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Electrochemistry
Electrochemistry is the study of production of electricity from energy released during
spontaneous chemical reactions and the use of electrical energy to bring about nonspontaneous chemical transformations.
Electrochemical Cells OR Galvanic Cells OR voltaic cell
A galvanic cell is a device that converts the chemical energy of a spontaneous redox
reaction into electrical energy.
Uses:
1. In this device the Gibbs energy of the spontaneous redox reaction is converted into
electrical work which may be used for running a motor or other electrical gadgets like
heater, fan, geyser, etc.
2. Electrochemical cells are extensively used for determining the pH of solutions, solubility
product, equilibrium constant and other thermodynamic properties and for
potentiometric titrations
potential
2+
to
2+
concentration of Zn and Cu
1.1
when
ions is unity).
called anode
and it has a
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Salt Bridge
Right
Anode
Cathode
Oxidation
Reduction
Loss of electrons
Gaining of electrons
Negative
Positive
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(1) Zn is being oxidised , therefore it acts as anode , hence it is negatively charged .
Ans:
+2
(2) Zn and Ag
(3) Two half cell reactions are
Zn(s)
Zn+2 (aq) + 2e
2Ag+ (Aq) + 2e
Ag(s)
Electrode potential(E):
between the
potential.
electrode
and
The
the
X-
According
to
IUPAC
rules
Reduction
potentials
is
taken
Electromotive force (emf) : The potential difference between the two electrodes of a
galvanic cell is called the cell potential when no current is drawn through the cell.
Cell Potential:
The potential difference between the two electrodes of a galvanic cell is called the cell
potential (Or) the difference between the electrode potentials (reduction potential) of
the cathode and anode.
It is measured in volts.
cell
=E
right
Question: Write the half cell reactions and depict the cell for the cell reaction:
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Cu(s) + 2Ag+(aq) Cu2+(aq) + 2 Ag(s)
Half-cell reactions:
Cathode (reduction): 2Ag+ (aq) + 2e 2Ag(s)
Anode (oxidation): Cu(s) Cu2+ (aq) + 2e
Cu(s) |Cu2+ (aq) ||Ag+ (aq) |Ag(s)
Ecell = Eright Eleft = E (Ag+/Ag) E (Cu2+/Cu)
We can measure only the difference between the two half-cell potentials that gives the
emf of the cell.
If we arbitrarily choose the potential of one electrode (half- cell) then, that of the other
can be determined with respect to this.
For this purpose we use, a half-cell called standard hydrogen electrode, represented
by Pt(s)H2(g)/H+(aq). It is assigned a zero potential at all temperatures corresponding
to the reaction H+ (aq) + e H2 (g)
If the concentrations of the oxidised and the reduced forms of Zn2+ / Zn, the species
in the right hand half-cell are unity, then the cell potential is equal to standard
electrode potential,
of the given half-cell.
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As
The measured emf of the cell: Pt(s) | H2 (g, 1 bar) | H+ (aq, 1 M) | | Zn2+ (aq, 1M) | Zn
is -0.76V
SHE is connected at the left (anode) and Cu2+/ Cu electrode at the right (cathode) gives
the reduction potential of this half-cell.
If the concentrations of the oxidized and the reduced forms of Cu2+ / Cu the species in
the right hand half-cell are unity, then the cell potential is equal to standard electrode
potential
As
The measured emf of the cell: Pt(s) | H2 (g, 1 bar) | H+ (aq, 1 M) | |Cu2+ (aq, 1 M) | Cu
is
0.34 V
Electrochemical Series:
The arrangement of elements in order of increasing reduction potential values is known
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Q.
Ans:
Ag<Hg,Cr,Mg<,K
Potassium is the strongest reducing agent while silver is the weakest reducing
agent. Higher the oxidation potential, more easily it is oxidized, hence Greater is
the reducing power.
Q.
Ans:
Any metal will be able to displace any other metal which is placed below it in the
electrochemical series.
Mg will displace all metals
Zn will displace all metals except Mg
Fe will displace Cu and Au
Cu will displace only Au
Au will displace none.
Q.
Knowing that :
Cu2+ (aq) + 2 e Cu (s)
E = + 0.34 V
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Reason out whether, 1 M AgNO3 solution can be stored in Copper Vessel or
1 M CuSO4 solution in Silver Vessel.
EOI2/I0.54v
EOAg+/Ag
0.80v
EOCu+2/Cu
0.34v
EO Br2/Br1.o9v
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Note: Cu does not dissolve in HCl. In Nitric acid it is oxidized by nitrate ion and not by
hydrogen ion.
1
How would you determine the standard electrode potential of the system Mg2+/Mg?
Consult the table of standard electrode potentials and suggest three substances that can oxidise
ferrous ions under suitable conditions. EOFe+2/Fe+3 = -0.77V
Arrange the following metals in the order in which they displace each other from the solution of their
salts. Al, Cu, Fe, Mg and Zn.
