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है”ह”ह

IS 5182-21 (2001): Methods for Measurment of Air Pollution,Part 21: Non Methane Hydrocorbons in Air by GasChromatography [CHD 32: Environmental Protection and WasteManagement]

IS 5182( Part 21 ) :2001

Indian Standard

METHODS FOR MEASUREMENT OF AIR POLLUTIONPART 21 NON METHANE HYDROCARBONS IN AIR BY GAS CHROMATOGRAPHY

ICS 13.040.20; 71.040.50

0 BIS2001

BUREAU OF INDIAN STANDARDSMANAK BHAVAN, 9 BAHADUR SHAH ZAFAR MARG

NEW DELHI 110002

June 2001 Price Group 3

Air Environment Protection Sectional Committee, CHD 032

FOREWORD

This Indian Standard was adopted by the Bureau of Indian Standards, afier the draft finalized by the Air EnvironmentProtection Sectional Committee had been approved by the Chemical Division Council.

The measurement of non methane hydrocarbons provides data for assessing atmospheric hydrocarbon pollutionfrom motor vehicles, filling stations, petroleum refineries and a variety of industrial processes employing solvents.The term non methane hydrocarbons is chosen for two reasons. Firstly, methane concentration in atmospheric airis so high that no pre-concentration is required for its measurement, unlike for the other hydrocarbons. Secondly,the role of methane in atmospheric photochemical reactions is negligible in comparison with the other hydrocarbonsput together. The method given in this standard is applicable for determining the hydrocarbon concentrations inworking environment, urban environment as well as for measuring in clean air atmospheres. The data obtained bythis method will be useful for determining the air quality as well as to determine the contribution of different sourcesto atmospheric hydrocarbon levels. This test method is one among the different parts being published underIS 5182 series of standards.

The composition of the committee responsible for 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 orcalculated, is to be rounded off, it shall be done in accordance with IS 2:1960 ‘Rules for rounding off numericalvalues ( rwised )’.

IS 5182( Part 21 ): 2001

Indian Standard

METHODS FOR MEASUREMENT OF AIR POLLUTIONPART 21 NON METHANE HYDROCARBONS IN AIR BY GAS CHROMATOGRAPHY

1 SCOPE

1.1 This standard prescribes the method ofmeasurement of non methane hydrocarbons in theatmosphere. The lower limit of detection is 0.1 partsper billion ( 1 part in 1010parts of air) by volume bypre-concentration method.

1.2 Two separate columns are recommended for theseparation of hydrocarbons, one for C2-C3 and thesecond for Cband above hydrocarbon. Approximately25 minare recorded for each analysis. The separationof ethane-ethylene on n-octane poracil C column needssub-ambient temperature programming. Programmedtemperature is needed for the separation of complexmixture of%ydrocarbons.

2 REFERENCE

The following Indian Standard contains provisionswhich through reference in this text, constitutesprovision of this standard. At the time of publication,the edition indicated was valid. All standards aresubject to revision and parties to agreements basedon this standard are encouraged to investigate thepossibility of applying the most recent edition of thestandard indicated below.

IS No. Title

4167:1980 Glossary ‘of terms relating to airpollution (jht revision)

3 TERMINOLOGY

For the purpose of this standard, definition given inIS 4167 shall apply.

4 OUTLINE OF THE METHOD

4.1 This method is applicable for routine analysis ofhydrocarbons in air samples collected in stainless steelcanisters, glass bulbs with teflon stopcock or inflatableteflon bags fitted with on/off valves. Since some ofthe hydrouirbons are modified in atmospheric air bysunlight and by reaction with oxides of nitrogen, airSaxnplbg for hydrocarbons is recommended to be donebetween 6 and 9 AM. Direct injection of 1 to 2 ml ofthe sample air into a gas chromatographyequipped withmolecular sieve 13X, 80-100 mesh filled in 1830 mmx3 mm inner diameter ( L D. ) stainless steel columnkept at 100”C in a helium or nitrogen gas flow, willgive peak corresponding to methane concentrationin sampled air. The retention time for methane at the

above operating conditions with helium flow rate of80 ml/min is 1.08 min.

