CHAPTER 7: Atomic Structure and Periodicity

7.1 Electromagnetic Radiation

wave - a periodic disturbance through a wavelength l

medium
amplitude
frequency n cycles per second

velocity of propagation
v = ln
8
for electromagnetic radiation, velocity of propagation = c = 3.0 x 10 m/s or c = ln
(see fig. 7.2, pg 281)

Figure on pg. 294 shows pickle emitting light at 589 nm due to excited Na atoms
8
c 3.0 x 10 m/c 14
n=l = -9 = 5.09 x 10 Hz
589 x 10 m

7.2 The Nature of Matter

By 1900, physicists believed they knew most about matter and energy, and that there was little yet to learn.

Max Planck - 1900 - attempted to explain the absorption and emission of light by hot bodies. Theories
based on classical ideas of the continuous wave nature of light failed to give equations which fit the data.

Planck had to assume that energy could be lost or gained only in whole number multiples of hn, where h =
-34
6.626 x 10 Jsec

∆E = nhn

Energy is quantized; it can be absorbed or emitted in discrete bundles called quanta.

What is the energy of the quanta emitted by the pickle light?

-34 14 -19
∆E = hn = (6.626 x 10 Jsec)(5.09 x 10 Hz) = 3.37 x 10 J

Photoelectric Effect - Albert Einstein - 1905

light shining on electrode causes electrons to be ejected, causing a photocurrent. It was

found that the current increased with the intensity of the light, but that if the light were
below a certain frequency, no current was produced regardless of the intensity of the
light

hc
Einstein proposed that light consisted of quanta of energy E = hn =
l
light behaves as if it is made up of discrete bundles called photons.

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Chapter 7 Atomic Structure and Periodicity

2 E
Einstein also derived E = mc or m = 2
c
2 2
If E = mc and E = hn, then mc = hn. Since n = c/l, mc = h/l. This equation relates the momentum of a
photon (a particle property) with its wavelength (a wave property).

Since energy and matter are the same thing, Louis deBroglie proposed (1923) that, for a real particle with
velocity v,

mv = h/l. or l = h/mv

For a 80 kg person running at 6.7 m/sec (a 4-min mile)

-34 -36
l = h/mv = (6.626 x 10 Jsec)/(80 kg)(6.7 m/sec) = 1.24 x 10 m

-15
compared to nucleus, 1 x 10 m, this number is so small as to be meaningless.

-31 6
For an electron (9.11 x 10 kg) with a velocity of 6.7 x 10 m/sec

-34 -31 6 -10

l = h/mv = (6.626 x 10 Jsec)/(9.11 x 10 kg)(6.7 x 10 m/sec) = 1.1 x 10 m = 0.11 nm

This is in the range of x-rays. Atoms are 1Å to 2 Å (0.1 - 0.2 nm) in diameter, and a regular crystal (such as
NaCl) acts as a diffraction grating for X-rays, causing a diffraction pattern.
At Bell labs, in 1927, an electron beam was diffracted through a Ni crystal and found to exhibit a diffraction
pattern nearly identical to an X-ray diffraction pattern. This shows that electrons display both particle and
wave properties.

7.3 The Atomic Spectrum of Hydrogen

A rainbow, or the light passing through a diffraction grating or prism is a continuous spectrum of light.

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Chapter 7 Atomic Structure and Periodicity

Under some conditions, atoms and molecules are seen to absorb or emit discrete wavelengths rather than
continuous spectra of light. This is called a line spectrum. (fig. 7.6, pg. 288). This means that there are only
certain energy levels that the H atom can have, the energy of H is quantized.

hc
∆E = hn = l

7.4 The Bohr Model

In the old planetary model, electrons were believed to orbit the nucleus like planets
around the sun; however, a charged particle moving in a circle generates a magnetic field
which opposes the current, thus radiating energy. This would cause the orbit to decay
-7
and the electron to spiral into the nucleus in about 10 seconds

1913 Neils Bohr proposed a model of the H atom in which angular momentum is quantized.

nh
mvr = where m = mass of electron n = 1, 2, 3, 4…
2p
-34
v = velocity of electron h = 6.626 x 10 J sec
r = radius of orbit

n=4 From the classical centripetal and electrostatic forces, n = •, E = 0

n=3 n = 4, E = -R/16
n = 3, E = -R/9
n=2 4 2
n=1 2e p m -18 1 n = 2, E = -R/4
E=- 2 2 = -2.178 x 10 J 2
n h n

Zero energy corresponds to the energy of a free

(unattached) electron. Negative energy corresponds to a
bound electron. n = 1, E = -R

