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Isotopes of lithium

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Naturally occurring lithium (3Li) is composed of two stable isotopes, lithium-6 (6Li) and lithium-7 (7Li), with the latter being far more abundant on Earth. Both of the natural isotopes have an unexpectedly low nuclear binding energy per nucleon (5332.3312(3) keV for 6Li and 5606.4401(6) keV for 7Li) when compared with the adjacent lighter and heavier elements, helium (7073.9156(4) keV for helium-4) and beryllium (6462.6693(85) keV for beryllium-9). The longest-lived radioisotope of lithium is 8Li, which has a half-life of just 838.7(3) milliseconds. 9Li has a half-life of 178.2(4) ms, and 11Li has a half-life of 8.75(6) ms. All of the remaining isotopes of lithium have half-lives that are shorter than 10 nanoseconds. The shortest-lived known isotope of lithium is 4Li, which decays by proton emission with a half-life of about 91(9) yoctoseconds (9.1(9)×10−23 s), although the half-life of 3Li is yet to be determined, and is likely to be much shorter, like 2He (helium-2, diproton) which undergoes proton emission within 10−9 s.

Isotopes of lithium (3Li)
Main isotopes[1] Decay
abun­dance half-life (t1/2) mode pro­duct
6Li [1.9%, 7.8%] stable
7Li [92.2%, 98.1%] stable
Significant variation occurs in commercial samples because of the wide distribution of samples depleted in 6Li.
Standard atomic weight Ar°(Li)

Both 7Li and 6Li are two of the primordial nuclides that were produced in the Big Bang, with 7Li to be 10−9 of all primordial nuclides, and 6Li around 10−13.[4] A small percentage of 6Li is also known to be produced by nuclear reactions in certain stars. The isotopes of lithium separate somewhat during a variety of geological processes, including mineral formation (chemical precipitation and ion exchange). Lithium ions replace magnesium or iron in certain octahedral locations in clays, and lithium-6 is sometimes preferred over 7Li. This results in some enrichment of 6Li in geological processes.

In nuclear physics, 6Li is an important isotope, because when it is bombarded with neutrons, tritium is produced.

Both 6Li and 7Li isotopes show nuclear magnetic resonance effect, despite being quadrupolar (with nuclear spins of 1+ and 3/2−). 6Li has sharper lines, but due to its lower abundance requires a more sensitive NMR-spectrometer. 7Li is more abundant, but has broader lines because of its larger nuclear spin. The range of chemical shifts is the same of both nuclei and lies within +10 (for LiNH2 in liquid NH3) and −12 (for Li+ in fulleride).[5]

List of isotopes

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Nuclide
[n 1] 		Z N Isotopic mass (Da)[6]
[n 2][n 3] 		Half-life[1]

