Experiment 6 - Redox Titration

Experimental Skills
1. How to prepare a solution of primary standard with a volumetric flask
2. How to prepare burets for titration
3. How to titrate a sample

Learning Objectives
1. Be able to compare and contrast a redox equation (or reaction) and a precipitation
equation (or reaction)
2. Be able to write the complete ionic equation for any reaction, especially redox
3. Be able to balance a redox equation
4. Be able to identify the reduction half reaction and the oxidation half reaction
5. Be able to identify the reducing and oxidizing agent in a redox reaction (given the half
reactions)
6. Be able to compare and contrast stoichiometric point and endpoint
7. Be able to compare and contrast titrant and analyte
8. Be able to compare and contrast a standardization titration with a regular titration
9. Be able to compare and contrast a primary and secondary standard
10. Given data from a titration experiment, be able to calculate the desired results (molarity
of the other reactant if a standardization or grams of the analyte or grams of part of the
analyte if regular titration).
11. Be able to compare and contrast an Erlenmeyer flask with a volumetric flask
12. Given data for the preparation of a solution of a primary standard, be able to calculate its
molarity

I. Introduction

The purpose of this experiment is to determine the percent by mass of the active
ingredient in bleach, sodium hypochlorite. Most bleaches contain 5.25%. You will use titration
as the method for quantification. Before titrating the bleach, however, you will need to
determine accurately the amount of sodium thiosulfate in a solution you will make. The reason
for knowing this is because you will react the sodium hypochlorite with the sodium thiosulfate,
thus in order to quantify the sodium hypochlorite, you must also quantify the thiosulfate. The
titration reactions are redox reactions.

A. Redox Reactions
Thus far in the laboratory, you have seen two types of reactions. Job's
method involved a precipitation reaction where two ionic aqueous solutions were
mixed to form an ionic salt that was not very soluble in water. The products of
these types of reactions were easy to predict because the charges of the ions in the
reactants did not change during the course of the reaction. You were able to
calculate the moles of each ion in each solution given the solution's Molarity and
volume used in the reaction.
The other type of reaction that you observed was a redox reaction. In the
metal oxide experiment, you combusted magnesium in the presence of oxygen to
obtain magnesium oxide, see equation 3. The magnesium is composed of atoms.
(Remember that atoms do not have charge, only ions do.) During the reaction
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 with oxygen, the charge on magnesium changes to +2, see equation 1. Likewise,
oxygen atoms in O2 gained two electrons, thus going from a zero charge to a -2
charge, see equation 2. Magnesium undergoes a process called oxidation and
oxygen undergoes reduction. The reactant that undergoes oxidation is called a
reducing agent because that is the action it does to the other species. Oxygen is,
therefore, the oxidizing agent. In this lab, you will observe more redox reactions
as well as learn about the technique known as titration.

oxidation Mg ---? Mg2+ + 2 e- (1)

reduction 1/2 O2 + 2 e- ---? O2- (2)
overall reaction Mg (s) + 1/2 O2 (g) --? MgO (s) (3)

B. Titration of Bleach
Titration is used when we want to quantify the amount of a given chemical
in a solution. For this experiment, you will find out how many grams of the
active ingredient, ClO - which is hypochlorite, are present in commercial bleach.
In order to find the grams of hypochlorite, we need to find another substance (an
inexpensive solution) with which it will react so that we will have some visual
indication as to when we have added stoichiometric amounts of the two solutions.
Sodium thiosulfate would be a good choice except that when it is added to
NaClO, no color change occurs, see equations 4 and 5. The NaClO remains
colorless throughout the addition of sodium thiosulfate.

Hypothetical Titration Reaction of "Bleach" with Sodium Thiosulfate

unbalanced complete eq. NaClO (aq) + Na2 S2 O3 (aq) ---? NaCl (aq) + Na2 S4 O6 (aq) (4)

unbalanced net ionic eq. ClO - (aq) + S2 O3 2- (aq) --? Cl- (aq) + S4 O62- (aq) (5)

An answer is to react the hypochlorite with another substance, in our case I - ions
from KI, which then produces I2 (colored), see equation 6, with which the
thiosulfate can react, see equation 8. We will add starch to our titration so that we
can see the color of I2 more readily. The I2 /starch complex is violet colored in
low concentrations but can look blackish in higher concentrations.

