Chemistry: for

Engineering Students

Chapter 6: The Periodic Table and Atomic Structure

6.1 INSIGHT INTO Incandescent and Fluorescent Lights
6.2 The Electromagnetic Spectrum
6.3 Atomic Spectra Simplified presentation
6.4 The Quantum Mechanical Model of the Atom
6.5 The Pauli Exclusion Principle and Electron Configurations
6.6 The Periodic Table and Electron Configurations
6.7 Periodic Trends in Atomic Properties
Chemistry: for
Engineering Students Fluorescent Lights
Excitation
of some Light emission
Electricity
substance
or material

The interaction of light with atoms is essential in the

development of our model for the structure of atoms
Feb-16 Chapter-6 2
Chemistry: for
Engineering Students
The Electromagnetic Spectrum

The wave nature of light

Visible light is one form of electromagnetic radiation, which consists of

oscillating electric and magnetic fields travelling through space.

Propagation of a linearly polarized

Fundamental electromagnetic wave
relationship of
wave propagation
frequency
amplitude
c=λν
speed wavelength

Speed of light
in vacuum
c=299792458 ms-1 ≈3.00·108 ms−1
Feb-16 Chapter-6 3
Chemistry: for
Engineering Students
The Electromagnetic Spectrum

Analysis of electromagnetic radiation

Refraction is the bending of a wave when it passes from

one medium to another. The refraction angle depends on
λ and the refractive index of materials.

quartz
prism

Feb-16 Chapter-6 4
Chemistry: for
Engineering Students
The Electromagnetic Spectrum

• Visible light is just the small portion that our eyes can detect.
• Other regions are used in many technological applications
(remote controls, cell phones, …).

Microwaves

Ultraviolet
Infrared

Visible

X Rays
c=λν
Radio

Rays
Visible spectrum

Feb-16 Chapter-6 5
Chemistry: for
Engineering Students
The Electromagnetic Spectrum

6.17 (TCS) (a) What is the frequency of radiation that has a wavelength of
10 µm, about the size of a bacterium? (b) What is the wavelength of
radiation that has a frequency of 5.5’·1014s-1? (c) Would the radiations in
part (a) or part (b) be visible to the human eye? (d) What distance does
electromagnetic radiation travel in 50 µs ?

Feb-16 Chapter-6 6
Chemistry: for
Engineering Students
The Electromagnetic Spectrum

The particulate nature of light

In the photoelectric effect, light
strikes the surface of a metal and e-
are ejected. The kinetic energy of the
e- is independent of the light intensity,
but it depends on its frequency.
# (e−) KE(e−)

ν0 ν ν0 ν
When light is imparting energy to
another object, it behaves as a
collection of packets of energy, called
photons. The energy of a photon is:

Planck’s constant:
Planck’s law E = hv h=6.626075·10−34 J·s.
Feb-16 Chapter-6 7
Chemistry: for
Engineering Students
The Electromagnetic Spectrum
• When a fluorescent tube is turn on, the electric arc excites the mercury
atoms, which, in turn, emit wavelengths in the ultraviolet (UV) region of the
spectrum, predominantly at the wavelength of 253.7 nm. Knowing that the
wattage of the fluorescent tube is 54W and that the power conversion has
an efficiency of 85%, calculate the rate of UV photon emission by the
mercury atoms. Data: h= 6.626·10-34 J·s. c=3.000·108 ms-1.

The energy E of each photon emitted by Hg* is given E=hν. The light
frequency ν is related with the wavelength λ through c=λν.
Combining the wave relationship and the Planck’s law:
8 −1
c 3.000·10 ms
E = hν = h = 6.626·10−34 J ·s = 7.835·10 −19
J
λ −9
253.7·10 m
Knowing E photon, we transform power (rate of energy consumption) into
brightness/luminance (rate of photon emission) using conversion factors.
J 85 J transformed 1photon 19 photon
54 · · −19
= 5.8·10
s 100 J 7.835·10 J s

Feb-16 Chapter-6 8
Chemistry: for
Engineering Students
The Electromagnetic Spectrum

The particulate nature of light

Molybdenum metal must absorb radiation with a minimum frequency of
1.09·1015s-1 before it can eject an electron from its surface via the p
photoelectric effect.
(a) What is the minimum energy needed to eject an electron?
(b) What wavelength of radiation will provide a photon of this energy?
(c) If molybdenum is irradiated with light of wavelength of 120 nm, what is
the maximum possible kinetic energy of the emitted electrons?

