NAME _______________________________SECTION____________

CHEM 1 ME Chemistry for Engineers

Problem Set 5. Standard Electrode Potentials of Electrochemical Cells

Learning Outcomes:

1. Describe the anode and cathode chemical reactions and relate to cell potentials
2. Calculate the cell potential (or voltage) and predict chemical redox spontaneity.
3. Describe the activity series of metals and relative strengths of redox reactions based on
standard reduction or oxidation potentials.

The reduction oxidation activity of electrochemical cells is quantified by measuring the potentials
(or voltage). In electrochemistry, energy accompanying the transfer of electrons is measured in
volt unit. A volt unit is one joule of energy per one coulomb of charge (V = J/C). An oxidation
half-reaction is always coupled with a reduction half-reaction. If there is a donor of electrons
there must be an acceptor. A half-cell potential cannot be measured alone. The standard
potential of an electrode is measured relative to the standard hydrogen electrode (SHE),
assigning zero potential for hydrogen:

Standard Hydrogen Electrode when coupled with a less active metal, the SHE can serve as an anode.
Anode oxidation half-reaction: H2 (g) → 2H+ (aq) +2e– E° = 0.00 volts
Cathode reduction half reaction: Cu2+(aq) +2e– → Cu(s) E° = +0.34 volts

The table below shows some selected values of standard reduction potential of elements taken
from scientific publications of Chemical and Physical Data, such as yearly publication of CRC
Handbook of Chemistry and Physics. Most tables show the standard reduction potentials in unit
of volts. Some tables show oxidation potentials. The metal oxidation-reduction reactions are
reversible depending which couple of electrodes are used. The activity series of metals are
listed from the most reactive Group 1 and 2 metals followed by Group 13 (aluminum), some
Transition metals and Group14 metals (Sn and Pb). Metals listed below hydrogen, such as
copper, silver, platinum, gold, etc. are less reactive so that their cations are reduced by more
reactive metals above them in the series.

To predict spontaneity of oxidation- reduction reaction of metals, use the standard oxidation-
reduction potentials. The anode is the metal which has higher oxidation potential and the
cathode is the metal with lesser oxidation potential ( or high reduction potential). Calculate the
sum of their oxidation-reduction potentials to obtain the total electrode potential of the cell, E 0
cell.
 When E0 cell potential is positive, chemical oxidation-reduction is spontaneous
“Electrons flow from a high potential to a lower potential”.
 Electricity can be generated by the galvanic or voltaic cell.
 The magnitude of E0 cell relates to the voltage of the galvanic cell.

When the E0 cell potential is negative, oxidation-reduction is not spontaneous. Reverse the
anode to cathode to make a spontaneous oxidation reduction reaction in galvanic cell.When the
E0 cell is negative, electricity is required to make the chemical oxidation-reduction reaction
possible such as in an electrolytic cell. In secondary cells (such as reversible battery),
electricity input reverses the reaction and restore chemical energy in the cell.
In galvanic or voltaic cell, oxidation half-reaction occurs at the anode (negative electrode) and
the reduction half-reaction occurs at the cathode (positive electrode). To write the
electrochemical notation, write the anode components at the left and cathode components at
the right. At the anode, write the metal electrode and use a single vertical line that separate the
aqueous solution. A double vertical line separates the cathode solutions and the single vertical
line separates the metal electrode. The concentration of the solutions are not written when in
standard state, 1 M ( M=mole/Liter) at 250C and 1 atm pressure. Otherwise, concentration is
specified in the electrochemical notation.

Example1: Interpret the electrochemical notation: Cu(s)│ Cu2+(aq) ││Ag+ (aq) │ Ag(s)
The copper metal electrode is the anode dipped in Cu 2+ aqueous solution (usually copper (II)
nitrate which is very soluble in water). In the anode, Ag+ aqueous solution is used and the metal
electrode is silver.

Write the oxidation half-reaction at the anode and reduction half reaction at the cathode.

Electrode Type of Reaction Half-Reaction Potential E0( volts)

Anode oxidation Cu(s) → Cu2+(aq) +2e– –0.34
Cathode reduction Ag+ (aq) +e– → Ag (s) + 0.80
Cu(s + 2 Ag+ (aq → Cu2+(aq) + 2 Ag (s) E0 cell = + 0.46 V

Balance the net equation by balancing the number of electrons lost in the anode and electrons
gained in the cathode:
Anode oxidation half reaction: Cu(s) → Cu2+(aq) +2e– 2 electrons lost
Cathode reduction half reaction: 2( Ag+ (aq) +e– → Ag(s) ) multiply by 2
2 Ag+ (aq) +2e- → 2 Ag(s)

Net equation is the sum of two reactions: Cu(s + 2 Ag+ (aq → Cu2+(aq) + 2 Ag (s) E0cell = +0.46 V
When the net electrode potential of the electrochemical cell is positive, the reaction is
spontaneous. This galvanic cell can produce electricity.

