-------
-------
NOTICE
This document has been reviewed in accordance with U.S. Environ-
mental Protection Agency policy and approved for publication. Mention
of trade names or commercial products does not constitute endorsement
or recommendation for use.
-------
FOREWORD
Source measurement and monitorinq efforts are designed to antici-
pate potential environmental problems, to support regulatory actions by
developing data bases needed in developing regulations and to provide
means of monitoring compliance with regulations. The Environmental
Monitoring Systems Laboratory, Research Triangle Park, North Carolina,
has the responsibility for implementation of agency-wide Quality Assur-
ance programs for air pollution measurement systems; and supplying
technical support to other groups in the Agency including the Office of
Air and Radiation, the Office of Toxic Substances, and the Office of
Enforcement.
The need for reliable standards for auditing and documenting the
accuracy of source emission measurement of gaseous hydrocarbons, halo-
carbons, and sulfur compounds is well established. The Quality Assur-
ance Division of EPA's Environmental Monitorinq Systems Laboratory has
responded to this need through the development of an extensive reposi-
tory of gaseous compounds. The primary objectives of this ongoinq pro-
ject are (1) to provide accurate gas mixtures to EPA, state/local aqen-
cies, or their contractors for performance audits to assess the accu-
racy of source emission measurements in certain organic chemical manu-
facturing industries, (2) to verify the vendor's certified analysis of
the gas mixtures, (3) to determine the stability of the qas mixtures
with time, and (4) to develop new audit materials as requested by EPA.
This report describes the current status of this project. Included in
the report are (1) a descriotion of the experimental procedures used
for the analyses of qas mixtures, (2) a description of the audit proce-
dure, and (3) currently available audit results and stability data.
Thomas R. Hauser, Ph.D.
Director
Environmental Monitoring Systems Laboratory
Research Trianqle Park, North Carolina
-------
ABSTRACT
A repository of 45 qaseous compounds including hydrocarbons, halo-
carbon, and sulfur species has been established under contract with the
U.S. Environmental Protection Agency (USEPA). The main objectives of
this on-qoinq project are (1) to provide qas mixtures to EPA, state/
local agencies, or their contractors, as performance audits to assess
the accuracy of source emission measurements in certain organic chemi-
cal manufacturing industries, (2) to corroborate the vendor's certified
analysis of the gas mixtures by in-house analysis, (3) to determine the
stability of the qas mixtures with time by in-house analysis, and (4)
to explore the feasibility of new audit materials as requested by EPA.
Thus far, 31 compounds have been used to conduct 149 different
audits. The results of these audits and a descriotion of the experi-
mental procedures used for analyses and available stability data are
presented in the status report. Generally the audit results are within
15 percent of the expected values.
Compound stabilities have been determined throuqh multiple anal-
yses of the cylinders containing them. Stability data for up to 7
years is available for many compounds and over 4 years for most com-
pounds. Compounds that are unstable and not suitable for use as an
audit material are identified.
-------
CONTENTS
FOREWORD iii
ABSTRACT i v
TABLES , vi
ACKNOWLEDGEMENT v i i
1. INTRODUCTION 1
Objectives 1
Audit Materials Contained in the Repository 1
2. EXPERIMENTAL PROCEDURES 5
Instrumentation 5
Calibration 5
Quality Control 6
3. PERFORMANCE AUDITS 8
4. STABILITY STUDIES 25
5. SUMMARY AND CONCLUSIONS 27
REFERENCES 28
ATTACHMENT 1 - STABILITY DATA AS OF JULY 1985 30
-------
TABLES
Number Page
1 Audit Materials Currently in the Repository 3
2 Orqanic Calibration Mixtures Verified by Byron
401 Analyzer 7
3 Summary of Performance Audit Results 9
-------
ACKNOWLEDGEMENTS
This work is beina carried out under EPA Contract Nos. 68-02-
2725, 68-02-3222, 68-02-3431 and 68-02-3767. The authors thank J.
Lodqe, C. Ewald, R. Wright, S. Cooper, R. Mueqqe and W. F. Gutknecht
for their contributions to this study.
-------
SECTION 1
INTRODUCTION
OBJECTIVES
The need for reliable standards for auditing source emission mea-
surement of qaseous hydrocarbons, halocarbons and sulfur compounds is
well established. The Research Triangle Institute (RTI), under con-
tract to the U.S. Environmental Protection Agency (USEPA), has respond-
ed to this need through the development of an extensive repository of
39 qaseous compounds. The primary objectives of this ongoinq project
are (1) to provide accurate qas mixtures to EPA, state/local agencies,
or their contractors for performance audits to assess the relative
accuracy of source emission measurements in certain orqa'nic chemical
manufacturing industries, (2) to examine the vendor's certified analy-
sis of the qas mixtures by in-house analysis, (3) to determine the
stability of the qas mixtures with time by in-house analysis, and (4)
to develop new audit materials, as requested by EPA.
This report describes the current status of this project. In-
cluded in the report are (1) a description of the experimental proce-
dures used for initial cylinder analyses and collection of stability
data, (2) a description of the audit procedure, and (3) currently
available audit results and stability data. Complete details of the
study with statistical analyses for ten (10) halocarbons and eiqht (8)
other orqanics are presented in two journal publications (1,2). Sta-
tistical analysis for the remaining compounds will be presented in a
future report.
AUDIT MATERIALS CONTAINED IN THE REPOSITORY
Currently, 45 qaseous compounds have been investigated as audit
materials. Six of these qaseous compounds have been found to be un-
stable in cylinders and not suitable as audit materials. The other 39
qaseous compounds in the repository are suitable for conductinq perfor-
mance audits durinq source testinq. The compounds were selected based
on the anticipated needs of the Emission Measurement Branch, Office of
Air Quality Planning and Standards, USEPA. Table 1 lists the 45 com-
-------
pounds, the concentration ranges, the number of cylinders of each
compound currently in the repository, and the cylinder construction
material. In Table 1, the audit materials fall into two concentration
ranges. The low concentration range between 5 and 50 parts per million
(ppm) simulates possible emission standard levels. The high concentra-
tion range between 50 and 700 ppm simulates expected source emission
levels. The balance gas for all gas mixtures is nitrogen.
-------
TABLE 1. AUDIT MATERIALS CURRENTLY IN THE REPOSITORY
Low Concentration Range High Concentration Range
Compound No. of
Cy 1 Inders
Benzene
Ethylene
Propylene
Methane/Ethane
Propane
Toluene
Hydrogen Sul fide
Meta-Xy 1 ene
Methyl Acetate
Chloroform
Car bony 1 Sul fide
LAn+h.il UA»»j~a »% + art
Methyl MercapTan
Hexane
1,2-Olchloroethane
Cyclohexane
Methyl Ethyl Ketone
Methano 1
1,2-Dlchloropropane
Tr Ic hi oroethy 1 ene
1 , 1-Dlchl oro-
ethy 1 ene
** 1,2-0 ibromo-
ethy lene
Perc hi oro-
ethy 1 ene
Vinyl Chloride
1,3-Butad I ene
Aery lonltr lie
JHt An 1 1 I na
nn 1 1 1 n@
Methyl Isobutyl Ketone
7
4
3
-
4
5
7
1
2
2
1
2
4
-
1
2
2
2
-
2
9
1
1
1
Concentration
Range (ppm)
5
5
5
5
5
5
5
5
5
5
20
5
30
^n
jv
5
5
5
5
5
5
5
5
- 20
- 20
- 20
- 20
- 20
- 50
- 20
- 20
- 20
- 20
t f\
- 10
- 80
- 20
- 80
— an
ou
- 20
- 20
- 20
- 20
- 30
- 30
- 20
- 20
Cy 1 inder
Construction*
S
Al
Al
—
Al
S
Al
S
S
S
S
A 1
n 1
Al
Al
—
S
A 1
n 1
Al
Al
Al
—
S
S
S
Al
Al
No. of Concentration Cylinder
Cylinders Range (ppm) Construction*
11
4
6
3
4
4
4
4
7
2
2
1
3
1
4
1
-
2
2
2
-
2
-
-
1
-
60
300
3000
300
1000
200
300
1000
100
100
300
300
300
100
1000
100
80
300
100
100
300
300
- 400
- 700
- 20,000
- 700
- 6000 (M),
- 700(E)
- 700
- 20,000
- 700
- 700
- 700
- 700
- 700
- 300
- 3000
- 600
- 200
- 700
- 600
- 600
- 700
- 500 .
S
Al
Al
Al
Al
Al
Al
LS
Al
LS
S
S
S
LS
Al
S
-
Al
Al
Al
—
LS
--
~
Al
~
Cylinder constructions: Al = Aluminum, S = Steel, LS = Low-Pressure Steel
Cylinders are no longer available; the compounds were found to be unstable in the cylinders.
-------
TABLE 1. AUDIT MATERIALS CURRENTLY IN THE REPOSITORY (Continued)
Low Concentration Range
Compound
No. of Concentration Cylinder
Cylinders Range (ppm) Construction*
High Concentration Range
No. of Concentration Cylinder
Cyl inders Range (ppm) Construction*
**Ethylamine
**Formaldehyde
MeTnyiene unioride
Carbon Tetrachl oride
Freon 113
Methyl Chloroform
Ethyl ene Oxide
Propyl ene Oxide
Al lyl Chloride
Acrolein
Carbon Dl sul fide
**Cyclohexanone
***EPA Method 25 Gas
Ethyl ene Dl bromide
Tetrachl oroethane
-
1
1
1
5
1
1
1
-
6
2
1
-__
5 -
5 -
5 -
5 -
5 -
5 -
5 -
100 -
5 -
5 -
/u
20
20
20
20
20
20
20
200
20
20
c
Al
Al
Al
Al
Al
Al
S
Al
Al
Al
Al
S
S
_ _________ __
1 75 - 200 Al
1 75 - 200 S
1 75 - 200 Al
3 750 - 2000 Al
2 100-300 S
_________ —
Cylinder construction: Al = Aluminum, S = Steel, LS = Low Pressure Steel
*
Cylinders are no longer available; the compounds were found to be unstable in the cylinders.
The gas mixture contains an al iphatic hydrocarbon, an aromatic hydrocarbon, and carbon dioxide in
nitrogen. Concentrations shown are reported in ppmC.
-------
SECTION 2
EXPERIMENTAL PROCEDURES
Analysis of the cylinder qases is required to corroborate the con-
centrations reported by the company which prepared the gas mixtures and
also to measure concentration changes with time, that is, estimate sta-
bility of the compounds.
INSTRUMENTATION
Analyses are presently performed with (1) a Perkin-Elmer Siqma 4
Gas Chromatoqraph with a flame ionization detector, and (2) a Tracor
560 Gas ChromatoqraDh with a flame photometric detector. The flame
photometric detector has been used principal ly for measurement of the
sulfur-containinq species. The qaseous samples are injected onto the
columns by means of qas sampling valves constructed of Hast alloy C
(hiqh nickel content and low adsorptive properties). These valves are
equipped with interchangeable sample loops to allow the injection of
variable volumes of gas. A.thermal oxidation system consisting of a
3/8 inch O.D. stainless steel tube heated to 1350°F in a tube furnace
is used to oxidize calibration mixtures to C02 for verification of
concentration. The C02 concentration is measured with a Byron Model
401 eauipped with a nickel based reduction catalyst and flame ioniza-
tion detector.
The qas chromatonraphic parameters used in the measurement of
individual compounds and any problems with the analysis are listed in
Attachment 1.
CALIBRATION
Calibration of the qas chromatographs has involved measurement of
known concentrations of qases in air or nitrogen. The source or method
of preparation of calibration standards varies dependinq on the qas in-
volved.
National Bureau of Standards, Standard Reference Materials (NBS-
SRMs) of methane and propane were used for the calibration of the GC
for the measurement of methane, ethane, propane, ethylene, and propyl-
ene audit materials. NBS-SRM of benzene was used for the calibration
-------
of the GC for the measurement of low concentration benzene audit cylin-
ders.
A second method for preparation of calibration standards involves
the use of permeation tubes. For example, the calibration qases for
vinyl chloride and ethylene oxide have been generated in this manner.
The permeation tube is placed in a temperature-controlled chamber and
nitrogen is passed over the permeation tube at a known flow rate. The
resultant gaseous mixture is further diluted, if necessary, using addi-
tional nitrogen in a glass dilution bulb. The final mixture is col-
lected in a gas sampling syringe and analyzed by GC-FID. The permea-
tion rates of the tubes are determined periodically by weiaht loss.
A third method for developing a calibration standard is the
pressure-dilution technigue. A known volume of the compound, either
gas or liguid, is injected into an evacuated glass bulb or stainless
steel sphere of known volume. The volume of the bulb or sphere is
determined gravimetrically. The bulb or sphere is then pressurized
with a balance qas of choice. If a pure liquid is injected, total
vaporization is assumed and the concentration is calculated by using
the ideal gas law. Additional dilutions are also made, if necessary,
by partially evacuating to a known pressure and pressurizing with a
balance gas to a known pressure.
With each of these approaches, multipoint calibration curves are
prepared each time a sample is analyzed.
QUALITY CONTROL
Replicate injections of both audit cylinder qases and calibration
standards are performed until no trends in the detector response are
observed and the relative standard deviation of replicate injections is
less than 1 percent.
Instead of depending totally upon the pressure-dilution technique
for the determination of calibration mixture concentrations, an inter-
nal gualitv control has been implemented to allow verification of the
calibration mixture concentration. This involves passing a portion of
the lowest concentration calibration mixture of a particular compound
prepared in a bulb or sphere through the thermal oxidizer described in
-------
Section 2.1 and analysis of the C02 produced with a Byron 401 analyzer.
The C02 response is calibrated with a primary standard (+ 1%) mixture
of C02 in air. The concentration determined by this technique was then
assigned to the lowest concentration calibration mixture and the con-
centrations of hiqher calibration mixtures were calculated by assuming
quantitative dilution. This procedure was used for those orqanics
listed in Table 2. The lowest standard calibration mixtures were only
verified with this technique in order to limit the production of corro-
sive by-products of haloqenated organics by the oxidizer.
