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Inorganic Chemistry
Farrah Cañavera Buelvas

•! The term oxidation was originally used to describe

reactions in which an element combines with
oxygen.
•! The term reduction comes from the Latin stem
meaning "to lead back."
•! After electrons were discovered, chemists became
convinced that oxidation-reduction reactions
involved the transfer of electrons from one atom to
another.

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Oxidation and reduction steps complement one another

Oxidation refers to gaining oxygen, losing hydrogen or

losing one or more electrons. Reduction refers to losing
oxygen, gaining hydrogen or gaining one or more
electrons.

•! Oxidation is loss of electrons.

•! Reduction is gain of electrons.

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An oxidising agent oxidises Or you could think it out like this:

something else.
Loss of electrons is Oxidation (LEO)
That means that an oxidising agent
takes electrons from that other
substance.
So an oxidising agent must gain
electrons.
Reduction is gain of electrons (OIL RIG)
Oxidation is loss of electrons (OIL RIG)
An oxidising agent oxidises something
else.
That means that the oxidising agent
must be being reduced.
Gain of electrons is Reduction
(GER).
So an oxidising agent must gain
electrons.

Identify the species being oxidized and reduced in each

of the following reactions:
a. 2 Cr+ + Sn4+! Cr3+ + Sn2+ Cr+: oxidized, Sn4+: reduced
b. 3 Hg2+ + 2 Fe (s) ! 3 Hg2 + 2 Fe3+ Hg2+: reduced, Fe: oxidized

c. 2 As (s) + 3 Cl2 (g) ! 2 AsCl3 As: oxidized, Cl2: reduced

Would you use an oxidizing agent or reducing agent in

order for the following reactions to occur?

a.! ClO3– ! ClO2 reducing agent

b.! SO42– ! S2– reducing agent
c.! Mn2+ ! MnO2 oxidizing agent
d.! d. Zn ! ZnCl2
oxidizing agent

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•! Step 1. Identify and write the incomplete half-reactions.

•! Step 2. Balance just the elements other than O and H (and
charges).
•! Step 3. Balance O by adding H2O and then balance H
atoms using one of the following methods:
"!In the case of an acidic medium reaction: by adding H+.
"!In the case of a basic medium reaction: by adding H2O and
countering the O atoms by adding the same number of
OH– on the other side.
•! Step 4. Balance electric charge by adding electrons.
•! Step 5. Ensure extent of oxidation is equal to the extent of
reduction and combine the balanced half-equations.

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•! Step 1. Identify and write the incomplete half-reactions.

•! Step 2. Balance just the elements other than O and H (and
charges).
•! Step 3. Balance O by adding H2O and then balance H atoms
using one of the following methods:
"! In the case of an acidic medium reaction: by adding H+.
"! If the reaction is in basic solution: add equal amount of OH– to
both sides of the equation. The OH– and H+ combine to form
water and leaves excess of OH– on the other side. Cancel any
water that appears on both side.
•! Step 4. Balance electric charge by adding electrons.
•! Step 5. Ensure extent of oxidation is equal to the extent of
reduction and combine the balanced half-equations.

Escriba en forma iónica:

¿Es ionizado [H+(ac) + Cl–(ac)]
¿Es soluble (HCl se ioniza
o disociado
en agua? completamente)
en H2O?

[2Na+(ac) + SO42–]
(Na2SO4 es una sal iónica
soluble.
Escribir la fórmula Escribir la fórmula
completa: completa:
PbSO4(s) CH3COOH(ac)

Las únicas sustancias comunes que pueden escribirse como iones en

ecuaciones iónicas son (1) ácidos fuertes, (2) bases fuertes y (3) sales
iónicas solubles.
10

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1.! El estado de oxidación en un elemento libre, sin combinar

es cero (0).
2.! La suma de todos los estado de oxidación en:
1.!Una molécula neutra, es decir, un elemento aislado, un
compuesto neutro o una unidad fórmula, es cero (0).
2.!Un compuesto iónico, es la carga del ion.
3.! Los metales del grupo 1 tienen en sus compuestos EO +1 y
los del grupo 2 EO +2.
4.! El estado de oxidación del flúor en sus compuestos es –1.

