Basic solutions oxidation-reduction

Plutonium(III) in aqueous solution, Pu " ( 4)> is pale blue. Aqueous plutonium(IV) is tan or brown the nitrate complex is green. Pu(V) is pale red-violet or pink in aqueous solution and is beUeved to be the ion PuO Pu(VI) is tan or orange in acid solution, and exists as the ion PuO. In neutral or basic solution Pu(VI) is yellow cationic and anionic hydrolysis complexes form. Pu(VII) has been described as blue-black. Its stmcture is unknown but may be the same as the six-coordinate NpO (OH) (91). Aqueous solutions of each oxidation state can be prepared by chemical oxidants or reductants... 

Ghromium(III) Compounds. Chromium (ITT) is the most stable and most important oxidation state of the element. The E° values (Table 2) show that both the oxidation of Cr(II) to Cr(III) and the reduction of Cr(VI) to Cr(III) are favored in acidic aqueous solutions. The preparation of trivalent chromium compounds from either state presents few difficulties and does not require special conditions. In basic solutions, the oxidation of Cr(II) to Cr(III) is still favored. However, the oxidation of Cr(III) to Cr(VI) by oxidants such as peroxides and hypohaUtes occurs with ease. The preparation of Cr(III) from Cr(VI) ia basic solutions requires the use of powerful reducing agents such as hydra2ine, hydrosulfite, and borohydrides, but Fe(II), thiosulfate, and sugars can be employed in acid solution. Cr(III) compounds having identical counterions but very different chemical and physical properties can be produced by controlling the conditions of synthesis. 

Figure 11.8 Oxidation states of nitrogen showing standard reduction potentials in volts (a) in acid solution at pH 0, and (b) in basic solution at pH 14.

Balance each of the following skeletal equations by using oxidation and reduction half-reactions. All the reactions take place in basic solution. Identify the oxidizing agent and reducing agent in each reaction. 

The aluminum-air fuel cell is used as a reserve battery in remote locations. In this cell aluminum reacts with the oxygen in air in basic solution, (a) Write the oxidation and reduction half-reactions for this cell, (b) Calculate the standard cell potential. See Box 12.1. 

In the goethite process, the precipitation of iron from solution occurs in the form of hydrated ferric oxide, FeOOH. The commercial development of the process was due to Societe de La Vielle Montagne. The process basically involves the reduction of iron to the ferrous state, and this is followed by oxidation by air at a temperature of around 90 °C and at a pH controlled at around 3.0. The reaction can chemically be shown as ... 

Alternatively, as an oxidizing agent, H202 yields H20 (or OH- in basic solution) as the oxygen atoms undergo reduction to the —2 oxidation state ... 

Common chemical titrations include acid-base, oxidation-reduction, precipitation, and complexometric analysis. The basic concepts underlying all titration are illustrated by classic acid-base titrations. A known amount of acid is placed in a flask and an indicator added. The indicator is a compound whose color depends on the pH of its environment. A solution of base of precisely known concentration (referred to as the titrant) is then added to the acid until all of the acid has just been reacted, causing the pH of the solution to increase and the color of the indicator to change. The volume of the base required to get to this point in the titration is known as the end point of the titration. The concentration of the acid present in the original solution can be calculated from the volume of base needed to reach the end point and the known concentration of the base. 

Perhaps the most important application of redox chemicals in the modern laboratory is in oxidation or reduction reactions that are required as part of a preparation scheme. Such preoxidation or prereduction is also frequently required for certain instrumental procedures for which a specific oxidation state is essential in order to measure whatever property is measured by the instrument. An example in this textbook can be found in Experiment 19 (the hydroxylamine hydrochloride keeps the iron in the +2 state). Also in wastewater treatment plants, it is important to measure dissolved oxygen (DO). In this procedure, Mn(OH)2 reacts with the oxygen in basic solution to form Mn(OH)3. When acidified and in the presence of KI, iodine is liberated and titrated. This method is called the Winkler method. 

Figure 11-15 shows the corrosion rate observed for a metallic nickel electrode in aerated aqueous sulfate solutions as a function of pH. In addic solutions, nickel corrodes in the active state at a rate which is controlled by the diffusion of hydrated oi en molecules (oxidants). In solutions more basic than pH 6, however, nickel spontaneously passivates by hydrated oiQ n molecules and corrosion is negligible. As shown in the inserted sub-figures in Fig. 11-15, the maximum current of anodic nickel dissolution in the active state is greater in the range of addic pH however, the Tnaximnm current of anodic nickel dissolution is smaller in the range of basic pH than the current of cathodic reduction of os en molecules (dashed curve) which is controlled by the diffusion of hydrated oiQ gen molecules. Consequently, metallic nickel remains in the active state in addic solutions but is spontaneously passivated by hydrated ojQ n molecules in basic solutions. It... 

The oxidation-reduction potential or redox potential ( h) is a measure of the tendency of a solution to be oxidizing or reducing. Oxidation and reduction are basically electrical processes that are readily measiued by an electrode potential. All measurements are referred to die standard hydrogen electrode, the potential of which is taken as 0.00 V at 298 K, the H2 pressure as 101325 N/m (1 atm) and activities of H2 and as unity. When the half-cell reaction is written as an oxidation reaction ... 

The most important reactions of hydrogen peroxide involve oxidation-reduction. It is a powerful oxidizing agent, both in acidic and basic solutions. Usually a 30% aqueous solution of H2O2 is used in oxidation. While oxidation with H2O2 in basic solution is fast, it is slow in acid solution. The half-reaction in acidic solution is ... 

Practically in every general chemistry textbook, one can find a table presenting the Standard (Reduction) Potentials in aqueous solution at 25 °C, sometimes in two parts, indicating the reaction condition acidic solution and basic solution. In most cases, there is another table titled Standard Chemical Thermodynamic Properties (or Selected Thermodynamic Values). The former table is referred to in a chapter devoted to Electrochemistry (or Oxidation - Reduction Reactions), while a reference to the latter one can be found in a chapter dealing with Chemical Thermodynamics (or Chemical Equilibria). It is seldom indicated that the two types of tables contain redundant information since the standard potential values of a cell reaction ( n) can be calculated from the standard molar free (Gibbs) energy change (AG" for the same reaction with a simple relationship... 

Consequently, reduction of cobalt(III) ammines in basic solution is not favorable. A variety of reducing agents has been used to effect reaction (11). The fortunate coincidences that cobalt(III) complexes are substitution inert while cobalt(II) systems are labile and that cobalt(II) is resistant to oxidation or further reduction in acid solution offer many advantages in the study of redox processes. Not surprisingly, work with cobalt(III) complexes forms the basis for much of the present understanding of oxidation-reduction reactions. 

Write partial equations for the oxidation and the reduction. Then (1) Balance charges by adding in acid solutions or OH in basic solutions. (2) Balance the number of O s by adding H O s to one side. (3) Balance the number of H s by adding H s to one side. The number added is the number of equivalents of oxidant or reductant. 

Reduction of (oxidation fcy) 02 in basic solution the reverse is the oxidation (destruction) of water as solvent. 

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