LECTURE 1

Redox Review
Redox reactions: electron transfer processes
Oxidation: loss of 1 or more e-
Reduction: gain of 1 or more e-
Oxidation numbers: imaginary charges
(Balancing redox reactions)
• Oxidation Numbers (O.N.)
1. Pure element O.N. is zero
2. Monatomic ion O.N. is charge
3. Neutral compound: sum of O.N. is zero
Polyatomic ion: sum of O.N. is ion’s charge
*Negative O.N. generally assigned to more electronegative element
• Oxidation Numbers (O.N.)
4. Hydrogen
assigned +1
(metal hydrides, -1)
5. Oxygen
assigned -2
(peroxides, -1; OF2, +2)
6. Fluorine
always -1
• Oxidation-reduction
Oxidation is loss of e-
O.N. increases (more positive)
Reduction is gain of e-
O.N. decreases (more negative)
Oxidation involves loss OIL
Reduction involves gain RIG
• Redox
Oxidation is loss of e-
causes reduction
“reducing agent”
Reduction is gain of e-
causes oxidation
“oxidizing agent”
• Zn (s) + CuSO4 (aq) → ZnSO4 (aq) + Cu (s)
The oxidation half-reaction can be written as: Zn → Zn2+ + 2e–
The reduction half-reaction can be written as: Cu2+ + 2e– → Cu
• Balancing Redox Reactions
1. Write separate equations (half-reactions) for oxidation and reduction
2. For each half-reaction
a. Balance elements involved in e- transfer
b. Balance number e- lost and gained
3. To balance e-
multiply each half-reaction by whole numbers
• Balancing Redox Reactions: Acidic
4. Add half-reactions/cancel like terms (e-)
5. Acidic conditions:
Balance oxygen using H2O
Balance hydrogen using H+
Basic conditions:
Balance oxygen using OH-
Balance hydrogen using H2O
6. Check that all atoms and charges balance
• Examples
Acidic conditions:

Basic conditions:
• Electrochemistry and Redox
Oxidation-reduction: “Redox”
Electrochemistry:
study of the interchange between chemical change and electrical work
Electrochemical cells:
systems utilizing a redox reaction to produce or use electrical energy
• Types of cells
Voltaic (galvanic) cells:
a spontaneous reaction generates electrical energy.
produce electrically from chemical reaction between a cat ion and anion.
Electrolytic cells:
absorb free energy from an electrical source to drive a non spontaneous reaction
use electricity to cause the reaction to occur.
• Electrode Potential (E0)
• Determine the proposed half cell reaction whether the reaction will occur or not.
• + E0 value = spontaneous
• -E0 value = non spontaneous
• A large negative value means that the element or compound ionizes easily, in other words, it
releases electrons easily. This element or compound is easily oxidized and is therefore a
good reducing agent (RA).
• A large positive value means that the element or compound gains electrons easily. This element
or compound is easily reduced easily reduced and is therefore a good oxidizing agent (OA).
• The reducing ability (i.e. the ability to act as a reducing agent) of the elements or compounds in
the table decreases as you move down in the table.
• The oxidizing ability of elements or compounds increases as you move down in the table.
• Significance of Electro Motive Force (Emf)
• It is used to calculate the amount of electrical energy , equivalent constant(k) and std free
energy change ( G)
G = -nFE0 F = 96500 J/V.mol

n= no of moles
E0 = values
• Common Components
Electrodes:
conduct electricity between cell and surroundings
Electrolyte:
mixture of ions involved in reaction or carrying charge
Salt bridge:
 completes circuit (provides charge balance)
• Electrodes
Anode:
Oxidation occurs at the anode
Cathode:
Reduction occurs at the cathode
Active electrodes: participate in redox
Inactive: sites of ox. and red.
• Voltaic (Galvanic) Cells
A device in which chemical energy is changed to electrical energy.
Uses a spontaneous reaction.
• Zn2+(aq) + Cu(s) → Cu2+(aq) + Zn(s)
Zn gives up electrons to Cu
– “pushes harder” on e-
– greater potential energy
– greater “electrical potential”
Spontaneous reaction due to
– relative difference in metals’ abilities to give e-
– ability of e- to flow
Common Components
Electrodes:
conduct electricity between cell and surroundings
Electrolyte:
mixture of ions involved in reaction or carrying charge
Salt bridge:
completes circuit (provides charge balance)
A salt bridge refers to a device used to form an electrochemical cell by providing a means to
support the free flow of ions between the oxidation and reduction half-cell components.
A salt bridge facilitates corrosion because corrosive reactions typically occur in the presence of
electrochemical cells.
A salt bridge is a device used in an electrochemical cell for connecting its oxidation and
reduction half cells wherein a weak electrolyte is used.
In other words, a salt bridge is a junction that connects the anodic and cathodic compartments
in a cell or electrolytic solution.
A salt bridge isolates the reactants but maintains electrical contact between the two halves of
the cell. When a voltmeter of high internal resistance is connected or the electrodes are not
connected externally, the cell is said to be at open circuit and delivers the full cell potential.
Electrochemical cells
* An electrochemical cell consists of two conductors called electrodes, each of which is
immersed in an electrolyte solution.

Types of Electrochemical Cells

Representing Cells Schematically
Electrodes
Anode:
Oxidation occurs at the anode
Cathode:
Reduction occurs at the cathode
Active electrodes: participate in redox
Inactive: sites of ox. and red.
Voltaic (Galvanic) Cells
A device in which chemical energy is changed to electrical energy.
Uses a spontaneous reaction.

Zn2+(aq) + Cu(s) → Cu2+(aq) + Zn(s)

Zn gives up electrons to Cu
“pushes harder” on e-
greater potential energy
greater “electrical potential”
Spontaneous reaction due to
relative difference in metals’ abilities to give e-
ability of e- to flow
Cell Potential
Cell Potential / Electromotive Force (EMF):
The “pull” or driving force on electrons
Measured voltage (potential difference)
Sacrificial Anodes
sacrificial Anodes are highly active metals that are used to prevent a less active material surface
from corroding.
Sacrificial Anodes are created from a metal alloy with a more negative electrochemical
potential than the other metal it will be used to protect. The sacrificial anode will be consumed
in place of the metal it is protecting, which is why it is referred to as a "sacrificial" anode.
Cathode Protection
When metal surfaces come into contact with electrolytes, they undergo an electrochemical
reaction known as corrosion.
Corrosion is the process of returning a metal to its natural state as an ore and in this process,
causing the metal to disintegrate and its structure to grow weak.
These metal surfaces are used all around us -- from pipelines to buildings to ships. It is
important to ensure that these metals last as long as they can and thus necessitates what is
known as cathode protection.
Sacrificial anodes are among several forms of cathode protection. Other forms of cathode
protection are
plating,
galvanization, and
the formation of alloys.
Metal in seawater is one such example with the iron metal coming into contact with electrolytes.
Under normal circumstances, the iron metal would react with the electrolytes and begin to
corrode, growing weaker in structure and disintegrating.
The addition of zinc, a sacrificial anode, would prevent the iron metal from "corroding".
According to the table of Standard Reduction Potentials, the standard reduction potential of zinc
is about -0.76 volts. The standard reduction potential of iron is about -0.44 volts. This difference
in reduction potential means that Zinc would oxidize much faster than iron would. In fact, zinc
would oxidize completely before iron would begin to react.
What materials are used for sacrificial anodes?

The materials used for sacrificial anodes are either relatively pure active metals, such as zinc or
magnesium, or are magnesium or aluminum alloys that have been specifically developed for
use as sacrificial anodes. In applications where the anodes are buried, a special backfill material
surrounds the anode in order to insure that the anode will produce the desired output.
Since the sacrificial anode works by introducing another metal surface with a more negative
electronegative and much more anodic surface. The current will flow from the newly
introduced anode and the protected metal becomes cathodic creating a galvanic cell. The
oxidation reactions are transferred from the metal surface to the galvanic anode and will be
sacrificed in favor of the protected metal structure.
How are sacrificial anodes put on?

