Ontario Tech University CHEM 1010U, W24; Exp. 2-20.

29

2. DETERMINATION OF STOICHIOMETRY BY TITRATION

Objectives

1) To practise using the pipette and the burette, two essential pieces of volumetric glassware; 2) to
practise stoichiometry calculations; 3) to determine the stoichiometric coefficients for the reaction
between potassium iodate, potassium iodide and hydrochloric acid.

Introduction

The “titration” is a very common method of analysis in chemistry to determine the

concentration of a reactant in a solution. In a titration a solution of a reactant in a burette is slowly
added to an accurately known volume of a solution of a second reactant in a flask. The concentration
of one of the reactants must be accurately known. The reactant of unknown concentration is called
the “analyte”. The solution in the burette is called the “titrant”. Once the analyte is completely
consumed (the reaction is “complete”), the addition of the titrant is stopped and the volume of added
titrant is determined. Because the concentration and volume of one of the reactants and the volume
of the other reactant are all accurately known, the concentration of the analyte can be calculated
using the stoichiometry of the reaction.

To know when the reaction is complete - when to stop adding titrant - a small amount of
“indicator” is added to the flask. An indicator is a substance which changes some physical property,
most often its colour, when the reactant in the flask is completely consumed. At the “end point” the
indicator changes its property and titrant is no longer added - the titration is “ended”. The
“equivalence point”, however, is what the analyst really wants to know; it is the point at which the
two reactants are present in their stoichiometric ratio. The “end point” and the “equivalence point”

93
 Ontario Tech University CHEM 1010U, W24; Exp. 2-20.29

are not, to be completely rigorous, the same thing. If the indicator is properly chosen, the difference
is very small and in first-year experiments the equivalence point and the end point are assumed to
be the same. A more detailed examination of this question is undertaken in advanced analytical
chemistry courses.

In this experiment, titration is used to determine the coefficients of a chemical equation for
the reaction between potassium iodate (KIO3), potassium iodide (KI) and hydrochloric acid (HCl).
When these three species are mixed, iodine is produced and the solution turns dark brown. The
unbalanced net ionic equation is:
IO3-(aq) + I-(aq) + H+(aq) ÿ I2(aq) + H2O(l) (2.1)
An accurately known number of moles of IO3- (as potassium iodate) is mixed with an excess of I- (as
potassium iodide) and H+ (as hydrochloric acid). The IO3- is the limiting reagent and it is completely
consumed. Therefore, the number of moles of IO3- consumed by the reaction is the same as the
number of moles of IO3- added.

The iodine atoms produced in reaction (2.1) come from both the iodate and the iodide. In
each species (the iodate or the iodide) the number of moles of iodine atoms equals the number of
moles of the species because the mole ratio of I to IO3- is 1:1 and the mole ratio of I to I- is 1:1.
Therefore, the total number of moles of iodine atoms is given by:
(2.2)

We find from the total number of moles of molecular iodine ( ) produced in reaction

(2.1). is found by titration (see below). The number of moles of iodate consumed in reaction

(2.1), , is the same as the number of moles of iodate added because iodate is the limiting

reagent. Therefore, the number of moles of iodide ( ) that reacted can be calculated. Having the

numbers of moles of IO3-, I- and I2 allows the calculation of the mole ratio IO3-: I- : I. Finally, the

94
 Ontario Tech University CHEM 1010U, W24; Exp. 2-20.29

coefficients for H+ and H2O in reaction (2.1) are found by inspection.

The number of moles of molecular iodine, , produced by reaction (2.1) is determined by

titration. Iodine reacts with thiosulphate according to:

I2(aq) + 2S2O32-(aq) ÿ S4O62-(aq) + 2I-(aq) (2.3)
S2O32-(aq), S4O62-(aq) and I-(aq) are all colourless while I2(aq) is dark brown. At the end point the
colour disappears because all of the I2(aq) has been consumed. As the thiosulphate is added to the
iodine solution, the colour fades from dark brown to light yellow because the amount of iodine
decreases. Unfortunately, the disappearance of the colour is gradual, therefore the end point is hard
to see. To solve this problem a small amount of starch is added once the solution is pale yellow.
Starch and iodine form an intensely blue complex. Once all the iodine is consumed (the end of the
reaction) the complex no longer exists and the colour disappears. The change from blue to
colourless is very sudden (or “sharp”), so the end point is very easy to detect. The sharpness of the
end point makes this a popular titration in analytical chemistry. The starch must not be added too
early because the colour change is then no longer sharp and the end point is difficult to see.

