ELECTROQUIMICA

Types of electrodes. Potential

Normal hydrogen electrode: called the reference electrode (activity A = 1 to the

pressure of 1 atm.). Its potential is considered zero.

The following diagram represents the case of Zn vs. hydrogen (H2)

If we graph the value of the reduction potential for each of the agents we get:

The highest value for the Zn/hydrogen torque (H2 is 0.00 volts corresponding to the
hydrogen.)

Therefore, the H2 will remain in its reduced form and necessarily the Zn will have to
oxidize.

Of the potential table:

Electrode Reduction reaction E (volts) reduction
1
H+ ; H2 H+ +1e- H2 0.00
2
-
Zn2+ ; Zn +
Zn +2e Zn -0.763

By establishing the redox reactions we obtain:

1
( A) ... H + + 1e - H 2 ... EH + / H = 0.00
2 2

2+ -
( B) ... Zn Zn + 2e ... EZn / Zn2+ = +0.763

Adding 2 (A) + (B) we obtain:

2 H + + Zn + 2e- H 2 + Zn 2+ + 2e - ... ETOTAL = 0.00 + 0.763

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ETOTAL = +0.763V

Rxn Spontaneous
Copper case:

of the tables:
ElectrodE Reduction reaction E (volts) reduction
1
H+ ; H2 H+ +1e- H2 0.00
2
Cu2+ ; Cu Cu+ +2e- Cu +0.337

Of the reduction potentials, the one with the greatest reduction potential will maintain
the sense of reduction, therefore the other half-reaction change of direction, and sign.

Setting the 2 half reactions:

1
( A) ... H 2 2 H + + 1e - ... EH / H + = 0.00
2 2

2+ -
( B) ... Cu + 2e Cu ... ECu 2+ / Cu = +0.337

Adding 2 (a) + (b) we obtain:

H 2 + Cu 2+ + 2e - 2 H + + 2e- + Cu ... ETOTAL

= +0.337V

We see that the H2 hydrogen electrode; H + acts as electrode (+) in the case and as
electrode (-) in the second case.

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EXAMPLE:

Ni Ni 2+ + 2e - ... E Ni / Ni2+ = +0.250

Pb 2+ + 2e- Pb ... EPb

2+
/ Pb
= -0.126
Ni + Pb 2+ Ni 2+ + Pb ... ETOTAL

= 0.124V

Otro Ejm:

Electrodo Reaccin de reduccin E(voltios) de reduccin

Pt ; Fe2+, Fe3+ Fe3+ +1e- Fe2+ 0.771
Pt ; Cl2 ; Cl- Cl2 + 2e- 2Cl- +1.360

Of these potentials, the greater indicates that the sense of reduction in the respective
semireaccion is maintained.

Therefore, the lower potential of reduction must be reversed; at the same time, the
meaning of the equation is reversed:
Fe 2+ Fe3+ + 1e - ... EFe

2+
/ Fe3+
= -0.771V ( Anodo)
Cl2 + 2e - 2Cl - ... ECl / Cl -
= +1.360V (Catodo)
2

2 Fe 2+ + Cl2(g) 2 Fe3+ + 2Cl- ... ETOTAL

= +0.589V (Catodo)

Rxn espontnea

Note: The semireaccion is multiplied by 2 in this case, but the E potential is not
multiplied .

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Representation of a stack:

Oxidacin Reduccin
2+ 2+
(-) Zn Zn (1M ) Cu (1M ) Cu ( +)
nodo Ctodo

Saline Bridge

Nernst equation
It is used to calculate the potentials of electrodes or potentials of the cells for
concentrations and partial pressures other than the values of the standard state.
The electromotive force of a chemical reaction depends. Of the activities (or
concentrations) of reactionary substances and products.

