ELECTROCHEMISTRY

GALVANIC CELL

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Lecture outline
Basic principle of Galvanic Cell
Cell notation
Quantitative aspects:
Electroanalytical cell: determination of total
voltage needed in the redox reaction

Standard electrochemical potentials, emf

(same concentration of the electrolyte)
Nonstandard electrochemical cells: Nerst Equation
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 Recall and comparison:
• Electrolysis
• conversion of electrical energy to chemical
energy.
(when electrical energy is supplied
externally)
• Non spontaneous redox reactions and
require an external current in order to force
the reaction to proceed.
• anode electrode : oxidation will occur
(positive electrode)
• cathode electrode: reduction will occur.
(negative electrode)
DRY CELL … or Leclanchè battery cell --- George
Leclanchè (1865)
• Galvanic Cell
• conversion of chemical energy to electrical
energy.
• a spontaneous redox reaction occur to
create a flow of electrons.
• anode electrode : oxidation will occur
(negative electrode)
• cathode electrode: reduction will occur.
(positive electrode)
• the energy released (potential) in a
spontaneous redox reaction is used to
perform electrical work.
• Lead Storage battery cell…… Daniell Cell
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 ELECTROCHEMICAL CELLS
Components of Galvanic cell:
The instrument consist of :
two (2) electrodes: anode & cathode
(metallic conduction)
electrolyte container

electrolyte solution

external source/circuit

***salt bridge : for Galvanic cell

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 Galvanic/Voltaic/Daniel Cell:
Galvanic Consist of :
• Electrodes : anode (oxidation reaction) and cathode
(reduction reaction)
• Electrolyte solution : used for oxidation and reduction in
the electrodes.
• Salt bridge : used to complete the electrical circuit and to
neutralize the solution.
• External circuit : electrons flow and are transported from
the anode to the cathode passing into a voltmeter.
• Voltmeter : to indicate the flow of current.
MOVEMENTS OF ē : from anode to the cathode. 6
Example:

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Application:

Discover How Car Batteries Work.flv

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 Lead-Acid Battery (wet cell)

A 12 V car battery consists

of 6 cathode/anode pairs each producing 2 V.
• Anode: Pb (oxidation)
• Cathode : PbO 2 (reduction)
• Electrolyte solution :
H 2SO 4 , battery solution
• Separator : glass-fiber spacers or wood are
used to prevent the electrodes from
touching.

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 Lead – acid battery cell (wet cell)
• Anode: oxidation half – reaction … Pb reacts with
sulfate ions from sulfuric acid

Pb(s) + SO42-(aq)  PbSO4(s)

Pb(s) + SO42-(aq)  PbSO4(s) + 2e-

• Cathode: reduction half –reaction : PbO2 on a metal

grid;
reacts with sulfate ion from sulfuric acid:
PbO2(s) + SO42-(aq)  PbSO4(s)
PbO2(s) + SO42-(aq) + 4H+(aq)  PbSO4(s) + 2H2O(l)
PbO2(s) + SO42-(aq) + 4H+(aq) + 2e-  PbSO4(s) + 2H2O(l)
Overall reactions??????

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Galvanic Cell: consider the spontaneous redox reaction between
Zn (s) and Cu 2+(aq)
During the reaction:
Anode: oxidation half – reaction:
Zn(s)  Zn2+ (aq)
Zn(s)  Zn2+ (aq)+ 2ē

Cathode: reduction half – reaction:

Cu2+  Cu (s)
Cu2+ + 2 ē  Cu(s)
Overall reaction???
The entire process is spontaneous….
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 Cell notation : Principle
• shorthand way of expressing/representing a reaction in an electrochemical cell:
anode cell- oxidation reaction and the cathode cell- reduction
• physical states of the substances must be included in writing the cell notation.
• anode half – cell is on the left side:
bar is used to separate the reactant and product reaction.

• cathode half – cell is on the right side:

bar is used to separate the reactant and product reaction.

• anode and cathode (half-cells) are separated by two bars or slashes representing a
salt bridge.

