PAGE 1 Oil Analysis Analysis of this oil sample was conducted in the Chemical Engineering laboratories at the University REDACTED of Tennessee Chattanooga by Dr. Soubantika Palchoudhury, Assistant Professor, Chemical REDACTED Engineering and her graduate student, Armel Boutchuen. Experimental Method The liquid oil sample was characterized on a Bruker Alpha fourier transform infrared spectroscope (FTIR) equipped with attenuated total reflectance (ATR) capabilities over a wavelength range of 4004000 cm-1 at room temperature to determine the surface functional groups in the sample and thereby identify the oil type. FTIR spectra were reported based on five consecutive runs for reliability. Motor oil and three different varieties of commercial edible oil (e.g., Great Value vegetable oil, Publix brand vegetable oil, and Golden Chef vegetable oil) were also characterized using the same conditions for comparison. Finally, the FTIR spectrum of oil sample was compared with the four other commonly used oils analyzed, literature reports, and spectral libraries available in literature to identify the oil type. 1 Results and Discussion Figure 1. Image of oils analyzed via FTIR for this project. (Left to right) oil sample, Great Value vegetable oil (edible oil 1), Golden Chef vegetable oil (edible oil 3), Publix vegetable oil (edible oil 2), O Reilly motor oil, and food grade mineral oil. Figure 1 shows the oil sample and the four other common oils characterized. The oil sample was transparent, but had an odor. The major peaks in FTIR spectrum of the oil sample (Figure 2a) and their attributed chemical bonds are highlighted in Table 1. Two sharp FTIR peaks observed at 2919 cm -1 and 2851 cm-1 with a shoulder at 2939 cm-1 were attributed to the CH2 aliphatic bend.2,3 The spectrum contained a weak peak at 1651 cm-1, characteristic of C=C aromatic stretch. 3 The transmittance at 1458 cm-1 were due to contributions from the CH 2 and CH3 bending modes while methyl bending vibrations induced the peak at 1374 cm -1.3 A broad peak was observed at 1308 cm -1 due to ester linkages and the peak at 719 cm-1 corresponded to the aromatic C-H out-of-plane bending vibrations. 3 The peaks at 2361 cm-1 and 2340 cm-1 are due to CO2. The FTIR profile matched with literature data and spectral profiles of petroleum based oils such as motor oil, crude oil, diesel, or kerosene. 2,4,5,6,7 Table 1. Summary of FTIR analysis for the oil sample No. Wavelength of major FTIR peaks (cm - Corresponding chemical bond ) 1 1January 6th, 2020 PAGE 2 1 2 3 4 5 6 2919 and 2851; shoulder at 2939 1651 1458 1374 1308 719 CH2 aliphatic bend C=C aromatic stretch CH2 and CH3 bending Methyl bending Ester C-O bond C-H out-of-plane bend Figure 2. Representative FTIR plots. (a) oil sample, (b) comparative FTIR plot of the oil sample with three different edible oils, a commercially available motor oil, and food grade mineral oil, and (c) comparison of the oil sample with mineral and motor oil. In the next step, a comparison of this spectrum was made with different edible oils, mineral oil, and motor oil (Figure 2b). A strong peak was observed at 1742 cm -1, characteristic of saturated C=O stretch of aldehydes for the edible oils.8 This characteristic peak was also present in all oils derived from 2January 6th, 2020 PAGE 3 plant and fatty acid or triglyceride sources, based on a detailed literature review. 9,10 This peak was absent in the FTIR spectrum of the oil sample. In addition, two prominent peaks were observed at 1162 cm -1 and 1098 cm-1 corresponding to C-O ester linkage for edible oils as compared to one ester peak for the oil sample. The fingerprint region of the edible oils showed broad peaks from 719 cm -1 – 668 cm-1, markedly different from the spectrum of the oil sample. Therefore, the spectrum of the oil did not match with edible oil or hydrogenated edible oil. The data confirmed that the analyzed oil sample was not an edible oil or ghee. The FTIR spectrum of oil sample matched with petroleum derived oils such as mineral oil and motor oil as shown in Figure 2c. Motor oil is not a clear liquid, unlike the provided oil sample. A closer match was observed with mineral oil, which is also a transparent colorless liquid obtained as a by-product of crude refining for the production of gasoline or diesel. The results strongly suggest that the oil sample is mineral oil. Conclusion Our detailed analysis based on FTIR suggest that this oil sample does not belong to the class of edible oils or oils derived from fatty acids, triglycerides, and plant sources. The FTIR profile indicate a petroleum derived product, particularly mineral oil. Further analysis such as gas chromatography mass spectrometry, solvent extraction, and nuclear magnetic resonance could be used to confirm these results. References 1. Coates, J., Interpretation of infrared spectra, A practical approach. In Encyclopedia of Analytical Chemistry, Meyers, R. A., Ed. John Wiley & Sons Ltd. 2. Riley, B. J.; Lennard, C.; Fuller, S.; Spikmans, V., An FTIR method for the analysis of crude and heavy fuel oil asphaltenes to assist in oil fingerprinting. Forensic Science International 2016, 266, 555-564. 