Analytical and Process Instrumentation - Analytical Chemistry (ACS

Analytical and Process Instrumentation. J. W. LovelandC. N. White. Anal. Chem. , 1979, 51 (5), pp 238–256. DOI: 10.1021/ac50041a023. Publication Dat...
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A N A L Y T I C A L CHEMISTRY, VOL. 51, NO. 5, APRIL 1979

or of alkyl phenyl phosphite, respectively. Methods applicable to phosphorus and nitrogen [Kolb et al. (94K) and PerkinElmer ( I 4 1 K ) l and two methods applicable to phosphorus and sulfur [Patterson (136K) and Patterson and Howe (137K)l are described in the sulfur and nitrogen portions of this review. T h e determination of arsenic in catalytic reformer feedstocks by flameless atomic adsorption published by La Villa and Queraud (103K) involves adding 5 mL of 1% iodine in toluene, extracting twice with 10 mL of 1 7 ~nitric acid, evaporating the extract to dryness, adding 2 mL of 1%nitric acid, running the sample in the spectrometer, and comparing the results with those for a blank and for standard solutions of arsenic and magnesium. Michelot (114K) determined silicon in coking naphthas contaminated with siloxane antifoam agents by using a direct reading emission spectrometer equipped with a graphite rotating-disk electrode; the naphtha is diluted with mineral oil sufficient to reduce the combustion rate but not to affect the sensitivity.

Analytical and Process Instrumentation J. W. Loveland and C. N. White Suntech, I n c , , Newtown Square, Pennsylvania

In this year’s review, we have retained the same section headings as were used in 1977. Because of the frequent reference to familiar techniques and terminology. we are again using abbreviations to aid the reader in his perusal of the text. Abbreviations recommended by Chemical Abstracts will be used and are not itemized here. Other abbreviations are as follows: AA, atomic absorption; IR, infrared: UV, ultraviolet; MS. mass spectrometry; GC, LC, TLC, gas, liquid, and thin-layer chromatography, respectively; XRA, XRD, XRF, X-ray absorption, diffraction, and fluorescence, respectively; NMR, nuclear magnetic resonance; TC, thermal conductivity (detector); FID, flame ionization detector, FPD, flame photometric detector; std. dev., standard deviation; vis., viscosity: psig, pounds per square inch gauge; a d . , id., outer and inner diameter; in., inch; and HC. hydrocarbon(s). In preparing this review, increased activity was noted in several areas. The use of simulated distillation via GC is increasing, and there were numerous references to applications of GC-MS and LC. Increased activity in the computerization-automation of lab equipment and techniques was also noted. In the Process Instrumentation area, there is an increasing attempt to combine two or more techniques or modifying GCs to resolve on-line analysis problems. The increased use of thermography IR to determine hot spots in boilers and reactors has been noted. X-ray analyzers continue to make inroads in the analysis of S, and metals in petroleum products. The following are recommended for a general reading and cover a broad spectrum of techniques and/or applications.

B R O A D REVIEWS Laboratory. Kajikawa (88L) surveyed the system established by the U.S. Bureau of Standards for standard reference materials and test methods and their role in industrial quality control. Also reviewed are types of petroleum-related reference materials available in the U S . , and Japan Petroleum Institute methods for the prepn. and testing of std. reference samples, illustrated with their N-in-oil stds. Fujita (57L) surveyed instrumental analyses for petroleum products. Topics covered chromatographic techniques, illustrated mostly with lube oil additive analyses, and organic analyses of petroleum and petroleum products by IR, NMR, MS, and inorganic analyses by AA, emission, XRF, and XRD of materials such as sludge, scale, and metals in lubes. Amthor ( 7 L ) discussed principles of laboratory automation in oil industry analytical labs. Included are the mechanization of individual tests (bp, mp, viscosity, d, base no.. pour pt., cloud pt., IR, IJV, NMR, GC, titration, photometry, and elemental analyses), on-line data processing, the suitability of the test for automation, problems of standardization, economic justification, factors affecting the decision to automate and the state of automation in several typical labs in the petroleum industry.

