Introduction to Inorganic
Chemistry
Chem 3340
Inorganic Chemistry by Shriver
and Atkins
6th Edition
Anindya Ghosh
Inorganic Chemistry: Principles of Structure
and
Reactivity Huheey, J. E., Keiter, E. A., Keiter,
R. L., 4th ed., HarperCollins College Publishers,
NY, 1993.
Shriver and Atkins
6th Edition, 2010, Freemanoxford
Anindya Ghosh
What is inorganic chemistry?
Inorganic chemistry is the chemistry of all the elements organic
refers to a few at the top right-hand part of the periodic table.
Chemistry of nonliving
To understand inorganic chemistry properly we need to be aware of
aspects of physical chemistry, analytical and even organic chemistry.
Because Inorganic comprises all the elements, we need some way to
understand the underlying connections and to figure out why things
work the way they do.
Fortunately, the nature of the elements themselves provides us with
such a guide and we can understand a lot from the arrangement of the
periodic table itself.
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Distribution of Elements on Earth
The universe began about 1.8x1010 years ago.
Earth was much hotter during its early life, and the materials
fractionated into gaseous, liquid and solid.
As the surface of the Earth cooled, the lighter materials in the crust
solidified.
Earth has a core of iron and nickel, and outer half of the earths
radius is composed of silicate materials and sulfide minerals and a
wide variety of materials.
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Distribution of Elements on Earth
Siderophiles (Iron-loving elements) concentrate in the metallic
core. They exhibit metallic bonding.
Lithophiles (Rock-loving elements) combine primarily with
oxygen and the halides and more abundant in the crust. They
typically bond to oxygen in silicates and oxides.
Chalcophiles The elements combine readily with sulfur, selenium,
and arsenic and are also found in the crust
Atmophiles are noble gases and covalently bonded gaseous
molecules. The atoms and molecules are bonded by weak Van der
Waals forces and so these elements remain gaseous at room
temperature.
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The geochemical periodic table of the
elements
Anindya Ghosh
History of Inorganic Chemistry
The first metals used were Gold and Copper. Silver, tin, antimony and
lead were also known as early as 3000 BC.
2Cu2(OH)2CO3 + 2C 4Cu + 4CO2 + 2H2O
Iron appeared in the Mediterranean Sea by 1500 BC.
Fe3O4 + 2C 3Fe + 2CO2
Chemists were very active in China, Egypt in the first centuries AD.
Although much effort went into attempts to transform base metals into
gold, scientists described many chemical reactions.
Distillation, sublimation, crystallization and many other techniques
were developed.
Gunpowder was used in Chinese fireworks as early as 1150 AD.
Anindya Ghosh
History of Inorganic Chemistry
Roger Bacon (1214) recognized as one of the first great experimental
scientists. Chemistry began to take shape as a science around 1600.
By the 17th century, the common strong acids were known.
Neutralization reactions were discovered.
By 1869, the concepts of atoms and molecules were established.
Mendeleev and Meyer established the early forms of the periodic
table.
By 1896, Becquerel discovered radioactivity.
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History of Inorganic Chemistry
Studies of subatomic particles, spectra and electricity led to atomic
theory of Bohr in 1913.
In 1926, Schrdinger and Heisenberg described quantum mechanics
Inorganic chemistry was extremely important to help identify
minerals and to assess their purity and value.
By the 20th century, plants for the production of ammonia, nitric
acid, sulfuric acid, sodium hydroxide and many other inorganic
chemicals produced on a large scale were common.
Anindya Ghosh
History of Inorganic Chemistry
The need for inorganic chemists to work on military projects during
World War II rejuvenated interest in the field.
A great expansion of inorganic chemistry started in the 1940s.
In 1950s, Crystal Field Theory and Ligand Field Theory for
coordination compounds were discovered
In 1955, Ziegler and Natta discovered organometallic compounds
that could catalyze polymerization of ethylene at low temperatures
Biological molecules containing metal atoms such as chlorophyll or
vitamin B12 coenzyme were discovered.
