EPA-600/7-82-063

                                    November 1982
        EVALUATION OF POTENTIAL VOC
           SCREENING INSTRUMENTS
                     by

             Kenneth T. Menzies
               Rose E. Fasano
           Arthur D. Little, Inc.
            Cambridge, MA  02140
            Contract 68-02-3111
              Task Number 121
                 EPA
              Project Officer

             Merrill D.  Jackson
          Technical Support Staff
Industrial Environmental Research  Laboratory
     Research Triangle Park,  NC 27711
     OFFICE OF RESEARCH AND DEVELOPMENT
    U.S.  ENVIRONMENTAL PROTECTION AGENCY
     RESEARCH TRIANGLE PARK, NC  27711

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                                                              PB83-139733
    Evaluation of Potential VOC
    Screening Instruments
    Arthur D. Little,  Inc.
    Cambridge, MA
    Prepared for

    Industrial  Environmental Research Lab,
    Research Triangle Park, NC
    Nov 82
U.S. Department of Commerce
National Technka! Information Sen*
NT1S

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                               .  TECHNICAL REPORT DATA
                           fftetlr rtod luitnictioni on tht nvmt btfort completing)
It. REPORT NO. 2.
IEPA-600/7-82-063
14 TITLE AND SUBTITLE
(Evaluation of Potential VOC Screening Instruments
i
17. AUTMCRIS*.
1 Kenneth T. Menzies and R.E. Fasano
1 ' '
J9 PERFORMING ORGANIZATION NAME AND ADDRESS
Arthur D. Little, he.
I Acorn Park
1 Cambridge, Massachusetts 02140
117 SPONSORING AGENCY NAME AND ADDRESS
1 EPA Office of Research and Development
1 Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
is. SUPPLEMENTARY NOTES j£RL-RTP project officer is Merrill
919/541-2559.
3. RECIPIENT'S ACCESSION NO.
PB83 139733
V REPORT DATE 1
November 1982
ft. PERFORMING ORGANIZATION CODE 1
8. PERFORMING ORGANIZATION REPORT NO. 1
C-82-480-03
10. PROGRAM ELEMENT NO. I
11. CONTRACT/GRANT NO. 1
68-02-3111, Task 121
^fcTiSTjW'-W'H
1«. SPONSORING AGENCY CODE 1
EPA/600/13
L D. Jackson. Mail Droo 62. 1
Reproduced from grrel 1
best available copy, TJfflRJ^ ^\
 •                »                               ->          «•
 [screening instruments for analysis of volatile organic compounds (VOCs). An initial
 I review of available portable VOC detection instruments  indicated that detectors
 I operating on several principles (i.e., flame ionization, catalytic combustion, photo-
 I ionization, infrared absorption, and thermal conductivity) might be useful for VOC
 analysis. However, flame ionization and catalytic combustion devices evaluated pre-
 viously showed poor sensitivity for highly  substituted aliphatic and aromatic organic
 compounds.  Instruments utilizing photo ionization and infrared may be able to meet
 necessary criteria for practical and accurate VOC analysis of highly substituted or-
 ganics. Therefore, three commercially  available instruments (i.e., HNU PI-101,
 AID 580, and Foxboro Miran 80) were modified and evaluated for 32 such compounds
 in concentrations of 100-10,000 ppmv. Results show that photo ionization may be
 suitable for general VOC screening, but a  reliable instrument/dilution system does
 not exist. Infrared absorption will apparently not provide suitable general VOC
 screening, but may be useful for analyzing some classes of organic compounds.
117.
                             KEY WORDS AND DOCUMENT ANALYSIS
\i DESCRIPTORS
[Pollution Photochemical Reac-
1 Analyzing tions
Organic Compounds Infrared Radiation
Volatility Electromagnetic Ab-
Selection sorption
Photo ionization Processing
Leakage
[19 DISTRIBUTION STATEMENT
Release to Public
b IDENTIFIERS/OPEN ENDED TERMS
Pollution Control
Stationary Sources
Volatile Organic Com-
pounds (VOCs)
Screening Instruments
Fugitive Emissions
IB. SECURITY CLASS iThil Rtportl
Unclassified
JO SECURITY CLASS tThil pogt)
Unclassified
o. COS ATI 1 if Id Croup |
13B
14B 07E 1
07C 20F
20M
14G 20C
07B 13H
71 NO. Of PAGES 1
96
37. PRICE I
CPA Form 2210-1 (»-7J)

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                               ACKNOWLEDGMENT
This report Is submitted in partial fulfillment of the requirements of
EPA Contract No. 68-02-3111, Technical Directive 121.  The authors wish
to acknowledge the support of she Project Officer for this work,
Merrill Jackson of the Technical Support Staff, IERL-RTP.      Robert
O'Neil,     Kenneth Alder and     Koyong Cho also contributed to the
project.
                                   ii

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                            TABLE OF CONTENTS
     Acknowledgement                                            ji

     List of Tables and Figures                                 iv

     ABSTRACT                                                    1

 1.   INTRODUCTION                                                2

 2.   INSTRUMENT SELECTION                                        6

     A.   General Rationale                                       6
     B.   Unit Selection                                         18
     C.   Unit Modification                                      21

 3.   COMPOUND SELECTION                                         25

 4.   EXPERIMENTAL PROCEDURES                                     30

     A.   Introduction                                            30
     B.   Instrument  Operation                                    30
     C.   Preparation of Gas Standards/Samples                    30
     D.   Calibration Protocol                                    33
     E.   Instrument  Sampling                                     33
     F.   Data Analysis                                           34

5.   TEST RESULTS                                                35

6.   DISCUSSIONS AND CONCLUSIONS                                 63

    A.  Photoionization Detection                               63
    B.   Infrared Detection                                      64
    C.  Conclusions                                             71

7.  LITERATURE CITED                                           72

8.  APPENDICES                                                 72

    A.  HNU Systems, Inc.- Model PI-101                       A-l
    B.  AID, Inc. -Model 580                                   B-l
    C.  Foxboro/Wilks, Inc.  - Miran 80                        C-l
                                   ill

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                      LIST OF TABLES AND FIGURES
Table No.                                                      Page

   1           Compounds with Response Factors
               Equal to or Greater than Five                   3

   2           Portable VOC Detection Instrument
               Certification                                   4

   3           Portable lonization Detectors                   7

   4           Portable Infrared Instruments                   9

   5           Portable Combustibles  Analyzers                n

   6           Potential VOC Detectors                         19

   7           Additional Compounds to  Test                    26

   8           Synthetic  Organic  Compounds with  Vapor
               Pressure Greater  than  0.3 kPa  (20°C)
               and Not  Tested Previously                       27

   9            Compounds  for Evaluation                        29

 10            Calibration Scheme for Miran-80                 31

 11           Response Factors on PI-101                      36

 12           Response Factors on Miran 1A/80                 39

 13           Calibration Data for Miran 80     ,             66
                                                         «
 14           Substituted Aliphatic Compounds with
              Response Factors Less than Twenty at
              3.3 ym                                          68

 15           Chlorinated Compounds and Response
              Factors at 13.5 ym                              69
                                  ivr

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                 LIST OF TABLES AND FIGURES (Continued)
 Table  No.                                                      Pa^e

  Al            Specifications for Model PI 101
                Photoionization Analyzer                        A-2

  A2            Brief Description of Instrument
                Controls and Functions                          A-4

  Cl            Specifications                                  C-2

  C2            Systems Specifications                          C-4
Figure No.

   1           Photoionization Efficiency Curves as
               a Function of Photon Energy for an
               Aromatic Hydrocarbon and an Alkane              14

   2           Instrument Response vs lonization
               Potential for Several Classes of
               Compounds                                       15

   3           HNU Systems,  Inc.  Dilution Probe «               22

   4           AID,  Inc.  Dilution System                       23

   5           Calibration Curve  for 1,2-Dichloro-
               ethane for the HNU Instrument                   65

  Al           Control Panel Functions                       A-5

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                                ABSTRACT
 This  report  describes  the  evaluation of potential fugitive source
 emission screening  instruments  for analysis of volatile organic
 compounds (VOC).  An initial  review of available portable VOC detection
 instruments  indicated  that detectors operating on several principles,
 i.e., flame  ionization, catalytic combustion, photoionization, infrared
 absorption and thermal conductivity, might be useful for VOC analysis.
 However,  flame ionization  and catalytic combustion devices evaluated
 previously have shown poor sensitivity for highly substituted aliphatic
 and aromatic organic compounds.  Instruments operating on the photo-
 ionization and infrared principles may be able to meet necessary
 criteria  for practical and accurate VOC analysis of highly substituted
 organics.  Therefore, three commercially available instruments were
 selected, modified, and evaluated for 32 such compounds in the
 concentration range of 100 ppmv to 10,000 ppmv.  The results indicate
 that the photoionization principle may be suitable for general VOC
 screening but a reliable instrument/dilution system does not exist at
present.  The infrared absorption principle will apparently not provide
a suitable general VOC screening device but may be useful for analysis
of some classes of organic compounds.

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  1.    INTRODUCTION

  The U.S. Environmental Protection Agency has issued performance standards
  and guidelines1 to limit emissions of volatile organic compounds (VOC)
  from several stationary source categories such as surface coating oper-
 ations.  These guidelines apply to industries which emit significant
 quantities of air pollutants.  It has become apparent that sources other
 than classical point sources may also emit large amounts of VOCs into
 the workplace and surrounding atmosphere.  The EPA's Office of Air
 Quality Planning and Standards (OAQPS) is, therefore, evaluating the
 need for the control of fugitive emissions of VOCs from such sources
 as valves,  pumps and drains.  As described in EPA Method 21, Determina-
 tion of Volatile Organic Compound Leaks,2 technically and economically
 feasible devices suitable for monitoring such leaks include only a few
 portable detectors.   These devices can be placed near possible points
 of emissions and will respond to releases of the organic compounds.
 Specific instruments  suitable for this purpose include,  but are not
 limited to,  catalytic oxidation,  flame ionization, infrared absorption
 and photoionization  detectors.

 Unfortunately,  due to the chemical complexity of many fugitive VOCs
 and the lack of universal sensitivity of these  detectors,  the detectors
 previously  evaluated  cannot adequately measure  the concentration of  all
 chemicals likely to be released.   This fact  has been documented3 for
 two commercially available  detectors  using flame ionization (FID)  and
 catalytic combustion  principles.   Among 168  compounds tested, 23 showed
 sufficiently poor response  that  the actual and  measured  concentrations
 differed by  a factor  of greater  than  five (Table 1).   The  classes  of
 compounds which show  the  poorest  agreement with the actual concentration
 generally incorporate functional  groups  such as halides, hydroxyl
 (alcohols),  carbonyl  (aldehydes,  ketones)  and carboxylate  (acid) and
 include  both substituted  aromatic hydrocarbons  and lew molecular weight,
 highly  substituted aliphatic  compounds.

Additional portable devices which respond accurately  to  these compounds
 are needed for  VOC screening.  Instruments other  than  flame  ionization
 or  catalytic oxidation detectors which might meet  this goal  operate
 on  the principles of  infrared  absorption, photoionization  and thermal
 conductivity.1*

The first step  in this task was to select and procure one  or  more units
of  those detectors which meet  the specifications of Method 21.  The VOC
instrument must be rugged, reliable, relatively inexpensive,  portable
and easy to operate.   Of course, it must respond to the organic compounds
of  interest and be able to measure the leak definition concentration
specified in the regulations.  According to Method 21, the instrument
must be intrinsically safe for operation in explosive atmospheres as
defined by the applicable National Electric Code.  At this time, there
are few detectors which are "approved" for such an environment (Table 2).

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                                  TABLE 1

                      COMPOUNDS WITH RESPONSE FACTORS

                      EQUAL TO OR GREATER THAN FIVE
  OCPDB3                                                        FID
  ID No.           Compound Names                          Response Factor

  120             Acetophenone                                 10.98
  —              Acetyl-1-propanol, 3-                        10.87
  490             Benzcyl Chloride                              6.40
  790             Carbon Disulfide                            571.92
  810             Carbon Tetrachloride                    '     21.28
  •830             Chloro-Acetaldehyde                          13.40
  —             Dichloro-1-propanol, 2,3-                    61.51
  —             Dichloro-2-propanol, 1,3-                    29.34
  —             Diisopropyl Benzene, 1,3-        ^             9.43
  —             Dimethyl Styrene, 2,4-           *         •„ 37.09
 2060            Formic Acid                                  34.87
 1221            Freon 12                                      9.65
 2073            Furfural                                      7.96
 2105            Glycidol                                      8.42
  —             Hydroxyacetone                                8.70
 2500            Methanol                                      5.69
  —             Methyl-2,4-pentanediol, 2-                   96.34
 2690            Methylstyrene, a-                             10.24
 1660            Monoethanolanlne                             28.04
 2770            Nitrobenzene                                 29.77
 2910             Phenol                                       11.75
  —              Phenyl-2-propanol,2-                          89.56
 3291             Tetrachloroethane,l,l,2,2                      6.06
aOrganic Chemical Producers Data Base
'Response Factor - A^tual Concentration
                   Measured Concentration
Cource:  Reference 3

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                                              TABLE  2

                          PORTABLE VOC DETECTION INSTRUMENT CERTIFICATION
       Manufacturer
 Model No.
                      Certification
Bacharach Instrument  Co.,
Santa Clara,  California
Century Systems,
Arkansas City,  Kansas

HNU Systems, Inc.
Newton Upper Falls,
Massachusetts

Mine Safety Appliance Co.,
Pittsburgh, Pennsylvania

Survey and Analysis, Inc.
Norchboro, Massachusetts
TLV Sniffer
 OVA-128
 OVA-108

  PI-101
   AO
 OnMark
 Model 5
Intrinsically safe, Class I, Division 1, Groups C & D
Intrinsically safe, Class I, Division 1, Groups C & D, and
   Class I, Division 2, Groups A & B

Intrinsically safe, Class I, Division 1, Groups A, B, C & D
Intrinsically safe, Class I, Division 1, Groups A, B, C & D

Intrinsically safe, Class I, Division 2, Groups A, B, C & D
Intrinsically safe, Class I, Division 1, Group D, and
Class I, Division  2, Groups A, B, & C

Intrinsically safe, Class I, Division 1, Groups A, B, C & D
 Source:  Reference A

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 The  second  step  in  this  task was  to set up a laboratory system
 capable  of  mixing known  volumes of vapors with air and delivering the
 mixtures of known concentration to the detectors.  Tedlar bags and
 a volumetric mixing system were selected for sample preparation since
 they provide adequate accuracy/precision and require little cost ov
 time to set up.

The third step in this task was evaluation of the detectors for
response to the compounds of interest.  The response factors were
determined at several concentrations over the range of 100 ppmv to
10,000 ppmv.  Measurements were limited to concentrations approaching
about 90% of the saturation concentration or 75% of the lower explosive
limit (LEL).  In order to permit statistically valid interpretation of
the measured response factors,  five replicate measurements at three
concentrations were conducted.   Data analysis included calculations
of mean response factors and confidence intervals.

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  2.   INSTRUMENT  SELECTION

  A.  •General Rationale

  A recent summary of available portable VOC detection devices'* lists a
  number of instruments operating on the following principles:

           Flame lonization (FID)
           Photoionization (PID)

           Infrared Absorption (IR)

           Thermal Conductivity (TC)
           Hot Wire/Catalyst Combustion (Combustion).

 The majority of available instruments operate on one of three principles,
 i.e., FID,  IR or Combustion (Tables 3, 4, 5).  As noted above and in
 previous work,3  two specific  FID and Combustion devices show poor
 sensitivity to several substituted organic compounds.   Due to this
 observation and with the understanding that other FID or Combustion
 detectors available from different manufacturers probably do not differ
 significantly in construction or sensitivity, alternative VOC screening
 devices  were evaluated.   These were selected from instruments operating
 on  other detection  principles,  including photoionization,  IR and thermal
 conductivity.   Fhotoionization or thermal conductivity detectors are
 highlighted in Tables  3  and 5,  respectively,  while infrared detectors
 are  listed  in Table 4.

 The  selection  of potential VOC detectors from this list depends  in
 several  criteria which are outlined in EPA Method 21.   That is,  an
 instrument  suitable for  screening  should hav». the following characteristics:

           (1)  Fast response  (<30  seconds);
           (2)  Measurement range 100  to 10,000 ppmv;

          (3)  Similar responsiveness  to  a variety  of organic vapors;

          (4)  Portable;

          (5)  Rugged;
          (6)  Reliable;
          (7)  Inexpensive;
          (8)  Easy to operate; and
          (9)  Intrinsically safe  (as per National Electric Code).

Each of the first tiu.'r»e characteristics is of primary importance in
providing a practical instrument for VOC screening.  Fast response time
is necessary for rapid screening of a large number of fugitive sources.
The specified measurement range is required by the need to limit
significant leaks of volatile organic compounds.  Equal molar sensitivity

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                                              TABLE 3


                                  PORTABLE IONIZATION DETECTORS
Manufacturer
Ar^lvtUnl
IntftTuavnC
Inc.
.\votu1alr.




i
I
i
'



Sendtx.
Environmental
ar.d ?rccess
Instruaents
Otvlsioa
West Virginia
C«ntury
Svitcis, Inc.
Arkansas City,
Kansas




General Elec-
tric Instro-
nent Products
tynn.
Massachusetts
Heath Consul-
tants. Inc.
Jtotighlon,
Hassachasett
Hods I
Mo.
J)0b
end
JM


jjjC


511-12*




8401*





OVA-U8

OVA-128*
OVA-98

OVA-108*

TVH-1-
-


Detecto
PAR II1

Pollutant (•)
Detected
Nonncthnnc
total hydro-
carbons


Total hydro-
carbons

Total hydro-
carbons and
Individual
troop ounds
with CC
Total hydro-
carbons




Total hydro-
carbons
Total hydro-
carbons
Total hydro-
carbons
Total hydro-
carbons
Ualogcnated
ccapounds



Total hydro-
carbons

Principle
o(
Operation
FID




rio


FID/CC




no





FID

FID/CC
FID

FID/CC

capture0



FID


Cost
»
3711




3987


4968




3193





3300

4200
3500

420C

4060



2930


Weight
Ib
16.5




20.3


41




40





12

12
12

12

23



8


ppa
0-200 and
O-ZOOO far
Model 550;
n-rao nnj
o-lu.ooo lor
H.'iU-l iil
0- lo.uon.
0-2UOU, and
0-100





1-1000





0-10 and 0-100

0-1000
0-10,000

0-10,000

9 ranges:
0-1 through
0-10,000

1
0-10
0-100
0-1000
Acourscy
+3




+1







±-





+2

+2
±-

+2

+10



J
+4
1
Mensttlvltjr
0.1 ppa on
n Bviilt- of
0-200 ppa


1 pim on •
Mcala of
0-2000 ppa
0.03 ppa ea
propane



0.01 ppa





0.2 ppa
•ethane
0.2 ppa
•ethane
0.5 ppa
•ethane
0.5 ppa
nt thane
0.1 ppa



2 opa
2 ppa
3 PC"
Precision
X
+3




+3







±2





+2


+2










Raoponnc
Tine
3




3







8





2


2



120



13


Hois*
U.--S than
0.1 t-pa on
0-200 ppa


1 ppa on •
(IClllli Of
O-20OO ppu





±-s



















Anbimt
Teop«rature
•c
0-/.0

1

I
0-40


5-43




3-40





-20 to 40

-20 to 40
-20 to 40

-20 to 40

0-5S



0-30


Drift*













s - +U «4>
• a *1£ 124)
» ^ _^»» V*— /




S - ±11 (1}

*- +11 (1)
s " +1!! (?)

s - +;z (i>

Be.ll.iil.





s - ^41 (7)
Reproduced from
bett available copy.

