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Principles of General Chemistry, 2nd ed. By M.

Silberberg
Chemistry, 8th ed. by W. Whitten, R. Davis, R., M. L. Peck, and G. Stanley.

Outline
1. The Wave Nature of the Electron
The Electronic 2. The Quantum Mechanical Picture of the Atom

Structure of 3. Quantum Numbers


4. Atomic Orbitals
Atoms 5. Electron Configurations
6. Paramagnetism and Diamagnetism
7. The Periodic Table and Electron Configurations

Review The Wave Nature of the Electron


• according to Louis de Broglie (1925) in his Ph.D.
• The fundamental particles make up atoms: dissertation:
– electrons have wave-like properties.
P a rtic le M a s s (a m u ) C h a rg e – electron wavelengths can be described by the
following relationship:
-
E le c tro n (e ) 0 .0 0 0 5 4 8 5 8 -1
h
λ=
+ mv
P ro to n (p ,p ) 1 .0 0 7 3 +1
h = Planck’ s constant
0
N e u tro n (n ,n ) 1 .0 0 8 7 0 m = mass of particle
v = velocity of particle

The Quantum Mechanical The Quantum Mechanical


Picture of an Electron Picture of an Electron
• according to Werner Heisenberg (1927) • consequently, we must must speak of the
• it is impossible to determine simultaneously both electrons’ position about the atom in terms of
the position and momentum of an electron (or any probability functions
other small particle)
• also known as Uncertainty Principle • these probability functions are represented as
orbitals in quantum mechanics
– detecting an electron requires the use of
electromagnetic radiation which displaces the electron • orbitals - are the volume that the electrons
– (today) electron microscopes use this phenomenon occupy 90-95% of the time (Heisenberg’s
Uncertainty principle)
Basic Postulates of Quantum Theory Basic Postulates of Quantum Theory

1. Atoms and molecules can exist only in 2. Atoms or molecules emit or absorb
certain energy states. In each energy radiation (light) as they change their
state, the atom or molecule has a
energies. The frequency of the light
definite energy. When an atom or
molecule changes its energy state, emitted or absorbed is related to the
it must emit or absorb just enough energy change by a simple equation.
energy to bring it to the new energy (E = energy, λ = wavelength)
state (the quantum condition). hc
E = hν =
λ

Basic Postulates of Quantum Theory Basic Postulates of Quantum Theory


3. The allowed energy states of atoms and
molecules can be described by sets of
numbers called quantum numbers.

• Quantum numbers are the solutions of the


Schrodinger, Heisenberg & Dirac equations.
• Four quantum numbers are necessary to describe
energy states of electrons in atoms.

Basic Postulates of Quantum Theory Quantum Numbers


• Schrodinger equation calculates the
particle's allowed wavefunctions and
• Principal quantum number (n)
corresponding energy levels
• Azimuthal quantum number (ll)

• Magnetic quantum number (ml)

Hamiltonian Operator to the ψ function


• Spin quantum number (ms)
Energy or
Wavefunction obtained from quantum mechanical “Eigenvalue” as a
oscillators as applied to electrons behaving as waves function of the Q.N.
Quantum Numbers Quantum Numbers
• angular momentum quantum number
• principal quantum number - has the symbol l
- has the symbol n
l = an integer from 0 to (n - 1)
n = a positive integer
n = 1, 2, 3, 4, ……) l = 0, 1, 2, 3, 4, 5, ... or l = s, p, d, f, g, h, ...
n l l
- describes the “shells” 1 0 s
of an atom 2 0, 1 s, p
- designates the energy 3 0, 1, 2 s, p, d
level of the electron - describes the energy sublevel of the electrons
- describes the shape of the orbitals

Quantum Numbers Quantum Numbers


• magnetic quantum number
• spin quantum number
- has the symbol ml
- has the symbol ms
ml = an integer from -ll  + l ms = +1/2 or -1/2 (two possible values only)
l ml
- describes spin and orientation of the
0=s 0
magnetic field of the electrons
1=p -1, 0, +1
2=d -2, -1, 0, +1, +2 History: Wolfgang Pauli in 1925 discovered the Exclusion
Principle stating that “No two electrons in an atom can
- designates the particular orbital have the same set quantum numbers.”
- descibes space orientation

Atomic Orbitals Atomic Orbitals


• are regions of space where the probability of finding • p orbitals are peanut or dumbbell shaped
an electron about an atom is highest

• s orbitals are spherically symmetric

l ml ml
the 1s, 2s, and 3s orbitals 1=p -1, 0, +1 Px, py, pz
Atomic Orbitals Atomic Orbitals
• f orbital shapes
• d orbital are clover shaped

l ml ml
2=d -2, -1, 0, +1, +2 dxy, dxz dyz, dz2, dx2-y2

Properties of Atomic Orbitals Properties of Atomic Orbitals


DEGENERACY • GROUND STATE
– the state if all of the electrons are present
Orbitals of the same azimuthal quantum in their respective orbitals
number are degenerate or they have – associated with an specific energy level &
the same energies. the lowest possible level that can be
occupied

p, d, and f have degenerate orbitals • EXCITED STATE


– the state if the electrons absorb energy
and are promoted on the next empty &
higher orbital

Properties of Atomic Orbitals Quantum Numbers


• VALENCE ELECTRONS

– the electrons at the


outermost orbitals
– are responsible for
the CHEMICAL
CHARACTERISTICS
of a given atomic
species
Writing Electron Configurations Order for filling
energy sublevels
• Aufbau Principle – electrons are distributed with electrons
among the various orbitals, occupying the
lowest possible states first • Aufbau Principle
• Pauli’s Exclusion Principle – a maximum of - the electron that
two electrons (only) can occupy one orbital, distinguishes an
each having opposite spins element from the
previous element
• Hund’s Rule of Maximum Multiplicity – in enters the lowest
filling-up degenerate orbitals, electrons must energy atomic
occupy them singly first before pairing orbital available

