STATE UNIVERSITY OF MAKASSAR

BASIC CHEMISTRY

INTERNATIONAL CLASS PROGRAM

DEPARTEMENT OF CHEMISTRY
HANDOUT, 2009

ATOMIC STRUCTURE

Indikators
Students are able to
Explain the atomic theory according to Dalton and Thomson
Explain about basic particles
Explain the atomic theory of quantum mechanics
Explain and determine the quantum numbers
Explain about Rutherfords and Bohrs atomic theory
Describe the atomic orbital shapes
Explain the atomic shell and subshell and their relations to the quantum numbers
Use Aufbau principle, Pauli exclusion principle, and Huds rule in writing an
electron configuration and describing the orbital diagram
A. ATOMIC STRUKTURE
Matter is made up of small particles that are in constant motion. The particles
in solids are packed closely together and, even though their positions are fixed in the
crystal, the individual particles can vibrate. The particles in liquids can move about
(or flow) because they are not locked into fixed positions. The particles in gases are
widely separated and move very much faster than those in liquids. The rapid motion
of gas particles allows them to spread out rapidly so that they eventually occupy the
entire space of their container.
Solids and liquids are often classified as condensed matter. The closeness of
the particles makes solids and liquids almost incompressible. Gas, however, are easy
to compress as there is considerable free space between their particles.
Chemists have discovered that there are many different types of particles that
make up matter. These include:
Atoms; the smallest particles of an element that can take part in a chemical reaction.
Atoms are composed of three fundamental particles called protons, neutrons and
electrons.
Molecules; the smallest part of a pure substance that can exist separately. Molecules
are usually composed of two or more atoms chemically bonded together, although
the noble gases (including helium and argon) are regarded as monatomic (singleatom) molecules.
Ions; charged atoms or charged molecules. Ions can be positively or negatively
charged.

1. Daltons Atomic Theory

As weve noted, laws of conservation of mass and definite proportions are
based solely on experimentally measured masses of chemicals in compounds and
chemical reactions. Chemists of the late eighteenth century could not help but wonder
what matter must be like in order for these laws to hold, and 1803 an English
schoolteacher- scientist named John Dalton proposed an explanation, called the
atomic theory, that changed the course of chemical science.
The concept of atoms was not new, Greek philosophers as early as 500 B.C.
had pondered the possibility that matter might be composed of tiny indivisible
particles. In fact, the word atoms comes from the Greek atomos meaning indivisible.
The ancient Greeks, however, had no data to explain and their proposals were little
more than exercises in thought Daltons theory was different, though, because his had
to explain the observed laws of conservation of mass and definite proportions.
The theory Dalton proposed can be expressed by following postulates:
1) Matter is composed of tiny indivisible particles called atoms.
2) All atoms of a given element are identical, but differ from atoms of other
elements. This means that all atoms of a given element have the same mass, but
this mass differs from the masses of atoms of other elements.
3) A chemical compound is composed of the atoms of its elements in a definite fixed
numerical ratio.
4) A chemical reaction merely consists of reshuffling of atoms from one set of
combinations to another. The individual atoms themselves, however, remain intact
and do not change.
Daltons idea that different elements had different atoms was unlike the
Democrituss idea about atoms. The properties of Daltons atoms determined the
chemical and physical properties of a substance. For example, carbon atoms can form
both diamonds and graphite atoms because both substances are composed of the same
chemical elements. Whereas according to the Democrituss idea about atom, diamond
atoms would be very different from graphite atoms.
Dalton observed that two elements can combine in more than one way. For
example, modern scientist knows that carbon monoxide (CO) and carbon dioxide
(CO2) are both compounds of carbon and oxygen. According to Daltons experiments,
the quantities of an element needed to compose the different compounds are always
whole-number multiples of one another, For example, oxygen needed to form a liter
of CO. Based on the result of his experiment, Dalton concluded that compounds were
created when atoms of pure elements joined together to form a unit called molecule in
fixed proportions. This Daltons conclusion is also called doubled multiple laws.