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                                                                            TABLE  3  (Continued)
Manufacturer
HXV Syatema.
Inc.
N.-vton
Vrrtt r»ll».
X.iMi«4>-liuii»)tts






M*lre>v lab*.
SrrliUflcld,
VI r 'laid
!
Mlo* Safety
Appliance* Go.
Pittsburgh.
Pennsylvania
Survey and
Analysis. lac.
Scrthhcrought
Massachuietts





Model
He.
FI-1011










UC-500


Total BC
analyser


Snlfty
Model
A-SOO*






Follut«nt>l iiv light
rcnults In
lOlllailtiull
Total hydro-
cnrbons

Total hydro—
carboos


Total hydro-
carbon*






t
Principle
of
Operation
Fbotolon-
fttation









FID


FID



FID








Cost
»
3395













3S50



1695 for
baste
unit.
2295 for
entire
porta-
bility
package

Weight
Ib.
<9










40


35



17








Range
ppm
0-20.
0-200 and
0-2000








0-10.
0-50.
0-100. and
0-1000
0-4 and
0-12.000


0-10

0-100

0-1000

0-10.000


Ace iracy
I

-7
-7








11 on low
seal*

11



-55

-35

-3

+20


Sensitivity
1 ftm










0.1 ppa
CH,





2 rr*








Freelaion
X


*








±1















teeponsa
Tins
a
5










45


1



4








Kol.e











tO. 05 ppsi
aI4

±0.5












Aaiblent
Teaperatur*
•c
-IS to 50










10-40


4-45



0-50








Drift*
« • IX (7)
s - 32 (6)
for a, rAnga ef
0-20 ftm; no drift
for other rtnrjf*






S • 0.2 fpm (2*)
s - 0.2 ppa (24)
0-10 H-o
• - 0.51 (24)



• *20I (7)
- »12X (7)
- 0
- «; (7)
• 40.71 (7)
• 0
- 10.71 (7)
• 0 »

00
          The letters "x" and "s" indicate zero drift and span drift.   The nuabera  of hours over which drift occur* 1* liven in pareotheali.
          A charcoal tube 1* used to  adsorb organic*, except methane,  and • rang* of 0-10 ppn 1* available with the recorder.  The instrument can be used
          as alara by selling in 0-1000 range.  Thia 1* a screening and leak detection device.
          cThe following features are  available!  a range of 0-100 ppa with recorder only; Internal power, oxygen, and hyi'roge" •uppl.lea; a heated probe;
          'and a battery-operated recorder with a range of 0-100 oV d.c.
          Ca;abilities equal or exceed those of Models 550 and 555.
          'Capabilities to detect higher concentrations require further investigation.  This aay be suitable for ambient fir measurement only.
          'Optional CC.
          •optional CC.
          A heated pletinua wire embedded  In rubidium combusts incoming gases.   Combustion of halogenated material* cause* electron* to flow from the
           rubidlua.  The electric*! flow measured 1* proportional to the amount of  htlogenated material* present.
          ^erforaence characteristic* •• measured by KIOSB.  Reference 6. Section 3.
          ^Inaccurate.
          Source:  lafarenc* 4

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                                              TABLE  4

                                    PORTABLE INFRARED INSTRUMENTS
>Uuuf«cturar
An.itv.u. Inc..
California









'
•
Ajtro
Resources
Corp. .
KC-JI ton.
Texas
Chrysler
HunttvlUe
Electronics
Division.
Hvn-. jvllle.
Al.ibio.1

foxboro
Analytical.
MU« Infra-
red Center,
S. Xorvalk,
Connecticut



Us Tech. Inc.
Mountain View,
California

Mndel
Mo.
A«-400b












S000e


III-C'1
HDpAe?
it
Atlasd

Hlran
-104*



Hlraa-lA


Dallde
Detector

Pollutant (e)
Detected
Individual
species
abnorblns. XR











Individual
hydrocarbons


Total hydro-
carbons
Total hydro-
carbons
Total hydro-
carbons
Any species
absorbing IK •
between 2.5
and 14.5 vm
in wavelength

Any species
absorbing I*
between 2.5
and 14.5 la
in wavelength
Ualogenated
hydrocarbons

Principle
of
Operation
IR












XX


IK
IX

IK

IK



IK .


Inhancement .
>f radiation
from a spark
>y halogen*
Coet
S
2393
or an
nalyier
•ensuring
nliiMlu
gas
»7*i
far an
analylur
Measuring
hrce
gate*
Model
403)








Not sold
in U.S.
but price
osy be
siallar to
Uran-lA
6600


112'

Weight
Ib.













25


20
20

30

24



32


13

Range
PPM













Specified by
customer, up
to 100Z


0-300 and
0-2000
0-300 and
0-2000
0-300 and
0-2000
ppa to
percent




-------
                                                                   TABLE  4  (Continued)
Manufacturer
Infrared
InJuiit rtf».
Inc.
*alUtf«ii*r"'






1
1
|


Xlae Safety
Arpllacce Co.
Pittsburgh.
PeansTlvanla
Model
No.
Ut-711


1R-702*


1R-703*

f
U-703





LIRA 301*



P<
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                                        TABLE  5

                           PORTABLE COMBUSTIBLES ANALYZERS
Manufacturer
M.ri«r«h
Ln»truovnt Co.
Sjnu Clara.
California

3U-:urlne
Industries,
Inc.
Malvern.
Pennsylvania

Control
Instru>e3ts
Cor;.
Fiilrflcld,
New Jersey
las Tech. lac.
Mcuntaln View.
California

International
Sensor
Technology
Santa Ana,
California

tine Safety
Appliance Co.
Pittsburgh,
Pennsylvania


HoJel
Ha.
C
L
l|b
TLV
Snlfferc
922


900. 900t
and 300RS

rrAPd




1177

. 1238

AC5100





20*

30*
40«

Pollutant (a)
Detected
Co&bustlbl*
gases



Coabustibla
tases and
vapors
Coabustibla
gases and
vapors
Fl unable
gases and
vapors


Combustible.
gases
Coabustibla
gases
Coabustlbl*
gasea and
vapora



Combustible
gases
Combuatlbla
gases
Coobustlbla
gases
rrlnclpla
of
Operation
Catalytic
combuatlon

Catalytic
combustion
Catalytic
coabustlon

Catalytic
coabuatlon

Thermal
coobustlon



Catalytic
combustion
Catalytic
combustion
Change in
resistance*
within
detector


Catalytic
combustion
Catalytic
conbustlon
Catalytic
combustion
Cost
233
160
279
896

495


685.
695 and
715





523

695

1200
for ppm
scale;
825
for LEL
acala
374

374
374

Volght
It
4
4
3
5

1.3


3

28




6

7







6




Range
O-IOOX LEL
o-ioo: LEL
0-100X LEL
0-100. 0-1000
t 0-10.000 ppm
0-100X LEL


0-100X LEL

0-100X LEL




0-1001 LEL

0-1001 LEL
4 0-500 ppm
LEL and ppa





0-100X LEL

0-1001 LEL
0-lOX and
0-100Z LEL
Accuracy
X



±3

J5t LEL


15X LEL

0




13

t2

t3










ganaltlvlty



2 ppm.


























Precision
X



13






±1




12

±2

15










Rcaponaa
Time
a





3


5

<10




4

10

10 on LEL
scale and
60 on ppm
*Cfll4







Ambient
Tmmperatura
•c
O-50




-15 to 40


-15 to 40

0-52




0-40

-20 to 50












Drift*










c • <±5X (1 yr)
a - <15X (1 yr)







negligible in a
3 -month period









Reproduced from
    available rnpy

-------
                                                          TABLE  5   (Continued)
Manufacturer
Survcv and
Analyrl*. Inc.
Xortliboro.
MlSfJchutettS
Tcicdvnc
Analytical
Instruments,
San Gabriel.
California
He-del
No.
OnKark
Model Sh


980




pollutant (a)
Detected
Combustible
f,as«a and
vapors

Total com-
bustibles
and oxygen


Principle
o(
Operation
thermal con-
luctlvlty


Catalytic
combustion



Coat
»
285








Height
Ib
<3



17




Range
fP*
0-5 and
0-100X


Scale: O-5X
'nethane; othera
are available


Accuracy
X
13



12




Senaltlvtty




0.5X of
Cull «cal.



fraclalon
X
a








lUfiponae
Tla«
a
<10



20




Ambient
T»l>uratur«
•c
0-50



0-50




Drift*
« - 1*1 (2 mo)








*lhe lettera "t" and "a" Indicate  sero drift and apan drift given a* percent of scale over the time specified la par on the «l.
 Catalytic coobuallon (hotwire)  In low range and thernal conductivity  la Ugh range.
cTie raage* of TLV caa be nultlplied by 10 with a dilution probe.
 ihe FFAP uses a propane flaae to  coabust aanple gas and la fully portable.
*Can be factory calibrated for five gases, such as pentane.
 Calibrated  to oeasure natural gas and petroleum vapors In air nlxturea.
^Factory calibrated for pentane.                       %
Nllacent for the 0-1001 scale are thereal aensors heated to 300* to  400*F. and fllaMntS) for the 0-51 seal* are
 catalytic  sectors heated to 1200* to  1300'F.
Source:  Reference

-------
  to compounds of widely differing functional character is not achievable
  with currently evaluated instruments but is a desirable goal.   The
  other characteristics such as portability and instrlnsic safety are
  also important but none should be considered individually critical to
  the acceptance of a potential detector.

  Assuming that characteristics of fast response and appropriate measurement
  range are available in potential VOC detectors,  the ability of the devices
  to meet the criterion of similar responsiveness  needs to be reviewed prior
  to final instrument selection.   Thus, the efficacy of various  operating
  principles to meet this criterion is discussed below.

       (1)  Fhotoionization

  Fhotolonization detectors utilize ultraviolet radiation to ionize  a. small
  fraction of molecules introduced into an ionization chamber.   The  ioniza-
  tion  process is initiated by  absorption  of a photon of sufficient  energy,
  i.e., greater than the ionization potential,  to  remove an electron from
  its ground state  to infinity.  A  free electron  and positively charged
  ion are  thus formed:

                             R +  hv •*• R+ + e~

  If the energy of  the  UV lamp  is  less  than the ionization  potential of
  the compound, no  ionization takes place.   Ions formed  in  the detector/
  ionization chamber may reach  the  electrodes under  the  influence of an
  electric field and produce a  small current.   The number of ions which
  reach the  electrode is  proportional  to the concentration, although
  only a very small fraction (M3.012) of Che molecules in the ionization
  chamber are  ionized by  incident radiation.  Depending  on  the character
  of the electrons,  e.g., sigma ys pi electrons, the yield  of ions
  (photoionization efficiency) may vary as a function of the energy  of
 incident photons  (Figure 1).   At present, UV  sources are-available for
 commercial instruments which emit photons of approximately 9 eV, 10 eV
 or 12 eV.  Based on the ionization potentials of organic compounds,5
 it is apparent that certain classes of compounds, e.g., aromatics and
 aliphatics greater than carbon number C7, can be ionized by a 10 eV lamp
 while many substituted aliphatics require photons of at least 11 eV
  (Figure 2).  This  observation leads to the conclusion that with sufficient
. energy most organic compounds can be ionized and detected.  A practical
 upper energy limit for VOC analysis is about 12 eV since the major
 components of air  such as nitrogen, carbon monoxide, carbon dioxide
 and water have ionization potentials above this level.  As well as  the
 ionization potential, the photoionization efficiency is Important since
 this parameter determines sensitivity of  the technique to different
 compounds.  A recent report6  indicates that the molar sensitivity of
 aliphatic and oxygenated aliphatic compounds is several times less  than
 that of aromatic compounds if  incident radiation  is about 10.2  eV.   In
 fact,  for aliphatic hydrocarbons  of carbon number less than C8,  the
 relative sensitivity is less  than one-tenth that  for benzene.   If
 incident radiation is about 11.7  eV,  the  relative sensitivity of aliphatic
                                    13

-------
RELATIVE
PHOTO-
IONIZATION
                 AROMATIC'
                                                        ENERGY OF
                                                        UV LAMP
                                                   ALKANE
              J	I
I    I    I
I	I
                              95                  10p

                                 PHOTON ENERGY («V)
I	I
 ;  Figure 1.  Photo ionizat ion efficiency! curves as a function of photon energy
f~~"         for an aromatic hydrocarbon and an alkane (source: Ref. 5).
                                     14
                                                   TYPING GUIDi: NHfltIT

-------
                              NITROGEN
                              HELIUM
                              CARBON  MONOXIDE
                              CARSON  DIOXIDE
                              -lYOROGEN
                              SULFUR OIOXIOE

                              ACETONITRILE
                              WATER
                                                     HEXANE
                                                     CYCLOHEXANE
                                                     METHYLBROMIOE
                                                     HYDROGEN SULFIOE
                                                     ETHYLENE
                                                     ETHYLENE OXIDE
                                                     ACETIC ACID
                               METHANE
       /CHLOROFORM
       / CARSON TETHACHLORIOE
       / METHYLENE CHLORIDE
       / METHYL CHLORIDE
      / FORMALDEHYDE
      / FORMIC ACID
11.7—L ACRYLONITRILE
      I  METHANOC
     /  METHYL FORMATE
IB.^^*  NITROMETHANE
FREONS
PHOSGENE
                                                   ETHANE  PROPANE   BUTANES
                                                               I        _L
                                     CARBON OISULFIOE
                                     AMMONIA
                                     PMOSPHIN6
                                     AASINf
                                     ETHANOL
                                     TRICHLOROETHYLENE
                                     BUTYL ACETATE

                                     OlETHYL ETHER
                                     ACETONE
                                     ACETALOEHYOE
                                     VINYL CHLORIDE
                                     VINYL BROMIDE
                                     BROMINE
                                     NITROBENZENE
     / BENZENE AND AROMATICS COMPOUNDS
     / AMINES
    / ORGANIC SULFUR
    / METHYL iOOIDE
    /  PROPYL ETHE^
   /  MIBK
  1.  OMF
 A   VINYL ACETATE
/ /   PHENOL
                                                                                     '  I   ANILINE
                                                                                    9.5
                                                                                            CHLOROBENZENE
                                      OCTANES
                                     	I
           OECANES
            I
                                                                                10
                               IONIZATION  POTENTIAL
H!
                   Figure  2.  iistrument response  vs.  ionization potential for several classes of compounds (Ref.  5).

-------
  and  aromatic  compounds is similar7 and perhaps within a factor of two.
  Based  on  this assumption, a commercially available photoionization
  instrument with a lamp of about 12 eV may provide a generally applicable
  VOC  detection technique.

      (2)  Infrared Detection

 Typical nondispersive infrared devices operate by passing infrared
 radiation through two separate absorption cells:  ?. reference cell and
 a sample cell.  The sealed reference cell is filled with nonabsorbing
 gas,  such as nitrogen or argon.  The sample cell is physically identical
 to the reference cell and receives a continuous stream of gas b3ing
 analyzed.   Subsequently,  the net radiation in the two beams are passed
 into  and absorbed in matched selective detectors (e.g.,  Luft detector)
 containing the vapor to be detected.   When organic vapors are present
 in the sample cell,  energy is absorbed,  and the temperature and
 pressure in the  corresponding detector is reduced relative to that
 in the detector,  on the reference side of the analyzer.   A diaphragm
 between the two  detectors is  displaced and the amount of displacement
 is detected,  electronically  amplified,  and an output  signal proportional
 to concentration produced;   In other  NDIR systems,  narrow bandwidth
 filters which pass energy which corresponds to that absorbed by the
 compound of  interest are  used  along with simple solid state IR detectors.
 In both cases, interference from compounds with overlapping absorption
 bands is possible.   More  importantly,  the maximum absorbing wavelength
 for different  organic species  in the  sample gas may not  correspond to
 the maximum absorbing wavelength of the  calibration compound used in
 the detector.  Within reason,  several different calibration compounds
 could be used in the detector  to  improve  responsiveness  for several
 compounds.  Alternatively, by  selection of  a single narrow bandwidth
 filter  with a wavelength  corresponding to a general alir' atic C-H
 stretch, many aliphatic hydrocarbons might  be detected   _te uniformly.
 Based on the maximum  absorption wavelength  of aromatic hydrocarbons,  a
 separate filter or cell would  be needed for  this  class of  compounds.
 In  practice, the specificity of the detection principle has  precluded
 the manufacture of an NDIR device suitable as  a general  (i.e., both
 aliphatic and aromatic) organ/.c vapor detector.

