App Chem. Module 3-Periodic Prop.
App Chem. Module 3-Periodic Prop.
The periodic table of elements is organized so that elements with similar electron configurations are near each
other. Elements in similar groups or columns can be categorized together into blocks based on which electron orbital
their outermost electrons (i.e., valence electrons) occupy. There are a total of 4 blocks for 4 different electron
orbitals: s, d, p, and f. Elements in the same block have their last valence electron occupying that same orbital.
Structure of the Periodic Table
• The elements in the far left-hand column (Li, Na, K, Rb, and Cs) are known
collectively as alkali metals.
• Similarly, Be, Mg, Ca, Sr, and Ba are called alkaline earths, and F, Cl, Br, and I are
referred to as halogens.
• He, Ne, Ar, Kr, and Xe were discovered much later than most of the other elements,
and they have been named rare gases or noble gases.
• At the bottom of the periodic table, two important categories of elements are arranged
which are called as Lanthanides and Actinides.
The modern periodic table arranges elements
in two important ways:
horizontal rows of the table, called periods,
and the vertical columns, called groups.
The elements are divided into metals, nonmetals, and metalloids according to their physical and chemical properties.
The organization of elements into the form resembling the modern periodic table is accredited to Mendeleev.
s-block elements:
• s-block elements are the elements found in Group 1 and Group 2 on the periodic table.
• Group 1 are the alkali metals which have one valence electron. They have low ionization energies which
makes them very reactive.
• Group 2 is the alkali earth metals which have two valence electrons, filling their s sublevel. Because they
have 2 valence electrons they are less reactive than group 1.
• Hydrogen is a nonmetal grouped with the alkali metals because it has one electron in its valence shell.
p-block elements:
• p-block elements are those in which the last electron occupies p- orbitals and are found in groups
13, 14, 15, 16,17 and 18 (except helium).
• Because p-block orbitals can only hold a maximum of six electrons, p-block elements are classified
into six groups.
•Includes carbon, nitrogen, oxygen, sulfur, halogens, and many other common elements.
•Interact with other chemicals by losing, gaining, or sharing the valence electrons.
•Mostly form covalent compounds (Exception: halogens form ionic compounds with s-block metals).
d-block elements:
• D block elements are the elements that can be found from the third group to the twelfth group of the modern
periodic table.
• D-block elements fall between the group numbers of 3 and group number 12 on the periodic table and
extend four rows downward. With ten columns and four rows of the periodic table located in the d block, that
makes for a total of 40 elements in this group. Example of First row d-block elements is shown below
• These elements are often characterised by metallic qualities such as malleability and ductility, strong electrical
and thermal conductivities and high tensile strength.
Sc Ti V Cr Mn Fe Co Ni Cu Zn
4s23d1 4s23d2 4s23d3 4s13d5 4s23d5 4s23d6 4s23d7 4s23d8 4s13d10 4s23d10
f-Block elements
• The elements in which the last electron enters (n-2) f orbital are known as f-block elements. The last electron
enters the pre-penultimate shell.
• Depending upon whether the last electron enters a 4f orbital or a 5f orbital, the f–block elements have
been divided into two series as lanthanides and actinides.
• The elements include 4f series of Ce to Lu and 5f series of Th to Lr. 14 elements are there that fill up the ‘f’
orbital in each series.
• Classification of F-Block Elements
• Lanthanides and actinides are the two series of the f-block elements or inner transition elements.
• Lanthanide series: The first series of elements are the lanthanides which include elements with atomic
numbers from 57 to 71. These elements are non-radioactive (except for promethium). In the lanthanide series
the last electron gets into the 4f orbital.
• Actinide series: The second series of elements are actinides which include elements with atomic numbers
from 89 to 103. These elements are generally radioactive in nature. In the actinide series the last electron gets
into the 5f orbital.
Periodic Properties
• The periodic table arranges the elements by periodic properties
• Electrons are added one at a time moving from left to right across a period. As this happens, the
electrons of the outermost shell experience increasingly strong nuclear attraction, so the electrons
become closer to the nucleus and more tightly bound to it.
• Moving down a column in the periodic table, the outermost electrons become less tightly bound to
the nucleus. This happens because the number of filled principal energy levels (which shield the
outermost electrons from attraction to the nucleus) increases downward within each group.