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 Cell notation:

reactant side product side reactant side product side

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Cell notation:
Types of electrodes and rules:
1. Active electrodes
2. Inactive (inert) electrode

NOTE: Generally: more active metals will oxidize and less active metal will
reduce…..
Activity series of metal: Li, K, Ba, Ca, Na, Mg, Al, Zn, Fe, Cd, Ni, Sn, Pb, (H),
Cu, Hg, Ag, Au

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Cell notation:
Types of electrodes and rules:
1. Active electrodes – electrodes are the metals of electrolyte solution

Salt bridge

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 Cell notation:
Types of electrodes and rules:
2. Inactive (inert) electrode – metals of
electrolyte solution is not involved in the
electrode half-reaction (inert solid
conductors served as the contact between
solution and the external electrical circuit.

Zn(s) / Zn2+ (aq) // H+ (aq) / H2 (g) / Pt (s)

anode cathode platinum

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Cell notation:
Types of electrodes and rules:
3. For concentration of 1 M it is not included in the cell notation.

Zn(s) / Zn 2+(aq) // Cu 2+ (aq) / Cu (s)

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 Cell notation:
Types of electrodes and rules:
4. If concentration is given (other than 1 M) then it is written in the cell notation.
Example:
Concentration of Zn 2+ (aq) = 0.1 M Concentration of Cu 2+ (aq) = 1 M
Zn(s) / Zn 2+(aq, 0.1 M) // Cu 2+ (aq) / Cu (s)

Concentration of Zn 2+ (aq) = 1.5 M Concentration of Cu 2+ (aq) = 2.0 M

Zn(s) / Zn 2+(aq, 1.5 M) // Cu 2+ (aq, 2.0 M) / Cu (s)

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Cell notation:
Types of electrodes and rules:
5. If there are two or more substances involve in the oxidation and/or
reduction half reactions; separate the substances by a comma.
Oxidation reaction at the anode: H 2O(l)  O 2(g) + H +(aq)
Reduction reaction at the cathode: H2O(l)  H2(g) + OH – (aq)
Cell notation:
H 2O(l)/ O 2(g) , H +(aq) // H2O(l) /H2(g) ,OH – (aq)

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 Cell notation: Active electrodes
Active electrodes – involved in the electrodes half- Answers: chemical reactions
reaction are the metals of electrolyte solution.
Oxidation reaction:
1. Write the overall equation and the cell Zn(s)  Zn 2+ (aq)
notation of the given diagram : Zn(s)  Zn 2+ (aq) + 2ē
Reduction reaction:
In the chemical reaction: Cu 2+ (aq)  Cu(s)
• Write the balance oxidation reaction.
2ē + Cu 2+ (aq)  Cu(s)
• Write the balance reduction reaction. overall reaction: (cancel spectator substances)
• Write the overall reaction.
Zn(s)  Zn 2+ (aq) + 2ē
In the cell notation:
2ē + Cu 2+ (aq)  Cu(s)
• anode compartment.
-------------------------------------------------
• cathode compartment.
Zn(s) + Cu 2+ (aq)  Zn 2+ (aq) + Cu(s)
• salt bridge

Cell notation:
Zn(s) / Zn 2+ (aq) //Cu 2+ (aq) / Cu(s) 21
 Example: active electrodes
2. Write the oxidation and reduction half-reaction and the overall reaction of the given cell
notation:
Al (s) / Al 3+ (aq) // Pb 2+ (aq) / Pb (s)
Oxidation reaction: Reduction reaction:
Al (s)  Al 3+ (aq) + 3ē 2ē + Pb 2+ (aq)  Pb (s)
Balance the electrons:
(Al (s)  Al 3+ (aq) + 3ē) 2 3(2ē + Pb 2+ (aq)  Pb (s))
2 Al (s)  2 Al 3+ (aq) + 6ē 6ē + 3 Pb 2+ (aq)  3 Pb (s)
Overall reactions:
2 Al (s)  2 Al 3+ (aq) + 6ē
6ē + 3 Pb 2+ (aq)  3 Pb (s)
-------------------------------------------------------------------------

