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The Quantum
Mechanical Atom
Electromagnetic Energy
Electromagnetic Radiation
Light energy or wave
Travels through space at speed of light in vacuum
c = speed of light = 2.9979 x 108 m/s
Successive series of these waves or oscillations
Waves or Oscillations
Systematic fluctuations in intensities of electrical
and magnetic forces
Varies rhythmically with time
Exhibit wide range of energy
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
Properties of Waves
Wavelength ()
Distance between two successive peaks or troughs
Unit = meter
Frequency ()
number of waves per second that pass a given point in
space
Unit = Hertz (Hz) = cycles/sec = 1/sec = s1
Related by =c
8
c 2.9979 10 m/s
650 10 9 m
= 4.61 × 1014 s–1 = 4.61 × 1014 Hz
White light
Equal amount of all these colors
Can separate by passing through prism
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
Important Experiments in Atomic Theory
Late 1800’s:
Classical physics incapable of describing atoms and
molecules
Matter and energy believed to be distinct
Matter: made up of particles
Energy: light waves
Beginning of 1900’s:
Several experiments proved this idea incorrect
Experiments showed that electrons acted like:
Tiny charged particles in some experiments
Waves in other experiments
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
Particle Theory of Light
Max Planck and Albert Einstein (1905)
Electromagnetic radiation is stream of small packets
of energy
Quanta of energy or photons
Each photon travels with velocity = c
Pulses with frequency =
Energy of photon of electromagnetic radiation is
proportional to its frequency
Energy of photon E = h
h = Planck’s constant
= 6.626 x 1034 J·s
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
What is the frequency, in sec–1, of radiation which
has an energy of 3.371 x 10–19 joules per photon?
E
h
3.371 10 19 J
6.626 10 34 J s
= 5.087×1014 s–1
+ gas
1 1 1 1
( 1 12 ) 0.110
7.13455 4 n
2
n2 4 7.13455
2
1
2
n2 9.10
0.110 n2 = 3
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
What is the wavelength of light (in nm) that is
emitted when an excited electron in the hydrogen
atom falls from n = 5 to n = 3?
A. 1.28 × 103 nm 1 1 1 1
109,678 cm 2 2
B. 1.462 × 104 nm 3 5
C. 7.80 × 102 nm 1
7799 cm 1
D. 7.80 × 10–4 nm
E. 3.65 × 10–7 nm 1 1 10 7 nm
7799 cm1 1cm
E s are quantized
Every time e drops from n = 3 to n = 1
Same frequency photon is emitted
Yields line spectra
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
Bohr Model of H
E is negative number
Reference point E = 0 when n =
e not attached to nucleus
Sign arises from Coulombic attraction between +
and – charges (oppositely charged bodies)
Coulomb's Law Attractive force
(charge on A)(charge on B)
E
distance between them
Stronger attractive force = more negative E
Constructive interference
Waves “in-phase” lead to greater amplitude
Add
Destructive interference
Waves “out-of-phase” lead to lower amplitude
Cancel out
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
Diffraction and Electrons
Light
Exhibits interference
Has particle nature
Electrons
Known to be particles
Also demonstrate interference
= 7.27 x 10–11 m
4s 4p 4d
3s 3p 3d
Energy
1s 2s 2p
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
Energy Level Diagram for Multi e
Atom/Ion
4f
6s
5p
4d
5s
4p
4s 3d
3p
3s
Energy
1s
4p
4s 3d
3p
3s
Energy
2p
2s Each arrow represents electron
1s
4p
4s 3d
3p
3s
Energy
2p
2s
Each arrow represents an electron
1s2 2s2 2p6 3s2 3p6 4s2 3d3
1s
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
Give electron configurations and orbital diagrams
for Na and As
6s
5p
4d
5s
4p
4s 3d
3p
3s
Energy
2p
2s Na Z = 11 1s22s22p63s1
As Z = 33
1s22s22p63s23p64s23d104p3
1s
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
The ground state electron configuration for Ca
