AAS-Biographical memoirs-Alan Parker

Jim Parker was born on 21 December 1933 at South Perth, Western Australia, the elder son of John and Winifred. When he died suddenly on the morning of 30 August 1982, Australian chemistry lost one of its most distinguished scholars at the highest point of his career.

Jim's father's family had lived in Victoria where John had won a scholarship to Wesley College, Melbourne, and had gone on to study engineering at the University of Melbourne. At Queen's College, John was a contemporary of Noel Bayliss (later Professor Sir Noel Bayliss CBE, FAA) who was later greatly to influence his son's career in chemistry. In the late 1920s, after graduation, John moved to 'the West' to a post with the WA Main Roads Department. In a long and successful career with the Western Australian Government he became successively Director of Engineering in the Public Works Department, Coordinator of Development associated particularly with the iron ore fields in the Pilbara region of the North-west, and Chairman of the State Electricity Commission. He was knighted in 1975.

Jim's maternal grandmother had been a school teacher on the Kalgoorlie goldfields and had married a farmer in the Harvey region, where Winifred grew up and Jim subsequently spent many school holidays.

After being dux of Wesley College, Perth, in 1950, Jim entered the University of Western Australia, graduating in 1954 with first class honours and distinctions in both organic and physical chemistry. His honours research project, supervised by Joe Miller, introduced him to physical organic chemistry and, in particular, to aromatic nucleophilic substitution. He continued with this work for his doctorate, although he considered for some time undertaking instead a joint project with Sir Noel Bayliss and staff from the Institute of Agriculture of the University of Western Australia on nitrogen fixation.

Parker's PhD thesis, 'The Mechanism of Aromatic Nucleophilic Substitution Reactions', submitted in 1957, was praised highly by the examiners and led to five publications. He became a competent experimenter and quickly developed a sense of how good an experiment needed to be. He had the capacity to remind many of us, to our advantage, of the futility of striving for ever-increasing accuracy in data to test theories which, when applied to condensed phases, can only be approximate anyway. He had seemingly endless patience in the accumulation of data through repetitive activity and his PhD research involved at least 7,000 electrometric titrations.

Parker quickly realised the need to travel overseas for post-doctoral experience, and between 1958 and 1961 spent periods in a number of leading laboratories. He went first to the University of Southern California where Norman Kharash introduced him to sulfur chemistry. There he learned some new experimental techniques and, of far greater importance, he gained a new skill in the construction of internationally significant review articles. This skill he maintained and developed to the stage where we can now judge that the capacity to assemble his own data with that of others, to weigh the evidence, to identify the irrelevant and to point clearly to the path forward, was one of his greatest contributions to chemistry.

While in California, on 12 July 1958 Parker married Lesley Hannah Paterson who, in 1957, had graduated as top student in organic chemistry at the University of Western Australia, a distinction she would, no doubt, have achieved even without Jim's constant attention. Lesley's commitment, her ambitions for her family and for Jim, her capacity to establish her own professional career as she pursued her accepted primary role of mother to four sons and wife of a scientist on the move, must not be underestimated.

In 1959 Jim moved, in common with many other young Australian chemists, to University College London, where he spent two years with Sir Christopher Ingold and E.D. Hughes. It was here that his insight into non-aqueous chemistry developed. His early work had shown that remarkable changes in rate of reaction, sometimes of the order of one-million-fold, could be brought about by changing from protic to dipolar aprotic solvents as the medium for reaction. In London he became particularly interested in the use of the solvents dimethyl sulfoxide (DMSO), dimethylformamide (DMF) and dimethylacetamide (DMA). His review entitled 'Effects of Solvation on the Properties of Anions in Dipolar Aprotic Solvents', written during a short stay in Bergen in late 1960, gave a significant qualitative explanation of the effects of solvents on the rates of organic substitution reactions and became one of the most quoted articles in the history of scientific literature.

The Institute for Scientific Information recently confirmed that, by the first quarter of 1986, this paper had no fewer than 870 citations in the Science Citation Index, making it far and away the most-cited paper from the journal in which it appeared, Quarterly Reviews of the Chemical Society. The impact of this and three other reviews written between 1961 and 1969 on the scientific understanding of the role of the solvent in determining the yield and rate of a chemical reaction cannot be overstated. In this field Jim Parker was, for a decade, a leading figure. He forced many other chemists to realise that many of the properties they had ascribed to chemicals were predominately properties of the surrounding medium.

