United States
Environmental Protection
Agency
Environmental Monitoring
Systems Laboratory
P.O. Box 93478
Las Vegas NV 89193-3478
EPA/600/4-90/008
March 1990
Research and Development
Field Demonstration
for Mobile FT-IR for
Detection of Volatile
Organic Chemicals
-------
FIELD DEMONSTRATION FOR MOBILE FT-IR
FOR
DETECTION OF VOLATILE ORGANIC CHEMICALS
by
William G. Fateley and Robert M. Hammaker
Department of Chemistry - Villard Hall
Kansas State University
Manhattan, Kansas 66506
and
Donald F. Gurka
Quality Assurance and Methods Development Division
Environmental Monitoring Systems Laboratory
Las Vegas, Nevada 89193-3478
Contract #: CR81405903
Project Officer
Donald F. Gurka
Quality Assurance and Methods Development Division
Environmental Monitoring Systems Laboratory
Las Vegas, Nevada 89193-3478
ENVIRONMENTAL MONITORING SYSTEMS LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
LAS VEGAS, NEVADA 89193-3478
-------
NOTICE
This document is intended for internal Agency use only. Mention of trade
names or commercial products does not constitute endorsement or recommendation
for use.
ii
-------
ABSTRACT
A mobile laboratory for on-site analyses of volatile organic compounds
(VOCs) in the atmosphere using a Fourier transform infrared (FT-IR)
spectrometer is described. Laboratory calibration measurements are presented
and discussed. Estimates of detection limits as an average concentration over
a path length of 100 meters are made for 26 mid-infrared absorption bands of
21 compounds. These estimated detection limits vary from 5 to 76 parts per
billion (ppb). Some results of field measurements carried out at path-lengths
near 100 meters are presented and discussed. Field measurements at a number
of path lengths up to 600 m at an industrial site are presented.
Included in this report is a small collection of uncalibrated reference
spectra. These spectra have been added to Appendix 3 because they are part of
our spectral library.
iii
-------
iv
-------
CONTENTS
Abstract iii
Figures vi
Tables viii
Abbreviations and Symbols ix
Acknowledgment xi
1. Introduction 1
2. Conclusions 2
3. Recommendations 3
4. Materials and Methods 4
Mobile Laboratory 4
FT-IR Spectrometer 6
GC Measurements 6
Field Study Design 6
5. Results and Discussion 9
Laboratory Calibration Results 9
Field Work Results 12
6. Technology Transfer 32
Demonstrations of the Technique 32
Oral and Written Presentations 32
References 34
Appendices
A. Spectra from Field Work at Lawrence, KS 36
B. Spectra from Field Work at Site A 49
C. Spectra from Laboratory Calibration and Beer's Law Plots .... 55
-------
FIGURES
Number
1 A photograph (A) (top) and a schematic diagram (B) (bottom) of
the mobile laboratory 5
2 The PT-IR spectrometer and its collection telescope (A) (top)
and the source of infrared radiation and its collimating
telescope (B) (bottom) 7
3 A possible sampling arrangement for obtaining a grid of
64 intersection points by taking 16 spectral scans 8
4 Single beam mid-infrared transmission spectra of 100 meters of
ambient air at 0.1 cm-1 resolution. (A) (top) Full
spectrum shoving both windows. (B) (bottom) Lower
frequency window expanded 13
5 Mid-infrared absorbance spectra of 1,1,1-trichloroethane
(1,1,1-TCA). (A) (top) Laboratory calibration spectrum
in 16 cm cell at 0.5 cm-1 resolution. (B) (bottom) Field
spectrum for 117 meters at 0.5 cm-1 resolution 14
6 Mid-infrared absorbance spectra of methanol. (A) (top)
Laboratory calibration spectrum in 16 cm cell at 0.5 cm-1
resolution. (B) (bottom) Field spectrum for 100 meters
at 0.5 cm-1 resolution 15
7 Mid-infrared laboratory calibration absorbance spectra of
benzene. (A) (top) 16 cm cell at 0.1 cm-1 resolution.
(B) (bottom) 16 cm cell at 0.5 cm-1 resolution 16
8 Mid-infrared field absorbance spectra of 1,1,1-trichloroethane
(1,1,1-TCA) for 117 meters. (A) (top) 0.1 cm-1
resolution. (B) (bottom) 0.5 cm-1 resolution 18
9 Mid-infrared laboratory calibration absorbance spectra of
1,2-dichloroethane in 16 cm cell. (A) (top) 0.1 cm-1
resolution degraded to 0.5 cm-1 by smoothing the spectrum.
(B) (bottom) 0.1 cm-1 resolution degraded to 0.5 cm-1 by
truncating the interferogram 19
10 Mixture 3, KU tests compared against calibration spectra 21
11 Mixture 3, KU tests compared against calibration spectra 22
vi
-------
FIGURES (Continued)
Number Page
12 Mixture 3, KU tests with methanol subtracted out. Resultant
spectrum compared against calibration spectra 23
13 Single beam spectrum, "216 meters path length, Site A 25
14 Single beam spectrum, "600 meters path length, Site A, shoving
strong hydrocarbon absorption 26
15 Figure 14 absorbance spectrum, ratioed against Figure 13
spectrum, Site A 27
16 Absorbance spectrum, expanded Figure 15, Site A, compared
against isobutane calibration spectrum 28
17 Absorbance spectrum, two single beams same location, different
time and wind direction, Site A 29
18 Single beam spectrum, shoving methane absorbances betveen vater
lines, 147 feet path length, Site A 30
19 Absorbance spectrum, shoving change in CO and N20
concentration, "216 meters, Site A 31
vii
-------
TABLES
Number Page
1 Some major features of the Journey mobile laboratory 4
2 Parameters used in recording calibration spectra 9
3 Estimated detection limits (ppb) for some volatile organic
compounds (VOCs) at a path-length of 100 meters using
an appropriate absorption band from the mid-infrared
spectral region 11
4 Preliminary results from the testing at the University
of Kansas in May 1989 20
viii
-------
ABBREVIATIONS AND SYMBOLS
COADD:
cm
.-i
A Absorbance (Iog10 (TQ/T) where TQ is background transmittance
and T is sample transmittance) in Beer's Lav
Am Minimum detectable absorbance
APER Aperture for light stop
APOD Apodization
A Absorbance in calibration spectrum recorded at the lowest
concentration
a Absorption coefficient in Beer's Law
Beer's Law A = abc
BTU British thermal unit
b Path length in Beer's Law
BG Base Gain
bm Path length of 100 meters chosen for estimation of detection
limit corresponding to minimum detectable absorbance
br Path length 0.160 meters used in recording calibration spectra
B/S Beam splitter
c Concentration in Beer's Law
c_ Minimum detectable concentration as detection limit
16 Coaddition of spectra, 16 spectra in this.example
Concentration for calibration spectrum recorded at the lowest
concentration
Centimeter
Waves per centimeter or wavenumber
DA02 The model number of the Bomem interferometer
D.C. District of Columbia
DET Detector
EPA Environmental Protection Agency
EV: El Specific aperture
FACSS Federation of Analytical Chemistry and Spectroscopy Societies
FAX Facsimile machine for transmitting and reproducing printed
materials by telecommunication
FT1 Digital filter
FT-IR Fourier transform infrared
FT-IRS Fourier transform infrared system
f/4 Relative aperture or f number of 4 as ratio of focal length to
diameter
GA Georgia
GC Gas chromatography
GC/FID/ECD Gas chromatography with flame ionization and electron capture
detection
Ge Germanium as in KBr/Ge beam splitter
GL1 Nernst globar source of infrared radiation
HP High pass filter
IN Indiana
ix
-------
ABBREVIATIONS AND SYMBOLS (Continued)
K Degree Kelvin
KBr Potassium bromide as in KBr/Ge beam splitter
KS Kansas
KSU Kansas State University
KU University of Kansas
KW Kilowatt
Ib Pound
LP Low pass filter
MCI Mercury-cadmium-telluride No. 1 detector
MCT Mercury-cadmium-telluride as in MCT detector
m Meter
N Peak to peak noise in the absorbance baseline spectrum of
ambient air for a path length of 100 meters
N The molecule nitrogen
OH Ohio
PG Positional gain
ppb Parts per billion
P Pressure
RES Resolution expressed in wavenumbers, cm'1
s Second
SM Signal post
SOURCE Source of infrared radiation
SP Speed
SYO Identification of spectrum file
T Absolute temperature
1,1,1-TCA 1,1,1-trichloroethane
VA Virginia
VOC(s) Volatile organic compound(s)
-------
ACKNOWLEDGMENT
We wish to acknowledge Dr. Billy J. Fairless and Dr. Thomas Holloway
(Region 7), U.S. Environmental Protection Agency, for their interest in this
program and valuable advice on the critical problems to be investigated. The
experimental work done by the Kansas State University group was performed by
Martin L. Spartz, Jonathan H. Fateley, and Mark R. Witkowski. We wish to
thank Ray E. Carter, Mark Thomas, and Dr. Dennis D. Lane, Department of Civil
Engineering, University of Kansas, and Jody L. Hudson and Dr. John Helvig, EPA
Region 7, for their assistance with the field work.
xi
-------
SECTION 1
INTRODUCTION
Today, one of the major environmental problems is the identification of
the origin and amounts of volatile organic compounds (VOCs) being actively
emitted from the soil and other area sources into the atmosphere (1-7). There
are many sources of VOCs, e.g., landfills (both closed and active), grain
elevators (where chemical fumigants have been used), industrial sites, surface
waters (lakes and lagoons), surface impoundments (both closed and active),
container storage areas (drums and other containers), chemical spills (both
old and recent), leaking tanks (underground, in-ground, and above ground),
land treatment units, waste piles (both closed and active), water sludge
deposits, air stripping plants, and indoor areas. The presence of many
possible sites containing VOCs makes a rapid and reliable method for on-site
analysis extremely attractive. Such a method should provide a survey of a
site without the necessity of collecting many samples in canisters for later
analysis at a central laboratory. An open path infrared spectrometer shows
promise for this application.
A mobile system has been developed at Kansas State University (KSU) to
measure volatile organic compounds (VOCs) in the atmosphere using a Fourier
transform infrared (FT-IR) spectrometer (8-13). The mobile FT-IR spectrometer
system was developed to do on-site measurements and analyses so that results
can be obtained and reported more quickly. This technique has been tested in
controlled and field locations as part of the Superfund Innovative Technology
(SITE) program of the U.S. EPA.
As will be described in more detail in the Field Study Design subsection
of the Materials and Methods section, 16 spectral scans will suffice to probe
64 points in a sampling grid on a site. Rather than collecting 64 individual
samples in 64 canisters, at a cost of up to $1,000 and an analysis time of up
to 1 hour each, it may be possible to pinpoint a few sites for sampling by
canister to supplement the open-path infrared spectra. The savings in time
and cost for doing the 16 spectral scans and analyzing a few sampling
canisters with the mobile laboratory will be substantial compared to collec-
tion and transportation to a central laboratory and detailed analysis (by
cryogenic infrared spectrometer or other methods such as gas chromatography or
mass spectroaetry) of 64 sampling canisters.
Our program, up to February 1, 1990, in the development of open path
infrared spectrometry is described in the Results and Discussion section which
consists of subsections about the laboratory calibration results and field
work results. Representative spectra are discussed, and additional spectra
appear in appendices.
-------
SECTION 2
CONCLUSIONS
A mobile high resolution Fourier transform interferometer has been
evaluated in the field for detection and measurement of VOCs in the
atmosphere. The high resolution capability of the instrument allowed the
measurement of target compounds in the presence of atmospheric water and
carbon dioxide. The instrument was transported by a mobile laboratory to a
hazardous waste site where measurements of the compounds present were
completed in a matter of hours.
A self-contained mobile laboratory that contains the FT-IR has been
equipped to travel to any site in the continental United States for rapid
examination and detection of toxic atmospheric compounds. Experiments during
field studies at various sites in June 1989, demonstrated its capability to
measure volatiles in the parts-per-billion range.
