- Email: [email protected]
Geoffrey Pilcher and his scientific career
M-3132(P) J. Chem. Thermodynamics 1995, 27, 561–564
Geoffrey Pilcher and his scientific career Manuel A. V. Ribeiro da Silva Centro de Investigac¸a˜o em Quı´ mica, Faculdade de Cieˆncias, Universidade do Porto, P-4050 Porto, Portugal
Geoffrey Pilcher was born in Portsmouth on 8 November 1927. He attended St. Mary’s Elementary School from 1932 to 1939, and subsequently the Portsmouth Southern Grammar School from 1939 to 1946. During the Second World War, 1939–1945, the Secondary School was evacuated from Portsmouth to Brockenhurst, in the New Forest. Neither school exists nowadays; both sets of school buildings were destroyed by German bombing during the war. After finishing secondary education, Geoff obtained an Exhibition to Magdalen College, Oxford, from 1946 to 1953. In Oxford, his Tutor and later his Supervisor, was the distinguished chemist Professor L. E. Sutton. In 1950, Geoff received his B.A. degree with First Class Honours in Chemistry, and in 1953 he obtained his M.A. and D. Phil., with a thesis entitled ‘‘Heats of Formation of Chemical Compounds and their Relation to Molecular Structure’’. This title seems to have set the tone for the major part of Geoff’s research work from then on! For his D. Phil., Geoff constructed an aneroid bomb calorimeter, with which he started his long and outstanding work in combustion calorimetry. His first published measurement was for succinic acid: −Dc u°/(kJ·g−1 )=(12638.121.8), in exact agreement with the value now recommended when succinic acid is used as an auxiliary test substance. Following the completion of his D. Phil., Geoff went to the United States, from 1953 to 1956, to become a Post-Doctoral Research Fellow at the Carnegie Institute of Technology (now Carnegie-Mellon University), Pittsburgh, PA, working with Professor F. D. Rossini on the development and construction of a low-temperature calorimeter to be used for determining purities of hydrocarbon samples from equilibrium temperatures, during fractional melting. In 1956 Geoff returned to the U.K., for another Post-Doctoral Research Fellowship (1956 to 1962), now at the University of Manchester, with Professor Henry A. Skinner, to construct and operate a flame-calorimeter. This was the beginning of a long and fruitful career of 37 years of research and teaching at the Victoria University of Manchester. In 1968 he married Marion Steel, and they raised one child: Nicholas John. During these decades, the field of thermochemistry went through a very active and flourishing period, with many research laboratories, all over the world, engaged not only in the establishment and development of new experimental techniques, but also 0021–9614/95/060561+04 $08.00/0
7 1995 Academic Press Limited
562
Geoffrey Pilcher and his scientific career
on the measurement of very accurate and precise thermochemical quantities. It was exactly during this time that the University of Manchester had the luck of bringing together, in the same Department, Hank Skinner and Geoff Pilcher, no doubt two of the most high-standing British thermochemists of this century. With two very different styles and personalities, Hank and Geoff complemented very well each other’s attitudes through research, and have been close colleagues for 25 years, supporting each other’s research efforts and often collaborating on joint research projects. This was one of the reasons why the University of Manchester took not only an outstanding place in the world’s thermochemistry research but, most surely, the leading place in the U.K. After his Post-Doctoral Fellowship in Manchester, Geoff became, successively, Lecturer (1962 to 67), Senior Lecturer (1967 to 91), and Reader (1991) until his retirement in 1993, at the Department of Chemistry of the University of Manchester. His major research endeavours have focussed on the accurate measurement of standard molar enthalpies of formation of several different classes of chemical compounds and their relation with molecular structure, using combustion (flame, static bomb, and rotating bomb) and solution-reaction calorimetry. Between 1963 and 1972, in eight papers on flame calorimetry were reported 27 enthalpies of formation which included the alkanes C1 to C5 , some simple and cyclic ethers, formaldehyde and glyoxal, as well as the alkyl chlorides C1 to C3 . A hot-zone calorimeter, developed from the flame calorimeter, was used to determine the enthalpies of formation of the copper and lead oxides by reduction, and of the hexacarbonyls of chromium, molybdenum, and tungsten, by thermal decomposition. In 1982, the combustion-calorimetric equipment at the National Physical Laboratory, Teddington, was transferred to Manchester enabling an increase in activity in bomb calorimetry. Static-bomb measurements were made on substituted pyridines, substituted catechols, aminophenols, quinones, cyclohexanediones, and hydroxynaphthalenes. Studies on lactones, cyclic anhydrides, and cyclic imides showed, for the first time, that the