Chem 251 Experiment 4

Analysis of a Mixture of Carbonate and Bicarbonate

Purpose:

This experiment entails first standardizing a NaOH solution with the primary standard
potassium hydrogen phthalate (KHP) and then standardizing an HCl solution using your
standardized NaOH as a secondary standard. You will also be determining the amount of
carbonate and bicarbonate, respectively, in a mixture.

Background:

For background information on primary standards and the use of indicators in acid-base
titrations refer to sections 12-6 and 12-7 in Harris (Tables 12-4 and 12-5).

Procedure:

Note: For best results, you should try to perform both standardizations on the same day.

Section A: Standardization of NaOH

1.) Transfer ~750 ml (so bottle is ~3/4 full) of ~0.1 M NaOH into one of your capped, labeled
polyethylene bottles.

2.) Dry ~3 g of primary standard grade potassium hydrogen phthalate (KHP) for 1 hour in a
110oC oven. Cool the KHP in a desiccator for ~20 minutes.

3.) Calculate the appropriate amount of KHP (MW = 204.223) that will require a volume of
~25 mL of ~0.1 M NaOH using the balanced equation shown below.

CO2-K+
CO2-K+
+ NaOH + H2O
CO2H
CO2-Na
Potassium hydrogen phthalate (KHP)

Weigh four samples of solid KHP and dissolve each in ~25 mL of distilled water. Add three
drops of phenolphthalein (see Table 12.4) to each and titrate one of them rapidly (this is called
a "scout titration") to find the approximate endpoint.

4.) Titrate the remaining samples carefully. During each titration, periodically tilt and rotate
the flask to wash all the liquid from the walls into the bulk solution (you may use small
amounts of distilled water to aid in this process). When near the very end, deliver less than one
drop of titrant at a time by carefully suspending a fraction of a drop from the buret tip. Touch
it to the inside wall of the flask and wash it into the bulk solution with swirling. The end point

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is the first appearance of faint pink that persists for 15 seconds. (The color will slowly fade as
CO2 from the air slowly dissolves in the solution.)

5.) Calculate the mean, the standard deviation, the relative standard deviation and the 95%
confidence interval of the NaOH molarity. If you have used care, the relative standard
deviation should be <0.2%.

Section B: Standardization of HCl (with NaOH standardized in Section A above)

1.) Transfer ~750 ml (so the bottle is ~3/4 full) of ~0.1 M HCl into one of your capped,
labeled polyethylene bottles.

2.) Transfer 25 mL of your HCl solution, using your calibrated pipet, and three drops of
phenolphthalein indicator into a 125-mL flask.

3.) Perform at least three replicate trials; calculate the mean, the standard deviation, the
relative standard deviation and the 95% confidence interval of the HCl molarity. Again, the
relative standard deviation should be <0.2%.

Section C: Analysis of a Mixture of Sodium Carbonate and Sodium Bicarbonate

This procedure involves two titrations. First, total alkalinity (= [HCO3-] + 2[CO32-]) is measured
by titrating the mixture with standard HCl to a bromocresol green end point:

HCO3- + H+ → H2CO3

CO32- + 2H+ → H2CO3

A separate aliquot of unknown is treated with excess standard NaOH to convert HCO3- to CO32-:
HCO3- + OH- → CO32- + H2O

Then all the carbonate is precipitated with BaCl2:

Ba2+ + CO32- → BaCO3(s)

The excess NaOH is immediately titrated with standard HCl to determine how much HCO3-
was present. A blank titration is required for the Ba2+ addition because Ba2+ precipitates some of
the NaOH:

Ba2+ + 2OH- → Ba(OH)2(s)

From the total alkalinity and bicarbonate concentration, you can calculate the original
carbonate concentration.

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Reagents

Standard 0.1 M NaOH and standard 0.1 M HCl (both from sections A and B, respectively)

CO2-free water: Boil 500 mL of distilled water to expel CO2 and pour the water into a 500-mL
plastic bottle. Screw the cap on tightly and allow the water to cool to room temperature. Keep
tightly capped when not in use.

10 wt % aqueous BaCl2: 35 mL/student.

Bromocresol green and phenolphthalein indicators: See Table 12-4 in the textbook.

Unknowns: Solid unknowns (~2.5 g/student) can be prepared from reagent-grade sodium
carbonate or potassium carbonate and bicarbonate. Unknowns should be stored in a
desiccator but should not be heated. Heating at 50°–100°C converts NaHCO3 to Na2CO3.

Procedures

1.) Use freshly boiled (as described in the “Reagents” section above) and cooled water to
prepare the unknown solution by quantitatively transferring (with multiple rinsings of CO2-free
water) all the unknown into the 250-mL volumetric flask (the total weight will be written on
the outside of the vial for you). Dilute to the mark (with the same water) and mix well.

2.) Total alkalinity: Pipet a 25.00-mL aliquot of unknown solution into a 250-mL flask and
titrate with standard 0.1 M HCl, using bromocresol green indicator. Carefully titrate the
solution until it just turns from blue to green (yellow is past the endpoint, indicating acidity).
Then boil the solution to expel CO2. The solution should return to a blue color. Carefully add
HCl from the buret until the solution turns green again. (Refer to the HCl standardization
details on page 256 for a description of the procedure and page 242 for the color changes
associated with bromocresol green indicator). Repeat this procedure with two more 25.00-mL
aliquots.

3.) Bicarbonate content: Pipet 25.00 mL of unknown and two 25.00 mL aliquots of standard
0.1 M NaOH into a 250-mL flask. Why would you use two 25.00 mL aliquots rather than one
50 mL aliquot? Swirl and add 10 mL of 10 wt % BaCl2, using a graduated cylinder. Swirl
again to precipitate BaCO3, add 2 drops of phenolphthalein indicator, and immediately titrate
with standard 0.1 M HCl. Repeat this procedure with two more 25.00-mL samples of unknown.

4.) Blank titration: Titrate with standard 0.1 M HCl a mixture of 25 mL of water, 10 mL of 10
wt % BaCl2, and 50.00 mL of standard 0.1 M NaOH, and 2 drops of phenolthalein indicator.
Repeat this procedure twice more. The difference in moles of HCl needed in steps 4 and 3
equals the moles of bicarbonate in the mixture.

5.) From the results of step 2, calculate the total alkalinity and its standard deviation. But first,
recall the following nomenclature:

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[HCO3-] Bicarbonate Ion Concentration

[CO32-] Carbonate Ion Concentration

[HCO3-] + 2[CO32-] Total Alkalinity

From the results of steps 3 and 4, calculate the bicarbonate concentration and its standard
deviation. Using the standard deviations as estimates of uncertainty, calculate the
concentration (and uncertainty) of carbonate in the sample. Express the composition of the
solid unknown in a form such as 63.4 (±0.5) wt % Na2CO3 and 36.6 (±0.2) wt % NaHCO3
(Depending on what your unknown mixture was made up of). Note: The unknown mixture
also contains an inert species (NaCl). As a result, your percentages will not add up to 100
weight percent as is the case for the example in the text book.

6.) Review Harris Section 3-5 (Propagation of Uncertainty) in order to determine the
uncertainty in the carbonate concentration and the uncertainty in the weight percent for each
component.

Reference:

Harris, D.C., Quantitative Chemical Analysis, 6th edition, W.H. Freeman and
Company, New York, 2002.

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