Oxidation-reduction reactions spontaneous process

MUTAROTATION The a- and /T forms of monosaccharides are readily interconverted when dissolved in water. This spontaneous process, called mutarotation, produces an equilibrium mixture of a- and /1-forms in both furanose and pyranose ring structures. The proportion of each form differs with each sugar type. Glucose, for example, exists primarily as a mixture of a- (38%) and j8- (62%) pyranose forms (Figure 7.11). Fructose is predominantly found in the a-and /J-furanose forms. The open chain formed during mutarotation can participate in oxidation-reduction reactions. 

Electrochemistry is the branch of chemistry that deals with the interconversion of electrical energy and chemical energy. Electrochemical processes are redox (oxidation-reduction) reactions in which the energy released by a spontaneous reaction is converted to electricity or in which electrical energy is nsed to cause a nonspontaneous reaction to occur. Although redox reactions were discnssed in Chapter 4, it is helpful to review some of the basic concepts that will come np again in this chapter. 

Electrochemistry is best defined as the study of the interchange of chemical and electrical energy. It is primarily concerned with two processes that involve oxidation-reduction reactions the generation of an electric current from a spontaneous chemical reaction and the opposite process, the use of a current to produce chemical change. 

Oxidation-reduction reactions are the basis of the branch of chemistry called electrochemistry. Such a reaction may occur spontaneously and produce electrical energy, as in a galvanic cell. If the reaction does not occur spontaneously, the addition of electrical energy may initiate a chemical change, a process called electrolysis. 

Further examples of optical electron transfer processes are listed in Table 1.1. In some caseswhen reaction is not spontaneous, irradiation in the IT band leads to net oxidation-reduction reactions. In the... 

The opposite of any spontaneous process is a nonspontaneous process. Spontaneous oxidation-reduction reactions can take place in galvanic cells. Their opposites require electrolytic cells to take place. 

An electrochemical cell is a device by means of which the enthalpy (or heat content) of a spontaneous chemical reaction is converted into electrical energy conversely, an electrolytic cell is a device in which electrical energy is used to bring about a chemical change with a consequent increase in the enthalpy of the system. Both types of cells are characterised by the fact that during their operation charge transfer takes place at one electrode in a direction that leads to the oxidation of either the electrode or of a species in solution, whilst the converse process of reduction occurs at the other electrode. 

The energy available from spontaneous cell reactions can be used to power vehicles or generate electricity (Box 12.2). To calculate the standard cell potential for a spontaneous process, we must combine the standard potential of the cathode half-reaction (reduction) with that of the anode half-reaction (oxidation) in such a way as to obtain a positive... 

If a voltaic cell is to run spontaneously, the reduction potential at the cathode must be higher (more positive) than the reduction potential at the anode. This will allow the reaction at the anode to proceed as an oxidation (rather than a reduction). The greater the difference in potentials between the cathode and anode, the greater the cell voltage. Eor E° will be positive for spontaneous processes and negative for nonspontaneous ones. 

The over-all reduction of CO2 to CH4 is expected to be a spontaneous process that goes through the reduction levels of formate, formaldehyde, and methanol with only a limited, perhaps early requirement for activation by ATP. At the lowest reduction stages, extra ATP may even be generated. In the fermentation of methanol by M. barkeri which utilizes only the last reduction step for methane formation (Reaction 12) somewhat more than 1 mole of ATP appears to be generated for each mole of CH3OH oxidized to CO2, judging from cell yields (14). 

In writing the equation this way, we have dropped the subscript cell to indicate that the calculated emf does not necessarily refer to a voltaic cell. Also, we have generalized the standard reduction potentials by using the general terms reduction and oxidation rather than the terms specific to voltaic cells, cathode and anode. We can now make a general statement about the spontaneity of a reaction and its associated emf, E A positive value of E indicates a spontaneous process a negative value of E indicates a nonspontaneous process. We use E to represent the emf under nonstandard conditions and E° to indicate the standard emf. 

The positive value of E indicates that the displacement of silver by nickel resulting from oxidation of Ni metal and reduction of Ag is a spontaneous process. Remember that although we multiply the silver half-reaction by 2, the reduction potential is not multiplied. 

As discussed in Chapter 4, oxidation is the loss of electrons in a chemical reaction, and reduction is the gain of electrons, ooo (Section 4.4) Thus, oxidation-reduction (redox) reactions occur when electrons are transferred from an atom that is oxidized to an atom that is reduced. Redox reactions are involved not only in the operation of batteries but also in a wide variety of important natural processes, including the rusting of iron, the browning of foods, and the respiration of animals. Electrochemistry is the study of the relationships between electricity and chemical reactions. It includes the study of both spontaneous and nonspontaneous processes. 

Zinc metal is oxidized and Cu aq) is reduced in this reaction. These substances are in direct contact, however, so we are not producing usable electrical work the direct contact essentially "short-circuits" the cell. Nevertheless, the driving force for the reaction is the same as that in a voltaic cell, as in Figure 20.5. Because the E°gd value for the reduction of Cu (0.34 V) is more positive than the E°gd value for the reduction of Zn " (-0.76 V), the reduction of Cu aq) by Zn(s) is a spontaneous process. 

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