An alternative IR detection scheme involves dispersive infrared analysis
 in which the specific wavelength absorbed by  the organic vapor of interest
 is passed through a single sample cell.  In this case, selectivity is
provided by a monochromatic light source rather than a. selective detector.
 Such  a device is inherently more selective than an NDIR and thus may be
 less  appropriate as a VOC screening device.  However,  by successive,
rapid monitoring of IS. absorption at several selected wavelengths
corresponding to the mavimim absorption wavelengths for several organic
functional groups, e.g., aliphatic CH, aromatic CH, C-C1, OO, it may
be possible to identify and quantify a wide variety of organic vapors
in a fugitive emission source.
                                  16

-------
       (3)  Thermal Conductivity

 Thermal conductivity  (TC) of gases and vapors provides a physical
 method used extensively in gas chromatography where mixtures of compounds
 are resolved into individual components and quantified.  The detector
 responds proportionally to a change in thermal conductivity of the trace
 gas in a background (helium, for example).   The physical property of
 thermal conductivity is not specific to any class of compounds.  In fact,
 the conductivity of many gases with the exception of hydrogen and helium
 is quite similar as shown below:

                                        Thermal Conductivity
             Gas              "       flO"5 Cal/SeC"Cm2/(°C/cm)1

           Air                                  7.5
           Hydrogen                            53.4

           Helium                              41.6

           Nitrogen                             7.5

           Oxygen                               7.6

           Carbon Dioxide                        5.3

           Methane                            10.9

           Ethane                               7.3
           Propane                              6.3

As molecular weight increases, the thermal  conductivity decreases
somewhat,  but for organic compounds of interest  in fugitive sources
the thermal conductivity does not differ from that of air by more
than a factor of  two.8  Thus, the concentrations of organic contaminants
in air must be very large (e.g., 1-100%) in order  for the vapor to be
detected against  the air matrix which has a similar thermal conductivity.
This severely limits the usefulness of TC detectors for VOC screening.
Two additional problem.?, exist for TC detectors in  this application.
First, inorganic  gases (e.g., C02, H20, HC1) which may be present in
fugitive sources will be detected along with any organic vapors.  Second,
most thermal conductivity detectors consist of heated wires which are
subject to degradation by oxidizing or humid atmospheres or by the
presence of chlorinated hydrocarbons.  Thus, the practical application
of TC detectors to VOC screening is in doubt.

     (4)  Other Detection Schemes

Two other detection principles, implicitly limited in response only
to chlorinated organic compounds, may be appropriate for this  compound
class.  They include electron capture,  which is used commonly  in gas
chromatography,  and enhancement of radiation from halogens by  a spark
source.  Each scheme depends on a unique property of halogens:
electronegativity and electron energy levels,  respectively.  Their
                                   17

-------
  application for organic  detection  is very limited and their practical
  use for VOC screening  is in  doubt.

  B.  .Unit Selection

  On  the  basis of  the factors discussed above, both the IR and photoion-
  ization principles might be suitable for general VOC screening.  However,
  a comparison of  the specifications 'of commercially available instruments
  (Tables 3, 4) operating by these principles and the criteria of Method 21
  lead to a rather unfortunate conclusion:  no commercial instruments of
  these types are available for VOC screening.  In terms of a desire to
  expand  the list of potential detectors, such a finding is unsatisfactory.

 What criteria led to this finding?   The most obvious answer is the
 requirement for an intrinsically safe device.   No IR or FID devices are
 certified for use in Class I, Division 1 environments (Table 2).   One
 PID device is certified for use in  Class I,  Division 2.   It should be
 noted,  however,  that in the future  other devices may be  modified so
 as to meet Class I,  Division 1 certification.   Alternatively,  the use
 of an instrument only in  less hazardous environments may not be
 considered as particularly restrictive.   For these reasons,  the criterion
 of intrinsic safety  was given lesser significance and not used to rule
 out potential devices for screening in  this  program.

 The other criteria listed previously were ranked in  approximately
 descending order of  importance.   Thus,  a response time of less than
 30 seconds was given the  highest importance.   In fact, fast  response
 time is  very important  to practical measurement  of VOC leaks  and  several
 instruments  with faster than  30-second  response  time  are available.
 Thus, it was  decided  that this  criterion must  be met  by  any  instrument
 to be evaluated.   The criteria  of portability, ruggedness  and  ease  of
 operation are also important  but were not chosen as absolute selection
 criteria.  Portability  can be evaluated  subjectively  and devices
 operated with automobile  batteries  placed on a small  cart may be  con-
 sidered  to have adquate portability.  Devices operated with AC power
 are  less practical in many industrial environments.

 Tables 3 and A and additional manufacturers' literature were reviewed
 using the modified criteria described above.  A  list of potential VOC
 detectors was developed (Table 6).  This  list includes instruments
 which operate on photoionization and IR principles and which meet most
 of the Method 21 criteria.  It is obvious that not all of the IR
 instruments that meet most of the criteria are included.   Since the
 goal of  this study is to evaluate the usefulness of  the IR principle
 rather than all available IR devices, only selected IR devices suitable
 on the basis of the criteria for VOC screening were included.

The list, therefore,  includes a dispersive IR device  and  NDIR devices
with or without solid state detectors.  The  NDIR devices  may be useful
 for a specific group  of organics, i.e.,  aliphatic hydrocarbons.   Also
 included are two devices operating on other  detection principles,  i.e.,
 ion capture and UV spark.   These instruments  are only useful  for a


                                  18

-------
TABLE 6
PO
Instrument Principle Range (ppra)
HNU Systems, Inc. Photo- 0-20, 0-200,
(PI-101) ionization 0-2000
CENTIAL VOC DETECTORS1*
Wgt
Response (a) (Ibs) Pump Power
5 9 Yes Battery
General Electric Ion Capture 0-1 •*• 0-10,000 120 23 Yes No
(TVM 1) (Halogenated'
Gas Tedh, Inc. UV Spark 0-100, 0-10,
(Halid'e) (Halogenated)
Foxboro, Inc. IR ppra •> %
Miran 1A/80
103 IR ppm -*• %
000 5 13 Yes AC
1-40 32 Yes Car Battery
(37 Ibs)
1-40
ANARAD, Inc. IR 100-10,000 ppm 5 24 Yes AC
AR-400 <5»J
Infrared IR 1000 ppra,
Industries Solid State 100% LEL
IR-711 <5n
AID, Inc. Photo- 0-200
(580) ionization 0-2000
5-120 9 Yes Battery
2 8 Yes Battery

Intrinsically
Safe
Yes
No
No
No

No
Yes
Pending

-------
  specific class of organics,  i.e.,  halogenated hydrocarbons, but were
  included due to the  widespread  industrial use of these solvents.

  The  final instruments  selected  for evaluation were as follows:

       Instrument     Manufacturer             Principle of Operation

      Model 580       AID, Inc.                Photoionization

      PI 101          HNU Systems,  Inc.        Photoionization

      Miran 80        Foxboro/Wilks, Inc.      Dispersive Infrared

 The rationale for the selection of these instruments is based on both
 suitability and availability.  As noted previously, photoionization
 may be a particularly suitable VOC detector for aliphatic,  aromatic,
 and substituted organic vapors.   Either of the two commercially
 available, portable instruments meet  most Method 21 criteria and may
 be suitable for evaluation.   Both photoionization instruments were
 selected on the basis of the following considerations:

      1.   Each was supplied  free  of charge;   '      „
                                                           «
      2.   Each was modified  by the manufacturer with a dilution
          probe (see discussion in Section 2c);

      3.   The  location of HNU Systems,  Inc. provided the potential
          for  rapid modification/repair;  and

      4.   Negligible additional time would be expended in
          evaluating both devices due  to  similarity  of design.
                                              I

The Miran  instrument  is  the  one  available infrared  device which pennies
a  selection of wavelength as  opposed  to  selection of  a test compound in
a  reference cell.   This  option permits the rapid  (a few seconds)
assessment of  the  suitability of  several wavelengths  for the measurement
of the substituted organics of interest.  Specific  examples are an
aliphatic C-H stretch, arociatic  C-H stretch or a C=0  stretch.  Other
portable IR devices utilize a  filter at  one specific  wavelength band
corresponding, for example, to an aliphatic C-H stretch.  Thus, they
have an inherent selectivity against aromatic or substituted species.
Since all three  classes of compounds are  of interest, the latter devices
are not preferred  as VOC screening  devices.  It is possible that one
wavelength may be  suitable for analysis of a wide variety of organic
vapors.  If that is the case,  other IR instruments could potentially
be used for VOC  leak detection.  In summary,  the Miran 80 (with
associated microprocessor) permits the most rapid and cost-effective
assessment of the  IR principle as a general VOC detector.   Other IR
devices were, therefore, not evaluated.•

The halocarbon specific detectors, i.e.,  General Electric TVM-1 and
Gas Tech Halide Detector, were not selected for  evaluation  despite
                                   20

-------
  the potential  usefulness  of  such  a device  in environments  subject  to
  halocarbon  solvent  combination.   Neither the GE TVM-1 nor  an equivalent
  model is now sold.  The Gas  Tech  device could not be modified  to meet
  the intrinsic  safety requirements of Method 21 due to the  presence of
  a spark in  the detector section.

  No  other instruments appeared to  have a reasonable expectation of
  meeting the Method  21 criteria and of providing a significantly
  different performance than those  devices evaluated previously or
  selected for evaluation in this study.

  C.  Unit Modification

 Both photoionization devices operate with a maximum quoted linear  range
 of 0-2000 ppmv.  In fact,  the linear range is frequently reported  to be
 only about 1500 ppmv.   Since the ma yttrium concentration of concern  in
 VOC screening  is 10,000 ppmv, dilution of sample air is necessary for
 both instruments to operate in the linear range.   Both HNU Systems, Inc.
 and AID,  Inc.  provided  their instruments with dilution systems designed
 in their  respective laboratories.   The HNU Systems,  Inc.'design (Figure 3)
 consisted of (1)  a fine bore restrictor which limited the flow of sample
 air, and  (2) a charcoal tube which passed an excess  (lOx) of hydrocarbon-
 free air  (methane is not removed but  does  not respond in the detector).
 The sample stream is thus  diluted about 1 to 10.   The AID,  Inc.  design
 (Figure 4) consisted of  a  pump and needle valve which diverted  90%  of
 the  incoming sample  air  through  a charcoal  tube and  10%  to  the  norm*' .
 exhaust point.   The  hydrocarbon-free  (except for methane) sample air  ij
 combined with the incoming sample  stream and thus  a  continuous  tenfold
 dilution is  provided.

 Problems were observed with these  dilution  systems and the  UV lamps
 provided with both instruments.  The absolute accuracy of the dilution
 ratios is in some doubt since independent flow rates were difficult to
 measure.  The UV  lamps provided with both instruments were  subject  to
 degradation  during the life of the study.   In fact, the 11.8 eV lamp
 supplied with the AID, Inc. device failed during the study  and,
 unfortunately, a  replacement  could not be obtained in  time  to collect
 useful data with  this instrument.  The 11.7 eV lamp supplied with the
 HNU  Systems, Inc.  device failed during the study and a replacement  was
 provided.   The difference in  energy output from the two HNU Systems, Inc.
 lamps was large (i.e.,  a factor of three to ten depending on the age
 of the lamp).  This variation affected the linear range of  the instrument
 and  created problems in obtaining  consistent results.  In some cases
with the new lamp, saturation of the detector occurred even with the
 dilution probe attached to the instruments.   The test results reported
 in Section 5 must, therefore, be carefully interpreted and conclusions
narrowly drawn.

The Miran 80 operates over the concentration range  from ppm to percent.
The wide dynamic range is provided by a cell in which the pathlength of
 IR radiation can be changed by optical folding of  the incident beam.
                                    21

-------
FigureS.  HNU Systems, Inc. dilution probe.




                          22

-------
                                      Reproduced  from
                                      best available copy.
Figure 4.   AID,  Inc.  dilution system.

                           23

-------
Ac the concentration range of interest, i.e., 100 ppnv to 10,000 ppmv,
the incident beam traversed a distance of about 0.75 m.  At this
pathlength, the full-scale absorbance for vapors of interest at a
concentration of 10,000 ppmv was about one absorbance unit.  Once the
cell pathlength was set, no other modifications of operating conditions
were required.
                                  24

-------
  3.   COMPOUND SELECTION

  As noted in  the Introduction, 168 compounds had previously been tested
  for  response factor on two commercially available VOC detectors.3
  Twenty-three  showed sufficiently poor response that the actual and
 measured concentrations differed by a factor of greater than five
  (Table 1).  The classes of compounds showing poor agreement were
 generally highly substituted aliphatic and aromatic compounds and those
 compounds incorporating functional groups such as carbonyl and hydroxyl
 groups.

 These 23 compounds were selected for testing on the alternative VOC
 screening devices to be evaluated in this study.   Several other compounds
 (Table 7),  which were not evaluated in the previous work, were added to
 the list.

 These compounds (Tables 1 and 7) include only a portion of those
 commonly used in chemical production.   At the request of OAQPS, other
 industrial  compounds which have a vapor pressure greater than 0.3  kPa
 but which were not considered previously have been tabulated  (Table 8).
 This  extensive list of 76 compounds includes many species for which an
 FID or catalytic combustion detector would respond well.  However,
 others are  highly substituted compounds which will probably not give
 adequate response  on these two detectors.   Selected substituted
 compounds froa Table 8 were included in the detector evaluation.

 The selection criteria required  a response to several questions:

      1.  Are  substituent  groups  present or absent?   If absent,  don't test,

 	2.  Are  the compounds similar (functionally and/or isomerically)
         to others  previously evaluated?   If  they are,  don't  test,

      3.  Are  response  factors on an FID instrument  likely  to  exceed
         five?  If  not, don't test, and

      4.  Do the compounds  pose a serious health hazard  to laboratory
         personnel?  If they  do, cautiously consider evaluation.

As a  result of the responses, the compounds were separated into two
groups:  compounds  that should and those that need not be analyzed.
Within the first group, the compounds were prioritized on the basis
of (1) their similarity to other vapors to be analyzed (for example,
positional isomers of compounds selected for testing were given lower
priority), and (2) their health hazard  (extremely toxic compounds with
little commercial application or likelihood of release &nd which require
complex/expensive Katun-ing were given lover priority).  •  -

The compounds selected for evaluation in this program are listed in
Table 9.  They are listed in the approximate order of testing.
                                   25

-------
                         TABLE 7

              ADDITIONAL COMPOUNDS TO TEST
 OCPDBa
 ID No.                     Compound Name

 1660                    Ethanol

 —                     Formaldehyde

 1235,  1236              Ethylene Dichloride  (Dichloroethylene)

 —                     Chlorinated Ethanes  (C2H.C1, etc.)
                       Chlorinated Methanes  CCH-Cl, etc.)
aOrganic Chemical Producers Data Base
                         26

-------
                                TABLE 8

           SYNTHETIC ORGANIC COMPOUNDS WITH VAPOR PRESSURE

        GREATER THAN 0.3 kPa (20°C)  AND NOT TESTED PREVIOUSLY


 Compound.                                             Vapor Pressure  (kPa)

 Acctal    •                                                   2.7
 Acetaldehyde                                                98.6
 Acrolein                                                    29.7
 Acrylic esters:   methyl aerylace                             8.7
 Allyl chloride             .                                 A0.8
 Arayl acetate                                                 0.5
 Amyl amine                                                   2.0
 Amyl chloride                  .                               2.2
 Amyl mercaptans:   1-pentanethiol                             1.5
                   2-methyl-2-butanethiol                      5.0
                   2-methyl-l-butanethiol             .         2.0
                   3-mechyl-l-butanethiol       -               2.1
 Aniline  hydrochloride                                  '  -    4.0
 Benzyl benzoate                                               0.5
 Chlorobenzoyl  chloride                                        2.6
 Chlorodifluoromethane                                         G
 Chlorodifluoromethane                                         G
 Chloroprene                                                 23.1
 Chlorotrifluproraethane                                        G
 Cyanoacetic acid-                                              2.9
 Cyanogen chloride                                             G
 Cyclooctadiene (1,5-)                                         3.3
 Dichlorodifluorotne thane                                       G
Dichloropropene (isomers)                                   70.3
Diethylamine                                                24.0
Difluoroethane                                                G
Diketene                                                      1.6
Dimethylamine                                                 G
Dimethyl ether                                                G
Dimethyl sulfide                                            48.8
Dioxolane                     '                               9.3
 Ethyl bromide                                               51.4
Ethyl chloride                                                G
 Ethylene ehlorohydrin                                        0.7
 Ethylene dibroraide                                           1.5
 Ethylene glycoldimethyl ether                                7.8
            .'  monoethyl ether                               0.6
               monoethyl ether acetate                       0.3
               monomethyl ether                              1.2
               monomethyl ether acetate                      0.3
               monopropylether                               0.5
 Ethyl orthoformate                                           0.4
 Glycerol dichlorohydrin                                      0.9

 SOURCE:  REFERENCE 3              27

-------
                                     TABLE  8 (continued)
          Compound                                              Vapor  Pressure  (kPa)

          Hydrogen cyanide                                            66.6
          Isoamylene                                                    G
          Isobutanol                                                   1.0
          Isobutyl acetate                                             1.9
          Isobutyraldehyde                                            18.3
          Isopentane                                                  76.5
          Isopropylamine                                              29.3
          Ketene                                                        G
          Methallyl chloride (isoraers)                                 70.3
          Methylamine                                                   G
          Methyl bromide                                                G
          Methylene chloride                                          46.1
          Methyl isobutyl carbinol                                    ,0.6
          Methyl isobutyl carbinol                                     2.1
          Neopentanoic  acid                                             1.1
          Nonene                                                       0.5
          Paraldehyde                                                  3.4
          Pentene                                                     70.3
          Perchloroethylene                                             1.8
          Perchloromethyl mercaptan                                     0.6
          o-Phenylene diaraine                                           1.18
          Phosgene   t                                                    G
          Propylamine                                                 33.0
          Propylchloride                                               37.3
          Propylene chlorohydrin                                        0.7
          Propylene dichloride                                          5.3
          Quinone                                                      5.0
          Tetramethyllead                                              3.0
          Toluene sulfonic acids                                       70.3
          Toluene sulfonylchlorides                                    70.3
          Trichlorofluoromethane                                       79.5
          Trichlorotrifluoroethane                                     31.8
          Trimethylamine                                                G
SOURCE:   Vapor pressure distribution of synthetic organic chemicals,
          Weber, R.C.; P. Parker and M. Bowser.  IERL, Cincinnati,
          Draft Report, November 1980.

