Quantitative Analysis of Soda Ash by Double-Indicator Titration

Patrick Aldrei C. Costales

Department of Chemical Engineering, College of Engineering
University of the Philippines, Diliman, Quezon City, Philippines
Date Due: January 16, 2014
Date Submitted: January 16, 2014

the base, with carbonate ion (CO32-) as the

product. The boiled water was then allowed to
cool to room temperature because hot solutions of
base still absorb CO2 from the atmosphere.2

RESULTS AND DISCUSSION

The components of a soda ash sample was
quantitatively determined in the experiment using
the principle of double-indicator titration.

Furthermore, the prepared basic solutions should

not be stored in glass containers because of the
chemical reactions that would occur such as the
formation of sodium silicates. There would be a
buildup of these silicate compounds in the
container, especially for glass-stoppered
containers. This leads to the stopper being stuck
and hard to remove and the decrease in
concentration of the base solution due to the
chemical reaction with glass. To prevent these
unwanted reactions, basic solutions must be
stored in polyethylene or plastic bottles.2

Soda ash is a white, crystalline alkaline powder

prominently used for the manufacturing of glass,
soaps and detergents.1 The composition of
commercially available soda ash may be one or a
mixture of the following compounds: sodium
carbonate (NaCO3), sodium hydroxide (NaOH)
and sodium bicarbonate (NaHCO3).2 However, a
combination of NaOH and NaHCO3 cannot be
observed because of its instability. A chemical
reaction occurs producing a mixture of NaCO3
and the excess reactant.
The titration of carbonate by HCl proceeds by
converting all of the CO32- ions into HCO3- at the
first equivalence point (Equation 1) and all the
HCO3- ions are converted into H2CO3 at the
second equivalence point (Equation 2). In reality,
carbonic acid does not exist in solution because it
decomposes into carbon dioxide and water
(Equation 3).
CO32-(aq) + H3O+(aq) HCO3-(aq) + H2O(l)

(1)

HCO3-(aq) + H3O+(aq) H2CO3(aq) + H2O(l)

(2)

H2CO3(aq) CO2(g) + H2O(l)

(3)

Before titration, the 0.05 M HCl solution was

standardized against a NaCO3 solution prepared
by weighing the appropriate amount of sodium
carbonate and dissolving it in water. The
standardization step determines the true value of
the concentration of the titrant, since the primary
standard used is of high purity. Sodium hydroxide
cannot be used as primary standard in the
standardization of HCl because NaOH is not of
high purity and its true concentration may vary
over time since exposure to the atmosphere
causes dissolution of water and carbon dioxide
which may lead to a decrease in concentration of
the NaOH.3

In the preparation of base solutions such as

NaOH, the distilled water to be used for
dissolution and dilution was boiled beforehand to
remove any dissolved carbon dioxide (CO2)
which may interfere with the solution. Dissolved
CO2 would react with the hydroxide ions (OH-) of

Sodium carbonate (MW=105.98844 g/mol) with

a purity of 99.9% was used in the experiment.
Table 1 presents the titration data during
standardization.

Table 1. Standardization of HCl

Trial
1
2
Standard
0.109
0.102
weight, g
Net volume 42.1
39.6
HCL, mL
Concentration 0.0488
0.0486
HCl, mol/L
Average
0.0477
concentration
HCl, mol/L

contributes to the larger amount of bicarbonate

than carbonate ions. In other words, the sample
used in the experiment is composed of Na2CO3
and NaHCO3. Table 3 presents the calculated
composition of the sample.

3
0.1026
42.2

Table 3. Composition of Soda Ash Sample

Trial
1
2
3
mmol Na2CO3
0.258
0.176
0.234
% Na2CO3
20.7
18.5
18.7
mmol NaHCO3 0.262
0.0668 0.0191
% NaHCO3
21.2
7.10
1.54

0.0458

The second end point is used to determine the end

of the standardization instead of the first because
of the sharper and steeper change in pH with
respect to the change in volume of the titrant. In
addition, the solution was boiled prior to the
endpoint indicated by a color change of the
methyl orange indicator from yellow to pale
orange in order to restore the alkalinity of the
solution by removing the carbonic acid, thus
creating a much sharper change in pH during the
endpoint and a more prominent color change.2

All percentage values for the components are

accepted when a Q-test is performed at 95%
confidence level. Table 5 presents some values of
statistical parameters for Trials 2 and 3 at a 95%
confidence level, where there are three replicate
measurements (n = 3).
Table 5. Statistical Parameters
% NaCO3
Range
2.2 %
Mean
19.3 %
Standard
1.22 %
Deviation
Relative SD
63.2 ppt
Confidence
3.03 %
Limit

The soda ash sample was titrated with the

standardized HCl solution and the components
were determined from the volume relationship of
the first and second end points, indicated by
phenolphthalein and methyl orange, respectively.
Table 2 shows the titration data for the analysis of
the composition of the soda ash sample.

