key: cord-0848526-otjq6ne8
authors: Wilhelm, Emmerich
title: In Memoriam: Jean-Pierre E. Grolier (1936–2022)
date: 2022-05-11
journal: J Solution Chem
DOI: 10.1007/s10953-022-01166-y
sha: 17f447dfd2d5d40c5b5c4608641560d9153f87a1
doc_id: 848526
cord_uid: otjq6ne8

nan

such as the garden restaurant at Marseille's main train station Gare Saint-Charles, at "Ma Verte Campagne" or at "L'Entrecôte" at the Vieux Port. Additional early members of our "thermodynamics research group," who contributed significantly to the scientific output, were Americo Inglese from the Istituto di Chimica Fisica, Università di Bari, Bari, Italy, and Mohammad H. Karbalai Ghassemi, later known as Mohammad H. Hamedi, from Iran, who received his Ph.D. degree in Marseille in 1977 (in the 1980s, he became Professor of Mechanical Engineering at the K.N. Toosi University of Technology in Tehran, Iran, was Dean of the Faculty of Mechanical Engineering, and Vice President and President of the University; he retired in 2018). In 2003, he "returned to the roots" and spent a sabbatical period with Jean-Pierre at UBP in Clermont-Ferrand.

After transferring all the laboratory equipment (by private car, that is, with a Mustang Grande!) to Jean-Pierre's home university in Aubière/Clermont-Ferrand (it is situated in the Auvergne, the central region of France, about 500 km north of Marseille, and is the hometown of the well-known Michelin tire company), since 1978 experimental work continued at the Université Clermont II (later renamed Université Blaise Pascal), capably and reliably supported by Alain H. Roux and Geneviève Roux-Desgranges. A few years later, Henry Kehiaian, already Directeur de Recherches, moved from Marseille to Paris (the city of his dreams) to work at the Institut de Topologie et de Dynamique des Systèmes (ITO-DYS/CNRS): thus, the research triangle Clermont-Ferrand-Paris-Wien (Vienna) was established and remained operative for the next three decades. In fact, in the late 1970s and in the 1980s, based on the "Picker flow-technique," Jean-Pierre's laboratory became the internationally leading research center for the determination of excess heat capacities at constant pressure of liquid mixtures with unparalleled precision. Of particular note is the determination of C E P of the liquid mixture {benzene x 1 + cyclohexane x 2 } at 298.15 K and atmospheric pressure: it was measured with an imprecision characterized by a standard deviation from the selected Redlich-Kister fitting equation of ± 0.025 J ⋅ K −1 ⋅ mol −1 (which is less than 1% of the maximal

, thus strongly supporting the use of this system as a test mixture for calorimetric measurements of excess heat capacities of binary liquid nonelectrolyte systems [3] .

Altogether, I spent about 6 years in France, predominantly in Clermont-Ferrand, and Jean-Pierre was a frequent visitor at the IPC in Wien (Vienna). For 28 years, our collaborative research was funded via bilateral peer-reviewed research grants (for 2 years each) within the Austrian-French Program on Scientific-Technical Cooperation: to the best of my knowledge, it was the longest continuously funded collaboration ever, resulting in more than 80 scientific articles, book contributions, and reports, in numerous posters, oral presentations, invited lectures, and plenary lectures. Some of the scientific articles Jean-Pierre considered to be most characteristic of our cooperation are listed as Refs. [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] , with reviews focusing on excess heat capacities and excess volumes being provided by Refs. [16, 17] . Note that Ref. [7] reports the first W-shaped C E P (x) curves ever (two minima and one maximum), while a (weakly) M-shaped C E P (x) curve (two maxima and one minimum) was found for the mixture {(1 − x)H 2 O + xCH 3 COOH} [5] . M-shaped excess molar enthalpies H E (x) are reported in Ref. [13] . I still remember the animated discussions of some of these novel results Jean-Pierre and I had with Donald Patterson (McGill University, Montreal, Quebec, Canada) in Clermont-Ferrand, focusing on the importance of random/nonrandom contributions to H E (x) of liquid nonelectrolyte solutions [18, 19] . They came about because during summer, he and his wife, Geneviève Delmas, occasionally visited her family home situated only about 50 km south of Clermont-Ferrand. On December 15, 2016, Donald Patterson passed away at the age of 89, To further international research cooperation, Jean-Pierre participated in an early Erasmus network (focusing on chemical thermodynamics/physical chemistry of the liquid state) that included colleagues in Germany (R. N. Lichtenthaler, Physikalisch-Chemisches Institut, Universität Heidelberg, Heidelberg, see Ref. [20] ), Spain, UK, and Austria (E. Wilhelm, Institut für Physikalische Chemie, Universität Wien (Vienna), see Ref. [13] ). In addition, within the Erasmus Program, in 2006 and 2007, he taught courses on Thermal Methods (2nd year Master level) at the University of Aberdeen, UK.