       G - Gas; VP >101.3 kPa.
                                            28

-------
                                       TABLE 9

                             CCMPOCHDS FOR EVAtGATXOS
2*3-
1,3-
1,3-
 Carbon Bisulfide
 Carbon Tetrachloride
 Chloro-Acetaldehyde
 Dichloro-1-propanol,
 Dichloro-2-propanol,
 Diisopropyl Benzene,
 Dimethyl Styrene,  2,4-
 Formic Acid
 Freon 12
 Methanol
 Methylstyrene,  o-
 Tetrachloroe thane,  1,1,2,2
 Ethanol
 Formaldehyde
 Ethylene Bichloride (Dichloroethylene)
 Chlorinated Ethanes ^^Cl, etc.)
 Chlorinated Methanes (C^Cl, etc.)
 Acetophenone
 Benzoyl  Chloride
Furfural
Monoe thanolamine
Nitrobenzene
Phenol
Acetyl-1-propanol,  3-
Glycidol
Hydroxyacetone
Methyl-2,4-pentanediol, 2-
Phenyl-2-propanol, 2-
An^^•fw» Hydrochloride
DiHnoroetbaae
 Diketene
 Dimethylsulfide
 Glyceroldichlorohydrin
 Paraldehyde
 Perchloromethylmercaptan
 Propylene Chlorohydrin
 Toluenesulfonic Acid
 Toluene  Sulfonylchloride
 Ethyleneglycoldimethyl Ether
 Ethyleneglycolmonoethyl  Ether Acetate
 1-Pentanethiol
 Acetal  .
 Chlorobenzoylchlorl.de
 Chlorodifluoromethane
 Chlorotrifluoromethane
 Trichlorofluoromethane
 Trichlorotrifluoroethane
 Cyanoacetic Acid
Neopentanoic Acid
Any Inercap cans
   2-methyl-2-butanethiol
   2-methyl-l-butanethiol
   3-me thy1-1-butanethio1
Glycols
   Ethylene Glycolmonoethyl Ether
   Ethylene Glycolmonomethyl Ether
   Ethylene Glycolmonomethyl
      Ether Acetate
   Ethylene Glycolsonopropyl Ether
   Glycolaethyl Ether (Dioxolane)
                                       29

-------
 4.  EXPERIMENTAL PROCEDURES

 A.  Introduction  •

 Determination of response factors required initial calibration of the
 VOC detectors with a gas or gases of known concentration.  Methane
 had been used previously for calibration of FID and combustion analyzers.3
 However, the photoionization instruments do not respond to this compound
 and the multiple wavelength analysis by dispersive infrared spectrometry
 cannot be carried out by the use of methane as a single calibration gas.

 Therefore,  1,2-dichloroethane was selected as the calibration gas for
 the photoionization detectors.   This compound can be detected by the
 instruments and it  has a response factor of about one (compared to
 methane) when analyzed on an FID instrument.   As a result, data collected
 in this study may be comparable to data collected in a previous EPA
 study.3

 Several calibration compounds were used for the IR evaluation•since
 several wavelengths  were scanned in the dispersive infrared•instrument
 to determine if  any  wavelength  gave similar response factors  for all
 the compounds of interest.  The wavelengths were selected to  correspond
 to key  functional groups of the test compounds to be analyzed.   The
 •aveleagtas,  functional groups  and calibration cospouods are  listed
 in Table 10.

 Once calibrated, the instruments were used to analyze the test  compounds
 at three concentrations over  the range  of  100-10,000 ppmv.  The response
 factor  was determined by ralculgting the ratio of the actual  concentration
 to the  concentration indicated  by the instrument.   The following sections
 describe the  procedures involved in calibration and operation of the
 instruments,  preparation of test gas samples,  and calculation of response
 factors.

 B.  Instrument Operation

 Three instruments were  selected for  evaluation as VOC screening devices.
 Two iastmaeats operated on the photoionization principle, i.e., AID, lac.
Model 580 and BSD Sysceas, Inc. Model PI-101.   The other in instruaeat
was the Foxboro/lrilks,  Inc. Miran 80 which operates on the principle
 of dispersive infrared  spectrophotometry.  Details of  the operation of
 each instrument are given in the appendices.

 During  the. tests, the lamp in the Model 580 failed and a replacement
 could not be  obtained.  Therefore, only the PI-101 and Miran 80 were
 evaluated.

 C.  Preparation of Gas Standards/Saaples

 Gas mixtures  tested in  this study were prepared in Tedlar gas  sampling
 bags of a nominal 25 liter volume.  These bags provide a relatively
                                   30

-------
                                  TABLE 10

                      CALIBRATION SCHEME FOR MIRAS-80
Wavelength (urn)       Functional Groups(3)               Calibration Compound

      3.3             Aromatic & Unsaturated C-H         Toluene

      3.4             Saturated C-H                      Pentane

      3.6             Aldehyde C-H                       Butyraldehyde

      4.0             Reference Wavelength               Air

      5.7             Carhonyl C»0                       Acetone

      6.35            Aromatic C-C,                      .Toluene
                      conj  C«C (also N-H,  C-S)

      8.8             Ether C-O-C                        Diisopropyl Ether

      9.5             Alcohol C-O-H                       Isopropanol

     13.5             C-C1                                1,2-dirhl oroethane

-------
  inert  surface  to preclude adsorption, reaction, or permeation.  They
  also perait visual inspection of the bag interior to provide as.
  indication of  sample condensation or reaction.  The bags are equipped
  with two valves to facilitate flushing of sample gas and a septum
  to permit injection of sample liquid with a syringe.

  Gas samples were prepared by the following procedure:

      1.  Flush and evacuate bag three tizes with hydrocarbon-free
          air (i.e.,  until no hydrocarbons are detected on each
          instrument).

      2.  Fill bag with 20.0 L of hydrocarbon-free air.

      3.  Inject a known voluae of test coopcuod into the bag.
      4.   Permit at least one hour equilibration to insure adequate
          evaporation and mixing.              •*

      5.   Draw gas saaple froa bag with each instrument.

 The  hydrocarbon-free air was prepared by passing house compressed air
 through  silica gel,  charcoal and  a high efficiency filter.   A known
 volume  (20.0 L)  of air was introduced into the  hose fitting of the
 Tedlar bags  through a calibrated  rotameter.   The volume was calculated
 on the basis of  rotaaeter flow rate (L/xdn)  and duration of flow (zin)
                                                                 a"3 y?>rm
                                                                ©3SSTT3C.
 Known volumes of the test compounds (all liquids) were injected through
 the  septa of the bags with Hamilton microliter  syringes.  The volumes
 injected  were in the range of  10  to 100 uL.   The mass  of material
 injected  was calculated from density data.   Manual manipulation of
 the  bag,  visual  observation and at least one hour equilibration period
 were used to ensure  complete mixing.
    target concentrations prepared for each cospound were 500, 1000,
5000 and 10,000 ppav.  In several cases, it was not possible to prepare
the higher concentrations due to the low vapor pressure of the coapound
or due to safety reasons, that is, such a concentration would exceed
the lower explosive limit.  In these cases, a concentration of 100 ppn
was often prepared.  For each target concentration, the required volume
of liquid was calculated and measured in a microliter syringe.  The
volume required to produce the test concentration was calculated
according to the following equation:

            VL - (C) (VA) flay (BP)/ (62.36 x 106) (OL) (T)

where V  Is the voluae of liquid ccapound in the syringe in oilliliters,
       \f
      C is the target concentration of compound "L" in parts per aillion
         by volume (ppmv),~ -
                                  32

-------
       VA is the sample bag volume in liters  (i.e., 20.0 L),

       MW  is the molecular weight of compound "L,"
         Id

       BF is the barometric pressure in mm Hg,

       62.36 x 10  is a combined constant with the unit (liters) (mm Hg)
          (g-mols) (°K).  This constant incorporates the ideal gas
          volume of 22.4 liters per g-mol, standard temperature and
          pressure, and a factor of 10& to go from volume fraction
          to ppmv,

       PT  is the liquid density in g/ml,  and
        Ij

       T is  the laboratory temperature in °K.

 D.   Calibration Protocol

 Each instrument was  initially calibrated (spanned)  with a  gas sample
 prepared in triplicate at a  concentration of 10,000 ppmv.   Calibration
 curves vere then prepared by introducing samples  of the calibration
 gas,  prepared in triplicate  at five  concentrations  over the range of
 100  to 10,000 ppmv,  into  the  instruments and recording  the  response.
 The  PI-101 was  calibrated with 1,2-dichloroe thane while the Miran 80
 was  calibrated  at individual  analytical  wavelengths with the compounds
 listed in Table 10.

 During subsequent analysis of each test  compound, the HNU PI-101
 instrument was  spanned with an 8040  ppmv 1,2-dichloroethane certified
    standard provided by  Scott Specialty Gas, Inc.  of Plumsteadville,
Pennsylvania.  This span was carried out just prior to analysis of
each set of sample bags for each test compound.

The Foxboro/Wilks Miran instrument was electronically zeroed and
spanned according to the manufacturer's instructions.  This zero and
span check was carried out prior to analysis of each set of sample bags
for each test compound.

Z.  Instrument Sampling

The procedure used to obtain response data involved the following
steps for each of five replicate sample bags for each of three target
concentrations of each test compound:

    1.   Span and zero instruments.

    2.   Connect bag  to photoionization instrument (PI-101).

    3.   Observe instrument response and record  three instrument
        readings at  equilibrium point.
                                   33

-------
      4.  Remove bag and permit instrument response to return to
          zero,

      5.  Repeat steps 1-4 with each sample bag.

      6.  Connect bag to infrared instrument (Miran 80); start pump.

      7.  Empty bag to approximately 10% of original volume; stop pump.

      8.  Record instrument response at each of eight analytical
          wavelengths and one reference wavelength.

      9.  Repeat steps 6-8 with each replicate sample bag at first
          target concentration.

     10.  Remove bag,  start pump and rezero instrument on .zero air
          (room air was adequate).

     11.  Repeat steps  6-10 for  each target concentration.

 F.   Data  Analysis

 The  response factor reported  in the following  test  results  section  is
 the  number  that, when multiplied by the apparent  concentration  based on
 instrument  response, yields the actual concentration  as  calculated  to
 exist in  the gas bag sample.  That  is:
     _        _       ,__N    Actual Bag Concentration  (C)
     Response Factor  (RF) -  concentration Calculated  from
                                 Instrument Response
Response factors were determined at three actual concentrations,
i.e., generally 100, 500, 1000, 5000 or 10,000 ppmv.  No attempt was
made to fit the three response factors for each compound to a
particular function.  For some compounds, the response factor is
nearly identical for each concentration whereas for others it differs
dramatically and in a complex manner.  The response factor for
individual compounds is, therefore, not reported for an observed instru-
ment response of 10,000 ppmv.  Instead, the mean response factors
calculated from up to five replicate data points at each of the three
actual bag concentrations are reported along with the standard deviation.
Also reported is the 95% confidence intervals for the response factors
as calculated from Student's t-test.
                                    34

-------
 5.  TEST RESULTS

 The response factors for the compounds tested in this instrument
 evaluation program are listed on the following tables.   The response
 factors for all 16 compounds tested on the HNU Systems,  Inc.  Model PI-101
 are reported in Table 11.   The data are limited due  to several factors
 including:

      1.  The low vapor pressure of  many compounds of interest and  thus
         the low concentration prepared in the sample bag and found
         in the dilutor outlet;

      2.  .The failure  of the dilution system to operate suitably;
                                                »
      3.  The declining intensity of  the UV lamp; and    • .

      4.  Saturation of  the  instrument's  detector.

The response factors for 32  individual  compounds tested  on  the Miran
are reported in Table  12.   The response  factors are  reported  only for
those wavelengths where the detector was sufficiently sensitive to
yield an absorbance value above the background noise.  Where  this is
not the case, the response factor would be much greater  than  ten.
The remainder of the 57 compounds listed in Table 9 were not  tested
for several reasons including:.

     1.  Similarity with compounds tested, e.g., amylmercaptans
         with pentanethiols and glycols with ethyleneglycol-
         monoethylethe.r acetate,

     2.  Low vapor  pressure, e.g.,  phenyl-2-propanol,

     3.  Solid state,  e.g.,  phenol,

     4.  Reactivity in Tedlar bags,  e.g., toluene sulfonylchloride,

     5.  Poor availability of gaseous fluorinated methanes,  and

     6.  Difficulties  with operation of analyzer.
                                 35

-------
                                                              TABLE 11

                                                     RESPONSE  FACTORS  ON PI-101
                Compound
  Actunl
Concentration
  (ppmv)	
 Instrument
Concentration
  (ppmv)	
Standard         Response
Deviation  (n)*   Factor
   957.
Confidence
 Interval
Acetal



Carbon Disulfidu
! '

Carbon Tetrachloride



Chloroform



Diketene













»






1 1000
5000
10000

1000
10000

500
1000
10000

1000
5000
10000

1000
5000
10000
925
7200
13200

1990
12900

784
1070
6070

756
2550
5250

148
318
460
13 (5)
10 (5)
mo (5)

71 (5)
921 (5)

59 (5)
72 (5)
475 (5)

«• * (5)
!0 (5)
10 (A)

7.6 (5)
13 (4)
7.1 (5)
1.1
0.69
.0.76

0.50
0.78

0.64
0.94
1.6

1.3
2.0
1.9

6.8
16
22
1.1 - 1.0
(0.69)
(0.76)

0.57 - 0.45
0.97 - 0.65

0.94 - 0.48
1.2 - 0.77
2.1 - 1.3

,1.4 - 1.3
(2.0)
(1.9)

7.9 - 5.9
18 - 14
23 - 21
to
o>
           *Numbcr of replicates analyzed

-------
                                          TABLE 11 (Cont.)
                                     RESPONSE FACTORS  ON PI-101
Compound
  Actual
Concentration
  (pprov)	
 Instrument
Concentration
  (ppmv)	
Standard
Deviation (n)
Response
 Factor
   957.
Confidence
 Interval
Dime thy laulfida.



Ethanol
I
•

EthyleneglycoldAmethyl

Ethvlene DichlorAde (tr«
»
Methanol



Pentanethiol. l-









Ef.her

r,B)
*






1000
5000
_IOOOO

1000
5000
10000

1000

IPOJO

1000
5000
10000

1000

1180
9200
11000

360
1330
3630

7620

1040

125
798
1060

1260

10 (4)
10 (4)
100 (5)

20 (5)
45 (5)
250 (5)

250 (5)

55 (4)
•
12 (5)
4.5 (5)
54 (4)

69 (4)

0.85
0.54
0.9l

2.8
3.8
2.8

1.3

0.96

8.0
6.3
9.4

0.79

(0.85)
(0.54)
(0.91)

3.4 - 2.4
4.9 - 3.4
3.4 - 2.3

1.4 - 1.2

1.1 - 6.84

11 - 6.3
6.4 - 6.2
11 - 8.3

0.96 - 0.68


-------
                                         TABLE 11 (Cent.)
Compound
                                    RESPONSE FACTORS ON PI-101
  Actual
Concentration
  (ppmv)	
 Instrument
Concentration    Standard        Response
  (ppmv)         Deviation  (n)    Factor
   95%
Confidence
..Interval
Perchloromethyl Mercapt

Toluene

Tet rnchloroethane, 1 , 1 , 2 ,
i


Trichloroe thane, 1,1,



Trlclilorotrifluoroethane


,


n



-






•
1,1,2-





5000

1000

1000
5000
10000

1000
5000
10000

5000
10000




103

1180

736
1170
1880

1020
6170
9430

155
430




2.9 (5.)

120 (5)

5.5 (4)
10 (4)
10 (4)

77 (5)
66 (5)
200 (5)

1 (5)
1 (5)
,
'


48

0.85

1.4
4.3
5.3

0.98
0.81
1.1

32
23




55 - 43

1.2 - 0.67

1.4 - 1.3
(4.3)
(5.3)

1.4 - 0.74
0.84 - 0.79
1.1 - 1.0

(32)
(23)





-------
                                                TABLE  12
                                      RESPONSE FACTORS ON MIRAN 1A/80
       Compound
Wavelength
   (um)
  Actual
Concentration
  (ppmv)
 Instrument
Concentration
  (ppmv)
Standard        Response
Deviation (n)*   Factor
   95X
Confidence
 Interval
Acetal

»


i
i





»


•
'



3.3



3.4



3.6


»
5.7



8.8


1000
5000
10000

1000
5000
10000

1000
5000
10000

1000
5000
10000

1000
5000
10000
9670
28000
37600

1500
8480
22600

226
1420
2980

698
1150
1840

1890
9640
15800
149 (4)
150 (4)
386 (4)

49.3 (4)
64.5 (4)
50 (4)

119 (4)
79.4 (4)
164 (4)

115 (3)
129 (4)
257 (4)

75.7 0)
540 <5)
141 <«>
0.103
0.179
0.266

0.667
0.590
0.442

4.42
3.52
3.36

1.43
4.35
. 5.34
•
0.529
0.519
0.633
0.109 - 0.0986
0.182 - 0.176
0.275 - 0.258

0.744 - 0.604
0.604 - 0.576
(0.442)

7.82 - 1.65
4.28 - 2.99
4.07 - 2.86

4.91 - 0.839
6.76 - 3.20
9.78 - 3.76
•
0.639 - 0.451
0.614 - 0.449
0.651 - 0.615
*Number of replicates analyzed

-------
                                    TABLE 12  (Cont.)
Compound
Wavelength
   (UP)
                            RESPONSE FACTORS ON MIRAN 1A/80
  Actual
Concentration
  (ppmv)	
 Instrument                                     95%
Concentration   Standard        Response     Confidence
  (ppmv)	   Deviation (n)    Factor       Interval
Acetal



Acetyl-l^propanol, 3-
1

i
i


Benzoyl Chlori'de


j
Carbon Tetrachlorido


9.5



3.3


9.5



6.35



5.7


1000
5000
10000

500
1000

100
500
1000

100
500
1000

500
1000
10000
6690
23400
27200

247
813

39.2
217
406

•<70
5080
5420

115
232
390
672 (^
699 (5)
54.8 (5)

33.7 (5)
66.7 (5)

12.9 (4)
11.4 (5)
41.5 (5)

80.1 (5)
50.3 (5)
270 (5)

5.13 (3)
42.9 (4)
45.7 (5)
0.149
0.214
0.368

2.02
1.23

2.55
2.30
2.46

0.0209
0.0984
0.185
•
4.35
4.31
25.6
0.220 - O.lp
0.233 - 0.197
0.370 - 0.366

3.26 - 1.47
1.59 - 0.501

3.78 - 1.25
2.70 - 2.01
1.44 - 1.92
'
.0215 - 0.0196
.101 - 0.0192
.214 - 0.162

.38 - 3.65
0.5 - 2.71
8.0 - 19.3

-------
TABLE 12 (Cont.)