TABLE 2. ORGANIC CALIBRATION MIXTURES VERIFIED BY
BYRON 401 ANALYZER
Toluene
M-xylene
Methyl acetate
Chloroform
1,1-dichloroethane
Methanol
1,2-dichloropropane
1,1-dichloroethylene
Perchloroethylene
Methyl isobutyl ketone
Methylene chloride
Carbon tetrachloride
Freon 113
Allyl chloride
Acrolein
Chlorobenzene
EPA Method 25 gas mixture
-------
SECTION 3
PERFORMANCE AUDITS
RTI supplies repository cylinders for audits upon request from the
EPA, state or local agencies or contractors. A contractor must be per-
forminq source emission tests at the request of EPA or a state or local
agency in order to qualify for the performance audit. When a request
is received, the contents of the cylinders are analyzed, the tank pres-
sures are measured and the cylinders are shipped by overland carrier.
Tank regulators are also provided when requested. A letter is included
with the cylinders which provides general instructions for performance
of the audit. The audit material concentration and cylinder pressure
are provided to the requesting agency audit coordinator.
To date, 149 individual audits have been initiated, and 140 are
complete. The audit results currently available are presented in Table
2. Generally, the results of the audits show agreement of _+ 15 percent
with the audit material concentrations measured by RTI.
-------
TABLE 3. SUMMARY OF PERFORMANCE AUDIT RESULTS
Audit
No.
1
2
3
4
5
6
7
8
9
10
1 1
12
Client***
A
A
A
A
A
A
B
C
D
E
F .
F
Industry
Ethyl ene oxi de
production
Ethyl ene oxide
productl on
Ethyl ene oxi de
production
Acetone
product! on
Mai etc anhydride
productl on
Ethyl ene oxi de
productl on
Mai etc anhydride
production
Malelc anhydride
production
Ethyl benzene
styrene
manufacturer
Gasoll ne bulk
terml nal
Gasoll ne transfer
terml nal
Gasoll ne transfer
terml nal
Audi t materi al
Ethyl ene in N«
Ethyl ene In No
Methane/ethane I n N~
Methane/ethane 1 n N2
Methane/ethane i n N~
Methane/ethane i n N2
Benzene 1 n N_
Benzene In N2
Benzene i n N~
Benzene 1 n N2
Ethyl ene 1 n N_
Ethyl ene in N2
Benzene i n N2
Benzene i n N2
Benzene i n N
Benzene i n NU
Benzene i n N_
Benzene 1 n N2
Benzene 1 n N2
Benzene 1 n N2
Benzene i n N2
Benzene i n N2
Benzene 1 n N~
Benzene In N~
RTI audit
cone, (ppm)
3,240
21,200
1,710Me/220Et
8,130Me/597Et
1,021Me/315Et
6,207Me/773Et
79.0
374.0
138
300
5,440
18,900
80.0
355
101
387
71.0
229
62.0
80.0
142
294
268
343
Client audit
% bias (Avg.)*
-22.5
-20.0
+9/-20
+9/-1.00
+21.5/-4.50
+23.5/-4.50
-19.0
-11.0
-9.40
+4.70
-27.0
-33.0
+2.30
+27.5
+12.9
+ 14.5
-2.80
-3.90
+3.80
+3.40
-3.50
+3.20
-11.8
-1.00
Status of
audit**
E
E
E
E
E
E
E
E
E
E
E
E
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TABLE 3. SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
Audit
No.
13
14
15
Client***
F
F
C
Industry
Gasol Ine
terminal
Gasol ine
terminal
transfer
transfer
Nitrobenzene
manufacturing
16
17a
17b
18
19
20
21
F
F
F
G
F
F
F
Gasol Ine
terminal
Gasol Ine
terminal
Gasol ine
terminal
Coke oven
Gasol Ine
terminal
Gasol Ine
terml nal
bulk
bulk
bulk
bulk
bulk
LJnear alkyl-
benzene manu-
22
23
F
F
f actur I ng
Gasol Ine
terminal
Gasol ine
term 1 na 1
bulk
bulk
Audit
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Hydrogen
Hydrogen
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
material
In
In
In
In
in
in
in
In
in
In
in
N
N
N
N
N
N
N
N
N
N
N
sul
sul
in
In
in
in
In
In
In
in
in
in
In
N
N
N
N
N
N
N
N
N
N
N
2
2
2
2
2
2
2
2
2
2
2
fide In N2
fide In N
2
2
2
2
2
2
2
2
2
2
i
RTI Audit
cone, (ppm)
129
318
10.7
9.73
269
8.20
140
9.50
127
9.50
127
7.05
.9.73
12.0
218
7.65
396
98.0
294
331
9.85
81.0
10.2
61.0
Cl lent Audit
% bias (Avg.)*
+4
+8
+2
-4
-2
-2
-1
+10
-2
+12
-6
-24
-22
-0
+7
+ 16
+ 1
+5
+6
+4
-4
-6
+4
-9
.70
.70
.60
.60
.60
.30
.80
.4
.80
.5
.30
.8
.9
.80
.30
.3
.50
.70
.80
.50
.10
.80
.60
.50
Status of
audit**
E
E
E
E
E
E
E
E
E
E
E
E
-------
Audi t
No.
24
25
26
27
28A
28B
28C
29
TABLE 3. SUMMARY
Client*** Industry
H Industrial
surface coating
process
C Acryl 1 c acl d and
ester Production
C Acrylic acid and
ester Product! on
E Malelc anhydride
A Carbon adsorber
A Carbon adsorber
A Carbon adsorber
EPA, QAD Instrument
check-out
OF PERFORMANCE AUDIT RESULTS (Continued)
Audi t materl al
To 1 uene 1 n N2
Propyl ene 1 n N2
Propane In N2
Methane/ethane I n N2
Propane 1 n N2
Propane 1 n N2
Propane 1 n N2
Propane 1 n N2
Benzene In N2
Benzene In N2
Toluene In N2
Toluene 1 n N2
Toluene In N2
Toluene In N2
Toluene In N2
Toluene 1 n N2
Ethyl ene In ^
Ethyl ene In N2
Ethyl ene In N2
Ethyl ene In N2
Ethyl ene In N2
RTI audit
cone, (ppm)
14.8
474
20.3
1,640Me/195et
10.1
710
5.1
607
10.2
218
8.55
405
8.55
405
8.55
405
4.75
19.6
312
3020
20400
Client audit Status of
% bias (Avg.)* audit**
-1.90 E
+0.20
-2.30
-13.5(as methane)
+8.60 E
+5.60
+17.6 E
-3.60
NA F
NA
-6.40 E
-1.00
+4.10 E
NA
-8.80 E
NA
+4.00 E
+3.10
-0.80
+5.30
-8.60
-------
TABLE 3. SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
Audit
No.
30
31
32
33
34
35a
35b
Client*** Industry
EPA, QAD Instrument
check-out
EPA, QAD Instrument
check-out
EPA, QAD Instrument
check-out
EPA, QAD Instrument
check-out
EPA, QAD Instrument
check-out
1 Vegetable ol 1
plant
1 • Vegetable ol 1
plant
Audit material
Benzene 1 n N_
Benzene 1 n N~
Benzene 1 n N^
Benzene 1 n N~
Toluene In N2
To 1 uene 1 n N2
Methyl acetate In N2
Methyl acetate In N2
Methyl acetate In N2
Methyl acetate In N2
Propylene In Nj
Propylene 1 n N2
Propylene In N2
Propylene In N2
Propane 1 n N_
Propane 1 n N2
Propane 1 n Ny
Hexane 1 n N2
Hexane 1 n N2
Hexane 1 n N2
Hexane 1 n N2
RTI Audit
cone, (ppm)
8.20
78.0
133
348
405
579
6.80
17.2
326
455
4.90
19.7
300
685
14.6
303
439
82.2
1980
82.2
1980
Client Audit Status of
% bias (Avg.)* audit**
+0.30 E
-0.90
-4.00
-0.90
+3.20 E
+ 1.00
-2.60 E
+ 1.70
-1.50
-1.30
-22.4 E
-7.80
+ 1.00
-1.80
-0.70 E
+7.60
+6.20
+8.10 E
+3.00
-1.20 E
-1.30
36
Carbon adsorber Toluene In N_
8.20
-2.40
-------
TABLE 3. SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
Audi t
No. Client*** Industry
37 B Coke oven
38 D Ethyl benzene/
styrene
39 B Coke oven
Byproduct
40 D Coke oven
Byproduct
41 H Pal nt spray
42 H Tl re
manuf acturl ng
43 B Coke oven
44 D Ethyl benzene/
styrene
45 F Industrial
' surface coatl ng
46 EPA, QAD Tire
manufacturl ng
Audi t materi al
Benzene 1 n N2
Benzene 1 n N2
Benzene 1 n N2
Benzene 1 n N2
Benzene 1 n N2
Benzene 1 n N2
Benzene 1 n N2
Benzene 1 n N2
Benzene 1 n N2
Benzene 1 n N~
m-Xy 1 ene 1 n N2
Cyclohexane In N2
Benzene 1 n No
Benzene 1 n N2
Benzene In N2
Benzene 1 n N2
Propane 1 n N2
Propane 1 n Al r
Propane 1 n Al r
Propane 1 n Al r
Propane 1 n Al r
RTI audit
cone, (ppm)
12.1
105
9.90
77.9
345
8.20
85.4
10.9
147
10.8
16.4
93.4
7.54
225
8.20
74.5
10.6
316
450
15.0
316
Client audit Status of
% bias (Avg.)* audit**
+0.80 E"
+2.90
+5.70 E
+3.60
+ 1.50
-2.60 E
-8.70
+20.0
+6.80
NA F
NA
-11.1 E
+0.10 D
+0.40
-3.40 D
-0.20
-3.00
-3.20 E
-2.00
NA F
NA
-------
TABLE 3. SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
Audi t
No.
47
48
49
50
51
52
53
54
Client*** Industry
EPA, QAD Tire
manufacturl ng
0 Dimethyl
terephthalate
production
EPA, QAD Instrument
check-out
EPA, QAD Tl re oven
manufacturl ng
EPA, QAD Instrument
check-out
D Styrene
manufacturl ng
1 Veg. ol 1
manufacturl ng
M Research
Audi t mater 1 al
Propane 1 n al r
Propane 1 n al r
Meta-xy 1 ene 1 n 1^
Toluene i n N2
Methane 1 In N2
Propane 1 n al r
Propane 1 n al r
Propane 1 n al r
Propane i n al r
Propane 1 n al r
Benzene 1 n N2
Benzene 1 n N2
1 ,3-Butadi ene 1 n N2
Cyclohexane In N_
Ch 1 orof orm 1 n N_
Chloroform In N~
RTI audit
cone, (ppm)
20.8
453
487
61.5
55.2
4.90
613
718
20.8
316
106
358
20.9
99.0
16.5
531
Client audit Status of
% bias (Avg.)* audit**
-18.4 E
+13.4
-2.10 E
NA F
NA
-48.8 E
+ 16.9
+ 16.8
+20.0 E
-9.20
-4.90 E
-3.70
+23.8
-3.50 E
NA F
NA
55
Research
Ethylene In N«
300
+1.40
-------
TABLE 3. SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
Audit
No.
56
57
58
59
60
61
62
63
64
65
Client*** Industry
K Reactivity of
vent actl vated
charcoal
EPA, QAD Instrument
check-out
C Col 1 coatl ng
L Malelc
anhydride
M Research
EPA (State of Conn.) Malelc
anhydride
0
M Paper and pulp
P Research
E Coke oven
Byproduct
Recovery
Audit materl al
Chloroform In N2
Hydrogen sulflde
In N2
Propane 1 n Ai r
Propane 1 n Al r
Benzene 1 n N2
Benzene 1 n N«
Audi t not 1 nl tl ated
Benzene 1 n N2
Meta-xylene In N«
Hexane 1 n N2
Methyl mercaptan
In N2
Benzene In N2
Methyl ethyl ketone
In N2
Benzene 1 n N«
Benzene 1 n N^
RTI audit
cone, (ppm)
8.11
16.2
5.20
472
9.45
341
—
133
760
1990
4.44
13.4
44.5
7.93
132
Client audit Status of
% bias (Avg.)* audit**
NA F
NA F
NA E
-8.40
NA F
NA
__
NA F
NA F
NA
NA F
NA F
NA
-2.90 E
+ 1.39
-------
TABLE 3. SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
cr>
Audi t
No.
66
67
68
69
70
71
72
73
Client*"* Industry
D Rubber
manufacturl ng
E Coke oven
Byproduct
Recovery
EPA, Region II Vinyl chloride
manufacturl ng
EPA, QAD Instrument
Check
EPA, Region 1 Vinyl chloride
manufacturl ng
E Degreasi ng
vent
EPA, QAD Instrument
check-out
EPA, QAD Combustion
ef f 1 ci ency
test
Audit mater! al
Benzene 1 n N2
Benzene In N2
Benzene 1 n N2
Benzene 1 n N2
Hexane I n N2
Hexane 1 n N2
Propane I n Al r
Propane 1 n Al r
Benzene 1 n N2
Benzene 1 n N2
VI nyl chloride In N2
VI nyl chloride In N2
Propylene In N2
Propylene In N2
VI nyl chloride In N2
Trlchloroethylene In N2
Trl ch 1 oroethy 1 ene In N2
Hexane 1 n N2
Hydrogen sulflde 1 n N2
Methyl mercaptan In N2
RTI audit
cone, (ppm)
12.0
10.2
100
335
79.8
3080
9.97
314
8.29
75.7
5.74
28.3
328
725
7.50
14.9
566
3080
16.2
8.22
Client audit Status of
% bias (Avg.)* audit**
+14.2 E
0
+6.40
+6.00
+1.80
-7.50
-3.20
-10.8
-2.20 E
-2.50
NA F
NA
-7.00 E
-8.30
NA F
-0.40 E
-8.70
NA F
-7.50 E
-8.90
-------
TABLE 3. SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
Audi t
No.
