Experiment 3: Determination of Mixed Alkali

Ragasa, Charissma Leiah R., Solibaga, Nathaniel Joseph R.

Group 3, Chem 27.1, WEJ, Ms. Jireh Sacramento
April 8, 2015
I. Abstract
In the determination of mixed alkali through neutralization titration, two indicators namely
phenolphthalein (base-range) and methyl orange (acid-range) are used. Neutralization titration involves the
reaction of an analyte and a standard solution and is usually employed to convert the analyte (i.e., polyfunctional
acids) into different species that could be determined. After three titrations of the standard with HCl, the volume
in the phenolphthalein and methyl orange endpoints are compared to determine the composition of the analyte.
In this experiment, the students were given an unknown which resulted to the conclusion that the sample
contains NaHCO3 and Na2CO3. Furthermore, the %(w/v) Na2CO3 is 0.4875 % and %(w/v)NaHCO3 0.2942 % .
II. Keywords: alkalinity, double titration, double indicator, carbonates, %(w/v) Na 2CO3, %(w/v)NaHCO3
III. Introduction
Alkalinity is primarily a way of measuring the
acid neutralizing capacity of water. The acid
neutralizing capacity of water is due to hydroxyl
(OH-), carbonate (CO32-) and bicarbonate (HCO3-)
ions present in water. The ability of natural water to
act as a buffer is controlled in part by amount of
calcium and carbonate ions in solution from calcium
carbonate (CaCO3) or limestone. Natural water that
comes in contact with limestone has therefore high
levels of Ca2+ and CO32- ions and has elevated
hardness and alkalinity.
No more than two of the three constituents that
contribute to acid neutralizing capacity of water can
exist in an appreciable amount in any solution
because reaction will eliminate the third.
HCO3-+ OH- -> CO32-+ H2O
Consequently only the mixture of the alkali can
only exist in 5 possible combinations namely NaOH,
Na2CO3,
NaHCO3,
NaOH+Na2CO3,
and
NaHCO3+Na2CO3.

Fig. 1 Sample Titration Curve

It can be seen in the figure that the titration
of carbonates in the solution has two endpoints
(and thus needs two different indicators) and the

volume of H+ required to reach each endpoint is

used to determine its fraction in the solution. In the
same way, the titration of OH in the solution
requires certain amount of H + to reach its
phenolphthalein endpoint and this volume is also
considered in determining the composition of a
mixed alkali.
IV. Methodology
A. Preparation of 0.1M HCl.
The volume of concentrated hydrochloric acid
(HCl) needed to prepare 1L of 0.1M concentration
was calculated. A volume equal to the calculated
amount was transferred into a 500-mL beaker with
300 mL CO2-free distilled water. The solution was
mixed and transferred to a 1-L volumetric flask and
diluted to the mark. The final solution was
transferred to a 1-L amber bottle.
B. Standardization of 0.1M HCl.
Five grams of primary-standard grade Na 2CO3
was dried at 110C for 2 hours and was cooled in
desiccator. After drying, three 0.20 to 0.21 g of the
dried sodium carbonate was weighed by difference
and transferred to three labeled Erlenmeyer flasks.
The weights of the samples were noted and
recorded. Each sample was dissolved in 25 mL
distilled water and 2 drops of methyl orange was
added as indicator. Each sample was titrated with
0.1M HCl until the color changed gradually from
yellow to red-orange. After the color change, the
solution was boiled gently for 2 minutes, until the
yellow color returned. The sample was allowed to
cool while covered with a watch glass. The titration
was continued until a sharp yellow to red-orange
color change was observed. The molarity of the
titrant was calculated from the recorded volumes.

