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Reduksi-Oksidasi dalam Kimia

Anorganik
Struktur, Sifat dan Reaktivitas Senyawa
Anorganik (SSRSA)
by
Hamzah Fansuri, Ph.D
Rencana Pembelajaran
Oksidasi: pengurangan elektron dari suatu
zat/bahan
Reduksi: penambahan elektron pada suatu
zat/bahan

Mengembangkan konsep untuk memahami


mengapa terjadi reaksi oksidasi dan reduksi
berdasarkan aspek termodinamika.
Menjelaskan prosedur untuk menganalisis
reaksi redoks dalam larutan dan mengamati
bahwa potensial elektrode dari zat/bahan
yang aktif secara elektrokimia, merupakan
data yang berguna dalam menentukan dan
memahami kestabilan zat/bahan dan
kelarutan garam-garamnya
Menjelaskan prosedur untuk menunjukkan
kecenderungan dalam kestabilan bermacam-
macam keadaan oksidasi, termasuk juga
pengaruh pH.
Ekstraksi logam-logam dari bijihnya
Reaksi Redoks
A large class of reactions of inorganic compounds
can be regarded as occurring by the transfer of
electrons from one species to another.
The species that supplies electrons is the
reducing agent (or reductant) and the species
that removes electrons is the oxidizing agent (or
oxidant).
Many redox reactions release a great deal of
energy and they are exploited in combustion or
battery technologies.
Contoh reaksi redoks
Many redox reactions occur between reactants in
the same physical state. Some examples are:
Dalam gas:
2 NO(g) + O2(g) 2 NO2(g)
2 C4H10(g) + 13 O2(g) 8 CO2(g) + 10 H2O(g)

Dalam larutan:
Fe3+(aq) + Cr2+(aq) Fe2+(aq) + Cr3+(aq)
3 CH3CH2OH(aq) + 2 CrO42-(aq) + 10 H+(aq)
3CH3CHO(aq) + 2 Cr3+(aq) + 8 H2O(l)
Contoh reaksi redoks
Many redox reactions occur between reactants
in the same physical state. Some examples are:
Dalam sistem biologi:
Mn4(V,IV,IV,IV) + 2 H2O(l) Mn4(IV,III,III,III) +
4H+(aq) + O2(g)

Dalam Padatan:
LiCoO2(s) + C(s) Li@C(s) +
CoO2(s)
Pengolahan Bijih Logam Logam
Smelting is a form of Smelting involves more than just
melting the metal out of its ore.
extractive metallurgy; Most ores are a chemical
its main use is to compound of the metal with
other elements, such as oxygen
produce a base metal (as an oxide), sulfur (as a sulfide)
or carbon and oxygen together
from its ore. This (as a carbonate). To produce the
metal, these compounds have to
includes production of undergo a chemical reaction.
silver, iron, copper and Smelting therefore consists of
using suitable reducing
other base metals from substances that will combine with
those oxidizing elements to free
their ores the metal.
Proses
Roasting
- Untuk senyawa karbonat dan sulfida
- Membuang karbon atau belerang yang tidak diinginkan
sehingga mineralnya menjadi oxida yang dapat direduksi
langsung
- Biasanya dilakukan dalam suasana yang mengoksidasi
Contoh:
Malachite (a common ore of copper) kandungan utamanya
adalah copper carbonate hydroxide
Cu2(CO3)(OH)2. Mineral ini terurai menjadi 2CuO, CO2, and
H2O dalam beberapa tahap pada 250 C dan 350 C. Oksida
tembaga (copper(II) oxide) yang tersisa dapat direduksi
langsung menjadi tembaga.
Proses
Roasting
- Untuk senyawa karbonat dan sulfida
- Membuang karbon atau belerang yang tidak diinginkan
sehingga mineralnya menjadi oxida yang dapat
direduksi langsung
- Biasanya dilakukan dalam suasana yang mengoksidasi
Contoh:
Galena (the most common mineral of lead) memiliki
kandungan utama timbal sulfida (PbS). The sulfida
tersebut dioksidasi menjadi sulfit (PbSO3) yang
selanjutnya diuraikan menjadi oksida timbal dan gas
belerang dioksida (PbO and SO2).
Proses
Reduction
- Merupakan tahap akhir bersuhu tinggi pada proses smelting
- Oksida diubah menjadi logam.
- Dilakukan dalam lingkungan yang mereduksi (seringkali disediakan
oleh karbon monoksida yang dihasilkan dari pembakaran tidak
sempurna) yang mengkonsumsi oksigen dari bahan baku.
Dibutuhkan sangat tinggi namun variasinya sangat luas, tergantung
pada reaksinya dan titik leleh logam
Contoh:
Oksida besi menjadi besi pada suhu seitar 1250 C (300 oC lebih
rendah dari titik leleh besi 1538 C)
Oksida raksa menjadi uap pada suhu 550 C (hampir 600 oC di atas
titik didik raksa: -38 C)
Fluks dan slag mempunyai fungsi tambahan setelah tahapan reduksi
yaitu menutupi permukaan logam cair agar tidak teroksidasi.
Proses
Fluxes (Fluks)
Fluks digunakan untuk beberapa
tujuan yang salah satunya
adalah mengkatalisis reksi-reaksi
yang diinginkan dan terikat
secara kimia pada pengotor yang
tidak diinginkan atau produk.
Oksida kalsium (batu
kapur/lime) sering dgiunakan
sebagai fluks. Oksida Kalsium
bereaksi dengan CO2 dan SO2.
Smelting: Bijih Besi Besi
Menyeimbangkan Persamaan Redoks

