Chemistry

What is the world made of?

Why does “stuff” do what it does?

Electronic Structure
Start at the bottom: Matter is made of atoms (and ions).

Properties of atoms and ions are determined by their electronic structure –

the arrangement of the electrons.

To understand how we can know about the electronic structure of atoms, we

must first learn about light.

It is through the interaction of light and matter that the electronic structure of
atoms was elucidated.

-1-
Light

Light is an electromagnetic wave which carries energy. Different colors of light

correspond to different wavelengths (and frequencies).

In one period, t, one wavelength passes an observation point. The wave travels
one wavelength which equals c× t, where c is the speed of light. Since
frequency, ν = 1/ t,

c = λν

Frequency, ν, is the number of peaks passing the observation point per unit time.
The SI unit of frequency is Hz, (1 Hz = 1 s‒1).

Wavelength is the distance between peaks measured in m.

Nanometers (1 nm = 10‒9 m) are often used in the case of visible light.

-2-
 wavelength

direction of
propagation

The speed of light in a vacuum, c = 2.9979×108 m s‒1, is the same for all
wavelengths. Consequently, wavelength and frequency have a simple reciprocal
relationship.

c c
λ= and ν= .
ν λ

-3-
The electromagnetic spectrum
wavelength, λ, in m

100 1 10-2 10-4 10-6 10-8 10-10 10-12 10-14

radio TV microwave infrared ultraviolet X-ray gamma ray cosmic ray

visible

3x106 3x108 3x1010 3x1012 3x1014 3x1016 3x1018 3x1020 3x1022

frequency, ν, in Hz

red yellow green blue violet

red
orange ↑ λ increases
yellow
green
blue ↓ ν increases
white light violet

-4-
Blackbody Radiation

Except at absolute zero temperature, all objects emit electromagnetic radiation

due to thermal energy. This is called blackbody radiation.

Classical wave theory could not predict the observed spectrum – the ultraviolet
catastrophe.

500 Power emitted per unit

frequency and unit surface
400
area vs. frequency
T = 600 K
300
units:
200 vertical axis: pJ m‒2
horizontal axis: THz
100 T = 300 K

0
20 40 60 80 100
x 120 140 160 180 200

-5-
Planck explained the observed spectrum – its exact shape – by postulating that
light energy is quantized.

The smallest increment of light energy is the energy of a single particle of

light, a photon.

The energy of one photon of light with frequency, ν, is given by

Ephoton = hν ,

where h = 6.62606957×10‒34 J s is called Planck’s constant.

Other evidence for the particle character of light (and that of matter) comes from
Einstein’s explanation of the photoelectric effect.

Photoelectric Effect

Sufficiently high frequency photons eject electrons from the surface of a metal.
The photon energy equals the energy required to eject the electron plus the
kinetic energy of the ejected electron.

-6-
 1
Ephoton = hν = mu 2 + ϕmetal ,
2
where m and u are the electron mass and velocity, respectively, and ϕmetal is
called the work function of the metal.

Alkali metals have the smallest work functions - it takes less energy to eject an
electron from an alkali metal.

According to decreasing work function,

lithium > sodium > potassium > rubidium > cesium.

-7-
 ammeter
measures current
1 2 34
0 5 an electron, e-

variable a photon, Ephoton = h ν

voltage

-8-
Observed photoelectric effect:

ejected electrons
kinetic energy of
cesium
sodium iron

507 551 1086

frequency, ν / THz

Since electron kinetic energy must be positive, there is a lowest frequency of

light that can emit electrons – the threshold frequency, ν thres = ϕmetal / h .

-9-
Example: The work function for calcium is 4.64×10‒19 J (or 279 kJ mol‒1 – this is
the energy needed to eject 1 mol of electrons).

(a) What is the threshold frequency above which calcium will exhibit the
photoelectric effect?

(b) What is the kinetic energy of an electron ejected from calcium by a photon of
wavelength, 300. nm?

