Chemical Sciences Electrochemistry Industrial Electrochemistry Electrochemical Power Sources There are three significant types of power sources

which produce electricity by reaction within electrochemical cells. The two types which use reactants stored within them are called primary cells and secondary cells. Groups of primary or secondary cells are called batteries, although the term battery has been extended to include also a single cell used as a power source. Secondary cells, unlike primary cells, can be driven in reverse or charged by external electrical power. The third type, fuel cells, employ reactants which are continuously supplied to the cell; products are also continuously removed. In primary and secondary cells, the reactants and products are contained within the cell. Primary Cells Primary cells are electrochemical cells in which a spontaneous electrochemical reaction serves as a source of electrical power. A primary cell is not designed to be recharged after use and must be discarded when its internal supply of reactants is exhausted. Attempts to recharge sealed primary cells can produce explosions because the cells are not designed to withstand the pressure of gases generated within the cell by electrolysis. Primary cells are most useful in providing lowcurrent DC power, particularly when the demand is intermittent. The oldest practical primary cell is the now-obsolete Daniell cell or wet cell which was used to power electrical telegraphs at the turn of the century. These cells consisted of a large glass jar (now called a battery jar) filled

with two solutions of aqueous sulfuric acid. The lower half of the jar was filled with a denser solution of CuSO4 in the acid, while the upper half was filled with the acid alone. A zinc electrode was placed in the upper half of the cell and a copper electrode was placed in the lower half. This cell provided a voltage of about one volt. If the cell was connected constantly and not agitated, the difference in density between the solutions kept them from mixing for months. The overall cell reaction is Zn(s) + Cu2+(aq) --> Zn2+(aq) + Cu(s) in the cell: (-) Zn(s)/Zn2+(aq),H2SO4(aq)//Cu2+(aq),H2SO4(aq)/Cu(s) (+) The common flashlight cell or dry cell is the acidic Zn/MnO2 cell designed by Leclanche' in 1887. The structure of this cell is shown in the Figure below.

Figure is not available. The zinc casing serves as the anode and is consumed in the anodic electrode reaction Zn(s) --> Zn2+ + 2e-; the zinc ion dissolves in the moist ZnCl2-NH4Cl electrolyte. A carbon rod serves as the cathode, but it is chemically inert. The cathodic electrode reaction which consumes MnO2 is best written as: [Mn4+ + 2O2-] + H2O + e- --> [Mn3+ + O2- + OH-] + OHwhere the square brackets indicate the species present in the solid phase at the cathode. The cathode reaction actually occurs within the solid structure; the carbon rod serves only to transfer electrons from the external circuit.

The dry cell has a potential difference of about 1.25 V; the zinc electrode is negative. It is a good source of electrical power and the materials of construction are relatively cheap. The cell voltage during discharge falls off rather badly and the dry cell is not a good source of power when a constant voltage is needed. The alkaline manganese cell, or alkaline cell, is a variant of the dry cell in which the acidic NH4Cl(aq) electrolyte is replaced by a concentrated solution of NaOH. The carbon electrode is replaced by a steel rod or brass tube. In this battery the anode reaction is Zn + 2OH- --> ZnO(c) + H2O + 2e-, since ZnO is insoluble in the alkaline electrolyte solution. Alkaline cells cost two to three times as much as their counterpart dry cells because a more elaborate internal construction is required to prevent leakage of the caustic electrolyte. They do, however, have almost twice the charge capacity and a higher available current. The voltage of alkaline manganese cells is the same as the voltage of dry cells, but under heavy current drain their output voltage decreases less. These advantages have led to their increasing use in battery-powered electronic equipment. The mercury cell, also known as the Ruben cell, was developed in 1947. Its reaction on discharge is Zn(s) + HgO(s) --> ZnO(s) + Hg(l), and it takes place in the cell (-) Zn(s)/KOH,ZnO(s),H2O/HgO(s),Hg(l) (+) Mercury cells are much more expensive to manufacture than are dry cells or alkaline cells. This is due to the high cost of the mercury and mercury (II) oxide they contain. However, the discharge curve of mercury cells is very flat, which is to say that the potentials of mercury cells do not drop off significantly as the cell discharges, and the temperature coefficient of the mercury cells is also less. At 250C the cell

