Molecular Oxygen (O2)

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Isotopes

Stable Isotopes

oxygen element
Oxygen is a gaseous element forming 21% of the atmosphere. There are 3 stable isotopes of Oxygen: 16O, 17O, and 18O. Including the hydrogen isotopes H and D there are 9 different water isotopic combinations possible (and 18 if tritium is considered).
Natural Abundance
  Atomic Mass

Abundance

16O

15.99491463

99.7587%

17O

16.9991312

0.0374%

18O

17.9991603

0.2039%
The low enrichments of the 17Oxygen and 18Oxygen species means the chemical and physical properties of oxygen on earth are determined almost entirely by the 18Oxygen isotope
 

Oxygen-16

Abundance = 99.7587%

Cost:

~$20

oxygen cylinder

16O2
CAS 7782-44-7
16O-Water
CAS 7732-18-5

Oxygen-17

The Rarest Isotope

Applications in:

  • Spectroscopy - due to the property of nuclear spin (I=5/2) this oxygen isotope is unique. It can be used in magnetic resonance experiments (i.e. NMR and EPR) to study water and oxygen interactions.

Cost:

1L (20%) of 17O2 gas ~$2,000 (USD).
1g (80%) of 17O-water ~$1,250

This cylinder (right) cost $16,000

Abundance = 0.0374%

17Oxygen

17O2
CAS 67321-81-7
17O-Water
CAS 13768-40-6

Oxygen-18

Applications in:

  • Labeling studies - pathways (fluxes) of enzymatic and geochemical reactions.
  • Isotopic fractionation - insight into chemical reactions and transition states.
  • Vibrational spectroscopy - incorporation of the heavier 18O causes molecular vibrations to decrease in frequency.
  • PET - Positron Emission Tomography (medical imaging) uses H218O as a precursor. This application accounts for the vast increases in world-wide consumption of 18-Oxygen.

Cost:

1L (@95%) of 18O2 gas ~$1,000 USD.
1g (@95%) of 18O-water ~$150–200.

All prices USD 2004

Abundance = 0.2038%

18Oxygen

18O2
CAS 32767-18-3
18O-Water
CAS 14314-42-2

 

Commercial Fractionation of Oxygen Isotopes.

 

The oxygen isotopes are prepared via enrichment procedures of the oxide and total global 18O water generation is about 500 kg/year. Gas diffusion is apparently not commercially viable. Commercial quantities are however, produced by fractional distillation of water or cryogenic distillation of NO (nitrous oxide) or CO (carbon monoxide). Typically operation begins with NO and enrichment proceeds to a level of 10-30% , whereupon subsequent enrichment then proceeds via fractional distillation of water using long columns. Due to the low enrichment of the 18O (and especially 17O isotopes) and small difference in vapour pressures, a large number of theoretical plates are needed during the distillation process. This in practice translates to a slow process with a long lead time (6-12 months) as well as high energy requirements. Fractional distillation of water then also must contend with the natural abundance of Hydrogen and Deuterium (99.985% and 0.015% respectively). Therefore, when the water is distilled a mixture of the H- and D-water products are isolated. Isolation of pure >95% H218O is achieved after isotopic normalisation: electrolysis of water (liberating the gases H2 and O2) and reaction of the 18O2 with pure H2 to generate the oxide again. The same process is also implemented with D2 if D218O is required.
The difference in the physical properties (boiling points) of the 17O and 18O isotopic water are small and are the basis of the difficulty in separation. Due to the industrial scale and level of commercial investment, not a great deal of information is available concerning the practicalities of the distillation; however, Dostrovsky, I and Raviv, A. (1957) outline some of the early design considerations for sizes and packing material for the columns.

Dostrovsky, I. & Raviv, A. (1957) "Separation of Heavy Isotopes of Oxygen by Distillation" in Proceedings of the symposium on isotope separation (Ed. Kistemaker, J., Bigeleisen, J. & Nier, A.O.C.) pp. 336-349. North-Holland Publishing Company, Amsterdam.

Table of Physical properties

 
H216O
H217O
H218O
D216O
D217O
D218O
Calculated Mass (amu)
18.01079
19.01501
20.01504
20.02217
21.02639
22.02642
Boiling point (°C)
100.00
100.08 ± 0.05
100.15± 0.05
101.42
101.47 ± .05
101.54 ± 0.05
Density at 20°C
0.99797
 
1.11064
1.10513
 
1.21622
Temperature of max. Density
0.00
 
0.28
3.81
 
4.02
Heat of Evaporation (kJ/mol)
2,513.8
 
2,516.7
2,597.5
 
2,599.9
Viscosity at 20°C (cP)
1.0020
 
1.0564
1.2471
 
1.3050
CAS
7732-18-5
13768-40-6
14314-42-2
7789-20-0
20205-58-7
14674-67-0
Jancso, G. & Van Hook, W. A. (1974) Chem Rev. 74, 689
Staschewski, D. (1974) Angew. Chem. 13, 357.
 
Commercially then the gas is available in small cylinders and the water (oxide) available in a small ampules.
(see pictures below)
18O water small oxygen 18 cylinders
 
Currently one of the main uses of 18O water is P.E.T. or positron emission tomography. This technique has gained a wide acceptance for medical imaging and used in particular for cancer screening. The basic approach is to take 18O water and to add an additional proton (from a nuclear accelerator) and to generate a short-lived 18F isotope, which in turn is used to label molecules. This procedure is done on-site in the hospital as the 18F has a half life of 110 min. Particular medical interest is with 18F-fluoro deoxyglucose ( 2-[18F]FDG ) which is one of the most commonly labeled small biomolecules.
 

Radioisotopes

 
A number of radioisotopes have been synthesised for oxygen. They are generated via a cyclotron which provides high energy protons (originally from hydrogen ions). The collision energies of these high energy particles can be adjusted such that different isotopes can be isolated. The application of oxygen isotopes is for research and for nuclear medicine. Due to their half-life they are used in specialist applications.
 

 

 

Atomic Mass

(a.m.u.)

Half-Life

(s)

Atomic number

(i.e. Neutrons)

12O 12.0344   4
13O 13.0248 8.58 x 10-3 5
14O 14.0086 70.606 6
15O 15.0031 122.24 7
- - - -
19O 19.0036 26.91 11
20O 20.0041 13.51 12
21O 21.0087 3.42 13
22O 22.01 2.25 14
23O 23.016 82 x 10-3 15
24O 23.016 61 x 10-3 16

emissionln

Stable Isotope Manufactures Principle source manufacturers with distillation plants: Cambridge , Isotec and 18O uses from Cambridge <pdf>.

<List of Suppliers>

Plants from Google Earth Two manufacturing plants in the USA are less than 50 km appart. The reason for this is that were spun off from the DOE Mound Facility - with Isotec right down the street. Google earth links to <Isotech> and <CIL> (right click, save as, then reopen)

 

Mass Spectrometers The isotopic distribution of 16O, 17O and 18O materials (chemical, biological) is determined via isotope ratio mass spectrometry ( VG instruments / Thermo-Finnigan ). Measurements of isotopic distributions allow a range of geological and biological process to be resolved.

More Radioisotopes A nice summary of radioactive elements <here>.

 

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