Feb-16 Chapter-6 9
Chemistry: for
Engineering Students
The Electromagnetic Spectrum

The particulate nature of light

Carotenoids are yellow, orange, and red
pigments synthesized by plants. The observed
color of an object is not the color of light it
absorbs but rather the complementary color, as
described by a color wheel such as the one
shown here. On this wheel, complementary
colors are across from each other.(a) Based on
this wheel, what color is absorbed most strongly
if a plant is orange? (b) If a particular carotenoid
absorbs photons at 455 nm, what is the energy
of the photon?

Feb-16 Chapter-6 10
Chemistry: for
Engineering Students
The Electromagnetic Spectrum

Summarizing wave-particle duality: light is sometimes best

described as a wave, whereas in other cases, is described as
beam of particles (photons) carrying momentum with them.

c
Planck’s law E = hv = h
λ p=
h Momentum
of photon
λ
Einstein law E = mc = pc
2
Chemistry: for
Engineering Students The Atomic Spectra

Solar spectrum

Hg*
Phosphor coating

Fluorescent lamp

Hand-held spectroscope
Feb-16 Chapter-6 12
Chemistry: for
Engineering Students The Atomic Spectra

• The particular pattern of

wavelengths absorbed and emitted
by an element in the gas-phase is
called its atomic spectrum.
• All elements in the gas-phase
display discrete spectra exhibiting
well-separated frequencies.

Chemical bar code

Feb-16 Chapter-6 13
Chemistry: for
Engineering Students The Atomic Spectra
Summarizing: Atomic line spectra reveal the discrete
(quantum) structure of electronic configurations.
εi
3s 3p 3d
Line n=3
Emission
spectra spectrum 2s 2p
n=2
of H·
4.57 6.17 6.91 7.3 7.54
ν·1014 Hz
Energy levels
 1  (En) of H·
E n = (− R H ) 2  n = 1, 2, 3, ... 1s

me e 4  n  n=1
R H = 2 = 2.18 • 10 −18 J
8ε 0 h Rydberg’s constant
QM
Feb-16 Chapter-6 14
Chemistry: for
Engineering Students The Quantum Mechanical Model of the Atom
Quantum numbers
Orbital notation and allowed values for n, l, m and s
Principal quantum number n = 1, 2 , 3…..
Azimuthal, angular or secondary quantum number l = 0, 1,…, n − 1
Magnetic quantum number m = −l, −l + 1, …, 0,…, l −1, l
Spin quantum number s= −1/2, 1/2

• An electron shell comprises all orbitals with the same n.

• A subshell groups orbitals having the same n and l labels.
Subshells are termed s, p, d, f, when l = 0, 1, 2, 3, …
respectively.
The compact notation of a subshell 1s, 2p, 3d,… reflects both
the principal and the angular quantum numbers.
Chemistry: for
Engineering Students The Quantum Mechanical Model of the Atom
Visualizing Orbitals:
Orbitals do have both size and shape

ψ n ,l , m ( r ) = Rn ( r )·Yl , m (θ ,ϕ )
If spin s is
neglected, then
orbitals are real
functions in 3D
space

The greater n, Spherical harmonics

the bigger orbital. give “shape”
l=0
Different Space region that
orbital sizes. concentrates the
99% probability
of finding the
electron
n=1 described by the
orbital
n=2
n=3
Chemistry: for
Engineering Students The Quantum Mechanical Model of the Atom
http://azufre.quimica.uniovi.es/harmonics/harmonics.html
m=0

Spherical
m=-1 s m=1 Harmonics

m=-2 p m=2

m=-3 d m=3

f
Chemistry: for
Engineering Students
The Pauli Exclusion Principle and Electron Configurations

According to Quantum Mechanics, each electron in an

atom can be described as occupying a particular orbital.

