CHEM122

Fundamentals of Chemistry

Dr. Vivek Mishra (AICCRS)

Mob. No. 8130384042 (J1-119)
MON 02:15 (J3-310) Group-AIB-GR-1 BSc(H)BT Research
Thursday 09:15 (J3-311) Group-AIB-GR-1
Friday 11:15 12:15 fundamental of Chemistry-1 Lab ( J3-205) Group-AIB-GR-1
Module I Periodic Table
CHM122
Modern periodic law and the present form of periodic table, position of hydrogen in periodic table, periodic trends in properties of 30
elements : size ,relationship,(atomic radii, ionic radii, inert gas radii), ionization potential, electron affinity, electro negativity.
Module II Chemical Bonding and molecular structure

Valence electrons, ionic bond, covalent bond, energy consideration in ionic bonding, Lattice energy and solvation energy and their 20
importance in the context of stability and solubility of ionic compounds, bond parameters, Lewis structure, polar character of covalent
molecules, bond moment, dipole moment, concept of hybridization involving s, p and d orbitals and shape of molecules, concept of
resonance and resonating structures, hydrogen bond.
Module III Acid and Bases

• Arrhenius concept, Bronsted-Lowry concept, Relative strength of acids and bases, hard and soft acid-base principle, role of water in 20
acids and bases, modern concept of acids and bases (aqueous and in non-aqueous solution); Lewis theory of acid-base
Module IV Coordination Chemistry

• Basic concepts of coordination chemistry (double salts, complex salts, coordination number of central metal atom or ion); 30
nomenclature and types of ligands; Werner’s theory of coordination compounds and Effective Atomic Number (EAN) rule
List of Experiments:
1. Qualitative analysis of inorganic mixtures, containing not more than four ionic species (excluding insoluble substances) out of the
following: Pb2+, Hg2+, Hg22+, Ag1+, Bi3+, Cu2+, Cd2+, As3+, Sn2+ , Sn4+, Fe2+ , Fe3+, Al3+ , CO2+ , Ni2+ , Mn2+, Zn2+, Ba2+ , Sr2+,
Ca2+ , Mg2+, NH41+ , K1+ , CO32-, S2-, SO3 2- , S2O32-, NO21-, CH3COO1-, F1-, Cl1-, Br1-, I1-, NO31-, SO42-, C2O42- , PO43- , BO33-.
2. Preparation of Inorganic Compounds: Chrome Alum, Cuprammonium sulphate, cuprous chloride, Prussion blue.
Pedagogy for Course Delivery:
History of the Periodic Table
 Law of Triads
The German chemist, Johann Dobereiner in early 1800’s was the first to consider the idea of trends
among properties of elements.

By 1829 he noted a similarity among the physical and chemical properties of several groups of three
elements (Triads). In each case, he noticed that the middle element of each of the Triads had an
atomic weight about halfway between the atomic weights of the other two. Also the properties of
the middle element were in between those of the other two members. Since Dobereiner’s
relationship, referred to as the Law of Triads, seemed to work only for a few elements, it was
dismissed as coincidence.

Johann Dobereiner
THE LAW OF OCTAVES
The English chemist, John Alexander Newlands in 1865 profounded the Law of Octaves. He arranged
the elements in increasing order of their atomic weights and noted that every eighth element had
properties similar to the first element. The relationship was just like every eighth note that resembles
the first in octaves of music. Newlands’s Law of Octaves seemed to be true only for elements up to
calcium. Although his idea was not widely accepted at that time, he, for his work, was later awarded
Davy Medal in 1887 by the Royal Society, London.
Mendeleev and Chemical Periodicity

Unlike Newlands, Lothar Meyer observed a change in length of

that repeating pattern. By 1868, Lothar Meyer had developed a

table of the elements that closely resembles the Modern

Periodic Table. However, his work was not published until after

the work of Dmitri Mendeleev, the scientist who is generally

credited with the development of the Modern Periodic Table.

