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5-Redox_S11.

doc
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OXIDATION-REDUCTION REACTIONS (Redox Reactions) (SJ, p. 316)



1. Oxidation-reduction (Redox) reactions

a. Redox reaction consists of two half-reactions:

1) Oxidation reaction (LEOs) - in which a substance loses or donates electrons (e
-
)
2) Reduction reaction (GERs) - in which a substance gains or accepts electrons (e
-
)

LEO said GER
Oil Rig oxidation in lose, reduction in gain

c. An oxidation reaction and a reduction reaction must be always coupled.

- Two rules apply to redox reaction:

1) "free" electron cannot exist in solution.
2) electron must be conserved.

d. All redox reactions involve a change in Oxidation State (Oxidation Number).



2. Oxidation State (Oxidation Number)

- is the hypothetical electronic charge that each atom has in a reaction.

- is a very useful concept in balancing chemical reactions.

All redox reactions involve a change in oxidation state.

- In general,

H has oxidation state of 1+ (+1)
O has oxidation state of 2- (-2)
Cl has oxidation state of 1- (-1)


H
2
has oxidation state of 0
O
2
has oxidation state of 0
H
2
O
2
has oxidation state of 0
Cl
2
has oxidation state of 0
N
2
has oxidation state of 0


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b. Rules

1) The oxidation state of a monoatomic substance is equal to its own electronic charge (valence).

e.g., Cu
2+
Cu(II)
Cd
2+
Cd(II)
Ni
2+
Ni(II)

2) In a covalent compound, the oxidation state is the charge remaining on the atom when each
shared pair of electrons is assigned completely to the more electronegative of the two atoms
sharing them (divide the electrons equally if the two atoms are the same)

3) Sum of charges must equal charge on ion.


Example: Find the oxidation number of

S H
2
S S
8
SO
3
2-
SO
4

2-


C HCO
3
-
HCOOH C
6
H
12
O
6
C
6
H
5


N NH
4
+
N
2
NO
2
-
NO
3
-
HCN


(Solution)


2(1+) 2- 0 4+ 3(2-) 6+ 4(2-)
S H
2
S S
8
[SO
3
]
2-
[SO
4
]
2-

sulfite sulfate


1+ 4+ 3(2-) 1+ 2+ 2- 2- 1+ 0 12(1+) 6(2-) 6 (-5/6) 5(1+)
C [HCO
3
]
-
HCOOH C
6
H
12
O
6


C
6
H
5



3- 4(1+) 0 3+ 2(2-) 5+ 3(2-) 1+ 2+ 3-
N [NH
4
]
+
N
2
[NO
2
]
-
[NO
3
]
-
H C N
nitrite nitrate


Example: Write the oxidation number of

7+ 2(7+) 7(2-)
Cl in Cl
2
O
7
Cl in Cl
2
O
7

4+ 4+ 3(2-)
S in SO
3
2-
S in [SO
3
]

2-


3+ 1+ 3+ 2(2-)
N in HNO
2
N in H N O
2

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6+ 2(1+) 2(6+) 7(2-)
Cr in K
2
Cr
2
O
7
Cr in K
2
Cr
2
O
7


+1 2+ 2(+1)
H in CaH
2
H in CaH
2



Example

2+ 3 2(1+)(2) 4+ 3 2 2(1+)
[CN ]

+ H
2
O C N O

+ 2H
+
+ 2e



Example Nitrogen

NH
4
+
+ 1.5 O
2
NO
2
-
+ H
2
O + 2H
+

NO
2
-
+ 0.5 O
2
NO
3
-

- All oxidation reduction reactions involve a change in oxidation state.


0
N
2

Anammox Denitrification
process (denitrifyer)



3- 4(1+)
---------
3+ 2(2-)
---------------
5+ 3(2-)

N H
4
+
--------- N O
2
-
---------------- N O
3
-
1st stage 2nd stage
nitrification nitrification
Nitrosomonas sp. Nitrospira sp., Nitrobacter sp.

Slower rxn Faster rxn



Example Sulfur


0 6+ 4(2) 2(1+) 2
S
8
-------> S O
4

2-
------> H
2
S
REO GER






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3. Oxidizing and Reducing Agents

a. Oxidizing Agent - a substance which causes an oxidation to occur, while being reduced itself.
e.g.,
O
2
Oxygen
O
3
Ozone
H
2
O
2
Hydrogen peroxide
Cl
2
Chlorine
OH Hydroxyl radical
MnO
4

Permanganate (as KMnO


4
)
Cr
2
O
7
2
Dichromate (as K
2
Cr
2
O
7
)



0 2(1+) 2 0 4+ 2(2) 2(1+) (2)
Formaldehyde C H
2
O + O
2
--- C O
2
+ H
2
O

O: 0 2- O is reduced (GERs)
C: 0 4+ C is oxidized (LEO)



Organic Chemistry: Aldehydes

General Functional
Formula Group

R-C=O -C=O H-C=O CH
3
-C=O
\ \ \ \
H H H H

Common: Formaldehyde Acetaldehyde
IUPAC: Methanal Ethanal


No of C IUPAC
1 Methanal
2 Ethanal
3 Propanal
4 Butanal
5 Pentanal
6 Hexanal
7 Heptanal


