This is the last chapter……

Chapter 20
Electrochemistry
Review: Oxidation, Reduction, Agents
and Oxidation numbers

Simulation: Activity Series

 Reduction →

On your table, locate the following WRA

SOA
substances:
Ag+, Cu2+, Zn2+, Mg2+
and Ag, Cu, Zn and Mg.

What do you notice?

A spontaneous
reaction will occur if:
the SOA is higher

than the SRA

A non-spontaneous
reaction will occur if:
the SRA is higher

than the SOA

WOA SRA

← Oxidation
A redox reaction will always be between the
strongest oxidizing agent (SOA) (highest on left),
with the strongest reducing agent (SRA) (lowest on
right).

In other words – electrons transfer from the species

that is best at losing them, to the one that is best at
gaining them.
 Balancing Redox Reactions

Previously, when you have balanced a chemical equation, you

made sure that you had the same number of atoms of an
element on each side of the equation. If not, you placed a
coefficient in front of the species to make it balance.

You do the same thing with redox reactions, but you must also
make sure that you BALANCE the ELECTRONS.

The electrons being lost (in the oxidation) must equal the
electrons being gained (in the reduction).

There are a few different ways by which we can balance redox

reactions:
1. Using Half-Reactions from the Table:

A number of chemical species can be found in already

balanced half-reactions on the Standard Reductions Table.
For this method, you only need to locate the substance
(reactants and products) on the table, ensuring that you have
an oxidation and a reduction, and then balance the electrons
being lost to electrons being gained, before adding the two
half-reactions together.
For Example: MnO4-(aq) + Al(s) → Mn2+(aq) + Al3+(aq)

Step 1: Either assign oxidation numbers to each species to identify what is

being oxidized or reduced Or locate the reactants on your table to see if
they are being reduced or oxidized (make sure they form the same products
as shown). You might not use all the substances that are in the equation.

MnO4-(aq) + H+(aq) + Al(s) → Mn2+(aq) + Al3+(aq) + H2O(aq)

+7 0 +2 +3

reduced (on left)

oxidized (on right)
 Or – just look on your table.

MnO4-(aq) + H+(aq) + Al(s) → Mn2+(aq) + Al3+(aq) + H2O(aq)

When going to your table, ALWAYS start at the

top left hand corner and work your way down
the OAs.
Stop when you find any of the reactants
in the given question . Make sure the
product matches the equation given.

Once you find one of the reactant species,

then go to the bottom right corner and work
your way up the RA. (since it’s an oxidation
you read from right to left)(switch the arrow).

Again – make sure the product matches.

 Step 2: Find the species on your
table and write out the complete
half-reactions (one oxidation and
one reduction). Include
everything. In order to write
the oxidation, you must REVERSE
the equation.

Reduction: MnO4- + 8H+ + 5e- → Mn2+ + 4H2O

Oxidation: Al → Al3+ + 3e-

Step 3: Make the number of electrons lost = number of
electrons gained by multiplying the whole half-reaction with
a coefficient if necessary.

Reduction MnO4- + 8 H+ + 5 e- → Mn2+ + 4 H2O X3

:

Oxidation: Al → Al3+ + 3 e- X5

Reduction: 3 MnO4- + 24 H+ + 15 e- → 3 Mn2+ + 12 H2O

Oxidation: 5 Al → 5 Al3+ + 15 e-
Step 4: Add the two half-reactions together, keeping all
reactants as reactants and all products as
products. Cancel out anything found on both sides of the
equation – rewriting the final answer.

