1478 ANALYTICAL CHEMISTRY

and Refining Company and the Atomic Energy Commission for
permission to publish these data.
LITERATURE CITED
(1) Delfosse, J., and Hippie, J. A., Phys. Rev., 54, 1060 (1938).
(2) Evans, M., Bauer, N., and Beach, J. Y., J. Chem. Phys., 14, 701
(1946).
(3) Fischer, R. B., Potter, R. A., and Voskuyl, R. J., Anal, Chem.,
20, 571 (1948).
(4) Flexner, L. B., Gellhorn, A., and Merrell, M., J. Biol. Chem..
144, 35 (1942).
(5) Hevesy, G., and Jacobsen, C. F., Acta Physiol. Scand., 1, 11
(1940).
(6) Mohler, F. L., and Dibler, V., Phys. Rev., 72, 158A (1947).
(7) Orchin, M., Wender. I., and Friedel, R. A., Anal. Chem., 21,
1072 (1949).
(8) Smyth, H. D., “Atomic Energy for Military Purposes,” Prince-
ton, Princeton University Press, 1945.
(9) Swann, H. G., U. S. Air Force Air Matériel Command, A.F.
Tech. Rept. 5972, Wright-Patterson Air Force Base. Dayton,
Ohio, August 1949.
(10) Swann, H. G., Brucer, M., Moore, CM and Vezien, B. L.. Texas
Repts. Biol. Med., 5, 423 (1947).
(11) Taylor, R. C., and Young. W. S. Ind. Eng. Chem., Anal. Ed.,
17,811 1945).
(12) Thomas, B. W., and Seyfried, W. D., Anal. Chem., 21, 1022
(1949).
(13) Turkevich, J., Friedman, L.. Solomon, E., and Wrightson,
F. M., J. Am. Chem. .Sac., 70, 2638 (1948).
Received February 27, 1950. Presented at the Consolidated Engineering
Corporation Mass Spectrometer Annual Conference, New York, N. V.. May
1949.

Infrared Absorption Spectra of Minerals and

Other Inorganic Compounds
JOHN M. HUNT, MARY P. WISHERD, AND LAWRENCE C. BONHAM1
The Carter Oil Company, Tulsa, Okla.

A method is described for utilizing the infrared spectrophotometer in the

analyses of minerals and other inorganic compounds. Mineral samples are
ground to a powder having an average particle diameter smaller than 5 microns.
The powder is deposited as a film on a conventional rock salt window. The
spectra of 64 minerals, rocks, and inorganic chemicals are shown for the wave-
length region from 2 to 16 microns. Spectral positions of the principal absorp-
tion bands of these compounds are tabulated. The technique is used in the
study of fine-grained rocks. Analytical chemists in other fields such as catalysis,
soils, and ceramics may find the same methods applicable to their problems.

spectroscopy' is used extensively for the identifica-
INFRARED
tion of organic molecules (2, 4), but its application to the field
of inorganic analysis has been rather limited. Inorganic solids
cannot be analyzed in polar solvents such as water because such
solvents generally' have strong absorption bands of their own in
the infrared range. Spectra have been obtained from thin sheets,
but many' substances cannot be sliced thin enough to prevent
them from being opaque to infrared radiation. Conventional
methods of mulling the sample in Nujol (S) produce spectra
which are poorly defined because of reflection and refraction of
the incident radiation by' crystal particles. In addition, the
absorption bands of Nujol must be distinguished from those of
the substance being analysed.
The infrared technique described herein was developed as a
means of analyzing rocks, but the same methods are applicable to
analytical problems in other fields such as catalysis and ceramics.
The technique involves grinding the sample to a powder having
an average particle diameter of less than 5 microns. This powder
is spread as a thin film over the sodium chloride window through
which the infrared radiation passes. Qualitative determinations
of the major constituents of rocks can be obtained rapidly' by this
technique. Semiquantitative data may' be obtained if all of a
sample is ground to the desired particle size.
The infrared absorption of very small particles was first studied
extensively by Pfund and associates (9, 10). They' found that
when a crystalline material is ground to a size finer than the wave
length of the infrared radiation, its spectrum is sharpened con-
siderably.
1
Present address, Washington University, St. Louis, Mo.
Pfund also found that films made from particles larger than
the wave length tended to scatter the infrared radiation at all but
a few wave lengths. At these few positions most of the radiation
was transmitted through the film, giving rise to transmission
bands.
Barnes and Bonner (1) demonstrated that the scattering of
radiation by large particles was due mainly to refraction. They'
established that the transmission peaks observed by' Pfund were
due to a lack of refraction at wave lengths where the refractive
index of the particles is 1.0. Such abnormally low refractive
indexes occur on the short wave-length side of absorption bands
as a result of the phenomenon of anomalous dispersion.
Henry (6) studied the effect of particle size and layer thickness
on the infrared transmission of dry films of quartz powder. True
absorption spectra were obtained from thin films of quartz par-
ticles 1 micron in average diameter. Scattering by' refraction
occurred only' at the very' short (less than 3-micron) wave lengths.
With large particles none of the light was transmitted in the 2- to
16-micron range except at the few wave lengths where refraction
was at a minimum.
The authors separated fine particles into uniform sizes by
sedimentation. Transmission spectra were obtained from pow-
der films made up of only large particles (>20 microns), whereas
absorption spectra were obtained from powder films of only small
particles (<5 microns).
Transmission spectra of four minerals are shown in Figure 1.
The major transmission bands on these spectra occur at the fol-
lowing wave lengths: 7.3, 12.2, and 14.2 microns for quartz;
7.9 microns for montmorillonite; 6.1, 11.2, and 13.9 microns for
VOLUME 2 2, NO. 12, DECEMBER 1950 1479