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5.! El estado de oxidación del hidrógeno en sus compuestos es

+1.
6.! El estado de oxidación del oxígeno en sus compuestos es –
2. En los peróxidos es –1.
7.! Los elementos del grupo 17 en sus compuestos binarios
con metales tienen estado de oxidación –1, los del grupo
16 tienen EO –2; y los del grupo 15 tienen EO –3.[LiO,
KCl, Li3N]
#!Por convención los números de oxidación se escriben +n y –n,
mientras que las cargas iónicas se escriben n+ y n–

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•! Reacciones en las que dos o más sustancias se

combinan para formar un compuesto.
•! Pueden involucrar:
$!Dos elementos que forman un compuesto.
$!Un elemento y un Compuesto para formar un
solo compuesto.
$!La combinación de dos compuestos para formar
un nuevo compuesto. (No son redox)

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Muchos metales reaccionan con no metales para formar

compuestos iónicos binarios.

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El número de oxidación del elemento más positivo suele ser

variable, dependiendo de las condiciones de reacción:

En general, un estado de oxidación mayor de un no metal es

formado cuando se reacciona con un exceso de otro no metal.

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No son redox
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•! Reacciones en las que un compuesto descompone

para producir (1) dos elementos, (2) uno o más
elementos, o (3) dos o mas compuestos.

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Una reacción de descomposición puede o no ser una reacción Redox

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•! Reacciones donde un elemento desplaza a otro en un

compuesto.
•! Siempre son reacciones Redox.
•! Comúnmente, un metal desplaza metales menos activos o
hidrógeno de sus compuestos en solución acuosa
generando la forma oxidada del metal más activo y la
forma reducida (metal libre) del otro metal o hidrógeno.

Metal más activo + Metal menos activo

Sal del Metal + Sal del Metal mas
menos activo activo
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Serie Actividad de Algunos Elementos

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•! Una gran pieza de zinc metálico se coloca

en solución de sulfato de cobre (II). La
solución azul se decolora y cobre metálico
caen al fondo del recipiente. La solución
resultante tiene sulfato de zinc. Escriba las
ecuaciones balanceadas: unidad formula,
iónica total e iónica neta.

Reacción de desplazamiento: el metal más activo (Zn) desplaza los

iones del metal menos activo (Cu) de la solución.
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Metal activo + Hidrógeno + Sal del

Ácido no oxidante Ácido

Cualquier metal ubicado por encima del H2 en la serie

actividad, al ser adicionado a una solución de ácido no
oxidante como HCl y H2SO4, el metal se disuelve para
producir hidrógeno, y una sal es formada.
HNO3 es un ácido oxidante, reacciona con metales activos
para producir oxido de nitrógeno, pero no H2
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No Metal activo + No Metal menos

Sal de No Metal activo + Sal de No
menos activo Metal más activo

Cada halógeno desplazará halógenos

menos activos (más pesados) de sus
sales binarias.

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Un mismo elemento en un estado de oxidación se oxida

y se reduce al mismo tiempo.

Siempre hay un elemento que puede tener por lo menos 3

estados de oxidación. El elemento mismo está en un estado
de oxidación intermedio.

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Un mismo elemento químico pasa de tener dos estados

de oxidación diferentes a un único estado de oxidación.
El mismo elemento es oxidado y reducido en la misma
reacción.

NH4NO2 -> N2 + 2 H2O

2 H2S + SO2 -> 2 H2O + 3 S
Cu + CuCl2 -> 2 CuCl

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•! In any electrochemical process, electrons flow from

one chemical substance to another, driven by an
oxidation–reduction (redox) reaction.
•! The associated potential energy is determined by
the potential difference between the valence
electrons in atoms of different elements.
•! The tendency of an electron to migrate from one
species to another is expressed in terms of the
differences between their standard potentials.

