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

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Thermodynamic Properties of Alkali Metal Hydroxides. Part 1. Lithium and Sodium Hydroxides Thermodynamic Properties of Alkali Metal Hydroxides. Part 1. Lithium and Sodium Hydroxides Cite as: Journal of Physical and Chemical Reference Data 25, 1211 (1996); https://doi.org/10.1063/1.555982 Submitted: 03 November 1993 . Published Online: 15 October 2009 L. V. Gurvich, G. A. Bergman, L. N. Gorokhov, V. S. Iorish, V. Ya. Leonidov, and V. S. Yungman ARTICLES YOU MAY BE INTERESTED IN Thermodynamic Properties of Alkali Metal Hydroxides. Part II. Potassium, Rubidium, and Cesium Hydroxides Journal of Physical and Chemical Reference Data 26, 1031 (1997); https:// doi.org/10.1063/1.555996 JANAF Thermochemical Tables, 1974 Supplement Journal of Physical and Chemical Reference Data 3, 311 (1974); https:// doi.org/10.1063/1.3253143 Erratum: Liquid–Liquid Demixing from Solutions of Polystyrene. 1. A Review. 2. Improved Correlation with Solvent Properties [J. Phys. Chem. Ref. Data 25, 637 (1996)] Journal of Physical and Chemical Reference Data 25, 1277 (1996); https:// doi.org/10.1063/1.555984 Journal of Physical and Chemical Reference Data 25, 1211 (1996); https://doi.org/10.1063/1.555982 25, 1211 © 1996 American Institute of Physics for the National Institute of Standards and Technology. Thermodynamic Properties of Alkali Metal Hydroxides. Part 1. Lithium and Sodium Hydroxides L. V. Gurvich, G. A. Bergman, L. N. Gorokhov, V. S. lorish, V. Va. Leonidov, and V. S. Vungman Thermocenter of the Russian Academy of Sciences, Izhorskaya st. 13119, IVTAN, Moscow, 127412, Russia (Received November 3, 1993; revised manuscript received November 30, 1995) 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. © 1996 American Institute of Physics and American Chemical Society. Key words: bond energy; dissociation energy; enthalpy; enthalpy of formation; entropy; fusion; heat capacity; hydroxides; molecular (vibrational) constants and structure; phase transition; thermodynamic properties. Contents 1. Introduction ................................ 1213 3.2.4. Appendix. Tables of Experimental and 1.1. References for the Introduction ............ 1214 Evaluated Data for Na202H2(g) ........ 1269 2. Lithium Hydroxide .......................... 1215 4. References for Lithium and Sodium Hydroxides .. 1271 2.1. Lithium Hydroxide in Condensed Phases .... 1215 5. Recommendations for Future Measurements ..... 1276 2.1.1. Heat Capacity and Enthalpy List of Tables Measurements ...................... 1215 2.1.2. Enthalpy of Formation of LiOH(cr) ..... 1219 1-1. Crystal structure and lattice parameters of the 2.1.3. Appendix. Tables of Experimental and alkali metal hydroxides ..................... 1214 Evaluated Data..................... 1222 2-1. Experimental heat capacity values of LiOH 2.2. Lithium Hydroxide in Gaseous Phase ....... 1226 [50BAU/JOH]. ........................... 1222 2.2.1. Lithium Hydroxide Monomer. ........ 1226 2-2. Experimental enthalpy values HO (T) - HO 2.2.2. Appendix. Tables of Experimental and (298.15 K) of LiOH [54POWIBLA]. ......... 1222 Evaluated Data for LiOH(g) ........... 1237 2-3. Experimental enthalpy values HO (T) - HO (298.15 K) of LiOH [55SHO/COH]. .......... 1223 2.2.3. Lithium Hydroxide Dimer............ 1240 2-4. Comparison of the heat capacity, enthalpy, 2.2.4. Appendix. Tables of Experimental and entropy, and enthalpy of formation values for Evaluated Data for Li 0 H (g) ........ 1244 2 2 2 LiOH(cr) ................................ 1223 3. Sodium Hydroxide .......................... 1246 2-5. Temperature of fusion of LiOH .............. 1223 3.1. Sodium Hydroxide in Condensed Phases .... 1246 2-6. Enthalpy of fusion of LiOH ................. 1224 3.1.1. Heat Capacity and Enthalpy 2-7. Thermal functions of LiOH(cr) below Measurements ...................... 1246 298.15 K................................ 1224 3.1.2. Enthalpy of Formation of NaOH(cr) .... 1253 2-8. Differences (in J K- 1 mol-I) between the 3.1.3. Appt:Illlix. Tabks uf Expt:rimt:ulal amI thermal functions of LiOH(cr and liq) Evaluated Data for NaOH(cr) ......... 1255 calculated in the present work and in 3.2. Sodium Hydroxide in Gaseous Phase ....... 1260 [82GURlVEY] and in [85CHAIDA V]. ........ 1224 3.2.1. Sodium Hydroxide Monomer .......... 1260 2-9. The enthalpy of formation of LiOH(cr) from 3.2.2. Appendix. Tables of Experimental and measurements of the enthalpy of solution of Evaluated Data for NaOH(g) .......... 