1

Electrochemistry

2
Index
19.1 Galvanic cells use redox reactions to generate electricity
19.2 Cell potentials can be related to reduction potentials
19.3 Standard reduction potentials can predict spontaneous
reactions
19.4 Cell potentials are related to free energy changes
19.5 Concentrations in a galvanic cell affect the cell potential
19.6 Electrolysis uses electrical energy to cause chemical
reactions
19.7 Stoichiometry of electrochemical reactions involves
electric current and time
19.8 Practical applications of electrochemistry

3
A galvanic cell is an electrochemical cell that derives electrical
energy from spontaneous redox reaction taking place within the
cell.
Zn(s) | Zn
2+
(aq) || Cu
2+
(aq) | Cu(s)

Galvanic cells use redox reactions to generate electricity 4
Anatomy of a Galvanic Cell
Cells (compartments containing reactants for each
half-reaction)
Electrodes to conduct current through the solution.
Salt bridge to offset ion movement
Supporting electrolyte

Sel Elektrokimia
reaksi redoks
spontan
anoda
oksidasi
katoda
reduksi
Menarik anion Menarik kation


Galvanic cells use redox reactions to generate electricity 7
Electrochemical Cells
In all cells, electrons transfer between the cathode
(the reduction half-cell) and the anode (the
oxidation half-cell)
Electrical current is conducted through the passage
of electrons and ions
To prevent charge buildup,
a salt bridge allows ions
to move between the
cells


Galvanic cells use redox reactions to generate electricity 8
Standard Cell Notation (Line Cell Notation)
Cell reactions separated by || that represents the salt
bridge
Electrodes appear at the outsides
Reaction electrolytes in inner section
Phases separated with |
Concentrations shown in ( )

Galvanic cells use redox reactions to generate electricity 9
Learning Check
Balance and identify the cathode and anode
CrO
3
(s) + MnO
2
(s) MnO
4
-
(aq) + Cr
3+
(aq)

(basic)
CrO
3
(s) + MnO
2
(s)

+ H
2
O MnO
4
-
(aq) + Cr
3+
(aq) +
2OH
-
(aq)
CrO
3
+ 3H
2
O + 3e
-
Cr
3+
+ 6OH
-

MnO
2
+ 4OH
-
MnO
4
-
+ 2H
2
O + 3e
-

Cathode: CrO
3

Anode: MnO
2


Galvanic cells use redox reactions to generate electricity 10
Learning Check:
Balance and identify the cathode and anode
H
2
O
2
(aq) + CO
2
(g) H
2
C
2
O
4
(aq) + O
2
(g) (acidic)
H
2
O
2
(aq) + 2CO
2
(g) H
2
C
2
O
4
(aq) + O
2
(g) (acidic)
H
2
O
2
O
2
+ 2H
+
+ 2e
-

2H
+
+ 2e
-
+ 2CO
2
H
2
C
2
O
4
(acidic)
Cathodic reaction: 2H
+
+ 2e
-
+ 2CO
2
H
2
C
2
O
4
Anodic reaction: H
2
O
2
O
2
+ 2H
+
+ 2e
-

Cell potentials can be related to reduction potentials 11
Electrical Potential
Every substance has the potential to gain
electrons, or be reduced in oxidation state
The relative ease of gaining electrons is termed the
reduction potential, and is symbolized E
red

If the matter being observed is in standard state
then E is termed the standard reduction potential
and is symbolized as E
red
Units are Volt 1 V = 1 J C
-1


Cell potentials can be related to reduction potentials 12
Standard Reduction Potentials (E
red
)
E
red
are tabulated for nearly
every known substance
A high value of E
red
(E
red
> 0)
means that the substance is easily
reduced
All substances are compared to
H
+
, which has a E
red
of 0.00 V

The hydrogen electrode. The half-reaction
is 2H
+
(aq) + 2e

H
2
(g).

Cell potentials can be related to reduction potentials 13
Cell Potentials
The standard cell potential is calculated as:
E
cell
= E
cathode
- E
anode

If the cell is non-standard:
E
cell
= E
cathode
- E
anode

In spontaneous redox reactions, the cathode
portion of the reaction has a higher
reduction potential than that of the anode
(E
cathode
> E
anode
)

Cell potentials can be related to reduction potentials 14
Your Turn
Given the two half reactions, what would be E
cell
for
the reaction:
Ni(s) + H
2
O
2
(aq) + 2H
+
(aq) 2H
2
O + Ni
2+
(aq)

