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Determination of Percent Potassium & Percent Iron in an Iron Oxalate Salt by Ion Exchange

Introduction: This experiment involves determining both the percent potassium (K) and iron
(Fe) in a single titration after passing a solution containing a known mass of complex salt through an ion exchange column.

Ion Exchange: Certain materials called ion exchange resins consist of rather large molecules
which contain ions that can be displaced. The resins are solids, insoluble in water, usually granular in texture, which when added to water swell to form a slurry. The ionizable group on the resin ionizes in the presence of water, a process represented by Equation 1 for a resin containing a sulfonic acid group. (-SO3-H). R-SO3-H + H2O R-SO31- , H3O+ (1)

R represents the large insoluble resin molecule to which a sulfonic acid group is chemically bonded, H3O+ represents acid hydronium ion bound to the resin sulfonate ion. This particular type of resin is called a cation exchange resin for reasons described later, and the chemical form of the resin represented in Equation 1 is called the acid form for obvious reasons. When a slurry of the resin in water is poured into a vertical glass or plastic column equipped with a porous plug at the bottom to trap the resin and excess water is allow to flow out, the column becomes filled with water soaked resin, as shown in Figure 1.

resin porous plug

Figure 1 If an aqueous solution of a salt such as KCl (K + + Cl-) is poured into the resin filled column, the KCl solution will displace the solution surrounding the resin and that solution will elute from the bottom of the column. In the process, as the KCl solution passes down the column, K + ions displace (exchange with) H3O+ ions and aqueous HCl (H 3O+ + Cl-) elutes from the column, Equation 2. R-SO3-,H3O+ + K+ + ClR-S)3-,K+ + H3O+ + Cl(2)

Thus the solution coming out of the column will contain a quantity of H 3O+ ions equal to the number of K+ ions that were added to the column. If enough K + ions are added, all of the acid form of the resin will be converted to potassium form and at that point the resin will become incapable of exchanging any more H3O+ for K+ ions. However, it is possible to restore the resin completely to its acid form by pouring an aqueous solution of HCl ion the K + saturated column. As the HCl solution passes down the column, the H 3O+ ions displace the bound K+ ions and the reaction represented by Equation 2 is reversed with aqueous KCl eluting from the column. Other cations such as Na+, Li+, Ca2+, etc. will exchange with the resin bound H 3O+ ions in a manner similar to that of K+ - hence the term cation exchange resin. Anion exchange resins are also available, but will not be used in this experiment. Ion exchange resins are widely used in industry and in research laboratories to selectively remove certain ions from solution. Some water softening units, for example, are packed with sodium (Na+) form of cation exchange resin which removes cations such as Ca 2+, Mg2+, and Fe2+ that cause water hardness. These resins can be regenerated after they become saturated with the above ions by passing an aqueous solution of NaCl through the unit.

Determining Percent Potassium (K) in KxFe(C2O4)y Exchange:

z H3O Using Ion

When a weighed quantity of KxFe(C2O4)y . z H3O is dissolved in water, the salt dissociates into ions according to Equation 3. KxFe(C2O4)y . z H3O x K+(aq) + Fe(C2O4)y + z H2O (3)

If this solution is passed down a column containing a cation exchange resin in the acid form, the K= ions will replace the resin bound H3O+ ions according to Equation 4. x R-SO3-,H3O+ + x K+(aq) + Fe(C2O4)yx-(aq) x R-SO3-,K+ + x H3O+(aq) + Fe(C2O4)yx-(aq) (4)

For each mole of K+ added to the column one mole of H3O+ elutes from the column. mol K+(aq) added = mol H3O+ eluted (5)

If the eluted solution is titrated with standard NaOH, the moles of H 3O+ in the solution eluted from the column (hence moles of K+ added to the column) can be determined. moles K+(aq) added = moles H3O+(aq) eluted = moles NaOH required in titration = VL x M (6) (VL = volume in liters of standard NaOH, M = the molarity of the standard NaOH)

Once the number of moles of K+ in the weighed sample of green salt has been determined the mass of K+ can be calculated (Equation 7). w = mol K+ x 39.10 g Combining equations 6 & 7 gives Equation 8, an expression for the mass of K+ w = VL x M x 39.10 g (8) (7)

in the weighed sample of complex iron salt. Since the mass of the salt sample used in the experiment is known, the percentage of potassium in the salt is given by Equation 9. Percent Potassium =
w VxMx39.10 x100 x 100 = where m = the mass of sample (9) m m