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b. Reducing Agent - a substance which causes a reduction to occur, while being oxidized itself.

e.g., SnCl
2
Na
o
Na
2
SO
4

4+ 2(2) 6+ 4(2)
Sn
2+
Sn
4+
+ 2e

S O
2
(S O
4
)
2-
tin

Na
o
---> Na
+
+ e




Balancing Redox Reaction - the half reaction method

Example 7-1 (SJ, 317): Balance the reaction in which ferrous ion (Fe
2+
) is oxidized to ferric ion (Fe
3+
)
by permanganate (MnO
4

-
) which itself is reduced to manganese dioxide (MnO
2(s)
). The reaction takes
place in alkaline solution.

Reaction: Fe
2+
+ MnO
4

-
Fe
3+
+ MnO
2(s)

STEP

1. Identify principal Reactants Products
reactants and
2+ 3+

products Fe
2+
Fe
3+
Oxidation

7+ 4(2-) 4+ 2(2-)
MnO
4
-
MnO
2(s)
Reduction

2. Obtain balanced Fe
2+
Fe
3+

half-reactions
(balance the charge MnO
4
-
MnO
2(s)

w/ e
-
)

3. Balance the oxygen Fe
2+
Fe
3+
w/ H
2
O MnO
4
-
MnO
2(s)
+ 2H
2
O


4. Balance the hydrogen Fe
2+
Fe
3+
w/ H
+
4H
+
+ MnO
4
-
MnO
2(s)
+ 2H
2
O



5. Balance the charge Fe
2+
Fe
3+
+ e
-
w/ e
-
3e
-
+ 4H
+
+ MnO
4
-
MnO
2(s)
+ 2H
2
O

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6. Multiply each half -rxn 3Fe
2+
3Fe
3+
+ 3e
-
by an appropriate integer
so that both contain the 3e
-
+ 4H
+
+ MnO
4
-
MnO
2(s)
+ 2H
2
O
same number of e
-
-------------------------------------------------------------------------
4H
+
+ 3Fe
2+
+ MnO
4
-
3Fe
3+
+ MnO
2(s)
+ 2H
2
O


7. If the rxn takes place in alkaline 4H
+
+ 3Fe
2+
+ MnO
4
-
3Fe
3+
+ MnO
2(s)
+ 2H
2
O
solution,add the water dissociation 4H
2
O 4H
+
+ 4OH
-
equation to eliminate H
+
-----------------------------------------------------------------------
as a reactant 2H
2
O + 3Fe
2+
+ MnO
4
-
3Fe
3+
+ MnO
2(s)
+ 4OH
-


8. We know that in alkaline 2H
2
O + 3Fe
2+
+ MnO
4
-
3Fe
3+
+ MnO
2(s)
+ 4OH
-
solution, Fe
3+
and OH
-
3Fe
3+
+ 9OH
-
3Fe(OH)
3(s)

will combine to form -----------------------------------------------------------------------
Fe(OH)
3(s)
2H
2
O + 3Fe
2+
+ MnO
4
-
+ 5OH
-
3Fe(OH)
3(s)
+ MnO
2(s)



Net:
1. Ferrous iron (Fe
2+
) is oxidized, it loses e
-
(REO)
2. Permanganate (MnO
4

-
) is reduced, it gains e
-
(GER)



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Other Method (Sato)

Balance the following equation by the half reaction method:

Reaction: Fe
2+
+ MnO
4

-
Fe
3+
+ MnO
2(s)

1. Identify principal Reactants Products
reactants and
2+ 3+

products Fe
2+
Fe
3+
LEO - Oxidation

7+ 4(2-) 4+ 4-
MnO
4
-
MnO
2(s)
GER - Reduction


2. Obtain balanced Fe
2+
Fe
3+
+ e
-
half-reactions
(balance the charge Mn
7+
+ 3e
-
Mn
4+
w/ e
-
)

3. Multiply each half rxn (x3) 3Fe
2+
3Fe
3+
+ 3e
-
by an appropriate integer
so that both contain the Mn
7+
+ 3e
-
Mn
4+

same number of e
-
----------------------------------------------------------------
3Fe
2+
+ Mn
7+
3Fe
3+
+ Mn
4+

4. Replace y compound

5. Write the equation 3Fe
2+
+ MnO
4
-
3Fe
3+
+ MnO
2(s)

w/ compounds

6. Balance O w/ H
2
O 3Fe
2+
+ MnO
4
-
3Fe
3+
+ MnO
2(s)
+ 2H
2
O

7. Balance H
+
4H
+
+ 3Fe
2+
+ MnO
4
-
3Fe
3+
+ MnO
2(s)
+ 2H
2
O


8. In alkaline solution 4H
+
+ 3Fe
2+
+ MnO
4
-
3Fe
3+
+ MnO
2(s)
+ 2H
2
O
- balance H
+
with H
2
O
4H
2
O 4H
+
+ 4OH
-
-------------------------------------------------------------------------
2H
2
O + 3Fe
2+
+ MnO
4
-
3Fe
3+
+ MnO
2(s)
+ 4OH
-