Apparatus and Materials

1) 50 mL burette; 2) funnel; 3) 250 mL beaker; 4) 400 mL beaker; 5) 5.00 mL pipette; 6) pipette

bulb; 7) 150 mL beaker; 8) 50 mL beaker; 9) 3 x 250 mL Erlenmeyer flasks; 10) wash bottle; 11)
~0.2 mol L-1 Na2S2O3; 12) ~0.12 mol L-1 KIO3; 13) 0.5 mol L-1 KI; 14) 1.0 mol L-1 HCl; 15) starch
indicator.

95
 Ontario Tech University CHEM 1010U, W24; Exp. 2-20.29

Safety

• Most of the solutions used here are quite dilute, therefore not particularly dangerous.

• HCl spills should be neutralized with a small amount of sodium bicarbonate and then
cleaned up with a sponge.

• Small spills can be cleaned up with a sponge. Wear gloves. Rinse the sponge afterwards
with plenty of tap water. Wipe down the bench top. Clean hands thoroughly.

• In the event of eye exposure - rinse thoroughly with running water for 15 minutes (30
minutes for HCl) and seek medical attention immediately. Notify teaching assistant /
technician / senior laboratory instructor as soon as possible. Other students should stop
their experiments.

• In the event of skin exposure - rinse thoroughly with cool running water for 15 minutes. If
irritation develops, seek medical attention.

• Accidental mixing of HCl and S2O32- will precipitate sulphur and release SO2 gas. The
solution will turn cloudy and release a foul smell (from the SO2). Such solutions should be
disposed of in the fume hood in the waste bucket provided (with the thiosulphate waste)
immediately.

• KIO3 is an oxidizing agent. Waste KIO3 solutions should be collected separately from the
other solutions in the waste vessels provided. Waste HCl can be flushed down the sink with
plenty of water. Waste thiosulphate should be collected in the waste vessels provided. The
waste solutions from the titration should be collected in the waste vessels provided.
Thiosulphate and titration waste can be collected together.

96
 Ontario Tech University CHEM 1010U, W24; Exp. 2-20.29

Procedure

You should review the techniques used in this experiment: pipetting, the burette and titrating
which are described in the introductory pages of the laboratory manual; Videos: transfer pipettes,
titrating.

1. Obtain a 50 mL burette and rinse it three times with small amounts (~10 mL) of tap water.
To rinse the burette, ensure the stopcock is closed, add the water (from a beaker), hold the
burette almost horizontally and rotate the burette so that the entire inner surface is rinsed.
Allow some water to drain through the stopcock so that there are no bubbles in the tip. Close
the stopcock and pour the rest of the water out the top of the burette.

Be careful not to knock the tip against the bench - it is fragile and it may break.

2. In a similar fashion, rinse the burette three times with deionized water.

3. Collect ~100 mL of the standard Na2S2O3 solution in a clean, dry beaker. The beaker must
be dry otherwise the Na2S2O3 solution will be diluted, changing its concentration. Record
the concentration of the Na2S2O3 solution. Do not take more than 100 mL without the
permission of an instructor.

4. Using a small amount of the Na2S2O3 solution rinse the inner surface of a funnel (rinsing into
a waste beaker). Use this funnel to add Na2S2O3 your burette.

5. Rinse the burette three times with small portions of the Na2S2O3 solution in the same manner
you rinsed the burette with deionized water. Drain a portion of the Na2S2O3 solution through
the stopcock into a waste beaker. With the stopcock closed, pour the remainder out the top
of the burette into a waste beaker.

