Lecture Presentation

Inorganic Chemistry
1

By :
Agung Nugroho CS,S.Pd.,M.Sc.
CS,S.Pd.,M.Sc
 Studying Atoms

Seeing the Invisible

 The Big Debate

Can matter be divided

into smaller and smaller
pieces forever?
Aristotle Democritus

YES!
NO!
Atomic Models: Greek
Democritus (460-370 B.C.)
Matter can not be divided
forever

Smallest piece = atom

(Greek atomos =
uncuttable)

He had no way of knowing

what atoms looked like!
Strictly philosophy no
scientific evidence
Most followed Aristotle
The word atom comes from a Greek
word that means uncuttable or
indivisible
and you
Imagine
kept on cutting
you had a and then you
the leftover
piece cut one of
piece of
in half
gold that these smaller
you then pieces in half
cut in
half
Go ld
Gold
 Eventually you would have
and kept
and kept 1 piece of gold left. If you
going
going and
cut it in half, you kept
wouldnt
have gold anygoing
more. This
tiny, tiny single piece of
gold is called an atom of
An atom of gold
gold. An atom is the
smallest particle of an
element that acts like the
element.
 Democritus
He hypothesized that atoms were:
Small & Solid
Different in shape & size
Infinite
Always moving
Capable of joining

4 Greek Elements 7:29

 Let see !!!
History of the Atomic Theory
development
The Atomic Theory and
Electronic Structure
A Visual-Historical Approach

David A. Katz
Department of Chemistry
Pima Community College
Tucson, AZ U.S.A.
Voice: 520-206-6044 Email:
dkatz@pima.edu
Web site: http://www.chymist.com
 Theories of Matter
The Greeks and Hindus appear to have
developed theories on matter.
Most of the writings are attributed to the
Greeks due to the amount of recorded
information that has survived to the present.
Greeks thought substances could be
converted or transformed into other forms.
They observed the changing of states due to
heat and equated it with biological
processes.
The Greeks were philosophers and thinkers,
not experimentalists, so they did not conduct
experiments to verify their ideas.
 Thales of Miletus (about 624-about 527
B.C.)
Proposed that water is the primal matter
from which everything originated.
He is also credited with defining a soul as
that which possesses eternal motion.
Anaximander (610-546 B.C.)
The primary substance, the apeiron, was
eternal and unlimited in extension. It was
not composed of any known elements and it
possessed eternal motion (i.e., a soul).
Anaximenes (585-524 B.C.)
Stated that air is the primary substance
Suggested it could be transformed into other
substances by thinning (fire) or thickening
(wind, clouds, rain, hail, earth, rock).
 Heraclitus of Ephesus (544-484 B.C.)
fire is the primeval substance
Change is the only reality.
The Pythagoreans (Pythagoras (570-490
B.C.))
Reduced the theory of matter to a mathematical
and geometric basis by using geometric solids
to represent the basic elements:
cube = earth
octahedron = air
tetrahedron = fire
icosahedron = water
dodecahedron = ether

Empedocles of Agrigentum (492-432 B.C.)