Compound

Wavelength
(um)
RESPOND
E FACTORS
Actual
Concentration
(ppmv)
ON MIRAN 1A/80
Instrument
Concentration
(ppmv)

Standard
Deviation (n)

Response
Fnctor

95%
Confidence
Interval
Carbon Tetrachlorlde



i



Chloro-Acetaldehyde




.
-




6.35

9.5

13.5



3.3


3.4

3.6


5.7


10000

10000

500
1000
10000

1000
10000

10000

1000
10000

500
1000
10000
7920

64

1810
4300
33100

116
3660

580

64.0
2020

1870
2350
7620
330 (5)

4.28 (3)

143 (5)
309 (5)
572 (5)

92.3 (5)
384 (4)

40.9 (4)

3.80 (5)
127 (4)

13.0 (5)
28.8 (5)
356 (4)
1.26

156

0.276
0.233
0.302

8.62
2.73

17.2

15.6
4.95

0.267
0.426
1.31
.1.43 - 1.13

219 121

0.354 - 0.226
0.291 - 0.194
0.317 - 0.288

14.71 - 2.68
3.00 - 0.205

22.2 - 14.1

18.7 - 13.4
6.00 - 4.21

0.273 - 0.262
0.441 - 0.412
1.54 - 1.14

-------
                                                     TABLE 12  (Cont.)
                                              RESPONSE FACTORS ON MIRAN 1A/80
                 Compound
Wavelengtn
   (urn)
ts>
  Actual
Concentration
  (ppmv)
 Instrument
Concentration
  (ppmv)
Standard
Deviation (n)
Response
 Factor
   95*
Confidence
 Interval
Chloro-Acetaldohyde




)
!

I



Chloroform

.
'
Dlchloro-1-proponol, 2, 3-

6.35



9.5



13.5


%
13.5



3.3

500
1000
10000

500
1000
10000

500
1000
10000

1000
5000
10000

1200

4840
5680
6760

76
228
1880

709
2300
21800

6680
22200
34200

64.9

55.9 . (5)
151 (5)
813 (4)

12.9 (5)
5.89 (5)
64.3 (3)

29.9 (4)
82.9 (5)
802 (3)j

747 (5)
1260 (5)
2430 (4)

22.6 (3)

0.103
0.176
1.48

6.58
4.39
5.32

0.705
0.435
0.459

0.150
0.225
0.292

18.5
'


2.40 - 1 07

12.5 - 4.47
4 71 - L HO
6.27 - 4.64

0.814 - 0.621
0.483 - 0 V)s
0.545 - 0.396

0,217 - 0.114
0.267 - 0 1QS
0.378 - 0.239

29.7 - 7.40


-------
                                                       TABLE 12  (Cont.)
                  Compound
                                               RESPONSE FACTORS ON MIRAN 1A/80
Wavelengtn
(um)
Actual
Concentr
(pprav)
Instrument
atlon Concentration
(ppmv)
Standard
Deviation (n)
Response
Factor
95%
Confidence
Interval
Dlchloro-1-propanol, 2, 3




i
i - -~- -

Dichloro-2-propanol, 1, 3-



* •


t
>
Dlisopropy 1 Benzene ,1,3


9.5



13.5


3.3

9.5

t

13.5


3.3


100
500
1200

500
1200

1200

100
500
1200

500
1200

100
500
1225
85.2
447
. 747

1160
2230

227

65.4
304
653

1070
2300

133
703
1270
12.2 (5)
6.81 (3)
20.6 (4)

58.0 (4)
154 (4)

10.1 (3)

6.95 (5)
22.3 (3)
35.2 (4)

70.9 (3)
177 (3)

30.8 (4)
60.1 (5)
108 (3)
1.17
1.12
1.61

0.431
0.538

5.29

1.53
1.64
1.84

0.467
0-.522
' '
0.774
0.716
0.965
.95 - 0.840
.20 - 1.05
.76 - 1.48

.513 - 0.372
.690 - 0.441

6.54 - 4.44
•
M7 - 1.18
2.40 - 1.25
2.22 - 1.57

0.653 - 0.364
0.780 - 0.392
•
2.94 - 0.446
0.938 - 0.578
1.52 - 0.706
j    J^i"
  OJ

-------
                                     TAJJL.E.
                             RESPONSE FACTORS ON MIRAN 1A/80
Compound
           Wavelength
  Actual
Concentration
  (ppmv)	
 Instrument                                      95^
Concentration   Standard         Response     Confidence
  (ppmv)	   Deviation  (n)     Factor       Interval
Dii sop ropy 1 Benzene , 1 , 3-




i
Diketene




»


,
'


6.35


5.7


3.3


5.7

»

9.5




500
1225

100
500
1225
5000
10000

1000
5000
10000

1000
5000
10000

•
134
507

311
343
380
354
1240

2280
6390
8600

69.4
377
580


34 (3)
77.9 (3)

8.04 (5)
12.5 (4)
14.2 (3)
13.9 (3)
197 (3)

226 (5)
171 (4)
487 (4)

15.7 (4)
23.6 (5)
65.9 (4)


3.75
2.42

0.331
1.47
3.22
14.1
8.06

0.439
0.782
1.16.

14.4
13.4
17.2


5.65 - 1.80
7.12 - 1.45

0.359 - 0.309
1.66 - 1.31
3.84 - 2.78
17.0 - 12.1
25.5 - 4.79
•
0.605 - 0.344
0.855 - 0.721
. 1.42 - 0.985

51.4 - 8.38
16.1 - 7.41
27.0 - 12.7



-------
                                                    TABLE 12 (Cont.)
                                             RESPONSE  FACTORS ON MIRAN  1A/80
               Compound
Wavelength
   (um)
  Actual
Concentration
  (ppmv)	
 Instrument
Concentration
  (pptnv)	
Standard
Deviation (n)
Response
 Factor
   95Z
Confidence
^Interval
Dimethyl Styrene,2,4-




i





Dlmethylsulflde »


•
'


3.3


5.7



6.35



3.3



3.4


500
1170

100
500
1170

100
500
1170

1000
5000
10000

1000
5000
10000
146
567

956
964
978

2540
2710
3010

2030
10100
20500

66.0
1510
3250
23.1 (4)
27.0 (5)

8.81 (5)
4.55 (5)
7.56 (5)

73.0 (5)
50.7 (5)
33.6 (5)

49.9 (4)
394 (4)
462 (5)

5.96 (4)
55.1 (3)
48.3 (5)
3.43
2.06

0.105
0.520
1.20

0.394
0.185
0.389

0.493
0.495
0.488

15.2
3.31
3.08
6.91 - 2.28
2.38 - 1.82

0.107 - 0.102
0.527 - 0.513
1.22 - 1.17

0.0428 - 0.0365
0.195 - 0.184
0.401 - 0.377

fr.534 - 0.457
0.565 - 0.440
0.520 - 0.459
•
21.3 - 11.8
3.93 - 2.86
3.21 - 2.95
en

-------
                                    TABLE 12 (Cont.)
                             RESPONSE FACTORS ON MIRAN 1A/80
Compound
Wavelength
   (urn)
  Actual
Concentration
  (pprov)	
 Instrument
Concentration
  (ppmv)	
Standard
Deviation (n)
Response
 Factor
   95%
Confidence
 Interval .
Dimathvlaulflde




	 r '-
1
1



;

»
Ethanol

»




S.7



6.35

•

9.5

•
*
3.3



3.4


1000
5000
10000

1000
5000
10000
' i
1000
5000
10000

1000
5000
10000

1000
5000
10000
S22
1010
1180

2A80
4590
6540

15.3
120
270

3830
18500
34300

430
3420
7530
33. s (4)
52.4 (4>
95.4 m

90.7 (4)
112 (4)
190 (4)

2.90 (4)
3.51 (3)
27.4 (4)

181 (5)
432 (5)
217 (5)

16.8 (4)
47.2 (5)
72.1 (5)
1.92
4.95
8.47

0.403
1.09
1.53

65.4
41.7
37.0

0.261
0.270
0.292 ,

2.33
1.46
1.33
1.40 - 1L08
5.93 - 4,25
13.0 - 6.29

0.456 - 0.361
1.18 - 1.01
1.68 - 1.40

165 - 40.8
47.7 - 37.0
54,7 - 28.0
*
0.301 - 0.231
0.289 - 0.254
0.297 - 0.287
•
2.66 - 2.07
1.52 - 1.41
1.36 - 1.29.

-------
                         'I'AHLE 12  (Cont.)
Wavelength
   (uro)  __
                  RESPON8IJ  FACTORS  ON MIRAN 1A/80
  Actual
Concentration
  (ppniv)
 Instrument
Concentration
  (ppmv)
Standard
Deviation  (11)
Response
 Fnctor
   95%
Confidence
 Interval
Ethunol





i
i - - . . . .


i
Etlmnolamine

»r» *l


Etliylene Dicliloridc (tr
j


3.6


8 8


9.5



9.5

»
13.5

ns) 5.7



5000
10000

10000


1000
5000
10000

100
500

500

1000
5000
10000

386
941

668


2210
8440
16800

25.9
135

5620

684
815
940

4.24 (4)
10.7 (5)

20 8 (51


53.2 (4)
290 (4)
255 (5)

3.67 (4)
8.38 (4)

1050 (4)

14.5 (3)
8.02 (4)
19.1 (4)

13.0
10.6

15.0


0.452
0.592
0.595

3.86
3.70

0.089'

1.46
6.13
10.6

13.4 - 12.6
11.0 - 10.3

1 ft A _ 1 i H
J.0 .1 — JLJ. o

0.490 - 0.420
0.665 - 0.534
0.621 - 0.571
.
7.03 - 2.66
4.61 - 3.09
»
0.219 - 0.075

Is 61 - 1.34
6.33 - 5.95
11.4 - 9.99


-------
                                    TABLE 12 (Cont.)
                            RESPONSE FACTORS ON HIRAN  1A/80
Compound
Wavelength
   (um)
  Actual
Concentration
  (ppmv)	
 Instrument
Concentration
  (ppmv)	
Standard
Deviation (n)
Response
 Factor
   957.
Confidence
 Interval
Ethylene Dichloride (tra


.

i
|

£ | Ethyleneglycoldlmethyl
Er.her



w

*
i


B) 6.35



8.8


3.3



3.4



3.6


1000
5000
10000

5000
10000

1000
5000
10000

1000
5000
10000

1000
5000
10000
1160
1760
2270

658
1540

5110
21100
33800

2310
11700
20600

284
1870
3920
34.1 (4)
30.0 (3)
136 <5)

23.1 (3)
41.2 (4)

86.2 (5)
460 (5)
351 (6)

42.8 (5)
358 (5)
501 (6)

7.09 (5)
74.6 (5)
93.5 (6)
0.862
2.84
4.41

7.60
6.49
.
0.196
0.237
0.296

0.433
0.427
0.485

3.52
2.67
2.55
0.951 - 0.78fl
3.07 - 2.65
5.29 - 3.78

8.95 - 6.60
7.10 - 5.98

0.205 - 0.187
0.252 - 0.223
0.304 - 0.288

0.456 - 0.412
0.431 - 0.394
0.518 - 0.457
•
3.78 - 3.29
3.01 - 2.41
2.72 - 2.40

-------
                                     TABLE 12  (Cont.)
Compound
Wavelength
   (u«n)
                             RESPONSE FACTORS ON MIRAN  1A/80
  Actual
Concentration
  (ppmv)	
 Instrument
Concentration
  (ppmv)	
Standard
Deviation (n)
Response
 Factor
   95%
Confidence
 Interval
Ethyleneglycoldimethyl
Ether



t
	 1 --
!





Ethyleneglycolmonoethyl
Ether Acetate




6.35



8.8



9.5


*
»
3.3

»
i
3.4
•
1000
5000
10000

1000
5000
10000

1000
5000
10000

200
1000
2GOO

1000
2000
1040
2280
4110

1570
9160
16000

1230
5130
9620

410
3570
4890

457
817
150 (5)
169 (5)
324 (6)

82.0 (5)
342 (5)
268 (6)

72.8 (5)
202 (5)
195 • (5)

51.2 (4)
122 (4)
50.3 (3)

67.0 (5)
80.0 (3)
0.962
2.19
2.43

0.637
0.546
0.625

0.813
0.975
1.04

0.488
0.280
0.409

2.19
2.45
1.61 - 0.686
2.76 - 1.82
3.0$ ~ 2.02

0.745 - 0.556
0.609 - 0.435
0.653 - 0.599

0.973 - 0.698
1-Q9_- 0.87?
1.10 - 0.934
*
0.809 - 0.349
0.314 - 0.253
0.428 - 0,392
•
3.69 - 1.55
4.23 - 1.72

-------
                                     TABLE 12 (Cont.)
                             RESPONSE FACTORS ON MIRAN  1A/80
Compound
Wavelength
   (um)
  Actual
Concentration
  (ppmv)	
 Instrument
Concentration
  (ppmv)	
Standard
Deviation (n)
Response
 Factor
   95%
Confidence
 Interval
Ethyleneglycolmonoethyl
Ether Acetate



i
!


1
i 	




Formaldehyde



3.6


5.7



8.8


9.5
V
•


3.3
i

3.4
1000
2000

200
1000
2000

1000
2000

200
1000
2000

500
1000

1000
50.8
158

2590
5110
6960

261
808

472
2190
3470

266
916

72.4
5.79 (3)
6.93 (3)

75.5 (3)
177 (4)
230 (4)

32.7 (3)
58.3 (3)

9.63 (4)
165 (4)
129 (3)

36.4 (6)
27.7 (6)

11.2 (6)
19.7
12.7

0.0772
0.196
0.287

3.83
2.48

0.424
0.457
0.576

1.88
1.09

13.8
8.6 - 13.2
15.6 - 10.6

0.0883 -.0.0686
0.220 - 0.176
0.321 - 0.260

8.31 - 2.49
3.59 - 1.89

0.453 - 0.398
0.600 - 0.368
0.686 - 0.497

2.90 - 0.991
1.18 - 1.01

22.9 - 9.88

-------
                                    TABLE 12 (Cont.)
                            RESPONSE FACTORS ON MIRAN 1A/80
Compound
Wavelength
   (um)
  Actual
Concentration
  (ppmv)	
 Instrument
Concentration
  (ppmv)	
Standard
Deviation (n)
Response
 Factor
   952
Confidence
 Interval
Formaldehyde




t
i
i i
i
i

Formic Acid








3.6


5.7


9.5


3.3

x
V
3.4

»
3.6


500
1000

500
1000

500
1000

5000
10000

5000
10000

5000
10000

234
626

2490
3290
1
180
347

6930
18900

906
2860

1410
4510

47.1 (7)
34.2 (6)

147 (8)
99.4 (7)

19.8 (6)
44.0 (6)

79.7 (5)
335 (5)

11.5 (5)
51.3 (5)

22.8 (5)
101 (5)

2.14
1.60

0.201
0.304

2.78
2.88

0.722
0.529

5.52
3.50

3.55
2.22

4.22 - 1.43
1.86 - 1.40

0.233'- 0.176
0.328 - 0.283

3.87 - 2.17
4.27 - 2.17
•
0.745 - 0.699
0.557 - 0.504

5.72 - 5.33
3.61 - 3.38

3.95 - 3.22
2.36 - 2.09


-------
                                                   TABLE 12  (Cont.)
                                             RESPONSE FACTORS  ON  MIRAN IA/80
               Compound
Wavelength
   (urn)
  Actual
Concentration
  (ppmv)	
 Instrument
Concentration
  (ppmv)	
Standard
Deviation (n)
Response
 Factor
   95%
Confidence
 Interval
Formic Acid



,
1





Freon 12

*




5.7



8.8


9.5



6.35



8.8


500
5000
10000

5000
10000

500
5000
10000

- 1212.5
2425
4850
•
1212.5
2425
4850
4990
23600
31300

1000
2920

1190
9120
14100

5940
6470
7490

1714
3130
4680
136 (5)
89.4 (5)
182 (5)

26.0 (5)
60.6 (5)

66.7 (5)
111 (5)
130 (5)

270 (5)
140 (5)
92.6 (5)

263 (5)
74.3 (5)
49.3 (5)
0.100
0.212
0.319

5.00
3.42

0.420
0.548
0.709

0.204
0.375
0.648

0.707
0.775
1.04
0.108 - 0.0931
0.214 - 0.210
0.325 - 0.314

5.39 - 4.66
3.63 - 3.24

0.498 - 0.364
0.567 - 0.530
0.728 - 0.691

0.234 - 0.181
0.399 - 0.354
0.671 - 0.626

1.23 - 0.496
0.830 - 0.727
1.07 - 1.01
to

-------
                                                     TABLE 12  (Cont.)
                Compound
                                              RESPONSE FACTORS ON Mlran 1A/80
Wavelength
(ura)
Actual
Concentn
(pprav)
Instrument
ition Concentration
(ppmv)
Standard
Deviation (n)
Response
Factor
95%
Confidence
Interval
Freon 12



Furfural
i
i


i









9.5



3.6

5.7



6.35
ft


9.5



1212.5
2425
4850

1200

100
500
1200

100
. 500
1200

100
500
1200

6280
55000
72600

53.4

1230
1310
1420

4240
8040
13400

32.3
138
321

730 (5)
2130 (5)
1290 (5)

6.74 (5)

9.57 m
12.6 <4)
26.3 U)

113 (4)
120 (4)
420 (4)

3.50 (4)
8.66 (4)
15.2 (4)

0.193
0.0441
0.0668

22.5

0.0813
0.382
0.845

0.0236
0.0622
0.0896

3.10
3.26
3.74

.285 - 0.14b
0.0494 - 0.0398
0.0703 - 0.0637

34.8 - 16.6

0.0837 - 0.0793
0.394 - 0.370
0.898 - 0.798

0.0258 - 0.0217
0.0652 - 0.0594
0.0995 - 0.0814

4.72 - 2.30
4.53 - 3.02
4.40 - 3.25

Ul
to

-------
                                     TABLE 12  (Cont.)
                              RESPONSE FACTORS ON MIRAN 1A/80
            Wavelength
Compound       (ym)
  Actual
Concentration
  (pprov)	
 Instrument
Concentration
  (ppmv)	
Standard
'Deviation (n)
Response
 Factor
   95%
Confidence
 Interval
Furfural



Glycidol ;
i

o, I
*- 1





Hydroxyacetone




13.5



3.3
•
3.6

5.7

6.35
%
9.5

5.7

6.35

9.5
100
500
1200

100

100

100

100
»
100

100

100

100
656
5470
12200

262

572

3100

6540

132

1950

6870

24.6
24.9 (3)
260 (4)
532 (4)

24.6 (3)

27.0 (4)

52.6 (A)

99.3 (4)

10.4 (4)

24.3 (8)

72.8 (7)

3.58 (8)
0.152
0.0914
0.0984

0.382

0.175

0.0323

0.0153

0.758

0.0513

0.0146

4.07
0.182 - 0.131
0.108 - 0.0794
0.114 - 0,864

0.640 - 0.272

0.206 - 0.152

0.0341 - 0.0306

0.0161 - 0.0146

1.01 - 0.606

0.0528 - 0.0498
• •
0.0149 - 0.0142

6.21 - 3.02

-------
                                                     TABLE 12 (Cont.)
                                              RESPONSE FACTORS ON MIRAN 1A/80
                            Wavelength
                 Compound       (pm)
  Actual
Concentration
  (ppmv)	
 Instrument
Concentration
  (ppjnv)	
Standard
Deviation (ri)
Response
 Factor
   95X
Confidence
 Interval
Methanol




i
i

•









3.3



3.4



3.6


6.35



9.5


1000
5000
10000

1000
5000
10000

5000
10000

1000
5000
10000

1000
5000
10000
2520
17000
24400

101
1810
3840

10.3
181

2920
4230
5540
•
'438
1940
2870
102 (5)
7800 (5)
340 (4)

9.56 (5)
20.5 (5)
45.1 (4)
•
1.63 (5)
3.40 (4)

226 (5)
785 (4)
90.9 (4)

303 (4)
57.4 (4)
116 (4)
0.397
0.294
0.410

9.90
2.76
2.60

485
55.2

0.342
1.18
1.81

2.28
2.58
3.48
0.447 - 0.357
0.458 - 0.129
0.429 - 0.392

13.4 - 7.84
2.85 - 2.6B
2.71 - 2.51

867 - 337
58.8 - 52.1

0.436 - 0.282
1.26 - 1.12
1.90 - 1.72

2.93 - 1.07
2.81 - 2.3H
4.00 - 3.09
\J\

-------
                                                     TABLE 12 (Cont.)
                Compound
                                              RESPONSE FACTORS ON MIRAN  1A/80
Wavelength
(um)
i Actual
Concentra
(pprov)
Instrument
tion Concentration
(ppmv)
Standard
Deviation (n)
Response
Factor
95X
Confidence
Interval
Methyl Styrene, o-



'
	 i -
!