2. Thomsons Atomic Model

Since the found of electron as the elementary negatively charged particle, so
the validity of Daltons atomic theory begin to the questionable. In 1899, a British

physicist. Sir Joseph Thomson, proposed an atomic model called raisin plum
pudding model. Thomson described atom as a positively charged sphere containing
several negatively charged particles called electrons. The electrons are scattered in
the sphere like raisins in a plum pudding.
The first important experiments that led to an understanding of atom were
done by J.J. Thomson ( 1856-1940 ) during the period from 1898 to 1903.
Thomsons experiments involved electrical discharges in partially evacuated
tube called of cathode-ray tube ( CRT ), early predecessor of todays television and
computer display. The first cathode-ray tube was made by Michael Faraday about 163
years ago. As illustrated in Figure 8.2, a cathode-ray tube is a glass tube from which
the air has been removed, using a vacuum pump, and is which two thin pieces of
metal, called electrodes, have been sealed. There are two kinds of electrode, one is
negatively charged electrode called cathode, the other is positively charged electrode
called anode.
When a sufficiently high voltage is applied across the electrodes, an electric
current flows through the tube from the negatively charged electrode (the cathode) to
the positively charged electrode (the anode). If the tube is not fully evacuated but still
contains a small amount of air or the gas, the flowing currents is visible as a glow
called a cathode ray (because it emanated from the cathode). Furthermore, if the
anode has a hole in it and the end of the tube is coated with a phosphorescent
substance such as zinc sulfide, the rays pass through the hole and strike the end of the
tube, where they are visible as a bright spot of light. (In fact, this is exactly what
happens in television set). Because the rays are deflected toward a positive plate,
Thomson proposed that cathode rays consist of tiny negatively charged particles,
which we not called electrons. Electron is a fundamental particle or subatomic
particle.
One of Thomsons primary goals in his experiments was to gain an
understanding of the structure of the atom. He reasoned that since electrons are
emitted from electrodes made of many different metals and all of the metals consist
of atoms, therefore all these different atoms must contains electrons. Since atoms
were known to be electrically neutral, Thomson further proposed that atoms must
contain some positive charge. Based on these arguments Thomson postulated that an
atom consisted of a diffuse sphere cloud of positive charge with negative electrons
embedded randomly in it. This model, shown in Figure 8.3, is often called the plum
pudding model because the electrons are like raisins dispersed in a pudding (the
positive charge cloud), as in plum pudding, a favorite English dessert.
By carefully measuring the amount of deflection of cathode ray caused by
electric field and magnetic field of known strength, Thomson was able to calculate
the ratio of the electrons charge to its mass-its charge-to-mass ratio, e/m. The value is
e/m = - 1.758 820 x 108 C/g
Where e is the magnitude of the charge on the electron in coulombs (C) and m is the
mass of the electron in grams.

Thomson was able to measure the ratio of charge to mass of the electron, not
charge or mass it self. In 1909 Robert Millikan (1969-1953), working at the
University of Chicago, performed very clever experiments involving charged oil
drops as shown in Figure 8.4.
In Millikans experiment, a fine mist of oil was sprayed into a chamber, and
the tiny droplets were allowed to fall between two horizontal plates. Observing the
spherical oil drops through a telescopic eyepiece made it possible to determine how
rapidly they fell through the air, which in turn allowed their masses to be calculated.
The air between the plates was irradiated with X-rays, knocking electrons out
of nitrogen and oxygen molecules. Some of these electrons collided with the oil drops
and become attached to them, giving the oil drops a negative charge. The fall of the
drops under gravity could then be stopped by charging the plates, the upper plate
positively and the bottom plate negative.
Millikan observed individual oil drops with a microscope and adjusted the
charge on the plates until the force acting on the drop due to the charged plates just
balanced the force due the gravity and a drop remained stationary. With the voltage
on the plates and the mass of the oil drops known, Millikan was able to show that the
charge on a given drop was always small whole-number multiple of e, whose value is
-1.602 176 x 10-19 C. Substituting the value of e into Thomsons charge-to-mass
ratio gives the mass of the electron m.
e/m = - 1.758 820 x 108 C/g
e
Then m

