Cerium chemical properties

Although rare-earth ions are mosdy trivalent, lanthanides can exist in the divalent or tetravalent state when the electronic configuration is close to the stable empty, half-fUed, or completely fiUed sheUs. Thus samarium, europium, thuUum, and ytterbium can exist as divalent cations in certain environments. On the other hand, tetravalent cerium, praseodymium, and terbium are found, even as oxides where trivalent and tetravalent states often coexist. The stabili2ation of the different valence states for particular rare earths is sometimes used for separation from the other trivalent lanthanides. The chemicals properties of the di- and tetravalent ions are significantly different. 

Separation Processes. The product of ore digestion contains the rare earths in the same ratio as that in which they were originally present in the ore, with few exceptions, because of the similarity in chemical properties. The various processes for separating individual rare earth from naturally occurring rare-earth mixtures essentially utilize small differences in acidity resulting from the decrease in ionic radius from lanthanum to lutetium. The acidity differences influence the solubiUties of salts, the hydrolysis of cations, and the formation of complex species so as to allow separation by fractional crystallization, fractional precipitation, ion exchange, and solvent extraction. In addition, the existence of tetravalent and divalent species for cerium and europium, respectively, is useful because the chemical behavior of these ions is markedly different from that of the trivalent species. 

Hydrolysis is very extensive in Pu(IV) solutions, less so in Pu(Ill) and Pu(VI), and least in Pu(V). The chemical properties of Pu(IV) are somewhat similar to those of Ce(IV) and U(IV) (see Cerium AND cerium compounds). The hydrolysis thermodynamics of Pu(IV) have been assessed in perchlorate solutions (105). The first hydrolysis equiUbrium is... 

A predominant feature of the atomic structure of the lanthanide group is the sequential addition of 14 electrons to the 4f subshell (Table 1). The /"electrons do not participate in bond formation and in ordinary aqueous solutions all of the lanthanides exhibit a principal (III) state. The common (III) state confers a similarity in chemical properties to all lanthanide elements. Some of the lanthanides can also exist in the (II) state (Nd, Sm, Eu, Tm, Yh) or in the (IV) state (Ce, Pr, Nd, Tb, Dy). Except for Ce(IV), Eu(II), and Yb(II), these unusual lanthanide oxidation states can only be prepared under drastic redox pressure and temperature conditions, and they are not stable in aqueous solutions. Cerium (IV) is a strong oxidizing agent... 

The chemical properties of berkehum are rare earth-like character because of its half-filled 5/ subsheU and should be simdar to cerium. The element readily oxidizes to berkelium dioxide, Bk02 when heated to elevated temperatures (500°C). In aqueous solutions, the most common oxidation state is -i-3 which may undergo further oxidation to +4 state. A few compounds have been synthesized, the structures of which have been determined by x-ray diffraction methods. These include the dioxide, Bk02 sesquioxide, Bk203 fluoride,... 

Promoters Promoters are elements or compounds, such as cerium oxide or zirconia, used as additives to improve the physical or chemical properties of the catalysts. They can act in various ways ... 

Polyhydroxy compounds are oxidized by such metal ions as vanadium(V), chromium(VI), cerium(IV), iridium(IV), and gold(III), among others. These oxidations were found to be catalyzed by acids.171 173 Vanadium(V) and chromium(VI) are closely related in their chemical properties, but the reduction of V(V) is difficult compared with that of Cr(VI) because of its lower redox potential [V(V)-V(IV) = 1.00 V Cr(VI)-Cr(III) = 1.20 V], However, the redox potential increases at lower pH values, facilitating the oxidation of sugars. 

Three places after xenon there follows the remarkable group of the elements of the Rare Earths, because here, beginning with cerium, the Nf or 4f shell (/ — 3, m = —3, —2, —1, o, 1, 2, 3) is filled up. There is thus produced a group of 14 elements from cerium (58) to lutecium (71), which all possess the same electron configuration of the outermost shell as lanthanum and thus also show a great similarity in chemical properties [group of the lanthanides or lanthanons]. 

VII.22 CERIUM, Ce (At 140-12) - CERIUM(IV) The most important physical and chemical properties of cerium have been described in Section IV.22. 

Despite Brauner s belief in the validity of the Mendeleev methodology, he also had to admit that he had not yet succeeded in resolving the rare-earth crisis. Thus Brauner wrote in 1901 with reference to praseodymium that its maximum valency was tetravalent, like that of cerium but that no place had been found in the periodic table for an element possessing the physical and chemical properties of praseodymium and its compounds (Brauner, 1901b). He also admitted that the difficulties of finding a place for neodymium in the periodic table were even greater than in the case of praseodymium. 