Sacrificial anodes are normally supplied with either lead wires or cast-m straps to facilitate their
connection to the structure being protected. The lead wires may be attached to the structure
by welding or mechanical connections. These should have a low resistance and should be
insulated to prevent increased resistance or damage due to corrosion. When anodes with cast-
in straps are used, the straps can either be welded directly to the structure or the straps can be
used as locations for attachment.
A low resistance mechanically adequate attachment is required for good protection and
resistance to mechanical damage. In the process of providing electrons for the cathodic
protection of a less active metal the more active metal corrodes. The more active metal (anode)
is sacrificed to protect the less active metal (cathode). The amount of corrosion depends on the
metal being used as an anode but is directly proportional to the amount of current supplied.
Applications
Sacrificial Anodes are used to protect the hulls of ships, water heaters, pipelines, distribution
systems, above-ground tanks, underground tanks, and refineries.
The anodes in sacrificial anode cathodic protection systems must be periodically inspected and
replaced when consumed.
References
"Corrosion Control" NAVFAC MO-307 September 1992
Petrucci, Ralph H., William S. Harwood, Geoffrey Herring, and Jeffry D. Madura. General
Chemistry: Principles & Modern Applications. Ninth ed. Upper Saddle River, N.J.: Pearson
Education, 2007. 848. Print.
Evaluation
Problems
What are the purposes of using sacrificial anodes?
How do sacrificial anodes function?
What other forms of cathode protection?
What different metals can be used as sacrificial anodes?
Cell Potential, E0cell
E0cell
cell potential under standard conditions
elements in standard states (298 K)
solutions: 1M
gases: 1 atm
Standard Reduction Potentials

E values for reduction half-reactions with solutes at 1M and gases at 1 atm

SHE : Std Hydrogen Electrode
Cu2+ + 2e- ® Cu

E = 0.34 V vs. SHE

SO42- + 4H+ + 2e- ® H2SO3 + H2O

E = 0.20 V vs. SHE

E0cell and G0

E0cell > 0 G0 < 0 Spontaneous

E0cell < 0 DG0 > 0 Not

E0cell = 0 G0 = 0 Equilibrium

Calculating E0cell
E0cell = E0cathode - E0anode

Br2(aq)+2V3+ +2H2O(l) → 2VO2+(aq)+ 4H+(aq)+ 2Br-(aq)

Given: E0cell = +1.39 V
E0Br2 = +1.07 V
What is E0V3+ and is the reaction spontaneous?
E0 values
More positive:
Stronger oxidizing agent
More readily accepts e-
More negative:
Stronger reducing agent
More readily gives e-

Stronger R.A. + O.A. → Weaker R.A. + O.A.

Free Energy and Cell Potential
n: number of moles of e-
F: Faraday’s constant
96485 C
mol of e-
G0, E0, and K
At equilibrium: DG0 = 0 and K = Q
At 298 K:
Nernst Equation
Under nonstandard conditions
Concentration Cells
... a cell in which both compartments have the same components but at different
concentrations
Application of Galvanic Cell
Batteries
A battery is a galvanic cell or, more commonly, a group of galvanic cells connected in series.
Fuel Cells
Galvanic cells
Reactants are continuously supplied.
2H2(g) + O2(g) ® 2H2O(l)
anode: 2H2 + 4OH- ® 4H2O + 4e-

cathode: 4e- + O2 + 2H2O ® 4OH-

Corrosion
Some metals, such as copper, gold, silver and platinum, are relatively difficult to oxidize.
These are often called noble metals.
Electrolysis
Forcing a current through a cell to produce a chemical change for which the cell potential is
negative.
How it was happened?
When an Ionic compound is melted or dissolved in water, the force of attraction are broken and
the ions are free to move
These liquids and solutions can now conduct electricity.
These liquids or solutions are called ELECTROLYTES.
Stoichiometry
How much chemical change occurs with the flow of a given current for a specified time?
current and time ® quantity of charge ®
moles of electrons ® moles of analyte ®
grams of analyte

Anatomy of a Chemical Equation

CH4 (g) + 2O2 (g) CO2 (g) + 2 H2O (g)
Anatomy of a Chemical Equation
Reactants appear on the left side of the equation.
CH4 (g) + 2 O2 (g) CO2 (g) + 2 H2O (g)
Anatomy of a Chemical Equation
Products appear on the right side of the equation.
CH4 (g) + 2 O2 (g) CO2 (g) + 2 H2O (g)
Anatomy of a Chemical Equation
The states of the reactants and products are written in parentheses to the right of each
compound.
CH4 (g) + 2 O2 (g) CO2 (g) + 2 H2O (g)
Anatomy of a Chemical Equation
Coefficients are inserted to balance the equation.
CH4 (g) + 2 O2 (g) CO2 (g) + 2 H2O (g)
Formula Weights

The amu unit

Defined (since 1961) as:
1/12 mass of the 12C isotope.
12C = 12 amu
Formula Weight (FW)
Sum of the atomic weights for the atoms in a chemical formula
So, the formula weight of calcium chloride, CaCl2, would be
 Ca: 1(40.1 amu)
+ Cl: 2(35.5 amu)
111.1 amu
These are generally reported for ionic compounds
Molecular Weight (MW)
Sum of the atomic weights of the atoms in a molecule
For the molecule ethane, C2H6, the molecular weight would be
Percent Composition
One can find the percentage of the mass of a compound that comes from each of the elements
in the compound by using this equation:
Percent Composition
So the percentage of carbon and hydrogen in ethane (C2H6, molecular mass = 30.0) is:
Moles
Therefore:
The mole
The mole is just a number of things
1 dozen = 12 things
1 pair = 2 things
1 mole = 6.022 x1023 things
Molar Mass
The trick:
By definition,
this is the mass of 1 mol of a substance (i.e., g/mol)
The molar mass of an element is the mass number for the element that we find on the periodic
table
The formula weight (in amu’s) will be the same number as the molar mass (in g/mol)
Using Moles
Moles provide a bridge from the molecular scale to the real-world scale
The number of moles correspond to the number of molecules. 1 mole of any substance has the
same number of molecules.
Mole Relationships
One mole of atoms, ions, or molecules contains Avogadro’s number of those particles
One mole of molecules or formula units contains Avogadro’s number times the number of
atoms or ions of each element in the compound
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ee procedures we may undergo).
| | * Standards allow exposure to as much as 5,000 mrems a
1 Monty ; year for those who work with and around. radioactive
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terms of the time required for half of the
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chemicals in the Saline Test. His doctor advised never. o let nicl
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radioactive decay A po!
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Half-Life
Bene — Ejected Helium ‘Terrestrial (from the ground)
if you live in a state that borders the Gulf or Adanuc Coasts, add 16 mrem
Lfyoulive in the Colorado Plateau ares, add 63 mrem
eta— Ejected Electron |if you live anywhere alse in the continental US, add 30 mrem
||House Construction
The time required for the
= Positron — Ejected Anti-Beta | Fyoulive ina stone, adobe, brickor concrete building, add 7 mrem
|PowerPlants 1000 ~« amount of radioactive material
{if youlive within 50 miles of a nuclear power plant, add 0.01 mrem
- particle jifyoulive within $0 miles ofa coal-fired power plant, add 0.03 mem
{From food (Carbon-14 and Potassium-40) & from water (radon dissolvedin water)
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 Half-life\
: Number of Fraction of Amount * Originates from U-238 which occurs naturally /
Ess) - ‘Half-Lives Initial Amount Remaining( Nin most types of granite
FE Remaining ian
._.* Radon-222 has a half-life of 3.825 days
ait, 20.00 (initial) —~
‘a i oe alpha emissions
1/2 10.00.
1/4 5.00
1/8 2.50
1/16 125.
1/32 9.625
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Decay of Plutonium-238

Lo sf
Ts
Radioactivity

Radon
3.8 Days

Half-Lives
Radium
1,620 Years
i. * Aplot the logarithm of activity vs. the time isa straight
) Nine. se
The quantity of any radioactive element will | dirtinish: by-< a ;
factar of 1000 during-a 1( val At span. | Jinan
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URANIUM 238 (U238) LLL

RADIOACTIVE DECAY
2 [pe of nuclide
ie4 + |jradiation
4.510% years
i
uranium—238

thorium—234 24.5 days

KKK DDR

protactiniurmn—234 1.14 minutes

RF DBDRBDBRRK

uranium—234 2:33 x1 oS years

thoriurn—230 8.3 x104 years
radiurn—226 1530 years
radon—222 3.825 days
polonium—218 3.05 minutes
lead—214 26.8 minutes

bismuth—214 13.7 minutes

poloniurn—214 1.5x1074seconds
lead—210 22 years

bismuth—210 5 days

polonium—210 140 days

lead—206 stable

Area within a mineral grain

from which radon can poten-
tially escape into pore space.

) Radium atom betore it decays

to radon
\a
PX } ~ Parent #ofDecay Final Product
e Radioisotope Steps of Series” Newly formed
radon atom

A -Uranium-238 (14) Lead-206 — Most of the racon produced

© Thoriuin-232 10 Lead-208.) 8 within a mineral grain remains

embedded in the grain, only
10 to 50 percent escapes to

| Uranium-235 1 Lead-207
enter the pore space. If water
is present in the pore space,
the radon atom can more easily
remain in the pore space; if

__Plutonium-241 3 Bismuth-209 the pore space is dry. the radon

atom may shoot across the pore
and embed in another grain
where it cannot move

pe
High i
Permeability |
Uranium Series Thorium Series | Actinium Series
Half i
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Half Life “TheeEmits |' Half Life
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Low
Permeability

5 0.1

. Originates from U-238 which occurs naturally : , 1

in most types of granite BBE: 10

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=
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 Characteristic of a Good Fuel
e High Calor ific Value
© Moderate Ignition Temperature
e Low Moisture Content
e Low Content of non combustible matter
© Incase a solid fuel , the ash content should be less and
the size should be uniform
© Readily available in bulk at low cost
© Products of combustion should not be harmful
¢ Combustion should be easily controllable.
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© Caloric Value; the amount of heat liberated when unit mass of

fuel is completely burnt in air.

