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A.
Introduction
1.
Electrochemistry is _______________________________________________________
________________________________________________________________________
________________________________________________________________________
Electrochemical reactions involve the _________________________________________
________________________________________________________________________
(analogous to proton transfer in acids and bases).
2.
OXIDATION HALF-REACTION
REDUCTION HALF-REACTION
Chemistry 12
2Al
3+
________________________________________________________________________
________________________________________________________________________
while Cu
2+
________________________________________________________________________
________________________________________________________________________
B.
Oxidation Numbers
1.
2.
__________________________________________________________________
b)
__________________________________________________________________
__________________________________________________________________
i)
ii)
2+
2+
2+
iii)
c)
d)
e)
Chemistry 12
EXAMPLE 5.1
Problem:
Solution:
Na = _____
CCl4 = 0 = C + 4(_____)
Cl = _____, C = _____
N2O4 = 0 = 2N + 4(_____)
O = _____, N = _____
PO43- = 3- = P + 4(_____)
O = _____, P = _____
PbSO4 = 0 = Pb2+ + SO42 Pb = _____
SO42- = 2- = S + 4(_____)
O = _____, S = _____
3.
OXIDATION = __________________________________________________________
REDUCTION = _________________________________________________________
C.
1.
INCREASING
TENDENCY
TO REDUCE
F2 + 2e-
2F
Ag+ + e-
Ag
INCREASING
TENDENCY
TO OXIDIZE
Cu2+ +2e-
Cu
INCREASING
STRENGTH
AS AN
OXIDIZING AGENT
Zn2+ + 2e-
Zn
Li + + e-
Li
INCREASING
STRENGTH
AS A
REDUCING AGENT
The following observation can be made from the Table of Reduction Potentials:
i)
In general, __________________________________________________
____________________________________________________________
____________________________________________________________
ii)
In general, __________________________________________________
____________________________________________________________
____________________________________________________________
iii)
Chemistry 12
____________________________________________________________
e.g.
Cu+ + e-
Cu
(s)
Cu2+ + 2e-
Cu(s)
+
Cu2+ +e-
Cu
The Cu+ ion is found on both left and right sides. Similarly, Sn2+ and
Fe2+ are also found on both sides of the table.
iv)
____________________________________________________________
____________________________________________________________
____________________________________________________________
The table of Standard Reduction Potentials is used in a similar way to the table of
Relative Strengths of Acids. The species at the _______________ __________ have a
tendency to go _______________ while the species at the _______________
__________ have a tendency to go _______________. Each reaction in the table can go
________________________________________________________________________
The half-reaction for Zn and Zn2+ is
Zn Zn2+ + 2e-
(written as a _______________)
(written as an _______________)
Note: When referring to an isolated half-reaction, use equilibrium arrows to show that
the reaction can go forward or backward.
Ag+ + e-
Ag
If the half-reaction is made to undergo either reduction or oxidation as a result of
being part of a redox reaction, the use a one-way arrow.
Ag+ + e- Ag
3.
Zn2+ + 2e-
Zn
Of the two oxidizing agents, _____ and _____, the _____ is _______________ on the
left side of the table and has a greater tendency to become _______________. The
reduction reaction will be
Cu2+ + 2e- Cu
Chemistry 12
Of the two reducing agents, _____ and _____, the _____ is _______________ on the
right side of the table and has a greater tendency to become _______________. The
oxidation reaction will be
Zn2+ + 2e- Zn
or re-written as
Zn Zn2+ + 2eThe overall redox reaction which will spontaneously occur is found by adding the two
half-reactions.
Cu2+ + 2eZn
Cu
Zn 2+ + 2e-
If ________________________________________________________________
__________________________________________________________________
(i.e., both are oxidizing agents (left) or both reducing agents (right)) then
__________________________________________________________________
Cu
+ 2e Cu
-
Zn 2+ + 2e- Zn
b)
If __________________________________________________ (oxidizing
agent) and __________________________________________________
(reducing agent) there are two possible cases.
i)
Zn 2+ + 2e-
10
Chemistry 12
ii)
EXAMPLE 5.2
Problem:
11
Solution:
b) Sn and Mn
___________________________________________________________
___________________________________________________________
12
Chemistry 12
5.
In _____________________________________________________________________
________________________________________________________________________
When H+ is present, _______________________________________________________
For example, if you asked whether the reaction of SO42- in a solution of Na2SO4 will
reduce:
SO42- + 4H+ + 2e- H2SO3 + 2H2O
+0.17
0.00
13
D.
1.
