SOP'S FOR AIR

Sr. No. SOP's Name

1 FREE CHLORINE (AIR)
2 FLUORIDE (AIR)
3 AMMONIA IN AIR
4 HYDROGEN SULFIDE (AIR)
5 SULPHUR DI OXIDE IN AMBIENT AIR
6 LEAD NICKEL and ARSENIC IN AMBIENT AIR
7 RESPIRABLE SUSPENDED PARTICULATE MATTER(PM10) IN AMBIENT AIR
8 RESPIRABLE SUSPENDED PARTICULATE MATTER(PM2.5) IN AMBIENT AIR
9 NITROGEN DIOXIDE (NOX) (AIR-AMBIENT)
10 DETERMINATION OF OZONE IN THE ATMOSPHERE
11 SO2
12 HCL
13 NH3
14 CHLORINE
15 ACIDMIST
16 H2S (STACK & FOR AMBIENT USE ONLY)
17 CS2
 WI No.
FREE CHLORINE Rev. No.
Date
Method : Methyl Orange

Principle : Near a pH of 3.0 the colour of methyl orange solution ceases to vary with acidity. The dye is quantitatively
bleached by free chlorine & the extent of bleaching can be determined colorimetrically.

Absorbing Media: NA
Apparatus : NA

Interface : NA

Sr. No. PROCEDURE RESPONSIBILITY

1 NA NA

Reagents: 1) Methyl Orange Stock Solution (0.05%) :-

Dissolve 0.5gm reagent grade methyl orange in D.W. & dil. to 1 lit. This solution is stable indefinitely if fresh
boiled & cooled D.W. is used.

2) Methyl Orange (0.005%) :-

Dilute 100ml of stock solution to 1 lit. with D.W. Prepare fresh for use.

3) Absorbing Media :- 6ml of 0.005% methyl orange reagent is diluted to 100ml with D.W. and 3 drops of
5M HCl is added.

4) Acidified Water :- To 100ml D.W. add drops of 5M HCl.

5) Potassium Dichromate Solution (0.1M) :-

Dissolve 4.904gm anhydrous K2Cr2O7 in D.W. & diluted to 1lit.

6) Starch :- Prepare a thin paste of 1gm soluble starch in a few ml D.W. bring 200ml D.W. to a boil remove
from heat & stir in the starch paste.

7) Sodium Thiosulfate (0.1M) :-

Dissolve 25gm of Na2S2O3 5H2O in freshly boiled & cooled D.W. dil. to 1lit. Add 5ml chloroform as
preservative & allow to age for 2 weeks before standardizing as follows :-
To 80ml of D.W. & with constant stirring 1ml conc. H2SO4. 10ml 0.1N K2Cr2O7 & approximately 1gm
of KI. Allow thiosulfate solution upon approaching the end point (brown colour changing to yellowish green)
& 1ml of starch indicator solution & continue titrating to the end point (blue to light green).

Normality of Na2S2O3 = 1 / ml of Na2S2O3 used

8) Sodium Thiosulfate Solution (0.01N) :-

Dilute 100ml of the 0.1N Na2S2O3 solution to 1 lit. with freshly boiled cooled D.W. Add 5ml chloroform as a
preservative & stored in glass stoppered bottle. Standardise frequently with 0.1N K 2Cr2O7.

9) Chlorine Solution :-
Approximately 10ppm - prepare by serial dilution of household bleach (approxi. 50000ppm) or by dilution of
strong chlorine water made by bubbling chlorine gas through cold D.W. The diluted solution should contain
approxi. 10ppm of free (available) chlorine. Prepare 1lit.

Standardize 10ppm chlorine solution as follows:

To a flask containing 1gm KI & 5ml glacial acetic acid add 400ml of chlorine solution. Mix well.
Titrate with 0.01N Na2S2O3 until the iodine colour becomes faint yellow. Add 1ml of starch indicator solution
& continue the titration to the end point (blue to colourless).

1ml of 0.01N Na2S2O3 = 0.3546mg of free chlorine

Standardization NA

Calculation :- NA

Reference :- Air APHA

Date Of Change Description of Change Prepared By Reviewed By Approved By

 WI No.
FLUORIDE Rev. No.
Date
Method : NA

Principle : Reaction of fluoride with the metal ion moiety of a metal-dye complex results in fading zirconium - SPANDS
reagent or increase in the absorbance of the solution.

Apparatus : NA

Interface : NA

Media: 0.1N NaOH (4gm NaOH in 1 lit. D.W.)

Sr. No. PROCEDURE RESPONSIBILITY

1 NA NA

Reagents: Sodium Fluoride Stack Solution = (1ml = 1mgF)

Dissolve 2.2105gm of 100% sodium fluoride or the equivalent weigh of reagent grade sodium. Fluoride
in water & dilute to 1 lit. store in polythene bottle.

Sodium Fluoride Working Solution = (1ml = 10ugF)

Dilute 5ml of the stock solution to 500ml. Store in plastic bottle.

SPADNS Solution - 4.5 - dihydroxy - 3 - (P - sulfophenylano) - 2%

1 - naptholine disulforic acid trisodium salt. Dissolve 0.925gm SPADNS dye in water & dilute to 500ml.

SPADNS Reference Solution :- Add 10ml SPADNS solution in 100ml D.W. & acidity with solution
prepared by diluting 1ml conc. HCl to 10ml. This solution may be stored and reused repeatedly.

