Post by 1dave on Jul 27, 2023 23:08:43 GMT -5
We don't have a place to talk about this important subject.
forum.rocktumblinghobby.com/post/726888/thread
Bob Rollins, my lapidary teacher used only Cerium oxide, so that is what I used, never thought much about it.
WHAT IS CERIUM OXIDE?
en.wikipedia.org/wiki/Cerium(IV)_oxide
en.wikipedia.org/wiki/Cerium
Bastnäsite and the phosphate mineral monazite are the two largest sources of cerium and other rare-earth elements.
forum.rocktumblinghobby.com/post/726888/thread
Bob Rollins, my lapidary teacher used only Cerium oxide, so that is what I used, never thought much about it.
WHAT IS CERIUM OXIDE?
en.wikipedia.org/wiki/Cerium(IV)_oxide
en.wikipedia.org/wiki/Cerium
Bastnäsite and the phosphate mineral monazite are the two largest sources of cerium and other rare-earth elements.
History
The dwarf planet and asteroid Ceres, after which cerium is named.
Jöns Jakob Berzelius, one of the discoverers of cerium
Cerium was discovered in Bastnäs in Sweden by Jöns Jakob Berzelius and Wilhelm Hisinger, and independently in Germany by Martin Heinrich Klaproth, both in 1803.[33] Cerium was named by Berzelius after the asteroid Ceres, discovered two years earlier.[33][34] The asteroid is itself named after the Roman goddess Ceres, goddess of agriculture, grain crops, fertility and motherly relationships.[33]
Cerium was originally isolated in the form of its oxide, which was named ceria, a term that is still used. The metal itself was too electropositive to be isolated by then-current smelting technology, a characteristic of rare-earth metals in general. After the development of electrochemistry by Humphry Davy five years later, the earths soon yielded the metals they contained. Ceria, as isolated in 1803, contained all of the lanthanides present in the cerite ore from Bastnäs, Sweden, and thus only contained about 45% of what is now known to be pure ceria. It was not until Carl Gustaf Mosander succeeded in removing lanthana and "didymia" in the late 1830s that ceria was obtained pure. Wilhelm Hisinger was a wealthy mine-owner and amateur scientist, and sponsor of Berzelius. He owned and controlled the mine at Bastnäs, and had been trying for years to find out the composition of the abundant heavy gangue rock (the "Tungsten of Bastnäs", which despite its name contained no tungsten), now known as cerite, that he had in his mine.[34] Mosander and his family lived for many years in the same house as Berzelius, and Mosander was undoubtedly persuaded by Berzelius to investigate ceria further.[35][36][37][38]
The element played a role in the Manhattan Project, where cerium compounds were investigated in the Berkeley site as materials for crucibles for uranium and plutonium casting.[39] For this reason, new methods for the preparation and casting of cerium were developed within the scope of the Ames daughter project (now the Ames Laboratory).[40] Production of extremely pure cerium in Ames commenced in mid-1944 and continued until August 1945.[40]
Occurrence and production
Cerium is the most abundant of all the lanthanides, making up 66 ppm of the Earth's crust; this value is just behind that of copper (68 ppm), and cerium is even more abundant than common metals such as lead (13 ppm) and tin (2.1 ppm). Thus, despite its position as one of the so-called rare-earth metals, cerium is actually not rare at all.[41] Cerium content in the soil varies between 2 and 150 ppm, with an average of 50 ppm; seawater contains 1.5 parts per trillion of cerium.[34] Cerium occurs in various minerals, but the most important commercial sources are the minerals of the monazite and bastnäsite groups, where it makes up about half of the lanthanide content. Monazite-(Ce) is the most common representative of the monazites, with "-Ce" being the Levinson suffix informing on the dominance of the particular REE element representative.[42][43][44] Also the cerium-dominant bastnäsite-(Ce) is the most important of the bastnäsites.[45][42] Cerium is the easiest lanthanide to extract from its minerals because it is the only one that can reach a stable +4 oxidation state in aqueous solution.[46] Because of the decreased solubility of cerium in the +4 oxidation state, cerium is sometimes depleted from rocks relative to the other rare-earth elements and is incorporated into zircon, since Ce4+ and Zr4+ have the same charge and similar ionic radii.[47] In extreme cases, cerium(IV) can form its own minerals separated from the other rare-earth elements, such as cerianite (Ce,Th)O
2(correctly named cerianite-(Ce)[48][44][42]).[49][50][51]
Crystal structure of bastnäsite-(Ce). Color code: carbon, C, blue-gray; fluorine, F, green; cerium, Ce, white; oxygen, O, red.
