EXPERIMENT 15

Electrochemistry

Cruz, S.M.M, Zaragosa, Z.G.C

Institute of Chemistry, College of Science
University of the Philippines, Diliman, Quezon City 1101 Philippines
Calculations:
1. Cell Notation: Zn(s)|Zn2+(aq) (0.1M) ||Cu2+(aq) (0.1M)|Cu(s)

Anode: Zn(s)

Zn2+(aq) + 2e-

Cathode: Cu2+(aq) + 2e-

Cu(s)

Overall: Cu2+(aq) + Zn(s)

Zn2+(aq) + Cu(s)

Ecell = 1.06V
E0cathode = 0.34V

2+
Zn

2+
Cu

Ecell =E0cell

RT
ln
zF

2 mol e

mol e
96485 C

8.3145 J
( 298.15 K )
molK
0
1.06 V =E

= 1.06V

E0cell = E0cathode E0anode

1.06V = 0.34V E0anode
E0anode = -0.72V
% error =

0.72
( 0.763
)|x 100

= 5.64%

2. Cell notation: C(s)|Fe2+(aq)(0.1M),Fe3+(aq)(0.1M)||Cu2+(aq) (0.1M)|Cu(s) , Ecell =

0.40V

Anode: 2Fe2+(aq)

2Fe3+(aq) + 2e

Cathode: Cu2+(aq) + 2e-

Overall: Cu2+(aq) + 2Fe2+(aq)

Cu(s)

2Fe3+(aq) + Cu(s)

E0cathode = 0.34V

3+
Fe

Cu

2+
Fe

2+

Ecell =E0cell

RT
ln
zF

2mol e

mol e
96485 C

8.3145 J
( 298.15 K )
molK
0
0.40V =E

= -0.370V

E0cell = E0cathode E0anode

-0.370V = 0.34 E0anode

3+ /Fe2 +=0.710V
Fe
0
E
%Error:

| ( )|
1

0.710
x 100
0.771

= 7.91%

3. Cu(s)|Cu2+(aq) (0.01M)||Cu2+(aq) (0.1M)|Cu(s) , Ecell = -0.0092V

 Cu2+(aq) (0.01M) + 2e-

Anode: Cu(s)

Cathode: Cu2+(aq) (0.1M)+ 2e-

Cu(s)

Cu2+(aq) (0.01M)

Reaction: Cu2+(aq) (0.1M)

E0cathode = 0.34V

Ecell =E0cell

RT [ 0.01 M ]
ln
zF
[ 0.1 M ]

2 mol e

mol e
96485 C

8.3145 J
( 298.15 K )
molK
0
0.0092V =E

= E0cell = -0.0388V

E0cell = E0cathode E0anode

-0.0388V = 0.34 E0anode
E0anode = 0.3788V
4. Cell Notation: Cu(s)|[Cu(NH3)4]2+(aq) (0.01667M), NH3(aq) (0.01667M) ||Zn2+(aq)
(0.1M)|Zn(s)
Anode: Cu(s) + 4NH3(aq)
Cathode: Zn2+(aq) + 2e-

[Cu(NH3)4]2+(aq) + 2e-

Zn(s) , E0 = -0.72 (From number 1).

Reaction: Cu(s) + 4NH3(aq) + Zn2+(aq)

Zn(s) + [Cu(NH3)4]2+(aq)

Ecell = 0.184V

0.184 V =E 0cell

( 8.3145 ) ( 298.15 )
0.01667
ln
( 2 ) ( 96485 )
0.1 ( 0.01667 )4

E0cell = 0.371V
0.371V = -0.72 E0anode
E0anode = -1.091
Anode: Cu(s) + 4NH3(aq)

Cathode: Cu2+(aq) + 2e-

Cu(s) , E0 = 0.34

[Cu(NH3)4]2+(aq) + 2e-

E0cell = 0.34+1.091= 1.431V

5. KCl: Cgraphite|Cl2(aq), Cl-(aq) (0.1M)||Cu2+(aq) (0.1M)|Cu(s)
Anode: 2Cl-(aq)

Cl2(aq) + 2e-

Iaverage =

120+156.3+ 149.6
3

Cathode: Cu2+(aq) + 2e-

= 141.97mA

Cu(s)

Overall Reaction: 2Cl-(aq) + Cu2+(aq)

