 Final Volume KMnO4 ___________ ___________ ___________ ____________ ___________ ___________ ___________ ____________ ___________ ___________ ___________ ____________ ___________ ___________ ___________ ____________

Volume of KMnO4 used (mL) __________ ___________ __________ ____________ Molarity of KMnO4 Average Molarity of KMnO4 _________M, _________ M, _________M, _________M __________ M (**Report this value on p.45**) Instructors signature: ________________

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Experiment #2. Preparation and Analysis of Potassium trioxalato ferrate (III) trihydrate

Preparation and Analysis of Potassium trioxalato ferrate (III) trihydrate

Name: _________________ Date: _________________

Analysis of the of Potassium trioxalato ferrate (III) trihydrate A. % H2O in the Green Crystals: Mass of the evaporating dish Mass of green crystals & the evaporating dish before heating Mass of green crystals before heating Mass of green crystals & the evaporating dish after heating Mass of green crystals after heating B. % oxalate ion in the Green Crystals: Trial #1 Trial #2 Trial #3 Trial #4 _____________g _____________g _____________g _____________g _____________g

Mass crystals & container (g) ___________ ___________ ___________ ____________ Mass container (g) ___________ ___________ ___________ ____________

Mass green crystals used(g) ___________ ___________ ___________ ____________ Initial Volume KMnO4 Final Volume KMnO4 ___________ ___________ ___________ ____________ ___________ ___________ ___________ ____________

Volume of KMnO4 used (mL) __________ ___________ ___________ ____________ C. % of Iron in the Green Crystals: Mass of green crystals before heating Initial Volume KMnO4 Final Volume KMnO4 Volume of KMnO4 used (mL) ______________g ___________ mL ___________ mL ___________ mL Instructors signature: ________________

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Experiment #2. Preparation and Analysis of Potassium trioxalato ferrate (III) trihydrate

Experiment #2 Report Sheet:

Preparation of K3[Fe(C2O4)3] 3H2O Name:_______________________

Sample # _____________ Date:_______________________ Show example calculations on the back of the report sheets or append separate sheets. 1. Balanced Equations: Step #1.

Step #2. (The equation is in the manual, write a balanced equation in the hydrated form)

2.

Theoretical Yield (Show your work): Using your experimental mass of starting material for each calculation. Step #1.

Step #2.

3.

Per Cent Yield (Show your work): Step #1.

Step #2.

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Experiment #2. Preparation and Analysis of Potassium trioxalato ferrate (III) trihydrate

Experiment #2 Report Sheet:

Characterization of K3[Fe(C2O4)3] 3H2O Name:_______________________ Lab Section:__________________

Balanced titration and reaction equations for: Fe3+ & Zn; MnO4- & C2O42- ; and Fe2+ & MnO4- . 1.

2.

3.

Molarity of KMnO4: (From page 42). Average Molarity of KMnO4 = __________ M. Experimental weight % of C2O42- in the prepared green crystals: Trial #1.

Trial #2. Trial #3. Trial #4. Average weight % of C2O42- :

46

Experiment #2. Preparation and Analysis of Potassium trioxalato ferrate (III) trihydrate

Experimental weight % of Fe in the prepared green crystals: Trial #1:

Experimental weight % H2O in the prepared green crystals:

Experimental weight % K in the prepared green crystals:

Formula Weight % of Fe, H2O, C2O42- , K in K3[Fe(C204)3] 3H20:

% Deviation of the Experimental weight % values compared to Formula Weight % values:

Conclusions:

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Experiment #2. Preparation and Analysis of Potassium trioxalato ferrate (III) trihydrate

Preparation and Analysis of Potassium trioxalato ferrate (III) trihydrate

Example Pre-Lab Questions: 1. 2. Write the chemical formula of potassium permanganate. A mixture of 5.00 g of H2(g) and 10.00 g 02 (g) is ignited. Water forms according to the following reaction: 2H2 (g) + O2(g) 2 H2O (g) Which is the limiting reagent? How much water will be produced? Name this compound: K3[Fe(C2O4)3]3H2O Write the chemical formula for ferrous oxalate dihydrate. Describe the proper procedure for diluting 18 M concentrated sulfuric acid to prepare 100 mL of 3 M sulfuric acid. A solution of potassium permanganate was prepared by dissolving 21.08 g of KMnO4 in water and diluting to a total volume of 800mL. What is the molarity of the prepared solution? Is oxalic acid a liquid or a solid under normal laboratory conditions? Is oxidation or reduction occurring in the following reaction? Indicate why. MnO4 + 8 H+ + 5e Mn2+ + 4H2O DDT (dichlorodiphenyltrichloroethane) is an insectide banned in Canada becauce it is hazardous to fish,birds and humans. The reaction for its preparation is; 2C6H5Cl (chlorobenzene) + C2HOCl3(chloral) C14H9Cl5 (DDT) + H2O If 450 g of chlorobenzene reacts with 899 g of chloral calculate (a) the theoretical yield of DDT in grams and (b) the % yield if 650 g of DDT is actually isolated. What color change occurs at the endpoint of the permanganate - oxalate reaction? Why should potassium permanganate be handled carefully? What is the catalyst used in the permanganate - oxalate reaction? What is the color of ferrous oxalate? What color are the crystals of K3[Fe(C2O4)3]3H2O? Why are you analyzing the crystals of K3[Fe(C2O4)3]3H2O?

3. 4. 5. 6.

7. 8.

9.

10 11. 12. 13. 14. 15.