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B.R.Thorat
Department of Chemistry
Govt. of Maharashtra
Electrochemistry
Branch of chemistry which deals with relationship between chemical reactions
(Redox reaction, Chemical Energy) and Electrical Energy
With proper arrangement
Electrolytic cell
ELECTROLYTIC CELL:
It is the arrangement in which electric energy is used to begin about a chemical change or it
is a device which can convert electric energy into chemical energy.
E.g. Charging of lead storage battery
GALVANIC CELL:
It is the arrangement in which chemical energy can be transformed into electrical energy.
E.g. Discharging of lead storage battery, Daniel cell.
Electrodes: Conduct
electricity between cell and
surroundings
Inactive
electrode: sites
for oxid. & red.
Active electrode:
Participate in
redox reaction
Cell
Battery
E.g.:- An ordinary 6-volt lead storage battery is a combination of 3-volt cells connected
in series
+ +
+ +
+ +
+ +
++ +
salt solution
electric double layer
There are three cases as(1) PS >PO:In such case, positive (metal ) ions passed more rapidly into solution leaving behind the
electrons on the surface of the electrode so that the electrode become negative charged
and solution become positive charged for example- Active metals like Zn ,Cd , Mn Ni
alkali metals etc.
Zn Metal rod
Zn
Vessel
+
+
+
+
+
+
+ + +
+
+
+
+
+
+
+
ZnSO4
salt solution
electric double layer
(2) Po >Ps:
In such case, the positive ions of metals in the solution are
deposited more rapidly on the metal rod, so that the
electrode become positively charged and solution become
negatively charged for example less active metals like Cu,
Ag, Au etc. in its salt solution.
Cu Metal rod
Cu
Vessel
+ +
+ +
+ +
+ +
++ +
(3)Ps = Po:In such case, neither the metal ion into the solution nor the metal
ion deposited ion on the surface of metal rod, so that metal and
solution do not acquire any charge and no potential difference
can be exist such electrode is called as null electrode.
ELECTROCHEMICAL CELL
Electrochemical cell is a device is used to generate
electrical energy at the expense of spontaneous
oxidation-reduction.
The electrochemical cell is also called Galvanic cell or
Voltaic cell i.e. the electrochemical cell can be convert
chemical energy into electrical energy.
A single electrochemical cell is formed by the
combination of two electrodes One act as anode
(negative electrode) and other act as cathode
(positive electrode).
E.g.:- A simple galvanic cell is set up by dipping Zinc and copper rods / plates
into sulphuric acid solution or by dipping Zinc and Copper rods or plates into the
solution of their respective salts.
The electrical neutrality is maintained by using the porous partition or by a salt
bridge. These can be explaining with the help of typical example- Daniel cell.
DANIEL CELL
[Zn(s) | ZnSO4 | CuSO4 | Cu(s)]
(A) CONSTRUCTION:
A Daniel cell consist of two half electrodes. The metallic copper is dipped into its salt
solution such as CuSO4. This half cell can be represented as- Cu | CuSO4 or Cu | Cu++
and the another half cell is the metallic Zinc is dipped into its salt solution such as
ZnSO4 .This half cell can be represented as- Zn | Zn++ or Zn | ZnSO4.
The single vertical line indicates the electrode-electrolyte interface. These two half cells
are combined by using three difference methods are-
(a) BY
USING
POROUS
PARTITION:
A porous partition is kept in the vessel which
divides it into two compartments. A one
compartment containing ZnSO4 solution and
another containing a CuSO4. The Zinc and
copper rods are dipped into its respective salt
solution. This zinc and copper electrodes are
connected by the metallic wire. The electron is
flow from the zinc to copper electrode.
e
Zn electrode
e
+
Copper vessel (Cu electrode)
porous spot
ZnSO4 solution
CuSO4 solution
e
Cu electrode
Zn electrode
Glass vessel
porous spot
ZnSO4 solution
CuSO4 solution
The two half cells are connected by the salt bridge. The solution of CuSO4 and ZnSO4
are taken into two different vessels containing zinc and copper rod in respective salt
solution. These two vessels are connected by a salt bridge. The zinc and copper
electrode are connected by a metallic wire. The electron flows from zinc to copper
electrode.
