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Oxidatio

n
✓an increase in oxidation
state
✓loss of electron
✓in organic chemistry, it is
the loss of H atom/s or the
gain of O atom/s.
Oxidizing agent
✓an electron acceptor
✓a reactant that accepts
electron from another
reactant.
✓the reactant that is
reduced in a redox
Reduction
✓a decrease in oxidation
state
✓gain of electron
✓in organic chemistry, it is
the loss of O atom/s or the
gain of H atom/s.
Reducing agent
✓an electron donor
✓a reactant that gives up
electron/s to another
reactant thus decreasing
the oxidation state of one
of its atom.
✓the reactant that is
Oxidation
Number
For an element or
radical, it is the same as
the charge of the ion
formed from an atom of
the element or the ion of
the same composition as
the radical
Oxidation
Number
✓Example: NaCl
the oxidation number of
Na and Cl are +1 and –1
+ –
NaCl → Na + Cl
and it can be said that
sodium and chlorine are in
a +1 and –1 oxidation
Oxidation
State
A concept that
provides a way to keep
track of electrons in
redox reaction
according to certain
rules.
Fundamental
➊ The sum ofRules
the oxidation state
for all atoms in the formula for an
electrically neutral compound is
zero.
➋ The oxidation state for any
element in the free or
uncombined state is zero.
➌ The oxidation state for an ion is
Special
➊ In allConventions
hydrogen compounds,
the oxidation state for H is
+1.
Exception: in hydrides where H is –
1

➋ In all oxygen compounds, the


oxidation state for O is –2.
Special
➌ In allConventions
halides, the oxidation
state for the halogens is –1.
➍ In all sulfides, the oxidation
state for sulfur is –2.
➎ In binary compounds, the element
with the greatest attraction for
electrons is assigned a negative
oxidation state equal to its charge
Some Important Concepts
➊ Corrosion: When a metal
undergoes corrosion it is
oxidized forming cations:
Mg(s) + 2 H+(aq) → Mg2+(aq) + H2(g)
❋ Metals are also oxidized by acids to
form salts:
Mg(s) + 2 HCl(aq) → MgCl2(aq) + H2(g)
❋ Metals can also be oxidized by other
salts:
Some Important Concepts
➋ Activity series: A list of
metals arranged in
decreasing ease of oxidation.
❋ Some metals are easily oxidized
whereas others are not.
❋ The higher the metal on the
activity series, the more active that
metal.
❋ Any metal can be oxidized by the
Some Important Concepts
➌ Solution Composition:
❋ Solution - solute dissolved in a
solvent
❋ Aqueous solution - solution in
which water is the dissolving
medium or solvent (ex. HCl(aq),
H+(aq), Ni2+(aq))
❋ Solute - a substance dissolved in a
solvent to form a solution
Some Important Concepts
➌ Solution Composition:
❋ Concentration - amount or
measure of solute in a solution
(generally measured as molar
concentration)
❋ Molarity - moles of solute per
volume of solution in liters (or
simply moles/liter)
Balancing
Redox
Reaction
Oxidation States
Method
➊ Assign the oxidation states
of all the atoms.
➋ Determine which element
is oxidized and which is
reduced. Take note also of
the change
(increase/decrease) in
Oxidation States
Method
➌ Choose the coefficients for
the compound containing the
element oxidized and the
element reduced such that
the total increase in oxidation
state equals the total
decrease in oxidation state.
➍ Balance the remainder of
Practice Problem
Balance the following redox
reaction using the oxidation
states method:

CH3OH (l) + O2 (g) ➔ CO2 (g) + H2O (g)

MnO2 (s) + Al (s) ➔ Mn (s) + Al2O3 (s)


CH3OH (l) + O2 (g) ➔ CO2 (g) + H2O
C: -2
(g)
O: 0 C: +4 H:
+1
H: +1 O: -2 O: -2
O: -2
C: -2 ➔ +4 & O: 0 ➔ -2
C: loss 6 e- & O: gain 2 e-
2CH3OH + 6O2 ➔ CO2 + H2O
2CH3OH + 6O2 ➔ 2CO2 + 4H2O
CH3OH (l) + O2 (g) ➔ CO2 (g) + H2O
(g)
2CH3OH + 6O2 ➔ 2CO2 + 4H2O
2CH3OH + 6O2 ➔ 2CO2 + 4H2O
Recall: O: 0 to -2 ➔ 2e-/O not 2e-/O2

