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Isotopes of thorium

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Isotopes of thorium (90Th)
Main isotopes[1] Decay
abun­dance half-life (t1/2) mode pro­duct
227Th trace 18.68 d α 223Ra
228Th trace 1.9116 y α 224Ra
229Th trace 7917 y[2] α 225Ra
230Th 0.02% 75400 y α 226Ra
231Th trace 25.5 h β− 231Pa
232Th 100.0% 1.405×1010 y α 228Ra
233Th trace 21.83 min β− 233Pa
234Th trace 24.1 d β− 234Pa
Standard atomic weight Ar°(Th)

Thorium (90Th) has seven naturally occurring isotopes but none are stable. One isotope, 232Th, is relatively stable, with a half-life of 1.405×1010 years, considerably longer than the age of the Earth, and even slightly longer than the generally accepted age of the universe. This isotope makes up nearly all natural thorium, so thorium was considered to be mononuclidic. However, in 2013, IUPAC reclassified thorium as binuclidic, due to large amounts of 230Th in deep seawater. Thorium has a characteristic terrestrial isotopic composition and thus a standard atomic weight can be given.

Thirty-one radioisotopes have been characterized, with the most stable being 232Th, 230Th with a half-life of 75,380 years, 229Th with a half-life of 7,917 years,[2] and 228Th with a half-life of 1.92 years. All of the remaining radioactive isotopes have half-lives that are less than thirty days and the majority of these have half-lives that are less than ten minutes. One isotope, 229Th, has a nuclear isomer (or metastable state) with a remarkably low excitation energy,[5] recently measured to be 8.35574 eV[6] It has been proposed to perform laser spectroscopy of the 229Th nucleus and use the low-energy transition for the development of a nuclear clock of extremely high accuracy.[7][8][9]

The known isotopes of thorium range in mass number from 207[10] to 238.