Transitions between energy levels require ∆E = Efin - Einit

For a transition from level 3 to level 2, ∆E = E2 - E3

-18 1 -18 -19

E2 = -2.178 x 10 J 2 = -(2.178 x 10 J)(0.25) = -5.445 x 10 J
2
-18 1 -18 -19
E3 = -2.178 x 10 J 2 = -(2.178 x 10 J)(0.111) = -2.420 x 10 J
3
-19 -19 -19
∆E = (-5.445 x 10 J) - (-2.420 x 10 J) = -3.025 x 10 J
(negative because the electron is losing energy)

This energy change requires the emission of a photon with exactly the right energy
Ephoton = |∆Eelectron| = hc/l

-34 8 -19 -7
l = hc/∆E = (6.626 x 10 J sec)(3.0 x 10 m/sec)/(3.025 x 10 J) = 6.571 x 10 m

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Chapter 7 Atomic Structure and Periodicity

compare with figure 7.6, pg. 298 orange line at 656 nm

The Bohr model gives good results only for 1 electron atoms.

-18 Z2
E = -2.178 x 10 J where Z =atomic number (1 for H)
n2

7.5 The Quantum Mechanical Model of the Atom

Erwin Schroedinger attempted to describe an electron’s behavior by emphasizing the wave aspect rather than
the particle aspect.

2 2 2 2
∂ Y ∂ Y ∂ Y 8p m
2 + 2 + 2 + 2 (E - V) Y = 0 time independent Schroedinger equation
∂x ∂y ∂z h

Y is the wave function, a function which gives the amplitude of the electron wave as a function of x, y, z, t.
E is the energy operator and V is the potential energy operator. The solution of the Schroedinger equation
gives an infinite number of solutions (just as the Bohr model of the H atom gave an infinite number of
orbits). Each of these is called an orbital, and can be described by a set of 3 numbers called quantum
numbers, which are analagous to the number n in the Bohr model.

h
Heisenberg Uncertainty Principle Dx D(mv) ≥
4#
direct consequence of the fact that a particle has wave properties l = h/mv

2
The physical properties of the electron (charge and mass) are correlated to the value of Y (the wave
intensity)

Y vs r 2
Y vs r

2
The electron acts like a cloud distributed through space everywhere the value of Y is nonzero.

Orbital - a volume of space which an electron cloud may occupy

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Chapter 7 Atomic Structure and Periodicity

7.6 Quantum Numbers

Principle Quantum Number n = 1, 2, 3, 4…

n determines the size of the electron cloud and the energy of the orbital
electrons with the same value of n are said to be in the same shell

Angular Momentum Quantum Number l = 0, 1, 2, 3, …, n-1

l determines the sape of the orbital (angular distribution of the electron cloud)
electrons with the same value of l are said to be in the same subshell
th
each shell has 1 more subshell as the previous shell (the n shell has n subshells)
n=1 l=0
n=2 l=0
l=1
n=3 l=0
l=1
l = 2, etc.

l=0 1 2 3
subshell = s p d f
sharp, principle, diffuse, fine

shell and subshells are identified as 1s, 2s, 2p, 3d, 4f, etc.

Magnetic Quantum Number ml = -l, …, -2, -1, 0, 1, 2, …, +l

ml determines the orientation of an orbital
each subshell has 2 more orbitals than the previous subshell
(the l subshell has 2l + 1 orbitals)

n=1 l=0 1s ml = 0
n=2 l=0 2s ml = 0
l=1 2p ml = -1, 0, +1
n=3 l=0 3s ml = 0
l=1 3p ml = -1, 0, +1
l=2 3d ml = -2, -1, 0, +1, +2
n=4 l=0 4s ml = 0
l=1 4p ml = -1, 0, +1
l=2 4d ml = -2, -1, 0, +1, +2
l=3 4f ml = -3, -2, -1, 0, +1, +2, +3

7.7 Orbital Shapes and Energies

Orbital shapes are defined as the volume of space which contains 90% of the electron cloud density. Each
orbital is a 3-dimensional wave, where the energy of the wave is related to the number of nodes (areas where
Y = 0). Nodes can be planar surfaces, spherical surfaces, or more complicated surfaces.

The Principle quantum number n determines how many nodes there are: n-1 nodes.

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Chapter 7 Atomic Structure and Periodicity

The Angular Momentum quantum number l determines how many of the nodes are planar surfaces: l planar
surfaces, n - l - 1 spherical surfaces.

s orbitals (l = 0) have no planar nodes, so they are spherically symmetric

p orbitals (l = 1) have 1 planar node, so they have a peanut or dumbbell shape
d orbitals (l = 2) have 2 planar nodes (90° apart), so they have a cloverleaf shape
f orbitals (l = 3) have 3 planar nodes ( 90° apart), so they have a double cloverleaf shape

1s orbital 2p orbital 3d orbital

2s orbital 3p orbital 4d orbital

Higher order orbitals have spherical nodes in addition to planar nodes.