calcite; 5.9, 10.9, and 13.5 microns for dolomite. Each trans-
mission band occurs where the refractive index of the mineral
approaches 1—that is, on the short wave-length side of an absorp-
tion band. Spectral positions of the transmission bands are
characteristic for different minerals and could be used for ana-
lytical work if the particle size were controlled. The peaks tend
to shift somewhat, depending on the average particle diameter (5).
The absorption spectra of 100 minerals, polymineralie sedi-
ments, and inorganic chemicals were obtained and are shown for
tlie wave-length region from 2 to 16 microns. Spectral positions
of the principal absorption bands of these compounds are tabu-
lated.
EXPERIMENTAL
The absorption spectra were obtained from powders having
particle diameters smaller than 5 microns in all cases except for
those minerals which were difficult to disperse by sedimentation,

COMPOUND

QUARTZ
SiO,

SOURCE AND PURITY

CANADA

STATE SOLID
TEMPERATURE 25-30*0
THICKNESS fOmgm/em2
PARTICLE
DIAMETER >66/a
1480
such as pyrite and galena. About 0.2 gram of powder smaller than
,5 microns is sufficient for analysis. This can be obtained by grind-
ing about 5 grams of the sample to a fineness that will pass a 150-
mesh screen. This pow'der is added to 250 ml. of distilled water
with a small amount of a dispersing agent. For clays the dis-
persing agent is 15 ml. of 0.2 N sodium oxalate, and for carbonates,
silicates, and the inorganic chemicals it is 5 drops of sodium
metasilicate. The mixture is violently agitated in a Waring
Blendor for about 10 minutes. The suspension which forms is
poured from the blender into a 250-ml. graduated cylinder and
ANALYTICAL CHEMISTRY
allowed to stand 2 hours. At the end of this time the upper 5
inches of the suspension will contain particles less than 5 microns
in diameter.
The exact particle-size distribution can be calculated from
Stokes’ law. It -will vary somewhat, depending on the specific
gravity of the sample and the temperature. The upper
5 inches (12.5 cm.) of suspension are drawn off and centrifuged
to separate the sediment from the solution of the dispersing agent.
The sediment is then dried in an oven at 105° to 110° C. for 24
hours, and placed in a desiccator prior to use.

WAVE NUMBERS IN CM’1

COMPOUND
TREMOLITE
AND
CALCITE
SOURCE AND PURITY

CONNECTICUT

STATE SOLIO
TEMPERATURE 25-50 C
THICKNESS I.Smgm/em8
CURVE I-REF SHUTTER OPEN
CURVE 2-REF SHUTTER
LOWERED 16 TURNS

MAGNESITE

SOURCE AND PURITY

WASHINGTON

STATE S0..0
TEMPERATURE 25-30*C
THICKNESS 0.2 mgm/em2

DOLOMITE
Ca r/g:C02 )2

SOURCE AND PURITY

NEW YORK

STATE SOLID
TEMPERATURE 25- 30’C
THlCKN'ESS c.2 rngm/em8

COMPOUND

CALCITE

SOURCE AND PURITY

MEXICO

STATE SO.ID
TEMPERATURE 25-30 C
THICKNESS 0 3 mgm/em2
VOLUME 2 2, NO. 12, DECEMBER 1950 1481

A number of samples can be sedimented concurrent!}·, so that
the time required for any one sample is short. Smaller particle
sizes may be obtained by drawing off less suspension or by allow-
ing it to stand longer.
Some difficulty is experienced in preventing coagulation of fine
suspensions, particularly clays. If a sharp line of demarcation
forms in the graduate while standing, it indicates that coagulation
has taken place and the sample must be dispersed again with
another agent. Some samples have a tendency to gel. This
can be broken by diluting the suspension about 4 to 1 with dis-
tilled water and adding 0.1 gram of sodium hexametaphosphate.
Clays such as montmorillonite have a tendency to coagulate on
drying. Sometimes this may be avoided by drying at a lower
temperature. If not, the sample is sedimented in isopropyl,
alcohol and kept as a paste until analyzed.
If equipment for very fine grinding is available, it is preferable

COMPOUND

ARAGONITE

SOURCE AND PURITY

CALIFORNIA

CALCITE IMPURITY

STATE SOLIO
TEMPERATURE 25-30*0
THICKNESS 0.4mgm/cm*

COMPOUND

RH0D0CHR0SITE
MnC0$

SOURCE AND PURITY

MONTANA

STATE SOLIO
TEMPERATURE 25-30*0
THICKNESS 04 mgm/cm*

VE NUMBERS IN CM'1

COMPOUND

S1DERITE

SOURCE AND PURITY

CONNECTICUT

STATE SOLID
TEMPERATURE 25-30*0
THICKNESS 0 5 mgm/cm*

WAVE NUMBERS IN CM'1

COMPOUND

SMITHSONITE

SOURCE AND PURITY

MISSOURI

STATE SOLID
TEMPERATURE 25-30*0
THICKNESS 0.5 mgm/cm*
1482 ANALYTICAL CHEMISTRY

to grind a small sample completely to particles less than 5 microns
in diameter. Such samples can be run directly by infrared with-
out going through the steps of sedimenting, centrifuging, and
drying to isolate the fine particles. This saves considerable
time, and, in addition, the substance is handled in the dry state.
The spectra were recorded on a Baird Model B double-beam
infrared recording spectrophotometer. The oven-dried sample is
crushed in a small mortar to separate particles which have ad-
hered together, and some of the powder is placed on a standard
sodium chloride window. A few drops of isopropyl alcohol are
added to form a paste. The paste is smoothed out on the window
with a microscope slide whose edges have been beveled and pol-
ished to prevent scratching. When the slide is removed, the alco-
hol evaporates, leaving a thin film of sample on the window.
The window- with the powder film on it is inserted in the sample
beam and a blank sodium chloride window is placed in the
reference beam. The shutters in front of both source mirrors are
left wide open. When the recording is finished, the window with

