DOI: 10.1063/1.4742340. Melting and dissociation of ammonia at high pressure and high temperature

Melting and dissociation of ammonia at high pressure and high temperature

10.1063/1.4742340

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

Raman spectroscopy and synchrotron x-ray diffraction measurements of ammonia (NH3) in laser-heated diamond anvil cells, at pressures up to 60 GPa and temperatures up to 2500 K, reveal that the melting line exhibits a maximum near 37 GPa and intermolecular proton fluctuations substantially increase in the fluid with pressure. We find that NH3 is chemically unstable at high pressures, partially dissociating into N2 and H2. Ab initio calculations performed in this work show that this process is thermodynamically driven. The chemical reactivity dramatically increases at high temperature (in the fluid phase at T &gt; 1700 K) almost independent of pressure. Quenched from these high temperature conditions, NH3 exhibits structural differences from known solid phases. We argue that chemical reactivity of NH3 competes with the theoretically predicted dynamic dissociation and ionization.

Bibliography

Ojwang, J. G. O., Stewart McWilliams, R., Ke, X., & Goncharov, A. F. (2012). Melting and dissociation of ammonia at high pressure and high temperature. The Journal of Chemical Physics, 137(6).

Authors 4

J. G. O. Ojwang (first)
R. Stewart McWilliams (additional)
Xuezhi Ke (additional)
Alexander F. Goncharov (additional)

References 45 Referenced 27

10.1126/science.214.4517.145 / Science (1981)
10.1126/science.283.5398.44 / Science (1999)
10.1126/science.240.4853.779 / Science (1988)
10.1126/science.253.5020.648 / Science (1991)
10.1038/ncomms1198 / Nat. Commun. (2011)
10.1038/nmat2261 / Nature Mater. (2008)
10.1021/j100223a030 / J. Phys. Chem. (1982)
10.1107/S0108270184008994 / Acta Crystallogr., Sect. C: Cryst. Struct. Commun. (1984)
10.1103/PhysRevLett.76.74 / Phys. Rev. Lett. (1996)
10.1063/1.2903491 / J. Chem. Phys. (2008)
10.1103/PhysRevB.79.100101 / Phys. Rev. B (2009)
10.1103/PhysRevB.37.2102 / Phys. Rev. B (1988)
10.1103/PhysRevB.73.174111 / Phys. Rev. B (2006)
10.1107/S0909049509033433 / J. Synchrotron Radiat. (2009)
10.1080/08957950802050718 / High Press. Res. (2008)
10.1063/1.3626860 / J. Chem. Phys. (2011)
10.1103/PhysRevLett.101.095502 / Phys. Rev. Lett. (2008)
10.1103/PhysRev.140.A1133 / Phys. Rev. B (1965)
10.1103/PhysRev.136.B864 / Phys. Rev. B (1964)
10.1103/PhysRevLett.45.566 / Phys. Rev. Lett. (1980)
10.1016/0927-0256(96)00008-0 / Comp. Mat. Sci. (1996)
10.1103/PhysRevB.54.11169 / Phys. Rev. B (1996)
10.1103/PhysRevB.50.17953 / Phys. Rev. B (1994)
10.1103/PhysRevB.59.1758 / Phys. Rev. B (1999)
10.1103/PhysRevB.13.5188 / Phys. Rev. B (1976)
10.1103/PhysRevLett.78.4063 / Phys. Rev. Lett. (1997)
{'year': '2005', 'key': '2023062003510610000_c27'} (2005)
{'volume-title': 'Theory of Lattice Dynamics in the Harmonic Approximation in Solid State, Physics Supplement', 'year': '1971', 'key': '2023062003510610000_c28'} / Theory of Lattice Dynamics in the Harmonic Approximation in Solid State, Physics Supplement (1971)
10.1103/PhysRevLett.83.332 / Phys. Rev. Lett. (1999)
10.1103/RevModPhys.66.671 / Rev. Mod. Phys. (1994)
10.1063/1.462356 / J. Chem. Phys. (1992)
10.1103/PhysRevLett.102.049601 / Phys. Rev. Lett. (2009)
10.1088/0953-8984/7/45/007 / J. Phys.: Condens. Matter (1995)
10.1002/zaac.19291780123 / Z. Anorg. Allg. Chem. (1929)
10.1103/PhysRevB.65.052102 / Phys. Rev. B (2001)
10.1103/PhysRevLett.94.125508 / Phys. Rev. Lett. (2005)
10.1146/annurev.physchem.51.1.763 / Annu. Rev. Phys. Chem. (2000)
10.1073/pnas.0808137105 / Proc. Natl. Acad. Sci. U.S.A. (2008)
10.1029/2005GL022499 / Geophys. Res. Lett. (2005)
10.1088/0953-8984/16/14/028 / J. Phys.: Condens. Matter (2004)
10.1103/PhysRevLett.108.165702 / Phys. Rev. Lett. (2012)
{'key': '2023062003510610000_c43', 'first-page': '1882', 'volume-title': 'CRC Handbook of Chemistry and Physics', 'year': '1960', 'edition': '42nd ed.'} / CRC Handbook of Chemistry and Physics (1960)
10.1038/ncomms1184 / Nat. Commun. (2011)
10.1086/172440 / Astrophys. J. (1993)
10.1006/icar.1994.1045 / Icarus (1994)

Dates

Type	When
Created	13 years ago (Aug. 14, 2012, 6:51 p.m.)
Deposited	2 years, 2 months ago (June 19, 2023, 11:52 p.m.)
Indexed	1 month ago (July 30, 2025, 6:58 a.m.)
Issued	13 years ago (Aug. 14, 2012)
Published	13 years ago (Aug. 14, 2012)
Published Online	13 years ago (Aug. 14, 2012)
Published Print	13 years ago (Aug. 14, 2012)

Funders 1

U.S. Department of Energy 10.13039/100000015
Region: Americas
gov (National government)
Labels8
1. Energy Department
2. Department of Energy
3. United States Department of Energy
4. ENERGY.GOV
5. US Department of Energy
6. USDOE
7. DOE
8. USADOE
Awards2
1. W-31-109-Eng-38
2. DE-AC02-06CH11357

BibTeX

@article{Ojwang_2012, title={Melting and dissociation of ammonia at high pressure and high temperature}, volume={137}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.4742340}, DOI={10.1063/1.4742340}, number={6}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Ojwang, J. G. O. and Stewart McWilliams, R. and Ke, Xuezhi and Goncharov, Alexander F.}, year={2012}, month=aug }

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    "date-time": "2023-06-20T03:52:47Z",
    "timestamp": 1687233167000
  },
  "score": 1,
  "resource": {
    "primary": {
      "URL": "https://pubs.aip.org/jcp/article/137/6/064507/72736/Melting-and-dissociation-of-ammonia-at-high"
    }
  },
  "subtitle": [],
  "short-title": [],
  "issued": {
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  "URL": "http://dx.doi.org/10.1063/1.4742340",
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  "ISSN": [
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    "1089-7690"
  ],
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