Bastnäsite, LnIIICO3F, is usually lacking in thorium and the heavy lanthanides beyond samarium and europium, and hence the extraction of cerium from it is quite direct. First, the bastnäsite is purified, using dilute hydrochloric acid to remove calcium carbonate impurities. The ore is then roasted in the air to oxidize it to the lanthanide oxides: while most of the lanthanides will be oxidized to the sesquioxides Ln2O3, cerium will be oxidized to the dioxide CeO2. This is insoluble in water and can be leached out with 0.5 M hydrochloric acid, leaving the other lanthanides behind.[46]
The procedure for monazite, (Ln,Th)PO
4, which usually contains all the rare earths, as well as thorium, is more involved. Monazite, because of its magnetic properties, can be separated by repeated electromagnetic separation. After separation, it is treated with hot concentrated sulfuric acid to produce water-soluble sulfates of rare earths. The acidic filtrates are partially neutralized with sodium hydroxide to pH 3–4. Thorium precipitates out of solution as hydroxide and is removed. After that, the solution is treated with ammonium oxalate to convert rare earths to their insoluble oxalates. The oxalates are converted to oxides by annealing. The oxides are dissolved in nitric acid, but cerium oxide is insoluble in HNO3 and hence precipitates out.[16] Care must be taken when handling some of the residues as they contain 228Ra, the daughter of 232Th, which is a strong gamma emitter.[46]
Applications
Carl Auer von Welsbach, who discovered many applications of cerium
Cerium has two main applications, both of which use CeO2. The industrial application of ceria is for polishing, especially chemical-mechanical planarization (CMP). In its other main application, CeO2 is used to decolorize glass. It functions by converting green-tinted ferrous impurities to nearly colorless ferric oxides.[52] Ceria has also been used as a substitute for its radioactive congener thoria, for example in the manufacture of electrodes used in gas tungsten arc welding, where ceria as an alloying element improves arc stability and ease of starting while decreasing burn-off.[53]
Gas mantles and pyrophoric alloys
The first use of cerium was in gas mantles, invented by Austrian chemist Carl Auer von Welsbach. In 1885, he had previously experimented with mixtures of magnesium, lanthanum, and yttrium oxides, but these gave green-tinted light and were unsuccessful.[54] Six years later, he discovered that pure thorium oxide produced a much better, though blue, light, and that mixing it with cerium dioxide resulted in a bright white light.[55] Cerium dioxide also acts as a catalyst for the combustion of thorium oxide.
This resulted in commercial success for von Welsbach and his invention, and created great demand for thorium. Its production resulted in a large amount of lanthanides being simultaneously extracted as by-products.[56] Applications were soon found for them, especially in the pyrophoric alloy known as "mischmetal" composed of 50% cerium, 25% lanthanum, and the remainder being the other lanthanides, that is used widely for lighter flints.[56] Usually iron is added to form the alloy ferrocerium, also invented by von Welsbach.[57] Due to the chemical similarities of the lanthanides, chemical separation is not usually required for their applications, such as the addition of mischmetal to steel as an inclusion modifier to improve mechanical properties, or as catalysts for the cracking of petroleum.[46] This property of cerium saved the life of writer Primo Levi at the Auschwitz concentration camp, when he found a supply of ferrocerium alloy and bartered it for food.[58]
Pigments and phosphors
The photostability of pigments can be enhanced by the addition of cerium, as it provides pigments with lightfastness and prevents clear polymers from darkening in sunlight.[59] An example of a cerium compound used on its own as an inorganic pigment is the vivid red cerium(III) sulfide (cerium sulfide red), which stays chemically inert up to very high temperatures. The pigment is a safer alternative to lightfast but toxic cadmium selenide-based pigments.[34] The addition of cerium oxide to older cathode-ray tube television glass plates was beneficial, as it suppresses the darkening effect from the creation of F-center defects due to the continuous electron bombardment during operation. Cerium is also an essential component as a dopant for phosphors used in CRT TV screens, fluorescent lamps, and later white light-emitting diodes.[60][61] The most commonly used example is cerium(III)-doped yttrium aluminium garnet (Ce:YAG) which emits green to yellow-green light (550–530 nm) and also behaves as a scintillator.
