Designation: D7884 − 13

Standard Test Method for

Determination of 4-Carboxybenzaldehyde and p-Toluic Acid
in Purified Terephthalic Acid by Reverse Phase High
Performance Liquid Chromatography1
This standard is issued under the fixed designation D7884; 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.

1. Scope ASTM Test Methods

1.1 This test method covers the determination of the E682 Practice for Liquid Chromatography Terms and Rela-
4-Carboxybenzaldehyde (4-CBA) and p-Toluic acid (p-TOL) tionships
in purified terephthalic acid (PTA) by reverse phase high E691 Practice for Conducting an Interlaboratory Study to
performance liquid chromatography (HPLC). This method is Determine the Precision of a Test Method
applicable for 4-CBA from 2 to 500 mg/kg and for p-TOL from 2.2 ISO Document:3
10 to 500 mg/kg, respectively. EN ISO 8213 Chemical products for industrial use—
Sampling techniques—Solid chemical products in the
1.2 In determining the conformance of the test results using form of particles varying from powders to coarse lumps
this method to applicable specification, results shall be rounded 2.3 Other Document:4
off in accordance with the rounding-off method of Practice OSHA Regulations, 29 CFR paragraphs 1910.1000 and
E29. 1910.1200
1.3 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this 3. Summary of Test Method
standard. 3.1 Reverse Phase HPLC Method—PTA sample is dissolved
1.4 This standard does not purport to address all of the in ammonium hydroxide solution, and a fixed volume of this
safety concerns, if any, associated with its use. It is the solution is injected into a high performance liquid chromato-
responsibility of the user of this standard to establish appro- graph equipped with a UV detector. A C18 chemically bonded
priate safety and health practices and determine the applica- column is used to separate the impurities 4-CBA and p-TOL
bility of regulatory limitations prior to use. from PTA. The external standard calibration is used for
quantification.
2. Referenced Documents
4. Significance and Use
2.1 ASTM Standards:2
4.1 The presence of 4-CBA and p-TOL in PTA used for the
D1193 Specification for Reagent Water
production of polyester is undesirable because they can slow
D4790 Terminology of Aromatic Hydrocarbons and Related
down the polymerization process and 4-CBA imparts color-
Chemicals
ation to the polymer due to thermal instability.
D6809 Guide for Quality Control and Quality Assurance
Procedures for Aromatic Hydrocarbons and Related Ma- 4.2 Determining the amount of 4-CBA and p-TOL remain-
terials ing from the manufacture of PTA is often required. This test
E29 Practice for Using Significant Digits in Test Data to method is suitable for setting specifications and for use as an
Determine Conformance with Specifications internal quality control tool where these products are produced
E177 Practice for Use of the Terms Precision and Bias in or are used.
5. Apparatus
1
This test method is under the jurisdiction of ASTM Committee D16 on 5.1 High Performance Liquid Chromatograph (HPLC)—
Aromatic Hydrocarbons and Related Chemicals and is the direct responsibility of any HPLC capable of pumping the mobile phase at flow rates
Subcommittee D16.02 on Oxygenated Aromatics.
Current edition approved Aug. 1, 2013. Published October 2013. DOI: 10.1520/
3
D7884-13. Available from American National Standards Institute (ANSI), 25 W. 43rd St.,
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or 4th Floor, New York, NY 10036, http://www.ansi.org.
4
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Available from U.S. Government Printing Office Superintendent of Documents,
Standards volume information, refer to the standard’s Document Summary page on 732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401, http://
the ASTM website. www.access.gpo.gov.

