Experiment 8: Redox: Analysis of the Oxidizing Capacity of Bleach

PURPOSE
In this experiment, you will show how redox reactions can be used to quantitatively determine the amount of
oxidizing agent in liquid hypochlorite household bleach.

There are two oxidation-reduction reactions for determining the oxidizing capacity of bleach. Initially an excess of
iodide ions are added to a bleach solution. The iodide ions are oxidized to iodine after the solution has been
acidified. Starch is added to the resulting iodine solution as an indicator. The solution is then titrated with sodium
thiosulfate until the color of the solution changes indicating the endpoint of the reaction. Data collected from the
titrations will be used to calculate the mass of the sodium hypochlorite in an unknown solution of bleach. Given the
original mass of the unknown solution and the calculated mass of the sodium hypochlorite in the unknown solution,
the percent by mass of the sodium hypochlorite can be determined. The oxidizing capacity of the unknown bleach is
effectively the percent by mass of the sodium hypochlorite in the unknown bleach sample.

OJECTIVES
1) Titration of a sample of bleach with thiosulfate.
2) Determining the end point of the titration with starch indicator.
3) To determine oxidizing capacity of bleach by determining the percentage by mass of the bleach that is sodium
hypochlorite.
4) Balance and summarize the two redox reactions to determine the overall chemical reaction that occurs during
the titration.

PRINCIPLES
Oxidizing Capacity of Bleach
The effectiveness of a bleach to whiten and remove stains in white clothing is related to the oxidizing (bleaching)
strength of an oxidizing agent, such as OCl−, which is found in common household bleaches. The hypochlorite ion is
generally present as a sodium salt, NaOCl, or a calcium salt, Ca(ClO)2.

There are two redox reactions involved in this experiment, see equations [1] and [2] below. Initially, an excess of
potassium iodide solution, KI (aq), is added to the bleach sample. The iodide ions, I–, are oxidized to iodine, I2, (see
equation [1]). After the solution is acidified – the addition of a strong acid to the solution will cause the conversion
of the hypochorite ion to hypochlorous acid. The iodine that is formed is then titrated with sodium thiosulfate,
Na2S2O3, solution that reduces the iodine to iodide (see equation [2]).

1) Acidified iodide ion is added to hypochlorite ion solution and the iodide is oxidized to iodine by the
hypochlorite ion.

HOCl ( aq ) + 2 I − ( aq) + H + ( aq) 

→ I 2 ( aq ) + Cl − ( aq) + H 2 O (l ) [1]

a. The iodine produced forms a complex ion called the triiodide ion with any excess iodide ions.
Triiodide is a combination of a neutral I2 molecule with an I- ion. The triiodide ion is yellow in dilute
solution.

I2 (aq) + I– (aq) → I3– (aq) (yellow solution)



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The triiodide is titrated with a standard solution of thiosulfate ions, which reduces the iodine back to iodide ions.

I3-(aq) + 2 S2O32-(aq) → 3 I-(aq) + S4O62-(aq)



2) The overall stoichiometry of the two reactions is given in equations [1] and [2].

2−
2 S 2 O32 − (aq ) + I 2 (aq ) → 2 I − (aq ) + S 4 O6
 (aq ) [2]
Starch is used as an indicator and it is added near the endpoint where the concentration of iodine is low and the
iodine solution has changed to a pale or light yellow. When the starch is added, the yellow color will change to a
blue or blue-black color. The end point of the titration is determined when a drop of the thiosulfate (S2O32-) causes
the solution to become colorless. Generally, it requires 2-10 drops to reach endpoint once the starch indicator is
added.

Starch and iodine form a complex that appears blue-black as shown in equation [3].

I 3− ( aq ) + starch 
→ starch • I 3− (complex ) [3]
yellow blue − black
NOTE: If the starch is added too soon in the titration, the formation of the blue-black complex is very large and is
not easily reversed, which makes the end point very slow to reach and difficult to detect.

There are two reasons why the indicator is not added at the beginning of the titration when the iodine concentration
is high. First, large amounts of iodine would be absorbed by the starch forming a very large complex resulting in a
very slow dissociation of the starch-iodine complex. The titration of such a large starch-iodine complex would take
an exorbitant amount to time to complete and the endpoint would be exceedingly difficult to distinguish. This is the
main reason that it is important that the color of the solution becomes yellow, where the iodide concentration is low,
before adding the starch.

