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EXPERIMENT VI

COMPLEXOMETRIC METHODS OF ANALYSIS:


DETERMINATION OF CALCIUM ION IN A HARD-WATER SAMPLE
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INTRODUCTION
Complex-forming titrations (sometimes called complexometric methods) have been used
for more than a century. The rapid growth in their application began in the 1940's with the
development of a class of coordination compounds called chelating agents. These are generally
aminopolycarboxylic acids which can form a stable complex (a chelate) with many metal ions.
The formation of a stable complex allows for the titration of a metal ion by the complexing
compound provided a suitable indicator is available. In this experiment you will determine the
hardness of water (the combined [Ca2+]/[Mg2+] content of water) by titration with Ethylenediaminetetraacetic acid (EDTA) using either a calcium ion-selective electrode or a chemical
indicator to provide an end-point signal.
In many jurisdictions the available natural water contains high concentrations of calcium
and magnesium ions. While the presence of these ions in the water supply poses no health
hazard they do have a profound effect on the efficacy of soaps. Soap in water with a high
calcium or magnesium content will not lather and as a consequence their cleaning ability is
inhibited. Water with such a high calcium/magnesium content is termed Hard Water. For this
reason local municipal water supplies are continually monitored to determine the
calcium/magnesium content of the water in order to avoid this problem. The preferred analytical
method for this determination is titration of a sample of water using EDTA as the titrating agent.
The so called "Hardness of Water" is generally reported in parts per million (ppm) (mg/L or
g/mL) CaCO3 even through some unknown fraction of the material present is Mg2+.
THEORY
Most metal ions [the exceptions are the alkaline (Group I) metals] react with electronpair donors to form coordination compounds. The electron-pair donor is more generally called
the ligand. The ligand must have at least one pair of unshared electrons available for bond
formation. The type of bond formed is termed a covalent bond. The number of covalent bonds a
metal ion forms with the ligand is called its coordination number. The resulting compound, or
complex, formed between the metal ion and the ligand may be electrically positive, negative or
neutral. Particularly stable complexes are formed when the ligand can form more than one
covalent bond with the metal ion. A class of such ligands are the so called chelating agents
(from the Greek khete meaning claw). A complex is produced when a metal ion coordinates
with two (or more) donor groups of a single ligand to form a five or six membered hetereocyclic
ring with the metal ion. A ligand that has a single electron-donor group is called a unidentate
(single-toothed from the Latin dentatus meaning tooth) ligand, bidentate (2 electron-donor
groups), tridentate (3 electron-donor groups) etc., chelating agent.
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Aminopolycarboxylic acids are a group of compounds which form very stable chelates
with many metal ions. Ethylenediaminetetra-acetic acid (EDTA) is one such aminopolycarboxylic acid and is widely used to determine metal ions. The structure of EDTA is shown in
Figure 1 below:
CH2-COOH

HOOC-H2C

:N

CH2

CH2

HOOC-H2C

N:
CH2-COOH

Figure 1
EDTA is a hexadentate ligand and forms complexes with many metal ions the general
structure of which is shown in Figure 2 below:

Figure 2

For convenience EDTA is more generally written as H4Y where the "H" correspond to the
acidic proton of the carboxylic acid group and Y is the rest of the molecule. In solution EDTA
can undergo the following dissociations:

H4Y + H2O
H3Y- + H3O+

H3Y- + H2O H2Y2- + H3O+

H2Y2- + H2O HY3- + H3O+

HY3- + H2O Y4- + H3O+

It is the Y4- species that complexes with metal ions to form a variety of electrically
charged species.

Ag+ + Y4-
AgY3
Cu2+ + Y4- CuY2
Al3+ + Y4- AlY-

Notice however that in all cases the metal ion and the EDTA ligand always react in a 1:1
stoichiometry regardless of the charge on the ion. (This is an important fact to remember when
calculating results from an EDTA titration).
A number of indicators are available for use in EDTA titration the most common is
Eriochrome Black T. Eriochrome Black T undergoes the following color transition at the
equivalence point.
wine-red pure blue
This color change results from the conversion of the indicator complexed with Mg 2+,
MgIn-, which is red, to free indicator, In3-, which is blue, at or just beyond the equivalence point.
The EDTA first complexes all free Ca 2+ and Mg2+, the small amount of Mg2+ bound to the
indicator is titrated last (it is less available simply because it is complexed with the indicator)
and the color change results:
MgIn - Y 4- MgY 2- In 3red

blue

DETERMINATION OF THE HARDNESS OF WATER


USING A CHEMICAL INDICATOR
PROCEDURE
Preparation of One Liter of Approximately 0.01M EDTA
Weigh approximately 4g of disodium ethylenediaminetetraacetic acid dihydrate into a
clean 400-mL beaker. Dissolve the solid in water, transfer the solution to a clean 1-liter plastic
bottle and dilute the solution to 1-liter with deionized water. If the solution is not clear, add a
few drops of 0.1M sodium hydroxide solution and mix thoroughly, until a clear solution is
obtained.
Prepare a Standard CaCl2 Solution from Primary Standard CaCo3
Obtain a sample of CaCO3 (Primary Standard Grade) from the instructor. Dry in an oven
for ~ 1 12 hours. Weigh accurately by difference, approximately 0.4g of the calcium carbonate
into a 500-mL volumetric flask. Add about 10-mL of deionized water and then add, in small
quantities, a 1:1 HCl solution until effervescence ceases and the resulting solution is clear. The
addition of HCl converts the CaCO3 to CaCl2 according to the following reaction:
2H 3 O aq 2Cl - aq CaCO 3 (s) Ca 2 aq H 2 O(l) CO 2 (g)