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

1
 D7884 − 13
TABLE 1 Recommended Operating Conditions of sufficiently high purity to permit its use without lessening
Column C18 the performance or accuracy of the determination. Reagent
Stationary phase
Octadecylsilane chemically chemicals shall be used for all tests.
bonded silica NOTE 1—Calibration and detection limits of this test method can be
Particle size 5 µm biased by the purity of the reagents.
Material of column stainless steel
Length of column 150 mm 6.2 Ammonium Hydroxide—25 to 28 %.
Inner diameter 4–5 mm
0.06 % H3PO4 solution: 6.3 Phosphoric Acid—HPLC grade.
Mobile phase
acetonitrile = 82:18
Flow rate 1.0 mL/min 6.4 Acetonitrile—HPLC grade. (Warning—Acetonitrile is
UV detector
254 nm for 4-CBA flammable and hazardous in case of skin or eye contact,
240 nm for p-TOL ingestion, or inhalation.)
Injection amount 20 µL
Column temperature 40°C 6.5 Water—HPLC grade.
6.6 Ammonium Hydroxide Solution—ammonium hydroxide
mixed with water as 1:1 (V:V).
between 0.1 and 2.0 mL/min, with a pressure between 0 and 40
MPa and a pulsation of less than 1 % full scale deflection under 6.7 PTA Standard for Calibration—A certified PTA calibra-
the test conditions described in Table 1. The S/N (signal to tion standard with known amounts of 4-CBA and p-TOL is
noise) ratio should be 3:1 or greater for 2 mg/kg 4-CBA and 10 required. If it is not commercially available, please refer to
mg/kg p-TOL. Annex A1 for determining the concentrations of 4-CBA and
p-TOL in a PTA sample. The calibrated PTA sample can be
5.2 Sample Injection System—capable of injecting 1 to 25 served as a PTA calibration standard.
µL, using either partial or full loop mode, with a repeatability
of 61 %. 6.8 Mobile Phase:
6.8.1 0.06 % H3PO4 Solution:Acetonitrile = 82:18—
5.3 Detector–Variable Wavelength Ultraviolet Photometric Pipette 0.6 mL H3PO4 into a 1000 mL volumetric flask with
Detector (VWD), Multi-wavelength Detector, or Photometric 900 mL of water and make up to the mark with water to give
Diode Array Detector (PDA)—capable of operating at 240 and 0.06 % H3PO4 solution. Mix 820 mL of H3PO4 solution and
254 nm. 180 mL of acetonitrile. Methanol could be used as an alterna-
5.4 Column Oven—any suitable HPLC column oven (block tive to acetonitrile in the mobile phase.
heating or air circulating) capable of maintaining a constant
NOTE 2—It is recommended to degas and filter the mobile phase before
temperature of 61°C within the range of 20 to 70°C. use; degassing can be done conveniently, on-line or off-line by helium
5.5 Chromatography Data System. sparging, vacuum degassing or ultrasonic agitation.

5.6 HPLC Columns: 7. Hazards

5.6.1 A stainless steel HPLC column packed with an octa- 7.1 Consult current federal regulations, supplier’s Material
decylsilane (C18) chemically bonded silica stationary phase is Safety Data Sheets, and local regulations for all materials used
suitable. See Table 1 for recommended operating conditions. in this test method.
5.6.2 A C18 column with different dimensions (inner
diameter, length, particle size, etc.) that provides adequate 8. Sampling, Test Specimens, and Test Units
resolution to quantitate 4-CBA and p-TOL in a PTA sample can 8.1 Use only representative samples obtained as described
also be used. in EN ISO 8213, unless otherwise specified.
5.7 Analytical Balance—readable to 60.0001 g.
9. Preparation of Apparatus
5.8 Sample Filter—A disposable syringe filter made of
cellulose acetate, with a pore size between 0.22 and 0.45 µm, 9.1 Set up the pump, sample injection system, column,
and is chemically inert to aqueous solutions, is recommended oven, detector, and chromatography data system in accordance
for the removal of particulate matter from the sample solution. with the manufacturer’s instructions. Adjust the instrument to
the recommended conditions described in Table 1, allowing
6. Reagents and Materials sufficient time for the equipment to reach equilibrium which is
6.1 Purity of Reagents—Unless otherwise indicated, it is indicated by a stable horizontal baseline. For a new column, 4
intended that all reagents shall conform to the reagent grade to 6 hours of equilibration time may be required.
NOTE 3—Separation between peaks of 4-CBA and PTA can be
specification for analytical reagents of the American Chemical optimized by carefully varying the aqueous-organic ratio and flow rate.
Society, where such specifications are available.5 Other grades NOTE 4—It has been found for a reverse-phase HPLC, separation
may be used, provided it is first ascertained that the reagent is between 4-CBA and PTA can be improved by adding a certain amount of
trifluoroacetic acid (TFA) in acetonitrile water solution as a mobile phase.
NOTE 5—A gradient mobile phase can also be used for improving
5
Reagent Chemicals, American Chemical Society Specifications, American chromatograph.
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory 10. Calibration
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, 10.1 Weigh, to the nearest 0.0001 g, about 0.5 g of PTA
MD. standard in a 25 mL beaker, add 3 mL of ammonium hydroxide

