Anindya Ghosh

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, Freeman-

oxford

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 earth’s

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, Schrödinger 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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Pt

Cl

NH3H3N

Cl

2H2O → O2 + 4H+ + 4e

Inorganic Chemistry: Applications

Haemoglobin

Cis-platin-anticancer drug

Photosynthesis

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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 10-

20%.

• This reaction produces over 120

million tons of ammonia in 1990

worldwide.

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Zeolites

Mg2+ + Ca2+ + Na4Z→ CaMgZ + 4 Na+

Boggsite: made up of

Na, K, Si, O

Softening of water

ZSM-5

6NOx + 4xNH3 → (3+2x)N2 + 6xH2O

NOx removal by zeolite catalyst

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Organometallic Chemistry-Part of Homogeneous

catalysisWilkon’s catalyst (Rh(PPh3)3Cl

RHC=CH2 + H2 → RCH2-CH3

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Polymerization is the reaction of an unsaturated organic reactant, typically a

C=C, with itself over and over again to produce a polymer chain:

**

nn

Initiation: generating the active catalyst from a less active catalyst precursor

LnM-Cl LnM-R + AlR2Cl+ AlR3

+ MAO (methylalumoxane)

+ ZnR2

LnM-Cl LnM-H+ H- + Cl-

Propagation: the polymer chain growth portion of the reaction that occurs over and

over again

M CH3 M CH3

M

H3C

M

H3C

MCH3

Polymerization Reaction

TiCl3 + R3Al Ziegler-Natta Catalyst, Nobel prize 1963

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N2 + 8H+ + 8e¯ + 16MgATP .......> 2NH3 + H2 + 16MgADP + 16Pi

Enzymes to catalysts

RH + O2 + 2H+ + 2e– → ROH + H2O

Cytochrome P450

Nitrogenase

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invertebrate

Hemocyanine

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Model study

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Goal: Achieve a sustainable civilization in which human

activities and technologies will be compatible to the

assets of Nature

Matter

flows from

ecosphere

into human

economy

Spent

matter

flows out of

human

economy to

ecosphere

Human

Economy

Sustainability: A responsibility of Chemists

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Sustainability: A responsibility of chemists

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Limitations of ScienceLimitations of ScienceCl

Cl

Cl

Cl

1

2

4

5

1,2,4,5-tetrachlorobenzene

NaOH, 180 °C

OH

Cl

Cl

Cl

2,4,5-trichlorophenolstarting material for phenoxyherbicides

Overheat

Cl

Cl

Cl

Cl

O

O

O

Cl

Cl

Cl

O

OH

2,3,7,8-tetrachlorodibenzo-p-dioxin2,4,5-T

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O

O

O

1

2

3

46

7

8

9

98

7

6 4

3

21

Chlorinated Dibenzodioxin

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, Plume-

Penguin, New York, 1997

DioxinDioxinPhotograph and story

by Annie O’Neill

November 5, 2000 (with permission of

Pittsburgh Post Gazette)

Photograph and story

by Annie O’Neill

November 5, 2000 (with permission of

Pittsburgh Post Gazette)

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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

Adipic acid

Precursor of Nylon

Multiple steps

Use of nitric acid is a problem

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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OH

COOH

Ibuprofen

CO Pd / tppts /H+

Pd2+ L water

air

R

OH

Aqueous Biphasic Cataysis

1. Carbonylation 2. Aerobic Oxidation

NN

SO3NaNaO3SP SO3Na

SO3Na

NaO3S

tppts

R1 OH

R2 H

Pd2+/L

+ 0.5 O2

R1

R2

O + H2O

ten Brink, Arends, Sheldon, Science 287 (2000) 1636

Papadogianakis, Verspui (2001) ten Brink (2001)Moiseev

R

O

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• 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

Fe-amide-based catalyst catalyst

+

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 = 25ºC

1.5

1.0

0.5

0.0

A

800700600500400

wavelength / nm

spent dye bath

TAML activator/H 2O2

decolorized dye bath decolorized pure dyes

Fresh

dye

bath

Spent

dye

bath

Bleached

Spent

Dye Bath

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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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FerrofluidsIron oxide in water

or in organic solvent

Stabilized by surfactant