Reduction: 3 MnO4- + 24 H+ + 15 e- → 3 Mn2+ + 12 H2O

Oxidation: 5 Al → 5 Al3+ + 15 e-

Redox: 3 MnO4- + 24 H+ + 15 e- + 5 Al → 3 Mn2+ + 12 H2O + 5 Al3+ + 15 e-

Now Cancel: 3 MnO4- + 24 H+ + 15 e- + 5 Al → 3 Mn2+ + 12 H2O + 5 Al3+ + 15 e-

Final answer: Redox: 3 MnO4- + 24 H+ + 5 Al → 3 Mn2+ + 12 H2O + 5 Al3+

Another example:
Balance: Na + MnO2 →Mn2+ + Na+

Reduction: proceed down the top left of your

table until you find either Na or MnO2
Check to see that the products match: Mn2+
If it does, write out the COMPLETE equation.
If not – keep looking.
MnO2 + 4H+ + 2e- → Mn2+ + 2H2O
Oxidation: proceed up the bottom right of your
table until you find Na
Check to see that the products match: Na+
If it does, write out the COMPLETE equation (in
reverse). If not – keep looking.
Na → Na+ + e- 2
Now balance e- by multiplying the half-reactions.
Add together and cancel.
MnO2 + 4H+ + 2e- → Mn2+ + 2H2O
2 Na → 2 Na+ + 2e-
MnO2 + 4H+ + 2 Na → Mn2+ + 2H2O + 2Na+
 Practice: Balancing Redox Half-Reactions
Try page 10!

1. Cl2(g) + Cr(s) → Cl-(aq) + Cr3+(aq)

Red. (Cl2(g) + 2e- → 2Cl-(aq)) 3 Oxid: (Cr(s) → Cr3+ + 3 e-) 2

Redox: 3Cl2(g) + 2 Cr → 6Cl- + 2 Cr3+

2. MnO4-(aq) + Fe(s) → MnO2(s) + Fe2+(aq)

Red. (MnO4- + 2H2O + 3e- →MnO2 + 4OH-)2 Oxid: (Fe(s) → Fe2+ + 2 e-) 3

Redox: 2MnO4- + 4H2O+ 3Fe → 2MnO2 + 8OH- + 3Fe2+

3. Cu2+(aq) + H2O2(aq) → Cu1+(aq) + O2(g) + H+(aq)

Red. (Cu2++ 1e- → Cu1+ )2 Oxid: H2O2 → O2 + 2H+ + 2e-

Redox: 2Cu2+ + H2O2 → 2Cu1+ + O2 +2H+

4. O2(g) + H+(aq) + Al(s) → H2O(l) + Al3+(aq)

Red: 3(O2+ 4H+ + 4e- →2H2O) Oxid. 4( Al → Al3+ + 3e-)

Redox: 3 O2+ 12 H+ + 4 Al →6 H2O + 4 Al3+

5. Ni2+(aq) + SO2(aq) + H2O(l) → Ni(s) + SO42-(aq) + H+(aq)

Red: Ni2+ + 2e- → Ni Oxid.: SO2 + 2 H2O→ SO42- + 4 H+ + 2e-

Redox: Ni2+ + SO2 + 2 H2O→ Ni + SO42- + 4 H+

6. Cr2O72-(aq) + H+(aq) + Zn(s) → Zn2+(aq) + Cr3+(aq) + H2O(l)

Red: Cr2O72- + 14 H+ + 6e- →2 Cr3+ + 7H2O Oxid.: 3(Zn → Zn2+ + 2e-)

Redox: Cr2O72- + 14 H+ + 3 Zn →2 Cr3+ + 7H2O + 3 Zn2+

2: Writing your own balanced half-reactions

Not all substances are found in balanced half-reactions on your

redox table, so sometimes you might have to generate your own
half-reactions before you can add them together.

It is important to note that redox reactions most often occur

in water solution which often can be acidic or basic.

We can use this information to help us balance the atoms in

the equation. For example, water, H2O, provides a source of
O and H atoms for balancing. If the solution is acidic there
are hydrogen ions (H+) available and, if basic, there are
hydroxide ions (OH-) in the solution.
 For acidic solutions:

Balance the following half-reaction in acidic solution:

ClO3- → Cl2
+5 0
Step 1: Determine the oxidation numbers for the substances present.

Step 2: If necessary, balance the substance that is undergoing

oxidation or reduction by placing a coefficient in front of the term(s).

2 ClO3- → Cl2
Step 3: Place the correct number of electrons into the
equation. If it is a reduction, electrons are being gained,
so they are placed on the reactants side. If it is
an oxidation, electrons are lost, so they are placed on
the products side.