MENYEIMBANGKAN REAKSI
REDOKS
Menyeimbangkan Persamaan Redoks
1. Write the unbalanced half-reactions for the two species as
reductions.
2. Balance the elements other than hydrogen.
3. Balance O atoms by adding H2O to the other side of the
arrow.
4. If the solution is acidic, balance the H atoms by adding H+; if
the solution is basic, balance the H atoms by adding OH- to
one side and H2O to the other.
5. Balance the charge by adding e-.
6. Multiply each half-reaction by a factor to ensure that the
numbers of e- match.
7. Subtract one half-reaction from the other and cancel
redundant terms.
Menyeimbangkan Persamaan Redoks
Example 1:
I- is oxidized to IO3- by MnO4-, which is reduced
to Mn2+.
How can this reaction be balanced? In the ion-
electron method we follow a series of four
steps:
Menyeimbangkan Persamaan Redoks
Step 1A: Write out the (unbalanced) reaction and identify
the elements that are undergoing redox.

MnO4- + I- IO3- + Mn2+ (The elements undergoing redox


are Mn and I)

Step 1B: Separate the reaction into two half reactions,


balancing the element undergoing redox in each.

MnO4- Mn2+
I- IO3-
Menyeimbangkan Persamaan Reaksi
Redoks
Step 2A: Balance the oxygen atoms by adding water to one
side of each half reaction.

MnO4- Mn2+ + 4H2O


3H2O + I- IO3-

Step 2B: Balance the hydrogen atoms by adding H+ ions.


8H+ + MnO4- Mn2+ + 4H2O
The left side has a net charge of +7 and the right side has a
net charge of +2
3H2O + I- IO3- + 6H+
The left side has a net charge of -1 and the right side has a net
charge of +5
Menyeimbangkan Persamaan Reaksi
Redoks
Step 2C: Balance the overall charge by adding electrons

8H+ + 5e- + MnO4- Mn2+ + 4H2O


The left side has a charge of +2 while the right side has a
charge of +2. They are balanced.
3H2O + I- IO3- + 6H+ + 6e-
The left side has a charge of -1 while the right side has a
charge of -1. They are balanced.
Note: We did not need to explicitly determine the
oxidation states of Mn or I to arrive at the correct number
of electrons in each half reaction.
Menyeimbangkan Persamaan Reaksi
Redoks
Step 3: Combine the half reactions so that there are equal
numbers of electrons on the left and right sides

6 x (8H+ + 5e- + MnO4- Mn2+ + 4H2O)


5 x (3H2O + I- IO3- + 6H+ + 6e-)

48 H+ + 30 e- + 15 H2O + 6 MnO4- + 5 I- 5 IO3- + 6 Mn2+ +


24H2O + 30 e- + 30 H+

Cancel the H+, electrons, and water:

18 H+ + 30 e- + 15 H2O + 6 MnO4- + 5 I- 5 IO3- +


6Mn2+ + 9H2O + 30 e- + 30 H+
Menyeimbangkan Persamaan Reaksi
Redoks
Check your work by making sure that all elements and charges are
balanced.

Step 4: If the reaction occurs under basic conditions, we add OH- to


each side to cancel H+
18H+ + 18OH- + 6MnO4- + 5I- 5IO3- + 6Mn2+ + 9H2O + 18OH-

The 18H+ + 18OH- will become 18H2O so the overall balanced reaction
is:

9H2O + 6MnO4- + 5I- 5IO3- + 6Mn2+ + 18OH-

Again, it is a good idea to check and make sure that all of the elements
are balanced, and that the charge is the same on both sides. If this is
not the case, you need to find the error in one of the earlier steps.
Latihan
5.1 Assign oxidation numbers for each of the
elements participating in the following
reactions.
2 NO(g) + O2(g) 2 NO2(g)
2 Mn3+(aq) + 2 H2O(l) MnO2 + Mn2+ + 4 H+(aq)
LiCoO2(s) + C(s) Li+@C(s) + CoO2(s)
Ca(s) + H2(g) CaH2(s)
Latihan
5.6 Balance the following redox reaction in acid
solution: MnO4- + H2SO3 Mn2+ + HSO4-.
Predict the qualitative pH dependence on
the net potential for this reaction (that is,
increases, decreases, remains the same).
Pertemuan ke dua

POTENSIAL STANDAR DAN


SPONTANITAS
Spontan-Tidak Spontan

Suatu reaksi bersifat spontan secara


termodinamik dalam artian K > 1, jika E0 > 0. E0
adalah selisih potensial standarsetengah reaksi
(half-reaction)
0
=

Tetapan
Kesetimbangan
Reaksi redoks selalu
berpasangan hanya
perubahan energi bebas
Gibbs (DGr0)nya yang
penting
Untuk menentukan
besaran DGr 0, salah satu
setengah reaksi dapat
dipilih sebagai referensi
(DGr = 0)

H+(aq) + e- H2(g) DG = 0
pada semua suhu
Gr0 untuk reduksi Zn2+ ions ditentukan secara
eksperimen:

Zn2+(aq) + H2(g) Zn(s) + 2 H+(aq); rG0=+147 kJ.mol-1

karena setengah reaksi reduksi H+ memberi


kontribusi nol terhadap energi bebas Gibbs
(sesuai dengan kesepapakan/convention), maka:

Zn2+(aq) + 2e- Zn(s) rG0 = +147 kJ/mol


Pengukuran DGr0
Reaksi yang diamati adalah reaksi yang
mendorong adanya arus elektron melewati
lintasan luar (external circuit) lalu diukur beda
potensialnya.
Katoda - reduksi (Ka-Red)
Anoda oksidasi (An-Oks)
Beda potensial dapat diubah menjadi energi
bebas Gibbs reaksi dengan:
rGr0 = -FE0
koefisien stoikiometri elektron-elektron yang
berpindah ketika setengah reaksi digabungkan
dan
F = konstanta Faraday (96.480 C.mol-1).
Sel Galvani
Daftar Istilah
E0 = Potensial Standar/Standard Potential
E0cell = Potensial sel standar
emf = gaya elektromotif (electromotive force)
sebutan lain untuk potensial sel
The energy in joules is equal to the voltage in volts
times the electrical charge in coulombs. A
coulomb is a fundamental unit of electrical
charge, and it is the charge transported by a
constant current of 1 ampere in one second.
Potensial Sel
Potensial yang berhubungan dengan rG0 dari suatu setengah reaksi
ditulis sebagai E0 dimana:

rG0 = -FE0
E0 = potensial standar (atau potensial reduksi standar) ( to
emphasize that, by convention, the half-reaction is a reduction and
written with the oxidized species and electrons on the left).
Karena Gr0 untuk reduksi H dinyatakan sebagai nol maka potensial
standar pasangan H/H2 juga nol di semua suhu:

H+(aq) + e- H2(g) E0(H+, H2) = 0


Potensial Sel
Illustrasi
For the Zn2/Zn couple, for which = 2, it follows
from the measured value of rG0 that at 25 oC:
Zn2+(aq) + 2e- Zn(s) E0(Zn2+, Zn) = -0.76 V

Untuk sepasang setengah reaksi, selisih


potensialnya dalam keadaan standar disebut
potensial sel E0Cell
Pada reaksi:
2H+(aq) + Zn(s) Zn2+(aq) + H2(g)

Pasangan setengah sel:

H+(aq) + e- H2(g) E0(H+, H2) = 0 } x 2


Zn2+(aq) + 2e- Zn(s) E0(Zn2+, Zn) = -0.76 V
2H+(aq) + 2e- H2(g) E0(H+, H2) = +0.00 V
Zn(s) Zn2+(aq) + 2e- E0(Zn2+, Zn) = +0.76 V
-------------------------------------------------------------- +
2H+(aq) + Zn(s) Zn2+(aq) + H2(g) E0 = +0.76 V
TRENDS IN STANDARD POTENTIALS
The atomization and ionization of a metal and the
hydration enthalpy of its ions all contribute to the
value of the standard potential
Nilai absolut (bukan yang sesuai
konvensi di mana DfH (H+, aq) =
0) entalpi pembentukan M+ dan
H + adalah yang digunakan di sini.
Jadi, digunakan DfH (H+, aq) =
445 kJ.mol-1, yang didapatkan
dengan mengambil
pembentukan sebuah atom H
dari H2(g) (+218 kJ.mol-1),
ionisasi menjadi H+(g) (1312
kJ.mol-1) dan hidrasi H+(g) (sekitar
1085 kJ.mol-1).
The factors that contribute to the standard potential of
the couple M/M can be identified by consideration of a
Potensial
thermodynamic
Elektronegativitas cycle and the corresponding changes in
semakin kecil
semakin kecil
Gibbs energy that contribute to the overall reaction
Lithium has a higher enthalpy of
E (V)
sublimation and ionization energy than
Li+/Li 2,2 (1,0) -3,04 Cs, and in isolation this difference would
Na+/Na 0,9 -2,71 imply a less negative standard potential
as formation of the ion is less favourable.
K+/K 0,8 -2,93 However, Li has a large negative enthalpy
Rb+/Rb 0,8 -2,98 of hydration, which results from its small
Cs+/Cs 0,79 (0,7) -2,94 (-3,03) size (its ionic radius is 90 pm) compared
with Cs (181 pm) and its consequent
Ag+/Ag +0,80 strong electrostatic interaction with
water molecules. Overall, the favourable
The relatively less negative standard enthalpy of hydration of Li outweighs
potential for Na+/Na in comparison with terms relating to the formation of Li(g)
Group 1 (close to 2.9 V) is a result of a and gives rise to a more negative
combination of a fairly high sublimation standard potential.
enthalpy and moderate hydration
enthalpy
K Rb

410 403

-2.93 -2.98

-3.04
The oxidized member of a couple is a strong oxidizing
agent if E0 is positive and large; the reduced member is
a strong reducing agent if E0 is negative and large
Potensial standar negatif (E0 < 0) menunjukkan bahwa pasangan
tereduksi (misalnya Zn in Zn2+/Zn) adalah pereduksi ion H+ dalam
keadaan standar dalam larutan berair.

jika E0 (Ox, Red) < 0, maka zat Red cukup kuat berlaku sebagai
agen pereduksi ion H+ (dalam hal ini K > 1).

