Cerium nitrates#Cerium(IV) nitrates

File:Cerous nitrate 6 water.png

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.{{cite journal|last=Garner|first=J.P.|author2=P.S.J. Heppell|year=2005|title=Cerium nitrate in the management of burns|journal=Burns|volume=31|issue=5|pages=539–547|issn=0305-4179|doi=10.1016/j.burns.2005.01.014|pmid=15955636}}{{cite journal|last=Wassermann|first=D.|author2=M. Schlotterer, F. Lebreton, J. Levy, M.C. Guelfi|year=1989|title=Use of topically applied silver sulphadiazine plus cerium nitrate in major burns|journal=Burns|volume=15|issue=4|pages=257–260|issn=0305-4179|doi=10.1016/0305-4179(89)90045-4|pmid=2765148}} At 150 °C the hexahydrate loses water of crystallization to make a trihydrate, which itself decomposes above 200 °C.{{cite book|last1=Latimer|first1=Wendell M.|last2=Hildebrand|first2=Joel H.|title=Reference Book of Inorganic Chemistry|edition=3|year=1951|publisher=Macmillan|location=New York|page=581}} Cerous nitrate hexahydrate has pinacoidal triclinic crystals.{{cite book|last=Groth|first=Paul|title=Chemische Krystallographie|author-link=Paul Heinrich von Groth|url=https://archive.org/details/chemischekrystal02grotuoft|volume=2|year=1908|page=[https://archive.org/details/chemischekrystal02grotuoft/page/131 131]|publisher=Leipzig W. Engelmann}}

Hydronium cerium(III) nitrate hydrate, Ce(NO₃)₅(H₃O)₂.H₂O{{cite journal|last1=Guillou|first1=N.|last2=Auffredic|first2=J.P.|last3=Louër|first3=M.|last4=Louër|first4=D.|year=1993|title=The Crystal Structure of Hydronium Cerium (III) Nitrate Hydrate, Ce(NO₃)5(H₃O)₂ · H₂O|journal=Journal of Solid State Chemistry|volume=106|issue=2|pages=295–300|issn=0022-4596|doi=10.1006/jssc.1993.1289|bibcode=1993JSSCh.106..295G}} is monoclinic with space group P2/c. The diaquapentanitratocerate(III) anion (Ce(NO₃)₅(H₂O)₂)²⁻ occurs in several salts. The salts have extreme non-linear optical properties.

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.{{cite web|url=https://www.fas.org/sgp/othergov/doe/lanl/lib-www/la-pubs/00356861.pdf|title=Optical Properties of some Compounds of Uranium, Plutonium and Related Elements|last=Staritscky|first=Eugene|author2=Donald I Walker|date=29 August 1952|pages=20–21|access-date=9 February 2014}}

Ceric nitrate is quite soluble in non polar solvents such as ethyl ether. Ether will extract the cerium nitrate from 5N nitric acid. In nitric acid, nitrato ceric acid{{cite journal|last=Smith|first=G. Frederick|author2=C. A. Getz|year=1940|title=Cerate Oxidimetry|journal=Industrial & Engineering Chemistry Analytical Edition|volume=12|issue=6|pages=339–340|issn=0096-4484|doi=10.1021/ac50146a012}} (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.{{cite journal|last=Wylie|first=A. W.|year=1951|title=338. Extraction of ceric nitrate by solvents|journal=Journal of the Chemical Society (Resumed)|pages=1474–1480|issn=0368-1769|doi=10.1039/JR9510001474}}

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.{{cite journal|last=Meyer|first=Richard Jos.|author2=Richard Jacoby|year=1901|title=Die Doppelnitrate des vierwertigen Ceriums und des Thoriums|journal=Zeitschrift für Anorganische Chemie|volume=27|issue=1|pages=359–389|issn=0863-1778|doi=10.1002/zaac.19010270131|hdl=2027/uc1.b2651462|url=https://zenodo.org/record/1428092}} When this meets ammonia in water solution it reacts to form ceric ammonium nitrate and ceric hydroxide.

