INSPECTION MANUAL
FOR
TOXIC AIR POLLUTANT
EMISSIONS
U.f., CfH'iTtnrosotal Pratecton Agaacy
U fj;en III info;matron
C2..tar (3F«;52)
{XI CfeKtsat Street ''/
arPA 1§107 /
Research & Consulting in Pollution Control
EPA Report Collection
Information Resource Center
US EPA Region 3
Philadelphia, PA 19107
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ACKNOWLEDGMENTS
WAPORA, Incorporated wishes to acknowledge
the invaluable assistance, comments and criticisms
received from many individuals during the course
of this inspection manual's preparation and field
testing. Those in the industrial sector providing
the greatest amount of help include Messrs. W.
Rakita and G. Schnabel of Rohm and Haas; F. Winter-
kamp and G. Lamb of DuPont; E. Fike and C. Reich
of Fike Chemical; H. Kabernagel and W. King of
FMC; H. Karawan, H. Coombs and R. Foster of Union
Carbide; C. Strauss and L. Mattioli of Allied
Chemical; G. Strickier and C. Dilmore of PPG; R.
Weicker, H. Klotz and L. Mount of iSTease Chemical;
and C.E. Cooper of Borg-Warner. In addition, of
those in the state and local environmental regula-
tory agencies offering assistance, the Maryland
Bureau of Air Quality's Messrs. G. Ferreri and
J. McQuade were most helpful in explaining the
development of their toxic substances control pro-
gram. Finally, WAPORA gratefully acknowledges
the guidance and assistance rendered throughout
this manual's development by the EPA Project Officer,
Mr. Abraham Ferdas.
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TABLE OF CONTENTS
Chapter Page
Acknowledgments iii
List of Exhibits vi
1 Introduction 1-1
2 Authority to Inspect 2-1
3 Toxicity of Substances 3-1
4 Emission Sources 4-1
5 Control Techniques 5-1
6 Start-ups, Malfunctions and Shut-downs 6-1
7 Instrumentation, Monitoring, Record- 7-1
keeping and Reporting
8 Field Investigations 8-1
References ix
v
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LIST OF EXHIBITS
Exhibit Page
2-1 Selected Sections of the Clean Air Act 2-3
3-1 Threshold Limit Values Adopted by the 3-7
Occupational Safety and Health
Administration
3-2 Additional Toxic and Hazardous Sub- 3-14
stances Regulated by the Occupational
Safety and Health Administration
3-3 Relationships of Threshold Limit Values 3-15
to Selected Ambient Air Quality
Standards
3-4 Correlation Between Threshold Limit 3-16
Values and Lethal-Dose 50's
3-5 Known and Potential Carcinogens As 3-17
Listed by the Maryland Bureau of Air
Quality
3-6 Odor Descriptions and Thresholds for 3-18
Various Materials
4-1 Vapor Pressures of Organic Materials 4-9
4-2 Vapor Pressures of Inorganic Materials 4-22
4-3 Method for Estimating Storage Tank 4-25
Emissions
5-1 Air Velocities Required at Locations 5-6
of Contaminant Releases
8-1 Items of Safety and Inspection Equip- 8-22
ment
8-2 Pre-Entry Chemical Emission Source 8-23
Inspection Form
VI
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Exhibit Page
8-3 Reactor Inspection Form 8-24
8-4 Dryer Inspection Form 8-25
8-5 Grinding or Milling Operation Inspec- 8-26
tion Form
8-6 Storage Tank Inspection Form 8-27
8-7 Pump and Compressor Inspection Form 8-28
8-8 Hood and Ductwork Inspection Form 8-29
8-9 Industrial Waste Incinerator Inspec- 8-30
tion Form
8-10 Emission Control Equipment Inspection 8-31
Form
8-11 Chemical Substance Emission Source 8-32
Summary Form
8-12 Toxic Emission Preliminary Assessment 8-33
Procedure
8-13 Principal Reference Documents Recom- 8-34
mended for Use by Toxic Air Pollutant
Emission Investigators
Vll
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CHAPTER 1
INTRODUCTION
This Inspection Manual for Toxic Air Pollutant
Emissions has been prepared in order to aid air
pollution control agency surveillance personnel
in their inspections of facilities that manufacture
or process certain chemical substances that may
be released into the atmosphere and subsequently
threaten human health or other aspects of the
environment. Since it is recognized that most
air pollution inspectors are neither degreed chemi-
cal engineers nor experienced in the chemical process
industries, this manual presupposes only a knowledge
of air pollution fundamentals and elementary prin-
ciples of chemistry on the part of the user. Never-
theless, it is hoped and intended that the informa-
tion presented in this document will also prove
to be useful to many of the more experienced control
agency personnel who must deal with toxic substance
problems.
In the absence of directly applicable source
facility emission regulations (except in the cases
of those few industries regulated by the National
Emission Standards for Hazardous Air Pollutants,
or by similarly-designed state standards - cases
considered to be outside the scope of this manual),
the inspector's job as related to toxic substances
can be an extremely difficult one. Although the
Clean Air Act and State Implementation Plan air
pollution prohibitions apply to all air contaminants
adversely affecting human health or welfare, demon-
strating that observed effects are attributable
to a specific emission source is a task that cannot
ordinarily be accomplished by an inspector alone,
and more often cannot be accomplished at all.
The Toxic Substances Control Act (Public Law
94-469) may provide some degree of relief from
such difficulties through the provisions of Section
6, "Regulation of Hazardous Chemical Substances
1-1
-------
and Mixtures," which, allows the EPA to propose
and adopt rules to prevent any "unreasonable risk
of injury to health or the environment"; Section
7, "Imminent Hazards," which allows the EPA to
immediately commence court action to prevent any
"imminent and unreasonable risk of serious or wide-
spread injury"; and other sections. It is conceiv-
able that field inspectors may become involved
in the implementation of this act, but this matter
is beyond the scope of this manual.
Because of the great significance of the general
lack of toxic substance emission standards to
the field investigator, the first post-introductory
chapter of this manual is devoted to a discussion
of his authority to conduct toxic substance emission
inspections, and of the limits that have been placed
upon that authority.
While the purpose of preparing this document
was not to develop a definition of toxicity, which
could be a very complex task indeed, it was neverthe-
less necessary to describe what is meant by the term
toxic substance as used in this manual. A chapter
has also been devoted to this important point.
The subjects of the remaining chapters are
emission sources; control techniques; start-ups,
malfunctions and shut-downs; instrumentation, moni-
toring, record-keeping and reporting; and, most
important, field investigations, including discus-
sions of the inspection procedures to be employed
and the forms to be completed.
1-2
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CHAPTER 2
AUTHORITY TO INSPECT
The primary source of authority for conducting
facility inspections is set forth in the Clean
Air Act under Section 114, entitled "Inspection,
Monitoring, and Entry." Although there are (with
few exceptions) no specific toxic substance imple-
mentation plan provisions, standards of performance,
or emission standards with which compliance may
need to be determined, Section 114 also authorizes
inspections for the purposes of "developing or
assisting in the development of" such plans and
standards, and carrying out Section 303, "Emer-
gency Powers."
Since the effectiveness of an emission regula-
tion is ordinarily highly dependent on its enforce-
ability through a field surveillance program, the
need for conducting inspections as regulations
are developed is apparent; however, in order to
insure that the field inspection experience gained
is actually utilized in the development of regula-
tions, those responsible for such activities should
be kept informed of inspection plans and programs,
requested to provide comments and suggestions,
and provided with copies of inspection reports.
In this way, the need to duplicate inspection visits
will be avoided, and regulations will not need
to be drafted, proposed or promulgated without
the benefit of sufficient field experience to insure
their enforceability simply because of the lack.
of time to initiate a trial inspection program,
or the lack of knowledge that an inspection program
has been on-going.
The justification for inspections needed to
carry out the provisions of Section 303 of the
Clean Air Act should require no elaboration here.
Similarly, the penalties provided under Section
113, "Federal Enforcement," that are applicable
to cases in which field investigators are refused
2-1
-------
access Csee paragraph. 113CblC4ll need not be dwelled
upon. The sections of the Clean Air Act discussed
above are presented as Exhibit 2-1.
2-2
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CHAPTER 3
TOXICITY OF SUBSTANCES
As mentioned in the introductory chapter of
this manual, it is not intended to give a general
definition of toxicity here; rather, what is meant
by the term as used throughout this document will
be explained.
Although virtually any material may be con-
sidered to be toxic if it is sufficiently concen-
trated and pervasive, in common air pollution termi-
nology only those gases that are potentially harmful
when inhaled at concentration levels of below per-
haps 10 parts per million (ppm) by volume in air,
or 0.001 percent, are generally regarded as being
of significant toxicity. Even so, the description
of a material as toxic usually carries the conno-
tation that harmful effects may result from con-
centrations well below those that are acceptable
for the major air pollutants (which include gases
such as carbon monoxide, nitrogen dioxide, and
sulfur dioxide), for which the National Ambient
Air Quality Standards range down to 0.05 ppm.
Regarding particulate substances, which are not
present in the air as separate molecules and are
thus not reported on a parts-per-million basis,
a material would not usually be described as toxic
if it were not potentially harmful at concentrations
well below the 75 ug/m^ total suspended particulate
matter ambient standard.
While Threshold Limit Values CTLV's) and other
such standards have been adopted by the Occupa-
tional Safety and Health Administration (OSHA) (1)
for a significant number of substances (see Exhi-
bits 3-1 and 3-2), comparisons of these occupational
exposure guidelines with ambient air quality stan-
dards may often prove misleading, and result in
a serious underestimation of a material's toxi-
city. This may be explained by the fact that the
3-1
-------
ambient standards are designed to protect a much-
larger and more varied population (^including the
very young, the old, and the unusually sensitive)
than are the TLV's. As a result, the occupation-
al standards are typically about two orders of
magnitude less restrictive than the roost stringent
Clong-term) ambient standards. Some of these rela-
tionships are presented in Exhibit 3-3. If one
keeps this difference (and its variability) in
mind, the TLV compilation can serve as a useful
guide to material toxicity in many cases.
One particularly serious shortcoming of relying
on TLV's as toxicity indicators is that for the
great preponderance of chemicals in use, even those
for which toxicity studies have been performed,
TLV's have neither been adopted nor proposed. The
results of these studies are summarized in the
National Institute of Occupational Safety and Health.
(NIOSH) publication entitled "Toxic Subtances List"
(2). Unfortunately, the data presented in it (e.g.,
lethal doses in milligrams per kilogram of body
weight for various species of animals) would proba-
bly not prove to be very useful to most toxic sub-
stance field investigators directly.
Another book, authored by N. Irving Sax and
entitled "Dangerous Properties of Industrial Mat-
erials" (3), is about as extensive as the NIOSH
publication but includes toxicity ratings on a scale
of 3 units, with the maximum rating of 3 indicating
severe toxicity. Ratings are assigned for both
acute and chronic effects, and for different modes
of exposure (e.g., inhalation).
For the purposes of a toxic substances air
pollution field investigator, the chemical substance
could be looked up in the Sax book's alphabetically-
ordered listing (which includes cross-referencing
in cases of multiple chemical names) and the
toxicity rating listed for chronic inhalation expo-
sures could be noted. The reason for the selection
of a chronic exposure rating is that this would
3-2
-------
almost invariably be the type of effect for which.
an inspector would be looking. The inhalation
mode of exposure is obviously that type which, is
most closely related to possible air pollution
effects. The material in question could be con-
sidered to be toxic Gas described above) if the
rating were a 3; lower ratings could be considered
to indicate that the material is not particularly
toxic. Such a functional definition of toxicity
would of course be imperfect, but would typically
be found to approximate the common conception of
air pollutant toxicity reasonably well, and to
more often be on the conservative side.
For chemical substances for which the letter
"U" (for "unknown") is given instead of a numerical
toxicity rating, or for which no space for a rating
has even been provided, there is frequently a com-
ment, reference to related chemical listings, or
other information that may enable the toxicity
of the material in question to be estimated. Occa-
sionally, a chemical substance may be found to
be unlisted. In such cases, the toxicity ratings
of several other closely-related chemicals may
be checked. (If the chemical structure or any
other relevant property of the unlisted chemical
is not known to the field investigator, he may
first consult the Chemical Rubber Company (CRC)
"Handbook of Chemistry and Physics" (4) listings
of either organic or inorganic materials, as may
be appropriate.) Both the NIOSH and Sax books
mentioned above are also useful in that they catalog
and cross-reference materials by their trade names
as well as by their chemical names.
The development of a means to quantify poten-
tially toxic levels is described in the document
"Estimation of Permissible Concentrations of Pollu-
tants for Continuous Exposure" (5). This document
presents the intentionally conservative (on the
average) relationships:
xp = 1.65 x 10~3 CTLV)
3-3
-------
and:
x
where:
p = 4.77 x 10 J CLD50I
= maximum permissible long-term
Cabout monthly] average ambient
air concentration
TLV = threshold limit value (mg/m3)
LD50 = lethal dose for 50% of rats Cor
else mice) when administered
orally (orl) , or else by intra-
peritoneal (ipr) , but not by intra-
muscular (ims) , injections (mg/kg
of animal body weight)
The above formulae are based on the ambient air
to working-place air exposure time ratio (168 hr/40
hr) , the small child to adult respiratory volume
per unit of body weight ratio (a factor of about
2) , and the lower 95% confidence limit of a TLV-
LDcjQ correlation (see Exhibit 3-4) . In addition,
the above-mentioned document indicates that, for
carcinogenic materials (which are believed to be
characterized by an exposure-risk relationship
having no threshold) , an ambient concentration
of 1 ng/m3 is the lowest of concern and may thus
be considered to be permissible. (See Exhibit
3-5 for carcinogens listed as part of Maryland
Bureau of Air Quality's progressive toxic emission
control program.) The results of either ambient
monitoring or dispersion modeling can be compared
to the calculated maximum permissible ambient air
concentration in order to aid in the assessment
of a potential toxic air pollution problem.
In keeping with the generally recommended
practice for determining whether occupational expo-
sures to mixtures of air contaminants are consistent
with TLV's, the consistency of ambient exposures
to mixtures with maximum permissible concentrations
can be assumed if:
3-4
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n
< 1
where :
n
Z = summation of terms for all n mix-
ture components
xf = actual concentration of mixture
component i
xpi = maximum permissible concentration
of mixture component i
This approach is equivalent to the statement that:
n
xpm = 1/z (fi/Xpo.)
where :
Xpm = maximum permissible total mixture
concentration
n
I = summation of terms for all n
mixture components
f-L = fraction of component i in mixture
(mass fraction if concentrations
are expressed in mass/volume
units, volume fraction if concen-
trations are expressed in volume/
volume units)
Xpi = maximum permissible concentration
of mixture component i
When the toxicity of a material or mixture
cannot be determined with a reasonable degree
of certainty by methods such as those described
above, it may be prudent for the field investigator
to assume that the material or mixture in question
is a toxic one.
It is worth noting at this point that, while
3-5
-------
many materials are potentially toxic at concentra-
tions so low as to be below the sensitivity of
most commonly used measurement techniques, many
materials are also odorous at extremely low concen-
trations C6,7,8). In cases where a field investi-
gator can smell a material whose odor threshold
is known to be above the permissible concentra-
tion, a toxicity problem may well exist. Conversely,
if an inspector cannot smell a material whose odor
threshold is below the permissible level (assuming
he is at a suitable downwind location), a toxicity
problem may well not exist, though the difficulty
of detecting odors in the outdoor air at laboratory-
test thresholds must be taken into account. Because
of the value of odor in assessing potential atmos-
pheric contaminant toxicity problems, an extensive
list of odor descriptions and thresholds is included
as Exhibit 3-6. These data should only be utilized
with an understanding of the great uncertainties
inherent in measuring odors (see the large ranges
listed for some substances).
3-6
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EXHIBIT 3-1
THRESHOLD LIMIT VALUES ADOPTED 3Y THE
OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION
Subpart Z — Toxic and Hazardous
Substances
Souxcr: 39 FR 23502. June 27, 1974,
otherwise noted, Redeslgr*t«d at 40 Fa
27073, May 28. 1876.
§ 1910.1000 Air contaminant*.
An employee's exposure to any mate-
rial listed in table Z-l, 21-2, or Z-3 ol
this section shall be limited In accord-
ance with the requirements of the follow-
ing paragraphs of this section.
(a) Table Z-l:
(1) Materials with names preceded off
"C"— Ceiling Values. An employee's ex-
posure to any material in table Z-l, the
name of -which is preceded by a "C" (e.g..
C Boron trifluoride), shall at no time
exceed the ceiling vaiue given ior that
material in the table.
(2) Other materials — 8-hour time
weighted averages. An employee's expo-
sure to any material in table Z-l, the
name of which is not preceded by "C", in
£27 8-hour work shift of a 40-hour work
•week, shall not exceed the 8-hour time
•weighted average given for that material
in the table.
(b) Table Z-2:
(1) S-hovr time weighted averages. An
employee's exposure to any material
listed in table Z-2, in any 8-hour work
shift of a 40-hour work week, shall not
exceed the 8-hour time weighted average
limit given lor that material in the table.
(2) Acceptable ceiling concentrations.
An employee's exposure to a material
listed in table Z-2 shall not exceed at
any time during an 8-hour shift the ac-
ceptable ceiling concentration limit given
for the material in the table, except for
a time period, and up to a concentration
not exceeding the maximum duration
and concentration allowed in the column
under "acceptable maximum peak above
the acceptable celling concentration for
an 8-hour shift".
(3) Example. During an 8-hour work
shift, an employee may be exposed to a
concentration of Benzene above 25 p.pjn.
(but never above 50 p.p.xn.) only for a
maximum period of 10 minutes. Such ex-
posure must be compensated by expo-
sures to concentrations less than 10
p.pjn. so that the cumulative exposure
for the entire 8-hour work shift does not
exceed a weighted average of 10 p.pjn.
(c) Table Z-3: An employee's expo-
sure to any material listed in table Z-3,
in any 8-hour work shift of a 40-hour
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Chapter XVII—Occupational Safety and Health Admin.
$ 1910.1000
work week, nVm.ii cot exceed the 8-hour
time weighted average limit given for
that material in the table.
(d) Computation formulae:
(1) (i) The cumulative exposure for an
8-hour work shift shall be computed aa
follows:
.. c.r. "
Where:
S la tha equivalent expocum for tb» work-
ing shift.
C '-» the concentration during any period
of ttsta r where tba concentration remain*
constant.
T Is the duration In horn* of tha exposure
at tba concentration C.
The valua of E . Assume that an
employee is subject to tha following
exposure:
Two hours exposure at 15Op.p.m.
Two hours exposure at 73 p.pjjo.
Four noun exposure at 50 p.p-zo.
Substituting this Information In the
formula, we have
3X15Q4-3X73+4X50
8
• =81.25 p.p-m.
Since 81.25 p.pjn. is leas than 100 p.p.m»
the 8-hour time weighted average limit,
the exposure is acceptable.
(2) (i) In case of a mixture of air con-
taminants an employer shall compute the
equivalent exposure as follows:
Where:
E« Is tha equivalent exposure for tha
mixture.
O Is tha concentration of a particular con-
taminant.
£ la tha exposure limit for that contami-
nant, from table 2-1. Z-2, or Z-3.
The value of K« sftaU not exceed unity
(1).
(ii) To illustrate the formula pre-
scribed In subdivision (i) of this sub-
paragraph. consider the following
exposures:
Aetna] coa- 8-hoor ttaa
ceaCrsUoa Velgbttd
ol Miour avera*»
«macen
Ac«ton» (Tabla Z-l) _______ SOOp.pja... 1.000 p.pon.
2-Bntaoaaa (TabU 2-1) ___ 45 p.pja.... 200 p.pjn.
Tolaeae (Tabls Z-T). ...... 40p.pja._. 2DOp.pja.
Substituting in the formula, we have:
800 45 40
1.000 200 300
=0.500 +0.223 4-0-200
Since E. Is less than unity (1). the expo-
sura combination is within acceptable
limits.
(e) To achieve compliance with para*
graph (a) through (d) of this section.
administrative or engineering controls
must first be determined and imple-
mented whenever feasible. When such
controls are not feasible to achieve full
compliance, protective equipment or any
other protective measures shall be used
to keep the exposure of employees to air
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§ 1910.1000
TJLBLB Z-l—Continued
SubsUnc*
ANTO (alpha naphthyl
thloorea)
Ars«nlc and compounds (a» As).
A nine
Ai'-nphca-methyl—Skin
Barium (solcbfo eonjpooarts)...
p-Benioqulnone. M* Qaloooa. .
Benioyl p*ro»lde..._
Bpruyl chloride —.....
Blphenyl, see Dlph»nyl ....
Blsprxool A. an Dtgiycidyl
Title 29—Labor
a 05
2-BuUnone_. —
3-Butoiy rthanol (Butyl Cel-
lasolvr)—Skta
Batyl aceut* (n-baryl acetate).
sec-Butyl acetaU
tert-Butyl acetaU
Butyl alcohol.
200
BO
150
200
200
100
150
t*rt-Batyl alcohol 100
C Butylamlne—Skin . S
C tert-Batyl chromate (as
CrOi)—Skin
n-Botyl glyddyl ether (B 0 E)_ 60
•Buryl mereaptan 10
p-tert-Butyltolaane._... 10
Calcium araenaU ...
CVictnm oiida . ....—.
"Camphor 2
C-u-hary! (3«Tln®)
Cvbon blark—
Carbon dioxide S.COO
C&rbon monoilda . SO
Chlordane—Skin
Chlorinate*! csnphtne—S!t(n.
Chlorinated dlpbenyl ortde
•Chlorine
Chlortno dloilde
C Chlorine waaorldi
C Chloroacetaldehyde ...
a-Chloroacetoph«none
(phenacykhlortda)
Chlorob«ni«ne (monocbloro-
benzene)
c-Chlorob»nryltden •
malononltnie (OCBM).
Chlorobrotnornrthane .._
2-Chiorr-1.3-butadiene. s«»
Chloronrene..
Chlnrodiphenyl (42 percent
Chlorine)—Skin
Chlorodiphenyl (54 percent
Chlorine)—Skla
l-Chloro,2,3"eporypropane, s»«
Epichlorhydrin
2-Chlorc*lliano], sea Etbylsne
chlorobydrln
Chloroetbylene, s*« Vinyl •
chloride
C Chloroform (trlcbloro-
1
0.1
ai
i
a os
7B
aos
2fJO
as
0.2
as
Boron odde.. ........... IS
C Boron trtauorlde....... 1 3
Bromine .. ttl a7
Bromofoiiu Ckin ............ as 5
Butadiene (1.34>at»dlfne) J,000 2,200
Buwrwthtol, see Bntyl mar-
cap tan.
S90
240
710
SSQ
«50
300
450
300
15
ai
270
35
60
1
3
3.S
9.000
&5
as
a»
as
3
as
0-4
3
as
350
0.4
uoro
Z-l—Continued
SabsUoo*
p.pjn.«
Coal tar pitch volatile* (ben-
zene mlabi* fraction) an lira.
cane. BaP. pu.»asntbrea»,
acrtdine. chryvens. pyrecei ______________
Cobalt, rceul fczia and dut ______________
Coppwltzie ..... .......... ________ ... —
Dusts aod Mats _______________________
Cotton dus: (raw) ------------ ..... -----
Crap® hfrb'.ciis.. . ............ ____________
Cresoi (aU Isomers)— SJria ------ 5
Crotonaldehyd*.. ------------ 2
Cum^np— Ekla... ...... ........ SO
Cyanide (as CS)— Skin.. ............... _.
CyclobMir.e ....... _______ ..... 300
Cyclohfiacol __________________ SO
Cyc!ob«anooe ............... .. 60
Cyclohnene _________________ 300
Cydopratidlece _______________ 75
2,4-D ..................................... .
DDT— Stia ............... . ...............
DDVP. see DIMorras. ------ ............. ,
]>c»boran»-S)rtn ____________ 0.05
.............
Dlacrtone aicobol (4-hydroiy-
4-rn»thyl•2^o«.'ltanone) -- ....
SO
1
as
Dlm«thylanili2e(N-dIrDethyl-
Sirla
1-Chloro-l-nUropropane
Chloroplono
Chloroprene (S^hloro-l.S-
butadiene)—Sk!a_._
Chronlam. sol. chromic,
chromora salts as Cr
Metal and insol. salts
so
20
ai
25
240
100
a?
00
as
i
Dimethyl 1.2-d:brenio-2,2-d!.
cbloroȣ"?! phosphate.
(Dlbrom).. ........................
Dte"thyl:'orrnamld«— Bkia.__ 10
2,6-D!ra»t'T7lhi-3tanone. 6*»
See footnotes at end of table.
l.l-Dtaetbyihjdratlne—Skin 0.6
DLrnethylph'.balate
Dtaetbrta:U3V»—ekln 1
Dlnlrrob*=i»29 (all lsora»rj)—
Stln
See footnotes at end of table.
a:
0.1
0.1
i
i
15
22
a
245
5
1,050
200
200
1,015
200
10
1
as
ai
340
DiMonwtbAca
Pttwrnno .... .......
Pthntyl^hthnlaU. ,„ „ _, ..
&-Dlchlorob«nzw8., - >-........
DlchIf?rtxllfluon?rTi^than»— .....
l>DIchlort>*^-dliBnliyl
1,1-Dichloro^thane..
UZ-Dlchioro^tri'lpn* . . _
C DIcMoro»thyl t ther— Sklo. ..
Dlchlaromechsae. s*«
Dichloromcnonaorometbana...
C 1.1-DlchJcro-l-nItroiithana
Propyl»r.!«1i-hloride .
DIchlorotetrRo'JcrOPthana
Dlcblorrca (DDVP)— Skin.
Dicldrln— S'sln . .
Dlethy!a=ilne
Di'thylclher. s« Ethyl ether
Dlfluorod!Drorro!nethan? .
C Dtelydtl-1 e-.3er (DQE)
DIUobntyl ketone
Dteietboiynethane, se»
Methvlal
Dlmetriyl aona=lde— Skin
liiTnpthyiajnir1*
Xylldene '.
tt2
SO
75
1,000
100
200
IS
LOOO
10
1.000
25
10
100
as
so
S
10
10
ai
.1
300
450
4,650
az
400
790
90
4,200
60
7.000
1
a 25
75
SO
860
2.8
290
20
35
18
25
3
30
-------
Chapter XVII—Occupational Safety and Health Admin. §1910.1000
Z-l—•Continued TABU Z-l—Continued
Snb*t*BC*
Sabstanc*
p.p.m.* xag./M*»
DInltrotoluene— Skin. . ..........
Oloxan* (DW thy lane dioxide)—
flkta. .
Dloftffiyl
(SM Methylem b&pbenyl
bmynnat* (MDI). ............
Dlpropylen* glyeoi nut by 1
ether— Skin..................
Dl-w. octyl phthalac* (Dl-3-
•thylbeiytphtniUce)
Endrtn—Sktn.., .......... „.,
Eptenlorhydrtn— 8Wa.. — ....
EPN— Skin..
1^-Epoxypropane, se»
Olyddol ......
Ethaaethloi. sea E thy liner-
2-E tiwryet hanol— Skin ..
2-Stlxnye«hylaeetBte> (Cello
«o4T» acetate)— 8 Ba
Ethyl acetate . ..... ...
Ethyl aeryiato— 8kta .
Ethyl alcohol (ethanoV)
Ethyl s*«unyi kstone «•"
Ethyl bntyl ketoo* f>
H&pt&none) ^ ......^ — -.*-*-,
Ethyl chloride _
Ethyl ether
C Ethylrnercsptan.-.— — .--
Ethyl silicate. . ...
Ethylene chlorobydrta— Skin. .
Ethylen* dlbromlde, see 1.2-
Etnyletie dlchloride. »ee 1^.