(a) The threshold photon energy equals the work function,

hν thres = ϕcalcium = 4.64 ×10−19 J
Therefore,
ϕcalcium 4.64 ×10−19 J
ν thres = = = 700 THz
h 6.626 ×10−34 J s
(b) The frequency of the incident light is
2.9979 ×108 m s−1
c
ν= = −9
= 999.3 THz
λ 300 ×10 m

- 10 -
 The kinetic energy of the ejected electron is
1 2
Ekin = mu = hν − ϕcalcium
2
= 6.626 ×10−34 J s × 999 ×1012 s −1 − 4.64 ×10−19 J
= 1.98 ×10−19 J .

Quantum Mechanics and the Hydrogen Atom

Atoms can also absorb photons of light.

An electron can be ejected from the atom - this is called ionization).

For lower energy photons (i.e., lower frequency), an excited state of the atom can
be produced.

A transition to an excited state results when the photon energy equals the
difference in energy between the initial state (typically the ground state – the
lowest energy state of the atom) and the excited state.

- 11 -
Quantum mechanics tells us that an atom has a discrete set of energy levels –
i.e., only certain energies are allowed.

Quantization of energy arises from wave properties of matter described by

quantum mechanics.

The hydrogen atom – the simplest atom with only one electron – has the simplest
set of energy levels,

RE
En = − 2 , n = 1, 2,3,…
n
where RE = 2.17987×10‒18 J is the Rydberg energy, and n is called the principal
quantum number.

The difference between two of these energies determines a transition energy

equal to the energy of the photon emitted or absorbed. The associated transition
frequency is the frequency of the photons emitted or absorbed – it is given by
dividing the transition energy by h.

- 12 -
  1 1 
∆E = En ' − En = − RE  2 − 2  = hν , n ' > n
 n' n  .
Example:

(a) Determine the frequency of the emission lines resulting when an excited
state with n’ = 3 drops to the (i) n = 2 , or (ii) n = 1 level. Are either of these
emissions in the visible range?

(b) Of all the absorption frequencies associated with transitions between all
levels up to n = 4, which transitions have the largest and the smallest
frequencies?

(a)
RE  1 1 
ν=  2 − 2 
h  n n' 
2.17987 × 10−16 J  1 1 
= −34
× 2 − 2 
6.62607 ×10 J s  2 3 
= 4.57 ×1016 s −1 = 457 THz (rounded to 3 significant digits)

- 13 -
for n = 2. For n = 1, we have ν = 2924 THz . The first of these absorption
lines is in the visible range. It corresponds to violet-blue light. In general, all
transitions with n equal to 2 produce an absorption or emission line in the
visible range. This series of lines is called the Balmer series. If n is 1, then
the line is the UV range. This series of lines is called the Lyman series.
Other named series are the Paschen (n = 3) and the Brackett (n = 4) series,
both in the infrared range.

(b) The largest transition frequency corresponds to the n = 1 to n′ = 4

absorption transition - or the reverse, the n′ = 4 to n = 1 emission transition.
The lowest frequency corresponds to n = 3 to n′ = 4 absorption or
corresponding emission transition.

- 14 -
Electrons & nuclei, & light are all treated as wave-like & particle-like

de Broglie first suggested that particles, such as electrons, are wave-like,

characterized by a wavelength …

λ = h_
mu particle momentum
u = velocity
Heavy &/or fast particles have very small wavelength
 they behave like simple particles

Electrons in an atom are light & fast-moving

 the wavelength is ~ size of the atom
 quantum effects are important

There is uncertainty in the position of an electron in an atom.

One can only speak of the probability of finding the electron in a volume within
the atom.

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Orbitals of Hydrogen

Because of the spherical symmetry of the hydrogen atom (and electron spin),
there is more than one state for each energy level.

The electron in hydrogen has an orbital angular momentum associated as it

orbits about the proton nucleus.

Angular momentum has a magnitude, with associated quantum number -

angular momentum quantum number

ℓ = 0, 1, 2, …, n ‒1 ,

and an orientation, with associated quantum number - magnetic quantum

number

mℓ = ‒ℓ, ‒ℓ + 1, …, ℓ ‒1, ℓ.

Specifying the (n, ℓ, mℓ) values determines an orbital of the hydrogen atom, which
determines the state of the electron with respect to its motion about the nucleus.

- 16 -
For n = 1, there is only one ℓ value, ℓ = 0.

For ℓ = 0, there is only one mℓ value, mℓ = 0. Therefore, the n = 1 energy

level has only one orbital – the 1s orbital.

