Electrochemistry & Electrochemical Cells (Batteries)

Electricity Chemistry
(A Chicken-and-Egg Question: Who Came First?
Introduction: Direct Reaction
Zn (no useful work is being done; E = q + w
Energy released by the rxn. Is dissipated as heat, q)

Zn Zn

Cu
Zn2+
Cu2+ Cu2+ Zn2+
Cu2+ Cu2+ Cu2+ Zn2+ Cu2+ Cu
Reduction Half-Rxn.: Cu2+ + 2e Cu(s)
Oxidation Half-Rxn.: Zn(s) Zn2+ + 2e
Net-Ionic Redox Reaction: Cu2+(aq) + Zn(s) Cu(s) + Zn2+(aq)

1
Spontaneous Rxn.: G < 0
Prof. Zvi C. Koren 20.07.2010
 Galvanic Cell (also Voltaic or Self-Driven Cell)
Indirect Reaction: Daniell Cell with Porous Semi-Permeable Membrane
Electrode: e e
Object that conducts external circuit External circuit:
(releases/collects) voltmeter + Electronic

Cathode
porous conduction by

Anode
electrons. semi-permeable
Zn membrane Cu free electrons
Two Electrodes: Internal circuit:
Oxidation always Zn2+ Cation Electrolytic
occurs at the Anode. Cu2+ conduction by
Anion
Reduction always electrolytes
SO42
occurs at the (ions)
Cathode Copper-plating
Anode Half-Cell Cathode Half-Cell
Red Cat Cathode: Reduction Half-Rxn.: Cu2+ + 2e Cu(s)
An Ox Anode: Oxidation Half-Rxn.: Zn(s) Zn2+ + 2e -"
Cell Reaction: Cu2+(aq) + Zn(s) Cu(s) + Zn2+(aq)
Spontaneous Rxn.: G < 0
Questions: Why is the Anode ()? Why do the ions diffuse, migrate, to the electrodes?
2 (Energy released by the rxn.can perform useful work!) Prof. Zvi C. Koren 20.07.2010
 Daniell Cell with Salt Bridge
Indirect Reaction

e e

+
NO3

Cathode
Na+
Anode Zn Cu
porous
semi-permeable
membrane
Zn2+
SO42 Cu2+

Anode Half-Cell Cathode Half-Cell

Note: Salt ions must not themselves undergo reduction or oxidation

3 Prof. Zvi C. Koren 20.07.2010

 Line Notation
(Shorthand Notation for Electrochemical Cells)
e
Anode half-cell Cathode half-cell

electrode sp.1(aq), sp.2(aq) sol. liq. gas sp.1(aq), sol. liq. gas electrode

Notes:
1. Only the species appearing in each net-ionic half rxn. are listed.
2. Species in same solution are separated by a comma.
3. Species in different phases are separated by a vertical line.
4. The first half-cell listed is always for the Anode.
5. The electrodes are listed at the extremes.
6. A double line is used if there is a physical separation between the two half-
cell compartments.

Example for the Daniell cell (with and without the salt bridge cells before):
Zn Zn2+ Cu2+ Cu

Question: How would you design an electrochemical cell for which the net-ionic rxn. is:
Ni + 2Ag+ Ni2+ + 2Ag
4 Prof. Zvi C. Koren 20.07.2010
 Cell Potential (), units in Volts
e The existence of a
potential difference
e
between the two electrodes
HIGH
Anode
voltmeter + is the
driving force ,
electric
also known as the

Cathode
potential low
electric electromotive force (emf),
potential for the electron flow, and
thus for the rxn.
Electrical Work (Electrical Energy), wel
1 J of energy is released when 1 C of charge passes through a potential drop of 1 V:
1 J 1 VC C Coulomb,
In general: wel = Q Q charge (in C) = neF
ne # of moles of electrons
F Faraday constant = 96,485 C/mol e
Thermodynamics, G
If wel is the maximum work that the system can perform, then it also represents the
available energy: G = wel = neF
For a spontaneous rxn. (self-driven cell, battery): > 0, G < 0
5 Prof. Zvi C. Koren 20.07.2010
 Measuring Standard Half-Cell Potentials
Standard Cell Potential.
Standard conditions: [solute] = 1.0 M, Pgas = 1.0 atm
cell = anode + cathode
oxidation + reduction
For example, for the Daniell cell:
Anode (Oxidation): Zn Zn2+ + 2e, A,ox
Cathode (Reduction): Cu2+ + 2e Cu, C,red
Cell Reaction: Zn + Cu2+ Zn2+ + Cu, cell,redox

Note: is an intensive property; it depends on concentration and not on amount.

