IS 3025 (Part 51) :2001

Indian Standard
METHODS OF SAMPLING AND TESTS
(PHYSICAL AND CHEMICAL) FOR WATER
AND WASTE WATER
PART 51 CARBONATE AND BICARBONATE

(First Revision )

ICS 13.060.50; 13.060.60

0 BIS 2001

BUREAU OF INDIAN STANDARDS

MANAK BHAVAN, 9 BAEIADUR SHAH ZAFAR MARG
NEW IDELHI 110002

Price Group 3
Water Environment Protection Sectional Committee, CHD 12

FOREWORD

This Indian standard (Part 51) (First Revision) was adopted by the Bureau of Indian Standards, after the draft
finalized by Water Environment Protection Sectional Committee had been approved by the Chemical Division
Council.

Alkalinity of water is its acid neutralizing capacity. It is the sum of all the titratable bases. Alkalinity is significant
in many uses and treatments of natural water and wastewater. The alkalinity of many surface water is primarily
a function of carbonate, bicarbonate and hydroxide content. It is taken as an indicator of the concentration of
these constituents. Alkalinity measurements are used in the interpretation and control of water and wastewater
treatment processes.

The technical committee responsible for formulation of IS 3025:1964 ‘Methods of sampling and test (physical
and chemical) for water used in industry’ had decided to revise the standard and publish it in separate parts.
This standard supersedes 44 of IS 3025:1964 and is one among the different parts being published under
IS 3025 series of standards.

Considerable assistance has been derived from the following documents:

— Standard methods for the examination of water and waste water, 17th edition. American Public Health
Association; American Water Works Association; and Water Pollution Control Federation, U.S.A.
— 1S0 3196:1975 Sodium hydroxide for industrial use — Determination of carbonates content —
Titrimetric method.
— ASTM D 513-88.

The composition of the committee responsible for the preparation of this standard is given in Annex A,

In reporting the result of a test or analysis made in accordance with this standard if the final value, observed or
calculated, is to be rounded off, it shall be done in accordance with IS 2: 1960 ‘Rules for rounding off numerical
values (revised)’.
 IS 3025 (Part 51) :2001

Indian Standard
METHODS OF SAMPLING AND TESTS
(PHYSICAL AND CHEMICAL) FOR WATER
AND WASTE WATER
PART 51 CARBONATE AND BICARBONATE

(First Revision )
1 SCOPE be subjected to microbial action and to loss or gain of
carbon dioxide or other gases when exposed to air,
This standard prescribes two methods for the analyse samples without delay, preferably within one
determination of carbonate and bicarbonate in water day. If biological activity is suspected, analyse within
and wastcwater: six hours. Avoid sample agitation and prolonged
a) Titrimetric method, and exposure to air.
b) Calculation method.
6 INTERFERENCES
2 REFERENCES Soaps, oily matter, suspended solids, or precipitates
The following Indian Standards contain provisions may coat the glass electrode and cause a sluggish
which through reference in this text, constitute response. Allow additional time between titrant
additions to let electrode come to equilibrium or clean
provision of thik standard. At the time of publication,
the electrodes occasionally. Do not filter, dilute,
the editions indicated were valid. All standards are
subject to revision, and parties to agreements based concentrate, or alter sample.
on this standard are encouraged to investigate the
7 TITRIMETRIC METHOD
possibility of applying the most recent editions of the
standards indicated below: 7.1 Principle

IS No. Title The titration may be performed potentiometrically or

7022 Glossary of terms relating to water, with phenolphthalein indicator. The total OH- ,c@
(Part 1) :1973 sewage and industrial effluents, and HCO~ content is first determined by titration with
Part 1 standard acid using methyl orange/bromocresol green
7022 Glossary of terms relating to water, indicator. Another equal portion of the sample is
(Part 2) :1979 sewage and industrial effluents, titrated against the same acid using phenolphthalein/
Part 2 metacresol purple indicator.

3 TERMINOLOGY 7.2 Apparatus

For the purpose of this standard, the definitions given 7.2.1 Electrometric Titrator
in IS 7022 (Part 1) and 7022 (Part 2) shall apply.
Use any commercialpH meter or electrically operated
4 GENERAL titrator that uses a glass electrode and maybe read to
0.05 pH unit. Standardize and calibrate according to
Carbonate, bicarbonate and hydroxide contribute to
manufacturer’s instructions. Pay special attention to
the alkalinity of water. When the total alkalinity of a
temperature compensation and electrode care, if
water is due almost entirely to hydroxides, carbonates
automatic temperature compensation is not provided,
or bicarbonates, and the total dissolved solids is not
titrate at 25 + 5°C.
greater than 500 mgll, the carbonate and bicarbonate
concentrations as CaC03 may be calculated from the 7.2.2 Titration Vessel
sample pH and total alkalinity.
For conventional sized electrodes, use a 200 ml, tall-
5 SAMPLING AND STORAGE form Berzelius beaker without a spout. Fit beaker with
a stopper having three holes, to accommodate the two
Collect samples in polyethylene or borosilicate glass electrodes and the burette.
bottles and store at a low temperature. Fill bottles
completely and cap tightly. Because waste samples may 7.2.3 Magnetic Stirrer