Throughout his career, Jean-Pierre loved to travel extensively, be it by car or by airplane, to attend conferences/symposia and science-related workshops, and to interact with fellow scientists, thereby initiating many important research connections. These activities, in combination with the general thermodynamic expertise reflected by the publications originating in Marseille and subsequently in Clermont-Ferrand, and the steadily increasing number of available cutting-edge experimental techniques, made his laboratory (Laboratoire de Thermodynamique, for short) a magnet in the field of chemical thermodynamics for colleagues as well as young aspiring scientists from all over the world as far as Japan [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] [31] [32] [33] . The large number of TOM-inspired cooperations with Spanish scientists has certainly stimulated/influenced research in chemical thermodynamics in Spain [5, 10-12, 23-25, 27, 28] .

Major driving forces for progress in instrumentation are the desire (I) to increase the area of applicability, that is, for instance, to cover larger temperature and pressure ranges, or to study new kinds of systems, (II) to improve precision and accuracy of the experimental methods used, and (III) to increase the speed of measurements. Indeed, over the years, in Jean-Pierre's laboratory, several new/improved types of instruments, covering important areas of thermodynamics, were developed.

One of the most important experimental techniques introduced during the last decades is known as scanning transitiometry [34] [35] [36] [37] [38] [39] [40] [41] [42] [43] [44] [45] [46] [47] . It is the hallmark of the longstanding French-Polish collaboration that started in the early 1990s between Jean-Pierre E. Grolier and Stanisław L. Randzio (Institute of Physical Chemistry, Polish Academy of Sciences, Warszawa (Warsaw), Poland), and included, in addition, Jaques R. Quint (also from Laboratoire de Thermodynamique, UBP), and somewhat later, Miroslaw A. Chorążewski (Institute of Chemistry, University of Silesia, Katowice, Poland). This technique has been successfully used to determine isobaric thermal expansivities P = V −1 ( V∕ T) P , isothermal compressibilities, T = −V −1 ( V∕ P) T , isochoric thermal pressure coefficients V = ( P∕ T) V = P ∕ T , isochoric molar heat capacities C V , and isobaric molar heat capacities C P of liquids at pressures up to 700 MPa, and over wide temperature ranges (up to 500 K). Of particular interest is the observation that for many simple liquids there exists a crossing point of the P -isotherms at elevated pressures. Consider, for instance, P -isotherms for liquid n-hexane [37] between 253.15 and 503.15 K: below (62 ± 2) MPa, P increases with increasing temperature, while for higher pressures, P decreases with increasing temperature. Jean-Pierre E. Grolier and Stanisław L. Randzio were co-inventors of this technique and hold several patents.

The collaboration with Robert H. Wood on using high-temperature and high-pressure flow techniques to measure densities and heat capacities started in 1979 (see above) and led to the transfer of these versatile technologies from Newark to Clermont-Ferrand. Jean-Pierre valued Bob's wise counsel: nick-naming the resulting experimental techniques the Calvet-Picker-Wood cocktail, he used them for developing improved instruments for measuring heat capacities of gases and liquids, for determining heats of mixing of fluids at flow conditions, and for the simultaneous measurement of heats of mixing and densities of mixtures at superambient conditions [48] [49] [50] [51] [52] [53] [54] [55] [56] [58] , at the University of Delaware in Newark, at the University of Wien (Vienna), Austria, and, perhaps most enjoyable, during leaves of absence at UBP in Clermont-Ferrand: he too enjoyed his stays in the Auvergne greatly! Bob passed away on February 3, 2019, at the age of 86.