[resonance width] 		Decay
mode[1]
[n 4] 		Daughter
isotope
[n 5] 		Spin and
parity[1]
[n 6][n 7] 		Natural abundance (mole fraction)
Excitation energy Normal proportion[1] Range of variation
3
Li
[n 8] 		3 0 3.03078(215)# p ?[n 9] 2
He
 ? 		3/2−#
4
Li
 		3 1 4.02719(23) 91(9) ys
[5.06(52) MeV] 		p 3
He
 		2−
5
Li
 		3 2 5.012540(50) 370(30) ys
[1.24(10) MeV] 		p 4
He
 		3/2−
6
Li
[n 10] 		3 3 6.0151228874(15) Stable 1+ [0.019, 0.078][7]
6m
Li
 		3562.88(10) keV 56(14) as IT 6
Li
 		0+
7
Li
[n 11] 		3 4 7.016003434(4) Stable 3/2− [0.922, 0.981][7]
8
Li
 		3 5 8.02248624(5) 838.7(3) ms β− 8
Be
[n 12] 		2+
9
Li
 		3 6 9.02679019(20) 178.2(4) ms β−n (50.5(1.0)%) 8
Be
[n 13] 		3/2−
β− (49.5(1.0)%) 9
Be
10
Li
 		3 7 10.035483(14) 2.0(5) zs
[0.2(1.2) MeV] 		n 9
Li
 		(1−, 2−)
10m1
Li
 		200(40) keV 3.7(1.5) zs IT 1+
10m2
Li
 		480(40) keV 1.35(24) zs
[0.350(70) MeV] 		IT 2+
11
Li
[n 14] 		3 8 11.0437236(7) 8.75(6) ms β−n (86.3(9)%) 10
Be
 		3/2−
β− (6.0(1.0)%) 11
Be
β−2n (4.1(4)%) 9
Be
β−3n (1.9(2)%) 8
Be
[n 15]
β−α (1.7(3)%) 7
He
β−d (0.0130(13)%) 9
Li
β−t (0.0093(8)%) 8
Li
12
Li
 		3 9 12.05378(107)# < 10 ns n ?[n 9] 11
Li
 ? 		(1−, 2−)
13
Li
 		3 10 13.061170(80) 3.3(1.2) zs
[0.2(9.2) MeV] 		2n 11
Li
 		3/2−#
This table header & footer:
  1. ^ mLi – Excited nuclear isomer.
  2. ^ ( ) – Uncertainty (1σ) is given in concise form in parentheses after the corresponding last digits.
  3. ^ # – Atomic mass marked #: value and uncertainty derived not from purely experimental data, but at least partly from trends from the Mass Surface (TMS).
  4. ^ Modes of decay:
    IT: Isomeric transition
    n: Neutron emission
    p: Proton emission
  5. ^ Bold symbol as daughter – Daughter product is stable.
  6. ^ ( ) spin value – Indicates spin with weak assignment arguments.
  7. ^ # – Values marked # are not purely derived from experimental data, but at least partly from trends of neighboring nuclides (TNN).
  8. ^ Discovery of this isotope is unconfirmed
  9. ^ a b Decay mode shown is energetically allowed, but has not been experimentally observed to occur in this nuclide.
  10. ^ One of the few stable odd-odd nuclei
  11. ^ Produced in Big Bang nucleosynthesis and by cosmic ray spallation
  12. ^ Immediately decays into two α-particles for a net reaction of 8Li → 24He + e−
  13. ^ Immediately decays into two α-particles for a net reaction of 9Li → 24He + 1n + e−
  14. ^ Has 2 halo neutrons
  15. ^ Immediately decays into two 4He atoms for a net reaction of 11Li → 24He + 31n + e−

Isotope separation

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Colex separation

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Main article: COLEX process

Lithium-6 has a greater affinity than lithium-7 for the element mercury. When an amalgam of lithium and mercury is added to solutions containing lithium hydroxide, the lithium-6 becomes more concentrated in the amalgam and the lithium-7 more in the hydroxide solution.

The colex (column exchange) separation method makes use of this by passing a counter-flow of amalgam and hydroxide through a cascade of stages. The fraction of lithium-6 is preferentially drained by the mercury, but the lithium-7 flows mostly with the hydroxide. At the bottom of the column, the lithium (enriched with lithium-6) is separated from the amalgam, and the mercury is recovered to be reused with fresh raw material. At the top, the lithium hydroxide solution is electrolyzed to liberate the lithium-7 fraction. The enrichment obtained with this method varies with the column length and the flow speed.

Other methods

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In the vacuum distillation technique, lithium is heated to a temperature of about 550 °C in a vacuum. Lithium atoms evaporate from the liquid surface and are collected on a cold surface positioned a few centimetres above the liquid surface.[8] Since lithium-6 atoms have a greater mean free path, they are collected preferentially. The theoretical separation efficiency of this method is about 8.0 percent. A multistage process may be used to obtain higher degrees of separation.

The isotopes of lithium, in principle, can also be separated through electrochemical method and distillation chromatography, which are currently in development.[9]

Lithium-3

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Lithium-3, also known as the triproton, would consist of three protons and zero neutrons. It was reported as proton unbound in 1969, but this result was not accepted and its existence is thus unproven.[10] No other resonances attributable to 3
Li
 have been reported, and it is expected to decay by prompt proton emission (much like the diproton, 2
He
).[11]

Lithium-4

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Lithium-4 contains three protons and one neutron. It is the shortest-lived known isotope of lithium, with a half-life of 91(9) yoctoseconds (9.1(9)×10−23 s) and decays by proton emission to helium-3.[12] Lithium-4 can be formed as an intermediate in some nuclear fusion reactions.

