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Chapter 4:

ELECTRON STRUCTURES
&
PERIODIC TABLE
ELECTRONS IN ATOMS

Atomic Models
 Systems of atomic and subatomic entities can be
explained by following the establishment of principles and
laws set which known as quantum mechanic.
 Therefore, to understand the behaviour of electron in
atoms and crystalline solids, discussion of quantum-
mechanical concepts are necessarily involved.
 Quantum mechanics of atoms was simplified and called
as Bohr atomic model
Bohr Atomic Model

 Bohr Rules:
1. Electrons can orbit only at certain
allowed distances from the
nucleus.
2. Atoms radiate energy when an
electron jumps from a higher-
energy orbit to a lower-energy
orbit. An atom absorbs energy
when an electron gets boosted
from a low-energy orbit to a high-
energy orbit.
 Bohr model was eventually found to
have some significant limitations:
 The electron does not orbit the
nucleus in circles as Bohr
suggested (as popular drawing),
but in ‘fuzzy’ orbit.
Wave-Mechanical Model

 The electron states are described by orbitals. Orbitals are


nothing like orbits. The electron’s path could not precisely
described, only able to predict the probabilities of finding
the electron at given points in space around the nucleus.
 The electron position (electron cloud or distribution) is
considered to be at various locations around the nucleus.
 Exhibit both wave-like and particle-like characteristics’

The probability map (or orbital) that


describes that H electron in its lowest
possible energy state. The more intense the
colour, the more likely that the electron will
Electron in the H atom be found at that point.
Bohr atomic model Wave-mechanical model

 The Bohr theory (left) sees an electron as a particle occupying


certain orbits, which correspond to certain energy levels. The orbits
are labelled n = 1, n = 2, etc. An electron can move from one energy
level to another, for example, through paths a, b, c, or d.
 Wave-mechanics (right) sees an electron as a wave washing back
and forth in the atom in certain patterns only.
Energy Levels of Electrons

Prinsipal energy levels


Designated by “n”
n=1, n=2 and so on…

Sublevels
If n=1  one sublevel: s
If n=2  two sublevels: s and p

Orbitals
Space for electrons
If n=2, electron occupy in 1s, 2s and 2px, 2py, 2pz
s orbital

 s orbital has spherical in shape.


 The electron does not move around on the surface of the sphere, but
rather the surface encloses a space where there is a 90% probability
that the electron may be found.
 All s orbitals are spherical in shape but differ in size, which increases
as n increases.
z z z

x x x
y y y

1s orbital 2s orbital 3s orbital


p orbital

 p orbital has two lobes on opposite sides of the nucleus.

 The space enclosed by these surfaces represent the regions of


probability for finding the electrons 90% of the time.
 Like s orbitals, p orbitals increases in size as n increases.

z
z z

x
x x
y
y y

px py pz
Electron configuration

 How the electron are distributed among the various


atomic orbitals, in order to understand electronic
behaviour.
 Configuration of atom Hydrogen:

1s1
Guidelines to Write Electron Configuration

1. No. of sub-shells for each principal energy level (shell).


Shell (n) No. of sub-shells Sub-shell
1 1 s
2 2 s, p
3 3 s, p, d
4 4 s, p, d, f

2. Max. 2 electrons can occupy one orbital.

Sub-shell no. of atomic orbitals max no.of electrons


s 1 2
p 3 6
d 5 10
f 7 14
3. Electrons occupy the lowest energy orbitals available.
They enter a higher energy orbital only after the lower
orbitals are filled.
 Orbital energies: s < p < d < f
Shell
1
2
1 1s2 3
4
Energies increase 2 2s2 2p6 5
6
3 3s2 3p6 3d10 7
8
4 4s2 4p6 4d10 4f14

5 5s2 5p6 5d10 5f14

6 6s2 6p6 6d10

7 7s2 7p6

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

Orbital energies increase


How to write orbital diagram

1. Pauli exclusion principle:


 Only two electrons may occupy the same atomic
orbital, and must have opposite spins.

 Consider, how to write orbital diagram for helium (no of


electron = 2). Which one is correct?