(Other examples are: d, T, P, M)
Thus, if a half-rxn is multiplied by a number, its half-cell potential is not multiplied
by that number.
For example: A: Zn Zn2+ + 2e, ox
C: 2(Ag+ + e Ag), red (and not 2 red )
Cell: Zn + 2Ag+ Zn2+ + 2Ag, cell = ox + red
6 Prof. Zvi C. Koren 20.07.2010
 Standard Hydrogen Electrode (SHE)
Standard Conditions:
[H+] = 1.0 M
H2(g) 0
PH2 = 1.0 atm
1 atm
SHE
o
0.0 V M

Pt
If SHE is the Cathode:
2H+ + 2e H2(g)
H+(1 M)H2(1 atm)Pt Pt
If SHE is the Anode: H+ Mm+
H2(g) 2H+ + 2e
PtH2(1 atm) H+(1 M) SHE Unknown
Platinum black is a Pt film plated onto Pt metal:
Advantages: Pt is inert (does not corrode);
Pt film increases surface area and serves as a catalyst for the rxn.;
adsorbs H2(g) onto it.
Problem: Given the following cell: Zn Zn2+ H+ H2 Pt, cell 0.76 V
o

Determine the half-rxns at the electrodes, the cell rxn, wel, G rxn , Zn .
o o

7 Prof. Zvi C. Koren 20.07.2010

 Saturated Calomel Electrode (SCE)
calomel is an old name for mercury(I) chloride
Replaces the technically difficult SHE as a reference for electrode potential
measurements of other half-cells.

Crystal structure of Hg2Cl2

4.5 M

Hg2Cl2(s) + 2e 2Hg(l) + 2Cl, SCE,25 oC = 0.24 V (Note: this is not o)

8 Prof. Zvi C. Koren 20.07.2010

 Standard Reduction Potentials at 25 oC
Half-Reaction 0 (V) Sn4+(aq) + 2 e- -----> Sn2+(aq) 0.13
Li+(aq) + e- -----> Li(s) 3.05 Cu2+(aq) + e- -----> Cu+(aq) 0.13
K+(aq) + e- -----> K(s) 2.93 SO42-(aq) + 4 H+(aq) + 2 e- -----> SO2(g) + 2 H2O 0.2
Ba2+(aq) + 2 e- -----> Ba(s) 2.9 AgCl(s) + e- -----> Ag(s) + Cl-(aq) 0.22
Sr2+(aq) + 2 e- -----> Sr(s) 2.89 Cu2+(aq) + 2 e- -----> Cu(s) 0.34
Ca2+(aq) + 2 e- -----> Ca(s) 2.87 O2(g) + 2 H2 + 4 e- -----> 4 OH-(aq) 0.4
Na+(aq) + e- -----> Na(s) 2.71 I2(s) + 2 e- -----> 2 I-(aq) 0.53
Mg2+(aq) + 2 e- -----> Mg(s) 2.37 MnO4-(aq) + 2 H2O + 3 e- -----> MnO2(s) + 4 OH-(aq) 0.59
Be2+(aq) + 2 e- -----> Be(s) 1.85 O2(g) + 2 H+(aq) + 2 e- -----> H2O2(aq) 0.68
Al3+(aq) + 3 e- -----> Al(s) 1.66 Fe3+(aq) + e- -----> Fe2+(aq) 0.77
Mn2+(aq) + 2 e- -----> Mn(s) 1.18 Ag+(aq) + e- -----> Ag(s) 0.8
2 H2O + 2 e- -----> H2(g) + 2 OH-(aq) 0.83 Hg22+(aq) + 2 e- -----> 2 Hg(l) 0.85
Zn2+(aq) + 2 e- -----> Zn(s) 0.76 2 Hg2+(aq) + 2 e- -----> Hg22+(aq) 0.92
Cr3+(aq) + 3 e- -----> Cr(s) 0.74 NO3-(aq) + 4 H+(aq) + 3 e- -----> NO(g) + 2 H2O 0.96
Fe2+(aq) + 2 e- -----> Fe(s) 0.44 Br2(l) + 2 e- -----> 2 Br-(aq) 1.07
Cd2+(aq) + 2 e- -----> Cd(s) 0.4 O2(g) + 4 H+(aq) + 4 e- -----> 2 H2O 1.23
PbSO4(s) + 2 e- -----> Pb(s) + SO42-(aq) 0.31 MnO2(s) + 4 H+(aq) + 2 e- -----> Mn2+(aq) + 2 H2O 1.23
Co2+(aq) + 2 e- -----> Co(s) 0.28 Cr2O72-(aq) + 14 H+(aq) + 6 e- -----> 2 Cr3+(aq) + 7 H2O 1.33
Ni2+(aq) + 2 e- -----> Ni(s) 0.25 Cl2(g) + 2 e- -----> 2 Cl-(aq) 1.36
Sn2+(aq) + 2 e- -----> Sn(s) 0.14 Au3+(aq) + 3 e- -----> Au(s) 1.5
Pb2+(aq) + 2 e- -----> Pb(s) 0.13 MnO4-(aq) + 8 H+(aq) + 5 e- -----> Mn2+(aq) + 4 H2O 1.51
2 H+(aq) + 2 e- -----> H2(g) 0 Ce4+(aq) + e- -----> Ce3+(aq) 1.61
PbO2(s) + 4 H+(aq) + SO42-(aq) + 2 e- -----> PbSO4(s) + 2 H2O 1.7
(strong oxidizing agent) H2O2(aq) + 2 H+(aq) + 2 e- -----> 2 H2O 1.77
Co3+(aq) + e- -----> Co2+(aq) 1.82
ored O3(g) + 2 H+(aq) + 2 e- -----> O2(g) + H2O
F2(g) + 2 e- -----> F-(aq)
2.07
2.87
Great interactive table in Wikipedia data:
9 (strong reducing agent) http://en.wikipedia.org/wiki/Standard_electrode_potential_(data_page)
Prof. Zvi C. Koren 20.07.2010
 Alphabetical List

