Galvanic Cells
➢ Galvanic cells, half-cell reactions
➢ Nernst equation and electromotive force
➢ Measurement of emf. of cell
➢ Different types of electrodes: Standard hydrogen electrode,
Secondary reference electrode (calomel electrode, Ag-AgCl
electrode, Quinhydrone electrode)
➢ Liquid Junction Potential, Salt bridge
➢ Concentration cell
➢ Relation between thermodynamic quantity and emf
➢ Nernst equation for electrode potential in terms osmotic pressure and
solution pressure
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❑ Half Cell Reactions
❖ Let us consider the reaction
2 Na + Cl2 → 2Na+ + 2Cl –
❖ It occurs by the transfer of electrons from Na to Cl.
❖ Na loses an electron and is said to be oxidized to Na+ ion.
❖ At the same time, Cl gains an electron and is reduced to Cl– ion.
❖ Such a reaction which is brought about by loss of electrons (oxidation)
and gain of electrons (reduction) simultaneously, is called an Oxidation-
Reduction reaction or Redox reaction in brief.
❖ It may be noted that in the overall redox reaction no free electrons are
generated. The redox reaction can be considered as made up of two
reactions.
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❖ For example, the redox reaction 2Na + Cl2 → 2Na+ + 2Cl – is composed
of two half-reactions :
2Na → 2Na+ + 2e (oxidation)
Cl2 + 2e → 2Cl – (reduction)
❖ Each of the two reactions shows just its oxidation or just the reduction
portion of the overall redox reaction.
❖ Being half components of the redox reaction, these reactions are called
Half-reactions.
❖ The first half-reaction that proceeds by oxidation is often referred to as
the Oxidation half-reaction.
❖ The second half-reaction that occurs by reduction, is referred to as the
Reduction half-reaction.
❖ When the two half-reactions are added together, the sum is the net
redox reaction.
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❑ Voltaic Cells
A Voltaic cell, also known as a
galvanic cell is one in which electrical
current is generated by a spontaneous
redox reaction.
The spontaneous reaction of zinc metal
with an aqueous solution of copper
sulphate is used.
Figure: A simple voltaic (galvanic) cell
Zn + Cu2+ → Zn2+ + Cu
➢ A bar of zinc metal (anode) is placed in zinc sulphate solution in the left
container. A bar of copper (cathode) is immersed in copper sulphate solution
in the right container.
➢ The zinc and copper electrodes are joined by a copper wire. A salt bridge
containing K2SO4 solution interconnects the solutions in the anode
compartment and the cathode compartment.
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➢ The oxidation half-reaction occurs in the anode compartment.
Zn → Zn2+ + 2e
➢ The reduction half-reaction occurs in the cathode compartment.
Cu2+ + 2e → Cu
➢ When the cell is set up, electrons flow from zinc electrode through the
wire to the copper cathode. As a result, zinc dissolves in the anode
solution to form Zn2+ ions. The Cu2+ ions in the cathode half-cell pick up
electrons and are converted to Cu atoms on the cathode.
➢ At the same time, SO42- ions from the cathode half-cell migrate to the
anode half-cell through the salt bridge. Likewise, Zn2+ ions from the anode
half-cell move into the cathode half-cell.
➢ This flow of ions from one half-cell to the other completes the electrical
circuit which ensure continuous supply of current.
➢ The cell will operate till either the zinc metal or copper ion is completely
used up.
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❑ Standard Hydrogen Electrode
❖ The standard hydrogen half-cell or Standard Hydrogen Electrode (SHE), is selected
for coupling with the unknown half-cell.
❖ It consists of a platinum electrode immersed in a 1 M solution of H+ ions maintained
at 25°C. Hydrogen gas at one atmosphere enters the glass hood and bubbles over the
platinum electrode.
❖ The hydrogen gas at the platinum electrode passes into solution, forming H+ ions and
electrons.
H2 → 2H+ + 2e
The emf of the standard hydrogen electrode
is arbitrarily assigned the value of zero volts.
So, SHE can be used as a standard for other
electrodes.
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The half-cell whose potential is desired, is combined with the hydrogen
electrode and the emf of the complete cell determined with a voltmeter.
Ecell = ER - EL = 0 – 0.76 = – 0.76 V
The complete electrochemical cell may be represented as –
Zn | Zn2+ || H+ | H2 (1 atm), Pt
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❑ Limitations of standard hydrogen electrode
✓ It is difficult to maintain the pressure of hydrogen gas and concentration of HCl.
✓ It is difficult to get pure, dry hydrogen gas and prepare ideal platinized platinum plate.