List of isotopes

[edit]
Nuclide
[n 1] 		Historic
name 		Z N Isotopic mass (Da)
[n 2][n 3] 		Half-life
[n 4] 		Decay
mode
[n 5] 		Daughter
isotope
[n 6] 		Spin and
parity
[n 7][n 8] 		Natural abundance (mole fraction)
Excitation energy Normal proportion Range of variation
207Th[10] 90 117 9.7(+46.6−4.4) ms α 203Ra
208Th[11] 90 118 208.01791(4) 1.7(+1.7-0.6) ms α 204Ra 0+
209Th[12] 90 119 209.01772(11) 7(5) ms
[3.8(+69−15)] 		α 205Ra 5/2−#
210Th 90 120 210.015075(27) 17(11) ms
[9(+17−4) ms] 		α 206Ra 0+
β+ (rare) 210Ac
211Th 90 121 211.01493(8) 48(20) ms
[0.04(+3−1) s] 		α 207Ra 5/2−#
β+ (rare) 211Ac
212Th 90 122 212.01298(2) 36(15) ms
[30(+20-10) ms] 		α (99.7%) 208Ra 0+
β+ (.3%) 212Ac
213Th 90 123 213.01301(8) 140(25) ms α 209Ra 5/2−#
β+ (rare) 213Ac
214Th 90 124 214.011500(18) 100(25) ms α 210Ra 0+
215Th 90 125 215.011730(29) 1.2(2) s α 211Ra (1/2−)
216Th 90 126 216.011062(14) 26.8(3) ms α (99.99%) 212Ra 0+
β+ (.006%) 216Ac
216m1Th 2042(13) keV 137(4) μs (8+)
216m2Th 2637(20) keV 615(55) ns (11−)
217Th 90 127 217.013114(22) 240(5) μs α 213Ra (9/2+)
218Th 90 128 218.013284(14) 109(13) ns α 214Ra 0+
219Th 90 129 219.01554(5) 1.05(3) μs α[n 9] 215Ra 9/2+#
220Th 90 130 220.015748(24) 9.7(6) μs α[n 10] 216Ra 0+
221Th 90 131 221.018184(10) 1.73(3) ms α 217Ra (7/2+)
222Th 90 132 222.018468(13) 2.237(13) ms α[n 11] 218Ra 0+
223Th 90 133 223.020811(10) 0.60(2) s α 219Ra (5/2)+
224Th 90 134 224.021467(12) 1.05(2) s α 220Ra 0+
CD (rare) 208Pb
16O
225Th 90 135 225.023951(5) 8.72(4) min α (90%) 221Ra (3/2)+
EC (10%) 225Ac
226Th 90 136 226.024903(5) 30.57(10) min α 222Ra 0+
227Th Radioactinium 90 137 227.0277041(27) 18.68(9) d α 223Ra 1/2+ Trace[n 12]
228Th Radiothorium 90 138 228.0287411(24) 1.9116(16) y α 224Ra 0+ Trace[n 13]
CD (1.3×10−11%) 208Pb
20O
229Th 90 139 229.031762(3) 7.916(17)×103 y α 225Ra 5/2+ Trace[n 14]
229mTh 8.355733554021(8) eV[13] 7(1) μs[14] IT[n 15] 229Th+ 3/2+
229mTh+ 8.355733554021(8) eV[13] 30(1) min[15] γ[n 15] 229Th+ 3/2+
230Th[n 16] Ionium 90 140 230.0331338(19) 7.538(30)×104 y α 226Ra 0+ 0.0002(2)[n 17]
CD (5.6×10−11%) 206Hg
24Ne
SF (5×10−11%) (Various)
231Th Uranium Y 90 141 231.0363043(19) 25.52(1) h β− 231Pa 5/2+ Trace[n 12]
α (10−8%) 227Ra
232Th[n 18] Thorium 90 142 232.0380553(21) 1.405(6)×1010 y α[n 19] 228Ra 0+ 0.9998(2)
SF (1.1×10−9%) (various)
CD (2.78×10−10%) 182Yb
26Ne
24Ne
233Th 90 143 233.0415818(21) 21.83(4) min β− 233Pa 1/2+ Trace[n 20]
234Th Uranium X1 90 144 234.043601(4) 24.10(3) d β− 234mPa 0+ Trace[n 17]
235Th 90 145 235.04751(5) 7.2(1) min β− 235Pa (1/2+)#
236Th 90 146 236.04987(21)# 37.5(2) min β− 236Pa 0+
237Th 90 147 237.05389(39)# 4.8(5) min β− 237Pa 5/2+#
238Th 90 148 238.0565(3)# 9.4(20) min β− 238Pa 0+
This table header & footer:
  1. ^ mTh – 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. ^ Bold half-life – nearly stable, half-life longer than age of universe.
  5. ^ Modes of decay:
    CD: Cluster decay
    EC: Electron capture
    IT: Isomeric transition
  6. ^ Bold symbol as daughter – Daughter product is stable.
  7. ^ ( ) spin value – Indicates spin with weak assignment arguments.
  8. ^ # – Values marked # are not purely derived from experimental data, but at least partly from trends of neighboring nuclides (TNN).
  9. ^ Theoretically capable of β+ decay to 219Ac[1]
  10. ^ Theoretically capable of electron capture to 220Ac[1]
  11. ^ Theoretically capable of electron capture to 222Ac[1]
  12. ^ a b Intermediate decay product of 235U
  13. ^ Intermediate decay product of 232Th
  14. ^ Intermediate decay product of 237Np
  15. ^ a b Neutral 229mTh decays rapidly by internal conversion, ejecting an electron. There is not enough energy to eject a second electron, so 229mTh+ ions live much longer, decaying by gamma emission. See § Thorium-229m.
  16. ^ Used in Uranium–thorium dating
  17. ^ a b Intermediate decay product of 238U
  18. ^ Primordial radionuclide
  19. ^ Theorized to also undergo β−β− decay to 232U
  20. ^ Produced in neutron capture by 232Th

Uses

[edit]

Thorium has been suggested for use in thorium-based nuclear power.

In many countries the use of thorium in consumer products is banned or discouraged because it is radioactive.

It is currently used in cathodes of vacuum tubes, for a combination of physical stability at high temperature and a low work energy required to remove an electron from its surface.

It has, for about a century, been used in mantles of gas and vapor lamps such as gas lights and camping lanterns.