Cu(s) + Cl2(aq)

e
96485 C

2 mol e
=2.21x10-3M
1mol Cl 2

( 0.14197 A ) ( 60 s )
1 mol

[Cl2(aq)] =

Ecell = -0.168V
0.168V =E0cell

( 8.3145 )( 298.15 )
0.00221
ln
( 2 ) ( 96485 )
( 0.1 )2 ( 0.1 )

E0cell = -0.158V
-0.158V = 0.34V E0Cl2/ClE0Cl2/Cl- = 0.498V
0.498
1
x 100
%Error:
= 63.3%
1.358

| ( )|

6. KBr: Cgraphite|Br2(aq), Br-(aq) (0.1M)|| Cu2+(aq) (0.1M)|Cu(s)

Anode: 2Br-(aq)
Iaverage =

Br2(aq) + 2e-

85+173.6+176.6
3

Cathode: Cu2+(aq) + 2e-

= 145.07mA
Cu(s)

Overall Reaction: 2Br-(aq) + Cu2+(aq)

[Br2(aq)] =

Cu(s) + Br2(aq)

e
1 mol
96485 C

2 mol e
=2.26x10-3M
1mol Cl 2

( 0.14507 A ) ( 60 s )

Ecell = -0.168V

0.345V =E0cell

( 8.3145 )( 298.15 )
0.00226
ln
( 2 ) ( 96485 )
( 0.1 )2 ( 0.1 )

E0cell = -0.335V
-0.335V = 0.34V E0Br2/BrE0Br2/Br- = 0.675V
0.675
1
x 100
%Error:
= 26.2%
0.535

| ( )|

7. KI: Cgraphite|I2(aq), I-(aq) (0.1M)|| Cu2+(aq) (0.1M)|Cu(s)

Anode: 2I-(aq)
Iaverage =

I2(aq) + 2e-

51+110.6 +109
3

Cathode: Cu2+(aq) + 2e-

= 90.2mA

Cu(s)

Overall Reaction: 2I-(aq) + Cu2+(aq)

Cu(s) + I2(aq)

e
96485 C

2 mol e
=1.40x10-3M
1 mol Cl 2

( 0.0902 A )( 60 s )
1 mol

[I2(aq)] =

Ecell = -0.220V
0.220V =E0cell

( 8.3145 )( 298.15 )
0.00140
ln
( 2 ) ( 96485 )
( 0.1 )2 ( 0.1 )

E0cell = -0.216V
-0.216V = 0.34V E0I2/IE0I2/I- = 0.556V
0.556
1
x 100
%Error:
= 47.8%
1.065

| ( )|

8. Cu(OH)2: Cu(s)|Cu(OH)2(s)|OH-(aq) (0.025M)||Zn2+(aq) (0.1M)|Zn(s)

Cu2+ + 2OH- = [Cu2+][OH-]2
K = Cu(OH)
sp

2(s)

(aq)

(aq)

Anode: Cu(s) + 2OH-(aq)

Cu(OH)2(s) + 2e-

Cathode: Zn2+(aq) + 2e-

Zn(s)

Reaction: Cu(s) + Zn2+(aq) + 2OH-(aq)

Cu(OH) + Zn
2(s)
(s)

Ecell = 0.242V
E0cell =

0.242V +

Anode: Zn(s)

( 8.3145 ) ( 298.15 )
1
ln
2
( 2 ) ( 96485 )
0.1 ( 0.025 )

= 0.366V

Zn2+(aq) + 2e-

Cathode: Cu2+(aq) + 2e-

E0cell =

Cu(s)

2+

Zn

2+
Cu

RT
Ecat Ean +
ln
zF
2+
Cu

0.10

0.366 V =0.34 V + 0.72V +

( 8.3145 ) ( 298.15 )
ln
( 2 ) ( 96485 )

References:
[1] Petrucci, R., et al. General Chemistry: Principles and Modern
Applications (10th ed.). Toronto, Ont: Pearson Canada. 2011
[2] Brown, T., Lemay, et al. Chemistry, The Central Science (11th ed.). Jurong,
Singapore: Pearson Education South Asia PTE.2009
[3] Silberberg, M.. Chemistry: The Molecular Nature of Matter and Change.
Boston: McGraw-Hill 2006
[4]Chang, R. (2010). Chemistry. Boston: McGraw-Hill.
[5]Whitten, K. W. (2009). Chemistry: The Core. Belmont, Ca: Brooks/Cole Cengage
Learning.