Krieger and Worthy (945) discussed the instruments shown a t the Pittsburgh Conference on Analytical Chemistry and Applied Spectroscopy in 1977. T h e survey covers photoacoustic spectroscopy, GC/MS systems, GC, LC, AA, IR, UV, and visible spectroscopy, emission spectroscopy, XKD, and XRF. Three papers on GC in the oil industry were presented at a Joint Meeting of the Chromatography and Electrophoresis Group, the Scottish Region, and the Chromatography Discussion Group of the Analytical Division of The Chemical Society held a t Grangemouth, Scotland, Nov. 1976 (128L). Topics treated were heat desorption of trapped vapors from personnel air-monitoring tubes, sources of error in GC analysis and applications of GC in petroleum prospecting. Emergy (44L) surveyed automated chromatography equipment in use a t Monsanto Industrial Chemicals Co., including applications in HC anal. Engelhardt (4SL) discussed the capabilities and limits o f LC and its use in petroleum and coal problems. The prepn. and characterization of sepn. columns, and the advantages of polar and nonpolar stationary phases and of partition, ion-exchange, and exclusion chromatography were covered. Gaylor (61L) reviewed gel permeation (steric excluusion) chromatography for the period Dec. 1975-Nov. 1975. Topics treated include reviews, literature services, apparatus, fundamental studies (non-exclusion effects. resolution, bandspreading, calibration), techniques (branching studies, prep. scale) and applications (analysis of oils and pitches). Alter (6L)surveyed XRF spectrometry, covering equipment and measuring principles, efficiency with respect to accuracy and sample size, sample prepn. and matrix effects, types of equipment available and important applications. In the petroleum industry, applications covered were detn. of P b in fuels, Cu in transformer oils, V and Ni in heating oils, S in crude oils and finished products, C in hydrocarbons, and the combination of XRF with sepn. methods such as TLC. Welz ( I 8 4 L )surveyed the application of A.4 in industrial analysis, covering instrumentation (flame and furnace), analysis of engine, hydraulic and transmission oils of trucks for wear metals, detection of trace metals in wastewater. polymer analysis. and control of metals in fuel oils for high-speed gas turbines. Keil et al. (89L) reviewed inelastic electron tunneling spectroscopy (IETS). Application of IETS to anal. chem. and surface interactions is illustrated by reviewing spectra that have been obtained from 1966 to the present. West (285L) edited the Proceedings of the Sixth Conference on Molecular Spectroscopy organized by the Institute of Petroleum, Hydrocarbon Research Group, Durham, England, March-April 1976. Topics covered include NMR (instrumentation; applications for ( I ) nuclei in low natural abundance, (2) petroleum and coal, (3) solids; spin mapping); Fourier-transform NMR (anal. of crude oils and heavy cuts); IR spectroscopy (multiplex vs. single channel, Laser applications); Raman (petroleum applications); electron spectroscopy (chem. anal., recent developments, depth resolution, surface investigations): molecular spectroscopy (forensic); spectroscopy (polymers, isoprenoid HC in coal and petroleum). Process Analyzers. Utterback ( I 74L)provided a succinct discussion of on-line process analyzers including: sampling systems; pH systems; various spectrophotometric analyzers; quadrupole MS; water and analyzers; LC and GC and various detectors; special application analyzers; computer-analyzer systems; maintenance, calibration, and various factors promoting acceptance of on-line process control. Sandford ( 1 4 4 L ) discusses analyzers as being faster and more reliable than previously. Systems covered were: GC to monitor catalytic crackers and ammonia production units; computer-controlled GC such as Honeywell’s hi-speed multistream analyzer and Foxboro’s GC with pneumatic transmitter; nn-line LC, MS, IR, UV, chemiluminescence, colorimetry, electrochemical systems for ions, pH and 02. Application of some of these analyzers to specific problems are given for process and pollution control. Zakaib (190~5)looks at both on-line and off-line analyzers as they apply to studies and control of major processes such as fractionation, reforming, catalytic cracking, alkylation, and sulfur recovery. Various improvements in process control are discussed and 40 references are given. Broussard (2615)discussed proper sampling techniques with particular emphasis on proportional flow sampling of high

ANALYTICAL CHEMISTRY, VOL. 51, NO.

ethane content natural gas-liquid mixtures. Covered are the difficulties with continuous sampling systems including: control of temp. and press., stratification and vaporization of light ends. Also reviewed were the components of a continuous sampling system; advantages of a constant pressure sampler in preventing thermal expansion and composition changes during sample transfer; and the importance of ensuring all samples are thoroughly mixed. An example of the metering errors which can result from inadequate sampling is given. Erk (47L) outlines an engineering procedure for justifying, specifying, and installing on-line process analyzers. Aspects covered were: review of process requirements; detg. type of analysis needed; locating best sample point with respect to system response; prepg. data specification sheets for bids; developing sample handling system, calibration system and wiring system; and reviewing acceptable fabrication shops with respect to cost and scheduling.

