DETERMINATION OF COMPOSITION OF A

CARBONATE BICARBONATE MIXTURE: METHOD

OF ALIQUOT AND pH TITRATION
BACKGROUND
Crude sodium carbonate, called soda ash, is commonly used as a
commercial neutralizing agent. The titration with standard acid to the
bromocresol green end point gives the total carbonate content. The
results are usually expressed as the weight percent of sodium
carbonate in the crude sample. Since the samples are frequently nonhomogeneous, the method of aliquot portions is employed. In this
experiment, the same basic principle is used to find the percent
composition of a mixture of sodium carbonate, sodium bicarbonate in
unknown sample. This is done in two ways: acid-base titration using
two different indicators and the pH titration using a pH meter. You are
then asked to compare the two methods.

PROCEDURE
PART I: Standardization of HCl
Follow the attached procedure for the standardization of HCl.
PART II: Analysis of a mixture of carbonate and bicarbonate
Follow attached procedures (from Harris web site).
OR,
PART II: Method of aliquots in the determination of percent
sodium carbonate in an unknown mixture
Weigh precisely into a clean 250-ml beaker a 5.0 g sample of
the dried (110 oC for one hour followed by cooling in a desiccator)
unknown. Dissolve the sample in about 125 ml of distilled water. Place
a clean funnel in a 250 ml volumetric flask and transfer the solution
from the beaker to the flask. Rinse the beaker, add the rinsate to the
flask, and finally dilute to the calibration mark with distilled water.
Mix the contents of the volumetric flask by inversion and shaking.
Pipet a 25 ml aliquot into a 125 mL Erlenmeyer flask and add
3-5 drops of bromocresol green. Titrate with standard hydrochloride
acid (prepared in part I) until the indicator turns from blue to green.
Then boil the solution to expel CO2. The solution should return to blue
color. Carefully add HCl from the buret until the solution turns green
again. Repeat the titration with at least two other 25 ml aliquots. At

the end of the titration clean the volumetric flak thoroughly. An

alkaline solution should never be left in a volumetric flask for a long
period of time (why?). Transfer the solution into a plastic bottle for
later use.
Report the mass percentage of sodium carbonate (Na2CO3) in
the unknown. A precision of 3 to 5 parts per thousand is not unusual
for this analysis.

PART III. Analysis of a mixture of carbonate and bicarbonate by

pH Titration.
The unknown soda ash is titrated with standard HCl using a
potentiometric (pH) end point measured with a pH meter and
combination electrode. The indicator (bromocresol green) end point
results are compared with potentiometric end point results to observe
the clarity and variability of various techniques. The relevant
reactions and end point changes are as follows:
8.3)

CO32- + H+ HCO3-

(First end point, pH =

HCO3- + H+ H2O + CO2

(Second end point, pH

= 4.5)
The purpose of the first titration is to locate approximately each
of the two equivalence points in the titration of carbonate ion with
HCl. The second, or final, titration is used to determine the second
equivalence point in the titration.
Manual Titration Procedure
First, calibrate the pH meter using two standard pH buffers (pH 4.00 and pH
7.00). Transfer using a volumetric pipet a 25.00 mL aliquot of the sample
soda ash solution to a 250 mL beaker containing a magnetic stirring bar.
Add approximately 25 mL of distilled water (Of which the exact volume is
not important. Why?) to the beaker. Place the beaker on a stirrer, immerse
the pH electrode, and start the stirrer being careful not to touch the
electrode to the stirring bar. Titrate with standard HCl, taking both pH
and mV readings every 2.00 mL. Plot a curve (using any spreadsheet
software) of pH versus volume of HCl added and locate the approximate end
points (both of them) on the graph.
For the final titration, after transferring a 25.00 mL sample aliquot from the
original sample solution and diluting with 25 mL of deionized water, take pH
readings every 5 mL to within 3 mL of the second equivalence point
(including both sides of equivalence point). Then take readings every 0.50mL interval. Near the equivalence point, take readings as quickly as possible
because the pH will tend to drift as carbon dioxide escapes from the
solution. Enter your data into a spreadsheet and set up data entry as mL HCl
added in one-column and mV readings in the other.
Repeat the titration focusing at the second end point. From 0.9V e2 to Ve2, add
HCl in 0.5 mL increments.
Automated Titration