2 Al (s) + 3 Pb 2+ (aq)  2 Al 3+ (aq) + 3 Pb (s)

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Example: active electrodes
3. Write the cell notation of the given equation:
2 Ag(s) + Cu 2+ (aq)  2 Ag + (aq) +Cu (s)

Ag(s) / Ag +(aq) // Cu 2+ (aq) / Cu (s)

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 Example: active electrodes
4. Draw the Galvanic cell diagram and write a cell notation for a voltaic cell
that consists of one half-cell with a silver bar in a silver nitrate solution,
AgNO3 and another half-cell with a copper bar in copper (II) nitrate solution,
Cu(NO3)2 and a potassium nitrate,KNO3 use as a salt bridge solution.
Measurements indicate that the copper electrode is negative in relative to
the silver electrode.
Anode: oxidation : Cu (s)  Cu 2+(aq) + 2e
Cathode : reduction: [ 1 e +Ag+ (aq) Ag(s) ]2
2 e + 2Ag+ (aq) 2 Ag(s)
overall reaction: Cu (s) + 2Ag+ (aq)  Cu 2+(aq) + 2 Ag(s)
Cu (s)/ Cu 2+(aq)// Ag+ (aq) Ag(s) 24
Example : active electrodes
5. A galvanic cell consists of a chromium, Cr bar in a chromic sulfate
solution, Cr2(SO4)3 and a silver, Ag bar in a silver sulfate solution, Ag2SO4
and a sodium sulfate solution use as a salt bridge solution. The silver
electrode is positive relative to the chromium electrode. Sketch the
galvanic cell diagram and write the cell notation.

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 Lead – acid battery cell: active
electrodes
6. Write the overall reaction and cell notation of the given half reactions:
• Anode: oxidation half – reaction … Pb reacts with sulfate ions from sulfuric acid
Pb(s) + SO42-(aq)  PbSO4(s)
Pb(s) + SO42-(aq)  PbSO4(s) + 2e-

• Cathode: reduction half –reaction : PbO2 on a metal grid;

reacts with sulfate ion from sulfuric acid:
PbO2(s) + SO42-(aq)  PbSO4(s)
PbO2(s) + SO42-(aq) + 4H+(aq)  PbSO4(s) + 2H2O(l)
PbO2(s) + SO42-(aq) + 4H+(aq) + 2e-  PbSO4(s) + 2H2O(l)

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Additional exercises:
Write the cell notation of the given reaction: (assume: using active electrodes)
1. Ag +(aq) + Mg(s)  Mg 2+ (aq) + Ag (s)
2. Pb2+(aq) is displaced from solution by Al
3. Ca (s) + Ni2(SO4)3(aq)  CaSO4(aq) + Ni(s)

Write the half-reactions and overall reactions of the following given cell notation. (active
electrode)
1. Ba (aq) / Ba2+ (s) // Cu2+ (s) / Cu (aq)
2. Al(s) / Al3+(aq) // Sn2+(aq) / Sn(s)
3. Cd (s) / Cd2+ (aq) //Ag+ (aq) / Ag (s)

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 Cell notation: inactive electrode/s
Inactive (inert) electrode – metals of • Oxidation:

electrolyte solution is not involved Zn(s)  Zn 2+ (aq)

Zn(s)  Zn 2+ (aq) + 2ē
in the electrode half-reaction (inert • Reduction:
solid conductors served as the H+(aq) +  H 2(g)

contact between solution and the 2 H+(aq) +  H 2(g)

2 H+(aq) + 2ē  H 2(g)
external electrical circuit. • Overall reaction:

1. Write the overall equation and Zn(s)  Zn 2+ (aq) + 2ē

2 H+(aq) + 2ē  H 2(g)
the cell notation of the given ---------------------------------------------
diagram Zn(s) +2 H+(aq)  Zn 2+ (aq) + H 2(g)