ELEMENTAL ANALYSIS Laboratory Methods--Single Elements. Swinehart (161L) discussed the detn. of C in organic materials using the LECO IR-12 automatic analyzer. The sample is combusted in an O2 atm. in an induction furnace to produce CO and CO?. CO in the sample is converted to COYover a heated Pt catalyst, and the gases are measured in an IR cell. Methods for achieving complete combustion are described. Measurement of total C in automatic catalyst analyzer agreed well with a standard sample. Sengupta et al. (15OL)described and evaluated an elec. cond. app. for detg. rate of C deposition and gasification in a pilot-plant for catalytic steam-naphtha reforming. Masuko (105L)compared the analysis of S in fuel oils using two Japanese X-ray S analyzers, one with a W tube and one with a Ti tube. Instrument parameters, the effect of contaminants and various measuring and data evaluation techniques were discussed. Vitovec ( I 78L) patented an automatic computerized apparatus for determining S concn. in petroleum products based on radiation absorption. Detection is accomplished with a Geiger tube, and readout of S content is numerical. S a t 5 2 and 2-4% can be detd. with a std. deviation of f0.02 and *0.0370 S. resps. Fraisse and Andrianjafintrimo (53L) described a com. available automatic analyzer for the rapid micro detn. of O2 in org. and some inorg. compds. The technique is based on the Schuetze- Unterzaucher principle. It involves flash pyrolysis of the sample in Iv atm. and redn. of pyrolytic gases with C-black a t 1120 OC to produce CO which is oxidized to CO,; the latter is titrated coulometrically. Complete automation is made possible by using a vertical reactor. Analysis time is 5--7 min. ,4n autosampler can he added to the unit. Fine (51L) described the thermal N2 analyzer, a new highly sensitive and N-selective detector for LC. The eluate is mixed with O2 and oxidized a t 1000 "Cto CO,, H 2 0 :and nitrosyl radical, which is then reacted with O3 to form excited NO,. T h e N O p decays hack to the ground state with the emission of light: the intensity of which is a direct measure of N content. Kulke and Umland ( 9 5 L ) discussed improvements in the Wickbold apparatus for combustion of heavier oils and used lubricating oils for trace analysis of inorg. components. The modifications provide greater control over flame temp.. improved burner efficiency. and improved efficiency in trapping combustion products. Elemental anal. after combustion was accomplished with flameless AA. The method was applied successfully to the detn. of V in used lube oil (in methyl ethyl ketone). Bremstedt et al. (2,jL) used a Pariametrics portable XRF analyzer to determine Ru on catalytic surfaces. Results agreed with those obtained using a Philips universal vacuum spectrometer and AA.

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Laboratory Methods-Multielement

Analysis.

Hoodless et al. (801,) investigated the main operating parameters and performance of a com. %electrode thermionic GC detector for P, S, and N. Max. sensitivities of this detector are compared with those of the FID. The detector may be operated in various modes to improve simplicity of operation for routine use, to ohtain selective responses individually for each type of compd., or to give equal response to P-, S- and N-contg. compds. while discrimination against HC. Reliable set-up procedures and use for routine analysis are discussed. Sensitivity is greatest for P-compds. Ilugan (43L)described