Dilute to the mark and thoroughly mix the solution. Then perform either Part I or Part II below,
depending on your instructors preference.
PART I
DETERMINATION USING A 50-mL BURET
Standardization of the approximately 0.01 M EDTA
Pipet 50-mL portions of the Standard Calcium Chloride (CaCl 2) solution into each of
three 250-mL Erlenmeyer flasks. Add 5-mL of NH 3-NH4Cl buffer solution, 5 drops of the
Eriochrome Black T indicator solution and 5 drops of the magnesium/EDTA complex solution.
Titrate with the approximately 0.01 M EDTA solution. Calculate a molarity for the EDTA
solution from the data obtained in each titration. Average these values. If the difference between
the two most divergent values is more than 0.001M or if the relative average deviation is > 5ppt,
consult with your instructor for further details.
Determination of the Hardness of an unknown Water Sample
Obtain a sample bottle from the instructor containing approximately 500-mL of a sample
of tap water. Pipet three 50-mL aliquots into each of three 250-mL Erlenmeyer flasks. Add 5mL of NH3-NH4Cl buffer solution to each flask, 5 drops of the Eriochrome Black T indicator
solution and 5 drops of the magnesium/EDTA complex solution. Titrate with the previously
standardized EDTA solution.
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PART II
DETERMINATION USING A 10-mL BURET
Standardization of the approximately 0.01 M EDTA solution
Pipet three 10-mL portions of the Standard Calcium Chloride (CaCl 2) solution into each
of three 250-mL Erlenmeyer flasks. Add 1-mL of NH3-NH4Cl buffer solution, 10-mL of
deionized water, three drops of the Eriochrome Black T indicator solution and three drops of the
magnesium/EDTA complex solution. Titrate with the approximately 0.01 M EDTA solution.
Calculate a molarity for the EDTA solution from the data obtained in each titration. Average
these values. If the difference between the two divergent values is more than 0.0001M or if the
relative average deviation is >5 ppt, consult with your instructor for further directions.
Determination of the Hardness of an unknown Water Sample
Obtain a sample bottle from the instructor containing approximately 500-mL of a sample
of tap water. Pipet three 10-mL aliquots into each of three 250-mL Erlenmeyer flasks. Add 1mL of NH3-NH4Cl buffer solution to each flask, 10-mL of deionized water, three drops of the
Eriochrome Black T indicator solution and three drops of the magnesium/EDTA complex
solution. Titrate with the previously standardized EDTA solution.
CALCULATION OF RESULTS (either Part I or Part II)
Calculate the total hardness of your water sample as parts per million (ppm) of calcium
carbonate (CaCO3). Be certain to report each individual value the mean value, the absolute
deviation from the mean of each value, the relative average deviations in parts per thousand, the
standard deviation and the confidence interval at an appropriate confidence level.
DETERMINATION OF THE HARDNESS OF WATER
USING A CALCIUM ION SELECTIVE ELECTRODE
PROCEDURE
Preparation of One Liter of Approximately 0.01M EDTA
Weigh approximately, but accurately 4g of disodium ethylenediaminetetraacetic acid
dihydrate previously dried at 80oC in an oven for one hour into a clean 1-L voltmetric flask.
Dissolve the solid in water, dilute to the mark and mix well. Calculate the concentration
(molarity) of the EDTA. Then perform either Part I or Part II below, depending on your
instructors preference.

PART I
DETERMINATION USING A 50-mL BURET
Determination of the Hardness of an unknown Water Sample
Obtain a sample bottle from the instructor containing approximately 500-mL of a sample
of tap water. Pipet three 25-mL aliquots into each of the three 100-mL (or 150-mL) beakers.
Add 5-mL of NH3-NH4Cl buffer solution and 25-mL deionized water to each beaker. Titrate
with the previously standardized EDTA solution using the meter/electrode (Calcium Ion
Selective Electrode)/ stirer assembly for a potentimetric titration (See Experiment V).
Data Collection, Organization, and Calculation of the Unknown Water Hardness.
Enter your data into a spreadsheet (e.g., Excel) and graph the results as you collect them.
Similarly, set up the spreadsheet to calculate the first derivative function, and plot that data as
well. [NOTE: Refer to Experiment V (acid-base potentiometer determination.) that you have
already performedthe strategy here is similar]. Calculate the total hardness of your water
sample as parts per million (ppm) of calcium carbonate (CaCO 3). Report each individual value,
the mean value, the absolute deviation from the mean of each value, the relative average
deviation from the mean in parts per thousand (ppt), the standard deviation and the confidence
interval at an appropriate confidence level.
PART II
DETERMINATION USING A 10-mL BURET
Determination of the Hardness of an unknown Water Sample
Obtain a sample bottle from the instructor containing approximately 500-mL of a sample
of tap water. Pipet three 10-mL aliquots into each of three 100-mL beakers. Add 1-mL of NH 3NH4Cl buffer solution and 10-mL of deionized water to each beaker. Titrate with the standard
EDTA solution using the meter/electrode (Calcium Ion selective electrode)/stirer assembly for a
potentiometer titration. (see Experiment V).
Data Collection, Organization, and Calculation of the Unknown Water Hardness.
Enter your data into a spreadsheet (e.g., Excel) and graph the results as you collect the
data. Similarly, set up the spreadsheet to calculate the first derivative function, and plot that data
as well. [NOTE: Refer to Experiment V (acid-base potentiometer determination.) that you have
already performedthe strategy here is similar]. Calculate the total hardness of your water
sample as parts per million (ppm) of calcium carbonate (CaCO 3). Report each individual value,
the mean value, the absolute deviation from the mean of each value, the relative average
deviation from the mean in parts per thousand (ppt), the standard deviation and the confidence
interval at an appropriate confidence level.