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.
2+ -
( B) ... Zn Zn + 2e ... EZn / Zn2+ = +0.763
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.
2+ -
( B) ... Cu + 2e Cu ... ECu 2+ / Cu = +0.337
We see that the H2 hydrogen electrode; H + acts as electrode (+) in the case and as
electrode (-) in the second case.
EXAMPLE:
Otro Ejm:
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
Rxn espontnea
Note: The semireaccion is multiplied by 2 in this case, but the E potential is not
multiplied .
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
[ 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 )
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.
Solution:
96489 cal
F= = 23060
4.18 Volt
Ejm:
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+
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
Prob:
Calculate the potential at 298 K of the cell
Cd Cd 2+ (1.0M ) Fe 2+ (1.0M ) Fe
Solucin:
The semireactions are:
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
(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.
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
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
Prob:
Solucin:
La Rxn ser:
Ag + Fe 2+ Ag + + Fe
A. reductor A. Oxidante
Fe 2+ + 2e - Fe EFe2+ / Fe = -0.440V
Ecelda = E Ag
/ Ag +
+ EFe
2+
/ Fe
Ecelda = -0.799 + (-0.440)
Ecelda = -0.239V
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 )
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