Chemistry:Thallium halides
The thallium halides include monohalides TlX, where thallium has oxidation state +1, trihalides TlX
3, where thallium generally has oxidation state +3, and some intermediate halides containing thallium with mixed +1 and +3 oxidation states. X is a halogen. These salts find use in specialized optical settings, such as focusing elements in research spectrophotometers. Compared to the more common zinc selenide-based optics, materials such as thallium bromoiodide enable transmission at longer wavelengths. In the infrared, this allows for measurements as low as 350 cm−1 (28 μm), whereas zinc selenide is opaque by 21.5 μm, and zinc sulfide optics are generally only usable to 650 cm−1 (15 μm).
Monohalides
The monohalides, also known as thallous halides, all contain thallium with oxidation state +1. Parallels can be drawn between the thallium(I) halides and their corresponding silver salts; for example, thallium(I) chloride and bromide are light-sensitive, and thallium(I) fluoride is more soluble in water than the chloride and bromide.[citation needed] Unlike the silver salts, however, thallous halide complex salts are very weakly bonded in solution, and practically nonexistent in the solid state.[1]: 30–31 The dissolved complexes are generally of the form (TlX
3)2− and (TlX
4)3−.
The solid-state forms of thallous chloride (TlCl) and bromide (TlBr) are isostructural with caesium chloride, but the fluoride (TlF) and iodide (TlI) adopt distorted structures.[1]: 19 The room temperature structures of Tl-F[2] and Tl-I have been explained through an interaction between Tl 6s and the halide p states; orbital mixing produces producing strongly antibonding Tl-X states. The structure distorts to minimise these unfavourable covalent interactions.[1]: 21–22
Structurally, TlF resembles α-PbO, distorted rock-salt with essentially five-coordinate thallium and a distant sixth fluoride. At 62 °C it transforms to a tetragonal structure, unchanged up to 40 GPa pressure.[3] At room temperature, TlI also adopts an eponymous distorted rock salt structure, the β-TlI structure, with five-coordinate thallium but two distant iodides. At 170 °C or 5 kbar, it transforms to the CsCl structure.[1]: 20
As the anions become less electronegative, the bonding in thallium halides becomes less ionic, and the substances begin to show color. TlF and TlCl are white, TlBr is pale yellow,[citation needed] and TlI is bright yellow. The high-temperature or -pressure modification of TlI is red,[4] darkening as further pressure is applied, until around 160 kbar TlI becomes a metal.[1]: 21
The melting point of thallium halides also increases with anion mass.[citation needed] Little is known about the molten state. Gaseous thallous fluoride is a dimer, (TlF)2, but its structure is unclear and may include a thallium-thallium bond.[1]: 22–24
Thallium(I) mixed halides
Thallium bromoiodide or thallium bromide iodide (TlBr
xI
1-x) and thallium bromochloride or thallium bromide chloride (TlBr
xCl
1-x) are mixed salts of thallium(I) that are used in spectroscopy as an optical material for transmission, refraction, and focusing of infrared radiation. The materials were first grown by R. Koops in the laboratory of Olexander Smakula at the Carl Zeiss Optical Works, Jena in 1941.[5][6] The red bromoiodide was coded KRS-5[7] and the colourless bromochloride, KRS-6[8] and this is how they are commonly known. The KRS prefix is an abbreviation of "Kristalle aus dem Schmelz-fluss", (crystals from the melt). The compositions of KRS-5 and KRS-6 approximate to TlBr
0.4I
0.6 and TlBr
0.3Cl
0.7. KRS-5 is the most commonly used, its properties of being relatively insoluble in water and non-hygroscopic, make it an alternative to KBr, CsI, and AgCl.[9]
Trihalides
The thallium trihalides, also known as thallic halides, are less stable than their corresponding aluminium, gallium, and indium counterparts and chemically quite distinct. The triiodide does not contain thallium with oxidation state +3 but is a thallium(I) compound and contains the linear I−
3 ion.
