CHEM 15 Chapter 3-1

CHEM 15
Chapter 3 ATOMIC STRUCTURE

The Wave Nature of Light Relationship between Wavelength and Frequency

Light travels through space as a wave - a disturbance that transmits energy through a medium.
  c where: c (speed of light) = 3.0 x 108 m/s
Electromagnetic radiation - a form of energy transmission through vacuum or a medium in
which electric and magnetic fields are propagated as a wave. It carries energy through space and When light is passed through a transparent medium such as a prism, the “white” light is refracted
is therefore also known as radiant energy. or dispersed into an unbroken or continuous band or spectrum of colors as a rainbow -
ROYGBIV.

Classical Descriptions of Matter

John Dalton (1803) - atoms are hard, indivisible particles. Atoms have distinct masses that
distinguish one type of atom from another. All atoms of same element are the same.

J.J. Thomson (1890s) - discovered charge-to-mass ratios of electrons; atoms are divisible
because the electrons are one part of atom.

Ernest Rutherford (1910) - shot positive alpha particles at a thin foil of gold from which he
discovered the atomic nucleus.

James Maxwell (1873) - visible light consists of electromagnetic waves.

Transition between Classical and Quantum Theory

Max Planck (1900) - noted matter did not emit energy in continuous bursts but in whole-number
multiples of certain well-defined quantities.
Figure 3.7 The electromagnetic spectrum
Quantum theory - Matter absorbs or emits energy in bundles or “quanta.” Radiant
energy is quantized, it is limited to a discrete set of specific values. The smallest amount of
Visible region - portion of the electromagnetic spectrum within the wavelength range of 400 -
energy that can be emitted or absorbed as electromagnetic radiation is called quantum.
750 nm that we can perceive as color.
Photoelectric effect (Albert Einstein, 1905) - a beam of electrons is produced when light
Waves have the following characteristics:
strikes a clean metal surface.
1. Wavelength,  - distance between two identical points of the wave
2. Frequency, ν - the number of troughs or crest that passes through a given point per unit of
time.
3. Amplitude, A - relates to the intensity of radiation.

Figure 3.8 Characteristics of a wave


Figure 3.9 The photoelectric effect
Observations:
 When a light strikes the metal, its energy is transferred to an electron in a metal. A certain
minimum amount of energy, threshold energy, is required for an electron to overcome the
attractive forces that hold it within the metal.
 If the light has a less energy than the threshold energy, the electron cannot escape from the
surface of the metal even if the light beam is intense.
 If the light has more energy than the minimum requirement to free an electron, the excess
appears as the kinetic energy of the emitted electron.
To explain the photoelectric effect, Einstein assumed that the radiant energy striking the metal
surface is a stream of tiny energy packets. Each energy packet behaves like a tiny particle of light
which is called a photon having a characteristic energy E = hν. Light exists as a stream of
“particles” called photons.
Energy is proportional to the frequency, ν, and wavelength, λ, of radiation, and the
proportionality constant h which is called Planck's constant.
c
E  h  h where: h = 6.63 x 10-34 Js
 in certain circular orbits around the nucleus in certain specific radii.
Radiant energy may be considered to consist of fluctuating electric and magnetic fields which
travel through space in a wavelike motion. It may be described in two ways:
1. Waves of photons - possessing wave-like properties.
2. Stream of photons - possessing particle-like properties.
Dual nature of matter (Louis de Broglie) - The electron can be imagined as both particle (it
has mass) and a wave (it moves rapidly) and either of these two natures can become
predominant at a given time.
If light can behave like a wave and a particle, matter also (electron) can behave like waves. If
electron behaves like a standing wave, it can only have specific wavelengths and specific
frequencies and thus, energies:
For wave: E  mc 2 For matter: E  h
Combining the two equations, we can solve for the wavelength for any matter.
h Unfortunately, the Bohr Model failed for all other elements that had more than one proton and
De Broglie relation:  where: m = mass in kg
m
ν = velocity m/s
This relation is true for all matter whether microscopic or macroscopic.
CHEM 15 Chapter 3-2
Illustration:
1. A baseball with a mass of 0.143 kg is thrown towards a batter at a velocity of 42.5 m/s.
a. Calculate the wavelength in m associated with the baseball’s motion.
6.63x10 34 Js
  1.89 x10 34 m
(0.143kg)(42.5m / s)
b. How does the wavelength compare in size to the baseball (diameter = 0.08 m)?
The baseball’s wavelength is very much less than its diameter.
2. Calculate the wavelength in m associated with an electron traveling at the same velocity. (The
mass of the electron is 9.1095 x 10-31 kg.)
6.63x10 34 Js
  1.71x10 5 m
(9.1095 x10 31 kg)(42.5m / s)
The wavelength of the electron is much larger than its diameter.
Thus, although all matter can have wave properties, such properties are only
significant for microscopic particles.
Bohr model of a hydrogen atom (Neils Bohr, 1913) - The electron of the atom can exist only
“Tennis ball and stairs” analogy for electrons and energy levels, respectively - a ball can bounce
up to or drop from one stair to another but it can never be halfway between two levels.
According to the Bohr’s model:
1. The electron has a definite energy characteristic of the orbit in which it is moving (like the
planetary model of the solar system).
2. When the electron of an atom is as close to the nucleus as possible, it is in a state of lowest
possible energy called the ground state. The ground state is the lowest energy state for
atom when the electron is in most stable orbit.
3. When the atom absorbs energy, an electron can jump from a lower energy level to a higher
energy level. The electron is said to be in the excited state when the electron is in a higher
energy orbit (n = 2, 3, 4, etc.).
4. When an electron falls back to the lower level, it emits a definite amount of energy in the
form of a quantum of light.
Limitations of the Bohr Model - Quantum Mechanical Model
one electron. (The multiple electron-nuclear attractions, electron-electron repulsions, and nuclear
repulsions make other atoms much more complicated than hydrogen.)
In 1920s, a new discipline, quantum mechanics, was developed to describe the motion of
submicroscopic particles confined to tiny regions of space. Quantum mechanics makes no attempt
to specify the position of a small particle at a given instant or how the electron got there. It only
 CHEM 15 Chapter 3-3
gives the probability of finding small particles - just like taking snapshot of a location and 0 s 1 spherical
estimating where greatest number of people is likely to be, it takes a snapshot of the atom at 1 p 3 dumbbell
different times and “see” where the electrons are usually found. 2 d 5 four-lobe
Heisenberg’s uncertainty principle - It is impossible to determine accurately both the exact 3 f 7 eight-lobe
position and momentum of a particle simultaneously.

