Redox Titration: Analysis of Bleaches

Like acid-base reactions, oxidation-reduction reactions can be used as an analytical tool.

In this experiment, we will determine the percentage of hypochlorite ion in laundry bleaching
solutions. In liquid bleaching solutions, this ion is present in the form of sodium hypochlorite. In
solid bleaches, the ion is more commonly present in the form of calcium hypochlorite. There are
also non-chlorine containing bleaches available at the supermarket. The active ingredient in
these products is hydrogen peroxide.

The effectiveness of a bleach solution is related to its ability to oxidize substances.

Detergents help to remove dirt and grease from clothes by both an emulsification process and
agitation. Most liquid bleaches use the hypochlorite ion (usually present in the form of sodium
hypochlorite originally) as an oxidizing agent.

Commercial bleaching solutions are made by reacting chlorine gas with the hydroxide
ion. If the base is sodium hydroxide, the resulting substance is sodium hypochlorite. Bleaching
solutions remove colors from a fabric because of an interaction between the hypochlorite ion and
a colored species.

The general process (that occurs in acidic solutions) is as follows:

The hypochlorite ion is converted into the chloride ion

ClO(aq)  Cl(aq) (eq 1)

The iodide ion is converted to elemental iodine (I2)

I(aq)  I2(aq) (eq 2)

The balanced net ionic equation is

ClO(aq) + 2I(aq) + 2H+  I2(aq) + Cl(aq) + H2O(l) (eq 3)

This reaction goes to completion, meaning that all of the hypochlorite ions have completely
reacted with the iodide ion.

Typically we add some KI solution to distilled water and then add a strong acid. At this point the
solution is likely to have a yellowish color. Next, a known volume of bleaching solution is added
to the reaction vessel. This results in the immediate formation of elemental iodine (I 2) and the
solution turns a deep dark red color.

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 You may ask how we can measure the amount of hypochlorite ions from this process.
The answer is that we cannot determine the amount of hypochlorite from this process. We do
know that we added excess iodide ion to a known quantity of the hypochlorite ion. We assume
that the iodine formed can be used as a measure of the amount of hypochlorite. There is a very
simple and easy reaction that we can perform to determine the amount of elemental iodine
formed. It is in fact a reaction that we have previously used in the kinetics experiment. It is to
react elemental iodine with the thiosulfate ion as follows:

I2(aq) + 2 S2O32(aq)  2I(aq) + S4O62(aq) (eq 4)

red-brown colorless colorless colorless

In this reaction the elemental iodine is converted back into the iodide ion.

The next step will be to titrate the iodide solution with a known concentration of sodium
thiosulfate. As we add the thiosulfite ion, the amount of I 2 constantly decreases. This is observed
by noticing that the very dark red-brown color becomes reddish, then becomes orange, then
yellow, and finally colorless. It is very difficult to see when the yellow color has vanished so
determining the end point becomes somewhat a guess. However, if we add some starch to the
light yellow solution, we can make a much more stunning end point. In the kinetics experiment
you performed, the solution eventually turned blue-black because elemental iodine was
produced. In this reaction we can perform the reverse process where iodine is being used up and
colorless iodide ion is being formed. When we add a small amount of starch to the light yellow
iodide solution, it turns dark blue-purple. As the thiosulfate solution is added, the color becomes
lighter eventually become a light bluish purple color. At this point it will require only one or two
more additional drops of thiosulfate solution to turn the reaction mixture colorless.

NOTE:If the starch solution is added too early in the titration, the formation of the blue-black
substance is not easily reacted causing the end point to occur very slowly and making it difficult
to observe.

We can now determine the amount of hypochlorite ion in the commercial bleaching
solution. From the known concentration of the sodium thiosulfate solution and the volume of
this solution we can determine the moles of sodium thiosulfite used in the titration. Using
equation 4 we can calculate the mole of elemental iodine formed. Then using equation 2, we can
find the moles of hypochlorite ion in the initially solution.

In this reaction it is difficult to know exactly the sodium thiosulfate concentration

because a small quantity of the thiosulfate ion undergoes decomposition on mixing with water.
A more concentrated version of the thiosulfate solution you will use will be provided to you.
You will be required to determine the exact concentration of a diluted thiosulfate solution using
a standard solution (a solution whose concentration is known). In this case the standard solution
will be potassium iodate. The reaction between the iodate and the thiosulfate ion also will create
iodine and will visually appear identical to the process previously described.