!
!







Methylene Chloride

3.3
.

5.7



6.35


9.5
»

13.5


3.3

1030
5000

103
1030
5000

1030
5000

1030
5000

1030
5000

5000
10000
976
2830

330
1230
1570

4490
6960

73.6
178

167
948

1740
3740
38.6 (4)
229 (5)

9.20 (4)
10.0 (5)
48.3 (5)

128 (5)
322 (5)

3.67 (4)
» 5.57 (3)

49.2 (5)
' 92.2 (4)

62.7 (5)
144 (5)
1.06
1.77

0.312
0.837
3.18

0.229
0.718

14.0
28.1

6.17
5.27

2.87
2.67
1.21 - 0.937
2.28 - 1.44

0.342 - 0.287
0.858 - 0.819
3.48 - 2.93

0.249 - 0.213
0.824 - 0.637

16.6 - 12.1
32.5 - 24.8

34.1 - 3.39
7.64 - 4.03

3.19 - 2.61
2.99 - 2.42
Ul

-------
                                                    TABLE 12 (Cont.)
                                             RESPONSE FACTORS ON MIRAN 1A/80
                Compound
Wavelength
   (lim)
  Actual
Concentration
  (pprov)	
 Instrument
Concentration
  (ppmv)	
Standard
Deviation (n)
Response
 Factor
   95%
Confidence
 Interval
•fethylene Chloride



Pentanethiol, 1-
- i












13.5



3.3



3.4


%
3.6


9.5


1000
5000
10000

1000
5000
10000

1000
5000
10000

5000
10000

1000
5000
10000
30050
98400
119000

3180
11300
15800

648
4590
8650

267
634

89.4
483
886
933 (4)
4760 (5)
2880 (5)

15.3 (3)
370 (5)
265 (3)

14.8 (A)
115 (4)
97.1 (3)
«
23.4 (5)
18.5 (4)
i
18.6 (3)
51.6 (A)
50.7 (3)
0.0333
0.0508
0.0840

0.314
0.442
0.633

L.54
1.09
1.16

18.7
15.8

11.2
10.4
11.3
0.0369 - 0.0303
0.0587 - 0.0448
0.0901 - 0.0787

0.321 - 0.308
0.487 - 0.406
0.682 - 0.590

.1.66 - 1.44
1.18 - 1.01
1.21 - 1.10

24.8 - 15.1
17.4 - 14.4

106 - 5.90
15.7 - 7.73
12.7 - 10.1
O)
-J

-------
                                                    TABLE 12 (Cent.)
                                             RESPONSE FACTORS ON MI RAN  1A/80
                           Wavelength
                Compound       (uro)
  Actual
Concentration
  (ppmv)
 Instrument
Concentration
  (ppmv)	
Standard
Deviation (n)
Response
 Factor
   95X
Confidence
 Interval
Pentunethiol. 1-


Perchloromethvlmercaptan

!

;
i









13.5


3.3

3.6

5.7



8.8

9.5




5000
10000

5000

5000

500
1000
5000

5000

500
1000
5000


,- 5300
10«iOO

612

64.0

1730
3410
7660

426

36.7
132
303


217 (4)
289 f3)

28,2 (5)

4.99 (5)

•570 (3)
112 (4)
306 (5)

31.4 m

2,65 (1)
13.3 m
20,7 f4)


0.941
0.9S2

ft. 17

78.1

0.289
0.293
0.653

11.7

13.6
7.58
16.5


-1, OH_- 0 fl35
-1.08 - O.H52

_9J7 - 7,24

99t7 - fiA.2


-------
                                                    TABLE 12 (Cont.)
                                            RESPONSE FACTORS ON MIHAN 1A/80
Compound
                           Wavelength
                              (um)
  Actual
Concentration
  (ppmv)	
 Instrument
Concentration
  (ppmv)
Standard
Deviation  (n)
Response
 Factor
   95X
Confidence
 Interval
Propylene Chlorohydrln

*

1
i

•
i









3.3



3. 4


3.6
•
6.35

%

8.8

9.5


500
1000
5000

1000
5000

5000

500
1000
5000

5000

500
1000
5000
1240
2990
14200

36.6
1490

51.6

3040
3630
3960
•
795

462
966
4470
31.1 (4)
92.0 (5)
81.6 (4)

3.39 (4)
39.6 (5)

2.30 (3)

151 (4)
69.4 (5)
37.7. (5)

53.3 (5)
>
ll.'A (4
45.4 (5
157 (5
0.403
0.334
0.352

27.3
3.36

96.9

0.164
0.275
1.26

6.29

1.08
1.04
1.12
0.438 - 0.373
0.366 - 0.308
0.359 - 0.346

38.7 - 21.1
3.62 - 3.12

120 - 81.3
•
0.195 - 0.142
0.291 - 0.262
1.30 - 1.23

7.73 - 5.30

1.17 - 1.00
1.19 - 0.916
1.24 - 1.02
in

-------
                         TABLE 12 (Cont.)
                  RESPONSE FACTORS ON MIRAM 1A/80
Compound
Wave Length
     ,m\
  Actual
Concentration
  (pprov)	
 Instrument
Concentration
  (ppmv)	
Standard
Deviation  (n)
Response
 Factor
   953!
Confidence
 Interval
Propylene Chlorohydrin



Tetrachloroe thane, 1, 1, 2,
i
i
i





»
Trichloroethane, 1, 1, 1-

j



13.5



- 3.3


8.8

13.5

%

3.3



3.4

500
1000
5000

5000
10000

10000
t
1000
5000
10000

1000
5000
10000

5000
10000
3800
8510
38600

582
1010

404

20000
73000
101000

266
2910
5920

38.8
421
128 (4)
194 (4)
904 (5)

26.1 (4)
21.6 (4)

25.1 (4)

616 (4)
2750 (4)
1670 ^4)

17.5 (4)
8.16 ,(4)
28.9 ' (4)

3.25 (4)
2.59 (5)
0.132
0.118
0.130

8.59
9.90

24.8

0.0500
0.0685
0.0990

3.76
1.72
1.69

129
23.8
0.147 - 0.119
0.127 - 0.110
0.139 - 0.122

10.0 - 7.52
10.6 - 9.27

30.8 - 20.7
•
0.0554 - 0.0455
0.0778 - 0.0612
0.105 - 0.0941

4.75 - 3.11
1.73 - 1.70
1.72 - 1.66

175 - 102
24.2 - 23.4

-------
                                    TABLE 12  (Cent,)
                             RESPONSE FACTORS ON MIRAN IA/80
           Wavelength
Compound      (urn)	
  Actual
Concentration
  (ppmv)
 Instrument
Concentration
  (ppmv)
Standard
Deviation (n)
Rcsponne
 Factor
   95X
Confidence
 Interval
Trichloroethaner 1,1,1- 1 6.35



9'5
,'

,
: 13.5
.

1 »
Trichlorotrlfluoro- j 5.7
ethane, 1,1, 2- ]
-
'
6.35


1000
5000
10000

1000
5000
10000

1000
5000
10000

1000
5000
10000

1000
5000
10000
3010
14500
27400

4330
13900
19900

4120
16400
29100

640
856
1060

1390
2390
3520
87*2 (3)
114 (5)
95.7 (4)

238 (5)
283 (5)
1520 (4)

431 (4)
171 (4)
340 (4)

46.5 (4)
26.7 (5)
55.1 (3>
-
181 (3)
97.8 (5)
189 (4)
0.332
0.345
0.365

0.231
0.360
0.503

0.243
0.305
0.344

1.56
5.84
9.43

0.719
2.09
2.84
.380. - 0.295
0.353 - 0.337
0.369 - 0.361

0.273 - 0.200
0.381 - 0.340
0.664 - 0.404

0.364 - 0.182
0.315 - 0.295
0.357 •• 0.331

2.03 - 0.127
6.40 - 5.38
12.1 - 7.71

1.69 - 0.544
2.36 - 1.8U
3.43 - 2.43

-------
                                                    TABLE 12 (Cont.)
                Compound
Wavelength
   (um)
                                             RESPONSE FACTORS ON MIRAN 1A/80
  Actual
Concentration
	(ppray)	
 Instrument                                      95%
Concentration    Standard        Response      Confidence
      v)	    Deviation (n)    Factor        Interval
Trichlorotrlfluoro-
ethane,l,l,2-


.'



•




*
j



8.8



9.5



13.5


\






1000
5000
10000

1000
5000
10000

5000
10000








5840
16100
18500

977
3690
6280

1100
2270








76. A (5)
50.0 (4)
134 (5)

55.0 (5)
6.93 (3)
58.0 (4)

28.9 (4)
132 (4)








0.171
0.311
0.541

1.02
1.36
1.59
•
4.55
4.41
• »


>
j



0.178 - 0.165
0.314 - 0.308
0.552 - 0.530

1.21 - 0.885
1.37 - 1.34
1.64 - 1.55

4.96' - 4.19
5.40 - 3.72





•


ro

-------
 6.  DISCUSSIONS AND CONCLUSIONS

 A.  Photoionization Detection

 As noted previously, the photoionization technique vas evaluated for a
 limited number of compounds due to both chemical and, more significantly,
 equipment problems.  The PI-101 was calibrated with dichloromethane so
 as to permit direct comparison with response factors reported in
 Reference 3.  The response factors observed for the 16 compounds tested
 on the photoionization detector, PI-101, range from 0.50 to 48.  Seventy-
 five percent (12) of the compounds have response factors of less than
 five and greater than 0.2.  There appears to be no obvious trend of
 response factor with molecular weight (carbon number) or functionality
 within this group.   On the other hand,  it is interesting to note that for
 both alcohols tested,  i.e., methanol and ithanol,  the response factors are
 inversely proportional to carbon number.  Thus, it appears that non-
 binding electrons on the oxygen atom of the alcohols do not provide a
 much greater photoionization yield than other sigma-bonded electrons in
 compounds with similar carbon numbers.   The high response factor for
 trichlorotrifluorethane is consistent with  its high ionization poten-
 tial (11.78 eV).   In fact,  this ionization  potential is slightly higher
 than the quoted energy of the UV lamp used  in the  study.   This may
 indicate that thermal  energy provides sufficient additional energy  to
 permit some ionization when coupled to  the  energy  provided by the UV
 light.

 Although the specific  response  factors  for  the limited  number of com-
 pounds  tested do not unequivocally confirm  the suitability of photo-
 ionization  as a  general VOC screening technique, an important but cautious
 observation can be made.   That  is,  based on this small  sample of com-
 pounds  tested, which includes an aromatic compound  (i.e.,  toluene),  an
 ether  (i.e.,  acetal), an alcohol  (i.e.,  ethanol) and chlorinated alkanes
 (i.e.,  trichloroethane  and  chloroform),  the  response factor over a  con-
 centration  range of 500  ppmv  to 10,000 ppmv  may be  within  a factor  of
 five.   This  result is consistent with an expectation (Figure  1)  of  more
 similar photoionization  yield from sigma and pi electrons when the  com-
 pound is influenced by UV radiation of approximately 12 eV  rather than
 10 eV.   The  expectation  that photoionization yield  for aliphatic and
 aromatic compounds may be similar  indicates  the potential usefulness
 of photionization as a VOC  screening tool.

 In terms of  current availability as a potential VOC detector,  the most
 significant  result with  respect to  the photoionization detector  (HNU
 Systems, -Inc. PI-101 and AID, Inc.  580)  is probably  the difficulty
 observed in  operating the prototype dilution system.  Both dilution
 probes were  designed and fabricated by the respective manufacturers
under severe  time limitations.  Neither probe was designed in a manner
which permitted reliable independent measurement of dilution ratio or
 reproducible  adjustment.  Thus, the absolute dilution ratio is in some
doubt.  The ability to adjust the dilution ratios was practically non-
 existent.  As noted previously, the fixed dilution ratio's were inappropriate
                                   63

-------
 for analysis of vapor concentrations which yielded instrument responses
 much above 10,000 ppnrv or much below 1000 ppmv.  Detector saturation
 was observed somewhat above an instrument response of 10,000 ppmv.  At
 the span settings required for adequate operation, the background
 instrument response to zero air was quite high.
                                                    *
 Whenever the intensity of the UV lamps began to decrease (note that the
 AID,  Inc. lamp failed early in the program),  the instrument span had to
 be increased regularly.   Some alteration to the span potentiometer
 setting could be made to correct for this decrease in response.   However,
 for some tests the correction was not sufficient to yield an identical
 calibration.   Under these conditions,  response factors were calculated
 at a  different absolute instrument response.   The data included in
 Table 11 reflects this variation in span point.  However, since the
 calibration curve is linear over the range of 0-10,000 ppmv (with
 dilution,  that is about  0-1000 ppmv) (Figure  5), no systematic error
 should  occur  due to the  change in absolute response.

 Due'to  declining instrument response and low  vapor pressure of many •
 compounds,  one-half of the  compounds tested did not yield reliable
 response factors.   The problems  noted  above and limited data obtained
 indicate :hat,  at  the present  time,  a  reliable photoionization system
 does not exist  to  operate over a  VOC concentration range of  100  ppmv to
 10,000  ppmv.  More accurately, a  reliable  dilution/photoionization system
 is  not  available.

 B.  Infrared Detection

 The results of  the  evaluation of  the Miran 80 are much more  complete.
 A total of 32 compounds were analyzed.  As noted previously, other
 compounds were not  tested for several reasons,  including  (1) low vapor
 pressure; (2) reactivity; (3) lack of availability; and  (4)  close
 chemical similarity to compounds previously tested.  Prior to  testing,
 the instrument was calibrated with individual  span gases at  eight
 analytical wavelengths which correspond to individual functional groups,
 e.g.,  C-H; C-C1; C-OH.  The calibration curve data  (Table 13) indicate
 that the absorbance values observed over the concentration range of
 100 to 10,000 ppmv are linear.  Test compounds were then run and the
 instrument response calculated on the basis of the response indicated
 by  the specific span gas used at individual analytical wavelengths.

An analysis of the data in Table 12 indicates that the response factors
 for most compounds with a particular functional group,  determined at an
analytical wavelength which corresponds to that functional group
 (Table 10), are generally less than a value of twenty.   This is consistent
with the general observation that the functional group is more important
 than the remainder of the molecule in determining the IR extinction
 coefficient of the compound at the wavelength of interest.
                                                   •
 For example, three of the four aromatic compounds tested have -
 reasonable response factors (<5)_at 6.35 urn as shown below.   This
                                   64

-------
                                     SLOPE: 0.711
                                     IBTZBCEPT: 6£4
                                     S- 15
                                     COU. OOEFF: 0.995
 4         6         8
ACTUAL CONCDtTRAXXOH  a
                                                   10
5. Calibration curve for 1,2-dichloroethaneJor the HNU instrument.
        ...                    ~I~.~~	~                              >
        l5                  '    f^.9^

-------
                                                TABLE 13

                                     CALIBRATION DATA FOR MIRAN 80
Wavelength
   (um)

   3.3
   3.4

   3.6

   5.7

   6.35



   8.8


   9.5

  13.5
Functional
Group(a)

Aromatic and
Unsaturated C-H

Saturated C-H

Aldehyde C-H

Carbonyl C-0

Aromatic C-C,
conj C-C. N-H,
C-S

Ether C-O-C


Alcohol C-O-H

C-C1
Calibration
Compound

Toluene
Pentane

Butyraldehyde

Acetone

Toluene
Dllsopropyl
ether

Isopropanol

1,2-dichloro-
ethane
   Slope
(xlO-4 AU/ppm)

     .255
Y-Intercept
   (AU)

  .0114
Correlation
Coefficient

  .999
1.35
.436
.307
.059
.640
.587
.105
.0495
.00675 •
.00449
.0153
.0552
.00227
.00670
.994
.999
.999
.999
.992
.999
.992
AU - Absorbance Units

-------
 wavelength is within a broad aromatic ring stretch area.

           Compound                   Response Factor Range
                                                          A
           Diisopropyl Benzene          2.42  - 3.75

           Dimethyl Styrene,2,4-        0.185 - 0.934

           Methyl Styrene               0.229 - 0.718

 Within this group,  the addition of the large aliphatic group (isopropyl)
 on the benzene ring appears to reduce the sensitivity (larger response
 factor) at the aromatic C ~ C stretch wavelength as compared to less
 alkylated aromatics.

 In the case of aliphatic and substituted aliphatic compounds,  the OH
 stretch wavelength  of  3.3 ym yields suitable response factors (<5)  for
 about 52% of  those  tested.   The classical aliphatic C-H stretch is
 observed at  3.4  ym, but some overlap of  3.3  and  3.4 ym IR bands may
 occur in the  Miran  due  to incomplete resolution.   Also,  some shift  of
 the  CH stretch wavelength probably occurs due to nearby oxygen or
 halogens.  A  list of aliphatic  compounds and  corresponding response
 factor ranges at this wavelength are shown in Table 14.   If  one includes
 alkylated  aromatic  compounds (4) in the  list  of  compounds with response
 factors less  than five  at  3.3 ym - 3.4 ym, the percentage of  compounds
 tested  with suitable response factors increases  to  62%.

