Designation: E1252 − 98 (Reapproved 2013)´1

Standard Practice for

General Techniques for Obtaining Infrared Spectra for
Qualitative Analysis1
This standard is issued under the fixed designation E1252; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.

ε1 NOTE—Warning statements were editorially corrected in January 2013.

1. Scope eters: Level Zero and Level One Tests

1.1 This practice covers the spectral range from 4000 to 50 E1642 Practice for General Techniques of Gas Chromatog-
cm−1 and includes techniques that are useful for qualitative raphy Infrared (GC/IR) Analysis
analysis of liquid-, solid-, and vapor-phase samples by infrared
3. Terminology
spectrometric techniques for which the amount of sample
available for analysis is not a limiting factor. These techniques 3.1 Definitions—For definitions of terms and symbols, refer
are often also useful for recording spectra at frequencies higher to Terminology E131.
than 4000 cm–1, in the near-infrared region.
4. Significance and Use
1.2 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this 4.1 Infrared spectroscopy is the most widely used technique
standard. for identifying organic and inorganic materials. This practice
describes methods for the proper application of infrared
1.3 This standard does not purport to address all of the spectroscopy.
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro- 5. General
priate safety and health practices and determine the applica-
5.1 Infrared (IR) qualitative analysis is carried out by
bility of regulatory limitations prior to use. Specific precau-
functional group identification (1-3)3 or by the comparison of

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tions are given in 6.5.1.
IR absorption spectra of unknown materials with those of
known reference materials, or both. These spectra are obtained
2. Referenced Documents
(4-8) through transmission, reflection, and other techniques,
2.1 ASTM Standards:2 such as photoacoustic spectroscopy (PAS). Spectra that are to
E131 Terminology Relating to Molecular Spectroscopy be compared should be obtained by the same technique and
E168 Practices for General Techniques of Infrared Quanti- under the same conditions. Users of published reference
tative Analysis spectra (9-16) should be aware that not all of these spectra are
E334 Practice for General Techniques of Infrared Micro- fully validated.
analysis 5.1.1 Instrumentation and accessories for infrared qualita-
E573 Practices for Internal Reflection Spectroscopy tive analysis are commercially available. The manufacturer’s
E932 Practice for Describing and Measuring Performance of manual should be followed to ensure optimum performance
Dispersive Infrared Spectrometers and safety.
E1421 Practice for Describing and Measuring Performance
5.2 Transmission spectra are obtained by placing a thin
of Fourier Transform Mid-Infrared (FT-MIR) Spectrom-
uniform layer of the sample perpendicular to the infrared
radiation path (see 9.5.1 for exception in order to eliminate
1
This practice is under the jurisdiction of ASTM Committee E13 on Molecular
interference fringes for thin films). The sample thickness must
Spectroscopy and Separation Science and is the direct responsibility of Subcom- be adequate to cause a decrease in the radiant power reaching
mittee E13.03 on Infrared and Near Infrared Spectroscopy. the detector at the absorption frequencies used in the analysis.
Current edition approved Jan. 1, 2013. Published January 2013. Originally For best results, the absorbance of the strongest bands should
approved in 1988. Last previous edition approved in 2007 as E1252 – 98 (2007).
DOI: 10.1520/E1252-98R13. be in the range from 1 to 2, and several bands should have
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
3
Standards volume information, refer to the standard’s Document Summary page on The boldface numbers in parentheses refer to a list of references at the end of
the ASTM website. this standard.

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 E1252 − 98 (2013)´1
absorbances of 0.6 units or more. There are exceptions to this 6.2 Capillary Films—Some liquids are too viscous to force
generalization based on the polarity of the molecules being into or out of a sealed cell. Examination of viscous liquids is
measured. For example, saturated hydrocarbons are nonpolar, accomplished by placing one or more drops in the center of a
and their identifying bands are not strong enough unless the flat window. Another flat window is then placed on top of the
C-H stretch at 2920 cm−1 is opaque and the deformation bands liquid. Pressure is applied in order to form a bubble-free
are in the range from 1.5 to 2.0 absorbance units (A) at 1440 capillary film covering an area large enough that the entire
to 1460 cm− 1. Spectra with different amounts of sample in the radiation beam passes through the film. The film thickness is
radiation path may be required to permit reliable analysis. If regulated by the amount of pressure applied and the viscosity
spectra are to be identified by computerized curve matching, of the liquid. A capillary film prepared in this manner has a
the absorbance of the strongest band should be less than 1; path length of about 0.01 mm. Volatile and highly fluid
otherwise, the effect of the instrument line shape function will materials may be lost from films prepared in this manner.
cause errors in the relative intensities of bands in spectra Demountable spacers can be used when a longer path length is
measured by dispersive spectrometers and by FT-IR spectrom- required to obtain a useful spectrum.
eters with certain apodization functions (specially triangular). 6.3 Internal Reflection Spectroscopy (IRS)—Viscous mate-
5.2.1 Techniques for obtaining transmission spectra vary rials can be smeared on one or both sides of an internal
with the sample state. Most samples, except free-standing thin reflection element (IRE). See Practices E573 for detailed
films, require IR transparent windows or matrices containing information on this technique.
the sample. Table 1 gives the properties of IR window
materials commonly employed. Selection of the window ma- 6.4 Disposable IR Cards4—These can be used to obtain
terial depends on the region of the IR spectrum to be used for spectra of non-volatile liquids. A very small drop, usually less
analysis, on the absence of interference with the sample, and than 10 µL of the liquid, is applied near the edge of the sample
adequate durability for the sample type. application area. If the sample does not easily flow across the
substrate surface, it may be spread using an appropriate tool.
5.3 Spectra obtained by reflection configurations commonly The sample needs to be applied in a thin layer, completely
exhibit both reflection and absorption characteristics and are covering an area large enough that the entire radiation beam
affected by the refractive indices of the media and the inter- passes through the sample. Note that any volatile components
faces. Spectral interpretation should be based on references run of a mixture will be lost in this process, which may make the
under the same experimental conditions. In particular, it should use of a disposable card a poor choice for such systems.
be realized that the spectrum of the surface of a sample
--`,,``,`````````,`,,``````,`,,-`-`,,`,,`,`,,`---