2CH3OH + 3O2 ➔ 2CO2 + 4H2O

CH3OH: loss 12 e- from O: 2e-


/O
O2: gain 12 e- from O: 6e-/C
2
MnO2 (s) + Al (s) ➔ Mn (s) + Al2O3
Mn:
(s)
+4 Al: 0 Mn: 0 Al:
+3
O: -2 O: -2

Mn: +4 ➔ 0 & Al: 0 ➔ +3


Mn: gain 4 e- & Al: loss 3 e-
3MnO2 + 4Al ➔ Mn + Al2O3
3MnO2 + 4Al ➔ 3Mn + 2Al2O3
MnO2 (s) + Al (s) ➔ Mn (s) + Al2O3
(s)
3MnO2 + 4Al ➔ 3Mn + 2Al2O3
MnO2: gain 12 e- from Mn: 4e-
/Mn
Al: loss 12 e- from Al: 3e-/Al
Half-Reaction Method
➊ Identify the elements
that is oxidized and
reduced.
➋ Write the equations for
the oxidation and
reduction half reactions
Half-Reaction
✓parts of a redox
reaction
✓2 types (oxidation
half reaction and
reduction half
Example
✓Ce4+(aq) + Sn2+(aq)➔ Ce3+(aq) +
Sn4+(aq)

✓Reduction half-reaction:
Ce4+(aq) ➔ Ce3+(aq)

✓Oxidation half-reaction:
Half-Reaction Method
➌ For each half-reaction:
✓Balance all the elements
except H and O.
✓Balance O using H2O
✓Balance H using H+
✓Balance the charge using
Example
✓Ce4+(aq) + Sn2+(aq) ➔ Ce3+(aq) + Sn4+(aq)

✓Reduction half-reaction:
Ce4+(aq) + e- ➔ Ce3+(aq)

✓Oxidation half-reaction:
Sn2+(aq) ➔ Sn4+(aq) + 2e-
Half-Reaction Method
➍ Check if the electrons
transferred in the two
half- reactions are equal.
If not, multiply one or
both equation by an
integer to balance the e –
Example
✓Reduction half-reaction:
Ce4+(aq) + e- ➔ Ce3+(aq)

✓Oxidation half-reaction:
Sn2+(aq) ➔ Sn4+(aq) + 2e-

Reduction half-rxn lacks 1 e-


2 [ Ce4+(aq) + e- ➔ Ce3+(aq) ]
Half-Reaction Method
➎ Add the two half-
reactions and cancel
identical species.
➏ Check to ensure that
the elements and
charges are balance.
Example

2Ce4+(aq) + 2e- ➔ 2Ce3+(aq)


Sn2+(aq) ➔ Sn4+(aq) + 2e-
_____________________________________________

2Ce4+(aq) + Sn2+ ➔ 2Ce3+(aq) Sn4+(aq)


Practice Problem
Balance the following redox
reaction using the half-
reaction method:

acid
MnO4 –
(aq) + Fe
2+
(aq) → Fe3+(aq) + Mn2+(aq)

base

Ag(s) + CN–(aq) + O2 → Ag(CN)2– (aq)


Half-Reaction Method
(Basic)
➊ Follow the same step
as in the acidic
solution.
➋ In the final equation,
identify the H and
+

add OH equal to the


+
Half Reaction Method
(Basic)
➌ Combine the H and OH
+ –

ions by forming H2O.


➍ Eliminate the number of
H2O that appears on both
sides of the equation.
➎ Check to ensure that the
equation is balance.
Electrochemistry
 the study of the
interchange of chemical
and electrical energy
 primarily concerned with
current generation by
chemical reaction and the
use of current to produce a
Electrochemical Cell
➊ galvanic cell or voltaic cell
➋ a device that converts
chemical energy into
electrical energy
➌ utilizes a spontaneous
redox reaction to produce
current that can be used to
Electrochemical Cell
➊ can be divided into to half
cell, one cell containing Zn
metal and ZnSO4 while the
other one Cu and CuSO4
➋ Zn metal is oxidized (to
Zn ) into solution while
2+

Cu2+ are reduced forming


Electrochemical Cell
➌ a point of contact between
the metal and the solution is
called an electrode
➍ the reaction in the cell
occurs at the interface
between the electrode and
the solution (its also the
place where electron
Electrochemical Cell
➎ oxidation occurs at the
anode while reduction at
the cathode
➏ oxidation of Zn causes a
transfer of 2 electrons to
occur
➐ electron flow is measured
Voltmeter

