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 (electron-pair donors) in which a coordination

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