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Environmental Impact
for solid or liquid cal/g , kcal/kg or J/kg
For gaseous fuel kcal/cm3 or J/m3
LECTURE 5
Gross or Higher Calorific value (GCV)
the amount of heat liberated when unit mass/ volume of the
fuel is burnt completely in air and the products of
combustion are cooled to room temperature

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US Energy Consumption by Source
© Net or Lower Calorific Value (NCV)
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material which on proper burning in air gives a are allowed to escape the atmosphere. Natural Renewables , 8%
large amount of heat that can be used Gas
23%
economically for domestic and industrial © GCV = NCV + latent Heat of condensation of steam
purposes. ¢ NCV = GCV - 9x Mass of Hydrogen x Latent Heat of
Steam
¢ NCV = GCV — 0.09 x % of Hydrogen x latent Heat of
¢ Example: wood, charcoal, coal, kerosene, petro,
Steam
diesel, producer gas, water, gas, natural gas etc. Petroleum
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¢ During the process of combustion, C and H of the fuel © Coal
¢ The calorimeter used to determine the energy change during
combine with oxygen of air to form CO2 and H20
a reaction accurately is known as a bomb calorimeter. The © Petroleum
respectively
modern Bomb calorimeter is a development of the original © Natural Gas
calorimeter of Berthelot. The modern bomb calorimeter is
© Nuclear Fission
¢ Heat content of combustion products (CO2 and H20 , etc) made of corrosion resisting steel in which the combination
being lower that that of reactants (C,H, etc of fuel) the Bomb Calorimeter.
chemical fuel release heat during their combustion process

se y
(e

2 By

&
a a a x
The bomb calorimeter is a type of constant-volume calorimeter
COAL
COAL
Classification used to measure the combustion heat of oxygen-burnable samples.
Four critical parts are needed in every bomb calorimeter.
¢ Based on their Origin The bomb calorimeter is a laboratory instrument used to measure

|. Primary(Natural) Fuels
the amount of a sample’s combustion heat or heat power when World Coal Consumption
excess oxygen combustion occurs. The purpose of this research is
to determine the effect of using the bomb calorimeter on the © World coal consumption is projected to
2. Secondary (Derived) Fuels ability of physics students to process science. Influences involve
increase from 5.3 billion tons in 1997 to 7.6
the efficacy of using the devices and learning how to develop the
abilities of the scientific method of students before and after using billion tons in 2020.
These are again subdivided into solid, liquid materials.
¢ US annual coal consumption is approximately
If the heat of the capacity calorimeter Ccal of to the calorimeter is
and gaseous according to their physical known, then one determines the heat generated by a only needs to 1 billion tons
note the change in the temperature process. Calorimetryis widely
state.
used in present-day laboratories.

XX wy
Ee =
Uses of Bomb Calorimeter ‘e
L
S

Table-1. Classification of Fuels

Physical state Primary fuel Secondary fuel

To calculate the amount of heat (calories) in food, oxygen
Solid Wood, Peat, Charcoal, Coke bomb calorimeters are useful in food testing laboratories.
Coal, Lignite
The total heat of the fuel is désermined by increasing the Coal Reserves (M metric tons)
Liquid Crude petroleum Petrol, Kerosene,
temperature and the real mass of the fuel.
Africa, 67.7 North
Diesel, Synthetic
Far East
petrol
© Heat given by the combustion of coal + Heat given by the and

Gas Natural gas Producer gas, combustion of fuse wire = Heat taken by the water and Oceania,

Water gas, Coal gas, calorimeter. 322.2 US— 275.5

Biogas, LPG World -1088.6

cas WwW. ee

) America,
23.7 Middle
East, 0.2
ee

288.3
5

XS Source: http:
/ / www.cia.dB6RE40?ePinapatica/table82_html y
(i a)
PETROLEUM
PETROLEUM
Coal Analyses fi = How long can we depend on Petroleum?
© Proximate Analysis e World =
© Ultimate Analysis Petroleum 1016,000 million barrels /73 million bbls /day = 13,967
days= 38.1 years
© Calorific Value
Us
= 21,800 million bbls / 18.9 million bbls / day
© Naturally occurring liquid containing a complex mixture = 1,153 days or 3.16 years
of hydrocarbons (molecules made of C and H atoms) if we keep importing at the current rate
= 21,800 million bbls /9.3 million bbls / day
© Also contains few compounds containing N, S, and O = 2,344 days or 6.4 years
atoms

‘e aS
) 7
a
NATURAL GAS
GAS
EGEE 102-Pisupati
NATURAL
Proximate Analysis (i >
© Moisture
© Volatile Matter Natural Gas
Petroleum Composition WHAT IS IT?
e Ash
Fixed Carbon (obtained by difference) ® Principally methane, CH,, with some ethane (C,H,) and
Element Range (wt%)
propane (C;Hs), and impurities such as CO,, H,S, and N).
Carbon 85-90%
CALORIFIC VALUE
Hydrogen 9-15% © Approximately 1,000 Btu/cu.ft (22,500 Btu/Ib)

Nitrogen 0-0.1%

Sulfur ppm- 4%

‘e Oxygen ppm

(~ a Re EGEE 102-Pisupati ae y
&
eo EGEE 102-Pisupati
y
Ultimate Analysis (elemental composition)
f 2)
Carbon 60
96%
- | Natural Gas Types
Crude Oil Reserves (B bbls)
US—21.8
Hydrogen 2-6% World— 1,016
North S. and e WET- contains HC, other than Methane and ethane
Nitrogen 1-2% America, 55.1 Central
merica, 89.5 W. Europe, ¢ SOUR- contains H ,S,which is highly undesirable due to
18.8
Sulfur 0.5-5% corrosion, and SO, formation upon combustion.
Far East and
Oceania, 44
Oxygen 1-30%
Africa, 74.9

E Europe &
Se y FSU, 58.9 Reserves (Trillion Cu. Ft)
a
& é "i yy Far East and North America,
Oceania, 375.4 261.3 W. Europe,
Ga
Calorific Value (Heating Value) Africa, 409.7 169.5

¢ Heating or Calorific Value is the amount of heat released

when a unit mass of fuel is burned (Btu/b. or cal/g) Production and Consumption (mn bbls/day)
BP Amoco Statistical Review of World Energy 2000 (http://www.bp.com) Middle East,
E. Europe and

© Calorific value has implications for pollution measurements FSU, 1947.6

1836.2
such as SO2 whose emissions are calculated on a Ib per
million Btu basis US - 167T Cu. ft
© World
World - 5210T cu. ft
© Production — 73
c.&S.

>
America, 227.9
EGEE 102-Pisupati
© United States
© Production — 9.2 oN
© Consumption— 18.9 How long can we depend on Natural
Gas?
‘eo
(E ay / e US= 166 T. Cu. Ft/ 21.7 T. Cu. Ft per year
(1999) = 7.6 years
Coal Ranks (~ This simplified drawing shows many of ”)
e World = 5240 T cu. Ft/84.2 T. Cu.ft per year
¢ There are 4 general ranks for coals: ; a refinery's most important processes.
enero! f Lee
=62 years
© Lignite low rank
© Subbituminous
¢ Bituminous
e Anthracite High rank
j) Jer Frew

EGEE 102-Pisupati
oO

AMATION Fue
&

Utilization-Combustion
Premium Fuel
© J
INDUSTRIAL FUEL

ASPHALT BASE
© Highest calorific value of any fossil fuel (1,000 Btu/cu. ft. or
24,000 Btu/Ib)
a 1) Eup propuersS

© Noash in the fuel - no mess

¢ Easy transportation and no storage space required
Coal’s Future © Better combustion efficiency
One Barrel of Oil (42 US gallons) © Less CO, emissions compared to oil and coal for the same
Lifetime (of a resource) = _Reserves heat release
produces ...
Annual Use

Reserves to Production Ratio (R/P Ratio) © Gasoline (19.5 Gallons)

World 1173 G Tons / 4.33 G Tons/y © Distillate Fuel Oil (9.2)
= 271 Years © Kerosene (4.1) EGEE 102-Pisupati
(e

USA 277 G Tons/0. 99 G Tons/y

&

© Residual Fuel Oil (2.3)

= 280 Years ° Lubricating Oil, Asphalt, Wax (2)

Note: Reserves are likely to increase as well as ¢ Petrochemicals for plastics and polymers (2)
decrease, usage is also expected to change © Total Yield: 44.4 gallons
‘S
GF a

Comparison of Fossil Fuels Greenhouse Gas Emissions

Distr of U.S. Emissi by ih Gas, 1999
Composition Heating Value
Coal CH 98 13, 000
Btu/ 1b
Oil CH, 20,000
Btu/ lb
Natural Gas CH, 22,000 Btu/1lb
All also contain oxygen, sulfur,
nitrogen etc.
1 gal of Petroleum = 10 Ib of Coal = Source: ELA, Emissions of Greenhouse Gases in the United States 1999

ea =ee
150 cu. ft Gas
X y ay
Gi By
Nitrogen Oxides (NO,)
Cost of Energy/MMBtu for oil Nitrogen oxides, like hydrocarbons, are precursors to
© Price of oil is usually given in $ / barrel the formation of ground level ozone and thereby to
¢ If the price is $22/barrel photochemical smog
© One Barrel of oil has 5,800,000 Btu e Precursors to the formation of acid rain
¢ Long-term exposures to NO, may lead to increased
susceptibility to respiratory infection and may cause
permanent alterations in the ling.

