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OXIDATION AND REDUCTION

REACTION

REDOX 1
Types of Reactions

REDOX 2
Redox Reaction

 Is the reaction that involve the


transfer of electrons from a reducing
agent to an oxidizing agent

REDOX 3
TYPE OF REDOX REACTION

 OUT OF BODY  IN THE BODY

REDOX 4
Electrochemistry

 Is the branch of chemistry that


deals with the interconversion of
electrical energy and chemical
energy
 Electrochemical processes are
redox reactions in which the energy
released by a spontaneous reaction
is converted to electricity or in
which electrical energy is used to
cause a nonspontaneous reaction
to occur REDOX 5
Definition of Oxidation and
Reduction

Oxidation: Reduction:
Is defined as the is defined as the gain
removal of electrons of electrons

REDOX 6
Common uses of the terms
oxidation and reduction
Term Meaning
Oxidation To Combine with oxygen
To lose hydrogen
To lose electron
To increase in oxidation
Reduction number
To lose oxygen
To combine with hydrogen
To gain electron
To decrease in oxidation
number REDOX 7
Oxidation of Ferrous to
ferric ion

REDOX 8
OXIDATION NUMBER

 Oxidation numbers are the charges


atoms in a compound would have if
the electrons of each bond belonged
to the more electronegative atoms.

REDOX 9
Properties of oxidizing and
reducing agents

oxidizing agents reducing agents


- Gains electrons - Loses electron
- Oxidation number - Oxidation number
decrease increase
- Becomes reduced - Becomes oxidized

REDOX 10
THE RULES FOR ASSIGNING
OXIDATION NUMBER

1. Atoms of any element not


combined with atoms from another
element have oxidation numbers of
zero.

Examples: The oxidation number of


the atom in N2, Br2, Cl2, P4 and S2
are zero

REDOX continued 11
2. The oxidation numbers of
monatomicions equal their ionic
charge.

Examples:
The oxidation numbers of Na+ and
K+ are +1, of Ca2+, Cu2+, and Mg2+
are +2, and Cl¯ and Br¯ are –1.

REDOX
continued 12
3. In their compounds, the
oxidation number of any
atoms of the
- Group I A elements is +1
(e.g., Na+, K+)
- Group II A elements is +2
(e.g., Cu2+, Mg2+)
- Group III A is +3

REDOX
continued 13
4. The oxidation number of any
nonmetal in its binary compounds
with metals equals the charge of the
monatomic anion
e.g., The oxidation number of Br in
CrBr3 is –1 because the monatomic
ion of Br is the bromide ion, which
has
a charge of 1-.

REDOX continued 14
5. In compounds, the oxidation number
of
- O is almost always –2.
(Exceptions occur only when the
rules for H or F would be violated)
- H is almost always +1.
(the exceptions are binary
compounds with metals, like NaH, in
which the H has the oxidation
number –1.)
- F is always –1. (No exceptions.
Fluorine is the most electronegative
of all elements). continued
REDOX 15
6. The sum of the oxidation numbers
of all the atoms in the formula of
the atom, ion, or molecule must
equal the overall charge given for
the formula – the sum rule

continued
REDOX 16
Problem No. 1
Calomel, long use in medicine, has the
formula Hg2Cl2. What are the oxidation
numbers on the atoms in this compound?

The rule for assigning oxidation number: No. 4 & 6


4. The oxidation number of any nonmetal in its
binary compounds with metals equals the
charge of the monatomic anion
6. The sum of the oxidation numbers of all the
atoms in the formula of the atom, ion, or
molecule must equal the overall charge given
for the formula – the sum rule
REDOX 17
The oxidation number of Hg (x)

Hg2Cl2
Rule 4 : Cl 2 atoms X (-1) = -2
Hg 2 atoms X (x) = 2x _
Rule 6 : sum = 0
The value of x comes from the sum,
2x + (-2) = 0
2x = +2
x = +1
The oxidation number of Hg in the Hg2Cl2 is +1
REDOX 18
Which one of the compounds below, that
the element Br has the highest
oxidation number?
(oxidation numbers of: O = -2; K = +1).

