Professional Documents
Culture Documents
visible light
ultraviolet radiation (UV)
infrared radiation (IR)
radio waves
microwaves
x-rays
?sound waves?
3
The Wave Nature of Light
The wavelength, λ, is the distance
between crests in a wave
The frequency, ν, of a wave is the
number of cycles which pass a point in
one second.
The speed of a wave, c, is given by its
frequency multiplied by its wavelength:
c = νλ
where c = 3 x 108 m.s-1 (the “speed of
light”)
4
Short wavelength
High frequency as λ ν
Long wavelength
Small frequency as λ ν
5
The Wave Nature of Light
6
7
Quantized Energy and Photons
Some problems affecting science in 1900:
Blackbody radiation
Photoelectric effect
Line spectra
Spiraling of electrons into nucleus
8
Quantized Energy and Photons
Planck: energy can only be absorbed or released from
atoms in certain amounts called quanta.
ΔE = nh υ where n=integer
9
Quantized Energy and Photons
The Photoelectric Effect
•The photoelectric effect provides evidence for the
particle nature of light -- “quantization”.
•If light shines on the surface of a metal, there is a
point at which electrons are ejected from the metal.
•The electrons will only be ejected once the threshold
frequency, υ, is reached.
11
The Photoelectric Effect
Energy of threshold
ejected frequency
electrons
νo frequency, ν
13
Lothar Meyer 1830-1895.
Codiscoverer of Periodic Table.
15
Bohr’s Model of the Hydrogen Atom
Line Spectra
Colors from excited gases arise because electrons
move between energy states in the atom. These are
called line spectra.
Na
16
Line Spectra
prism
gas discharge
tube
17
Bohr’s Model of the Hydrogen Atom
Absorption Emission
E4
E3
E2
E1
18
E3
E2 Absorption
E1
Emission
19
Bohr’s Model of the Hydrogen Atom
The first orbit in the Bohr model has energy E1 and is
assigned a quantum number, n=1. The next orbit has
energy E2 and quantum number, n=2.
BUT.......
The Bohr model doesn’t work! 20
The Wave Behavior of Matter
Knowing that light has a particle nature, it seems
reasonable to ask if matter has a wave nature.
Using Einstein’s and Planck’s equations, de Broglie
supposed:
23
Quantum Mechanics and Atomic
Orbitals
Orbitals and Quantum Numbers
If we solve the Schrödinger equation, we get wave
functions (orbitals), energies and quantum numbers.
Schrödinger’s equation requires 3 quantum numbers:
24
Quantum Mechanics and Atomic
Orbitals
Orbitals and Quantum Numbers
Azimuthal Quantum Number, l. This quantum number
depends on the value of n. l=0,1,2,....n-1
We usually use letters for l (s, p, d and f for l = 0, 1, 2, and 3).
l has to do with orbital shape.
l= 0 1 2 3 4
s p d f g
Magnetic Quantum Number, ml. This quantum number
depends on l. The magnetic quantum number has integral
values between -l and +l. Magnetic quantum numbers give the
3D orientation of each orbital.
25
Sub
n l ml Shell Shell
1 0 (s) 0 1s K
2 0 (s) 0 2s L
1 (p) 1,0,-1 2p
3 0 (s) 0 3s
1 (p) 1,0,-1 3p M
2 (d) 2,1,0,-1,-2 3d
4 0 (s) 0 4s
1 (p) 1,0,-1 4p N
2 (d) 2,1,0,-1,-2 4d
3 (f) 3,2,1,0,-1,-2,-3 4f
26
Representation of Orbitals
The s Orbitals
All s-orbitals are spherical in shape.
27
Representation of Orbitals
The p Orbitals
There are three p-orbitals px, py, and pz in each l=1 subshell.
These correspond to allowed values of ml
of -1, 0, and +1.)
The orbitals are dumbbell shaped.
As n increases, the p-orbitals get larger.
All p-orbitals have a node at the nucleus.
28
Representation of Orbitals
The p Orbitals
29
Representation of Orbitals
The d and f Orbitals
30
Representation of Orbitals
The d Orbitals
31
Quantum Mechanics and Atomic
Orbitals
Orbitals and Quantum Numbers
Orbitals can be ranked in terms of increasing energy to
yield an Aufbau diagram.
Note that the Aufbau diagram on next slide is for a
single electron system.
As n increases, note that the spacing between energy
levels becomes smaller.
32
Quantum Mechanics and Atomic Orbitals
33
Orbitals in Many Electron Atoms (everything above
hydrogen) Energies of Orbitals
Note: 2p above 2s
3p above 3s
3d above 3p
BUT: 4s below 3d
All due to screening
(next chapter).
Rule:for given value of n
energy of orbital increases
with increasing value of l
Example: for n=3
l= 0 1 2
s < p < d
Increasing energy 34
Orbitals in Many Electron Atoms
Mnemonic Device to remember Orbital Sequence
1s 2s 2p3s 3p4s 3d4p5s 4d5p6s
1s When filled with electrons, it’s
2s 2p 1s22s22p63s23p64s23d104p65s2...
