Transition metal colors

Alkali or alkaline-earth salts of both complexes are soluble in water (except for Ba2[Fe(CN)g]) but are insoluble in alcohol. The salts of hexakiscyanoferrate(4—) are yellow and those of hexakiscyanoferrate(3—) are mby red. A large variety of complexes arise when one or more cations of the alkah or alkaline-earth salts is replaced by a complex cation, a representative metal, or a transition metal. Many salts have commercial appHcations, although the majority of industrial production of iron cyanide complexes is of iron blues such as Pmssian Blue, used as pigments (see Pigments, inorganic). Many transition-metal salts of [Fe(CN)g] have characteristic colors. Addition of [Fe(CN)g] to an unknown metal salt solution has been used as a quaUtative test for those transition metals. 

Transition metals can be divided into two groups according to the characteristics of their peroxides. The first group comprises those metals that, in their highest oxidation states, have no d electrons, eg, TP" and These metals form peroxides from hydrogen peroxide, the colors of which result from... 

The other group of transition metals comprises those metals that retain d electrons in their normal valence states, eg, Co " and Pp". These metals form peroxides from dioxygen or from hydrogen peroxide. Their colors result from d—d transitions. These peroxo species act as nucleophiles. 

Stmctures are highly varied among the transition metals. The titanium atom in titanium tetraethoxide has the coordination number 6 (Fig. 1). The corresponding zirconium compound, with coordination number 8, has a different stmcture (Fig. 2). Metal alkoxides are colored when the corresponding metal ions are colored, otherwise they are not. 

The sohd-state, transition-metal example in Table 1 of [(CH2)2NH2]3CuCl illustrates another form of thermochromism the color shifts gradually and continuously because of changes in bandwidth with either heating or cooling (6). It is not unique, as this behavior has been mentioned for the class of... 

Color from Transition-Metal Compounds and Impurities. The energy levels of the excited states of the unpaked electrons of transition-metal ions in crystals are controlled by the field of the surrounding cations or cationic groups. Erom a purely ionic point of view, this is explained by the electrostatic interactions of crystal field theory ligand field theory is a more advanced approach also incorporating molecular orbital concepts. 

There are a number of ways to obtain color in a ceramic material (1). First, certain transition-metal ions can be melted into a glass or dispersed in a ceramic body when it is made. Although suitable for bulk ceramics, this method is rarely used in coatings because adequate tinting strength and purity of color caimot be obtained this way. 

The colors obtained depend primarily on the oxidation state and coordination number of the coloring ion (3). Table 1 Hsts the solution colors of several ions in glass. AH of these ions are transition metals some rare-earth ions show similar effects. The electronic transitions within the partially filled d andy shells of these ions are of such frequency that they fall in that narrow band of frequencies from 400 to 700 nm, which constitutes the visible spectmm (4). Hence, they are suitable for producing color (qv). 

Cobalt. Without a doubt cobalt 2-ethyIhexanoate [136-52-7] is the most important and most widely used drying metal soap. Cobalt is primarily an oxidation catalyst and as such acts as a surface or top drier. Cobalt is a transition metal which can exist in two valence states. Although it has a red-violet color, when used at the proper concentration it contributes very Httie color to clear varnishes or white pigmented systems. Used alone, it may have a tendency to cause surface wrinkling therefore, to provide uniform drying, cobalt is generally used in combination with other metals, such as manganese, zirconium, lead, calcium, and combinations of these metals. 

Most of ions do not interfere to the determination of P(V) or As(V). Big access of colored transition metals can be tolerated by using those metals solution as reference solution. It was already shown that high selectivity of the proposed method with respect to metal ions gave the opportunity to determine phosphoms in a number of nonferrous (brass, bronze) and ferrous alloys without preliminai y sepai ation. 

Flowever, ionic liquids acting as transition metal catalysts are not necessarily based on classical Lewis acids. Dyson et al. recently reported the ionic liquid [BMIM][Co(CO)4] [38]. The system was obtained as an intense blue-green colored liquid by metathesis between [BMIM]C1 and Na[Co(CO)4]. The liquid was used as a catalyst in the debromination of 2-bromoketones to their corresponding ketones. 

Transition metal ions. Transition metal ions impart color to many of their compounds and solutions, (a) Bottom row (left to right) iron(lll) chloride. copper ll) sulfate, manganese(ll) chloride, cobalt(ll) chloride. Top row (left to right) chromium(lll) nitrate, iron(ll) sulfate, nickel(ll) sulfate, potassium dichromate, (b) Solutions of the compounds in (a) in the order listed above. 

The transition metals, unlike those in Groups 1 and 2, typically show several different oxidation numbers in their compounds. This tends to make their redox chemistry more complex (and more colorful). Only in the lower oxidation states (+1, +2, +3) are the transition metals present as cations (e.g., Ag+, Zn2+, Fe3+). In higher oxidation states (+4 to +7) a transition metal is covalently bonded to a nonmetal atom, most often oxygen. 

Color. Many solid compounds of the transition metals and their aqueous solutions are colored. This color indicates light is absorbed in... 

Polynuclear transition metal cyanides such as the well-known Prussian blue and its analogues with osmium and ruthenium have been intensely studied Prussian blue films on electrodes are formed as microcrystalline materials by the electrochemical reduction of FeFe(CN)g in aqueous solutionThey show two reversible redox reactions, and due to the intense color of the single oxidation states, they appear to be candidates for electrochromic displays Ion exchange properties in the reduced state are limited to certain ions having similar ionic radii. Thus, the reversible... 

The initial step of the reaction with tin(II) chloride reduces the highly oxidized metal in the transition metal anions to low valency cations these are capable of forming stable colored complexes with thiocyanate. 

Most pure transition metals have the shiny gray appearance that is termed silvery because of the appearance of silver metal. However, some transition metals have other colors—for example, the orange color of copper and the yellow hue of gold. 

Color changes often provide evidence for the interaction of ligands and metal cations, particularly for the transition metals. The Ni + cation provides an example. Figure 20-5 shows that nickel(It) sulfate, a white crystalline solid, dissolves in water to give a green solution. The green color cannot be due to Ni or S04 , which the white solid shows to be colorless. Rather, the color comes from the octahedral complex that forms when each nickel ion binds to six water molecules NiS04(. ) -I- 6H2 0(/) [Ni (H2 0)g] (ag) + SOY (gg)... 

Color is a spectacular property of coordination complexes. For example, the hexaaqua cations of 3 transition metals display colors ranging from orange through violet (see photo at right). The origin of these colors lies in the d orbital energy differences and can be understood using crystal field theory. 

Further resolution of the details of oxidative dehydrogenation requires the measurement of a catalyst s degree of reduction carried out during steady state reaction. We note that UV-visible spectroscopy offers a way to perform this measurement since many of the transition metal oxides which are active as oxidation catalysts exhibit striking color changes between their oxidized and reduced states. 

Molecular Metal Complexes Compounds of this type do not form delocalized electronic bands in the sohd state, and their color is due to intramolecular electronic transitions. Many complexes of transition metals with organic ligands belong to this class. complexes with phenanthroline (red/colorless) and Ru + + with 2,2 -... 

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