Lithium-6

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Lithium-6 is valuable as the source material for the production of tritium (hydrogen-3) and as an absorber of neutrons in nuclear fusion reactions. Between 1.9% and 7.8% of terrestrial lithium in normal materials consists of lithium-6, with the rest being lithium-7. Large amounts of lithium-6 have been separated out for placing into thermonuclear weapons. The separation of lithium-6 has by now ceased in the large thermonuclear powers[citation needed], but stockpiles of it remain in these countries.

The deuterium–tritium fusion reaction has been investigated as a possible energy source, as it is currently the only fusion reaction with sufficient energy output for feasible implementation. In this scenario, lithium enriched in lithium-6 would be required to generate the necessary quantities of tritium. Mineral and brine lithium resources are a potential limiting factor in this scenario, but seawater can eventually also be used.[13] Pressurized heavy-water reactors such as the CANDU produce small quantities of tritium in their coolant/moderator from neutron absorption and this is sometimes extracted as an alternative to the use of Lithium-6.

Lithium-6 is one of only four stable isotopes with a spin of 1, the others being deuterium, boron-10, and nitrogen-14,[14] and has the smallest nonzero nuclear electric quadrupole moment of any stable nucleus.

Lithium-7

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Lithium-7 is by far the most abundant isotope of lithium, making up between 92.2% and 98.1% of all terrestrial lithium. A lithium-7 atom contains three protons, four neutrons, and three electrons. Because of its nuclear properties, lithium-7 is less common than helium, carbon, nitrogen, or oxygen in the Universe, even though the latter three all have heavier nuclei. The Castle Bravo thermonuclear test greatly exceeded its expected yield due to incorrect assumptions about the nuclear properties of lithium-7.

The industrial production of lithium-6 results in a waste product which is enriched in lithium-7 and depleted in lithium-6. This material has been sold commercially, and some of it has been released into the environment. A relative abundance of lithium-7, as high as 35 percent greater than the natural value, has been measured in the ground water in a carbonate aquifer underneath the West Valley Creek in Pennsylvania, which is downstream from a lithium processing plant. The isotopic composition of lithium in normal materials can vary somewhat depending on its origin, which determines its relative atomic mass in the source material. An accurate relative atomic mass for samples of lithium cannot be measured for all sources of lithium.[15]

Lithium-7 is used as a part of the molten lithium fluoride in molten-salt reactors: liquid-fluoride nuclear reactors. The large neutron absorption cross section of lithium-6 (about 940 barns[16]) as compared with the very small neutron cross section of lithium-7 (about 45 millibarns) makes high separation of lithium-7 from natural lithium a strong requirement for the possible use in lithium fluoride reactors.

Lithium-7 hydroxide is used for alkalizing of the coolant in pressurized water reactors.[17]

Some lithium-7 has been produced, for a few picoseconds, which contains a lambda particle in its nucleus, whereas an atomic nucleus is generally thought to contain only neutrons and protons.[18][19]

Lithium-8

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Lithium-8 has been proposed as a source of 6.4 MeV electron antineutrinos generated by the inverse beta decay to Beryllium-8. The ISODAR particle physics collaboration describes a scheme to generated Lithium-8 for immediate decay by bombarding stable Lithium-7 with 60 MeV protons created by a cyclotron particle accelerator.[20]

Lithium-11

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Lithium-11 is a halo nucleus consisting of a lithium-9 core surrounded by two loosely-bound neutrons; both neutrons must be present in order for this system to be bound, which has led to the description as a "Borromean nucleus".[21] While the proton root-mean-square radius of 11Li is 2.18+0.16
−0.21 fm, its neutron radius is much larger at 3.34+0.02
−0.08 fm; for comparison, the corresponding figures for 9Li are 2.076±0.037 fm for the protons and 2.4±0.03 fm for the neutrons.[22] It decays by beta emission and neutron emission to 10
Be
, 11
Be
, or 9
Be
 (see tables above and below). Having a magic number of 8 neutrons, Lithium-11 sits on the first of five known islands of inversion, which explains its longer half-life compared to adjacent nuclei.[23]

Lithium-12

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Lithium-12 has a considerably shorter half-life. It decays by neutron emission into 11
Li
, which decays as mentioned above.

