Henry JS Sand (1873-1944), A Well-Remembered ... - ACS Publications

Chapter 32

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Henry J. S. Sand (1873-1944), A Well-Remembered Tutor John T. Stock Department of Chemistry, University of Connecticut, Storrs, CT 06268 The name "Sand" usually conjures up only a particular electrochemical equation. Older workers can recall the flow of papers from what is now the City of London Polytechnic, where Sand and his students made notable advances in the practice of electrogravimetric analysis. Actually Sand's Ph.D., obtained under Bamberger, was in organic chemistry. Nevertheless he soon began electrochemical work, but by no means restricted himself to this field. Studies on the dissociation pressures of alkali metal bicarbonates and on fermentation by yeast cells are examples of his diverse interests. He held several patents on glass working and the like. His joint authorship of "Dyestuffs and Coal Tar Products" showed that he had not forgotten his doctoral area. John Stock was in Sand's lecture group in 1936 and had one of Sand's few but very able graduate students as laboratory supervisor. Nowadays, most chemists know the name "Sand" only because it appears attached to a particular equation in texts that describe chronopotentiometry. This technique can be useful in the diagnosis of electrode reactions (l). A current step i is impressed across an electrochemical cell containing unstirred solution, the potential of the working electrode is measured with respect to time and the transition time T is noted. According to the Sand equation, the product iT1/2 should be constant for an uncomplicated linear diffusion-controlled electrode reaction at a planar electrode. Sand did the work that led to this equation before my time. However, I was around when Sand and his students were developing apparatus and techniques that greatly influenced electrogravimetric analysis. Like other gravimetric processes, electrogravimetry is now overshadowed by more rapid methods. This deposition method, capable of giving high precision and accuracy, 0097-6156/89/0390-0469$06.00/0 © 1989 American Chemical Society

Stock and Orna; Electrochemistry, Past and Present ACS Symposium Series; American Chemical Society: Washington, DC, 1989.


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has at least one satisfying advantage; if a metal is being determined, it is usually obtained in the elementary state. The technique is faster than "precipitate" gravimetry; routine electrogravimetric depositions can sometimes be run in a few minutes. Henry Julius Salomon Sand was born on December 7, 1873, in Dundee, Scotland, and was educated in that city. He then went to Germany, where Walther Hempel, Professor at the Technical University of Dresden, was one of his teachers. Hempel is best remembered for his work on gas analysis. Sand then moved to Switzerland, to become a student at the Zurich Polytechnicum. There he obtained his Ph.D degree under the direction of Bamberger. Sand's first publication, jointly with Bamberger and Busdorf, appeared in June, 1898 (2). It was based on his thesis work and was submitted from the Analytical Laboratory of the Polytechnicum! However, it concerns typical "react and isolate" organic chemistry. I never thought to ask Sand about this, but I imagine that his "analytical chemistry" was largely concerned with the tedious business of numerous combustion analyses of his products! Returning to Britain, he spent a short period with William Ramsay at University College, London. Having by then discovered the noble gases of the atmosphere, Ramsay was famous. Here Sand began the work that eventually led to the "Sand equation." What a switch from classical-style organic chemistry! He became Bowen Research Scholar at Mason University College (later, Birmingham University) in 1899, working under Percy Frankland. Here he continued the work begun in London, publishing a full account in 1901 (3). This contains both theory and an extensive description of the apparatus and experiments that Sand developed to test his ideas on acidified copper sulfate solution. He noted that stirring can arrest hydrogen evolution that occurs when the solution is not stirred. Sand referred to this observation when he began his work on electrogravimetric analysis. This places him at the threshold of the present-day interest in hydrodynamic voltammetry. In 1901, Sand became Lecturer and Demonstrator at University College, Nottingham, and remained there for about 13 years. Here he continued his electrochemical investigations (4,5), when a definite trend towards analytical chemistry occurred. He studied the trace determination of arsenic (6), the estimation of the acidity of tanning liquors (7,8), including the description of an improved hydrogen electrode, and the absorption of oxygen by effluents (9). Accounts of his work on the rapid electrolytic deposition and separation of metals began to appear in 1907 (10-14). This involved the development of improved electrode systems and other equipment (15, 16). He received the D.Sc. degree from the University of Birmingham in 1905. Not all of Sand's efforts at Nottingham were devoted to analytical chemistry. With R.M. Caven, he studied the dissociation pressures of various alkali metal bicarbonates (17,18). Diffusion in liquids obviously interested him (12,20). Some other publications from the Nottingham period concern the radiative evaporation of liquids (2l) and the sealing of wires into glass (22). He was granted several patents, including one for sealing


32. STOCK

Henry J. S. Sand

metal to glass (23) and glass (2k).

