Wt871rwp Electrochemistry 440 Electrochemistry-Presentation 2012-03-31

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Electrochemistry
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Electrochemistry
Electrochemistry deals with relationships between
reactions and electricity
In electrochemical reactions, electrons are transferred
from one species to another.
Provide insight into batteries, corrosion, electroplating,
spontaneity of reactions
Slide 3 / 144
Electrochemical Reactions
In electrochemical reactions, electrons are transferred
between various reactant and product species in reactions.
As a result, oxidation state/number of one or more
substances/species change
Oxidation number is the formal charge on the atom when it is
connected to other atoms.
In order to keep track of what species loses electrons and
what gains them, we assign oxidation numbers/oxidation states
to individual atoms.
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Oxidation Numbers
Take a look at this reaction between Zn metal and acid with
assigned oxidation numbers.
How do we know what number goes with each atom?
Where do these numbers came from?
Zn(s) + 2H+(aq) Zn2+ + H2(g)

0
+1
+2
Slide 5 / 144
How do we assign oxidation numbers ?

Rules for Assigning Oxidation Numbers
Elements
Elements in their elemental form have an

oxidation number of 0.
Compounds
The sum of the oxidation numbers in a

neutral compound is 0.
Monoatomic
ions
The oxidation number of a monatomic

ion is the same as its charge.
Polyatomic
ions
The sum of the oxidation numbers in a

polyatomic ion is the charge on the ion.
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-1 when bonded to a metal
Hydrogen
+1 when bonded to a nonmetal
Fluorine always has an oxidation
Fluorine number of -1.

Other
halogens
Usually -1.
May have positive oxidation numbers in
oxyanions.
For example, Cl has an oxidation number of +5 in ClO3-.
Slide 7 / 144
Nonmetals tend to have negative

Nonmetals oxidation numbers although some are
positive in certain compounds or ions.
Oxygen
Oxygen has a oxidation number of -2,

except in the peroxide ion, when its
oxidation number is -1.
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What is the oxidation number of each oxygen

atom in the compound MnO2 ?
A -2
B
-1
C 0
D +1
E
+2
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What is the oxidation number of the manganese

atom in the compound MnO2 ?
A
+3
+2
+1
+4
+7
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What is the oxidation number of oxygen atom in

MnO41-, the permanganate ion?
A -2
B
-1
C 0
D +2
E +4
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What is the oxidation number of the manganese

atom in MnO41-, the permanganate ion?
A
+1
+2
+5
+4
+7
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What is the oxidation number of sulfur in HSO41-,

the hydrogen sulfate ion?
A
-2
+1
+2
+4
+6
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Oxidation and Reduction

Zn(s) + 2H+(aq) Zn2+ + H2(g)
0
+1
+2
Oxidation-loss of electrons
A species is oxidized when it loses electrons.
Here, zinc loses two electrons to go from neutral Zn metal to
the Zn2+ ion.
Zn is also a reducing agent- provides electrons (reductant)
Reducing agent loses electrons.
LEO
OIL
RIG
The lion says
GER
Slide 14 / 144

Zn(s) + 2H+(aq) Zn2+ + H2(g)
0
+1
+2
Reduction- gaining of electrons

A species is reduced when it gains electrons.
Here, each of the H+ gains an electron, and they combine to
form H2.
H is an oxidizing agent- accepts electrons (oxidant)
An oxidizing agent gains electrons.
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Zn(s) + 2H+(aq) Zn2+ + H2(g)
0
+1
+2
What is reduced is the oxidizing agent.

H+ oxidizes Zn by taking electrons from it.
What is oxidized is the reducing agent.
Zn reduces H+ by giving it electrons.
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Redox Reactions
Zn(s) + 2H+(aq) Zn2+ + H2(g)
0
+1
+2
An electrochemical reaction in which oxidation and

reduction occurs is known as a REDOX reaction
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Which of the following is/are an oxidationreduction (redox) reactions?

(a) K2CrO4 + BaCl2 KCl + BaCrO4
(b) Pb2+ + 2 Br1- PbBr2
(c) Cu + S CuS
A
a only
b only
c only
a and c
b and c
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Which substance is oxidized in the following

reaction? (First, assign oxidation numbers.)
Cu + S CuS
A Cu
B S
C Cu and S
D CuS
E
This is not a redox reaction.
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Which substance is the reducing agent below?

Cu + S CuS
A Cu
B S
C Cu and S
D CuS
E
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Which substance is oxidized in the following

reaction? (First, assign oxidation numbers.)
Ca + Fe3+ Ca2+ + Fe
A Ca
B
Fe3+
C Ca2+
D Fe
E
Slide 21 / 144
10
Which substance is the oxidizing agent below?

Ca + Fe3+ Ca2+ + Fe
A Ca
B
Fe3+
C Ca2+
D Fe
E
Slide 22 / 144
11
Which substance is reduced in the following reaction?

(First, assign oxidation numbers.)
3 K + Al(NO3)3 Al + 3 KNO3
A K
B Al
C N
D O
E
Slide 23 / 144
12
Which substance is the reducing agent?