He He He
1s 1s 1s
2. Hund’s rule:
 the most stable arrangement of electrons in
sublevel is the one with the greatest number of
parallel spins.
 Consider, how to write valence orbital diagram for
atom carbon:
1s2 2s2 2p2  electron configuration

2px 2py 2pz 2px 2py 2pz 2px 2py 2pz


3. Electrons are added singly to the atomic orbital with
parallel spins to minimize repulsion between them
 the arrows are shown in the same direction (same
spin).

4. Then the electrons pair up in the orbital sub-shells with


opposite spin
 the arrows are shown in opposite directions.
Example

Li: no. of electron = proton number = 3

Electron configuration: 1s2 2s1

Orbital diagram:

1s 2s

N: no. of electron = proton number = 7

Electron configuration: ________________

Orbital diagram:

1s 2s 2p
Mg: no. of electron = proton number = _____

Electron configuration:_____________________

Orbital diagram:

1s 2s 2p 3s

Cl: no. of electron = proton number = _____

Electron configuration: ______________________

Orbital diagram:
Core electron and valence electron

 Valence electron – electron in the valence orbitals


 all others – core electrons
 Core electrons – highly stabilized and isolated from external attack
by the electrons in outer orbitals.
 Valence electrons – less stable and less isolated. The chemical
properties of any species depend on its valence electrons.
Examples of electron configurations written
with the core/valence notation
full configuration
atom full core Valence
using core/
configuration Conf.
valence notation
Li 1s2 2s1 1s2 or He 2s1 [He] 2s1

N 1s2 2s2 2p3 1s2 or He 2s2 2p3 [He] 2s2 2p3

O 1s2 2s2 2p4 1s2 or He 2s2 2p4 [He] 2s2 2p4

Mg 1s2 2s2 2p6 3s2 1s2 2s2 2p6 or 3s2 [Ne] 3s2
Ne

Cl 1s2 2s2 2p6 3s2 3p5 1s2 2s2 2p6 or 3s2 3p5 [Ne] 3s2 3p5
Ne

Al 1s2 2s2 2p6 3s2 3p1 1s2 2s2 2p6 or 3s2 3p1 [Ne] 3s2 3p1
Ne
Quantum Numbers

 A set of mathematical equations, called wave functions is


obtained by solving the Schrödinger equation.
 Wave function for an electron in an atom is called
an atomic orbital. It describes a region of space in which
there is a high probability of finding the electron.
 Each electron in an atom is characterized by four
parameters called quantum numbers.
 The first three (n, l, ml) specify the particular orbital of
interest, and the fourth (ms) specifies how many electrons
can occupy that orbital.
1. Principle quantum number (n)
 The first of a set of quantum numbers
 Signifies the shell
 Only have positive integer values
n = 1,2,3,4…..
 Describe the size of the orbital
 As n increases, the orbital becomes larger, the
electron is at a higher potential energy and
therefore less tightly bound to the nucleus.
2. Angular quantum number (ℓ)
 Also known as azimuthal quantum number or secondary
quantum number.
 Determines the orbital angular momentum and describes
the shape of the orbital.
 Signifies the subshells (sublevels)
 number of subshell/orbital ℓ = n-1
ℓ = 0, 1, 2, 3, ……, n-1
ℓ = s, p, d, f…..
 The shape of the orbitals can be describes as spherical
(orbital s, ℓ = 0), polar or three dumbbells (orbital p, ℓ = 1)
and cloverleaf or four dumbbells (orbital d, ℓ = 2)
y y y

x x x

z z z
s orbital
1s orbital 2s orbital 3s orbital

z z z

x x x
y y y
p orbital
px py pz
3. Magnetic quantum number (mℓ)
 describes the orientation in space of an orbital of a given
energy (n) and shape (ℓ).
 It called the magnetic quantum number because the
effect of different orientations of orbitals was first
observed in the presence of a magnetic field.
 m is entitled to be any integer from -ℓ up to ℓ.
 Given a particular ℓ, there are 2ℓ+1 magnetic quantum
numbers, m ranging from -ℓ to ℓ
 Thus, s subshell has only one orbital, the p subshell has
three orbitals, and so on.
Relationship between Quantum Numbers

orbital ℓ value m value Number of


values for mℓ
s ℓ=0 m=0 1
p ℓ=1 m = -1, 0, +1 3
d ℓ=2 m = -2, -1, 0, +1, +2 5
f ℓ=3 m = -3, -2, -1, 0, +1, +2, +3 7
ml = -1, 0, or 1