• Cell notation:
Platinum
as electrode in the Zn /Zn2+ // H+/ H2 /Pt (s)
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cathode electrode
 Example:
2. Write the cell notation of the given reaction using a platinum solid as
electrode in the reduction reaction.
Cu(s) + 2 Fe +3(aq)  Cu+2(aq) + 2 Fe+2(aq)

Cu(s) /Cu+2(aq) // Fe +3(aq) / Fe+2(aq) /Pt(s)

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Additional exercises:
Write the oxidation and reduction half reactions and overall reaction of the
following cell notation:
1. Fe(s) / Fe+3(aq) // Cl2(g) / Cl – (aq) / Pt
2. Zn(s) / Zn2+(aq) // O2(g) , H+(aq) / H2O(l) / Pt(s)
3. Pt(s) / H2(g) / H+(aq) // Ag+(aq) /Ag(s)
Write the cell notation of the given overall reaction:
1. 2 K (s) + 2H2O(l)  2K +(aq)+ 2 OH –(aq) + H2(g) (platinum electrode is in
cathode electrode)

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Additional exercises:
Draw the cell notation of the given reaction: (assume: using active electrodes)
1. Ag +(aq) + Mg(s)  Mg 2+ (aq) + Ag (s)
2. Pb2+(aq) is displaced from solution by Al
3. Ca (s) + Ni2(SO4)3(aq)  CaSO4(aq) + Ni(s)

Write the half-reactions and overall reactions of the following given cell notation. (active
electrode)
1. Ba (aq) / Ba2+ (s) // Cu2+ (s) / Cu (aq)
2. Al(s) / Al3+(aq) // Sn2+(aq) / Sn(s)
3. Cd (s) / Cd2+ (aq) //Ag+ (aq) / Ag (s)

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Problems:
I. Draw the cell notation of the given reaction:
1. Ag +(aq) + Mg(s)  Mg 2+ (aq) + Ag (s)
2. I2 (s) + Cl –1 (aq)  Cl2 + I –1(aq) (using platinum electrode in both compartment of the cell)
3. Ca (s) + Ni3+(aq)  Ca2+(aq) + Ni(s)
4. MgBr2(aq) is produced from Mg(s) and Br2(l) (using platinum electrode at the anode cell)

II. Write the half-reactions and overall reactions of the following given cell notation.
1. Mg(s) / Mg2+(aq) // Hg+(aq) / Hg(s)
2. Al(s) / Al3+(aq) // Sn2+(aq) / Sn(s)
3. Ba(s) / Ba+2(aq) / F2(g) / F –(aq) / Pt
4.Na(s) / Na+(aq) // Al3+(aq) / Al(s)
5. Cd (s) / Cd2+ (aq) // Pb+2 (aq) / Pb (s)
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6. Pt(s) /H2(g) / H+ (aq) // Au+3 (aq) / Au(s)
QUANTITATIVE ASPECTS OF
ELECTROANALYTICAL CELLS
Based on the measurement of:
• the current in the electrochemical cell at a fixed electrode potentials.

• the electrode potential of a cell while the current is fixed at some

constant level.

• Voltage of the cell can be determined.

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Example:

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Electrode potentials determination.
• Standard electrochemical potentials, emf
(same concentration of the electrolytes)
emf --- electromotive force
• Nonstandard electrochemical cells: Nernst Equation
(different concentration of the electrolytes)

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 ELECTRODE POTENTIAL, emf
Electromotive force, emf
• It is the electrical potential due to the tendency of the ions to give off
and take in electrons. (in volts)

• The standard, E 0 electrode potential of a cell (E 0 cell) can be calculated

from standard hydrogen electrode (SHE)
E 0 cell = E cathode + E anode

• Convenient tabulation of electrochemical data.

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 ELECTRODE POTENTIAL
• Standard Hydrogen Electrode (SHE)

• Reduction Half-reaction value

• For oxidation Half-reaction value reverse the sign

• The more positive the electrode potential, the stronger

the oxidizing agent (easily reduced).