Other uses
Cerium salts, such as the sulfides Ce2S3 and Ce3S4, were considered during the Manhattan Project as advanced refractory materials for the construction of crucibles which could withstand the high temperatures and strongly reducing conditions when casting plutonium metal.[39][40] Despite desirable properties, these sulfides were never widely adopted due to practical issues with their synthesis.[39] Cerium is used as alloying element in aluminium to create castable eutectic aluminium alloys with 6–16 wt.% Ce, to which Mg and/or Si can be further added. These Al-Ce alloys have excellent high temperature strength and are suitable for automotive applications e.g. in cylinder heads.[62] Other alloys of cerium include Pu-Ce and Pu-Ce-Co plutonium alloys, which have been used as nuclear fuel.
Other automotive applications for the lower sesquioxide are as a catalytic converter for the oxidation of CO and NOx emissions in the exhaust gases from motor vehicles.[63][64]
Biological role and precautions
Cerium Hazards
GHS labelling:[65]
Pictograms
GHS02: Flammable
Signal word
Danger
Hazard statements
H228
Precautionary statements
P210
NFPA 704 (fire diamond)
NFPA 704 four-colored diamond
2
0
0
The early lanthanides have been found to be essential to some methanotrophic bacteria living in volcanic mudpots, such as Methylacidiphilum fumariolicum: lanthanum, cerium, praseodymium, and neodymium are about equally effective.[66][67] Cerium is otherwise not known to have biological role in any other organisms, but is not very toxic either; it does not accumulate in the food chain to any appreciable extent. Because it often occurs together with calcium in phosphate minerals, and bones are primarily calcium phosphate, cerium can accumulate in bones in small amounts that are not considered dangerous.
Cerium nitrate is an effective topical antimicrobial treatment for third-degree burns,[34][68] although large doses can lead to cerium poisoning and methemoglobinemia.[69] The early lanthanides act as essential cofactors for the methanol dehydrogenase of the methanotrophic bacterium Methylacidiphilum fumariolicum SolV, for which lanthanum, cerium, praseodymium, and neodymium alone are about equally effective.[70]
Like all rare-earth metals, cerium is of low to moderate toxicity. A strong reducing agent, it ignites spontaneously in air at 65 to 80 °C. Fumes from cerium fires are toxic. Water should not be used to stop cerium fires, as cerium reacts with water to produce hydrogen gas. Workers exposed to cerium have experienced itching, sensitivity to heat, and skin lesions. Cerium is not toxic when eaten, but animals injected with large doses of cerium have died due to cardiovascular collapse.[34] Cerium is more dangerous to aquatic organisms, on account of being damaging to cell membranes; this is an important risk because it is not very soluble in water, thus causing contamination of the environment .[34]
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Bibliography
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vte
Periodic table
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
1 H He
2 Li Be B C N O F Ne
3 Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
7 Fr Ra Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
s-block f-block d-block p-block
vte
Cerium compounds
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The dwarf planet and asteroid Ceres, after which cerium is named.
Jöns Jakob Berzelius, one of the discoverers of cerium
Cerium was discovered in Bastnäs in Sweden by Jöns Jakob Berzelius and Wilhelm Hisinger, and independently in Germany by Martin Heinrich Klaproth, both in 1803.[33] Cerium was named by Berzelius after the asteroid Ceres, discovered two years earlier.[33][34] The asteroid is itself named after the Roman goddess Ceres, goddess of agriculture, grain crops, fertility and motherly relationships.[33]
Cerium was originally isolated in the form of its oxide, which was named ceria, a term that is still used. The metal itself was too electropositive to be isolated by then-current smelting technology, a characteristic of rare-earth metals in general. After the development of electrochemistry by Humphry Davy five years later, the earths soon yielded the metals they contained. Ceria, as isolated in 1803, contained all of the lanthanides present in the cerite ore from Bastnäs, Sweden, and thus only contained about 45% of what is now known to be pure ceria. It was not until Carl Gustaf Mosander succeeded in removing lanthana and "didymia" in the late 1830s that ceria was obtained pure. Wilhelm Hisinger was a wealthy mine-owner and amateur scientist, and sponsor of Berzelius. He owned and controlled the mine at Bastnäs, and had been trying for years to find out the composition of the abundant heavy gangue rock (the "Tungsten of Bastnäs", which despite its name contained no tungsten), now known as cerite, that he had in his mine.[34] Mosander and his family lived for many years in the same house as Berzelius, and Mosander was undoubtedly persuaded by Berzelius to investigate ceria further.[35][36][37][38]
