Solution For Exercise Series 2: E E E G E VF

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Solution for exercise series 2

CHEM465/865, 2006-3, 13th Sep., Dr. M. Eikerling


Ata Roudgar, [email protected], x3699

1. Write down explanations of the following terms or answers on the queries


(a) What is the EMF of a galvanic cell? Specify the relation between
the maximum reversible work of a reaction and the EMF.

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 .

(b) Why can Galvani potentials between distinct phases not be


measured?

The two contacting phases will have distinct chemical composition.


Therefore, upon transferring charged particles (which could be seen as
test particles for probing the local Galvani potentials) between these
phases not only electrostatic work but also chemical work will have to be
performed (in other words: there will also be a difference in chemical
potentials, look up definitions of chemical potentials and electrochemical
potentials). Moreover, charges will have to be moved across the metal
surface which possesses a rather nonuniform charge distribution, resulting
in the so-called surface potential (look up definitions of Volta potential and
Galvani potential).

(c) What are the properties of a good reference electrode?

An ideal reference electrode should have a stable, well-defined (i.e.


reproducible) electrochemical potential. Common reference electrodes
(SCE, Ag/AgCl, Cu/CuSO4) meet this criterion when they are functioning
properly. An ideal reference electrode should also have zero impedance.
(d) Specify the known “standard conditions” as complete as
possible.

T = 25°C,
gas pressures 1 atm
concetrations 1 mol/l
activities a = 1

(e) What is an ideally polarizable electrode?

An electrode at which no charge transfer processes occur in the


considered range of electrode potentials. There will be no Faradaic
currents, only double layer charging effects, i.e. only capacitive currents.
Such electrodes are needed for instance in supercapacitors. Now you
already know that this situation reaquires that the exchange current
density of this electrode has to be extremely small.

2. The Weston cell, invented by Edward Weston in 1893, is an


electrochemical cell. Due to its highly stable voltage it is suitable as a
laboratory standard for calibration of voltmeters. It was adopted as the Int.
Standard for EMF in 1911.

The Weston Cell

Saturated CdSO4
solution

CdSO4 (s)
Hg2SO4 (s)

Cd(Hg) (l)
Hg (l)

— +

The anode is an amalgam of cadmium with mercury, the cathode is of pure


mercury, and the electrolyte is a solution of cadmium sulphate. The overall
cell reaction is
2+ 2–
Cd(Hg) + Hg2SO4(s) ↔ 2 Hg(l) + Cd (aq) + SO4 (aq.)

(a) What are the half reactions of this cell?


Anode: Cd → Cd 2+ (aq ) + 2e −
Cathode: Hg 2 SO4 ( s ) + 2e − → 2 Hg (l ) + SO4 2− (aq )

(b) Write the Nernst-equation for the cell reaction.

RT
Ecell = ϕ C − ϕ A = E 0 − ln aCd2+ aSO2-
2F 4

(c) The EMF is E = 1.0180 V (at 25°C) . What is the corresponding


reaction Gibbs free energy? What is the corresponding rate
constant.

∆rG
Ecell = − ⇒ ∆ r G = −2 FEcell = −196.4 kJ / mol
2F

Equilibrium rate constant


⎛ ∆ G⎞
K = exp ⎜ − r ⎟ = 2.71 ⋅ 1034
⎝ RT ⎠
The reaction proceeds spontaneous. The rate constant is >>> 1.

(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)?

Consider a variation in cell potential. In general form this is given


by
RT
∆Ecell = − ∆ ln aCd2+ aSO2-
2F 4

Since the solution remains saturated

⇒ ∆ ln aCd2+ aSO2- ≈ 0
4

⇒ ∆Ecell ≈ 0 is very stable. Even fluctuations in temperature


will not significantly affect the cell potential.

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+

T = 298K, aH+ = 1 , PH2 =1atm


2
RT cFe2+
0.712 V = 0.771 V − ln 2
2F cFe3+
Ecell − E 0 = −0.059 V
cFe2+
= 10
cFe3+
Only the ratio can be calculated

(b) What is the ratio of these concentrations if the cell potential is


E = 0.830 V (at 25°C) ?

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+

4. Nernst equation demonstrates that the electrode potential depends upon


concentration. A cell made of the same materials, but with different
concentrations, will also produce a potential difference. Consider a cell
Cu | Cu2+ (0.001 M) || Cu2+ (1.00 M) | Cu
(a) What is standard potential of this cell?

E 0 = E 0C − E 0A = ϕ 0C − ϕ 0A = 0

(b) Write down the Nernst-equation (using for simplicity


concentrations of ions in solution instead of activities). What is
the number ν e of electrons being transferred?

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

Two separate compartments (inside & outside), different potential on each


side.

Separate reactions → mixed potential.

Electrode chemical equilibrium:


µiin = µiout
µ i = µi + zi F ϕ , µi = µi 0 + RT ln ci

µi 0 + RT ln ciin + zi F ϕ in = µi 0 + RT ln ciout + zi F ϕ out

RT ciout
⇒ ∆ϕ = ϕ in − ϕ out = ln in
zi F ci

3 species, specified concentrations


⇒ over determined system of egs. (only 2 unknowns! ϕ in , ϕ out )
Not all species in equilibrium

(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 −

∆ r G K + = − F ∆ϕ K + = +9.984 ⋅ 103 J ⋅ mol −1


∆ r G Na + = − F ∆ϕ Na + = −6.048 ⋅ 103 J ⋅ mol −1
∆ r GCl − = − F ∆ϕ Cl − = −5.53 ⋅ 103 J ⋅ mol −1

⇒ ∆ r G = −1.586 ⋅ 103 J ⋅ mol −1

∆rG
∆ϕ = − = +0.0165V
F

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