An American National Standard

Designation: D 5292 – 99

Standard Test Method for

Aromatic Carbon Contents of Hydrocarbon Oils by High
Resolution Nuclear Magnetic Resonance Spectroscopy1
This standard is issued under the fixed designation D 5292; 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 (e) indicates an editorial change since the last revision or reapproval.

1. Scope D 3238 Test Method for Calculation of Carbon Distribution

1.1 This test method covers the determination of the aro- and Structural Group Analysis of Petroleum Oils by the
matic hydrogen content (Procedures A and B) and aromatic n-d-M Method2
carbon content (Procedure C) of hydrocarbon oils using D 3701 Test Method for Hydrogen Content of Aviation
high-resolution nuclear magnetic resonance (NMR) spectrom- Turbine Fuels by Low Resolution Nuclear Magnetic Reso-
eters. Applicable samples include kerosenes, gas oils, mineral nance Spectrometry2
oils, lubricating oils, coal liquids, and other distillates that are D 4057 Practice for Manual Sampling of Petroleum and
completely soluble in chloroform at ambient temperature. For Petroleum Products2
pulse Fourier transform (FT) spectrometers, the detection limit E 386 Practice for Data Presentation Relating to High-
is typically 0.1 mol % aromatic hydrogen atoms and 0.5 mol % Resolution Nuclear Magnetic Resonance (NMR) Spectros-
aromatic carbon atoms. For continuous wave (CW) spectrom- copy3
eters, which are suitable for measuring aromatic hydrogen 2.2 Institute of Petroleum Methods:
contents only, the detection limit is considerably higher and IP Proposed Method BD Aromatic Hydrogen and Aromatic
typically 0.5 mol % aromatic hydrogen atoms. Carbon Contents of Hydrocarbon Oils by High Resolution
1.2 The reported units are mole percent aromatic hydrogen Nuclear Magnetic Resonance Spectroscopy4
atoms and mole percent aromatic carbon atoms. 3. Terminology
1.3 This test method is not applicable to samples containing
more than 1 mass % olefinic or phenolic compounds. 3.1 Definitions of Terms Specific to This Standard:
1.4 This test method does not cover the determination of the 3.1.1 aromatic carbon content—mole percent aromatic car-
percentage mass of aromatic compounds in oils since NMR bon atoms or the percentage of aromatic carbon of the total
signals from both saturated hydrocarbons and aliphatic sub- carbon:
stituents on aromatic ring compounds appear in the same aromatic carbon content 5 100
chemical shift region. For the determination of mass or volume 3 ~aromatic carbon atoms!/~total carbon atoms! (1)
percent aromatics in hydrocarbon oils, chromatographic, or 3.1.1.1 Discussion—For example, the aromatic carbon con-
mass spectrometry methods can be used. tent of toluene is 100 3 (6/7) or 85.7 mol % aromatic carbon
1.5 The values stated in SI units are to be regarded as the atoms.
standard. 3.1.2 aromatic hydrogen content—mole percent aromatic
1.6 This standard does not purport to address all of the hydrogen atoms or the percentage of aromatic hydrogen of the
safety problems, if any, associated with its use. It is the total hydrogen:
responsibility of the user of this standard to establish appro- aromatic hydrogen content 5 100
priate safety and health practices and determine the applica- 3 ~aromatic hydrogen atoms!/~total hydrogen atoms! (2)
bility of regulatory limitations prior to use. Specific precau-
tionary statements are given in 7.2 and 7.4. 3.1.2.1 Discussion—For example, the aromatic hydrogen
content of toluene is 100 3 (5/8) or 62.5 mol % aromatic
2. Referenced Documents hydrogen atoms.
2.1 ASTM Standards:

1
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products and Lubricantsand is the direct responsibility of Subcommittee
2
D02.04.0Fon Absorption Spectroscopic Methods. Annual Book of ASTM Standards, Vol 05.02.
3
Current edition approved Nov. 10, 1999. Published December 1999. Originally Annual Book of ASTM Standards, Vol 14.01.
4
published as D 5292 – 92. Last previous edition D 5292 – 93. Available from Institute of Petroleum Standards.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