9. We know that in alkaline 2H
2
O + 3Fe
2+
+ MnO
4
-
3Fe
3+
+ MnO
2(s)
+ 4OH
-
solution, Fe
3+
and OH
-
3Fe
3+
+ 9OH
-
3Fe(OH)
3(s)

will combine to form -----------------------------------------------------------------------
Fe(OH)
3(s)
2H
2
O + 3Fe
2+
+ MnO
4
-
+ 5OH
-
3Fe(OH)
3(s)
+ MnO
2(s)




5-Redox_S11.doc
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Example A B + C

Reactants Products


S
2
O
4
2

S
2
O
3
2





HSO
3

(aq)

1) Identify principal reactants and products

Reactants Products

2(3+) 4(2) 2(2+) 3(2)
S
2
O
4
2
S
2
O
3
2




1+ 4+ 3(2-)

H S O
3


Note:
2S
3+
+ 2S
2+
S
3+
S
4+


2) Balance e-

S
3+
+ e- S
2+
S
3+
S
4+
+ e-
-----------------------------------------------------------------------------

3) Balance S

(x 2) 2S
3+
+ 2e- 2S
2+
(x 2) 2S
3+
2S
4+
+ 2e-
------------------------------------------------------------------------------
4S
3+
2S
2+
+ 2S
4+


4) Replace by compound

2S
2
O
4
2
(aq)
S
2
O
3
2
+ 2HSO
3



5) Balance O with H
2
O

2 S
2
O
4
2

+ H
2
O S
2
O
3
2

+ 2HSO
3



6) Balance H
+
with H
2
O - balanced



5-Redox_S11.doc
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Example
Reactants Products

CN

+ Cl
2
CO
2
+ N
2
+ Cl


2+ 3 0 4+ 2(2) 0 1
C N

+ Cl
2
CO
2
+ N
2
+ Cl


1) Identify principal reactants and products

Reactants Products

2+ 4+ 2(2)
C CO
2

3 0
N N
2
0 1
Cl
2
Cl

---------------------------------------------------------------------------------------------------------
2)
Ox: C
2+
C
4+
+ 2e-

0
Ox: (x2) 2N
3
N
2
+ 6e-

0
Re: Cl
2
+ 2e- 2Cl

----------------------------------------------------------------------------------------------------------

3)
Ox: (x2) 2C
2+
2C
4+
+ 4e-

0
Ox: 2N
3
N
2
+ 6e-

Re: (x5) 5Cl
2
+ 10e- 10Cl

-------------------------------------------------------------------------------------------------------------
2CN

+ 5 Cl
2
2CO
2
+ N
2
+ 10 Cl


4) Balance O with H
2
O

2CN

+ 5 Cl
2
+ 4H
2
O 2 CO
2
+ N
2
+ 10Cl


5) Balance H
+
with H
2
O

2CN

+ 5 Cl
2
+ 4H
2
O 2 CO
2
+ N
2
+ 10Cl

+ 8H
+



Note:
NaCN + H
2
O HCN + NaOH
KCN + H
2
O HCN + KOH


5-Redox_S11.doc
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Organic Chemistry - Nitriles

Cyanide any chemical compound that contains the cyano group, -CN

General Functional Example:
Formula Group

R-CN -CN CH
3
-CN

Common: Acetonitrile or Methyl cyanide
IUPAC: Ethanenitrile

- Nitrile do not release cyanide ions.


Direction of Reaction (SJ, 322)

Example: Chemical Oxygen Demand (COD) test
- Redox reaction between potassium dichromate K
2
Cr
2
O
7
and ferrous iron, Fe
2+
.

1) Balance the reaction
2) Determine the equilibrium constant, K
3) Determine if the reaction proceeds spontaneously if [Fe
2+
] = 10
-4
, [Fe
3+
] = 10
-3
,
[Cr
3+
] = 10
-2.4
, [Cr
2
O
7

2-
] = 10
-2.7
, [H
+
] = 10
+1.3
(Ignore ionic strength).


(Solution)

1. Balance the reaction
Reactants Products
step 1:

2(6+) 7(2-) (3+)
Cr
2
O
7

2-
W Cr
3+
Fe
2+
W Fe
3+
step 2:
Cr
6+
+ 3e
-
W Cr
3+
Fe
2+
W Fe
3+
+ e
-

step 3:

(x 2) 2Cr
6+
+ 6e
-
W 2Cr
3+
(x 6) 6Fe
2+
W 6Fe
3+
+ 6e
-

------------------------------------------------------
Cr
2
+ 6Fe
2+
W 2Cr
3+
+ 6Fe
3+

5-Redox_S11.doc
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step 4: Replace with compounds
Cr
2
O
7
2-
+ 6Fe
2+
W 2Cr
3+
+ 6Fe
3+


step 5: Balance O with H
2
O
Cr
2
O
7
2-
+ 6Fe
2+
W 2Cr
3+
+ 6Fe
3+
+ 7 H
2
O

step 6: Balance H with H
+
14H
+
+ Cr
2
O
7
2-
+ 6Fe
2+
W 2Cr
3+
+ 6Fe
3+
+ 7 H
2
O

