ElectroCh GRM
ElectroCh GRM
ElectroCh GRM
Electrochemistry
1
Electrochemistry
• Electrochemical reactions are oxidation-reduction
reactions.
• The two parts of the reaction are physically separated.
– The oxidation reaction occurs in one cell.
– The reduction reaction occurs in the other cell.
• There are two kinds electrochemical cells.
1. Electrochemical cells containing in no spontaneous
chemical reactions are called electrolytic cells.
2. Electrochemical cells containing spontaneous chemical
reactions are called voltaic or galvanic cells.
2
Electrical Conduction
• Metals conduct electric currents well in a
process called metallic conduction.
• In metallic conduction there is electron flow
with no atomic motion.
• In ionic or electrolytic conduction ionic motion
transports the electrons.
– Positively charged ions, cations, move toward the
negative electrode.
– Negatively charged ions, anions, move toward the
positive electrode.
3
Electrodes
• The following convention for electrodes is
correct for either electrolytic or voltaic cells:
• The cathode is the electrode at which
reduction occurs.
• The cathode is negative in electrolytic cells and
positive in voltaic cells.
• The anode is the electrode at which
oxidation occurs.
• The anode is positive in electrolytic cells and negative
in voltaic cells.
4
Electrodes
• Inert electrodes do not react with the
liquids or products of the electrochemical
reaction.
• Two examples of common inert electrodes
are graphite and platinum.
5
Voltaic or Galvanic Cells
• Electrochemical cells in which a spontaneous chemical
reaction produces electrical energy.
• Cell halves are physically separated so that electrons (from
redox reaction) are forced to travel through wires and creating
a potential difference.
• Examples of voltaic cells include:
Auto batteries
Flashlight batteries
Computer and calculator batteries
6
The Construction of Simple
Voltaic Cells
• Voltaic cells consist of two half-cells which
contain the oxidized and reduced forms of an
element (or other chemical species) in contact
with each other.
• A simple half-cell consists of:
– A piece of metal immersed in a solution of its ions.
– A wire to connect the two half-cells.
– And a salt bridge to complete the circuit, maintain
neutrality, and prevent solution mixing.
7
The Construction of Simple
Voltaic Cells
8
The Zinc-Copper Cell
• Cell components for the Zn-Cu cell are:
1. A metallic Cu strip immersed in 1.0 M copper (II) sulfate.
2. A metallic Zn strip immersed in 1.0 M zinc (II) sulfate.
3. A wire and a salt bridge to complete circuit
• The cell’s initial voltage is 1.10 volts
9
The Zinc-Copper Cell
Anode reaction Zn 0 Zn 2+ 2e
Cathode reaction Cu 2+ 2e Cu 0
Overall cell reaction Zn 0 Cu 2+ Zn 2+ Cu 0
This is a spontaneou s reaction w ith E 0
cell 1.10V
10
The Zinc-Copper Cell
• There is a commonly used short hand notation
for voltaic cells.
– The Zn-Cu cell provides a good example.
species (and concentrations)
in contact with electrode surfaces
salt bridge
electrode surfaces 11
The Copper - Silver Cell
• Cell components:
1.A Cu strip immersed in 1.0 M copper (II) sulfate.
2.A Ag strip immersed in 1.0 M silver (I) nitrate.
3.A wire and a salt bridge to complete the circuit.
• The initial cell voltage is 0.46 volts.
12
The Copper - Silver Cell
Anode reaction Cu 0 Cu 2 2e
Cathode reaction
2 Ag + + e - Ag 0
Overall cell reaction Cu 0 + 2 Ag + Cu 2+ + 2 Ag 0
This is a spontaneou s reaction w ith E 0cell 0.46V
• Compare the Zn-Cu cell to the Cu-Ag cell
– The Cu electrode is the cathode in the Zn-Cu cell.
– The Cu electrode is the anode in the Cu-Ag cell.
• Whether a particular electrode behaves as an anode or as a
cathode depends on what the other electrode of the cell is.
13
The Copper - Silver Cell
• These experimental facts demonstrate that Cu2+ is a stronger oxidizing agent
than Zn2+.
– In other words Cu2+ oxidizes metallic Zn to Zn2+
• Similarly, Ag+ is is a stronger oxidizing agent than Cu2+.
– Because Ag+ oxidizes metallic Cu to Cu 2+.
• If we arrange these species in order of increasing strengths, we see that:
Zn 2+ < Cu 2+ < Ag +
strength as oxidizing agent
Zn 0 > Cu 0 > Ag 0
strength as reducing agent
14
Standard Electrode Potential
• To measure relative electrode potentials, we must
establish an arbitrary standard.
• That standard is the Standard Hydrogen Electrode
(SHE).
– The SHE is assigned an arbitrary voltage of 0.000000… V
15
The Zinc-SHE Cell
• For this cell the components are:
1. A Zn strip immersed in 1.0 M zinc (II) sulfate.
2. The other electrode is the Standard Hydrogen Electrode.
3. A wire and a salt bridge to complete the circuit.
• The initial cell voltage is 0.763 volts.