Given the standard electrode potentials,
K+/K = 2.93V, Ag+/Ag = 0.80V, Hg2+/Hg = 0.79V Mg2+/Mg = 2.37 V, Cr3+/Cr = 0.74V. Arrange
these metals in their increasing order of reducing power.
Depict the galvanic cell in which the reaction
Zn(s)+2Ag+(aq)
Knowing that :
Cu2+ (aq) + 2 e Cu (s)
E = + 0.34 V
Can a nickel spatula be used to stir a solution of Copper Sulphate ? Justify your answer.
(ENi+/Ni = 0.25 V
ECu+/Cu = 0.34 V)
9.
11
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12
13
If an external opposite potential is applied and increased slowly, we find that the reaction
continues to take place
When the opposing voltage reaches the value 1.1 V then, the reaction stops altogether and
no current flows through the cell.
Further increase in the external potential again starts the reaction but in the opposite
direction. It now functions as an electrolytic cell, a device for using electrical energy to
carry non-spontaneous chemical reactions.
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State the direction of flow of electrones and also specify if Zinc and Copper are
deposited or dissolved at their respective electrodes. When :
(a)
(b)
NERNST EQUATION
The standard electrode potentials (given in table) are measured when the
concentration of all the species involved in the electrode reaction is unity and
temperature is 298K.
This need not be always true. Nernst showed that the electrode potential depends on
the concentration of the electrolyte solution and temperature .
1.
a) For the reaction Zn2+ (aq) +2e----- Zn(s) Write the Nernst equation
b) For the reaction Cu+2 + 2e Cu write the single electrode potential
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Zn(s)+2Cu+2(aq)
Zn2+(aq)+2Cu(s)
Converting the natural logarithm to the base 10 and substituting R, F and T=298K
We should use the same number of electrons (n) for both the electrodes.
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2+
2+
It can be seen that E (cell) depends on the concentration of both Cu and Zn ions.
It increases with increase in the concentration of Cu 2+ions and decrease in the concentration
of Zn2+ions.
1.
Solution
2.
solution
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If the circuit in Daniell cell is closed then we note that the reaction:
Zn(s) + Cu2+ (aq) ----Zn2+ (aq) + Cu(s) takes place and as time passes
1.
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But when we write the reaction 2 Zn (s) + 2Cu2+ (aq) ---2 Zn2+ (aq) +2Cu(s)
rG = 4FE (cell)
and we have
we can obtain the thermodynamic quantity, rG, standard Gibbs energy of the
a) Calculate the emf of the cell in which the following reaction takes place:
Ni(s) + 2Ag+ (0.002 M) Ni 2+ (0.160 M) + 2Ag(s)
Given that E (cell) = 1.05 V
b) The cell in which the following reaction occurs:
at 298 K.
Calculate the standard Gibbs energy and the equilibrium constant of the cell
reaction.
ELECTRO CHEMISTRY
CLASS:12( CBSE)
ASSIGNMENT :
TOPIC: GALVANIC CELL
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Further show:
1. Write Individual reaction at each electrode
2. Which of the electrode is negatively charged?
3. The carriers of the current in the cell.
2.
How would you determine the standard electrode potential of the system Mg 2+/Mg?
Consult the table of standard electrode potentials and suggest three substances
that can oxidise ferrous ions under suitable conditions. EOFe+2/Fe+3 = -0.77V
Arrange the following metals in the order in which they displace each other from the
solution of their salts. Al, Cu, Fe, Mg and Zn.
Knowing that :
Cu2+ (aq) + 2 e Cu (s)
9
E = + 0.34 V
10
Can a nickel spatula be used to stir a solution of Copper Sulphate ? Justify your answer.
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(ENi+/Ni = 0.25 V
ECu+/Cu = 0.34 V)
11
EOI2/I0.54v
EOAg+/Ag
0.80v
EOCu+2/Cu
0.34v
EO Br2/Br1.o9v
12
Zn (s) / Zn2+ (aq) // Cu2+ (aq) / Cu. It has an electrical potential of 1.1 V when
concentration of Zn2+ and Cu2+ ions is unity.
State the direction of flow of electrones and also specify if Zinc and Copper are
deposited or dissolved at their respective electrodes. When :
(a)
(b)
13
14
The standard electrode potential for the Zn+2/Zn is o.76v .Write the reactions occurring at
Electrodes when coupled with standard hydrogen electrode (SHE)
NERNST EQUATION:
EOFe+3/Fe+2
0.77v
ELECTRODES
Mg2+ /Mg(s)
Cu2+/Cu
Fe2+/ Fe(s)
Sn2+/ Sn(s)
EOI2/I0.54v
EOAg+/Ag
0.80v
EOCu+2/Cu
0.34v
EO Br2/Br1.o9v
EO
-2.37v
0.34v
-0.44
-0.40v
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Br2(l)/Br
Cr3+/Cr
Cd2+/Cd
Zn+2/Zn
Ag+ /Ag
1
0.74
-0.40
-0.76v
0.80v
2Cr3+(aq) + 3Cd
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