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4.1 Oxidation Reduction Reactions

Acid-Base equilibrium, complexation equilibrium and solubility equilibrium. These three equilibria have some thing in common, that is there is no change in oxidation state of the species involved in the reaction. In an oxidationreduction reaction, also known as a redox reaction, electrons are not shared, but are transferred from one reactant to another. As a result of this electron transfer, some of the elements involved in the reaction undergo a change in oxidation state. Those species undergoing an increase in their oxidation state are oxidized, while those undergoing a decrease in their oxidation state are reduced. For example, in the following redox reaction between Fe3+ and oxalic acid, H2C2O4, iron is reduced since its oxidation 1 state changes from +3 to +2.

2Fe3+(aq) + H2C2O4(aq) + 2H2O(l) 2Fe2+(aq)+ 2CO2(g)+2H3O+(aq) Oxalic acid, on the other hand, is oxidized since the oxidation state for carbon increases from +3 in H2C2O4 to +4 in CO2. Redox reactions, such as the one shown in the above equation, can be divided into separate halfreactions that individually describe the oxidation and the reduction processes. H2C2O4(aq) + 2H2O(l) 2CO2(g) + 2H3O+(aq) + 2e Fe3+ (aq) + e- Fe2+(aq)

It is important to remember, however, that oxidation and reduction reactions always occur in pairs. This relationship is formalized by the convention of calling the species being oxidized a reducing agent, because it provides the electrons for the reduction half-reaction. Conversely, the species being reduced is called an oxidizing agent. Thus, in reaction given above example, Fe3+ is the oxidizing

Redox reaction: is an electron-transfer reaction. Oxidation: loss of electrons Reduction: gain of electrons. Reducing agent: A species that donates electrons to another species. Oxidizing agent: A species that accepts electrons from another species
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agent and H2C2O4 is the reducing agent.

2.4.2 Electrochemical Cells

An electrochemical cell is a device that permits interconvertion of chemical energy into electrical

Two kinds of Electrochemical cells Galvanic cells( spontaneous) Chemical energy Electrical energy
( non-spontaneous)

energy.

Electrolytic cells (electrolysis)

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Important terms about electrochemical cells(Galvanic Cell)

Standard Electrode Potentials

Because the voltage associated with a given reaction gives a measure of the reactions tendency to take place, it would be useful to have a set of voltage for different half reactions. These could then be combined to give the voltage for large number of redox reactions. Unfortunately, the voltage produced by a single electrode in a cell cannot be measured directly. Solution to the problem is to choose one reference electrode and arbitrarily assign some voltage to it. Then voltages can be assigned to any other electrode merely by measuring the voltage produced by a cell utilizing the electrode in question plus the reference electrode. The reference electrode chosen by international agreement is the standard hydrogen electrode.
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To prevent direct reactionions in eachflow of O.A. To salt bridge circuit bythree R.A. and ions To complete charge of between purposes A balance thethe serves allowing half-cell

e e

e e

Loss of ve charge is cancelled by cations Gain of -ve Electrolytes Zn, Ptor active Inertreplenished anion Mg, etc. or C

Oxidation half-cell

Reduction half-cell Anions

Cations () (+)
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standard hydrogen electrode is constructed with 1mol/L

The standard hydrogen electrode A standard electrode is one in which all reactants and products of the electrode half reaction are in their standard states. The standard state for an ion in a solution is the one for which the activity of the ion is defined as being unity. This is the ion at 1mol/L concentration in an ideal solution (activities approximated by concentrations). The
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HCl solution, hydrogen gas (H2) at 1atm pressure as show in the diagram.

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Figure 5.3 Schematic diagram of the standard hydrogen electrode (SHE).

H2(g) at 1 atm and 298 K Platinum electrode coated with platinum black Solution containing 1M H+(aq) at 298K Outlet for H2(g)

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The potential or voltage arbitrarily assigned to the standard hydrogen electrode is 0 V whether it operates as an anode or cathode. When a cell is constructed with standard hydrogen electrode plus some other standard electrode (all reactants and products in their standard state), the measured potential is assigned solely to the other electrode. Example:1. A standard copper-copper ion electrode is combined with a standard hydrogen electrode to make a cell. The cell voltage is measured as 0.34 V at 25C, and electrons are found to enter the external circuit from the hydrogen electrode. a) Write the cell diagram for the cell 12 b) Write the overall redox reaction of the cell.

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c) What is the potential for the standard copper-copper ion electrode?