97
 Ontario Tech University CHEM 1010U, W24; Exp. 2-20.29

6. Fill the burette with your Na2S2O3 solution. While doing so, make sure the top of the burette
is below eye-level. If the top of the burette is above eye-level, solution may be spilled on the
face. Fill the burette to just above the zero mark. Remove the funnel and drain some
Na2S2O3 through the stopcock. Ensure no bubbles are in the tip of the burette. If the level
of the Na2S2O3 is below the zero mark, this does not matter. The level of the Na2S2O3 must
not be above the zero mark. If you spill any Na2S2O3 on the outside of the burette, be sure
to clean it off with some paper towel.

7. Record the volume on the burette to two decimal places. This will require you to estimate
the position of the meniscus between two graduations on the burette (failure to record the
volume to two decimal places will result in the loss of marks). This reading is the “initial”
volume reading of the Na2S2O3 solution. Remember, the scale reads from 0 at the top to
50.00 mL at the bottom and represents the volume dispensed from the burette, NOT the
volume remaining in the burette. You do not have to do any arithmetic; simply record this
initial volume.

8. Obtain a 5.00 mL pipette. Rinse it three times with tap water followed by three rinsings with
deionized water. To rinse the pipette use the bulb to draw enough liquid into the pipette to
half fill, roughly, the wide part of the pipette. Ensure the tip of the pipette remains
submerged otherwise liquid will be sucked into the pipette bulb. Remove the bulb, place
your finger over the end and hold the pipette horizontally. Remove your finger and rotate
the pipette to thoroughly rinse the inner surfaces of the pipette. Allow the liquid to drain
through the tip of the pipette. Do NOT pour the liquid out the top of the pipette or allow
liquid to enter the bulb.

9. 30 mL aliquots of standard KIO3 solution (of accurately known concentration) will have been
dispensed into test tubes. Obtain one of these test tubes and pour the solution into a clean,
dry 150 mL beaker. It is important that the beaker be dry so the KIO3 is not diluted. Record

98
 Ontario Tech University CHEM 1010U, W24; Exp. 2-20.29

the exact concentration of the KIO3 solution. You will not be able to get more KIO3 so do
not waste it.

10. Pour ~10 mL of the KIO3 solution into a clean, dry 50 mL beaker. Do not use a larger
beaker otherwise it will be difficult to ensure the pipette tip is submerged while drawing
liquid into the pipette. Using this portion of the KIO3 solution, rinse the 5.00 pipette three
times (as in step 8). Throw away any extra KIO3 solution in the 50 mL beaker.

11. From the 150 mL beaker pipette exactly 5.00 mL of the KIO3 solution into a clean 250 mL
Erlenmeyer flask. The flask does not need to be dry.

12. Add 10 mL of 0.5 mol L-1 KI and 10 mL of 1.0 mol L-1 HCl to the Erlenmeyer flask. Be sure
to add the acid last. Swirl to mix well. I2 should be produced immediately turning the
solution a deep, reddish brown.

13. Immediately place the flask underneath the burette and titrate the solution with the Na2S2O3.
The tip of the burette should be just below the top of the flask. This ensures all the titrant
run out of the burette ends up in the flask. Open the stopcock to allow Na2S2O3 to flow into
the flask. As the Na2S2O3 flows into the flask, the flask should be continuously swirled to
promote good mixing.

14. Initially, the Na2S2O3 can be added quite quickly. As the Na2S2O3 solution is added the
brown colour will lighten becoming, eventually, a pale yellow. At this point add 2 - 3 drops
of starch indicator. The solution should turn a deep blue. If the starch is added a bit too early
the solution may turn “mucky” green. The titration can still be done, but this is not ideal.
Do NOT add the starch at the beginning of the titration!

15. The end point is very “sharp” - the colour will change suddenly - and indicated by the

99
 Ontario Tech University CHEM 1010U, W24; Exp. 2-20.29

complete discharge of the colour (blue to colourless). As you approach the end point you
should slow down your additions of Na2S2O3. Close to the end point you should add Na2S2O3
drop-wise or even (if you are skilled!) half drops at a time. At this point touch the tip of the
burette to the side of the flask and use the wash bottle to wash down the sides of the flask.
This ensures any Na2S2O3 dispensed from the burette reacts with the I2.

