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Great Lakes Water Authority

Water Works Park Treatment Plant


Determination of Hardness

SOP # 14
March 2015

Great Lakes Water Authority


Water Works Park Treatment Plant
Standard Operating Procedure for the Determination of Water Hardness
Written By: Abul Ahmed

Author

Date

Reviewed

Approved

Approved

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Date

Plant Manager

Water Operations Director

Date

Date

Great Lakes Water Authority


Water Works Park Treatment Plant
Determination of Hardness

SOP # 14
March 2015

Table of Contents
1
2
3
4
5
6
7

Purpose and Applicability


Method Summary
Health and Safety
Sample Preservation, Containers, handling and Storage
Interferences
Personnel Qualifications
Procedural Steps
7.1 Apparatus and Materials
7.2 Reagents
7.3 Standardization of EDTA Titrant

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3
3
4
4
4
4
5
5
5
7

7.4 Sample Analysis

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Data Records and Managements

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8.1 Calculation

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8.3 Reporting

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Quality Control

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10 References

1.0

Purpose and Applicability:


1.1
1.2

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Water hardness is an expression for the sum of the calcium and magnesium
cations concentration in a water sample. It is expressed as mg CaCO3/liter.
Calcium is usually found in highest concentrations in natural water. The presence
of calcium in water results from deposits of lime stone, gypsum etc.

Great Lakes Water Authority


Water Works Park Treatment Plant
Determination of Hardness

1.3

These cations form insoluble salts with soap and decrease the cleaning
effectiveness of soap.
These cations also form hard water deposits in hot water heaters, on piping and
drains.
Water low in hardness (<70mg/l CaCO3) is corrosive and sometimes treated to
increase hardness.
Determination of hardness serves as a basis for routine control of softening
process.
Determination of water hardness is a useful test that provides a measure of quality
of water for households and industrial uses.
This method is applicable to Drinking, Surface, and Saline waters, Domestic and
Industrial wastes.

1.4
1.5
1.6
1.7
1.8

2.0

SOP # 14
March 2015

Method Summary:
The ions involved in water hardness, i.e. Ca 2+ (aq) and Mg2+(aq), can be
determined by titration with a chelating agent, ethylenediaminetetraacetic acid
(EDTA), usually in the form of disodium salt (H2Y2-). The titration reaction is:

2.1

Ca 2+(aq) + H2Y2- (aq)


HOOC
N
-

CH2

OOC
EDTA (anionic form)

CaY2-(aq) + 2H=(aq)
COOH
CH2

N
COO

Calmagite indicator solution [ 1-(hydroxyl-4-methyl-2-phenylazo)-2-napthol-4sulfonic acid] as indicator for the above titration. At pH 10, Ca (aq) or Mg (aq)
ion first complexes with the indicator as CaIn +(aq) or MgIn+ which is wine red. As
the stronger ligand EDTA is added, the CaIn + (aq) or MgIn+ (aq)complex is
replaced by the CaY2- (aq) or MgY2- (aq) complex which is blue. The end point of
titration is indicated by color change from wine red to blue.
2.2

3.0

The method is suitable for all concentration ranges of hardness; however, in order
to avoid large titration volumes, measure less sample volume for titration if hardness
is high.

Health and Safety:

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Great Lakes Water Authority


Water Works Park Treatment Plant
Determination of Hardness

3.1
3.2
3.3
3.4

4.0

Safety precautions must be taken while handling samples and solutions.


Avoid skin contact with chemicals
The hardness buffer contains NH4OH. Use this reagent in a well-ventilated area or
in a hood.
Spillage adhering to skin should be immediately washed with plenty of water.

Sample preservation, Containers, Storage, and Handling:


4.1
4.2
4.3
4.4

5.0

SOP # 14
March 2015

Samples to be analyzed for hardness may be collected in plastic or glass


containers.
If analysis is to be carried out within two hours of collection, cool storage is not
necessary.
If analysis is delayed more than six hours aqueous samples should be preserved
with HNO3 to a pH <2, and stored at 40C.
Do not allow samples to freeze.

Interferences:
5.1
5.2

The test method is not suitable for highly colored waters or highly cloudy waters,
which obscure the color change of the indicator.
Excessive amount of heavy metals can interfere, EDTA complex formation with
Ca2+ or Mg 2+.

6.0

Personnel Qualifications:
6.1

Personnels are required to be knowledgeable of the procedures in this SOP

6.2

All personnel who perform analyses within this SOP must have qualifications
required by Great Lakes Water Authority and Michigan Department of
Environmental Quality.

6.3

Before an analyst is permitted to do reportable work, competence in performing


analysis with acceptable precision must be demonstrated.

6.4

The analyst must know and observe the normal safety procedures required in the
laboratory while preparing, using, disposing of samples, reagents, material and
while operating equipments.

