Copper Cu ions

The last cytochrome complex is cytochrome oxidase, which passes electrons from cytochrome c to O2 (see Fig. 21.5). It contains cytochromes a and a and the oxygen binding site. A whole oxygen molecule, O2, must accept four electrons to be reduced to 2 EI2O. Bound copper (Cu ) ions in the cytochrome oxidase complex facilitate the collection of the four electrons and the reduction of O2. 

In Chapter 19, you read that all redox reactions involve a transfer of electrons from the species that is oxidized to the species that is reduced. Figure 20.1 and Figure 20.2 illustrate the simple redox reaction in which zinc atoms are oxidized to form zinc (Zn +) ions. The two electrons donated from each zinc atom are accepted by a copper (Cu +) ion, which becomes an atom of copper metal. The following net ionic equation illustrates the electron transfer that occurs. 

One common example of a redox reaction in electrochemistry involves the transfer of electrons from zinc (Zn) metal to copper (Cu) ions in an electrochemical cell. 

The second method or common naming system uses the endings (suffixes) to distinguish between chemical forms. If an experiment calls for cuprous sulfate, it is talking about a copper Cu" ion. The ending ous is used to name... 

The second method or common naming system uses the endings (suffixes) to distinguish between chemical forms. If an experiment calls for cuprous sulfate, it is talking about a copper Cu" ion. The ending "ous is used to name the lesser charged ion of the different copper forms. The copper ion Cu " is known as a cupric ion, while Cu" is called the onerous ion, since it is the lesser charged ion of the two forms. The iron ion Fe " is called a ferric ion, while Fe " is known as a ferrous ion. 

On heating the pentahydrate, four molecules of water are lost fairly readily, at about 380 K and the fifth at about 600 K the anhydrous salt then obtained is white the Cu " ion is now surrounded by sulphate ions, but the d level splitting energy does not now correspond to the visible part of the spectrum, and the compound is not coloured. Copper(Il) sulphate is soluble in water the solution has a slightly acid reaction due to formation of [CufHjOijOH] species. Addition of concentrated ammonia... 

The rate of the uncatalysed reaction in all four solvents is rather slow. (The half-life at [2.5] = 1.00 mM is at least 28 hours). However, upon complexation of Cu ion to 2.4a-g the rate of the Diels-Alder reaction between these compounds and 2.5 increases dramatically. Figure 2.2 shows the apparent rate of the Diels-Alder reaction of 2.4a with 2.5 in water as a lunction of the concentration of copper(II)nitrate. At higher catalyst concentrations the rate of the reaction clearly levels off, most likely due to complete binding of the dienophile to the catalyst. Note that in the kinetic experiments... 

In the reactions of 10.13a with alkali metal terr-butoxides cage expansion occurs to give the sixteen-atom cluster 10.15, in which two molecules of MO Bu (M = Na, K) are inserted into the dimeric structure. The cluster 10.13a also undergoes transmetallation reactions with coinage metals. For example, the reactions with silver(I) or copper(I) halides produces complexes in which three of the ions are replaced by Ag" or Cu" ions and a molecule of lithium halide is incorporated in the cluster. ... 

The importance of the o-hydroxyl moiety of the 4-benzyl-shielding group of R,R-BOX/o-HOBn-Cu(OTf)2 complex was indicated when enantioselectivities were compared between the following two reactions. Thus, the enantioselectivity observed in the reaction of O-benzylhydroxylamine with l-crotonoyl-3-phenyl-2-imi-dazolidinone catalyzed by this catalyst was 85% ee, while that observed in a similar reaction catalyzed by J ,J -BOX/Bn.Cu(OTf)2 having no hydroxyl moiety was much lower (71% ee). In these reactions, the same mode of chirality was induced (Scheme 7.46). We believe the free hydroxyl groups can weakly coordinate to the copper(II) ion to hinder the free rotation of the benzyl-shielding substituent across the C(4)-CH2 bond. This conformational lock would either make the coordination of acceptor molecules to the metallic center of catalyst easy or increase the efficiency of chiral shielding of the coordinated acceptor molecules. 

In the Lummus process (Figure 10-15), the reaction occurs in the liquid phase at approximately 220-240°C over Mg " + Cu " benzoate. Magnesium benzoate is an initiator, with the Cu " reduced to Cu ". The copper (1) ions are reoxidized to copper (II) ions. 

Crevice corrosion of copper alloys is similar in principle to that of stainless steels, but a differential metal ion concentration cell (Figure 53.4(b)) is set up in place of the differential oxygen concentration cell. The copper in the crevice is corroded, forming Cu ions. These diffuse out of the crevice, to maintain overall electrical neutrality, and are oxidized to Cu ions. These are strongly oxidizing and constitute the cathodic agent, being reduced to Cu ions at the cathodic site outside the crevice. Acidification of the crevice solution does not occur in this system. 

Most cases of crevice corrosion take place in near-neutral solutions in which dissolved oxygen is the cathode reactant, but in the case of copper and copper alloys crevice corrosion can occur owing to differences in the concentration of Cu ions however, in the latter the mechanism appears to be different, since attack takes place at the exposed surface close to the crevice and not within the crevice in fact, the inside of the crevice may actually be cathodic and copper deposition is sometimes observed, particularly in the Cu-Ni alloys. Similar considerations apply in acid solutions in which the hydrogen ion is the cathode reactant, and again attack occurs at the exposed surface close to the crevice. 

