Thermodynamic Properties of Alkali Metal Hydroxides. Part 1. Lithium and Sodium Hydroxides

Abstract

The data on thermodynamic and molecular properties of the lithium and sodium hydroxides have been collected, critically reviewed, analyzed, and evaluated. Tables of thermodynamic properties (C; ,<1>0 =-(Go-HO(O)/T, So, HO-HO(O), tJ.fHo, tJ.rG°) of these hydroxides in the condensed and gaseous states have been calculated using the results of the analysis and some estimated values. The recommendations are compared with earlier evaluations given in the JANAF Thermochemical Tables and Thermodynamic Properties of Individual Substances. The properties considered are: the temperature and enthalpy of phase transitions and fusion, heat capacities, spectroscopic data, structures, bond energies. and enthalpies of formation at 298.15 K. The thermodynamic functions in solid, liquid, and gaseous states are calculated from T= 0 to 2000 K for substances in condensed phase and up to 6000 K for gases.

Lithium monoxide anion: A ground-state triplet with the strongest base to date

“…1. To the best of our knowledge, BDE(LiO-H) has not been reported, but the heats of formation of LiOH (Ϫ56.0 Ϯ 1.5 kcal⅐mol Ϫ1 ) (3,18,19) and LiO ⅐ (9.1 Ϯ 3.0 kcal⅐mol Ϫ1 ) (20)(21)(22)(23)(24)(25) are known. This leads to BDE(LiO-H) ϭ 117.2 Ϯ 3.4 kcal⅐mol Ϫ1 , which is somewhat lower than our theoretical values of 121.1 [BD(T)], 122.4 (W1), 122.2 (W2C), and 121.4 (CAS-AQCC) kcal⅐mol Ϫ1 .…”

Ab initio study of the neutral and anionic alkali and alkaline earth hydroxides: Electronic structure and prospects for sympathetic cooling of OH−

“…Neutral alkali and alkaline earth hydroxides (MOH) have been extensively studied both theoretically [10][11][12][13][14][15][16][17][18][19][20] and experimentally [21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] (see also the reviews of A.Ellis 36 and Gurvitch et al 37 ). The interest lies in the general context of molecular structure and the understanding of the M-O bond.…”

A re-assessment of the thermodynamic properties of iodine condensed phases

“…However, apparently not wishing to discard any of their measurements, then the resultant curve showed a peculiar and unnatural behaviour above 170 K which can be traced to the inclusion of three highly discrepant data points at 273.32 K, 282.02 K, and 291.14 K. In their later assessment Gurvich et al [2] appeared to have simply accepted the specific heat curve as given by Shirley and Giauque without any comment as to the unnatural behaviour and they did not carry out any corrections. Similarly other assessments giving selected values at 298.15 K such as those of Hultgren et al [3], CODATA [4], and JANAF [5] also appear to have accepted this anomalous behaviour without comment.…”

“…The calorimeter used by Frederick and Hildenbrand was calibrated using a simple specific heat equation for copper: C p ðcal Á g À1 Þ ¼ 0:09076 þ 4:15 Á 10 À5 ðt= CÞ which is due to Bronson, Chisholm, and Dockerty [10] but both Gurvich et al [2] and JANAF [5] consider that the derived specific heat values were much too high and therefore both corrected the enthalpy values of Frederick and Hildenbrand. However when the above equation is compared with a combination of the high precision specific heat measurements of copper by Robie et al [11], Martin [12], Stevens and Boerio-Goates [13], and Bronson et al [10] evaluated over the range 200 K to 400 K then the agreement is to within ±0.2% over the common temperature range 273 K to 373 K which is to be considered to be entirely satisfactory and therefore no corrections to the enthalpy measurements of Frederick and Hildenbrand should have been applied.…”