Ox/Red couple with strongly positive E0 [Ox is strongly oxidizing]


.
.
.
Ox/Red couple with strongly negative E0 [Red is strongly reducing]
Deret Elektrokimia
Among the couples in
Table 5.2, is the
permanganate ion,
MnO4-, the common
analytical reagent
used in redox
titrations of iron.
Which of the ions
Fe2+, Cl-, and Ce3+ can
permanganate
oxidize in acidic
solution?
Answer: We need to note that a reagent that is capable of reducing MnO4-
ions must be the reduced form of a redox couple having a more negative
standard potential than the couple MnO4-/Mn2+. The standard potential of
the couple MnO4-/Mn2+ in acidic solution is 1.51 V. The standard
potentials of Fe3+/Fe2+, Cl2/Cl-, and Ce4+/Ce3+ are 0.77, 1.36, and 1.76 V,
respectively. It follows that MnO4- ions are sufficiently strong oxidizing
agents in acidic solution (pH = 0) to oxidize Fe2+ and Cl-, which have less
positive standard potentials. Permanganate ions cannot oxidize Ce3+,
which has a more positive standard potential. It should be noted that the
presence of other ions in the solution can modify the potentials and the
conclusions (Section 5.10); this variation with conditions is particularly
important in the case of H+ ions, and the influence of pH is discussed in
Section 5.6. The ability of MnO4- ions to oxidize Cl- means that HCl cannot
be used to acidify redox reactions involving permanganate but H2SO4 is
used instead.

Self-test 5.3 Another common analytical oxidizing agent is an acidic


solution of dichromate ions, Cr2O72-, for which E (Cr2O72-, Cr3+) = 1.38 V. Is
the solution useful for a redox titration of Fe2+ to Fe3+? Could there be a
side reaction when Cl- is present?
Persamaan Nernst
The cell potential at an arbitrary composition of
the reaction mixture is given by the Nernst
equation
DrG = DrG0 + RT lnQ Reaction
Quotient

a OxA + b RedB a RedA + b OxB



[ ] [ ]
=
[ ] [ ]
Karena:
Ecell = -rG/F dan Ecell0 = -DrG 0 /F

sehingga:

DrG = DrG0 + RT lnQ

0
=

Dalam keadaan
setimbang, Ecell = 0 dan
Q = K sehingga:

0
0 =

0

=
= 1; T = 25 oC
Dalam hal potensial sel Ecell adalah selisih antara
dua potensial reduksi sebagaimana Ecell0 adalah
selisih dua potensial reduksi standar maka:


0
=

Tapi dengan
a Ox + e- a Red

[ ]
maka: =
[ ]
Kaitan antara potensial sel standar dengan suhu
dapat digunakan untuk menentukan entropi
reaksi redoks:

0
= 0 = 0 0

Pada perubahan suhu yang kecil, DH0 dan DS0


tidak terpengaruh oleh suhu sehingga:

0 2 0 1
= (2 1 ) 0
0 0
0
2 1
=
2 1

The standard reaction entropy DrS often reflects the


change in solvation accompanying a redox reaction: for
each half-cell reaction a positive entropy contribution is
expected when the corresponding reduction results in a
decrease in electric charge (solvent molecules are less
tightly bound and more disordered). Conversely, a
negative contribution is expected when there is an
increase in charge.
Entropy contributions to standard potentials are usually
very similar when comparing redox couples involving the
same change in charge.
Example
Calculate the cell potential (measured using a
load of such high resistance that negligible
current flows) produced by a fuel cell in which
the overall reaction is 2 H2(g) + O2(g) 2 H2O(l)
with H2 and O2 each at 1 bar and 25 oC.
(Note that in a working PEM fuel cell the
temperature is usually 80-100 oC to improve
performance)
Answer We note that under zero-current conditions, the cell potential
is given by the difference of standard potentials of the two redox
couples. For the reaction as stated, we write:
Right: O2(g) + 4 H+(aq) + 4 e- 2 H2O(l) E0 = +1.23 V
Left: 2 H(aq) + 2 e- H2 (g) E0= 0 V
Overall (Right-Left) 2 H2(g) + O2(g) 2 H2O(l)

The standard potential of the cell is therefore


Ecell = (+1.23 V) - 0 = 1.23 V
The reaction is spontaneous as written, and the right-hand electrode is
the cathode (the site of reduction).

Self-test 5.4 What potential difference would be produced in a fuel cell


operating with oxygen and hydrogen with both gases at 5.0 bar?
Pertemuan ke tiga

STABILITAS REDOKS
When assessing the thermodynamic stability of
a species in solution, we must bear in mind all
possible reactants: the solvent, other solutes,
the species itself, and dissolved oxygen. In the
following discussion, we focus on the types of
reaction that result from the thermodynamic
instability of a solute. We also comment briefly
on kinetic factors, but the trends they show are
generally less systematic than those shown by
stabilities.
PENGARUH pH
Many redox reactions in aqueous solution involve transfer of H+ as well as
electrons and the electrode potential therefore depends on the pH.