SAFETY PROFILE Cerium resembles aluminum in its pharmacological action as well as in its chemical properties. The insoluble salts such as the oxalates are stated to be nontoxic even in large doses. It is used to prevent vomiting in pregnancy. The average dose is from 0.05 to 0.5 g. 

The use of CeOs-based materials in catalysis has attracted considerable attention in recent years, particularly in applications like environmental catalysis, where ceria has shown great potential. This book critically reviews the most recent advances in the field, with the focus on both fundamental and applied issues. The first few chapters cover structural and chemical properties of ceria and related materials, i.e. phase stability, reduction behaviour, synthesis, interaction with probe molecules (CO. O2, NO), and metal-support interaction — all presented from the viewpoint of catalytic applications. The use of computational techniques and ceria surfaces and films for model catalytic studies are also reviewed. The second part of the book provides a critical evaluation of the role of ceria in the most important catalytic processes three-way catalysis, catalytic wet oxidation and fluid catalytic cracking. Other topics include oxidation-combustion catalysts, electrocatalysis and the use of cerium catalysts/additives in diesel soot abatement technology. 

Cerium is an iron-gray metal with a melting point of 1,460°F (795°C) and a boiling point of 5,895°F (3,257°C). It is ductile and malleable. Ductile means capable of being made into thin wires. Malleable means capable of being hammered into thin sheets. Cerium s density is 6.78 grams per cubic centimeter. It exists in four different allotropic forms. Allotropes are forms of an element with different physical and chemical properties. 

Cerium resembles aluminum in its biologic and chemical properties. 

The lanthanide series of metals includes the 15 elements with atomic numbers 57-71, plus yttrium (atomic number 39). The lanthanides occur in the earth s crust at concentrations exceeding some commonly used industrial elements making the term rare earths something of a misnomer. For example, yttrium, cerium, lanthanum, and neodymium are present in the earth s crust at higher concentrations than lead. Of the 15 lanthanides, only promethium does not occur in nature - it is a man-made element. All of the lanthanides have similar physical and chemical properties. Because of similarities in their chemistry and toxicity, the characteristics of the lanthanides are often described as a group. Within the lanthanide group, however, there are differences between the toxicity of the individual lanthanide elements and their compounds. 

Cerium (Ce, at. mass 140.12), which is the most popular rare-earth element, occurs also in the IV oxidation state. In chemical properties, cerium(IV) resembles Th and U(IV). The yellow Ce(OH)4 precipitates at pH 1. Cerium(III) is oxidized to Ce(lV) in acidic media by bismuthate, silver(II) oxide, or persulphate (in the presence of Ag ). 

In caesium (Z = 55) one electron occupies the 6s orbital of the P shell, and in barium (Z = 56) there are two electrons in this orbital. Thereafter the development of the P shell is interrupted, and lanthanum (Z = 57) initiates the third transition series with one electron in the 5 d orbital of the 0 shell. The development of this series, however, proceeds no further at this stage, and in the elements from cerium (Z = 58) to lutecium (Z = 71) electrons are entering the hitherto vacant 4/orbitals of the N shell. These elements constitute the rare earths or elements of the lanthanide series, and the fact that the differentiating electrons are so deep in the electronic structure is responsible for the close similarity of their chemical properties. 

The most important physical and chemical properties of cerium have been described in Section 6.21. 

One of the characteristic chemical properties of the group, and certainly the most useful in connection with analysis and isolation, is the ease and completeness of precipitation of the hydrated oxalates from acidic solutions. When the oxalates are ignited at 900°, the oxides (R.E.)203, are obtained, except in the case of cerium(III) oxalate, which gives the dioxide. 

In fact, the classification of chemical elements is valuable only in so far as it illustrates chemical behaviour, and it is conventional to use the term transition elements in a mote restricted sense. The elements in the irmer transition series from cerium (58) to lutetium (71) are called the lanthanoids those in the series from thorium (90) to lawrencium (103) are the actl-noids. These two series together make up the /block in the periodic table. It is also common to include scandium, yttrium, and lanthanum with the lanthanoids (because of chemical similarity) and to include actinium with the actinoids. Of the remaining transition elements, it is usual to speak of three main transition series from titanium to copper from zirconium to silver and from hafnium to gold. All these elements have similar chemical properties that result from the presence of unfilled d-orbltals in the element or (in the case of copper, silver, and gold) in the ions. The elements from 104 to 109 and the undiscovered elements 110 and 111 make up a fourth transition series. The elements zinc, cadmium, and mercury have filled d-orbltals both in the elements and in compounds, and are usually regarded as nontransition elements forming group 12 of the periodic table. 

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