Langbeinites

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Langbeinites are a family of crystalline substances based on the structure of langbeinite with general formula M2M'2(SO4)3, where M is a large univalent cation (such as potassium, rubidium, caesium, or ammonium), and M' is a small divalent cation (for example, magnesium, calcium, manganese, iron, cobalt, nickel, copper, zinc or cadmium). The sulfate group, SO2−4, can be substituted by other tetrahedral anions with a double negative charge such as tetrafluoroberyllate (BeF2−4), selenate (SeO2−4), chromate (CrO2−4), molybdate (MoO2−4), or tungstates. Although monofluorophosphates are predicted, they have not been described. By redistributing charges other anions with the same shape such as phosphate also form langbeinite structures. In these the M' atom must have a greater charge to balance the extra three negative charges.

Contents

At higher temperatures the crystal structure is cubic P213. [1] However, the crystal structure may change to lower symmetries at lower temperatures, for example, P21, P1, or P212121. [1] Usually this temperature is well below room temperature, but in a few cases the substance must be heated to acquire the cubic structure.

Crystal structure

The crystal structures of langbeinites consist of a network of oxygen vertex-connected tetrahedral polyanions (such as sulfate) and distorted metal ion-oxygen octahedra. [2] The unit cell contains four formula units. In the cubic form the tetrahedral anions are slightly rotated from the main crystal axes. When cooled, this rotation disappears and the tetrahedra align, resulting in lower energy as well as lower crystal symmetry.

Examples

Sulfates include dithallium dicadmium sulfate, [3] dirubidium dicadmium sulfate, [4] dipotassium dicadmium sulfate, [5] dithallium manganese sulfate, [6] and dirubidium dicalcium trisulfate. [7]

Selenates include diammonium dimanganese selenate. [1] A diammonium dicadmium selenate langbeinite could not be crystallised from water, but a trihydrate exists. [8]

Chromate based langbeinites include dicaesium dimanganese chromate. [1]

Molybdates include Rb2Co2(MoO4)3. [1] Potassium members are absent, as are zinc and copper containing solids, which all crystallize in different forms. Manganese, magnesium, cadmium and some nickel double molybdates exist as langbeinites. [9]

Double tungstates of the form A2B2(WO4)3 are predicted to exist in the langbeinite form. [10]

An examples with tetrafluroberyllate is dipotassium dimanganese tetrafluoroberyllate (K2Mn2(BeF4)3). [11] Other tetrafluoroberyllates may include: Rb2Mg2(BeF4)3; Tl2Mg2(BeF4)3; Rb2Mn2(BeF4)3; Tl2Mn2(BeF4)3; Rb2Ni2(BeF4)3; Tl2Ni2(BeF4)3; Rb2Zn2(BeF4)3; Tl2Zn2(BeF4)3; Cs2Ca2(BeF4)3; Rb2Ca2(BeF4)3; RbCsMnCd(BeF4)3; Cs2MnCd(BeF4)3; RbCsCd2(BeF4)3; Cs2Cd2(BeF4)3; Tl2Cd2(BeF4)3; (NH4)2Cd2(BeF4)3; KRbMnCd(BeF4)3; K2MnCd(BeF4)3; Rb2MnCd(BeF4)3; Rb2Cd2(BeF4)3; RbCsCo2(BeF4)3; (NH4)2Co2(BeF4)3; K2Co2(BeF4)3; Rb2Co2(BeF4)3; Tl2Co2(BeF4)3; RbCsMn2(BeF4)3; Cs2Mn2(BeF4)3; RbCsZn2(BeF4)3; (NH4)2Mg2(BeF4)3; (NH4)2Mn2(BeF4)3; (NH4)2Ni2(BeF4)3; (NH4)2Zn2(BeF4)3;KRbMg2(BeF4)3; K2Mg2(BeF4)3; KRbMn2(BeF4)3; K2Ni2(BeF4)3; K2Zn2(BeF4)3. [12]

