Module 3 (Part 2)

Subject CHM012 Chemistry for Engineers

Chapter/Unit 3
Lesson Title Atomic Structure and the Periodic Table
Timeframe Week 3
Lesson Objectives 1. Compare the Bohr model, Rutherford model and the Quantum
mechanical model of the atom
2. Explain the four quantum numbers
3. Elucidate the quantum mechanical model of the atom
4. Give the electronic configuration of an element
5. Compare similarities and contrast differences of element within a
group/period in the periodic table
Overview/Introduction In this chapter we begin by looking at the nature of light and how our
description of light was changed by the quantum theory. We will
explore some of the tools used in quantum mechanics, the “new”
physics that had to be developed to describe atoms correctly. We will
then use the quantum theory to describe the arrangements of electrons
in atoms— what we call the electronic structure of atoms. The
electronic structure of an atom refers to the number of electrons in the
atom as well as their distribution around the nucleus and their energies.
We will see that the quantum description of the electronic structure of
atoms helps us to understand the arrangement of the elements in the
periodic table—why, for example, helium and neon are both unreactive
gases, whereas sodium and potassium are both soft, reactive metals.
Activity Exercises/Assignment
Assessment Problem Set
References Brown, T.L., LeMay Jr., H.E., Bursten, B.E., Murphy, C.J., Woodward, P.M.,
“Chemistry – The Central Science”, (14th edition), Prentice-Hall International,
Inc. (Chapter 1)

Electronic Structure of Atoms

 refers to the number of electrons in the atom as well as their distribution around the nucleus and their energies. It is
the arrangement of electrons in an atom

THE WAVE NATURE OF LIGHT

Electromagnetic Radiation
 also known as radiant energy since it carries energy through space
 is a form of energy transmission through vacuum or a medium in which electric and magnetic fields are propagated as
wave.
.
Types of Electromagnetic Radiation

Visible region: portion of the EM spectrum that we can perceive as color (λ: 400 – 750 nm)
For example:

A "red-hot" or "white-hot" iron bar freshly removed from a high temperature source has forms of energy in different parts
of the EM spectrum

 red or white glow = radiation within the visible region

 warmth = radiation within the infrared region

Common Terms

Wave: a disturbance that transmits energy through a medium.

Wavelength,  (Greek “lambda”) - distance between two identical points of the wave
Frequency.  (Greek “nu”) - the number of troughs or crest that passes through a given point per unit of time.
Amplitude, A – relates to the intensity of radiation.
Relationship of Wavelength and Frequency

  c
Where c = speed of light = 3.0 x 108 m/sec

 When light is passed through a transparent medium such as a prism, the “white” light is refracted or dispersed into an
unbroken or continuous band or spectrum of colors. e.g. rainbow - ROYGBIV

Exercise 1:
1. The yellow light given off by a sodium vapor lamp used for public lighting has a wavelength of 589 nm. What is the
frequency of this radiation?
2. (a) A laser used in eye surgery to fuse detached retinas produces radiation with a wavelength of 640.0 nm. Calculate
the frequency of this radiation. (b) An FM radio station broadcasts electromagnetic radiation at a frequency of 103.4
MHz. Calculate the wavelength of this radiation. The speed of light is 2.999 x 108 m/s to four significant digits.

Solution:
1. 5.09 x 1014 s-1

QUANTIZED ENERGY AND PHOTONS

Classical Descriptions of Matter

John Dalton (1803)

 atoms are hard, indivisible, billiard-like particles
 atoms have distinct masses (what distinguishes on type of atom from another)
 all atoms of same element are the same

JJ 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
 discovery of the atomic nucleus

James Maxwell (1873)

 visible light consists of electromagnetic waves

Transition between Classical and Quantum Theory

When solids are heated, they emit radiation, as seen in the red glow of an electric stove burner or the bright white light of a
tungsten lightbulb. During the late 1800s, a number of physicists studied this phenomenon, trying to understand the
relationship between the temperature and the intensity and wavelength of the emitted radiation. The prevailing laws of
physics could not account for the observations.