Since:
[ C ] [ D]
c d

DG = DG + RTLn (1)
[ A] [ B ]
a b

In a chemical process such as:

aA + bB cC + dD

Y DG = -nFE ... (2)

Relationship between F.E.M. and free energy change () see page below

We can write: DG = -nFE ... (3)

Replacing (2) y (3) In (1):

[ C ] [ D]
c d

-nFE = - nFE + RTLn

[ A] [ B ]
a b

Dividing between ( - nF ) All the expression:

[ C ] [ D ] ... (4)
c d
RT
E = E - Ln (Ecuacin de NERNST)
[ A] [ B ]
a b
nF
Simplifying:
J
R = 8.314
mol. K
J
F = 96847
V .mol e - MOL electrons

T = 298 K (25 C )

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Using decimal logarithm instead of logarithm Napierian, we obtain:

[ C ] [ D]
c d
0.059
E = E - Log ... (4)
[ A] [ B ]
a b
n
Potential in Potential under
non-standard standard conditions at Moles/L (molarity m in
conditions 25 C and 1 ATM solution) or ATM pressure
for gases.
n = number of electrons in
the semirreaccion

Note: [ H 2O ] = 1
[ Solidos puros ] = 1
() the expression (2) of the previous page shows that: in a chemical reaction G
represntale useful net work made as the reaction proceeds to temperature and P
ctes. Electrical work is performed when there is rxn in a galvanic cell. The
magnitude of work is determined by the difference in potential of the electrodes
and by the number of electrons circulating in the external circuit.

Ejm: Write the Nernst equation corresponding to the semireaccion:

Cu 2+ + 2e- Cu

Solution:

The correct expression will be:

0.059 1 0.059 1
ECu 2+ / Cu = E 2+ - Log 2+
= +0.337 - Log
Cu / Cu n
Cu
2 Cu 2+

Indicate the direction of

the rxn (sense of
reduction)

Note: According to Mahan (p. 300)

RT
DE = DE - LnK
nF
cal
Being: R = 1.98
mol. K
cal
F = 23060
Voltio
T = 298 K
Volt.C J
Equivalences F = 96489 C = 96489 = 96489
Volt Volt
1cal = 4.18 J

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96489 cal
F= = 23060
4.18 Volt

Ejm:

Write the Nernst equations corresponding to C/U of the following semireactions:

+ -
1) 2 H + 2e H 2( g )
2- + - 3+
2) Cr2O7 + 14 H + 6e 2Cr + 7 H 2O

Solution:
2
0.059
Cr 3+

1) ECr2O72- / Cr 3+ = ECr2O72- / Cr 3+ -

Log 14
n 2-
Cr2O7 H+

2
0.059
Cr 3+

2) ECr2O72- / Cr3+ = +1.33 - Log 14
6 2-
Cr2O7 H+

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Calculating Equilibrium constants

Of the EC. (1) When the reactants and products are in equilibrium. Then:

DG = - RTLnK

[ C ] [ D]
c d

K=
[ A] [ B ]
a b

In addition, the normal free energy G and the f. e. m of a reaction in normal state are
equaled according to:
DG = -nFE

Combining the 2 equations we obtain:

RTLnK = nFE
nFE
LnK =
RT
Si:
J
F = 96847
V .mole-
J
R = 8.314
K .mol
T = 298 K
Ln Log
Entonces:
nE
LogK =
0.059

Prob:
Calculate the potential at 298 K of the cell
Cd Cd 2+ (1.0M ) Fe 2+ (1.0M ) Fe
Solucin:
The semireactions are:

Cd Cd 2+ + 2e - (nodo (-)) se da la oxidacin

Fe 2+ + 2e - Fe (Ctodo (+)) se da la reduccin

0.059 Cd 2+

= +0.402 - 0.059 Log 1.0 = 0.402 nodo
ECd / Cd 2+ = E
- Log
Cd / Cd 2+ n [ Cd ] 2 1

EFe2+ / Fe = EFe

-
0.059
Log
[ Fe] = -0.44 - 0.059 Log 1 = -0.44
2+ Ctodo
/ Fe
n Fe 2+

2 1.0
Ecelda = Eanodo + Ecatodo = 0.402 - 0.44 = -0.038Voltios
Ecelda = Etotal = -0.038Voltios

El valor negativo de la celda indica la no realizacin espontnea de la reaccin.

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Ejm: For the following galvanic cell:

(a) Type the 2 semireactions and the total reaction in the cell.
(b) Calculate the F.E.M. of C/cell from the Nernst equation.
(c) Calculate the equilibrium constant of the reaction in the cell
(d) Identify the anode and the cathode and mark the electrodes with the (+) or (-) sign
accordingly.