Isothermal titration calorimetry (ITC) has been developed to measure the heat of reaction resulting from a binding process between two (or more) species in solution and is in use since the 1960s. During the last decades, however, the sensitivity of the instruments used has greatly improved, thereby allowing application of this technique in a large variety of fields, notably in biochemistry and biophysics, in biology, and in drug discovery. In fact, there is a steady rise in the number of ITC relevant publications, thus making periodical critical surveys/reviews highly desirable [59] [60] [61] [62] [63] [64] [65] [66] [67] . ITC was one of the last experimental techniques adopted in Clermont-Ferrand and provided much of the basis of the French-Mexican collaboration, centering on José Manuel del Rio (Instituto Mexicano del Petróleo, Ciudad de México, México).

Although most of Jean-Pierre's scientific work focused on nonelectrolyte systems, the collaboration with Glenn T. Hefter (Chemistry Department, Murdoch University, Murdoch, Western Australia) represents an excursion into the field of electrolyte solutions. At 25 °C, apparent molar volumes and isobaric apparent molar heat capacities for NaCl, LiCl, NaF, KI, sodium tetraphenylborate (NaBPh 4 ), and tetraphenylphosphonium chloride (Ph 4 PCl) dissolved in aqueous solutions containing up to 40% by mass t-butyl alcohol have been determined by flow densitometry and flow microcalorimetry, respectively [68] . Analogous measurements were reported in Ref. [69] for NaCl, KCl, KNO 3 , AgNO 3 , KI, NaBPh 4 , and Ph 4 PCl dissolved in acetonitrile (AN)-water mixtures containing up to x AN = 0.25 . Volumetric properties of, and ion pairing in, aqueous solutions of Na 2 SO 4 and K 2 SO 4 have been reported at temperatures ranging from 298 K to 573 K, and for pressures up to 30 MPa, in Ref. [70] . An analogous study reports densities and apparent molar volumes of NaF and KF, respectively, dissolved in water at temperatures ranging from 25 °C to 354 °C, and at pressures up to 30 MPa [71] . Jean-Pierre visited Glenn several times "down under."

Investigation of the thermophysical properties of polymers, in particular at elevated temperatures and pressures, and identification of optimal operating conditions in polymer synthesis and (industrial) polymer modifications and transformations through different processes, such as foaming, were topics Jean-Pierre became interested in rather late in his career [72] [73] [74] [75] [76] [77] [78] [79] [80] [81] [82] . The main coworkers during this period of his scientific life were Florin Dan, from the Macromolecular Chemistry Department, Gh. Asachi Technical University, Iasi, Romania, who later moved on to become Research Scientist (Core R&D, Analytical Sciences) with The Dow Chemical Company at Midland, MI, USA, Séverine A. E. Boyer, who is now with MINES Paris Tech, PSL Research University, Sophia Antipolis, France, and Hirohisa Yoshida, from Urban Environmental Science, Tokyo Metropolitan University, Tokyo, Japan. In fact, over the years, interaction with Japanese colleagues at both the professorial level (for instance, to name but a few, Profs. Suga, Yoshida, Kimura, Ogawa, Murakami, Nakazawa, Saito, Takagi) as well as via accepting post-docs from Japan, has played an important role in the scientific development of the laboratory at UBP. In turn, Jean-Pierre visited Japan frequently: for instance, he attended Japanese Conferences on Calorimetry and Thermal Analysis (JCCTA), he visited the Research Center for Thermal and Entropic Science in Osaka (current Director is Prof. Yasuhiro Nakazawa), he participated at the 14th ICCT in Osaka (1996) , the 26th International Conference on Solution Chemistry in Fukuoka (1999), and the 21st ICCT in Tsukuba (2010). At the latter conference, the Japanese Emperor and Empress joined the Conference Reception, and Jean-Pierre and his wife, Geneviève, had the honor and pleasure to directly participate in the welcoming of the Royal couple-a rare experience indeed! Towards the end of his career Jean-Pierre became interested in the thermodynamic investigation of properties of fluids in confined spaces [83] [84] [85] [86] [87] [88] . In collaboration with Valentin Eroshenko [89] and Yaroslav Grosu (both from the Laboratory of Thermomolecular Energetics, National Technical University of Ukraine, Kyiv, Ukraine), and Jean-Marie Nedelec (Institut de Chimie de Clermont-Ferrand, Université Clermont Auvergne, formerly UBP), experiments focused on systems consisting of a porous material (metal organic frameworks, such as the exceptionally stabile Zeolite Imidazolate Frameworks, ZIFs [90] ) and water as a non-wetting fluid. High-pressure intrusion-extrusion of water into hydrophobic porous solids is a promising technology to store, release, or transform mechanical energy (leading to shock-absorbers and molecular springs).

