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Determination of Aqueous (Feii) & (Feiii) With Ferrozine

This document describes a procedure for determining the concentrations of Fe2+ and Fe3+ in aqueous samples using ferrozine. Ferrozine selectively binds to Fe2+, forming a colored complex that can be measured with spectroscopy. Stock solutions and calibration standards of known Fe2+ concentrations are prepared to generate a calibration curve. This curve allows the concentration of Fe2+ in unknown samples to be determined. To measure Fe3+, a reducing agent is used to convert all Fe3+ to Fe2+, then ferrozine is added to bind Fe2+ and allow quantification of the total iron that was originally present as Fe3+. This procedure allows separate measurement of the oxidation states of iron in water, which has applications in

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230 views4 pages

Determination of Aqueous (Feii) & (Feiii) With Ferrozine

This document describes a procedure for determining the concentrations of Fe2+ and Fe3+ in aqueous samples using ferrozine. Ferrozine selectively binds to Fe2+, forming a colored complex that can be measured with spectroscopy. Stock solutions and calibration standards of known Fe2+ concentrations are prepared to generate a calibration curve. This curve allows the concentration of Fe2+ in unknown samples to be determined. To measure Fe3+, a reducing agent is used to convert all Fe3+ to Fe2+, then ferrozine is added to bind Fe2+ and allow quantification of the total iron that was originally present as Fe3+. This procedure allows separate measurement of the oxidation states of iron in water, which has applications in

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Absorption Spectroscopy Revised: 3/19/13

DETERMINATION OF AQUEOUS [FeII] & [FeIII] with FERROZINE

Background

While the total concentrations of various metals in aqueous samples are typically measured with
atomic absorption spectroscopy (AAS), sometimes the detection of specific chemical oxidation
states of a metal ion in water samples is required. For example, Cr(III) is ingestion (poisoning)
is much more serious than exposure to small amounts of Cr(VI). For the case of Fe(II) and
Fe(III), Fe2+and Fe3+ are absorbed by the body differently1. Additionally, remediation of iron
waste in mine run-off water is handled differently depending on the oxidation state of the iron2.
As such, determining not only the total iron concentration in water, but also the oxidation state of
the iron in water is beneficial.

In order to determine amount of FeII or FeIII in water, reagents must be found that react
selectively with just FeII or just FeIII. Ferrozine is one such reagent.

Na +
-O
3S

N
N

N
N

-
O 3S
Na +
Figure 1. Ferrozine

Ferrozine is a bidentate ligand that binds to FeII (not FeIII) in a 3:1 ratio (3 ferrozines bind to one
FeII center) to create the colored octahedral transition metal coordination compound,
Na4Fe(ferrozine)3 (shown in Figure 2). As a bidentate ligand, ferrozine creates a more stable
Fe2+ complex than will a monodentate ligand (e.g. SCN-). This enhanced stability is known as
the chelate effect. Also, the two sulfite (-SO3-) groups on each ferrozine keep the resulting
complex soluble in water an important asset when working on environmental or biological
systems.

1
Hoffman R, Benz E, Shattil S, Furie B, Cohen H, Silberstein L, McGlave P. Hematology: Basic Principles and Practice, 3rd ed.
ch 26: Disorders of Iron Metabolism: Iron deficiency and overload. Churchill Livingstone, Harcourt Brace & Co, New York,
2000
2
Current Information on Mine Waste Treatment Technologies , Environmental Protection Agency,
http://www.epa.gov/aml/tech/appenc.pdf, accessed, July 14, 2012

1
Absorption Spectroscopy Revised: 3/19/13

Figure 2. Na6Fe(ferrozine)3

Most importantly for this experiment, the formation of a colored complex allows for the
determination of iron concentration with visible spectroscopy (using Beers Law). The
procedure below is derived from a U.S. Geological Survey protocol used to find if dangerously
high levels of Fe2+ and Fe3+ are being released from abandoned iron mines into nearby rivers and
ground water.

Safety

Safety goggles and aprons must be worn at all times. All chemicals used are hazardous if
ingested.