Dalam larutan berair,


potensial elektroda
bervariasi bersama pH
karena spesies
tereduksi dari
pasangan redoks
umumnya merupakan
basa Brnstedt
Untuk pasangan redoks di mana terjadi transfer
elektron e dan proton H:

+ + +
+


+
= +
+
+
0
=
+ +

+ +
0
= + +

+
Jika: = 0
maka:

+ 10

=

Pada 25 oC:
(0.059) +

=

ln x = ln (10 log x) dan pH = -log[H+], dan kombinasi


konsentrasi Red dan Ox maka E0 menjadi E. F=
96.480 C.mol-1; R= 8.314 4621(75) J.K1.mol1
Contoh
ClO4-(aq) + 2H+(aq) + 2e ClO3- (aq) + H2O(l)

Sehingga pada pH = 0, E = +1.201 V sedangkan


pada pH = 7, potensial reduksipasangan ClO4-
- 0.0592
/ClO3 menjadi 1.201 7 V = 0.788 V.
2
Anion perklorat adalah oksidan yang kebih kuat
dalam kondisi asam
Catatan tambahan
Standard potentials in neutral solution (pH = 7) are denoted EWo .
These potentials are particularly useful in biochemical discussions
because cell fluids are buffered near pH = 7. The condition pH = 7 (with
unit activity for the other electroactive species present) corresponds to
the so-called biological standard state; in biochemical contexts they
are sometimes denoted either E or Em7, the m7 denoting the
midpoint potential at pH = 7.

A brief illustration. To determine the reduction potential of the H/H2


couple at pH = 7.0, the other species being present in their standard
states, we note that E = Eo (H+,H2) = 0. The reduction half-reaction is
2H+(aq) + 2e H2(g), so e = 2 and H = 2. The biological standard
0.0592
potential is therefore E = 0 7 V = 0.41 V
2
Reaksi dengan Air
Air dapat bertindak sebagai pengoksidasi ketika ia tereduksi menjadi H2:
H2O (l) + e- H2 (g) + OH- (aq)
Untuk reduksi ekivalen ion hidronium dalam air pada sembarang pH (tekanan
parsial H2 = 1 bar), persamaan Nernst-nya adalah:
H+ (aq) + e- H2 (g) V pH E = -0 059 V x pH
Yang disebut the reduction of water. Air juga dapat bertindak sebagai
pereduksi ketika ia teroksidasi menjadi O2:
2H2O (l) O2 (g) + 4H+ (aq) + 4e-
Reaksi dengan Air
Ketika tekanan parsial O2 is 1 bar, persamaan Nernst nya untuk setengah
reaksi O2,2H+/2H2O adalah:

E=1.23V - (0.059V x pH)

karena H+/e- = 4/4 = 1.


Baik H maupun O2 memiliki ketergantungan pH yang sama untuk setngah
reaksi reduksi.
1. Oksidasi oleh Air
For metals with large, negative standard potentials, reaction with aqueous acids leads
to the production of H2 unless a passivating oxide layer is formed.
The reaction of a metal with water or aqueous acid is in fact the oxidation of the metal
by water or hydrogen ions because the overall reaction is one of the following
processes (and their analogues for more highly charged metal ions):

M (s) + H2O (l) M+ (aq) + H2 (g) + OH- (aq)


M (s) + H+ (aq) M+ (s) + H2 (g)

These reactions are thermodynamically favourable when M is an s-block metal, a 3d-


series metal from Group 3 to at least Group 8 or 9 and beyond (Ti, V, Cr, Mn, Ni), or a
lanthanoid. An example from Group 3 is:

2Sc (s) + 6H+ (aq) 2Sc3+ (aq) + 3H2 (g)

When the standard potential for the reduction of a metal ion to the metal is negative,
the metal should undergo oxidation in 1 M acid with the evolution of hydrogen.
1. Oksidasi oleh Air
For metals with large, negative standard potentials, reaction with aqueous acids leads
to the production of H2 unless a passivating oxide layer is formed.

Although the reactions of magnesium and aluminium with moist air


are spontaneous, both metals can be used for years in the presence of
water and oxygen. They survive because they are passivated, or
protected against reaction, by an impervious film of oxide. Magnesium
oxide and aluminium oxide both form a protective skin on the parent
metal beneath. A similar passivation occurs with iron, copper, and zinc.
The process of anodizing a metal, in which the metal is made an
anode in an electrolytic cell, is one in which partial oxidation produces
a smooth, hard passivating film on its surface. Anodizing is especially
effective for the protection of aluminium by the formation of an inert,
cohesive, and impenetrable Al2O3 layer.
Reaksi oksidasi air secara heterogen:
2H2O O2 + 4H+ + 4e Oxidation (generation of dioxygen)
4H+ + 4e 2H2 Reduction (generation of dihydrogen)
2H2O 2H2 + O2 Total Reaction
Potensial reduksi standar pada pH = 0:

Oksidasi 2H2O 4H+ + 4e + O2 E = 1.23 V vs.