Examples n=1, l=0, m=0, s=1/2

n=1, l=0, m=0, s=1/2 n=1, l=0, m=0, s=−1/2
n=1, l=0, m=0, s=1/2 n=1, l=0, m=0, s=−1/2 n=2, l=0, m=0, s=1/2

H He Li

The Pauli exclusion principle states that no more than 2 electrons can
be described by the same orbital (2 electrons cannot have the same set
of four quantum numbers).

Feb-16 Chapter-6 18
Chemistry: for
Engineering Students
The Pauli Exclusion Principle and Electron Configurations
Orbital energies: In the ground state of an atom,
electrons will occupy the lowest energy orbitals available.

Hydrogenoid atoms (1 electron) Multielectron atoms

 Z 2 me e 4  1 
ε i = En =  −  2  n = 1, 2, 3, ... 4p ε i = function of n and l
 8ε 0 h
2
 n 
εi εi 4s
3d

3s 3p 3d
n=3 3p

2s 2p 3s
n=2
2p
e- interact with an
e- in smaller orbitals 2s effective nuclear
are held more tightly charge that is
to the nucleus, so smaller than the full
they have lower 1s charge because of
1s
energies. shielding effects of
n=1
the rest of e-.
Chemistry: for
Engineering Students
The Pauli Exclusion Principle and Electron Configurations

The electron configuration of an atom specifying the occupied

orbitals (the way that electrons are distributed among orbitals) are predicted
with the help of the Aufbau Principle

4p
4’’
3d
εi 4s

4 3p 4’
1) Subshells are filled in order 3s
3
of increasing energy 2p
Assuming ground
(1s→2s→2p→3s→3p→ 4s→3d→4p, etc.); 2s

2 state configuration
1s
2) Maximum occupancy is: 1
2 e− for an s subshell 6 e− for a p subshell
10 e− for a d subshell, etc.
Chemistry: for
Engineering Students
The Pauli Exclusion Principle and Electron Configurations

Element # of e Orbital Diagram

H 1 1s 2s 2p 3s
The diagrams
represent the
He 2 1s 2s 2p 3s labels of the
Li 3
1s 2s 2p 3s atomic orbitals
1s 2s
Be 4 2p 3s
Hund’s rule: within a subshell, e−
1s 2s 2p 3s occupy orbitals individually
B 5
whenever possible.
1s 2s 2p 3s
C 6
1s 2s 2p 3s
N 7
1s 2s 2p
O 8 3s

1s 2s 2p 3s
F 9
Chemistry: for
Engineering Students
The Pauli Exclusion Principle and Electron Configurations

Element Nº of e Configuration # of
The inner electrons, valence
e
which lie closer to the
H 1 1s1 1
nucleus, are referred
to as core electrons.
He 2 1s2 2

The outer electrons, Li 3 1s2 2s1 1

which lie far apart
Be 4 1s2 2s2 2
from the nucleus in
the last e- shell, are
B 5 1s2 2s22p1 3
referred to as valence
electrons. C 6 1s2 2s2 2p2 4

N 7 1s2 2s2 2p3 5

The number of e− in the O 8 1s2 2s2 2p4 6
valence shell determines
the chemical properties of F 9 1s2 2s2 2p5 7
the elements.
Chemistry: for
Engineering Students
The Periodic Table and Electron Configurations

Block diagram of the Periodic Table

1 18

1 1
Hidróg
Elements in a group have the 2
Helio
eno
He
H
1.0079
same number of valence 4.0026

2 13 14 15 16 17
3 4
electrons. 5 6 7 8 9 10
2
Litio Berilio Boro Carbon Nitróge Oxígen Flúor Neón
Li
6.941
Be
9.0122
An electron shell is filled along a B
10.811 C
o no
N
o
O
F
18.998
Ne
20.179
12.011 14.006 15.999 4

period of the Periodic Table. 2 7 4

ns
3 11 12 13 14 15 16 17 18

np
Sodio Magne Alumini Silicio Fósforo Azufre chloro Argón
sio o
Na Si P S Cl Ar
22.989 Mg Al 28.086 30.973 32.064 35.453 39.948
24.305 26.981 8
3 4 5 6 7 8 9 10 11 12 5

