PPT file only for
reference
This material is for reference only. Points present in the slides are only for
assistance and their elaboration are present in book.
Examination questions will be in depth and can be solved by following text
book only.
ELECTROCHEMISTRY
Helmholtz double layer (HDL) refers to the structural representation of the
accumulation of electrical charges present at the boundary of an electrode and
electrolyte when they are in contact with each other. HDL is most readily identifiable in
fluid-based mixture systems, such as paints used for corrosion prevention.
Helmholtz electric double layer
(HDL)
• HDL is established at the metal-aqueous
solution interface
• Tendency of electrode depends upon the
direction of the equilibrium shift
• Forward direction- oxidation
• reverse direction- reduction
• Across HDL (HED) layer movement of charge occurs, it results in electrode
potential
• Potential exist between the metal (substrate) and its ions in an aqueous
solution at their equilibrium when they are in contact.
• Tendency of metal to loose or gain electron when it is in contact of its own salt
solution
Oxidation Potential
If oxidation occurs at the electrode, at equilibrium the
potential of the electrode can be termed as oxidation
potential. For the zinc electrode, the reaction can be
represented as:
Reduction Potential
If reduction occurs at the electrode, at equilibrium the
potential of the electrode is referred to as reduction
potential. For the zinc electrode, the reaction can be
represented as:
Standard Electrode Potential (E0)
If is defined as the potential that exists between the metal or
the gas and its aqueous solution of unit concentration at 298
K when the sum of all partial pressures of the gaseous
reactants and products, if any, is equal to 1 atm pressure.
Among other cells, a galvanic cell is a type of electrochemical cell. It is used to supply
electric current by making the transfer of electrons through a redox reaction. A galvanic
cell is an exemplary idea of how energy can be harnessed using simple reactions
between a few given elements.
Galvanic Cells
+
anode - cathode
oxidation reduction
spontaneous
redox reaction
19.2
Galvanic Cells
The difference in electrical potential between the anode
and cathode is called:
• cell voltage
• electromotive force (emf)
• cell potential
Cathode + in Galvanic cell Cell Diagram
Cathode – in Electrolytic cell
Zn (s) + Cu2+ (aq) Cu (s) + Zn2+ (aq)
CAR = Cathode [Cu2+] = 1 M & [Zn2+] = 1 M
Reduction
Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)
Anode Cathode
(Oxidation) (Reduction)
A redox reaction is spontaneous if the standard electrode potential for the redox
reaction, Eo(redox reaction), is positive. If Eo(redox reaction) is positive, the reaction will proceed
in the forward direction (spontaneous). ... Note: The reaction will be spontaneous in
the reverse direction!
Spontaneous and non-spontaneous
If Eo(redox reaction) is positive, redox reaction is
spontaneous
If Eo(redox reaction) is negative, redox reaction is not
spontaneous (non-spontaneous).
For the reaction Ca2+ + Zn → Ca + Zn2+, Eo is -2.11 V
The reaction Ca2+ + Zn → Ca + Zn2+ will not proceed
spontaneously in the forward direction
What is salt bridge?
Salt bridge is usually an inverted U-tube filled with con
centrated solution of inert electrolytes. An inert electrolyte
is one whose ions are neither involved in any
electrochemical change nor do they react chemically with
the electrolytes in the two half-cells. Generally salts like
KCl, KN03, NH4NO3, etc., are used
