Lippmann Equations (Surface Excess)

Weierstrass Institute for
Applied Analysis and Stochastics
The Lippmann equation for liquid metal electrodes
Wolfgang Dreyer, Clemens Guhlke, Manuel Landstorfer, Rüdiger Müller
Mohrenstrasse 39 · 10117 Berlin · Germany · Tel. +49 30 20372 0 · www.wias-berlin.de

more than one quantity may be obtained. Consequently cannot be considered as
equivalent to the physical charge on a particular region of the interphase. It is in fact
an alternative
Lippmann equation way of expressing a surface excess or combination of surface excess of
charged species.
Source: doi:10.1351/goldbook.L03577
PAC, 1974, 37, 499 (Electrochemical nomenclature) on page 508
Lippman's equation
PAC, 1986, 58, 437 (Interphases in systems of conducting phases (Recommendations
1985)) on page 445
An equation which gives the electric charge per unit area of an interface (electrode):
where is the interfacial tension, is the potential of a cell in which the reference
electrode has an interfacial equilibrium with one of the ionic components of A, is
the charge on unit area of the interface, is the chemical potential of the combination
of species whose net charge is zero, is the thermodynamic temperature and is
the external pressure. Since more than one type of reference electrode may be chosen,
more than one quantity may be obtained. Consequently cannot be considered as
equivalent to the physical charge on a particular region of the interphase. It is in fact
an alternative way of expressing a surface excess or combination of surface excess of
charged species.
Source:
PAC, 1974, 37, 499 (Electrochemical nomenclature) on page 508
PAC, 1986, 58, 437 (Interphases in systems of conducting phases (Recommendations
1985)) on page 445
IUPAC Compendium of Chemical Terminology Copyright © 2014 IUPAC
Lippmann Equation · March 3. 2015 · Page 2 (29)

Lippmann equation
Lippmann
dγ
= −Q
Ω− dE
q
S
γ
S
Ω+
S

Lippmann equation
Lippmann
dγ
= −Q
Ω− dE
q
S E well defined ?
γ
S
Ω+
S

Lippmann equation
Lippmann
E ~q − dγ
= −Q
Ω− dE
q
S E well defined ?
~q +
~γ −
~γ + Q = Q(q , qe+ , qe− )
γ s
S γ = γ(γ , γ e− )
e+ , γ
Ω+ s
S

Lippmann equation
Lippmann
E ~q − dγ
= −Q
Ω− dE
q
S E well defined ?
~q +
~γ −
~γ + Q = Q(q , qe+ , qe− )
γ s
S γ = γ(γ , γ e− )
e+ , γ
Ω+ s
S
differential capacity
dQ d γ 2
C := dE = − dE 2

Outline
1 Ion transport in electrolyte bulk

Shortcomings of Nernst-Planck model
General continuum model for the bulk
2 Electrochemical double layer

Surface balances and adsorption
Free energy models for metals
Double-layer capacity
3 Lippmann equation for liquid mercury electrode

Matched asymptotic analysis
Numerical results

diluted solution of anions A, cations C in solvet S +

−
− −
+
+ − +
−
+ −
∂t (mα nα ) + div(mα nα v + Jα ) = 0 for α = A, C
+ − − +
−ε∆ϕ = zA nA + zC nC metal + −
− electrolyte
−
ϕ ϕE
s
Nernst-Plack (1890):
Jα = −M (∇nα + zα nα ∇ϕ) for α = A, C

diluted solution of anions A, cations C in solvet S +

−
− −
+
+ − +
−
+ −
∂t (mα nα ) + div(mα nα v + Jα ) = 0 for α = A, C
+ − − +
−ε∆ϕ = zA nA + zC nC metal + −
− electrolyte
−
ϕ ϕE
s
Nernst-Plack (1890):
Jα = −M (∇nα + zα nα ∇ϕ) for α = A, C
1.5
yA
equilibrium → Poisson-Boltzmann y
C
yS
1
0 = ∇nα + zα nα ∇ϕ for α = A, C
y
0.5
−ε∆ϕ = zA n̄A exp(−zA ϕ) + zC n̄C exp(−zC ϕ)