A half-reaction ___________________________________________________________
When balancing half-reactions ______________________________________________
________________________________________________________________________
The steps to balancing a half-reaction are as follows:
Typically you will be starting with a skeleton equation containing the major atoms
involved.
a)
Balance ___________________________________________________________
__________________________________________________________________
b)
Balance ___________________________________________________________
__________________________________________________________________
c)
d)
Balance ___________________________________________________________
__________________________________________________________________
14
Chemistry 12
EXAMPLE 5.3
Problem:
Solution:
Step 1:
Balance ATOMS.
Cr2O72- ____Cr3+
Step 2:
Balance OXYGEN.
Cr2O72- 2Cr3+ + ________
Step 3:
Balance HYDROGEN.
________ + Cr2O72- 2Cr3+ + 7H2O
Step 4:
Balance CHARGE.
________ + 14H+ + Cr2O72- 2Cr3+ + 7H2O
Note:
2.
EXAMPLE 5.3
Problem:
15
Solution:
Step 1:
Balance ATOMS.
MnO4- MnO2
Atoms already balanced.
Step 2:
Balance OXYGEN.
MnO4- MnO2 + ________
Step 3:
Balance HYDROGEN.
________ + MnO4- MnO2 + 2H2O
Step 4:
Balance CHARGE.
________+ 4H+ + MnO4- MnO2 + 2H2O
Step 5:
16
Chemistry 12
E.
1.
EXAMPLE 5.4
Problem:
Solution:
Step 1:
Step 2:
Step 3:
17
Step 4:
Once again, in basic solutions the final equation can be converted by ________________
________________________________________________________________________
________________________________________________________________________
-
18
Chemistry 12
3.
F.
1.
EXAMPLE 5.5
Problem:
19
Solution:
Step 1:
Balance atoms.
ClO4 + I2 Cl + 2IO3
Step 2:
ClO4
Step 3:
I2
Cl
2IO 3
____ClO4
Step 4:
____I2
____Cl
____IO3
Remember, ______________________________________________________________
________________________________________________________________________
________________________________________________________________________
20
Chemistry 12
SAMPLE
PROBLEM 5.1
Problem:
Solution:
MnO4- + Fe2+ Mn2+ + Fe3+
S2- + ClO3- Cl - + S
CN - + IO3- I - + CNO -
21
G.
Redox Titrations
1.
Acid-base titrations are useful for determining the concentration of an unknown sample
of acid or base. In a similar manner, __________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
2.
OXIDIZING AGENTS
One of the most common oxidizing agents used in redox titrations is ________________
The half-reaction:
MnO4- + 8H+ + 5e- Mn2+ + 4H2O
E = 1.49 V
has such a strong tendency to reduce that it will be able to oxidize a large number of
other substances. (The K+ in KMnO4 is left out because it is a spectator ion.)
In acid-base titrations, an ____________________ which changes colour is added to help
identify the ____________________ _______________ of the titration. An indicator is
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
If MnO4- (oxidizing agent) in a burette is added to a solution containing Fe2+ (reducing
agent), the MnO4- is converted to Mn2+ (colourless). ____________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
22
Chemistry 12
EXAMPLE 5.6
Problem:
Solution:
2+
2+
+ MnO4 Fe
3+
+ Mn
3+
2+
+ Mn
2+
+ _______
- 27.45 mL
0.100 M MnO4 x 1000 mL = _______________ mol MnO4
5 mol Fe
2+
1 mol MnO4
= _______________ mol Fe
Determine CONCENTRATION.
0.0137 mol Fe2+
= _______________M Fe2+
0.100 L
and since Fe2+ and FeCl2 are in a 1:1 ratio, [FeCl2] = _______________.
2+
3.
23
REDUCING AGENTS
first, _____________________________________________________________
__________________________________________________________________
b)
second, ___________________________________________________________
__________________________________________________________________
__________________________________________________________________
No attempt is made to add exactly enough I- to react with the OCl-. Rather, __________
________________________________________________________________________
The excess I- does not affect the results; however, _______________________________
________________________________________________________________________
The above reaction between OCl- and I- is the initial reaction because the actual redox
titration involves a second reaction between the I2 produced and the reducing agent
sodium thiosulphate, Na2S2O3.
I2 + 2e- 2I2S2O32- S4O62- + 2e___________________________
24
Chemistry 12
When the addition of S2O32- has reacted most of the I2 present, the brown colour of I2
almost disappears (pale yellow). Some starch solution is then added to the titration,
producing a dark blue colour (from the reaction of starch with the remaining I2 in
solution). After adding the starch, ___________________________________________
________________________________________________________________________
________________________________________________________________________
EXAMPLE 5.7
Problem:
25
The TWO reactions are linked together. The I2 produced in the first
reaction is used up in the second
2H+ + OCl- + 2I- Cl- + H2O + I2
2S2O32- + I2 S4O62- + 2I-
Solution:
I2
2S2O32-
= _______________ mol I2
26
Chemistry 12
H.