C. Analysis of the Unknown.

0.0122 L HCl

The unknown was dried at 110C for 2 hours

and cooled in a desiccator. After drying, 0.20-0.21g
unknown was weighed and transferred to three
numbered Erlenmeyer flasks. Twenty five milliliters
of CO2-free distilled water was transferred to the
flasks to dissolve the sample. Two drops of
phenolphthalein was added as indicator. The
solution was immersed in ice bath and then titrated
with the standardized HCl until the pink color
disappears. The solution was boiled gently for 2
minutes, until yellow color returns. After boiling, the
solution was cooled while covered with watch glass
and then titrated with the standardized HCl until
color changes from yellow to red-orange. The %
(w/v) Na2CO3 and NaHCO3 as calculated for the
sample.
V. Results
Table 1: Standardization of HCL Solution
Trial
1
2
3
Ave M

Wt. Na2CO3
.2048 g
.2008 g
.2025 g
.09151 M

V of HCl
43.8 mL
42.9 mL
39.0 mL

M of HCl
0.08823 M
0.08832 M
0.09798 M

Sample computation for M of HCl:

1
0.0438 L HCl
2 moles H +
1 mole Na 2CO 3
0.248 g Na 2CO 3 x
x
105.99 g Na2 CO
1 mole C 032 x

=0.4733 % Na2CO3
Sample computation for %(w/v)NaHCO3:

( 0.02230.0122 ) L HCl

Titration of Diprotic Brnsted Base CO32There are several species of interest in

analytical chemistry that have two or more acidic or
basic functional groups. These species are said to
exhibit polyfunctional acidic or basic behavior.
Generally, with a polyfunctional (diprotic) Brnsted
base such as sodium carbonate (Na2CO3), the
deprotonated/protonated species (CO32-, HCO3-,
H2CO3) differ enough in their dissociation constants
(at least by 104) that they exhibit multiple (two) end
points in a neutralization titration.
The alkalinity of water can be determined by
titration - with a standardized strong acid - of these
carbonate species in a solution. Reaction between
H3O+ from aqueous strong acid and Na2CO3 (aq)
takes place in two stages:
(1) CO32- + H3O+
Kb1=

Kb2=
Table 2: Analysis of Unknown Using Double
Indicator Method

Trial

1
2
3

12.2 mL
12.7 mL
12.8 mL

V of HCl
to methyl
orange
endpoint

%(w/w)
Na2CO3

%(w/w)
NaHCO3

22.3 mL
21.8 mL
22.3 mL
Average:

0.4733 %
0.4927 %
0.4966 %
0.4875 %

0.3105 %
0.2798 %
0.2921 %
0.2942 %

Sample computation for %(w/v) Na2CO3:

0. 09151 moles HCl 1 mole NaHCO

1 L HCl
1mole HCl
25 mL

=0.3105 % NaHCO3
VI. Discussion

HCO3- + H2O

Kw
-4
K a 2 = 2.1x10

(2) HCO3- + H3O+

=0.08823M

V of HCl
to
phenolph
thalein
endpoint

0. 09151moles HCl 1 mole Na 2CO 3 105.99

1 L HCl
2 mole HCl
1 mole
25 mL

H2CO3

Kw
-8
K a 1 = 2.3x10

2H2O + CO2 (gas)

After the titration has begun, part CO32 is

converted to HCO3- and a CO32 /HCO3- buffer
region is established. Beyond the first equivalence
point, the HCO3 is partially converted to H 2CO3
(CO2) and a second buffer region is established, the
pH being established by [HCO 3]/[CO2]. These
buffer regions cause less defined endpoints.
Fortunately this endpoint can be sharpened,
because the CO2 produced from the neutralization
of HCO3 is volatile and can be boiled out of the
solution. This mainly is the reason the solutions
were boiled in the experiment.
Conversely, in analysis of unknown, the solution
was also titrated in an ice bath. As seen in

equations (1) and (2), decreasing the temperature

of the solution increases the solubility of CO2 and
this will result to non-loss of CO 32 that are needed
to be titrated.
The titration of OH- in the unknown solution is a
strong acid - strong base titration with the equation
(3) OH- + H3O+ 2H2O.
Use of Appropriate Indicators

Solution mixture of reaction (1) at the

equivalence point is alkaline, that of reaction (2) is
acidic and that of reaction (3) is neutral.
The analysis of the mixture requires two
indicators:
1) alkaline-range indicator for the first
endpoint, such as phenolphthalein (pH 8.2- pH 9.8),
2) acid-range indicator for the final
endpoint, such as bromocresol green (pH 3.8- pH
5.4) or methyl orange (pH 3.1- pH 4.4).

