Eisspeedway

Fluorocarbonate

An example of a fluorocarbonate: bastnäsite from Zagi Mountain, Federally Administered Tribal Areas, Pakistan. Size: 1.5×1.5×0.3 cm.

A carbonate fluoride, fluoride carbonate, fluorocarbonate or fluocarbonate is a double salt containing both carbonate and fluoride. The salts are usually insoluble in water, and can have more than one kind of metal cation to make more complex compounds. Rare-earth fluorocarbonates are particularly important as ore minerals for the light rare-earth elements lanthanum, cerium and neodymium. Bastnäsite is the most important source of these elements. Other artificial compounds are under investigation as non-linear optical materials and for transparency in the ultraviolet, with effects over a dozen times greater than Potassium dideuterium phosphate.[1]

Related to this there are also chlorocarbonates and bromocarbonates. Along with these fluorocarbonates form the larger family of halocarbonates. In turn halocarbonates are a part of mixed anion materials. Compounds where fluorine connects to carbon making acids are unstable, fluoroformic acid decomposes to carbon dioxide and hydrogen fluoride, and trifluoromethyl alcohol also breaks up at room temperature. Trifluoromethoxide compounds exist but react with water to yield carbonyl fluoride.

Structures

MI MII MIII Charge CO3 F
3 3 1 1
1
1 1
1 1 4 1 2
2
2 1 5 2 1
1 1 1 3
1 2
3 1 6 2 2
4 1 7 3 1
2 3
2 1 1 5
1 2 8 3 2
3 1 9 1 7
3 2 12 5 2
2 3 13 5 3

The structure of the carbonate fluorides is mainly determined by the carbonate anion, as it is the biggest component. The overall structure depends on the ratio of carbonate to everything else, i.e. number (metals and fluorides)/number of carbonates. For ratios from 1.2 to 1.5 the carbonates are in a flat dense arrangement. From 1.5 to 2.3 the orientation is edge on. From 2.5 to 3.3 the arrangement is flat open. With a ratio from 4 to 11, the carbonate arrangement is flat-lacunar.[2]

The simplest formula is LnCO3F, where Ln has a 3+ charge.

For monocations there is A3CO3F, where A is a large ion such as K, Rb or Tl.[2]

For M = alkali metal, and Ln = lanthanide: MLnCO3F2 1:1:1:2; M3Ln(CO3)2F2 3:1:2:2; M2Ln(CO3)2F 2:1:2:1; M4Ln(CO3)2F3·H2O 4:1:2:3; M4Ln2(CO3)3F4 2:3:3:4.[2] M2Ln(CO3)F2 2:1:1:3.

For B = alkaline earth and Ln = lanthanide (a triple-charged ion) BLn(CO3)2F 1:1:2:1; BLn2(CO3)3F2 1:2:3:2 B2Ln3(CO3)5F3 2:3:5:3; B2Ln(CO3)2F3 2:1:2:3; B2Ln(CO3)F5 2:1:1:5 B2Ln(CO3)3F 2:1:3:1; B3Ln(CO3)F7 3:1:1:7; B3Ln2(CO3)5F2 3:2:5:2.[2]

For alkali with dication combinations: MB: MBCO3F MB3(CO3)2F3·H2O.[2]

For dications A and B there is ABCO3F2 with a degenerate case of A = B.[2]

KPb2(CO3)2F is layered. Each layer is like a sandwich, with lead and carbonate in the outer sublayers, and potassium and fluoride in the inner layer. K2.70Pb5.15(CO3)5F3 extends this structure with some of the layers also being a double-decker sandwich of carbonate, fluoride, carbonate, fluoride, carbonate.[3]

In the rare-earth fluorocarbonates the environment for the rare-earth atoms is 9-coordinated. Six oxygen atoms from carbonate are at the apices of a trigonal prism, and fluoride ions cap the rectangular faces of the prism.[4]

