Experiment 3 Determination of Mixed Alkali

LOGRONIO, Alvin J. PAYNAGANAN, Renlyn Ivy DG.

Group 1, Chem 27.1 TEJ, Ms. Jireh Joy E. Sacramento
February 21, 2012
I. Abstract

This determination of mixed alkali focused on the application of the acid-base titration in the
determination of the composition of alkali mixtures of bases, such as carbonate or bicarbonate, either alone or in
combination in a solution. This method is used for the determination of the safeness of water for irrigation and
the determination of the buffer capacity of natural waters. In the process, the unknown is titrated with a
hydrochloric acid solution, which was standardized by titration with a sodium carbonate primary standard. Then,
the two-indicator method was used, with phenolphthalein and bromocresol green as indicators. The said method
aimed to determine the two endpoints typically shown by the polyfunctional carbonate base, if applicable. The
data gathered predicted the presence of NaHCO3, Na2CO3 or NaOH and their percent composition in the
unknown. For a double-indicator method, the amount of carbonate and hydroxide present is taken from the
amount of hydrochloric acid required to reach the phenolphthalein end point. While the amount of bicarbonate
present is found by the amount needed to reach the bromocresol green end point.

II. Keywords
acid-base titration, mixed alkali, standardization, two-indicator method, carbonate, bicarbonate

III. Introduction given sample using a two-indicator neutralization

Alkalimetry is a specialized analytic use of titration with a standardized HCl solution as the titrant.
acid-base titration to determine the concentration of a
base. It also involves the determination of the quantity IV. Experimental
of real alkaline in alkali solutions or salts, either The standard HCl solution required in the
through gravimetric or volumetric analysis. experiment was prepared by diluting 8.23 mL of the
Carbonates and bicarbonates of alkali concentrated HCl solution in sufficient amounts of CO 2
mixtures are important industrial chemicals since they free distilled water to make a 1 liter solution. Three
are the salts of a strong base and a weak acid and are 0.20-0.21 g samples of the dried standard Na 2CO3
only readily available salts of these anions that are was transferred to three numbered 250 mL flasks
soluble in water. Presence of these compounds may where 250 mL of CO2 free distilled water and 2 drops
occur in different combinations that can be identified of bromocresol green indicator was added. These
using titrations that involve neutralization reactions three samples was then titrated with the 0.1 M HCl
with strong acids. solution until the color changed from yellow to light
The carbonates and bicarbonates in the blue. When the color changed, the solution was then
solution can be present in the forms CO 32-, HCO3- and boiled for 2 minutes and the flask was then covered
OH-. Neutralization titrations are employed in the with a watch glass or inverted beaker to retard the
quantitative determination of the constituents of a absorption of CO2 and allow the solution to cool. After
mixed alkali solution. Two methods can be used to cooling, the solution was supposed to return into its
determine a mixture of bases by titration: the two- yellow color. The titration was then continued until the
titration method and the two-indicator titration method. yellow color was changed into a distinct blue color.
In our experiment, we used the two-indicator method The molarity was computed and noted for future
to determine the carbonate and bicarbonate mixtures computations.
in the unknown. The two volumes of the endpoints of Three 0.20-0.21g samples was weighed by
the two indicators used will help in determining the difference into three 250mL Erlenmeyer flasks. 25 mL
carbonate and bicarbonate contents of the given of CO2 free water and 2 drops of phenolphthalein
sample. indicator was then added to the sample. The flask was
Indicators used in titrating your samples must immersed in an ice bath while it was being titrated with
be carefully chosen to be able to detect the endpoints the 0.1 M standardized HCl solution. The solution was
of the neutralization reactions employed in the slowly titrated with constant vigorous swirling until the
experiment. In this two-indicator titration, pink color just disappeared. The volume was then
phenolphthalein and bromocresol green was used. recorded on the table provided.
Phenolphthalein was used in titrating Na2CO3, while The titrated solution was removed from the ice bath
bromocresol green was used in titrating NaHCO3. and 2 drops of bromocresol green indicator was
The aim of this experiment is to determine added. It was then titrated once more with the 0.1 M
carbonate and bicarbonate mixtures present in the standardized HCl solution until the yellow color just