The element played a role in the Manhattan Project, where cerium compounds were investigated in the Berkeley site as materials for crucibles for uranium and plutonium casting.[39] For this reason, new methods for the preparation and casting of cerium were developed within the scope of the Ames daughter project (now the Ames Laboratory).[40] Production of extremely pure cerium in Ames commenced in mid-1944 and continued until August 1945.[40]
Occurrence and production
Cerium is the most abundant of all the lanthanides, making up 66 ppm of the Earth's crust; this value is just behind that of copper (68 ppm), and cerium is even more abundant than common metals such as lead (13 ppm) and tin (2.1 ppm). Thus, despite its position as one of the so-called rare-earth metals, cerium is actually not rare at all.[41] Cerium content in the soil varies between 2 and 150 ppm, with an average of 50 ppm; seawater contains 1.5 parts per trillion of cerium.[34] Cerium occurs in various minerals, but the most important commercial sources are the minerals of the monazite and bastnäsite groups, where it makes up about half of the lanthanide content. Monazite-(Ce) is the most common representative of the monazites, with "-Ce" being the Levinson suffix informing on the dominance of the particular REE element representative.[42][43][44] Also the cerium-dominant bastnäsite-(Ce) is the most important of the bastnäsites.[45][42] Cerium is the easiest lanthanide to extract from its minerals because it is the only one that can reach a stable +4 oxidation state in aqueous solution.[46] Because of the decreased solubility of cerium in the +4 oxidation state, cerium is sometimes depleted from rocks relative to the other rare-earth elements and is incorporated into zircon, since Ce4+ and Zr4+ have the same charge and similar ionic radii.[47] In extreme cases, cerium(IV) can form its own minerals separated from the other rare-earth elements, such as cerianite (Ce,Th)O
2(correctly named cerianite-(Ce)[48][44][42]).[49][50][51]
Crystal structure of bastnäsite-(Ce). Color code: carbon, C, blue-gray; fluorine, F, green; cerium, Ce, white; oxygen, O, red.
Bastnäsite, LnIIICO3F, is usually lacking in thorium and the heavy lanthanides beyond samarium and europium, and hence the extraction of cerium from it is quite direct. First, the bastnäsite is purified, using dilute hydrochloric acid to remove calcium carbonate impurities. The ore is then roasted in the air to oxidize it to the lanthanide oxides: while most of the lanthanides will be oxidized to the sesquioxides Ln2O3, cerium will be oxidized to the dioxide CeO2. This is insoluble in water and can be leached out with 0.5 M hydrochloric acid, leaving the other lanthanides behind.[46]
The procedure for monazite, (Ln,Th)PO
4, which usually contains all the rare earths, as well as thorium, is more involved. Monazite, because of its magnetic properties, can be separated by repeated electromagnetic separation. After separation, it is treated with hot concentrated sulfuric acid to produce water-soluble sulfates of rare earths. The acidic filtrates are partially neutralized with sodium hydroxide to pH 3–4. Thorium precipitates out of solution as hydroxide and is removed. After that, the solution is treated with ammonium oxalate to convert rare earths to their insoluble oxalates. The oxalates are converted to oxides by annealing. The oxides are dissolved in nitric acid, but cerium oxide is insoluble in HNO3 and hence precipitates out.[16] Care must be taken when handling some of the residues as they contain 228Ra, the daughter of 232Th, which is a strong gamma emitter.[46]
Applications
Carl Auer von Welsbach, who discovered many applications of cerium
Cerium has two main applications, both of which use CeO2. The industrial application of ceria is for polishing, especially chemical-mechanical planarization (CMP). In its other main application, CeO2 is used to decolorize glass. It functions by converting green-tinted ferrous impurities to nearly colorless ferric oxides.[52] Ceria has also been used as a substitute for its radioactive congener thoria, for example in the manufacture of electrodes used in gas tungsten arc welding, where ceria as an alloying element improves arc stability and ease of starting while decreasing burn-off.[53]
Gas mantles and pyrophoric alloys
The first use of cerium was in gas mantles, invented by Austrian chemist Carl Auer von Welsbach. In 1885, he had previously experimented with mixtures of magnesium, lanthanum, and yttrium oxides, but these gave green-tinted light and were unsuccessful.[54] Six years later, he discovered that pure thorium oxide produced a much better, though blue, light, and that mixing it with cerium dioxide resulted in a bright white light.[55] Cerium dioxide also acts as a catalyst for the combustion of thorium oxide.
