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# H

+
+SO
2
(aq) + Cr
2
O
7
2-
(aq) H
2
O + SO
4
2-
(aq) + Cr
3+
(aq)

Use half-reactions to balance the equation for the reaction between sulfur
dioxide and the dichromate ion in acidic solution.
STEP 1:Write a skeleton equation for the reaction.

STEP 2: Assign oxidation numbers to atoms on both sides of the equation.
STEP 3: Determine which atoms are oxidized and which are reduced.

STEP 4: Divide the reaction into oxidation and reduction half-reactions and balance
these half-reactions.
Add electrons to each equation
Reduction equation (What happens to the Oxygen atoms?):

Oxidation equation:

Add water and H
+

Step 5 combine equations:
a) Multiply the whole of Reduction equation by the number of electrons in
oxidation equation:
b) Multiply the whole of the Oxidation equation by the number of electrons in
reduction reaction.

Step 6 simplify equations:
MnO
4
-
(aq) + H
2
O
2
(aq)

Mn
2+
(aq) + O
2
(g)
Use the half-reaction method to determine the correct stoichiometry for this reaction.
FOLLOW STEPS AS BEFORE:
STEP 1:

STEP 2:

STEP 3:

STEP 4:

STEP 5:

STEP 6:

(b) (i) Part of the unbalanced equation for the preparation of nitrogen monoxide from
nitric acid is shown below.

Ag(s) + HNO 3 (aq) NO(g) + AgNO 3 (aq)

Identify the elements which are oxidized and reduced and give their oxidation
numbers.

Element oxidized .....................................................

Oxidation number initial ..................................... final .....................................

Element reduced .......................................................

Oxidation number initial ..................................... final .....................................

(ii) Complete and balance the equation for the reaction between silver and nitric
acid.

...............Ag(s) + ............... HNO3(aq) NO(g) + ............... AgNO3(aq) + ...................................

STEP 1:Write a skeleton equation for the reaction.
SO
2
+ Cr
2
O
7
2-
SO
4
2-
+ Cr
3+

STEP 2: Assign oxidation numbers to atoms on both sides of the equation.
SO
2
+ Cr
2
O
7
2-
SO
4
2-
+ Cr
3+

+4 -2 +6 -2

+6 -2

+3
STEP 3: Determine which atoms are oxidized and which are reduced.

STEP 4: Divide the reaction into oxidation and reduction half-reactions and balance
these half-reactions. This reaction can be divided into the following half-reactions.
Oxidation:

SO
2
SO
4
2-

+4

+6
Reduction:

Cr
2
O
7
2-
Cr
3+

+6

+3
It doesn't matter which half-reaction we balance first, so let's start with reduction. Because
the Cr
2
O
7
2-
ion contains two chromium atoms that must be reduced from the +6 to the +3
oxidation state, six electrons are consumed in this half-reaction.
Reduction: Cr
2
O
7
2-
+ 6 e
-
2 Cr
3+

This raises an interesting question: What happens to the oxygen atoms when the chromium
atoms are reduced? The seven oxygen atoms in the Cr
2
O
7
2-
ions are formally in the -2
oxidation state. If these atoms were released into solution in the -2 oxidation state when the
chromium was reduced, they would be present as O
2-
ions. But it doesn't make sense to write
this half-reaction as follows.
Reduction: Cr
2
O
7
2-
+ 6 e
-
2 Cr
3+
+ 7 O
2-

The reaction is being run in an acidic solution and the O
2-
ion is a very strong base that would
immediately react with the H
+
ions in this solution to form water, as shown in the figure
below.

The following is therefore a more realistic equation for this half-reaction.
Reduction: Cr
2
O
7
2-
+ 14 H
+
+ 6 e
-
2 Cr
3+
+ 7 H
2
O
We can now turn to the oxidation half-reaction, and start by noting that two electrons are
given off when sulphur is oxidized from the +4 to the +6 oxidation state.
Oxidation: SO
2
SO
4
2-
+ 2 e
-

The key to balancing the charge on both sides of this equation is remembering that the
reaction is run in acid, which contains H
+
ions and H
2
O molecules. We can therefore add H
+

ions or H
2
O molecules to either side of the equation, as needed. The only way to balance the
charge on both sides of this equation is to add four H
+
ions to the products of the reaction.
Oxidation:

SO
2
SO
4
2-
+ 2 e
-
+ 4 H
+

We can then balance the number of hydrogen and oxygen atoms on both sides of this
equation by adding a pair of H
2
O molecules to the reactants.
Oxidation:

SO
2
+ 2 H
2
O SO
4
2-
+ 2 e
-
+ 4 H
+

EXTRA UNDERTANDI NG:
This equation can be understood in terms of the Lewis structures shown in the figure below.

