Chemistry and Electricity:

ELECTROCHEMISTRY
Ruth Tolentino-Libag, RMT, RPT, MA Chem
Professor
 DEFINITION OF TERMS
 Oxidation number – used
interchangeably with oxidation state
- are positive or negative numbers
assigned to individual atoms in substances
to keep track of the number of valence
electrons lost or gained
 Oxidation # vs real charge

 Oxidation number •The charge of the

of oxygen is -2 oxide ion is 2-
 Oxidation number
•The charge of the
of N in nitrate ion
ion is 1-
(NO31-) is +5
 Oxidation number
 For ionic compounds, oxidation numbers are the
same as the ionic charges
Na1+Cl1-
 For covalent compounds, oxidation numbers are
the charges the atom would have if the electrons
of each bond belonged to the more
electronegative atom
H+1O-2N+3O-2
 GEROA & LEORA

 GEROA – When an atom gained

electrons, it is reduced and acts as
an oxidizing agent
 LEORA – When an atom lost
electrons, it is oxidized and acts as a
reducing agent
 Determine the oxidation #
1. Cl in KCl and KClO3
2. S in H2S, NaHSO3, Na2S4O6
3. C in C6H6, CO2 and HCHO
4. Mn in MnSO4, MnO2 and KMnO4
 Which of the following is not a
redox reaction?
1. 2Al + 3Br2 2AlBr3
2. S + O2  SO2
3. 2KOH + H2SO4  K2SO4 + H2O
4. 2KNO3  2KNO2 + O2
5. C6H12O6 + 6O2  6CO2 + 6H2O
 Identify the oxidizing and reducing
agents in the following reactions
1. Ca + Cl2  CaCl2
2. Zn + CuSO4  ZnSO4 + Cu
3. C + ZnO  CO + Zn
4. 3Ag + 4 HNO3  3AgNO3 + NO + 2H2O
5. 2H2O2 2H2O + O2
 Which of the following reagents
would be good oxidizing agents:

Fe2+, Fe3+,MnSO4, MnO4-, F2,F-

The good oxidizing agents are the

electron-poor species or easily reduced
ones -- Fe3+, MnO -, F
4 2
 Oxidation number-electron
method
Exercises:
1. S + HNO3  SO2 + NO+ H2O
2. [Cr2O7]2- + S2- + H+  Cr3+ + S + H2O
3. HClO  HClO3 + HCl
 ASSIGNMENT
1. Describe the components of the dry cell. Identify the
anode and cathode in the dry cell. (section 10.1
Snyder)
2. A car battery delivers hundreds of amperes at a
potential of 12v. To what can you compare this, a wide
river flowing slowly or a small but sharp jet of water like
that used by a dentist? (Snyder’s voltage-water
pressure and ampere-rate of flow analogies)
3. Identify the anode and cathode when the lead storage
battery is a.) discharging b.) charging (section 10.14
Snyder)
4. An iron pipe is embedded in concrete. When
examined, the portion of the pipe very near the junction
of the cement surface and the pipe is badly corroded.
Explain why this happens.
 The Electricity of Chemistry
Oxidation-reduction is at the core of the
relationship between the transfer of
electricity.
 The transfer of electrons from one
chemical specie to another is utilized to
produce energy in electric batteries
 The chemistry of redox reactions applied
to meet the needs of society .
 Zinc-carbon flashlight battery
 A dry cell consists of graphite carbon as
the positive electrode
 Zinc casing as the negative electrode
 And a paste mixture of MnO2, NH4Cl and
ZnCl2 as electrolyte
 The Dry Cell
 Zinc Casing is the anode
- Zn loses e’s, source of
e’s and is (-)
 The graphite carbon is
the cathode
- Graphite receives e’s
from outside, and is (+)
Chemical reactions in the flashlight
Zn  Zn2+ + 2e
2MnO2 + 2NH4+ + 2e  2NH3 + 2MnO(OH)
 The NH3 produced combines with Zn2+ holding
down the latter’s conc.
 It also prevents a condition known as polarization
or the accumulation of NH3 on the cathode surface
 The Zinc-carbon battery is an example of an
electrochemical cell of the voltaic type.
 The Daniell Cell
 Daniell cell is the simplest example of a
voltaic cell (galvanic cell)
 In voltaic cell, the chemical energy of a
spontaneous reaction is converted to
electrical energy
 The electrolytic cell, on the other hand,
requires a source of electric energy to
affect chemical change
 The Daniell Cell