Zirconium Solution :- Dissolve 0.265gm of zirconyl. Chloride octahydrate (ZrOCl2 8H2O) in 50ml water.
add 700ml conc. HCl & dilute to 1lit. with D.W.

Zirconium Spadns Reagent :- Mix equal volume of the SPADNS and zirconium solution cool to room
temp. before use. This reagent may be stored for several months at room temp. in polythene bottle.

Standardization NA

Calculation :- NA

Reference :- APHA method is followed.

Date Of Change Description of Change Prepared By Reviewed By Approved By

 WI No.
AMMONIA IN AIR Rev. No.
Date
Method : Nesslerisation Method

Principle : Ammonia is collected in a dilute sulfuric acid. Solution in a midget impinger to form ammonia sulfate. The
solution is reacted with Nessler reagent to produce a yellow-brown complex.
The ammonia concentration is determined by reading the absorbance at 440nm.

Apparatus : NA

Calibration : 1ml of stock solution 20µg + 2ml Nessler reagent

Make up 25ml with absorbing media. Wait for 10min.
6ml 120µg

Interface : NA

Media: NA

Sr. No. PROCEDURE RESPONSIBILITY

1 NA NA

Reagents: 1) Absorbing Media : Dilute 2.8ml of conc. H2SO4 (18N) to 1 lit. with D/w to form 0.1N H2SO4.

2) Nessler Reagent : Dissolve 100gm mercuric iodide (HgI2) and 70gm potassium iodide (KI) in a small
quantity of D.W. (100gm HgI2 in 250ml D/w and 70g KI in 250ml D/w) and 160g sodium hydroxide (NaOH)
in 500ml D/w. Cool NaOH and then mix IgI2 & KI in NaOH. Dilute to 1lit.

3) Standard Ammonium Sulfate Solution : Dissolve 0.0776g of ammonium sulfate in 1 lit. D/w. 1ml of
this solution contain 20µg of ammonia. Discard solution after a week.

Sample Analysis : 23ml sample + 2ml Nessler reagent. Mix well wait for 10min. Measure the absorbance at 440nm.
Standardization : NA

Calculation :- NH3 µg/m3 = Conc. Of NH3 (µg/25ml) × 1000

Vol. of air passed (lit.)

Reference :- We use mercuric iodide & sodium hydroxide. (APHA Water)

Date Of Change Description of Change Prepared By Reviewed By Approved By

 WI No.
HYDROGEN SULFIDE (AIR) Rev. No.
Date
Method : NA

Principle : Determination of hydrogen sulfide by colorimetric method is based on the reaction which takes place under
suitable conditions between N-M-dimethyl-p-phenylenediamine sulphate, ferric sulfate and sulphid ions
resulting in the formation of methylene blue.

Absorbing Media: Dissolve 4.3g of cadmium sulphate (cdSO4.8H2O) in water. Add 0.3g of sodium hydroxide dissolved in a
small amount of water & dilute to 1lit. Mix well before use. Store the solution in a refrigerator.

Apparatus : NA

Calibration : NA

Interface : NA

Media: NA

Sr. No. PROCEDURE RESPONSIBILITY

For Sample : sample + 1.5ml of amine test + 0.5ml of ferric chloride. Mix well &
1 wait for 30min. NA
Λ = 670nm.

Reagents: 1) Amine Sulphuric Acid Stock Solution : Add 50ml conc. H2SO4 to 30ml water & cool. Dissolve 12g of
N-M-dimethyl-p-phenylenediamine dihydrochloride in the acid. Do not dilute the stock solution may be
stored indefinitely under refrigerator.

2) Amine Test Solution : Dilute 25ml of stock solution to 1lit. with 1:1 sulfuric acid.

3) Ferric Chloride Solution : Dissolve 100g of ferric chloride FeCl3.6H2O in water & dil. to 100ml.

4) Sodium Sulphide Standard Solution : Dissolve 1.2g of sodium sulphide of analytical grade
(Na2S.9H2O) in one lit. of pre-refrigerated D/w & stopper it. Since the solution is very unstable it shall be
prepared just before use.

Take 100ml of D.W. in 250ml. Conical flask & add 20ml of std. iodine solution (0.1N). Add 25ml of
hydrochloric acid (0.1N) & titrate with the thiosulphate solution using starch solution as indicator. Note
down the titrant reading as A.

Take 100ml of D.W. in 250ml conical flask & add 20ml std. iodine solution (0.1N) . Add 25ml of HCl (0.1N)
& 20ml of sodium sulphide solution & repeat the titration with the thiosulphate solution. Note down the
reading as B.

Sample Analysis : NA
Standardization : NA

Calculation :- Sodium Sulfide (µg/ml) = (A-B) × Normality of thiosulphate × 17 × 1000

'20
= (A-B) × 0.1 × 17 × 1000
'20
A = B. R. of Blank
B = B. R. of sodium sulfide solution
From stock of H2S prepare 10µg/ml

Reference :- In APHA for preparing sulphide standards H2S permention tube are used where as follows NEERI method
for preparation of standards.

Date Of Change Description of Change Prepared By Reviewed By Approved By

 WI No.
SULPHUR DIOXIDE IN AMBIENT AIR Rev. No.
Date
Method : Modified West And Gaeke Method & Colorimetric Method

Principle : Sulphur dioxide from air is absorbed in a solution of potassium tetreachloromercurate (TCM). A
dichlorosulphitomercurate complex, which resists oxidation by the oxygen in the air, is formed. The complex is made to
react with pararosaniline and formaldehyde to form the intensely colored pararosaniline methlysulphuric acid. The
absorbance of the solution is measured by means of a suitable spectrophotometer.

