Fluorocarbonate Explained

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

M^I	M^II	M^III	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.

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.

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. 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.

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

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

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. K_2.70Pb_5.15(CO₃)₅F₃ extends this structure with some of the layers also being a double-decker sandwich of carbonate, fluoride, carbonate, fluoride, carbonate.

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.^[2]

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.

Bastnäsite along with lukechangite (and petersenite) can be precipitated from a mixed solution of CeCl₃, NaF, and NaOH with carbon dioxide.^[3] 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).^[4]

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.

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. The visible spectrum of the rare-earth fluorocarbonates is almost entirely due to narrow absorption bands from neodymium. 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.

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.

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.^[5]

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

KCu(CO₃)F → CuO + KF + CO₂at 340 °C.

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.

2 Ce(CO₃F) + O₂ → 2 CeO₂ + 2 CO₂ + F₂

Na₃Ce₂(CO₃F)₄F + O₂ → 2 CeO₂ + 3 CO₂ + NaF + Na₂CO₃

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

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

LaCO₃F → LaOF + CO₂^[6]

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.^[7]

KCdCO₃F when heated yields cadmium oxide (CdO) and potassium fluoride (KF).^[8]

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

LaCO₃F + CO₂ → LaSF + 1.5 CO₂^[9] 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:^[10]

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.^[11]

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.^[12] Rare-earth fluorocarbonate minerals can form in bauxite on carbonate rocks, as rare-earth fluoride complexes react with carbonate.^[13] Carbonate fluoride compounds of rare-earth elements also occur in carbonatites.

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	P	a = 13.569, b = 13.419, c = 11.622 Å, α = 115.82, β = 107.61, γ = 92.84° Z=	1774.6	2.69		^[14]
aravaite	Ba2Ca18(SiO4)6(PO4)3(CO3)F3O			trigonal	Rm	a = 7.1255, c = 66.290 Z=3	2914.8			^[15]
arisite-(Ce)	NaCe2(CO3)2[(CO<sub>3</sub>)<sub>1–''x''</sub>F<sub>2''x''</sub>]F				P6̅m2	a=5.1109 c=8.6713 Z=1	196.16	4.126	dissolves in dilute HCl	^[16]
barentsite	Na7AlH2(CO3)4F4	9:0:1:12:4:4	505.95		P	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				^[17]
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°
Cordylite = Baiyuneboite	NaBaCe2(CO3)4F	1:1:2:9:4:1	699.58		P63/mmc	a=5.1011 c=23.096
Doverite	CaY(CO3)2F	0:1:1:5:2:1	268.00							^[18]
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				^[19]
Huanghoite-(Ce)	BaCe(CO3)2F	0:1:1:5:2:1	416.46	Trigonal	Rm	a=5.072 c=38.46				^[20]
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
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							^[21]
Montroyalite	Sr4Al8(CO3)3(OH,F)26.10-11H2O									^[22]
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	^[23]
qaqarssukite-(Ce)	BaCe(CO3)2F	0:1:1:5:2:1	416.46
röntgenite-(Ce)	Ca2Ce3(CO3)5F3	0:2:3:13:5:3	857.54		R3	a=7.131 c=69.40
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
	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		^[24]
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
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
Thorbastnäsite	CaTh(CO3)2F2.3H2O				P6̅2c	a = 6.99, c = 9.71 z=3	410.87		brown	^[25]
zhonghuacerite	Ba2Ce(CO3)3F	0:2:1:7:3:1	613.80	Monoclinic						^[26]

