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C3 Electrochemistry
C3 Electrochemistry
C3 Electrochemistry
1
R = cath
O = anode
At the end of this chapter , students should be able to
1. Write balanced half-cell reaction and overall cell reaction
for
electrochemical processes.
2. Explain the differences between voltaic and electrolytic cell.
3. Understand the relationship between chemical energy (Gibbs free energy
change for a redox reaction) and electrical,energy (electromotive force or
cell potential) in an electrochemical cell.
4. C a lculate cell potentials for electrochemical cells using the
Nernst equation.
5. Relate the concentration of solutes to the cell potential
6. Explain the nature of electrolysis and use the electrolysis
information quantitatively
2
REDOX REACTION
1. Free elements have an oxidation state of 0. (e.g., He, N 2 , O 2 has an oxidation state of 0)
2. The oxidation state of one atom ion must equal the net charge. (e.g., F- oxidation state
is -1, K + oxidation state is +1)
3. The sum of the oxidation state has to equal the total net charge for a compound. (e.g.,
MnO 4 - has a net charg e of -1, Mn(+7)O (-8)= -
4. 1) 4
The alkali metals (Group I elements) have an oxidation state of +1. (e.g., Li 2 O, Li= +1)
5. The alkaline earth metals (Group II elements) always have an oxidation state of +2.
(e.g ., C a O, C a = + 2)
6. Oxygen has an oxidation state of -2 in a compound
7. Fluorine has an oxidation state of -1 in a compound
8. Hydrogen has an oxidation state of +1 in a compound.
9. Transition metals and other metals may have more than one common ionic charge.
(e.g ., Chromium's common ionic charg es are C r + 2 and Cr + 3 )
4
Balancing Redox Reactions in Acidic
Solution
Cr2O72-(aq) + I-(aq) Cr3+(aq) + I2(aq)
Cr2O72- Cr3+
Oxidation number of Cr is decreased from +6 to +3 →
reduction
2 I- I2 + 2e- X3
7
Permanganate ion is a strong oxidizing agent, and its deep purple color makes it useful as an
indicator in redox titrations. It reacts in basic solution with the oxalate ion to form carbonate ion
and solid manganese dioxide. Balance the skeleton ionic reaction that occurs between NaMnO 4
and Na 2 C 2 O 4 in basic solution:
MnO -(aq) + C O 2- (aq) MnO (s) + C O 2- (aq)
4 2 4 2 3
MnO 4-(aq) + 4H+ (aq) + 3e - → MnO 2(s) + 2H2 O(l) × 2 Reduction: oxidation number Mn decreased from +7 to
C 2 O 42-(aq) + 2H2O(l) → 2 C O 3 2-(aq) + 4H+ (aq) + 2e- ×3 +4
2MnO 4-(aq) + 3C 2O 42-(aq) + 2H 2O(l) → 2MnO2 (s) + 6 C O 3 (aq) + 4H (aq) Overall redox reaction in acidic condition
2- +
O xidation: oxidation number of C increased from +3 to +4
Additional step: Add equal number of OH - ions both side to make solution basic:
8
VOLTAIC CELL ELECTROLYTIC CELL
VOLTAIC CELL ELECTROLYTIC CELL
System
Energydoes work on
is released its
from Surroundings(power
Energy is absorbed tosupply)
drive a
surroundings
spontaneous redox reaction nonspontaneous redox
do work on system(cell)
reaction
Anode Oxidation -
Voltaic <0 >0
Cathode Reduction +
Cathode Reduction -
1
0
VOLTAIC / GALVANIC CELL
A single vertical line indicates a phase boundary The double vertical line represents a salt bridge
14
HOW DOES A VOLTAIC CELL WORK
The spontaneous reaction occurs as a result of the different abilities of materials (such as
metals) to give up their electrons and the ability of the electrons to flow through the circuit.