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One current challenge that bridges
organometallic chemistry and bioinorganic
chemistry is the conversion of N2 to NH3
N2 + 3 H2 2 NH3
The Haber Process is a method of producing ammonia developed in
WWI. The Germans needed nitrogen for making their
explosives. When the Allies blocked off all trade routes going to and
from Germany, they lost all source of sodium nitrate and potassium
nitrate, their source of nitrogen.
They found their source of nitrogen in the air, which was 80%
nitrogen. The chemist Fritz Haber and Carl Bosch developed the
Haber Process in WWI, which takes molecular nitrogen from the air
and combines it with molecular hydrogen to form ammonia gas,
which the chemical formula is NH3.
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Inorganic Chemistry: Applications
2H2O O2 + 4H+ + 4e
Photosynthesis
H3N
Haemoglobin
NH3
Pt
Cl
Cl
Cis-platin-anticancer drug
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Catalysis: Importance
Catalysis is key to various chemical transformations
Most Industrial synthesis and almost all biochemical
reactions are catalytic
Catalysis is the most important technology for
environmental protection.
Example: Catalytic converter in your car
70-90% of processes in the chemical industry use catalysts.
Catalyst sales in 2005 were estimated to be worth around US$11
billion. Growth in catalyst sales is estimated to be increasing at
about 4.5% per year. In excess of US$3 trillion in goods and
services in world-wide Gross Domestic Product annually can be
attributed to catalysts.
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Classification of Catalysts
Here we shall classify the catalysts according to the state of aggregation in
which they act.
Generally two: Homogeneous catalysts and heterogeneous catalysts.
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Haber-Bosch Process: Heterogeneous
Catalyst
Ammonia is also used in the production
of urea, NH2CONH2, which is used as
a fertilizer, used in the plastic industry.
Ammonia could be used to make nitric
acid
This process produces ammonia,
NH3(g), yield of approximately 1020%.
This reaction produces over 120
million tons of ammonia in 1990
worldwide.
Anindya Ghosh
Zeolites
Mg2+
Softening of water
+ Ca2+ + Na4Z CaMgZ + 4 Na+
ZSM-5
Boggsite: made up of
Na, K, Si, O
NOx removal by zeolite catalyst
6NOx + 4xNH3 (3+2x)N2 + 6xH2O
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Organometallic Chemistry-Part of Homogeneous
catalysis
Wilkons catalyst (Rh(PPh3)3Cl
RHC=CH2 + H2 RCH2-CH3
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Polymerization Reaction
Polymerization is the reaction of an unsaturated organic reactant, typically a
C=C, with itself over and over again to produce a polymer chain:
*
n
TiCl3 + R3Al Ziegler-Natta Catalyst, Nobel prize 1963
Initiation: generating the active catalyst from a less active catalyst precursor
LnM-R
LnM-Cl + AlR3
+ AlR2Cl
+ MAO (methylalumoxane)
+ ZnR2
LnM-Cl + H-
LnM-H
+ Cl-
Propagation: the polymer chain growth portion of the reaction that occurs over and
over again
H3C
H3C
CH3
CH3
CH3
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Enzymes to catalysts
N2 + 8H+ + 8e + 16MgATP .......> 2NH3 + H2 + 16MgADP + 16Pi
Nitrogenase
Cytochrome P450
RH + O2 + 2H+ + 2e ROH + H2O
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Hemocyanine
invertebrate
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Model study
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Sustainability: A responsibility of Chemists
Goal: Achieve a sustainable civilization in which human
activities and technologies will be compatible to the
assets of Nature
Spent
matter
flows out of
human
economy to
ecosphere
Human