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Great Lakes Water Authority


Water Works Park Treatment Plant
Determination of Hardness

7.0

SOP # 14
March 2015

Procedural Steps:
7.1

Apparatus and Materials:


7.1.1
7.1.2
7.1.3
7.1.4
7.1.5
7.1.6
7.1.7
7.1.8
7.1.9
7.1.10
7.1.11

7.2

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Burette with stand


Erlenmeyer flasks, 100mL, 250mL
Graduated cylinder, 100mL
Volumetric flasks, 100mL, 1000mL
Pipettes and Pipette bulb
Hot plate
Desiccator
Oven
pH meter
Analytical balance
Stir plate and Stir bar

Reagents:
7.2.1

De-ionized water or distilled water.

7.2.2

Calmagite indicator:
Dissolve 0.1g calmagite in 100mL de-ionized water.

7.2.3

Buffer Solution:
If magnesium EDTA is available: Dissolve 16.9g NH 4Cl in 143mL
conc.NH4OH in a 250mL volumetric flask, add 1.25g of magnesium salt
of EDTA and dilute to the mark with distilled water.
If magnesium EDTA is unavailable: Dissolve 1.179g disodium EDTA
(reagent grade) and 780mg MgSO4.7H2O (or 644mg MgCl2.6H2O) in
50mL distilled water. Add this solution to a 250mL volumetric flask
containing 16.9g NH4Cl and 143mL conc. NH4OH with mixing and dilute
to the mark with distilled water.
Store the buffer solution in a tightly stoppered plastic or borosilicate glass
bottle. Buffer solution is stable for approximately one month. Discard
when 1 or 2 mL added to sample fails to produce a pH of 10.0 +/- 0.1 at
end point of titration. The buffer is toxic and gives toxic vapors. A wellventilated area should be used when handling the buffer.
Commercially available odorless buffer which is more stable, may be
used.

7.2.4

Standard EDTA titrant, 0.01M or 0.02N


Place 3.723g reagent grade disodium ethylenediamine tetraacetate
dehydrate, Na2H2C10H12 O8N2.2H2O in a 1 liter volumetric flask and dilute

Great Lakes Water Authority


Water Works Park Treatment Plant
Determination of Hardness

SOP # 14
March 2015

to the mark with distilled water. Check with standard calcium solution by
titration. Store in polyethylene. Check periodically because of gradual
deterioration.
7.2.5

Standard calcium solution 0.02N


Dry 5.0g of anhydrous calcium carbonate at 110 0C for one to two hours.
Weigh 1.00g of the anhydrous CaCO3 powder into a 500mL Erlenmeyer
flask. Add a little at a time, 1:1 HCL until all of the CaCO 3 has dissolved.
Add 200mL distilled water. Boil for a few minutes to expel CO 2. Cool.
Add a few drops of methyl red indicator and adjust to intermediate orange
color by adding 3N NH4OH or 1:1 HCL as required. Quantitatively
transfer to a 1 liter volumetric flask and dilute to the mark with distilled
water.

7.2.6

Hydrochloric acid solution 6M or 1:1


Place 50mL of concentrated HCL solution in 100mL volumetric flask and
dilute it to the mark with distilled water.

7.2.7

Methyl red indicator


Dissolve 0.10g methyl red in distilled water in a 100mL volumetric flask
and dilute to the mark.

7.2.8

Ammonium hydroxide solution, 3N


Dilute 210mL of conc. NH4OH to1 liter with distilled water.

7.3 Standardization of EDTA Titrant:


7.3.1
7.3.2

7.3.3
7.3.4
7.3.5

The standardization is performed in triplicate.


Measure a 25mL aliquot of calcium chloride standard into each 100mL
Erlenmeyer flask. Add 50mL of distilled water, 2mL buffer solution and 1mL
calmagite indicator
To avoid precipitation of CaCO3, allow for completion of titration within 5
minutes of addition of the buffer solution.
Titrate using EDTA titrant. Add titrant slowly, with continuous stirring to a
pale blue end point (color changes from wine red to pale blue).
Calculate the factor for the EDTA titrant:
Factor = 25mL standard calcium used mL of titrant (EDTA) used.

7.4 Sample Analysis:


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Great Lakes Water Authority


Water Works Park Treatment Plant
Determination of Hardness

7.4.1

Measure 100mL of raw or tap water into a clean 250mL Erlenmeyer flask.

7.4.2

Add 2mL of buffer solution and 1mL of calmagite indicator solution.


Allow only 5 minutes to complete titration to avoid precipitation of CaCO3.
Titrate with 0.02N or 0.01M EDTA titrant to a pale blue end point.

7.4.3

8.0

SOP # 14
March 2015

Data Records and Managements:


8.1

Calculation:
Calculate Hardness, expressed as mg CaCO3/L:
Hardness, mg/L = A X B X 1000
mL of Sample
Where:
A = mls of titrant
B = Factor from step 7.3.5

8.2

9.0

Reporting:
Enter the results in the Daily Laboratory- Bacteriological- Quality Control Record
work sheet and also in the computer Daily Lab Record.

Quality Control:
For quality control purposes, all the required informations are documented on the
appropriate form.

10.0

References:
10.1
10.2

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Standard Methods for the Examination of Water and Wastewater; 20th Edition.
Method 2340 A and 2340 C
EPA methods for Chemical Analysis of Water and Wastes
EPA Method 130.2

Great Lakes Water Authority


Water Works Park Treatment Plant
Determination of Hardness

8 | Page

SOP # 14
March 2015