Order for filling energy sublevels Writing Electron Configurations


with electrons
• an orbital can hold a maximum of 2 e- only
1s Configuration other the orbital diagrams

1H ↑ 1s1
2 He ↑↓ 1s 2

• electronic configuration may either be: in


expanded form (complete) or in condensed
form (the use of a noble gas’ configuration)

Writing Electron Configurations Writing Electron Configurations


(expanded) (condensed)
1s 2s 2p Configuration

3 Li ↑↓ ↑ 1s 2 2s1
4 Be ↑↓ ↑ ↓ 1s 2 2s 2
5 B ↑↓ ↑ ↓ ↑ 1s 2 2s 2 2p1
6 C ↑↓ ↑ ↓ ↑ ↑ 1s 2 2s 2 2p 2
7 N ↑↓ ↑ ↓ ↑ ↑ ↑ 1s 2 2s 2 2p 3
8 O ↑↓ ↑ ↓ ↑↓ ↑ ↑ 1s 2 2s 2 2p 4
9 F ↑↓ ↑ ↓ ↑↓ ↑↓ ↑ 1s 2 2s 2 2p 5
Writing Electron Configurations Writing Electron Configurations
(condensed) (transition metals)
3s 3p Configurat ion 3d 4s 4p Configuration

11 Na [Ne ] ↑ [Ne ] 3s1 19 K [Ar ] ↑ [Ar ] 4s1


12 Mg [Ne ] ↑↓ [Ne ] 3s 2 20 Ca [Ar ] ↑↓ [Ar ] 4s 2
13 Al [Ne ] ↑↓ ↑ [Ne ] 3s 2 3p 1 21 Sc [Ar ] ↑ ↑↓ [Ar ] 4s 2 3d1
14 Si [Ne ] ↑↓ ↑ ↑ [Ne ] 3s 2 3p 2 22Ti [Ar ] ↑ ↑ ↑↓ [Ar ] 4s 2 3d 2
15 P [Ne ] ↑↓ ↑ ↑ ↑ [Ne ] 3s 2 3p 3 23V [Ar ] ↑ ↑ ↑ ↑↓ [Ar ] 4s 2 3d3
[Ne ] ↑↓ ↑↓ ↑ ↑ [Ne ] 3s 2 3p 4 Cr [Ar ] ↑ ↑ ↑ ↑ ↑ ↑ [Ar ] 4s1 3d 5
16 S
24

17 Cl [Ne ] ↑↓ ↑↓ ↑↓ ↑ [Ne ] 3s 2 3p 5 There is an extra measure of stability associated

18 Ar [Ne ] ↑↓ ↑↓ ↑↓ ↑↓ [Ne ] 3s 2 3p 6 with half - filled and completely filled orbitals.

Writing Electron Configurations Electron Configurations


(transition metals)  Quantum Numbers
3d 4s 4p Configuration
• Consider the last entering electron of sodium
25 Mn [Ar] ↑ ↑ ↑ ↑ ↑ ↑↓ [Ar] 4s 2 3d 5
26 Fe [Ar] ↑↓ ↑ ↑ ↑ ↑ ↑↓ [Ar] 4s 2 3d 6 3s 3p Configuration
27 Co [Ar] ↑↓ ↑↓ ↑ ↑ ↑ ↑↓ [Ar] 4s 2 3d 7 11 Na [Ne] ↑ [Ne] 3s1
28 Ni [Ar] ↑↓ ↑↓ ↑↓ ↑ ↑ ↑↓ [Ar] 4s 2 3d 8
29 Cu [Ar] ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ [Ar] 4s1 3d10
n=3 ml = 0
30 Zn [Ar] ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ [Ar] 4s 2 3d10 3s1 :
For Cu : Another exception like Crfor essentially the same reason l=0 ms = +½

Electron Configurations Electron Configurations


 Quantum Numbers  Quantum Numbers
Write a set of quantum numbers for the third electron and
a set for the eighth electron of the F atom.

9F

1s 2s 2p

third electron is in the 2s orbital, quantum #s are:


1
n= 2 l= 0 ml = 0 ms= + or -
2
eighth electron is in a 2p orbital, quantum #s are:
1
n= 2 l= 1 ml = -1, 0, or +1 ms= + or -
2
Electron Configurations Electron Configurations
 Quantum Numbers  Quantum Numbers
• magnetic quantum # ml.
• principal quantum # n: 1, 2, 3, 4....
ml = - l  +ll
⇔ main period ⇔ orbital and orientation
• angular momentum # l:
• spin quantum # ml.
l = 0  (n-1)
ms = +1/2 or -1/2
l = s, p, d, f, g, h, ....
⇔ paramagnetic or diamagnetic
⇔ sub group

Paramagnetism and Paramagnetism and


Diamagnetism Diamagnetism
• Unpaired electrons have their spins • Paired electrons have their spins
aligned ↑ or ↓ unaligned ↑↓
– increases the magnetic field of the atom – have no net magnetic field
• Atoms with unpaired electrons are called • Atoms with paired electrons are called
paramagnetic diamagnetic
– are attracted to a magnet – atoms are repelled by
a magnet

“the best prize that life can


offer is working hard on a
Next meeting:
work worth doing”
doing”
- Theodore Roosevelt More about the Periodic Table
Chemical Periodicity

questions?

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