Oxidation number transition elements

Group lA and group 2A metals have only one oxidation number. Transition metals and metals on the right side of the periodic table often have more than one oxidation number. To distinguish between multiple oxidation numbers of the same element, the name of the chemical formula must indicate the oxidation number of the cation. The oxidation number is written as a Roman numeral in parentheses after the name of the cation. For example, the compound formed from Fe + and has the formula FeO and is named iron(II) oxide. The compound formed from Fe + and has the formula Fe203 and is named iron(III) oxide. 

Multiple oxidation states are characteristic of the transition elements. Remember that iron gives up two electrons and forms the Fe + ion in its oxide, FeO. In another oxide, Fe203, iron gives up its two 4s electrons and one 3d electron to form the Fe ion. Many of the transition elements can have multiple oxidation numbers ranging from 2+ to 7+. These oxidation numbers are due to involvement of the d electrons in chemical bonding. Recall that only some of the heavier main group elements such as tin, lead, and bismuth have multiple oxidation numbers. These elements also have d electrons that can be involved in bonding. 

The UV/vis spectra of transition metal ions show d-d transitions and charge transfer bands that are highly sensitive to oxidation state and environment (301). There are a number of reports regarding the use of UV/vis spectroscopy in the characterization of LDHs and derived oxides containing transition elements (271,315-321). For example, Roussel et al. used UV/vis spectroscopy as well as EXAFS to examine the formation of ZnCr-Cl-LDH. They studied the species during precipitation at a constant pH = 5 by slow addition of metal chloride and NaOH solutions simultaneously to C02-free water. The continuous changes in peak position and intensity of the Cr species indicated the formation of Cr monomer, dimer, trimer, and tetramer species at different addition stages (315). 

Oxidation numbers of elements in compounds generally increase regularly as you move across periods 2 and 3 in the periodic table (Table 9.2). For example, the maximum oxidation number of the elements in oxides increases from +1 in sodium to +7 for chlorine. Elements not in the transition block are known as main group elements. 

Trialkyl- and triarylarsine sulfides have been prepared by several different methods. The reaction of sulfur with a tertiary arsine, with or without a solvent, gives the sulfides in almost quantitative yields. Another method involves the reaction of hydrogen sulfide with a tertiary arsine oxide, hydroxyhahde, or dihaloarsorane. X-ray diffraction studies of triphenylarsine sulfide [3937-40-4], C gH AsS, show the arsenic to be tetrahedral the arsenic—sulfur bond is a tme double bond (137). Triphenylarsine sulfide and trimethylarsine sulfide [38859-90-4], C H AsS, form a number of coordination compounds with salts of transition elements (138,139). Both trialkyl- and triarylarsine selenides have been reported. The trialkyl compounds have been prepared by refluxing trialkylarsines with selenium powder (140). The preparation of triphenylarsine selenide [65374-39-2], C gH AsSe, from dichlorotriphenylarsorane and hydrogen selenide has been reported (141), but other workers could not dupHcate this work (140). 

The redox behaviour of Th, Pa and U is of the kind expected for d-transition elements which is why, prior to the 1940s, these elements were commonly placed respectively in groups 4, 5 and 6 of the periodic table. Behaviour obviously like that of the lanthanides is not evident until the second half of the series. However, even the early actinides resemble the lanthanides in showing close similarities with each other and gradual variations in properties, providing comparisons are restricted to those properties which do not entail a change in oxidation state. The smooth variation with atomic number found for stability constants, for instance, is like that of the lanthanides rather than the d-transition elements, as is the smooth variation in ionic radii noted in Fig. 31.4. This last factor is responsible for the close similarity in the structures of many actinide and lanthanide compounds especially noticeable in the 4-3 oxidation state for which... 

For most of the transition elements, several oxidation numbers are possible. 