74
75
76
77
78
79
80
81
82
83
Client*** Industry
E Vinyl chloride
manufacturl ng
N Col 1 coatl ng
F Col 1 coatl ng
D. Ma 1 el c
anhydrl de
EPA, Region VII Instrument
checkout
D Ma 1 el c
anhydrl de
F Plywood/veneer
dryl ng
P Plywood/veneer
dryl ng
J Polypropylene
manufacturl ng
1 Coke oven
Audit material
1 , 2-DI ch 1 oroethane 1 n N2
1,2-Dlchloroethane In N2
Propane 1 n al r
Propane 1 n al r
Propane 1 n al r
Propane 1 n al r
Benzene 1 n N2
Benzene 1 n N2
Benzene 1 n N2
Hexane 1 n N2
Benzene I n N2
Benzene 1 n N2
Propylene In N2
Propylene In N2
To 1 uene 1 n N2
Propylene In N2
Propylene In N2
Toluene 1 n N2
Propylene In N2
Propane 1 n N2
Propane 1 n N2
Hydrogen sulflde In N2
Hydrogen sulflde In N2
Carbonyl sulflde
RTI audit
cone, (ppm)
9.30
462
10.0
309
10.0
309
9.46
66.9
120
30.2
9.46
128
14.8
328
430
20.3
479
487
9.63
19.7
296
437
647
101
Client audit Status of
% bias (Avg.)* audit**
+6.00 E
+3.70
NA F
NA
NA F
NA
-6.60 E
-11.7
NA F
NA
-4.60 E
+ 12.5
-4.70 E
+4.40
-0.80
+18.2 E
-22.5
+32.5
-0.35 E
+0.84
+0.45
+4.90 E
-16.5
+ 1.98
-------
TABLE 3. SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
00
Audi t
No.
84
85
86
87
88
89
90
91
Client*** Industry
J Compliance
test! ng
1 Steel
manuf acturl ng
1 01 1 shale
0 Malelc Anhy-
dride Produc-
tion
R Refining
Air Quality Bureau, Refining
New Mexl co
S 01 1 shale
F Compliance
testl ng &
demonstration
Audit material
Benzene 1 n N£
Hexane 1 n N2
Toluene In N2
Methyl mercaptan
Hydrogen sulflde
Carbonyl sulflde
Hydrogen sulflde
Carbonyl sulflde
Methyl mercaptan
Benzene 1 n N2
Hexane 1 n N2
Hydrogen sulflde
Hydrogen sulflde
Hydrogen sulflde
Carbonyl sulflde
Methyl mercaptan
Hydrogen sulflde
Trlchlorethylene
Propane 1 n N2
Propane 1 n N2
Propane 1 n N2
In N2
In N2
In N2
In N2
In N2
In N2
In N2
In N2
In N2
In N2
In N2
In N2
In N2
RTI audit
cone, (ppm)
7.45
72.6
15.0
5.40
647
9.08
437
117
8.42
55.7
324
17.5
437
647
117
8.42
437
94.6
10.0
309
73.8
Client audit
% bias (Avg.)*
23.0
0.6
-8.7
NA
5.0
1.0
-3.0
-4.6
-13.3
+528.4
+20.5
21.1
22.0
NA
-29.1
-14.8
-3.65
NA
NA
-54.0
8.7
Status of
audl t*«
E
E
E
E
E
F
E
E
-------
TABLE 3. SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
Audit
No. Cl lent»*»
92 EPA, Region 1
93 D
94 US EPA, Region 1
95 E
96 USEPA, Region 1
97 Tewksbury State
Hospital, MA
98 T
99 U
Industry
Research Method
Development
Method
Val idatlon
Research-
Method
Development
Acrylonltr 1 le
Production
Resource Re-
covery Garbage
Burning Emis-
sions
Research-
Method Develop-
ment
Plywood
Veneer
Hazardous
Materials
Incineration
RTI audit
Audit material cone, (ppm)
Toluene In N2
Hydrogen sul fide In N2
Vinyl chloride In N2
1, l-dlchloroethylene In N2
Trlchloroethylene In N2
Perch loroethylene In N2
Acrylonltrl le In N2
Acrylonltr 1 1 e In N2
Propane In N2
Propane In N2
Vinyl chloride In N2
1,1-dlchloroethylene In
N2
Trlchloroethylene in N2
Tetrachloroethylene In N2
Method 25 gas In N2
Method 25 gas In N2
Trlchloroethylene In N2
Perchloroethylene In N2
Chloroform In N2
347
8.32
8.39
14.2
13.5
7.94
413
10.8
10.0
296
8.39
14.2
13.5
7.94
102 as C
1940 as C
8.91
7.94
16.5
Client audit
% bias (Avg.)*
NA
NA
-20.2
+10.6
+55.6
+48.1
NA
6.94
-35.0
-17.2
+57
-9.9
-4.4
+48.6
NA
NA
NA
NA
NA
Status of
audit**
F
F
E
E
E
E
F
F
-------
TABLE 3. SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
ro
o
Audit
No. Client*** Industry
100 USEPA, Region 1 Research Method
Development
101 U Hazardous
Materials
Incl neratl on
102 Allegheny Source Testl ng
County
103 1 Hazardous
Waste Incln-
eratl on
104 1 Hazardous
Waste Incln-
eratl on
105 USEPA, Region VI Plastics
106 USEPA, Region VI Vinyl Chloride
Manufacturl ng
107 V Instrument
Check
108 0 Gasoline Termi-
nal
109 P Chemicals
Manufacturl ng
110 MD Dept. of Health Instrument
Check
RTI audit
Audit material cone, (ppm)
Chlorobenzene In N2
Benzene 1 n N2
Hexane 1 n N2
Meta-xylene In N2
Trl chloroethylene In N2
Perch loroethylene In l^
Toluene In N2
Methyl ethyl ketone In N2
Acrylonl trl le In N2
Methyl Isobutyl ketone In N
Vlnylldlene chloride In N2
Vlnylldlene chloride In N2
VI nyl chloride In N2
Vinyl chloride In N2
Methyl chloroform In N2
Perch loroethylene In N2
Propane 1 n al r
To 1 uene 1 n N2
Benzene 1 n N2
1,2-dl chloroethane In N2
Benzene 1 n N2
Perch loroethylene In N2
9.20
128
30.2
6.82 (cold
2.68 (warm
13.5
14.5
8.51
38.7
11.6
2 9.49
14.2
9.00
8.41
8.44
10.2
7.94
1.18*
16.4
7.3
8.1
9.64
14.5
Client audit
% bias (Avg.)*
NA
NA
NA
bulb) NA
bulb)
NA
NA
NA
NA
NA
NA
12.3
10.0
NA
NA
+7.8
+ 15.9
-4.2
17.3
NA
NA
-6.6
+60.1
Status of
audl t»*
F
F
F
E
E
F
F
E
E
E
E
-------
TABLE 3. SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
Audit
No. Client***
111 V
112 J
113 6A State EPA
114 Sacremento County,
Cal ifornla
115 W
116 V
117 X
118 F
119 K
120 Z
121 K
122 LA State EPA
123 C
Industry
Instrument
Check
Research, Method
Development
Plastics
Instrument
Check
Instrument
Check
Instrument
Check
Carbon Adsorp-
tion
Surface Coating
Source Testing
Source Testing
Source Test! ng
Source Testing
Paper Manufac-
tur I ng
Aud 1 1 mater I a 1
Chloroform In N2
Carbon tetrachlor Ide In N2
Tr Ichloroethylene in N2
Freon 113 In N2
Propane in N2
Toluene in N2
Vinyl chloride in N2
Ethyl ene oxide In N2
Benzene In N2
Ch 1 orobenzene In N2
Methanol In N2
Toluene in N2
Methyl ethyl ketone In N2
Methyl ene chloride in N2
Method 25 gas In N2
Freon 113 In N2
Toluene in N2
Toluene In N2
Perch loroethyl ene In N2
Benzene in N2
Vinyl chloride In N2
1,2-dichloroethane In N2
Carbon tetrachl or Ide In N2
Vinyl chloride in N2
RTI audit
cone, (ppm)
16.5
10.5
13.5
9.76
628
347
8.44
10.1
389
9.20
55.2
16.1
38.7
9.67
96.8 as C
9.76
8.51
558
7.94
9.64
8.44
13.8
10.5
6.60
Client audit
% bias (Avg.)*
+3
+33.0
+4.0
0
+0.6
+2.0
+ 10.2
NA
-35.7
-43.1
NA
NA
NA
NA
+127.3
NA
+38.8
-3.1
NA
-30.5
191.5
-37.0
-40.0
NA
Status of
audit**
E
E
E
F
E
F
F
E
F
E
F
E
F
-------
TABLE 3. SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
IV)
ro
Audit
No. Client***
124 LA State EPA
125 Y
126 1
127 F
128 Y
129 J
130 Region V[ 1
131A South Coast Air
Qual Ity Manage-
ment District
131B South Coast Air
Qual ity Manage-
ment District
132 Maryland Dept.
of Health
133 State of Cal 1-
fornla Air
Resources Board
Industry
Instrument
Check
Surface Coating
Oil Shale
Surface Coating
Surface Coating
Research, Method
Development
Source Testing
Hazardous Waste
Landf i 1 1
Hazardous Waste
Landfill
Instrument
Check
Qual ity Assur-
ance Aud It of
Standards
Audit material
Toluene In N2
Methyl ene chloride in N
Method 25 gas In N2
Method 25 gas In N2
Car bony 1 sul fide In N2
Carbonyl sul fide In N2
Hydrogen sul fide
Methyl mercaptan
Method 25 gas in N2
Method 25 gas in N2
Method 25 gas in N2
Methyl ethyl ketone in
Aery Ion Itr 1 1 e in N2
Benzene In N2
Methane in N2
Methane In N2
Benzene in N2
Tr Ichloroethylene In N2
Hexane in N2
Methyl isobutyl ketone
1,2-Dichloroethane in N
Methyl ene chloride in N
Chloroform In N2
RTI audit
cone, (ppm)
8.51
2 9.67
107 as C
775 as C
10.7
116
627
8.42
775 as C
205 as C
1040 as C
N2 38. 7
11.6
134
6460
6460
7.9
9.4
32.8
In N2 8.4
2 13.9
2 9.2
4.6
Perch loroethyl ene In N2 10.5
Carbon tetrachlor Ide in
Trich loroethyl ene In N2
Freon-1 13 I n N2
N2 9. 6
14.0
11.0
Cl lent audit
% bias (Avg.)*
-34.2
96.8
80.4
39.5
NA
NA
NA
NA
-26.5, -18.7
21.5
18.9
NA
-29.3
-28
+0.6
-2.5
-11.1
-31.6
-18.5
+ 15.4
-2.1
+7.6
+2.2
+14.3
+ 1.0
+7.1
-9.1
Status of
audit**
E
E
F
E
E
F
E
E
E
E
E
-------
TABLE 2. SUMMARY OF PERFORMANCE AUDIT RESULTS (Continued)
Audit
No.
134
135
136
137
138
139
140
141
ro
CO
142
143
144
145
146
147
148
149
Client***
AA
FF
J
1
F
BB
EPA Region 1 1
Commonwealth of
Massachusetts
EPA Region 1 1
State of Dela-
ware
EE
DD
State of Dela-
ware
CC
F
BB
Industry
Source Testing
Source Testing
Instrument
Check
Source Testing
Com pi lance
Testl ng
Source Testing
Metal Refining
Instrument
Check
Source Testing
Plastic
Manufactur Ing
Plastic
Manufacturing
Paper Coating
Instrument
Check
Gasol ine Terminal
Vinyl Coating
Plastic
Manufacturing
RTI audit Cl lent audit
Audit material cone, (ppm) % bias (Avg.)*
Benzene in N2
Method 25 gas in N2
Benzene In N2
Benzene in N2
Method 25 gas in N2
Methanol in N2
Methyl ethyl ketone in N2
Method 25 gas In N2
Benzene in N2
Benzene in N2
Tr Ichloroethylene In N2
Methyl ethyl ketone in N2
Benzene in N2
Vinyl chloride in N2
Vinyl chloride in N2
Method 25 gas in N2
Propane in air
Toluene in N2
Benzene in N2
Propane In N2
Propane In N2
Methyl ethyl ketone In N2
Method 25 gas In N2
310
103.8 as C
10.3
121
195 as C
48.8
40.4
1060
376
7.9
14.0
40.4
7.8
7.75
20.3
96.1 as C
10.9
546
7.9
2052
308
40.4
1017 as C
+5.2
+28.1
+ 12.2
+6.2
+ 10.7
-11.2
+5.1
-4.3
+31.2
-5.1
-11.0
-10.3
-24.5
-4.6
-20.6
Status of
audit**
E
E
E
A
E
A
E
E
D
E
E
A
E
A
A
A
-------
NA = Not anal yzed
Cllent-Measured Concentration - RTI-Measured Concentration
*CIlent % Bias = 100 X
RTI-Measured Concentration
ro
**Status Codes:
A = Cylinder shipped; audit results not yet received;
B = Audit results received;
C = Audit report submitted to EPA;
0 = Audit results received, audit report submitted to EPA, cylinder not yet returned by client;
E = Audit complete;
F = Audit completed without analysis of audit materials by client.
*** When ever the audltee Is known, an alphabetical letter Is shown. Whenever the audltee Is unknown,
the name of the agency requesting the audit Is shown.
