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Electrochemistry: Physical Chemistry
Electrochemistry: Physical Chemistry
Physical Chemistry
Daniel Cell
1. Electrochemistry is the study of the interconversion of electrical and
chemistry energy.
2. Voltaic cell, in which a spontaneous reaction generates electrical energy.
3. Electrolytic cell: electrical energy is used to bring about a non spontaneous
reaction.
Solution:
a) Cathode: Cl2 + 2e 2Cl- Anode: 2Br- Br2 + 2e
b) From anode to cathode
c) Anion to anode, cations to cathode
Writing Redox Equation
Oxidation Number
Determine the oxidation number of the underlined atom:
a) V2O5
b) SO42--
c) SO32-
d) OCl-
e) HCO3-
f) MnO4-
Changes in Oxidation Number
1. xA + yB Product
x(+a) + y(-b) = 0
Practice:
1. What are the oxidation numbers of KIO3, KIO, Na2SO3 and Na2SO4. Thus,
balance the equation.
xKIO3 + y Na2SO3 cKIO + d Na2SO4
2. ClO3- + 6e Cl-
2I- I2 + 2e
Mg2+ / Mg -2.37
Zn2+ / Zn -0.76
Cu2+ / Cu +0.34
Ag+ / Ag +0.80
Practice
1. Consider the following equilibrium involving I2 and Fe3+:
I2 + 2e 2I- EӨ = +0.54 V
Fe3+ + e Fe2+ EӨ = +0.77 V
a) Write the ionic equation for the overall cell reaction.
b) State the observation after the half cell have been connected for a short
while.
c) Determine the polarity of the electrode in the electrochemical cell.
Solutions
a) 2Fe3+ + 2I- 2Fe2+ + I2
b) The beaker on the right (Fe3+) : yellow to green
The beaker on the left (I-) : yellow to brown
c) I2 + 2e 2I- is anode cause oxidation happen.
to construct the cell
The electrochemical Series
1. The electrochemical series shows the ease of a species accept or loses
electrons.
2. The higher a species the easier it loses electron (oxidized)
3. The EӨ value shows the possibility of a reaction but not the quantity of
substances involved.
4. If EӨ for I2 + 2e 2I- +0.54 V, then ½ I2 + e I- not (1/2 x 0.54V) but is
+0.54V.
5. The reactivity of metals increases as the electrode potential become more
negative while the reactivity if non metal increases as the electrode
potential become more positive.
6. The strength of oxidizing agents increases on descending the series while
the strength of reducing agents increases on ascending the series.
Practice
1. Arrange the following substances in the ascending order of their
oxidizing strength:
a) Na, Cl2, Cu
b) Zn, Ag+, Ag
c) Cl2, Br2, Br-
Br2 is able to oxidize I- into I2 but cannot oxidize Cl- into Cl2
Predicting the Possibility of Redox Reaction.
1. The possibility of a spontaneous reaction occurring can be predicted by
using:
a) EӨ value for the overall reaction
Hints:
Mg2+ + 2e Mg EӨ = -2.38 V
Sn2+ + 2e Sn EӨ = -0.14 V
--------------------------------------------------------------------
Cr2O72- + 14H+ + 6e 2Cr3+ + 7H2O EӨ = +1.33 V
Cl2 + 2e Cl- EӨ = +1.36 V
Predicting the Stability of Aqueous Ions
1. The relative stability of Cr and Cr2+ can be explain as follow:
Cr2+ + 2e Cr EӨ = -0.91 V
2H+ + 2e H2 EӨ = 0.00 V
-------------------------------------------------------
Cr + 2H+ Cr2+ + H2 EӨ = + 0.91V
-------------------------------------------------------
2. This implies that Cr2+ is more stable than Cr because the forward reaction
can occur spontaneously.
3. The Co3+ ion can be stabilized in aqueous solution by complexing it with
other ligands like ammonia.
The Nernst Equations
1. The value of the electrode potential depends on:
a) The concentration of the ion and the temperature of the
solution
b) The pH value (acidity) of the solution
c) The effect of complex formation.
For the electrode system:
oxidized species + ne reduced species
E = EӨ - 0.059/n {lg Q}
If the concentration of Cu2+ ions in the copper half cell is reduced, the ECu is
less than EӨ and the emf of the electrochemical cell increases.
If the concentration of Cu2+ ions in the copper half cell is reduced, the
equilibrium will shift to the right.
The Nernst Equation and Solubility Product
1. When a silver electrode is immersed into a saturated silver chloride
solution, the electrode potential at 298 K is 0.51 V. Calculate the solubility
product of silver chloride at 298 K. EӨ Ag+/Ag = +0.80 V.
E = EӨ + 0.059/1 lg[Ag+]
0.051 = 0.80 + 0.059 lg[Ag+]
[Ag+] = 1.22 x 10-5 moldm-3
Ksp = [Ag+][Cl-]
= (1.22 x 10-5 )2
= 1.49 x 10 -10 mol2dm-6
The Nernst Equation and Solubility Product
1. Consider the cell:
Pt(s) /H2 (g, 1.0 atm)/HCl(0.01M)// AgCl(aq)/Ag(s)
The measured cell emf is 0.046 V at 25oC and EӨ Ag+/Ag = +0.80 V
0 = EӨ - 0.059/n lg Kc
EӨ = 0.059/n [lg Kc]
pH = (0.76 – 0.54)/0.059
= 3.7