4.2 Pre-Concentration

Atmospheric non methane hydrocarbons are to bepre-concentrated to determine their concentrationsat below the detection limit of 0.01 ppm by directinjection using aflame ionization detector ( FID ). Therecommended method for pre-concentration of gasphase hydrocarbons is by cryogenic condensationusing liquid argon [ Boiling point ( B.P. ) : 186°C ],liquid oxygen (B. P. : 183°C ) or liquid nitrogen(B. P.: 196%2). Liquid nitrogen is most used cryogenicfluid in laboratories and hence the current method isbased on the use of this cryogen. However, if alaboratory has an easy supply of liquid argon or liquidoxygen, it should be used in place of liquid nitrogen.The use of liquid argon prevents condensation ofoxygen and nitrogen during pre-concentration. Useof liquidoxygenrequires extreme caution as the reactionsof most organic compounds with liquid oxygen arehighly exothermic.

4.3 n-octane poracil C, 80-100 mesh, filled into3050 mm x 1mm inner diameter ( I.D. ) stainless steelcolumn is recommended for separation of C2-C5hydrocarbons. A column temperature of 27°C and ahelium flow rate of 40 ml/min are recommended. Ifhelium is not available nitrogen could be also used.Flame ionization detector is used-for detection. Zeroair or oxygen is used for supporting the flame in FID.

4.4 Since ethane and ethylene can not be separatedat 27°C, alternate calurrmrecommended for separationof C2-C4hydrocarbons is porapak Q , 80-100 meshfilled in a stainless steel column of 1830 mm x 3 mminner diameter ( I. D. ) at 50”C in a nitrogen flow of30 ml/min.

4.5 Capillary Column

Of fused silica, porous, -open tubular column of50 m x 0.32 mm inner diameter or other equivalentcolumn for hydrocarbon analysis.

5 ERRORS IN SAMPLING AND MEkJREMENT

5.1 Generally, for a homogeneous urban air mass,hydrocarbon contaminants would be expected to fallwithin the ranges given in Table 1. Stainless steelcanisters are ideal for storage of gases, but have thelimitation of low volume, large weight. Glass bulbswith teflon stop cocks are preferred next, but havethe risk of breaking. Teflon bags can be used tocollect samples upto 5 litres, but are not available

1

IS 5182( Part 21 ) :2001

indigeno-usly. The loss in storage in teflon bags couldbe 10 percent and higher due to ‘breathing’ by thebags. The problem of contamination due to needlevalves should be checked while using stainless steelcanisters.

Table 1 Ranges of Hydrocarbon ConcentrationsExpected in Urban Air

( Clause 5.1 )

C@mpound Range ( ppm )

Methane

Ethane

Ethylene

Propane

Propene

Acetylene

iso-butane

n-butane

1-butene

2-methyl propene

2,2, dimethyl propane

Trans-2 butene

cis-2-butene

iso-pentane

n-pentane

1.6 -15

0.005 -0.5

0.004 -0.3

0.003 -0.3

0.001-0:1

0.001 -0.2

0.001 -0.1

0.004 -0.4

0-0.02

0-0.02

0-0.01

0-0.01

0-0.01

0.002 -0.2

0.002 -0.2

5.2 As a general rule, if methane, ethane or propaneconcentrations are high relative to other identifiedhydrocarbons, look for local source emission of naturalgas. If acetylene and the butenes are high, look forautomobile exhaust source. If n-butane and iso-butaneare high, look for liquid petroleum gas filling leakagesource and if n-pentane and iso-pentane are high, lookfor a source of gasoline evaporation.

6 APPARATUS

6.1 Gas Chromatography ( GC )

A gas chromatography modified to facilitate pre-concentration of non methane hydrocarbons is shownin Fig. 1.

