5.
Page 76
Dr. M. Gerken
So far we have only mentioned the fact that transition elements have multiple oxidation states, but we have ignored the
impact of this on chemical behavior. We will do so now, and then we will continue to use redox principles to treat the
chemistry of the p-block elements. Redox chemistry is probably the most interesting (and complex) aspect of the chemical
behavior of the elements, and careful study of this material will greatly reward the effort expended. The majority of the
reactions which you do in Part II of the lab are in some sense redox reactions.
As background to this section, you should review how to balance redox reactions and other basic electrochemical
principles from General Chemistry.
5.1
Oxidation-Reduction reactions, better known by the short-form redox reactions, involve the transfer of electrons between
atoms and molecules during the reaction. They represent one of the major classes of chemical reactions. We can detect redox
reactions by monitoring the oxidation states of the atoms in the reactants and products. Any change in these formal oxidation
states during the reactions means that a redox reaction has taken place. Oxidation states were introduced in Chem2000, and
you should go through as many exercises on assigning oxidation states as possible. You may wish to review the section in your
Chem2000 textbook.
.. ..
H O
.. O
.. H
.. ..
H( O
.. )( O
.. )H
+
H
...
:O
..
.. .O :
..
+
H
..
.
:O
..
..
.O :
..
+I -I.. -I
.. +I
H O
.. H
.. O
Dr. M. Gerken
Page 77
6.
When H forms a binary compound with a metal, the metal forms a positive ion and H becomes a hydride ion,
H. Thus, in CaH2 the oxidation number of Ca is +II (equal to the group number) and that of H is I. [The
deciding factor remains the electronegativity of the bonding partner]
Oxygen can have an oxidation number of I in a class of compounds called peroxides, compounds based on
the O22 ion. For example, in H2O2, hydrogen peroxide, H is assigned its usual oxidation number of +I, and
so O is I. [If O is bonded to fluorine you have to use the definition given in 7.1.1]
The algebraic sum of the oxidation numbers in a neutral compound must be zero; in a polyatomic ion, the sum
must be equal to the ion charge. Examples of this rule are the previous compounds and others found in Example
4.8.
Page 78
Dr. M. Gerken
MnO4
Mn2+
MnO4
+ 8 H+ Mn2+ + 4 H2O
MnO4
+ 8 H+ + 5 e Mn2+ + 4 H2O
2 MnO4
+ 16 H+ + 10 e 2 Mn2+ + 8 H2O
3 H2O
Finally, check that the atoms and charges balance at the right and at the left
The following reaction takes place in standard basic solution (1 M OH-)
Fe(OH)2(s)
+ CrO42(aq) Fe2O3(s)
+ Cr(OH)4(aq)
We recognize that Fe changes oxidation state from +2 to +3, while Cr changes from +6 to +3. The two half reactions are:
Fe(OH)2
Fe2O3
Oxidation:
Material balance
2 Fe(OH)2 + 2 OH Fe2O3 + 3 H2O
Electron balance
2 Fe(OH)2 + 2 OH Fe2O3 + 3 H2O + 2 e
Multiply by 3
6 Fe(OH)2 + 6 OH 3 Fe2O3 + 9 H2O + 6 e
Reduction:
Material balance
Electron balance
Multiply by 2
Overall reaction:
CrO42
Cr(OH)4
2
CrO4
+ 4 H2O Cr(OH)4 + 4 OH
2
CrO4
+ 4 H2O + 3 e Cr(OH)4 + 4 OH
2
2 CrO4
+ 8 H2O + 6 e 2 Cr(OH)4 + 8 OH
H 2O
Finally, check that the atoms and charges balance at the right and at the left
ve G
+ve G
or
or
+ve E
ve E
Why do we have such a confusing convention? The origin of this discrepancy comes from the way that physicists define
current flow: although electrical current is entirely due to the migrations of electrons in a circuit, a forward current flow is
defined in standard theories of electricity as the direction of positive charge flow. It is when harmonizing standard electrical
conventions with chemical definitions that these apparently contradictory conventions are generated. In electrochemistry, a
reaction which is product favoured produces a voltage, and is therefore called a Voltaic cell, in honor of Alessandro Volta. A
Dr. M. Gerken
Page 79
reaction which is reactant favoured can be driven forward by the application of a greater opposite voltage; such reactions are
called electrolytic cells, and the process is named electrolysis.