After his visit to Bergen as a Royal Norwegian Research Council Fellow (August 1960-February 1961), Parker returned to London for ten more months on an ICI Fellowship. Then, in January 1962, he rejoined the University of Western Australia as a Senior Lecturer in Organic Chemistry. He was promoted to Reader in 1966.

During the period 1962-69, Parker expanded his interests from rate data to a range of thermodynamic parameters including solubilities, vapour pressures and electromotive force measurements. Three fundamental conflicts were personally absorbing throughout this period. First, as he developed his ideas qualitatively about the nature of ionic solvation, he saw the need to quantitate these effects and also to develop a thermodynamic basis for them. He was concerned greatly about the validity of the extra-thermodynamic assumptions that were needed to divide the measured properties of total electrolytes between the anions and cations that constituted those electrolytes. Secondly, he was concerned about the discrepancy between the accuracy he could obtain on transfer between solvents, based upon solubility and EMF data in particular, and the more conventional data produced by physical chemists studying smaller concentration effects in a single solvent. Thirdly, he was constantly concerned about the validity of his method of applying solvent transfer activity coefficients to transition state theory in accounting for rate variations.

By the time he published his Chemical Reviews article in 1969, Parker had resolved these problems in his own mind, helped by the industry and friendship of Dr Bob Alexander who collected the vast amount of data that gave credibility to Jim's theories about solvent transfer free energy and activity. Throughout, Jim had been primarily concerned with anions and molecules in organic reactions. Any cation data came about incidentally, mostly because cations were, of necessity, present in his solutions. Some additional information on cations was collected from the study of cobalt chemistry in non-aqueous solvents by one of us (D.W.W.).

An accidental happening in the late 1960s is worth interpolating here. In one of his electro-chemical experiments aimed at determining anion activities in one of his non-aqueous solvents, Parker used a silver/silver chloride electrode. He was somewhat surprised when the silver chloride – known by most school students to be 'insoluble' (i.e. in water) – dissolved. The electrode was ruined and for some time he considered this to be a 'failed' experiment. However, in science, no experiment is a failure – some merely give unexpected results. Jim's experience of the incredible change in solubility of silver chloride resulting from a change of solvent was the forerunner of many such discoveries of far-reaching importance in the next few years.

In 1969, Parker moved to a position as Professorial Fellow in the Research School of Chemistry at the Australian National University in Canberra. This shift to the ANU totally changed the thrust of his work. He now had available to him a whole new range of techniques, an increase in manpower and, of course, more time to think. He embarked upon a study of cation solvations that was to lead to many exciting discoveries in the field of mineral chemistry.

The mental jump from organic reaction mechanisms to practical mineral chemistry might seem too large for the average mind, but in his case it was completely logical. Though Parker had for twenty years studied pure chemistry and had been justly acclaimed by his peers, he felt uneasy at the thought that his results were not being used by anyone outside academic laboratories. He himself had not been in an industrial chemistry laboratory, and he knew virtually nothing about economics or about the chemical engineering that is used to produce almost everything we use in our everyday lives. Furthermore, especially at ANU, he was surrounded by brilliant young graduates who were finding it difficult to obtain employment after getting their PhDs. He began to talk to industrial chemists and soon became convinced that academic chemists must learn to explain their new discoveries to chemists in industry and help them to understand how 'pure' results could be developed in an applied sense. In this he was undoubtedly influenced by his father, Sir John Parker, who, as has been mentioned, played an important role in the development of new large-scale mineral industries in Western Australia, commencing about 1966.

At Christmas 1971, while on holiday in Perth, Jim visited the Western Mining Company's Kwinana nickel refinery, purely as a tourist, and obtained a sample of the by-product copper sulfide that was apparently difficult to process to obtain copper metal by normal chemical methods. Let us tell the beginning of the 'copper story' in his own words:

Early in 1972, back in Canberra, it occurred to me that new methods of copper processing might be a spectacular project to undertake with good PR appeal. The environmental problems of S0₂ emission by copper smelters were a very live issue in 1972 and the concepts of 'added value' and processing of minerals in Australia by Australian technology were popular ones with both major political groups. My problem was, how could I apply to copper processing my knowledge of the rates and mechanisms of organic reactions and the chemistry of ions in non-aqueous solvents? This was the only type of advanced chemistry where I had any real expertise, indeed I had not thought deeply about the chemistry of copper, or of any other metal, since my days as an undergraduate chemist, and my teaching had always been the chemistry of carbon compounds.