Formation

Carbonate fluoride compounds can be formed by a variety of related methods involving heating the precursor ingredients with or without water. Thallous fluoride carbonate was made simply by evaporating a fluoride thallium solution in ethanol and water in air. It absorbed sufficient carbon dioxide to yield the product. Most other carbonate fluorides are very insoluble and need high-temperature water to crystallise from. Supercritical water heated between 350 and 750 °C under pressures around 200 bars can be used. A sealed platinum tube can withstand the heat and pressure. Crystallisation takes about a day. With subcritical water around 200 °C, crystallisation takes about 2 days. This can happen in a teflon-coated pressure autoclave. The starting ingredients can be rare-earth fluorides and alkali carbonates. The high pressure is needed to keep the water liquid and the carbon dioxide under control, otherwise it would escape. If the fluoride levels are low, hydroxide can substitute for the fluoride. Solid-state reactions require even higher temperatures.[2]

Bastnäsite along with lukechangite (and petersenite) can be precipitated from a mixed solution of CeCl3, NaF, and NaOH with carbon dioxide.[5] Another way to make the simple rare-earth fluorocarbonates is to precipitate a rare-earth carbonate from a nitrate solution with ammonium bicarbonate and then add fluoride ions with hydrofluoric acid (HF).[6]

Pb2(CO3)F2 can be made by boiling a water solution of lead nitrate, sodium fluoride and potassium carbonate in a 2:2:1 molar ratio.[7]

Properties

structure carbonate vibration, cm−1
ν1 ν2 ν3 ν4
bastnäsite 1086 868 1443 728
synchysite
parisite 1079 1088 870 1449 734 746
KCdCO3F 853 1432
RbCdCO3F 843 1442

The visible spectrum of fluorocarbonates is determined mainly by the cations contained. Different structures only have slight effect on the absorption spectrum of rare-earth elements.[4] The visible spectrum of the rare-earth fluorocarbonates is almost entirely due to narrow absorption bands from neodymium.[4] In the near infrared around 1000 nm there are some absorption lines due to samarium and around 1547 nm are some absorption features due to praseodymium. Deeper into the infrared, bastnäsite has carbonate absorption lines at 2243, 2312 and 2324 nm. Parisite only has a very weak carbonate absorption at 2324 nm, and synchysite absorbs at 2337 nm.[4]

The infrared spectrum due to vibration of carbon–oxygen bonds in carbonate is affected by how many kinds of position there are for the carbonate ions.[4]

Reactions

An important chemical reaction used to prepare rare-earth elements from their ores, is to roast concentrated rare-earth fluorocarbonates with sulfuric acid at about 200 °C. This is then leached with water. This process liberates carbon dioxide and hydrofluoric acid and yields rare-earth sulfates:

2 LnCO3F + 3 H2SO4 → Ln2(SO4)3 + 2 HF + 2 H2O + 2 CO2.

Subsequent processing precipitates a double sulfate with sodium sulfate at about 50 °C. The aim is to separate out the rare-earth elements from calcium, aluminium, iron and thorium.[8]

At high enough temperatures the carbonate fluorides lose carbon dioxide, e.g.

KCu(CO3)F → CuO + KF + CO2

at 340 °C.[2]

The processing of bastnäsite is important, as it is the most commonly mined cerium mineral. When heated in air or oxygen at over 500 °C, bastnäsite oxidises and loses volatiles to form ceria (CeO2). Lukechangite also oxidises to ceria and sodium fluoride (NaF). Ce7O12 results when heated to over 1000 °C.[5]

2 Ce(CO3F) + O2 → 2 CeO2 + 2 CO2 + F2[5]
Na3Ce2(CO3F)4F + ⁠1/2⁠ O2 → 2 CeO2 + 3 CO2 + NaF + Na2CO3[5]

At 1300 °C Na2CO3 loses CO2, and between 1300 and 1600 °C NaF and Na2O boil off.[5]