Secondly, titrations with iodide are carried out in strongly acid solutions, a condition that promotes the reaction
between oxidizing agents and iodide to form I2. Starch has a tendency to decompose (hydrolyze) in acidic solutions,
which abolishes its indicator qualities.

After adding equations [1] and [2], equation [4] is produced:

HOCl ( aq) + 2 S 2 O32− ( aq) + H + (aq ) 

→ Cl − (aq ) + S 4 O62 − + H 2 O (l ) [ 4]

From equation [4], the stoichiometry of the overall reactions requires two moles of the thiosulfate ion to react with
every mole of hypochlorite. Therefore, from the volume of thiosulfate that is required to react with the liberated
iodine and the weight of the bleach sample, the percentage by mass of oxidizing agent can be calculated.

Example: An excess of KI was added to a 0.501g sample of bleach. The liberated iodine required 10.21 mL of
0.06292M Na2S2O3 solution for the titration to reach the end point. What is the oxidizing capacity of the NaOCl in
the bleach?

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Two moles of Na2S2O3 are required for every mole of hypochlorite in the reaction.

 0.0692 mol Na2 S2O3  1 mol NaClO  −4

( 0.01021 L Na2 S2O3 )    = 3.53×10 moles NaClO
 L Na2 S2O3  2 mol Na2 S2O3 

Convert the moles of NaClO to grams of NaClO:

 74.5 g NaClO 
( 3.53 ×10 mol NaClO ) 
−4
 = 0.0263 g NaClO
 mol NaClO 
the percentage by mass of NaClO :
0.0263 g
% NaClO = ×100 = 5.25% this is the oxidizing capacity of the bleach
0.501 g

Oxidation-Reduction Reactions:
Reactions that involve the transfer of electrons from one reactant to another reactant, regardless of the substances
involve, are collectively called oxidation-reduction reactions (redox). The reactants in these reactions will lose or
gain electrons and change their charge (oxidation number) as they form the products.
• Oxidation is the process in which a substance in a chemical reaction loses electrons.
• Reduction is the process in which a substance in a chemical reaction gains electrons.

A mnemonic that may help you remember what is oxidized and reduced is OIL RIG.
OIL
oxidation is loss of electrons
RIG
reduction is gain of electrons

Chemists often refer to these elements or compounds that are oxidized and reduced in another manner:
1) Oxidizing agents are those elements that cause loss of electrons (cause oxidation) – oxidizing agents are
reduced by gaining electrons.
2) Reducing agents are those elements that give up electrons (cause reduction) – reducing agents are oxidized
by giving up electrons.

To determine the reactants which are undergoing oxidation and reduction as well as the oxidizing agent and
reducing agent, we will divide the redox reaction into two half reactions. One-half of the reaction represents the
oxidation reaction and the other half represents the reduction reaction. To establish which substance is oxidized and
which is reduced, we must determine the original and final oxidation states of each substance in the chemical
equation.

Some of the rules to assigning oxidation states to elements in a chemical reaction are: (For a complete list, see
Experiment 3: Reactions of a Copper Cycle).

a. The oxidation number of any free, uncombined element is zero. The oxidation number (or charge on each atom)
is written above the atom.
0 0 0 0 0

Na (s), Mg (s), Cu (s), Fe (s) and Zn (s)

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b. All naturally occurring diatomic molecules have zero oxidation states.

0 0 0 0 0 0 0

Br2 I2 N2 Cl2 H2 O2 F2
c. For simple Group A binary ionic compounds (salts), the oxidation state is the charge of the element:
i. Metals (Group I A, IIA, and IIIA) are assigned a positive oxidation state – determined by the number
of electrons the element has lost.
• Group IA metals
+1 (Li+, Na+, K+, Rb+, Cs+)
• Group IIA metals
+2 (Mg2+, Ca2+, Sr2+, Ba2+)
• Group IIIA metals
+3 (Al3+, Ga3+, In3+)
ii. Nonmetals (Group VA, VIA, VIIA) are assigned a negative oxidation state determined by the number
of electrons the element has gained.

d. Hydrogen, H, has an oxidation number of +1 unless it is combined with metals, where it has the oxidation
number -1. Examples
LiH, BaH2

e. Oxygen usually has the oxidation number –2.