We now want to remember another aspect of the meaning of G, which is that it tells for any given reaction the maximum
amount of the total energy change that may be harnessed for useful work. The electrochemical equivalent of this idea is the
maximum voltage of the electrochemical cell. This maximum potential is obtainable only from a fully charged cell running
under zero load. This means that we can calculate the maximum cell voltage from standard free energies for the reaction.
Consider the reaction:
Zn2+(aq)
+
Cu(s)
Zn(s) +
Cu2+(aq)
1
fG (kJ mol )
0
65.52
147.0
0
Since rG = {fG (products)} {fG(reactants)}, rG = (-147.0 kJ/mol) (65.52 kJ/mol) = 212.5 kJ mol1, and we
would predict this to be a spontaneous reaction. It is spontaneous, but frankly quite useless unless you need some finely
divided metallic copper and have only these reactants at hand. Let us now see if it is indeed possible to harness the useful
work from this reaction.
2 e
Cu(s)
Reduction
G 0
212.5 kJ mol 1
E =
=
= +1.10V
nF
2 96.485 kC mol 1
0
Dr. M. Gerken
Page 80
the left hand side of the notation. A convenient mnemonic device to remember this convention is Right Red Cat, i.e. that the
cathode process is a reduction process and is placed at the right of the cell notation. The vertical lines, |, in the notation
indicate a phase boundary, such as between a solid and a liquid. Double lines, ||, indicate double boundaries, such as
commonly occur when a salt bridge is placed between the two half cells. If the components of a redox reaction co-exist in
solution without a phase interface, they are listed together with a comma separating oxidized and reduced forms. This is often
the case when the current is introduced into a solution via an inert electrode (usually platinum metal); an example is the
oxidation of iron(II) to iron (III) for which the notation could be: Pt(s) | Fe2+(1 M), Fe3+(1 M).
The operation of a voltaic cell is summarized in Figure 21.4. It represents a complete electrical circuit. In the wires
external to the cell, the current is carried exclusively by a moving stream of electrons. However, within the solution, the
current must be carried by migrating ionic species, such as in our example cell Zn2+ and Cu2+ ions. Within the salt bridge, if
one is used, inert ions such as K+ and Cl carry the charges and provide for current flow.
Standard Half-Cell Reduction Potentials
From the construction of our electrochemical demonstration cell, and from the cell notation, it should now be obvious to
you that electrochemical half-reactions, which we arbitrarily introduced as a tool to balance redox reactions, have some
degree of physical reality they can after all be built into electrochemical half-cells. It should, for example, be possible to
uncouple the copper/zinc cell and construct other voltaic cells from them, for example a copper/lithium or a silver/zinc cell, etc.
This is indeed possible. It would also be nice to be able to assign a voltage to each half-cell, but this turns out to be
impossible, since the voltage depends on a complete electrical circuit being established. Nonetheless, this idea of a half-cell
potential is so attractive, that chemists have figured out a way to do so. We do it by arbitrarily setting one redox half-reaction
to zero, and measuring all other cells with respect to this arbitrary zero reference point. The universal reference standard for
electrochemistry is the standard hydrogen electrode, or SHE. For example, if the zinc half-cell is combined with the SHE, as
shown in the Figure below, a voltage is measured as +0.76 V. We assign this cell voltage entirely to the zinc half cell, since
SHE is zero. Alternatively, we combine the SHE with the copper half cell, and get +0.34 V. Then we can establish the
potential of the copper zinc cell as E = + 0.76 + 0.34 V = +1.10 V.
Since for any given combination of two half-cells, we can never be sure which half will act as the anode and which as the
cathode, electrochemists have a standardized way of expressing half-cell potentials, and that is always to depict them as
reductions. This leads to the compilation of the standard reduction potentials in aqueous solution which are compiled in
the Table below.