The phosphate containing langbeinites were found in 1972 with the discovery of KTi2(PO4)3, and since then a few more phosphates that also contain titanium have been found such as Na2FeTi(PO4)3 and Na2CrTi(PO4)3. By substituting metals in A2MTi(PO4)3, A from (K, Rb, Cs), and M from (Cr, Fe, V), other langbeinites are made. The NASICON-type structure competes for these kinds of phosphates, so not all possibilities are langbeinites. [1] Other phosphate based substances include K2YTi(PO4)3, K2ErTi(PO4)3, K2YbTi(PO4)3, K2CrTi(PO4)3, [1] K2AlSn(PO4)3, [13] KRbYbTi(PO4)3. [14] Sodium barium diiron tris-(phosphate) (NaBaFe2(PO4)3) is yet another variation with the same structure but differently charged ions. [15] Most phosphates of this kind of formula do not form langbeinites, instead crystallise in the NASICON structure with archetype Na3Zr2(PO4)(SiO4)2. [1]

A langbeinite with arsenate is known to exist by way of K2ScSn(AsO4)3. [16]

Properties

Physical properties

Langbeinite-family crystals can show ferroelectric or ferroelastic properties. [1] Diammonium dicadmium sulfate identified by Jona and Pepinsky [17] with a unit cell size of 10.35 Å becomes ferroelectric when the temperature drops below 95 K. [18] The phase transition temperature is not fixed, and can vary depending on the crystal or history of temperature change. So for example the phase transition in diammonium dicadmium sulfate can occur between 89 and 95 K. [19] Under pressure the highest phase transition temperature increases. ∂T/∂P = 0.0035 degrees/bar. At 824 bars there is a triple point with yet another transition diverging at a slope of ∂T/∂P = 0.103 degrees/bar. [20] For dipotassium dimanganese sulfate pressure causes the transition to rise at the rate of 6.86 °C/kbar. The latent heat of the transition is 456 cal/mol. [21]

Dithallium dicadmium sulfate was shown to be ferroelectric in 1972. [22]

Dipotassium dicadmium sulfate is thermoluminescent with stronger outputs of light at 350 and 475 K. This light output can be boosted forty times with a trace amount of samarium. [23] Dipotassium dimagnesium sulfate doped with dysprosium develops thermoluminescence and mechanoluminescence after being irradiated with gamma rays. [24] Since gamma rays occur naturally, this radiation induced thermoluminescence can be used to date evaporites in which langbeinite can be a constituent. [25]

At higher temperatures the crystals take on cubic form, whereas at the lowest temperatures they can transform to an orthorhombic crystal group. For some types there are two more phases, and as the crystal is cooled it goes from cubic, to monoclinic, to triclinic to orthorhombic. This change to higher symmetry on cooling is very unusual in solids. [26] For some langbeinites only the cubic form is known, but that may be because it has not been studied at low enough temperatures yet. Those that have three phase transitions go through these crystallographic point groups: P213 – P21 – P1 – P212121, whereas the single phase change crystals only have P213 – P212121.

K2Cd2(SO4)3 has a transition temperature above room temperature, so that it is ferroelectric in standard conditions. The orthorhombic cell size is a=10.2082 Å, b=10.2837 Å, c=10.1661 Å. [27]

Where the crystals change phase there is a discontinuity in the heat capacity. The transitions may show thermal hysteresis. [28]

Different cations can be substituted so that for example K2Cd2(SO4)3 and Tl2Cd2(SO4)3 can form solid solutions for all ratios of thallium and potassium. Properties such as the phase transition temperature and unit cell sizes vary smoothly with the composition. [29]

Langbeinites containing transition metals can be coloured. For example, cobalt langbeinite shows a broad absorption around 555 nm due to the cobalt 4T1g(F)→4T1g(P) electronic transition. [30]

The enthalpy of formation (ΔfHm) for solid (NH4)2Cd2(SO4)3 at 298.2 K is −3031.74±0.08 kJ/mol, and for K2Cd2(SO4)3 it is −3305.52±0.17 kJ/mol. [31]

