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    Introduction To Inorganic Chemistry Chem 3340

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    Philip
    This document provides an introduction to inorganic chemistry. It begins with definitions of inorganic chemistry as the chemistry of all the elements except for organic compounds. It describes how inorganic chemistry relates to other fields like physical chemistry and how the periodic table can help understand connections between elements. It then discusses the distribution of elements on Earth based on their bonding properties. The document continues with the history of inorganic chemistry from early uses of metals to modern developments. It provides examples of inorganic applications and catalysts. It concludes with discussions of green chemistry and sustainability as important responsibilities for chemists.

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    Introduction To Inorganic Chemistry Chem 3340

    Uploaded by

    Philip
    47 views40 pages
    This document provides an introduction to inorganic chemistry. It begins with definitions of inorganic chemistry as the chemistry of all the elements except for organic compounds. It describes how inorganic chemistry relates to other fields like physical chemistry and how the periodic table can help understand connections between elements. It then discusses the distribution of elements on Earth based on their bonding properties. The document continues with the history of inorganic chemistry from early uses of metals to modern developments. It provides examples of inorganic applications and catalysts. It concludes with discussions of green chemistry and sustainability as important responsibilities for chemists.

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    Inorganic Chemistry chem 3340

    Original Title

    1st-Class Lecture 1

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    This document provides an introduction to inorganic chemistry. It begins with definitions of inorganic chemistry as the chemistry of all the elements except for organic compounds. It describes how inorganic chemistry relates to other fields like physical chemistry and how the periodic table can help understand connections between elements. It then discusses the distribution of elements on Earth based on their bonding properties. The document continues with the history of inorganic chemistry from early uses of metals to modern developments. It provides examples of inorganic applications and catalysts. It concludes with discussions of green chemistry and sustainability as important responsibilities for chemists.

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    © All Rights Reserved
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    Download as pdf or txt
    47 views40 pages

    Introduction To Inorganic Chemistry Chem 3340

    Uploaded by

    Philip
    This document provides an introduction to inorganic chemistry. It begins with definitions of inorganic chemistry as the chemistry of all the elements except for organic compounds. It describes how inorganic chemistry relates to other fields like physical chemistry and how the periodic table can help understand connections between elements. It then discusses the distribution of elements on Earth based on their bonding properties. The document continues with the history of inorganic chemistry from early uses of metals to modern developments. It provides examples of inorganic applications and catalysts. It concludes with discussions of green chemistry and sustainability as important responsibilities for chemists.

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    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.
    Anindya Ghosh

    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.

    Anindya Ghosh

    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.
    Anindya Ghosh

    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.

    Anindya Ghosh

    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.
    Anindya Ghosh

    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.
    Anindya Ghosh

    Inorganic Chemistry: Applications

    2H2O O2 + 4H+ + 4e
    Photosynthesis
    H3N

    Haemoglobin

    NH3

    Pt
    Cl

    Cl

    Cis-platin-anticancer drug
    Anindya Ghosh

    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.
    Anindya Ghosh

    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.

    Anindya Ghosh

    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

    Anindya Ghosh

    Organometallic Chemistry-Part of Homogeneous


    catalysis
    Wilkons catalyst (Rh(PPh3)3Cl
    RHC=CH2 + H2 RCH2-CH3

    Anindya Ghosh

    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

    Anindya Ghosh

    Enzymes to catalysts
    N2 + 8H+ + 8e + 16MgATP .......> 2NH3 + H2 + 16MgADP + 16Pi
    Nitrogenase

    Cytochrome P450

    RH + O2 + 2H+ + 2e ROH + H2O

    Anindya Ghosh

    Hemocyanine
    invertebrate

    Anindya Ghosh

    Model study

    Anindya Ghosh

    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

    Anindya Ghosh

    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
    Anindya Ghosh

    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


    Anindya Ghosh

    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

    Anindya Ghosh

    Dye bleaching

    Anindya Ghosh

    Biocatalysts: Enzymes are used

    Anindya Ghosh

    Nanoparticles

    Anindya Ghosh

    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
    Anindya Ghosh

    Nanomaterials and surface area

    Anindya Ghosh

    Carbon
    nanotubes

    Graphene

    Anindya Ghosh

    Nanocatalysis

    Ruthenium
    nanocatalyst

    Anindya Ghosh

    Quantum Dots

    Anindya Ghosh

    Ferrofluids

    Iron oxide in water


    or in organic solvent
    Stabilized by surfactant

    Anindya Ghosh

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