ELECTROCHEMISTRY Chapter 1

Introduction Electrochemistry 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: 1. The chemical reaction is spontaneous and produces electricity.

This is called a voltaic cell or a galvanic cell. 2. The chemical reaction is non-spontaneous and is forced by electricity from an external This kind of cell is called an electrolysis cell. source.

Galvanic or Voltaic cells Consider a piece of zinc foil placed in a beaker of copper sulphate. The copper sulphate solution is blue because of the presence of the Cu2+ ions. When the zinc is added, the solution changes to colourless and the zinc metal is dissolved and replaced by a reddish orange powder. The colourless solution no longer has Cu2+ in it and the reddish orange powder is Cu(s). The Zn(s) is dissolved and is now Zn 2+. [I know this because of my vast knowledge of chemistry ;-)] If we write an overall reaction for this process, we get: Zn + Cu2+ Zn2+ + Cu. This doesn't help us in our quest for electrochemistry knowledge. Let's rewrite this in half-reaction form. Zn Zn2+ + 2e Cu2+ + 2e Cu Now, we can set up two half cells, one with a zinc electrode in a Zn2+ solution (say ZnSO4) and the other with a copper electrode in a Cu2+ solution (say CuSO4) as follows.

The centre line in the diagram, recall, is either a semi-permeable membrane or a salt bridge. Now, at the anode, we have the reaction Zn(s) Zn2+(aq) + 2e(aq) and at the cathode, we have Cu2+(aq) + 2e(aq) Cu(s) Electrons pass through the wires and SO42 pass through the membrane to keep the solutions neutral.

Cell Potentials Electrons from solution pushed onto the anode, around the external circuit and onto the cathode where they are pulled out into the solution. That's one way of thinking of the electrical circuit part of the electrochemical cell. The electrons pushed around the external circuit can do work. The amount of work possible is a function of both the voltage (potential) and of the current (number of electrons) in the circuit. Pushing one Coulomb of charge around a circuit at a potential of 1 Volt does One Joule of work. OR, mathematically, 1J = 1V 1C. The cell potential (voltage of the cell) depends on the chemicals used. For example, the chemicals in dry-cells (batteries) are such that the potential is always about 1.5 V. This has become a standard and is now a limiting factor in deciding which chemicals can be used to create a battery. The cell potential is given a symbol of Ecell. If all chemicals are at activity of 1 (conc. = 1 M, p = 1 bar) then the cell potential is the standard cell potential and is given as Ecell. Any redox reaction has the potential (pun) to be used in an electrochemical cell. We merely need to be able to divide the oxidizing and reducing agents into two half cells (half reactions). Take for example, the reaction of zinc metal dissolving in hydrochloric acid. The reaction is: Zn(s) + 2H+(aq) Zn2+(aq) + H2(g) We need to separate the zinc from the hydrogen. We can use zinc as an electrode but what about the hydrogen. In this case, we need to set up a special electrode, which allows H 2 gas molecules to interact directly with H+ dissolved in water and with the electrons from the external circuit simultaneously. Such a system is pictured below.

A blow-up of the surface of the platinum electrode is shown below so the location of reaction can be better understood.

The other half-cell would look much like that pictured in a previous diagram. The whole cell diagram, of course would include the external part of the circuit and the salt bridge or membrane to complete the circuit. We can abbreviate this diagram as follows: Zn(s)/ZnSO4(aq)//H2SO4(aq)/H2(g),Pt(s) [Anode Where the single slash mark

//

Cathode]

/ represents the boundary between solution and electrode

and the double slash // represents the salt bridge or semi-permeable membrane. The external circuit, of course, joins the two electrodes (solid) and is not explicitly shown here. The overall cell voltage can be summed from the half-cell potentials of the oxidation and of the reduction reactions. Ecell = ERed + Eox.

Standard Reduction Potentials

As before, we wish to tabulate thermodynamic data in some useable way. We define a standard set of conditions under which all half-reactions can theoretically operate and we tabulate the half-cell potentials for the reactions under standard conditions. Since the potential of an oxidation reaction (loose electron) is merely the negative of the potential for a reduction reaction reaction (gain electron), we choose to tabulate only the reduction half-reactions. Any oxidation half reactions are merely the reverse of the tabulated reduction reaction and the oxidation potential is the negative of the tabulate reduction potential.

Reduction potentials of half cell reactions 1 2 3 4 5 6 7 Reduction O2 + 4H+ + 4e 2H2O Ag+ + e Ag Cu2+ + 2 e Cu Fe2+ + 2 e Fe Zn2+ + 2 e Zn 2H2O + 2e H2 + 2OH Na+ + e Na E/volts +1.229 +0.7996 +0.3419 0.447 0.7628 0.83 2.71

The first reaction in this 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 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). 2Na + 2 H2O 2Na+ + H2 + 2OH Thus, the overall standard cell potential for this reaction is Ecell = Ered + Eox = 0.83 + 2.71 = 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).

Gibbs' Free Energy and Cell potential 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 G. 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 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.

(V = J/C)

We already have seen that G is a measure of the maximum work obtainable from a system. Thus, G = wmax G=QE G = nFE. In this case, the potential is the cell potential Ecell. G = RT lnK = nFEcell.

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 G and K. Two half-reactions can be determined by looking in the table of standard reduction potentials. Oxidation iron: Reduction O2 Overall: of 4[Fe2+ Fe3+ + e ] of O2 + 4H+ + 4e 2 H2O 4Fe2+ + O2 + 4H+ 4Fe3+ + 2H2O n = (4 mol electrons / mol equation) Eox = 0.77 V Ered = 1.23 V

Ecell = 0.46 V (Positive means spontaneous)

G = nFEcell = 4 mol 96485 C/mol 0.46 V = 1.8105 J = 180 kJ (per mole of reaction)

K = e72.7 = 3.71031.

SUMMARY Gibbs G<0 Q vs. K Q<K Cell potentials Ecell > 0 Spontaneous direction

 G=0 G>0

Q=K Q>K

Ecell = 0 Ecell < 0

Equilibrium