strain energy in a 6-membered ring could exceed that in a 5-membered ring. More recently, in eight publications were reported enthalpies of formation of compounds containing the (N+–O−) dative covalent bond in order to investigate how the molar dissociation enthalpy of this bond is affected by its molecular environment. Rotating-bomb measurements were made on several bromine compounds: CBr4 , the bromobenzoic acids, 2,4,6-tribromophenol, and 2,4,6-tribromoaniline. Sulphur compounds have also received proper attention: some dialkylammonium dialkyldithiocarbamates, thiobenzamides, and some amino sulfonic acids were studied. Whenever feasible, enthalpies of sublimation were measured, by microcalorimetry, to derive enthalpies of formation in the gaseous state. Reaction-solution calorimetric measurements have been a continuing interest. Studies have been made on various metal complexes, mainly pentanedionates and oxinates, to derive metal–ligand binding enthalpies. The method of hydrolysis with oxidation on compounds containing metal–metal, double, triple, and quadruple bonds led to values for the binding energies of these unusual multiple bonds. Enthalpies of micellization of both cationic and anionic surfactants were studied by microcalorimetry and the interaction between surfactants and various catalases, e.g. Aspergillus niger.
Geoffrey Pilcher and his scientific career
563
Geoff always supported and encouraged the efforts of young scientists and made his large expertise and laboratory facilities available to collaboration in research. He enjoyed the stimulation of over 40 Research Students, Research Associates, Post-Doctoral Fellows, and Visiting Research Workers, from several different countries, mainly U.K., Portugal, Spain, Soviet Union, Australia, Egypt, P. R. China, Malaysia, Uganda, Saudi Arabia, Guyana, etc. Among other foreign research laboratories, Geoff maintained a strong scientific collaboration with Professor F. Andruzzi, University of Pisa, Italy, on the measurement of the enthalpies of polymerization of strained ring compounds, with Professor W. E. Acree, Jr. University of North Texas, U.S.A., on the determination of Dm(N–O) in a variety of compounds containing this dative covalent bond, and with myself, at the University of Porto, Portugal, on determination of enthalpies of formation of various ligands and of metal–ligand binding enthalpies in complexes. Looking back at Geoff’s scientific work (he has authored and co-authored more than 120 publications in national as well as international journals, chapters of scientific books, etc.), one is struck by the diversity of topics with which he has dealt; he also lectured at several international conferences and Post-Graduate Schools, in several countries, mainly in Finland, Italy, Portugal, and Spain. The contribution of Geoff to the development and construction of scientific equipment can not be overlooked; neither can his outstanding contribution to the thermochemical scientific literature, both through the Royal Society of Chemistry Annual Reports on Thermochemistry and especially for the widely known and famous Cox and Pilcher Book, published in 1970, which has been known as the Thermochemistry Bible. Although published 25 years ago, this book is still very useful in every laboratory and there are no doubts that it marked the beginning of a new epoch in the thermochemical literature. Although Geoff devoted most of his time to his research, he also became involved in other important activities related to thermochemistry: he was Secretary of the Experimental Thermodynamics Conferences at Lancaster (1972), Leeds (1974), Bristol (1976), as well as Chairman for the same Conference at University College London in 1978, and served on the Advisory Board of Journal of Chemical Thermodynamics (1979–1981, 1982–1984, 1987–1989, 1990–1992, and since 1994). His activities were officially honoured in 1987 by the awarding of the Royal Society of Chemistry Medal for Thermodynamics. Besides his interests in science, Geoff likes cats, gardening, and photographing wild flowers. Although this is a sad moment, since all of us have deeply to regret the closing down of such an important thermochemistry laboratory as the Manchester University one, where for more than four decades, under the leadership of both Professor Henry Skinner and Dr Geoffrey Pilcher, some of the most valuable and elegant work in British thermochemistry was performed, I am most honoured in having promoted the publication of this special issue of The Journal, which is not only a tribute to the outstanding work of Hank and Geoff, but a mark of appreciation of the excellent work in the field of thermochemistry performed by the Department of Chemistry of the University of Manchester.
564
Geoffrey Pilcher and his scientific career
This special issue of The Journal of Chemical Thermodynamics is dedicated to Geoffrey Pilcher. It consists of 15 papers on various aspects of chemical thermodynamics, contributed by collaborators and friends, to show how he is appreciated by them.