Note:
1) dichromate is reduced to chromic ion - gained e
-
2) ferrous ion is oxidized to ferric ion - lost e
-

or
Dichromate is reduced to chromic ion (GER):
Cr
2
O
7

2-
+ 14H
+
+ 6e
-
W 2Cr
3+
+ 7 H
2
O Reduction

Ferrous ion is oxidized to ferric ion (LEO):
6Fe
2+
W 6Fe
3+
+ 6e
-
Oxidation
---------------------------------------------------------------------------------------------------
14H
+
+ Cr
2
O
7

2-
+ 6Fe
2+
W 2Cr
3+
+ 6Fe
3+
+ 7 H
2
O


f
G

(kcal/mol) 0 -315.4 -20.30 -51.5 -2.52 -56.69


GE = (3<
i
f
G
)
products
- (3<
i
f
G
)
reactants


where <
i
= stoichiometric coefficient of species i
f
G

= free energy per mole of species i at 25EC and 1 atm, kcal/mol.
G E = standard free energy change, kcal

GE = [ 7(-56.69) + 6(-2.52) + 2(-51.5) ] - [ 6(-20.30) + (-315.4) + 14(0) ]
= 77.8 kcal/mol

GE = RT ln Keq
9 . 131
) 298 )( / 10 99 . 1
) / 8 . 77 (
ln
3
=

=

=

K K mol kcal x
mol kcal
RT
G
K
eq


K
eq
= e
131.9
= 1.92 x 10
57

5-Redox_S11.doc
1
or

ln Keq = 131.9

2.302 log
10
K
eq
= 131.9

log K
eq
= 57.27

K
eq
= 10
57.27
= 1.92 x 10
57

or

G E = RT ln K
eq
= (2.303) RT log K
eq
3 . 57
) 298 )( / 10 99 . 1 ( 303 . 2
) / 8 . 77 (
303 . 2
log
3 10
=

K K mol kcal x
mol kcal
RT
G
K
eq


K
eq
= 10
57.3

3) Determine if the reaction proceeds spontaneously if [Fe
2+
] = 10
-4
, [Fe
3+
] = 10
-3
,
[Cr
3+
] = 10
-2.4
, [Cr
2
O
7

2-
] = 10
-2.7
, [H
+
] = 10
+1.3
.




G = G E + RT ln Q

= -77.8 kcal/mol + (1.99 x 10
-3
kcal/mol K) (298 K) ln 10
-14.3

= - 97.2 kcal/mol < 0 This reaction is spontaneous as written.

or

This reaction is spontaneous as written.



This reaction is utilized in the titrimetric finish of the COD test.
3 6 3 2 3 6 2.4 2
14.3
2 6 2 14 4 6 2.7 1.3 14
2 7
[ ] [ ] (10 ) (10 )
10
[ ] [ ][ ] (10 ) (10 )(10 )
Fe Cr
Q
Fe Cr O H
+ +

+ + +
= = =
14.3
57.3
10
1
10
eq
Q
K

= <
5-Redox_S11.doc
1
Free Energy (G) and Electrode Potential (E) (SJ, p. 324)

G = G + RT ln Q (1)
G = - RT ln K
eq
(2)

G = - n F E (3)
G = - n F E (4)

where G = free energy change
G = standard free energy change
E = electrode potential, volt
E = standard electrode potential, volt (Read Chap 7.3.2, SJ 324-330)
n = number of electrons involved in the reaction
F = Faradays constant
= 23.06 kcal/(volt e- equivalent) = 96,500 coulombs/ e- equivalent

- the charge per mole of electron or the charge per equivalent

Note: 1 coulomb is the amount of electric charge transported by a current of 1 ampere in 1 second.
1C = 1A 1s

Unit check: G = n F E

kcal e- kcal volt
-------- = ------- -------------------- --------
mole mole volt e- equiv




Note: From (2) G = - RT ln Keq = - (2.303) RT log10 Keq

at 25C
G = - (2.303)(1.99 x 10
-3
)(298) = -1.364 log10 Keq

G = -1.364 log10 Keq
or
log10 Keq = - 0.733 G

Keq = 10
- 0.733 G


5-Redox_S11.doc
1
7.3.2 Free Energy and Potential of Half-Reaction (SJ, 324)

Example. Winkler Method for DO

The titration of iodine, I
2(aq)
, to iodide, I
-
, using thiosulfate, S
2
O
3

2-
(Na
2
S
2
O
3
)
blue clear
(SJ 328-329; 450-451)

Reactants Products
1)
(0) (1-)
I
2
I
-

2(2+) 3(2) 4(2.5+) 6(2)
S
2
O
3

2-
S
4
O
6
2
thiosulfate tetrathionate


2) balance e-

(0) 2(1-)
I
2
+ 2e

2 I
-



(2+) (2.5+)
S S + 0.5 e





(0) 2(1-)
I
2
+ 2e

2 I
-


4(2+) 4(2.5+)
(x4) 4S 4S + 2 e


---------------------------------------------------

4(2+) 4(2.5+)

