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Voltaic cells can do work because G for the redox reaction is negative. The voltaic cell continues to do work until
an equilibrium is reached between the reactants and products.
As the cell does work, electrons flow, the redox reaction takes place, the concentrations of reactants and
products change towards equilibrium, and the cell potential continually decreases.
Think about it: At equilibrium the voltaic cell has:
E = ?
Q = ?
G = ?
REMEMBER: emf, E or E, are INTENSIVE properties (J/C) and do not depend upon the extent of the reaction.
Changing the balancing coefficients in a 1/2 reaction does not change the value of E or E. HOWEVER,
changing the balancing coefficients will change G and G (extensive property) as we shall see latter.
Coulomb (C):
Fundamental unit of electric charge.
One electron has a charge of 1.602x10-19 C.
1 C = 6.241x1018 e = 1.0364x10-5 mole e
Faraday (F):
Absolute charge of one mole of electrons.
F = 9.6485x104 C/mole
Voltage (V):
The driving force or electrical pressure
electrons feel to complete a process.
1 V = 1 J/C
Energy (J):
1 J = kgm2/s2 = 1 V*C
Current (A):
the number of electrons that flow per second.
ampere (A or Amp), 1 A = 1 C/s
Work (w):
Voltaic cell (process is spontaneous, system can do work):
wmax = -nFE = G (max work done by system)
Electrolytic cell (process is non-spontaneous, work must be done
on system by surroundings, Eexternal, to drive reaction):
w = nFEext (work done on system)
Watt (W):
electrical power unit. The rate of energy expenditure per second.
1 W = 1 J/s=VA
1 kWh = 3.6x106 J = (1000 W * 3600 s)
Electrochemistry
Using this, an equation can be written that directly relates the standard emf of a redox reaction to its
equilibrium constant.
What does this mean? For redox reactions, we can determine G and K for the reaction if we
know (measure or calculate) the cell potential under standard conditions.
Calculate G and the equilibrium constant for the disproportionation of copper(I) ion at 25C. Are copper(I)
ions stable in aqueous solution?
2 Cu+(aq) <> Cu2+(aq) + Cu(s)
1Faraday,
Michael: The English chemist and physicist Michael Faraday, (b. Sept. 22, 1791, d. Aug.
25, 1867), is known for his pioneering experiments in electricity and magnetism. Many consider
him the greatest experimentalist who ever lived. Several concepts that he derived directly from
experiments, such as lines of magnetic force, have become common ideas in modern physics.
Electrochemistry
G = G + RT ln Q = -RT ln(K/Q)
where Q is the reaction quotient. (Remember the magnitude of Q compared to K can be used to predict the
direction of chemical change to reach equilibrium.) Since G = -nFEcell and G= -nFEcell we can derive an
equation (The Nernst Equation2) that allows us to calculate the cell potential under nonstandard conditions.
Lets derive this equation!
Nernst, Walther: The German physical chemist and inventor Hermann Walther Nernst, b. June 25,
1864, d. Nov. 18, 1941, was awarded the NOBEL PRIZE for chemistry in 1920 for his discovery (1906)
of the third law of thermodynamics, which states that entropy approaches zero as temperature
approaches absolute zero. He introduced the Nernst equation (1889), which relates electric potential
to various properties of the electric cell.
Electrochemistry
G
(Q = ?)
Ecell
Spontaneous
Forward
Reaction?
K vs
Q
Ecell
>0
>0
<0
<0
Spontaneous
Forward
Reaction?
Electrochemistry
ANODE
CATHODE
1.
Write the balanced net ionic redox equation for the reaction
2.
Without doing ANY calculations, determine if the reaction is spontaneous under the conditions given.
3.
4.
Electrochemistry
1.2. G = 166 kJ
1.3. K = 1.4x1029
1.4. If [Ag+] = 1.0 M, the pH = 7.00, and the over pressure of O2 is 0.20 atm, find E = 0.005 V
2. Now consider this redox reaction:
2.1. Determine E = ?
2.2. G = ?
2.3. K = ?
2.4. If [Ag+] = 1.0 M, the pH = 7.00, and the over pressure of O2 is 0.20 atm, find E = ?
Electrochemistry
1.
2.
A voltaic cell is constructed using the reaction shown above. The concentration of Sn2+ in the cathode half-cell
is 1.00 M. The anode compartment contains [SO42] = 0.50 M and an unknown concentration of Pb2+ ions in
equilibrium with PbSO4(s) at 25C. Under these conditions, the cell generates an emf of +0.220 V. Determine
Ksp for PbSO4.
Electrochemistry
What is the effect on the cell emf of each of the following changes?
1.
2.
3.
A solution of Zn(NO3)2(aq) is added to the anode compartment, increasing the moles of Zn2+, but not
changing its concentration.
4.
5.
E is zero:
E = Ered + Eox = -0.28 V + (+0.28 V) = 0.00 V.
However, if the concentrations of the Ni2+ ions are different in the half-cells, then a cell
potential exists, E, and electricity will flow until the Ni2+ concentrations in the half-cells become equal.
Determine E at 25C for the
concentration cell depicted on the
left.
Electrochemistry
In what direction will electrons flow to equalize the Ag+ ion concentrations between the two cells? Which
electrode corresponds the the anode half-cell? the cathode? (Sketching a drawing of the cell is helpful here.)
2.
Write the half reaction for each electrode and the overall cell reaction.
A:
B:
4.
5.
Think about it: What are the signs of Hsys, Ssys, Ssurr, Suniv and G for this process?
Electrochemistry
10
Measuring pH
A pH meter employs a voltaic cell for which the cell potential is very sensitive to pH. A simple (but impractical) pH meter
can be constructed by using two hydrogen electrodes: one standard hydrogen electrode (H2 = 1 atm [H+] = 1.00 M) and
another electrode (H2 = 1 atm [H+] = ?) dipped into the solution of unknown pH > 0. The two half-cells are connected by
a salt bridge or porous glass disk. This is essentially a concentration cell for H+ ions.
1.
If a solution produces an emf of 0.293 V at 25C with this pH probe, what is the pH of the unknown solution?
Electrochemistry
11
E = +0.0895 V
1. Combine this reduction half-reaction with an oxidation half-reaction to obtain the chemical reaction for the Ksp of
AgSCN(s).
Note: What we have done is written a non-redox reaction, a Ksp reaction, as a sum of redox half-reactions! This is
not common but can be done for some systems to determine equilibrium constants.
Electrochemistry
12
Ered = 1.51 V
If the reduction of 1.0 M MnO4 is carried out in a pH = 2.00 buffer with 1.0 M Mn2+ , what is Ered? (Note: under
standard conditions pH = 0.00 = 1 M [H+].)
E = Eo
RT ln(Q)
0.0257Vmol
[Mn 2+ ]
= 1.51V
ln
2
+ 8
nF
5mol
[MnO4 ][H ]
1.1. Repeat the calculation for a pH = 7.00 buffer. How sensitive is this reduction voltage to pH change?
Electrochemistry
13