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From page 147... ... From the mid-1940s to the mid-1990s he established a position of authority on the basic principles behind organic reactions in many ways similar to that of Louis Hammett, who originally coined the term "physical organic chemistry" as the title of his groundbreaking monograph of 1940. Unlike his illustrious predecessor, Grunwald arrived on the scene when most of the traditional barriers between physical and organic chemistry were breaking down and a postwar golden age of enthusiasm and financial support for chemistry was in full swing. Read the entire page →
From page 148... ... 148 B I O G R A P H I C A L M E M O I R S Born in Wuppertal, Germany, in 1923, Grunwald grew up in a middle-class Jewish family. His father had served in the German army and had received terrible wounds that required two years of hospitalization and finally amputation of his leg. Read the entire page →
From page 149... ... Fortunately he was granted a Jewett Fellowship in 1949 to study at Columbia for a year. He had already been identified as a rising star, and in 1949 was recruited to join the chemistry department at Florida State University, which had embarked on a major program hoping to convert it from a prewar teachers college into "the Harvard of the South." In 1952 he married his wife, Esther. Read the entire page →
From page 150... ... During the same period he established himself as a leading authority on the physical chemistry underlying organic reaction mechanisms through his lecture presentations at important conferences and his incisive comments during discussions. The exciting progress being made in mechanistic organic chemistry during this period inevitably led to vigorous arguments at conferences that occasionally became quite Read the entire page →
From page 151... ... During his tenure at Florida State Grunwald also began productive discussions with his colleague, John Leffler, on how the structures of organic molecules affected their thermodynamics in solution and those of associated ions and transition states. The results were published in 1963 as Rates and Equilibria of Organic Reactions, a volume whose lasting influence on the development of organic chemistry is probably second only to Hammett's original monograph. Read the entire page →
From page 152... ... This made it possible for Grunwald and Leffler to probe not only the free energy relationships between rates and equilibria as a function of structure but also correlations of enthalpies of activation with heats of reaction and the corresponding free-energy terms. A solid theoretical understanding developed of how the effects of structure change were related to the energies of neutral reacting species, reactive intermediates (such as ions or radicals) Read the entire page →
From page 153... ... Benefiting from his training in organic chemistry, Grunwald was one of the leaders in recognizing that site-specific solvent-solute interactions could also play an important role. His careful studies of ion solvation in dioxane-water mixtures bear particular comment. Read the entire page →
From page 154... ... This dramatically counter-intuitive discovery played an important role in developing the practical use of a variety of dipolar aprotic solvents and polyethers to selectively tie up organic cations and thereby activate organic anions that otherwise would be associated with their counter-cation, and thus opened up a whole new area of synthetic organic chemistry. In one carefully crafted and analyzed study after another through the years Grunwald and his students added London dispersion forces and hydrogen bonding to the list of important interionic interactions. Read the entire page →
From page 155... ... In 1961 he resigned from Florida State and joined Saul Meiboom, who had the best equipment in the world for studying the systems of interest to Grunwald. The prospect of having hands-on access to this marvelous new tool was overpoweringly attractive. Read the entire page →
From page 156... ... 156 B I O G R A P H I C A L M E M O I R S university. In several chats with him during these years I began to hear wistful comments comparing the sometimes stressful life of total concentration on one or two problems at a research institute to teaching and working with students on a variety of problems and enjoying the interactions with colleagues in different areas of the sciences and other disciplines. Read the entire page →
From page 157... ... Back in the department Grunwald's responsibilities expanded as he became an associate editor for physical organic chemistry for the Journal of the American Chemical Society in 1977, serving for four years under Cheves Walling and later Allen Bard. Earlier he had served on the editorial boards of Accounts of Chemical Research and The Journal of Solution Chemistry. Read the entire page →
From page 158... ... 158 B I O G R A P H I C A L M E M O I R S editors would be familiar to most members of the National Academy of Sciences, but I do not recall having seen them organized and described step by step in one place before. His essay would be of value to any young faculty member entering the complicated and often misunderstood culture of peer review on which so much of the credibility of the scientific effort depends. Read the entire page →
From page 159... ... E R N E S T G R U N W A L D 159 the making and breaking of hydrogen bonds between ions and the solvent and eventually on the perennial problem of the microscopic structure of liquid water. In the mid-1970s his research moved in the direction of attempts to use megawatt infrared lasers to selectively stimulate and cleave specific bonds in organic molecules. Read the entire page →
From page 160... ... To pursue this goal he took advantage of every advance that was offered by new instrumentation during the 50 years of his research career. At the beginning, in the 1940s, he relied on classical physicochemical methods to determine important thermodynamic properties, such as activity coefficients, in order to analyze solvent effects on reaction rates. Read the entire page →
From page 161... ... Organic reactions occurring in or on mi celles. Read the entire page →
From page 162... ... Rates and Equilibria of Organic Reactions. New York: John Wiley. Read the entire page →
From page 163... ... 87:4387. 1984 Thermodynamic properties, propensity laws, and solvent models in solutions of self-associating solvents. Read the entire page →

From page 147...

... From the mid-1940s to the mid-1990s he established a position of authority on the basic principles behind organic reactions in many ways similar to that of Louis Hammett, who originally coined the term "physical organic chemistry" as the title of his groundbreaking monograph of 1940. Unlike his illustrious predecessor, Grunwald arrived on the scene when most of the traditional barriers between physical and organic chemistry were breaking down and a postwar golden age of enthusiasm and financial support for chemistry was in full swing.