We can use this table in numerous ways. First of all, we can now construct an electrochemical cell out of any
combination of half cell reactions. Thus we can go and obtain potentials for the examples cited above:
Dr. M. Gerken
Page 81
Au (aq) + 3 e
Au(s)
Cl2(g) + 2 e
2 Cl (aq)
Cr2O7 2 (aq) + 14 H3O + (aq) + 6 e
2 Cr 3+ (aq) + 21 H2O(l)
+
I2(s) + 2 e
2 I (aq)
O2(g) + 2 H2O(l) + 4 e
4 OH (aq)
2+
Cu (aq) + 2 e
Cu(s)
Sn 4+ (aq) + 2 e
Sn 2+ (aq)
2 H3O + (aq) + 2 e
H2(g) + 2 H2O(l)
Sn 2+ (aq) + 2 e
Sn(s)
Ni 2+ (aq) + 2 e
Ni(s)
V 3+ (aq) + e
V 2+ (aq)
PbSO4(s) + 2 e
Pb(s) + SO4 2 (aq)
2+
Cd (aq) + 2 e
Cd(s)
Fe 2+ (aq) + 2 e
Fe(s)
Zn 2+ (aq) + 2 e
Zn(s)
2 H2O(l) + 2 e
H2(g) + 2 OH (aq)
3+
Al (aq) + 3 e
Al(s)
Mg 2+ (aq) + 2 e
Mg(s)
Na + (aq) + e
Na(s)
K + (aq) + e
K(s)
Li + (aq) + e
Li(s)
E (V)
+2.87
+1.77
+1.685
+1.52
+1.50
+1.360
+1.33
+1.229
+1.08
+0.96
+0.89
+0.855
+0.80
+0.789
+0.771
+0.535
+0.40
+0.337
+0.15
0.00
0.14
0.25
0.255
0.356
0.40
0.440
0.763
0.8277
1.66
2.37
2.714
2.925
3.045
Li (aq) + e Li(s)
E = 3.045 V
We now combine them in such a way as to get a positive overall cell potential. This means we must reverse the lithium
equation, making it the anode (where the oxidation will take place.)
E = +3.045 V
Li(s) Li + (aq) + e
now we have the cell potential for the overall reaction
Cu(s) + 2 Li + (aq)
Ecell = +3.382 V
Cu 2+ (aq) + 2 Li(s)
Note here very carefully, that the voltage was not doubled when the coefficients are doubled. However, n for this
reaction = 2. Cell voltages are therefore independent of stoichiometry. The stoichiometric information is stored in the
value of n.
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Dr. M. Gerken
silver/zinc cell
From the table we get the half-reactions:
Zn 2+ (aq) + 2 e Zn(s)
Ag + (aq) + e Ag(s)
E = 0.763 V
E = +0.80 V
We now combine them in such a way as to get a positive overall cell potential. This means we must reverse the zinc
equation, making it the anode (where the oxidation will take place.)
E = +0.763 V
Zn(s) Zn 2+ (aq) + 2 e
now we have the cell potential for the overall reaction
2Ag(s) + Zn2+(aq)
Ecell = +1.563 V
2Ag+ (aq) + Zn(s)
These examples should be sufficient to show how cell potentials are determined for standard reduction potentials. Remember
that voltaic cells must have a positive cell potential.
a)
Spontaneity of reaction
Combine any two standard reduction reactions by reversing one of the couples and adding the resulting potentials together.
If the E cell is positive, the reaction as written is spontaneous. If negative, the reverse reaction is spontaneous.
b)
Any species with a negative Eelectrode will tend to be a reducing agent, and elements with large negative electrode
potentials are strong reducing agents.
c)
Any species with a positive Eelectrode will tend to be an oxidizing agent, and elements with large positive electrode
potentials are strong oxidizing agents.
5.2
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Dr. M. Gerken
Latimer diagrams
The main disadvantage of the Table of Redox Potentials is that it is organized by the voltage of the process, rather than by
the chemical species involved. This is great if you want to build a battery, or to use an electrochemical process in an analytical
technique, e.g. to monitor the concentration of a given species. But it is not great if you want to understand the complex redox
chemistry of an element such as iron, copper or manganese. To address this issue, Latimer devised a very helpful way to
display redox potentials for the elements. These are given in an Appendix in the text by Shriver, Atkins and Langford.
We illustrate both the need for, and the method of construction, of Latimer diagrams with the following example: What
happens when Fe(s) is reacted with a strong, non-oxidizing, acid (for example, hydrochloric or perchloric acid)? Now there
are two common oxidation states of Fe, 2+ and 3+. We thus need to decide which of these two species is predicted by
thermodynamics to form in acid solution?