0
0 10 −10
ξL

“Extended” Nernst-Planck models
+ − −
postulated layer structure − +
+ − +
[Stern:1924] −
+ −
+ − − +
metal + − −
− electrolyte
ϕ ϕE
s

+ − −
+ − +
[Stern:1924] −
+ −
−
finite size of ions, volume exclusion + − +
metal + − −
− electrolyte
[Bikerman:1942], [Eigen,Wicke:1952], [Carnahan,Starling:1969],
ϕ ϕE
s
[Borukhov,Andelman,Orlando:1997], [Ajdari,Bazant,Kilic:2007]
... molecular dynamics, statistical mechanics,
Langevin, Monte Carlo, DFT ...
→ Poisson-Fermi

+ − −
+ − +
[Stern:1924] −
+ −
−
finite size of ions, volume exclusion + − +
metal + − −
− electrolyte
[Bikerman:1942], [Eigen,Wicke:1952], [Carnahan,Starling:1969],
ϕ ϕE
s
[Borukhov,Andelman,Orlando:1997], [Ajdari,Bazant,Kilic:2007]
... molecular dynamics, statistical mechanics,
Langevin, Monte Carlo, DFT ...
→ Poisson-Fermi
1.5
yA
400
layers not diluted yC
y
S
300 1
pressure dependence,
p [MPa]
y
200
momentum balance 0.5
100
[Freise:1952], [Sanfeld:1968],
0 0
[DGM13] 0
ξL
10 0
−10
ξR ξL
10
0 −10

General Framework
non-equilibrium thermodynamics distinguishes

general balance laws
material dependent constitutive equations

General Framework
non-equilibrium thermodynamics distinguishes

general balance laws
material dependent constitutive equations
constitutive equations restricted by

2nd law of thermodynamics (cf. [Bothe,Dreyer:2014])
principle of material frame indifference

Electrolyte bulk model
+ −
constituents: A0 , A1 , · · · , AN
− +
− +
− + + +
atomic mass: m0 , m1 , · · · , mN − −
− +
+ +
charge number: z0 , z1 , · · · , zN −
− − +
fields of matter electromagnetic fields

ρ0 , · · · , ρN mass density E electric field
ρv momentum B magnetic field
ρu internal energy

+ −
− +
− +
− + + +
atomic mass: m0 , m1 , · · · , mN − −
− +
+ +
− − +

ρ0 , · · · , ρN mass density E = −∇ϕ electric field
ρu internal energy

+ −
− +
− +
− + + +
atomic mass: m0 , m1 , · · · , mN − −
− +
+ +
− − +

ρ0 , · · · , ρN mass density E = −∇ϕ electric field
ρu internal energy
partial mass balances ∂t ρα + div(ρα v + Jα ) = 0 for α = 0, 1, · · · , N
quasi-static momentum − div(Σ) = ρb

electrostatic Poisson eqn. −ε0 (1 + χ)∆ϕ = nF
Entropy production
[Guhlke:2015]

Constitutive modeling
free energy c = ρψ(T,ρ0 ,ρ1 ,··· ,ρN ,) + χ|E|2

ρψ
N
∂ρψ X
µα = , p := −ρψ + ρα µα (Gibbs-Duhem)
∂ρα
α=0

Constitutive modeling
free energy c = ρψ(T,ρ0 ,ρ1 ,··· ,ρN ,) + χ|E|2

ρψ
N
∂ρψ X
µα = , p := −ρψ + ρα µα (Gibbs-Duhem)
∂ρα
α=0
N N
µ −µ zβ e0
X X
1 z0 e 0
Jα = − Mαβ ∇ β T 0 − T mβ − m0 E , J0 = − Jα
β=1 α=1
Σ = −p + ε0 (1 + χ)(E ⊗ E − 21 |E|2 1)