15
STANDARD REDUCTION POTENTIAL
16
DETERMINING AN UNKNOWN E0HALF-CELL WITH THE
STANDARD REFERENCE (HYDROGEN) ELECTRODE
Oxidation half-reaction
Zn(s) Zn2+(aq) + 2e-
Reduction half-reaction
Overall (cell) reaction 2H3O+(aq) + 2e- H2(g) + 2H2O(l)
Zn(s) + 2H3O+(aq) Zn2+(aq) + H2(g) + 2H2O(l)
17
FREE ENERGY AND ELECTRICAL WORK
1V = 1J/C G0 = - RT ln K
18
0E
0
THE INTERRELATIONSHIP OF G cell K
Reaction at
G0 G
G00 KK EE00cell
REACTION OF
cell standard-state
STANDARD STATE
conditions
CONDITION
E0cell = RT lnK
nF
K
E0cell 19
CALULATING
PROBLEM: Lead can displace silver from solution:
ln K = G0 / -RT
G0= -RT ln K
-179490 J = - 8.314 J / K mole e x 298K ln K
K = 2.9 X 10 20
EFFECT CONCENTRATION ON CELL POTENTIAL
Eo - voltage/potential at std cond.
If non std cond = Nernst eq
RT Nernst equation
Ecell = E0cell - ln Q
nF
•When Q < 1 and thus [reactant] > [product], lnQ < 0, so Ecell > E0cell
•When Q >1 and thus [reactant] < [product], lnQ > 0, so Ecell < E0cell
21
USING NERNST EQUATION TO CALCULATE E CELL
PROBLEM:
In a test of a new reference electrode, a chemist constructs a voltaic cell consisting of a
Zn/Zn2+ half-cell and an H2/H+ half-cell under the following conditions:
Find EO cell
Calculate Ecell at 298 K.
2H+ + 2e H2(g) 0.00 V
Zn(s) Zn2+(aq) + 2e 0.76V
2H+ + Zn(s) H2(g) + Zn2+(aq) EO+0.76V
cell = 0.00 + 0.76 = +0.76V
2
3
CONCENTRATION CELL BASED ON THE
CU / CU 2+ HALF REACTION
Oxidation half-reaction
2H2O(l) → 4H+(aq) + O2(g) + 4e- E o
= +1.23 V
(at pH = 7) ⇒ E
= +0.82 V
28
PRODUCTS OF ELECTROLYSIS
2
2 NaCl(l) 2 Na(s) + Cl 2 (g)
9
PRODUCTS OF ELECTROLYSIS
Electrolysis of aqueous solutions
Overvoltage needs to be taken into account when predicting the products of electrolysis for
aqueous solutions.
32
Summary of the Electrolysis of Aqueous Salt Solutions
• Cations of less active metals (Au, Ag, Cu, Cr, Pt, Cd) are
reduced to the metal.
33
A summary diagram for the stoichiometry of electrolysis.
AMOUNT (MOL)
AMOUNT (MOL)
of substance Faraday
of electrons
oxidized or constant
transferred
reduced (C/mol e-)
34
Relationship Among Current, Time, and Amount of
Substance
PROBLEM: A technician is plating a faucet with 0.86 g of Cr from an electrolytic
bath containing aqueous Cr2(SO4)3. If 12.5 min is allowed for the
plating, what current is needed?
PLAN: mass of Cr needed SOLUTION: Cr3+(aq) + 3e- Cr(s)
divide by M
mol of Cr needed 0.86g (mol Cr) (3 mol e-) = 0.050 mol e-
3mol e-/mol Cr (52.00 gCr) (mol Cr)
mol of e- transferred
0.050 mol e- (9.65x104 C/mol e-) = 4.8x103 C
9.65x104C/mol e-
charge (C) 4.8x103 C (min)
= 6.4C/s = 6.4 A
12.5 min (60s)
divide by time
current (A)
35
DEC18 Q3
Water goes oxidation to produce hy