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an automatic analyzer for the simultaneous detn. of C, H,, N p ,and S in org. compds. The method utilizes uncatalyzed, dynamic, flash-combustion of the sample in an (),/He atm. in a quartz tube, followed by detn. of the combustion gases, N,, C 0 2 , SO,, and H 2 0by GC (Poropak QS column, 130 O C , T C detector). Van den Bosch et al. (175L) developed an elemental analyzer system controller for automated data processing of automatic C-H-N analyzer output. After starting the C-H-N analyzer, this system processes all data and calculates the blanks, calibration factors, and percentage, successively. The system uses a digital voltnieter or integrator. electronic microbalance, calculator, and C-H-N analyzer. Harrington and Bramstedt (73L)adapted the Perkin-Elnier 240 C-H-N analyzer for on-line data acquistion with a remote PDP-l5/76 computer. Sample wts. (Cahn electrobalance) are entered into the computer and the output from the 3 T C detectors are monitored for 10 s! and signal-averaged by the computer. A final report is printed out on a (Silent 700) remote terminal. Precision of results compared favorably with those calcd. manually. A 38% improvement in efficiency was obtained. Kunze (96L) modified an automatic C, H, N, analyzer to det. S. The sample is burned in O 2 and the resulting SO, measured via TC. Anal. time is 13 min. Housseau et al. (139L)totally automated the coulometric detn. of C. H, and 0, in petroleum products. Reproducibility at 95% confidence level was 0.6-1.0 for C, 0.3M.6 for H?, 0.18--1.04 for 02,and 0.10--0.40 for C-H. Yousif and Al-Shahristani (1891,) described a rapid instrumental method for simultaneous detn. of S and V in various Iraqui crude oils by XRF using radioisotope exciting radiation and a semiconductor detector. Changes in crude oil d. or compn. did not affect the S detn. The V concn. measurement was influenced by the S content of the crude. Tolles and Turner (168L) compared the analytical capabilities of coherent anti-Stokes Raman spectroscopy ( I ) , Raman scattering (11) and absorption spectroscopy. 'I'he signal-to-noise ratio for each was derived themetica the calcns. were applied to H?, N2,0, and CO under a temps. and partial pressures. At pressures -sis. Spent carrier fluid from the sepn. can be used as the diluting stream. Dilution ratios of total fluid to sample are possible within a range from 1 : 2 0 to 2OO:l. The technique is particularly useful in the dilution of a material such as C-black feedstock oii or other heaty oil, and was demonstrated on C,H,. Aihaiigh and Query ( 3 L ) used exclusion chromatography with multiple detectors for following compositional changes of petroleurn residuals during desulfurization. Detectors included a differential refractometer, a I - V absorption detector. and an improved FID. The method was applied to residual samples before and after desulfurization 147c and 0 . 