Free energy
N N
X X nα
ρψ = ρα gαRef (T ) +kT nα ln +ρψ M
n | {z }
α=0 α=0 elastic energy
| {z } | {z }
reference values entropy of mixing
PN Ref
elastic law: p = pRef + K ( α=0 vα nα − 1)
vαRef : specific volume of Aα

Free energy
N N
X X nα
n | {z }
| {z } | {z }
PN Ref
Ref
ρψ M = (p − pRef )( N
P
incompressible limit K → ∞: α=0 vα nα − 1)
Ref
µα = gαRef + m
kT
α
ln nnα + vmα α (p − pRef )

mα v0Ref

Ref
Jα = −Mα ∇nα − m α nα
m0 n0 ∇n 0 + v α 1− Ref ∇p + zα e0 ∇ϕ
m0 vα

Free energy
N N
X X nα
n | {z }
| {z } | {z }
PN Ref
Ref
ρψ M = (p − pRef )( N
P
incompressible limit K → ∞: α=0 vα nα − 1)
Ref
µα = gαRef + m
kT
α
ln nnα + vmα α (p − pRef )

mα v0Ref

Ref
Jα = −Mα ∇nα − m α nα
m0 n0 ∇n 0 + v α 1− Ref ∇p + zα e0 ∇ϕ
m0 vα
Nernst-Planck: Jα = −Mα (∇nα + zα e0 ∇ϕ),

Solvated ions
cation
specific volumina:
Ref
A: vA
Ref
C: vC
S: vSRef
anion solvent molecules

Solvated ions
bounded solvent solvated cation

molecules
specific volumina:
Ref Ref
A: vA ∗ + κA vS
Ref Ref
C: vC ∗ + κC vS
S: vSRef
solvated anion free solvent molecules

Solvated ions

molecules
specific volumina:
Ref Ref
A: vA ∗ + κA vS
Ref Ref
C: vC ∗ + κC vS
S: vSRef
solvated anion free solvent molecules

Solvated ions

molecules
specific volumina:
Ref Ref
A: vA ∗ + κA vS
Ref Ref
C: vC ∗ + κC vS
S: vSRef
solvated anion free solvent molecules Z X
qe = zα nα dx
α
at ϕL − ϕR = 0.25V :
µC
experiment: |e
q | ≈ (0 − 50) cm2
µC
Nernst-Planck: |e
q | ≈ 600 cm 2
µC
simple mixture: |e
q | ≈ 100 cm 2
µC
solvated ions: |e
q | ≈ 28 cm2



Numerical results

Surface balances
volume: A0 , A1 , · · · , AN surface: A0 , A1 , · · · , AN , · · · , ANS
bulk Ω± surface S
∂t ρα + div(ρα v + Jα ) = 0 ∂t ρα + [[(ρα (v − w) +Jα ) · ν]] = 0

s
−Σ = ρb −[[Σ ·ν]] = ρb + 2kM γ ν

ss s
F
−ε0 (1 + χ)∆ϕ = n F −ε0 [[(1 + χ)∂n ϕ]] = n
s

Surface balances
volume: A0 , A1 , · · · , AN surface: A0 , A1 , · · · , AN , · · · , ANS
∂t ρα + div(ρα v + Jα ) = 0 ∂t ρα + [[(ρα (v − w) +Jα ) · ν]] = 0

s
−Σ = ρb −[[Σ ·ν]] = ρb + 2kM γ ν

ss s
F
−ε0 (1 + χ)∆ϕ = n F −ε0 [[(1 + χ)∂n ϕ]] = n
s
c = ρψ(T,ρ0 ,ρ1 ,··· ,ρN ) + χ|E|2

ρψ ρψ = ρψ (Ts ,ρ0 ,ρ1 ,··· ,ρNS )
ss ss s s s
∂ρψ
∂ρψ ss
µα = µα =
∂ρα s ∂ρα
N s NS
X X
p := −ρψ + ρα µα γ := ρψ − ρα µα
s ss s s
α=0 α=0