Example 2. Write the electrochemical notation given the description of the electrochemical cell
and calculate the cell potential, E0cell, to determine whether the redox is spontaneous or not.

The aqueous solution of Sn4+ in Platinum electrode is reduced to Sn2+, while the zinc metal
electrode is oxidized to Zn2+ in aqueous solution.

Anode oxidation half-reaction: Zn(s) → Zn 2+(aq) +2e– E0 = +0.76

Cathode reduction half-reaction: Sn4+(aq) +2e– → Sn2+(aq) E0 = +0.15
Cell net reaction Zn(s) + Sn4+(aq) → Zn 2+(aq) + Zn 2+(aq) E0cell = +0.91 spontaneous

Electrochemical notation: Zn(s) │Zn2+(aq) ║ Sn4+(aq), Sn2+(aq)│Pt(s)

Note: Reduction of Sn4+(aq) to Sn2+(aq) occurs in aqueous solution. These are written
separated by comma then separated from the Pt metal by single vertical line. The cathode is a
Platinum metal that is inert which passes on the electrons to Sn4+(aq).
Complete the table by writing the oxidation half-reactions and corresponding standard oxidation
potential of the selected elements and their ions. Keep the table for next Problem Sets.
Table 2 . Standard Electrode Reduction and Electrode Oxidation Potentials in Aqueous
Solution at 250C of Selected Elements

ELEMEN REDUCTION HALF- Reduction OXIDATION HALF- OXIDATION

T REACTION E0(volt) REACTION E0(volt)
Li Li+ (aq)+ e– → Li (s) –3.05 Li (s) → Li+ (aq)+ e– +3.05
K K+ (aq) + e– → K (s) –2.93 K (s) → K+ (aq) + e– +2.93
Ba Ba2+ (aq) +2e– → Ba (s) –2.90 Ba(s) → Ba2+ (aq) +2e– + 2.90
Ca Ca2+(aq) +2e– → Ca(s) –2.87 Ca(s) → Ca2+(aq) +2e– + 2.87
Na Na+ (aq) +e– → Na (s) –2.71 Na (s) → Na+ (aq) +e– +2.71
Mg Mg2+ (aq) + 2e– → Mg(s) –2.37 Mg(s) → Mg2+ (aq) + 2e– +2.37
Al Al3+ (aq) + 3e– → Al(s) –1.66 Al(s) → Al3+ (aq) + 3e– +1.66
Zn Zn 2+ (aq) +2e– → Zn(s) –0.76 Zn(s) → Zn 2+ (aq) +2e– +0.76
Cr Cr3+ (aq) +3e– → Cr (s) –0.74 Cr (s) → Cr3+ (aq) +3e– +0.74
Fe Fe2+ (aq) +2e– → Fe (s) –0.44 Fe (s) → Fe2+ (aq) +2e– +0.44
Cd Cd2+(aq) + 2e– → Cd(s) –0.40 Cd(s) → Cd2+(aq) + 2e– +0.40
Co Co2+ (aq) +2e– → Co(s) –0.28
Ni Ni2+(aq) +2e– → Ni(s) –0.25
Sn Sn2+(aq) +2e– → Sn(s) –0.14
Pb Pb2+ (aq) +2e– → Pb(s) –0.13
H2 2H+ (aq) +2e– → H2 (g) 0.00 H2 (g) → 2H+ (aq) +2e– 0.00
Sn Sn4+(aq) +2e– → Sn2+(aq) +0.15
Cu Cu2+(aq) +2e– → Cu(s) +0.34 Cu(s) → Cu2+(aq) +2e– –0.34
I2 iodine I2 (s) + 2e– → 2I– (aq) +0.54
Fe Fe3+(aq) +e– → Fe2+(aq) +0.77
Hg Hg2+(aq) +2e– → Hg(ℓ) +0.79
Ag Ag+ (aq) +e– → Ag(s) +0.80 Ag(s) → Ag+ (aq) +e– -0.80
Br2 Br2 (ℓ) +2e– → 2Br– (aq) +1.08
Cl2 Cl2 (g) +2e– → 2Cl– (aq) +1.36
Au Au3+(aq) +3e– → Au(s) +1.42
Au Au+(aq) + e– → Au(s) +1.68
F2 F2 (g) +2e– → 2F– (aq) +2.57 2F– (aq) → F2 (g) +2e– –2.57

Name _________________________ Section ______________ due date September 16, 2020

Chem 1 ME Problem Set 5
1. Interpret the following electrochemical cell notations and calculate the cell potentials:

a. Ni(s) │ Ni2+(aq) ││ Ag+(aq) │ Ag (s)

b. Fe (s) │Fe2+(aq) ││ Cu2+(aq) │Cu (s)

c. Cd(s) │ Cd2+(aq) ││ Pb2+(aq) │ Pb(s)