A. 1.52 V
B. -1.52 V
C. 2.02 V
D. -2.02 V
Reaction E
cell

Ni
2+
+ 2e
-
Ni -0.25
H
2
O
2
+ 2H
+
+ 2e
-
2H
2
O 1.77

Standard reduction potentials can predict spontaneous reactions 15
Learning Check
Calculate E
cell
. Which are spontaneous?
Cu(s) + Ag
+
(aq) Cu
2+
(aq) + Ag(s)

Pb + Cu
2+
Pb
2+
+ Cu

Cr
2
O
7
2-
(aq) + MnO
2
(s) MnO
4
-
(aq) + Cr
3+
(aq)
Cu
2+
/Cu 0.34 V Cr
2
O
7
2-
/Cr
3+
1.33 V
Ag
+
/Ag 0.80 V MnO
4
-
/MnO
2
1.695 V
Pb
2+
/Pb -0.13 V
[0.80 - 0.34] V = 0.46 V
[0.34 - (-0.13)] V = 0.47 V
[1.33-1.695] V = -0.365 V

Standard reduction potentials can predict spontaneous reactions 16
Your Turn
Which of the following is not spontaneous?
A. Ni
2+
+ Pb Pb
2+
+ Ni
B. Ni + Pb
2+
Pb

+ Ni
2+
C. Zn + Pb
2+
Pb

+ Zn
2+

D. All are spontaneous
E
red

Ni
2+
+ 2e
-
Ni -0.25
Zn
2+
+ 2e
-
Zn -0.76
Pb
2+
+ 2e
-
Pb -0.13

Cell potentials are related to free energy changes 17
The Thermodynamics of Electrochemistry
It can be related to the free energy of a system,
however as: G = -nF
cell

n = the number of moles of electrons
transferred in the process
F = Faradays Constant, 96,500 C/mol e
-
If the system is not standard, G can be defined
as: G = -nF
cell


Energi Bebas Gibbs
Untuk proses suhu-konstan:
AG = AH
sis
-TAS
sis

Energi Bebas
Gibbs(G)
AG < 0 Reaksi spontan dalam arah maju.
AG > 0 Reaksi nonspontan. Reaksi ini spontan dalam
arah yang berlawanan.

AG = 0 Reaksi dalam kesetimbangan.

Cell potentials are related to free energy changes 19
Learning Check
Calculate G

in kJ
.
Which are spontaneous under standard
conditions?
Cu(s) + Ag
+
(aq) Cu
2+
(aq) + Ag(s)



Pb + Cu
2+
Pb
2+
+ Cu

Cr
2
O
7
2-
(aq) + MnO
2
(s) MnO
4
-
(aq) + Cr
3+
(aq)


Cu
2+
/Cu 0.34 V Cr
2
O
7
2-
/Cr 1.33 V
Ag
+
/Ag 0.80 V MnO
4
-
/MnO
2
1.695 V
Pb
2+
/Pb -0.13 V
G = -2 mol 96,500 C mol
-1
0.46 J C
-1
= -88.8 kJ
G = -2 mol 96,500 C mol
-1
0.47 J C
-1
= -90.7 kJ
G = -6 mol 96,500 C mol
-1
(-0.365 J C
-1
) = 211 kJ
Not spontaneous

Cell potentials are related to free energy changes 20
Your Turn
Given that G = 65.3 kJ , what is the value for E
cell

for the reaction Cu
2+
(aq) + Hg(l) Hg
2+
(aq) + Cu(s)?
A. 6.53 V
B.
.
+0.338 V
C. -0.338 V
D. -0.676 V
E. None of these

Cell potentials are related to free energy changes 21
Relating E to the Equilibrium Constant
Many redox reactions are reversible, thus the whole
cell reactions have equilibrium constants, K
G= nFE
and, G= RT ln K
thus,

ln
e
| |
|
\ .
=
=
nFE
RT
RT K
E
nF
K

Cell potentials are related to free energy changes 22
Learning Check:
Calculate K for the following cells.
Cu(s) + Ag
+
(aq) Cu
2+
(aq) + Ag(s)






Pb(s) + Cu
2+
(aq) Pb
2+
(aq) + Cu(s)




-1 -1
-1 -1
2 mol 96,500 C mol 0.47 J C

8.314 J mol K 298.15 K

15
e e 7.8 10
| |

| |
|
| |

\ . \ .
= = =
nFE
RT
K
-1 -1
-1 -1
2 mol 96,500 C mol 0.46 J C
nFE

8.314 J mol K 298.15 K
15 RT
e e 3.58 10
| |

| |
|
| |

\ . \ .
= = = K
E = 0.47 V
E

= 0.46 V

Cell potentials are related to free energy changes 23
Learning Check (Cont.)

