Anomalous properties of water

(electrolyte)

 Close to interface
 When it is confined
 When it is controlled
Surface is unknown
 Gibbs and Guggenheim model of interface

Bulk Guggenheim Bulk

Bulk Bulk
phase α ideal phase β
phase α phase β
Interface σ

Gibbs ideal Interface σ

Total volume V (since = 0)

U
𝑁 𝜎𝑖
Γ𝑖= Interfacial excess
𝐴
S
Gibbs and Guggenheim model of interface

1 • No interfacial excess
• Region 1 and 2 balance each other
• Ideal situation
2

• Actual number < Number estimated

• Region 1 >2
• Negative surface excess

• Actual number > Number estimated

• Region 1 < 2
• Positive surface excess
 Gibbs and Guggenheim model of interface
For single component in multi-phasic system

For multiple component in

multi-phasic system

H.W. 3 (deadline : 22nd Aug)

Relative adsorption of component i with respect to component 1

 What is an electrochemical reaction?

- Electrode Solution Electrode Solution

(Solid) (Liquid)

Vacant MO

Energy level
of electrons
Occupied
+ MO
• Reduction involves driving the electrode to more negative
potential and thereby raising its energy.
• Reduction current is flow of electrons from electrode to
solution.
 What is an electrochemical reaction?

- Electrode Solution Electrode Solution

(Solid) (Liquid)

Vacant MO

Energy level
of electrons
Occupied
+ MO

• Oxidation involves lowering the energy of electrons using a

more positive potential.
• Oxidation current is flow of electrons from solution to
electrode.
Electron-transfer reaction : Homogeneous vs heterogeneous

• Directional
• Both reduction and oxidation possible at same interface

J. Chem. Educ. 2018, 95, 197−206

 Comparing thermodynamic potentials

- Pt Fe3+ Sn 4+ Ni2+
-0.25 V

0.15 V

0.77 V
Pt (0)
+ Potential for
zero current
(equilibrium)

• Species with least negative (most positive) value will be

reduced.
• Fe3+ is reduced first.
• Similar order for oxidation.
 Comparing thermodynamic potentials

- Au Sn2+ Fe2+
Au (0)
-0.15 V Potential for
zero current

-0.77 V

+
Which is easier to oxidise?
• Species with least positive (most negative) value will be
oxidised first.
• Sn2+ is oxidised first
• Charge transfer electrodes & Faradic reactions
Electrochemical series
 Comparing thermodynamic potentials

- Hg Cr3+ Zn2+
-0.76 V

-0.41 V

0V
Hg (0)
+
• Expected : H2 reduction reaction
• Observed : Cr3+ reduction.
• Purely thermodynamic considerations.
• NO Kinetics taken into account.