ELECTROCHEMISTRY

Chapter 21

• redox reactions
• electrochemical cells
• electrode processes
• construction Electric
• notation automobile
• cell potential and Go
• standard reduction potentials (Eo)
• non-equilibrium conditions (Q)
• batteries
• corrosion
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CHEMICAL CHANGE  ELECTRIC CURRENT

Zn metal
With time, Cu plates out
onto Zn metal strip, and
Zn strip “disappears.”
Cu2+ ions

• Zn is oxidized and is the reducing agent

Zn(s)  Zn2+(aq) + 2e-

• Cu2+ is reduced and is the oxidizing agent

Cu2+(aq) + 2e-  Cu(s)
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 wire
ANODE CATHODE
electrons
OXIDATION REDUCTION
Zn salt
bridge Cu

Zn2+ ions Cu2+ ions

• Electrons travel thru external wire.

• Salt bridge allows anions and cations to
move between electrode compartments.
• This maintains electrical neutrality.
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CELL POTENTIAL, Eo

For Zn/Cu, voltage is 1.10 V at 25C

and when [Zn2+] and [Cu2+] = 1.0 M.

• This is the
STANDARD CELL POTENTIAL, Eo
• Eo is a quantitative measure of the tendency
of reactants to proceed to products when all
are in their standard states at 25 C.

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 E and G
o o

Eo is related to Go, the free

energy change for the reaction.

Go = - n F Eo
• F = Faraday constant Michael Faraday
= 9.6485 x 104 J/V•mol 1791-1867
•n = the number of moles of Discoverer of
electrons transferred. • electrolysis
• magnetic props. of matter
Zn / Zn2+ // Cu2+ / Cu • electromagnetic induction
• benzene and other
n for Zn/Cu cell ? n=2 organic chemicals

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 Eo and Go (2) Go = - n F Eo

• For a product-favored reaction

– battery or voltaic cell: Chemistry  electric current
Reactants  Products
Go < 0 and so Eo > 0 (Eo is positive)

• For a reactant-favored reaction

- electrolysis cell: Electric current  chemistry
Reactants  Products
Go > 0 and so Eo < 0 (Eo is negative)

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 STANDARD CELL POTENTIALS, Eo

• Can’t measure half- reaction Eo directly.

Therefore, measure it relative to a standard
HALF CELL:
the Standard Hydrogen Electrode (SHE).

2 H+(aq, 1 M) + 2e- H2(g, 1 atm)

Eo = 0.0 V

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 STANDARD REDUCTION POTENTIALS

Oxidizing ability of ion

Half-Reaction Eo (Volts)
Cu2+ + 2e-  Cu + 0.34
2 H+ + 2e-  H2 0.00
Zn2+ + 2e-  Zn -0.76

BEST Oxidizing agent ?

Cu?2+
Reducing ability
BEST Reducing agent ?Zn
? of element
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 Using Standard Potentials, Eo
• See Table 21.1, App. J for Eo (red.) H2O2 /H2O +1.77
• Which is the best oxidizing agent: Cl2 /Cl- +1.36
O2, H2O2, or Cl2 ? O2 /H2O +1.23

Hg2+ /Hg +0.86

• Which is the best reducing agent:
Sn2+ /Sn -0.14
Sn, Hg, or Al ?
Al3+ /Al -1.66
• In which direction does the following reaction go?
Cu(s) + 2 Ag+(aq)  Cu2+(aq) + 2 Ag(s)

As written: Eo = (-0.34) + 0.80 = +0.43 V Ag+ /Ag +0.80

reverse rxn: Eo = +0.34 + (-0.80) = -0.43 V Cu2+ / Cu +0.34

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 Cells at Non-standard Conditions
For ANY REDOX reaction,
• Standard Reduction Potentials allow prediction of
direction of spontaneous reaction
If Eo > 0 reaction proceeds to RIGHT (products)
If Eo < 0 reaction proceeds to LEFT (reactants)

• Eo only applies to [ ] = 1 M for all aqueous species

• at other concentrations, the cell potential differs

• Ecell can be predicted by Nernst equation

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 Cells at Non-standard Conditions (2)
Eo only applies to [ ] = 1 M for all aqueous species
at other concentrations, the cell potential differs
Ecell can be predicted by Nernst equation
n = # e- transferred
RT F = Faraday’s constant
E = Eo - ln (Q)
nF = 9.6485 x 104 J/V•mol

Q is the REACTION QUOTIENT (recall ch. 16, 20)

Go, Eo At equilibrium
refer to G = 0
ALL REACTANTS E= 0
relative to Q=K
ALL PRODUCTS
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Example of Nernst Equation E = Eo -
RT
ln (Q)
nF

Q. Determine the potential of a Daniels cell with

[Zn2+] = 0.5 M and [Cu2+] = 2.0 M; Eo = 1.10 V

A. Zn / Zn2+ (0.5 M) // Cu2+ (2.0 M) / Cu

[Zn2+]
Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s) Q=?
[Cu2+]
E = 1.10 - (0.0257) ln ( [Zn2+]/[Cu2+] )
2
E = 1.10 - (-0.018) = 1.118 V

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 Nernst Equation (2) RT
E = Eo - ln (Q)
nF
Q. What is the cell potential and
the [Zn2+] , [Cu2+] when the cell is completely discharged?