In the course of this study, staff from EPA Region 7 have been trained to
use the mobile laboratory. Laboratory calibration of the infrared
interferometer has been demonstrated as applicable for field use for some
compounds. Performance of field operation of the instrument has been compared
with Dr. Dennis Lane's canister sampling and gas chromatography with flame
ionization (Method T1A and Method 8010) at the University of Kansas (KU).
-------
SECTION 3
RECOMMENDATIONS
During the course of this work certain recommendations for future work
were recognized. A summary of these recommendations is presented below:
1) Apply this technique to the examination of a variety of new different
sites, e.g., grain elevators, lagoons, chemical spills, gasoline
stations, storage tanks, incinerators.
2) Evaluate instrument sensitivity with open path lengths up to 2,000
meters.
3) Design a simple, inexpensive, backpack-size instrument for in situ
studies. A near infrared Hadamard transform spectrometer is one
possibility to be considered here.
4) Finish field test program designed by Mr. Jody Hudson, EPA, Region 7.
This program is entitled "Project Overview for Performing a Comprehensive
Evaluation of a Field Portable FT-IRS Remote Sensing Instrument,
January 9, 1989".
5) Expand the target list of compounds. Ve anticipate a target list of
about 70 volatile organic solvents.
6) Complete the calibration of target compounds.
«
7) Install the vacuum system and the Hanst long-path cell (160 meters) in
mobile laboratory. This will be applicable for sampling of small areas
or in those situations where a viable open-path is unattainable. This
unit can also be used to examine the contents of a canister.
8) Prof. Peter Griffith's mobile supercritical fluid gas chromatograph
system vould enhance the capabilities of the mobile laboratory. This
system has the capability to analyze semi and non-volatile compounds
without solvent extraction.
-------
SECTION 4
MATERIALS AND METHODS
MOBILE LABORATORY
Mobility is provided by a Journey mobile home designed to house and
transport the necessary measurement instruments and the crew. A listing of
some of the major features of the Journey mobile laboratory is presented in
Table 1. A photograph and a schematic diagram of the general layout of the
mobile laboratory is shown in Figure 1. The conversion of the mobile home to
a mobile laboratory vill be a continuing process. At the time of this
writing, the unit is configured to house a crew of three and the following
instrumentation: the FT-IR spectrometer with its collection telescope, the
source of infrared radiation and its collimating telescope, appropriate
computers, a weather station, a FAX machine, and a cellular telephone. The
additions of a specially designed vacuum system, and a variable-path
multireflection cell (White cell) to provide path lengths from 6 to 160 meters
are in progress. Once the vacuum system and the variable path cell are
operational, the capabilities of the mobile laboratory will include canister
collection of either atmospheric gases or soil gases for analyses in the
variable-path cell.
TABLE 1. SOME MAJOR FEATURES OF THE JOURNEY MOBILE LABORATORY
Journey 40' Mobile Laboratory
-Ford 460 cu. in. Engine
-John Deere Chassis
-95 Gallon Fuel Capacity
-160 Ib. Propane Capacity
-80 Gallon Water Capacity
-6.5 kv Generator
-Dual 13,500 BTU Air Conditioners
-Dual 30,000 BTU Furnaces
-Hydraulic Leveling Jacks
-10 Cubic Foot Refrigerator
-4 Burner Range w/Conventional Oven and Microwave Oven
-Three Overhead Storage Pods
-Murata FAX Machine
-Uniden CP1200 Cellular Telephone
-------
WEATHER STATION
WEATHER STATION COMPUTER
STORAGE
CREW LIVING QUARTERS
PLOTTER 1
r^^ /
1 | ( , i / FTJ 1
U-J
COMPUTER
(^0
~ ~| ~
1 °\ «
! X
I \
'-' r\,N
1 1^ tj.).!:'.
v^wifcnM
| 1 1 X
...}.... | | LABI
EQUIPMENT DOOR
SINK
STOVE
1
I
1
1
i
1MU
CUM HACK
: I '
: 1 1
^v * * '
"*S
5RATORY WORK AREA
1
1
1
CREW E
/
\
w
/
ITRANCE. EXIT
INTERIOR VIEW OF MOBILE LABORATORY
Figure 1. A photograph (A) (top) and a schematic diagram (B) (bottom) of the
mobile laboratory.
-------
FT-IR SPECTROMETER
The FT-IR spectrometer, shown in Figure 2A, is a Bomem DA02 system
equipped with a KBr/Ge beam splitter, a MCT detector (liquid nitrogen cooled),
a variable-height/depth tripod and a Gibralter 3 degree of motion head; the
collection telescope is a 10-inch Cassegrainian.
The source of infrared radiation, shown in Figure 2B, is an air cooled
and quartz shielded Nernst glower operating at 2,000 degrees Kelvin. This
source is located at the focal point of a 20-inch Newtonian telescope (of
80 inch focal-length and f/4 optics with gold-coated mirrors) in order to
generate a collimated beam of infrared radiation.
The mobile laboratory is driven to one side of the site to be surveyed,
and the FT-IR spectrometer with its collection telescope is set up adjacent to
the mobile laboratory. The source of infrared radiation and its collimating
telescope are positioned on the opposite side of the site to be surveyed so
the collimated beam of infrared radiation may be sent across the site to enter
the collection telescope of the FT-IR spectrometer. An alternative
arrangement is to place both the source of infrared radiation and its
collimating telescope and the FT-IR spectrometer with its collection telescope
adjacent to the mobile laboratory. Then a reflector is placed on the opposite
side of the site so the collimated beam of infrared radiation is sent across
the site to the reflector and reflected back to the collection telescope of
the FT-IR spectrometer. In either arrangement, the infrared absorption
spectrum of the atmosphere above the site being surveyed is used to identify
any VOCs that are present in the path of the collimated beam of infrared
radiation.
GC MEASUREMENTS
A limited number of confirmatory analyses were performed at Kansas
University using air samples collected in Summa canisters using Method T14.
The volatile compounds in these samples were measured using gas chromatography
with flame ionization and electron capture detection (GC/FID/ECD).
FIELD STUDY DESIGN
The arrangement with the FT-IR spectrometer and the source on opposite
sides of the site is illustrated in Figure 3 for a grid pattern of 8 spectral
scans in one direction and 8 spectral scans in a perpendicular direction.
Thus, a total of 16 spectral scans is necessary to spectroscopically
interrogate a total of 64 intersection points. If a point source of pollutant
emission is located within the grid, appropriate comparisons among the sixteen
spectral scans can identify which intersection point is nearest the point
source. If the emission is more uniformly distributed, comparisons among the
16 spectral scans will also identify such a condition. A crew of three can
set up the instrumentation in about 30 minutes, take data for up to
30 minutes, and take down the instrumentation and move to the next scan
position in an additional 30 minutes. The 16 spectral scans would then
require 24 working hours and would require 2 to 3 working days. Once the site
has been surveyed in this manner, individual samples at intersection points of
-------
Figure 2. The FT-IR spectrometer and its collection telescope (A) (top) and
the source of infrared radiation and its collimating telescope (B)
(bottom).
-------
Grid Pattern
Source
o
Figure 3. A possible sampling arrangement for obtaining a grid of
64 intersection points by taking 16 spectral scans.
interest may be taken for delivery to an appropriate EPA laboratory for more
detailed analysis. The savings in time and money (estimated $500-1000/sampl«)
promise to be substantial compared to taking canister samples at all 64
intersection points and returning 64 samples to an appropriate EPA laboratory
for detailed analysis.
-------
SECTION 5
RESULTS AND DISCUSSION
LABORATORY CALIBRATION RESULTS
The task of building a library of calibration spectra has begun. Two
uses of the calibration spectra are: (1) to identify the VOCs that are
present in the path of the collimated beam of infrared radiation between the
source of infrared radiation and the FT-IR spectrometer; (2) to make estimates
of the detection limits corresponding to one or more of the absorption bands
in the infrared spectrum of each compound in the library. The parameters
chosen for recording these calibration spectra appear in Table 2. These
calibration spectra were all recorded in a fixed path cell of length 16 cm.
We are now using a variable path, multi-reflection cell (White cell).
This variable path cell may be used in a normal laboratory setting for
obtaining calibration spectra at a variety of path lengths if necessary or may
be installed in the mobile laboratory and used for on-the-spot analysis. Ve
currently have an air sampling canister containing accurately known concentra-
tions of a multi-component volatile organic compound (VOC) mixture. This was
supplied by the EPA Region 7 laboratory for analysis as a test of our
methods. A preliminary analysis using the fixed path-cell of length 16 cm
suggests that the variable path-cell will be helpful in the complete analysis
of the sample supplied by the EPA Region 7 laboratory.
The calibration spectra are used in conjunction with ambient air
background spectra obtained in field measurements to make estimates of
TABLE 2. PARAMETERS USED IN RECORDING CALIBRATION SPECTRA
Cell length: 16 cm
Partial Pressure: variable-in range 0.006 - 0.28 torr
Total Pressure (with N2): "740 torr (nominal)
Resolution*: 0.1 cm"1 or 0.5 cm"1
Number of Coadded Scans: 256
Scan Speed: 1.5 cm s"1
Apodization: Boxcar
'All spectra were recorded at 0.1 cm"1 spectral resolution and in many cases
the resolution was degraded to 0.5 cm"1 by smoothing.
-------
detection limits as follows. Single beam ambient air spectra taken in the
field for a path-length of 100 meters are ratioed to obtain the absorbance
baseline spectrum of ambient air. The minimum absorbance that would be
detectable in a path-length of 100 meters is taken as 3 N. N is the peak to
peak noise at the wavenumber of the absorption band in the absorbance baseline
spectrum of ambient air for a path-length of 100 meters. Then use is made of
Beer's Law (i.e., A = abc where A is the absorbance of the band, a is
absorption coefficient in units of [(path lengthXconcentration)]'1, b is
path-length, and c is concentration). For a band of the minimum detectable
absorbance, Am, Beer's Law is An = 3N = abBca with DB = 100 meter and cm the
minimum detectable concentration in parts per billion (ppb). For the
laboratory calibration spectrum, Beer's Law is AC = abrc where b is
0.160 meter and cf is the lowest measured concentration in ppb. The value of
cn, the minimum detectable concentration in ppb, is obtained by taking the
ratio of the two Beer's Law equations and solving for c = (3N/A )
(0.160/100)cr = (4.8xKT3 N/Ar)cr. In doing these calculations it is critical
to note that concentration in molarity does not change in the gas cell for a
given amount of material in the fixed volume as total pressure and/or
temperature change but concentration in ppb does change. Thus, the value of
cr in molarity must be converted to ppb for the same total pressure and
temperature as those for which CB is being calculated in ppb.
Table 3 contains the minimum detection limits in a path-length of
100 meters for all compounds in the library of calibration spectra at the time
of this writing, and estimated by the method described in the previous
paragraph. These detection limits correspond to a concentration averaged over
a path length of 100 meters at a given total pressure and temperature. Thus,
the amount of material between the source of infrared radiation and the FT-IR
spectrometer if uniformly distributed along the 100 meter path would be at the
concentration given in ppb in Table 3. Atmospheric interferences will often
raise these minimum detection limits. The applicability of Beer's Law to the
absorption bands used to make the calculations in Table 3 was examined by
obtaining all calibration spectra at four different concentrations and
plotting the results as absorbance versus concentration.