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.{{cite journal|last1=Guillou|first1=N.|last2=Auffrédic|first2=J.P.|last3=Louër|first3=D.|year=1994|title=Synthesis, Crystal Structure, and Thermal Behavior of Cerium(IV) Oxide Nitrate Ce₂O(NO₃)₆(H₂O)6 · 2H₂O|journal=Journal of Solid State Chemistry|volume=112|issue=1|pages=45–52|issn=0022-4596|doi=10.1006/jssc.1994.1262|bibcode=1994JSSCh.112...45G}}

The diaquapentanitratocerate(III) anion (Ce(NO₃)₅(H₂O)₂)²⁻ occurs in several salts. The salts have extreme non-linear optical properties.

K₂Ce(NO₃)₅{{cite journal|last=Xue|first=Dongfeng|author2=Siyuan Zhang|year=1998|title=Calculation of nonlinearities of K₂Ce(NO₃)₅• 2H₂O and K₂La(NO₃)₅• 2H₂O|journal=Molecular Physics|volume=93|issue=3|pages=411–415|issn=0026-8976|doi=10.1080/002689798169096|bibcode=1998MolPh..93..411X}} 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.{{cite journal|last=Held|first=P.|author2=H. Hellwig, S. RuÈhle and L. Bohaty|date=24 Jan 2000|title=Polar potassium rare earth nitrates K₂[RE(NO₃)₅(H₂O)₂] (RE = La, Ce, Pr and Nd). I. Crystal growth and crystal structures|journal=Journal of Applied Crystallography|volume=33|issue=2|pages=372–379|issn=0021-8898|doi=10.1107/s0021889800000868|last3=Rühle|first3=S.|last4=Bohatý|first4=L.|bibcode=2000JApCr..33..372H }} It can be grown into optical quality crystals of around 100 cm³ in 12 weeks. Crystals are colourless. The space group of the crystal is Fdd2 and their form is orthorhombic. Potassium cerium nitrate was probably discovered by L. Th. Lange in 1861.{{cite journal|last=Th. Lange|first=L.|year=1861|title=Ueber einige neue Cerverbindungen|journal=Journal für Praktische Chemie|volume=82|issue=1|pages=129–147|issn=0021-8383|doi=10.1002/prac.18610820119|url=https://zenodo.org/record/1427824}} However it was only properly described in 1894 by Fock.{{cite journal|last=Fock|first=A.|title=Krystallographisch - chemische Untersuchungen|year=1894|journal=Zeitschrift für Kristallographie|volume=22|issue=1–6|pages=29–42|doi=10.1524/zkri.1894.22.1.29|s2cid=101725643|url=https://zenodo.org/record/1448948}}{{cite book|last=Groth|first=Paul|title=Chemische Krystallographie|url=https://archive.org/details/chemischekrystal02grotuoft/page/n3|volume=2|year=1908|publisher=Leipzig W. Engelmann}} 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.{{cite journal|last=Jantsch|first=G.|author2=S. Wigdorow|year=1910|title=Zur Kenntnis der Doppelnitrate der seltenen Erden. 1. Mitteilung. Über die Doppelnitrate der seltenen Erden mit den Alkalielementen|journal=Zeitschrift für Anorganische Chemie|volume=69|issue=1|pages=221–231|issn=0863-1778|doi=10.1002/zaac.19110690117|url=https://zenodo.org/record/1428120}} The non-linear optical effects were found in 1993. For optical applications it is known as KCN.{{cite journal|last=Ebbers|first=C.A.|author2=L.D. DeLoach, M. Webb, D. Eimerl, S.P. Velsko, D.A. Keszler|year=1993|title=Nonlinear optical properties of K ₂La(NO ₃)₅.2H₂O and K₂Ce(NO₃) ₅.2H₂O|journal=IEEE Journal of Quantum Electronics|volume=29|issue=2|pages=497–507|issn=0018-9197|doi=10.1109/3.199304|bibcode=1993IJQE...29..497E|last3=Webb|first3=Mark|last4=Eimerl|first4=David|last5=Velsko|first5=Stephan P.|last6=Keszler|first6=Douglas A.}}