A. When cell is fully discharged:

• chemical reaction is at equilibrium
•E=0 G = 0
Determine Kc from Eo by
•Q=K and thus
(nFEo/RT)
0 = Eo - (RT/nF) ln (K) Kc = e
or Eo = (RT/nF) ln (K)
or ln (K) = nFEo/RT = (n/0.0257) Eo at T = 298 K
(2)(1.10)/(.0257)
So . . . K = e = 1.5 x 1037
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Primary (storage) Batteries

Anode (-)
Zn  Zn2+ + 2e-
Cathode (+) Common dry cell
2 NH4 + 2e-  2 NH3 + H2
+
(LeClanché Cell)

Anode (-)
Zn (s) + 2 OH- (aq)
 ZnO (s) + 2H2O + 2e-
Cathode (+)
Mercury Battery HgO (s) + H2O + 2e-
(calculators etc)  Hg (l) + 2 OH- (aq)
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 Secondary (rechargeable) Batteries

Nickel-Cadmium

11_NiCd.mov
21m08an5.mov

Anode (-)

Cd + 2 OH  Cd(OH)2 + 2e-
-

DISCHARGE
Cathode (+)

NiO(OH) + H2O + e-  Ni(OH)2 + OH-
RE-CHARGE

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 Secondary (rechargeable) Batteries (2)

11_Pbacid.mov Lead Storage

21mo8an4.mov Battery

• Con-proportionation
reaction - same species
Anode (-) Eo = +0.36 V
produced at anode and
Pb(s) + HSO4- 
 PbSO4(s) + H+ + 2e- cathode
• RECHARGEABLE
Cathode (+) Eo = +1.68 V
PbO2(s) + HSO4- + 3 H+ + 2e- 
 PbSO4(s) + 2 H2O
Overall battery voltage = 6 x (0.36 + 1.68) = 12.24 V
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 Corrosion - an electrochemical reaction
Electrochemical or redox reactions are tremendously
damaging to modern society e.g. - rusting of cars, etc:
anode: Fe -  Fe2+ + 2 e- EOX = +0.44
cathode: O2 + 2 H2O + 4 e-  4 OH- ERED = +0.40

net: 2 Fe(s) + O2 (g) + 2 H2O (l)  2 Fe(OH)2 (s) Ecell = +0.84

Mechanisms for minimizing corrosion
• sacrificial anodes (cathodic protection) (e.g. Mg)
• coatings - e.g. galvanized steel
•- Zn layer forms (Zn(OH)2.xZnCO3)
• this is INERT (like Al2O3); if breaks, Zn is sacrificial

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 Electrolysis of Aqueous NaOH
Electric Energy  Chemical Change
Anode : Eo = -0.40 V
4 OH-  O2(g) + 2 H2O + 2e-
11_electrolysis.mov
Cathode : Eo = -0.83 V 21m10vd1.mov

4 H2O + 4e-  2 H2 + 4 OH-

Eo for cell = -1.23 V

since Eo < 0 , Go > 0
- not spontaneous !
- ONLY occurs if Eexternal > 1.23 V is applied
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ELECTROCHEMISTRY
Chapter 21

• redox reactions
• electrochemical cells
• construction
• electrode processes Electric automobile
• notation
• cell potential and Go
• standard reduction potentials (Eo)
• non-equilibrium conditions (Q)
• batteries
• corrosion

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Phosphorus and Sulfur
Chemistry Kotz, Ch 22

• the elements
• physical properties
• chemical reactions
• redox chemistry
• acid/base chemistry

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Elemental Sulfur
- Obtained from:
- free element in volcanic vents
‘mined’ by Frasch process

- minerals : FeS2 (pyrite), PbS2 (galena)

Cu2S (chalcocite)
(S produced as by-product of metal extraction)

- natural gas and oil processing

desulfurization:
2 H2S (g) + SO2 (g)  3 S (s) + 2 H2O (g)
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 Elemental Phosphorus

- not found free in nature - too easily oxidized

“phosphate rock”

Ca3 (PO4)2 calcium phosphate

Ca5 (PO4)3 F fluoro apatite
Ca5 (PO4)3 OH hydroxy apatite (teeth etc)
Ca5 (PO4)3 Cl chloro apatite
• Isolate phosphorus from these ‘rocks’
by burning with charcoal and sand
2 Ca3 (PO4)2 (l) + 6 SiO2 (s)  P4O10 (g) + 6 CaSiO3 (l)
P4O10 (g) + 10 C (s)  P4 + 10 CO (g)
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 Structure of P

P4 - white (or yellow)

phosphorus (m.p. 44oC)

Pn - red or black phosphorus

m.p. > 400 oC
Allotropes :
- different structural forms of the same element or compound
OTHER EXAMPLES ??