Free energy of metal
incompressible simple mixture of metal ions M and electrons e

veRef := 0, p = pe + pM
goal: ρψ = ρM ψM (ρM ) + ρe ψe (ρe ), ρψ (ρ0 , · · · , ρN , ρe , ρM )
ss s s s s
Ref 3 2/3 h 2/3

ρM ψM = pRef + vM

nM , µe = 8π 2me ne (Drude-Sommerfeld)

Free energy of metal
incompressible simple mixture of metal ions M and electrons e

veRef := 0, p = pe + pM
goal: ρψ = ρM ψM (ρM ) + ρe ψe (ρe ), ρψ (ρ0 , · · · , ρN , ρe , ρM )
ss s s s s
Ref 3 2/3 h 2/3

ρM ψM = pRef + vM

nM , µe = 8π 2me ne (Drude-Sommerfeld)
coupling to surface
Constitutive laws (fast adsoption limit)
µα −µ0 µ0
µ± ±
α −µ0 s s µ± s
0= T − T , 0= T
0
− T
s s

Free energy of metal surface
Volume mixture Surface mixture

adsorption sides
Solvent
Cation
Solvent
Cation nM = nRef
M
Anion Anion s s
Vacancy
Partial
vacancies
Solvation Bound
solvation shell
shell
P
solvent nV = nM − αn α

nα
s s s
µα = µRef
α +
kT
mα ln s
nV
s s s

aRef nV
µM = µRef
M − M
mM γ+ kT
mM ln s
nM
s s s s


adsorption sides
Solvent
Cation
Solvent
Cation nM = nRef
M
Anion Anion s s
Vacancy
Partial
vacancies
Solvation Bound
solvation shell
shell
P

nα
s s s
µα = µRef
α +
kT
mα ln s
nV
s s s

aRef nV
µM = µRef
M − M
mM γ+ kT
mM ln s
nM
s s s s
[Kohn,Lang:1971]
metal – vacuum: ϕM − ϕV ∼ 7V
metal – surface: ϕM − ϕV ∼ 2V
s


adsorption sides
Solvent
Cation
Solvent
Cation nM = nRef
M
Anion Anion s s
Vacancy
Partial
vacancies
Solvation Bound
solvation shell
shell
P

nα
s s s
µα = µRef
α +
kT
mα ln s
nV
s s s

aRef nV
µM = µRef
M − M
mM γ+ kT
mM ln s
nM
s s s s
[Kohn,Lang:1971]
metal – vacuum: ϕM − ϕV ∼ 7V
metal – surface: ϕM − ϕV ∼ 2V
s
µe = µRef
e (!) depending on surface orientation
s s
Capacity
dQ
differential capacity: C := Q := q + qe
dE s
G. Valette, J. Electroanal. Chem. 122 (1981), 285-297 W. Dreyer, C. Guhlke, M. Landstorfer, Electrochim. Acta, submitted,
(2015)

Electrochemical double layer
D. Kolb, Surface Science, 500(1-3),722-740, (2002)
O. Stern, Z. Elektrochem. angew. phys. Chem., 20(21-22),508-516, (1924)

Electrochemical double layer
D. Kolb, Surface Science, 500(1-3),722-740, (2002) W. Dreyer, C. Guhlke, M. Landstorfer, Electrochem. Commun., 43,
75-78, (2014)
O. Stern, Z. Elektrochem. angew. phys. Chem., 20(21-22),508-516, (1924)



Numerical results

Challanges
dγ
Lippmann dE = −Q
e0 e0
R = Rf0 exp αf kT ηS Rb0 exp −αb kT

Butler-Volmer ηS
s s
s
thermodynamic variable: E not ϕ

Challanges
dγ
Lippmann dE = −Q
e0 e0

Butler-Volmer ηS
s s
s
sharp boundary layers, Debye length: λLRef
−(1 + χ)ε0 ∂xx ϕ = nF −λ2 (1 + χ)∂ξξ ϕ bF