10 e- + 2 ClO3- → Cl2
+5 0

Reduction: 5 e- gained per atom x 2 atoms of chlorine = 10 e-

Step 4: Balance the oxygen atoms by adding water (H2O) to the
side needing oxygen.

10 e- + 2 ClO3- → Cl2 + 6 H2O

Step 5: Balance the hydrogen atoms by adding H+ (recall –
acidic solution) to the side that requires hydrogen.

12 H+ + 10 e- + 2 ClO3- → Cl2 + 6 H2O

Step 6: Cancel if possible.

12 H+ + 10 e- + 2 ClO3- → Cl2 + 6 H2O

 For Basic Solutions: (Have H2O and OH-)

If you are balancing in a basic solution, you balance first in

acidic solution. There should be excess H+ in your equation.

12 H+ + 10 e- + 2 ClO3- → Cl2 + 6H2O

Step 7: Continue by adding as much OH- as you have H+,

but add it to BOTH sides of the equation.

12 OH- + 12 H+ + 10 e- + 2 ClO3- → Cl2 + 6H2O + 12 OH-

Step 8: Combine any OH- and H+ found on the same side to make
water. (OH- + H+ → H2O)

12 OH- + 12 H+ + 10 e- + 2 ClO3- → Cl2 + 6 H2O + 12 OH-

12 H2O + 10 e- + 2 ClO3- → Cl2 + 6 H2O + 12 OH-

Step 9: Cancel out anything that is the same on both sides of

the equation. Rewrite your final answer.

12 H2O + 10 e- + 2 ClO3- → Cl2 + 6H2O + 12OH-

6 H2O + 10 e- + 2 ClO3- → Cl2 + 12OH-

Practice: Try to write balanced half-reactions for the following reduction or
oxidation reactions. Note the type of solution used.

1. BrO3-(aq) → Br2(l) (acidic)

2. NH3(g) → NO3-(aq) (basic)

3. PO33- → PO43- (basic)

4. SO2(g) → SO42-(aq) (basic)

5. NO3- → N2O (acidic)

6. I2 → IO3- (acidic)

7. Cr2O72- → Cr3+ (basic)

8. SO32- → SO42- (basic)

Answers:

1. 12 H+ + 10e- + 2 BrO3-(aq) → Br2(l) + 6 H2O (acidic)

2. 9 OH- + NH3(g) → NO3- + 8e- + 6 H2O (basic)

3. 2 OH- + PO33- → PO43- + 2e- + H2O (basic)

4. 4 OH- + SO2(g) → SO42- + 2e- + 2H2O (basic)

5. 10 H+ + 8e- + 2 NO3- → N2O + 5 H2O (acidic)

6. 6 H2O + I2 → 2 IO3- + 10e- + 12 H+ (acidic)

7. 7H2O + 6e- + Cr2O72- → 2 Cr3+ + 14 OH- (basic)

8. 2OH- + SO32- → SO42- +2e- + H2O (basic)

 3. Balancing Using Oxidation Numbers and
Half-Reactions:

This method involves splitting the given unbalanced

reaction into two half-reactions, balancing each, then
putting them back together.
In acidic solution:
NO3-(aq) + I2(g) → IO31-(aq) + NO2(g)

Step 1: Divide the reaction into 2 half-reactions

and assign oxidation numbers.

NO3-(aq) → NO2(g) I2(g) → IO3-(aq)

+5 +4 0 +5
reduction oxidation
Step 2: Balance the atoms changing oxidation
states and add the electrons accordingly.

1e- + NO3-(aq) → NO2(g)

+5 +4
Red. Gain of 1 e- per atom.

I2(g) → 2 IO3-(aq) + 10 e-
0 +5
Oxid. Loss of 5e- / atom x 2 atoms =10e-
Step 3: Balance all other atoms, then balance oxygen
by adding H2O to the side needing O.

1e- + NO3-(aq) → NO2(g) + H2O

I
6 H2O + 2(g) → 2 IO -
3 (aq)
+ 10 e-
Step 4: Balance the hydrogen by adding
H+ to the side requiring it.