recorded by reflection will often differ from the spectrum of the 6.5 Solution Techniques:
bulk material as recorded by transmission spectroscopy. This is 6.5.1 Analysis of Materials Soluble in Infrared (IR) Trans-
because the chemistry of the surface often differs from that of parent Solvent: The Split Solvent Technique—Many solid and
the bulk, due to factors such as surface oxidation, migration of liquid samples are soluble in solvents that are transparent in
species from the bulk to the surface, and possible surface parts of the infrared spectral region. A list of solvents com-
contaminants. Some surface measurements are extremely sen- monly used in obtaining solution spectra is given in Table 2.
sitive to small amounts of materials present on a surface, The selection of solvents depends on several factors. The
whereas transmission spectroscopy is relatively insensitive to sample under examination must have adequate solubility, it
these minor components. must not react with the solvent, and the solvent must have
appropriate transmission regions that enable a useful spectrum
5.3.1 Reflection spectra are obtained in four configurations:
to be obtained. Combinations of solvents and window materi-
5.3.1.1 Specular reflectance (7.5),
als can often be selected that will allow a set of qualitative
5.3.1.2 Diffuse reflectance (7.6), solution-phase spectra to be obtained over the entire IR region.
5.3.1.3 Reflection-absorption (7.7), One example of this “split solvent” technique utilizes carbon
5.3.1.4 Internal reflection (7.9). Refer to Practices E573. tetrachloride (CCl4) and carbon disulfide (CS2) as solvents.
This technique is also called Attenuated Total Reflection (Warning—Both CCl4 and CS2 are toxic; keep in a well
(ATR), and ventilated hood. Use of these solvents is prohibited in many
5.3.1.5 Grazing angle reflectance. laboratories. In addition, CS2 is extremely flammable; keep
5.4 Photoacoustic IR spectra (11.2). away from ignition sources, even a steam bath. Moreover, CS2
is reactive (sometimes violently) with primary and secondary
5.5 Emission spectroscopy (11.4). aliphatic amines and must not be used as a solvent for these
TEST METHODS AND TECHNIQUES compounds. Similarly, CCl4 reacts with aluminum metal.
Depending on conditions such as temperature and particle size,
6. Analysis of Liquids the reaction has been lethally violent.)
6.5.1.1 Absorption by CCl4 is negligible in the region 4000
6.1 Fixed Cells—A wide range of liquid samples of low to to 1330 cm−1 and by CS2 in the region 1330 to 400 cm−1 in
moderate viscosity may be introduced into a sealed fixed-path cells of about 0.1 mm thickness. (Other solvents can be used.)
length cell. These are commercially available in a variety of
materials and path lengths. Typical path lengths are 0.01 to 0.2
mm. See 5.2 for considerations in selection of cell materials 4
The 3M disposable IR Card is manufactured by 3M Co., Disposable Products
and path lengths. Division.

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 E1252 − 98 (2013)´1
TABLE 1 Properties of Window Materials (in order of long-wavelength limit)
Chemical Cutoff RangeA Useful Transmission Range Water Refractive at
Window Material Remarks
Composition (µm) (cm−1) (µm) (cm−1) Solubility Index (;µm)
Glass SiO2+ ;2.5 ;4000 0.35–2 28 570–5000 insoluble 1.5–1.9 HF, alkaliB
Quartz (fused) SiO2 ;3.5 ;2857 0.2–4 50 000–2500 insoluble 1.43 4.5 HFB
SIlicon Nitrate Si3N4 0.3–4.5 33 000–2200
Silicon Carbide SiC 0.6–5 16 600–2000
Calcite CaCO3 0.2–5 50 000–2000 1.65, 1.5 0.589C Reacts with acids
Sapphire Al2O3 ;5.5 ;1818 0.2–5.5 50 000–1818 insoluble 1.77 0.55 Good strength, no cleavage
ALON 9AI2O3.5AIN 0.2–5.5 50 000–1700 1.8 0.6
Spinel MgAI2O4 0.2–6 50 000–1600 1.68 0.6
Strontium Titanate SrTiO3 0.39–6 25 000–1700 insoluble 2.4 HFB
Titanium Dioxide TiO2 0.42–6 24 000–1700 insoluble 2.6–2.9 H2SO4 and AlkaliB
Lithium Fluoride LiF ;6.0 ;1667 0.2–7 50 000–1429 slightly 1.39 1.39 AcidB
Zirconia ZrO2 0.36–7 27 000–1500 insoluable 2.15 HF and H2SO4B
Silicon Si 1.5–7 and 6600–1430 insoluble 3.4 11.0 Reacts with HF, alkaliD
10–FIR
Yttria Y2 0.25–8 40 000–1250 1.9 0.6
Yttria (La-doped) 0.09La2O3- 0.25–8 40 000–1250 1.8 0.6
0.91Y2O3
IRTRAN IE MgF2 2–8 5 000–1 250 slightly 1.3 6.7 HNO3B
Magnesium Oxide MgO 0.4–8 25 000–1300 insoluble 1.6 5 Acid and NH4 saltsB
Fluorite CaF2 ;8.0 ;1250 0.2–10 50 000–1000 insoluble 1.40 8.0 Amine salt and NH4 saltsB
Strontium Fluoride SrF2 0.13–11 77 000–909 slightly 1.4
IRTRAN IIIE CaF2 0.2–11 50 000–909 insoluble 1.34 5.0 Polycrystalline, no cleavage
Gallium Phosphide GaP 0.5–11 20 000–910
GaP
Lead Fluoride PbF2 0.3–12 3450–833 1.7 1
ServofraxF As2S3 1–12 10 000–833 insoluble 2.59 0.67 AlkaliB , softens at 195°C
slightly (hot)
Barium Fluoride BaF2 ;11 ;909 0.2–13 50 000–769 insoluble 1.45 5.1
AMTIR GeAsSe Glass 0.9–14 11 000–725 insoluble 2.5 10 Hard, brittle, attacked by alkali, good
ATR material
IRTRAN IIE ZnS 1–14 10 000–714 insoluble 2.24 5.5 Insoluble in most solvents
Indium Phosphide InP 1–14 10 000–725
Potassium Floride KF 0.16–15 62 500–666 soluble 1.3 0.3 Extremely deliquescent: not
recommended for routine use
Rock salt NaCl ;16 ;625 0.2–16 50 000–625 soluble 1.52 4.7 Soluble in glycerineG
Cadmium Sulfide CdS 0.5–16 20 000–625
Arsenic Triselenide As2Se3 0.8–17 12 500–600 slightly 2.8 Soluble in bases
Gallium Arsenide GaAs 1–17 10 000–600 insoluble 3.14 Slightly soluable in acids and bases
Germanium Ge 2–20 5 000–500 insoluble 4.0 13.0
Sylvite KCl 0.3–21 33 333–476 soluble 1.49 0.5 Soluble in glycerineG
IRTRAN IVE ZnSe 1–21 10 000–476 insoluble 2.5 1.0 Polycrystalline
Sodium Bromide NaBr 0.2–23 50 000–435 soluble 1.7 0.35
Sodium Iodide NaI 0.25–25 40 000–400 soluble 1.7 0.5
Silver Chloride AgCl ;22 ;455 0.6–25 16 6667–400 insoluble 2.0 3.8 Soft, darkens in lightH reacts with
metals
Potassium Bromide KBr ;25 ;400 0.2–27 50 000–370 soluble 1.53 8.6 Soluble in alcohol; fogs
Cadmium Telluride CdTe ;28 ;360 0.5–28 20 000–360 insoluble 2.67 10 Acids, HNO3B
Thallium Chloride 0.4–30 25 000–330 slightly 2.2 0.75 Toxic
TICI
KRS-6 Tl2CIBr 0.4–32 25 000–310 slightly 2.0–2.3 0.6–24 Toxic
Silver Bromide AgBr ;35 ;286 2–35 5 000–286 insoluble Soft, darkens in lightH , reacts with
metals
KRS-5 Tl2Brl ;40 ;250 0.7–38 14 286–263 slightly 2.38 4.0 Toxic, soft, soluble in alcohol, HNO3B
Cesium Bromide CsBr ;35 ;286 0.3–40 33 333–250 soluble 1.66 8.0 Soft, fogs, soluble alcohols
Potassium Iodide Kl 0.15–45 66 600–220
Thallium Bromide TIBr 0.45–45 22 000–220 slightly 2.3 0.6–25 Toxic
Cesium Iodide CsI ;52 ;192 0.3–50 33 330–220 soluble 1.74 8.0
Low-density (CH2CH2)n 20–220 500–45 insoluble 1.52 Very soft, organic liquids penetrate
polyethylene into polymer at ambient
temperature
Type 61I (CH2CH2)n 2–220 5 000–45 insoluble 1.52 Softens at 90°C
Type 62I (CF2CF2)nJ 2–220 5 000–45 insoluble 1.52 Useful to 200°C for short durations
J
Diamond 2-4 and 4500-2500 insoluble 2.4 10 K2Cr2O7 , H2SO4B
6-300 and 1667-33
A
Cutoff range is defined as the frequency range within which the transmittance of a 2 cm thick sample is greater than 0.5. FT-IR spectrometers may be able to work outside
this range.
B
Reacts with.
C
Ordinary and extraordinary rays.
D
Long wavelength limit depends on purity.
E
Trademark of Eastman Kodak Co.
F
Trademark of Servo Corp of America.
G
Window material will react with some inorganics (for example, SO2, HNO3, Pb(NO3)2).
H
These materials should be stored in the dark when not being used, and should not be placed in contact with metal frames.
I
Trademark of 3M.
J
Microporous polytetrafluoroethylene.
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 E1252 − 98 (2013)´1
TABLE 2 Commonly Employed IR Solvents
NOTE 1—Data obtained from IR spectra recorded in the Analytical Laboratories, Instrumental Group, Dow Chemical Company, Midland, MI. It is
recommended that the user of these tables record the spectrum for any solvent used in this application, since minor impurities may exhibit total absorption
in the region of interest when using relatively long path length cells.
CompoundA Structure Transmission Windows (cm−1 ) Path Length (mm)
carbon tetrachloride CCl4 5000-909, 666-36B 0.1
5000-1316 (absorption; 1666-1429) 0.1
5000-1666, 1499-1299 1.0
250-36 2.0
perchloroethylene C2Cl4 5000-1042B 0.1
5000-1408B 1.0
C
chloroform CHCl3 5000-3125, 2941-1299, 1136-870B 0.1
5000-3226, 2941-2532, 2222-1587B 1.0
chloroform-d1C CDCl3 5000-1000 cm−1B 0.1
5000-3225, 2778-2439, 2000-1538B 1.0
methylene chlorideC CH2Cl2 5000-1449, 1205-854, 625-200B 0.1
5000-3225, 2000-1538, 1111-1000, 625-500B 1.0
methylene chloride-d2 C CD2Cl2 5000-2500, 2000-1449, 1333-1177, 625-400B 0.5
bromoformC CHBr3 5000-3125, 2941-1250, 1111-800, 500-200 0.1
5000-3125, 2941-1408, 1111-1000 1.0
carbon disulfideD CS2 5000-2350, 2100-1600, 1400-410B 0.1
5000-2439, 2000-1666, 1.0
1351-909, 800-704 2.0
333-278, 238-36
acetonitrile CH3CN 5000-3225, 2778-2500, 2000-1587, 1299-1099, 1000-952, 0.1
909-787, 714-400B
5000-3333, 2000-1666, 1298-1141, 704-400B 1.0
acetonitrile-d3 CD3CN 5000-2380, 2000-1250, 800-714, 645-400B 0.1
5000-3448, 1852-1333, 645-400B 1.0
acetone (CH3)2CO 3448-3125, 2703-1852, 1053-952, 885-813, 746-588B 0.1
3448-3225, 870-813, 746-606, 357-200B 1.0
dimethyl sulfoxide (CH3)2SOE 5000-3333, 2703-1539, 1266-1149, 870-769, 645-200B 0.1
dimethyl-d6 sulfoxide 1,4-dioxane (CD3)2 SOE O(CH2- 5000-2381, 1961-1190, 606-400 0.1
CH2)2O
5000-3125, 2632-2040, 1923-1539, 800-666, 588-385 0.2
water H2O 5000-3846, 2857-1754, 1492-1000 0.025
heavy water D2O 5000-2778, 2000-1299 0.07
A
Recommended handling and storage is in ventilated hood for these organic solvents.
B
Some bands may be present, but their absorption is readily compensated by placing solvent in a variable path length cell in the reference beam, or by spectral subtraction
using computer techniques for full-range utility in the ranges given.
C
These compounds decompose and are often stabilized with a small amount of a compound such as ethanol. These compounds will react with amines.
D
Carbon disulfide will react with primary and secondary amines, sometimes violently. It is highly flammable and toxic.
E
Picks up H2O from the atmosphere if not well capped.

