Cerium nitrates
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ECHA InfoCard | 100.030.257 |
PubChem CID
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UNII |
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CompTox Dashboard (EPA)
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Properties | |
Ce(NO3)3 | |
Molar mass | 326.12 g/mol |
Appearance | Colorless crystals (hexahydrate) |
Density | 2.38 g cm−3 |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Cerium nitrate refers to a family of nitrates of cerium in the +3 or +4 oxidation state. Often these compounds contain water, hydroxide, or hydronium ions in addition to cerium and nitrate. Double nitrates of cerium also exist.
Cerium(III) nitrates
[edit]Anhydrous cerous nitrate, also called cerium(III) nitrate, is the anhydrous salt with the formula Ce(NO3)3.(CAS number 10108-73-3).
Cerium nitrate hexahydrate, with the formula Ce(NO3)3.6H2O (CAS number 10294-41-4) is the most common nitrate of cerium(III). It is a component in a burn treatment cream that also includes silver sulphadiazine. Concentrations used are 0.5 M for the cerium nitrate. For very serious burns it reduces the death rate.[1][2] At 150 °C the hexahydrate loses water of crystallization to make a trihydrate, which itself decomposes above 200 °C.[3] Cerous nitrate hexahydrate has pinacoidal triclinic crystals.[4]
Hydronium cerium(III) nitrate hydrate, Ce(NO3)5(H3O)2.H2O[5] It is monoclinic with space group P2/c.[5] The diaquapentanitratocerate(III) anion (Ce(NO3)5(H2O)2)2− occurs in several salts. The salts have extreme non-linear optical properties.[6]
Cerium(IV) nitrates
[edit]Cerium tetranitrate pentahydrate is prepared by evaporating a solution of ceric nitrate in concentrated nitric acid. It forms orthorhombic crystals with bipyramidal shape. The common crystal face Miller index is {111}, But it can have smaller faces with Miller index {010} and {110}. The density is 2.403 g/cm3. Its optical properties are that it is biaxial with 2V of 34°, and strongly dispersive. On its B and C axes it appears yellow, but orange red on the A axis.[7]
Ceric nitrate is quite soluble in non polar solvents such as ethyl ether. Ether will extract the cerium nitrate from 5N nitric acid.[8] In nitric acid, nitrato ceric acid[9] (H2[Ce(NO3)6] and H[Ce(NO3)5.H2O]) are present. The solubility of this nitrate in non-polar solvents allows the separation of cerium from other rare earths.[8]
Basic cerium(IV) nitrate has the formula Ce(NO3)3.OH.3H2O. It also forms upon evaporation of solutions of cerium(IV) in nitric acid.[10] When this meets ammonia in water solution it reacts to form ceric ammonium nitrate and ceric hydroxide.[10]
Basic dicerium nitrate has the formula Ce2O(NO3)6(H2O)6·2H2O. Again it crystallizes from solutions of cerium(IV) in nitric acid. It crystallises as monoclinic crystals with space group P21lc with unit cell dimensions a=8.723 Å b=8.940 Å c=13.981 Å,
Ammonium and alkali metal cerium nitrates
[edit]The diaquapentanitratocerate(III) anion (Ce(NO3)5(H2O)2)2− occurs in several salts. The salts have extreme non-linear optical properties.[6]
K2Ce(NO3)5[12] crystals can be grown by evaporating a solution of potassium nitrate, cerous nitrate, and nitric acid. Each cerium atom is surrounded by the oxygen atoms of five bidentate nitrate groups and two water oxygen atoms.[6] It can be grown into optical quality crystals of around 100 cm3 in 12 weeks.[6] Crystals are colourless.[6] The space group of the crystal is Fdd2 and their form is orthorhombic.[6] Potassium cerium nitrate was probably discovered by L. Th. Lange in 1861.[13] However it was only properly described in 1894 by Fock.[14][15] Even then the amount of water in the substance was wrong and it took till 1911 when Jantsch & Wigdorow correctly stated that there were two water molecules.[16] The non-linear optical effects were found in 1993. For optical applications it is known as KCN.[17]