6.1.1 The gas chromatography column inlet insteadof connecting to injection port is connected to port 2of a 6-port valve. A capillary stainless steel tube isconnected from injection port of GC to port 1 of the6-port valve.

6.1.2 AU-column of 30 cm length, 3 mm outer diameter,partially filled with glass beads 60-80 mesh isconnected to ports 3 and 4 of the valve. During pre-concentration, this column is dipped to 1 cm into aliquid nitrogen bath in a Dewar flask.

6.1,3 Sampling canister or glass bulb or tefion bagis connected by means of a thin stainless steel tubeto port 5 of the gas sampling valve via a needle valve.Another stainless steel canister of 1 litre capacity

fitted with a vacuum gauge and a needle valve isconnected to port 6 of the 6-port valve. This canisteris partially evacuated so that when the needle valvesare opened after the U-column is cooled by liquidnitrogen, sample air flows through the U-column andthe hydrocarbons are condensed.

6.1.4 A water bath ( 60-70”C ) replaces the Dewarflask afier the sample pre-concentration.

6.1.5 The U-column is connected to the two canistersin the pre-concentration mode and by turning the knobof the 6-port valve, gets connected to the injectionport and the analytical column.

6.1.6 Flame Ionization Detector and ElectrometerAmplifier

6.1.7 Integrator/Recorder gives the area/peak heightof the chromatographic peaks.

6.2 Bor the purpose of calibration, sample canisteris replaced by a stainless steel canister with a syntheticmixture of known composition.

7 PROCEDURE

7.1 Evacuated stainless steel canister of 500-mlcapacity is tilled with sample air. The sample maybedried with a short column of silica gel to prevent moisturegetting into the canister. The -sample is brought tothe laboratory and connected to the 6-port valve asshown in Fig, 1. At this stage, both the needle valvesshould be completely closed. The U-column shouldbe dipped about 1 cm into liquid nitrogen bath.

Caution : If the U-column is completely dipped intoliquidnitrogenbath,largevolume of oxygen and nitrogencondense in the U-column; on the other hand, if thecooling is not sufficient, condensation of non methanehydrocarbons does not take place.

The pressure of the partially evacuated canister shouldbe adjusted to 400 mm of mercury. By keeping theneedle valve on the sample canister closed,open theneedle valve on the partially evacuated canister. Thepressure in the canister does not change if the gasline connections are leak tight. After cooling theU-column for 3-5 rein, open the needle valve on thesample canister gently so that sample airflows throughthe U-column at a slow rate. Continue pre-concentrationtill the pressure in the partially evacuated canister risesfrom 400 mm to 480mm as read on the vacuum gaugeattached to the canister. Close the two needle valves.Connect a vacuum pump to the partially evacuatedcanister and reduce the pressure in thk canister to160 mm. Open the upper needle valve for 3 to 5 s,keeping the needle valve on the sample canister closedtight. By this, the pressure in the U-column isreducedto 160 mm and any nitrogen or oxygen which may havecondensed re-evaporates. Close both the needle valves,heat the U-column with water bath and turn the knob

2

IS 5182( Part 21 ): 2001

-

t 1 ll&J&CT1014 F[D

r] ‘wNEEDLEVALVEL J

EQUALISERCANISTER

(IL)

DEWAR FLASK

x GC WITHCOLUMN

.

ElINTEGRATORRECORDER

/ \SAMPLECANISTER

(0.5L)

FIG.1 PRE-CONCENTRATIONSYSTEMANDGAS CHROMATOGRAPHFORNON METHANEHYDROCARBONMONITORING

of the 6-port vaIve so that the U-column is connectedbetween the injection and the analytical column,simultaneously starting the stop-watch to record theretention times of peaks.

7.2 The chromatogram of pre-concentrttted sampleis shown in Fig. 2. The first peak is due to methane.Since the boiling point of methane is - 165”C, it doesnot condense at the pre-concentration temperature( which is kept at about-110°C ). However, methanepresent in the free volume of the U-column will berecorded in the chromatogram, Ethane-ethylene willemerge as a single peak, followed by acetylene,propane, _propylene, butene isomers, iso-butane,n-butane, iso-pentane, n-pentane and neo-pentane.The retention times of higher hydrocarbons are muchlarger at 27°C on n-octane poracil C column and hencea separate column is recommended for the analysisof Cc and above hydrocarbons.