I
2
+ 4S 4S + 2I


I
2
+ 2 S
2
O
3
2-
S
4
O
6
2-
+ 2I




Note:
I
2
+ 2 S
2
O
3

2-
S
4
O
6
2-
+ 2I
-


f
G
+3.93 -127.2 -246.3 -12.35
(kcal/mole)


G = [(-246.3) +2 (-12.35)] - [ (3.93) + 2 (-127.2)] = -20.53 kcal/mole






5-Redox_S11.doc
1

From Table 7-1, (SJ 328-329; 450-451)

Half Reaction (same as above example reaction) E (v)

Re: I
2
+ 2e
-
2 I

+ 0.62

Ox: 2 (S
2
O
3
)
2
(S
4
O
6
)
2
+ 2e
-
- 0.18
--------------------------------------------------------------------------------------------

Reduction: I
2
+ 2 e

2 I

+ 0.62
G
f
3.93 0 -12.35
(kcal/mole)

Oxidation 2 (S
2
O
3
)
2-
(S
4
O
6
)
2-
+ 2 e
-
- 0.18
G
f
-127.2 - 246.3 0
(kcal/mole)

Species G
f
(kcal/mol)
------------------------------------------
e
-
0
I
2
+3.93
I
-
-12.35
S
2
O
3

2-
-127.2
S
4
O
6

2-
-246.3
------------------------------------------

Standard free energy change:

Reduction rxn: G = ( G
f
)
products
- (G
f
)
reactants

= 2 (-12.35) [(+3.93) + 2 (0)] = -28.63 kcal/mole

Oxidation rxn: G = ( G
f
)
products
- (G
f
)
reactants

= [- 246.3 + 2(0)] [2 (-127.2)] = + 8.1 kcal/mole

The overall reaction E G - n F E
(v) (kcal/mole) (kcal/mole)

2 e
-
+ I
2(aq)
2 I
-
+ 0.62 -28.63 -2 (23.06)(+0.62) = -28.59

2 S
2
O
3
)
2-
S
4
O
6

2-
+ 2 e
-
- 0.18 +8.1 -2 (23.06)(-0.18) = +8.3
-----------------------------------------------------------------------------------------------------------------
I
2(aq)
+ 2 S
2
O
3

2-
S
4
O
6
2-
+ 2I
-
-20.53 -20.29

F = 23.06 kcal/ (volt e-equivalent)


5-Redox_S11.doc
1

Combination of Half-Reactions

Example 7.5 (SJ, p. 331) see Table 7-1 (p. 329)

Determine E
Fe3+, Fe(s)
for the half reaction: Fe
3+
+ 3e

Fe
(s)

G = - n F E

E (V) - n F E
Fe
2+
+ 2e- Fe
(s)
-0.44 - 2 F (-0.44)

Fe
3+
+ e- Fe
2+
0.77 -1 F (+0.77)

Fe
3+
+ 3e- Fe
(s)
-3F (E
Fe3+, Fe(s)
)


-n F (E
Fe3+, Fe(s)
) = (-n FE
Fe2+, Fe(s)
) + (-n F E
Fe3+, Fe2+
)

-3F (E
Fe3+, Fe(s)
) = [-2 F (-0.44)] + [-1 F(0.77) ]

-3F (E
Fe3+, Fe(s)
) = F (0.88 0.77)

(E
Fe3+, Fe(s)
) = (F/-3F) (0.88 0.77) = - 0.037 volt



Example
E(volt)
Fe
2+
Fe
3+
+ e
-
-0.771
O
2
+ H
+
+ e
-
H
2
O +1.229


Determine free energy for each half reaction and equilibrium constant.

Given: Table 1 (SJ 64)

Species G (kcal/mole)

e
-
0
Fe
2+

(aq)
-20.30
Fe
3+

(aq)
-2.52

O
2

(g)
0
H
+

(aq)
0
H
2
O
(aq)
-56.69
_________________________


5-Redox_S11.doc
1
(Solution)
Fe
2+
Fe
3+
+ e
-

G -20.30 -2.52 0
(kcal/mol)

G (kcal/mol) = (-2.52) + 0 (-20.30) = +17.78

O
2
+ H
+
+ e- H
2
O
G 0 0 0 -56.69
(kcal/mol)

G (kcal/mol) = (-56.69) 0 = -28.35

Combine the half reactions (balanced) G (kcal/mole) E(volt)__- nFE____

Fe
2+
Fe
3+
+ e
-
+ 17.78 -0.771 - (1)F(-0.771)
O
2
+ H
+
+ e - H
2
O -28.35 +1.229 - (1)F (+1.229)
_________________________________________________________________________
Fe
2+
+ O
2
+ H
+
Fe
3+
+ H
2
O -10.57 (-0.458) -(1)F E
cell


[- (1)F(-0.771) ] + [ - (1)F (+1.229)] = -(1)F E
cell


-F (-0.771+1.229)
E
cell
= --------------------- = +0.458 volt
- F

G = - n F E = - (1) (23.06 kcal/volt. e
-
equiv)(0.458 volt)
= -10.56 kcal/ e
-
equiv (-10.56 kcal/mole)