Erwin Schrödinger (1926) - developed a differential equation that allows us to find the
electron's wave function, ψ which ultimately allows us to determine the probability of finding the
electron in a given place.

Probability density for an electron - called the “electron cloud” which dictates the shape of s orbital
the area where the electron resides. Regions where there is a high probability of finding the
electron are said to be regions of high electron density.

Schrodinger equation - describes an electron in an atom by a mathematical expression called a

wave function, .
It determines the following:
1. The shape of the orbital the electron occupies
2. The energy of the electron in the orbital
3. The probability of finding the electron in some region
p orbitals
The complete solution to Schroedinger’s equation yields a set of wave functions called orbitals
and their corresponding energies. Each orbital describes a specific distribution of electron density
in space.

Quantum numbers - dimensionless numbers which completely describe the state of an

electron. Four quantum numbers describe distribution and behavior of electrons in atoms. Each
wave function, ψ, corresponds to a set of three quantum numbers and is referred to as an
atomic orbital.

The four quantum numbers:

1. Principal quantum number, n - describes the distance between the nucleus and the
shell. A shell is the level to which the electrons belong - as n increases, on the average, the
electron is found farther out of the nucleus. It also describes the energy level of the shell - as
n increases, the energy of the electron increases and is therefore less tightly bound to the
nucleus.
The principal quantum number, n can have integral values 1, 2, 3, etc.
The number of electrons that can be accommodated in a given shell is equal to 2n2.

2. Azimuthal quantum number, l - defines the shape of the orbital. It describes the
energy level of the subshells. The number of subshells in a shell is equal to n.
It has any integral value starting from 0  (n - 1). d orbitals

Table 3.2 Azimuthal quantum number values

l values Symbol No. of orbitals Shape
 CHEM 15 Chapter 3-4

Electronic Configuration of an Atom

Electronic configuration - the arrangement of electrons in the orbital of an atom.
It is described by:
a. a number that designates the number of principal shell
b. a letter that designates the subshell (orbital)
c. a superscript that designates the number of electrons in that particular subshell (orbital)
e.g. 2p4 indicates 4 electrons in the p subshell of the 2nd shell
3d8 indicates 8 electrons in the d subshell of the 3rd shell

Guidelines:
1. Aufbau (building-up) principle
f orbitals Electrons are distributed in orbitals of increasing energy levels where the lowest energy
Figure 3.10 Shapes of the s, p, d, and f orbitals, respectively orbitals are filled first. Once an orbital has the maximum number of electrons it can hold, it is
considered “filled.” Remaining electrons must then be placed into the next highest energy
orbital, and so on.
Each subshell consists of a set of orbitals. All the orbitals in the same subshell have the same The orbitals in order of increasing energy:
energy. So within a given shell, the energies of electrons in the orbitals increase in the 1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f < 5d < 6p < 7s < 5f < 6d
following order: ns < np < nd < nf. < 7p

c. Magnetic quantum number, ml - determines the spatial orientation of an orbital (the

axes/planes to which the orbital is oriented). It has an integral value of +l, … 0, … ,-l.

