Brooklyn College Inorganic Chemistry (Spring 2006)

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Lecture 1
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Brooklyn CollegeInorganic Chemistry(Spring 2006)

• Prof. James M. Howell
• Room 359NE
• [phone] jhowell_at_brooklyn.cuny.edu
• Office hours Mon. Thu. 1000 am-1050 am
  Wed. 5 pm-6 pm
• Textbook Inorganic Chemistry, Miessler Tarr,
• 3rd. Ed., Pearson-Prentice
  Hall (2004)

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What is inorganic chemistry?
Organic chemistry is the chemistry of life the
chemistry of hydrocarbon compounds C, H, N, O
Inorganic chemistry is The chemistry of
everything else The chemistry of the whole
periodic Table (including carbon)
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Organic compounds Inorganic compounds
Single bonds ? ?
Double bonds ? ?
Triple bonds ? ?
Quadruple bonds ? ?
Coordination number Constant Variable
Geometry Fixed Variable
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Single and multiple bonds in organic and
inorganic compounds
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Unusual coordination numbers for H, C
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Typical geometries of inorganic compounds
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Inorganic chemistry has always been relevant in
human history

• Ancient gold, silver and copper objects,
  ceramics, glasses (3,000-1,500 BC)
• Alchemy (attempts to transmute base metals
  into gold led to many discoveries)
• Common acids (HCl, HNO3, H2SO4) were known by
  the 17th century
• By the end of the 19th Century the Periodic
  Table was proposed and the early atomic theories
  were laid out

• Coordination chemistry began to be developed at
  the beginning of the 20th century
• Great expansion during World War II and
  immediately after
• Crystal field and ligand field theories
  developed in the 1950s
• Organometallic compounds are discovered and
  defined in the mid-1950s (ferrocene)
• Ti-based polymerization catalysts are discovered
  in 1955, opening the plastic era
• Bio-inorganic chemistry is recognized as a major
  component of life

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Nano-technology
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Hemoglobin
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The hole in the ozone layer (O3) as seen in the
Antarctica
http//www.atm.ch.cam.ac.uk/tour/
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Some examples of current important uses of
inorganic compounds Catalysts oxides, sulfides,
zeolites, metal complexes, metal particles and
colloids Semiconductors Si, Ge, GaAs,
InP Polymers silicones, (SiR2)n,
polyphosphazenes, organometallic catalysts for
polyolefins Superconductors NbN, YBa2Cu3O7-x,
Bi2Sr2CaCu2Oz Magnetic Materials Fe, SmCo5,
Nd2Fe14B Lubricants graphite, MoS2 Nano-structure
d materials nanoclusters, nanowires and
nanotubes Fertilizers NH4NO3, (NH4)2SO4 Paints
TiO2 Disinfectants/oxidants Cl2, Br2, I2,
MnO4- Water treatment Ca(OH)2,
Al2(SO4)3 Industrial chemicals H2SO4, NaOH,
CO2 Organic synthesis and pharmaceuticals
catalysts, Pt anti-cancer drugs Biology Vitamin
B12 coenzyme, hemoglobin, Fe-S proteins,
chlorophyll (Mg)
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Atomic structure A revision of basic concepts
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Atomic spectra of the hydrogen atom
Paschen series (IR)
Balmer series (vis)
Bohrs theory of circular orbits fine for H but
fails for larger atoms elliptical
orbits eventually also failed0
Lyman series (UV)
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The fundamentals of quantum mechanics
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Quantum mechanics provides explanations for many
experimental observations
From precise orbits to orbitals mathematical
functions describing the probable location and
characteristics of electrons electron density
probability of finding the electron in a
particular portion of space
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Characteristics of a well behaved wave function

• Single valued at a particular point (x, y, z).
• Continuous, no sudden jumps.
• Normalizable. Given that the square of the
  absolute value of the eave function represents
  the probability of finding the electron then sum
  of probabilities over all space is unity.

It is these requirements that introduce
quantization.
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Electron in One Dimensional Box

• Definition of the Potential, V(x)
• V(x) 0 inside the box 0 ltxltl
• V(x) infinite outside box x lt0 or xgt l

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Q.M. solution in atomic units

• ½ d2/dx2 X(x) E X(x)
• Standard technique assume a form of the
  solution.
• Assume X(x) a ekx
• Where both a and k will be determined from
  auxiliary conditions.
• Recipe substitute into the DE and see what you
  get.

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• Substitution yields
• ½ k2 ekx E ekx
• or
• k /- i (2E)0.5
• General solution becomes
• X (x) a ei sqrt(2E)x b e i sqrt(2E)x
• where a and b are arbitrary consants
• Using the Cauchy equality
• e i z cos(z) i sin(z)
• Substsitution yields
• X(x) a cos (sqrt(2E)x) b (cos(-sqrt(2E)x)
• i a sin (sqrt(2E)x) i b(sin(-sqrt(2E)x)

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Regrouping X(x) (a b) cos (sqrt(2E)x) i (a
- b) sin(sqrt(2E)x) Or X(x) c cos (sqrt(2E)x)
d sin(sqrt(2E)x) We can verify the solution as
follows ½ d2/dx2 X(x) E X(x) (??) - ½ d2/dx2
(c cos (sqrt(2E)x) d sin (sqrt(2E)x) ) - ½
((2E)(- c cos (sqrt(2E)x) d sin (sqrt(2E)x)
E (c cos (sqrt(2E)x d sin(sqrt(2E)x)) E X(x)
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We have simply solved the DE no quantum effects
have been introduced. Introduction of
constraints -Wave function must be
continuous at x 0 or x l X(x) must equal
0 Thus c 0, since cos (0) 1 and second
constraint requires that sin(sqrt(2E) l )
0 Which is achieved by (sqrt(2E) l ) n p Or
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• In normalized form

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• Atomic problem, even for only one electron, is
  much more complex.
• Three dimensions, polar spherical coordinates r,
  q, f
• Non-zero potential
• Attraction to nucleus
• For more than one electron, electron-electron
  repulsion.
• The solution of Schrödingers equations for a one
  electron atom in 3D produces 3 quantum numbers
• Relativistic corrections define a fourth quantum
  number

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Quantum numbers
Orbitals are named according to the l value
 
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Principal quantum number n 1, 2, 3, 4 .
determines the energy of the electron in a one
electron atom indicates approximately the
orbitals effective volume
n 1 2 3
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Angular momentum quantum number l 0, 1, 2, 3,
4, , (n-1) s, p, d, f, g, ..
determines the shape of the orbital
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See http//www.orbital.com
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Electrons in polyelectronic atoms (the Aufbau
principle)

• Electrons are placed in orbitals to give the
  minimum possible energy to the atom
• Orbitals are filled from lowest energy up
• Each electron has a different set of quantum
  numbers (Paulis exclusion principle)
• Since ms ? 1/2, no more than 2 electrons may be
  accommodated in one orbital
• Electrons are placed in orbitals to give the
  maximum possible total spin (Hunds Rule)
• Electrons within a subshell prefer to be unpaired
  in different orbitals, if possible

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Placing electrons in orbitals
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