At equilibrium,
G = - RT ln K
eq
= - (2.303) RT log
10
K
eq

= -(2.303)(1.9872 x 10
-3
kcal/mol K)(298K) log
10
K
eq
-10.57 kcal/mole = -(1.3638 kcal/mol) log
10
K
eq


-10.57
log
10
K
eq
= --------- = 7.79
-1.36

K
eq
= 10
7.79
= 6.15 x 10
7

( )
3
7.79
1/ 4
2
2
10
eq
o
Fe
K
Fe H P
+
+ +
(

= =
( (

= 6.15 x 10
7



Po
2
can be computed knowing Fe
2+
, Fe
3+
, and pH


5-Redox_S11.doc
1

The Nernst Equation (SJ 331)

G = G + RT ln Q (1)
G = - RT ln K
eq
(2)

G = - n F E (3)
G = - n F E (4)

From (3) E
G
nF
=

(3)

From (4) E
G
nF
=

(4)

Divide each term of Eq (1) by nF

G
nF
G
nF
RT
nF
Q

ln (1() (1)

Substitute (3) and (4) into (1)

E E
RT
nF
Q = ln or or
10
2.303 log
RT
E E Q
nF
=
(5)
where
R = 8.32 J/mole K = 8.32 volt. coulomb /mole K = 1.9872 x 10
-3
kcal/mol K
T = 273 +25 =298 K at 25C
F = 23.06 kcal/ (volt e-equiv) = 96,500 coulomb/e-equiv

This is the Nernst equation.

Note: 1 Joule = 1 volt. coulomb = 0.2389 calorie
1 calorie = 4.185 Joule

At 25C (298 K)

( )
3
10
1.9872 10
2.303 298
log
23.06
x kcal
K
mole K
E E Q
kcal
n
volt e equiv

| |
|
\
=
| |
|
\
i



or
5-Redox_S11.doc
1
( )
10
8.32 .
2.303 298
log
96, 500
volt coulomb
K
mole K
E E Q
coulomb
n
e equiv

| |
|
\
=
| |
|
\


E E
n
Q =
0 059
10
.
log

At equilibrium, G = 0, E = 0, and Q = K
eq

E
n
K
eq
=
0 059
10
.
log

10
log 16.9
eq
K nE =
at 25C



Example Find the electrode potential, E (V), for the half reaction of sulfate, SO
4
2-
to sulfite, SO
3
2-
at
25C. The reaction takes place at [SO
4
2-
] = 1 x10
-5
and [SO
3
2-
] = 1 x10
-5
at pH = 5.0

E (V)
SO
4
2-
+ 2H
+
+ 2e
-
SO
3
2-
+ H
2
O -0.04


10
2
3
10 2
2
4
0.059
log
0.059
log
E E Q
n
SO
E
n
SO H

+
=
(

=
( (



( ) ( )
5
10 2
5 5
10
0.059 0.059
log 0.04 10 0.335
10 10
E E V
n n


(

= = =
( (



5-Redox_S11.doc
2

Example 7-6: Daniel cell (SJ 332)

A zinc electrode in a zinc chloride solution connected to a copper electrode in a cupric chloride
solution. What is the equilibrium constant of the cell reaction at 25C?

e
-
e
-
Zn K
+
Cl
-
Cu
Salt Bridge
Zn
2+
Cl
-
Cu
2+
Cl
-
Zn Zn
2+
+ 2e
-
Cu
2+
+ 2e
-
Cu
Anode Cathode
(negative) (positive)
Voltim
eter


Note: Anode is where oxidation occurs An Ox
Cathode is where reduction occurs Red Cat



From Table 7-1 (SJ 329)

Half reaction E(V) G= -nFE

Ox: Zn
(s)
Zn
2+
+ 2e
-
+0.76 -2F(0.76)
Re: 2e
-
+ Cu
2+
Cu
(s)
+0.34 -2F(0.34)
---------------------------------------------------------------------------------------
Redox: Zn
(s)
+ Cu
2+
Zn
2+
+ Cu
(s)
+1.10 -2FE
Zn(s),Cu2+



Note:
-2FE
Zn(s),Cu2+
= -2F(0.76) -2F(0.34) = -2F(0.76 - 0.34)

E
Zn(s),Cu2+
= +1.10

The Nernst Equation at equilibrium:
ln
eq
RT
E K
nF
=


At 25C,
10
0.059
log
eq
E K
n
=

10
0.059
1.10 log
2
eq
K + =
K
eq
= 10
37.2

5-Redox_S11.doc
2
or
10
log 16.9 16.9(2)(1.10) 37.18 K nE = = =
K
eq
= 10
37.2


Free Energy Eq:
G G RT Q = + ln
(1)

The Nernst Eq: E E
RT
nF
Q = ln (2 (2 (2)