= - 1.602 176 x 10-19 C

= - 1.602 176 x 10-19 C
- 1.758820 x 108 C/g
= 9.109 382 x 10-28 g

At the time Thomson proposed his atomic model, evidence for the existence
of positively charged particles was available from cathode-ray tube experiment. In
1886 Eugen Goldstein noted that cathode-ray tube with a perforated cathode emitted
glow from the end of the tube near the cathode. Goldstein concluded that in addition
to the electrons, or cathode rays, that traveled from cathode to anode, there was
another ray that traveled in the opposite direction, from the anode toward the cathode.
Because these rays passed through the holes, or channels, in the cathode, Goldstein
called them canal rays. Since the canal rays travel in the opposite direction of cathode
rays, as shown in Figure 8.5, they must carry positive charge.
These positive rays are created when cathode rays knock electrons from the
gaseous atoms in the tube, forming positive ions. Different elements give positive
ions with different charge-to-mass ratios; e/m. Canal rays have e/m many times
smaller than those of electron due to their much charge equal to that of electron, or
+1.

3. Rutherfords Atomic Model

In 1991, Ernest Rutherford, Geiger and Marsden was doing experiment by
shooting the alpha particle () on the thin plate of gold to prove Thomsons atomic
theory. From the result of experiment, Rutherford proposed a theory or model of atom
as follows.
.a. The atom consist of atomic nuclei which is positively charged. The nucleus
contains almost entire mass of the atom and surrounded by electrons which are
negatively charged as in solar system model.
b. Entirely, the atom has neutral characteristic because the sum of positive charges
and equal to the sum negative charges.
c. During revolving the nucleus, the centripetal force on the electrons is formed from
the attractive force among electrons and nucleus (Coulombs force)

Figure 2. Rutherfords atomic model

D. Atomic Spectrum and Bohrs Atomic Model

1. Continuous Spectrum
Light from many sources, such as the sun or light bulb appears white. If white
light passes through a prism, it is separated into a spectrum with different colors. The
prism separates the light by refracting or bending light of different colors at different
angles. In this case, a white light consists of electromagnetic wave components with
different in frequencies, wavelengths, and colors. Thus, spectrum is a distribution of
colored light (monochromatic light) produced when a beam of white light
(polychromatic light) is dispersed into its components. In other words, a given
spectrum consists of a range of radiation frequencies of electromagnetic wave which
has a specific property.
A spectrum emitted by a solid object heated to incandescence or by a liquid or
a high dense gas is usually a continuous spectrum. In this case, the continuous

spectrum is a sequence of electromagnetic wave frequencies that is without breaks

over a relatively wide range of wavelengths.
In a continuous spectrum, the light of all colors is present in it and the colors
blend continuously into one another and form a rainbow-like pattern. A continuous
spectrum can be analyzed only by using spectrophotometric methods.
2. Line Spectrum
If a tube filled by a gas or vapor of a certain element such as lithium, barium,
mercury, sodium, and neon, is conducted with a high-voltage electricity, atoms of the
elements will emit electromagnetic wave (light) for several wavelengths. If this light
is passes through a spectrometer and is analyzed, there will come up with a certain
spectrum called the line spectrum. In this case, the line spectrum is a spectrum made
of a series of distinct lines and this spectrum is a characteristic of emission or
absorption by atoms.
3. Hydrogen Atom Spectrum
A light produced by hydrogen gas atoms can be analyzed by using a
spectrometer and there is found that hydrogen atom spectrum is a line-spectrum (not
continuous spectrum).
In 1885, J.J. Balmer discovered an empirical formula to explain the spectrum of
hydrogen atom, that is as follows :
1
1 1
R 2 2

2 n
where :
= wavelength (m)
R
= Rydbergs constant (1,0974 x 107 m-1)
n
= 3,4,5,
The equation above is known as the Balmers series, and in this case, for n = 3
there is found wavelength of light is 656,3 nm, while for n = ~ there is found
wavelength of light of 364,6 nm. Therefore, the wavelength of hydrogen spectrum is
located in visible light region, that is between 364,6 nm to 656,3 nm.
Some time later, after Balmer had discovered the empirical formula for
representing the wavelength of hydrogen spectrum, other scientists succeeded in
formulating series which are similar to Balmers series, they are Lyman (1906),
Paschen (1908), Bracket (1922), and Pfund (1924)
.
1
1 1
R 2 2
Lymans series } n = 2,3,4,

