Redox Reactions

& Electrochemistry

Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Reaksi Redoks

Elektrokimia : cabang ilmu kimia yang

berkenaan dengan interkonversi energi
listrik dan energi kimia
 Electrochemical processes are oxidation-reduction reactions
in which:
• the energy released by a spontaneous reaction is
converted to electricity or…
• electrical energy is used to cause a nonspontaneous
reaction to occur

2Mg (s) + O2 (g) 2MgO (s)

2Mg 2Mg2+ + 4e- _______ half-reaction (____ e-)

O2 + 4e- 2O2- _______ half-reaction (____ e-)

19.1
 Review
Oxidation – a species is oxidized when it
loses one or more electrons, and it is
called a reducing agent
Reduction – a species is reduced when it
gains one or more electrons, and it is
called an oxidizing agent
Oxidation and reduction always occur
together, never in isolation. If something
gains electrons, something else had to
lose them.
 Oxidation Number
The charge the atom would have in a molecule (or an
ionic compound) if electrons were completely transferred.

1. Free elements (uncombined state) have an oxidation

number of ______.

Na, Be, K, Pb, H2, O2, P4 = 0

2. In monatomic ions, the oxidation number is equal to
the __________________.

Li+, Li = +1; Fe3+, Fe = +3; O2-, O = -2

3. The oxidation number of oxygen is usually _________.
In H2O2 and O22- it is __________.
19.4
 Oxidation Number

4. The oxidation number of hydrogen is ___ except when

it is bonded to metals in binary compounds. In these
cases, its oxidation number is ___. (LiAlH4)

5. Group IA metals are ___, IIA metals are ___ and

fluorine is always ___.

6. The sum of the oxidation numbers of all the atoms in a

molecule or ion is equal to ________________________.

19.4
 Oxidation Number

Identify all of the oxidation

numbers of the atoms in HCO3—

H=

C=

O=

19.4
 Balancing Redox Equations p.606f

Balance the oxidation of Fe2+ to Fe3+ by Cr2O72- in acid solution

1. Write the unbalanced equation for the reaction in ionic form.

Fe2+ + Cr2O72- Fe3+ + Cr3+

2. Separate the equation into two half-reactions.

+2 +3
Oxidation: Fe2+ Fe3+
+6 +3
Reduction: Cr2O7 2- Cr3+

3. Balance the atoms other than O and H in each half-reaction.

Cr2O72- 2Cr3+
19.1
 Balancing Redox Equations
4. For reactions in acid, add H2O to balance O atoms and H+ to
balance H atoms.
Cr2O72- 2Cr3+ + 7H2O
14H+ + Cr2O72- 2Cr3+ + 7H2O
5. Add electrons to one side of each half-reaction to balance the
charges on the half-reaction.
Fe2+ Fe3+ + 1e-
6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O
6. If necessary, equalize the number of electrons in the two half-
reactions by multiplying the half-reactions by appropriate
coefficients.
6Fe2+ 6Fe3+ + 6e-
6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O
19.1
 Balancing Redox Equations
7. Add the two half-reactions together and balance the final
equation by inspection. The number of electrons on both
sides must cancel.

Oxidation: 6Fe2+ 6Fe3+ + 6e-

Reduction: 6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O
14H+ + Cr2O72- + 6Fe2+ 6Fe3+ + 2Cr3+ + 7H2O

8. Verify that the number of atoms and the charges are balanced.

14x1 – 2 + 6x2 = 24 = 6x3 + 2x3

9. For reactions in basic solutions, add OH- to both sides of the

equation for every H+ that appears in the final equation.
19.1
Contoh : tulislah persamaan ionik yang
setara untuk menyatakan oksidasi ion
iodida (I-) oleh ion permanganat (MnO4-)
dalam larutan basa untuk mengasilkan
iodin (I2) dan mangan (IV) oksida (MnO2)
Sel Galvani

• Dari gambar diperlihatkan komponen penting dari sel

galvani. Sebatang Zn dicelupkan kedalam larutan
ZnSO4, dan sebatang Cu dicelupkan kedalam CuSO4.
sel bekerja berdasarkan asas bawa Zn menjadi Zn2+ dan
reduksi Cu2+ menjadi Cu dapat dibuat berlangsung
serentak dalam lokasi-lokasi yang terpisah dimana
transfer elektron antara lokasi-lokasi tersebut terjadi
melalui sebuah kawat eksternal.
• Batang Zn dan Cu dinamakan elektroda.
• Berdasarkan definisi, anoda dalam sel galvani ialah
elektroda tempat terjadinya oksidasi dan katoda ialah
elektroda tempat terjadinya reduksi
 Electrochemical Cells p.610