Cost per MMBtu= SEE Teer

1Barrel 5.8MMBtu
Carbon Monoxide
© Product of incomplete combustion
© Reduces the flow of oxygen in the bloodstream
7
© Particularly dangerous to persons with heart disease.
3 By

Cost of Energy per MMBtu- Natural gas Sulfur Dioxide

© Usually price is given as $/ 1,000 Cu. Ft
High concentrations of SO, can result in temporary
breathing impairment for asthmatic children and adults
© Say $7.44/1000Cu. Ft (PA) * in conjunction with high levels of PM, include respiratory
e Energy Content 1,000 Btu/Cu. Ft illness, alterations in the lungs’ defenses, and aggravation of
existing cardiovascular disease.
e Together, SO, and NO, are the major precursors to
6 acidic deposition (acid rain)
Cost pee MMBea = $7.44 ye Cuft 10° Btu
® major precursor to PM,;, which is a significant health
1000 Cu.Ft 1,000 Btu MMBtu concern

Particulate Matter
¢ Health effects
S y
° Visibility impairment
¢ Atmospheric deposition
US Energy use and Environmental
° Aesthetic damage
Consequences
Emissions

co, Additional Resources

co © http: //www.epa.gov/air/aqtrnd00/

= NO,
© http: / / www.epa.gov/airmarkets/acidrain/
© http://www. epa.gov/globalwarming,
Carbon http: / /www.epa.gov/oar/oaqps/gooduphigh/
Hydrogen Particulate Matter
e http: Lf WWW. €pa. gov /air/ concerns /#smog
Nitrogen PMio
Sulfur PM,;
Oxygen NH,
& y
a

US Air Emissions, Mtons (1999)

Gas Emissions

Carbon Dioxide 1,520

Carbon Monoxide 97.4

Lead 4.1

NO, 25.4
SO, 18.8
Particulate Matter 2351;

‘S
~
Flash Estimate of U.S. Carbon Dioxide Emissions from
Fossil Energy Consumption by Fuel
(Million Metric Tons of Carbon)

mkt Y 1990 1991 1992 1993 1994 1995 1996 7 TS Pa ad

Petroleum 590 576 587 588 600 596 619 625 634 650 657
Coal 485 481 486 502 508 510 533 547 550 552 570
Natural Gas 273 «278 «= 286 S295) 302: 314 320. 3321 310 315 330

Total Fossil 1,349 1,335 1,359 1,385 1,410 1,421 1,471 1,493 1,49! 1,517 1,558
Fuels

Notes:
Preliminary estimate.
Source: Energy Information Administration.
 Chemical Fuels

LECTURE 6 ee ay

Before the dinosaurs, many Over millions of years, the plants Heat and pressure turned
giant plants died in swamps. —_ were buried under water and dirt. the dead plants into coal.
RTT
Source: www.emc.maricopa.edu/faculty/farabee/BIOBK/aK.

The US has the wo il reserves, over

do Work 267 billion tons, Ni years at the
current usage rate.
(http://factsonenergy.com/wp-content/uploads/2007/09/coal_most_abundant_energy_source.pdf

Non-Renewable ° Surface Mining= Method 1

— Solar forms: — Least expensive method.
Carriers of US Coal Deposits
(Million Short Tons)
— Wind © Coal — Used when coal is less than 200 ft below the
Energy: (=
¢ Oil CV aila=m
— Geothermal Electricity — Topsoil layers are removed and then REPLACED after
— Water e Natural Gas
coal layer has been extracted, allowing for the area
* Hydroelectric Rance ¢ Nuclear to be re-planted or used for other natural sites.
* Tidal — Inthe US, it is mandatory that land be returned as
— Biomass closely as possible as was its original state prior to
coal removal.

lur Energy: (20 Surface

U.S. ENERGY CONSUMPTION BY SOURCE

Nearly 50% of the nitrogen oxide (Nox)

| B nonrenewa
2.9% PETROLEUM

transportation Transportation, ng in the atmosphere and 70% of sulfur

HYDROPOWER
renewable
2.7% | y NATURAL GAS 22.9% dioxide are direct result of emissions
nonrenewable
Electricity Heating. manufacturing, electricity released when coal is burned.
GEOTHERMAL 0.3% / ) COAL 23.2%
renewable nonrenewable
} Heating, electricity Electricity, manufacturing

+ WIND 0.1% URANIUM 8.1%

These are directly responsible for crop
renewable
Electricity | eS ) =< nonrenewable
failuresfrom §=—~—_—«s formation (later
explained in this presentation).
SOLAR & OTHER 0.1% | PROPANE
renewable nonrenewable
Light, heating. electricity Manufacturing, heating

Source: EIA Photos courtesy of

Human Healt

common Si source, but

what /S a fossil fuel? Also called Deep Mining, used when deposits Workers can contract
are between 200ft and 1,000ft deep. lung diseases, skin
diseases and ulcers from
w-Winyvdrocarbon deposit ©. 9) = Elevators must be used to haul machinery and
coal dust and other
petroleum, coal, or natural gas, personnel. impurities mined.
Expensive process, includes much specialized
derived from living matter of a Burning coal produces
machinery. huge amounts of smog, a , Ny
previous geologic time and used also related to illness.
Risk of cave-ins and suffocation hazards. Photos courtesy of
for fuel. coalcampmemories.com

Avail ,
Another i Y
Global Fossil Fuel Consumption in 2004

United States hai ;

* Oilis derived from Petroleum, a definition of
Over half of the European Union -19 By ma
which is : k, flamma
fossil fuels in the Japan i I

world are Russia si ma

consumed by
Other

China and Hong Kong

ne
Developed

hay Malice il} )fy<1

ERaram ufone) noo
“countries? ll aa
Other Develop
Union
countries that 0 soo 1,000 1,500 2,000
Million Tonnes of Oil Equivalent
are considered Coal oil 1 Natural Gas
Diagram
“advanced.” 1 includes 25 countries. 2 includes 135 Countries
Source: EarthTrends and the international Energy Agency, 2006.

ee Ri | eatne Value and

ig a smelly, yellow-to-black liquid
Allow for Cleaner Burning and is usually found in underground areas
called reservoirs (crude oil = petroleum).
* Common impurities are removed : The top 5 OIL-producing nations are Saudi
OL) Arabia, USSR, USA, Iran, China.
NVI ena 58% of the crude oil used for fuel and products
RON crexs ara
Seis in the US is imported from other nations.
—Dirt The top 5 oil-producing states are Texas,
Alaska, California, Louisiana, and Oklahoma.
— Other unwanted materials
 st First be REFINED to derive Hydrogen-t 4
Oil, Gas, and other Fuels!
¢ Ablend of natural gas and hydrogen,
* Here’s a partial! list of what oil is currently used
Refineries are tremendously expensive operations. usually 12% H and 80% NG.
for:
Petroleum (crude) is carefully heated to specific * Can reduce emissions of Nitrogen Oxides by
temps, and the fumes are collected and cooled back 30-50% without affecting the performance
Cooling, computers, fertilizer, feedstocks, heating, into liquid form (condensates). of regular natural gas engines.
adhesives, paint, plastics, clothing, building materials,
medicine, trucks, cars, tractors, fencing, tools, rope,
Gasoline, diesel, kerosene, etc, all are products of * These 2 fuels come mainly from domestic
diesel, gasoline, solvents, lubricants, laboratory various fume-collection and distillation. supplies, lessening the US’s dependency on
materials, colognes, detergents, and much, much The danger of explosions is constant and extreme. icelg-ti-4aneelelalag (=1o8
more ... (you are probably wearing oil-related products right A typical refinery can process 500,000gal of
now!) petroleum per day.

Why Do We Peel wal =

The world population has been steadily increasing,
more people means greater energy demand. * Fuel that is easily stored in
Several countries are achieving higher levels of pressurized tanks.
development today, more building and
¢ Used as fuel for cooking,
transportation means greater demand for energy.
transportation.
Oil is an extremely versatile fuel, it can be
transformed into many other products. Also a by-product of oil
Oil-derived fuels (such a gasoline) burn easily, burn refining.
HOT, and the current transportation industry is Burns cleaner than gasoline or
designed to use it nearly exclusively. diesel.

* Drilling “Rigs” are constructed Fossil Fuel, formed similarly oil, found in Coal, Oil and Natural Gas products are
both on land and in the ocean petroleum. extremely widespread, and in higher demand
to dig into oil reservoirs and Removed from Earth by drilling, the each passing day.
search for new oil deposits.
pressure is usually sufficient to allow it flow
Supplies will eventually be depleted.
to the surface.
Working these rigs can be very m Use of these products are filling landfills,
Colorless, odorless gas with a simple Boch t)
hazardous, safety is a major
chemical structure (CH,)
polluting land, rivers, lakes, oceans, and air.
concern since any petroleum
found is under pressure and
Courtesy of BVM Corp.
24% of the world’s energy is derived by Oil spills are common, on average, 12 spills
highly flammable. burning natural gas. over 1000 gallons each occur every day.

has Greatly
S

¢ Land-based rigs are Canals dug for pipelines promote soil erosion.
Both Natural Gas and Oil
smaller and more Roads and levees erected for access to rigs
are often found along
numerous than offshore. hinders natural water flow, re-directing it into
smaller faults deep within
waterways causing additional soil loss.
Smaller crews are idatea lado p
needed to operate (usually ia
ay Pollutants from drilling enters the environment,
Coastal and northern
5-8 workers). ’ killing delicate wetland vegetation.
Roe larNee-lelelarer-laimnw alan
, , AYO (hoes: Increased use of larger drilling equipment
Fairly easily moved from ics pe ra) natural gas reserves.
necessitates deeper dredging of access canals,
place to place. Baan li
i \\ |

Louisiana is one of the top

compounding the erosion problem.
Photo: Compliance Partners, Inc 5 natural gas-producing
states in the US.

DR Bin; NI
Disrupts Earth’s natural strata
| ¢ Threat of producing sinkholes
Offshore rigs are much
larger and more Used in homes, businesses, industry, vehicles ¢ Possibility of water
expensive to build. and power plants. contamination

Larger crews are needed Consumption is expected to rise by 50% by

to operate (usually 25-40 2025. OIL SPILLS
workers).
Since it is colorless and odorless, a scent is
Extremely hard to move Destroy environment
added to it for safety purposes — called a
from place to place. Kills Wildlife
“mercaptan” — giving it a sulfur-based, rotten-
(Credit: Minerals Management Service, Expensive to clean-up
US Department of the Interior) egg type smell that cannot be removed.

* Compressed Natural Gas (CNG) is an alternative fuel Environment is damaged, usually coastline
for gas and diesel engines, is stored in tanks similar wildlife losses are high.
« “Pump jacks” move the
crude up from the well to acetylene. Most of the oil is never recovered (usually only
into pipelines and * Liquefied Natural Gas (LNG) is used in large-scale 10-20%) can be salvaged.
storage tanks. industry. Cooled to -260F, it is now being used as a Oil sinks to seafloor, killing important
Other stations pump the fuel for trucking and ocean-going vessels. decomposers, natural balance is interrupted.
oil to larger tanks or Oil is eventually decomposed by marine
* CNG and LNG Only accounts for 4% of natural gas
waiting barges. organisms, however, it could enter the food
consumption worldwide. r om
Crude is taken to refinery chain of ocean wildlife, possible human
for production into fuel.
a ee contamination threat.

LNG
 Fossil F
ollution
CWolceleVlacM cat
=n eT aol
a
* Ran aground in Prince of greenhouse gases (CO5) (source: us Pa).
William Sound, Alaska, * Failing to reduce these emissions may likely
spilling more than 11 million cause our global climate to change ... and if it
gallons of crude. changes, agriculture will definitely change.
¢ Human Illness
The average temp has
risen 1.6 deg F since
Crop failures 1880, and at a steep
rate since 1960. To see
NASA’s data on global
Acid Rain temps, click

Acid Rain( Explained via

eee
ch as coal or solar
to create electricity.
The Valdez Atmosphere
spill affected
over 1,200
SOURCES i Pollutants in i
miles of Coud Water
Alaskan coast. voc NX & Preciptiaon 5
Wet
Deposition

DAY 56, May 18

470 miles RECEPTORS
(farthest southwest observation)
Courtesy of MIT

BURNING COAL
TO MAKE ELECTRICITY
Power Plant
Currently, most
_ boiler
electricity is
based rigs, pump-jacks, storage containers, pxefatec
leo dal celta
refineries, and transport vehicles. nonrenewable
Spills on agricultural-producing land and irrigation Normal Rain (5.6)
energy sources.
sources usually result in costly clean-up and Pure Water (7.0) *
containment procedures.
Often spills can alter the land’s ability to produce,
rendering the soil unusable for decades or longer.
To report an oil spill, contact the EPA at (800) 424-
8802

Calcium, a neces soil filtration, is Water Generator

pies Transformer
depleted by acid rain.
Condenser Cooling Water eS
The loss of calcium can harm plant growth and
result in plant die-offs.
Heavy metals (such as aluminum) can be absorbed
Wheat crop fails to grow where Oil by plants due to calcium depletion, resulting in
Production rig once stood —30 yrs ago
diminished growth rates and plant die-offs.
« oe wl
Sludge pits, storage tanks, fuel tank leaks, as
| ae >
bl om
we
Aluminum has been linked to Alzheimer’s disease in
well as numerous waste products from oil and aes
gas production can devastate the soil’s ability
to grow marketable crops in the US. Research also links acid rain to climate changes.

Another En Most electricity in the U.S.A. is generated by coal

burning power plants because it is the cheapest to
use and produces large amounts of energy.
* Areas where pipelines * As you recall, Fossil fuels are NON-renewable,
are buried cannot be and are found beneath the Earth’s crust.
used to grow crops. * Fossil fuels do not burn clean.
Fossil fuels are the most commonly
* Strips of land are
usually of is also mined from beneath the Earth’s
used nonrenewable resources.
considerable length. crust, and by controlling a reaction called The ultimate source of the energy in
* Blowouts can occur. “fission”, tremendous heat can be achieved.
fossil fuels is from the sun.
* Supplies are limited, but the energy it can create
burns much cleaner than fossil fuels. Photosynthetic plants and marine algae
lock this energy into organic matter.
When we burn plants, coal, oil, or gas,
Drilling for F
we release the sun's trapped energy.
— several types, must be mined, acid rain, Coal is an organic rock that
« As more workers transportation expensive.
originally came from dead swamp
are needed for — Hazardous retrieval and refining process, most
increased is imported (costly), spills, acid rain. grass that compacted over millions
supplies, an a — Same problems of production as oil,
of years.
le Li aN high transportation costs.
injuries can be vais (Uranium) — public acceptance a problem, The fossil fuel coal formed from the
expected if safety ; dangerous waste, plants are expensive to build.
MISMO Ct-1e- 110) Le ad remains of plants that lived and died
strictly enforced.
Courtesy
of Canadian-Wellsite.com
around 100 to 400 million years ago,
when parts of the earth were covered
with huge swampy forests.
 ws Be SG
CRYSTALLIZATION
CRYSTALLIZATION ¢ Allotropes 2 ¢ ea
ff] Unconventional

Conventional
e*.? sia aed
cet , = ae cee if me =
Crystallization Py) ee Fee

flese ee SEAL

GAS/SOURCE ROCK
ive eee Eee ay
|

bk
LECTURE 7
d
In diamond, each
carbon atom in the
erior of the diamond
In graphite, the
carbon atoms are
linked in widely
* Itis defined as a spontaneous arrangement of the particle into ingly bonded to spaced layers of
a repetitive order. t . The array hexagonal arrays.
OS + In other words a process in which crystals are formed either ompact. gons ani
from something that has been melted or from a solution is
Of the fossil fuels, natural gas produces usually termed as crystallization.
« The process of crystallization involves adsorption of solutes at Diamond, graphite, and fullerenes are
the least amount of pollution. growing crystal surfaces or planes.
* Acrystal is defined as a solid particle,which is formed by the
solidification process under suitable environment in which
crystalline allotropes of carbon.
structural units are arranged by a fixed geometric pattern.
Natural gas is an energy source ¢ Allotropes are two or more different molecular forms of the same
Crystal Structure and element in the same physical state.
often used for heating, cooking, and Unit Cells

electricity generation. Only a few elements have allotropes.

* Crystal Structure and Unit Cells
Petroleum oil is a nonrenewable fossil ¢ Inaddition to carbon, these include phosphorus, sulfur, oxygen (O, and
What determines the shape of a crystal? O;), boron, and antimony.
fuel usually found underground in
reservoirs located in sandstone or ¢What structural properties make
fullerene nanotubes the strongest
limestone. This fossil fuel is made from lattice
lattice
material inthe world?
sea plants and animals.
The shape of a crystal reflects the
Gasoline is made from the fossil fuel arrangement of the particles within the Each carbon atom is covalently bonded to three other carbon atoms. The
structure creates a spherical cage or cylindrical tube. This shape allows force to be
oil. solid. distributed evenly across the surface so that the entire structure can withstand
great force and is extremely strong.