WAVE NUMBERS IN CM-1

WAVE NUMBERS IN CM'1

COMPOUND

BARITE

SOURCE AND PURITY

MISSOURI

STATE SOLID
TEMPERATURE 25-30 C
THICKNESS 0.7 mgnvemZ

WAVE LENGTH IN MICRONS

COMPOUND

PYRITE

SOURCE AND PURITY

UTAH

STATE SOLID
TEMPERATURE 25-30*C
THICKNESS 0.3 mgm/em*
VOLUME 2 2, NO. 12, DECEMBER 1950 1483

the powder film is weighed before and after removing the film with
alcohol. The difference in weight divided by the area is recorded
on the spectrogram as milligrams per square centimeter. Care
must be used to handle the window with rubber finger tips, or
tongs, to prevent it from changing weight.
For purposes of correlation it is sometimes desirable to expand
the scale of the spectrum in order to bring out weak absorption
bands. By mounting a very thick sample the intensity of the
absorption bands can be increased, but the over-all transmitted
radiation is seriously decreased. With a single-beam spectro-
photometer the slits can be opened to compensate for the over-all
loss in transmitted radiation. With a double-beam instrument
the same result can be achieved by lowering the shutter in front
of the reference beam. This has the effect of increasing the dif-
ference between the two beams.
The expansion of the spectrum of a mixture of tremolite and

WAVE NUMBERS IN CM'1

COMPOUND

GALENA

SOURCE AND PURITY

ILLINOIS

STATE SOLID
TEMPERATURE 25-30*0
THICKNESS O.S mgm/cm8

WAVE NUMBERS IN CM*1

COMPOUND

d-OUARTZ
s;o8

SOURCE ANO PURITY

OTTAWA, CANADA

STATE SOLID
TEMPERATURE 26-30* C
THICKNESS 0.2 mgih/e/n*

WAVE NUMBERS IN CM*1

COMPOUND

CHERT

_»o,_
SOURCE AND PURITY

MISSOURI

STATE SOLID
TEMPERATURE 25-10*0
TH'CKNESS 0 3 mgm/cm8

COMPOUND

OPAL

SOURCE AND PURITY

WYOMING

STATE SOUD
TEMPERATURE 26-30*0
ThiCKNESS 0.2 myn/cm8
1484 ANALYTICAL CHEMISTRY

calcite by this technique is illustrated by the first set of curves in
Figure 2. Curve 1 was obtained with the reference shutter open,
and No. 2 with it partly closed. The peaks in the 13- to 15-
micron range are more prominent in curve 2 than in No. 1. For
quantitative work, the measurement of optical densities from a
background line on the expanded scale is inaccurate, because the
line is actually off the scale. However, “base line” optical den-
sity measurements ( ), which are independent of the background
line, may be used. The spectra of minerals and inorganic com-
pounds are shown at two powder film thicknesses. The thin
films were run with the normal transmission scale, but in a few
cases the thicker films were run with the expanded scale.
MINERALS AND ROCKS
Absorption spectra of minerals and sediments are shown in
Figures 2 to 13. The clay minerals were obtained through the

COMPOUND

HEMATITE

SOURCE AND PURITY

MINNESOTA

STATE SCL-0
TEMPERATURE 25-10 C
THICKNESS 0.5 mgm/cm2

ILMENITE

SOURCE AND PURITY

NORWAY

TEMPERATURE 25- 30* C

THICKNESS ß mgm/em*

OLIVINE
(Mg, F$)2 Si 0«

SOURCE AND PURITY

NORTH CAROLINA

TEMPERATURE 25-10*0
THiCKNESS 0.2 rngm/em^

COMPOUND

GARNET

SOURCE AND. PURITY

NEW YORK

TEMPERATURE 2S-30°C
1 THICKNESS Clmgrr./cm2
VOLUME 2 2, NO. 12, DECEMBER 1950 1485

courtesy of R. E. Grim of the Illinois Geological Survey. Most
of the other minerals were purchased from Wards Natural Science
Establishment. Chemical analyses of the minerals were not
available, but from optical examination it was estimated that the
impurities in most cases did not exceed 5%. Wave-length posi-
tions of the absorption maxima (or shoulders) for each mineral
are listed in Table I. The spectrometer was calibrated from the
known wave lengths of absorption bands of benzene and pyridine.
The wave-length measurements are accurate to about ±0.04
micron in the 2- to 5-micron region, and ±0.02 micron in the Si-
to 15-micron region. The amount of powdered mineral traversed
by the beam is expressed in terms of milligrams per square centi-
meter. The relative intensities of the absorption bands are indi-
cated by the letters s, m, and w, signifying strong, less than 25%
transmission; medium, 25 to 75% transmission; and weak, moré
than 75% transmission. These values are for the transmittance

