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Technological Institute of the Philippines

363 P. Casal St., Quiapo, Manila

Project in PCHM413L1
( Physical Principles 2 )
Prepared by:
John P. Bandoquillo
CH41FB1

Required and Checked by:


Engr. Frefe C. Rupinta
Chapter 3:

Atomic Structure
Fundamentals of Physical Chemistry
Samuel H. Maron / Jerome B. Lando
Introduction
The first modern attempt at an explanation of
chemical reactivity of chemical elements is
Dalton’s atomic theory formulated in 1808.
Dalton postulated that every elements
consists of invisible particles called atoms,
each of which has the same mass for a given
elements, and that these atoms react with
each other to form compounds.
However, he made no effort to establish
any relation between the atoms of various
elements. This was first done in 1815 by
Prout, who reasoning from the proximity
of the atomic weights of elements to whole
numbers on the basis of hydrogen as unity,
suggested that all elements were composed
of multiples of hydrogen atoms.
Another important principle which indicated the
existence of a regular relationship among the
elements was the periodic law discovered
independently by Mendeléeff (1869) in Russia
and Lothar Meyer (1870) in Germany. This
law, that the chemical and physical properties of
the elements are periodic functions of their
atomic weights, pointed to regularities in the
structure of atoms and to the fact that certain
structures repeated themselves periodically to
yield similarity of chemical and physical
properties.
Finally, the electrical researches of
Nicholson and Carlisle, Davy, Berzelius and
Faraday showed that matter and electricity are
intimately associated and that electricity itself
is corpuscular in nature. These findings,
followed by studies of electric discharges
through rarefied gases and the discovery of
radioactivity, eventually established that atoms
consist of the same structural units. Primarily,
these are the electron, the proton and the
neutron.
The Electron
Gases are as a rule poor conductors of
electricity. However, when a tube filled with
gas is evacuated to pressures of 0.01 mm or
lower and an electric potential is applied
across a pair of electrodes sealed into the tube,
a discharge takes place between the electrodes
during which a stream of cathode rays is
emitted from the cathode.
The particles constituting the cathode rays
have been named electrons. The fact that
electrons are independent of the nature of the
source from which they come suggests that
they are constituents of all matter. From the
relations of the forces involved, the ratio of the
electron charge e to its mass m may then be
evaluated, and Thomson found thus e/m to be
1.79 x 10^7 electromagnetic units per gram.
More refined measurements have modified this
value to:
e/m = 1.75880 x 10^7 emu/g
= 1.75880 x 10^8 abs. coulombs/g

J.J. Thomson’s apparatus for determination of e/m for electron.


In order to resolve to resolve this ratio, the charge on
the electron must be ascertained independently. This
determination was first carried out with a high degree of
precision in 1913 by R.A Millikan through his famous
oil-drop experiments.

Millikan’s oil-drop apparatus


If we let ν1 be the rate of fall of the particle under gravity g,
v2 the rate of rise of the particle against gravity when an
electrostatic field strength X is applied, and m’ and e’ the
mass of and charge on the oil droplet, then in the oil drop
experiments these quantities are connected by the relation

v1/v2 = m’g/(Xe’ – m’g)


