The Nature of Matter and Periodicity

of Atomic Properties CHAPTER #

1

d
n
o
b
Ionic
The bond which is formed by the complete
transfering of electrons from one atom to
another atom
Example;
1)Na
Na+1eCl+1eCl-

The Nature of Matter

Max Planck (1858 - 1947)
Studied the radiation profiles emitted by solid
bodies heated to incandescence (i.e., heated
so hot that the objects gave off light)
These profiles could not be explained with
classical physics

The Nature of Matter

Classical Physics - matter could absorb or
emit any quantity of energy
Planck observed that energy could be gained
or lost only in whole number multiples of a
quantity, h
h = Plancks constant
h = 6.626 x 10-34 J.sec
= the frequency of the energy absorbed or
emitted

The Nature of Matter

Max Plancks equation for the change in energy for
a system:
E = nh ( where n = 1, 2, 3, )
From Plancks work, we learn that energy is
quantized
energy occurs in discrete packets called quanta;
one packet of energy is called a quantum
THUS, Energy seems to have particulate
properties!

Plancks Constant
Transfer of energy is quantized, and can
only occur in discrete units, called quanta.

hc
E = h =

E = change in energy, in J
h = Plancks constant, 6.626 1034 J s
= frequency, in s1
= wavelength, in m

 Example: The Blue color in fireworks is often achieved by

heating copper (I) chloride (CuCl) to about 1200oC. Then
the compound emits blue light having a wavelength of 450
nm. What is the increment of energy (the quantum) that is
emitted at 4.50 x 102 nm by CuCl?
The quantum of energy can be calculate from the equation
E = h
The frequency for this case can be calculated as follows:
8

14
c
2 .9 9 7 9 1 0 m / s

6 .6 6 1 0 s 1
7

4 .5 0 1 0 m

So,
E = h = (6.626 x 10-34J.s)(6.66 x 1014 s-1)
= 4.41 x 10-19J
A sample of CuCl emitting light at 450 nm can only lose
energy in increments of 4.41 x 10-19J, the size of the
quantum in this case.

Energy and Mass

According to Einstein theory of relativityEnergy has mass; Einstein equation,
E = mc2 where, E = energy, m = mass
c = speed of light
After rearrangement of the equation,

E
m
c

Now we can calculate the mass associated

with a given quantity of energy

 Einstein suggested that electromagnetic radiation

can be viewed as a stream of particles called
photons. The energy of each photon is given by,

E
m

p h o to n

p h o to n

= h =

hc

E
hc /
h
=
=
2=
2
c
c
c

It was Einstein who realized that light could not be

explained completely as waves but had to have
particle properties. This is called the dual nature
of light.

Wavelength and Mass

de Broglie thought if waves like light could have
particle properties that particles like electrons could
have wave properties. We have,

h
h
m
m
v e lo c ity

de Broglies equation,

m
= wavelength (m); m = mass (kg); = velocity (m/s)
h = Plancks constant, 6.626 1034 J s = kg m2 s1
This equation allows us to calculate the wavelength
of a particle.

 Example: Compare the wavelength for an

electron (mass = 9.11 x 10-31 kg) traveling at a
speed of 1.0 x 107 m/s with that for a ball (mass =
0.10 kg) traveling at 35 m/s.
We use the equation = h/m, where
h = 6.626 1034 J.s or 6.626 1034 kg m2 /s
since, 1 J = 1 kg. m2 /s2
For the electron,
34 kg .m .m
e

6 .6 2 6 1 0

11

7 .2 7 1 0 m
7
9 .1 1 1 0 k g 1 . 0 1 0 m / s
31

For the ball,

b

6 .6 2 6 1 0

34 kg .m .m

34
s
1 .9 1 0 m
0 .1 0 k g 3 5 m / s

Quantum Numbers (QN)

When we solve the Schrodinger equation, we find many wave
functions (orbitals) that satisfy it. Each of these orbitals is
characterized by a series of numbers called quantum
numbers, which describe various properties of the orbital.
1. Principal QN (n = 1, 2, 3, . . .) - related to size and energy
of the orbital.
2. Angular Momentum QN (l = 0 to n 1) - relates to shape
of the orbital. l = 0 is called s; l = 1 is called p; l = 2 is called d;
l = 3 is called f.
3. Magnetic QN (ml = l to l including 0) - relates to
orientation of the orbital in space relative to other orbitals.
4. Electron Spin QN (ms = +1/2, 1/2) - relates to the spin
states of the electrons.

The Order in which the Orbitals Fill in Polyelectronic Atoms

The Nature of Matter

Conclusions:
Energy is quantized
Energy can occur is discrete units called
quanta

EMR can show characteristics of

particulate matter (photons) as well as
wavelike characteristics
This phenomenon is known as the dual nature
of light

History of the Periodic Table

Periodic Table
constructed to represent the patterns
observed in the chemical properties of
elements
Johann Dobereiner (1780 - 1849)
found several groups of three elements with similar
properties
e.g., Cl, Br, and I
recognized triads of elements

History of the Periodic Table

John Newlands, 1846
suggested elements be arranged in octaves
some properties seem to repeat every eighth element

Julius Lothar Meyer (1830 - 1895)

Dmitri Mendeleev (1834 - 1907)
both men independently developed what is the
modern periodic table
Mendeleev correctly predicted the properties and
existence of Sc, Ga, and Ge (ekasilicon)
Modern periodic table arranges elements by atomic
number rather than atomic mass

The Aufbau Principle and the Periodic Table

Aufbau (building up) Principle
electrons are added one by one to hydrogen-like
atomic orbitals
Orbital Filling Diagrams show this principle

Hunds rule
lowest energy arrangement occurs when electrons
occupy separate orbitals with parallel spins
I.e., w/in a sublevel, there is no doubling up w/in an
orbital until each orbital on the sublevel has one
electron

 Valence electrons
electrons in the outermost principle quantum
level of an atom
most important electrons to chemists
electrons involved in bonding

Inner electrons = core electrons

Electron Configurations of Valence-Shells

Elements in the same group have the same valence-shell electron
configurations thus explains the similarity in their properties.
Groups: Electron Configurations

1A
2A
3A
4A
5A
6A
7A
8A

ns1
ns2
ns2 np1
ns2 np2
ns2 np3
ns2 np4
ns2 np5
ns2 np6

Main Group Elements

Periodic Trends
Model of the atom can be used to
account for important atomic properties
ionization energy
electron affinity
atomic size
metallic character

Periodic Trends
Atomic Radius
The atomic radius cannot be measured
exactly
defined as half the distance between two
nuclei of identical atoms
otherwise, the atomic radii for an element
are estimated from the elements various
covalent compounds

Periodic Trends
Periodic Trend for Atomic Radii
Going across a row
atomic radii decreases
increased # of protons means each outer
electron feels a greater nuclear charge.
This results in the electrons being pulled
closer to the nucleus, and the atomic radius
will decrease

Periodic Trends
Periodic Trend for Atomic Radii
going down a column
atomic radii increases
e- are being added to higher energy levels
that are farther from the nucleus

Periodic Trend of Atomic Sizes

Ionization Energy
Energy needed to remove an electron from
a gaseous atom:
M(g) + Ip M+(g) + e-;
(Ip = ionization potential or ionization energy)

What is Ionization Energy?

The Periodic Trend of Ionization Energy

Ionization Energy of Main Group Elements

Ionization Energies of 3rd Period Elements

Ionization Energy of Magnesium

Mg(g) Mg+(g) + e-;
Mg+(g) Mg2+(g) + e-;
Mg2+(g) Mg3+(g) + e-;

I1 = 736 kJ/mol
I2 = 1445 kJ/mol
I3 = 7730 kJ/mol

Electron Affinity = Energy released when an

electron is added to a gaseous atom
X(g) + e- X-(g) + Energy (EA)

Electron Affinity
Electron affinities of the halogen atoms
EA (kJ/mol)
F(g) + e- F-(g);
-328 kJ/mol
Cl(g) + e- Cl-(g);
-349 kJ/mol
Br(g) + e- Br-(g);
-325 kJ/mol
I(g) + e- I-(g);
-295 kJ/mol

Electron Affinity
Electron affinities of oxygen:
O(g) + e- O-(g);
Ho = EA1 = -141 kJ/mol
O-(g) + e- O2-(g);
Ho = EA2 = 878 kJ/mol

O(g) + 2e- O2-(g);

Ho = EA = 737 kJ/mol
EA2 is positive because energy is needed to overcome
repulsion force between two negatively charged
particles (O- and e-)

Electron Affinity

Electronegativity
The relative ability of bonded atoms to
draw (pull) shared electrons closer to
its center.

Trend in Electronegativity

Trends of Atomic Properties

Trends in Metallic, Ionic, and Covalent Characters

Periodic Trends in Atomic Properties

Which atom is larger, Li or Cs? Why?

Periodic Trends in Atomic Properties

Which atom is larger, Na or Cl? Why?

Periodic Trends in Atomic Properties

Rank the following element in order of

increasing (smallest to largest) atomic radii:
1. C, N, Mg, Al, and Si;
2. Li, Na, K, Rb, and Cs;
3. Si, P, S, Cl, and Ar;

Periodic Trends in Atomic Properties

Which atom requires more energy to remove
an electron, Li or Cs? Why?

Periodic Trends in Atomic Properties

Which atom requires more energy to remove
an electron, Na or Cl? Why?

Periodic Trends in Atomic Properties

Rank the following atoms in order of

increasing ionization energy.
1. Al, Si, P, S, Cl;
2. Li, Na, K, Rb, Cs;
3. Al, C, Ca, Mg, N;

Periodic Trends in Atomic Properties

Atom A has valence electrons that are lower
in energy than the valence electrons of Atom
B. Which atom has the higher ionization
energy? Explain.

Periodic Trends in Atomic Properties

Which of the following processes requires

the most energy? Explain your choice.
1. Na(g) Na+(g) + e-;
2. Na+(g) Na2+(g) + e-;
3. Mg(g) Mg+(g) + e-;
4. Mg+(g) Mg2+(g) + e-;

Periodic Trends in Atomic Properties

Which of the following reaction releases the

most energy?
1. N(g) + e- N-(g)
2. F(g) + e- F-(g)
3. Cl(g) + e- Cl-(g)
4. Br(g) + e- Br-(g)