3. Wilt, B. K.; Welch, W. T.; Rankin, J. G., Determination of asphaltenes in petroleum crude oils by Fourier transform infrared spectroscopy. Energy & Fuels 1998, 12 (5), 1008-1012. 4. Asemani, M.; Rabbani, A. R., Detailed FTIR spectroscopy characterization of crude oil extracted asphaltenes: Curve resolve of overlapping bands. Journal of Petroleum Science and Engineering 2019. 5. Fodor, G. E.; Kohl, K. B.; Mason, R. L., Analysis of gasolines by FT-IR spectroscopy. Analytical Chemistry 1996, 68 (1), 23-30. 6. Samanta, A.; Ojha, K.; Mandal, A., Interactions between acidic crude oil and alkali and their effects on enhanced oil recovery. Energy & Fuels 2011, 25 (4), 1642-1649. 7. Revathy, T.; Jayasri, M. A.; Suthindhiran, K., Biodegradation of PAHs by Burkholderia sp. VITRSB1 Isolated from Marine Sediments. Scientifica 2015, 867586, 9 pages. 8. Lewis, R.; McElhaney, R. N.; Pohle, W.; Mantsch, H. H., Components of the carbonyl stretching band in the infrared-spectra of hydrated 1,2-diacylglycerolipid bilayers - a reevaluation. Biophysical Journal 1994, 67 (6), 2367-2375. 9. Rohman, A.; Windarsih, A.; Riyanto, S.; Sudjadi; Ahmad, S. A. S.; Rosman, A. S.; Yusoff, F. M., Fourier transform infrared spectroscopy combined with multivariate calibrations for the authentication of avocado oil. International Journal of Food Properties 2016, 19 (3), 680-687. 10. Rohman, A., Infrared spectroscopy for quantitative analysis and oil parameters of olive oil and virgin coconut oil: A review. International Journal of Food Properties 2017, 20 (7), 1447-1456. 3January 6th, 2020 PAGE 4 Oil Analysis Analysis of this oil sample was conducted in the Chemical Engineering laboratories at the University REDACTED of Tennessee Chattanooga by Dr. Soubantika Palchoudhury, Assistant Professor, Chemical REDACTED Engineering and her graduate student, Armel Boutchuen. Experimental Method Two liquid oil samples were characterized on a Bruker Alpha fourier transform infrared spectroscope (FTIR) equipped with attenuated total reflectance (ATR) capabilities over a wavelength range of 4004000 cm-1 at room temperature to determine the surface functional groups in the sample and thereby identify the oil type. FTIR spectra were reported based on five consecutive runs for reliability. Motor oil, mineral oil, and three different varieties of commercial edible oil (e.g., Great Value vegetable oil, Publix brand vegetable oil, and Golden Chef vegetable oil) were also characterized using the same conditions for comparison. Finally, the FTIR spectra of oil samples were compared with the four other commonly used oils analyzed, literature reports, and spectral libraries available in literature to identify the oil type. 1 Results and Discussion Figure 1. Image of oils analyzed via FTIR for this project. (Left to right) oil sample, Great Value vegetable oil (edible oil 1), Golden Chef vegetable oil (edible oil 3), Publix vegetable oil (edible oil 2), O Reilly motor oil, food grade mineral oil, and oil sample 2. Figure 1 shows two oil samples and the four other common oils characterized in our study. Both oil samples were transparent, but had an odor. Both oil samples showed similar characteristics. The major peaks in FTIR spectrum of the oil sample (Figure 2a) and their attributed chemical bonds are highlighted in Table 1. Two sharp FTIR peaks observed at 2919 cm -1 and 2851 cm-1 with a shoulder at 2939 cm -1 were attributed to the CH2 aliphatic bend.2,3 The spectrum contained a weak peak at 1651 cm -1, characteristic of C=C aromatic stretch.3 The transmittance at 1458 cm-1 were due to contributions from the CH2 and CH3 bending modes while methyl bending vibrations induced the peak at 1374 cm -1.3 A broad peak was observed at 1308 cm-1 due to ester linkages and the peak at 719 cm -1 corresponded to the aromatic C-H out-of-plane bending vibrations.3 The peaks at 2361 cm-1 and 2340 cm-1 are due to CO2. The FTIR profile matched with