Artificial

These are non-linear optical crystals in the AMCO₃F familyKSrCO₃FKCaCO₃FRbSrCO₃FKCdCO₃FCsPbCO₃FRbPbCO₃FRbMgCO₃FKMgCO₃FRbCdCO₃FCsSrCO₃FRbCaCO₃FKZnCO₃FCsCaCO₃FRbZnCO₃F^[27]

formula	name	weight	crystal	space group	unit cell	volume	density	UV	thermal stability	properties	reference
		g/mol			Å	Å^3		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	^[28]
K3(CO3)F		196.30		Rc	a=7.4181 c=16.3918
KLi2CO3F		131.99	Hexagonal	P63222	a=4.8222 c=10.034 Z=2	202.06	2.169	190		SHG; transparent	^[29]
KMgCO3F		142.42	Hexagonal	P62m	a=8.8437 c=3.9254 z=3	265.88	2.668	200			^[30]
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	^[31]
KCaCO3F		158.18	Hexagonal	Pm2	a=5.10098 c=4.45608 Z=1	100.413	2.616			≤320 °C	^[32]
KCaCO3F		158.18	Hexagonal	P2m	a=9.1477 c=4.4169 Z=3	320.09	2.462			≥320 °C
KMnCO3F		173.04	Hexagonal	Pc2	a=5.11895 c=8.42020 Z=2	191.080	3.008
KCuCO3F		181.65									^[33]
NaZnCO3F		167.37	hexagonal	P2c	a=8.4461 c=15.550 Z=12	960.7	3.472				^[34]
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		^[35]
KZnCO3F		183.48	hexagonal	P2c	a=5.0182 c=8.355 Z=2	182.21	3.344			colourless	^[36]
Rb3(CO3)F		335.41		Rc	a=7.761 c=17.412
RbCaCO3F		204.56	hexagonal	P2m	a=9.1979 c=4.4463 Z=3	325.77	3.128				^[37]
RbMgCO3F		188.79	Hexagonal	P62m	a=9.0160 c=3.9403 z=3	277.39	3.39			colourless
RbZnCO3F		229.85	hexagonal	P2c	a=5.1035 c=8.619 Z=2	194.4	3.926			white
KRb2(CO3)F		289.04		Rc	a=7.6462 c=17.1364
K2Rb(CO3)F		242.67		Rc	a=7.5225 c=16.7690
KSrCO3F		205.73	hexagonal	P2m	a=5.2598 c=4.696 Z=1	112.50	3.037
RbSrCO3F		252.10	hexagonal	P2m	a=5.3000 c=4.7900 Z=6	116.53	3.137
KCdCO3F		230.51	Hexagonal	P6̅m2	a=5.1324 c=4.4324 z=1	101.11	3.786	227	320	colourless
RbCdCO3F		276.88	hexagonal	P6̅m2	1=5.2101 c=4.5293 z=1	106.48			350	colourless
Li2RbCd(CO3)2F			hexagonal	P63/m	a=4.915 c=15.45 Z=2,	323.3				colourless	^[38]
Cs9Mg6(CO3)8F5		1917.13	Orthorhombic	Pmn21	a=13.289 b=6.8258 c=18.824 z=2	1707.4	3.729	208
CsCaCO3F		252.00	hexagonal	P2m	a=9.92999 c=4.5400 Z=3	340.05	3.692
CsSrCO3F		230.51	Hexagonal	P6̅m2	a=9.6286 c=4.7482 Z=3	381.2		<200	590		^[39]
KBa2(CO3)2F		452.8	trigonal	R	a=10.119 c=18.60 Z=9	1648	4.106			colourless	^[40]
Ba3Sc(CO3)F7		649.91	Orthorhombic	Cmcm	a=11.519 b=13.456 c=5.974 Z=4	926.0	4.662			colourless	^[41]
BaMnCO3F2		290.27	Hexagonal	P63/m	a=4.9120, c=9.919 Z=2						^[42]
BaCoCO3F2		294.27									^[43]
Ba2Co(CO3)2F2		491.60	Orthorhombic	Pbca	a=6.6226, b=11.494, c=9.021 and Z=4	686.7					^[44]
BaNiCO3F2		294.03
BaCuCO3F2		298.88		Cmcm	a=4.889 b=8.539 c=9.588						^[45]
BaZnCO3F2		300.72	Hexagonal	P63/m	a=4.8523, c=9.854
RbBa2(CO3)2F		499.19	trigonal	R	a=10.2410 c=18.8277 Z=9	1710.1	4.362			colourless
Ba2Y(CO3)2F3		540.57		Pbcn	a=9.458 b=6.966 c=11.787
Cs3Ba4(CO3)3F5		1223.12	hexagonal	P63mc	a=11.516 c=7.613 Z=2	874.4	4.646
Na3La2(CO3)4F	Lukechangite-(La)	605.81	Hexagonal	P63/mmc	a=5.083, c=23.034, Z=2						^[46]
Na2Eu(CO3)F3		314.94	Orthorhombic	Pbca	a=6.596 b=10.774 c=14.09 Z=8	1001.3	4.178				^[47]
Na2Gd(CO3)F3		320.24	orthorhombic		a=14.125 b=10.771 c=6.576 Z=8	1000.5	4.252	<200	250	colourless	^[48]
KGd(CO3)F2		294.35	Orthorhombic	Fddd	a=7.006, b=11.181 and c=21.865						^[49]
K4Gd2(CO3)3F4		726.91		R32	a=9.0268 c=13.684
BaSm(CO3)2F		426.70		Rm	a=5.016 c=37.944
Yb(CO3)(OH,F)·xH2O
NaYb(CO3)F2		294.04			a=6.897, b=9.118, c=6.219					Horvathite structure	^[50]
Na2Yb(CO3)2F		358.04	monoclinic	C2/c	a=17.440, b=6.100, c=11.237, β=95.64° Z=8	1189.7
Na3Yb(CO3)2F2		400.02	monoclinic	Cc	a=7.127, b=29.916, c=6.928, β=112.56°; Z=8	1359
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	^[51]
Na5Yb(CO3)4·2H2O		564.05
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		^[52]
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
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
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	^[53]
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				^[54]
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	^[55]
KPb2(CO3)2F		592.5	Hexagonal	P63/mmc	a=5.3000 c=13.9302 z=2	338.88	5.807		250	colourless	^[56]
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
K2Pb3(CO3)3F2		917.8	Hexagonal	P63/mmc	a=5.2989 c=23.2326 z=2	564.94	5.395	287		colourless	^[57]
RbPbCO3F		371.67	Hexagonal	P6̅m2	a=5.3488 c=4.8269 Z=1	119.59	5.161			colourless mon-linear	^[58]
CsPbCO3F		419.11	Hexagonal	P6̅m2	a=5.393 c=5.116 z=1	128.8	5.401			colourless non-linear
BaPb2(CO3)2F2		709.74		Rm	a=5.1865 c=23.4881