_______ _______
__________ __________

spontaneous
redox reaction

19.2
• Dalam percobaan selisih potensial listrik antara
anoda dan katoda diukur dengan voltmeter dan
angkanya disebut voltase sel. Namun, dua
istilah lain, gaya elekrtomotif atau emf (E) dan
potensial sel juga digunakan untuk mnyatakan
voltase sel
• Diagram selnya
Zn(s)Zn2+ (1M)  Cu2+ (1M)  Cu(s)
 Electrochemical Cells p.611

The difference in electrical

potential between the anode
and cathode is called:
• ____________________
• ____________________
• ____________________
Cell Diagram
Zn (s) + Cu2+ (aq) Cu (s) + Zn2+ (aq)
[Cu2+] = 1 M & [Zn2+] = 1 M
Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)
anode cathode
19.2
 Standard Electrode Potentials p.612

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

Anode (oxidation): Zn (s) Zn2+ (1 M) + 2e-
Cathode (reduction): 2e- + 2H+ (1 M) 2H2 (1 atm)

19.3
 Standard Electrode Potentials(Potensial Reduksi Standar)

Standard reduction potential (E0) is the voltage associated

with a reduction reaction at an electrode when all solutes
are 1 M and all gases are at 1 atm.
Any time you see º, think
“standard state conditions”

Reduction Reaction

2e- + 2H+ (1 M) 2H2 (1 atm)

E0 = 0 V

Tekanan H2 1 atm, [HCl] 1 M,

T = 25 0C
Standard hydrogen electrode (SHE)
 Standard Electrode Potentials p.612
0 = 0.76 V
Ecell

0 )
Standard emf (Ecell
0 = E0
Ecell 0
cathode - Eanode

0 = E0
Ecell 0
reduct’n - Eoxid

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

0 = E 0 + - E 0 2+
Ecell H /H2 Zn /Zn

0.76 V = 0 - EZn0 2+
/Zn
0 2+
EZn /Zn = -0.76 V

Zn2+ (1 M) + 2e- Zn E0 = ____________

19.3
 Standard Electrode Potentials

0 = 0.34 V
Ecell
0 = E0
Ecell 0
cathode - Eanode

Cu /Cu – EH +/H 2
0 = E 0 2+
Ecell 0

0 2+
0.34 = ECu /Cu - 0
0 2+
ECu /Cu = 0.34 V

Pt (s) | H2 (1 atm) | H+ (1 M) || Cu2+ (1 M) | Cu (s)

Anode (oxidation): H2 (1 atm) 2H+ (1 M) + 2e-
Cathode (reduction): 2e- + Cu2+ (1 M) Cu (s)

19.3
• Nilai-nilai E0 pada reaksi setengah-sel adalah nilai
untuk reaksi pada arah maju (kiri kekanan)
• Semakin positif E0, semakin besar kecenderungan zat
untuk tereduksi
• Reaksi-reaksi setengah sel pada tabel adala reaksi
reversibel.bergantung pada kondisinya, setiap elektroda
dapat berfungsi sebagai anoda atau katoda.
• Pada kondisi keadaan-standar, setiap spesi disebelah
kiri dari suatu reaksi setengah sel akan bereaksi
spontan dengan spesi yang muncul disebelah kanan
dari semua reaksi setengah sel
• Mengubah koefisien stoikiometri suatu reaksi setengah
seltidak mempengaruhi nilai E0 sebab potensial
elektroda adalah sifat intensif
 Can Sn reduce Zn2+ under standard-state conditions?

How do we find the answer?

Look up the Eº values in Table 19.1, p.616.
Zn2+(aq) + 2e- —> Zn(s) (Is this oxidation or reduction?)

Which reactions in the table will reduce Zn2+(aq)?

Practice Exercise 19.2, p.616

 What is the standard emf of an electrochemical cell made
of a Cd electrode in a 1.0 M Cd(NO3)2 solution and a Cr
electrode in a 1.0 M Cr(NO3)3 solution?

Cd2+ (aq) + 2e- Cd (s) E0 = -0.40 V Cd is the stronger oxidizer

Cr3+ (aq) + 3e- Cr (s) E0 = -0.74 V Cd will oxidize Cr

Anode (oxidation): Cr (s) Cr3+ (1 M) + 3e- x 2

Cathode (reduction): 2e- + Cd2+ (1 M) Cd (s) x3

0 = E0
Ecell - E 0
cathode anode

0 = -0.40 – (-0.74)
Ecell
0 = _________
Ecell
Practice Exercise 19.3, p.617 19.3
 Spontaneity of Redox Reactions
DG = -nFEcell n = number of moles of electrons in reaction
J
DG0 = 0
-nFEcell F = 96,500 = 96,500 C/mol
V • mol
DG0 = -RT ln K = -nFEcell
0

