Assay of Commercial Bleach

Introduction
Many commercial bleach products we buy to whiten and brighten clothing contain the hypochlorite ion, OCl -(aq).
Hypochlorite is an excellent oxidizing agent, and works well in low concentrations in products such as PurexTM and
ChloroxTM, etc. In this laboratory experiment, we will analyze for the concentration of sodium hypochlorite in
commercially available bleach products by titrating with sodium thiosulfate. Outcomes from this lab exercise will be:
 Determining the assay of the active ingredient in bleach.
 Exploring the use and types of volumetric glassware.
 Understanding and using new chemical terminology.
 Introduction to titration—a key experimental skill.
 Performing standard chemical stoichiometric calculations.

Sodium hypochlorite fully dissociates in aqueous solution, so the chemically active species is the hypochlorite ion,
OCl-. The overall net-ionic stoichiometry of the reaction of bleach (hypochlorite ions) with thiosulfate ions is given
in Equation (1).

2H+(aq) + ClO-(aq) + 2S2O32-(aq) → Cl-(aq) + S4O62-(aq) + H2O(l) (1)

Please see the appendix I for further information about the chemistry of the titration.

Experimental Procedure
Since this is your first titration lab, we will focus on the procedures and skills necessary for obtaining excellent data.
This experiment can be performed individually or in pairs as indicated by the instructor.

Apparatus and Approach

The sketch on the next page shows the equipment you will need in order to perform the titration. Attach the 50 mL
buret to the ring stand using a buret clamp. You will titrate into a 250 mL Erlenmeyer flask. A word should also be
given about the glassware you will be using. Laboratory glassware is typically stamped on the glassware as TD or
TC with a temperature and perhaps an accuracy value. TD means “To Deliver” and is manufactured in such a way
that it will deliver the volume required. Do not blow through TD glassware to “get the last drop,” since the glassware
is calibrated to leave the internal walls and tip moist with the “last drop” retained in the tip. Burets and pipets are TD
glassware. TC or “To Contain” means that the internal volume of the glassware at the mark has the value stamped
on the glassware. Therefore solutions of known concentration are prepared in TC glassware such as volumetric
flasks, and known volumes are delivered through TD glassware.

Setup Procedure:
1. Make sure that your buret is clean. (1) Wash the buret in hot, soapy water using a long handled buret
brush. (2) Rinse the buret, including the tip and valve, with several 10-15 mL portions of water until soap
suds are no longer visible. (3) Rinse the buret three times with 10-15 mL portions of deionized water, being
sure that the tip and valve are also clean and rinsed. (4) Introduce 2 or 3 mL of the solution that will be used
in the buret. Rolling the buret barrel in a near horizontal plane, rinse the interior of the buret with the solution
and drain through both the stopcock and buret tip and the top of the buret. Repeat this procedure three times.
Properly discard this drained material. At this point the buret should be ready to be used. You can tell if the
buret is clean enough by the walls of the buret remaining droplet free during the course of the titration. If
solution beads on the walls and doesn’t flow smoothly, you will need to re-clean your buret.

2. Filling the buret. Use a clean funnel to pour solution into the buret. Initially you should pour in around 30-
40 mL of solution. Drain enough solution through the buret until no air bubbles remain in the tip. Properly
discard this drained material. Now fill the buret to somewhere between the 0 and 5 mL marks. There is no
reason to expend effort to get exactly 0.00 mL. This volume will be the beginning volume of your titration.

3. Reading the buret. At the beginning and end of the titration you will need to read the volume. The inset
shows an expanded section of the barrel of the buret. Read the volume of the buret at the bottom of the
meniscus. You should attempt to read the volume to the nearest 0.01 mL. The inherent precision of a 50
mL buret is ±0.02 mL, and the accuracy is ±0.05 mL. Be sure not to go beyond the numbers during a

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 titration. If you start getting uncomfortably close to the 50 mL mark, then take a good volume reading, add
more solution, take another good volume reading, and continue on. Make sure to take your volume reading
with your eye parallel to the bottom of the meniscus. Also, many chemists find that the meniscus bottom is
more sharply defined by holding a white piece of paper with a line on it behind the buret barrel, and moving
the card up and down until the lowest point of the meniscus is made apparent.