1977 - Audits 1-8 1982 - Audits 83-86
1978 - Audits 9-28 1983 - Audits 87-106
1979 - Audits 29-49 1984 - Audits 107-130
1980 -Audits 50-75 1985 -Audits 131-149
1981 - Audits 76-82
-------
SECTION 4
STABILITY STUDIES
An ideal calibration standard or audit material should be stable
over its total time of usage. The stabilities of the compounds in the
repository were studied through periodic analysis of the cylinder con-
tents. In this project, the gas mixtures in the repository are ini-
tially analyzed upon receipt from the specialty gas vendor to corrobo-
rate the vendor's analysis. If the RTI analysis result differs from
the vendor's value by more than 10 percent, the cylinder is given to a
third party (EPA or NBS) for analysis. The gas mixtures are again ana-
lyzed at 1 month, at 2 months, and at one year following the initial
analysis to determine the stability of the gas mixtures. In some
cases, analyses are not performed on the dates specified above; how-
ever, every attempt is made to acquire the data on this schedule. Cyl-
inder concentrations are also usually determined prior to each perfor-
mance audit, providing additional data for use in stability studies.
As the number of analyses oer cylinder increases, statistical sta-
bility analvses will be performed. The results will be presented in a
future report. Statistical stability analyses for ten (10) halocarbons
and eiaht (8) other organics were recently published in the open liter-
ature (1,2).
Absolute accuracies of the cylinder analyses have not been deter-
mined due to lack of NBS standards for most of the organic gas mixtures
above one ppm. Recently NBS has issued SRMs for tetrachloroethylene
and benzene and is in the process of certifying a 4-component SRM con-
taining aromatic species (benzene, toluene, chlorobenzene, and bromo-
benzene) and a 4-component SRM containing halocarbons (chloroform, car-
bon tetrachloride, tetrachloroethylene and vinyl chloride). Once these
NBS-SRMs are available, they will be used in the future to estimate the
absolute accuracy. An examination of the data in Attachment 1 shows
values for individual cylinder analyses usually vary by less than 10
percent for 4-8 analyses over 2-6 years. This variation indicates
changes in cylinder contents (i.e., instability) and the imprecision of
the measurement process. The possible sources of experimental error
25
-------
that could result in apparent differences in concentrations include (1)
the variability of the analytical technique used for analysis, (2) sta-
bility of and/or accuracy of calibration standards, and (3) the accura-
cy of reproducing standards for which NBS-SRMs do not exist. Each of
these sources of variability contributes to the net uncertainty of the
resulting data presented in Attachment 1. Estimates of day-to-day mea-
surement uncertainty (repeatability) for all compounds have not been
performed. However, the measurement uncertainties for ten halocarbons
were recently published (2). The measurement uncertainty varied from
<1 to 10 percent depending on the compound, and the major portion of
the uncertainty was attributed to the method of preparation of the cal-
ibration standard. The uncertainty for the gas chromatographic analy-
sis was determined to be less than 2 percent by multiple injections of
the gas during same day analysis. For some recent analyses of those
organics listed in Table 2, the uncertainty in the concentration has
been estimated. These estimates are based on consideration of the
uncertainties of several parameters involved in the measurement and
calibration standard preparation procedures. For example, for those
analyses involving the use of the thermal oxidizer and Byron 401, the
estimated uncertainties (percent coefficient of variation) were deter-
mined to be as follows:
o C02 standard response uncertainty - 2%
o C02 standard concentration uncertainty - 1%
o C02 analyzer response linearity uncertainty - 1%
o oxidized organic calibration mixture response uncertainty - 1%
o organic calibration mixture GC response uncertainty - 1%
o repository mixture GC response uncertainty - 1%.
The equation below was then used to estimate the total uncertainty
based on the above individual uncertainties.
/ n
= 2(2
\i=l
<2V/2
Total Uncertainty
Where°
2 = two standard deviations (95 percent confidence limit)
ST = individual component error, (percent coefficient of
variation)
n = total number of error components.
26
-------
Thus, a total uncertainty of 7.0 percent was obtained for all the
compounds listed in Table 2. For those analyses involving the use of
NBS-SRM's for calibration, the total uncertainty was determined to be
3.5 percent.
27
-------
SECTION 5
SUMMARY AND CONCLUSIONS
Cylinder gases of hydrocarbons, halocarhons, and sulfur containing
organic species have been used successfully as aud.it materials to as-
sess the relative accuracy of gas chromatographic systems used to mea-
sure source emissions. Absolute accuracy has not been determined due
to the lack of NBS standards for most of the organic gas mixtures above
1 ppm; instead an estimated inter laboratory bias has been reported for
the performance audits conducted during source testing. This inter-
laboratory bias has been generally within 15 percent for both low and
high concentration gases (Table 3).
Of the 45 gaseous compounds studied or currently under study, 39
have demonstrated sufficient stability in cylinders to be used further
as audit materials. Five compounds (ethylamine, paradichlorobenzene,
cyclohexanone, 1,2-dibromoethylene, and aniline) are not recommended as
audit materials for various reasons as discussed in Attachment 1. One
gaseous compound (formaldehyde) was ordered but the speciality gas man-
ufacturer indicated that cylinder gases of this compound could not be
prepared. Detailed statistical analvses which would separate statisti-
cal deviations from true concentration changes with time for 18 gaseous
compounds have been published in a journal publication, and statistical
analyses for the remaining compounds will be presented in a future re-
port.
28
-------
REFERENCES
R. K. M. Jayanty, C. Parker, C. E. Decker, W. F. Gutknecht, J. E.
Knoll and D. J. VonLehmden, "Quality Assurance for Emissions Anal-
ysis Systems," Environmental Science and Technology, _17 (6),
257-263A (1983).
G. B. Howe, R. K. M. Jayanty, A. V. Rao, W. F. Gutknecht, C. E.
Decker and D. J. VonLehmden, "Evaluation of Selected Gaseous Halo-
carbons for Use in Source Test Performance Audits," J. of Air Pol-
lution Control Association, 33 (9), 823-826 (1983).
29
-------
ATTACHMENT 1
Stability Data
as of
July 1985
1.0 BENZENE STABILITY STUDY
2.0 ETHYLENE STABILITY STUDY
3.0 PROPYLENE STABILITY STUDY
4.0 METHANE/ETHANE STABILITY STUDY
5.0 PROPANE STABILITY STUDY
6.0 TOLUENE STABILITY STUDY
7.0 HYDROGEN SULFIDE STABILITY STUDY
8.0 META-XYLENE STABILITY STUDY
9.0 METHYL ACETATE STABILITY STUDY
10.0 CHLOROFORM STABILITY STUDY
11.0 CARBONYL SULFIDE STABILITY STUDY
12.0 METHYL MERCAPTAN STABILITY STUDY
13.0 HEXANE STABILITY STUDY
14.0 1,2-DICHLOROETHANE STABILITY STUDY
15.0 CYCLOHEXANE STABILITY STUDY
16.0 METHYL ETHYL KETONE STABILITY STUDY
17.0 METHANOL STABILITY STUDY
18.0 1,2-DICHLOROPROPANE STABILITY STUDY
19.0 TRICHLOROETHYLENE STABILITY STUDY
20.0 1,1-DICHLOROETHYLENE STABILITY STUDY
21.0 1,2-DIBROMOETHYLENE STABILITY STUDY
22.0 PERCHLOROETHYLENE STABILITY STUDY
30
-------
23.0 VINYL CHLORIDE STABILITY STUDY
24.0 1,3-BUTADIENE STABILITY STUDY
25.0 ACRYLONITRILE STABILITY STUDY
26.0 ANILINE STABILITY STUDY
27.0 METHYL ISOBUTYL KETONE STABILITY STUDY
28.0 CYCLOHEXANONE STABILITY STUDY
29.0 PARADICHLOROBENZENE STABILITY STUDY
30.0 ETHYLAMINE STABILITY STUDY
31.0 FORMALDEHYDE STABILITY STUDY
32.0 METHYLENE CHLORIDE STABILITY STUDY
33.0 CARBON TETRACHLORIDE STABILITY STUDY
34.0 FREON 113 STABILITY STUDY
35.0 METHYL CHLOROFORM STABILITY STUDY
36.0 ETHYLENE OXIDE STABILITY STUDY
37.0 PROPYLENE OXIDE STABILITY STUDY
38.0 ALLYL CHLORIDE STABILITY STUDY
39.0 ACROLEIN STABILITY STUDY
40.0 CHLOROBENZENE STABILITY STUDY
41.0 CARBON DISULFIDE STABILITY STUDY
42.0 METHOD 25 GAS MIXTURE
43.0 ETHYLENE DIBROMIDE
44.0 1,1,2,2-TETRACHLOROETHANE
NOTE: PPM concentrations shown in Attachment 1 are expressed on a
mole/mole basis, except for EPA Method 25 mixture which is on a
mole carbon/mole basis.
31
-------
1.0 BENZENE STABILITY STUDY
Cyl inder No.
Cylinder Construction*
Manufacturer
Concentration
RTI
Concentration
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
1A
Al
65.4
7/27/77
(79.0)
136
(74.0)
156
(78.0)
167
(80.0)
630
(77.9)
**
IB 1C
Al Al
324 200
7/27/77 7/27/77
(374) (241)
136 247
(337) (216)
156 252
(350) (215)
167 381
(355) (218)
402 **
(331)
433
(343)
969
(358)
1274
(348)
1491
(324)
2056
(305)
2438
(319)
ID
Al
117
7/27/77
(138)
29
(144)
157
( 134)
252
(129)
290
(127)
414
(127)
1247
(132)
2438
(121)
IE
S
61.0
2/10/78
(62.0)
78
(62.0)
216
(61.0)
385
(65.0)
722
(66.9)
1337
(55.7)
1858
(58.7)
2246
(60.4)
IF
S
71.0
2/10/78
(71.0)
232
(73.0)
385
(75.0)
586
(74.5)
882
(75.7)
1292
(65.7)
2246
(70.0)
16
S
80.0
2/10/78
(80.0)
78
(81.0)
216
(81.0)
385
(84.0)
504
(85.4)
1292
(74.0)
2246
(78.3)
Al = Aluminum; S = Steel; LS = Low-pressure Steel.
Cy I Inder empty.
ANALYTICAL CONDITIONS: Flame lonizatlon detector, \0% OV-101 on Chromosorb WHP column at 60°C.
CALIBRATION: Reagent-grade "Benzene" liquid Is used as a standard. Pressure-dilution tech-
nique Is used for making the series of standards for calibration.
32
-------
1.0 BENZENE STABILITY STUDY (Continued)
Cyl Inder No.
Cylinder Construction*
Manufacturer
Concentration
RTI
Concentration
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
1H
S
100
2/8/78
(101)
65
( 102)
206
(98.0)
237
(101)
434
(105)
773
(106)
831
(100)
1294
(92.0)
2380
(96.0)
11
S
139
2/9/78
(139)
49
(139)
50
( 142)
96
(139)
127
( 140)
205
(138)
505
(147)
1293
(128)
1338
(128)
2380
(134)
U IK IL
S S S
232 265 296
2/9/78 2/9/78 2/9/78
(229) (264) (295)
233 49 49
(237) (261) (292)
386 50 5 1
(243) (268) (294)
557 69 93
(225) (254) (298)
** 84 205
(269) (294)
** 237
(302)
809
(295)
1294
(290)
2379
(285)
IM
S
326
2/9/78
(319)
49
(316)
51
(318)
96
(323)
433
(345)
830
(335)
1294
(320)
2379
(310)
IN
S
344
2/9/78
(332)
49
(327)
54
(342)
69
(335)
809
(342)
**
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
Cylinder empty.
33
-------
1.0 BENZENE STABILITY STUDY (Continued)
Cyl inder No.
10
Cyl Inder Construction* S
Manufacturer
Concentration
RTl
Concentration
ppm 389
Date 2/9/78
ppm (387)
Day 64
ppm (369)
Day 205
ppm (396)
Day 809
ppm (396)
Day 1294
ppm (389)
Day 2247
ppm (376)
Day
ppm
Day
ppm
Day
ppm
Day
ppm
IP
S
8.04
4/21/78
(8.37)
4
(8.33)
25
(8.20)
26
(8.34)
56
(8.19)
134
(7.81)
434
(8.21)
766
(7.93)
1222
(7.68)
2175
(7.90)
1Q IR IS IT
S S S S
9.85 9.89 9.93 10.0
4/21/78 4/21/78 4/21/78 4/21/78
(9.99) (10.0) (10.0) (10.7)
5 4 4 25
(9.88) (10.1) (10.1) (10.2)
25 13 26 146
(10.1) (9.73) (9.80) (9.20)
332 332 56 362
(9.71) (9.77) (9.50) (9.90)
** 1018 146 1222
(9.46) (8.90) (9.56)
1270 628 **
(9.64) (9.57)
738
(9.45)
*#
IU
S
10.9
4/21/78
(11.5)
4
(10.7)
25
(10.8)
332
(10.7)
434
(10.9)
759
(10.2)
1222
(9.69)
2175
(9.90)
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
Cy I Inder empty.
34
-------
1.0 BENZENE STABILITY STUDY (Continued)
Cyl Inder
No.
Cylinder Construction*
Manufacturer
Concentration
RTI
Concentration
ppm
Data
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
IV
S
12.2
4/25/78
(12.7)
1
(12.5)
21
(12.3)
109
(12.0)
358
(12.1)
755
(12.0)
1218
(11.7)
2171
(11.9)
1W IX
S S
8.09 11.0
5/19/78 5/4/78
(8.10) (11.2)
105 132
(7.70) (10.2)
287 **
(8.10)
488
(8.20)
784
(8.30)
1194
(7.45)
2147
(7.80)
1Y IZ IAA
S S S
11.2 8.09 9.14
5/4/78 5/4/78 5/4/78
(10.9) (8.20) (9.10)
132 132 132
(9.90) (7.04) (7.80)
302 302 302
(10.7) (7.70) (8.50)
393 473 1005
(10.8) (7.54) (8.17)
2162 ** 1209
(10.3) (8.42)
2162
(8.40)
1AB
S
270
7/27/77
(300)
29
(319)
157
(312)
2056
(305)
**
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
CylInder empty.