For n = 2, there are two ℓ values, ℓ = 0 and 1.

For ℓ = 0, we have only (n, ℓ, mℓ) = (2, 0, 0) (the 2s orbital).

For ℓ = 1, we have (2, 1, ‒1), (2, 1, 0) and (2, 1, 1), the three 2p orbitals.

Orbitals are labeled by their principal and angular momentum quantum numbers,
n and ℓ. The ℓ value is denoted by a letter (s for ℓ = 0, p for ℓ = 1, d for ℓ = 2, f for ℓ
= 3, g for ℓ = 4, …).

In addition to the orbital quantum numbers already introduced, the electron has a
spin quantum number,

ms = ½ or ‒½, spin angular momentum pointing up or down,

respectively.

- 17 -
There are two states associated with the lowest energy level:

(n, ℓ, mℓ, ms) = (1, 0, 0, ½) and (1, 0, 0, ‒½)

The ground state of hydrogen is actually two states differing only in the
orientation of electron spin. All other states of hydrogen are excited states.
If excited states are produced, they lose energy by emitting photons until the
ground state is reached. Thus, in the absence of radiation exciting the
hydrogen atoms, they will be in their ground state.

In general, there are two states (with opposite spin) for every orbital. Hydrogen
orbitals can be arranged according to energy and angular momentum as follows:

- 18 -
 Energy

∞ E∞ = 0
5 E5 = − RE / 52
d orbitals
4 E4 = − RE / 4 2

p orbitals
3 E3 = − RE / 32
4s 4p 4d 4f
2 E2 = − RE / 2 2
3s 3p 3d
2s 2p

1s
1 E1 = − RE
s orbitals

For the hydrogen atom, the orbital energy depends only on the principal quantum
number. The number of orbitals with energy En is

1 + 3 + 5 + … + 2 n ‒ 1 = n2.

- 19 -
Numbers of orbitals and states of hydrogen

n ℓ Number of Number of States

Orbitals
total total
1 0 1 1 2 2
2 0 1 2
1 3 4 6 8
3 0 1 2
1 3 6
2 5 9 10 18
4 0 1 2
1 3 6
2 5 10
3 7 16 14 32

- 20 -
Example:

(a) Which of the following sets of quantum numbers, (n, ℓ, mℓ, ms), corresponds
to an actual state of a hydrogen atom?

(i) (1, 0, 1, ½) (ii) (2, 1, ‒1, ‒½) (iii) (2, 2, 0, ‒½) (iv) (3, 1, ‒1, 0)
(v) (3, ‒2, ‒2, ½)

(b) How many orbitals are there with energy up to and including E4? How many
electron states are there with energy up to this value?

(a) Only (2, 1, ‒1, ‒½) corresponds to an actual state of hydrogen.

(1, 0, 1, ½) violates mℓ ≤ ℓ.
(2, 2, 0, ‒½) violates ℓ ≤ n – 1
(3, 1, ‒1, 0) violates ms = ±½
(3, ‒2, ‒2, ½) violates 0 ≤ ℓ

(b) There are 1 + 4 + 9 + 16 = 30 orbitals with energy up to and including

E4. There are 2×30 = 60 electron states up to this energy.

- 21 -
An orbital of hydrogen corresponds to a wave function which (together with the
spin) describes the state of the electron in the atom.

A wave function is an oscillatory function of position about the nucleus.

They can be positive or negative values – or even complex.

The square of the wave function at each position gives the likelihood of
finding the electron in that location. Where the magnitude of the wave
function is largest is where the electron is likely to be.

The ℓ = 0 orbitals have spherical shape.

The 1s orbital is like a spherical ball.

The 2s orbital has a single oscillation in the radial direction. It consists of a

small inner sphere surrounded by a large outer spherical layer. Between
these radial lobes is a nodal sphere where the wave function is zero.

The 3s orbital has two nodal spheres. The ns orbital has n – 1 nodal
spheres.

- 22 -
The ℓ = 1 orbitals have a barbell shape with two lobes – positive and negative –
pointing in opposite directions along an axis. These lobes are separated by a
nodal plane where the wave function is zero.

There are three np orbitals.

The mℓ = 0 orbital is called npz orbital. It is concentrated about the z axis.