4. Titrating the solution. The solution in the Erlenmeyer 17 17.11 mL

flask should be swirled by hand or stirred using a magnetic
stirrer with a Teflon coated stir bar while adding the titrant.
A squeeze bottle with deionized water should also be used Move your eyes to the level of the
to rinse the sides of the flask and the tip of the buret. You liquid surface and try to read the
can add partial drops of the titrant to the Erlenmeyer flask value of the bottom of the
meniscus with 1/10 of the smallest
by releasing a partial drop of the titrant from the buret and
scale marked on the buret
rinsing the buret tip with deionized water into the flask.
18
Titration Procedure
1. Note the product name and wt% sodium hypochlorite (if provided on label) for
the assigned bleach you are analyzing on your data sheet. If no sodium hypochlorite concentration is
specified, write N/A.
2. Weigh a clean and dry 250 mL volumetric flask. Record this weight on the data page.
3. Use a clean and dry 10 mL volumetric pipet to measure precisely 10.00 mL of your assigned commercial
bleach solution into the 250 mL volumetric flask. You may also use the volumetric pipet if you first rinse it
with the solution you are transferring. Weigh and record the weight of the volumetric flask with bleach
sample.
4. Use deionized water to dilute the bleach in the 250 mL volumetric flask to the 250.0 mL volume mark on the
flask. Stopper the flask with a number 2 rubber stopper and mix well.
5. Use a clean and dry (or rinsed with fluid to be transferred) 25 mL volumetric pipet to measure 25.00 mL of
the diluted bleach solution into a clean 250 mL Erlenmeyer flask.
6. Weigh out between 1.4 and 1.6 g of solid potassium iodide, KI(s). The exact amount is unimportant since it
is being added in excess. Add the KI(s) along with another 25 mL of deionized water to the Erlenmeyer
flask. Swirl to dissolve the KI(s). The Erlenmeyer flask should now contain around 50 mL of solution.
7. Slowly add 5 mL of 1 M HCl from your 10 mL graduated cylinder into the Erlenmeyer flask while swirling or
stirring. The solution will turn dark yellow to reddish-brown depending on the concentration of triiodide ions.
8. Properly fill the buret with the thiosulfate solution as per the description above. Record the initial volume
and concentration on the data sheet.
9. Titrate the solution in the Erlenmeyer flask until the color of the solution fades to light yellow. Remember to
constantly swirl or stir the flask. Rinse the flask and buret tip with deionized water at the end of this stage of
the titration.
10. Now add one Beral pipet full (~1 mL) of starch solution into the Erlenmeyer flask. The blue color of the
starch-iodine complex should appear—if it doesn’t, you have over-titrated the sample. (start over!)
11. CAREFULLY continue the titration until the addition of one drop (or less) of the thiosulfate solution causes
the blue color to disappear. Record the final buret reading.
12. Repeat the titration procedure, starting at step 5 above until you have three or four well-performed titrations.
If you are aware of experimental issues that cause a titration run to have poor results, you should not use
that titration result in your data analysis. If you are working in pairs, each partner must individually
contribute at least two titration runs (total of at least four runs). Initial your runs on both students’ sheets.
13. When you are done, clean the volumetric pipets and volumetric flask by draining the glassware thoroughly
and completely rinsing them three times with deionized water. Place them in the glassware oven to dry.
Clean the buret by completely draining it and thoroughly rinsing three times with deionized water. Place the
buret back in the clamp on the ring stand, but upside down with the stopcock in the open position.
14. Deionized water rinses and the diluted bleach solution may be drained down the sink, but all other
chemicals need to be collected into the inorganic waste croc in the fume hood.
15. Average your three or more good titration results and calculate the standard deviation. Determine the
percent difference if the wt% of your sodium hypochlorite solution was given.

