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Redox

Why electrochemistry?

REDOX reactions are important in

Purifying metals (e.g.


Al, Na, Li)
Producing gases (e.g.
Cl2, O2, H2)

C3H8O + CrO3 + H2SO4


Cr2(SO4)3 + C3H6O + H2O

Electroplating metals
Electrical production (batteries, fuel cells)

Protecting metals from corrosion


Balancing complex chemical equations
Sensors and machines (e.g. pH meter)

Oxidation Reduction Chemisty: Redox Chemistry


Oxidation and Reduction reactions always take
place simultaneously.
Loss of electrons oxidation (Increase in
Oxidation Number)
Ex:Na ------> Na+1 + e-1
Gain of electrons - reduction ( Decrease in
Oxidation Number)
Cl2 + 2 e-1 ------> 2 Cl-1

Oxidation occurs when a molecule


does any of the following:

Loses electrons
Loses hydrogen
Gains oxygen

If a molecule undergoes oxidation, it has


been oxidized and it is the reducing agent
(aka reductant).

Reduction occurs when a molecule does any of the


following:
Gains electrons
Gains hydrogen
Loses oxygen

If a molecule undergoes reduction,


it has been reduced and it is the
oxidizing agent (aka oxidant).

zinc is being oxidized while the copper is


being reduced. Why?

Redox reactions involve electron transfer:


Lose e - =Oxidation
Cu (s) + 2 Ag + (aq)

Cu 2+ (aq) + 2 Ag(s)

Gain e - =Reduction

Oxidation Numbers
- the charge an atom would have if the electrons belonged to
the more EN atom
- there are a few rules to help us out

Na

Na0

H2

H20

F2

F20

Oxidation Numbers
- the charge an atom would have if the electrons belonged to
the more EN atom

Na

Na+1

Ca

Ca+2

S-2

N-3

Oxidation Numbers
- the charge an atom would have if the electrons belonged to
the more EN atom

NaCl

Na+1Cl-1

AsI5

As+5I5-1

Cu(NO3)2

Cu+2(N+5O3-2)2

H2Cr2O7

H2+1Cr2+6 O7-2

Oxidation Numbers
- the charge an atom would have if the electrons belonged to
the more EN atom

H is ALWAYS +1 (for us)


Disclaimer there are compounds where H has a -1
oxidation number, ex: NaH

Oxidation Numbers
- the charge an atom would have if the electrons belonged to
the more EN atom

O is ALWAYS -2 (for us)


Important exception:
peroxides

Oxidation Numbers
- the charge an atom would have if the electrons belonged to
the more EN atom

(SO4)-2

(S+6O4-2)-2

(NO3)

(N+5O3-2)-

(Cr2+3O4)-2

(Cr2O4)

-2

Oxidation Numbers

Rules for Assigning Oxidation States


The oxidation state of an atom in an uncombined element is 0.
The oxidation state of a monatomic ion is the same as its charge.
Oxygen is assigned an oxidation state of 2 in most of its covalent
compounds. Important exception: peroxides (compounds
containing the O2 2- group), in which each oxygen is assigned an
oxidation state of 1)

In its covalent compounds with nonmetals, hydrogen is assigned


an oxidation state of +1
For a compound, sum total of ON s is zero.
For an ionic species (like a polyatomic ion), the sum of the
oxidation states must equal the overall charge on that ion.

Oxidation Numbers
Do the five problems on your notes sheet

a. Cr2O3

d. KCl

b. H2Cr2O7

e. Mg(OH)2

c. AsCl5

Redox:
Reduction occurs when an atom gains one or more
electrons.
Ex:
Oxidation occurs when an atom or ion loses one or
more electrons.
Ex:
LEO goes GER
Copper metal reacts with silver nitrate to form silver
metal and copper nitrate:
Cu + 2 Ag(NO3) 2 Ag + Cu(NO3)2.