RT (8.314 J/K•mol)(298 K)
0
Ecell = ln K = ln K
nF n (96,500 J/V•mol)

0 0.0257 V
Ecell = ln K
n
0 0.0592 V
Ecell = log K
n

Follow along on pp.617ff! 19.4

 Spontaneity of Redox Reactions

If you know one, you can

calculate the other…
If you know K, you can
calculate DEº and DGº
If you know DEº, you can
calculate DGº

19.4
 p.619
Spontaneity of Redox Reactions

Relationships among DG º, K, and Eºcell

19.4
 What is the equilibrium constant for the following reaction
at 250C? Fe2+ (aq) + 2Ag (s) Fe (s) + 2Ag+ (aq)

0 0.0257 V
Ecell = ln K
n
Oxidation: 2Ag 2Ag+ + 2e-
n = ___
Reduction: 2e- + Fe2+ Fe

2+/Fe – EAg + /Ag

0
E0 = EFe 0

E0 = -0.44 – (0.80)
E0 = ___________ 0
Ecell xn -1.24 V x 2
K = exp = exp
0.0257 V 0.0257 V

K = ________________

Practice Exercise 19.4, p.619 19.4

 Calculate DG0 for the following reaction at 250C.
2Al3+(aq) + 3Mg(s) 2Al(s) + 3Mg+2(aq)

Oxidation: 2Mg 2Mg2+ + 6e-

n=?
Reduction: 6e- + 3Al3+ 3Al

0 = E0
Ecell 0
cathode - Eanode

DG0 = -nFEcell
0

Practice Exercise 19.5, p.620 19.4

 Calculate DG0 for the following reaction at 250C.
2Al3+(aq) + 3Mg(s) 2Al(s) + 3Mg+2(aq)

Oxidation: 2Mg 2Mg2+ + 6e- E0 = __ V

Reduction: 6e- + 3Al3+ 3Al E0 = __ V

n = __
0 = E0 0
Ecell cathode - Eanode = ___ V

DG0 = -nFEcell
0 = ___ X (96,500 J/V mol) X ___ V

DG0 = _______ kJ/mol

Practice Exercise 19.5, p.620 19.4

 The Effect of Concentration on Cell Emf

DG = DG0 + RT ln Q DG = -nFE DG0 = -nFE 0

-nFE = -nFE0 + RT ln Q

RT
_____________ equation E = E0 - ln Q
nF

At 298K

0.0257 V 0.0592 V
E = E0 - ln Q E = E0 - log Q
n n

Work through derivation on pp.620ff 19.5

The Nernst equation enables us to
calculate E as a function of
[reactants] and [products]
in a redox reaction.
 Batteries

Dry cell

Leclanché cell

Anode: Zn (s) Zn2+ (aq) + 2e-

Cathode: 2NH+4 (aq) + 2MnO2 (s) + 2e- Mn2O3 (s) + 2NH3 (aq) + H2O (l)

Zn (s) + 2NH4 (aq) + 2MnO2 (s) Zn2+ (aq) + 2NH3 (aq) + H2O (l) + Mn2O3 (s)

19.6
 Batteries

Mercury Battery

Anode: Zn(Hg) + 2OH- (aq) ZnO (s) + H2O (l) + 2e-

Cathode: HgO (s) + H2O (l) + 2e- Hg (l) + 2OH- (aq)

Zn(Hg) + HgO (s) ZnO (s) + Hg (l)

19.6
 Batteries

Lead storage
battery

Anode: Pb (s) + SO2-4 (aq) PbSO4 (s) + 2e-

Cathode: PbO2 (s) + 4H+ (aq) + SO2-

4 (aq) + 2e
- PbSO4 (s) + 2H2O (l)

Pb (s) + PbO2 (s) + 4H+ (aq) + 2SO2-

4
(aq) 2PbSO4 (s) + 2H2O (l)

19.6
 Batteries

Solid State Lithium Battery 19.6

 Batteries

A fuel cell is an
electrochemical cell
that requires a
continuous supply of
reactants to keep
functioning

Anode: 2H2 (g) + 4OH- (aq) 4H2O (l) + 4e-

Cathode: O2 (g) + 2H2O (l) + 4e- 4OH- (aq)

2H2 (g) + O2 (g) 2H2O (l)

19.6
Corrosion

19.7
 Cathodic Protection of an Iron Storage Tank

p.631 19.7
Electrolysis is the process in which electrical energy is used
to cause a nonspontaneous chemical reaction to occur.

19.8
Electrolysis of Water

19.8
 Electrolysis and Mass Changes

charge (C) = current (A) x time (s)

1 mole e- = 96,500 C

So what is the charge on a single electron?

19.8