When other rare-earth carbonate fluorides are heated, they lose carbon dioxide and form an oxyfluoride:

LaCO3F → LaOF + CO2[9]

In some rare-earth extraction processes, the roasted ore is then extracted with hydrochloric acid to dissolve rare earths apart from cerium. Cerium is dissolved if the pH is under 0, and thorium is dissolved if it is under 2.[10]

KCdCO3F when heated yields cadmium oxide (CdO) and potassium fluoride (KF).[11]

When lanthanum fluorocarbonate is heated in a hydrogen sulfide, or carbon disulfide vapour around 500 °C, lanthanum fluorosulfide forms:

LaCO3F + ⁠1/2⁠ CO2 → LaSF + 1.5 CO2[12]

Note that this also works for other lanthanides apart from cerium.

When lanthanum carbonate fluoride is heated at 1000 °C with alumina, lanthanum aluminate is produced:[13]

LaCO3F + 2 Al2O3 → LaAlO3 + CO2 + equiv AlOF

Within the hot part of the Earth's crust, rare-earth fluorocarbonates should react with apatite to form monazite.[14]

Minerals

Some rare-earth fluorocarbonate minerals exist. They make up most of the economic ores for light rare-earth elements (LREE). These probably result from hydrothermal liquids from granite that contained fluoride.[15] Rare-earth fluorocarbonate minerals can form in bauxite on carbonate rocks, as rare-earth fluoride complexes react with carbonate.[16] Carbonate fluoride compounds of rare-earth elements also occur in carbonatites.[17]