Notes and References

1. Rao . E. Narsimha . Vaitheeswaran . G. . Reshak . A. H. . Auluck . S. . Effect of lead and caesium on the mechanical, vibrational and thermodynamic properties of hexagonal fluorocarbonates: a comparative first principles study . RSC Advances . 2016 . 6 . 102 . 99885–99897 . 10.1039/C6RA20408B. 2016RSCAd...699885R .
2. Turner . D. J. . Rivard . B. . Groat . L. A. . Visible and short-wave infrared reflectance spectroscopy of REE fluorocarbonates . American Mineralogist . 1 July 2014 . 99 . 7 . 1335–1346 . 10.2138/am.2014.4674. 2014AmMin..99.1335T . 97165560 .
3. Corbel . Gwenaël . Courbion . Georges . Le Berre . Françoise . Leblanc . Marc . Le Meins . Jean-Marc . Maisonneuve . Vincent . Mercier . Nicolas . Synthesis from solutions and properties of various metal fluorides and fluoride salts . Journal of Fluorine Chemistry . February 2001 . 107 . 2 . 193–198 . 10.1016/S0022-1139(00)00358-4.
4. Gavrilova . G. V. . Konyukhov . M. Yu. . Logvinenko . V. A. . Sedova . G. N. . Study of the thermal decomposition kinetics of some rare earth carbonates, fluorocarbonates and fluorooxalates . Journal of Thermal Analysis . April 1994 . 41 . 4 . 889–897 . 10.1007/BF02547168. 96635485 .
5. Kul . M. . Topkaya . Y. . Karakaya . İ. . Rare earth double sulfates from pre-concentrated bastnasite . Hydrometallurgy . August 2008 . 93 . 3–4 . 129–135 . 10.1016/j.hydromet.2007.11.008. 96914838 .
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