16
The Zinc-SHE Cell
E0
Anode reaction Zn 0 Zn 2+ + 2 e - 0.763 V
Cathode reaction 2 H + + 2 e - H 2g 0.000 V
Cell reaction Zn 0 + 2H + Zn 2+ + H 2g E 0cell 0.763 V
17
The Copper-SHE Cell
• The cell components are:
1. A Cu strip immersed in 1.0 M copper (II) sulfate.
2. The other electrode is a Standard Hydrogen Electrode.
3. A wire and a salt bridge to complete the circuit.
• The initial cell voltage is 0.337 volts.
18
The Copper-SHE Cell
• The cell components are:
1. A Cu strip immersed in 1.0 M copper (II) sulfate.
2. The other electrode is a Standard Hydrogen Electrode.
3. A wire and a salt bridge to complete the circuit.
• The initial cell voltage is 0.337 volts.
19
The Copper-SHE Cell
E0
Anode reaction H 2g 2 H + + 2 e - 0.000 V
Cathode reaction Cu 2+ + 2e - Cu 0 0.337 V
Cell reaction H 2g + Cu 2+ 2H + + Cu 0 E 0cell 0.337 V
20
21
22
Uses of Standard Electrode
Potentials
• Electrodes that force the SHE to act as an anode are
assigned positive standard reduction potentials.
• Electrodes that force the SHE to act as the cathode are
assigned negative standard reduction potentials.
• Standard electrode (reduction) potentials tell us the
tendencies of half-reactions to occur as written.
• For example, the half-reaction for the standard potassium
electrode is:
K e K 0 0
E = -2.925 V
The large negative value tells us that this reaction
will occur only under extreme conditions.
23
Uses of Standard Electrode
Potentials
• Compare the potassium half-reaction to fluorine’s half-
reaction:
0 - - 0
F2 + 2e 2F E = +2.87 V
• The large positive value denotes that this reaction occurs
readily as written.
• Positive E0 values denote that the reaction tends to occur to
the right.
– The larger the value, the greater the tendency to occur to the
right.
• It is the opposite for negative values of Eo.
24
Uses of Standard Electrode
Potentials
• Use standard electrode potentials to
predict whether an electrochemical
reaction at standard state conditions will
occur spontaneously.
• Example 21-3: Will silver ions, Ag+, oxidize
metallic zinc to Zn2+ ions, or will Zn2+ ions
oxidize metallic Ag to Ag+ ions?
• Steps for obtaining the equation for the
spontaneous reaction.
25
Uses of Standard Electrode Potentials
1. Choose the appropriate half-reactions from a table of standard
reduction potentials.
2. Write the equation for the half-reaction with the more positive E0 value
first, along with its E0 value.
3. Write the equation for the other half-reaction as an oxidation with its
oxidation potential, i.e. reverse the tabulated reduction half-reaction
and change the sign of the tabulated E0.
4 Balance the electron transfer.
5 Add the reduction and oxidation half-reactions and their potentials.
This produces the equation for the reaction for which E0cell is positive,
which indicates that the forward reaction is spontaneous.
26
Cell EMF
Standard Reduction Potentials
• The oxidation of Zn with the SHE is spontaneous.
• Changing the stoichiometric coefficient does not
affect Ered.
• Therefore,
2Zn2+(aq) + 4e- 2Zn(s), Ered = -0.76 V.
• Reactions with Ered > 0 are spontaneous
reductions relative to the SHE.
• Reactions with Ered < 0 are spontaneous
oxidations relative to the SHE.
27
Cell EMF
Standard Reduction Potentials
• The larger the difference between
Ered values, the larger Ecell.
• In a voltaic (galvanic) cell
(spontaneous) Ered(cathode) is more
positive than Ered(anode).
• Recall
Ecell = Ered(cathode) - Ered(anode)
28
Cell EMF
Oxidizing and Reducing Agents
• The more positive Ered the stronger the oxidizing
agent on the left.
• The more negative Ered the stronger the reducing
agent on the right.
• A species on the higher to the left of the table of
standard reduction potentials will spontaneously
oxidize a species that is lower to the right in the table.
• That is, F2 will oxidize H2 or Li; Ni2+ will oxidize Al(s).
• Any species on the right will spontaneously reduce
anything that is higher to the left in the series.
29
Cell EMF
Oxidizing and Reducing Agents
30
Spontaneity of Redox Reactions
• Consider the displacement of silver by nickel:
Ni(s) + 2Ag+(aq) Ni2+(aq) + 2Ag(s)
has
E = Ered(Ag+/Ag) - Ered(Ni2+/Ni)
= (0.80 V) - (-0.28 V)
= 1.08 V,
which indicates a spontaneous process.
31
Uses of Standard Electrode Potentials
E0
Reduction 2(Ag + + e - Ag 0 ) + 0.7994 V
Oxidation 1(Zn Zn 2+ + 2 e - ) - (-0.7628 V)
Cell reaction 2Ag + + Zn 0 2Ag 0 + Zn 2+ E 0cell = +1.5662 V
32
Electrode Potentials for Other Half-Reactions
35
Effect of Concentrations (or Partial
Pressures) on Electrode Potentials
The Nernst Equation
• Standard electrode potentials, those compiled
in appendices, are determined at
thermodynamic standard conditions.
• Reminder of standard conditions.
