REDOKS

(Reduction and Oxidation)

 Copper wire can be oxidized to copper
ions by the reduction of silver ions to
silver

Cu(s) + 2 Ag+ Cu2+ + 2 Ag(s)

 Copper weathering
 Iron rust

2/3 Fe(s) + CCl4 + 2 H2O = 2/3 Fe(OH)3(s) +

CHCl3 + Cl- + H+
 Pengenalan
Tindakbalas redoks melibatkan pertukaran
elektron di antara 2 spesis kimia.
Sebatian yang kehilangan elektron
dikatakan sebagai teroksida (oxidized)
manakala yang menerima elektron
sebagai terturun (reduced).
Bahan yang teroksida dinamakan sebagai
agen penurunan manakala bahan yang
terturun sebagai agen pengoksidaan
 Tindakbalas Gabungan Ion (Ion
Combination Reactions) Bukan REDOKS
Ada beberapa tindakbalas yang merupakan
tindakbalas gabungan ion.
Tindakbalas seperti ini TIDAK melibatkan
pertukaran VALENSI (nombor pengoksidaan)
bahan kimia yang bertindakbalas.
Contoh tindakbalas Gabungan Ion:

CuSO4 + 2NaOH Cu(OH)2 + Na2SO4

Dalam tindakbalas di atas, Kuprum (Cu) dalam

bentuk ionik Cu2+ disebelah kiri persamaan, dan
disebelah kanan juga dalam bentuk Cu2+. Oleh
itu tida pertukaran dalam nombor pengoksidaan.

Cu2+ + SO42- + 2Na+ + 2OH-

(Cu2+ + 2OH-) pepejal + 2Na+ + SO42-
 Nombor Pengoksidaan
sama dengan valensi tetapi mempunyai
tanda + atau - , bertujuan
mengekspresikan bentuk cas pada spesis
tertentu apabila terbentuk dari atom yang
neutral
Sebagai contoh, nombor pengoksidaan
klorin dalam asik klorik HClO3 ialah +5
manakala dalam asik perklorik HClO4
adalah +7.
 Dalam tindakbalas redoks, valensi
(nombor pengoksidaan) bahan tindakbalas
(reactants) berubah.
Contoh:

2Fe3+ + Sn2+ 2Fe2+ + Sn4+

Besi (III) dan Timah (II) telah

bertindakbalas untuk menghasilkan besi
(II) dan Timah (IV).
Tindakbalas ini berjalan dengan kehadiran
asid hidroklorik, tetapi tindakbalas
pengoksidaan dan penurunan hanya
melibatkan besi dan timah sahaja.
Fe (logam) + Cu2+ Fe2+ + Cu (logam)

Fe mendermakan 2 elektron kepada Cu2+ untuk

membentuk Cu (logam).

Fe yang kehilangan 2 elektron, teroksida; manakala

Cu2+ yang mendapat 2 elektron, terturun.

Zn + 2HCl Zn2+ + H2 +2Cl-

Dalam tindakbalas ini:

Zn + 2H+ Zn2+ + H2

Zn teroksida manakala H+ terturun.

 Separuh sel
Kadangkala, adalah lebih mudah untuk melihat
pertukaran elektron dalam sesuatu sistem jika
dipisahkan kepada langkah yang tetap, iaitu
pengoksidaan untuk satu bahan dan penurunan
untuk bahan yang lain.
Contoh:
2Fe3+ + Sn2+ 2Fe2+ + Sn4+

Pisahkan kepada 2 langkah:

2Fe3+ + 2e- 2Fe2+ (penurunan)

(6+) + (2-) (4+) (keseimbangan cas)

Sn2+ Sn4+ + 2e- (pengoksidaan)

