CHEM 311 Laboratory Manual - Fall 2021 Page 40
Analysis for Sodium Carbonate
In this experiment, a solution of hydrochloric acid is prepared, standardized against pure sodium carbonate,
and used to determine the percentage of carbonate in a sample.
4.1 Introduction and Background
General Background: Standardization
Primary standards are stable, nonhygroscopic substances that react quantitatively, and are easy to purify and
handle. This means that they provide a very accurate reference when used in a reaction. There are many
compounds used as primary standards, such as potassium hydrogen phthalate, benzoic acid, and relevant to
this experiment, sodium carbonate. Pure anhydrous sodium carbonate, besides having all the properties of a
suitable primary standard base, has the added advantage in this experiment of being the same compound as
the substance determined in your “unknown” sample. This helps to compensate for any systematic errors in
endpoint determination (if the standard and analyte react differently, an error is introduced).
Standard sodium carbonate is used in this lab to standardize a solution of HCl – you will use the (very well
known/measured) primary standard sodium carbonate to determine the exact concentration of your
(approximately known) secondary standard HCl solution.
In some titrations, a primary standard can be used directly as the titrant. However, none of the strong acids are
convenient to handle and measure accurately in concentrated form. Therefore, a solution of the approximately
desired molarity is prepared, and the exact value is determined by standardization against a primary-standard
base (in this case, sodium carbonate).
General Background: Alternation and Drop-Splitting
Alternation, in the context of quantitative analysis, means carrying out a series of operations on standards and
samples in alternating sequence. i.e. titrate standard → titrate sample → titrate standard → titrate sample.
In this way, errors resulting from changes in solution concentrations, instrument drift, end-point judgment, and
so forth, can be reduced. It also helps ensure you have a reasonable number of replicates of both standard
and sample in case you run out of time. (ending with 4 standards and 0 unknown titrations is not ideal).
Competent analytical chemists use this technique whenever possible, even though it is not written into the
procedures. You may need a little extra planning to use alternation, but your results will be the better for it.
In titrations that have a very crisp, sharp endpoint, drop-splitting or “fractional drops” can be used to increase
the precision of the endpoint determination. To do this, open your buret slightly to let a small hanging drop
form at the tip. Rinse the drop into the titrand solution with a small amount of DI water, or use a stir rod to
touch the drop onto the rod and then into the titrand.
Technique Background: Reactions of Sodium Carbonate
An aqueous solution of hydrochloric acid is almost completely dissociated into hydrated protons and chloride
ions. Therefore, in a titration with hydrochloric acid the active titrant species is the hydrated proton. This
species is often written as H3O+ (hydronium ion), although the actual form in solution is more correctly
(H2O)nH+.
Carbonate in aqueous solution can act as a base, that is, it can accept a proton to form the bicarbonate ion:
𝐶𝑂2− + −
3 + 𝐻3 𝑂 ⇌ 𝐻𝐶𝑂3 + 𝐻2 𝑂 (3-1)
The bicarbonate formed may also act as a base by combining with another proton to give carbonic acid:
𝐻𝐶𝑂− +
3 + 𝐻3 𝑂 ⇌ 𝐻2 𝐶𝑂3 + 𝐻2 𝑂 (3-2)
The equilibrium constant expressions for the dissociation of bicarbonate and carbonic acid may be written as
[𝐻3 𝑂+ ][𝐶𝑂32− ]
𝐾2 = [𝐻𝐶𝑂3− ]
(3-3)
and
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[𝐻3 𝑂+ ][𝐻𝐶𝑂3− ]
𝐾1 = (3-4)
[𝐻2 𝐶𝑂3 ]
where K1 and K2 are the acid dissociation constants for carbonic acid and bicarbonate, respectively. (The “acid
dissociation” reactions are the reverse of Reactions 3-1 and 3-2.)
When two sequential protonation reactions occur, the extent to which the first reaction proceeds before the
second begins depends on the relative magnitudes of the two acid dissociation constants. (i.e. how much CO32-
is still in solution when the HCO3— begins to react). Importantly – we know that since the values of Ka1 and Ka2 for
these acids are not “well separated, there WILL be a significant amount of CO32- remaining when the HCO3—
begins to react. For more on how we can predict this – hang on until the “systems of equilibria” section in class
or read ahead in Harris Chapters 8 & 10.
This means that:
• After the point at which HCO3— begins to react, any strong acid (H3O+) added could react with either the
carbonate or the bicarbonate – the reaction of strong acid with carbonate is not quantitative when
significant amounts of both bases are present. (we can’t guarantee that our titration reaction 3-1 is the
only important reaction anymore!)
• The presence of the bicarbonate – and the overlapping reactions – will act to blur the endpoint of the
titration. This means the change in pH will be less sharp, and the endpoint (both by pH and by colour)
will be more difficult to detect.