7.3 Quantification

7.3.1 “Todetermine the concentrations, it is requiredtodeterrnine the volume of pre~concentrated sample.Let Vbe the volume in Iitres, of partially evacuatedcanister. If the pressure of this canister rises from400mm to 480 mm dut%g pre-concentration, the volumeof air sampled is

(480 - 400) ~ ~ 80= — x V litres

760 760

If the temperature of this canister is t°C, then the

corrected gas volume at standard temperature andpressure is

80 273v

iii ‘(273+t)

Column : n-octaneporacil C80-100 mesh1.8m~lmmlDX3mm OD

Temp : 27°C(iso-Thermal)Carrier : HeliumFlawRate :40 ml/minDetector : FIDSample : 140ml of Air pre-concentrated

FIG.2 CHROMOTOORAMOF PRE-CONCENTWTEDAIRSAMPLEANALYSEDFORC2-C3HYDROCARBONS

3

IS 5182 (Part 21 ): 2001

7.3.2 Similar pre-concentration stepis donereplacingthe sample canister with a canister containing standardgas mixture. If the same volume of gas mixture is usedfor pre-concentration, then the concentration of eachhydrocarbon component is simply given by

Ac=

sample

Astandard

where C is the concentration in ppm of the componentin the standard gas mixture and AW~P1.,A,,,n~,,~ arethe respective areas in the chromatogram for thexampleand standard hydrocarbons.

7.4 Sample collection, pre-concentration and analysisas described above maybe repeated with the analyticalcolumn replaced byOV-101, 10percent on ChromosorbWAW “80-100 mesh, stainless steel column of3000 mm x 1mm inner diameter for the determinationof C~and above hydrocarbons. Following operatingconditions are maintained:

Column temperature: Initial temperature: 60”C;Initial time: 5 rein;Rate: 5°C/min;Final temperature: 100”C

Carrier gas : Helium/nitrogen at 40 mlhninFlame ionization detector

. ... . . .7.4.1 Typical chromatogram for pre-concentratedsample is shown in Fig. 3.

7.4.2 Quantification

The volume of air sampled is determined as in 7.3.

The amount of each solvent is determined by comparingthe chromatogram with standards injected.

Concentrations of solvents are expressed in eithermg/i or ppm.

Column : 10% OV-101 on ChromosorbWAW, 80-100 mesh

Initial Temp : 60”C

Initial Time : 5 min

Rate : 5“C/min

Final Temp : IOO”C

Carrier Gas : Helium

Flow Rate : 40 ml/min

Detector : FID

Sample : 0.5 a.ofcs

(Containing 0.25 x 10-3L of each compound)

FIG. 3 CHROMOTOGRAMOFPRE-CONCENTRATED

HYDROCARBONSONOV-101COLUMN

4

IS 5182 (Part 21 ): 2001

ANNEX A

( Foreword)

COMMITTEE COMPOSITION

Air.Environment Protection Sectional Committee, CHD 32

Chairman Representing

SHRIDILIPBISWAS Central Pollution Control Board, Delhi

Members

SHRIRAM GOPALSHRIS. C. BHARADWAJ(Alternate )

DR M. Z. HASAN

DR S. SADASIVANDR T. N. MAHADEVAN(Alternate)

SHRIR. K. DASDR K. C. NARANG( Alternate )

DR V. M. SHASTRI

SHRID. N. SINGHDR JANARDANSINGH(Alternate )

SHRIA. K. GUWASHRIANIL JAIN( AJ(ernate )

RepreSentatiVe

DR P. N. VMHWAFJATHANJIR S. K. BHARGAVA

SHRIS. C. NIGAM

DR B. V. BAPATSHRIP. R. SHINGLE(

SHRIASHOKBHATIA

SHRIS. S. GAUTAM

Alternate )

