EXPERIMENTAL ANALYTICAL CHEMISTRY II LAB WORK 2 3+ DETERMINATION OF THE Fe AND 3+ Al CONCENTRATIONS IN A FLOCULANT FROM A WATER TREATMENT PLANT AFTER

THEIR SEPARATION BY ION EXCHANGE

DEPARTMENT OF ANALYTICAL CHEMISTRY UNIVERSITY OF THE BASQUE COUNTRY 2007-2008 - Second Term

In order to reach the aims stated for this Course, the following partial objectives are pursued in this lab work: 1. To reinforce the use, understanding and valuation of the chemical methods of analysis 2. To get initiated in the experimentation for the elimination of interferences 3. To practice the ion exchange processes and to check their advantages and drawbacks 4. To reinforce the lab performance protocols in order to produce exact and precise quantitative values, comparing them with those obtained in Lab Work 1.

Theoretical Background

Ion exchange processes allow the separation of species with different ionic properties (same sign but different charge or different sign species). In this particular case, before being able to determine the total concentrations of iron and aluminum in a oculant used in a water treatment plant, by means of complexometric titrations with EDTA, it is necessary to carry out the separation of both meta ions because their interfere with each other in their reaction with EDTA. The Fe(III) and Al(III) separation can be achieved by ion exchange taking advantage of the Fe(III) to form an anionic chlorocomplex while Al(III) can not form such complexes and remains in solution as a cationic species. Thus, both metals can be separated in concentrated HCl media by ion exchange with the strongly basic Purolite A100 anionic resin. The Fe(III) tetrachlorocomplex is captured by the resin as long as it remains as such anion (for instance, in a 6 M HCl media). As Al(III) does not form anionic complexes under these conditions it is not retained in the resin which allows the following separation process: Al3+ + FeCl aq + R+ Cl R+ FeCl res + Cl + Al3+ aq res aq aq 4 4 In this way, Al(III) stays in the aqueous phase (take an aliquot for its titration), while Fe(III) is quantitatively retained in the resin. In order to determine the Fe(III) concentration it is necessary to elute it from the resin phase to an aqueous phase. This can be done according to: R+ FeCl res + NOaq (pH = 2) FeCl4aq + R+ NOres 4 3 3 1

Therefore, Fe(III) is quantitatively returned to an aqueous phase (take an aliquot for its titration) without Al(III) being present now.

Operating Procedure
Column preparation The ion exchange resin may have been stored dry. Because of the phenomena known as swelling, the resin must be properly hydrated and conditioned before use. To do this, add the dry resin to the column with a spoon and then add distilled water to facilitate settling. Keep doing this until the length of swollen hydrated resin in the column is 15 cm. Use a slim glass stick to remove any bubbles that might have formed. Once the resin in the column is completely hydrated and has settled, it should be cleaned by pouring about 200 mL of deionized water. Column use For all the experiments in this lab work, the column ow should not be higher than 4 mL/min. The ow can be measured with a graduated test tube while cleaning the resin with water as mentioned before. When not in use, the column should be left with at least 2 cm of liquid above the column head (stand-by position, Figure 1a). Before starting any elution operation, the column should be brought to the start position: the level of the liquid is at the same level of the resin head (Figure 1b). In a normal elution operation there should be at least 2 cm of the eluting solution above the resin (operation position, Figure 1c). Fe(III) and Al(III) separation in concentrated HCl media using the PUROLITE A100 resin 1. Prepare a 6 M HCl solution and condition the resin in chloride form by pouring about 50 mL of this solution through it. To do this, go from the stand-by to the start and to the operation positions. 2. Go to the start position again, take a 20 mL sample and pour it through the resin. Use a glass stick to lead the sample through the column wall in order no to stir the resin. 3. When the last part of the 20 mL sample has already gone under the resin head (that is, in the start position again), begin the addition of the 6 M HCl solution until 100 mL have been collected in a 100 mL volumetric ask. Al(III) concentration will be determined from the collected solution. Fe(III) elution with HNO3 at pH = 2 1. Prepare 250 mL of HNO3 at pH = 2. 2. Go to the start position and pour this solution trough the resin containing Fe(III). 3. In the operation position, start collecting the eluate in a 100 mL volumetric ask. Keep pouring the HNO3 solution until the ask is full to the mark. Fe(III) concentration will be determined from this solution.

