THE ELEMENTS

Inorganic chemistry III

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 1811 1869 1899 1909
460~370 BC
Amadeo Meyer & Marie Robert
Democritus
Avogadro Mendeleev Curie Millikan

Equal Lets arrange Radioactive Lets

Matter
volumes of elements atoms measure the
might be
gas should into a table release charge of
made of
have equal with periodic particles the electron
atoms
numbers of properties smaller than
particles atoms

Elements may Lets use Some 1897: Canal rays

be made of Avogadros elements are Cathode rays are positively
one type of Law to get radioactive 1912: charged
atom the atomic Canal rays particles
masses

1860 1896 Joseph 1870

1808
Stanislao Henri John Eugen
John Dalton
Cannizzaro Becquerel Thomson Goldstein

HISTORY OF THE ATOM

 1932 1913 Discovery 1927
James Henry of line Werner
Chadwick Moseley spectra Heisenberg

Neutrons Lets sort the The line spectra You cant

exist atoms in the follow a determine both
periodic table specific a particles
based on equation for momentum
atomic number their and position
wavelengths

An atom Orbits of Wave? Cat.

consists of a electrons Particle?
nucleus and around the Also his
mostly empty nucleus are Why not equation.
space quantized both? Orbitals.

1911 1913 1924 1926

Ernst Niels Louis Erwin
Rutherford Bohr De Broglie Schrodinger

HISTORY OF THE ATOM II

H

He

Li

IN THE BEGINNING
THE BIG BANG, 13.798 GYA

The expansion of spacetime from a singularity generated

hydrogen, deuterium, helium-3, helium-4, and lithium.
C-Fe

Cu Zn As

Sr-Ru

Pd-Sn

Ba-Sm

Yb Hf Ta W Hg Tl

STELLAR NUCLEOSYNTHESIS
SYNTHESIS OF HEAVIER NUCLEI

Nuclear reactions inside stars synthesize heavier elements

Al Si Ti V Fe Mo

Ru Pd-Sn

Pr-Sm Yb Hf Ta W

Hg Tl

Everything else
up to Pu

SUPERNOVAE
SYNTHESIS OF REALLY HEAVY NUCLEI

Other elements could only be synthesized during the final stages

of the lives of large stars
 Elements with odd number of
protons are less abundant

ELEMENT ABUNDANCE
NOT ALL ELEMENTS ARE CREATED EQUAL

The abundances of elements in the Universe reflect the ways

they are synthesized.
Why is helium scarce on Earth?
 Proton
1.008 amu

Neutron
1.009 amu

Electron
1 amu / 1823

WHATS IN AN ATOM
TODAYS ATOMIC STRUCTURE

Thanks to all those who gave their lives cutting the uncuttable

Now we find out its mostly empty space

xaotherion.deviantart.com
 Areas with zero electron density are
called nodes

ORBITALS
ELECTRONS *MIGHT* BE HERE

The orbitals are locations in 3-d space that contain high

probability of finding the electron
Cartesian coordinate system Spherical coordinate system
(x, y, z) (r, , )

3D COORDINATES
LETS NOT GET LOST IN 3D SPACE

There are two coordinate systems to guide us here.

 Hamiltonian Energy
Wavefunction
operator eigenvalue

*A function
corresponding to
the total energy of
the system Properties of
Single-valued

H = E Continuous
Must approach zero as
r infinity
Normalizable
Orthogonal

THE SCHRODINGER EQUATION

THIS ONE IS FOR PYSCHE3

The Schrodinger Equation describes the wave function and is

applied to determine the areas of probability of locating the
electron
 Principal Orbital quantum Magnetic
quantum number number quantum number
n l ml

THE SCHRODINGER EQUATION II

THIS ONE IS FOR PYSCHE3

As applied to the hydrogen atom

RADIAL PROBABILITY
OF FINDING THE ELECTRON AT A CERTAIN DISTANCE

Just 2D for now

THE ORBITALS
THEIR SHAPES COME IN HANDY
n Principal quantum
number
Electron shell 1 to any
integer n

Sharp S=0

l
Angular momentum
Azimuthal Principal P = 1
and the shape of the
quantum number Diffuse D = 2
orbital Fundamental F = 3

ml
Projection of the
Magnetic angular momentum From l to +l
quantum number along an axis