Reminder: thermodynamic data will predict which reactions ought to occur, but cannot determine whether they
happen at an observable rate or not. Most of the redox reactions of inorganic compounds are rapid reactions, but there are
many times when thermodynamics predicts more than one possible product, and where the actual product is selected by the
rate of reaction. We will say a bit more about this later on. The example dealt with here can be decided unambiguously by
thermodynamics.
From the table of reduction potentials, we pick out the data that is available for iron. We then remember that the free energies
of chemical reactions, i.e. G, obey algebra (often called Hess' Law of Heat Summation). This allows us to combine the two
equations to obtain the unknown redox potential relating iron in the 3+ state to the element. The calculations are summarized:
Reaction
Potential
G = nFE
2+
Fe + 2e Fe
-0.440 V
-2 F -0.440
Fe3+ + e- Fe2+
+0.771 V
-1 F +0.771
Fe3+ + 3e- Fe
NOT +0.331V!!!!
= +0.109 F
= -3 F -0.036
Thus we have obtained the desired potential, the so-called skip potential, for the direct conversion of elemental iron to
iron(III):
E = -0.036 V
Fe3+ + 3e- Fe
and we can answer the original question. When Fe is dissolved in acid, we consider the reverse of reactions 1 and 3. We see
that the potential for the formation of Fe(II) is greater than
for the formation of Fe(III). Thus, even though the
3+
formation of Fe3+ is overall favored, the reaction has an even
+0.036 V
Fe
3+
Fe
Fe
greater tendency to stop at the Fe(II) stage. We can diagram
2+
G
Fe
this effectively by plotting the free energy terms (as Fe
+0.440 V
2+
multiples of the Faraday constant) as a function of oxidation
Fe
state. In effect, the reaction will stop in the "well" at Fe2+,
0
+I
+II
+III
because it would cost energy to rise up from the Fe(II) state
oxidation state
up to the Fe(III) state.
Latimer diagrams are convenient for the display of all redox potentials relating to a given element, including the skip
potentials. Thus the three redox potentials we have considered so far for iron are displayed as follows:
-0.036
+0.771
Fe
3+
Fe
2+
-0.440
Fe
For clarity I have added arrows to the Latimer diagram. Thus the numbers as written are standard reduction potentials, i.e.
the sign of the redox potential refers to the reaction as it proceeds from left to right. If you need to consider the reverse
reaction, as in our question above, the sign must be reversed. Latimer diagrams do not normally have such arrows, so that you
need to remember this convention!
Page 84
Dr. M. Gerken
Cu
The free energy diagram is plotted at right, and the Latimer diagram becomes:
+0.340
+1.8
Cu
a)
3+
Cu
2+
+0.159
Cu
Cu
2+
Cu
+0.520
Cu
+I
+II
What happens when Cu(s) is placed in water or acid? The reverse of the reactions leading to Cu+ and Cu2+ are both
negative! Under standard conditions, copper will not be oxidized by acid! Remember that in your lab experiment on the
reactions of metals, you had to use HNO3 to dissolve copper wire. In other words, we needed to add a reagent capable of
supplying the energy required to overcome the barrier depicted in the above graph. This depends on the additional redox halfreaction:
E = +0.803 V
2 NO3- + 4 H+ + 2 e- N2O4 + 2 H2O
The overall reaction is:
Cu + 2 NO3- + 4 H+ Cu2+ + N2O4 + 2 H2O E = +0.463
You may also ask why the product of the nitric acid oxidation is Cu(II) rather than Cu(I). We need to work out the
potential for an overall reaction to form Cu(I):
Cu + NO3- + 4 H+ Cu+ + N2O4 + H2O E = +0.283
However, the overall reaction to Cu+ has E > 0; since this is a less positive EMF, the reaction proceeds directly to Cu2+ and
does not halt at Cu+. This is of course also clear from the free-energy diagram above.
NOTE: be sure that you can obtain such balanced redox reactions from the three redox half-reactions involved in this question.
Past experience has shown that even the best students consistently fail this task!
b)
Copper(I) in acid solution has an interesting property. Consider the possible reactions of Cu+: it can be reduced to Cu or
oxidized to Cu2+. Let us consider both of these processes.