Low dispersion lenses

[edit]

Thorium was also used in certain glass elements of Aero-Ektar lenses made by Kodak during World War II. Thus they are mildly radioactive.[16] Two of the glass elements in the f/2.5 Aero-Ektar lenses are 11% and 13% thorium by weight. The thorium-containing glasses were used because they have a high refractive index with a low dispersion (variation of index with wavelength), a highly desirable property. Many surviving Aero-Ektar lenses have a tea colored tint, possibly due to radiation damage to the glass.

These lenses were used for aerial reconnaissance because the radiation level is not high enough to fog film over a short period. This would indicate the radiation level is reasonably safe. However, when not in use, it would be prudent to store these lenses as far as possible from normally inhabited areas; allowing the inverse square relationship to attenuate the radiation.[17]

Actinides vs. fission products

[edit]
Actinides and fission products by half-life
Actinides[18] by decay chain Half-life
range (a) 		Fission products of 235U by yield[19]
4n 4n + 1 4n + 2 4n + 3 4.5–7% 0.04–1.25% <0.001%
228Ra№ 4–6 a 155Euþ
244Cmƒ 241Puƒ 250Cf 227Ac№ 10–29 a 90Sr 85Kr 113mCdþ
232Uƒ 238Puƒ 243Cmƒ 29–97 a 137Cs 151Smþ 121mSn
248Bk[20] 249Cfƒ 242mAmƒ 141–351 a

No fission products have a half-life
in the range of 100 a–210 ka ...

241Amƒ 251Cfƒ[21] 430–900 a
226Ra№ 247Bk 1.3–1.6 ka
240Pu 229Th 246Cmƒ 243Amƒ 4.7–7.4 ka
245Cmƒ 250Cm 8.3–8.5 ka
239Puƒ 24.1 ka
230Th№ 231Pa№ 32–76 ka
236Npƒ 233Uƒ 234U№ 150–250 ka 99Tc₡ 126Sn
248Cm 242Pu 327–375 ka 79Se₡
1.53 Ma 93Zr
237Npƒ 2.1–6.5 Ma 135Cs₡ 107Pd
236U 247Cmƒ 15–24 Ma 129I₡
244Pu 80 Ma

... nor beyond 15.7 Ma[22]

232Th№ 238U№ 235Uƒ№ 0.7–14.1 Ga

Notable isotopes

[edit]

Thorium-228

[edit]

228Th is an isotope of thorium with 138 neutrons. It was once named Radiothorium, due to its occurrence in the disintegration chain of thorium-232. It has a half-life of 1.9116 years. It undergoes alpha decay to 224Ra. Occasionally it decays by the unusual route of cluster decay, emitting a nucleus of 20O and producing stable 208Pb. It is a daughter isotope of 232U in the thorium decay series.

228Th has an atomic weight of 228.0287411 grams/mole.

Together with its decay product 224Ra it is used for alpha particle radiation therapy.[23]

Thorium-229

[edit]

229Th is a radioactive isotope of thorium that decays by alpha emission with a half-life of 7917 years.[2] 229Th is produced by the decay of uranium-233, and its principal use is for the production of the medical isotopes actinium-225 and bismuth-213.[24]

Thorium-229m

[edit]

229Th has a nuclear isomer, 229m
Th
, with a remarkably low excitation energy of 8.355733554021(8) eV.[13]

Due to this low energy, the lifetime of 229mTh very much depends on the electronic environment of the nucleus. In neutral 229Th, the isomer decays by internal conversion within a few microseconds.[25][26][14] However, the isomeric energy is not enough to remove a second electron (thorium's second ionization energy is 11.5 eV), so internal conversion is impossible in Th+ ions. Radiative decay occurs with a half-life 8.4 orders of magnitude longer, in excess of 1000 seconds.[26][27] Embedded in ionic crystals, ionization is not quite 100%, so a small amount of internal conversion occurs, leading to a recently measured lifetime of ≈600 s,[6][15] which can be extrapolated to a lifetime for isolated ions of 1740±50 s.[6]

