Determination of Iron in Ore by Redox Titration 

Oxidation‐reduction reactions are suitable for titration reactions if they are rapid and
quantitative. The end point can be seen by indicators or by instrumental methods such as
potentiometry.

Potentiometric Titration of Ferrous Ion
The reaction of ferrous ion with ceric ion meets the above requirements.
Fe2+ + Ce4+ Fe3+ + Ce3+ (1)
The course of the titration may be followed potentiometrically with a platinum electrode.
The following cell may be used:
Pt | Titration mixture of Fe3+, Fe2+, Ce4+, Ce3+ || SCE
The potential of the Pt electrode must obey the Nernst equation since the half reactions
between Fe3+ and Fe2+ and between Ce4+ and Ce3+ are nearly reversible.

[Fe3 ] [Ce4 ]

EPt  E 0 (Fe3 ,Fe2 )0.5916 log 2  E 0 (Ce4 ,Ce3 )0.05916 log 3  (2)
[Fe ] [Ce ]

Equation 2 states that the Pt electrode can have only one potential, and the ratios of
[Fe3+]/[Fe2+] and [Ce4+]/[Ce3+] must be such that the Nernst equation is satisfied for both
half reactions. Reaction 1 will occur spontaneously to such an extent that equation 2 will be
true. The ratios [Fe3+]/[Fe2+] and [Ce4+]/[Ce3+] change greatly at the equivalence point. The
equivalence point is determined from the break in the titration curve.

Indicator Titration of Ferrous Ion
Specific indicators and true oxidation‐reduction indicators are available for redox
titrations. Specific indicators are substances that react with one or more of the participants
in a titration to produce a color change. A classic example is starch that forms a dark blue
complex with I2. In redox titrations with I2 as the titrant, blue color develops to mark the
end point of the reaction when I2 begins to accumulate in the solution. Thiocyanate is an
indicator that forms a red complex with Fe3+ but not with Fe2+, and thus can be used to
indicate the formation or disappearance of Fe3+. Sometimes a redox reagent itself is deeply
colored and can be used to indicate the end point. For example, MnO4‐ is a purple ion often
used as an oxidizing agent. The first trace of purple color indicates that the MnO4‐ is no
longer being reduced by the titration reaction.

A true oxidation‐reduction indicator is a substance that has different colors when in
different oxidation states.
Inox + n e‐ Inred (3)

Determination of Iron Ore by Redox Titration

If the indicator reaction is reversible, the Nernst equation applies.
E = E˚ + 0.05916 log {[Inox]/[Inred]} (4)
The color change is observed when the titration mixture goes from one containing mostly
Inred to one containing mostly Inox or vice versa.

An appropriate indicator for the Fe2+ oxidation with Ce4+ is Ferroin, which is a stable
chelate compound of orthophenanthroline with Fe2+.

N N

Fe+3 + e- Fe+2

N N

3 3
Space‐filling model is shown on left, with the chemical reaction on the right.

For convenience, orthophenanthroline will be abbreviated phen. The complex with ferrous
ion, Fe(phen)32+, is intensely red while the complex with ferric ion, Fe(phen)33+, is a pale
blue color.
Fe(phen)33+ + e‐ Fe(phen)32+ E˚ = 1.06 V
In the titration of Fe2+ with Ce4+, the sharp rising portion of the titration curve occurs
between 0.9 and 1.2 V. The orthophenanthroline iron complex is therefore a suitable
indicator for monitoring this reaction.

Procedure (Students will work in pairs for the standardization part of this
experiment.)

For each part of the experiment, a quick titration should be done in order to establish the
approximate volume of titrant required to reach the end point. Then three careful titrations
will be performed. Because the redox reaction is a little slow, the titrant must be added
relatively slowly, (e.g., 1 mL in 10 seconds when far from the endpoint) even after the
approximate endpoint is known. Each student should perform two titrations for the
standardization part of the experiment. A 0.05 M Ceric ammonium sulfate will be provided.
Students should take 300 mL of the solution per pair. The solution must be standardized,
and then the same solution must be used for the iron ore determination.

