Monograph pubs.acs.org/doi/book/10.1021/acsreagents
Phthalate Esters Part 5, Assay and Identification of Standard-Grade Reference Materials: Specifications and Tests eISBN: 9780841230460 Tom Tyner Chair, ACS Committee on Analytical Reagents James Francis Secretary, ACS Committee on Analytical Reagents
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ABSTRACT This ACS Reagent Chemicals Standard-Grade Reference Materials monograph for Phthalate Esters, in addition to common physical constants, details the following specifications and corresponding tests for verifying that a substance meets ACS Standard-Grade specifications including: Identity by Infrared Spectroscopy, Identity by Gas Chromatography−Mass Spectrometry, Assay by Gas Chromatography, and Assay by Thin-Layer Chromatography.
SPECIFICATIONS Identity by Infrared spectroscopy. . . . . . . . . . . . . . . . . Passes test Gas chromatography–mass spectrometry . . . . . Passes test
Assay by Gas chromatography . . . . . . . . . . . . . . . . . ≥98.0% Thin-layer chromatography . . . . . . . . . . . . . Passes test
TESTS Identity by Infrared Spectroscopy Analyze the sample using the general procedure cited in [Part 2: Infrared Spectroscopy]. The spectrum must be consistent with either (1) the identifying ions listed for the compound in Table 5-8 or (2) the spectrum listed for the compound in the NIST standardized library of compounds. However, absorbance frequency and intensity may be different due to different analysis techniques. The spectrum may also be compared to other published libraries of infrared spectra, if available. Table 5-8. Phthalate Ester Compound Data
Name
CAS No.
Chemical Formula
Formula Weight
MS (m/z) MS-1
MS (m/z) MS-2
MS (m/z) MS-3
IR (cm−1) IR (cm−1) IR (cm−1) IR-1 IR-2 IR-3
Dimethyl isophthalate
1459-93-4
C10H10O4
194.2
163
135
194
1728
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DOI:10.1021/acsreagents.5009 ACS Reagent Chemicals, Part 5
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Table 5-8. Phthalate Ester Compound Data (continued)
Name
CAS No.
Chemical Formula
Formula Weight
MS (m/z) MS-1
MS (m/z) MS-2
MS (m/z) MS-3
IR (cm−1) IR (cm−1) IR (cm−1) IR-1 IR-2 IR-3
Dimethyl phthalate
131-11-3
C10H10O4
194.2
163
77
194
1729
11291
1126
Diethyl phthalate
84-66-2
C12H14O4
222.2
149
177
150
1727
1286
1074
Diallyl phthalate
131-17-9
C14H14O4
246.3
149
189
98
1728
1277
1126
Di-n-propyl phthalate
131-16-8
C14H18O4
250.3
149
76
150
1728
1281
1124
Di-n-butyl phthalate
84-74-2
C16H22O4
278.3
149
150
57
1731
1287
1122
Diisobutyl phthalate
84-69-5
C16H22O4
278.3
149
57
223
1727
1287
1123
Bis(2-methoxy-ethyl) phthalate
117-82-8
C14H18O4
282.3
59
58
149
1728
1288
1123
Diamyl phthalate
131-18-0
C18H26O4
306.4
149
150
237
1729
1288
1123
Bis(2-ethoxy-ethyl) phthalate
605-54-9
C16H22O4
310.3
72
73
149
1270
1128
1744
Butyl benzyl phthalate
85-68-7
C19H20O4
312.4
149
91
206
1726
1286
1122
Diphenyl phthalate
84-62-8
C20H14O4
318.3
225
226
77
1270
1190
1736
Dicyclohexyl phthalate
84-61-7
C20H26O4
330.4
149
167
55
1719
1293
1128
Bis(4-methyl-2-pentyl) phthalate
146-50-9
C20H30O4
334.5
149
85
150
Dihexyl phthalate
84-75-3
C20H30O4
334.5
149
150
55
1729
1283
1124
Dibenzyl phthalate
523-31-9
C22H18O4
346.4
91
107
149
1285
1127
1735
Bis(2-n-butoxy-ethyl) phthalate
117-83-9
C20H30O6
366.5
149
57
56
1728
1286
1121
Bis(2-ethylhexyl) isophthalate
137-89-3
C24H38O4
390.6
112
167
70
1726
1234
1302
Bis(2-ethylhexyl) phthalate
117-81-7
C24H38O4
390.6
149
167
57
1729
1280
1123
Di-n-octyl phthalate
117-84-0
C24H38O4
390.6
149
279
57
1729
1286
1124
Dinonyl phthalate
84-76-4
C26H42O4
418.6
149
293
71
1729
1284
1127
Diisononyl phthalate
68515-48-0
C26H42O4
418.6
149
293
Di-n-decyl phthalate
84-77-5
C28H46O4
446.7
149
307
107
1750
1285
1124
Diisodecyl phthalate
26761-40-0
C28H46O4
446.7
149
307
1729
1287
1125
Diundecyl phthalate
3648-20-2
C30H50O4
474.7
149
57
321
1729
1287
1123
Ditridecyl phthalate
119-06-2
C34H58O4
530.8
149
57
71
1730
1272
1124
Note: Disononyl phthalate and diisodecyl phthalate are mixtures of branched chain isomers. The GC and GC–MS chromatograms indicate this mixture by the presence of many peaks over time. These compounds are best analyzed by GC–MS. See the following method for additional information: Consumer Products Safety Commission, Test Method: CPSC-CH-C1001-09.3 Standard Operating Procedure for Determination of Phthalates (http://www.cpsc.gov/about/cpsia/CPSC-CH-C1001-09.3.pdf).
