Titrimetric Procedures – ALKALINITY

HARDNESS, Ca, Mg and CHLORIDES

D.S.S.SRIN IVAS
QUALITY MANAGER
Environment Protection Training & Research
Institute, (EPTRI)
METHODS OF ANALYSIS
Mainly the following techniques are used
for the determination of Physico-Chemical
Parameters in the water and waste water.

1.Electrometry-PH,E.C,
2.Titrometry-Total Alkalinity, Total Hardness
Calcium Hardness,Chlorides,N-NH3
TKN, COD, Bio-Chemical oxygen demand

3.Gravimetry-T.S, T.D.S,T.S.S,T.V.S,T.D.V.S,T.F.S, &Oil and Grease

METHODS OF ANALYSIS
4.Colourimetry- NO2-,NO3-,PHOSPHATES,
FLOURIDE,
5.Turbidometry- Turbidity, Sulphates
6.Ion selective Electrodes: F-,Cl, CN,
N-NH3,
7.INSRUMENTAL ANALYSIS: METALS
PESTICIDES
PAHS,VOC,S,
ALKALINITY
Introduction: The alkalinity of water is a measure of its capacity to neutralise
acids. The alkalinity of natural waters is due to the salts of carbonates,
bicarbonates, borates, silicates and phosphates along with the hydroxyl ions in the
Free State. However the major portion of the alkalinity in natural waters is caused
by hydroxide, carbonate and bicarbonate, which may be ranked in order of their
association with high pH values. Alkalinity values provide guidance in applying
proper doses of chemicals in water and wastewater treatment processes,
particularly in coagulation, softening and operational control of anaerobic
digestion.

A. Titrimetric method The alkalinity in sample can be determined by titrating at

room temperature with 0.02N sulphuric acid by using phenolphthalein and methyl
orange indicator. Alkalinity of sample can be estimated by titrating with standard
sulphuric acid (0.02N). Titration to decolourisation of phenolphthalein indicator
will indicate complete neutralisation of OH- and 1/2 of CO3-- while sharp change
from yellow to orange of methyl orange indicator will indicate total alkalinity,
(complete neutralisation of OH-, CO3--, HCO3-).
Apparatus 5
a. Beakers - The size and form will depend upon the electrode and the size of
the sample to be used for determination of alkalinity
b. Pipettes (volumetric)
c. Flasks (volumetric): 1000 mL, 200 mL, 100 mL
Reagents and standards
a. Standard H2SO4, 0.02 N: Prepare 0.1 N H2SO4 by diluting 3.0 mL conc.
H2SO4 to 1000 mL. Standardise it against standard 0.1N Na2CO3 solution.
Dilute appropriate volume of H2SO4 to 1000 mL to obtain standard 0.02 N
H2SO4.
b. Phenolphthalein indicator: Dissolve 0.5 g in 500 mL 95% ethyl alcohol.
Add 500 mL distilled water. Add dropwise 0.02 N NaOH till faint pink
colour appears (pH 8.3)
c. Methyl orange indicator: Dissolve 0.5 g and dilute to 1000 mL with CO2-
free distilled water (pH 4.3-4.5). OR Bromo-cresol green indicator: Dissolve
0.1 g bromocresol green, sodium salt, in 100 mL distilled water (pH 4.5).
PREPARATION OF KNOWN
STRENGTHS FROM STOCK
SOLUTIONS
REQUIRED STRENGTH X REQUIRED VOLUME
--------------------------------------------------------------
STRENGTH OF THE STOCK SOLUTION

EX:PREPARATION OF 0.1 N SULPHURIC ACID

REQUIRED STRENGTH=0.1N
REQUIRED VOLUME =1000mL
STRENGTH (NORMOLITY)
OF THE AVAILABLE CON H2SO4=36N
0.1 N X1000
-------------- =2.78 Ml or 3 mL
36 N
PROCEDURE
Take 25 or 50 mL sample in a conical flask and add 2-3 drops of
phenolphthalein indicator

b. If pink colour develops titrate with 0.02 N H2SO4 till it disappears or pH is

8.3. Note the volume of H2SO4 required.
c. Add 2-3 drops methyl orange to the same flask, and continue titration till
yellow colour changes to orange. Note the volumes of H2SO4 required.
d. In case pink colour does not appear after addition of phenolphthalein continue
as above.
e. Alternatively, perform potentiometric titration to preselected pH using
appropriate volume of sample and titration assembly. Titrate to the end point
pH without recording intermediate pH. As the end point is approached make
smaller additions of acid and be sure that pH equilibrium is reached before
adding more titrant. The following pH values are suggested as equivalence
points for corresponding alkalinity concentration as mg CaCO3/L
Data analysis and calculations

Calculate total (T), phenolphthalein (P) alkalinity as follows:

P - alkalinity, as mg CaCO3/L = A x 1000/mL sample
T - alkalinity, as mg CaCO3/L = B x 1000/mL sample In case H2SO4 is
not 0.02 N apply the following formula:
In case H2SO4 is not 0.02 N apply the following formula
Alkalinity, as mg CaCO/L =A/B x N x 50000
mL of sample
where,
A = mL of H2SO4 required to bring the pH to 8.3
B = mL of H2SO4 required to bring the pH to 4.5
N = normality of H2SO4 Once, the phenolphthalein and total alkalinities
are determined, three types of alkalinities i.e. hydroxide, carbonate and
bicarbonate are easily calculated from the table given as under:
ALKALINITY RELATIONSHIPS
RESULT OF HYDROXIDE CARBONATE BICARBONATE
TITRATION ALKALINITY ALKALINITY CONCENTRATION
AS CACO3 AS Cco3 AS CACO3

1.P=0 0 0 TOTAL ALKALINITY

2.P=<1/2 T 0 2P TOTAL-2P

3.P=1/2 T 0 2P 0

4.P>1/2 T 2P-T 2(T-P) 0

5.P=T TOTAL.ALK 0 0
Hardness
Water hardness is a traditional measure of the capacity of water to
precipitate soap. Hardness of water is not a specific constituent but
is a variable and complex mixture of cations and anions. It is
caused by dissolved polyvalent metallic ions. In fresh water, the
principal hardness-causing ions are calcium and magnesium which
precipitate soap. Other polyvalent cations also may precipitate
soap, but often are in complex forms, frequently with organic
constituents, and their role in water hardness may be minimal and
difficult to define. Total hardness is defined as the sum of the
calcium and magnesium concentration, both expressed as CaCO3,
in mg/l.
Degree Of Hardness Of Drinking Water

Soft 0-60 mg/L

Medium 60-120 mg/L

Hard 120-180 mg/L

Very hard >180 mg/L

Carbonate and Non – carbonate Hardness

Carbonate (temporary / equivalent to total alkalinity,)

Non-carbonate (permanent / excess of total alkalinity )

When total hardness is numerically greater than that of total alkalinity expressed as
CaCO3, the amount of hardness equivalent to total alkalinity is called 'carbonate
hardness'.

When the hardness is numerically equal to less than total alkalinity, all hardness is
carbonate hardness.

Carbonate hardness refers to the amount of carbonate and bicarbonates in solution

that can be removed or precipitated by boiling. This type of hardness is responsible
for the deposition of scale in hot water pipes and kettles

When total hardness is numerically greater than that of total alkalinity expressed as
CaCO3, the amount of hardness which is more than the total alkalinity is called ‘non
carbonate hardness'.

Non-carbonate hardness is caused by the association of the hardness-causing cation

with sulfate, chloride or nitrate and is referred to as "permanent hardness". This
type of hardness cannot be removed by boiling.
Total Hardness
EDTA method in alkaline condition
EDTA and its sodium salts form a soluble chelated complex with certain
metal ions.
Calcium and Magnesium ions develop wine red colour with Eriochrome
black T in aqueous solution at pH 10.0 ± 0.1.
When EDTA is added as a titrant, Calcium and Magnesium divalent ions
get complexed resulting in a sharp change from wine red to blue which
indicates end-point of the titration.
Mg ion must be present to yeild end point, neutral Mg salt of EDTA is
added to the Buffer
EDTA

Total Hardens

Sample +
End Point
Eriochrome black T
+ Buffer
Calcium Hardness
At a higher pH i.e. at about 12.0 Mg++ ions precipitate and only
Ca++ ions remain in solution.
At this pH Murexide (ammonium purpurate) indicator forms a pink
colour with Ca++. When EDTA is added Ca++ gets complexed
resulting in a change from pink to purple which indicates end point
of the reaction.
To minimize the tendency towards CaCO3 precipitation limit the
duration of titration period to 5 minutes.

EDTA

Calcium
Hardens
Sample + Murexide
End Point
Interferences

Some metal ions interfere by causing fading or

indistinct end points or by stoichiometric
consumption of EDTA but can be reduced by
addition of inhibitors. Suspended or colloidal organic
matter may also interfere with the end point. This
interference can be eliminated by evaporating 50
mL sample to dryness on a steam bath and then
heating in a muffle furnace at 550oC. Residue may
be dissolved in 20 mL of 1N hydrochloric acid and
on neutralisation to pH 7 with 1N sodium hydroxide,
volume be made to 50 mL with distilled water. Run
a reagent blank following the same procedure.
Analytical Instruments

a. Conical flasks 100 mL

b. Burette

c. Pipette

d. Spatula
Reagents and Standards

Buffer solution
Inhibitor
MgCDTA
Eriochrome black T indicator
Murexide indicator
NaOH 2N
Standard EDTA Solution 0.01 M
Standard calcium solution
Calibration and Standardization

The EDTA solution needs be standardised

against standard calcium solution such that
the strength of EDTA will be 1ml = 1 mg as
CaCO3.
Procedure for Total hardness
Take 25 or 50 mL well mixed sample in porcelain dish or
conical flask

Add 1-2 mL buffer solution followed by 1 mL inhibitor.

Add a pinch of Eriochrome black T and titrate with standard

EDTA (0.01M) till wine red colour changes to blue, note
down the volume of EDTA required (A).

