Dr. B. Farrell
Email: bfarrell@bcm.tmc.edu
References on Electrochemistry: Many books published or edited by Allen J. Bard (of University
of Austin, TX)
Interfacial Electrochemistry J. Lyklema. 1991. Fundamentals of Interface and Colloid Science.
vol 1 and 2. (references on Thermodynamics)
Electrochemical Cells
¾ In electrochemistry we are interested in the processes that
affect the transport of charge at interfaces usually between a
conductor (electrode) and an ionic conductor (electrolyte).
¾ Anode
H+(aq) + e → 1/2H2 (g)
¾ Cathode
AgCl(s) + e → Ag(s) + Cl-(aq)
¾ Potential of cell is
Ecell = Ecathode - Eanode
¾ Sometimes written as
Ecell = ERight - ELeft cathode
anode
¾ At standard state
Eo = Eocathode- Eoanode ½ H2(g)+ AgCl(s) → H+(aq) + Ag(s) + Cl-(aq)
At standard state Eocathode is determined relative to the
Standard Hydrogen Electrode (SHE)
¾ Hydrogen ions at unit activity
in equilibrium with hydrogen
gas at 1 atmosphere)
¾ At all temperatures
¾ Ecell= Eocathode-Eoanode
Eoanode = ESHE= 0.0 V
¾ Therefore
anode cathode
mechanical electrical
EO > 0 → dG0 < 0 → spontaneous reaction
¾ Eo negative
e.g.,
Zn2+(aq) + H2(g)→ Zn(s) + H+(aq)
is not favorable
¾ Zn | ZnS04(a=1), CuSO4(a=1) | Cu
Anode
Zn2+(aq) + 2e → Zn(s)
¾ Problem
Calculate Ecell for cell, where temperature is
at 25 ºC and mean activity coefficients of HCl
is 0.758
pP + ze ⇔ qQ
Reactants
p
RT a p
E = Eo + ln q
zF a Q
Products
o
E : standard potential of cell, V
T : temperature, Kelvin
Products -1 -1
q R : gas constant, (8.314 JK mol )
RT a
E = Eo −
-1
ln Qp F : Faraday constant (96490 Cmol )
zF a P z : number of electrons
Reactants
Chemical Potential of Electrolyte Solutions
+ -
r
Activities of ions
Therefore
µ Na + µ Cl = µ NaCl
o
µ NaCl = µ NaCl + 2RTln a± E.10a
o o o
µ Na + µCl = µ NaCl
a − ≡ γ Cl − C Cl − E.11
γ 2 = (γ +γ − )
Cl
2 ln(γ ± ) = ln(γ +γ − )
o
µ NaCl = µ NaCl + RTlnγ C γ C
Na + Na + Cl − Cl −
If we also use
C NaCl = C Na = CCl
+ −
¾ Problem
Calculate Ecell for cell, where temperature is
at 25 ºC and mean activity coefficients of HCl
is 0.758
Eo =Ecathode- Eanode=0.222 V
Example, continued
Poggendorf circuit
¾ EMF is defined as the cell
potential when there is no 1
current through the cell. Ex G
The emf is sometimes coined
the zero-current or open-circuit 2
cell potential.
Es
¾ Measuring EMF
Potentiometer slide wire is R
adjusted until there is no current Io
through the galvonmeter, G
when the switch is in position 2.
In this position R=Rs. The Rb
Eb
process is repeated for switch
position 1 where R=RX.
E: power supply
Ex = IoRx and Es = IoRs Es: standard cell of known potential
EX: unknown cell potential
Ex= (Rx/Rs)Es
Exchange Current Density is a function of the rate constant
of the reaction (at equilibrium)
For any redox reaction
zFmo k f
kf
jo = jcathode = (at equilibrium)
A
O + e⇔ R
kb zFmR kb
jo = janode = (at equilibrium)
kf rate constant of the forward reaction A
kb rate constant of the backward reaction
anode
Hg2Cl2 + 2e → 2Hg + 2Cl- Eo=0.242
anode cathode
cathode
Cd2+ + 2e → Cd Eo= -0.403
oxidation
of Cd
Anodic current: is an oxidation current electron
flow from species in solution to an electrode. cathode anode
Defined as negative current.
.. application of a potential, Eapp can cause the surface of the
electrode to become charged forming a double layer. This
alters the I vs E curve
Eapp
negatively charged
electrode surface diffuse layer
− + + + + −
− −
Number density
+ − +
− + − −
− +
+ +
− + + +
− − − counterions
+ − − +
− +
− + + bulk
+ + − −
−
coions
Distance
0 d
-Ψbulk
Diffuse layer
-Ψd
i i
Ecell E
Ecell
overpotential, η = E - Ecell
Consequences of double layer effects
Final voltage
Potential (V)
time (s)
Current
peaks at (C). The current then
decays for the rest of the forward E -ve direction
scan.
¾ At (D) the polarity of the voltage is
reversed and the cathodic current F
anodic current
decays till it reaches (E) where the
analyte starts to be oxidized. The
anodic current then peaks at F as E vs reference electrode
more analyte is re-oxidized. It then
decays as the voltage is made more
positive and the scan is complete
Currents measured are usually small nAmps require
sophisticated electronic instrumentation and working
electrodes with small surface areas
Computer + Software
(DAQ + software) or working electrode in
Amplifier sample or solution,
Hardware (reference in solution)
(voltage generator)
¾ Know what is meant by cathodic and anodic current and the exchange
current density, jo of a redox reaction