• Because of these trends, variation in elemental properties such as, atomic volume, atomic radius,
ionization potential, electron affinity and electronegativity varies along periods and groups.
Atomic Size
• Atomic size is the distance between the centre of the nucleus of an atom and its outermost shell.
• Atom size increases down a group because you keep moving to a new shell of electrons.
• It may be explained in terms of a new electron shell being added, when we pass from one element to another in
a group.
• It decreases across a period because you keep adding protons to the nucleus, which has a bigger effect than
adding an electron.
• The extra charge on the nucleus which draws the electrons inward resulting in smaller size for the atoms.
The trend of decrease in size of atoms, continues from left to right. Trends in Atomic Size
Ionic radius
• An ion is basically an atom with a positive or negative charge.
• The Ionic radius can be described as the distance between the nucleus of an ion and the
outermost shell of the ion.
• Atoms of metallic elements tend to form positive ions (cations) by losing one or more
electrons.
• Atoms of non-metallic elements tend to form negative ions (anions) by gaining one or more
electrons.
• Cations are smaller than the atoms from which they are formed.
• Anions are larger than the atoms from which they were formed.
Positive and negative ions form when electrons are transferred between atoms.
Cations are smaller than the atoms from which they are formed
Anions are larger than the atoms from which they were formed
Ionic Size
Few More examples:
Trends in Ionic Size
• Ionic radius increases as you move from top to bottom on the periodic table.
• Ionic radius decreases as you move across the periodic table, from left to right.
Ionization Energy
1. Ionization energy (IE) is the minimum energy (kJ/mol) required to remove an electron from a
gaseous atom in its ground state.
2. The higher ionization energy, the more difficult it is to remove the electrons.
3. The first ionization energy is the amount of energy required to remove the 1st electron from an
atom in the gaseous state.
I1 + X (g) + e- I1 first ionization energy Periodic Trend
(g)
I2 + X (g) X2+ - I2 second ionization energy Going down a column, IE's decrease.
(g) + e
I1 < I2 < I3
• Ionization energy generally increases moving from left to right across an element period (row). This is because
the atomic radius generally decreases moving across a period, so there is a greater effective attraction between
the negatively charged electrons and positively-charged nucleus.
• Ionization decreases moving top to bottom down an element group (column). This is because the principal
quantum number of the outermost electron increases moving down a group. There are more protons in atoms
moving down a group (greater positive charge), yet the effect is to pull in the electron shells, making them
smaller and screening outer electrons from the attractive force of the nucleus. More electron shells are added
moving down a group, so the outermost electron becomes increasingly distance from the nucleus.
• The IE of the first member of any group is the highest within that group and the IE of
the last member in the same group, is the least.
Table: First IE of the elements (in kJ mol-1)
Electron affinity (EA) or Electron Gain enthalpy
• Every atom, in general, has a tendency to gain or loose electrons in order to acquire a noble gas
configuration.
• Ex: Halogens, have seven electrons in their outermost orbit. Thus they show a tendency to
accept one more electron and attain the nearest noble gas configuration.
• Electron affinity is the amount of energy released when one electron is added to a neutral atom
(A) in order to form a –1 anion. The reaction (with energy shown) is
• The energy change (ΔE) for this process is called electron gain enthalpy of that atom.
Electron gain enthalpy is the energy released or adsorbed for one mole of neutral
atoms in a gaseous state when electron is accepted by each atom.
• The negative value shows release of energy and hence tendency to greater stabilization.
• The electron gain enthalpy becomes more in negative from left to right in a period.
• Electron gain enthalpies becomes less negative as we go down the group showing that the
electropositive character of the atoms increases.
• This is because the size of the atom increases down the group and the electron added goes to the
higher shells.
• The electron gain enthalpy of chlorine is more in negative value as compared to that of fluorine.
• This is due to the small size of the F atom and experiences repulsion from other electrons.
Table: Electron gain enthalpy in kJ mol-1
Electronegativity
Electronegativity is the ability of an atom of an element to attract electrons when the atom
is in a compound.
Towards the left of the table, valence shells are less than half full, so these atoms (metals)
tend to lose electrons and have low electronegativity.
Towards the right of the table, valence shells are more than half full, so these atoms
(nonmetals) tend to gain electrons and have high electronegativity.
• Homonuclear diatomic molecule H2 or F2, the electron pair of the covalent bond in each
molecule experiences equal attraction by each atom.