Sample Preparation for Bleach Titration

unbalanced NaClO (aq) + KI (aq) + HC 2 H3O2 (aq) --? NaCl (aq) + H2 O (aq) + I2 (aq) + (6)
complete eq. KC2 H3O2 (aq)

unbalanced ClO - (aq) + H+ (l) + I- (aq) ---? Cl- (aq) + H2O (aq) + I2 (aq) (7)
net ionic eq.

The I2 will undergo a redox reaction with the sodium thiosulfate and at the
endpoint , the solution will change from violet to colorless. We want there to be
stoichiometric amounts present at the endpoint.

Titration of Iodine Formed from Bleach

unbalanced complete eq. Na2 S2 O3 (aq) + I2 (aq) --? Na2 S4 O6 (aq) + NaI (aq) (8)
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unbalanced net ionic eq. S2 O32- (aq) + I2 (aq) ---? I- (aq) + S4O62- (aq) (9)

This type of titration is known as an indirect titration. The sodium

thiosulfate (the titrant) does not react directly with the sodium hypochlorite (the
analyte) but instead reacts with iodine (I2 ) [see equation 8] which was formed
from the reaction of the analyte with potassium iodide (KI) [see equation 6].
Therefore, the moles of thiosulfate will determine the moles of iodine and through
iodine you can find the moles of hypochlorite, hence the "indirect" part of the
name.

Before finding the grams of NaClO, we need to find accurately the

molarity of the sodium thiosulfate. We could theoretically add a carefully
weighed mass of sodium thiosulfate into a volumetric flask, then calculate the
molarity of the solution by dividing the grams of sodium thiosulfate by its molar
mass and then dividing the resulting moles by the liters of solution prepared. The
reason we cannot do this is because it is not pure enough. Therefore we need to
accurately find the molarity of a solution of sodium thiosulfate by another
titration. Because the purpose of this titration is different, it is called
standardization. In standardization, a primary standard is used. A primary
standard is any substance that is 99.9% (or better) pure, does not decompose
under normal storage conditions, is stable when dried, and whose composition is
known.

C. Standardization of Sodium Thiosulfate (The Titrant)

Because sodium thiosulfate is not a primary standard, we will determine
its molarity against a chemical that is a primary standard, KIO 3 , potassium iodate.
Like sodium hypochlorite, potassium iodate is a clear colorless solution and
therefore we will not have a visual indicator of when a stoichiometric amount of
sodium thiosulfate has been added. Also like hypochlorite, iodate can react with
iodide in KI to form iodine, I2 , see equation 10.

Sample Preparation for Standardization of Sodium Thiosulfate

unbalanced complete eq. KIO 3 (aq) + KI (aq) + H2 SO4 (aq) --? H2O (aq) + I2 (aq) + K 2 SO4 (aq) (10)

unbalanced net ionic eq. IO 3 - (aq) + I- (aq) + H+ (aq) ---? H2O (l) + I2 (aq) (11)

Once the sample is prepared, it can be titrated.

Titration to Standardize Sodium Thiosulfate

unbalanced complete eq. Na2 S2 O3 (aq) + I2 (aq) --? Na2 S4 O6 (aq) + NaI (aq) (12)

unbalanced net ionic eq. S2 O32- (aq) + I2 (aq) ---? I- (aq) + S4O62- (aq) (13)

D. Summary of Titrations
To summarize, the first procedure you will perform in the laboratory will
be to make a KIO 3 solution in a volumetric flask, so that you can calculate its
Molarity to at least four significant figures. It is a primary standard. After adding
KI so that you will have a way to see the stoichiometric point in the reaction, you
will titrate the solution of Na2 S2 O3 so that you will know its molarity to four
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 significant figures. Sodium thiosulfate can now be labeled a secondary
standard. Now, the bleach can be titrated (after adding KI) with the sodium
thiosulfate because now you know the molarity of thiosulfate.