A few weeks later, on a Sunday evening, I was baby sitting at a friend's home and was bored. While aimlessly scribbling on the back of an envelope I came to the following very simple conclusions about the Western Mining copper sulphide and how to process it.

My pure research on solvation of ions had told me that cuprous ions, Cu⁺, were strongly and specifically solvated by acetonitrile (CH₃CN), a common and cheap organic solvent. Acetonitrile, however, is a poor solvent for protons. Copper sulphide, Cu₂S, is only very very slightly soluble in water: its solubility product is about 10^-50. Even in strong sulphuric acid very little of it dissolves. After some simple calculations, using some concepts I had developed about equilibria in non-aqueous solvents, I predicted confidently that copper sulphide would dissolve readily in anhydrous acetonitrile when a little sulphuric acid was added. The dissolution is represented by the following equation and I predicted a solubility product of about 10⁵.

Cu₂S + H₂SO₄ → Cu₂SO₄ + H₂S
Next morning I suspended copper sulphide in dry acetonitrile in a test tube and added a drop of dry sulphuric acid. Success! The prediction was right; we had a new method for leaching copper sulphides. There was a vigorous evolution of evil-smelling hydrogen sulphide and all the copper sulphide dissolved to give a clear colourless solution, confirming that, as required by the equation, the product was colourless cuprous sulphate and not the more common blue cupric sulphate solution, CuSO₄. Western Mining copper sulphide reacted even more vigorously than synthetic copper sulphide and dissolved in a few seconds. One day we added water to a colourless solution of cuprous sulphate in anhydrous acetonitrile. The solution was made by our reaction from copper sulphide and sulphuric acid, but this time the solution had aged and was free of the smell of hydrogen sulphide. To our surprise, the solution remained colourless although we had expected blue cupric sulphate. It was left overnight in an open beaker in a fume hood for no particular reason. The next morning the beaker contained blue cupric sulphate solution and bright copper powder. What had happened was that the acetonitrile had evaporated. This left a solution of cuprous sulphate in water. The cuprous ion, Cu⁺, cannot exist in water in the absence of acetronitrile, so two cuprous ions change to copper and cupric ions in a process known as disproportionation. We had 'discovered' a method of copper recovery from solution, a method now known as thermal disproportionation.

Cu₂SO₄/CH₃CN/H₂0
distil
→
CuS0₄/H₂O + Cu↓ + CH₃CN↑

The discoveries that acidic solutions of cuprous sulfate were stable in aqueous solutions containing acetonitrile, and that copper could be recovered from such solutions by thermal disproportionation (distillation), were soon the subjects of provisional patent applications by the Australian National University. Work on the 'ANU Copper Project' then began in earnest, with advice, funding and materials supplied by CSIRO and a variety of Australian companies, in particular Copper Refineries Pty Ltd of Townsville, a subsidiary of MIM Holdings Pty Ltd.

The next discovery was that crude copper or scrap copper could be dissolved into an acetonitrile-water mixture by the action of the relatively common cupric sulfate. The resulting cuprous sulfate solution would yield pure copper metal either by thermal disproportionation as described above or by electro-winning. The latter process would require much less electrical power than the conventional electro-refining process.

Some fourteen provisional patent applications in this area were lodged by the Australian National University during 1972. During 1973 the group received very generous financial support for their laboratory work from Copper Refineries Pty Ltd, together with samples and valuable advice from a variety of other mining companies in Australia. In order to hold and exploit the copper patents, the Australian National University, in the period 1972-73 and under the guidance of Mr Ross Hohnen, set up the wholly owned company ANUMIN Pty Ltd with a nominal capital of $10,000 and an issued capital of seven shares of one dollar.