C E thy 1«» glyeoi dlnltrate
£lu7!czta glycu« liiuuooie&yi
ether acetatr. am Methyl
Ethylidln* chloride, SM 1,1-
N -E t hyLrnorpboUue— flktn— .
Fluorldo (aa F). ................
Fit: orotrichlororaethane.. ......
Olydrtol (2>Epoxy-l-
Olyco! monoethyl ethsr, see
Outhlon ®. see A-tlnphos-
H^ptachlor — Rkln .....
Hpxachlon^thanr— Skln.^.,. —
H'Tachloronaph thalene— Skla_
Hexon» (Mrthyl Isohatyl
kptonp) . .... —
100
100
"" 6
3
. 200
100
400
25
1.000
- 10
• - 2S ..
-' 100 •
200
SO
1,000
400
100
10
100
5
10
l«lde_. a 05
Hydroqalnaa*
^ IOD
Isoamyi alcohol., ,IHL.I ~ 100
Isobutyl acetata 150
bobutyt alcohol 100
Isophcrona „. 25
Isopropyl acetat*,. ... 250
Isopro?y! alcohol . 400
l30prcpyUmlQt__..__._..— 5
Isopropylelher — 800
Isnprcpyl glycldyl ether OOE). 50
l,o»d arssnate.^.™.. ~J~.
Undone—Skin........
Lithium hydride.
L.P.Q. (Uqolfled petroleum
gas)..»..........-......_..- 1.000
MagTjrittm oxide fame....___..... ._
MalattiiciQ—Skin
Malele anbydrid* a 25
C Manganeea.*...............**..*..... •»
Merftyl oxide 25
Mothanethlol, se* Metbyl
mercapuo......
2-Methoryethaaol, see Metbyl
csUoooWs
Methyl aceUte.
Methyl acetylene (propyne}.._
Methyl acetylene-propadlene
mlrtnre (MAPP) -
Methyl acrylate—Skin
Mothylal (dlmethoxymetham) ..
Methyl alcohol (methaool)—....
Methylsmlne .
Mothyl amyl alcohol, se«
Msthy! Uobatyl carblnol „..-
Mothyl (a-amyl) ketona (Z-
Eepcanong)—
C Methyl bromide—Skin
M^hy! buSvi k»U'De, v» *•
Eexanooe _
Methyl celloaolTe—Skin...
Metbyl ceUoaolre acetate—SUn
Methyl chloroform ...
Methyleyclohexans _
MsthylcyclohManol . „
o-Matbylcyclobexanone—Skin..
Methyl ethyl ketona (MEE),
see 2-Ratanooe.. ...... -..._...
Methyl formate .
Methyl lodlda—Skin
Methyl laobutyl carblnol—SMa.
Metbyl Laobutyl ketone, se«
Heiorss
Methyl Uocyansta—Skln.
C Metbyl mercsptan_.
200
1.000
1.000
10
1.000
200
10
1.3
10
7
II
1.4
aa
3
1
10
525
sea
TOO
300
140
950
980
12
2,100
240
a»
0.15
as
'••S
IS
1
100
LI50
35
3.1U)
260
12
100
20
485
80
25
25"
350
fiOO
100
100
80
120
1,900
2.000
470
460
100
5
25
250
23
100
0.02
10
100
Methyl methacrylate .
Methyl propyl k«ton», see 2-
Pent£^OQa ~
C a Methyl styrene 100
C Methylene blsohenyl
Isocyanate (MDI) a02
MolyManam:
Salable compounds.———.............
Insoluble compounds
Konomethyl aniline—Skin 2
C Monomathyl hydraiine—
SMn 0.2
Morphollns—Skin ... 20
Naphtha (co<ar) 100
Naphthalene 10
See footnotes at end of table.
aoi
20
410
480
0.2
5
11
9
0.35
70
400
50
-------
§1910.1000 Title 29—tabor
TABLB Z-l—Continued TASM 21-1—Continued
Soboujace p.p.m.* mg./M* *
Nickel carbonyl
Nickel, meul and soluble
cnpdi, a« Nl... .....
Nicoane— Skin.. --
Nitric add
Nitric odda
p-NltnwoUlna— Skin
Nitrobenzene— Skin
p-Nltrochlorobeiu«a*— Skia.....
Nl^mflhon.
Nltrogsn dloride. . .............
Nltrogjycartn— Skin
NlSrra ethane
2-NI:ro propane.... ........
Nitrotoluana— Skin. .
NltraolebloroimUune, see)
Ciiioroplcrln.. ...
OctacaloronapbtbaUoe— Skin.. .
*Otl raise, mineral..........
Osolua Utrodda
Oia lie acid
Oiygandlflnorlda..... — ......
Paraquat— SMn
Paraui ton— Skia
Penlachloronaphtbalene—Skla
*FeataJM ....... .......
Pejthloromethyl mercaptan
Perchloryl flomlde
Petrolenm distill it*j (naphtha).
Phenol— Skln_
p-Pbenylene diamlne— Skin.....
Phenyl ether (Taper)
Pbenyl etber-blphenyl
mixture (vapor)
Pbenylf thylene, se« Styrgne.
Pbsnylglreidyl other (PO£).._
Pbenylhyd.'aztns— Skin
Phosdrsn (.Merinpbos @ )—
Skin.
Phosgene (carbonyl chloride) —
Phosphine
Phosphoric acid..
Phosphorus (yellow)
Phosphorus pentasulfide
Phosphom* trichloride
Phtnalic aohydrfrle
Picric acid— Skin
Pival ® (2-PlTalyU,3-
Indandlone)
Platinum (Potable salts) as
Pt
Propargyl alcohol— Skin ...
Propane
n-Propyl acetate — .
Propyl alcohol
n-Propyl nitrate
Propylsnedlchlorlds .
Propvlene oilde
Pyr'thrnm
Pyridlns
RDX-Skin
Rhodium, Mrtal fame and
dusts, as Rh
Soluble salts — ...
Ronnel
Kotenone (coonaerrial)
Selenium heiafloarfde
a ooi
2
25
1
1
100
5
10
0.2
100
25
25
5
a 05
ai
a oos
1,000
200
ai
3
too
5
1
1
10
5
ai
as
as
2
1
1,000
200
200
25
73
100
S
0.1
0.05
a 007
1
as
5
30
8
S
1
310
1
29
2
250
90
SO
30
0.1
•5
a 002
i
ai
a2
0.5
an
a 01
as
a s
2,950
700
0.8
US
2,000
19
at
7
7
60
22
ai
0.4
0.4
1
ai
i
i
3
12
ai
ai
aooz
1.800
840
800
no
3JO
5
240
5
15
0.4
LS
ai
a ooi
10
s
a4
Se< footnotes at end of table.
Sabit&nce p.p.m-* i
Silver, metal and Kilobit com-
pounds.
Sodium fiaoroaotUte (1080)—
Skin _
Sodium hydrodda_...... ........... —
6:ib'.n» ai
•Stoddard solvent 800
Sclfor dloilde 5
Eolhir hMafluortde. 1.000
Sulfurlcacld --
Eclfur pentafluoride 0.025
Salfuryl fluoride 5
2.4.5T „. „.
Tantalum .
TEDP-Skln
r«!!irrlHTTi . ,, ..
'"•Unrlum hexaduorlde — _.-.. 0.02
C Terphenyb 1
.,l,1.2-Tetraehlony2J-dlSaor>
ethane 500
i,l,2,2-Tetracaloro-1.2-dl£aoTO>
ethane 600
l,lA2-Tetrachloroethane— SWn i
Tetrachlorwthylene. sea Per-
Tetrachloromnhaoa, ie« Carbon
Te£rachloronaplitialen»— Btla
T»;nu>t?iyl V>^1 («• Ph)— Slrlii_
Tetrahydrofuranl 200
Tetramethyl lead (as Pb)—
Skla
Tetraraethyl suodnoalcrile—
Skin as
Tetranltromethane 1
Tetryl (2,4.fi-trirtitrophenyl-
ciethylnltrjcnlne)— Skin
Thallium (soluble com-
pounds)— Skia S3 Tl - -
Thiram
Tla (Inorganic anpds, eicept
elides
Tin (orjianis cnpds) -
C Tolufn*.2,4-d!>socyaaat6 0. 02
o-Toluldlne— Skin 5
Toisphene, see Chlorinated
Tributrl phosphate.. ...
l,l,l-Tricnlcrro»thane, see
1,1^-Trlchloronhane— Skin 10
Titanlnmdiorlde _...„„...
Trlchloromithane, :«• Cbloro-
Trichloronaphthatene— SHn_...
1.2,3-Trlehloropropane . SO
1,1,2-Trlchloro 1,2^-trlflnoro.
ethane 1,000
Triathylsjniiia . 25
TrlflaoroTTionobi uui'jmethane — 1.000
2,4,6-Trialcropbenol, see Picric
2,4.6-TriniOTJpheiT7ltD«thyl-
Trt^ltrototaene— S»In .
Trisrthocresyl phosphate ...
Trlphenyl pbosphata. — -
Turpentine.. 100
Uranium (wlchle compounds) .
ttraninra (lasohlble cotnpoonds). .
C Vanadium:
VKJjdast
VjOifume —
Vlnylcyanide. s*« Acrylonltrlle
Se« footnotes at end of table.
ac-/M« »
a 01
a 05
2
as
2,950
a is
13
6,000
1
6
a 25
20
10
S
a2
ai
a2
n i*tv
•
4,170
4.170
35
2
a or*
£30
a or
3
s
1.8
0.1
S
ai
a 14
22
S
45
15
5
300
7.600
100
6.100
1.6
ai
3
660
0.05
az»
0.1
-------
Chapter XVH—Occupational Safety and Health Admin. - 51910,1000
Z-l—Conttauad TABL> Z-4—Coatteocd
Substinct
p.p.m,* ms./M'
Substance
p P m •
Vinyl tolaaaa
Warfarin................
TyUn« (lylol) ,„--.„.,
.
100
100
.... . a
480
0.1
435
23
Vttrlnm _.__..
Zlac chloride fama .».. . .... . ......
1
A
•1970 Addition.
• Parti of Tspor or ga* p«r million parti ol contaml-
natad air by vnluraa at 25* C. and 780 mm. Hg prnsora.
'Approximate milligrams o( pantcciau par cabin
meter of air.
(No toolnou "c" Is mad to m-?old contosloa with
ealllna valua notations.)
atmospheric eoocaatrstioa of not more th»a
0.03 p.pjn^ or penoasl prot«cUon may b* nacosa^r
to aTold beadacba.
• As sampled by coibod that do« not caDatt rspor.
/For control of central room air. biologic monitoring
Is e&MQtial tor penooiuk control.
TABUZ-2
Ustetad
8-hoorttm» AcceptabU
weljhtad eaulnj
' eoaeantnttoa
AccaptabU m&zmmm paak abOT«
the accaputblt eeiUnt ooaoantrao
Hon tor an 8-honr shlR.
Cooeantratlon
BMUMM , , 0.1mg./M>
Cadmium dost (Z37JW970)_ „___.. O.J mj./M'
Carbon dfeolflda
JOp.pjn.
SOp.pjn.
3p.p-m
do
2.4 mgJM» ---
Organo (aliryl) marenry (Z3T.30-lSd9)
Btyrens i2i7.1S-1369) .................
lOOp.pjn. —
BOO p.pjn
0.01 rngTM »..
100 p.pjn ----
. SOOp.pja.
. l,CCOp.pjci.
. 300p.pjn
, 3,000p.p^a.
{Z37.19-19«n ________ ...
Tolnena (Z37.12-198D 200 p.pja—
Hydrogen snlfld» (Z37J-19W)
. 300 p.poa..
. 20p.pua...
KOp.pjn...
. BOp.pjn.-..
. lOmtsnta*.
. 30 mlnntaa.
Do.
BmlmztMln
any 4 hours.
Jmlnntw.
ftmlmttasla
aa? 3 boon.
SOminatat.
BnJnotasln
any 3 boon.
tmlootailn
any 2 boars.
Smlnatasln
any J hours.
ffmlnotaaln
any 2 boors.
Sra!nnt»ta
any 3 boon.
lOmlcntas.
10 mtonta» one*
only U no
otbarmaaiur'
Kerenrr (Z37.»-13n) .......................... ----- —
Cbromu add and enramaUi (Z37.7-1971)
OCCOT.
do'
-------
§ 1910.1001
TABU Z-3—Ursiiii Dvm
Substance MppcJ •
Silica:
Crj'taUlne:
Quartz (respirsble) ......... 250' lUBiz/M>
Quart! (total dust) ____________ ........ 30Ej/M»
Crisloh»!!td:
value calculated from the
count or mas* formulae tar
quarts.
Tndymita: Use H th« value
calculated from lie for*
mulaA for quaru.
Amorphous, Including natural
diatomaeeous earth __________ 20 8Qmg/M'
%S10,
EQicates Oess than 1% ery>
talllne sllka):
Mica 20
Soapslone . 20
T»lc (non-«she'tos-fonn)... 20*
Talc (fibrous). Use asbe'toi
limit
Tremollte (see talc, fibrous)
Portland cement. _ 60
Graph ite (natural) 15
Coil duM (r»sptrable fraction
less than 6% SiOi) „ 2.tog/M»
or
For more than 5% SlOj.............. lOmg/M1
Inert or Nuisance Dust;
Rpsptrable fraction , 15
Total dust 60
NOTE" Conversion factors—
mppcfXi5.3—million particles per cubic
—panicles per c.c.
• Millions or particle* P«T cubic foot of sir, bued on
boplnger samplfs counted by light-field Uchrjcs.
' The pern-mag? of crystaHlnf silica !a the formula
Is the axaour.t determined froT3 air-born? *^mple5. ei-
etpl In those Instance* In which other methods hava been
shown to be applicable.
I As dneraiinsd by the membrane filter method at
iSOXph&i* contrast magntacatlon.
• Both concentration and percent Quarts for the appli-
cation of this limit are to be d*termln«J frora the fraction
passing a slti-selector wish the following characierisilcs:
• Coatalnlai < 1% qnarti; If > 1% qoarti, u» qnartz
Aerodynamic diameter
(nalt density sphere)
2
it
3.5
8.0
10
Percent passing
selector
SO
75
SO
25
0
Tbe raesscrsments under this note refer to the us* o
an AEC Instrument.Cr the respirabls fraction of coal
dost Is determined wllh a M HE the fijure eorrespondtnz
to that of 2.4 Mp/M< in the table for coal dust Is 4 5M#M«.
139 FR 23502. June 27, 1974. Redeslgnat«d
and amended at 40 PH 23073. May 23. 1975]
-------
EXHIBIT 3-2
ADDITIONAL TOXIC AND HAZARDOUS SUBSTANCES' REGULATED BY THE
OCCUPATIONAL SAFETY AND HEALTH! ADMINESTOATION
29. CFR Section
1910.10Q1
1910.. 10Q2
1910.
1910.
1910.
1910,
1910.
1910.
1910.
1910,
1910,
1910,
1910,
1910,
1910,
1910
1910
1003
1004
1QQ5
1006
1007
1008
1009
1010
1011
1012
1013
1014
1015
1016
1017
Material
Asbestos C8-hr avg. 2 flBers/cm , ceil-
ing 10 fibers/cm3I
Coal tar pitch, volatiles Cinterpretation
of terml
4 -N itr ob ipheny 1
alpha-Naphthylamine
4,4' Methylene bis C2-chloroaniline)
Methyl chloromethyl ether
3,3'-Dichlorobenzidine (and its saltsl
bis-Chloromethyl ether
beta-Naphthylamine
Benzidine
4-Aminodiphenyl
Ethyleneimine
beta-Propiolactone
2-Acetylaminofluorene
4-Dimethylaminobenzene
N-Nitrosodimethylamine
Vinyl chloride C8-hr avg. 1 ppm, 15-min
avg. 5 ppm)
3-14
-------
EXHIBIT 3-3
RELATIONSHIPS OF THRESHOLD LIMIT VALUES TO
SELECTED AMBIENT AIR QUALITY STANDARDS
Most Stringent TLV/
Ambient Ambient
Pollutant Standard TLV Standard
Beryllium 0.01 ug/m3 2 ug/m3 200
Mercury 1.0 ug/m 50 ug/m3 50
Nitrogen dioxide 0.05 ppm 5 ppm 100
Sulfur dioxide 0.03 ppm 5 ppm 167
Geometric mean 114
3-15
-------
EXHIBIT 3-4
CORRELATION BETWEEN THRESHOLD LIMIT VALUES AND LETHAL-DOSE 50'S
(5)
5
h-
^•^
a>
0
-1
-2
X
/
/ T
/
. x •:
/ 8,
x.-.**^^5
X> •*•**•£**
•
•2 •.
/
/ • .
/ rf>3
* m
/
/
/
/
/
» c4
/
/
A A
0
-------
EXHIBIT 3-5
KNOWN AND POTENTIAL CARCINOGENS
AS LISTED BY THE MARYLAND BUREAU OF AIR QUALITY
Known Carcinogens
2-Acetylamino Fluorene
4-Aminodipheny1
Arsenic
Arsenic Pentoxide
Arsenic Trioxide
Asbestos (all forms)
Auramine
Benzidine and its Salts
Beryl
Beryllium
Beryllium Oxide
Beryllium Sulfate
Calcium Arsenate
Calcium Arsenite (CaAsO3H)
N,N,-bis(2 Chloroethyl) 2-
Naphthylamine
bis-Chloromethyl Ether
3,3' - Dichlorobenzidine
4-Dimethylaminoazobenzene
Disodium Hydrogen Arsenate
Ethyleneimine
Methyl Chloromethyl Ether
alpha-Naphthylamine
beta-Naphthylamine
Nitrobiphenyl
Nitrosodimethylamine
Potassium Arsenate
Potassium Arsenite
beta-Propiolactone
Sodium Arsenate
Sodium Arsenite (NaAs02)
Vinyl Chloride Monomer
Potential Carcinogens
Benzene
Benzo (a) Pyrene
Bertrandite
Beryllium Zinc Silicate
Cadmium Oxide
Chromite
Chromium Oxide
Coal Tar Pitch
Pyrenes
Anthracenes
Phenanthrenes
Acridines
Benzpyrenes
Chrysene
Dimethyl Sulfate
Hydrazine
Lead Chromate
4,4' - Methylene-bis-
Chloroaniline
Nickel Carbonyl
Nickel Sulfide
Propane Sultone
Sodium Dichromate
Zinc Chromate
3-17
-------
EXHIBIT 3-6
ODOR DESCRIPTIONS AND THRESHOLDS FOR VARIOUS MATERIALS
Material
Acetaldehyde
Acetic acid
Acetic anhydride
Acetone
Acetophenone
Acrolein
Acrylic acid
Acrylonitrile
Allyl chloride
Allyl disulfide
Allyl mercaptan
Ammonia
Amyl acetate
(primary, mixed
isomers)
Amyl alcohol
Aniline
Apiole
Benzene
Benzyl chloride
Benzyl sulfide
Bromine
1,3-Butadiene
n-Butanol
2-Butanol
n-Butyl acetate
Butyl acetate (iso-
mers unspecified)
n-Butyl amine
Butyl cellosolve
Butyl cellosolve
acetate
C6,7,8)
Odor
Description
Green sweet,
oxidized
Sour
Chem . sweet, pungent
Burnt, sweet, pungent
Onion/garlic-
pungency
Fishy
Barn-like, pungent
Oily, solvent,
pungent
Solvent
Solvent
Cedary, sulfidy
Irritation, bleach
Odor
Threshold
(ppm)
0.21
1.0
0.36
100.0-320.
0.60
0.21-15.
1.04
21.4
0.47
0.0001
0.00005
0.037-46.8
0.21
1.0-10.
1.0
0.0063
4.68-60
0.047
0.0021
0.047
1.3
2.0-11.
0.56
7.
0.037
0.24
0.48
0.20
3-18
-------
.Material
n-Butyl chloride
Butylene oxide
n-Butyl ether
n-Butyl formate
Butyraldehyde
Butyric acid
Camphor
Carbitol acetate
Carbitol solvent
Carbon disulfide
Carbon tetrachloride
(chlorination of
CS2)
Carbon tetrachloride
(chlorination of
CH4)
Carbon tetrachloride
(source unspeci-
fied)
Cellosolve acetate
Cellosolve solvent
Chloral
Chlorine
Chlorobenzene (mono-
chlorobenzene)
p-Cresol
Cumene
Cyclohexanone
Diacetone alcohol
Diacetyl
Di-N-butyl amine
1,2-Dichloroethane
Dicyclopentadiene
Diethyl amine
Diethyl ethanolamine
Diethyl ketone
Diisobutyl carbinol
Diisobutyl ketone
Odor
Description
Sour
Vegetable sulfide
Sweet, pungent
Sweet, fruity
Pungent, bleach
Chlorinated, moth
balls
Tar-like, pungent
Odor
Threshold
(ppm)
16.7
0.71
0.47
17.
0.039
0.00028-
0.001
16.
0.263
1.10
0.21-7.7
21.4
100.0
200.
0.250
1.3
0.047
0.01-0.214
0.21
0.001
0.047
0.24
1.7
0.025
0.48
110.
0.20
0.06
0.04
9.
0.160
0.31
3-19
-------
.Material
Diisopropyl amine
Dimethyl acetamide
Dimethyl amine
Dimethyl ethanol-
araine
Dimethyl formamide
Dimethyl sulfide
1-4, Dioxane
Dioxane (isomerCsl
unspecified)
1-3, Dioxolane
Diphenyl ether (per-
fume grade)
Diphenyl sulfide
Di-N-propyl amine
Ethanol (synthetic)
Ethanol (source
unspecified)
2-Ethoxy-3,4-dihyro-
1,2-pyran
Ethyl acetate
Ethyl acrylate
Ethyl amine (10-12%
in water)
2-Ethyl butanol
Ethylene
Ethylene diamine
Ethylene dichloride
Ethylene glycol
Ethylene oxide
2-Ethyl hexanol
Ethyl hexyl acetate
2-Ethyl hexyl acry-
late
Ethylidene norbor-
nene
Ethyl mercaptan
Odor
Description
Amine, burnt, oily
Fishy
Fishy, floral, pun-
gent
Cooked vegetable
Odor
Threshold
Sweet, floral
Hot plastic, earthy
Earthy, sulfidy
0.85
46.8
0.047-6.
0.045
100.0
0.001-0.02
5.7
170.
128.0
0.1
0.0047
0.10
10.0
50.
0.60
13.2-50.
0.00036-
0.00047
0.83
0.77
700.
11.2
40.0
25.
500.
0.138
0.21
0.18
0.073
0.000016-
0.001
3-20
-------
Material
N-Ethyl rmorpholine
Ethyl selenide
Ethyl selenoraer-
captan
Ethyl sulfide
Formaldehyde
Glycol diacetate
Heptane
1-Hexanol
Hydrogen chloride
Hydrogen selenide
Hydrogen sulfide
(from Na2S)
Hydrogen sulfide
(source unspeci-
fied)
lodoform
lonone
Isobutanol
Isobutyl acetate
Isobutyl acrylate
Isobutyl cellosolve
Isobutyraldehyde
Isodecanol
Isopentanoic acid
(mixed isomers)
Isophorone
Isopropanol
Isopropyl acetate
Isopropyl araine
Isopropyl ether.
Mesityl oxide
Methanol
Methyl acetate
Methyl amine
(monomethlyl amine]
Methyl amyl acetate
Methyl amyl alcohol
Odor
Description
Hay/straw-like,
pungent
Pungent, burnt
Boiled eggs
Sweet r fruity
Fishy, pungent
Odor
Threshold
(ppm)
0.25
0.000052
0.00000018
0.00025
1.0
0.321
220.
0.09
10.0
3.
0.0047
0.00047-
0.0011
0.00037
0.000000059
2.05-40.
0.50-4.
0.012
0.191
0.236
0.042
0.026
0.54
28.2-40.
0.27-30.
0.95
0.053
0.051
53.3-5900.
200.
0.021
0.40
0.52
3-21
-------
JMaterial
2-Methyl butanol
Methyl cellosolve
Methyl cellosolve
acetate
Methyl chloride
Methylene chloride
Methylene glycol
Methyl ethanolamine
Methyl ethyl ketone
2-Methyl-5-ethyl
pyridine
Methyl formate
Methyl isoamyl
alcohol
Methyl isoamyl ketone
Methyl isobutyl
ketone
Methyl mercaptan
Methyl methacrylate
2-Methyl pentaldehyde
2-Methyl-l-pentanol
Methyl propyl ketone
a-Methyl styrene
Morpholine
Motor fuel
Nitrobenzene
Octane
Ozone
2,4-Pentanedione
n-Pentanol
Perchloroethylene
Phenol
Phosgene
Phosphine
2-Picoline
n-Propanol
Propionaldehyde
Propionic acid
Odor
Description
Sweet
Sweet, floral
Sulfidy, pungent
Pungent, sulfidy
Shoe polish, pun-
gent
Chlorinated
Medicinal, sweet
Hay-like
Oniony, mustard
Odor
Threshold
(ppm)
0.23
0.40
0.64
10.
150.-214.
60.
3.4
6.0-25.
0.010
2000.
0.20
0.070
0.28-8.
0.0011-
0.0021
0.21-0.34
0.136
0.082
8.
0.156
0.14
30.-800.
0.0047
150.
0.1
0.024
0.31
4.68
0.047-3.
1.0
0.021
0.46
0.13-30.
0.80
0.034
3-22
-------
-Material
n-Propyl acetate
Propylene
Propylene diamine
Propylene dichloride
Propylene oxide
Propyl mercaptan
Pyridine
Skatole
Styrene (inhabited)
Styrene (uninhibited)
Styrene (type unspec-
ified)
Styrene oxide
Sulfur dichloride
Sulfur dioxide
Tetrachloroethylene
Tetraethyl o-sili-
cate
Tetrahydrofuran
Toluene (from coke)
Toluene (from petro-
leum)
Toluene (source
unspecified)
Toluene diisocyanate
1,1,1-Trichloroethane
Trichloroethylene
Trichloromonofluoro-
methane (Ucon-11)
Trichlorotrifluoro-
ethane (Ucon-113
solvent)
Triethyl amine
Trimethyl amine
Odor
Description
Burnt, pungent,
diamine
Solventy, rubbery
Solventy, rubbery,
plasticky
Sulfidy
Oppressive
Floral, pungent,
solventy
Moth balls, rub-
bery
Medicated bandage,
pungent
Solventy
Fishy, pungent
Odor
Threshold
(ppjnl
0.15-20.
67.6
0.067
0.60
35.0
0.000075
0.012-0.021
0.000000075
0.1
0.047
0.15
0.40
0.001
0.47-30
50.
7.2
30.
4.68
2.14
1.74-40.
2.14
400.
2.14-250.
209.0
135.0
0.28
0.00021-4
3-23
-------
Odor
Odor Threshold
JMaterial Description
Trinitro-tert-butyl O.OQQ00042
xylene Csynthetic
musk)
Valeric acid O.Q0062
Vanillin 0.000000032
Vinyl acetate 0.55
p-Xylene Sweet, moth, balls- 0.47
Xylene (isomerCs)
unspecified) 0.27-20.
3-24
-------
CHAPTER 4
EMISSION SOURCES
Since all air pollutants can be divided into
two categories, gases and participates, one must
consider two types of potential atmospheric emis-
sions. Gaseous emissions normally result from
the evaporation of liquid materials orr less fre-
quently encountered, the sublimation (change to
the gaseous state without first passing through
the liquid state) of solid materials. The rate
of evolution of such emissions is almost always
highly dependent on the volatility of the material
under consideration.