Uternate )

SHRIM. R. RAJPUT( Alternate )

SHRIT. K. RAY

DR T. S. PATEL

REPRESENTATIVE

SHRIS. K. JAINSHRIS. K. JAIN(Alternate)

DR B. SENGUFTADR C. S. SHARMA(Alternate)

RepreSentatiVe

DR A. EHASKASrSH~IA. JHAVAR(Ahernate-I jSHRIRAKESHAGARWAL(Alternate-II )

DR ( Ms ) B. SWAMINATHANDR S. NAND (Alternate)

R2pRFsENTATIvESHRIS. S. BHANIXWAD(Alternate )

Environment Management, NTPC, New Delhi

Air Pollution Cootrol Division, Nagpur

Bhabha Atomic Research Centre, Mumbai

Cement Manufacturers Association, Chennai

Steel Authority of India Ltd, New Delhi

Central Fuel Research Institute, Dhanbad

Bharat Heavy Electrical Ltd, Tamil Nadu

Coal India Ltd, Calcutta

Industrial Toxicology Research Centre, Lucknow

Dhrmamsi Morarji Chemical Co Ltd, Mumbai

National Organic Chemical Industries Ltd, Maharashtra

Ministry of Environment and Fo~ests, New Delhi

Directorate General, Factory Advice Service and Labour Institu:e,Kanpur

ABB Alstom Power India Ltd, West Bengal

National Institute of Occupational Health, Ahmedabad

Indian Oil Corporation, Faridabad

Department of Industrial Policy and Promotion, New Delhi

CPCB, CBD cum Office Complex, Delhi

Indian Chemical Manufacturers Association, New Delhi

Hindustan Lever Ltd, Mumbai

The Fertilizer Association of India, New Delhi

Municipal Corporation of Greater .Bombay, Mumbai

( Continued on page b )

5

IS 5182( Part 21 ): 2001

( Continued from page 5, )

— .—

Memlwrs

SHR]THiRUS. BALAKRISHNAN

DR S. K. KAPOOR

DRG. S. BAINS

DR G. V. PRASADSHRIM. JANARDHAN( AJternate J

REPRi3ENTATIW

REPWsENTATlvE

REPRESENTATWE

Representative

SHRI U. K. NANDWANISHRIRAW SONDHI(AJternate )

DR GURDEEPSINGH

REP-ENTATWESHRII. M. SHARMA(Alternate)

SHRIY. K. SAXENA

SHRIM. M. MALHOTRA,Director ( Chem )

Representing

Tamil Nadu Pollution Control Board, Chennai

Centre for Environment & Explosive Safety, Delhi

Punjab Pollution Control BoarJ, Prttiala ( Punjab )

Vimta Labour Ltd, Hyderabad

Bhagwati Analab, Hyderabad

Automotive Research Association of India, Pune

Instrumentation India Ltd, Kota ( Rajasthan )

Gujarat Pollution Control Board, Gandhinagar

Sulzer Flovel Hydro Limited, Faridabad

Standardisation, Testing & Quality Certification Directorate,New Delhi

Indian School of Mines, Dhanbad

Eternit Everest Limited, New Delhi

Gujarat Ambuja Cements Limited, New Delhi

Director General, BIS ( Ex-officio Member )

Member-Secretirry

DR R. K. SINGH

Additional Director ( Chem ), BIS

6

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Review of Indian Standards

Amendments are issued to standards as the need arises onthebasis of.comments. Standards are also reviewedperiodically a standard along with amendments is reaff~med when such review indicates that no changes areneeded; if the review indicates that changes are needed, it is taken up for revision. Users of Indian Standardsshould ascertain that they are in possession of the latest amendments or edition by referring to the latest issueof ‘BIS Catalogue’ and’ Standards: Monthly Additions’

This Indian Standard has been developed from Doc : No. CHD32(512 ).

Amendments Issued Since Publication

Amend No. Date of Issue Text Affected

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