Let's focus, for the moment, on the middle Lewis structure and remove two electrons from the sulphur atom.

Let's now form two new sulfur-oxygen bonds by donating pairs of non bonding electrons from neighbouring water molecules.

The product of this hypothetical reaction can now lose a pair of H
+
ions to form sulphuric acid.

STEP 5: Combine the two half-reactions so that electrons are neither created nor
destroyed. Six electrons are consumed in the reduction half-reaction and two electrons are
given off in the oxidation half-reaction. We can combine these half-reactions so that electrons
are conserved by multiplying the reduction half-reaction by 3.
(Cr
2
O
7
2-
+ 14 H
+
+ 6 e
-
2 Cr
3+
+ 7 H
2
O)
+ 3(SO
2
+ 2 H
2
O SO
4
2-
+ 2 e
-
+ 4 H
+
)
__________________________________________
Cr
2
O
7
2-
+ 3 SO
2
+ 14 H
+
+ 6 H
2
O 2 Cr
3+
+ 3 SO
4
2-
+ 12 H
+
+ 7 H
2
O
STEP 6: Balance the remainder of the equation by inspection, if necessary. Although the
equation appears balanced, we are not quite finished with it. We can simplify the equation by
subtracting 12 H
+
ions and 6 H
2
O molecules from each side to generate the following
balanced equation.
Cr
2
O
7
2-
(aq) + 3 SO
2
(aq) + 2 H
+
(aq) 2 Cr
3+
(aq) + 3 SO
4
2-
(aq) + H
2
O(l)

MnO
4
-
(aq) + H
2
O
2
(aq)

Mn
2+
(aq) + O
2
(g)
Use the half-reaction method to determine the correct stoichiometry for this reaction.

Solution
STEP 1: Write a skeleton equation for the reaction.
MnO
4
-
+ H
2
O
2
Mn
2+
+ O
2

STEP 2: Assign oxidation numbers to atoms on both sides of the equation.
MnO
4
-
+ H
2
O
2
Mn
2+
+ O
2

+7 -2

+1-1

+2

0
STEP 3: Determine which atoms are oxidized and which are reduced.

STEP 4: Divide the reaction into oxidation and reduction half-reactions and
balance these half-reactions. We balanced the reduction half-reaction in the previous
exercise.
Reduction: MnO
4
-
+ 8 H
+
+ 5 e
-
Mn
2+
+ 4 H
2
O
To balance the oxidation half-reaction, we have to remove two electrons from a pair
of oxygen atoms in the -1 oxidation state to form a neutral O
2
molecule.
Oxidation:

H
2
O
2
O
2
+ 2 e
-

We can then add a pair of H
+
ions to the products to balance both charge and mass in
this half-reaction
Oxidation: H
2
O
2
O
2
+ 2 H
+
+ 2 e
-

STEP 5: Combine the two half-reactions so that electrons are neither created nor
destroyed. Two electrons are given off during oxidation and five electrons are
consumed during reduction. We can combine these half-reactions so that electrons are
conserved by using the lowest common multiple of 5 and 2.
2(MnO
4
-
+ 8 H
+
+ 5 e
-
Mn
2+
+ 4 H
2
O)
+ 5(H
2
O
2
O
2
+ 2 H
+
+ 2 e
-
)
________________________________________________________
2 MnO
4
-
+ 5 H
2
O
2
+ 16 H
+
2 Mn
2+
+ 5 O
2
+ 10 H
+
+ 8 H
2
O
STEP 6: Balance the remainder of the equation by inspection, if necessary. The
simplest balanced equation for this reaction is obtained when 10 H
+
ions are
subtracted from each side of the equation derived in the previous step.
2 MnO
4
-
(aq) + 5 H
2
O
2
(aq) + 6 H
+
(aq) 2 Mn
2+
(aq) + 5 O
2
(g) + 8 H
2
O(l)
STEP 1
Ag + HNO3 NO + AgNO3
STEP 2
Ag (0) N (5+) N (2+) Ag (1+)

