Chemistry
Topics
● 1. Introduction
● 2. Daniel cell
● 3. Salt Bridge
● 4. Measurement of electrode potential in a cell
● 5. Standard hydrogen electrode
● 6. Nernst Equation
● 7. Electrochemical Cell
● 8. Electrical resistance
● 9. Electrical conductance
● 10. Measurement of resistance of a solution
● 11. Arrangement for measurement of Resistance
● 12. Molar conductivity
● 13. Variation of Conductivity and Molar Conductivity with Concen
● 14. Strong electrolytes
ElectrochemistryIntroduction
● Electrochemistry refers to the conversion of chemical energy to electrical energy
and vice versa. It is basically the study of Production of electricity from energy
released during spontaneous reaction and use of electrical energy to bring about
non-spontaneous chemical transformation.
● A spontaneous chemical reaction is a reaction which happens on its own and
releases free energy. This reaction produces electric energy from chemical
reaction. For example, burning of coal, rusting of iron, melting of ice, etc.
● On the other hand non-spontaneous reaction occurs by providing an external
source like electricity. For example, Hydrolysis of water.
● Electrochemistry is used for the following purposes.
● Production of metals like sodium hydroxide, chlorine, fluorine and many other
chemicals.
● It is also used for purification of metals.
● The process is used in batteries as well as fuel cells which converts the chemical
energy into electrical energy and is used in several instruments and devices.
● This process is used in electroplating.
● The reactions carried out using the process of electrochemistry are energy
effective and less polluting.
Daniel cell
● The cell that converts the chemical energy liberatedas a result of redox reaction
to electrical energy is called a Daniel cell.
● It has anelectrical potential of 1.1 V.
● The setup for Daniel cell is as follows:
○ In a beaker a plate of zinc is dipped in a solution of zinc sulfate (ZnSO 4).
○ In another beaker a plate of copper is dipped in a solution of copper (II)
sulfate in another container. These plates of metal are called the
electrodes of the cell.
○ These electrodes behave as terminal to hold the electrons.
○ The two electrodes are connected via wire.
○ A salt bridge is placed between the two beakers. This provides a path for
the movement of ions from one beaker to the other in order to maintain
electrical neutrality.
○ Zinc electrode gets oxidized and hence releases electrons that flow
through the wire towards the copper electrode.
○ The copper (II) sulfate solution releases copper ions Cu2+.
○ At the anode:
Oxidation ---------------- loss of electrons.
Zn --> Zn2+ + 2e-
At cathode,
Reduction -------------gain of electrons.
Cu2+ + 2e- --> Cu
○ Zinc atoms being more reactive have a greater tendency to lose electrons
than that of copper.
The electrons in this cell moves from zinc anode to copper cathode
through the wire connecting the two electrodes in the external circuit
○ A bulb placed within this circuit will glow and a voltmeter connected within
this circuit will show deflection.
○ The net reaction of this cell is the sum of two half-cell reactions.
Zn(s) + Cu2+ (aq) --> Zn2+ (aq) + Cu(s)
In a Daniel cell a salt bridge is placed between the two beakers containing a solution of
zinc sulfate (ZnSO4) and a solution of copper (II) sulfate respectively. This provides a
path for the movement of ions from one beaker to the other in order to maintain
electrical neutral
Electrochemical Cell and Gibbs Energy of the Reaction
Standard hydrogen electrode
● The electrode is connected to a standard hydrogen electrode (SHE) to constitute a
cell
● It consists of a platinum electrodecoated with a layer of platinum black.
● The electrode is immersed in an acidicsolution and the pure hydrogen gas is bubbled
through it.
● Theconcentration of the reduced form and the oxidized form of hydrogen issustained
at unity with following conditions:
● Pressure of hydrogen gas = 1 bar
● Concentration of hydrogen ion in the solution = 1 molar
Ecell = Ecathode – Eanode
Ecell = Ecathode – 0 = Ecathode
● The measured Emf of the cell:
Pt| H2 (1 bar)| H+ (1M) || Cu2+ (1M)| Cu is 0.34 V.
The positive value of the standard electrode potential signifies the easy reduction of Cu 2+
ions than H+ ions.
● The measured Emf of the cell
Pt| H2 (1 bar)| H+ (1M) || Zn2+ (1M)| Zn is -0.76 V.
The negative value of the standard electrode potential signifies that the hydrogen ions
oxidizes the zinc (or it can be said that zinc can reduce hydrogen ions).
● An electrode with standard electrode potential greater than zero is stable in its
reduced form compared tohydrogen gas.
● Whereas an electrode with negative standard electrode potential is less stable in its
reduced form compared to hydrogen gas.
● This decreases the standard electrodepotential which in turn decreases the oxidizing
power ofthe specific electrode on the left and increases the reducing power of the
electrodeto the right of the reaction.