ms
Spin angular
Spin quantum momentum of the From - to +
number electron

THE QUANTUM NUMBERS

SOLUTIONS TO THE SCHRODINGER EQUATION
1s 2s 2p 2p 2p 3s 3p 3p 3p

4s 3d 3d 3d 3d 3d 4p 4p 4p

4f 4f 4f 4f 4f 4f 4f

THE ELECTRON CONFIGURATION

1S2 2S2 2P6 ITS LIKE YOUR THIRD ALPHABET

Be familiar with the different shapes of the orbitals

1s 2s 3s

2p 3p 4p
THE ORBITALS II
THEY EVOLVE
3d 4d 5d

3d 4d 5d
THE ORBITALS III
THEY EVOLVE
1s

2s 2p-1 2p0 2p+1

3s 3p-1 3p0 3p+1 3d-2 3d-1 3d0 3d+1 3d+2

4s 4p-1 4p0 4p+1 4d-2 4d-1 4d0 4d+1 4d+2

4f-3 4f-2 4f-1 4f0 4f+1 4f+2 4f+3

5s 5p-1 5p0 5p+1 5d-2 5d-1 5d0 5d+1 5d+2

THE ELECTRON CONFIGURATION II

WE ADD ELECTRONS IN SEQUENCE

There are sets of rules that we use to determine where to put the
next electron
 Rule #1 Aufbau principle

1s
Fill up orbitals with the
lowest energy first.
2s 2p
Hunds rule of
Rule #2
3s 3p 3d maximum multiplicity

In filling orbitals of the

4s 4p 4d 4f same subshell, there
should be maximum
number of parallel spins
5s 5p 5d 5f 5g
Rule #3 Paulis exclusion principle

6s 6p 6d 6f 6g 6h
No two electrons will have
the same set of 4
quantum numbers

THE ELECTRON CONFIGURATION III

EFFECT OF SHIELDING

The shielding effect has effectively reorganized the orbital

energy sequence
 c Coulombic energy of
repulsion
2p 2p 2p The energy of repulsion is positive

none

2p 2p 2p

e Exchange energy

2p 2p 2p Exchange energy is negative, so it lowers total energy

These electrons are switchable

HUNDS RULE OF MAXIMUM MULTIPLICITY

A SIMPLE EXPLANATION

In short, a subshell configuration with the maximum number of

parallel spins has lower energy than other configurations
1 Write down the electron
configuration of the atom
Z *
Effective
=Z-S
Number Shielding
Nuclear of Protons Constant

2 Higher electrons do not shield

lower electrons
Charge

For same ns or np: S = 0.35 except for 1s, where S = 0.30

3 For n-1, S = 0.85

For n-2, S = 1
Add all S for all the lower
electrons relative to your
reference electron
4 For same nd or nf: S = 0.35
For all lower electrons: S = 1

SHIELDING EFFECT
SLATERS RULES

Electrons in lower energy levels will negate part of the nuclear

charge felt by higher electrons
 4s 3d-2 3d-1 3d0 3d+1 3d+2

3d +

3d -

4s +

4s -

ENERGY

Sc Ti V Cr Mn Fe Co Ni Cu Zn

HOW ABOUT THE D

SOME CONFIGURATIONS DO NOT FOLLOW AUFBAU

The shielding effect lowers the energy of partly-filled D orbitals

PERIODIC PROPERTIES
WHAT REALLY THE PERIODIC TABLE IS FOR

The periodic properties describe many chemical characteristics of

the elements
 2P -
3P +
c 4P -

IONIZATION ENERGY
ENERGY REQUIRED TO REMOVE (ONE) ELECTRON FROM A GASEOUS ATOM

Ionization energy depends on how shielded the electron youre

removing is.
 Z * =Z-S
For same ns or np: S = 0.35 except for 1s, where S = 0.30

3 For n-1, S = 0.85

For n-2, S = 1

4 For same nd or nf: S = 0.35

For all lower electrons: S = 1

0.35 0.85 0.85 0.85 0.85 0.85 0.35 0.35 0.35

4s 0.35
3d 4p 0.35 0.35 0.35
0.85 0.85 0.85 0.85 0.85
0.85 0.85 0.85 0.85
4s 0.85
3d 2 2 2 2 2 4p
0.85 0.85 0.85

5s 0.35 4d 5p

EFFECTIVE NUCLEAR CHARGE

THE REAL MEANING OF SLATERS RULES

The effective nuclear charge, or Z*, increases along a period but

decreases down a group
 A-(g) A(g) + e- E = EA

ELECTRON AFFINITY
ENERGY REQUIRED TO REMOVE AN ELECTRON FROM A NEGATIVE ION

Similar to ionization energy, but it is generally easier to remove

an electron from an anion than a neutral atom
 Cl Cl

Half this distance

ATOMIC AND IONIC RADIUS

HOW FAT IS YOUR ATOM

An interaction of the nuclear charge and the electron-electron

repulsion in higher orbitals
ATOMIC AND IONIC RADIUS II
HOW FAT IS YOUR ATOM
Lose Gain
electrons = electrons =
strips outer causes
orbitals of repulsive
electrons forces to
dominate
greater outer
effective electrons
nuclear
charge felt More
shielding
from nuclear
charge felt

ATOMIC AND IONIC RADIUS III

HOW FAT IS YOUR ATOM
ELECTRONEGATIVITY
HOW (ELECTRON) HUNGRY IS YOUR ATOM

An estimated property based on how well an atom attracts

shared electrons to itself