Sulfates

Properties of langbeinites with sulfate anions
FormulaWeight (g/mol)Comment / SymmetriesTransition temperature (K)DensityCell size (Å)Refractive index
123 [32]
Na2Mg2(SO4)3382.783 phases, 1–2, >3250350575 [33]
K2Mg2(SO4)3414.994 phases langbeinite 5154.963.82.832 [34] 9.9211 [35] 1.536 [36]
Rb2Mg2(SO4)3507.73made3.367 [37] 10.0051 [38] 1.556 [38]
Cs2Mg2(SO4)3602.61no compound [10]
(NH4)2Mg2(SO4)3372.87 Efremovite [39] 241 [40] 220 [40] 2.49 [41] 9.979 [41]
Tl2Mg2(SO4)3745.56≥3 phase227.8 [40] 330.8 [40]
K2CaMg(SO4)3430.77made2.723 [42] 10.1662 [42] 1.525 [42]
K2Ca2(SO4)3446.544 phases calciolangbeinite [43] [44] [45] 4572.69 2.683 [46] 10.429Å a=10.334 b=10.501 c=10.186Nα=1.522 Nβ=1.526 Nγ=1.527
Rb2Ca2(SO4)3539.282 phases1833.034 [47] 10.5687 [47] 1.520 [47]
Cs2Ca2(SO4)3634.153.417 [48] [49] 10.72131.549
Tl2Ca2(SO4)3no compound [10]
(NH4)2Ca2(SO4)3404.42made1582.297 [50] 10.5360 [51] 1.532 [51]
(NH4)2V2(SO4)3colour clear green [52] 2.76 [53] 10.089 [52]
K2Mn2(SO4)3476.26manganolangbeinite [54]
2 phases
pale pink [55] 		1913.02 [35] 10.014 [35]
(orthorhombic)
a=10.081, b=10.108, c=10.048 Å [56] 		1.576 [55]
Rb2Mn2(SO4)3569made [57] 3.546 [58] 10.2147 [58] 1.590 [58]
Cs2Mn2(SO4)3663.87predicted [10]
(NH4)2Mn2(SO4)2434.14made2.72 [41] 10.1908 [59]
Tl2Mn2(SO4)3806.83made5.015 [60] 10.2236 [60] 1.722 [60]
K2Fe2(SO4)3478.07made?130
Rb2Fe2(SO4)3predicted [10]
Tl2Fe2(SO4)3808.64exists [10]
(NH4)2Fe2(SO4)3 [52] 435.95mineral ferroefremovite 2.84 [41] 10.068 [41] 1.574 [61]
K2Co2(SO4)3484.252 phases
deep purple		1263.280 [34] 9.9313 [35] 1.608 [62]
Rb2Co2(SO4)3576.99made3.807 [63] 10.0204 [63] 1.602 [63]
Cs2Co2(SO4)3671.87
(NH4)2Co2(SO4)3442.13made2.94 [41] 9.997 [41]
Tl2Co2(SO4)3813.82made5.361 [64] 10.03121.775
K2Ni2(SO4)3483.77made [65] light greenish yellow [66] 3.369 [34] 9.8436 [66] 1.620 [66]
Rb2Ni2(SO4)3576.51made3.921 [67] 9.9217 [67] 1.636 [67]
Cs2Ni2(SO4)3671.39predicted [10]
(NH4)2Ni2(SO4)3441.65made [65] 1603.02 [41] 9.904 [41]
Tl2Ni2(SO4)3814.34predicted [10]
Rb2Cu2(S04)3predicted [10]
Cs2Cu2(S04)3predict not [10]
Tl2Cu2(S04)3predicted [10]
K2Zn2(SO4)3497.14 phases751383.376 [34] 9.9247 [68] 1.592 [68]
Rb2Zn2(S04)3predicted [10]
Cs2Zn2(S04)3predict not [10]
Tl2Zn2(S04)3predicted [10]
K2Cd2(SO4)3591.212 phases4322.615 3.677 [69] a=10.212 b=10.280 c=10.171Nα=1.588 Nγ=1.592
Rb2Cd2(SO4)3683.954 phases661031294.060 [35] [70] 10.3810 [35] [70] 1.590 [70]
(NH4)2Cd2(SO4)3549.094 phases953.288 [35] 10.3511 [35]
Tl2Cd2(SO4)3921.784 phases921201325.467 [35] 10.3841 [35] 1.730 [71]