The xy plane is the corresponding nodal plane.

For mℓ = ±1, the orbitals are complex valued. However, since these orbitals
have identical properties (except in the presence of a magnetic field), it is
admissible to form + and – combinations that are real. These are npx and
npy – like npz, except aligned with x and y axes, respectively.

Like s orbitals, p orbital have nodal spheres. The np orbital has n – 2 nodal
spheres.

- 23 -
The ℓ = 2 orbitals have a double barbell or cloverleaf pattern with four lobes –
alternately positive and negative. Each d orbital has two nodal planes where the
wave function is zero. There are five (2ℓ+1) nd orbitals. The mℓ = 0 orbital is
called n d z 2 . It is concentrated about the z axis, with a doughnut-shaped lobe in
the xy plane. The mℓ = ±1 orbitals are combined to make n d xz and n d yz
orbitals, while the mℓ = ±2 orbitals are combined to make n d xy and nd x2 − y 2
orbitals.

- 24 -
 z

z z
px - + x
d x2 − y 2 d xy
z -
y z + -
+ + x + x z
- -

y y

+
s + x -
py x d z2 -
+ x
y z

+
z
y
y
z -
+ - +
d yz d xz
x x
+
+

- + -
pz
x y y
-
y

- 25 -
 s Orbital Radial Probability Distributions
♣

r r
r

1s orbital 2s orbital 3s orbital

- 26 -
The Periodic Table

Ions with only one electron – i.e., He+, Li2+, … – have the same orbitals as
hydrogen, except that they held more closely to the nucleus by the larger nuclear
charge.

The larger nuclear charge also lowers (i.e., further stabilizes), the energy
levels of the ion – in comparison with hydrogen.

Z 2 RE
En = − 2 , n = 1, 2,3,…
n

for nuclear charge, +Ze. Thus, the energy levels of He+ are four times
deeper than those of H because the nuclear charge is doubled.

- 27 -
For atoms and ions with more than one electron – i.e., almost all atoms and ions
– the states and associated energy levels are calculated on computers.

The difficulty arises because of repulsion between electrons.

If there were no electron repulsion, then each electron in a many electron atom
would be in a hydrogen-like orbital – an orbital of hydrogen, shrunken into the
nucleus, with lower energy because of the +Ze nuclear charge.

Electron repulsion modifies this picture. Though, the independent electron

approximation is a good starting point. It provides an approximate state
which corresponds to each electron assigned to a hydrogen-like orbital
(henceforth just called orbital). The energy of the state is given by summing
the occupied orbital energies, then adding corrections to account for electron
repulsion.

The above picture is complete when we account for electron spin and the Pauli
exclusion principle: two electrons with the same spin cannot occupy the same
orbital. This is a fundamental property of fermions, and electrons are fermions.

- 28 -
The electron configuration is the set of occupied orbitals. The ground state
electron configuration is obtained if the orbitals are filled in order of increasing
energy.

Ground state electron configurations:

H: 1s1
He: 1s2
Li: 1s22s1

The ground state electron configuration of lithium is not 1s22p1 because, in a

lithium atom,
2p has higher energy than 2s
- the two 1s electrons screen a 2p electron better than a 2s electron.

- 29 -
Energy

2s 2p
2p
2s
2p
1s
2s

H ground state

1s

He ground state

1s

Li ground state

- 30 -
 ♣
A 2p electron is better shielded by the two 1s electrons than is a 2s electron.
The 2s electron has lower energy.

The electron configurations of Be, B and C:

Repulsion between the two 2p electrons in C is minimized
Be: 1s22s2
when the electrons have the same-spin – they are in
B: 1s22s22p1
different orbitals.
C: 1s22s22p2
Electrons in different orbitals are further apart, on average,
than electrons in the same orbital.

Electrons with the same spin avoid each other and thereby
minimize repulsion.
- 31 - Hund’s Rule
E nergy

2s 2p
2p
2s 2p

2s

1s

B e g ro u n d sta te

1s

B g ro u n d s ta te 1s

C g ro u n d s ta te

- 32 -
 Box Diagrams & Hund's Rule

Box Diagram Electron

for Configuration
Ground State Atom
of Ground
1 2 2p
s s
States
1 s1 H
1 s2 He
1 s2 2s1 Li
1 s2 2s2 Be
1 s2 2s2 2p1 B
1 s2 2s2 2p2 C

- 33 -
 Diamagnetic versus Paramagnetic

Electrons behave as tiny magnets, because of their charge and spin.