Geoffrey Pilcher and his scientific career Manuel A. V. Ribeiro da Silva Centro de Investigac¸a˜o em Quı´ mica, Faculdade de Cieˆncias, Universidade do Porto, P-4050 Porto, Portugal
Geoffrey Pilcher was born in Portsmouth on 8 November 1927. He attended St. Mary’s Elementary School from 1932 to 1939, and subsequently the Portsmouth Southern Grammar School from 1939 to 1946. During the Second World War, 1939–1945, the Secondary School was evacuated from Portsmouth to Brockenhurst, in the New Forest. Neither school exists nowadays; both sets of school buildings were destroyed by German bombing during the war. After finishing secondary education, Geoff obtained an Exhibition to Magdalen College, Oxford, from 1946 to 1953. In Oxford, his Tutor and later his Supervisor, was the distinguished chemist Professor L. E. Sutton. In 1950, Geoff received his B.A. degree with First Class Honours in Chemistry, and in 1953 he obtained his M.A. and D. Phil., with a thesis entitled ‘‘Heats of Formation of Chemical Compounds and their Relation to Molecular Structure’’. This title seems to have set the tone for the major part of Geoff’s research work from then on! For his D. Phil., Geoff constructed an aneroid bomb calorimeter, with which he started his long and outstanding work in combustion calorimetry. His first published measurement was for succinic acid: −Dc u°/(kJ·g−1 )=(12638.121.8), in exact agreement with the value now recommended when succinic acid is used as an auxiliary test substance. Following the completion of his D. Phil., Geoff went to the United States, from 1953 to 1956, to become a Post-Doctoral Research Fellow at the Carnegie Institute of Technology (now Carnegie-Mellon University), Pittsburgh, PA, working with Professor F. D. Rossini on the development and construction of a low-temperature calorimeter to be used for determining purities of hydrocarbon samples from equilibrium temperatures, during fractional melting. In 1956 Geoff returned to the U.K., for another Post-Doctoral Research Fellowship (1956 to 1962), now at the University of Manchester, with Professor Henry A. Skinner, to construct and operate a flame-calorimeter. This was the beginning of a long and fruitful career of 37 years of research and teaching at the Victoria University of Manchester. In 1968 he married Marion Steel, and they raised one child: Nicholas John. During these decades, the field of thermochemistry went through a very active and flourishing period, with many research laboratories, all over the world, engaged not only in the establishment and development of new experimental techniques, but also 0021–9614/95/060561+04 $08.00/0
7 1995 Academic Press Limited
562
Geoffrey Pilcher and his scientific career
on the measurement of very accurate and precise thermochemical quantities. It was exactly during this time that the University of Manchester had the luck of bringing together, in the same Department, Hank Skinner and Geoff Pilcher, no doubt two of the most high-standing British thermochemists of this century. With two very different styles and personalities, Hank and Geoff complemented very well each other’s attitudes through research, and have been close colleagues for 25 years, supporting each other’s research efforts and often collaborating on joint research projects. This was one of the reasons why the University of Manchester took not only an outstanding place in the world’s thermochemistry research but, most surely, the leading place in the U.K. After his Post-Doctoral Fellowship in Manchester, Geoff became, successively, Lecturer (1962 to 67), Senior Lecturer (1967 to 91), and Reader (1991) until his retirement in 1993, at the Department of Chemistry of the University of Manchester. His major research endeavours have focussed on the accurate measurement of standard molar enthalpies of formation of several different classes of chemical compounds and their relation with molecular structure, using combustion (flame, static bomb, and rotating bomb) and solution-reaction calorimetry. Between 1963 and 1972, in eight papers on flame calorimetry were reported 27 enthalpies of formation which included the alkanes C1 to C5 , some simple and cyclic ethers, formaldehyde and glyoxal, as well as the alkyl chlorides C1 to C3 . A hot-zone calorimeter, developed from the flame calorimeter, was used to determine the enthalpies of formation of the copper and lead oxides by reduction, and of the hexacarbonyls of chromium, molybdenum, and tungsten, by thermal decomposition. In 1982, the combustion-calorimetric equipment at the National Physical Laboratory, Teddington, was transferred to Manchester enabling an increase in activity in bomb calorimetry. Static-bomb measurements were made on substituted pyridines, substituted catechols, aminophenols, quinones, cyclohexanediones, and hydroxynaphthalenes. Studies on lactones, cyclic anhydrides, and cyclic imides showed, for the first time, that the strain energy in a 6-membered ring could exceed that in a 5-membered ring. More recently, in eight publications were reported enthalpies of formation of compounds containing the (N+–O−) dative covalent bond in order to investigate how the molar dissociation enthalpy of this bond is affected by its molecular environment. Rotating-bomb measurements were made on several bromine compounds: CBr4 , the bromobenzoic acids, 2,4,6-tribromophenol, and 2,4,6-tribromoaniline. Sulphur compounds have also received proper attention: some dialkylammonium dialkyldithiocarbamates, thiobenzamides, and some amino sulfonic acids were studied. Whenever feasible, enthalpies of sublimation were measured, by microcalorimetry, to derive enthalpies of formation in the gaseous state. Reaction-solution calorimetric measurements have been a continuing interest. Studies have been made on various metal complexes, mainly pentanedionates and oxinates, to derive metal–ligand binding enthalpies. The method of hydrolysis with oxidation on compounds containing metal–metal, double, triple, and quadruple bonds led to values for the binding energies of these unusual multiple bonds. Enthalpies of micellization of both cationic and anionic surfactants were studied by microcalorimetry and the interaction between surfactants and various catalases, e.g. Aspergillus niger.