 Mendeleev and Chemical Periodicity
While Dobereiner initiated the study of periodic relationship, it was
Mendeleev who was responsible for publishing the Periodic Law for the
first time. It states as follows :

“The properties of the elements are a periodic function

of their atomic weights.”
Mendeleev arranged elements in horizontal rows and vertical columns of a
table in order of their increasing atomic weights in such a way that the
elements with similar properties occupied the same vertical column or
group. Mendeleev’s system of classifying elements was more elaborate
than that of Lothar Meyer’s. He fully recognized the significance of
periodicity and used broader range of physical and chemical properties to
classify the elements.
• He placed the name of each known element on a card, together with
the atomic mass of the element and a list of its observed physical and
chemical properties

• He then arranged the cards according to various properties and

looked for trends or patterns

• Mendeleev noticed that when the elements were arranged in order

of increasing atomic mass, certain similarities in their chemical
properties appeared at regular intervals

• Such a repeating pattern is referred to as periodic

• Mendeleev’s procedure left several empty spaces in his periodic table

• In 1871, he predicted the existence and properties of the elements that would fill three of the

spaces

• By 1886, all three elements had been discovered

• Scandium, Sc, Gallium, Ga, and Germanium, Ge

• Their properties are very similar to those predicted by Mendeleev

• Success of Mendeleev’s predictions persuaded most chemists to accept his

periodic table and earned him credit as the discoverer of the periodic law

• Two questions remained

• (1) Why could most of the elements be arranged in the order of increasing atomic

mass but a few could not?

• (2) What was the reason for chemical periodicity?

Moseley and the Periodic Law

• In 1911 → English scientist Henry Moseley

examined the spectra of 38 different metals

• Moseley discovered a previously unknown pattern

• The elements in the periodic table fit into patterns better when they were
arranged in increasing order according to nuclear charge, or the number of
protons in the nucleus

• Henry Moseley observed regularities in the characteristic X-ray spectra of the

elements. A plot of √𝑣 (where √𝑣 is frequency of X-rays emitted) against atomic
number (Z) gave a straight line and not the plot of √𝑣 vs atomic mass.

• He thereby showed that the atomic number is a more fundamental property of

an element than its atomic mass. Mendeleev’s Periodic Law was, therefore,
accordingly modified. This is known as the Modern Periodic Law and can be
stated as :

• The physical and chemical properties of the elements are periodic functions of
their atomic numbers.
Write a short notes on the anomalous position of hydrogen in
Mendeleev’s periodic table

The anomalous position of hydrogen in Mendeleev's periodic table was a significant challenge and point of
contention in the early development of the periodic table. Dmitri Mendeleev, the Russian chemist who created
the first widely accepted periodic table in 1869, placed hydrogen in Group 1, which is now known as the alkali
metals group. However, the placement of hydrogen in this group was anomalous for several reasons:
1.Diverse Properties: Hydrogen possesses a unique combination of properties that make its placement in any
single group challenging. It can behave as both a metal and a non-metal, and its properties can vary widely
depending on the conditions and the elements it is combined with.
2.Isotopes: Hydrogen has several isotopes, including protium (the most common), deuterium, and tritium. These
isotopes have different atomic masses and properties. The varying atomic masses of hydrogen isotopes
complicated its placement in the periodic table.
3.Electronegativity: Hydrogen's electronegativity is closer to that of the non-metals in Group 17 (the halogens) rather
than the alkali metals in Group 1. This made its placement in Group 1 questionable.
4.Hydrogen Bonding: Hydrogen can form unique bonds called hydrogen bonds with other elements, especially
oxygen, nitrogen, and fluorine. This behavior was not well-understood at the time of Mendeleev's table, and it made
hydrogen's classification more complex.
5.Lack of Typical Metallic Properties: While hydrogen exhibits some metallic properties, such as conducting electricity
under certain conditions, it lacks many of the typical characteristics of metals found in Group 1, like sodium and
potassium.
Mendeleev recognized these challenges but chose to place hydrogen in Group 1 based on its atomic mass and
chemical reactivity with other elements. He hoped that further research would clarify its position. Over time, as our
understanding of atomic structure and chemical behavior improved, hydrogen's anomalous position in Group 1
became more evident.
In the modern periodic table, hydrogen is placed at the top of Group 1 as a non-metal, recognizing its unique
properties and its tendency to form bonds with other elements. Its placement at the top signifies its distinctiveness
from the alkali metals below it. The anomalous position of hydrogen in Mendeleev's periodic table played a crucial
role in the development of our understanding of atomic structure and chemical bonding.
Electronic Configuration and the Periodic Table
An electron in an atom is characterized by a set of four
quantum numbers, and the principal quantum number (n )
defines the main energy level known as shell.