They are attracted to regions of increasing magnetic field.
They are paramagnetic.

Atoms with unpaired electrons in their ground state electron configuration are
paramagnetic – they are attracted to a magnetic field.

e.g., C:[He] 2s2 2p2 is paramagnetic because of Hund’s rule – the two 2p
electrons are unpaired. F: [He] 2s2 2p5 is also paramagnetic. Most elements (in
atomic gas form) are paramagnetic.

The magnetic fields of two paired electrons cancel. Pairs of electrons are
diamagnetic. They are repelled by a magnetic field. However, the effect is very
small. While all atoms, except H, have paired electrons, they are paramagnetic
even if they have just one unpaired electron.

e.g.s of diamagnetic atoms: Be: [He] 2s2 and Ne: [He] 2s2 2p6 = [Ne]

- 34 -
The ground state electron configurations of all the atoms is determined in this
way - the Aufbau principle (“building up”).

Orbital Subshell filling order:

1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p 7s

1s

2s 2p
3s 3p 3d
4s 4p 4d 4f

5s 5p 5d ...

6s 6p ...

7s ...

- 35 -
Example:

(a) Determine ground state electron configurations for the following atoms. Use
the noble gas shorthand notation (except in case of Ne). The electron
configuration of Ar determines the core of fourth row elements. The electron
configuration of fourth row elements is then written as [Ar] followed by the
valence configuration.

(i) N (ii) Ne (iii) P (iv) Ca (v) V

(b) To which element does the following atomic ground state electron
configuration correspond?

1s22s22p63s23p64s23d7

(a) N: 1s22s22p3
Ne: 1s22s22p6
P: [Ne] 3s23p3
Ca: [Ar] 4s2
V: [Ar] 4s23d3

- 36 -
 (b) There are 27 electrons in this atom. Therefore, it is cobalt (Z = 27).

Chromium and copper are the two exceptions to the orbital filling order of Fig.
3.9, that occur in the first 40 elements. The electron configurations of chromium
and copper are as follows ( noble gas shorthand notation to the right):

Cr: 1s22s22p63s23p64s13d5 [Ar] 4s13d5 half-filled 3d subshell

Cu: 1s22s22p63s23p64s13d10 [Ar] 4s13d10 filled 3d subshell

Patterns in the electron configuration of the atoms determine the block structure
of the periodic stable. The periodic table is arranged in blocks according to the
subshell of the highest energy electrons. Elements in the same column, group,
have the same number of valence electrons – the number of electrons in the
outer shell.

- 37 -
The block structure of the periodic table

s block f block d block p block

1s
2s 2p
3s 3p
4s 3d 4p
5s 4d 5p
6s 4f 5d 6p
7s 5f 6d 7p

- 38 -
Periodic Properties
Atomic/Ionic Radius

Size of an atom is determined by its shell structure.

Atoms with the same number of valence electrons – i.e., atoms in the same
group – increase in size with increasing number of shells – i.e., atomic
radius increases going down a group.

For example, with respect to atomic radius, Li < Na < K < Rb < Cs

Atoms in a row of the periodic table have the same number of shells – and
the same number of inner shell electrons. They differ in the number of
valence electrons, and in the charge on the nucleus. Since nuclear charge
increases across a row, with fixed number of screening electrons, the
effective nuclear charge felt by the valence electrons increases across the
row. Larger effective nuclear charge pulls the valence shell closer to the
nucleus, and atomic radius decreases across a row – from left to right.

- 39 -
 For example, with respect to atomic radius,

Li > Be > B > C > N > O > F > Ne

The effective nuclear charge is approximated by core charge, the charge of the
nucleus plus the (negative) charge on the inner shell electrons – core charge
equals group number for main group elements.