II. New Techniques

A. Microburets - A microburet is a 2 mL graduate pipet with a syringe attached

to the top. With this device, you will be able to controllably add quantifiable
drops of a titrant into a solution. Remember to not let the level of the solution
drop below the last line with a measurement on the buret. Refill the buret with
solution after recording the position of the meniscus before refilling. NOTE: an
air space of 1 cm must be maintained at all times. Never push the plunger
completely to the bottom of the syringe. Doing this will generate unwanted air
bubbles into your buret.

B. Automatic Micropipets - Automatic micropipets are used to measure

microliters of solution accurately.
Use: Attach a disposable tip to the end of the pipet. Push the plunger of
the pipet down till you feel resistance, known as the first stop. (Do NOT push the
plunger ALL the way down; this is known as the second stop.) Next, place the tip
into the solution to be measured. Leaving the tip submerged under the solution
and having the pipet perfectly perpendicular, slowly and with control, release the
plunger. Once the plunger has been fully released, move the tip of the pipet over
the vessel into which you want the solution to be. Push the plunger down to the
first stop. Wait a couple of seconds and then push the plunger down all the way.
If any drops adhere to the tip, transfer them to the side of the vessel by touching
the tip to the wall of the vessel. No solution should remain in or on the tip. When
you are not using the micropipet, hang it on a microclamp or in its holder; always
keep it perpendicular or nearly perpendicular.
Changing the volume: To change the volume, push the plunger down first
stop and turn the plunger clockwise to lock it. Now turn the ring to change the
volume. (Alternative: At the base of the plunger is a ring that locks the volume
into place. Push the plunger down to the first stop and turn the ring; this changes
the hundreds value. While still holding the plunger down, lift the ring. Turning
the ring while the plunger is at the first stop changes the tens and ones values.
When you have dialed the volume you want, push the ring back down into
position and release the plunger.) You should find that the height of the plunger
is directly proportional to the relative value of the volume.

C. Volumetric Flasks - A volumetric flask is used to measure the volume of a

solution accurately and precisely out to two places past the decimal. For example,
a 100 mL volumetric flask really measures a volume of 100.00 mL, thus having
five significant figures. Volumetric flasks have only one line etched on them.
When the bottom of the meniscus falls directly on the line, the volume is accurate
and precise.

D. Single Pan Balance - Some substances in the laboratory are added in excess to
a reaction. Because they are not limiting reagents, we do not need to find their
masses to a great deal of precision. The instructor will demonstrate how to obtain

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 masses quickly of excess reagents (in this experiment -- potassium iodide) using a
single pan balance.

III. Procedure

A. Standardization of the thiosulfate solution

1. Making solutions and filling burets: Obtain ~2.5 g of sodium
thiosulfate pentahydrate, Na2 S2 O3 . 5H2 0 in 50 mL beaker.
Dissolve in ~50 mL of distilled H2 O. Obtain a microburet and
label it for sodium thiosulfate. Rinse the buret with distilled water
three times. Now rinse the buret with sodium thiosulfate three
times and then fill the buret.
Obtain a 25 mL volumetric flask. Rinse well with distilled
water. With the cap on (or with parafilm), obtain the mass of the
volumetric flask. Leave the cap on until you add the potassium
iodate.
In a weighing boat or with weighing paper, obtain 0.268 ?
0.001 g of potassium iodate. Remember to record all four places
past the decimal for the mass. Place all of the solid into a well-
rinsed (with distilled water) 25 mL volumetric flask. Place the cap
back on the vo lumetric flask and obtain the mass of the ensemble.
Next, add distilled water (can use the wash bottle) to fill the
bottom of the volumetric flask half way. Swirl to dissolve all of
the crystals. You may add water incrementally in order to dissolve
the crystals, if necessary. Once all are dissolved, add distilled
water with a clean disposable pipet such that the meniscus hits the
bottom of the line in the neck of the flask.
Rinse another microburet three times with distilled water,
then three times with the potassium iodate and then fill the buret.
Label it.