name formula pattern formula weight crystal system space group unit cell volume density comment references
albrechtschraufite MgCa4(UO2)2(CO3)6F2⋅17–18H2O 0:7:0:14:6:2 triclinic P1 a = 13.569, b = 13.419, c = 11.622 Å, α = 115.82, β = 107.61, γ = 92.84° Z= 1774.6 2.69 [18]
aravaite Ba2Ca18(SiO4)6(PO4)3(CO3)F3O trigonal R3m a = 7.1255, c = 66.290 Z=3 2914.8 [19]
arisite-(Ce) NaCe2(CO3)2[(CO3)1–xF2x]F P6̅m2 a=5.1109 c=8.6713 Z=1 196.16 4.126 dissolves in dilute HCl [20]
barentsite Na7AlH2(CO3)4F4 9:0:1:12:4:4 505.95 P1 a=6.472 b=6.735 c=8.806 92.50 β=97.33 119.32
Bastnäsite (Ce, La)CO3F 0:0:1:2:1:1 P62m a=7.094 c=4.859
Bastnäsite-(La) La(CO3)F 0:0:1:2:1:1 217.91 P62c
Bastnäsite-(Nd) Nd(CO3)F 0:0:1:2:1:1 223.25
Brenkite Ca2(CO3)F2 0:2:0:4:1:1 178.16 orthorhombic Pbcn a=7.650 b=7.550 c=6.548 [2]
Cebaite Ba3(Nd,Ce)2(CO3)5F2 0:3:2:12:5:2 Monoclinic a=21.42 b=5.087 c=13.30 β=94.8° [2][21]
Cordylite = Baiyuneboite NaBaCe2(CO3)4F 1:1:2:9:4:1 699.58 P63/mmc a=5.1011 c=23.096 [2]
Doverite CaY(CO3)2F 0:1:1:5:2:1 268.00 [22]
Francolite
Horvathite-Y (horváthite) NaY(CO3)F2 1:0:1:4:1:2 209.90 Pmcn a=6.959 b=9.170 c=6.301
[23]
Huanghoite-(Ce) BaCe(CO3)2F 0:1:1:5:2:1 416.46 Trigonal R3m a=5.072 c=38.46 [21][2]
Kettnerite CaBi(CO3)OF
kukharenkoite-(Ce) Ba2Ce(CO3)3F 0:2:1:7:3:1 613.80 P21/m a=13.365 b=5.097 c=6.638 β=106.45 [2]
Lukechangite-(Ce) Na3Ce2(CO3)4F 3:0:2:9:4:1 608.24 P63/mmc a=5.0612 c=22.820
lusernaite Y4Al(CO3)2(OH,F)11.6H2O 0:0:5:15:2:11 Orthorhombic Pmna a=7.8412 b=11.0313 c=11.3870 Z=2 984.96
Mineevite-(Y) Na25BaY2(CO3)11(HCO3)4(SO4)2F2Cl 2059.62 [24]
Montroyalite Sr4Al8(CO3)3(OH,F)26.10-11H2O [25]
Parisite [LaF]2Ca(CO3)3 0:1:2:8:3:2 535.91 Rhombohedral R3 a=7.124 c=84.1
Parisite-(Ce) [CeF]2Ca(CO3)3 0:1:2:8:3:2 538.33 monoclinic Cc a = 12.305 Å, b = 7.1056 Å, c = 28.2478 Å; β = 98.246°; Z = 12
Podlesnoite BaCa2(CO3)2F2 0:3:0:6:2:2 375.50 Orthorhombic Cmcm a = 12.511 b=5.857 c=9.446 Z=4 692.2 3.614 named after Aleksandr Semenovich Podlesnyi 1948 [26]
qaqarssukite-(Ce) BaCe(CO3)2F 0:1:1:5:2:1 416.46 [2]
röntgenite-(Ce) Ca2Ce3(CO3)5F3 0:2:3:13:5:3 857.54 R3 a=7.131 c=69.40 [2]
rouvilleite Na3Ca2(CO3)3F 3:2:0:7:3:1 348.15 Cc a=8.012 b=15.79 c=7.019 β =100.78 [2]
Schröckingerite NaCa3(UO2)(CO3)3F(SO4)·10H2O 1:6:13:3:1+ 888.49 also with sulfate
Sheldrickite NaCa3(CO3)2F3·(H2O) 1:3:0:7:2:3 338.25 Trigonal a = 6.726 Å; c = 15.05 Å Z = 3 2.86 [27]
stenonite Sr2Al(CO3)F5 0:2:1:7:1:5 357.22 P21/n a=5.450 b=8.704 c=13.150 β=98.72 [2]
Synchysite Ca(Ce,La)(CO3)2F 0:1:1:5:2:1 C2/c a=12.329 b=7.110 c=18.741 β=102.68 [2]
Thorbastnäsite CaTh(CO3)2F2.3H2O P6̅2c a = 6.99, c = 9.71 z=3 410.87 brown [28]
zhonghuacerite Ba2Ce(CO3)3F 0:2:1:7:3:1 613.80 Monoclinic [29]

Artificial

These are non-linear optical crystals in the AMCO3F family KSrCO3F KCaCO3F RbSrCO3F KCdCO3F CsPbCO3F RbPbCO3F RbMgCO3F KMgCO3F RbCdCO3F CsSrCO3F RbCaCO3F KZnCO3F CsCaCO3F RbZnCO3F[30]