Absorbing Media: NA
Apparatus : NA

Calibration : NA

Interface : NA

Media: NA

Sr. No. PROCEDURE RESPONSIBILITY

For calibration curve with sulphite solution

1 NA
Measure by pipette 0, 0.5, 1, 1.5, 2, 2.5 ml of working sulphite TCM solution.

2 Add sufficient TCM solution to each flask to bring the volume to approximately 10ml. NA

3 Prepare a reagent blank by addind 10ml of unexposed TCM solution. NA

Add 1ml sulphamic acid to each flask and allow to react 10min. to destroy the nitrite resulting
4 NA
from oxides of nitrogen.

5 Add 2ml of formaldehyde solution and 2ml pararosaniline solution. NA

6 Bring all flasks to volume with TCM solution and mix thoroughly. NA

7 After 30 minutes and before 60 minutes determine the absorbance of samples at 560 nm. NA

Plot the absorbance against the total concentration in micrograms sulphur dioxide for the
corresponding solution. The total micrograms sulphur dioxide in solution equals the
8 concentration of the standard in micrograms sulphur dioxide per milliliter times the milliliter of NA
sulphite solution added (µg SO2 = µg/ml SO2 × ml added).

Determine the slope of the line of best fit , calculate its reciprocal, and denote as B, the
9 NA
calibration factor.
Reagents: 1) Absorbing Reagent, 0.04 M Potassium Tetrachloro Mercurate (TCM) : Dissolve 10.86g, mercuric chloride, 0.066g.
EDTA (di-sodium salt of EDTA), and 5.96g. Potassium chloride or sodium chloride 4.68 gm in water and bring to the
mark in a 1 litre volumetric flask. (Caution: highly poisonous, if spilled on skin, flush off with plenty of running tap water
immediately.) The pH of this reagent should not be less than 5.2. The absorbing reagent is normally stable for six
months. If, a precipitate forms, discard the reagent after recovering the mercury.

2) Sulphamic Acid (0.6%) Dissolve 0.6 g sulphamic acid in 100 ml distilled water. Prepare fresh whenever required.

3) Formaldehyde (0.2%) Dilute 5ml formaldehyde solution (36-38%) to litre with distilled water. Prepare fresh daily.

4) Stock Iodine Solution (0.1 N) Place 12.7 g iodine in a 250 ml beaker, add 40 g Potassium Iodide and 25 ml water
stir until all is dissolved, then dilute to 1 litre with distilled water.

5) Iodine solution (0.01N) Prepare approximately 0.01N iodine solution by diluting 50 ml of stock solution to 500ml with
distilled water.

6) Starch Indicator Solution Dissolve 0.4 gm soluble starch and 0.002 g mercuric iodide preservative with a little D/w
water and add the paste slowly to 200 ml boiling water. Continue boiling until the solution is clear, cool, and transfer to a
glass-stoppered bottle.

7) Stock Sodium Thiosulphate Solution (0.1 N) Prepare a stock solution by placing 25 g sodium thiosulphate
(Na2S2O3.5H2O) in a beaker, add 0.1 g sodium carbonate and dissolve uing boiled, cooled distilled water making the
solution up to final volume of 1 litre. Allow the solution to stand one day before standardizing. To standardize, accurately
weigh 1.5 g (± 0.001) primary standard potassium iodate dried at 180°C, dissolve, and dilute to volume in a 500 ml
volumetric flask. Into a 500 ml iodine flask, transfer 50 ml iodate solution by pipette. Add 2 g potassium iodide and 10 ml
of a 1:10 dilution of concentrated hydrochloric acid and stopper the flask. After 5 min, titrate with stock thiosulphate
solution to a pale yellow. Add 5 ml starch indicator solution and continue the titration until the blue color disappears.
Calculate the normality of the stock solution.

8) Sodium Thiosulphate Titrant (0.01 N) Dilute 100 ml of the stock thiosulphate solution to 1 litre with freshly boiled
and cooled distilled water.

9) Standardized Sulphite Solution for Preparation of Working Solution- Dissolve 0.3 g sodium metabisulphite
(Na2S2O5) or 0.40 g sodium sulphite (Na2SO3) in 500ml of recently boiled, cooled, distilled water. Sulphite solution is
unstable; it is, therefore, important to use water of the highest purity to minimize this instability. This solution contains the
equivalent of 320-400 µg/ml of SO2. The actual concentration of the solution is determined by adding excess iodine and
back-titrating with standard sodium thiosulphate solution. To back-titrate:-
i) Measure by pipette, 50 ml of 0.01 N iodine solution into each of two 500 ml iodine flask A and B.
ii) To flask A (blank) add 25 ml distilled water and into flask B (Sample) measure 25 ml sulphite solution by pipette.
Stopper the flask and allow to react for 5 min.Prepare the working sulphite TCM solution at the same time iodine solution
is added to the flask.
iii) With 0.01 N thiosulphate, titrate each flask in turn to a pale yellow.
iv) Then add 5 ml starch solution & continue the titration until the colour disappears.

10) Working Sulphite TCM Solution Measure 2 ml of the standard solution into a 100 ml volumetric flask by pipette &
bring to mark with 0.04M TCM. Calculate the conc.

Normality of thiosulfate = Wt. (gms of KIO3) × 103 × 0.1

ml of liter × 35.67
of sulphur dioxide in the working solution in micrograms of sulphur dioxide per milliliter. This solution is stable for 30 days
if kept in refrigerator at 5°C.