Electrochemical Cells
1.
Cu
2+
+ Zn Cu + Zn
A spontaneous reaction will occur when zinc metal is placed into a solution of CuSO4;
however, ________________________________________________________________
________________________________________________________________________
This same reaction can used to produce electricity if _____________________________
________________________________________________________________________
2.
An electrochemical cell:
a)
+ 0.34
- 0.76
27
__________________________
2+
Cu
2+
+ Zn Cu + Zn
28
Chemistry 12
b)
__________________________________________________________________
__________________________________________________________________
Cu
+ 2e Cu
Zn Zn
+ 2e
29
__________________________________________________________________
__________________________________________________________________
A __________ _______________ composed of a concentrated solution of a
strong electrolyte, usually KNO3 or KCl, connects the two cells to complete the
circuit. As the two half-reactions occur, _________________________________
__________________________________________________________________
__________________________________________________________________
Water and certain ions, Zn2+ and SO42-, will pass through the salt bridge from
one cell to the other. The positive Zn2+ ions are attracted to the CATHODE so
they are called _______________ while the negative SO42- ions are attracted to
the ANODE so they are called _______________.
__________________________________________________________________
__________________________________________________________________
30
Chemistry 12
Note: There are NO electrons flowing in the solution, only ions. ____________
____________________________________________________________
The salt bridge allow __________________________________________
____________________________________________________________
Since oxidation occurs at the anode, ______________________________
and since reduction occurs at the cathode, the _______________________
__________ as the electrochemical cell operates.
EXAMPLE 5.8
31
Problem:
Solution:
- 0.13
Zn2+ + 2e-
Zn
- 0.76
Since Pb2+ is the stronger oxidizing reagent, it will become reduced and Zn(s)
will become oxidized.
The two half-reactions are
Pb2+ + 2e-
Pb
Zn2+ + 2e__________________________
Zn
Pb
2+
+ Zn
Pb + Zn
2+
32
Chemistry 12
I.
1.
________________________________________________________________________
________________________________________________________________________
Since electrons cannot flow in an isolated half-cell, ______________________________
________________________________________________________________________
However, the ____________________________________________________________
________________________________________________________________________
A ______________________________________________________________________
________________________________________________________________________
The voltage for the HYDROGEN HALF-CELL is defined to be
2H+ + 2e- H2
E = __________
it is at __________, and
all elements are in their standard states (normal phases at 25 C), and
2.
33
E = + 0.34
This half-cell has a voltage which is 0.34 V ____________________ than that of the
hydrogen half-cell.
Zn2+ + 2e-
Zn
E = - 0.76
This half-cell has a voltage which is 0.76 V __________ than that of the hydrogen halfcell.
Since the voltage is a measure of the work done, reversing a reduction reaction such as
Zn2+ + 2e- Zn
E = - 0.76
produces ________________________________________________________________
Zn Zn2+ + 2e-
E = + 0.76
________________________________________________________________________
________________________________________________________________________
3.
Hg2+ + 2e-
Hg
E = + 0.85 V
Cu2+ + 2e-
Cu
E = + 0.34 V
34
Chemistry 12
E = __________ V
E = __________ V
_______________________________________________
ECELL = __________ V
________________________________________________________________________
________________________________________________________________________
EXAMPLE 5.9
Problem:
Solution:
Ni 2+ + 2e-
Ni
Fe2+ + 2e-
Fe
E = - 0.26 V
E = - 0.45 V
E = __________V
E = __________ V
_________________________________________
Note:
ECELL = __________
EXAMPLE 5.10
35
Problem:
Solution:
Ni 2+ + 2e-
Ni
Fe2+ + 2e-
Fe
E = - 0.26 V
E = - 0.45 V
E = __________ V
Fe2+ + 2e- Fe
E = __________ V
_______________________________________________
Note:
EXAMPLE 5.11
ECELL = __________
Problem:
Solution:
Ag+ + e-
Ag
E = + 0.80 V
Al 3+ + 3e-
Al
E = - 1.66 V
E = __________ V
E = __________ V
_______________________________________________
Note:
ECELL = __________
36
Chemistry 12
____________________
If E is ____________________ for a redox reaction, the reaction is
_________________________
__________________________________________________________________
__________________________________________________________________
Remember the ____________________ _______________ of a reaction
determines the rate.
