Experiment Three: Titration Analysis of Percent Purity of K3Fe(C2O4)3•3H2O

Pre-Lab Questions:
1. What is the indicator for the endpoint of the titration of oxalate (C2O42-) with permanganate
(MnO4 ).
2. Why can’t we just make a solution of KMnO4 and determine the concentration by
calculation? Why do we have to use titration?
3. Prepare your own data tables for this lab. Write them in your lab book and reproduce them to
hand in for the pre-lab questions. If you show up in lab with no data tables or if you spend the
first 10 minutes of lab copying data tables from your lab partner you will not be permitted to
participate in the lab. The point of designing a data table is so that you will carefully read the
lab, think about the steps in the lab, and know exactly what you will be doing.

Purpose
To determine the percent purity of K3Fe(C2O4)3•3H2O.

Introduction
The percent purity of the complex iron salt, K3Fe(C2O4)3•3H2O, is determined by analyzing the
sample for oxalate (C2O42-) content. The iron salt is titrated with permanganate (MnO4 ) to
determine the amount of oxalate present. The iron salt reacts with permanganate according to.

5 Fe(C2O4)33-(aq) + 6 MnO4-(aq) + 48 H+(aq)  5 Fe3+(aq) + 6 Mn3+(aq) +30 CO2(g) + 24 H2O(l)

Although iron seems the more likely redox agent, oxalate is the reactive species in this titration
given our conditions. Following the reaction, the oxalate content can be determined
experimentally by titrating a known mass of the sample with a standardized solution of KMnO4.
Note that in acid solution, oxalate is present as oxalic acid H2C2O4.

Please note that the reaction above and all subsequent reactions are the net ionic reactions.
Therefore, spectator ions are omitted. Also the oxalate ion C2O42- is present acidified under
the experimental conditions. Therefore, C2O42- is present as H2C2O4 (oxalic acid).

Given that MnO4- is intensely purple in solution, and its reduction product Mn2+ is colorless, the
MnO4- functions as its own indicator. When the purple MnO4- is added from the buret to the
oxalate solution, it is decolorized when it is completely reduced to Mn+2. When all of the oxalate
is consumed, the solution in the titration flask will be a light pink because of a slight excess of
MnO4-. This is the end point of the reaction (i.e. all oxalate has been reacted).

As with all titrations, from the moles of MnO4- required in titration, we can use the balanced
equation to calculate the grams of C2O4-2 in our weighed sample of K3Fe(C2O4)33H2O. By
comparing the grams of C2O4-2 by titration analysis to the theoretical grams given by the
formula, we can calculate the percent purity of the sample.

Burets and Titration

Titration is a method for accurately determining the concentrations of solutions. Commonly,
titration is done to determine the concentration of an acid by titrating with a base. The base
solution is standardized; that is, its concentration is accurately known. The amount of acid can
be determined by neutralizing it with the known amount of base.

Because most acid and base solutions are colorless, a method is needed to tell when
neutralization has occurred, that is, when equal molar amounts of acid and base have been
mixed. An indicator compound is used for this purpose. Acid-base indicators change color in
acidic solutions or basic solutions. A typical acid-base indicator is phenolphthalein. It is
colorless in acidic solution and pink in basic solution. The change from colorless to pink is the
signal which tells you that just enough base has been added to react completely with the acid.
This is called the endpoint of the titration. As mentioned in the introduction our experiment does
not require the use of an indicator given that MnO4- is intensely purple in solution, and its
reduction product Mn2+ is colorless. Thus the MnO4- functions as its own indicator.

A buret is a precisely sized glass tube with graduations that measure the volume of liquid it
contains. The liquid placed in the buret is called the titrant. By reading the beginning volume,
adding titrant from the buret during the titration, and then reading the ending volume, you can
tell how much solution has been drained from the buret.

Figure 1. Buret Setup and reading the buret

http://water.me.vccs.edu/buret.htm

As with graduated pipets and cylinders, the liquid level is read from the bottom of the meniscus
observed straight on to minimize parallax error. Proper scale reading skills should be used to
determine the correct number of decimal points and significant figures for each reading. The
thing about burets is that are graduated from the top down because they are calibrated to deliver
a volume not to contain it. This can create some confusion when taking readings. The correct
volume to be recorded from the buret in this figure is between 11.4 and 11.5 mL. 11.45 is a good
estimate. Always remember to record an estimated value.

