7/17/2010

Whichreactantisoxidizedandwhichisreducedinthefollowing?
0

+8

+6

+6

+4

+4

+2

+2

Theironschargehasbecome
morenegative,soitisreduced.

Thetinschargehasbecome
morepositive,soitisoxidized.

+2

+2

+4

2FeCl3 +SnCl2 2FeCl2 +SnCl4

reduced

Fe

Sn

Rxn:

+3

+4

(acidic conditions)

MnO4 + C2O42 Mn2+ + CO2

1. Determine the oxidation number of the redox active species.

2. Split the redox reaction into two half reactions (remember
OIL RIG) and add in the #e being transferred.
Red:

2 8

Ox:

16

H+

H+

5e

+ MnO4

Mn2+

+ 4 H2O

+ 2 MnO4 + 5 C2O4 2
2

Mn2+

+1

+2

2)Cu+2AgNO3 Cu(NO3)2 +2Ag

oxidized
reduced
+5

-2

-1

3)2KClO3 2KCl+3O2

Singlereplacement

Notethataredox
reactioncanalsobe
anothertypeof
Decomposition reaction.
KClO3
+1 + x + 3(2) = 0
x = +5

oxidized
reduced

+ 10 CO2 + 8 H2O

Voltaic (alt. Galvanic) Electrochemical Cells

Zn|Zn2+||Cu2+|Cu
0.92

1. Balance reaction using acidic conditions.

16 H+ + 2 MnO4 + 5 C2O42 2 Mn2+ + 10 CO2 + 8 H2O
+16 OH

+16 OH
8 16 H2O

3. Cancel out excess water and rewrite reaction equation.

3. Balance the oxygens with H2O and the hydrogens with H+.
4. Multiply both half-reactions by a factor that will make the
#e transferred equal.
5. Add the two half-reactions to get the final balanced redox rxn.

Anode||Cathode

reduced

2. Add OH to both sides to neutralize the H+.

5 C2O42 2 CO2 + 2e

Synthesis

Balancing Redox Reactions Under Basic Conditions

Balancing Redox Reactions

+7

-1

oxidized

+8 oxidized

+3

+4

-1

1)Cl2 +SnCl2 SnCl4

Aredoxreactionisoneinwhichthereactantsoxidation
numberschange.
Whataretheoxidationnumbersof
themetalsinthereactionbelow?

+2

Ecell = EA + EC
Ecell = 0.763V
+ 0.153 V
0.916 V

Salt bridge

8 H2O + 2 MnO4 + 5 C2O42 2 Mn2+ + 10 CO2 + 16 OH

Example: What are the standard cell potentials for the folllowing?
Al3+ + 3e Al

Eo= 1.66 V
Br2 + 2e 2Br

Ag+ + e Ag

Eo= +0.80 V

Eo= +1.06 V

1. Al|Al3+||Ag+|Ag
Ox: Al Al3+ + 3e

+1.66 V

Red: Ag+ + e Ag

+0.80 V

+2.46 V

2. Ag|Ag+||Br2|Br
EA = +0.763 V

Oxidation takes place

at the anode.

EC = +0.153 V

Reduction takes place

at the cathode.

Ox: Ag Ag+ + e

0.80 V

Red: Br2 + e 2 Br +1.06 V

+0.26 V

Note: Voltaic cells ALWAYS have positive cell emfs (voltages).

7/17/2010

Some terminology
SHE Standard hydrogen electrode; Eo = 0 V by definition.
Standard conditions Solution concentrations = 1 M and gas
pressures = 1 atm
Oxidizing agent is reduced during redox rxn
Reducing agent is oxidized during redox rxn
Faradays constant = 96485 C/mol e transferred
R = 8.314 J/molK
1 A = 1 C/s
(C Coulomb = a quantity of charge)

1 V = 1 J/C

A voltaic cell generates current as a result of a spontaneous

redox reaction. The equations relating E, G and K are:

G = -nFE

K =e

G
RT

=e

nFE
RT

lnK = -G/RT = nFE/RT

R = 8.314 J/molK, T = temperature in Kelvin, F = 96485 C/mol

n = # electrons transferred in reaction

SHE

Good reducing agent = large,

negative reduction potential

Operating under non-standard conditions:

0.0592 [products]
o

log
Nernst Eq. = Ecell = Ecell
[reactants]

20.50 What is the cell potential for the following if [Ce4+]=2.0M,

[Ce3+] = 0.010 M and [Cr3+] = 0.010 M?
3Ce4+ + Cr(s) 3Ce3+ + Cr3+

20 58 What are G and K for: 2VO2+ + 4H+ + 2Ag VO2+ + 2H2O + 2Ag+
20.58

Ecell = EC + EA = 1.00 V + (0.799 V) = 0.201 V

Good oxidizing agent = large,

positive reduction potential

Table of Standard R
Reduction Potentials

emf Electromotive force; force causing e to move

n = 2 e

(Remember 1 V = 1 J/C)

G = -nFE = -(2 e)(96485 C/mol e)(0.201 V) = -38787 J/mol

K = eG/RT = e(38787 J/mol)/(8.314 Jmol*298K) = e15.7 = 6294875

RED

n = 3e

OX

Eo = EC + EA = +1.61 V + +0.74 V = 2.35 V

E = 2.35 V (0.0592/3)log

[0.010 M]3[0.010 M]
[2.0 M]3

= 2.53 V

Because [reactants]>>[products] AND the reaction has a large

positive Eo, the emf has increased to produce more product.

Electrolysis: Decomposition of a compound by passing

electricity through it.
20.80 Metallic magnesium can be made by the electrolysis of
molten MgCl2. What mass of Mg is formed by passing a
current of 5.25 A through molten MgCl2 for 2.50 days?
Calculate total time:2.50 days x

24 hrs 60 min 60 s
x
x
= 216000 s
day
hr
min

Calculate
C l l t ttotal
t l charge
h
passed
d = 5.25
5 25 C/s
C/ * 216000 s = 1134000 C
Divide by 2 because it takes 2e/equiv Mg2+= 567000 C
Calculate mol Mg = 567000 C /(96485 C/mol) = 5.877 mol Mg(s)
Calculate grams Mg = 5.877 mol Mg(s) * 24.305 g/mol = 142.8 g
Ans: 143 g of Mg will be formed