The thallium(III) salts are all highly moisture-sensitive.[1]: 44 All can be synthesized through action of the halogen in an appropriate solvent on the corresponding thallium(I) salt;[1]: 44 [10] analogous mixed halide salts (e.g. TlFBr2) are also possible. Thallic fluoride (TlF3) can also be made by fluoridation of Tl2O3 with F2, BrF3,[1]: 44 or SF4 at 300 °C.[citation needed]
Thallic chloride (TlCl3) forms a number of hydrates. Thallic bromide (TlBr3) is only known to form a tetrahydrate.[1]: 44 Both can only be dehydrated through chemical means: heating the hydrates to 40 °C causes decomposition to the corresponding thallous salt.[1]: 44 [11]
Physical properties are as follows:
- Thallium(III) fluoride
- TlF3 is a white solid, mp 550 °C. Its structure is the same as YF
3 and β-BiF
3. Thallium atom is 9 coordinate (tricapped trigonal prismatic), but one distant fluoride is only dubiously coordinated.[1]: 45 - Thallium(III) chloride
- TlCl
3 has a monoclinic yttrium chloride structure like AlCl
3 and InCl
3. It melts at 155 °C.[1]: 45–46 - Thallium(III) bromide
- Thallium(I) triiodide
- TlI
3 is a black crystalline solid prepared from TlI and I
2 in aqueous HI. It does not contain thallium(III), but has the same structure as CsI
3 containing the linear I−
3 ion.[1]: 73
The compounds are relatively oxidizing, and halogenate pnictogen(III) compounds.[1]: 69, 81
Halide complexes and mixed valence
Although thallous halides resist complex formation (see § Monohalides), the trihalides are relatively Lewis acidic in the solid state. (The compounds are rather basic as aqueous species. TlF3 generally does not form complexes, and dichloro- and dibromothallium(III) complexes of the form [TlX2]+ are "amongst the most stable of metal halide complexes in aqueous solution".[1]: 46–47 Nevertheless, thallic chloride and bromide both form complexes with ammonia.[1]: 65 ) The mixed-valence salts are not well characterised, but are generally the Tl(I) salt of an anionic Tl(III) complex, e.g. TlCl−
4.
- Thallium(III) fluoride complexes
- The salts NaTlF
4 and NaTlF
4 do not contain discrete tetrahedral anions. They both adopt the fluorite (CaF2) structure. ContrariwiseK
3TlF
6 and K
3TlF
6 both have distinct, octahedral [TlF6]3− anions.[1]: 56–57 Both compounds are usually considered to be mixed salts of Na+
and Tl3+.
- Thallium(III) chloride complexes
- Salts of tetrahedral TlCl−
4 and octahedral TlCl3−
6 are known with various cations.[1]: 48, 57–58, 61
- Salts containing TlCl2−
5 with a square pyramidal structure are known. Some salts that nominally contain TlCl2−
5 actually contain the dimeric anion Tl
2Cl4−
10, long chain anions where TlIII
is 6 coordinate and the octahedral units are linked by bridging chlorine atoms, or mixed salts of TlIII
Cl
4 and TlIII
Cl
6.[12]
- The ion Tl
2Cl3−
9, where thallium atoms are octahedrally coordinated with three bridging chlorine atoms, has been identified in the caesium salt, Cs
3Tl
2Cl
9.[1]: 62
- Thallium(III) bromide complexes
- Salts of TlIII
Br−
4 and TlIII
Br3−
6 are known with various cations.
- The TlBr2−
5 anion has been characterised in a number of salts and is trigonal bipyramidal. Some other salts that nominally contain TlBr2−
5 are mixed salts containing TlBr−
4 and Br−
.[13]
- Thallium(III) iodide complexes
- Salts of TlIII
I−
4 are known. The anion is stable even though neutral TlI3 is a thallium(I) compound.[1]: 49
Additionally, mixed halide complexes are known to precipitate from acetonitrile solutions with relatively bulky cations (e.g., tetraethylammonium).[1]: 53
- TlCl
2 - This is formulated as TlI
TlIII
Cl
4. It is yellow, darkening to orange as it is heated.[1]: 73
- Tl
2Cl
3 - This yellow compound is formulated TlI
3TlIII
Cl
6.[14]
- Tl
2Br
3 - This compound is similar to Tl
2Cl
3 and is formulated TlI
3TlIII
Br
6[15]
- TlBr
2 - This pale brown solid is formulated TlI
TlIII
Br
4[1]: 71
- Tl
3I
4 - This compound has been reported as an intermediate in the synthesis of TlI
3 from TlI and I
2. The structure is not known, but the material is diamagnetic.[1]: 75
References
- ↑ 1.00 1.01 1.02 1.03 1.04 1.05 1.06 1.07 1.08 1.09 1.10 1.11 1.12 1.13 1.14 1.15 1.16 1.17 1.18 1.19 1.20 1.21 1.22 1.23 1.24 Lee, A. G. (1971). The Chemistry of Thallium. Topics in Inorganic and General Chemistry. Amsterdam: Elsevier. ISBN 0-444-20112-2. https://archive.org/details/chemistryofthall0000leea/.
- ↑ Mudring, Anja Verena (2007). "Thallium Halides – New Aspects of the Stereochemical Activity of Electron Lone Pairs of Heavier Main Group Elements". European Journal of Inorganic Chemistry (Wiley) 2007 (6): 882–890. doi:10.1002/ejic.200600975. ISSN 1434-1948.
- ↑ Häussermann, Ulrich; Berastegui, Pedro; Carlson, Stefan; Haines, Julien; Léger, Jean-Michel (2001-12-17). "TlF and PbO under High Pressure: Unexpected Persistence of the Stereochemically Active Electron Pair" (in de). Angewandte Chemie (Wiley) 113 (24): 4760–4765. doi:10.1002/1521-3757(20011217)113:24<4760::aid-ange4760>3.0.co;2-6. ISSN 0044-8249. Bibcode: 2001AngCh.113.4760H.
