CHEMISTRY - practice lecture

AA 2016-2017

3 - Balancing redox reactions

Dr. Cristina Pagliano

Department of Applied Science and Technology
Politecnico di Torino
Phone number: 0131-229301
E-mail: cristina.pagliano@polito.it

1/36 Practice lecture 3 – BALANCING REDOX REACTIONS

The meaning of Reduction and Oxidation (1/2)
Oxidation-reduction reactions (or redox reactions) are a type of
chemical reaction that involves a transfer of electrons between
two species. An oxidation-reduction reaction is any chemical
reaction in which the oxidation number (O.N.) of a molecule, atom,
or ion changes by gaining or losing electrons.

Oxidation Number
Every atom, ion or polyatomic ion has a
formal O.N. associated with it.
In many cases, the O.N. reflects the actual
charge on the atom, but there are many cases
where it does not. Think of O.N. as a book-
keeping exercise simply to keep track of
where electrons go.
2/36 Practice lecture 3 – BALANCING REDOX REACTIONS
The meaning of Reduction and Oxidation (2/2)

Reduction Oxidation
refers to the fact that the O.N. of Oxidation is the reverse process:
an atom is reduced during the the O.N. of an atom is increased
reduction. during the oxidation.
This is accomplished by adding e-, This is done by removing e-. The
which, being negative, reduce the e-, being negative, make the
overall O.N. of the atom receiving atom that lost them more
the e-. positive.
3/36 Practice lecture 3 – BALANCING REDOX REACTIONS
 Examples of Oxidation-Reduction reactions
Here there are two examples of fundamental biological redox
reactions:
• Cellular respiration is the oxidation of glucose (C6H12O6) to CO2
and the reduction of oxygen to water.
The summary equation for cell respiration is:
C6H12O6 + 6 O2 → 6 CO2 + 6 H2O
• Photosynthesis involves the reduction of carbon dioxide into
sugars and the oxidation of water into molecular oxygen.
The summary equation for photosynthesis is:
6 CO2 + 6 H2O + light energy → C6H12O6 + 6 O2
Redox equations need to be balanced but, except for the most
simple ones, it cannot be done by inspection.
There are two main methods used to balance redox reactions:
1. Method based on the oxidation number
2. Method based on half-reactions (or semi-reactions)
4/36 Practice lecture 3 – BALANCING REDOX REACTIONS
 Balancing Redox Reactions
Following the Law of Conservation of Mass you learned that the
number of atoms of each element must be the same on both the
reactant and product side of the equation.
Many redox reactions cannot easily be balanced just by counting
atoms. Consider the following net ionic equation:

Cu(s) + Ag+(aq) → Cu2+(aq) + Ag(s)

If you simply count atoms, the equation appears to be balanced: one

copper atom or ion on each side of the equation, and one silver. But
do you see what isn't balanced? the charges! If you total the electrical
charge on the reactant side of the equation you find a total charge of
+1, versus +2 on the product side. Charges represent gain or loss of
electrons, and, like atoms, electrons are conserved during chemical
reactions.
5/36 Practice lecture 3 – BALANCING REDOX REACTIONS
Balancing Redox Reactions using Oxidation Numbers (1/7)
You may have already guessed how we will balance equations using
the oxidation number method. Let's create our summary table for
the copper-silver reaction:

We can see that the number of electrons lost by copper does not
equal the number gained by silver. We need to correct that, so we
will multiply Ag by 2, giving us a total of two silvers.
6/36 Practice lecture 3 – BALANCING REDOX REACTIONS
Balancing Redox Reactions using Oxidation Numbers (2/7)
We'll multiply copper by one - it won't change anything but will help
keep us organized:

We now are balanced for electrons - two electrons will transfer,

from copper to silver.
The highlighted values - our multipliers to balance electrons - will
become our balancing coefficients in the equation. Our chart helps
us to keep organized and see that we should put a "1" in front of
copper and a "2" in front of silver. Our balanced equation is:
1 Cu(s) + 2 Ag+(aq) → 1 Cu2+(aq) + 2 Ag(s)

7/36 Practice lecture 3 – BALANCING REDOX REACTIONS

Balancing Redox Reactions using Oxidation Numbers (3/7)
Other examples & some tricks.
Balance the following equation:
NH3 + O2 → NO2 + H2O
Determine oxidation numbers and set up a summary table - but
don't finish it just yet:

8/36 Practice lecture 3 – BALANCING REDOX REACTIONS

Balancing Redox Reactions using Oxidation Numbers (4/7)

We now have our multipliers for the balanced equation: "4" for nitrogen
and "7" for oxygen - but which oxygen??? The one on the reactant side or
the two different compounds that contain oxygen on the product side???
Here's where our trick becomes more useful, but will require some trial
and error. Since we were counting oxygen atoms in the O2 molecule on the
reactant side of the equation, that's where we'll use the "7". (You could
make the same argument about NO2, but since nitrogen's oxidation
number also changed we will use nitrogen's balancing coefficient there).