b=n
nRef
s
ε0 kT s
λ= 2 , λδ =
e0 n (LRef )2
Ref nRef LRef

Challanges
dγ
Lippmann dE = −Q
e0 e0

Butler-Volmer ηS
s s
s
sharp boundary layers, Debye length: λLRef
−(1 + χ)ε0 ∂xx ϕ = nF −λ2 (1 + χ)∂ξξ ϕ bF

b=n
nRef
s
ε0 kT s
λ= 2 , λδ =
e0 n (LRef )2
Ref nRef LRef
LRef = 1cm, nRef = 6.022 · 1025 m−3 , nRef = 7.3 · 1018 m−2
s
λ ≈ 1.54 · 10 , λδ ≈ 1.21 · 10 , λ|b| ≈ 2.38 · 10−8 .
−8 −5

Rescaled equations
Assumptions
equilibrium: ∂t · = 0, v = 0
δ ∼ O(1)
kM · λLRef 1
∇(µα + zα ϕ) = 0 (µα + zα ϕ))± = µα + zα ϕ

s s
∂x Σ = λρb [[Σ · ν]] = λδ(ρb + 2kM γ )
ss s
−λ2 (1 + χ)∂xx ϕ = nF F
−[[λ(1 + χ)∂x ϕν]] = δn
s

Formal Asymptotic Expansion
rescale in layer
x = r(s1, s 2 ) + z ν
u
e(r, z) := u(r + λzν)
ν formal asymptotics expansions for 0 < λ 1
r(s1, s 2 )
Ω− Ω+ in bulk: u = u(0) + λu(1) + O(λ2 )
S
in layer: u e(0) + λe
e=u u(1) + O(λ2 )

Formal Asymptotic Expansion
rescale in layer
x = r(s1, s 2 ) + z ν
u
e(r, z) := u(r + λzν)
ν formal asymptotics expansions for 0 < λ 1
r(s1, s 2 )
Ω− Ω+ in bulk: u = u(0) + λu(1) + O(λ2 )
S
in layer: u e(0) + λe
e=u u(1) + O(λ2 )
matching conditions: S
(0) (0),± (0) λ uλ(x)
u
e (z) − u (xS ) = o(1/|z|)
(0)
∂z u
e (z) = o(1/|z|)
~uλ(z )
in higher order
e(1) (z) − z ∂ν u(0),± − u(1),± = o(1/|z|)

u
e(1) (z)−∂ν u(0),± = o(1/|z|)
∂z u
Inner equations
∇u = λ−1 ∂z u
e ν + |τ1 |−1 ∂1 u
e τ1 + |τ2 |−1 ∂2 u
e τ2 + O(λ) ,
div(u) = λ−1 ∂z u
e · ν + divτ (e
u) + O(λ) ,
−∆u = −λ−2 ∂zz u
e − λ−1 2kM ∂z u
e + O(1) ,
1+χ
e νν = −e
Σ p+ e2
2 |∂z ϕ| + O(λ2 )
layer
λ−1 (∂z pe + nF ∂z ϕ)
e + O(λ) = λρb
−(1 + χ)(∂zz ϕ e + O(λ2 ) = nF
e + λ 2kM ∂z ϕ)
S
e νν ]] = λ δ 2kM γ + λ2 δ ρb · ν + O(λ2 )
−[[Σ
s ss
F
−[[(1 + χ)∂z ϕ]] = δn + O(λ)
s

Leading order
(0) 1+χ (0)

p(0) +
e νν = −e
layer: Σ e(0) |2
2 |∂z ϕ bulk: Σνν = −p(0)
layer S
e (0) = 0 ,
−∂z Σ e (0) ]] = 0 ,
−[[Σ
νν νν
e(0) = n
−(1 + χ)∂zz ϕ eF,(0) . e(0) ]] = δ nF,(0)
−[[(1 + χ)∂z ϕ
s
e (0)
Σ e (0)
νν (−∞) = Σνν (∞) =⇒ [[[p(0) ]]] = 0

