EXPERIMENT 7: QUANTITATIVE DETERMINATION
OF TOTAL HARDNESS IN DRINKING WATER BY
COMPLEXOMETRIC EDTA TITRATION
B.F. SOSA and G.P. FORTU
1 1
INSTITUTE OF BIOLOGY, COLLEGE OF SCIENCE
1
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY 1101, PHILIPPINES
DATE SUBMITTED: 30 MARCH 2016
DATE PERFORMED: 18 MARCH 2016
ANSWERS TO QUESTIONS
1.! What is water hardness and why is it
expressed as ppm CaCO3?
Water hardness is classified as the
concentrations of calcium and magnesium ions
and it normally goes beyond the concentrations
of other meta ions. It is presently expressed as
ppm of calcium carbonate because the overall
concentration of all multivalent cations in the
water sample is equivalent to the concentration of
calcium carbonate thus it represents the water
hardness of the sample. Ppm of calcium
carbonate is also equivalent to the hardness of
100ppm that contains an equivalent of 100g
calcium carbonate in 1 million grams of water. It
is also equivalent to 0.1g in 1L of water.
2.! How does complexometric titration
work?
In this experiment, it is a volumetric analysis
that produces an endpoint that is made visible
because of the formation of a colored complex
and it is called complexometric titration. It is to
determine the water hardness of the Viva mineral
water. Usually, it is used to know the metal ion
contained in a solution. In this titration, a solution
with a free metal ion is titrated using a solution of
the chelating agent, titrate until all the metal ions
are complexed completely, this will result to the
endpoint using a ligand indicator that produces a
colored complex containing the metal ion.
3.! Why was EDTA used as complexing
agent/ -titrant?
Since compexometric titration is used,
titrants used for metal ions like calcium ion
analyte are complexing agents. This will result to
the reaction of the metal cation with a Lewis Base
(electron-pair donors) in which a coordination
complex is formed. This coordination compound
has a complex ion, a species with a central metal
atom, a transition metal enclosed to several
Ligands. The complexing agents of the metal
cations are the ligands acting like it. For
complexation, multidentate ligands also known
as chelating agents gives off more than a single
electron pair and these produces multiple
coordinate bonds to bond the ligand and the
metal cation. The chelates then are very stable
thus having large formation constant. EDTA is a
important chelating agent. Almost all metal ions
produces complexes with the tetrabasic form
(acid form) of EDTA. It is a hexadentate ligand, It
means one electron pair is given off by each acid
oxygen and each amine nitrogen to the electron.
Acid dissociation is needed so that EDTAs
electron pair of carboxylic groups to be available
to the metal cation therefore the need of a high
pH but at very high pH, most metal ions react
and form complexes with hydroxide ions. This
then states that theres a pH maximum for EDTA
complexation to occur. For any chelating agent
and metal ion, there is a corresponding pH for the
titration that depends on pKa. For calcium ions,
it has a pH above 8 in which a
ammonia/ammonium buffer is used for its ph
maintenance.
4.! Why were MgCl2 6H2O crystals and
NaOH pellets added in the precipitation
of EDTA solution?
The reason behind adding MgCl2 6H2O
crystals and NaOH pellets is for us to determine
water hardness of the sample by determining the
concentration of calcium carbonate easier. This is
also known as displacement titration, the process
of determining calcium ions via EDTA but EDTA
is very slow in binding calcium ions. This is the
reason behind adding another metal ion, usually
Magnesium but in the form of a salt, this will help
the binding to be faster that will form metal-
EDTA complex. Ca-EDTA complex is more stable
than the metal-EDTA formed. Then Mg ions will
be replaced by the free calcium ions in the
solution that will make the formation of Ca-
EDTA complex possible. This formation will
result to free magnesium ions that will be easily
titrated. The original concentration of calcium
ions is equal to the free magnesium ions.
5.! Why was HCl added in the preparation
of CaCO3 solution?
There is the need to add HCl in the
preparation of calcium carbonate because it will
help dissolve calcium carbonate easier. This will
be used as the primary standard that will help
determine the concentration of the solution thus
leading to determining the water hardness of the
sample.
6.! What are the pertinent chemical
equations involved during titration?
Explain how the color of the solution
turns to blue using the stability of
complexes involved in the titration.
The equation involved in making the
primary standard is
"#"$% + 2(")* "#"), + "$, + (, $
dissolving the calcium carbonate that will be
used in titration. From the free Calcium ions this
will determine the concentration of the EDTA
solution. The equation of the titration will be
"# ,- + ./0123 "#./01,3
With the addition of EDTA to calcium, it will
form the chelate Ca-EDTA (refer to no. 3). This
solution is colorless but to be able to recognize the
endpoint, an indicator is needed called
eriochromschwartz-T or EBT, the equation is
23 ,3 ,3
45*67 + ./01 * 45./01 + )7
red blue
Since calcium is not stable with the complex
formation in the EBT indicator, the titration will
not produce a sharp indicator in the endpoint
thats why magnesium is used in the titration
because it is stable with the EBT indicator, this is
known as displacement titration (refer to no. 4).
"#)7 + * 45,3 "#9 ,3 + 45)73
7.! What is the importance of maintaining
the pH at 10 and choosing NH3-NH4Cl
as buffer?
It is important to maintain a pH of 10 because
EDTA and EBT both displays polyprotic
properties that shows being unstable. It is also
because only one endpoint needs to be observed.
Also a pH of 10 is enough for a sharp endpoint,
too much buffer that results in resistance to
change in pH will produce a weaker endpoint
thats why addition of buffer must be just
enough. Another reason is there is a minimum
solution pH required for both metal ions of
calcium and magnesium to complexate with
EDTA. Calcium needs 7.3 while magnesium
needs 10. Therefore the minimum solution pH is
10. This supports the stability of tha Ca-EDTA
solution and any magnesium ion will not
interfere the reaction. Since the pH that needs to
be maintained is 10, the buffer that should be
used id NH3-NH4Cl.
8.! What are the possible resources of error
and their effect on the calculated
parameters? Rationalize.
There are possible sources of error in this
experiment, it is when there is too much buffer in
the system. This will make the solution be too
resistant to the change in pH thus there will be a
dull change of color in the indicator or worse, it
will not show any indication of change.
Therefore, this will affect all the calculations
needed. The water hardness that will be
computed will not be accurate because the
volume of the water sample will be wrong.
Another is an error in solution preparation that
will yield to mistakes in almost all of the
calculations since solution preparation is the root
of the experiment. Another is over titration that is
the most common error in titration, with this
error, the experiment should be repeated because
it will not be fixed.
REFERENCES
[1] Skoog, D. (2014). Fundamentals of Analytical
Chemistry. (p. 401, p.434, p.436). Belmont, CA:
Brooks Cole, A Part of Cengage Learning.
[2] Zumdahl, S.S., & Zumdahl S.A. (2012).
Chemistry. (pp.983-985). Belmont, CA: Brooks
Cole, A Part of Cengage Learning.
[3] Silbeberg, M. (2010). Principles of General
Chemistry. (pp.763-764, 773). New York, NY: The
McGraw- Hill Companies, Inc.
APPENDIX A: SAMPLE CALCULATIONS