16. Once the end point has been reached, stop adding Na2S2O3. Wait a few moments and record
the final volume of Na2S2O3 (again, to 0.01 mL). The volume of Na2S2O3 added to the flask
is the difference between the final and initial volumes.

17. First titrations are often not as accurate as subsequent ones. The first titration should give
you a reasonable idea about the volume of Na2S2O3 that will be used in subsequent titrations.
Do at least three titrations (starting from step 11). Continue the titrations until two titration
volumes agree within ±0.1 mL, but do not do any more than five titrations. The number of
titrations you can perform is limited by the KIO3 that you have - do not waste it!

18. Before each titration ensure the amount of Na2S2O3 remaining in the burette is sufficient for
the titration. If you have any doubt about whether there is sufficient Na2S2O3, fill the burette.

19. If you must do more than three titrations, empty the flasks, rinse well with tap water followed
by deionized water and use the flasks again. The flasks do not need to be dry. Do not take
more KIO3 solution without the instructor’s permission.

20. Average all the titration volumes (titres) that are within 0.1 mL and use the average volume
in the calculations.

21. When you have finished, drain the burette and rinse it 3 times with tap water followed by 3
rinsings with deionized water. Leave the stopcock open and clamp the burette upside down

100
 Ontario Tech University CHEM 1010U, W24; Exp. 2-20.29

in the stand.

22. Rinse the pipette and flasks 3 times with tap water followed by 3 times with deionized water.

101
 Ontario Tech University CHEM 1010U, W24; Exp. 2-20.29

Experiment 2 - Stoichiometry by Titration

Name: ____________________________

Day ____________________________

Time: ____________________________

TA Name ____________________________

You must submit this sheet with your report.

102
 Ontario Tech University CHEM 1010U, W24; Exp. 2-20.29

DATA SHEET - Stoichiometry by Titration

If you are submitting your lab report electronically, you must scan or photograph all the data sheets
with your data as recorded in the laboratory period, signed and dated by the teaching assistant, and
submit them with your report.

Student Name: _____________________________

Student Number: _____________________________
Date: _____________________________
TA Signature: _____________________________

Volume of 0.5 mol L-1 KI / mL: _____________________________

Volume of 1.0 mol L-1 HCl / mL: _____________________________

Concentration of KIO3 / mol L-1: _____________________________

Volume of KIO3 per titration / mL: _____________________________

Concentration of Na2S2O3 / mol L-1: _____________________________

Indicator: _____________________________

Colour change at end point: _____________________________

Volumes of Na2S2O3
I II III IV
Final Volume / mL
Initial Volume / mL
Volume of Na2S2O3 / mL

Average Volume of Na2S2O3 (average of volumes within ±0.1 mL):_______________________

103
 Ontario Tech University CHEM 1010U, W24; Exp. 2-20.29

Calculations and Questions

1. Calculate the number of moles of Na2S2O3 in the average volume of Na2S2O3. Using
equation (2.3) calculate the number of moles of molecular iodine. This is the same as the
number of moles of molecular iodine produced by reaction (2.1).

2. All of the iodine produced by reaction (2.1) is in the form of I2 (molecular iodine). Calculate
the number of moles of atomic iodine (I) produced by reaction (2.1).

3. Calculate the number of moles of KIO3 consumed by reaction (2.1). Remember, it is the
limiting reagent.

4. Calculate the number of moles of I- consumed by reaction (2.1).

5. Determine the ratio for IO3- : I- : I2 for reaction (2.1). Express this as a ratio of integers.

6. Using the results for question 5 complete the balancing of:

____IO3-(aq) + ____I-(aq) + ____H+(aq) ÿ ____I2(aq) + ____H2O(l)

7. In this experiment you were given a precise concentration for the KIO3 solution but not for
the KI solution. Explain why it is not necessary to know precisely the number of moles of
KI added.

8. A funnel is often used to fill the burette with titrant, but is removed before the titration is
begun. Why must the funnel be removed?

9. Volumetric glassware (pipettes, burettes, volumetric flasks, etc.) is usually designated as “TC
at 200C” or “TD at 200C”. What do “TC” and “TD” indicate? What is the difference?

104