STEP 3
Silver is Oxidised loss 1e-
Nitrogen is Reduced gain 3e-

STEP 4
OXIDATION
Ag Ag
+
+ e- AND HNO
3
NO
3
-
+ H
+

OR
Ag + HNO
3
AgNO
3
+ e- + 1H
+

REDUCTION
3H
+
+ 3e- + HNO
3
NO + 2H
2
O
STEP 5
3Ag + 3H
+
+ 4HNO
3
NO + 2H
2
O + 3Ag NO
3
+ 3H
+
OR

COMBINE REDOX
3Ag + 3H
+
+ HNO
3
NO + 2H
2
O + 3Ag
+

COMBINE NITRIC ACID
HNO
3
H
+
+ HNO
3
(multiply by three to balance with Ag+)
3HNO
3
3H
+
+ HNO
3

=
3Ag + 3H
+
+ 4HNO
3
NO + 2H
2
O + 3AgNO
3
+ 3H
+

STEP 6
3Ag + 3H
+
+ 4HNO
3
NO + 2H
2
O + 3AgNO
3
+ 3H
+

= 3Ag + 4HNO
3
NO + 2H
2
O + 3AgNO
3

OH
-
+ Br
2
Br
-
+ BrO
3
-

STEP 1: Write a skeleton equation for the reaction.
Br
2
+ OH
-
Br
-
+ BrO
3
-

STEP 2: Assign oxidation numbers to atoms on both sides of the equation.
Br
2
+ OH
-
Br
-
+ BrO
3
-

0

-2 +1

-1

+5 -2
STEP 3: Determine which atoms are oxidized and which are reduced.
Br
2
to Br
-
= Reduced
Br
2
to BrO
3
-
= Oxidised
STEP 4: Divide the reaction into oxidation and reduction half-reactions and
balance these half-reactions. Bromine is oxidized from the 0 to the +5 oxidation
state in this reaction.
Oxidation:

Br
2
BrO
3
-

0

+5
Bromine is also reduced in this reaction, from the 0 to the -1 oxidation state.
Reduction:

Br
2
Br
-

0

-1
If we assume that two Br
-
ions are produced for each molecule of Br
2
reduced, the
reduction half-reaction would be written as follows.
Reduction: Br
2
+ 2 e
-
2 Br
-

If we assume that two BrO
3
-
ions are formed each time a Br
2
molecule is oxidized, the
oxidation half-reaction involves the loss of 10 electrons.
Oxidation: Br
2
2 BrO
3
-
+ 10 e
-

Because the reaction occurs in basic solution we can add OH
-
ions or H
2
O molecules
to either side of the equation, as needed. The trick, as always, is deciding which side
of the equation gets the OH
-
ions and which side gets the H
2
O molecules. In this case,
the only way to balance the charge on both sides of the equation is to add 12 OH
-
ions
to the reactants.
Oxidation: Br
2
+ 12 OH
-
2 BrO
3
-
+ 10 e
-

Six of the oxygen atoms in the OH
-
ions end up in the BrO
3
-
ions. What happens to
the other six oxygen atoms and the 12 hydrogen atoms? The most reasonable answer
is that they combine to form six H
2
O molecules.
Oxidation:

Br
2
+ 12 OH
-
2 BrO
3
-
+ 10 e
-
+ 6 H
2
O
STEP 5: Combine the two half-reactions so that electrons are neither created nor
destroyed. Ten electrons are given off in the oxidation half-reaction and two
electrons are consumed in the reduction half-reaction. We can therefore combine
these half-reactions as follows.
5(Br
2
+ 2 e
-
2 Br
-
)
+ (Br
2
+ 12 OH
-
2 BrO
3
-
+ 10 e
-
+ 6 H
2
O)
___________________________________________
6 Br
2
+ 12 OH
-
10 Br
-
+ 2 BrO
3
-
+ 6 H
2
O
STEP 6: Balance the remainder of the equation by inspection, if necessary. The
equation generated in the previous step is balanced, but it is not quite correct. The best
answer to this exercise would be the equation with the smallest possible coefficients,
so we divide all of the coefficients by 2.
3 Br
2
+ 6 OH
-
5 Br
-
+ BrO
3
-
+ 3 H
2
O
We now complete the exercise by identifying the states of the reactants and products,
as follows.
3 Br
2
(aq) + 6 OH
-
(aq) 5 Br
-
(aq) + BrO
3
-
(aq) + 3 H
2
O(l)