¢ Insodium chloride,
HOW ARE OIL AND GAS MADE sodium ions and chloride * Non-Crystalline Solids I
ions are closely packed in
OCEAN
300-400 million years ago
[ OCEAN
50-100 million years ago
a regular array. Not all solids are crystalline in form; some
a ae ta z
¢ Theions vibrate about solids are amorphous. —
fixed points in the crystal.
* Anamorphous solid lacks an ordered internal structure.

* Crystal Systems * Rubber, plastic, and asphalt are amorphous solids.

Tiny sea plants and animais died Over millions of years, the remains Today, we drill down through laye
per an of sand, silt, and rock to reach ¢ Theiratomsare randomly arranged.
Over time, they were covered by the rock formations that contain
layers of silt and sand. oll and gas deposits. Crystals are classified into seven groups, or
Oil and gas are formed from the crystal systems.
A\ ¢ Non-Crystalline Solids a
remains of marine plants, animals and \
‘ '
c Te, lc ‘ Ie! Other examples of amorphous solids are glasses.
microorganisms that lived in seas fa ‘ | ita,
Wa
her IST
rd
ffTs
a ag =) a © Aglass is a transparent fusion product of inorganic substances that have
millions of years ago. azbec
a=B=y7=90°
atbte
a=P=y=90"
atbeec
B=y=90% a
atbec
at Btyt90° a=B=90",
y= 120°
asbte cooled to a rigid state without crystallizing.

© Glasses are sometimes called supercooled liquids.

Propane is a nonrenewable fossil ¢ Theirregular internal structures are intermediate between those of a
crystalline solid and those of a free-flowing liquid.

fuel that is a derivative of natural *The general properties of solids reflect the orderly
gas and petroleum arrangement and the fixed locations of their
particles.

‘Gen The shape of a crystal reflects the arrangement of

When present i the particles within the solid.
supplies of
nonrenewable Crystal Shapes

up, there will be The seven crystal systems differ in terms

of the angles between
the faces and in. ¢ Shape is determined by atomic arrangemen
e number of edges of equal length on each face. |
no more. * Some directions grow faster than others

210 YEARS The shape of a crystal depends on the

¢ Morphology can be distinct for the conditions
42 YEARS arrangement of particles within it. and speed of mineral nucleation/growth (an
¢ Thesmallest group of particles within a crystal that retains the geometric
60 YEARS shape of the crystal is known as a unit cell. growth along specific axes) frackous

Acrystal lattice is a repeating array of any

one of fourteen kinds of unit cells. Ostwald Ripening
¢ Each crystal system can be composed of from one to four types of unit cells.
Primary Sources re RT Larger crystals are more stable than smaller crystals — the
The figure below shows the three kinds of unit cells that can make up a cubic energy of a system will naturally trend towards the
Oil Gasoline crystal system.
formation of larger crystals at the expense of smaller ones
a MCU avT Rey]
a etre aS
Blowing Wind a Tadilelay B

Flowing Water Hydrogen

eifeyaate bs) (crcl
Seal ital ense, the smaller crystals are ‘feeding’ the larg
le Cubic Body-Centered ugh a series of dissolution and precipit
unit cell, Ina body-centered cubic unit inatececentend
cell, the atoms or ions are atthe there are
corners and in the center of an e

Small crystals...
¢ Allotropes =
In the absence of ripening, get a lot of very
Some substances can exist in more than one
small crystals forming and no larger crystals.
form.
This results in a more massive arrangement

* Diamondis one crystalline form of carbon.

Microcrystalline examples (Chert)
© Adifferent form of carbon is graphite. Massive deposits (common in ore deposits)
* 1n1985, a third crystalline form of carbon was discovered. This form is
called buckminsterfullerene.
 3.1. Crystal structures \C. Zinc blende or sphalerite structure
Topotactic Alignment (Mineralogical term for zinc sulfide (ZnS)
.4. Ceramic crystal structures atoms are located in all corners and face positions of a cubic,
gnment of smaller grains in space — due to magnetic att: Zn atoms fill the interior in tetrahedral positions in covalent

1%‘ characteritic:
nitude of the electrical charge on each of the compor
cations must be in balance with the anions. 3 .1.4.2.A,,X,-type crystal structures
chemical formula of a compound indicates the ratio of cations
; or the composition that achieves this charge balance.
This structure has dissimilar charges
iicium ion has a +2 charge (Ca?*) of cations and anions.
A fluorine ion has a —1 charge (F’) — The chemical formula is A,,X,
where m and/orp #1. ~—
E or amorphous material is a material that dc Example : CaF,
-range atomic order. ae rolta isis 0.8 and the c

Table 3.3 Coordination Numbers and Geometries for

Various Cation-Anion Radius Ratios (re/ra)
Coordination Cation~Anion “Coordination — 3.1. Crystal structures
Number Geometry

.5. Silicate ceramics

les are materials composed primarily of silicon and oxygen.

unit cell defines the crystal structure by virtue of its geometry— unit of silicates is SiO, + tetrahedron, which is each ato:
|the atom positions within O.185-0,225
(located in the corners of tetrahedron) is bonded to four«
ated at the center of tetrahedron).
on silicates are rocks, clays, sand, anda

0,225-0,414

0.414-0.732

Crystal structures
mane crystal structures a or silicon dioxide (SiO2) is the most simple silicate.
- structure has a cubic geometry with atoms located at each of n atom at every corner of each tetrahedron shares the !
1e corners and the centers of all the cube faces. n atoms with the adjacent tetrahedral and this configuration.
1y metals have this FCC structure. network structure. i
rial is electrically neutral and all atoms have stable

3.1.4. Ceramic crystal structures

fost ceramics are composed by an equal number of cations

pre relation between the cube edge length,a and the atomic rad
a=2R 2 TETRAHEDRAL
TETRAHEDRAL
FCC structure has 4 whole atoms [= (8 x 1/8) + (6 x %)]
p crystalline structure is formed if these tetrahedra are arrayed in a
dination number (CN) is a number that an atom touc gular and ordered manner. There are 3 primary polymorphic
st neighbour atoms. stalline forms of silica, they are: quarts, cristobalite, and tridymite.
ination number of FCC is 12

ing factor (APF) apr = Y°L0f atomsi interatomic bonding is strong so that they have relati
perature. (€g Tmnquartz 1710 °C).

Anonerystalline solid
or g
_can also be formed from

BCC structure has a cubic unit cell with atoms located at each
the comers and a single atom at the cube center.

3.1.5.2. The Silicates

cygen atom at every corner of each tetrahedron shares the other
edral to form complex structures.
om positively charged cations such as Ca?* Mg _, and Al can
| B. Cesium chloride structures ° of the structures. These cations compensate the negativ
_ The anions are situated a each of the corners of a cube, whereas of SiO, * to form
je cube center is a single cation. l compound and
his is not a BCC crystal structure! ni E bonding
e coordination number of both cations and anions is 8.
Atomic
view

crystal
structure

2D - cut

Spatial agglomeration of crystals Guling plane

One of the most common clay minerals and simple two-layer silicate
sheet structure is kaolinite.
Its formula is Al2(Siz05)(OH),4 Purpose of Crystallizer
The OH: and the O7 ions in the anion midplane has a strong ionic-
covalent bonding, whereas
the adjacent sheets
* Used to recover pure solids from solution NUCLEATION
have weak van der Waals A.Primary Nucleation: This type of nucleation is
bondings. + Highly desirable end product because of: homogenous(spontaneous).
— Exceptional purity
— Ease of handling
— Long shelf life
B. Secondary Nucleation(induced by crystals): It is of
heterogenous type(induced by foreign particles).
* One of the final treatment steps in the
purification and concentration of insulin

* 98% of the insulin must be crystallized

Callister Jr, W.D., 2005
CRYSTALLIZATION UNIT

3.1. Crystal structures

3.1.6. Carbon

Carbon is an element that exsist in various forms, from poymo a Continuous or Batch Design |
to amorphous sates. a CRYSTAL
Carbon is not classified as metal, ceramic or polymer, however
sometimes it is classified as a ceramic ———-+ polymorphic
* Benefits of Continuous CinO) als
— Can maintain solution in supersaturated state
3.1.6.1. Diamond * Every crystal is sorrounded by a layer of liquid known as
— Large fluidized bed for crystallization stagnant layer.
a D — Minimizes operation costs * Once the crystals are formed,nuclei formation stops and
Diamond is a metastable carbon polymorph = @-—-}-_s._ — Minimize down time (startup and shutdown) crystal growth begins.
at RT and atmospheric pressusre. | 2
* From the bulk solution a solute particle diffuse through this
The crystal structure is a variant of the zinc & 6'.. stagnant layer and then reaches the surface of the crystal.
blende. ~~ @, 1? * Benefits of Batch % \ * These particles then organize themselves in the crystal lattice.
Itis called the diamond cubic crystal oa a
— Good when have low concentration of product, high —
structure. | @6——o+@_@ * This phenomenon continues at the surface at a slow rate.
e@ @ rm viscosity or many impurities
Callister Jr, W.D., 2005 @
— Can produce high quality crystal
CRYSTALLIZATION UNIT
3.1.6.3. Fullerenes and carbon nanotubes

Fullerenes is a polymorphic of carbon (1985).