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•! In a reduction half-reaction, a substance gains

electrons:

•! In an oxidation half-reaction, a substance loses

electrons:

•! Electrons are not ascribed a state in the equation

of a half-reaction: they are ‘in transit’.
•! The oxidized and reduced species in a half-reaction
constitute a redox couple.

A couple is written with the oxidized species before the

reduced:

It is useful to represent oxidation half-reactions by the

corresponding reduction half-reaction. To do so, we simply
reverse the equation for the oxidation half-reaction.
Thus, the reduction half-reaction associated with the
oxidation of zinc is written:

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A galvanic (voltaic) cell uses the energy released during a

spontaneous redox reaction (
G < 0) to generate
electricity. This type of electrochemical cell is often called
a voltaic cell after its inventor, the Italian physicist
Alessandro Volta (1745–1827).

An electrolytic cell consumes electrical energy from an

external source, using it to cause a nonspontaneous redox
reaction to occur (
G > 0).

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In a galvanic cell, a spontaneous redox reaction occurs and

generates an electrical current. In such a cell, electrical work is
done by the system.

One type of simple electrochemical half-cell consists of a

metal strip dipping into a solution of its ions, No chemical
reaction occurs in such a half cell, although an equation
describing the half cell refers (by convention) to the
appropriate reduction process
e.g. a Cu strip immersed in an aqueous
solution of a Cu(II) salt.

Let’s consider the reaction of metallic zinc with cupric

ion (Cu2+) to give copper metal and Zn2+ ion.

All the energy released

is in the form of heat
rather than in a form
that can be used to do
work.

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When two such half-cells are combined in an electrical

circuit, a redox reaction occurs if there is a potential
difference between the half-cells.

A simple electrochemical cell called the Daniell cell after its

inventor, John Daniell.

Salt bridge, (KCl or KNO3 The difference in the electrical potentials

solution) permits ions to of the two half-cells results in a potential
pass between the two half- difference (which can be measured on
cells but does not allow the the voltmeter)
copper(II) and zinc(II)
Electrons flow along the wire from one
solutions to mix too
cell to the other as the reaction proceeds.
quickly

The electrical circuit is

completed by the
passage of ions across
the salt bridge.

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The electrolyte in the salt bridge serves

two purposes: it completes the circuit by
carrying electrical charge and maintains
electrical neutrality in both solutions by
allowing ions to migrate between them.

The identity of the salt in a salt bridge is

unimportant, as long as the component
ions do not react or undergo a redox
reaction under the operating conditions
of the cell.

In the absence of a salt bridge or some

other similar connection, the reaction
would rapidly cease because electrical
neutrality could not be maintained.

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The overall electrochemical cell is

denoted by the cell diagram:

An experimental set-up for the

Daniell cell.
where the solid vertical lines represent boundaries between phases,
and the dotted line stands for the salt bridge.
The spontaneous process reads from left to right across the cell
diagram. The reduction process is always drawn on the right-hand side of
the cell diagram.

The potential difference between the two half-cells is denoted

by Ecell and its value (in volts) is directly related to the change
in Gibbs energy for the overall reaction.

Equation 1 relates Ecell to !G and

Equation 2 is the standard cell potential

The temperature must always be stated, because !G (and

hence Ecell) is temperature-dependent

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The standard cell potential refers to the conditions:

For a spontaneous reaction, Eºcell is always positive, and this

corresponds to a negative value of !Gº.

Strictly, the standard conditions refer to unit activity, but for a dilute
solution, the concentration is approximately equal to the activity.

The standard pressure may in some tables of data be taken as 1 atm

(101 300 Pa);

Example: The Gibbs energy change in a Daniell cell

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This large negative value of !Gº is consistent with a spontaneous

reaction.

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In the Zn/Cu system, the valence

electrons in zinc have a substantially
higher potential energy than the valence
electrons in copper because of shielding
of the s electrons of zinc by the electrons
in filled d orbitals.