The vapor pressures of a large number of
organic materials are presented as a function
of temperature in Exhibit 4-1, and similar data
for inorganic materials are presented in Exhibit
4-2 (9). In order to use these exhibits to determine
a material's vapor pressure (in millimeters of
mercury), the temperature of the material (in
degrees Centigrade) must be located on the line
on which the material's name appears. At the
top of the column in which the temperature is
listed, the vapor pressure is indicated. Interpo-
lation and extrapolation may be employed as needed;
for accurate results, the listed data should be
used to plot a smooth vapor pressure-versus-
temperature curve, from which the vapor pressure
at any temperature can be read. For cases in
which the chemical of concern is not listed in
the vapor pressure tables, the vapor pressures
of chemicals having similar molecular weights
and structures should be checked. (As noted pre-
viously, molecular weights and structures can
be determined by using either the organic or
inorganic tables of chemical properties that
can be found in the CRC "Handbook of Chemistry
and Physics.")
4-1
-------
For example, consider the case of benzyl
chloride, a toxic substance that has a Threshold
Limit Value (TLVJ of 1 part per million Cppml,
to be present at a temperature of 70 degrees
Fahrenheit, which is equivalent to C70-32J/1.8,
or 21.1 degrees Centigrade (°C)~, and under normal
atmospheric pressure C760 millimeters of mercury).
The closest temperature to this on the line labeled
benzyl chloride in Exhibit 4-1 is 22.0°C, which.
is located in the first vapor pressure column on
the left, the column headed 1 millimeter of mercury
(mm Hg). Since the actual temperature of 21.1°C
is slightly below the listed temperature of 22.0°Cf
the actual vapor pressure is slightly less than
1 mm Hg. The equilibrium benzyl chloride concentra-
tion above the liquid phase would therefore be
just under 1 mm Hg/760 mm Hg, 0.13 percent, or
1300 ppm.
Such a concentration would require efficient
containment, emission control (for example, by
activated carbon adsorption or thermal incineration -
see the following chapter for details), or atmos-
pheric dilution by a factor of well over three
orders of magnitude before it could be safely
inhaled for a significant period of time. Such
degrees of dilution are in fact ordinarily obtained
in cases of elevated release locations; however,
it should also be recalled that ambient levels
should typically be kept far below TLV concentra-
tions . (The methods that can be used to evaluate a
situation's potential for toxic air pollution problems
are summarized in Exhibit 8-12).
Repeating the above calculation for a somewhat
different case, in which the benzyl chloride is
maintained under a pressure of 30 pounds per
square inch gauge (psig), i.e., above the atmospheric
pressure of about 14.7 psi, which is the same
as 30 + 14.7 or 44.7 pounds per square inch absolute
(psia), or 3.04 atmospheres (atm), or 2310 mm Hg,
the equilibrium pollutant concentration would be
reduced to 1 mm Hg/2310 mm Hg, 0.043 percent, or
430 ppm. On the other hand, if the benzyl chloride
4-2
-------
were to be kept under 3 10 psi vacuum (below the
atmospheric pressure of 14.7 psi), which, is the
same as 4.7 psia, 0.32 atmospheres, or 243 mm Hg,
the equilibrium pollutant concentration would be
increased to 1 mm Hg/243 mm Hg, 0.41 percent, or
4100 ppm.
The above example calculations should serve
to provide the toxic substance air pollution inspec-
tor with an indication of how to estimate emitted
concentrations. (When mixtures of chemicals are
involved, somewhat more complex calculations may
be required, based on various approximate relation-
ships, such as Raoult's Law, that are described
in detail in physical chemistry textbooks.)
One additional example will be presented
to show how mass emission rates, rather than just
emitted concentrations, may be estimated. Suppose
a 1500-gallon, or 200-cubic foot, vessel at atmos-
pheric pressure that is almost empty but is saturated
with benzyl chloride vapor is to be refilled with
the chemical within a ten-minute period. At the
0.13 percent equilibrium concentration calculated
above, the vessel's benzyl chloride vapor of 200
x 0.13% or 0.26 cubic feet, or (.from the ideal
gas law) 0.085 pounds, will be displaced during
the operation, at an average rate of 0.085/10
or 0.0085 pounds per minute. (If this seems to
be a low emission rate, one might consider that
the dilution air that would be required to reduce
0.0085 pounds per minute of benzyl chloride to
its 1 ppm TLV amounts to 26,000 cubic feet per
minute.)
A final general point that should be made
regarding evaporative emission estimations is
that, depending on the process situation, it
may often be more appropriate to assume that
considerably less than the equilibrium pollutant
concentrations may be present, especially when
the time element is small and the degree of mixing
is low. A method for estimating storage tank
4-3
-------
evaporative emissions based on vapor pressure data
is presented as Exhibit 4-3, which, has been repro-
duced from EPA Publication Number AP-42, "Compilation
of Air Pollutant Emission Factors" (TOI. For fixed-
roof petrochemical storage tanks, conservatively
assuming the number of turnovers Cthe ratio of
annual throughput to tank capacity) to be
no greater than 36 per year, the evaporative emis-
sion formulae can reduced to the expression:
E = MP CO.0104 D1'73 H°*51 AT°*5° FpC +
0".000024 G)
where:
E = evaporative emission rate (Ib/yr)
M = molecular weight of petrochemical (Ib/mole)
P = true vapor pressure of petrochemical at
bulk liquid storage temperature (psia)
D = diameter of storage tank (ft)
I*.
H = average vapor space height (typically half I
of storage tank height, and including a I
correction for concave roof volume) (ft)
AT = average daily ambient temperature change,
maximum minus minimum (typically about 20°F)
F = paint factor, ranging from 1.00 for tanks
whose roofs and shells are coated with
white paint in good condition, to 1.58 for
medium-gray painted tanks in poor condition
(see Exhibit 4-3)
C = correction factor for tanks with diameters
of less than 30 feet, approximately equal
to D/20 - D4/l,600,000 (see Exhibit 4-3)
G = annual throughput of petrochemical (gal/yr)
4-4
-------
The first term enclosed within the parentheses
is needed to calculate the standing storage (breath--
ing) loss, while the second term is needed to calcu-
late the working Cfilling and emptying 1 loss-.
Other potentional sources of evaporative emis-
sions of toxic substances include such chemical
process equipment as reactor vessels, distillation
columns, pumps, and compressors. Pollutant release
points include stacks, vents, ejectors, and leaking
ducts and pipes, and such occurrences as overflows
and spills must also be considered. In addition,
wastewater streams and solid waste accumulations
should not be overlooked as possible sources of
toxic evaporative emissions to the atmosphere,
and treatment processes may actually result in
increased releases of certain chemicals into the
air. Such processes may often include the incinera-
tion of liquid or solid industrial waste materials.
Particulate emissions are ordinarily the
result of the small particles present in
a finely-divided (granular or powdered) solid
material becoming airborne, or sometimes of very
small droplets being entrained in an air stream
flowing through a quantity of liquid, or over
a liquid surface, or simply past a point where
liquid splashing, spraying, or atomization (as
at a high-pressure nozzle) occurs. (In cases where
particulates are created by the condensation, re-
action, or other transformation of gaseous pollu-
tants , evaporative or other gaseous emission for-
mation mechanisms are usually responsible.)
Just as gaseous emissions are most often
attributable to the volatility of substances, parti-
culate emissions are usually related to the degree
to which materials are present in finely-divided
form. This is due to the fact that coarser parti-
cles are much less likely to become and remain
airborne. For example, 100-micrometer (or 0.1
mm) diameter particles settle to the ground so
quickly that they are usually transported beyond
4-5
-------
plant boundaries in significant quantities only
in cases involving high, initial release elevations
and/or high, wind speeds. Intermediate-sized parti-
cles/ which, have diameters of about 10 micrometers
Cor 0.01 mm) and are extremely- difficult to distin-
guish, as individual particles with, the naked eye,
are much, more readily transported by the air over
considerable distances. Very small particles,
which have diameters of about 1 micrometer CO.001
mm) and are very difficult to see even with- the
aid of an optical microscope because their sizes
approximate the wave-length of light, behave in
many respects like gaseous molecules and have
no significant tendency to undergo gravitational
settling.
The percentage of small particles (those with,
diameters of less than a specified value) present
in a finely-divided material which have the
potential to become airborne may be determined
based on a knowledge of the particle size distri-
bution of the material. In air pollution work,
the distribution most often encountered is the
log-normal type, within which the logarithm of
the particle diameter is distributed normally (ac-
cording to the error function, or the standard
bell curve) with respect to the mass of particles.
For example, if one considers a granular material
having a log-normal size distribution that is
characterized by a mass median diameter of 100
micrometers and a geometric standard deviation
of 2.5, it is known by definition that 68 percent
of the mass of particles is between 100/2.5 and
100 x 2.5, or 40 micrometers and 250 micrometers,
in diameter, while 16 percent of the mass is below
40 micrometers in diameter and the remaining 16
percent is above 250 micrometers in diameter.
Through the utilization of graphical techniques
or tabular data, the percentage of the mass of
a finely-divided material below any size (chosen
because of its likelihood of becoming airborne
and being transported to the plant boundary or
to a potentially sensitive or adversely affected
receptor location) can be readily determined;
4-6
-------
however, all of the particles, below such, a size
may not actually be emitted, and in .most cases
only a small fraction of them will Be released,
depending on the degree to which, the finely-divided
material is exposed to the air, especially air
in motion.
For some types of operations in which, particu-
late emissions may be generated, emission rates
may be estimated based on the data presented in
EPA Publication Number AP-42, "Compilation of Air
Pollutant Emission Factors." In cases where the
source operation involved is not listed in AP-42,
emission factors for similar operations may be
considered for use, keeping in mind that the
size distributions of the finely-divided process
materials involved and their degrees of exposure
to the air and its motion should be comparable.
In the case of a solid material, its degree of
dryness, dampness or stickiness may be highly
significant. Since toxic substances may constitute
only a fraction of the total emitted particulate
matter, the composition of the finely-divided pro-
cess material should be taken into account, including
any systematic difference between the total and
the toxic particle size distributions that may
exist. Operations that may result in toxic sub-
stance particulate emissions include atomizing,
blending, charging, conveying, crushing, cutting,
drilling, mixing, packing, pulverizing, spraying,
and others.
In the estimation of emission rates of poten-
tially toxic materials, it may often be necessary
to consider the differences in the weights of
alternative chemical forms. For example, consider
a process in which 4 pounds per day of vanadium
Catomic symbol V, atomic weight 51) is converted
to vanadium pentoxide fumes (molecular formula
V2°5/ molecular weight 51 x 2 + 16 x 5, or 182)
and subsequently released to the atmosphere.
Since the V205 has a mass of 182/C51 x 2), or 1.75,
times the mass of the vanadium it contains, the
4-7
-------
emission rate of 3^05 would be 4 .x 1.75, or 7,
pounds per day. Ambient concentrations calculated
from this emission rate could then be compared
directly to the V^Og fume TLV of 5Q ug/m3. It
should be noted that in the cases of many toxic
chemicals no such calculations would be required;
for example, for the oxidation and emission of
selenium, the increase in weight need not be
calculated for the purpose of an ambient concentra-
tion evaluation, since the TLV for selenium com-
pounds is 200 ug/m3 expressed as the weight of
selenium only (not including the weight of oxygen
or other atoms compounded with the selenium).
This concludes the chapter on the types of
toxic substance emissions that can be expected
from the various sources, and on how these emis-
sions may be estimated.
4-8
-------
EXHIBIT 4-1
VAPOR PRESSURES OF ORGANIC MATERIALS (9).
Compound
Name
Atrnapbtbalflw. , . . , , .
Acctal
Antaldcbyd*. 1
AceUuUd*
AceloiM
AcvUxutrila
ArrtV) rhkrid*. . 1LJIt ± f.,..i
AoetyleiM .
A"7'"? »rkL.... .,„. , ltl...
Mime 'jrrradMWi) , , ,,..,..„,, ^., ,
Aiiyi »£abol (prof»-iK)i-3)
ehtorid* (3-eMcropwpeae)
4-AUyiTwfrdb.
*- Aaiyf alooboi.
iso-Ajajl mleohol . . „
•ec-Axiyl akohul (2-*M>UnoJ) . .
twi-Amrl »lwAfll_ , ,.
broaudc (Wroow^HnetbylbotMie)
n-butyr»4«...,
iodida (l-wotrichk>rkI«fczf£Mx-rr]rich]oro(otaen«)......
B«a»oji bcorajd»
Beastf acettt*
•loobol
B^nsyMicMrtpfwilArm , , ..,,.,,,
Beiayl ethyl ether
Bipbenyl
d-Bornyl acetate ..'..". .' .,
Bomyl n-btitjrat»......
formate ;....
fcobotyrsU
proptcnato
Brasndic aod
BrocDoacctie acid
4-BromowjaoJe
Formal*
CuHu
C«H,.O,
C-B&
dHjJJO
C«EJiO
C.H.O,
c^aoi
C»H«O
CtHJJ
C,£U>
C-JtrOa
C=Hi
CuH,N
C,H<0
C^O,
CXHaOt
CJB«
GEUO
CaHsQ
CJHM)
C
OrBbNO
CiiEii
C,.
CiH«0.
CVHuO
Ci^BjoKi
CrHsCli
CrHrf)
CuEuO
C
309.8
197.5
222.2
190.2
218.
211.2
359.6
165.7
197.5
277.5
102.2
20.2
222.0
303. S
118.1
139.6
56.5
81.8
202.4
50.«
-84.0
34A.O
52.5
141.0
337.J
-35.0
96.6
44.6
79.3
150.7
90.5
248.0
142.0
137.8
130.6
119.7
101.7
193.0
262.0
120 '
178.6
1233
148.2
168.8
160.2
194.0
253.2
247.9
1475
266.0
235.31
140.0
184.4
279.6
248.0
218.5
342.0
379 9
356.5
185.0
293.0
214.0
179.0
80. 1
251.5
347.0
249.2
360.0
343.0
190.6
305.'
213.5
102.2
218.5
197.2
203.0
213'5
204 7
IS4.5
179.4
350.0
194.3
185.0
287.0
243.0
254.9
3400
223.0
247.0
2140
2«j
235.0
382.
208.0
223 0
Mdt-
m«
pogW
95
-I23.S
81
113.5
16.7
IS.6
—41
20.5
-112.0
-81.5
110.5
-87.7
14
152
-136
-129
-136.4
-80
-117.2
-«.»
93
22.5
-6.2
2.5
5.2
217.5
236
106.5
£8
-16.1
-26
174
+5.5
14.5
95
121.7
42
132
-12.9
48. S
-21.2
-29.3
0
-0.5
33.5
-51.5
-15.3
-4
-39
39
69.5
29
61.5
49.5
12.5
• Compiled from the extended Ubles pubUsi-jd by D. R. Stn3 in Ind. Eny. Cltm.. S3, 5)7 (1947).- For information on fuefa ta» EibbwL KJLCjL Rtxank
Km. E56I21. 1956. For methane am Johiaoo (ed.), WADI>-TIWO-56.1960.
-------
Cbcpouad
Nam.
l-Brooo-4-ethyl beein*
(2-B.-omoethyl)-bwu»o»
2-Bromorthyl 2-chlcrtMtlijl atbtf.
2-Bratn»4^)beD7iplunai.
2^Brono»l 4«iyl«<** *
l,2-Butadim*(nuiMaJim)
13-ButadUcw.'.
1,3-Bntansiol. '.
1,7.3-Bntmtriol. ,.,,,, ,, ... ......
t-Butrae
alcohol
uo-Butyl alcohol
tert-Bnttrl alcohol.
tart-Butylbecstns
n-Butyibroarid0(1-bromobtit3D0)
iso-Batyl n-butyrkto
Butyl csrbitol (diethyfero glyed butyl ethw). ...
n-Bctyl chloride (l-chlorabutaiu)
iso-Butyl chloride ........
lee-Butyl cHorida (2-ChIorobatam)
tert-Butyl chloride
2-tgt-Bntyl.4<«jol
4-tert-Butyl-2-craol
Sso-Butyl dichlaraseetat*
2,3-Butylw« glycol (23-batanedioQ
2-Butyl.2-eUiylbni3n«.|,3-diol
2-tert-Butri-4-«thjipbMol
iso-Batyl forest*
Bee-Butyl format*. ......... .
SK-Butyl glyeoIaU
naphthyUnten* (1-Bcrnlenmphthoro)
2-eec-But?lph«nol
2-tert-Baty1ph«eol.
i^4"lsrtJi\i1:»tah»oor^Bllr7l acftbta
tert-BntyTpfiesTl ketoo* (p"iraloph«one)
4-tert-Butyl-2.6-iyl«ol
6-tert*Butyl-2,4-iylenol .
6-i«rt-Butyl-3t4-xyl«aol
Butyric acid
Formola
CsHsBf
CtfiiBf
JiBVBrO
:,HrBr
C.HrBr
CiHjBr
CdJrBr
:,BYBr
iHiBrCl
J-HtBrCl
CiHiBrCliO
l&Bc
iiHjBrClO
CsHiiBr
JiBiBr
CHBn
JiaHiBr
Ju-HiBrO
j'aBr
Ci&BrCbO
CjEiBr
C«S»
CvH.
CiHu
3iHi»
:«HuOi
3iH*
SiEbOj
CiSvoO
C
-108
-114.7
25.3
-85.0
-S3.0
-51.5
-75.5
-58
-112.4
65
-123.1
-131.2
-131.3
—25.5
22.3
-95.3
-90.7
-80.7
99
-71
-74
-------
Compound
Nam*
Canrtidthyd*.
Cnrlmifllfi ,, ...
Cvbon (iiocodf .
donlfida
nonaxidit
t^tnbctrinidc
tftrr^hJcrida
ChiVibetol
faydr»to (trtchlflro*mtaJdetoriahyd:ratft)
3-CUorauulinB
2-CbIonbauotncfakrid« (2-o^a-Utrschlcro-
tolucse)
2*ChkffroasaotnflaorM» (Z-chkrtMXrCMr-in&w
2-Cyorebipbeiyi ,
4-Chlorobi phenol
l-Chloro-2-cthcctybenieoe
2-{2-CbJQroeihaxy) ethauaot
bis-2-Cblopocthyl aceUcetal
l-ChIoro»2'«thylbeQ)en«.
1-CbJoro-4-*tiijlbenMi»
1 -CMfTtJmpb tiaJftwi
4-Chloroph*«tiyl alccfcoL
2-Cfaloropbeool
3«Chloropb«Bol
4-ChloropWo! ,
2-Chloro-Vpbenybhraol.
2-Chkro^j&enylpb«ncl
^-ChJ orcstyrw*
4-Cblorcat7T»n«. . . ... .
2-C£]crctol o*o«
3-ChIorotolueaa
Colorotri HhTiailazM
j Oi'r»v>ti'^J
O.trctwiiio acid.
Citrooeijoi
Cocmarin
Fomabk
CiHjO»
CuHiiO
ICioHu
CioHicOi
CicHiiO
CioHiiN
C...JTW1
Ctc£boOa
C«BuO>
CiHieOa
CsHuN
CsHiiO
CiEuOi
CuHaN
CO,
CS,
CO
COS*
C03
CBn
ecu
CF«
CuHiiO
CioHnO
CjHCM)
C«C1 Qi
CiEiClO,
C6H.C1N
CtHaCIN
CtHsCl
c,acu
C-H.CF,
Pi-H,ri
CuHsCl
CiHsGO,
CEC1F:
CsKjClO
CeHo-CbOi
C.HjCl
CsHiCl
CsHaCl
CsHioCW)
CsHwCl-O
CioHtiQO
CHCU
CioBjCl
CJEUCIO
GBiClO
CsHiCIO
c^aao
CCUNOi
CiEsCl
f* .pr^-n
CsHrCl
C tH?«Cl
C-HrCl
C-HTCI
CsHisClS
CjClFi
CC1P1
^vrqrrt
C^KisO
CsHsO
CioHitO
CiaSuO
CioHuOi
C'*H— Oi
C.H.O!
i
14.7
—200
58.3
97 6
41 5
45.3
51.9
125.0
71.4
66.2
38.3
9.2
32.8
73.4
92.3
43.0
—134.3
—73.8
—7770
— 117.1
—132.4
—50.0
—184 6t
70.0
57.4
83 6
-37.8
—9.8i
70.3
43.0
67.2
46.3
63.5
59.3
-13.0
69.0
0 0
89. J
96.4
70.0
—122.8
29.8
45.8
53.0
56.2
17.2
18.6
19 2
46 0
24.7
29 8
623
-58.0
80.6
84.0
12 1
44 2
49 6
118 0
119.8
—25 5
—81 3
13 3
25 3
28 0
98 5
j j'p
! r *
- j'n
—116 0
—149 5
—62 8
127 5
72 6
76 1
47 1
61 7
44 0
99 5
66 4
74 7
106.0
5 |
39.31
+2 1
87. 0
125 7
63 6
74 0
78.8
142.0
89.5
£3 0
66.4
34.6
57.6
92 0
114.1
67.6
-124.4
—54.3
—217.2
— 102.3
-119.8
— 30. C
—174 1
98.4
66. 1
113 3
-16.0
+10. C
89.3
63.3
94.1
72.3
89. S
87. S
+10.6
101.8
24 7
109.81
12J.8
95.6,
-no 2
56 ;
72.8
7S.3
83.7
43.0
45.2
46 4
72 1
50.1
56 5
91 4
-39.1
104.8
114.3
38.2
72 0
78.2
152.?
153.7
—3 3
—63.4
33.8
51.3
54 5
131 8|
30 6
30 3
31 0
+19 8
— 102 5
— 139 2
—43 6
157 8
102 5
105 8
74 i
90 0
71 4
127 3,
93 6
100 2
137.8
10 1
51 2
13.4
101.4
47 2
139 8
82 3
O 7
92.0
152.2
99.5
940
80.3
47.5
70.0
101.2
124.0
£0.4
— 119.5
—44.7
—2150
-95.0
-113.3
—196
—169 3
113 2
100.4
127 0
-5.0
19 5
97.8
81 0
1030
84.8
102.0
102.1
22.2
117.9
37 1
134.7
146.0
103.0
-103.7
70.0
S6.5
90.7
97.6
56.1
53.1
60 0
860
63.0
70 0
1060
-29.7
118.6
129.0
51 2
86 1
92 2
169 7
170.7
+7 8
—54 1
51 7
65 2
67 5
143 2
43 2
43 2
43 8
32 0
—95 9
— 134 1
—34 0
173 0
117 8
120 0
83 9
103 9
84 &
141 4
107 0
113 0
153.4
20 1
640
25.7
116.8
60 4
153 9
97 5
976
106.3
165.0
111.8
107.0
95.7
61.7
83.3
110.2
136.4
94.6
-114.4
-34.3
—212.8
-86.3
—106.0
-8.;
—164.3
127.S
116.1
143.2
29.;
106. t
94.2
122.4
99.2
116.7
117.!
35.3
135.8
50 6
151.2
164.0
121.2
-96.5
84.7
101.5
104.1
112.2
70.3
73.0
75.5
100 0
77.2
£4.8
121.8
-19.0
134.4
145.0
65.9
101.7
108 1
186 7
189 8
20 0
—440
65.8
80 0
82 0
166 2
56 9
57 4
57 8
45 5
— 88 2
—123 5
—23 2
139 5
133 7
135 7
103 8
119 4
99 8
155 6
121 5
1Z6 0
170 0
Pmsura,
40 |
reaper*!
77.8,
38.4
133.8
757
170 0
114 0
112 5
122.2
179.9
125.0
120.4
112.3
76.9
98.0
120.0
150.6
110.6
— 1C3.6
—22.5
—210.0
—76.4
-98.3
96.3
+4.3
—1588
145.2
133.0
159.8
20.2
393
116.1
109.2
138.2
115.6
133.6
I35.C
49.7
155.0
659
169.9
183.8
135.6.
-88.6
101.2
117.8
113.4
127.8
86.2
89.;
91 8
116.0
92.4
101.5
139.61
-7.1
153.;
162.0
82 0
118.0
125.0
207.4
208.2
33 &
—32.7
81.7
96.5
93 0
187 0
72 0
73 0
73 5
60 2
— 79.71
—121 9
—11 4
207 1
151 0
152 2
120 3
135 9
116 1
171 9
137 2
140 5
189.0
m^_ frt»
60 I
hire. M
86.3
47.3
144.6
850
180.0
1240
122.0
132.0
189.8
133.3
129.6
123.2
86.8
107.4
I26.C
160.0
121.2
243.2
—104.8
—15.3
—208.1
—70.2
— 93.C
106.3
12.3
—1554
155.3
143.8
1707
29.1
463
122 C
1183
143.0
125.7
144.1
145 i
58.3
167.8
754
132.1
196.0
144.4
-13.4
111.5
127.8
127.5
138.0
96.
—201.3
—49.8
-75.0
139.7
38.3
—1436
191.2
179.6
206 i
57.8
630
140 3
149 0
177.8
160.0
179.5
182.3
89.^
208.0
108 3
219.6!
337.8
173.8,
—65.8,
145.5
162.0
157.2
169.6
130.2
133.8,
137 0
159.8
135.7
146 3
186:31
25'.9
204.'2
210.0
126>
164.-8
172.0
261.3
261 16
71.8
+1.3
125.0
142:;
143 5
240.3
115 0
116 6
117 1
101 6
—55.0
—102 5
21 9
253 3
199 &
199 3
165 8
181 t
160 0
214 5
179 8
173 8
240.0
400
134.5
96.6
204.2
138.7
234.0
132.0
173.8
186.3
240.3
131.0
181 .C
132.1
I4I.C
157.5
156.5
213.S
179.5,
323.0
-85.3
28.C
-196.3
-35.6!
—62.3
163.5,
57.8
—135 5
213.8
203.5
229 8
77.5
82 1
151 3
169 0
197 0
183.7
203.5
206.6
110.0
233.0
130 0
243.8
264.5
193.2
—53.6
163.6
185.5
176.5
190.5
152.2
156.7
159 8
182.2
156.5
169.8
210 8
42.7
230.8
234.5
149.8
188.7
196 0
289.4
289.5
91 8
is:o
147.7
165.7
166 0
267.5
137 1
139 7
139 8
123 6
—41 7
—92 7
39 4
276 7
224 6
7" 4
169 8
205 0
183 8
236 6
201 0
197 8
264.7
760
154.5
117.5
228.0
160.5
256.0
209.2
195.0
208.5
268. 4
232.C
207.7
207.C
163.7
173.5
168.5
237.5
204.5
354.1
—78.;
46.5
-191.3
-21 .'.
-49.'.
189.5
76.i
—127 ;
237.0
227.5
254 0
97.7
96 :
162.6
189 5
217 0
208.8
228.5
230.5
132.2
262.1
152 2
267.5
292.9
212.0
—40.8
193.5
203.0
196.0
212.6
177.6
181.
184 3
205 0
180.0
194.1
235 0
61.3
259.3
259.)
174.5
214.0
220 0
317 5
317.8
111 9
37 0
170 2
190 0
191 0
296 0
159 3
162 3
162-3
146 3
—27 9
—81 2
57 9
300 0
250 0
246 0
213 5
22S 0
20n 5
257 C
221 5
217 0
29l'fl
MeJU
ni
"•C.
-47
50
178.5
31.5
-1.5
-35
-33.6
16
244.8
-57.5
—110.8
-205.0
—138.8
90.1
—22.6
—183 7
+0.5
—57
51 7
290
61.2
46
0
—10.4
70.5
—45.1
28.7
—6 0
M
75.5
—160
—80.2
—53.3
—62 6
—63.5
—20
7
32 5
42
+6
—64
—99 0
—15 0
+0 9
4-7 -I
—157 5
33
7 5
70
-------
Coapooad
Forma]*
dl-L_
E«o-i3-Dibron!obn!w>»..
1,2-DibromwUeso*
Di(2-brom<»tM) ether..
13-Dibroo»-2-m*thyll*flj!«D«..
l,2-Dibromop«oUn9
1,2-DifaromoproFw*.
13-DibroEiopro>p»o».
2i3-Dibroaio$rep«!«
23-Ditromo-l-fn>p»Dol
DibobutTiaming
2,6-Ditert-butjrM-craol.
