Progress in Equipment and Tools: 1959

MICROCHEMICAL

Progress HOWARD

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387-396 (1960)

1959

J. FRANCIS, JR., Pennsalt Chemicals Corporation, Philadelphia, Pennsylvania

This review of “Equipment and Tools” considers only those items appearing in the literature during 1959. A further qualification is imposed that the particular reference must, in the reviewer’s estimation, be not only novel, but also of interest or of potential value to the microchemist. While the greater part of the papers considered in this review will be treated in tabular form (Table I) it may be well to comment, on a few of the more outstanding contributions and trends. An interesting and very ingenious development in t,he field of molecular weight determination is the recent use of thermistors in the vapormetric method. In principle the method can be traced back through the literature for at least 25 years; however it was not until Mtiller and Solten utilized the tremendous advantage of thermistors as temperature-sensitive elements that the method reached a Neumayer,hl Wilson and Bini’Ol level amiable to routine application. and Hofstader31 independently improved the technique by employing a hanging drop of solution on the thermistor bead. This method appears to be one of the most promising developments in recent years. Ogg,63 in a private communication, stated that in a preliminary A. 0. A. C. survey on molecular weight determination the results submitted by collaborators using the Thermistor-Vaporimetric method appeared to be superior to values obtained by other procedures. The method is not only thermodynamically rigorous, but also has the added advantage of requiring a truely microsized sample, e.g., one drop of solution. Automatic and recording titrators appear to have an enduring popularity. It is perhaps in the micro level of volumetric determinations that the value of instrumental means of detect,ing the equivalence point of titrations has its greatest value. 387

388

H. J. FRANCIS, TABLE

Equipment

for

Elemental determination

Functional group determinations

Titrimetric procedures

Spectrophotometry

Method

JR. I

or device

References

Sutomatic apparatus for the determination of carbon and hydrogen Bomb combustion technique for determination of carbon, hydrogen, and boron Comparative study of combustion catalyst efficiency Automatic vacuum fusion apparatus for the determination of gases in metals Nitrogen determination by the Dumas method Modified nitrometers for the Dumas determination Modified micro-Kjeldahl still Traces of nitrogen by the ter Meulen method Modified Schijniger flasks Oxy-hydrogen burners for determining halogens, sulfur, and metals Still for fluoride distillation Still for the separation of mercury from organic compounds Determination Determination Determination Determination Determination Determination Equipment for

of carbon monoxide of carbon dioxide of methane of acetone in biological of acetyl groups of unsaturation ultramicro analysis

fluids

Automatic and recording titrators Photometric titrators Amperometric circuits, electrodes, and equipment Coulometric devices High frequency apparatus Burets, stirrers, stopcock turners Electrodes Illuminators Flame photometers Ultraviolet photometer Continuous calorimetric analyzer Modified absorption cell to allow photometry without separation of extract Test tube adapter for Beckman Model DIJ

38,83 3 33 102 30,34 1,40,55 5 76 17,49 221 80 13

47,87 46 91 93 38 14 9 36,96,100 32,71,89 25, 69, 84 23,44 45 35,65 4,57,85 99 l&26,42 88 24 29 104

EQUIPMEXT TABLE Equipment

Equipment and circuitry for the Fischer method By direct amperometric measurement instrumental method Equipment for paper chromatograph> Centrifugal force application Modified ring oven

Chromatography

Molecular weight determinations Determination of physical properties

Electrophoresis Weighing

Miscellaneous apparatus

References

or device

27,50 74,94 19 22

Semimicro distilling equipment Molecular stills Steam distillation Fraction collector for vacuum distillation

Water determination

Sampling and handling

389

TOOLS

I (continued)

Method

for

Distillation

Zone refining sublimation

AKD

Thermistor

vapormetric

Karl 8, 43,53 and 41 15,56, 68, 73 48 6 31,61,101

method

Equipment for the determination points Boiling point apparatus

of melting 67,95 12

and Fractionation via sublimation Devices for and theoretical zone refining

77,79 treatment’

of

Gas samplers Polystyrene sponges as sample carriers Millipore filters as sample carriers Vacuum manipulation of samples Electrophoretic devices Recording thermobalance, vacuum and pressure Electra-automatic balance Balance table and mounting Device for reducing weighings to standard conditions Fabricating and calibrating polyethylene pipets Micro solvent extractor Thermistorized differential thermal analysis equipment Micro filtration Solution evaporators