1
IS 3025 (Part 51) :2001

7.2.4 Pipettes, Volumetric stirring. Filter, if precipitate forms, then add 0.02 N
NaOH drop-wise until a faint purple colour appears.
7.2.5 Flasks, Volumetric
7.3.7 Sodium Thiosulphate — 0.1 M
7.2.6 Barettes, Borosilicate Glass
Dissolve 25 g sodium thiosulphate (NazS,0j.5HzO)
7.2.7 Polyolejin Bottles
in water and dilute to 1 000 ml with distilled water.
7.3 Reagents
8 PROCEDURE
7.3.1 Sodium Carbonate Solution — Approximately
8.1 Sample Size
0.05 h’
The range of carbonate and bicarbonate concentrations
Dry 5 g primary standard sodium carbonate, at 250°C
found in wastewater is so large that a single sample
for 4 hours and cool in a desicator. Weigh 2.5 f 0.2 g,
size and normality of titrant can not be specified. For
transfer to 1 Iitre volumetric flask, dissolve in distilled
alkalinities less than 1000 mg as CaCOJl, take 20
water and make up the volume. Do not store for longer
ml of sample and titrate with 0.02 N hydrochloric acid;
than one week.
while for alkalinities more than 1000 mg, as CaCOJl,
7.3.2 Standard Hydrochloric Mid — O.IN take 5 ml of the sample and titrate with 0.1 N
hydrochloric acid.
Prepare acid solution of approximate normality by
diluting 8.3 ml of concentrated hydrochloric acid to 8.2 The end point may be determined by any of the
1 Iitre. Standardize against 40 ml of 0.05N sodium following:
carbonate solution, with about 60 ml of water, in a
a) By colour change, and
beaker, by titrating potentiometrically to pH 5. Lift
out electrodes, rinse into the same beaker and boil b) Potentiometrically.
gently for 3 to 5 minutes under a water glass cover. 8.2.1 Colour Change
Cool to room temperature, rinse cover glass into
beaker, and finish titrating to pH inflection point. Colour indicators maybe used for routine and control
Calculate normality as follows: titrations in the absence of interfering colour and
turbidity and for preliminary titrations to select sample
size and strength of titrant. Take sample size and
AxB
Normality, N= —xc normality of titrant according to 8.1. If free residual
53 chlorine is present, add 0.05 ml (1 drop) of 0.1 M
where sodiumthiosulphate solution, or destroy with
ultraviolet radiation. Add 5 drops of phenolphthalein
A= Sodium carbonate in g weighed in 11flask; indicator solution and titrate over a white surface to
B= Sodium carbonate solution, in ml, for persistent colour change, characteristic of the
titration; and equivalence of indicator used with sample to a buffer
c= Acid, in ml, used. solution at the designated pH. Repeat the titration
7.3.3 Standard Hydrochloric Acid — 0.02 N using bromocresol green indicator solution. The two
titrations represent the phenolphthalein and the total
Dilute 200 ml of 0.1000 N standard acid to 1000 ml alkalinity respectively.
with distilled or deionised water. Standardize by
potentiornetric titration against 15 ml 0.05N sodium 8.2.2 Potentiometric Titration
carbonate as per procedure in 7.3.2. 8.2.2.1 Potentiometric titration curve
7.3.4 Methyl Orange/ Boromocresol Green Indicator Rinse electrodes and titration vessel with distilled
Solution water and drain. Select sample size and normality of
Dissolve 100 mg of methyl orange/bromocresol green, titrant according to criteria of 8.1.
in 100 ml distilled water. Measure sample pH. Add standard hydrochloric acid
7.3.5 Metacresol Purple Indicator Solution in increments of 0.5 ml or less, such that a change of
less than 0.2 pH units occur per increment. After each
Dissolve 100 mg of metacresol purple in 100 ml water addition mix thoroughly but gently with a magnetic
(pH 8.3 indicator). stirrer. Avoid splashing. Record pH when a constant
7.3.6 Phenolphthalein Solution reading is obtained. Continue adding titrant and
measure pH. Titrate to pH 8.3 and record the
Dissolve 1 g ofphenophthalein in 100 ml of ethanol cumulative milliliters of titrant added. Continue
and add 100 ml of distilled water with constant titrating to pH 4.5 and again record the total volume