Millikan found that e’ was not constant.
However, he did find that there was a
common factor for all the values of e’ which
made the various charges observed whole
number multiples of the common factor. The
value of this least common factor deduced by
Millikan was 4.774 x 10 ^ -10 electrostatic
unit, and this must be, therefore, the charge
of the unit of electricity, or the electron.
Since this work a redetermination of the
viscosity of the air and other corrections have
shown that a better value of the electronic
charge, e, is
e = 4.80298 x 10^ -10 esu/electron
= 1.60210 x 10^ -20 emu/electron
= 1.60210 x 10^ -19 abs. coulomb/electron
From e/m and e the mass of the electron
follows as
m = e/(e/m)
= 1.60210 x 10^ -19/1.75880 x 10^ 8
= 9.1091 x 10^ -28 g per electron (Eg. 1)
This mass of the electron may be compared
with the mass of a hydrogen atom, which is, of
course, the atomic weight of hydrogen divided
by Avogadro’s number, namely,
mH = 1.00797/6.0225 x 10^ 23
= 1.673 x 10^ -24 g
From mH and m it is seen that the mass of the
hydrogen atom is 1836 times greater than the
mass of the electron.
The mass of the electron given in Eq. 1 is the rest
mass, the mass when the electron is either at rest or
moving with velocities that are low compared with
that of light. However, when the electron is moving at
very high speeds, then according to the theory of
relativity the mass of the electron is increased in line
with the equation
m = m0/[ 1 – (v/c)^2]^1/2
Where:
m0 = mass of the electron at rest
m = mass of the electron is moving
v = velocity
c = velocity of light.
Wave Nature of the Electrons. The duality of
behavior, exhibited also by light and even
atoms, is an illustration of the Heisenberg
uncertainty principle enunciated in 1927,
which states that it is impossible to define
simultaneously the exact momentum and
position of a body. Precisely, Heisenberg
showed that the product of the uncertainty in
the position of a body ∆x, and the uncertainty
in the momentum ∆p, and hence the velocity,
is even in the perfect experiment related to
Planck’s constant h.
(∆x) (∆p) ≥ h/(4π)
where:
h = 6.6256 x 10^ -27 erg second
Now, in studying the electron in discharge
experiments we concentrate on the exact
definition of its velocity and momentum, and
arrive thus at the conclusion that electron is a
particle. On the other hand, when the electron
diffraction experiments are performed, the
emphasis is on the position of the electron.
The Proton
When this atom is converted into ion, it is
found that its charge is exactly equal to that of
the electron but is opposite in sign. Further, the
mass of the positively charged hydrogen ion,
or proton, is very nearly the same as that of
the hydrogen atom. By perforating the
cathode these positive of canal rays can be
made to pass through the holes to the rear, and
there be studied by the effect of electric and
magnetic fields upon them.
Positive Ray Analysis and
Isotopes
A method of investigating positive rays is
the Aston mass spectrograph, with which
masses of positively charged particles can be
determined with an accuracy greater than one
part in a million. More recent designs of mass
spectrographs dispense with the photographic
plate by substituting for it detecting and
recording devices which yield directly plots of
current intensity versus atomic mass.
Schematic Diagram of Aston’s Spectrograph
Atomic Masses Deduced From Mass Spectrometry
Atomic No. Atom Rounded Mass Atomic Weight( C Basis ) Abundance( % )

1 H 1 1.00782 99.985
2 2.0141 0.015
2 He 3 3.10603 10^ -5
4 4.0026 100
3 Li 6 6.01511 7.4
7 7.01599 92.6
4 Be 9 9.01217 100
5 B 10 10.01295 18.83
11 11.00942 81.17
6 C 12 12 98.892
13 13.00333 1.108
7 N 14 14.00307 99.64
15 15.00009 0.36
8 O 16 15.99491 99.76
17 16.00013 0.04
18 17.99916 0.2
From a study of the mass spectra it is
possible to deduce very precise values of the
atomic weights. The mass spectrograph also
reveals that many elements, which from
ordinary atomic weight determinations were
considered to consist of atom of the same
mass, are in reality mixtures of atoms of
different masses although of the same atomic
number. Such atoms of different mass but
same atomic number are called isotopes.
Hydrogen and Deuterium
Among the methods which have been employed to
separate or enrich isotopes are the mass
spectrograph, diffusion, centrifuging, thermal
diffusion, electrolysis, fractional distillation and
chemical exchange. It is of interest to point out the
differences found between ordinary hydrogen and
its heavier isotope deuterium, symbol D.
Deuterium was discovered spectroscopically in
1932 by Urey and his co-workers at Columbia
University.
In ordinary hydrogen gas deuterium is present
as about one part in 6600 parts of light
hydrogen. The heavier isotope is usually
concentrated by electrolysis of aqueous alkali
solutions, in which instance the lighter
hydrogen atoms escape more rapidly than the
heavier deuterium, and the solution becomes
more concentrated in D2O, heavy water. By
repeating the electrolysis a number of times,
pure D2O can be prepared and studied.
Comparison of Properties of Hydrogen Isotopes
Property H2 D2

