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Objectives:

 Applying oxidation-reduction concept


 Balancing redox reaction
 Distinguishing kinds of electrochemistry cell
 Explaining hydrogen electrode potential
 The study of the exchange of chemical and
electrical energy.

 Oxidation-Reduction reactions take place in


electrochemical cells.

 Each electrochemical cell consists of two solid


conductors called electrodes and electrolytic
solution
Electrochemical processes are oxidation-reduction
reactions in which:
• the energy released by a spontaneous reaction is converted to
electricity or
• electrical energy is used to cause a non-spontaneous reaction
to occur
0 0 2+ 2-
2Mg (s) + O2 (g) 2MgO (s)

2Mg 2Mg2+ + 4e- Oxidation half-reaction (lose e-)

O2 + 4e- 2O2- Reduction half-reaction (gain e-)

19.1
Terminology for Redox
Reactions
• OXIDATION—loss of electron(s) by a species; increase
in oxidation number; increase in oxygen.
• REDUCTION—gain of electron(s); decrease in oxidation
number; decrease in oxygen; increase in hydrogen.
• OXIDIZING AGENT—electron acceptor; species is
reduced.
• REDUCING AGENT—electron donor; species is
oxidized.
You can’t have one… without
the other!
 Reduction (gaining electrons) can’t happen without an oxidation
to provide the electrons.
 You can’t have 2 oxidations or 2 reductions in the same
equation. Reduction has to occur at the cost of oxidation

LEO the lion says GER!

GER!
Redox concept
 Oxidation is reaction in which :
 Releasing electrons
 Accepting oxygen
 increasing in oxidation number (oxidation state)
 Occur in anode of electrochemistry cell
 Reduction is reaction in which:
 Accepting electrons
 Releasing oxygen,
 Decreasing in oxidation number (oxidation state)
 Occur in cathode of electrochemistry cell
A. Half-reaction method

B. Oxidation number changing


1. Identifying the species being oxidized or
reduced
2. Writing separate half-reactions for the
oxidation and reduction process
3. Balancing these half-reactions with respect
to both nuclei (atom) and electrical charge
a. Adding H2O (acidic medium) or adding OH-
(basic medium)
b. Balancing electron charge
4. Combining the balanced half-reactions to
form the overall net oxidation-reduction
reaction
1. Writing reactants and products
2. Assigning oxidation number to all elements
3. Calculating the increasing and the
decreasing of oxidation number then
balancing it
4. Balancing the electrical charge in both sides
by adding H+ (acidic medium) and OH-
(basic medium)
5. adding H2O molecule to balance H atom in
both sides
Balance the following in acid solution—
VO2+ + Zn  VO2+ + Zn2+
Step 1: Write the half-reactions
Ox Zn  Zn2+
Red VO2+  VO2+
Step 2: Balance each half-reaction for mass.
Ox Zn Zn2+
Red
2 H+ +VO2+  VO2+ + H2O
Add H2O on O-deficient side and add
H+ on other side for H-balance.
Step 3: Balance half-reactions for charge.
Ox Zn  Zn2+ + 2e-
Red e- + 2 H+ + VO2+  VO2+ + H2O
Step 4: Multiply by an appropriate factor.
Ox Zn  Zn2+ + 2e-
Red 2e- + 4 H+ + 2 VO2+
 2 VO2+ + 2 H2O
Step 5: Add balanced half-reactions
Zn + 4 H+ + 2 VO2+
 Zn2+ + 2 VO2+ + 2 H2O
 Never add O2, O atoms, or
O2- to balance oxygen.
 Never add H2 or H atoms to
balance hydrogen.
 Be sure to write the correct
charges on all the ions.
 Check your work at the end
to make sure mass and
charge are balanced.
 PRACTICE!
 Balance the reaction below

1. H2SO3 + HNO2  NO + SO42- (acidic medium)

2. Fe2+ + MnO4-  Fe3+ + Mn2+ (acidic


medium)

3. Br2 + IO3-  Br- + IO4- (basic medium)

4. AsO2- + Br2  AsO43- + Br- (basic


medium)
Two types of electrochemical cells:

 Voltaic Cell

 Electrolytic Cell
Comparing a chemical (voltaic) cell
and an electrolytic cell
Chemical (voltaic) Electrolytic cell
cell
Reactions at Reduction Oxidation (anode)
positive (Cathode)
electrode
Reactions at Oxidation (anode) Reduction (Cathode)
negative
electrode
Voltaic Cell

 Reactions are spontaneous


 Redox reactions produce electrical
energy

 Lets look at an example:

Cu+2 (aq)+ Zn (s)  Cu (s) + Zn+2 (aq)


Chemical or Voltaic or Galvanic cell
Anode Cathode
Oxidation Reduction
occurs occurs
Electrons Electrons are
produced consumed
Has negative Has positive
sign (-) sign (+)
Anions migrate Cations migrate
toward toward
• Each Voltaic cell is composed of two half
cells.

Zinc electrode Copper electrode


The anode, is the electrode where
the oxidation of zinc occurs:

Zn (s)  Zn+2 (aq) + 2e-

As zinc is oxidized, the zinc


electrode will slowly dissolve to
produce zinc ions, which enter into
the solution.

