On Thursday, 16 April 2009, Professor H. Donald. B. Jenkins presented an Exaugural Lecture to a packed audience at the University of Warwick, at a Symposium held to honour his retirement and to celebrate his 44-year career. This is a transcript of that lecture, which describes the evolution of a new approach to thermodynamics: volume-based thermodynamics (VBT) which is gaining in popularity and which is relatively simple to use. Reported also are a number of other simple relationships, capable of estimation of standard thermodynamic data, currently under development. Some of these are immensely powerful and they are described.
HaoC., SharrettS.M., and SunderlinL. (2007) The gas-phase thermochemistry of PCl4+: a test of lattice energy calculations. Int. J. Mass Spectrom., 267, 357–362.
2.
JollyW., and GinC. (1977) The estimation of heats of formation of gaseous cations from core electron binding energies. Int. J. Mass Spectrom. Ion Phys., 25, 27–30.
3.
FinchA., GatesP.N., JenkinsH.D.B., and ThakurK.P. (1980) Ionic isomerism in phosphorus (V) chloride. J. Chem. Soc. Chem. Commun., 579–580.
4.
JenkinsH.D.B., ThakurK.P., FinchA., and GatesP.N. (1982) Isomerisation. 2. Calculations of thermodynamic properties of phosphorus (V) chloride isomers: ΔfH°(PCl+4, g), and ΔfH°(PCl-6, g). Inorg. Chem., 21, 423–426.
5.
JenkinsH.D.B., SharmanL., FinchA., and GatesP.N. (1996) Ionic isomerisation. 3. Estimation of the enthalpies of formation of the gaseous tetrachlorophosphonium ion, ΔfH°(PCl+4, g), and of the gaseous hexachlorophosphate ion, ΔfH°(PCl-6, g). Lattice enthalpy calculations for bis(tetrachlorophosphonium) hexachlorophosphate halides, [PCl4]2[PCl6]X where X = Cl or Br. Bond enthalpies of phoshorus(V) chloro compounds. Inorg. Chem., 35, 6316–6326.
6.
CahayR., WongP. T.T., and WhalleyE. (1979) The ionization of PCl6- in the solid state under pressure. II. Raman spectra of phosphorus pentachloride III. J. Chem. Phys., 70, 5539.
JenkinsH.D.B., and PrattK.F. (1980) LATEN–a lattice energy program. Comput. Phys. Commun., 21, 257–265.
11.
JenkinsH.D.B., and PrattK.F. (1978) Calculation of the first derivatives of madelung constants with respect to cell lengths. Comput. Phys. Commun., 13, 341–348.
12.
JenkinsH.D.B., and PrattK.F. (1978) Single ion properties by lattice energy minimisation. J. Chem. Soc, Faraday Trans II, 74, 968–981.
13.
JenkinsH.D.B., and PrattK.F. (1977) On “basic” radii of simple and complex ions and the repulsion energy of ionic crystals. Proc. R. Soc. (Lond.), A356, 115–121.
14.
MuirA.S. (1991) Preparation and spectroscopic characterization of caesium hexachlorophosphate. Polyhedron, 10, 2217.
15.
FinchA., FitchA.N., and GatesP.N. (1993) Crystal and molecular structure of a metastable modification of phosphorus pentachloride. J. Chem. Soc. Chem. Commun., 957.
16.
JenkinsH.D.B., SharmanL., FinchA., and GatesP.N. (1994) Energetics of the tetrachlorophosphonium cation, PCl4+,g, the hexachlorophosphate anion, PCl6- and metastable phosphorus (V) chloride [PCl+4]2[PCl-6][Cl-], c. Polyhedron, 13, 1481–1482.
17.
MalloukT.E., RosenthalG.L., MuellerG., BusascoR., and BartlettN. (1984) Fluoride ion affinities of gaseous tetrafluoride and boron trifluoride from thermodynamic and structural data for (SF3)2GeF6, ClO2GeF5 and ClO2BF4. Inorg. Chem., 23, 3167–3173.
18.
BartlettN. (1962) Xenon Hexafluoroplatinate(v) Xe+[PtF6]-. Proc. Chem. Soc., 218.
19.
MalloukT.E. (1983) University of California, PhD thesis.
20.
JenkinsH.D.B. (2005) Thermodynamics of the relationship between lattice energy and lattice enthalpy. J. Chem. Ed., 82, 950–952.
21.
JenkinsH.D.B., RoobottomH.K., PassmoreJ., and GlasserL. (1999) Relationships among ionic lattice energies, molecular (formula unit) volumes, and thermochemical radii. Inorg. Chem., 38, 3609–3620.
JenkinsH.D.B. (1983–84) In: WeastR.C. (ed.), CRC Handbook of chemistry and physics, CRC Press, Inc, Boca Raton, Florida.
24.
JenkinsH.D.B., and GlasserL. (2006) Volume-based thermodynamics-estimations for 2: 2 salts. Inorg. Chem., 45, 1754–1756.