Max Planck (1900); Blackbody Radiation

 solved the problem by assuming that energy can be either released or absorbed by atoms only in discrete “chunks” of
some minimum size.
 heated solids to red or white heat; noted matter did not emit energy in continuous bursts, but in whole-number
multiples of certain well-defined quantities
 matter absorbs/emits energy in bundles = "quanta" (single bundle of energy= "quantum")

“Radiant energy is quantized, i.e. it is limited to a discrete set of specific values. The smallest amount of energy that can
be emitted or absorbed as electromagnetic radiation is called quantum.”
Albert Einstein (1905); Photoelectric Effect
A few years after Planck presented his quantum theory, scientists began to see its applicability to many experimental
observations. Einstein used Planck’s theory to explain photoelectric effect.
 Photoelectric Effect: Light shining on a clean metal surface causes the surface to emit electrons.

“A beam of electrons is produced when light strikes a clean metal surface.”

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 and is called a photon having a characteristic
energy, given by Planck’s equation, E = h.

Einstein applied Planck's quantum theory to light: 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) is now called
Planck's constant (6.626×10–34 J·s)
hc
E  h 


Exercise 2
1. Calculate the energy of one photon of yellow light that has a wavelength of 589 nm. How much energy will one mole
of these photons supply? (Hint: Use Avogadro’s number: 6.02 x 10 23 photons/mol).
2. (a) A laser emits light that has a frequency of 4.69 x 10 23 s-1. What is the energy of one photon of this radiation? (b) If
the laser emits a pulse containing 5.0 x 1017 photons of this radiation, what is the total energy of that pulse? (c) If the
laser emits of energy 1.3 x 10-2 J of energy during a pulse, how many photons are emitted?

Solution:
1.
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:

WAVES OF PHOTONS (possessing wave-like properties)

RADIANT ENERGY
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.”

Particle (with particle properties)

electron
Wave (with wavelike properties)

De Broglie relationship (Louis de Broglie)

 Explains the dual behavior of matter
 If light can behave like a wave and a particle  matter (like an electron) can behave like waves; if electron behaves
like a standing wave  an electron can only have specific wavelengths  an electron can only have 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
De Broglie relation:   true for all matter whether macroscopic or microscopic
mv
Where v = velocity/speed
m = mass
Exercise 3.
1. Determine the de Broglie wavelength (in nm) associated with a neutron traveling at a speed of 5.0 × 103 m/s. The
mass of a neutron is 1.67 × 10–24 g.
2. Calculate the wavelength associated with a 42 g baseball with speed of 80 m/s. Is this wavelength very small? Why or
why not?

LINE SPECTRA AND THE BOHR MODEL

A particular source of radiant energy may emit a single wavelength, as in the light from a laser. Radiation composed of a
single wavelength is monochromatic. However, most common radiation sources, including lightbulbs and stars, produce
radiation containing many different wavelengths and are polychromatic.

Emission Spectra: produced when radiation from such sources is separated into its component wavelengths; Radiation
emitted by substances either be continuous or line spectra

 Continuous spectrum = spectrum containing all wavelengths of light, like a rainbow

o Example: A heated solid (e.g. the filament in an incandescent light bulb) emits light that can be spread out
 Line spectrum: A spectrum containing radiation of only specific wavelengths
o Example: An atom in the gas phase emits light only at specific wavelengths =
o each element has a unique line spectrum → can be used to identify unknown atoms in chemical analysis
o Line spectrum for each element is called its "atomic fingerprint"

The Bohr Model of a Hydrogen Atom (Neils Bohr, 1913)

When scientists first detected the line spectrum of hydrogen in the mid-1800s, they were fascinated by its simplicity. At
that time, only four lines at wavelengths of 410 nm (violet), 434 nm (blue), 486 nm (blue-green), and 656 nm (red) were
observed.

To explain the line spectrum of hydrogen, Bohr assumed that electrons in hydrogen atoms move in circular orbits around
the nucleus, but this assumption posed a problem. According to classical physics, a charged particle (such as an electron)
moving in a circular path should continuously lose energy. As an electron loses energy, therefore, it should spiral into the
positively charged nucleus. This behavior, however, does not happen — hydrogen atoms are stable. So how can we explain
this apparent violation of the laws of physics? Bohr approached this problem in much the same way that Planck had
approached: He assumed that the prevailing laws of physics were inadequate to describe all aspects of atoms and he
adopted Planck’s idea that energies are quantized.

The Bohr’s Model

1. The electron of the atom can exist only in certain circular orbits around the nucleus in certain specific radii.
 "tennis ball and stairs" analogy for electrons and energy levels
 a ball can bounce up to or drop from one stair to another, but it can never be halfway between two levels

2. The electron has a definite energy characteristic of the orbit in which it is moving.

3. 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. (lowest energy state for atom; when the electron is in most stable orbit.