Credited with the first announcement of the
concept of four elements: earth, air, fire, and
water, which were capable of combining to form
all other substances.
Elements combined by specific attractions or
repulsions which were typified as love and hate.
 Anaxagoras of Klazomenae (c. 500-428
B.C.)
Considered the universe to be composed of an
infinite variety of small particles called seeds.
These seeds were infinitely divisible and
possessed a quality which allowed "like to
attract like" to form substances such a flesh,
bone, gold, etc.
Leucippus (5th century B.C.) and
Democritus (460-370 B.C.)
First atomic theory.
All material things consisted of small
indivisible particles, or atoms, which were all
qualitatively alike, differing only in size, shape,
position and mass.
Atoms, they stated, exist in a vacuous space
which separates them and, because of this
space, they are capable of movement. (This
can be considered at the first kinetic theory.)
 Pierre Gassendi (1592-1655)
Revived the atomic theory (1650)
Atoms are primordial, impenetable,
simple, unchangeable, and
indestructible bodies
They are the smallest bodies that can
exist
Atoms and vacuum, the absolutely full
and the absolutely empty, are the
only true principles and there is no
third principle possible.
Atoms differ in size, shape and weight
Atoms may possess hooks and other
excrescences
Atoms possess motion
Atoms form very small corpuscles, or
molecules, which aggregate into
larger and larger bodies
 Robert Boyle (1627-1691)
Hypothesized a universal matter, the
concept of atoms of different shapes and
sizes
Defined an element (The Sceptical
Chymist, 1661)
And, to prevent mistakes, I must
advertise You, that I now mean by
Elements, as those Chymists that speak
plainest do by their Principles, certain
Primitive and Simple, or perfectly
unmingled bodies; which not being
made of any other bodies, or of one
another, are the Ingredients of which all
those calld perfectly mixt Bodies are
immediately compounded, and into
which they are ultimately resolved.
He could not give any examples of
elements that fit his definition.
 Sir Isaac Newton (1642
-1727)
Modified atomic theory to
atoms as hard particles
with forces of attraction
between them
Events Leading to the Modern Atomic
Theory
Stephen Hales (1677-
1761)
Devised the pneumatic
trough, 1727
Allowed for generation
and collection of gases

Joseph Black (1728-

1799)
Mass relationships in
chemical reactions, 1752
Magnesia alba and fixed
air.
MgCO3 MgO + CO2
 Henry Cavendish (1731-
1810)
Inflammable air,
Hydrogen, 1766
Later: H2 + O2 H2O
Joseph Priestley (1733-
1804)
and
Carl Wilhelm Scheele
(1742-1786)
Dephlogisticated air/ feuer
luft Oxygen, 1774
 Antoine Laurent
Lavoisier (1743-1794)
(and Marie-Anne
Pierrette Paulze
Lavoisier (1758-
1836)?)
Nature of combustion,
1777
Elements in Trait
lmentaire de chemie,
1789
 The Atomic Theory
John Dalton (1766-1844)
New System of Chemical
Philosophy, 1808
All bodies are constituted of a
vast number of extremely
small particles, or atoms of
matter bound together by a
force of attraction
The ultimate particles of all
homogeneous bodies are
perfectly alike in weight,
figure, etc.
John Dalton 1803

English chemist and school teacher

Studied gasses and how they exert
pressure in air.
Concluded they are made of tiny
particles
proposed his atomic theory
 The Atomic Theory
Atoms have definite relative weights
expressed in atoms of hydrogen,
each of which is denoted by unity
Atoms combine in simple numerical
ratios to form compounds
Under given experimental conditions a
particular atom will always behave in
the same manner
Atoms are indestructible
 Daltons Atomic Theory:
1. All elements composed of atoms
2. Atoms of the same element are
exactly alike
3. Compounds contain atoms of more
than one element
4. In a given compound, atoms of
different elements always combine in
the same way
(i.e. Calcium Chloride CaCl2 always has
1 Calcium atom for every 2 Chlorine
atoms)
Daltons
symbols, 1808
Daltons atomic
weights, 1808
Jon Jakob Berzelius, 1813: Letters for element symbols
Name Symbol Name Symbol Name Symbol Name Symbol

Oxygen O Tungsten Tn Palladium Pa Uranium U

Sulphur S Antimony Sb Silver Ag Cerium Ce

Phosphorus P Tellurium Te Mercury Hg Yttrium Y

Muriatic
Columbium Glucinum
radicle M Cl Copper Cu Gl
(nioblium) (beryllium)
(chlorine)
Fluoric
F Titanium Ti Nickel Ni Aluminum Al
radicle
Boron B Zirconium Zr Cobalt Co Magnesium Ms

Carbon C Silicium Si Bismuth Bi Strontium Sr

Nitric radicle N Osmium Os Lead Pb Barytium Ba

Hydrogen H Iridium I Tin Sn Calcium Ca

Arsenic As Rhodium Rh Iron Fe Sodium So

Molybdenum Mo Platinum Pt Zinc Zn Potassium Po

Chromium Ch Gold Au Manganese Ma

 Pieces of Atoms the
Heinrich
electron
Geissler (1814-
1879)

Julius Plcker
(1801-1868)

Evacuated tube
glowed, 1859
Rays affected
by a magnet
 Johann Wilhelm Hittorf
(1824-1914)
Maltese cross tube, 1869
Rays travel in straight line
Cast shadows of objects
 William Crookes (1832-1919)
Verified previous observations,
1879
Caused pinwheel to turn
Composed of particles
Have negative charge
 Joseph John Thomson (1846-
1940)
e/m = -1.759 x 108 coulomb/gram - 1897
 Robert Millikan (1868-1923)
Oil drop experiment 1909
e = -1.602 x 10-19 coulomb
N = 6.062 x 1023 molecules/g-molecule
 Pieces of Atoms the
proton
Eugen Goldstein (1850-
1930)
Canal rays - 1886
 Pieces of Atoms the
neutron
James Chadwick (1891-1974)
Discovered the neutron 1932
 The Subatomic Particles

Particle Symbo Charge Mass Relativ Relative

l coulomb g e Mass
Charge amu
0
1 e or e -1.602 x 10- 9.109 x 10- 0.0005486
electron -1
19 28
0
p or 11H 1.602 x 10- 1.673 x 10-
proton 19 24 +1 1.0073
n or 01n 1.675 x 10-
neutron 0 24
0 1.0087
 Models of the Atom
Philipp Lenard (1862-
1947)
Dynamids 1903

Hantaro Nagaoka
(1865-1950)
Saturnian model - 1904
 J. J. Thomson
Plum pudding
1904
Partly based on A.
M. Mayers (1836-
1897) floating
magnet experiment

A. M. Mayer
 Atomic Models: J.J. Thomson 1897

Passed electricity through vacuum tube

Glowing beam attracted to positively charged plate
Beam was NEGATIVELY charged
Negative charges came from inside atom!
Thomson discovered the Electron
Evidence: different metal plates produced same result
First experiment to prove atoms made of smaller
particles! JJ Thomsons Cathode Ray 2:49
 But wait

We know atoms are

neutral, or all matter
would be repelling all
other matter.
How can atoms be
NEUTRAL if they are full
of negatively charged
electrons?
Atomic Models: J.J. Thomson

Thomsons Model
Daltons Model

+ charges must be present to

balance charge of electron
+ & - lumped in a cluster he said
looked like plum pudding
We suppose that the atom consists of a
number of corpuscles moving about in a
sphere of uniform positive
electrification
when the corpuscles are constrained to
move in one plane the corpuscles will
arrange themselves in a series of
concentric rings.
When the corpuscles are not constrained
to one plane, but can move about in all
directions, they will arrange themselves in
a series of concentric shells
J. J. Thomson, 1904
Photo Reference: Bartosz A. Grzybowski,
Howard A. Stone and George M. Whitesides,
Dynamic self-assembly of magnetized,
millimetre-sized objects rotating at a liquidair
interface, Nature 405, 1033-1036 (29 June 2000)
Ernest Rutherford (1871-1937)
Hans Geiger and Ernest Marsden
1908
Geiger and Marsden were running
experiments on scattering of alpha
particles when passing through thin foils of
metals such as aluminum, silver, gold,
platinum, etc. A narrow pencil of alpha-
particles under such conditions became
dispersed through one or two degrees and
the amount of dispersion,,varied as the
square root of the thickness or probable
number of atoms encountered and also
roughly as the square root of the atomic
weight of the metal used.