4 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

5
Potasi
o
K
39.098

37
Calcio
Ca
40.08

38
Escandio
Sc
44.956

39
Titanio
Ti
47.90

40
Vanadio
V
50.942

41
(n-1)d
Cromo
Cr
51.996

42
Mangan
eso

Mn
54.938

43
Hierro
Fe
55.847

44
Cobalt

Co
o

58.953

45
Níquel
Ni
58.71

46
Cobre
Cu
63.546

47
Cinc
Zn
65.38

48
Galio
Ga
69.723

49
Germa
nio
Ge
72.59

50
Arsénic

As
o

74.922

51
Selenio
Se
78.96

52
Bromo
Br
79.904

53
Kriptón
Kr
83.80

54
Rubidi Estronc Ytrio Circonio Niobio Molibd Tecnec Ruteni Rodio Paladio Plata Cadmi Indio Estaño Antimo Telurio Iodo Xenón
o io eno io o o nio
Y Zr Nb Rh Pd Ag In Sn Te I Xe
Rb Sr 88.905 91.22 92.906 Mo Tc Ru 102.90 106.4 107.86 Cd 114.82 118.69 Sb 127.60 126.90 131.30
85.468 87.62 95.94 (99) 101.07 5 8 112.40 121.75 4

6 55 56 57 * 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cesio Bario Lantan Hafn Tantalio Wolfra Renio Osmio Iridio Platino Oro Mercuri Talio Plomo Bismuto Polonio Astato Radón
Cs Ba o io
Ta mio
Re Os Ir Pt Au o
Tl Pb Bi Po At Rn
132.90 137.34 La Hf 180.948 W 186.2 190.2 192.2 195.09 196.96 Hg 204.37 207.19 208.98 (209) (210) (222)
5 138.91 178. 183.85 7 200.59 0
49

7 87 88 89 ** 104 105 105 107 108 109 110 111 112

Rutherf
Franci Radio Actinio odio
Hahnio Seabor Nielsbo Hassio Meitne
o gio rio rio
Ra Ac Rf Ha Hs
Fr (226) (227) (261 (262) Sg Ns (265) Mt
(223) ) (263) (261) (266)
Chemistry: for
Engineering Students
The Periodic Table and Electron Configurations

Energetic significance of electron configurations

1 18

1 1 2
Hidróg Helio
eno
He
H
1.0079 If a neutral atom has a completely 4.0026

2 13 14 15 16 17
3 4
filled valence shell then it is a 5 6 7 8 9 10
2
Litio
Li
Berilio
Be noble gas and its electron Boro
B
Carbono
C
Nitróg
eno
Oxígen
o
Flúor
F
Neón
Ne
6.941 9.012 10.811 12.0112 N O 18.998 20.179
2
configuration is highly stable. 14.006
7
15.999
4
4

3 11 12 13 14 15 16 17 18
Sodio Magn Alumin Silicio Fósfor Azufre chloro Argón
esio io o
Na Si S Cl Ar
22.989 Mg Al 28.086 P 32.064 35.453 39.948
24.30 26.981 30.973
5
3 4 5 6 7 8 9 10 11 12 5 8

4 19
Potasi
o
20
Calcio
TendTi to lose
21
Escandio
22
Titanio
23
Vanadio
24
Cromo
25
Mangan
eso
26
Hierro
27
Cobalt
o
28
Níquel
29
Cobre
30
Cinc Tend to gain
31
Galio
32
Germanio
33
Arséni
co
34
Seleni
o
35
Bromo
36
Kriptón
Ca Sc V Cr Mn Fe Ni Cu Zn Ga Ge Br Kr
K
39.098
40.08 44.956

electrons
47.90 50.942 51.996
54.938
55.84
7
Co
58.953
58.71 63.546 65.38
electronsAs Se
69.723 72.59
74.922 78.96
79.904 83.80

5 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rubidi

Rb
o
Estron
cio
Sr
Ytrio
Y
88.905
Circonio
Zr
91.22
Niobio
Nb
92.906
Molibd
eno
Mo
Transition
Tecne
cio
Tc Ru
Rh
Ruteni
Pdo
Rodio