11) Purified Pararosaniline Stock Solution (0.2% Nominal) Dissolve 0.5 gm of specially purified pararosaniline in 100
ml distilled water. Kept it for two days and filter the solution. The solution is stable for 3 months if stored in a refrigerator.

12) Pararosaniline Working Solution 10 ml of stock PRA solution is taken in 250 ml volumetric flask. Add 15 ml conc.
HCl & make up to volume with distilled water.

Sample Analysis : NA
Standardization : NA
Calculation :- Normality of Thiosulfate Solution :- The normality of the solution. N, is calculated as follows:
N = W × 103 × 0.1
V × 35.67
Where, V = Volume thiosulfate used, ml
W = Weight of potassium iodate, g
35.67 = Equivalent weight of potassium iodate
Concentration of Sulphite Solution
The amount of sulphur dioxide per milliliter in the standard solution, is calculated as follows:
SO2 µg/ml = (A-B) N K
V
Where: A = number of ml for blank,
B = number of ml for sample,
N = normality of thiosulfate solution,
K = micro equivalent weight for SO2 is 32,000
V = sample volume taken

Reference :- APHA

Date Of Change Description of Change Prepared By Reviewed By Approved By

 LEAD NICKEL AND ARSENIC IN THE WI No.
Rev. No.
AMBIENT AIR Date
Method : Sampling by use of Wattman GFA Inductive Coupled Plasma (ICP) Spectroscopy

Principle : The elements in the solution vaporized and subjected to the high temperature i.e. up to 6000°C thereby obtaining
plasma. The element spectral lines so produced are specific to element. Strenght of the unique spectra is proportional to
the concentration.

Absorbing Media: NA
Apparatus : NA

Calibration : NA

Interface : NA

Media: NA

Sr. No. PROCEDURE RESPONSIBILITY

The procedure for analyses the elemental metal components in ambient air particulate matter
collected on high volume filter material.
1 NA
Filters are numbered, pre-weighed, field deployed and sampled, returned to the laboratory for
analysis purpose.

Reagents: NA

Sample Analysis : NA
Scope: Suspended particulate matter (SPM) in air generally is a complex multi-phase system consisting of all airborne solid and
low vapor pressure liquified particles having aerodynamic particle sizes ranging from below 0.01-100µm and larger.

Significance: The area of toxic pollutants has been the subject of interest. Accurate measurements of toxic air pollutants at trace
levels are essential for proper assessment. The advent of Indutively Coupled Plasma Spectroscopy has improved the
speed and performance of metal analysis in many applications.

Sample Digestion: Digestion Solution I (For Nickel and Lead): 5.55% HNO3 and 16.75% HCl
Prepare by adding in 500ml Type I Distilled Water, 55.5ml Conc. HNO3, and 16.75ml Conc. HCl, dilute to one liter with
Type I Distilled Water.

Digestion solution II (For Arsenic): 10% HNO3

100 ml Conc. HNO3 dilute to one liter with Type I Distilled Water
Do separate digestion for 1. Nickel and Lead and 2. Arsenic

Digestion Method
1) Cut a 1" × 8" strip from the 8" × 10" filter paper.
2) Cut small pieces of strip in to 100 ml beaker. (Take appropriate strips)
3) Pour 30 ml of Digestion solution I for Nickel and Lead, and Digestion solution II For Arsenic.
4) Reflux gently for 30 minutes at 95°C.
5) After refluxing, add 10 ml of clean Distilled water and allow the extract to cool for 30 minutes.
6) Filter the extract using Whatman Filter paper.
7) Dilute to 20 ml with Distilled water. The filtered sample is now ready for analysis.
8) Same procedure is repeated for blank using blank filter paper.

Standardization : NA

Calculation :- Sampled Air Volume

At standard temperature and pressure (STP 25°C and 760 mm Hg) for sample air volume rotameter, use the following
equation
Vstd = [(Qi + Qf) /2] T
Where,
Vstd = Air volume sampled, m3
Qi = Initial air flow rate, m3 / min. at STP
Qf = Final air flow rate, m3 / min. at STP
T = Sampling period in minutes
Calculate total metal conc.
Fblank = (µg metal/ml) × (final extraction volume [20ml] / strip) × (9)
Where,
Fblank = amount of metal per 465 sq. cm (722 ") of blank filter, µg
µg metal/ml = metal concentration from ICP
g = 464.52 cm2/51.61 cm2 or (72 / 8)"
Calculation of metal concentration of the exposed filter:
C = [(µg metal/ml × (final extraction volume [20ml] / strip) × (9) - Fblank] /V std
Where,
C = Concentration µg metal/ std. m3
Fblank = Amount of metal per 465 sq. cm (722 ") of blank filter, µg
µg metal/ml = Metal concentration from ICP
Vstd = Air volume sampled, m3

Reference :- USEPA Method IO-3.4

Date Of Change Description of Change Prepared By Reviewed By Approved By

 WI No.
RESPIRABLE SUSPENDED PARTICULATE
Rev. No.
MATTER (PM10) IN AMBIENT AIR Date
Method : Cyclonic Flow Technique

Principle : Air is drawn through a size selective inlet & through a filter. Particulates with diameter less than 10µm in ambient air are
collected by the filter. The mass of these particles is determined by the difference in filter weights prior to and after
sampling. The concentration of PM 10 in the designated size range is calculated by dividing the weight gain of the filter
by the volume of air sampled.