An instrument that
measures cell potential
by drawing electric
current through a known
resistance
Electrochemical Cell
➑ a U-tube filled with
electrolyte is responsible for
the maintaining a zero net
charge for the cells.
➒ the electrolyte-filled U-tube
is called a salt bridge and
allows the ion flow without
Electrolyte
➊ substances whose solution
conducts electric current
➋ a material that dissolves in
water to give a solution
that conducts electric
current
➌ a solution that conducts
Electrolytic Cell
➊ uses electrical energy to
produce a chemical
change that would
otherwise not occur
spontaneously
➋ a device that converts
electrical energy into
Electrolytic Cell
➊ utilizes a power source to
force a chemical reaction
➋ electrons from the
battery are forced towards
the Zn anode causing
electrolysis
➌ the salt bridge maintains
Electrolytic Cell
➍ Zn metal is formed from
the solution of ZnSO4 while
the Cu metal is oxidized
➎oxidation occurs in the
anode and reduction at the
cathode
➏ migration of cations is
Cell Notation
✓ a shortcut to indicate the
parts of an electrochemical
cell
✓also called “line cell
notation”
✓the salt bridge is
symbolized by a double
Cell Notation
✓the anode and the cathode
reaction are separated from
the electrode by a slash (/)
✓the line format goes:
Anode electrode/Anode rxn//Cathode
rxn/Cathode electrode
Cell Notation
Representation of
electrochemical cells

Zn(s) / Zn (1M) // Cu (1M) /


2+ 2+

Cu(s)
Cell Notation
The half reactions indicate the
oxidation of magnesium:
Mg(s) → Mg2+ + 2e-
and the reduction of H+:
2H + 2e → H2(g)
+ -

Since there is no conductive


material in the cathode, we
Cell Potential, Ecell
➊ electromotive force (emf)
➋ the “pull” or driving force
on the electrons from the
reducing agent towards the
oxidizing agent through a
wire
➌ measured in volts (V) and
Cell Potential

Just as a redox reaction


can be divided up into
two half reactions, the
cell potential can be
divided up into two half
cell potentials.
Standard Cell Potentials
➊ emf or the “pull” or driving
force on the electrons
➋ measured in volts
➌ intensive property
➍ based on the assignment of
0 volts to “2H+ + 2e- ➙ H2”
process
Standard Hydrogen
Electrode
➊ consists of a platinum
electrode for its cathode
➋ Pt electrode is in
contact with 1M H+ ions
➌ H2 gas at 1 atm passes
through the Pt electrode
2H+ + 2e- ➙
H2 E° =
0.00
Standard Hydrogen Potential

It is the reference
potential against which all
half-reaction potentials are
assigned
0.00 V
- 0.76 V 0.34 V
Table of Standard
Reduction Potentials
➊ half-reactions are given as
reduction processes
➋ if the half-reaction is
reversed, the sign of E° is
also reversed
➌ if the half-reaction is
multiplied by an integer, E°
Practice Problem
Using the standard
reduction potential table,
calculate the cell potential
based on the following
galvanic cell reactions:
➊ Zn + Cu2+ ➜ Zn2+ + Cu
➋ Cu2+ + Fe ➜ Cu + Fe2+
➌ 2Al + 3Mn2+ ➜ 2Al3+ + 3Mn
Galvanic Cell

A galvanic cell
runs spontaneously
in the direction that
gives a positive cell
potential.
Galvanic Cell

➊ Dry batteriesanare self-


Cell electrochemic
contained and need
al cell that
no salt bridge
➋ Mercury Battery
requires a
continuous
supply of
➌ Lead Storage Battery
reactants to
keep
➍ Hydrogen-Oxygen Fuel
functioning.
Anode: Zn(s)  Zn2+(aq) + 2e-
Cathode: 2NH4+ (aq) + 2MnO2(s) + 2e-  Mn2O3(s) +
2NH3(aq) + H2O(l)
erall: Zn(s) + 2NH4 (aq) + 2MnO2(s)
+

 Zn2+(aq) + Mn2O3(s) + 2NH3(aq) + H2


Anode: Zn(s) + 2OH-(aq)  ZnO(s) +
H2O(l) + 2e-
Cathode: HgO
rall: Zn(s) + HgO
(s) + H O +
2(l)ZnO2e -

+ Hg
Hg (l) +
(s) (s) (l)
2OH-(aq)

