Calcium

Title
Determination of Calcium by EDTA Titrimetric Method.

General
The most common forms of calcium are calcium carbonate (Calcite) and calcium magnesium
carbonate (dolomite). Calcium compounds are widely used in pharmaceuticals, photography, lime,
de-icing salts, pigments, fertilizers, and plastics. Hardness is based on the concentration of calcium
and magnesium salts, and often is used as a measure of potable water quality. Calcium is
necessary in plant and animal nutrition and is essential component of bones, shells and plant
structures. The presence of Ca in water supplies results from passage over deposits of limestone,
dolomite, gypsum and gypsiferrous shale. Small concentrations of calcium carbonate combat
corrosion of metal pipes by laying down a protective coating. Because precipitation of calcite in
pipes and in heat exchanges can cause damage, the amount of calcium in domestic and industrial
waters is often controlled by water softening. (e.g., iron exchange, reverse osmosis)

Scope
This method is applicable for determination of calcium in water and wastewater samples

Principle
Calcium can be determined directly with EDTA, when the pH is made sufficiently high that the
magnesium is largely precipitated as the hydroxide and an indicator is used that combines with
calcium only. Several indicators give a colour change, when all the calcium has been complexed
by the EDTA at a pH of 12 to 13.

Interference
Under condition of this test, the following concentrations of ions cause no interference with the
calcium hardness determination. Cu
2+
, 2 mg/l, Fe
2+
, 20 mg/l, Fe
3+
, 20 mg/l, Mn
2+
, 10 mg/l, Zn
2+
, 5
mg/l, Pb
2+
, 5 mg/l, Al
3+
, 5 mg/l and Sn
4+
, 5 mg/l. Orthophosphate precipitates calcium at the pH of
the test. Strontium and barium give a positive interference and alkalinity in excess of 300 mg/l
may cause an indistinct end point in hard waters.

Apparatus
Conical Flask: 250 ml
Burette: 50 ml
Pipettes: 10 ml, 5 ml, 25 ml, 1.0 ml.
pH meter or pH paper.
Reagents
Standard EDTA titrant (0.01 M): Weigh 3.723 gm analytical reagent grade disodium
ethylenediaminetetraacetate dehydrate, dissolve in distilled water and dilute to 1000 ml.
Standardize against standard calcium solution. Store in a polyethylene (preferable) or borosilicate
glass bottle.
Sodium Hydroxide NaOH, (1N)
Indicators
Murexide (Ammonium Purpurate) indicator This indicator changes from pink to purple at the
end point. Prepare by mixing 200 mg murexide with 100 g solid Sodium Chloride, NaCl grinding
the mixture to 40-50 mesh. This indicator is unstable in alkaline condition.
Eriochrome Blue Black R Indicator Prepare a stable form of the indicator by grinding together in
a mortar 200 mg produced dye and 100 gm solid NaCl to 40-50 mesh. Stored in a tightly stopper
bottle. Use 0.2 gm of ground mixture for the titration in the same manner as murexide indicator.
During titration the colour changes from red through purple to bluish purple to a pure blue with no
trace of reddish or purple tint.
Standard Calcium Solution: Weigh 1.000 gm anhydrous CaCO
3
(Calcium Carbonate) powder
(primary standard) with low heavy metals, alkalies and magnesium into a 500 ml Erlenmeyer
flask. Place a funnel in the flask neck and add, a little at a time, 1 + 1 HCL until all CaCO
3

dissolve. Add 200 ml distilled water and boil for few minutes to expel CO
2
. Cool, add a few drops
of methyl red indicator adjust the intermediate orange colour by adding NH
4
OH (3N) or 1 +1 HCl
as required. Transfer quantitatively a 1000 ml volumetric flask and dilute to 1000 ml.

Pretreatment of water and wastewater samples, if required
Transfer a measured volume (50 -100 ml) of well-mixed, acid preserved samples to a flask or
beaker. In a hood, add 5 ml concentrated HNO
3
. If a beaker is used, cover with a ribbed watch
glass to minimize contamination, glass beads may be added to aid boiling and minimize spatter
where concentration levels (>10 mg/l) are being determined. Bring to a slow boil and evaporate on
a hot plate to the lowest volume possible (about 10-20 ml) before precipitation occurs.
Continue heating and adding concentrated HNO
3
as necessary until digestion is complete as
shown by a light coloured, clear solution. Do not let sample dry during digestion. Wash down the
flask or beaker walls and watch glass cover with distilled water and then filter, if necessary.
Transfer filtrate to a 100 ml volumetric flask with two 5 ml portions of water and then rinsing to
the volumetric flask. Cool, dilute to mark and mix, thoroughly. Take portions of this solution for
required Ca determinations.

Procedure
Use 50 ml sample or a smaller portion diluted to 50 ml so that calcium content is about 5 to 10
mg. Analyze hard water with alkalinity higher than 300 mg CaCO
3
/L by taking a smaller portion
and diluting to 50 ml, alternatively, stir. Adjust sample pH into the acid range (pH < 6), boil for 1
min to dispel CO
2
, and cool before beginning titration. Add 0.1 to 0.2 g indicator mixture. Add
EDTA titrant slowly, with continuous stirring to the proper end point. When using murexide,
check end point by adding 1 to 2 drops of titrant in excess to make certain that no further colour
change occur. Carry a blank in the above manner.

Calculations
mg equivalent of Ca per Lit. =
Volume of EDTA Consumed Molarity of EDTA 401000
Volume of Sample used for Test



Reference
APHA (American Public Health Association), (1998): Standard method for examination of water
and wastewater, 20
th
edition, Washington, DC, USA, p. 3.63 3.65 (3500-Ca B).


Calcium

50 ml sample

2-5 ml sodium hydroxide to maintain pH 12

Patton Reader indicator (Pinch) or Murexide Indicator (Pinch)

Titrate against EDTA (0.01 N)

(End point sky blue)


Calculation:-
Vol. 40 10
3
N
Sample taken