H+
MnO4-
Fe+2
Galvanic Cell
Salt
Bridge
allows
current
to flow
H+
MnO4-
Fe+2
Electricity
H+
MnO4-
e-
Fe+2
Voltmeter
Zn ()
Zn2+
Salt bridge
Na+
SO42
(+) Cu
Cu2+
Voltmeter
e
Anode Salt bridge
+
Zn () Na
SO 2
(+) Cu
Zn2+
Oxidation half-reaction
Zn(s)
Zn2+(aq) + 2e
Cu2+
e
2e lost
per Zn atom
oxidized
Zn
Zn2+
Voltmeter
e
Anode Salt bridge
+
Zn () Na
SO 2
(+) Cu
Zn2+
Oxidation half-reaction
Zn(s)
Zn2+(aq) + 2e
Cu2+
e
2e lost
per Zn atom
oxidized
Zn
Zn2+
Voltmeter
e
e
Anode Salt bridge Cathode
+
Zn () Na
SO 2 (+) Cu
4
Zn2+
Cu2+
Oxidation half-reaction
Zn(s)
Zn2+(aq) + 2e
Reduction half-reaction
Cu2+(aq) + 2e
Cu(s)
e
2e gained
per Cu2+ ion
reduced
2e lost
per Zn atom
oxidized
Zn
Cu2+
Zn2+
Cu e
Voltmeter
e
e
Anode Salt bridge Cathode
+
Zn () Na
SO 2 (+) Cu
4
Zn2+
Cu2+
Oxidation half-reaction
Zn(s)
Zn2+(aq) + 2e
Reduction half-reaction
Cu2+(aq) + 2e
Cu(s)
e
2e gained
per Cu2+ ion
reduced
2e lost
per Zn atom
oxidized
Zn
Cu2+
Zn2+
Cu e
Voltmeter
e
e
Anode Salt bridge Cathode
+
Zn () Na
SO 2 (+) Cu
4
Zn2+
Cu2+
Oxidation half-reaction
Zn(s)
Zn2+(aq) + 2e
Reduction half-reaction
Cu2+(aq) + 2e
Cu(s)
Overall (cell) reaction
Zn2+(aq) + Cu(s)
Zn(s) + Cu2+(aq)
Cu++ + 2e- Cu
The liberated electron at zinc electrode travel
towards the copper electrode through an
external circuit. The Cu2+ ions in the solution
of CuSO4 go and get discharged at Cuelectrode by taking electrons which is coming
from the Zn rod. It is called reduction of Cu++
The current is flow from the Cu- electrode (cathode) to Zn- electrode (anode). At anode Znatoms from the rod enter into solution as Zn++ therefore, size of zinc rod reduces continuously
and at cathode Cu- atoms deposited on the copper electrode, so that size of copper-rod
increases.
Represented of cell: - Zn(s) | ZnSO4 || CuSO4 | Cu(s).
(1) The negative electrode or electrode having oxidation potential is written to the
left hand side in the cell. The oxidation reactions take place at negative electrode
(4) The double vertical line between two salt solutions indicates indirect contacts between
them .i.e. two half cells are connected by salt bridge.
E.g.:- Zn- | ZnSO4 (aq) || CuSO4 (aq) | Cu+
(5) In case of gas-electrode, inert metal conductor is used for electrical contact & for ionization. E.g.: In the hydrogen electrode, platinized platinum foil is dipped into dilute HCl
solution and over which hydrogen gas bubbled. Pt, H2 | HCl (aq), Pt, Cl2 |Cl- (aq).
(6) When concentrations or activities of solution and pressures of gases are required, these
are written in the bracket.
Zn- | ZnSO4 (0.1m) || CuSO4 (0.1m) | Cu+; Pt-, H2 (1atm) | HCl (aH+ = 1), AgCl (s) |Ag+.
(7) For spontaneous cell reaction, electrons are flows from LHE to RHE, where as current
is flows in opposite direction.
(8) The total emf of a cell is the sum of oxidation potential of LHS electrode and reduction
potential of the RHS electrode. Ecell = EOx (LHS) + ERed (RHS) = EOx (LHS) EOx (RHS).
Standard cell
The accuracy of the measurement of emf will be depends on the accuracy of the emf of
standard cell. There are some condition which must satisfied by the standard cell-
1. It should show the characteristic reversibility and does not damage permanently
due to passage of current through it.