Professor Grolier's scientific oeuvre comprises more than 280 scientific articles in refereed journals and book chapters, and 5 patents. His name is also associated with over 500 conference contributions, which number includes 47 Plenary Lectures and 78 Invited Lectures.

In addition to his university position, Professor Jean-Pierre Grolier held many offices in professional organizations. Nationally, he was influential in the Association In the 80s and 90s, my wife Olga and our daughter, Katja Dagmar, frequently visited me in Clermont-Ferrand during summer (I usually rented an apartment in Chamalières, only a few kilometers away from Jean-Pierre's home). I treasure the warm hospitality of Jean-Pierre and his wife, Geneviève, during these scientifically and socially so memorable times. On a larger scale, I always enjoyed the receptions in their garden (weather permitting), that was/is a green island harmonizing beautifully with their elegant house on Boulevard Lavoisier.

At the young age of 52, Americo Inglese passed away in 1998. Our old friend Henry Kehiaian passed away at the age of 80 in 2009, and Jean-Pierre and I published an obituary in the Journal of Chemical & Engineering Data [91] and in Fluid Phase Equilibria [92] . Now Jean-Pierre Grolier has left us at the age of 86. The Funeral Mass was celebrated at the church Notre-Dame de Chamalières, and its musical frame was selected by Jean-Pierre himself pour un jour spécial. The three pieces of music by Fryderyk Chopin, Wolfgang Amadeus Mozart, and Antonín Dvořák, respectively, reflect his longtime relation with Poland, Austria, and America, and with friends and colleagues therefrom. The collegial fraternity of thermodynamicists (of many fields), will miss him dearly: we will miss his science input and inquisitive mind, his helpfulness and generosity, his personal charm and joie de vivre, in short, his friendship.

Jean-Pierre, you lived a long and successful life, you were a wonderful friend, and you will be fondly remembered. Requiescat in pace.

Last greetings, Emmerich Wilhelm, Institute of Materials Chemistry and Research (former Head of IPC), University of Wien (Vienna), Austria

Enthalpies of mixing of organic liquids measured directly as a function of composition by means of scanning dynamic flow microcalorimetry

Simultaneous measurements of heat capacities and densities of organic liquid mixtures-systems containing ketones

Molar heat capacity and isothermal compressibility of binary liquid mixtures: carbon tetrachloride + benzene, carbon tetrachloride + cyclohexane and benzene + cyclohexane

Thermodynamics of binary mixtures containing alkynes. II. Excess enthalpies of binary mixtures of 1-hexyne and 3-hexyne with carbon tetrachloride, dipropyl ether, and triethylamine at 298.15 K

Excess volumes and excess heat capacities of (water + alkanoic acid)

Excess volumes and excess heat capacities of water + ethanol at 298.15 K

Excess molar heat capacities of (1,4-dioxane + an n-alkane): an unusual composition dependence

Excess molar enthalpies, excess molar heat capacities and excess molar volumes of (fluorobenzene + an n-alkane)

Excess enthalpy, excess heat capacity and excess volume of 1,2,4-trimethylbenzene +, and 1-methylnaphthalene + an n-alkane