• The more negative the electrode potential the weaker

the oxidizing agent (stronger reducing agent …. easily
oxidized)

• A positive E 0 of the cell (E 0 cell ) indicates a

spontaneous process, galvanic cell.

• A negative E 0 of the cell (E 0 cell ) indicates a non

spontaneous process, electrolytic cell 39
 STANDARD HYDROGEN ELECTRODE
(SHE)
• The SHE is the cathode. It consists of
a Pt electrode in a tube placed in 1 M
H+ solution. H2 is bubbled through
the tube.
For the SHE :
• 2H+(aq, 1M) + 2e-  H2(g, 1 atm)

• E  reduction value is zero. From the

table
platinum

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ELECTRODE POTENTIALS (emf, cell voltage, standard cell difference)
Electrode potential for a reaction: E 0 cell = E cathode + E anode

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 ELECTRODE POTENTIALS, emf
Example:
1. Zn(s)/ZnSO4(aq, 0.0100M) // CuSO4(aq, 0.0100M) /Cu(s)
OR
Zn(s)/Zn2+(aq, 0.0100M)// Cu2+(aq, 0.0100M)/Cu(s)

Anode: Zn(s)  Zn2+ (aq)+ 2e-

2e + Zn 2+  Zn(s) --------- (reduction half- rxn., emf = - 0.76V)
but the reaction is oxidation which is a reverse reaction then the value becomes …. +0.76 V
Cathode: Cu2+ + 2e-  Cu(s) -------- +0.34 V

• From the table of standard electrode potential

E 0 cell = E cathode + E  anode
= + 0.34 + (+ 0.76)
= + 1.10 V spontaneous , galvanic cell 42
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Electrode potential of dry cell battery
Example:
2. Anode: Zn cap: Zn(s)  Zn2+(aq) + 2e-
Cathode: MnO2, NH4Cl and C paste:
2NH4+(aq) + 2MnO2(s) + 2e-  Mn2O3(s) + 2NH3(aq) + 2H2O(l)
From the table:
Anode: Zn(s)  Zn2+(aq) + 2e- 0.76 V
Cathode:
2NH4+(aq) + 2MnO2(s) + 2e-  Mn2O3(s) + 2NH3(aq) + 2H2O(l) 0.74 V

-------------------
1.5 V
E0 cell = E0 reduction + E0 oxidation 44
 Example:
3. Calculate the cell voltage of the given reaction, indicate if it spontaneous or non spontaneous, galvanic cell or electrolytic cell and
write the cell notation.
A) Ag + (aq) + Fe2 + (aq)  Ag (s) + Fe 3+ (aq)
cathode reaction: 1 ē + Ag + (aq)  Ag (s) + --------- from the table, emf value = + 0.80 V
anode reaction: Fe 2 + (aq)  Fe 3+ (aq) + 1 ē ---------- from the table, emf = + 0.77 V (reduction)
since it is a reverse reaction the emf value = – 0.77 V
E0 cell = E0 cathode + E0 anode
= + 0.80 V + (-0.77 V) = + 0.03V
it is a positive emf therefore it is spontaneous and galvanic cell
cell notation: Fe2 + (aq) /Fe 3+ (aq) // Ag + (aq) / Ag (s)
B) Ag (s) + Fe 3+ (aq)  Ag + (aq) + Fe2 +(aq)
cathode reaction: 1 ē + Fe 3+ (aq)  Fe2 +(aq) ------------- from the table, mf value = + 0.77 V
anode reaction: Ag (s)  Ag + (aq) + 1 ē ----------------- from the table, emf value = + 0.80 V (reduction)
since it is a reverse reaction the emf value = – 0.80 V
E0 cell = E0 cathode + E0 anode
= + 0.77 V + (- 0.80V) = – 0.03 V
it is a negative emf therefore it is nonspontaneous and electrolytic cell
cell notation: Ag (s) / Ag + (aq) // Fe 3+ (aq) / Fe2 +(aq) 45
 Example:
4. What is the standard potential of the cell represented below:
Pt / H2 (g) / H+(aq) // Cu2+(aq) / Cu(s)
Determine the cathode and anode half – reactions
Determine the overall reaction. Indicate if is spontaneous or nonspontaneous; galvanic cell or electrolytic cell
Cathode reaction: 2ē + Cu2+(aq)  Cu(s) -------- from the table, emf value = 0.34 V
Anode reaction: H2 (g)  2 H+(aq) + 2ē ------- from the table, emf value = 0 (reduction)
E0 cell = E0 cathode + E0 anode
= + 0.34 V + 0
= + 0.34 V
it is a positive emf, therefore it is spontaneous and galvanic cell.
Overall reaction:
2ē + Cu2+(aq)  Cu(s)
H2 (g)  2 H+(aq) + 2ē
----------------------------------------------------------------