The potentials of film-free a-brass and /3-brass in solutions comparable to those existing inside the alloy at the advancing front of attack were found to be —0-38V and —0-56V (v. S.H.E.), respectively. It was also established, taking into account the activities of copper ions in equilibrium with the sparingly soluble corrosion product CU2CI2, that whereas Cu ions can be reduced to copper at —0 -16 V the reduction of Cu ions is possible only at potentials more negative than —0-41 V. Thus whereas the /3-phase of an a/3-brass can reduce both Cu and Cu ions, the a-brass can reduce only the Cu ion. 

K has the value of about 1 x 10 at 298 K, and in solutions of copper ions in equilibrium with metallic copper, cupric ions therefore greatly predominate (except in very dilute solutions) over cuprous ions. Cupric ions are therefore normally stable and become unstable only when the cuprous ion concentration is very low. A very low concentration of cuprous ions may be produced, in the presence of a suitable anion, by the formation of either an insoluble cuprous salt or a very stable complex cuprous ion. Cuprous salts can therefore exist in contact with water only if they are very sparingly soluble (e.g. cuprous chloride) or are combined in a complex, e.g. [Cu(CN)2) , Cu(NH3)2l. Cuprous sulphate can be prepared in non-aqueous conditions, but because it is not sparingly soluble in water it is immediately decomposed by water to copper and cupric sulphate. 

Colon of copper complexes. When ammonia is added to 0.2 MCu2. the [Cu(NH3)4]2+ complex ion forms. The ammonia-containing ion is an intense deep blue, almost violet. The hydrated copper complex ion [Cu(H20)4]2+ is light blue. 

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. 

Like all the coinage metals, copper forms compounds with oxidation number + 1. However, in water, copper(I) salts disproportionate into metallic copper and copper(II) ions. The latter exist as pale blue [Cu(H20)6]2+ ions in water. 

Many of the d-block elements form characteristically colored solutions in water. For example, although solid copper(II) chloride is brown and copper(II) bromide is black, their aqueous solutions are both light blue. The blue color is due to the hydrated copper(II) ions, [Cu(H20)fJ2+, that form when the solids dissolve. As the formula suggests, these hydrated ions have a specific composition they also have definite shapes and properties. They can be regarded as the outcome of a reaction in which the water molecules act as Lewis bases (electron pair donors, Section 10.2) and the Cu2+ ion acts as a Lewis acid (an electron pair acceptor). This type of Lewis acid-base reaction is characteristic of many cations of d-block elements. 

Related compounds with other transition metals have been studied only sparsely, e.g., with nickel(II) [198], cobalt(III) [174], and rhodium(lll) [199, 200]. A series of dimeric copper(ll) complexes [[Cu(L BF2)S][X] is also known and exhibits interesting magnetic effects associated with electron spin exchange between the copper(ll) ions [201]. 

The extrapolation of physical attributes of substances to the submicroscopic level of representation was evident when students explained the changes in the displacement reaction between zinc powder and aqueous copper(II) sulphate. The decrease in intensity of the blue colour of the solution was attributed by 31% of students to the removal of blue individual Cu + ions from aqueous solution. The suggestion that individual Cu + ions (the submicroscopic level) are blue may be indicative of the extrapolation of the blue colour of the aqueous copper(II) sulphate (the macroscopic level) to the colour of individual Cu + ions (the submicroscopic level). Thirty-one percent of students also suggested that reddish-brown, insoluble individual atoms of copper were produced in this chemical reaction, again suggesting extrapolation of the bulk properties of copper, i.e., being reddish-brown and insolnble in water (the macroscopic level), to individual copper atoms having these properties (the snbmicroscopic level). 

Apart from the three broad categories of student conceptions discussed above, students displayed several inappropriate conceptions relating to the stractural properties of substances. For example, 14% of students suggested that Mg + ions were present in magnesium ribbon. A second example involved the chemical reaction between copper(II) oxide powder and dilute sulphuric acid. In this instance, 25% of students suggested that Cu + ions were present only in aqueous solution but not in the solid and liquid states. This view was rather unexpected because students had earlier been introdnced to ionic and covalent compounds. It is likely that students had merely rote-learned the general rale without sufficient understanding that ionic solids are formed between metallic and non-metallic elements. 

The biological impact of starch capped copper nanoparticles on mouse embryonic fibroblast (3T3L1) cells in vitro) was also evaluated by various parameters. More than 85 % of the 3T3Llcells were found to be viable, even after 20 hours time exposure which implies minimum impact on cell viability and morphology. The study demonstrates dose dependent cytotoxic potential of SCuNPs, that is non cytotoxic in the nanogram dose and moderately cytotoxic in the microgram doses (Fig. 10). Comparison of SCuNPs with Cu ions and uncapped copper nanoparticles (UCuNPs) revealed that, ions are more cytotoxic than SCuNPs. This observation supports the theory of slow release of ions from starch coated nanoparticles. 

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