Redox reactions acidic solutions

In order to ensure that both species do not precipitate or form oxo ions during their redox reactions, all. solutions are prepared with fairly concentrated acid, thus causing all of the ionic strengths I to have high values. 

The neutralisation of acids with bases provides many valuable volumetric methods of chemical analysis and redox titrations are useful as well. But here we encounter an important difference between acid/base and redox reactions in solution. Acid/base reactions which involve the transfer of protons are very fast indeed they are usually instantaneous for all practical purposes. In protonic solvents, polar H-X bonds are very labile and undergo rapid proton exchange. For example, if B(OH)3 - a very weak acid - is recrystallised from D20, we obtain a fully-deuterated product. Redox reactions, on the other hand, are often very slow under ordinary conditions. To return to the analogy between acid/base and redox titrations, many readers will be familiar with the reaction between permanganate and oxalic acid the reaction is very slow at room temperature and, for titrimetric purposes, should be carried out at about 60 °C. The mechanism whereby a redox reaction takes place tends to be... 

We have covered a great deal of territory. We discussed the nature of chemistry, the structure of atoms and chemical compounds, and the properties of elements as reflected in the periodic table. We explored fundamental classes of chemical reactions such as redox reactions, acid-base reactions, and displacement reactions. We laid out the theory that describes the nature of the chemical bond and the principles of chemical reactions. We discussed the practical considerations of intermolecular forces and concentration and considered the rarefied properties and reactions of gases. We contrasted the slippery properties of solutions with the concrete properties of solids. We delved into thermo-... 

Equations for redox reactions in solution are best balanced via the appropriate half equations. These are combined in such away as to eliminate the electrons in them. For example, for the dissolution of aluminium in acid, the half equations are... 

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. 

Although this treatment of buffers was based on acid-base chemistry, the idea of a buffer is general and can be extended to equilibria involving complexation or redox reactions. For example, the Nernst equation for a solution containing Fe + and Fe + is similar in form to the Henderson-Hasselbalch equation. 

Balance the following redox reactions, and calculate the standard-state potential and the equilibrium constant for each. Assume that the [H3O+] is 1 M for acidic solutions, and that the [OH ] is 1 M for basic solutions. 

Stannous Sulfate. Stannous sulfate (tin(Il) sulfate), mol wt 214.75, SnSO, is a white crystalline powder which decomposes above 360°C. Because of internal redox reactions and a residue of acid moisture, the commercial product tends to discolor and degrade at ca 60°C. It is soluble in concentrated sulfuric acid and in water (330 g/L at 25°C). The solubihty in sulfuric acid solutions decreases as the concentration of free sulfuric acid increases. Stannous sulfate can be prepared from the reaction of excess sulfuric acid (specific gravity 1.53) and granulated tin for several days at 100°C until the reaction has ceased. Stannous sulfate is extracted with water and the aqueous solution evaporates in vacuo. Methanol is used to remove excess acid. It is also prepared by reaction of stannous oxide and sulfuric acid and by the direct electrolysis of high grade tin metal in sulfuric acid solutions of moderate strength in cells with anion-exchange membranes (36). 

For solvent extraction of a tetravalent vanadium oxyvanadium cation, the leach solution is acidified to ca pH 1.6—2.0 by addition of sulfuric acid, and the redox potential is adjusted to —250 mV by heating and reaction with iron powder. Vanadium is extracted from the blue solution in ca six countercurrent mixer—settler stages by a kerosene solution of 5—6 wt % di-2-ethyIhexyl phosphoric acid (EHPA) and 3 wt % tributyl phosphate (TBP). The organic solvent is stripped by a 15 wt % sulfuric acid solution. The rich strip Hquor containing ca 50—65 g V20 /L is oxidized batchwise initially at pH 0.3 by addition of sodium chlorate then it is heated to 70°C and agitated during the addition of NH to raise the pH to 0.6. Vanadium pentoxide of 98—99% grade precipitates, is removed by filtration, and then is fused and flaked. 

The aqueous solution chemistiy of nitrous acid and nitrites has been extensively studied. Some reduction potentials involving these species are given in Table 11.4 (p. 434) and these form a useful summaiy of their redox reactions. Nitrites are quantitatively oxidized to nitrate by permanganate and this reaction is used in titrimetric analysis. Nitrites (and HNO2) are readily reduced to NO and N2O with SO2, to H2N2O2 with Sn(II), and to NH3 with H2S. Hydrazinium salts yield azides (p. 432) which can then react with further HNO2 ... 

