ESTIMATION OF CARBONATE, NON-CARBONATE AND TOTAL

HARDNESS IN THE GIVEN WATER SAMPLE

AIM
To estimate the total hardness, carbonate hardness and non-carbonate hardness of
the given sample of water using standardized EDTA.

PRINCIPLE

EDTA reacts with Ca2+ and Mg2+ forming highly stable metal ion complexes in the
pH range 9‐10.

M2+ + H2Y2- MY2‐ + 2H+

where H2Y2‐ is the anion of the disodium salt of EDTA and M2+ = Ca2+ & Mg2+

Being a reversible reaction, its extent and hence the titration value will vary slightly
with the concentration of H+. Hence a buffer is used to keep this factor constant. In order
to detect the end point, a metal‐ion indicator, Eriochrome Black‐T (EBT), is used. EBT
forms wine‐red coloured complexes with metal ions like Ca2+, Mg2+, Zn2+ etc. These are,
however, less stable than EDTA complexes. When EDTA solution is added, initially the
free M2+ ions react to form M‐EDTA complex and finally the metal ion from M‐EBT
complex reacts to form M‐EDTA releasing free indicator, which is blue in the pH range 9‐
10. The end point is the change of colour from wine‐red to blue.

EDTA EBT

[Ca/Mg-EDTA] – Octahedral complex [Ca/Mg-EBT] – Octahedral complex

1
 Direct titration of water using standardized EDTA and EBT indicator gives the total
hardness. Non‐Carbonate hardness can be determined by precipitating the carbonate
hardness by boiling, followed by titration with EDTA solution. The difference between the
total hardness and non‐ carbonate hardness corresponds to the carbonate hardness.

Ca(HCO3)2 → CaCO3↓ + H2O + CO2↑

Mg(HCO3)2 → Mg(OH)2↓ + 2CO2↑

PROCEDURE
Standardization of EDTA

The given standard ZnSO4 solution is quantitatively made up to 100 mL by following

all the usual precautions. The 20 mL of ZnSO4 solution is pipetted out into a clean conical

flask, 1 mL of buffer (pH = 10; NH4Cl/NH4OH) is added followed by 1‐2 drops of EBT

indicator. The contents of the conical flask are titrated against EDTA taken in the burette,
with constant shaking. The end point is the colour change from wine red to blue. The titration
is repeated to get concordant value.
Estimation of total hardness
The 20 mL of the given sample of water is pipetted into a clean conical flask. The 1
mL of buffer (pH = 10, NH4Cl/NH4OH) and 1‐2 drops of EBT are added. The solution in

the conical flask is titrated against EDTA until the wine-red colour just changes to blue. The
titration is repeated for concordance.
Estimation of carbonate and non‐carbonate Hardness
The 20 mL of the given sample of water is taken in a clean beaker. The beaker is covered
with a watch glass and its contents gently boiled for 5 min.
Now, the watch glass is removed, after washing its bottom into the beaker with
freshly boiled and cooled distilled water. The solution is filtered into a clean conical flask.
The beaker and the precipitate are washed twice with freshly boiled and cooled water. The
washings are also collected in the same flask. 1.5 mL of the buffer and 2 drops of EBT are
added to the filtrate.
The solution is titrated against standard EDTA until the wine-red colour changes to blue.
The titration is repeated, adding the buffer towards the end point.

The total hardness, carbonate hardness and non‐carbonate hardness are

calculated.

2
Titration – 1: Standardisation of EDTA

Titrand : Water sample

Titrant : EDTA
Indicator : EBT
End Point : Wine red to Blue

Standard solution vs EDTA solution

S. No. Volume of standard Burette Reading Volume of EDTA Concordant

solution (mL) Initial Final Solution (mL) Value (mL)
1 20

2 20

3 20

Calculations
Volume of standard solution (V1) = 20 mL

Normality of standard solution (N1) = N

Volume of EDTA (V2) = mL

Normality of EDTA (N2) =?

𝑉𝑆𝑡𝑑.𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑋 𝑁𝑆𝑡𝑑.𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
Normality of the EDTA (N2) =
𝑉𝐸𝐷𝑇𝐴

3
 Titration – 2: Estimation of total hardness

Titrand : Water sample

Titrant : EDTA
Indicator : EBT
End Point : Wine red to Blue

Standard EDTA solution vs Water sample

S. No. Volume of sample Burette Reading Volume of EDTA Concordant

water (mL) Initial Final Solution (mL) Value (mL)
1 20

2 20

3 20

Calculations
Volume of EDTA (V2) = 20 mL

Normality of EDTA (N2) = N

Volume of water sample (V3) = mL

Normality of water sample (N3) =?

𝑉𝐸𝐷𝑇𝐴 𝑋 𝑁𝐸𝐷𝑇𝐴
Normality of the given water sample =
𝑉𝑊𝑎𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒

Total Hardness of water sample = Nwater sample X Eq. Wt. of CaCO3 X 1000 ppm as CaCO3 eq

Total Hardness of water sample = N water sample X 50 X 1000

4
 Titration – 3: Estimation of non‐carbonate hardness

Titrand : Filtrate of boiled Water sample

Titrant : EDTA
Indicator : EBT
End Point : Wine red to Blue

Standard EDTA solution vs Boiled Water sample

S. No. Volume of standard Burette Reading Volume of EDTA Concordant

solution (mL) Initial Final Solution (mL) Value (mL)
1 20

2 20

3 20

Calculations
Volume of EDTA (V2) = 20 mL

Normality of EDTA (N2) = N

Volume of boiled water sample (V4) = mL

Normality of boiled water sample (N4) =?

𝑉𝐸𝐷𝑇𝐴 𝑋 𝑁𝐸𝐷𝑇𝐴
Normality of boiled water sample =
𝑉𝑏𝑜𝑖𝑙𝑒𝑑 𝑊𝑎𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒

Non-Carbonate Hardness of water sample = Nboiled water sample X Eq. Wt. CaCO3 X 1000

Non-Carbonate Hardness of water sample = N water sample X 50 X 1000

Carbonate Hardness of the given water sample = Total Hardness – Non-carbonate Hardness

5
RESULT

Total hardness = ppm as CaCO3 eq.

Carbonate hardness = ppm as CaCO3 eq.

Non – carbonate hardness = ppm as CaCO3 eq.