Determining Percent Iron (Fe) in KxFe(C2O4)y . z H3O Using Ion Exchange:


An examination of equation 4 indicates that the solution which elutes from the column contains the acid, x H3O+ + Fe(C2O4)yx-. When this acid is titrated with standard NaOH the reaction that occurs first is given by Equation 10 which is the basis for the determination of potassium described above. H3O+ + OH2 H2O (10)

After all of the acid is neutralized in the titration, further addition of NaOH results in the reaction represented by Equation 11. Fe(C2O4)yx- + 3 OHFe(OH)3 + y C2O42(11)

The Fe(OH)3 precipitates from the solution as a reddish-brown gelatinous precipitate. Equation 11 indicates that 3 moles of OH- are required to react with each mole of Fe in the salt. Or, stated in a different way, one mole of Fe is chemically equivalent to three moles OH - in the reaction(Equation 12). 1 mol Fe = 3 mol OH(12)

Thus if it requires VL liters of standard NaOH solution of concentration M (moles per liter) to completely precipitate all of the Fe in a weighed sample of green salt, it follows that the number of moles of Fe in the sample is given by the Equation 13. Mol Fe = mol OH- x (VL x M)
1molFe 3molOH

(13)

The mass of Fe present is given by Equation 14. w =


molFex55.85 g / moleFe 3

(14)

w = the mass of Fe in the sample, and 55.85 is the atomic mass of Fe Finally, if the sample mass is m, the % Fe in the salt is given by Equation 15. Percent Fe =
w VxMx55.85 x100 x 100 or m 3 xm

(15)

Where m = the mass of the sample.

The Titration Curve: When the eluate from the ion exchange column is titrated with
standard NaOH using a pH meter to follow the reaction, a titration curve looking something like that in Figure 2 is obtained.

pH

V1 Volume of NaOH Figure 2

V2

Two titrimetric equivalence points are obtained: the first, after the addition of V 1 mL of NaOH and the second after V2 mL of NaOH have been added. The first equivalence point represents the completion of neutralization of H3O+ (equation 10) and the second the completion of the precipitation of Fe(OH)3 (equation 11). Thus V1, converted to liters, is the value of V L in equations 8 and 9 while V2 V1, converted to liters, is the value of V L in the equation 13, 14, and 15. Thus, from a single pH titration curve of a weighed sample of KxFe(C2O4)y . z H3O that has

been passed through a cation exchange resin, it is possible to determine both the percent K and percent Fe in the compound.

Notes on Experimental Protocol:


1. Mount the ion exchange column vertically on a ring stand using a utility clamp ( Figure 3). The column should always be filled with liquid up to or above the top of the resin so that air pockets cannot form in the resin bed.

Ion Exchange Column Beaker Figure 3 2. When you receive the column it will contain an acid solution which has been added to insure that all of the resin is in its acid form. It is absolutely necessary to rinse out all of this acid or incorrect results will be obtained. Never allow the liquid level to fall below the top of the resin. 3. During the time the solution of KxFe(C2O4)y . z H3O and rinses are moving down the column, the K+ ions from the dissolved crystals are exchanging with the H 3O+ of the resin (equation 4). 4. As the HCl solution moves down the column, the H3O+ ions of the acid exchange with the K+ ions bound to the resin (the reverse of equation 4). This regenerates the resin to the acid form so that the column will be ready for another trial. 5. Be alert!!! The first equivalent point may come before 10 mL of NaOH have been added and the second equivalence point before 20 mL of NaOH have been added.

Experimental Protocol:

This experiment should be started at the beginning of the laboratory period in order to complete it is one period. Mount an ion exchange column on a ring stand (note 1). It is important to make sure that the resin bed is filled with liquid at all times. Using a clean 10 mL graduated cylinder rinse the column by pouring 4 mL of distilled water into the column and collecting the liquid that elutes from the column in a small beaker.