1
 D 5292 – 99
3.2 Definitions of chemical shift (reported in parts per 5.3 The aromatic hydrogen and aromatic carbon contents
million (ppm)), internal reference, spectral width, and other determined by this test method can be used to evaluate changes
NMR terminology used in this test method can be found in in aromatic contents of hydrocarbon oils due to changes in
Practice E 386. processing conditions and to develop processing models in
3.3 Chloroform-d refers to chloroform solvent in which which the aromatic content of the hydrocarbon oil is a key
hydrogen is replaced by deuterium, the heavier isotope of processing indicator.
hydrogen. Chloroform-d is available from a variety of chemi-
cal and isotope suppliers. 6. Apparatus
6.1 High-Resolution Nuclear Magnetic Resonance
4. Summary of Test Method Spectrometer—A high-resolution continuous wave (CW) or
4.1 Hydrogen (1H) nuclear magnetic resonance (NMR) pulse Fourier transform (FT) NMR spectrometer capable of
spectra are obtained on solutions of the sample in being operated according to the conditions in Table 1 and Table
chloroform-d, using a CW or pulse FT high-resolution NMR
spectrometer. Carbon (13C) NMR spectra are obtained on
TABLE 1 Sample and Instrument Conditions for Continuous
solutions of the sample in chloroform-d using a pulse FT
Wave (CW) Measurements of1 H NMR Spectra
high-resolution NMR spectrometer. Tetramethylsilane is pre-
Solvent Chloroform-d
ferred as an internal reference in these solvents for assigning Sample concentration Up to 50 % v/v for distillable oils
the 0.0 parts per million (ppm) chemical shift position in Sample temperature Instrument ambient
both1H and13C NMR spectra. Internal lock None
Sample spinning rate As recommended by manufacturer, typically 20 Hz
4.2 The aromatic hydrogen content of the sample is mea- r-f Power level As recommended by instrument manufacturer
sured by comparing the integral for the aromatic hydrogen Signal to noise level A minimum of 5:1 for the maximum height of the
band in the 1 H NMR spectrum (5.0 to 10.0 ppm chemical shift smaller integrated absorption band
Chemical shift reference Preferably tetramethylsilane (0.0 ppm) at no
region) with the sum of the integrals for both the aliphatic greater than 1 vol % concentration
hydrogen band (−0.5 to 5.0 ppm region) and the aromatic Integration Integrate over the range − 0.5 to 5.0 ppm for the
hydrogen band (5.0 to 10.0 ppm region). aliphatic band and 5.0 to 10.0 ppm for the aromatic
band
4.3 The aromatic carbon content of the sample is measured
by comparing the integral for the aromatic carbon band in
the13C spectrum (100 to 170 ppm chemical shift region) with
the sum of the integrals for both the aliphatic carbon band (−10 2 and of producing peaks having widths less than the frequency
to 70 ppm region) and the aromatic carbon band (100 to 170 ranges of the majority of chemical shifts and coupling con-
ppm region). stants for the measured nucleus.
4.4 The integral of the aromatic hydrogen band must be 6.1.1 1H NMR spectra can be obtained using either CW or
corrected for the NMR absorption line due to residual chloro- pulse FT techniques but13C measurements require signal aver-
form (7.25 ppm chemical shift) in the predominantly aging and, therefore, currently require the pulse FT technique.
chloroform-d solvent. Low resolution NMR spectrometers and procedures are not
4.5 The integrals of the aliphatic hydrogen band and of the discussed in this test method (see Test Method D 3701 for an
aliphatic carbon band must be corrected for the NMR absorp- example of the use of low resolution NMR).
tion line due to the internal chemical shift reference tetrameth- 6.2 Tube Tubes—Usually a 5 or 10 mm outside diameter
ylsilane (0.0 ppm chemical shift in both1H and13C spectra). tube compatible with the configuration of the CW or pulse FT
spectrometer.
5. Significance and Use
5.1 Aromatic content is a key characteristic of hydrocarbon 7. Reagents and Materials
oils and can affect a variety of properties of the oil including its 7.1 Purity of Reagents—Reagent grade chemicals shall be
boiling range, viscosity, stability, and compatibility of the oil used in all tests. Unless otherwise indicated, it is intended that
with polymers. all reagents shall conform to the specifications of the Commit-
5.2 Existing methods for estimating aromatic contents use tee on Analytical Reagents of the American Chemical Society,
physical measurements, such as refractive index, density, and where such specifications are available.6 Other grades may be
number average molecular weight (see Test Method D 3238) or used, provided it is first ascertained that the reagent is of
infrared absorbance5 and often depend on the availability of sufficiently high purity to permit its use.
suitable standards. These NMR procedures do not require 7.2 Chloroform-d—For1H NMR, chloroform-d must con-
standards of known aromatic hydrogen or aromatic carbon tain less than 0.2 vol % residual chloroform. Care must be
contents and are applicable to a wide range of hydrocarbon oils taken not to contaminate the solvent with water and other
that are completely soluble in chloroform at ambient tempera- extraneous materials. (Warning: Health hazard. Highly toxic.
ture.