d. Spin quantum number, ms - describes the direction of spin of an electron about its own
axis: counterclockwise, ms = -½; and clockwise, ms = +½.
Electrons with the same spin quantum numbers are said to have parallel spins while
those with different ms values are said to have opposite spins. Figure 3.11 The Aufbau principle
2. Pauli’s exclusion principle - No two electrons in the same atom can have the same set of
Table 3.3 Relationship among n, l, ml values through n = 4 four quantum numbers. That is, the maximum number of electron in an orbital is limited to
No. of Total no. of two and the two electrons in the same orbital must have opposite spins.
l Subshell
n ml values orbitals in orbitals in
values designation
subshell subshell For 1s orbital: one electron: n = 1, l = 0, ml = 0, ms = +½
1 0 1s 0 1 1 another electron: n = 1, l = 0, ml = 0, ms = -½
2 0 2s 0 1
1 2p 1, 0, -1 3 4 For example, with the helium atom, there are three ways to represent two electrons in 1s orbital
3 0 3s 0 1
1 3p 1, 0, -1 3
2 3d 2, 1, 0, -1, -2 5 9 (where spin is represented with the electron pointing up or down):
4 0 4s 0 1 But the Pauli exclusion principle rules out (a) and (b) since these show two electrons in the same
1 4p 1, 0, -1 3 orbital with the same spin.
2 4d 2, 1, 0, -1, -2 5
3 4f 3, 2, 1, 0, -1, -2, -3 7 16 An orbital can hold a maximum of two electrons:
 An s orbital can hold up to 2 electrons.
 A set of p orbitals can hold up to 6 electrons.
 A set of d orbitals can hold up to 10 electrons.

 A set of f orbitals can hold up to 14 electrons.
3. Hund’s rule - Every orbital in a subshell (degenerate orbitals - same energy) is occupied
with one electron first before any one orbital is doubly-filled and all electrons in singly-
occupied orbitals have the same spin.
The most stable arrangement of electrons in subshells has the greatest number of
parallel spins.
To do this, distribute electrons with same spin (up or down) and do not pair electrons until all
subshells have an electron.
CHEM 15 Chapter 3-5
For example, O2-, F-, Ne, Na+, and Mg2+ have a total number of electrons
which is equal to 10. If this is so, hence, they have the same electronic configuration 1s2 2s2 2p6
and are therefore isoelectronic.
Magnetic behavior - the effect of magnetic field on an atom.
1. Diamagnetism - atoms with completely paired electrons which are slightly affected by
magnetic field.
2. Paramagnetism - atoms with unpaired electrons which are greatly affected by magnetic
field.

For example, the electron configuration of carbon is: 1s2 2s2 2p2.
The orbital diagram can be shown in the following ways:
Exceptions to the Building-Up Principle
Atoms gain extra stability when their d subshells are half-filled or completely filled.
If we can fill or half-fill a d subshell by promoting an electron from an s orbital to a d orbital, we
do so to gain the extra stability.

For example, chromium has a total number of electrons equal to 24. Its electron configuration is
1s2 2s2 2p6 3s2 3p6 4s2 3d4 and an orbital diagram as follows:

But from Hund's rule, we know (c) would be the most stable. However, chromium assumes a more stable configuration by promoting one 4s electron to the 3d
subshell to attain half-filled stability. Its actual configuration becomes 1s2 2s2 2p6 3s2 3p6 4s1
3d5 with an orbital diagram as shown.

Orbital diagrams of some elements

Total Orbital diagram Electronic Valence
Element
electrons 1s 2s 2p 3s configuration electrons
H 1  1s1 1
He 2  1s2 2 Similarly, silver assumes a more stable configuration by promoting one 4s electron to the 3d
Li 3   1s2 2s1 1 orbital via completely filled stability. From 1s2 2s2 2p6 3s2 3p6 4s2 3d9, its actual configuration
Be 4   1s2 2s2 2 becomes 1s2 2s2 2p6 3s2 3p6 4s1 3d10.
B 5    1s2 2s2 2p1 3
C 6     1s2 2s2 2p2 4
N 7      1s2 2s2 2p3 5 Writing Electron Configurations Using the Periodic Table
Ne 10      1s2 2s2 2p6 8 The periodic table's shape actually corresponds to the filling of energy sublevels. The numbers on
Na 11       1s2 2s2 2p6 3s1 1 atop the columns in the following figure gives the ml values of the corresponding subshell. In the
Valence electrons - outer shell electrons. first half of the set of ml values, the electrons have +½ spin quantum number while the on other
half, they will assume -½ spins.

Isoelectronic - atoms or ions of different elements that have the same electronic configuration.
 CHEM 15 Chapter 3-6

Figure 3.12 The periodic table showing the different sublevels

Abbreviated Electron Configurations
Since noble gases are at the end of each row in the periodic table, all of their electrons are in
filled orbitals. Such electrons are called core electrons since they are more stable (less reactive)
when they belong to completely filled orbitals.

Noble gas core notation - noble gas electron configurations can be used to abbreviate the core
electrons of all elements.

[He] = 1s2
[Ne] = 1s2 2s2 2p6
[Ar] = 1s2 2s2 2p6 3s2 3p6
[Kr] = 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6
[Xe] = 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6

a. shell where n = 3
b. shell with n = 4 before the first electron enters the shell with n = 5