1 n
1
1 1
R 2 2
Paschens series } n = 4,5,6,

3 n

1
1 1
R 2 2

4 n
1
1 1
R 2 2

5 n

Brackets series } n = 5,6,7,

Pfunds series } n = 5,6,7,

If the wavelength of hydrogen spectrum according to Balmers series is

located un the visible light region (H = violet light, H = blue light, H = blue-green
light, and H = red light), according to Lymans series, the wavelength is located in
the ultraviolet region, and according to Paschen, Bracket, and Pfund series are located
in the infra-red region.
4. Bohrs Atomic Model
The weakness of Rutherfords atomic theory in explaining the line spectrum
of hydrogen atom was successfully corrected by Niels Bohr, in 1913, based on
Rutherfords atomic theory and Plancks quantum theory, Bohr proposed postulates
about atomic models, those are as follow :
1. Electrons in atom revolve the nucleus at a certain path called stationary path.
At this path, they do not absorb nor release energy and they have angular
momentum, the magnitude of which is multiplication of h

2 .

2. Electrons will release energy (in the form of photon) if they displace from a
higher energy level to a lower one (from outer to the inner path) and electrons
will absorb energy when they displace from a lower energy level to a higher
one (from the inner to the outer space).

Figure 3. Bohrs atomic model

Based on the Bohrs postulates, several electron quantities in hydrogen atom

such as velocity of electron in revolving the nucleus and energy of electron can be
determined. From the Bohrs first postulate, the angular momentum of electron
complies the equation as follows :

Lmvr

where :
L = angular momentum of electron
m = mass of electron
v = velocity of electron
r = distance of electron to the nucleus
h = Plancks constant
n = 1,2,3,

nh

By rearranging the equation of electron angular momentum, the linear

velocity of electron in revolving the nucleus can be determined as follows :
v

nh
2 m r

Meanwhile, the total energy of electron in each orbit is as follows :

13,6
En
eV
n2
where :
En = energy of electron at n-th shell
These energy levels of electron can be diagrammatically depicted as follows :
n=~

0 eV

n=7
n=6
n=5

-0,28 eV
-0,38 eV
-0,54 eV

n=4

-0,85 eV

n=3

-1,51 eV

n=2

-3,40 eV

n=1

-13,6 eV

Figure 4. Energy levels of electron

If an electron occupies the lowest energy level (n=1), the atom is said to be in the
ground state. In the above diagram, the electron which is in the ground state is shown
as .
As an electron absorbs an amount of energy, which corresponds to the
difference in energy between its present energy level and some other energy level, the
electron will displace to a higher energy level (outer shell). The displacement of
electron from the inner to the outer shell is called excitation, while the displacement
of electron fro the excited state to the initial state is called transition. According to
Bohr, in an excitation state, the electron absorbs energy, while in a transition state, the
electron release energy. The energy absorbed or released by the electron is in the form
of photon or light. The amount of energy absorbed or released by the electron at
excitation or transition can be determined as follows :
E hf h

c
E final E initial

Energy difference between the ground state (n = 1) and energy level where n =
2 is 10,2 eV. This amount of energy corresponds to energy which must be absorbed
by the electron in order to jump from n = 1 to n = 2. Similarly, if the electron
absorbs of 13.6 eV, the electron will displace to the energy level for n = 5.
Sample Problem 1.1.
An electron of hydrogen atom is in transition from the 2nd to the 1st shell, determine :
a. the energy released
b. the frequency of photon emitted
Solution
a. the energy released
E E

final

initial

E E 1 E 2

13,6 eV

13,6 eV
10,2 eV

2 2

in Joule :
E = -10,2 x 1,6 x 10-19 Joule
= -1,63 x 10-18 Joule
Thus, the energy released by the electron is 10,2 eV or 1,63 x 10-18 Joule.
b. the frequency of photon
E = hf
f

1,63 x 10 18 J
E

2,45 x 1015 Hz
h
6,63 x 10 34 Js

Thus, the frequency of photon is 2,45 x 1015 Hz.

