Oxidation-Reduction

In the last chapter, we looked at what happened in a reaction where a
proton was transferred from one chemical species to another. A proton is not,
however, the only part of an atom that can be moved. An electron can also be
moved from one chemical species to another.

Demonstration : Aluminum foil in CuCl
2
solution.


Where did those electrons go ?
-
-

In order for the aluminum to lose electrons, there must have
been something to gain the electrons. (If this were not the case, the
aluminum foil would disintegrate as soon as it was made.) Conversely,
in order for the copper ions to turn into copper solid, that is to gain
electrons, something must lose the electrons. Clearly, these
reactions are dependant on each other. One doesn't happen
without the other.

Defnitions :
The loss of electrons (as the aluminum did above) is known as
_____________________. It is called oxidation because this is what happens when
a metal oxidizes.
The gaining of electrons (as the copper ions did above) is known as
_____________________________. It is called reduction because when ores are
mined and refned, a large amount of ore is reduced to a small amount of metal.
1
The overall reaction that occurred is known as an ___________________________
reaction, sometimes shortened to a REDOX equation.
OXIDIZING AGENT
REDUCING AGENT

Looking at the above reaction once again, this time in terms of the
HALF-REACTIONS, we get :

oxidation
and
reduction


One other thing about the reaction, if we closely examined the solution, we
would fnd that there are NO free electrons foating around. Nature detests a
solution that has an electrical charge (a POLARIZED solution) therefore we must
look at the reaction once again. If these are the half reactions, one would think
that if we simply added them together,
We would get the overall reaction. When we do this:


We get an excess of electrons produced. This will not happen. We will
not have polarization occurring. In order for us to account for the extra electron,
we must add the two equations together mathematically to eliminate the
electrons .
2
Balancing REDOX reactions (version 1):
a) Write the two half -cell reactions:

b) The least common multiple of the electrons in the two half reactions is 6,
therefore we multiply each equation in order to make 6 electrons in each :

c) Now we can add together the two equations and eliminate the electrons :


The equation is now balanced.
NOTE : -The total number of atoms of each element is balanced.
- All the charges are balanced.
Easy way to remember what reactions are taking place:
Translation:
Another easy way to remember what is going on:
Translation:
Chemistry 12.
3
Oxidation-Reduction Instant Practice #1
1. Determine which of the following processes are oxidations and which are
reductions:
a) Co
2+
becomes Co
b) 2 I
-
becomes I
2
c) e
!+
becomes e
2+
d) "n
2+
becomes "n
#+
2. $hat is an oxidi%ing agent& $hat is a reducing agent&
!. 'ow do (ou )now when a redox reaction is balanced&
#. In the following reactions* indicate the
a) the species oxidi%ed +b) species reduced +c) oxidi%ing agent +d) reducing
agent
a) 'g
2+
,n --- 'g + ,n
2+
b) '
2
+ "n
#+
--- 2 '
+
+ "n
2+
c) 2 -i +
2
-- 2 -i + + 2
-
4
.. $hen cesium metal is exposed to chlorine gas* a bright flash occurs as
the elements react. /he product* cesium chloride* is a white solid
composed of cesium ions and chloride ions.
a) $rite the balanced o0erall reaction that occurs between chlorine and
cesium.
b) $rite the half-reactions which occur and identif( which half-reaction is
the reduction and which is the oxidation.
c) Identif( the reducing and oxidi%ing agents.
1. 2alance the following redox reactions. Identif( what has been reduced
and what is the reducing agent.
a) 3a + Cl
2
---- 3a
+
+ Cl
4
b) Cu
2+
+ ,g ---- Cu + ,g
2+
c) e
!+
+ 5l ---- e
2+
+ 5l
!+
d) 5u
!+
+ Cd ------ 5u + Cd
2+
5
Oxidation Numbers
Another easy way to tell if oxidation or reduction has occurred is to
calculate the oxidation number of the element in the compound. The oxidation
number is something like the valence of the element. It is assigned to atoms in
order to keep track of the redistribution of electrons during a chemical reaction.
By keeping account of the oxidation numbers of the reactants and products, it is
possible to determine how many electrons are gained or lost in each atom. The
oxidation number of an atom in a compound is assigned according to the
following rules:
1. The oxidation of any substance in its elemental form is ZERO.
examples:
2. The common oxidation number of hydrogen is +1 except in compounds
called hydrides ( here it is -1 )
examples:
3. The common oxidation number of oxygen is -2 except in compounds
known as peroxides ( here it is -1)
examples:
4. The oxidation of Alkali metals ( Group I A ) in a compound is always +1.
examples:
5. The oxidation of Alkali Earth ( Group IIA ) in a compound is always +2.
examples:
6
6. The oxidation number for halogens is usually -1, however, there are
exceptions. It can range from -7 to + 7.
examples:
7. The sum of the oxidation numbers of all the atoms in a neutral
compound is zero. The sum of the oxidation numbers of the atoms present
in a polyatomic ion is equal to the charge of the ion.
examples:
** To determine the oxidation nymber, we use the above rules and the **
electrical charge on the substance
example 1: Determine the oxidation number for Cr in Cr
2
O
7