✓ The gas has to be carefully controlled and hydrogen gas can form explosive mixtures
with air.
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Problem
❑ Predict whether the reaction -
2 Ag(s) + Zn2+ (aq) → Ag+ (aq) + Zn(s)
is feasible or not. The standard emf for half cell Ag | Ag+ and Zn2+ | Zn is 0.80 and -0.76
V respectively .
❑ Calculate the emf of the cell.
Zn | Zn2+ (0.001M) || Ag+ | Ag (0.1M).
The standard potential of Ag/Ag+ half-cell is + 0.80 V and Zn/Zn2+ is – 0.76 V.
Calculate the Equilibrium constant for the cell reaction.
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The Standard Ag - AgCl Electrode
➢ Ag wire (or strip) is covered with AgCl (a highly
insoluble substance).
➢ It is dipped in KCl solution in which [Cl–] = 1 M.
➢ This electrode can be represented as –
Ag, AgCl | Cl– (1 M)
The half-cell reaction of the Ag-AgCl
electrode is
AgCl + e → Ag + Cl–
We can set up a cell involving this electrode
and the hydrogen electrode
Pt , H2 | H+ (1 M) || AgCl, Ag | Cl– (1 M)
with a KCl salt bridge connecting the two
Figure: Schematic diagram of Ag-AgCl solutions. The emf of the combined cell is
electrode coupled with SHE (salt bridge found to be 0.2224 V. Thus the standard
replaced by porous partition). electrode potential for the silver-silver
chloride electrode is 0.2224 V.
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❑ The Calomel Electrode
✓ It is the most commonly used secondary standard reference electrode.
✓ The standard calomel electrode, SCE, consists of a wide glass-tube with a narrow
side-tube.
✓ A platinum wire is dipping into liquid Hg covered with solid Hg2Cl2 (calomel).
✓ The tube is filled with a 1 M solution of KCl (or saturated KCl solution).
✓ The side-tube containing KCl solution provides the salt bridge which connects
the electrode to any other electrode.
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The calomel electrode is represented as
Cl– (1M) | Hg2Cl2, Hg
and the half-cell reaction is
Hg2Cl2 + 2e → 2Hg + 2Cl–
The emf of the cell
Pt , H2 | H+ || KCl (1 M) | Hg2Cl2, Hg
at 25°C is + 0.280 V. That is, the calomel electrode emf with respect to the
standard hydrogen electrode is + 0.280 V. This means that 0.280 must be added
to any electrode potential measured against a calomel electrode.
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Quinhydrone Electrode: It is a widely used secondary standard electrode. It involves the
redox reaction between quinone (Q) and hydroquinone (QH2),
Q + 2H+ + 2e → QH2
✓ The hydroquinone half-cell consists of a Pt strip immersed in a
saturated solution of quinhydrone at a definite H+ ion concentration
(buffered solution).
✓ Quinhydrone is a molecular compound which gives equimolar amounts of Q and QH2 in
solution. The electrode system may be represented as Pt | QH2, Q, H+
✓ The potential developed is measured against a hydrogen electrode or calomel electrode.
✓ The emf with respect to a standard hydrogen electrode is 0.2875 V at 25°C.
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Determination of pH of a Solution
➢ A half-cell is set up with the test solution as electrolyte.
➢ The emf of the cell depends on the concentration of H+ ions or pH of the solution.
➢ The emf of the half-cell is determined by coupling it with another standard half-cell and
measuring the emf of the complete cell.
➢ The commonly used standard electrodes are :
i. The hydrogen electrode
ii. The calomel electrode
iii. The quinhydrone electrode
Pt | H2 (1 atm) | H + (1 M) || H + (Unknown) | H2 (1 atm) | Pt
Test Solution 1 M HCl
Figure: Determination of pH with Hydrogen electrode 15
Pt | H2 (1 atm) | H + (Unknown) || H + (1 M) | H2 (1 atm) | Pt
Reaction at anode: H2 → 2H + +2e Reaction at Cathode: 2H + +2e → H2
ER = 0
In reduction form: 2H + +2e → H2
EL = ELo – (RT/2F) ln ([H2]/[H+]2) Ecell = ER – EL
= 0 – (RT/2F) ln (1/[H+]2) = 0 – (– 0.0591 pH)
= (RT/F) ln [H+] = 0.0591 pH
= 2.303(RT/F) log [H+]
pH = Ecell / 0.0591
= – 2.303(RT/F) {-log [H+]}
= – 0.0591 pH
= – 0.0591 pH
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Determination of pH of a Solution by SCE Determination of pH of a Solution by
EL = – 0.0591 pH Standard Ag - AgCl Electrode
ER = 0.280 V EL = – 0.0591 pH
Ecell = ER – EL ER = 0.2224 V
= 0.280 – (– 0.0591 pH) Ecell = ER – EL
= 0.280 + 0.0591 pH = 0.2224 – (– 0.0591 pH)
pH = (Ecell – 0.0280)/0.0591 = 0.2224 + 0.0591 pH
pH = (Ecell – 0.2224)/0.0591
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Concentration Cells
✓ Cell potentials depend on concentration of the electrolyte.
