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Equilibrium Electrochemistry
Equilibrium Electrochemistry
Equilibrium Electrochemistry
Because at 25C, RT/F = 25.7 mV, a practical form of the Nernst equation is
E = E (25.7 mV/) ln Q
For a reaction with = 1, if Q is decreased by a factor of 10, the emf becomes more positive by
59.2 mV. The reaction has a greater tendency to form products. If Q increases by a factor of 10,
then the cell potential falls by 59.2 mV and the reaction has a lower tendency to form products.
Concentration cells
We can use the Nernst equation to derive an expression for the emf of an electrolyte
concentration cell: M|M+(aq, L)|M+(aq, R)|M
M+(aq, R) + e- M Right The standard emf of the cell is zero.
+ -
M (aq, L) + e M Left RT aL RT bL
+ +
M (aq, R) M (aq, L) Q = aL/aR, = 1 E = ln ln
F aR F bR
If R is the more concentrated solution, E > 0. The positive potential arises because positive ions tend
to be reduced, so withdrawing electrons from the electrode. This process is dominant on the right.
One important example of a concentration cell the biological cell membrane more
permeable to K+ ions than either Na+ or Cl- ions. In the enzyme (Na+-K+)-ATP, the hydrolysis
of ATP drives the pumping of ions across the membrane. The concentration of K+ inside an
inactive nerve cell is about 20 times that on the outside, whereas the concentration of Na+
outside the cell is about 10 times that on the inside. The difference in concentrations of ions
results in a transmembrane potential difference of about 62 mV. This negative potential
difference the resting potential of the cell membrane.
The transmembrane potential difference important for the transmission of nerve
impulses. Upon receiving an impulse (called an action potential), a site in the nerve cell
membrane becomes transiently permeable to Na+ and the transmembrane potential difference
changes. To propagate along a nerve cell, the action potential must change the transmembrane
potential by at least 20 mV, to values less negative than 40 mV. Propagation occurs when an
action potential in one site of the membrane triggers an action potential in an adjacent site,
while sites behind the moving action potential return to the resting potential.
Cells at equilibrium
A special case of the Nernst equation reaction at equilibrium. Q = K, K the equilibrium
constant of the cell reaction. Because chemical reaction at equilibrium cannot do work, it generates
zero potential difference between the electrodes. Q = K and E = 0 gives
ln K = FE/RT
Using this equation we can predict equilibrium constants from standard cell potentials.
The standard potential of the Daniell cell is +1.10 V. Then we can calculate the
equilibrium constant for the cell reaction as
Cu2+(aq) + Zn(s) Zn2+(aq) + Cu(s)
ln K = 2(9.6485104 C mol-1)(1.10 V)/{(8.3145 J K-1 mol-1) (298.15 K)} = 42.81
K = 1.51037
The displacement of copper by zinc virtually goes to completion.
If E > 0, K > 1 at equilibrium the cell reaction lies in favor of products. If E < 0,
K < 1 the reactants are favored at equilibrium.
Standard potentials
Each electrode in a galvanic cell makes a characteristic contribution to the overall cell
potential. It is not possible to measure the contribution of a single electrode one electrode
can be assigned a value zero and the others assigned relative values on that basis. The
specially selected electrode the standard hydrogen electrode (SHE):
Pt(s)|H2(g)|H+(aq) E = 0 at all T.
The standard potential, E(Ox/Red), is then measured by constructing a cell in which
the couple of interest form the right-hand electrode and the standard hydrogen electrode is on
the left. For example, the standard potential of the Ag+/Ag couple is the standard potential of
the cell Pt(s)|H2(g)|H+(aq)||Ag+(aq)|Ag(s) +0.80 V
AgCl/Ag,Cl- couple: the standard emf of the following cell:
Pt(s)|H2(g)|H+(aq)||Cl-(aq)|AgCl(s)|Ag(s) E( AgCl/Ag,Cl-) = E = +0.22 V
Although a standard potential is written like it refers to a half reaction
AgCl(s) + e- Ag(s) + Cl-(aq) E(AgCl/Ag,Cl-) = +0.22 V
it should be understood as the potential for the overall reaction:
AgCl(s) + 1/2 H2(g) Ag(s) + H+(aq) + Cl-(aq) E = +0.22 V
The standard potential is thus determined by properties of both the hydrogen electrode and the
couple to which the potential refers.
An important feature of standard emf of cells and standard potentials of electrodes they
are unchanged if the chemical equation for the cell reaction or a half-reaction is multiplied by
a numerical factor. A numerical factor increases rG but it also increases the number of
electrons transferred by the same factor, so the value of E remains unchanged.