471 another

for making

"bubble-free silica


Career at the Sir John Cass Technical Institute In 1914, Sand moved back to London as Senior Lecturer in Chemistry at the Sir John Cass Technical Institute (now the City of London Polytechnic). This photograph (Figure l) may have been made during the early years of his tenure. He became Head of the Department of Inorganic and Physical Chemistry in 1921 (there was no separate Department of Analytical Chemistry) and retained this position until he retired in 1938. In the 1920's, Sand wrote a number of papers concerning the phenomenon of overpotential (25-29). His other interests are reflected in publications concerning a steam drying oven (30), the cadmium vapor lamp (31), the anomaly of strong electrolytes (32), an arrangement for alternating current electrolysis (33), and the evaporation of liquids (34). Sand had not forgotten his "organicker" training; he was joint author of the text "Dyestuffs and Coal Tar Products," a fourth edition of which appeared in 1926 (35). Sand retained his interest in electrolytic deposition (36). However, real emphasis on this field did not return until the end of the 1920's. Then he opened the series of papers on electrogravimetry that came from his Department with accounts of new apparatus (37) and separations by internal electrolysis (38). Sand certainly attracted some very able research students. He and his research group gave great impetus to the practice of electrogravimetric analysis. Interestingly enough, Sand's name appears only on the papers that concern the separation of lead and antimony (with E.M. Collin) (32), then graded potential separations (40), antimony alloys (4l), and microelectrolytic techniques (42) (all with A.J. Lindsey). Dr. Lindsey tells me that Sand was most anxious that the credit should go to those who needed it much more than he. Accordingly, other papers by his students do not bear his name, except for an acknowledgment of his interest. Collin wrote three papers on the determination of bismuth (43-45) and one on spelter analysis (46). Lindsey, who became a faculty member of the Institute and was one of my instructors, continued the electrogravimetric program, including the microchemical aspects. His improved microelectrode system became a standard item (47-53). Other active members of Sand's research group were A.J. Fife (5k-60), S. Torrance (6l-66), and F.C. Kny-Jones (51,67-69). Sand's retirement in 1938 might have reduced this outflow of results. The collapse was due to the outbreak of World War II in 1939. Lindsey joined the Royal Air Force; doubtless the other members of the group were soon involved in the war effort. I became an undergraduate in Sand's lecture group in 1936. Holding a full-time job while studying in the evening, I was a bit older than most of the other students. This helped me to understand Sand's obviously failing powers due, I suspect, to ill health. Nearing the end of my list of assigned analytical experiments, I asked "HJS" if I might go on to some of the




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Figure 1. Henry J. S. Sand (Reproduced by permission of the Journal of Chemical Education 1977, 54, 637.)



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Henry J. S. Sand

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electrogravimetric techniques that were being developed by his graduate students. I remember his penetrating look and his remark, "we'll see!" He was a kindly man, but I think that he had had his fill of undergraduates in general! I never did get to "try out" but, several decades later, did actually publish something on electrogravimetry (70). In his retirement, Sand wrote "Electrochemistry and Electrochemical Analysis." This appeared in three slender volumes during the War years (7l). Volume II, which carries the subtitle "Gravimetric Electrolytic Analysis and Electrolytic Marsh Tests," surveys apparatus and experimental techniques and gives concise instructions for the performance of numerous analyses. It acknowledges Sand's earlier contribution to Lunge and Keane's encyclopedic work (72). Even in his later years, Sand retained his interest in fundamentals in his case, heats of reaction (73). Fittingly, his last paper (74), published in the year of his death, reflects a major theme (microelectrolytic methods of chemical analysis) of the research group that he founded. Obviously, Sand was a talented chemist whose activities ranged very widely. Advances in Electrogravimetry Electrogravimetry has quite a long history. The technique was successfully performed in the 1860's by both Wolcott Gibbs and by Luckow. By 1903, both Gooch and Exner had shown that analysis could be speeded up by the use of vigorous stirring. Deposition on the large area afforded by a gauze type of platinum electrode had been practiced by Winkler in 1899. Controlled-potential deposition, proposed by Kiliani in 1893, had been demonstrated by Freudenberg some ten years later. Sand did not claim to have discovered any of these phenomena. His great contribution was to tie them all into a theoretically sound and completely practical procedure. He realized that the key was the design of an electrode system that provided maximum stirring efficiency, low electrolytic resistance, permitted the use of a reference electrode for closely monitoring the potential of the working electrode, and allowed easy washing and drying before the reweighing. His answer was to use an inner electrode that could be rotated in a glass sleeve within the outer, or working, electrode. The interelectrode distance of only a few millimeters enabled the electrolytic resistance to be kept small. A glass plate was fixed diametrically within the rotating electrode to increase the stirring efficiency. Because the working electrode surrounds the rotating electrode and thus confines the interelectrode current, the potential of the working electrode can be closely measured by placing the fine tip of a reference electrode near the working electrode. Freudenberg did not use a third, or reference, electrode. More than one half of Sand's long paper (10) is devoted to experimental details for determinative separations and the results obtained. Sand's original electrodes were constructed from about 2 ounces of platinum. Much later (37), he redesigned the system. The outer electrode, which usually carries the analytical deposit, was reduced in weight to about 10 grams, and was easier to wash, dry,