4. 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,...)
5. When an electron falls back to the lower level, it emits a definite amount of energy in the form of a quantum of light
(E = hʋ).

Bohr’s Atomic Model

Limitations of the Bohr Model → Quantum Mechanical Model

Unfortunately, the Bohr Model failed for all other elements that had more than one proton and 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
o It only gives the probability of finding small particles
o Just like taking snapshot of a location and estimating where greatest number of people is likely to be
o Instead we take a snapshot of the atom at different times and “see” where the electrons are usually found

Heisenberg’s Uncertainty Principle

The German physicist Werner Heisenberg proposed that the dual nature of matter places a fundamental limitation on how
precisely we can know both the location and the momentum of an object at a given instant.

“It is impossible to determine accurately both the exact position and momentum of a particle simultaneously.”

When applied to the electrons in an atom, this principle states that it is impossible for us to know simultaneously both the
exact momentum of the electron and its exact location in space.

Erwin Schrödinger (1926)

 proposed an equation, now known as Schrödinger’s wave equation, that incorporates both the wave-like behavior of
the electron and its particle-like behavior

Schrodinger Equation

 describes an electron in an atom by a mathematical expression called a wave function,  (psi).

  determines the following:
o the shape of the orbital the electron occupies
o the energy of the electron in the orbital
o the probability of finding the electron in some region
 the wave function has no direct physical meaning, the square of the wave function (ψ2) provides information about
the electron’s location when it is in an allowed energy state
 ψ2 at a given point in space represents the probability that the electron  probability density/electron density for
an electron  “shape”
ORBITALS AND QUANTUM NUMBERS
 The solution to Schrödinger’s equation for the hydrogen atom yields a set of wave functions called orbitals. Each
orbital has a characteristic shape and energy
 Note that an orbital (quantum mechanical model, which describes electrons in terms of probabilities, visualized as
“electron clouds”) is not the same as an orbit (Bohr model). The quantum mechanical model does not refer to orbits
because the motion of the electron in an atom cannot be precisely determined (Heisenberg uncertainty principle).
 In the quantum mechanical model, there are 4 quantum numbers

QUANTUM NUMBERS
 dimensionless numbers which completely describe the state of an electron.
o 4 quantum numbers describe distribution and behavior of electrons in atoms
o Each wave function corresponds to a set of 3 quantum numbers and is referred to as an atomic orbital
 The location and energy of every electron in an atom is determine by a set of 4 quantum numbers that describe
different atomic orbitals

1. Principal Quantum Number, n

 describes the distance between the nucleus and the shell ( shell is the level to which the electrons belong); as n
increases, on the average, the electron is found farther out of the nucleus.
 describes the energy level of the shell; as n increases, the orbital becomes larger and spends more time farther from
the nucleus; As n increase also means that the energy of the electron increases and is therefore less tightly bound to
the nucleus.
 can have integral values; 1, 2, 3, ….

*Note: the number of electrons that can be accommodated in a given shell = 2n2

Principal quantum numbers in the Bohr Model

2. Azimuthal Quantum Number, l (Angular momentum quantum number)
 describes the energy level of the subshells ( the number of subshells in a shell is equal to n)
 defines the shape of the orbital
 has any integral value starting from 0  n-1 for each value of n
o Example: if n=3  l =0, 1, 2 (because 2 is n-1)
 Remember! These shapes are not electrons but just regions in space where electrons can be

l values symbol Number of Orbitals shape

0 s 1 spherical
1 p 3 dumbbell
2 d 5 four-lobe
3 f 7 eight-lobe

*Note: Each subshell consists of a set of orbitals. All the orbitals in the same subshell have the same energy.
Within a given shell, the energies of electrons in the orbitals increase in the following order:
ns<np<nd<nf e.g 4s<4p<4d<4f

3. Magnetic Quantum Number, ml

 determines the spatial orientation of an orbital
 has an integral value of +l,…0,…,-l
o Example: if l is 2  ml = -2, -1, 0, 1, 2
 This quantum number determines how many orbitals there are of a type per energy level and therefore describes a
specific orbital amongst a particular set
Note: The collection of orbitals with the same value of n is called an electron shell. The set of orbitals that have the same n
and l values is called a subshell.