 (A) Br2 (C) KBrO3


 (B) KBr (D) K2BrO3
 (E) Br2O

REDOX 19
Does the series, from compounds (a)
to(c) [(a), C2H2; (b). C2H4; (c). C2H6],
(oxidation number of: H = +1), which can
be carried out experimentally, represent:

 A. Oxidation C. Oxidation-reduction
 B. Reduction D. Neutralization
 E. Acid-base

REDOX 20
BALANCING REDOX REACTIONS

Redox reaction

Oxidation reaction Reduction reaction

REDOX 21
BALANCING REDOX REACTIONS
BY THE ION-ELECTRON METHOD

Simply list the steps to balance a redox


reaction in an acidic (or neutral) medium.
Balancing redox reactions by the
ion-electron method has 8 steps.

REDOX 22
Those are:
1. Write a skeletal equation that shows only
the ions or molecules involved in the
reaction.
2. Divide the skeletal equation into two half-
reactions.
3. Balance all atoms that are not H or O.
4. Balance O by adding H2O.
5. Balance H by adding H+ (not H or H2 or H¯,
but H+).
6. Balance the net charge by adding e¯.
(remember its minus sign.)
REDOX continued 23
7. Multiply Entire Half-reactions by
simple whole numbers, as needed,
to get the gain of e¯ in one half-
reaction to match the loss of e¯ in
the other. Then add the half-reactions.
8. Cancel whatever is the same on
both sides of the arrow.

REDOX 24
The oxidation of methyl alcohol, CH3OH, to
formic acid, HCHO2, using the dichromate ion,
Cr2O72¯ in an acidic medium.
As this reaction proceeds, the chromium in
Cr2O72¯ change to Cr3+.
Step 1. Write a skeletal equation showing
reactants and products as given.
CH3OH + Cr2O72¯ HCHO2 + Cr3+
Step 2. Divide the skeletal equation into two
half-reactions. Except for H and O, the
same elements must appear on both sides
of each half-reaction.
CH3OH HCHO2
Cr2O72¯ Cr 3+
REDOX continued 25
Step 3. Balance all atoms that are not H or O
CH3OH HCHO2 (No change, yet.)
Cr2O72¯ 2Cr3+ (Balances Cr atoms.)

Step 4. Balance O by adding H2O


CH3OH + H2O HCHO2 (Cs and Os balance.)
Cr2O72¯ 2Cr3++ 7H2O (Crs and Os balance)

Step 5. Balance H by adding H+


CH3OH + H2O HCHO2 + 4H+ (All atoms
now balance.)
Cr2O72¯ + 14H+ 2Cr3+ + 7H2O (All atoms
now balance.)
REDOX continued 26
LOOK AT THE STEP 5, AND THEN
MAKE THE NET CHARGE ON THE LEFT
SIDE OF THE ARROW EQUAL TO THE
NET CHARGE ON THE RIGHT SIDE.

Step 5. Balance H by Step 6. Balance the net


adding H+ charge by adding e¯.
(a) CH3OH + H2O (a) CH3OH + H2O
HCHO2 + 4H+ HCHO2 + 4H++ 4e¯

2¯ +
(b) Cr2O7 14H+ (b) Cr2O72¯ + 14H++ 6e¯
2Cr3+ + 7H2O 2Cr3+ + 7H2O

REDOX continued 27
Step 7. Multiply half-reaction by whole
numbers so that the electrons will
cancel when the half-reactions are
added.
3 X [CH3OH + H2O HCHO2 + 4H++ 4e¯]
2 X [Cr2O72¯ + 14H++ 6e¯ 2Cr3+ + 7H2O]
+
Sum:
3CH3OH + 2Cr2O72 ¯+ 3H2O + 28H++ 12e¯
3HCHO2 + 4Cr3++ 12H+ + 14H2O +12e¯

REDOX continued 28
Step 8. Cancel everything that can be canceled
a). The 12 electrons on each side obviously
cancel.
b). Water molecule: there are 3 on the left and
14 on the right, so we can strike those on
the left and change those on the right to 11.
…. + 3H2O +…. …. + 14H2O +….
becomes: …. .… + 11H2O + ….
c). And then also cancel some H+
…. + 28 H+ + …. …. + 12 H+ + ….
becomes: …. + 16 H+ + …. …..
REDOX continued 29
3CH3OH(aq) + 2Cr2O72 ¯(aq) + 16H+(aq)
3HCHO2(aq) + 4Cr3+(aq) +11H2O

Check to see that both material and electrical


balance exist.