The filling of electrons into different subshells, also referred

to as orbitals (s, p, d, f ) in an atom.

The distribution of electrons into orbitals of an atom is called

its electronic configuration.
The Modern Periodic Table
• “Periodic” - Repeating patterns

• Listed in order of increasing number of protons (atomic #)

• Properties of elements repeat
• Periodic Law- “the physical and chemical properties of the elements are periodic
functions of their atomic numbers.”
Periods and Blocks of the Periodic Table
• Elements are arranged vertically in the periodic table in groups that
share similar chemical properties
• They are also organized horizontally in rows, or periods

• The length of each period is determined by the number of electrons

that can occupy the sublevels being filled in that period
Electronic Configurations are explained on the basis of PERIODS or in GROUPS
Electronic Configurations in group
main group elements
 Metals
• Most solids (Hg is liquid)
• Luster – shiny.
• Ductile – drawn into thin wires.
• Malleable – hammered into
sheets.
• Conductors of heat and
electricity.
• Include transition metals –
“bridge” between elements on
left & right of table
 Non-Metals
• Properties are generally opposite
of metals
• Poor conductors of heat and
electricity
• Low boiling points
• Many are gases at room
temperature
• Solid, non-metals are brittle
(break easily)
• Chemical properties vary
Metalloids

• stair-step pattern
• Have properties similar to
metals and non-metals
• Ability to conduct heat
and electricity varies with
temp
• Better than non-metals
but not metals
• semiconductors
 Periodic Trends
(i) Atomic Radius

• In periodic table, there is a DECREASE in

atomic radii across the periods from
left to right
Atomic radius decreases across a period because valance
electrons are being added to the same energy level at
the same time the nucleus is increasing in protons.

• Caused by increasing positive charge of

nucleus (more protons = more positive
charge)
The increase in nuclear charge attracts the electrons more
strongly, pulling them closer to the nucleus.
Group Trends

• Radii of elements decrease as you go UP a group

• Electrons occupy sublevels in consecutively higher main energy levels

(located further away from nucleus)

• In general, the atomic radii of the main-groups elements decrease

from the bottom to the top of a group

2. Ionic radii
The removal of an electron from an atom results in the formation of a cation, whereas gain of an
electron leads to an anion.

The ionic radii can be estimated by measuring the distances between cations and anions in ionic
crystals.

In general, the ionic radii of elements exhibit the same trend as the atomic radii.

A cation is smaller than its parent atom because it has fewer electrons while its nuclear charge
remains the same.

The size of an anion will be larger than that of the parent atom because the addition of one or
more electrons would result in increased repulsion among the electrons and a decrease in
effective nuclear charge.
 Quantum Mechanical Model

Effective Nuclear Charge: The s, p, d, and f orbitals within a given

shell have slightly different energies.

The difference in energies between subshells result in electron–electron

repulsion which shields outer electrons from the nucleus.
The net nuclear charge felt by an electron is called the effective nuclear
charge ( Zeff ).

Zeff
 Quantum Mechanical Model

Zeff is lower than actual

nuclear charge.