Decay chains

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While β− decay into isotopes of beryllium (often combined with single- or multiple-neutron emission) is predominant in heavier isotopes of lithium, 10
Li
 and 12
Li
 decay via neutron emission into 9
Li
 and 11
Li
 respectively due to their positions beyond the neutron drip line. Lithium-11 has also been observed to decay via multiple forms of fission. Isotopes lighter than 6
Li
 decay exclusively by proton emission, as they are beyond the proton drip line. The decay modes of the two isomers of 10
Li
 are unknown.

 

See also

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References

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  1. ^ a b c d e Kondev, F. G.; Wang, M.; Huang, W. J.; Naimi, S.; Audi, G. (2021). "The NUBASE2020 evaluation of nuclear properties" (PDF). Chinese Physics C. 45 (3): 030001. doi:10.1088/1674-1137/abddae.
  2. ^ "Standard Atomic Weights: Lithium". CIAAW. 2009.
  3. ^ Prohaska, Thomas; Irrgeher, Johanna; Benefield, Jacqueline; Böhlke, John K.; Chesson, Lesley A.; Coplen, Tyler B.; Ding, Tiping; Dunn, Philip J. H.; Gröning, Manfred; Holden, Norman E.; Meijer, Harro A. J. (4 May 2022). "Standard atomic weights of the elements 2021 (IUPAC Technical Report)". Pure and Applied Chemistry. doi:10.1515/pac-2019-0603. ISSN 1365-3075.
  4. ^ Fields, Brian D. (2011). "The Primordial Lithium Problem". Annual Review of Nuclear and Particle Science. 61 (1): 47–68. arXiv:1203.3551. Bibcode:2011ARNPS..61...47F. doi:10.1146/annurev-nucl-102010-130445. S2CID 119265528.
  5. ^ "(Li) Lithium NMR".
  6. ^ Wang, Meng; Huang, W.J.; Kondev, F.G.; Audi, G.; Naimi, S. (2021). "The AME 2020 atomic mass evaluation (II). Tables, graphs and references*". Chinese Physics C. 45 (3): 030003. doi:10.1088/1674-1137/abddaf.
  7. ^ a b "Atomic Weight of Lithium". ciaaw.org. Retrieved 21 October 2021.
  8. ^ Katal'nikov, S. G.; Andreev, B. M. (1 March 1962). "The separation factor of lithium isotopes during vacuum distillation". The Soviet Journal of Atomic Energy. 11 (3): 889–893. doi:10.1007/BF01491187. ISSN 1573-8205. S2CID 96799991.
  9. ^ Badea, Silviu-Laurentiu; Niculescu, Violeta-Carolina; Iordache, Andreea-Maria (April 2023). "New Trends in Separation Techniques of Lithium Isotopes: A Review of Chemical Separation Methods". Materials. 16 (10): 3817. Bibcode:2023Mate...16.3817B. doi:10.3390/ma16103817. ISSN 1996-1944. PMC 10222844. PMID 37241444.
  10. ^ Audi, G.; Kondev, F. G.; Wang, M.; Huang, W. J.; Naimi, S. (2017). "The NUBASE2016 evaluation of nuclear properties" (PDF). Chinese Physics C. 41 (3): 030001–21. Bibcode:2017ChPhC..41c0001A. doi:10.1088/1674-1137/41/3/030001.
  11. ^ Purcell, J. E.; Kelley, J. H.; Kwan, E.; Sheu, C. G.; Weller, H. R. (2010). "Energy Levels of Light Nuclei (A = 3)" (PDF). Nuclear Physics A. 848 (1): 1. Bibcode:2010NuPhA.848....1P. doi:10.1016/j.nuclphysa.2010.08.012. Archived from the original (PDF) on 1 February 2018. Retrieved 3 January 2020.
  12. ^ "Isotopes of Lithium". Retrieved 20 October 2013.