The net ionic reaction for this overall process is:

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IO3(aq) + 6S2O32(aq) + 6H+(aq)  I(aq) + 3S4O62 (aq) + 3H2O(l)

From this reaction, we can see that 6 moles of thiosulfate ions are required for each mole of
iodate ions used. Using this information we can convert the concentration of the iodate ions to
the concentration of thiosulfate ions.

In this experiment you will first standardize an unknown sodium thiosulfate solution and
then use this information to determine the concentration of hypochlorite ion in a commercial
bleaching sample.

One possible source of error can arise due to the ability of iodide ions being able to be oxidized
to I2 by oxygen present in the air. The reaction is

4 I + O2 + 4H+  2 I2 + 2H2O

This reaction is quite slow in neutral solution. However, the reaction rate increases with acid
concentration. To prevent excess I2 formation that results in extra thiosulfate solution being
needed to reach the end point of your titration, one should perform the titration immediately
after adding the sulfuric acid solution.

CHEMICAL RESPONSIBILITY

Sodium thiosulfate (Na2S2O3)slightly toxic by ingestion, body tissue irritant

Potassium iodate (KIO3)oxidizer, moderately toxic, tissue irritant
Potassium iodide (KI)no major health risks
Sulfuric acid (H2SO4)corrosive, can cause skin burns
Commercial bleachcorrosive liquid, causes skin burns, moderately toxic by ingestion and
inhalation
Starchno major health risks

Caution: Comercial liquid bleaches containing sodium hypochlorite are corrosive to the
skin and eyes. If you get any on your skin, wash it off immediately.

PROCEDURE
Step 1: Standardization of Sodium Thiosulfate Solution

Prepare about 250 mL of an approximate 0.1M solution of sodium thiosulfate by diluting a 1.0
M solution of sodium thiosulfate.

Obtain a 50 mL buret and clean it out with tap water. Then rinse it with about 15 mL of tap
water. These rinses can be discarding into the sink. Use a 400 mL or 600 mL beaker as a waste
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collection vessel. Lastly rinse it twice with 5 mL portions of your sodium thiosulfate solution.
Discard these two rinses in your waste collection beaker. Now you are ready to fill your buret
with the sodium thiosulfate solution. To do this, use your gravity funnel. Make sure you do not
overfill the funnel or the solution will overflow. You want to add the thiosulfate solution until
the liquid level is slightly above the zero mark. Drain down (collecting the waste in your waste
beaker) so you are exactly at the zero mark or slightly below it. Read and record (to the nearest
0.02 mL) this volume.

Next obtain a 25 mL pipet and a pipet pump from the supply table in your lab room. Pipet 25
mL of the standard 0.010 M potassium iodate (KIO3) solution into a clean (it does not need to be
dry) 125 mL Erlenmeyer flask. Next, add about 10 mL of 10% KI solution to the flask. Finally
add about 5 mL of 1.0 M sulfuric acid to the flask. At this point the solution should have turned
a dark red-brown color. Immediately start to titrate this solution with the sodium thiosulfate
solution in your buret. As this titration proceeds, the red-brown color will change to red, then to
orange, and then to yellow. When the solution has become a very pale yellow, add about 1 mL
of 1 % starch (a squirtful) to the solution. This should change the solution color to dark blue.
Continue titrating (drop by drop) until the blue color disappears. After each drop is added, swirl
your flask. If the blue color persists, add an additional drop and repeat the procedure until the
blue color disappears. If you go beyond the end point, you cannot go back in this process.

Discard your waste into your waste beaker.

If needed, refill your buret with additional sodium thiosulfate solution (as described earlier.

Repeat this titration twice more, so that you have three total titrations for the standardization of
the sodium thiosulfate solution. Since everybody’s dilution will be slightly different, you cannot
use your neighbor’s data.

Note: All three titrations should yield identical results. So when you do the second and third
titrations, you can very quickly add the sodium thiosulfate solution until you get within about 1
to 2 mL of the expected end point. For example, if your first titration required 32.4 mL of
sodium thiosulfate, you can very quickly drain in about 31 mL of sodium thiosulfate for the
second and third titrations, add your starch, and finish the titration.

After finishing the third titration you can empty your waste beaker into the waste container in
the hood (probably a 5 gallon plastic container).

From this data, one can calculate the concentration of your diluted sodium thiosulfate solution.

Step 2: Titration of Commercial Bleach with Sodium Thiosulfate

Refill your buret with sodium thiosulfate solution.

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Obtain a 1 mL calibrated pipet from the supply table. Next, pour about 10 mL of commercial
bleach into your 50 mL beaker (do not use a larger beaker as you will not be able to pipet any
liquid out).