Recollections by Sir Ernest Marsden, J. B. Birks,

editor, Rutherford at Manchester, W. A. Benjamin Inc.,
1963
 In a discussion with Geiger, regarding Ernest Marsden,
Rutherford stated that I agreed with Geiger that young
Marsden, whom he had been training in radioactive
methods, ought to begin a research. Why not let him
see if any -particles can be scattered through a large
angle? I did not believe they would be
Recollections by Ernest Rutherford, J. B. Birks, editor, Rutherford at Manchester, W.
A. Benjamin Inc., 1963

The observations, however, of Geiger and Marsden**

on the scattering of a rays indicate that some of the
particles, about 1 in 20,000 were turned through an
average angle of 90 degrees in passing though a layer
of gold-foil about 0.00004 cm. thick, It seems
reasonable to suppose that the deflexion through a
large angle is due to a single atomic encounter,
** Proc. Roy. Soc. lxxxii, p. 495 (1909)
*** Proc. Roy. Soc. lxxxiii, p. 492 (1910)
 From the experimental results, Rutherford
deduced that the positive electricity of the atom
was concentrated in a small nucleus and the
positive charge on the nucleus had a numerical
value approximating to half the atomic weight.
Recollections by Sir Ernest Marsden, J. B. Birks, editor, Rutherford at
Manchester, W. A. Benjamin Inc., 1963
 It was quite the most incredible event that has
ever happened to me in my life. It was almost as
incredible as if you had fired a 15-inch shell at a
piece of tissue-paper and it came back and hit you.
Recollections by Ernest Rutherford, J. B. Birks, editor, Rutherford at
Manchester, W. A. Benjamin Inc., 1963
Atomic Models: Rutherford
1911

Passed + Charged
alpha particles thru
gold foil
Most passed right
through
Some bounced off
at odd angles
Very few bounced
Rutherfords Gold Foil Experiment 4:06
straight back
Rutherfords Gold Foil
Experiment
Rutherfords Work
 Rutherfords Conclusion
the results showed that
something + was repelling
+alpha particles
More direct alpha particles
hit mysterious + charge,
greater deflection
+ charge concentrated in
small central area -
Rutherford called nucleus The atom 1:15
Atom is mostly empty
space!
 Ok, so heres what we know
so far..
The atom is made up of
+ particles in nucleus,
and negative electrons.
Where are these
electrons found in the
atom?
The Atom Song 3:28
 The
Rutherford
Atom
Model
The atom is mostly empty space with a dense nucleus
Protons and neutrons in are located in the nucleus.
The number of electrons is equal to the number of
protons.
Electrons are located in space around the nucleus.
Atoms are extremely small: the diameter of a hydrogen
atom is 6.1 x 10-11 m (61 pm)
 Radioactivity and
Stability of the nucleus
Wilhelm Conrad Roentgen
1845-1923
Discovered x-rays - 1895

Barium
platinocyanide
Henri Becquerel (1852-1908)
Radiation activity, 1896

Uranium nitrate

Image of potassium uranyl

sulfate
Pierre Curie (1859-1906)
Marie Curie (1867-1934)
Radioactivity- 1898
Polonium - 1898
Radium - 1898

pitchblende

Radium bromide
Marie Curie with inset
photo of Pierre Curie
Ernest Rutherford (1871-
1937)
, , - 1903

In his lab at McGill University, 1903

Glenn T. Seaborg (1912-1999)
Extending the periodic table
Spectra
 The Electromagnetic
Spectrum
Viewing spectra using holographic
diffraction grating (Flinn Scientific
C-Spectra)

Hydrogen spectrum Helium spectrum

The Balmer Series of Hydrogen
Lines
In 1885, Johann Jakob Balmer (1825 -
1898), worked out a formula to
calculate the positions of the spectral
lines of the visible hydrogen spectrum
m2
(
364.56 2 2
m 2
)
Where m = an integer, 3, 4, 5,
In 1888, Johannes Rydberg
generalized Balmers formula to
calculate all the lines of the hydrogen
spectrum1 1 1

RH ( 2
n2 n1
2)
Where RH = 109677.58 cm-1
The Quantum Mechanical
Model
Max Planck (1858 -1947)
Blackbody radiation 1900
Light is emitted in bundles
called quanta.
e = h
h = 6.626 x 10-34 J-sec

As the temperature
decreases, the peak of the
black-body radiation curve
moves to lower intensities
and longer wavelengths.
The Quantum Mechanical

Model
Albert Einstein (1879-1955)
The photoelectric effect 1905
Plancks equation: e = h
Equation for light : c =
Rearrange to c


hc
e
Substitute into Plancks equation

From general relativity: e = mc2
Substitute for e and solve for
h

mc
Light is composed of particles called
photons
 The Bohr Model - 1913
Niels Bohr (1885-1962)
 The Bohr Model Bohrs
Postulates
1. Spectral lines are produced by
atoms one at a time
2. A single electron is responsible for
each line
3. The Rutherford nuclear atom is the
correct model
4. The quantum laws apply to jumps
between different states
characterized by discrete values of
angular momentum and energy
 The Bohr Model Bohrs
Postulates
5. The Angular momentum is given
by h
p n ( 2 ) n = an integer: 1, 2, 3,
h = Plancks constant

6. Two different states of the

electron in the atom are involved.
These are called allowed
stationary states
 The Bohr Model Bohrs
Postulates
7. The Planck-Einstein equation, E = h
holds for emission and absorption. If an
electron makes a transition between two
states with energies E1 and E2, the
frequency of the spectral line is given by
h = E1 E2
= frequency of the spectral line
E = energy of the allowed stationary state
8. We cannot visualize or explain,
classically (i.e., according to Newtons
Laws), the behavior of the active
electron during a transition in the atom
from one stationary state to another
 Bohrs calculated radii of
hydrogen energy levels
r = n2A0
r = 53 pm

r = 4(53)
pm
= 212
r = 9 (53)
pm pm
= 477r = 16(53)
pm pm r = 25(53)
= 848 pm
pm = 1325 r = 36(53) pm r=
pm 49(53) pm
= 1908 pm =
2597 pm
 Lyman Series
Balmer Series

Paschen Series

Brackett Series

Pfund Series

Humphreys Series
The Bohr Model
The energy absorbed or
emitted from the process of an
electron transition can be
calculated by the equation:
1 1
E RH ( 2
2
n2 n1
)
where
RH = the Rydberg constant, 2.18
1018 J,
and
n1 and n2 are the initial and final
energy levels of the electron.
 The Wave Nature of the Electron
In 1924, Louis de Broglie (1892-
1987) postulated that if light can act
as a particle, then a particle might
have wave properties
De Broglie took Einsteins equation
h

mc

and rewrote it as
h

mv
where m = mass of an electron
v = velocity of an electron
 The Wave Nature of the Electron
Clinton Davisson (1881-
1958 ) and Lester
Germer (1886-1971)
Electron waves - 1927
 Werner Heisenberg (1901-
1976)
The Uncertainty Principle, 1927
The more precisely the position
x
p
4
h

is determined, the less precisely

the momentum is known in this
instant, and vice versa.
h
x p
4
As matter gets smaller, approaching
the size of an electron, our measuring
device interacts with matter to affect
our measurement.
We can only determine the probability
of the location or the momentum of
the electron
 Quantum Mechanics
Erwin Schrodinger (1887-1961)
The wave equation, 1927
Uses mathematical equations of wave
motion to generate a series of wave
equations to describe electron behavior in
an atom
The wave equations or wave functions are
designated by the Greek letter

wave function mass of electron potential energy at x,y,z

d2 d2 d2 8 2m
+ + + (E-V(x,y,z)(x,y,z) = 0
dx 2
dy2
dz 2
h 2

how changes in space total quantized energy of

the atomic system
 Quantum Mechanics

The square of the

wave equation, 2,
gives a probability
density map of where
an electron has a
certain statistical
likelihood of being at
any given instant in
time.
 Quantum Numbers
Solving the wave equation gives a set
of wave functions, or orbitals, and
their corresponding energies.
Each orbital describes a spatial
distribution of electron density.
An orbital is described by a set of
three quantum numbers.
Quantum numbers can be considered
to be coordinates (similar to x, y,
and z coodrinates for a graph) which
are related to where an electron will
be found in an atom.
 Solutions to the Schrodinger Wave Equation
Quantum Numbers of Electrons in Atoms
Name Symbol Permitted Values Property

principal n positive integers(1,2,3,) Energy level

angular l integers from 0 to n-1 orbital shape (probability

momentum distribution)
(The l values 0, 1, 2, and 3
correspond to s, p, d, and f
orbitals, respectively.)

