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Redox determination of Iron

The purpose of this lab is to teach you about:


Redox chemistry
Quantitative analysis
Error propagation

Theory behind the lab


Iron commonly exists in the +2 and +3 oxidation states.

FeO

Fe2O3

If we want to determine the total iron content in a


sample how do we do it?

1. dissolution of the sample


q Fe compounds are often insoluble in water
q They will dissolve in hot, concentrated HCl.
q Silica which does not dissolve in hot, concentrated HCl will appear as a white
residue.
2.

quantitative conversion of iron(III) to iron(II) with a suitable reducing agent

2Fe3+ + SnCl42 + 2Cl 2Fe2+ + SnCl62


Chloride complexes of Fe(III) are yellow while complexes of Fe(II) are colorless
Add Sn(II) DROPWISE until the yellow color just disappears. Then add ONE
DROP of EXCESS Sn(II).
3.

removal of the excess reducing agent


Remove excess Sn(II) by adding HgCl2

SnCl42 + 2HgCl42 SnCl62 + Hg2Cl2(s) + 4Cl


Mercurous chloride (white preciptate)

If you have TOO MUCH Sn(II) (i.e. you screwed up Step 2) you will get the reaction

SnCl42 + HgCl42 SnCl62 + Hg(l) + 4Cl

colloidal, grey-black
preciptate DISCARD
SAMPLE

4. Addition of special reagents to aid in detection of the endpoint and to


ensure that the proper reaction occurs during the subsequent titration
The reaction we want to study is:

6Fe2+ + Cr2O72 + 14H+


Ferrous
ion

Dichromate
ion = orange

6Fe3+ + 2Cr3+ + 7H2O

Ferric ion

Chromic ion
(green)

Since dichromate ion cant serve as its own indicator, we need an indicator for the
dichromate-chromic ion redox. WHY cant we use dichromate ion cant serve as its
own indicator?
N
H

irreversible

N
H

diphenylamine (colorless)
diphenylbenzidine (colorless)

N
H

+ 2H+ +2e

diphenylbenzidine (colorless)

diphenylbenzidine violet (violet)

The diphenylbenzidine/diphenylbenzidine violet system is reversible a


good characteristic of an indicator.

+ 2H+ +2e

5. Quantitative titration of Fe(II) to Fe(III)

Oxidizing agent: a species that oxidizes something else, in this case


Fe2+ Fe3+
Potassium dichromate is an excellent oxidizing agent for iron(II) for three reasons:
a) dichromate and iron(II) react quantitatively and with a known stoichiometry;
b) the reaction is sufficiently fast to be practical for a titration; and
c) the E is large enough to produce a well-defined endpoint.

Potassium dichromate is a primary standard


i) it can be purchased as a high-purity solid.
ii) Standard solutions of potassium dichromate can be prepared from a weighed
quantity of the dried solid and need not be standardized
iii) the prepared solutions are very stable.

Procedure
1) Preparation of the standard potassium dichromate solution
A. You will be provided by dried K2Cr2O7 that has already cooled.
B. Weigh the sample to the nearest mg. Then transfer the contents to a
CLEAN BEAKER.
C. Now re-weigh the empty sample bottle to determine how much
K2Cr2O7 has been transferred to the beaker.
D. Dissolve the K2Cr2O7 by adding a small amount of distilled water.
E. Clean the volumetric flask thoroughly so that you do not get beading.
F. Transfer the solution to a 500 mL volumetric flask using a funnel.
G. Rinse the beaker 3 times making sure to get ALL of the solution into the
volumetric flask.
H. Add distilled water to the volumetric flask up to the calibration mark.
I. Stopper the flask and mix thoroughly.
J. Calculate the concentration of your K2Cr2O7 solution and label the
standard solution with BOTH the concentration and your name.

2) Preparation of the sample solution (Fe)


A) Transfer 2.0 2.5 g of the iron ore containing sample into a
weighing bottle.
B) Dry at 100 C for one hour. Allow to cool
C) Divide into three roughly equal portions. Weigh each portion and
place in a 500 mL Erlenmeyer flask.
D) Add 10 mL of distilled water to each flask
E) Add 10 mL of concentrated (12M) HCl to each flask.
F) In a ventilation hood gently heat each flask to dissolve the
sample. The silica residue can be ignored.

From this point on, treat each flask all the way through
the experiment before working up the next flask.

3. Adjusting the oxidation state of iron (Fe3+ Fe2+ )


A) In a ventilation hood, heat to boiling the sample solution in the Erlenmeyer
flask.
B) Add dropwise the 0.5 M SnCl2 solution until the yellow color that signals the
presence of Fe3+ disappears. Add ONE or TWO additional drops.
C) Cool the flask to a temperature below 25 C.
D) Add ALL AT ONCE 10 mL of 0.18 M HgCl2. A silky whit preciptate should
form.
E) IF A GREY-BLACK preciptate forms you had too much SnCl2 from Step B)
and you should discard the sample and start with a new sample.
F) Afetr 2-3 minutes (but not longer) add 150 mL of distilled water to the
Erlenmeyer flask.

You are now ready to add the special reagents,


indicator and start titrating.

4) Addition of special reagents, indicators, and titration.


A) Add 10 mL of the sulfuric acid phosphoric acid solution to the flask
B) Add 8 drops of barium diphenylamine sulfonate (indicator)
C) Titrate with your potassium dichromate until the appearance of a deep
violet color throughout the solution.