In some texts, the reduction of neutral water is given as
2H+ (10-7 M) + 2e-
E = - 0.41 V
H
2(g)
2(g)
E = - 0.41 V
If a redox reaction occurs in acidic water, the reduction of H+ (at 0.00 V) may
occur and if a redox reaction occurs in a neutral solution, the reduction of neutral
water (at - 0.41 V) may be possible.
4.
37
E = + 0.34 V
If the [Cu2+] is _______________ than 1.0 M the equilibrium shifts __________ and the
reduction potential ____________________.
Cu2+ + 2e-
Cu
E > + 0.34 V
If the [Cu2+] is __________ than 1.0 M the equilibrium shifts __________ and the
reduction potential ____________________.
Cu2+ + 2e-
Cu
E < + 0.34 V
Notice that the is omitted from the E symbol since it is not at standard state.
6.
38
Chemistry 12
Cu2+ + 2e- Cu
INITIALLY
AS TIME
PASSES
FINALLY
Voltage
ECELL = + 0.46
V
Cu2+ + 2e- Cu
________________________________________________________________________
________________________________________________________________________
39
J.
1.
Ag
Zn
Zn 2+
-
NO 3
Cu
Ag +
Cu 2+
NO 3
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
Therefore, the __________ will reduce and form __________
40
Chemistry 12
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
Therefore, the __________ will oxidize to form __________
2.
First, _____________________________________________________________
__________________________________________________________________
EXAMPLE 5.12
41
Problem:
An iron strip is placed in a mixture of Br2(aq) and I2(aq). What is the preferred
reaction which occurs?
Solution:
E = + 1.09 V
I 2 + 2e-
2I
E = + 0.54 V
Fe2+ + 2e-
Fe
E = - 0.45 V
The preferred reduction involves __________ and the only oxidation possible
involves __________. The overall reaction is
___________________________
__________________________________________________________________
__________________________________________________________________
__________________________________________________________________
Similarily, any ion capable of being ____________________________________
__________________________________________________________________
__________________________________________________________________
__________________________________________________________________
The following ions are generally considered to be spectator ions:
Na+, K+, Ca2+, Mg2+, SO42- (in neutral solution), and Cl-
42
Chemistry 12
K.
Corrosion of Metals
1.
Precipitate of
Fe(OH) 2
Fe
anode region
(oxygen-poor)
At the __________________________________________________________________
________________________________________________________________________
Fe(s) Fe2+ + 2eAfter being formed, the Fe2+ ions ____________________________________________
________________________________________________________________________
________________________________________________________________________
As the Fe2+ ions move away, they expose fresh Fe(s) for further oxidation. In the
meantime, the reaction
1
2
is proceeding at the oxygen-rich outer surface of the drop. When the Fe2+ meets the OH, it _____________________________________________________________________
The Fe(OH)2 is eventually __________________________________________________
________________________________________________________________________
43
2.
PREVENTING CORROSION
A.
i)
Apply ______________________________________________________
____________________________________________________________
If oxygen and water cannot reach the metal, it will not corrode.
ii)
Apply ______________________________________________________
____________________________________________________________
Tin can be applied to the surface of steel cans. The tin is quickly oxidized
to produce a thin layer of tin oxide which protects the underlying metal
from further corrosion.
44
Chemistry 12
B.
Electrochemical Methods
i)
Cathodic Protection
Zinc blocks are bolted to iron-hulled ships to prevent them from rusting.
Some modern ships pass a low voltage electric current into the hull from
an electrical generator. This forces electrons into the metal and prevents it
from becoming oxidized.
Galvanized iron involves coating zinc onto the surface of iron sheets.
45
Some buried gas and oil tanks made from steel have thick braided wire
connected to them. The wire is attached to posts made of magnesium or
zinc.
ii)
When iron is placed in contact with water containing oxygen, the halfreaction
1
2
L.
Electrolysis
1.
ELECTROLYSIS is ______________________________________________________
________________________________________________________________________
________________________________________________________________________
An ____________________ __________ or ELECTROLYSIS CELL is an apparatus
in which electrolysis can occur.
46
2.
Chemistry 12
+
Na
is sometimes used)
Cl
There is ________________________________________________________________
________________________________________________________________________
The only reactants present are Na+ and ClCl2 + 2e- 2ClNa+ + e- Na
E = - 1.36 V
Na+ + e- Na
E = - 2.71 V
Ecell = - 4.07 V
47
Since the half-cells are not at standard state, the reduction potentials will be different
from those listed on the table.
3.
D.C.
