- Chemical Principles (Sixth Edition), Peter Atkins, Loretta Jones and Leroy LavermanW. H.

Freeman-2012
Week 1 & 2: Chapter 1 - Atoms: The Quantum World
Week 3: Chapter 2 - Chemical Bonds
Week 4: Chapter 3 - Molecular Shape and Structure
Week 5: Chapter 4 - The Properties of Gases
Week 6: Chapter 5 - Liquids and Solids
Week 7: Midterm Exam
Week 8: Chapter 7 - Thermodynamics: The First Law
Week 9: Chapters 7 & 8 - Thermodynamics: The First Law & Thermodynamics: The Second and
Third Laws
Week 10: Chapters 8 & 9 - Thermodynamics: The Second and Third Laws & Physical Equilibria
Week 11: Chapters 9 & 10 - Physical Equilibria and Chemical Equilibria
Week 12: Chapters 10 & 11 - Chemical Equilibria & Acids and Bases
Week 13: Chapters 11 & 12 - Acids and Bases & Aqueous Equilibria
Week 14: Chapter 12 - Aqueous Equilibria & Current Topics (If Time Permits)
Week 15: Final Exam
- : 20%, : 10%, : 30%, : 40%
503 429 (888-6817); (cys0614@snu.ac.kr) &
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Chapter 1.
Atoms: The Quantum World

Key Ideas
Goal

Atomic Structure in terms of Quantum Mechanics

Periodic variation of atomic properties
(periodic table)
Quantum mechanics Atomic structure
Atomic properties Chemistry

Chemical insight
Failure of classical mechanics on electrons
Quantum mechanics in the early 20th century

INVESTIGATING ATOMS
Three major subatomic particles; electrons, protons, neutrons

Components of the Atom

Atomic theory raised more questions t
han it answered
Could atoms be broken down into smalle
r particles
100 years after atomic theory was propos
ed, the answers were provided by experi
ment

Fundamental Experiments
J.J. Thomson, Cavendish Laboratories, Camb
ridge, England
Ernest Rutherford
McGill University, Canada
Manchester and Cambridge Universities, Englan
d

Investigating Atoms
1.1. The Nuclear Model of the Atom

Electrons
First evidence for subatomic particles came from the
study of the conduction of electricity by gases at low
pressures
J.J. Thomson, 1897
Rays emitted were called cathode rays
Rays are composed of negatively charged particles
called electrons
Electrons carry unit negative charge (-1) and have
a very small mass (1/2000 the lightest atomic mas
s)

Cathode Ray Apparatus

The Electron and the Atom

Every atom has at least one electron
Atoms are known that have one hund
red or more electrons
There is one electron for each positive
charge in an atom
Electrical neutrality is maintained

Protons and Neutrons The Nucleus

Ernest Rutherford, 1911
Bombardment of gold foil with particles (helium atoms with
out electrons)
Expected to see the particles pass through the foil
Found that some of the alpha particles were deflected by t
he foil
Led to the discovery of a region of heavy mass at the cente
r of the atom
Alpha particles (named after and denoted by the first letter in
the Greek alphabet, ) consist of two protons and two neutrons
bound together into a particle identical to a helium nucleus,
which is generally produced in the process of alpha decay, but
may be produced also in other ways and given the same name.
From wikipedia.org

Rutherford Backscattering

The Plum-Pudding Model

J.J. Thomson proposed the atom
as a positively charged sphere
Within the sphere are electrons
Plum-pudding or raisin-bread
model

Rutherfords Model
Rutherfords experiment revealed a sm
all, dense core with positive charge
Electrons are outside this core
Most of the atom is empty space

Nuclear Particles
1. Protons
Mass nearly equal to the H atom
Positive charge

2. Neutrons
Mass slightly greater than that of the proto
n
No charge

Mass and the Atom

More than 99.9% of the atomic mass
is concentrated in the nucleus
The volume of the nucleus is much sm
aller than the volume of the atom

Subatomic Particles

1.3. Atomic Spectra

Balmer series (1885)

(Johann Balmer, 18251898, Swiss mathematics schoolteacher)

Rydberg formula (Johannes Rydberg, 1888)

Absorption spectrum of H

Absorption lines have the same wavelengths as the emission lines!

Absorption spectra to identify elements in the outer layers of stars
Fig 1.11; Sun
How to explain the experimental observations?
1. An electron in an atom can have only certain energies.
2. A spectral line arises from a transition between two of
the allowed energies.