The name of a monatomic cation is the same as the name of the element forming it, with the addition of the word ion, as in sodium ion for Na+. When an element can form more than one kind of cation, such as Cu+ and Cu2+ from copper, we use the oxidation number, the charge of the cation, written as a Roman numeral in parentheses following the name of the element. Thus, Cu+ is a copper(I) ion and Cu2+ is a copper(II) ion. Similarly, Fe2+ is an iron(II) ion and Fe3" is an iron(III) ion. As shown in Fig. C.6, most transition metals form more than one kind of ion so unless we are given other information we need to include the oxidation number in the names of their compounds. 

Table 6.4 Ionic radii for transition elements according to SHANNON [69], based on r(02 ) = 140 pm. Numbers with signs oxidation states Is = low spin, hs = high spin roman numerals coordination numbers if other than 6...

The rules above gave maximum and minimum oxidation numbers, but those might not be the only oxidation numbers or even the most important oxidation numbers for an element. Elements of the last six groups of the periodic table for example may have several oxidation numbers in their compounds, most of which vary from each other in steps of 2. For example, the major oxidation states of chlorine in its compounds are -1, +1, +3, +5, and +7. The transition metals have oxidation numbers that may vary from each other in steps of 1. The inner transition elements mostly form oxidation states of + 3, but the first part of the actinoid series acts more like transition elements and the elements have... 

Hydrogen is capable of forming compounds with all elements except the noble gases. In compounds with nonmetals, hydrogen usually behaves like a metal instead of a nonmetal. Therefore, when hydrogen combines with a nonmetal, it usually has a +1 oxidation number. When hydrogen combines with a metal, it usually has a —1 oxidation number. Hydrogen compounds with the transition metals are usually nonstoichiometric. Nonstoichiometric compounds have no definite formula. 

Transition metah—found in the groups located in the center of the periodic table, plus the lanthanide and actinide series. They are all solids, except mercury, and are the only elements whose shells other than their outer shells give up or share electrons in chemical reactions. Transition metals include the 38 elements from groups 3 through 12. They exhibit several oxidation states (oxidation numbers) and various levels of electronegativity, depending on their size and valence. 

Scandium is the first element in the fourth period of the transition elements, which means that the number of protons in their nuclei increases across the period. As with all the transition elements, electrons in scandium are added to an incomplete inner shell rather than to the outer valence shell as with most other elements. This characteristic of using electrons in an inner shell results in the number of valence electrons being similar for these transition elements although the transition elements may have different oxidation states. This is also why all the transition elements exhibit similar chemical activity. 

Symbol La atomic number 57 atomic weight 138.91 a rare-earth transition metal, precursor to a series of 14 inner-transition elements known as the lanthanide series electron configuration [XejSdiGs oxidation state -i-3 atomic radius 1.879A ionic radius (LaS+) 1.061A electronegativity 1.17 two natural isotopes are La-139 (99.911%) and La-138 (0.089%). 

The three elements to be treated in this chapter (V, Cr, Mn) are the third, fourth, and hfth members of the first transition series. The first two members (Sc, Ti) have been treated in previous chapters (Chapters 12 and 13). The ten elements of this first transition series (Sc through Zn) are characterized by electron activity in the 3d-4s levels. All elements in the 3d transition series are metals, and many of their compounds tend to be colored as a result of unpaired electrons. Most of the elements have a strong tendency to form complex ions due to participation of the d electrons in bonding. Since both the 4s and the 3d electrons are active, most of the elements show a considerable variety of oxidation states (Sc and Zn being exceptions). For the first five (Sc through Mn), the maximum oxidation number is the total number of electrons in the 4s and 3d levels. Complexing is often so strong that the most stable oxidation state for simple compounds may differ from that for complex compounds. 

Manganese is the third most abundant transition element [1]. It is present in a number of industrial, hiological, and environmental systems, representative examples of which include manganese oxide batteries [2] the oxygen-evolving center of photosystem II (PSII) [3] manganese catalase, peroxidase, superoxide dismutase (SOD), and other enzymes [4, 5] chiral epoxidation catalysts [6] and deep ocean nodules [7]. Oxidation-reduction chemistry plays a central role in the function of most, if not all, of these examples. 

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