Corrosion or mixed potentials (a) Active corrosion in acid solutions (b) Passive metal in acid solutions Potential dependent on the redox potential of the solution and the kinetics of the anodic and cathodic reactions. Potential dependent on the kinetics of the h.e.r. on the bare metal surface. Potential is that of an oxide-hlmed metal, and is dependent on the redox potential of the solution. Zn in HCI Stainless steel in oxygenated H2SO4... 

Another common type of reaction in aqueous solution involves a transfer of electrons between two species. Such a reaction is called an oxidation-reduction or redox reaction. Many familiar reactions fit into this category, including the reaction of metals with acid. 

Stoichiometric calculations for redox reactions in water solution are carried out in much the same way as those for precipitation reactions (Example 4.5) or acid-base reactions (Example 4.7). 

Many oxidation-reduction reactions (nicknamed redox reactions) take place in aqueous solution. One of these was mentioned in Section 11-2.1 when we characterized acids ... 

The mechanistic assignment of terms in empirical rate laws for complexation and redox reactions of metal ions in aqueous solution acid dependences in perchlorate media. G. Davies, Coord. Chem. 

When we mix two solutions the result is often simply a new solution that contains both solutes. However, in some cases the solutes can react with each other. For instance, when we mix a colorless aqueous solution of silver nitrate with a clear yellow aqueous solution of potassium chromate, a red solid forms, indicating that a chemical reaction has occurred (Fig. 1.1). This section and the next two introduce three of the main types of chemical reactions precipitation reactions, acid-base reactions, and redox reactions, all of which are discussed in more depth in later chapters. (The fourth type of reaction discussed in this text, Lewis acid-base reactions, is introduced in Section 10.2.) Because many chemical reactions take place in solution, particularly in water, in this section we begin by considering the nature of aqueous solutions. 

The following redox reaction is used in acidic solution in the Breathalyzer test to determine the level of alcohol in the blood ... 

The following redox reaction between persulfate ions and chromium ions is carried out in aqueous acidic solution ... 

The concentration of Fe2+ ions in an acid solution can be determined by a redox titration with either KM11O4 or K2Cr207. The reduction products of these reactions are Mir4 and Cr5+, respectively, and in each case the iron is oxidized to Fe3+. In one titration of an acidified Fe2 solution, 25.20 mL of 0.0210 m K2Cr207(aq) was required for complete reaction. If the titration had been carried out with 0.0420 M KMn()4(aq), what volume of the permanganate solution would have been required for complete reaction ... 

Redox reactions of metals with acids are described in Chapter 4. Oxidation of the metal generates hydrogen gas and an aqueous solution of ions. Suppose that 3.50 g of magnesium metal is dropped into 0.150 L of 6.00 M HCl in a 5.00-L cylinder at 25.0 °C whose initial gas pressure is 1.00 atm, and the cylinder is immediately sealed. Find the final partial pressure of hydrogen, the total pressure in the container, and the concentrations of all ions in solution. 

When an alkali metal contacts water, metal atoms donate electrons to water molecules, producing hydrogen gas and a solution of the metal cation (for example, Na ). When a metal such as Ca, Zn, or Fe is treated with a strong aqueous acid, hydronium ions in the acid solution accept electrons from metal atoms, creating cations that then dissolve. We describe these redox reactions in Chapter 4. Zinc metal, for example, reacts with hydrochloric... 

The corrosion of iron occurs particularly rapidly when an aqueous solution is present. This is because water that contains ions provides an oxidation pathway with an activation energy that is much lower than the activation energy for the direct reaction of iron with oxygen gas. As illustrated schematically in Figure 19-21. oxidation and reduction occur at different locations on the metal surface. In the absence of dissolved ions to act as charge carriers, a complete electrical circuit is missing, so the redox reaction is slow, hi contrast, when dissolved ions are present, such as in salt water and acidic water, corrosion can be quite rapid. 

C19-0083. Dichromate ions, C r2 0-j, oxidize acetaldehyde, CH3 CHO, to acetic acid, CH3 CO2 H, and are reduced to Cr . The reaction takes place in acidic solution. Balance the redox reaction and determine how many moles of electrons are required to oxidize 1.00 g of acetaldehyde. What mass of sodium dichromate would be required to deliver this many electrons ... 

C19-0113. Balance the redox reactions between M11O4 and each of the following sulfur-containing species. The final products are and HSO4 and the solution is acidic (a) H2 SO3 (b) SO2 (c) H2 S ... 

Trigonal, metallic selenium has been investigated as photoelectrode for solar energy conversion, due to its semiconducting properties. The photoelectrochemistry of the element has been studied in some detail by Gissler [35], A photodecomposition reaction of Se into hydrogen selenide was observed in acidic solutions. Only redox couples with a relatively anodic standard potential could prevent dissolution of Se crystal. 

---