10 Prof. Zvi C. Koren 20.07.2010

Problems (consult Table of Standard Half-Cell Reduction Potentials):

Question: Can Cu2+ oxidize H2 with all species in their standard state?
(Show all reactions.) Answer: Yes; orxn = +0.34 V.

Question: Can Ag reduce Cu2+ with all species in their standard state?
(Show all reactions.) Answer: No; orxn = 0.46 V

What happens to cell with time?

or

time time

11 Prof. Zvi C. Koren 20.07.2010

 Inert Electrodes:
Pt, Au, C(graphite)
Problem: Show a diagram of the following cell and all the relevant reactions,
and calculate the standard cell potential:
Pt Fe2+, Fe3+ MnO4, Mn2+, H+ C
e e
+
NO3

Cathode
Na+
Anode

Pt C

H+
Fe2+ Fe3+ MnO4 Mn2+

5(Fe2+ Fe3+ + e), oAn = 0.77 V

5e + 8H+ + MnO4 Mn2+ + 4H2O, oCath = 1.52 V
5Fe2+ + 8H+ + MnO4 5Fe3+ + Mn2+ + 4H2O, ocell = 0.75 V
12 Prof. Zvi C. Koren 20.07.2010
 Nernst Equation: Non-Standard Cell Potentials
The calculation of and G from o and Go, respectively.
Consider the following overall rxn.: aA + bB cC + dD
From Lewis:
G = Go + RTlnQ (will be proved in the Thermodynamics course)
Reaction Quotient for solutes and gases: Q = [C]c[D]d/[A]a[B]b
Q has the same expression as K, but Q is for any time, whereas K is only for equilibrium.
For example, for the previous rxn.: 5Fe2+ + 8H+ + MnO4 5Fe3+ + Mn2+ + 4H2O
Q = [Fe3+]5[Mn2+]/[Fe2+]5[H+]8[MnO4]
From before: G = wel = neF Go = neFo
= o (RT/neF)lnQ Nernst Eqn.: conc.
At equilibrium, = 0: o = (RT/neF)lnKeq = (RT/neF)ln(Keq /Q)
Could also prove this from Geq = 0: Go = RTlnK
Problem: Calculate cell and Grxn for the following cell at 25 oC (and show all rxns.):
Au AuCl4(0.50 M), Cl(2.0 M) ClO3(0.60 M), ClO4(0.80 M), H+(3.0 M) Pt
Answer (partial): Q = [AuCl4]2 [ClO3]3 / [Cl]8 [ClO4]3 [H+]6 = 5.65 x 107.
ocell = 0.19 V; ne = 6. cell = 0.25 V (spontaneous rxn.)
13 (Note: ocell could be , but the actual cell could be +.) Prof. Zvi C. Koren 20.07.2010
 Another Nernst Eqn. Problem (Note : mixed concentrations and pressures):
The permanganate ion is a powerful oxidizing agent that oxidizes water to oxygen
under acidic conditions, while it gets reduced to Mn2+.
What is the potential of a permanganate-oxygen cell operating at pH = 7.00, with
oxygen at 0.200 atm, 0.100 M MnO4, and 0.100 M Mn2+?

