Sunteți pe pagina 1din 8

QUANTITATIVE DETERMINATION OF TOTAL HARDNESS

IN DRINKING WATER BY COMPLEXOMETRIC EDTA


TITRATION
A. P. AMBA1 and N. J. C. TANGGAAN2
1,2NATIONAL

INSTITUTE OF GEOLOGICAL SCIENCES, COLLEGE OF SCIENCE


UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY 1101, PHILIPPINES
DATE SUBMITTED: 7 JULY 2015
DATE PERFORMED: 3 JULY 2015

ABSTRACT
Water is very vital in sustaining life because no organism is independent of water for survival. Humans
need water in a daily basis. About an average of 3 liters is recommended for daily water intake.
Drinking water which comes from below the ground dissolves calcium and magnesium from rocks and
the soil which makes the water hard. Water hardness is simply the amount of calcium and magnesium
dissolved in water. Hard water can be beneficial since it contains minerals that the body needs but it
also has disadvantages such as clogging of pipes when it builds up. The experiment aims to determine
the total water hardness of a water sample by complexometric titration. It involves the formation of a
complex through the reaction of the titrant and the analyte. Water samples of commercialized mineral
water, specifically Hidden Spring, were titrated with EDTA using Eriochrome Black T indicator.
Endpoint is indicated with a color change from wine red to clear blue. Through experimentation, it
was found out that the average total hardness of the mineral water sample was 187.29 ppm with a
percent error of 9.33% based from the theoretical value of the total water hardness that is 206.57 ppm
and a relative standard deviation of 12.67ppt. The calculated total hardness states that the mineral
water sample is hard which means that it has a high calcium and magnesium content.

INTRODUCTION
When astronomers search for life outside the
earth, they would first try look at the
presence of water because when there is
water, there might, just possibly, be life.
Water is vital in sustaining life. This is
because there isnt an organism in this world
that does not depend on water. There are also
other uses of water in our lives. We grow
plants using water, keep livestock using
water, and drink water. Water is even a part
of us. The human body contains about 70
percent water. [1] A certain amount of water
intake is necessary for humans to survive or
at least be healthy. Eleven to fifteen glasses or
approximately 2.7-3.7 liters is recommended

for daily intake of water. Drinking water is


primarily obtained from surface water or
groundwater which is then transported to
homes and other facilities to provide wider
and easier access to consumers. [2] However,
as the water is collected from below, it picks
up minerals from the rocks and soil such as
magnesium and calcium which then
contributes to water hardness.
The simple definition of water hardness is the
amount of dissolved calcium and magnesium
in the water. The more calcium and
magnesium dissolved in the water, the higher
the level of water hardness. One can observe
it by washing hands or the dishes. With hard
water, one requires more soap or detergent

to clean things because soap reacts with the


calcium forming soap scum. But hard water
can be beneficial to. Humans need minerals to
stay healthy and hard drinking water
generally contributes a small but significant
amount toward total calcium and magnesium
dietary needs. [3] Some studies even showed
that hard water can lessen heart illnesses and
provide calcium ions for bone growth. [4] But
it also brings setbacks especially in
residential settings. Minerals an build up in
pipes and block the water transport, causes
surfaces to be hazy as it leaves mineral
deposits behind, and produces soap curd
which reduces cleansing action of soaps and
irritates the skin. [5] Water hardness is
expressed in ppm CaCO3 although the
hardness is not entirely because of the
calcium.
In the experiment, a certain type of titration
called complexometric titration was used.
Complexometric titration is a form of
volumetric analysis in which the formation of
a colored complex is used to indicate the end
point of a titration. Complexometric titrations
are particularly useful for the determination
of a mixture of different metal ions in solution.
An indicator capable of producing an
unambiguous color change is usually used to
detect the end-point of the titration. In theory,
any complexation reaction can be used as a
volumetric technique provided that the
reaction reaches the reaction rapidly after
portion of titrant is added, interfering
situations do not arise, and a complexometric
indicator capable of locating equivalence
point with fair accuracy is available. [6]
Ethylenediaminetetraacetic acid (EDTA) was
used in the experiment. In a complexometric
titration, the analyte and the titrant react to
form
a
coordination
complex
[7].
Coordination compounds are complexes
consist of a transition metal as the central
atom bound to ions called ligands [8]. A
ligand could be any ion with a pair of
nonbonding electron. Ligands are classified as
monodentate, bidentate, or polydentate
depending on the number of electron pairs