Cr
2
O
7
2-
(aq) + MnO
2
(s) MnO
4
-
(aq) + Cr
3+
(aq)



-1 -1
-1 -1
6 mol 96,500 C mol 0.365 J C

8.314 J mol K 298.15 K

37
e e 1.1 10
| |

| |
|
| |

\ . \ .
= = =
nFE
RT
K
E = 0.365 V

Cell potentials are related to free energy changes 24
Your Turn!
What is the value of K for the reaction at 298.15 K:
E
cell
= 4.33 V 3PbO
2
+ 4Al 3Pb + 2Al
2
O
3


-1 -1
-1 -1
-1 -1
-1 -1
-1 -1
2 mol 96,500 C mol 4.33 J C
8.314 J mol K 298.15 K
3 mol 96,500 C mol 4.33 J C
8.314 J mol K 298.15 K
6 mol 96,500 C mol 4.33 J C
8.314
A. e
B. e
C. e
| |

|
|

\ .
| |

|
|

\ .

-1 -1
J mol K 298.15 K
D. None of the above
| |
|
|

\ .
|
|
|
|
.
|

\
|

K K Jmol
JC Cmol mol
e
15 . 298 314 . 8
33 . 4 96500 12
1 1
1 1

Concentrations in a galvanic cell affect the cell potential 25
The Nernst Equation
ln

= +
RT
E E Q
nF
For non- standard
conditions,
Substituting for the free
energy, G, terms gives us
Dividing by nF, we get
the Nernst Equation
When the temperature is
298 K and ln is converted
to log,

0.0592 log
=
Q
E E
n
AG = AG + RT ln Q
nFE = nFE + RT ln Q

Concentrations in a galvanic cell affect the cell potential 26
Learning Check: Calculate E
cell

Al|Al
3+
(aq) (0.5 M)||Zn
2+
(aq) (0.2 M)|Zn




Al|Al
3+
(aq) (0.5 M)||Zn
2+
(aq) (1 M)|Zn
2
3
E ( 0.76 ( 1.66)) 0.90 V
0.0592 [0.5]
E 0.90 log 0.906 V
6 [1]
= =
= =
Al
3+
/Al -1.66 V Zn
2+
/Zn -0.76 V
2
3
E ( 0.76 ( 1.66))
0.0592 [0.5]
E 0.90 V log 0.885 V
6 [0.2]
=
= =

Concentrations in a galvanic cell affect the cell potential 27
Learning Check
Al|Al
3+
(aq) (0.5 M)||Al
3+
(aq) (0.2 M)|Al




Al|Al
3+
(aq) (0.5 M, 25 C )||Al
3+
(aq) (0.5 M, 50 C )|Al

cell cathode anode
8.314 (323 K) 1
(-1.66) ln 1.6664 V
3 96,500 [0.5]
8.314 (298 K) 1
(-1.66) ln 1.6659 V
3 96,500 [0.5]
0.0005 V

= =

= =

= =
E
E
E E E
3
( 1.66 ( 1.66)) 0 V
0.0592 [0.5]
0 log 7.85 10 V
3 [0.2]

= =
= =
E
E
Al
3+
/Al -1.662 V

Concentrations in a galvanic cell affect the cell potential 28
Learning Check: Find the Unknown
Cr|Cr
3+
(?? M) ||Ni
2+
(0.5 M)|Ni
E
cell
= +0.494 V



Pt|H
2
(1atm)| H
+
(? ?pH)||H
+
(1 M)|H
2
(1 atm)|Pt
E
cell
= 0.000571 V


2
3
0.0592 [x]
0.494 ( 0.25 ( 0.74)) log
6 [0.5]
=
H
+
/H
2
0.00 V Cr
3+
/Cr -0.74 V
Ni
2+
/Ni -0.25 V Cu
2+
/Cu 0.34 V
0.978 M = x; pH = 0.00965
2
2
0.0592 [x]
0.000571 (0.00 0.00) log
2 [1]
=
0.222 M = x

Concentrations in a galvanic cell affect the cell potential 29
Learning Check
A galvanic cell consisting of a Cu versus hydrogen electrode was used to
determine the pH of an unknown solution. The unknown was placed in the
hydrogen electrode compartment and the pressure of the hydrogen gas was
controlled at 1 atm. The concentration of Cu
2+
was 1 M and the E
cell
at 25C
was determined to be +0.48 V. Calculate pH of this unknown solution. E
cell

was +0.34 V

Reaction: Cu
2+
(1M) + H
2
(g)(1 atm) Cu(s) + 2H
+
(?M)