Procedure

A. Stock & Standard Solution Preparation.

1. FeII stock solution 1 In a 50 mL volumetric flask, prepare a 5.0 mM ferrous ammonium


sulfate hexahydrate (Fe(NH4)2(SO4)26H2O) solution. Before diluting to volume with
deionized water, add 1.0 mL of 6 M HCl to the flask. (Acidification will prevent iron
hydroxide from precipitating out of solution.)

2. FeII stock solution 2 - In a 25 mL volumetric flask, dilute the solution above to 0.2 mM.
Before diluting to volume with deionized water, add 40 mg ferrozine and 1.25 mL
ammonium acetate buffer. Let the solution to sit for 2 minutes and observe the color change.
This solution must be used within 30 minutes of its preparation to avoid precipitation of
insoluble red FeIII oxide. If a considerable amount of solid forms, prepare another solution
before moving forward.

2
Absorption Spectroscopy Revised: 3/19/13

3. FeII standard solutions Using the 0.2 mM solution just created above, prepare four 25.0 mL
solutions with the following concentrations: 0.04 mM, 0.024 mM, 0.016 mM, and 0.008 mM.

B. Calibration Curve Creation.

1. Plug the spectrometer into your computer and calibrate with DI water. Pour the first standard
solution mixture into a prerinsed cuvette and take the absorbance spectrum. Determine the
max you will use in this experiment and report its absorbance.

2. Take the absorbance spectrum of all remaining FeII standards. Create a calibration curve of
absorbance (at max) versus FeII concentration. Save the spectrum and calibration curve on
your computer and print it out.

C. Molecular Weight Determination of Unknown FeII salt.

1. Obtain an unknown FeII salt from your TA and mass it.

2. Put the salt into a 25 mL volumetric flask and add 1.0 mL of 6 M HCl before diluting to
volume with DI water.

3. Transfer 1.0 mL of the solution in #2 to a 100 mL volumetric flask, add 1.25 mL buffer and
40 mg ferrozine and dilute to volume with DI water.

4. Take visible spectrum of the above solution and record the absorbance at max. If the
absorbance is too high for your calibration curve, perform quantitative dilution(s) until the
absorbance is in range.

5. Calculate the concentration of the unknown using the calibration curve created above. From
the concentration and the known mass, calculate the molecular weight of your salt. Show all
work and record the final number in your notebook.

The five possible unknowns: FeSO47H2O, FeCl26H2O, Fe(NH4)2(SO4)26H2O,


FeBr26H2O, and FeI26H2O. Match the unknown you were given to one of these.

D. Determination of FeIII Concentration Determination in an Aqueous Sample

1. Request a ferric ammonium sulfate dodecahydrate (NH4Fe(SO4)212H2O) aqueous solution


of unknown concentration from your TA. (Your TA will need to prepare this for you, as rust
precipitates out of solution over time.)

3
Absorption Spectroscopy Revised: 3/19/13

2. Place 1.0 mL of the ferric ammonium sulfate dodecahydrate solution in a 25 mL volumetric


flask. Add 40 mg ferrozine and 1.25 mL of ammonium acetate buffer. Then dilute volume
with DI water. Take a visible spectrum of this solution.

3. Place 1.0 mL of the ferric ammonium sulfate dodecahydrate solution in a 25 mL volumetric


flask. Add 1.5 mL hydroxylamine hydrochloride (H3NOHCl, 10% w/v) (a reducing agent).
Stir by swirling the flask for at least one minute. Add 40 mg of ferrozine and 1.25 mL of
ammonium acetate buffer. Then dilute volume with DI water. Wait for 5 minutes, watching
for a color change. Record changes in your notebook. Take a visible spectrum of this
solution. Is there any unreacted Fe3+ left in solution?

4. If the absorbance is outside of the range of your calibration curve, prepare a new solution
with more or less ferric ammonium sulfate dodecahydrate solution, recording the exact
amount used. From this information, calculate the concentration of FeIII according to your
calibration curve and calculate the concentration of the undiluted salt in the solution obtained
in step a.

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