Because the
overall
reaction
doesn’t have
any aqueous
solutions,
conc. doesn’t
change and
Anode: Pb(s) + SO42-(aq)  PbSO4(s) + 2e-
Cathode: PbO2(s) + 4H+(aq) + SO42-(aq) + 2e- 
l:PbSO
Pb(s) +
4(s) +
PbO2H O
+ 2SO
2(s)2 (l)
2-
4 (aq) + 4H +
(aq)  2PbSO4(s) +
Overall: 2H2(g) + O2(g)  2H2O(l)
Spontaneity of Reactions
electrical energy = volts x
F = Faradaycoulombs
Constant
= 96,485 C/mol
= the charge on a mole of
electrons

A = = synonymous
Ampere with 1 mole
of e-
= 1 coulomb of charge per
For Chem 16, we will only be
considering this:

ΔG = -nFEcell
or
ΔG° = -nFE°
Spontaneity of Reactions

CONDITIONS Reaction under


standard state
ΔG° K E°cell
<0 >1 >0 Spontaneous

0 =1 0 At equilibrium
Reverse reaction is
>0 <1 <0 spontaneous
Practice Problem
Calculate the ∆G° for the
following reaction and predict
if it is spontaneous:

Cu2+ + Fe ➜ Cu + Fe2+
-o1o.5o1 x 1o5 J

Au(s) + NO3–(aq) + 4H+(aq) ➜


Au3+(aq) + NO(g) + 2H2O(l)
Solution
Cu2+ + 2e- → Cu 0.34V
Fe2+ + 2e- → Fe -0.44V
Cu2+ + Fe → Cu + Fe2+ 0.78V

Au3+ + 3e- → Au 1.50V


NO3- + 4H+ + 3e- → NO + 2H2O 0.96V

Au + NO3- + 4H+ → Au3+ NO + 2H2O


-0.54V
Solution
ΔG° = -nFE°cell

ΔG° = -(2 mol e-)(96,485 C/mol e-)


(0.78V)
ΔG° = -(2 mol e-)(96,485 C/mol e-)
(0.78J/C)
ΔG° = -1.51 x 10 J5
Solution
ΔG° = -nFE°cell

ΔG° = -(3 mol e-)(96,485 C/mol e-)


(-0.54V)
ΔG° = -(3 mol e-)(96,485 C/mol e-)
(-0.54J/C)
ΔG° = 1.56 x 10 J 5
Electrolysis
a method of separating
elements and compounds
by passing electric current
through them
a process of forcing
electrons through a
chemical cell thus causing a
QUANTITATIVE ASPECTS OF ELECTROLYSI
•The number of electrons
transferred in the half reactions
can be used as in stoichiometry.
•A common problem would
involve calculating the amount
(in grams) of a substance that
would be formed during
electrolysis.
•Ex. In electrolysis, one can
calculate how many grams of Na
would be formed if given the
information to obtain the number
QUANTITATIVE ASPECTS OF ELECTROLYSI

•Current is measured in Amperes (A)


•1C = 1 A x 1 s or 1 A = 1 C/1 s
•Therefore if given the current and
time, one can calculate the charge of
electrons that passed through the
electrolytic cell.
•Once you know the charge (in C), you
can use the Faraday constant
(96,500 C/mol e-) to calculate the
number of electrons that are passed
through the electrolytic cell.
Practice Problem
Thirty minutes of
electrolysis of a solution of
CuSO4 produced 3.175g Cu
at the cathode. How many
Faradays and how many
Coulombs passed through
the cell? What is the
Practice Problem
3.175g 1 mol Cu
= 0.05 mol Cu
Cu 63.5g Cu
2 mol e-
0.05 mol = 0.10 mol e-
Cu 1 mol Cu
96,485 C
0.10 mol = 9,648.5 C
e- 1 mol e-

9,648.5 C 30 min 60 sec = 5.36 A


1 min
Take Home Problem
➊ Calculate the amounts of Cu
produced in 1.0 h at inert
electrodes in a solution of
CuBr2 by a current of 2.50 A.
➋ If a steady current was
passed through molten Al2O3
and 15.0 g of Al was collected.
How many coulombs of
Metallurgy
the science and
technology of
extracting metals
from Pyrometallurgy
➊ minerals.