For hydrogen, E depends only on n. The types of nodes have no effect on E so all orbitals in the same shell
have the same energy (as in the Bohr atom). For multielectron atoms, the shape does have an effect on the
energy.
For H (only) (1s) (2s 2p) (3s 3p 3d) (4s 4p 4d 4f) …

7.8 Electron Spin and the Pauli Principle

Spin Quantum Number ms = +1/2, -1/2

ms determines the magnetic moment of the electron

Pauli Exclusion Principle: no two electrons can have the same set of 4 quantum numbers (n, l, ml, ms)

7-6
Chapter 7 Atomic Structure and Periodicity

Each orbital can hold up to two electrons, if they have opposite spins.

n=1 l=0 1s ml = 0 1 orbital 2 electrons

n=2 l=0 2s ml = 0 1 orbital 2 electrons
l=1 2p ml = -1, 0, +1 3 orbitals 6 electrons
n=3 l=0 3s ml = 0 1 orbital 2 electrons
l=1 3p ml = -1, 0, +1 3 orbitals 6 electrons
l=2 3d ml = -2, -1, 0, +1, +2 5 orbitals 10 electrons
n=4 l=0 4s ml = 0 1 orbital 2 electrons
l=1 4p ml = -1, 0, +1 3 orbitals 6 electrons
l=2 4d ml = -2, -1, 0, +1, +2 5 orbitals 10 electrons
l=3 4f ml = -3, -2, -1, 0, +1, +2, +3 7 orbitals 14 electrons

7.9 Polyelectronic Atoms

For atoms with more than one electron, the Schroedinger equation cannot be solved exactly because of
problems with electron-electron repulsion. As an approximation, each electron can be treated as if it were
alone, and attracted to the nucleus by an effective nuclear charge which includes the nuclear attraction and
the other electrons’ repulsions

Z eff = Z - (electronic repulsion)

This allows a calculation of orbitals which are similar to those of the 1 electron H atom, but vary in energy.
In particular, subshells within a shell are found not to be degenerate.

7.10 The History of the Periodic Table

Johann Dobereiner(1780 - 1849) - triads : sets of three elements with similar properties
John Newlands (1864) octaves: noticed that elements seemed to repeat properties in groups of eight.

Julius Lothar Meyer (german, 1830 - 1895) and Dmitri Mendeleev (russian, 1834 - 1907) “modern” periodic
table. Mendeleev gets most credit because he used the chart to predict the properties of yet undiscovered
elements Ga, Sc, Ge, Tc, Re. Elements listed in order repeat chemical and physical properties periodically
originally listed by increasing mass, now by atomic number.

7.11 The Aufbau Principles and the Periodic Table

Aufbau (building up) principle: the electronic structure of an atom can be determined by adding one electron
to the atom before it.

7-7
Chapter 7 Atomic Structure and Periodicity
1
H 1s electron configuration ≠ orbital diagram
2
He 1s ↑Ø
2 1
Li 1s 2s ↑Ø ↑
2 2
Be 1s 2s ↑Ø ↑Ø
2 2 1
B 1s 2s 2p ↑Ø ↑Ø ↑
2 2 2
C 1s 2s 2p ↑Ø ↑Ø ↑ ↑
2 2 3
N 1s 2s 2p ↑Ø ↑Ø ↑ ↑ ↑
2 2 4
O 1s 2s 2p ↑Ø ↑Ø ↑Ø ↑ ↑
2 2 5
F 1s 2s 2p ↑Ø ↑Ø ↑Ø ↑Ø ↑
2 2 6
Ne 1s 2s 2p ↑Ø ↑Ø ↑Ø ↑Ø ↑Ø

Hund’s Rule: Electrons enter orbitals in a subshell singly, with parallel spin, until each orbital is half full
before pairing up.