6 % . resp.) t o determine changes in weight, S.and aromatic distribiitions as a function of size and mol. wt. Shen and Bradley i153L) developed a versatile 1115 inlet system for high-boiling liquid samples and for thermoanal) of nonvolatile materials. T h e system uses a seal maric of DuPont Vespel (to 3.50 "C) for the high-temp. vacuum F t q e and glass-lined stainless steel tubing for most of the sarnp!e lines. T h e system can he applied to high t)oiling petroleum cuts in the boiling range from 600 "F to at least 1300 O F . McLafferty and Bockhoff (202L) explored the sensitivity. selectivitym and value of the analbTica1 information obtained by mass sepn. and mass spectral characterization OlS/ hIS) applied t o a variety of org. mixts. Identific,ation utilizes collision activation (CA) and metastable ion (LII) mass spectra. Interpretation of MI/CA mass spectra of mol. (M9, (M+ H ) + and fragment ions using known correlations can provide valuable structural information. Thiciphene. tetrahydropyran. and n-propylbenzene can be detected in gasoline at levels of iva, 15, 23 (1976). (76C) Robinson, J. W., Kiesel, E. L., Goodbread, J. P., Bliss, R., Marshall, R., Anal. Chim. Acta. 92. 321 (1977). (77C) Ruo. T. C. S., Selu'cky, M. L.. Strausz, 0. P., Anal. Chem., 49, 1761 (1977). (78C) Schulz, H., ErdoelKohle, Erdgas, Petrochem. Brennst, Chem.. 30, 182 (1977). (79C) Sekiyu Gakkai Shi, 20 1143 (1977). (8OC) Sheen, Thomas L., Proc. Int. Sch. Hydrocarbon Meas, 49, 128 (1974). (81C) Shikhalizade, P. O., Yusufzade, A. A , , Safarov. G. I . , Sitaraman, I z v . Vyssh. Uchebn, Zaved., Neft Gaz, 19, 60 (1976). (82C) Shinagawa, K., Hishiyama, S., Ito, S., Kayama, K., Taniguchi, S., Jpn. Kokai 76 00394,January 6, 1976: C . A . , 85, 28274w (1976). (83C) Shishkina, M. V., Chertkox. Ya. B., Kirsanova, T. I., Neffekhimiya, 17, 297 (1977). 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Offen., 2639851, March 17, 1977. (96C) Zeiaskowski, C. A., Carlisi, J. J., U.S. Patent, 3 955 927, May 11, 1976. (97C) Zhukhovitskii, A. A., Novikova, L. G.. Yanovskii, S. M.. Kanunnikova, E. V., Shvartsman, V. P., Zh. Anal. Khim., 3 0 , 2251 (1975). (98'2) Zrelov, V. N.. Marinchenko, N. I., Boiko, L. V., Postnikova. N. G., Krasnaya, L. V., Khim. Tekhnol. Top/. Masel(8), 57 (1977). (99C) Zueva, N. A., Chuevskaya, A. I., Shadrin, L. P., Prom-st. Sint. Kauch., 1976(12). 21; C . A . , 87, 41474x (1977). Lubricants, Olls, and Greases (1D) Adinoff, E., Drakos, I., Kostello. E.M., Soc. Automat. Eng.. Fuels Lubric. Meet., (Tulsa 617-9177), Paper No. 770641, 6 pp, (2D) Agnesi, M., Arrigoni, V., Polinelli, E., Lanza, G. P,., Tribol. Lubrificazione, 11, 139 (1976); C . A . , 87, 1 0 4 1 2 1 ~ (1978). (3D) Ahlborn, G. H., A m . SOC.Lubr. Eng., Trans., 20, 209 (1977). (4D) Asseff, P. A., Soc. Automat. Eng., Fuels Lubric. Meet., (Tulsa 6/7-9/77), Paper No. 770642, 11 pp. (5D) Baldwin. B . A., A m . SOC. Lubric. Eng., Trans., 19. 335 (1976). (6D) Bartl, P., Schaaff, A., Zeman, A., Dtsch. Ges. Mineraloelwiss; Kohlechem. e . v . , Compend., 1977-78, 176. (7D) Beerbower, A., Lubr. Eng., 32, 285 (1976). (8D) Blaine, R. L., NLGI(Nat. Lubric. Grease Inst.) Spokesman. 40, 94 (1976). (9D) Blanco, M., Ion (Madrid), 35, 507 (1975); A . A . . 31, 26169 (1976). (10D) Blum. A., Nowak. Z.. Wachal, A,. Tech. Smarownicza, 1976(4). 114; C'.A., 87, 87456w (1977). (11D) Bogdanova, G. F.. Ivanova, E. A., Levin, A. Y., Fufaev. A. A , , Volkova, V. N., Neftepereab. Neftekhim. (Moscow),1976 (9), 20. (12D) Bose, A. C., Khus. E. E., Tewskbury, E. J., Am. SOC.iubric. Eng., Trans.. 19, 287 ( 1 976). (13D) Brooks, F. C., Hopkins. V.. ibid., 20, 25 (1977). (14D) Buyanova, Z. I., Dagaev, V. A . , Maskaev, A. K.. Tanchuk. Y . , Zh. Prikl. Khim. (Lenninorad).50. 