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CHAPTER 3

THE ELECTRONIC STRUCTURE


OF ATOMS AND PERIODIC TABLE

NORAINI BINTI MAT HUSSIN


FACULTY OF APPLIED SCIENCES
UiTM PAHANG
CHAPTER OUTLINE

3.1 Electron, Proton, Neutron, Atomic Number, Mass Number, and


Isotope.
3.2 Introduction to Hydrogen Emission Spectrum, Bohrs Theory.
3.3 Quantum Numbers
3.4 Arrangement of Electrons
3.5 Periodic Trends of Elements

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MODEL OF ATOM
Proton
Shell

Neutron
Electron
COMPOSITION OF ATOMS
Electron
Has a negative (-) charge
Has a relative mass of 0 (zero)
Determines the ion
Found outside the nucleus
Bohr model electrons are in specific
energy levels
Electron cloud model electrons are in a
random cloud
Nucleus center of the atom
Home of Protons and Neutrons
Proton
Has a positive (+) charge
Has a relative mass of 1
Determines the atomic number
Found inside the nucleus
Neutron
Has no (0) charge
Has a relative mass of 1
Determines the isotope
Isotopes are two of the same
element with different masses
Found inside the nucleus
Number of protons = atomic number

Number of electrons = number of protons in a neutral atom

Number of protons + number of neutrons = atomic mass


ATOMIC NOTATION
Mass number, A
the number of protons and
neutrons in an atom
*determine the identity of atom Chemical Symbol

Atomic number, Z
the number of protons in an atom

number of electrons = number of protons


number of neutron = mass number atomic number
1 4 12 16 63
1
H 2 He 6
C 8O 30
Zn

Mass number (A)

Atomic number (Z)


Sodium has 11 protons and 12 neutrons. Write an atomic
notation of sodium.
Solution:
Atomic number = 11
Atomic mass = 11+12 = 23
Atomic notation of sodium
Definition : atoms of the same element that have the same number of
protons (atomic number) but different number of neutrons (mass
numbers).
- same Z value, different A value
Example;
H have 3 isotopes
Cl have 2 isotopes
The chemical properties of an element are determined primarily by the
protons & electrons in its atoms.
Neutrons do not take part in chemical reactions under normal conditions.
Show similar chemical properties, due to the same number of electrons
in the atoms.
Posses different physical properties.
1 12 235
H 6
C 92 U
1

2 13 238
1H 6
C 92 U

3 14
1H 6
C

Light travels through space as a wave.

Wavelength () the distance between two consecutive crests and


troughs. It is measured in meters or nanometers (1 nm = 10-9 m)

Frequency () the number of wave cycles (successive crests and


troughs) that pass a given point in unit time. The unit is Hertz (Hz)
represents one cycle per second.

The speed at which a wave moves through space can be found by


multiplying the length of a wave cycle () by the number of cycles
passing a point in unit time ().

c = where c = speed of light (3.0 x 108 m/s)


= wavelength (m) or (nm)
= frequency (Hz)
Light is considered to be generated as a stream of particles called
photons, whose energy, E, is given by

E = h = hc S.I. Unit : Joule (J)


The electron in its lowest energy state, referred to as the ground


state, for which n = 1. When an electron absorbs enough energy, it
moves to a higher, excited state. In a H atom, the first excited state
has n = 2, the second, n = 3, and so on.

When an excited electron gives off energy as a photon of light, it drops


back to a lower energy state. The electron can return to the ground
state (for ex: from n = 2 to n = 1) or to a lower excited state (from n = 3
to n = 2).
1 1 1
= R -
Rydberg equation n 2 n 2
1 2

R is the Rydberg constant = 1.096776x107 m-1

for the visible series, n1 = 2 and n2 = 3, 4, 5, ...

= RH 1 1 Where RH = 2.18 x 10-18 J


h nlo2 nhi 2
h = 6.626 x 10-34 J.s

E = Efinal Einitial = -2.18 x 10-18 J 1 - 1


n2 final n2 initial
ACTIVITY

1. Calculate the wavelength in nm of the line in the Balmer series that


results from the transition n = 4 to n = 2.

2. A green line of wavelength 4.86 x 10-7 m is observed in the


emission spectrum of hydrogen. Calculate the energy of one
photon of this green light.

