Chemistry:Polycarbonyl
Polycarbonyl, (also known as polymeric-CO, p-CO or poly-CO) is a solid, metastable, and explosive polymer of carbon monoxide.[1] The polymer is produced by exposing carbon monoxide to high pressures. The structure of the solid appears amorphous, but may include a zig zag of equally-spaced CO groups.[2]
Formation
Poly-CO can be produced at pressures of 5.2 GPa; it is amorphous and yellow to dark red in color.[3] Polymerisation is catalysed by blue light at slightly lower pressures in the δ-phase of solid CO.[4] Another white, crystalline phase can be made at higher temperatures at 6 or 7 GPa.[1]
R. J. Mills discovered this solid, which was first produced in a tungsten carbide anvil in 1947. Originally this was thought to be polymeric carbon suboxide, but the formation does not yield any gas byproduct such as carbon dioxide.[5] The yield of the solid can be up to 95%.[6]
Properties
The polymer is stable above about 80 K. Below this temperature the ε form of solid molecular CO is formed instead. When the pressure is released the polymer remains stable at atmospheric pressure. The solid dissolves in water, alcohol and acetone.[5] When exposed to the atmosphere it is hygroscopic, becomes gluey, and changes colour, becoming darker.[6] The reaction with water produces carboxylic groups.[7][8]
The solid stores a high energy. It can decompose explosively forming glassy carbon and carbon dioxide.[6] The energy density stored can be up to 8 kJ/g. During the decomposition the temperature can be 2500 K.[6] The density is 1.65 g/cm3, however most of the solid produced is porous, so the true density is likely to be higher.[6]
Infrared spectroscopy shows bands at 650, 1210, 1440, 1650 and 1760 cm−1. The 1760 band is likely to be due to the -C-(C=O)-C- structure.[4] The 1600 is due to vibration of a C=C double bond.[6]
The solid is electrically insulating with an electronic gap energy of 1.9 eV.[4]
Nuclear magnetic resonance for the material made from 13CO shows sharp resonance at 223 ppm due to ester or lactone attached carbon, and 151 ppm due to C=C double bonds. There is also broad resonance at 109 and 189 ppm. Over time of a few days, the 223 ppm peak reduces and all the other features increase in strength.[6]
Structure
Ideas of the structure include a zig zag chain of CO pointing in opposite directions, or five atom rings connected by CO and C–C bonds. The rings are lactones of tetronic acid: –C:–(C=O)–(C–O−
)–(C=O)–O–. Interconnections between the rings are zig zags of CO.[4]
Other ideas of the structure of the solid, include graphitic carbon with carbon dioxide under pressure, and a polymer with this C
3O
2 monomer: –(C=O)–O–(C−
)=C<. Yet other ideas are that the solid is the same as the polymer of carbon suboxide with oxalic anhydride.[9]
References
- ↑ 1.0 1.1 Rademacher, N.; L. Bayarjargal (2011). "Preparation and characterization of solid carbon monoxide at high pressure in the diamond anvil cell". http://photon-science.desy.de/annual_report/files/2011/20111732.pdf. Retrieved 30 May 2013.
- ↑ Podeszwa, Rafał; Rodney J. Bartlett (2003). "Crystal orbital study of polycarbonyl". International Journal of Quantum Chemistry 95 (4–5): 638–642. doi:10.1002/qua.10655. ISSN 0020-7608.
- ↑ Rademacher, Nadine; Lkhamsuren Bayarjargal. "High Pressure Investigations of Liquid and Polymerized CO up to 20 GPa Using Pair Distribution Function Analysis". http://www.dxcicdd.com/13/abstracts/D-26.pdf. Retrieved 30 May 2013.
- ↑ 4.0 4.1 4.2 4.3 Bernard, Stephane (Feb 1998). "DECOMPOSITION AND POLYMERIZATION OF SOLID CARBON MONOXIDE UNDER PRESSURE". Trieste. http://streaming.ictp.trieste.it/preprints/P/98/010.pdf. Retrieved 30 May 2013.
- ↑ 5.0 5.1 Mills, R. L.; D. Schiferl; A. I. Katz; B. W. Olinger (1984). "New Phases and Chemical Reactions in Solid Co Under Pressure". Le Journal de Physique Colloques 45 (C8): C8–187–C8–190. doi:10.1051/jphyscol:1984833. ISSN 0449-1947. http://hal.archives-ouvertes.fr/docs/00/22/43/33/PDF/ajp-jphyscol198445C833.pdf.
- ↑ 6.0 6.1 6.2 6.3 6.4 6.5 6.6 Lipp, Magnus J.; William J. Evans, Bruce J. Baer, Choong-Shik Yoo; Baer, Bruce J.; Yoo, Choong-Shik (2005). "High-energy-density extended CO solid". Nature Materials 4 (3): 211–215. doi:10.1038/nmat1321. ISSN 1476-1122. PMID 15711555. Bibcode: 2005NatMa...4..211L. https://dco.gl.ciw.edu/sites/dco.gl.ciw.edu/files/Lipp%20Nat%20Mat%202005.pdf.
- ↑ Ceppatelli, Matteo; Anton Serdyukov; Roberto Bini; Hans J. Jodl (2009). "Pressure Induced Reactivity of Solid CO by FTIR Studies". The Journal of Physical Chemistry B 113 (19): 6652–6660. doi:10.1021/jp900586a. ISSN 1520-6106. PMID 19368397.
- ↑ Katz, Allen I.; David Schiferl; Robert L. Mills (1984). "New phases and chemical reactions in solid carbon monoxide under pressure". The Journal of Physical Chemistry 88 (15): 3176–3179. doi:10.1021/j150659a007. ISSN 0022-3654.
- ↑ Lipp, M.; W. J. Evans; V. Garcia-Baonza; H. E. Lorenzana (1998). "Carbon Monoxide: Spectroscopic Characterization of the High–Pressure Polymerized Phase". Journal of Low Temperature Physics 111 (3/4): 247–256. doi:10.1023/A:1022267115640. ISSN 0022-2291. Bibcode: 1998JLTP..111..247L.
Other reading
- Batyrev, I. G.; W. D. Mattson; B. M. Rice (2012). "Modeling of Early Stages of Formation of Poly-CO". MRS Proceedings 1405. doi:10.1557/opl.2012.345. ISSN 1946-4274.
- Sun, Jian; Dennis D. Klug; Chris J. Pickard; Richard J. Needs (2011). "Controlling the Bonding and Band Gaps of Solid Carbon Monoxide with Pressure". Physical Review Letters 106 (14): 145502. doi:10.1103/PhysRevLett.106.145502. ISSN 0031-9007. PMID 21561202. Bibcode: 2011PhRvL.106n5502S. http://discovery.ucl.ac.uk/1305843/1/1305843.pdf.
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