Overview of Procedure
Part One: Prepare oxalate solution (Na2C2O4) and calculate molarity.
Part Two: Determine the concentration of permanganate solution (KMnO4) by titration (using
the oxalate solution from Part One).
Part Three: Titrate iron salt K3Fe(C2O4)3•3H2O to determine percent purity of the sample.
Now that you know the exact concentration of your permanganate solution. You can use it to
titrate your iron salt and determine the percent purity.
Procedure

Part One: Preparation of a Standard Solution of sodium oxalate Na2C2O4

In order to perform a quantitative analysis of our crystals, we must know the molarity of the
titrant, KMnO4, to at least three significant digits (standardized). Because of its high reactivity,
it is not possible to prepare a standard solution of KMnO4 by direct weighing. Instead, we will
prepare a standard solution of Na2C2O4 by direct weighing and use this solution to standardize
(determine the exact concentration of) the KMnO4 solution.

The KMnO4 solution is initially known to only approximate concentration. Your titration will
allow you to determine the molarity, which will be close to this value.

1. Weigh appx 1 g of pure, dry Na2C2O4 into a clean 100 mL beaker.

2. Record the exact mass in the data table in your lab notebook.
3. Add about 70 mL of distilled water to dissolve the sample completely. This may require
some gentle warming and stirring using a hotplate.
4. Transfer the solution quantitatively to a 100 mL volumetric flask using several small rinses ( 5
mL or so) of the beaker with distilled water. Allow the solution to cool to room temperature,
then carefully dilute to the calibration mark. Mix well.
5. Calculate the molarity of the oxalate solution before moving to the next step. Do the
calculations in the analysis and calculations section of the lab report.

Part Two: Standardization of KMnO4 Solution

The reaction of MnO4- with oxalate shown below is the reaction for the standardization, which is
different from the reaction of MnO4- with Fe(C2O4)2-. Note that oxalate is present as oxalic acid
under these conditions. This reaction requires a modest temperature of 75oC.
2 MnO4-(aq) + 6 H+(aq) + 5 H2C2O4 (aq)  8 H2O + 2 Mn2+(aq) + 10 CO2 (g)

Note: High temperatures will cause an unwanted side reaction (the formation of MnO2 as an
orange solid will appear). If your reaction turns orange while you are titrating, you will need to
restart the trial at a lower temperature. If it turns orange after you finish that's obviously okay.

1. Pipet a 10.00 mL aliquot of the sodium oxalate solution into a 250 mL Erlenmeyer.
2. Using a graduated cylinder, add 10 mL of distilled water and 20 mL of 1 M H2SO4 to the
same Erlenmeyer in step 1 above.
3. Using a hot plate, heat the solution to be titrated to about 68oC.
4. Place the stir bar in the solution and set at a moderate rate for stirring. Don't let it stir so fast
that solution splashes out of the container.
5. While you are waiting, obtain about 200 mL of KMnO4 solution into a labeled clean, dry
beaker. Rinse a buret with three times with 3 – 4 m L of the KMnO4 solution. Discard each
rinsing into a labeled waste container, then fill the buret. Be sure to eliminate any air
bubbles from the tip of the buret. 6. Once the oxalate solution is at temperature, position
the buret over the beaker for titration. Read and record the initial buret reading.
7. Add a 1-2 mL of KMnO4 to the beaker, stir, and wait for the MnO4- to be reduced to the
colorless Mn+2.
8. Continue the titration, keeping tight control of the rate of addition so that the color of the
MnO4 is discharged before the next portion of titrant is added.
9. Keep the temperature about 70oC during the titration. Continue the addition of titrant until a
permanent pink color is obtained.
10. Read and record the final buret reading.
11. Do a second and third titration with additional 10.00 mL aliquots of standard sodium oxalate
following the same set of procedures.
Part Three: Analysis of K3Fe(C2O4)3•3H2O
In aqueous solution, the complex iron salt exists as K+(aq) and the yellow green Fe(C2O4)33-(aq)
complex ion. In acidic solution, MnO4- oxidizes the complex ion according to the net balanced
ionic equation below.

5 Fe(C2O4)33-(aq) + 6 MnO4-(aq) + 48 H+(aq)  5 Fe3+(aq) + 6 Mn+2(aq) + 30 CO2(g) + 24 H2O(l)

Note: The oxidation and reduction products are the same as in the standardization reaction.
Fe+3(aq) is also present in the solution, but has not changed oxidation state.

