Electrochemical Energy

Electrochemistry

- study of the relationships between electricity and chemical reactions.

- includes the study of both spontaneous and nonspontaneous processes.

Oxidation-Reduction Reactions

Oxidation – loss of electrons

Reduction – gain of electrons

Oxidation-reduction reaction (Redox reaction) – reactions involving the transfer of electrons

When a clean copper wire is placed

into a colorless solution of silver
nitrate, it is quickly apparent that a
chemical reaction takes place.
Crystals of silver metal form on the
wire, and the solution takes on a
blue color.

What has happened chemically?

The blue color of the solution is indicative of the presence of aqueous Cu2+ ions. These ions
must originate from the copper wire because no other source of copper is available.

In forming the cations, copper atoms must have lost electrons. We say that copper has been
oxidized

Cu(s) → Cu2+ (aq) + 2 e–

If copper loses its electrons, where did the electrons go?

The accumulation of silver on the copper wire provides us with the answer. The only
apparent way to form metallic silver in this system is from the silver ions in the original solution.

The silver cations in solution must have accepted the electrons lost by the copper. We say that
silver has been reduced.

Ag+ (aq) + e → Ag(s)

Copper loses two electrons in the oxidation half-reaction, whereas silver gains only one electron in
the reduction half-reaction. To conserve electrons, two silver ions must be reduced for every
copper atom that is oxidized.

Cu(s) → Cu2+ (aq) + 2 e–

2 Ag+ (aq) + 2 e → 2 Ag(s)

Adding the two half-reactions together, the electrons will cancel.

2 Ag+(aq) + Cu(s) –> 2 Ag(s) + Cu2+(aq)

A molecular equation can be written to include the spectator ions (NO3–).

2 Ag+(aq) + Cu(s) → 2 Ag(s) + Cu2+(aq)

2 AgNO3(aq) + Cu(s) → 2 Ag(s) + Cu(NO3)2 (aq)

Reducing agent (reductant) – substance that is oxidized; causes reduction of other substance

Oxidizing agent (oxidant) – substance that is reduced; causes the oxidation of other substance

We determine whether a given chemical reaction is

an oxidation-reduction reaction by keeping track of
the oxidation numbers (oxidation states) of the
elements involved in the reaction.

Oxidation Number

Each atom in a neutral substance or ion is assigned an oxidation number.

Monatomic ions – oxidation number is the same is the same as the charge

Neutral molecules and polyatomic atoms – oxidation number of a given atom is a hypothetical
charge -- assigned by artificially dividing up the electrons among the atoms in the molecule or ion.

Rules for Assigning Oxidation Numbers

1. For an atom its elemental form, oxidation number is always zero

*Each H atom in the H2 molecule has an oxidation number of 0 and each P atom in the P4
molecule has an oxidation number of 0.

2. For any monatomic ion, the oxidation number equals the ionic charge.
*K+ has an oxidation number of 1+, S2- has an oxidation number of -2, and so forth. In ionic
compounds, the alkali metal ions (group 1A) always have a 1+ charge and therefore, an oxidation of
+1. The alkaline metals (group 2A) are always +2, and aluminum (group 3A) is always +3 in ionic
compounds. (oxidation number – sign before the number)

3. Nonmetals usually have negative oxidation numbers, although they can sometimes be positive:
a) The oxidation number of oxygen is usually -2 in both ionic and molecular compounds. The
major exception s in compounds called peroxides, which contain the O22- ion, giving each
oxygen an oxidation number of -1
b) The oxidation number of hydrogen is usually +1 when bonded to nonmetals and -1 hen
bonded to metals
 c) The oxidation number of fluorine s -1 in all compounds. The other halogens have an
oxidation number of -1 in most binary compounds. When combined with oxygen, however,
they have positive oxidation states.