2-
example 2: Determine the oxidation number for C in C
3
H
2
O
2
.
example 3: Determine the oxidation number for Mn in KMnO
4
.
To determine whether reduction or oxidation has occurred, determine the
change in oxidation numbers. If the change is negative, reduction has
occurred. If the change is positive, oxidation has occurred.
7
example: MnO
4

-
-------> MnO
2
example: As ------> HAsO
2
CHEMISTRY 12 OXIDATION NUMBERS
Determine the oxidation numbers of the element underlined in the following
formula :
1. SO
3
16. UO
3
31.SO
2
2-
46.CH
3
OH

2. PF
3
17.U
3
O
8
32.SrSiO
3
47.C
4
H
4
O
4
2-

3.PCl
5
18.U
2
O
5
33.S
2
OCl
4
48.C
5
H
10
O

4. Na
3
P 19.K
2
UO
4
34.S
2
O
3
Cl
4
49.C
2
H
3
O
2
-

5.S
2
F
10
20.MgU
2
O
7
35.H
2
SO
5
50.C
7
H
5
O
2
-
6.S
2
O
7
21.MnSO
4
36.SO
2
ClF
7.NO
3
-
22.MnO
2
37.NH
2
OH
8.NO
2
23.KMnO
4
38.C
2
O
4
2-
9. N
2
O
3
24.MnO
3
+
39.WO
4
2-
10.NO 25.MnCl
4
-
40.NO
2
-

11.N
2
O 26.H
2
SO
3
41.ClO
4
-
12.N
2
27.H
2
S
2
O
3
42.HIO
6
4-
13.N
3
-
28.H
2
S
2
O
7
43.P
2
O
7
4-
8
14.N
2
H
5
+
29.KHSO
4
44.CH
4
15.NH
4
+
30.S
4
45.CH
3
Cl
ANSWERS :
1. +6 11. +1 21. +2 31. +2 41. +7
2. +3 12. 0 22. +4 32. +4 42. +7
3. +5 13. -1/3 23. +7 33. +3 43. +5
4. -3 14. -2 24. +7 34. +5 44. -4
5. +5 15. -3 25. +3 35. +8 45. -2
6. +7 16. +6 26. +4 36. +6 46. -2
7. +5 17. +16/3 27. +2 37. -1 47.+1/2
8. +4 18. +5 28. +6 38. +3 48. 8/5
9. +3 19. +6 29. +6 39. +6 49. 0
10. +2 20. +6 30. 0 40. +3 50. 2/7
9
Determining if a REDOX reactions will proceed:
Mini Lab: Reactions between metals and metal ions.
Procedures:
Results:
Reactans:
Metal electrode +
Metal ion in solution
Observations Reaction?
or no
Reaction?
ION that is
stronger oxidizing
Agent (stronger
attraction to
electrons)
Cu + Zn
2+
Cu + Mg
2+
Cu + Pb
2+
Zn + Cu
2+
Zn + Mg
2+
Zn + Pb
2+
Mg + Cu
2+
Mg + Zn
2+
Mg + Pb
2+
Pb + Cu
2+
Pb + Zn
2+
Pb + Mg
2+
Analysis of Results:
1. Arrange the metal ions in terms of increasing the ability to oxidize (from
weaker to stronger oxidizing agent).
10
2. Write a balanced REDUCTION Half-Reaction for each metal ion on the table
below making sure to arrange the equations in order of decreasing strength of
oxidizing agents.
Table of Standard Reduction of Half Cell.