2H+ + 1e- + NO3-(aq) → NO2(g) + H2O

6H2O + I2(g) → 2 IO3-(aq) + 10 e- + 12 H+

 Step 5: Make the number of electrons being
lost equal to the number of electrons being
gained by multiplying the whole half-reaction by
a whole number.

2H+ + 1e- + NO3-(aq) → NO2(g) + H2O X 10

6H2O + I2(g) → 2 IO3-(aq) + 10 e- + 12 H+ X 1

Step 6: Add your two half-reactions together and
cancel.

20 H++ 10 e- +10 NO3-(aq) → 10 NO2(g)+ 10 H2O

6H2O + I2(g) → 2 IO3-(aq) + 10 e- + 12 H+

20 H+ + 10e- + 10 NO3- + 6H2O + I2 →

10 NO2 + 10H2O + 2 IO3- + 10e- + 12 H+

8H+ + 10 NO3- + + I2 → 10 NO2 + 4 H2O + 2 IO3-

If basic:
Step 7: You would now continue by adding OH-
(equal to the # of H+) to both sides.

8 OH- + 8H+ + 10 NO3- + I2 →10 NO2 + 4 H2O + 2 IO3- + 8 OH-

8 H2O (since an H+ + OH- = H2O)

Step 8: Combine OH- and H+ to make water.
(same side of equation)
8H2O + 10 NO3- + I2 →10 NO2 + 4 H2O + 2 IO3-+ 8 OH-
 Step 9: Cancel out anything that appears on both
sides of the equation.

8H2O + 10 NO3- + I2 →10 NO2 + 4 H2O + 2 IO3-+ 8 OH-

Rewrite the final answer:

4H2O + 10 NO3- + I2 →10 NO2 + 2 IO3-+ 8 OH-

 4. Balancing the whole equation:
Let’s do the same problem as we did with method #3.
In acidic solution:
NO3-(aq) + I2(g) → IO3-(aq) + NO2(g)

Step 1: Assign oxidation numbers and change

coefficients for those substances that are being
oxidized or reduced.
NO3-(aq) + I2(g) → 2 IO3-(aq) + NO2(g)
+5 0 +5 +4
 Step 2: Change coefficients to make the loss of
electrons equal to the gain of electrons.

10 NO3-(aq) + I2(g) → 2 IO3-(aq) + 10 NO2(g)

+5 0 +5 +4

Reduction – (gain of 1e-/atom) X 10 = 10e-

Oxidation – (loss of 5e-/atom) x 2atoms = 10e-

Step 3: Balance all other atoms, then balance oxygen by
adding H2O to the side needing O.

10 NO3-(aq) + I2(g) → 2 IO3-(aq) + 10 NO2(g) +4 H2O

30 O atoms 26 O atoms
+ 4 O atoms
 Step 4: Balance the hydrogen by adding H+ to the
side requiring it.

8 H+ + 10 NO3- + I2 → 2 IO3- + 10 NO2 + 4 H2O

Step 5: Cancel out anything that is the same

on both sides.

Nothing needs canceling in this example.

8 H+ + 10 NO3- + I2 → 2 IO3- + 10 NO2 + 4 H2O
If basic:

Step 7: You would now continue by adding OH-

(equal to the # of excess H+) to both sides.
8OH- + 8 H++10 NO3- + I2 → 2 IO3- + 10 NO2 + 4 H2O + 8OH-

Step 8: Combine OH- and H+ to make water.

8 OH-+ 8 H++10 NO3- + I2 → 2 IO3- +10 NO2 + 4 H2O+ 8 OH-

8 H2O +10 NO3- + I2 → 2 IO3- +10 NO2 + 4 H2O+ 8 OH-

Step 9: Cancel out anything that appears on both
sides of the equation.

8 H2O +10 NO3- + I2 → 2 IO3- +10 NO2 + 4 H2O+ 8 OH-

4 H2O +10 NO3- + I2 → 2 IO3- +10 NO2 + 8 OH-

Rewrite the final answer:

4 H2O +10 NO3- + I2 → 2 IO3- +10 NO2 + 8 OH-