Predictions oxidation-reduction reactions

Oxidation-reduction reactions must be balanced if correct predictions are to be made. Just as in selecting a route for a trip from San Francisco to New York, there are several ways to reach the desired goal. Which route is best depends to some extent upon the likes and dislikes of the traveler. We will discuss two ways to balance oxidation-reduction reactions—first, using half-reactions and, next, using the oxidation numbers we have just introduced. 

In Sec. 13.2 we will learn to determine oxidation numbers from the formulas of compounds and ions. We will learn how to assign oxidation numbers from electron dot diagrams and more quickly from a short set of rules. We use these oxidation numbers for naming the compounds or ions (Chap. 6 and Sec. 13.4) and to balance equations for oxidation-reduction reactions (Sec. 13.5). In Sec. 13.3 we will learn to predict oxidation numbers for the elements from their positions in the periodic table in order to be able to predict formulas for their compounds and ions. 

Oxidation—reduction reactions, commonly called redox reactions, are an extremely important category of reaction. Redox reactions include combustion, corrosion, respiration, photosynthesis, and the reactions involved in electrochemical cells (batteries). The driving force involved in redox reactions is the exchange of electrons from a more active species to a less active one. You can predict the relative activities from a table of activities or a halfreaction table. Chapter 16 goes into depth about electrochemistry and redox reactions. 

The activity series has long been used to predict the direction of oxidation-reduction reactions. Consider, for example, the oxidation of Cu by metallic zinc that we have mentioned previously. The fact that zinc is near the top of the activity series means that this metal has a strong tendency to lose electrons. By the same token, the tendency of Zn to accept electrons is relatively small. Copper, on the other hand, is a poorer electron donor, and thus its oxidized form, Cu, is a fairly good electron acceptor. We would therefore expect the reaction... 

Processes which involve oxidation (the loss of electrons or the gain of relative positive charge) and reduction (the gain of electrons or the loss of relative positive charge) are typical of these reactions. Use of Table 8.1, the activity series of common metals, enables chemists to predict which oxidation-reduction reactions are possible. A more active metal, one higher in the table, is able to displace a less active metal, one listed lower in the table, from its aqueous salt. Thus aluminum metal displaces copper metal from an aqueous... 

One of the main purposes for using oxidation numbers is to follow the movement of electrons during an oxidation-reduction reaction. Doing so helps to predict the products and determine the outcomes of such reactions. There are a few different ways to analyze redox reactions, but we will focus on only one the ion-electron method (also called the half-reaction method). The procedure requires that you know the reactants and products of the reaction, but, by going through the process, you will gain a better understanding of the mechanisms by which these reactions proceed. 

REDOX REACTIONS IN GALVANIC CELLS When discussing oxidation-reduction reactions we have not mentioned ways in which the directions of such reactions can be predicted. In other words, discussions in the previous chapters were aimed at understanding how oxidation-reduction reactions proceed, but there was no mention of why they take place. In this and the next few sections the problem will be dealt with in some detail. 

In Chapter 5, we learned to write formulas for ionic compounds from the charges on the ions and to recognize the ions from the formulas of the compounds. For example, we know that aluminum chloride is AICI3 and that VCI2 contains ions. We cannot make comparable deductions for covalent compounds because they have no ions there are no charges to balance. To make similar predictions for species with covalent bonds, we need to use the concept of oxidation number, also called oxidation state. A system with some arbitrary rules allows us to predict formulas for covalent compounds from the positions of the elements in the periodic table and also to balance equations for complicated oxidation-reduction reactions. 

It is important to know redox potentials of elements if one wants to predict the directions of oxidative-reductive reactions between different oxidation states of elements. If E for individual elements or semireactions are known, then the total redox potential of the system can be obtained by combining the equations that incorporate these elements or semireactions. The reactions occur when this potential is positive. 

We now discuss chemical reactions in further detail. We classify them as oxidation-reduction reactions, combination reactions, decomposition reactions, displacement reactions, and metathesis reactions. The last type can be further described as precipitation reactions, acid-base (neutralization) reactions, and gas-formation reactions. We will see that many reactions, especially oxidation-reduction reactions, fit into more than one category, and that some reactions do not fit neatly into any of them. As we study different kinds of chemical reactions, we will learn to predict the products of other similar reactions. In Chapter 6 we will describe typical reactions of hydrogen, oxygen, and their compounds. These reactions will illustrate periodic relationships with respect to chemical properties. It should be emphasized that our system is not an attempt to transform nature so that it fits into small categories but rather an effort to give some order to our many observations of nature. 

In combination reactions, two substances, either elements or compounds, react to produce a single compotmd. One type of combination reaction involves two elements. Most metals react with most nonmetals to form ionic compounds. The products can be predicted from the charges expected for cations of the metal and anions of the nonmetal. For example, the product of the reaction between aluminum and bromine can be predicted from the following charges 3-1- for aluminum ion and 1— for bromide ion. Since there is a change in the oxidation numbers of the elements, this type of reaction is an oxidation-reduction reaction ... 

An excellent energy match between the base s HOMO and the acid s LUMO leads to adduct formation with a coordinate covalent bond. More disparate energy gaps between the frontier orbitals can result in oxidation-reduction reactions initiated by electron transfer from the base to the acid. While this model must be considered in concert with other considerations (most notably thermodynamics) to predict the fate of potential reactants, the frontier orbital perspective provides a conceptual framework for analyzing reactions. 

The great simplification introduced by this procedure can be seen by examining Table 11-1. This table contains only 56 entries, which correspond to 56 different electron reactions. By combining any two of these electron reactions the equation for an ordinary oxidation-reduction reaction can be written. There are 1540 (56 x- ) of these oxidation-reduction reactions that can be formed from the 56 electron reactions. The 56 numbers in the table can be combined in such a way as to give the 1540 values of their equilibrium constants accordingly, this small table permits a prediction to be made as to whether any one of these 1540 reactions will tend to go in a forward direction or the reverse direction. 

Predicting the Spontaneous Direction of an Oxidation-Reduction Reaction... 

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