|
|
|||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
Readings for this sectionPetrucci: Section 3-1, Chapter 20; Introduction 02/09/2006Electrochemistry is the study of interchange of chemical and electrical energy. Oxidation/Reduction involves the exchange of electrons from one chemical species to another. Normally, this is done when the two chemicals contact each other in the activated complex (when two species bump into each other in solution for example). We are interested in separating the chemical species such that the electrons transfer via an external circuit. That way, we can measure the electrochemical effects. To properly understand the connection between the redox reaction and the electricity, we should balance the overall redox reaction using a half-reaction method such as the one described in the previous section of these notes. We can set up the physical reaction vessel such that the chemicals from one half reaction are separated from those of the second half reaction. For reaction to occur, we still need to connect the solutions to complete the circuit. This is done by attaching wires between electrodes in the two half cells and by connecting the solutions of the two half cells via a salt bridge or by some other device such as a semi-permeable membrane.
In general, such a cell is called an electrochemical cell. These cells could be used in one of two types of situations:
We will look at the first situation first. Back to Top
|
|||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
| reduction | Eº/volts | |
|---|---|---|
| 1 | O2 + 4H+ + 4e– ® 2H2O | +1.229 |
| 2 | Ag+ + e– ® Ag | +0.7996 |
| 3 | Cu2+ + 2 e– ® Cu | +0.3419 |
| 4 | Fe2+ + 2 e– ® Fe | –0.447 |
| 5 | Zn2+ + 2 e– ® Zn | –0.7628 |
| 6 | 2H2O + 2e– ® H2 + 2OH– | –0.83 |
| 7 | Na+ + e– ® Na | –2.71 |
| A few years ago, a city experienced a number of very serious water main breaks on sections of pipe that had been recently replaced. The City engineer was fired. His only defence was "How was I to know that brass fittings (mostly copper) on cast iron pipes would corrode so fast." Was the city justified in firing him? Can you explain their reasoning for calling him incompetent? |
Let's look at this small reduction potential table and see if we can use it to explain certain experimentally observable properties of matter. First off, I should point out that the more positive reduction potentials refer to more spontaneous reduction reactions.
The first reaction in this mini-table shows the reduction of oxygen. This is higher in the table than many other things. That makes sense since we know that oxygen is a good oxidizing agent (it makes other things oxidize while it itself is reduced).
We can see that water can be both oxidized (-1) and reduced (2). It is oxidized to oxygen and reduced to hydrogen. These two reactions, in fact, serve as a set of boundaries for aqueous solutions. Any materials harder to oxidize than water will not oxidize since the water will. Similarly, any materials harder to reduce than water will never reduce (in water). For example, sodium ions will never reduce to sodium metal in the presence of water since the water will reduce first. In fact, sodium metal in water will spontaneously (explosively) oxidize to Na+ ions and the water will reduce to hydrogen gas and leave a basic solution (equation 6). The overall reaction for this process is the sum (#6) – 2×(#7).
| NOTE: when we add half-cells, their potentials are strictly additive. We don't multiply or divide by any factors even though we do so to the stoichiometric coefficients of the equations in order to balance the overall equation. Potentials don't depend on the total amount or size of the cell, just the concentrations. You already know this. If you buy a AA cell or a D cell, their voltages are both 1.5V. However, their capacity to do work is not the same. |
2Na + 2 H2O ® 2Na+ + H2 + 2OH–
Thus, the overall standard cell potential for this reaction is
Eºcell = Eºred + Eºox = –0.83 + 2.71 (reverse reaction => change sign) = 1.88 V.
Positive cell potential means spontaneous reaction.
When pairing up metals, we know that zinc will dissolve in a copper (II) solution. Here we see that the copper (II) (3) is easier to reduce than the zinc (II) (5).
Let's now relate the electrochemistry ideas we've explored with the thermodynamic parameter called Gibbs' Free Energy.
We saw,
w = –QE (work = – charge times potential),
where Q is the charge and can be defined as Q = nF where F is the Faraday constant (96485 C/mol), named after Michael Faraday.
In our case, we're interested in the maximum work since this can be related to the thermodynamic parameter DG.
Thus, for the case where the work is done infinitely slowly (chemical system
is always at equilibrium with the electrodes, electrical resistance is zero
since current is essentially zero, etc…) we have
wmax = – QEmax where Emax for
standard conditions is simply E° as calculated from the tabulated
half-cell potentials.