Quantum Theory
1.4. Radiation, Quanta, and Photons
Blackbody Radiation ( )

Quantization of Electromagnetic Wave

h = 6.626 10-34 Js (Plank constant)

Ultraviolet catastrophe:
Any hot body should emit intense short-wavelength radiations
according to a prediction of classical physics, contrary to the
Stefan-Boltzmann law and Wien's law.
Planck's hypothesis: Quantum of radiation energy, Max Planck
(1900, 1918)
Planck's constant

 Radiation of frequency = E/h can be generated only when

enough E is acquired.
At low T, there is not enough E to stimulate oscillations of
high . No ultraviolet catastrophe!
Planck's hypothesis explains the S-B law and Wien's law
almost exactly including the curve.
Continuous values of energy (classical)
Discrete values of energy (quantum)

Photoelectric effect
Experimental results
1. No electron is ejected when .
2. Electrons are immediately ejected
even if
3. The kinetic energy of e- linearly
increases with

The Bohr frequency condition explains the spectrum of H.

1.5. The Wave-Particle Duality

Diffraction and interference wave
Photoelectic effect particle

1.6. The Uncertainty Principle

Heisenberg uncertainty principle

de Broglies material wave

1.6 The Uncertainty Principle

Classical mechanics; definite trajectory, both the location and
momentum specified precisely
Quantum mechanics; wave-like trajectory
Heisenberg uncertainty principle (1927);
complementarity of location and momentum

The location and momentum of a particle are complementary;

i.e., both the location and the momentum cannot be known
simultaneously with arbitrary precision.

Ex 1.7a

of a marble of 1.0 g with a speed known to

within
mm/s?

Ex 1.7b

of an electron confined to within the diameter

of a typical atom (200. pm)?

For macroscopic objects, the uncertainty principle can be neglected.

For subatomic particles, it is of profound importance.

1.7. Wave functions and Energy Levels

Wave function ()
Probability density (2)

Schrdinger equation

H=E

1.7 Wavefunctions and Energy Levels

Schrdinger equation for wavefunctions;
Erwin Schrdinger (1927, 1933)

For a one-dimensional system in a potential energy V(x)

Therefore, (x) satisfies the Schrdinger equation,

Fig 1.25

THE HYDROGEN ATOM

1) An electron is described by a wavefunction governed
by the Schrdinger equation.
2) The nuclear model for an atom
To explain the ladder of energy levels suggested by
spectroscopy

1.8 The Principal Quantum Number

Constraints (boundary conditions) in solving
the Schrdinger equation
Quantization of energies, discrete energy levels corresponding
to a set of quantum numbers
To solve the Schrdinger equation for y and energy levels of
an electron in a hydrogen atom, the potential energy term V
in the hamiltonian H is needed.

The solution by Schrdinger (1927)

Energy levels of a hydrogen atom

Fig 1.28

For other one-electron atoms such as He+, , C5+ with atomic number Z,

Z2 dependence;
1) nucleus of charge Ze

2) Z times closer distance to the nucleus

* Degeneracy - different quantum states having the same energy

1.9 Atomic Orbitals

Atomic orbitals; wavefunctions of electrons in atoms
(orbital; wave-like orbit)

Fig 1.36
Detailed solutions of the Schrdinger
equation for a hydrogen atom require three
quantum numbers.
Three dimensional boundary
conditions
Principal quantum number (n);
energy & size

Shell; atomic orbitals of the same principal

quantum number n
As n increases, the energy (1/n2) and the nucleus-electron
distance (n2) increase.
All the orbitals of a given shell of hydrogen-like atoms have
the same energy; degenerate
Orbital angular momentum quantum
number (l); shape
Angular momentum;

l = 0, 1, 2, , n 1; n different values of l, n subshells

Subshell; group of orbitals with the same value of l
s (sharp); l = 0, p (principal); l = 1, d (diffuse);
l = 2, f (fundamental); l = 3, g, h,
Orbital angular momentum of an electron in a subshell
=
; measure of the rate at which the electron
circulates around the nucleus

Shape of orbitals

Boundary surface;
a smooth surface that encloses most (typically 90%) of the
electron cloud
All s-orbitals have spherical boundary surfaces
(with internal structures such as nodes).

p-Orbitals;
3 orbitals in each subshell;

The Boundary surface of

each p orbital has two lobes
and one nodal plane.
A p-electron will never be
found at the nodal plane nor
at the nucleus.