Pipet 5.0 mL of the unknown solution and add 25.0 mL of water in the
titration beaker. Prime the pump with the standard HCl. Measure pump flow
rate by delivering a known volume of HCl in a 10.0 mL measuring cylinder
for a fixed time. Assemble the titration setup and ready for the program run.
Ask your instructor to help you in this step. The computer controlled pH
measurement system must be started the same time the pump is on. Record
the pH until it drops to a stable acidic range. The real time titration graph
shows the two end points and the end of the titration. The titration data- pH
vs. time is recorded in XL format. You must convert the time to volume of
HCl added by the flow rate. A typical auto-titration plot is shown in the
following figure.

Gran Plot
A Gran plot will be used to graphically determine the
equivalence points from the titration data. This will be discussed in
class. Other descriptions of plotting potentiometric end points are
provided in the textbook. Be sure and review these pages before you
plot your data according to the Gran function. Use the titration data at

V H x 10 pH =

K a1

A-
( V e2 - V H )
HA

preceding and up to the equivalence point (i.e., 0.9Ve to Ve) for the
Gran plot. The acid dissociation equilibrium equation for the
protonation of carbonate and bicarbonate ions can be used to derive
the Gran function below (read Harris web book!).
Where, VH = volume of HCL added; Ka1 = acid dissociation constant
for first dissociation of carbonic acid; = activity coefficients; Ve2 =
second equivalence volume; HA and A are the conjugate acid base
pairs, respectively. The above equation is given for the second end
point region. The fist equivalence point can be obtained similarly by
using the data near the first end point region. Which Ka value did you

get from this region? Convince yourself by writing appropriate

equilibrium expression. For this experiment you can assume the
activity ratio as unity.
A plot of the Gran plot of VH x 10pH vs. VH for titration volumes
near and up to the equivalence point provides a straight line which is
extrapolated to the x-axis to find Ve. You should only consider the
straight line portion to find the slope and the intercept. Calculate Ka
from the slope of the Gran plot. A typical Gran plot is shown below.
The Gran plot shown here
was done with the above
titration data in the region
of first infection point. This
region should be selected
such that it covers data
points from the foot to the
peak of the second
derivative (as your guide).
Then chose the linear
portion to extrapolate
volume on the x-axis as
shown by the straight line.
Alternatively, you can use
trend line to calculate the
volume only on the
straight-line portions of the
data. You can find the Ka1
of carbonic acid from the
slope which is = -1/Ka1.

DATA AND RESULTS

1. This is a composite lab. A complete lab report should be submitted
with the following information.
2. Present your data for the standardization of HCl. You also need to
use the NaOH previously standardized.
3. Present your data for the indicator based titration of the mixture.
Use the attached example calculation to calculate the percent
composition. If a group is using the same unknown, then you must
present all the data of the group and calculate the average, relative
standard deviation and 95% . Make sure to have all the raw data
from your group members.

4. pH titration: Obtain the pH titration XL file. Plot the pH-volume,

the first derivative, and the Gran plots. Find the exact titration
inflection points and the volume of HCl from the Gran plots. You
must do two Gran plots: one for the first inflection region and the
other for the second inflection region.
5. Also, obtain the Ka value from the Gran plot. Compare the Ka1 and
Ka2 with those of the literature.
6. Calculate the percent composition (and errors) of the mixture by
using the inflection volumes obtained from Gran plots. Example
calculations are shown in the following pages.
7. Finally, compare and contrast the two methods as an analytical tool
for this analysis.

QUESTIONS
(Submit answers to the following questions with your lab
report)
1. Explain why is it necessary to expel CO2 near the end of the
titration?
2. The alkalinity of natural waters is usually controlled by OH-, CO32-,
and HCO3-, which may be present singularly or in combination.
Titrating a 100.0 mL sample to a pH of 8.3 requires 18.70 mL of a
0.0281 M solution of HCl. A second 100.0 mL aliquot requires
48.20 mL of the same titrant to reach pH of 4.5. Calculate the
concentrations of CO32- and HCO3- in ppm. (Alkalinity is a measure
of water's ability to neutralize acid)

NOTES

With appropriate planning of the work, the sample should be

placed in the oven overnight for proper drying.
Be extremely careful in the weighing and sample transfer
operations because any error here has a grave consequence. The
results of the subsequent determination will be incorrect even if
the results of repeated titrations of aliquots of the sample solution
agree well.