The structure consists of a hollow spherical cluster of 60 carbon atoms
and is called a C60 molecule.
Amolecule is composed of groups of carbon atoms that are bonded to
One another to from both hexagon (six-carbon atom) and pentagon MECHANISM OF
(five-carbon atom) geometrical configurations.
CRYSTALLIZATION CRYSTAL GROWTH
erga Its commercial name is buckminsterfullerene.
* The formation of crystal from solution involves three steps:
; a Y os Invented by R. Buckminster Fuller (1985) Keep crystal growth vessel away from sources of mechanical
A. Supersaturation agitation(eg:vibrations)
K a D ®
ee \ / © “Soccer ball symmetry” B. Nucleation
| = —e 20 hexagon and 12 pentagon are arrayed Set-up away from vacuum pumps, hoods, doors, drawers and
q2 é \ a Q) e in such way that no two pentagons share onelan
x Ss vee a common side. C. Crystal growth
a > Q © Callister Jr, W.D., 2005 Leave samples alone for one week.
o by

Carbon nanotube structure consists of a single sheet of graphite,

rolled into a tube & both ends are capped with fullerene hemispheres.
The nano represents that the tube diameter is on the order of a
nanometer.
Ithas a very good aspect ratio; which the length of the molecule is much
greater than its diameter.
Mechanism of Crystallization
PRESENCE OF ANOTHER
Crystal nucleation and amorphous precipitates SUBSTANCE
are in competition during supersaturation Sodium chloride(NaCl) crystallized from aqueous solutions
conditions produces cubic crystals.

If NaCl is crystallized from a solution containing a small

* Nucleation favored by slowly exceeding the
Callister Jr, W.D., 2005
amount of urea,the crystals obtained will have octahedral
Special properties of CNT: if
- Extremely strong and stiff, relatively ductile equilibrium point of saturation
- Relatively low density — permits time for the protein structure
- Unique and structure-sensitive electrical characteristics
to orient in a crystalline lattice

Some properties:
Another form:
Tensile strength 50-200 GPa
Multiple-walled CNT
Elastic modulus > 10° GPa CRYSTALLIZATION UNIT
(consists of concentric cylinders)
Fracture strain 5% - 20%

SOLVENT
3.1.7. Polymorphism
SUPERSATURATION
CONSIDERATIONS
Polymorphism is a phenomenon when some metals and nonmetals The solvent with moderate solubility is prefer for
may have more than one crystal structure. crystallization.
+ Supersaturation can be achieved by the following methods:
(In elemental solids, it is called allotropy). A. Evaporation of the solvent from the solution.
Example: Presence of benzene can help crystal growth.
“Graphite is stable at ambient condition, whereas diamond is formed
B. Cooling of the saturated solution.
at extremely high pressures.
Avoid highly volatile solvents.
*slron has a BCC structure at RT and FCC structure at 912 °C.
C. Addition of a substance, which is more soluble in solvent
than the solid to be crystallized.

Solvent Method

Sete clear ete Let * Solvents are generally good protein

pom ILENE SSIES SEE ai) precipitants
* Their low dielectric constants lower the
solvating power of their aqueous solutions
* Requires acidic solvent
— For crystallization, an insulin protein falls } |
out of solution at isoelectric point
PH 5.4-5.7

CRYSTALLIZATION UNIT
 Energy and Packing
Solvent Method Evaporation Method * Non dense, random packing

o
y & >
¢ Advantages: « Advantages:
IoC
* at
— Proteins viability not at risk due to — high purity levels downstream
temperature change Disadvantages: Se
* Disadvantages: — Vaporization chamber requires high pressures Cis BY -1 5-1
- Puen nanan oF-(0L.41
01 4
— Possible protein contamination due to — Protein viability very sensitive to high
insufficient downstream solvent recovery temperatures

CRYSTALLIZATION UNIT CRYSTALLIZATION UNIT

Materials and Packin

| <a
Per: / .
Crystal Size and Growth Rate Addition of Zinc lons
Butt)
* Crystal size distribution is important for the production « In the presence of zinc ions, insulin proteins -many ceramics
process; affects: orient to form hexamer structures -some polymers
— downstream processing crystalline SiOz
— solids transport
— caking and storage properties of the material « Zinc ions render insulin insoluble which results
* Correct crystal size vital for economic production in micro-crystallization and precipitation
fare ee
* Crystals produced in commercial crystallization
processes are usually small Human Insulin Hexamer with Zinc ion
— 30 to 100 um in diameter -complex structures
-rapid cooling

CRYSTALLIZATION UNIT noncrystalline SiOz

CRYSTALLIZATION UNIT

Metallic Crystal Structures

Seeding Techniques ¢ How can we stack metal atoms to minimize empty
RATE OF COOLING/TIME space?
* Primary nucleation is the first step in’
* Quality crystals grow best over time in near equilibrium
crystallization - growth of a new crystal 2-dimensions
conditions.
—Can bypass primary nucleation (creation of
* The longer the time, the better the crystals
new crystals) by "seeding" the solution

* Faster crystallization is not as good as slow crystallization. * Secondary nucleation is crystal growth
initiated by contact
* Faster is the crystallization, higher is the chances of lower — Accelerated by "seeding" adding existing
quality crystals.
insulin crystals to perpetuate crystal growth

CRYSTALLIZATION UNIT
Now stack these 2-D layers to make 3-D structures

Metallic Crystal Structures

Cooling Method Crystallizer Design © Tend to be densely packed.

© Reasons for dense packing:

Concentrated solution * Addition of acidic solvent to decrease pH to
gradually cooled below achieve supersaturation
- Typically, only one element is present, so all atomic
saturation temperature radii are the same.
(50-60°C) to generate a Addition of Zinc ions to initiate Insulin - Metallic bonding is not directional.
supersaturated state precipitation
- Nearest neighbor distances tend to be small in
Yields well defined Implementing of “seeding” technique order to lower bond energy.
micron-sized crystals =| * Minimize heat variation to maintain protein - Electron cloud shields cores from each other
Shell and tube heat ga 8 || ogee || |e, stability
exchanger is used to 68 Canada eanl lima ie lead lode co
* Washing and extensive solvent recovery
cool solution
downstream

Atomic Packing Factor (APF)

CRYSTALLIZATION UNIT CRYSTALLIZATION UNIT

Cooling Method Design Equations

Advantages: Crystal quantity = retentiontime- flowrate
APF for a simple cubic structure = 0.52
— High purity downstream Slurry quality = crystal quantity/0.25
Disadvantages: (sg of solution): (sg of crystals)
Specific gravity of slurry=
— Temperature change does not always have a positive 0.25-(sg of solutio)+ 0.75-(sg of crystals) i 5
effect on supersaturation in proteins quality of slurry 1) — 7 (0.5a) 3
— Protein stability may be at risk Volume = : ‘ 3
6.24- (specificgravi tyof slurry)
— Solubility can be relatively insensitive to temperature
at high salt concentrations
— Cooling will only help reach supersaturation in
systems where solubility and temperature are directly
related

CRYSTALLIZATION UNIT CRYSTALLIZATION UNIT

Atomic eal
© APF for a body-centered cubic structure =
a elo) sae
The Structure of Crystalline Solids
Evaporation Method
* Solute dissolves in solution when heated to a
certain temperature (75°C)
* Slowly cooled until crystals precipitate
* Shell and tube heat exchanger is used. to heat
and cool solution

CRYSTALLIZATION UNIT
 FCC Stacking Sequence _ X-Ray Diffraction Pattern
© ABCABC... Stacking Sequence
© 2D Projection
ah ,

Intensity (relative)
uf dtinat home pomdaeeiv deriva
Metals
Hexagonal Close-Packed Structure
60 70 80

Diffraction angle 20
Diffraction pattern for polycrystalline a-iron (BCC) LECTURE 9
(HCP)
© ABAB... Stacking Sequence

© 3D Projection e 2D Projection SUMMARY

Properties of Metals

I ¢ What is a metal?
¢ Take a moment to describe a familiar metal,
a4 such as iron, copper, gold, or silver.
¢ What words did you use— hard, shiny,
PM Xele cele e ie wes PF ielryaiae| smooth?
¢« Chemists classify an element as a metal
based on its properties.
We (ek mee}
¢ Look again at the periodic table.
¢ All of the elements in blue-tinted square
Theoretical Density, p the left of the zigzag line are metals.

pak tha ome

Physical Properties
¢ The physical properties of metals include
shininess, malleability, ductility, and
conductivity.
¢ A malleable (mal ee uh bul) material is one
that can be hammered or rolled into flat
sheets and other shapes.
¢ A ductile material is one that can be pulled
out, or drawn, into a long wire.
¢ For example, copper can be made into thin
ee and wire because it is malleable ai
uctile.