2. Standardizing the thiosulfate solution: Record the initial

volume on each buret. From the potassium iodate buret, measure
out a little more than 1.000 mL of the iodate solution into a 25 mL
Erlenmeyer flask and record the final volume on the buret. Add 5
mL of distilled water to the flask followed by 6 drops of 2 M
sulfuric acid (or 4 drops of 3 M). Weigh out ~600 mg of
potassium iodide. Visually divide this mass into three and add one
of the masses to the solution. (The other two masses will be used
for other trials.) [See equations 10 and 11.] Add 2 drops of starch
solution. Titrate with the thiosulfate solution until the solution
becomes colorless. [See equations 12 and 13.] Repeat the process
for two more thiosulfate samples. Remember to record the initial
and final volumes of the both burets.

B. Titrating the bleach solution: Next, obtain the mass of a 10 mL Erlenmeyer

flask. Using a automatic micropipet, add 100 ? L of the bleach solution and get
the mass of the bleach plus the flask. Add 2 mL of distilled water and 1 mL of 6
M acetic acid. To this solution add ~200 mg of potassium iodide and swirl. [See

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 equaitons 6 and 7.] Add 2 drops of starch. Titrate with sodium thiosulfate until
the solution turns colorless. [See equations 8 and 9.] Remember to record the
initial and final volumes on the buret.
Repeat this entire process for two more trials using different volumes of
bleach where the volumes should be different by at least 50 ? L. Once finished,
clean up and wipe down the bench top.1

IV. Calculations
A. Standardization of thiosulfate
1. Calculate the molarity of KIO 3 in the volumetric flask.
2. For each trial calculate
a. the volume of KIO 3 used to reach the endpoint
b. the volume of thiosulfate used to reach the endpoint
c. the moles of potassium iodate and iodate at the endpoint
d. the moles of sodium thiosulfate and thiosulfate at the endpoint
e. molarity of thiosulfate
3. Average the molarities
B. Titration of bleach
1. For each trial, calculate
a. mass of bleach sample
b. volume of sodium thiosulfate at endpoint
c. the moles of thiosulfate at the endpoint
d. the moles of sodium hypochlorite at the endpoint
e. the grams of NaClO at the endpoint
f. the percent by mass of NaClO in the bleach
2. Average the percents of NaClO

V. Results

Make a table of your results.

VI. Post Lab Questions

1. Why is starch added to the titration?

2. Could the starch be added before starting the titration? Why or why not?
3. If you added one drop too many (what is the approximate volume of a drop?) in order to reach
the endpoint for your bleach, what would be the percent by mass of bleach be? What is the
percent error? Assume that the volume of one drop of sodium thiosulfate is 0.015 mL and use
your data from one of your bleach trials and compare your two answers.
4. Look at the website www.clorox.com/science and find how bleach is made and how
it works. Summarize the chemistry.

VII. Quote of the Week

Many things are lost for want of asking. --English Proverb

VIII. References

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1. Singh, M. M., Pike, R.M., Szafran, Z., Microscale and Selected Macroscale Experiments for
General and Advanced General Chemistry, John Wiley and Sons, Inc., New York, 1995, pg.
252-253.

IX. Copyright Information

Reprinted by permission of John Wiley and Sons, Inc. from Singh, M. M., Pike, R.M., Szafran,
Z., Microscale and Selected Macroscale Experiments for General and Advanced General
Chemistry, John Wiley and Sons, Inc., New York, 1995, Copyright ? 1995, by John Wiley and
Sons, Inc.

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Section: ____________________ Name: _____________________________

Pre Lab Questions for Redox Titration

Directions: Answer the questions assigned by your instructor using this paper. Resources that
are valuable are your chemistry lecture text, the dictionary, etc. If a calculation is requested,
show every step involved in the calculation, remembering to record units and to round answers to
the correct number of significant figures.

