Cerium nitrates

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Cerium(III) nitrate
Cerium nitrate.jpg
Identifiers
ECHA InfoCard 100.030.257 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
Properties
Ce(NO3)3
Molar mass 326.12 g/mol
AppearanceColorless 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).

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.

Contents

Cerium(III) nitrates

Cerium(III) nitrate crystal with Miller index notation Cerous nitrate 6 water.png
Cerium(III) nitrate crystal with Miller index notation

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

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, β = 94.91°. Each unit cell contains two formula units Ce2O(NO3)6(H2O)3 and Ce2O(NO3)6 form when this basic nitrate is heated slowly to 180 °C in a vacuum. [11]

Ammonium and alkali metal cerium nitrates

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]

nameformulameltdensityabcβ°VolZ
dipotassium diaquapentanitratocerateK2Ce(NO3)5·2 H2O2.54311.26321.40412.2309029488 [6]
dipotassium hexanitratocerate [22] K2Ce(NO3)6
tripotassium dicerium(III) nitrate [22] K3Ce2(NO3)92.52513.59713.59713.5979025144
diammonium diaquapentanitratocerate dihydrate(NH4)2Ce(NO3)5·4 H2O2.12811.098.93617.96101.771743 [23] [18] 4
dirubidium diaquapentanitratocerate dihydrateRb2Ce(NO3)5·4 H2O70°2.49711.0508.97717.859100.88 [24]
dicaesium diaquapentanitratocerate dihydrate ?Cs2Ce(NO3)5·4 H2O
dithallium diaquapentanitratocerate dihydrate ?Tl2Ce(NO3)5·4 H2O64.5°3.326
Bis{4-[(4H-1,2,4-triazol-4-yl)iminomethyl]pyridinium} diaquapentanitratocerate(C8H8N5)2[Ce(NO3)5(H2O)2]10.32216.12617.575100.1072883.24
1,10-Phenanthroline-H diaquapentanitratocerateHPhen2[Ce(NO3)5(H2O)2]1.837.55348.08325.837789.947 β=89.937 γ=86.9811572.942 [25]
Hydronium Cerium (III) Nitrate HydrateCe(NO3)5(H3O)2·H2O21.367.89915.13391.028

Divalent double nitrates

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

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 β=90.657 V=2576 formulas per cell Z=8. The way the components are arranged in the crystal is that there are six nitrates around each cerium atom, however to get to the average of five per cerium, two nitrate groups on each, link the atoms into a chain along the a axis. [28]

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

Diammonium cerium(IV) nitrate Ceric ammonium nitrate.jpg
Diammonium cerium(IV) nitrate

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]

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 β = 91.55°. [22]

Ceric potassium nitrate also has a hydrate with 1.5 mols of water. [10]

Divalent metals

Other compounds

Proposed application

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]

Related Research Articles

<span class="mw-page-title-main">Ceric ammonium nitrate</span> Chemical compound

Ceric ammonium nitrate (CAN) is the inorganic compound with the formula (NH4)2[Ce(NO3)6]. This orange-red, water-soluble cerium salt is a specialised oxidizing agent in organic synthesis and a standard oxidant in quantitative analysis.

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

Cerium(IV) sulfate, also called ceric sulfate, is an inorganic compound. It exists as the anhydrous salt Ce(SO4)2 as well as a few hydrated forms: Ce(SO4)2(H2O)x, with x equal to 4, 8, or 12. These salts are yellow to yellow/orange solids that are moderately soluble in water and dilute acids. Its neutral solutions slowly decompose, depositing the light yellow oxide CeO2. Solutions of ceric sulfate have a strong yellow color. The tetrahydrate loses water when heated to 180-200 °C.

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">Magnesium nitrate</span> Chemical compound

Magnesium nitrate refers to inorganic compounds with the formula Mg(NO3)2(H2O)x, where x = 6, 2, and 0. All are white solids. The anhydrous material is hygroscopic, quickly forming the hexahydrate upon standing in air. All of the salts are very soluble in both water and ethanol.

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

Calcium pyrophosphate (Ca2P2O7) is a chemical compound, an insoluble calcium salt containing the pyrophosphate anion. There are a number of forms reported: an anhydrous form, a dihydrate, Ca2P2O7·2H2O and a tetrahydrate, Ca2P2O7·4H2O. Deposition of dihydrate crystals in cartilage are responsible for the severe joint pain in cases of calcium pyrophosphate deposition disease (pseudo gout) whose symptoms are similar to those of gout. Ca2P2O7 is commonly used as a mild abrasive agent in toothpastes, because of its insolubility and nonreactivity toward fluoride.

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">Cobalt(II) nitrate</span> Chemical compound

Cobalt nitrate is the inorganic compound with the formula Co(NO3)2.xH2O. It is cobalt(II)'s salt. The most common form is the hexahydrate Co(NO3)2·6H2O, which is a red-brown deliquescent salt that is soluble in water and other polar solvents.

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

Bromous acid is the inorganic compound with the formula of HBrO2. It is an unstable compound, although salts of its conjugate base – bromites – have been isolated. In acidic solution, bromites decompose to bromine.