To determine if two species in the table will proceed spontaneously, note
the relative placement of each specie.
*** Any oxidizing agent will react with any reducing agent on the right
which is LOWER on the list***
3. Using the table above, determine if the following reactions will occur
spontaneously or if the reaction is non-spontaneous:
a) Cu
(s)
+ Mg(NO
3
)
2(aq)
-------->
b) Zn
(s)
+ Pb(NO
3
)
2(aq)
---------- >
c) Pb
(s)
+ Cu(NO
3
)
2(s)
---------- >
11
Standard Reduction Potential Chart

The table you have in front of you is a much more complete list than the one you made
in the lab. It will be provided for you on the fnal exam. It is important that you know how to use
this table.
As you can see, there are several reactions that simply involve the transfer of electrons
from an ion to an element (as we did in the lab). Also, there are a number of other reactions that
have either H
+
ions and water in them or OH
-
ions and water in them. These are the half
reactions that will take place in either acidic or basic solutions.
It should be stressed that These are only half of the reaction that will take place. They
are all reduction reactions. We have seen that reduction can only take place if oxidation is also
occurring. To get an oxidation half reaction all we have to do is to write the reaction in the
reverse order. Notice that the arrows are bidirectional - this does not mean that they are in
equilibrium but that they can proceed in either direction.
As we said before, in order for a reaction to occur spontaneously, both oxidation
and reduction must occur and the reduction reaction must be above the oxidation
reaction on the chart.


Assignment: Standard reduction potential ws.
12
Chemistry 12
Standard Reduction Potential WS
1. Calculate the 6
o

cell
for each reaction and state whether the reaction is expected to be
spontaneous.
a) Cr +

! 5g
+
--- Cr
!+
+ ! 5g
b) Cu + e
!+
-- Cu
2+
+ e
2+
c) ,n
2+
+ 2 '
2
7 + I
2
-- ,n7
2
+ # '
+
+ 2 I
4
d d) ! Cu + 2 37
!
-
+ 8 '
+
--- ! Cu
2+
+ # '
2
7 + 2 37
e e) 2 Cr
! +
+ 9 '
2
7 + ! :b
2+
--- Cr
2
7
9

2-
+ 1# '
+
+ ! :b
2. $hen sil0er metal is placed in 1 , 'Cl solution under standard conditions* there is no
obser0able reaction. 'owe0er* when magnesium metal is placed in the same 'Cl
solution* the metal oxidi%es and h(drogen gas is produced. 6xplain these two
phenomena.
!. $hat will happen if an aluminum spoon is used to stir a solution of e+37
!
)
!
&
#. Can a 1, solution of Iron III sulfate be stored in a container made of nic)el metal&
6xplain (our answer.
13
Balancing Half-Reactions -
The chart we have is good to use if we have a reaction that is on it (or if we actually
have it in our possession at the time we need it). If it isn't on the chart, or if we don't have a
chart handy, there is a straight forward, simple way to balance all half reactions :


Rules for balancing half reactions :

1. alance all elements e!cept hydrogen and o!ygen. "o this
the same way we would normally balance e#uations, by
changing coe$cients.
%. alance the o!ygen atoms by adding water molecules.
&. alance the hydrogen atoms by adding '
(
ions.
). alance the electrical charge by adding electrons.
**+. ,o ma-e the solution basic (if as-ed for) add the e!act same
number of O'. ions as '( ions to both sides of the e#uation. ,his will
eliminate '( ions by producing water. Cancel the e!cess water.

