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Thermochemical studies of 2,2,6,6-tetramethyl-3,5-heptanedione chelates of scandium group elements

✍ Scribed by Luiz S. Santos; Jr; Sirlei Roca; Claudio Airoldi


Publisher
Elsevier Science
Year
1997
Tongue
English
Weight
154 KB
Volume
29
Category
Article
ISSN
0021-9614

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✦ Synopsis


The standard molar enthalpies of formation of crystalline chelates M(thd)3, (M = Sc, Y, La; and thd = 2,2,6,6-tetramethyl-3,5-heptanedionate), determined by reaction-solution calorimetry at T = (298.15 2 0.02) K, were found to be -(2317.83 2 11.7) kJ•mol -1 , -(2386.1 2 11.4) kJ•mol -1 , and -(2442.2 2 11.8) kJ•mol -1 , respectively. The corresponding molar enthalpies of sublimation, (79.6 2 2.4) kJ•mol -1 , 117 kJ•mol -1 , and (156.0 2 4.6) kJ•mol -1 , were obtained by differential scanning calorimetry or vapour pressure measurements, and enabled the calculation of the standard molar enthalpies of formation of the gaseous chelates. From the standard molar enthalpies of dissociation of the chelates (1575 2 62) kJ•mol -1 , (1652 2 62) kJ•mol -1 , and (1679 2 62) kJ•mol -1 , respectively, the mean metal-to-oxygen bond enthalpies were also calculated to be (263 2 10) kJ•mol -1 , (275 2 10) kJ•mol -1 , and (280 2 10) kJ•mol -1 , by assuming the equivalence of all bonds in the chelates. This first sequence of values obtained for the scandium group elements showed a tendency towards an increase of values with the increase of the metal's atomic number in this series.


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