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 Calculations and Analysis
We want to confirm or obtain the mass percent (wt%) of sodium hypochlorite in our bleach sample. The “mole map”
or stoichiometric approach we use will start with the thiosulfate solution volume titrated, since that is our known.

Mole-Map for calculating wt-% sodium thiosulfate in bleach

mL moles moles grams wt-%

thiosulfate titrated → thiosulfate → sodium hypochlorite → sodium hypochlorite → sodium hypochlorite

Measured Step 1 Step 2 Step 3 Step 4

Step 1. The moles of thiosulfate used in the titration, n , can be calculated by the familiar relationship
S2 O2−
3

nS2 O2−
3
= (VS2 O2− ). (𝑀S2 O2− )
3 3
(6)

Where 𝑀S2 O2− is the molar concentration of thiosulfate, mol/L, and the volume you titrated, VS2 O2− , is in liters.
3 3

Step 2. From equation (1) we see that two moles of thiosulfate will react with one mole of hypochlorite, so the
moles of hypochlorite (and sodium hypochlorite) at the equivalence point are

nOCl− = nNaOCl = 0.5∙nS2 O2−

3
. (7)

Step 3. The grams of sodium hypochlorite in the titrated sample are simply the molar mass of sodium hypochlorite,
74.44 g/mol, multiplied by the moles of sodium hypochlorite.
g
mNaOCl = (74.44mol )∙ nNaOCl (8)

Step 4. The amount of undiluted bleach solution you are titrating is 1.000 mL (convince yourself!). This means the
mass of sodium hypochlorite you determined in Step 3 above is the mass of sodium hypochlorite in 1.000 mL of
bleach solution. The mass of 1 mL of bleach solution is simply the density of the bleach solution, dbleach, which you
measured at the beginning of the experiment. Therefore, the wt% sodium hypochlorite in the bleach is:

mNaOCl
wt%NaOCl = ( )∙100% (9)
dbleach

Appendix II contains an example calculation for this lab.

Disposal and Cleanup

1. All solutions that contacted the sodium thiosulfate must be disposed of in the labelled waste croc in the
fume hood.
2. Water washes/rinses and extra dilute bleach solutions can be disposed of down the sink drain.
3. Triple DI water rinse the buret and place it back in the buret clamp, upside-down with the stopcock open.
4. Triple DI water rinse the rest of the volumetric glassware and place in the lab drying oven.
5. Dispose of the plastic Beral pipets in the lab trash receptacle.
6. Rinse the magnetic stir bar with DI water and return.
7. Clean your assigned equipment, rinse with DI water, dry and put away for next time!
8. Clean your desk area and also other areas as directed by the instructor.

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 Assay of Commercial Bleach

Advance Study Assignment

(May be on Canvas)

The series of questions 1-9 examine your understanding of the processes of using laboratory glassware and the
methods of titration.

1. Define the following terms stamped on glassware, and explain how they are used and how they are different.

 TD

 TC

 titrant

2. The last drop in TD glassware is not transferred (circle answer): TRUE FALSE

3. The buret must be filled to the 0.00 mL mark before beginning a titration (circle answer): TRUE FALSE

4. Buret readings are taken at the ______________________ of the meniscus.

5. It is possible to add a partial drop from a buret (circle answer): TRUE FALSE

6. It is fine if the solution you are titrating beads up on the walls of the buret (circle answer): TRUE FALSE

7. Describe the steps used to clean the buret.

8. What color change will you see at the equivalence point? From ________________ to ________________.

9. Deionized water rinses of the buret tip and walls of the flask should only be performed at
the start of the titration process (circle answer): TRUE FALSE