3 K + Al(NO3)3 Al + 3 KNO3
A K
B Al(NO3)3
C KNO3
D This is not a redox reaction.
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Redox Practice 1
H2S (g)
+ Cl2 (g)
-->
2HCl (g)
+ S (s)
a) Assign oxidation numbers to each element above.

b) Which element is oxidized?
c) Which element is reduced?
d) Name the reducing agent.
e) Name the oxidizing agent.
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Redox Practice 2
SnCl2(aq)
2HgCl2 (aq)
-->
SnCl4 (aq)
a) Assign oxidation numbers to each element above.

b) Which element is oxidized?
c) Which element is reduced?
d) Name the reducing agent.
e) Name the oxidizing agent.
Hg2Cl2 (s)
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13
Which element is oxidized in the

reaction below?
Fe2+ + H+ + Cr2O72- Fe3+ + Cr3+ + H2O
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14
H2S (g)
+ Cl2 (g)
Which is oxidized?
Which is reduced?
-->
2HCl (g)
+ S (s)
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15
SnCl2(aq) + 2HgCl2 (aq) --> SnCl4 (aq) + Hg2Cl2 (s)

Which is oxidized?
Which is reduced?
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Redox reactions in aqueous solutions

A large number of redox reactions occur in aqueous
solutions.
Unlike acid base nutralization and precipitation
reactions,most of the reaction proceed slowly.
Each redox reaction is the sum of two half reactions:
Consider the reaction of iodide ions and hydrogen
peroxide.
2I- (aq) + H2O2(aq) + 2e- I2 + 2OH- (aq) + 2e-
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Redox reactions in aqueous solutions

This reaction involves two parts as represented below.
2I- (aq) + H2O2(aq) + 2e- I2 + 2OH- (aq) + 2e1. Oxidation half reaction
2. Reduction half reaction.
2I- (aq) I2 + 2eH2O2(aq) + 2e- 2OH- (aq)
oxidation
reduction
Add the two half reactions to get the overall reaction.

2I- (aq) + H2O2(aq) + 2e- I2 + 2OH- (aq) + 2eHow do we balance a redox reaction?
Slide 31 / 144
Balancing Redox reactions

Half-reaction method (oxidation # method)
Assign oxidation numbers to determine what is
oxidized and what is reduced.
Identify the oxidation and reduction process.
Write down the individual oxidation and reduction
equations.
Balance these half reactions
Combine them to attain the balanced equation for
the overall reaction.
This method can be used in general to balance any
redox reaction unless any specific condition such as
acidic or basic is mentioned
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Let us consider the simple replacement reaction of Mg
with AgCl
Mg + AgCl Ag + MgCl2
0
Oxidation:
+1
-1
+2
-1
Mg --> Mg2+ + 2 e- --------(1)
Reduction: Ag+ + 1 e- --> Ag
---------(2)
Since all the atoms are balanced, we need to balance

only electrons. Multiply equation (2) x 2
Oxidation:
Mg --> Mg2+ + 2 e- --------(1)
Reduction: 2Ag+ + 2 e- --> 2Ag
---------(3)
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Adding the half-reactions (1) and (3) yields the following:
Oxidation: Mg --> MgCl2 + 2eReduction: 2AgCl + 2e- --> 2Ag

Overall: Mg + 2AgCl + 2e- --> MgCl2 + 2e- + 2Ag
and we cancel out electrons from both sides:
Overall: Mg + 2AgCl + 2e- --> MgCl2 + 2e- + 2Ag

Net equation: Mg + 2AgCl --> MgCl2 + 2Ag
Since the original equation is given with chlorine you would keep it
here in the final balanced equation too.
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Redox reactions -balancing
Practice
Fe3O4 +C --> Fe + CO
Fe3O4 + 4C --> 3Fe + 4CO
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Redox reactions -balancing

Practice:
SnO2 + C --> Sn + CO
SnO2 + 2C --> Sn + 2CO
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The Half-Reaction Method
In acidic medium:
This diagram shows the steps involved in

balancing half-reactions.
Write down the individual half reaction.

First balance atoms other than H and O.
Balance oxygen atoms by adding H2O.
Balance hydrogen atoms by adding H+.
Balance charge by adding electrons.
Multiply the half-reactions by integers so

that the electrons gained and lost are the
same.
Other atoms
e-
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In acidic medium: Continued
Add the half-reactions, subtracting things
that appear on both sides.
Make sure the equation is balanced
according to mass.
Make sure the equation is balanced
according to charge.
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In acidic medium:
Consider the reaction between MnO4 and C2O42 :
MnO4 (aq) + C2O42 (aq) Mn2+ (aq) + CO2 (aq)
+7
+3
+2
+4

First, we assign oxidation numbers.
We only assign oxidation numbers to elements whose
oxidation numbers CHANGES.
Here, oxygen's oxidation number remains constant at -2.
Slide 39 / 144

In acidic medium:
+7
+3
+2
+4
Which substance gets reduced?