Geoffrey Pilcher and his scientific career
563
Geoff always supported and encouraged the efforts of young scientists and made his large expertise and laboratory facilities available to collaboration in research. He enjoyed the stimulation of over 40 Research Students, Research Associates, Post-Doctoral Fellows, and Visiting Research Workers, from several different countries, mainly U.K., Portugal, Spain, Soviet Union, Australia, Egypt, P. R. China, Malaysia, Uganda, Saudi Arabia, Guyana, etc. Among other foreign research laboratories, Geoff maintained a strong scientific collaboration with Professor F. Andruzzi, University of Pisa, Italy, on the measurement of the enthalpies of polymerization of strained ring compounds, with Professor W. E. Acree, Jr. University of North Texas, U.S.A., on the determination of Dm(N–O) in a variety of compounds containing this dative covalent bond, and with myself, at the University of Porto, Portugal, on determination of enthalpies of formation of various ligands and of metal–ligand binding enthalpies in complexes. Looking back at Geoff’s scientific work (he has authored and co-authored more than 120 publications in national as well as international journals, chapters of scientific books, etc.), one is struck by the diversity of topics with which he has dealt; he also lectured at several international conferences and Post-Graduate Schools, in several countries, mainly in Finland, Italy, Portugal, and Spain. The contribution of Geoff to the development and construction of scientific equipment can not be overlooked; neither can his outstanding contribution to the thermochemical scientific literature, both through the Royal Society of Chemistry Annual Reports on Thermochemistry and especially for the widely known and famous Cox and Pilcher Book, published in 1970, which has been known as the Thermochemistry Bible. Although published 25 years ago, this book is still very useful in every laboratory and there are no doubts that it marked the beginning of a new epoch in the thermochemical literature. Although Geoff devoted most of his time to his research, he also became involved in other important activities related to thermochemistry: he was Secretary of the Experimental Thermodynamics Conferences at Lancaster (1972), Leeds (1974), Bristol (1976), as well as Chairman for the same Conference at University College London in 1978, and served on the Advisory Board of Journal of Chemical Thermodynamics (1979–1981, 1982–1984, 1987–1989, 1990–1992, and since 1994). His activities were officially honoured in 1987 by the awarding of the Royal Society of Chemistry Medal for Thermodynamics. Besides his interests in science, Geoff likes cats, gardening, and photographing wild flowers. Although this is a sad moment, since all of us have deeply to regret the closing down of such an important thermochemistry laboratory as the Manchester University one, where for more than four decades, under the leadership of both Professor Henry Skinner and Dr Geoffrey Pilcher, some of the most valuable and elegant work in British thermochemistry was performed, I am most honoured in having promoted the publication of this special issue of The Journal, which is not only a tribute to the outstanding work of Hank and Geoff, but a mark of appreciation of the excellent work in the field of thermochemistry performed by the Department of Chemistry of the University of Manchester.
564
Geoffrey Pilcher and his scientific career
This special issue of The Journal of Chemical Thermodynamics is dedicated to Geoffrey Pilcher. It consists of 15 papers on various aspects of chemical thermodynamics, contributed by collaborators and friends, to show how he is appreciated by them.