4. The sum of the oxidation numbers f all atoms in a neutral compound is zero. The sum of the
oxidation numbers in a polyatomic ion equals the charge of the ion.
*example: In the hydronium ion H3O+, the oxidation number of each hydrogen is +1 and
that of the oxygen is -2. Thus, the sum of the oxidation is 3(+1) + (-2) = +1, which is equal to the net
charge of the ion. This rule is useful in obtaining the oxidation number of one atom in a compound
or ion if you know the oxidation numbers of other atoms

Half Reactions

- Equations that show either oxidation or reduction alone

In the overall redox reaction, the number of electrons lost in the oxidation half-reaction must
equal the number of electrons gained in the reduction half-reaction.

When this condition is met and each half-reaction is balanced, the electrons on the two sides
cancel when the two half-reactions are added to give the balanced oxidation-reduction equation.

Sample Problem 3.1

Consider the oxidation of Cu(s) by Ag+.
2 Ag+(aq) + Cu(s) –> 2 Ag(s) + Cu2+(aq)

Sample Problem 3.2

Consider the oxidation of Sn2+ by Fe3+.
Sn2+(aq) + 2 Fe3+(aq) –> Sn4+(aq) + 2 Fe2+(aq)

Sample Problem 3.3 Given the half reaction, write the balanced redox reaction
Balancing Redox Reactions

Electrochemical Cell

The energy released in a spontaneous redox reaction can be used to perform electrical work

Voltaic or Galvanic Cell - device in which the transfer of electrons takes place through an external
pathway rather than directly between reactants present in the same reaction vessel.

Galvanic cell – any electrochemical cell in which a spontaneous chemical reaction can be used to
generate an electric current.

*Each compartment of a voltaic cell is called a half-cell.

*One half-cell is the site of the oxidation half-reaction, and the other is the site of the reduction
half-reaction.

Electrodes – the electrically conducting sites at which either oxidation or reduction take place are

Anode – electrode at which oxidation occurs is

Cathode – electrode at which reduction occurs

A salt bridge contains a strong electrolyte that

allows either cations or anions to migrate into the
solution where they are needed to maintain charge
neutrality.

The salt bridge is crucial in a galvanic ell. By allowing

ions to flow into each half- cell, the bridge closes the
circuit and allows current to flow. A wire can carry a
current of electrons, but it cannot transport the ions
needed to complete the circuit.
Cell Notation

- a shorthand notation for representing the specific chemistry of so many possible

electrochemical cells.
- lists the metals and ions involved in the reaction.

vertical line, | - denotes a phase boundary

double line, || - represents the salt bridge.

The anode is always written on the left and the cathode on the right.

Anode | Electrolyte of Anode || Electrolyte of Cathode | Cathode

The previous example of copper and silver would be written as follows:

Zn(s) | Zn2+(aq)(1 M) || Cu2+(aq)(1 M) | Cu(s)

The assigned concentrations for the standard state of an electrochemical cell is 1 M.

Sample Problem 3.4

Consider the oxidation of Cu(s) by Ag+.
2 Ag+(aq) + Cu(s) –> 2 Ag(s) + Cu2+(aq)

Cell Potential
If the electrochemical half-reaction includes the production or consumption of a gas, the
standard state is a pressure of 1 atm.

A standard state also implies that the electrode material is in its thermodynamic standard
state, which is commonly the case because most electrode materials are solids at room
temperature.

If we take the charged electrodes of a galvanic cell and connect them to a high impedance
voltmeter, what will happen?
Cell potential, Ecell – potential difference between the two electrodes of a voltaic cell
- also called electromotive (“causing electron motion”) force, or emf - because the potential
difference provides the driving force that pushes electrons through the external circuit
- also called the voltage of the cell because it is measured in volts

One volt (V) is the potential difference required to impart 1 joule (J) of energy to a charge of 1
coulomb (C):
1 V = 1 J/C
The cell potential of any voltaic cell is positive.

The magnitude of the cell potential depends on the reactions that occur at the cathode
and anode, the concentrations of reactants and products, and the temperature, which we will
assume to be 25 °C unless otherwise noted.

We will focus on cells that are operated at 25 °C under standard conditions, that is, 1 M
concentrations for reactants and products in solution and 1 atm pressure for gaseous reactants
and products.