Valence Shell: the outermost occupied shell

Valence Electrons: electrons in the outermost occupied shell
Core electrons (inner shell electrons): electrons in all shells smaller than the valence shell

1 2 6 2 5 2 10 1
Na:[Ne] 3s Ar:[Ne]3s 3p Mn:[Ar]4s 3d Ga:Ar]4s 3d 4p
2 1 2 6 1 10 2
Mg:[Ne]3s K:[Ar] 4s Fe:[Ar]4s 3d Ge:[Ar]4s 3d 4p
2 1 2 2 7 2 10 3
Al:[Ne]3s 3p Ca:[Ar]4s Co:[Ar] 4s 3d As:[Ar]4s 3d 4p
2 2 2 1 2 8 2 10 4
Si:[Ne]3s 3p Sc:[Ar]4s 3d Ni:[Ar]4s 3d Se:[Ar]4s 3d 4p
2 3 2 2 1 10 2 10 5
P:[Ne]3s 3p Ti:[Ar]4s 3d Cu:[Ar]4s 3d Br:Ar]4s 3d 4p
2 4 2 3 2 10 1 10 6
S:[Ne]3s 3p V:Ar]4s 3d Zn:[Ar]4s 3d Kr:[Ar]4s 3d 4p
2 5 1 5
Cl:[Ne]3s 3p Cr:[Ar]4s 3d

Order of filling of subshells: 1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p 7s 5f 6d 7p 8s

rs rp
(r-1)d
La
Ac

(r-2)f

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Chapter 7 Atomic Structure and Periodicity

Z eff = Z - electron screening

3s inner shell electrons are able to screen part or all

of the nuclear charge, but this screening is offset
3p by orbital penetration.
ns > np > nd > nf
3d most penetration least penetration
distance from the nucleus

Because of penetration, subshells within a shell are not degenerate, and always fill in the order s - p - d - f

The energy levels of the subshells split so much that they actually overlap between shells.
6f
7p
5f 6d
7s
5d 6p
4f 6s
5p
4d
5s
4p
3d
4s
3p
3s
2p
2s
1s
As an approximation, Zeff = Z - (inner shell electrons)

7.12 Periodic Trends in Atomic Properties

Ionization Energy: energy required to remove an electron from a gaseous atom in its ground state.
+ -
M (g) Æ M (g) + e first ionization energy
+ 2+ -
M (g) Æ M (g) + e second ionization energy

Ionization energy increases because of reduced electron-electron repulsion (increases Zeff) and more tightly
bound shells/subshells

Ionization energy increases across a row and decreases down a column. Lowest for metals and highest for
nonmetals.

metals lose (group number) electrons because these are the least tightly held

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Chapter 7 Atomic Structure and Periodicity

Electron Affinity: energy change when an electron is added to a gaseous atom in its ground state.
- -
E(g) + e Æ E (g)

Electron affinities generally become more negative across a row and up a column.

Atomic Radius [Covalent radius: determined from covalently bonded atoms]

Size decreases across a row, increases down a column (see fig. 7.35, pg 333)

Lanthanide Contraction

2.09 2.00 1.92 1.85 1.79 1.72 1.67 1.62 1.57 1.53
Sc Ti V Cr Mn Fe Co Ni Cu Zn
3.0 4.50 5.8 7.19 7.43 7.86 8.90 8.90 8.96 7.14
2.27 2.16 2.08 2.01 1.95 1.89 1.83 1.79 1.75 1.71
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
4.5 6.49 8.55 10.2 11.5 12.2 12.4 12.0 10.5 8.65
2.74 2.16 2.09 2.02 1.97 1.92 1.87 1.83 1.79 1.76
La Hf Ta W Re Os Ir Pt Au Hg
6.7 13.1 16.6 19.3 21.0 22.4 22.5 21.4 19.3 13.53

7.13 The Properties of a Group: The Alkali Metals

Information Contained in the Periodic Table - Elements in the same group have the same outer electron
(valence) configuration. Chemistry is determined by valence electron configuration. Electron configuration
can be determined from position on the periodic table

Know: Alkali metals, Alkaline earth metals, halogens, noble gases, lanthanides, actinides, metals, non-metals,
metalloids

The Alkali Metals - see table 7.8, pg.335

Properties of Five Alkali Metals

density 1st hydration
at 25° ionization atomic ionic energy for
Element valence 3 mp bp energy radius radius cation
(g/cm )
config °C °C (kJ/mol) (pm) (pm) (kJ/mol)
Li 1 0.53 180 1330 520 155 60 -510
2s
Na 1 0.97 98 892 495 190 95 -402
3s
K 1 0.86 64 760 419 235 133 -314
4s
Rb 1 1.53 39 688 409 248 148
5s
Cs 1 1.87 29 690 382 267 169
6s
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Chapter 7 Atomic Structure and Periodicity

Density: mass usually increases faster than size, so density increases

mp and bp: usually not a clear correlation between mp/bp and position on the chart

Ionization energy: lowest on the chart. very reactive metals, never found in uncombined state.
2M + X2 Æ 2MX (X = F, Cl, Br, I)
2M + 2H2O Æ 2MOH + H2

+
reducing ability Cs > Rb > K > Na > Li, but in water, Li > K > Na because Li is smaller and has a larger
hydration energy.

7 - 11