Zeff increases
toward nucleus
ns > np > nd > nf

This explains certain periodic

changes observed.
 Z*

The effective nuclear charge in the actual charge from the

nucleus that an electron feels due to attractive forces from
the nucleus but also repulsive forces from the other
electrons, mainly the core electrons.
3. Ionization Energy
• Electrons can be removed from an atom if enough energy is supplied
• Using A as a symbol for an atom of ANY element, the process can be
expressed as follows:

A + energy → A+ + e-
• A+ represents an ion of element A with single positive charge (a 1+
ion)

• Ion → an atom or group of bonded atoms that have a positive or

negative charge

• Ionization → any process that results in the formation of an ion

Trends in Ionization Potential:
➢Ionization energy generally increases from left to right in a period because of the
increase in nuclear charge and decrease in atomic radius.

• Ionization energies generally decrease down a group due to the shielding effect*
and increase in atomic size.
*(The phenomena in which the inner shell electrons shield the outer electrons in an atom from the
attractive force (pull) of the Nucleus is known as Shielding. So, more is the shielding ⇒ more the
outer electrons are shielded ⇒ The attractive pull by the nucleus on the outer electrons decreases
⇒ Thus, the size (radius) of the atom increases.)

➢Departures from these trends can usually be traced

to repulsion between electrons, particularly electrons
occupying the same orbitals.
➢ It requires more energy to remove each successive electron.
➢When all valence electrons have been removed, the ionization energy
takes a quantum leap.
Trends in First Ionization Energies

➢As one goes down a column, less

energy is required to remove the first
electron.
For atoms in the same group, Zeff
is essentially the same, but the
valence electrons are farther from
the nucleus.
Generally, as one goes across a
row, it gets harder to remove an
electron.
As you go from left to right, Zeff
increases.

The second occurs between

Groups VA and VIA.
Electron removed comes from
doubly occupied orbital.
Repulsion from other electron in
orbital helps in its removal.
➢ Elements in the lower
left of the periodic
table tend to have
lower ionization
energies than those in
the upper right.

➢ These are the elements

in the s block, d block,
f block and the lower
left of the p block -
metallic solids
Period Trends

• In general, ionization energies of the main-group elements

INCREASE across each period

• Caused by increasing nuclear charge

• Higher charge more strongly attracts electrons in same energy

level
Group Trends
• Ionization energies generally INCREASE going UP a group

• Electrons going down in group are in higher energy levels, so further

away from the nucleus

• Removed more easily

• Also more electrons between outermost electrons and the nucleus

(shields them from attraction to positive nucleus)
Ionization Energy
➢Ionization : The process of removing an electron from an isolated atom to
form a positive ion.

First ionization energy (I1): amount of energy required to remove the

most loosely bound electron from an isolated gaseous atom to form a
cation.

Second ionization energy (I2): amount of energy required to remove a

second electron from the gaseous monopositive cation to form dipositive
cation.

• Greater the IE, the more difficult to remove the electron

 Trends of Ionization Energy

• I1< I2 < I3 < I4

• With each removal, the ion becomes more positive

• Strengthens nucleus’s hold on its electrons

• Sharp increase in IE when inner-shell electrons are removed

➢ Ionization energies are usually expressed in electron volts
(eV) per atom or in kilojoules per mol (kJ/mol)
1eV/atom=96.48 kJ/mol

➢ Value of each ionization energy will increase with each

removed electron, since the attractive influence of the
nucleus increases and will and will require more energy for
the removal of an electron from more positive charges.