1. Using the milligram balance, weigh about one gram of the dry green K3Fe(C2O4)3•3H2O
crystals into a 100 mL beaker. Record the accurate mass in your data table.
2. Dissolve the crystals in 50-70 mL of distilled H2O and transfer the solution quantitatively to a
100 mL volumetric flask. You may need to heat the solution as before, prior to transfer into
the volumetric flask.
3. Once at room temperature, dilute the solution to the mark. Mix well by inversion, keeping
hold of the stopper in the flask.
4. Pipet a 10.00 mL aliquot of the new K3Fe(C2O4)33H2O solution into a 250 mL Erlenmeyer.
Add 10 mL of distilled water and 20 mL of 1 M H2SO4. As in part two, heat the solution to
68oC and titrate with the KMnO4 solution.
5. Review the instructions in part two before you begin.
6. Note: In this titration, the yellow green color of Fe(C2O4)3+3 will be present during the
titration. Just before the end point, the yellow green color fades and then the permanent light
pink color appears in the solution.
7. Titrate a second and third 10.00 mL aliquot of K3Fe(C2O4)3•3H2O solution.

Data
Record all data in your notebook. Show your data to the instructor before you leave the lab.

Analysis and Calculations

The purpose of this experiment is to determine the percent purity of K3Fe(C2O4)3. Based on the
data you have collected in this lab, report the following:

1. Determine the molarity of the Na2C2O4 solution you prepared in part 1.

• Clearly indicate this answer.
2. Determine the molarity of the standardized KMnO4 solution you analyzed in part 2.
• Calculation Help: Standardization of KMnO4 Calculations
• Use the volume used and molarity of the sodium oxalate solution (calculated in step 1) to
find the moles of sodium oxalate titrated.
• This is the same as the moles of oxalic acid, H2C2O4.
• Use the stoichiometry of the titration reaction (part II) of oxalic acid to find the moles of
permanganate ion, MnO4-.
• Divide the moles of MnO4-, by the average KMnO4 titration volume to obtain the molarity of
the KMnO4 solution. Clearly indicate this answer.
• Watch your significant figures!

3. Percent purity of K3Fe(C2O4)3 you analyzed in part 3.

Determination of the percent purity requires you to do two calculations.

 First, determine the number of moles of K3Fe(C2O4)3 that you reacted. Since you don't know
how much of the solid that you put into the flask was pure, you must rely on the amount of moles
of KMnO4 titrated. Use the number of moles of KMnO4 (you know the volume that you used and
the concentration of KMnO4 from part 2) and use the stoichiometry of the reaction (part III) to
determine the number of moles K3Fe(C2O4)3 present in solution. This is moles of K3Fe(C2O4)3
titrated. Clearly indicate this answer.

Second, do another calculation where you assume that the sample is 100% pure.
Here you just use the mass that you weighed out to determine the molarity of the solution as if
the compound was 100% pure. Then determine the number of moles in the titration based on the
volume you pipeted and the molarity. This is moles of K3Fe(C2O4)3 if pure. Clearly indicate
this answer.

Finally, the percent purity is:

moles of K 3Fe(C 2O 4 ) 3 titrated
x 100%
moles of K 3Fe(C 2O 4 ) 3 if pure

Your answer should be a value between 50-100%. Clearly indicate this answer.
€
A very common mistake will give you a result less than 10% pure. If you get a number that is
below 10% purity, double check your math (hint: be careful about the number of moles you use
in parts 1 and 2 - you are making solutions that have a volume of 100.00 mL, but you are only
using part of these solutions).

Show all calculations that lead to the results for parts 1-3.

Results
See the lab report format for a description of the results table.

Discussion
The discussion is a qualitative and quantitative description of the experiment. Describe what you
did (qualitative) and what the result was (quantitative – number). Indicate two sources of error
(indicate if the error was random or systematic) and indicate specifically how they would affect
your data. You should make sure the error is quantifiable and actually relates to your data. (For
example, don’t say that your over-titrated, if your calculated concentration is too low…that
wouldn’t make any sense.)

Post Lab Questions

1. In part 2 you determined the concentration of your KMnO4 by titrating a solution of sodium
oxalate. How would your concentration of KMnO4 have been off if you had overshot the
endpoint of your titration (added to much KMnO4)?
2. If your calculation of the concentration of KMnO4 from part 2 is incorrectly low, how will
this affect your determination of moles of K3Fe(C2O4)3 in part 3. If you answer “it will be
wrong” you will not receive any credit. Your answer should explain the specific way this
inaccuracy will affect the calculation (higher or lower) in part 3.