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Cd+2 + Fe Cd + Fe+2
This reaction is divided into two parts, the reduction part, where cadmium
receives two electrons:
Cd+2 + 2e- Cd
Fe Fe+2 + 2e-
The oxidation of organic matter by oxygen is also an oxidation reduction
reaction. Organic matter, here represented by CH2O, reacts with O2:
Fe(H2O)6+3 Fe(H2O)5OH+2 + H+
and
Fe(H2O)6+3 + e- Fe(H2O)6+2
In the first case, one of the water molecules that has complexed with the
Fe+3 loses an H+ (this is how iron acidifies soil and water), however, the
oxidation state of the iron remains the same. In the second case, the water
molecules are not affected; the Fe+3 gains an electron, forming the more
soluble species Fe+2.
However, the real world tends towards maximum complexity. The transfer
of electrons is frequently accompanied by the transfer of hydrogen ions.
Manahan gives the example:
2 Fe+3 + H2 2 Fe+2 + 2 H+
2 Fe+3 +2 e- 2 Fe+2
and
H2 2 H+ + 2 e-
When we add the two half-reactions together, we get the overall reaction:
2 Fe+3 + H2 2 Fe+2 + 2 H+
Note that the electrons on each side of the half-reactions must cancel; there are
not electrons shown in the overall reaction.
The reaction shown above could go to either the left or right; we can deduce the
direction from the initial half-reactions. If we assume that the initial activities of
Fe+2, Fe+3, H+ are 1 (i.e., they are present at 1 molar concentration), and that H2
is present at 1 atmosphere pressure, hydrogen would be oxidized to H+, and Fe+3
would be reduced to Fe+2. We can visualize the half-reactions by separating
them schematically, as in figure 4.2.
Environmental Chemistry, 7th Edition, Stanley E. Manahan. Lewis Publishers, Boca Raton, 1999.
and
E° E°
pE° = = (at 25° C)
2.303 R T 0.0591
F
R is the molar gas constant, 8.3144 joule/˚K-mole, T is the absolute
temperature, and F is the Faraday constant, 96,493 Coulombs/ equiv. The
2.303 term is the conversion from natural log to base 10 log. It will take a
minute to explain why it’s included, so please be patient.
4.4 The Nernst Equation: Look back at figure 4.2 on p. 103. If the
concentration of Fe+3 ion is higher than the concentration of Fe+2, the
tendency of the electron deficient Fe+3 to acquire electrons will make the
electrode potential more positive. If the converse is true, than the potential
will become less positive. So the concentration of the various species
affects the electrode potentials.
-
Fe+3 + e → Fe+2 E0 = 0.77 Volts and pE0 = 13.2
We want to quantify the effect of the change in concentration of the
reactants, so we write:
2.303 R T [ Fe +3 ] 0.0591 [ Fe +3 ]
E=E + 0
log +2
=E +
0
log
nF [ Fe ] n [ Fe +2 ]
1 [ Fe+3 ]
pE = pE + log
0
n [ Fe+ 2 ]
This is why we used the “natural log to base 10 log conversion earlier.”
Later, we’ll see why we have a natural log involved.
If, for example, [Fe+3] is present at 10-3 M, and [Fe+2] is present at 10-5 M,
then the value of pE is:
1 [10−3 ]
pE = pE + log
0
= 15.2
n [10−5 ]
We can see that increasing the electron deficient species (Fe+3) relative to
the electron-rich species (Fe+2) increased the cell potential, and pE. Since
pE = -log(ae-), this means that the “activity” of the electron has decreased.
All of this should make sense.
In the case of the previous reaction, where Fe reduction was paired with
hydrogen oxidation, the whole reaction potential is the same as the Fe cell
reaction potential. For cases other than reduction by hydrogen, we must
find the difference between two cells in order to find the whole reaction
potential, and hence the reaction direction and equilibrium.
For the case of a solution of Cu+2 flowing through a lead pipe, the following
reaction can be written:
Cu+2 + Pb Cu + Pb+2
For the half-reaction Cu+2 + 2 e- Cu, pE0 = 5.71, while for the reaction
Pb+2 +2 e- Pb, pE0= -2.13.
If we assume that all reactants are present at unit activity, we can obtain the
overall reaction potential by subtracting the two reactions. The reason we
subtract is that, one of the reactions must go in the opposite direction from
what is written above. That is, one of the species must be oxidized in order
for the other to be reduced.
