savant Lend-Red Batery Halal Reactions ~ [Contents Copyright © 2004 jsd 1 Lead-Acid Battery Half-Cell Reactions ‘The factory makes each cell in the battery as follows: Connected to the “-” terminal is a thick, porous plate of metallic lead. Connected to the “+” terminal is a plate consisting mostly of porous lead dioxide paste, supported ona thin metal grid. In between the plates is fairly concentrated sulfwic acid (about 4M). By way of preliminaries, we note that sulfuric acid is a strong acid with respect to its first proton, so even before the acid has been added to the battery, the following reaction has gone to completion: H)SO, > H* + HSO,” wo ‘This reaction is associated withthe bulk electrolyte, independent of the plates of the battery. It is not an electrochemical reaction and is independent of the charging and discharging of the battery. We do not expect sulfiric acid to release its its second proton with any great likelihood — only a faction ofa percent — since Ka? is only 0.012. As the battery discharges, the following half-cell reaction takes place at the “-” plate: Pb + HSO; — PbSO4 + H* + 2e © @) dis © @@) Q) ‘This reaction makes a lot of sense, As discussed in reference 1, when the cells under load, there is an electric field in the electrolyte that causes negative ions (in this case bisulfite) to drift toward the “-” plate, The negative ion is consumed by reacting with the plate, The reaction also produces a positive ion (proton) which Arifis away under the influence of the aformentioned field. Two electrons are left behind in the plate, to be delivered to the terminal, There’s nothing surprising about any of that As waitten, equation 2 represents the discharge operation. To represent the charge (aka recharge) operation, just reverse the direction of the arrow. The result makes sense, too. Meanwhile, the other half of the discharge reaction takes place at the “+” plate, This can be written in various ‘ways, of which the following is conventional: PbO, +3H™ +HSO, +2e7 — PbSO4 + 2H,0 © @ @) dis) @) Ass, equation 3 is not very easy to understand, as will be discussed in section 2, But frst, let's discuss a few things that do make sense: Ateach plate, the lead compounds are insoluble and stay attached to the plate; there is never any significant amount of lead in solution. The other reaction products (water and sulfuric acid) are completely soluble. ww avn comiphysistond-2. hm 18tors Lesa Baty Halll Reactons ‘These properties are an important part of why the cell is rechargeable. (In contrast, in non-rechargeabke batteries, there are typically reaction products that become unavailable for re-use, departing as a gas or as an insoluble precipitate.) If we add the two halE-cell reactions together, we get the fll-cell discharge reaction: Pb + PbO, + 2H;SO, — 2PbSO, + 2Hy 0 © @ ds © During the discharge operation, acid is consumed and water is produced. During the charge operation, water és consumed and acid is produced. Because sulfuric acid is much denser than water, a widely-used technique for checking the state-of charge ofa battery is to measure the specific gravity of the electrolyte. (Non- ‘experts sometimes guess that the change in density is due to the presence of heavy lead compounds in solution, as ifsome sort of lead-plating reaction were involved, but this is not the case.) During discharge, at the “-” plate, the lead is oxidized from metallic Pb to divalent Pb(II), while at the “+” plate, the lead is reduced from tetravalent Pb(IV) to divalent Pb(II). Of course during recharge, the opposite redox reactions occur Beware of some tricky terminology: ‘© During the discharge operation, the “” plate is called the anode (since the plate material is being oxidized), while the “+” plate is called the cathode (since the plate material is being reduced). ‘© During the charge operation, the “-” plate must now be called the cathode (since the plate material is now being reduced), while the “+” plate must now be called the anode (since the plate material is now being reduced). From this we can conclude that for a rechargeable battery, you should never mark the words “cathode” or “anode” on the terminals, See reference 2 for more about this, inchuding a proper definition of “anode” and “cathode”. 2 Mysteries Itis not easy to understand what sort of microscopic processes are associated with equation 3. Its distressingly hard to look up information about this. A standard book on lead-acid batteries is reference 3, but it doesn’t delve into this issue. Some tantalizing web pages are reference 4 and reference 5. If anybody knows any good references on this subject, please ket me know. In particular, in equation 3 it's not at all clear how or why the bisulfite ion moves uphill (against the gradient of the electrochemical potential) to approach the “+” plate. ‘There are two ways of looking at this: 21 Integral Viewpoint ‘One way to look at this starts by observing that the electrochemical potential is a potential ie. the energy of the bisulfite ion isa function of position, independent of how the ion got to that position. ‘The height of this potential can be considered a “barrier” to the reaction, ws avn comiphysistond-2. hm 218tors LesaAed Baty Hall Reactons In equilibrium, ic. when the cell is open-cireuited, the electrochemical potential is everywhere an. equipotential, i. the height is independent of position. The mystery arises when I place the cell under load, This manifestly shifs the potential, The terminal marked "+" will become less positive, ie. more negative, becoming nattractive to negatively-charged ions. We can calculate the density of fons using the Boltzmann factor, p 0 exp(-E / KD). ‘This can be called the "static" or “integral” view of the situation 2.2 Differential Viewpoint In equilibrium, ic. when the cellis open-circuted, diffusion is the only game in town. Then, when I place the cell under load, there willbe a contest between diffusion and drif, Non-experts may be tempted to imagine a situation where difiusion continues to dominate, but this is not possible, because of the Einstein relation: D=kTb © where D is the diffusion constant for a particular species and b is the mobility for that species. ‘When I place the cell under load, the electric field is sufliciently large that it causes negatively-charged ions to Adrift away from the “+” electrode. Diffusion in the opposite direction will be of only minor significance, leading to depletion of bisulfate ions at the "+" plate, which in tum makes equation 3 appear inconsistent with the commonly-observed properties of the cell. ‘The Einstein relation guarantees that the “integral viewpoint” and the “differential viewpoint” make exactly the ‘same predictions. 3 Other Perspectives We now try to shed some additional light on the mystery, by contrasting cquation 3 with various hypothetical reactions. Among other things, we need to see whether we can wrigele out of the dificuity by finding an acceptable alternative to equation 3 (but alas we will not really find onc), PbO, + Ht +e7 + POOH () (aq) dis (8) © PbO) + 2H" + 2e7 + POH), () @q) dis (8) @ PbO) + H* + 2e7 — PbO +OH™ © dis) (aq) (8) It would be much easier to understand the microscopics of such reactions. For equation 8 in particular, we can re-use the logie that we used for equation 2: A positive ion (proton) drifis in under the influence of the electric field in the electrolyte, and is consumed ina reaction. The reaction produces a negative ion (hydroxy) ww avn comiphysistond-2. hm as