Diammonium diaquapentanitratocerate dihydrate.{{cite journal|last=Najafpour|first=Mahdi|author2=Przemysław Starynowicz|year=2006|title=Diammonium diaquapentanitratocerate(III) dihydrate|journal=Acta Crystallographica Section E|volume=62|issue=7|pages=i145–i146|issn=1600-5368|doi=10.1107/S1600536806006593|bibcode=2006AcCrE..62I.145N }} Its Raman spectrum has been published.{{cite book|last1=Nyquist|first1=Richard A.|last2=Kagel|first2=Ronald O.|title=Handbook of Infrared and Raman Spectra of Inorganic Compounds and Organic Salts: Infrared Spectra of Inorganic Compounds|url=https://books.google.com/books?id=RhJg4WCbm0gC&pg=PA146|access-date=8 February 2014|date=1972-03-30|publisher=Academic Press|isbn=9780080878522|pages=146–147}} It is quite soluble in water with 100 ml dissolving 235 grams at 9 °C and 817 grams at 65°.

• dirubidium diaquapentanitratocerate dihydrate.
• 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'.{{cite web|url=http://cerium.atomistry.com/cerous_nitrate.html|title=Cerous nitrate, Ce(NO₃)₃|year=2012|access-date=8 February 2014}}
• dithallium diaquapentanitratocerate dihydrate.
• 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.{{cite journal|last=Sun|first=Qiaozhen|author2=Feng Zheng|author3=Xiaodan Sun|author4=Wei Wang|year=2008|title=Bis{4-[(4H-1,2,4-triazol-4-yl)iminomethyl]pyridinium} diaquapentanitratocerate(III)|journal=Acta Crystallographica Section E|volume=65|issue=1|pages=m124|issn=1600-5368|doi=10.1107/S1600536808043109|pmid=21581488|pmc=2968024}}

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.{{cite journal|last=Bertinat|first=M. P.|author2=D. F. Brewer|author3=J. P. Harrison|year=1970|title=Surface area of powdered cerous magnesium nitrate|journal=Journal of Low Temperature Physics|volume=2|issue=1|pages=157–160|issn=0022-2291|doi=10.1007/BF00628109|bibcode=1970JLTP....2..157B|s2cid=98479942}}

{{cite journal|last=Abel|first=W.|author2=A. Anderson|author3=W. Black|author4=J. Wheatley|year=1966|title=Thermal Equilibrium Between Liquid He^{3} and Powdered Cerium Magnesium Nitrate at Very Low Temperatures|journal=Physical Review Letters|volume=16|issue=7|pages=273–275|issn=0031-9007|doi=10.1103/PhysRevLett.16.273|bibcode=1966PhRvL..16..273A}}

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.{{cite journal|last1=Audebrand|first1=Nathalie|last2=Louër|first2=Daniel|year=2000|title=Cerous sodium nitrate monohydrate, Na₂Ce(NO₃)₅·H₂O|journal=Acta Crystallographica Section C|volume=56|issue=8|pages=913–915|issn=0108-2701|doi=10.1107/S0108270100006211|pmid=10944270}}

There are anhydrous double nitrates such as Ce₂Rb₃(NO₃)₉ and Ce₂K₃(NO₃)₉.{{cite journal|last1=Guillou|first1=N.|last2=Auffrédic|first2=J.P.|last3=Louër|first3=D.|year=1996|title=Thermal Behavior and Crystal Structure of Ceric and Cerous Rubidium Nitrates|journal=Journal of Solid State Chemistry|volume=122|issue=1|pages=59–67|issn=0022-4596|doi=10.1006/jssc.1996.0082|bibcode=1996JSSCh.122...59G}} 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 ų 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.