(2+) (4+) + (2-)
 Dalam menulis persamaan separuh sel bagi
pengoksidaan; elektron sentiasa ditulis pada sebelah
kanan (produk tindakbalas) menunjukkan
kehilangan;
manakala persamaan separuh sel untuk penurunan,
elektron ditulis pada sebelah kiri (bahan
tindakbalas) menunjukkan ia diterima
Jika dicampur kedua-dua persamaan setengah
sel:

2Fe3+ + 2e- + Sn2+ 2Fe2+ + Sn4+ + 2e-

Elektron kedua-dua belah membatalkan satu sama lain,

maka persamaan menjadi:

2Fe3+ + Sn2+ 2Fe2+ + Sn4+

 Menyeimbangkan
Persamaan Redoks
Identify the species being oxidised and the
one being reduced by the changes in
oxidation number.
For:
MnO4-(aq) + C2O42-(aq) Mn2+(aq) + CO2(g)

The oxidation number of Mn decreases

from +7 to +2.
Therefore MnO4- ion is reduced.
The oxidation number of carbon increases
from +3 to +4 so the oxalic acid is
oxidised
 Write the two unbalanced half equations
for the oxidation and reduction reactions

Oxidation: C2O42- CO2

Reduction: MnO4- Mn2+

Balance all elements in half reactions

except O and H

C2O4 2CO2
MnO4- Mn2+
 In acidic solution balance O by using
H2O, then balance H by using H+
Balance the O atoms with H2O

C2O42- 2CO2
MnO4- Mn2+ + 4H2O

Balance the H atoms with H+

C2O42- 2CO2
MnO4- + 8H+ Mn2+ + 4H2O
 In basic solution balance O by H2O, balance H
by adding H2O to the side of each half
reaction that requires H and adding OH- to
the other side.
Balance the electric charges by adding
electrons to the left for the reduction
equation and to the right for the oxidation.

C2O42- 2CO2 + 2e-

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

Multiply all species in either one or both

equations by factors that will result in an
equal number of electrons in both half
reactions. Then add both half equations
together.
 Multiply the oxalic acid equation by 5
and the permanganate by 2

5C2O42- 10CO2 + 10e-

2MnO4- + 16H+ + 10e- 2Mn2+ + 8H2O

Overall:

2MnO4- + 5C2O42- + 16H+ 2Mn2+ + 10CO2 + 8H2O

 Ecological aspects of redox
OM degradation
Fastest under oxidized conditions
Toxic by-products may accumulate (reduced)
Ethylene gas, alcohols, and organic acids
Redox of elements
Nutrients (Fe3+ vs. Fe2+, SO42- vs. S2-)
Toxic elements
Soil colors
CH4 production
Plant growth
Lack of energy
Reduce root elongation
 Redox
Oxidation
loss of electrons
compound that loses electrons is oxidized
compound that causes electron loss is the
oxidant (a.k.a. electron acceptor)

Reduction
gain of electrons
compound that gains electrons is reduced
compound that causes electron gain is the
reductant
(a.k.a. electron donor)
 Oxidation state
difference between number of protons and
electrons