Add 25 mL of distilled water to a clean (does not need to be dry) 125 mL or a 250 mL
Erlenmeyer flask. Next, add 5 mL of 10% KI solution to the flask and then pipet exactly 1 mL
of the commercial bleach solution into the flask. Finally, add about 10 mL of 1.0 M sulfuric acid
to the flask. At this point the solution should have turned a dark red-brown color. Immediately
start to titrate this solution with the sodium thiosulfate solution in your buret. As this titration
proceeds, the red-brown color will change to red, then to orange, and then to yellow. When the
solution has become a very pale yellow, add 1 mL (about a squirtful) of 2 % starch to the
solution. This should change the solution color to dark blue. Continue titrating (drop by drop)
until the blue color disappears. After each drop is added, swirl your flask. If the blue color
persists, add an additional drop and repeat the procedure until the blue color disappears. If you
go beyond the end point, you cannot go back in this process.

Discard your waste into your waste beaker.

If needed, refill your buret with additional sodium thiosulfate solution (as described earlier.

Repeat this titration twice more, so that you have three titrations for the determination of the
percentage of sodium hypochlorite in commercial bleaching solution. Since everybody’s
concentration of sodium thiosulfate will be slightly different, you cannot use your neighbor’s
data.

Note: All three titrations should yield identical results. So when you do the second and third
titrations, you can very quickly add the sodium thiosulfate solution until you get within about 1
to 2 mL of the expected end point. For example, if your first titration required 32.4 mL of
sodium thiosulfate, you can very quickly drain in about 31 mL of sodium thiosulfate for the
second and third titrations, add your starch, and finish the titration.

After finishing the third titration, you can empty your waste beaker into waste container in the
hood (probably a 5 gallon plastic container).

You can now calculate the concentration and weight percent of sodium hypochlorite in liquid
bleaches.

CALCULATIONS

1. Standardization of sodium thiosulfate

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 Using the equation:

IO3(aq) + 6S2O32(aq) + 6H+(aq)  I(aq) + 3S4O62 (aq) + 3H2O(l)

You can calculate the concentration of your diluted sodium thiosulfate solution.

From the known concentration of the potassium iodate solution (found on the reagent
bottle) and volume used (25 mL), we can calculate the moles of potassium iodate reacted.
Using the coefficients of the above balanced equation, we can convert the moles of
potassium iodate to moles of sodium thiosulfate. Lastly, using the volume of sodium
thiosulfate used in each trial and the moles of sodium thiosulfate calculated above, you
can determine the molar concentration of your sodium thiosulfate solutions.

2. Determining the molar concentration of commercial bleach solution:

From the calculated concentration of sodium thiosulfate solution calculated above and
the volume of sodium thiosulfate used in each titration in part 2, we can determine the
moles of sodium thiosulfate needed for each titration.

Then, using the equation:

I2(aq) + 2 S2O32(aq)  2I(aq) + S4O62(aq) (eq 4)

red-brown colorless colorless colorless

We can convert the mole of sodium thiosulfate into moles of iodine (I 2).

Note: When sodium thiosulfate dissolves, it produces one mole of thiosulfate ions.
That is, the mole of sodium thiosulfate used in each titration is the same as the mole
of thiosulfate ion used up.

Na2S2O3  2Na+ + S2O32

Next, using the equation

ClO(aq) + 2I(aq) + 2H+  I2(aq) + Cl(aq) + H2O(l)

we can convert the moles of iodine (I2) into the mole of hypochlorite ions.

Again, when sodium hypochlorite dissolves, we see that the moles of hypochlorite ions
must equal the moles of sodium hypochlorite.

NaClO  Na+ + ClO

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We have now calculated the concentration of sodium hypochlorite (or the hypochlorite
ion in commercial liquid bleaches).

However, most commercial bleaching solutions are reported as a weight percent of

sodium hypochlorite. We will need to convert the molarity of sodium hypochlorite into a
weight percent.

That is

From the moles of sodium hypochlorite used, we can determine the mass of sodium
hypochlorite.

We can find the mass of commercial bleaching solution by using the density of the
commercial bleach. This value is 1.084 g/mL. This mass is calculated by

mass = density x volume

The volume is the amount of commercial bleach pipetted (1 mL).