4.6-ISl«rt-baty!-3.crwot.
Kbobatyl cml»i»..
iibntyi
milEde"
DiuobutyTd^larlnta.
Ihchloravcetio wad..
I,2-Dichlorob*»«»..
1,4-Dichlort*«*s»..
1,2-UicMorwmtao*...
Dkhloroiifeorwae'.iaM
D'chlomdiplanyl jilac«
Di^hlorodiaotirejiTl t&rr....
Di(2^41cr«tho^) net'nan*.,
Dichlon>!»boiynettylfllaa»..
l,2-Dichlon>3-eOi7ib«M-«..
l,2~B'.cMor>4-5''c7ro»a3i*nB..
o-Oool (2-cra>ol: 2-nwt^ylphw.aO. C;3/)
p^>-«l(4ol) CiH.0
cia-Crotoaic acid -.• CiH^Ox
truu-Crotomc uid. CiBliol CwHaO
DecrltrimttlirfeilMM. CuHnSi
DshydrwertM Mid. CsHiOt
DaozybmMia. CiiHuO
DiaceUmida C«H7>"
~ CiHa
CvHuCljSi
CtHiaS
Diiaiunyl rtiw CioHaQ
5uj£d» ....!..!.,...... CuBS
DibtmriamiM CiiHuN
1,4-D:bromol»o»M>«..
CjHJBr,
CiHJBn
CiorlsBn
CiHiBriO
C.H:Br:0,
CiHsBn
CsHicBn
CiHjBn
CjH
-------
fteerore* ^^* Bg
T3ET
Sag
point,
•C.
' I 5 I 10 I 20 I 40 | 60 I 100 I 200 1 400 | 760
Nun.
Formula
76 0,
-58.6
79.0
92.4
14.6
13.7
44.8
107.7
115.5
113.8
133.1
+6.0
120.5
111.8
114.0
105.5
116.2
111.8
172.5
162.0
-63.5
97.8
67.3
62.0
25.3
174.3
138.3
-22.6
107.2
88.0
76.'
74.5
74.7
36.1
118.2
125. S
148.0
212.0
63.0
100.
—38 '
106!
110.2
125.4
213.
lll.l
27.
141.
115.
95.'
120.
96.
173.
189.
103.
111.
94.
102.
+3.
59.
164.
163.
90.
24.
106.
115.
282.
—42.
-56
84.
65
160.
-31.
—24.
106
23.
31.
25.
27.
23.
27.
22.
-85.
15.
22.
17
17
Temperature, ^CL
TsTbT
-20.9
133.3
155.5
65.8
68.9
96.1
165.2
175.5
176.2
202.8
57.0
185.7
176.0
178.0
169.0
181.
176.0
245.6
238.5
-26.3
153.5
129.(
121.8
74.2
243.1
198.;
21.1
168.2
141.9
136.7
134.
136.1
86.5
182.3
188.0
207.0
271.5
118.0
159.0
+2.2
166.0
172.2
189.
292,
177.
7o.e
205.
177.1
155.
IS.
147.'
243.)
255.
173.
171.
155.
162.
51.
115.
230.
230
152.
77.
171.
163.
377.
146!
119.
229.
DtchloroflooromeUiaaa..
1,5-Dichlorcbcxuaet]
JjiclUoromeUiylpbeoybUi
l.l-Dicblaro-i-mrthyltropftoe.
l4-Dichloro-2.metij]prop»n»..
OHiCL-0
CHCU
CtHiiCKhSif
CrHjCUSi
CiHsCli
Z4-l>ichlorophenoi..
2.6-DKhkropbenal
a^p-DieUaraplwayUeetaaitrile..
DiehJorrpheny'iarsDe.
1,2-Diehloropropao*
2>DxilorcBtyreo«.
Z4-Dieh>orostyren«
CiHiCli
&H.CL-0
C.H>AaCli
CiHiCb
CiHtCb
2,6-Diehlaratyrene.
3.4-DichloratyniM.
3,5-Diehlcrortyren«
I^DicblorotelneUrsIbeniem.
l,4-Dicl>lorotetn-cMvi-triihlOtSi
CioHuOi
C*3uN
CitHuN
CioHuAaNOi
ioHu
CioHu
CioHii
iHioOi
CiHuQt
etaie
CtHinOi
C«HuOft
gjycof ethyl ether CeHiiOi
Diethyl ether CxHnO
ethylnaloBiU
tonirsto ,
glutarate ,
T}i»tkylfi^TTM3»*yl!»minDicMthylbnta&e. CsHu
Z3-Dim*thylboUn« CtHu
Pioethyi atrueruta --
1,1-Dunethyicydoheiaae CiHii
ea-I,2-Dim«tiylcydohexan« CsHu
erai»-1,2-Kmethyleycloh«ian« CsHu
caia-I.J-DimetbylCTcloheDiae CsHu
eu-l^-Dimethylcydohcrane CsHu
ca-l,4-DuDethykydohean»...,
Dimethyl ether
Z2-Dittethylh«au>'» CsHu
23-Dimethylh«t»o« CiHu
2,4~DicD^thylhuADo
-'"• "•• " : GBi
B.5.
-91.3
26.0
35.7
-31.0
-25.8
-3.0
53.0
59.5
56.0
61.8
-33.5
61.0
53.5
55.5
47.8
57.
53.5
105.6
91.7
-95.4
46.
11.0
-19". 1
111.5
74.0
49.3
49.
38.0
22.:
20.7
2or
-10.1
59.8
70.0
91.
148.3
13.0
45.3
-74.
50.
53.2
65.6
139.S
51.
-12.
80.
57.3
40.0
62.
47.4
103.
125.
49.
54.
39.
47.
-39.
10.
102.
100.
34.
—22.
46.
68.
196.
-73.
—87.
29
15.
96.
—69.
-63.
50.
-24.
-15.
-21.
-19.
-22
-20.
-24.
-115.
-29.
-23.
-26.
-25
-8.4
-4.2
+20.6
80.0
87.6
840
100.0
-17.0
90.1
82.2
83.9
75.7
86.0
82.2
138.7
126.1
-80.0
71.3
38.3
34.1
&8I
106.6
78.0
62.6
48..
46.8
47.1
+12.3
88.?
93.0
120.0
180.0
37.6
72.0
-56.
77.
81.2
94.
175.8
60.2J
+7.5
110.4
85.6
67.5
91.0
71.8
140,7
156.2
78.4
83.0
66.7
74.0
-18.6
34.
1330
131.7
61.5
0.0
75.5
91.7
239.8
—57.9
—72.
56.3
39.6
123.3
—50
—44.
?a.
— 1.4
tfi
62.0
-67.5
65.1
77.4
+26
+6.7
32.0
92.8
101.0
98.1
116.0
-6.1
104.6
97.4
98.2
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Coapouad
Pmsan,"""- Hs
Nam,
Formula
'1*1
10
| 20 I 40 | 60 I 100 I 200 | 400 | 760
Temperature *C-
pjgt.
3,3-Dinethyihnaat CsHu
3,4-D:!£*thylhuaa« CjHuN
N,N-Du3
Et-n-propyl snceioAta CioHuOi
Di-o^wopyl d4artrst« CisHuOj
Diappn^yl d-tartrsU C-oHuOj
13-DiriDylbtaacoa. '.'.""11.1 CuiHa
Docoaaa C=sHu
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l-Dods«n»
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DcxiscyUene Ci^HrrX
JJodecylfriineUiyWIsiw....................... Ci»Hj*Si
Elaidicscid ,. CuSMi
EpwUorobTdria CjHsCIO
\,2-Eptxsy-2-m-HhjlprOi*B* CUHtO
Ereciemad....... G=HuOi
EstrsgoU (piettioir *Uyl beosaw) CioEuO
Ethaoa CiHj
EthoxTtliineihy'phenyiaflan*................... CioHnQSi
EthiyjytrimaUjybUan* CiHuOSi
E thoiytepheoyijibnev CwHaiOSi
Ethyl a«tat« CiEsO;
scetoscetat* CsHuOj
cr-Bthybcry!ii!aiid....'.'.ll"r.l"llll!l!!li!! CsHsOj
ct-EthyiKT7!oniSri!» CsHrN
Ethyl almhoJ (^thacol) C=HiO
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299.5
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Comrwitvi
KUD*
Etijyt b««c*tfl .... ...
Eth;l chiorkU
Ethyl &htr«rrtifc» ... . . . ......
V*f •rftrlhrlticiSBtfl
Ei^rlene
E;hy)eQ«-bis-(ch]oro«e*Ut«)
Etbyleoe ekkrobydrin (2 . .'
jiyccl SiSby1 ether (l,2-dirti2ane)
fiuCiidfl (l.I-difluoroethane)
Etbji iodide
Erhyl l-^-rcr»t*
Ethjl Irrafimte
r.*\fl nv»— >.>t»i, (»i^.n-t),'«J) . . , , ,
Etbyi oetiryl ether
l-Ethylnsp!it)ii!«i»
Ethyl ccHmphthyi kp*oo« ( j -prapicoaj&thoiu). .
Elhvl 3-aitrobenioat«
3-Ethylpentio«
4-Eihylpbeoetole
2-EtbyWMoot
3-Etbyh>beooI
4-EibylpJienoI
Ethyl propiomta. „
Ethyl propyl'etlisr
Ethrl saScylite
3-Ethyl3tyren8
4-EtiybtyTeoe . .
EAylrsothiocyanaie . . ...
2-Eibvixhiene ......
3-EtfayHrfww.
4-Etbyhjiuene
Ethyl trietiorouctati
Ethjritrimetiybilaiie
Ethyltrrawtiyltm
Ethyl iwr«WBt»
2-Elbyl-1.4-T3-irae
4-Ethyl-1.3-iy]cie.. . .
S-E-Jiyi-13-iyUM
E-jgroL
t*>-£u3eooi
Zuftayi ioetalo
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franun; am. Hg
1 I 5 1 10 1 23 1 40 60 I 100 | 200 I 4UO | 760
Tempentare. *C.
29.7
33.7
33.5
- 9.8
44.0
107.6
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10.6
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149.8
35.8
65.8
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108.5
55.5
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142.4
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165.0
48.0
77.8
143.7
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37.5
29.9
41.9
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68.8
72.0
106.0
20.6
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121.7
146.0
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-6.8
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63.3
66.3
22.8
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62.1
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132.4
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83.5
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33.6
101.4
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61.8
27.8
20.6
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61.7
91.0
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50.4
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54.3
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83.6
86.7
119.8
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59.5
137.7
162.8
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173.5
42.5
33.0
32.7
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105.8
14.7
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106.3
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168.8
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110.3
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33.5
123.7
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106.0
117.7
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152.0
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192.6
17.5
119.8
117.9
130.0
131.3
86 6
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99 2
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77.3
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113.8
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53.5
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187.9
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86.0
76.6
89.3
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69.0
45.0
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180.3
209.8
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215.0
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29.1
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51.8
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58.9
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112.0
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36.9
143.5
141.8
152.0
154.2
103.4
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121.5
71.9
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96.3
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121 2
116.5
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132 3
214.7
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248.5
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-------
Compound
Nam*
2-Fbcrotoluco*
Giularyl chkriiU.
Glyord ,
Pac*y^f*ifn
iffpnt^tiflfardv f rrfuAUuidcfaT'l't}
1 -Wp ptiO4
Hrptipoia scid (imathia icirf)
I jff»f»t»«j
Heptwoyl chkrida (enathyi chloride)
2-Heptna.. . . ." ".
Eepiylbeoaww
TTpji^t ryjHtkl* (pntfltiMnitnlt))
n-HiiadseTi a&ofaoi (cetyl alcohol)
n-H^Y^n*
1-Hf*anoI
2-Henaol
l-HiI*Q9
2-Iodotoltt«w
Trtfiric acid J .,....,,. , . , . , ,
1 -Menthol
Meolhyl acotiU
foroaU
Methaa*
Metfcaae&iol
Methyl 3i**ato
Formula
ooooooooooopoooooooooopppooppppppopppoppppoooppppppppopppppoppppppgogoggo
2§J«5'^gP&§'&B&&^
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Presnirvi mia. jig
1 1 5 I 10 20 40 1 60 | ICO 1 200 | 400 | 760
Tcastntere.-C.
-24.2
-22.4
-21.8
70.5
—20.0
+15.0
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100.8
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56.1
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38.3
52.4
152.6
211.7
115.0
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32.7
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1000
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119.6
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133.8
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84.0
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52.2
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32.7
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74.7
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76.3
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295.21
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189.5
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318.3
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30.6
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160.7
247.0
212.5
205.5
151.8
220.1
114.8
123.0
173.2
144.0
272.0
333.5
223.0
84.0
41.8
160.0
119.5
102.7
41.3
170.2
116.8
235.5
124.:
323.2
208.:
205.:
251.7
245.8
216.0
15 8
102.8
87.3
81.8
13.0
193.6
204.
209.0
-17.1
216.
233.5
157.7
125.0
129.0
108.:
157.
114.
118.3
159.
138.
181.
—16.
184.
227.
121.
190.
103.
151.
133.
102.
149.
156.
230.
148.
72.
1C6.
32.
—131.
—34.
144.
179.
+9.
-61.
23.
21.
(' —43.
73.0,
75.4
76.0
—46.0
175.5
61.4
120.0
I2I-.8
133.1
I85.«
196.3
214.0
207.6
182.6
265.0
236.5
230.0
172.4
240.0
133.3
147.8
194.0
162.7
296.5
359.4
247.8
102.0
58.7
179.5
136.6
116.3
58.6
193.3
137.7
253.5
143.1
348. 41
231.7
226.8
230.2
272.2
241.7
31.6
119.6
103.7
93.3
29.Q
215.7
225.0
230.8
—5.3
238.0
256.8
175.2
142.0
146.5
125.8
173.0
135.6
139.8
179.0
160.0
202.
207:
142J
203.
123.
173.
155.
122.
168.
178.
253.
169.
90.C
123.
50.
-175.
-22.
163.
202.
24.
-49.
43.
34.
-32.
92.8)
95.4
96.1
-33.0
193.5
80.3
140.0
141.8
151. {
207.8
219.8
235.0
223.5
205.8
233.5
261.0
257.3
195.3
263.0
153.!
163.3
217.0
184.1
323.8
335.0
274.5
125.:
78.0
199.6
155.6
130.7
78.1
217.8
160.0
233.5
163.8
374.6.
258.3
250.0
312.7
300.4
263.5
49.6
138.0
121.8
117.0
46.8
241.0
248.:
255.0
+10.2
262.5
232,6
193.8
159.8
165.5
147.5
200.0
157.8
163.9
199.:
185.7
225.2
+15.
231.
273.
164.
227.
151.
196.
179.
146.
190.
202.
277.
194.
109.
142.
70.
-168.
I84J
227.
40.
-37.
61.
49.
-19
114.0
116.0
117.0
-19.5
210.5
100.6
160.0
161.8
170.0
230.0
243.3
257.4
251.0
230.0
303.0
287.C
286.2
217.0
290.0
174.3
190.5
240.0
205.0
358.J
4MJ.6
303.0
155.0
98>
221.!
175.8
145.0
98.5
244.0
184.6
309.4
185.6
399.8
287.5
274.0
344.0
330.0
298.3
68.7
157.0
139.9
135.5
66.0
266.3
271.3
279.8
25.9
236.2
310.0
212.0
173.8
135.0
167.9
221.0
131.6
183.6
219.5
211.0
250.0
257.0
299.2
137.0
245.
175.0
220 C
202.0
169.
212.
227.
301.0
219.0
130.0
16i.fi
90.
-161.
+6
204.
253
57.
-23.
80.
64.
*
—80
-110.8
-92
8.2
97.5
17.9
-31
97
28.3
40.4
59.3
22.5
-98.*
-10
34.6
230
106,6
56.4
13.5
49.3
130
-95.3
-51.6
-98.5
48.5
-13.2
170.3
115.5
79
-47
-2
-146.7
44.5
43
33.5
-96.9
53
42.5
54.5
-59
15
-132.5
-121
102
-S8.7
-102.7
—97.8
-93.5
-------
Compound
Nux*
K MMhThnilnw
MrtlivlbMuvl klooliotL
2-MethyU2-baieiM
Methyl iwbutyl cmrbboi (2-m*Uul-*-p«UooI). .
B-botyJ ketooe (2-benoooe)
cobctyl ketooo (-i-mrthjl-2-pcnUaooe)
M*l*irl n-d^«f'Ti\'H<*H» fn-dodjmn-2-OBcS
&chlorcMoet»U .
Methyl n-dod«yi ketoo«(24e(nd«caaooe)
Mpt^ethyikHan«(2-bat*DOM)..,
VMetliy.-3-«lhylp«ot*oft.
Methyl elyeolat*. ,
2-MethytbepUcieeaiM.
^-VftiyVifptaiHi
4-Methyfi>*pt»n«
6-MrthyV-3-bepteo-2-oL
t-Methyl-5-b«pUo.2^
5-MetlrrIb«aae...
Meifcyi iodide
myrixtate
2.Mettty4peQUrfl.
'-Mftbvl-1-ftwtinol
2-Methy!-2-«fl taooi
Methyl n-pentyl ketom (2-h«ptaDODe)
2-M«tiiyippcp«w. *
Methyl propioo»t«. „.,
-Mrthyiprepiophenoo*
2-Mfthyipropiooyl breraida
iwprqpyl ketooe (3-^>fetbyl-2-batuooe)
2.M»thykrriooline ' I. ...
Methyl sJwylat*
o-Melhyl elyieue
4-Msthyl rtyrene
Methyl o-t*tr»deejl kstoo* (2-lendecuooe). . .
thjocywuit« .. . .
codeeyl k*too» (2-tridecanooe)
Moooriaytfccetylwo (botenyne)
W ynstwj^hirj e
Mjretie &ad (Utiidecauxjk »dd)
^8pCt^3L^QA
1 -N !*pilthoic M3d
2-KtphtbcJc acid
I-XupbtioI
2-Niphtbol .
1-NipbtiyUaun»
Formula
iiEUNOi
3«HLo
CHjBr
CsH,.
CiHu
JiHuO
^EZ-O
CiHioOi
CtBioOi
CuH=0«
3rHi<0>
SioHwOi
CJECi
CJLCL-O,
CuHoN
CiiH=O
CHjBr,
CH.-OI
CJBW)
(XHu
C>B<0>
CiiHa
&Hi.
CsHu
CtHu
C.HU
C^Hi!
CHJ
CuHxO.
CuHioO
CuE=O
c«a!
OHiiO
07BM)
CioHuO
CUHvBtO
CiHJoO
C»Hi»
CuHk>
CiHuOi
CioHu
Ci.HnOi
CicHi
CuHX)i
CuEsOi
diH^
FMnxe, nuaTHg
1 I 5 I 10 1 20 40 1 60 1 100 1 200 1 400 1 76*
36.0
77.6
39.0
70.0
49.0
-96.3
-89.1
-75.4
-0.3
-26!a
-34.1
63.7
+5.0
34.2
~ZM
125.7
-35.9
-53.7
-96.0
77.1
3.2
103.5
99.3
-35.1
-70.(
—43.3
-24.0
-23.9
-147.3
-74.2
93.8
+9.6
119.8
—21.0
-19.8,
-20.4
-16.1
41.6
41.9
-40.4
-39.0
"87'.8
39.8
-30.5
115.0
115.6
120.2
68.2
134.:
. 129.6
-60.9
-59.0
15.4
19.3
+5 4
-105.
—42.0
59.6
13.
-12.0
-19.
75.
54.(
16'.
109.
-14.)
86'.
-19.
-93.
14.
99.
142.
52.
156.
160.
94.
"m.
THE wmtort, *C.
62.8
109.0
64.4
97.5
75.2
-80.6
-72.8
-57.0
+22.1
28.8
tSi
-a?
30.0
61.7
-99.5
19.0
108. 1
155.0
-14.0
-33.8
-80.6
106.0
26.7
134.0
130.0
-13.2
-52.1
-28.0
-1.8
-1.4
-137.0
-57.(
33'.:
1
~i
1
1
|
-i.:
•6.7
65.0
66.0
19.5
18.
55.0
17.9
66.4
100
45.7
46.3
52.3
95.5
Mi A
161.6
-41.7
-39.8
33 0
+16.8
43.6
30 0
-96.5
-21.5
1
1
1
1
1
38.4
H8.0
04.
81.
34.
42.
51.
H.
-8
17.
f2.
77.
40.
32.
74.
74.
M.
69.
25.
28.
37.
76.2
124.2
77.3
111.2
83.0
-72.8
-64.3
—47.9
33.3
38.8
30.0
+5.0
-2.9
1080
42.0
74.9
—92.4
30.0
123.0
169.6
-3.2
-23.7
-72.8
120.4
33.1
149.7
145.5
-2.4
-43.3
-17.7
49.5
+9.9
-131.6
-48.6
141.8
45.3
168.7
12.3
13.3
12.4
17.8
76.7
77.8
-9.
-7.8
—15.?
133 2
79.7
+ 1.0
160.8
161.5
163.5
108-9
184.3
178 0
-32
-30.
49 6
27.6
55.5
42 2
-81.9
-11.8
103
50
17.9
+8
119.
95.
47.
55.
167.
21
+5.
131.
14.
-70
53.
143
190
e;.
196
202.
142
145
153
90.5
141.5
91.8
125.5
102. 1
-64.0
-54.8
-37.9
45.4
50.0
40.8
16.7
+8.4
123.0
55.4
89.C
-84.8
41.5
140.0
185.2
+8.7
-12.8
-64.0
1360
50.7
165.8
161.3
+9.7
-33.4
-6.5
21.7
22.3
-125.9
-39.2
157.7
58.1
186.0
-24.4
25.4
24.5
30.4
89.3
90..
-35i!
149.0
93.7
11.0
177.8
1784
185.7
123.
202 0
196.4
-21.4
-19.4
61 6
38.
67.7
55
-73.'
120'.:
64.
28.
18.
134.
110.
61.
69.
184.
34.
20.
147.
26.
-61.
67.
166.
207.
101.
211.
216.
158.
161.
171.
106.0
159.7
107.8
141.2
117.8
-54.2
—44.1
-26.7
58.2
62.0
52.8
29.6
21.0
139.0
70.0
105.3
-76.0
54.5
157.9
201.8
22.0
-0.6
-54.2
152.4
64.7
184.0
179.8
23.3
-22.2
36'.!
-119.1
-28.7
177.5
72.3
204.8
37.9
38.9
38.0
44.0
102.7
104.0
14.9
16.4
-24.2
166.0
109.5
25.5
195.8
196.8
203.8
139.0
-9.:
"74'i
si.;
81.2
70 7
-63.8
+11.0
133.0
79.4
39.
29.
150.
126.
77.
85.
203.
49.
38.
165.
39.
-51.
82.
186.
. 223.
119.
225.
231.
177.
181.
191.
115.8)
172.0
117.4
150.4
127.4
—48.0
-37.3
-19.4
67.0
69.8
60.4
37.4
28.9
148.6
79.7
115.3
-70.4
63.0
170.0
212.0
30.5
+7.2
-48.0
163.8
73.6
195.4
191.4
31.6
-15.7
14.0
43.9
45.0
-115.0
-21.9
189.9
81.8
216.3
46.6
47.6
46.6
52.8
111.5
112.8
23.0
24.5
-16.9
176.81
119.3
34.5j
207.5
2086
214.7
148.6
226.7
-1.9
+0-
83.4
58.8
89.8
80
-57.7
18.7
149.:
88.8
-17.4
47.3
36.
161.
136.
es.
95.0
215.
58.
47.
176.
48.
-45.
92.
198.
237.
130.
234.
241.
190.
193.
203.
129.8
187.8
130.8
163.9
140.3
-39.4
-28.0
-9.9
78.0
79.8
70.4
48.0
39.6
161.5
91.4
128.0
-63.0
73.5
185.8
224.8
42.1
17.9
-39.3
177.5
85.4
210.1
206.0
42.3
-6.3
25.0
55.7
57.1
-109.0
-12.9
205.0
93.7
231.5
58.:
59.4
58.3
64.6
122.6
123.8
34.1
35.6
-710
190'. 8
133.0
47.0
222.6
223.8
229.8
161.0
242.0
+8.
10.5
94.2
69.2
100.0
93.0
—49.3
29.0
164.2
101.6
-8.
56.
45.
176.
150.
102.
108.
230.
70.
59,
191.
59.
-37.
106.
214.
250.
145.
245.
252.
206.
209.
220.
149.3
212.4
151.4
183.2
159.0
—26.5
-13.8
+4.9
94.9
94.3
85.6
64.3
55.7
181.6
109.8
148.1
-51.2
90.5
209.6
245.0
59.6
34.0
—26.0
199.0
103.2
232.8
228.2
58.5
+8.0
41.6
73.6
75.3
- 99.9
+0.8
229.
111.8
254.5
76.0
77.1
76.1
82.3
139.5
140.0
50.8
52.4
+8.0
63J
245.3
246.7
251.6
181.2
265.8
24.
26.5
111.3
85.0
116.
112.3
44".
120.
+6.
71.
59.
197.
172.
121.
128.
254.
89.
77.
214.
77.
-24.
125.1
272'.
167.
263.
270.
229.
234.
244.
172.0
238.5
174.7
204.5
180.7
-11.9
+2.5
21.6
113.5
111.0
102.0
63.1
73.6
SD2.9
129.8
170.0
-38.0
109.5
235.0
266.8
79.6
52.3
-11.3
222.5
122.6
257.0
253.3
79.0
24.1
60.0
94.0
96.2
—89.5
16.0
255.5
131.7
279.8
97.4
96.3
102.2
156.6
156.1
7l"
25.3
"\75.t
82.0
269.8
270.5
275.8
202,3
291.:
41.6
44.:
129.
102.
133.
133
—22,:
212".
141.
22.
K.
73.
211.
197.
143.
151.
279.
110.
97.
238.
96.
-10.
143.
267.
294.
193.
231.
289.
255.
260.
272.
195.5
266.5
199.5
225.5
204.0
+3.6
20.2
38.5
131.7
127.5
119.0
102.3
52.6
224.0
150
193.0
-24.0
130.3
263.0
288.0
100.9
71.8
+4.5
246.5
143.0
2S2.0
278.0
98.6
40.7
79.6
115.6
118.3
-78.2
32.C
282.5
151.5
306.5
118.'
117.7
122.5
175.
174.3
90.0
91.9
42.4
197.7
101.0
295.
295.
301.0
224.0
319.
60.
63.
147.
121.
150.
155.
-6.
79.
238.
163.
39.
103.
88.
246.
223.
165
175.
307.
132.
119.
262.
116.
+5.
171.
297.
318.
217.
300.
308.
232.
283
309
ioc
24
-12.5
15-4
-93
-135
-135
-56.9
-84.7
-84.7
-18
—40
-97.7
-31.9
33.4
-126.4
-142.4
-7.6
-52.8
-96.7
—85.9
-114.5
-90
-99.8
-109.5
-120.8
-121.1
-118.2
-64.4
18.5
55.5
15
30
-154
-118
-103
—37.3
-140.3
-87.5
-77.8
-92
-8.3
-23.2
-51
35.5
23.5
23.5
57 5
80.2
160.5
184
96
122.5
50
-------
Coapouad
NMW
2-NnpbthyUiaiat
VNi*m>>in»aWriijd« ,
2 Ni^phfrnyl noitaiu
3-Nitrotolo*>l,3»X7l«a» (4-cutKxa-xyle»)
1-NrniMol
n-0ct*n*, . •
ifHWf»{l-Icflotwt»nt) ., ,,..
Pfti'nftaldiliyb _,..,...,,.. , - , , . , - - -
FfXltaCCUflft • • • • i .
FectadecsoA
1 VP*n^adt*n* ,..,.... , .... L .---.-
1.4-Pentadiwto
pprt-ppnfanfi (?,2-dLmw*Lnylprojn:i*} .............