When energy (heat, electricity, etc.) is added to an atom,
the electrons within the atom jump to higher energy
levels.
When the electrons fall back to their original energy level,
they release the energy that they absorbed in the form of
light.
Therefore, in order to understand the electronic structure
of the atom we must first understand the nature of light
itself!
Atomic structure elucidated by interaction of matter with
light.
Light = electromagnetic radiation, a wave of oscillating
electric and magnetic influences called fields.
Light travels through space as a wave, similar to an ocean
wave.
Light properties: characterized by wavelength,, and
frequency,.
Frequency and wavelength inversely proportional to each
other.
c =
where c = the speed of light = 3.00x108 m/s;
= frequency, s1
= wavelength, m
Example: Red light has = 700 nm.
Calculate the frequency, .

3.00 x 108 m/s


= c = = 4.29 x 1014 Hz
7.00 x 10-7 m
1. Calculate the frequency of light with a wavelength of 500
nm.

2. Calculate the frequency of light if the wavelength is 400


nm.
Max planck found that :

Energy of radiation is proportional to frequency.

E = h
= hc /
where h = Plancks constant = 6.63 x 10-34 Js

Light with large (small n) has a small E.

Light with a short (large n) has a large E.


E.g. determine the energies of photons with
wavelengths of 650 nm, 700 nm and
frequencies 4.50 x 1014 s1, 6.50 x 1014 s1

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Main postulates of Bohrs atomic theory are:
CONSTANT ENERGY CONCEPT
Energy of an electron is constant in one of its
allowed orbits. As long as an electron remains in its
orbit, it neither absorbs nor radiates energy.
CONCEPT OF ENERGY LEVELS
Electrons revolve around the nucleus of atom in
circular orbits in which energy of electrons is
constant. These circular paths are known as
"energy levels" or "stationary states".
RADIATION OF ENERGY
If an electron jumps form higher energy level to a
lower energy level, it radiates a definite amount
of energy.
ABSORPTION OF ENERGY
If an electron jumps from lower energy level to a
higher energy level, it absorbs a definite amount of
energy.
When excited, the Emission: The atom
electron is in a higher gives off energyas Upon emission, the
energy level. a photon. electron drops to a
lower energy level.
Excitation: The atom
absorbs energy that is
exactly equal to the
difference between two
energy levels.

Each circle represents an


allowed energy level for the
electron. The electron may be
thought of as orbiting at a
fixed distance from the
nucleus.
AMOUNT OF ENERGY

Energy released or absorbed by an electron is equal to


the difference of energy of two energy levels.

Let an electron jumps from a higher energy level E2 to a


lower energy level E1. The energy is emitted in the form
of light. Amount of energy released is given by:
E = E2 -E1
The energy absorbed or emitted from the process of an
electron transition can be calculated by the equation:

RH is a Rydberg constant in energy units:


2.18 X 10-18 J.
n1 and n2 are the initial and final energy levels of the
electron.
Calculate the wavelength of light corresponding by an electron transition
from n = 4 to n = 2

-ve sign indicates that this energy associated with an emmission. To


calculate the , omit the ve sign because the wavelength must be +ve.
Calculate the energy of the photon when the electron drops
from the fifth orbit to the second orbit. Calculate also the
frequency and the wavelength of the photon in nm.

Quantum Mechanics:
A theory explaining the electron motions in an atom

Why must we study about the electron?


Electron determine the chemical properties of a
substance

Orbital : region of space around the nucleus which has


the greatest probability of finding an electron. Each
orbital has a definite shape and energy.
From the atomic model explanation,
o Electrons surrounding the nucleus are distributed in shells
or specific energy levels with discrete amounts of energy.

o Electrons are free to move between these shells.

o Shells are divided into subshells or energy level, within


these subshells, electrons is grouped into orbital.
The quantum mechanics model identifies 4 quantum
numbers.
n
l to describe the electron orbital.
m
s explains the spin direction of electron in
the orbital.
Indicates the average distance of an electron from the nucleus
The larger n is, the greater is the average distance of an electron in
the orbital from the nucleus.
It is normally to refer the energy levels as electron shells.
Function: Determine the
- shell
- distance of e from nucleus
- size of shell
- the energy of e-
Allowed Value: positive integers., 1,2,3,4.
Relationship between n and orbital in an atom.
Quantum Number (n) Shell
1 K
2 L
3 M
4 N

The energy level n = 1 is the nearest to the nucleus. Thus, an electron


residing in n = 1 is most strongly held by the nucleus.
The maximum number of electron that can occupy a given shell
depends on the shell number.

Maximum e = 2n2 n = shell number

Each shell can hold a maximum of 2n2 electrons, n = 1,2,3,4


The different of n
Function: Determine the shape of orbitals in a shell

Called subshells

Allowed Value: from 0 to (n 1).