This excitation energy corresponds to a photon frequency of 2020407384335±2 kHz (wavelength 148.3821828827(15) nm).[13][28][6][15] Although in the very high frequency vacuum ultraviolet frequency range, it is possible to build a laser operating at this frequency, giving the only known opportunity for direct laser excitation of a nuclear state,[29] which could have applications like a nuclear clock of very high accuracy[8][9][30][31] or as a qubit for quantum computing.[32]

These applications were for a long time impeded by imprecise measurements of the isomeric energy, as laser excitation's exquisite precision makes it difficult to use to search a wide frequency range. There were many investigations, both theoretical and experimental, trying to determine the transition energy precisely and to specify other properties of the isomeric state of 229Th (such as the lifetime and the magnetic moment) before the frequency was accurately measured in 2024.[6][28][15]

History

[edit]

Early measurements were performed via gamma ray spectroscopy, producing the 29.5855 keV excited state of 229Th, and measuring the difference in emitted gamma ray energies as it decays to either the 229mTh (90%) or 229Th (10%) isomeric states.

In 1976, this technique first indicated that 229Th has a nuclear isomer, 229mTh, with a remarkably low excitation energy.[33] At that time the energy was inferred to be below 100 eV, purely based on the non-observation of the isomer's direct decay. However, in 1990, further measurements led to the conclusion that the energy is almost certainly below 10 eV,[34] making it one of the lowest known isomeric excitation energies. In the following years, the energy was further constrained to 3.5±1.0 eV, which was for a long time the accepted energy value.[35]

Improved gamma ray spectroscopy measurements using an advanced high-resolution X-ray microcalorimeter were carried out in 2007, yielding a new value for the transition energy of 7.6±0.5 eV,[36] corrected to 7.8±0.5 eV in 2009.[37] This higher energy has two consequences which had not been considered by earlier attempts to observe emitted photons:

  • Because it is above thorium's 6.08 eV first ionization energy, neutral 229mTh will not decay radiatively at all, and
  • Because it is above the 6.2 eV vacuum ultraviolet cutoff, the produced photons cannot travel through air.

But even knowing the higher energy, most of the searches in the 2010s for light emitted by the isomeric decay failed to observe any signal,[38][39][40][41] pointing towards a potentially strong non-radiative decay channel. A direct detection of photons emitted in the isomeric decay was claimed in 2012[42] and again in 2018.[43] However, both reports were subject to controversial discussions within the community.[44][45]

A direct detection of electrons being emitted in the internal conversion decay channel of 229mTh was achieved in 2016.[46] However, at the time the isomer's transition energy could only be weakly constrained to between 6.3 and 18.3 eV. Finally, in 2019, non-optical electron spectroscopy of the internal conversion electrons emitted in the isomeric decay allowed for a determination of the isomer's excitation energy to 8.28±0.17 eV.[47] However, this value appeared at odds with the 2018 preprint showing that a similar signal as an 8.4 eV xenon VUV photon can be shown, but with about 1.3+0.2
−0.1 eV less energy and an 1880 s lifetime.[43] In that paper, 229Th was embedded in SiO2, possibly resulting in an energy shift and altered lifetime, although the states involved are primarily nuclear, shielding them from electronic interactions.

In a 2018 experiment, it was possible to perform a first laser-spectroscopic characterization of the nuclear properties of 229mTh.[48] In this experiment, laser spectroscopy of the 229Th atomic shell was conducted using a 229Th2+ ion cloud with 2% of the ions in the nuclear excited state. This allowed probing for the hyperfine shift induced by the different nuclear spin states of the ground and the isomeric state. In this way, a first experimental value for the magnetic dipole and the electric quadrupole moment of 229mTh could be inferred.