Fluoroberyllates

Properties of langbeinites with fluoroberyllate (BeF2−4) anion
FormulaWeight (g/mol)Cell size (Å)VolumeDensityComment
K2Mn2(BeF4)3 [11] 4 phases transition at 213
K2Mg2(BeF4)3 [72] 9.875962.81.59
(NH4)2Mg2(BeF4)3 [72] 9.9681.37
KRbMg2(BeF4)3 [72] 9.9331.72
Rb2Mg2(BeF4)3 [72] 9.9711.91
Tl2Mg2(BeF4)3 [72] 9.9972.85
K2Ni2(BeF4)3 [72] 9.8881.86
Rb2Ni2(BeF4)3 [72] 9.9742.19
Tl2Ni2(BeF4)3 [72] 9.9933.13
K2Co2(BeF4)3 [72] 9.9639881.82
(NH4)2Co2(BeF4)3 [72] 10.0521.61
Rb2Co2(BeF4)3 [72] 10.0612.14
Tl2Co2(BeF4)3 [72] 10.0783.05
RbCsCo2(BeF4)3 [72] 10.1152.28
K2Zn2(BeF4)3 [72] 9.9321.89
(NH4)Zn2(BeF4)3 [72] 10.0361.67
Rb2Zn2(BeF4)3 [72] 10.0352.20
Tl2Zn2(BeF4)3 [72] 10.0603.14
RbCsZn2(BeF4)3 [72] 10.1022.36
K2Mn2(BeF4)3 [72] 10.1021.72
KRbMn2(BeF4)3 [72] 10.1871.82
(NH4)2Mn2(BeF4)3 [72] 10.2171.50
Rb2Mn2(BeF4)3 [72] 10.2432.00
Tl2Mn2(BeF4)3 [72] 10.2552.87
RbCsMn2(BeF4)3 [72] 10.3272.12
Cs2Mn2(BeF4)3 [72] 10.3762.26
K2MnCd(BeF4)3 [72] 10.1331.92
KRbMnCd(BeF4)3 [72] 10.2202.04
Rb2MnCd(BeF4)3 [72] 10.1331.92
RbCsMnCd(BeF4)3 [72] 10.3802.28
Cs2MnCd(BeF4)3 [72] 10.4512.41
(NH4)2Cd2(BeF4)3 [72] 10.3421.87
Rb2Cd2(BeF4)3 [72] 10.3852.32
Tl2Cd2(BeF4)3 [72] 10.4023.16
RbCsCd2(BeF4)3 [72] 10.4742.43
Cs2Cd2(BeF4)3 [72] 10.5582.53
RbCsCdCa(BeF4)3 [72] 10.5012.15
Rb2Ca2(BeF4)3 [72] 10.4801.74
RbCsCa2(BeF4)3 [72] 10.5831.86
Cs2Ca2(BeF4)3 [72] 10.6721.98
Cs2Mg2(BeF4)3does not exist [72]