oxidation state > 0: oxidized

oxidation state < 0: reduced

compounds can be transformed (through redox

reactions) over a wide range of oxidation state
Carbon: C(-IV) to C(+IV)
Sulfur: S(-II) to S(+VI)
Nitrogen: N(-III) to N(V)
Manganese: Mn(+II) to Mn(+VII)
Iron: Fe(0) to Fe(III)
 Hukum Memberi
Nombor Pengoksidaan
Nombor pengoksidaan atom atau
unsur bebas (tidak bergabung)
adalah 0
Contoh: Na, Ca, mempunyai nombor
pengoksidaan 0.
Nombor pengoksidaan untuk unsur
yang bergabung sendiri sentiasa 0
Contoh: H2, O2, P4 mempunyai
nombor pengoksidaan 0.
 Kebanyakan sebatian yang
mengandungi hidrogen, nombor
pengoksidaan H adalah +1.
Pengecualian adalah apabila H bergabung
dengan logam alkali (alkaline metals) atau
alkali tanah (alkaline earth) untuk
membentuk logam hidrid sperti: NaH, LiH,
CaH2. dimana, nombor pengoksidaan H
adalah -1.
Dalam sebatian melibatkan logam
alkali (alkali metals) unsur diberi
nombor pengoksidaan +1.
Dalam sebatian melibatkan logam
alkali bumi (alkaline earth metals),
the elements are asasigned oxidation
number of +2.
 Oksigen biasanya diberi nombor pengoksidaan
-2 untuk oksidanya. Dan mempunyai nombor
pengoksidaan -1 dalam peroksida (H2O2).
Fluorine sentiasa mempunyai nombor
pengoksidaan -1 dalam sebatian. Unsur lain
dalam kumpulan tersebut juga mempunyai
nombor pengoksidaan -1 dalam sebatian yang
mempunyai unsur yang berelektronegatifan
rendah.
Jumlah semua nombor pengoksidaan
semua atom dalam formula untuk sebatian
yang neutral adalah 0.
Jumlah nombor pengoksidaan untuk ion
atau kompleks ion adalah sama dengan
cas pada ion tersebut.
 Nombor pengoksidaan yang negatif untuk
sebatian yang mempunyai atom yang berbeza
diberi kepada atom yang lebih
elektronegatif.

Contoh Nombor pengoksidaan

HCl H = +1, Cl = -1
H2O H = +1, O = -2

Gabungan bukan logam yang TIDAK melibatkan

Hidrogen atau Oksigen, bukan logam yang lebih
elektronegatif dianggap sebagai negatif.

Contoh Nombor pengoksidaan

CCl4 C = +4, Cl = -1
SF6 S = +6, F = -1
CS2 C = +4, S = -2
 What is the oxidation numbers of
the following chemical species
MnOOH
NO3-
MnO2
Fe(OH)3
SO42-
NO2-
 pE concept
The aquesous electron is a very useful
conceptual device for describing redox
status of soils, just as the aqueous proton
iis so useful in decribing the acid-base
status of soils
As pH is expressed as negative log of free-
proton activity, similarly soil oxidizability
can be expressed by the negative log of
the free-electron activity

pE = -log10(e-)
 Free electron does not exist in
aqueous solutions
Virtual electron activity
Oxidation and reduction
high pe (> 0): oxidizing
low electron activity
low pe (< 0): reducing
high electron activity
Unlike pH, pE can take negative
values
 Another way to express electron
activity
oxidation/reduction potential
a.k.a. redox potential
designed EH (also Eh)
E for electrical potential
H denotes baseline is H+/H2(g) redox
potential
EH and EH0
an electrochemical potential
presented as a voltage, but not the actual
electrical potential in a solution
a virtual potential
 Redox potential (EH)
General (IUAC) convention writes the general half-
reaction as a reduction with the electrons on the
left as

Oxidized + mH+ + ne- = Reduced

The theoretical voltage for this reaction (eqn. 1) is

given by Nernsts equation:

EH = EoH 0.059/n log [(reduced/oxidized)]

Where EH = potential half cell

EoH = standard state pontential half-cell
 EH will equal EoH only when the last term
is unity, a state which will never exist in
soil
For reaction
MnO2(s) + 4H+ + 2 e- = Mn2+ + 2H2O EoH = 1.23 V

EH = EoH (0.059/2)log[(Mn2+)/(H+)4]
EH = 1.23 0.0295log (Mn2+) - 0.118pH

If (Mn2+) = 10-5 M, then

EH = 1.378 0.118pH
We would be able to plot a graph relating EH and pH
 Relation between EH and pe
For any redox reaction:
Oxidized + ne- = reduced
log K = log [(reduced)/(oxidized)] + npe (1)

From Nernst equation,

EH = EoH 0.059/n log [(reduced/oxidized)] (2)