Hence electrons flow spontaneously

from zinc to copper(II) ions, forming
zinc(II) ions and metallic copper

Because the Zn(s) + Cu2+(aq) system is

higher in energy by 1.10 V than the Cu
(s) + Zn2+(aq) system, energy is released
when electrons are transferred from Zn
to Cu2+ to form Cu and Zn2+.

Because the potential energy of valence electrons differs greatly from one
substance to another, the voltage of a galvanic cell depends partly on the
identity of the reacting substances.

The measured potential of a cell also depends strongly on the

concentrations of the reacting species and the temperature of the system.

To develop a scale of relative potentials that will allow us to predict the

direction of an electrochemical reaction and the magnitude of the driving
force for the reaction, the potentials for oxidations and reductions of
different substances must be measured under comparable conditions.

To do this, chemists use the standard cell potential (E°cell), defined as the
potential of a cell measured under standard conditions—that is, with all
species in their standard states (1 M for solutions, 1 atm for gases, pure
solids or pure liquids for other substances) and at a fixed temperature,
usually 25°C.

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It is physically impossible to measure the potential of a single

electrode: only the difference between the potentials of two
electrodes can be measured.

We can, however, compare the standard cell potentials for two

different galvanic cells that have one kind of electrode in
common. This allows us to measure the potential difference
between two dissimilar electrodes.

All tabulated values of standard electrode potentials by

convention are listed for a reaction written as a reduction, not
as an oxidation, to be able to compare standard potentials for
different substances.

The standard cell potential (E°cell) is the difference between

the tabulated reduction potentials of the two half-reactions,
not their sum:

E°cell = E°cathode  E°anode

Although it is impossible to measure the potential of any
electrode directly, we can choose a reference electrode whose
potential is defined as 0 V under standard conditions

The standard hydrogen electrode (SHE) is universally used

for this purpose and is assigned a standard potential of 0 V.

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It consists of a strip of
platinum wire in contact
with an aqueous solution
containing 1 M H+.

The [H+] in solution is in

equilibrium with H2 gas at
a pressure of 1 atm at the
Pt-solution interface

Protons are reduced or

hydrogen molecules are
oxidized at the Pt surface.

One especially attractive feature of the SHE is that the Pt metal electrode
is not consumed during the reaction.

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cathode:
2H+(aq)+2eH2(g)
Ecathode=0 V

anode:
Zn(s)Zn2+(aq)+2e
Eanode=0.76 V

Overall:
Zn(s)+2H+(aq)Zn2+(aq)+H2(g)


Ecell=EcathodeEanode=0.76 V

The potential of a half-reaction measured against the SHE under

standard conditions is called the standard electrode potential for that half-
reaction.

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The standard electrode potential for the reaction that occurs

at the anode, the oxidation of Zn to Zn2+, often called the
Zn/Zn2+ redox couple, or the Zn/Zn2+ couple, is (0.76 V)
= 0.76 V.

Because electrical potential is the energy needed

to move a charged particle in an electric field,
standard electrode potentials for half-reactions
are intensive properties and do not depend on the
amount of substance involved.

E° values are independent of the stoichiometric

coefficients for the half-reaction, and, most
important, the coefficients used to produce a
balanced overall reaction do not affect the value of
the cell potential.

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Pt (s)|H2 (g) |H+ (ac)|| Cu2+(ac)| Cu (s)

Eºcelda = Eº cathode – Eºanode

0.34 V = EºCu2+/Cu – EºH+/H2

0.34 V = EºCu2+/Cu – 0

EºCu2+/Cu = 0.34 V

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If the value of E°cell is positive, the reaction will occur spontaneously as

written.
If the value of E°cell is negative, then the reaction is not spontaneous,
and it will not occur as written under standard conditions; it will,
however, proceed spontaneously in the opposite direction

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EXAMPLE

A galvanic cell with a measured standard cell potential of 0.27

V is constructed using two beakers connected by a salt bridge.
One beaker contains a strip of gallium metal immersed in a 1
M solution of GaCl3, and the other contains a piece of nickel
immersed in a 1 M solution of NiCl2. The half-reactions that
occur when the compartments are connected are as follows:

cathode: Ni2+(aq) + 2e  Ni(s)

anode: Ga(s)  Ga3+(aq) + 3e
If the potential for the oxidation of Ga to Ga3+ is 0.55 V
under standard conditions, what is the potential for the
oxidation of Ni to Ni2+?