2
 D7884 − 13

FIG. 1 Chromatogram of a PTA Sample (Reverse Phase HPLC)

1–PTA, 2–4-CBA, 3—p-TOL

solution, and 7 mL water to dissolve PTA completely. Then 13.2.2 Any deviation from the procedure specified (for
accurately transfer the resulting solution to a 250 mL volumet- example, detailed description of column and operating condi-
ric flask, and dilute with water to the mark. Inject 20 µL of the tions).
calibration standard solution into chromatograph for analysis. 13.2.3 Results of the test.
Record chromatogram and peak area values for 4-CBA and 13.2.4 Any abnormal situations observed during the test.
p-TOL respectively with data system.
NOTE 6—It is recommended that a calibration standard be run after 14. Precision and Bias6
every ten samples to check the stability of the chromatograph system.
14.1 The precision of this test method is based on an
11. Procedure intralaboratory study of Test Method D7884 conducted in
2012. One laboratory tested one PTA sample and one qualified
11.1 Weigh, to the nearest 0.0001 g, about 0.5 g of PTA terephthalic acid (QTA) sample for 4-CBA and p-TOL. Every
sample, repeat the remaining steps in 10.1, and record peak test result represents an individual determination. The labora-
area values of 4-CBA and p-TOL respectively. After each tory reported 20 replicate results for each analysis/material
analysis, rinse the column with mobile phase until the baseline combination in order to estimate the repeatability limits of the
is stabilized for the next run. The representative chromato- standard. Practice E691 was followed for the design and
grams of a PTA sample is shown in Fig. 1. analysis of the repeatability data; the details are given in
Research Report RR:D16-1048.
12. Calculation 14.1.1 Repeatability Limit (r)—Two test results obtained
12.1 Calculate the concentration of 4-CBA or p-TOL in within one laboratory shall be judged not equivalent if they
mg/kg, using the following equation: differ by more than the “r” value for that material; “r” is the
m s ·A·C s interval representing the critical difference between the two test
X5 (1) results for the same material, obtained by the same operator
m·A s
using the same equipment on the same day in the same
where: laboratory.
X = concentration of 4-CBA or p-TOL in the PTA sample, 14.1.1.1 Repeatability limits are listed in Table 2.
mg/kg, 14.1.2 Bias—At the time of the study, the test specimens
A = peak area of 4-CBA or p-TOL in the PTA sample, chosen for analysis were not accepted reference materials
m = weight of the PTA sample, g, suitable for determining the bias for the test method, therefore
As = peak area of 4-CBA or p-TOL in the PTA standard, no statement on bias is being made.
Cs = concentration of 4-CBA or p-TOL in the PTA standard,
mg/kg, 15. Quality Guidelines
ms = weight of the PTA standard, g.
15.1 Laboratories shall have a quality control system in
13. Report place.
13.1 Report the value of 4-CBA or p-TOL content in mg/kg,
to the nearest 1.0 mg/kg.
6
Supporting data have been filed at ASTM International Headquarters and may
13.2 Report the following information in the report: be obtained by requesting Research Report RR:D16-1048. Contact ASTM Customer
13.2.1 The complete identification of the sample tested. Service at service@astm.org.

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 D7884 − 13
TABLE 2 Repeatability Limits 15.1.3 When QA/QC protocols are already established in
Average Repeatability
Repeatability the testing facility, these protocols are acceptable when they
Sample Analyte Limit
(wt. mg/kg) Sr
r
confirm the validity of test results.
4-CBA 8.6 0.14 0.41 15.1.4 When there are no QA/QC protocols established in
PTA
p-TOL 135.1 1.72 4.86 the testing facility, use the guidelines described in Guide
4-CBA 231.2 1.42 4.02
QTA
p-TOL 23.1 0.68 1.92
D6809 or similar statistical quality control practices.

16. Keywords
15.1.1 Confirm the performance of the test instrument or 16.1 purified terephthalic acid; 4-Carboxybenzaldehyde;
test method by analyzing a quality control sample following p-Toluic acid; high performance liquid chromatograph;
the guidelines of standard statistical quality control practices. reverse-phase HPLC
15.1.2 A quality control sample is a stable material isolated
from the production process and representative of the sample
being analyzed.