Leading order
(0) 1+χ (0)

p(0) +
e νν = −e
layer: Σ e(0) |2
2 |∂z ϕ bulk: Σνν = −p(0)
layer S
e (0) = 0 ,
−∂z Σ e (0) ]] = 0 ,
−[[Σ
νν νν
e(0) = n
−(1 + χ)∂zz ϕ eF,(0) . e(0) ]] = δ nF,(0)
−[[(1 + χ)∂z ϕ
s
e (0)
Σ e (0)
νν (−∞) = Σνν (∞) =⇒ [[[p(0) ]]] = 0
R∞
e(0) dz
−∞ ∂zz ϕ = ∂z ϕ e(0) |∞
e(0) |0−∞ + ∂z ϕ 0 e(0) ]]
= −[[∂z ϕ
R∞ R0
qe+ := 0 eF,(0) dz ,
n qe− := −∞ n
e F,(0)
dz
global electro-neutrality of double layer: δn F,(0)
+ qe− + qe+ = 0
s

Higher order
e (1)
Σ p(1) + (1 + χ)∂z ϕ
νν = −e e(0) ∂z ϕ
e(1)
layer S
∂z pe(1) + n
eF,(0) ∂z ϕ
e(1) + n
eF,(1) ∂z ϕ
e(0) = 0 , e (1) ]] = δ 2kM γ
−[[Σ νν
s
−(1 + χ) ∂zz ϕ e(1) + 2kM ∂z ϕ e(0) = n eF,(1)

Higher order
e (1)
Σ p(1) + (1 + χ)∂z ϕ
νν = −e e(0) ∂z ϕ
e(1)
layer S
∂z pe(1) + n
eF,(0) ∂z ϕ
e(1) + n
eF,(1) ∂z ϕ
e(0) = 0 , e (1) ]] = δ 2kM γ
−[[Σ νν
s
−(1 + χ) ∂zz ϕ e(1) + 2kM ∂z ϕ e(0) = n eF,(1)
e (1)
∂z Σ e(0) )2
νν = −2kM (1 + χ)(∂z ϕ

Higher order
e (1)
Σ p(1) + (1 + χ)∂z ϕ
νν = −e e(0) ∂z ϕ
e(1)
layer S
∂z pe(1) + n
eF,(0) ∂z ϕ
e(1) + n
eF,(1) ∂z ϕ
e(0) = 0 , e (1) ]] = δ 2kM γ
−[[Σ νν
s
−(1 + χ) ∂zz ϕ e(1) + 2kM ∂z ϕ e(0) = n eF,(1)
e (1)
∂z Σ νν = −2kM (1 + χ)(∂z ϕ e(0) )2
R∞ R0
e+ := 0 (1 + χ)(∂z ϕ
γ e(0) )2 dz , e− :=
γ −∞ (1 e(0) )2 dz
+ χ)(∂z ϕ
Young-Laplace [[[p(1) ]]] = 2kM (γ + γ e− )

e+ − γ
s

Lippmann equation
interfacial tension γ := γ + γ e−
e+ − γ
s
Ω+ metal, apply potential E := ϕ − ϕ−
s
d +
µe = const. → constant layer in metal =⇒ dE γ
e =0
s

Lippmann equation
e+ − γ
s
s
d +
e =0
s
R0
e− = (1 + χ) −∞ (∂z ϕ
γ e(0) )2 dz
R0p
= (1 + χ) E p(ϕ e + ϕ− ) dϕ e [DGM13]
d − √ − −
e = −(1 + χ) p|S = −e
dE γ q [DGL2014pre]