6
“Reagent Chemicals, American Chemical Society Specification.” American
5
Brandes, G., “The Structural Groups of Petroleum Fractions. I. Structural Chemical Society, Washington, D.C. For suggestions on the testing of reagents not
Group Analysis With the Help of Infrared Spectroscopy,” Brennstoff-Chemie Vol 37, listed by the American Chemical Society, see “Analar Standards for Laboratory
1956, p. 263. U.K. Chemicals,” BDH Ltd., Poole, Dorset, and the “United States Pharamacopeia.”

2
 D 5292 – 99
TABLE 2 Sample and Instrument Conditions for Pulse Fourier 7.4 Chromium (III) 2,4-Pentanedionate, relaxation reagent
Transform Measurements of1 H and13 C NMR Spectra for13C NMR spectra, typically 97 % grade.
Solvent:
1
H NMR Chloroform-d 8. Sampling
13
C NMR Chloroform-d
Sample concentration: 8.1 It is assumed that a representative sample acquired by a
1
H NMR Must be optimized for the instrument in use but procedure of Practice D 4057 or equivalent has been received
may be as high as 5 % v/v
13
C NMR Up to 50 % v/v for petroleum distillates and 30 % in the laboratory. If the test is not to be conducted immediately
v/v for coal liquids upon receipt of the sample, store in a cool place until needed.
Relaxation agent Chromium (III) 2,4-pentanedionate recommended 8.2 A minimum of approximately 10 mL of sample is
for13 C NMR solutions only. Where used, a 20 mM
solution (about 10 mg per mL) required for this test method. This should allow duplicate
Sample temperature Instrument ambient determinations, if desired.
Internal lock Deuterium (when chloroform-d is used for 1 H 8.3 All samples must be homogeneous prior to subsam-
NMR)
Sample spinning rate As recommended by manufacturer, typically 20 Hz pling. If any suspended particles present are attributable to
1
H Decoupling Only for13 C NMR. Broadband over the whole of foreign matter such as rust, filter a portion of the sample to be
the1 H frequency range, gated on during13 C data tested through a small plug of glass wool, contained in a clean
acquisition only with a decoupler rise time less
than 2 m/s small funnel, into a clean and dry vial or NMR sample tube
Pulse flip angle Approximately 30° containing chloroform-d.
Sequence delay time:
1
8.4 If the sample contains waxy materials, heat the sample
H NMR > 10 s
13
C NMR > 3 s with and> 60 s without relaxation in the container to approximately 60°C and mix with a
agent high-shear mixer prior to sampling. It may be necessary to
Memory size for Choose to give a minimum digitizing rate of 0.5
acquisition: Hz/point for1 H and 1.2 Hz/point for13 C NMR. If
transfer a portion of the sample to an NMR tube containing
necessary, increase memory size and zero fill chloroform-d by means of a pipet which has been heated to
Spectral width:
1
approximately 60°C to maintain the homogeneity of the
H NMR At least 15 ppm in frequency and centered, as
close as possible, to the 5 ppm chemical shift
sample.
value 8.5 For a valid test result, samples must be completely