Solutions are prepared, usually in the 5 to 10 % weight/volume and CS2 solutions can be presented on the same hard copy over
range, and are shaken to ensure uniformity. The solutions are the region 4000 to 400 cm−1, or the presentation can be over
transferred by clean pipettes or by syringes that have been the 4000 to 1330 cm−1 region for the CCl4 solution and over
cleaned with solvent and dried to avoid cross-contamination the 1330 to 400 cm−1 region for the CS2 solution. The former
with a previous sample. If the spectrum of a 10 % solution choice is preferable because both band frequencies and band
contains many bands that are too deep and broad for accurate intensities are affected differently by the different solvents (due
frequency measurement, thinner cells or a more dilute solution to solvent-solute interaction).
must be used. 6.5.1.3 Split solution spectra are acceptable without solvent
NOTE 1—New syringes should be cleaned before use. Glass is the compensation, but recognition of the solvent bands that are
preferred material. If plastic is used as containers, lids, syringes, pipettes, present is mandatory when such spectra are compared with
and so forth, analytical blanks are necessary as a check against contami-
those recorded, either with solvent compensation or with
nation.
computer-assisted solvent subtraction. The IR spectrum of a
6.5.1.2 A spectrum obtained by the split-solvent technique solution over the entire 4000 to 400 cm−1 region can be useful,
in cells up to 0.5 to 1.0 mm-thickness, can be compensated for but it is not recommended for solutions of unknown materials
all solvent bands to yield the spectrum of only the sample because pertinent spectral data may be masked by solvent
itself. When a spectrometer that is capable of storing digital absorption. It is not possible to compensate fully absorbing
data is employed, the desired spectrum is obtained by a
bands such as CS2 (|; 1400 to 1600 cm− 1), CCl4 (| ;730 to
computer-assisted subtraction of the stored data for the solvent
800 cm−1), and CHCl3 (about 790 to 725 cm− 1) when using a
from the data for the solution. The user should refer to the
0.1-mm path length.
manufacturer’s manual for each instrumental system to per-
--`,,``,`````````,`,,``````,`,,-`-`,,`,,`,`,,`

form the computer-assisted manipulation of the spectral data NOTE 2—Attempted compensation of such totally absorbing bands can
necessary for hard copy presentation. Spectra from both CCl4 obscure sample bands.