Which substance gets oxidized?
Which substance is the reducing agent?
Which substance is the oxidizing agent?
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In acidic medium:
+7
+3
+2
+4

Since the manganese goes from +7 to +2, it is reduced.
The MnO4- ion is the oxidizing agent.
Since the carbon goes from +3 to +4, it is oxidized.
The C2O4 ion is the reducing agent.
2-
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Oxidation Half-Reaction
In acidic medium:
C2O42 CO2
To balance the carbon, we add a coefficient of 2:
C2O42 2 CO2
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Oxidation Half-Reaction
In acidic medium:
C2O42 2 CO2
The oxygen is now balanced as well. To balance
the charge, we must add 2 electrons to the right
side.
C2O42 2 CO2 + 2 e
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Reduction Half-Reaction
In acidic medium:
MnO4 Mn2+
The manganese is balanced; to balance the
oxygen, we must add 4 waters to the right side.
MnO4 Mn2+ + 4 H2O
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In acidic medium:
MnO4 Mn2+ + 4 H2O

To balance the hydrogen, we add 8 H+ to the left side.
8 H+ + MnO4 Mn2+ + 4 H2O
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In acidic medium:
8 H+ + MnO4 Mn2+ + 4 H2O

To balance the charge, we add 5 e to the left side.
5 e + 8 H+ + MnO4 Mn2+ + 4 H2O
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Combining the Half-Reactions

In acidic medium:
Now we evaluate the two half-reactions together:
C2O42 2 CO2 + 2 e
5 e + 8 H+ + MnO4 Mn2+ + 4 H2O
To attain the same number of electrons on each
side, we will multiply the first reaction by 5 and the
second by 2.
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In acidic medium:
5 C2O42 10 CO2 + 10 e
10 e + 16 H+ + 2 MnO4 2 Mn2+ + 8 H2O
When we add these together, we get:
10 e + 16 H+ + 2 MnO4 + 5 C2O42 -->
2 Mn2+ + 8 H2O + 10 CO2 +10 e
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In acidic medium:
10 e + 16 H+ + 2 MnO4 + 5 C2O42
2 Mn2+ + 8 H2O + 10 CO2 +10 e
The only thing that appears on both sides are the
electrons. Subtracting them, we are left with:
16 H+ + 2 MnO4 + 5 C2O42
2 Mn2+ + 8 H2O + 10 CO2
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In acidic medium:
Practice 1
Cd(s) + NiO2 (s) --> Cd(OH)2(s ) + Ni(OH)2(s )

0
a)
b)
c)
d)
e)
+4 -2
+2 -2 +1
Write the oxidation half reaction.

Write the reduction half reaction.
Write the balanced net reaction.
Identify the oxidizing agent.
Identify the reducing agent.
+2 -2 +1
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In acidic medium:
Practice 2
Cu + NO3- --> NO2 + Cu2+
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Practice 3
Cr2O72- + Fe2+ + H+ --> Cr3+ + Fe 3+ + H2O
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Practice 4 :MnO4- + Br- --> Mn2+ + Br2 in acidic solution
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Practice 5 : Cr2O72- + C2H4O --> C2H4O2 + Cr3+ in acidIc

solution
2-
3+
Cr2O7 + 8H+ + 3C2H4O --> 3C2H4O2 + 2Cr
+ 4H2O
Slide 54 / 144
Redox reaction in basic medium

Some redox reactions requires basic medium to
occur.In this case the following steps need to be
performed to balance the reaction.
1- Assign the oxidation numbers
2- Balance the "other atoms" involved
3- Separate the half reactions
4- Add water molecules to balance oxygen atom whatever side
deficient in O atoms
5- Add water molecules equal in number to the deficiency of H
atoms.
6- Add same number of OH- to the other side.
7- Balance the charge by adding electrons on the appropriate
side
8- Balance the electrons lost /gained by multiplying the reactions
by integers
9- Add the two reactions removing any duplication if any of
common species on either side.
Can also be performed without splitting the two equations.
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Balancing in Basic Solution

Zn + NO3- --> Zn2+ + NH4+ in basic medium:
Oxidation half reaction:
Zn ----> Zn2+ + 2e-
Reduction half reaction: NO3- ---> NH4+

NO3- ---> NH4+ + 3H2O
10H2O +
NO3- ---> NH4+ + 3H2O
10H2O + NO3- ---> NH4+ + 3H2O + 10OH8e- 10H2O + NO3- ---> NH4+ + 3H2O + 10OH4Zn ----> 4 Zn2+ + 8e-
4Zn + 1NO3- + 7H2O--> 4Zn2+ + 1NH4+ + 10 OH-
Slide 56 / 144
**
Can also be performed without splitting the two equations.

Zn + NO3- --> Zn2+ + NH4+ in basic medium:
1. Assigh oxidation #s:
Increases by 2
Zn + NO3- --> Zn2+ + NH4+

0
+5
2-
+2
-3 +1
decreases by 8
2. Balance the change in Oxidation # change on either side.

increases by 8
+
4Zn + 1NO3- --> 4Zn2+decreases
+ 1NHby
4
8
Slide 57 / 144

4Zn + 1NO3- --> 4Zn2+ + 1NH4+
3. Balance O atoms by adding H2O molecules to the side deficient in O atoms.
3 O atoms on the LHS so add 3 water on the RHS
4Zn + 1NO3- --> 4Zn2+ + 1NH4+ + 3H2O

4. The H atoms are then balanced by adding H2O to the side lacks H.
10 H on the RHS, so add 10 water on the LHS.
4Zn + 1NO3- + 10H2O--> 4Zn2+ + 1NH4+ + 3H2O