Thermodynamics of liquid mixtures containing n-alkanes and strongly polar components: V E and C P E of mixtures with either pyridine or piperidine

Thermodynamics of (1,4-difluorobenzene + an n-alkane) and of (hexafluorobenzene + an n-alkane)

Heat capacities and concentration fluctuations in mixtures of 1,2-dibromoethane + alkane

Thermodynamics of liquid mixtures consisting of a very polar and a non-polar aromatic: (benzonitrile + benzene, or toluene)

Thermodynamic and acoustic properties of mixtures of 1,6-dichlorohexane with heptane from 293 K to 313 K

Jumping transition in the liquid's heat capacity revealed by the scanning transitiometry

Heat capacities and related properties of liquid mixtures

Excess volumes of liquid nonelectrolyte mixtures

The W-shape concentration dependence of C P E and solution nonrandomness: ketones + normal and branched alkanes

Chemical thermodynamics: a journey of many vistas

Excess molar heat capacities C E P, m and excess molar volumes V E m of {x 1 CH 3 (CH 2 ) 5 CH 3 + x 2 CH 3 C(CH 3 ) 2 CH 2 CH(CH 3 )CH 3 + x 3 CH 3 C(CH 3 ) 2 OC 2 H 5 + (1-x 1 -x 2 -x 3 )C 2 H 5 OH}(l) II. Ternary mixtures and prediction of quaternary values

Enthalpies de mélanges des chlorures organiques avec des hydrocarbures

Thermodynamics of organic mixtures. A generalized quasichemical theory in terns of group surface interactions

Excess enthalpies of some binary mixtures. n-alkane + aliphatic ether, n-alkane + hydroxy ether, aliphatic ether + hydroxy ether

Thermochemical behaviour of mixtures of n-alcohol + aliphatic ether: heat capacities and volumes at 298.15 K

Thermodynamic properties of mixtures containing esters. I. Analysis of the properties of n-alkanoate + n-alkane and n-alkanoate + n-alkanoate mixtures in terms of a quasichemical group-contribution model

Thermal and volumetric properties of chloroform + triethylamine mixtures and the ideal associated solution model of complex formation

Molar excess heat capacities and volumes for mixtures of alkanoates with cyclohexane at 25 °C

Thermodynamics of alkanoates + alkane binary mixtures. Concentration dependence of excess heat capacities and volumes

Molar heat capacities and volumes of transfer of cytosine, thymine, caffeine and 1,3-diethylthymine to aqueous solutions of glycyl-glycine and L-α-alanyl-L-α-alanine at 25 °C

Experimental measurements of the speed of sound in n-hexane from 293 to 373 K and up to 150 MPa

Thermodynamic properties of binary mixtures (an alkoxyethanol + n-octane). Excess molar enthalpies and excess molar heat capacities at 298.15 K. Fluid Phase Equilib

Determination of Henry's law constants for aqueous solutions of tetradeuteriomethane between 285 and 325 K and calculation of the H/D isotope effect

Thermoporosimetry: a powerful tool to study the cross-linking in gels networks

Scanning calorimeters controlled by an independent thermodynamic variable: definitions and some metrological problems

Calorimetric determination of pressure effects

An isothermal scanning calorimeter controlled by linear pressure variations from 0.1 to 400 MPa. Calibration and comparison with the piezothermal technique

n-Hexane as a model for compressed simple liquids

Thermophysical properties of 1-hexanol over the temperature range from 303 to 503 K and at pressures from the saturation line to 400 MPa

Scanning transitiometry

State variables in calorimetric investigations: experimental results and their theoretical impact

Isobaric thermal expansivities of binary mixtures of n-hexane with 1-hexanol at pressures from 0.1 to 350 MPa and at temperatures from 303 to 503 K

Thermomechanical coefficients obtained in the vicinity of the critical point by scanning transitiometry

Isobaric thermal expansivities of toluene measured by scanning transitiometry at temperatures from (243 to 423) K and pressures up to 200 MPa

Scanning transitiometry and its use to determine heat capacities of liquids at high pressures

Thermophysical properties of Normafluid (ISO 4113) over wide pressure and temperature ranges