Absorbing Media: NA

Apparatus : NA

Calibration : NA

Interface : NA

Media: NA

Sr. No. PROCEDURE RESPONSIBILITY

After sampling place the exposed filters in controlled temperature & relative humidity
1 environment (15 to 27 DC) for 24 hours prior to weighing. & then take the wt. on balance. NA
Record it as the final wt. of filter.

Reagents: NA

Sample Analysis : NA
Standardization : NA

Calculation :- Calculation of volume of air sampled

V = QT
V = Volume of air sampled in m3
Q = Average flow rate in m3/minute
T = Total sampling time in minute
Calculation of PM 10 in Ambient air
PM 10 = (Wf - Wi) × 106
'V
Where:
PM 10 = Mass concentration of particulate matter less than 10 micron diameter in µg/m3
Wi = Initial wt. of filter in g
Wf = Final wt. of filter in g
V = Volume of air sampled in m3
106 = Conversion of g to µg

Reference :- CPCB Guidelines for Ambient Air Quality Monitoring

Date Of Change Description of Change Prepared By Reviewed By Approved By

 WI No.
RESPIRABLE SUSPENDED PARTICULATE
Rev. No.
MATTER (PM2.5) IN AMBIENT AIR Date
Method : Cyclonic Flow Technique

Principle : Air is drawn through a size selective inlet & through a filter. Particulates with diameter less than 2.5µm in ambient air are
collected by the filter. The mass of these particles is determined by the difference in filter weights prior to and after
sampling. The concentration of PM 2.5 in the designated size range is calculated by dividing the weight gain of the filter
by the volume of air sampled.

Absorbing Media: NA
Apparatus : NA

Calibration : NA

Interface : NA

Media: NA

Sr. No. PROCEDURE RESPONSIBILITY

After sampling place the exposed filters in controlled temperature & relative humidity
1 environment (15°C to 27°C) for 24 hours prior to weighing. & then take the wt. on balance. NA
Record it as the final wt. of filter.

Reagents: NA

Sample Analysis : NA
Standardization : NA

Calculation :- Calculation of volume of air sampled

V = QT
V = Volume of air sampled in m3
Q = Average flow rate in m3/minute
T = Total sampling time in minute
Calculation of PM 2.5 in Ambient air
PM 2.5 = (Wf - Wi) × 106
'V
Where:
PM 2.5 = Mass concentration of particulate matter less than 10 micron diameter in µg/m3
Wi = Initial wt. of filter in g
Wf = Final wt. of filter in g
V = Volume of air sampled in m3
106 = Conversion of g to µg

Reference :- CPCB Guidelines for Ambient Air Quality Monitoring

Date Of Change Description of Change Prepared By Reviewed By Approved By

 WI No.
NITROGEN DIOXIDE (NOX) Rev. No.
[AIR-AMBIENT] Date

Method : Modified Jacobs & Hocheiser Method

Principle : Ambient nitrogen dioxide (NO2) is collected by bubbling air through a solution of sodium hydroxide & sodium arsenite.
The concentration of nitrite ion (NO2-) produced during sampling is determined colourimetrically by reacting by nitrite ion
with phosphoric acid, sulfanil-amide & N-(I-naphthyl)-ethylenediamine di-hydrochloride (NEDA) & measuring the
absorbance of the highly coloured. azo-dye at 540 nm.

Absorbing 0.1 N NaOH with sodium arsenite

Solution: 4 g NaOH + 1 gm sodium arsenite for 1 lit.

Apparatus : NA

Calibration : NA

Interface : NA

Media: NA

Sr. No. PROCEDURE RESPONSIBILITY

13 ml sample + 1 ml H2O2 + 10 ml Sulphanilamide + 1 ml NEDA and mix well.
1 For Blank take 13 ml absorbing media. NA
After 10 min. measure the absorbance at 540nm.

Reagents: 1) Hydrogen Peroxide : Dilute 0.2 ml of 30% hydrogen peroxide to 250 ml with D/w.

2) Sulfanilamide Solution : Dissolve 10gm of sulfanilamide in 400ml. D/w then add 25ml of conc. (85%) phosphoric
acid. Make up to 500ml. This solution is stable for several months if stored in a brown bottle.

3) N-(l-Napthyl)-Ethylenediamine Dihydrochloride (NEDA) : Dissolve 0.1gm of NEDA in 100ml of D/w. This solution is
stable for a month if kept in a brown bottle in the refrigerator.

4) Nitrite Stock Solution : Dissolve 0.135 g of sodium nitrite in 1 lit. D/w. The solution contains 90 µg of nitrite / ml
which corresponds to 100 µg NO2 (gas)/ml.

Standardization : Standardization With Nitrite Solution:

Transfer 1 ml of nitrite stock solution into a 50 ml volumetric flask & dilute with absorbng media. The working solution
contains 1.8 µg NO2/ml which corresponds to 2 µg NO2(gas)/ml.

Nitrite Working Solution:

1 ml 2 µg + 1 ml H2O2 + 10 ml Sulphanilamid + 1 ml NEDA
2 ml 4 µg
6 ml 12 µg
Make up volume with absorbing solution

Calculation :- NOX µg/m3 = Absorbance × Factor × 1000

Vol. of air passed (liters)
25 ml for sampling
13 ml for analysis
Therefore 25 = 1.92
'13

Reference :- In APHA the absorbing solution given is Triethanol amine (15gm triethanol amine in 500ml D/w & 3 ml butanol dil. To 1
lit. with D/w).

Sodium hydroxide + Sodium Arsenite reagent as absorbing media is given in CPCB Manuals.
(IS 5182 Part 6 Methods for Measurement of Air Pollution : Oxides of nitrogen).