5. Add 10 OH- on the other side of the reaction to balance the extra H and O.
4Zn + 1NO3- + 10H2O--> 4Zn2+ + 1NH4+ + 3H2O + 10 OH-
6. If this produces water on both sides, you might have to subtract water from
each side.
4Zn + 1NO3- + 7H2O--> 4Zn2+ + 1NH4+ + 10 OH-
Slide 58 / 144

Practice: 1 Fe(OH)2 + H2O2 --> Fe(OH)3 + H2O in basic solution
Oxidation:
decrease by 1 for each O atom, total 2 e- taken
+2
-1
+3
-2
Fe(OH)2 + H2O2 --> Fe(OH)3 + H2O in basic solution

increase by 1, 1 e- given
2 Fe(OH)2 + H2O2 --> 2Fe(OH)3 + H2O in basic solution

Balance O atoms by adding 2 H2O to LHS
2 Fe(OH)2 + 2H2O --> 2Fe(OH)3

Balance H atoms by adding 2 H2O to RHS
2 Fe(OH)2 + 2H2O --> 2Fe(OH)3 + 2H2O

Add 2 OH- on the LHS
2 Fe(OH)2 + 2H2O + 2OH- --> 2Fe(OH)3 + 2H2O
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Practice 2: Fe(OH)2 + H2O2 --> Fe(OH)3 + H2O in basic solution
Reduction
H2O2 --> H2O

Add 1 H2O on RHS
H2O2 --> H2O + H2O

Add
2H2O on LHS to balance H atoms
A
2H2O + H2O2 --> H2O + H2O
Add 2 OH- to RHS
2H2O + H2O2 --> H2O + H2O +2OHAdd the two equations: 2Fe(OH)2 + H2O2 --> 2Fe(OH)3
Slide 60 / 144

Practice 3 : Bi(OH)3 + SnO2 --> Bi + SnO3
2Bi(OH)3 + 3SnO2 --> 2Bi + 3SnO3 + 3H2O
Slide 61 / 144
Practice 4:
Cr(OH)4-1 + H2O2 --> (CrO4) 2- + H2O
-1
2Cr(OH) + 2OH + 3H2O2 --> 2CrO4
2- +
8H2O
Slide 62 / 144
Voltaic Cells
The energy released in a spontaneous reaction can

be used to perform electrical work.
Such a set up through which we can transfer
electrons is called a voltaic cell or galvanic cell or
electrochemical cell
Slide 63 / 144
Voltaic Cells
Zn + Cu2+ Zn2+ + Cu
single replacement
Zn2+
2e-
Zn metal
Cu atom
Cu
2+
Cu2+
Zn metal
Zn metal strip
placed in CuSO4
In spontaneous oxidation-reduction (redox)

reactions, electrons are transferred and energy is
released.
In the above stup, lectron transfer takes place inside
the beaker
Note that the blue color fades as more Cu is reduced to metallic copper
Slide 64 / 144
Voltaic Cells
This shows what is occurring on an atomic level at the anode
and the cathode.
http://www.che m.ias tate .e du/group/Gre e nbowe /s e ctions /proje ctfolde r/animations /

ZnCutrans fe r.html
Slide 65 / 144
Voltaic Cells
Here the Cu and Zn strips are in two different beakers
Cu/CuNO3
Cu2+ + 2e- Cu
RED- Half reaction
Zn/ZnNO3
Zn Zn2+ + 2eOXD- Half reaction
We can use the energy to do work if we make the electrons

flow through an external device.
Slide 66 / 144
Voltaic Cells
Here the Cu and Zn strips are in two different beakers
esalt bridge
Cu/CuNO3
Cu2+ + 2e- Cu
RED- Half reaction
Zn/ZnNO3
The salt bridge allows the migration of the ions to

keep electrical neutrality
Electrons are generated at the anode and flows
through the external line to the cathode.
Slide 67 / 144
Voltaic Cells
http://www.che m.ias tate .e du/group/Gre e nbowe /s e ctions /proje ctfolde r/

animations /CuZnce ll.html
Slide 68 / 144
Voltaic Cells
A typical cell looks like this.
The oxidation occurs at the anode.
The reduction occurs at the cathode.
2+
Zn
NO3-
Slide 69 / 144
Voltaic Cells
Once even one electron flows from the anode to the
cathode, the charges in each beaker would not be
balanced and the flow of electrons would stop.
more Zn2+ are

produced
more NO3- are

created in solution
Slide 70 / 144
Voltaic Cells
Therefore, we use a salt bridge, usually a Ushaped tube that contains a gel of a salt solution,
to keep the charges balanced.
Cations move toward the cathode.
Anions move toward the anode.
more Zn2+ are

produced
more NO3- are in

solution
The increase in Zn2+ and NO3- ions in the two compartment create
electrical imbalance.
The salt bridge ions will neutralize these ions and create neutrality.
Slide 71 / 144
Voltaic Cells
e-
In the cell, then,

electrons leave the
anode and flow
through the wire to the
cathode.
As the electrons
leave the anode, the
cations formed
dissolve into the
solution in the anode
2+
Zn
2e-
Zn metal
Cu atom
Cu2+
Cu
Zn metal
2+
Slide 72 / 144
Voltaic Cells
e-
As the electrons reach