Asked for: standard electrode potential of reaction occurring at the

cathode

We have been given the potential for the oxidation of Ga to

Ga3+ under standard conditions, but to report the standard
electrode potential, we must reverse the sign.
For the reduction reaction Ga3+(aq) + 3e  Ga(s),
E°anode = 0.55 V.

We can calculate the standard potential for the reduction of

Ni2+ to Ni :

Eºcell = Eºcathode – Eºanode

0.27 V = Eºcathode – (–0.55 V)
Eºcathode = – 0.28 V
Because we are asked for the potential for the oxidation of Ni
to Ni2+ under standard conditions, we must reverse the sign of
E°cathode. Thus Eº=–(–0.28V) = 0.28 V

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•! When using a galvanic cell to measure the concentration of

a substance, we are generally interested in the potential of
only one of the electrodes of the cell, the so-called indicator
electrode, whose potential is related to the concentration of
the substance being measured.
•! To ensure that any change in the measured potential of the
cell is due to only the substance being analyzed, the
potential of the other electrode, the reference electrode, must
be constant
•! The potential of a reference electrode must be unaffected by
the properties of the solution, and if possible, it should be
physically isolated from the solution of interest.

•! To measure the potential of a solution, we select a

reference electrode and an appropriate indicator
electrode.
•! Whether reduction or oxidation of the substance being
analyzed occurs depends on the potential of the half-
reaction for the substance of interest (the sample) and the
potential of the reference electrode.

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The silver–silver chloride electrode, which consists of a silver wire coated

with a very thin layer of AgCl that is dipped into a chloride ion solution with
a fixed concentration. The cell diagram and reduction half-reaction are as
follows:
Cl(aq)AgCl(s)Ag(s)
AgCl(s)+e Ag(s)+Cl(aq)

If a saturated solution of KCl is used as the chloride solution, the potential

of the silver–silver chloride electrode is 0.197 V versus the SHE.
That is, 0.197 V must be subtracted from the measured value to obtain the
standard electrode potential measured against the SHE.

The saturated calomel electrode (SCE), which has the same general form as
the silver–silver chloride electrode. The SCE consists of a platinum wire
inserted into a moist paste of liquid mercury (Hg2Cl2; called calomel in the
old chemical literature) and KCl.
This interior cell is surrounded by an aqueous
KCl solution, which acts as a salt bridge between
the interior cell and the exterior solution

Pt(s)Hg2Cl2(s)KCl(aq, sat)

Hg2Cl2(s) + 2e  2Hg(l) + 2Cl(aq)

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A glass electrode is generally used for this purpose, in which an

internal Ag/AgCl electrode is immersed in a 0.10 M HCl solution that
is separated from the solution by a very thin glass membrane

The glass membrane absorbs protons,

which affects the measured potential.
The extent of the adsorption on the inner
side is fixed because [H+] is fixed inside the
electrode, but the adsorption of protons on
the outer surface depends on the pH of the
solution.
The potential of the glass electrode depends
on [H+]

Eglass = E + (0.0591 V " log[H+]) = E‘  0.0591 V " pH

In practice, a glass electrode is calibrated.

Ion-selective electrodes are used to measure the concentration of a

particular species in solution; they are designed so that their potential
depends on only the concentration of the desired species

These electrodes usually contain an

internal reference electrode that is
connected by a solution of an electrolyte to
a crystalline inorganic material or a
membrane, which acts as the sensor.

For example, one type of ion-selective

electrode uses a single crystal of Eu-doped
LaF3 as the inorganic material.
When fluoride ions in solution diffuse to the
surface of the solid, the potential of the
electrode changes, resulting in a so-called
fluoride electrode.

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The thermodynamic criterion of spontaneity is that, at

constant temperature and pressure, the reaction Gibbs
energy change,
rG, is negative.