REDOX 30
Home work
Problem No. 1
What is the oxidation number of carbon in
ethane, C2H6?
Problem No. 2
What are the oxidation numbers of the
atoms in the nitrate ion, NO3¯?
Problem No.3
Balance the following equation, which
occurs in an acidic medium.
Cu(s) + NO3¯(aq) Cu2+(aq) + NO2(g)
REDOX 31
To Balance a Redox Equation When
the Medium is Basic.
MnO4¯(aq) + SO32¯(aq) MnO2(s) + SO42¯(aq)
1. First Balance it for an Acid Medium and
2. Then Neutralize the Acid
Step 1. Through 8 for acidic solutions
2MnO4¯ + 3SO32¯ + 2H+ 2MnO2 + 3SO42¯ + H2O

Step 9. Add as many OH as there are H+ to both


sides of equation. There are two H+ on the left.
So we add 2OH¯ to both sides.
2OH¯ + 2MnO4¯ + 3SO32¯ + 2H+
2MnOREDOX
+ 3SO 2¯ + H O + 2OH¯
2 4 2 32
Step 10. When they occur on the same
side of the arrow, combine H+
and OH¯ into H2O.
2OH¯ + 2MnO4¯ + 3SO32¯ + 2H+
2MnO2 + 3SO42¯ + H2O + 2OH¯
The left side has 2OH¯ and 2H+, so we
combine them into 2H2O.
The equation:
2H2O + 2MnO4¯ + 3SO32¯
2MnO2 + 3SO42¯ + H2O + 2OH¯

REDOX continued 33
Step 11. Cancel H2O molecules as possible

Step 10. Step 11.


2H2O + 2MnO4¯ + Cancel H2O molecule
3SO32¯ as possible.
2MnO2 + 3SO42¯ The final equation:
+ H2O + 2OH¯ H2O + 2MnO4¯(aq) +
3SO32¯(aq)
2MnO2(s)+ 3SO42¯(aq)
……… + 2OH¯(aq)

REDOX 34
Reduction Potentials or Redox Potentials


Half Reaction (volts)
Fe3+ (aq) + e¯ ⇌ Fe2+(aq) + 0.77
Fe2+(aq) + 2e¯ ⇌ Fe(s) - 0,44
½ O2 + 2H+ + 2 e¯ ⇌ H2O + 0.815
NAD+ + H+ + 2 e¯ ⇌ NADH - 0.315

REDOX 35
Rule for Combining Reduction
Half-Reactions

When two reduction half-


reactions are combined into a
full redox reaction the one with
the more positive E° always runs
as written, as a reduction, and it
forces the other, with the less
positive E°, to run in reverse, as
an oxidation.

REDOX 36
Na(s) and Cl2(g).
Will sodium react with chlorine?
Na+(aq) + e¯ ⇌ Na(s) E°= -2,71 V
Cl2(g) + 2 e¯ ⇌ 2Cl¯ E°= +1.36V
When two reduction half-reactions are combined
into a full redox reaction the one with the more
positive E° always runs as written, as a
reduction, and it forces the other, with the less
positive E°, to run in reverse, as an oxidation.

Na(s) → Na+(aq) + e¯ (oxidation)


Cl2(g) + 2 e¯ → 2Cl¯ (aq) (reduction)
Continued
REDOX
next slide 37
to get the net reaction, multiply the coefficients
of the first half-reaction by 2.
2X [Na(s) → Na+(aq) + e¯ (oxidation)]
2 Na(s) → 2Na+(aq) + 2e¯ (oxidation)
Cl2(g) + 2e¯ → 2Cl¯ (aq) (reduction)

Sum: 2Na(s) + Cl2(g)  2Na+(aq) + 2Cl¯ (aq)

Thus sodium and chlorine spontaneously react.

REDOX 38
TYPE OF REDOX REACTION

 OUT OF BODY  IN THE BODY

REDOX 39
Biological Oxidation

 The processes of oxidation are


essential for maintaining life
because oxidation and the
simultaneously occuring reduction
supply the free energy for the vital
work

REDOX 40
Organic Reaction Mechanisms

 Organic reactions mechanisms has


classified biochemical reactions into four
categories:
 1. Group-transfer reactions
 2. Oxidations and reductions
 3. Eliminations, isomerizations, and
rearrangements
 4. Reactions that make or break carbon-
carbon bonds
REDOX 41
Covalent bonds

 A covalent bond consists of an electron


pair shared between two atoms.
 In breaking such a bond, the electron pair
can either remain with one of the atoms
(heterolytic bond cleavage) or separate
such that one electron accompanies
each of the atoms (homolytic bond
cleavage).

