REVIEWER  The atomic spectra for hydrogen gas

together with the corresponding electronic

THE ATOMIC TABLE AND ATOMIC transitions responsible.
STRUCTURE

ATOMIC SPECTRA
 Atomic spectra: particular pattern of
wavelengths absorbed and emitted by an
element
 Wavelengths are well separated or
discrete  Excited state: It is the grouping of electrons
 Wavelengths vary from one element that is not at the lowest possible energy
to the next state
 Atoms can only exist in a few states with  Ground state: It is the grouping of electrons
very specific energies that is at the lowest possible energy state
 When light is emitted, the atom goes  Atoms return to ground state by
from a higher energy state to a emitting energy
lower energy state
2. THE QUANTUM MECHANICAL MODEL OF
1. ATOMIC SPECTRA THE ATOM
 Electrical current dissociates molecular H2  Quantum mechanical model replaced the
into excited atoms, which emit light that Bohr model of the atom
separates into four discrete wavelengths  Bohr model depicted electrons as
after being passed through a prism particles in circular orbits of fixed
radius
 Quantum mechanical model depicts
electrons as waves spread out or
delocalized through a region of space
called an orbital
 The energy of the orbitals is
quantized like the Bohr model
THE BOHR ATOM  Electrons exhibit wave-like behaviour
 Bohr model has electrons orbiting the  Wave behavior was described using
nucleus in stable orbits a wave function, called as the
 Although not a completely accurate model, Schrodinger equation
it can be used to explain absorption and
emission POTENTIAL ENERGY AND ORBITALS
 Electrons move from low energy to  Total energy for electrons includes both
higher energy orbits by absorbing potential and kinetic energies
energy  Potential energy is more important in
 Electrons move from high energy to describing atomic structure
lower energy orbits by emitting  It is associated with the coulombic
energy attraction between the positively
 Electron energy is quantized charged nucleus and the negatively
charged electrons
 Wave function can be written in terms of
two components
 Radial component: It depends only
on the distance of the electron from
the nucleus
  Angular component: It may depend  In magnetic fields, some emission
on the direction or orientation of the lines split into three, five, or seven
electron with respect to the nucleus components.
 The wave function may have positive and  A third quantum number describes
negative signs in different regions. splitting.
 Square of the wave function is  The third quantum number is the magnetic
always positive and gives probability quantum number, 𝑚ℓ, which
of finding an electron at any  has integer values.
particular point.  may be either positive or negative.
 Each solution of the wave function defines  must have an absolute value less than
an orbital. or equal to ℓ.
 Each solution labeled by a letter and  – for ℓ = 1, 𝑚 sub ℓ = -1, 0, +1
number combination: 1s, 2s, 2p, 3s,  Note the relationship between number of
3p, 3d, etc. orbitals within s, p, d, and f and 𝑚 subℓ.
 An orbital in quantum mechanical
terms is actually a region of space
rather than a particular point.

QUANTUM NUMBERS
 Quantum numbers are the solutions to the
functions used to solve the wave equation
 Quantum numbers are used to name
atomic orbitals
 When solving the Schrödinger equation,
three quantum numbers are used.
 Principal quantum number, 𝒏 (𝑛 = 1,
2, 3, 4, 5, …)
 Secondary quantum number, ℓ
 Magnetic quantum number, 𝒎 sub ℓ VISUALIZING ORBITALS
 The principal quantum number, 𝑛, defines  s orbitals are spherical
the shell in which a particular orbital is  p orbitals have two lobes separated by a
found nodal plane.
 𝑛 must be a positive integer  A nodal plane is a plane where the
 𝑛 = 1 is the first shell, 𝑛 = 2 is the probability of finding an electron is
second shell, and so on zero (here the xy plane).
 Each shell has different energies  d orbitals have more complicated shapes
 The secondary quantum number, ℓ, indexes due to the presence of two nodal planes.
energy differences between orbitals in the
same shell in an atom.
 ℓ has integer values from 0 to 𝒏 - 1.
 ℓ specifies subshells
 Each shell contains as many ℓ values
as its value of n.

 Nodes are explained using the Uncertainty

Principle.
 It is impossible to determine both the
position and momentum of an
 The energies of orbitals are specified electron simultaneously and with
completely using only the 𝒏 and ℓ quantum complete accuracy.
numbers.
  An orbital depicts the probability of  Two electrons can have the same
finding an electron. values of the first three quantum
 The radial part of the wave function numbers but must have different
describes how the probability of finding an values of ms.
electron varies with distance from the  There are two electrons maximum
nucleus. per orbital.
 Spherical nodes are generated by the  Two electrons occupying the same
radial portion of the wave function. orbital are spin paired: one is +1/2
 Cross sectional views of the 1s, 2s, and 3s and the other is -1/2.
orbitals
ORBITAL ENERGIES AND ELECTRONS
CONFIGURATIONS
 Electrons in smaller orbitals are held more
tightly and have lower energies.
 Orbital size increases as the value of
n increases.
 True for hydrogen atoms, but not
entirely true for multielectron atoms.
 As nuclear charge increases,
 Electron density plots for 3s, 3p, and 3d orbital size decreases.
orbitals showing the nodes for each orbital  Electrons interact with other
electrons as well as the
positively charged nucleus.
 For electrons in larger orbitals, the charge
“felt” is a combination of the actual nuclear
charge and the offsetting charge of electrons
in lower orbitals.
 The masking of the nuclear charge is
called shielding.
 Shielding results in a reduced,
effective nuclear charge.
 The energy ordering for atomic orbitals is
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s,
4f, 5d, 6p, 7s, 5f, 6d, and 7p.
 Electronic configurations are written in
order of energy for atomic orbitals.