Sodium hydroxide solution as absorbing media is given in ,"Analytical Toxicity of Industrial. Inorganic Poison by Jacobs.
(Absorbing efficiency is better than 90%).

Date Of Change Description of Change Prepared By Reviewed By Approved By

 DETERMINATION OF OZONE IN THE WI No.
Rev. No.
ATMOSPHERE Date
Method : NA

Principle of the 1 Air containing ozone is drawn through a midget impinger containing 10ml of 1% potassium iodide in a neutral
Method: (pH 6.8) buffer composed of 0.1 M disodium hydrogen phosphate and 0.1 M potassium dihydrogen phosphate.

1.2 The iodine liberated in the absorbing reagent is determined spectrophotometrically be measuring the absorption of
the tri-iodide ion at 352 nm.

1.3 The stoichiometry (1) is approximated by the following reaction:

03 + 3 KI + H2O KI3 + 2KOH + O2

1.4 The analysis must be completed within 30 min to 1 hr after sampling.

Absorbing Media: NA
Advantages and 1.1 The method is simple, precise and believed to be more accurate than the alkaline iodide method (2).
Disadvantages: 1.2 The analysis must be completed during the period of 30 to 60 min after sampling due to the instability of the colors.

Apparatus : 1.1 SAMPLING EQUIPMENT. The sampling unit for the impinger collection method consists of the following
components.
1.1.1 A graduated midget impinger containing the absorbing solution or reagent.
1.1.2 A pump suitable for delivering desired flow rates. The sampling pump is protected from splashover or water
condensation by an absorption tube loosely packed with a plug of glass wool and inserted between the exit arm of the
impinger and the pump.
1.1.3 An integrating volume meter such as a dry gas or wet test meter.
1.1.4 Thermometer
1.1.5 Manometer
1.1.6 Stopwatch

1.2 SPECTROPHOTOMETER. Capable of measuring the yellow color at 352 nm.

1.3 MATCHED CELLS OR CUVETTES OF 2 CM PATH LENGTH.

1.4 ASSOCIATED LABORATORY GLASSWARE.

Calibration and 1.1 Freshly prepare 0.00125 M (0.0025 N) iodine standard by pi petting exactly 5 ml of the 0.025 M (0.05 N) standard
Standards: stock. Solution into a 100-ml volumetric flask and diluting to the mark with the absorbing reagent.

1.2 Pipet Q.2, 0.4, 0.6, and 0.9 ml portions of the diluted standard iodine in separate 25-ml volumetric flasks and dilute to
the mark with absorbing reagent. Mix thoroughly. The concentrations of these solutions (must be based on exact molar
concentration as determined from the molarity of the standard iodine solution) are respectively- 0.25, 0.50, 0.75, and
1.125 µmoles 12 per 25 ml or more conveniently expressed as 0.10/0.20, 0.30, and 0.45 µmoles of 12 per 10 ml of
absorbing reagent.

1.3 Immediately after the preparation of this known series, read the absorbance of each at 352 nm in the usual manner.

1.4 Plot the corrected absorbance (absorbance minus absorbance of reagent blank) of the known standards against the
exact calculated molar concentrations (in µmoles /10 ml). Draw the straight line that gives the best fit. Beer's Law is
followed.

Interface : NA

Interferences : 1.1 The negative interference of reducing glass such as sulfur dioxide and hydrogen sulfide are very serious (probably
on a mole-to-mole equivalency)
1.2 Interference from high concentrations of sulfur dioxide can be eliminated by using a prefilter consisting of a U-tube
filled with strips of glass fiber paper impregnated with chromium trioxide.
1.3 The procedure is very sensitive to reducing dusts which may be present in the air or on the glassware. Losses of
iodine occur even on clear glass surfaces, and thus the manipulations should minimize the exposure.
1.4 Halogens, hydrogen peroxide, organic peroxides, organic nitrites and various other oxidants will liberate iodine or
cause positive interference by this method.
1.5 Peroxyacetyl nitrate gives a response approximately equivalent to 50% of that of an equimolar concentration of
ozone (1). Concentrations in the atmosphere may range up to 0.1 ppm.

Media: NA

Precision and 1.1 The precision of the method within the recommended range is about ± 5% deviation from the mean. Major errors are
Accuracy: from reducing impurities in the reagent, apparatus and air (see section 3.3) and from losses of iodine during longer
sampling periods. The latter can be reduced by using a second impinger in series.
1.2 The accuracy of this method has not been established. Calibration is based on the assumed stoichiometry of the
reaction with the absorbing solution.
 Sr. No. PROCEDURE RESPONSIBILITY

1.1 CLEANING OF EQUIPMENT. All glassware should be clean with dichromate cleaning
1 NA
solution followed by thorough rinsing with tap water and distilled water.