literature data and spectral profiles of petroleum based oils such as motor oil, crude oil, diesel, or kerosene.2,4,5,6,7 Table 1. Summary of FTIR analysis for the oil samples No. Wavelength of major FTIR peaks (cm - Corresponding chemical bond 1 ) 1January 31st, 2020 PAGE 5 1 2 3 4 5 6 2919 and 2851; shoulder at 2939 1651 1458 1374 1308 719 CH2 aliphatic bend C=C aromatic stretch CH2 and CH3 bending Methyl bending Ester C-O bond C-H out-of-plane bend Figure 2. Representative FTIR plots. (a) oil sample, (b) comparative FTIR plot of the two oil samples with three different edible oils, a commercially available motor oil, and food grade mineral oil, and (c) comparison of the oil samples with mineral and motor oil. In the next step, a comparison of this spectrum was made with different edible oils, mineral oil, and motor oil (Figure 2b). A strong peak was observed at 1742 cm -1, characteristic of saturated C=O 2January 31st, 2020 PAGE 6 stretch of aldehydes for the edible oils.8 This characteristic peak was also present in all oils derived from plant and fatty acid or triglyceride sources, based on a detailed literature review. 9,10 This peak was absent in the FTIR spectrum of the oil sample. In addition, two prominent peaks were observed at 1162 cm -1 and 1098 cm-1 corresponding to C-O ester linkage for edible oils as compared to one ester peak for the oil sample. The fingerprint region of the edible oils showed broad peaks from 719 cm -1 – 668 cm-1, markedly different from the spectrum of the oil samples. Therefore, the spectrum of the oil did not match with edible oil or hydrogenated edible oil. The data confirmed that the analyzed oil sample was not an edible oil or ghee. The FTIR spectrum of oil sample matched with petroleum derived oils such as mineral oil and motor oil as shown in Figure 2c. Motor oil is not a clear liquid, unlike the provided oil sample. A closer match was observed with mineral oil, which is also a transparent colorless liquid obtained as a by-product of crude refining for the production of gasoline or diesel. The results strongly suggest that the oil sample is mineral oil. Conclusion Our detailed analysis based on FTIR suggest that this oil sample does not belong to the class of edible oils or oils derived from fatty acids, triglycerides, and plant sources. The FTIR profile indicate a petroleum derived product, particularly mineral oil. In addition, both oil samples showed similar FTIR profiles. Further analysis such as gas chromatography mass spectrometry, solvent extraction, and nuclear magnetic resonance could be used to confirm these results. References 1. Coates, J., Interpretation of infrared spectra, A practical approach. In Encyclopedia of Analytical Chemistry, Meyers, R. A., Ed. John Wiley & Sons Ltd. 2. Riley, B. J.; Lennard, C.; Fuller, S.; Spikmans, V., An FTIR method for the analysis of crude and heavy fuel oil asphaltenes to assist in oil fingerprinting. Forensic Science International 2016, 266, 555-564. 3. Wilt, B. K.; Welch, W. T.; Rankin, J. G., Determination of asphaltenes in petroleum crude oils by Fourier transform infrared spectroscopy. Energy & Fuels 1998, 12 (5), 1008-1012. 4. Asemani, M.; Rabbani, A. R., Detailed FTIR spectroscopy characterization of crude oil extracted asphaltenes: Curve resolve of overlapping bands. Journal of Petroleum Science and Engineering 2019. 5. Fodor, G. E.; Kohl, K. B.; Mason, R. L., Analysis of gasolines by FT-IR spectroscopy. Analytical Chemistry 1996, 68 (1), 23-30. 6. Samanta, A.; Ojha, K.; Mandal, A., Interactions between acidic crude oil and alkali and their effects on enhanced oil recovery. Energy & Fuels 2011, 25 (4), 1642-1649. 7. Revathy, T.; Jayasri, M. A.; Suthindhiran, K., Biodegradation of PAHs by Burkholderia sp. VITRSB1 Isolated from Marine Sediments. Scientifica 2015, 867586, 9 pages. 8. Lewis, R.; McElhaney, R. N.; Pohle, W.; Mantsch, H. H., Components of the carbonyl stretching band in the infrared-spectra of hydrated 1,2-diacylglycerolipid bilayers - a reevaluation. Biophysical Journal 1994, 67 (6), 2367-2375. 9. Rohman, A.; Windarsih, A.; Riyanto, S.; Sudjadi; Ahmad, S. A. S.; Rosman, A. S.; Yusoff, F. M., Fourier transform infrared spectroscopy combined with multivariate calibrations for the authentication of avocado oil. International Journal of Food Properties 2016, 19 (3), 680-687. 10. Rohman, A., Infrared spectroscopy for quantitative analysis and oil parameters of olive oil and virgin coconut oil: A review. International Journal of Food Properties 2017, 20 (7), 1447-1456. 3January 31st, 2020