2. Standard cell potentials are reproducibly constant with time and well known.
3. Standard cell have low temperature coefficient of emf.
The cell which satisfied all these properties is the Western saturated and unsaturated
standard cell
+
H (aq)
H2 (g)
Hg
salt bridge
Pt wire
Platinised platinum plate
1M HCl solution
Therefore, instead of SHE, some other secondary reference electrodes are used whose
potentials are known exactly, and its construction is simple. The calomel electrode is
quite satisfactory as secondary reference electrode.
1 M calomel
0.1M KCl
1 M KCl
Hg2Cl2 (S) + 2e- 2Hg(l) + 2Cl-
Pt wire
Saturated Calomel
Sat. KCl
The reduction potential of an electrode is equal to the oxidation potential for the
same electrode but having different (reversed) sign.
... E(oxi) = - E(red)
***NERNST EQUATION***
In electrochemical cell- one electrode undergoes oxidation where as other get reduction. Therefore, the total
electrode potential is the algebric sum of the single electrode potentials:
Ecell = E(oxi) + E(red) = Eox(LHE) + Eox(LHE)
The value of the single electrode potential of electrode undergoes oxidation as:
M Mn+ + ne... According to the Nernst equation Eox = Eox0 RT/nF ln a+
Where, a+ is the activity or concentration of the metallic ion in the solution.
Oxidation
The value of the single electrode potential of electrode undergoes reduction as:
Reduction
Mn+ + ne- M
... According to the Nernst equation Ered = Ered0 - RT/nF ln 1/a+
Where, Eox0 = Standard oxidation potential, Ered0 = Standard reduction potential, R = Gas constant =
8.314 Joules, T = Absolute temperature of electrode, F = Faradays constant = 96500 joules, n = number
of electrons involved in the oxidation or reduction process.
For the dilute solutions the activity can be expressed in term of concentration. At 250C considering the
value of R, F and ln = 2.303 log10, therefore above equation can be written asEox = Eox0 0.059/n log10 a+
Ered = Ered0 0.059/n log 1/ a+
In general, the Nernst equation can also be stated asEox = Eox0 RT/nF ln aoxidant/areductant
Ered = Ered0 RT/nF ln areductant/aoxidant
And
Redox
Calculation of cell emf from single electrode potentials:If the single electrode potentials and its reactions are available, the cell reaction and its emf
can be calculated by using following steps1) The standard oxidation or reduction potential of each electrode can be determined by
coupling the electrode with SHE at 250C.
2) The electro-chemical cell which is under study can be written with the convention with
respect to the cell reaction.
3) The electrode potential of anode and cathode can be determined by using Nernst equation
after knowing the activity of the cations in the solutions.
Eox = Eox0 RT/nF ln a+ = Eox0 RT/nF ln aoxidant/areductant
Ered = Ered0 RT/nF ln 1/a+ = Ered0 RT/nF ln areductant/aoxidant
4) The emf of the cell is the algebric sum of the two electrode potentials forming the cell,
thus Ecell = Eox + Ered
And the standard cell potentials (E0cell) is determined after knowing Ered0 and Eox0 of the
electrodes forming the cell.
Ecell0 = E0ox + E0red
5) The emf of the cell is directly calculated after knowing the activities of the ions in their
solutions by using Nernst equation.
Ecell = Ecell0 RT/nF ln acC x adD x . / aaA x abB x .
Summary of Rules:The various rules introduced above with respect to cell reactions and emfs are
summarized below1) Any cell reaction is the sum of the single electrode reactions as they occur in cell
a) At anode, the oxidation reaction can be take place. b) At cathode, the reduction
reaction can be occurred.
2) The cell emf is the algebric sum of the single electrode potentials: Ecell = Eox + Ered
3) The negative electrode can be written at the left hand side and the positive
electrode can be written at the right hand side. So that the electrons can flow from
left to right through an external circuit, the cell reaction deduced by the rule- a) Is
spontaneous and emf deduced by the rule, b) Is positive.
4) If the wrong assumption is done with respect to the polarity of the electrode, the emf
of cell is negative and cell reaction is non spontaneous.
5) Oxidation potential of all metals above hydrogen in electro-chemical series is
positive and those below are negative.
6) Activities of pure solid, liquid, insoluble solids and pure gases with unit
atmospheric pressure are taken as unity.
7) The oxidation or reduction potential of the SHE is assumed to be zero.
Classification of the electrodes:The electrodes are in two types- ion selective electrodes and ion specific electrodes.