d-Orbitals;
5 orbitals in each subshell;

f-Orbitals;

Figs 1.38

Total number of orbitals in a shell = n2

n: principal quantum number

related to the size and energy of the
orbital

l: orbital angular momentum quantum

number (l = 0, 1, 2, ..., n-1)
related to the orbital angular
momentum of the electron

ml: magnetic quantum number (ml = l, l1, l-2, , -l)

related to the orientation of the
orbital motion of the electron

1.10. Electron Spin

ms: spin magnetic quantum number (ms = +1/2, -1/2)
related to the spin of electron

1.11. The Electronic Structure of Hydrogen Atom

In the ground state,
n = 1, l = 0, ml = 0, ms = +1/2 or -1/2
In the excited state
n = 2 (four orbitals)
n = 3 (nine orbitals)
n = k (k2 orbitals)
n = infinite (ionization)
Degeneracy: same energy for all orbitals in the same n

MANY-ELECTRON ATOMS
1.12 Orbital Energies
Greater attractions between electrons and the nucleus
Higher charge of the nucleus
Repulsions between electrons
He atom with 2 electrons

Analytical solution impossible! Numerical solution!

Hydrogen-like atoms;
one electron, no electron-electron repulsion
All orbitals of a given shell are degenerate
(of the same energy).
Many-electron atoms;
electron-electron repulsion
Orbitals of a given shell are
nondegenerate (of different energies).

Fig 1.41

1.12. Orbital Energies

Coulomb potential for many-electron atoms

For example, in a helium atom,
r1: e1~nucleus
r2: e2~nucleus
r12: e1~e2
Shielding and Penetration effect

- Each electron is shielded by the other (e-)s.

Zeff: effective nuclear charge
- (e-)s in p orbital penetrate less than (e-)s in s
orbital Es < Ep

energy split

Shielding due to the electron-electron repulsions

Other electrons do not block the influence of the nucleus; they
simply provide additional repulsive coulombic interactions
that partly counteract the pull of the nucleus.
Effective nuclear charge; Zeff < Z

Penetration; an s-electron can be found very

close to the nucleus while a p-electron
approaches the nucleus less closely due to its
orbital angular momentum (l=1(0) = 0).

 An s-electron penetrates more than a p-electron through

the inner shells of the atom.
An s-electron is shielded less than a p-electron (an selectron feels a higher nuclear charge).
An s-electron is bound more tightly than a p-electron.
An s-electron has a lower (more negative) energy than a pelectron.
The order of energies of orbitals in a given shell due to effects
of penetration and shielding:
s<p<d<f
A 4s-electron may even have a lower energy than that of a 3delectron of the same atom.

1.13. The Building-Up Principles

Pauli exclusion principle
no more than 2 (e-)s in any
given orbital
Hunds Rule
parallel spin rather than paired

closed shell
valence shell
core electron
valence electron

Pauli exclusion principle (Wolfgang Pauli, 1925)

No more than two electrons may occupy any given orbital. When
two electrons occupy one orbital, their spins must be paired ( ).
No two electrons in an atom can have the same set of four quantum
numbers (n, l, ml, ms).
Hund's rule (Friedrich Hund)
If more than one orbital in a subshell is available, add electrons
with parallel spins to different orbitals of that subshell rather
than pairing two electrons in one of the orbitals.
Different orbitals less repulsion
Parallel spins () slightly lower energy than paired spins ()

Period 1; n = 1

Closed shell; fully occupied shell

Period 2; n = 2

Valence shell; partially occupied shell with the largest n

Building-up principle (Aufbau principle)

1. Pauli exclusion principle: Maximum of 2 electrons
per orbital (fermions).
2. Hund's rule: spins to different orbitals, if available.

Period 3; n = 3

Period 4; n = 4, first long (10 3d + 2 4s + 6 4p = 18) period

of the periodic table
1. The 4s orbital has a slightly lower energy than those of
3d orbitals.

2. Once they contain electrons, the 3d orbitals lie lower in

energy than the 4s orbital.
Transition metals; Group 3 (Sc) to Group 11 (Cu)
Properties of the d-block metals are transitional between the
s- and the p-block elements.
3. The half-full 3d5 and the full 3d10 have a lower energy.