3 orientations is space
ml = -2, -1, 0, 1, or 2 5 orientations is space
4. Spin quantum number (ms)
 Specifies the orientation of the spin axis of
an electron
 An electron can spin in only one of two
directions (sometimes called up and down)
+½ (↑) or -½ (↓)

ms = +½ or -½
The Pauli exclusion principle (Wolfgang Pauli,
Nobel Prize 1945) states that no two electrons in
the same atom can have identical values for all four
of their quantum numbers.

 Meaning that no more than two electrons can


occupy the same orbital, and that two electrons in
the same orbital must have opposite spins.
Table of Allowed Quantum Numbers

Number of Orbital Number of


n l ml
orbitals Name electrons
1 0 0 1 1s 2
2 0 0 1 2s 2
1 -1, 0, +1 3 2p 6
3 0 0 1 3s 2
1 -1, 0, +1 3 3p 6
2 -2, -1, 0, +1, +2 5 3d 10
4 0 0 1 4s 2
1 -1, 0, +1 3 4p 6
2 -2, -1, 0, +1, +2 5 4d 10
-3, -2, -1, 0, +1,
3 7 4f 14
+2, +3
Schematic
representation of the
relative energies of the
electrons for the
various shells and
subshells
Energy of orbitals in a multi-electron atom
Energy depends on n and l

n=3; l = 2

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

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

n=1; l = 0
Example
Write all sets of quantum numbers that describe the 6 electrons of
carbon atom.

Electron configuration: 1s2 2s2 2p4


Orbital diagram:

1s 2s 2p

1,0,0,+½ 2,0,0,+½ 2,1,-1,+½


1,0,0,-½ 2,0,0,-½ 2,1,0,+½

n=1 n=2 n=2


l=0 l=0 l=1
ml = 0 ml = 0 ml = -1, 0
ms = +½ & -½ ms = +½ & -½ ms = +½
Exercise

1. Write the 14 sets of quantum numbers that describe the


14 electrons of silicon, Si.
2. For each of the following, indicate the maximum number
of electrons in an atom that can have as part of their set
of four quantum numbers.
i. n = 3
ii. n = 4, l = 2
iii. n =2, l = 2
iv. n = 3, l = 2, ml = -1, ms = +1/2
Periodic Table

• 19th Century arrange element using atomic masses


• Arrange elements according to their atomic masses
• J.Newlands  every 8 element have the similar
properties : law of octaves
• D.Mendeleev & L.Meyer  group according to
properties and can make prediction.
• Rutherford & Moseley discovery of proton  arrange
according to atomic number.
Periodic Table Classification

 Element arranged according to atomic number


 Electron configuration explain physical and chemical properties

Noble
Group Period
gases
1 18
1
2 13 14 15 16 17
2
3 4 5 6 7 8 9 10 11 12 3
Transition metals

Representative Lanthanides
(Main Group)
Actinides
Electronic Configuration & Periodic Table
 Elements in the same group have the same numbers of outer
electron (valence electron)

 Group 1  incomplete s subshell


11Na: 1s2 2s2 2p6 3s1

 Group 13 to 17  incomplete p subshell

16S: 1s2 2s2 2p6 3s2 3p4


 Group 18, Noble gases  completely filled s and p subshells

 Transition metals  incomplete d subshell

 Lanthanides and Actinides  Incomplete f sub-shell


How to determine group & period from the electron configuration

 Look at the outermost shell

Na: 1s 2 2s2 2p6 3s1


11

S: 1s 2 2s2 2p6 3s2 3p4


16
Cations and Anions

 Ions form from neutral atom  noble gas outer-electron


configuration
Cation
Na: 1s2 2s2 2p6 3s1 Na+: 1s2 2s2 2p6

Ne: 1s2 2s2 2p6


Anion 10

F: 1s2 2s2 2p5 F-: 1s2 2s2 2p6

Isoelectronic
EXERCISE
1. Write the electron configuration and orbital diagram for the
following elements.
2. Determine the group and period (WITHOUT LOOKING AT THE
PERIODIC TABLE).

