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Φ2 – Φs is wasted!!
dy
Field strength dx x x 2 is critical!!
Electrified Interfaces
GR =(T, P, nRi)
GS = (T,P, A, nSi)
Interfacial zone
(few hundred angstroms)
Real surface/interface has a
tendency to expand or contract
to minimize free energy.
Chapter 13 – Electric Double Layer
μi = (G/ni)T,P i = ni/A
M = -Fe
S = - M = F(K+ + Cl-)
M(H2O) = M – (XM/XH2O)H2O
At more negative potentials, the surface has excess negative charge and at more
positive potentials excess positive charge. The units of positive charge
composing any excess repel each other, hence they counteract the ability of the
surface to contract.
Differential capacitance, ability of an Cd = (M/E)
interface to store charge.
Chapter 13 – Electric Double Layer
K+(H2O) = -(/μKF)E_, μM
Epzc
F-
μKF = μ0KF + RTlnaKF
+ -
K+ E-Epzc
F-
Simple electrostatics
1 1 1
CTotal CCompact C DL
Chapter 13 – Electric Double Layer
zi F ( ( x) s )
Ci ( x) Ci exp
RT
( x) zi FCi ( x)
i
Due to their dipole moments, the water molecules will compete with ions
for sites on the surface. Cations retain hydration layer. Anions will have
solvent shell partially or fully stripped and can form bonds with metal
atoms on surface.
Chapter 13 – Electric Double Layer
Predicts U-
shaped C-E
profile!!
Chapter 13 – Electric Double Layer
A. Helmholtz Model
Proposed two sheets of charge adjacent to one another – capacitor-like
behavior of the interface. Two sheets of opposite polarity – this is where
the idea of the double layer comes from.
B. Gouy-Chapman Model
Even though charge on the electrode is confined to the surface, the
same is not the case for the solution.
It may take some significant thickness of solution to accumulate
enough charge to counterbalance M.
Finite thickness arises because there is an interplay between tendency
of charge on the metallic phase to attract or repel carriers (ions) and the
tendency of thermal processes to randomize them.
Φ = Φo exp (-κx)
C. Stern Model
G-C model predicts an unlimited rise in Cd with E because the ions are
not restricted with respect to location in solution.
They are considered as point charges with no real size!
Therefore, at high polarization potentials, the effective distance
between the metallic and solution charge zones decreases toward zero
and d increases.
Model takes into account aspects of both the Helmholtz and G-C models!
Chapter 13 – Electric Double Layer
At large electrolyte
concentrations and or large
polarization potentials, CD
becomes large so it does
not contribute to Cd.
Chapter 13 – Electric Double Layer
Specific Adsorption
Specific versus nonspecific adsorption
Non-specific adsorption provides no mechanism for the electrode
potential to vary with the electrolyte concentration.
Surface tension plots diverge at E-Epzc > 0 due to specific anion
interactions with the surface.
I- > Br- > Cl- > F- More polarizable, the greater the tendency to
specifically adsorb.
Full or partial charge transfer with the electrode, but often the
negative charge is retained.
Essentially, specific or contact adsorption of an anion makes the
surface potential more negative.
-
Chapter 13 – Electric Double Layer
1 E
Esin – Markov Effect
RT ln asalt M
Concentration (M) Epzc (NaF) Epzc (KI)
1.0 -0.472 V -0.820 V
0.1 -0.472 V -0.720 V vs. SCE
0.01 -0.480 V -0.660 V
Adsorption Isotherms
Adsorption isotherm – relationship between i, ai, & E or qM
aia = aib exp(-Go/RT) = βiaib
A. Langmuir Isotherm
No interactions between adsorbed molecules.
No heterogeneities in the surface sites.
Monolayer coverage at saturation. s
Conc.
Chapter 13 – Electric Double Layer
A. Frumkin Isotherm
Oz + e- Rz-1 io = nFAkoCo(1-)CR