is:
A.[Ar] 3s1
B.1s2 2s2 2p6 3s2 3p5 4s2
C.[Ar] 4s2
D.[Kr] 4s1
E.[Kr] 4s2
58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
90 91 92 93 94 95 96 97 98 99 100 101 102 103
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
Read Periodic Table to Determine
e- Configuration – He
n= 1 1 2
Read from left to H He “ns” orbital being filled
n= 2 3 4 “np” orbital being filled
right Li Be “(n – 1)d” orbital being filled
n= 3 11 12
1st e– goes into Na Mg
“( n – 2)f” orbital being filled
period 1 n= 4 19 20 21 22 23 24 25 26 27 28
K Ca Sc Ti V Cr Mn Fe Co Ni
1st type of sublevel n= 5 37 38 39 40 41 42 43 44 45 46
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd
to fill = “1s” n= 6 55 56 57 72 73 74 75 76 77 78
Cs Ba La Hf Ta W Re Os Ir Pt
He has 2 e– n= 7 87 88 89 104 105 106 107 108 109 110
Fr Ra Ac Rf Db Sg Bh Hs Mt Ds
e– configuration for
He is: 1s2
B has 5 e–
Fill first shell…
Fill two subshells in 2nd shell, in order of increasing E
Electron Configuration B = 1s22s22p1
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
Noble Gas Core Notation for Mn
Find last noble gas that is filled before Mn
Next fill sublevels that follow [Ar] 4s 2 3d 5
n= 1 1 2
“ns” orbital being filled
H He
n= 2 3 4 “np” orbital being filled 5 6 7 8 9 10
Li Be “(n – 1)d” orbital being filled B C N O F Ne
n= 3 11 12 13 14 15 16 17 18
“( n – 2)f” orbital being filled
Na Mg Al Si P S Cl Ar
n= 4 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
n= 5 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
n= 6 55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
n= 7 87 88 89 104 105 106 107 108 109 110 111
Fr Ra Ac Rf Db Sg Bh Hs Mt Ds Rg
58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
90 91 92 93 94 95 96 97 98 99 100 101 102 103
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
Writing Electron Configurations
Fill pattern across row in Periodic Table is:
ns [(n2)f ] [(n1)d ]np
where n = row number in periodic table
Must rearrange e configuration
List in order of increasing n
Within n level, list in order of increasing
Why?
Once 3d and 4f are filled, they become part of core e
Harder to remove e in core or with lower n
Ru [Kr]
4d 5s
S [Ne]
3s 3p
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
Valence Shell Electron Configurations
One last type of electron configuration
Use with representative elements (s and p block
elements)—longer columns
Here only e’s in outer shell important for bonding
Only e’s in s and p subshells
Valence Shell = outer shell
= occupied shell with highest n
Result - use even more abbreviated notation
for e configurations
Sn = 5s2 5p2
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
Electronic Configurations:
A few exceptions to rules
A.
1s 2s 2p
B.
1s 2s 2p
C.
1s 2s 2p
D.
E. 1s 2s 2p
1s 2s 2p
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
Which of the following choices is the correct
electron configuration for a cobalt atom?
4s 3d
A.[Ar] ↑↓ ↑↓ ↑↓ ↑↓ ↑
B.[Ar] ↑ ↑↓ ↑↓ ↑↓ ↑↓
C.[Ar] ↑ ↑↓ ↑↓ ↑↓ ↑ ↑
D.[Ar] ↑↓ ↑↓ ↑↓ ↑↓ ↑
E.[Ar] ↑↓ ↑↓ ↑↓ ↑ ↑ ↑
a. Dot-density diagram
b. Probability of finding electron around given point,
ψ2, with respect to distance from nucleus
c. Radial probability distribution = probability of
finding electron between r and r + x from nucleus
rmax = Bohr radius
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
e Density Distribution
Determined by Shape
Size n
Orientation m
e density
No sharp boundary
Gradually fades away
―Shape‖
Imaginary surface enclosing 90% of e density of
orbital
Probability of finding e is same everywhere on
surface
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E
Effect of n on s Orbital
In any given direction
probability of finding e
same
All s orbitals are
spherically shaped
Size as n
A. B. C.
D. E. z
Change: EA(kJ/mol)
O(g) + e– O–(g) –141