Take for example, a cell with a maximum cell potential of 2.50 V. If 1.33 mol of e– passes through the cell at an average potential E = 2.10 V. What is the efficiency?
w = – Q E = – nFE. = 1.33 mol × 96485 C/mol × 2.10 V (V = J/C)
w = – 2.69 × 105 J = – 269 kJ
wmax = – nFEmax = 1.33 mol × 96485 C/mol × 2.50 V
= – 321 kJ
efficiency = w/wmax × 100% = –269/–321 × 100% = 83.8 %
Of course, since wmax is only achievable if the work is done reversibly (infinitely slowly), we can never reach 100% efficiency in any system in the real world.
We already have seen that DG is a measure of the maximum work obtainable from a system. Thus,
DG = wmax
DG = – Q E
DG = – nFE. In this case, the potential is the cell potential Ecell.
DG° = – RT lnK = – nFE°cell.
Thus, we now have a link between free-energy, equilibrium and electrochemical thermodynamic parameters.
Example:
Is Fe2+ spontaneously oxidized by the oxygen of the air in acidic solution? Calculate DG and K.
Two half-reactions can be determined by looking in the table of standard reduction potentials.
| Oxidation of iron: | 4[Fe2+ ® Fe3+ + e– ] | –E°ox = –0.77 V |
|---|---|---|
| Reduction of O2 | O2 + 4H+ + 4e–
® 2 H2O |
E°red = 1.23 V |
| Overall: | 4Fe2+ + O2 + 4H+
® 4Fe3+ + 2H2O n = (4 mol electrons / mol equation) |
E°cell = 0.46 V (Positive means spontaneous®) |
DG = –nFE°cell = – 4 mol × 96485 C/mol × 0.46 V = – 1.8×105 J = –180 kJ (per mole of reaction)
![]()
K = e72.7 = 3.7×1031.
SUMMARY
|
Gibbs |
Q vs. K |
Cell potentials |
Spontaneous direction |
|---|---|---|---|
|
DG < 0 |
Q < K |
Ecell > 0 |
® |
|
DG = 0 |
Q = K |
Ecell = 0 |
Equilibrium |
|
DG > 0 |
Q > K |
Ecell < 0 |
¬ |
Consider the following set of half-reactions
| Reduction | Fe2+ + 2e–
|
E°red = –0.44 V |
|---|---|---|
| Oxidation | Zn |
E°ox = +0.76 V |
| Overall | Zn + Fe2+
|
E°cell = 0.32 V |
This is valid only if all species have concentrations of 1 M.
What if not all the species are at Standard Conditions?
Le Châtelier's principle gives us some ideas. Look at the overall reaction. Consider the reaction to be at equilibrium (Ecell = 0 V). If we add more Fe2+ to the reaction mixture, The equilibrium will shift to the right to use up the excess Fe2+. This will, of course cause a positive cell potential to be measurable.
Conversely, if we removed Fe2+ from the reaction mixture, the equilibrium would shift to the left to try to replace some of the missing Fe2+. This would result in a measurable negative potential (reaction goes left).
If the reaction were not at equilibrium then these preceding two changes would me additive to the measured voltage (say standard voltage). So, if we add Fe2+ to a mixture at Standard Conditions, then the voltage would be more positive and if we removed some Fe2+ from a mixture at Standard Conditions the measured voltage would be lower (less positive).
The reverse results would be found for addition or removal of Zn2+ (a product). More Zn2+ would give a lower positive potential and vice versa.
Now we try to quantify the previous hand-waving discussion.
Recall the relation: DG = DG° + RT ln Q (for non-standard conditions)
Substitute the new definition of DG and we get
–nFE = –nFE° + RT ln Q
(This
is called the Nernst Equation).
Thus, we can calculate the cell potential of any cell, given only the initial conditions (to calculate Q) and the reduction potentials (to calculate E°).
Now, looking back at the reaction cell discussed at the beginning of this section we can calculate the voltage for the situation where the concentrations are not standard. For example, consider [Fe2+] = 0.1 M and [Zn2+] = 1.9 M.
For this reaction, we also know that there are two electrons transferred for each equation (n = 2).
Although the reaction is 90% complete (from Standard Conditions initial) the cell potential has only dropped by a small amount (0.04 V). This is normal. For example, the batteries in your flashlight will put out almost full voltage until the last traces of chemical are almost used up at which point the voltage will drop off rather sharply. This is an especially useful characteristic of cells powering electronic equipment, (like a calculator or CD player, etc.) which require a certain minimum (and dependable) voltage to operate successfully.
We can also use the Nernst equation to calculate such things as equilibrium constants.