The trends in atomic radius

Atomic radius increases down and to the left

- 40 -
Rules regarding ionic radius:

The radius of the ions of an element – i.e., nuclear charge is fixed –

increases with increasing number of electrons. Thus,

… < X3+ < X2+ < X+ < X < X‒ < X2‒ < X3‒ < …

The radius of ions, or atoms, with the same number of electrons -

isoelectronic species – increases with decreasing nuclear charge. For
example,

Ca2+ < K+ < Ar < Cl‒ < S2‒

Example:

(a) Order the following elements according to increasing atomic radius:

Cs F N He Ga As

- 41 -
(b) Order the following ions/atoms according to increasing radius:

(i) O2‒ Mg2+ Ne Na+ F‒

(ii) Se2‒ Br‒ Kr+ Br Rb2+

(a) He is the highest and rightmost element. The He atoms are the
smallest. The next such element is F, then N, As, Ga and Cs – i.e.,

He < F < N < As < Ga < Cs.

- 42 -
(b) (i) These are isoelectronic species. The smallest radius occurs for the
highest atomic number. Therefore,

Mg2+ < Na+ < Ne < F‒ < O2‒

(ii) Br‒ and Se2‒ are isoelectronic. Therefore,

Br‒ < Se2‒.

Br, Kr+ and Rb2+ are also isoelectronic. Therefore,

Rb2+ < Kr+ < Br.

Since, Br < Br‒, we have

Rb2+ < Kr+ < Br < Br‒ < Se2‒.

- 43 -
Atomic Radii of Main Group Elements (in pm)

H He
32 37
Li Be B C N O F Ne
130 99 84 75 71 64 60 62
Na Mg Al Si P S Cl Ar
160 140 124 114 109 104 100 101
K Ca Ga Ge As Se Br Kr
200 174 123 120 120 118 117 116
Rb Sr In Sn Sb Te I Xe
215 190 142 140 140 137 136 136
Cs Ba Tl Pb Bi Po At Rn
238 206 144 145 150 142 148 146

- 44 -
Ionic Radii of Main Group Elements (in pm)

Li+ Be2+ N3‒ O2‒ F‒

76 45 171 140 133

Na+ Mg2+ Al3+ P3‒ S2‒ Cl‒

102 72 54 212 184 181

K+ Ca2+ Ga3+ Se2‒ Br‒

138 100 62 198 196

Rb+ Sr2+ In3+ Sn4+ Sb3+ Te2‒ I‒

152 118 80 69 76 221 220

- 45 -
Ionization Energy

The first ionization energy, I1, is the energy needed to eject an electron from an
atom in the gas phase – the change in energy for

X(g) → X+(g) + e‒

The second ionization energy, I2, of X is the ionization energy of the cation, X+ –
i.e., the energy change for

X+(g) → X2+(g) + e‒

First ionization energy generally increases, moving from left to right across the
periodic table.

The highest energy electron (the electron ejected) is in the same shell for
these elements – while the effective nuclear charge increases from left to
right.

- 46 -
First ionization energy decreases moving down a group.

Electrons ejected upon ionization of each successive element come from

successive shells – successively more distant from the nucleus, and are less
tightly held.

For example, with respect to ionization energy, Li > Na > K > Rb > Cs

General trends in ionization energy

First ionization energy increases up and to the right

- 47 -
The first trend – ionization energy increases across a row – requires adjustment.

Ionization energy exhibits filled and half-filled subshell effects. Consider the
second row:
2000

first ionization energy (kJ/mol)

Ne

1500 N F

1000 O
Be C

Li B
500

3 4 5 6 7 8 9 10
atomic number

First ionization energy drops from Be to B because the electron ejected from Be
is in the 2s subshell whereas the electron ejected from B is in the higher energy
2p subshell – Be has a filled subshell.

- 48 -
For N, the electron is ejected from a half-filled 2p subshell, 2p3. Each electron in
the half-filled subshell occupies a different orbital, but with the same spin – this
configuration minimizes repulsion.

Ionizing O achieves the stable 2p3 configuration starting from 2p4.

Ionization of O is more favorable than ionization of N, in spite of the
increased nuclear charge of O.

The same increasing zigzag pattern is seen for the third row elements, Na, Mg,
Al, Si, P, S, Cl and Ar, with local peaks at Mg and P.