• Thus none of the two atoms is able to shift the bond pair of electrons to itself.
• In heteronuclear diatomic molecule, the bond pair electrons get shifted towards the atom
which is more electronegative than the other.
Electronegativity Decreases
Electronegativity Increases
Electronegativity (Pauling’s scale)
The ELECTRONEGATIVITY of an element helps us understand the
difference between ionic and covalent bonding
Elements with a HIGH electronegativity When two atoms form a bond their
DIFFERENCE in electronegativity
have a STRONG pull on electrons. determines the bond type.
• Effective Nuclear Charge is the net attraction force an outer electron feels. Net means that attraction
and repulsion forces are taken into account.
• Zeff takes both of these factors into account and represents an estimate of the net electric field
experienced by an electron
• The term "effective" is used because the shielding effect of negatively charged electrons prevents
higher orbital electrons from experiencing the full nuclear charge by the repelling effect of inner-
layer electrons.
The effective nuclear charge is mathematically expressed as,
Zeff = Z − S
Z = number of protons in the nucleus
S = Screening constant; the number of core electrons that screen the
Outer electrons from the positive charge in the nucleus.
Zeff = Z − S
Factors affecting Zeff
Z = number of protons in the nucleus
• Size of an atom S =the number of core electrons that screen the
Outer electrons from the positive charge in the nucleus.
• Total nuclear charge (Z)
• The screening and shielding of the inner shell and neighboring electrons of the same shell
• The extend of penetration of outermost electrons into the charge cloud.
Calculating Effective Nuclear Charge of Sodium Calculating Effective Nuclear Charge of Magnesium
Zeff = Z - S
Attractive Atomic Inner Core of
Charge felt Number Shielding e- =
by valence (#p+) screening
electrons constant
Effective Nuclear Charge Trend
• As you travel left to right across a period:
– Atomic number increases
– Shielding stays roughly the same
– Therefore Zeff increases significantly across a period
• As you travel down a family
– Atomic number increases sharply
– Shielding increases sharply
– Zeff does increase down a family but not as much as you might expect.
Orbital Diagram Rules for Filling Electrons in Orbitals
Aufbau Principle:
Electrons are added in orbitals in order of
increasing energy values
Hund’s Rule:
Electrons occupy equal energy orbitals so that a
maximum number of unpaired electrons results.
Penetration of Orbitals
• Penetration describes the proximity of electrons in an orbital to the nucleus. Electrons
which experience greater penetration experience less shielding and therefore experience a
larger Effective Nuclear Charge (Zeff) but shield other electrons more effectively.
• The repulsion an electron feels is shielding and the attraction it feels to the nucleus is
penetration.
• Penetration is not the outer electrons penetrating through the shield of the core electrons.
It is actually just how well the electrons feel the nucleus.
• It is essentially the number of protons charge minus the number of electrons shielding-
basically how effective the nucleus is at attracting the electrons.
A) Effective Nuclear Charge (Zeff) The effective nuclear charge increases from left to right and increases from
top to bottom on the periodic table.
B) Atomic Radius The atomic radius decreases from left to right, and increases from top to bottom.
C) Ionization Energies The ionization energies increase from left to right, and decrease from top to bottom.
D) Electronegativity The electronegativity of the elements is highest near fluorine. In general, it increases from
left to right and decreases from top to bottom.
Shielding and De-shielding
• Shielding refers to the core electrons repelling the outer rings and thus lowering the 1:1 ratio. The nucleus has
"less grip" on the outer electrons and are shielded from them.
• Shielding describes the amount of screening from nuclear charge that one electron can do with respect to its
neighbouring electrons. Electrons that have greater penetration can get closer to the nucleus and effectively
block out the charge from electrons that have less proximity.
• For example, Zeff is calculated by subtracting the magnitude of shielding from the total nuclear charge. The
value of Zeff will provide information on how much of a charge an electron actually experiences.
• Because the order of electron penetration from greatest to least is s, p, d, f; the order of the amount of
shielding done is also in the order s, p, d, f.
Polarizability
The ability of a cation to distort an anion is known as its polarization power and the tendency
of the anion to become polarized by the cation is known as its polarizability. It is enhanced by
the following factors.
Small cation:
The high polarizing power stems from the greater concentration of positive charge on a
small area. This explains why LiBr is more covalent than KBr (Li+ 90 pm cf. K + 152
pm).