The compromise between resolution and signal-to-noise ratio will be a
matter of great significance in the field work. For bands that are broad
relative to the spectral resolution chosen, in the operation of the FT-IR
spectrometer, a higher resolution scan (smaller value of the resolution in
cm'1) will have approximately the same absorbance at the band maximum and a
higher noise level causing a signal-to-noise ratio decrease and a poorer
(i.e., higher) detection limit. Here the lower resolution scan is to be
preferred. For the case where the band-width is comparable to the spectral
resolution, chosen in the operation of the FT-IR spectrometer, a higher
resolution scan (smaller value of the resolution in cm'1) may yield a dramatic
increase in the absorbance at the band maximum along with the higher noise
level. In this case, the effect on the signal-to-noise ratio and the
detection limit is not easily predictable and each case needs to be evaluated
individually. The calibration spectra were recorded at 0.1 cm"1 resolution to
give the flexibility of degrading the resolution, if desired. This
degradation of the resolution is accomplished in the data processing either
by smoothing the spectrum or by truncating the interferogram prior to
10
-------
TABLE 3. ESTIMATED DETECTION LIMITS (ppb) FOR SOME VOLATILE ORGANIC
COMPOUNDS (VOCs) AT A PATH LENGTH OF 100 METERS USING AN
APPROPRIATE ABSORPTION BAND FROM THE MID-INFRARED REGION
Compound
Chlorinated hydrocarbons
Allyl chloride
Carbon tetrachloride
Chlorobenzene
Chloroform
1 , 2-Dichloroe thane
Methylene chloride
Te t rachloroe thy lene
1,1, 1-Trichloroe thane
Tr i chloroe thy lene
Aromatic hydrocarbons
Benzene
Ethylbenzene
Pyridine
Toluene
Alkane
Cyclopentane
Alcohols
n-Butanol
Ethanol
Isopropanol
Methanol
Ke tones
Acetone
Methyl ethyl ketone
Methyl isobutyl ketone
Ester
Ethyl acetate
Ethers
Diethyl ether
1 , 4-Dioxane
Te t rahydrof uran
Vavenumber
(cm'1)
756.9
795.2
741.2
772.6
731.3
749.5
916.3
726.3
849.4
673.9
2794.0
700.3
694.3
2966.0
2967.4
1068.8
1066.1
2982.7
956.5
1033.4
1033.4
1217.7
1174.2
2965.4
1241.4
1142.9
2863.1
1138.3
2981.7
1084.4
Resolution
. (cm'1)
0.5
0.5
0.1
0.5
0.5
0.5
0.5
0.5
0.5
0.1
0.5
0.1
0.1
0.5
0.5
0.5
0.5
0.5
0.5
0.1
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
Detection Limit
(ppb)'
67
6.3
26
b
34
20
19
8.1
18
c
31
c
c
7.2
22.4
35
31
19
76
18
8.1
36
40
18
5.0
9.3
11
9.9
17
26
These detection limits using concentration in parts per billion (ppb)
are for P < 740 torr and T - 298 K.
'These measurements are being repeated.
cThese bands fall in spectral regions containing sharp water vapor
absorption bands and the detection limits are dependent on humidity.
11
-------
transformation to the spectrum. The calibration spectra in the library
contain examples of both cases and some of these examples are presented and
discussed later (see Field Work Results). The situation becomes more
complicated for spectral regions containing many sharp water-vapor absorption
bands. Here, the higher resolution data may show the effect of these water-
vapor bands more clearly and lead to better decisions about the best way to
proceed. One option would be to use the higher resolution data to subtract
out some of the water vapor bands and then degrade the resolution to reduce
the noise. This procedure might minimize errors caused by sharp water vapor
absorption bands broadened under lower resolution making unsuspected
contributions to absorption bands from VOCs.
FIELD WORK RESULTS
Open path scans have been done at different controlled locations using
five path lengths of 65, 100, 117, 120, and 250 meters. Initial observations
at different industrial sites involved various open path-lengths from a few
meters to 600 meters. The need for a variety of path lengths will be
discussed later. Extensive initial work was done indoors at a path length of
65 meters along the length of the hallway on the third floor of Villard Hall
at Kansas State University in Manhattan, Kansas. The work at the other four
path lengths was done outdoors at Lawrence, Kansas in collaboration with the
group from the Department of Civil Engineering at the University of Kansas
headed by Dr. D. D. Lane. The University of Kansas group has developed a
plume generator that releases a plume of VOCs of known characteristics as
measured by gas chromatography. Work at 120 meters was done in February 1989.
Work completed the week of May 15-19, 1989, was done at 100, 117 and 250
meters. The spectra to be discussed here are from the work completed in May
and are for a 100 meter path or a 117 meter path (i.e., 385 feet).
The interferences caused by water vapor and carbon dioxide in the
atmosphere are illustrated by the single beam transmission spectra in
Figure 4. In Figure 4A (top) the full mid-infrared spectrum containing useful
windows is shown while Figure 4B (bottom) contains an expansion of the window
that appears to be most attractive for our purposes. Figure 5 illustrates the
interference caused by water vapor lines and the poorer signal-to-noise ratio
of field spectra for 1,1,1-trichloroethane by comparing the laboratory
calibration spectrum in Figure 5A (top) with the field spectrum Figure 5B
(bottom) both at 0.5 cm'1 resolution. A more favorable comparison occurs for
methanol in Figure 6 where the laboratory calibration spectrum in Figure 6A
(top) differs little from the field spectrum in Figure 6B (bottom) both at
0.5 cm'1 resolution. The average concentration of methanol in spectrum 6B is
calculated to be 250 ppb and here an amount approximately 20 times smaller
would give the minimum detectable absorbance.
The compromise between resolution and signal-to-noise ratio is
illustrated for laboratory calibration spectra for benzene in Figure 7 where
the absorption band is of comparable width to the spectral resolution chosen
in the operation of the FT-IR spectrometer. Changing from a resolution of
0.1 cm"1 in Figure 7A (top) to 0.5 cm'1 in Figure 7B (bottom) lowers the peak
absorbance by a factor close to 2 and reduces the noise by a comparable but
larger factor making it somewhat subjective to choose which presentation is to
12
-------
X 1.0E+04
3. 30
2150
r
100. CM-1
-0. 09
X i . OF! 4-0 4
3.30 -j r
3.02-
2. 24 -I
1. 46 -
0. 69 -
1300.
I
1025.
\ T
r t
750. CM-1
Figure A. Single beam mid-infrared transmission spectra of 100 meters of
ambient air at 0.1 cm"1 resolution. (A) (top) Full spectrum
shoving both windows. (B) (bottom) Lower frequency window
expanded.
13
-------
0. 120
1 1 1 1
950.
700. CM-1
o. :2
-0.005
1 200.
950.
700. CM-1
Figure 5.
Mid-infrared absorbance spectra of 1,1,1-trichloroethane
(1,1,1-TCA). (A) (top) Laboratory calibration spectrum in 16 cm
cell at 0.5 cm~x resolution. (B) (bottom) Field spectrum for
117 meters at 0.5 cm'1 resolution.
14
-------
X 0. 1
0.5800
-0.0340
1 100.
1020.
940. CM-1
X 0.
0.5200 I
-0.0350
1 100.
1020.
Figure 6. Mid-infrared absorbance spectra of metHanoi. (A) (top) Laboratory
calibration spectrum in 16 cm cell at 0.5 cm"1 resolution. (B)
(bottom) Field spectrum for 100 meters at 0.5 cm"1 resolution.
15
-------
U . J 1 U -|
-
IJ-k) . 2 9 5 -
^
Z
<
CD
cr o . 2 2 o -
O
CO
CD
<0. 144 -
-
0. 069 -
-
-0 . 006
1 1 1 1 1 r
m >»n*.i»n). jUtiii i.i. . '"^*fr||jg
1 1 1 1 1
-
-
-
-
1
-i
1
i i i i 1 i i i i 1 r°~ ~i
750 687. 625. CM-}
U . J / U
-
Li-lQ 295 -
O
CD
CCO . 2 2 0 -
O
00
CD
<0. 144 -
-
0. 069 -
-0. 006
I i , , , | i
'
i
»
^
H
-
-
i i i i i i i i i i i 1
750
687.
625. CM-1
Figure 7. Mid-infrared laboratory calibration absorbance spectra of benzene.
(A) (top) 16 cm cell at 0.1 cm'1 resolution. (B) (bottom) 16 cm
cell at 0.5 cm"1 resolution.
16
-------
be preferred for the best detection limit. The decision is complicated by the
fact that the 720 to 670 cm"1 region contains many sharp water-vapor
absorption bands and high resolution may be necessary to pick out the benzene
absorption band among the absorption bands of water vapor. A definite choice
is easily made for the case of the field spectra of 1,1,1-trichloroethane
shown in Figure 8 where the absorption band is broad relative to the spectral
resolution chosen in the operation of the FT-IR spectrometer. Changing from a
resolution of 0.1 cm"1 in Figures 8A (top) to 0.5 cm"1 in Figure 8B (bottom)
makes little difference in the peak absorbance and reduces the noise
dramatically. Clearly, the spectrum in Figure 8B (bottom) will yield the
better detection limit. Experience to date has been that the most favorable
resolution to use for a given spectrum may need to be determined on-site. Our
procedure to date has been to record all spectra at 0.1 cm"1 resolution and
then degrade the resolution by reprocessing the data. Then a comparison of
the different presentations as illustrated in Figures 7 and 8 is used to
select the best presentation in each case.
Vhen the choice is made to take data at this higher resolution, we then
have the capability to degrade the resolution by reprocessing the data. There
are two alternatives: smoothing the spectrum or truncating the interferogram
and then transforming to the spectrum. Experience to date with these two
alternatives is illustrated for 1,2-dichloroethane in Figure 9 where both
spectra were recorded at 0.1 cm"1 resolution and degraded to 0.5 cm"1. The
spectrum in Figure 9A (top) is for smoothing the spectrum and the spectrum in
Figure 9B (bottom) is for truncating the interferogram. Clearly the spectrum
in Figure 9A (top) will yield the better detection limit.
The field work in February 1989 involved the release of methylene
chloride as a known, and both the Kansas State University and University of
Kansas groups measured an average concentration near 300 ppb. Ve believe that
agreement between long-path FT-IR and GC/FIO/ECD within 20 percent is
excellent. The field work in May 1989 involved the separate release of four
single materials and four multiple component samples that were unknown to KSU
investigators. The following table shows the results of this testing to date.
The qualitative results presented in Table 4 are very encouraging to the
authors; however, the quantitative results seem to be on the low side. This
could possibly be due to error, but a greater possibility is that the infrared
beam observes the atmosphere at different heights from the canisters used in
this measurement. This is equivalent to stating that the canister and open-
path approaches are analyzing different samples. In new testing at the
University of Kansas this fall height factors will be addressed, as well as
many other operational parameters.
The bulk of the spectral data can be reviewed in Appendix A-l. One
mixture has been added to the text so it can be discussed in greater detail.
Figures 10, 11, and 12 are of Mixture 3 from the KU tests. In Figure 10, we
can see some fairly large interfering atmospheric absorptions. The two
features most easy to identify are methanol and acetone. One immediately
notices the contour of the R-Spectral Branch of methanol has changed
dramatically in the region of 1055 cm"1. This undoubtedly is due to the
presence of n-butanol or ethanol or both. The spectrum of ethanol in
17
-------
0. 170
0. 170
-0.023
1 150.
975.
I ' r
800. CM-1
Figure 8. Mid-infrared field absorbance spectra of 1,1,1-trichloroethane
(1,1,1-TCA) for 117 meters. (A) (top) 0.1 cm"1 resolution.
(B) (bottom) 0.5 cm"1 resolution.
\*J .» y * * W** / ^ V & A * * Mft^ ^ ^> ^ h? y V* ^ ^
(B) (bottom) 0.5 cm"1 resolution.
18
-------
X 0. 1
0.4500 T
M). 3520 -
CQ
Q3). 2540 -
O
CO
CD
.2540
O
CO
CQ
"S. 1560 -
0.0530 -
-0.0400
P..
-i
I I
1400.
1075,
750. CM-1
Figure 9. Mid-infrared laboratory calibration absorbance spectra of
1,2-dichloroethane in 16 cm cell. (A) (top) 0.1 cm"1 resolution
degraded to 0.5 cm'1 by smoothing the spectrum. (B) (bottom)
0.1 cm"1 resolution degraded to 0.5 cm"1 by truncating the
interferogram.