Identity by Gas Chromatography−Mass Spectrometry Analyze the sample by gas chromatography–mass spectrometry using method GCMS–PE1 described below. Method GCMS−PE1 Ionization Mode . . . . . . . . . . . . . . . . . . . . Electron ionization/70 eV Column . . . . . . . . . . . . . . . . . . . . . . . . . . 5% Diphenyl–95% dimethylpolysiloxane, 30 m × 0.25 mm i.d., 0.25 µm film thickness
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DOI:10.1021/acsreagents.5009 ACS Reagent Chemicals, Part 5
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Temperature Program. Carrier Gas . . . . . . . Injector . . . . . . . . . Injector Temperature . Scan Range . . . . . . . Sample Size . . . . . . .
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. 50 °C for 1 min, then 10 °C/min to 300 °C, then hold 10 min . Helium at 1 mL/min . Split/splitless (50:1 split) . 250 °C . 50–550 amu . 1 µL of a 100 µg/mL solution
The identifying ions for the compound listed in Table 5-8 must be present. The spectrum is compared to a known reference material or the NIST standardized library of compounds, if available.
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Assay by Gas Chromatography Analyze the sample by gas chromatography using method GCMS–PE1 described below. Method GC–PE1 Column . . . . . . . . . . . . . . . . . . . . . . . . . . 50% Diphenyl–50% dimethylpolysiloxane, 30 m × 0.53 mm i.d., 1.5 µm film thickness Detector . . . . . . . . . . . . . . . . . . . . . . . . . Flame ionization Detector Temperature . . . . . . . . . . . . . . . . 300 °C Injector . . . . . . . . . . . . . . . . . . . . . . . . . Split/splitless (10:1 split) Injector Temperature . . . . . . . . . . . . . . . . . 250 °C Sample Size . . . . . . . . . . . . . . . . . . . . . . . 1 µL of a 2500 µg/mL solution Carrier Gas . . . . . . . . . . . . . . . . . . . . . . . Helium at 5 psi Temperature Program. . . . . . . . . . . . . . . . . 50 °C for 1 min, then 10 °C/min to 300 °C, then hold 10 min Measure the area under all peaks (excluding the solvent peak), and calculate the analyte content in area percent for each analysis.
Assay by Thin-Layer Chromatography Analyze the sample by thin-layer chromatography using the general procedure described in [Part 2: Chromatography; Recommended Procedures; Thin-Layer Chromatography]. The following specific conditions are also required. Stationary Phase . . . . . . . . . . . . . . . . . . . . Silica Mobile Phase . . . . . . . . . . . . . . . . . . . . . . 1:3 (v/v) ethyl acetate: hexane. The ratio of ethyl acetate to hexane may need to be adjusted depending on the polarity of the compound. Detection Method . . . . . . . . . . . . . . . . . . . UV at 254 nm and iodine Compound must exhibit a single spot.
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ACS Reagent Chemicals ACS Reagent Chemicals; American Chemical Society: Washington, DC, 2017.
DOI:10.1021/acsreagents.5009 ACS Reagent Chemicals, Part 5