25.
JenkinsH.D.B., TudelaD, and GlasserL. (2002) Lattice potential energy estimation for complex ionic salts from density measurements. Inorg. Chem., 41, 2364–2367.
26.
GlasserL., and JenkinsH.D.B. (2000) Lattice energies and unit cell volumes of complex ionic solids. J. Am. Chem. Soc., 122, 632–638.
27.
JenkinsH.D.B., and GlasserL. (2003) Standard absolute entropy, So298, values from volume or density. 1. Inorganic materials. Inorg. Chem., 42, 8702–8708.
28.
GlasserL., and JenkinsH.D.B. (2003) Standard absolute entropies, So298, from volume and density. Part II. Organic liquids and solids. Thermochim. Acta, 414, 125–130.
29.
JenkinsH.D.B. (2008) Complex thermochemistry simplified. volume-based thermodynamics (VBT) as an approach for the estimation of standard enthalpies of formation of gas phase ions: ΔfH°(PCl+4, g) and ΔfH°(PCl-6, g). Inorg. Chem., 47, 8420–8425.
30.
JenkinsH.D.B., and PrattK.F. (1977) Thermochemistry of azide salts and the azide ion using direct minimisation equations to obtain the lattice energy of the univalent azide salts. J. Phys. Chem. Solids, 38, 573–579.
31.
FauS., WilsonK.J., and BartlettR.J. (2002) On stability of N+5 N-5. J. Phys. Chem. A, 106, 4639–4644.
32.
DixonD.A., FellerD., ChristeK.O., WilsonW.W., VijA., VijV., JenkinsH.D.B., OlsonR.M., and GordonM.S. (2004) Enthalpies of formation of gas-phase N3, N3-, N5+, and N5- from ab initio molecular orbital theory, stability predictions for N3-N5+ and N5+N3-, and experimental evidence for the instability of N5+N3-. J. Am. Chem. Soc., 126, 834–843.
33.
JenkinsH.D.B. (2007) Chemical thermodynamics–at a glance, Blackwell, Oxford.
34.
ChristeK.O., WilsonW.W., SheehyJ.A., and BoatzJ.A. (1999) N5+: a novel homoleptic polynitrogen ion as a high energy density material. Angew. Chem. Int. Ed., 38, 2004–2009.
35.
VijA., WilsonW.W., VijV., ThamF.S., SheehyJ.A., and ChristeK.O. (2001) Polynitrogen chemistry. synthesis, characterization and crystal structures of surprisingly stable fluoroantimonate Salts of N5+. J. Am. Chem. Soc., 123, 6308–6313.
36.
WagmanD.D., EvansW.H., ParkerV.B., SchummR.H., HalowI., BaileyS.M., ChurneyK.L., and NuttallR.L. (1982) The NBS tables of chemical thermodynamical properties Selected values for inorganic and C1 and C2 organic substances in SI units, J. Phys. Chem. Ref. Data, 11, Suppl. No. 2.
37.
ByrdE., and RiceB. (2009) A comparison of methods to predict solid phase heats of formation of molecular energetic salts. J. Phys. Chem. A, 113, 345–352.
38.
JenkinsH.D.B., and GlasserL. (2002) Ionic hydrates, MpXq.nH2O: lattice energy and standard enthalpy estimation. Inorg. Chem., 41, 4378–4388.
39.
JenkinsH.D.B., and GlasserL. (2004) Difference rule-a new thermodynamic principle: prediction of standard thermodynamic data for inorganic solvates. J. Am. Chem. Soc., 126, 15809–15817.
40.
GlasserL., and JenkinsH.D.B. (2007) The thermodynamic solvate difference rule: solvation parameters and their use in the interpretation of the role of bound solvent in condensed-phase solvates. Inorg. Chem., 46, 9768–9778.
41.
JenkinsH.D.B., and LiebmanJ.F. (2009). Extensions and corollaries of the thermodynamic solvate difference rule. J. Chem. Engng. Data, 54, 351–358.
42.
BrownridgeS., CalhounL., JenkinsH.D.B., LaitinenR.S., MurchieM.P., PassmoreP., PietikäinenJ., RautiainenJ.M., SandersJ.C.P., SchrobilgenG.J., SuontamoR.J., TuononenH.M., ValkonenJ.U., and WongChi-Ming (2009) 77Se NMR spectroscopic, DFT MO, and VBT investigations of the reversible dissociation of solid (Se6I2)[AsF6]2 · 2SO2 in liquid SO2 to solutions containing 1, 4–Se6I22+ in equilibrium with Sen2+(n = 4, 8, 10) and seven binary selenium iodine cations: preliminary evidence for 1, 1, 4, 4–Se4Br42+ and cyclo–Se7Br+. Inorg. Chem., 48, 1938–1959.
43.
BarinI. (1993) Thermochemical data of pure substances, VCH, Weinheim, FDR.