the cathode, cations in
the cathode are
attracted to the now
negative cathode.
Zn2+
2e-
Zn metal
Cu atom
Cu2+
Cu2+
Zn metal
Slide 73 / 144
Voltaic Cells
e-
The electrons are taken

by the cation, and the
neutral metal atoms
are deposited onto the
cathode.
2+
Zn
2e-
Zn metal
Cu atom
Cu2+
Cu
Zn metal
2+
Slide 74 / 144
Voltaic Cells
This shows how a typical voltaic cell works
http://www.che m.ias tate .e du/group/Gre e nbowe /s e ctions /proje ctfolde r/

flas hfile s /e le ctroChe m/volticCe ll.html
Slide 75 / 144
16
The electrode at which

oxidation occurs is called
the _______________.
Slide 76 / 144
17
In a voltaic cell, electrons

flow from the ______ to the
________.
Slide 77 / 144
18
Which element is oxidized in the

reaction below?
Fe2+ + H+ + Cr2O72- Fe3+ + Cr3+ + H2O
Slide 78 / 144
19
Fe2+ + H+ + Cr2O72- Fe3+ + Cr3+ + H2O
If a voltaic cell is made with Fe and Cr electrode in

contact with their own solution, the electrons will
flow from ------ to --------- electrode.
Slide 79 / 144
20
The purpose of the salt bridge in

an electrochemical cell is to
________________.
A) maintain electrical neutrality in the half-cells via

migration of ions.
B) provide a source of ions to react at the anode and
cathode.
C) provide oxygen to facilitate oxidation at the anode.
D) provide a means for electrons to travel from the anode
to the cathode.
E) provide a means for electrons to travel from the
cathode to the anode.
Slide 80 / 144
21
A cell was made with Mg and Cu as two electrodes. The

electrons will flow from ------- to --------- electrode.
Slide 81 / 144
22 The electrode where reduction is taking place is the ----------
Slide 82 / 144
23 The cation concentration increases in the solution where

oxidation occurs.
Yes
No
Slide 83 / 144
24 the cations move towards the anode and anions move

towards the cathode in a voltaic cell.
True
False
Slide 84 / 144
25 The salt bridge ions may react with the Ions in the cell
compartments to form a precipitate.
Yes
No
Slide 85 / 144
26
Which of the following substances

would NOT provide a suitable salt
bridge?
A KNO3
B Na2SO4
C LiC2H3O2
D PbCl2
Slide 86 / 144
27
Which of the following substances

would provide a suitable salt
bridge?
A AgBr
B KCl
C BaF2
D CuS
Slide 87 / 144
28
In a Cu-Zn voltaic cell, which of the following is

true?
A Both strips of metal will increase in mass.
B Both strips of metal will decrease in mass.
C Cu will increase in mass; Zn will decrease.

D Cu will decrease in mass; Zn will increase.
E
Neither metal will change its mass, since

electrons have negligible mass.
Cu/CuNO3
Cu2+ + 2e- Cu
RED- Half reaction
Zn/ZnNO3
Slide 88 / 144
29
In any voltaic cell, which of the following is true?

A The cathode will always increase in mass.
B The anode strip will always decrease in mass.
C The anode strip will always increase in mass.

D Both A and B
Slide 89 / 144
Electro motive force

Water only spontaneously flows one way in a
waterfall.
Likewise, electrons only spontaneously flow one
way in a redox reactionfrom higher to lower
potential energy.
The accumulation of large number of electrons at
the anode create higher potential at the anode.
Natural flow will occur to cathode where there is
less potential
Higher - to - lower
Slide 90 / 144

The potential difference between the anode and
cathode in a cell is called the electromotive force
(emf).
It is also called the cell potential and is designated
Ecell.
Slide 91 / 144

The difference in potential energy /electon charge is
measured in volts.
1 volt is the potential required to impart 1joule energy to a
charge of 1coulomb
1v = 1J / 1C
The potential difference between the electrodes is the
driving force that pushes the electrons - so called EMF
In a voltaic cell, EMF = Ecell
Slide 92 / 144
Electromotive Force (emf)

Cell potential is measured in volts (V).
1V = 1J/C
In a spontaneous reaction, Ecell is positive
EMF depends on the cell reaction involved
Standard condition: 1M, 1atm and 25C
Ecell = standard cell potential
Slide 93 / 144
Standard Reduction Potentials

Electrode potential: The tendency of an electrode to lose or gain
electrons is called electrode potential ( oxidation or reduction potential)
Reduction potentials for many electrodes have been

measured and tabulated.
By convention, the process is viewed as a reduction and the
values are reported as reduction potential
Li+ (aq) + e- Li(s)

Na+(aq) + e- Na(s)
Al3+(aq) + 3e- Al(s)
2H+(aq) + 2e- H2(g
Cu2+(aq) + 2e- Cu(s)
F2(g) + 2e- 2F-(aq)
-3.05
-2.71
-1.66
0
+ 0.34
+ 2.87
The more negative value indicate that, reduction is unlikely at

that electrode
The more positive the value is, reduction is highly likely at that
electrode.
This parallels their activity in single replacement reaction.
Slide 94 / 144

Standard Hydrogen Electrode ( SHE)
By definition, the reduction potential for hydrogen is 0 V:

2 H+ (aq, 1M) + 2 e H2 (g, 1 atm)
H2, 1 atm
Pt
HCl, 1M
Slide 95 / 144

How did we measure the reduction potential of all lements?
Their values are referenced to a Standard Hydrogen

Electrode (SHE).
The metal electrode will be connected to the SHE
By definition, the reduction potential for hydrogen is 0 V:
The reduction potential measured will be that of the
metal
H2, 1 atm
Zn
Pt
Zn(NO3)2
HCl, 1M
Slide 96 / 144
30
If a volatic cell is made with iron and

zinc, which metal will be reduced?
Use the reduction potential table and compare the values.