Period 5; n = 5, long (10 4d + 2 5s + 6 5p = 18) period

1. The 5s orbital has a slightly lower energy than the
4d orbitals.
2. Once they contain electrons, the 4d orbitals lie lower in
energy than the 5s orbital.
3. Disruptions due to very close energies of 4d and 5s
orbitals.

Period 6; n = 6, 4f-orbitals

(6s < 4f < 5d << 6p)

Lanthanoids (lanthanides); La (Z = 57) to Lu (Z = 71)

cf. Rare earth elements; 15 lanthanoids + Sc + Y
1. 4f-orbitals
(disruptions due to very close energies of 4f and 5d orbitals)

2. 5d-orbitals
3. 6p-orbitals

In Summary,
1. Add electrons in the order shown in Figs. 1.41 and 1.44
observing the Pauli exclusion principle.
2. Hund's rule when more than one orbital in a subshell are
available.
3. Parallel spins for electrons in different orbitals; paired
spins for electrons sharing an orbital.
4. Group number = number of valence electrons, Period
number = n

1.14. Electronic Structure and the Periodic Table

He belongs to Group 18/VIII due to the filled shell.

H, one electron short of a noble gas configuration, can act like a
member of Group 17/VIII.
Main groups; s- and p-blocks
Roman numerals (I-VIII) with or without "A"
The number of valence electrons is equal to the Roman
numerals.
For 1-18 group labels, the number of valence electrons is
equal to (Group number 10).

THE PERIODICITY OF ATOMIC PROPERTIES

Zeff vs. Z; effective nuclear charge for the outmost valence electron
Zeff = Z S
S; average number of electrons inner to the electron in question

Across the periodic table (left to right), Zeff increases (generally).

Oversimplified: If the 3s valence electron were completely outside
the ten core electrons (perfect shielding),
Zeff(Na) < Zeff (Mg).

Less simplified: 1) Valence electrons can also penetrate

inner shells depending on the l values.
2) Core electrons are not all equally
effective in shielding valence electrons.
3) Valence electrons shield one another for the
nucleus charge a little bit.

Down the periodic table (top to bottom),

Zeff increases (slightly).
Oversimplified: Zeff(Li) = Zeff(Na)

Less simplified: The 2s- and 2p-electrons have lower

shielding capabilities than the 1s-electrons.

1.15. Atomic Radius

related to Zeff

Periodic variation in the atomic radii of the elements

Down a group, n increases.

Larger shell Larger radius
Across a period, Zeff increases.
Stronger attraction Smaller radius

1.16 Ionic Radius

Ionic radius; share of the distance
between neighboring ions in an ionic solid

isoelectric ions

All cations are smaller than their parent atoms;

attraction between excess protons and (lower n) electrons
All anions are larger than their parent atoms; repulsion
between excess electrons
Isoelectronic; same electron
configuration; F, Ne, Na+, Mg2+

1.17. Ionization Energy

The minimum E need to remove an electron from an atom in the gas phase.
X (g) X+ (g) + e- (g)I = E(X+) E(X)
Typically, I1 increases across a period

Typically,
I1 decreases down a group

Table: the 1st I (kJ mol-1)

Periodic property

Small but regular departures from the general trend due to the
extra stability of a closed s2 subshell and a half-filled p3 subshell
Fig 1.51

ST 1.14A
2nd ionization energy

Evidence of a shell structure

Fig 1.52

Table: the 1st and 2nd I (kJ mol-1)

1.18. Electron Affinity

The E released when an electron is added to an atom in the gas phase.
X (g) + e- (g) X- (g)

Eea (X) = E(X) E(X-)

Typically, Eea increases across a period

Typically,
Eea decreases down a group

electron affinity (kJ mol-1)

Periodic property;
much less periodic than the variations in radius and
ionization energy

Highest toward the (upper) right side of the periodic table except
for noble gases

Noble gases have negative Eea due to their stable closed shell.
Group 17/VII;
positive first Eea and very negative second Eea.

Group 16/VI;
positive first Eea and negative second Eea.

No gaseous atom with a positive electron affinity for a second

electron; e-e repulsion
Doubly charged anions are stable only when surrounded
by cations or solvent molecules.

1.20 Diagonal Relationship

Diagonal relationship; similarity between
diagonal neighbors in the main groups
1) Atomic radius increases down a
group and decreases across a
period.
2) Ionization energy decreases down a
group and increases across a period.
Diagonal neighbors have similar
r and I1.
Similar chemical properties

Fig 1.58

1.21. The General Properties of the Elements