__________________________
Examples :
Mn
3+
-----> MnO
4
-
acidic conditions
14
o To check, count all the individual atoms on both sides of the equation.
o As well, the TOTAL CHARGE on both sides of the equation MUST be EQUAL.

example:
I
2
-----> IO
3
-
acidic
Example:
MnO
4
-
----> MnO
2
basic
How do we tell whether or not oxidation or reduction has occurred?
Example: FeHPO
3
------- > PO
4
3-
+ Fe(OH)
3
(acidic)

15
- Assignment :


16

CHEMISTRY 12 BALANCING HALF-CELL REACTIONS

Balance the following half-cells.

1. Ce
4+
---> Ce
2+

2. I
2
---> I
-

3. Mn
2+
---> MnO
2
(acidic solution)

4. O
2
---> H
2
O
2
(acidic solution)

5. S
2
O
8
2-
---> HSO
4
- (acidic solution)

6. MnO
4
- ---> MnO
2
(acidic solution)

7. NO
3
-
---> NO (acidic solution)

8. ClO
3
- ---> Cl- (acidic solution)

9. H
3
AsO
4
---> HAsO
2
(acidic solution)

10. H
2
SeO
3
---> Se (acidic solution)

11. HO
2
-
---> O
2
(basic solution)

12. N
2
H
4
---> N
2
(basic solution)

13. Cr
2
O
7
2-
---> Cr
3+
(acidic solution)

14. HXeO
4
-
---> HXeO
6
3-
(basic solution)

15. Cr(OH)
3
---> CrO
4
2-
(basic solution)

16. FeS ---> Fe
3+
+ SO
4
2-
(acidic solution)

17. Cu
2
S ---> Cu
2+
+ H
2
SO
3
(acidic solution)

18. FeHPO
3
---> PO4
3-
+ Fe(OH)
3
(basic solution)

17
ANSWERS :

1. Ce4+ + 2e- ---> Ce2+

2. I2 + 2e- ---> 2I-

3. Mn2+ + 2H2O ---> MnO2 + 4H+ + 2e-

4. O2 + 2H+ + 2e- ---> H2O2

5. S2O82- + 2H+ + 2e- ---> 2HSO4-

6. MnO4- + 4H+ + 3e- ---> MnO2 + 2H2O

7. NO3- + 4H+ + 3e- ---> NO + 2H2O

8. ClO3- + 6H+ + 6e- ---> Cl- + 3H2O

9. H3AsO4 + 2H+ + 2e- ---> HAsO2 + 2H2O

10. H2SeO3 + 4H+ + 4e- ---> Se + 3H2O

11. HO2- + OH- ---> O2 + H2O + 2e-

12. N2H4 + 4OH- ---> N2 + 4H2O + 4e-

13. Cr2O72- + 14H+ + 6e- ---> 2Cr3+ + 7H2O

14. HXeO4- +4OH- ---> HXeO63- + 2H2O + 2e-

15. Cr(OH)3 + 5OH- ---> CrO42- + 4H2O + 3e-

16. FeS + 4H2O ---> Fe3+ + SO42- 8H+ + 9e-

17. Cu2S + 3H2O ---> 2Cu2+ + H2SO3 + 4H+ + 8e-

18. FeHPO3 + 6OH- ---> PO43- + Fe(OH)3 + 2H2O + 3e-
18
Balancing Full Reactions
In order to balance overall equations, it is important to do the following:
1. Isolate the two half reactions
2. Balance each half reaction separately
3. Find Least Common Multiple for the electrons
4. Add equations together to get rid of free
electrons
Example: Mn
3+
+ Au
3+
-------> MnO
4
-
+ Au
Note: in the overall balanced equation the numbers of atoms of each type are the same on
each side of the equation. Also, the electrical charges are equal. Both of these rules
are the same as with half reactions but, most importantly, in an overall reaction, there
are NO ELECTRONS FREE TO ROAM AROUND!!!