30, 52, 72 28, 59, 92 90 37 75 11, 50,86,98 70 8” 78 62

10,57 81 64 16 7,54,66,

10, 3

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H. J. FRANCIS,

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The classical Karl Fischer method of determining water has had a renewed interest; a number of papers have dealt with the reduction of the size of apparatus or the increase in sensitivity as a means of extending the method to lower concentrations of water. Although variations on the Schiiniger oxygen flask theme appear to have reached a plateau, there is an increasing interest in flame comAlbert and Granatelli2 bustion methods in elemental determinations. and Ehrenberger 21 have used modified oxy-hydrogen burners in determining halogens and in the determination of arsenic. As in the original Wickbold method,s’ materials difficult to decompose by other means are handled with ease and a high degree of precision and accuracy. A very valuable adjunct to these methods would be the estimation of carbon simultaneously with the other elements. A. noteworthy piece of equipment which should prove to be of great interest to the clinical and biological chemist is the unitized ultramicro analytical system as devised by Dr. M. C. Sanz of Geneva, Switzerland, and recently made available by the Spinco division of Beckman Instruments.s The complete equipment consists of a spectra-calorimeter utilizing a stationary self-emptying cuvet, an ultramicro centifuge, a titrating unit capable of being read to 0.005 ~1. and various kits of packaged reagents to perform those tests One of the most novel features common to the clinical laboratory. of this equipment is the use of polyethylene microliter pipets mounted directly on the caps of the individual reagent bottles, the pipets are self-filling, self-leveling, unbreakable, and require no cleaning. While zone refining has not had the impetus as predicted in last year’s review, it is heartening to see a number of excellent papers on equipment for this processs2J2 and the paper by Herington30 on the theoretical aspects and analytical applications of this principle. A very noticeable trend in the scientific journals is the ever-increasing number of papers dealing with instrumentation, and particularly electronic devices. Many of the papers appear to be of interest more to those skilled in the “Electronic Art” than to be of first-hand value to the practicing microchemist. A question arises in the reviewer’s mind whether the analytical and microchemical journals are the proper outlets for these contributions. Another criticism is on the most exasperating practice of describing electronic circuitry in an incomplete and in many cases erroneous manner. Having need for an instrument described in the literature, building MICROCHEMICAL

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the instrument, and then discovering that it will either not work at all or will not perform as claimed in the original paper is an experience which will not be unfamiliar to many readers. Of course the reason (or reasons) for this disappointment is usually found in t’he next month’s issue under the heading (‘Corrections” or “A.ddenda.” Censure may be well directed at the author, but at the same time a quizzical eye may be cast at the persons refereeing these papers. Perhaps it will become necessary for the editorial boards to add an electronic expert to their membership, or at least to insist that the instrument can be duplicated from instructions furnished in the text by anyone with a reasonable mechanical aptitude. A number of authors have very graciously supplied additional detailed plans and instructions to those persons sincerely interested in constructing those instruments and equipment described in their papers. This practice may be the solution to avoid cluttering up the scientific journals with details not related to the chemistry or analytical techniques involved in the paper or method under consideration.

