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

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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.
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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.
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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.
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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

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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
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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)
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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)

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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

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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

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