Investigation of the Vaporization of Boric Acid by Transpiration Thermogravimetry and Knudsen Effusion Mass Spectrometry

• Published in: The journal of physical chemistry. B 2008-11, Vol.112 (44), p.13873-13884
• Main Authors: Balasubramanian, R, Lakshmi Narasimhan, T. S, Viswanathan, R, Nalini, S
• Format: Article
• Language: English
• Subjects: B: Statistical Mechanics, Thermodynamics, Medium Effects
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp8058883

The vaporization of H3BO3(s) was studied by using a commercial thermogravimetric apparatus and a Knudsen effusion mass spectrometer. The thermogravimetric measurements involved use of argon as the carrier gas for vapor transport and derivation of vapor pressures of H3BO3(g) in the temperature range 315−352 K through many flow dependence and temperature dependence runs. The vapor pressures as well as the enthalpy of sublimation obtained in this study represent the first results from measurements at low temperatures that are in accord with the previously reported near-classical transpiration measurements (by Stackelberg et al. 70 years ago) at higher temperatures (382−413 K with steam as the carrier gas). The KEMS measurements performed for the first time on boric acid showed H3BO3(g) as the principal vapor species with no meaningful information discernible on H2O(g) though. The thermodynamic parameters, both p(H3BO3) and Δsub H°m(H3BO3,g), deduced from KEMS results in the temperature range 295−342 K are in excellent agreement with the transpiration results lending further credibility to the latter. All this information points toward congruent vaporization at the H3BO3 composition in the H2O−B2O3 binary system. The vapor pressures obtained from transpiration (this study and that of Stackelberg et al.) as well as from KEMS measurements are combined to recommend the following: log [p(H3BO3)/Pa] = −(5199 ± 74)/(T/K) + (15.65 ± 0.23), valid for T = 295−413 K; and Δsub H°m = 98.3 ± 9.5 kJ mol−1 at T = 298 K for H3BO3(s) = H3BO3(g).