References 1. Abramson, E., and J. Laurent, Mikrochim. Acta, 1959, 786. “Sur le microdosage de traces d’azote dans les substances organiques par la methode modifike de Pregl-Dumas.” 2. Albert, D. K., and L. Granatelli, Anal. Chem., 31, 1593 (1959). “Determination of microgram quantities of arsenic in napthas with oxy-hydrogen burner.” 3. Allen, H., Jr., and S. Tannenbaum, Anal. Chem., 31, 265 (1959). “Analytical procedure for compounds containing boron, carbon, and hydrogen.” 4. Al-Qaraghuli, N., and K. G. Stone, Anal. Chem., 31, 1448 (1959). “Chloride-free reference electrode for use in acetic acid solvent.” 5. Asami, T., Anal. Chem., 31, 630 (1959). “A simple micro-Kjeldahl apparatus.” 6. Ballczo, H., Mikrochim. Acta, 1959, 314. “Eine Erweiterung der Ringofen-methode.” 7. Barr, L. W., and D. A. Blackburn, J. Sci. In.&., 36,197 (1959). “Simple evaporator for radioactive metals.” 8. Bastin, E. L., H. Siegel, and A. B. Bullock, Anal. Chem., 31, 467 (1959). “Microdetermination of water by titration with Fischer reagent.” 9. Beckman/Spinco Division, Stanford Industrial Park, Palo Alto, California. “An ultramicro clinical system.” 10. Biggs, P. H., J. Sci. In&., 36, 45 (1959). “Method for filling capillary pipets with mercury for calibration purposes.” 11. Bloemendal, H., and L. Bosch, Anal. Chem., 31, 1446 (1959). “Improved cutting device for starch block electrophoresis.”

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12. Bohme, H., and R. Bohm, Mikrochim. Aeta, 1959, 270. “Eine Mikromethode zur Siedepunktsbestimmung mit direkter Temperaturmessung.” 13. Brooks, H. E., and L. E. Solomon, Analyst, 84, 622-629 (1959). “The determination of mercury by distillation from its compounds and preparations.” 14. Chaphekar, M. R., and T. S. Gore, Mikrochim. A&z, 1959,664. “Microdetermination of unsaturation in organic compounds.” 15. Chesbro, W. J., J. Chem. Educ., 36, 83 (1959). “A simple rapid method for loading paper chromatograms.” 16. Corliss, J. M., Chemist Analyst, 48, 16 (1959). “Expedient for microfiltration.” 17. Corner, M., Analyst, 84, 41 (1959). “Rapid micro-determinat,ion of organically bound halogens, arsenic, phosphorus and boron.” 18. Dreisbach, R. H., Anal. Chem., 31, 479 (1959). “Simplified recording photometer for flame analysis.” 19. Duboff, G. S., An&&, 84,.619 (1959). “An all-glass self-cleaning steamdistillation apparatus.” 20. Eder, K., Mikrochim. Actu, 1959, 631. “Uber eine einfache Schnellmethode der Stickstoffmikrobestimmung nach Dumas.” 21. Ehrenberger, L., Mikrochim. Actu, 1959,192. “Neue Schnellmethode zur mikroanalytischen Bestimmung von Chlor, Brom, und Fluor in organischen Substanzen.” 22. Evans, D. W. S., Chem. & Ind. (London), 1959, 219. “Useful fraction collector for small-scale vacuum distillation.” 23. Feldberg, S. W., and C. E. Bricker, Anal. Chem., 31, 1852 (1959). “Ion exchange membranes in coulometry.” 24. Ferrari, A., F. M. Russo-Alesi, and J. M. Kelly, Anal. Chem., 31, 1710 (1959). “A completely automated system for the chemical determination of streptomycin and penicillin in fermentation media.” 25. Freedman, R. W., Anal. Chem., 31, 1287 (1959). “Transistorized deadstop end point detector.” See also Anal. Chem., 31,1686 (1959). 26. Fuwa, K., R. E. Thiers, and B. L. Vallee, Anal. Chem., 31, 1419 (1959). “A burner for cyanogen flame spectroscopy.” 27. Hall, R. A., Anal. Chem., 31, 437 (1959). “Vapor take-off still head.” 28. Hanson, D. N., and A. Maimoni, Anal. Chem., 31, 158 (1959). “Gasblending apparatus.” 29. Henderson, S. R., and L. J. Snyder, Anal. Chem., 31,2113 (1959). “Modified absorption cell and cell compartment for the Beckman Model DU spectrophotometer.” 30. Herington, E. L. G., Analyst, 84, 680 (1959). “Zone melting with some comments on its analytical potentialities.” 31. Hofstader, R., American Cyanamid Company, Bound Brook, N. J., private communication. 32. Holasek, A., H. Lieb, and K. Winsauer, Mikrochim. Acta, 1959, 402. “Ein Mikrophotometer fir kolorimetrische Titrationen.” 33. Horacek, J., and Korbl, Mikrochim. Actu, 1959, 303. “Determination of carbon and hydrogen in organic compounds. I. Efficiency of combustion catalysts.” MICROCHEMICAL

