Solution For Exercise Series 2: E E E G E VF
Solution For Exercise Series 2: E E E G E VF
Solution For Exercise Series 2: E E E G E VF
The maximum potential of a cell that could be put at work in order to move
electrons from anode to cathode through the external wiring,
EelC − EelA = Ecell = ϕ C − ϕ A
∆rG
It is directly proportional to the reaction Gibbs free energy, Ecell = −
ve F
i.e. it is only determined by the thermodynamic properties of the cell.
Ideally, it could only be harvested, if no current were flowing through the
cell, i.e. under open circuit conditions. Under real conditions, i.e. in an
operating electrochemical cell, a finite current will be drawn, electrons will
perform work and the cell will operate at a certain power density, given by
P = j · ∆V, where ∆V is the actual potential difference between cathode
and anode that forces electrons to move. Finite currents always imply
irreversible voltage losses and thus, ∆V < Ecell .
T = 25°C,
gas pressures 1 atm
concetrations 1 mol/l
activities a = 1
Saturated CdSO4
solution
CdSO4 (s)
Hg2SO4 (s)
Cd(Hg) (l)
Hg (l)
— +
RT
Ecell = ϕ C − ϕ A = E 0 − ln aCd2+ aSO2-
2F 4
∆rG
Ecell = − ⇒ ∆ r G = −2 FEcell = −196.4 kJ / mol
2F
(d) The EMF given in (c) is not the standard EMF, but it is
nevertheless very stable. Can you explain why (hint: you can
assume that the solution remains saturated, what about other
parameters)?
⇒ ∆ ln aCd2+ aSO2- ≈ 0
4
3. Consider the cell Pt | H2(g, 1 atm) | H+(aq, a=1) | Fe3+(aq),Fe2+ | Pt, given
that Fe3+ + e- → Fe2+ and E 0 = 0.771 V
(a) If the cell potential is E = 0.712 V (at 25°C) , what is the ratio of
concentrations of Fe3+(aq) and Fe2+(aq)? Could you determine
the absolute values of concentrations or just their ratio?
H 2 ( g ) → 2 H + (aq ) + 2e−
Fe3+ (aq ) + e − → Fe 2+ (aq)
Overall: H 2 ( g ) + 2 Fe3+ (aq) + 2e− → 2 H + (aq) + 2 Fe2+ (aq) + 2e −
RT
Ecell = EelC − EelA = 0.771 V − ln Q
2F
2 2
RT aH+ cFe2+
= 0.771 V − ln 2
2 F PH2 cFe 3+
Ecell − E 0 = +0.059V
Note: this is the same absolute value as in (a)!
c 2+
⇒ Fe = 0.1 (the reciprocal of the ratio found in (a))
cFe3+
E 0 = E 0C − E 0A = ϕ 0C − ϕ 0A = 0
RT 0.001 M RT
E = E0 − ln =− ln 0.001 = 0.089V , ve = 2
2F 1.0 M 2F
(c) Calculate E at 25°C for the specified concentrations – see (b)
5. Living cells maintain a small voltage drop across their membrane in its
resting state due to the directed transport of sodium ions from inside to
outside and the transport of potassium ions in the opposite direction
(driven by pumping mechanisms). The inside of the cell is negative with
respect to the outside. Consider a mammalian muscle cell with the internal
and external ion concentrations:
inside outside
[K]i = 140 mM [K]o = 2.5 mM
[Na]i = 10 mM [Na]o = 115 mM
[Cl]i = 15 mM [Cl]o = 140 mM
RT ciout
⇒ ∆ϕ = ϕ in − ϕ out = ln in
zi F ci
(a) What are the equilibrium potentials for each of these ions?
RT [ K + ]out RT 2.5
K+ : ∆ϕ K + = ln = ln = −0.104V
zi F [ K + ]in F 140
RT [ Na + ]out RT 115
Na + : ∆ϕNa+ = ln = ln = 0.063V
zi F [ Na + ]in F 10
RT [Cl − ]out RT 140
Cl − : ∆ϕ Cl- = ln − in
=− ln = −0.058V
zi F [Cl ] F 15
(b) Calculate the total molar Gibbs free energy of reaction and the
corresponding voltage across the cell membrane.
∆ r G = ∆ r GK + + ∆ r G Na + + ∆ r GCl −
∆rG
∆ϕ = − = +0.0165V
F