3s 3p 3d
4s 4p 4d 4f
5s 5p 5d 5f 5g
6s 6p
(superscripts are numbers of
electrons in orbital series)
35
Orbitals in Many Electron Atoms
Electron Spin and the Pauli Exclusion Principle
36
Orbitals in Many Electron Atoms
Electron Spin and the Pauli Exclusion Principle
ms=+1/2 ms =-1/2
37
Orbitals in Many Electron Atoms
Electron Spin and the Pauli Exclusion Principle
Pauli’s Exclusion Principle: no two electrons can have
the same set of 4 quantum numbers.
Therefore, two electrons in the same orbital must have
opposite (+1/2 and -1/2) spins.
3p Hund’s Rule
3s
2p Hund’s Rule
2s
1s
1s2 2s2 2p6 3s2 3p6 4s2 3d10
40
Electron Configurations
41
Electron Configurations and the Periodic
Table
42
Electron Configurations and the Periodic
Table
There is a shorthand way of writing electron
configurations
Write the core electrons corresponding to the preceding
filled Noble gas in square brackets.
Write the valence electrons explicitly.
Example, P: 1s22s22p63s23p3
but Ne is : 1s22s22p6
Therefore, P: [Ne]3s23p3.
43
Development of the Periodic Table
•How do we organize elements in a meaningful way
that will allow us to make predictions about
undiscovered elements?
•Arrange elements to reflect the trends in chemical and
physical properties.
•First attempt (Mendeleev and Meyer) arranged the
elements in order of increasing atomic weight.
•Modern periodic table: arrange elements in order of
increasing atomic number.
•Elements in same column (group) have same or similar
properties.
•Properties are periodic.
44
Effective Nuclear Charge and Screening
Screening occurs when you have more than one
electron to consider.
this electron
e- is partially shielded
from this nucleus
e
by all the other
e
+ e surrounding electrons
in atom
47
Development of the Periodic Table
48
Sizes of Atoms
Covalent (atomic) radii
Array of Au atoms:
(1 Å = 10-10 m)
49
Sizes of Atoms
•As a consequence of the ordering in the periodic
table, properties of elements vary periodically.
•Atomic size varies consistently through the periodic
table.
•As we move down a group, the atoms become larger.
50
Sizes of Atoms
•As we move across a period, atoms become
smaller.
inc
inc
inc
Atomic Size
52
Atomic
Radii
53
Problem: Estimate the As-I bond length
Radii:
As = 1.19 A
I = 1.33 A
Bond Length=
1.33 1.19
1.33 + 1.19=
2.52 A
I As
54
Ionization Energy
• The first ionization energy, I1, is the amount of energy
required to remove an electron from a gaseous atom:
Na(g) → Na+(g) + e-.
•The second ionization energy, I2, is the energy required
to remove an electron from a gaseous ion:
Na+(g) → Na2+(g) + e-.
The larger the ionization energy, the more difficult it is
to remove the electron.
There is a sharp increase in ionization energy
when a core electron is removed.
55
Ionization Energy
59
Ionization Energy
In general, ionization energy increases this way
in the table.
inc
inc
inc
Ionization Energy
60
Electron Affinities
•Electron affinity is the opposite of ionization energy.
•Electron affinity is the energy change when a gaseous
atom gains an electron to form a gaseous ion:
Cl(g) + e- → Cl-(g)
•Electron affinities are usually exothermic (as in the
above example)
inc
inc
inc
Electron Affinity
61
Electron Affinities
The added electron in Cl is placed in the 3p orbital to form
the stable 3p6 electron configuration.
62
Ionic Radii
Just as atom size is periodic, ion size is also periodic.
Cations (+ ions)
•To form cations, outermost or valence electrons are
removed.
•The effective nuclear charge has increased.
•Therefore, the cation is smaller than the parent.
Anions (- ions)
To form anions, electrons are added to the
outermost orbital.
•The nuclear charge has remained the same, but
the number of screening electrons is increased.
•Therefore, anions are larger than their parents.
63
Ionic Radii
For ions of the same charge, ion size increases down a
group.
Size Decreases
65
Ionic and Atomic Radii
66
Ionic Radii
Which of the following species is the largest?
B B+ Al Al+
P P- S S-
Which of the following species is the largest?
N- P + P- P
Which of the following species is the smallest?
Rb+ K+ Cl- Ar
67
Metals, Nonmetals, and Metalloids
Metals
•Metallic character refers to the properties of metals
(shiny or lustrous, malleable and ductile)
• Metals react with acids (H+)
inc inc
•Metals have low ionization
energies. 68
Metals
•When metals are oxidized they tend to form
characteristics cations.
•All group 1A metals form M+ ions.
•All group 2A metals form M2+ ions.
•Most transition metals have variable charges.
69
Nonmetals
When nonmetals react with metals,
nonmetals tend to gain electrons
metals tend to lose electrons:
metal + nonmetal → salt
e.g. 2Al(s) + 3Br2(l) → 2AlBr3(s)
Mg(s) + P → ?
K(s) + O2 (g) → ?
Ca(s) + Cl2 → ?
Nonmetal oxides tend to be acidic:
CO2 + H2O → H2CO3
NO2 + H2O → HNO3
SO3 + H2O → H2SO4
70
Semimetals
As an acid:
B2O3 + 6NaOH → 2Na3BO3 + 3H2O
strong base
As a base:
B2O3 + 4HCl → 2Cl2B(OH) + H2O
strong acid
71