COMPOUND

AUGITE
CaMg!S.0$)2

SOURCE AND PURITY

ONTARIO, CANADA

S’AT E SOLO
TEMPERATURA 25-30° C
THICKNESS , ·-2

COMPOUND

TREMOLITE
;OH)2 Co2Mg5(S<4Ol|)2

SOURCE and PURITY

CONNECTICUT

STATE SOLID
TEMPERATURE 25-30 C
THICKNESS 0 3mgm/cm2

COMPOUND

ACTINOLITE
(OHlgC^MgFsl^Si^lj
SOURCE AND PURITY

VERMONT

STATE SOLID
TEMPERATURE 25-30° C
THICKNESS 0 2 mgm/em2

WAVE numbers in cm-1

COMPOUND

HORNBLENDE
C<i(MgFt)3Sl4Oj2;
GgMgg(AlF»2Si30|2
SOURCE AND PURITY

ONTARIO, CANADA

STATE SOLIO
TEMPERATURE 25- 30*0
THICKNESS Oamgrr/cm2
 Table 1. Spectral Positions of Infrared Absorption Bands of Minerals and Chemicals'* U86

Wave-Length Range, Microns _

2-3µ 4µ 5µ 6µ 7µ 8µ 9µ _10µ_ 11µ 12µ 13µ 14µ 15µ

. Minerals
('arbonates
Magnesite, Mg( Oj 4.00 w G.9 a 11 70 w 13.33 m
Dolomite, (.'aMg((’OjV· 4 ,00 w 6.9 s 11¡30 m 11 70 w 13.70 m
t’alcite. CaCOg 4.03 w 5.58 w 6.95 s 11.40 m 11 80 w 14.02 m
Aragouite, CaCOg 4.02 w 6.95 s 11.40m 11 65 m 14.02 m
14.30 w
Rhodochroaite, MnCOg 4.05 w 5.58 w 7.0 s 11.50 m 11 95 w 13.72 m
Siderite, FeCOg 4.05 w 5.58 w 7.0s 11.50 m 11 95 w 13.50 m
Smithsonite, ZnCOg 4.05 w 5.58 w 7.0 s 11.47 m 11 90 w 13.40 m

Sulfates
Gypsum, OaSOi.2HiQ 2.85 m ... ... ti.tSm 7.ÓÓW 8.72 3 9.14 s 9.92 m 12.72 w 15.15 m
8.97 a
Gypsurn, CaSOi (dehydrated) V! 6.90 w 8.72 s 9.10 s 9.85 w 11.42 w 14 AJÓ m
Barite, BaSOi 6.15 w 7.55 w 8.45 in 9.2 s 10.16 m 11.30 w 12.75 w ... ... ... lo.70 m
6.80 w 8.9 s
Sulfides
Pyrite, P'eSz 8.9 m 9.7 s 9.9 s 10.95 m 12.6w
Galena, PbS V! 6.9 m 9.5 w 11.5 w

Oxides
-Quartz, S1O2 5.1 w 6.2 w 8.60s 9.2 s 10.95 w 12.52 m 12.82 m 14.42 m
5.38 w
5.6
5.95 w
Chert, S1O2 5.1 w 6.2 w 8.60 s 9.2 s 12 ¡ 52 m 12*82 m 14¡42 m
5.38 w
5.6 w
5.95 w
Opal, SiOz.ntlzO 3.0 w 5.38 w 6.1 w 8.2 m 9.2 m 10.5 m ... 12.55 m
Hematite, FezOg 7.05 w 10.2s 12.3 w 13.3 m '

Ilmenitc, (Fe,Mg)OTiOz 10.0m 10.3 m 16 s'

Silicates
Olivine, (Mg.FehSiO* 2.75 w 6.1 w 10.0s 10.5 s 11.2 s 11 90 m 13.1 w
Garnet, FegAUSiíOiz (almandite) 6.9 w 9.8m 10.35 s 11.13 s 11 47 s
Augite, CaMgiSiOaV 6.9 w 9.37 s 9.8 s 10.38 s 10 V) m 11.45 s 14.95 m 15.8m
Tremolite, (OHhCazMgitSiiOiOz 9.0 s 9.9 s 10.55 s 10.85 m 13.15 m 14.6 m
9.3 s 14.95 m
Actinolite, (OH)2Caz(Mg,Fe)5(Si.tOii)2 9.0 s 10. Vs 10¡5s 10.85s 13!15 m 14.6 111
9.35 s 14.95 m
Hornblende 6.15 w 7.55 w 9.8 s 12.75 w 14.95 m 15.05 w

Wollastonite, CaSiOg 9.10 s 9.75 s 10.33 s 10.72 s 11.05 s 14.7 m 15.5 m

9.40 s
Biotite, K(Mg,Fe)g(AlSigOio)(OH)2 10 ¡Ós 10¡3 s 12.8 w 14 ¡3 in
Muscovite, KAl2(ALSigOio)(01i)z 2.78 m 9.35 s 9.7 s 11'0 m 12.1 w 12.5 w 13.35 m 14.8 w
Talc, Mgg(Si40io)(OH)z 9.8s 14.9 m 15 .V w

Microcline, KAlSigOe 6.15 w 7.55 w 8.80s 9.1s 9.9 s 12.95 m 13.70 m 15.42 w
9.5 s
Albite, NaAlSigOs 6.8 w V! 8.70 s 9.1s 9.9 s 12!68 m 13.ÍÓ m 15.4 m
9.7 s 13.40 m
13.80m
Oligoclase, (80% albite, 20% anorthite) 6.15 m 7.55 w 8.7s 9. Vs 9.9 s 12 70m 13.15 m 15.6 m
9.6 s 13.8 m
Anorthite, CaAlgSizOg 6.9 vv 9.1 m ioVVs 10¡9 w 12! 2 w 13.2m 14.6 w
10.5 s 13.7 w ANALYTICAL