Measuring Ksp Potentiometrically

Recall those very low values for Ksp, even 1050 ? How were they measured?
For example,
PbCl2(s) Pb2+ + 2Cl, Ksp = [Pb2+][Cl]2 From before: o = (RT/neF)lnKeq
We can create this chemical equation from the following two half-rxns.:
Pb(s) Pb2+ + 2e, oox = e e
PbCl2(s) + 2e Pb(s) + 2Cl, ored = +
An NO3 Na+ Cat
PbCl2(s) Pb + 2Cl ,
2+ cell =
o
Pb Pb
Thus: ocell = (RT/neF)lnKsp
Note: A non-redox rxn. was created from
a reduction and oxidation half-rxns. Pb2+ Cl PbCl2
14 Prof. Zvi C. Koren 20.07.2010
 Electrolysis
Galvanic cell, Voltaic cell, Self-Driven cell (battery): Chemistry Electricity
Electrolytic cell (in an electrolysis process): Electricity Chemistry

In an electrolytic cell, a power source a battery is used.

The battery acts like a bully with two strong arms:
takes es with one and gives with the other

e e
+ Electrolysis of H2O
battery
An. (Ox.): 2H2O(l) O2(g) + 4H+ + 4e, o = 1.23 V
+ Cat. (Red.): 2(2H2O(l) + 2e H2(g) + 2OH), o = 0.83 V
Cell: 6H2O(l) O2(g) + 2 H2(g) + 4H+ + 4OH, ocell = 2.06 V
Anode

Cathode

2H2O(l) O2(g) + 2 H2(g)

H2(g)
O2(g)
Pt Pt Note the different signs at the electrodes.
SO42 Na+ But Oxidation always occurs at the Anode,
Anion Cation no matter what the cell type.
15 Prof. Zvi C. Koren 20.07.2010
 Electrolysis of Pure Molten NaCl
Schematic NaCl(s) + This is a pure molten
Na (l) + Cl (l)
Lab liquid, a melt, not in an
Diagram aqueous solution.

e
+ e An (ox): 2Cl(l) Cl2(g) + 2e
2(Na+(l) + e Na(l))
battery 2Na+(l) + 2Cl(l) 2Na(l) + Cl2(g), ocell = 4.07 V
+
Anode

Na(l) floats through

Cathode

the molten NaCl(l) Schematic

and is collected Industrial
Pt Pt Diagram:
Downs Cell
Cl Na+
Anion Cation

Need to keep the products

separated to prevent them reacting
(explosively) with each other.
16 Prof. Zvi C. Koren 20.07.2010
 Electrolysis of Aqueous NaCl
NaCl(aq) Na+(aq) + Cl(aq)
If there are competing half-rxns., the one with the higher will be the most favored.

What are the possible reduction rxns.?