13
C NMR At least 250 ppm in frequency and centered, as soluble in chloroform-d. Check to ensure that the final solution
close as possible, to the 100 ppm chemical shift
value
is homogeneous and free of undissolved particles.
Filter bandwidth Set to be equal to or greater than the spectral
width and as permitted by the instrument’s filter 9. Procedures
hardware
Exponential line Set at least equal to the digitizing rate 9.1 Three different procedures are described in this section
broadening for determining the aromatic hydrogen content, (see 9.6)
Signal to noise levels: Procedures A and B (see 9.7), and the aromatic carbon content
1
H NMR A minimum of 20:1 for the maximum height of the
smaller integrated band of hydrocarbon oils, Procedure C (see 9.8).
13
C NMR A minimum of 60:1 for the maximum height of the 9.2 The procedure selected by the analyst will depend on the
chloroform-d resonance appearing between 75 and available NMR instrumentation and on whether an aromatic
80 ppm on the chemical shift scale
Chemical shift reference: hydrogen or aromatic carbon content is of greater value in
1
H NMR Preferably tetramethylsilane (0.0 ppm) at no evaluating the characteristics of the hydrocarbon oil.
greater than 1 vol % concentration 9.3 Appendix X1 and Practice E 386 should be used in
13
C NMR Preferably tetramethylsilane (0.0 ppm) at no
greater than 1 vol % concentration. If this conjunction with the NMR spectrometer manufacturer’s in-
reference is not used, the central peak of structions in order to ensure optimum performance of the NMR
chloroform-d is set to 77.0 ppm
instrument in the application of these procedures.
Integration:
1
H NMR Integrate over the range − 0.5 to 5.0 ppm for the 9.4 If tetramethylsilane is used as an internal chemical shift
aliphatic band and 5.0 to 10.0 ppm for the aromatic standard, prepare a 1 % v/v TMS in solvent solution by adding
band
13
C NMR Integrate over the range − 10 to 70 ppm for the
tetramethylsilane to chloroform-d solvent. Since TMS is very
aliphatic band and 100 to 170 ppm for the aromatic volatile, this solution should be refrigerated or replaced if the
band characteristic absorption due to TMS is no longer evident in
the1H or13C NMR spectrum.
9.5 If it is inconvenient to prepare the test solution directly
in the NMR sample tube as suggested in the following
Cancer suspect agent. Can be fatal when swallowed and procedures, the test solution can be prepared in a small vial and
harmful when inhaled. Can produce toxic vapors when transferred into the NMR sample tube after solvent addition
burned.) and sample dissolution. Care should be exercised to ensure that
7.3 Tetramethylsilane, American Chemical Society (ACS) the final solution concentrations are not different from those
reagent internal chemical shift reference for1H and 13C NMR indicated in the procedures and that no contamination occurs
spectra. (Warning: Flammable liquid.) during the transfer process.