Nepheline, NaAlSiOi 6.1 w 9.2 s 10.1 s 13.0 m 14¡05 m 15 ¡Óm

6.6 vv 13.60 m 14.5 m

Clay minerals
Kaolinite, AUSiz06(OH)4 2.73 m 6.0 w 7.55 w 8.93 s 9.65s 9.90s 10.68 m 10.95 s 12.50 m 12.65 m 13.3 w 14.5 m
6.1 w
Illite 2.78 to 6.0 w 7.55 w 8.95 m 9.7 s 10.95 m 12.05 w 13.3 w
3.2 m 6.1 w
Montmorillonite 2.8 to 6.15 m 7.55 w 8.95 in 9.6 s 10.95 m 11.4 m 11* 85 m 12.75 w
3.2 m CHEMISTRY
VOLUME 2 2, NO. 12, DECEMBER 1950 1487

5 5.......3 > obtained with a powder film having 0.6 mg. of powder per square
centimeter. The low transmittance of several spectra in the 2-
to 5-micron region is not due to absorption, but to scattering. It
-
= 3 t * 3 a 5 _ can be eliminated by using only particles less than 1 micron in
"N ·
&copy;
— O <N CC &copy; h-
diameter, but this was not practical for the present work. Small
*r Tt tf- tp ir
peaks at 4.3 and 15.0 microns in the spectra are due to carbon
dioxide in the atmosphere.
The spectra of minerals containing the same structural groups
were found to have absorption bands of the same general shape
and relative intensities at slightly different wave-length positions.
By comparing several such spectra, it was possible to assign some
of these bands to specific structural groups, as discussed in the
following sections.
Carbonates. The infrared spectra of seven carbonates are
shown in Figures 2 and 3. All the spectra have a broad band in
the 6.5- to 7.5-micron region, two sharp bands in the 11- to 14-
micron region, and three very small peaks which appear in the
spectra of thick films. Any one of the carbonates can be dis-
tinguished from the others by the spectral positions of the three
stronger bands. The most pronounced difference is in the band
which varies between 13.3 and 14.0 microns. For calcite and
dolomite it is a full 0.3 micron apart. The spectrum of aragonite
differs from the general carbonate pattern in having two promi-
nent absorption bands in the 11- to 12-micron region.
The infrared curves of the carbonates also show an absorption
band in the 9- to 10-micron region. This may arise from the
carbonates or from impurities. Silicates absorb strongly in this
&copy;
‘ ‘ '

'&copy;&copy;CC&copy; o&copy; &copy;c region.

Sulfates. Three sulfates were examined: gypsum, dehydrated
* gypsum, and barite (Figure 4). The sulfates have strong bands
at about 9 and 15 microns. The band at 9 microns differs in

í £ a * *
shape for gypsum and barite. The water in gypsum causes
S
^ ·3 . .
.s; .

: : strong absorption at 2.85 and 6.15 microns. Dehydration by

: (NX
&copy; &copy;&copy;&copy;&copy; &copy; ® &copy;
* &copy;
*
&copy;&copy; &copy;&copy;
heating for 2 hours at 300° C. eliminates these bands and con-
siderably alters the over-all spectrum. A new band appears at
&copy;^&copy;xox ; 6.9 microns, bands at 7.5, 9.9, and 12.7 microns are suppressed or
XXXXXX
XXX X
eliminated, and the band at 15.15 microns is shifted 0.25 micron
in

s
toward a shorter wave length. Both barite and dehydrated
: : :
18
gypsum have the band at about 6.9 microns.
&copy;
^*^ &copy; &copy;&copy; ·
t- O t-
Sulfides. Infrared spectra of pyrite and galena are shown in
£ a i
- E
Figures 4 and 5. There is poor resolution in these two spectra
—
=&copy;&copy;=&copy;“
t-· &copy; &copy; &copy; X oooy * ; _

due to scattering of the light b}· large particles. These minerals

&copy; &copy; &copy; &copy; &copy; &copy; &copy;&copy;&copy; &copy;
x> &copy;
&copy; &copy; &copy; &copy;

could not be sedimented, and so were examined as a finely ground

a a a
powder. Both appear to have absorption bands in the region
. a a .
a . . .

&copy; &copy; &copy; &copy; &copy;

from 9.5 to 10.0 microns. Galena has an additional band at 6.9
microns that does not appear in pyrite.
*
Oxides. The spectra of three forms of silicon dioxide are shown
.....

a
»>&copy; M
'r *
= in Figure 5. -Quartz and chert have the same spectra except
j^sj near 11 microns, where a band appears in «-quartz that is
3 fi cc a £ £ a g
&copy; &copy; &copy;

.&copy;«&copy;&copy;t·»&copy;
&copy; u-i
5
T°1 o absent in chert. Opal, the hydrate, differs considerably from the
others. The double band around 12.5 microns, typical of quartz,
.5
·|§3"
S g
is changed to a single broad band in opal. Bands due to water
appear in opal at 3.0 and 6.1 microns. The bands at 8.6 and
»
£-3 -

93 >—
- &copy;
'3 “=
^
14.4 microns in quartz are absent in opal.
55

3 53 gj2 Keller and Pickett (8), in a study of the infrared spectra of pow-
J3j3.2·-
ß·~ « * dered silica minerals, listed several absorption bands for quartz
.2 *·= a
agi'l that coincide with the data presented here. They also recognized
.a « «
o*3 a.2 some differences in the spectra of opal as compared to quartz.
-=5 3
ß43 ®
d
*t!
565 = Unfortunately, their spectra were partly obscured by scattering
3-a a
§»ll
a&copy;

5 a
’

gh·- due to the presence of large particles.