Phosphates

Properties of langbeinites with phosphate (PO2−4) anion
FormulaWeight (g/mol)Cell size (Å)DensityCommentref
LiCs2Y2(PO4)3735.4810.59454.108 [73]
LiRb2Y2(PO4)3non-linear optical [74]
K2YTi(PO4)3578.2510.10533.192 [1]
K2ErTi(PO4)3584.0310.0943.722 [1]
K2YbTi(PO4)3499.8910.13183.772 [1]
K2CrTi(PO4)3462.989.80013.267 [1]
(NH4)(H3O)TiIIITiIV(PO4)3417.719.9384 [75]
K2Ti2(PO4)3458.849.8688Also K2−x; dark blue [76]
Rb2Ti2(PO4)3551.589.9115 [76]
Tl2Ti2(PO4)3789.419.9386 [76]
Na2FeTi(PO4)39.837 [77]
Na2CrTi(PO4)39.775 [77]
K2Mn0.5Ti1.5(PO4)39.9033.162dark brown [78]
K2Co0.5Ti1.5(PO4)39.8443.233dark brown [78]
Rb4NiTi3(PO4)61113.99÷29.9386 [79]
K2AlTi(PO4)3437.969.76413.125colourless [80]
K2TiYb(PO4)3 [81]
Li2Zr2(PO4)3481.24 [82]
NaZr2(PO4)3980,7110.20883.06125negative thermal expansion 25-500 °C [83]
K2(Ce, ..., Lu)Zr(PO4)3594.45...629.310.29668 [84]
Rb2FeZr(PO4)3602.9210.1199 [85]
K2FeZr(PO4)3510.1810.0554dark grey Note Na2FeZr(PO4)3 is not a langbeinite. [86] [87]
K2YZr(PO4)3543.2410.3346random Y and Zr [88]
K2GdZr(PO4)3611.5810.3457random Gd and Zr [88]
K2YHf(PO4)3630.5110.30753.824 [89]
Li(H2O)2Hf2(PO4)3684.8710.1993 [90]
K2BiHf(PO4)3750.58 [91]
Li(H2O)2Zr2(PO4)3510.3310.2417 [82]
K2AlSn(PO4)3508.789.798 [13]
K2CrSn(PO4)39.8741[ citation needed ]
K2InSn(PO4)310.0460[ citation needed ]
K2FeSn(PO4)39.921[ citation needed ]
K2YbSn(PO4)310.150[ citation needed ]
K4Al3Ta(PO4)6988.119.7262 [92]
K4Cr3Ta(PO4)61063.169.8315 [92]
K4Fe3Ta(PO4)61074.709.9092 [92]
K4Tb3Ta(PO4)610.3262 [93]
K4Ga3Ta(PO4)6 [94]
K4Gd3Ta(PO4)6 [94]
K4Dy3Ta(PO4)6 [94]
K4Ho3Ta(PO4)6 [94]
K4Er3Ta(PO4)6 [94]
K4Yb3Ta(PO4)6 [94]
Rb4Ga3Ta(PO4)6 [94]
Rb4Gd3Ta(PO4)6 [94]
Rb4Dy3Ta(PO4)6 [94]
Rb4Ho3Ta(PO4)6 [94]
Rb4Er3Ta(PO4)6 [94]
Rb4Yb3Ta(PO4)6 [94]
K4Fe3Nb(PO4)6986.669.9092 [92]
KBaEr2(PO4)3795.857 [95]
RbBaEr2(PO4)3842.227 [95]
CsBaEr2(PO4)3889.665 [95]
(Rb,Cs)2(Pr,Er)Zr(PO4)3 [95]
KCsFeZrP3O12603.9910.103 [96]
CaFe3O(PO4)3508.53 [97]
SrFe3O(PO4)3556.1 [97]
PbFe3O(PO4)3675.6 [97]
KSrFe2(PO4)3523.329.8093.68yellowish [98]
Pb1.5VIV2(PO4)3697.69.78184.912 [99]
K2TiV(PO4)39.855green [100]
BaTiV(PO4)39.9223.54at high temperature > 950 °C dark grey [100]
KBaV2(PO4)39.873greenish yellow [100]
Ba1.5V2(PO4)39.884grey [100]
Ba1.5Fe3+2(PO4)3 [101] [102] 602.59
KSrSc2(PO4)3 [103] 501.54
Rb0.743K0.845Co0.293Ti1.707(PO4)3 [104] 9.8527
K2BiZr(PO4)6 [105] 663.3210.3036
KBaSc2(PO4)3 [106] 503.25
KBaIn2(PO4)3 [107]
KBaRZrP2SiO12 [2] R = La, Nd, Sm, Eu, Gd, Dy, Y
KBaYSnP2SiO12 [2] 666.07
KBaFe2(PO4)3 [108] 525.039.8732 (at 4 K)
KBaCr2(PO4)3 [109] 517.339.7890
Rb2FeTi(PO4)3 [110] 511.569.8892Na2FeTi(PO4)3 has NZP structure [87]
KBaMgTi(PO4)3 [111] 485.519.914KSrMgTi crystallises in kosnarite form
KPbMgTi(PO4)3 [111] 555.399.8540KSrMgTi in kosnarite form
RbBaMgTi(PO4)39.954531.88CsBa does not form [111]
RbPbMgTi(PO4)3601.769.9090CsPb does not form [111]
KSrMgZr(PO4)3479.1610.165 [111]
KPbMgZr(PO4)3598.7410.111 [111]
KBaMgZr(PO4)3528.8710.106 [111]
RbSrMgZr(PO4)3525.5310.218 [111]
RbPbMgZr(PO4)3645.1110.178 [111]
RbBaMgZr(PO4)3575.2410.178 [111]
CsSrMgZr(PO4)3572.9710.561over 1250 °C forms kosnarite phase [111]
Ba3In4(PO4)610.1129 [112]
Ba3V4(PO4)61185.589.88254.08yellow-green [113]
KPbCr2(PO4)39.7332 [114]
KPbFe2(PO4)39.8325beige [114]
K4NiHf3(PO4)6660.192 (half)10.122014.228yellow [115]
NaBaBi2(PO3)3 [116]