10. What volume of 0.955 M HCl in mL is required to titrate 2.152 g of Na2CO3 to the equivalence point?

Na2CO3(aq) + 2HCl(aq) → H2O(l) + CO2(g) + 2NaCl(aq)

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 Assay of Commercial Bleach - Data/Report Sheet
Stephen Henry
Name: _________________________________ 10/13/2016
Date: _________________________

George and Susana

Partner: _________________________________ CHEM 1411.152FA
Section: _______________________

1. Trade name of assigned commercial bleach product: NaOCl

_________________________________

2. Reported weight percent, wt%, on bleach container (if available): 8.25%

_________________________________

3. Mass of 250 mL volumetric flask: 85.833 g

_________________________________

4. Mass of volumetric flask with 10.00 mL bleach sample: 96.765 g

_________________________________

5. Mass of 10.00 mL bleach sample: 10.932 g

6. Density of bleach product in g/mL: _________________________________

(Show calculations)

7. Reported molarity of sodium thiosulfate Na2S2O3 solution: _________________________________

Titration Data: Run 1 Run 2 Run 3 Run 4 Run 5 Run 6

8. Volume of diluted bleach, mL 25.00 mL __________

__________ 25.00 mL __________
25.00 mL 25.00 mL __________
__________ 25.00 mL 25.00 mL

9. Mass of weighing boat, g 2.280 g

__________ 2.293 g
__________ 2.240 g
__________ 2.350 g
__________ 2.466 g
__________ 2.466 g

10. Mass of weighing boat and KI, g 3.249 g

__________ 3.865 g
__________ 3.829 g
__________ 3.426 g
__________ 3.743 g
__________ 3.648 g

11. Mass of KI added to titration flask, g 1.606 g

__________ 1.567 g
__________ 1.593 g
__________ 1.470 g
__________ 1.594 g
__________ 1.599 g

12. Initial buret volume, mL 1.80 mL

__________ 2.20 mL
__________ 1.30 mL
__________ 1.40 mL
__________ 1.00 mL
__________ 0.700 mL

13. Final buret volume, mL 28.70 mL

__________ 29.28 mL __________
__________ 28.49 mL __________
20.60 mL __________
20.80 mL 20.40 mL

Initials of titrating student __________ __________ __________ __________ __________

14. Total volume titrated, mL __________ __________ __________ __________ __________

15. Total volume titrated, L __________ __________ __________ __________ __________

16. Moles of thiosulfate __________ __________ __________ __________ __________

17. Moles of sodium hypochlorite __________ __________ __________ __________ __________

18. Mass of sodium hypochlorite __________ __________ __________ __________ __________

19. Calculated wt% NaOCl in bleach __________ __________ __________ __________ __________

20. Average NaOCl wt% in bleach ____________ 21. %-Difference _______________

22. Standard deviation (of wt%) ____________

Attach all calculations to the lab report.

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 Assay of Commercial Bleach

Appendix I: Details of Chemistry

The hypochlorite ion is readily prepared by bubbling chlorine gas, Cl2(g), through strongly basic solutions. For the
chemical equation below, the ionic compound would be sodium hypochlorite, NaOCl(aq), although potassium
hypochlorite based bleach is also common.

Cl2(g) + 2NaOH(aq) → NaOCl(aq) + NaCl(aq) + H2O(l) (2)

Commercial bleach solutions are strongly basic, primarily to avoid the regeneration of chlorine gas which is
particularly toxic. We will determine the amount of sodium hypochlorite in these bleach solutions by performing an
oxidation-reduction titration, or redox titration. Titration is a very useful chemical technique that allows for precise
delivery of a measured amount of one substance to a solution of another substance. This allows us to construct a
stoichiometric balance for the reaction between the two solutions from which we can determine the concentration of
the unknown solution. A number of different techniques can be used to indicate when the stoichiometric
equivalence point has been reached, which is defined as having the exact molar ratios of reactants required for
complete reaction with no excess reactants left over. For this lab, we will use a visual indicator.

