Some thermodynamic aspects

This section is largely devoted to the results of thermodynamic studies of equilibria in aqueous solution involving hydrated cations M +(aq), ligands and the complexes formed by these. Some of the thermodynamic properties of M +(aq) ions have already been discussed 

The reader may wonder at this point whether bond energies for coordination compounds can be tabulated and utilised in chemical arguments, in the same way as in Main Group chemistry. The complexity of most coordination/organometallic compounds makes this very difficult, and the ways in which the formation of a coordinate bond affects the bonding within the ligand renders the bond energy concept distinctly dubious. Consider, for example, the relatively simple case of hexacar-bonylchromium(O). For the reaction  

Consider a hydrated cation M and a ligand L (which may be neutral or anionic) in aqueous solution (for clarity and simplicity, charges are not specified). If the coordination number of M is 6, and if L is unidentate, we can form complexes ML (n = 1-6). The equilibria can be written in two ways  

The constants kn are stepwise formation constants, while the K are overall formation constants. They are simply related by  

Since formation constants are often very large, it is more convenient to adopt the logarithmic formation. (Stepwise and overall formation constants are often given the symbols K and (3 respectively.) 

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Tetenbaum, M. "Some Thermodynamic Aspects of the Pu-0 System" presented at the ACS Symposium on the Chemistry of Plutonium, Kansas City, September 13-15, 1982. 

Johnson, D.A. Some Thermodynamic Aspects of Inorganic Chemistry, 2 ed Cambridge University Press, 1982 Chapter 6 and problems 6.6-6.9. 

Some Thermodynamic Aspects of Interactions on Oxide Surfaces... 

For a vary thorough discusson of enthalpy, entropy, and the solubility of ionic compounds, see Johnson. D. A. Some Thermodynamic Aspects of Inorganic Chemistry Cambridge University London. 1968. Chafrter 5. 

See Moffitt. W. Prnc. Roy. Soc. (London) 1950. A202. 548. For very readable accounts of the valence slate see McWeeny. R. CotAsoa i Valence. Oxford University London, 1979 pp 150, 201-201.208-209 Johnson. D. A. Some Thermodynamic Aspects of Inorganic CTicmisiry, 2nd cd. Cambridge University Cambridge, 198% pp 176-177.200-206. 

Johnson, A. D. Some thermodynamic aspects of inorganic chemistry, pp. 158-160. Cambridge University Press, 1968... 

Bidard, R. A., "Energy Conservation in Chemical Reactions Some Thermodynamic Aspects," In reference 16, p. 11 (1978). 

Some thermodynamic aspects of the glass transition Free volume, entropy and enthalpy theories. J. Chem. Phys. To be published (1964). 

Helgeson, H. C. (1985). Some thermodynamic aspects of geochemistry. Pure and Applied Chemistry, 57, 31 4. 

Brice J. C. (1975) Some thermodynamic aspects of the growth of strained crystals. J. Cryst. Growth 28, 249-253. 

D. H. Everett, Some Thermodynamic Aspects of Aggregation Phenomena, Colloids Surf., 1986, 21, 41. 

Bocherens H, Tresset A, Wiedemarm F, Giligny F, Lafage F, Lanchon Y, Mariotti A (1997) Diagenetic evolution of mammal bone in two French Neolithic sites. Bull Soc Geol France 168 555-564 Brice JC (1975) Some thermodynamic aspects of the growth of strained crystals. J Crystal Growth 28 249-253... 

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