3
 D 5292 – 99
9.6 Procedure A—1H NMR Measurements Using a Con-
tinuous Wave (CW) NMR Spectrometer:
9.6.1 Pipette a homogeneous sample of the hydrocarbon oil
into an NMR sample tube compatible with the configuration of
the CW spectrometer, usually a 5 mm outside diameter capped
NMR tube.
9.6.2 Add chloroform-d to the NMR sample tube to gener-
ate a final solution consisting of up to 50 % v/v hydrocarbon oil
in solvent. The concentration of hydrocarbon oil in solvent
should be optimized for the spectrometer in use but can be as
high as the indicated value. Check to ensure that the final
solution is homogeneous and free of undissolved particles.
9.6.3 Using the instrumental conditions indicated in Table 1,
acquire and plot the CW1H NMR spectrum. If tetramethylsi-
lane has been used as an internal standard, assign this absorp-
FIG. 1 80 MHz1 H NMR Spectrum of a Gas Oil
tion a chemical shift value of 0.0 ppm.
9.6.4 Integrate the NMR spectrum over two chemical shift
regions, from 5.0 to 10.0 ppm (Region A) and from − 0.5 to 5.0
apparent or if carbon tetrachloride was used as solvent, make
ppm (Region B). See Appendix X1 for recommendations on
no correction to the Region A integral value.
the integration procedure.
9.7.7 If tetramethylsilane was used as an internal chemical
9.6.5 Subtract the portion of integral contributed by the
shift reference, subtract the portion of integral contributed by
NMR absorption line of residual chloroform solvent (7.25 ppm
the NMR absorption line of TMS (0.0 ppm in the1H NMR
in the1H NMR spectrum) from the total integral value for
spectrum) from the total integral value for Region B.
Region A. If a residual chloroform absorption line is not
9.7.8 Calculate the aromatic hydrogen content using the
apparent, make no correction to the Region A integral value.
corrected integral values for Regions A and B and the instruc-
9.6.6 If tetramethylsilane was used as an internal chemical tions in 10.1 and 10.2.
shift reference, subtract the portion of integral contributed by 9.8 Procedure C—13C NMR Measurements Using a Pulse
the NMR absorption line of TMS (0.0 ppm in the1H NMR Fourier Transform (FT) NMR Spectrometer:
spectrum) from the total integral value for Region B. 9.8.1 Pipette a homogeneous sample of the hydrocarbon oil
9.6.7 Calculate the aromatic hydrogen content using the into an NMR sample tube compatible with the configuration of
corrected integral values for Regions A and B and the instruc- the pulse FT spectrometer, usually a 5 or 10 mm outside
tions in 10.1 and 10.2. diameter capped NMR tube.
9.7 Procedure B—1H NMR Measurements Using a Pulse 9.8.2 If a relaxation reagent is used, weigh 10 mg of
Fourier Transform (FT) NMR Spectrometer: chromium 2,4-pentanedionate per 1 mL of final solution
9.7.1 Pipette a homogeneous sample of the hydrocarbon oil volume directly into the tube or vial containing the hydrocar-
into an NMR sample tube compatible with the configuration of bon oil.
the pulse FT spectrometer, usually a 5 or 10 mm outside
diameter capped NMR tube. NOTE 1—A relaxation reagent is recommended but is not required for
this procedure (see X1.4.3). If relaxation reagent is not used, however,
9.7.2 Add chloroform-d to the NMR sample tube to gener- the“ sequence delay time” (see Practice E 386) instrumental setting must
ate a final solution consisting of up to 5 % v/v hydrocarbon oil be increased to a significantly longer time than that used when relaxation
in solvent. The concentration of hydrocarbon oil in solvent reagent is present. Failure to use the longer “sequence delay time” as
should be optimized for the spectrometer in use but can be as indicated in Table 2 will generate erroneous results.
high as the indicated value. Check to ensure that the final 9.8.3 Add chloroform-d to the NMR sample tube to gener-
solution is homogeneous and free of undissolved particles. ate a final solution consisting of up to 50 % v/v for petroleum
9.7.3 Using the instrumental conditions indicated in Table 2, distillates in solvent and up to 30 % v/v for coal liquids in
acquire and plot the pulse FT1H NMR spectrum. If tetrameth- solvent. The concentrations of sample oil in solvent should be
ylsilane has been used as an internal standard, assign this optimized for the spectrometer in use but can be as high as the
absorption a chemical shift value of 0.0 ppm. indicated values. Check to ensure that the final solution is
9.7.4 Fig. 1 shows an acceptable pulse FT 1H NMR spec- homogeneous and free of undissolved particles.
trum of a gas oil test sample dissolved in chloroform-d. 9.8.4 Using the instrumental conditions indicated in Table 2,
9.7.5 Integrate the NMR spectrum over two chemical shift acquire and plot the pulse FT13C NMR spectrum. If tetram-
regions, from 5.0 to 10.0 ppm (Region A) and from −0.5 to 5.0 ethylsilane has been used as an internal standard, assign this
ppm (Region B). See Appendix X1 for recommendations on absorption a chemical shift value of 0.0 ppm.
the integration procedure. 9.8.5 Fig. 2 shows an acceptable pulse FT 13C NMR
9.7.6 Subtract the portion of integral contributed by the spectrum of a gas oil test sample dissolved in chloroform-d
NMR absorption line of residual chloroform solvent (7.25 ppm containing relaxation reagent.
in the 1 H NMR spectrum) from the total integral value for 9.8.6 Integrate the NMR spectrum over two chemical shift
Region A. If a residual chloroform absorption line is not regions, from 100 to 170 ppm (Region A) and from −10 to 70