- ↑ Mir, Wasim J.; Warankar, Avinash; Acharya, Ashutosh; Das, Shyamashis; Mandal, Pankaj; Nag, Angshuman (2017). "Colloidal thallium halide nanocrystals with reasonable luminescence, carrier mobility and diffusion length" (in en). Chemical Science 8 (6): 4602–4611. doi:10.1039/C7SC01219E. PMID 28970882.
- ↑ Koops, R. (1948). "Optical structural subjects from binary mixed crystals". Optik (3): 298–304.
- ↑ Smakula, A.; Kalnajs, J.; Sils, V. (March 1953). "Inhomogeneity of Thallium Halide Mixed Crystals and Its Elimination". Laboratory for Insulation Research Technical Report 67. Massachusetts Institute of Technology. https://docs.google.com/viewer?a=v&q=cache:NsfLFcXY8OQJ:www.dtic.mil/cgi-bin/GetTRDoc%3FAD%3DAD0008948+&hl=en&gl=nz&pid=bl&srcid=ADGEESiGn5WoJc2xFvblN62oU19Sb_DPH8xnbL40R2liaoPVYG5QUEHebV_2rSjFEchjQC41LbtYT6eKeX1xrM23nRim4vcLiVFhc7y5IW52zmgixui72dOtSH-ppKEwBlCME2T-xz-P&sig=AHIEtbSwEWXnARSOjawhenrSc3QLPk4JlA.
- ↑ Crystran Data for KRS5 https://www.crystran.co.uk/optical-materials/krs5-thallium-bromo-iodide-tlbr-tli
- ↑ Crystran Data for KRS6 https://www.crystran.co.uk/optical-materials/krs6-thallium-bromo-chloride-tlbr-tlcl
- ↑ Frank Twyman (1988) Prism and Lens Making: A Textbook for Optical Glassworkers CRC Press ISBN 0-85274-150-2, page 170
- ↑ E. Dönges (1963). "Thallium(IIl) Chloride". in G. Brauer. Handbook of Preparative Inorganic Chemistry, 2nd Ed.. 2. NY, NY: Academic Press. pp. 890.
- ↑ Glaser, Julius; Fjellvåg, Helmer; Kjekshus, Arne; Andresen, Arne F.; Sokolov, V. B.; Spiridonov, V. P.; Strand, T. G. (1979). "Crystal and Molecular Structure of Thallium(III) Bromide Tetrahydrate and Thallium(III) Chloride Tetrahydrate, a Redetermination.". Acta Chemica Scandinavica (Danish Chemical Society) 33A: 789–794. doi:10.3891/acta.chem.scand.33a-0789. ISSN 0904-213X.
- ↑ James, Margaret Ann; Clyburne, Jason A.C.; Linden, Anthony; James, Bruce D.; Liesegang, John; Zuzich, Vilma (1996-08-01). "Structural diversity in thallium chemistry: structures of four chlorothallate(III) salts including a novel compound containing three geometrically different anions". Canadian Journal of Chemistry (Canadian Science Publishing) 74 (8): 1490–1502. doi:10.1139/v96-166. ISSN 0008-4042.
- ↑ Linden, Anthony; Nugent, Kerry W.; Petridis, Alexander; James, Bruce D. (1999). "Structural diversity in thallium chemistry". Inorganica Chimica Acta (Elsevier BV) 285 (1): 122–128. doi:10.1016/s0020-1693(98)00339-9. ISSN 0020-1693.
- ↑ Böhme, Reinhild; Rath, Jörg; Grunwald, Bernd; Thiele, Gerhard (1980-11-01). "Über zwei Modifikationen von "Tl2Cl3"-valenzgemischten Thallium(I)-hexahalogenothallaten(III) Tl3 [TlCl6] / On Two Modifications of "Tl2Cl3"-Mixed Valence Thallium(I)-hexahalogenothallates(III)". Zeitschrift für Naturforschung B (Walter de Gruyter GmbH) 35 (11): 1366–1372. doi:10.1515/znb-1980-1108. ISSN 1865-7117.
- ↑ Ackermann, Rupprecht; Hirschle, Christian; Rotter, Heinz W.; Thiele, Gerhard (2002). "Mixed-Valence Thallium(I, III) Bromides The Crystal Structure of α—Tl2Br3" (in de). Zeitschrift für anorganische und allgemeine Chemie (Wiley) 628 (12): 2675–2682. doi:10.1002/1521-3749(200212)628:12<2675::aid-zaac2675>3.0.co;2-4. ISSN 0044-2313.
Further information
- Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
- Cotton, F. Albert; Wilkinson, Geoffrey; Murillo, Carlos A.; Bochmann, Manfred (1999), Advanced Inorganic Chemistry (6th ed.), New York: Wiley-Interscience, ISBN 0-471-19957-5
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