REDOX 42
Homolytic Bond Cleavage

 Homolytic bond cleavage, which


usually produces unstable radicals,
occurs mostly in oxidation-
reduction reactions

REDOX 43
Heterolytic Bond Cleavage

 Heterolytic C-H bond cleavage


involves either carbanion and proton
(H+) formation or carbocation
(carboniun ion) and hydride ion (H-)
formation.

REDOX 44
Biologically Importan
Nucleophillic Groups

Nucleophiles are the conjugate bases


of weak acids
REDOX 45
1. Group-transfer reactions

 Types of metabolic group-transfer: Acyl group


transfer involves addition of a nucleophile (Y)
to the electrophilic carbon atom of an acyl
compound to form a tetrahedral intermediate.
The original acyl carrier (X) is then expelled to
form a new acyl compound.
REDOX 46
2. Oxidations and reductions

General
Base Alcohol NAD+

General
Ketone NADH
acid

NAD+ IS AN ELECTRON ACEPTOR (OXIDATOR);


REDOX TWO ELECTRON FROM GENERAL47
BASE ARE TRANSFERRRED TO AN ELECTRON ACCEPTOR SUCH AS NAD+.
In Living Systems

The electron-transfer process


connecting these half-reactions occurs
through a multistep pathway that
harnesses the liberated free energy to
form ATP.

REDOX 48
For Example: Biologic Oxidation

 The principal use of oxygen is in


respiration. Which may be defined as
the process by with cells derive
energy in the form of ATP from the
controlled reaction of hydrogen with
oxygen to form water.

REDOX 49
For Example:
oxidation of primary alcohols in
the Body

REDOX 50
ACCUT TOXICITY

Toxicity test SUBCHRONIC TOXICITY

CHRONIC TOXICITY

REDOX 51
Toxicity test

ORGAN TEST CHEMICAL


BLOOD TEST

REDOX 52
ORGAN TEST

REDOX 53
CHEMICAL
BLOOD TEST

 BLOOD UREA NITROGEN DETERMINATION


 ALT OR GPT DETERMINATION IN THE
SERUM
 BLOOD CREATININE DETERMINATION

REDOX 54
ORGAN TEST

MICROSCOPIC TEST

REDOX 55
Microscopic: Liver

REDOX 56
Microscopic liver of rat at 1000 x enlargement
REDOX 57
Microscopic liver of rat at
1000 x enlargement
REDOX 58
Microscopic: Liver
Blood vessel

Cava vein

REDOX 59
ORGAN TEST

MACROSCOPIC TEST

REDOX 60
Microscopic: KIDNEY

REDOX 61
calcium oxalate crystals

Microscopic of
Microscopic of rat kidney
Phylanthus niruri leaf
at 1000 x enlargement
at 1000 x enlargement
REDOX 62
FREE ENERGY CHANGES CAN BE
EXPRESSED IN TERMS OF REDOX POTENTIAL

 In reaction involving oxidation and


reduction, the free energy change is
proportionate to the tendency of reactants
to donate or accept electrons. Thus, in
addition to expressing free energy change
in terms of ΔG0.
 It is possible, in an analogous manner, to
express it numerically as an oxidation-
reduction or redox potential (E0).
REDOX 63
Oxidation of a Metabolite catalyzed
by an oxidase forming H2O

REDOX 64
Oxidation of a metabolite by Hydrogenases
and Finally by an Oxidase in a Respiratory
Chain.

REDOX 65
The Citric Acid Cycle

REDOX 66
The complete oxidation of glucose
by molecular oxygen

C6H12O6 + 6O2 6CO2 + 6H2O


Break this equation down into two half- reactions

1). C6H12O6 + 6H2O 6CO2 + 24H+ + 24e¯


The glucose carbon atoms are oxidized
2). 6O2 + 24H+ + 24e¯ 12H2O
Molecular oxygen is reduced

REDOX 67
The sites of electron transfer that form
NADH and FADH2 in glycolysis and
the citric acid cycle.

REDOX 68
Cytochrome P450 hydroxylase cycle in
microsomes

REDOX 69
A sugar that can be oxidized by Cu2+ (cupric
sulfate) solution or Fehling A reagent

REDOX 70

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