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and weigh. This electrode slips over the legs of a glass tripod that is part of the guiding system for the rotating electrode. This electrode system and the stand that carried the drive, meters, and other auxiliary equipment became commercially available. Sand coined the term "internal electrolysis" to describe a method introduced by Ullgren in 1868. The principle is that of a short-circuited cell; no external power supply is needed. In his apparatus (38), designed originally for the determination of bismuth and copper in lead bullion (44), hollow lead anodes are used. These are immersed in acidified lead nitrate solution contained in parchment thimbles. The lid of the cell supports these anodes, four glass rods that guide the platinum gauze cylindrical cathode, and also the glass tube that serves as a bearing for the centrifugal stirrer. As far as I can ascertain, the originals of the apparatus developed by Sand and by Lindsey have vanished. In the case of the electrodes, this is not surprising; platinum has a high value in the scrap-metal market. Apparently, we have yet another instance of "a scientist's instruments are his successors' junk!" Acknowledgment Part of this work was carried out under Program of the Science Museum, London.

the Research

Fellowship

Literature Cited 1. Heineman,, W.R.; Kissinger, P.T. Laboratory Techniques in Electroanalytical Chemistry: Dekker: New York, 1984, p. 132. 2. Bamberger, E.; Büsdorf ,H.; Sand, H. Ber. 1898, 31, 1513-22. 3. Sand H.J.S. Phil. Mag., 6th series, 1901, 1, 45-79. 4. Sand, H. Z. Elektrochem. 1904, 10, 452-54. 5. Sand H.J.S. Phil. Mag., 6th series, 1905, 9, 20-41. 6. Sand, H.J.S.; Hackford, J.E. Trans. Chem. Soc. 1904, 85, 1018-28. 7. Sand, H.J.S.; Law, D.J. J. Soc. Chem. Ind. 1911, 20. 3-5. 8. Wood, J.T.;Sand, H.J.S.; Law, D.J. J. Soc. Chem. Ind. 1911, 29, 872-77. 9. Sand, H.J.S.; Trotman, S.R. J. Soc. Chem. Ind. 1912, 31, 1166-67. 10. Sand, H.J.S. Trans. Chem. Soc. 1907, 91, 373-410. 11. Sand, H.J.S. Trans. Chem. Soc. 1908, 93, 1572-92. 12. Sand, H. Z. Elektrochem. 1907, 13, 326-27. 13. Sand, H.J.S. Analyst 1908, 33, 395-6. 14. Sand. H.J.S. Chem. News 1909, 100, 269-70. 15. Sand, H.J.S. Trans. Faraday Soc. 1909, 5, 159-64. 16. Sand, H.J.S. Trans. Faraday Soc. 1911, 6, 205-11. 17. Caven, R.M.; Sand, H.J.S. Trans. Chem. Soc. 1911, 99, 1359-69. 18. Caven, R.M.; Sand, H.J.S. Trans. Chem. Soc. 19l4, 105, 2752-61. 19. Sand, H.J.S. Proc. Roy. Soc. 1905, 74, 356-69. 20. Slater, A.; Sand, H.J.S. Trans. Chem. Soc. 1910, 97, 922-27. 21. Sand, H.J.S. J. Soc. Chem. Ind. 1907, 26, 1225-26.


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22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43. 44. 45. 46. 47. 48. 49. 50. 51. 52. 53. 54. 55. 56. 57. 58. 59. 60. 61. 62. 63. 64. 65. 66. 67. 68. 69. 70.