4 NH3 + 7 O2 → 4 NO2 + H2O

9/36 Practice lecture 3 – BALANCING REDOX REACTIONS
 Balancing Redox Reactions using Oxidation Numbers (5/7)
4 NH3 + 7 O2 → 4 NO2 + H2O

The last step is to balance for hydrogen atoms (and finishing oxygen),
which will mean placing a 6 in front of H2O:
4 NH3 + 7 O2 → 4 NO2 + 6 H2O
---------------------------------------------------------------------------------------------------------
One more tricky. Balance:
Zn + HNO3 → Zn(NO3)2 + NO2 + H2O
Determine oxidation numbers and create your summary chart:

10/36 Practice lecture 3 – BALANCING REDOX REACTIONS

Balancing Redox Reactions using Oxidation Numbers (6/7)
Zn + HNO3 → Zn(NO3)2 + NO2 + H2O
The main thing to notice is that N appears in two separate products -
Zn(NO3)2 and NO2. Should we consider the subscript for nitrogen from
Zn(NO3)2? In this case no, because this compound also contains Zn, the
oxidized element. Also, the oxidation number for nitrogen does not
change from HNO3 to Zn(NO3)2.

We now get our balancing coefficients from our summary table. A "1"
will be placed in front of Zn, but which N should we use for the "2"? If
you put it in front of both HNO3 and NO2 you'll find you cannot
balance for nitrogen atoms.
11/36 Practice lecture 3 – BALANCING REDOX REACTIONS
Balancing Redox Reactions using Oxidation Numbers (7/7)
Zn + HNO3 → Zn(NO3)2 + NO2 + H2O

Since the oxidation number for nitrogen changed in becoming NO2, we

will try it there first.
Some trial-and-error may be required:

1 Zn + HNO3 → 1 Zn(NO3)2 + 2 NO2 + H2O

With the 2 in place in front of NO2, we can now balance the rest of the
equation for atoms. Doing so gives us the final answer:
1 Zn + 4 HNO3 → 1 Zn(NO3)2 + 2 NO2 + 2 H2O

12/36 Practice lecture 3 – BALANCING REDOX REACTIONS

 Balancing Redox Reactions using half-reactions (1/10)
What is a half-reaction?
A half-reaction is simply one which shows either reduction or
oxidation, but not both. Here is the example redox reaction used
before:
Cu(s) + Ag+(aq) → Cu2+(aq) + Ag(s)
Identify the atoms which get reduced and get oxidized. Here there are
the two half-reactions from the above example:
Ag+ ---> Ag
Cu ---> Cu2+
The silver is being reduced, its oxidation number going from +1 to
zero.
The copper's oxidation number went from zero to +2, so it was
oxidized in the reaction.
In order to figure out the half-reactions, you must be able to calculate
the oxidation number of an atom.
13/36 Practice lecture 3 – BALANCING REDOX REACTIONS
 Balancing Redox Reactions using half-reactions (2/10)
The total amount of charge on each side of the half-reaction MUST be
the same.
When you look at the two half-reactions above, you will see they are
already balanced for atoms with one Ag on each side and one Cu on
each side. So, all we need to do is balance the charge. To do this you
add electrons to the more positive side. You add enough to make the
total charge on each side become EQUAL.
To the silver half-reaction, we add one electron:
Ag+ + e¯ ---> Ag
To the copper half-reaction, we add two electrons:
Cu ---> Cu2+ + 2e¯
One point of concern: notice that each half-reaction would end up
with a total charge of zero on each side.
This is not always the case. You need to strive to get the total charge
on each side EQUAL, not zero.
14/36 Practice lecture 3 – BALANCING REDOX REACTIONS
 Balancing Redox Reactions using half-reactions (3/10)
Here there are the two half-reactions to be combined:
Ag+ + e¯ ---> Ag
Cu ---> Cu2+ + 2e¯
The rule to follow is: the number of electrons in each half-reaction
MUST be equal when the two half-reactions are added.
This means that one (or both) equations must be multiplied through
by a factor. The value of the factor is selected so as to make the
number of electrons equal.
In our example problem, the top reaction (the one with silver) must
be multiplied by two, like this:
2Ag+ + 2e¯ ---> 2Ag
Notice that each separate substance is increased by the factor amount.
When the two half-reactions are added, we get:
2Ag+ + 2e¯ + Cu ---> 2Ag + Cu2+ + 2e¯
With two electrons on each side, they may be canceled, resulting in:
2Ag+ + Cu ---> 2Ag + Cu2+
This is the correct answer.
15/36 Practice lecture 3 – BALANCING REDOX REACTIONS
 Balancing Redox Reactions using half-reactions (4/10)
Summarizing general rules for this method:
• The overall equation is broken down into two half-reactions. If there
are any spectator ions, they are removed from the equations.
• Each half-reaction is balanced separately - first for atoms and then
for charge. Electrons are added to one side of the equation or the
other in order to balance charge. For example, if the reactant side
of the equation has a total charge of +3, the product side must also
equal +3.
• To balance charges, add ions H+ in an acidic solution, or OH- in a
basic solution. Then add H2O to balance total masses.
• Next the two equations are compared to make sure electrons lost
equal electrons gained. One of the half reactions will be an
oxidation reaction, the other will be a reduction reaction.
• Finally the two half-reactions are added together, and any spectator
ions that were removed are placed back into the equation.
16/36 Practice lecture 3 – BALANCING REDOX REACTIONS
 Balancing Redox Reactions using half-reactions (5/10)
Other examples & some tricks.
Balance the following equation:
Cu(s) + AgNO3 (aq) → Cu(NO3)2 (aq) + Ag(s)
Identify the elements undergoing oxidation (Cu) and reduction (Ag).
The nitrate group (NO3) is a spectator ion, which will not be included
in our half-reactions.

