EMF, Gibbs Free Energy (ΔG) and K

• Gibbs free energy (ΔG) – is a measure of spontaneity of a process

that occurs at constant temperature and pressure.
• The emf, E, of a redox reaction also indicates whether the reaction is
spontaneous.
ΔG = -nFEcell
Where: n – is a positive number without units that represents the
number of electrons transferred in the reaction.
Ecell – maximum voltage the cell can achieve
Faraday’s constant (F) – charge of one mole of electron
1 F= 6.022 x 103 e-/mol e- x 1.602 x 10-19 C/e-
= 9.645 x 104 C/ mol e- mol or 96,500 J/V mol

“A positive value of E and a negative value of ΔG both indicate that a reaction is

spontaneous.” - a condition for spontaneity.

For Reactants and Products under Standard Conditions:

ΔGo = -nFEocell
Relationship of Eocell to the Equilibrium Constant (K):
Dependence of the Cell Potential on Concentration
• Under standard condition (all concentrations 1M) the cell with the reaction:
cell voltage= 1.36V

What will the cell potential be if {Ce4+} is greater than 1.0 M?

***Le Chatelier’s principle.
An increase in the concentration of Ce4+ will favor the forward reaction and thus
increase the driving force on the electrons; cell potential increases.
An increase in the concentration of a product Cu2+ or Ce3+ will oppose the forward
reaction, thus decreasing the cell potential.
The Nernst Equation
-The dependence of the cell potential on concentration results directly
from the dependence of free energy on concentration.
At 25 degrees Celsius and log (base -10
form):
The Nernst Equation
-givesthe relationship between the cell potential
and the concentrations of the cell components.
- Named after German chemist Walter Hermann
von Nernst
Calculating Equilibrium Constant, K:
At Equilibrium: no net transfer of electrons, thus ΔG= 0; E= 0; and Q= K
-dead battery (the cell is no longer capable of doing
work)
BATTERY
- a galvanic cell, or a series of combined galvanic cells,
that can be used as a source of direct electric current
at a constant voltage.
- has the advantage of being completely self-contained
and requiring no auxiliary components such as salt
bridges.
TYPES OF BATTERY:
•Dry Cell Battery
•Mercury Battery
•Lead Storage Battery
•Lithium- Ion Battery
The Dry Cell Battery
- the anode of the cell consists of a zinc can or
container that is in contact with manganese
dioxide (MnO2) and an electrolyte. The
electrolyte consists of ammonium chloride and
zinc chloride in water, to which starch is added
to thicken the solution to a paste-like
consistency so that it is less likely to leak. A
carbon rod serves as the cathode, which is
immersed in the electrolyte in the center of
the cell.
- the most common dry cell, that is, a cell
without a fluid component, is the Leclanché
cell used in flashlights and transistor radios.
Cell Reactions:

Cell Voltage = 1.5V

The Mercury Battery
The mercury battery is used extensively in
medicine and electronic industries and is
more expensive than the common dry cell.
Contained in a stainless steel cylinder, the
mercury battery consists of a zinc anode
(amalgamated with mercury) in contact
with a strongly alkaline electrolyte
containing zinc oxide and mercury(II)
oxide.
Cell Reactions:

Cell Voltage =1.35V (provides more constant voltage

compared to the Leclanché cell).

-has a considerably higher capacity and longer life. These

qualities make the mercury battery ideal for use in
pacemakers, hearing aids, electric watches, and light meters.
The Lead Storage Battery
- commonly used in automobiles consists of six identical cells joined
together in series. Each cell has a lead anode and a cathode made of lead
dioxide (PbO2) packed on a metal plate. Both the cathode and the anode
are immersed in an aqueous solution of sulfuric acid, which acts as the
electrolyte.
Cell Reactions:

- Under normal operating conditions, each cell produces 2 V; a total of 12 V from the
six cells is used to power the ignition circuit of the automobile and its other
electrical systems. The lead storage battery can deliver large amounts of current
for a short time, such as the time it takes to start up the engine.
- Is rechargeable unlike the dry cell and mercury battery.
The Lithium-Ion Battery
- the anode is made of a conducting
carbonaceous material, usually
graphite, which has tiny spaces in its
structure that can hold both Li atoms
and Li+1 ions. The cathode is made of
a transition metal oxide such as CoO2,
which can also hold Li+1 ions. Because
of the high reactivity of the metal, non-
aqueous electrolyte (organic solvent
plus dissolved salt) must be used.
Cell Reactions:

- The advantage of the battery is that lithium has the most negative standard
reduction potential and hence the greatest reducing strength.
- Lithium is the lightest metal so that only 6.941 g of Li (its molar mass) are needed
to produce 1 mole of electrons. A lithium-ion battery can be recharged literally
hundreds of times without deterioration.
- use in cellular telephones, digital cameras, and laptop computers.
Fuel Cells
• To generate electricity, heat produced by the reaction is first used to
convert water to steam, which then drives a turbine that drives a
generator. An appreciable fraction of the energy released in the form of
heat is lost to the surroundings at each step; even the most efficient
power plant converts only about 40 percent of the original chemical
energy into electricity. Because combustion reactions are redox
reactions, it is more desirable to carry them out directly by
electrochemical means, thereby greatly increasing the efficiency of power
production. This objective can be accomplished by a device known as a
fuel cell, a galvanic cell that requires a continuous supply of reactants to
keep functioning.
Hydrogen-Oxygen Fuel Cell
• In its simplest form, this consists of an electrolyte solution, such as
potassium hydroxide solution, and two inert electrodes. Hydrogen
and oxygen gases are bubbled through the anode and cathode
compartments (Figure 19.11), where the following reactions take
place: