Chemistry 4362. Advanced Inorganic Chemistry. Instructor: Dr. Byron K. Christmas Class Time: Tue & Thur - 5:29 to 6:49 p.m. Classroom: N-936 C-320 Phone: (713) 221-8169 FAX: (713) 221-8528 E-Mail: ChristmasB@uhd.edu. Introduction.
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Advanced Inorganic Chemistry
Instructor: Dr. Byron K. Christmas
Class Time: Tue & Thur - 5:29 to 6:49 p.m.
Classroom: N-936 C-320
Phone: (713) 221-8169 FAX: (713) 221-8528
What is Inorganic Chemistry ?
Elemental Composition of the Sun and the Universe
Hydrogen92.5 % 90.87 %
Helium7.3 % 9.08 %
All Others 0.2 % 0.05 %
Elemental Composition of the Earth’s Crust
Oxygen 45.5 % Iron 6.20 %
Silicon 27.2 % Calcium 4.66 % Aluminum 8.30 % All Others 8.14 %
U.S. Production of Top 10 Chemicals (x 109 lb.) - 1997
Sulfuric Acid 95.58
Phosphoric Acid 26.83
Ethylene Dichloride 26.29
From C&EN, June 29, 1998
*Calculated from “billion cubic feet at STP”
Total Organics 279.17
Total Inorganics 450.19
Grand Total 729.36
essential to life - 28 in addition to carbon and
for over 30 years.
Definition: “…the study of the composition, structure,
and properties of matter….” - thefacts about the
elements and their compounds.
Comments from the Experts: “…evident differences
between this and previous editions…is the absence of much
theoretical material previously included…the continuing
rapid growth of chemistry…required the addition of impor-
tant new factsto all of the descriptive material…over the
years, become less persuaded of the value of certain types of
theorizing….Thus, we felt obliged to make space forfacts at
the expense of theoretical material.” Cotton and Wilkinson,
Advanced Inorganic Chemistry, 5th Edition, 1988.
the properties and reactions of substances are the very
essence of chemistry. Facts undergo little if any
change in contrast to constantly changing theories.
Moreover, …a chemist needs a solid background of
facts in order to appreciate the need for theories….”
R. J. Gillespie in the Forward of Chemistry of the
Elements, Greenwood and Earnshaw, 1st Edition,
“Over the years, the theoretical part tended to grow at the expense of
the descriptive material….The theoretical part tended to become the
end rather than the means….By the 1970’s many teachers had to
abandon any attempt to cover descriptive inorganic chemistry in the
traditional sense. Thus we can encounter the student who can
write an erudite account of structural minutiae in copper(II)
chemistry, ligand field spectra and…,but who knows little about
the more mundane compounds of the transition elements and
would be hard pressed to locate indium in the Periodic Table, let
alone venture anything about its chemistry.” Derek W. Smith,
Inorganic Substances: A Prelude to the Study of Descriptive
Inorganic Chemistry, 1st Edition, 1990.
American professor told me he divided inorganic chemistry books into
two types: theoretical and practical. In deciding how to classify any
particular book, he first looked to see if the extraction of the two most
produced metals (Fe and Al) was adequately covered, what impurities
were likely to be present, and how the processing was adapted to re-
move them. Second, he looked to see if the treatment of the bonding
in xenon compounds and ferrocene was longer than that of the pro-
duction of ammonia. Third, he looked to see if the production and
uses of phosphates were covered adequately….For some years there
has been a trend for chemistry teaching to become more theoretical.
There is always theoretical interest in another interesting oxidation
state or another unusual complex, but the balance of this book is
tilted to ensure that they do not exclude the commonplace, the mun-
dane and the commercially important.”J. D. Lee, Concise Inorganic
Chemistry, 5th Edition,1996.
programs have used this approach.
preparing for industry.
work in chemistry.
(Page 338 in Text)
Questions to Ponder:
1. Would you know an Inorganic Polymer if you saw one?
2. How could you determine if an inorganic material was, in fact,
3. List important types of Inorganic Polymers.
4. How would you determine what is and what is NOT an
Is NaCl a Polymer? Is Graphite a Polymer? What about Diamond?
Is Aluminum a Polymer? What about Window Glass?
5. What general principles of chemical bonding, atomic size, etc.
lead to effective polymer formation for different types of
6. What are commercially important inorganic polymers?
Catenation – What are the requirements?
Valence of two or more?
Bond Energies – kJ/mole
Study Hand-outs and your text on Inorganic Polymers
Find three to five ADDITIONAL references on the Web
and study them
Prepare for next Thursday’s Silicone laboratory
(Page 176 in Lab Manual)
Atomic Structure & the Periodic Table
Properties of the Elements
Introduction to Chemical Bonding
The Ionic Bond
The Covalent Bond
The Metallic Bond
Intermolecular Attractive Forces
Acids and Bases
Definition of Chemistry:
The study of the properties, composition, and
STRUCTURE of matter, the physical and
chemical changes it undergoes, and the energy
liberated or absorbed during those changes.
The foundation for theSTRUCTUREof inorganic
materials is found in theSTRUCTUREof the atom.
The “Atomists” (Democritus, Lucippus,
Epicurus, et. al.) - Matter consists ultimately
of “indivisible” particles called “atomos” that
canNOT be further subdivided or simplified.
If these “atoms” had space between them,
nothing was in that space - the “void”.
“picture” of reality.
Modern Concepts of Matter
John Dalton (1803)- An atomist who formalized
the idea of the atom into a viable scientific theory
in order to explain a large amount of empirical
data that could not be explained otherwise.
other in mass but different from the atoms of other
elements bound together in fixed proportions
of atoms but atoms are not created nor destroyed
during such reactions.
Present Concepts - An atom is an electrically
neutral entity consisting of negatively charged
electrons (e-) situated outside of a dense, posi-
tively charged nucleus consisting of positively
charged protons (p+) and neutral neutrons (n0).
Electron - 1 9.109 x 10 -28 g
Proton +1 1.673 x 10 -24 g
Neutron 0 1.675 x 10 -24 g
Model of a
How did we get this concept? - This portion of our
program is brought to you by:
Democritus, Dalton, Thompson, Planck, Einstein, Millikan,
Rutherford, Bohr, de Broglie, Heisenberg, Schrödinger,
Chadwick, and many others.
With the electric field off, the cathode ray is not deflected.
With the electric field on, the cathode ray is deflected
away from the negative plate. The stronger the electric
field, the greater the amount of deflection.
With the magnetic field present, the cathode ray is
deflected out of the magnetic field. The stronger the
magnetic field, the greater the amount of deflection.
e/m = E/H2r
e = the charge on the electron
m = the mass of the electron
E = the electric field strength
H = the magnetic field strength
r = the radius of curvature of the electron beam
Thompson, thus, measured the charge/mass ratio
of the electron - 1.759 x 108 C/g
what metal was being used.
matter and, thus, appeared to be a “sub-atomic”
of 1.7588 x 108 C/g.
R. A. Millikan - Measured the charge of the electron.
In his famous “oil-drop” experiment, Millikan was able to
determine the charge on the electron independently of its
mass. Then using Thompson’s charge-to-mass ratio, he
was able to calculate the mass of the electron.
e = 1.602 10 x 10-19 coulomb
e/m = 1.7588 x 108 coulomb/gram
m = 9.1091 x 10-28 gram
Goldstein - Conducted “positive” ray experiments that
lead to the identification of the proton. The charge
was found to be identical to that of the electron and
the mass was found to be 1.6726 x 10-24 g.
Ernest Rutherford - Developed the “nuclear” model
of the atom.
The Plum Pudding Model of the atom:
A smeared out “pudding”
of positive charge with
negative electron “plums”
imbedded in it.
- - - - -
- - - - -
- - - - -
The Metal Foil Experiments:
If the plum pudding model is correct, then all of
the massive a-particles should pass right through
without being deflected.