𝐶𝑂2−
3 +𝐻
+
→ 𝐻𝐶𝑂3−
𝐻𝐶𝑂3− + 𝐻 + → 𝐻2 𝐶𝑂3
Accumulating excess H+
Figure 3.5: pH curve for the titration of carbonate with hydrochloric acid.
Technique Background: Detection of the Endpoint and Equivalence Point
The predicted titration curve for a carbonate solution is shown in Figure 3.5. You can see that there are two
“endpoints” (the sharp “S” shape in the curve). The first (V1, at ~20 mL) is for the reaction of carbonate with the
strong acid, and the second (V2. at ~40 mL) is for the reaction of bicarbonate.
Using V1 to determine the carbonate concentration is complicated by the points raised above – that bicarbonate
will also be reacting with the strong acid at this pH. This endpoint is less sharp, and harder to detect precisely.
The second endpoint (V2) is also less sharp than in some other acid-base titrations, but this can be improved
by removing the H2CO3 that is formed during the reaction. Conveniently, shaking or boiling a solution of
carbonic acid causes the equilibrium shown in Equation 4-5 to be pushed to the right through loss of carbon
dioxide:
𝐻2 𝐶𝑂3 (𝑎𝑞) ⇌ 𝐻2 𝑂 (𝑙) + 𝐶𝑂2 (𝑔) ↑ (3-5)
As the solution is boiled and CO2 removed, the pH of the solution will increase (due to the conversion of
H2CO3 to form more CO2 – and the reduced H2CO3 will in turn affect the equilibrium position of Reaction 3-2…
and then 3-1).
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During the titration, if the solution is boiled just before reaching the second endpoint, this increase in pH will
make the endpoint sharper and easier to pinpoint. The effect of boiling off CO2 does not change the
stoichiometry of the reaction (you still need 1 mol of strong acid to react with every mol of bicarbonate) – only
the equilibrium position of the reaction when both species are present in solution (i.e.before the equivalence
point) is affected. Therefore, the overall reaction remains quantitative.
This effect on the titration curve can be seen in Figure 3.6. The solid blue line is the region of the titration curve
near the second endpoint when performed normally, with no boiling. The dashed red line shows the effect of
boiling the solution on pH – the titration pauses, and the solution is boiled after ~39 mL titrant was added. The
pH increase caused by the loss of CO2 makes the endpoint sharper, and the colour change easier to see.
Figure 3.6: Effect of carbon dioxide removal on pH change at the second equivalence point in the hydrochloric acid-
carbonate titration. Solid blue line: unmodified titration. Dashed red line: Titration with boiling after adding 39 mL of
HCl.
4.2 In Your Notebook This Week
This experiment does not require any special treatment – prepare your procedure, data tables, and annotations
before you come to lab. Remember, your TA will check your book sometime during lab. Page 8 has the lab
notebook entry requirements, if you need a refresher.
As you prepare your notebook, think about:
• What steps require waiting? What other steps (or cleanup) can you perform or prepare during this
time?
• What steps must be performed at a specific time or in a specific order?
• In Step 1, do you prepare your HCl solution with high precision? Why is this preparation method
appropriate for this solution?
• In Steps 2a and 4a, why is it important that the sample for weighing be cool? What kind of error would
be introduced if they were still warm from baking?
• In Step 3, you are instructed to boil only one of the flasks you prepared. Why not boil all of them now?
(What kind of error would happen if you did?)
4.3 Procedure
Both sample and reference standard need to be dried at least overnight before weighing and stored in a
desiccator. Your teaching assistant will provide vials of pre-dried sample1 and reference standard.
1. Your TA will provide you with a vial of dried NaCO3 standard and a vial of unknown. Put the sticker with
your unknown number into your lab notebook and also write it down in your notebook. We keep no
1Na2CO3 tends to absorb H2O from the air to form Na2CO3·H2O, and CO2 to form NaHCO3. At least several hours
of drying at 110 C is necessary to remove all H2O and CO2.
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record of unknown numbers, so it is impossible to retroactively determine a lost unknown number -
your results will be ungradable without it (automatic 1.0 / 5).
2. Make your HCl titrant:
a. Calculate the amount of 6 M HCl required to prepare 500 mL of 0.3 M HCl and measure this
quantity into a graduated cylinder. Record this value in your lab book and check it with your TA
as you arrive.
b. Put a little less than 500 mL of deionized water into a clean 1-liter bottle.
c. Measure out the volume of 6M HCl you calculated in (a) and transfer it to the bottle. Mix
thoroughly. Label.
3. Prepare your primary standards:
a. Weigh (to the nearest 0.1 mg) two 0.35 g portions of the dried, cool, sodium carbonate into
clean 250 mL conical flasks.
b. Add about 50 mL of deionized water to each and swirl to dissolve the salt.