Ion specific electrodes:These electrodes are reversible to its own ions in the solution with which it is directly
contact. They are constructed by using solid metal rod/trip/wire in contact with its
aqueous solution or gas molecules. The various electrodes used in electrochemical work
are classified into following five groupsi) Metal-metal ion electrodes.
ii) Amalgam electrodes.
iii) Gas electrodes.
iv) Metal-insoluble salt electrodes.
v) Oxidation-reduction electrodes.
Ion selective electrodes:These are electrochemical sensors. They are used for the potentiometric determination
of activity of particular ion in presence of other ions.
The selective membrane can be prepared from glass, solid crystalline ceramic or
polymer. The change in activity of certain ion in the sample causes change of membrane
potential and therefore electrode.
1) Glass electrode.
2) Solid crystalline ceramic electrode.
1. Metal-metal ion electrode:The electrodes of this type involve a metal in equilibrium with a solution
of its ion. The electrode consists of a rod or a strip of metal dipped in a
solution containing its ion. All these electrodes operate on the general
reaction.
M Mn+ + neThe electrode potential corresponding to the oxidation can be calculated
by using the following equationEm = E0m RT/nF ln amn+
Where, amn+ is activity of metal ions. Each of these electrodes is said to
be reversible to its own ions. Examples are the Zinc, Copper, Cadmium
and Sodium electrodes.
2. Amalgam electrode:In same cases of metal-metal ion electrodes, the pure metals are too active and not stable in its
metallic form in aqueous solution.
E.g. - K, Na, Ca etc. are highly active metals and can not be used in their pure form in metal
electrode. The activity of such metals can be lowered some what by dilution in the mercury i.e.
forming its amalgam. These amalgams can be used to construct the electrode. Therefore it is
called as amalgam electrode. They are constructed by dipping the amalgam of the desired metal
in solution of its salt.
The general reaction take place at the electrode is
M(Hg) Mn+ + ne- + Hg
The corresponding oxidation electrode potential can be calculated by using the equationEa = E0m (RT/nF) ln (amn+/am)
Where, Ea = Electrode potential
amn+ = Activity of metallic ions in the solutions
am = Activity of metal in the amalgam.
The amalgam electrodes have some advantageous over the metallic electrodes1) The equilibrium between the metals and their ions can be established rapidly than the pure
metal electrodes.
2) Due to amalgamation, the impurities present in the metals are diluted; therefore, they do not
affect practically the behavior of the electrodes and gives satisfactory and reproducible results.
3) If the amalgam is saturated with metal, then electrode becomes equivalent to metal-metal ion
electrodes; (i.e. am =1), it is because the chemical potential of a component in its saturated
solution equals the chemical potential of pure metal.
3. Gas Electrode:Gas electrodes consist of inert metal wire or foil immersed in a solution
containing ions to which gas molecules are reversible. The gas bubbling
about the inert metal; so that gas is absorbed over the surface of the inert
metal and become saturated. The absorbed gas molecules and their ions
in solutions are brought in contact through the inert metal. The metal foil
established the equilibrium between the gas and its ions in solution. The
most common inert metal used is platinumPt, M2 (g) (PM2) | Mn+ (aMn+)
E.g. M2 (g) Mn+ + neThe oxidation potential is E = E0M2 RT/nF ln (amn+/a1/2M2)
At low pressure the activity of the gas is equal to pressure of gas in
atmosphere.
E = E0M2 RT/nF ln (amn+/PM2)
4. Metal-insoluble salt electrode:The various types of calomel electrodes, the silver-silver chloride electrode, the lead-lead
sulphate electrode, silver-silver bromide electrode etc. are the examples of such type of electrode.
These electrodes consist of a metal in contact with one of its sparingly soluble salt and solution
containing the ion present in the salt other than the metal.
For example- Silver-Silver chloride electrode composed of a silver wire coated with silver
chloride and dipped in the solution of chloride ions. In the Lead-Lead sulphate electrode the lead
metal is used in its amalgam is covered with a crystal of lead sulphate and surrounded by the
sulphate. In all instances these electrodes are reversible to the ions other than those of metal
present in the insoluble salt e.g. Silver-silver chloride electrode is reversible to the chloride ions.
Consider the silver electrode dipping in the solution of chloride ions and is saturated by the
silver chloride. If the electrode is acts as ordinary metal-metal ion electrode, then silver ion will
pass from the electrode into the solution according to the equationAg(S) Ag+ + eBut the solution is saturated with silver chloride and the introduction of any silver ions into the
solution distributed the solubility product principle of the salt, therefore to re-establish the new
equilibrium, backward reaction (reaction between Ag+ and Cl-) can be take place forming undissociated AgCl.