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 E1252 − 98 (2013)´1
6.5.1.4 Often the same IR spectrum can be recorded using solvent because it is strongly absorbing throughout most of the
1 % solutions in 1.0-mm sealed cells as with 10 % solutions in useful mid-IR region and because it attacks many of the
0.1-mm cells. Interferences from the solvents, however, are window materials commonly used in transmission cells. When
larger with 1-mm cells (see Table 2). In cases where there is aqueous solutions are the most convenient form to handle
strong intermolecular association, such as intermolecular hy- particular materials, however, internal reflection cells with a
drogen bonding between solute molecules, the resulting IR short enough effective pathlength to permit recording of
spectra obtained with 1 % solutions will be different from the spectra from the near infrared to about 850 cm−1 (except
ones obtained with the 10 % solutions, because of the different between about 3800 and 2900 cm−1 and between about 1700
concentration of unassociated solute molecules, and in the and 1600 cm−1) can be used. These cells are commonly
different concentrations of intermolecularly hydrogen bonded cylindrical or rectangular. The water background can be
dimeric, trimeric, tetrameric, etc., solute molecules. subtracted in FT-IR and computer-assisted dispersive instru-
6.5.1.5 A distinct advantage is gained by recording IR ments. The spectrum of the solute obtained by this method will
spectra under a set of standard conditions, such as 5 to 10 % usually be quite different from the spectrum of the dry solute so
solutions in a 0.1-mm path length sealed cell. This practice that a library of aqueous solution spectra is ordinarily required
allows approximate quantitative analyses to be readily per- for the identification materials dissolved in water.
formed at a future date on samples where the utmost accuracy 6.5.4 Analysis of Water-Containing Solutions: Disposable
is not required. Moreover, for qualitative analyses, the spectra IR Card—This technique would be appropriate for samples
recorded will have comparable band intensities, assuming that such as latexes, mayonnaise, and other colloidal or emulsion
identical concentrations and path lengths are employed and that type samples. For many such samples there is also an organic
the instrumental parameter settings are identical. modifier present, such as a surfactant or organic liquid, which
6.5.1.6 Spectra that are to be used for computer searches facilitates wetting of the sample application area. In these cases
should be measured carefully. The search algorithms typically a drop of the sample is applied to the sample application area
normalize the strongest spectral feature to an arbitrary absor- as in 6.5.2.1, or it is smeared on as in 6.4.
bance level. Because of this, the spectrum of the solute should
be measured using a concentration/path length combination 7. Analysis of Solids
that results in the strongest solute band having an absorption 7.1 High-Pressure Diamond Anvil Cells—Samples can often
that does not exceed an absorbance of 1.0. be run in a high-pressure diamond anvil cell in accordance with
6.5.2 Analysis of Materials Soluble in Volatile Organic Practice E334.
Solvents: Use of Disposable IR Cards—Many solid samples
are soluble in volatile organic solvents which easily wet the 7.2 Alkali Halide Pressed Pellet Technique:
sample application area of an IR transparent window or a 7.2.1 This technique involves grinding a solid sample,
disposable IR card. Any solvent may be utilized that totally mixing it with an alkali halide powder, and pressing the
dissolves the component(s) of interest, is volatile enough to resulting mixture into a pellet or disk. Scattering of IR
quickly evaporate after sample application, is not reactive with radiation is reduced by having the sample particles embedded
the sample, and does not react with the sample application area. in a matrix of comparable refractive index. Alkali halides are
used because they have properties of cold flow and absence of
NOTE 3—A spectrum obtained using the disposable IR Card4 can be absorption in a wide spectral region. KBr is the most com-
compensated for the polymer bands to yield the spectrum of only the monly used, but KCl and CsI are also used for better matching
sample. When a spectrometer that is capable of storing digital data is
employed, the desired spectrum is obtained by a computer-assisted of refractive index, extended spectral range, or to avoid ion
subtraction of the stored data for the blank sample card from the data for exchange with another halide salt sample. The pellet technique
the applied sample. The user should refer to the manufacturer’s manual for is applicable to many organic materials, but there are limita-
each instrumental system to perform the computer-assisted manipulation tions associated with several chemical types of materials.
of the spectral data necessary for hard copy presentation. Amine salts, carboxylic acid salts, and some inorganic com-
6.5.2.1 A solution of the sample in appropriate solvent is pounds may react with alkali halides and produce a spectrum
prepared usually in the 10 % or greater weight/volume range, that does not represent the original sample.
and is shaken to ensure uniform solution. A drop of the solution 7.2.2 Because the spectrum obtained depends on particle
is applied to the center of the sample application area using a size, it is important to prepare both sample and reference
clean pipette, or syringe. If necessary, the sample can be spread materials in the same manner in order to ensure that the particle
out on the substrate surface using the blunt applicator tip such size distributions are reproduced. It should also be noted that
as from an disposable pipette. The solvent(s) used for sample the crystal structure of a compound may be changed by
dissolution are allowed to evaporate, leaving a deposit of the grinding or by the high pressure exerted in forming the pellet,
solid or liquid sample on the sample application area. In many causing an alteration of the IR spectrum.
cases, the solvents used will evaporate quickly. If evaporation 7.2.3 Both the sample and the alkali halide powder must be
time needs to be reduced, a gentle stream of clean dry air or dry in order to produce a clear pellet. Usually, the ratio of the
nitrogen can be blown across the surface or the card can be quantities of sample to KBr powder should be the range from
heated gently in an oven or with an infrared heat lamp for very 1/50 to 1/1000, depending on the type of sample. The solid
short duration. sample is ground using a mortar and pestle or a mechanical
6.5.3 Analysis of Aqueous Solutions: Internal Reflection vibrating mill until the particle size is smaller than the
Cells—Water is not generally recommended as an infrared wavelength of the IR radiation (for example, <2 µm) to
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 E1252 − 98 (2013)´1
minimize the scattering of IR radiation. The mortar and pestle TABLE 3 Mulling Agents
should be made of agate, alumina, or boron carbide to avoid NOTE 1—For the least amount of absorption from the mulling agent use
contamination of the sample during grinding. Adequate grind- Nujol™ in the region of approximately 1350 to 400 cm−1 and Fluorol-
ing will usually produce a glossy layer adhering to the mortar. ube™ in the region 4000 to 1350 cm−1 . It is recommended that IR
The KBr (or other alkali halide) is added and thoroughly mixed reference spectra be recorded of the mulling agents used in your
laboratory.
with the sample. The KBr sample mixture is then placed in a
Maximum Peaks of
special die and compressed to a small disk with a thickness of Mulling Agents
Absorption; cm−1
about 1 mm. The amount of force applied depends on the

--`,,``,`````````,`,,``````,`,,-`-`,,`,,`,`,,`---
Mineral Oil (NujolA ) 2952
diameter of the die. The best pellets are formed by evacuating 2921
the die filled with the KBr sample mixture before applying 2869
2952
pressure. This process minimizes the amount of water in the 1460
pressed pellet. 1378
7.2.4 For routine qualitative analysis of many compounds, 721
Fluorocarbon Oil (FluorolubeB ) 1275
adequate grinding and mixing can be realized by grinding the 1230
KBr-sample mixture in a vibrating mill for 30 to 60 s. 1196
7.2.5 Alkali halide powder may be used as a gentle abrasive 1141
1121
to collect samples of surface layers of materials such as paint. 1094
Pellets made from these powders have been used to study 1034
environmental exposure of surface finishes, and for forensic 961
896
comparison of automotive finishes. 830
7.2.6 A miniature press is often employed to press pellets as 735
small as 0.5-mm diameter. The quality of the spectrum ob- 650
594
tained is improved by placing the small pellet in a beam 543
condenser in the IR spectrometer sample compartment. This 519
results in an additional focusing of the IR beam, usually by a A
Formerly trademarked by Stanco Incorporated, New York, NY, expired 1996.
B
factor of 4 to 6 in the linear dimension. Trademark by Gabriel Performance Products, LLC, in Baton Rouge, LA.