Hydrometallurgy
Principal Mineral Sources of Some
Common Metals
METAL MINERAL Composition
Aluminum Bauxite Al2O3
Chromium Chromite FeCr2O4
Copper Chalcocite Cu2S
Chalcopyrite CuFeS2
Malachite Cu2CO3(OH)2
Iron Hematite Fe2O3
Magnetite Fe3O4
Lead Galena PbS
Manganese Pyrolusite MnO2
Mercury Cinnabar HgS
Molybdenum Molybdenite MoS2
Tin Cassiterite SnO2
Titanium Rutile TiO2
Ilmenite FeTiO3
Zinc Sphalerite ZnS
Five Important
➊Mining Steps
(getting the ore
Refining is the processout of the
ground)
during which a crude,
➋Concentrating (preparing it for
impure metal is converted
further treatment)
into a(topure
➌Reduction obtainmetal.
the free
metal in the zero oxidation state)
➍Refining (to obtain the pure
metal)
➎Mixing with other metals (to form
Pyrometallurgy

utilizes high
temperatures to
obtain the free
metal
Steps involved in the process
✓Calcination - it is heating of ore to cause
decomposition and elimination of a
volatile product:
PbCO3(s) → PbO(s) + CO2(g)
✓Roasting - it is heating which causes
chemical reactions between the ore and
the furnace atmosphere:
2ZnS(s) + 3O2(g) → 2ZnO(s) + 2SO2(g)
2MoS2(s) + 7O2(g) → 2MoO3(s) + 4SO2(g)
✓Smelting - it is a melting process that
causes materials to separate into two or
Pyrometallurgy of iron
Pyrometallurgy of iron
Pyrometallurgy of iron
✓The ore, limestone and coke are
added to the top of the blast
furnace.
✓Coke is coal that has been
heated to drive off the volatile
components.
✓Coke reacts with oxygen to form
CO (the reducing agent):
2C +O → 2CO , ∆H = -221 kJ
Pyrometallurgy of iron
✓CO is also produced by the reaction
of water vapor in the air with C:
C(s) + H2O(g) → CO(g) + H2(g), ∆H = +131
kJ
Since this reaction is endothermic, if
the blast furnace gets too hot, water
vapor is added to cool it down
without interrupting the chemistry.
✓At around 250°C limestone is
calcinated (heated to decomposition
Pyrometallurgy of iron
✓Also around 250°C iron oxides are
Slag consists
reduced by CO:
mostly of
molten
Fe O + 4COsilicates
3 4(s) → 3Fe + 4CO
(g)
in , ∆H = -15
(s) 2(g)

addition
Fe O + 4H
to aluminates,
kJ
→ 3Fe + 4H O , ∆H =
3 4(s) 2(g) (s) 2 (g)

phosphates, fluorides,
+150 kJ

and other inorganic


✓Molten iron is produced lower down
the furnace and removed at the
materials.
bottom.
✓Slag (molten silicate materials) is
Hydrometallurgy

the extraction of
metals from ores
using water
Leaching

✓ it is the selective
dissolution of the desired
mineral.
✓ typical leaching agents are
dilute acids, bases, salts,
and sometimes water.
Hydrometallurgy of
gold
✓Gold can be extracted from
low-grade ore by cyanidation:
NaCN is sprayed over the crushed ore
and the gold is oxidized:
4Au(s) + 8CN-(aq) + O2(g) + 2H2O(l) →
4Au(CN)2-(aq) + 4OH-(aq)
✓The gold is then obtained by
reduction:
2Au(CN)2-(aq) + Zn(s) → Zn(CN)42-(aq) +
Hydrometallurgy of aluminum
✓Aluminum is found in bauxite as
Al2O3•xH2O.
✓Extraction involves the Bayer
process:
The crushed ore is digested in 30%
NaOH (by mass) at 150 - 230°C and
high pressure (30 atm to prevent
boiling).
Al2O3.H2O(s) + 2H2O(l) + 2OH-(aq) → 2Al(OH)4-(aq)
The aluminate solution is separated by
Electrometallurgy

the process of
obtaining metals
through
electrolysis.
Electrometallurgy of sodium
✓Two different starting materials:
molten salt or aqueous solution.
✓Sodium is produced by
electrolysis of molten NaCl in a
Downs cell.
✓CaCl2 is used to lower the
melting point of NaCl from 804°C
to 600°C.
Electrometallurgy of sodium
✓ At the cathode
(iron): 2Na+(aq) +
2e- → 2Na(l)
✓ At the anode
(carbon): 2Cl-(aq) →
Cl2(g) + 2e-
Electrometallurgy of
aluminum
✓Hall-Heroult process
✓Hall electrolysis cell is used to
produce Al
✓Al2O3 melts at 2000°C and it is
impractical to perform electrolysis
on the molten salt.
✓Purified Al2O3 in molten cryolite
(Na3AlF6, m.p. 1012°C) is used
✓Graphite rods are employed and are
Electrometallurgy of
aluminum
Anode: C(s) + 2O2-(l) → CO2(g) + 4e-
Cathode: 3e- + Al3+(l) → Al(l)