Molar Volume of Solid 26.15 cc 23.17 cc

Triple Point 13.92°K 18.58°K

Heat Fusion 28 cal/mole 47 cal/mole

Boiling Point 20.38°K 23.50°K

Heat of Vaporization at Triple Point 217.7 cal/mole 303.1 cal/mole


Comparison of Properties of H2O and D2O
Property H2O D2O

Relative Density, 25° / 25°C 1 1.1079

Melting Point 0.00°C 3.82°C

Boiling Point 100.00°C 101.42°C

Surface Tension, 20°C 72.75 dynes/cm 67.8 dynes/cm

Temperatute of Maximum Density 4.0°C 11.6°C

Dielectric Constant, 25°C 78.54 78.25

Viscosity, 20°C 10.09 millipoises 12.6 millipoises

Heat of Fusion 1436 cal/mole 1510 cal/mole

Heat of Vaporization 10,480 cal/mole 10,740 cal/mole


The Neutron
In 1920 Rutherford suggested that there may
also be present in atoms a particles of essentially
the same mass as the proton but with no charge.
The existence of such uncharged particles, called
neutrons, was actually established in 1932 by
Chadwick. These particles have been found to be
independent of their source in their properties, to
be unaffected by electric and magnetic fields,
indicating thus absence of charge, and to have a
mass of 1.00866 atomic weight units, which is
almost identical with that of the proton, 1.00728.
Rutherford’s Theory of the Atom
The Alpha (α) particle:
 emission products of certain radioactive
disintegrations.
 they have the mass approximately four times
that of the proton bear two positive charges.
 directed against a thin metallic foil should be
able to pass through it without deflection as
long as they do not approach too near to a
positive nucleus.
• directed as to come near the nucleus, the
strong repulsive force developed between the
nucleus and the positive α particle causes the
latter to be deflected sharply.
The Charge on the Nucleus
The first precise statement that the nuclear
charge of an atom is identical with its atomic
number was made by van der Broeck in
1913. Nevertheless, the first direct evidence
on this point is due to Moseley’s studies
(1913, 1914) of the X radiations emitted by
various elements. The various sets of line thus
obtained can be divided into series designated
in turn as the K, L, M, etc. ,series, while the
lines within each series are referred to in
sequence as the α, β, γ, etc., lines.
Thus, the Kα line is the first line in the K series,
the Lβ is the second line in the second series, etc.
He also found that if we take the frequencies of
any particular line in all the elements, such as the
Kα or Kβ lines, then the frequencies are related to
each other by the equation given below. Moseley
concluded that the change in atomic number from
element to element represents the regular
variation in the number of extra nuclear electrons
in the neutral atom, the number of extra nuclear
electrons is identical with the atomic number of
an element.
v ^ ½ = a (Z –k)
where:
v = frequency of any particular Kα or Kβ
Z = atomic number
a and k = constant for any particular type of
line.
Distribution of Electrons, Protons
and Neutrons in an Atom
Rutherford believed that the external
electrons may occupy any and all positions
outside the nucleus and possess thereby
energies with can vary continuously. However,
this concept of continuous variation in energy
is contradicted by atomic spectra, which are
not continuous but discontinuous.
To overcome this difficulties inherent in the
Rutherford atom, Niels Bohr advanced in
1913 his famous theory of atomic structure.
Before this theory can be presented, however,
two other subjects must be introduced first: the
quantum theory of radiation, and the emission
of line spectra by excited atoms.
The Quantum Theory of Radiation
When radiation strikes any surface of a
body, part of the radiant energy is generally
reflected, part is absorbed, and part is
transmitted. The reason for the incomplete
absorption is that ordinary bodies are as a rule
imperfect absorbers of radiation. In contrast to
this, we have the black body, which by
definition is the perfect absorber of energy and
retains any radiant energy that strikes it.
A black body is not only a perfect absorber of
radiant energy, but also a perfect radiator. In
fact, all bodies heated to a given temperature,
it is the black body which will radiate the
maximum amount of energy possible for the
given temperature. The total amount of energy
E radiated by a black body per unit area and
time is given by Stefan-Boltzmann fourth
power law.
Stefan-Boltzmann fourth power law:
E = σT
where:
T = absolute temperature
σ = universal constant equal to 5.6697 x
10^-5
for energy in ergs, time in second,
and are
in square centimeters
Max Planck in 1990 says that black
bodies radiate energy not continuously,
but discontinuously in energy packets
called quanta.
E = hv
where:
E = quantum of energy radiated
v = frequency
h = Planck’s constant equal to 6.6256 x
10^-27
ergs-second.
This equation is the fundamental relation of
the quantum theory of radiation. Planck
considered the black body to consist of
oscillators of molecular dimensions, each with
a fundamental vibration frequency v, and that
each oscillator could emit energy either in the
unit quantum E1 = hv, or in the whole number
multiples n thereof, En = nhv. On this basis he
was able to deduce for the energy Eλ radiated
by a black body at any wave length λ given by
the relation:
Relation:
Eλ = [ 8πhc/λ ] [ 1/(e^hc/kTλ) –
1]
where:
c = velocity of light
T = absolute temperature
k = gas constant per molecule or R/N
Planck’s success with the quantization of black
body radiation led Albert Einstein in 1905 to a
generalization of quantum theory. Einstein
postulated that all radiate energy must be
absorbed or emitted by a body in quanta whose
magnitude depends in the frequency according
to Planck’s equation or multiples thereof.
The Line Spectra of Atoms
Gases and vapors yield a series of lines
called line spectra, or bands called band
spectra, which consist of many lines close
together. The band spectra are radiations
emitted by molecules, whereas line
spectra are due to atoms. Each series of
lines is related by a formula, which for the
Balmer series, appearing in the visible
spectral range, takes the form
1/λ = v = RH [( 1/2²) – (1/n²)]
Here λ is the wave length of line, whose
reciprocal, v, is called the wave number, the
number of wave per centimeter, RH is a
constant called the Rydberg constant and equal
to 109,677.58/cm, and n is a running number
taking on for the various lines of this series
values of 3, 4, 5, etc.
V = RH [(1/n1²) – (1/n2²)]
where:
n1 and n2 = spectral series observed in atomic
hydrogen
Spectral Series Observed in Atomic Hydrogen
Series n1 n2 Spectral Region