1353 11977). (15D) Castle, P. li., Greenhow, E.'J., Inst. Pet. Meth., IP 75-015, (1975) 16 PP. (16D) Chernova, K. S., Mikheichev, P. A.. 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(18D) Curcic, M., Goriva Maziva, 14, 3 (1975). (19D) Czichos, H., Grimmer, W., Mittmann, H. U., Wear, 40, 265 (1976). (20D) Driatskaya, Z. V., Zhmykhova. N. M., Mkhchiyan, M. A,, Arenbrister, L. P., Rasshir. Utochnenie Programmy Issled. Neftei, Sb. Izbr. Dokl. Mater. Vses. NauchnO-Tekh. Konf., 1975, (Pub. 1976) 86; C.A.,88, 123484k (1978). (21D) Duval, M., Lamarre, C., I€€€ Trans. Electr. Insul. 1977, 340. (22D) Ellison, L. E., U.S. Patent 4029554, June 14, 1977. (23D) Farmer, S., Chem. Ind. (London), 1975 (24), 1061. (24D) Fassel, V. A., Peterson, C. A., Abercrombie, F. N., Kniseley, R. N., Anal. Chem., 48, 516 (1976). (25D) Fialko. M. M.. Balashova. A. N.. Zh. Anal. Khim., 30. 1637 (1975). (26D) Grampurohit, S. V., Rao, P.M.R., Indian J . Pure Appl. Phys., 15, 424 (1977): C . A . , 87, 1 8 6 8 6 8 ~(1978). (27D) Ibid., Indian, A . E . C . Bhabha At. Res. Cent. (Rep.),1976, 853;C . A . , 86., 1 . 5.7.9.8. -1 ~ 11977), (286) Grigor'eva, N. I.. Lapin, V. P., Shor. G. I . , Ivankina. E. B., Badyshtova, K. M., Zuev, G. V.. Khim. Tekhnol. Topi. Massel, 6 , 55 (1976). (29D) Grigor'ev, P. F., Tyurin, Y. A., Trusenev, M. G., Vakhmyanina, M. M., ibid., 11, 55 (1977). (30D) Grimmer, G., Boehnke, H., Chromatography, 9, 30, 1976. (31D) Hala, S., Kuras, M., Zachar, P., Sb. Vys. S k . Chem.-Techno/.Praze, Techno/. Paliv, 1976(D 33), 305. (320) Halasz, I., Erdoel. Kohle, Erdgas. Petrochem. Brennst. Chem.. 30, 228 (1977). (33D) Hillman, D. E., Lindlev, H. M., Paul, J. I., Pickles, D.. B r . Polym. J . , 7, 397 (1975). (34D) Hoffmann, H. E., Altmann, F.. Schmierungstechnik, 8, 59 (1977). (35D) Hoffmann. H. E., Nathansen, H., Altmann, F.. Jena Rev., 21, 302 (1976); C . A . . 87. 104116e 11978). (36D) House, J. L., Hagnauer: G. L., U . S . Natl. Tech. Inform. Serv., ADIPB Rep., 1976, AD-A038840, 13 pp, (37D) Johnson, T. W.. O'Shaughnessy, M. T., SOC.Automat. Eng., Spec. Publ., 416, 57 (1977). (38D) Kaegler, S . H., Erdoel Kohle, Erdgas. Petrochem.. Brennst. Chem., 29, 362 (1976). (39D) Kamykowski. E. A., Schneid. E. J., Kuehne. F J. D'Agostino, M. D., Proc. 3rd. Conf. Appl. Accel., 1974 (1975). (40D) Kapoor, S. K., Singh, I.D., Gupta, P. L., Indian J Technol., 15, 162 (1977). (41D) Kas'yan, 0. S., Volnyanskaya, N. V., Zavod. Lab., 44, 58 (1978). (42D) Ke, P. J., Ackman, R. G.. Guzman-Henriquez, B. L., Anal Chim. Acta, 87, 445 (1976). (430) Kolbin, M. A., Vasil'eva, R. V.. Shklovskii, Y . A,, Khim. Tekhnol. Topl. Massel, 2, 54 (1978). T r . , Vses. Nauchno-Issled. (44D) Kotova, G. G.. Sosina, N. S., Zimina, K. I., I n s t . Pererab. Nefti, 1976(14), 234. (45Dl Kozak. P.. Rabl, V., Kubelka, V.. Sb. Vys. S k . Chem.-Techno/. Praze, Technol. Paliv, 1976 (D 33), 367. (46D) Krawetz, A. A., Krawetz, G. A., Tovrog, T., U . S . Natl. Tech. Inform. Serv., ADIPB Rep., 1976, AD-A037299, 349 pp. (47D) Kudryavtseva, N. A,, Fufaev, A. A., Lulova, N. I., Borshchevskii, S. B., Chesnokova. R. I . , Zavod. Lab., 43, 986 (1977). Fufaev, A. A,. Borschevskii, S. 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