7.3 Polymer Matrix Technique—Powdered low-density

polyethylene can be used as the matrix material in the region
500-50 cm−1. Because absorption bands in the far IR usually a thin film by gently rotating the top plate, with the exception
have low intensity, a relatively high sample-to-polyethylene that IR cards and LDPE windows do not require this step. At
powder ratio is required. The well-dispersed sample- this point, a properly prepared mull should be reasonably
polyethylene mixture is placed in a die and heated to 90°C. transparent to visible light (a frosty or cloudy appearance
This results in a pressed film with evenly dispersed sample. means that further grinding is needed).
This procedure is applicable only to compounds that are stable 7.4.3 For split mulls, two mortars and pestles are useful for
at 90°C. working with the two mulling agents. The difficult part of this
7.4 Mull Technique: process is adjusting the mull film thicknesses so that the band
7.4.1 This technique involves grinding a solid sample with absorbances in both spectral regions yield true relative values.
a small amount of a liquid known as a mulling agent. This is accomplished by selecting a sample band that is free
Fluorocarbon oil is used for the region 4000 to 1300 cm−1 and from interference in both mulling fluids and in adjusting the
mineral oil is used for the region 1300 to 50 cm−1. Split mulls film thicknesses so that the absorbances of this band are
using both liquids are necessary to obtain an optimal complete essentially identical in the spectra of the two mulls. The
spectrum. Qualitative spectra can be obtained using only one of adjustment of film thicknesses is simplified by the use of an
the mulling agents (usually mineral oil), provided that absorp- instrument (FT-IR or dispersive), capable of storing digital data
tion by the mulling agent used does not mask spectral regions and thus enabling the adjustment to be made by computer-
of analytical importance. assisted calculations based on a sample band that is free from
7.4.2 Approximately 3 to 10 mg of sample is placed in an interference. The user should refer to the manufacturer’s
agate, alumina, or boron carbide mortar, ground to a particle manual in order to perform the calculations for each type of
size less than 2-µm diameter, and spread uniformly over the system employed.
surface of the mortar. At this stage, the sample should have a 7.4.4 Another technique that has been used to prepare
glossy appearance. One to a few drops of the mulling fluid is high-quality mulls is to grind the sample and mulling agent
added, and vigorous grinding is continued until all the particles with a grinder having two motor-driven rotating ground-glass
are suspended in the mulling agent and the mixture is a paste plates. This method is useful for preparing mulls of many
of creamy consistency. This paste is then transferred with a organic materials. It is not recommended for hard materials,
clean rubber policeman onto a flat NaCl, KBr, or other plate since glass may be introduced into the sample as a contami-
(disposable IR cards are useful for the mid-IR to far IR, while nant. Grinding may also be done manually with large diameter
low-density polyethylene (LDPE) windows are useful below ground glass joints.
200 cm−1) and spread uniformly across the middle section of 7.5 Specular Reflection Spectroscopy—A flat surface will
the plate. A second flat plate is used to squeeze the paste into allow an incident beam to be reflected off the surface at an

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angle of reflection equal to the angle of incidence. The the surface contact by warming both the IRE and the material
reflectance spectrum measured includes information on the while in contact under pressure. However, this technique will
absorbing properties of the material, and often appears to be often ruin the IRE.
highly distorted. Application of the Kramers-Kronig transfor-
mation to the observed spectrum can be used to extract the 8. Analysis of Vapor-Phase Samples
normal absorption spectrum from this information (see Practice 8.1 Use of Simple Gas Cells:
E334). 8.1.1 Samples that are gases at ambient conditions of
7.6 Diffuse Reflection Spectroscopy: temperature and pressure, or even liquids that have a vapor
7.6.1 When used in conjunction with a Fourier Transform pressure as low as 0.1 torr (;13 Pa) at ambient temperature,
infrared spectrometer, this technique is commonly referred to are readily examined by IR. A spectrum satisfactory for routine
as DRIFT (Diffuse Reflection Infrared Fourier Transform) qualitative identification can be recorded of most gases by
spectroscopy. It has gained wide acceptance for analysis of a purging, in a hood, a small-volume cell (one having, for
range of materials, due to its simplicity and ease of sample example, 1 3-mm pathlength) with the sample gas to flush out
preparation. It is also preferred for samples that strongly reflect the air. The stopcocks are then closed. Longer pathlengths can
or scatter infrared energy. be used if the goal is to identify impurities in the gaseous
sample.
7.6.2 This technique is generally applicable to solid samples 8.1.2 A 5 or 10-cm glass cell equipped with windows of
that are ground (as in the preparation of an alkali halide pellet KBr, CsI, or other suitable material, is frequently used to
or a mull) and then mixed with KBr, KCl powder, or other record vapor-phase IR spectra. Several pressures may be
optical transparent powdered materials, or combination employed so that the shapes of both weak and strong bands can
thereof. Spectra below 400 cm−1 can be obtained using be observed. Band shapes and intensities in gas phase spectra
polyethylene powder. The mixture is loaded into a sample cup vary with both the total pressure and with the nature of the
that is then placed in a diffuse reflectance accessory. The diluent. It is a useful procedure, therefore, to obtain gas spectra
resulting spectra can differ significantly from those obtained by adjusted to some constant dilution with an inert IR transparent
transmission spectroscopy. For details and applications, see gas, such as nitrogen, for example, to a total pressure 600 torr.
(17-29). This aspect is particularly important if quantitative analyses are
7.6.3 Another method utilized to obtain solid samples for contemplated. Moreover, infrared spectra of strongly intermo-
use in DRIFT spectroscopy relies on an abrasive pad sampler, lecular hydrogen bonded molecules, such as carboxylic acids
made of silicon carbide, diamond, or other hard substance. (monomer-dimer) are especially affected by both pressure and
These disposable sample holders, available from a number of temperature.
sources, offer a simple means of sampling hard inorganics (for 8.1.3 Certain gases such as NO2 or SO2 react with the alkali
example, minerals) and organics (for example, thermoset halide windows, causing the formation of ionic species on the
resins). window surface. In this case, ZnSe or another substance which
7.7 Reflection-Absorption Spectroscopy—This technique is is not attacked by SO2 or NO2, should be used as window
used to obtain absorption spectra of insoluble coatings on material if the artifact-bands interfere excessively with the
reflecting substrates, such as smooth metallic surfaces. Spectra sample spectrum.
of coatings as thin as 1 µm can be obtained using a spectral 8.1.4 A 10-cm glass cell equipped with high-density poly-
reflectance attachment. (For details and applications, see (30- ethylene windows several millimetres thick can be used to
33).) record vapor-phase IR spectra in the region 500 to 50 cm−1 and
below.
7.8 Total Reflectance—Accessories are available that can
8.2 Use of Multipass Gas Cells:
measure both diffuse and specular components of the infrared
8.2.1 Long path length cells are required in order to record
reflectance spectrum. One special type of accessory is an
IR spectra of chemicals with low vapor pressure at ambient
integrating sphere, which captures reflected energy from all
temperatures. The same type of cell is employed in order to
angles, and often incorporates a purpose-built detector having
detect parts per million (ppm) levels of contaminants (impuri-
a large surface area. Under certain conditions, the specular
ties) in air or other gas. In the latter case, the H2O and CO2
--`,,``,`````````,`,,``````,`,,-`-`,,`,,`,`,,`---

component of the reflected energy can be reduced or even

present in air can be compensated by placing a comparable cell
removed before the energy reaches the detector. This type of
filled with ordinary air in the reference beam with the appro-
accessory if useful for measuring the total reflected energy
priate path length setting. For instruments capable of storing
from a sample, for examining samples (such as fabrics) that are
digital spectra, the same cell can be used to obtain the reference
not easily handled in any traditional manner.
air spectrum, and then this spectrum can be subtracted from the
7.9 Internal Reflection Spectroscopy—Bulk samples, in- sample spectrum. The usual path length employed in trace
cluding polymer films and liquids, can be analyzed by this analyses is ;20 m. A comparable path length setting is
technique if the surface is representative of the sample interior. required for chemicals with low vapor-pressure at ambient
For further information, see Practices E573. In the case of temperatures.
materials with hard surfaces where it may be difficult to get 8.2.2 A disadvantage of utilizing multipass cells is that the
good contact between the internal reflection element (IRE) and optics are in contact with the sample, and this can cause even
the sample using the IRS technique, it is possible to improve the gold-coated mirrors to deteriorate. Another disadvantage is