voltage is 1.344 V with the zinc electrode negative. The constancy of the mercury cell voltage makes it useful in sensitive instruments but the high cost prevents its use as a general power source. Other types of primary cells, such as the lithium cell, have been developed for special uses where long life, small size, and very low power are required. Cameras, heart pacemakers, and electronic wrist watches are powered by these cells. Secondary Cells The familiar automobile battery is a group of secondary cells connected in series. A 12-volt automobile battery consists of six leadacid cells in series. Each lead-acid cell is represented as follows: (-) Pb(s)/PbSO4(s),H2SO4(aq)//H2SO4(aq),PbO2(s)/Pb(s) (+) Modern automobile batteries are remarkably rugged in both the physical and electrical sense. A typical automobile battery rated at 54 amperehours can provide currents as high as 300 A for short periods and a continuous drain of 25 A for over two hours. The electrode reaction at the negative electrode of a lead-acid cell is PbSO4(s) + 2e- --> Pb(s) + SO42-(aq), for which E0 = -0.356 V, as measured by Kolthoff in 1931. At the positive electrode the reaction is PbO2(s) + SO42- + 4H+ + 2e- --> PbSO4(s) + 2H2O, for which E0 = +1.685 V, as measured by Harned and Hamer, also in 1931. The standard cell potential difference is then 2.041 V, and the spontaneous direction is for the PbO2 side to be positive. There is therefore in the external circuit a spontaneous electron flow from the lead metal side to the lead dioxide side which means that the spontaneous reaction must be, at the less positive or more negative electrode, Pb --> PbSO4(s),

giving electrons. This is an oxidation process and so this electrode must be the anode. At the more positive electrode, the spontaneous reaction must be PbO2(s) --> PbSO4(s), taking electrons; this is a reduction process and so this electrode must be the cathode. As the battery is being charged, the reaction is forced to proceed in the nonspontaneous direction Pb(II) --> Pb(IV) + Pb(0) and therefore the amount of PbSO4(s) decreases, the amount of H2SO4(aq) increases, the amount of PbO2(s) increases, and the amount of lead metal increases. Another rechargeable secondary cell, used for hand-held devices such as electric razors, is the nickel-cadmium cell (NiCd cell or nicad cell). This cell contains an alkaline electrolyte. The spontaneous reactions on cell discharge at the anode and cathode are to the right: 2NiOOH(s) + 2H2O &lt--> 2Ni(OH)2(s) + Cd(OH)2(s) These reactions take place in the cell (-) steel/Cd(s),Cd(OH)2(s)/LiOH(aq)/NiOOH(s),Ni(OH)2(s)/steel (+) The discharge reactions are reversed when the cell is recharged. A fully charged nicad cell has a potential of about 1.4 V, and the cadmium terminal is negative. Nicad cells are available in standard flashlight cell sizes and can replace them in many applications. Nicad cells do lose stored charge (self-discharge) over a period of a few months and so they are not suitable for very intermittent use. Fuel Cells A fuel cell is an electrochemical cell to which reactants are continually supplied and from which products are continually removed so that there is a continuous production of electrical power. The best known fuel cell,

and the most highly developed, is the hydrogen/oxygen fuel cell known as the Bacon cell, which is used in the United States space program. An idealized drawing of this cell is shown in the Figure below.

The spontaneous reactions in this cell are oxidation of hydrogen at the anode and reduction of oxygen at the cathode: Pt,H2(g) --> 2H+(aq) + e-; E0 = 0.0000 V Pt,O2(g) + 4H+(aq) + 4e- --> 2H2O; E0 = +1.2288 V The overall cell reaction, which yields 1.2288 V under standard conditions, is the formation of water, O2(g) + 2H2(g) --> 2H2O. Cost is a major problem with this cell; pure hydrogen, pure oxygen, and platinum are expensive. The platinum electrodes tend to pick up any trace of impurity in the oxygen or hydrogen and are poisoned by it, so that the cell efficiency is degraded severely. Fuel cells have been suggested as future power sources, because they are not as restricted in efficiency as are power sources based on heat engines. The amount of heat obtainable and work obtainable from a fuel are roughly the same. However, the conversion of heat into work with 100% efficiency is not possible; the maximum efficiency possible depends on the temperature of the input and output heat. Efficiencies of 30 - 40% are commonly found in practice. The theoretical advantage in

avoiding the heat step is about a factor of three, a considerable advantage if electrical power rather than heat is desired.

Example. Suppose we used methanol as a fuel in a fuel cell and in a heat engine. The net reaction in either case would be 2CH3OH(l) + 3O2(g) --> 2CO2(g) + 4H2O(g) DG0 = 2(-394.359) + 4(-228.572) - 2(-166.36) - 3(0) = -1370.29 kJ A total of -685.14 kJ/mole methanol of work are possible. The heat which could be obtained is -638.49 kJ/mole methanol: DH0 = 2(-393.509) + 4(-241.818) - 2(-238.66) - 3(0) = -1276.97 kJ

Practical fuel cells using the oxidation of methane (natural gas) operate at 800oC to 1000oC with a molten carbonate salt serving as the electrolyte. Long-term operation of these cells is compromised by impurities in natural gas which react irreversibly with the molten carbonate electrolyte. For example, sulfur-containing impurities such as H2S are oxidized to sulfate ion which accumulates in the cell electrolyte. [NEXT: Principles of Electrolysis] [PREVIOUS: Introduction to the Nernst Equation] Copyright 1995 James A. Plambeck (Jim.Plambeck@ualberta.ca). Updated May 06, 1997 jp.