The displacement of electrons in an atom from n th shell to the infinity shell

will cause the atom to be charged (ionized) and the amount of energy required to
release electrons from the nth shell to the infinity shell is called the ionization energy,
which can be determined as follows :
E ionization = E final E initial
= E ~ - En
13,6 eV
13,6 eV

= 0
2
n
n2

E. Quantum Mechanics Theory

Although the Bohrs atomic theory can explain the phenomenon of hydrogen
atom spectrum and it can be used to determine the electron quantities such as velocity
and energy, it still has several weakness, among others are Bohrs atomic model can
only explain the hydrogen atom, while many electrons atoms cannot be explained
using the Bohrs atomic model ; the actual electron path is not so simple as proposed
by Bohr (circular path), but it is more complicated and has the orbital subshells ; and
the Bohrs atomic theory cannot explain the occurrences in chemical bonds and the
effect of magnetic field to an atomic spectrum.
Based on the above mentioned facts, the Bohrs atomic theory was developed
and corrected by other scientists and finally there obtained a modern atomic theory
known as quantum mechanics theory. The followings are explanations about the
quantum mechanics theory initiated by de Broglie wave and Heisenberg uncertainty
principle.
1. de Broglie Wave
In 1923, Louis de Broglie proposed that all particles (not merely photon) have
both wave and particle properties. de Broglie calculated that every particle has a
wavelength which is equal to the Plancks constant (h) divided by the momentum of
particle (p).

h
p

In this case, is called de Broglie wavelength and any particles such as

electrons and atoms have de Broglie wavelength. Because momentum of a certain
particle depends on its speed and mass, the de Broglie wavelength of a particle can be
formulated as follows :

where :
= wavelength of particle (m)
m = mass of particle (kg)
v = speed of particle (m/s)

h
mv

de Broglies idea about the wave behavior possessed by a particle has

successfully been proved by Davisson and Germer in 1927 through an experiment
using electrons within a vacuum tube. In their experiment, Davisson and Germer
accelerated electrons by using an electric field produced by an electric potential
difference of V = 54 volt, so the electron have an amount of kinetic energy.
Although a particle can behave like a wave, the common objects do not show
the behavior of wave, it is because the symptoms of a particle can occur if the particle
has an extremely large in velocity (approaching the velocity of light). For example, a
ball that moves with speed of 150 km/hour has wavelength about 1,1 x 10 -34 m. The
wavelength is not sufficient to make the ball behave like a wave.
2. Heisenberg Uncertainty Principle
The presence of particles behavior for light (electromagnetic wave) and wave
behavior for the particles causes an uncertainty in measuring quantities, such as
momentum and position of a particle. For example, the measurement of electrons
momentum using the instrument that involves light will resulting a measurement
followed by the uncertainty. In fact, we cannot explain the motion of electrons based
on the classical physic theories (Newtonian mechanics).
Based on the collision principle in classical mechanics consideration, in a
collision between photon and electron there will be obtained measurement of
momentum uncertainty which has value of at least equal to the momentum of photon,
that is :
p

where :
p = momentum of uncertainty

From the formulation above, the momentum of uncertainty of particle

(electron) is inversely proportional to the wavelength of light (photon). The
wavelength of light can be used to determine the value of the electrons position
uncertainty. The value of the electrons position uncertainty is at least equal to the
wavelength of light.
x
where :
x = position uncertainty
The notation of p

and x

in the relation to momentum

measurement has a meaning that, reducing the momentum uncertainty it can be done
by increasing the wavelength of light and at the same time the position uncertainty
will increase.

Based on the above case, in 1927, Warner Heisenberg formulated a principle

known by Heisenberg uncertainty principle or indeterminacy principle. This
principle plays role in the development of quantum mechanics.
In this case, the Heisenberg uncertainty principle prescribes that It is
impossible to measure or to specify the momentum and the position of a particle
simultaneously with unlimited precision. Or in other words the measurement of
momentum and position of a particle simultaneously always results in an uncertainty
which is never less than Plancks constant. Mathematically, Heisenberg uncertainty
principle can be expressed in the following equation :
p x h

3. Schrodingers Wave Function

Based on de Broglies idea and Heisenberg uncertainty principle, in 1926
Erwin Schrodinger proposed an idea that if electrons have characteristics of wave, of
course they have a wave function representing their state. According to Schrodinger,
the wave function of electrons in revolving the nucleus of an atom can be represented
by the free wave function of time as follows :
( x ) A sin kx

where :
A = wave amplitude
k = wave number
Because electrons have wave characteristics, according to Schrodinger,
electrons in an atom do not orbit the nucleus, but they behave more likely as waves
traveling at a certain distance with a given energy around the nucleus.
Schrodingers atomic model was proved to be more accurate and based on this
model, physicists no longer try to find the electrons path and its position in an atom.
Instead, they use the equation describing the electron wave to find the region in which
the electron is most likely to be found.
Based on the Schrodingers atomic model, the quantization of angular
momentum of electron as it has been proposed by Bohr can occur because the
electron wave forms a stationary wave. In this case, the atomic model based on wave
characteristics of electron described by using this Schrodingers wave function is
called the atomic model of quantum mechanics or atomic model of wave mechanics.