In fact, most of the a - particles DID pass right
through. However, a few of them were deflected at
high angles, disproving the “plum pudding” model.
Rutherford concluded from this that the atom con-
sisted of a very dense nucleus containing all of the
positive charge and most of the mass surrounded by
electrons that orbited around the nucleus much as
the planets orbit around the sun.
Assume the diameter of the nucleus of a hydrogen
atom is 1 x 10 -13 cm and the diameter of the atom
is 1 x 10 -8 cm.
1. Calculate the volume of the nucleus and the volume
of the atom in cm3 .
2. Calculate the volume of empty space in the atom.
3. Calculate the ratio of the volume of the nucleus to
volume of the whole atom.
4. Calculate the density of the nucleus if the proton’s
mass is1.6726 x 10-24 g
It was known from experiment and electromagnetic
theory that when charges are accelerated, they
continuously emit radiation, i.e., they loose energy
continuously. The “orbiting” electrons in the atom
were, obviously, not doing this.ATOMIC STRUCTURE
were known to be DIScontinuous.
Atomic Spectra - Since the 19th century, it had
been known that when elements and compounds
are heated until they emit light (glow) they emit
that light only at discrete frequencies, giving a
When white light is passed through a sample of
the vapor of a substance, only discrete frequencies
are absorbed, giving an absorption ban spectrum.
These frequencies are identical to those of the
line spectrum of the same element or compound.
For hydrogen, the spectroscopists of the 19th
Century found that the lines were related by the
n/c = R[(1/m2) - (1/n2)]
n = frequency
R = Rydberg Constant
c = speed of light
m = 1, 2, 3, ….
n = (m+1), (m+2), (m+3), ….
Max Planck - In 1900 he was investigating the nature
of black body radiation and tried to interpret his
findings using accepted theories of electromagnetic
radiation (light). He was NOT successful since these
theories were based on the assumption that light had
To solve the problem he postulated that light was
emitted from black bodies in discrete packets he
called “quanta”. Einstein later called them
“photons”. By assuming that the atoms of the black
body emitted energy only at discrete frequencies, he
was able to explain black body radiation.
E = hn
indicated that atoms emitted energy only at
discrete frequencies or energies rather than
Is light a particle or a wave??
Why do atoms emit only discrete energies?
What actually happens when light interacts
What was wrong with Rutherford’s Model?
around the nucleus.
NEVER residing in between orbits.
another, it absorbs or emits a photon of light with a
specific energy that depends on the difference in
energy between the two orbits.ATOMIC STRUCTURE
The Bohr Model of the Atom
is called the GROUND STATE. All other states
are called EXCITED STATES.
En = (- 2.179 x 10-18 J)/n2
Ephoton = Ehigh - Elow
Ephoton = [(- 2.179 x 10-18 J)/n2high]
-[(- 2.179 x 10-18 J)/n2low]
= - 2.179 x 10-18 J[(1/n2high) - (1/n2low)]
Does this equation look familiar?
n/c = R[(1/m2) - (1/n2)]
Niels Bohr won the Nobel Prize for his work.
However, the model only worked perfectly for
hydrogen. What about all of those other elements??
Louis de Broglie - Thought that if light, which was
thought to have wave characteristics, could also have
particle characteristics, then perhaps electrons, which
were thought to be particles, could have characteristics
l = h/mv
An electron in an atom was a “standing wave”!
Werner Heisenberg - Developed the “uncertainty”
principle: It is impossible to make simultaneous and
exact measurements of both the position (location)
and the momentum of a sub-atomic particle such as
Our knowledge of the inner workings of atoms and
molecules must be based on probabilities rather
than on absolute certainties.
Erwin Schrödinger - Developed a form of quantum
mechanics known as “wave mechanics”.