Anode
(negative)
The cathode is the electrode
where the reduction of copper
occurs:

Cu+2 (aq)+ 2e-  Cu (s)

As copper is reduced, copper


atoms accumulate on the surface
of the solid copper electrode.

Cathode
(positive)
Looking at the two cells, can a redox reaction
take place?

The reaction will not occur.


There is no way for the electrons lost by Zinc to
get over to the Copper ions and reduce them to
Copper metal.
What if we provide a path for the electrons released
by the oxidation of the zinc to get over to the copper?

Now that the electrons have a path to the


Cu/Cu2+ side it wouldWhy?
appear that the reaction
can proceed,
but it does not.
• As the redox reaction proceeds:

• There is a build up of Zn2+ ions in the solution where the


Zinc is being oxidized

• At the same time, Cu2+ ions are removed from solution


where the Copper ion is being reduced

• As a result, there is a build up of a positive charge in the


zinc solution, and a negative charge in the copper
solution. These charges do not allow electrons to flow.

• The positive charge in the zinc solution makes it harder for


the negative electrons to leave and the negative charge in
the copper solution repels the electrons that are trying to
come over from the zinc side
We need a way to neutralize the charge build-up in
the solutions due to the change in ion concentration
What if we had a tube filled with aqueous solution
that connected the two redox reactions?

Electron flow

This tube
contains
an
electrolyte
and is called
a salt bridge.
The salt bridge allows the electrons to flow,
keeping the overall concentration of ions in balance
between the two sides.

By connecting the salt bridge we have


movement of both types of ions:

anions are going into the oxidation side and


cations are going into the reduction side
Sel Volta
Galvanic Cell
Shorthand Notation for Cells

Shorthand Notation for:


Zn° + Cu+2 Zn+2 + Cu°
Anode Cathode
electrode
electrode
Shorthand Notation for Cells
• Write shorthand notation for:
Fe(s) + 2Fe+3(aq)  3Fe+2(aq)

Fe  Fe2+ + 2e- = oxidation (anode)


Fe3+ + 1e-  Fe2+ = reduction (cathode)

Anode Cathode

Fe° Fe+2 Fe+3 Fe+2


Shorthand Notation for Cells
Write shorthand notation for:

2Ag+1(aq) + Ni (s) 2Ag (s) + Ni+2 (aq)

Ni° Ni+2 Ag+1 Ag°


Standard Cell potential

 Electrical energy produced by a redox reaction is


measured as voltage
 a quantitative measure of the tendency of reactants
to proceed to products when all are in their standard
states at 25 ˚C.
 Some standard electrode potentials are listed below.
Electrode Process Eo/V
Li+(aq) + e-  Li(s) -3.03
K+(aq) + e-  K(s) -2.92
Zn2+(aq) + 2e-  Zn(s) -0.76
Cu2+(aq) + 2e-  Cu(s) +0.34
Standard Electrode Potentials

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)


Anode (oxidation): Zn (s)  Zn2+ (1 M) + 2e-
Cathode (reduction): 2e- + 2H+ (1 M)  H2 (1 atm)
Zn (s) + 2H+ (1 M)  Zn2+ + H2 (1 atm)
19.3
Standard Cell Potential for Zn and Cu
is 1.1 volts
Calculating Cell Voltage
• Balanced half-reactions can be added
together to get overall, balanced equation.
Zn(s)  Zn2+(aq) + 2e- (anode)
Cu2+(aq) + 2e-  Cu(s) (cathode)
--------------------------------------------
Cu2+(aq) + Zn(s)  Zn2+(aq) + Cu(s)
If we know Eo for each half-reaction, we could get Eo
for net reaction.
Or Eo cell = Eo cathode - Eo anode
TABLE OF STANDARD
REDUCTION POTENTIALS
oxidizing
ability of ion Eo (V)

Cu2+ + 2e- Cu +0.34

2 H+ + 2e- H2 0.00

Zn2+ + 2e- Zn -0.76


To determine an oxidation from a
reduction table, just take the opposite
sign of the reduction! reducing ability
of element
 Oxidizing agent with negative Eo having
lower oxidation potential than hydrogen ion
but its reducing agent having stronger
reduction potential than hydrogen atom in
gaseous phase at 1 atm.
 Zn is stronger reduction agent than Cu

 Oxidizing agent with positive Eo having


stronger oxidation potential than hydrogen
ion but its reduction agent having lower
reducing potential than hydrogen atom in
gaseous phase at 1 atm.
 Cu2+ is stronger oxidation agent than Zn2+
Electrolytic Cell

 Reactions are non spontaneous

 Redox reactions require electrical


energy to occur
Anions are attracted towards the anode
where they undergo oxidation.
Electrons flow from the anode to the
cathode where cations undergo
reduction.
Voltaic Cell vs Electrolytic Cell
Commercial uses of electrolysis

 Manufacture of hydrogen, chlorine and


sodium hydroxide and bleaching solution
 Refining of copper
 Electroplating
 Extracting reactive metals
 Aluminium anodization
Sel Volta
vs
Sel Elektrolisa

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