Example: Cr
2
O
7
2-
+ HXeO
4
-
----> Cr
3+
+ HXeO
6
3-
19
example: MnO
4
-
(aq)
+ Fe
2+
(aq)
---------- > Fe
3+
(aq)
+ Mn
2+
(aq)
Example: Ag
(s)
+ CN
-
(aq)
+ O
2(aq)
-------------- > Ag(CN)
2
-
(aq)
20
Further Notes on Balancing Redox Eqations
1. Sometimes, there are bizarre circumstances where the reactant
undergoes BOTH oxidation and reduction. In order to balance
these equations, we must make two equations -- one oxidation and
one reduction. From here, we can go through the procedures we did
in the previous section.
example: Br
2
----> HBr + HBrO
3
2. Sometimes there are more than one species undergoing either
oxidation or reduction ( an even more bizarre case ). In situations
such as these, we should try and isolate one element in its own half
reaction and place the others in a separate half reaction.
example: Mn
3+
+ FeSO
4
----> MnO
4
-
+ Fe + SO
2
( basic )
21
example: Gold metal will not dissolve in either concentrated nitric acid or
concentrated hydrochloric acid. It will dissolve, however, in aqua regia, a mixture
of the two concentrated acids. The products of the reaction are the AuCl
4
-
and
gaseous NO. Write a balanced equation for the dissolution of gold in aqua regia.
example: Chlorine was frst prepared in 1774 by C.W. Scheele by oxidizing
sodium choloride with manganese (IV) oxide. The reaction is:
NaCl
(aq)
+ H
2
SO
4(aq)
+ MnO
2(s)
---------> Na
2
SO
4(aq)
+ MnCl
2(aq)
+ H
2
O
(l)
+ Cl
2(aq)
Balance this equation:
22
CHEMISTRY 12
BALANCING OXIDATION-REDUCTION EQUATIONS

1. Cl
2
+ SO
2
---> Cl
-
+ SO
4
2-
(acidic)
2. Cu + NO
3
- ---> Cu
2+
+ NO (acidic)

3. S
2-
+ ClO
3
- ---> Cl
-
+ S (basic)

4. Zn + As
2
O
3
---> AsH
3
+ Zn
2+
(acidic)

5. Fe
2+
+ Cr
2
O
7
2-
---> Cr
3+
+ Fe
3+
(acidic)

6. U
4+
+ MnO
4
-
---> Mn
2+
+ UO
2
2+
(acidic conditions)

7. CN
-
+ IO
3
-
---> I
-
+ CNO
-


8. Mn
2+
+ HBiO
3
---> Bi
3+
+ MnO
4
-
(acidic)

9. HSO
3
-
+ IO
3
-
---> I
2
+ SO
4
2-
(acidic)

The following equations involve a species which undergoes BOTH oxidation and reduction at
the same time. Use two separate half cells with the same reactant.

10. OCl
-
---> Cl
-
+ ClO
3
-


11. HNO
2
---> HNO
3
+ NO

12. Br
2
---> Br
-
+ BrO
3
-
(basic)

The following equations involve three changes in oxidation numbers. HINT : One of the species
can be isolated. Use this in a half cell by itself. The other two can not be separated. Use a half
cell involving both.

13. Sb
2
S
3
+ NO
3
-
---> NO
2
+ SO
4
2-
+ Sb
2
O
5
(acidic)

14. As
2
S
3
+ NO
3
-
---> NO + SO
4
2-
+ H
3
AsO
4
(acidic)

15. FeS + NO
3
-
---> NO + SO
4
2-
+ Fe
3
+

(acidic)