1266 lithium hydroxide in water. ................. 1224 3.2.3. Sodium Hydroxide Dimer. ........... 1268 2-10. The enthalpy of formation of LiOH(cr) based on dissociation pressure measurements for reaction 2LiOH(cr,liq) = Li2O(cr) ©1996 by the U.S. Secretary of Commerce on behalf of the United States. + H 0(g) (kJ mol-I) ....................... 1224 All rights reserved. This copyright is assigned to the American Institute of 2 Physics and the American Chemical Society. 2-11. Experimental data on the equilibrium constants Reprints available from ACS; see Reprints List at back of issue. (Klatm) at different temperatures (TIK) for the 0047-2689/96/25(4)/1211/66/$18.00 1211 J. Phys. Chern. Ref. Data, Vol. 25, No.4, 1996 1212 GURVICH ET AL. reaction 2LiOH(cr,liq) = Li20(cr) + H20(g) ..... 1225 NaOH(cr). .. 1257 2-12. Thermodynamic properties at 0.1 MPa: 3~9. Temperatures of phase transformations of LiOH(cr and liq) .... ".................... " 1226 NaOH................................... 1258 2-13. Bond lengths (in A.) and vibrational frequencies :;·10. Tempp-f::ltllre of fl1~ion of NaOH........... '" 1258 (in cm - I) of LiOH in the ground electronic 3~11. Enthalpy of ,B-y transition of NaOH.......... 1258 state. .. 1229 3-12. Enthalpy of fusion of NaOH. .. 1259 I 2-14. Differences (in J K- 1 mol-I) between the 3-13. Differences (in J K- mol-I) between the thermal functions of LiOH(g) calculated in thermal functions of NaOH(cr and liq) the present work and in [82GURlVEY, calculated in the present work and in 85CHAIDA V]. ......................... " 1230 [82GURlVEY] and in [85CHAlDAV]. ...... " 1259 2-15. Equilibrium constant values for reaction Li(g) 3-14. The enthalpy of formation of NaOH(cr) from + HzO(g)= LiOH(g)+ H(g) ................ " 1237 measurements of the enthalpies of solution of 2-16. Equilibrium constant values for reaction sodium hydroxide in water ....... , ......... , 1259 3-15. Thermodynamic properties at 0.1 MPa: Li20(cr)+H20(g)=2LiOH(g) .............. " 1238 2-17. Results of experimental determinations of NaOH(cr( a,p, y) and liq). .. 1260 LlfHO(LiOH,g,O), kJ mol-I ................ " 1238 3-16. Bond lengths (in A) and vibrational frequencies 2-18. Results of quantum-mechanical calculations of (in cm -1) of NaOH in the ground electronic LlfHO(LiOH,g,O) .. ...................... " 1239 state .................................. " 1262 1 2-19. Comparison of the heat capacity, enthalpy, 3-17. Differences (in J K- mol-I) between the entropy, and enthalpy of formation values for thermal functions of NaOH(g) calculated in LiOH(g) ............................... " 1239 the present work and in [82GURlVEY, 85CHN 2-20. Thermodynamic properties at 0.1 MPa: DAV]. ................................ " 1263 LiOH(g) ............................... " 1239 3-18. Total vapor pressure over sodium hydroxjde, 2-21. Bond lengths (in A), angles (in deg) and [21WARJALB]. .......................... 1266 vibrational frequencies (in cm - I) of 3-19. Results of experimental determinations of ~fHO(NaOH,g,O), kJ mol-t, ...... , ... , ... " 1266 Li20 2H2 in the ground electronic state....... " 1241 2-22. Differences (in J K- 1 mol-I) between the 3-20. Results of quantum-mechanical determinations of LlfHO(NaOH,g,O), kJ mol-I ............... 1267 thermal functions of Li20 2H2(g) calculated 3 21. Comparison of the heat capacity, enthalpy, in the present work and in [~2(jURI VEY, 85CHAJDA V] ..................... " 1242 entropy, and enthalpy of formation values for 2-23. Equilibrium constant values for reaction NaOH(g). , .... , .................. , ...... 1267 3-22. Thermodynamic properties at 0.1 MPa: Li20 2Hig)=2LiOH(g), [60BERJMES] ........ 1244 2-24. Results of experimental determinations of NaOH(g). .. 1267 AfHO(Li202H2 ,g,O), kJ mol-I ............. " 1244 3-23. Bond lengths (in A), angles (in deg), and vibrational frequencies (in cm - 1) of 2-25. Results of quantum-mechanical calculations of o Na202H2 in the ground electronic state ... , .. " 1268 AfH (Li20 2H2 ,g,O) ...................... " 1244 3-24. Differences fin J K- 1 I)1ol-1) between the 2-26. Comparison of the heat capacity, enthalpy, entropy, and enthalpy of formation values for thermal functions of Na202H2(g) calculated in the present work and in [82GURJ Li,01H2(g). .. 1244 VEY, ~5CHNDAV J. .. 1268 2-27. Thermodynamic properties at 0.1 MPa: o LizOzHig) ............................
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