Reaction
Potential
G = nFE
+
Cu + e Cu
+0.520 V
-1 F +0.520
Cu+ Cu2+ + e-0.159 V
-1 F -0.159
2Cu+ Cu + Cu2+
+0.3611
= - 0.361F
-1 F +0.361
NOTE: The combination of these two redox half reactions describe a balanced redox reaction, i.e. effectively the final reaction
describes an electrochemical cell. Whenever this is the case, the potentials obtained via the free energy calculation is the same
as just adding the redox potentials (with the correct sign!) together.
What we have demonstrated is that Cu+ is unstable towards disproportionation, the process in which a compound
undergoes an autoredox reaction to produce forms of the element with higher and lower than the original oxidation state. The
reverse of this equation, the conversion of Cu and Cu2+ to 2 Cu+ is called comproportionation. Thermodynamics tells us that
for copper, the disproportionation reaction is product-favored, whereas comproportionation is not product-favored.
0.771
-0.44
Fe 2+
Fe
-0.04
3
[Fe(CN)6 ] -
0.361
-1.16
[Fe(CN)6 ] 3+
We remember from our discussion of acid/base chemistry that Fe in acid solution is a short-hand representation for the aqua
complex, [Fe(OH2)6]3+, while Fe2+ is really [Fe(OH2)6]2+. Thus the two branches of the diagram actually reflect identical redox
2
Page 85
Dr. M. Gerken
processes for iron in the presence of two ligand systems. We can now see at a glance that the hexacyano complex of Fe(III) is
more stable than the aqua ion with respect to reduction to Fe(II). Also, the oxidation of Fe(0) to Fe(II) is considerably more
favorable in the cyanide/acid mixture than in aqueous acid. A Latimer diagram can thus be extended to include any number of
related redox systems. We could just as well construct a branch in which iron was coordinated to ammonia or chloride ions,
for example.
In general, anything which alters the free energy of the system will change the redox potentials. The following factors all
affect the size of G :
(1)
Concentration
(2)
Temperature
(3)
Other reagents which are not inert
(4)
pH (a special case of (3))
In practice, the most important of these two examples for aqueous element chemistry is pH changes. It has become
conventional to construct Latimer diagrams for the two extremes of pH = 0 and pH = 14 (respectively 1 M acid and 1 M base).
This is shown for the element manganese below:
+VII
+VI
+V
+IV
+III
+II
acidic solution
MnO4-
0.90
HMnO4-
1.28
(H3MnO4)
2.9
MnO2
0.95
Mn3+
1.5
Mn2+
-1.18
Mn
basic solution
MnO4-
0.56
MnO42-
0.27
MnO43-
0.93
MnO2
0.146
Mn2O3
-0.234
Mn(OH)2
-1.56
Mn
Note that dramatic differences in redox potentials occur for these two sets of conditions. The reason for this is that large
numbers of H+ and OH ions are usually involved in the redox half reactions. Anything that affects the concentration of these
ions will therefore have a dramatic effect on the redox potentials. This is such an important consideration that it has led to the
wide-scale use of a graphical presentation of the free energy changes that accompany redox reactions. We now consider such
Frost diagrams.
5.3
Frost diagrams
Frost diagrams are essentially the same as the graphs of free energy against oxidation state, where G is given in units of nF
(i.e. in Volts). They are simply quantitative versions of the graphs we have already been considering. We demonstrate the
construction of complex Frost diagrams for the element manganese, which has as complicated a redox chemistry as any
element known.