1.00 M solution concentrations
1.00 atm of pressure for gases
All liquids and solids in their standard thermodynamic
states.
Temperature of 250 C.
36
The Nernst Equation
• The value of the cell potentials change if
conditions are nonstandard.
• The Nernst equation describes the electrode
potentials at nonstandard conditions.
• The Nernst equation is:
37
The Nernst
2.303RT
Equation
E = E0 - log Q
nF
E = potential under condition of interest
E 0 potential under standard conditions
R = universal gas constant = 8.314 J
mol K
T = temperatur e in K
n = number of electrons transferr ed
F = the faraday = (96,487 C/mol e - ) 1 J .
CV
96,487 J/V mol e -
Q = reaction quotient
38
The Nernst Equation
• Substitution of the values of the constants into
the Nernst equation at 25o C gives:
2.303 RT 2.303 8.314 J mol K 298 K
-
0.0592
F 96,487 J/V mol e
0 0.0592
Thus E = E - log Q
n
39
The Nernst Equation
• For this half-reaction:
2+
Cu e Cu - 0
E = +0.153 V
• The corresponding Nernst equation is:
E=E -
0.0592
0
log
Cu +
1 Cu 2
40
The Nernst Equation
• Substituting E0 into the above expression gives:
E = 0.153 V -
0.0592
log
Cu +
1 Cu 2
• If [Cu2+] and [Cu+] are both 1.0 M, i.e. at standard
conditions, then E = E0 because the concentration
term equals zero.
0.0592 1
E = 0.153 V - log
1 1
41
The Nernst Equation
42
Write the Nernst equation and
emf of the cell given below
• Mg (s) / Mg 2+ (0.001M) //
Cu 2+ (0.0001M) / Cu(s)
TRY THIS
43
The Nernst Equation
• Example 21-6: Calculate the potential for
the Cu2+/ Cu+ electrode at 250C when the
concentration of Cu+ ions is three times
that of Cu2+ ions.
Cu 2+
+ e Cu
-
Cu 3 Cu
+
3
2+
Q=
Cu Cu 2+ 2+
44
The Nernst Equation
• Example 21-6: Calculate the potential for
the Cu2+/ Cu+ electrode at 250C when the
concentration of Cu+ ions is three times
that of Cu2+ ions.
00.0592
E=E - log Q
1
0.0592
E = 0.153 V - log 3
1 45
The Nernst Equation
• Example 21-6: Calculate the potential for
the Cu2+/ Cu+ electrode at 250C when the
concentration of Cu+ ions is three times
that of Cu2+ ions.
0 0.0592
E=E - log Q
1
0.0592
E = 0.153 V - log 3
1
E = 0.153V - 0.05920.477 V
E = 0.153 - 0.0282 V 46
The Nernst Equation
• Example 21-7: Calculate the potential for the
Cu2+/Cu+ electrode at 250C when the Cu+ ion
concentration is 1/3 of the Cu2+ ion concentration.
Cu 2+ -
+ e Cu
Cu + 1 Cu 2+
3 2+ 0.333
Q=
Cu 2+
Cu
You do it!
47
The Nernst Equation
• Example 21-7: Calculate the potential for the
Cu2+/Cu+ electrode at 250C when the
concentration of Cu+ ions is 1/3 that of Cu2+
ions.
0.0592
0
E=E - log Q
1
0.0592
E = 0.153 V - log 1
1 3
48
The Nernst Equation
0 0.0592
E=E - log Q
1
0.0592
E = 0.153 V - log 1
1 3
E = 0.153V - 0.0592- 0.477 V
E = 0.153 + 0.0282 V
E = 0.181 V
49
The Nernst Equation
• Example 21-8: Calculate the electrode potential for
a hydrogen electrode in which the [H+] is 1.0 x 10-3
M and the H2 pressure is 0.50 atmosphere.
+
2H +2e H -
2
Q=
PH 2
0.50
H 1.0 10
+ 2 3 2
Q 5.0 10 5
50
The Nernst Equation
• Example 21-8: Calculate the electrode potential for
a hydrogen electrode in which the [H+] is 1.0 x 10-3
M and the H2 pressure is 0.50 atmosphere.
E=E -
0.0592
0
2
log 5.0 105
0.0592
E 0 5.699
2
E 0.168 V
51
The Nernst Equation
• The Nernst equation can also be used to
calculate the potential for a cell that consists of
two nonstandard electrodes.
• Example 21-9: Calculate the initial potential of a
cell that consists of an Fe3+/Fe2+ electrode in
which [Fe3+]=1.0 x 10-2 M and [Fe2+]=0.1 M
connected to a Sn4+/Sn2+ electrode in which
[Sn4+]=1.0 M and [Sn2+]=0.10 M . A wire and salt
bridge complete the circuit.
52
The Nernst Equation
• Calculate the E0 cell by the usual
procedure. E 0
Reduction
2 Fe3+ + e Fe 2+ 0.771 V
Oxidation 1Sn 2+
Sn 4+ + 2 e - - 0.15 V
Cell reaction 2 Fe3+ Sn 2+ 2 Fe 2+ Sn 4+ E 0cell 0.62 V
53
The Nernst Equation
• Substitute the ion concentrations into Q to
calculate Ecell.
0 0.0592
E cell = E cell - log Q
2
= 0.62 V -
0.0592
log
Fe
2 2
Sn4
Sn
2
2 Fe3 2
E cell = 0.62 V -
0.0592
log
. 10
010 .
2
2
10 2 2
. 10 010 . 54
The Nernst Equation
E cell = 0.62 V -
0.0592
log
0.10 1.0
2
0.0592
E cell 0.62 V - 3.00
2
E cell 0.62 0.09 V
E cell = 0.53 V
55
Relationship of E0cell to G0
and K
• From previous chapters we know the
relationship of G0 and K for a reaction.
G -RT lnK
0
or
G 2.303 RT log K
0
56
Relationship of E0cell to G0 and
K
• The relationship between G0 and E0cell is also a
simple one.
G -n F E
0 0
cell
n number of e -
57
Relationship of E0cell to G0 and
K
• Combine these two relationships into a
single relationship to relate E0cell to K.
-n FE 0
cell - RT lnK
or
0
n FE
ln K cell
RT
58
Relationship of E0cell to G0 and
K
• Example 21-10: Calculate the standard
Gibbs free energy change, G0 , at 250C
for the following reaction.
2 2
Pb Cu Pb Cu
59
Relationship of E0cell to G0 and
K
1. Calculate E0cell using the appropriate half-
reactions.
0
E
2
Cu 2 e Cu 0
0.337 V
2
Pb Pb 2 e
- - 0.126 V
2 2
Cu Pb Pb Cu E 0 0
cell 0.463 V
60
Relationship of E0cell to G0 and
K
2. Now that we know E0cell , we can calculate G0 .
G 0
nFE 0
0cell
G 0
0
n F E cell
- 0.463 V
G 2 mol e 96,500 J
G 0
2 mol e 96,500 J V mol -e0.463 V
V mol e
G 0
8.94 10 J (per " mol of rxn" )
4
G -89.4 kJ
0
61
Relationship of E0cell to G0 and
K
• Example 21-11: Calculate the
thermodynamic equilibrium constant for
the reaction in example 21-10 at 250C.
G RT ln K
0
G 0 8.94 10 J
4
mol
ln K
RT - 8.314 J
mol K
298 K
ln K 36.1 K 5 1015
Pb 2
Cu 2
62
Relationship of E0cell to G0 and
K
• Example 21-12: Calculate the Gibbs Free
Energy change, G and the equilibrium
constant at 250C for the following reaction
with the indicated concentrations.
Zn 2 Ag 0.30 M 2Ag Zn
2
0.50 M
63
Relationship of E0cell to G0 and K
64
Relationship of E0cell to G0 and K
Q=
Zn 0.50
2+
5.6
Ag 0.30
+ 2 2
Q=
Zn 0.50
2+
5.6
Ag 0.30
+ 2 2
Q=
Zn 0.50
2+
5.6
Ag 0.30
+ 2 2
G = -297 kJ/mol
• The negative G tells us that the reaction is
spontaneous.
68
Relationship of E0cell to G0 and K
• Equilibrium constants do not change with reactant
concentration.
• We can use the value of E0cell at 250C to get K.
-n FE 0
cell 2.303 RT log K
- n F E 0cell
log K =
2.303 RT
2 96,500 1.562
log K
2.3038.314 298
log K 52.8
K = 6 10 52
Zn 2+
Ag + 2 69
Electrolytic Cells
• Electrical energy is used to force
nonspontaneous chemical reactions to
occur.
• The process is called electrolysis.
• Two examples of commercial electrolytic
reactions are:
1. The electroplating of jewelry and auto parts.
2. The electrolysis of chemical compounds.
70
Electrolytic Cells
• Electrolytic cells consist of:
1. A container for the reaction mixture.
2. Two electrodes immersed in the reaction
mixture.
3. A source of direct current.
71
The Electrolysis of Molten
Potassium Chloride
• Liquid potassium is produced at one
electrode.
– Indicates that the reaction K+() + e- K()
occurs at this electrode.
– Is this electrode the anode or cathode?
• Gaseous chlorine is produced at the other
electrode.
– Indicates that the reaction 2 Cl- Cl2(g) + 2 e-
occurs at this electrode.
– Is this electrode the anode or cathode?
72
The Electrolysis of Molten
Potassium Chloride
Diagram of this electrolytic cell.
e-
e- Generator-source
of DC
- electrode + electrode
molten KCl
74
The Electrolysis of Molten
Potassium Chloride
• In all electrolytic cells, electrons are
forced to flow from the positive electrode
(anode) to the negative electrode
(cathode).
75
The Electrolysis of Aqueous
Potassium Chloride
• In this electrolytic cell, hydrogen gas is produced at one electrode.
Anode reaction 2 Cl Cl
-
– The aqueous solution becomes basic near this electrode.
2(g) 2e
-
– What reaction is occurring at this electrode? You do it!
Cathode reaction 2 H O 2 e H -
• Gaseous chlorine is produced at the other electrode.
2
– What reaction is occurring at this electrode? You do it! 2 g 2 OH -
K is a spectator ion. Note that wate r is electrolyz ed!
76
The Electrolysis of Aqueous
Potassium Chloride
- pole of battery + pole of battery
Cell diagram Battery, a source
e- flow of direct current e- flow
- electrode + electrode
aqueous KCl
2 H2O + 2e- H2 (g) + 2 OH- 2Cl- Cl2 (g) + 2e- 77
cathode reaction anode reaction
The Electrolysis of Aqueous
Potassium Sulfate
• In this electrolysis, hydrogen gas is produced at
one electrode.
– The solution becomes basic near this electrode.
– What reaction is occurring at this electrode?
You do it!
• Gaseous oxygen is produced at the other electrode
– The solution becomes acidic near this electrode.
– What reaction is occurring at this electrode?
You do it!
• These experimental facts lead us to the following
electrode reactions:
78
The Electrolysis of Aqueous
Potassium Sulfate
Anode reaction 2 H 2 O O 2(g) 4 H 4 e -
Cathode reaction 2(2 H 2 O 2e- H 2(g) 2OH - )
Cell reaction 6 H 2 O 2 H 2(g) O 2(g) 4H 4 OH
-
4 H 2O
79
The Electrolysis of Aqueous
Potassium Sulfate
- pole of battery + pole of battery
Cell diagram Battery, a source
e- flow of direct current e- flow
- electrode + electrode
H2 gas O2 gas
aqueous K2SO4
2 H2O + 2e- H2 (g) + 2 OH- 2H2O O2 (g) + 4H+ + 4e- 80
cathode reaction anode reaction
Electrolytic Cells
• In all electrolytic cells the most easily
reduced species is reduced and the most
easily oxidized species is oxidized.
81
Counting Electrons: Coulometry
and Faraday’s Law of Electrolysis
• Faraday’s Law - The amount of substance undergoing chemical
reaction at each electrode during electrolysis is directly proportional
to the amount of electricity that passes through the electrolytic cell.
• A faraday is the amount of electricity that reduces one equivalent of
a species at the cathode and oxidizes one equivalent of a species
at the anode.
82
Counting Electrons: Coulometry
and Faraday’s Law of Electrolysis
• A coulomb is the amount of charge that passes
a given point when a current of one ampere (A)
flows for one second.
• 1 amp = 1 coulomb/second
1 faraday 6.022 10 e 96,487 coulombs
23 -
83
Counting Electrons: Coulometry
and Faraday’s Law of Electrolysis
• Faraday’s Law states that during electrolysis, one faraday
of electricity (96,487 coulombs) reduces and oxidizes,
respectively, one equivalent of the oxidizing agent and the
reducing agent.
– This corresponds to the passage of one mole of electrons
through the electrolytic cell.
84
Counting Electrons: Coulometry
and Faraday’s Law of Electrolysis
• Example 21-1: Calculate the mass of palladium
produced by the reduction of palladium (II) ions during
the passage of 3.20 amperes of current through a
solution of palladium (II) sulfate for 30.0 minutes.
2+ + - -Pd 0
Cathode: Pd +
Cathode : Pd + 2e 22e
Pd 0
Anode : 2 H 2 O O 2g + 4H + + 4e -
2 mol 1 mol 4 mol 4 mol
2 mol 1 mol 4 mol 4 mol
22.4
22.4LSTP
L STP 496,500
496,500 C
C
60 s 3.20 C 22.4 LSTP O 2
? LSTP O 2 30.0 min
min s 496,500 C
0.334 LSTP O 2 or 334 mL STP O 2 86
Commercial Applications of
Electrolytic Cells
Electrolytic Refining and Electroplating of
Metals
• Impure metallic copper can be purified
electrolytically to 100% pure Cu.
– The impurities commonly include some active metals
plus less active metals such as: Ag, Au, and Pt.
• The cathode is a thin sheet of copper metal
connected to the negative terminal of a direct
current source.
• The anode is large impure bars of copper.
87
Commercial Applications of
Electrolytic Cells
• The electrolytic solution is CuSO4 and H2SO4
• The impure Cu dissolves to form Cu2+.
• The Cu2+ ions are reduced to Cu at the cathode.
0 2
Anode impure Cus Cuaq 2e
2+ 0
Cathode very pure Cuaq 2e Cus
Net rxn. No net rxn.
88
Commercial Applications of
Electrolytic Cells
• Any active metal impurities are oxidized to cations that are more
difficult to reduce than Cu2+.
– This effectively removes them from the Cu metal.
2
Zn Zn
0
2e
2
Fe Fe 2e
0
= 0.0585 L = 58.5 mL
91
Quantitative
Quantitative Aspects
Aspects of
of
Electrochemistry
Electrochemistry
Consider electrolysis of aqueous silver
ion.
Ag+ (aq) + e- ---> Ag(s)
1 mol e- ---> 1 mol Ag
If we could measure the moles of e-, we
could know the quantity of Ag formed.
But how to measure moles of e-?
92
Quantitative
Quantitative Aspects
Aspects of
of
Electrochemistry
Electrochemistry
Consider electrolysis of aqueous silver
ion.