C (diamond, graphite, fullerene)

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 Structure of S
Solid sulfur :
various solid state structures
orthorhombic
monoclinic
plastic (amorphous)

Liquid Sulfur: < 160oC - free flowing - S8 rings

> 160oC - very viscous - Sn chains

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 Bonding in 3rd row versus 2nd row

Gp V
P4
N2

Gp VI

O2 S8

Multiple bonding between two 3rd-row elements is

uncommon due to their LARGER SIZE

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Chemistry of Sulfur Compounds
Lewis diagram ? Molecular structure ?
Oxides .. ..
O=S=O . angular, bent
SO2 .. ..
.. ..
SO3 O=S=O
.. .. planar triangular
.. O..

S can have more than 8 electrons / 4 electron pairs

expanded (>4) valence usually occurs with O, F or Cl
Sulfuric Acid
- STRONG, diprotic acid
- 1st H fully ionized H2SO4 + H2O  H3O+ + HSO4-
HSO -
+ H O  H O+ + SO 2-
- 2nd partially ionized 4 2  3 4

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Reactions of Sulfuric Acid

1. Strong acid
NaNO3 + H2SO4  HNO3 + NaHSO4

2. Dehydrating agent
C11H22O11 + H2SO4  12 C + 11 H3O+ 11 HSO4-

3. Strong oxidizing agent

2 Br- + 2 H2SO4 (conc.)  2 Br2 + SO42- + SO2 + 2H2O

4. Useful solvent : m.p. 10oC b.p. 338oC

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Oxidation States of Sulfur and Phosphorus

Both S and P have many oxidation states

- and lots of redox chemistry

Sulfur Phosphorus
O.N. e.g. name O.N. e.g. name

-2 H 2S sulfide -3 AlP phosphide

0 S8 0 P4
+2 SCl2 +3 PCl3, H3PO3 phosphorus
+4 SF4, H2SO3 sulfurous PO33- phosphite
SO32- sulfite +5 PF5, H3PO4 phosphoric
+6 SF6, H2SO4 sulfuric PO43- phosphate
SO42- sulfate
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 Redox chemistry of sulfur compounds
Compounds in intermediate oxidation states S(2) or S(4)
can act as both oxidizing and reducing agents
SO2 can act as a reducing agent . . .

SO2 (g) + Br2 (aq) + 6 H2O  2 Br-(aq)+ SO42- (aq) + 4 H3O+ (aq)

5 SO2 (g) + 2MnO4- (aq) + 6 H2O  5SO42- (aq) + 2Mn2+ (aq) + 4 H3O+ (aq)

and can act as an oxidizing agent:

SO2 (g) + 2 H2S (g)  3 S(s) + 2 H2O

Water is both CATALYST and product ! - autocatalysis

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Chemistry of phosphorus compounds
OXIDES

P4 + 3 O2  P4O6

P4 + 5 O2  P4O10

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 Phosphoric acid

P4O10 + 6 H2O  4 H3PO4 - phosphoric acid

H3PO4 is a weak tri-protic acid
- even 1st H+ not fully ionized
Kc (eq)

H3PO4 (aq) + H2O  H3O+(aq) + H2PO4- (aq) dihydrogen 7.5x10-3
phosphate

H2PO4- (aq) + H2O  H3O+(aq) + HPO42- (aq) hydrogen 6.2x10-8
phosphate

HPO4 (aq) + H2O
2-  H3O+(aq) + PO43- (aq) phosphate 3.6x10-13

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 Phosphorus Chemistry (2)
P4O6 + 6 H2O  4 H3PO3 - phosphorus acid
H3PO3 is a weak di-protic acid
WHY ONLY 2 IONIZABLE hydrogens ?
The P-H bond is strong and non-polar - not ionizable

P (III) oxide and its acid are easily oxidized to P (V) so

they act as REDUCING agents:
- 2 e-

Cu2+(aq) + H3PO3(aq) + 3 H2O  Cu (s) + H3PO4(aq) + 2H3O+

- 2 e-

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 Phosphorus Chemistry (3)
Phosphine. PH3 - like NH3 but weaker base
P 3-
Phosphide - ionic compounds with some metals
6 Ca + P4  2 Ca3P2 (Ca2+)3 ( P 3-
)2

P5+ Phosphoric acid, phosphate compounds

Polyphosphates - condensation of hydroxy-acids

X-O-H + H-O-X  X-O-X + H2O
O O

e.g. 2 H3PO4  H-O-P-O-P-O-H + H2O

O O di-phosphoric acid
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 Phosphorus Chemistry (4)
Phosphate condensation/hydrolysis
important in Biochemistry:

+ H2O
R +
enzymes

[R-O-(PO2)-O-PO3]3-(aq) + H2O  [R-O-(PO3)]2-(aq)+ H2PO4-(aq)

ATP 3-
+ H2O  AMP + H2PO4 (aq)
2- - Go = -30.5 kJ/mol
Energy from - removal of e--e- repulsion in reactant (ATP)
- P-O bond converted to P=O bond
- more resonance stabilization in products
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P and S Chemistry
Kotz, Ch 22

• Physical properties
• Chemical reactions
• redox chemistry
• acid/base chemistry

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