35
-------
2.0 ETHYLENE STABILITY STUDY
Cyl Inder No.
Cylinder Construction*
Manufacturer
Concentration
RTI
Concentration
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
2A
Al
2920
2/23/78
(3070)
49
(3120)
198
(2880)
809
(3200)
2291
(3280)
28
Al
3000
2/23/78
(3130)
49
(3180)
198
(2940)
809
(3270)
2291
(3350)
2C
Al
4960
2/23/78
(5210)
48
( 5340)
201
(4660)
809
(5380)
2291
(5520)
20
Al
4970
2/23/78
(5200)
48
(5280)
201
(4910)
809
(5340)
2291
(5480)
2E
. Al
19900
2/24/78
(20400)
48
(20800)
200
(20200)
808
(18900)
2290
(20600)
2F
Al
19900
2/24/78
(20600)
48
(20800)
200
(20300)
808
(19000)
2290
(20700)
1
26
Al
4.95
4/27/78
(4.70)
29
(4.70)
106
(4.85)
741
(4.62)
1180
(5.12)
2224
(4.50)
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, Durapak n-octane on Porasll C column
at 30 degrees Celsius.
CALIBRATION: NBS-SRM Propane Is used for standard calibration.
36
-------
2.0 ETHYLENE STABILITY STUDY (Continued)
Cyl Inder No.
Cylinder Construction*
Manufacturer
Concentration
RTI
Concentration
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
2H
Al
10.0
4/27/78
(9.70)
29
(9.60)
106
(9.90)
740
(8.40)
1180
(10.0)
2224
(9.50)
2587
(9.54)
21
Al
15.0
4/28/78
(14.4)
28
( 14.4)
104
(14.9)
739
(18.0)
1179
(14.4)
2223
(14.2)
2J
Al
19.9
4/28/78
(19.2)
28
( 19.3)
104
(20.3)
739
(21.5)
1179
(18.9)
2223
(18.9)
2K
Al
300
4/28/78
(306)
33
(319)
105
(312)
728
(300)
2225
(291)
2L
Al
448
4/28/78
(466)
33
(493)
104
(473)
740
(457)
2225
(435)
2M
Al
603
4/28/78
(629)
34
(646)
104
(636)
740
(606)
2225
(583)
2N
Al
701
4/28/78
(740)
34
(749)
104
(737)
740
(703)
2225
(678)
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
37
-------
3.0 PROPYLENE STABILITY STUDY
Cyl Inder Mo.
Cylinder Construction*
Manufacturer
Concentration
.
RTI
Concentration
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
3A
Al
4.94
4/27/78
(4.86)
26
(4.94)
27
(4.78)
104
(4.98)
749
(4.93)
2229
04.80)
2601
(4.75)
3B
Al
9.91
4/27/78
(9.83)
26
(9.85)
104
(10.3)
749
(9.76)
1250
(9.63)
2229
(9.80)
3C
Al
14.8
4/27/78
( 14.6)
26
(14.5)
104
(14.8)
749
(14.8)
**
3D
Al
20.0
4/27/78
(19.8)
27
( 19.0)
104
(20.0)
749
(20.3)
2229
(19.7)
3E
Al
298
4/27/78
(296)
27
(286)
104
(317)
750
(324)
820
(328)
**
3F
Al
446
4/27/78
(442)
27
(428)
105
(474)
750
(479)
2229
(444)
3G
Al
585
4/27/78
(577)
27
(560)
104
(629)
750
(620)
2229
(579)
3H
Al
683
4/27/78
(672)
27
(655)
105
(729)
750
(721)
820
(725)
2229
(676)
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
**Cyl Inder empty.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, Durapak n-octane on Porasll C column at 30 degrees
Cel si us
CALIBRATION: N3S-SRM Propane Is used for standard calibration.
38
-------
4.0 METHANE/ETHANE STABILITY STUDY
Cyl Inder No. 4A
Cyl Inder Construction* Al
Audit Material**
Manufacturer
Concentration
RTI
Concentration
M
ppm 6000
Date 7/21/78
ppm (6210)
Day 264
ppm (5980)
Day 662
ppm (6580)
Day 2145
ppm (6460)
Day
ppm
Day
ppm
E
714
7/21/78
(773)
163
(715)
264
(684)
662
(703)
2145
(730)
4B
Al
M
8130
7/21/78
(8130)
35
(7550)
264
(7820)
662
(8590)
2145
(8430)
E
597
7/21/78
(654)
35
(663)
163
(606)
264
(577)
662
(598)
2145
(619)
4C
Al
M E
1000 295
7/21/77 7/21/77
(1020) (315)
264 163
(983) (292)
1 027 264
(1290) (283)
2510 1027
(1068) (284)
2510
(300)
40
Al
M
1670
7/21/77
( 1710)
35
(1560)
264
(1640)
1027
(1950)
2510
(1770)
E
202
7/21/77
(220)
29
(218)
157
(202)
258
(195)
1027
(206)
2510
(207)
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
*M = Methane; E = Ethane.
ANALYTICAL CONDITIONS: Flame ionizatlon detector, Durapak n-octane on Porasll C column at 30 degrees
eel si us.
CALIBRATION: NBS-SRM methane Is used for standard calibration.
39
-------
5.0 PROPANE STABILITY STUDY
Cyl Inder No.
Cylinder Construction*
Manufacturer ppm
Concentration
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
RTI ppm
Concentration
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
5A
Al
5.01
4/25/78
(4.90)
24
(4.90)
108
(5.10)
605
(4.89)
729
(5.20)
»*
58
Al
10.0
4/25/78
(9.70)
24
(9.80)
108
(10.1)
513
(10.6)
752
(10.0)
914
(10.0)
2220
(10.9)
5C
Al
14.6
4/25/78
( 14.3)
25
(14.5)
108
(14.9)
582
(15.0)
736
(14.7)
2220
(14.8)
2589
(14.8)
50
Al
20.0
4/25/78
(19.5)
25
( 19.8)
108
(20.3)
582
(20.8)
736
(20.1)
1252
(19.7)
2220
(20.0)
5E
Al
303
4/26/78
(304)
24
(301)
107
(305)
530
(316)
581
(316)
735
(313)
752
(314)
913
(309)
1251
(296)
2219
(308)
5F
Al
439
4/26/78
(441)
24
(436)
107
(440)
530
(450)
581
(453)
728
(472)
*»
5G
Al
604
4/26/78
(615)
27
(615)
107
(607)
604
(613)
735
(628)
2218
(607)
5H
Al
708
4/27/78
(730)
26
(723)
106
(710)
603
(718)
734
(734)
2218
(715)
Al = Aluminum; S = Steel, US = Low Pressure Steel.
**Cyl Inder empty.
ANALYTICAL CONDITIONS: Flame lonizatlon detector, Durapak n-octane on PorasiI C column at 30 degrees
Cel slus.
CALIBRATION: NBS-SRM Propane is used for standard calibration.
UNCERTAINTY OF REPORTED CONCENTRATIONS: + 3.5$
40
-------
5.0 PROPANE STABILITY STUDY (Continued)
Cyl inder No.
Cylinder Construction*
Manufacturer
Concentration
RTI
Concentration
ppm
Date
ppm
Day
ppm
Day
ppm
51
Al
1000
3/3/83
(1027)
452
(1070)
734
(1006)
5J
Al
2000
3/3/83
(2100)
452
(2180)
734
(2052)
5K
Al
10,000
3/3/83
(11800)
452
(13000)
734
(13021)
5L
Al
20,000
3/3/83
(20700)
452
(21000)
734
(21302)
Al = Aluminum; S = Steel, LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame ionization detector, Durapak n-octane
on PorasiI C column at 30 degrees Celsius.
CALIBRATION: NBS-SRM Propane is used for standard calibration.
UNCERTAINTY OF REPORTED CONCENTRATIONS: + 3.5?
41
-------
6.0 TOLUENE STABILITY STUDY
Cyl Inder No.
Cylinder Construction*
Manufacturer ppm
Concentration
Date
ppm
Day
ppm
Day
RT 1 ppm
Concentration
Day
ppm
Day
ppm
Day
ppm
6A
LS
408
12/6/78
(405)
3
(405)
86
(394)
100
(393)
**
6B
LS
606
12/6/78
(585)
3
(579)
86
(577)
358
(615)
2079
(663)***
2338****
(603)
6C
S
16.2
10/3/78
(17.3)
48
(14.9)
365
(15.0)
1373
(14.8)
**
60
S
9.11
10/3/78
(9.62)
64
(8.50)
66
(8.60)
160
(8.20)
**
6E 6F
S S
9.00 430
3/29/83 7/1/80
(8.51) (430)
744»**» 861
(8.04) (347)
1115
(338)
1505
(427)***
1765****
(351)
Al = Aluminum, S = Steel, LS = Low Pressure Steel.
Cyl Inder empty.
»**
Questionable value.
Concentration uncertainty: _+_ 7?
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 10? OV-101 on Chromosorb WHP column at 60
degrees Celsl us.
CALIBRATION: Reagent grade "Toluene" liquid Is used as a standard. Pressure-dilution technique
Is utilized for generation of series of standards for calibration.
42
-------
6.0 TOLUENE STABILITY STUDY (Continued)
Cyl Inder No.
Cylinder Construction*
Manufacturer ppm
Concentration
Date
ppm
RT 1 Day
Concentration ppm
6G 6H 61 6J 6K 6L
Al Al Al Al US LS
18.2 9.0 10.3 21.7 196 310
7/27/83 7/1/80 12/11/84 12/11/84 12/11/84 12/11/84
(16.1) (8.50) (9.27) (20.3) (183) (290)
383 1505 192*»»* i2l»*»# i4i»»*» i4i«*«*
(19.1)*** (9.40) (8.70) (18.9) (184) (281)
»* #*
AI = AI urn I nun, S = Steel, LS = Low Pressure Steel.
Cyl Inder empty.
Questionable value.
Concentration uncertainty: _+_ 7?
ANALYTICAL CONDITIONS: Flame ionlzation detector, 10* OV-101 on Chromosorb WHP column at 60
degrees Celsius.
CALIBRATION: Reagent grade "Toluene" liquid is used as a standard. Pressure-dilution technique Is
utilized for generation of series of standards for calibration.
43
-------
7.0 HYDROGEN SULFIDE STABILITY STUDY
Cy 1 inder No.
Cylinder Construction*
Manufacturer ppm
Concentration
Date
ppm
Day
ppm
Day
ppm
RT 1 Day
Concentration ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
7A
Al
399
10/1/78
(371)
38
(424)
111
(414)
1030
(437)
2270
(444)
2446
(401)
7B
Al
9.15
7/7/78
(9.73)
87
(6.72)
124
(7.11)
197
(6.36)
696
(6.23)
1116
(8.32)
2399
(8.0)
2424
(6.6)
2545
(6.0)
7C
Al
16.7
10/1/78
(16.1)
38
(16.5)
111
(15.7)
580
(16.2)
1030
(17.5)
2270
(14.5)
2300
(15.3)
2446
(15.6)
70 7E
Al Al
649 6. 95
10/1/78 10/1/78
(641) (7.05)
38 87
(655) (5.75)
111 • 124
(690) (5.62)
1030 197
(647) (5.23)
696
** (5.14)
1116
(5.38)
2325
(4.6)
2446
(4.4)
7F
Al
6.45
10/1/78
(4.94)
38
(5.14)
111
(4.81)
580
(4.35)
1030
(3.71)
2325
(4.3)
2446
(4.1)
7G
Al
671
3/2/83
(628)
687
(683)
833
(654)
Al = Aluminum, S = Steel, IS = Low Pressure Steel.
Cy I Inder empty.
ANALYTICAL CONDITIONS: Flame photometric detector, Chromosil 330 column at 60 degrees Celsius.
CALIBRATION: Reagent grade pure "Hydrogen sulflde" gas is used as a standard. Dilutions are made in a
Tedlar bag for generation of series of standards for calibration. Permeation tube is used as a standard
for calibration for the last two analyses of low concentration cylinders.
ANALYTICAL PROBLEMS: Only a Teflon® column and Teflon® lines should be used. The air-to-hydrogen ratio
Is critical to the sensitivity of the FPD.
44
-------
7.0 HYDROGEN SULFIDE STABILITY STUDY (Continued)
Cyl inder No.
Cylinder Construction*
Manufacturer
Concentration
RTI
Concentration
ppm
Date
ppm
Day
ppm
Day
ppm
7H
Al
20.77
1/17/85
(17.7)
25
(20.6)
146
(21.0)
71
Al
29.27
1/17/85
(22.6)
25
(30.4)
146
(30.5)
7J
Al
39.14
1/17/85
(31.6)
25
(42.4)
146
(40.5)
7K
Al
97.31
1/17/85
(83.7)
146
(92.1)
7L
Al
206.3
,1/16/85
(200)
147
(210)
7M
Al
323.2
1/16/85
(291)
147
(320)
7N
Al
417
1/16/85
(398)
147
(415)
70
Al
503.2
1/16/85
(489)
147
(514)
Al = Aluminum, S = Steel, LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame photometric detector, Chromosil 330 column at 60 degrees Celcius.
CALIBRATION: Reagent grade pure "Hydrogen sulfide" gas Is used as a standard. Dilutions are made in a
Tedlar bag for generation of series of standards for calibration. Permeation tube is used as a standard
for calibration for the last two analyses of low concentration cylinders.
ANALYTICAL PROBLEMS: Only a Teflon* column and Teflon® lines should be used. The air-to-hydrogen ratio
is critical to the sensitivity of the FPD.
45
-------
8.0 M-XYLENE STABILITY STUDY
Cyl inder No.