2
 IS 3025 (Part 51) :2001

of titrant used. As the end point is approached make of the total alkalinity;
smaller additions of alkali and be sure that pH c) Bicarbonate ( HCO~ ) alkalinity is present if
equilibrium is reached, before making the next phenolphthalein alkalinity is less than half
addition. of the total alkalinity. These relationships
may be calculated by the following scheme,
9 CALCULATION
where P is, phenolphthalein alkalinity and T
9.1 Calculate phenolphthalein alkalinity by using the is total alkalinity.
volume of acid used for phenolphthalein end point or
9.3 Select the smaller value of P or (T–P). Then ,
titrate potcntiometrically topH 8.3. Calculate the total
carbonate alkalinity equals twice the smaller value.
alkalinity by using the volume of acid used for
When the smaller value is P, the balance (T–2P) is
bromocrcsol green end point or titrate potentio-
bicarbonate. When the smaller value is (T–P) the
mctrically to pH 4.5.
balance (2P–T,I is hydroxide. All results are expressed
as CaCOJ. The mathematical conversion of the results
AX NX50 is shown in Table 1 (A modification of Table 1 is
Alkalinity (CaC03 mg/1) =
ml of sample” desirable when P is greater than T).

where Table 1 Alkalinity Relationships

A= ml of standard acid used, and Result of Hydroxide Carbonate Bicarbonate
N = Normality of acid. Titration Alkalinity .Mkalinity Concentration
as CaC03 as CaC03 as CaC03
9.2 The results obtained from the phenolphthalein and (1) (2) (3) (4)
total alkalinity determinations offer a means for the P=o o 0 T
calculation of carbonate and bicarbonate, concen- P<l/2T o 2P T-2P
trations as CaCO1. The method ascribes the entire P= I12T o 2P o
alkalinity to bicarbonate, carbonate and hydroxide and P>l/2T 2P-T 2(T-P) o
it assumes the absence of other (weak) inorganic or P=T T o 0
organic acids, such as silicic, phosphoric and boric where

acids. It further presupposes the incompatibility of P = Phenolphthalein alkalinity, and

hydroxide and bicarbonate alkalinities. Because the T = Total alkalinity.
calculations are made on a stoichiometric basis, ion
10 PRECISION AND BIAS
concentrations in the strictest sense are not represented
in the results, which may differ significantly from 10.1 No general statement may be made about
actual concentrations especially at pH greater than 10. precision because of the great variation in sample
.4ccording to this scheme, characteristics. The precision of the titration is likely
to be much greater than the uncertainty involved in
a) Carbonate ( Co~- ) alkalinity is present when
sampling and sample handling before the analysis.
phenolphthalein alkalinity is not zero but is
Icss than total alkalinity; 10.2 In the range of 10 to 500 mg/1 when the alkalinity
is due entirely to carbonates or bicarbonates, a standard
b) Hydroxide ( OH-) alkalinity is present if
deviation of 1 mg/1 (as CaCOJ may be achieved.
phenolphthalein alkalinity is more than half
IS 3025 (Part 51) :2001

ANNEX A

(Foreword)