Lippmann equation
e+ − γ
s
s
d +
e =0
s
R0
e− = (1 + χ) −∞ (∂z ϕ
γ e(0) )2 dz
R0p
= (1 + χ) E p(ϕ e + ϕ− ) dϕ e [DGM13]
d − √ − −
e = −(1 + χ) p|S = −e

d d P
dE γ = dE ρψ − n α µα
s s
s ss

= dE ρψ − α∈Ω− nα (µα |−
d P
S + zα E)
ss
= −q [Guhlke2015]
s

Lippmann equation
e+ − γ
s
s
d +
e =0
s
R0
e− = (1 + χ) −∞ (∂z ϕ
γ e(0) )2 dz
R0p
= (1 + χ) E p(ϕ e + ϕ− ) dϕ e [DGM13]
d − √ − −
e = −(1 + χ) p|S = −e

d d P
dE γ = dE ρψ − n α µα
s s
s ss

= dE ρψ − α∈Ω− nα (µα |−
d P
S + zα E)
ss
= −q [Guhlke2015]
s
double layer charge: Q := q + qe− Lippmann: d

dE γ = −Q
s
Numerical results
240
cNaClO4 = 0.1
cNaClO4 = 0.04
230 cNaClO4 = 0.02
cNaClO4 = 0.01
220 cNaClO4 = 0.005
Interfacial tension γInt [10−3 N/m]
210
200
190
180
170
160
−0.4 −0.2 0 0.2 0.4 0.6
Potential E (vs. U R ) [V]

Numerical results
240
cNaClO4 = 0.1 Salt concentration: c = 0.01M
cNaClO4 = 0.04 240
230 cNaClO4 = 0.02
cNaClO4 = 0.01
230 KPF6
220 cNaClO4 = 0.005 NaClO4
220 NaF

210
210
200
200
190
190
180
180
170
170
160 160
−0.4 −0.2 0 0.2 0.4 0.6 −0.4 −0.2 0 0.2 0.4 0.6
Potential E (vs. U R ) [V] Potential E (vs. U R ) [V]

Validity of asymptotic results
rS = 25nm , c = 0.1 M rS = 5nm , c = 0.04 M

[10−3 N/m]
[10−3 N/m]
0 0
−50 −50
Boundary layer tension γBL

E
E
−100 −100
−150 −150
ε0 (1 + χ) (rS /r)Er2 dr (numercial solution) ε0 (1 + χ) (rS /r)Er2 dr (numercial solution)

´ ´
−200 −200
asymp. approximation asymp. approximation
−250 −250
−1 −0.8 −0.6 −0.4 −0.2 0 0.2 0.4 0.6 0.8 1 −1 −0.8 −0.6 −0.4 −0.2 0 0.2 0.4 0.6 0.8 1
Cell voltage E [V] (vs. SCE) Cell voltage E [V] (vs. SCE)

Validity of asymptotic results
rS = 25nm , c = 0.1 M rS = 1nm , c = 0.04 M

[10−3 N/m]
[10−3 N/m]
0 0
−50 −50

E
E
−100 −100
−150 −150
ε0 (1 + χ) (rS /r)Er2 dr (numercial solution) ε0 (1 + χ) (rS /r)Er2 dr (numercial solution)

´ ´
−200 −200
asymp. approximation asymp. approximation
−250 −250
−1 −0.8 −0.6 −0.4 −0.2 0 0.2 0.4 0.6 0.8 1 −1 −0.8 −0.6 −0.4 −0.2 0 0.2 0.4 0.6 0.8 1
Cell voltage E [V] (vs. SCE) Cell voltage E [V] (vs. SCE)

Summary & Conclusions
pressure dependence, momentum balance necessary

thermodynamically consistent complete model derived
incompressible mixture model for metal surface; µe = const.
s
qualitative & quantitative prediction of differential capacity
jump conditions by formal asymptotic analysis
electric field contributes to interfacial tension

Lippmann equation recovered within asymptotic limit
asymptotic not valid in nm range

Summary & Conclusions
pressure dependence, momentum balance necessary

thermodynamically consistent complete model derived
incompressible mixture model for metal surface; µe = const.
s
qualitative & quantitative prediction of differential capacity
jump conditions by formal asymptotic analysis
electric field contributes to interfacial tension

Lippmann equation recovered within asymptotic limit
asymptotic not valid in nm range
Thank you for your attention! Questions?