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34. Hozume, K., and S. Amako, M
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55. Miller, D. M., and R. A. Latimer, Anal. Chem., 31, 1926 (1959). “Simplified nitrometer for use in the Dumas nitrogen determination.” 56. Miller, G. J., and R. J. McColloch, Anal. Chem., 31, 320 (1959). “A simple ascending paper-strip chromatography device for rapid exploratory studies.” 57. Leeds and Northrup Company, 4934 Stenton Avenue, Philadelphia, 44, Pa. “Miniature pH electrodes, Model 124138 pH assembly.” 58. Miiller, R. H., and H. J. Solten, Anal. Chem., 25, 1103 (1953). ‘(Use of thermistors in precise measurement of small temperature differences.” 59. Neale, E., and B. J. Perry, Analyst, 84, 226 (1959). “The sampling and analysis of toxic vapours in the field.” 60. Nerheim, A. G., Anal. Chem., 31, 2114 (1959). “Improved head and flask for miniature distillation.” 61. Neumayer, J. J., Anal. Chim. Ada, 20, 519 (1959). “The determination of molecular weight using thermistors.” 62. van Niewvenburg, C. J., Anal. Chim. Acta, 20, 127 (1959). “Reduction of micro and semi-micro weighings to normal temperature and normal pressure.” 63. Ogg, C. L., U. S. Agricultural Research Service, Eastern Utilization Research Branch, Wyndmoor, Pa., private communication. 64. Pakulak, J. M., Jr., and G. W. Leonard, Anal. Chem., 31, 1037 (1959). “Thermistorized apparatus for differential thermal analysis.” 65. Pefar, M., Micro&em. J., 3, 557 (1959). “Some simple devices for microtitration.” 66. Perold, G. H., Mikrochim. Actu, 1959,251. “Aspects of organic analysis. VII. Dust free evaporation of solutions for crystallisations on a small scale.” 67. Pinkus, A. G., and P. G. Waldrop, Mikrochim. Acta, 1959, 772. “A simple method for obtaining melting points of compounds reacting with moisture or oxygen.” 68. Porteous, J. B., J. Chromafog., 2, 58 (1959). “A semiautomatic multipipetting device for paper chromatography.” 69. Price, D., and L. R. Coe, Analyst, 84, 55 (1959). “The volumetric determination of chloride in titanium and zirconium by a polarization end-point procedure.” 70. Rabatin, J. G., and C. S. Card, Anal. Chem., 31, 1689 (1959). “Simple recording thermobalance for vacuum and pressure studies.” 71. Rehm, C., J. I. Bodin, K. A. Connors, and T. Higuchi, Anal. Chem., 31, “Circulation apparatus for photometric titrations.” 483 (1959). 72. Ronald, A. P., Anal. Chem., 31, 964 (1959). “Automatic multistage semimicro zone melting apparatus.” 73. Roth, L., Mikrochim. Actu, 1959, 582. “Papierscheiben-Saulenchromatographie.” 74. Sanders, G. R., and H. L. Helwig, Anal. Chum., 31, 484 (1959). “A molecular distillation unit for organic particulates in air.” 75. Schacher, G. P., Anal. Chem., 31, 161 (1959). “Device for opening small sealed objects under vacuum.” 76. Schluter, E. C., Anal. Chem., 31, 1576 (1959). “Trace analysis for total nitrogen in petroleum fractions.” MICROCHEMICAL