➢ Ionization energies measure how tightly electrons are

bound to atoms.
➢ Low energies indicate ease of removal of electrons and vice
versa.
Irregularities
• I does not always increase across rows
• Decrease from Be to B
Be: [He] 2s2
B: [He]2s2 2p1

• The most easily removed electron in B is that in the 2p orbital, higher in

energy than the 2s electrons in Be

• 2p electron of B needs less energy for total removal than does the 2s
electron of Be
Irregularities
• O is lower than N
• N: [He]2s2 2p3
• O: [He]2s2 2p4

• Important difference in the way electrons are distributed

• Hund’s rule: 3 e- in the 2p orbitals of a nitrogen atom all have the same spin, but e- are
paired in one of the 2p orbitals of oxygen
• Electrons try to stay as far apart as possible to minimize repulsion

• Force of repulsion between these electrons is minimized to some extent by pairing

electrons
• Slightly easier to remove an electron
Factors affecting the magnitude of Ionization Potential:
1. Effective nuclear charge
2. Atomic size i. e. atomic radius
3. Principle quantum number
4. Shielding effect
5. Half filled and completely filled orbitals
6. Nature of orbitals
7. The extent of penetration of valence electrons

Effective Nuclear Charge: Effective nuclear charge refers to the charge that the outermost (valance) electron have.

Greater the magnitude of effective nuclear charge, higher is the amount of energy needed to remove the

outermost shell electron. Thus, with the increase of the magnitude of effective nuclear charge, the

magnitude of ionization potential also increases.

The effective nuclear charge increases from left to right in a period.

Atomic size:

Greater is the atomic size of an atom, more far is the

outermost shell electron from the nucleus and hence lesser
will be the force of attraction exerted by the nucleus on the
outermost shell electron. Thus, higher the value of atomic
radius of an atom, lower will be the ionization energy.

Principal Quantum Number (n):

Greater is the value of n for the valence shell

electron of an atom, further away this electron will be from
the nucleus and hence lesser will be the force of attraction
exerted by the nucleus on it so lesser energy will be
required to remove the valence shell electron. Thus, with
increase the principal quantum number of the orbital from which
the electron is to be removed, the magnitude of ionization
potential decreases.
Ionization energy vs. atomic number
2500 He

Ionization energy (kJ/mol)

Ne
2000
F Ar
1500
N
H O Cl
1000 Be C P S
B Mg Si
Al Ca
500
Li Na K
0
0 2 4 6 8 10 12 14 16 18 20
Element
Shielding Affect:

The magnitude of shielding effect determines the magnitude of the force of

attraction between the nucleus and the valence-shell electron. Greater is
the magnitude of shielding effect working on the valence shell electron.
Thus with the increase of shielding effect ionization potential increases.

Half-filled and completely-filled orbitals:

According to Hund’s rule, half-filled (ns1, np3, nd5) or completely-

filled (ns2. ns6, nd10) orbitals are comparatively more stable and hence
more energy is needed to remove an electron from such orbitals. Thus the
ionization potential of an atom having half-filled or completely-filled orbitals in its
electronic configuration is relatively higher than that expected normally from its
position in the periodic table .
Nature of Orbitals:
The nature of orbitals of the valence-shell from which the
electron is to be removed also influences the magnitude of ionization potential.
The relative order of energy of s, p, d and f orbitals of a given nth shell is as:
ns < np < nd < nf
This order clearly shows that to remove an electron from f-orbital will be easiest
while to remove the same from s-orbital will be the most difficult.

The extent of penetration of valence electrons:

The degree of penetration of valence electrons in a given principal energy level

decreases in the order s>p>d>f, since ns electron is more tightly bound than any
np electron, which in turn is more tightly bound than any nd electron etc.
What are Valence electrons?
• outermost e-’s
• Responsible for chem props
• Elements in same group…
same # of VE
• ALL atoms want full outer
energy level (usually 8 VE)
• To get full outer energy level, some elements:
• lose e- (metals)
• gain e- (non-metals)
• share electrons (some non-metals & metalloids)
• Main-group elements – valence e- are in outermost s
and p sublevels
• Inner e- held too tightly by nucleus to be involved in
compound formation
3. Electronegativity

• Linus Pauling is the one who did extensive work with this
trend. Also made a simple scale of electronegativity