Large anion:
The high polarizability stems from the larger size where the outer electrons are more
loosely held and can be more easily distorted by the cation. This explains why for the
common halides, iodides, are the most covalent in nature (I206 pm).
Molecular Orbital Theory
Introduction:
• The Molecular Orbital Theory (often abbreviated to MOT) is a theory on chemical bonding developed
at the beginning of the twentieth century by F. Hund and R. S. Mulliken to describe the structure and
properties of different molecules and electronic distribution.
• MOT is helpful in predicting molecular properties such as, shape, magnetism, and bond order.
• According MOT, individual atomic orbitals combine to form molecular orbitals, as the electrons of an
atom are present in various atomic orbitals and are associated with various nuclei
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Molecular orbitals are classified based on their energy:
1) Bonding orbitals
2) Anti-bonding orbitals
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• When addition of wave function takes place, the type of molecular orbital formed
are called bonding molecular orbitals. It is represented as ψMO = ψA + ψB. They
have low energy than atomic orbital involved.
• When subtraction of wave function takes place, the type of molecular orbital
formed are called anti-bonding orbitals. It is represented as ψMO = ψA - ψB. They
have higher energy.
The key features of the molecular orbital theory are listed below.
•The total number of molecular orbitals formed will always be equal to the total number of
atomic orbitals offered by the bonding species.
•There exist different types of molecular orbitals viz; bonding molecular orbitals, anti-
bonding molecular orbitals, and non-bonding molecular orbitals. Of these, anti-bonding
molecular orbitals will always have higher energy than the parent orbitals whereas bonding
molecular orbitals will always have lower energy
•The electrons are filled into molecular orbitals in the increasing order of orbital energy
(from the orbital with the lowest energy to the orbital with the highest energy).
•The most effective combinations of atomic orbitals (for the formation of molecular orbitals)
occur when the combining atomic orbitals have similar energies.
The filling of molecular orbitals takes place according to certain rules:
• Molecular orbitals can have maximum of two electrons and these must have
opposite spin (Pauli’s exclusion principle)
• Pairing of electrons in degenerate molecular orbitals does not takes place until
each of them has one electron each (Hund’s rule of maximum multiplicity)
When two atomic orbitals combine there are two resultant orbitals
Example: S-Orbital High energy anti-bonding
orbitals
Probability of finding the electrons is more in the case of Probability of finding electrons is less in antibonding
bonding molecular orbitals molecular orbitals. There is also a node between the anti-
bonding molecular orbital between two nuclei where the
electron density is zero.
These are formed by the combination of + and + and – These are formed by the overlap of + with – part.
with – part of the electron waves
The electron density, in the bonding molecular orbital in The electron density in the antibonding molecular orbital
the internuclear region, is high. As a result, the nuclei are in the internuclear region is very low and so the nuclei are
shielded from each other and hence the repulsion is very directly exposed to each other. Therefore the nuclei are less
less. shielded from each other.
The bonding molecular orbitals are represented by σ, π, δ The corresponding anti-bonding molecular orbitals are
represented by σ∗ , π∗, δ∗.
MO theory takes the idea of atomic orbitals overlapping to a new level, where new molecular
orbitals are generated using a mathematical process called linear combination of atomic
orbitals (LCAO).
Constructive interference
+. . + .
+. g bonding
cA = cB = 1
g = N [A + B ]
Amplitudes of wave
functions added
+. -. .
+. -
Destructive interference
A- B
Anti-bonding
Bond Order
• It is defined as half of difference between the number of electrons present in the
bonding orbital and antibonding orbitals that is,
• Those with positive bond orders are considered as stable molecules while those
with negative bond orders or zero bonder orders are unstable molecules.
Bond Order for H2
Electronic Configuration of H atom: (σ1s)2
Bond order = 2 – 0 / 2
higher bond order = stronger bond
Bond order = 1
It means a single covalent bond exists in H2 molecule, and diamagnetic since there is no unpaired
electron.