Phosphate silicates

substanceformula weightunit cell edge Ådensitycommentref
K2Sn2(PO4)2SiO4 [117] Stable to 650 °C
K2Zr2(PO4)2SiO4 [117] Stable to 1000 °C
Cs2Zr2(PO4)2SiO4 [118]
CsKZr2(PO4)2SiO4 [118]
KBaZrY(PO4)2SiO4 [119]
KBaZrLa(PO4)2SiO4 [119]
KBaZrNd(PO4)2SiO4 [119]
KBaZrSm(PO4)2SiO4 [119]
KBaZrEu(PO4)2SiO4 [119]

Mixed anion phosphates

substanceformula weightunit cell edge Ådensitycommentref
K2MgTi(SO4)(PO4)2 [120]
K2Fe2(MoO4)(PO4)2 [121]
K2Sc2(MoO4)(PO4)2 [121]
K2Sc2(WO4)(PO4)2 [121]

Vanadates

The orthovanadates have four formula per cell, with a slightly distorted cell that has orthorhombic symmetry.

formula weightcommentCell dimensions ÅVolumedensityrefractive
Formulag/molsymmetriesabcindex
LiBaCr2(VO4)3 [122] 593.08Orthorhombic9.9810.529.519984.02
NaBaCr2(VO4)3 [122] 609.13Orthorhombic9.9910.529.5310024.09
AgBaCr2(VO4)3 [122] 694.00Orthorhombic10.0210.539.5310054.62

Arsenates

substanceformula weightunit cell edge Ådensity
K2ScSn(AsO4)3 [123] 658.6210.3927
Zr2NH4(AsO4)3·H2O [124] 632.55810.5323.379

Selenates

Langbeinite structured double selenates are difficult to make, perhaps because selenate ions arranged around the dication leave space for water, so hydrates crystallise from double selenate solutions. For example, when ammonia selenate and cadmium selenate solution is crystallized it forms diammonium dicadmium selenate trihydrate: (NH4)2Cd2(SeO4)3·3H2O and when heated it loses both water and ammonia to form a pyroselenate rather than a langbeinite. [125]

substanceformula weightunit cell edge Ådensitynote
(NH4)2Mn2(SeO4)3 [126] 574.8310.533.26forms continuous series with SO4 too

Molybdates

substanceformula weightunit cell edge Ådensityref
Cs2Cd2(MoO4)3970.511.239 [127]
Rb2Co2(MoO4)3768.7
Cs2Co2(MoO4)3 [128]
Cs2Fe2(MoO4)310.9112 [129]
Cs2Ni2(MoO4)3863.0110.7538 [130]
(H3O)2Mn2(MoO4)3627.7510.8713 [131]
K2Mn2(MoO4)3 [132]

Tungstates

substanceformula weightunit cell edge Ådensity
Rb2Mg2(WO4)3 [133] 963.0610.766
Cs2Mg2(WO4)3 [133] 1057.9310.878

Preparation

Diammonium dicadmium sulfate can be made by evaporating a solution of ammonium sulfate and cadmium sulfate. [19] Dithallium dicadmium sulfate can be made by evaporating a water solution at 85 °C. [22] Other substances may be formed during crystallisation from water such as Tutton's salts or competing compounds like Rb2Cd3(SO4)4·5H2O. [134]

Potassium and ammonium nickel langbeinite can be made from nickel sulfate and the other sulfates by evaporating a water solution at 85 °C. [65]

Dipotassium dizinc sulfate can be formed into large crystals by melting zinc sulfate and potassium sulfate together at 753 K. A crystal can be slowly drawn out of the melt from a rotating crucible at about 1.2 mm every hour. [135]

Li(H2O)2Hf2(PO4)3 can be made by heating HfCl4, Li2B4O7, H3PO4, water and hydrochloric acid to 180 °C for eight days under pressure. [90] Li(H2O)2Hf2(PO4)3 converts to Li2Hf2(PO4)3 on heating to 200 °C. [82]

The sol-gel method produces a gel from a solution mixture, which is then heated. Rb2FeZr(PO4)3 can be made by mixing solutions of FeCl3, RbCl, ZrOCl2, and dripping in H3PO4. The gel produced was dried out at 95 °C and then baked at various temperatures from 400 to 1100 °C. [85]

Langbeinites crystals can be made by the Bridgman technique, Czochralski process or flux technique.