Standard Cell Potential, E°cell

Standard cell potential or standard emf (E°cell) – cell potential under standard conditions
- is the standard reduction potential of the cathode reaction, E°red (cathode), minus the
standard reduction potential of the anode reaction, E°red (anode):

E°cell = E°red (cathode) - E°red (anode)

By convention, the potential associated with each electrode is chosen to be the potential for
reduction at that electrode. Thus, standard half-cell potentials are standard reduction potentials,
denoted E°red.

It is not possible to measure the standard reduction potential of a half-reaction directly.

By assigning a standard reduction potential to a certain reference half-reaction, the standard

reduction potentials of other half-reactions can be determine relative to that reference value.

The reference half-reaction is the reduction of H+(aq) to H2(g) under standard conditions, which is
assigned a standard reduction potential of exactly 0 V.

2 H+(aq, 1 M) + 2 e- → H2(g, 1 atm) E°red = 0 V

Standard Hydrogen Electrode (SHE)

- The electrode designed to produce the reference half-reaction
- consists of a platinum wire connected to a piece of platinum foil covered with finely
divided platinum that serves as an inert surface for the reaction.
- allows the platinum to be in contact with both 1 M H+(aq) and a stream of hydrogen
- gas at 1 atm.
- can operate as either the anode or cathode of a cell, depending on the nature of the other
electrode
Graphical representation of
standard cell potential of a
voltaic cell
Sample Problem 3.5

Batteries and Fuel Cells

Battery – is a portable, self-contained electrochemical power source

that consists of one or more voltaic cells.

Primary cells or batteries – single-use batteries that cannot be

recharged

Alkaline batteries – most prevalent type of primary battery in use

today

- The anode is powdered zinc metal immobilized in a gel in

contact with a concentrated solution of KOH (hence, the name
alkaline battery).
- The cathode is a mixture of MnO2(s) and graphite, separated
from the anode by a porous fabric.
- The battery is sealed in a steel can to reduce the risk of any of
the concentrated KOH escaping.

Rechargeable batteries

- increasingly common in consumer products

- represent examples of secondary cells or secondary
batteries.
- With the increasing popularity of cellular phones, digital
cameras, and miniaturized computer devices such as palmtop
and laptop computers, nickel-cadmium, or ni-cad, batteries,
have become familiar to many consumers.

Nickel-metal-hydride batteries – find use in many of the

same devices as ni-cad cells, and larger versions serve as
the main batteries in hybrid cars like the Toyota Prius.
The most widely selling rechargeable batteries. That
distinction still belongs to the lead-acid storage
battery in automobiles.

Fuel Cell
- a voltaic cell in which the reactants can be supplied continuously and the
products of the cell reaction are continuously removed.
- Like a battery, it uses a chemical reaction to produce electrical energy.
- But unlike a battery, it can be refueled on an ongoing basis

Galvanic Cells vs. Electrolytic Cell

Voltaic cells are based on

spontaneous redox reactions. It
is also possible for
nonspontaneous redox
reactions to occur, however, by
using electrical energy to drive
them.

Electrolysis – process of passing

an electric current through an
ionic solution or molten salt to
produce a chemical reaction.

lectrolytic Cell

- consists of two electrodes immersed either in a molten salt or in a

solution.
- A battery or some other source of electrical energy acts as an
electron pump, pushing electrons into one electrode and pulling
them from the other.
- Just as in voltaic cells, the electrode at which reduction occurs is
called the cathode, and the electrode at which oxidation occurs is
called the anode.

Electrolysis changes the polarity of the electrodes in a system.

*Instead of the reactions that would occur spontaneously at the electrodes, the external power
supply causes the reverse reactions to occur.
Thus, for reduction, electrons are forced to the cathode in an electrolytic reaction.
The cathode is still the site of reduction, but in electrolysis, it is negatively charged because the
external power supply forces electrons (and their negative charges) to the location of the reaction.

