Chapter 18: Electrochemistry: Key Topics
Chapter 18: Electrochemistry: Key Topics
Chapter 18: Electrochemistry: Key Topics
Key topics:
Galvanic cells
Nernst equation
Batteries; electrolysis
In a redox reaction both the mass and the charge must be balanced
example: (net ionic equation)
Al(s) + Ni2+(aq) → Al3+(aq) + Ni(s)
balanced by mass, but not by charge
What do we do?
Fe2+ ! Fe3+
2. Balance by mass for elements other than H and O
Cr2 O27 ! 2Cr3+
Fe2+ ! Fe3+
3. Balance O using H2O
Cr2 O27 ! 2Cr3+ + 7H2 O
Fe2+ ! Fe3+
4. Balance H using H+
14H+ + Cr2 O27 ! 2Cr3+ + 7H2 O
Fe2+ ! Fe3+
5. Balance change using e–
6e + 14H+ + Cr2 O27 ! 2Cr3+ + 7H2 O
Fe2+ ! Fe3+ + e
Galvanic Cells
The reaction will stop when the copper metal gets covered
with silver.
If we want to use this spontaneous reaction to extract energy
and do work we need to separate the two half reactions by
building a galvanic cell (also called a voltaic cell):
Electrodes
o anode, oxidation
o cathode, reduction
Half-cell
o one container, electrode, and solution
Salt bridge
o conducting medium through which ions can move from
one half-cell to the other half-cell
o this is electrolytic conduction (the movement of ions
carrying electrical charge)
o contrast with metallic conduction (electrons through wire)
Ion migration
o anions migrate towards the anode
o cations migrate towards the cathode
Conduction of charge
o Cu2+ enters anode solution (+ charge builds up)
o anions from the salt bridge counter this buildup
o Ag+ leaves cathode solution (– charge builds up)
o cations from the salt bridge counter this buildup
o salt bridge maintains electrical neutrality
(otherwise the reaction will quickly stop)
Measured current
o called the overall cell potential (Ecell)
o is the difference between the electrical potentials at the
two electrodes (the two half-cell potentials)
o varies with concentration, temperature, metals/ions used.
Measure the
current: 0.34 V
Cu2+ + 2e ! Cu(s) Ecell = Ered, Cu2+ /Cu + Eox, H+ /H2
H2 (g) ! 2H+ + 2e 0.34 V = Ered, Cu2+ /Cu + 0
Measure the
current: 0.76 V
Solution:
The relevant entries in Table 18.1 are:
Pb2+(aq) + 2e– → Pb(s), E° = -0.13 V
Cd2+(aq) + 2e– → Cd(s), E° = -0.40 V
Solution:
The relevant entries in Table 18.1 are:
Pb2+(aq) + 2e– → Pb(s), E° = -0.13 V
Ni2+(aq) + 2e– → Ni(s), E° = -0.25 V
– –
Cl2(g) + 2e → 2Cl (aq) E° = +1.36 V
2H+(aq) + 2e– → H2(g) E° = 0 V
The Cl half-reaction will not occur because it would have to run
as a reduction, but there is no Cl2(g) present.
(a) The Pb half-reaction will not occur because it would have
to run as a reduction, but there are no Pb2+(aq) ions present.
(b) The Pb half-reaction would have to run as an oxidation and
the hydrogen reaction would have to run as a reduction. This
works because Pb(s) and H+(aq) are present. The reaction is
2H+(aq) + Pb(s) → H2(g) + Pb2+(aq)
G= n F Ecell G = n F Ecell
n = number of moles of electrons
F = Faraday constant = electric charge contained in one mole of electrons
Ecell measured in V
G = nFEcell = RT ln K
RT
and rearrange to get Ecell = ln K
nF
plug in the values of R, F, and room temperature (298 K) :
0.0257 V
Ecell = ln K
n
and then convert “ln” to “log”
0.0592 V
Ecell = log K
n
e.g., Calculate ΔG° for the following reaction at 25°C
Pb(s) + Ni2+(aq) Pb2+(aq) + Ni(s)
Solution:
The relevant entries in Table 18.1 are:
Pb2+(aq) + 2e– → Pb(s), E° = -0.13 V
2+ –
Ni (aq) + 2e → Ni(s), E° = -0.25 V
Solution:
The relevant entries in Table 18.1 are:
Ag+(aq) + e– → Ag(s), E° = +0.80 V
Fe2+(aq) + 2e– → Fe(s), E° = -0.44 V
Solution:
Solution:
0.0592 V 0.10
E=0 log = 0.030 V
the cell potential is 2 1.0
Solution:
We have 0.175 V = 0 – (0.0592 V) (log [Cu+]), Cu+ of the CuCl
so [Cu+] = 1.11 x 10–3 and Ksp = (1.11 x 10–3)2 = 1.22 x 10–6
Batteries
Lithium-ion battery
o Ecell = 3.4 V, a relatively large potential
o can be recharged hundreds of times
Fuel cells
o direct production of electricity (electrochemical process)
o requires a continuous supply of reactants
o very efficient
o the only waste product is water !
Electrolysis
is the use of electrical energy to drive a non-spontaneous
redox reaction.
Electrolysis of water
o overall reaction is 2H2O(l) → O2(g) + 2H2(g)
o need to add an electrolyte (e.g., H2SO4) to provide
enough ions to create a current.
Solution:
2+ –
We know the reduction
✓ half-reaction
◆✓ is Mg
◆ ✓ + 2e ◆→✓ Mg ◆
3600 s 1 mol e 1 mol Mg 24.31 g Mg
grams Mg = (0.912 A)(18 h)
1h 9.65 ⇥ 104 C 2 mol e 1 mol Mg
= 7.44 g
Solution:
We know the oxidation half-reaction is 2Cl–(aq) → Cl2(g) + 2e–