Cylinder Construction*
Manufacturer
Concentration
RTI
Concentration
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
8A
LS
405
10/5/78
(480)
63
(445)
158
(425)
412
(487)
606
(507)
**
88
LS
613
10/5/78
(720)
63
(676)
158
(656)
606
(760)
2140
(598)
*»
8C
S
17.3
10/5/78
( 16.6)
63
(17.2)
166
(20.8)
302
(16.4)
1036
(19.0)
**
80 8E 8F 86
S LS LS Al
7.33
10/5/78 6/7/85*** 6/7/85*** 6/7/85***
(6.20) (596) (362) (11.5)
63
(6.81)
166
(6.82)
1036
(5.66)
»»
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
Cyl Inder empty.
Concentration uncertainty: _+_ 7%
CALIBRATION: Reagent grade "M-Xy I ene" liquid is used. Pressure-dilution technique is used for
generation of series of standards for calibration.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 10* OV-101 on Chrcmosorb WHP column at 60, 120
or 140 degrees Celsius.
-------
9.0 METHYL ACETATE STABILITY STUDY
Cyl inder No.
Cylinder Construction*
Manufacturer
Concentration
RTI
Concentration
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
9A
S
326
10/13/78
(271)
230
(340)
286
(324)
629
(348)
2442**
(336)
9B
S
455
10/13/78
(428)
230
(437)
286
(442)
629
(479)
2442**
(470)
9C
S
6.84
10/13/78
(5.29)
230
(4.86)
286
(5.02)
630
(5.88)
2442**
(5.32)
90
S
17.2
10/13/78
(12.9)
230
(12.5)
286
(11.8)
630
(12.5)
2442**
(17.2)***
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
Concentration uncertainty: ±_T%
Questionable value.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, }Q% OV-275 on Chrcmosorb WHP
column at 50 degrees Celsius.
CALIBRATION: Reagent grade "Methyl acetate" liquid is used as a standard.
Pressure-dilution technique Is utilized for generation of series of
standards for cal Ibratlon.
47
-------
10.0 CHLOROFORM STABILITY STUDY
Cyl Inder No.
Cylinder Construction*
Manufacturer ppm
Concentration
Date
ppm
Day
ppm
Day
RTI ppm
Concentration
Day
ppm
Day
ppm
IOA
S
520
10/17/78
(529)
161
(515)
256
(514)
553
(531)
**
IOB
S
348
10/17/78
(345)
161
(351)
256
(340)
975
(325)
2422***
(333)
IOC
S
8.70
10/17/78
(3.08)
161
(7.39)
256
(7.50)
553
(8.11)
2422***
(4.26)
IOD
S
16.9
10/17/78
(17.6)
161
(16.5)
256
(16.2)
553
(16.5)
2422*»*
(14.9)
Al = Aluminum; S = Steel; LS = Low Pressure.
Cyl Inder empty.
Concentration uncertainty: +_ 1%.
ANALYTICAL CONDITIONS: Flame lonization detector, 10? OV-101 on Chromosorb
WHP column at 50 or 100 degrees Celsius.
CALIBRATION: Reagent grade "Chloroform" liquid Is used as a standard.
Pressure-dilution technique Is utilized for generation of series of standards
for calibration.
48
-------
11.0 CARBONYL SULFIDE STABILITY STUDY
Cyl Inder No.
Cylinder Construction*
Manufacturer
Concentration
RTI
Concentration
ppm
Date
ppm
Day
ppm
Day
ppm
11A
S
251
1 1/3/78
(276)
78
(281)
185
(275)
**
11B
S
100
1 1/3/78
(109)
78
(111)
185
(95.0)
»*
11C
S
9.96
1 1/3/78
(9.10)
78
(8.66)
185
(8.23)
**
110
S
7.03
1 1/3/78
(6.81)
78
(6.48)
185
(6.41)
»»
11E
AL
9.54
9/18/81
(12.9)
35
(12.5)
222
(9.08)
11F
AL
101
9/18/81
(111)
35
(117)
»*
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
Cy I Inder empty.
ANALYTICAL CONDITIONS: Flame photometric detector, Carbopak B column at 50 degrees Celsius or
Chromes I I 330 column at 60 degrees Celsius.
CALIBRATION: Reagent grade pure "Carbony I Sulfide" gas Is used as a standard. Dilutions are made
In Teflon* bag for generation of series of standards for calibration.
ANALYTICAL PROBLEMS: Only a Teflon column and Teflon lines should be used. The air-to-hydrogen
ratio Is critical to the sensitivity of the FPD.
49
-------
11.0 CARBONYL SULFIOE STABILITY STUDY (Continued)
Cy 1 1 nder No.
Cylinder Construction*
Manu facturer
Concentration
RTI
Concentration
ppm
Date
ppm
Day
ppm
116
Al
99.2
1/11/85
(101)
150
(96.5)
11H
Al
225
1/11/85
(228)
150
(199)
111
Al
414
1/11/85
(423)
150
(404)
Al
Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame photometric detector, Carbopak B column
at 50 degrees Celsius or Chrcmosll 330 column at 60 degrees Celsius.
CALIBRATION: Reagent grade pure "Car bony I Sul fide" gas Is used as a
standard. Dilutions are made In Teflon* bag for generation of series
of standards for calibration.
ANALYTICAL PROBLEMS: Only a Teflon column and Teflon lines should be
used. The alr-to-hydrogen ratio Is critical to the sensitivity of the
FPO.
50
-------
12.0 METHYL MERCAPTAN STABILITY STUDY
Cyl Inder
No.
Cylinder Construction*
Manufacturer
Concentration
RTI
Concentration
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
I2A
Al
8.03
1/24/79
(5.66)
104
(5.60)
139
(5.65)
985
(5.40)
2194
(5.45)
2331
(4.70)
I2B
Al
10.0
1/24/79
(7.94)
104
(8.10)
139
(7.90)
985
(8.42)
2194
(8.00)
2331
(8.00)
I2C
Al
3.55
1/24/79
(3.65)
104
(3.50)
139
(3.56)
985
(3.64)
2194
(3.80)
2331
(3.40)
I2D
Al
4.22
1/24/79
(4.23)
104
(4.76)
139
(4.54)
**
*
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
**
Cyl Inder empty.
ANALYTICAL CONDITIONS: Flame photometric detector, Carbopak B column at
50 degrees Celsius or Chrcmosil 330 column at 60 degrees Celsius.
CALIBRATION: Reagent grade pure "Methyl mercaptan" gas is used a standard.
Dilutions are made In a Teflon* bag for generation of series of standards for
cal Ibratlon. Permeation tube was used as a standard for cal ibratlon for the
last two analyses.
ANALYTICAL PROBLEMS: Only a Teflon column and Teflon lines should be used.
The air-to-hydrogen ratio Is a critical variable.
51
-------
13.0 HEXANE STABILITY STUDY
Cyl inder No.
Cylinder Construction*
Manufacturer ppm
Concentration
Date
ppm
Day
ppm
Day
ppm
RTI Day
Concentration ppm
Day
ppm
Day
ppm
Day
ppm
I3A
LS
1975
2/6/79
(2170)
6
(1980)
337
(2070)
469
(1990)
1886
(1990)
I3B
LS
2973
2/6/79
(3070)
6
(2860)
338
(2950)
469
(3080)
1886
(2980)
**
I3C
Al
30.6
2/6/79
(30.8)
296
(30.1)
337
(30.6)
469
(32.0)
523
(30.0)
835
(30.2)
1886
(32.8)
130 13E
Al Al
79.2 80.0
2/6/79 3/25/83
(82.2) (83.2)
296 376
(81.0) (88.2)
337
(81.3)
469
(79.8)
835
(80.2)
1247
(82.7)
»*
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
Cyl Inder empty.
ANALYTICAL CONDITIONS: Flame ionizatlon detector, 10* OV-101 on Chromosorb WHP column at 60
or 100 degrees Celsius.
CALIBRATION: Reagent grade "Hexane" liquid is used as a standard. Pressure-dilution
technique is utilized for making series of standards for calibration.
52
-------
14.0 1,2 DICHLOROETHANE STABILITY STUDY
Cyl Inder No.
Cylinder Construction*
Manufacturer ppm
Concentration
Date
ppm
Day
ppm
Day
ppm
Day
RTI ppm
Concentration
Day
ppm
Day
ppm
Day
ppm
Day
ppm
I4A
Al
14.4
1/19/79
(14.1)
58
(15.2)
155
(14.9)
811
(14.2)
835
(13.5)
1964
(13.9)
2333***
(14.1)
14B
Al
9.64
1/19/79
(9.20)
58
(10.8)
155
(10.0)
811
(9.56)
835
(9.19)
1964
(9.68)
2333***
(9.30)
I4C
Al
100
1/19/79
(96.2)
58
(103)
155
(98.2)
501
(87.3)
920
(102)
1964
(94.9)
2333***
(96.7)
14D
Al
526
1/19/79
(498)
58
(534)
155
(524)
501
(592)**
920
(502)
1964
(477)
2333***
(496)
I4E
Al
6.92
4/5/79
(10.0)
30
(9.42)
69
(9.30)
586
(9.14)
811
(9.70)
835
(9.16)
2247***
(9.32)
14F
Al
12.5
4/5/79
(15.2)
30
(14.7)
69
(14.3)
811
(14.5)
835
(13.8)
1888
(13.9)
2247***
(14.3)
I4G
Al
97.9
4/5/79
(102)
30
(105)
69
(99.0)
425
(87.3)
844
(101)
1888
(92.4)
2247***
(96.0)
14H
Al
439
4/5/79
(463)
30
(451)
69
(462)
589
(432)
697
(451)
844
(453)
1888
(416)
2247***
(427)
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
Questionable value.
£
Concentration uncertainty: _f_ 7%
ANALYTICAL CONDITIONS: Fl'ame lonlzatlon detector, 10$ OV-101 on Chromosorb WHP column at 100
degrees Cel si us.
CALIBRATION: Reagent grade "1,2 Dichloroethane" liquid Is used as a standard. Pressure-dilution
technique Is utilized for making series of standards for calibration.
53
-------
15.0 CYCLOHEXANE STABILITY STUDY
CylInder No. ISA
Cylinder Construction* Al
Manufacturer ppm 99.1
Concentration
Date 3/19/79
ppm (106)
Day 147
ppm (93.4)
RTI Day 394
Concentration ppm (99.0)
Day 926
ppm (102)
Day 1966
ppm (95.9)
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame ionizatlon detector, 10? OV-101 on
Chromosorb WHP column at 100 degrees Celsius.
CALIBRATION: Reagent grade "Cyclohexane" liquid is used as a stan-
dard. Pressure-dilution technique is used for making series of
standards for cal ibration.
54
-------
16.0 METHYL ETHYL KETONE STABILITY STUDY
Cylinder No. I6A
Cylinder Construction* S
Manufacturer ppm 43.7
Concentration
Date 5/23/79
ppm (42.3)
Day 28
ppm (40.0)
Day 58
RTI ppm (39.9)
Concentration
Day 380
ppm (44.5)
Day 653
ppm (38.7)
Day 1847
ppm (40.4)
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame lonizatlon detector, Chromosorb 101
column at 180 degrees Celsius.
CALIBRATION: Reagent grade "Methyl ethyl ketone" liquid is used as a
standard. Pressure-dlultion technique Is utilized for making series
of standards for calibration.
55
-------
17.0 METHANOL STABILITY STUDY
Cyl inder No.
Cylinder Construction*
Manufacturer
Concentration
RTI
Concentration
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
1 7A 1 7B
Al Al
50.0 97.2
5/17/79 11/28/84
(58.8) (106)
21 202**
(52.3) (88.4)
51
(51.1)
196
(55.2)
2020
(48.8)
2224**
(45.8)
AI = Aluminum; S = Steel; LS = Low Pressure Steel.
£
Concentration uncertainty: ±_~l%
ANALYTICAL CONDITIONS: Flame lonizatlon detector, Chromosorb 101
column at 50 degrees Celsius or 0.2$ Carbowax 1500 plus 0.1$ SP-2100
on Carbowax C at 60 degrees Celsius.
CALIBRATION: Reagent grade "Methanol" Is used as a standard.
Pressure-dilution technique is utilized for making series of stan-
dards for calibration.
56
-------
18.0 1,2-DICHLOROPROPANE (PROPYLENE DICHLORIDE) STABILITY STUDY
Cy 1 i nd er No.
Cylinder Construction* •
Manufacturer
Concentration
RTI
Concentration
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
ISA
Al
7.07
7/10/79
(6.06)
28
(5.52)
48
(5.94)
497
(6.03)
749
(5.59)
1793
(3.12)
1845
(3.86)
2155**
(3.49)
18B
Al
14.6
7/10/79
(15.6)
28
(16.4)
48
(15.0)
749
(16.3)
1793
(12.1)
1845
(13.2)
2155**
(13.3)
18C
Al
476
7/10/79
(496)
28
(455)
48
(480)
372
(497)
1793
(402)
1845
(424)
2155**
(441)
18D
Al
664
7/10/79
(685)
28
(621)
48
(675)
372
(685)
1793
(557)
1845
(574)
2155**
(594)
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
Concentration uncertainty: _+_ 7%
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 10$ OV-101 on Chromosorb WHP
column at 100 degrees Celsius.
CALIBRATION: Reagent grade "1,2-Dlchloropropane" liquid is used as a standard.
Pressure-dilution technique Is utilized for making series of standards for cali-
bration.
57
-------
19.0 TRICHLOROETHYLENE STABILITY STUDY
Cyl inder No.
Cylinder Construction*
Manufacturer ppm
Concentration
Date
ppm
Day
ppm
Day
RTI ppm
Concentration
Day
ppm
Day
ppm
Day
ppm
19A
Al
9.23
5/24/79
(9.58)
77
(10.2)
92
(9.78)
683
(9.03)
820
(8.91)
1853
(9.40)
19B
Al
14.7
5/24/79
(14.3)
77
(15.1)
92
(14.9)
683
(13.6)
820
(13.5)
1853
(14.0)
19C
Al
100
5/24/79
(102)
77
(103)
92
(100)
810
(105)
820
(94.6)
1853
(105)
19D
Al
505
5/24/79
(506)
77
(503)
92
(499)
810
(522)
820
(490)
1853
(523)
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame ionization detector, 10? OV-101 on Chromosorb WHP
column at 100 degrees Celsius.