At equilibrium, Q = K and Ecell = 0 so the Nernst equation becomes
or
Example:
What is the equilibrium constant for the reaction of copper metal with bromine to form copper(II) ions and bromide ions in aqueous solution at 25°C?
| Cathode | Br2 + 2e–
|
E°red = 1.09 V |
|---|---|---|
| Anode | Cu |
E°ox = –E°red
= –0.34 V |
| Cell | Cu + Br2
|
E°cell = 0.75 |

Example:
What is the value of the solubility product constant for AgCl?
We could calculate this by breaking the overall Ksp reaction into a series of redox reactions as follows:
| Anode | Ag(s) ® Ag+ + e– | E°ox = –0.80 V |
|---|---|---|
| Cathode | AgCl + e–
® Ag(s) + Cl– |
E°red = 0.22 V |
| Overall (º Ksp reaction) |
AgCl
|
E°cell = –0.58 V (not very spontaneous) |

K = 6.3 × 10-9
Ion Concentrations can also be calculated...
Consider the Platinum-Hydrogen electrode coupled with a copper/copper(II) electrode.
The overall reaction is Cu2+ + H2 ® Cu + 2H+.
The Nernst equation is


If [Cu2+] = 1 M and P(H2) = 1 bar (both their activities are 1) then
![]()
E = E° – 0.0257 V ln [H+] (Note: ln Y = 2.303 × log Y and .-257×2.303=.05917)
E = E° + 0.05917 V (–log [H+])
E = E° + 0.05917 V × pH.
We see here that the cell potential is a function of pH. The probes in pH meters are set up this way. A complete electrochemical cell is contained within the probe casing. All chemicals are at standard conditions and a porous glass membrane allows only H+ ions to pass through. The diagram of the set-up is given here.

A concentration cell is one in which the half-reactions in the two half cells are identical but the concentration of the ions is different. In this case, the reduction and the oxidation half reaction are identical. Take for example a concentration cell where both half cells have an iron electrode in a Fe2+ solution. We would have the following:
Consider the following set of half-reactions
| Reduction (half-cell 1) | Fe2+ + 2e–
|
E°red = –0.44 V |
|---|---|---|
| Oxidation (half-cell 2) | Fe |
E°ox = +0.44 V |
| Overall | Fe + Fe2+
|
E°cell = 0.00 V |
if all concentrations are identical (or if they are all standard) then obviously the cell voltage is zero. If, however there is a different concentration on one half cell than on the other one, we could use the nernst equation to calculate, for example the cell potential.
| E = E° – RT/nF ln Q |
NOTE: Q = a(Fe2+)2/a(Fe2+)1
Where the subscripts 1 and 2 refer to half-cells 1 and 2 NOTE: E° = 0.00 |
| E = RT/nF ln {a(Fe2+)2/a(Fe2+)1} | Normally, we set the concentration of half-cell 1 to be fixed (at say, activity=1) and vary the the activity of the Fe2+ in half-cell 2. |
| E = RT/nF ln a(Fe2+)(in half-cell 2) | if a (Fe2+)1 = 1 |
The Nernst equation can also be used to calculate half-cell potentials. In this case, Q is simply the ratio of ions of the half-cell equation rather than the full-cell and the value for E° is that of the half-cell. No other changes to the equation are made.
There are three classes of batteries:
| Primary Cells | Chemical reaction occurs irreversibly. The
battery cannot be recharged. This can happen for several reasons, including
the chemical properties and the design of the cell. Examples include
standard Alkali batteries or their less common precursors the carbon/zinc
battery.
Leclanché cell (improperly called Zinc-Carbon dry cell) This is the common dry-cell available in most stores that we use to power
toys and flashlights. These involve a zinc casing (anode) and a carbon
rod in the centre (cathode) with a paste of MnO2, NH4Cl,
ZnCl2 and graphite.
Notice that the products can slowly build up in this type of cell and cause the overall cell potential to drop. Alkaline cell (alkaline meaning basic) In the alkaline cell, the product of the cathode reaction is used up again in the anode reaction, no build up of products means the voltage drops (as water is used up) more slowly than the previous cell. Since the cell voltage is also about 1.5 V, this alkaline dry cell can be used in the same devices as the normal dry cell. Notice, the only real difference between these is the fact that the reaction in this case occurs in a basic medium.
Ruben-Mallory (mercury) cell This type of cell is used in application where the cell potential must remain very constant over the life of the battery (commonly computers and watches, etc). The products and reactants are all pure substances (standard state). Since the voltages of these cells are not the same as the previous two, this type of battery is not interchangeable with the first two types.
|
||||||||||||||||||||||||||||||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| Secondary Cells | Chemical reaction is reversible. The battery
can be recharged. Examples include NiCd batteries and Lead/acid batteries
found in cars. These are also called storage cells or rechargeable cells. In
theory, alkaline batteries can also be recharged, the process, however is
dangerous and can lead to explosions if not done with the proper equipment.
