OUR LADY OF FATIMA UNIVERSITY

COLLEGE OF PHARMACY
Pharmaceutical Analysis I

EXERCISE NO. 7
Assay of Hardness of Water
[COMPLEXATION METHOD]
Post Laboratory Discussion
OBJECTIVES
1. To perform analysis of water by
determining pH and presence of
sulfate and chloride ions
2. To describe the hardness of
water
3. To develop the skills necessary
to perform volumetric analysis
Introduction
• Hardness in water is due to the presence of dissolved salts
of calcium and magnesium. The total hardness of water is
expressed as CaCO3. Generally considered as unfit for
drinking, bathing, washing, and in water heaters.🡪 WHY?
•
It is therefore important to determine the the amount of
hardness-producing substances present in the water
sample.
Complexation
VS: EDTA
PRIMARY STANDARD: CaCO3
INDICATORS: Hydroxynapthol Blue, Eriochrome Black, Dithizone,
Calmagite, Murexide, Pyrocathecol Violet

MASKING AGENTS:
Triethanolamine 🡪 Al, Fe, Mn
Thioglycol( 2-3 -dimercaptopropanol) 🡪 Hg, Cu, Bi
Cyanide 🡪 Zn, Co, Ni,Cu
Flouride 🡪 Ca, Mg, Al

DIRECT TITRATION: CaCO3, ZnO and Magnesium

RESIDUAL TITRATION: Al and Bi
Hardness of Water
TITRANT: EDTA
ANALYTE: Water
Sample
INDICATOR:
Eriochrome black T
ENDPOINT:
Blue-colored solution
 Answers – Hardness of Water
Water – must meet the requirements of National
Primary Drinking Water Regulations (NPDWR) issued by
U.S. Environmental Protection Agency (EPA) or the WHO
drinking water guidelines.
Disinfectants are added for microbial control 
Chlorine-containing substances, ozone, chloramines or
chlorine dioxide
Types:
Monographed
Non-monographed
Drinking water
  Analytical water
 Answers – Hardness of Water
• pH –between 5.0 – 7.0
• Ammonia – alkaline mercuric potassium
iodide TS
• Calcium – ammonium oxalate TS
• Carbon dioxide – calcium hydroxide TS
• Chloride – silver nitrate TS
• Sulfate – barium chloride TS
• Oxidizable substances – 0.1 N
potassium permanganate
• * Sterility
 Answers
When is the hardness of water determined?

At the source
Determines the dissolved Calcium and Magnesium if the source
is ground water
General guidelines for classification of waters (milligrams per liter) as
calcium carbonate are:
0 to 60 mg/L as soft
61 to 120 mg/L as moderately hard
121 to 180 mg/L as hard
and more than 180 mg/L as very hard.
 Answers – Hardness of Water
• hard water causes the poor formation of lather with soap.
•

Bicarbonates cause temporary hardness while the more soluble

sulfates of Ca and Mg results to permanent hardness.
• Temporary hardness is removed by boiling
 Answers – Hardness of Water
• Adding washing soda results to insoluble carbonates
•

•
Other processes include Calgon Process using sodium
hexametaphosphate (trade name is Calgon)
 Answers – Hardness of Water
• Using Ion exchange resin
•

Acid resins exchange their H ions for Ca and Mg, while basic their OH
ions for HCO3-, Cl- and SO4-
Reference/s:
•Hardness of water. Retrieved from:
https://www.usgs.gov/special-topic/water-
science-school/science/hardness-water
•Knevel, A.M; DiGangi, F.E; (1977) Jenkins’
Quantitative Pharmaceutical Chemistry
Seventh Edition. Merriam Webster Bookstore
Any questions??