Cu → Cu+2 + 2 e- Ag+ + 1 e- → Ag
oxidation reduction

After balancing for atoms and for charge, we see that the two
equations do not have the same number of electrons - there are 2 in
the copper reaction but only one in the silver reaction. Multiply
everything in the silver reaction by 2, then we will add the equations
together.
17/36 Practice lecture 3 – BALANCING REDOX REACTIONS
 Balancing Redox Reactions using half-reactions (6/10)
We work as follows:

18/36 Practice lecture 3 – BALANCING REDOX REACTIONS

 Balancing Redox Reactions using half-reactions (7/10)
Reaction occurring in an acid solution
MnO4- + Fe2+ + H+ → Mn2+ + Fe3+ + H2O
In this example, spectator ions have already been removed. Even
though hydrogen and oxygen do not undergo changes in oxidation
number they are not spectators and we need to work with them in our
half-reactions.
We determine that Mn undergoes reduction (+7 to +2) while Fe
undergoes oxidation (+2 to +3). The iron half-reaction is straight
forward, but the manganese reaction is more complex - we must
include hydrogen and oxygen in its half-reaction:
Fe2+→ Fe +3 + 1e- MnO4- + 8 H+ + 5e- → Mn2+ + 4 H2O
oxidation reduction
To balance the manganese half-reaction - first balance for Mn and O
atoms. Next balance the H atoms, and finally add enough electrons to
balance the charge on both sides of the equation.
19/36 Practice lecture 3 – BALANCING REDOX REACTIONS
Balancing Redox Reactions using half-reactions (8/10)

20/36 Practice lecture 3 – BALANCING REDOX REACTIONS

 Balancing Redox Reactions using half-reactions (9/10)
Redox reactions when there are three half-reactions involved
Here is the sample equation, in acidic solution:
FeS + NO3¯ ---> NO + SO42¯ + Fe3+
Step One: separate out the half-reactions. The only issue is that there
are three of them.
Fe2+---> Fe3+
S2¯---> SO42¯
NO3¯ ---> NO
How did we recognize that there were three equations? you must
know the oxidation states of all the elements on EACH side of the
original equation.
By knowing this, you are able to determine that there were two
oxidations (the Fe going +2 to +3 and the S going -2 to +6) with one
reduction (the N going +5 to +2).
21/36 Practice lecture 3 – BALANCING REDOX REACTIONS
 Balancing Redox Reactions using half-reactions (10/10)

Step Two: balancing all half-reactions in the normal manner.

Fe2+---> Fe3+ + e¯
4H2O + S2- ---> SO42- + 8H+ +8e¯
3e¯ + 4H+ +NO3¯---> NO + 2H2O

Step Three: equalize the electrons on each side of the half-reactions.

Please note that the first two half-reactions (both oxidations) total up
to nine electrons. Consequently, a factor of three is needed for the
third equation, the only one shown below:
3 [3e¯ + 4H++ NO3¯--->NO +2H2O]

Adding up the three equations:

FeS + 4H+ + 3NO3- ---> Fe3+ + SO42- + 3NO + 2 H2O

22/36 Practice lecture 3 – BALANCING REDOX REACTIONS

Exercises (1)

2 2

23/36 Practice lecture 3 – BALANCING REDOX REACTIONS

Answers (1) (1/5)

2 2

1 2 2

24/36 Practice lecture 3 – BALANCING REDOX REACTIONS

Answers (1) (2/5)

25/36 Practice lecture 3 – BALANCING REDOX REACTIONS

Answers (1) (3/5)

26/36 Practice lecture 3 – BALANCING REDOX REACTIONS

Answers (1) (4/5)

27/36 Practice lecture 3 – BALANCING REDOX REACTIONS

Answers (1) (5/5)

28/36 Practice lecture 3 – BALANCING REDOX REACTIONS

Exercises (2)

29/36 Practice lecture 3 – BALANCING REDOX REACTIONS

Answers (2)

30/36 Practice lecture 3 – BALANCING REDOX REACTIONS

Exercises (3)

31/36 Practice lecture 3 – BALANCING REDOX REACTIONS

Answers (3)

32/36 Practice lecture 3 – BALANCING REDOX REACTIONS

Exercises (4)

33/36 Practice lecture 3 – BALANCING REDOX REACTIONS

Answers (4) (1/3)

34/36 Practice lecture 3 – BALANCING REDOX REACTIONS

Answers (4) (2/3)

35/36 Practice lecture 3 – BALANCING REDOX REACTIONS

Answers (4) (3/3)

36/36 Practice lecture 3 – BALANCING REDOX REACTIONS