ANNEX

(Mandatory Information)

A1. RECOMMENDED PROCEDURE FOR CALIBRATION OF PTA SAMPLE

When a PTA standard with known amounts of 4-CBA and p-TOL is not available, a PTA sample with granularity of 80 to 160 µm, contain-
ing 4-CBA and p-TOL at concentrations of 10 to 25 mg/kg and 100 to 200 mg/kg, respectively, may be analyzed to determine the concen-
trations of 4-CBA and p-TOL by using the following standard addition method. This PTA sample with calibrated concentrations of 4-CBA
and p-TOL can be used as the PTA standard for sample analysis.

A1.1 Reagents and Materials calibration standard p-TOL to the above flasks and dilute with
water to the mark. The concentrations of 4-CBA and p-TOL
A1.1.1 4-CBA—Purity >98.0 %.
added in these PTA solutions are as follows:
A1.1.2 P-TOL—Purity >98.0 %.
4-CBA ~mg/kg!: 0.0, 10.0*K, 20.0*K, 30.0*K, and 40.0*K
A1.2 Calibration Solutions where:
A1.2.1 Calibration Standard 4-CBA (10 µg/mL)—Weigh, to K = weight of 4-CBA from A1.2.1/0.0250
the nearest 0.0001 g, about 0.0250 g of 4-CBA in a 25 mL p-TOL ~mg/kg!: 0.0, 80.0*J, 160.0*J, 240.0*J, and 320.0*J
beaker, add some water and a few drops of ammonium
hydroxide solution, and stir until 4-CBA is completely dis- where:
solved. Adjust the pH value of the solution to 6–7 by using J = weight of p-TOL from A1.2.2/0.0200
phosphoric acid solution. Then accurately transfer the resulting
solution to a 50 mL volumetric flask and dilute with water to A1.3 Procedure
the mark to give a 500 µg/mL 4-CBA stock solution. Then A1.3.1 Follow steps in 10.1 to analyze the series PTA
dilute with water 50 times to 10 µg/mL. spiked solutions and record the peak area values of 4-CBA and
NOTE A1.1—Care must be taken to ensure a quantitative transfer of the p-TOL respectively. Each sample should be run in duplicate to
solution from the beaker, and also any material that is removed by the pH obtain an average value of peak area.
probe, into the 50 mL volumetric flask.
A1.2.2 Calibration Standard p-TOL (80 µg/mL)—Weigh, to A1.4 Calculation
the nearest 0.0001 g, about 0.0200 g of p-TOL, following steps A1.4.1 Construct a calibration curve (see Fig. A1.1) by
in A1.2.1 to give a 400 µg/mL p-TOL stock solution. Then plotting the spiked concentration on the X-axis and the average
dilute with water five times to 80 µg/mL. peak area on the Y-axis based on the theory of least square
A1.2.3 PTA Spiked Solutions—Accurately weigh 0.500 6 linear regression. A linear calibration curve is required with a
0.001 g of PTA in five 25 mL beakers each and follow steps in correlation coefficient (r2) greater or equal to 0.99, otherwise
10.1 to dissolve PTA samples. Then accurately transfer the the whole procedure should be repeated. A computer or data
solutions to five 250 mL volumetric flasks. Add 0.00, 0.50, system may be used to interpret the calibration.
1.00, 1.50, and 2.00 mL of calibration standard 4-CBA and A1.4.1.1 The linear equation is as follows:

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 D7884 − 13

FIG. A1.1 Standard Addition Method for Calibration of 4-CBA or p-TOL in PTA
C = concentration of added 4-CBA or p-TOL in the PTA sample, mg/kg
A = average peak area of 4-CBA or p-TOL in the PTA sample

A 5 a1 bC (A1.1) a
C0 5 (A1.2)
b
where:
C = spiked concentration of 4-CBA or p-TOL in the PTA where:
sample, mg/kg, C0 = concentration of 4-CBA or p-TOL in the PTA sample,
A = average peak area of 4-CBA or p-TOL in the PTA mg/kg,
sample, b = slope obtained from Eq A1.1,
b = slope obtained from Eq A1.1, a = intercept obtained from Eq A1.1.
a = intercept obtained from Eq A1.1.
A1.4.1.2 Calculate the concentrations of 4-CBA and p-TOL
in this PTA sample using the following equation:

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