Difference in volumes required for each

endpoint arises from differences in each method.
The composition of the solution can then be
deduced from the relative volumes of strong acid
needed to reach each endpoint.
Analysis of the Unknown
There are five different possible combinations
of unknown in the experiment, namely, NaOH only,
Na2CO3 only, NaHCO3 only, mixture of NaOH and
Na2CO3, and lastly, mixture of Na 2CO3 and
NaHCO3. NaOH and NaHCO3 cannot exist in the
solution for it will undergo self-titration as shown.
HCO3-(aq) + OH-(aq)

CO32-(aq) + H2O

The possible combination and its amount in the

unknown solution are analyzed in the experiment
using Double Indicator Method.

The wide endpoint range of reaction (3) can

either be indicated by phenolphthalein and
bromocresol green/methyl orange shown by its
titration curve.

Two Methods of Acid-Base Titration

Double Titration Method
For simplicity, the double titration method is the
titration of two aliquots (from one same solution) in
separate Erlenmeyer flasks containing different
indicators. The volume of strong acid required for
each endpoint is recorded.
Double Indicator Method
The double indicator method is the subsequent
application of two indicators in a single aliquot in
one Erlenmeyer flask. This is the method used in
the experiment. After reaching the first endpoint
(wherein the experiment it is phenolphthalein
endpoint), the next indicator is added (methyl
orange or bromocresol green). The volume of
strong acid required for the first endpoint is
recorded. From the first endpoint, the volume of
strong acid required to reach the final endpoint is
recorded.

1. Na2CO3 only
The volume (mole) of H+ needed to titrate one
equivalent volume (mole) of CO32 to HCO3
(phenolphthalein endpoint) is the same as the
volume (mole) of H+ to titrate HCO3 from first
endpoint to final endpoint as H2CO3.
Hence, Voph = Vphm.o.
2. NaHCO3 only
Since
HCO3
does
not
cross
the
phenolphthalein endpoint, addition of H + will skip
the first endpoint titrating HCO3 directly to final
endpoint as H2CO3.
Hence, Voph =0; Vphm.o.>0
3. NaOH only
In using double indicator method, the next
indicator (methyl orange) is added only after
reaching the phenolphthalein endpoint. Thus, the
volume required for its only endpoint is already met
before adding the second indicator leaving zero

volume of HCl to reach the expected methyl orange

endpoint.
Hence, Voph >0; Vphm.o.=0
4. mixture of Na2CO3 and NaHCO3
Every Na2CO3, will be titrated to HCO3 at
phenolphthalein endpoint. All of these HCO 3 will
require same amount of H+ to reach methyl orange
endpoint yielding H2CO3. Since there is additional
HCO3 from NaHCO3, additional volume of H + is
needed to reach methyl orange endpoint.
Hence, Voph < Vphm.o..

3. NaOH only
As shown in its titration curve, the endpoint of
this titration covers both the range for
phenolphthalein and methyl orange endpoint. Thus
same volume of H+ is needed to reach both
endpoints in different Erlenmeyer flasks.
Hence, Voph = V0m.o.

5. mixture of NaOH and Na2CO3

Similar to the previous one, all Na 2CO3 require
equal amount of H+ to reach first and final endpoint.
However unlike the previous mixture, there is
additional volume of H+ needed to titrate OH from
NaOH to phenolphthalein endpoint.
Hence, Voph > Vphm.o..
Analysis of Unknown Using Double Titration
Method
1. Na2CO3 only
Since same amount of H+ is required to reach
both endpoints, twice the volume required to reach
the phenolphthalein endpoint is the volume of H +
needed to reach the methyl orange endpoint.
That is Voph = V0m.o. or 2 Voph = V0m.o..