HUND’S RULE AND THE AUFBAU PRINCIPLE

3. THE PAULI EXCLUSION PRINCIPLE AND  Aufbau principle - when filling orbitals, start
ELECTRON CONFIGURATIONS with the lowest energy and proceed to the
 The spin quantum number, ms, determines next highest energy level.
the number of electrons that can occupy an  Hund’s rule
orbital.  Every orbital in a sublevel is singly
 ms = ±1/2 occupied before any orbital is doubly
 Electrons are described as “spin up” occupied.
or “spin down”.  All of the electrons in singly
 An electron is specified by a set of occupied orbitals have the same spin
four quantum numbers. (to maximize total spin).
 Pauli Exclusion Principle - no two electrons  Electron configurations are sometimes
in an atom may have the same set of four depicted using boxes to represent orbitals.
quantum numbers. This depiction shows paired and unpaired
 electrons explicitly. See the example for  The periodic table is broken into s, p,
carbon below: d, and f blocks.
 Elements in each block are similar in
that the electron in the highest
energy orbital comes from the same
subshell.
 Example Problem  Structure of periodic table can be
 What is the electron configuration used to predict electronic
for the sulfur atom? configurations.
16
S  The shape of the periodic table can be
broken down into blocks according to the
type of orbital occupied by the highest
 A simplified depiction uses superscripts to energy electron in the ground state.
indicate the number of electrons in an
orbital set.
 1s2 2s2 2p2 is the electronic
configuration for carbon.
 Noble gas electronic configurations are used
as a shorthand for writing electronic
configurations.  We find the element of interest in the
 [He] 2s2 2p2 is the shorthand for periodic table and write its core electrons
carbon using the shorthand notation with the
 Electrons in outermost occupied orbitals previous rare gas element. Then we
give rise to chemical reactivity of an determine the valence electrons by noting
element. where the element sits within its own period
 The inner electrons, which lie closer to the in the table.
nucleus, are referred to as core electrons.  Example Problem
 Core electrons can be represented by  Tungsten alloys are often used for
the noble gas with the same parts that must withstand high
electronic configuration. temperatures. Use the periodic table
 The outer electrons are usually referred to as to determine the electron
valence electrons. configuration of tungsten (W).
 Valence electrons are shown
explicitly when a noble gas [Xe]6s2 4f 145d4
shorthand is used to write electronic
configurations.
 Valence electrons determine
reactivity.
 Example Problem
 Rewrite the electron configuration
for sulfur using the shorthand
notation.

 [Ne] 3s2 3p4

4. THE PERIODIC TABLE AND ELECTRON 5. PERIODIC TRENDS IN ATOMIC

CONFIGURATIONS TEMPERATURE
 The periodic table and the electronic  Using the understanding of orbitals and
configurations predicted by quantum atomic structure, it is possible to explain
mechanics are related. some periodic properties.
  Atomic size S<Se<Fe<K<Rb
 Ionization energy
 Electron affinity

ATOMIC SIZE
 The shell in which the valence electrons are
found affects atomic size.
 The size of the valence orbitals
increases with n, so size must
increase from top to bottom for a
group.

IONIZATION ENERGY
 Ionization energy - the energy required to
 The strength of the interaction between the remove an electron from a gaseous atom,
nucleus and the valence electrons affects forming a cation.
atomic size.  Formation of X+ is the first
 The effective nuclear charge ionization energy, X2+ would be the
increases from left to right across a second ionization energy, etc.
period, so the interaction between X(g) → X+(g) + e -
the electrons and the nucleus  The more strongly held an electron is, the
increases in strength. higher the ionization energy must be.
 As interaction strength increases,  As valence electrons move further from the
valence electrons are drawn closer to nucleus, they become easier to remove and
the nucleus, decreasing atomic size. the first ionization energy becomes smaller.
 Graph of the first ionization energy (in
kJ/mol) vs. atomic number for the first 38
elements.

 Graph showing atomic radius as function of

atomic number.
 Different colors represent periods

 From nitrogen to oxygen, there is a slight

decrease in ionization energy.
 Nitrogen has a half-filled p subshell.
 Oxygen has a pair of p electrons in
one 2p orbital.
 Ionization of oxygen relieves
electron-electron repulsion, lowering
its ionization energy.
 Example Problem
 Using only the periodic table, rank
the following elements in order of
increasing size: Fe, K, Rb, S, and Se.  Ionization energies increase with successive
ionizations for a given element.
  Effective nuclear charge for valence  The greater (more negative) the electron
electrons is larger for the ion than affinity, the more stable the anion will be.
the neutral atom.  Graph of electron affinity (in kJ/mol) vs.
 Filled subshells of electrons are difficult to atomic number for the first 20 elements.
break up, which is why it is difficult to
remove electrons from noble gases.
 The first four ionization energies in kJ/mol
for elements Z = 1 to 9.

 Example Problem
 Using only the periodic table, rank
the following elements in order of
increasing ionization energy: Br, F,
Ga, K, and Se.

ELECTRON AFFI NITY

 Electron affinity - energy required to place
an electron on a gaseous atom, forming an
anion.
X(g) + e -  X – (g)
 Electron affinities may have positive
or negative values.
 Negative values - energy
released
 Positive values - energy
absorbed
 Electron affinities increase (numerical value
becomes more negative) from left to right
for a period and bottom to top for a group.