19.8
Elektrolisis adalah proses di mana energi listrik digunakan
agar reaksi kimia nonspontan dapat terjadi.

Elektrolisis air
19.8

Electrolysis uses electrical energy to cause chemical reactions 32
Electrolytic Reactions:
Some reactions are not favored as written
(E
cath
< E
anode
), yet we would like them to occur
To do this, we apply electrical potential to the
system which exceeds the energy need, and we
remove any possible competing reactions
These reactions can often be performed in one
container, without resistance

Electrolysis uses electrical energy to cause chemical reactions 33
Electrolysis vs. Electrolytic vs. Galvanic
Note that electrolysis means the application of
electricity
Electrolytic means that the particular reaction
is not spontaneous

Electrolytic Cell Galvanic Cell
Cathode is negative (reduction)
Anode is positive (oxidation)
Non-spontaneous
Requires a battery
Cathode is positive (reduction)
Anode is negative (oxidation)
Spontaneous
Is a battery

Stoichiometry of electrochemical reactions involves electric current and time 34
The Kinetics of Electrolysis
Faradays Equation: q = It = nF
q = charge (coulombs, C)
I = current (Amperes, A, or C/s)
t = time (s)
n = moles of electrons transferred in the process
F = Faradays constant (96,500 C mol
-1
)
Using units tell us how these quantities are related

Elektrolisis dan Perubahan Massa
muatan (C) = arus (A) x waktu (s)
1 mol e
-
= 96.500 C
19.8
Analisis Kuantitatif
Berapa besar arus?
waktu ?
produk?

Berapa banyak Ca yang dihasilkan sel elektrolitik dari
lelehan CaCl
2
jika arus sebesar 0,452 A dialirkan
melalui sel selama 1,5 jam?

Berapa banyak Ca yang dihasilkan sel elektrolitik dari
lelehan CaCl
2
jika arus sebesar 0,452 A dialirkan
melalui sel selama 1,5 jam?
anoda:
katoda:
Ca
2+
(l) + 2e
-
Ca (s)
2Cl
-
(l) Cl
2
(g) + 2e
-

Ca
2+
(l) + 2Cl
-
(l) Ca (s) + Cl
2
(g)
2 mol e
-
= 1 mol Ca
mol Ca = 0,452
C
s
x 1,5 jam x 3600
s
jam 96.500 C
1 mol e
-

x
2 mol e
-

1 mol Ca
x
= 0,0126 mol Ca
= 0,50 g Ca

e
-
+ Ag
+
Ag katoda:
2 H
2
O O
2

(g) + 4 H
+
+ 4 e
-
anoda:
Stoikiometri dari sebuah sel elektrolitik:
Berapakah arus (dalam ampere) yang dibutuhkan utk
mengubah 0,100 mol Ag
+
jadi Ag dalam 10,0 menit?

e
-
+ Ag
+
Ag katoda:
2 H
2
O O
2

(g) + 4 H
+
+ 4 e
-
anoda:
Stoikiometri dari sebuah sel elektrolitik:
Berapakah arus (A) yang dibutuhkan utk mengubah 0,100 mol Ag
+
jadi Ag dalam 10,0 menit?
1 mol elektron = 1 F A = C/detik
Q = nF I = Q / t
Cari Q
Q = 0,10 mol Ag 1 mol elektron 1 F 96.500 C
=
mol Ag mol elektron F
Q = 9.650 C
t = 10 menit 60 detik = 600 detik
1 menit
I = 9.6500 C / 600 s = 16 C/s = 16 A

e
-
+ Ag
+
Ag katoda:
2 H
2
O O
2

(g) + 4 H
+
+ 4 e
-
anoda:
Stoikiometri Produk pada Elektroda yang Berbeda
Berapakah pH dari anoda setengah-sel (misalkan volumenya 0,100
L) setelah 6,00 g Ag diletakkan di katoda? Ag (107.0 g/mol)

e
-
+ Ag
+
Ag katoda:
2 H
2
O O
2

(g) + 4 H
+
+ 4 e
-
anoda:
Stoikiometri Produk pada Elektroda yang Berbeda
Berapakah pH dari anoda setengah-sel (misalkan volumenya 0,100
L) setelah 6,00 g Ag diletakkan di katoda? Ag (107.0 g/mol)
Cari [H
+
]
6,00 g Ag 1 mol Ag 1 mol elektron 4 mol H
+

107,9 g Ag 1 mol Ag 1 mol elektron
= 0,05567 mol H
+

[H
+
] = 0,0556 mol = 0,56 M
0,10 L
pH = 0,25

Practical applications of electrochemistry 42
Batteries - Galvanic Cells
Primary Cell Secondary Cell
Non-rechargeable
Alkaline dry cell
Rechargeable
Pb storage Battery


Practical applications of electrochemistry 43
Purification of Copper by electrolysis




44