Electrochemistry

Electrochemistry is the study of the relationship between chemical reactions and electrical work. Galvanic cells are cells where chemical reactions give rise to electrical energy. Electrolytic cells are cells where a supply of electrical energy is converted into chemical energy. Galvanic cells chemical energy electrical energy When a metal is immersed in a solution of its ions, two possible electron transfer reactions can take place:

At equilibrium, there is a potential difference between the metal and an aqueous solution of its ions called its electrode potential. This arrangement is called a half-cell. The electrode potential of a metal depends on its : -temperature and pressure -nature of the metal -concentration of its ions. The absolute electrode potential of a metal cannot be measured. We have to compare the previous half-cell to another half-cell , called the hydrogen half-cell, and measure the potential difference between the two half-cells using a voltmeter. A standard hydrogen electrode or standard hydrogen half-cell is the half-cell represented by the equation:

Under standard conditions. Standard conditions refer to: Temperature of Pressure of any gas involved is Concentration of any ion involved is The standard hydrogen electrode consists of a platinum electrode dipped into H+ ions with pure H2 gas bubbling over it under a pressure of 1 atm and at 298K. 1

Arbitrarily, the standard electrode potential for this system E (H+/H2) is assigned a value of The standard electrode potential (E ) of a half-cell is the potential difference between this half-cell and the standard hydrogen electrode, measured under standard conditions.

To measure the standard electrode potential of Zn The standard zinc half-cell is connected to the standard hydrogen half-cell by a salt bridge, which contains K+NO3- ions. The salt-bridge completes the circuit by allowing the passage of charged ions between electrodes but physically separating the two half-cells. There is a voltmeter. The cell registers its max. Potential difference, which is called the emf of the cell. In this case, Ecell at 298K is found to be 0.76V. The standard electrode potential E , for Zn2+/Zn is -0.76V. The reactions at the electrodes are : oxidation Reduction Giving an overall cell reaction:

When an electrode is connected to the standard hydrogen electrode: E >0, reduction is taking place at the electrode. E <0, oxidation takes place at the electrode. On the left hand side of the equation, it is the placement of the oxidised species and the electrons, on the right hand side of the equation, it is the reduced species. Electrons are on the left. The electrochemical series is also called the redox potential series. It is an activity series in which the metals are placed in order of increasing electrode potential. The more reactive metals are placed higher in the series. The more reactive the metal, the greater is its tendency to react and to form positive ions, therefore more negative E value. A large positive value of E indicates a high likelihood of reduction, a high likelihood of the above reaction proceeding from left to right. A large negative value of E indicates a high likelihood of oxidation, a high likelihood of the above reaction proceeding from right to left. 2

If a half-equation is multiplied by a number, E value stays the same. If you reverse a half-equation, the E value is inverted. A galvanic cell showing a Zn2+/Zn half-cell connected to a Cu2+/Cu half-cell.

Data :

When given two reduction half-reactions, the reduction half-reaction with the more positive E always takes place as written as a reduction, while the other half-reaction is forced to run in reverse as an oxidation.

Oxidation : Zn Reduction : Cu2+ + 2 e Overall cell reaction: Anode: Zn Cathode : Cu Anode is where oxidation occurs, cathode is the electrode where reduction occurs. Zn anode : negatively charged. Cu electrode : positively charged. E cell = Ereduction Eoxidation = +0.34 (-0.76) = +1.10V The reaction is feasible because Ecell >0. The electrons flow from the zinc anode via the external wire to the Cu cathode. The salt bridge: An electrolyte is a liquid that conducts electricity as a result of the presence of positive and/or negative ions. Usually aqueous ionic solutions. Strong electrolytes, weak electrolytes and non-electrolytes. Given 2 reactants, use E to predict redox reaction.

If Ecell >0, redox reaction is feasible or spontaneous. If Ecell <0, redox reaction is not feasible or non spontaneous.

Limitations of Ecell. Energetic vs kinetics We can use Ecell to predict whether a redox reaction is energetically feasible (delta G <0) but that does not give any information about the rate of reaction. Many reactions could have a high activation energy. Eg. H2 bubbled into Cu2+ ions. Ecell is feasible , but in reality no reaction occurs. We say that the reaction is energetically feasible but kinetically unfavourable. E values relate only to standard conditions. Changes in temp, pressure and concentration will affect the values of electrode potentials. We can use Le Chateliers principle to predict these changes. Practical applications of galvanic cells batteries and fuel cells. Batteries Zn (anode), MnO2 (cathode) Zn (anode), Ag2O (cathode) Rechargeable lead acid battery. Pb (anode), PbO2 (cathode) Fuel cell The electrode reactants in a fuel cell are supplied continuously and the cell is able to operate without theoretical limit as long as you supply reactants. Hydrogen-oxygen fuel cell:

H2 (anode) O2 (cathode) Alkaline electrolyte Advantages of fuel cells: No pollution They convert about 75% of the chemical energy of the fuel into useable power. Low maintenance cost as there is no moving parts to replace. 4

Disadvantages of fuel cells: Electrode reactions are slow. For cars, hydrogen must be transported either in cylinders or at very low temperature as a liquid. Bulky and expensive. Expensive Alkali may absorb carbon dioxide form air to form carbonates that clog up the porous electrodes. Electric cars: High mass of batteries Short driving ranges Low recharging rates High replacement costs of batteries.

Alternative to this fuel cell methanol fuel cell.

Copy out the two half-equations. Multiply the half-equations by appropriate factors so that the number of electrons involved in each is the same. Add the two half-equations together, cancelling out any ions or molecules that appear on both sides of the equation.