formula name weight crystal space group unit cell volume density UV thermal stability properties reference
g/mol Å Å3 nm °C
K2(HCO3)F·H2O Dipotassium hydrogencarbonate fluoride monohydrate 176.24 monoclinic P 21/m a=5.4228 b=7.1572 c=7.4539 β=105.12 Z=2 279.28 2.096 transparent below 195 nm [31]
K3(CO3)F 196.30 R3c a=7.4181 c=16.3918 [2]
KLi2CO3F 131.99 Hexagonal P63222 a=4.8222 c=10.034 Z=2 202.06 2.169 190 SHG; transparent [32]
KMgCO3F 142.42 Hexagonal P62m a=8.8437 c=3.9254 z=3 265.88 2.668 200 [33]
Na3Ca2(CO3)3F rouvilleite 348.16 monoclinic Cm a=8.0892 b=15.900 c=3.5273 β=101.66 Z=2 444.32 2.602 190 white [34]
KCaCO3F 158.18 Hexagonal P6m2 a=5.10098 c=4.45608 Z=1 100.413 2.616 ≤320 °C [35]
KCaCO3F 158.18 Hexagonal P62m a=9.1477 c=4.4169 Z=3 320.09 2.462 ≥320 °C [35]
KMnCO3F 173.04 Hexagonal P6c2 a=5.11895 c=8.42020 Z=2 191.080 3.008 [35]
KCuCO3F 181.65 [36]
NaZnCO3F 167.37 hexagonal P62c a=8.4461 c=15.550 Z=12 960.7 3.472 [37]
Na3Zn2(CO3)3F 398.74 monoclinic C2/c a=14.609 b=8.5274 c=20.1877 β=102.426 Z=12 2456.0 3.235 213 200 [38]
KZnCO3F 183.48 hexagonal P62c a=5.0182 c=8.355 Z=2 182.21 3.344 colourless [39]
Rb3(CO3)F 335.41 R3c a=7.761 c=17.412 [2]
RbCaCO3F 204.56 hexagonal P62m a=9.1979 c=4.4463 Z=3 325.77 3.128 [40]
RbMgCO3F 188.79 Hexagonal P62m a=9.0160 c=3.9403 z=3 277.39 3.39 colourless
RbZnCO3F 229.85 hexagonal P62c a=5.1035 c=8.619 Z=2 194.4 3.926 white [39]
KRb2(CO3)F 289.04 R3c a=7.6462 c=17.1364 [2]
K2Rb(CO3)F 242.67 R3c a=7.5225 c=16.7690 [2]
KSrCO3F 205.73 hexagonal P62m a=5.2598 c=4.696 Z=1 112.50 3.037 [40]
RbSrCO3F 252.10 hexagonal P62m a=5.3000 c=4.7900 Z=6 116.53 3.137 [40]
KCdCO3F 230.51 Hexagonal P6̅m2 a=5.1324 c=4.4324 z=1 101.11 3.786 227 320 colourless [41]
RbCdCO3F 276.88 hexagonal P6̅m2 1=5.2101 c=4.5293 z=1 106.48 350 colourless [11]
Li2RbCd(CO3)2F hexagonal P63/m a=4.915 c=15.45 Z=2, 323.3 colourless [42]
Cs9Mg6(CO3)8F5 1917.13 Orthorhombic Pmn21 a=13.289 b=6.8258 c=18.824 z=2 1707.4 3.729 208 [33]
CsCaCO3F 252.00 hexagonal P62m a=9.92999 c=4.5400 Z=3 340.05 3.692 [40]
CsSrCO3F 230.51 Hexagonal P6̅m2 a=9.6286 c=4.7482 Z=3 381.2 <200 590 [43]
KBa2(CO3)2F 452.8 trigonal R3 a=10.119 c=18.60 Z=9 1648 4.106 colourless [44]
Ba3Sc(CO3)F7 649.91 Orthorhombic Cmcm a=11.519 b=13.456 c=5.974 Z=4 926.0 4.662 colourless [45]
BaMnCO3F2 290.27 Hexagonal P63/m a=4.9120, c=9.919 Z=2 [46][47]
BaCoCO3F2 294.27 [48]
Ba2Co(CO3)2F2 491.60 Orthorhombic Pbca a=6.6226, b=11.494, c=9.021 and Z=4 686.7 [49]
BaNiCO3F2 294.03 [48]