Similarly, lead/acid car batteries can explode if they are charged too fast
but for a different reason. Lead/acid battery has an overall reaction of
Nickel/Cadmium batteries have reactions
.We see that none of the reactants or products are in solution so the
voltage will remain very constant during the discharge period.
Unfortunately, the cell voltage is lower than standard dry cells and are not
always interchangeable. |
||||||||||||||||||||||||||||||||||||
| Fuel Cells | Reactants are flowed through the cell. This is an irreversible reaction but by refilling the reservoir of fuel the cell can be reused. The space shuttle uses this type of battery to run much of its electrical equipment. | ||||||||||||||||||||||||||||||||||||
We've seen how spontaneous reactions can be harnessed to produce electricity. In electrolytic cells, electricity is used to force non-spontaneous reactions to proceed. Electrolysis is used to prepare certain compounds and metals. Products of electrolysis are found in every day life: Chrome plated bumpers, Silver and gold plating on some inexpensive jewellery, among other things.
In setting up an electrolysis cell, we must take into account all possible reactions and make sure the conditions are set so that the desired reaction occurs. We will do this at first by using only inert electrodes and then by using pure electrolyte liquids rather than aqueous (or other) solutions.
We will use a non-aqueous system such as molten NaCl as our medium, and non reactive electrodes like platinum. We can successfully separate out pure Na. Consider the following electrolytic cell.
This is a very important method of producing sodium metal. At the anode, Cl2
is evolved in the reaction
2Cl– ® Cl2(g)+ 2e–.
At the Cathode, the molten sodium ions are converted to sodium metal (liquid
at these temperatures) in the reaction
Na+ + e– ® Na(l).
Alkali earth metals which are also highly reactive can be prepared using electrolysis of molten chloride salts as in the reaction MgCl(l) ® Mg(l) + Cl2(g)
Other metals which are not quite as reactive as the above two families but are sufficiently reactive that they cannot be produced in an aqueous cell can be produced this way. Aluminum is one such metal.
The Hall process invented before the turn of the century allowed for the production of aluminum on an industrial scale.
A molten mixture of aluminum ore (Al2O3) and cryolite (Na+)3(AlF6–)(l). The cryolite is the solvent and it is used because it has a lower melting point than pure Al2O3. A carbon electrode acts as the anode and aluminum forms the cathode such that the following reactions occur:
Al3+ + 3e– ® Al(l)
C(s) + 2O2– ® CO2(g) + 4e–
This process needs lots of electricity per kg of aluminum so you will most commonly find aluminum production plants very close to electric power stations to reduce the cost of electricity.
Consider the reaction in the molten NaCl electrolysis cell.
2Cl– ® Cl2(g) + 2e–. 2 moles of electrons per mole of Cl2(g) Na+ + e– ® Na(l). 1 mole of electrons per mole of Na metal Recall that the charge on the electron is Q = nF where F is the Faraday constant (96485 C/mol), named after Michael Faraday.
Thus, to produce one mole (23 g) of sodium, we need Q = 1×96485 C = 96500 C.
To produce one mole (70.9 g) of chlorine gas, we need 2×96500 = 1,930,000 C.
Current is defined as the amount of charge passing a point in a circuit in one second.
I = Q/s The units are 1 Ampere = 1 Coulomb/second (1A = 1C/s).
Now, if we have a current of 50.0 A passing through an NaCl(l) electrolysis cell in 1 hour, how much sodium and chlorine will we produce.?
50.0 A × 3600 s = 180,000 C (NOTE: 1As = 1C)
n = Q/F = 180,000/96,485 = 1.87 mol e–
It takes lots of current to produce very little sodium and chlorine.
We can do other types of calculations similar to this.
What mass of aluminum will be produced in 1.00 h by electrolysis of Molten AlCl3 using a current of 10.0 A?
Q = I×t = 10.0 A × 3600 s = 3.60×104 C.
It takes three moles of electrons for every mole of Aluminum. So...
n = Q/F = 3.60×104 C / 96485C/mol e– ×1/3 × 27.0 g/mol = 3.36 g Al.
What volume of Cl2(g) at STP (0°C, 1 atm) will be produced by a current of 20.0 A in 2.00 h in the same cell as used in the previous example?
Note that in this problem, we used
R=0.08206 Latm/mol K.This was to facilitate the conversion to volume. You could have also used the more standard value of R=8.314 J/mol K but conversion to volume would have involved one more step of calculations.