Approaches to a number of Australian companies and government agencies seeking a joint venture to build a small scale pilot plant were unsuccessful. However, a casual query from the Long Range Development Division of Air Products and Chemicals Inc (APCI), an American company based in Delaware, finally led in June 1975 to an agreement between APCI and Anumin, whereby the former undertook to carry out market research and within two years to design and build a pilot plant for the recovery of copper by the Parker process. APCI would be given exclusive rights to the copper patents throughout the world except in Australia and PNG. In return Anumin would receive royalties from any commercial production.

By the time the APCI agreement was finally signed, Jim had moved to Murdoch University, where he was appointed foundation professor of chemistry in 1974. The Murdoch University Senate set up a Mineral Chemistry Research Unit (MCRU) with Jim as director. He assembled a research team including David Muir and Dion Giles, who had worked with him in developing the patents at ANU, to continue the study of 'non-aqueous hydrometallurgy' with emphasis always on the unique properties of the dipolar aprotic solvents.

With the transfer of Parker's research work to Murdoch, the two universities agreed that the management of Anumin should also be transferred to Western Australia. After protracted negotiations about the legal details, Murdoch became the owner of Anumin in August 1978 by purchasing the seven issued dollar shares and taking over some debts owed by Anumin to ANU. Profits from any future exploitation of the copper patents would be shared between ANU and Murdoch, subject to the commitment to APCI. It was implicit that Murdoch University alone would benefit from the proceeds of work done at Murdoch subsequent to Jim's appointment there.

Unfortunately, the late seventies saw a fall in the price of copper and a slackening world demand for the metal. By early 1980, having already spent about $500,000 on the project, APCI could see no possibility of exploiting the Parker patents in the forseeable future, and invoked the escape clause to terminate the 1975 agreement. Its rights to the copper patents were surrendered back to Anumin. In return APCI, in view of the expense they had incurred, would receive substantial royalties if commercial production ever did eventuate. The collapse of the copper project, which earlier had been optimistically forecast to bring an income of millions to Murdoch, was the first of Jim's great disappointments.

Although this revolutionary new process has not, as yet, been fully applied in the minerals industry, it served to illustrate that, for too long, the practice of chemistry had been retarded by a preoccupation, especially in the industrial sphere, with water as the only solvent.

During the years following Parker's appointment to Murdoch, the research work at MCRU diversified into other fields in addition to the metallurgy of copper. Patents were taken out relating to the extraction of gold and silver, to lithium batteries (in conjunction with CSIRO), to solar cells, and to the zinc-bromine battery.

Amongst several batteries that were receiving world-wide attention at the time, notably the zinc-chlorinehydrate, sodium-sulfur, lithium-ironsulfide, nickel-iron and aluminium-air batteries, the zinc-bromine battery was probably the most favoured for its future potential. Jim's interest in it was at first as a power unit for an electric car, and it was in this connection that he came in contact with the Perth businessman Frank Parry, who had imported one of the first prototype electric cars into Western Australia. Parry later acted in an entrepreneurial capacity for Anumin in the battery project. With the easing of the oil crisis of the 1970s, the interest in the battery shifted to its static use as a load leveller, or as an adjunct to alternative power sources such as wind and solar energy. It derives its energy from the reaction

Zn + Br₂ → Zn²⁺ + 2Br^–

which is reversed in the charging process. Owing to the reactivity of bromine, the electrolyte is of critical importance.

The giant American corporation Exxon had already brought an experimental zinc-bromine battery to an advanced stage using an electrolyte based on a quaternary morpholinium derivative – the Exxon 'oil'. Working with Pritam Singh, Jim found that a laboratory-scale battery using the dipolar aprotic solvent propionitrile (PN) as electrolyte seemed to offer definite advantages over the Exxon oil. With financial help from CRA Ltd and the Swan Brewery, he was able to invite Dr Fritz Will, a senior research electrochemist of the General Electric Company, Schenectady, to come to Perth to evaluate the Murdoch battery. After a study of some three months, Will's comprehensive report in December 1981 concluded that the Parker electrolyte 'exhibits a combination of unique properties which makes it superior, in certain aspects, to the organic bromine complexes employed by Exxon and others. When combined with the advanced battery technology developed at Exxon, an improved zinc-bromine system could indeed result'.