Quantitative Determination Methods

Both metals will be determined by complex formation titration using EDTA as ligand. As with any titration, it is not only necessary to have a quantitative reaction free from interferences but also to have an adequate indicator which allows the detection of the end point. In this case, Fe(III) can be directly titrated because an indicator is available. However, no good indicators can be found for Al(III) and thus a back titration will be employed.

2 cm

2 cm

15 cm

15 cm

15 cm

Flow = 0 a)

Flow = 0 b)

Flow = 4 mL/min c)

Figure 1: Column use: a) Stand-by mode, b) Start mode, c) Operation mode. Legend: 1 = Resin, 2 = Resin bed, 3 = Liquid above resin.

3.1

EDTA standardization with ZnO at pH = 10.5 using EBT as indicator

EDTA (approx. 0.01 M) standardization must be carried out rst with ZnO as primary standard in a 1 M NH4 + /NH3 buffer at pH = 10.5 using Eriochrome Black T1 as indicator. EDTA mol weight = 372.24 g/mol ZnO mol weight = 81.37 g/mol At least 3 titrations must be performed for EDTA standardization. For each titration, weight (in a dry Erlenmeyer ask at ambient temperature) the ZnO amount which involves the use of about 20 mL EDTA. Dissolve ZnO in the minimum amount of concentrated HCl drops (maybe 5 or 6 are enough). Add about 50 mL water and neutralize with 0.01 M NaOH until pH is in the interval 5-10. Add 25 mL of the buffer solution and make sure pH is in the 10-10.5 interval. If pH is more acidic than that, add a base (NaOH or NH3 ) directly to the Erlenmeyer. Finally, add the EBT indicator (a violet color -red on a blue background- should be observed). Titrate with the EDTA solution until the indicator changes color to blue (the red disappears from the blue background). After this EDTA standardization both metals can be titrated.

3.2

Al+3 titration with EDTA by means of a back titration with Zn+2 at pH = 5 using Xylenol Orange as indicator
First, the standardization of the Zn+2 solution (approx. 0.01 M) must be carried out Zn(NO3 )2 .6H2 O mol weight = 297.47 g/mol This standardization is performed taking an 10 or 20 mL aliquot of the Zn+2 solution and titrating it with the standardized EDTA solution using the previous procedure. To titrate Al(III), take a 10 mL aliquot from the volumetric ask where the Al(III) eluate was collected, neutralize2 it to a pH of about 5 and add 25 mL of the 0.01 EDTA solution. Check that, in any case, pH is in the 3 - 5.5 interval and adjust it with diluted HNO3 or NaOH if needed. Now, heat the Erlenmeyer in a sand bath for about 10 minutes to make sure all the Al(III) is complexed with EDTA. After cooling the Erlenmeyer, add 25 mL of a 1 M HAc/Ac solution and the Xylenol Orange indicator (a yellow color should be observed). Finally, proceed to titrate the excess EDTA with the Zn+2 solution until the rst orange/red shades are observed.

3.3

Direct Fe+3 titration with EDTA at pH = 2 using SCN as indicator

Take a 10 mL aliquot from the volumetric ask where the Fe(III) eluate was collected. Add about 100 mL of water and adjust to pH = 1.5 - 2 if needed. Add either some drops of a 0.1 M SCN solution or half a microspoonful of the solid KSCN or NH4 SCN indicator until the yellow Fe(III) turns to red (the more red the more SCN is added). Titrate with 0.01 M EDTA until all shades of red/orange have disappeared from the yellow (greenish) background of the solution containing the Fe-EDTA complex.

in Spanish. do this, a concentrated NaOH solution (or even solid NaOH) can be used. Perform the necessary calculations to know the volume of solution or weight of solid to be added.
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