19
-------
TABLE 4. PRELIMINARY RESULTS FROM THE TESTING AT THE
UNIVERSITY OF KANSAS IN MAY 1989
FT-IR Assignment and Quantitation
Sample Assignment Average
Label Concentration
100 m (ppb)
GC/FID/ECD Measurement
Actual
Compound
Average
Concentration
100 m (ppb)
Sample A
Sample B
Sample C
Sample D
Mixture 1
Mixture 1
Mixture 1
Mixture 2
Mixture 2
Mixture 2
Mixture 3
Mixture 3
Mixture 3
Mixture 3
Mixture 4
Mixture 4
Mixture 4
Acetone
Methanol
Methylene Chloride
Toluene6
Acetone
Methylene Chloride
Toluened
Isopropanol
n-Butanol
f
Acetone
Methanol
Ethanol
n-Butanolh
1,1,1-TCA
Methylene Chloride
i
44.5"
148
24.4"
73
37
40.4
36.8
58
14.4
97.7
64
g
g
18.6
42.3
Acetone
Methanol
Methylene Chloride
Toluene0
Acetone
Methylene Chloride
Toluene*1
Isopropanol
n-Butanol
Acetone
Methanol
Ethanol
n-Butanol
1,1,1-TCA
Methylene Chloride
Toluene
b
b
60
110
b
75
80
e
e
e
e
e
e
e
e
e
e
"Average concentration at 232 meters path length.
bKU group could not be quantitative due to the GC column in use that day.
CKSU group was not 100X sure of assignment of toluene. Later a viable
spectral pattern for toluene vas recognized and successfully used for
identification.
dKSU group informed of toluene presence. The pattern recognization
previously discovered and reported in footnote c vas used to measure
concentration.
"No canister samples were collected.
'Presence of n-pentane is suspected due to the presence of one specific
band the carbon-hydrogen shielding region.
Overlapping bands present; therefore, calibration has some uncertainty.
hlnformed of its presence and were able to confirm its presence using
a smaller band.
Presence of toluene suspected, spectral overlap vith 1,1,1-TCA.
20
-------
-]- 1 T 1 I ] 1 1 I T
Atmospheric obsorbar.ce spectrum
Unknown mixture 3 KU tests
T
a lib rat ion sp»«. tru*n
^/VvJ
Calioration spectrum
Me t haro I
800. CM-1
Figure 10. Mixture 3, KU tests compared against calibration spectra.
-------
T r i"
T
AI mo , |j l:i-1 ic ab so r bonce spectrum
Unknown mixture 3 KU tests (top)
Calioration spectrum
Ethanol (middle)
Co lie rot ion spectrum
Ace t one
1175
r"'"1
300. CM-1
Figure 11. Mixture 3, KU tests compared against calibration spectra.
-------
N>
A t mo spheric a b s o i b a r c e -j p c c t r u m w i 1 h. me t h a P. o 1
subtracted: Unknown mixture 3 KU tests (top)
Colioratior spectrum
E t haro I (middle)
Cciioration spectrum
Ac e t one
!0i)0
92 '.>.
300. CM-1
Figure 12. Mixture 3, KU tests with methanol subtracted out. Resultant spectrum compared against
calibration spectra.
-------
Figure 11 confirms this possible overlap. Figure 12 represents the resultant
spectrum after the methanol has been spectrally removed. The band remaining
now resembles ethanol; however, at closer observation n-butanol (not shown
here) contributes to this absorbance as well.
The remainder of this section presents some results obtained at an
industrial site, to which the study was allowed access so long as it was not
identified. For this reason, those samples are labeled as Site A. Figure 13
contains the single beam atmospheric background spectrum upwind of Site A for
a path-length of "216 meters. A single beam atmospheric spectrum for a path-
length, of ~600 meters downwind of a ditch within Site A appears in Figure 14.
Although the two spectra differ in path-length by a factor of "2.8, a
comparison of Figures 13 and 14 reveals the presence of a large hydrocarbon
absorption in the C-H stretching region (3,000 - 2,850 cm'1) in Figure 14.
This hydrocarbon absorption is illustrated in Figure 15 which is an absorbance
spectrum obtained using Figure 14 as the sample and Figure 13 as the
reference. Thus, the excess water-vapor spectrum for a 600 meter path ratioed
against a 216 meter path is superimposed on the hydrocarbon absorption in
Figure 15. An expansion of the 3,000 - 2,848 cm'1 region of Figure 15 appears
in Figure 16 along with a laboratory calibration spectrum of isobutane. The
laboratory calibration spectrum of isobutane matches rather well with extra
features among the water-vapor bands which appear to be too broad to be water-
vapor bands. Figure 17 reveals a change in hydrocarbon concentration at a
stationary location north of an installation within site A due to a change
only in time and wind direction. Here two single beam spectra for a path-
length of 147 feet at this location at different times with different wind
directions are ratioed to give the absorbance spectrum in Figure 17. The
hydrocarbon spectrum in Figure 17 is similar to but not identical to the
laboratory calibration spectrum of isobutane in Figure 16. Methane is a
common constituent of the air and three lines can be recognized among the
water in Figure 18 with a path-length of 147 feet on Site A. The
vibration-rotation bands for both CO and N.O are changing with time upwind of
site A as shown in Figure 19 which is an absorbance spectrum obtained by
ratioing the single beam spectra for a path-length of 216 meters taken at
different but closely spaced time intervals. Open-path data has been acquired
at additional industrial sites, but at the writing of this report these have
not yet been calculated.
It seemed important to test the usefulness of this FT-IR observation on a
major site as soon as possible in this program so that modifications in
hardware could be made. No major difficulties were encountered in hardware.
However, because of the desire to make these first early measurements, much of
the calibration vork and mixtures studies were left to a later date. The lack
of important spectral library data and mixture analysis did slow the
identification process on site. The larger target compound library which will
soon be available will facilitate compound identification on site.
24
-------
Ul
X 1.0C+04
4. 31
Atmospheric Spectrum at -216 meter
Upwind of Sile A (background)
3. 43
2. 55
1. 67
0. 79
-0.09
3200
2450
T -
950. CM-1
Figure 13. Single beam spectrum, ~216 meters path length, Site A.
-------
ro
X 1.0E+04
2. 43
1.94-
1. 45-
Atmospheric Spectrum at ~600 meters
Large Hydrocarbon continuum on Site A
0. 95-
"" T ^ T
'J50 CM-1
Figure 14. Single beam spectrum, "600 meters path length, Site A, shoving strong hydrocarbon
absorption.
-------
2.00
~1
1.65 -
1.30 -
o
NJ Z
CO
o:
o
CO
CD
AI mo spheric Absorbance Spectrum
-600 meter sample on Site A
0.96 -
i 1
?edo. CM-1
Figure IS. Figure 14 absorbance spectrum ratioed against Figure 13 spectrum, Site A.
-------
? 00
to
CO
(Top) Atmospheric Spectrum -600m.
(bottom) Isobutane Spectrum
0.04 I _.
3000.0
r T
T r
2395.0
2860.0 CM-1
Figure 16. Absorbance spectrum, expanded Figure 15, Site A, compared against isobutane calibration
spectrum.
-------
ro
vO
X 0. 1
0.2500
0. 1340-
0. 1130 -
16 scans 147 feet; Two ratioed upcctrti at same place
change of wind direction; charge in hydrocarbon cone
2810. CM-1
Figure 17. Absorbance spectrum, two single beams same location, different time and wind direction,
Site A.
-------
X 1.0E+04
1 2411 "TTscan
T 1 p- 1 "I r- ' -T T-" T
ins 147 feet din lor ce; Me I hor.ir
0.981-
0.721-
0.460-
0.200-
-0.060 I ,_. ..._,_.
3010.0
T "I T I T "I -r I T T
?990 0 ^970.0
2950.0CM-1
Figure 18. Single beam spectrum, shoving methane absorbances between water lines, 147 feet path length,
Site A.
-------
0.411
.
0.336 -
i i i
IIIIT-
Atmospheric absorbance t;pec
CO 1 ines(2240-2040) and N20
1
i
0.26 -
UJ
O
z
CO
cc
g 0..85-
CO
-
0.110-
I
[ *
twdllii
0 . 035
r~ i i
2240.
i
[
i!
U
Ii
u
i 1
i
i
| J
|
I
111
-r- -T-
i j
Jul
4-
]
i
u
T- T- T V
2190.
1
t r ur
1
r
TT- , * ,
> showing
e-j(2240-2190)
!
1
l
J
[
d
l
ill
4
J
T i- -r
1
i
!
j
il
Jj
U
i
V
i
!
j
T T
,
1
JJ
- T-
i
i
u
T
,
ii
ii .
Jj]
i
Y
i
\
1
.1 i
i i
.1
-------
SECTION 6
TECHNOLOGY TRANSFER
DEMONSTRATIONS OF THE TECHNIQUE
Four demonstrations of the mobile laboratory in its current configuration
were performed at the request of Dr. Billy J. Fairless of the EPA Region 7
Laboratory in Kansas City, Kansas.
1. April 11, 1989, at the EPA Region 7 offices at 726 Minnesota Avenue in
Kansas City, Kansas, for State EPA Directors by J. H. Fateley,
R. M. Hammaker, and M. L. Spartz.
2. April 15, 1989, at the EPA Region 7 laboratory at 25 Funston Road in
Kansas City, Kansas, for a group of Korean scientists whose visit was
arranged through the office of Senator Robert Dole by J. H. Fateley,
V. G. Fateley, R. M. Hammaker, and M. L. Spartz.
3. April 28, 1989, at the EPA Region 7 laboratory at 25 Funston Road in
Kansas City, Kansas, for the Deputy Director of EPA by J. H. Fateley,
R. M. Hammaker, and M. L. Spartz.
4. June 30, 1989, at EPA EMSL-ORD at 26 V. Martin Luther King Drive in
Cincinnati, Ohio, for ESD Directors Meeting by J. H. Fateley,
M. L. Spartz, and M. R. Vitkowski.
ORAL AND WRITTEN PRESENTATIONS '
1. "Observation and Measurements of Volatile Organic Compounds (VOC) in the
Atmosphere", M. L. Spartz, R. M. Hammaker, and V. G. Fateley, Hazardous
Vaste Research Conference, May 25, 1988, Manhattan, Kansas (published in
the conference proceedings).
2. "Remote Sensing of Volatile Organic Compounds (VOC) Using a Mobile
Infrared Spectrometer System", M. L. Spartz, M. R. Vitkowski,
R. M. Hanaker, and V. G. Fateley, Paper 624 Pittsburgh Conference on
Analytical Chemistry and Applied Spectroscopy, March 6-10, 1989,
Atlanta, Georgia.
3. "Design and Calibration of a Mobile Laboratory for On-Site Measurements
of Volatile Organic Compounds (VOC) Using Fourier Transform Infrared
Spectrometry (FT-IR)", M. L. Spartz, J. H. Fateley, M. R. Vitkowski,
R. M. Hammaker, and V. G. Fateley, Conference on Hazardous Vaste
Research, May 23-24, 1989, Kansas State University, Manhattan, Kansas (a
32
-------
manuscript will be published in the conference proceedings). The mobile
laboratory was displayed at this conference.
4. "A Mobile FT-IR to Measure On-Site Emissions of Volatile Organic
Compounds (VOC)", M. L. Spartz, J. H. Fateley, M. R. Vitkovski,
R. M. Hammaker, and V. G. Fateley, Poster Paper 7th International
Conference on Fourier Transform Spectroscopy, June 19-23, 1989, George
Mason University, Fairfax, Virginia (a manuscript is required in addition
to the abstract and poster and will be published in S.P.I.E.
Proceedings). The mobile laboratory was displayed at this conference.
5. "Development of a Mobile Laboratory System for On-Site Analyses of
Atmospheric Volatile Organic Compounds Using FT-IR", M. L. Spartz,
M. R. Vitkovski, J. H. Fateley, R. M. Hammaker, and V. G. Fateley,
Department of Chemistry, Villard Hall, Kansas State University,
Manhattan, Kansas 66506; R. E. Carter, M. Thomas, D. D. Lane, Department
of Civil Engineering, G. A. Marotz, Department of Physics and Astronomy,
University of Kansas, Lawrence, Kansas 66045; B. J. Fairless, J. Helvig,
J. Hudson, U. S. Environmental Protection Agency Region 7, 25 Funston
Road, Kansas City, Kansas 66115; Fifth Annual Waste Testing and Quality
Assurance Symposium, July 24-28, 1989, Washington, D.C. (published in the
conference proceedings).