Same value of n, energy increase as l increase.

This means electron occupying a 3d subshell (l = 2) has higher energy


than an electrons occupying a 3p (l = 1) or 3s subshell (l = 0)

Energy of electrons, s < p < d < f .


Quantum Number (n) l
Relation between n and l
1 0
2 0,1
3 0,1,2
4 0,1,2,3

Energy sublevels (orbital) notation by l values.

l (n-1) Energy sublevel


(orbital)
0 s
1 p
2 d
3 f
4 g
Suborbital notation (energy sublevels)

n l Suborbital notation
1 0 1s
2 0 2s
1 2p
0 3s
3
1 3p
2 3d
0 4s
1 4p
4
2 4d
3 4f
Describe the orientation of the orbital in space.

Function: determine:
- direction of orbital ( x, y, z axis)
- determine number of orbital

for a given value of l


ml = -l, ., 0, . +l

if l = 0 (s orbital), ml = 0
if l = 1 (p orbital), ml = -1, 0, or 1
if l = 2 (d orbital), ml = -2, -1, 0, 1, or 2

orientation of the orbital in space


Table : Relation between n, l, and m

Shell n l m Orbital Number of


orbital
K 1 0 0 1s 1
L 2 0 0 2s 1
1 -1, 0, +1 2p 3
M 3 0 0 3s 1
1 -1, 0, +1 3p 3
2 -2, -1, 0, +1, +2 3d 5
N 4 0 0 4s 1
1 -1, 0, +1 4p 3
2 -2, -1, 0, +1, +2 4d 5
3 -3, -2, -1, 0, +1, +2, 4f 7
+3
l =0, ml = 0
l =0, s orbital.
There are 1 type of s orbital.
l =1, ml = -1, 0, +1
l =1, p orbital.
There are 3 type of p orbital.
Px, Py and Pz
l =2, ml = -2, -1, 0, +1, +2
l =2, d orbital.
There are 5 type of d orbital.
The Hierarchy of Quantum Numbers for Atomic Orbitals

Name, Symbol
(Property) Allowed Values Quantum Numbers

Principal, n Positive integer


1 2 3
(size, energy) (1, 2, 3, ...)

Angular
momentum, l 0 to n-1 0 0 1 0 1 2
(shape)

0 0 0
Magnetic, ml
-l,,0,,+l -1 0 +1 -1 0 +1
(orientation)

-2 -1 0 +1 +2
Function : determine spin (direction)

of the electron

Allowed Value: +1/2 and -1/2

An electrons for which s is:

+1/2, the sign of that spin are up (),

-1/2, the sign of s is down ().


ms = + ms = -
Shell electrons with the same value of n
Subshell electrons with the same values of n and l
Orbital electrons with the same values of n, l, and ml
How many electrons can an orbital hold?
If n, l, and ml are fixed, then ms = or -

= (n, l, ml, ) or = (n, l, ml, -)

An orbital can hold 2 electrons


The arrangement of the electron in the orbitals must
obey 3 principles:

1. Aufbau Principle: The lowest energy orbitals are filled


first, with a maximum of two electrons in any orbital.

2. Pauli Exclusion Principle: A maximum of two spin paired


electrons may be placed in each orbital.

3. Hunds Rule: One electron is added to each degenerate


(equal energy orbital) before a second electron is
added.
The lowest energy orbitals are filled first, with a
maximum of two electrons in any orbital

Question :
1. Between 2s and 3s, which one will be filled first
by the electron?
2. How many 2p orbitals are there in an atom?
3. How many electrons can be placed in the 3d
subshell?
Fill up electrons in lowest energy orbitals (Aufbau principle)

? ?
B 5 electrons B 1s22s22p1
Be 4 electrons Li 1s22s1

Li 3 electrons Be 1s22s2
He 2 electrons He 1s2
H 1 electron H 1s1

CHM081/chapter5/ZMH
Order of orbitals (filling) in multi-electron atom

1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s
Outermost subshell being filled with electrons
A maximum of two spin paired electrons may be placed in
each orbital
No two electrons in an atom can have the same set of
quantum number (n, l, ml and ms)

If 2 electrons in an atom should have the same n, l, m


value (that is, these 2 electrons are in the same atomic
orbital) then they must have different values of s
(opposite spins).

Example:
n = 1, l = 0, m = 0, s = -1/2
n = 1, l = 0, m = 0, s = +1/2
One electron is added to each degenerate (equal energy orbital)
before a second electron is added

States that an electron will not enter an orbital containing another


electron if an empty orbital of the same energy level is available.
s will occupy all orbitals of the same energy level singly
before they start pairing up.

