QASIM ALI 2007-CIVIL-130 SECTION C

Observations and Calculations

TOTAL HARDNESS
Volume of
Volume of
Titrant Mean Volume Total Hardness as CaCO3
Sample No. sample
used (ml) (mg/l)
(ml)
(ml)
11
1 11 11 50 440
11
18.5
2 19.5 19.33 50 773.2
20
3.9
3 4.0 3.9 25 156
3.8

8.7

Total Hardness as CaCO3 (mg/L) = (Volume of Titrant used x 1000)/Volume of sample

CALCIUM HARDNESS, MAGNESIUM HARDNESS AND CALCIUM IONS

Calcium Hardness as CaCO3 (mg/l) = (Volume of Titrant used x 1000)/Volume of sample

Magnesium Hardness as CaCO3 (mg/l) = Total Hardness as CaCO3 - Calcium Hardness as CaCO3
Calcium Ions (mg/l) = (Volume of Titrant used x 400.8)/Volume of sample

Comments
The World Health Organization says that "there does not appear to be any
convincing evidence that water hardness causes adverse health effects in humans”. But according
to WHO guidelines hardness of water should not exceed 500 mg/L of CaCO3 and a commomn
water treatment goal is to provide water with a hardness in the range of 75-120 mg/liter as
CaCO3. The tap water that we use in UET shows hardness of 342 mg/liter which is within the
permissible limit.
Hard water is provide us calcium which is health ful for the bones but
large concentration of it make the bones brittle. It also require more amount of soap for cleaning
purpose which is much costly and the particle may silt in the pipelines and other utilities.
 There is a limit of 150mg/liter as CaCO3 b/w the hard and soft water so all the samples
tested in the lab have more hardness so we call them as hard water.
 Sample 2 shows the maximum value of total hardness.
QASIM ALI 2007-CIVIL-130 SECTION C

 In all the samples major contribution in hardness is a due to calcium hardness (excluding
UET tap water where calcium hardness is approximately equal to Magnesium Hardness).
There may be a difference b/w the values calculated by different groups
which may be because of the following reasons
 There was intermixing of the measuring culinder of different samples with each other and
also with the mineral water cylinders.
 After titrations the flasks were not cleaned properly with the mineral water.
 There is a variation of blue colour obtained at the end.
 There is some leaksge from the burette which may be a cause of error.

Questions and Answers

1). What is pseudo hardness?

The action exhibited by sea, brackish, and other waters containing high
concentrations of sodium that interferes with the normal behavior of soap.
This sodium behaves in the similar way as divalent metallic cations. This
behavior is due to common ion effect. Hence, it is termed as pseudo hardness.

2). Why hardness is always calculated in terms of CaCO3 ?

Hard water is due to metal ions (minerals) that are dissolved in the
ground water. These minerals include Ca2+, Mg2+, Fe3+, SO42-, and HCO3-. Hard water is due to rain
moving through the vast amount of limestone, CaCO 3 that occurs in our area to the aquifer. This
is why we measure hardness in terms of CaCO 3. The concentration of the Ca 2+ ions is greater than
the concentration of any other metal ion in water.

As any combination of calcium and magnesium cations having the

same total molarity as a pure calcium solution will yield the same degree of hardness.
Consequently, hardness concentrations for naturally occurring waters (which will contain both
Ca2+ and Mg2+ ions), are usually expressed as an equivalent concentration of pure calcium in
solution. So we define hardness in terms of concentrations of calcium carbonate in water.

3). What causes hardness in water?

Hardness   is   caused   by   the   Soluble Divalent Metallic Ions  of Salts   of
Calcium, Magnesium, Iron, Manganese, Strontium, Sodium, Sulfates, Chlorides, and Nitrates.
The  degree  of hardness  depends  on  the  type  and  amount  of impurities  present  in  the
water.  Hardness also depends on the amount of Carbon Dioxide in solution. Carbon Dioxide
influences the volubility of the impurities that cause hardness. By absorbing carbon dioxide from
air carbonates are converted to bicarbonates. Temporary Hardness is generally due to presence of
bicarbonates of calcium and magnesium. Permanent Hardness is due to the chlorides and
sulphates of calcium and magnesium.

The hardness caused by carbonates and bicarbonates is called Carbonate

Hardness. The hardness caused by all others (chlorides, sulfates, nitrates) is called Noncarbonated
Hardness.
QASIM ALI 2007-CIVIL-130 SECTION C

4). Why NaOH is used in the determination of Calcium hardness?

In calcium hardness, Ca2+ is analyzed separately after precipitating

Mg(OH)2 with strong base. As PH of NaOH used is 9. It will precipitate Mg(OH) 2 (alcium and
magnesium ions present in hard water are exchanged with sodium ions in the permutit) and only
calcium hardness is determined. Moreover “sample + water” is titrated against 0.01M EDTA (Ethyle
Diamine Tetra Acetic Acid). So in order to perform acid- base titration NaOH (BASE) is added in the
sample.

5) The EDTA titration is known as complex-metric titration why?

EDTA is a versatile chelating agent. A chelating agent is a substance
whose molecules can form several bonds to a single metal ion. Chelating agents are multi-dentate
ligands. A ligand is a substance that binds with a metal ion to form a complex ion. Multidentate
ligands are many clawed, holding onto the metal ion to form a very stable complex. EDTA can form
four or six bonds with a metal ion.

Complexometric titration is based on the formation of a complex ion.

Ethlyenediaminetetraacetic acid (EDTA or H4Y, where Y = C10H12N2O8 is a complexing agent
designed to bind metal ions quantitatively, forming stable, water soluble complexes with a 1:1
stoichiometry for most metal ions (i.e., 1 EDTA binds to 1 metal ion). EDTA binds to both calcium
and magnesium, but binds more tightly to calcium, thus:

Ca2+ + Y4– → CaY2–

Mg2+ + Y4– → MgY2–
Ca2+ + MgY2– → CaY2– + Mg2+

Thus due to formation of this complex ion, EDTA titration is known as complexometric titration