COMMITTEE COMPOSITION

Water Environment Protection Sectional Committee, CHD 12

Chairman Representing
SF{R[D. K. BISWAS Central Pollution Control Board, Delhi
Members
DR P. K. MATHUR Bhabha Atomic Research Centre, Mumbai
DR T. N. MAHADAVE~(Alternate)
SHRIlMRAhtIRRAHMA?X Central Mechnical Engineering Research Institute, Durgapur
SHIUB. RUJ(Alternate)
SHRIA. K, GUPTA Bharat Heavy Electrical Ltd, Handwar
(Alternate)
SHIUN. G. SRIVASTAVA
DR P. S. RAMA~ATH.4~ Gharda Chemicals Ltd, Maharash&
DR S. R. JAKALI(Nfemate)
SHRIR. A. RAMANIJAM Central Leather Research Institute, Chennai
Suro N. SAMWELU(Akernute)
SHRIS. K, JAIN Department of Industrial Development, Ministry of Industry, Govt ofIndia, New Delhi
SHRIANLJAIN Engineers India Ltd, Gurgaon
D~ (Ms) B. SWAMI~ATKO’ The Fertiliserx Association of India, New Delhi
Dn S. NAN’D(Ahernate)
DR S. D. MACHUAh’I Central Pollution Control Board, Delhi
DR R, C. TRNEDI (Altenzafe)
StisuSAmwmc KUMARMEHRA ABB Alstom Power India Ltd, West Bengal
SHRISUBRATOKOMARBASU(A/femate)
SHRIBAKULB. DAVE Hindustan LeverLtd, Mumbai
SHRIU. P. SIXGH(Alternate)
DR ANILBHASKER ICMA, Mumbai
SHRIB. B. NARNLA(Alternate)
DR K. R. P. SIXGH Industrial Toxicology Research Centre, Lucknow
DR KRIStINAGOPAL(~kemute)
SHRIM. N. VYAS Indian Petro Chemicals Corpn Ltd, Vadodra, Gujarat
DR J. D. DESAI(,4/~emafe)
DR V. K. VIW.MA Shnram Institute for Industrial Research, Delhi
SHRIM. S. DHIA’GRA(Alternate)
DR M. P. SmGH Indian Oil Corporation Ltd, Faridabad
DR A. S. MATHUR(Alternate)
DR P. S. MINHAS Central soil Salinity Research Institute, Kamal
SHRIP. M. KHAiXDERJA Tata Chemicals Ltd, Gujarat
SHRIJ. M. KHAN(A/terrrate)
SHRISUINLSACHDEVA Tbermax Limited, Pune
(Alternate)
SHRIS. S. BASARGEKAR
SHRIA. K. JmDAL Thermax Fuji Electric Ltd, Pane
DR S. K. GHOSH National Institute of Occupational Health, Ahmedabad
Stnu S. B, SAHAY National Thermal Power Corpn Ltd, West Bengal
SHRIR. L. SRNASTAVA(Alternate) .. .
SHRIS. M. SHINGOTE National Uirncil for Cement and Building Materials, New Delhi
(Akemufe)
SHRIV. P. CHA?TERJEE
DR G. K. GURE.IA Thermax Limited (CII), Pane
SHRIS, K. CHOPRA(Alternate)
DR S. K. KAPCJOR DRDO, New Delhi
(Alternate)
DR (SHRIMATI)KSHIPRAMLSHRA
SIiRIM. R. RAJPUT Regional Labour Institute, Kanpur
(,=t/tema[e)
DR S. N, BATWRJLZ
St{ru D. K. DUA Punjab Pollution Control Board, Punjab
DR (SHRIMATI)H. K. PARWANA(Alternate)
REPRESEXTAI?VE The Dharamsi Morarji Chemical Co Ltd, Mumbai
RWIWSEhTAIIVE Indian Meteorological Department, Safdacjung Airport, New Delhi
DR DIPAKCHAKRABORTY West Bengal Polhrtion Control Board, Calcutta
(Alternate)
DR UJJALMUKHEIUEE
REIIREYATATWE Maharashtra State Pollution Central Board, Mumbai

(Continuedonpage 5)

4
 IS 3025 (Part 51) :2001

(Con(inuedj-om page 4)

Members Representing

SHRIS. BLLAKRISHNAN Tamil Nadu Pollution Control Board, Chennai

StmrA. K. SAXIZNA National Productivity Council, New Delhi
SHWM. A, PATTL(Alternate)
REPREWhTATNE Department of Rural Development, New Delhi
RIIVWSEhTATIVE Panchayat Raj Department, Hyderabad
DR C. M. A~RAWAL Directorate General ofHealth Services, New Delhi
SHNASHOKBHAnA Min of Environment & Forests, New Delhi
DR S. P. PA~DE Water Technology Engineering Div, Nagpur
REPIWSENTATIVE RDSO, Ministry of Railway, Lucknow
SHRtA. K. DEY Central Fuel Research Institute, Dhanbad
SHRIM. M. MALHOTRA, Director General, BIS (Ex-ojlcio Member)
Director (Chem)
Merrrber-Secretary
DR R. K. SINGH
Addl Director (Chem), BIS

5
Bureau of Indian Standards

BIS is a statutory institution established under the Bureau of Indian Standards Act, 1986 to promote
harmonious development of the activities of standardization, marking and quality certification of goods
and attending to connected matters in the country.

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implementing the standard, of necessary details, such as symbols and sizes, type or grade designations.
Enquiries relating to copyright be addressed to the Director (Publications), BIS.

Review of Indian Standards

Amcndlments arc issued to standards as the need arises on the basis of comments. Standards are also reviewed
periodically; a standard along with amendments is reaffirmed when such review indicates that no changes are
needed; if the review indicates that changes are needed, it is taken up for revision. Users of Indian Standards
should ascertain that they are in possession of the latest amendments or edition by referring to the latest issue of
‘B] S Catalogue’ and ‘Standards: Monthly Additions’.

This Indian Standard has been developed from Doc : No. CHD 12 (304).

..
Amendments Issued Since Publication

Amend No. Date of Issue Text Affected

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