- 49 -
First Ionization Energies of Main Group Elements (in kJ mol‒1)

H He
1312.1 2372.3

Li Be B C N O F Ne
520.2 899.5 800.6 1086.5 1402.3 1313.9 1681.1 2080.7

Na Mg Al Si P S Cl Ar
495.9 737.8 577.5 786.5 1011.8 999.6 1251.2 1520.6

K Ca Ga Ge As Se Br Kr
418.8 589.8 578.9 762.2 944.5 941.0 1139.9 1350.8

Rb Sr In Sn Sb Te I Xe
403.0 549.5 558.3 708.6 830.6 869.3 1008.4 1170.4

Cs Ba Tl Pb Bi Po At Rn
375.7 502.9 589.4 715.6 703.0 811.8 1037.1

- 50 -
Example:
(a) Order the following elements according to increasing first ionization energy:

Cs F N He Ga As

(b) Which of the following orderings, according to increasing first ionization

energy, is correct?

(i) Mg < Si < P < Ar

(ii) Li < N < O < F

(iii) Ga < Ca < Se < As

(iv) Mg < Al < S < P

(a) Cs has the lowest first ionization energy in the group. Next is Ga, then
As, N, F and He. The filled and half-filled subshell effects do not arise in this
series of elements. Therefore, according to increasing first ionization
energy,

- 51 -
 Cs < Ga < As < N < F < He.

(b) (i) This is correct – this ordering is in accord with the general trend.
(ii) N < O is incorrect. O < N because of the half-filled subshell effect.
(iii) This is correct. Here, we see the filled subshell effect, Ga < Ca, and the
half-filled suhshell effect, Se < As.
(iv) S < P is correct – the half-filled subshell effect. However, Mg < Al is
not correct because of the filled subshell effect.

Successive ionization energies – ionization of A, A+, A2+, and so on.

Each successive ionization process takes more energy – there are successively
fewer electrons and correspondingly less screening of the nucleus. Thus,

I1 < I2 < I3 < … the sequence is strictly increasing

When the next electron comes from a lower energy shell than the previous
electron, there is a big jump in ionization energy. For example, the first five
ionization energies of Al:

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 Big jump between I3, I4.
Ionization Energy
(In) in kJ mol‒1 Al3+(g) → Al4+(g) + e‒

1 578 electron comes from 2nd shell

2 1817
3 2745 requires much more energy than
4 11577
5 14842 Al2+(g) → Al3+(g) + e‒

electron comes from 3rd shell

Electrons in the second shell are much more

tightly held – they experience a much larger
core charge.

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Example:

An atom exhibits the following pattern of successive ionization energies:

I1 < I2 << I3 < I4 < I5 < I6

Which element would this most likely be, among Ar, Na, Al or Ca?

The element is in group 2. Therefore, it is Ca.

Electron Affinity

Electron affinity, A1, is the energy change when an gas phase atom gains an
electron.

X(g) + e‒ → X‒(g).

Whenever the anion is stable (usually so), electron affinity is negative.

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 There are some positive electron affinities – e.g., He, Ne, Be and N. These
atoms form singly charged anions in the gas phase, but the anions are not
stable – they lose the electron and return to the neutral atom state.

Since the electron affinity is otherwise negative, it is customary to compare

electron affinities in terms of absolute value.

For example, we say the magnitude of the electron affinity of fluorine (A1
= ‒328 kJ mol‒1) is greater than that of oxygen (A1 = ‒141 kJ mol‒1).

A larger magnitude of electron affinity corresponds to a more favorable

singly charged anion.

Magnitude of electron affinity generally increases up and to the right, just like
ionization energy.

However, there are many exceptions – primarily because of very strong filled
and half-filled subshell effects. For example, group 2 and 15 elements have
much lower magnitude of electron affinity than the general trend suggests.

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 Magnitude of electron affinity generally increases up and to the right

Example:

Order the following elements according to increasing magnitude of electron

affinity:

Rb F O Sn Ge As

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Electron Affinities of Main Group Elements (in kJ mol‒1)

H He
‒72.8 +
Li Be B C N O F Ne
‒59.6 + ‒27.0 ‒121.8 + ‒141.0 ‒328.2 +
Na Mg Al Si P S Cl Ar
‒52.9 + ‒41.8 ‒134.1 ‒72.0 ‒200.4 ‒348.6 +
K Ca Ga Ge As Se Br Kr
‒48.4 ‒2.4 ‒41.5 ‒118.9 ‒77.6 ‒195.0 ‒321.9 +
Rb Sr In Sn Sb Te I Xe
‒46.9 ‒4.6 ‒29 ‒107.3 ‒100.9 ‒190.2 ‒295.2 +
Cs Ba Tl Pb Bi Po At Rn
‒45.5 ‒14.0 ‒36.4 ‒35.1 ‒90.9 ‒183.3 ‒270.2 +

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Chemical Properties

So far, we have considered non-interacting atoms – separated atoms in the gas

phase.