Na+(aq) + e Na(s), o = 2.71 V
2H2O(l) + 2e H2(g) + 2OH, o = 0.83 V
What are the possible oxidation rxns.?
2Cl(aq) Cl2(g) + 2e, o = 1.36 V
2H2O(l) O2(g) + 4H+ + 4e, o = 1.23 V (So, is it really a bit easier to oxidize H2O)
But , note the following:
1. Non-Standard State effects favor Cl oxidation: The cell is never allowed to reach
standard-state conditions. The solution is typically 25% NaCl by mass, which
significantly decreases the potential required to oxidize the Cl ion.
2. pH Effects do not favor oxidation of H2O: The pH of the cell is also kept very high
(see H2O reduction above), which decreases the oxidation potential for water.
3. Overvoltage: This is the deciding factor. It is the extra voltage that must be
applied to a reaction to get it to occur at the rate at which it would occur in an
ideal system.
17 Prof. Zvi C. Koren 20.07.2010
 Electrolysis of Aqueous NaCl (continued)
So the actual rxns. are: Cat (Red): 2H2O(l) + 2e H2(g) + 2OH(aq)
An (ox): 2Cl(aq) Cl2(g) + 2e
Cell: 2Cl(aq) + 2H2O(l) Cl2(g) + H2(g) + 2OH (aq)
Compare with the electrolysis of molten NaCl: 2Na+(l) + 2Cl(l) 2Na(l) + Cl2(g)
Because the demand for chlorine is much
larger than the demand for sodium,
electrolysis of aqueous sodium chloride is
a more important process commercially.
Electrolysis of an aqueous NaCl solution
has two other advantages. It produces H2
gas at the cathode, which can be
collected and sold. It also produces
OH
NaOH, which can be drained from the
bottom of the electrolytic cell and sold.
If the porous barrier is removed, the products of the electrolysis of aqueous sodium
chloride react to form sodium hypochlorite, which is the first step in the preparation of
hypochlorite bleaches, such as Chlorox.
Cl2(g) + 2OH(aq) Cl(aq) + OCl(aq) + H2O(l)
18 Prof. Zvi C. Koren 20.07.2010
 Electroplating

The process of depositing one metal on top

of another.
Done usually for cosmetic reasons.

19 Prof. Zvi C. Koren 20.07.2010

 Faradays Laws: Electrochemical Stoichiometry
If 96,485 C of charge is passed through a cell,
equivalent amounts react and are produced
The charge on 1 mol of es is 96,485 C and an equivalent amount of any substance is
that quantity that reacts with or is produced from 1 mol of es in a redox rxn.:
96,485 C 1 mol es 1 eq. of substance
In short, use stoichiometry on the half-rxns. or the overall rxn. (example to follow)
Some Relevant Electrical Properties
Property Symbol Unit Equation
Time t s, second
Potential , E V, Volt
Charge Q C, Coulomb
Current I A, Ampere I = Q/t
Resistance R , ohm = IR
Power P W, Watt P = wel/t
J, Joule wel = Q
Energy, work wel wel = Pt
kilowatt-hour, kWh (1000 W)(3600 s)
1 kWh = 3.6 MJ
20 Prof. Zvi C. Koren 20.07.2010
 Faraday Problems
Question:
If 1.50 A of current flows through an aqueous solution containing CuCl2 for 15.0 min,
how many grams of Cu(s) are deposited at the _____ode?
Answer:
Write the relevant net-ionic half-rxn.: Cu2+ + 2e Cu(s)
Use the Unit-Factor Method for the Electrical Stoichiometry:
1.5 C 1 mol e 1 mol Cu 63.546 g Cu
900. s _________ g Cu
s 96,485C 2 mol e 1 mol Cu
Q=It
Question:
In the electrolysis of CuCl2(aq) above, the _____tion of Cl to Cl2(g) occurs at the
_____ode. ? Assume that standard state conditions apply with the current and time
from the problem above, how much electrical energy (in J and in kWh) and power (in
W) were needed?
Answer:
ocell wel = Q P = wel/t
21 Prof. Zvi C. Koren 20.07.2010
Problem:
If the electrolytic cell for the electrolysis of water draws a current of 0.775 A for 45.0
minutes, calculate the volumes of H2 and O2 produced if each gas is collected at 25 oC
and P = 1.00 atm.

Problem:
An electroplating apparatus is used to coat jewelry with gold. What mass of gold can
be deposited from a solution that contains Au(CN4) ions if a current of 5.0 A flows for
30.0 min?

