Quasi-ice-like CP behavior of molecular H2O in Hemimorphite Zn4Si2O7(OH)2· h2O: CP and entropy of confned H2O in microporous silicates

American Mineralogist

Volumn 94, Issue 4, 2009, Pages 634-637

  Geiger, Charles A ^a   Dachs, Edgar ^b  

^a UNIVERSITY OF KIEL   (Germany)

^b UNIVERSITY OF SALZBURG   (Austria)

Author keywords

Confined H 2O; Entropy; Heat capacity; Hemimorphite; Microporous minerals

Indexed keywords

DEHYDRATION; ENTROPY; HYDROGEN BONDS; ICE; LIQUIDS; MICROPOROSITY; MOLECULES; SILICATE MINERALS; SILICON; SPECIFIC HEAT; ZEOLITES;

CONFINED H2O; DEHYDRATION REACTIONS; ENTROPY VALUE; HEMIMORPHITE; LOW TEMPERATURES; MICRO-CALORIMETRY; MICROPOROUS; TETRAHEDRAL COORDINATION;

ZINC COMPOUNDS;

CALORIMETRY; DEHYDRATION; ENTROPY; HEAT CAPACITY; HYDROXYL RADICAL; OXYGEN; SILICATE; SILICON; WATER; ZEOLITE; ZINC;

EID: 67650441945     PISSN: 0003004X     EISSN: None     Source Type: Journal    
DOI: 10.2138/am.2009.3138     Document Type: Article

References (30)

1. Angell, C. A., Oguni, M., and Sichina, W. J. (1982) Heat capacity of water at extremes of supercooling and superheating. Journal of Physical Chemistry, 86, 998-1002.
2. Benisek, A. and Dachs, E. (2008) The uncertainty in determining the third law entropy by the heat-pulse calorimetric technique. Cryogenics, 48, 527-529.
3. 2 molecular sieves from T = 0 K to 400 K. Journal of Chemical Thermodynamics, 34, 205-227.
4. Breck, D. W. (1974) Zeolite Molecular Sieves, p. 771. Wiley, New York.
5. Chase Jr., M. W. (1998) NIST-JANAF Thermochemical Tables, 4th edition, Monograph No. 9 (Part I and Part II). Journal of Physical and Chemical Reference Data, American Institute of Physics, Melville, New York.
6. Cooper, B. J., Gibbs, G. V., and Ross, F. K. (1981) The effects of heating and dehydration on the crystal structure of hemimorphite up to 600 °C. Zeitschrift für Kristallographie, 156, 305-321.
7. Dachs, E. and Bertoldi, C. (2005) Precision and accuracy of the heat-pulse calorimetric technique: low-temperature heat capacities of milligram-sized synthetic mineral samples. European Journal of Mineralogy, 17, 251-261.
8. 12) garnet solid solutions: A low-temperature calorimetric and a thermodynamic investigation. American Mineralogist, 91, 894-906.
9. Dunitz, J. D. (1994) The entropic cost of bound water in crystals and biomolecules. Science, 264, 670.
10. Eisenberg, D. and Kauzmann, W. (1969) The Structure and Properties of Water. Oxford University Press, U. K.
11. Giauque, W. F. and Stout, J. W. (1936) The entropy of water and the third law of thermodynamics. The heat capacity of ice from 15 to 273 °K. Journal of American Chemical Society, 58, 1144-1150.
12. Helgeson, H. C., Delany, J. M., Nesbitt, H. W., and Bird, D. K. (1978) Summary and critique of the thermodynamic properties of rock-forming minerals. American Journal of Science, 278-A, 1-229.
13. Hill, R. J., Gibbs, G. V., Craig, J. R., Ross, F. K., and Williams, J. M. (1977) A neutrondiffraction study of hemimorphite. Zeitschrift für Kristallographie, 146, 241-259.
14. Jeffrey, G. A. (1997) An Introduction to Hydrogen Bonding, 303 p. Oxford University Press, New York.
15. Johnson, G. K., Flotow, H. E., O'Hare, P. A. G., and Wise, W. S. (1982) Thermodynamic studies of zeolites: Analcime and dehydrated analcime. American Mineralogist, 67, 736-748.
16. - (1983) Thermodynamic studies of zeolites: Natrolite, mesolite and scolecite. American Mineralogist, 68, 1134-1145.
17. - (1985) Thermodynamic studies of zeolites: Heulandite. American Mineralogist, 70, 1065-1071.
18. 77, 85-93.
19. 2O molecule and hydroxyl groups in the channels of hemimorphite. American Mineralogist, 91, 1355-1362.
20. 2O molecules in the channels of natrolite and scolecite: A Raman and IR spectroscopic investigation of hydrous microporous silicates. American Mineralogist, 91, 1039-1048.
21. Libowitzky, E. and Rossman, G. R. (1997) IR spectroscopy of hemimorphite between 82 and 373 K and optical evidence for a low-temperature phase transition. European Journal of Mineralogy, 9, 793-802.
22. Libowitzky, E., Kohler, T., Armbruster, T., and Rossman, G. R. (1997) Proton disorder in dehydrated hemimorphite; IR spectroscopy and X-ray structure refinement at low and ambient temperatures. European Journal of Mineralogy, 9, 803-810.
23. 2O. Zeitschrift für Kristallographie, 213, 659-668.
24. Paukov, I. E., Moroz, N. K., Kovalevskaya, Yu. A., and Belitsky, I. A. (2002) Lowtemperature thermodynamic properties of disordered zeolites of the natrolite group. Physics and Chemistry of Minerals, 29, 300-306.
25. 2O molecule in selected hydrous micro and nanoporous silicates. American Mineralogist, 92, 388-396.
26. 5 Pascals) pressure and at higher temperatures. U. S. Geological Survey Bulletin 2131, 461 p.
27. Robinson, G. R. and Haas Jr., J. L. (1983) Heat capacity, relative enthalpy, and calorimetric entropy of silicate minerals: An empirical method of prediction. American Mineralogist, 68, 541-553.
28. Taylor, H. F. W. (1962) The dehydration of hemimorphite. American Mineralogist, 47, 932-944.
29. Van Hinsberg, V. J., Vriend, S. P., and Schumacher, J. C. (2005) A new method to calculate end-member thermodynamic properties of minerals from their constituent polyhedra I: enthalpy, entropy and molar volume. Journal of Metamorphic Geology, 23, 165-179.
30. Velde, B. and Besson, J. M. (1981) Raman spectra of analcime under pressure. Physics and Chemistry of Minerals, 7, 96-99.