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Ionic and Electronic DC Conduction

Electrolyte : a substance with ionic dc conductivity
Charge carrier = ion(ionic current), not electron (electronic
current) in metals

Two current carrying electrodes in an electrolyte are the

source and sink of electrons: from electrons of the metal
to ions or uncharged species of the electrolyte.

The electrode is the site of charge carrier exchange

between electrons and ions.
Migration velocity of
Electrons in metal = ~0.3mm/s
Ions in solution = ~10mm/s
Living tissue = electrolytic
conductor : both intra- &
extracellular liquids contain
ions free to migrate

Ionic and Electronic DC Conduction

Electric current flow
No transport of substance
Dc current flow without changing the conductor
Ionic current
Transport of substance
Externally applied dc current changes the conductor
First near the electrode, then spread to the bulk
Electrolytic long duration dc conductivity is a difficult
concept in a closed system
Transfer of electric charge across the solution
electrode interphase: electrochemical reaction at
each electrode(electrolysis).
We must keep the phenomena in the bulk of the
solution separate from the phenomena at the
electrodes.

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 Ionization

Electrochemical properties Forces acting between atoms in a solid;

Determined by the inclination of Ionic bonding
an atom to attain noble gas Covalent bonding
configuration of the outer Metallic bonding
electron shell Van der Waals bonding

Electronegativity
Relative ability of an atom to
gain electrons and become a
negative ion
Useful to predict the strength &
polarities of ionic bonds
between atoms, and thus
possible electrochemical
reactions.

Paulings scale of electronegativity

for some selected atoms

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Basic Electrolytic Experiment

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Pt & Carbon
There must be energy barriers in the system
Nonlinear system, not obeying Ohms law
Bulk solution obeys Ohms law
Energy barrier is not in the bulk but near the electrodes
Without dc current, no electron transfer, no chemical reaction,
no faradaic current

At the cathode
Na+ ions migrate and are discharged ? (hint : Na+ has a very
small electronegativity)
Two processes with non-charged species transferred by
diffusion
Reduction of dissolved neutral oxygen : at small current
Decomposition of water molecules : at larger current
2H2O + 2e = H2 (gas) + 2OH- (base)
Na+ need not be considered but is necessary for the conductivity of
solution, voltage drop in the solution is not too high
Ag+ ions are reduced, AgCl layer is decomposed, pure Ag
appears

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 At the anode
discharge of Cl- :
chloride is highly electronegative, but less energy is necessary for
taking electrons from the chloride ions than from water
molecules
Neutral Cl2 gas reacts with carbon, not with Pt
Water decomposition
2H2O = O2 (gas) + 4H+ + 4e-(acid)
Ag is oxidized and forms more AgCl

Redox process : the transfer of electrons oxidising or

reducing species at an electrode
the results indicate that if we are to apply large dc
currents to tissue, and we are to use noble metals as
electrode material directly on the tissue, the passage of
dc current is accompanied by the development of H2 gas
and a basic milieu at the cathode, and Cl2 gas and
perhaps oxygen and an acidic millieu at the anode

Electrochemical Reactions
An electrochemical reaction is a reaction involving the
transfer of charge as a part of a chemical reaction.
Typical electrochemical reactions in corrosion are metal
dissolution and oxygen reduction
In contrast a chemical reaction, such as the precipitation
of a metal hydroxide, does not involve a transfer of
charge
Note that reduction and oxidation reactions have been
shown going in one direction only. While the reverse
reactions are perfectly possible, the reverse of an anodic
reaction is a cathodic reaction and vice versa.

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 Electrical Double Layer

Electrical Double Layer

There is a tendency for charged species to be attracted to
or repelled from the metal-solution interface.
This gives rise to a separation of charge, and the layer of
solution with different composition from the bulk solution
is known as the electrical double layer.
There are a number of theoretical descriptions of the
structure of this layer, including the Helmholtz model, the
Gouy-Chapman model and the Gouy-Chapman-Stern
model.
As a result of the variation of the charge separation with the
applied potential, the electrochemical double layer has
an apparent capacitance (known as the double layer
capacitance).

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 Electrical Double Layer
--perpendicular fields
Charge transfer
At the electrode-liquid interface the transformation from
electronic to ionic conduction occurs
The electrode exchanges charges with the arriving ions or
ionizes neutral substances
Oxidization of the electrode metal; the metal ion enters the
solution
Electric double layer (EDL)
In the solution, at the electrode surface an EDL is formed as soon
as the metal is wetted
In all interphases, such as metal of an electrode & the electrolyte,
tissue or gel, or at a cell surface
There will be a non-uniform distribution of charges -> an electric
potential across the interphase
Particularly pronounced at the interphase between a solid and a
polar medium (e.g. water)
When the polar medium is liquid and the ion mobility high, the
formation of an EDL will take place in the liquid phase.