__________________________________________________________________
There are two possible oxidations:
1
2
= + 0.82 V
I2 + 2e-
= + 0.54 V
48
Chemistry 12
= - 0.41 V
= - 2.71 V
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
________________________________________________________________________
The half-reactions and the overall reaction involving the electrolysis of NaI(aq) are
2H2O + 2e- H2(g) + 2OH- (10-7 M)
2I- I2 + 2e-
= - 0.41 V
= - 0.54 V
= - 0.95 V
49
Note: The concentrations of the materials in cells will not be of concern; as long as
there is sufficient material in the cell you can assume the reactions proceed as
predicted.
In NEUTRAL aqueous solutions, there are two water equations which must be
considered.
OXIDATION:
1
2
= + 0.82 V
REDUCTION:
= - 0.41 V
In ACIDIC solutions there are also two water equations which must be
considered.
4.
OXIDATION:
1
2
REDUCTION:
= + 1.23 V
= 0.00 V
In practice, it is found that a higher potential than calculated must be applied to cause
electrolysis. The causes are _________________________________________________
________________________________________________________________________
The difference between actual potentials required for electrolysis and the calculated
potential is termed ___________________________________. Overpotentials vary for
each half-cell but the difference in potentials is _________________________________
________________________________________________________________________
As a result of the overpotential effect, when dilute neutral solutions (< 1.0 M) containing
_____ or _____ are electrolyzed
50
Chemistry 12
OXIDATION:
1
2
Cl 2 + 2e- 2Cl -
= + 1.09 V
= + 0.82 V
= + 1.36 V
Strength of
Reducing
Agent
we would expect that _____ will be produced. In practice however, we find that _____
or _____ are actually produced.
In addition when dilute solutions of ____________________ are electrolyzed
REDUCTION:
2H2O + 2e- H2(g) + 2OH - (10-7 M)
Strongest
Oxidizing
Agent
= - 0.41 V
Fe2+ + 2e- Fe
= - 0.45 V
Cr3+ + 3e- Cr
= - 0.74 V
Zn 2+ + 2e- Zn
= - 0.76 V
Electrolysis of aqueous solutions containing Cl- or Br- will produce Cl2 or Br2 at the
anode.
Electrolysis of aqueous solutions containing Fe2+, Cr3+, or Zn2+ will produce Fe, Cr,
or Zn at the cathode.
EXAMPLE 5.13
51
ELECTROLYSIS REACTIONS
Problem:
What products are formed at the anode and cathode wand what is the overall
reaction when a solution containing NiSO4(aq) is electrolyzed using inert
electrodes? Determine the minimum voltage required.
Solution:
+ 4H + + 4e- H2SO3 + H 2O
= +0.17 V
+ 2e- Ni
= - 0.26 V
= -0.41 V
OXIDATION
1
2
O2(g) + 2H + (10-7 M) + 2e -
= +0.82 V
______________________________________________________________
______________________________________________________________
so the half -reactions that occur are:
Anode:
H2O
Cathode:
H2O + Ni 2+
1
2
1
2
O2(g) + 2H + (10-7 M) + 2e - E
Ni2+ + 2e- Ni
O2(g) + 2H + (10-7 M) + Ni
=
= - 0.26 V
CELL
52
Chemistry 12
EXAMPLE 5.14
ELECTROLYSIS REACTIONS
Problem:
Solution:
First, the species present H+, Cl -, H2O (acidic) and the possible reactions are
REDUCTION
+ 2e- H2
= +0.00 V
= -0.41 V
OXIDATION
1
2
Cl2(g) + 2e-
= +1.36 V
O2(g) + 2H + (10-7 M) + 2e -
= +0.82 V
Due to the high overpotential of H2O, the Cl- is oxidized so the two half
reactions are
H+ + 2e- H2
= + 0.00 V
Cathode
Anode
CELL
5.
53
ELECTROPLATING
ELECTROPLATING is __________________________________________________
________________________________________________________________________
________________________________________________________________________
The ____________________is made out of the material which will receive the metal
plating.
The _______________ may be made of the same metal which is to be plated out
onto the cathode. (This is normal but an inert electrode can also be used.)
54
Chemistry 12
EXAMPLE 5.15
ELECTROPLATING CELLS
Problem:
Solution:
The medallion must have the Ni(s) plated onto it, so it must be the
_______________.
The ions needed in solution will Ni2+ and some anion that does NOT form a
precipitate with Ni2+. The NO3- is always a good choice since all nitrates
are soluble.
6.
55
ELECTROREFINING
ELECTROREFINING is _________________________________________________
________________________________________________________________________
________________________________________________________________________
DC Power
Source