CALIBRATION: Reagent grade "Trichloroethylene" liquid is used as a standard.
Pressure-dilution technique is used for making series of standards for calibra-
tion.
5d
-------
20.0 1,1-DICHLOROETHYLENE (VINYLIDENE CHLORIDE) STABILITY STUDY
Cyl Inder No.
Cylinder Construction*
Manufacturer
Concentration
RTI
Concentration
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
20A
Al
9.58
6/1/79
(10.3)
35
(9.90)
62
(10.1)
404
(11.5)**
813
(9.00)
1831
(9.00)
2190***
(8.78)
20B
Al
14.8
6/1/79
(15.6)
35
< 1 5. 1 )
62
(15.5)
404
(17.1)**
818
(14.2)
1831
(13.2)
2190***
(14.1)
20C
Al
96.8
6/1/79
(101)
35
(99.0)
62
(102)
817
(94.0)
1831
(98.4)
2190***
(94.7)
200
Al
490
6/1/79
(524)
35
(510)
62
(505)
404
(498)
1831
(488)
2190***
(479)
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
g
Questionable value.
Concentration uncertainty: _+_ 7$.
ANALYTICAL CONDITIONS: Flame ionlzatlon detector, \Q% OV-101 on Chromosorb WHP
column at 100 degrees Celsius or 10? SP-2100 on Supelcoport col unn at 100
degrees Celsius.
CALIBRATION: Reagent grade "1, 1-Dichloroethyl ene" pure liquid Is used as a
standard. Pressure-dilution technique Is utilized for making series of stan-
dards for calibration.
59
-------
21.0 1,2-OIBROMOETHYLENE STABILITY STUDY
Cyl Inder No.
Cylinder Construction*
Manufacturer
Concentration
RTI
Concentration
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
21A
LS
10.0
6/18/79
(7.90)
61
(7.80)
89
(7.40)
722
(7.72)
**
21B
LS
14.9
6/18/79
(12.2)
61
(12.0)
89
(11.6)
772
(8.02)
»*
21C
LS
99.9
6/1/79
(110)
61
(107)
89
(105)
787
(99.2)
**
21D
LS
301
6/18/79
(265)
61
(266)
89
(257)
643
(309)
**
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
Cylinders returned due to partial conversion to an unknown compound.
ANALYTICAL CONDITIONS: Flame ionlzation detector, 10$ OV-101 on Chromosorb WHP
column at 100 degrees Celsius.
CALIBRATION: Reagent grade "1,2-Dibromoethylene" pure liquid Is used as a
standard. Pressure-dilution technique is utilized for making series of
standards for calibration.
ANALYTICAL PROBLEMS: The gas mixtures and the calibration standards contain
substantial amounts of both the els and the trans isomers of
1,2-DIbromoethylene. The first three sets of analyses are questionable because
only one Isomer was measured during the calibrations and cylinder analyses.
During the GC analyses on Day 1864, It was found that dIbromoethylene partially
converted to an unknown compound. Hence, d I bromoethyl ene Is not practical as an
aud it material.
60
-------
22.0 PERCHLOROETHYLENE STABILITY STUDY
Cyl Inder No.
Cylinder Construction*
Manu facturer
Concentration
RTI
Concentration
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
22A
S
7.98
7/6/79
(8.40)
35
(7.97)
52
(7.92)
376
(7.94)
1818
(6.88)
2162**
(6.88)
228
S
13.0
7/6/79
(15.0)
35
(14.9)
52
(14.7)
376
(14.5)
1818
(13.7)
2162**
(13.3)
22C
US
487
7/6/79
(419)
35
(453)
52
(440)
677
(361)
713
(387)
1818
(349)
2162**
(353)
22D
LS
629
7/6/79
(624)
35
(642)
52
(619)
677
(542)
713
(571 )
1818
(557)
2162**
(564)
Al » Aluminum; S = Steel; LS = Low Pressure Steel.
Concentration uncertainty: + 7$.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 10? OV-101 on Chromosorb
WHP column at 50 or 100 degrees Celsius.
CALIBRATION: Reagent grade "Perchloroethylene" liquid Is used as a standard.
Pressure-dilution technique Is utilized for making series of standards for
calIbratlon.
61
-------
23.0 VINYL CHLORIDE STABILITY STUDY
Cyl Inder No.
Cylinder Construction*
Manufacturer ppm
Concentration
Date
ppm
Day
RTI ppm
Concentration
Day
ppm
Day
ppm
23A
S
5.94
10/1/79
(5.87)
18
(5.74)
700
(6.60)
1812
(6.10)
23B 23C
S S
8.00 8.03
10/1/79 10/1/79
(7.71) (7.82)
18 18
(7.50) (7.45)
»* 700
(8.44)
1812
(8.10)
230
S
8.52
10/1/79
(7.85)
18
(7.61)
700
(8.41)
1812
(8.15)
23E
S
20.0
10/1/79
(19.7)
18
( 1 9. 1 )
700
(20.7)
1812
(20.3)
23F
S
20.1
10/1/79
(20.1)
18
(19.3)
700
(20.9)
1812
(20.6)
236
S
30.0
10/1/79
(29.6)
18
(28.3)
700
(29.4)
1812
(30.3)
23H
S
30.3
10/1/79
(29.8)
18
(28.7)
700
(29.4)
1812
(30.6)
231
S
7.98
10/1/79
(7.31)
18
(7.12)
700
(8.39)
1812
(7.75)
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
Cyl Inder empty.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 0.4$ Carbowax 1500 on Carbopak C at 50 degrees Celsius.
CALIBRATION: Vinyl chloride permeation tube purchased from Metron Ics Is used for calibration. Permeation
tube Is maintained at 30°C.
62
-------
24.0 1,3 BUTADIENE STABILITY STUDY
Cyl inder No.
Cylinder Construction*
24A
S
Manufacturer
Concentration
ppm
22.6
Date
ppm
3/21780
(20.9)
RTI
Concentration
Date
ppm
Day
ppm
95
(23.1)
480
(24.0)
Day
ppm
1718
(22.9)
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame ionizatlon detector, 0.1$
SP-1000 on Carbopak C column at 90 degrees Celsius or 10?
OV-101 on Chromosorb WHP column at 60 degrees Celsius.
CALIBRATION: Reagent grade "1,3 Butadiene" liquid Is used
as a standard. Pressure-dilution technique Is utilized for
making series of standards for calibration.
63
-------
25.0 ACRYLONITRILE STABILITY STUDY
Cyl Inder No.
Cylinder Construction*
Manufacturer
Concentration
RTI
Concentration
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
25A
LS
20.1
7/24/79
(14.6)
185
(12.7)
349
(13.2)
841
(9.96)
**
258
LS
348
7/24/79
(411)
185
(416)
349
(441)
841
(397)
»*
25C
. LS
11.7
7/24/79
(6.38)
185
(3.35)
349
(2.87)
841
(4.05)
**
250
LS
638
7/24/79
(678)
185
(699)
349
(703)
841
(667)
*»
25E 25F
AL AL
400 10.0
11/8/82 11/18/82
(413) (10.8)
134 139
(410) (11.7)
787 787
(421) (10.8)
Al = Aluminum; S = Steel; LS= Low Pressure Steel
Cyl inder empty
ANALYTICAL CONDITIONS: Flame lonizatlon detector, 4% Carbowax 20M on Carbopak B at 50
or 150 degrees Celsius.
CALIBRATION: Aery I onltr 11 e permeation tube or pressure-dilution technique is used for
GC-FID calibration. Permeation tube Is maintained at 30° _+_ 0.1 °C.
ANALYTICAL PROBLEMS: The large changes noted at the low concentration levels are,
at least In part, a result of difficulty in making precise measurements at these
I evel s.
64
-------
26.0 ANILINE STABILITY STUDY
Cyl Inder No. 26A 26B
Cy I Inder Construction* Al Al
Manufacturer ppm 11.3 18.4
Concentration
RTI See Analytical Problems
Analysis
*
Al = Aluminum; S = Steel; LS = Low Pressure Steel. •
ANALYTICAL CONDITIONS: Flame lonlzation detector, 10? OV-101 on
Chromosorb WHP column at 250 degrees Celsius.
CALIBRATION: Reagent grade "Aniline" pure liquid Is used as a
standard. "Glass bulb" dilution technique Is utilized for making
series of standards for calIbratlon.
ANALYTICAL PROBLEMS: Because aniline has an extremely high boil-
Ing point (186"C), special handling would be required to measure
this compound. A completely heated system for sampling In the
vapor phase and for preparing standards would be required. Temper-
ature-dependent condensation In the cylinder and the regulator
causes the amount of aniline which Is delivered by the cylinder to
vary. As a result, aniline Is not considered to be practical as an
audit material.
65
-------
27.0 METHYL ISOBUTYL KETONE STABILITY STUDY
Cyl inder No.
Cylinder Construction*
27A
Al
27C
Al
Manufacturer
Concentration
ppm
9.51
72.9
Date
ppm
12/18/80
(10.2)
7/8/81
(75.4)
Day
ppm
27
(10.6)
See Analytical
Problems
RTI
Concentration
Day
ppm
Day
ppm
83
(9.53)
202
(9.49)
Day
ppm
1275
(8.40)
Day
ppm
1643**
(10.3)
Al = Aluminum; S = Steel; LS = Low Pressure Steel
Concentration uncertainty: _+_ 1%.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 0.\% SP-1000
on
Carbopak C column at 180° degrees Celsius.
CALIBRATION: Reagent grade "Methyl Isobutyl ketone" liquid Is
used as a standard. Pressure-dilution technique Is utilized for
making series of standards for calibration.
ANALYTICAL PROBLEMS: Methyl Isobutyl ketone at high concentra-
tratlons Is not practical as an audit material because
pressurizatlon of the cylinder above approximately 200 psl
results in condensation of the analyte.
66
-------
28.0 CYCLOHEXANONE STABILITY STUDY
CylInder No. 28A 28B
Cy 11 nder Construction* Al Al
Manufacturer ppm 10.1 19.0
Concentration
RTI
Anal ysl s
Date
ppm
Day
ppm
12/11/80
(8.19)
85
(3.26)
12/11/80
(25.5)
85
(17.1)
See Analytical Problems.
Al = Aluminum; S = Steel; LS = Low Pressure Steel
ANALYTICAL CONDITIONS: Flame ionization detector, 10* SP-1000 on
Supelcoport column at 200 degrees Celsius.
CALIBRATION: Reagent grade "Cyclohexanone" liquid Is used as a
standard. Pressure-dilution technique Is used for making series
of standards for calibration.
ANALYTICAL PROBLEMS: The analysis of Cyclohexanone gas Is de-
pendent on the temperatures of the cylinder and the regulator and
on the length of the sampling line between the regulator and the
gas chromatograph. The concentration In the cylinder decreases
with time. Therefore, Cyclohexanone is not practical as an audit
mater i a I.
67
-------
29.0 PARADICHLORCBENZENE STABILITY STUDY
Cyl inder No. 29A
Cy I Inder Construction* S
298
S
Manufacturer
Concentration
ppm
15.6
38.1
RTI
Analysls
See Analytical Problems
Al = Aluminum; S = Steel; LS = Low Pressure Steel
ANALYTICAL CONDITIONS: Flame lonizatlon detector, 10? SP-1000 on
Supelcoport column at 200 degrees Celsius.
CALIBRATION: Reagent grade "Parad Ichlorobenzene" Is used as a
standard. "Glass bulb" technique Is used for making series of
standards for calibration.
ANALYTICAL PROBLEMS: The stability study for this compound was
terminated bacause of analytical difficulties and because the
cylinder pressure was less than 200 pslg. ParadIchlorobenzene Is
a solid at room temperature with a melting point of 54°C.
Condensation In the cylinder, regulator and sampling lines was
extreme. ParadIchlorobenzene Is not practical as an audit
material.
68
-------
30.0 ETHYLAMINE STABILITY STUDY
Cyl inder No. 30A 308
Cylinder Construction* S S
Manufacturer ppm 10 20
Concentration
RTI
Analysis See Analytical Problems
AI = Aluminum; S = Steel; LS = Low Pressure Steel
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 10$ OV-101
on Chromosorb WHP column at 250 degrees Celsius.
CALIBRATION: Reagent grade "Ethylamine" liquid Is used as a
standard. "Glass bulb" technique Is utilized for making
series of standards for calibration.
ANALYTICAL PROBLEMS: Because of vapor pressure considera-
tions, the cylinders could not be fully pressurized. The
pressure in the cylinder is less than 200 psi. A completely
heated system for samplIng In the vapor phase and for prepar-
ing standards would be required. Temperature-dependent
condensation in the cyl Inder and the regulator causes the
amount of ethyl am ine which Is delivered by the cylinder to
vary. As a result of these problems, ethylamine is not con-
sidered to be practical as an audit material.
69
-------
31.0 FORMALDEHYDE STABILITY STUDY
RTI
Requested ppm 10 20
Concentration
The speciality gas supplier Indicated that they could not
make gas mixtures containing formaldehyde.
70
-------
32.0 METHYLENE CHLORIDE STABILITY STUDY
Cyl Inder No.
Cyl Inder Construction*
Manufacturer
Concentration
RTI
Concentration
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
32A 32B 32C
Al Al Al
10.2 1.0** 5.0**
3/5/82
(10.8)
31
(10.8)
70
(10.6)
96
(11.2)
124
(11.4)
160
(10.9)
278
(10.2)
381
(9.70)
843
(9.20)***
1198****
(11.5)
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
Nominal concentrations ordered from the manufacturer.
Questionable value.
£
Concentration uncertainty: + 1%.
ANALYTICAL CONDITIONS: Flame ionizatlon detector, 20 ft. x
1/8" SS column packed with 10* SP-1000 on 80/100 Supelcoport.
