Course 10

Electrochemistry

1.Introduction 2.Galvanic cells and electrodes 3.Cell potentials and thermodynamics 4.The Nernst equation 5.Applications of the Nernst equation 6.Batteries and fuel cells 7.Electrochemical corrosion 8.Electrolytic cells and electrolysis

1. Introduction The connection between chemistry and electricity is a very old one, going back to Alessandro Volta's discovery, in 1793, that electricity could be produced by placing two dissimilar metals on opposite sides of a moistened paper.

(-) Anode oxidation

galvanic cell

electrolyte
(+) cathode reduction

Electrochemical cell electrolysis cell

A battery is a galvanic cell or, more commonly, a group of galvanic cells connected in series, where the potentials of the individual cells add to give the total battery potential. Batteries are a source of direct current.

Electrode: 1st degree conductor (e- conductor) 2nd degree conductor (ionic conductor)

All this process are characterized by a potential decay, Eox respectively Ered
red ox EM E / M z M / M z

Nernst Equation:

red M / M z

(M , T , CM z ) E

0 M / M z

RT ln C M z zF

Where:
0 EM / M z = standard reduction potential (depends only on the nature of

the chemical specie) R = gas constant 8317 [J/kmol K] T = absolute temperature [K] z = number of exchanged electrons in the oxidation/reduction process F = the Faraday number (96 489 C)

Each type of electrode can be anode or cathode depending on the partner electrode. The electrode with the less potential is anode.

()M / M z (CM z )
( ) M 1 / M
z1 1

EM / M z

(C M )
z 1

E M1 / M E M / M
z 1 z

Symbolizing a cell:

() M / M (C
0 1 M

z1 1

z 1

) // M

/ M 0 ()

(-)

(+)

diaphragm (semi-permeable layer)

Half cell reactions:

A(-)

oxidation

K(+)

reduction

General reaction:

2. Galvanic cells and electrodes We can measure the difference between the potentials of two electrodes that dip into the same solution, or more usefully, are in two different solutions. In the latter case, each electrode-solution pair constitutes an oxidation-reduction half cell, and we are measuring the sum of the two half-cell potentials. A typical cell might consist of two pieces of metal, one zinc and the other copper, each immersed each in a solution containing a dissolved salt of the corresponding metal. The two solutions are separated by a porous barrier that prevents them from rapidly mixing but allows ions to diffuse through.

1. Potential: - electromotive force, open circuit voltage (VOC): maximum theoretical potential. VOC depends on the materials of the cathode (K) and anode (A)

- battery potential: U (U< VOC) 2. Current: depends on the size of the electrodes

3. Power: P = UI The electrolyte used in all cell must have a low resistance (a high conductivity) a high ions concentration. Therefore, an electrolyte contains salts, acids or basis.

-function in static regime Ech Eel primary cell

Type of galvanic cell

Ech Eel rechargeable battery

-function in dynamic regime Ech Eel, fuel cell

Primary cells
1. 2. 3. 4. Galvanic (-) Zn / H2SO4 / Cu (+) Lclanch Alkaline Lclanch Lithium batteries

Rechargeable Batteries; Fuel cells

Ech Eel
- acid batteries
Types: - alkaline batteries - lithium batteries

If the battery is deeply discharged the lead sulfate from the plates can fall and producing a short circuit- sulfactation. During discharging the battery consumes H2SO4 and produces water and the acid solution will be less concentrate. Long storage periods has as consequence structural modifications of lead sulfate which increases in volume. The adherence is less and the possibility of falling is increasing. Therefore, it is not recommended to store the battery with the electrolyte inside (e.g. during winter). High temperatures, over 40C have the same consequence of increasing the volume of lead sulfate, therefore it is recommended to park the car, during summer, on shadowy places.

Charging batteries:
a.
c PbSO4 2 H 2 O Pb PbO2 2 H 2 SO4

Uc = 2.08 V After finishing this reaction it starts the electrolysis of water starts.
b.
c H 2O H 2 1 / 2O2

U = 2.12V The two gases are bubbling: the battery boils The battery must not boil because: -gas bubbles have an abrasive effect -hydrogen can be adsorbed on lead (acting as an insulator) and modifies the lead potential (overpotential). The battery output is decreasing because the result is a decrease in VOC (and in the potential, U) To prevent this fact, modern batteries have: A (-) Pb + 9% Sb (poison for hydrogen)

! The alkaline batteries require profound discharging Overcharging is: -recommended for lithium ion batteries (with ceramic electrolyte) because heating increases the ionic conduction -is not recommended for lithium polymer batteries (heating may damage the polymer electrolyte).

Fuel Cells
A fuel cell is a galvanic cell for which the reactants are continuously supplied. To illustrate the principles of fuel cells, lets consider the exothermic redox reaction of methane with oxygen: CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (g) + energy Usually the energy from this reaction is released as heat to warm homes and to run machines. However, in a fuel cell designed to use this reaction, the energy is used to produce an electric current: the electrons flow from the reducing agent (CH4) to the oxidizing agent (O2) through a conductor.

The H2 O2 fuel cell (-) Ni H2: H2 2 H+ + 2 e(+) Fe O2: O2 + 2 e- + H2O 2 HOThe fuel cell based on the reaction of hydrogen and oxygen to form water: 2H2 (g) + O2 (g) 2H2O (l) The half-reactions are: Anode reaction: 2H2 + 4OH- 4H2O + 4eCathode reaction: 4e- + O2 + 2H2O 4OH-