 Ten  chlorinated hydrocarbons tested  in this program yielded measurable
 response factors of 13.5 ym.  Seventy percent  were  observed  to yield
 response factors less than five  at this wavelength.  The  compounds
 and respective response factors  are  given in Table  15.

 Since the ultimate goal of this  instrument evaluation is  to assess  the
 suitability of IR as a general VOC screening technique, an assessment of
 the usefulness of a single wavelength for measurement of  orgauic compounds
of varied molecular weight and functionality is in order.  A review of the
data in Table 12 indicates that the number of  test compounds  (total of 32)
which yield response factors of less than 20 or greater than 0.05 at each
analytical wavelength are as follows:

          Wavelength (ym)                Number of Compounds

              3.3                                23
              3.4                                12

              3.6                                13
              5.7                                17*
              6.35                                17

              8.8                                11
              9.5                                25

             13.5                                1A
                                   67

-------
                               TABLE 14

       SUBSTITUTED ALIPHATIC COMPOUNDS WITH RESPONSE FACTORS
              LESS THAN TWENTY AT  3.3 ym  (Mlran  80)


    Compound                                  Response Factor Range
 Acetyl-l-propanol,3-                             1.23  -  2.02
 Chloro-acetaldehyde                              2.73  -  8.62
 Dichloro-l-propanol,2,3-                             18.5
 Dichloro-2-propanol,l,3-                              5.29
 Diketene                                         8.06  -  14.1
 DimethyIsulfide             .                      0.488-0.495
 Ethanol                                           0.261 -  0.292
 Ethyleneglycoldimethyl Ether                      0.196 -  0.296
 Ethyleneglycolmonoethyl Ether Acetate             0.280 -  0.488
 Formaldehyde                                      1.09  -  1.88
 Formic Acid                                       0.529 -  0.722
 Glycidol                                               0.382
 Methanol                                          0.294-0.410
 Methylene Chloride                                2.67  -  2.87
 Pentanethiol,!-                                   0.314 -  0.633
 Propylene Chlorohydrin                            0.334 -   0.403
Tetrachloroethane,l,l,2,2-                        8.59-9.90
Trichloroethane,1,1,1-                            1.69   -   3.76
                                  68

-------
                              TABLE 15
        CHLORINATED COMPOUNDS  AND RESPONSE FACTORS AT  13.5  ym
                           (Miran 80)
    Compound
Carbon Tecrachloride
Chloro-acetaldehyde
Chloroform
Dichloro-1-propanol,2,3-
Dichloro-1-propanol,lf3-
Methylene Chloride
Propylene Chlorohydrln
Tecrachloroethane,1,1,2,2-
Trichloroethane,1,1,1-
Trichlorotrifluoroethane,1,1,2-
Response Factor Range
   0.233  - 0.302
   0.435  - 0.705
   0.150  - 0.292
   0.431  - 0.538
   0.467  - 0.522
   0.0333 - 0.0840
   0.118  - 0.132
   0.0500 - 0.0990
   0.243  - 0.344
   4.41   - 4.55
                                 69

-------
  In some cases,  the response factors at a particular wavelength
  (e.g.,  5.7 urn)  are strongly a function of concentration.   It  appears
  that this may be due to a concentration broadening phenomenon which is
  frequently observed in gas phase infrared spectrometry.  If only those
  compounds which show a response factor between 5 and 0.2, and those
 which show no strong variation in response factor with concentration
  (i.e.,  < a factor of two from 1000 to 10,000 ppmv) are summarized as
 above,  fewer compounds yield suitable response factors:

           Wavelength (urn)                Number of Compounds

                3.3                              12

                3.4                               4

                3.6                               3
                5.7                               1

                6.35                              3

                8.8                               4

                9.5                               15

              13.5                                7
The results indicate  that only 3.3,  9.5 and 13.5  ym  analytical wavelengths
respond acceptably for a large number  of  compounds  (i.e., greater  than
10% of the total number of compounds).  However,  in  any  case, fewer  than
50% of the compounds  are reliably detected.  The  aliphatic and aromatic
compounds do not overlap at 6.35 ym  but do overlap at 3.3 ym.  However,
note that only alkylated aromatics have good response at 3.3 ym.   Thus,
there is apparently no useful agreement in response  factors between,
for example, a large  number of aromatic compounds and aliphatic compounds
(e.g., 50% of those tested) at analytical wavelengths specific to  each
compound class.  It is apparent that the overlap of  IR absorbance  bands
of different functional groups is not sufficient to  yield one analytical
wavelength which might be used to quantify both compound classes with
the expectation of agreement within a factor of five.  This observation
indicates that infrared spectrophotometry is not particularly suitable
for general VOC screening.

On the other hand, the fact that the response factors do not vary by
large values (i.e.,  greater than five)  for some classes of compounds,
e.g.,  halogensted aliphatics at 13.5 ym and aliphatic and alkylated
aromatics at 3.3 - 3.4 urn,  corroborates the suitability of infrared
spectrophotometry for VOC screening of  compounds belonging to one
functional group.   Even in this case, only 30 to 80% of the  compounds
in a given class may yield response factors less than five at a  single
specific IR wavelength.
                                  70

-------
C.  Conclusions

In summary, based on the results of this evaluation,  it  appears  that:

    1.   Infrared (IR)  spectrophotometry may not  be  suitable  for
        general VOC screening,  with the exception of  analysis
        of VOC emissions of  a single organic functional  group
        character.

    2.   IR screening of  organic compounds  of a single functional
        class,  e.g., C-C1, may  be suitable for as much as 80%
        of compounds in  the  class.

    3.   IR screening at  a wavelength corresponding  to both
        aliphatic and aromatic  CH stretches  may  be  suitable
        for as much  as 30-50% of  organic compounds.

    4.   A  portable photoionization device  is not  currently
        available for VOC screening  in  the concentration range
        of  100 ppmv  to 10,000 ppmv.

    5.   The development of a reliable dilution probe for use on
        a photoionization device is  close at hand.

   6.  With such a dilution probe,  it appears that a photoionization
       device with an 11.7 or 11.8 eV UV lamp may be used for
       reliable analysis of VOC fugitive emissions.
                                71

-------
  7.  LITERATURE CITED
                                                 tf
  1.  U.S. Environmental Protection Agency, "Measurement of Volatile
     Organic Compounds," Report No. PB80-221674 (September 1979).

 2.  U.S. Environmental Protection Agency, "Method 21.  Determination
     of Volatile Organic Compound Leaks," proposed regulations, Federal
     Register.  .46 (Monday,  January 5, 1981).

 3.  Brown,  G.E.,  D.A.  DuBose,  W.R. Phillips  and 6.E. Harris, "Response
     Factors of VOC Analyzers Calibrated with Methane for Selected
     Organic Chemicals," Task Report, U.S. Environmental Protection
     Agency, EPA 600/2-81-002 (September 1980).

 4.  Anastas, M.Y.  and  H.J.  Belknap,  "Summary of Available Portable
     VOC Detection Instruments," U.S. Environmental Protection Agency,
     Report  No.  EPA-340/1-80-010 (March 1980).

 5.  Spain,  D.,  J.J.  Decorpo, J.R.  Holtzclaw,  "Use of a Photoionization
     Detector as a  Hydrocarbon Trace  Gas Analyzer," Naval Research
     Laboratory, Memo Report No.  4239 (August 1980).

 6.   Langhorst, M.L., "Photoionization Detector  Sensitivity of  Organic
     Compounds," J. Chromat. Sci.,  19.  98-103 (February 1981).

 7.   Driscoll, J., HNU  Systems,  Inc.,  personal communication (June 1981)

 8.   Dietz,  W., J. Gas  Chromatog.. j>,  68 (1967).
8.  APPENDICES

The attached appendices include instrument operating procedures which
were abstracted from instruction manuals provided by the manufacturers.
                                  72

-------
  A.   HNU Systems,  Inc. - Model PI- 101

      (1)   Introduction

  The Model PI-101  has been designed to measure the concentration of
  trace gases in many industrial or plant atmospheres.  The analyzer
  employs the principle of photoionization for detection.  This process
  is teraed photoionization since the absorption of ultraviolet light
  (a photon) by a molecule leads to ionization via:

                             RH + hv -*• RH+ + e~

 where RH - trace gas, and
       hv - a photon with an energy J> ionization potential of RH.
     sensor consists of a sealed ultraviolet light source that emits
 photons which are energetic enough to ionize oany trace species
 (particularly organics) but dc not ionize the major components of air
 such as 02,  N2,  CO, C02 or H20.  A chamber adjacent to the ultraviolet
 source ocntains  a pair of electrodes.   When a positive potential is
 applied to one electrode, the field created drives any ions,  formed by
 absorption of UV light, to the collector electrode where the  current
 (proportional to concentration) is measured.

 To minimize  absorption of various sample gases,  the ion chamber is
 made  of an inert fluorocarbon material,  is located at  the sampling
 point,  and a rapid flow of sample gas  is maintained through the small
 ion chamber  volume.

 The analyzer will operate either froa  a  rechargeable battery  for acre
 than  ten hours or continuously from the  AC battery charger.   A solid
 state amplifier  board  in the  probe and a removable power supply board
 in the  readout module  enable  rapid servicing  of  the unit in the field.

 The useful range of the instrument is  from a  fraction of a  ppm to  about
 2,000 ppm.  For  measurement at  levels  above 2,000  ppm, dilution of  the
 sample  stream  with clean air  is recommended.  Some typical  specifications
 for the Model  PI-101 Photoionization Analyzer are  given  in  Table Al.

    (2)  Operation

Turn  the function switch to the battery check position.  The needle on
 the meter should read within or above  the green battery arc on the scale-
plate.  If the needle is in the lower portion of the battery arc, the
instrument should be recharged prior to naV-ing any measurements.  If red
LH> coaes on,  the battery should be recharged.

Sext, turn the function switch to the on position.  In this position, the
UV light source should be on.   Look into the end of the probe  to see the
purple glow of the lamp.
A brief description, Table A2^ of the instrument controls  and  functions
is shown in Figure Al.

                                   A-l

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                                 TABLE Al

         SPECIFICATIONS FOR MODEL PI 101 PHOTOIONIZATION ANALYZER



 Performance (benzene referred)

      Range:              0.1 to 2000 ppm
      Detection limit:    0.1 ppm
      Sensitivity (max):   0-2 ppm FSD over 100 division meter scale
      Repeatability:       ±1% of FSD
      Linear Range:        0.1 to 600 ppm
      Useful Range:        0.1 to 2000 ppm
      Response  Time:       <3  sec to 90% full scale
      Ambient humidity to 95% RH
      Operating temperature ambient to 40°C*


Physical

      Size:     Probe 6.3  DIA  x 28.5  L (cm)      (2-1/2  x 11-1/4")
               Readout  21W x  13D x  16.5H (cm)   (8-1/4  x 5-3/16 x 6-1/2")
               Stowed 21W x 13D x 24H (cm)      (8-1/4  x 5-3/16 x 9-1/2")
               Cable 80 cm long (32")

     Weight:   Probe .55 kg (20 ounces)
               Readout 3.2  kg  (7 pounds)
              Total (shipping)  5.4  kg  (12 pounds)


Controls and functions

     Mode switch OFF, Battery  Check, Standby  (zero),  0-2000,  0-200,
        0-*20 ppm
     Low battery indicator light
     Zero (10 turn £ 300% FSD max)
     Span (10 turn counting dial 1.0 to 10 times nominal sensitivity)
     Readout 4-1/2" (11.3 cai) meter Taut Band movement graduated 0-5-10-
        15-20 divisions
     Signal output for recorder 0-(-5V) FSD
     Power output for recorder 12 VDC - jack on side of instrument
 Instrument is temperature compensated so that a 20°C change in
 temperature corresponds to a change in reading of < ±2% full-
 scale at ;r.n?rlmm sensitivity.
                                  A-2

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                         TABLE Al (Continued)
 Power requirements of operating times

      Continuous use,  battery > 10 hours
      Continuous use with HNU recorder reduces  instrument  battery
         operating time to 1/2 normal  time
      Recharge time, max < 14 hours, 3 hours  to 902  of  full  charge
      Recharge current,  max .4 amps @  15 VDC
 Construction

      Designed  to withstand the  shock and  abuse  to  which portable  instru-
      ments  are often subjected.  The readout is housed  in a  two-piece
      aluminum  case,  and finished with a solvent resistant baked
      acrylic textured paint.

      The probe is fabricated from extruded aluminum sections and
      machined  plastic.
Serviceability

     The probe and readout are of a modular design allowing rapid servicing
     and/or replacement of mechanical and electrical components.  All
     module interwiring includes quick disconnects.
Maintenance

     The instrument contains only one moving part, and consumes no gases
     or reagents.  The only routine maintenance procedure is cleaning the
     light source window every several weeks.
Calibration check

     Check instrument calibration at least once per week with HNU
     calibration standard to ensure that the high sensitivity of the
     instrument is
                                  A-3

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                                  TABLE A2

          BRIEF lESCRIPTION OF INSTRUMENT CONTROLS AND FUNCTIONS*



     Control                              Function

 Six Position Switch           OFF - Shuts off all power and removes DC
                                     voltages.

                               CN  - In any other function position or
                                     measuring mode,  the electronics are en.

                               BATTERY CHECK - Indicated the condition of
                                     the battery.   If needle position is in
                                     lower portion of green battery arc,  the
                                     instrument should be recharged.

                               STANDBY -  UV lanp  is off but electronics are
                                     on.   This position will conserve  power
                                     and  extend the useful operating  time
                                     between recharges of  the battery.   This
                                     position is also  utilized to adjust the
                                     electronic zero.

                              RANGES.- 0-20,  0-200,  0-2000 direct  reading
                                    ranges  available  at minimum gain  for
                                    benzene.   More sensitivity is  available
                                    by adjusting the  span  potentiometer.

Zero Potentioiteter            A ten-turn potentiometer is  employed to adjust
                              the zero electronically when  the instrument is
                              placed in the standby position with  the probe
                              attached.  This eliminates the need for a hydro-
                              carbon-free gas.

Span Potentiometer            A ten-tuii counting potentiometer is utilized
                              for upscale setting of  the meter on calibration
                              gas.  Counter-clockwise rotation increases the
                              sensitivity (M.O times}.  This pot can increase
                              the sensitivity to make the instrument direct
                              reading for nearly any  gas which the instrument
                              responds to.
 For position of layout controls  see Figure  Al.
                                    A-4

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                                       Battery Cfieck
Low Battery Indicator
Light (LED)
          Power Off
        Sensitivity
        Aoji'Stment
        Hi-Voltage
           Interlock
                                                    12 Pin Interface Connector
                                                    between readout unit and
                                                    seosor.
                                                                             Ranges (ppm)
                                                                                   Function
                                                                                   Switch
                                                                                  Zero Adjustment
Recorder Output
  1-5VDC)
                Figure Al.   Control panel functions.

                                           A-5

-------
 To zero the instrument, turn the function switch to the standby position
 and rotate the zero potentiometer until the meter reads zero.  Clockwise
 rotation of the zero potentiometer produces an upscale deflection while
 counterclockwise rotation yields a downscale deflection.  Note:  No zero
 gas is needed, since this is an electronic zero adjustment (see below).
 If the span adjustment setting is changed after the zero is set, the
 zero should be rechecked and adjusted, if necessary.  Wait 15 or 20
 seconds to ensure that the zero reading is stable.   If necessary,
 readjust the zero.

 The instrument is now ready for calibration or measurement by switching
 the function switch to the proper measurement range.  The instrument is
 supplied calibrated to read directly in ppm (v/v)  0-20,  0-200, 0-2000
 of benzene with the span position set at 9.8.   For additional sensitivity,
 the span potentiometer is  turned counterclockwise  (smaller numbers) to
 increase the gain.   By changing thci span setting from 10.0 to 1.0 the
 sensitivity is increased approximately tenfold.  Then,  the 0-20, 0-200,
 and 0-2000 ppm scales  become 0-2,  0-20,  and  0-200  ppm full scale,
 respectively.   This span control is also utilized  to make  the instrument
 scale read directly in ppm of  the  compound being measured,  e.g.,  it is
 adjusted to match the  value of  a calibration gas to  that same reading
 on the  instrument scale.   The span  control can be utilized to calibrate
 nearly  any compound, measured by photoionization,  to be  direct reading
 on the  0-20 ppm range.

 A  small DC-operated fan is  used to  pull  air  through  the  photoionization
 sensor  at  a flow rate  of three  to seven  hundred  centimeters per minute
 (ca. 0.5 1pm).  The fan provides nearly  instantaneous response times
 while consuming little  power.   The  characteristics of a  fan are such
 that it cannot tolerate a significant  pressure drop  without affecting
 the flow rate and,  therefore, either the instrument  reading or response
 time.  Since photoionization is essentially a nondestructive  technique,
 changes in flow rate do not affect the signal but if a large  pressure
 drop is imposed at  the  inlet of the probe, the sample may not  reach
 the sensor.

The instrument was designed ta measure trace gases over a concentration
 range from less than 1 ppm to 2000 ppm.  Higher levels of various gases
 (to percentage range) can be measured but the recommended procedure is
 to dilute the sample with clean air to a concentration of less than
500 ppm.  This is generally within the linear range of the instrument
and if the measured concentration is mult ID He'd by the dilution ratio
the correct concentration in the stream cats be determined.   A calibration
curve for diluted dichloroethane was included in the basic report.

If the probe is held close to AC power lines or powar transformers,  an
error may be observed.   For measurements made in close proximity to
such items, their effect on measurements can tr. determined  by  the
following procedure.  Zero the instrument in aa electrically Quiet.
area,  in the standby pocition,  then move the instrument:  to  the
                                 A-6

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 questionable area involved.   If AC pickup is  going to be a  problem,
 the meter (in the standby position) will indicate  the magnitude of
 the error.

 The instrument is equipped with an automatic  solid state battery
 protection circuit.   When the battery voltage drops below A* 11 volts,
 this circuit  will automatically turn off the  power to the instrument.
 This prevents deep discharging of  the battery and  considerably extends
 the battery life.  If the instrument is  unintentionally left on over-
 night,  the battery will be unharmed because of the battery  protection
 circuit.   If  the  instrument battery check reads low and the lamp doesn't
 fire, plug the charger into the instrument.   The power to the analyzer
 should  then be returned.

 To  charge  the battery, place  the mini-phone plug into the jack on left
 side  of the bezel  prior to plugging charger into 120 VAC.   When
 disconnecting charger, remove  from  102 VAC before  removing  mini-phone
 plug.  The battery is  completely recharged overnight (ca. 14 hours).
 To  ensure  that  the charger is  functioning, turn the function switch
 to  the battery check position,  place phone plug into jack and plug
 charger into AC outlet.   The meter should go upscale if the charger is
working and is correctly  inserted into the jack.