Since the electrons leave the cell from the hydrogen electrode, it must be the anode. The cell diagram and reactions are: Pt(s)/H2(g)/H+(aq)//Cu2+/Cu(s) Anode half reaction H2 (g) 2H+ (aq) + 2e-E = 0 Cathode half reaction Cu2+ (aq) + 2e- Cu (s)E = ? H2 (g) + Cu2+ (aq) 2H+ (aq) + Cu (s) E = 0.34V Ecell = Ecathode - Eanode Ecathode = Ecell + Eanode = 0.34 + 0 = 0.34V Since an anode reaction is an oxidation, the potential produced at such an electrode is called oxidation potential. Similarly, the potential produced at a cathode is called reduction potential. Either oxidation potential or reduction potentials could be assembled in a table, but by international agreement the latter are tabulated, as standard reduction potentials.
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After the standard potentials of any electrode have been determined that electrode can be used with another to find its potential. This is how Table of Standard Reduction Potentials can be complied.

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Table of Standard Reduction Potentials can be used for: Predicting the voltage that a given standard galvanic cell would produce. Predicting the spontaneity of a given redox reaction. If the standard electrode potential is positive the redox reaction is spontaneous. Other wise it is non-spontaneous. Comparing the relative strengths of oxidizing and reducing agents. Example: Zn can displace Cu in electrochemical reaction Li can displace Fe in electrochemical reaction
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Redox Equilibrium
Unlike the reactions that we have already considered, the equilibrium position of a redox reaction is rarely expressed by equilibrium constant. Since redox reactions involve the transfer of electrons from a reducing agent to an oxidizing agent, it is convenient to consider the thermodynamics of the reaction in terms of the electron. The free energy, G, associated with moving a charge, Q, under a potential, E, is given by 5.5.1 G = EQ
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Charge is proportional to the number of electrons that must be moved. For a reaction in which one mole of reactant is oxidized or reduced, the charge, in coulombs, is Q = nF 5.5.2 where n is the number of moles of electrons per mole of reactant, and F is Faradays constant (96,485 C mol1 ). The change in free energy (in joules per mole; J/mol) for a redox reaction, therefore, is G = nFE
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where G has units of joules per mole. The appearance of a minus sign in equation is due to a difference in the conventions for assigning the favored direction for reactions. In thermodynamics, reactions are favored when G is negative, and redox reactions are favored when E is positive. 5.5.4 G =G+RT ln Q The relationship between electrochemical potential and the concentrations of reactants and products can be determined by substituting equation 5.5.3 into the equation 5.5.4 nFE =nFE+RT ln Q 5.5.5 where E is the electrochemical potential under standard-state conditions. Dividing through out by nF leads to the well-known Nernst equation.
E = E
o

RT nF

lnQ

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Effect of Concentration on Cell Potential

G =G0 + RTlnQ G0 = -nFE0cell -nFEcell= -nFE0cell + RTln Q

Ecell= E0cell - RTln Q nF Ecell= E0cell - 0.0257ln Q n Ecell= E0cell 0.0592log Q n

Nernst equation: An equation relating electrochemical potential to the concentrations of products and reactants. The standard-state electrochemical potential, E, provides an alternative way of expressing the equilibrium constant for a redox reaction. Since a reaction at equilibrium has a G of zero, the electrochemical potential, E, also must be zero. Substituting into equation 5.5.7 and rearranging shows that
0 ECell =

0.0257 0.0592 ln K = logK n n

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Example: Calculate: 1. the standard-state potential, 2. equilibrium constant and 3. the potential when [Ag+] = 0.020 mol/L and [Cd2+] = 0.050 mol/L, for the following reaction taking place at 25 C.( EAg+/Ag = 0.7996 V, ECd2+/Cd = -0.4030 V) Cd(s) + 2Ag+ (aq) Cd2+ (aq) + 2Ag(s)

Solution: a) In this reaction from the given reactants, which one is oxidized? And which one is reduced? Cd2+ is undergoing oxidation, and Ag+ is undergoing reduction. The standard-state cell potential, therefore, is E = EAg+/Ag- ECd2+/Cd = 0.7996 V-(-0.4030 V) = 1.2026V b) To calculate the equilibrium constant, we substitute the values for the standard-state potential and number of electrons into equation . Solving for K gives the equilibrium constant as log K = 40.6558 K = 4.527 x 1040 c) The potential when the [Ag+] is 0.020 mol/L and the [Cd2+] is 0.050 mol/L is calculated using Nernst equation employing the appropriate relationship for the reaction quotient Q.
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