+VI
+V
+IV
+III
+II
acidic solution
MnO4-
0.90
HMnO4-
1.28
(H3MnO4)
2.9
MnO2
0.95
Mn3+
1.5
Mn2+
-1.18
Mn
basic solution
MnO4-
0.56
MnO42-
0.27
MnO43-
0.93
MnO2
0.146
Mn2O3
-0.234
Mn(OH)2
-1.56
Mn
Page 86
Dr. M. Gerken
OxSt
Species
Calculation
value of nE
(V)
0.0
Mn
+II
Mn2+
2 1.18
2.36
+III
Mn3+
1 1.5 + 2.36
0.86
5
(HMnO4)4
MnO2
1 0.95 + 0.86
0.09
+V
H3MnO4
1 2.9 + 0.09
2.99
+VI
HMnO4
1 1.28 + 2.99
4.27
+VII
MnO4
1 0.90 + 4.27
5.17
nE (V)
+IV
H3MnO4
Acid
1
Base
Mn
MnO2
II
III
-1
IV
Mn3+
VI
(MnO4)2-
VII
(MnO4)-
-2
Mn2+
-3
(MnO4)3MnO2
Mn(OH)2
Mn2O3
-4
Oxidation State
a)
Species lying high on the diagram are oxidizing agents towards species on their left, while species high on the diagram act
as reducing agents to other oxidizing agents on their right. Another way to visualize this is by considering the lines connecting
the higher and lower lying species. If the line has a postitive slope, the higher-lying species is an oxidizing agent. If the line
has a negative slope, the higher-lying species is a reducing agent.
Thus for Mn in both acid and base solution, MnO4 is an oxidizing agent (the line has a positive slope), being reduced to
several possible manganese species of lower oxidation state. In acid solution, the remaining forms of manganese down to Mn3+
are all potential oxidizing agents, while in base the lowest oxidizing agent is MnO2. Elemental manganese, (i.e. manganese
metal) is a reducing agent (the line has a negative slope), being itself oxidized most readily to Mn2+ in acid solution, and Mn2O3
in base. In base only, Mn(II) can also act as a reducing agent.
b)
Once we have identified potential oxidizing and reducing agents from the slopes of the lines, their relative strength can be
determined by the steepness of the slope of the lines. The steeper the slope, the stronger the agent. Thus MnO4 is a much
more powerful oxidizing agent in acidic solution than in basic solution. On the other hand, metallic manganese is a slightly
stronger reducing agent in basic solution.
c)
Dr. M. Gerken
Page 87
Species at the bottom of the graph have low free-energy, thus little tendency to react. The lowest species on the graph are
the thermodynamic final product(s) of the redox reactions involving that element. Note that many Frost diagrams display a
thermodynamic well. This is the case for manganese, for which the well is Mn2+ in acid and Mn2O3 (i.e. Mn(III)) in base.
d)
If a species lies above the line connecting its neighbors, it is thermodynamically unstable towards disproportionation. This
has been described as a point lying along a concave line. For example, in basic solution MnO43 lies on a point which is above
the line connecting MnO42 and MnO2. This means that the reaction:
2 MnO43 + 2 H2O MnO42 + MnO2 + 4 OH
is predicted to be product-favored.
e)
Species likely to undergo comproportionation to a third species are located to left and right of a point which lies below the
line connecting the two species. Thus in acid solution, a mixture of MnO2 and Mn are expected to react together to form Mn2+.
The rate of this reaction may be hindered by the insolubility of both species, but thermodynamically it is favored. Similarly, in
base, a mixture of MnO2 and Mn(OH)2 should comproportionate to Mn2O3. Note an important difference between
disproportionation and comproportionation. The former process renders a single species unstable, in that an autoredox reaction
can occur at any time. Comproportionation, on the other hand, requires both reactants to be present at the same time, and if
one is missing the other species remains stable.
Dr. M. Gerken
Page 88
We see that all the metals are potent reducing agents, with the exception of copper, for which the oxidized forms have a
higher free energy than the element. The reducing strength of the metals goes down smoothly from calcium to nickel,
across the period, with nickel being only a mild reducing agent. The jump to copper is fairly large, but its behavior is
consistent with the trend towards weaker reducing power - copper simply has none.
The earlier transition elements favor the +3 oxidation state as the most stable form (bottom of the diagram), while for the
latter elements +2 is more stable, sometimes (as for cobalt) considerably more stable.
The elements in the middle of the series - Mn and Fe - have the largest range of accessible oxidation states. But the free
energies of the highest oxidation states of these elements are extremely high, and they are all potent oxidizing agents. In
fact, only Ti in its highest state (+4) has virtually no oxidizing power (if we ignore the calcium and scandium ions, which
immediately form stable noble-gas configurations forms and are extremely stable and totally non-oxidizing.)