16. FeHPO
3
+ Cr
2
O
7
2-
---> Cr
3+
+ H
3
PO
4
+ Fe
3+
(acidic)

17. SnS
2
O
3
+ MnO
4
-
---> Mn
2+
+ SO
4
2-
+ Sn
4
+
(acidic)

18. FeHPO
3
+ OCl
-
---> Cl
-
+ PO
4
3-
+ Fe(OH)
3
(acidic)
23

24
Answers :

1. Cl2 + SO2 + 2H2O ---> 2Cl- + SO42- + 4H+

2. 3Cu + 2NO3- + 8H+ ---> 3Cu2+ + 2NO + 4H2O

3. 3S2- + ClO3- + 3H2O ---> 3S + Cl- + 6OH-

4. 6Zn + As2O3 + 12H+ ---> 2AsH3 + 6 Zn2+ + 3H2O

5. 6Fe2+ + Cr2O72- + 14H+ ---> 2Cr3+ + 6Fe3+ + 7H2O

6. 2H2O + 5U4+ + 2MnO4- ---> 2 Mn2+ + 5UO22+ + 4H+

7. 3CN- + IO3- ---> I- + 3CNO-

8. 2Mn2+ + 5HBiO3 + 9H+ ---> 5Bi3+ + 2MnO4- + 7H2O

9. 5HSO3- + 2IO3- ---> I2 + 5SO42- + 3H+ + H2O

10. 3OCl- ---> 2 Cl- + ClO3-

11. 3HNO2 ---> HNO3 + 2NO + H2O

12. 3Br2 + 6OH- ---> 5Br- + BrO3- + 3H2O

13. Sb2S3 + 22H+ + 28NO3- ---> 3SO42- + Sb2O5 + 28NO2 + 11H2O

14. 3As2S3 + 4H2O + 10H+ + 28NO3- ---> 9SO42- + 6H3AsO4 + 28NO

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

16. 2FeHPO3 + Cr2O72- + 14H+ ---> 2H3PO4 + 2Fe3+ + 2Cr3+ + 5H2O

17. SnS2O3 + 2MnO4- + 6H+ ---> 2SO42- + Sn4+ + 2Mn2+ + 3H2O

18. 2FeHPO3 + 5H2O + 3OCl- ---> 2PO43- + 2Fe(OH)3 + 6H+ + 3Cl-

19. 6Hg4Fe(CN)6 + 66H+ + 47ClO3- ---> 36NO + 36CO2 + 6Fe3+ +

24Hg2+ + 47Cl- + 33H2O

25
Stoichiometry and Redox Reactions: Redox Titrations
Similar to acid base titrations.
1.Oxidizing Agents: Acidic Potassium permanganate:
- strong oxidizing agent.
- MnO
4
-
- purple ----- > Mn
2+
- colourless
- Other oxidizing agents:
Use standard KMnO
4
to determine the concentration of an unknown solution of
Fe
2+
.
Equation: MnO
4
-
+ Fe
2+
----- Mn
2+
+ Fe
3+
Balanced equation:
Example 1:
Example: A 3.00 g sample of pure iron is dissolved in hydrochloric acid and the
resulting solution treated to produce Fe
2+
. The fnal volume of the solution is
500.0 mL. What volume of 0.0500 M KMnO
4
is required to titrate 25.0 mL
sample of Fe
2+
solution? (10.8 mL)
26
2.Reducing Agents: NaI, or KI (for I
-
)
Thiosulphate (S
2
O
3

2-
)
Sulphite (SO
3

2-
)
Oxalic acid (H
2
C
2
O
4
)
Example:
Analysis of Bleach can be done by reacting the solution with an excess amount
of I
-
. The reaction:
Titrate a known volume of this sample by reacting the solution with Na
2
S
2
O
3
and
using starch solution as indicator. The solution is a dark blue colour because of
the reaction between the starch and the Iodine.
At the endpoint, the iodine reacts completely, forming I-. The endpoint is
reached when the blue colour fades.
Example: A 25 mL sample of bleach is reacted with an excess amount of NaI.
The solution is then titrated with 0.500M solution of sodium thiosulphate. If 35.00
mL of the thiosulphate solution was required to bring the solution to endpoint,
what is the [OCl -] in bleach? (0.35 M)
Assignment: , Hebden p. 213 # 28, 31, 32, 33.
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Mini test coming on the frst part of electrochemistry coming up on Tuesday
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