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77. Schmidt, G., Mikrochim. Acta, 1959, 406. “Ein Vakuumsublimationsgerat sur Trennung und Reinigung kleiner Substansmengen.” 78. Schoniger, W., Mikrochim. Acta, 1959, 382. “Erschutterungsfreie Aufstellung von Mikrowaagen.” 79. Shead, A. C., Mikrochim. Acta, 1959, 657. “Sublimation giving crystals suited for the measurement of profile angles.” “De80. Singer, L., and W. D. Armstrong, And. Chem., 31, 105 (1959). termination of fluoride in blood serum.” 81. Slee, L. J., G. Phillips, and E. N. Jenkins, Analyst, 84,596 (1959). “The determination of small amounts of neptunium in plutonium metal.” 82. Smith, B. O., and J. W. Stevens, J. Sci. Znstr., 36, 206 (1959). “Quick acting chemical balance.” 83. Stehr, E., Anal. Chem., 31, 1274 (1959). “Carbon and hydrogen microdetermination by automatic combustion control.” titration with 84. Stock, J. T., Microchem. J., 3,54 (1959). “Amperometric two indicator electrodes and allied techniques.” 85. Stock, J. T., Chemist An&yet, 48,8 (1959). “Construction of thread-type salt bridge and immersion-type silver-silver chloride electrode.” 86. Strickland, R. D., P. A. Mack, F. T. Gurule, T. R. Podleski, 0. Salome, “Determining serum proteins and W. A. Childs, Anal. Chem., 31, 1410 (1959). gravimetrically after agar electrophoresis.” 87. Sverak, J., Mikrochim. Acta, 1959,908. “Beitrag sur Bestimmung kleiner Mengen Kohlenoxyd in Wasserstoff und methanhaltigen Gasen.” 88. Thiers, R. E., M. Margoshes, and B. L. Vallee, Anal. Chem., 31, 1258 “Simple ultraviolet photometer.” (1959). 89. Thoburn, J. M., C. M. Jankowski, and M. S. Reynolds, Anal. Chem., 31, of a commercial automatic calorimetric titrator.” 124 (1959). “Development 90. Thomas, R. S., Mikrochim. Actu, 1959, 830. “A convenient specimen carrier for use with the quartz-fiber fishpole microbalance.” 91. Toby, S., Anal. Chem., 31, 1444 (1959). “Simple apparatus for microdetermination of methane.” 92. Tong, B. L., and D. G. Timms, Chem. & Znd. (London), 1959,155. “Molecular sieves as gas samplers.” 93. Tsao, M. U., G. H. Lowrey, and E. J. Graham, Anal. Chem., 31, 311 of acetone in biological fluids.” (1959). “Microdetermination 94. Ungnade, H. E., Anal. Chem., 31, 1126 (1959). “Modified molecular pot still.” 95. Ungnade, H. E., E. A. Brixner, and E. A. Igel, Anal. Chem., 31, 1432 (1959). “Melting point apparatus for simultaneous observation of samples in transmitted and reflected light.” 96. Waterbury, G. R., Anal. Chem., 31, 1138 (1959). “Modified SargentMalmstadt automatic titrator for remote control use with plutonium solutions.” 97. Wickbold, R., Angew. Chem., 64, 133 (1952). “A new rapid method for determining halogen in organic substances.” 98. Wieme, R. J., C&n. Chim. Acta, 4,317 (1959). “Improved technique of agar-gel electrophoresis on microscope slides.”

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99. Wilkins, D. H., Talanta, 2, 88 (1959). “Apparatus for titrations using ultra-violet light.” 100. Williams, R. C., R. S. R&Fin, and L. A. Mounter, ilnal. Chem., 31, 611 (1959). “A recording titrator.” 101. Wilson, A., and L. Bini, paper presented at the North Jersey Section of the American Chemical Society, Meeting-in-Miniature, January 26, 1959. “A thermistor-molecular weight apparatus.” 102. Yanagisawa, S., M. Seki, Y. Watanabe, and S. Nakamura, Mikrochim. Ada, 1959, 1. “Automatic micro-analytical apparatus for the determination of gases in metals.” 103. Zacharius, R. M., and S. Krulick, Anal. Chem., 31,211l (1959). “Heavy metal contamination from use of some rotary evaporators.” 104. Zak, B., and L. A. Williams, Chemist Analyst, 48, 17 (1959). “Test-tube adapter for Beckman DU spectrophotometer.”

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