5.4
Page 89
Dr. M. Gerken
A detailed consideration of the kinetics of redox processes is beyond the scope of this course. However, in order to make
sense of redox reactions, particularly those of the non-metals, we will require to take account of a few kinetic principles.
H2
0.040
0.288
0.801
0.875
0.588
0.977
1.223
1.179
1.064
1.216
1.1
0.818
1.048
1000 A/m2
O2
0.638
1.28
0.660
0.984
1.244
0.726
H2
0.048
0.676
1.254
1.089
0.798
1.220
1.230
1.262
1.229
1.254
1.1
1.292
1.241
10000 A/m2
O2
0.766
1.49
0.793
1.131
1.63
0.853
For the simple reaction of hydrogen evolution by a metal dissolving in water or acid, the overpotential is ~0.6 V. This
explains why Zn, Fe, Ni and Pb do not evolve hydrogen gas when placed in water. Although the E for Zn is 0.76 V in 1 M
acid, this is reduced considerably when the [H3O+] is 1 10-7 in neutral solution. [HINT: use the Nernst equation!] Thus we
found in the lab that Zn did not react with boiling water, but produced H2 rapidly from 6 M H3O+.
ASIDE: The presence of overpotentials is often exploited in the design of electrochemical experiments and industrial cells.
Thus redox reactions can be studied at voltages where H2 or O2 evolution from water should be occurring, but does not due to
the overpotential. This is where the table from Harris becomes useful in finding an electrode material with in this case the
highest possible overpotentials. On the other hand, there is a great deal of interest in photoelectrochemistry, in which
sunlight is harnessed directly in a suitable electrochemical cell to split water into H2 and O2. Such cells require electrodes with
the lowest overpotential, and thus they often use platinized Pt (Pt covered with a colloidal deposit of fresh Pt on the surface) as
the electrode material.
Dr. M. Gerken
Page 90
The inner-sphere mechanism is common for redox reactions involving oxoanions. For example, the reduction of
oxoanions by NO2- occurs by attack of N on the oxygen atom of the oxoanion:
NO2- + OCl- NO3 + ClThe rate of reduction are found to be:
ClO4- < ClO3- < ClO2- < ClOand
ClO4- < SO42- < HPO42Thus the lower the oxidation state of the central atom, the faster the reaction is found to be. Why? Because the O-E bond is
strongest for the highest oxidation state, and this bond must be broken for the reaction to proceed. Further evidence in favor
of this hypothesis is the effect of size:
ClO4- < BrO4- < IO4The strength of the bond is reduced as the central atom size is increased.
5.5
Pourbaix diagrams
We now wish to discuss the fate of the metallic elements in aqueous solution in somewhat more detail. This ties in with a lot
of the work in the lab so far, and has important implications particularly for environmental chemistry.
Dr. M. Gerken
Page 91
Dr. M. Gerken
Page 92
To test your ability to read Pourbaix diagrams, see if you can find answers to the following:
(a) The form of iron which is the strongest oxidizing agent: FeO42- at [H+] 1 M
(b) The form of iron which is the strongest reducing agent: Fe(0), elemental iron
(c) The predominant form at pH = 7 and E = 0.0 V:
Fe(OH)3 predominates, but close to Fe2+/Fe(OH)2
3+
2(d) E for (acid) reduction of FeO4 to Fe :
1 M, 0 pH = 0 so E = 2.2 V
(e) E for reduction of Fe2+ to Fe(s):
E = 0.5 V (This MUST be an acid process. Why?)
On the diagram, dashed lines d and e represent respectively the normal and overpotential for oxygen evolution according to:
2 H2O 4 H+(aq) + O2 + 4 eE = +1.229 V.
The actual E for hydrogen evolution is given by f, while the overpotential is given by line g:
E = 0.00 V
2H+ + 2e- H2
Dr. M. Gerken
Page 93
Note that there are some limitations to this approach. First of all, the concentration of the elements in natural waters is
often much lower than standard conditions. Furthermore, these data are only valid for pure water plus the element in
question. For example, on this basis we would say gold cannot exist in sea water. However, it does, as a chloro complex,
which is soluble. This is due to a complexation equilibrium. Nevertheless the combined E/pH diagrams provide a very
comprehensive insight into the behavior of the elements in aqueous solution, and this is clearly the most important set of
conditions relevant to the terrestrial environment.