2 ^ 4-P'mnt:uiMrifTl . ..,.,.. . -, .
1-Peatena . ....
Phenol
2-Ph*fiO^Bthyl acotafcd »
Phetyrt acetate . . .... . . i , . , .. ... ,
PhgDyUcet?! chloride
4-PheayI-3-bot«>-ioi» .
PhenTtcydohesaoa.
Pfaenyl ckblorophcepb&t*
m-Pbeoylea* ^hmimi (I3-pfaea7leQediamLne)..
1-?hi»nyl"l^-pHit3nM^m%. ..,.,,, 4 ^ . . , .
2-Pheaylpheaol „
4-Ph«ay!pbKjol ,
Ph&ahc anhydride
P^VO,H- ,. ,.. .. .
Pblhaltyl chloride
2-PicoUae
PiOWl'lc ,V\li
a-PineaB
Pberidma.
Formula
JwHiX
CttHuX*
CsEaN'sOs
CsHtXaO)
CaHiNiOs
CrHsNOs
C?HiNO)
CaHiNOi
CiHiNOs
Ci&N«Oi
CHiKOt
C&HiNOs
CaHrNO*
CjHiNOs
CiHiNOs
CTHrNOi
CTHrNOs
C7HyNOi
CaHaNOi
CaHai
CaH*
CTHa
CaHiaO
CgHiiO
CaHu
C«Eu
CsHuO
CsHuO
CuHaOi
CjHirl
CuHjJJi
CuHsO
CwHaOt
CijHaN
CiHuCH
C»HCU
dHCU
CjHsCU
CsECUO
CjjHsi
CuHji
CsHi
C»Ha
Ci«E»
Ci^HaCl
CiHi,
CsHi-
CsHu
CsHuOi
CsHio
CioHii
CiiHu
CjHuO
CsHuNO
CiEUO
CsH,oO.
CwHi^Ji
dad
CjHjO.
CAN
CsHTCIO
CuHioO
CioHioO
C?HsNO
C7HsN
CuHii
C«HsCtiO-P
c*sm«
CsHjO-
C«H)Ni
CiaHuNOi
CuHi-0-
CuHwO
CuHuO
CjHrO
CvHsNS
C3Hi*0
O>HuO
CC1-0
C*HiO,
C3H.O!
CsaajO-
CaHiN
CTHoOi
CicHu
CioHn
CsHuN
1 1
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-------
Cooipowxi
y^m*
iso-Propyl ^-naphthyl kctcm (2-aobatyroeapb.
tbonf)
Propyl iw7a;«r*ie
Pyrocu«cioi
Pyrogallol
Eafrole
aOicylaWchydf.
fikatoie
&ttaricft6d .-
Btearyl alcohol (1-ocUdeeanol)
Btyreaa
Suberic acid
Buccinie anhydride.
Baraarl chloride..
Terpenolio* . . _
U.l^Trtrabramoethana
Trtrsiaobutyfope
•i ttraccRfcEfS
• *2^,*-X*t?acW orob^ciwTW
«»2»3*>-i *&athlorob*nz?2ft
1 .2,4(5-TefracfcIort7ben jetie
1,1^2,2-TetracMoro-l Z-difiooroethaas
I.U-2-Teb-KhJororthane
*« '»*vZ*Trtnicfllorwthin€
'*wJ.^Tct^-^A]oro 4'ethylbgcjco8
23.4,6-Tetrtcbjon>pi»»nol
Formula
CsHiOi
CjHi
C,H!NO
C,HuOi
CiEUN
CtHioO
CsHmOj
CsHioOi
CiHsO
CiHiN
C,Hu
CjoHi-Oi
CiHiBr
C7HnO»
CrHuOi
C?Hi<0>
CiEUNOi
CjHrCl
CjHjCl
CsHsClOi
CjHjClOi
CiH«
CiHsOi
C»H«O
CtHjOz
CisHi'Ox
CjHrl
CjH?I
CsHi.Ot
C»H
-------
Compound Pressure, am. K*
Nona -
l.23,4-fetn*tb7ibMaa*
Tetraith/Hcad
Tetalia
l.23.4-TeteuneUvibea»M«
l,2,3,5-Tetram£thvlb»OMO»
1,2.4 5-T"*rvnt1hy'>-m«t , ,
7 7,3 VTVT'in«*W'"t«JW ,
Tetnautiiyleaa dibremid* (1,4-ditroraobuOa*).
TVnrarthyUniii, , . . , ,
T»feam«thyltia
Tetnpropytaw jl/nl mooouoproprl ether
TMMiflJjml (WMhiodiMhMoO
TV^hnwl (bflmHAhiol},
Th/Biol
TisbUehydft,
7-Trluiu ttifcril* (Z-fcrinnifeifo)
IJ 2TTribfomobut»m»x * 4
Trj3obutyLiniu>*
TrLvibulylsrti* t
l,23-TrichIcrob««e»
l»2,4-Tncfciarob*o5«n*
I 35-TricMorob«aen».... .... ...
I 2,3-Triehlorobutans
1,1 1-Trichlaroethaae
2,4,5-Tricblcropbecol
J,4i^-Trifihlo»oir»l'»ftrM»l ,,,.,....
1,1,1-TrichJcropropaiw
l,2,J-TricbIofOpropan«
1 J,2-Tricliloro-IA3-trifiQoro«tban«
l3.4-Trtetii7lbftti«o».
Tri»thyi or (hoformsU
TrT^hyl 'bnJiiuci .-1-,r,1--.T-, --....
TrLSncropfaaay lafl»/»«.
TriTi»tbailyl pha§pb»t«
2 3 5-Tr imet*aykce*opb«Kin«
2,4 S-TrJnsUiyballin*
I 2,Vrrim»thylbenu«»
1,3, 5-Tr im stay liwasen*
2,2,5-Trra»th7lbutaG« . . .
Trun-*hjl ci'rst*
Formula
C;»HwN
Ci;Hh&
C^H^oOiSi
CiiHa
C*Ht,Oi
CiHiiClO*
CiH^Pb
C&ftSi
JwHa
2ioHu
?icHu
2iiHn
?iHu
CiHjBri
CiHisPb
C«Hi£a
CiiHaO.
CiH.03
CiHwOdB
CUES
:aHfiS
CioHi«O
CisHuO
CsEiO
C^HjOj
CsHTN
CrHi
C;HioNt
CiHjN
CsHrN
dH£f
C7H3N
CTE,N
C3H7N
C;HisJf;
CiHBrrf)
C»H7Br>
CiH;Bn
CiHjBn
GHiBn
CiEsBn
CuTIsN"
C.JLuO
CiECi.Oi
CiCIaOj
CzBrCW)
CACUN
C*HjCU
CsHjCU
CJtCIi
CiH:CU
OHjCh
C:5iCu
C-HCU
CCljF
CiHjCbO
CiHiCW)
CISHu£UOjP3
CiHsCU
CjHiCU
aaj,
C:,H»
CuHa
CuitisO,
C;HnChSi
CuHaOfi
CL:HU
CuHu
Cva,i3
C.iHr.0.
CnTtoOr
CiHitOi
CuHafii
CuHrSi
CrHuO,
CsUiiOiP
GfluTl
CiKiFiSi
Ci^nPOl
C:,F£.,0
CjHtN
C,Hi,N
C,EUs
C,H,t
C-JIu
C7Ku
CiHi.Or
I | 5 1 10 I 20 40 t 60 I ICQ | 200 t 400 t 760
Tempentee, "C.
102.6.
I20.W
16.0!
65.7
153.9
110 1
33.4
-1.0
38.0
42.6
40.6
45.0
-17.4
32.0
-29.0
-51.3
116.6
60.0
42.0
-40.7
13.6
33.3
64.3
—25.0
52.0
-25.5
-26 7
106.5
36.7
42.5
44.0
41.0
42.0
25 2
82.4
18.5
45.0
41.0
33 2
32.6
47.5
323
13.0
95.2
51.0
56 2
-7.4
134.0
40.0
38.4
+0 5
-^52.0
—24.0
-43.«
-84.3
72.0
76 5
188.2
-23.8
+9.0
-68.0
170 0
59.4
137.8
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71.0
46.0
47.9
107.0
114 0
70. D
73.7
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+9.3
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93.7
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63.1
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150.7
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64.0
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67 3
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105.9
217.2
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166.3
+22.8
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74.2
76.0
150.2
133.7
144.0
99.8
104 8
29.2
67.8
37.6
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103 C
-81 7
95.9
42 5
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34.3
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197.1
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163.0
101.5
1230
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56.0
79.3
107.4
+10.0
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151.7
77.9
85.8
81.4
82.0
81.8
64 0
123.8
530
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83. 2
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70.6
90.0
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59.6
29 3
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85 6
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73 0
40 0
-21.9
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117 3
120.2
231 2
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1-40 3
223.0
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112.6
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— 143.0
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183.5!
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127.7
212.3
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95.8
91.0
83.0
24.6
87.6
16.6
-9.3
179.8
115.8
165.0
0.0
69.7
93.7
122.6
23.2
103.8
22.1
18.4
167.9
93.0
101.7
95.1
96.7
95.8
73.2
133.6
72.1
103.2
93.6
94.6
84.2
105.8
83.0
700
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101.8
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93.7
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135.8
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30.3
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110.0
139.8
37.0
119.0
36.7
31 8
185.7
110.0
109.5
110.0
113.5
111.5
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154.1
87.8
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100.0
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85.7
177.4
1!6 3
131 2
57 2
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119.8
114.8
110.8
71 5
+1 6
35.2
+11.9
-39.0
151.5
152.:
261.7
29.9
74.0
— 18 5
261.3
137.:
212 4
61.
143.
121.
122.
-131.
201.
190
191.
143.
155.
67.
115.7
85.4
25.4
192.0
154. 2
-55.2
139.S
85.4
79.S
76.1
+5.3
194.;
200.21
213.3
90.7
156.7
237.8
200.5
111.7
74.8
121.3
121.8
115.4
114.8
44.5
1 15.1
39.2
11.7
209.0
142.0
240.5
20.1
93.9
120.2
149.8
45.8
127.8
46.0
40.3
196.2
120.8
130.0
119.8
123.8
121.5
1040
165.0
97.5
131.6
127.0
122.2
110.0
134.0
107.3
S6.7
183.0
125.9
Ml.S
66.7
204.5
131 9
125.7
121.8
820
9 5
440
20.0
-32.3
162.5
153.5
271.5
38. 3
83.6
—n ;
273 8
148.2
222.0
704
153 :
132.2
133.4
213.5
202.
201.
153.
168.0
76.0
125.
95.
33.
207.
165.
-43.
149.
95.
S9.
as. a
.13.3
2C5.5
215.7
227.8
103.6
172.4
250.0
214.7
123.8
83.0
135.3
135.7
128.3
123. 1
54.8
128.7
50.8
22.8
223.3
154.0
235
30.5
106.6
134.0
164.1
57.7
140.5
58.2
51.9
211.5
135.0
145.2
133.0
136.7
133.7
117.7
173.0
110.2
t-M.O
141.8
136.3
123.5
143.0
119.7
110. 0
203.0
137.8
155.2
79.5
214.6
146.0
140.0
136.0
96 2
20.0
55 7
31.4
-23.0
173.0
177.8
233.8
50.0
96.
289.8
162 5
236.0
82.
167.
146.
147.7
223.
217.
214.
17J.
134.
83
141.
112.
44.
225.
179.
-40.
162.
108.
102.
1 93.
1 24-
.1 219.
239.81
250.0
123.5
196.0
263.4
236.5
142.0
toa.o
157.2
155.7
149.9
149.5
70.2
149.8
63.8
39.8
245.0
46.5
125.8
154.2
185.5
75.4
158.0
77.8
69.5
232.8
156.0
167.3
153.0
157.6
154.0
137.8
193.0
130.0
167.8
163.5
157.8
143.5
170.0
133.0
22S.2
155.4
176 2
93 4
229.8
168 2
162.0
157.7
118.0
36.2
73.3
48.0
-9.
201.5
199.0
302.8
67.7
115.6
+13.5
313.5
135.0
255.
101.0
1S3.
168.
158.
— 101.
250.
242.
235.
1%.
203.
1D6.
163.
136.
60.
255.
201.
-27.
182.
I21).
122.
113.
41.
241.3
264.6
275.0
146.2
221.4
288.0
253.2
161.8
130.2
181. 8
180.0
173.7
172.1
87.4
173.8
89.0
58.5
268.3
64.7
146.7
177.8
209.2
95.!
179.2
99.7
89.5
256.0
180.0
193.0
176.2
180.6
176.9
159.9
219.5
151.6
192.0
138.0
182.2
165.4
195.0
157.8
153.0
250.6
175.
199.o
120.2
246 4
193 5
187.7
163.0
143 0
54.6
93.0
67.0
+6.8
226.
222.
322.0
87.
137.0
30.
339.!
209.
276.
121.
210.
193.
193.
—81.
276.
267.
256.
221.
235.
125.
187.
163.
73.
223.
224.
-12.
203.
152.
145.
141.
60.
l 264.
291.2
300.0
163.5
243.0
307.3
231.5
IS3.0
153.0
207.2
204.4
197.9
195.9
106.3
197.5
110.0
78.0
292.7
84.4
168.0
201.0
231.8
116.'
199.5
m.o
110.6
2JO.O
205.;
217.1
199.7
203.3
200.4
183.5
24X0
174.0
216.2
213.81
2C6.5
183.4
220.0
179.0
179.0
276.3
195.6
223.0
143.0
262.0
213.5
213.0
208.4
169.0
74.
113.
84.
23.
251.
246.0
341.
103.
158.
47.
366.
234.
259.
143.
233.
218.
217.
-56.
301.
294.
273.
247.
242.
146.
211.
192.
98.
324.
247.
+2.
234.
176.
169.
164.
SO.
237
irasr
**»
"SO-
IL*
-136
-31.0
-6.2
-24.0
79.5
—102.2
-20
-27.5
-16.5
—38.3
51.5
*4.5
-95.0
99
—13
2».S
-M.3
-31.5
44.5
65.5
-26
16.5
—22
57
73
52.5
17
63.5
-30.«
—36.7
-73
62
63.5
-77.7
-14.7
-35
47.7
-6.2
41
135
-63.O
-117.1
67
-25.5
-44.1
-44.8
-15.3
73 S
-------
Compound
Xun.
Tcnmila
Preggre, mm. Ha
1 I 5 I 10 I 20 | 40 I 60 I 100 | 300 I 400 I 760
. *C.
point.
2.3.3-TWsDethylpentaM.
23.4-ThmethylpoiUM
Z2,4-Tm»rthyl-3-p«it»oH,0>
CuHii
CuHi«
CtHu
CiHu
CiEn
CiBi
.
2,4,6-Triajeibj-btyrrae
Ttlmethyiracctiue uihydridt
CiiHi4
CuHii
OH:oO»
Tripropylawglycol
Triiolylpbc«ph»U.
tfodeeme.
Uodtouioie uad
CuHnOi
Ci:Hr>0«
CuH_-<
CuHsOi
BO-Y>lmeKki
T-Vilovhctom.
CiiH»O
CsHioOi
CsHioOi
VniHin
Vu-yJ »eri»tfc
2-Vbyl»oiso1«
CsHjN
CsHsOi
.
4-Vmylaai»oU
VnyitWmde
cyanide (acrylonidrfle)
CsHioO
CtHioO
CjHiN
C-HJ?
CnHtO
Z4-Xy»ld-iyde
2-Xy!n>* (2-xyltD*)
C.Hi,
CsH.s
CvHu
CsHuN
.
M.8
-29.0
-36.5
-25.8
-26.3
147
26.0
43.1
37.5
53.5
169.7
193.5
96.0
101.5
82.4
154.6
32.7
101.4
114.0
71.1
42.2
34.5
37.5
—6.0
107.0
—48.0
4T.9
43.4
45.2
—105.6
-51.0
-149.3
-77.2
64.0
153.2
59.0
-3.8
-6.9
-8 1
52.6
44 0
87.2
71.2
67.0
-7.1
-15.0
-3.9
-4.1
36.0
53.7
77.0
65.7
82.6
183.4
230.4
125.7
131.6
112.4
184.2
59.7
133.1
142.8
99.0
67.7
59.6
65.6
+18.1
133.4
—23.0
63.0
69.9
72.0
—90.8
-30.7
-138.0
-60.0
91.7
171.1
85.9
-f20.2
-f 16 8
-H5.5
79.8
72.61
100.6
84.6
E0.5
.
+7.1
46.4
67.8
91.6
79.7
97.4
197.0
249.8
140.5
147.0
127.3
193.0
73.9
149.0
156.3
112.8
79.8
71.3
79.8
30.0
154.0
-18.0
81.0
S3.0
85.7
-S3.7
-20.3
-132.2
-51.2
105.6
187.0
99.0
3Z
23
27.3
S3
87 0
115.5
99.7
96.0
16.0
+7.5
19.2
19.3
57.6
83.0
107.1
94.8
113.8
206.8
269.7
155.8
161.8
143.7
213.2
85.6
166.0
172.0
127.5
93.1
84.0
95.2
43.3
170.5
-7.0
94.7
97.2
100.0
-75.7
-9.0
-125.4
—41.7
120.3
205.0
114.0
45.
41.
40.1
1576
102.7
131.0
106.0
113.2
29.5
20.7
33.0
32.9
69.8
100.0
124.2
111.8
131.0
215.5
290.3
173.7
179.8
161.4
229.7
104.4
185.6
188.7
143.7
107.8
98.0
101.9
57.8
13S.7
+5.3
110.0
112.5
116.0
+3.8
118.0
-31.1
136.3
223.8
129.7
59.5
55.3
54.4
123.8
120
141.1
126.3
123.8
38.1
29.1
41.8
41.6
77.3
110.0
135.5
122.3
142.2
221.2
305.2
184.6
190.2
173.2
239.8
115.2
197.2
199.5
153.7
116.6
107.3
122.4
66.9
199.8
13.0
1)9.8
122.3
126.1
-61.1
11.8
—113.0
-24.0
146.4
236.0
139.8
68.8
64.4
63.5
133.7
131.5
153.41
140.3
137.9
49.9
40.7
53.8
53.4
87.6
124.0
149.8
136.8
156.5
228.4
322.5
199.0
204.4
187.8
252.2
128.1
212.5
213.5
167.2
128.3
118.9
136.5
78.6
214.5
23.3
132.3
135.3
139.7
—53.2
22.3
-106.2
—15.0
159.8
251.5
152.2
81.3
76.8
75.9
1468
146.0,
172.81
160.3
153.4
67.8
58.1
72.0
71.3
102.2
145.0
171.8
157.6
179.8
239.7
349.8
220.2
224.4
209.7
271.8
149.3
237.8
232.8
187.7
146.0
136.2
157.7
97.7
237.3
38.4
151.0
154.0
159.0
—41.3
38.7
-95.4
-1.0
1800
275.3
172.3
100.2
95.5
94.6
166
163.01
193.8
184.5
183.5
88.2
78.0
92.7
91.8
118.4
167.8
196.1
182.3
205.5
249.8
379.2
244.3
247.0
232.8
292.7
171.9
262.8
254.0
209.8
165.0
155.2
182.3
118.7
260.0
55.5
172.1
175.8
182.0
-28.0
58.3
-84.0
+14.8
202.8
301.5
194.1
121.7
116.7
115.9
188.3
193.7
214.2
203.1
208.0
109.8
99.2
114.8
113.5
135.0
192.7
221.2
207.0
231.0
259.2
413.5
267.2
269.5
256.6
313.0
195.8
290.0
275.0
232.0
134.4
175.1
207.5
140.8
285.0
72.5
194.0
197.5
204.5
-13.8
78.5
—72.2
31.7
225.0
328.5
215.5
144.4
139.1
1333
211.5
217.9
-112.3
-107.3
-101.5
-109.2
93.4
49.4
-25.6
29.5
24.5
-34.5
—37.6
81.5
153.7
-82
160.5
122.5
.
—47.9
+13.3
Reprinted by permission from CHEMICAL ENGINEERS' HANDBOOK, 5th Ed., edited by
R.H. Perry and C.H. Chilton. Copyright 1973 by McGraw-Hill Inc. All Rights
Reserved. Printed in USA. No part may be reproduced, stored for retrieval or
transmitted, in any form or by any means, electronic, mechanical, photocopy-
ing, recording or otherwise, without prior written permission from McGraw-Hill.
-------
EXHIBIT 4-2
VAPOR PRESSURES OF INORGANIC MATERIALS C9)
Corwjrf
Ku»
ch!o-''s
pentafluocida
triouda
chlorida.
iodide
Boroo hydrides
Ceamca
Chromium
Cobalt chloride
CuprP'is bromide
tlcri'U
Formula
y
.trBHOj
J:Cli
A1F,
ill.
CD,
JEUBf
rales
\H,H3
N'HJt
Sb
SbBn
SbCli
SbCU
Sbli
SbiOt
A
As
AsBo
AsCU
AsFa
AaF.
As;0.
AsHi
Se(BHt}«
BeBct
Bed.
Belt
Bi
BiBo
BiCti
B.-Hi3f
BHjOO
BuEii
B-Hj
B;Hj
BCHu
BiHio
BBrj
BCU •
BFi
Bn
B-F.
Cd
CdCla
CdFt
Cdl.
CdO
Ci
c
CO!
C&
CO
cos»
C03
cs»
CCli
CF*
Cs
CoBf
CsCl
Cs?
Cal
Cl;
CIF
OF,
CM)
CIO,
ChO:
H30iCl
Cr
C'rfCO).
CrO:Cb
CoCn
Co(CO)>NO
CbFi
Cu
CvuBra
Cu:Cl«
C'J:r3
C:N',
CNBr
CNC1
CXF
Frnaun, ma. Eg
1 I 5 1. 10 I 20 40 | 60 100 | 250 400 | 760
Temoerature, "C.
1234
ioo!o
1233
173.0
2143
— 109.1
198.3
-26.1
160.4
-50.6
-31.1
210.9
836
93.9
49.2
22.7
163.6
574
-218.2
372
41.8
-11.4
-117.9
212.5
-142.6
+1.0
289
291
283
1021
-93.3
-139.2
-63.0
60 0
-159.7
'-so!
-90.
-41.4
-91.5
-154
-48.
-69.3
394
1112
416
1000
'3586'
-134.
-73.
-222.
-117.
-132.
-47.
14.
-50.
-134.
279
743
744
712
733
-113.
'-9d!
-45.
32.
1616
36.
-18.
1523
572
546
-35.
-75.
-134 '
1421 1
-522^
103.3
116.4
1293
207.7
2306
-97.5
234.5,
-10.4
193.8
-35.7
-36.0
247.0
934
126.0
71.'
436
203.8
626
-213.9
416
70.6
+11.7
-103.0
242.6
-130.3
934
19.8
325
328
322
1099
261
242
-75.3
-127.3
-45.0
80.8
-149.
-40 4
-29.9
-73.1
-20 4
-75.2
-145.4
-32,a
-51.0
455
613
1231
431
1100
926
3323
-124.4
-54.3
-217.2
-102.3
-119.8
-26.5
41.2
-30.0
-174.1
341
838
837
798
823
— 106.7
-143.4
-80.4
-81.6
-23.8
53 5
1763
58.0
+3.2
1795
666
645
610
-83 2
-13.3
-61 •)
|l -123 8
14W . 1555 1 I63i
-42 9. -32. 4 -209
113 0 134.
-------
Compound
V m^
•J
v A '
T.T^iiopcgertBan*
G0ld
ieida
train (nt«r) , . . , , ,
j«l£d«
cbloridt
sul£d»
chlorida
iodid*
Nickel
Nitrosyt chloride
(white)
Or/sen
Phosgetw
Phwpbora (yellow)
(Hoist).... ';;.
tribrocudft
jxatachloridfl
Pfaojphiaa
chloride
iodide. . .
penUrdda
cxTchloride
tiuochlcrids
Platinum
Potassium
bromide
chloride
tuorida
hydro rid*. .
icxlid*
B.-.doa
Kifniuin heptotid*
IVwniil a.
3CM
* j
"-O
GeBri
GeCU
GfHi
GsHC!>
Ge)4
je-Ht
GeiBt
Ao
Sa
B»
WQr
sci
HCN
HJfi
HI
EM)
w-a
E3SH
TI-A.
HiT»
I,
DV
Fa
Fe(CO)§
FeS,
FeCU
Kr
Pb
PbBn
PbCU
PbFj
Pbli
PbO
Pb3
Li
T.iRf
LiCl
T.ip
111
Mz
MgCU
Mn
MaCb
Eg
ms-3
E^Cli
Fill
jito
MoF»
MoOt
N»
Ni
Ni(CO)4
NiCU
NJ
NO
NOj
V-Oi
N-O
NOC1
OsOt
QjO«
0>
COClj
p
p
PBn
PCU
PHi
PHtBr
PHiCl
PHiI
P<0i
P»Oa
POO.
PSBn
PSCU
Pt
K
KBr
KC1
KF
KOBE
TTT
Ea
Z»fh
1 1
-63.9
-223.0
— 196.1
-45.0
-163.0
-41.3
-73.2
-88.7
-36.9
1869
-271.7
—263.3
-138.1
-150.«
-71. t
-123.2
-17.3
-134.3
—43 2
—115.3
—56.4
33.;
—87 0
1787
194.0
—199;
973
513
547
479
943
- 852
723
748
783
1047
723
621
778
1292
126 2
136 5
136 2
157 5
3102
—65 5
734
—237.3
1310
671
—226 1
— 184 5
—55 6
—36 8
—143 4
3.2
—5 6
—219.1
—92.9
76.6
237
7.8
55.5
—43 7
—91 0
—25 2
334
50 0
— 18 3
2730
-341
795
821
835
719
745
-144.2
212.5
5 I
-54.0
-216.9
-IS6.6
43.3
-24.9
-151.0
-22.3
-54.6
-69.8
-I2.J
2059
-271.5
-261.9
-127>
—140.7
-55.3
-74.3
-109.6
+1.2
-122.4
-24.X
—103.'
— 82. «
62.:
—70.;
1957
-6.5
221.1
—191.:
1099
578
615
861
540
1039
928
828
840
830
1156
802
702
877
1434
736
164 8
1653
166 0
169 2
3393
—49 0
785
-255
1979
731
—221
— ISO 6
—42 7
—23 0
—133 4
22 0
+15 6
-213.4
-77 0
III 2
271
34.4
74 C
—23 5
—79 6
—9 0
39 7
424
72 4
+4 6
3007
403
892
919
988
814
840
-132.4
237.5
10 |
-46 7
-214.1
-182.3
56.8
-15.0
-145.3
-13.0
-45.2
-60.1
-0.9
2)54
-271.3
-261.3
-121. £
-135.6
-47.7
-65.8
-102.2
11.2
-116.3
-15.3
-97.S
-75.4
73.2
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K*m»
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dioxide t ......
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cr-'tixlond*
teti-*ciiioride
Silicon
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tetrachloride
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Pullman
Trisitaae
TWrWJjq. , , i
OctachlorotruilaM.
fT.iY'vMnrfy'l'ci'jivrviu x
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^•Tl fl IKTOdisil^Qft
DibromochlorofluoroBibaft
SlIOM
Stiver
chloride
cyaaida...
fluoride ......
hydroxide
iodids ,,,....
fib-onhi'7^ t ,.,...,.
Ph-onniirfl flildff
Sulfur
dODOchlorido
Bulfuryl chloride
triodde (
SiCl4
SF«
SiFCU
SIR,!
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-------
EXHIBIT 4-3
METHOD FOR ESTIMATING STORAGE TANK EMISSIONS
4.3 STORAGE OF PETROLEUM PRODUCTS
Revised by William M. Vatavuk
and Richard K. Burr
Fundamentally, the petroleum industry consists of three operations (1) crude oil production. (2) petroleum
refining, and (3) transportation and marketing of finished products. Associated with these operations are
evaporative emissions of various organic compounds, either in pure form or as mixtures.