6. "Evaluation of a Mobile FT-IR System for Rapid VOC Determination: Part
1, Preliminary Qualitative and Quantitative Calibration Results"
M. L. Spartz, M. R. Witkovski, J. H. Fateley, J. M. Jarvis, J. S. White,
J. V. Paukstelis, R. M. Hammaker, W. G. Fateley, R. E. Carter,
M. Thomas, D. D. Lane, G. A. Marotz, B. J. Fairless, T. Hollovay, J. L.
Hudson and D. F. Gurka. American Environmental Laboratory. July 1989,
15-30.
7. "Field Monitoring of Air Toxics by Open-Path Fourier Transform Infrared
Spectrometry." D. F. Gurka, B. J. Fairless, J. Hudson, H. Kimball,
J. Helvig, J. Arello, T. Hollovay, W. G. Fateley, R. M. Hammaker,
M. L. Spartz, M. R. Witkovski, J. Fateley, D. D. Lane, R. Carter,
M. Thomas and G. A. Marotz. Anal. Chem. 1990, 62, 0000.
33
-------
REFERENCES
1. Hanst, P. L. Fourier Transform Infrared Spectroscopy Applications to
Chemical Systems, Vol. 2, Ferraro, J. R. and Basile, L. J., eds.,
Academic Press 1979. pp. 79-110.
2. Gurka, D. F., Betovski, D. L., Hinners, T. A., Heithmar, E. M.,
Titus, R., and Henshaw, J. M. Anal. Chem. 1988, 60, 454A-467A.
3. Herget, W. F. Fourier Transform Infrared Spectroscopy Applications to
Chemical Systems, Vol. 2, Ferraro, J. R. and Basile, L. J., eds.
Academic Press 1979. pp. 111-127.
4. Krost, K. J., Pellizzari, E. D., Walburn, S. G., and Hubbard, S. A.
Anal. Chem. 1982, 54, 810-817.
5. Marotz, G. A., Lane, D. D., Carter, R. E. Jr., Trippe, R., and
Helvig, J. Paper presented at the 80th Annual Meeting APCA, New York,
New York, June 21-26, 1987.
6. McClenny, V. A., Pleil, J. D., Holdren, M. V., and Smith, R. N. Anal.
Chem. 1984, 56, 2947.
7. Beebe, K. R. and Kowalski, B. R. Anal. Chem. 1987, 59, 1007A-1017A.
8. M. L. Spartz, R. M. Hammaker, and V. G. Fateley. Observation and
Measurements of Volatile Organic Compounds (VOC) in the Atmosphere.
In: Proceedings of the Hazardous Waste Research Conference,
May 25, 1988, Manhattan, Kansas.
9. M. L. Spartz, J. H. Fateley, M. R. Vitkovski, R. M. Hammaker,
V. G. Fateley. Design and Calibration of a Mobile Laboratory for On-Site
Measurements of Volatile Organic Compounds (VOC) Using Fourier Transform
Infrared Spectrometry (FT-IR). In: Proceedings of the Conference on
Hazardous Waste Research, May 23-24, 1989, Kansas State University,
Manhattan, Kansas.
10. M. L. Spartz,. J. H. Fateley, M. R. Witkovski, R. M. Hammaker,
W. G. Fateley. A Mobile FT-IR to Measure On-Site Emissions of Volatile
Organic Compounds (VOC). Poster Paper 7th International Conference on
Fourier Transform Spectroscopy, June 19-23, 1989, George Mason
University, Fairfax, Virginia (a manuscript is in S.P.I.E. Proceedings).
11. M. L. Spartz, M. R. Witkowski, J. H. Fateley, R. M. Hammaker, and W. G.
Fateley, Department of Chemistry, Willard Hall, Kansas State University,
Manhattan, Kansas 66506; R. E. Carter, M. Thomas, and D. D. Lane,
34
-------
Department of Civil Engineering, G. A. Marotz, Department of Physics and
Astronomy, University of Kansas, Lawrence, Kansas 66045; B. J. Pairless,
J. Helvig, and J. Hudson, U.S. Environmental Protection Agency Region 7,
25 Funston Road, Kansas City, Kansas 66115. Development of a Mobile
Laboratory System for On-Site Analyses of Atmospheric Volatile Organic
Compounds Using FT-IR. In: Proceedings of the Fifth Annual Waste
Testing and Quality Assurance Symposium, July 24-28, 1989,
Washington, D.C.
12. "Evaluation of a Mobile FT-IR System for Rapid VOC Determination: Part
1, Preliminary Qualitative and Quantitative Calibration Results"
M. L. Spartz, M. R. Witkowski, J. H. Fateley, J. M. Jarvis, J. S. White,
J. V. Paukstelis, R. M. Hammaker, W. G. Fateley, R. E. Carter,
M. Thomas, D. D. Lane, G. A. Marotz, B. J. Fairless, T. Hollovay, J. L.
Hudson and D. F. Gurka. American Environmental Laboratory. July 1989,
15-30.
13. "Field Monitoring of Air Toxics by Open-Path Fourier Transform Infrared
Spectrometry." D. F. Gurka, B. J. Fairless, J. Hudson, H. Kimball,
J. Helvig, J. Arello, T. Hollovay, W. G. Fateley, R. M. Hammaker,
M. L. Spartz, M. R. Witkovski, J. Fateley, D. D. Lane, R. Carter,
M. Thomas and G. A. Marotz. Anal. Chem. 1990, 62, 0000.
35
-------
APPENDIX A
SPECTRA PROM FIELD WORK AT LAWRENCE, KS
CONTENTS
Page
Single Component Unknown From University of Kansas Tests 37
Analysis of Unknown Mixture 1 37
Analysis of Unknown Mixture 2 37
Analysis of Unknown Mixture 3 37
Analysis of Unknown Mixture 4 47
FIGURES
Number Page
A-l Unknown Sample A (Acetone). Kansas University tests for EPA testing
5-16-89, 760 feet source 0.1 cm'1 res. unk. comp. A 38
A-2 Unknown Sample B (Methanol). Kansas University tests for EPA
testing 5-17-89, 100 meter source 0.1 cm'1 res. Reference unknowns
11:45 a.m., unknown B 39
A-3 Unknown Sample C (Methylene chloride). Kansas University tests for
EPA testing 5-16-89, 760 feet source 0.1 cm'1 res. unknown C 40
A-4 Unknown Sample D (Toluene). Kansas University tests for EPA testing
5-17-89, 100 meter source 0.1 cm'1 res. Reference unknowns
12:45 p.m., unknown D 41
A-5 Unknown Mixture 1. Kansas University tests for EPA testing 5-17-89,
100 meter source 0.1 cm'1 res. Reference unknowns 2:11 p.m.,
Mixture 1 42
A-6 Unknown Mixture 1. Kansas University tests for EPA testing 5-17-89,
100 meter source 0.1 cm'1 res. Reference unknowns 2:11 p.m.,
Mixture 1 43
36
-------
Number Page
A-7 Unknown Mixture 1. Kansas University tests for EPA testing 5-17-89,
100 metersource 0.1 cm'1 res. Reference unknowns 2:11 p.m.,
Mixture 1 44
A-8 Unknown Mixture 2. Kansas University tests for EPA testing 5-19-89,
100 meter source 0.1 cm"1 res. Phase work 57-58 counts Mixture 2. .45
A-9 Unknown Mixture 2. Kansas University tests for EPA testing 5-19-89,
100 meter source 0.1 cm"1 res. Phase work 57-58 counts Mixture 2. .46
A-10 Unknown Mixture 4. Kansas University tests for EPA testing 5-19-89,
100 meter source 0.1 cm"1 res. Phase work 57-58 counts, Mixture 4. . 48
SINGLE COMPONENT UNKNOWN FROM UNIVERSITY OF KANSAS TESTS
The four single component samples were analyzed and were found to be, in
order: (A) acetone, (B) methanol, (C) methylene chloride, and (D) toluene.
The concentrations were then calculated approximately and placed in Table 4.
All but toluene (Sample D) provided firm results. After the analysis was
confirmed by Ray E. Carter (KU) the concentration was calculated.
ANALYSIS OF UNKNOWN MIXTURE 1
There were three compounds in Mixture 1. Two of these compounds (acetone
and methylene chloride) were identified by observations of the base line
pattern. The third compound (toluene) was also present in this mixture. Once
this was known, the presence of toluene was confirmed. See Figure A-7 where
toluene, in the spectrum, can be recognized. This recognition was used in
other mixtures which contained toluene.
ANALYSIS OF UNKNOWN MIXTURE 2
There were three compounds present in Mixture 2. In Figure A-8 one sees
three compounds that could match the atmospheric spectrum to some extent, the
isopropanol was easily recognized from the contour of the baseline. After
successfully subtracting out the isopropanol, we can see the resultant
subtracted spectrum in Figure A-9. It is evident that the n-butanol appears
to best match the resulting spectrum. The possibility of ethanol present was
not disregarded. However, it was later confirmed not to be in the mixture.
The third compound was reported to be n-pentane. The ability to get a
confident match and identification of n-pentane was seriously hampered by the
fact that the isopropanol and n-butanol both have strong absorbances in the CH
region in the same region as n-pentane.
ANALYSIS OF UNKNOWN MIXTURE 3
See the Field Work Results subsection for a discussion of this mixture.
37
-------
-o.isoo
Atmospheric obsorborce spectrum ]
Unknown A University of Kansas Tests I
Colioration spectrum
Ace t ore
1275.0
1245.0
1185.0
1155.0 CM-1
Figure A-l. Unknown Sample A (Acetone). Kansas University tests for EPA testing 5-16-89, 760 feet
source 0.1 cm"1 res. unknown A.
-------
X 0. 1
0.450
O.?40-
0.030-
O
CO
oc
o
CO
CD
-0. 130-
-0.390-
-0.600
Calibration spectrum
Met Hanoi
Atmospheric absorbance spectrum
Unknown B University of Kansas Tests
1100.0
950.
0 CM-1
Figure A-2. Unknown Saaple B (Methanol). Kansas University tests for EPA testing 5-17-89, 100 meter
source 0.1 cm"1 res. Reference unknowns 11:45 a.m., unknown B.
-------
o
X 0. 1
0.1700
o. toao
Atmospheric absorbonce spectrum
Unknown C University of Kansas Tests
0.0460-
UJ
o
2
<
00
oc
o
CO
m
-o.oieo -
-0.0730 -
-0. MOO
Calibration, spoc t i uMI
Methylene Chloride
850.0
812.5
775.0
737.5 700.0 CM-1
Figure A-3. Unknown Sample C (Methylene chloride). Kansas University tests for EPA testing 5-16-89,
760 feet source 0.1 en"1 res. unk. coup. C.
-------
X 0. 1
1.000
0.720 H
0.440 H
O
z
<
CD
DC
O
CD
0. 160 H
-0.120 H
Atmospheric obsorbonce spectrum
Unknown D University of Kansas Tests
Calibration Spectrum
To Juene
-0.400
AA
-------
tsl
I
0.05JO
0.0160 H
-0.0610 "
, MOO
1260.
F
i
| ' 1
! i
il ;j
li !' i
ij j
1
1
!
!
t
1
I i
"»- T i
At m<
Urki
.
T"
sphe
!l '
r i c o
i o w p m i x I u
!
j
il
!
i
r T
b so rt
re 1
ance
KU t
1210.
tests
Calior'atior spectrum'
Ace t one
1110.
1060. CM-1
Figure A-5. Unknown Mixture 1. Kansas University tests for EPA testing 5-17-89, 100 meter source
0.1 cm'1 res. Reference unknowns 2:11 p.m., mixture 1.
-------
X 0. 1
0. 700
0.540 -
0.380 -
CD
DC.
