A detailed study has been made of the electrolyte conductance of a series of salts in methanolic solution. The pressure coefficients of the limiting equivalent conductances were evaluated over the range 2 - 25 x 10-4 moles litre-1, 5 - 45°C and 1 - 2000 atm. In conjunction with a separate study of the compressibility of methanol, these co-efficients were analysed in terms of the Transition State Theory of conductance. The significant variables are temperature and (Pi + P), the sum of the internal and external pressures. From a consistent representation of the transition state theory three principal parameters were evaluated; (i) the isochoric energy of activation, (ii) the volume of activation and (iii) an entropy term related to, but not equal to, the entropy of activation. The variation of these activation parameters with volume, temperature and ion-size is discussed and this leads to an improved conception of ionic migration in methanol and presumably other liquids. The rectilinearity of the isochores is a striking feature of the work and justifies the application of the constant volume principle.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:602216 |
| Date | January 1963 |
| Creators | Howard, Brian |
| Publisher | Imperial College London |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://hdl.handle.net/10044/1/13305 |
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