A negative value of
rGº corresponds to K > 1 and

therefore to a ‘favourable’ reaction in the sense that the
products dominate the reactants at equilibrium.

Because the overall chemical equation is the difference of two

reduction half-reactions, the standard Gibbs energy of the
overall reaction is the difference of the standard Gibbs
energies of the two half-reactions.

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By constructing the electrochemical

cell shown in the Figure, the standard
reduction potential or standard
electrode potential, Eº, for the Zn2+/Zn
couple could, in theory, be determined.

A negative standard potential (Eº< 0)

signifies a couple in which the reduced
species (the Zn in Zn2+/Zn) is a
reducing agent for H+ ions under
standard conditions in aqueous
solution.

That is, if Eº (Ox, Red) < 0, then the substance ‘Red’ is a

strong enough reducing agent to reduce H ions (in the sense
that K > 1 for the reaction).
A compilation of these values is known as the
electrochemical series:

An important feature of the electrochemical series is that the

reduced member of a couple has a thermodynamic tendency to
reduce the oxidized member of any couple that lies above it in the
series.
Note that the classification refers only to the thermodynamic aspect
of the reaction—its spontaneity under standard conditions and the
value of K, not its rate.

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Standard Potentials
for Selected
Reduction
Half-Reactions at
25°C

The strongest oxidant in

the table is F2,

All reactants that lie above

the SHE in the table are
stronger oxidants than H+,
and all those that lie below
the SHE are weaker.

The strongest reductant in

the table is thus metallic
lithium

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The apparent anomaly can be explained by the fact that electrode

potentials are measured in aqueous solution.

In aqueous solution intermolecular interactions are important, whereas

ionization potentials and electron affinities are measured in the gas phase.

Due to its small size, the Li+ ion is stabilized in aqueous solution by strong
electrostatic interactions with the negative dipole end of water molecules.

These interactions result in a significantly greater
Hhydration for Li+

compared with Cs+. Lithium metal is therefore the strongest reductant
(most easily oxidized) of the alkali metals in aqueous solution.

Using the electrochemical series

Any species on the left side of a half-reaction will spontaneously oxidize
any species on the right side of another half-reaction that lies below it in
the table.
Conversely, any species on the right side of a half-reaction will
spontaneously reduce any species on the left side of another half-reaction
that lies above it in the table.

Example: Among the couples in Table is the permanganate ion, MnO4–,

the common analytical reagent used in redox titrations of iron.
Which of the ions Fe2+, Cl–, and Ce3– can permanganate oxidize in
acidic solution?

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We need to note that a reagent

that is capable of reducing
MnO 4 – ions must be the
reduced form of a redox
couple having a more negative
standard potential than the
couple MnO4–/Mn2+.

MnO4– ions are sufficiently

strong oxidizing agents to
oxidize Fe2+ and Cl– but
cannot oxidize Ce3+

Consider the following three half-equations and their

corresponding standard reduction potentials:

In an electrochemical cell consisting of a standard hydrogen electrode and a

Ce4+/Ce3+ couple, reaction 1 is the spontaneous process

These results show that the Ce4+ ion is a more powerful oxidizing agent
than H+

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but if the hydrogen electrode is combined with the Cr3+/Cr2+ couple,

reaction 2 occurs:

Then, H+ is a better oxidizing agent than Cr3+ ions.

This means that Ce4+ ions will oxidize Cr2+ ions:

The thermodynamic favorability of each reaction can be

assessed by calculating Eº cell and !Gº (298 K).

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You must note carefully to what this value of !Gº refers:

!Gº (298K)= –332 kJ per mole of H2 or per two moles of

Ce4+.

i.e. 166 kJ per mole of Ce4+ or per half-mole of H2.

A useful (if somewhat artificial) ‘rule’ to remember is the anticlockwise

cycle which can be used with a table of standard reduction potentials
that are arranged as in Table 1.

