Oxidised

Zhabotinsky A M, Buohholtz F, Kiyatin A B and Epstein I R 1993 Csoillations and waves in metal-ion oatalysed bromate osoillating reaotion in highly oxidised states J. Phys. Chem. 97 7578-84... 

Let us now consider the reduction of a metal oxide by carbon which is itself oxidised to carbon monoxide. The reaction will become energetically feasible when the free energy change for the combined process is negative (see also Figure i.i). Free energies. 

Thus an oxidising agent is identified as an electron acceptor and the oxidation of iron(II) by chlorine can be written as two "half equations, viz. 

Thus, the reducing agent causes reduction to take place, i.e. causes a reduction in the positive charge it must therefore supply electrons. It follows immediately that the oxidising agent must accept electrons. 

Oxidation states can be used to establish the stoichiometry for an equation. Consider the reaction between the manganate(VII) (permanganate) and ethanedioate (oxalate) ions in acidic solution. Under these conditions the MnO faq) ion acts as an oxidising agent and it is reduced to Mn (aq), i.e. 

Half-reaction (i) means that Co(II) in aqueous solution cannot be oxidised to Co(III) by adding ammonia to obtain the complexes in (ii), oxidation is readily achieved by, for example, air. Similarly, by adding cyanide, the hexacyanocobaltate(II) complex becomes a sufficiently strong reducing agent to produce hydrogen from water ... 

When either hydrogen ions or hydroxide ions participate in a redox half-reaction, then clearly the redox potential is alTected by change of pH. Manganate(Vir) ions are usually used in well-acidified solution, where (as we shall see in detail later) they oxidise chlorine ions. If the pH is increased to make the solution only mildly acidic (pH = 3-6), the redox potential changes from 1.52 V to about 1.1 V, and chloride is not oxidised. This fact is of practical use in a mixture of iodide and chloride ions in mildly acid solution. manganate(VII) oxidises only iodide addition of acid causes oxidation of chloride to proceed. 

Thus chloride ions are oxidised to chlorine by manganate( VIl) under standard conditions... 

Thus under standard conditions chloride ions are not oxidised to chlorine by dichromate(Vr) ions. However, it is necessary to emphasise that changes in the concentration of the dichromate(VI) and chloride ions alters their redox potentials as indicated by the Nernst equation. Hence, when concentrated hydrochloric acid is added to solid potassium dichromate and the mixture warmed, chlorine is liberated. 

Identify the oxidising agent and the reducing agent in each reaction and write half-equations showing the donation or acceptance of electrons by each of these eight reagents. 

Boron, being chemically a non-metal, is resistant to attack by nonoxidising acids but the other members of the group react as typical metals and evolve hydrogen. Aluminium, gallium and indium are oxidised to the + 3 oxidation state, the simplified equation being... 

Strong oxidising acids, for example hot concentrated sulphuric acid and nitric acid, attack finely divided boron to give boric acid H3CO3. The metallic elements behave much as expected, the metal being oxidised whilst the acid is reduced. Bulk aluminium, however, is rendered passive by both dilute and concentrated nitric acid and no action occurs the passivity is due to the formation of an impervious oxide layer. Finely divided aluminium does dissolve slowly when heated in concentrated nitric acid. 

The oxidation state -1-4 is predominantly covalent and the stability of compounds with this oxidation state generally decreases with increasing atomic size (Figure 8.1). It is the most stable oxidation state for silicon, germanium and tin, but for lead the oxidation state +4 is found to be less stable than oxidation state +2 and hence lead(IV) compounds have oxidising properties (for example, see p. 194). 

Before this treatment, the cassiterite content of the ore is increased by removing impurities such as clay, by washing and by roasting which drives off oxides of arsenic and sulphur. The crude tin obtained is often contaminated with iron and other metals. It is, therefore, remelted on an inclined hearth the easily fusible tin melts away, leaving behind the less fusible impurities. The molten tin is finally stirred to bring it into intimate contact with air. Any remaining metal impurities are thereby oxidised to form a scum tin dross ) on the surface and this can be skimmed off Very pure tin can be obtained by zone refining. 

Dilute acids have no effect on any form of carbon, and diamond is resistant to attack by concentrated acids at room temperature, but is oxidised by both concentrated sulphuric and concentrated nitric acid at about 500 K, when an additional oxidising agent is present. Carbon dioxide is produced and the acids are reduced to gaseous oxides ... 

Graphite reacts rather differently with mixtures of oxidising agents and concentrated oxoacids. A graphite oxide is formed the graphite... 

Amorphous carbon, having a far greater effective surface area than either diamond or graphite, is the most reactive form of carbon. It reacts with both hot concentrated sulphuric and hot concentrated nitric acids in the absence of additional oxidising agents but is not attacked by hydrochloric acid. 

Concentrated nitric acid, however, is an oxidising agent and tin reacts to give hydrated tin(IV) oxide in a partly precipitated, partly colloidal form, together with a small amount of tin(II) nitrate, Sn(N03)2 ... 

Again, nitric acid readily dissolves lead but is unable to oxidise lead beyond the oxidation state -P 2. The reduction products of the nitric acid vary with the concentration of acid used, and a number of nitrogen oxides are usually obtained. Warm dilute nitric acid gives mainly nitrogen oxide, NO. 

The product is a solid yellow hydrated oxide. If prepared by a method in the absence of water, a black anhydrous product is obtained. Germanium(II) oxide is stable in air at room temperature but is readily oxidised when heated in air or when treated at room temperature with, for example, nitric acid, hydrogen peroxide, or potassium manganate(VII). When heated in the absence of air it disproportionates at 800 K ... 

Tin(II) oxide is a dark-coloured powder which oxidises spontaneously in air with the evolution of heat to give tin(IV) oxide, SnO, ... 

The white precipitate of lead hydroxide (or hydrated lead(ll) oxide) is then oxidised by the chloraie(I) lo the brown dioxide ... 

Lead(IV) oxide is found to have a considerable oxidising power, again indicating that the oxidation state +2 is generally more stable for lead than oxidation state +4. Concentrated hydrochloric acid, for example, reacts with PbO at room temperature to form lead(II) chloride and chlorine ... 

If this reaction is carried out at 273 K some unstable lead(IV) chloride is initially formed (p. 200). Other oxidising reactions of lead(lV) oxide include the evolution of oxygen when heated with concentrated sulphuric acid ... 

Tin(II) chloride is slowly oxidised in air. but keeping a piece of tin metal in the solution prevents this. 

All carbon compounds, if oxidised by either oxygen or an oxide (such... 

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