By substituting (1) in (2) well get

EH = 0.059pe
 Relationship between pe and pH
Previously, for reaction:
MnO2(s) + 4H+ + 2 e- = Mn2+ + 2H2O EoH = 1.23 V

EH = 1.23 0.0295log (Mn2+) - 0.118pH

Since EH = 0.059pe, then,

pe = 20.8 -0.5log(Mn2+) 2pH

We have an equation relating pe and pH

 Elements most affected by redox
reactions in soils
C, N, O, S, Mn and Fe
In contaminated soils, will include
As, Se, Cr, Hg, and Pb
 Measurement of soil redox
potential
Use Pt electrode and saturated calomel
electrode
Pt electrode responds to the electron transfer
associated with the oxidation half reaction
whose associated pe is to be measured
Calomel electrode undergoes the half cell
reaction

Hg2Cl2 (s) + e-(aq) = Cl+ + Hg(l)

log K = 4.53 at 25oC
 pe-pH diagrams
fields of stability of redox species
function of pH affects proton, hydroxide exchange
function of pe affects electron exchange
bounded by water stability
high pe
oxidation of water to oxygen gas
low pe
reduction of water to hydrogen gas
equilibrium
still must remember kinetics
big energy barriers
biological mediation
 pe-pH diagram of
Mn-CO2-H2O system
total Mn is 10-5 M; total CO2 is 10-3 M
 Reduction reaction sequence in
waterlogged soils
The EoH values are useful in understanding
the sequence of reactions likely to occur
as the soil becomes waterlogged and
molecular oxygen is depleted in the soil
due to its low solubility in water and its
consumption by continued biological
activity
Microbial activity changes from aerobic to
anaerobic when the dissolved oxygen
diminishes to trace levels (about 10-6M)
 Redox potential is said to be well poised
similar to buffering of soil pH by large
reserve of electron acceptors such as
MnO2 and Fe(OH)3
However, high amount of readily available
organic matter level in soils usually means
that the electron acceptors are
overwhelmed by the microbial activity ad
the redox potential decreases
The observable change that follows
waterlogging, once O2 is consumed in the
water-saturated soil by biological activity,
is a decrease in redox potential
accompanied by a rise in pH towards 7
 Most reduction reactions consume
H+, accounting for this pH change
Anaerobic organisms are able to use
oxidized chemical spesies such as
nitrate as electron aceptors in place
of molecular oxygen
Consequently, microbial reduction of
nitrate to N2 (denitrification) and Mn
oxide to Mn2+ occurs in the early
stages of soil reduction
 Reduced species such as nitrite (NO2-) and
Mn2+appear in solution
As more extreme reducing conditions
develop, NH4+ accumulates from nitrogen
reduction reactions and iron solubility
increases in the form of Fe2+
Ultimately, the prolonged anoxic conditions
cause sulfate to be reduced to sulfide which
then precipitated with Fe2+ forming FeS2
If the redox potential decreases below 0.2
V, organic carbon can undergo reduction,
forming methane
At extreme conditions, hydogen gas may be
generated in the soil
 Application

Oxygen reacts directly with Fe2+ to limit

iron solubility in aerated water. How to
relate (Fe2+) to pH in aerobic soil?

Fe(OH)3 + 3H+ + e- = Fe2+ + 3H2O EoH = 1.057V

H2O = O2+ H+ +e- EoH = -1.229V

Fe(OH)3 + 2H+ = Fe2+ + O2 + 5/2H2O EoH = -0.172V

E = Eo -0.059log[(Poxygen)1/4 (Fe2+)]
(H+)2
E = -0.172 (0.059)log(Poxygen)
0.059log(Fe2+) 2(0.059)pH

Since at equilibrium, E = 0, and we take

Poxygen = 0.2 atm,

log(Fe2+) = -2.74 - 2pH

Even at pH =2, log(Fe2+) = -6.74

(Fe2+) = 10-6.74M