Cu2+(aq) + H2 (g)  Cu(s) + 2 H+(aq) 46

Example:

5. From the given equation :

Write the cell notation ( using platinum in positive electrode), calculate the
electrode potential of the reaction:
O2(g) + 4H+(aq) + 2 Zn(s)  2H2O(l) + 2 Zn2+(aq)

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 Example: active electrodes
6. Draw the Galvanic cell diagram and write a cell notation for a voltaic cell
that consists of one half-cell with a silver bar in a silver nitrate solution,
AgNO3 and another half-cell with a copper bar in copper (II) nitrate solution,
Cu(NO3)2 and a potassium nitrate,KNO3 use as a salt bridge solution.
Measurements indicate that the copper electrode is negative in relative to
the silver electrode. Calculate the electrode cell potential.

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Example:
7. A galvanic cell consists of a chromium, Cr bar in a chromic sulfate
solution, Cr2(SO4)3 and a silver, Ag bar in a silver sulfate solution, Ag2SO4
and a sodium sulfate solution use as a salt bridge solution. The silver
electrode is positive relative to the chromium electrode. Sketch the
galvanic cell diagram. Write the cell notation. Calculate the electrode cell
potential.

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 Additional exercises:
I. Draw the cell notation of the given reaction and compute the electrode
potential of the cell:
1. Ag +(aq) + Mg(s)  Mg 2+ (aq) + Ag (s)
2. I2 (s) + Cl –1 (aq)  Cl2 + I –1(aq) (using platinum electrode in both compartment of the cell)
3. Br2(l) + Fe+2(aq)  FeBr3(aq) (using platinum electrode at the anode cell)
4. Pb2+(aq) is displaced from solution by Al
5. MgBr2(aq) is produced from Mg(s) and Br2(l) (using platinum electrode at the anode cell)
6. Cl2(g) is reduced to Cl –1 (aq) and Fe(s) is oxidized to Fe2+(aq)
(using platinum electrode at the reduction half-reaction)
7. Ag+ (aq) + Fe +2 (aq)  Ag(s) + Fe +3 (aq)

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Problems:
I. Draw the cell notation of the given reaction and calculate the E 0 cell
1. Ag +(aq) + Mg(s)  Mg 2+ (aq) + Ag (s)
2. I2 (s) + Cl –1 (aq)  Cl2 + I –1(aq) (using platinum electrode in both compartment of the cell)
3. Ca (s) + Ni3+(aq)  Ca2+(aq) + Ni(s)
4. MgBr2(aq) is produced from Mg(s) and Br2(l) (using platinum electrode at the anode cell)

II. Write the half-reactions and overall reactions of the following given cell notation. Compute the
electrode potential.
1. Mg(s) / Mg2+(aq) // Hg+(aq) / Hg(s)
2. Al(s) / Al3+(aq) // Sn2+(aq) / Sn(s)
3. Ba(s) / Ba+2(aq) / F2(g) / F –(aq) / Pt
4.Na(s) / Na+(aq) // Al3+(aq) / Al(s)
5. Cd (s) / Cd2+ (aq) // Pb+2 (aq) / Pb (s)
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6. Pt /H /H +
// Au +3
/ Au