A related series with ratio 1.5 of the monovalent ion to cerium includes 2Ce(NO₃)₃.3(NH₄)NO₃.12H₂O

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.{{cite journal|last=Roser|first=M.|author2=L. Corruccini|year=1990|title=Magnetic susceptibilities of rare-earth ions in an unusual tetrahedral site|journal=Physical Review B|volume=41|issue=4|pages=2359–2368|issn=0163-1829|doi=10.1103/PhysRevB.41.2359|pmid=9993972|bibcode=1990PhRvB..41.2359R}}

File:Ceric ammonium nitrate.jpg

The alkali metals form orange-red monoclinic crystals as a double salt with ceric nitrate: {{chem|M|2|[Ce(NO|3|)|6|]}} with M=K, Rb, Cs, or [NH₄].

• Ceric ammonium nitrate contains the icosahedral shaped ion {{chem|[Ce(NO|3|)|6|]|2-}} which has cerium in the +4 oxidation state.{{cite journal |author=Thomas A. Beineke |author2=J. Delgaudio |year=1968 |title=Crystal structure of ceric ammonium nitrate |journal=Inorg. Chem. |volume=7 |issue=4 |pages=715–721 |doi=10.1021/ic50062a020 |osti=4799348 }} It is used as a reagent in oxidimetry.
• Ceric potassium nitrate {{chem|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 {{chem|[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 1063.1ų and dimensions of a=13.5737Å c=6.6624Å with a density of 2.767 g/cm³.{{cite journal|last1=Guillou|first1=N.|last2=Louër|first2=M.|last3=Auffrédic|first3=J.P.|last4=Louër|first4=D.|year=1995|title=Two Polymorphic Forms of Ceric Potassium Nitrate, K₂Ce(NO₃)₆|journal=Acta Crystallographica Section C|volume=51|issue=6|pages=1029–1032|issn=0108-2701|doi=10.1107/S0108270194014927|bibcode=1995AcCrC..51.1029G }}

In the monoclinic form of {{chem|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 700.9ų and dimensions a = 12.707Å b = 6.6858Å c = 8.253Å and β = 91.55°.

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

• Ceric rubidium nitrate {{chem|Rb|2|[Ce(NO|3|)|6|]}} is reddish yellow.
• Ceric caesium nitrate {{chem|Cs|2|[Ce(NO|3|)|6|]}} is very insoluble in nitric acid and is bright yellow.
• The thallium double salt cannot be produced because the ceric ion oxidizes thallium(I) to thallium(III).

• Ceric magnesium nitrate {{chem|Mg|[Ce(NO|3|)|6|.8H|2|O]}}
• Ceric zinc nitrate {{chem|Zn|[Ce(NO|3|)|6|.8H|2|O]}}
• Ceric nickel nitrate {{chem|Ni|[Ce(NO|3|)|6|.8H|2|O]}}
• Ceric cobalt nitrate {{chem|Co|[Ce(NO|3|)|6|.8H|2|O]}}
• Ceric manganese nitrate {{chem|Mn|[Ce(NO|3|)|6|.8H|2|O]}}

• [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].{{cite journal|last=Calvez|first=Guillaume|author2=Carole Daiguebonne|author3=Olivier Guillou|author4=Florence Le Dret|year=2009|title=A New Series of Anhydrous Lanthanide-Based Octahedral Hexanuclear Complexes|journal=European Journal of Inorganic Chemistry|volume=2009|issue=21|pages=3172–3178|issn=1434-1948|doi=10.1002/ejic.200900283}}

Cerium magnesium nitrate (also known as cerous magnesium nitrate), is a highly paramagnetic salt, and is a possible refrigerant for use in magnetic refrigeration.{{cite arXiv|title=Magnetic refrigeration with paramagnetic semiconductors at cryogenic temperatures|quote=For comparison, a commonly used paramagnetic salt for magnetic cryo-refrigeration is cerous magnesium nitrate hydrate ...|eprint=1706.00458|last1=Vlasov|first1=A|last2=Guillemette|first2=J|last3=Gervais|first3=G|last4=Szkopek|first4=T|class=cond-mat.mes-hall|year=2017}}

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{{Cerium compounds}}

{{Nitrates}}

Category:Nitrates

Category:Cerium(III) compounds

Category:Cerium(IV) compounds