A Tutton's salt may be heat treated and dehydrate, e.g. (NH4)2Mn2(SeO4)3 can be made from (NH4)2Mn(SeO4)3·6(H2O) heated to 100 °C, forming (NH4)2(SeO4) as a side product. [136] Similarly the ammonium vanadium Tutton's salt, (NH4)2V(SO4)2, heated to 160 °C in a closed tube produces (NH4)2V2(SO4)3. At lower temperatures a hydroxy compound is formed. [52]

Use

Few uses have been made of these substances. Langbeinite itself can be used as an "organic" fertiliser with potassium, magnesium and sulfur, all needed for plant growth. Electrooptic devices could be made from some of these crystals, particularly those that have cubic transition temperatures as temperatures above room temperature. Research continues into this. Ferroelectric crystals could store information in the location of domain walls.

The phosphate langbeinites are insoluble, stable against heat, and can accommodate a large number of different ions, and have been considered for immobilizing unwanted radioactive waste. [137]

Zirconium phosphate langbeinites containing rare earth metals have been investigated for use in white LEDs and plasma displays. [105] Langbeinites that contain bismuth are photoluminescent. [105] In case of iron-containing ones complex magnetic behavior may be found. [138]

Related Research Articles

In chemistry, water(s) of crystallization or water(s) of hydration are water molecules that are present inside crystals. Water is often incorporated in the formation of crystals from aqueous solutions. In some contexts, water of crystallization is the total mass of water in a substance at a given temperature and is mostly present in a definite (stoichiometric) ratio. Classically, "water of crystallization" refers to water that is found in the crystalline framework of a metal complex or a salt, which is not directly bonded to the metal cation.

<span class="mw-page-title-main">Ammonium sulfate</span> Chemical compound

Ammonium sulfate (American English and international scientific usage; ammonium sulphate in British English); (NH4)2SO4, is an inorganic salt with a number of commercial uses. The most common use is as a soil fertilizer. It contains 21% nitrogen and 24% sulfur.

<span class="mw-page-title-main">Vanadyl sulfate</span> Chemical compound

Vanadyl(IV) sulfate describes a collection of inorganic compounds of vanadium with the formula, VOSO4(H2O)x where 0 ≤ x ≤ 6. The pentahydrate is common. This hygroscopic blue solid is one of the most common sources of vanadium in the laboratory, reflecting its high stability. It features the vanadyl ion, VO2+, which has been called the "most stable diatomic ion".

Indium(III) sulfate (In2(SO4)3) is a sulfate salt of the metal indium. It is a sesquisulfate, meaning that the sulfate group occurs 1⁠1/2⁠ times as much as the metal. It may be formed by the reaction of indium, its oxide, or its carbonate with sulfuric acid. An excess of strong acid is required, otherwise insoluble basic salts are formed. As a solid indium sulfate can be anhydrous, or take the form of a pentahydrate with five water molecules or a nonahydrate with nine molecules of water. Indium sulfate is used in the production of indium or indium containing substances. Indium sulfate also can be found in basic salts, acidic salts or double salts including indium alum.

<span class="mw-page-title-main">Tin(II) sulfate</span> Chemical compound

Tin(II) sulfate (SnSO4) is a chemical compound. It is a white solid that can absorb enough moisture from the air to become fully dissolved, forming an aqueous solution; this property is known as deliquescence. It can be prepared by a displacement reaction between metallic tin and copper(II) sulfate:

Tutton's salts are a family of salts with the formula M2M'(SO4)2(H2O)6 (sulfates) or M2M'(SeO4)2(H2O)6 (selenates). These materials are double salts, which means that they contain two different cations, M+ and M'2+ crystallized in the same regular ionic lattice. The univalent cation can be potassium, rubidium, caesium, ammonium (NH4), deuterated ammonium (ND4) or thallium. Sodium or lithium ions are too small. The divalent cation can be magnesium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc or cadmium. In addition to sulfate and selenate, the divalent anion can be chromate (CrO42−), tetrafluoroberyllate (BeF42−), hydrogenphosphate (HPO42−) or monofluorophosphate (PO3F2−). Tutton's salts crystallize in the monoclinic space group P21/a. The robustness is the result of the complementary hydrogen-bonding between the tetrahedral anions and cations as well their interactions with the metal aquo complex [M(H2O)6]2+.