• He used the 2nd row of the periodic table, Li through F

• He assigned Lithium 1.0 and Flourine 4.0

– +0.5 as you move across

• Used Flourine as standard to set other #’s

3. Electronegativity

• Valence e- hold atoms together in compounds

• In many compounds, negative charge centered around one atom

more than another

• Uneven distribution of charge has effect on compound’s properties

• Useful to have measurement of how strongly one atom attracts e- of

another atom
• Electronegativity → measure of the ability of an atom in a chemical

compound to attract electrons

• Most e-neg element (fluorine) – randomly assigned value of 4

• Other values calculated in relation to F

Period Trends

• e-negs tend to INCREASE across each period

• There are exceptions (of course)

• Alkali and alkaline-earth metals are least e-neg

• In compounds, their atoms have low attraction for e-

Group Trends

• Electronegativities tend to INCREASE going UP a group or stay the same

• At higher energy levels electrons being added are further away from the
nucleus

• Therefore, less attraction to the nucleus

• Also more electrons between outermost electrons and the nucleus (shields
them from attraction to positive nucleus)
4. Electron Affinity

• The opposite of Ionization

• Electron Affinity is the addition of electrons to an atom

Energy change accompanying addition of electron to

gaseous atom:

Cl + e− ⎯⎯→ Cl−
Electron Affinities

• Energy change that occurs when electron are added to a gaseous atom

• Measure of the attraction of an atom to an electron

• Negative values (energy is released during process)

• kJ/mol

• More negative affinity = greater attraction

Trends in Electron Affinities
• Not as evident as that of ionization energy
• Halogens have the greatest affinities (1 e- shy of a filled p subshell)
• Noble gases have affinities of 0
• Group 2A and 5A have very little affinity

In general, electron affinity

becomes more exothermic as you
go from left to right across a row.
Electron Affinity
Difference between electronegativity and electron affinity
Electronegativity and electron affinity are both concepts related to the behavior of electrons in atoms and
molecules, but they describe different aspects of electron behavior. Here are the key differences between
electronegativity and electron affinity:
1. Definition:
•Electronegativity: Electronegativity is a measure of an atom's ability to attract and hold onto electrons in a
chemical bond when it is part of a compound. It is a relative scale that quantifies the atom's tendency to pull
shared electrons towards itself.
•Electron Affinity: Electron affinity is the energy change that occurs when an atom or ion gains an electron to
form a negatively charged ion (anion). It measures the willingness of an atom to accept an additional electron.
2. Unit:
•Electronegativity: Electronegativity is typically expressed on various scales, such as the Pauling scale, and it does
not have a specific unit.
•Electron Affinity: Electron affinity is expressed in units of energy, often in electron volts (eV) or kilojoules per
mole (kJ/mol).
3. Measurement:
•Electronegativity: Electronegativity values are assigned to elements based on their chemical behavior and the
properties of compounds they form. These values are determined empirically.
•Electron Affinity: Electron affinity is measured experimentally by measuring the energy change when an atom or
ion gains an electron.
4. Purpose:
•Electronegativity: Electronegativity helps predict the nature of chemical bonds in molecules. It provides insight into the polarity of chemical
bonds and the distribution of electrons within molecules.
•Electron Affinity: Electron affinity is used to understand an element's tendency to form negatively charged ions. It is essential for predicting the
formation of anions in chemical reactions.
5. Direction:
•Electronegativity: Electronegativity increases from left to right across a period and decreases from top to bottom within a group on the periodic
table.
•Electron Affinity: Electron affinity generally becomes more negative (i.e., more exothermic) from left to right across a period and more negative
from bottom to top within a group on the periodic table.
6. Relationship to Chemical Behavior:
•Electronegativity: It is more related to the polarity and type of chemical bonds (ionic or covalent) formed between atoms in compounds.
•Electron Affinity: It is more directly related to the formation of ions and the energy change associated with gaining an electron in chemical
reactions.
In summary, electronegativity and electron affinity are related concepts, but they focus on different aspects of electron behavior in atoms and
molecules. Electronegativity deals with an atom's ability to attract electrons in a bond, while electron affinity deals with the energy change when
an atom gains an electron to form an ion.
Putting it all together