CO
0.060
-0.100
Atmospheric obsorbonce spectrum
Unknown mixture 1 KU tests (top)
Colioratior. Spectrum
MethyJene Chloride (bottom)
850.0
~ T"
312. 5
775.0
737. 5
700.0 CM-1
Figure A-6. Unknown Mixture 1. Kansas University tests for EPA testing 5-17-89, 100 meter source
0.1 en'1 res. Reference unknowns 2:11 p.*., mixture 1.
-------
x o. i
0.670
0.470
0.270 -
O
Z
<
CD
CC.
O
CO
CO
0.070 -
-0. 130
-0.330
(VA<
-r T -p T r T T -p T r- ~r
A t mo o p I: c r i r. o t< s o r l> a r. c e spectrum
Unknown mixture 1 KU tests
Calibration spectrum
Toluene
740.0
730.0
720. 0
710.0
700.0 CM-1
Figure A-7. Unknown Mixture 1. Kansas University tests for EPA testing 5-17-89, 100 meter source
0.1 cm"1 res. Reference unknowns 2:11 p.m., mixture 1.
-------
Calibration spectVum
Isop ropano1
Calibration spectrui
n-Bu ta no 1
Calioration spectrum
E t h a n o 1
730. CM-1
Figure A-8. Unknown Mixture 2. Kansas University tests for EPA testing 5-19-89, 100 meter source
0.1 en"1 res. Phase work 57-58 counts Mixture 2.
-------
X 0. 1
0.1500
0. 1200
0.0900
o
CD
CC.
O
(/>
CD
0.0600
0.0300 -
0.0000
T
r T
T
Atmospheric absorbance spectrum with isopropano
subtracted: Unknown mixture 2 KU tests
Calibration spectrum
nBu t a no I
Calibration spectrum
E t hano 1
1330.
1180.
830
730. CM-1
Figure A-9. Unknown Mixture 2. Kansas University tests for EPA testing 5-19-89, 100 meter source
0.1 cm"1 res. Phase work 57-58 counts Mixture 2.
-------
ANALYSIS OP UNKNOWN MIXTURE 4
Three compounds were reported to be present in Mixture 4, again two
compounds vere easily recognized (methylene chloride and
1,1,1-trichloroethane). The third compound was toluene at a concentration
which was not detectable at these path lengths.
47
-------
X 0. 1
0.6100
0.5700-
o.sioo -
O
g £
CO
0.4500-
0.3900-
0.3300
A t mo spheric obsorborce spectrum
Unknown mixture 4 KU tests
Calibration spectrum
Methylerse Chloride
Calioratior. spectrum
1. 1, 1 Tr i ch 1 o roe t hane
1130.
1030.
330
830
730. CM-1
Figure A-10. Unknown Mixture 4. Kansas University tests for EPA testing 5-19-89, 100 meter source
0.1 cm'1 res. Phase work 57-58 counts, mixture 4.
-------
APPENDIX B
SPECTRA FROM FIELD WORK AT SITE A
CONTENTS
Page
Discussion of Site A 49
Analysis of Absorbance Spectra Over Ditch, Site A 49
Analysis of Absorbance Spectrum Using Spectra from Two Sites on Site A . . 50
Emission From a Hot Stack Dovnwind of Site A 50
FIGURES
Number Page
B-l Atmospheric spectrum Site A; ratio of up and downwind of ditch. ... 51
B-2 Atmospheric spectrum Site A; isobutane subtracted out 52
B-3 Absorbance spectrum ratioed from two spectra in different places at
Site A ~44 meter distance 53
B-4 Emission from a hot stack downwind of Site A 54
DISCUSSION OF SITE A
Site A was chosen to test the field reliability of the mobile FT-IR
spectrometer system. Site A was analyzed in four different places in four
days. There was a large amount of data generated from this site and just a
fraction of it will be reviewed here. The site was expected to contain a high
concentration of aliphatic hydrocarbons with little or no substituent groups,
i.e., chlorine, and a reasonable amount of aromatics, i.e., benzene, toluene.
Analyses of a few spectra are included here.
ANALYSIS OF ABSORBANCE SPECTRA OVER DITCH, SITE A
The following spectra in Figure B-l show an atmospheric spectrum and two
calibrated spectra. The absorbance spectrum was produced by taking the ratio
49
-------
of the downwind to the upwind of the ditch on Site A. As can be seen below,
in the sample, there are two compounds whose structure looks as if it would
fit the atmospheric spectrum. However, after further analysis we find
n-hexane is probably not a component of this atmospheric spectrum. Isobutane
or a compound with a very similar chemical structure does appear to be
present, this can be seen in Figure B-2. The isobutane subtracted out of the
sample spectrum nicely and the resultant spectrum now no longer resembles the
n-hexane especially at "2885 cm"1. This spectra could then be further matched
if need be.
ANALYSIS OF ABSORBANCE SPECTRUM USING SPECTRA FROM TWO SITES ON SITE A
Two spectra from different places at Site A were ratioed to give the
following absorbance spectrum, Figure B-3. The resultant spectrum displays a
band due to benzene which is compared against the benzene calibration
spectrum. Both places in which the single beam spectra were taken had benzene
present, the resultant band intensity is thus decreased when the spectra are
ratioed.
EMISSION FROM A HOT STACK DOWNWIND OF SITE A
The spectrometer can be turned skyward to use the heat of a smoke stack
as a source. With this heat also, the vibrational-rotational bands of the
molecules present are excited to higher energy transitions and when they
relax give off radiation as can be seen in Figure B-4. The sharp positive
going lines are the emission lines, many of which here are due to C02.
Further analysis will be done with this and similar spectra for emission and
absorbance measurements. The stack for this spectrum was located about one
mile away.
50
-------
0. 120
0.084
0.049
0.013
GO
-0.022 -
-0.053
3050.
Atmospheric Spectrum Site A (top)
Ratio of up and down wind of ditch
Calibration Spectrum
n-Hexane (middle)
Calibration Spectrum
Isobutane (bottom)
2975.
?900
T"
2325.
2750. CM-1
Figure B-l. Atmospheric spectrum Site A; ratio of up and downwind of ditch.
-------
0. 1
in
N>
Atmospheric Spectrum Site
I'jobutare subtracted out
?900.
2825.
2750. CM-1
Figure B-2. Atmospheric spectrum Site A; isobutahe subtracted out.
-------
Ul
u>
X 0. 1
0. 760
0.580
0.400 -
0.040
-0.140
Absorbonce spectrum ratioed from two spectra
in- different places at Site A -44fiicter dislance
678.0
Calibration Spectrum
Benzene
674.0
670.0
666.0 CM-1
Figure B-3. Absorbance spectrum ratioed from tvo spectra in different places at Site A "44 meter
distance.
-------
Ul
X 1.0E+03
5.67
4. 49-
3. 32-
2. 14-
0.97
-0.21
1500.
Emission from a hot stack down wind of site A
Many emission lines can be seen as well as absorbances
1300.
"-T
1100.
900.
700. CM-1
Figure B-4. Emission from a hot stack downwind of Site A.
-------
APPENDIX C
SPECTRA FROM LABORATORY CALIBRATION AND BEER'S LAW PLOTS
This appendix contains the following three figure collections: (1) all
calibration spectra in the library at the time of this writing and (2) Beer's
Law plots of absorbance versus molar concentration for at least one
absorption band from each spectrum in the library with three exceptions
(carbon tetrachloride, chloroform, and toluene). For those three compounds
there are inconsistencies in the data and additional measurements are needed.
(3) 15 Reference spectra of 13 compounds that were taken in preparation for
Site A. A listing of the compounds showing the page number for the figures
for each compound follows.
FIGURES
Number Page
SPECTRUM
C-l Calibration of spectrometer at .255 torr for methylene chloride.
Source 25 cm from aperture and 16 cm cell 742.2 torr N2 59
C-2 Calibration of spectrometer at .2055 torr for chloroform.
Source 25 cm from aperture and 16 cm cell 739.0 torr N2 59
C-3 Calibration of spectrometer at .1014 torr for carbon tetrachloride.
Source 25 cm from aperture and 16 cm cell 740.0 torr N2 60
C-4 Calibration of spectrometer for tetrachloroethylene at .2134 torr.
Source 25 cm from aperture and 16 cm cell 741.1 torr 60
C-5 Calibration of spectrometer for 1,2-dichloroethane at .2292 torr.
Source 25 cm from aperture and 16 cm cell 739.7 torr 61
C-6 Calibration of spectrometer for trichloroethylene at 0.1564 torr.
Source 25-cm from aperture and 16 cm cell 740.0 torr 61
C-7 Calibration of spectrometer for chlorobenzene at 0.0967 torr.
Source 25 cm from aperture and 16 cm cell 740.7 torr 62
C-8 Calibration of spectrometer for 3-chloropropene at .2325 torr.
Source 25 cm from aperture and 16 cm cell 740.1 torr 62
55
-------
Number Page
C-9 Calibration of spectrometer for benzene at .1224 torr.
Source 25 cm from aperture and 16 cm cell 740.2 torr 63
C-10 Calibration of spectrometer for toluene at .1670 torr.
Source 25 cm from aperture and 16 cm cell 740.5 torr 63
C-ll Calibration of spectrometer for isopropanol at .1603 torr.
Source 25 cm from aperture and 16 cm cell 740.0 torr 64
C-12 Calibration of spectrometer for isopropanol at .1603 torr.
Source 25 cm from aperture and 16 cm cell 740.0 torr 64
C-13 Calibration of spectrometer for tetrahydrofuran at .1699 torr.
Source 25 cm from aperture and 16 cm cell 740.0 torr 65
C-14 Calibration of spectrometer for tetrahydrofuran at .1699 torr.
Source 25 cm from aperture and 16 cm cell 740.0 torr 65
C-15 Calibration of spectrometer for diethyl ether at .1375 torr.
Source 25 cm from aperture and 16 cm cell 740.7 torr 66
C-16 Calibration of spectrometer for diethyl ether at .1375 torr.
Source 25 cm from aperture and 16 cm cell 740.7 torr 66
C-17 Calibration of spectrometer for acetone at .1803 torr.
Source 25 cm from aperture and 16 cm cell 740.6 torr 23 C 67
C-18 Calibration of spectrometer for methanol at 0.1372 torr.
Source 25 cm from aperture and 16 cm cell 741.1 torr 67
C-19 Calibration of spectrometer for etHanoi at .1985 torr.
Source 25 cm from aperture and 16 cm cell 740.0 torr 68
C-20 Calibration of spectrometer for ethanol at .1985 torr.
Source 25 cm from aperture and 16 cm cell 740.0 torr . 68
C-21 Calibration of spectrometer for n-butanol at .1024 torr.
Source 25 cm from aperture and 16 cm cell 740.0 torr 69
C-22 Calibration of spectrometer for n-butanol at .1024 torr.
Source 25 cm from aperture and 16 cm cell 740.0 torr 69
C-23 Calibration of spectrometer for cyclopentane at .100 torr.
Source 25 cm from aperture and 16 cm cell 740.1 torr 70
C-24 Calibration of spectrometer for ethyl acetate at .1160 torr.
Source 25 cm from aperture and 16 cm cell 740.0 torr 70
C-25 Calibration of spectrometer for methyl ethyl ketone at .1234 torr.
Source 25 cm from aperture and 16 cm cell 740.0 torr 71
56
-------
Number Page
C-26 Calibration of spectrometer for methyl ethyl ketone at .1234 torr.
Source 25 cm from aperture and 16 cm cell 740.0 torr 71
C-27 Calibration of spectrometer for pyridine at .0973 torr.
Source 25 cm from aperture and 16 cm cell 740.1 torr 72
C-28 Calibration of spectrometer for 1,1,1-trichloroethane at .1530 torr.
Source 25 cm from aperture and 16 cm cell 740.0 torr 72
C-29 Calibration of spectrometer for 1,4-dioxane at .1086 torr.
Source 25 cm from aperture and 16 cm cell 740.1 torr 73
C-30 Calibration of spectrometer for 1,4-dioxane at .1086 torr.
Source 25 cm from aperture and 16 cm cell 740.1 torr 73
C-31 Calibration of spectrometer for methyl isobutyl ketone at .1124 torr.