From an air pollution standpoint, the petroleum industry is defined in terms of two kinds of evaporative
losses: (1) storage and (2) marketing and transportation. (See Figure 4.4-1 for schematic of the industry and its
points of emission.)
4.3.1 Process Description1 "5 .
Petroleum storage evaporation losses are associated with the containment of liquid organics in large vessels at
oi! fields, refineries, and product distribution terminals.
Six basic tank designs, are used for petroleum storage vessels: (1) fixed-roof (cone roof), (2) floating roof
(single deck pontoon and double deck), (3) covered floating roof, (4) internal floating cover, (5) variable vapor
space, and (6) pressure (low and high).
The fixed roof tank (Figure 4.3-1) is the least expensive vessel for storing cer/tain hydrocarbons and other
organics. This tank generally consists of a steel, cylindrical container with a conical roof and is equipped with a
pressure/vacuum vent, designed to operate at slight deviations (0.021 Mg/m2 maximum) from atmospheric
pressure.
PRESSURE-VACUUM
VENT
GAUGE HATCH,
MANHOLE
LIQUID LEVEL
Figure 4.3-1. Fixed roof storage tan'r.
-------
A floating roof tank is a welded or riveted circular vessel with an external float-type pan or pontoon roof
(single- or double-deck) equipped with single or double mechanical seals (Figure 4.3-2).
WEATHER SHIELD
HATCHES
LIQUID LEVEL
DRAIN
VENT
ROOF SEAL
(NONMETALLIC
OR
METALLIC)
HINGED CENTER SUPPORT
Figure 4.3-2. Double-deck floating roof storage tank (nonmetallic seal).
The floating roof prevents the formation of a volume of organic vapor above the liquid surface, which would
otherwise be vented or displaced during filling and emptying. The seal, which is designed to close the annular
space between the roof and vessel wall, consists of a relatively thin-gauge shoe ring supported against the tank
shell around the roof.
The covered floating roof tank, simply a steel pan-type floating roof inside a fixed roof tank, is designed to
reduce product losses and maintenance costs. Another type, the internal floating cover tank, contains a floating
cover constructed of a material other than steel. Materials used include aluminum sheeting, glass-fiber-rein forced
polyester sheeting, and rigid plastic foam panels.
The lifter and flexible diaphragm variable vapor space tanks are also used to reduce vapor losses (Figure 4.3-3).
With the lifter tank, the roof is telescopic; i.e., it can move up or down as the vapor above the liquid surface
expands or contracts. Flexible diaphragm tanks serve the same function through, the expansion and contraction of
a diaphragm.
Pressure tanks are especially designed for the storage of volatile organics under low (17 to 30 psia or 12 to 21
Mg/m2) or high (up to 265 psia or 186 Mg/m7) pressure and are constructed in many sizes and shapes, depending
on the operating range. The most popular are the noded hemi-spheroid and the noded spheroid for low pressure
and the spheroid for high pressure. Horizontal cylindrical forms are also commonly used for high pressure storage.
4.3.2 Emissions and Controls1 '3-5'7
There are six sources of emissions from petroleum in storage.
-------
ROOF CENTER SUPPORT
FLEXIBLE DIAPHRAGM ROOF
-GAUGE HATCH
ROOF SEAL
(LIQUID IN TROUGH)
LIQUID LEVEL
MANHOLE
Figure 4.3-3. Variable vapor storage tank (wet-seal lifter type).
Breathing losses are associated with fixed roof tanks and consist of vapor expelled from the tank because of
thermal expansion, barometric pressure changes, and added vaporization of the liquid.
Working losses consist of hydrocarbon vapor expelled from the vessel as a resua of emptying or filling
operations. Filling losses represent the amount of vapor (approximately equal to the volume of liquid input) that
is vented to the atmosphere through displacement. After liquid is removed, emptying losses occur, because air
drawn in during the operation results in growth of the vapor space. Both filling and emptying (together called
"working") losses are associated primarily with fixed roof and variable vapor space tanks. Filling losses are also
experienced from low pressure tankage, although to a lesser degree than from fixed roof tanks.
Primarily associated with floating roof tanks, standing storage losses result from the improper fit of the seal
and shoe to the tank shell.
Wetting losses with floating roof vessels occur when a wetted tank wall is exposed to the atmosphere. These
losses are negligible.
Finally, boiling loss is the vapor expelled when the temperature of the liquid in the tank reaches its boiling
point and begins to vaporize.
The quantity of evaporation loss from storage tanks depends on several variables:
(1) True vapor pressure of the liquid stored,
(2) Diurnal temperature changes in the tank vapor space,
-------
(3) Height of the vapor space (tatik outage),
(4) Tank diameter,
(5) Schedule of tank fillings and emptyings,
(6) Mechanical condition of tank, and
(7) Type of paint applied to outer surface.
The American Petroleum Institute has developed empiricaj formulae, based on extensive testing, that correlate
breathing, working, and standing storage losses with the abo-'e parameters for fixed roof, floating roof, and
variable vapor space vessels.
Fixed roof breathing losses can be estimated from:
B =•
2.74
0.68 D1.73 H0.51 AT0.50 F c
(0
p
C
where: B = Breathing loss, lb/day-103 gal capacity
P = True vapor pressure at bulk liquid temperature, psia
D = Tank diameter, feet
H = Average vapor space height, including correction for roof volume, feet
AT = Average daily ambient temperature change, °F
= Paint factor, determined from field tests (see Table 4.3-1)
= Adjustment factor for tanks smaller than 20 feet in diameter (see Figure 4.3-4)
Vc = Capacity of tank, barrels
K = Factor dependent on liquid stored:
= 0.014 for crude oil
= 0.024 for gasoline
= 0.023 for naphtha jet fuel (JP-4)
= 0.020 for kerosene
= 0.01 9 for distillate oil
W = Density of liquid at storage conditions, Ib/ga]
Table 4.3-1. PAINT FACTORS FOR FIXED ROOF TANKS3
Tank Color
Roof
White
Aluminum (specular)
White
Aluminum (specular)
White
Aluminum (diffuse)
White
Light gray
Medium gray
Shell
White
White
Aluminum (specular)
Aluminum (specular)
Aluminum (diffuse)
Aluminum (diffuse)
Gray
Light gray
Medium gray
Paint factor (Fp)
Paint condition
Good
1.00
1.04
1.16
1.20
1.30
1.39
1.30
1.33
1.46
Poor
1.15
1.18
1.24
1.29
1.38
1.46
1.33
1.44b
1.58b
Reference 2.
"Estimated from the ratios of the seven preceeding paint factors.
-------
1.00
g 0.60
o
Ul
0 10 20 30
DIAMETER, feet
Figure 4.3-4. Adjustment factor for small-diameter fixed roof tanks.2
Breathing losses of petrochemicals from fixed roof tanks can be estimated from the respective gasoline loss
factor, calculated at their storage temperature:
Bp = 0.08 \^l \-^l BG (2)
where: Bp, BQ, = Breathing losses of petrochemical (p) and gasoline (G), lb/day-103 gal
Mp = Molecular weight of petrochemical (p), Ib/mole
\V = Liquid density of gasoline, Ib/gal
Pp, PQ = True vapor pressures of petrochemical (p) and gasoline (G) at their bulk storage temperature,
psia
This same correlation can also be used to estimate petrochemical working loss, standing storage loss, or any other
kind of loss from any storage tank.
A correlation for fixed roof tank working loss (combined emptying and filling) has also been developed:
180+ N\
Ff = lOOOV/mP
6N
(3)
where: Ff = Working loss, lb,'10 gal throughput
-------
P = True vapor pressure at bulk liquid temperature, psia
N = Number of tank turnovers per year (ratio of annual throughput to tank capacity)
m = Factor dependent on liquid stored:
= 3x 10"4 for gasoline
= 2.25x 10-4 for crude oil
= 3.24 x 10"4 for naphtha jet fuel (JP-4)
= 2.95 x ID"4 for kerosene
= 2.76 x ID"4 for distillate oil
Standing storage losses from floating roof tanks can be calculated'from:
2.74 WK, 1.5 / p \°J 0.7
S = LD I —} V KSKCKD (4)
Vc \14.7-Py w s c p
where: S = Standing storage evaporation loss, lb/day-103 gal capacity
K{= Factor dependent on tank construction:
= 0.045 for welded tank, pan/pontoon roof, single/double seal
= 0.11 for riveted tank, pontoon roof, double seal
= 0.13 for riveted tank, pontoon roof, single seal
= 0.13 for riveted tank, pan roof, double seal
= 0.14 for riveted tank, pan roof, single seal
D = Tank diameter, feet; for D > 150 feet (45.8 m) use "EK/BCT instead of "D1-5"
Vw = Average wind velocity, mi/hr
Ks = Seal factor:
= 1.00 for tight-fitting, modem seals
= 1.33 for loose-fitting, older seals (typical of pre-1942 installation)
Kc = Factor dependent on liquid stored:-
= 1.00 for gasoline
= 0.75 for crude oil
= 0.96 for naphtha jet fuel (JP-4)
= 0.83 for kerosene
-------
= 0.79 for distillate oil
Kp = Paint factor for color of shell and roof:
= 1 .00 for light gray or aluminum
= 0.90 for white
Finally, filling losses from variable vapor space systems can be estimated by:
, . 0.25VeN)
where: m - Factor dependent on liquid stored (same as equation 3)
Fv = Filling loss, lb/103 gal throughput
Vt = Volume of liquid throughput, bbl/year
Ve = Volume of expansion capacity, barrels
N = Number of turnovers per year
W = Density of liquid at storage conditions, Ib/gal
Equations 1 through 5 can be used to calculate evaporative losses, provided the respective parameters are
known. For those cases where such quantities are unknown or for quick loss estimates, however, Table 4.3-2
provides typical emission factors. Refinement of emission estimates by using these loss correlations may be
desirable in areas where these sources contribute a substantial portion of the total evaporative emissions or are of
major consequence in affecting the air quality.
The control methods most commonly used with fixed roof tanks are vapor recovery systems, which collect
emissions from storage vessels and send them to gas recovery plants. The four recovery methods used are liquid
absorption, vapor compression, vapor condensation, and adsorption in activated chLiCoal or silica gel.
Overall control efficiencies of vapor recovery systems vary from 90 to 95 percent, depending on the method
used, the design of the unit, the organic compounds recovered, and the mechanical condition of the system.
In addition, water sprays, mechanical cooling, underground liquid storage, and optimum scheduling of tank
turnovers are among the techniques used to minimize evaporative losses by reducing tank heat input.
-------
Table 4.3-2. EVAPORATIVE EMISSION
EMISSION FACTOR
Product
Crude oilc
Gasoline0
Naphtha jet fuel
(JP-4)C
Kerosene0
Distillate fuel0
Acetone
Ammonium hydroxide
(28.8 % solution)
Benzene0
Isobutyl alcohol
Tertbutyl alcohol
Carbon tetrachloride
Cyclohexane0
Cyclopentanec
Ethyl acetate
Ethyl alcohol
Freon II
nHeptanec
nHexan8c
Hydrogen cyanide
lsooctanac
lsopentanec
Isopropyl alcohol
Methyl alcohol
nPentanec
Toluene0
Vapor
pressure
ratio
IP/PG>
0.543
1.53
0.2108
0.0263
0.0343
0.264
0.230
0.776
0.210
0.120
2.01
0.103
0.353
1.42
0.112
1.86
0.0933
0.272
1.26
0.0594
Mole
wt(M)
(Ib/mole)
64.5
58.8
63.3
72.7
72.7
58.1
35.1
78.1
74.1
74.1
153.8
84.2
70.1
88.1
46.1
137.4
100.2
86.2
27.0
114.2
72.2
60.1
32.0
72.2
92.1
Floating roof
Standing storage loss
"New tanK" conditions
Ib/day-
103 gal
0.029
0.033
0.012
0.0052
0.0052,
0.014
0.023
0.0074
0.00088
0.0029
0.018
0.0083
0.024
0.0081
0.0024
0.12
0.0045
0.013
0.017
0.0055
0.057
0.0024
0.0038
0.038
0.0024
kg/day-
10J liter
0.0034
0.0040
0.0014
0.00063
0.00063
0.0017
0.0028
0.00089
0.00010
0.00034
0.0021
0.0010
0.0028
0.00097
0.00029
0.014
0.00054
0.0016
0.0020
0.00065
0.0069
0.00029
0.00046
0.0046
0.00029
"Old tank" conditions
Ib/day-
103 gal
0.07T
0.088
0.029
0.012
0.012
0.03S
0.062
0.020
0.0023
6.0074.
0.048
0.022
0.062
0.021
0.0064
0.32
0.012
0.036
0.043
0.015
0.15
0.0064
0.010
0.10
0.0062
kg/day-
103 liter
0.0086
0.011
0.0034
0.0015
0.0015
0.0043
O.0074
0.0023
0.00023
0.00039
0.0057
0.0027
0.0074
0.0025
0.00074
0.033
0.0014
0.0043
0.00051
0.0013
0.018
0.00077
0.0012
0.012
0.00074
3Rsferences 2, 3, 6, and 7.
''Factors based on following conditions:
Storage temparature: 63°F(17.2°C).
Daily ambient temparatura change: 15°F (-9.5°C).
Wind velocity: 10 mi/hr (4.5 m/sec).
Crude oil
Gasoline
Naphtha jet
fuel UP-4)
Kerosene
Distillate
oil
Reid vapor
pressure
psia
7.0
10.5
2.5
<0.5
<0.5
Mg/m1
4.9
7.4
1.75
<0.35
<0.35
True vapor
pressure
psia
4.6
5.8
1.2
<0.5
<0.5
Mg/ma
3.2
4.1
0.84
<0.35
<0.35
—
Typical fixed-and floating-roof tanks
Diameter: 90 f l (27.4 m) for crude. JP-4. kerosene, and
distillate; 110 ft (33.6 m) for gasoline and all
petrochemicals.
Height: 44 ft {13.4 m) for crude, JP-4. kerosene, and
distillate; 43 ft {14.6 m) for gasoline and all
petrochemicals.
Capacity: 50,000 bbl (7.95 x 10* liter) for crude. JP-4,
kerosene, and distillate: 67,000 bb» (10.65 x 10*
liter) for gasoline and all petrochemicals.
Outage: 50 percent of tank height.
Turnovers per year: 30 for crude- oil; 13 for all othsn.
clndicates petroleum products whose evaporative emissions are exclusively hydrocarbons (i.e., compounds containing
only the elements hydrogen and carbon).
-------
FACTORS FOR STORAGE TANKS3- b
RATING: A
Fixed roof
Breathing toss
'New tank" conditions
Ib/day-
103 gal
0.15
0.22
0,069
0.036
0.036
0.093
0.16
0.050
0.0057
0.018
0.12
0.057
0.16
0.055
0.016
0.81
0.031
0.088
0.11
0.038
0.39
G.0;6
0.026
0.26
0.016
kg/day
103 liter
0.018
0.028
0.0033
0.0043
0.0043
0.01 T
0.018
0.0057
0.00067
0.0021
0.014
0.0067
0.019
0.0062
0.0019
0.098 '
0.0038
0.010
D.0',3
0.0043
0.047
0.00? S
0.0031
0.032
0.0019
"Old tank" conditions
Ib/day-
103 gal
0.17
0.25
0.079
0.041
0.041
0.10
0.18
0.057
0.0064
0.021
0.14
0.064
0.18
0.062
0.018
0.92
0.033
0.10
0.13
0.043
0.45
G.C19
0.029
0.30
0.018
kg/day-
103 liter
0.020
0.031
0.0095
0.0048
0.0048
0.013
0.021
0.0069
0.0079
0.0026
0.016
0.0079
0.022
0.0074
0.0022
0.11
0.0040
0.012
0.015
0.0051
0.053
0.0022
0.0034
0.036
0.022
Working loss
lb/103 gal
throughput
7.3
9.0
2.4
1.0
1.0
3.7
6.3
2.0
0.23
0.74
4.8
2.3
6.4
2.2
0.65
32.4
1.2
3.6
4.5
1.5
15.7
O.SS
1.0
10.6
0.64
kg/103 liter
throughput
0.88
1.1
0.29
' 0.12
0.12
0.45
0.76
0.24
0.028
0.90
0.58
0.28
0.77
0.27
0.079
3.9
0.15
0.43
0.54
0.18
1.9
0.080
0.13
1.3
0.077
Variable vapor
space
Working loss
lb/103 gal
throughput
Not used
10.2
2.3
1.0
1.0
4.2
7.1
2.3
0.2S
0.83
5.4
2.6
7.2
2.5
0.73
36.7
1.4
4.0
5.1
1.7
17.8
0.74
1.2
12.0
0.73
kg/1 0s liter
throughput
Not used
1.2
0.28
0.12
0.12
0.51
0.86
0.27
0.031
0.099
0.63
0.31
0.87
0.30
0.089
4.4
0.16
0.49
0.61
0.21
2.1
.X 0.090
" 0.14
1.4
0.087
Typical floating-roof tank
Paint factor (Kp): New tank-white paint, 0.90; Old
tank-white/aluminum paint, 0 95.
Seal factor (Ks): New tank-modern seals, 1.00; Old
tank-50 percent old seals. 1.14.
Tank factor (Kt): New tank-welded, 0.045; Old tank-
50 percent riveted, 0.083.
Typical fixed-roof tank
Paint factor (Fp): New tank whits paint, 1.00; Did
tank-white/alummum paint, 1.14.
Typical variable vapor space tank
Diameter- 50 ft (15 3 m).
Height: 30 ft (9.2m).
Capacity: 10,500 bbl (1.67 x 10* lit-r).
Turnovers per year: 6.
-------
REFERENCES FOR SECTION 4.3
1. Control of Atmospheric Emissions from Petroleum Storage Tanks. Petroleum Committee, Air Pollution
Control Association. J. Air Pol. Control Assoc. Z/(5):260-268, May 1971.
2. Evaporation Loss from Fixed Roof Tanks. American Petroleum Institute, New York, N.Y. API Bulletin
Number 2518. June 1962,
3. Evaporation Loss from Floating Roof Tanks. American Petroleum Institute, New York, N.Y. API Bulletin
Number 2517. February 1962.
«
4. Evaporation Loss in the Petroleum Industry — Causes and Control. American Petroleum Institute, New York,
N.Y. API Bulletin Number 2513. February 1959.
5. Personal communication with personnel in Engineering Services Branch, Emission Standards and Engineering
Division. Office of Air Quality Planning and Standards, Environmental Protection Agency, Research Triangle
Park, N.C.November 1972.
5. Petrochemical Evaporation Loss from Storage Tanks. American Petroleum Institute, New York, N.Y. API
Bulletin Number 2523. November 1969.
*
7; Use of Variable Vapor Space Systems to Reduce Evaporation Loss. American Petroleum Institute, New York,
:N.Y". API Bulletin Number 2520. September 1964.
-------
CHAPTER 5
CONTROL TECHNIQUES
This chapter will include a description of
the air pollution control techniques jnost applicable
to the reduction or elimination of toxic substance
emissions. For more details on the subject of
the techniques mentioned here, and for descriptions
of some of the less-generally applicable emission
reduction measures, the reader is referred to
such documents as EPA Publication Numbers AP-68,
"Control Techniques for Hydrocarbons and Organic
Solvent Emissions from Stationary Sources" (11),
AP-51, "Control Techniques for Particulate Air
Pollutants" (12), and AP-40, "Air Pollution Engi-
neering Manual" (13).
One of the simplest and most highly efficient
emission control techniques available is contain-
ment. The keeping of toxic materials in closed
tanks, vessels, containers and other processing
units that do not leak, are not allowed to overflow,
and are not vented to the atmosphere any more often
and in any greater quantity than is absolutely
necessary will go a long way toward reducing
atmospheric emissions. In the case of volatile
materials, such containment may require equipment
construction features that will enable considerable
vapor pressures to be withstood.
Process modifications often prove to be
a relatively easy method of effecting emission
reductions. As discussed previously, the lowering
of temperatures and raising of pressures tend
to reduce the equilibrium vapor-phase concentra-
tions of pollutants, and the minimization of
exposures to air currents tends to reduce evapora-
tion and aerosol generation rates. Reducing the
amounts of toxic materials used or formed in
processes, or substitution with a less-toxic or
non-toxic material, is another simple type of
emission control measure. Operating and maintenance
5-1
-------
practices that can help to reduce emissions include
the prevention of leaks, overflows, and spills, and
the inspection of pressure relief valves to insure
their proper closure and seating, and of gaskets,
packing, seals and emergency rupture discs to insure
their integrity.
Concerning types of add-on air pollution control
equipment, the most widely applicable to organic
gaseous toxic substance emissions are adsorbers
and afterburners. Both are versatile enough to
control the emissions of a very wide range of organic
materials, and can be highly efficient over wide
ranges of pollutant concentrations if properly
designed, operated, and maintained.
The adsorption of the toxic substance onto
activitated carbon or another suitable medium is
generally most economical when very low pollutant
concentrations are involved, or when the recovered
material would be of significant value and when
the pollutant is not too volatile to be effectively
adsorbed (such as is often the case for materials
normally occuring only in the gaseous state). When
the adsorptive capacity of the activated carbon or
other medium is attained, the medium must be either
replaced or regenerated (e.g., by steaming followed
by cooling), in which latter case the pollutant
can ordinarily be either re-used or incinerated.
The use of either direct-flame or catalytic
afterburners to convert gaseous organic pollutants
to harmless carbon dioxide and water (accompanied
in some cases by some less harmless combustion
products) is most economical at higher concentra-
tions of pollutants that are not worth recovering,
and for pollutants too volatile to be effectively
adsorbed. An afterburner should be designed to have
a sufficient gas stream residence time, or
volume-of-combustion-chamber to volumetric-flow-
rate-at-combustion-temperature ratio (normally at
least about 0.3 to 0.5 seconds), a sufficient combus-
tion chamber temperature (normally 1200°F to 2000°F
5-2
-------
for direct-flame units, but as little as about 5QQ°F
to 800°F for catalytic units.1, and a sufficient
entrance throat velocity tin direct-fired unitsJ
to result in good turbulence for thorough, mixing
(normally 25 to 50 feet per secondl.
Condensers (both, those involving indirect
heat transfer, such as shell-and-tube types, and
those involving direct cooling medium-gas stream
contact, such as the barometric types that cool
through, the latent heat effect as sprayed water
evaporates into the gas stream] and absorbers Cfor
example, packed columns with circulating liquids)
are often employed in chemical processing plants,
but typical process units would seldom be
efficient enough to serve as final gaseous emission
control devices.
In the case of inorganic gaseous emissions,
a wide variety of wet scrubbing techniques could
be considered for the achievement of emission
control. The solubility of the gas of concern
in the scrubbing liquid (which would often require
adjustment to either an acidic or an alkaline
condition) would be of primary concern; solubilities
can be checked in such references as the CRC "Hand-
book of Chemistry and Physics," and R.H. Perry
and C.H. Chilton's "Chemical Engineers' Handbook."
Other important scrubber parameters include the
liquid-to-gas flow rate ratio (L/G), the gas stream
pressure drop (AP) , and the contact time and condi-
tions.
Particulate toxic substance emissions are most
efficiently controlled by fabric filters Ce.g.,
as contained in baghouses) or by panel filters.
In the former case, the dust is generally removed
in place by shaking or reverse-air techniques,
while in the latter case the panels must be
removed at intervals for replacement or recondi-
tioning. Filtration is highly reliable if the
media are correctly installed and maintained.
The most important operational parameter is the
5-3
-------
gas stream pressure drop, which, will decrease if
the gas stream is by-passing the media because of
incorrect installation, excessive dust build-up,
defective seals, a loss of media integrity, or other
problems. For a toxic particulate pollutant whose
physical nature renders filtration unsuitable, wet
scrubbing is most likely to be employed. Cyclones,
impingement separators and settling chambers would
only infrequently provide adequate collection
efficiencies for the final control of toxic parti-
culate emissions. Electrostatic precipitators are
much more complex control devices that can be
very efficient but also sensitive and unrealiable
for most of the types of applications discussed
here.
The reduction of both gaseous and particulate
emissions depends not only upon the effective
operation of add-on air pollution control equip-
ment, but also upon the efficiency with which
fugitive contaminants are captured and ducted to the
control devices. In this regard, the importance
of adequate hood design should not be overlooked.
Hoods should be designed and operated so as to
provide air velocities at locations of contaminant
releases of at least the values indicated in Exhibit
5-1 (14).
A word on the utilization of tall stacks, or
other such elevated release points, is appropriate
at this point, since these are frequently employed
for the purpose of reducing ground-level air pol-
lutant concentrations. Many are of the opinion
that a tall stack constitutes a simple and effective
air pollution control device, resulting in the
greatly increased atmospheric dilution of emis-
sions; it is true that many of the principal pol-
lutants are formed in nature at rates approaching
or exceeding anthropogenic emission rates, but
are harmless because of their distribution over
wide areas of the globe. The same cannot usually
be said of toxic substance emissions, many of which
do not even exist in nature, and would tend to
reach intolerable levels if emitted indefinitely,
5-4
-------
even at low rates, because of the lack, of natural
means for their elimination from the. environment.
Thus, higher toxic substance release points may
simply result in the substances being distributed
over wider areas and adversely affecting more sen-
sitive individuals and receptors, before the effects
are noted, the causal substance detected, and the
source of the emissions identified. For these
reasons, tall stacks are not generally believed
to be the proper means of effecting toxic substance
air pollution control.
5-5
-------
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CHAPTER 6
START-UPS, .MALFUNCTIONS AND SHUT-DOWNS
This chapter deals with the excess emission.
situations that may be associated with process
start-ups, malfunctions and shut-downs, in that
these represent departures from normal operations
during which ordinary emission control techniques
may prove insufficient or ineffective.
Start-ups and shut-downs are relatively common
occurrences that are often responsible for substan-
tial portions of the total toxic substance emis-
sions . One of the reasons for this fact is that
many operations involving highly toxic materials
are specialty processes conducted on a small scale,
and in a batch rather than a continuous fashion,
so that start-ups are frequent.
The cleaning and drying of reaction vessels,
columns, piping and other appurtenances prior to
start-ups or following shut-downs often necessitates
the opening or exposure of this equipment to the
air, during which evaporative emissions may occur.
Such cleaning procedures may be especially common
at specialty facilities where many different products
are made in the same equipment.
When reaction vessels are charged with raw
materials prior to start-up, and when these must
be mixed, or when reaction vessels must be emptied
following shut-down, and the products must be
drummed, air that contains pollutants may be
displaced more rapidly than at any time during
the remainder of the operation, and spills and
subsequent aerosol generation and/or evaporation
may be the most likely to occur at these times.
Often start-ups and shut-downs must be effected
with some haste; often delays develop that prolong
the time of exposure of toxic substances to the
atmosphere; in either case, excess emissions may
often be the result.
6-1
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The multiplicity of tasks that need to be
accomplished during start-ups and shut-dowjis, and
the necessity that these be performed in a certain
order, results in a higher likelihood of accidents
and excessive emissions at these times. Air pollu-
tion control devices should be functioning before
the processes whose emissions are to be controlled
are started up, if possible, or else the devices
should be on very soon after start-up is. effected.
Similarly, when shutting down, the pollution control
devices should be turned off last, or as late as
possible. In addition, the opening of any heated
or pressured vessels containing toxic substances
must be done with care if excess boil-over emis-
sions are to be avoided.
Malfunctions that can result in excess toxic
substance emissions may be either process-related
or emission control device-related. When a process
malfunction occurs that requires the shutting
down of the operation, all of the types of excess
emissions described above with respect to normal
planned shut-downs may occur, but the abnormal
and unplanned nature of the event results in
an even greater likelihood of excess emissions.
