Hostname: page-component-78c5997874-lj6df Total loading time: 0 Render date: 2024-11-18T05:06:21.730Z Has data issue: false hasContentIssue false
  • English
  • Français

Crystallographic Studies of NH4Cl—NH4Br Solid Solutions

Published online by Cambridge University Press:  06 March 2019

Jane Edmund Callanan  and
Norman O. Smith
Jane Edmund Callanan
Affiliation:
Fordham University, New York, New York
Norman O. Smith
Affiliation:
Fordham University, New York, New York
Get access

Abstract

Both ammonium chloride and ammonium bromide undergo a transition, with rise in temperature, from an interpenetrating simple cubic (II) to a face-centered cubic (I) lattice at 183 and 137°C, respectively, and both the low- and high-temperature forms give a complete series of solid solutions. We have determined the lattice constants of the high-temperature solids at about 250° as a function of composition, and redetermined the lattice constants of the low-temperature solids at room temperature. The solutions were made by crystallization from water, followed by stirring in contact with mother liquor for at least three weeks at room temperature. Measurements were made with a Norelco- Philips diffractometer and recorder, with Cu Ko. radiation. For the high-temperature work, a simple, inexpensive heating apparatus was developed. The only previous data reported for the high-temperature forms are the lattice constants of the pure components given by Bartlett and Langmuir.

The low-temperature solutions showed negative deviations from Vegard's rule at both ends of the concentration range and a slight positive deviation elsewhere when high-angle data were used. The high-temperature solutions showed marked positive deviations from Vegard's rule over the whole compositions range. Values for the pure components agreed reasonably well with those of Bartlett and Langmuir.

The progress of the change II → I with time was followed for some of the solutions in the neighborhood of the transition temperature in an attempt to reveal the mechanism of the process.

Type
Research Article
Information
Advances in X-Ray Analysis , Volume 9: Fourteenth Annual Conference on Applications of X-ray Analysis, August 25-27, 1965 , 1965 , pp. 159 - 169
Copyright
Copyright © International Centre for Diffraction Data 1965

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

1. Bridgman, P. W., “Polymorphism at High Pressures,” Proc. Am. Acad. Arts. Sci, 52: 91, 1916.Google Scholar
2. Foyhônen, J., “Dilatometric Investigation of NH4Cl at 183.1°C and NH4Br at 137.2°C,” Ann. Acad. Sci. Fennicae, Ser. A VI, No. 58, 1960.Google Scholar
3. Flatt, R. and Burkhardt, G., “Investigation of Solid Solution Formation in Solutions,” Helv. Chim. Acta 27: 1605, 1944.Google Scholar
4. Rassow, H., “A Simple Method for the Determination of Melting Points and Critical Temperatures,” Z. anorg. u. allgem. Chem. 114: 117, 1920,Google Scholar
5. Costich, P. S., Maass, G. J. Jr., and Smith, N. O., “Transitions in Ammonium Chloride—Ammonium Bromide Solid Solutions,” J. Chem. Eng. Data 8: 26, 1963.Google Scholar
6. Vegard, L., “The Constitution of Mixed Crystals and the Space Occupied by Atoms,” Z. Pkysik 5: 17, 1921.Google Scholar
7. Grimm, H. G. and Herzfeld, K. F., “The Lattice Energy and Dimensions of Mixed Crystals,” Z. Physik 16: 77, 1923.Google Scholar
8. Retgers, J. W., “The Specific Gravity of Isomorphic Mixtures,” Z. physik. Chem. 3: 497, 1889.Google Scholar
9. Jette, E. R., “Interrnetailic Solid Solutions,” Trans. Am. Inst. Mining Met. Engrs. 111 : 75, 1934.Google Scholar
10. Havighurst, R. J., Mack, E. Jr., and Blake, F. C., “Precision Crystal Measurements on Some Alkali and Ammonium Halides,” J. Am. Chem. Sac. 46: 2368, 1924.Google Scholar
11. Havighurst, R. J., Mack, E. Jr., and Blake, F. C., “Solid Solutions of the Alkali and Ammonium Halides,” J. Am. Chem. Soc. 47: 29, 1925.Google Scholar
12. Zen, E., “Validity of ‘Vegard's Law','Mm. Mineralogist 41: 523, 1956.Google Scholar
13. Bartlett, G. and Langmuir, I., “The Crystal Structures of the Ammonium Halides Above and Below the Transition Temperatures,” J. Am. Chem. Soc, 43: 84, 1921.Google Scholar
14. Anselmo, V. C. and Smith, N. O., “Lattice Constants of Ammonium Chloride-Ammonium Bromide Solid Solutions, J. Phys. Chem. 63: 1344, 1959.Google Scholar
15. Wood, L. J., Secunda, W., and McBride, C. M., “Reactions Between Dry Inorganic Salts. IX. The Effect of Common Ions on the Transition Temperature of Cesium Chloride,” J. Am. Chem. Soc. 80: 307, 1958.Google Scholar
16. Klug, H. P. and Alexander, L. E., X-Ray Diffraction Procedures, John Wiley & Sons, Inc., New York, 1954, p. 340.Google Scholar
17. Swanson, H. E. and Tatge, E., “Standard X-Ray Diffraction Powder Patterns,” NBS Circular No. 539, Vol. I: 59, 1953.Google Scholar
18. Swanson, H. E. and Fuyat, R., “Standard X-Ray Diffraction Powder Patterns,” NBS Circular No. 539, Vol. II; 49, 1953.Google Scholar