Zn strip goes into the solution to form

Zn2+ ions
Cu2+ in the solution deposit as Cu metal
on the zinc strip
How does the Daniell cell work?
Half reactions:
Zn  Zn2+ + 2e (oxidation, anode, zinc surface)
Cu2+ + 2e  Cu (reduction, cathode, copper surface)

 The give and take of electrons between zinc

metal and copper ions are harnessed in
someway such that an electrical current is
produced. This is done by separating the
anode from the cathode and allowing the
electrons to move in the external circuit.
 How does the Daniell cell work?
•The electrons lost by zinc move
out of the anode into the outside
circuit, then flow through the
voltmeter and enter the cell again
through the copper plate
•Zinc plate serves as the source
The Daniell cell is a of electrons for the outside circuit
primary cell. It cannot (- polarity, + charge, anode )
be recharged
•Copper plate is where the
The salt bridge
preserves the electrons enter the cell from
electroneutrality of the outside (+ polarity, - charge,
electrolyte solution cathode)
 Voltage versus Ampere
 Voltage compared to water pressure in a
pipe
the voltage, the force that moves
an electron from point to point within an electric
circuit
 Ampere compared to the rate of flow of
water measured in quantities per unit time
- measures the rate of flow of current
 Voltage versus Ampere
 A wide river flowing slowly (low pressure, high
rate of flow because of the large volume of
water) can be compared to the flow of electricity
in a car battery (high current, low voltage). It is
not harmful because of the low voltage.
 Lahar flow during typhoon comes rampaging.
Both volume and rate are large. That is why it is
damaging. It can be compared to electric current
at high voltage and high amperage, which are so
harmful that may even kill people.
Why does the Daniel cell work?
Important concepts
 The potential to gain e’s is measured as
electrical voltage and is referred to as
reduction potential
 The potential to lose e’s is measured a
electrical voltage and is referred to as
oxidation potential
 the reference standard for measuring
potential is the reduction of two H+ ions to
a H2 molecule
Why does the Daniel cell work?
 When all participating substances are in their
respective standard state, the reduction potential
measured is referred to as the standard
reduction potential and is labeled Eored.
 A positive sign for the reduction or oxidation
potential means that the reaction is
spontaneous.
 A negative sign means the reaction is non
spontaneous.
Why does the Daniel cell work?
 Refer to the table of standard reduction
potential of substances in the order of
increasing tendency to be reduced
 Example:
Li+ + e  Lio Eored = -3.04 v
Lio  Li+ + e Eoox = +3.04 v
* Note: reduction /oxidation potential is an
intensive property and its value does not depend
on the number of atoms, molecule or electrons
involved in the reaction.
Why does the Daniel cell work?
 An electrochemical cell is obtained by
combining an oxidation half cell and a
reduction half cell.
 The cell generates electricity
spontaneously, if the resulting cell
potential is positive
Eocell = Eoox + Eored
Why does the Daniel cell work?
Cell potential of the Daniell cell :
Zn  Zn2+ + 2e Eoox = +0.76 v
Cu2+ + 2e  Cu Eored =+0.34 v
Zn + Cu2+  Zn2+ + Cu Eocell =+1.1 v
* The Eocell is positive, thus the reaction is
spontaneous and will serve as a source of
energy or voltaic cell
Why does the Daniel cell work?
The accepted convention in representing an
electrochemical cell
 Write the oxidation half cell on the left
 Write the reduction half cell on the right
 A single bar indicates the interface
between the electrode and electrolyte.
 A double bar represents a salt bridge
Zn / Zn2+ // Cu2+ / Cu
 Assignment
1. If an iron nail is placed in a solution of Zn2+
ions and Cu2+ions, what spontaneous reaction
will occur?
2. What will happen if both copper and silver are
placed in contact with solutions containing both
Cu2+ and Ag+ ions?
3. Would a household bleach solution containing
ClO- be able to remove the color of iodine
stains? Explain.
4. Calculate the cell potential for the following rxn
Fe(s) + Cl2(aq)  Fe2+(aq) + 2Cl-(aq)
Represent the electrochemical cell for this
reaction
 Lead storage battery
 Secondary cells
 These are voltaic cells which can be generated
by passing electric current in the reverse
direction of discharge.
 Rechargeable
 While in neutral position, the battery is being
recharged by the generator or alternator.
 The voltage output depends on the number of
cells that are joined in the series
 They are available in 6, 24 or 32 volts.
 Lead storage battery
 Each cell consists of parallel lead plates in
grid form.
 One plate is filled with spongy lead, the
other with lead (IV) oxide
 The electrolyte is dilute sulfuric acid which
at normal operating condition is about 38%
by mass
Lead storage battery