The emergency blow-down of an operation, during
which materials may be removed from process equip-
ment very rapidly in the interest of safety, can
often be expected to result in exceeding the
capacities of air pollution control devices to
function effectively. If a process malfunction
results in an excessive pressure build-up, an
emergency relief valve may open or a rupture disc
may burst, suddenly releasing a quantity of poten-
tially toxic materials directly into the atmosphere.
Other, and often less dramatic, malfunctions
involve only air pollution control equipment.
This could involve such occurrences as the over-
heating and automatic by-passing of an adsorber
or a baghouse Cor, alternatively, the destruction
of such equipment by heat or fire), or the loss
of a wet scrubber's water supply. In such cases,
6-2
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especially if there is no violation of applicable
air pollution emission standards (as is often
the case with toxic substance emissions) and
if the resulting increased emissions are believed
to be tolerable by the operator, the operation
may simply be continued, perhaps indefinitely, with-
out the benefit of air pollution emission controls.
6-3
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CHAPTER 7
INSTRUMENTATION, MONITORING,
RECORD-KEEPING AND REPORTING'
The basic types of instrumentation related
to toxic substance atmospheric emission evaluations
provide the values of parameters associated with.
process conditions, air pollution control equipment
operations, and gas stream properties. These
instrumentation types are discussed in turn below.
Process instrumentation can enable determina-
tions to be made of the concentrations and rates
at which toxic pollutants may be evolved within
process equipment. Conditions of temperature,
pressure or vacuum, flow rate, weight or density,
volume or level, and others in some cases are useful
in uncontrolled emission estimation, being indica-
tive (as discussed in greater detail previously)
of such significant factors as toxic material vapor
pressure and vapor-laden air displacement rates.
Unusually high temperatures, vacuums, flow rates,
levels, or rates of fluctuation of process conditions
may be accompanied by abnormally high emissions.
Air pollution control equipment instrumentation
is useful in estimating the removal efficiences
that may be obtained. In the case of an adsorption
unit, the temperature of the bed is most important
in determining the medium's capacity to adsorb
a specified toxic substance, and unusual temperature
increases may result in the bed actually becoming
an emission source, as accumulations of potentially
toxic materials may be desorbed. Such temperature
increases may be attributable to the process
emission source changing, a loss of cooling system
effectiveness (where such a system is employed),
or a latent heat of adsorption (which is related
to the latent heat of condensation, or of evapora-
tion, since the adsorption of a vapor is physically
similar to its liquefaction from the gaseous state)
7-1
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effect due to the. adsorption, of significant quan-
tities of pollutants from the gas stream in
a short period of time. The effectiveness of the
adsorption medium's steam regeneration, where
this step Ls employed, can be estimated By the
temperature to which the bed is raised, and the
temperature to which it is subsequently cooled
before re-use, as well as by the amounts of con-
densed steam and organic materials accumulating
during the regeneration stage. Finally, the
gas stream pressure drop through the adsorption
unit is related to the thickness of the bed,
and the gas stream volumetric flow rate is related
to the gas residence time in the bed, both of
which are important parameters for estimating con-
trol efficiences.
Afterburners may include combustion-zone tem-
perature (which is about the same as exhaust tem-
perature only if no heat recovery is employed)
instrumentation, but the inlet gas stream volumetric
flow rate, inlet temperature and pollutant heating
value, and the rates of firing with natural gas
(or other fuel, such as distillate oil if used)
and of combustion air injection (if needed for the
burner oxygen supply) can be used to calculate the
combustion temperature by means of an enthalpy
balance. The gas stream flow rate is also important
because, if it is unusually low, the required degree
of turbulence to effect complete pollutant combus-
tion may not be achieved; while, if the flow rate
is too high, in addition to the possibility of
the combustion temperature dropping too low, the
required residence time for complete combustion
may not be obtained.
When scrubbers are utilized for emission con-
trol, the pollutant removal efficiences obtained
are ordinarily dependent upon the gas stream pres-
sure drop and on the ratio of the liquid flow rate
to the gas stream flow rate (L/G). In addition, the
liquid stream pressure drop is of interest because
an abnormally low reading may be indicative of
insufficient atomization, and an unusually high
7-2
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reading .may be Indicative of nozzle plugging (.and
reduced liquid flowl. The acidity, alkalinity,
density or other composition-indicator of the.
scrubbant may also be measured.
The functioning of a particulate matter fil-
tration system is best indicated by the gas stream
pressure drop, since an unusually low differential
may result from gas stream by-passing Cdue to
leaks, defective seals, incorrect valve settings,
improper filter element installation or fit, tears
in the filter cloth, etc.}, and an unusually high-
pressure drop may indicate that emission control
problems may be developing Csuch as the plugging
of filter medium pores, or the malfunctioning
of filter cleaning devices such as shakers or
reverse-air equipment}. Temperature recording
instruments may indicate whether the filter ma-
terial 's upper temperature limit may be exceeded,
or whether the dew point of the gas stream may
be reached (which can result in filter material
damage or simply difficulties due to an excessive
pressure drop). The levels of collected particulate
material in the hoppers of baghouses can also
be checked to insure that the equipment is
functioning.
Toxic substance atmospheric emission monitoring
is not generally required by law and Is often
not practical because of the complexity and cost
of the monitoring equipment that would be required.
As a result, such monitoring would only infrequently
be found at a continuous-type, large-scale
operation and rarely found at a batch-type, small-
scale operation. The results of in-plant monitoring
undertaken to establish compliance with occupational safe-
ty and health standards, if available, may be useful in
some cases but cannot be used directly since both.
the in-plant and ambient air concentrations , and
the corresponding acceptable levels , will generally
differ.
The record-keeping and reporting of toxic
substance atmospheric emissions Is also not
7-3
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required; however, the authority to enter and in-
spect emission source premises discussed previously
includes provisions for access to relevant records-.
The inspection of process emission source and
air pollution control equipment parameter values,
as are often recorded either in log Books' or on
strip-type or circular chart recording machines,
can reveal not only typical values, But also de-
partures from normal that may be related to exces-
sive emissions as discussed in detail previously;
however, the possibilities of faulty instrument
readings and non-functioning sensors should be
kept in mind. Thus, process emission source and
air pollutuion control equipment operational records
may serve as a useful inspection and evaluation
aid if the reliability of the records is proper-
ly taken into account.
7-4
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CHAPTER 8
FIELD INVESTIGATIONS
This chapter is devoted to describing the
performance of field investigations of potential
toxic substance atmospheric emission facilities;
however, a thorough understanding of the previous
chapters included in this manual is required for
the successful performance of the inspection pro-
cedures outlined here, which are intended to insure
that atmospheric pollution attributable to the
release of toxic substances is not allowed to
occur.
Field investigations may be conducted either
as a matter of routine or for various other pur-
poses, such as in response to complaints, in check-
ing on a visible or odorous emission noticed by
chance, or in following up corrective measures
required to alleviate a known problem. Routine
facility visits may be made at a frequency to
be determined based on regulatory agency policy,
for example, on a quarterly schedule; however,
the visits should not be made at regular intervals
or on a pre-arranged basis if the most accurate
picture of routine operating and maintenance con-
ditions is to be gained by the inspector. On the
other hand, the cooperative arrangement of an
inspection visit can be beneficial in insuring
that production is scheduled to be on-going and
that time will not be wasted in gaining entry to
the plant and in presenting an itinerary of the
visit. Thus, the above factors must be weighed
in deciding whether or not the inspection should
be arranged with the facility owner or operator
in advance.
Certain items of safety and inspection equip-
ment should be taken on the visit by the field
investigator Csee Exhibit 8-1). The safety equip-
ment includes a hard hat, safety eyeglasses or
goggles, chemical-resistant safety shoes or boots,
and a gas mask equipped with activated carbon
canisters (or other suitable safety respirator).
8-1
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In some cases, such, additional safety items as
ear protectors (for example, cotton plucjsl, pro-
tective gloves, and fireproof clothing may be
required. • The investigator may find it advisable
to check on the existence of any unusual safety
requirements in advance, since source facility
owners and operators may refuse the investigator
entry if the required safety equipment is not
available.
Items of inspection equipment that the inves-
tigator may have need of include the appropriate
credentials, an inspection manual and forms, a
notebook and writing implements, a wristwatch,
a camera with film, a tape measure, a flashlight,
a compass (if directions in the plant area are
not well known to the inspector), and sample bags
Cwith ties) or containers, with a pocket knife
or scraper and a sample brush. The inspector may
know some of these items not to be required, de-
pending on the characteristics of the facility
to be visited.
Prior to attempting to conduct an emission
source facility inspection, the field investigator
should seek whatever relevant information may be
available in the files of environmental regulatory
agencies, and in some cases other governmental
agencies. This information may prove valuable
in helping the inspector to prepare an itinerary
for the visit, to fill in some of the information
required on the inspection forms in advance (so
that the data may simply be checked rather than
written out while at the plant, leaving more of
the inspection time for actual observation), and
to more readily detect variations from normal oper-
ating conditions. Before leaving to visit the
facility in question, the investigator should,
of course, be certain that he can locate it readily,
When the field investigator reaches the vicin-
ity of the plant, he should circumnavigate it
and complete a copy of the pre-entry chemical
J-2
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emission source inspection form presented here
as Exhibit 8-2. Many of the general items of infor-
mation to be filled out on the pre-entry inspection
form are of obvious relevance. These include the
facility name, th.e facility address, the person
to contact, his telephone number, the inspector's
name, the inspection date and time, and the reason
for the inspection. Meteorological conditions
such as temperature, wind speed, wind direction,
cloud cover and precipitation are relevant both.
as factors having some bearing on process condi-
tions, atmospheric emissions, ambient concentrations,
and the inspector's evaluations. It should be
noted that the atmospheric stability condition,
which may greatly influence the relationship between
emission rates and ground-level concentrations,
can be approximated based on the time of day, wind
speed and cloud cover Csee Turner's "Workbook of
Atmospheric Dispersion Estimates," EPA Publication
Number AP-26, for more details (15)).
While it is desirable for the inspector to
view the facility from all directions, any visible
emission evaluations should be accomplished with
the wind direction being roughly perpendicular
to an imaginary line drawn between the observation
point and the source, with the sun being roughly
at the observer's back (or, if the observation
is being made at night, with the moon or other
light source behind the plume as seen by the
observer), and with a suitable background against
which the plume can be viewed. Since toxic sub-
stance emissions may be of concern even in very
low concentrations and quantities, even the faintest
of visible emissions should be recorded as such.
The information to be recorded includes the plume
release location, its opacity and color, a descrip-
tion of the background against which the plume
opacity is judged, the observer's location, the
distance and direction from the observer to the
plume, and the photograph number Cif any is
taken). Visible emission evaluations should be
made in accordance with Method 9 of 40 CFR 60,
Appendix A.
8-3
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Th_e odorous emission section of the pre-entry
inspection form must of necessity be completed
with, largely subjective information. Odor strength,,
type and persistence should be judged carefully
and recorded. The observer's location, the apparent
release location, the distance and direction to
the apparent source, and the number of any photo-
graph taken should also be recorded. Any odorous
emission evaluations must of course be made in
the direction from the source toward which, the
wind is blowing at the time. As a guide for the
estimation of toxic substance ambient concentra-
tions, a list of odor descriptions and thresholds
was presented as Exhibit 3-6. It may at times
be advisable for a field investigator to familiarize
himself with the odors characteristic of toxic
substances that may be released from a plant that
he is about to visit or has just visited.
The pre-entry inspection form also includes
provisions for recording data regarding particulate
deposition and ecological effects on any type of
receptor. Observations of cumulative particulate
matter deposition or ecological effects (which
will probably only very seldom be evident, even
to a trained observer familiar with the area's
ecology) will most often be made in the direction
of the prevailing wind at the time of the inspec-
tion visit, but may also be more frequent where
the potentially sensitive ecological element is
particularly close to the source. In the case
of particulate matter deposition or a suspected
ecological effect, photographs should be taken
and samples should be obtained for subsequent
analysis.
The field investigator may also wish, to sketch
the emission source facility location, for the
purpose of showing relative source, receptor, and
observation locations, before entering the plant.
Such a sketch may help to clarify some of the
information recorded above on the pre-entry inspec-
tion form.
1-4
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When he has completed his pre-entry observa-
tions, the field investigator should proceed to
the plant admission gate. As may be necessary
to gain entry and to perform his duties, the in-
spector should present his credentials and state
his intent; acquaint any plant official question-
ing the inspector's right to enter, examine records
and copy information with the relevant provisions
of Section 114 of the Clean Air Act Gas discussed
previously); and inform any plant official refusing
to allow entry or inspection of the penalties
prescribed under Section 113 of the Clean Air
Act Cas also discussed previously). Should the
field investigator's right be persistently refused,
he should make a written record of the name and
position of the plant official involved and of
any other relevant factors, depart from the plant,
and report the incident to the environmental regula-
tory agency's attorney for further action.
If permitted to enter the premises of the
facility, the field investigator should meet with
the official in charge (who will often be the
plant manager) or his designated representative
(who may be the plant environmental engineer).
The inspector should explain the purpose of his
visit and propose an itinerary of what he would
like to see and about how long he expects his
visit to take. Ordinarily the inspector will want
to review the plant's operating and maintenance
records, logs and recording charts, making notes
of any important emission-related information; in-
quire about the day's operating schedule and any
unusual conditions, start-ups, malfunctions or
shut-downs that may be occurring; and proceed with
his observations' of the on-going operations, the
state of maintenance of process and control equip-
ment, visible and odorous releases, and instrumen-
tation readings related to atmospheric emissions.
A sample reactor inspection form is presented
as Exhibit 8-3. The first few items to be entered
on the form (facility name and address, inspector,
date, and name of system), as well as on additional
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forms to be described below, should not be omitted
as they axe necessary for the unambiguous identi-
fication of the inspection record, which..may at
some later time become inadvertently separated
from other papers on which, the identifying infor-
mation has been recorded. The next information
to be entered on the inspection form serves to
identify the subject item of equipment, in this
case the specific reactor, that may be a source
of toxic air contaminant emissions to the atmos-
phere. The roll film numbers of any photographs
taken of the reactor, whether from on or off the
plant property, should also be recorded Cas well
as any pertinent notes regarding the on-going
operation, the details of greatest interest, the
view of the reactor being shown, etc.) on the
inspection form; such photographs would generally
not be intended for use as part of any subsequent
litigation, but would rather serve to improve the
field inspector's recollection of his visit as
he writes his inspection report, to reveal details
that he may have overlooked, and to confirm the
identity of the subject reactor, should doubts
arise for any reason, subsequent to the completion
of the visit.
The remainder of the information to be entered
on the reactor inspection form is that which would
be required in order to arrive at an accurate judg-
ment as to whether the reactor may constitute a
significant source of potentially toxic atmospheric
emissions. All other factors being equalr the mag-
nitude of such emissions will often be approximately
proportional to, or at least directly related to,
the capacity of the reactor. Of the size—related
items (capacity, diameter, and height or length),
it would often be unnecessary to obtain the values
of all three parameters; any two could be used
to estimate the third Cfor a cylindrical vessel,
V=ird2h/4 or V=Trd^£-/4, where V is the volume in
cubic feet, d is the diameter in feet, h is the
height in feet, and £ is the length, in feet) , and
the capacity alone would usually be sufficient
for the field inspector's needs. While viewing
8-6
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the reactor for the purpose of size estimation,
the inspector should also note the equipment's
apparent physical condition, for example, the pres-
ence of leaks. Evidence of the leaking or spillage
of potentially toxic liquid or solid materials
Cwhich may later become airborneI may be seen
either on the reactor vessel itself, on the ground
or floor below, or elsewhere in the area. Indica-
tions of gaseous leaks may be visible either dir-
ectly, or through resulting particulate deposition
or corrosion patterns on equipment surfaces, or
may be noticeable due to the odorous nature of
the leaking gas.
The type of reactor operation, usually either
batch or continuous, should be check-marked on
the inspection form. Batch operations often entail
greater atmospheric emissions per unit of product,
since they involve frequent start-ups and shut-
downs, with the charging and removal of materials
and related displacements of particulate- and/or
vapor-laden air or other gas; continuous opera-
tions , while often larger in terms of total pro-
duction, are generally steadier in nature and more
fully enclosed, with little net volume change or
displacement occurring. The reactor charging method
should also be checked; dumping or pouring materials
into an open reactor porthole is far more likely
to result in atmospheric emissions than is charging
through a tightly connected pipe. Certain addition-
al items to be check-marked on the reactor inspec-
tion form apply to the use of agitation, which
may raise dust, liquid droplets, or vapors that
are subsequently released; heating, which may pro-
mote active boiling (similar to mechanical agitation
in effect) as well as increase the vapor pressures
and gas-phase concentrations of potentially toxic
materials; cooling, which usually has the reverse
effect and thus may decrease emissions; pressuri-
zation, which may decrease the vaporization of
potentially toxic materials but may also increase
losses through leakage; vacuum operation, whose
effects may be the reverse of those due to pres-
8-7
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surization; and certain types of auxiliary equip-
ment (for example, fractionation columns, reflux
condensers, steam or water ejectors, wet scrubbers,
combustible-gas burners, etc.I, which, may serve
to reduce emissions, whether primarily intended
as either process or air pollution control equip-
ment.
Further information to be recorded on the
reactor inspection form provides additional details
that may be needed by the field inspector for tlie
determination of the significance of toxic sub-
stance emissions. The processing time, in com-
bination with the reactor capacity noted previously,
can be used for the estimation of process weight
rate, to which the emission rate is ordinarily
related. Alternatively, plant log books may be
consulted for production rate data. The tempera-
ture cycle data (for example, 30 minutes heating,
60 minutes at 250°F, 30 minutes cooling) are useful
in determining that portion of the operation time
during which the critical reactor conditions and
maximum emissions may actually occur, and may often
be recorded automatically on circular charts; the
pressure cycle data may serve a similar purpose.
Abnormal values of recorded temperatures and/or
pressures may be indicative of emission-related
malfunctions. The discharging method and cleaning
method employed during the operation and mainte-
nance of the reactor, as they relate to its toxic
substance emission potential, should also be entered
on the inspection form.
One of the most important sections of the
reactor inspection form is that in which, the raw
materials, intermediates, products and by-products
are listed. Only the amounts of the raw materials
and products need ordinarily be listed, and the
amounts for either group alone may often be suffi-
cient to determine the amounts for the other group.
The emissions of a particular toxic material would
most often be expected to be proportional to
the amount of that material present. While reaction
-------
intermediates and by-products are usually only
present in small quantities, often not measured,
and may be estimated if necessary based on con-
siderations of chemical equilibria, kinetics/ and
stoichiometry, th,ese materials can sometimes be
of concern in terms of emission toxicity, parti-
cularly where the raw materials and products are
not toxic and emission controls are thus inefficient
or non-existent. In any case, a knowledge of the
materials present in the reactor is a prerequisite
to a determination of the equipment's potential
for significant toxic substance emissions. The
relevant biological, chemical and physical proper-
ties of the materials present can be investigated
in detail subsequent to the inspection visit in
order to permit as accurately as possible an assess-
ment of each material's toxicity and emission rate.
The reactor inspection form, as well as
additional forms described below, also includes
provisions for the recording of exhaust gas infor-
mation. As the field inspector makes a note of
the location and height above grade of the
exhause release point, he should also record the
plume opacity, the existence of any odor downwind,
and the numbers of any photographs he may have
the opportunity to obtain. Of the volumetric gas
flow rate, vent top-inside diameter, and gas exit
velocity, if any two are obtained, the third may
be directly calculated (from G=ird2v/4, where G
is the volumetric gas. flow rate in cubic feet per
second, d is the vent top-inside diameter in feet,
and v is the gas exit velocity in feet per second) .
Of the three parameters, the volumetric gas flow
rate is by far the most important Cas it represents
flow conditions elsewhere in the system, as well
as at the exit), and it alone may often be suffi-
cient for the inspector's needs; however, if in
addition to the estimation of emission rate Cfor
example, by multiplying the volumetric gas flow
rate times the exhaust-gas concentration of a toxic
material) the resulting ambient air concentration
or deposition rate is to be estimated through the
utilization of diffusion modeling techniques, either
8-9
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the vent diameter or the exit velocity, or botlx,
may first be required in order to estimate the
rise of the plume above the top of the stack or
vent. The gas exit temperature would be need-
ed by the field investigator in any case, for the
conversion of the volumetric gas flow rate to
that which would occur elsewhere in the system,
where the temperature may differ. Exhaust gas
monitoring equipment readings Cfor example, for
the concentration of total hydrocarbons}, if
available, should also be noted by the inspector.
A few additional items that pertain to poten-
tial exhaust gas release from reactors in particular
may also be entered on the inspection form. These
include the valve pressure setting (which should
prevent unnecessary releases), the rupture disc
pressure rating (which should be adequate to pre-
vent unnecessary blowouts), their conditions, and
the use of any blowdown and spill controls (for
example, diked areas, knockout drums or tanks for
containment, flares or scrubbers for emission
reduction, etc.). Finally, the reactor inspec-
tion form includes space for a sketch of the
system. This should be included for all but the
simplest operations. Flow rates and conditions
of temperature and pressure that vary locally
within the system may be indicated on the sketch.
The reverse side of the inspection form should
be used where more space is required, whether for
the sketch or for other information for which
the front side of the form contains insufficient
space.
A sample dryer inspection form is presented
as Exhibit 8-4. Since many of the items of infor-
mation required for the completion of this form
were discussed above in connection with the re-
actor inspection form, only the items unique to
the dryer inspection form x^ill be discussed
here. The type of dryer (agitated, fluid bed,
gravity, pneumatic conveying, rotary, screen, screw
conveyor, spray, or tray) and type of heat trans-
8-10
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fer (direct or indirect! should interest the in-
spector since the degree to which, the material
being dried is exposed to and mixed with, the drying
medium (air or other gasl is an important factor
in determining not only how much, drying occurs
but also how much, of any toxic material present
may be transferred to the gas stream. The chemical
composition of the drying gas stream, if other than
that of air, may be important for the determination
of the emission control efficiency obtainable
when using certain devices or techniques. The
composition of the material to be dried is of
obvious relevance, since the toxic substance of
concern would normally be contained in this
material, and its physical form Cfor example, pow-
dered, granular, pelletized, etc.), as well as
mesh size, would be necessary in order to evaluate
the possibility or degree of particle entrainment
expected. Since interparticle cohesion is also
of importance in this respect, the percentages
of moisture (or organic liquid) in the material
both before and after drying are also of interest.
A form intended for use during the inspection
of grinding and milling operations is presented
as Exhibit 8-5. Again, since many of the items
required to complete the grinding or milling operation
inspection form were discussed previously in
connection with the reactor inspection form, their
descriptions will not be repeated here. The
type of the mill (for example, ball, hammer, jet,
pebble, planetary, ring-roller, rod, roller, tube,
vibratory, etc.) is directly related to the inten-
sity of the grinding operation, the degree of size
reduction achieved, and, thus, the likelihood,
magnitude and nature of atmospheric emissions from
the equipment. It should be noted that only dry
grinding or milling operations would normally be
expected to result in particulate emissions.
In this regard, information concerning the chemical
composition of the material being processed should
be supplemented by the physical form and mesh
size of the material both before and after the
8-11
-------
grinding or milling operation.
A storage tank inspection form is included
as Exhibit 8-6. This particular form is designed
so that a single copy may be employed during the
inspection of a considerable number of material
storage tanks, such as may be encountered on a
tank farm or elsewhere on the grounds of a large
chemical production facility. The reasons for
the inclusion of specific identifying information
on the form were discussed previously in connection
with the reactor inspection form. Many of the
additional items to be completed (for example,
material stored, storage temperature, rated capa-
city, annual throughput, tank diameter, tank height,
roof color, shell color, condition of paint and
general state of repair, etc.) are employed directly
in the estimation of evaporative emissions accord-
ing to such methods as those detailed in "Compila-
tion of Air Pollutant Emission Factors," EPA Pub-
lication Number AP-42, Section 4.3, which was
presented earlier in this inspection manual.
Additional items required to complete the
storage tank inspection form may be employed in
modifying the results of such an emission calcu-
lation. For example, the tank vent pressure setting
may be sufficient to prevent some or even all
atmospheric releases from the equipment. Since
the storage tank evaporative emission calculation
procedure applies to equipment outdoors and in
the open, reductions in or the elimination of ex-
posure to direct solar radiational heating (as
well as to the clear nighttime conditions that
promote radiational cooling) and to the effects
of the wind may indicate that a downward adjustment
should be made to the calculated emission rate.
The storage tank level indicator reading is
more than just an evaporative emission calculation
input parameter (and suitable assumptions, such
as that the average condition is one in which
the tank if half-filled, could be made without
checking the indicator); rather, the level indicator
should be in a functioning and readable condition
8-12
-------
so as to serve as an aid in the prevention of
overfilling and spillage.
Finally, the storage tank, inspection form
includes provision for the recording of the use
of atmospheric emission control equipment. In
the case of storage tanks, a variety of control
techniques beyond the more generally applicable
gaseous emission reduction methods Cwhich, for
example, include absorption in a wet scrubber,
adsorption on activated carbon, condensation in
an indirect heat exchanger, incineration in a direct
flame afterburner, etc.) are often employed. Such.
methods may include storage tank design measures
such as floating- or expansion-roof or pressurized
construction; return lines to stationary tanks,
tank trucks, railroad tank cars, etc. for the
vapor-laden air displaced during filling operations;
other types of vapor balance and recovery systems,
some of which may be rather complex in nature (for
descriptions of these see such references as
"Air Pollution Engineering Manual," EPA Publica-
tion Number AP-40, Chapter 10); and spill con-
tainment measures such as the construction of
dikes around tanks that can allow spilled materials
to be removed by pumping or other collection meas-
ures before evaporation occurs.
A pump and compressor inspection form is pre-
sented as Exhibit 8-7. In general, the emissions
of any potentially toxic material that is being
handled may be expected to be dependent on the
flow rate through the equipment. The inlet and
outlet fluid temperatures and pressures are impor-
tant in determining the amount of material that
may escape at the locations of seals between moving
and stationary parts Cfor example, at rotating
impeller shafts and reciprocating piston connecting
rods) and, less often, at other points. Mechani-
cal seals (ordinarily flat face-plate pairs, one
rotating and one stationary, perpendicular to ro-
tating shafts) are generally superior (to packed
seals) for liquid containment purposes, espe-
8-13
-------
cially the internal type utilizing hydrostatic pres-
sure for a tighter seal. When double mechanical seals
are employed, a pressurized purge liquid may be
introduced between them to prevent leakage of the
toxic liquid being pumped. Labyrinth, seals, used
in handling gases, Include multiple knife-edges
or touch-points to achieve a cumulative pressure
drop through, the series of orifices that minimizes
gas leakage; in addition, a pressurized non-toxic
purge gas may be introduced into the seal to counter
such leakage. Except where a lubricant or purging
fluid is continuously introduced under pressure,
a small amount of leakage is to be expected even
from seals in good condition. Add-on emission
control equipment for pump and compressor leakage
is seldom employed. It should be noted that a
single pump and compressor form can be completed
for a number of similar items of equipment by
filling in ranges of data or typical values, ra-
ther than data representative of a single item of
equipment only.
A hood and ductwork inspection form is pre-
sented as Exhibit 8-8. These items are important
for the reduction of fugitive toxic substance emis-
sions. In general, the greater the volumetric
ventilation rate utilized In a potential fugitive
emission area, the greater the percentage of air
pollutants that may be captured for conveyance
to the air pollution control equipment. (If no
such equipment is employed, the hooding and venti-
lation only serve to alleviate in-plant toxicity
problems.) The hood type (.the design should en-
close the source area as much as possible, and
include flanges around entrance edges to keep
the air flow on the source side of the hood),
the hood dimensions and, most important, th.e dis-
tance to the source [whose inverse square is
usually roughly proportional to the induced air
velocity) are all factors that affect the hood's
fugitive emission capture efficiency (14). The
existence of a high air velocity near a central
duct opening in the hood, but very low velocities
8-14
-------
near the edges of the hood, can be remedied by
such, air flow distribution aids as multiple take-
off duct openings, baffles, filter banks, etc.