2.1 COLLECTION AND SHIPPING OF SAMPLES.

2.1.1 Pipet 10 ml of the absorbing solution (Section 7) into the midget impinger.
2.1.2 Connect the impinger (via the absorption tube) to the vacuum pump and the prefilter
assembly (if needed) with a short piece of flexible tubing (not rubber). The minimum amount of
tubing necessary to make the joint between the prefilter and impinger should be used. The air
being sampled should not be passed through any other tubing or other equipment before
entering the impinger.
2.1.3 Turn on pump to begin sample collection. Care should be taken tomeasure the flow rate,
time and/or volume as accurately as possible. The sample should be taken at a flow rate of 0.2
to 1 lpm. If the sample air temperature and pressure deviate greatly from 25°C and 760 Torr,
measure and record these values.
2 2.1.4 Sufficient air should be sampled so that the equivalent of 0.5 to 10 µl of ozone is NA
absorbed. Sampling periods of longer than 30 min should be avoided. For a flow rate of
2liters/min, a 30 min sample should yield a sensitivity of 0.01 ppm. Do not expose the
absorbing reagent to direct sunlight.
2.1.5 After sampling, the impinger stem can be removed and cleaned. Tap the stem gently
against the inside wall of the impinger bottle to recover as much of the sampling solution as
possible. Wash the stem with a small amount << 1 ml) of unused absorbing solution and add
the wash to the impinger. Seal the impinger with a hard, non-reactive stopper (preferably
Teflon). Do not seal with rubber.
2.1.6 The sample solutions must be analyzed within 60 min after sampling.
2.1.7 A "blank" impinger should be handled as the other samples (fill and seal) except that no
air is sampled through this impinger.

3.1 ANALYSIS.
3.1.1 Record the total volume of sample solution present in the graduated impinger. This is
usually 10 ml.
3.1.2 Transfer the exposed absorbing reagent ( avoiding dilution with rinse water) to a clean
cell or cuvette.
3.1.3 Determine the absorbance at 352 nm using a matched cell or cuvette freshly filled with
3 distilled water as the reference. This measurement must be done within 30 to 60 min after NA
sampling.
3.1.4 Determine daily the blank correction (to be deducted from sample absorbance) by
reading the absorbance of the blank" sample using distilled water as the reference.
3.1.5 Samples having a color too lrk to read may be quantitatively diluted with additional
absorbing reagent and the absorbance of the diluted solution read. The dilution factor must
then be introduced into the calculations.

Reagents: 1.1 PURITY. The reagents described must be made up using ACS reagent grade or better grade of chemical.

1.2 DOUBLE DISTILLED WATER. Double distilled water should be used for all reagents. The double distilled water can
be prepared in an all-glass still by adding potassium permanganate to produce a faint pink color and barium hydroxide to
alkalize the distilled water before the second distillation.

1.3 ABSORBING REAGENT. (1% KI in 0.1 M PHOSPHATE BUFFER). Dissolve 13.61 g of potassium dihydrogen
phosphate, 14.20 g of anhydrous disodium hydrogen phosphate (or 35.82 g of dodecahydrate salt) and 10.00 g of
potassium iodide successively and dilute the mixture exactly 1 liter with double distilled water. Age at room temperature
for at least 1 day before using. This solution may be stored for several weeks in a glass stopper brown bottle in the
refrigerator or for shorter periods of time at room temperature. Do not expose to sunlight. I

1.4 STANDARD IODINE SOLUTION,

0.025 MI2 (0.05N). Dissolve successively 16.0 g of potassium iodide and 3.1730 g of iodine with double distilled
water and make up to a volume of exactly 500 ml. Age for at least 1 day before using. Standardize shortly before use
against 0.025 M Na2S2O3. The sodium thiosulfate is standardized against primary standard bi-iodate, KH(IO3)2, or
potassium dichromate, K2Cr2O7.
Range And 1.1 The range extends from 0.01 ppm to about 10 ppm.
Sensitivity : 1.2 The sensitivity of the method is dependent on the volume of air sampled. When air sampling is conducted with a
midget impinger containing 10 ml of absorbing solution, between 1 and 10 µ l of ozone may be collected.

Sample Analysis : NA
Standardization : NA

Calculations :- 1.1 The absorbance of the "blank" sample (Section 8.3.4) must first be substracted from the sample absorbances.
1.2 As indicated by the stoichiometric equation in section 1.3Jt has been empirically determined that 1 mole of ozone
(03) liberates 1 mole of iodine (I2) by this procedure. Thus, one can read directly from the calibration curve (Section 9.4)
the equivalent µmoles of 03 per 10 ml of absorbing reagent. If the total volume of the sample solution is not 10 ml, or if
the sample solution has been diluted prior to analysis, the dilution factor must be included in the calculation.
1.3 The concentration of ozone in the air sampled can be expressed as ppm of ozone, defined as µl ozone per liter of
air.

Ppm, O3 = µmoles 03 × 24.45

Vs
Where:
µmoles 03 = micromoles ozone determined from calibration curve (Section 9.4) including the dilution factor, if any.
24.45 = molar volume of ozone (µl / µmole) at 25°C and 760 Torr.
Vs = volume of air sampled in l at 25°C and 760 Torr.
µg / m3 O3 = ppm, O3 × 48 × 1000
'24.45
48.00 = Molecular weight of ozone in grams
24.45 = molar volume of ozone (µl / µmole) at 25°C and 760 Torr.

Reference :- NA

Date Of Change Description of Change Prepared By Reviewed By Approved By

 WI No. xx.xx.xx
STACK - SO 2
Rev. No. 0
Date 10.12.2013
Method : N/A

Principle : N/A

Titration Reagents: 0.01 N NaOH

Apparatus : N/A

Absorbing Media: 3% H2O2 (10ml of 30% H2O2 diluted to 100ml)

Indicator : Mixed indicator; 0.6gm Bromocosel green + 0.4 gm methyl red diluted to 1 lit methyl alcohol.

