Triplet oxygen

Triplet oxygen

Names
Preferred IUPAC name Triplet oxygen
Systematic IUPAC name Dioxidanediyl (substitutive) dioxygen(2•)(triplet) (additive)
Identifiers
CAS Number	7782-44-7 Y
ChEBI	CHEBI:27140
EC Number	231-956-9
Gmelin Reference	492
Jmol 3D model	Interactive image Interactive image Interactive image
KEGG	D00003 Y
MeSH	Oxygen
RTECS number	RS2060000
UN number	1072
InChI InChI=1S/O2/c1-2 Key: MYMOFIZGZYHOMD-UHFFFAOYSA-N
SMILES [O]#[O] o:o [O][O]
Properties
Chemical formula	O2
Molar mass	32.00 g·mol−1
Appearance	Colorless gas
Melting point	−218.2 °C; −360.7 °F; 55.0 K
Boiling point	−183.2 °C; −297.7 °F; 90.0 K
Structure
Molecular shape	Linear
Dipole moment	0 D
Thermochemistry
Std molar entropy (So298)	205.152 J K−1 mol−1
Std enthalpy of formation (ΔfHo298)	0 kJ mol−1
Pharmacology
ATC code	V03AN01
Vapor pressure	{{{value}}}
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Triplet oxygen, systematically but less commonly, 1,2-dioxidanediyl, is a term that refers to normal, gaseous oxygen (O₂, dioxygen) in its ground state. It is therefore classified as an inorganic chemical, and more specifically as a particular electronic state of one allotrope of the inorganic chemical element, oxygen. In this particular state, according to one type of modern bonding theory, the electron configuration of the oxygen molecule has two electrons occupying two molecular orbitals (MOs) of equal energy (that is, degenerate MOs), therefore remaining unpaired. These orbitals are classified as antibonding and are of higher energy, so the resulting bonding structure between the oxygen atoms is weakened (i.e., is higher in energy)—for instance, it is higher in energy than the bonding in dinitrogen, where bonding MOs are filled instead. The spectroscopic molecular term symbol for triplet (ground state) oxygen is ³Σ_g⁻.

Spin

File:Valence orbitals of oxygen atom and dioxygen molecule (diagram).svg

The valence orbitals of molecular oxygen (middle); in the ground state, the electrons in the π^* orbitals have their spins parallel.

The s=1/2 spins of the two electrons in degenerate orbitals gives rise to 2x2=4 independent spin states in total. Exchange interaction splits these into a singlet state (total spin S=0) and a set of 3 degenerate triplet states (S=1). In agreement with Hund's rules, the triplet states are energetically more favorable, and the ground state of the molecule carries an electron spin of S=1. Excitation to the S=0 state results in much more reactive, metastable singlet oxygen.

Because the molecule in its ground state has a non-zero spin magnetic moment, oxygen is paramagnetic; i.e., it can be attracted to the poles of a magnet. The Lewis structure O=O does not accurately represent the diradical nature of molecular oxygen; molecular orbital theory must be used to adequately account for the unpaired electrons. Triplet oxygen is better described by a bond order of one and two halves instead of two to better reflect its unpaired bonding electrons. This allows for easier reasoning of the bond length.

Reaction

The unusual electron configuration prevents molecular oxygen from reacting directly with many other molecules, which are often in the singlet state. Triplet oxygen will, however, readily react with molecules in a doublet state, such as radicals, to form a new radical. Conservation of spin quantum number would require a triplet transition state in a reaction of triplet oxygen with a closed shell (a molecule in a singlet state). The extra energy required is sufficient to prevent direct reaction at ambient temperatures with all but the most reactive substrates, e.g. white phosphorus. At higher temperatures or in the presence of suitable catalysts the reaction proceeds more readily. For instance, most flammable substances are characterised by an autoignition temperature at which they will undergo combustion in air without an external flame or spark.

Further reading

• McNaught, A. D. & A. Wilkinson. (1997) "Singlet molecular oxygen (singlet molecular dioxygen)," In IUPAC Compendium of Chemical Terminology, 2nd edn. [the "Gold Book"], Oxford, GBR:Blackwell, ISBN 0967855098, DOI 10.1351/goldbook and 10.1351/goldbook.S05695; XML on-line corrected version created by M. Nic, J. Jirat, & B. Kosata, with updates compiled by A. Jenkins, see [1] or [2], accessed 11 August 2015.

External sources

• http://meta-synthesis.com/webbook/16_diradical/diradical.html

• Atkins, Peter; Julio de Paula & Ronald Friedman (2009) Quanta, Matter, and Change: A Molecular Approach to Physical Chemistry, pp. 341-342, Oxford, GBR:Oxford University Press, ISBN 0199206066, see [3]. accessed 11 August 2015.
• Christian Hill, 2015, "Molecular Term Symbols," self-published, from Post-Doctoral Research Associate at the Department of Physics and Astronomy, University College London, see [4], accessed 11 August 2015.