magnetic ml integers from -l to 0 to +l orbital orientation

spin ms +1/2 or -1/2 direction of e- spin

 Looking at Quantum
Numbers:
The Principal Quantum
Number, n
The principal quantum number,
n, describes the energy level
on which the orbital resides.
The values of n are integers
0.
n = 1, 2, 3, etc.
 Looking at Quantum
Numbers:
The Azimuthal Quantum
Number, l
The azimuthal (or angular
momentum) quantum number tells
the electrons angular momentum.
Allowed values of l are integers
ranging from 0 to n 1.
For example, if n = 1, l = 0
Value ifAngular
n = 2, momentum
l can equal 0 or 1
of l
0 None
1 Linear
2 2-directional
3 3-directional
 Looking at Quantum
Numbers:
The Azimuthal Quantum
Number,
The values of l relate
distribution.
l
to the most probable electron

Letter designations are used to designate the

different values of l and, therefore, the shapes of
orbitals.
Valu Orbital Orbital Name*
e of l (subshell) Shape * From
emission
Letter spectroscopy
designation terms

0 s sharp

1 p principal

2 d diffuse

3 f fine
 Looking at Quantum
Numbers:
The Magnetic Quantum
Number,
Describes the orientation ofm
anl orbital with
respect to a magnetic field
This translates as the three-dimensional
orientation of the orbital.
Values of ml are integers ranging from -l to l:
l ml l.

Values Values of ml Orbital Number

of l designat of
ion orbitals
0 0 s 1
1 -1, 0, +1 p 3
2 -2, -1, 0, +1, +2 d 5
3 -3, -2, -1, 0, +1, f 7
+2, +3
 Quantum Numbers and

Subshells
Orbitals with the same value of n form a shell
Different orbital types within a shell are called
subshells.
 Pictures of s and p orbitals

Imaging the atomic orbitals of carbon atomic chains

with field-emission electron microscopy
I. M. Mikhailovskij, E. V. Sadanov, T. I. Mazilova, V. A. Ksenofontov,
and O. A. Velicodnaja, Department of Low Temperatures and
Condensed State, National Scientific Center, Kharkov Institute for
Physics and Technology, Academicheskaja, 1, Kharkov 61108, Ukraine
Phys. Rev. B 80, 165404(2009)
 A
Summary
of Atomic
Orbitals
from 1s
to 3d
 Empty subshells
subshells subshells
Valence Full
Approximate energy levels for neutral atoms.
From Ronald Rich, Periodic Correlations, 1965
The Spin Quantum Number, ms

In the 1920s, it was

discovered that two
electrons in the same
orbital do not have
exactly the same
energy.
The spin of an
electron describes its
magnetic field, which
affects its energy.
 Otto Stern (1888-1969) and
Walther Gerlach (1889-1979)
Stern-Gerlach experiment, 1922
 Spin Quantum Number, ms

This led to a fourth

quantum number,
the spin quantum
number, ms.
The spin quantum
number has only 2
allowed values:
+1/2 and 1/2.
 Wolfgang Pauli (1900-1958)
Pauli Exclusion Principle,
1925
There can never be two or
more equivalent electrons in an
atom for which in strong fields
the values of all quantum
numbers n, k1, k2, m1 (or,
equivalently, n, k1, m1, m1) are
the same.
 Hunds Rule
Friedrich Hund
(1896 - 1997)
For degenerate
orbitals, the
lowest energy is
attained when the
electrons occupy
separate orbitals
with their spins
unpaired.
J. Mauritsson, P. Johnsson, E. Mansten, M. Swoboda, T. Ruchon, A.
LHuillier, and K. J. Schafer, Coherent Electron Scattering
Captured by an Attosecond Quantum Stroboscope,
PhysRevLett.,100.073003, 22 Feb. 2008
http://www.atto.fysik.lth.se/