4. Spin Quantum Number, ms

 describes the direction of spin of an electron about its own axis: counterclockwise, ms = -½; clockwise, ms = +½
 every electron in an atom has a unique set of quantum numbers

*Note: Electrons with the same spin quantum numbers are said to have parallel spins while those with different m s values
are said to have opposite spins.
Exercise 4
1. (a) Predict the number of subshells in the fourth shell (n = 4). Give the label for each of these subshells. B) How
many orbitals are in each of these subshells?
2. (a) What is the designation for the subshell with n = 5 and l = 1? (b) How many orbitals are in this subshell? (c)
Indicate the values of ml for each of these orbitals.

Solution
1. (a) There are 4 subshells in the fourth shell with four possible values of l (0, 1, 2, 3). These are labelled as 4s (l = 0),
4p (l = 1), 4d (l = 2), and 4f (l = 3).
(b) There is only one 4s orbital (l= 0, ml = 0). There are three 4p (l= 1, ml = -1, 0, 1).orbitals. There are five 4d
orbitals (l= 2, ml = -2, -1, 0, 1, 2) and there are seven 4f (l= 3, ml = -3, -2, -1, 0, 1, 2, 3) orbitals.

AT THIS PART OF THE MODULE, PLEASE PREPARE A COPY OF THE PERIODIC TABLE

ELECTRONIC CONFIGURATION
 the way electrons are distributed among the various orbitals of an atom
 described by:
o a number that designates the number of principal shell
o a letter that designates the subshell (orbital)
o a superscript that designates the number of electrons in that particular subshell (orbital)
Example:
 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:

a. Aufbau (building-up) Principle

 Electrons are distributed in orbitals of increasing energy levels, where the lowest energy 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.
 Orbitals in order of increasing energy

1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f < 5d < 6p < 7s < 5f < 6d < 7p
b. Pauli’s Exclusion Principle
“No two electrons in the same atom can have the same set of four quantum numbers, i.e., the maximum number of electron
in an orbital is limited to two.”

 Two electrons in the same orbital must have opposite spins

for 1s orbital:
o one electron: n=1, l=0, ml=0, ms=+½
o one electron: n=1, l=0, ml=0, ms=-½

 For example, with the helium atom (1s2), there are three ways to represent two electrons in 1s orbital (where spin is
represented with the electron pointing up or down):

for He:

o but the Pauli exclusion principle rules out (a) and (b) since these show two electrons in the same orbital
with the same spin.

 The representation shown above is called an orbital diagram wherein each orbital is denoted by a box and each
electron by a half arrow. The half arrow pointing up represents electron with a positive spin magnetic quantum
number (ms = +1/2) and a half arrow pointing down represents an electron with a negative spin magnetic quantum
number (ms = -1/2)

c. Hund’s Rule

“Every orbital in a subshell (degenerate orbitals) is occupied (filled) with one electron first before any one orbital is
doubly-filled, and all electrons in singly-occupied orbitals have the same spin.”

 Degenerate is used in quantum mechanics to mean “of equal energy”. It usually refers to electron energy levels or
sublevels. Example: The degeneracy of p orbitals: 3; d orbitals: 5; f orbitals: 7
 The most stable arrangement of electrons in subshells has the greatest number of parallel spins
o distribute electrons with same spin (up or down) and do not pair electrons until all subshells have an
electron
o For example, if carbon’s electron configuration is: 1s2 2s2 2p2
 carbon’s orbital diagram can be shown in the following ways:

o but using Hund's rule, we know (c) would be the most stable .
Orbital Diagram of Some Elements

THINGS AND TERMS TO REMEMBER

 Electronic Configuration
o s orbitals can hold 2 electrons
o a set of p orbitals can hold 6 electrons
o a set of d orbitals can hold 10 electrons
o a set of f orbitals can hold 14 electrons
 An orbital can hold a maximum of 2 electrons of opposite spins.
 Valence electrons – outer shell electrons involved in chemical bonding
 Isoelectronic – atoms or ions of different elements that have the same electronic configuration.
o Example: Ne, N3-, O2-,F-,Na+,Mg2+,Al3+) all have the electron configuration of 1s22s22p6
 Diamagnetism – slightly affected by magnetic field
 Paramagnetism – greatly affected by magnetic field (atoms with unpaired electrons)
 Diagonal Rule: Following the guidelines of electronic configuration
Exercise 5
1. Draw the orbital diagram for the electron configuration of oxygen, atomic number 8. How many unpaired electrons
does an oxygen atom possess?
2. (a) Write the electron configuration for phosphorus, element 15. (b) How many unpaired electrons does a phosphorus
atom possess?
3. Electronic Configuration:
a) Li  3 electrons b) F  9 electrons
 1s22s1  1s22s22p5

c) P  __ electrons d) Ca  __ electrons
 _____ 
e) Al  ____ electrons f) Sr  ____ electrons