Ag+ + Cl- AgCl
Therefore the over all reaction occurring at the electrode is Ag + Cl- AgCl + eIt indicates that the electrode is reversible with respect to Cl- ion. For this reaction the electrode
potential isEAg/AgCl = E0Ag/AgCl RT/F ln 1/aCl-
5. Oxidation-reduction electrode:In the oxidation-reduction electrode, the ions of a substance in two different oxidation
states are present in the same.
For example:- When a platinum wire is immersed in a solution containing Ferrous and
Ferric ions or in a solution containing both- Cerous-Ceric ions, Stannous-Stannic ions
etc a potential is developed called redox potential. This potential can be arises by the
electrode due to spontaneous conversion of one oxidation state of metal ion into another
stable oxidation state.
Fe3+ + e- Fe2+
Ce3+
Ce4+ + eThe function of platinum wire is to facilitate the exchange of electron from one species
to another and provides the electric contact to the electrode. The other redox electrodes
areSn2+ Sn4+ + 2eMn2+ + 4H2O MnO-4 + 8H+ + 5eHydroquinone [C6H4(OH)2] quinine (C6H4O2) + 2H+ + 2eIn general the equilibrium between oxidized and reduced state of the same substance
can represented asReduced state Oxidized state + neThe electrode potential can be derived by using the following Nearst equation.
ERedox = ERedox0 RT/nF ln aoxid state/aredu state
Classification of electrochemical calls:A large number of electrochemical calls are obtained from the combination of
various electrodes. The cells are broadly classified into two types1) Chemical cells, 2) Concentration cells.
Electrochemical cells
Chemical cells
Without transference
Concentration cells
With transference
Without transference
With transference
1. Chemical cells:It is a class of electrochemical cells in which the free energy of a cell is converted
into a electric energy, and
2. Concentration cells:It is a class of electrochemical cells in which electric energy can be generated due
to transfer of matter from one half cell into another half cell on account difference
in- Electrode composition or Concentration of the electrolyte.
Buffer solutions
1. The solution of a weak acid or weak base and its salt with strong base or strong acid.
2. It resist the change in pH of the solution by the addition of small amounts of strong acid
or base or upon dilution
e.g. A buffer of carbonic acid (H2CO3) and bicarbonate (HCO3-) is present in human blood
plasma to maintain pH between 7.35 and 7.45.
There are two types of buffer solutions as- acidic buffer and basic buffer.
Acidic buffer: It is the solution of weak acid and its salt with strong base. E.g. acetic acid
+ sodium acetate.
Basic buffer: It is the solution of weak base and its salt with strong acid. E.g. ammonium
hydroxide + ammonium chloride.
Buffer solutions
Hendersons equation for acidic and basic buffer solutions
Acid buffer solution: It is made from weak acid HA and its salt with strong base BA.
HA is weak electrolyte therefore dissociated partially and exist equilibrium with A- ions.
HA (aq)
H+(aq) +
A-(aq)
According to the Le Chateliers principle (or common ion effect), in presence of salt the
equilibrium will be shifted towards left. The salt BA will get dissociated completely into B+ and Awhich increases the concentration of A- and decreases the dissociation of acid HA. The equilibrium
constant isKa = [H+(aq)] [A-(aq)]/[HA(aq)]
Or
[H+(aq)] = Ka [HA(aq)] / [A-(aq)]
.. (1)
Taking the negative logarithum of both sides, we havepH = pKa + log[A-(aq)]/[HA(aq)]
.. (2)
Assume that [A (aq)] is only due to salt BA i.e. [BA] [A (aq)] i.e. amount of A- present in the
solution at equilibrium is approximately the same as the amount of salt AB present initially. Also very
small amount of acid undergoes dissociation therefore amount of acid in equilibrium is same as the acid
added initially.
pH = pKa + log[salt]/[acid]
.. (3)
The above equation is called as the Hendersons equation for acid buffer solution.
Base buffer solution: Similarly the Henderson equation for base buffer solution,
pOH = pKb + log[salt]/[base]
.. (4)
But
pH = 14 - pOH
Therefore, equation (4) become,
pH = 14 - {pKb + log[salt]/[base]}