NHE
Reduction 4H+ + 4e 2H2 E = 0.00 V vs. NHE
Overall 2H2O 2H2 + O2 Ecell = 1.23 V; G = -
475 kJ/mol
Of the two half reactions, the oxidation step is the most
demanding because it requires the coupling of 4 electron
and proton transfers and the formation of an oxygen-
oxygen bond. This process occurs naturally in
plants photosystem II to provide protons and electrons
for the photosynthesis process and release oxygen to the
atmosphere. Since hydrogen can be used as an
alternative clean burning fuel, there has been a need to
split water efficiently. However, there are known
materials that can mediate the reduction step efficiently
therefore much of the current research is aimed at the
oxidation half reaction also known as the Oxygen
Evolution Reaction (OER). Current research focuses on
understanding the mechanism of OER and development
of new materials that catalyze the process.[1]
2. Reduksi oleh Air
Water can act as a reducing agent, that is be oxidized by other species

Pasangan O2, H+/H2O (E = 1.23V - (0.059V x pH)) menunjukkan bahwa


air yang diasamkan adalah pereduksi yang lemah, kecuali terhadap
pengoksidasi yang kuat. Misalnya: Co3+(aq), di mana E(Co3+, Co2+) =
1.92 V. Ia tereduksi oleh air dan melepaskan O2. Karenanya, Co3+ tidak
dapat bertahan dalam larutan dengan pelarut air:

4Co3+(aq) + 2H2O (l) 4Co2+(aq) + O2(g) + 4H+(aq), Ecell = 0.69 V

Only a few oxidizing agents (Ag2+ is another example) can oxidize water
rapidly enough to give appreciable rates of O2 evolution. Standard
potentials greater than 1.23 V occur for several redox couples that are
regularly used in aqueous solution, including Ce4+/Ce3+ (E 1.76 V), the
acidified dichromate ion couple Cr2O72-/Cr3+ (E = 1.38 V), and the
acidified permanganate couple MnO4-/Mn2+ (E = 1.51 V).
2. Reduksi oleh Air
Water can act as a reducing agent, that is be oxidized by other species

The origin of the barrier to reaction is a kinetic one, stemming from the need
to transfer four electrons and to form an O-O bond. Given that the rates of
redox reactions are often controlled by the slow rate at which an O-O bond
can be formed, it remains a challenge for inorganic chemists to find good
catalysts for O2 evolution. The importance of this process is not due to any
economic demand for O2 but because of the desire to generate H2 (a green
fuel) from water by electrolysis or photolysis. Some progress has been made
using Co, Ru, and Ir complexes. Existing catalysts include the relatively poorly
understood coatings that are used in the anodes of cells for the commercial
electrolysis of water. They also include the enzyme system found in the O2
evolution apparatus of the plant photosynthetic centre. This system is based
on a special cofactor containing four Mn atoms and one Ca atom. Although
Nature is elegant and efficient, it is also complex, and the photosynthetic
process is only slowly being elucidated by biochemists and bioinorganic
chemists.
The stability field of water
The stability field of water shows the region of pH and reduction potential where
couples are neither oxidized by nor reduce hydrogen ions.

A reducing agent that can reduce


water to H2 rapidly, or an oxidizing
agent that can oxidize water to O2
rapidly, cannot survive in aqueous
solution.

The stability field of water is the


range of values of potential and pH
for which water is
thermodynamically stable towards
both oxidation and reduction.
The upper and lower boundaries of the stability field are identified by finding
the dependence of E on pH for the relevant half-reactions. As we have seen
above, both oxidation (to O2) and reduction of water have the same pH
dependence (a slope of 0.059 V when E is plotted against pH at 25 oC) and the
stability field is confined within the boundaries of a pair of parallel lines of
that slope.
Any species with a potential more negative than (0.056
v x pH) can reduce water to H2. The lower line defines
the low-potential boundary of the stability field.
Any species with a potential more positive than +(1.23V-
(0.059V x pH)) can liberate O2 from water and the upper
line gives the high-potential boundary.

Couples that are thermodynamically unstable in water lie outside (above or


below) the limits defined by the sloping lines: species that are oxidized by
water have potentials lying below the H2 production line and species that are
reduced by water have potentials lying above the O2 production line.
The stability field of water
The stability field of water shows the region of pH and reduction potential where
couples are neither oxidized by nor reduce hydrogen ions.

The stability field in natural


water is represented by the
addition of two vertical lines at
pH 4 and pH 9, which mark the
limits on pH that are commonly
found in lakes and streams. A
diagram like that shown in the
illustration is known as a
Pourbaix diagram and is widely
used in environmental
chemistry
Oksidasi oleh Oksigen di Udara
The oxygen present in air and dissolved in water can oxidize metals and metal ions in
solution.

The possibility of reaction between the solutes and dissolved O2 must


be considered when a solution is contained in an open beaker or is
otherwise exposed to air. As an example, consider an aqueous
solution containing Fe2+ in contact with an inert atmosphere such as
N2. Because E (Fe3+, Fe2+) = 0.77 V, which lies within the stability field
of water, we expect Fe2+ to survive in water. Moreover, we can also
infer that the oxidation of metallic iron by H+(aq) should not proceed
beyond Fe(II) because further oxidation to Fe(III) is unfavourable (by
0.77 V) under standard conditions. However, the picture changes
considerably in the presence of O2.
Oksidasi oleh Oksigen di Udara
The oxygen present in air and dissolved in water can oxidize metals and metal ions in
solution.

