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Project in PCHM413L1

( Physical Principles 2 )

Prepared by:

John P. Bandoquillo

CH41FB1

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

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.

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

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

Comparison of Properties of H2O and D2O

Property H2O D2O

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

Mvr = nh / 2π

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

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.

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

lanthanum to mercury

= 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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