Ag+ (aq) + e- ---> Ag(s)
1 mol e- ---> 1 mol Ag
If we could measure the moles of e-, we
could know the
Current quantity
Current==
charge
chargepassing
time
passing of Ag formed.
time
93
Quantitative
Quantitative Aspects
Aspects of
of
Electrochemistry
Electrochemistry
Consider electrolysis of aqueous silver
ion.
Ag+ (aq) + e- ---> Ag(s)
1 mol e- ---> 1 mol Ag
If we could measure the moles of e-, we
charge
charge passing
passing
could Current
know the
Current = quantity of Ag formed.
=
time
time
But how to measure coulombs
moles of e-?
II (amps) = coulombs
(amps) =
seconds
seconds 94
Quantitative
Quantitative Aspects
Aspects of of
Electrochemistry
Electrochemistry
charge
charge passing
passing
Current
Current==
time
time
coulombs
coulombs
II (amps) =
(amps) =
seconds
seconds
But how is charge related to moles of electrons?
Charge on 1 mol of e- =
(1.60 x 10-19 C/e-)(6.02 x 1023 e-/mol)
= 96,500 C/mol e- = 1 Faraday
95
Quantitative
Quantitative Aspects
Aspects of
of
Electrochemistry
Electrochemistry
coulombs
II(amps) coulombs
(amps)== seconds
seconds
1.50 amps flow thru a Ag+(aq) solution for
15.0 min. What mass of Ag metal is
deposited?
Solution
(a) Calc. charge
Coulombs = amps x time
= (1.5 amps)(15.0 min)(60 s/min) = 1350
C
96
Quantitative
Quantitative Aspects
Aspects of
of
Electrochemistry
Electrochemistry
coulombs
II(amps)coulombs
(amps)== seconds
seconds
1.50 amps flow thru a Ag+(aq) solution for 15.0
min. What mass of Ag metal is deposited?
Solution
(a) Charge = 1350 C
(b) Calculate moles of e- used
97
Quantitative
Quantitative Aspects
Aspects of
of
Electrochemistry
Electrochemistry
coulombs
II(amps)coulombs
(amps)== seconds
seconds
1.50 amps flow thru a Ag+(aq) solution for 15.0
min. What mass of Ag metal is deposited?
Solution
(a) Charge = 1350 C
(b) 1350 11 mol
Calculate ee
--
moles
mol of e-mol
used
1350C
C •• 0.0140
0.0140 mol -e
-e
96,500
96,500 C
C
98
Quantitative
Quantitative Aspects
Aspects of
of
Electrochemistry
Electrochemistry
coulombs
II(amps)coulombs
(amps)== seconds
seconds
1.50 amps flow thru a Ag+(aq) solution for 15.0 min. What
mass of Ag metal is deposited?
Solution
(a) Charge = 1350 C
(b) Calculate moles of e- used
11 mol
mol ee
--
1350
1350CC •• 96,500 C 0.0140
0.0140 mol
mol-e
-e
96,500 C
(c)0.0140
Calc. quantity
mol e- • of
11 mol
mol Ag
Ag
Ag
0.0140 mol Ag or 1.51 g A
- • 1 mol e- 0.0140 mol Ag or 1.51 g A
0.0140 mol e
1 mol e- 100
Quantitative
Quantitative Aspects
Aspects ofof
Electrochemistry
Electrochemistry
The anode reaction in a lead storage battery is
Pb(s) + HSO4-(aq) ---> PbSO4(s) + H+(aq) + 2e-
If a battery delivers 1.50 amp, and you have
454 g of Pb, how long will the battery last?
Solution
a) 454 g Pb = 2.19 mol Pb
b) Calculate moles of e-
101
Quantitative
Quantitative Aspects
Aspects of of
Electrochemistry
Electrochemistry
The anode reaction in a lead storage battery is
Pb(s) + HSO4-(aq) ---> PbSO4(s) + H+(aq) + 2e-
If a battery delivers 1.50 amp, and you have 454
g of Pb, how long will the battery last?
Solution
a) 454 g Pb22= 2.19
mol
mol ee
-- mol Pb
2.19
2.19mol
molPb
Pb •• 1 mol Pb == 4.38
4.38 mol
mol -e-e
b) Calculate1moles
mol Pb of e-
102
Quantitative
Quantitative Aspects Aspects of
of
Electrochemistry
The anode reaction in aElectrochemistry
lead storage battery is
Pb(s) + HSO4-(aq) ---> PbSO4(s) + H+(aq) + 2e-
If a battery delivers 1.50 amp, and you have 454 g of Pb, how long will the
battery last?
Solution
a) 454 g Pb = 2.19 mol Pb
b) Calculate moles of e-
22 mol
mol ee
--
2.19
2.19 mol
mol Pb
Pb •• == 4.38
4.38 mol
mol -e-e
c) Calculate charge 11 mol
mol Pb
Pb
103
Quantitative
Quantitative Aspects Aspects of
of
Electrochemistry
The anode reaction in aElectrochemistry
lead storage battery is
Pb(s) + HSO4-(aq) ---> PbSO4(s) + H+(aq) + 2e-
If a battery delivers 1.50 amp, and you have 454 g of Pb, how long will the
battery last?