they have that could attach to the metal ion


[8]. Bidentate or polydentate ligands can form
two or more bonds, respectively, to the metal
ion. Molecules that form multiple bonds to
the metal ion are called chelating compounds.
This chelate effect accounts for the higher
stability complex of the bidentate or
polydentate ligands than the monodentate
ones.
In the experiment, complexometric titration
was used to analyze the water sample using
ethylenediaminetetraaceticacid (EDTA) as
the titrant. EDTA is a hexadentate ligand
which means that it could form six bonds
with the metals in the water sample such as
the calcium or magnesium ions. This reaction
could then produce a coordination compound.
EDTA could give different numbers of
hydrogen depending on the pH required.
Calcium and magnesium react weakly with
EDTA; hence, the titration must be done in
basic solution. The experiment was then set
to achieve a constant pH of 10 for alkalinity.
To maintain this pH, EDTA should be fully
deprotonated to the form Y4-.Y is an even
shorter notation used by analytical chemists
for the EDTA.
Upon titration, EDTA, in this form, reacts with
both the calcium and magnesium ions in the
water sample as expressed in equations (1)
and (2).
(1)
(2)
At pH equal to 10, the Eirochrome Black T
(EBT) indicator was used and the endpoint of
the titration process was exhibited by the
color change from wine red to a clear blue. At
the endpoint, the ppm of CaCO3was measured
which consequently measured the total
hardness of the water sample.
METHODOLOGY
Firstly, the solutions that were needed for the
experiment were prepared, namely 500.0 mL
of 0.1000 M stock EDTA solution, 100.0 mL of

0.0500 M stock Ca2+ solution, and 250.0 mL of


1.0 M NH3-NH4+ with pH 10 buffer solution
obtained from NH4Cl solids and NH3 stock
solution. Then, 250.0 mL of 0.0100 M working
EDTA solution was prepared from the stock
EDTA solution and 50.0 mL of 0.0050 M
working standard Ca2+ solution from 0.0500
M stock solution.
For the standardization of the EDTA solution,
10.0 mL of the working calcium solution was
pipetted into each of three 250-mL
Erlenmeyer flasks and 75 mL of distilled
water was added to each flasks. 3 mL of
buffer solution was added, which was
followed with 2 drops of EBT indicator. The
flask was swirled. The initial volume of the
titrant was recorded. The calcium solution
was titrated until endpoint was reached,
which was a color change from wine red to
clear blue. The final volume was recorded and
the procedure was repeated for the other two
flasks.
For the analysis of the total hardness in
drinking water, a sample of drinking water
(in the case of this experiment, the brand was
Hidden Spring) was procured. Then, using a
50-mL volumetric pipette, 50.0 mL of the
water sample was measured and poured into
a 250-mL Erlenmeyer flask. The titration
steps in the standardization procedure were
followed, and this was performed in
triplicates.
RESULTS AND DISCUSSION
During the preparation of the stock EDTA
solution, MgCl26H2O crystals were added.
These crystals were added in order to achieve
a sharper endpoint. The EBT indicator forms
a complex with the magnesium ions, which
results to the wine red color in the solution.
The endpoint of direct calcium titration is not
that sharp compared to that of magnesiums
[9]. NaOH pellets were also added in order to
make the dissolution of EDTA faster. These
pellets convert EDTA into a more soluble salt,
therefore increasing the solubility of the
EDTA solution. Meanwhile, concentrated HCl

was added to the preparation of the stock


Ca2+ solution while it was heated to make the
dissolution of CaCO3 solids faster.
The pH of the analyte needs to be maintained
at pH 10. In order for EDTA to react with
metal ions, the hydrogens that are attached to
the carboxylate group in the molecule must
be removed. So this means that the solution
must be basic in order for the metal ions to
bond with EDTA [10]. This is why the pH
needs to be maintained at a basic level. A
NH3-NH4+ buffer solution was chosen as the
buffer because this is the solution that can be
easily prepared at pH 10.
The indicator used in the titration of the
analyte was Eriochrome Black T, or EBT. It is
widely known for its use in determining the
water hardness in a water sample, since it
bonds with magnesium and calcium, which
then produces a wine red solution [11].
For the chemical equations that will be
mentioned, EDTA will be denoted with the
letter Y while the indicator EBT will be
denoted with In. For the standardization of
the EDTA solution, the primary standard that
was used was calcium carbonate. Since it only
contains calcium ions and no magnesium ions,
the EBT indicator will then form a complex
with the calcium ions and forms a wine red
solution, which is shown in the equation
below (3):
Ca2+ + HIn- CaIn- + H+ (3)
It is noted that not all calcium ions form a
complex with the indicator. The free calcium
ions then form a complex with EDTA during
titration, shown in the equation below(4):
Ca2+ + Y4- CaY2- (4)
When all the calcium ions are consumed, the
calcium in Ca-EBT will then form a complex
with EDTA to form Ca-EDTA, since Ca-EDTA
has a higher formation constant (Kf = 5.0 x
1010) than Ca-EBT. The solution then returns
to its acidic form since it is titrated with EDTA

and then forms a clear blue solution


(endpoint), as shown in the equation below
(5):

interval of 187.29 5.95 ppm at 95%


confidence level. This was also classified as
very hard water.

CaIn- + Y4- + H3O+ CaY2- + HIn2- + H2O (5)


(wine red)
(clear blue)

The percent error of the experimental value


was found out to be 9.33% from the
theoretical value. Possible sources of error
could be overtitration of the analyte, since the
time it takes for EDTA to react is high, so the
titration process should be done slower. The
other ions that will also bond with EDTA are
also not accounted in the experiment, which
could be a source of error.