Will's report encouraged Parker to approach Exxon with the suggestion of some form of co-operation. However, at the August 1982 meeting of the Anumin board, he had to report that Exxon had shown no interest. This was only a few days before he died. It was learned afterwards that Exxon was already disposing of its interests in the zinc-bromine battery. During this period Jim also had hopes of a joint venture between CRA and Anumin to develop and manufacture zinc-bromine batteries in Australia. However, after early but slight indications of encouragement, CRA withdrew. This double brake on his hopes to develop the zinc-bromine battery was another major blow to Jim. The disappointments about the copper and the battery projects, together with frustrations to his attempts to commercialize the gold patents, overhung and darkened the weeks before his premature death at the end of August 1982.

In 1983 David Muir wrote:

It would be a tribute to Jim Parker's efforts and achievements if a high technology zinc bromine battery venture came to fruition in WA. We have seen how his ambition to share and apply his knowledge has led him into the fields of organic chemistry, physical and mechanistic chemistry, electrochemistry and mineral chemistry. High technology industries need high technology scientists like Jim who are able to share their expertise with others. They also need graduates who can both specialise and problem-solve yet can look around for new ideas. I hope Jim Parker's example will help produce such scientists and graduates to benefit Australia.

Work on the battery continued under the supervision of Pritam Singh in collaboration with David Muir and Jim Avraamides, with financial support at first from the National Energy Research Development and Demonstration Council and later from the Solar Energy Research Institute of WA. Contact was made with the Energy Research Corporation (ERC), a major US battery and fuel cell company based in Connecticut. ERC had made considerable progress in the design of a zinc-bromine battery using the Exxon oil as electrolyte. Towards the end of 1983 Pritam Singh and Frank Parry visited Connecticut and excited ERC's interest in the Murdoch electrolyte. Pritam Singh made an extended visit to ERC in 1984 to work with the ERC engineers. Anumin's name was legally changed to MURMIN Pty Ltd in April 1985, and then on Boxing Day 1985 a tripartite agreement was signed between Murmin, ERC, and Frank Parry's newly formed company ZBB, for the development and commercialization of the zinc-bromine battery with an exchange of technology between ERC and Murmin. The target for the first large scale model in Western Australia is of the order of 500 kWh capacity.

In his twenty-seven years of research and teaching, Jim Parker made distinguished contributions as a visiting scientist to the University of Bergen, the University of California, Los Angeles (where Saul Winstein played an important role in his development), the Technical University of Vienna and the National Institute for Metallurgy, Johannesburg. He was a Senior Fulbright Scholar in 1965, having previously held a Hackett Studentship of the University of Western Australia (1957), a CSIRO Overseas Studentship (1958), a Royal Norwegian Research Council Fellowship (1960), and an ICI Fellowship (1961). His research awards were many, and numbered among them the Rennie Medal (1963) and the H.G. Smith Medal (1970) of the Royal Australian Chemical Institute. He was elected to Fellowship of the Institute in 1967 and to Fellowship of the Australian Academy of Science in 1979.

His service to the community was never limited by his own academic and research interests. He served on the Council of Wesley College in Perth and participated actively in science education at the secondary school level. He also worked on many State Government advisory committees such as the Solar Energy Research Institute of Western Australia and the Western Australia Mining and Petroleum Research Institute. He served the Royal Australian Chemical Institute as chairman of the Electrochemistry Division and, at the time of his death, was president of the Western Australian Branch.

Sport played an important part in Jim's life and provided an understanding of the community outside academe. His participation in first-grade cricket, golf, hockey, squash and table tennis in earlier years and his continued competitive interest in hockey and golf formed the basis of many friendships.

Few chemists have contributed so widely to theory, practice and application in a career that was short and ended while still at its productive peak. Even fewer have combined this with such open friendship and concern for colleagues and students thus providing others around him with the benefits of wisdom, knowledge, inspiration and good common sense.

He is survived by his wife, Lesley, and four sons.

Acknowledgments

We gratefully acknowledge the assistance of Sir Noel Bayliss and Dr David Muir in the collection of information for this paper, and for reviewing the manuscript.

A.R.H. Cole, Professor of Physical Chemistry, University of Western Australia.

D.W. Watts, Director of the Western Australian Institute of Technology.

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