4
 D 5292 – 99
12. Precision and Bias 7
12.1 The precision of this test method is dependent on the
aromatic content of the sample.
12.2 Precision—The precision of this test method as deter-
mined by the statistical examination of inter-laboratory test
results in the range 1 to 78 (aromatic hydrogen content) and 8
to 93 (aromatic carbon content) is as follows:
12.2.1 Repeatability—The difference between successive
results obtained by the same operator with the same apparatus
under constant operating conditions or identical test material
would, in the long run, in the normal and correct operation of
this test method, exceed the following values only in one case
in twenty:
(Aromatic Hydrogen) (Aromatic Carbon)
Content Content
(% H(Ar)) (% C(Ar))
0.32 X ⁄
12 0.59 X ⁄
13

Where X is the aromatic content determined from the NMR

FIG. 2 100 MHz13 C NMR Spectrum of a Gas Oil
measurement.
12.2.2 Reproducibility—The difference between two single
ppm (Region B). See Appendix X1 for recommendations on
and independent results obtained by different operators work-
the integration procedure.
ing in different laboratories on identical test materials would, in
9.8.7 If tetramethylsilane has been used as an internal
the long run, exceed the following values only in one case in
chemical shift reference, subtract the portion of integral con-
twenty:
tributed by the NMR absorption line of TMS (0.0 ppm in
(Aromatic Hydrogen) (Aromatic Carbon)
the13C NMR spectrum) from the total integral value for Region Content Content
B. (% H(Ar)) (% C(Ar))
9.8.8 Calculate the aromatic carbon content using the cor- 0.49 X ⁄
12 1.37 X ⁄
13

rected integral values for Regions A and B and the instructions Where X is the aromatic content determined from the NMR
in 10.1 and 10.3. measurement.
10. Calculation NOTE 2—Precision limits are based on a round-robin test program
10.1 Calculate the aromatic hydrogen or aromatic carbon carried out in 1985 and 1986 by the Institute of Petroleum (see IP Method
BD) and ASTM Committee D02.04F. Twelve cooperator laboratories
content as follows:
tested five oils, namely a lubricating oil, a gas oil, two aromatic distillates,
aromatic hydrogen or aromatic carbon content 5 @A/~A 1 B!# 3 100 % and an anthracene oil, whose aromatic hydrogen and carbon contents
(3) varied as described in 13.2.

where: 12.2.3 Bias—For pure hydrocarbons consisting of a single

A = integral value of the aromatic portion of the spectrum, compound or a known mixture of known aromatic compounds
and where the aromatic hydrogen or carbon content is either known
B = integral value of the aliphatic portion of the spectrum. from the compound molecular structure or can be calculated
from the known concentrations of different molecular struc-
10.2 For the aromatic hydrogen content: A is the corrected tures, no bias of the NMR method with respect to the known or
integral value for Region A (from 5.0 to 10.0 ppm) and B is the calculated value is observed. Since there is no accepted
corrected integral value for Region B (from − 0.5 to 5.0 ppm). reference method suitable for measuring bias on a hydrocarbon
The result is expressed as mole percent aromatic hydrogen oil composed of an unknown mixture of many aromatic
atoms or % H(Ar). compounds, the bias cannot be determined on such materials.
10.3 For the aromatic carbon content: A is the integral value
for Region A (from 100 to 170 ppm) and B is the corrected 13. Keywords
integral value for Region B (from − 10 to 70 ppm). The result 13.1 aromatic carbon content; aromatic hydrogen content;
is expressed as mole percent aromatic carbon atoms or % continuous wave; Fourier transform; hydrocarbon oils; NMR;
C(Ar). nuclear magnetic resonance spectroscopy
11. Report
11.1 Report the mole percent aromatic hydrogen atoms or 7
The results of the cooperative test program, from which these values have been
the mole percent aromatic carbon atoms to one decimal place. derived, are filed at ASTM Headquarters.

5
 D 5292 – 99
APPENDIX

(Nonmandatory Information)