4. Standardization titrations:
a. Add four drops of bromocresol green indicator to one of the conical flasks and
titrate with the HCl solution to an intermediate blue-green color. This color
appears before the endpoint.
b. Stop the titration and boil the solution for 1 to 2 minutes, taking care that no
solution is lost during the process. Cover your flask with a watch glass to stop
splashes from escaping (See Figure 3.7).
c. Let the solution cool, wash the flask walls with deionized water from a wash
bottle, and then continue the titration to the first appearance of yellow color (the
solution will change from blue-green to “apple green”). Just before the end-
point the titrant is best added in fractions of a drop.
Figure 3.7: Correct
5. “Unknown” titrations: orientation for watch
a. Quantitatively transfer all contents of your unknown vial into a 100 mL glass "cover"
volumetric flask and dilute to volume with DI water.
b. Pipet 20 mL of this solution into a conical flask and add ~25 mL of DI water.
c. Titrate following the directions in Step 4 above.
Your “unknown” solution volume is very limited. Use your best technique when rinsing (to use a
total volume <20 mL) and do not waste any solution. You will only have enough solution for a
maximum of 4 replicate titrations if proper technique is used.
Note: Use alternation as described in the General Background for the experiment to make sure you get at least
1 standard and 1 unknown titration.
If you use your time well, you can get 3-4 of EACH titration (6-8 titrations total).
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4.4 Approximate Experiment Timeline
Time in Lab Activity Notes
Your TA may give a short intro – this is your
0m Begin work
chance to ask questions before you start!
0 h 45 m Completing the first titration (Standard 1) These are “at latest” times – if you’re ahead,
Completing the second titration (Unknown great! If you’re behind, pick up the pace, or you
1 h 30 m may not finish the experiment on time.
1)
2 h 30 m Completing fourth titration
3 h 15 m Complete final titration
3 h 30 m Stop work and begin cleanup.
Closing time – you don’t have to go home,
3 h 50 m
but you can’t stay here.
4.5 Data Analysis
For your graded analysis result, submit the total mass of carbonate as Na2CO3 in your ‘unknown’ sample.
Remember – a calculation error can get you a “1” grade as easily as poor technique. Check your calculations
carefully, and use the ranges posted to D2L to make sure your answer is “in range”. Use the Questions for
Study to verity your calculation method.
Calculate the molarity of your HCl solution from the standardization titrations:
• Since we are using the second endpoint (at pH 4-5), two moles of H+ are consumed for each mole of
Na2CO3:
2 𝐻𝐶𝑙 + 𝑁𝑎2 𝐶𝑂3 ⇌ 2 𝑁𝑎𝐶𝑙 + 𝐻2 𝐶𝑂3
• The mol of Na2CO3 in each titration can be calculated from the mass of the standard taken (and the
molar mass of Na2CO3).
• From the moles of Na2CO3, you can determine the moles of HCl used. You also know the volume of
HCl used in each titration – from there you can determine the mol/L of HCl in your titrant.
• If your technique was good, the variation in your titration values should be less than 2 parts per
thousand.
Once the [HCl] is known, determine the Na2CO3 in your analysis sample (assuming all CO3 is Na2CO3):
• Again, you are using the second endpoint of the titration, so each mol of Na2CO3 will react with 2 mol
of H+.
• Determine the mol of Na2CO3 in each titration, and from there the [Na2CO3] in the “unknown” solution
you prepared.
• From this concentration, determine the total number of moles of Na2CO3 in your volumetric flask (and
therefore provided in your “unknown” vial).
• Determine the total mass of Na2CO3 that was present in your original “unknown” vial that you obtained
from the TA.
The approximate range of “true values” for unknowns in this experiment is:
1.00 – 3.25 g Na2CO3 (liquid unknowns)
Check your work: all unknowns fall within this range – submitting an answer outside this range is a guaranteed
grade of 1.0/5.
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4.6 Questions for Study
Answers to Questions for Study are at the end of the lab manual.
1. A 0.3750 g sample of pure sodium carbonate required 38.20 mL of a hydrochloric acid solution to
reach the bromocresol green end-point. What is the molarity of the hydrochloric acid?
2. The aliquot of “unknown” solution required 28.94 mL of HCl to reach the endpoint.
a. How many mol of carbonate were in this sample?
b. What is the [CO32-] in the diluted “unknown” solution?
c. How many mol of CO22- were in the original “unknown” vial?
d. What is the mass (in g) of carbonate (reported as Na2CO3) in the original “unknown” vial?
3. What volume of 37% m/m hydrochloric acid of density 1.18 g/mL would be required to prepare 2
liters of 0.3 M solution?
4. What is the primary standard in this titration? How is its concentration determined?
5. What is the reaction in the analysis titrations?
6. What is the “secondary” standard used? Why does it not make a good primary standard?
7. If the sodium carbonate standard was not completely dried, would your final answer be too high or
too low?