Run a reagent blank. Note the volume of EDTA (B).

Calculate volume of EDTA required by sample, C = (A-B)

For natural waters of low hardness, take a larger
sample volume, i.e. 100-1000 mL for titration
and add proportionately larger amounts of
buffer, inhibitor and indicator. Add standard
EDTA titrant slowly from a microburette and run
a blank using redistilled, deionized water of the
same volume as
sample. Apply blank correction for computing the
results.
Calcium hardness
Take 25 or 50 mL sample in a porcelain dish

Add 1 mL NaOH to raise pH to 12.0 and a pinch of Murexide

indicator.

Titrate immediately with EDTA till pink colour changes to purple.

Note the volume of EDTA required (A)

Run a reagent blank. Note the mL of EDTA required (B) and keep it
aside to compare end points of sample titrations.

Calculate the volume of EDTA required by sample, C = (A-B).

Standardise the EDTA (0.1 M) solution following the procedure of

calcium hardness from 1 to 4,using standard calcium solution.
Data Analysis And Calculations

TH as CaCO3 mg/l = CxDx1000

ml sample

Where, C = volume of EDTA required by sample

D = mg CaCO3 equivalent to 1.0 mL EDTA titrant

CaH as CaCO3 mg/l = CxDx1000

ml sample

where C = volume of EDTA used by sample

D = mg CaCO3 equivalent to 1.0 mL EDTA titrant
Magnesium Hardness
Magnesium Hardness =TH as CaCO3 mg/l – Ca H as CaCO3
Alkaline (Carbonate) hardness and non-alkaline (non-carbonate)
hardness
These types of hardness can be calculated from total hardness and total
alkalinity as follows:
If total hardness as CaCO3 > Total alkalinity as CaCO3
Then,
a. Alkaline hardness = Total alkalinity
b. Non-alkaline Hardness = Total hardness – Total alkalinity
If total hardness as CaCO3 < Total alkalinity as CaCO3
Then,
1. Alkaline hardness = Total hardness
2. Nonalkaline hardness = Nil
Chloride
The presence of chloride in natural waters can be attributed to
dissolution of salt deposits, discharges of effluents from chemical
industries, oil well operations and seawater intrusion in coastal
areas. Each of these sources may result in local contamination of
both surface water and groundwater. The salty taste produced by
chloride depends on the chemical composition of the water. A
concentration of 250 mg/L may be detectable in some waters
containing sodium ions. On the other hand, the typical salty taste
may be absent in water containing 1000 mg/L chloride when
calcium and magnesium ions are predominant. High chloride
content may harm metallic pipes and structures as well as
agricultural plants.
Analytical Apparatus for Argentometric
Method

a. Porcelain dish 200 mL

b. Pipettes

c. Burettes

d. Glass rod
Reagents and Standards

Potassium chromate indicator

Silver nitrate, 0.0141N

Sodium chloride, 0.0141N

Calibration and Standardization

The silver nitrate solution should be

standardize against sodium chloride solution
of 0.0141 N. It gives the strength of silver
nitrate solution 1 mL = 0.5 mg chloride as Cl-
.
Procedure

Take 50 mL well mixed sample adjusted to pH 7.0-8.0 and add

1.0 mL K2CrO4.

Titrate with standard AgNO3 solution till AgCrO4 starts

precipitating

Standardise AgNO3 against standard NaCl

For better accuracy titrate distilled water (50 mL) in the same
way to establish reagent blank.
Data analysis and Calculations

Chloride mg/l as Cl-

(A-B) x N x 35.45 x 1000

mL sample

where, A = mL AgNO3 required for sample

B = mL AgNO3 required for blank, and
N = Normality of AgNO3 used
Ag+ + Cl- = AgCl (white ppt)
Ag+ + CrO4- = Ag2CrO4 (Red ppt)
Interferences

Bromide, iodide and cyanide are measured as

equivalent of chloride ions, if the sample contains
sufficient thiosulfate, thiocyanate, cyanide, sulfite
and sulfide to interfere seriously with the
determination.

If the sample is too coloured or turbid to allow the

end point to be readily detected, this interference
may be reduced by the following treatment with a
suspension of aluminium hydroxide.
FLAME PHOTOMETER

FLAME--- LENCE---FILTER----PHOTOCELL
AMPLIFIER
READ-OUT

BURNER GAS--- NEBULISER

MIXING CHAMBER
Drain Air Sample
Sodium
Sodium can be estimated by two methods
By A.A.S AT 589.6 WAVE LENGTH
DETECTION LIMIT-0.002 Mg/L
by Flame Photometer
Stock solution:2.542 of Nacl dreid at 140
degrees
Working stadards:0-25,50,75,100 ppm
POTASSIUM
Potassium can be estimated by two methods
By A.S.S. AT 766.5 nm
Detection limited:0.01 mg/L
by Flame photometer
Dissolve 0.1907 gr of KCl dried at 110 degrees
Working standards 0,25,50,75,100 mg/L
THANK YOU