30 cm^/minute He carrier gas. Column temp. = 100°C.
Detector temp. = 175°C.
CALIBRATION: Reagent grade "Methyl ene ch I or ide" liquid is
used as a standard. Pressure-dilution technique Is utilized
for making series of standards for calibration.
71
-------
33.0 CARBON TETRACHLORIDE STABILITY STUDY
Cyl inder No.
Cylinder Construction*
Manufacturer /
Concentration
RTI
Concentration
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
33A
AL
11.3
3/4/82
(12.7)
74
(11.7)
74
(10.2)
98
(11.1)
124
(10.6)
161
(10.2)
382
(10.5)
832
(9.60)**'
1 1 99***
(12.2)
Al = Aluminum; S = Steel; US = Low Pressure Steel.
Questionable value.
Concentration uncertainty: + 1%,
ANALYTICAL CONDITIONS: Flame ionization detector, 20 ft.
x 1/8" SS column packed with \Q% SP-1000 on 80/100 Supel-
coport. 30 cm-'/minute He carrier gas. Column temp. =
100"C. Detector temp. = 175"C.
CALIBRATION: Reagent grade "Carbon tetrachl oride" liquid
is used as a standard. Pressure-dilution technique is
utilized for making series of standards for calibration.
72
-------
34.0 FREON 113 STABILITY STUDY
CylInder No.
Cylinder Construction*
34A
Al
Manufacturer
Concentration
ppm
10.4
RTI
Concentration
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
3/3/82
(10.8)
34
(10.1)
70
(10.0)
70
(9.60)
98
(10.0)
125
(10.0)
162
(10.3)
384
(9.80)
857
(11.0)
1200**
(8.79)
Al = Aluminum; S = Steel; IS = Low Pressure Steel.
Concentration uncertainty: _+_ 1%.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 20 ft.
x 1/8" SS column packed with 10* SP-1000 on 80/100
Supelcoport. 30 otr/minute He carrier gas. Column temp.
100°C. Detector temp. = 175"C.
CALIBRATION: Reagent grade "Freon 113" liquid Is used as
a standard. Pressure-dilution technique Is utilized for
making series of standards for calibration.
73
-------
35.0 METHYL CHLOROFORM STABILITY STUDY
Cylinder No. 35A
Cy 11 nder Construction* Al
Manufacturer ppm 10.2
Concentration
Date 3/2/82
ppm (10.3)
Day 70
ppm (11.8)
Day 99
ppm (10.7)
RTI Day 136
Concentration ppm (10.6)
Day 161
ppm (10.0)
Day 381
ppm (10.4)
Day 858
ppm (10.0)
*AI = Aluminum; S = Steel; LS = Low Pressure Steel.
ANALYTICAL CONDITIONS: Flame lonization detector, 20 ft.
x 1/8" SS column packed with 10? SP-1000 on 80/100 Supel-
coport. 30 cm /minute He carrier gas. Column temp. =
100°C. Detector temp. = 175°C.
CALIBRATION: Reagent grade "Methyl chloroform" is used as
a standard. Pressure-dilution technique is utilized for
making series of standards for calibration.
74
-------
36.0 ETHYLENE OXIDE STABILITY STUDY
Cylinder No.
Cylinder Construction*
36A 368 36C 360 36E
Al Al Al Al Al
Manufacturer
Concentration
ppm
10.0
1.0** 5.0** 15.0** 20.0*
Date
ppm
3/12/82
(11.2)
Day
ppm
73
(9.60)
RTI
Concentration
Day
ppm
Day
ppm
88
(9.80)
122
(9.60)
Day
ppm
Day
ppm
157
(9.80)
1012
(9.70)
Al = Aluminum; S = Steel; IS = Low Pressure Steel.
£
Nominal concentrations ordered from manufacturer.
ANALYTICAL CONDITIONS: Flame ionization detector, 6 ft. x 1/8" SS column packed
with 80/100 mesh Porapak QS. 30 cm^/minute Helium carrier gas. Column temp. =
150°C. Detector temp. = 175°C.
CALIBRATION: Ethyl ene oxide permeation tube purchased from
Metronlcs Is used for GC-FID cal ibration.
Permeation tube Is maintained at 30°C.
ANALYTICAL PROBLEMS: There appeared to be some loss of ethyl ene oxide when a
brass regulator was used on the
cylinder.
75
-------
37.0 PROPYLENE OXIDE STABILITY STUDY
Cyl Inder No.
Cylinder Construction*
37A
Al
37B
Al
Manufacturer
Concentration
pptn
9.48
96.0
Day
ppm
8/4/82
(12.3)
8/4/82
(89.5)
Day
ppm
55
(11.8)
55
(86.9)
RTI
Concentration
Day
ppm
Day
ppm
76
(10.6)
743
(8.10)**
76
(83.6)
121
(90.8)
Day
ppm
844
(9.24)
743
(75.7)**
Day
ppm
1057
(9.65)
844
(82.8)
Day
ppm
1057
(91.7)
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
Questionable value.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 6 ft. x
1/8" SS column packed with 80/100 mesh Porapak QS. 30 cm-Vmtn
Heliun carrier gas. Column temp. = 150"C. Detector temp. =
175°C.
CALIBRATION: Reagent grade "propylene oxide" Is used as a
standard. Pressure-dilution technique Is utilized for making
series of standards for cal I brat ion.
76
-------
38.0 ALLYL CHLORIDE STABILITY STUDY
Cyl Inder No.
Cylinder Construction*
Manu facturer
Concentration
RTI
Concentration
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
38A
S
10.2
8/13/82»*
(11.6)
75
(5.25)
110
(5.08)
167
(5.36)
727
(4.53)
***
388 38C 38D
S S S
99.5 8.7 92.4
8/13/82** 4/24/85**** 4/30/85****
(124) (8.99) (95.7)
74
(87.2)
110
(87.7)
167
(83.4)
727
(53.6)
»**
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
Initial analysis was questionable
Returned due to Impurities.
Concentration uncertainty: _+_ 1%,
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 20 ft. x 1/8" SS column
packed with 10 % SP-1000 on Supelcoport. 30 cm3/mlnute Helium carrier
gas. Column temp. = 100°C. Detector temp. = 175°C,
CALIBRATION: Reagent grade "Allyl chloride" is used as a standard. Pressure-
dilution technique Is utilized for making series of standards for
calIbratlon.
77
-------
39.0 ACROLEIN STABILITY STUDY
Cyl inder No.
Cylinder Construction*
Manufacturer
Concentration
RTI
Concentration
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
39A
Al
10.2
8/18/82
(10.6)
28
(11.0)
69
(9.74)
728
(6.90)**
833
(8.97)
1031***
(9.11)
39B
Al
107
8/18/82
(90.4)
28
(103)
69
(106)
728
(80.8)**
833
(97.3)
1031***
(98.4)
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
Questionable value.
at
Concentration uncertainty: _+_ 1%.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 20 ft. x
1/8" SS column packed with 10 % SP-1000 on 80/100 Supelco-
port. 30 onVmln Helium carrier gas. Column temp = 100"C.
Detector temp. = 175"C.
CALIBRATION: Reagent grade "acroleln" Is used as a stan-
dard. Pressure-dilution technique Is utilized for making
series of standards for calibration.
78
-------
40.0 CHLOROBENZENE STABILITY STUDY
Cyl Inder No.
Cylinder Construction*
Manu facturer
Concentration
RTI
Concentration
ppm
Date
ppm
Day
ppm
Day
ppm
Day
ppm
Day
ppm
40A 40B
S Al
9.66 14.84
8/6/82 10/11/83
(9.03) (14.7)
39 612**
(9.15) (13.4)
75
(9.20)
380
(9.62)
1043**
(8.11)
40C
Al
4.89
10/11/83
(4.19)
612**
(4.74)
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
Concentration uncertainty: _+_ 1%.
ANALYTICAL CONDITIONS: Flame lonlzatlon detection, 20' X 1/8"
stainless steel column packed with 10$ SP-1000 on 80/100 mesh
Supelcoport. 30 cc/mln Helium carrier gas. Column temp. = 150°C.
Detector temp = 175"C.
CALIBRATION: Reagent grade chlorobenzene was used as a standard.
Pressure-dilution technique Is utilized for making a series of
standards.
79
-------
41.0 CARBON DISULHDE STABILITY STUDY
CylInder No.
Cylinder Construction*
41A
Al
41B
Al
Manufacturer
Concentration
pptn
108
108
Date
ppm
7/14/82
(100)
2/21/85
(101)
Day
RTI ppm
Concentration
Day
ppm
34
(114)
72
(116)
110
(98.0)
Al = Aluminum; S = Steel; LS = Low Pressure Steel.
*Cy I Inder empty.
ANALYTICAL CONDITIONS: Flame photometric detector, 4.6' X 1/4"
Teflon* column packed with Carbopak BHT 100. 90 cc/mln Helium
carrier gas. Column temp. = 75"C. Detector temp. = 175°C.
CALIBRATION: Reagent grade carbon dlsulflde Is Injected Into a
Teflon* bag being filled with N2 at 5 L/mln. through a mass
flow controller. The Injection fitting Is heated slightly to
ensure volatilization.
ANALYTICAL PROBLEMS: There Is significant peak "tailing" un-
less a very high flow rate Is used. "Tailing" is also caused by
"bleed" from the sample loop. Sample valve should be In the In-
ject position for exactly 5 seconds and then switched back to
the sampling position to attenuate tailing. All sample lines
and regulators must be conditioned extensively.
80
-------
42.0 EPA METHOD 25 GAS MIXTURE STABILITY STUDY*
Cyl inder No.
Cylinder Construction***
Manufacturer
Concentration
RTI
Concentration
ppmC
Date
ppmC
Day
ppmC
Day
ppmC
42A
Al
too
3/16/83
(102)
483
(97.9)
»*
42B
Al
100
3/16/83
(107)
483
(104)
**
42C 42D
Al Al
200 750
3/16/83 3/16/83
(205) (775)
»* 483
(779)
726****
(765)
42E
Al
1000
3/16/83
(1040)
483
(1060)
726****
(1020)
42F
Al
2000
3/16/83
(1940)
483
(1930)
726****
(1930)
Gas Mixture contains an aliphatic hydrocarbon, an aromatic hydrocarbon, and carbon
dioxide in nitrogen.
Cyl inder empty.
*AI = Aluminum; S = Steel; LS = Low Pressure Steel
Concentration uncertainty: _+_ 1%.
ANALYTICAL CONDITIONS: Flame ionization detector Durapak n-octane on Poracll C
column at 30°C for separation of aliphatic hydrocarbon and 10? OV-101 on chromosorb
WHP column at 60°C for separation of aromatic hydrocarbon.
CALIBRATION: NBS-SRM was used as a standard for aliphatic hydrocarbon and Reagent
grade liquid is used as a standard for aromatic hydrocarbon. Pressure-dilution
technique is utilized for generation of series of standards for calibration.
81
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42.0 EPA METHOD 25 GAS MIXTURE STABILITY STUDY* (Continued)
Cyl Inder No.
Cylinder Construction**
Manufacturer
Concentration
RTI
Concentration
ppmC
Date
ppmC
Day
ppmC
426
Al
96.7
12/1 1/84
(96.4)
90***
(95.8)
42H
Al
98.6
12/11/84
(98.9)
90***
(93.3)
421
Al
147.6
12/11/84
(149)
90***
(144)
42J
Al
151
12/11/84
(153)
90***
(145)
42K
Al
198
12/11/84
(195)
192
42L
Al
197.5
12/11/84
(195)
90***
(183)**** (187)
Gas Mixture contains an aliphatic hydrocarbon, an aromatic hydrocarbon, and carbon
dioxide in nitrogen.
Al = Aluminum; S = Steel; LS = Low Pressure Steel
Concentration uncertainty: _f_ 7$.
Questionable value.
ANALYTICAL CONDITIONS: Flame ionization detector Durapak n-octane on Poracil C
column at 30°C for separation of aliphatic hydrocarbon and 10? OV-101 on chrcmosorb
WHP column at 60°C for separation of aromatic hydrocarbon.
CALIBRATION: NBS-SRM was used as a standard for aliphatic hydrocarbon and Reagent
grade liquid is used as a standard for aromatic hydrocarbon. Pressure-dilution
technique is utilized for generation of series of standards for calibration.
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43.0 ETHYLENE DIBROMIDE STABILITY STUDY
Cyl Inder No.
Cylinder Construction*
Manufacturer
Concentration
RTI
Concentration
ppm
Date
ppm
Day
ppm
Day
ppm
43A
S
10
10/24/84
(9.3)
54
(9.3)
243
(8.66)
438
S
20
10/24/84
(17.5)
54
(17.5)
243
(15.4)
43C
S
100
10/24/85
(96.1)
55
(107)
243
(84.0)
43D
S
300
1 0/24/84
(266)
55
(344)**
Al = Aluminum; S = Steel; LS = Low Pressure Steel
Questionable value.
ANALYTICAL CONDITIONS: Flame lonlzatlon detector, 5t OV-101 on Chromo-
sorb WHP at 60°C.
CALIBRATION: Reagent grade "ethylene dlbromlde" liquid Is used as a
standard. Pressure-dilution technique Is utilized for making series of
standards for calIbratlon.
83
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44.0 1,1,2,2-TETRACHLOROETHANE STABILITY STUDY
CylInder No. 44A
Cy 11nder Construction* Al
Manufacturer ppm 12.2
Concentration
RTI Data 10/9/84
Concentration ppm (11.6)
Al = Aluminum; S = Steel; LS = Low Pressure
Steel
ANALYTICAL CONDITIONS: Flame lonlzatlon detec-
tor, 5% OV-101 on Chromosorb WHP at 100°C.
CALIBRATION: Reagent grade "1,1,2,2-Tetra-
chloroethane" liquid Is used as a standard.
Pressure-dilution technique Is utilized for
making series of standards for calibration.
84
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