In nature, atoms are constantly interacting, chemically and otherwise.

Chemical properties depend on the number of valence electrons and the

effective nuclear charge.

The oxides of third, fourth, … row elements exhibit a chemical trend.

Metal oxides are basic or amphoteric:

Basic oxides produce basic solutions when dissolved in water

Group 1 and 2 oxides – except beryllium oxide

Amphoteric oxides are insoluble in pure water. They dissolve in

aqueous acid or base solutions
For example, beryllium, aluminum, zinc and iron oxides

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 Metals – bottom left of the periodic table – do not hold their electrons as
tightly as oxygen.

Group 1 and 2 oxides (except BeO), are ionic. They dissolve in water
forming O2‒(aq) – a strong base – and subsequently, OH‒(aq) – also a
strong base.

In other metal oxides, the metal oxygen bond has covalent character –
electrons are shared. However, they are unequally shared – closer to
oxygen than the metal.

Electronegativity measures the pull of an atom on the electrons in covalent

bonds.
Electronegativity generally increases up and to the right

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Difference in electronegativity between bonded atoms indicates polarization of
the bond.

Electrons shift toward the more electronegative atom

Large difference – e.g., main group metal and nonmetal – indicates an ionic
bond.

Small difference – e.g., two different nonmetals – indicates a polar covalent

bond.

Zero difference – e.g., N2, O2, F2, Cl2, ... – indicates a nonpolar covalent
bond.

Basic metal oxides dissolve in water (or acidic aqeous solution) releasing a metal
cation and the oxide anion, O2‒ .

Acidic (nonmetal) oxides react with water to form oxoacids which have at least
one hydroxyl (-OH) attached to the nonmetal.

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The pull of all the oxygen atoms on the nonmetal deplete it of charge,
making it pull back harder.

The pull of the nonmetal stabilizes the oxoanion (-O‒) formed when the
oxoacid donates an H+ (i.e., it acts as a Brønsted-Lowry acid)

oxoacid

CO2 + H2O → H2CO3 carbonic acid

N2O5 + H2O → 2 HNO3 nitric acid
P4O10 + 6 H2O → 4 H3PO4 phosphoric acid
SO3 + H2O → H2SO4 sulfuric acid
Cl2O7 + H2O → 2 HClO4 perchloric acid

Bronsted-Lowry acids donate H+

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 oxoanion

H2CO3 → HCO3‒ + H+ hydrogen carbonate

HNO3 → NO3‒ + H+ nitrate
H3PO4 → H2PO4‒ + H+ dihydrogen phosphate
H2SO4 → HSO4‒ + H+ hydrogen sulfate
HClO4 → ClO4‒ + H+ perchlorate

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 Electronegativities of the Main Group and Elements and Transition Metals

H
2.20
Li Be B C N O F
0.98 1.57 2.04 2.55 3.04 3.44 3.98
Na Mg Al Si P S Cl
0.93 1.31 1.61 1.90 2.19 2.58 3.16
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br
0.82 1.00 1.36 1.54 1.63 1.66 1.55 1.83 1.88 1.91 1.90 1.65 1.81 2.01 2.18 2.55 2.96
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I
0.82 0.95 1.22 1.33 1.6 2.16 2.10 2.2 2.28 2.20 1.93 1.69 1.78 1.96 2.05 2.1 2.66
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At
0.79 0.89 1.10 1.3 1.5 1.7 1.9 2.2 2.2 2.2 2.4 1.9 1.8 1.8 1.9 2.0 2.2

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 ♣
Red is acidic (dark red = stronger acid)
Blue is basic (dark blue = stronger base)
Purple is amphoteric

Figures denoted by ♣ are courtesy of …

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