Identifying OX, RD, SI


Species
Ca0 + 2 H+1Cl-1 Ca+2Cl-12 + H20
Oxidation = loss of electrons. The species becomes more
positive in charge. For example, Ca0 Ca+2, so Ca0 is the
species that is oxidized.
Reduction = gain of electrons. The species becomes more
negative in charge. For example, H+1 H0, so the H+1 is
the species that is reduced.
Spectator Ion = no change in charge. The species does not
gain or lose any electrons. For example, Cl-1 Cl-1, so
the Cl-1 is the spectator ion.

Practice
Identify in the following reactions what is
oxidized and what is reduced

2K + Cl2 2KCl
K0 goes from 0 to +1, it is oxidized
Cl0 goes from 0 to -1, it is reduced

Practice
Identify in the following reactions what is
oxidized and what is reduced

2NaCl + 3SO3 Cl2 + SO2 + Na2S2O7

Cl-1 goes from -1 to 0, it is oxidized


S+6 goes from +6 to +4, it is reduced

Practice
Identify in the following reactions what is
oxidized and what is reduced

Zn + Pb+2(aq) Zn+2(aq) + Pb
Zn0 goes from 0 to +2, it is oxidized
Pb+2 goes from +2 to 0, it is reduced

Identify what atom is


oxidized and what atom is
reduced:
Fe + 2HCl FeCl2 + H2

Oxidizing Agent and Reducing Agent:


Oxidizing agent gets reduced itself and reducing
agent gets oxidized itself, so a strong oxidizing agent
should have a great tendency to accept e and a strong
reducing agent should be willing to lose e easily. What
are strong oxidizing agents- metals or non metals?
Why?
Which is the strongest oxidizing agent and which is the
strongest reducing agent?

Agents
Ca0 + 2 H+1Cl-1 Ca+2Cl-12 + H20
Since Ca0 is being oxidized and H+1 is being reduced, the
electrons must be going from the Ca0 to the H+1.
Since Ca0 would not lose electrons (be oxidized) if H+1
werent there to gain them, H+1 is the cause, or agent, of
Ca0s oxidation. H+1 is the oxidizing agent.
Since H+1 would not gain electrons (be reduced) if Ca0
werent there to lose them, Ca0 is the cause, or agent, of
H+1s reduction. Ca0 is the reducing agent.

Steps for Balancing a Redox Reaction:


Half Reaction Method
In half reaction method, oxidation and reduction halfreactions are written and balanced separately before
combining them into a balanced redox reaction. It is
a good method for balancing redox reactions
because this method can be used both for reactions
carried out in acidic and basic medium .

Writing Half-Reactions
Ca0 + 2 H+1Cl-1 Ca+2Cl-12 + H20
Oxidation: Ca0 Ca+2 + 2e Reduction: 2H+1 + 2e- H20

The two electrons lost


by Ca0 are gained by
the two H+1 (each H+1
picks up an electron).

PRACTICE SOME!

HALF REACTIONS
Write both half reactions for the following
reaction:
Cu + AgNO3 Cu(NO3)2 + Ag

Reduction: Ag+ Ag
Ag+ + 1e- Ag
Oxidation:

Cu Cu+2
Cu Cu+2 + 2eCu - 2e- Cu+2

HALF REACTIONS
Write both half reactions for the following
reaction:

HNO3 + I2 HIO3 + NO2


Reduction: N+5 N+4
N+5 + 1e- N+4
Oxidation:

I20 I+5
I20 2I+5 + 10eI20 - 10e- 2I+5

Half Reactions
Write both half reactions for the following
reaction:

Sn + 2AgNO3 Sn(NO3)2 + 2Ag


Reduction: Ag+1 Ag0
Ag+1 + 1e- Ag0
Oxidation:

Sn0 Sn+2
Sn0 Sn+2 + 2eSn0 - 2e- Sn+2

Practice Half-Reactions
Dont forget to determine the charge of each species first!
4 Li + O2 2 Li2O
Oxidation Half-Reaction:
Reduction Half-Reaction:
Zn + Na2SO4 ZnSO4 + 2 Na
Oxidation Half-Reaction:
Reduction Half-Reaction:

Steps for Balancing Redox Reaction Using


Half Reaction Method IN ACIDIC MEDIUM:
Step 1: Write unbalanced equation in ionic form.
Step 2: Write separate half reactions for the oxidation and
reduction processes. (Use Oxidation Numbers for identifying
oxidation and reduction reactions)
Step 3: Balance atoms in the half reactions
First, balance all atoms except H and O
Balance O by adding H2O
Balance H by adding H+
Step 4: Balance Charges on each half reaction, by adding
electrons.
Step 5: Multiply each half reaction by an appropriate number to
make the number of electrons equal in both half reactions.
Step 6: Add two half reactions and simplify where possible by
canceling species appearing in both sides.
Step 7: Check equation for same number of atoms and charges on
both sides.

BALANCING REDOX REACTIONS IN ACID


SOLUTION

STEP 1:
Balancing redox reactions in acid can be easy, if
you follow the rules. We'll work through an
example step by step introducing each rule in
turn.
Suppose you want to balance the following
equation:
Cr2O72- + NO2- --> Cr3+ + NO3- (acid)

STEP 2
First, split the reaction into two half
reactions. One half reaction will show the
oxidation; the other half reaction will show
the reduction. It is not necessary at this
point to know in advance which is which:
Cr2O72- --> Cr3+
NO2- --> NO3-

STEP 3
Balance any atom other than oxygen or
hydrogen first. Work with one half reaction
at a time. In the first half reaction, there are
2 Cr on the left hand side and only 1 Cr on
the right hand side. Balance the Cr first:
Cr2O72- --> 2 Cr3+
NO2- --> NO3-

Next, balance the O by adding as much H 2O


as needed to the side deficient in O. In this
case, 7 H2O is needed on the right hand side
to balance the 7 O on the left hand side:
Cr2O72- --> 2 Cr3+ + 7 H2O
H2O + NO2- --> NO3-

Since this reaction occurs in acid solution,


balance the H by using H+ ions. Add as many
H+ ions as needed to the side deficient in H. In
this case, 14 H+ ions are needed on the left
hand side of the half reaction:
14 H+ + Cr2O72- --> 2 Cr3+ + 7 H2O
H2O + NO2- --> NO3- + 2 H+

STEP 4

All that remains is charge balance. To balance the charge, find the net
charge on each side of the half reaction, and add as many electrons as
needed to the more positive side so as to equal the charge on the more
negative side. In this case the net charge on the left hand side of the
half reaction is +12 ( +14 for the 14 hydrogen ions and -2 for the
dichromate ion). The net charge on the right hand side is +6 (+6 due to
two Cr3+ ions and 0 for the 7 water molecules). The net charge on the
left hand side (+12) is more positive than the charge on the right hand
side (+6). By adding 6 electrons (6e-) to the left hand side, the net
charge will be the same on both sides of the half reaction:
6 e- + 14 H+ + Cr2O72- --> 2 Cr3+ + 7 H2O

H2O + NO2- --> NO3- + 2 H+ + 2 e-

STEP 5
You need to find the least common multiple (lcm)
of 2 and 6. In this case, the lcm is 6. Next, multiply
each of the half reactions by the factor needed to
obtain the 1 cm. Therefore, multiply the first half
reaction by 1 and the second half reaction by 3:
1 x ( 6 e- + 14 H+ + Cr2O72- --> 2 Cr3+ + 7 H2O )
3 x ( H2O + NO2- --> NO3- + 2 H+ + 2 e- )

STEP 6

Steps for Balancing Redox Reaction Using


Half Reaction Method IN BASIC MEDIUM:
For balancing redox reactions in basic solutions, all the
steps are the same as acidic medium balancing,
except you add one more step to it. The H+ ions can
then be neutralized by adding an equal number of
OH- ions to both sides of the equation. Ex.