Conductivity is the ability of an object ‘7

Crystals as Building Blocks transfer heat or electricity to another obj
© Some engineering applications require single crystals:
-- diamond single -- turbine blades
Most metals are good conductors.
crystals for abrasives In addition, a few metals are magnetic.
For example, iron (Fe), cobalt (Co), and
Sag Le CEL
lace
Pere coe me RT)
& ' permission.) nickel (Ni) are attracted to magnets and can
be made into magnets like the one in Figure
¢ Properties of crystalline materials
hic Me oir lecte heehee yealloat igo 12
-- Ex: Quartz fractures more easily
Most metals are also solids at room
along some crystal planes than temperature.
olde
However, one metal—mercury (Hg)—is a
liquid at room temperature.
Po lycrysta IS Anisotropic
© Most engineering materials are Figure 12 Properties of Metals: Metals have certain
physical and chemical properties.
Classifying Categorize each of the properties of
metals that are shown as either physical or chemical.

Isot
sotropici
-Hf-W plate with an electron beam weld.
loge c-Rel
Decleor © tect
overall component properties are not directional.
Grain sizes typically range from 1 nm to 2cm
(i.e., from a few to millions of atomic layers).

Teka
Single vs Polycrystals
joss ese 7 SANS EY mm a veteran, bevel a es hnsdeny
-Properties vary with Pg
direction:
-Example: the modulus
iL
a
., Chemical Properties
ey Veadks to Cl” ——» NaC|
a” 5 Lan
eR Elna a=,Q Once)aH . gGe and speed with which an element
combines, or reacts, with other elements and
compounds is called its reactivity. a
* Metals usually react by losing electrons to other
X-Ray Diffraction ¢
atoms. Ten =
Some metals are very reactive.
Cation (metal
face Cnn metal)
¢ For example, you read that sodium (Na) reacts
Electromagnetic Spectrum strongly when exposed to air or water.
¢ To prevent a reaction, sodium and metals like it
1Hz 1kHz 1MHz Frequency (Hz) must be stored under oil in sealed containers.
1.0 10? 108 10° 10"? 105 10'8 10?! 1074 ¢ By comparison, ee (Au) and platinum (Pt) are
als I Infrared l Ultravidlet I I i ' valued for their lack of reactivity and because they
Long Radio Waves Microwaves Visible Light are rare.
Gamma Rays
AM_ Short Radio Waves Rays
J
10? 1.0 107 10 10° 10°71? 105
Tkm Im Tum Tnm
Wavelength, 2 (m)

Diffraction gratings must have spacings comparable to the

wavelength of diffracted radiation. fot
Can’t resolve spacings <A
Spacing is the distance between parallel planes of atoms
¢ The reactivities of other metals fall ¢ The two most common alkaline earth Lanthanides
somewhere between those of sodium and metals are magnesium and calcium. Two rows of elements are placed below the mai
gold. ¢ Mixing magnesium and a small amount of part of the periodic table.
¢ Iron, for example, reacts slowly with oxyge aluminum makes a strong but lightweight This makes the table more compact.
in the air, forming iron oxide, or rust. material used in ladders, airplane parts, The elements in the top row are called the
lanthanides (lan thuh nydz).
¢ Ifiron is not protected by paint or plated automobile wheels, and other products.
Lanthanides are soft, malleable, shiny metals with
with another metal, it will slowly turn to ¢ Calcium compounds are an essential part of high conductivity.
reddish-brown rust. teeth and bones. They are mixed with more common metals to make
alloys.
¢ The destruction of a metal through this ¢ Calcium also helps muscles work properly.
An alloy is a mixture of a metal with at least one
process is called corrosion. ¢ You get calcium compounds from milk a other element, usually another metal.
other dairy products, as well as from gre Different lanthanides are usually found together in
Reading Checkpoint leafy vegetables. nature.
They are difficult to separate from one another
because they all share very similar properties.

¢ Which of the followingis NOT a Figure 17Lanthanides Neodymium is used in

manufacturing the tiny speakers inside stereo
property of metals?
headphones.
— dullness.
— malleability. Figure 14Alkaline
Earth Metals Calcium
— ductility. is one of the Group 2
— conductivity. elements.

Metals in the Periodic Tableff 8

Ra
4 Without calcium,
muscles and bones
Ractum cannot grow and
function.

¢ The metals in a group, or family, have

similar properties, and these family
properties change gradually as you
Transition Metals
move across the table. A

The reactivity of metals tends to ¢ The elements in Groups 3 through 12 are

decrease as you move from left to right called the transition metals. Actinides
across the periodic table ¢ The transition metals include most of the The elements below the lanthanides are called
familiar metals, such as iron, copper, actinides (ak tuh nydz).
nickel, silver, and gold. Of the actinides, only thorium (Th) and uraniu
(U) occur naturally on Earth.
Alkali Metals ¢ Most of the transition metals are hard and
Uranium is used to produce energy in nuclear
shiny. power plants.
The metals in Group 1, from lithium to francium, ¢ All of the transition metals are good All of the elements after uranium in the periodic
are called the alkali metals. conductors of electricity. table were created artificially in laboratories.
Alkali metals react with other elements by losing ¢ Many of these metals form colorful The nuclei of these elements are very unstable,
one electron. meaning that they break apart very quickly into
compounds.
These metals are so reactive that they are never smaller nuclei.
found as uncombined elements in nature. In fact, many of these elements are so unstable
¢ The transition metals are less reactive than
Instead, they are found only in compounds. In the the metals in Groups 1 and 2. that they last for only a fraction of a second after
laboratory, scientists have been able to isolate they are made.
alkali metals from their compounds. This lack of reactivity is the reason ancient
gold coins and jewelry are as beautiful and
¢ As pure, uncombined elements, some of the alkali
etailed today as they were thousands of
metals are shiny and so soft that you can cut them
years ago. Figure 18 sll
with a plastic knife.
¢ Even when iron reacts with air and water, Exploration Rover
¢ The two most important alkali metals are forming rust, it sometimes takes many
years to react completely. Curium, one of the
sodium and potassium.
¢ Some transition metals are important to actinide elements, is
¢« Examples of potassium are shown in Figure
13: your health. used as a source of
¢ Sodium compounds are found in large ¢ For example, you would not survive without high-energy particles
amounts
.in seawater and salt beds. iron. oe that heat and provide
¢ Your diet includes foods that contain It forms the core of a large molecule calle power for certain
compounds of sodium and potassium, hemoglobin, which carries oxygen in yout
bloodstream. scientific equipment
elements important for life.
aboard the Mars
¢ Another alkali metal, lithium, is used in
batteries and some medicines. Metals in Mixed Groups Exploration Rover.
Only some of the elements in Groups 13 throu
15 of the periodic table are metals. Reading Checkpoint |
¢ These metals are not nearly as reactive as thos
Figure 13A
the left side of the table.
Metals
The most familiar of these metals are aluminum, ¢ In the periodic table, the actinides are
Potassium is an
alkali metal.
tin, and lead. , located
¢ Aluminum is the lightweight metal used in
Making beverage cans and airplane bodies.
—in group 17, next to the noble gases.
Generalizations ¢ A thin coating of tin protects steel from corrosion —in group 2, next to the alkaline earth
What in some cans of food. metals.
characteristics
Lead was once used in paints and water pipes.
A. The reactions of some compounds do other —in period 1, next to the alkali metals.
containing potassium help get
fireworks off the ground. Group 1 But lead is poisonous, so it is no longer used for
these purposes. — In period 7, below the lanthanides
elements share
with potassium? Now, its most common uses are in automobile
batteries and weights for balancing tires. Synthetic Elements
Figure 16Metals in Groups 13, 14, and 15 Lead can
¢ Elements with atomic numbers higher t
be used in the borders around the glass sections in
92 are sometimes described as synthetic
stained glass objects. Tin can be fashioned intgy elements because they are not found
‘A Alkaline Earth Metals artistic objects, such as picture frames. naturally on Earth.
¢ Instead, elements that follow uranium are
¢ Group 2 of the periodic table contains the made—or synthesized—when nuclear
alkaline earth metals. particles are forced to crash into one
¢ Each is fairly hard, gray-white, and a good another.
conductor of electricity. ¢ For example, plutonium is made by |
bombarding nuclei of uranium-238 with
¢ Alkaline earth metals react by losing two neutrons in a nuclear reactor.
electrons.
¢ Americium-241 (Am-241) is made by
¢ These elements are not as reactive as the bombarding plutonium nuclei with
metals in Group 1, but they are more neutrons.
reactive than most other metals. i
¢ Like the Group 1 metals, the Group 2
metals are never found uncombined in
nature.
 electron sea

Americium-241 is
in nuclear
reactors. It is widely
used in smoke detectors.

The heaviest synthetic

elements are synthesized
in particle accelerators.

28