Exceptions:
• In peroxides O has oxidation number of –1. Examples: H2O2, CaO2, Na2O2
• In OF2, O has oxidation number of +2. (Fluorine is the most electronegative element and has the greater
share of electrons.)

f. ATOMS IN SUBSTANCES CAN HAVE FRACTIONS AS OXIDATION NUMBERS.

2.5 -2

• Example: S4O62−, the oxidation state of the sulfur in the tetrathionate ion has an oxidation number of +2.5.

Balancing Redox Equations

It is not always obvious how to balance a redox equation. For these more complex oxidation-reduction reactions,
we have a system by which to balance the equation by mass and by charge.

The half-reaction method is useful in that it is the method that is used in electrolysis. Balance the half-reactions by
the following rules:

Half reaction method rules for acidic conditions:

1. Write the unbalanced reaction. Balance the equation as much as possible without the spectator ions.

2. Set up half-reactions (oxidation and reduction) as we did in the previous reactions and balance.
One oxidation half-reaction and
One reduction half-reaction
3. Balance the oxygen by adding a H2O molecule for every oxygen atom needed on the side of the chemical
equation that is oxygen deficient.
4. Balance the hydrogen by adding H+ to the side of the chemical equation that is hydrogen deficient.

5. Once the half-reactions have been balanced, it is necessary that the same number of electrons are gained and
loss in the reactions. Therefore, to equalize the charge for both half-reactions, multiply each balanced half
reaction by a number to make the number of electrons in the oxidation half-reaction equal to the number of
electrons reduction half-reaction.

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6. Add the two half reactions.

7. Eliminate any common terms and reduce coefficients to smallest whole numbers, and if necessary, add the
spectator ions to the appropriate reactants and products.

In acidic conditions:
Example:
0 +1+5 −2 +4 −2 +4−2 +1 −2
C (s) + HNO3 (aq) → CO2 (g) + NO2 (g) + H2O

Set up the half-reactions: (Note: the hydrogen ion was removed as a spectator in the half reaction below.)

0 +4
C → CO2 + 4 e− oxidation (reducing agent)
+5 +4
NO3− + 1e− → NO2 reduction (oxidizing agent)

Balance the oxygen by adding H2O to the opposite side. (One H2O for each oxygen needed.)

2 H 2O + C → CO2 + 4 e−
NO3− + 1e− → NO2 + H2O

Balance the hydrogen by adding H+ to the opposite side.

2 H 2O + C → CO2 + 4 e− + 4 H+
2 H + NO3 + 1e−
+ −
→ NO2 + H2O

The number of e− must be the same on both sides of the equation.

Balance the charge by multiplying the half-reaction with the appropriate number to give the same number of
electrons to both of the half-equations.

2 H 2O + C → CO2 + 4 e− + 4 H+
+
4 (2 H + NO3− + 1e− → NO2 + H2O)

2 H 2O + C → CO2 + 4 e− + 4 H+
8 H + 4 NO3− + 4 e−
+
→ 4 NO2 + 4 H2O

Cancel e−, sum the water, sum the H+ from opposite sides of the equations, and sum the remaining reactants and
products.

2 H2O + C → CO2 + 4 e− + 4 H+
4 2
8 H+ + 4 NO3− + 4 e− → 4 NO2 + 4 H2O

4 H+ + 4 NO3− + C → 4 NO2 + CO2 + 2 H2O

Add the H+ back to the NO3− ions to complete the equation:

4 HNO3 + C → 4 NO2 + CO2 + 2 H2O

Disproportionation redox reactions are oxidation-reduction reactions where one reactant is both oxidized and
reduced.

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For example, potassium chlorite undergoes both oxidation and reduction in the following decomposition
reaction.

+1 +5 −2 +1 −1 +1 +7 −2
4 K ClO3 (s) 
→ K Cl(s) + 3K ClO4 (s)
Notice that chlorine in the reactant is
−6 oxidized and also reduced during the
decomposition reaction.
+2

The half reactions are below. Note: the reactants and products are solids in the above equation. No ions are involved
in the reaction.