102.90
Paladio

106.4
Plata
Ag
107.86
Cadmi

Cd
o
Indio
In
114.82
Estaño
Sn
118.69
Antimo
nio
Sb
Telurio
Te
127.60
Iodo
I
126.90
Xenón
Xe
131.30
85.468 87.62 95.94
metals
(99) 101.0
7
5 8 112.40 121.75 4

6 55 56 57 * 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cesio Bario Lantan Haf Tantalio Wolfra Renio Osmio Iridio Platino Oro Mercur Talio Plomo Bismut Poloni Astato Radón
o nio mio io o o
Cs Ba Ta Re Os Ir Pt Au Tl Pb At Rn
132.90 137.3 La Hf 180.948 W 186.2 190.2 192.2 195.09 196.96 Hg 204.37 207.19 Bi Po (210) (222)
5 4 138.91 178. 183.85 7 200.59 208.98 (209)
49 0

7 87 88 89 ** 10 105 105 107 108 109 110 111 112

Franci Radio Actinio 4 Hahnio Seabo Nielsb Hassi Meitne
o rgio orio o rio
Ra Ac Ruthe
rfodio Ha
Fr (226) (227)
Rf (262) Sg Ns Hs Mt
(223) (263) (261) (265) (266)
(26
1)
Chemistry: for
Engineering Students
The Periodic Table and Electron Configurations

· Knowing the location of an element in the Periodic Table, you must be able
to write down the electron configuration in its neutral or ionic forms.
Element Ζ Name # of e− Electron Configuration # of
valence
e−
Si
P
Cl
Ar
Fe
O2−
Mg2+
Rb
Zn2+
Chemistry: for
Engineering Students
Periodic Trends in Atomic Properties

The physical properties of isolated atoms (atomic size, ionization energy

and electron affinity) are directly influenced by their electron configuration.

The size of atoms is expressed in terms of the atomic radii

A − A bond distance
rA = The atomic radius decreases along a
2
period (from left to right).
The atomic radii come out from Experiment:
Spectroscopic or X-ray difraction data The atomic radius increases
downwards in a group
Chemistry: for
Engineering Students
Periodic Trends in Atomic Properties

The stability of the electronic structure of atoms can be measured by means of

thermochemical experiments that yield reaction energies. Two of these energetic
quantities, ionization potential and electron affinity, tell us about the tendency
of atoms to lose or gain electrons, respectively.

Ionization energy Electron affinity

A( g ) → A(+g ) + e − A( g ) + e − → A(−g )

The ionization energy increases

The electron affinity tends to
along a period (from left to right).
increase (in absolute value) along a
period although it shows oscillations
The ionization energy decreases
downwards in a group (less periodical)
Chemistry: for
Engineering Students
Problems and Exercises
6.3 What material is most commonly used for the filaments in an incandescent bulb?
Why is this particular material chosen?
6.6 What is the role of the electric arc in a fluorescent light bulb?

6.19 Various optical disk drives rely on lasers operating at different wavelengths, with
shorter wavelengths allowing a higher density of data storage. For each of the
following drive types, find the energy of a single photon at the specified wavelength.
(a) CD, λ = 780 nm, (b) DVD, λ = 650 nm, (c) Blu-ray disc, λ = 405 nm.
6.23 When light with a wavelength of 58.5 nm strikes the surface of tin metal,
electrons are ejected with a maximum kinetic energy of 2.69 × 10−18 J. What is the
binding energy of these electrons to the metal?
6.24 The electron binding energy for copper metal is 7.18 × 10−19 J. Find the longest
wavelength of light that could eject electrons from copper in a photoelectric effect
experiment.
6.30 A neon atom emits light at many wavelengths, two of which are at 616.4 and
638.3 nm. Both of these transitions are to the same final state. What is the energy
difference between the two states for each transition?