3 « 0 8
(5 O
The curves of hematite and ilmenite (Figure 6) have low trans-
g g-e S
s£ SI
3 a
1511
s*£aj « 3 2
mission in the short wave-length range (2 to 6 microns) due to
«
«·- s a
“|c e § e.a
scattering. Both spectra have an absorption band around 10
chemicals

.2
E to -r
ifli
·-
v q,
-
c 2 «83*— gj b
microns, which may be due to the FeO linkage. In ilmenite it is
-
·-
e* 6Í 3
&copy;
JC «3 8$ 83
üSü® ü Ü So CO ffl ccO
smaller and displaced 0.2 micron toward the shorter wave lengths.
rt ii ”
Ilmenite also absorbs strongly over a broad range starting at 13
Inorganic

11. microns.
1488 ANALYTICAL CHEMISTRY

Silicates. Infrared spectra of fifteen silicates are shown in
Figures 6 to 10. All these minerals absorb strongly in the region
from 9.5 to 11 microns, although the shape of the absorption band
differs considerably between the different silicates. The curves,
of garnet and olivine (silicates with Si04 groups) are easily dis-
tinguished in this range (Figure 6).
The spectra of augite (a pyroxene) and three members of the
amphibole group—tremolite, actinolite, and hornblende—are
shown in Figure 7. Tremolite and actinolite have strikingly
similar spectra with several strong bands in the region from 9 to
11 microns and a sharp band at about 13.2 microns. Hornblende
differs entirely from these two in having one strong band in the
9- to 11-micron region and another at about 15 microns.
Spectra of wollastonite, talc, and the two micas, muscovite and
biotite, are shown in Figure 8. Replacement of aluminum in
muscovite with magnesium and iron (biotite) eliminates bands at

COMPOUND

WOLLASTONITE

SOURCE AND PURITY

CALIFORNIA

STATE SOL'D
TEMPERATURE 25-30*0
THICKNESS 0 2 mgm/cm2

COMPOUND

BIOTITE
KlMgFelj 5 3 |(^0 )2

SOURCE AND PURITY

NORTH CAROLINA

STATE SOL'D
TEMPERATURE 25-30*0
THICKNESS 0 2 mgm/cm2

COMPOUND

MUSCOVITE
K
AljUlSijOj (0H)2

SOURCE AND PURITY

NORTH CAROLINA

STATE SOL'D
TEMPERATURE 25-30 0
THICKNESS 0.2 mgm/cm2

COMPOUND

TALC
M=
31Si4°,c?(OH)2

SOURCE AND PURITY

RHODE ISLAND

STATE SOLID
TEMPERATURE 25-30*0
THICKNESS 0 2mgm/cm2
VOLUME 2 2, NO. 12, DECEMBER 1950 1489

9.35, 11.0, and 13.35 microns, Talc, without aluminum or iron
in its structure, has only two clearly defined absorption bands.
The spectra of microcline and three of the plagioclase feldspars,
albite, oligoclase, and anorthite, are illustrated in Figure 9. The
feldspars have characteristic absorption bands in two regions,
one extending from 8.5 to 10.5 microns, and the other from 12.5 to
14 microns. Microcline can be recognized from its two sharp
bands at about 13 and 13.7 microns. Albite has four sharp
bands in this same region. Substitution of calcium for sodium
in the plagioclase series reduces these four bands to one promi-
nent band and shifts the broad band in the 9-micron region to
a. longer wave-length position. The spectrum of nepheline
(Figure 10) has four absorption bands similar to those of the
feldspars, but in a longer wave-length region.
Clay Minerals. The clay minerals absorb strongly in the region
from 9 to 11 microns (Figure 10). Kaolinite has absorption

WAVE NUMBERS IN CM'1

COMPOUND

OLIGOCLASE
(Aib-An)

SOURCE AND PURITY

NORTH CAROLINA

STATE SOLID
TEMPERATURE 25-30*0
THICKNESS 0.2 mgm/cm8

COMPOUND

ANORTHITE
C0Al2S,?O8

SOURCE AND PURITY

CALIFORNIA

STATE SOLID
TEMPERATURE 25-30° C
THICKNESS 0 2 mgm c*ri
490 ANALYTICAL CHEMISTRY

bands at 9.8, 10.7, 12.6, and 14.5 microns that do not appear in
the other clay spectra. The samples of montmorillonite and
illite are not easily distinguished except for the water bands
around 3.0 and 6.1 microns, and the peak position of the strongest
band which occurs at 9.6 microns in montmorillonite and 9.7
microns in illite.
The differences in absorption in the .2.7- to 3.2-micron region
for the clays are of particular interest. Two absorption bands are
clearly evident, one a sharp band at about 2.75 microns and the
other a broad band extending from 2.7 to 3.2 microns. Previous
work by Buswell and Dudenbostel (3) has established that the
2.75-micron band represents unbonded OH, and where hydrogen
bonding occurs there is a shift to longer wave lengths (3 microns).
They also found that this latter band around 3.0 microns is re-
duced by drying the clay.
The three clays studied by the authors were dried at 105° to