+5 +7
3 (KClO3 → KClO4 + 2e− )
3KClO3 → 3KClO4 + 6e−
+5 −1
KClO3 + 6e− → KCl
KClO3 + 6e− → KCl
____________________________________

4KClO3 → 3KClO4 + KCl

LAB MATERIALS
3- 250 mL beakers 50 mL burette
Wash bottle 6.0 M sulfuric acid, H2SO4, solution
stirring bars 3.0 M potassium iodide, KI, solution
10 mL graduated cylinder 1.0 M sodium thiosulfate, Na2S2O3, solution
50 or 100 mL graduated cylinder 3% ammonium heptamolybdate, (NH4)6Mo7O24 •4H2O, solution
analytical balance Starch indicator
utility clamp Commercial Bleach
ring stand 500 mL waste beaker

SAFETY
Safety goggles must be worn at all times in the laboratory. Sulfuric acid is corrosive and generates much heat on
exposure to water. Sodium hypochlorite is corrosive to the skin.

PRE-LAB PREPARATION

1. Calculate the volume of 1.0 M Na2S2O3 solution required to make 80.0 mL of 0.050M of the Na2S2O3 solution.

2. Calculate the volume of 6.0 M H2SO4 solution to make 10.0 mL of 3.0 M H2SO4 solution.

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PROCEDURE: Determination of the Oxidizing Capacity of Unknown Liquid Bleach (This is an individual
experiment.) Be sure to record the observations made in this experiment in your lab notebook.

NOTE: Starch is used as the indicator for this reaction. Careful not to add the starch solution until the dark bluish
colored solution has changed to a yellow color. Once the starch is added, the solution will become bluish-black. The
end point in the titration is reached when a drop of the sodium thiosulfate causes the solution to become colorless –
usually 2-10 drops are needed once the starch is added.

1. Your TA will distribute the unknown bleach samples. NOTE: You will only receive one unknown vial for this
experiment. The volume of the unknown is 3.0 mL; therefore, you will have a limited number of titrations
that can be performed with your unknown. Be careful not to waste your sample because you will not be
given another sample under any conditions.

2. Take a 10.0 mL sample of KI in a small beaker, a 2.0 mL sample of starch in a small beaker and 1.5 mL of 3%
ammonium heptamolybdate in a small beaker to your bench. Use only these quantities in your experiment.

3. From the dilution calculation, prepare 10.0 mL of 3.0 M H2SO4 for use later.

4. Dilute the 1.0 M sodium thiosulfate solution as determined in the pre-lab to 80.0 mL of 0.050M sodium
thiosulfate solution in a 100 mL beaker.

5. Clean, rinse and fill a 50.0 mL burette with sodium thiosulfate solution.

6. Weigh a clean 50.0 mL beaker.

7. Add approximately 0.50 mL of an unknown bleach sample into the clean 50.0 mL beaker and weigh. The total
mass of the bleach should be between 0.40 – 0.60 g.

8. Pour the bleach into a 250 mL beaker and rinse the 50 mL beaker several times with 5.0 mL aliquots of water to
ensure that all the bleach is transferred into the 250 mL beaker. The total volume of water added to the 250 mL
beaker should be 25.0 mL; including the water used to rinse the beaker.

9. Carefully add a stir bar to the 250 mL beaker.

10. Add 3.0 mL of 3.0 M KI to the beaker and swirl.

11. Add 2.0 mL of 3.0 M H2SO4 to the beaker and swirl.

12. Add 5 drops of 3% ammonium heptamolybdate, (NH4)6Mo7O24 •4H2O, catalyst immediately after the acid is
added. The molybdate ion catalyzes the reaction between the iodide and the oxidizing agent.

Word of warning; Iodide is also oxidized by oxygen in the air:

4 I– (aq) + O2(g) + H+ (aq) → 2I2 (aq) + H2O (l)

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The reaction is slow in neutral solution but is faster in acid and is accelerated by sunlight. After the reaction has been
acidified, it must be titrated as soon as possible or the production of I2(aq) will exceed its solubility limits and begin
precipitating as solid iodine. All of the iodine must be re-dissolved (turn up the speed for the stir bar) and reacted before
the titration can be completed. If too much solid iodine forms, the iodine will clump together and become more difficult
to dissolve and the titration must be discontinued.

