EXPERIMENT 3:

Determination of
Mixed Alkali
BY:
Galan,Kyla Monique
Miguel,Raphael

Objectives
At the end of the experiment, the student
should be able to:

Prepare a standard hydrochloric acid solution

Determine the bicarbonate and carbonate

content in a given sample

Introduction
The process of determining the
quantity ofreal alkaline in alkali
solutions orsalts, either through
gravimetric orvolumetric analysis is
called alkalimetry.
Most alkalimetric procedures are
performed by titration of a carbonate
solution with a strong acid (HCl or
HNO3) until a desired color change is
achieved.

Introduction
The concentrations of the alkali
analytes are determined by
neutralization titrations which
endpoints are observable with the use
of indicators.
The determination of mixed alkali
requires a double indicator titration
wherein phenolphthalein, a base
range indicator, and methyl red or
bromocresol green, an acid range
indicator, are used.

Indicators
Methyl Red
pH interval: 4.2-6.3
Color of acid form:red
Color of base form:yellow

 Phenolphtalein
pH interval: 8.3- 10.0
Color of acid form:colorless
Color of base form:pink

Introduction
The carbonates and bicarbonates ofalkali
mixtures are the salts of a strong base and a
weak acid and are soluble in water making
up significant portions of important
industrial chemicals.
Carbonate mixtures may contain Na2CO3,
NaHCO3 and NaOH eitheralone or
combined with the others. Only 2
components are allowed to coexist
since the third component would be
consumed or eliminated in the reaction.

Introduction
There are 5 possible systems that can
exist:
1.

Na2CO3 only,

2.

NaOH only,

3.

NaHCO3 only,

4.

Na2CO3, & NaHCO3, and

5.

Na2CO3, & NaOH.

Methodology
A. Preparation of 0.1
MThe
HCl
volume of the
concentrated
hydrochloric acid (HCl)
needed to prepare 1L of
0.1 M solution was
calculated.

The measured amount of

concentrated HCl was
transferred into a 500mL
beaker containing 300mL of
CO2-free (pre-boiled) distilled
water.

B. Standardization of 0.1 M
HCl
For two hours,
about 5 g of
primary-standardgrade Na2CO3 was
dried at 1100C

It was then
cooled in a
dessicator

.20-.21 g of the primary

standard grade reagent
was dissolved in a 1-L
volumetric flask with
pre-boiled water

Dissolve each sample in

25 ml distilled water and
2 drops of methyl red

The flask was covered

with a watch glass and the
solution was allowed to
cool.

Thetitrationwas
continued until a sharp
yellow-to- orange color

Each sample was titrated

with the 0.1 M HCl solution
until the indicator has
changed gradually from
yellow to definite orange

The titration was stopped

after the change in color
and the solution was
boiled gently for 2
minutes.

The molarity of the titrant

was calculated from the
recorded volumes.

C. Analysis of the Unknown

Unknowns were prepared
for analysis

Three 0.2-0.21 g samples of

unknown are weighed

25 mL of CO2 -free distilled

water were added with 2 drops
of phenolphthalein

The solution was immersed in an

ice-water bath and was titrated
slowly, with constant vigorous
swirling, until the pink color
disappeared

The % (w/w) Na2CO3 and

NaHCO3 were calculated.

Two drops of methyl red indicator

were added and the titration was
continued as in steps 4-7 of the
standardization procedure.

The solution was removed

from the ice-bath.

The volume of the titrant

used was recorded.

Results
Standardization of HCl
Na2CO3 + 2HCl H2CO3 + 2Na+ +
2Cl- Weight of
TRIAL
Volume of
Molarity of
1
2
3

Na2CO3 (g)

HCl

HCl

.203
.202
.201
Average
Molarity

38.3 mL
37.6 mL
37.9 mL

0.100 M
0.101 M
0.100 M
0.1003 M

Sample Computation:
0.203 g Na2CO3

1 mol Na2CO3
106 g Na2CO3

HCl

.0038302 mol HCl = 0.108 M

.0383 L

2 mol HCl
1 mol Na2CO3

= 0.0038302 mol

Analysis of the Unknow

TRIAL

Volume of HCl Volume of

(phenolphthale
HCl
in endpoint,
(methyl
mL)
red
endpoint,
mL)
2.6
22.3

% (w/w)