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that certain samples adhere to the large cell surface area, prepared. Silver bromide is less sensitive to strong visible or
causing a built-in memory when a different sample is intro- ultraviolet light than silver chloride (AgCl), but it will darken
duced into the cell. Extensive flushing with dry air or dry with time. The plates, therefore, should be stored in the dark
nitrogen with repeated cell evacuation is often necessary to when not in use. Only clear transparent AgBr plates should be
clean out the cell. Gentle heating with a heat lamp may also aid used for these measurements. Moreover, flat AgBr or AgCl
in reducing memory effects. In addition, the cell windows often plates should be 2 mm thick in order to eliminate interference
become coated with materials used to seal the cell window. fringes. The plates are readily cleaned by redissolving the cast
Ignoring these factors will result in obtaining IR spectra of the film in water.
sample plus contaminants from previous runs.
9.1.2 Films of water-soluble polymers cast on glass are
8.3 Use of Heated Gas Cells: readily examined by peeling off the film from the glass. Water
8.3.1 Vapor-phase IR spectra of solids and high boiling soluble polymers that do not form good films may be examined
liquids can be examined at an elevated temperature (200°C and using the alkali halide pellet technique (7.2.1).
above), using a relatively short path length vapor cell (0.1 to
9.1.3 Also see Practices E573 for details of the internal
0.75 m). The IR spectra recorded in this manner are especially

--`,,``,`````````,`,,``````,`,,-`-`,,`,,`,`,,`---
reflection spectroscopy (IRS) technique.
useful in the identification of GC-IR fractions of unknown
materials, since most GC-IR spectra are conveniently recorded 9.2 Polymers Soluble in Organic Solvents—A variety of
at high temperatures (see Practices E1642). solvents such as 1,2-dichlorobenzene, toluene, methyl ethyl
8.3.2 Recording IR spectra at high temperature, employing ketone, dimethylformamide, tetrahydrofuran (Note 3) can be
a dispersive instrument, requires that the IR radiation from the used to cast polymeric films on an alkali halide plate. The
source be chopped ahead of the sample to avoid recording IR solvent is removed by heating in a nitrogen atmosphere using
radiation emitted from the hot sample. Unless using very high an IR heat lamp or in an evacuated oven. The ideal cast
temperatures, this is not usually a problem when employing an uniform film is ;0.01 to 0.05 mm thick and has no spectral
FT-IR spectrometer, provided that the sample is held between evidence of solvent. In most cases, solutions of the polymer
the interferometer (which is a wavenumber-selective chopper) can be obtained only by heating; this necessitates preheating
and the detector. the KBr or NaCl plate before the polymer solution is applied to
9. Analysis of Polymers prevent fracturing the plate. A CsI plate allows a wider
NOTE 4—See Refs (8) and (34) for general methods of IR analysis of frequency range to be recorded, and it is not as sensitive to
polymers. See Refs (10-14) for compilations of polymer spectra. thermal shock. Table 4 gives a list of solvents used to dissolve
9.1 Polymers Soluble in Water: different classes of polymers. Films can also be cast from an
9.1.1 Film forming polymers which are soluble in water are organic solvent on an internal reflection element (IRE) and
readily examined in the region 4000-400 cm−1 as cast films on qualitative spectra recorded using the IRS technique. Further,
flat silver bromide (AgBr) plates (see Table 1 for other window for those materials soluble in solvents which may easily be
materials). In order to cast a film with a uniform thickness of volatilized at temperatures below 75°C, the disposable IR card
;0.01 mm, a suitably dilute water solution of the polymer is method described in 6.5.4 may be used.

TABLE 4 Solvents Used in Casting Polymer Films

Class Generic Name SolventsA

Acetate Resins Polyformaldehyde 1,2-dichlorobenzene
Acrylics ABS terpolymer 1,2-dichlorobenzene
Acrylic acid-ethylene copolymer 1,2-dichlorobenzene
Acrylonitrile-butadiene copolymer 1,2-dichlorobenzene
Polyacrylamide water
Polyethylacrylate 1,2-dichlorobenzene
Ethylacrylate 1,2-dichlorobenzene
Ethylacrylate-ethylene copolymer 1,2-dichlorobenzene
Polymethylacrylate 1,2-dichlorobenzene
Polymethylmethacrylate acetone
Methylmethacrylate-styrene copolymer 1,2-dichlorobenzene
Polyacrylonitrile dimethyl sulfoxide or dimethylformamide
Polymethacrylamide water
Polysodium acrylate water
B
Amino Resins Melamine-formaldehyde
B
Urea-formaldehyde
Cellulosics Cellulose acetate acetone
Cellulose acetate butyrate 1,2-dichlorobenzene or acetone
Cellulose nitrate acetone
Cellulose propionate acetone
Ethyl cellulose ethylene dichloride
Hydroxyethyl cellulose water
Methyl cellulose water
Sodium carboxymethyl cellulose water
Coumarone and Terpene Resins Coumarone-indene resin polyterpene 1,2-dichlorobenzene 1,2-dichlorobenzene
B
Epoxies Polymers based on the diglycidyl ether of bisphenol-A (cured)

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 E1252 − 98 (2013)´1
TABLE 4 Continued

Class Generic Name SolventsA

(uncured) 1,2-dichlorobenzene
Epoxylated phenolformaldehyde acetone
Ethylene Polyethylene 1,2-dichlorobenzene
Polymers Ethylene-propylene copolymer 1,2-dichlorobenzene
Polyethylene oxideC acetone or CCl4 orB
B
Fluorocarbons Polytetrafluoroethylene
Polyvinylfluoride dimethylformamide
Furane Resins Furfuraldehyde-phenol resins methylene chloride or methanol
Isoprene Polyisoprene toluene or 1,2-dichlorobenzene
Natural Resins Accroides acetone
Asphalt methylene chloride
Copals-fused congo 1,2-dichlorobenzene
Copals-gum congo dimethylformamide
Copals-kauri 1,2-dichlorobenzene
Copals-manilas dimethylformamide
East indias-batu 1,2-dichlorobenzene
East indias-pale 1,2-dichlorobenzene
Elemi 1,2-dichlorobenzene
Shellac dimethylformamide
Vinol acetone
Nylons Nylon 6 dimethylformamide
Nylon 6/10 dimethylformamide
Nylon 7 dimethylformamide
Nylon 11 dimethylformamide
Phenolics Phenol-formaldehyde tetrahydrofuran
Resorcinol-formaldehyde tetrahydrofuran
Polycarbonates Bis-phenol A carbonate polymer methylene chloride tetrahydrofuran 1,2-
dichlorobenzene
Polyesters Polyethyleneterephthalate 1,2-dichlorobenzene
Polybutylene Polyisobutylene 1,2-dichlorobenzene
Propylene Polymers Polypropylene 1,2-dichlorobenzene
Polypropylene oxide 1,2-dichlorobenzene
B
Protein Casein
B
Plastics Zein
Styrene Polymers Polystyrene 1,2-dichlorobenzene
Most styrene copolymers 1,2-dichlorobenzene
Polysulfones tetrahydrofuran
Polyurethanes Cured Hot DMSOB
Uncured tetrahydrofuran DMSO dimethylformamide
Thiokol Alkyl sulfide, disulfide alkyl ether copolymers 1,2-dichlorobenzene
Vinyl Polymers Polyvinyl acetal 1,2-dichlorobenzene