COfrtPOUNO

NEPHELINE
NoAIS104

SOURCE AND PURITY

ONTARIO, CANADA

STATE SOviO
TEMPERATURE 25- 30*C
THICKNESS 03 mgm,cm

COMPOUND

KAOLINITE
Alj Oj '2Si Oj’2 HjO

SOURCE AND PURITY

GEORGIA

STATE SOLIO
TEMPERATURE 25-30*0
THICKNESS 0.2

COMPOUND

ILLITE

SOURCE AND PURITY

ILLINOIS

STATE SOLID
TEMPERATURE 25*30 C
THICKNESS 0.3 mgm/cm*

COMPOUND

MONTMORILLONITE

SOURCE AND PURITY

MISSISSIPPI

STATE SOLIO
TEMPERATURE 25-30*0
THICKNESS 0.2 mgm/em2
VOLUME 2 2, NO. 12, DECEMBER 1950 1491

110° C. for 24 hours. The intensity of the two OH bands indi-
cates that for these three clays the percentage of unbonded OH
is greatest in kaolinite and least in montmorillonite, whereas the
opposite is true of the bonded OH. The bonded OH also shows
up as a strong band at 6.15 microns and a weaker band at 7.55
microns.
A more comprehensive study of the infrared spectra of clay
minerals has been published by Keller and Pickett (7).
Soil Samples. The spectra of several soil samples are shown in
Figures 11 and 12. Most of these have recognizable differences.
The clay soils bear a closer resemblance to kaolinite than do the
loams. Fuller’s earth is distinctly different from the others.
Diatomaceous earth has virtually the same spectrum as opal.
Sedimentary Rocks. The spectra of four rocks—a reef lime-
stone, a limey shale, and two oil shales—are shown in Figure 13.
The absorption bands of dolomite and a clay mineral (illite or

WAVE NUMBERS IN CM*'

COMPOUND

LOUISA LOAM

SOURCE ANO PURITY

STATE SOLIO
TEMPERATURE 25-30*0
THICKNESS OErngm/cm8

COMPOUND

CECIL CLAY LOAM

SOURCE AND PURITY

STATE SOUO
TEMPERATURE 25-SO*C
THICKNESS 0 2 myn/cw

COMPOUND

LOESS

SOURCE AND PURITY

IDAHO

STATE SOLIO
TEMPERATURE 25-30*0.
THICKNESS 0.3mgm/cm2

COMPOUND

RESIDUAL SOIL
FROM GRANITE
SOURCE AND PURITY

GEORGIA

STATE SOLID
TEMPERATURE 25-W*C
THICKNESS 0.2 myn/cm2
06
1492 ANALYTICAL CHEMISTRY

montmorillonite) are evident in the reef limestone. The limey
shale has absorption bands of calcite, dolomite, quartz, and a clay
mineral in its spectrum. The ratio of calcite to dolomite in this
sample is about 3 to 1. In the “mahogany” oil shale it is about
1 to 2.
Absorption bands of carbonates, quartz, and clay min-
erals show up in varying amounts in all the shales. The band at
6.15 microns in these spectra is probably due to water.
minerals has not been possible because of a lack of spectra of pure
minerals. As a library of reference spectra is obtained and wave-
length assignments are checked by other laboratories, it will be-
come possible to identify the mineral constituents of a rock with
more certainty.
INORGANIC CHEMICALS

Assignment of all absorption bands in these spectra to specific The spectra of several inorganic chemicals were examined.

COMPOUND

FLINT CLAY

SOURCE AND PURITY

NAT'l bureau of
STANDARDS N0.97

STATE SOLID
TEMPERATURE 25-30*0
THICKNESS 0·3 mgm/em2
0 7

COMPOUND
PLASTIC CLAY

SOURCE AND PURITY

NAT'L BUREAU OF
STANDARDS NO 99

STATE SOLID
TEMPERATURE 25-30*0
THICKNESS 0 2 mgm/ cm2
VOLUME 2 2, NO. 12, DECEMBER 1950 1493

Six carbonates are shown in Figures 14 and 15. Calcium and
strontium carbonate have spectra characteristic of the carbonate
minerals. The strong band around 11 microns has been dis-
placed to longer wave lengths in the strontium salt. Strontium
carbonate also shows á pair of prominent absorption bands in the
13- to 15-micron range, where the other carbonates have only one.
The most striking differences in the carbonate spectra are be-
tween the basic and the anhydrous carbonates.
basic magnesium and zinc carbonates bear no resemblance to
those of magnesite and smithsonite, respectively. The former
are characterized by a double absorption band in the 6.5- to 7.5-
micron range, whereas only one band occurs in the anhydrous
salts. Spectra of the basic salts also have five or more prominent
bands in the 9- to 15-micron range except for lead carbonate,
whereas tne anhydrous salts have only two. Basic carbonates
The spectra of have strong bands around 3 microns, probably due to bonded OH.

3000 «000

COMPOUND

REEF
LIMESTONE
SOURCE AND PURITY

WISCONSIN

STATE SOLID
TEMPERATURE 25-30 C
THICKNESS i I rrgm/ cm2

COMPOUND

LIMY OIL
SHALE
SOURCE AND PURITY

UINTA BASIN
UTAH

STATE SO D
TEMPERATURE 25-30* C
THICKNESS 0 4 mgm / cm2

wave length in microns

WAVE NUMBERS IN CM''

5000 «000 5000 2500 2000 1500 |«00 1300 iZOO uOO

COMPOUND '
xr~
LIMY SHALE \ 1
/T _ __L_i_
u
'

00L6MITE
AND PURITY '
SOURCE

UINTA BASIN \ \ \ CALCiTE

1

UTAH 'OUARTZ

j
STATE SOLID
TEMPERATURE 25-30 C
THICKNESS i 4 mgm/ 11 CARBONATE

OUPRTzK
CARBONATE'

WAVE LENGTH IN M CRONS

_i_
¿0MP0UN0

MAHOGANY
SHALE
SOURCE ANO PURITY

UINTA BASIN
UTAH

STATE SOLID
TEMPERATURE 25-30 C
THICKNESS 0.3 mgm/cm2

WAVE LENGTH IN MICRONS

1494 ANALYTICAL CHEMISTRY

The spectrum of bismuth subcarbonate is shown in Figure .
Its absorption around 7 microns resolves into a strong and a weak
band. Its band in the 14- to 15-micron region is very weak com-
pared to the other carbonates.
The spectra of magnesium, calcium, and cupric oxalates are
shown in Figures 15 and 16. They have a strong band at about
6 microns which appears to be the 7-micron band of carbonates
displaced to a shorter wave length. They also have two bands
between 7 and 8 microns and a strong band between 12 and 13
microns. Spectral positions and intensities of these bands vary
for the different oxalates. Absorption bands of bonded OH show
up at 3 microns in all the oxalates.
The spectrum of magnesium oxide (Figure 16) has a sharp band
at 2.75 microns and a broad one through 3 microns, indicating the
presence of unbonded and bonded OH. In general, the over-all
spectrum is very much like those of the iron and titanium oxides