The more positive the value is, that is where reduction takes
place, is the cathode.
Oxidation - at Anode
(vowels)
Reduction - at Cathode (consonants)
Zn
0.1M Zn(NO3)2
Fe
0.1M Fe(NO3)2
Slide 97 / 144
31
If a volatic cell is made with Cu and Na,

which metal will be the cathode?
A Cu
B Na
C Cu and Na cannot make a voltaic cell.
F2(g) + 2e- 2F-(aq)

2H+(aq) + 2e- H2(g
Na+(aq) + e- Na(s)
Li+ (aq) + e- Li(s)
+ 2.87
+ 0.34
0
-1.66
-2.71
-3.05
Slide 98 / 144
32
If a volatic cell is made with Li and Al,

which metal will be the anode?
A Li
B Al
C Li and Al cannot make a voltaic cell.
F2(g) + 2e- 2F-(aq)

2H+(aq) + 2e- H2(g
Na+(aq) + e- Na(s)
Li+ (aq) + e- Li(s)
+ 2.87
+ 0.34
0
-1.66
-2.71
-3.05
Slide 99 / 144
Cell Potentials
The cell potential at standard conditions can be found
through this equation:
Ecell = Eored.pot (cathode) Eored.pot (anode)

Because cell potential is based on the potential
energy per unit of charge, it is an intensive property.
This means that it does not depend on the amount of
substance (e.g. mass or moles).
Slide 100 / 144
Cell Potentials
A cell with Cu and Zn electrodes
For the oxidation in this cell,

E = - 0.76v
red
For the reduction,

E = + 0.34v
red
Cu
Zn
1M Zn(NO3)2
2+
Zn(s) Zn + 2e-
1M Cu(NO3)2
2+
Cu (aq) + 2e- Cu(s)
Slide 101 / 144
Cell Potentials
Ecell = Ered(cathode) - Ered(anode)
= +0.34V - (-0.76V)
Ered = +1.10V
Slide 102 / 144
Cell Potentials
The greater the difference between the two
electrode potential, the greater the voltage of
the cell.
More positive
+ 0.34
Cu
2+
+ 2e- --> Cu
EE0cell
=
0.34 --(-0.76)
= +0.34V
(-0.76V)
cell
== ++1.10V
1.10v
-0.76
2+
Zn --> Zn
+ 2e-
Slide 103 / 144
33
Which of the following volatic cells would

yield the greatest voltage (Eocell)?
A Cu-Al
B Cu-Na
C Al-Li
D F2 - Cu
F2(g) + 2e- 2F-(aq)

2H+(aq) + 2e- H2(g
Na+(aq) + e- Na(s)
Li+ (aq) + e- Li(s)
+ 2.87
+ 0.34
0
-1.66
-2.71
-3.05
Slide 104 / 144
34
Which of the following volatic cells would

yield the lowest voltage (Eocell)?
A Cu-Al
B Al-Na
C Na-Li
F2(g) + 2e- 2F-(aq)

2H+(aq) + 2e- H2(g
Na+(aq) + e- Na(s)
Li+ (aq) + e- Li(s)
+ 2.87
+ 0.34
0
-1.66
-2.71
-3.05
Slide 105 / 144
Most positive values
F2(g) + 2e-
--> 2F-
2.87v
Cl2(g) + 2e- --> 2Cl-
1.36v
I2(s) + 2e-
0.53v
Rb+ + e-
--> 2I-
--> Rb(s) -2.92v
Most negative values
Increasing strength of reducing agent
Increasing strength of oxidizing agent
Oxidizing and Reducing Agents
The strongest oxidizers have the most positive

reduction potentials.
The strongest reducers have the most negative
reduction potentials.
F is a strong oxidizing agent than Cl
Slide 106 / 144
35
The more _______ the value of

Ered, the greater the driving
force for reduction.
Slide 107 / 144
Class Practice:
Identify:
Cathode
Anode
Oxidation half reaction
Reduction half reaction
Combined cell reaction (balanced)
cell
Ni
1M Ni (NO3)2
Sn
1M Sn(NO3)2
Slide 108 / 144
Class Practice 2
Identify:
Cathode
Anode
Oxidation half reaction
Reduction half reaction
Combined cell reaction (balanced)
Fe
Sn
Ecell
1M Fe(NO3)3
1M Sn(NO3)2
Slide 109 / 144
36
Calculate E for the following reaction:

Sn4+(aq) + 2K(s) --> Sn2+(aq) + 2K+(aq)
A) +6.00 V
B) -3.08 V
C) +3.08 V
D) +2.78 V
E) -2.78 V
Slide 110 / 144
Free Energy
G for a redox reaction can be found by using the
equation
G = nFE
where n is the number of moles of electrons
transferred, and F is a constant, the Faraday.
1 F = 96,500 C/mol = 96,485 J/V-mol
Slide 111 / 144
Free Energy
Under standard conditions,
G = -nFE
Standard condition: 250C, 1 atm and 1M
Slide 112 / 144
Nernst Equation
Remember that
G = G + RT ln Q
This means
nFE = nFE + RT ln Q
Slide 113 / 144
Nernst Equation
Dividing both sides by nF, we get the Nernst
equation:
E = E - RT lnQ
nF
or, using base-10 logarithms,
E = E - [8.31 x 298] x 2.303 log Q
[n x 96500 ]
Slide 114 / 144
Nernst Equation
E = E - [8.31 x 298] x 2.303 log Q
[n x 96500 ]
At room temperature (298 K),
2.303 RT
= 0.0592 V
F
Thus, the equation becomes
0.0592
E = E logQ
n
Slide 115 / 144
Equilibrium Constant
G = G + RT ln Q
When E=0, -nFE = 0
E = E - 0.0592 logQ
n
0= E logK (0.0592/n)
E = logK (0.0592/n)
logK = nE/0.0592
Equilibrium constant for a redox reaction can be

calculated
using the above .
Slide 116 / 144
37
The relationship between the

change in Gibbs free energy and the
emf of an electrochemical cell is
given by __________________.
A) G = -nF/E
B) G = -E/nF
C) G = -nFE
D) G = -nRTF
E) G = -nF/ERT
Slide 117 / 144
Concentration Cells
Ni
0.001M [Ni2+]
Ni
2+
1M [Ni ]
Ni
**
Ni
2+
0.5M [Ni ]
2+
0.5M [Ni ]
Notice that the Nernst equation implies that a cell could be

created that has the same substance at both electrodes.
For such a cell, E would be 0, but Q would not.
E = E - 0.0592 logQ
n
log Q =
[dilute]
log ------------[concent]
Therefore, as long as the concentrations are different,

E will not be 0.
http://www.che m.ias tate .e du/group/Gre e nbowe /s e ctions /proje ctfolde r/flas hfile s /e le ctroChe m/
voltaicCe llEMF.html
Slide 118 / 144
38
A cadmium rod is placed in a 0.010M solution of

cadmium sulfate at 298K. Calculate the potential of the
electrode at the is temperature.
0.0592
logQ
n
= -0.0529/2 log0.01
= - 0.0591
E = E -
Slide 119 / 144
Elcectrolytic cell/ Electrolysis

Voltaic cells work as a result of a spontaneous
reaction
We can use electricity from outside source to make a
nonspontaneous reaction to become spontaneous.
A chemical reaction by using outside electricity is
known as electrolysis. Such a cell is known as an
electrolytic cell
Slide 120 / 144
Elcectrochemical/voltaic cell
Electrolytic Cell
Voltaic (Electrochemical) Cell
Energy is absorbed to drive

Energy is released from a
a nonspontaneous redox
spontaneous redox reaction
reaction
Surroundings (battery or
power supply) do work on
the system (cell)
System (cell) does work on the

surroundings (e.g. light bulb)
Slide 121 / 144
39
One of the differences between a

voltaic cell and an electrolytic cell
is that in an electrolytic cell,
_____________________.
A) an electric current is produced by a chemical reaction

B) electrons flow toward the anode
C) a nonspontaneous reaction is forced to occur
D) gas is produced at the cathode
E) oxidation occurs at the cathode
Slide 122 / 144
Electroplating
Uses an active electrode to deposit a thin layer of one
metal to another metal object
Item to be coated is cathode (metal ions get reduced
at the (-) electrode)
e-
Ag
Ag+
Ag+
Slide 123 / 144
Electrolysis
This flowchart shows the steps relating the quantity of electrical
charge used in electrolysis to the amounts of substances
oxidized or reduced.
Quantity of
charge
(Coulombs)
Current
(A)
and time
Moles of
substance
oxidized
or reduced
Moles of
electrons
(Faradays)
Grams of
substance
A typical problem will give the current (amperes) that is

applied for a specific amount of time (seconds). You
would be asked to solve for the mass of metal that can
be produced through electroplating.
Alternatively, you might be asked for either the time or
amount of current that is needed to produce a specific
amount (given mass) of metal.
Slide 124 / 144
Electrolysis
The quantity of charge passing through is measured in
coulombs
1 mole of electrons passage = 96500C = 1Faraday
1coulomb = 1 ampere passing in 1 second
Coulombs (C ) = ampere x seconds
Slide 125 / 144
40 The quantity of charge passing a

point in a circuit in one second
when the current is one ampere
is called a ___________________.
A) joule
B) coulomb
C)calorie
D)Newton
E) Mole
Slide 126 / 144
41
How many coulombs result from a current

of 50 amps (A) applied for 20 seconds?
A 2.5
B 10
C 70
D 700
E 1000
C
s
Slide 127 / 144
42
How many seconds must a current of 25 A be

applied in order to produce a charge of 100 C?
A 0.25
B 0.4
C 4
D 75
E 125
C
s
Slide 128 / 144
43
What amount of charge is required to release one

mole of electrons?
A 1 atm
B 25oC
C 0.0821 L-atm/mol-K
D 96,500 C
E 760 mm Hg
Slide 129 / 144
44
How many moles of electrons would be released