Source 25 cm from aperture and 16 cm cell 740.1 torr 74
C-32 Calibration of spectrometer for methyl isobutyl ketone at .1124 torr.
Source 25 cm from aperture and 16 cm cell 740.1 torr 74
C-33 Calibration of spectrometer for ethyl benzene at .0724 torr.
Source 25 cm from aperture and 16 cm cell 740.0 torr 75
C-34 Calibration of spectrometer for ethyl benzene at .0724 torr.
Source 25 cm from aperture and 16 cm cell 740.0 torr 75
BEER'S LAW PLOT
C-35 Methylene chloride 76
C-36 Tetrachloroethylene 76
C-37 1,2-Dichloroethane 77
C-38 Trichloroethylene 77
C-39 Chlorobenzene. 78
C-40 Allyl chloride (3-Chloropropene) 78
C-41 Benzene 79
C-42 Isopropanol.Dat 1 .79
C-43 Isopropanol.Dat 2 80
C-44 Tetrahydrofuran.Dat 1 80
C-45 Tetrahydrofuran.Dat 2 81
C-46 Diethyl ether 81
C-47 Aceton*. . .- 82
C-48 Methanol.Lof 82
C-49 Methanol.Cor 83
C-50 Ethanol 83
C-51 n-Butanol.Dat 1 84
C-52 n-Butanol.Dat 2 84
C-53 Cyclopentane 85
C-54 Ethyl acetate 85
C-55 Methyl ethyl ketone 86
57
-------
Number Page
C-56 Pyridine 86
C-57 1,1,1-Trichloroethane (1,1,1-TCA) 87
C-58 1,4 Dioxane.Dat 1 87
C-59 1,4-Dioxane.Dat 2 88
C-60 Methyl isobutyl ketone 88
C-61 Ethyl benzene 89
SPECTRUM
C-62 p-Xylene 90
C-63 o-Xylene 91
C-64 m-Xylene 92
C-65 n-Hexane 93
C-66 n-Pentane 94
C-67 Ethane 95
C-68 Isobutane 96
C-69 1,3-Butadiene 97
C-70 1,3-Butadiene 98
C-71 Propylene 99
C-72 Freon 13 100
C-73 Ethyl chloride . . 101
C-74 Dimethyl ether 102
C-75 Dimethyl ether 103
C-76 Iso-Octane 104
58
-------
X 0. 1
0. 760
. 604 -
CD
CEO. 443
o
CO
QQ
<0. 292 -
0.136 -
-0.020
1300.
1050.
800. CM-1
Figure C-l. Calibration of spectrometer at .255 torr for methylene chloride.
Source 25 cm from aperture and 16 cm cell 742.2 torr N2.
0. 134
CD
CCO .110-
O
CO
CD
<0. 074 -I
0.037 -
0. 000
T T
1300.
I
1050.
800. CM-1
Figure C-2. Calibration of spectrometer at .2055 torr for chloroform. Source
25 cm from aperture and 16 cm cell 739.0 torr N2.
59
-------
0. 135
. 107 -
CD
(TO. 079
O
GO
CO
^.052
0.024 -
-0. 004 l_Z
1300.
1050.
800. CM-1
Figure C-3. Calibration of spectrometer at .1014 torr for carbon
tetrachloride. Source 25 cm from aperture and 16 cm cell 740.0
torr N2.
X 0. 1
0. 760
. 604 -
CD
Cd>. 448
O
GO
CO
0. 136 -
-0.020
|
1300. 1050. 800. CM-1
Figure C-4. Calibration of spectrometer for tetrachloroethylene at .2134
torr. Source 25 cm from aperture and 16 cm cell 741.1 torr.
60
-------
X 0. 1
0.4500
1075.
I
750. CM-1
Figure C-5. Calibration of spectrometer for 1,2-dichloroethane at .2292 torr.
Source 25 cm from aperture and 16 cm cell 739.7 torr.
X 0. 1
0.5400
LM).4230
-0.0200
1300.
1050.
800. CM-1
Figure C-6. Calibration of spectrometer for trichloroethylene at 0.1564 torr.
Source 25 cm from aperture and 16 cm cell 740.0 torr.
61
-------
X 0. 1
0.6100
LMj.4842
GO
Cd>.3534
O
CD
CD
<^.2326 -
0. 1063 -
950.
700. CM-1
Figure C-7. Calibration of spectrometer for chlorobenzene at 0.0967 torr.
Source 25 cm from aperture and 16 cm cell 740.7 torr.
X 0. 1
0.2400
0.0260
1300.
1050.
800. CM-1
Figure C-8. Calibration of spectrometer for 3-chloropropene at .2325 torr,
Source 25 cm from aperture and 16 cm cell 740.1 torr.
62
-------
0. 370
. 295 -
CD
CCO. 220 -j
O
CO
CD
<0. 144 -
0.069 -
T r
1 1 r
687.
625. CM-1
Figure C-9. Calibration of spectrometer for benzene at .1224 torr. Source 25
cm from aperture and 16 cm cell 740.2 torr.
X 0. 1
0.6000
M).4800
0.0000
800.
720.
640. CM-1
Figure C-10. Calibration of spectrometer for toluene at .1670 torr. Source
25 cm from aperture and 16 cm cell 740.5 torr.
63
-------
X 0. 1
I«'''I
-0.0700 I
3100.
T r
2850. CM-1
Figure C-ll. Calibration of spectrometer for isopropanol at .1603 torr.
Source 25 cm from aperture and 16 cm cell 740.0 torr.
X 0. 1
0.1200
U-0.0960
0.0000
1450.
1125.
800. CM-1
Figure C-12. Calibration of spectrometer for isopropanol at .1603 torr.
Source 25 cm from aperture and 16 cm cell 740.0 torr.
64
-------
X 0. 1
0. 800 T r
Z
<
00
o
CO
CO
. 633 -
.467 -
. 300 -
0. 134 -
-0.033
T T
1 .
T T
3100.
i - 1 -- 1 - 1 - 1
2938.
2775. CM-1
Figure C-13. Calibration of spectrometer for tetrahydrofuran at .1699 torr.
Source 25 cm from aperture and 16 cm cell 740.0 torr.
X 0. 1
0.3000
T - 1 - r
875. CM-1
Figure C-14. Calibration of spectrometer for tetrahydrofuran at .1699 torr.
Source 25 cm from aperture and 16 cm cell 740.0 torr.
65
-------
X 0. 1
0.4SOO
"-"-0.3644
0.0220
3100.
2775. CM-;
Figure C-15. Calibration of spectrometer for diethyl ether at .1375 torr.
Source 25 cm from aperture and 16 cm cell 740.7 torr.
0.000
1450.
1250.
I
1050. CM-1
Figure C-16. Calibration of spectrometer for diethyl ether at .1375 torr.
Source 25 cm from aperture and 16 cm cell 740.7 torr.
66
-------
X 0. 1
0.3000
0.0200
1400.
1233.
075. CM-1
Figure C-17. Calibration of spectrometer for acetone at .1803 torr.
25 cm from aperture and 16 cm cell 740.6 torr 23 C.
X 0. 1
0.5300
Source
y>.4572
03
03.3344
O
CO
CO
"V2116
0.0800.
-0.0340
1100.
I
1020.
I ' '
940. CM-1
Figure C-18. Calibration of spectrometer for methanol at 0.1372 torr. Source
25 cm from aperture and 16 cm cell 741.1 torr.
67
-------
X 0. 1
0.6700
0.3500
3100.
2938.
2775. CM-1
Figure C-19. Calibration of spectrometer for ethanol at .1985 torr.
25 cm from aperture and 16 cm cell 740.0 torr.
X 0. 1
0.5400
Source
Lt-0.4760
CO
035.4120
O
CO
CO
"S.3480
0.2840-
0.2200
1450.
1188.
I ' '
925. CM-1
Figure C-20. Calibration of spectrometer for ethanol at .1985 torr. Source
25 cm from aperture and 16 cm cell 740.0 torr.
68
-------
X 0. 1
0. 1800
0.0110
3100.
2938,
2775. CM-1
Figure C-21. Calibration of spectrometer for n-butanol at .1024 torr. Source
25 cm from aperture and 16 cm cell 740.0 torr.
X 1.0E-02
0.5900
LM).4300
-0.2100
1450.
1
1188.
925. CM-1
Figure C-22. Calibration of spectrometer for n-butanol at .1024 torr. Source
25 cm from aperture and 16 cm cell 740.0 torr.
69
-------
X 0. 1
0..800
-0.011
3100.
i , r
2850. CM-1
Figure C-23. Calibration of spectrometer for cyclopentane at .100 torr.
Source 25 cm from aperture and 16 cm cell 740.1 torr.
X 0. 1
0. 920
. 739 -
CO cca
OlO .558-
O
CO
CO
^.377-
0. 196 -
0.015
1400.
1238.
I ' '
1075. CM-1
Figure C-24. Calibration of spectrometer for ethyl acetate at .1160 torr.
Source 25 cm from aperture and 16 cm cell 740.0 torr.
70
-------
X 0. 1
0.1550
2938.
I
2775. CM-1
Figure C-25. Calibration of spectrometer for methyl ethyl ketone at .1234
torr. Source 25 cm from aperture and 16 cm cell 740.0 torr.
0.0120
-0.0150
1400.
1150.
900. CM-1
Figure C-26. Calibration of spectrometer for methyl ethyl ketone at .1234
torr. Source 25 cm from aperture and 16 cm cell 740.0 torr.
71
-------
0.210
CD
Gd>. 124 -
O
CO
CD
. 081 -I
0.038 -
-0.005
800.
1 1
720.
640. CM-1
Figure C-27. Calibration of spectrometer for pyridine at .0973 torr. Source
25 cm from aperture and 16 cm cell 740.1 torr.
X 0. 1
0.940
y>.74ij
^ *,
CCP. 542 -
O
CO
CO
^.343 -
0. 144-
-0.055
1200.
950.
700. CM-1
Figure C-28. Calibration of spectrometer for 1,1,1-trichloroethane at .1530
torr. Source 25 cm from aperture and 16 cm cell 740.0 torr.
72
-------
X 0, 1
0. 670
2800. CM-1
Figure C-29. Calibration of spectrometer for 1,4-dioxane at .1086 torr,
Source 25 cm from aperture and 16 cm cell 740.1 torr.
X 0. 1
0.3900
<-M>.3060
-0.0300
1320,
1195.
1070. CM-1
Figure C-30. Calibration of spectrometer for 1,4-dioxane at .1086 torr,
Source 25 cm from aperture and 16 cm cell 740.1 torr.
73
-------
X 0. 1
0,2300
-0.0300
3100.
2975.
2850. CM-1
Figure C-31. Calibration of spectrometer for methyl isobutyl ketone at .1124
torr. Source 25 cm from aperture and 16 cm cell 740.1 torr.
X 0. 1
0.1900
o-'152M
z
CO
O3>. 1140-
o
CO
CD
^.0760-^
0.038041
f
0.0000 I
1400.
I
1275.
1150. CM-1
Figure C-32. Calibration of spectrometer for methyl isobutyl ketone at .1124
torr. Source 25 cm from aperture and 16 cm cell 740.1 torr.
74
-------
X 0. 1
0.1100
0.0016
3100.
2975
2850. CM-1
Figure C-33. Calibration of spectrometer for ethyl benzene at .0724 torr.
Source 25 cm from aperture and 16 cm cell 740.0 torr.
X 1.0E-02
0.9600
-0.0270
1300.
1025.
I
750. CM-1
Figure C-34. Calibration of spectrometer for ethyl benzene at .0724 torr.
Source 25 cm from aperture and 16 cm cell 740.0 torr.
75
-------
.075-
I
<
QQ
GS
o
CO
CO
.05-
.025-
METHYLENE CHLORIDE
749.5 cm-1 Res 0.5 cm-1
5e-6 te-5
CONCENTRATION (M)
1.5e-5
Figure C-35. Methylene chloride.