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 Redox Titration: Analysis of Bleach
Report Sheet (30 Points)
Name _________________________ Lab Day _______________

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Lab Instructor_____________________ Date __________________

Determination of the Concentration of the Potassium Iodate Standard

Titration Data

Trial 1 Trial 2 Trial 3

Sodium Thiosulfate Sodium Thiosulfate Sodium Thiosulfate
Final Buret Volume

Initial Buret Volume

Total Volume Used

Calculations for determining the concentration of potassium iodate

Trial 1 Trial 2 Trial 3

Moles KIO3 used

Mole Na2S2O3 Added

Volume Na2S2O3
Used
Molarity Na2S2O3

Average molarity of Na2S2O3 is _________________ M.

Determination of the Percentage of Sodium Hypochlorite in Bleach

Titration Data

Trial 1 Trial 2 Trial 3

Sodium Thiosulfate Sodium Thiosulfate Sodium Thiosulfate
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 Final Buret Volume

Initial Buret Volume

Total Volume Used

Trial 1 Trial 2 Trial 3

Average molarity of
Na2S2O3 (from 1st Part)
Volume Na2S2O3 Used

Moles of S2O32- ion

required for titration
Moles of I2 produced in the
titration mixture
Moles of OCl- ion in the
titration mixture
Moles of NaOCl present in
the bleaching solution
titrated
Mass of NaOCl present in
titration mixture
Volume of commercial 1 mL 1 mL 1 mL
bleaching solution used
Mass of commercial
bleaching solution used
(Density = 1.084 g/mL)
Percent NaOCl in
commercial bleach

Average percentage of NaOCl present in commercial bleach: _______________

Redox Titration: Analysis of Bleach

Post-Lab Questions (40 Points)
Name _________________________ Lab Day _______________

Lab Instructor_____________________ Date __________________

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1. In the titration between potassium iodate and the sodium thiosulfate solution, if the
titration is not performed immediately after the addition of the sulfuric acid, how would
this likely affect the calculated concentration of your diluted sodium thiosulfate solution?

2. Why did the titrations performed need to be started immediately after adding the sulfuric
acid?

3. A sample of bleach was analyzed as in this procedure. The only procedural difference is
that the student weighed out the bleach solution used instead of pipetting a certain
volume of bleach. The student weighed out 0.634 g of commercial bleach solution. It was
found that it required 13.24 mL of 0.0732 M sodium thiosulfate solution to react with the
iodine produced. What is the percentage of sodium hypochlorite in this bleach sample?

4. The active ingredient in many commercial liquid bleaches is sodium hypochlorite. The
bottle lists the percentage of sodium hypochlorite as 6.0%. If the density of commercial
bleach is 1.084 g/mL, how many mL of 0.150 M sodium thiosulfate is required to reach
the end point in a titration similar to the one performed in this experiment, if a student
analyzed a 2.0 mL sample of bleach.

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5. A student rushed through this experiment, but noted some procedural errors in their lab
notebook. If the following observations were listed in the lab notebook, how would
they affected the calculate sodium hypochlorite percentage? Would the calculated percentage be
too high, too low, or unchanged by their procedural error?

A. A student forced the remaining liquid in the pipet out with the pipet pump.

B. A student had an air bubble in the buret tip that remained there during the entire
titration.

C. A student had an air bubble in the buret tip that came out during the titration.

Redox Titration: Analysis of Bleach

Pre-Lab Questions (10 Points)
Name _________________________ Lab Day _______________

Lab Instructor_____________________ Date __________________

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1. To determine the concentration of a sodium thiosulfate solution as in this experiment, a
student pipetted 25.0 mL of 0.0100 M potassium iodate (KIO3) solution into a 125 mL
Erlernmeyer flask. Potassium iodide and sulfuric acid were added as in this experiment.
The titration needed 15.21 mL of the sodium thiosulfate to reach the end point. What is
the concentration of the sodium thiosulfate solution?

2. Into a 125 mL Erlenmeyer flask was added some KI and H2SO4 as described in the
procedure section of this experiment. Then 3.0 mL of bleach solution was added to the
flask and it was immediately titrated with 0.1261 M sodium thiosulfate solution. It
required 41.26 mL of this sodium thiosulfate solution to reach the end point of the
titration. What is the percentage of NaOCl in the bleach? Assume the density of
commercial bleaching solution to be 1.084 g/mL.

3. A. What should be the color of the solution being titrated after mixing the bleach,
potassium iodide, and sulfuric acid but before the addition of any sodium
thiosulfate?

B. What should be the color immediately after adding the starch solution?

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4. What is meant by the term standard solution?

5. What volume of sodium thiosulfate and water are needed to make 250 mL an
approximate 0.10 M solution starting with 1.0 M sodium thiosulfate solution.

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