If we had tried to electrolyse sodium Chloride in water, we would need to consider not only the Na+ and Cl– as possible reactants but also the water. We can never produce sodium in aqueous solution, because it will spontaneously react with the water to produce Na+(aq). Whether we tried to produce sodium metal either chemically or electrolytically, the chance of success would be equally bad. Thus, at the cathode of an aqueous NaCl cell, we would get the reduction of water happening
2H2O + 2e– ® H2 + 2OH– E°red = –0.83 V
rather than the reduction of the sodium
Na+ + e– ® Na E°red = –2.71 V
Notice that the reduction potential for the water reduction is a lot more positive than that for the sodium. This is a way we can look up reduction potentials and tell what will happen in our solution before hand.
Looking at the two possible reactions at the anode of the NaCl (aq) cell, we see that the Cl– and the H2O are both candidates for oxidation. The two possible half-reactions are:
2H2O ® O2 + 4H+ + 4e– E°ox = –E°red = –1.23
2Cl– ® Cl2 + 2e– E°ox = –E°red = –1.36
Since the water has a more positive oxidation potential than the chlorine reaction, it should be oxidized more readily. There is a complication, however. The water oxidation requires a considerable over-voltage (extra voltage) to make the reaction rate appreciable. Since the two possible reactions are quite close in potentials the extra voltage can quickly be sufficient to cause the chlorine oxidation to occur. Since this latter reaction is quite rapid in comparison to the water ® oxygen one, it will dominate at only slightly elevated voltages.
If we had used Na2SO4 rather than NaCl as the electrolyte, then the anode reaction would have been the water one since SO42– is very difficult to oxidize (very negative oxidation potential in comparison to water).
Consider the electrolysis of Copper(II)sulfate solution.
We find O2 produced at the anode and copper solid deposited at the cathode. This means, as we saw before that the water is more easily oxidized (to oxygen) than are the sulphate ions while the copper(II) ions are more easily reduced (to copper metal) than is water (to hydrogen). Hence, it is quite easy to set up an electrolytic purification process for copper metal. Unlike aluminum, where we needed molten baths of aluminum ore, we need only dissolve the copper in a water solution and then electrolyse it out as copper metal. If we do a crude separation chemically of the copper from the ore, we can use this impure copper as the anode and use pure copper as the cathode. Then, we will electrolyse copper ions off of the impure copper anode and then reduce them onto the pure cathode in the same solution. Impurities in the anode would merely settle to the bottom of the cell to be disposed of. We need to take care to adjust the voltage so that only the copper is oxidized from the anode and not some of the impurities. This done, we can successfully purify copper using electrolysis. The slower we take the reaction (less over voltage) the more pure will be the copper.
We've seen that the particular product of electrolysis we see at the electrodes depends on the ease of production of that particular species. There are three factors that determine product that we will find in any given electrolysis cell: the electrode material, the solvent and the electrolyte. Often, we use inert electrodes and/or pure liquids to help alleviate some of the complications from competing chemistry, other times, we must simply carefully adjust conditions (concentrations and voltages) to ensure that the desired product is achieved.
| @ Cathode | Reduction of substances most easily reduced
will be the one observed. For example, Na+, Ca+, Al+ all have more negative reduction potentials than water so they will not be reduced in aqueous solutions On the other hand, Cr3+, Cu2+, Ag+ have reduction potentials more positive than that for water so they will be preferentially reduced at the cathode. |
|---|---|
| @ Anode | Oxidation of substances most easily oxidized
will be observed. For example, Br–, I– will be oxidized but F– and Mn2+ will not. (check reduction potentials) |
Complication: Cl– we've seen to be more easily oxidized than water even though it has an oxidation potential (negative of the reduction potential for Cl2) which is more negative than that for water. This is due to kinetics. The water reaction is quite slow and requires a large voltage to force it to proceed with any speed. The Cl– oxidizes to Cl2 much more rapidly and the over voltage we apply in an attempt to force the water to oxidize is sufficient to produce Cl2 which occurs faster.
Summary:
| Reaction involves: | Anode | Cathode | |
|---|---|---|---|
| 1 | Electrolyte | Anions oxidized | Cations reduced |
| 2 | Solvent | Solvent oxidized | Solvent reduced |
| 3 | Electrode | Electrode oxidized | Electrode reduced |
We've seen that the oxygen from the air can be reduced to water and that the reduction potential for this half-reaction is very positive. More positive, in fact than that for most metal reduction process. This means that any metal in contact with oxygen from the air and in the presence of an electrolyte solution will oxidize. Since mining and production of metal is a fairly energy-intensive process, it is very useful to be able to find ways to reduce or eliminate the oxidation of these metals if at all possible. There are several ways to reduce oxidation of metals