 _____ 

Condensed Electron Configuration

 Look at your Periodic Table. The filling of the 2p subshell is complete at neon (shown above), which has a stable
configuration with eight electrons (an octet) in the outermost occupied shell. The next element, sodium, atomic
number 11, marks the beginning of a new row of the periodic table. Sodium has a single 3s electron beyond the stable
configuration of neon. We can therefore abbreviate the electron configuration of sodium as

 The symbol [Ne] represents the electron configuration of the ten electrons of neon.
 In writing the condensed electron configuration of an element, the electron configuration of the nearest noble-gas
element of lower atomic number is represented by its chemical symbol in brackets.
 Writing the condensed electron configuration focuses attention on the outermost electron of the atom. The inner-shell
electrons are referred to as the core electrons. The electrons given after the noble-gas core are called the outer-shell
electrons. The outer-shell electrons include the electrons involved in chemical bonding, which are called the valence
electrons
 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
Exceptions to the Building-Up Principle (Anomalous Electronic Configuration)
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.
 Starts after calcium (Ca)

Example:
1. Cr → 24 e–
electron configuration for Cr: 1s2 2s2 2p6 3s2 3p6 4s2 3d 4  [Ar]4s2 3d4
actual electron configuration for Cr: 1s2 2s2 2p6 3s2 3p6 4s1 3d5  [Ar]4s1 3d5

2. Cu → 29 e–
electron configuration for Cu: 1s2 2s2 2p6 3s2 3p6 4s2 3d9  [Ar] 4s2 3d9
actual electron configuration for Cur: 1s2 2s2 2p6 3s2 3p6 4s1 3d10  [Ar] 4s1 3d10

 d4 and d9 would shift with each other; This anomalous behavior is largely a consequence of the closeness of the 3d
and 4s orbital energies. It frequently occurs when there are enough electrons to form precisely half-filled sets of
degenerate orbitals (as in chromium) or a completely filled d subshell (as in copper). There are a few similar cases
among the heavier transition metals (those with partially filled 4d or 5d orbitals) and among the f-block metals.

Writing Electron Configurations Using the Periodic Table

Electron configurations of the elements correspond to their locations in the periodic table. Thus, elements in the same
column of the table have related outer-shell (valence) electron configurations
 The Periodic Table's shape actually corresponds to the filling of energy sublevels.
 Let’s use the periodic table to write the electron configuration of selenium (Se, element 34).

o We first locate Se in the table and then move backward from it through the table, from element 34 to 33 to
32 and so forth, until we come to the noble gas that precedes Se.
o In this case, the noble gas is argon, Ar, element 18. Thus, the noble-gas core for Se is [Ar].
o Our next step is to write symbols for the outer electrons. We do this by moving across period 4 from K,
the element following Ar, to Se. Because K is in the fourth period and the s block, we begin with the 4s
electrons, meaning our first two outer electrons are written 4s2.
o We then move into the d block, which begins with the 3d electrons. (The principal quantum number in the
d block is always one less than that of the preceding elements in the s block) Traversing the d block adds
ten electrons, 3d10.
o Finally we move into the p block, whose principal quantum number is always the same as that of the s
block. Counting the squares as we move across the p block to Se tells us that we need four electrons, 4p4.
o The electron configuration for Se is therefore [Ar]4s23d104p4.
o This configuration can also be written with the subshells arranged in order of increasing principal quantum
number [Ar]3d104s24p4.

Exercise 6

1. Which family of elements is characterized by an ns2np2 electron configuration in the outermost occupied shell?
2. (a) Based on its position in the periodic table, write the condensed electron configuration for bismuth. (b) How many
unpaired electrons does a bismuth atom have?
3. Give the full and condensed electron configuration of the following:
a. Fe
b. Cd
c. Ag
d. Ni
e. Au
f. Y
4. Write the full and condensed electron configuration for (a) Ca2+, (b) Co3+, and (c) S2-
.

Assignment
Exercise 1 (#2)
Exercise 2 (#2)
Exercise 3 (#1, #2)
Exercise 4 (#2)
Exercise 5 (#1, #2, #3c, #3d, #3e, #3f)
Exercise 6 (#1, #2, #3, #4)