Elements Proton no.

Silicon 14

Potassium 19

Bromin 35

Aluminium ion 13
Effective Nuclear Charge, Zeff

 Charge felt by an electron


 The larger Zeff, the stronger the hold of the nucleus on these
electron, and the smaller the atomic radius
 Shielding effect electrons close to the nucleus
 Presence reduces the electrostatic attraction between proton
& electron
 Repulsive forces between electron offset the attractive force
exerted by nucleus
Atomic Radius

 Is one-half the distance between the two nuclei in two


adjacent metal atoms.
 Determine by the strength of attraction between outer-shell
electron and the nucleus.
 Atomic radius increases as we going down a group of the
periodic table because of an increase in principal quantum
number, n.
 orbital size increase

 the larger the Zeff, the stronger the hold of the nucleus on
these electrons, and the smaller the atomic radius
 Atomic radius decreases as we move from left to right across
a period because of an increase in effective nuclear charge,
Zeff , for the valence shell electron

 moving across a period, the number of core electron


stays the same, the principal quantum number, n
remains constant, but Zeff increases.
 as Zeff increases, the electrons are drawn closer to the
nucleus. Thus, the atomic radius decreases.

Li: 1s2 2s1 C: 1s2 2s2 2p2 O: 1s 2 2s2 2p4


3 6 8

Atomic radius decrease


Ionic Radius
 The radius of a cation or an anion
 Cation are always smaller than the atom from which they were
formed.
 removing one or more electrons from an atom reduces electron-
electron repulsion but the Zeff remains the same. So the electron
cloud shrinks

 Anion are always larger than the atom from which they were
formed.
 Because the Zeff remains the same but the repulsion resulting
from the additional electron(s) enlarges the domain of the
electron cloud.

Na Na+ O O2-
186 pm 95 pm 73 pm 140 pm
• When comparing cations or anions within a column (group),
they get larger going down the column. Example:
Ca2+ > Mg2+ and I- > Br-

• When comparing cations or anions across a row (period),


they get smaller going across the row from left to right.
Example:
N3- > F- and K+ > Ca2+
Ionization Energy

 Ionization energy : the minimum energy (in kJ/mol) required to


remove an electron from a gaseous atom in its ground state
 First ionization energy (I1) : the energy needed to remove the
first electron from a neutral atom.
 Second ionization energy (I2) : the energy needed to remove
the second electron.
 Endothermic process

 Within each row (period) : I1 of elements in a period generally


increase with increasing atomic number.

 Within each group : I1 of the elements in a group generally


decrease with increasing atomic number.
 I1
Na (g)  Na+ (g) + e- E = 496 kJ/mol

 I2
Na+ (g)  Na2+ (g) + e- E = 4560 kJ/mol

 The greater the ionization energy, the more difficult it is to


remove the electron.
 Endothermic process

 Within each row (period) : I1 of elements in a period generally


increase with increasing atomic number.
 Within each group : I1 of the elements in a group generally
decrease with increasing atomic number.
Electron Affinity

 The energy change that occurs when an electron is


accepted by an atom in the gaseous state to form an anion.
 Exothermic process
 The greater the attraction between an atom and an added
electron, the more negative the atom’s electron affinity will
be.
 Within each row (period) : electron affinity generally
becomes increasingly negative as we across the row from
left to right.
 Electron affinity do not change greatly as we move down a
group.
Chemical Properties

 Elements in the same group resemble one another in


chemical behavior because they have similar outer electron
configuration.
 Group 1 and 2  all metals
 Group 17 and 18  all nonmetals
 Group 13 through 16
 The elements change either from nonmetals to
metals or from nonmetals to metalloids
 variation in chemical properties even though
members of the same group have similar outer
electron configurations.
Group 1 (ns1, n ≥1)