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General theory of Gouy-Chapman

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10
 Solid/Electrolyte Interface
Double layer Solid surface acquires charges in aqueous environment
Counter-ions migrate to the solid to form double layer
Electrically modeled as a capacitor
Surface Counter
charge ion Potential
Zeta potential:
Concentration
Potential across
double layer:
Counter-ion
charge
= Co-ion
Cdbl y
distance

Double layer/Debye length

Cdbl =

Electroosmosis and
Electrophoresis

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 Electro-Osmotic Flow (EOF)

High voltages
Bubble generation, pH
gradient

P. Mruetusatorn

Several KV is needed.
E~ 104 V/cm

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 Modulation of Zeta Potential
Passive interface at channel walls

Anode Cathode

Reactions
+ -
to conduct
electricity Gate--Field effect, Capacitive charging,
Induced ions can be externally modulated (+/-)

Fluid Surface Velocity:

u II = E II

double layer charge density x EII

Mixer

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Electrophoresis

Applications

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Capillary Electrophoresis

Principle of CE

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Microfabricated CE

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 DC Electrokinetics (EK)

Fluids Particles

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 Four electrokinetic effects due to the electric charge of the
double layer at the solid-liquid interphase

Electrophoresis : the migration of charged particles through a

liquid
Electro-osmosis : bulk liquid flow through a pore caused by a
migrating ionic sheath
Sedimental potential : potential difference generated by
falling charged particles
Streaming potential : potential difference when a liquid is
pressed through a pore

Body or podermotive forces :

Field-induced polarization will make uncharged particles move in
inhomogeneous or moving electric field,
The resultant forces increase with the volume of the particle
These forces are the basis of phenomena & techniques such
as electrorotation, levitation,dielectrophoresis, pearl
chain formation, travelling wave dielectrophoresis

Issues with DC Electrokinetics

+

High voltages -
1 sec 3 sec
Bubble generation, blocking channels,
open reservoirs, losing pressure Power
supply
pH gradients
DC EO
Electric insulation
Acid E Base
Impractical for large network
Poor mixing Electrochemical
Velocity scales linearly with voltage reaction

etc

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Active Solid/Electrolyte Interface
V _
+ Charges induced by external voltages can
_ be positive or negative.
+ Co-ions ~ _
+ Reactions
_ Counter-ions +
_
~Capacitance +
DC/AC path
V V
Electrode by Reactions DC/AC path Rrct
Rlead

AC path only Fluid bulk, Rsolu

Cdbl: Double layer capacitance

Charge transfer paths: Ccell: system

dielectric coupling

AC Voltage Case

At high frequency (~1MHz) : back and forth

migration process in the bulk electrolyte will take
palce, no accumulation or reaction will take
place at the electrodes

At low frequency (~0.1Hz) : result will depend on

the dimension of the cell and the degree of
reversibility of the reactions. Id the gas has time
to bubble away, the process is certainly
irreversible.

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 AC Electrokinetics

Dielectrophoresis (DEP)
Particle manipulation, positive & negative
DEP

AC electro-osmosis (ACEO)
Fluid force exerted by electrode/sidewall
charging

AC electrothermal (ACET) effect

Fluid force from thermal gradient in the
bulk

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 Vac exp( jt )

u II = E II E II = : voltage drop in the double layer
x

AC EO Principle (cont)
Surface Vortices and Stagnation
Four vortices on an isolated electrode pair.
FEA simulation of
electric field distribution

0 x
Electrode Electrode
a L+a
xstagn =
1
(L + a )2 + a 2
2
a : half of electrode gap
L : electrode width

Nulls of tangential field

Flow Flow
Stagnation point
E-field
+ + + + + + + + + + + + ++ - - - - - - - - - - - - - -
+ -
Particle trapping at
Capacitive Charging fluid velocity minimum

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 ACEO Features
Electric fields induce charge density on metal
surfaces
Induced charges cause electric double layer
formation
Electric field becomes tangential Bulk resistance
Electric field sets the double layer in motion
Double layer
capacitance

V cos t V cos t

Induced-Charge Electro-Osmosis

TODD M. SQUIRES
MARTIN Z. BAZANT

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 Induced-charge electro-osmosis:
Fundamental picture

The evolution of the electric field around a solid, ideally polarizable conducting
cylinder immersed in a liquid electrolyte, following the imposition of a DC field at t =
0 (a), where the field lines intersect normal to the conducting surface.
Over a charging time, a dipolar charge cloud forms in response to currents from the
bulk, reaching steady state (b) when the bulk field profile is that of an insulator.

Steady ICEO around an uncharged

conducting cylinder

The steady-state induced-charge electro-osmotic flow around (a) a conducting

cylinder with zero net charge and (b) a positively charged conducting cylinder.
The ICEO slip velocity depends on the product of the steady field and the
induced zeta potential. The charged cylinder (b) simply involves the super-
position of the standard electro-osmotic flow.

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Simple microfluidic devices
exploiting ICEO

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Induced-Charge Electrophoresis
of Metallodielectric Particles

Asymmetrical Particles

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 Nature Materials 6, 235 - 240 (2007)
Remotely powered self-propelling particles and
micropumps based on miniature diodes

Lab Chip, 2008, 8, 117 - 124,

Remotely powered distributed microfluidic pumps
and mixers based on miniature diodes

Orlin D. Velevs group, NDSU

http://www.che.ncsu.edu/velevgroup/nmat1843_movies.htm

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