Consider any pair of redox couples in the table; each couple is made up
of an oxidized and a reduced species.
The spontaneous reaction will be between the lower oxidized species and the
upper reduced species.
For example, Ag+ (an oxidized species) oxidizes Cu (a reduced species)
and the direction of the spontaneous reaction may be deduced by
constructing an anticlockwise cycle:

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Use the standard reduction potentials in Table 1 to

determine the products of the reaction between iron and
aqueous Br2.

This suggests two possible reactions:

The larger (more positive) Eº cell might initially suggest that

reaction 1 is the more thermodynamically favourable process,
but…

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Reaction 2 is therefore thermodynamically more favourable

than 1.
This example emphasizes that although a positive value of
Eº cell certainly indicates spontaneity, it is !Gº that is the
true indicator of the extent of reaction.

Example: The black tarnish that forms on silver objects is primarily Ag2S.
The half-reaction for reversing the tarnishing process is as follows:
Ag2S(s)+2e 2Ag(s)+S2(aq)
E°=0.69 V

1.! Referring to Table "Standard Potentials for Selected

Reduction Half-Reactions at 25°C", predict which
species—H2O2(aq), Zn(s), I(aq), Sn2+(aq)—can reduce
Ag2S to Ag under standard conditions.
2.! Of these species—H2O2(aq), Zn(s), I(aq), Sn2+(aq),
identify which is the strongest reducing agent in aqueous
solution and thus the best candidate for a commercial
product.
3.! From the data in Table "Standard Potentials for Selected
Reduction Half-Reactions at 25°C", suggest an
alternative reducing agent that is readily available,
inexpensive, and possibly more effective at removing
tarnish.

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H2O2(aq) + 2H+(aq) + 2e  2H2O(l) Eº= 1.78 V

O2(g) + 2H+(aq) + 2e  H2O2(aq) Eº= 0.70 V

I2(s) + 2e  2I(aq) Eº= 0.54 V

Sn2+(aq) + 2e  Sn(s) Eº= 0.14 V
Ag2S(s) + 2e  2Ag(s) + S2(aq) Eº= 0.69 V
Zn2+(aq) + 2e  Zn(s) Eº= 0.76 V

1. Zn(s) can reduce Ag2S(s) under standard conditions

2. The strongest reductant is Zn(s), the species on the right side of
the half-reaction that lies closer to the bottom of Table

Al3+(aq) + 3e  Al(s) Eº= 1.662 V

3. Of the reductants that lie below Zn(s) in Table; and therefore are
stronger reductants, only one is commonly available in household
products: Al(s), which is sold as aluminum foil for wrapping foods.

The effect of solution concentration on E

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•! Up to this point, we have considered only standard

reduction potentials, Eº.
•! It is more usual in the laboratory to work with solutions of
lower concentrations, and reduction potentials, E, depend
on the concentration of the solutions in the electrochemical
cells.
•! The dependence is given by the Nernst equation:

Temperature is a variable in the equation, although

normally experiments will be carried out at a specified
temperature

A 298 K:

Walther Hermann Nernst

(1864–1941).

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The oxidized forms of the half-cells are often on the left-

hand side and the reduced forms on the right at the table of
potential.

If the half-cell involves a metal ion/metal couple, the

activity of the solid metal is taken to be 1 and Nernst
equation simplifies to:

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Example:
The standard reduction potential of the Ag+/Ag couple is +0.80 V.
What is the value of E at 298K when the concentration of Ag+ ions is
0.020 mol dm–3?
The electrode is of the type Mn+/M, and so E can be found using the equation:
The half-equation for the couple is:

z= 1

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The Nernst equation may also be written in the form:

where Q is the reaction quotient

Equation:
is of the form: y = c + mx

and a plot of E against ln [Mn+] is

linear

The gradient of the line is

When [Ag+] = 1M, the cell is

under standard conditions,
this corresponds to ln[Ag+] =
0, and the reduction potential
is the standard value,
Eº=+0.80 V

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To judge the tendency of a reaction to run in a particular

direction at an arbitrary composition, we need to know
the sign and value of
G at that composition.

