Zinc ions, reactions

As an example of a different type of oxide, we may consider ZnO. This oxide evolves oxygen and forms cations in interstitial positions (Zn O) or (Zn O), and free electrons (eo). If the interstitial zinc ions are only singly charged, the reaction describing the non-stoichiometry may be written... 

In 1965, Breslow and Chipman discovered that zinc or nickel ion complexes of (E)-2-pyridinecarbaldehyde oxime (5) are remarkably active catalyst for the hydrolysis of 8-acetoxyquinoline 5-sulfonate l2). Some years later, Sigman and Jorgensen showed that the zinc ion complex of N-(2-hydroxyethyl)ethylenediamine (3) is very active in the transesterification from p-nitrophenyl picolinate (7)13). In the latter case, noteworthy is a change of the reaction mode at the aminolysis in the absence of zinc ion to the alcoholysis in the presence of zinc ion. Thus, the zinc ion in the complex greatly enhances the nucleophilic activity of the hydroxy group of 3. In search for more powerful complexes for the release of p-nitrophenol from 7, we examined the activities of the metal ion complexes of ligand 2-72 14,15). 

Each zinc atom loses two electrons in changing to a zinc ion, therefore zinc is oxidized. Each hydrogen ion gains an electron, changing to a hydrogen atom, therefore hydrogen is reduced. (After reduction, two hydrogen atoms combine to form molecular H2.) As before, reaction (7) can be separated into two half-reactions ... 

As a third oxidation-reduction example, suppose a strip of metallic zinc is placed in a solution of copper nitrate, Cu(N03)j. The strip becomes coated with reddish metallic copper and the bluish color of the solution disappears. The presence of zinc ion, Zn+2, among the products can be shown when the Cu+2 color is gone. Then if hydrogen sulfide gas is passed into the mixture, white zinc sulfide, ZnS, can be seen. The reaction between metallic zinc and the aqueous copper nitrate is... 

Listing the Zn-Zn+2 half-reaction first tells us that it releases electrons more readily than does the Cu-Cu+2 half-reaction. But if this is true, then the Zn-Zn+2 half-reaction must also release electrons more readily than does the Ag-Ag+ half-reaction. Our list leads us to expect that zinc metal will release electrons to silver ion, reacting to produce zinc ion and silver metal. 

Nickel metal reacts with cupric ions, Cu42, but not with zinc ions, Zn42 magnesium metal does react with Zn42. In each case of reaction, ions of +2 charge are formed. Use these data to expand the table of reactions on p. 206. 

At the zinc electrode, zinc ions pass into solution, leaving an equivalent negative charge on the metal. Copper ions are deposited at the copper electrode, rendering it positively charged. By completing the external circuit, the current (electrons) passes from the zinc to the copper. The chemical reactions in the cell are as follows ... 

A salt bridge serves as an ionconducting connection between the two half-cells. When the external circuit is closed, the oxidation reaction starts with the dissolution of the zinc electrode and the formation of zinc ions in half-cell I. In half-cell II copper ions are reduced and metallic copper is deposited. The sulfate ions remain unchanged in the aqueous solution. The overall cell reaction consists of an electron transfer between zinc and copper ions ... 

How would you use the solubility rules in Table 1.1 to separate the following pairs of ions In each case indicate what reagent you would add and write the net ionic equation for the precipitation reaction (a) barium and mcrcury(I) ions (b) silver and zinc ions. 

The emf of the Daniell cell for certain concentrations of copper and zinc ions is 1.04 V. What is the reaction Gibbs free energy under those conditions ... 

Many other metal displacement reactions can be visualized, but not all of them occur. Some metals are oxidized readily, but others are highly resistant to oxidation. Likewise, some metal cations are highly susceptible to reduction, but others resist reduction. Zinc displaces copper ions from aqueous solutions, but copper will not replace zinc ions, because Cu is easier to reduce than Zn . Zinc will not displace ions, because... 

When a zinc strip is dipped into the solution, the initial rates of these two processes are different. The different rates of reaction lead to a charge imbalance across the metal-solution interface. If the concentration of zinc ions in solution is low enough, the initial rate of oxidation is more rapid than the initial rate of reduction. Under these conditions, excess electrons accumulate in the metal, and excess cationic charges accumulate in the solution. As excess charge builds, however, the rates of reaction change until the rate of reduction is balanced by the rate of oxidation. When this balance is reached, the system is at dynamic equilibrium. Oxidation and reduction continue, but the net rate of exchange is zero Zn (.S ) Zn (aq) + 2 e (me t a i)... 