--`,,``,`````````,`,,``````,`,,-`-`,,`,,`,`,,`---
Polyvinyl acetate acetone
Polyvinyl alcohol water
Polyvinyl alcohol-acetate water
Polyvinyl ethyl ether 1,2-dichlorobenzene
Polyvinyl butyral dimethylformamide
Polyvinyl chloride 1,2-dichlorobenzene
Polyvinyl chloride-acetate 1,2-dichlorobenzene
Polyvinyl chloride-methyl acrylate copolymer 1,2-dichlorobenzene
Polyvinyl formal acetone or ethylene dichloride
Polyvinyl propionate 1,2-dichlorobenzene
Polyvinyl pyrolidone water
Poly N-vinyl carbazole dimethylformamide
Polyvinyl cyclohexane 1,2-dichlorobenzene
Vinylidene Copolymers Vinylidene chloride-acrylonitrile 1,2-dichlorobenzene dimethylformamide
Vinylidene chloride-butyl acrylate copolymer 1,2-dichlorobenzene
Vinylidene chloride-ethyl acrylate copolymer 1,2-dichlorobenzene
Vinylidene chloride-vinyl chloride copolymer 1,2-dichlorobenzene
Xylene Poly-p-xylene 1,2-dichlorobenzene
A
Other similar type solvents may be used.
B
For heavily crosslinked or insoluble polyurethane, run as pellets on split mulls or as a film if soluble in DMSO.
C
Solubility depends upon molecular weight.

NOTE 5—Tetrahydrofuran (THF) is used to dissolve certain classes of the inhibitor in the cast polymer film.
polymers. It is mandatory that either fresh or inhibited THF be employed.
Fresh THF slowly forms peroxides after the bottle has been opened. 9.3 Latex Suspensions (in Water)—Suitable films can be
Violent explosions can occur when THF containing THF peroxide is prepared from latex suspensions (in water) by casting a thin
heated to dissolve the sample. Inhibited THF will exhibit absorption from film (;0.01 mm) on glass, drying, and then removing the dried

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film from the glass and stretching it over a rigid frame. Even 10.1.4 Extractable Materials—One method of identifying
though these materials are not water soluble, the method materials dissolved in water is the extraction of a suitable
presented in 9.1 for water-soluble polymers is often used as an volume of solution with appropriate solvent (10 mL of solution
alternate method for casting a thin film on a AgBr or AgCl to 1 mL of extractant). The nonaqueous (bottom) layer is
plate. (See 9.5.2 for methods to eliminate interference fringes.) separated and salted with NaCl powder to remove water. The
solution is then placed in a 0.1 or 10-mm KBr sealed cell or
9.4 Insoluble Cross-Linked Polymers—Insoluble cross-
applied to a disposable IR card as described in 6.2.
linked polymers that cannot be pressed into a thin film can be
examined by the KBr pressed pellet or the split mull technique. 10.2 Gas Chromatographic Effluents—On-Line Method
Some rubbery polymers can be ground by cooling the polymer (GC/FT-IR)—The use of a Fourier transform spectrometer
with liquid nitrogen or solid carbon dioxide. Other techniques makes possible the obtaining of the vapor-phase absorption
that may be applicable are IRS (see Practices E573), PAS (see spectra of substances as they are being eluted from a gas
11.2), diffuse reflection, and pyrolysis (see 11.3). chromatograph. See Practice E1421 for details of this tech-
9.5 Hot-Pressed or Rolled Polymeric Films: nique.
9.5.1 Hot-pressed films are prepared by placing the polymer 10.3 Liquid Chromatographic Eluents (LC/IR)—The eluent
between sheets of aluminum foil and pressing at a temperature stream from a liquid chromatograh can be analyzed using
above the softening point. Hot-pressed or rolled films can be infrared spectroscopy. See Practice E334 for experimental
examined by mounting the film flat over a rigid frame. Such techniques.
films often give rise to interference fringes superimposed on
the spectrum of the polymer. Because the spacing of these 11. Special Types of Analysis
fringes depends on the thickness and refractive index of the 11.1 Temperature Effects on Materials: (See also emission
film, this spacing can be used to determine the film thickness if spectroscopy, 11.4).
the refractive index is known. When the fringes complicate the
11.1.1 The IR spectra of a substance obtained over a range
interpretation of the polymer spectrum, they can often be
of temperatures are helpful in the elucidation of molecular
reduced or eliminated by roughening the surface of the film;
structure. In these variable temperature studies, it is necessary
however, this results in some scattering of the IR radiation.
to employ a spectrometer that does not modulate the IR
Another method is to coat the film surface with a thin layer of
radiation emitted from the sample. (This is not usually a
mineral oil or fluorocarbon oil, depending on the frequency
problem when using a Fourier transform spectrometer.) A
range of interest (35). Another method is to place the film at
suitable accessory that can alter the temperature of the sample
Brewster’s angle to the radiation beam using parallel polariza-
will be necessary.
tion (5).
11.1.2 This technique can be used to obtain the IR spectra of
9.5.2 Interference fringes can be also removed from spectra
synthetic polymers and biomembranes in both their crystal and
recorded using FT-IR by modification of the raw interferogram
amorphous states, and in some cases to determine the changes
(36). Fringes arise from the presence of a weak secondary (and
in intermolecular association occurring between polymer
sometimes higher order) centerburst, superimposed on the
chains that affect their physical properties (37 and 38).
interferogram. Removal of this extraneous centerburst by
Changes into other crystalline solid forms with change in
generating a straight line in this region of the interferogram
temperature and changes from liquid to solid state amorphous
results in removal or reduction of the fringes from the
or crystalline forms can also be studied.
spectrum, but at the cost of generating a few weak extraneous
features in the spectrum. 11.1.3 Variable temperature experiments are important in
determining whether certain band pairs are the result of the
10. Analysis of Other Types of Materials presence of rotational isomers in either the vapor, liquid, or
solution phases, or in complete vibrational assignments in
10.1 Materials Soluble in Water: determining whether one or more bands in the spectrum is (are)
10.1.1 Substances dissolved in water can sometimes be suspected of being a hot band(s) (the band will increase in
identified directly by obtaining the spectrum of a film of the intensity with increased temperature). These experiments also
water solution between AgCl or AgBr plates or in a fixed path help to differentiate between band pairs resulting from Fermi
length cell with CaF2 or BaF2 windows. Absorption by water, resonance and those resulting from rotational isomers, since
however, masks much of the useful region of the infrared the band intensity ratios for rotational isomers are temperature
spectrum, and separation of the solute may be necessary. dependent. The less stable rotational isomers will increase in
10.1.2 Use of IRS—The absorption spectra of aqueous concentration with increased temperature (39). In both quali-
solutions can be obtained by the use of IRS (see 7.9). tative and quantitative analysis, however, the control of tem-
10.1.3 Nonvolatile Solutes—The water solution is evapo- perature is essential, since both frequencies and band intensi-
rated to dryness, and the residue is examined using the pressed ties are affected by change in temperature on materials such as
pellet (see 7.2) or the split mull (see 7.3) technique. Inorganic carbon disulfide (40) and polystyrene (41).
compounds identified using this technique are usually 11.1.4 When performing variable temperature experiments,
carbonates, phosphates, or sulfates. Nonvolatile organics the heat present in the sample and the sampling accessory can
soluble in CCl4 and CS2 are then examined using the method cause problems as a result of emission of infrared energy inside
in 6.5.1. the spectrometer.
--`,,``,`````````,`,,``````,`,,-`-`,,`,,`,`,,`---