F. Quantum Numbers and Atomic Orbitals

The Bohrs atomic model is a one-dimensional model using one quantum
number to describe the distribution of electrons in an atom. Such information only
relates to the size of the orbit of electrons in an atom, which was described by the n
quantum number. Schrodingers atomic model allows electron to occupy three-

dimensional space. Hence, to describe the orbitals in which electron can be found in
an atom three coordinates or three quantum number are required.
The three coordinates or quantum numbers which come from the exact
solution of Schrodingers wave equations are the principal quantum number (n),
azimuth or angular quantum number (), and magnetic quantum number (m).
Those quantum numbers describe the size, shape, and orientation of orbitals in an
atom.
1. Principal Quantum Number (n)
Principal quantum number (n) describes the size of the orbital which refers to
the quantum number n in the Bohrs atomic theory. For example, orbital for which n
= 2 is larger than that of for n = 1. The principal quantum number also indirectly
describes the energy level of an orbital.
Based on Bohrs atomic theory, the energy of electron in hydrogen atom (Z =
13,6 eV
1) is E
, but for atoms besides hydrogen, the energy of electron obeys
n2
the equation as follows :
13,6 eV 2
En
Z eV
n2
Where :
Z = atomic number
n = principal quantum number (n = 1,2,3, )
The position of electrons which appropriates to energy level of the electrons is
represented by atomic shells and symbolized by K, L, M, N, O, P and so forth. The
relation of the principal quantum number and the atomic shells is shown in the table
below :
n
Shell symbol

1
K

2
L

3
M

4
N

5
O

2. Azimuth Quantum Number ()

Azimuth quantum number or angular quantum number is the number which
represents the magnitude of angular momentum of electron and atomic subshell
which determines atomic orbital shapes. The angular momentum of electron to the
axis of atomic nucleus can be determined as follows :
L

( 1) h

In this case, is angular quantum number which has the values from zero to n
1.
= 0, 1, 2, , n-1

6
P

where :
n = principal quantum number
Each atomic subshell is symbolized by using letters of s, p, d, f, g, h, I, and so
forth, which appropriates to the state of angular quantum number (). Pay attention to
the following table :

Name of subshell

0
s

1
p

2
d

3
f

4
g

5
h

6
i

The naming of subshell is based on the empirical classification of spectrum,

suppose s from sharp, p from principal, d from diffuse, f from fundamental, and so
forth.
3. Magnetic Quantum Number (m)
In physics, we have known that angular momentum is a vector quantity, so it
has both a magnitude and direction.
If the magnitude of electron angular momentum is represented by angular
quantum number, the direction or orientation of it is represented by the magnetic
quantum number (m). Magnetic quantum number also represents a particular orbital
occupied by electrons in a certain subshell. It is called the magnetic quantum number
because the effect of different orientations of orbitals was initially observed in the
presence of a magnetic field.
The value of magnetic quantum number depends on the value of angular
quantum number, that is all integers begin from - to +, including zero.
m = -, , 0, , +
4. Atomic Orbitals
Atomic orbitals are mathematical descriptions of electrons position in an
atom which is most likely to be found. These descriptions are obtained by solving the
Schrodingers equation. Each orbital has a size, shape, and orientation determined by
the n, , m quantum numbers. The orbitals combine to form subshells and they can
combine to form shells or energy levels.
Among the orbital shapes are spherical, polar, and cloverleaf shapes as shown
in the following figure. The spherical shape occurs if = 0 ( s orbital) ; polar shape
occurs if = 1 (p orbital) ; and cloveleaf shape occurs if = 2 (d orbital).

Figure 5. Orbital shapes for = 0, = 1, and = 2