Molarity of primary standard

5*:;< %*@ABC;D =F)*"#"$% 1000=J

*KF)*:;<
=)*:;<* 15*:;< GH*"#"$% 1*J
= 4*"#"$%
LC7#)*KF)*MFBNC75*:;<

0.50005*:;< 0.9995*"#"$% 1=F)*"#"$% 1000=J

0.005J
250=)* 15*:;< 100.0865*"#"$% 1*J
0.05J
= 1.996223196103% 4*"#"$%

Concentration of the standard EDTA solution in molarity

Average net volume of EDTA: 2.367mL

VWWXY*Z[\] V*
KF)*FL*MFBNC75*"# 66 :;<**4*"#"$% =*M EDTA
VWWXY*^_^`a Wb*Z[\]
3% VWWXY*Z[\] V*
10.0=J*"#"$% *1.99622319610 4*"#"$% = 8.433811561103% M
VWWXY*^_^` ,.%cdWb*Z[\]
a
EDTA

Titer of the solution as mg CaCO3 per mL of standardized EDTA solution

==F)*./01 1==F)*"# ,- 1==F)*"#"$% =5*"#"$%

,-
GH*"#"$% = * *FB*"#"$% ;C;fB
=J*./01 1*==F)*./01 1==F)*"# =J*./01

0.01996223196*==F)*./01 1==F)*"# ,- 1==F)*"#"$% 100.086=5*"#"$%

*
2.367*=J*./01 1*==F)*./01 1==F)*"# ,- 1*==F)*"#"$%
=5*"#"$%
= 0.844*
=J*./01

Total hardness of water sample as ppm*"#"$%

Trial 1 of Sample analysis:

7f;*KF)*./01**;C;fB = =5*"#"$%
=5*"#"$%
7.8*=J*./01*0.844* = 6.5832*=5*"#"$%
=J*./01
Wh*^_^`a VqqqWb
= ppm
iXY*Xj*k_lmn*o_WpYm Vb
c.rs%,*Wh*^_^`a VqqqWb
= 131.664 ppm "#"$%
rq*Wb Vb

Total cation content based on the concentration of Ca and Mg on the water bottle

ppm Mg + ppm Ca = ppm Ca

GH*"# ,- + GH*45,-
@@=*"#"$% = @@=*"# ,-
GH*"#"$%
5 5
40.078 =F) *"# ,- + 24.305 =F) **45,-
131.664*@@=*"#"$% 5 = 84.7*@@=*"# ,-
100.086 =F) *"#"$%
Relative standard deviation

Trial 1 2 3
Total Hardness 131.664 ppm 129.976 131.664

(u3uv )x
S= = 0.9745672544
y3V
{
v|} uv
z =* = 131.1013333
y

~/ = *1000@@; = 7.43*@@;
z
Confidence limit (95%)

lo
Confidence limit = z = 130.45 131.75
y