Determination of Iron Ore by Redox Titration

Preparation of Standard Iron
Accurately weigh four 0.045 ‐ 0.050 g portions of reagent grade Fe powder. Avoid clumps
in the powder since they may contain Fe2O3. Transfer each to a 200 mL Erlenmeyer flask
and add 15 mL of concentrated HCl. Apply gentle heat in the hood until the powder is
completely dissolved. Note that the product of this reaction is FeCl3, and the iron is in the
Fe3+ oxidation state. But the titration reaction requires Fe2+ so the iron must be reduced
before it can be titrated. This is referred to as pre‐reduction.

Have everything set up so that the pre‐reduction of the iron and the ceric ion
standardization or titration can be carried out in rapid succession.

Pre‐reduction of Iron
Heat the FeCl3 solution gently and add stannous chloride (0.67 M SnCl2 in 6 M HCl)
dropwise until the yellow color of FeCl3 just disappears, then add 2 drops in excess. Add 75
mL of 2 M HCl, mix well, and rapidly add 8 mL of 5 % HgCl2 while stirring the beaker
contents. Allow the beaker to stand 5 minutes. (A small amount of white precipitate should
form. If no precipitate forms, not enough SnCl2 was added. If a black precipitate forms, too
much SnCl2 was added. In either case discard the solution and prepare a new solution.)
Proceed with the ceric ion standardization.

Titration with Ce4+ Solution

Be sure to take enough Ce4+ solution to do all the titrations for the entire experiment.
Each pair of students should require about 250 mL of this solution.

After allowing the Fe solution to stand for 5 minutes, add 3 ‐ 4 drops of
orthophenanthroline indicator solution. Titrate to the disappearance of the red color. Carry
a blank solution through the entire analysis, and if necessary, apply a correction for the
blank. Determine the concentration of the standard Ce4+ solution.

Analysis of Unknown Iron Sample

A cool, dry ore sample will be provided by the laboratory instructor. Weigh out 0.9 ‐ 1.1 g
into clean dry 200 mL Erlenmeyer flask, add 25 mL of concentrated HCl, cover with plastic
wrap with a small hole in the wrap (and allow to stand until the following laboratory period
‐ check lab schedule for whether 1 or 2 weeks is allotted for this experiment). Warm the
solutions if they have not completely dissolved. When the sample is in solution, transfer it
to a 250 mL volumetric flask and mix. Rinse the Erlenmeyer flask 3 times with ~ 25 mL of
DI water and transfer the rinse water to the volumetric flask. Dilute the solution to volume.
Transfer four 25 mL aliquots of the solution to four 200 mL Erlenmeyer flasks. Warm the
solution gently and perform the pre‐reduction of the iron as described above. Once the
samples have been pre‐reduced, you may proceed with the titration of the iron ore samples
with Ce4+ as described above. Report the average Fe content of the ore as percent Fe2O3.

Determination of Iron Ore by Redox Titration

Student Name:

Chemistry 3200 
Determination of Iron in Ore by Redox Titration 
Date: Lab Instructor: Section:

Unknown Number:

Grams Fe powder: ____________ ____________ ____________

Moles Fe: ____________ ____________ ____________
mL Ce4+ solution: ____________ ____________ ____________
mL Ce solution to titrate
4+
____________
blank:
Corrected titration volume: ____________ ____________ ____________
Molarity of Ce4+: ____________ ____________ ____________
Molarity of Ce4+ solution: ____________  __________

Unknown
Grams of iron ore sample: ____________
mL Ce4+ solution to titrate Fe ore sample:
____________ _____________ ___________
Corrected titration volume:
____________ _____________ ____________
Average titration
____________  __________
volume:
Moles Ce4+: ____________  __________
Grams Fe in ore: ____________  __________
Percent Fe in ore: ____________  __________
Grams Fe2O3 in ore: ____________  __________
Percent Fe2O3 in ore: ____________  __________

Determination of Iron Ore by Redox Titration

Student Name:

Calculation for grams of Fe2O3 in ore sample:

Calculation for percent Fe2O3 in ore sample:













Calculation for error analysis (Include a list of the errors and their
sources):

Determination of Iron Ore by Redox Titration