% (w/w)

Na2CO3

NaHCO3

13.6%

81.8%

2.7

22.4

14.2%

82.2%

3.6

22.9

15.5%

81.4%

average concentration of Na2CO3 by weight is 15.5%

average concentration of NaHCO3 is 81.4%

Discussion
Standardization
- Determination of the concentration of a
solution by calibration, directly or
indirectly, with a primary standard
- the process of determining the exact
concentration (molarity) of a solution,
commonly through titration wherein an
exact volume of one substance is reacted
with a known amount of another
substance

Discussion
Standardization is required in
titrimetric processes for higher accuracy
and better results in the analyses
involved
In this experiment, the standard
solution is the sufficiently stable HCl
(due to its complete ionization in water)
while the primary standard is the
anhydrous sodium carbonate

 The

composition of the solution can be

deduced from the relative volumes of
acid needed to titrate equal volumes of
the sample. There can be 5 cases:

The 1st case contains NaOH only.

NaOH + HCl NaCl + H2O

Vph = Vbcg/mr

This is a strong acid-strong base titration. NaOH is

the only alkali present so it has only one equivalence
point. Methyl red is not needed anymore since
neutralization
of
NaOH
is
reached
during
phenolphthalein titration and only HCO 3- is detected by
methyl red.

The 2nd case contains Na2CO3

only.

Na2CO3 + HCl NaHCO3 + NaCl

HCO3- + H30+ H2CO3 + H2O

Vph = Vbcg/mr

There are two endpoints in this case wherein the

volume of the titrant (HCl) for the phenolphthalein
endpoint will be equal to the volume of titrant (HCl)
from phenolphthalein to the methyl red endpoint since
the HCO3- detected by methyl red are only hydrolyzed
CO32-.

The 3rd case contains NaHCO3 only.

NaHCO3 + HCl NaCl + H2O + CO2
** H2O + CO2 H2CO3

Vbcg/mr > 0
Vph 0

The volume of phenolphthalein titration is zero. The

concentration of HCl is equal to the concentration of
NaHCO3 after methyl red endpont.

The 4th case contains Na2CO3 and NaOH.

Na2CO3 + HCl NaHCO3 + NaCl
NaOH + HCl NaCl + H2O

Vph > Vbcg/mr

Although HCO3- and OH- are both present in the sample, they
will not neutralize since they wontbe present at the same time.
Intially only OH- and CO32- will be present and would determine the
amount of titrant needed for phenolpthalein endpoint. At the
phenolphthalein endpoint, all OH- are neutralized while CO32- are
hydrolyzed into HCO3-. The converted HCO3- ,only, will determine
the amount of titrant needed for methyl red end point.

The 5th case contains Na2CO3 and NaHCO3.

Na2CO3 + HCl NaHCO3 + NaCl
NaHCO3 + HCl NaCl + H2O + CO2
** H2O + CO2 H2CO3

Vph < Vbcg/mr

The phenolphthalein titration volume is less than the

methyl red titration since only the CO 32- will be detected
by phelophthalein while the initial HCO3- and the
hydrolyzed CO32-, HCO3-, will be detected by methyl red.

Conclusion
The unknown substance provided was a combination
of sodium carbonate (Na2CO3) and sodium
bicarbonate (NaHCO3) since half the volume of HCl
used to reach the methyl red end point was greater
than the volume of HCl used to reach the
phenolphthalein end point. The average concentration
of Na2CO3 by weight is 15.5% while that of NaHCO3 is
81.4%

REFERENCES
Hargis ,L. Analytical Chemistry:
Principles and Techniques. Prentice Hall (1988)
Skoog, et al. Fundamentals of Analytical Chemistry. 8th
edition
7.0 EXPERIMENT ON THE DETERMINATION OF
ALKALINITY OF WATER (1st ed.). Retrieved from
http://nitttrc.ac.in/four%20quadrant/eel/quadrant
%20-%of Arts and Sciences, University of the
Philippines Manila.