WAVE NUMBERS IN CM*1

COMPOUND
MAGNESIUM
CARBONATE
3MgC0j Mg(OH)2 3^0

SOURCE AND PURITY

MALUNCKRODT
REAGENT

STATE SOLID
TEMPERATURE 25-30*0
THICKNESS 0 4 mgm/cm

COMPOUND
CUPRIC
CARBONATE
CuCOj Cu(0H)$

SOURCE AND PURITY

BAKER'S
REAGENT

STATE SOLID
TEMPERATURE 25-30 C
THICKNESS O.Bmgnvem2
VOLUME 2 2, NO. 12, DECEMBER 1950
in having a few very broad absorption bands. Spectra of addi-
tional inorganic chemicals are shown in Figures 16 and 17. The
strongest absorption bands of calcium phosphate occur at about
8.9, 9.4, and 11.1 microns. Several bands also appear in the
3- to 7.5-micron range. The spectrum of barium sulfate is
similar, but not identical to that of the mineral barite.
The powder film technique also can be used to obtain the
spectra of inorganic-organic salts such as barium diphenylamine-p-
1495
sulfonate (Figure 17). The spectra of amorphous substances
containing silicon-oxygen linkages such as silica gel and a
borosilicate glass (Pyrex glass No. 7740) are shown in Figure 17.
Both of these are similar to the spectra of opal and diatomaceous
earth in the shape of their bands at 9 and 12.5 microns. They
differ in having a more prominent band in the 10- to 11-micron
range. The spectrum of the borosilicate glass also differs in
having a strong band at 7.2 microns.
W6VC NUMBERS IN CM*1
1496 ANALYTICAL CHEMISTRY

A few empirical relationships were noted between spectra and
structure during the course of this work. In the spectra of the
carbonates, for example, the spectral position for the strong band
at about 11 microns is affected by the atomic weight of the cation.
It is displaced to successively longer wave lengths for the series
position on semilog paper, the data approximate a straight line.
Iron and manganese, which are of almost equivalent weight, have
this band in the same position.
ACKNOWLEDGMENT

magnesium (calcium, magnesium), calcium, iron, strontium, The authors are indebted to Parke A. Dickey for many valuable
bismuth, which is a series of increasing atomic weight. When suggestions during the course of this work, and to D. C. Bauman
the atomic weights for several cations are plotted against spectral for assistance in the experimental work. They also wish to thank

COMPOUND
CUPRIC
OXALATE
CuC204 ¿h20
SOURCE AND PURITY

SYNTHESIZED

STATE SOLD
TEMPERATURE 25-30*0
THICKNESS 08 mgm/cm2

COMPOUND
MAGNESIUM
OXIDE

SOURCE AND PURITY

MALLINCKRODT
REAGENT

STATE SOLID
TEMPERATURE 25-30 C
THICKNESS 0.4 mgm/err.2

COMPOUND
CALCIUM
PHOSPHATE

SOURCE AND PURITY

MALLINCKRODT
REAGENT

STATE SOLO
TEMPERATURE 25-30*0
THICKNESS 03 mgm/cm2
VOLUME 2 2, NO. 12, DECEMBER 1950 1497

the Carter Oil Company and the Standard Oil Development
Company for permission to publish this article.
LITERATURp; CITED
(1) Barnes, R. B., and Bonner, L. G.. Phys. Rev., 49, 732 (1936).
(2) Barnes. Gore, Stafford, and Williams, Ind. Eng. Chem., Anal.
Ed., 20, 402 (1948).
(3) Buswell and Dudenbostel, J. Am. Chem. Soc., 63, 2554 (1941).
(4) Gore, R. C., Anal. Chem., 22, 7 (1950).
(5) Heigl, J. J., Bell, M. F., and White, J. V., Ind. Eng. Chem.,
Anal. Ed., 19, 293 (1947).
(6) Henry, R. L., J. Optical Soc. Am., 38, 775 (1948).
(7) Keller, W. D., and Pickett, E. E., Am. J. Sci., 248, 264 (1950).
(8) Keller, W. D., and Pickett, E. E., Am. Mineral., 34, 855 (1949).
(9) Pfund. A. H., J. Optical Soc. Am., 23, 375 (1933).
(10) Ibid., 24, 143 (1934).
Received June 20, 1950.

compound
BARIUM
SULFATE
Bo
S04

SOURCE AND PURITY

MERCK
REAGENT

STATE SOuO
TEMPERATURE 25-30*0
THICKNESS 0.3 mgm/em2

WAVE LENGTH IN MICRONS

COMPOUND
BARIUM
DIPHENYLAMINE-p-
SULF0NATE
tC^. H4NHCeH^-4
-
SQj,8a
SOURCE AND PURITY

EASTMAN KODAK CO.

NO. 3104

STATE SOLID
TEMPERATURE 86-50 C
THICKNESS 0.4 mgm/em2

COMPOUND
BORO-SILICATE
GLASS
SOURCE AND PURITY

CORNING GLASS
WORKS

STATE SOLID
TEMPERATURE 26-50 C
THICKNESS 02 r*gr»./cm2