Solution
a) 454 g Pb = 2.19 mol Pb
b) Calculate moles of e-
22 mol
mol ee
--
2.19
2.19 mol
mol Pb
Pb •• == 4.38
4.38 mol
mol -e-e
c) Calculate charge 11 mol
mol Pb
Pb
4.38 mol e- • 96,500 C/mol e- = 423,000 C
104
Quantitative
Quantitative AspectsAspects of of
Electrochemistry
Electrochemistry
The anode reaction in a lead storage battery is
Pb(s) + HSO4-(aq) ---> PbSO4(s) + H+(aq) + 2e-
If a battery delivers 1.50 amp, and you have 454 g of
Pb, how long will the battery last?
Solution
a) 454 g Pb = 2.19 mol Pb
b) Mol of e- = 4.38 mol
c) Charge = 423,000 C
105
Quantitative
Quantitative Aspects Aspects of of
Electrochemistry
The anode reactionElectrochemistry
in a lead storage battery is
Pb(s) + HSO4-(aq) ---> PbSO4(s) + H+(aq) + 2e-
If a battery delivers 1.50 amp, and you have 454 g of Pb, how
long will the battery last?
Solution
a) 454 g Pb = 2.19 mol Pb
b) Mol of e- = 4.38 mol
c) Charge = 423,000 C
d) Calculate time
106
Quantitative
Quantitative Aspects Aspects of of
Electrochemistry
The anode reactionElectrochemistry
in a lead storage battery is
Pb(s) + HSO4-(aq) ---> PbSO4(s) + H+(aq) + 2e-
If a battery delivers 1.50 amp, and you have 454 g of Pb, how
long will the battery last?
Solution
a) 454 g Pb = 2.19 mol Pb
b) Mol of e- = 4.38 mol
c) Charge = 423,000 C Charge (C)
Time (s) == Charge (C)
d) Calculate time Time (s) II(amps)
(amps)
107
Quantitative
Quantitative Aspects Aspects of of
Electrochemistry
The anode reactionElectrochemistry
in a lead storage battery is
Pb(s) + HSO4-(aq) ---> PbSO4(s) + H+(aq) + 2e-
If a battery delivers 1.50 amp, and you have 454 g of Pb, how
long will the battery last?
Solution
a) 454 g Pb = 2.19 mol Pb
b) Mol of e- = 4.38 mol
c) Charge = 423,000 C Charge (C)
Time (s) == Charge (C)
d) Calculate time Time (s) II(amps)
(amps)
423,
423,0000
00 C
C= 282,000 s
Time(s) =
Time(s) = 1.50 amp = 282,000 s About 78 hours
1.50 amp
108
Conductance of Electrolytic
Solutions
Electrical resistance (R) of any object is
directly proportional to its length (l) and
inversely proportional to its cross-sectional
area (A), i.e.,
109
Where, ρ = Proportionality constant,
known as resistivity or specific
resistance
Its SI unit is ohm metre (Ω m) and is
often expressed in ohm centimetre.
110
Resistivity −
• − Resistance of a substance when it is 1
metre long and has 1 m2 cross-sectional
area
Conductance,
111
– SI unit of conductance is siemens (S), S
= ohm−1
– κ is called conductivity or specific
conductance
– Conductivity − Conductance of a
substance when it is 1 m long and has 1
m2 cross-sectional area. Its SI unit is S
m−1, but is often expressed in S cm−1
112
Molar Conductivity of ionic
solutions
• Molar conductivity of a solution at a given
concentration is the conductance of
volume V of a solution containing 1 mole
of the electrolyte, kept between two
electrodes with the cross-sectional area of
A and distance of unit length
113
• It is denoted as Λm.
•
Now, l = 1 and A = V (volume
containing 1 mole of the electrolyte)
Therefore, Λm =Κv Or, molar
conductivity is given by
114
Primary Voltaic Cells
• As a voltaic cell discharges, its chemicals
are consumed.
• Once the chemicals are consumed, further
chemical action is impossible.
• The electrodes and electrolytes cannot be
regenerated by reversing current flow
through cell.
– These cells are not rechargable.
115
The Dry Cell
• One example of a dry cell is flashlight, and radio, batteries.
• The cell’s container is made of zinc which acts as an
electrode.
• A graphite rod is in the center of the cell which acts as the
other electrode.
• The space between the electrodes is filled with a mixture
of:
1. ammonium chloride, NH4Cl
2. manganese (IV) oxide, MnO 2
3. zinc chloride, ZnCl2
4. and a porous inactive solid.
116
The Dry Cell
• As electric current is produced, Zn dissolves and
goes into solution as Zn2+ ions.
• The Zn electrode is negative and acts as the anode.
117
The Dry Cell
• The anode reaction
is:
0 2+ -
Zn Zn + 2 e
• The graphite rod is the positive electrode (cathode).
• Ammonium ions from the NH 4Cl are reduced at the cathode.
+ -
2 NH 4 2 e 2 NH 3g H 2g
118
The Dry Cell
• The cell reaction is:
Anode reaction Zn 0 Zn 2+ + 2 e -
Cathode reaction 2 NH +4 + 2 e - 2 NH3g H 2g
Cell reaction Zn + 2 NH Zn
0 +
4
2+
2 NH3g H 2g
119
The Dry Cell
• The other components in the cell are included to remove
the byproducts of the reaction.