13. Immediately begin the titration with the 0.050 M Na2S2O3 solution. As titrant is added, the color of the solution
in the flask will fade to light brown then yellow. As the titration proceeds and the solution turns yellow, be sure
that the solution is stirring to ensure that all of the iodine is dissolved.

14. Once the solution has reached yellow, add 0.50 mL of starch indicator and mix. The color of the solution will
turn dark blue-black. If you add the starch before the solution is yellow, a large iodide-starch complex will
form and the titration will have to be terminated. (read p 107)

15. Slowly continue to add titrant drop by drop until the dark blue-black solution becomes a lighter in color;
indicating that the end point is generally only a drop or two away.

16. At the end point, the solution will become colorless. Record the volume to the nearest 0.010 mL.
17. Dispose of the solution in a 500 mL waste beaker. Perform two more titrations.

18. At the end of the three titrations, the waste material in the beaker will be disposed as directed by your TA.

DATA TABLE Trial 1 Trial 2 Trial 3

Mass of unknown bleach (g)

Volume of Na2S2O3 added (mL)

DATA ANALYSIS (SHOW YOUR WORK.)

1. Complete and balance the following redox equations by the half reactions method (the oxidation reaction and
the reduction reaction). Note: These are two separate reactions, see equation 1 and 2 on pages 108- 109.
a. Equation [1] HOCl (aq) + I– (aq) + H+ (aq) →
b. Equation [2] S2O32– (aq) + I2 (aq) →

2. Sum the equations [1] and [2] to derive equation [4], see page 109.

3. From the concentration and volume of the added Na2S2O3 solution used to titrate each bleach sample, calculate
the weight of sodium hypochlorite, NaOCl, present in each trial.

4. Calculate the average percentage mass and standard deviation of the NaOCl in your unknown bleach sample.
(Calculate the percentage by mass of each trial and average the percentages. Take the standard deviation of the
percentages.)

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Report the average percentage mass of NaOCl ± std. deviation in your unknown bleach sample below (this is the
oxidizing capacity of the bleach).

Unknown bleach oxidizing capacity _______________________

DISCUSSION (Attach written discussion to end of lab report.)

1. In your own words, describe the objectives of this experiment?

2. What are the names of the salts that are the oxidizing agent’s in common household chlorine bleaches?
3. Describe the two redox reactions that occur in the experiment. What is the overall stoichiometry of the
reaction?
4. Briefly describe the titration process you used in this experiment? What is the color of the bleach sample
solution just before the starch solution is added, after the starch solution is added and at the end point?
What form of the iodine predominates just before the starch is added? What form of iodine predominates
after the endpoint has been reached?
5. There were two precautionary steps during titration; one that involved the addition of the starch and the
other involved the addition of the sulfuric acid. What was the main precaution of adding starch too soon?
What was the precaution associated with the addition of sulfuric acid? What were the unwanted results if
the two above precautions were ignored? What was the potential problem associated with the formation of
iodine during the titration? How would the formation of solid iodine affect the results of the titration?
6. What is oxidizing capacity? In the presence of a strong acid the hypochlorite ion, OCl−, is converted to
hypochlorous acid, why? How did you determine the oxidizing capacity of your of unknown bleach
sample? What was the oxidizing capacity of your unknown bleach sample?
7. Identify and report the possible errors that may have affected your results for this experiment.

Be sure to upload a copy of your discussion into SafeAssign before your next lab period.

SECOND HALF OF LABORATORY

During the second half of the laboratory, you will synthesize aspirin. Use the procedure in experiment 9, which is
also be posted on Blackboard. You may either bring the complete experiment or just print the procedure from
Blackboard to perform Part I of Experiment 9 – do not write the protocol for aspirin synthesis in the experiment 8
preliminary write up. Upon completion of the synthesis, place the covered aspirin in your equipment drawer so that
it will be thoroughly dry for next week’s analysis.

The preliminary write-up for experiment 9 will include the protocol for the synthesis of aspirin and the
spectrophotometric analysis of aspirin.

References:
Zumdahl, S. S. Chemical Principles, 5th Edition, Houghton Miffin Company, 2005, pp. 98, 115-130.
Atkins, P.W.; Jones, L. L. Chemical Principles: The Quest for Insight, 3rd Edition, W. H. Freeman and Company,
2005, pp. 444-445, F73, F77, F83

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