Once all the orbital are single occupied, subsequent electron


occupation will start to result in them pairing up.

Hunds rule state an atom can have as many unpaired electrons


as possible.
What is electronic configurations?
The electron configuration of an atom describes the
orbitals occupied by the electrons on the atom.

It shows the ways electrons are arranged in the subshells


of an atom.

Important things: you should understand the concept of


Energies of Atomic Orbitals
Two factors control the energy of an orbital for most atoms:

i) the size of the orbital

The most important factor

Depends on the value of the principal quantum number, n

Higher n, higher energy of the orbital


ii) The shape of the orbital

The more complex the shape of the orbital, the higher


the energy of the orbital

Depends on the azymuthal quantum number,l.

Larger value of l, larger energy of the subshells


n=3 l = 2

n=3 l = 1
n=3 l = 0

n=2 l = 1
n=2 l = 0

n=1 l = 0
Two general methods are used to denote configurations.
a) The subshell ( sub-energy level) notation, uses ;
- numbers to designate the principal energy levels or principal
shells
- the letters s, p, d, and f to identify the sublevels.
- superscript number following the letter indicates the number of
s in the designated subshell.

b) Orbital diagram, uses ;


- boxes to indicate orbitals within subshells, and
- arrows to represent s in these orbitals. The directions of the
arrows represent the directions of the spins.
Subshell notation : naming the orbital where the electron
is located
Electron configurations of some elements

Classifications of elements based on atomic number

Scientist :
Antoine Lavoiser (1789)
J.W. Dobreiner (1829)
John Newlands (1864)
Dimitri Mendeleev
The elements are arranged based on atomic number

Total number of elements = 112

Have two parts :


1) Group
2) Period
CHM138/Chapter5/NMH
Vertical column
There are 18 columns: main group (A)
transition group (B)
Numbering groups:
a. Arabic Number
1,2,3.18
b. Roman Number
IA to VIIIA, IB to VIIIB

Element in the same group has :


- the same number of valence electron
- same chemical properties
- different physical properties
SPECIFIC NAMES FOR SOME GROUP

Group 1, 2, 13 17 representative elements or main


group elements

Group 1 elements alkali metals


Group 2 elements alkaline earth metals
Group 17 elements halogens
Group 18 elements noble gases and chemically
unreactive

Group 3 12 transition elements or transition


metal
(*Located at the center of the periodic table between group 2
& 13)
Valence electron
electron which is located at the outermost shell of an atom
B : 5 electron 1s22s22p1
the electron valence is located at n=2
how many electron valence?: 3 electron

Group Valence electron configurations Number of valence electrons

1 ns1 1
2 ns2 2
3 ns2 np1 3
14 ns2 np2 4
15 ns2 np3 5
16 ns2 np4 6
17 ns2 np5 7

18 ns2 np6 8

Valence electron configurations and number of valence electron for group of elements
A periodic table of partial ground-state electron configurations

CHM138/Chapter5/NMH
Horizontal row

Each period = outermost energy level that has electrons


for elements in that period

Elements in a period has different physical and chemical


properties

The period number is equal to the principal quantum


number (n) of the valence shell.
Atomic
number
CHM138/Chapter5/NMH
Example

Give the period and group of element X which has 19 electron

Electron configuration :
1s2 2s2 2p6 3s2 3p6 4s1 or [Ar] 4s1
(19 electrons)

- Valence shell = 4, therefore Period = 4


- The no. of electron at valence shell = 1,
therefore Group = 1 or 1A
s block
Group** p block
Pe
rio
1 18
d IA VIIIA
1A 8A
d block
1 2 13 14 15 16 17 2
1 H IIA IIIA IVA VA VIA VIIA He
1.008 2A 3A 4A 5A 6A 7A 4.003

3 4 5 6 7 8 9 10
2 Li Be B C N O F Ne
6.941 9.012 10.81 12.01 14.01 16.00 19.00 20.18

11 12 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
3 Na Mg IIIB IVB VB VIB VIIB ------- VIII ------- IB IIB Al Si P S Cl Ar
22.99 24.31 3B 4B 5B 6B 7B ------- 8 ------- 1B 2B 26.98 28.09 30.97 32.07 35.45 39.95

19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.47 58.69 63.55 65.39 69.72 72.59 74.92 78.96 79.90 83.80

37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.94 (98) 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3