.075-1
TETRACHLOROETHYLENE
916.3 cm-1 Res 0.5 cm-1
W .06-
CD
a:
.025-
2.5^6 5e-6 75e-6 te-5
CONCENTRATION (M)
1.25«-5
Figure C-36. Tetrachloroethylene.
76
-------
.04-,
1,2-DICHLOROETHANE
731.3 cm-1 Res 0.5 cm-1
Cd
o
<
CQ
o:
o
CO
m
.03-
.02-
.01-
25e-6 5e-6 75e-6 le-5
CONCENTRATION (M)
125e-5
Figure C-37. 1,2-Dichloroethane.
.05-,
TRICHLOROETHYLENE
849.4 cm-1 Res 0.5 cm-1
.04-
U
O
<
00
OQ
.03-
.02-
.01-
2.5e-6 5e-6 7 5e-6
CONCENTRATION (M)
Figure C-38. Trichloroethylene.
77
te-5
-------
.06-,
W .04-
U
<
CO
' H
< .02H
CHLOROBENZENE
741.23 cm-1 Res 0.5cm-l
2e-6 4a-6
CONCENTRATION (M)
Figure C-39. Chlorobenzene.
6e-6
W
O
2
<
DQ
o:
.02-1
.01-
.006-
ALLYL CHLORIDE
756.9 cm-1 Res 0.5 cm-1
0 3.75e-fi 7.5e-6 t125a-6 l5e-5
CONCENTRATION (M)
Figure C-40. Allyl chloride (3-Chloropropene).
78
-------
4-1
BENZENE
673.93 cm-1 Res 0.1 cm-1
U
o
2
<
cn
.3-
.2-
.1-
1.5e-6 3e-6 45e-6 6e-6
CONCENTRATION (M)
7.6e-6
Figure C-41. Benzene.
.04-,
ISOPROPANOL.DAT1
2982.7 cm-1 Res 0.5 cm-1
W
O
2
<
PQ
.03-
.02-
03
.01-
2.5«-6 5e-6 7.50-6
CONCENTRATION (M)
Figure C-42. Isopropanol.Dat 1.
79
to-5
-------
.OH
ISOPROPANOL.DAT2
956.5 cm-1 Res 0.5 cm-1
U
O
2
<
00
.0075-
.006-
.0025-
2.5a-6 50-6 7.50-6
CONCENTRATION (M)
Figure C-43. Isopropanol.Dat 2.
te-5
06-,
TETRAIIYDROFURAN.DAT!
2901.7 cm-1 Res 0.5 cm-1
o
<
PQ
Oi
m
.04-
.02-
250-6 50-6 750-6 10-5
CONCENTRATION (M)
Figure C-44. Tetrahydrofuran.Dat 1.
80
-------
TETRAHYDROFURAN.DAT2
1084.4 cm-l Res 0.5 cm-l
u
o
<
03
a:
OQ
2;5e-6 5e-8 7.5e-6
CONCENTRATION (M)
Figure C-45. Tetrahydrofuran.Dat 2.
1e-5
.06-1
W
CJ
2
<
CQ
DIETHYL ETHER
1142.9 cm-l Res 0.5 cm-l
2e-6 40-6 6e-6
CONCENTRATION (M)
Figure C-46. Diethyl ether.
81
8e-6
-------
.03-1
U
o
z
<
m
OS
o
CO
OQ
.02-
ACETONE
1217.7 cm-1 Res 0.5 cm-1
2.5e-6 5e-6 75«-6
CONCENTRATION (M)
Figure C-47. Acetone.
te-5
W
O
2
<
CD
METHANOL.LOG
1033.3 cm-1 Res 0.1 cm-1
2a-6 4e-6 6«-6
CONCENTRATION (M)
Figure C-48. Methanol.Log.
82
8«-6
-------
.08-,
METHANOL.COR
1033.3 cm-1 Res 0.5 cm-1
W
CJ
<
ffl
.04-
03
.02-
2e-6 4e-6 6a-6
CONCENTRATION (M)
Figure C-49. Methanol.Cor.
8e-6
o
<
m
ct:
QQ
.02-
.01-
ETHANOL
1066.1 cm-1 Res 0.5 cm-1
2.5e-6 5e-6 75«-6 1e-5
CONCENTRATION (M)
l25«-5
Figure C-50. Ethanol.
83
-------
.02-,
ri-BUTANOL.DATl
2967.4 cm-l Res 0.5 cm-1
W
o
z
<
ffi
a:
o
CO
00
.015-
.01-
.005-
2e-6 4e-6
CONCENTRATION (M)
Figure C-51. n-Butanol.Dat 1.
6«-6
.008-,
n-BUTANOL.DAT2
1068.8 cm-1 Res 0.5 cm-1
W
O
2
<
OQ
04
.006-
.004-
.002-:
2e-6 4a-6
CONCENTRATION (M)
6a-6
Figure C-52. n-Butanol.Dat 2.
84
-------
.08-,
CYCLOPENTANE
8966.0 cm-1 Res 0.5 cm-1
u
2
<
03
K
O
CO
m
.06-
.04-
.02-
2e-6 40-6
CONCENTRATION (M)
Figure C-53. Cyclopentane.
6«-6
ETHYL ACETATE
1241.4 cm-1 Res 0.5 cm-1
U
u
<
m
.08-
.06-
.04-
.02-
-1 \ T
2e-6 4e-6 6e-6
CONCENTRATION (M)
Figure C-54. Ethyl acetate.
85
-------
u
o
<:
CD
a:
8
QQ
.015-
.005-
METHYL ETHYL KETONE
1174.2 cm-1 Res 0.5 cm-1
2e-6 4e-6 6«-6
CONCENTRATION (M)
Figure C-55. Methyl ethyl ketone.
8e-6
Z
<
m
PYRIDINE
700^8 cm-1 Res 0.1 cm-1
2»-6 4e-6
CONCENTRATION (M)
6e-6
Figure C-56. Pyridine.
86
-------
u
u
2
<
m
K
o
.09-1
.06-
.03-
l.U-TRICHLOROETHANE
726.3 cm-1 Res 0.5 cm-1
3e-6 6e-6
CONCENTRATION (M)
9e-6
Figure C-57. 1,1,1-Trichloroethane (1,1,1-TCA).
u
u
2
<
m
a:
.05-1
.04-
.03-\
.02-
.01-
1,4-DIOXANE.DATl
2863.1 cm-1 Res O.S cm-1
1 T
2a-6 4e-6
CONCENTRATION (M)
6a-6
Figure C-58. 1,4 Dioxane.Dat 1.
87
-------
.04-i
1.4-DIOXANE.DAT2
1138.3 cm-1 Res 0.5 cm-1
.03-
W
o
03
a:
o
.02-
.01-
2a-6 4e-6
CONCENTRATION (M)
6e-6
W
O
2
<
03
.02-
03
.01-
Figure C-59. 1,4-Dioxane.Dat 2.
.03-1
METHYL ISOBUTYL KETONE
2965.4 cm-1 Res 0.5 cm-1
2e-6 4e-6 6e-6
CONCENTRATION (M)
8«-6
Figure C-60. Methyl isobutyl ketone.
-------
.01-,
ETHYL BENZENE
2974.0 cm-1 Res 0.5 cm-1
.0075-
W
U
CD
a:
?>
CO
.005-
.0025-
1e-6 2e-6 3e-6
CONCENTRATION (M)
4«-e
Figure C-61. Ethylbenzene.
89
-------
X 0. 1
0.0240
1.0048
-0.03-16
O
2
<
VO m
° §
CO
CO
-0.0624 "I
-0.0912 "I
-0.1200
850. 0
T
825.
800.0
775. 0
750.0 CM-1
Figure C-62. Calibration of spectrometer for p-xylene at 0.0462 torr. Source 25 cm from aperture and 16
cm cell mirror 35 CD 740.3 torr.
-------
-0.1200 L
aoo.o
725.0
700.0 CM-1
Figure C-63. Calibration of spectrometer for o-xylene at 0.0687 torr. Source 25 cm from aperture and 16
cm cell mirror 35 cm 740.0 torr.
-------
vO
to
-0.1100
800.0
775.0
1 p
750.0
725.0
700.0 CM-1
Figure C-64. Calibration of spectrometer for m-xylene at 0.0868 torr. Source 25 cm from aperture and 16
cm cell mirror 35 cm 740.0 torr.
-------
0.0220
3100.
3025.
29!
2800. CM-1
Figure C-65. Calibration of spectrometer for n-hexane at 0.0844 torr. Source 25 cm from aperture and 16
cm cell mirror 35 cm 740.4 torr.
-------
0.0000
3100.
3025.
2950.
2875.
2800. CM-1
Figure C-66. Calibration of spectrometer for n-pentane at 0.0788 torr. Source 25 cm from aperture and 16
cm cell mirror 35 cm 740.0 torr.
-------
SO
Ul
X 0. 1
0.2000 f
0.2440-
0. 1980 -
O
Z
<
CO
Or
O
(/>
CD
0.1520 -
0. 1060-
0.0600
3050.
3000.
2950.
2900.
2850. CM-1
Figure C-67. Calibration of spectrometer for ethane at .06A9t ? Lect. bottles. Source 25 cm from
aperture and 16 cm cell mirror 35 cm 740.0 torr.
-------
I I I I I I
O.OS40
3050.
2975.
2900.
2825.
Figure C-68. Calibration of spectrometer for isobutane at .0746t ? Lect. bottles.
aperture and 16 cm cell mirror 35 cm 740.0 torr.
2750. CM-1
Source 25 cm from
-------
X 0. 1
0.3300
0.2664 1
0.2029-1
O
CD
DC
O
(A
CD
0.1392 H
0.0756-1
0.0120
1100.
1025
800. CM-1
Figure C-69. Calibration of spectrometer for 1,3-butadiene at .0910t lee. bot.
aperture and 16 cm cell mirror 35 cm 740.0 torr.
Source 25 cm from
-------
00
X 0. 1
0.2200
O
z
<
CD
CC
O
CO
m
0. 1794-
0. 1338 '
0.0902 *
0.0576 -
0.0170
3150.
3050.
29!
2850.
Figure C-70. Calibration of spectrometer for 1,3-butadiene at .0910 torr lee. hot.
aperture and 16 cm cell mirror 35 cm 740.0 torr.
2750. CM-1
Source 25 cm from
-------
X 0. 1
0.4800
0.3366-
0.2932 -
o
z
cc
m
0. 1994 -
0. 1064-
0.0130
1150.
Figure C-71. Calibration of spectrometer for propylene at 0.1915 torr ? Lee. hot.
aperture and 16 cm cell mirror 35 cm 740.0 torr.
750. CM-1
Source 25 cm from
-------
0.210
-O.OOS
1350.
1200.
900.
750. CM-1
Figure C-72. Calibration of spectrometer for Freon 13 (CC1F3) at .1225 torr ? Lect. hot. Source 25 cm
from aperture and 16 cm cell mirror 35'cm 740.0 torr.
-------
Figure C-73.
Calibration of spectrometer for ethyl chloride at .1015 torr ? Lect. hot.
aperture and 16 cm cell mirror 35 cm 740.1 torr.
650. CM-1
Source 25 cm from
-------
o
ro
X 0. 1
0.2000
0. 1600-
0. 1360-
O
CO
o:
o
V)
CD
0. 1040-
0.0720-
0.0400
3100.
2900.
2800.
Figure C-74. Calibration of spectrometer for dimethyl ether at .1220 torr ? Lect. hot.
aperture and 16 cm cell mirror 35 cm 740.0 torr.
2700. CM-1
Source 25 cm from
-------
o
u>
o.oiao
1350.
1200.
1050.
900.
Figure C-7S. Calibration of spectrometer for dimethyl ether at .1220 torr ? Lect. bot.
aperture and 16 cm cell mirror 35 cm 740.0 torr.
CM-1
Source 25 cm from
-------
0. 1200
3100.
3000.
2900.
2800.
2700. CM-1
Figure C-76. Calibration of spectrometer for iso-octane at .1040 torr ? Lect. bot. Source 25 cm from
aperture and 16 cm cell mirror 35 cm 740.0 torr.
------- |