22 Prof. Zvi C. Koren 20.07.2010

 Corrosion )(
The oxide of a metal is more stable than the metal itself:
M(s) + O2(g) ---> MxOy(s), G < 0 (spontaneous)
So all metals naturally want to be oxidized.
Rusting of Fe:
Anode: Fe Fe 2+ + 2e. Also: Fe2+ Fe3+ + e
Cathode (also Fe, but inert): 2H2O + 4e 4OH
O2 + 4H+ + 4e 2H2O (other rxns. are possible)
Also: 2Fe + 1O2(g) Fe2O3(s); Fe3+ + 3OH Fe(OH)3(s)

Galvanized Iron (Plated with Zn):

Zn is the sacrificial anode; easier to oxidize Zn than Fe (check it!).
Fe is now forced to be the cathode, but of course an inert one:
Anode: Zn Zn 2+ + 2e
Cathode: 2H2O + 4e 4OH

Aluminum:
Al undergoes passivation: 2Al + 1O2(g) Al2O3(s)
Once the oxide is formed, it serves as a thin film that prevents any more Al to come
into contact with the environment and react.
23 Prof. Zvi C. Koren 20.07.2010
 Different Types of Batteries
Alkaline Battery (Dry Cell):
An(-): Zn + 2OH ZnO + H2O + 2e
Cat(+): 2MnO2 + H2O + 2e Mn2O3 + 2 OH
Cell: Zn + 2MnO2 ZnO + Mn2O3, ocell = 1.54 V

24 Prof. Zvi C. Koren 20.07.2010

 Mercury Battery:
An: Zn + 2OH ZnO + H2O + 2e (as alkaline, above)
Cat: HgO + H2O + 2e Hg(l) + 2 OH

25 Prof. Zvi C. Koren 20.07.2010

 Zinc-Air Battery
Zinc Air Battery deteriorates quickly once exposed to air, Zn at the
anode and O2 at the cathode.
Used in watches, calculators, hearing aids and cameras.

Storage Batteries Rechargeable:

Ni-Cad:
An: Cd + 2OH Cd(OH)2 + 2e ocell = 1.35 V
Cat: 2[NiO(OH) + H2O + e Ni(OH)2 + OH]
Rechargeable because the nickel and cadmium hydroxides adhere tightly to the
electrodes.
26 Prof. Zvi C. Koren 20.07.2010
Lead Storage Battery:
An: Pb + SO42 PbSO4 + 2e
Cat: PbO2 + 4H+ + SO42 + 2e PbSO4 + 2H2O

27 Prof. Zvi C. Koren 20.07.2010

Problem:
Automobile headlights typically draw 5.9 A of current. The galvanic cell of a
lead storage battery consumes Pb and PbO2 as it operates. A typical
electrode contains about 250 g of PbO2. Assuming that the battery can
supply 5.9 A of current until all the PbO2 has been consumed, how long will it
take for a battery to run down if the lights are left on after the engine is
turned off?
Fuel Cell is an electrochemical cell that produces electricity from a fuel tank. The
electricity is generated through the reaction, triggered in the presence of an
electrolyte, between the fuel (on the anode side) and an oxidant (on the cathode
side). The reactants flow into the cell, and the reaction products flow out of it,
while the electrolyte remains within it. Fuel cells can operate virtually continuously
as long as the necessary flows are maintained.
Fuel cells are different from conventional electrochemical cell batteries in that they
consume reactant from an external source, which must be replenished a
thermodynamically open system. By contrast, batteries store electrical energy
chemically and hence represent a thermodynamically closed system.
Hydrogen Fuel Cell (70 140 oC):
An: 2H2(g) + 4OH 4H2O + 4e
Cat: O2(g) + 2H2O + 4e 4OH
28 Prof. Zvi C. Koren 20.07.2010
 The pH Meter Consists of a Combination Electrode
These two electrodes are combined into The net effective rxn. is:
one combo electrode H+(inside glass electrode)

H+(in the unknown solution)
Nernst:
= o (RT/neF)ln([H+]outside/[H+]inside)
= o + 2.303(RT/neF)(pHoutside pHinside)
pHinside is constant, so
= o + 2.303(RT/neF)pHoutside
pH meter is calibrated with the pH of known
buffer solutions, so o is cancelled.

This combo electrode is inserted into a 2.303(RT/neF)pHoutside
solution with unknown pH 1.98x104TpHoutside
pH logaH+
aH+ = H+ MH+
Kw = aH+aOH /aH2O
29 Prof. Zvi C. Koren 20.07.2010