  13. ^ Bradshaw, A.M.; Hamacher, T.; Fischer, U. (2010). "Is nuclear fusion a sustainable energy form?" (PDF). Fusion Engineering and Design. 86 (9): 2770–2773. doi:10.1016/j.fusengdes.2010.11.040. hdl:11858/00-001M-0000-0026-E9D2-6. S2CID 54674085.
  14. ^ Chandrakumar, N. (2012). Spin-1 NMR. Springer Science & Business Media. p. 5. ISBN 9783642610899.
  15. ^ Coplen, Tyler B.; Hopple, J. A.; Böhlke, John Karl; Peiser, H. Steffen; Rieder, S. E.; Krouse, H. R.; Rosman, Kevin J. R.; Ding, T.; Vocke, R. D., Jr.; Révész, K. M.; Lamberty, A.; Taylor, Philip D. P.; De Bièvre, Paul; "Compilation of minimum and maximum isotope ratios of selected elements in naturally occurring terrestrial materials and reagents", U.S. Geological Survey Water-Resources Investigations Report 01-4222 (2002). As quoted in T. B. Coplen; et al. (2002). "Isotope-Abundance Variations of Selected Elements (IUPAC technical report)" (PDF). Pure and Applied Chemistry. 74 (10): 1987–2017. doi:10.1351/pac200274101987. S2CID 97223816. Archived from the original (PDF) on 3 March 2016. Retrieved 29 October 2012.
  16. ^ Holden, Norman E. (January–February 2010). "The Impact of Depleted 6Li on the Standard Atomic Weight of Lithium". Chemistry International. International Union of Pure and Applied Chemistry. Retrieved 6 May 2014.
  17. ^ Managing Critical Isotopes: Stewardship of Lithium-7 Is Needed to Ensure a Stable Supply, GAO-13-716 // U.S. Government Accountability Office, 19 September 2013; pdf
  18. ^ Emsley, John (2001). Nature's Building Blocks: An A-Z Guide to the Elements. Oxford University Press. pp. 234–239. ISBN 978-0-19-850340-8.
  19. ^ Brumfiel, Geoff (1 March 2001). "The Incredible Shrinking Nucleus". Physical Review Focus. Vol. 7. doi:10.1103/PhysRevFocus.7.11.
  20. ^ Bungau, Adriana; Alonso, Jose; Bartoszek, Larry; Conrad, Janet (May 2018). "Optimizing the 8Li yield for the IsoDAR Neutrino Experiment". Journal of Instrumentation. 14 (3): 03001. arXiv:1805.00410. doi:10.1088/1748-0221/14/03/P03001. S2CID 55756525.
  21. ^ "A new particle accelerator aims to unlock secrets of bizarre atomic nuclei". 15 November 2021.
  22. ^ Moriguchi, T.; Ozawa, A.; Ishimoto, S.; Abe, Y.; Fukuda, M.; Hachiuma, I.; Ishibashi, Y.; Ito, Y.; Kuboki, T.; Lantz, M.; Nagae, D.; Namihira, K.; Nishimura, D.; Ohtsubo, T.; Ooishi, H.; Suda, T.; Suzuki, H.; Suzuki, T.; Takechi, M.; Tanaka, K.; Yamaguchi, T. (16 August 2013). "Density distributions of 11 Li deduced from reaction cross-section measurements". Physical Review C. 88 (2): 024610. Bibcode:2013PhRvC..88b4610M. doi:10.1103/PhysRevC.88.024610.
  23. ^ Brown, B. Alex (13 December 2010). "Islands of insight in the nuclear chart". Physics. 3 (25): 104. arXiv:1010.3999. doi:10.1103/PhysRevLett.105.252501. PMID 21231582. S2CID 43334780.
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Lewis, G. N.; MacDonald, R. T. (1936). "The Separation of Lithium Isotopes". Journal of the American Chemical Society. 58 (12): 2519–2524. doi:10.1021/ja01303a045.

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