The anode is still the site of oxidation, but in electrolysis, it is positively charged. In forcing oxidation
of the material, the external power supply pulls the electrons away from the region of the oxidation
reaction.

Electrolysis

Passive electrolysis – If the electrodes are chemically inert

materials that simply provide a path for electrons
- used in industry to purify metals that corrode
easily.

Active electrolysis – when the electrodes are part of the electrolytic

reaction
- used to plate materials to provide resistance to corrosion.

Electroplating – process of depositing a thin coat of metal by using

electricity

Corrosion: An Environmental Voltaic Cell

Corrosion reactions are spontaneous redox reactions in which a metal is attacked by some substance
in its environment and converted to an unwanted compound.

The rusting of iron is a familiar corrosion process that carries a significant economic impact.
Up to 20% of the iron produced annually in the United States is used to replace iron objects that
have been discarded because of rust damage.

Corrosion of Iron (Rusting)

- Rusting of iron requires both oxygen and water, and the process can be accelerated by other
factors such as pH, presence of salts, contact with metals more difficult to oxidize than iron, and
stress on the iron.
- The corrosion process involves oxidation and reduction, and the metal conducts electricity.
- electrons can move through the metal from a region where oxidation occurs to a region where
reduction occurs, as in voltaic cells.

Because the standard reduction potential for reduction of Fe2+(aq) is less positive than that for
reduction of O2, Fe(s) can be oxidized by O2(g):

Cathode: O2(g) + 4 H+(aq) + 4 e- → 2 H2O(l) E°red = 1.23 V

Anode: Fe(s) → Fe2+(aq) + 2 e- E°red = -0.44 V

 A portion of the iron, often associated with a dent or region of strain, can serve as an anode
at which Fe is oxidized to Fe2+. The electrons produced in the oxidation migrate through the metal
from this anodic region to another portion of the surface, which serves as the cathode where O2 for
is reduced.

The reduction of O2 requires H+, so lowering the concentration of H+ (increasing the pH)
makes O2 reduction less favorable. Iron in contact with a solution whose pH is greater than 9 does
not corrode.

The Fe2+ formed at the anode is eventually oxidized to Fe3+, which forms the hydrated iron(III) oxide
known as rust:

Fe2+(aq) + O2(g) + 4 H2O(l) + 2 xH2O(l) → 2 Fe2O3 xH2O(s) + 8 H+(aq)

Corrosion Prevention

Coatings - The most common means of protecting a material from corrosion is to apply some
sort of protective coating.

o Because paint is such a common means of combating corrosion, many paint companies
add chemicals to inhibit corrosion. A professional society of industrial painters lists 20 rust
inhibitors that are environmentally approved additives for paints.

Although the specific chemical content may vary, most of these corrosion inhibitors contain one of
the following ions: phosphate, borosilicate, chromate, or phosphosilicate. The
precise mode of corrosion inhibition depends on several factors, but when part
of a paint coating all of these ions form compounds with oxidized iron that
inhibit further formation of rust

Passivation - Much like an oxide coating on the surface of aluminum prevents

ongoing corrosion, these coatings stop the corrosion of the iron after only a
small amount of material has reacted.
Cathodic Protection

The fact that some materials are more easily oxidized than iron provides a way to construct
galvanic corrosion conditions intentionally to protect the iron.

If we choose a metal, such as magnesium, whose reduction potential is more negative than that of
iron, the magnesium is oxidized, and iron is reduced:

Fe2+ + 2 e– → Fe E°red = –0.41 V

Mg2+ + 2 e– → Mg E°red = –2.39 V

If we wish to prevent iron from corroding, we can use a

piece of magnesium as a sacrificial anode. Connecting the
piece of magnesium to the iron forces the iron to be the
cathode, thereby preventing the oxidation of iron. This
process is called cathodic protection. By making the iron
a cathode, we ensure that it cannot be an anode, and so
it will not corrode. To be effective, the sacrificial anode
must be replaced periodically, but this method finds many
uses, including the protection of iron or steel pipelines