Chemistry 27.1 Determination of Mixed Alkali Page 1 of 4

turned into a distinct light blue color. The second Sodium carbonate (Na2CO3) is the most common
volume was also recorded in the table. reagent used for standardization of acid solutions and
is readily available in the primary standard grade,
V. Results which is recommended for higher accuracy. Since this
Table 1. Standardization of HCl Solution reagent is hygroscopic, it is necessary to dry it in an
Weight of Volume of Molarity of oven before weighing in order to achieve a uniform
Trial
Na2CO3 (g) HCl (mL) HCl (M) and reproducible composition. It can be cooled and
1 0.2085 38.2 0.103 stored in a desiccator, which contains desiccants that
2 0.2082 42.7 0.092 absorb moisture, to prevent any absorption by the
3 0.2057 39.0 0.0995 reagent.
Average Molarity of HCl (M): 0.0982 It must be noted that before weighing any
reagents that are previously heated, they must be
Sample Computations: cooled to room temperature. This is because, inside
the analytical balance, any heat transfer from the
1mol Na2CO3 2 mol HCl reagent to the air can cause the production of air
0.2085gNa2CO3
105.99 g 1mol Na2CO3 currents, which results in erroneous measurements.
0.103M HCl Also, weighing must be done by difference since it
0.0382 L solution
gives more accurate measurements, and also the
Table 2. Analysis of Unknown
closed interior of the analytical balance prevents any
mL HCl mL HCl Na2CO3 NaHCO3 moisture absorption on the reagent.
Trial After weighing, the primary standard Na 2CO3 can
(ph) (bcg) M %(w/v) M %(w/v)
1 9.1 9.4 0.036 0.38% - - then be titrated by the HCl titrant by either
2 9.1 9.5 0.036 0.38% - - phenolphthalein (ph), forming HCO 3- or by
Ave. % (w/w) Na2CO3 in the sample 0.38 %
bromocresol green (bcg), forming carbonic acid
Ave. % (w/w) NaHCO3 in the sample -
(H2CO3). The latter is preferred due to the formation of
a larger pH break, reducing indicator error, and a
Sample Computations:
larger volume of titrant, reducing the relative error in
measurement. After standardization, the HCl titrant
0.0982 mmol HCl 1mmol CO32 can be used to determine unknown mixtures.
9.1mL HCl
mL 1mmol HCl In the determination of carbonate, bicarbonate
1mmol Na2CO3 1 and hydroxide mixtures, it must be noted that HCO 3-
2
0.0357 M Na2CO3 and OH- cannot coexist together since they react to
1mmol CO3 25mL solution
form CO32-.
0.0357mol Na2CO3 1L 105.99 g HCO3- + OH- -> CO32- + H2O
100 0.378%
L 1000 mL 1mol Na2CO3
From this, we can also say that the three
VI. Discussion constituents cannot coexist together because of the
Determination of carbonates (CO32-), previous reaction, resulting in CO32- and the excess
- -
bicarbonates (HCO3 ) and hydroxides (OH ) in a basic between HCO3- and OH- to be in solution. The five
mixture involves the titration of the mixture with a possible combinations, considering the above
strong acid using either a two-indicator method or a conditions are: CO32-, CO32-/OH-, CO32-/ HCO3-, OH-
two-titration method. In the two-indicator method, one and HCO3-.
titration set-up is used for the determination of two This determination involves the titration of the
equivalence points. After the first endpoint has been unknown with the HCl titrant. The indicators used for
detected using an indicator, another indicator is added this experiment are phenolphthalein (pKa = 9.3), which
to the analyte in order to detect the second endpoint. detects the endpoint of the first titration of CO 32- to
In the two-titration method, two titration set-ups are HCO3-, and bromocresol green (pK a = 4.8), which
used. For each set up, an endpoint is detected using detects the endpoint for the second titration of HCO 3-
its corresponding indicator. to H2CO3. Both of these indicators are chosen since
For this experiment, hydrochloric acid (HCl) was their indicator range (ph: 8.3-10 bcg: 3.8-5.4)
used as the titrant, since, like other strong acids, it coincides well with the pH break they detect. (pH
gives a large Ka in titration. Also, its dilute solutions are break for CO32- to HCO3- 7-10; pH break for HCO 3-
stable, it has very lttle oxidizing or reducing power, to H2CO3 2-6) There is a third pH break for titration
plus the chloride ion does not precipitate with most of OH- to H2O (around pH 11.34) but it is too small to
cations. The drawback for HCl is that it is not a be properly detected by any indicator.
primary standard and must be standardized to
determine its exact concentration.

Chemistry 27.1 Determination of Mixed Alkali Page 2 of 4


ph
bcg
Figure 1. Titration curve of CO32-, with HCl, showing indicator ranges
of phenolphthalein and bromocresol green
In the first titration reaction:
HCl(aq) + Na2CO3(aq) -> NaHCO3(aq) + H2O(l)
the analyte is expected to become colorless from a
pink color and HCO3- will predominate in the solution.
This reaction is a neutralization reaction and therefore,
is exothermic. Also, the solubility of the carbon dioxide
(CO2) gas formed by CO32- is higher at low
temperature. From these statements, titration inside
an ice bath is recommended. This would not only push
the equilibrium forward, making a higher pH break, but
also prevent a decrease in CO32- concentration.
H2CO3(aq) + H2O(l) + CO2(g)
bcg
Figure 2. Titration curve of CO32-, with HCl, showing the effect of
boiling the solution before second equivalence point
The second titration reaction:
HCl(aq) + NaHCO3(aq) -> NaCl(aq) + CO2(aq) + H2O(l)
which is also the titration reaction for the
standardization reaction is expected to change from a
Chemistry 27.1 Determination of Mixed Alkali
yellow to a blue color in solution and H 2CO3 will
predominate and will decompose into CO2 and H2O.
When the endpoint is reached, boiling the solution
would remove produced and dissolved CO2,
enhancing the sharpness of the pH break. This also
removes the buffer produced by H2CO3 and HCO3-,
preventing the slow change in pH. If the solution
remained blue, then the endpoint has been detected,
but if the solution becomes yellow, the solution is
cooled. Temperature changes the equilibrium
constant, and therefore the equivalence point so it is
important to cool the solution first before continuing
titration in order to obtain the proper equivalence
point. Not doing this leads to an error. After cooling,
the analyte is titrated further until endpoint.
The constituents present in the solution can be
determined based on the relative volumes of acid
used in the titration of the mixture. After confirming the
presence of the species, the concentration of the
respective components can be known from the
amounts of acid consumed. Figure 3 summarizes the
volume relationships in the analysis of mixtures
containing hydroxide, carbonate, and hydrogen
carbonate ions.
Relationship between Vph
and Vbcg in the Titration of
Constituents in Sample
an Equal Volume of
Sample
NaOH Vph > 0 Vbcg = 0
Na2CO3 Vph = Vbcg
NaHCO3 Vph = 0; Vbcg > 0
NaOH, Na2CO3 Vph > Vbcg
Na2CO3, NaHCO3 Vph < Vbcg
Figure 3. Volume relationships in the analysis of mixtures containing
hydroxide, carbonate or hydrogen carbonate Ions for a double-
indicator method
It is important that for the whole experiment, only
CO2-free distilled water must be used since dissolved
CO2 in water produces carbonic acid, which
dissociates, producing CO32- as one of its products.
H2O(l) + CO2(g) -> H2CO3(aq)
This would give a positive error to the final
amount of CO32- determined. CO2-free distilled water
prevents that problem. Also, to prevent any CO 2 to be
dissolved in the solution all containers must be sealed
at all times.
Even though we employ methods to prevent CO 2
gain or CO2 loss, we cannot fully protect the solution
from the atmosphere, giving a positive error, and we
cannot fully prevent the loss of dissolved CO 2 resulting
in a negative error.
Another error would be the misreading of the
color change at endpoint, along with the indicator error
produced by the indicators, which both indicator
ranges border the pH breaks they detect. Also,
Page 3 of 4
a wrong amount of indicator can be a cause for error Hargis, L. G. (1988). Analytical chemistry: principles
because indicators also contribute to the pH of the and techniques. NJ, USA: Prentice Hall.
solutions since they are also acidic or basic.
Another important point is that both calculations
of amount of carbonate and hydroxide are based on We hereby certify that we have given substantial
two measurements, which means final error can be contribution to this report.
twice as large as in the case of simple titration with
one end point.
The error that is produced from the
standardization of HCl is carried over to the
determination of unknown, stacking to the final error LOGRONIO, Alvin J.
obtained. Air locks that are hidden, or produced during
titrations is also a source of error. Error that is
obtained from not fully transferring 100% of the solids
or liquids to other containers is very common.
Accidental spills and leaks from burettes, even in a PAYNAGANAN, Renlyn Ivy D.G.
small amount can cause errors in the final values
obtained. Many more sources of error can be
obtained, so it is very important to be careful when
doing the experiment, in order to prevent them.

VII. Conclusions and Recommendations

Determination of mixed alkali is done through

acid-base titration of an unknown alkali mixture, such
as a carbonate and bicarbonate mixture, with a
standardized acid titrant such as hydrochloric acid.
This standardization is done through the titration of a
primary standard analyte, such as sodium carbonate
with the acid titrant in order to determine its
concentration. An unknown is then titrated against the
acid titrant with two indicators either on one setup or
on different ones to obtain the volume needed in order
to reach each of the equivalence points for the base.
These volumes would then determine what the
components of the mixture are and how much of each
component is in the mixture.
The final value for this experiment has a relative
error of around 3% compared to the theoretical data.
This error can be minimized by better controlling
the environment to prevent CO2 loss or addition or by
changing bromocresol green to methyl orange since
its pKa (3.47) is nearer to the pH at equivalence point
(4.03) compared to bromocresol green (4.8) and
would give a lower indicator error.

VIII. References
ChemBuddy. (2009, September 6). Warder titration -
simultaneous determination of sodium hydroxide
and carbonate. Retrieved from:
http://www.titrations.info/acid-base-titration-
sodium-hydroxide-and-carbonate

ChemBuddy. (2011, May 25). Titration and titrimetric

methods - sources of errors. Retrieved from:
http://www.titrations.info/titration-errors

Chemistry 27.1 Determination of Mixed Alkali Page 4 of 4