The reaction quotient has the same form as the equilibrium

constant K but the concentrations refer to an arbitrary stage of
the reaction; at equilibrium, Q = K.

The reaction is spontaneous at an arbitrary stage if
rG < 0.

*For reactions involving gas-phase species, the molar concentrations of

the latter are replaced by partial pressures relative to pº = 1 bar.

At equilibrium Ecell = 0 and Q = K, so Nernst equation

implies the following very important relationship between the
standard potential of a cell and the equilibrium constant of
the cell reaction at a temperature T:

The temperature dependence of a standard cell potential

provides a straightforward way to determine the standard
entropy of many redox reactions:

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If the half-cell of interest involves either H+ or [OH]– ions, then

the value of Eºhalf-cell will depend upon the pH of the solution.

For a redox couple in which there is transfer of e electrons

and H protons:

the potential of the electrode can be written

That is, the potential decreases (becoming more negative) as the pH

increases and the solution becomes more basic.

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Ejemplos uso Ecuación de Nernst

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Buelvas, Docente

Ejemplo 1:
Calcule el potencial, E, del electrodo Fe3+/Fe2+ cuando la concentración de Fe2+ es
exactamente cinco veces mayor que la de Fe3+.

Rta./
Fe3+ + e– ! Fe2+ Eº= +0.771 V
Concentración de [Fe2+] = 5[Fe3+]

[Red]y [Fe2+] 5[Fe3+]

Se calcula Q Q= –––––––x = ––––– = ––––– = 5
[Ox] [Fe3+] [Fe3+]

La semirreacción muestra que n=1, entonces:

0.0592 log 5 = (+0.771 – 0.041) V = +0.730V

E= +0.771 – ––––––
1

Química Inorgánica I–Farrah Cañavera

102
Buelvas, Docente

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Ejemplo 2:
Se construye una celda a 25ºC de la manera siguiente: Una media celda se
compone del par Fe3+/Fe2+ en la cual [Fe3+]= 1.00 M y [Fe2+]= 0.100 M; y
la otra contiene el par MnO4–/Mn2+ en solución ácida el la cual [MnO4–]=
1.00x10–2 M, [Mn2+]= 1.00x10–4 M y [H+]= 1.00x10–3 M. (a) calcule el
potencial de electrodo de cada media celda con estas concentraciones y (b)
determine el potencial global de celda.

(a) (i) Para la media celda MnO4–/Mn2+ como una reducción,

MnO4– + 8H+ + 5e– ! Mn2+ + 4H2O Eº= +1.507V

[Mn2+]
E= Eº – 0.0592
–––––– log ––––––––––
n [MnO4–] [H+]8

Química Inorgánica I–Farrah Cañavera

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0.0592 1.00x10–4
= +1.507V – ––––––– log –––––––––––––––––––––
5 (1.00x10–2) (1.00x10–3)8

0.0592
= +1.507V – ––––––– log (1.00 x 1022) = + 1.246V
5

(ii) Para la media celda Fe3+/Fe2+ como una reducción:

Fe3+ + e– ! Fe2+ Eº= +0.771 V

[Fe2+] 0.0592 0.100

E= Eº – 0.0592
–––––– log –––––– = +0.771V – –––––– log ––––––
n [Fe3+] 1 1.00

E= Eº – 0.0592
–––––– log (0.100) = +0.830 V
1

Química Inorgánica I–Farrah Cañavera

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(b) El potencial corregido de la media celda MnO4–/Mn2+ es mayor que

el de la media celda Fe3+/Fe2+, por lo que se invierte última, se balancea
la transferencia de electrones y se suman:

Pt|Fe2+(0.100M),Fe3+(1.00M)||H+(1.00x10–3),MnO4–(1.00x10–2M),Mn2+(1.00x10–4M)|P

Eº = Ered + Eoxid.

O, Eº= Ecátodo – Eánodo

Eº= +1.246 V – (+0.830 V)

Eº= 0.416 V Química Inorgánica I–Farrah Cañavera

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Buelvas, Docente

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