Diammonium diaquapentanitratocerate dihydrate.[16][18] Its Raman spectrum has been published.[19] It is quite soluble in water with 100 ml dissolving 235 grams at 9 °C and 817 grams at 65°.[20]
- dirubidium diaquapentanitratocerate dihydrate.[16]
- dicaesium diaquapentanitratocerate dihydrate, or caesium cerous nitrate Cs2Ce(NO3)5.2H2O forms monoclinic crystals with crystal parameters a/b=1.2052, c/b=0.9816 and
β = 103°41'.[20] - dithallium diaquapentanitratocerate dihydrate.[16]
- Bis{4-[(4H-1,2,4-triazol-4-yl)iminomethyl]pyridinium} diaquapentanitratocerate. (C8H8N5)2[Ce(NO3)5(H2O)2] is monoclinic with space group C2/c.[21]
name | formula | melt | density | a | b | c | Vol | Z | |
---|---|---|---|---|---|---|---|---|---|
dipotassium diaquapentanitratocerate | K2Ce(NO3)5·2 H2O | 2.543 | 11.263 | 21.404 | 12.230 | 90 | 2948 | 8[6] | |
dipotassium hexanitratocerate[22] | K2Ce(NO3)6 | ||||||||
tripotassium dicerium(III) nitrate[22] | K3Ce2(NO3)9 | 2.525 | 13.597 | 13.597 | 13.597 | 90 | 2514 | 4 | |
diammonium diaquapentanitratocerate dihydrate | (NH4)2Ce(NO3)5·4 H2O | 2.128 | 11.09 | 8.936 | 17.96 | 101.77 | 1743[23][18] | 4 | |
dirubidium diaquapentanitratocerate dihydrate | Rb2Ce(NO3)5·4 H2O | 70° | 2.497 | 11.050 | 8.977 | 17.859 | 100.88[24] | ||
dicaesium diaquapentanitratocerate dihydrate ? | Cs2Ce(NO3)5·4 H2O | ||||||||
dithallium diaquapentanitratocerate dihydrate ? | Tl2Ce(NO3)5·4 H2O | 64.5° | 3.326 | ||||||
Bis{4-[(4H-1,2,4-triazol-4-yl)iminomethyl]pyridinium} diaquapentanitratocerate | (C8H8N5)2[Ce(NO3)5(H2O)2] | 10.322 | 16.126 | 17.575 | 100.107 | 2883.2 | 4 | ||
1,10-Phenanthroline-H diaquapentanitratocerate | HPhen2[Ce(NO3)5(H2O)2] | 1.83 | 7.5534 | 8.083 | 25.8377 | 89.947 |
1572.94 | 2[25] | |
Hydronium Cerium (III) Nitrate Hydrate | Ce(NO3)5(H3O)2·H2O | 21.36 | 7.899 | 15.133 | 91.02 | 8 |
Divalent double nitrates
[edit]Cerous magnesium nitrate is the first discovered member of a divalent series CeM(II)(NO3)5. This has an extremely low Kapitza resistance to liquid 3He. At the time of discovery it value was only 1% of the previous record holder. Low thermal resistance is important at temperatures below 1K, because there is not much temperature difference to cause a large heat flow rate, and cooling can take an excessive time if there are barriers to heat transfer.[26] [27]
Other cerous double nitrates
[edit]Cerous sodium nitrate monohydrate, Na2Ce(NO3)5.H2O has density 2.641 g/cm3. It can be made by boiling the stoichiometric mixture of cerous nitrate, and sodium nitrate in nitric acid, and then evaporating at 40 °C. The crystals are clear rod shaped monoclinic with space group P2/c. Crystal cell sizes are a=21.387 b=7.9328 c=15.184
There are anhydrous double nitrates such as Ce2Rb3(NO3)9 and Ce2K3(NO3)9.[29] The potassium salt, Ce2K3(NO3)9 can be made by using the water solution of potassium nitrate and cerous nitrate in 3:2 molar ratio, evaporated at 40 °C. The crystals are colourless cubic from space group P4132. Its formula weight is 955.6. Three formulas exist in each unit cell which at 20 °C, has a volume of 2514.1 Å3 and cell side of a=13.597 Å. The density is 2.525 g/cm3. In this compound each cerium atoms is surrounded by twelve oxygen atoms from six nitrate groups. Three of the nitrates form a bridge in each of three dimensions. These bridges form three spirals each at 90° to each other along the crystal axes.[22]