Calculation Procedure
TITRATION OF A MIXTURE OF CARBONATE AND BICARBONATE

Part II. Titration using visual indicators

Find the volume of HCl for Phenolphthalein end point: Vp
Let MHCl = molarity of HCl and MOH = molarity of NaOH
Volume of NaOH added = Va
mols of bicarbonate = Va x MOH - Vp x MHCl
[HCO3-] = mols of HCO3- / Volume of aliquot
Calculate average, standard deviation and 95%
Find volume of HCl required for end point with Bromocresol Green (BG): V b
The BG end point indicates the complete conversion of carbonate and bicarbonate to
carbonic acid (pH about 4-5). We know
mols of CO32- / mols of HCl =

mols of HCl = 2 mols of CO32-

Total mols of HCl used = (Vb x MHCl) = mols HCl used for HCO3- + mols HCl used for CO32Vb x MHCl = mols of bicarbonate + 2 . mols of carbonate
Since mols HCO3- is known from the previous calculation, mols of CO32- can be calculated.
[CO32- ] = mols of CO32- / Volume of aliquot
Calculate average, standard deviation and 95%
Calculate alkalinity, Alkalinity = 2 [CO32- ] + [HCO3-]
molarity
Calculate error in alkalinity based on standard deviations of [CO 32- ] and [HCO3-]
(Do error propagation)
Calculate wt% of CO32- and HCO3Find mols of CO32- and HCO3- in original sample from molarity
Find gms of CO32- and HCO3- in original sample from mols
Find wt% of CO32- and HCO3- in original sample,
= (g found x 100) / g sample taken

Example Calculation
You are given a mixture containing NaHCO3 and Na2CO3. You took 3.5000 g of the sample and
dissolved to 250.0 mL in a volumetric flask with deionized water. A 25.0 mL aliquot of the sample
required 36.0 mL of standard 0.100 M HCl to reach the Bromocresol green end point. Another
25.0 mL aliquot was mixed with 50.0 mL of standard 0.100 M NaOH. Then the solution is treated
with BaCl2 to precipitate carbonate as BaCO3(s) and immediately titrated with standard 0.100 M
HCl to phenolphthalein end point. The volume of HCl required was 40.0 mL. Calculate the wt% of
NaHCO3 and Na2CO3 in the mixture.
Vp = 40.0 mL
Va = 50.0 mL
mmols of bicarbonate = 50.0 x 0.100 - 40.0 x 0.100 = 1.00 mmols
mg of NaHCO3 = 1.00 mmol x 84 mg/mmol = 84.0 mg (in 25.0 mL aliquot)
[HCO3-] = 1.00/ 25.0 = 0.04M
Vb = 36.00 mL

36.00 x 0.1000 = 2 * mmols of carbonate + mmols of bicarbonate

mmols of carbonate = 0.5 (3.6 - 1.00) = 1.30
mg of Na2CO3 = mmols of carbonate x MW of Na2CO3
= 1.300 mmol x 106 mg/mmol = 137.8 mg (in 25.0 mL aliquot)
[CO32-] = 1.300 mmols / 25.00 mL = 0.052 M
Wt% Na2CO3 = 137.8*100/350.0 = 39.4%

Wt% NaHCO3 = 84.0*100/350 = 24.0 %

Part III: pH titration of CO32- and HCO3- mixture

Use the final pH titration data for the following calculation
Plot mV vs. Volume of HCl added
Take first derivative of mV-mL data and find the volume of HCl at two inflection points: V 3 and

V4
Do Gran plot: Find precise V4, Ka1 and their errors from linear regression. Compare Ka1 with
that of literature value ( Ka1 = 4.45 x 10-7 for H2CO3 == H+ + HCO3- )
Use V3 from derivative and V4 from Gran plot to calculate CO32- and HCO3- as follows:

mols of CO32- = V3 x MHCl

mols of HCO3- = (V4 - 2V3) x MHCl

Calculate the molarity of CO32- and HCO3- in the original solution: mols/volume of aliquot
used. Also, calculate the alkalinity. Compare the results of the two methods.
Calculate the wt% of CO32- and HCO3- in the original mixture. Compare the results with that of
the indicator titration method.