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

Sodium metaborate is a chemical compound of sodium, boron, and oxygen with formula NaBO2. However, the metaborate ion is trimeric in the anhydrous solid, therefore a more correct formula is Na3B3O6 or (Na+)3[B3O6]3−. The formula can be written also as Na2O·B2O3 to highlight the relation to the main oxides of sodium and boron. The name is also applied to several hydrates whose formulas can be written NaBO2·nH2O for various values of n.

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

Silver cyanate is the cyanate salt of silver. It can be made by the reaction of potassium cyanate with silver nitrate in aqueous solution, from which it precipitates as a solid.

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

Bismuth oxynitrate is the name applied to a number of compounds that contain Bi3+, nitrate ions and oxide ions and which can be considered as compounds formed from Bi2O3, N2O5 and H2O. Other names for bismuth oxynitrate include bismuth subnitrate and bismuthyl nitrate. In older texts bismuth oxynitrate is often simply described as BiONO3 or basic bismuth nitrate. Bismuth oxynitrate was once called magisterium bismuti or bismutum subnitricum, and was used as a white pigment, in beauty care, and as a gentle disinfectant for internal and external use. It is also used to form Dragendorff's reagent, which is used as a TLC stain.

<span class="mw-page-title-main">Cerium(III) methanesulfonate</span> Chemical compound

Cerium(III) methanesulfonate is a white salt, usually found as the dihydrate with the formula Ce(CH3SO3)3·2H2O that precipitates from the neutralisation of cerium(III) carbonate with methanesulfonic acid, as first reported by L.B. Zinner in 1979. The crystals have a monoclinic polymeric structure were each methanesulfonate ion forms bonds with two cerium atoms, which present a coordination number of 8. The anhydrous salt is formed by water loss at 120 °C. Similar methanesulfonates can be prepared with other lanthanides. Cerium(III) methanesulfonate in solution is used as a precursor of electrogenerated cerium(IV), which is a strong oxidant and whose salts can be used in organic synthesis. The same principle of Ce(IV) electrogeneration is the fundamental reaction in the positive half-cell of the zinc–cerium battery.

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

Zirconium nitrate is a volatile anhydrous transition metal nitrate salt of zirconium with formula Zr(NO3)4. It has alternate names of zirconium tetranitrate, or zirconium(IV) nitrate.

<span class="mw-page-title-main">Thorium(IV) nitrate</span> Chemical compound

Thorium(IV) nitrate is a chemical compound, a salt of thorium and nitric acid with the formula Th(NO3)4. A white solid in its anhydrous form, it can form tetra- and pentahydrates. As a salt of thorium it is weakly radioactive.

The nickel organic acid salts are organic acid salts of nickel. In many of these the ionised organic acid acts as a ligand.

<span class="mw-page-title-main">Terbium(III) nitrate</span> Chemical compound

Terbium(III) nitrate is an inorganic chemical compound, a salt of terbium and nitric acid, with the formula Tb(NO3)3. The hexahydrate crystallizes as triclinic colorless crystals with the formula [Tb(NO3)3(H2O)4]·2H2O. It can be used to synthesize materials with green emission.

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

Iron(II) nitrate is the nitrate salt of iron(II). It is commonly encountered as the green hexahydrate, Fe(NO3)2·6H2O, which is a metal aquo complex, however it is not commercially available unlike iron(III) nitrate due to its instability to air. The salt is soluble in water serves as a ready source of ferrous ions.

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

Yttrium oxalate is an inorganic compound, a salt of yttrium and oxalic acid with the chemical formula Y2(C2O4)3. The compound does not dissolve in water and forms crystalline hydrates—colorless crystals.

<span class="mw-page-title-main">Transition metal nitrate complex</span> Compound of nitrate ligands

A transition metal nitrate complex is a coordination compound containing one or more nitrate ligands. Such complexes are common starting reagents for the preparation of other compounds.

References

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  29. ↑ Guillou, N.; Auffrédic, J.P.; Louër, D. (1996). "Thermal Behavior and Crystal Structure of Ceric and Cerous Rubidium Nitrates". Journal of Solid State Chemistry. 122 (1): 59–67. Bibcode:1996JSSCh.122...59G. doi:10.1006/jssc.1996.0082. ISSN   0022-4596.
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  33. ↑ Calvez, Guillaume; Carole Daiguebonne; Olivier Guillou; Florence Le Dret (2009). "A New Series of Anhydrous Lanthanide-Based Octahedral Hexanuclear Complexes". European Journal of Inorganic Chemistry. 2009 (21): 3172–3178. doi:10.1002/ejic.200900283. ISSN   1434-1948.
  34. ↑ Vlasov, A; Guillemette, J; Gervais, G; Szkopek, T (2017). "Magnetic refrigeration with paramagnetic semiconductors at cryogenic temperatures". arXiv: 1706.00458 [cond-mat.mes-hall]. For comparison, a commonly used paramagnetic salt for magnetic cryo-refrigeration is cerous magnesium nitrate hydrate ...
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