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Weierstrass Institute for

Applied Analysis and Stochastics

The Lippmann equation for liquid metal electrodes

Wolfgang Dreyer, Clemens Guhlke, Manuel Landstorfer, Rüdiger Müller

Mohrenstrasse 39 · 10117 Berlin · Germany · Tel. +49 30 20372 0 · www.wias-berlin.de

IUPAC Compendium of Chemical Terminology Copyright © 2014 IUPAC

Lippmann Equation · March 3. 2015 · Page 2 (29)

Lippmann Equation · March 3. 2015 · Page 3 (29)

Lippmann Equation · March 3. 2015 · Page 3 (29)

Lippmann Equation · March 3. 2015 · Page 3 (29)

Lippmann Equation · March 3. 2015 · Page 3 (29)

1 Ion transport in electrolyte bulk

2 Electrochemical double layer

3 Lippmann equation for liquid mercury electrode

Lippmann Equation · March 3. 2015 · Page 4 (29)

diluted solution of anions A, cations C in solvet S +

Lippmann Equation · March 3. 2015 · Page 5 (29)

diluted solution of anions A, cations C in solvet S +

−ε∆ϕ = zA n̄A exp(−zA ϕ) + zC n̄C exp(−zC ϕ)

Lippmann Equation · March 3. 2015 · Page 5 (29)

Lippmann Equation · March 3. 2015 · Page 6 (29)

Lippmann Equation · March 3. 2015 · Page 6 (29)

Lippmann Equation · March 3. 2015 · Page 6 (29)

non-equilibrium thermodynamics distinguishes

Lippmann Equation · March 3. 2015 · Page 7 (29)

non-equilibrium thermodynamics distinguishes

constitutive equations restricted by

Lippmann Equation · March 3. 2015 · Page 7 (29)

fields of matter electromagnetic fields

Lippmann Equation · March 3. 2015 · Page 8 (29)

fields of matter electromagnetic fields

Lippmann Equation · March 3. 2015 · Page 8 (29)

fields of matter electromagnetic fields

partial mass balances ∂t ρα + div(ρα v + Jα ) = 0 for α = 0, 1, · · · , N

quasi-static momentum − div(Σ) = ρb

Lippmann Equation · March 3. 2015 · Page 9 (29)

free energy c = ρψ(T,ρ0 ,ρ1 ,··· ,ρN ,) + χ|E|2

Lippmann Equation · March 3. 2015 · Page 10 (29)

free energy c = ρψ(T,ρ0 ,ρ1 ,··· ,ρN ,) + χ|E|2

Lippmann Equation · March 3. 2015 · Page 10 (29)

Lippmann Equation · March 3. 2015 · Page 11 (29)

Lippmann Equation · March 3. 2015 · Page 11 (29)

Nernst-Planck: Jα = −Mα (∇nα + zα e0 ∇ϕ),

Lippmann Equation · March 3. 2015 · Page 11 (29)

Lippmann Equation · March 3. 2015 · Page 12 (29)

bounded solvent solvated cation

Lippmann Equation · March 3. 2015 · Page 12 (29)

bounded solvent solvated cation

Lippmann Equation · March 3. 2015 · Page 12 (29)

bounded solvent solvated cation

Lippmann Equation · March 3. 2015 · Page 12 (29)

2 Electrochemical double layer

3 Lippmann equation for liquid mercury electrode

Lippmann Equation · March 3. 2015 · Page 13 (29)

volume: A0 , A1 , · · · , AN surface: A0 , A1 , · · · , AN , · · · , ANS

∂t ρα + div(ρα v + Jα ) = 0 ∂t ρα + [[(ρα (v − w) +Jα ) · ν]] = 0

−Σ = ρb −[[Σ ·ν]] = ρb + 2kM γ ν

Lippmann Equation · March 3. 2015 · Page 14 (29)

volume: A0 , A1 , · · · , AN surface: A0 , A1 , · · · , AN , · · · , ANS

∂t ρα + div(ρα v + Jα ) = 0 ∂t ρα + [[(ρα (v − w) +Jα ) · ν]] = 0