The chemistry we will be using to determine the hypochlorite concentration is performed in a series of steps. In the
first step we will carefully add acidified iodide ion to the hypochlorite solution. Iodide ion will be oxidized to iodine.

2H+(aq) + ClO-(aq) + 2I-(aq) → Cl-(aq) + I2(aq) + H2O(l) (3)

The second step, shown in equation 4 below, occurs without intervention and is necessary to keep the iodine
formed above in solution. Iodine is rather insoluble in water by itself, so we have introduced an excess of iodide ion
in reaction (3) above

I2(aq) + I-(aq) → I3-(aq) (4)

I3-(aq) is called the triiodide ion. The triiodide ion is yellow in dilute solutions, and red-brownish when more
concentrated. The triiodide ion is titrated with thiosulfate ions which reduces the triiodide ion back to iodide ions,
and oxidizes the thiosulfate ions to dithionate ions, S4O62-(aq).

I3-(aq) + 2S2O32-(aq) → 3I-(aq) + S4O62-(aq) (5)

The disappearance of the yellow color of the triiodide ion can by itself be used as an indicator of stoichiometric
equivalence. However, starch forms a reversible blue complex with the triiodide ion and the disappearance of this
color provides a much more visually sensitive indication of reaching the equivalence point. The starch should be
added towards the end of the titration to avoid building complexes that are too stable. Adding Equations (3), (4) and
(5) together provides the overall reaction equation

2H+(aq) + ClO-(aq) + 2S2O32-(aq) → Cl-(aq) + S4O62-(aq) + H2O(l) (1)

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 Assay of Commercial Bleach
Appendix II. An example calculation
A student titrated a sample of “Super-Duper” brand laundry bleach using the above procedure and obtained the
following data.

a) “Super-Duper” bleach b) 5.6 wt% NaOCl (from the bottle)

c) Mass of 250 mL flask = 120.650g d) Mass flask and sample = 131.443g

The density of the bleach in g/mL is calculated by obtaining the mass of bleach by difference of d) and c) above,
and knowing that 10.00 mL of bleach solution was transferred

131.443g−120.650g
e) dbleach = = 1.079 g/mL
10.00 mL

This number is filled into the data table as e). The molarity of the thiosulfate solution will be provided. In our
student’s case, the value is filled in the data table under f).

(f) 𝑀Na2 S2O3 = 0.05005 mol/L

For run 1, the student started with 2.35 mL at the beginning of the titration, line k), and ended the titration at 34.14
mL, line l). The total volume in mL is given in line m), and is converted to liters by dividing by 1000 mL/L.
VNaOCl titrated is 31.79 mL (34.15 mL – 2.35 mL) or 0.03179 L.

Using equation 6 in step 1, the student found the number of moles of thiosulfate added.

nS2 O2−
3
= (0.05005 mol/L)·(0.03179 L) = 0.001591 mol S2O3-
Equation 7 in step 2 allowed the student to calculate the number of moles of hypochlorite in the bleach sample.
The number of moles of hypochlorite ion is the same as the moles of sodium hypochlorite (sodium is a “spectator”
ion).
nOCl− = (0.5)·(0.001591 mol) = 0.0007955 mol OCl- = 0.0007955 mol NaOCL
For converting from moles of sodium hypochlorite to grams, the student used the molar mass of sodium
hypochlorite given in equation 8 in step 3.
g
mNaOCl = (74.44mol )∙(0.0007955 mol NaOCl) = 0.05922 g NaOCl

Using the density the student determined above, the wt% NaOCl in the bleach is

0.05922 g/mL
wt%NaOCl = ·100% = 5.488 wt%
1.079 g/mL

This value is reported in the data and report sheet on line n). The percent difference between the students
determined value and that reported on the data label (assumed to be correct) is

5.6g/100 mL−5.488g/100 mL
%-Difference = ∙100% = 2.0 %error.
5.6g/100 mL

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