Economy
Matter
flows from
ecosphere
into human
economy
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Sustainability: A responsibility of chemists
Anindya Ghosh
Limitations of Science
Cl
Cl
Cl
OH
Cl
Cl
NaOH, 180 C
5
2
Cl
Cl
2,4,5-trichlorophenol
starting material for
phenoxyherbicides
1,2,4,5-tetrachlorobenzene
Overheat
OH
Cl
Cl
Cl
Cl
Cl
Cl
Cl
2,4,5-T
2,3,7,8-tetrachlorodibenzo-p-dioxin
Anindya Ghosh
Dioxin
3
4
Chlorinated Dibenzodioxin
Photograph and story
by Annie ONeill
November 5, 2000
(with permission of
Pittsburgh Post Gazette)
1
2
O
6
Chlorinated Dibenzodifuran
(Substituents 1-4 and 5-9 = H, Cl;
2,3- and 7-8-chlorinated species are toxic)
Our Stolen Future, Theo
Colborn, Dianne Dumanoski,
John Peterson Myers, PlumePenguin, New York, 1997
Anindya Ghosh
Green Chemistry: Environmentally Friendlier
Chemistry
Environmental Protection Agency (EPA) defines green
chemistry as the use of chemistry for pollution prevention
and design of chemical products and processes that are
more environmentally benign
The 12 principles of Green Chemistry, originally developed
by Paul Anastas and John Warner in Green Chemistry:
Theory and Practice, provide a road map for chemists to
implement green chemistry
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Green chemistry examples: Simple and safe
process is green
Multiple steps
Use of nitric acid is a problem
Adipic acid
Precursor of Nylon
Much safer: Green method
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Use of safe solvents
Dry cleaning industry
uses perchloroethylene
(PERC) as a cleaning
solvent. The solvent is
highly toxic.
A new technology
known as
DryWash uses non
toxic liquid carbon
dioxide to clean cloths
(Green method)
Anindya Ghosh
Aqueous Biphasic Cataysis
2. Aerobic Oxidation
1. Carbonylation
OH
R2
R1
OH
CO Pd / tppts /H+
+ 0.5 O2
Pd2+/L
air
OH
COOH
Ibuprofen
NaO3S
NaO3S
tppts
Pd2+ L
+ H 2O
water
SO3Na
SO3Na
SO3Na
Papadogianakis, Verspui (2001)
Moiseev
ten Brink, Arends, Sheldon, Science 287 (2000) 1636
ten Brink (2001)
Anindya Ghosh
Fe-amide-based catalyst catalyst
Formed from biochemically common elements
prototype exhibits v. low toxicity
Water-soluble
Usable from pH 1 to 13
Effective at 0.1 to 4 ppm = nM to low mM
Not dominated by hydroxyl radical
chemistry
Amenable to modifications for
capturing novel selectivity
+
Hydrogen peroxide
Anindya Ghosh
Fe-amide catalyst Activated Bleaching of 3-Dye Composite
Textile Industry Effluent
Conditions: <5 mM Fe-TAML, 5 mM
H2O2, pH 9.1, T = 25C
spent dye bath
1.5
TAML activator/H 2O2
decolorized dye bath
decolorized pure dyes
Spent
dye
bath
Bleached
Spent
Dye Bath
Fresh
dye
bath
1.0
0.5
0.0
400
500
600
700
wavelength / nm
800
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Dye bleaching
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Biocatalysts: Enzymes are used
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Nanoparticles
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Properties
Nanoparticles have high surface to volume
ratio => and surface properties dominate
Particles add strength to composite
materials
Other size-dependent property changes
include quantum confinement in
semiconductor particles, surface plasmon
resonance in some metal particles and
superparamagnetism in magnetic materials
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Nanomaterials and surface area
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Carbon
nanotubes
Graphene
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Nanocatalysis
Ruthenium
nanocatalyst
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Quantum Dots
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Ferrofluids
Iron oxide in water
or in organic solvent
Stabilized by surfactant
Anindya Ghosh