Appendix:

Answers to Questions:
1. In the electrolysis of KX solution:
a. At which electrode, anode or cathode, is X2 generated? Is this the positive
(+) or negative (-) terminal of the electrolytic cell?
X2 is generated at the anode because the anode is the site of oxidation in
any electrochemical cell. Since the oxidation of Cl- is not spontaneous;
therefore, by electrolysing it, electrons are being forced to go to the
cathode from the anode and thus making the anode positive (+).
b. What will be formed at the other electrode? Write the ionic equation
involved at this electrode.
H2 bubbles will be formed along with OH- ions because of the reduction of
H+.
2H2O(l) + 2e-

H2(g) + 2OH-(aq)

c. Prove mathematically the assumption that the [X-] was not significantly
reduced in the electrolysis.
2. Which of the following reactions are possible sources of electrical energy?
Write the cathode and anode reactions for those that are.
a. Only the reaction between chlorine gas and bromide ion and the reaction
between hydrogen gas and oxygen gas can be the sources of electrical
energy because a redox reaction takes place in this reaction which
therefore involves the release of electrons and will generate electricity.
The other reaction left cannot generate electrical energy because it is not
a redox reaction. In the last reaction, the reaction is not a redox reaction
but it is a source of energy because it is a solid formation therefore there
is a change in entropy and energy is released by the reaction upon
forming a solid.
(1) Cathode: Cl2(g) + 2eAnode: 2Br-(aq)

2Cl-(aq)

Br2(g) + 2e-

Overall Reaction: Cl2(g) + 2Br-(aq)

(2) Cathode: O2(g) +2eAnode: H2(g)

Br2(g) + 2Cl-(aq)

O2-(aq)

2H+(aq) + 2e-

Overall: H2(g) + O2(g)

H2O(l)

3. Given the cell:

Pt(s)|Cl2(g) (1atm)|Cl-(aq) (0.1M)||H+(aq) (1M), MnO4-(aq) (0.1M), Mn2+(aq) (0.1M)|Pt(s)
For which: H+, MnO4-, Mn2+|Pt E0red = +1.51V
Cl-/Cl2|Pt
E0red = +1.36V
a. Calculate the:
i.
Cell potential:
RHR: 16H+(aq) + 2MnO4-(aq) +10eOHR: 10Cl-(aq)

5Cl2(g) + 10e-

2Mn2+(aq) +8H2O(l)

Overall Reaction: 16H+(aq) + 2MnO4-(aq) +10Cl-(aq)

2Mn2+(aq)

+8H2O(l) +5Cl2(g)

10 mol e

mol e
96485C

8.3145 J
( 298.15 K )
molK
Ecell =( 1.511.36 )

ii.

Ecell = 0.0908V
Free energy charge per mole of electrons transferred

mol e
96485 C

mol e
0.0908 J

b. Will the cell potential be greater or lesser or the same if:

i.
0.1M KCl is added to the anode half-cell. = Greater
ii.
A few crystals of AgNO3 are added to the anode half-cell = Lesser
iii.
A few crystals of KMnO4 are added to the cathode half-cell =
Greater
c. If NaOH is added to the cathode half-cell to make the H + concentration
decrease to 0.001M, and if the concentration of the other ions remains
essentially unchanged, write the ionic equation for the spontaneous cell
reaction. Show calculations to support your answer.
Cell potential:
RHR: 16H+(aq) + 2MnO4-(aq) +10eOHR: 10Cl-(aq)

2Mn2+(aq) +8H2O(l)

5Cl2(g) + 10e-

Overall Reaction: 16H+(aq) + 2MnO4-(aq) +10Cl-(aq)

+8H2O(l) +5Cl2(g)

2Mn2+(aq)


10 mol e

mol e
96485C

8.3145 J
( 298.15 K )
molK
Ecell =( 1.511.36 )

Ecell = -0.193V
Since the cell potential is still negative; therefore the reaction will
be reversed to make it spontaneous.
Eqn: 2Mn2+(aq) +8H2O(l) + 5Cl2(g)
+10Cl-(aq) Ecell = -0.193V

16H+(aq) + 2MnO4-(aq)