Thallium, thermodynamic data

No other thermodynamic data have been found for thallium selenites. 

O.J. Kleppa, Approximate Thermodynamic Data from the Systems Copper-bismuth, Copper-lead and Copper-thallium , J.Am.Chem.Soc.. Vol. 74,1952,6047-6051. 

Table 13.28 Thermodynamic data for thallium species at 25 °C and comparison with data availaUe in the literature.

Data for the thermodynamic parameters of thallium species (both thallium(I) and thallium(III) are listed in Table 13.28). Also listed in the table are thermodynamic data for Tl", TP" and Tl(s) taken from Bard, Parsons and Jordan (1985). The table also contains thermodynamic data reported by Bard et al. for the oxide phases of thallium and some hydrolysis species. There is good agreement between the data presented by Bard et al. for Tl20(s) and those accepted in the present review. However, there is much poorer agreement for the hydrolysis species of thallium(I) and the oxide phase of thallium(III). 

Propylene Carbonate (PC) and Water. Data from both spectroscopic and thermodynamic studies for other solvent systems are sparse and some of it is of doubtful quality. For propylene carbonate, Salomon (40) has obtained emf data using lithium metal and thallium amalgam-thallous chloride or bromide electrodes. 

It has long been assumed that since lead azide, for example, is more sensitive than sodium azide when impacted, the reactivity of the former is greater than that of the latter. That this is not so was demonstrated by Walker [58] and Fox [59], who compared the rates of slow thermal decomposition under identical experimental conditions for the azides of sodium, thallium, and lead. The results, summarized in Figure 7, show that over most of the temperature range studied lead azide is the least reactive, and that above about 560°K sodium azide reacts more rapidly than either lead or thallium azides. Moreover, above 590 K the rate of evolution of heat is greater in sodium than in lead azide. Alternatively, the application of data for the energetics of decomposition derived from slow reactions is not applicable to fast reactions, since in the latter thermodynamic equilibrium is not attained and the mechanism for slow decomposition discussed in Chapter 6 may not apply. There is some evidence that this is so [60]. 

Results for the standard thermodynamic functions, temperature derivatives thereof leading to and TA S° are shown in the review by Marcus and Hefter [29] for many electrolytes in several solvents. Some of these data are shown in Table 7.4. For the ion pairing of the thallium halides in the solvents shown in this table, the association is enthalpy driven, pointing to CIP formation with some coordinative bonding. For the other ion pairs shown, the association is entropy driven, for even if there are only 2SIPs being formed, fewer particles result in the solution than when only free solvated ions exist. 

Approximate thermodynamic formation constants of some complexes of lead(II) and thallium(I) from polarographic data. J. Am. Chem. Soc., 83, 323-326. 

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