by a charge of 158,000 C?
A 96,500 / 158,000
B 158,000 / 96,500
C 158,000*96,500
D 158,000 - 96,500
Slide 130 / 144
45
How many moles of electrons would be released

by a charge of 48,250 C?
A 0.25
B 0.5
C 1
D 48,250
E 96,500
Slide 131 / 144
Electrolysis
Quantitative aspect
If 10.0 A passes through molten AlCl3 for 60 minutes, how
much of Al will be deposited?
total charge C = 10.0 A x 60min x 60sec. = 3.6 x104 C
Remember!!
1mole e- = 96500C
How many moles of e- are we talking about in here?????
Moles of e- = 3.6 x 104 /96500 = 0.373 moles of eAl3+ + 3e- Al
1 mol Al = 3 mols eMoles of Al = 0.373 x 1 mole Al/3 mole e- = 0.124 mol Al
How many grams of Al ? = 27g x 0.124 mol = 3.36g Al
Slide 132 / 144
Electrolysis
practice:1
Calculate the number of grams of aluminum

produced in 30.0 minutes by electrolysis of at a
current of 12.0 A.
Slide 133 / 144
Electrolysis
practice:2
How many minutes will it take to plate out 6.36 g of Cu metal

from a solution of Cu2+ using a current of 12 amps in an
electrolytic cell?
Slide 134 / 144
46
Plating out 1 mol of chromium requires _______ of

electrons.
A 0.33 mol
B 0.5 mol
C 1.0 mol
D 3.0 mol
Cr3+(aq) + 3 e- --> Cr(s)
Slide 135 / 144
47
One mole of electrons would allow electroplating

of __________ mol of zinc.
A Zn cannot be electroplated.
B 0.5 mol
C 1.0 mol
D 2.0 mol
Zn2+(aq) + 2 e- --> Zn(s)
Slide 136 / 144
48
How many minutes will it take to plate out 16.22 g of Al

metal from a solution of Al3+ using a current of
12.9 amps in an electrolytic cell?
A 60.1 min
B 74.9 min
C 173 min
D 225 min
E 13,480 min
Slide 137 / 144
Electrochemistry -Applied
Batteries
Hydrogen fuel cells
Corrosion
Corrosion prevention
Biology
Slide 138 / 144
Batteries
Slide 139 / 144
Alkaline Batteries
Slide 140 / 144
Hydrogen Fuel Cells
Slide 141 / 144
Corrosion and
Slide 142 / 144
Corrosion Prevention
Slide 143 / 144
In Biology
electron transport in Mitochondria ......
Slide 144 / 144

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Slide 1 / 144

Zn(s) + 2H+(aq) Zn2+ + H2(g)

How do we assign oxidation numbers ?

Elements in their elemental form have an

The sum of the oxidation numbers in a

The oxidation number of a monatomic

The sum of the oxidation numbers in a

Rules for Assigning Oxidation Numbers

Fluorine number of -1.

For example, Cl has an oxidation number of +5 in ClO3-.

Rules for Assigning Oxidation Numbers

Nonmetals tend to have negative

Oxygen has a oxidation number of -2,

What is the oxidation number of each oxygen

What is the oxidation number of the manganese

What is the oxidation number of oxygen atom in

What is the oxidation number of the manganese

What is the oxidation number of sulfur in HSO41-,

Oxidation and Reduction

The lion says

Oxidation and Reduction

Reduction- gaining of electrons

Oxidation and Reduction

What is reduced is the oxidizing agent.

Oxidation and Reduction

An electrochemical reaction in which oxidation and

Which of the following is/are an oxidationreduction (redox) reactions?

Which substance is oxidized in the following

This is not a redox reaction.

Which substance is the reducing agent below?

This is not a redox reaction.

Which substance is oxidized in the following

This is not a redox reaction.

Which substance is the oxidizing agent below?

This is not a redox reaction.

Which substance is reduced in the following reaction?

This is not a redox reaction.

Which substance is the reducing agent?

a) Assign oxidation numbers to each element above.

a) Assign oxidation numbers to each element above.

Which element is oxidized in the

SnCl2(aq) + 2HgCl2 (aq) --> SnCl4 (aq) + Hg2Cl2 (s)

Redox reactions in aqueous solutions

Redox reactions in aqueous solutions

Add the two half reactions to get the overall reaction.

Balancing Redox reactions

Half-reaction method (oxidation # method)

Mg --> Mg2+ + 2 e- --------(1)

Reduction: Ag+ + 1 e- --> Ag

Since all the atoms are balanced, we need to balance

Mg --> Mg2+ + 2 e- --------(1)

Reduction: 2Ag+ + 2 e- --> 2Ag

Half-reaction method (oxidation # method)

Oxidation: Mg --> MgCl2 + 2eReduction: 2AgCl + 2e- --> 2Ag

and we cancel out electrons from both sides:

Overall: Mg + 2AgCl + 2e- --> MgCl2 + 2e- + 2Ag

Redox reactions -balancing

Fe3O4 + 4C --> 3Fe + 4CO

Redox reactions -balancing

SnO2 + 2C --> Sn + 2CO

The Half-Reaction Method

This diagram shows the steps involved in

Write down the individual half reaction.