A. During discharging
Anode: Pb (-)
Cathode: PbO2 (+)
B. During charging
Anode: PbO2 (+)
Cathode: Pb (-)
 Lead storage battery
 The spontaneous reaction when
discharging is:
Pb + PbO2 + 2 H2SO4  2PbSO4 + 2H2O
Eo= +2.04 v
 When the battery is charging, the reverse
non spontaneous reaction occurs:
2PbSO4 + 2H2O  Pb + PbO2 + 2 H2SO4
Eo= -2.04 v
 Lead storage battery
*Half cell reaction during discharge:
Pb  Pb2+ + 2e Eoox = +0.36 v
PbO2 + SO42- + 4H+ + 2e  PbSO4 + 2H2O
Eored =+1.69 v
*Half cell reaction during charging:
Pb2+ + 2e  Pb Eoox = -0.36 v
PbSO4 + 2H2O  PbO2 + SO42- + 4H+ + 2e
Eored =-1.69 v
 Lead storage battery
 How many individual cells in a Pb storage
battery should be connected in a series to
give a 24 volt output?
 Twelve individual cells connected in series
would give a 24 v output since one cell’s
output is 2.04v
*Take note that voltage is additive while current is
constant
 Lead storage battery
 What happens to the pH of the battery
solution when it is discharging? Charging?
 The pH rises during discharge (less
acidic) since H+ ions are used up forming
H2O. During charging, pH goes down
(acidic) since H+ ions are being produced
 Lead storage battery
 To check the degree of discharge of a Pb
storage battery, a hydrometer is used to
check the density of the electrolyte. What
is the basis of this procedure?
 The Pb2+ ions formed during discharge
react with SO42- forming insoluble PbSO4.
When taken out of solution, the density of
the solution decreases.
 Other Commercial Batteries
 Alkaline batteries
- has KOH mixed with
powdered Zn for
electrolyte.
- has porous sleeve that
separates the electrolyte
from the MnO2
-metal nail at the core
collects electrons from
the Zn and conducts
them to the (-) terminal
 Other Commercial Batteries
Overall reaction :
Zn(Hg) + HgO(s)  ZnO(s) + Hg(l)
 Mercury or Rubin-
Mallory Cell
 Used in hearing
aids, pace makers,
and watches
 Provides a constant
voltage of 1.35v
bec overall reaction
involves only solid
subs
 Longer lasting and
has higher capacity
 Other Commercial Batteries
 Silver oxide battery
 Cathode: Ag2O
 Anode: Zn
 Electrolyte medium:
moist alkaline paste

Cathode: Ag2O(s) + H20 + 2e  2Ag(s) + 2OH-(aq)

Anode: Zn(s) + 2OH-(aq)  Zn(OH)2(aq) + 2e
Zn(s) + Ag2O(s) + H2O(l)  2Ag(s) + Zn(OH)2
 Commercial Batteries
Type Feature Voltage