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● Electrical work done (1 second) = Electrical potentialX Total charge passed
● Passing the charges reversibly through the galvanic cell results in maximum
work.
● Reversible work done by galvanic cell = Decrease in Gibbs energy
● Let E = Emf of the cell
nF = Amount of charge passed
ΔrG = Gibbs energy of the reaction
ΔrG = -nFEcell
For the reaction,
Zn(s) + Cu2+ (aq) --> Zn2+ (aq) + Cu(s)
[ΔrG = -2FEcell ]
But when the equation becomes
2Zn(s) + 2Cu2+ (aq) --> 2Zn2+ (aq) + 2Cu(s)
[ΔrG = -4FEcell ]
Problem:
The cell in which the following reactions occurs:
has Eøcell = 0.236 V at 298 K. Calculate the standard Gibbs energy and the
equilibrium constant of the cell reaction.
Solution:
By using the formula,
ΔrG = -nFEcell
= -2 X 96487 X 0.236
= - 45541.864 J mol-1
= - 45.54 KJ mol-1
Now,lectrochemical Cell and Gibbs Energy of the Reaction
● Electrical work done (1 second) = Electrical potentialX Total charge passed
● Passing the charges reversibly through the galvanic cell results in maximum
work.
● Reversible work done by galvanic cell = Decrease in Gibbs energy
● Let E = Emf of the cell
nF = Amount of charge passed
ΔrG = Gibbs energy of the reaction
ΔrG = -nFEcell
For the reaction,
Zn(s) + Cu2+ (aq) --> Zn2+ (aq) + Cu(s)
[ΔrG = -2FEcell ]
But when the equation becomes
2Zn(s) + 2Cu2+ (aq) --> 2Zn2+ (aq) + 2Cu(s)
[ΔrG = -4FEcell ]
Problem:
The cell in which the following reactions occurs:
has Eøcell = 0.236 V at 298 K. Calculate the standard Gibbs energy and the
equilibrium constant of the cell reaction.
Solution:
By using the formula,
ΔrG = -nFEcell
Weak electrolytes
● A substance which forms ions in an aqueous solution do not dissociate
completely at moderate concentrations is known as weak electrolyte.
● For example, HC2H3O2 (acetic acid), H2CO3 (carbonic acid), etc.
● The conductance of the solution increases with dilution of solution.
● The interionic forces of attraction are not strong at a low concentration.
● The slope for Λm vs c1/2 is not linear even at a lower concentrations.
● These electrolytes have lower degree of dissociation at higher concentrations.
● The value of Λm changes with dilution due to increase in the degree of
dissociation.
● Ëm increases sharply on dilution exclusively at lower concentrations.
● At infinite dilutionwhen concentration approaches to zero, the electrolyte
dissociates completely. But at lower concentration the conductivity of a solution is
low to an extent that cannot be even measured.
Strong electrolytes
● A solute or substances that completely ionize or dissociates in a solution are
known as strong electrolyte. These ions are good conductors of electricity in the
solution.
● For example, HCl, HBr, HI, HNO3, NaOH, KOH, etc.
● For strong electrolytes, Λm increases slowly with dilution and can berepresented
by the equation:
● It dissociates completely at moderate concentrations.
● The conductance of the solution increases with dilution of solution.
● There exist strong interionic forces of attraction at moderate concentrations.
● The slope for Λm vs c1/2 is linear at low concentrations.
Fig. Molar conductivity Λm Vs. c1/2 for acetic acid and potassium chloride
Measurement of electrode potential in a cell
● The electrode is connected to a standard hydrogen electrode (SHE) to
constitute a cell.
● The electrode forming the negative terminal of the cell is allotted negative value
of electrode potential whereas the electrode forming the positive terminal of the
cell is allotted a positive value of electrode potential.
● The potential difference developed between the two terminals is measured using
a potentiometer.
● The direction of the flow of electric current in the external circuit is identified using
a galvanometer.
● This enables us to identify the positive and the negative terminal of the set up as
the current flows from positive terminal to negative terminal.
● This in turn will help us mark the anode and the cathode electrodes due to the
fact that the electrons will flow from anode to cathode.
Ecell = Ecathode – Eanode
● In case of Daniel cell
At the anode:
Oxidation ---------------- loss of electrons.
Zn --> Zn2+ + 2e-
At cathode,
Reduction -------------gain of electrons.
Cu2+ + 2e- --> Cu
The net reaction of this cell is the sum of two half-cell reactions.
Zn(s) + Cu2+ (aq) --> Zn2+ (aq) + Cu(s)
Emf of the cell = Ecell = Ecathode – Eanode
= 0.34 V – (- 0.76) V = 1.10 V
(Measured Emf of Cu is 0.34 V and that of Zn is 0.76 V).
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