X1. GENERAL OPERATING GUIDELINES FOR HIGH-RESOLUTION NMR SPECTROSCOPY

X1.1 The following guidelines are to be used in conjunc- time of data acquisition can be required to obtain
tion with the spectrometer manufacturer’s instructions for quantitative13C NMR results. Adding a suitable paramagnetic
optimum performance of the NMR spectrometer supplemented relaxation reagent, such as chromium (III) 2,4-pentanedionate,
by the information contained in Practice E 386. to the sample is recommended as a means to reduce the
relaxation times of all the carbon-13 nuclei and, in so doing,
X1.2 Practices for Obtaining Acceptable High-Resolution shorten the time required between r-f irradiation pulses. The
NMR Spectra: relaxation reagent does not change the number of scans that
X1.2.1 The homogeneity of the instrument’s magnetic field must be averaged to achieve an acceptable signal to noise ratio,
must be optimized so that the best possible spectral resolution however.
and signal to noise ratio are obtained. The tuning of the X1.4.4 Carbon-13 NMR spectra are acquired under condi-
detector must also be optimized according to the manufactur- tions such that the spin-spin coupling interaction between
er’s instructions. hydrogen and carbon nuclei is removed or decoupled. Under
X1.2.2 The solution concentration should remain constant certain hydrogen decoupling conditions, however, energy
from sample to sample for both1H and13C NMR measure- transfer from hydrogen to carbon nuclei may result in an
ments. In order to ensure an accurate integration in a CW enhancement in the carbon signal intensity known as the
spectrum, the solution concentration must be such that a nuclear Overhauser enhancement (nOe) (see Practice E 386).
sufficiently good signal to noise ratio is obtained on the The magnitude of this effect is broadly dependent on the
smallest band to be measured. Signal averaging in pulse FT number of hydrogen atoms bonded to a particular carbon, the
NMR should continue until a similar condition is reached. chemical environment of the specific carbon, and the magnetic
Recommended signal to noise ratios for CW and pulse FT field strength. In order to suppress this phenomenon and avoid
NMR techniques are indicated in Table 1 and Table 2. distorted integral data, gated decoupling must be used in which
the hydrogen decoupler is only switched on during acquisition
X1.3 NMR Chemical Shift References for NMR Spectra: of the13C signals. Gated decoupling should be used in conjunc-
X1.3.1 The preferred internal reference compound for 1H tion with the relaxation reagent indicated in X1.3.3 to minimize
NMR spectra is tetramethylsilane (TMS). The1H chemical shift the nOe effect on the13 C NMR integral data.
position for the single1H NMR absorption line observed for X1.4.5 The NMR spectrum obtained after Fourier transfor-
this compound is defined as 0.0 ppm. mation on a pulse FT spectrometer should have a computer-
X1.3.2 The preferred internal reference compound for13C limited spectral resolution sufficient to accurately define the
NMR spectra is tetramethylsilane (TMS). The13C chemical aromatic and aliphatic absorption bands.
shift position for the single13C NMR absorption line observed X1.4.6 The NMR spectrum must also have a reasonably flat
for this compound is defined as 0.0 ppm. baseline over the entire spectral region so that the areas under
these absorption bands can be accurately integrated. Two
X1.4 Quantitative Measurements by High-Resolution NMR techniques are available to obtain flat baselines: optimization
Spectroscopy: of the pulse FT data acquisition conditions (receiver dead time,
X1.4.1 Quantitative CW spectra can be obtained provided filter band width, etc.) and computer-assisted baseline correc-
the signals are not saturated by the application of the radiof- tion of the NMR spectrum after Fourier transformation. The
requency (r-f) field at too high a power level. Consult the first technique is preferable although often unachievable in
spectrometer manufacturer’s instructions for recommended r-f practice. The second technique should be applied with caution
field settings. as it can cause distortions in the spectrum and in the integral.
X1.4.2 Quantitative FT spectra which are acquired by col- Consult the spectrometer manufacturer’s instructions for rec-
lecting the signal response following short r-f pulses require ommended baseline correction procedures.
the consideration of a number of parameters. The duration and X1.4.7 It is absolutely essential that the spectrum, whether
the spacing of the r-f pulses must be selected to ensure that the collected on a pulse FT or CW spectrometer, be phased
sample’s1H and13C nuclei return to an equilibrium condition correctly before the integrals are measured. Consult the instru-
between pulses. Since this return to equilibrium occurs rapidly ment manufacturer’s instructions for proper and improper
in1H NMR (usually between 1 to 5 s) and a good signal to spectrum phasing. Power spectrum or absolute value spectrum
noise ratio can usually be obtained in a short time of data options must not be used.
acquisition, quantitative results can be obtained in 1H NMR X1.4.8 In order to obtain accurate integral data, analog
without placing major constraints on instrument time. integral traces must be horizontal both before and after the
X1.4.3 The corresponding relaxation times for13C NMR are peak or band being integrated.
much longer (usually between 2 to 20 s) and, coupled with its X1.4.9 Vertical expansion of the analog integral traces must
decreased sensitivity compared to1 H NMR, a considerable be as large as possible. If using manual measuring methods,

6
 D 5292 – 99
maximize the integral trace by vertical expansion and check the peak or band being integrated.
again that the integral trace is horizontal both before and after

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