Dividing Eq (2) by RT/nF and changing E to E
H
yields

E
RT nF
E
RT nF
Q
H
o
/ /
ln =

where E
H
= redox potential (see SJ 335)

nF
RT
E
nF
RT
E Q
H
o
= ln


nF
RT
E
nF
RT
E Q
H
o
= 2 303 . log



If n = 1

F
RT
E
F
RT
E Q
H
o
2 303 2 303 . .
log =


At equilibrium, G = 0 thus E
H
= 0

log
2.303
eq
F
E K
RT
=

2.303
log
eq
RT
E K
F
=

log
2.303
eq
F
K E
RT
=


exp
2.303
eq
F
K E
RT
| |
=
|
\


or based on natural logarithm

If n 1
5-Redox_S11.doc
2

E
RT
nF
K
K
nF
RT
E
K
nF
RT
E
eq
eq
eq
=
=
=
|
\

|
ln
ln
exp




Electrochemistry (FE manual)

An electrolyte is a substance that dissociate in solution to produce positive and negative ions.
- It can be an aqueous solution of a soluble salt, or it can be an ionic substance in molten
form.

Electrolysis is the passage of an electric current through an electrolyte driven by an external
voltage source.
- Electrolysis occurs when the positive terminal (the anode) and negative terminal (the
cathode) of a voltage source are placed in an electrolyte.
- Negative ions (anions) will be attracted to the anode, where they are oxidized.
- Positive ions (cations) will be attracted to the cathode, where they will be reduced.
- The passage of ions constitute the current.

Electrolytic (electrochemical) reactions
- Some reactions that do not proceed spontaneously can be forced to proceed by supplying
electrical energy. Such reactions are called electrolytic (electrochemical) reactions.

Faradays Laws of Electrolysis
- Faradays Laws of Electrolysis can be used to predict the duration and magnitude of a
direct current needed to complete an electrolytic reaction.

Law 1: The mass of a substance generated by electrolysis is proportional to the amount of
electricity used.
Law 2: For any constant amount of electricity, the mass of substance generated is
proportional to its equivalent weight.
Law 3: One faraday of electricity (96,485 C or 96,485 As) will produce one gram
equivalent weight.

The number of gram of a substance produced at an electrode in an electrolytic reaction can be
found from the equation:

( )
( ) no. of
96, 485 change in oxidation state
I t MW
m faradays GEW

= =
5-Redox_S11.doc
2

The number of gram-moles produced (n) is

( )( )
no. of
96, 485 change in oxidation state change in oxidation state
m I t faradays
n
MW

= = =


Example (FE manual): A current of 0.075 A passes through a solution of silver nitrate for 10 minutes.
How much silver is deposited?

(Solution)

The number of gram of a substance produced at an electrode in an electrolytic reaction can be found
from the equation (Faradays law):

( )
( ) no. of
96, 485 change in oxidation state
I t MW
m faradays GEW

= =

where m = mass of a substance produced, g
I = current, A
t = time, s
MW = molecular weight or AW = atomic weight

Given:
I = 0.075 A
t = (10 min)(60 s/min) = 600 s
change in oxidation state = 1/mol
AW of Ag = 107.87 g/mol.

( )( )( )
( )( )
0.075 600 107.87 /
0.050
96, 485 1 /
A s g mol
m g
A s mol
= =



Note: AgNO
3
Ag
+
+ NO
3

AgNO
3

is soluble.
Ag
+
+ e
-
Ag Ag
+
is readily reduced to Ag (metallic)

- Change in oxidation state, z = 1
- Silver exists as single atoms, so the molecular weight is the atomic weight, 107.87 g/mol.


5-Redox_S11.doc
2

Example(FE manual): How many grams of copper will be deposited at an electrode if a current of 1.5
A is supplied for 2 hours to a CuSO
4
solution?

Given:
The dissociation reaction for copper sulfate is: CuSO
4
Cu
2+
+ SO
4
2-

The electrolytic reaction equation is: Cu
2+
+ 2e
-


Cu

The change in oxidation number is 2 per atom of copper deposited; i.e.,
The change in oxidation state, z = 2/atom

I = 1.5 A
t = (2 hrs)(3600 s/hr) = 7200 s
AW of Cu = 63.5 g/mol.

Use Faradays law

( )
( ) no. of
96, 485 change in oxidation state
I t MW
m faradays GEW

= =

where m = mass of a substance produced, g
I = current, A
t = time, s
MW = molecular weight or AW = atomic weight

( )( )( )
( )( )
1.5 7200 63.5 /
3.55
96, 485 2 /
A s g mol
m g
A s mol
= =






5-Redox_S11.doc
2

Electron activity and the negative logarithm of electron activity (SJ 338)

Electron activity, {e
-
}
Negative logarithm of electron activity, log {e
-
} = p

- a measure of the availability of electrons in solution (even though no free electrons exist in
solution).