First period diatomic molecules
H H2 H
1s2
u*
Bond order: 1
Energy
(Single Bond)
1s 1s Stable molecule (450 KJ/mol)
g
Bond order =
½ (bonding electrons – antibonding electrons)
Diatomic molecules: The bonding in He2
He He2 He
1s2, *1s2
u*
Bond order: 0
Energy No Bond
1s 1s
Unstable Molecule
g 0 KJ/mole
Diatomic Molecules: MO diagrams for He2+ and
He2
s*1s s*1s
Energy
Energy
1s 1s 1s 1s
s1s s1s
AO of MO of AO of AO of MO of AO of
He He+ He+ He He2 He
2s 2s
Energy
2g
1u*
1s 1s
1g
Diatomic molecules: Homonuclear Molecules of the Second Period
Be Be2 Be
2u*
1s2, *1s2, 2s2,
2s 2s
*2s2
Energy
2g
Bond order: 0
1u*
1s 1s
1g
Application of MO Theory to H2, He2, N2, O2, HF and CO
An energy level diagram is a graphical representation of the energies of the various orbitals of
an atom or molecule. In most cases, the energy level diagram will be represented as a series of
horizontal lines, with each line representing an orbital.
Molecular Orbital Diagram for the O2 molecule
O2 = 1s22s22p4
B.O of O2 :2
B.O of N2 :3
B.O of CO : 3
B.O of HF :1
Magnetic Property: Diamagnetic
(Paired electrons)
A major feature of transition metals is their tendency to form complexes. A complex may
be considered as consisting of a central metal atom or ion surrounded by a number of
ligands. The interaction between these ligands with the central metal atom or ion is
subject to crystal field theory.
Crystal-Field Theory
Both electrons in the bond come from the ligand and are donated into an empty, hybridized
orbital on the metal.
Assumption in crystal field theory: the interaction between ligand and metal is electrostatic.
The more directly the ligand attacks the metal orbital, the higher the energy of the d orbital.
Crystal-Field Theory-Postulates
(i)In a coordination compound there are electrostatic interaction between metal atom/ion and
ligands. Ligand assumed to be a point charge
(ii) In an isolated metal atom or ion all five d-orbitals have equal energy i.e. they are
degenerate
(iii) When metal atom/ion gets surrounded by ligands, there occur interaction between d
electron cloud of metal atom/ion and ligands
(iv) If the field due to ligan around metal atom is spherically symmetrical, d-orbitals of metal
remains degenerated
(v) If filed due to ligand surrounding metal is unsymmetrical ( as in octahedral and tetrahedral
complexes) the degeracy of d-orbitals is splitted into two sets of orbitals
(vi) Orbitals lying in the direction of ligands (point charges) are raised to higher
energy state than those orbitals lying between the ligands ( point charges)
(vii) The energy difference between two sets of orbitals is denoted by ∆o for
octahedral and ∆t for tetrahedral
(viii) The magnitude of ∆o and ∆t depends upon the field strength of ligand around
the metal
(ix) Ligands which cause larger splitting ( large ∆) are called strong field ligands
while those which causes small splitting (small ∆) are called weak filed ligands
d-Orbitals in an Octahedral Field of
Ligands
In an octahedral field, the five d orbitals do not have the same energy: three
degenerate orbitals are higher energy than two degenerate orbitals.
The energy gap between them is called , the crystal field splitting energy.
Splitting of d-Orbital Energies by an Octahedral Field of Ligands
• Splitting of d-orbitals depends on the nature of the crystal field. [The energy
difference between t2g and eg level is designated by Δ and is called crystal
field splitting energy].
I− < Br− < S2− < SCN− < Cl− < NO3− < N3− < F− < OH− < C2O42− < H2O <
NCS− < CH3CN < py < NH3< en < bipy < phen < NO2− < PPh3 < CN− < CO
• Ligands for which Δo < P are known as weak field ligands and form high spin
complexes.
• If Δo > P, more energetically favorable for the fourth electron to occupy a t2g orbital with
configuration t42g eog. (where, P = energy required for e- pairing in an orbital).
• Ligands which produce this effect are known as strong field ligands and form low spin
complexes.
The Spectrochemical Series
Effect of the Ligand on Splitting Energy
Crystal field Splitting in Tetrahedral (Td) Complexes
• Orbital splitting energies are so low that pairing of electrons is not possible so these
are high spin complexes.
Splitting of d-orbital Energies by a Tetrahedral Field
Energy level diagrams for transition metal ions and their
magnetic properties.
Using crystal field theory, it is possible to draw the energy level diagram, electronic configuration
of a central metal atom/ion of a complex and to determine the magnetic moment value. Few
examples are given below.
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