Cu CuSO4 (0.02M ) Fe3+ (0.01M ), Fe 2+ (0.20M ), HCl (1M ) Pt

Solucin:

A) De la representacin tenemos:
Cu Cu 2+ + 2e -
2 Fe3+ + 2e- 2 Fe2 +
Cu + 2 Fe3+ Cu 2 + + 2 Fe 2+
(Ecuacin global o Rxn total)
B) Etotal de la celda

De las tablas
Cu 2+ + 2e - Cu ERe d = 0.34 V

Fe3+ + 1e - Fe 2 + ERe d = 0.771V

2+
0.059
Cu 0.059 0.02
ECu / Cu 2+ = E
- Log = -0.34 - Log = 0.402 (nodo)
Cu / Cu 2+ 2 [ Cu ] 2 1
Eanodo = -0.29V
0.059 Fe2+

= 0.771 - 0.059 Log 0.2
EFe3+ / Fe2+ = E
Fe3+ / Fe2+
- Log 3+
1
Fe
2 0.01
Ecatodo = 0.694V
Ecelda = Eanodo + Ecatodo = 0.29 + 0.694 = -0.038Voltios
Ecelda = 0.404V
The positive value of the indicates that the RXN was carried out spontaneously.
C) eq = ?
K
Se sabe que:

nETotal
LogK =
0.059
ETotal = ECu

/ Cu 2+
+ EFe

3+
/ Fe2+

ETotal = -0.34 + 0.771

ETotal = +0.431V
2.(0.434)
LogK = = 14.61
0.059
K = 4.07 x 1014

D) Ctodo: (+) Fe3+ / Fe 2+

nodo: (-) Cu / Cu 2+

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Prob:

Will a reaction occur if a AG bar is dipped in a 1 m FeSO4 solution at 25 C?

Solucin:
La Rxn ser:
Ag + Fe 2+ Ag + + Fe

A. reductor A. Oxidante

Las reacciones y sus potenciales son:

Ag Ag + + 1e- E Ag / Ag + = -0.799V

Fe 2+ + 2e - Fe EFe2+ / Fe = -0.440V

Ecelda = E Ag

/ Ag +
+ EFe

2+
/ Fe

Ecelda = -0.799 + (-0.440)

Ecelda = -0.239V

Since this value is negative, no reaction is recorded. It is convenient to see that if a FE

bar is inserted into a 1 m solution of AGNO3, a reaction will occur.

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Concentration cells

They are cells whose half cells similar, only differ in the concentration of their ions and
are able to generate a F.E.M.

Ag Ag + (0.001M ) Ag + (0.1M ) Ag
nodo = Oxidacin Ctodo = Reduccin
C2 ms diluida C1 ms concentrada

To generate voltage (+) The electrode immersed in the most diluted solution must be (-)
anode

\ C1 > C2
{ {
Catodo (0.1M ) Anodo (0.001M )

Ag ( s ) Ag + (C2 ) + 1e- E Ag / Ag + = -0.799V

nodo: Oxidacin
Ag + (C1 ) + 1e - Ag ( s ) E Ag + / Ag = +0.799V

Ctodo: Reduccin
Global equation: Ag + (C1 ) Ag + (C2 ) Ecelda

= 0.000V

The spontaneous rxn of the cell tends to match the 2 concentrations, where

Ecelda = 0.000V pero Ecelda

= (+ ) .
0.059 C2
E
Applying the EC. Cell to each semireaccion: 14 +
Ag / Ag ( C2 )
= E
+
Ag / Ag ( C2 )
- Log
2 43 14 2 43 1 1
Anodo Anodo

0.059 1
E Ag + ( C ) / Ag = E Ag

+ - Log
14 2 43 14 2(C143
1 ) / Ag
1 C1
Catodo Catodo

Sumando:
0.059 C
E Anodo + ECatodo = E Anodo

+ ECatodo

- Log 2
1 C1
C2
ETotal de celda = ETotal

de celda - 0.059 Log
C1
0.001
ETotal de celda = 0.000 - 0.059 Log
0.1
ETotal de celda = 0.118V

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