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11.1.4.1 In most FT-IR spectrometers, the sample location is pyrolyzates of intractable samples, such as insoluble thermoset
after the interferometer, and this emitted energy impinges on plastics and carbon-filled cross-linked elastomers. The col-
the detector as an unmodulated signal. This causes a DC offset lected pyrolyzate, however, may not represent all of the
to the signal (interferogram), and can be severe enough to components in the sample, and the sample may not yield the
swamp the detector response. In a noise-limited experiment, same spectrum in consecutive runs. Some components of a
such as GC/IR using a heated lightpipe, this becomes an blend or a copolymer may be missed entirely.
important consideration (see Practice E1642). 11.3.3 Pyrolysis is a technique-sensitive analytical method.
11.1.4.2 In addition, some of the emitted energy travels It is necessary, therefore, to standardize carefully in a highly
towards the interferometer, and a fraction is sent back along the repeatable system for consistent analysis. Consistency of the
sample beam after modulation by the interferometer. This can sample system necessarily means that samples are similar, and
cause spurious features to occur in the sample spectrum that similarity must even extend to the concentration of carbon
because the energy is out-of-phase with the normal source. In filler, the inorganic filler, or type of inorganic filler, or
general, this effect is a weak one, but can be a significant combination thereof.
problem when studying gases at high temperature, since the
11.3.4 Pyrolysis units for maximum utility in the identifica-
cell windows become a bright source, and the rotational spectra
tion of polymeric compositions should be evacuable, able to
of the gas may contain sharp absorption lines that are sensitive
control temperature and time, and provide for collection of
to phase. In this case some bands may appear as derivative of
both vapor-phase pyrolyzate and condensed pyrolyzate. Py-
negative features.
rolysis units that fit these requirements can be purchased from
11.1.4.3 When using certain other instrument designs, the
manufacturers. Useful information for utilizing the pyrolysis
sample location can be before the interferometer. In this case
technique are given (47-57).
the sample/cell emissions are modulated by the interferometer
along with the source signal. 11.4 Emission Spectroscopy (58):
11.2 Use of Photoacoustic Spectroscopy: 11.4.1 Some spectrometers can be modified, using accesso-
11.2.1 This method requires an IR system equipped with a ries supplied commercially, to measure infrared spectra of
photoacoustic detector. It is useful for the study of materials in samples by emission spectroscopy. In this case, the normal
any physical state. The modulated IR radiation absorbed by the infrared emitting source is either removed or shielded. Optics
sample is converted to heat waves within the sample. These are then inserted to bring energy emitted by the sample into the
heat waves are transduced to acoustic waves at the gas-solid or interferometer instead. The normal instrument functions then
gas-liquid interface, or in the gas itself. The acoustic frequen- are used to record a single beam spectrum of the emitted signal.
cies are dependent upon the modulation frequency of the 11.4.2 The overall energy profile of the emitted signal is
instrument. The lower the modulation frequency, the greater comparable to the blackbody emission profile for the material,
the depth of penetration into the sample. which thus is dependent of the temperature of the sample. It is
11.2.2 Photoacoustic spectra can be obtained using two often useful to measure a ratioed emission spectrum, using the
different types of FT-IR spectrometers. The conventional, rapid spectrum of carbon black recorded under the same experimen-
scanning, spectrometer records a PA spectrum that has a depth tal conditions. Carbon black can be considered as being close
of signal penetration varying with the signal wavelength, as to a perfect black body emitter. It is also possible to generate
well as the modulation frequency of the interferometer. The use theoretical black body curves for comparison. The ratio of the
of a step-scanning interferometer, however, allows for the use theoretical to experimental blackbody curves shows the instru-
of a single modulation frequency, which results in the depth of ment absorption function being superimposed on the spectrum.
penetration being the same across the spectral range. Alteration 11.4.3 This technique is valuable when measuring the spec-
of this modulation frequency results in the monitoring of trum of samples at elevated temperatures, since the black body
differing penetration depth, which means that spectra can be response (in terms of both intensity and frequency of maximum
obtained successively deeper into a surface (depth profiling). intensity) increases with temperature. If the sample tempera-
11.2.3 The theoretical and experimental aspects of photoa- ture is high enough, above approximately 100°C, then a room
coustic spectroscopy have been discussed in detail (42-44), and temperature pyroelectric DTGS detector can be used to mea-
photoacoustic cells designed specifically for FT-IR application sure the signal. Below this temperature, however, a liquid-
are commercially available. Reviews of PAS/FT-IR of solids nitrogen cooled MCT detector is required, so that a suitable
and liquids have been written and are recommended reading temperature differential exists between the sample and the
for those interested in applying this technique (45,46). detector. Emission spectra of materials at room temperature
11.3 Pyrolysis: have been reported, but they are generally low in intensity, and
11.3.1 In this technique a sample is heated rapidly in a show very little energy above about 1500 cm–1.
special cell and the vapor-state decomposition products are 11.4.4 Emission spectroscopy can be used to obtain infrared
studied. The infrared spectrum obtained for the pyrolizate can spectra from thin films, coatings, and single fibers, as well as
be complex, since the vapors examined can include many from bulk materials. In the case of a coating on the surface of
fragments arising from breakdown of the original sample. a strong emitter, the observed spectrum is sometimes obtained
11.3.2 Application of the pyrolysis-infrared technique is by reabsorption of the blackbody energy being emitted by the
best regarded as a highly valuable, but last-resort technique. It bulk and will therefore show characteristics similar to a
is valuable because it can be used to obtain spectra of transmission spectrum.
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 E1252 − 98 (2013)´1
12. Keywords cells; infrared solution spectra; infrared spectroscopy; latex
12.1 alkali halide pressed pellets; attenuated total reflection suspensions; liquid phase spectra; photoacoustic spectroscopy;
spectroscopy; diffuse reflection spectroscopy; disposable IR polymer analysis; qualitative infrared analysis; solid phase
cards; DRIFT spectroscopy; emission spectroscopy; gas chro- spectra; split mull technique; vapor phase spectra
matographic effluent spectra; gas phase spectra; heated gas

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 E1252 − 98 (2013)´1
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