This resulted in commercial success for von Welsbach and his invention, and created great demand for thorium. Its production resulted in a large amount of lanthanides being simultaneously extracted as by-products.[56] Applications were soon found for them, especially in the pyrophoric alloy known as "mischmetal" composed of 50% cerium, 25% lanthanum, and the remainder being the other lanthanides, that is used widely for lighter flints.[56] Usually iron is added to form the alloy ferrocerium, also invented by von Welsbach.[57] Due to the chemical similarities of the lanthanides, chemical separation is not usually required for their applications, such as the addition of mischmetal to steel as an inclusion modifier to improve mechanical properties, or as catalysts for the cracking of petroleum.[46] This property of cerium saved the life of writer Primo Levi at the Auschwitz concentration camp, when he found a supply of ferrocerium alloy and bartered it for food.[58]
Pigments and phosphors
The photostability of pigments can be enhanced by the addition of cerium, as it provides pigments with lightfastness and prevents clear polymers from darkening in sunlight.[59] An example of a cerium compound used on its own as an inorganic pigment is the vivid red cerium(III) sulfide (cerium sulfide red), which stays chemically inert up to very high temperatures. The pigment is a safer alternative to lightfast but toxic cadmium selenide-based pigments.[34] The addition of cerium oxide to older cathode-ray tube television glass plates was beneficial, as it suppresses the darkening effect from the creation of F-center defects due to the continuous electron bombardment during operation. Cerium is also an essential component as a dopant for phosphors used in CRT TV screens, fluorescent lamps, and later white light-emitting diodes.[60][61] The most commonly used example is cerium(III)-doped yttrium aluminium garnet (Ce:YAG) which emits green to yellow-green light (550–530 nm) and also behaves as a scintillator.
Other uses
Cerium salts, such as the sulfides Ce2S3 and Ce3S4, were considered during the Manhattan Project as advanced refractory materials for the construction of crucibles which could withstand the high temperatures and strongly reducing conditions when casting plutonium metal.[39][40] Despite desirable properties, these sulfides were never widely adopted due to practical issues with their synthesis.[39] Cerium is used as alloying element in aluminium to create castable eutectic aluminium alloys with 6–16 wt.% Ce, to which Mg and/or Si can be further added. These Al-Ce alloys have excellent high temperature strength and are suitable for automotive applications e.g. in cylinder heads.[62] Other alloys of cerium include Pu-Ce and Pu-Ce-Co plutonium alloys, which have been used as nuclear fuel.
Other automotive applications for the lower sesquioxide are as a catalytic converter for the oxidation of CO and NOx emissions in the exhaust gases from motor vehicles.[63][64]
Biological role and precautions
Cerium Hazards
GHS labelling:[65]
Pictograms
GHS02: Flammable
Signal word
Danger
Hazard statements
H228
Precautionary statements
P210
NFPA 704 (fire diamond)
NFPA 704 four-colored diamond
2
0
0
The early lanthanides have been found to be essential to some methanotrophic bacteria living in volcanic mudpots, such as Methylacidiphilum fumariolicum: lanthanum, cerium, praseodymium, and neodymium are about equally effective.[66][67] Cerium is otherwise not known to have biological role in any other organisms, but is not very toxic either; it does not accumulate in the food chain to any appreciable extent. Because it often occurs together with calcium in phosphate minerals, and bones are primarily calcium phosphate, cerium can accumulate in bones in small amounts that are not considered dangerous.
Cerium nitrate is an effective topical antimicrobial treatment for third-degree burns,[34][68] although large doses can lead to cerium poisoning and methemoglobinemia.[69] The early lanthanides act as essential cofactors for the methanol dehydrogenase of the methanotrophic bacterium Methylacidiphilum fumariolicum SolV, for which lanthanum, cerium, praseodymium, and neodymium alone are about equally effective.[70]
Like all rare-earth metals, cerium is of low to moderate toxicity. A strong reducing agent, it ignites spontaneously in air at 65 to 80 °C. Fumes from cerium fires are toxic. Water should not be used to stop cerium fires, as cerium reacts with water to produce hydrogen gas. Workers exposed to cerium have experienced itching, sensitivity to heat, and skin lesions. Cerium is not toxic when eaten, but animals injected with large doses of cerium have died due to cardiovascular collapse.[34] Cerium is more dangerous to aquatic organisms, on account of being damaging to cell membranes; this is an important risk because it is not very soluble in water, thus causing contamination of the environment .[34]
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vte
Periodic table
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
1 H He
2 Li Be B C N O F Ne
3 Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
7 Fr Ra Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
s-block f-block d-block p-block
vte
Cerium compounds
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