The reaction:
4 Fe2+(aq) + O2 (g) + 4H+ (aq) 4Fe3+ (aq) + 2H2O(l)
is the difference of the following two half-reactions:
O2(g) + 4H+(aq) + 4 e- 2H2O, E = 1.23 V
Fe3+(aq) + e- Fe2+(aq), E = 0.77 V
which implies that Ecell = 0.46 V at pH 0. The oxidation of Fe2+(aq) by O2 is
therefore spontaneous (in the sense K > 1) at pH = 0 and also at higher pH,
although Fe(III) aqua species are hydrolysed and are precipitated as rust.
Disproportionation and
comproportionation
Standard potentials can be used to define the inherent stability and instability of
different oxidation states in terms of disproportionation and comproportionation
Because E (Cu+, Cu) = 0.52 V and E(Cu2+, Cu) 0.16 V, and both potentials lie within
the stability field of water, Cu ions neither oxidize nor reduce water. Nevertheless,
Cu(I) is not stable in aqueous solution because it can undergo disproportionation, a
redox reaction in which the oxidation number of an element is simultaneously raised
and lowered. In other words, the element undergoing disproportionation serves as its
own oxidizing and reducing agent:

2Cu+(aq) Cu2+(aq) + Cu (s)


This reaction is the difference of the following two half-reactions:

Cu+(aq) + e- Cu (s), E = 0.52 V


Cu2+(aq) + e- Cu+ (aq) E = 0.16 V
Disproportionation and
comproportionation
Standard potentials can be used to define the inherent stability and instability of
different oxidation states in terms of disproportionation and comproportionation

Because Ecell = 0.52 V - 0.16 V = 0.36 V for the disproportionation reaction, K


= 1.3 x 106 at 298 K, so the reaction is highly favourable. Hypochlorous acid
also undergoes disproportionation:

5 HClO(aq) 2Cl2(g) + ClO3-(aq) + 2H2O(l) + H+(aq)

This redox reaction is the difference of the following two half-reactions:

4HClO(aq) + 4H+(aq) + 4e- 2Cl2(g) + 4H2O(l), E = +1.63 V


ClO3- (aq) + 5H+(aq) + 4e- HClO(aq) + 2H2O(l), E= +1.43 V

So overall Ecell = 1.63 V - 1.43 V = 0.20 V, and K = 3 x 1013 at 298 K.


Disproportionation and
comproportionation
Standard potentials can be used to define the inherent stability and instability of
different oxidation states in terms of disproportionation and comproportionation

In comproportionation, the reverse of disproportionation,


two species with the same element in different oxidation
states form a product in which the element is in an
intermediate oxidation state. An example is:

Ag2+(aq) + Ag(s) 2Ag+(aq), Ecell = 1.18 V

The large positive potential indicates that Ag(II) and Ag(0) are
completely converted to Ag(I) in aqueous solution (K = 1x1020
at 298 K).
Pengaruh Kompleksasi Senyawa
The formation of a more
thermodynamically stable
complex when the metal is in the
higher oxidation state of a
couple favours oxidation and
makes the standard potential
more negative
The formation of a more stable
complex when the metal is in the
lower oxidation state of the
couple favours reduction and the
standard potential becomes
more positive
The formation of metal complexes affects standard potentials because the ability of a
complex (ML) formed by coordination of a ligand (L) to accept or release an electron
differs from that of the corresponding aqua ion (M).

M+(aq) + e- M(-1)+(aq), E (M)


ML+(aq) + e- ML(-1)+(aq), E (ML)

The change in standard potential for the ML redox couple relative to that of M reflects
the degree to which the ligand L coordinates more strongly to the oxidized or reduced
form of M. The change in standard potential is analysed by considering the
thermodynamic cycle shown in Fig. 5.4. Because the sum of reaction Gibbs energies
round the cycle is zero, we can write:

-FE (M) - RT lnKox + FE(ML) + RT lnKred = 0

where Kox and Kred are equilibrium constants for L binding to M and M(-1)+, respectively
(of the form K [ML]/[M][L]), and we have used rG = RT ln K in each case. This
expression rearranges to:

=

At 25 oC and with ln x = ln 10 log x


= (. )

Thus, every ten-fold increase in the equilibrium constant for
ligand binding to M+ compared to M(-1)+ decreases the
reduction potential by 0.059 V.

A brief illustration. The standard potential for the half-reaction


[Fe(CN)6]3-(aq) + e- [Fe(CN)6]4-(aq) is 0.36 V; that is, 0.41 V more
negative than that of the aqua redox couple [Fe(OH2)6]3+(aq) + e-
[Fe(OH2)6]2+(aq). This equates to CN- having a 107-fold greater affinity
(in the sense Kox 107Kred) for Fe(III) compared to Fe(II).
The relation between solubility and
standard potentials
The standard cell potential can be used to determine the solubility product
The solubility of sparingly soluble compounds is expressed by an equilibrium constant
known as the solubility product, Ksp. The approach is analogous to that introduced
above for relating complexation equilibria to standard potentials. For metal ions M+
forming a precipitate MX with anions X-,

M+(aq) + X-(aq) = MX(s), Ksp = [M+][X-]

To generate the overall (non-redox) solubility reaction we use the difference of the
two reduction half-reactions
M+(aq) + e- M(s), E (M+/M)
MX(s) + e- M(s) + X-(aq), E (MX / M,X )
From which it follows that:
+

,
=

Tugas
1. Kerjakan soal-soal latihan No. 5.8 s/d 5.16

2. Buat ringkasan tentang The diagrammatic


presentation of potential data dari Bab 5.