The velocity at the source that must be induced
by the hood for efficient air pollutant capture
is dependent on both the source release velocity
(ranging from high, for grinding operations to
negligible for slow evaporation] and on the presence
of interfering air currents Cdue to open doors and
windows, nearby equipment operations, etc.).
Lengths of ductwork operating under conditions
of positive pressure may permit the escape of toxic
air pollutants, and connection locations that are
not tight-fitting should be checked for air leakage.
An industrial waste incinerator inspection form
is included as Exhibit 8-9. Such incinerators
should not be overlooked by the inspector, since
they may constitute highly significant sources of
toxic air pollutant emissions. The number of
internal combustion chambers (usually two or three)
physically separated by refractory walls is direct-
ly related to the incineration efficiency that may
be obtained, since abrupt changes in the direction
of gas flow that occur between chambers improve the
mixing of potential pollutants, combustion air,
heat and flame. The volume of each chamber can
be used to calculate the corresponding residence
time (volume divided by volumetric gas flow rate
at combustion temperature), which would normally
total about 0.3 to as much as 10 seconds. The
waste preparation and charging method is an impor-
tant factor in determining the controllability of
combustion conditions, which should be maintained
free of such effects as erratic burning or sudden
flame quenching. Similarly, the draft should be
well controlled, with the combustion air being
preheated for the most effective incineration.
The operating temperature of the unit should be
maintained as high as possible, the normal range
being 1600 to 2000°F. Temperature controls are
ordinarily also necessary for the protection of
the equipment itself.
8-15
-------
In order to provide for the recording of suf-
ficient information regarding air pollution emission
control equipment, whether used in conjunction
with, a reactor, dryer, grinder, mill, storage
tank, incinerator, or other potential source
of atmospheric contaminants, an emission control
equipment inspection form has been included as
Exhibit 8-10. The information that is to be enter-
ed on this form would be adequate to permit a reason-
able estimation of control effectiveness to be
made. Although a great number of additional items
could be employed for the most accurate determi-
nation of control efficiency, the specific data
required and the computational methods involved
have been detailed by others Cfor example, see
"Air Pollution Engineering Manual," EPA Publication
Number AP-40, Chapters 4 and 5), and their descrip-
tion is beyond the scope of this manual.
In addition to the usual identification infor-
mation, the emission control equipment inspection
form includes provisions for the entry of the
name of the process emission source whose emis-
sions are being controlled by the subject equipment.
Certain items should be recorded regardless of
the type or types of control equipment being em-
ployed. These include the gas volumetric flow
rate (specified as the inlet or outlet value),
the entrance temperature of the gas emanating from
the source equipment, the exit temperature of the
gas from the final control device, and the gas
stream pressure drop through the control system.
Space is also provided on the emission control
equipment inspection form for entering the operat-
ing condition Csatisfactory, or unsatisfactory
due to the leaking of gas, plugging of lines, over-
loading of hoppers, etc.) of each device.
The following sections of the emission control
equipment inspection form pertain to specific cate-
gories of devices; each category utilized for the
control of the subject process emission source
should be check-marked. For the vapor condenser
category, a knowledge of the type Cfor example,
8-16
-------
shell-and-tube, barometric, etc.) of device is
essential to the understanding of its operation.
A barometric condenser also functions as a wet
scrubber, effecting a removal of particulate matter
and additional control of soluble vapors contained
in the exhaust gas stream. Information regarding
the cooling fluid, the coolant flow rate, the
coolant inlet temperature and the coolant outlet
temperature is useful for calculating the total
amount of heat transferred, the reduction in
the exhaust gas stream temperature, and thus, the
quantity of vapor that is removed from the exhaust
gas stream and converted to liquid form. For an
indirect condenser (such as one of the shell-and-
tube variety), the heat transfer area may be
either used as a check Cthe total amount of heat
transferred should equal the product of the heat
transfer area, the average temperature difference
between the coolant and exhaust gas streams, and
the overall heat transfer coefficient, which may be
approximated in accordance with the data and methods
presented in "Chemical Engineers' Handbook" by
Perry and Chilton), or may be used in place of
accurate coolant flow rate and temperature data
to estimate the amount of heat transferred, the
decrease in exhaust gas temperature, and the con-
denser's effectiveness. If the exhaust gas tem-
perature is monitored and recorded, such calcula-
tions may not be necessary.
Scrubbers may vary considerably in design
and in effectiveness for the removal of either
particulate matter, vapors, or both. The type
of scrubber (for example, spray, packed, venturi
or ejector) being used is a good though highly
approximate indicator of the control efficiency
that may be obtained. A knowledge of the scrubbing
liquid composition and pH is important in the case of
gaseous contaminant emission control, since the
solubility or reactivity of the contaminant in
the liquid may be critical to the scrubber's
effectiveness. The scrubbant circulating flow
rate is also relevant to the device's ability to
remove contaminants from the exhaust gas stream
8-17
-------
for many types of scrubbers, and equipment removal
efficiency as a function of flow rate juay be
either calculated or located in pertinent reference
books. Because of the great variations in scrubber
designs often encountered, and the often strong
dependence of effectiveness on the scrubber's physi-
cal shape and size, space has been provided for
the entry of information regarding the device's
geometrical form and key internal dimensions Caf-
fecting gas and liquid flow inside the equipment).
Alternatively, the monitoring or analysis of scrub-
bant composition may be combined with blowdown
and make-up rates to result in an estimation of
contaminant removal efficiency and atmospheric
emission rate.
Afterburners for the incineration of vapors
or fine particulate matter in the exhaust gas stream
may be of the direct flame or catalytic type, either
of which may involve heat recovery Cwhere the
hot gases leaving the device preheat the gases
entering, through indirect heat exchange). Time,
temperature and turbulence are critical to the
effectiveness of the device, the residence time
of the gases being dependent upon the inside volume
of the device, the temperature attained being de-
pendent upon the fuel firing rate and utilization
of heat recovery, and the turbulence being a func-
tion of such factors as the linear gas velocity
as it passes through the device. The monitoring
of the maximum gas temperature would be a useful
indicator of the emission control efficiency that
may be obtained.
An adsorber may contain either activated carbon
or another suitable material having a characteristic
capacity Cin pounds of adsorbate per pound of
adsorbant in the bed) for the removal and retention
of any gas stream contaminant. Regeneration, usu-
ally with steam , causes the contaminant that has
been concentrated in the adsorbant while the bed
was on-line to be released, and a final emission
control step (^condensation, incineration, and/or
other methods) must then be employed. The tempera-
8-18
-------
ture of the adsorption medium, which may be mon-
itored and recorded throughout the control-
regeneration-cooling/drying [usually with, clean
airl cycle, may be used to gain important insight
regarding the functioning of the regenerating type
of adsorption system.
Filter types include fabric filters or "bag-
houses" from which'the accumulated particulate
material is removed by such methods as shaking
or blowing with reverse-direction air jets; and
panel filters, which are either cleaned or replaced
periodically. Both the filter material (because
of its resistance to corrosive or hot gases, which
may destroy the fabric) and the total filter surface
(because of the considerations of particulate load-
ing and gas stream pressure drop, which may lead
to excessive wear and by-passing) are important
in determining the success of filtration as a con-
trol measure. The field investigator should care-
fully note the disposition of the collected dust,
since the very high efficiency obtainable through
appropriate filtration procedures may be seriously
overestimated should portions of the collected
dust be lost because of careless handling. Filter
pressure-drop monitoring is very useful.
Cyclone types include simple, multiple (par-
allel) or series arrangements - any may be operated
wet so as to avoid the re-entrainment of particles
from the inside walls of the devices. The cyclone's
principle of operation involves the migration of
particles suspended in the gas stream, under the
influence of centrifugal force, across the dia-
meter of the device and toward the wall for collec-
tion, as the gas stream simultaneously spirals
downward. As a result, the collection efficiency
obtained with a cyclone is dependent on its diameter
and height. Since cyclones, when used as control
equipment, only collect the larger particles and
seldom attain extremely high efficiencies, the
amount of particulate matter that is removed from
the hopper is a good indicator of the amount that
may be emitted to the atmosphere.
8-19
-------
The emission control equipment inspection
form also includes provisions for the description
of any other type of control equipment that may
be encountered by the field investigator. For
such, equipment, the inspector should record th_e
type or name of the device involved, its mode
of operation (for example, centrifugal, diffu-
sive, electrostatic, gravitational, etc.), and its
geometric form and dimensions relevant to the
flow of the gas and the performance of the device.
A generally applicable emission source summary
form (which can also be filled out by environmental
regulatory personnel or by a source facility repre-
sentative prior to or subsequent to the inspection
visit) is presented as Exhibit 8-11. The form
is chemical-substance emission oriented; each
material of concern is to be listed in the first
column, the equipment related to the substance
is to be listed in the second column (along with.
any pertinent instrumentation readings, such as tem-
peratures, pressures, volumes and flow rates, as discussed
previously), and emission parameter information
(where known, or when subsequently calculated)
is to be listed in the remaining columns. A minimum
of proprietary information need be sought in
completing the form, since emission data are by
law not entitled to confidential status.
A self-explanatory toxic emission preliminary
assessment procedure that may be used by the in-
spector is outlined as Exhibit 8-12. Alternatively,
after having completed his inspection visit and
returned to his office, the field investigator
can utilize the information he has gathered in
estimating the uncontrolled emission rates and
the efficiencies of air pollution control devices
in reducing potentially toxic emissions (under
both normal and abnormal operating conditions),
approximating the ground-level ambient air
concentrations of the toxic substances (in consulta-
tion with agency personnel responsible for atmos-
pheric dispersion modeling, or employing appropriate
references to obtain dilution factors (6) and/or
8-20
-------
volumes (15)), and comparing the concentrations
to permissible ambient levels determined as dis-
cussed previously in this manual, or by other means
The principal reference documents that are recom-
mended for use by toxic air pollutant emission
field investigators are listed in Exhibit 8-13.
Finally, the field investigator should prepare a
report for his supervisor including his observa-
tions and describing his findings. Since there
are relatively few toxic substance emission stan-
dards , such inspection reports should be made
available to those involved in the development of
such regulations.
8-21
-------
EXHIBIT 8-1
ITEMS OF SAFETY AND INSPECTION EQUIPMENT
Safety Equipment
Hard hat
Safety eyeglasses or goggles
Chemical-resistant safety shoes or boots
Gas mask with activated carbon canisters Cor other
suitable safety respirator)
Ear protectors (e.g., cotton or synthetic plugs)
Protective gloves
Fireproof clothing
Any other items required of visitors by the plant
owner or operator
Inspection Equipment
Credentials to establish identity and authority
Inspection manual and forms
Notebook and writing implements
Wristwatch with sweep-second hand (or wristwatch and
stopwatch)
Camera with film
Tape measure
Flashlight
Magnetic compass
Sample bags (with ties) or containers, with pocket
knife (or scraper) and sample brush
8-22
-------
EXHIBIT 8-2
PRE-ENTRY CHEMICAL EMISSION SOURCE INSPECTION FORM
Facility name
Facility address
Person to contact Telephone no.
Inspector ^ Date Time //am //pm
Reason for insp://Routine (Last insp. date; ) //Other
Temperature °F Wind speed mph Wind direction
Cloud cover Precipitation Other observ.
VISIBLE EMISSIONS
Plume Back- Obser- Dist.(ft)
Exhaust Release Opacity Plume ground ver's & Dir. Photo
Type Location (%) Color Descrip. Location to Plume No.
Stacks
Vents
Fugitive
Undeter-
mined
ODOROUS EMISSIONS
Odor Apparent Dist. (ft)
Odor Persis- Observer's Release & Dir. Photo
Odor Type Strength tence Location Location to Source No.
PARTICULATE DEPOSITION
Photo Sample
Recep. Type Recep. LOG. Dust Color Dust Coverage No. No.
ECOLOGICAL EFFECTS
Recep. Type Recep. LOG. Effect Description Photo No. Sample No.
SKETCE OF FACILITY LOCATION
(With emission source locations, property lines and fences,
entrance gates, surrounding roads, homes and institutions, parks
and forests, lakes and streams, observation and receptor loca-
tions listed above, distances and compass directions, etc. - use
reverse if more space is required.)
-------
EXHIBIT 8-3
REACTOR INSPECTION FORM
Facility name and address
Inspector Inspection date
Name of system
EQUIPMENT DESCRIPTION
Name of reactor Loc./desig. on plant layout Photo no.
Capacity gal Diam ft Ht. or length ft Condition ]
TYPE: //Batch //Continuous //Other
AUX. EQUIP.: //Column //Ejector //Condenser/7Scrubber
//Afterburner //Other
CHARGING: //Port //Pipe //Other
AGITATION: //Yes //No HEATING: //Yes //No COOLING: //Yes //No
PRESSURIZATION: //Yes //No VACUUM: //Yes //No
Processing Time Temperature cycle Pressure cycle
min °j? min psig min
Discharging method Cleaning method
MATERIALS PRESENT
Materials & Wts.Cft) Intermediates Products & Wts.Cf) By-Products
EXHAUST GAS
Release loc. or desig. Release ht. Plume opacity Odor Photo
on plant layout ft % no.
Vol. flow rate acfm Vent diam. in Exit vel. fps Exit temp ~°"F
Valve pressure setting & Rupture disc pressure rating &
condition psig condition psig
Monitor, equip, rdgs. & units Slowdown & spill controls
SKETCH
(Use reverse if more space is required)
-------
EXHIBIT 8-4
DRYER INSPECTION FORM
Facility name and address
Inspector Inspection date
Name of system "
EQUIPMENT DESCRIPTION
Name of equip. Loc./desig. on plant layout Photo no.
TYPE: //Agitated //Fluid bed //Gravity //Pneumatic conveying
//Rotary //Screen //Screw conveyor //Spray //Tray
//Other
OPERATION: //Batch//Continuous//Other
HEAT TRANSFER: //Direct //Indirect
DRYING MEDIUM: //Air //Other gas
Capacity Temp, cycle Pressure cycle Condition
Ib °F min mm Hg min "
//in //out
MATERIALS PRESENT
Materials to Physical Mesh Size Moisture In Moisture Out
be Dried Form ( x ) (%) (%)
CONTROL EQUIPMENT
//Cyclone //Filter //Scrubber //Afterburner //Adsorber
//Condenser //Other
EXHAUST GAS
Release loc. or desig. Release ht. Plume opacity odor Photo
on plant layout ft % no-___
Vol. flow rate acfm Vent diam. in Exit vel. fps Exit temp °F
Monitoring equip, rdgs. & units
SKETCH
(use reverse if more space is required)
-------
EXHIBIT 8-5
GRINDING OR MILLING OPERATION INSPECTION FORM
Facility name and address
Inspector Inspection date
Name of system "
EQUIPMENT DESCRIPTION
Capacity Ib Condition
TYPE: //Ball //Hammer //Jet //Pebble //Planetary //Ring-roller
//Rod //Roller //Tube //Vibratory //Other
OPERATION: //Batch //Continuous //Other
MATERIAL PRESENT
Material to be ground or milled
Physical form before process
Material size before process x mesh
Physical form after process
Material size after process x mesh
CONTROL EQUIPMENT
//Cyclone //Filter //Scrubber //Other
EXHAUST GAS
Release loc. or desig. Release ht. Plume opacity Odor Photo
on plant layout ft %_ no.
Vol. flow rate acfm Vent diam. in Exit vel. fps Exit temp °F
Monitoring equip, rdgs. & units
SKETCH
(Use reverse if more space is required)
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EXHIBIT 8-7
PUMP AND COMPRESSOR INSPECTION FORM
Facility name and address
Inspector Inspection date
Location or designation on plant layout Photo no.
Name of system "
Name of equipment
Number of similar items of equipment described on this form_
Equipment type: //Pump //Compressor (No. of stages
Material handled Flow rate //lb/min
Inlet temp. °F Inlet pressure psia
Outlet temp. °F Outlet pressure psia
Seal type: //Packed
(Packing material Lubricant press psia
//Mechanical (//Internal //External
^Single //Double
Purge liquid pressure psia)
//Labyrinth (Purge gas pressure psia)
//O th e r
Seal condition Leakage
Emission control
SKETCH
(use reverse if more space is required)
-------
EXHIBIT 8-8
HOOD AND DUCTWORK INSPECTION FORM
Facility name and address__
Inspector Inspection date
Location or designation on plant layout^ Photo no.
Name of system ]
Name of source equipment controlled
Volumetric ventilation rate acfm at
Hood type: //Plain rectangular //Flanged rectangular
//Plain slot //Flanged slot
//Plain circular //Flanged circular
//Booth //Other _
Hood dimensions: Length in. Width in. Height in,
Diam. in. Flange in. Distance to source in.
Air flow distribution aids: //Multiple take-offs (No. }
//Baffles //Filter banks //Other //None
Source release velocity: //High //Moderate //Low //Negligible
Interfering air currents://High //Moderate //Low //Negligible
Ductwork operation: //Negative pressure //Positive pressure
Hood condition Ductwork condition
Connections
SKETCH
(use reverse if more space is required)
-------
EXHIBIT 8-9
INDUSTRIAL WASTE INCINERATOR INSPECTION FORM
Facility name and address
Inspector Inspection date
Name of system
EQUIPMENT DESCRIPTION
Name of equip. Loc./desig. on plant layout Photo no.
Operation: //Batch //Continuous //Other
No. of chambers Volumes of chambers ft-*
Waste preparation & charging method Charging rate Ib/hr
Aux. Fuel: //Oil gph //Gas scfh //None //Other & rate
Draft: //Forced //Induced //Natural //Preheated //Other
Operating temperature °T Temp, controls
Equipment condition
WASTE COMPOSITION
Material Physical Form Percent by Wgt.
CONTROL EQUIPMENT
//Afterburner //Scrubber //Other
EXHAUST GAS
Release loc. or desig. Release ht, Plume opacity Odor Photo
on plant layout ft %_ no.
Vol. flow rate acfm Vent diam. in Exit vel. fps Exit temp. °F
Monitoring equipment readings & units
SKETCH
(use reverse if more space is required)
-------
EXHIBIT 8-10
EMISSION CONTROL EQUIPMENT INSPECTION FORM
Facility name and address
Inspector
_
Location or designation on plant layout
Name of system
Inspection date
Photo no.
Name of source equipment controlled
acfm
Gas volumetric flow rate
Entrance temp. °
(//in //out)
Exit temp. °F Pressure drop "H^O
Check all types utilized to control the source equipment;
//Condenser
//Scrubber
//After-
burner
//Adsorber
//Filter
//Cyclone
//Other
TYPE: //Shell-and-tube //Barometric //Other_
Condition
Cooling fluid
Coolant inlet temperature
Coolant outlet temperature_
Heat transfer area
Coolant flow rate
gpm
TYPE: //Spray//Packed//Venturi/7Ejector/7Other_
Condition ~
Scrubbing liquid composition and pH
Scrubbant circulation rate
Geometric form
Dimensions
in.
TYPE: //Direct-flame //Catalytic //Heat recovery
//Other Condition
Dimensions: in.diam
in.long Temp,
TYPE: //Activated Carbon //Other_
Condition
No. of beds
Weight of adsorbate in each.
Ib
Time on-line before regeneration mln.
REGENERATION: //Steam //Condensation ^/Incineration
//Replacement //Other
TYPE: //Shaker //Reverse-air //Panel //Other
Condition
Filter material
Filter surface area ft2
Disposition of dust
TYPE: //Simple//Multiple//Series//Wet//Other
Condition NO. of clones
Diam. of each
Disposition of dust
Type or name
in. Hgt. of each
in.
Mode of operation_
Condition
Geometric form
Dimensions
in.
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EXHIBIT 8-12
TOXIC EMISSION PRELIMINARY ASSESSMENT PROCEDURE
1. What chemical substance is present that could be released?
a. Particulate less than 1 nun in size
b. Material with vapor pressure of at least 1 mm Hg
2. What are the source emissions prior to entering any con-
trol devices?
a. Concentration from vapor pressure or chemical equili-
brium data, etc.:
mg/m 3
Average _ ppm Maximum _ _ ppm
3. What is the expected emission control efficiency?
Average emission conditions _ %
Maximum emission conditions _ %
4. What are the emissions leaving the control devices?
mg/m^ mg/m^
a. Concentration: Average _ ppm Max. _ ppm
b. Release rate: Average _ Ib/hr Max. _ Ib/hr
5. What is the expected peak ambient concentration?
a. From concentration dilution factor =
3 (3.16 + Dist. to Boundary or Recep./lO Vent Diam.)
Average _ ppm Maximum _ ppm
b. From release rate dilution volume =
3.14 (Wind speed) (Release height)2
mg/m
Average _ ppm Maximum
_
c. From odor thresholds and perceptions
mg/m 3
Average _ ppm Maximum _ ppm
What is the permissible ambient concentration?
a. Ambient standard, guideline or criterion
mg/rn-^ mg/m^
Average _ ppm Maximum _ ppm for hr
mg/m ^
b. Calculated from 1.65 x 10~3 (TLV) _ ppm
c. Calculated from 4.77 x 10~5 (LD5Q in mg/kg body wgt.J
d. Carcinogen recommended limit: 1 ng/m3 or 0.000001
7. What is the potential for a toxic air pollution problem,
based on a comparison of the answers to Questions 5 and 6?
8-33
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EXHIBIT 8-13
PRINCIPAL REFERENCE DOCUMENTS RECOMMENDED FOR USE BY
TOXIC AIR
Title
Toxic Substances
List CNIOSH}
Dangerous Proper-
POLLUTANT EMISSION INVEST IGATORS
Author
Christensen
et al
Sax
Subject
LD5QfS, TLV*S,
trace names
Toxi city rat-
Reference
No.
C2)
C3)
ties of Industrial
Materials
Handbook, of Chem-
istry and Physics
(CRC)
Chemical Engi-
neers ' Handbook
Weast
Perry and
Chilton
Air Pollution Danielson
Engineering Manual
(AP-40)
Industrial Venti- ACGIH
lation
Workbook of Atmos- Turner
pheric Dispersion
Estimates (AP-26)
ings, LDcg's,
TLV's, etc.
Chemical formu— C4)
lae, physical
properties
Chenical pro- C9)
cesses, equip-
ment , etc.
Control methods, (13)
equ:' prrient, emis-
sion factors, etc.
Rood design, Q.4)
TLV's, etc.
Calculating am- 0-5)
bient exposures
-------
REFERENCES
1. U.S. Dept. of Labor, Occupational Safety and
Health. Administration, General Industry Safety
and Health. Standards, OSHA 2206 (29 CFR 19101,
January 1976.
2. Christensen, H.E., ed., Luginbyhl, T.T., ed. and
Carroll, B.S., asst. ed., Toxic Substances List,
HEW Publication No. CNIOSH) 74-134, Rockville,
MD, June 1974.
3. Sax, N.I., Dangerous Properties of Industrial
Materials, 4th ed., Van Nostrand Reinhold Co.,
New York, 1975.
4. Weast, R.C., ed., Handbook of Chemistry and
Physics, 45th ed., Chemical Rubber Co., Cleveland,
1964.
5. Handy, R. and Schindler, A., Estimation of Permis-
sible Concentrations of Pollutants for Continuous
Exposure/ Publication No. EPA-600/2-76-155, June
1976.
6. Phelps, A.H., "Odors," Chapter 8 in Stern, A.C.,
ed., Air Pollution, Vol. 3, 3rd ed., Academic
Press, New York, 1976.
7. Leonardos, G., "The Profile Approach to Odor
Measurement" in Proceedings: Mid-Atlantic States
Section, APCA Semi-annual Technical Conference on
Odors: Their Detection, Measurement and Control,
New Brunswick, NJ, May 1970, Air Pollution Con-
trol Association, Pittsburgh.
8. Summer, W., Odor Pollution of Air, CRC (Chemical
Rubber Co.) Press, Cleveland, 1971.
9. Perry, R.H. , and Chilton, C.H.., editors, Chemical
Engineers' Handbook, 5th ed., McGraw-Hill, New
York, 1973.
-------
10. U.S. EPA, Compilation of Air Pollutant Emission
Factors, 2nd ed., Publication No. AP-~42, Febru-
ary 1976.
11. U.S. DHEW, Control Techniques for Hydrocarbon
and Organic Solvent Emission from Stationary
Sources, NAPCA Publication No. AP-68, March.
1970.
12. U.S. EPA, Control Techniques for Particrulate Air
Pollutants, Publication No. AP-51, December
1972.
13. Danielson, J.A., ed., Air Pollution Engineering
Manual, 2nd ed., EPA Publication No. AP-40, May
1973.
14. American Conference of Governmental Industrial
Hygienists, Industrial Ventilation, llth. ed.,
Committee on Industrial Ventilation, Lansing,
MI, 1970.
15. Turner, D.B., Workbook of Atmospheric Dispersion
Estimates, EPA Publication No. AP-26, March
1972.
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1 REPORT NO.
EPA-903/9-77-028
3. RECIPIENT'S ACCESSION*NO.
i. TITLE AND SUBTITLE
INSPECTION MANUAL FOR TOXIC AIR POLLUTANT
EMISSIONS - A Field Investigator's Guide for
Assessing Unregulated Chemical Emissions
5. REPORT DATE
August 1977
6. PERFORMING ORGANIZATION CODE
7. AUTHOH(S)
Robert M. Cutler, Robert N. Rickles, James A.
Rogers and Thomas L. Sieger
8. PERFORMING ORGANIZATION REPORT NO.
635
J. PERFORMING ORGANIZATION NAME AND ADDRESS
WAPORA, Inc. Corporate headquarters:
Northeast Office WAPORA, Inc.
211 E. 43rd St. 6900 Wisconsin Ave., N.W.
N.Y., NY 10017 Washington, D.C. 20015
10. PROGRAM ELEMENT NO.
Task 3
11. CONTRACT/GRANT NO.
68-02-2555
12. SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency
Research Traingle Park, North Carolina
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
27711
15. SUPPLEMENTARY NOTES
Prepared with the cooperation of nine major chemical manufacturing
companies with facilities located in USEPA Region III
\a ABSTRACT
This inspection manual provides guidelines for federal, state and local
environmental agency enforcement personnel who need to arrive at pre-
liminary assessments of potential toxic air pollution problems associ-
ated with chemical processing facilities and other emission sources for
cases in which standards and regulations have not been promulgated.
Included in the manual are discussions of inspection authority, emis-
sion toxicity, emission sources, control techniques, unsteady opera-
tions, emission data, field investigations and a variety of inspection.
forms. These forms pertain to equipment as reactors, dryers, grinders,
mills, storage tanks, pumps, compressors, hoods, ductwork, industrial
waste incinerators and emission control devices. The manual also in-
cludes correlations for the estimation of emissions, dispersion, and
toxicity (from lethal dosages - LD5g's), and compilations of threshold
limit values (TLV's), other Occupational Safety and Health Administra-
tion (OSHA) standards, known and potential carcinogens, odor descrip-
tions and thresholds, vapor pressures, required air velocities for pol-
lutant capture, safety and inspection equipment, toxic emission prelim-
inary assessment procedures, and principal toxic emission references.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Air pollution
Air pollution con-
trol equipment
*Chemical plants
Chemical reactors
Drying equipment
Exhaust hoods
Incinerators
• Industrial
*Inspection
Lethal dosage
*0dors
Seals
Storage tanks
Chemical manufacturing
was te:;Enf or cement
Evaporative emissions
Inspection manual
Threshold limit value
Toxic emissions
>r\ i
ior>
11 1 1
04 Atmospher-
ic Sciences
07 Chemistry
14 Methods
and
T?rm i rirnont-
13. DISTRIBUTION STATEMENT
Release unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGE?
122
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
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