In the analysis of water sample, EBT will form


mostly with magnesium ions than it does
with calcium ions, since Mg-EBT (log Kf = 7.0)
has a higher formation constant than Ca-EBT
(log Kf = 5.4)[12]. Upon titration of the
sample, EDTA forms a complex with the free
calcium, shown in equation (4) and
magnesium ions, which is shown in the
equation below (6):
Mg2+

Y4-

MgY2-

(6)

When all the free metal ions have formed a


complex ion with EDTA, the magnesium in
Mg-EBT will then react with EDTA, since CaEDTA and Mg-EDTA have a higher formation
constant than Mg-EBT. The solution then
returns to its acidic form since it is titrated
with EDTA which then results to a clear blue
solution (endpoint), which is shown in the
equation below (7):
CaIn- + Y4- + H3O+ CaY2- + HIn2- + H2O (5)
(wine red)
(clear blue)
The molarity of the standardized EDTA
solution was found out to be 7.84 x 10-3 M
and a titer of 0.7847 mg CaCO3 per mL of
EDTA. Through these values, the calcium
carbonate content of the water sample can
then be obtained.
The theoretical ppm of CaCO3 or the total
cation content was obtained based from given
values from the bottle of the water sample. It
was found out that the theoretical value was
206.57 ppm CaCO3, which was classified to be
very hard water.
The concentration of CaCO3 obtained from the
titration of the sample was found out to be
187.29 ppm, with a relative standard
deviation of 12.67 ppt and a confidence

SUMMARY AND CONCLUSIONS


Determination of water hardness is
important for awareness. Water hardness can
be
quantitatively
determined
by
complexometric titration. The volume of
EDTA utilized in titration was used to
determine the amount CaCO3 in the sample
because of a complex formation reaction that
occurs.
The result of the experiment showed that the
water sample, having an average CaCO3
concentration of 187.29 ppm which slightly
differs with the theoretical value of 206.57
ppm, is hard. This value needs to be
considered if the water sample is to be used
for industrial purposes.
Errors in the calculated result could be
attributed to the possible miscalculation of
the EDTA concentration that could have
affected the calculated CaCO3 concentration.
Also, there could have been errors in titration
especially in volume measurements that
made the calculated 187.29 ppm of the
calcium carbonate lesser than the theoretical
value. Also, the tolerance of the glassware and
instruments used may be a possible source of
errors in the experiment.
Although the calculated and theoretical value
hardness proved that the water sample is
hard, it is highly recommended to conduct
more experiments like to test hardness which
gives
more
accurate
results.
The

standardization of EDTA and the titration of


the sample itself should be done carefully to
achieve the most accurate concentration
leading to a more accurate result.

[7] "Complexometric Titration." , EDTA


Titration. N.p., n.d. Web. 06 July 2015.

REFERENCES

[8] "Transition Metals." Coordination


Complexes and Ligands. N.p., n.d. Web. 06 July
2015.

[1] Atteberry, Jonathan. "Why Is Water Vital


to
Life?"
HowStuffWorks.
HowStuffWorks.com, n.d. Web. 06 July 2015.
[2] Water Quality Association. (May 2, 2000).
Retrieved
8
May
2014
from:
http://www.wqa.org/sitelogic.cfm?ID=477
[3] Water Quality Association. (May 2, 2000).
Retrieved
8
May
2014
from:
http://www.wqa.org/sitelogic.cfm?ID=477
[4] Lenntech. "Water Treatment Solutions."
Calcium (Ca) and Water. N.p., n.d. Web. 06
July 2015.
[5] Forbes, Rhomylly. "The Effects of Drinking
Hard Water." EHow. Demand Media, 12 Dec.
2010. Web. 06 July 2015.
[6] Schwarzenbach, Gerold, and Harry Irving.
Complexometric Titration. London: Methuen
and, 1960. Web.

[9] Kundu, P.C. Complexometric Titration of


the Sum of Calcium and Magnesium Using
Aluminon as Metal Indicator. Chemical
Laboratory, Presidency College, West Bengal,
India. 1962. Retrieved 5 July 2015.
[10] Southway, C. APCH231: Chemical Analysis
Complexometric
Titrations
EDTA.
ND.
Retrieved 5 July 2015.
[11] Young, A., Sweet, T. Complexes of
Eriochrome Black T with Calcium and
Magnesium. Ohio State University. 1954.
Retrieved 6 July 2015.
[12] Hulanicki, A., Glab, S. Complexometric
Indicators: Characteristics and Applications.
International Union of Pure and Applied
Chemistry. 1983. Retrieved 7 July 2015.

APPENDIX
Sample Calculations:
Molarity of Working Solution of CaCO3:

Standardization of EDTA solution:


Trial 1:

Trial 2:

Trial 3:

Average M EDTA:

Titer in mg CaCO3 per mL EDTA:

ppm CaCO3 from ppm Ca:

ppm CaCO3 from ppm Mg:

Total Water Hardness:

Sample Analysis:
Trial 1:

Trial 2:

Trial 3:

Average ppm CaCO3

Relative standard deviation (RSD):

Confidence Interval:

Percent Error:

S-ar putea să vă placă și