A related series with ratio 1.5 of the monovalent ion to cerium includes 2Ce(NO3)3.3(NH4)NO3.12H2O[20]
A mixed caesium, sodium cerium triple nitrate Cs2NaCe(NO3)6 crystallizes in the cubic system. The unit cell size is 1.1196 nm with volume of 1.4034 nm3 and four molecules per cell.[30]
Ceric double nitrates
[edit]The alkali metals form orange-red monoclinic crystals as a double salt with ceric nitrate: M
2[Ce(NO
3)
6] with M=K, Rb, Cs, or [NH4].[10]
- Ceric ammonium nitrate contains the icosahedral shaped ion [Ce(NO
3)
6]2−
which has cerium in the +4 oxidation state.[31] It is used as a reagent in oxidimetry.[9] - Ceric potassium nitrate K
2[Ce(NO
3)
6] has two different crystal forms, hexagonal and monoclinic. Slow evaporation and crystallization results in the monoclinic form. But fast crystallization results in a mixture of the two shapes. Both of these forms have six nitrate groups connected via two oxygens each to the cerium [Ce(NO
3)
6]2−
. The substance is made by dissolving ceric hydroxide in nitric acid with the appropriate stoichiometric amount of potassium nitrate. In the hexagonal form the cerium atoms are arranged along a threefold axis. In hexagonal form the potassium ions are surrounded by nine oxygen atoms. These crystals are orange hexagonal shaped plates. Crystal cells contain three molecules, with a volume of 1063.1Å3 and dimensions of a=13.5737Å c=6.6624Å with a density of 2.767 g/cm3.[32]
In the monoclinic form of K
2[Ce(NO
3)
6], the cerium atoms are in a body centred arrangement, with potassium surrounded by ten oxygen atoms. The density is 2.798 g/cm3 with a cell that contains two molecules with volume 700.9Å3 and dimensions a = 12.707Å b = 6.6858Å c = 8.253Å and
Ceric potassium nitrate also has a hydrate with 1.5 mols of water.[10]
- Ceric rubidium nitrate Rb
2[Ce(NO
3)
6] is reddish yellow.[10] - Ceric caesium nitrate Cs
2[Ce(NO
3)
6] is very insoluble in nitric acid and is bright yellow.[10] - The thallium double salt cannot be produced because the ceric ion oxidizes thallium(I) to thallium(III).[10]
Divalent metals
[edit]- Ceric magnesium nitrate Mg[Ce(NO
3)
6.8H
2O][10] - Ceric zinc nitrate Zn[Ce(NO
3)
6.8H
2O][10] - Ceric nickel nitrate Ni[Ce(NO
3)
6.8H
2O][10] - Ceric cobalt nitrate Co[Ce(NO
3)
6.8H
2O][10] - Ceric manganese nitrate Mn[Ce(NO
3)
6.8H
2O][10]
Other compounds
[edit]- [Ce6O(OH)8(NO3)6(H2O)16]·(NO3)2·2H2O is a hexanuclear cerium oxido and hydroxido complex. It can be dehydrated to form [Ce6O(OH)8(NO3)8].[33]
Proposed application
[edit]Cerium magnesium nitrate (also known as cerous magnesium nitrate), is a highly paramagnetic salt, and is a possible refrigerant for use in magnetic refrigeration.[34]
References
[edit]- ^ Garner, J.P.; P.S.J. Heppell (2005). "Cerium nitrate in the management of burns". Burns. 31 (5): 539–547. doi:10.1016/j.burns.2005.01.014. ISSN 0305-4179. PMID 15955636.
- ^ Wassermann, D.; M. Schlotterer, F. Lebreton, J. Levy, M.C. Guelfi (1989). "Use of topically applied silver sulphadiazine plus cerium nitrate in major burns". Burns. 15 (4): 257–260. doi:10.1016/0305-4179(89)90045-4. ISSN 0305-4179. PMID 2765148.
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For comparison, a commonly used paramagnetic salt for magnetic cryo-refrigeration is cerous magnesium nitrate hydrate ...