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MM 222 - Lecture 3

The document discusses electrochemistry concepts including chemical potential, electron energy levels, interface potentials, Gibbs free energy, the Nernst equation, and the standard electrochemical series. It explains how these concepts relate to the potential difference at electrode-electrolyte interfaces and galvanic cell notation.

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12 views

MM 222 - Lecture 3

The document discusses electrochemistry concepts including chemical potential, electron energy levels, interface potentials, Gibbs free energy, the Nernst equation, and the standard electrochemical series. It explains how these concepts relate to the potential difference at electrode-electrolyte interfaces and galvanic cell notation.

Uploaded by

12 34
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PPTX, PDF, TXT or read online on Scribd
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Recap

• Starting with the very basics of electrochemistry

• Chemical Potential and Electrochemical Potential

• Electron energy levels; taking Fermi Energy level (EF) as the


electrochemical potential in a bulk material.

• Interface potentials and relationship with work function


Potential difference at electrode/electrolyte interface
Now, let us consider that a solution containing equal amounts of A 3+ and A2+ ions in contact
with a bulk metal (electrode) M, and that the reaction is at equilibrium. A-ion can be any
ion, capable of changing oxidation state; like Fe-ion, Mn-ion etc.)We now transfer an
electron from the solution via the vacuum to the metal in the following way:
 Take an A2+ from the bulk level of the solution into the surface level above the
solution; with the work required being the negative of ∆Grsol(A2+), the Gibbs energy
of solvation of A2+.
 Take an electron from the A2+; A2+ → A3+ + e-; the work required being the 3rd
ionization energy I3 of A.
 Put the A3+ back into solution, and gain ∆Grsol(A3+).
 Take the electron from just outside the solution across to a position just
outside the metal electrode; the work required being -e0(ψm-ψs); m denotes the
metal and s denotes the solution.
 Take the electron to the Fermi level of the bulk metal, and gain -Φm in energy.
An Ion in Solution
 ion’s electronic structure: HOMO, LUMO, HOMO-LUMO gap.

Lowest Unoccupied Molecular Orbital

HOMO-LUMO Gap “Fermi” level

Highest Occupied Molecular Orbital


Gibbs Function and Work
Gibbs Free Energy and the Cell Potential

 Remember, negative free energy change is identified as defining a


spontaneous process.

GT, P  welectrical  n F E For O + ne- ↔ R

Basic Nernst equation relating chemical free energy change to electrical work done
 Note how a measurement of a cell or reaction potential directly calculates
the Gibbs free energy change for the process and vice versa
Nernst Equation (concentration effect)
 Expression for the Gibbs dependence on activity
 turn this around for an expression in terms of the cell potential
 For, A + B2+ ↔ A2+ + B
G  G  R T lnQ
 Q = [A2+]/[B2+]

 The relation between cell potential E and free energy gives


n F E  n F E  R T lnQ

 Rearrange and obtain the Nernst Equation.

RT
E E  lnQ
 nF
Standard Electrochemical Series
Based on the standard reduction potentials:
F2 + 2e– ® 2F– +2.87 2H+ + 2e– ® H2 0.0000
Co3+ + e– ® Co2+ +1.81 Pb2+ + 2e– ® Pb -0.13
Au+ + e– ® Au +1.69 Sn2+ + 2e– ® Sn -0.14
Ce4+ + e– ® Ce3+ +1.61 In3+ + 3e– ® In -0.34
Br2 + 2e– ® 2Br– +1.09 Fe2+ + 2e– ® Fe -0.44
Ag+ + e– ® Ag +0.80 Zn2+ + 2e– ® Zn -0.76
Cu2+ + 2e– ® Cu +0.34 V2+ + 2e– ® V -1.19
AgCl + e– ® Ag + Cl– +0.20 Cs+ + e– ® Cs -2.92
Sn4+ + 2e– ® Sn2+ +0.15 Li+ + e– ® Li -3.05

Note: In terms of basic materials chemistry, it is the energy level (or potential energy)
of the outermost electron, which influences these electrochemical potentials
Electrochemical Series and
periodic table

increasingly cathodic

increasingly anodic
Conventions
 The electrode at which oxidation is occurring is called the anode (which is
the more reducing agent !).
 The electrode at which reduction is occurring is called the cathode (which
is the lesser reducing agent !).
 A cell operating spontaneously in this configuration is said to have a positive
total cell potential
 When connecting a voltmeter, connect the positive terminal to the positive
electrode. If it reads a positive potential, you have correctly identified all the
terminals. If you read a negative potential, then you have misidentified the
reactions in the cells, and you have hooked it up backwards. Reverse your
assignment of anode and cathode.
 in a galvanic cell the cathode is +ve
 in an electrolytic cell the cathode is –ve.
Cell Notation
 A shorthand cell notation for the Daniell cell can be written as:

 Usually, anode appears on left hand side and cathode on right hand side
 write components in sequence
 separate phases with a single vertical line “|”
 A salt bridge or membrane is represented by a double vertical line “||” because it
separates two phase. If the two ‘half cells’ contain two different redox-active
species, but present in the same/common phase, then the two ‘half cells’ are
separated by a comma, ‘,’.
 included a specification of the species concentration
 ZnSO4 (1.0 M) or CuSO4 (1.0 M) can also be written in place of Zn 2+ and Cu2+,
respectively

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