Lyman 1 2, 3, 4… Ultraviolet

Balmer 2 3, 4, 5… Visible

Paschen 3 4, 5, 6… Infrared

Brackett 4 5, 6, 7… Infrared

Pfund 5 6, 7… Infrared
Bohr’s Theory of Atomic Structure
Bohr considered the atom to consist of a
nucleus with electrons revolving about it. Bohr
postulated that the only possible orbits for
electron revolution are those for which the
angular momentum is a whole number
multiple n of quantity (h/2π), h being Planck’s
constant. The second postulate introduces the
concept that there are definite energy levels or
stationary states within the atom in which an
electron possesses a definite and invariable
energy content.
Finally, Bohr assumed as his third postulate
that each line observed in the spectrum of an
element results from the passage of an electron
from an orbit in which the energy is E2 to one
of lower energy E1 and that this difference in
energy is emitted as a quantum of radiation of
frequency v in line with the equation
∆E = E2 –E1 = hv
Coulomb’s Law as Ze²/r²:
Ze²/r² = mv²/r

Angular Momentum of the electron is mvr:


Mvr = nh / 2π

Substitute angular momentum to Coulomb’s


Law:
R = n²h² / 4π²mZe²
The total energy E of the electrons in
its orbit is the sum of its kinetic and
potential energies. The kinetic energy
is given by ½ mv², and the potential
energy by -Ze²/r.
E = ½ mv² - Ze²/r
E = Ze²/2r - Ze²/r = -Ze²/2r
By substitution method
E = -2π²mZ²e / n²h²
n = principal quantum number
Origin of Spectral Series in Atomic Hydrogen (Schematic)
Ionization Potentials
In the previous figure the lowest energy level of
the electron is the one for which n = 1. This level
is called the ground state of the electron. Again,
the highest energy level is the one for which n =
∞, and this state corresponds to the removal of
the electron from the influence of the nucleus
ionization of the atom. The energy, I, required to
produce ionization from the normal or ground
state of the electron is called the ionization
potential, and it is usually expressed in electron
volts, eV.
Ionization Potentials of Atoms
Element Atomic Number I (eV) 1 I (eV) 2 I (eV) 3 I (eV) 4 I (eV) 5

H 1 13.6 0 0 0 0

He 2 24.58 54.4 0 0 0

Li 3 5.39 75.62 122.42 0 0

Be 4 9.32 18.21 153.85 217.66 0

B 5 8.3 25.15 37.92 259.3 338.5

C 6 11.26 24.38 47.86 64.48 390.1

N 7 14.54 29.61 47.43 77.45 97.4

O 8 13.61 35.15 54.93 77.39 113

F 9 17.42 34.98 62.65 87.23 113.7

Ne 10 21.56 41.07 64 97.16 0

Na 11 5.14 47.29 71.65 98.88 0

Mg 12 7.64 15.03 80.12 109.29 0


Quantum Number
The appearance of multiple fine lines in
place of a single line is referred to as mutiplet
or fine structure of spectral lines. The spin
quantum number s arises from a suggestion
made by Uhlenbeck and Goudsmit in 1925
that an electron in its motion in an orbit may
rotate or spin about its own axis.
The four quantum numbers and the values
they may take on may be summarized as
follows:
1. Principal Quantum Number, n. This
number can only have the integral values, n
= 1, 2, 3, etc.
2. Azimuthal Quantum Number, l. For each
value of n there may be n values of l, namely
l = 0, 1, 2…,(n = 1).
3. Magnetic Quantum Number, m. For each
value of l there may be (2l + 1) values of m.
These range from m = -l through m = 0 to m
= +l in integral values.
4. Spin Quantum Number, s. There
are only two possible values of s, s =
½ and s = -½, for each value of l.