For the half rxn: M
3+
+ 2 e
-
M
+


{M
+
}
K = -------------------
{M
3+
} {e
-
}
2

1 {M
+
}
{e
-
}
2
= ----- --------
K {M
3+
}
{M
+
}
2 log {e
-
}

= log K - log -------
{M
3+
}
Divide by 2:

1 1 {M
+
}
log {e
-
}

= --- log K --- log -------
2 2 {M
3+
}

1 {M
+
}
p

= p

--- log -------


2 {M
3+
}

where p

= log {e
-
}

p



= 1/n log K

---------------------------
General half reaction (reduction)

For the half rxn, Ox + n e
-
Red

General eqn
1 {Red}
p

= p

--- log -------


n {Ox}

where p

= log { e
-
} and p



= 1/n log K

Combining half reactions:

5-Redox_S11.doc
2
Reduction M
2+
+ e
-
M
+
K
1


Oxidation H
2(g)
H
+
+ e
-
K
2
----------------------------------------------------------------------------------------------------------------
Redox M
2+
+ H
2(g)
M
+
+ H
+
K
3
= K
1
K
2


Note: The reduction of H
+
to H
2(g)
at standard condition is assigned G = 0 and K
eq
= 1
(i.e., K
2
= 1 ). Since G = nFE , E = 0

{M
+
} {e
-
}
K
3
= K
1
because K
2
= ------------ = 1 by convention
{H
2
}
1/2


{M
+
}
K
1
= ---------------
{M
2+
} {e
-
}

1 {M
+
}
{e
-
}

= ----- ---------
K
1
{M
2+
}

{M
+
}
- log {e
-
}

= log K
1
- log ---------
{M
2+
}

{M
+
}
p

= p

log -------
{M
2+
}

where p

= log {e
-
}

p



= 1/n log K
1



Example (SJ 340): Reduction of ferric ion (Fe
3+
) to ferrous ion (Fe
2+
).

From Table 7-1 (p =16.9E see below)

Half Reaction ___ E (v) p___K = exp (nFE/RT)_______

(1) Fe
3+
+ e

Fe
2+
0.77 13 K
1
= 10
13

(2) H
2 (g)
H
+
+ e

0 0 K
2
= 1 (by convention)
_______________________________________________________________________

(3) Fe
3+
+ H
2 (g)
Fe
2+
+ H
+
0.77 K
3
= K
1
K
2
= 10
13

5-Redox_S11.doc
2

From Rxn (1)

{ }
{ }{ }
{ }
{ }
{ }
{ }
{ }
{ }
K
Fe
Fe e
e
K
Fe
Fe
e K
Fe
Fe
1
2
3
1
2
3
1
2
3
1
=
=
=
+
+

+
+

+
+
log log log

{ }
{ }
p p
Fe
Fe
=
+
+
log
2
3
(7-11)

where
p = - log {e
-
}
p = log K
1
(p = 1/n log K
1
)

when {Fe
2+
} = {Fe
3+
}, p = p = log K
1


For the reaction (3)

{ }{ }
{ }
{ }
K K K
Fe H
Fe H
g
3 1 2
2
3
2
1 2
= =
+ +
+
( )
/

Note {H
+
} / {H
2(g)
}
1/2
= 1 by convention

{ }
{ }{ }
{ }{ }
( )
{ }
{ }
2( )
2 2
1/ 2
3 3
g
H
Fe H e Fe
Fe e Fe
p
+ + +
+ +
=


From Free energy equation:

{ }
{ }
G G RT
Fe
Fe
= +
+
+
ln
2
3
(7-12)

From Nernst Equation:

{ }
{ }
E E
RT
nF
Fe
Fe
H
=
+
+
ln
2
3
(7-13)

5-Redox_S11.doc
2
Potential E E
H
redox potential (see p. 335)

Divide (7-13) by RT/nF

{ }
{ }
+
+

=
3
2
ln
/ / Fe
Fe
nF RT
E
nF RT
E
H



{ }
{ }
nF
RT
E
nF
RT
E
Fe
Fe
H
|
\

| =
|
\

|
+
+
ln
2
3


converting ln log yields

{ }
{ }
nF
RT
E
nF
RT
E
Fe
Fe
H
|
\

|
=
|
\

|

+
+
2 303
10
2
3
. log


Since n = 1

{ }
{ }
F
RT
E
F
RT
E
Fe
Fe
H
2 303 2 303
10
2
3
. .
log
|
\

| =
|
\

|
+
+
(7)

Comparing (7-11) and (7), we find

{ }
{ }
2
10
3
log
Fe
p p
Fe

+
+
=
(7-11)

p
F
RT
E p
F
RT
E
H
= =
2 303 2 303 . .


Since
( )
p
F
RT
E
p
kcal
volt equiv
x kcal
mole K
K
E E
H
H H

=
=
|
\

|
=

2 303
2306
2 303
1987 10
298
16 9
3
.
.
.
.
.
.
(7-14)

or
5-Redox_S11.doc
2
( )
p
F
RT
E
p
coulomb
equiv
J
mole K
K
E E
H
H H

=
=
|
\

|
=
2 303
96 500
2 303
8 314
298
16 9
.
,
.
.
.


16.9 16.9
2.303
H
F
p E E E
RT


= = =
(7-15)


Since G = nFE , FE = G/n
Since G = nFE , F E = G /n


p
G
nRT
=

2 303 .
(7-20)
and
p
G
n RT
=

2 303 .
(7-21)

p is proportional to the free energy change accompanying the transfer of 1 mole of electron
from a reducing agent at unit activity to H
+
at unit activity.