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1. Add the permanganate directly into the oxylate solution (not down the walls of the
beaker). Promptly wash down any KMnO4 that spatters on the walls of the beaker into
the bulk of the liquid using a wash bottle.
2. Finely divided MnO2 will form if the KMnO4 is added too rapidly and will cause the
solution to acquire a faint brown discoloring. This is not a serious problem if sufficient
oxylate remains to reduce the MnO2 to Mn2+; simply discontinue the titration until the
brown color disappears.
3. The surface of the permanganate solution rather that the bottom of the meniscus can
be used to measure titrant volumes. While you may use either the meniscus or the top of
the solution, you must be consistent, always making the same choice.
I. Introduction
As an oxidant, dichromate has some advantages over permanganate, but, as it is less powerful,
its use is much more limited. Furthermore, Cr(VI) is thought to be a carcinogen, so any use of
dichromate is discouraged so that the Cr(VI) burden in the environment is minimized. It is
obtainable in a state of high purity and can be used as a primary standard. Solutions of
dichromate in water are stable indefinitely. The half reaction for the dichromate system is:
The most important application of dichromate is in its reaction with iron(II) in which it is
often preferred to permanganate.
Unlike permanganate, dichromate titrations require an indicator. There are three indicators
that may be used for the titration of Fe2+ with K2Cr2O7. These are diphenylamine,
diphenylbenzidine and diphenylamine sulfonate. The colour change for all three indicators is
green to violet and the standard electrode potentials are all ca 0.78 V. According to Kolthoff
and Sandell, this should lie between the electrode potentials of the two reduction reactions.
This not being the case, phosphoric acid is added to reduce the electrode potential for the Fe3+
→ Fe2+ reaction by stabilizing the ferric ion.
3+
As the titration proceeds, the sample solution will turn green due to the presence of Cr . The
endpoint is reached when the very fine yellow color (at the beginning of titration curve) of the
6+
Cr titrant appears (at the end of titration curve).
II. Reagents:
Provided: - Potassium dichromate can be used as a primary standard if it is dried in an oven at
o
150- 200 C for two hours to remove any bound water.
- Zinc metal; conc. H2SO4; conc. H3PO4
To be prepared: Prepare a standard dichromate solution by dissolving an accurately weighed
sample of about 0.4 g in water and make up to 250 mL in a volumetric flask. Calculate the
concentration of dichromate solution in mol.L-1. (FW of K2Cr2O7 = 294.19).
Add about 1 g of zinc metal in 10.00 mL of solution A, replacing the watch glass
immediately. You should carry out titrations with 3 portions of solution A. Do not add all
of the zinc at once since this may reduce the Fe3+ to metallic iron. Heat the flask as
necessary while swirling it gently, to maintain a vigorous but not violent reaction until all
of the zinc is consumed. A few flecks of non-reactive black residue may be ignored. Add
a second 1 g of zinc in 3 portions and heat the solution as necessary.
Repeat the addition of zinc in smaller portions until reduction is complete. Usually this
means that the solution is clear with no trace of yellow. This reaction is, in essence, a
titration of the Fe3+ with Zn(s) . Adding too much extra zinc metal will greatly increase the
time required to dissolve all of the excess zinc. (In concentrated Fe2+ solutions, a very
light green hue of iron(II) may be apparent in a solution that is completely reduced; a
solution that appears green with a trace of yellow will require a small additional portion of
zinc. In addition, a solution that is too low in volume may appear to show a yellow-green
color — add some distilled water and see if the color of the solution turns clear, a sign that
all of the iron(III) has been reduced.)
When the solution appears to be completely reduced, add another 0.1 g of zinc and heat
nearly to boiling for about 5 min. (Approximately 3 g of zinc will suffice for reduction of
0.4 g samples dissolved as described above. The final portion of zinc should not be added
until one is ready to complete that particular titration, since iron(II) undergoes air
oxidation. If any zinc remains undissolved, add 5 mL of concentrated H2SO4 in 20 mL of
water, and swirl the flask until the remaining zinc is dissolved. Very fine bubbles of H2
will emanate from any undissolved zinc as opposed to the larger bubbles of a boiling
solution. Set your reaction mixture off the hotplate and allow the boiling to stop to check
for any "fizzing" unreacted zinc.
After waiting only about 2 to 3 minutes, add to the pre-reduced solution, about 5ml of
concentrated sulfuric acid and 7ml of syrupy phosphoric acid (measured in a graduated
cylinder). Dilute with distilled water to bring the volume to about 125ml. Again cool the
solution to room temperature by running the outside of the flask under cold water. Add 8
drops of diphenylamine sulfonate indicator and slowly titrate with your standard K2Cr2O7
solution from a blue-green, through a greyish tinge to the first permanent violet, which is
the end point. The titration should be conducted dropwise when the grey tinge is noted
because the oxidation of the indicator is somewhat slow at this point. Do a trial run first to
see the end point and determine the sample weight.
Then do three good trials. The average standard deviation should not exceed 0.02 mL.
Blank
There is a significant indicator blank for this titration. To run a blank, all the reagents
except for the iron unknown should be added to a 250ml Erlenmeyer flask and the volume
should then be brought up to the approximate volume at the end point using distilled
water.
Remember the actual end point change is slow. The blank should be no more than 1 to 4
drops (about 0.20ml) and its value needs to be subtracted from the volume of K2Cr2O7
required to titrate each iron sample. Do the blank twice.
NOTE: Solutions containing Cr or Hg should not be poured down the sink, since these metals
are highly toxic. Dispose of these solutions in the waste containers that are provided.