Types of electrochemical cells
Current passes in both types is Faradic current
Reaction in galvanic cell is spontaneous reactions Chemical energy is transferred to electrical energy Types of galvanic cells (chemical, concentration) Reaction in electrolytic cell is due to applied potential
Electrical energy is consumed to make possible the
electrochemical reaction
Reaction in electrochemical cell is result of Faradic processes at electrodes electrode? Cathode & anode Cathodic current results from electrons transferring from electrode to reactant in soln. Anodic current results from electrons transferring from reactant in soln. to electrode
cathodic current
anodic current
potential and current in electrochemical cell
cell shown is galvanic cell connected to power source
Assuming standard conditions Cell potential Eocell= 0.64V (SHE) Cadmium electrode is anode (-) Calomel electrode is cathode (+) If applied potential (Eappl) = 0.64V then current passed equal zero If Eappl > 0.64V cell is electrolytic cell and current passes Potential of cadmium electrode becomes more negative Electrodes reaction are
Cd2+ + 2e Cd 2Hg + 2Cl- Hg2Cl2 + 2e
Current is number of coulombs passed/s Relation between current and rate of electrode reaction
I (amperes)= dQ/dt (coulombs/s) Q/nF (coulombs/coulombs mol-1) = N (mol electrolyzed) Rate (mol/s) = dN/dt = I/nF Faraday law
Electrode reactions are heterogeneous
reactions
Rate depends on reaction area (electrode area)
Rate (mol /s cm2) = I/ nFA = i / nF (i) is current density with unit A cm-2
What is the current density for the reaction Ag+ +eAg That takes place on electrode with 1cm2 area when [Ag+] decreases by 0.1M in 30 minutes? (5.36 mA cm-2 )
Information can be collected when studying rate of electrode reaction as function of potential known as current-potential curves Equilibrium is established for the Cd2+ + 2e Cd when at equilibrium potential (Eeq) Net current (Inet) will be zero (reason!!!!!) Equilibrium shifts if net faradic current passes Potential will shift from its Eeq This shift in potential is known as polarization
Polarization is measured by overpotential () Overpotential is defined by:
= E Eeq
Current-potential curves are known also by polarization curves There are two types of electrodes
Reversible Irreversible Different rates for their electrode reaction
polarization curves for reversible and irreversible
Electrode potential can change because of activity change For the reaction Cu2+ + 2e Cu Eeq= +0.34V (SHE) Equilibrium will shift if Cu2+ activity changes
a, M
1.0 10-2 10-4 10-6
E, V +0.34 +0.28 +0.22 +0.16
Ecu shifts to more cathodic potentials and the equilibrium shifts to the left hand side
factors affecting rate of electrode reaction and the resultant current
For the general electrode reaction
O(aq) + ne R (aq)
Reaction consist of multi steps Reaction kinetics limited by RDS
Number of steps in the previous scheme Which step depends on potential? Electrode reactions may consists from chemical, multi electrons transfers, either in series or in parallel When the reaction rate is at steady state i.e. constant current, then all steps have similar rate Reaction rate is limited by rate determining step (RDS)
electron transfer Fermi level LUMO HOMO Electrode potential Overpotential Rate of reaction in one direction and sign and value of
)Ef > LUMO(
)Ef < LUMO(