Alkaline battery Contains KOH in 1.5 v

electrolyte; longer
lifetime
Lithium battery Li is the anode Over 3 v

Mercury battery Rxn between Zn 1.3 v

and HgO
Silver oxide Rxn between Zn 1.5 v
battery and Ag2O
 Nickel-Cadmium cell
 Nickel-cadmium cell
 Efficiently used for electrochemical storage for
space operations in Explorer, Gemini, Mariner
and Ranger satellites
 Secondary cells
 Anode: cadmium
 Cathode: Nickel (IV) oxide
 Electrolyte: Alkaline medium
Anode: Cd + 2H2O  Cd(OH)2 + 2e + 2H+
Cathode: NiO2 + 2H+ + 2OH- + 2e  Ni(OH)2 + 2OH-
Overall: Cd + NiO2 + 2H2O  Cd(OH)2 + Ni(OH)2
 Fuel Cell
 Fuel cells are claimed to have greater power
conversion efficiency
 Voltaic cells which operate as long as the fuel
(gas) is continuously supplied
 Used in spacecrafts e.g. Apollo missions
 Reactants: cryogenic H2 (fuel) and O2 (oxidizer)
 Anode: H2-O2 fuel cell made up of porous
electrode with finely divided Pd or Pt as catalyst
 Cathode: porous electrode with CoO, Pt or Ag
catalyst
 Electrolyte: concentrated solution of NaOH or
KOH
 Fuel Cell
Anode: (H2 + 2OH-  2H20 + 2e)2
Cathode: O2 + 2H20 + 4e  4OH-
Overall: 2H2 +O2  2H20
 Fuel Cell
 Advantage: H2-O2 fuel cell does not
produce any toxic waste product
 Disadvantage: The reactants or fuels are
gases and require large volumes of
container. This is not very portable.
Electrolysis and Electrolytic cells
 Electrolysis is the decomposition of a substance
into its constituents by means of electricity.
 Requires electrolytic cell
 Electrolytic cell is the opposite of voltaic cell
 Requires external source of energy, usually DC
current
 Essential parts: electrodes and electrolyte
 Anode: oxidation occurs; cathode: reduction
occurs
Polarities of the electrodes
 Electrolytic cell
 During electrolysis
Anode: Cl-  ½ Cl2 + e Eoox = -1.36 v
Cathode: H+ + e  ½ H2 Eored = 0 v
H++ Cl-  ½ H2 + ½ Cl2 Eocell = -1.36 v
• Ec is negative, the reaction is non
spontaneous
 Redox in everyday life
 The energy that we used in our homes,
factories and transportation is mainly
derived from the burning of fuels.
 Burning is a redox reaction
C8H18 + 25 O2  16CO2 +18H2O
 Redox in everyday life
 Use of chlorine to destroy pathogenic
bacteria during purification of drinking
water, extraction of metal from their ores,
photography and use of explosives
 Redox in everyday life
Assignment:
 Explain the oxidation-reduction processes
in developing photographic films
 Trinitroglycerin is a known explosive.
What structural features does it have that
give its explosive properties?
 The Chemistry of Corrosion
 Corrosion is the wearing away of materials
exposed to the elements of the
environment.
 Most common example of direct oxidation
of metals is rusting
 Fe is exposed to air and water
 Ideal condition for rusting is to have iron
partly exposed to oxygen and partly
protected from oxygen
 The Chemistry of Corrosion
 Anode: the part that is protected from
oxygen
 Cathode: the part that is exposed to air
Anode: Fe  Fe2+ + 2e
Fe2+  Fe3+ + e
Cathode: 2H2O(l) + O2(g) + 4e  4OH-

* The products of these separate reactions

then combine to form Fe2O3.H20, or rust
 The Chemistry of Corrosion
 Answer to the assignment:
The anode portion of the iron pipe undergoes
the corrosion process
Fe  Fe2+ + 2e
Fe2+  Fe3+ + e
The cathode portion of the pipe requires oxygen
for the reduction of water
2H2O(l) + O2(g) + 4e  4OH-

Thus, the part exposed to air becomes cathodic

and the embedded part becomes anodic and
corrodes.
 The end

Be ready for a long exam next

meeting in your lecture class…