<span class="mw-page-title-main">Tetrafluoroberyllate</span> Anion

Tetrafluoroberyllate or orthofluoroberyllate is an anion with the chemical formula [BeF4]2−. It contains beryllium and fluorine. This fluoroanion has a tetrahedral shape, with the four fluorine atoms surrounding a central beryllium atom. It has the same size, charge, and outer electron structure as sulfate SO2−4. Therefore, many compounds that contain sulfate have equivalents with tetrafluoroberyllate. Examples of these are the langbeinites, and Tutton's salts.

<span class="mw-page-title-main">Monofluorophosphate</span> Chemical compound

Monofluorophosphate is an anion with the formula PO3F2−, which is a phosphate group with one oxygen atom substituted with a fluoride atom. The charge of the ion is −2. The ion resembles sulfate in size, shape and charge, and can thus form compounds with the same structure as sulfates. These include Tutton's salts and langbeinites. The most well-known compound of monofluorophosphate is sodium monofluorophosphate, commonly used in toothpaste.

Tetracalcium phosphate is the compound Ca4(PO4)2O, (4CaO·P2O5). It is the most basic of the calcium phosphates, and has a Ca/P ratio of 2, making it the most phosphorus poor phosphate. It is found as the mineral hilgenstockite, which is formed in industrial phosphate rich slag (called "Thomas slag"). This slag was used as a fertiliser due to the higher solubility of tetracalcium phosphate relative to apatite minerals. Tetracalcium phosphate is a component in some calcium phosphate cements that have medical applications.

Sodium magnesium sulfate is a double sulfate of sodium and magnesium. There are a number of different stoichiometries and degrees of hydration with different crystal structures, and many are minerals. Members include:

<span class="mw-page-title-main">Vanadium(II) sulfate</span> Chemical compound

Vanadium(II) sulfate describes a family of inorganic compounds with the formula VSO4(H2O)x where 0 ≤ x ≤ 7. The hexahydrate is most commonly encountered. It is a violet solid that dissolves in water to give air-sensitive solutions of the aquo complex. The salt is isomorphous with [Mg(H2O)6]SO4. Compared to the V–O bond length of 191 pm in [V(H2O)6]3+, the V–O distance is 212 pm in the [V(H2O)6]SO4. This nearly 10% elongation reflects the effect of the lower charge, hence weakened electrostatic attraction.

Nickel is one of the metals that can form Tutton's salts. The singly charged ion can be any of the full range of potassium, rubidium, cesium, ammonium (), or thallium. As a mineral the ammonium nickel salt, (NH4)2Ni(SO4)2 · 6 H2O, can be called nickelboussingaultite. With sodium, the double sulfate is nickelblödite Na2Ni(SO4)2 · 4 H2O from the blödite family. Nickel can be substituted by other divalent metals of similar sized to make mixtures that crystallise in the same form.

<span class="mw-page-title-main">Nickel oxyacid salts</span>

The Nickel oxyacid salts are a class of chemical compounds of nickel with an oxyacid. The compounds include a number of minerals and industrially important nickel compounds.

<span class="mw-page-title-main">Sulfate carbonate</span> Class of chemical compounds

The sulfate carbonates are a compound carbonates, or mixed anion compounds that contain sulfate and carbonate ions. Sulfate carbonate minerals are in the 7.DG and 5.BF Nickel-Strunz groupings.

Borate phosphates are mixed anion compounds containing separate borate and phosphate anions. They are distinct from the borophosphates where the borate is linked to a phosphate via a common oxygen atom. The borate phosphates have a higher ratio of cations to number of borates and phosphates, as compared to the borophosphates.

A tellurite fluoride is a mixed anion compound containing tellurite and fluoride ions. They have also been called oxyfluorotellurate(IV) where IV is the oxidation state of tellurium in tellurite.

A selenate selenite is a chemical compound or salt that contains selenite and selenate anions (SeO32- and SeO42-). These are mixed anion compounds. Some have third anions.

The phosphate sulfates are mixed anion compounds containing both phosphate and sulfate ions. Related compounds include the arsenate sulfates, phosphate selenates, and arsenate selenates.

Oxalate sulfates are mixed anion compounds containing oxalate and sulfate. They are mostly transparent, and any colour comes from the cations.

Protactinium compounds are compounds containing the element protactinium. These compounds usually have protactinium in the +5 oxidation state, although these compounds can also exist in the +2, +3 and +4 oxidation states.

References

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