Determination of the asphaltene precipitation envelope and bubble point pressure for a Mexican crude oil by scanning transitiometry

High-pressure "Maxwell relations" measurements

Densities of toluene, of butanol and of their binary mixtures from 298 K to 400 K, and from 0.5 to 20.0 MPa

Densities and heat capacities of 1-butanol + n-decane from 298 K to 400 K

Modification of a Setaram C-80 calorimeter for measuring heat capacities of liquids at temperatures up to 548 K and pressures up to 20 MPa

Excess heat capacities of 1-butanol + toluene from 298 to 368 K

Measurements of excess enthalpies at high temperature and pressure using a new type of mixing unit

Isobaric heat capacities of carbon dioxide and argon between 323 and 423 K and at pressures up to 25 MPa

A vibrating tube flow densitometer for measurements with corrosive solutions at temperatures up to 723 K and pressures up to 40 MPa

Combined flow-mixing power-compensation calorimeter and vibrating tube densimeter for measurements at superambient condition

Excess enthalpy for {x 1-hexanol + (1-x)} hexane at temperatures from 323 to 513 K, and pressures from 3.5 to 15 MPa

From solutions to polymers: a high temperature-high pressure journey in experimental thermodynamics

In appreciation of Professor Robert H. Wood

Applications of isothermal titration calorimetry-the research and technical developments from 2011 to 2015

Applications of isothermal titration calorimetry in pure and applied research from 2016 to 2020

Isothermal titration calorimetry: a thermodynamic interpretation of measurements

Differential binding models for isothermal titration calorimetry: moving beyond the Wiseman isotherm

Isothermal titration calorimetry: application of the Gibbs-Duhem equation to the study of the relationship between forward and reverse titrations

Isothermal titration calorimetry

Titration calorimetry and differential scanning calorimetry of lipid-protein interactions

Simultaneous determination of equilibrium constants, enthalpy changes and stoichiometries by titration

Free energy in thermal and chemical protein unfolding

Apparent molar heat capacities and volumes of electrolytes and ions in t-butanol-water mixtures

Apparent molar heat capacities and volumes of electrolytes and ions in acetonitrile-water mixtures

Volumetric properties of, and ion-pairing in, aqueous solutions of alkali-metal sulfates under superambient conditions

Volumetric behavior of aqueous NaF and KF solutions up to 350 °C and 30 MPa

Simultaneous measurement of the solubility of gases in polymers and of the associated volume change

Spectrocalorimetric screening for complex process optimization

Caloric measurements of thermophysical properties for industry

The use of scanning transitiometry to investigate thermodynamic properties of polymeric systems over extended T and p ranges

Advanced experimental techniques in polymer thermodynamics

New developments and applications in titration calorimetry and reaction calorimetry

Iyoda, T: Isotropic transition behaviour of an amphiphilic di-block copolymer under pressure. Carbon dioxide or mercury as pressure medium

Developments and Applications in Solubility

Phase transitions of polymers over T and P ranges under various hydraulic fluids: polymer/supercritical gas systems and liquid to solid polymer transitions

Gas-polymer interaction: key thermodynamic data and thermophysical properties

Thermodynamics and thermokinetics to model phase transitions of polymers over extended temperature and pressure ranges under various hydrostatic fluids

Thermomechanics of the variation of interfaces in heterogeneous lyophobic systems

Water intrusion/extrusion in hydrophobized mesoporous silica gel in a wide temperature range: capillarity, bubble nucleation and line tension effects

A new working mode for molecular springs: water intrusion by cooling and associated isobaric heat capacity change of a {ZIF-8 + water} system

Exceptionally large and controlled effect of negative thermal expansion in porous heterogeneous lyophobic systems

Synergetic effect of temperature and pressure on energetic and structural characteristics of {ZIF-8 + water} molecular spring

A highly stable nonhysteretic {Cu 2 (tebpz) MOF + water} molecular spring

Energetics: a new field of application for hydrophobic zeolites

Energetic performances of "ZIF-71-aqueous solution" systems: a perfect shock-absorber with water

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