The instrument can be operated during the recharge cycle.  This will
 lengthen the  time required to completely recharge the instrument battery.
                                  A-7

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  B.   AID.  Inc. Model 580

  The Model  580 Organic Vapor meter has been designed for measurement of
  low levels of most organic vapors in an air sample.  The sample Is
  contlnously pulled Into the Model 580 by Its own Internal sampling pump
  at a rate of approximately 600 mL/mln.  The sample Is pulled directly
  into the Photionization Detector where high energy from a UV source
  causes ionlzation of organic materials in the sample.  The amount of
  ionlzation that occurs is determined by measuring the ion current in
  an electrical field.  This current is amplified through an electrometer-
  type amplifier and presented on a digital display on the front panel as
 well as being made available on the rear of the unit for attachement to
 a 100 millivolt recorder.   The Model 580 used in this study was equipped
 with a lamp providing an ionizing energy of 11.8 eV.  In general, anything
 with an ionization potential below 11.8 will be sensed by the Model 580.
 The ionlzation potentials  do not necessarily give an indication of the
 sensitivity of the ionlzation detector for that particular material.
 Some materials that have an ionlzation potential as high as 12.2 will
 also be ionized using ths  11.8 lamp.

 The Model 580 is  a completely portable instrument,  meaning that it
 can operate independent  of any power  requirements on its own internal
 battery system for a period of at  least  8  hours.   It is  also capable
 of  being  operated from a line  voltage using  the plug-in  charger circuit
 that accompanies  the instrument.   With the charger  plugged into the
 system, by  means  of  the  3-position selector  switch,  the  line voltage
 can be  used to  either recharge the batteries  in the  Model 850 or to
 operate the Model 580 from line voltage.   The  third  position on the
 selector  switch is  the operation of the  instrument  from  its  own internal
 batteries.

 The instrument may be set  up on a  bench with  the  charging  circuit
 plugged to a wall outlet and into  the  rear of  the Model  580.   The  power
 switch  on the rear of the  instrument should be  set for AC  operation.
 The switch  on the front panel  should then be  turned  to the ON position.
 When this occurs, the LCD  display  should be activated allowing  digits
 to appear,  the pump should be  activated, and the  lamp in  the  detector
 should  come on.  The lamp  can  be observed by the small hole in  the end
 of the detector housing.   The  lamp gives off a  pale blue light when it
 is in operation.

 Initial calibration of the 580 requires a supply of zero air.  This
 means simply it has to have zero concentration of the components to
which the 580 will respond.  Thus, it is not necessary to clean methane
 from ambient air for this zeroing.  In many cases, ambient air itself
will be sufficient for zeroing of the instrument.  When basically zero
 air is supplied to the instrument, the zero can be set through the ZERO
 adjust hole in the rear panel.  There is a small pot immediately inside
 this hole that will allow adjustment of this zero.  The Model 580 is
 then presented with a sample of known concentration of a span gas to  be
                                   B-l

-------
 measured.  The SPAN Pot, again located on the rear panel, is then
 adjusted via a screwdriver for proper reading of the concentration of
 this particular span gas.

 The Model 580, as it leaves the plant, has been calibrated on a mixture
 of butadiene in air.  The Model 580 has two ranges of operation, 0 to
 200 and 0 to 2000 ppm.  In general, the span gas used should be relatively
 close in concentration to the expected levels to be determined on the
 actual air being sampled.  This would also imply that the particular
 range of the unit should be on the same range for calibration as well
 as for measuring.

 The standard Model 580 is designed to obtain organic vapor concentrations
 in the ppm region with an upper limit of approximately 2000 ppm.  There
 are two basic reasons  for this upper limit.   The first reason is that of
 the electronics  in the system.  If the concentration or,  literally,
 the electrical signal  arriving at  the detector amplifier  gets much
 greater than  that  required  to  provide a readout of 2000 ppm,  the
 amplifier will begin moving into a nonlinear response region; thus,  not
 provide adequate  output  for the organics  present in the sample.

 The second  reason  is the  detector  design  itself.   This particular
 detector was  designed  for industrial hygiene-type  analysis  in which  the
 concentration ranges of Interest are certainly covered by the 2000 ppa
 upper lisdt.  As one exceeds the 2000 ppa, the detector response itself
 becomes  nonlinear; such that doubling the amount of organic concentra-
 tion in  the sample does not double  the  output  signal from the system.
 When it  becomes necessary,  such as  in the area of  fugitive  emissions,
 to measure concentrations at the 10,000 ppm  level  using the Photo-
 ionization Detector, it is necessary to dilute the  sample such  that
 the concentration actually presented to the  detector is below 2000 ppm.
 Dilution of the sample will lower  the  reading  by a  known  factor,  e.g.,
 1:10, on the instrument and raise  the minimum  discernible amount  of
 organic vapor from, for example, .1  ppm on a standard 580 to  1 ppm on
 the modified version for high  concentrations.
                                                  «
 In  the standard Model 580, the sample is  pulled in  through'the probe
 to  the probe fitting and from  there  into  the detector.  The detector
 exit then connects directly to the pump inlet.  The pump exit exhausts
 through the rear panel of the  instrument.  In order  to provide a 1:10
 dilution of the Incoming sample, it  is necessary to add, to that stream
 prior to the detector, clean air at  the flow ratio of 9-to-l.   Thus,
 directly behind the sample probe fitting on the front panel, a Teflon T
 arrangement was installed whereby diluent air is placed into the sample
 line.  This diluted sample then continues in the normal fashion through
 the detector out of the detector into the pump inl'et and exits at the
pump exit.   Just prior to exiting the instrument, another  T was placed
in  the sample line.  The pump exit connects to one part of the T.  The
second part of the T goes to a restrictor valve and then to the exit
connection on the rarea panel.   The third part of this T passes through
                                    B-2

-------
 tubing in the back panel to a charcoal filter.   The exit from the
 charcoal filter passes back into the SCO and connects  to an inlet of
 the Teflon T placed upstream of the  detector.   It is desired to  maintain
 500 mL/min through the detector.   Thus,  the  incoming sample should be
 50 mL/min and the  makeup air coming  from the charcoal  filter to  the
 inlet T should be  450 mL/min.   This  ratio is adjusted  by using the
 restrictor between the exit T and the exit port on the rear panel
 of the 580.   This  restrictor is closed until the inlet sample sampling
 rate is 50 mL/min.   The integrity of the system is checked  by measuring
 the exit flow at 50 mL/min.

 Under this type of system,  th^re  is  450  mL/min  of air  circulating
 from the pump outlet through the  charcoal filter into  the inlet  line to
 dilute the sample.   The charcoal  in  the  filter  removes interfering
 materials  that  would give a  response on  the  Photoionization Detector.
 Normally,  the charcoal will  remove,organic material, other  than  methane
 and  possibly  ethane,  from the  sample.  These materials will not  be
 ionized  in  the  Photoionization Detector.   The charcoal filter is  a
 disposable cartridge  and is  held  on  the  outside  rear panel  of the
 Model  580.  This provides easy replacement of this  charcoal filter.

 With  the 1:10 dilution  introduced into the Model  580 by the modification
 system described above, the  inlet sample  flow is  of  necessity  reduced
 to 50 mL/min.  With  the standard probe assemblies in the Model 580,
 this would Introduce a  serious  time  constant before  the sample is
 actually presented to  the detector for analysis.  For  this  reason,
 the probe has been altered to a 1/16" ID  tube to provide approximately
 the same time constant on the sampling tube, as one would obtain with
a larger probe.
                                     B-3

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 C.   Foxboro/Wilks, Inc. - Miran 80

      (1)  General Description

 The Miran 1A Portable Gas Analyzer-is a single-beam,  variable filter
 spectrometer, scanning the infrared spectral range between 2.5 and
 14.5 ym.  The instrument is equipped with a gas cell  having pathlength
 variable between 0.75 and 20.25 meters.  Other basic  equipment are a
 pump and 3 m (10 ft) air sampling hose with a particulate filter, a
 zero gas filter, and a carrying case.

 The Gas Analyzer System consists of two components, the gas cell and
 the analyzer (Table Cl).   The variable gathlength gas cell has a 5.6
 liter capacity body, vacuum-tight to 10 ^ torr and pressurizable to
 1000 kPa (10 atmospheres),  an internal optical path variable in 1.50
 meter increments between 0.75 and 20.25 rosters, a pair of windows
 transparent to infrared energy between 2.5 and 14.5 ym,  inlet and outlet
 ports and a safety valve.   The internal optics are gold plated and the
 inside  of the cell is  ptfe  coated to resist  sample absorption and
 corrosion.

 The analyzer consists  of a  radiation source,  mirror systea,  mechanical
 chopper,  circular filter  (variable in three  segments  between 2.5 and
 14.5 ym),  a  scanning motor,  pyroelectric detector,  a  signal  preamplifier,
 logarithmic  range compensating circuitry,  regulated power supplies,  a
 deter providing  absorbance  and percent-transmission scales and a 0-1
 volt  output  for  a strip chart  recorder.

 The Miran 1A System  operates  from either 110  or 220 V ac,  50-60 Hz
 power supply.  By means of  an  inverter, portable oper:r'on from a 12
 volt  battery  is  readily accomplished.  This expands the instrument's
 use  to monitoring beyond the confines of the  laboratory and  greatly
 facilitates  the  determination  of  environmental  pollutants  and meeting
 OSHA  (Occupational Safety and Health Administration)  industrial  require-
ments.

 The Wilks Model  80 is a quantitative analysis system  combining a high
performance single beam infrared spectrometer (Model  1A) with a
programmable microcomputer system (Table C2).  This results in an
instrument of speed and versatility.  The Model 80 accepts multicomponent
 liquids, solids and/or gaseous samples directly without the necessity
of vaporizing or dissolving them, separating them into their individual
 components.

 The Model 80 has  the following features:

     •    The measurement of up to 18 separate wavelengths in less than
          two minutes.  The interval between sets of measurements Is
          variable from 7 seconds to 30 minutes.
                                    C-l

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                                TABLE Cl

                             SPECIFICATIONS
 SPECTROMETER

 Type:

 Wavelength Range:



 Wavelength Range Control:

 Resolution (Approximate):



 Noise Level:
Drift:



Slit Settings:

Response Time Settings:

Absorbance Ranges:



Wavelength Drive Speed:

Infrared Source:

Infrared Detector:

Power Requirements:

Weight:
 Single-beam infrared spectrometer.

 2.5 to 14.5 ym in three steps:
 2.5 to 4.5; 4.5 to 8; 8 to 14.5 with
 small overlaps.

 Manual or motor driven.

 0.05 ym at 3  ym wavelength
 0.12 ym at 6  ym wavelength
 0.25 ym at 11 ym wavelength

 Maximum of 0.003 absorbance units/8  hours
 under the following  conditions:   20.25
 meter pathlength,  1  mm slit,  1 second
 time constant,  12.0  ym wavelength, 23°C
 oper  Ing temperature.

 Maxu  um of 0.006 absorbance units/8  hours
 using instrument conditions as specified
 above for noise level.

 Closed,  0.5,  1.0,  2.0 millimeters.

 1, 4,  10  and  40 seconds.
                   *
 0 to  0.025, 0 to 0.1, 0 to  0.25,
 0 to  1 absorbance units and 0  to
 100Z  transmission.

 2.5 minutes per segment.

Regulated nichrome wire heating element.

Pyroelectric type, lithium  tantalate  element.

25 watts at either 115 or 230 VAC, 50-60  Hz.

5.8 Kg (12.5 Ib) without cell.
11.6 Kg (30.0 Ib) with gas cell.
                                   C-2

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 Dimensions:
 Temperature Range:
TABLE Cl (Continued)


   245 x 155  x 155  mm without  cell.
   190 x 280  x 720  mm with  cell.

   0°  to +40"C (32°  to 104°F)  Operating.
   -20°  to +60°C  (-4°  to 140°F) Storage.
 VARIABLE PATH TWENTY METER GAS CELL

 Pathlength:                  0.75  to 20.25 meters  in steps  of 1.5 meter,
                             externally set.

 7oluae:                      5.6 liter.

 Pressure Range, Operating:   10~  torr vacmsm to 1000 k?a (10 acaospheres).
Valves:


Internal Finish:


Windows:
  Inlet and exhaust valves designed for both
  vacuum and pressure, ptfe sealed.

  ptfe lined, with mirrors and other components
  gold plated.

  NaCl or AgBr normally furnished.  Others
  on special order.
                                 C-3

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                                     TABLE C2

                             SYSTEM SPECIFICATIONS
 Type:

 Wavelength Range:

 Resolution of CVF:
   (full width at half height)

 Minimum (Wavelength Step Size):


 Wavelength Repeatability:


 Noise Level:
Drift:


Photometric Accuracy:

Slit Settings:

Time Constant:

Full Scale Range:

Wavelength Drive Speed:

Power Requirements:


Ambient Temperature Range:

Dimensions:
 Single-beam spectrometer.

 2.5 to 14.5 ym.

 0.05 y at 3.5 ym,  0.08 y at 6 urn,
 0.25 y at 12 ym.

 0.0005 pm at 3.5  urn*  0.0008 ym at  6 ym.
 0.0016 ym at 12  ym.

 0.0007 ym at 3.5  ym,  0.0003 ym at  12 ym,
 48 hrs at 23°C.

               -4
 Max.  of 1 x 10  absorbance units,  without
 cell,  1 mm slit; 3.5  microns,  1 x  10~3
 absorbance units at 12 microns;  23°C.

 Maximum of 0.002 absorbance units  at 23°C,
 3.5 microns,  24 hours.

 Better than 0.1%.

 0.5, 1,  2  mm,  and  closed.

 0.25 seconds  for recorder output.

 1.6 absorbance units  (useful range).
                           •
 Selectable  from 40 seconds to 1 hour.

100, 120,  220, 240 VAC + 152, -122, 50-60  3z,
75 watts.

0* to +40°C (32° to +104°F).

35 x 26 x 18 cm.
                                    C-4

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                                                                                   H I I
      •    Signal averaging,  256 measurements are made at each wavelength
           over a 1-180 second interval, enhancing the signal to noise
           and improving precision.

      •    Quantitates up to 11 components with one reference wavelength.
           Compensates for interferences.  Absorbance repeatability within
           the noise level.

      •    Keyboard entry of instrument settings and factors for data
           manipulation.  Changing instrumental conditions for a new
           analysis is rapid, i.e., less than 10 minutes to set up a
           5-component liquid analysis.

      •    Printout of memory parameters such as wavelengths, standard
           factors in data matrix, gain settings,  etc.

      •    Scans  a short section of the spectrum (automatical!y) and
           prints  out absorbance as a function of wavelength.

      •     Data printout presentation includes absorbance for each
           wavelength and concentration for each component.

      •     Digital display shows keyboard entry,  and displays wavelength
           during  the analysis routine.

      •     Compatible with all Wilks standard liquid,  gas  and solid
           sampling  accessories.

      (2)   Operation

           (a)  Precautions and Preliminary Steps

               Precautions

Using the  particulate filter whenever sampling to prevent  dust  and dirt
from damaging optical components.

Avoid water condensation in the cell when  the instrument is cold.  Before
use, purge the cell with dry air or  inert  gas, such as nitrogen or
helium.  Allow sufficient warm-up time to  prevent water condensation on
cold internal surfaces.

Before storage or transporting the instrument in a cold environment,
purge the  cell and close cell ports.
                                   C-5

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                Preliminary Steps

 The operator should first perform Initial Checkout.  The following
 quick tests verify proper instrument operation and detect long-term
 changes in performance.

      1.   Switch on POWER and allow 5 to 15 minutes warm up.  Adequate
           warm-up is indicated by no detectable down scale drift on
           the 0.1A scale.  Some random fluctuation due to noise is
           normal and should not be confused with drift.  Drift is
           indicated by uniform meter deflection in one direction over
           a period of a minute or two.

      2.    Set the following conditions:

                     RANGE               ZT

                     PATH                0.75 aeters

                     SLIT                1  mm

                     WAVELENGTH          3.5  urn

                     ZERO CONTROLS        XI,  minimum (0.0)

                     RESPONSE TIME        1.0  second

          Record  the reading.  This record will show long-term changes
          in instrument  performance.   Some degradation  in  infrared
          optical components should be  expected. ' After several years
          of normal  service, cell windows, for example, may have  to be
          replaced.  A continous record  of this test is useful  in
          deciding whether instrument  service is required.  It will also
          show sudden performance changes  as occur with exposure  of
          NaCl windows to very wet samples or exposure of AgBr windows
          to asmonia or pyridlne.

          (b)  Atmospheric Sampling Techniques

Atmospheric sampling requires only that samples be flushed directly
through the instrument via the sampling hose and particulate filter.
The analyzer's built-in pump is used.  To minitor a single material
or contaminant, the analyzer is set to the appropriate wavelength for
the substance and changes in concentration are recorded.  Periodic
flushings of the cell with zero gas or clean air is necessary to recheck
the zero absorbance setting.  Where there is high level local contamination
of certain orgr.r^ic compounds, bottled air may be necessary for cell
flushing purposes.  Such situations may arise during analysis within
closed environments such as r-jlvent tanks or storage areas or when
checking for leaks in pipes or duct work.
                                  C-6

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           (c)  Monitoring Concentration of a Test Gas

 Where several substances are of interest,  such as in VOC screening*
 select wavelengths to be used based on likely compounds (functional
 groups) and  proceed as follows:

      1.   The instrument should have first passed the Initial Checkout.

      2.   Set up instrument for wavelengths to be monitored.

      3.   Select a RESPONSE TIME setting that will-give a smooth
           meter response without being unduly sluggish.

      4.   With clean air or "zero gas" in  the cell, adjust for zero
           absorbance reading with the ZERO CONTROL.

      5.   With the FUNCTION SWITCH on the  0-1 absorbance scale,
           the meter should  read zero.

      6.   Select the desired absorbance  RANGE for aonitoring-

      7.    Connect  the sampling  hose and  particulate filter  to  the
           sample  inlet port.

     '8.    Open VALVES and switch on the  ambient air pump.

      9.    Read or  record absorbance values.
                                                  «
                                                          •
           (d)  Calibration  for  Quantitative Analysis

For optisnm accuracy,  it is necessary  to calibrate  the  analyzer at the
wavelengths used for  each sample.  This is a one-time procedure unless
the wavelength filter  ±s replaced or a new cell is installed.  Absorbance
is recorded at one-to-five concentrations and a calibration curve
prepared.  An inversion matrix may be used with the Model 80 micro-
processor  to convert directly to ppmv.

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