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Sand, H.J.S. Proc. Phys. Soc. London 1914, 26, 127-30. Sand, H.J.S.; Reynolds, E. Brit. Pat. 23 854, 1913. Sand, H.J.S. Brit. Pat. 15 639, 1913. Sand, H.J.S.; Weeks, E.J. Trans. Chem. Soc. 1923, 2896-2901. Sand, H.J.S.; Weeks, E.J. J. Chem. Soc. 1924, 125, 160-68. Sand, H.J.S.; Grant, J.; Lloyd, W.V. J. Chem. Soc. 1927, 378-96. Sand, H.J.S. Rec. Trav. Chim. 1927, 46, 342-49. Sand, H.J.S. Trans. Faraday Soc. 1930, 26, 19-26. Sand, H.J.S. J. Chem. Soc. 1929, 214. Sand, H.J.S. Phil. Mag. 1920, 39, 678-79. Sand, H.J.S., Phil. Mag. 1923, 45, 129-44. Sand, H.J.S.; Lloyd, W.V. J. Chem. Soc. 1926, 2971-73. Sand, H.J.S.; Brown & Son. Brit. Pat. 314 923, 1928. Becall, T.; Challenger, G.; Martin, G.; Sand, H.J.S. Dyestuffs and Coal Tar Products, 4th ed.; Technical Press, Ltd.: London, 1926. Sand, H.J.S. Brit. Assn. Adv. Sci., 4th Rept. 1921, 346-56. Sand, H.J.S. Analyst (London) 1929, 54,, 275-82. Sand, H.J.S. Analyst (London) 1930, 55, 309-12. Collin, E.M.; Sand, H.J.S. Analyst (London) 1931, 56, 90-93. Lindsey, A.J.; Sand, H.J.S. Analyst (London) 1934, 59, 328-35. Lindsey, A.J.; Sand, H.J.S. Analyst (London) 1934, 52, 335-38. Lindsey, A.J.; Sand, H.J.S. Analyst (London) 1935, 60, 739-43. Collin, E.A. Analyst (London) 1929, 54, 654-55. Collin, E.A. Analyst (London) 1930, 55, 312-18. Collin, E.A. Analyst (London) 1930, 55, 680-82. Collin, E.M. Analyst (London) 1930, 55, 495-501. Lindsey, A.J. Analyst (London) 1935, 60, 598-99. Lindsey, A.J. Analyst (London) 1935, .60, 744-46. Lindsey, A.J. Analyst (London) 1938, .63, 159-62. Lindsey, A.J. Analyst (London) 1938, 63, 425-26. Kny-Jones, F.C.; Lindsey, A.J.; Penney, A.C. Analyst (London) 1940, 65, 498-501. Lindsey, A.J. Analyst (London) 1948, 13, 67-73. Lindsey, A.J. Analyst (London) 1948, 73, 99. Fife, J G. Analyst (London) 1936, 6l, 681-84. Fife, J.G.; Torrance, S. Analyst (London) 1937, 62, 29-31. Fife, J.G. Analyst (London) 1937, 62, 723-27. Fife, J.G. Analyst London) 1938, 63, 650-51. Fife, J.G. Analyst (London) 1940, 65, 562-63. Fife, J.G. Analyst (London) 1941, 66, 192-93. Fife, J.G. Metallurgist 1948, 30 (177), 167-69. Torrance, S. Analyst (London) 1936, 61, 688-89. Torrance, S. Analyst (London) 1937, ,62, 719-22. Torrance, S. Analyst (London) 1938, 63, 104-07. Torrance, S. Analyst (London) 1938, 63, 488-92. Torrance, S. Analyst (London) 1939, 64, 109-11. Torrance, S. Analyst (London) 1939, 64, 263-64. Kny-Jones, F.C. Analyst (London) 1939, 64, 172. Kny-Jones, F.C. Analyst (London) 1939, 64, 575-77. Kny-Jones, F.C. Analyst (London) 1941, 66, 101-04. 01m, D.D.; Stock, J.T. Mikrochim. Acta 1977, 2, 575-82


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71. Sand, H.J.S. Electrochemistry and Electrochemical Analysis; Blackie: London, Vol. I, 1939; II, 1940: III, 1941. 72. Lunge, G.; Keane, C.A., Eds.; Technical Methods of Chemical Analysis; Gurney & Jackson: London, 1914. 73. Sand, H.J.S. Nature 1937, 140, 809-10. 74. Sand, H.J.S. Metallurgia 1944, 30 (176), 107-09.


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Henry JS Sand (1873-1944), A Well-Remembered ... - ACS Publications

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