In 2019, the isomer's excitation energy was constrained to 8.28±0.17 eV based on the direct detection of internal conversion electrons[47] and a secure population of 229mTh from the nuclear ground state was achieved by excitation of the 29 keV nuclear excited state via synchrotron radiation.[49] Additional measurements by a different group in 2020 produced a figure of 8.10±0.17 eV (153.1±3.2 nm wavelength).[50] Combining these measurements, the expected transition energy is 8.12±0.11 eV.[51]

In April 2024, two separate groups finally reported precision laser excitation Th4+ cations doped into ionic crystals (of CaF2 and LiSrAlF6 with additional interstitial F− anions for charge compensation), giving a precise (≈1 part per million) measurement of the transition energy.[28][7][6][15] A one-part-per-trillion (10−12) measurement soon followed in June 2024,[13] and future high-precision lasers will measure the frequency up to the 10−18 accuracy of the best atomic clocks.[13][9][31]

Thorium-230

[edit]

230Th is a radioactive isotope of thorium that can be used to date corals and determine ocean current flux. Ionium was a name given early in the study of radioactive elements to the 230Th isotope produced in the decay chain of 238U before it was realized that ionium and thorium are chemically identical. The symbol Io was used for this supposed element. (The name is still used in ionium–thorium dating.)

Thorium-231

[edit]

231Th has 141 neutrons. It is the decay product of uranium-235. It is found in very small amounts on the earth and has a half-life of 25.5 hours.[52] When it decays, it emits a beta ray and forms protactinium-231. It has a decay energy of 0.39 MeV. It has a mass of 231.0363043 grams/mole.

Thorium-232

[edit]
Main article: Thorium-232

232Th is the only primordial nuclide of thorium and makes up effectively all of natural thorium, with other isotopes of thorium appearing only in trace amounts as relatively short-lived decay products of uranium and thorium.[53] The isotope decays by alpha decay with a half-life of 1.405×1010 years, over three times the age of the Earth and approximately the age of the universe. Its decay chain is the thorium series, eventually ending in lead-208. The remainder of the chain is quick; the longest half-lives in it are 5.75 years for radium-228 and 1.91 years for thorium-228, with all other half-lives totaling less than 15 days.[54]

232Th is a fertile material able to absorb a neutron and undergo transmutation into the fissile nuclide uranium-233, which is the basis of the thorium fuel cycle.[55] In the form of Thorotrast, a thorium dioxide suspension, it was used as a contrast medium in early X-ray diagnostics. Thorium-232 is now classified as carcinogenic.[56]

Thorium-233

[edit]

233Th is an isotope of thorium that decays into protactinium-233 through beta decay. It has a half-life of 21.83 minutes.[1] Traces occur in nature as the result of natural neutron activation of 232Th.[57]

Thorium-234

[edit]

234Th is an isotope of thorium whose nuclei contain 144 neutrons. 234Th has a half-life of 24.1 days, and when it decays, it emits a beta particle, and in doing so, it transmutes into protactinium-234. 234Th has a mass of 234.0436 atomic mass units (amu), and it has a decay energy of about 270 keV (kiloelectronvolts). Uranium-238 usually decays into this isotope of thorium (although in rare cases it can undergo spontaneous fission instead).