4. mixture of Na2CO3 and NaHCO3

For the Na2CO3 content of the mixture, twice
the volume of H+ needed to titrate CO32 to HCO3 is
equal to the volume of H+ needed to titrate the
CO32 to H2CO3. The excess NaHCO3 requires
additional volume of H+ not to phenolphthalein
endpoint but to methyl orange endpoint.
That is, 2 Voph < V0m.o.
Voph (the volume of H+ required to reach
phenolphthalein endpoint) is equivalent to the
amount of Na2CO3 in the solution. Using difference
in volumes as approach, (V 0m.o.) 2(Voph) is
equivalent to the amount of NaHCO3 in the
solution.

2. NaHCO3
Similar to double indicator method, the titration
will skip the phenolphthalein endpoint and will
proceed directly to methyl orange endpoint.
Hence, as before, Voph =0; V0m.o.>0

5. mixture of NaOH and Na2CO3

If volume difference approach is used, and if
the solution contains only Na2CO3,
Voph = (V0m.o.Voph)
But since, there is an excess of NaOH, more
volume of H+ is needed to reach the
phenolphthalein endpoint than expected. That is,
Voph > (V0m.o. Voph)

orange endpoint from phenolphthalein endpoint was

significantly greater than the volume to reach the
first phenolphthalein endpoint, it is concluded that
the groups unknown contain NaHCO 3 + Na2CO3.
Its percentage in the sample can be calculated
through stoichiometry from the volumes of H+
required for each endpoint.

VII. Conclusion and Recommendations

The composition of the solution in a mixed alkali
can be deduced from the relative volumes of strong
acid needed to reach each endpoint. The required
volume of H+ to reach each endpoint is summarized
as follows.
Constituents

DOUBLE INDICATOR METHOD

Na2CO3
NaHCO3
NaOH
NaHCO3
+
Na2CO3
NaOH + Na2CO3

Voph = Vphm.o.
Voph =0; Vphm.o.>0
Voph >0; Vphm.o.=0

Constituents

DOUBLE TITRATION METHOD

Na2CO3
NaHCO3
NaOH
NaHCO3
+
Na2CO3
NaOH + Na2CO3

Voph < Vphm.o.

Voph > Vphm.o.

Voph = V0m.o. or
2 Voph = V0m.o..
Voph =0; V0m.o.>0
Voph = V0m.o.
2 Voph < V0m.o.
Voph > (V0m.o. Voph)

In order to determine the components of an

unknown mixed alkali solution, one must analyze
the results of the titrations- compare the volumes of
the titrant in phenolphthalein and bromocresol
green endpoints. Using the double indicator
method, since the volume of H+ to reach the methyl

Discrepancies in the data resulted from various

factors like improper lab techniques or over titration.
The reagents used may also result to errors if not
measured very well or if the standardized HCl is
exposed to the environment for a long time.
The students should take note of their titration
techniques so as to be aware whether they have
already reached the endpoint. Always use CO 2-free
distilled water so as to avoid contaminants. Cover
all reagents if necessary to avoid exposure to
contaminants. Instability of the carbonate mixtures
may occur due to CO2 exchange with the
environment. One must also be well-acquainted
with the procedures of the experiment.
VIII. References
Christian, G. et al. (2014). Analytical
Chemistry 7th Edition. Hoboken, NJ: John Wiley
and Sons Inc.
Skoog, D. et al. (2014). Fundamentals of
Analytical Chemistry 9th Edition. Belmont, CA:
Brooks/Cole Cengage Learning.

I hereby certify that I have given substantial

contribution to this report,
_____________________
Ragasa, Charissma Leiah R.
________________________
Solibaga, Nathaniel Joseph R.