% NaHCO3
19.7 %
9.95 %
10.1 %
1015 ppt
25.1 %

The value of the confidence limit for the

percentage of sodium carbonate implies that the
true value of the mean (19.3%) may lie within an
interval 3.03 above and below the value. On the
other hand, the true value of the mean for the
percentage of sodium bicarbonate present in the
sample (9.95%) may lie within an interval of 25.1
above and below the value, which is a rather large
interval.

Table 2. Sample Analysis

Trial
1
2
3
Sample weight, g 0.1324 0.1007 0.1323
Net volume HCl at 5.40
3.70
4.90
phenolphthalein
end point, mL
Net volume HCl at 10.90 5.10
5.30
methyl orange end
point, mL

Titration experiments are bound to have several

sources of error which may cause the measured
and calculated values to deviate from the real
value. One such error that may have been
encountered in the experiment is termed as
carbonate error where the concentration of the
basic solution is reduced due to the dissolved
carbon dioxide, forming carbonate ions in the
solution. When basic range indicators such as
phenolphthalein are used, the carbonate ions react

For all three trials, the net volume of HCl needed

to reach the methyl orange endpoint is greater
than the net volume of HCl needed to reach the
phenolphthalein endpoint. This implies that there
are more HCO3- ions present in the sample than
there are CO32- ions. Therefore, aside from the
sodium carbonate in the soda ash sample, an
amount of sodium bicarbonate is also present that

with hydronium ion in the solution, thus lowering

the effective concentration of the solution.2 The
presence of carbonate ions before titration also
decreases the sharpness of the end point, leading
to a less prominent change in color of the
indicator.
Another possible source of error takes into
account the method used for determination. The
phenolphthalein-methyl orange double-titration
system becomes unreliable at low concentration
of carbonate. This distorts the theoretical titration
curve and diminishes the prominence of the end
points, thus, making the color change more
difficult to distinguish. The method can be made
more accurate by using an indicator that changes
its color at a higher pH than methyl orange.4
REFERENCES
1. United Nation Environment Programme
Chemicals Branch. Sodium Carbonate.
http://www.chem.unep.ch/irptc/sids/OE
CDSIDS/Naco.pdf (accessed Jan 14,
2014).
2. Skoog, D.; West, D.; Holler, F.; Crouch
S.
Fundamentals
of
Analytical
Chemistry, 9th ed.; Brooks/Cole:
California, 2013.
3. Harris D. Quantitative Chemical
Analysis, 7th ed.; W.H. Freeman and
Company: New York, 2008.
4. Schroeder, W.C. Errors in the
Determination of Carbonate in Boiler
Water. Ind. Eng. Anal. Chem. Ed.
[Online]
1932,
4,
271-273.
http://pubs.acs.org/doi/pdf/10.1021/ac50
086a010 (accessed Jan 14, 2014).

APPENDIX
SAMPLE CALCULATIONS
A. Standardization of Hydrochloric Acid Solution
mol
MHCl , L

mg
% purity
)

FW Na2 CO3
100

2(

VHCl ,mL
0.0002 2

109 mg
0.999
105.98844 g/mol

42.1 mL

= .

0.1 2

r = 0.0488( 0.109 ) + (42.1) = .

Average MHCl ,

mol
L

0.0488 M+0.0486 M+0.0458 M

3

= .

r = (0.0001)2 + (0.0002)2 + (0.0001)2 = .

B. Composition of Soda Ash
mmol Na2 CO3 = MHCl Vphth = 0.0477 M (5.40 mL) = .
mmol NaHCO3 = MHCl (Vphth Vmo ) = 0.0477 M (10.90 mL 5.40 mL) = .
% Na2 CO3 =
% NaHCO3 =

(mmolFW)Na2CO3
mgsample

100% =

(mmolFW)NaHCO3
mgsample

(0.258)(105.98844)

132.4

100% =

100% = . %

(0.262)(106.99638)

132.4

100% = . %

C. Statistics
Range = 20.7 18.5 = .
Mean =

20.7+18.5+18.7
3

= .
(20.719.3)2 +(18.519.3)2 +(18.719.3)2

Standard deviation =

31

1.22

RSD = 19.3 1000 ppt = .

Confidence limits = 19.3

(4.30)(1.22)
3

= . . %

= .