References

[edit]
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  2. ^ a b c Varga, Z.; Nicholl, A.; Mayer, K. (2014). "Determination of the 229Th half-life". Physical Review C. 89 (6): 064310. doi:10.1103/PhysRevC.89.064310.
  3. ^ "Standard Atomic Weights: Thorium". CIAAW. 2013.
  4. ^ 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. (2022-05-04). "Standard atomic weights of the elements 2021 (IUPAC Technical Report)". Pure and Applied Chemistry. doi:10.1515/pac-2019-0603. ISSN 1365-3075.
  5. ^ E. Ruchowska (2006). "Nuclear structure of 229Th" (PDF). Physical Review C. 73 (4): 044326. Bibcode:2006PhRvC..73d4326R. doi:10.1103/PhysRevC.73.044326. hdl:10261/12130.
  6. ^ a b c d e f Tiedau, J.; Okhapkin, M. V.; Zhang, K.; Thielking, J.; Zitzer, G.; Peik, E.; et al. (29 April 2024). "Laser Excitation of the Th-229 Nucleus" (PDF). Physical Review Letters. 132 (18) 182501. Bibcode:2024PhRvL.132r2501T. doi:10.1103/PhysRevLett.132.182501. The nuclear resonance for the Th4+ ions in Th:CaF2 is measured at the wavelength 148.3821(5) nm, frequency 2020.409(7) THz, and the fluorescence lifetime in the crystal is 630(15) s, corresponding to an isomer half-life of 1740(50) s for a nucleus isolated in vacuum.
  7. ^ a b "Atomic Nucleus Excited with Laser: A Breakthrough after Decades" (Press release). TU Wien. 29 April 2024. Retrieved 29 April 2024.
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  9. ^ a b c Campbell, C.J.; Radnaev, A.G.; Kuzmich, A.; Dzuba, V.A.; Flambaum, V.V.; Derevianko, A. (2012). "A single ion nuclear clock for metrology at the 19th decimal place" (PDF). Physical Review Letters. 108 (12) 120802: 120802. arXiv:1110.2490. Bibcode:2012PhRvL.108l0802C. doi:10.1103/PhysRevLett.108.120802. PMID 22540568. S2CID 40863227. Retrieved 2024-04-30.
  10. ^ a b Yang, H. B.; et al. (2022). "New isotope 207Th and odd-even staggering in α-decay energies for nuclei with Z > 82 and N < 126". Physical Review C. 105 (L051302). Bibcode:2022PhRvC.105e1302Y. doi:10.1103/PhysRevC.105.L051302. S2CID 248935764.
  11. ^ Cardona, J.A.H. (2012). "Production and decay properties of neutron deficient isotopes with N < 126 and 74 ≤ Z ≤ 92 at SHIP". Goethe Universität Frankfury Allemagne.
  12. ^ H. Ikezoe; et al. (1996). "alpha decay of a new isotope of 209Th". Physical Review C. 54 (4): 2043–2046. Bibcode:1996PhRvC..54.2043I. doi:10.1103/PhysRevC.54.2043. PMID 9971554.
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  14. ^ a b Seiferle, B.; von der Wense, L.; Thirolf, P.G. (January 2017). "Lifetime measurement of the 229Th nuclear isomer". Physical Review Letters. 118 (4) 042501. arXiv:1801.05205. Bibcode:2017PhRvL.118d2501S. doi:10.1103/PhysRevLett.118.042501. PMID 28186791. S2CID 37518294. A half-life of 7±1 μs has been measured
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  16. ^ f2.5 Aero Ektar Lenses [permanent dead link] Some images.
  17. ^ Michael S. Briggs (January 16, 2002). "Aero-Ektar Lenses". Archived from the original on August 12, 2015. Retrieved 2015-08-28.
  18. ^ Plus radium (element 88). While actually a sub-actinide, it immediately precedes actinium (89) and follows a three-element gap of instability after polonium (84) where no nuclides have half-lives of at least four years (the longest-lived nuclide in the gap is radon-222 with a half life of less than four days). Radium's longest lived isotope, at 1,600 years, thus merits the element's inclusion here.
  19. ^ Specifically from thermal neutron fission of uranium-235, e.g. in a typical nuclear reactor.
  20. ^ Milsted, J.; Friedman, A. M.; Stevens, C. M. (1965). "The alpha half-life of berkelium-247; a new long-lived isomer of berkelium-248". Nuclear Physics. 71 (2): 299. Bibcode:1965NucPh..71..299M. doi:10.1016/0029-5582(65)90719-4.
    "The isotopic analyses disclosed a species of mass 248 in constant abundance in three samples analysed over a period of about 10 months. This was ascribed to an isomer of Bk248 with a half-life greater than 9 [years]. No growth of Cf248 was detected, and a lower limit for the β− half-life can be set at about 104 [years]. No alpha activity attributable to the new isomer has been detected; the alpha half-life is probably greater than 300 [years]."
  21. ^ This is the heaviest nuclide with a half-life of at least four years before the "sea of instability".
  22. ^ Excluding those "classically stable" nuclides with half-lives significantly in excess of 232Th; e.g., while 113mCd has a half-life of only fourteen years, that of 113Cd is eight quadrillion years.
  23. ^ "Thor Medical – production of alpha emitters for cancer treatment". May 2023.
  24. ^ Report to Congress on the extraction of medical isotopes from U-233 Archived 2011-09-27 at the Wayback Machine. U.S. Department of Energy. March 2001
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