Pauli’s Exclusion Principle – no two


electrons in an atom may have all
four quantum numbers the same.
Electrons Shells and Subshells
Just as the energy levels of electrons in
atoms may be considered to be divided into
levels and sublevels, so may the electrons be
considered to exist in groups and subgroups,
referred to respectively as shells and subshells.
This concept finds its justification in the
explanation of the origin of X-ray spectra. The
ordinary line spectra of elements are due to
electrons present in the outermost shell, the
optical electrons.
The Periodic Table and Atomic
Structure
The periodicity of the elements definitely
rules out mass as the determining factor in
chemical reactivity, and hence the nuclei of
atoms cannot possibly be responsible for
chemical behavior. The first satisfaction
suggestion about the number of electrons in
various shells and their possible arrangement
was advanced in 1921 independently by Bury
and Bohr.
These men proposed that the maximum
number of electrons in each shell should be
given by 2n², where n is the principal quantum
number. This would give for the maximum
number of electrons in successive shells 2, 8,
18, 32, and 50. Further, Bury and Bohr
suggested that there can be present no more
than eight electrons in the outermost shell of
an atom before the next shell is started. In
other words, in shells where more than eight
electrons can be present, only eight of these
enter then a new shell is started, and the
incompleted shell is left to be filled in later.
Arrangement of Electrons in Atoms
The elements are ordered according to
chemical similarity in vertical groups, and
horizontally in repetitive periods. The first
period consists of only 2 elements, hydrogen
and helium. The second and third, again,
contain 8 elements each, with each period
terminating with a rare gas, neon and argon.
On the other hand, before the next rare gas,
krypton, is reached in the fourth period 18
elements are traversed.
Of these the 8 elements potassium, gallium,
calcium, germanium, arsenic, selenium,
bromine and krypton. The latter are generally
referred to as the transition elements. In the
fifth period the situation is exactly the same as
in the fourth, the period is consisting again of
18 elements. However, when we come to the
sixth period, we find that 32 elements are
involved here. A study this shows that they
may be divided into three groups:
a. 8 more or less “normal” elements: cesium,
barium, thallium, lead, bismuth, polonium,
astatine, and radon

b. 10 transition elements ranging from


lanthanum to mercury

c. The rate earth falling between Z = 58 and Z


= 71.
Spectral Terms
When more than one electrons is
present, a different scheme has to be
employed to designate the energy
levels. The system commonly used is
that based on Russell-Saunders
coupling, and takes the form
n ^ (2S’ + 1)LJ
The symbol n refers to the major
energy level of the atom.
Quantum Mechanics
In 1925-1926 Werner Heisenberg and
Erwin Schrödinger independently
proposed a new quantum or wave
mechanics which takes cognizance of the
wave and particle duality of matter and
which deals with atomic and molecular
atomic scale problems in a totally different
manner.
Schrödinger wave Equation:
V²Ψ + (8π²m/h²)(E – U)Ψ = 0
Nature and Significance of Ψ. The
Schrödinger Equation implies in essence that a
moving body of mass m, velocity v, potential
energy U, and total energy E has a wave
associated with it of an amplitude given by the
wave function Ψ.
The particular values of Ψwhich yields
satisfactory solution of this equation are called
eigenfunctions or characteristic wave
functions, while values of the energy which
correspond to the eigenfunctions are called the
eigenvalues of the system.
Quantum Mechanics of the Hydrogen
Atom. Consider an atom consisting of a
nucleus of mass m’ and charge Ze around
which revolves one electron of mass m. In
mechanics such a combination can be looked
upon as a particle of reduced mass μ given by
1/μ = 1/m + 1/m’
The Hydrogenlike Wave Functions. The
wave function for an electron in an atom is
called an atomic orbital. Consider first the
radial distribution to Ψ for the hydrogen atom.
In each instance R² represents the probability
of finding the electron at a point between r and
r + dr in space. However, it is more
illuminating to consider the probability of
finding the electron in a spherical shell of
thickness dr at distance r from a center of the
mass, which practically identical with the
position of the nucleus.
This probability D(r), called the radial
distribution
function, is given by the expression
D(r) = 4πr²R²
Plots of the angular Parts of the Hydrogen Atom Wave Functions
The End of Slide Show…
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