Feb-16 Chapter-6 28
Chemistry: for
Engineering Students
Problems and Exercises
6.38 Which of the following represent valid sets of quantum numbers? For a set that is
invalid, explain briefly why it is not correct : (a) n = 3, l = 3, m= 0 (b) n = 2, l= 1, m= 0, (c) n
= 6, l= 5, m= −1, (d) n = 4, l = 3, m= −4.
6.40 Why are there no 2d orbitals?
6.42 How many orbitals correspond to each of the following designations? (a) 3p, (b) 4p
(c) 4px, (d) 6d, (e) 5d, (f ) 5f, (g) n = 5 (h) 7s.
6.50 Why does the size of an orbital have an effect on its energy?
6.54 Write the ground state electron configuration for (a) B, (b) Ba, (c) Be, (d) Bi, (e) Br.
6.56 From the list of atoms and ions given, identify any pairs that have the same
electron configurations and write that configuration: Na+, S2−, Ne, Ca2+, Fe2+, Kr, I−
6.58 Distinguish between the terms core electrons and valence electrons.
6.60 Why is there no element to the immediate right of magnesium in the periodic table?
6.70 Arrange the following atoms in order of increasing ionization energy: Li, K, C, and N.
6.72 Which element would you expect to have the largest second ionization energy, Na,
C, or F? Why?
6.74 Indicate which species in each pair has the more favorable (more negative)
electron affinity. Explain your answers. (a) Cl or S, (b) S or P, (c) Br or As
Feb-16 Chapter-6 29
Chemistry: for
Engineering Students
Problems and Exercises

6.6 (TCS) A certain quantum mechanical system has the

energy levels shown in the diagram below. The energy
levels are indexed by a single quantum number n that is
an integer.(a) As drawn, which quantum numbers are
involved in the transition that requires the most energy?
(b)Which quantum numbers are involved in the transition
that requires the least energy? (c) Based on the drawing,
put the following in order of increasing wavelength of the
light absorbed or emitted during the transition: (i) n=1 to
n=2 ; (ii) n=3 to n=2 ; (iii) n=2 to n=4 ; (iv) n=3 to n=1.

6.10 (TCS) State where in the periodic table these elements appear:
(a) elements with the ns2np5 valence-shell electron configuration
(b) elements that have three unpaired p electrons
(c) an element whose valence electrons are 4s24p1
(d) The d-block elements

Feb-16 Chapter-6 30
Chemistry: for
Engineering Students
Problems and Exercises

6.78 The compact fluorescent bulb is another fairly new light source that is likely to
have a large impact on home lighting. These bulbs combine the energy efficiency of
traditional fluorescent lights with the smaller size, “warmer” light, and dimming ability of
incandescent lights. Although compact fluorescent bulbs are expensive, manufacturers
claim that subsequent savings will more than offset the initial costs. Analyze the relative
cost of incandescent versus compact fluorescent lighting, assuming that the information
in the table below is accurate. Are industry claims of cost savings justified?
Compact fluorescent Incandescent
Initial cost 15.00€ 2.00 €
Electricity usage 18 W 75 W
Electricity cost 0.18 €/kW·h 0.18 €/kW·h
Lifetime 10000 h 2500 h

6.84 When a helium atom absorbs light at 58.44 nm, an electron is promoted from the 1s
orbital to a 2p orbital. Given that the ionization energy of (ground state) helium is 2372
kJ/mol, find the longest wavelength of light that could eject an electron from the excited
state helium atom.

Feb-16 Chapter-6 31
Chemistry: for
Engineering Students
Problems and Exercises

6.83 A metallic sample is known to be barium, Metal BE (J)

cesium, lithium, or silver. The electron binding Barium 4.30 x 10-19
energies for these metals are listed in the
Cesium 3.11 x 10-19
adjacent table. One way to identify the
element might be through a photoelectric effect Lithium 3.94 x 10-19
experiment. The experiment was performed Silver 7.59 x 10-19
three times, each time using a different laser as
the light source. The results are summarized Laser wavelength Photoelectrons?
below. (The kinetic energy of the ejected
532 nm No
photoelectrons was not measured.) Based on this
information, what conclusions can be drawn as 488 nm Yes
to the identity of the metal? 308 nm Yes

6.95 The photochemical reaction that initiates the production of smog involves the
decomposition of NO molecules, and the energy needed to break the N-O bond is 1.04
× 10−18 J. (a) Which wavelength of light is needed? (b) How many photons are needed
to decompose 0.32 mg of NO?

Feb-16 Chapter-6 32