1 [Cu +2 ]
pE = pE + log
0
n [ Pb + 2 ]
4.6 The Nernst Equation and Chemical Equilibrium: Realize that as long as we
have inserted a volt meter into the circuit shown in Fig. 4.3 on p. 107, the
reaction cannot proceed, as electrons cannot flow through the volt meter. If
we were to bypass the meter with a wire, the reaction could proceed until it
reached equilibrium. The equilibrium constant for the reaction would be
written:
[ Pb+2 ][Cu] [ Pb+2 ]
K eq = +2
or, since the activities of both Pb and Cu are 1, K eq =
[ Pb][Cu ] [Cu + 2 ]
Note that the Equilibrium constant is the inverse of the logarithmic term in
the Nernst equation. We can now write:
1 [Cu +2 ] 1 1
pE = pE + log
0
= pE 0
+ log
n [ Pb + 2 ] n K eq
To find the equilibrium concentration, we must find the point where pE=0:
1 1 1 [ Pb +2 ] 1
pE = 0.00 = pE + log
0
= 7.84 − log +2
= 7.84 − log K
n K eq 2 [Cu ] 2
4.7 The Relationship of pE to Free Energy: So far, we’ve said nothing about
where the Nernst equation comes from, or why it includes a logarithmic
term, which must be converted from natural log to base 10 log. We won’t
say too much here either. Recall from basic chemistry that for the reaction:
aA + bB cC +dD
{C}c {D}d
∆G = ∆G + R T ln
0
a b
= ∆G 0
+ R T ln Q
{ A} {B}
Where G is the Gibbs Free Energy, and G0 is the Gibbs Free Energy of
Formation. When G is equal to 0, the reaction is at equilibrium. In order
for this to happen, G0 must be equal to -RT ln Q. When the activities of
A, B, C, and D are of the correct magnitude to cause -RT ln Q to be equal
to G0, then Q is equal to the equilibrium constant, Keq. So, at equilibrium:
∆G 0 = − R T ln K eq
Now, we can see why we have to include the conversion from natural log to
base 10 log. Backing up, and continuing,
∆G = ∆G 0 + R T ln Q Eqn 1
We also know that the work obtained from a chemical reaction is:
∆G = −n F E
and
∆G 0 = −n F E 0
We know this because n is the number of electrons per mole of
reactant, F is the electric charge of a mole of electrons, and E is the
potential driving this electrical current. We know that the work obtained
from an electric current is:
w =V i
where V is the potential, in joules/coulomb (volts), and i is the electrical
current in coulombs/second (amperes). In the present case, this work, in
joules/second (Watts) is the Free Energy, G.
∆G ∆G 0 RT
= + ln Q
− nF − nF − nF
we obtain
joules
8.3144 298° K
RT deg mole 0.0591
E = E0 + ln Q = E 0 − 2.303 ln Q = E 0 − log Q
− nF coulomb n
n 96,493
equiv
Because we know that, at equilibrium, G = 0, so E = 0, and Q must be
equal to Keq. So:
∆G 0 RT 0.0591
E =
0
= ln K eq = log K eq
−n F n F n
Keeping in mind that E has the opposite sign of G, if Q/Keq is >1, than G is
>0, and E <0. So the reaction proceeds to the left. Conversely, if Q/Keq is <1,
than G is < 0, and E >0. So the reaction proceeds to the right, as written.
and
1/8 NH4+ + ¼O2 1/8 NO3- + ¼H+ + 1/8 H2O pE0 = 5.85
and
Now, each reaction involves the transfer of one electron. This allows us to
consider these equilibria based on the number of electrons (oxygen molecules)
available to perform oxidation. Let’s look at the equilibrium expression for
the first reaction:
Recall that log(Keq) = npE0. If n = 1, then log(Keq) = pE0. So
1 1
[ NO3− ] 8 [ H + ] 4
K eq = 1 1
+
[ NH ] PO24
4
8
Look at Table 4.1 on page 111 of your text. The table lists a series of important
reactions in natural water, and their associated pE0. Also shown is pE0(W). This
value is also frequently expressed as EH, the potential measured in a water
system. As the reactions given above show, the H+ concentration in water
affects the reaction. This value is the pE0 for a pH of 7.
Some Problems: Based on the above, one might get the impression that we can
just measure the potential present in a natural water system and, based on its
value, calculate the equilibrium concentrations of all the species present.
Unfortunately, nothing is ever that simple. Most of the reactions described in
Table 4.1 are calculated from thermodynamic data, rather than from actual
measurements. In reality, most of the reactions do not behave in a Nernstian
manner. First of all, the kinetics are often so slow that the reactions do not reach
equilibrium. Secondly, the reactions are frequently not reversible. Even more
unfortunately, the definition of a reversible reaction is not clear-cut. In fact,
there are at least 3 different definitions that apply. They are:
Pt/H2/H+,Cl-/AgCl/Ag
As a galvanic cell (no external voltage applied) the reaction proceeds as:
Zn/H+,SO4-2/Pt
2H++ 2e- → H2
So, measuring the potential in a natural water system will give us a number.
However that number usually cannot be related to any absolute values of
concentration, as found from the Nernst equation. However, it can give an idea
of the relative position of the system. The following figure illustrates this:
From: Chemistry of the Environment, 2nd ed., Spiro and Stigliani, Prentice Hall, 2003.
4.9 The Limits of pE in Water:
1
pE = pE + log pO 24 [ H + ]
0
pE = 20.75 − pH
and, given that the activity of H2 gas, at one atmosphere, is 1, as is the
activity of water:
(
pE = pE 0 + log [ H + ] )
pE = 0.00 − pH = − pH
What these mean is that if pE exceeds the first value, water is oxidized, and
if it is less than the second value, water is reduced. Thus, water can only
exist in the pE region bounded by the two equations. In practice, water
electrolyzed very slowly, and in the case of chlorine addition, the pE can
exceed the theoretical value calculated.
Your text chooses to assume that PCH4 = PCO2 and that the pH is 7. We can
write the Nernst equation:
1
P 8
CO2 [H + ]
pE = 2.87 + log 1
= 2.87 + log[ H + ] = −4.13
P 8
CH 4
This yields an oxygen partial pressure of 3.0 x 10-72 atm. Since we can’t possibly
measure a value this low, we can never confirm this (although it’s very
unlikely). However, we can assume that, under conditions so reducing as to
ferment carbon dioxide to methane, the dissolved oxygen concentration is very,
very low.
So we can see that pE, or EH, can give us some idea of what reactions are most
likely to occur, and how they relate to one another. But drawing quantitative
conclusions about precise equilibria is, at best, risky.