Using a piece of pHydrion paper test pH of the solution that first elutes from the column, to make sure it is distinctly acidic (pH<7). If it is not acidic, inform your teacher. Allow the level of rinse liquid in the column to fall to the top of the resin (note 1). Repeat the above rinse procedure two more time using 4-mL portions of distilled water. (note 2). When the level of water in the third rinse has dropped to the level of the top of the resin, test a drop of eluate with pHydrion paper to confirm that the pH is about that of the distilled water (note 2). If the eluate is still acidic, continue to rinse until it is about the pH of the distilled water. There will be some waiting time accompanying the rinse protocol; make good use of this time by looking ahead and preparing everything that will be needed for the laboratory. Using the mg electronic top-loader balance weigh a sample of your KxFe(C2O4)y . z H3O between 0.155 and 0.165 g to the nearest 0.001 g on a weighing dish and transfer it to a 50 mL beaker. Make sure that the sample mass does not exceed 0.165g. Using the 10 mL graduated cylinder add 4 mL of distilled water to the sample of crystals and gently swirl the beaker until the salt is completely dissolved. Place a clean 150 mL beaker under the ion exchange column and quantitatively transfer the solution to the column. Collect the eluate in the 150 mL beaker. Rinse the beaker that you just emptied into the column with 4 mL of distilled water and when the level of liquid in the column has dropped to the top of the resin, pour this rinse water into the column. Repeat this rinse protocol with two more 4 mL distilled water rinses (note 3), waiting each time until the liquid level in the column has dropped to the top of the resin level before adding more liquid to the column. Set up a clean buret and pH meter assembly, standardizing the pH meter with buffer solution as described by your teacher. Obtain about 30 mL of standard NaOH in a clean dry 50 mL beaker and after rinsing the buret three times with small amounts (about 5 mL portions) of the solution fill the buret with the standard NaOH solution. In order to fill the buret it will be necessary, of course, to obtain a second 30 mL of standard NaOH in the 50 mL beaker. Do not allow the NaOH to stand in the beaker expose to the air. Put it immediately into the buret where it has essentially no air contact. Prepare for titration by expelling air bubbles from the burets tip. After the last rinse has eluted from the ion exchange column, transfer the beaker containing the eluate to the surface of the magnetic stirrer to be used in the pH meter titration.

Before beginning the titration pour 10 mL of 1.0 M HCl into the ion exchange column and place a beaker under the column to collect the eluate (note 4). Take care that none of this acid gets into the solution of crystals that has been eluted from the column. Now return to your pH meter titration set-up. electrode bulb in solution. Add enough distilled water to immerse the

Titrate the solution with standard NaOH to obtain a titration curve similar to Figure 2. Add 0.5 mL portions of NaOH solution initially but reduce the volume of the additions to 0.1 mL as the pH starts to change more rapidly near the first equivalence point. Continue the 0.1 mL additions until the rapidly rising portion of the curve is complete then increase the volume of the additions to 0.5 mL as the pH changes decrease in size and the flat portion of the curve between the two equivalence points is defined. Decrease the volume of each additional to 0.1 mL through the second equivalence point and, after it has been defined, add 0.5 mL portions to complete the titration to about 15 mL beyond the second equivalence point (about 35 mL in all).

Report: Carefully plot your pH data vs. mL of standard NaOH added on graph paper (or on
your TI 83). Be sure that the x-axis is sufficiently expanded to allow estimations to the nearest 0.01 mL. Determine the equivalence points (V1 and V2) from your graph. You might find it helpful to make two expanded plots one from about 3 to 17 mL NaOH added, and the other from about 13 to 27 mL added. Show all calculations in your laboratory notebook. Complete the report form on the following page. Attach the pH titration graph(s). Be sure that the numerical results have been recorded in your laboratory notebook as well as on the report form. Submit the report packet.

STUDENT REPORT FORM


Determination of the Simplest Formula of Complex Iron Salt Percent Potassium and Iron by Ion Exchange
1. Mass of sample ___________ g 2. Molarity of standard NaOH used _________________ M 3. V1, volume of standard NaOH required for first equivalence point ____________mL 4. Mass of potassium in sample _______________g 5. Percent potassium in sample ________________% 6. V2, volume of standard NaOH required for second equivalence point __________mL 7. V2 - V1, volume of standard NaOH that reacted with iron ___________mL 8. Mass of iron in sample _____________g 9. Percent iron in sample ______________% Work for the above.

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