• MnO2 prevents H2 from collecting on graphite rod.
4 NH 3 Zn
2+ 2
Zn NH 3 4
120
The Dry Cell
121
The Dry Cell
• Alkaline dry cells are similar to ordinary dry cells
except that KOH, an alkaline substance, is
added to the mixture.
• Half reactions for an alkaline cell are:
Anode reaction Zn 0s + 2 OH- Zn OH2s 2 e
Cathode reaction 2 MnO 2s 2 H 2 O + 2 e - 2 MnO(OH) s + 2 OH-
Cell reaction Zn 0s + 2 MnO 2s 2 H 2 O Zn OH2s 2 MnO(OH) s
E 0cell 1.5 V
122
Mercury cell
123
The reactions taking place at the
anode and cathode are
At anode:
At cathode:
124
The Dry Cell
• Alkaline dry cells are similar to ordinary dry cells
except that KOH, an alkaline substance, is
added to the mixture.
• Half reactions for an alkaline cell are:
125
Secondary Voltaic Cells
• Secondary cells are reversible, rechargeable.
• The electrodes in a secondary cell can be regenerated by the
addition of electricity.
– These cells can be switched from voltaic to electrolytic cells.
• One example of a secondary voltaic cell is the lead storage or
car battery.
126
The Lead Storage Battery
• In the lead storage battery the electrodes are two sets of lead
alloy grids (plates).
• Holes in one of the grids are filled with lead (IV) oxide, PbO2.
• The other holes are filled with spongy lead.
• The electrolyte is dilute sulfuric acid.
127
The Lead Storage Battery
• Diagram of the lead storage battery.
128
The Lead Storage Battery
• As the battery discharges, spongy lead is oxidized
to lead ions and the plate becomes negatively
charged.
Pb 0s Pb 2+ 2 e -
This is the anode reaction.
The anode is the negative battery post during discharge.
• The Pb2+ ions that are formed combine with SO42-
from sulfuric acid to form solid lead sulfate on the Pb
electrode.
2+ 2-
Pb SO4 PbSO4s
129
The Lead Storage Battery
• The net reaction at the anode during discharge is:
0 2- -
Pbs SO4 PbSO4s + 2 e
• Electrons are produced at the Pb electrode.
• These electrons flow through an external circuit (the
wire and starter) to the PbO2 electrode.
• PbO2 is reduced to Pb2+ ions, in the acidic solution.
• The Pb2+ ions combine with SO42- to form PbSO4 and
coat the PbO2 electrode.
• PbO2 electrode is the positive electrode (cathode).
130
The Lead Storage Battery
PbO2s + 4 H + + SO2-
4 + 2 e -
PbSO4s + 2 H 2 O
• The cell reaction for a discharging lead storage battery is:
131
The Lead Storage Battery
• As the cell discharges, the cathode reaction is:
PbO2s + 4 H + + SO2-
4 + 2 e -
PbSO4s + 2 H 2 O
• The cell reaction for a discharging lead storage battery is:
132
The Lead Storage Battery
• What happens at each electrode during recharging?
• At the lead (IV) oxide, PbO2, electrode, lead ions are
oxidized to lead (IV) oxide.
PbSO 4s 2 H 2O PbO 2 s 4 H SO 2 e
+ 2-
4
-
Pb s PbO 2 s + 4H + 2SO
PbSO 2H O
discharge
+ 2-
4
charge 4 s 2
133
The Lead Storage Battery
• What happens at each electrode during recharging?
• At the lead (IV) oxide, PbO2, electrode, lead ions are
oxidized to lead (IV) oxide.
PbSO 4s 2 H 2 O PbO 2 s 4 H + SO 24- 2 e -
• The concentration of the H2SO4 decreases as the cell discharges.
• Recharging the cell regenerates the H2SO4.
134
135
Ni-Cad
Ni-Cad Battery
Battery
Anode (-)
Cd + 2 OH- ---> Cd(OH)2 + 2e-
Cathode (+)
NiO(OH) + H2O + e- ---> Ni(OH)2
+ OH-
136
The Nickel-Cadmium (Nicad)
Cell
• Nicad batteries are the rechargeable cells used
in calculators, cameras, watches, etc.
• As the battery discharges, the half-reactions are:
138
The Hydrogen-Oxygen Fuel Cell
Anode reaction 2H 2 OH 2 H O 2 e
2 g
-
(aq) 2 ( )
-
Cathode reaction O 2 H O 4 e 4 OH
2 g 2 ( )
- -
(aq)
140
Corrosion Protection
• Some examples of corrosion protection.
1 Plate a metal with a thin layer of a less active
(less easily oxidized) metal.
143
Corrosion Protection
4 Galvanizing, the coating of steel with zinc,
provides a more active metal on the exterior.
144
Corrosion Protection
5. Paint or coat with a polymeric material such as
plastic or ceramic.
145
Synthesis Question
• What are the explosive chemicals in the
fuel cell that exploded aboard Apollo 13?
146
Synthesis Question
• The Apollo 13 fuel cells contained
hydrogen and oxygen. Both are explosive,
especially when mixed. The oxygen tank
aboard Apollo 13 exploded.
147
Group Question
148
End of Chapter 21
149