Hy = Ey
H = Hamiltonian operator
E = Total energy of the system
y = Wave function
[(-h2)/(8p2m)]2 - [e2/r] = E
This is simply a quantum mechanical statement of the Law
of Conservation of Energy
two different probabilities of finding an electron at one
point in space).
in space must = 1.ATOMIC STRUCTURE
Y2dxdydz = 1
Y has many values that meet these conditions. They are
specified region of space.
Principle Quantum Number, n - An integer
greater than zero that represents the principle
energy level or “shell” that an electron occupies.
Energy # of orbitals
n Level Shell n2
1 1st K 1
2 2nd L 2
3 3rd M 9
4 4th N 16
etc. etc. etc. etc.
Azimuthal Quantum Number, l - The quantum
number that designates the “subshell” an electron
occupies. It is an indicator of the shape of an orbital
in the subshell. It has integer values from 0 to n-1.
l = 0, 1, 2, 3, …, n - 1
s p d f
Magnetic Quantum Number, ml - The quantum
number that determines the behavior of an electron
in a magnetic field. It designates the orbitaland
has integer values from -l to +l including 0.
ml = -l, …, -3, -2, -1, 0, +1, +2, +3, …, +l
n l Name ml Orbitals
1 0 1s 0 1
2 0 2s 0 1
1 2p -1, 0, +1 3
3 0 3s 0 1
1 3p -1, 0, +1 3
2 3d -2, -1, 0, +1, +2 5
etc. etc. etc. etc. etc.ATOMIC STRUCTURE
Spin Quantum Number, ms - The quantum number
that designates the orientation of an electron in a
magnetic field. It has half-integer values, +½ or -½.
So what do atoms look like?
A. Interpretation of Y: Theprobability of finding
an electron in a small volume of space centered
around some point is proportional to the value of
Y2at that point.
B. Electron Probability Density vs. r
C. Dot Density Representation: Imagine super-
imposing millions of photographs taken of an
electron in rapid succession.
D. Radial Densities
C. What are the differences in electron energy
levels in hydrogen vs. more complicated atoms?
Ground State Hydrogen Atom
Splitting of the Degeneracy
Splitting of the Degeneracy
1. In hydrogen, all subshells and orbitals in a
given principal energy level have the same energy.
They are said to be Degenerate.
2. In many-electron atoms, s-orbitals have lower
energy than p-orbitals which have lower energy
than d-orbitals which have lower energy than
f-orbitals, etc., etc.
3. Reason: Complex electrostatic interactions.
A. Shielding Effect - A decrease in the nuclear force
of attraction for an electron caused by the presence
of other electrons in underlying orbitals.
B. Effective Nuclear Charge - A positive charge
that may be less than the atomic number. It is the
charge “felt” by outer electrons due to shielding by
electrons in underlying orbitals.
The Pauli Exclusion Principle - No two electron in
the same atom can have the same four quantum
H + e- H -
Quantum Electron 1 Electron 2
n 1 1
l 0 0
ml 0 0
ms +1/2 -1/2
the electronic configuration of many-electron atoms
wherein each electron is added consecutively to the
lowest energy orbital available, taking into account
the Pauli exclusion principle.
Order of Filling -
1s 2s 2p 3s 3p 4s 3d 4p 5s
3s 3p 3d
4s 4p 4d 4f
5s 5p 5d 5f 5g
Li 1s2 2s1
Be 1s2 2s2
B 1s2 2s2 2p1
C 1s2 2s2 2p2
configuration wherein the outer shell electrons
are shown along with the “core” configuration of
the closest previous noble gas.
occupy a given subshell singly and with parallel spins
until each orbital in the subshell has one electron.
“Electrons try to stay as far apart as possible”
[He] 2s2 2p1
[He] 2s2 2p2
[He] 2s2 2p3
all three types of designation for lead (Pb).
Pb 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2
4f14 5d10 6p2
Pb [Xe] 6s2 4f14 5d10 6p2
Electronic Configuration for postive ions (cations) -
Cations are formed by removing electrons in order
of decreasing n value. Electrons with the same n
value are removed in order of decreasing l value.
Fe2+ Fe3+ Cr Cr3+Se2- ?