1. Balance the following reactions by ion-electron half-reactions.

A. Cu + HNO3 ? Cu(NO3 )2 + NO 2 + H2O
B. FeO + Al ? Fe + Al2 O3
C. HCl + KMnO 4 + H2 C2 O4 ? MnCl2 + CO2 + KCl + H2 O
2. Balance the following reactions:
A. KClO (aq) + KI + H2 O ? KCl + KOH + I2
B. I2 + Na2 S2O3 ? NaI + Na2 S4O6
C. KIO3 + KI + H2 SO4 ? I2 + H2O + K2 SO4
D. Na2 S2O3 + KIO 3 + H2 SO4 ? Na2 S4 O6 + KI + H2 O + Na2 SO4
3. What observations will you need to make in your notebook for this experiment?
4. Set up a data table for this experiment.
5. Define standard, standardization.
6. How does a volumetric flask differ from an Erlenmeyer flask?
7. Calculate the molarity of a potassium iodate solution is made from 1.2993 g of potassium
iodate dissolved in a 250 mL volumetric flask with distilled water.
8. What is the molarity of sulfuric acid if 15.00 mL of it were titrated to the endpoint with
standardized sodium hydroxide? 20.05 mL of 0.273 M sodium hydroxide was used. Need to
write the balance chemical equation for this acid/base reaction.
9. Balance the redox equations 6,8,10,12. Identify the reduction half-reaction and the oxidation
half- reaction. Circle the reducing agent and draw a box around the oxidizing agent in the
final balanced equation.
10. Balance the redox equations 7,9,11,13. Identify the reduction half-reaction and the oxidation
half- reaction. Circle the reducing agent and draw a box around the oxidizing agent in the
final balanced equation.
11. Define and contrast primary standard and secondary standard.
12. Define and contrast endpoint and stoichiometric point. Define analyte and titrant.
13. For the following reactions, balance them (if they are not already balanced -- but you must
check) and then find the number of grams of nitrogen dioxide that are required to make
13.80 g of aluminum iodate as the nitrogen dioxide reacts through the series of reactions.
3 NO2 + H2 O --? HNO3 + NO
HNO3 + I2 ---? 2 HIO 3 + 4 H2 O + 10 NO2
HIO 3 + AlCl3 ---? Al(IO 3 )3 + HCl
14. How many moles of Na2 S2 O3 . 5H2 O are there in 4.50 mL of a 0.20M stock solution? How
many moles of sodium ions are there? Of thiosulfate ions? How many moles of water are
added to the solution due to the release of the waters of hydration when the crystals
dissolve?

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15. Determine the molarity of the sodium thiosulfate solution from the following titration data
(this data is sample data for the standardization of sodium thiosulfate as in this experiment):

mass of empty 25 mL volumetric flask 25.4407 g

mass of 25mL volumetric flask with KIO 3 25.7028 g
initial volume of KIO 3 buret 0.100 mL
final volume of KIO 3 buret (at endpoint) 1.125 mL
initial volume of Na2 S2 O3 buret 0.250 mL
final volume of Na2 S2O3 buret 0.800 mL
16. Determine the percent by mass of NaClO in the bleach sample given the following data.
The molarity of the Na2 S2 O3 is 0.1200M.

mass of empty 10 mL flask 12.8465 g

mass of 10 mL flask with 200.00 µL bleach 13.2067 g
initial volume of Na2 S2 O3 buret 0.165 mL
final volume of Na2 S2O3 buret 0.280 mL

17. Write the balanced chemical equations for the following descriptions:
a) Solid sodium thiosulfate pentahydrate is dissolved in water.
b) Solid potassium iodate is dissolved in water.
c) Solid potassium iodide is dissolved in water.
d) The following clear solutions are added together in a beaker: potassium iodate,
potassium iodide, and sulfuric acid. The products are water, an aqueous solution of
potassium sulfate and an aqueous solution of iodine. (How does this chemical equation
change if the potassium iodide is added as a solid? Write this equation.)
e) A clear solution of thiosulfate pentahydrate is added to a clear solution of iodine
producing an aqueous solution of sodium tetrathionate and an aqueous solution of
sodium iodide. (Note: tetrathionate is S4 O62- )
18. Write the balanced chemical equations for the following descriptions:
a) Clorox bleach (sodium hypochlorite solution) is added to water.
b) The following are added together in a flask: Clorox bleach solution, potassium iodide
solid, and acetic acid. The products are sodium chloride, water, iodine, and
potassium acetate, none of which will precipitate.

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