Sr. No. PROCEDURE RESPONSIBILITY

1 Titrate from Pink to Green JSO/JSA

SO2 - mg/m3 = B.R x N x milli eq. of SO2 x 1000

volume of air passed in lit.
= B.R x 0.01 x 32 x 1000
Calculation :
volume of air passed in lit.
Kg/hr = mg/m3 x Total gas quality Nm3/hr
'1000000
1) APHA (air) 2nd edition, pg 737-743
Reference: 2) Analytical toxicology of Inorganic Poisons pg 530-532
Date Of Change Description of Change Prepared By Reviewed By Approved By
 WI No.
STACK - HCl Rev. No. 0
Date 10.12.2013
Method : N/A

Principle : N/A

Titration Reagents: 0.01 N NaOH

Apparatus : N/A

Absorbing Media: N/A

Indicator : Phenolphthaline Indicator

Sr. No. PROCEDURE RESPONSIBILITY

1 For NaOH : Titrate Pink to Colourless

JSO/JSA

2 For D.W. : Titrate Colourless to Pink

Calculation : HCl - mg/m3 = (A-B) x N x 36.5 x 1000

volume of air passed in lit.
A : ml of absorbing soln
B : ml of titer(H2SO4)
ppm = mg/m3 x 24.45/36.5
For d.w = B.R x 0.01 x 36.5 x 1000
vol of air passed
Reference: Analytical toxicology of Inorganic Poisons - Jacobs pg 641
Date Of Change Description of Change Prepared By Reviewed By Approved By
 WI No.
STACK - NH 3
Rev. No. 0
Date 10.12.2013
Method : N/A

Principle : N/A

Titration Reagents: 0.01 N NaOH

Apparatus : N/A

Absorbing Media: 0.01 N H2SO4

Indicator : Phenolphthaline Indicator

Sr. No. PROCEDURE RESPONSIBILITY

1 Titrate from pink to yellow JSO/JSA

Calculation : NH3 - mg/m3 = (A-B) x N x 0.01 x 1000

volume of air passed in lit.
A : ml of absorbing soln
B : ml of NaOH titer
ppm = mg/m3 x 24.45/17(mol.wt)
Reference: Analytical toxicology of Inorganic Poisons - Jacobs pg 609 - 611
Date Of Change Description of Change Prepared By Reviewed By Approved By
 WI No.
STACK - CHLORINE Rev. No. 0
Date 10.12.2013
Method : N/A

Principle : N/A

Titration Reagents: 0.01 N Na2S2O3

Apparatus : N/A

Absorbing Media: KI soln(21 or 41)

Indicator : Starch

Sr. No. PROCEDURE RESPONSIBILITY

1 Titrate from Blue to Colourless JSO/JSA

Calculation : Cl2 - mg/m3 = B.R. x N x 35.5 x 1000

volume of air passed in lit.
ppm = mg/m3 x 24.45/Molecular weight
A : ml of absorbing soln
B : ml of NaOH titer
ppm = mg/m3 x 24.45/17(mol.wt)
Reference: Analytical toxicology of Inorganic Poisons - Jacobs pg 636
Date Of Change Description of Change Prepared By Reviewed By Approved By
 WI No.
STACK - ACID MIST Rev. No. 0
Date 10.12.2013

Method : N/A

Principle : N/A

Titration Reagents: 0.01 N NaOH

Apparatus : N/A

Absorbing Media: Glass wood

Indicator : Phenolphthaline

Sr. No. PROCEDURE RESPONSIBILITY

1 Titrate from Colourless to pink JSO/JSA

Calculation : Acid mist - mg/m3 = B.R. x N x 49.04 x 1000

volume of air passed in lit.
ppm = mg/m3 x 24.45/Molecular weight
Reference: APHA(air) 2nd edition - pg 944-946
Date Of Change Description of Change Prepared By Reviewed By Approved By
 WI No.
STACK - H2S Rev. No. 0
Date 10.12.2013

Method : N/A

Principle : N/A

Titration Reagents: 25ml sample + 1.5 amine sulphuric acid + 0.5 ml FeCl3

Apparatus : N/A

Absorbing Media: CdSO4 - 4.3gm, NaOH in separate portion of d.w & dilute to 1 lit.
Indicator : N/A

Sr. No. PROCEDURE RESPONSIBILITY

Make the titration reagent and wait for 30 mins. Take reading using
1 JSO/JSA
spectrophotometer at 670 nm.

Calculation : H2S - mg/m3 = Mg (from graphs) x 1000

volume of air passed in lit.
ppm = mg/m x 24.45/34
3

Reference: APHA(air) 2nd edition - pg 676-681

Date Of Change Description of Change Prepared By Reviewed By Approved By
 WI No.
STACK - CS2 Rev. No. 0
Date 10.12.2013

Method : N/A

Principle : N/A

Titration Reagents: 0.006862N Iodine soln

Apparatus : N/A

Absorbing Media: 5% KOH soln in ethyl alcohol (5gm KOH in 100ml ethyl alcohol)
Indicator : Starch

Sr. No. PROCEDURE RESPONSIBILITY

Sample + Phenolphtaline indicatore + 5% acetic acid, add upto red litmus paper,
1 JSO/JSA
turn blue, add starch & titrate with 0.006862N T2 sol.

Calculation : CS2 - mg/m3 = B.R. x N x 76000

volume of air passed in lit.
ppm = 24800 x A x B
C
A = Vol. of 0.006862
B = Normality of I2
C = Vol. of air passed in liters
Reference: 1) Analytical toxicology of Inorganic Poisons - Jacobs pg 559-560
2) IS-11255 part 4-1985
Date Of Change Description of Change Prepared By Reviewed By Approved By