 Alkali metals
 Very reactive (why?)
 Have low first ionization energy  great tendency to lose the
its valence electron to form ions with a +1 charge.
 React with water  producing hydrogen gas and solutions of
alkali metal hydroxides
2Na (s) + 2H2O (l)  2NaOH (aq) + H2 (g)
 Reaction between alkali metals and oxygen:
 Lithium form metal oxides (which contain O2- ion)
4Li (s) + O2 (g)  2Li2O (s)
 other metals form metal oxides and peroxides (contain O22-
ion)
2Na (s) + O2 (g)  Na2O2 (s)
 K, Rb and Cs also form superoxides (contains O2- ion)
K (s) + O2 (g)  KO2 (s)
Group 2 (ns2, n ≥ 2 )

 Alkali earth metals


 Less reactive than alkali metals
 ionization energies decrease as we move down the group from Be
to Ba.
 reactivity increases from top to bottom
 Reactivity towards water
 Beryllium (Be) does not react with water
 Mg react with steam to form MgO and hydrogen gas
Mg (s) + H2O (g)  MgO (s) + H2 (g)
 Ca, Sr, Ba react with water at room temperature
Ca (s) + 2H2O (l)  Ca(OH)2 (aq) + H2 (g)
 Reactivity towards oxygen
 increase from Be to Ba
 Be and Mg form oxides (BeO and MgO) only at
elevated temperature
 Ca, Sr and Ba form oxides at room temperature
 Mg, Ca, Sr and Ba reacts with aqueous acid to produce
hydrogen gas
Mg (s) + 2H+ (aq)  Mg2+ (aq) + H2 (g)
Group 13 (ns2 np1, n ≥ 2 )

 First member, Boron – metalloid; the rest – metals


 Boron – does not form binary ionic compounds and
unreactive towards O2 (g) and water
 Aluminum – readily forms aluminum oxide when exposed to
air
4Al (s) + 3O2 (g)  2Al2O3 (s)
 Al forms only +3 ion (Al3+). Other elements form both +1
and +3 ions.
 Moving down the group  the +1 ions becomes more
stable than the +3 ion.
Group 14 (ns2 np2, n ≥ 2 )

 carbon  nonmetal Do not form ionic


 Si and Ge  metalloids compound

 Sn and Pb  metallic elements


 Do not react with water
 React with acid to produce hydrogen gas
Pb (s) + 2H+ (aq)  Pb2+ (aq) + H2 (g)
Group 15 (ns2 np3, n ≥ 2 )

 Nitrogen, phosphorus  nonmetals


 Arsenic and Antimony  metalloid
 Bismuth  metals
 Nitrogen exist as diatomic gas (N2). Nitrogen has a tendency
to accept 3 electrons to form nitride ion, N3-
 Phosphorus exist as P4 molecules.
Group 16 (ns2 np4, n≥2 )

Oxygen, sulfur and selenium  nonmetals


Tellurium and polonium  metalloids
Oxygen – diatomic gas  has a tendency to accept two
electrons to form oxide ion (O2-)
Sulfur exist as S8 molecule and selenium as Se8
Group 17 (ns2 np5, n≥2 )

 Are known as halogen


 All the halogen are nonmetals
 All halogen exist as diatomic molecules
 F2 and Cl2  gases at room temperature
 Br2  liquid
 I2  solid
 Halogens have highly negative electron affinities  great
tendency to gain electrons from other elements to form
halide ions
X2 + 2e-  2X- (X indicates a halogen elements)
 Fluorine and chlorine are more reactive than bromine and
iodine
 Fluorine is so reactive and removes electrons from almost
any substance with which it comes into contact, including
water.
2F2 (g) + 2H2O (l)  4HF (aq) + O2 (g)
2F2 (g) + SiO2 (s)  SiF4 (g) + O2 (g)
 As a result, fluorine gas is difficult and dangerous to use in
the laboratory and requiring special apparatus.
Group 18 (ns2 np6, n≥2 )

 Known as noble gases or inert gases


 All noble gases exist as monoatomic species.
 Their atoms have completely filled outer s and p subshells,
which give them great stability.
 Not reactive