55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9 137.3 138.9 178.5 180.9 183.9 186.2 190.2 190.2 195.1 197.0 200.5 204.4 207.2 209.0 (210) (210) (222)

87 88 89 104 105 106 107 108 109 110 111 112 114 116 118
7 Fr Ra Ac~ Rf Db Sg Bh Hs Mt --- --- --- --- --- ---
(223) (226) (227) (257) (260) (263) (262) (265) (266) () () () () () ()

58 59 60 61 62 63 64 65 66 67 68 69 70 71
Lanthanide Series* Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
140.1 140.9 144.2 (147) 150.4 152.0 157.3 158.9 162.5 164.9 167.3 168.9 173.0 175.0

90 91 92 93 94 95 96
CHM140/chapter2/NorainiMH
97 98 99 100 101 102 103 f block
Actinide Series~ Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
232.0 (231) (238) (237) (242) (243) (247) (247) (249) (254) (253) (256) (254) (257)
s block : elements in Group IA and IIA, include H & He
because a maximum of 2 electrons can occupy the single
orbital in an s-subshell.

p block : elements in Group III A to VIII A


because a maximum of 6 electrons can occupy the three
orbitals in a p-subshell.

d block : elements first appear after Ca (atomic number 20) with 10


column of elements of the transition metal
because a maximum of 10 electrons can occupy the five
orbitals in a d-subshell.

f block : elements include all the elements in the 2 rows at the bottom of
the periodic table
because a maximum of 14 electrons can occupy the seven
orbitals in a f-subshell.
Atomic size

Electropositivity & Electronegativity

Ionization energy

Electron affinity
Decreasing groups: ATOMIC SIZE INCREASE
WHY????

Li: 1s2 2s1


Outermost orbital n = 2

Na: 1s22s22p63s1
Outermost orbital n = 3
Across period: ATOMIC SIZE DECREASE
The atomic radius decrease because the valence electron
and effective nucleus charge increase

Effective nucleus charge


Ex: For Li Zeff = 3 2 = 1

CHM138/Chapter5/NMH
Atomic radii of the main group and transition elements.

CHM138/Chapter5/NMH
Ionic radius/radii is the radius of a cation or an anion.
If atom forms an anion, its size or radii increases,
because the nuclear charge remain the same but the
repulsion resulting from additional electrons enlarge the
electron cloud.
Cations are smaller than anions.
Example : Na+ is smaller than F-
Both ions have the same number of
electrons, but Na (Z = 11) has more proton
than F (Z = 9). The larger the effective
nuclear charge of Na+ results in a smaller
radius.
Tendency of element to become more positive by
removing electron

Describes the metallic properties of elements


(metal atom usually donate electron to form a positive
ion)

Descending groups : Electropositivity increase


Element become more electropositive
Tendency and ability of element to pull electron towards
itself in a chemical bond

Higher electronegativity : higher tendency to attract


electron

Nonmetals have higher electronegativity compare to


metal
The Electronegativities of Common Elements
The minimum energy (kJ/mol) required to remove an
electron from a gaseous atom in its ground state.

Ionization energy measure the energy needed to


overcome the attraction forces between nucleus and
valence electron
The first ionization energy I1, is the energy required to remove one
electron from the neutral atom.

The second ionization energy I2, is the energy required to remove


the second electron.

The greater the value of I, the more difficult it is to remove an


electron

The first electron is more readily removed than the second, etc.
I1 < I2 < I3 < I4

The 1st IE increase from left to right because atomic radius decrease,
the outer electrons are more tightly held to the nucleus.
o The 1st IE decrease moving down a group because the atomic radius
increase from top to bottom.
ability to accept one or more electrons

energy change that occur when an electron is accepted


by an atom in the gaseous state to form an anion

negative value means the energy is released when


electron is added to the atom

positive value means work has to be done (energy must


be absorbed) to force a stable atom to receive one
electron

non metals, especially halogen have higher electron


affinity compared to metal
o The more negative the electron affinity, the greater the tendency of
the atom to accept an electron.

F (g) + e F- (g) H = -320 kJ


Li (g) + e Li- (g) H = -61 kJ
Na (g) + e Na- (g) H = -54 kJ

o EA values become more negative from left to right because the


atomic radius of elements becomes smaller.

o EA values become less negative from top to bottom because the


increase in the atomic radius (attractive forces of the nucleus
decrease, so less tendency to accept an electron).
Example
Decreasing down the group, the value of electron affinities
decrease Or increase. Give reasons why?

Answers:
Decrease
CHM138/Chapter5/NMH
THE END
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Q&A

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