Tugas dikumpulkan hari Jumat 24 Maret 2017


paling lambat jam 16.00 di jurusan Kimia
THE DIAGRAMMATIC PRESENTATION
OF POTENTIAL DATA
1. Diagram Latimer

(suasana asam)

(suasana basa)

In a Latimer diagram, oxidation numbers decrease from left to right and the
numerical values of E in volts are written above the line joining the species involved
in the couple.
2. Diagram Frost
A Frost diagram (also known as
an oxidation state diagram) of
an element X is a plot of NE
for the couple X(N)/X(0) against
the oxidation number, N, of the
element. The general form of a
Frost diagram is given in Fig.
5.5.
Frost diagrams depict whether
a particular species X(N) is a
good oxidizing agent or
reducing agent. They also
provide an important guide for
identifying the oxidation states
of an element that are
inherently stable or unstable
Fig. 5.9 The interpretation of a Frost diagram to gauge (a) reduction potential, (b)
tendency towards oxidation and reduction, (c, d) disproportionation, and (e, f)
comproportionation.
1. The slope of the line joining any
two points in a Frost diagram is
equal to the standard potential of
the couple formed by the two
species that the points represent.
2. The oxidizing agent in the couple
with the more positive slope is
liable to undergo reduction.
3. The reducing agent of the couple
with the less positive slope is
liable to undergo oxidation
4. A species in a Frost diagram is
unstable with respect to
disproportionation if its point lies
above the line connecting the two
adjacent species (on a convex curve)
5. Two species will tend to
comproportionate into an
intermediate species that lies below
the straight line joining the terminal
species (on a concave curve).
Contoh
Data for nitrogen species
formed in aqueous solution at
pH = 0 and pH = 14. Only NH4+
(aq) is exergonic (fG < 0); all
other species are endergonic
(fG > 0). The diagram shows
that the higher oxides and
oxoacids are highly
endergonic in acid solution
but relatively stabilized in
basic solution. The opposite is
generally true for species with Fig. 5.6 The Frost diagram for nitrogen: the steeper the
N < 0, except that slope of a line, the higher the standard potential for the
hydroxylamine is particularly couple. The red line refers to standard (acid) conditions
(pH = 0), the blue line refers to pH = 14. Note that
unstable regardless of pH. because HNO3 is a strong acid, even at pH = 0 it is present
as its conjugate base NO3-
Contoh: using a Frost diagram to judge the
thermodynamic stability of ions in solution
The Figure on the right shows the
Frost diagram for manganese.

Answer: We approach this


question by inspecting how the
NE value for Mn3+(N = +3)
compares with the values for
species on either side (N < +3, N >
+3)). Because Mn3+ lies above the
line joining Mn2+ to MnO2, it
should disproportionate into
these two species. The chemical
reaction is:
2 Mn3+ (aq) + 2 H2O(l) Mn2+(aq) +
MnO2(s) + 4 H+(aq)
3. Diagram Pourbaix
A Pourbaix diagram is a map
of the conditions of potential
and pH under which species
are stable in water. A
horizontal line separates
species related by electron
transfer only, a vertical line
separates species related by
proton transfer only, and
sloped lines separate species
related by both electron and
proton transfer.
Diagram Pourbaix
A Pourbaix diagram (also known
as an E - pH diagram) indicates
the conditions of pH and potential
under which a species is
thermodynamically stable. The
diagrams were introduced by
Marcel Pourbaix in 1938 as a
convenient way of discussing the
chemical properties of species in
natural waters and they are
particularly useful in
environmental and corrosion
science.
Natural Water
Pourbaix diagrams show that iron can exist in solution as Fe2+ under acidic reducing
conditions such as in contact with soils rich in organic matter.
Exercise
5.2 Use data from Resource section 3 to suggest chemical reagents
that would be suitable for carrying out the following transformations
and write balanced equations for the reactions: (a) oxidation of HCl to
chlorine gas, (b) reduction of Cr(III)(aq) to Cr(II)(aq), (c) reduction of Ag+
to Ag(s), (d) reduction of I2 to I-.

5.3 Use standard potential data from Resource section 3 as a guide to


write balanced equations for the reactions that each of the following
species might undergo in aerated aqueous acid. If the species is
stable, write no reaction. (a) Cr2+, (b) Fe2+, (c) Cl-, (d) HClO, (e) Zn(s).

5.4 Use the information in Resource section 3 to write balanced


equations for the reactions, including disproportionations, that can be
expected for each of the following species in aerated acidic aqueous
solution: (a) Fe2+, (b) Ru2+, (c) HClO2, (d) Br2.
Exercise
5.5 Explain why the standard potentials for the
half-cell reactions:

[Ru(NH3)4]3+(aq) + e- [Ru(NH3)6]2+ (aq)

[Fe(CN)6]3- (aq) + e- [Fe(CN)6]4- (aq)

vary with temperature in opposite directions.


1. On going from N to P, how does the
thermodynamic stability of the +5 oxidation state
alter?
2. What do the diagrams tell you about the
thermodynamic stability of N2 and of P4 with
respect to other N- or P-containing species?
3. Estimate values for Eo N2/[NH3OH]+ and
Eo[NH3OH]+/[N2H5]- and comment on the
thermodynamic stability of [NH3OH]+ in aqueous
solution at pH 0.
CHEMICAL EXTRACTION OF THE
ELEMENTS
Reduksi Kimia
Oksidasi Kimia