✓ A cell can be constructed by pairing two half-cells, in which identical electrodes are
dipping in solution of different concentrations of the same electrolyte.
The concentration of Ag+ ions in the left
compartment is lower (0.1M) and in the right
compartment it is higher (1M). There is a natural
tendency to equalize the concentration of Ag+
ions in the two compartments. This can be done
if the electrons are transferred from the left
compartment to the right compartment. This
electron transfer will produce Ag+ ions in the
right compartment by the half-cell reactions :
Ag → Ag+ + e (left compartment)
Ag+ + e → Ag (right compartment)
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Emf of Concentration Cell
Suppose the concentrations in the two half-cells are C1 and C2 at 25°C, C2 being greater
than C1. Then emf, E, of the concentration cell will be given by the difference between the
two electrode potentials. In terms of Nernst equation
0 RT [Ag] 0 RT [Ag]
Ecell = (EAg - ln ) - (EAg - ln + )
nF [Ag+](c2) nF [Ag ](c1)
RT RT
Ecell = (EAg0 + ln [Ag+](c2)) - (EAg0 + ln [Ag+](c1))
nF nF
RT [Ag+](c2)
Ecell = ln
nF [Ag+](c1)
where EAg0 is the standard electrode potential of Ag and n is the valence of the ions in
contact with it. For example, the emf, E, of the concentration cell
Ag | Ag+ (c1) || Ag+ (c2) | Ag ; c2 > c1
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At Anode: M → Mn+ + ne (Oxidation)
Reaction in reduction form: Mn+ + ne → M
EAnode = E0Mn+/M – (RT/nF) ln ([M]/[Mn+] (c1)
= E0Mn+/M + (RT/nF) ln ([Mn+] (c1)/[M] Here, c2> c1
At Cathode: Mn+ + ne → M (Reduction)
ECathode = E0Mn+/M – (RT/nF) ln ([M]/[Mn+] (c2)
= E0Mn+/M + (RT/nF) ln ([Mn+] (c2)/[M]
ECell = ECathode – E Anode
= E0Mn+/M + (RT/nF) ln ([Mn+] (c2)/[M] - E0Mn+/M - (RT/nF) ln ([Mn+] (c1)/[M]
= (RT/nF) ln ([Mn+] (c2) - (RT/nF) ln ([Mn+] (c1)
= (RT/nF) ln {([Mn+] (c2) / ([Mn+] (c1)}
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❑ Laws of Osmotic Pressure
For dilute solutions :
(a) The osmotic pressure of a solution at a given temperature is directly
proportional to its concentration.
✓ If π is the osmotic pressure and C its concentration,
π ∝ C, when temperature is constant.
✓ If the concentration of the solute is expressed in moles per liter and V is
the volume of the solution that contains 1 mol of solute,
This relationship is similar to the Boyle’s law for gases and is known as
the Boyle-van’ t Hoff law for solutions.
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(b) The osmotic pressure of a solution of a given concentration is directly
proportional to the absolute temperature.
If T is the absolute temperature,
π ∝ T, if concentration is constant
This relationship is similar to the Charles’ Law for gases and is known
as Charles-van’t Hoff law for solutions.
Van’t Hoff Equation for Solutions
– As shown above the osmotic pressure (π) of a dilute solution is inversely
proportional to the volume (V) containing 1 mole of the solute and is
directly proportional to the absolute temperature (T).
Therefore,
π 1/V
πT
Combining (1) and (2) van’t Hoff gave the general relationship
π V = R’ T
where R’ is a constant.
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✓ He showed that this equation was parallel to the general Gas
Equation (PV = RT), as the value of R’ calculated from the
experimental values of π, V, and T came out to be almost the same as
of the Gas constant, R.
✓ It is noteworthy that the van’t Hoff Equation was derived for 1 mole
of solute dissolved in V liters.
✓ If n moles of solute are dissolved in V litres of solution, this
equation assumes the form
πV=nRT
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