Crisp et al. (1978) were able to follow the course of the cement-forming reaction using infrared spectroscopy and to confirm previous observations. They found that the technique could be used to distinguish between crystalline and amorphous phases of the cement. Hopeite shows a number of bands between 1105 and 1000 cm this multiplicity has been explained by postulating a distortion of the tetrahedral orthophosphate anion. (Two-thirds of the zinc ions are tetrahedrally coordinated to four phosphate ions, and the remainder are octahedrally coordinated to two phosphate and four water ligands.)... 

This hypothesis received support from the electrical studies of Braden Clarke (1974) and Crisp, Ambersley Wilson (1980), who attributed maxima in curves of permittivity and conductivity against time to the liberation of water and its subsequent reabsorption into the matrix (Figure 93a,b). Crisp, Ambersley Wilson (1980) also considered that these maxima were due to generation of both water and ionic zinc species. Subsequently, as the reaction proceeds the zinc ions are fixed as insoluble zinc eugenolate. 

For instance, when current flow is from the right to the left in galvanic cell (1.19), the zinc electrode will be the cathode, and its surface is the site of the cathodic reaction involving the deposition of zinc by discharge of zinc ions from the solution ... 

This reaction satisfies the requirements listed above the zinc ions and electrons arriving at the surface from different sides disappear from the reaction zone. The anodic reaction... 

Electron withdrawal from a material is equivalent to its oxidation, while electron addition is equivalent to its reduction. In the anodic reaction, electrons are generated and a reactant (in our example, the chloride ions) is oxidized. In the cathodic reaction the reactant (the zinc ions) is reduced. Thus, anodic reactions are always oxidation reactions, and cathodic reactions are reduction reactions for the initial reactants. 

The resulting water helps to extend the life of the dry cell by providing moisture for the movement of the ionic species. A second reaction, that extends the usefulness of this cell, is the formation of an amine complex of zinc ions in the cell ... 

Iminium ions, generated in aqueous solution from secondary amines and formaldehyde, undergo a Barbier-type allylation mediated by tin, aluminum, and zinc. The reaction is catalyzed by copper and produces tertiary homoallylamines in up to 85% yield.67 The imines generated in situ from 2-pyridinecarboxaldehyde/2-quinolinecarboxaldehyde and aryl amines undergo indium-mediated Barbier allylation in aqueous media to provide homoallylic amines.68 Crotyl and cinnamyl bromides... 

For example, consider a system in which metallic zinc is immersed in a solution of copper(II) ions. Copper in the solution is replaced by zinc which is dissolved and metallic copper is deposited on the zinc. The entire change of enthalpy in this process is converted to heat. If, however, this reaction is carried out by immersing a zinc rod into a solution of zinc ions and a copper rod into a solution of copper ions and the solutions are brought into contact (e.g. across a porous diaphragm, to prevent mixing), then zinc will pass into the solution of zinc ions and copper will be deposited from the solution of copper ions only when both metals are connected externally by a conductor so that there is a closed circuit. The cell can then carry out work in the external part of the circuit. In the first arrangement, reversible reaction is impossible but it becomes possible in the second, provided that the other conditions for reversibility are fulfilled. 

As demonstrated in Section 5.2, the electrode potential is determined by the rates of two opposing electrode reactions. The reactant in one of these reactions is always identical with the product of the other. However, the electrode potential can be determined by two electrode reactions that have nothing in common. For example, the dissolution of zinc in a mineral acid involves the evolution of hydrogen on the zinc surface with simultaneous ionization of zinc, where the divalent zinc ions diffuse away from the electrode. The sum of the partial currents corresponding to these two processes must equal zero (if the charging current for a change in the electrode potential is neglected). The potential attained by the metal under these conditions is termed the mixed potential Emix. If the polarization curves for both processes are known, then conditions can be determined such that the absolute values of the cathodic and anodic currents are identical (see Fig. 5.54A). The rate of dissolution of zinc is proportional to the partial anodic current. 

Calorimetry investigations of zinc ions with functionalized pyridines have been carried out in both dimethylformamide and acetonitrile. The pyridines used were pyridine, 3-methylpyridine, and 4-methylpyridine. In DMF, for all three pyridines, four- and six-coordinate species formed and their formation constants, reaction enthalpies and entropies were determined. The stability increases linearly with increasing basicity of the pyridine derivative. The formation of the 3-methylpyridine complex is enthalpically less favorable and entropically more favorable than... 

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