BaCuCO3F2 298.88 Cmcm a=4.889 b=8.539 c=9.588 [46]
BaZnCO3F2 300.72 Hexagonal P63/m a=4.8523, c=9.854 [47]
RbBa2(CO3)2F 499.19 trigonal R3 a=10.2410 c=18.8277 Z=9 1710.1 4.362 colourless [44]
Ba2Y(CO3)2F3 540.57 Pbcn a=9.458 b=6.966 c=11.787 [2]
Cs3Ba4(CO3)3F5 1223.12 hexagonal P63mc a=11.516 c=7.613 Z=2 874.4 4.646 [40]
Na3La2(CO3)4F Lukechangite-(La) 605.81 Hexagonal P63/mmc a=5.083, c=23.034, Z=2 [50]
Na2Eu(CO3)F3 314.94 Orthorhombic Pbca a=6.596 b=10.774 c=14.09 Z=8 1001.3 4.178 [51]
Na2Gd(CO3)F3 320.24 orthorhombic a=14.125 b=10.771 c=6.576 Z=8 1000.5 4.252 <200 250 colourless [52]
KGd(CO3)F2 294.35 Orthorhombic Fddd a=7.006, b=11.181 and c=21.865 [53]
K4Gd2(CO3)3F4 726.91 R32 a=9.0268 c=13.684 [2]
BaSm(CO3)2F 426.70 R3m a=5.016 c=37.944 [2]
Yb(CO3)(OH,F)·xH2O [54]
NaYb(CO3)F2 294.04 a=6.897, b=9.118, c=6.219 Horvathite structure [54]
Na2Yb(CO3)2F 358.04 monoclinic C2/c a=17.440, b=6.100, c=11.237, β=95.64° Z=8 1189.7 [54]
Na3Yb(CO3)2F2 400.02 monoclinic Cc a=7.127, b=29.916, c=6.928, β=112.56°; Z=8 1359 [54]
Na4Yb(CO3)3F 464.03 monoclinic Cc a=8.018 b=15.929 c=13.950 β=101.425 Z=8 1746.4 3.53 263 300 nonlinear deff=1.28pm/V [55]
Na5Yb(CO3)4·2H2O 564.05 [54]
Na8Lu2(CO3)6F2 899.92 monoclinic Cc a=8.007 b=15.910 c=13.916 β=101.318 Z=4 1738 3.439 250 [56]
Na3Lu(CO3)2F2 401.96 monoclinic Cc a=7.073 b=29.77 c=6.909 β=111.92 Z=8 1349 3.957 220 [56]
Na2Lu(CO3)2F 359.97 monoclinic C2/m a=17.534 b=6.1084 c=11.284 β=111.924 Z=8 1203.2 3.974 [56]
Tl3(CO3)F thallous fluoride carbonate 692.16 Monoclinic P21/m a=7.510 b=7.407 c=6.069 γ=120° Z=2 hexagonal prisms [57]
Pb2(CO3)F2 lead carbonate fluoride 512.41 Orthorhombic Pbcn a=8.0836 b=8.309 c=6.841 Z=4 444.6 7.41 [2][7]
NaPb2(CO3)2F0.9(OH)0.1 Hexagonal P63/mmm a=5.275 c=13.479 Z=2 325 5.893 <269 260 band gap 4.28 eV; high birefringence [58]
KPb2(CO3)2F 592.5 Hexagonal P63/mmc a=5.3000 c=13.9302 z=2 338.88 5.807 250 colourless [3]
K2.70Pb5.15(CO3)5F3 1529.65 Hexagonal P-6m2 a= 5.3123 c=18.620 z=1 455.07 5.582 250 colourless non-linear peizoelectric [3]
K2Pb3(CO3)3F2 917.8 Hexagonal P63/mmc a=5.2989 c=23.2326 z=2 564.94 5.395 287 colourless [41]
RbPbCO3F 371.67 Hexagonal P6̅m2 a=5.3488 c=4.8269 Z=1 119.59 5.161 colourless mon-linear [59]
CsPbCO3F 419.11 Hexagonal P6̅m2 a=5.393 c=5.116 z=1 128.8 5.401 colourless non-linear [59]
BaPb2(CO3)2F2 709.74 R3m a=5.1865 c=23.4881 [2]

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Quelle: https://en.wikipedia.org/wiki/Carbonate_fluoride