I.

ATOMS AND THE PERIODIC TABLE

The Atomic Theory
Dalton’s work marked the beginning of the modern era of chemistry. The hypotheses
about the nature of matter on which Dalton’s atomic theory is based can be
summarized as follows:
1. Elements are composed of extremely small particles called atoms.
2. All atoms of a given element are identical, having the same size, mass, and
chemical properties. The atoms of one element are different from the atoms of
all other elements.
3. Compounds are composed of atoms of more than one element. In any
compound, the ratio of the numbers of atoms of any two of the elements present
is either an integer or a simple fraction.
4. A chemical reaction involves only the separation, combination, or
rearrangement of atoms; it does not result in their creation or destruction.
Atoms
- The atom is the smallest part of matter that represents a particular element
- For quite a while, the atom was thought to be the smallest part of matter that
could exist. But in the latter part of the 19th century and early part of the 20th,
scientists discovered that atoms are composed of certain subatomic particles
and that no matter what the element, the same subatomic particles make up
the atom. The number of the various subatomic particles is the only thing that
varies.
Three major subatomic particles:
1. Proton- positively charged particles (Plum-pudding Model)
2. Electrons- negatively charged particles (Cathode Ray Experiment)
3. Neutrons- electrically neutral particles having a mass slightly greater than that
of protons
Atomic Number (Z)
- the number of
protons in the nucleus of each atom of an element.
Mass Number (A)
- the total number of neutrons and protons present in the nucleus of an atom of
an element.
For example, if the mass number of a particular boron atom is 12 and the atomic
number is 5 (indicating 5 protons in the nucleus), then the number of neutrons is 12 –
5 = 7. Note that all three quantities (atomic number, number of neutrons, and mass
number) must be positive integers, or whole numbers.

Isotopes
- Atoms that have the same atomic number (Z) but different mass numbers (A)
are called isotopes
- All neon atoms have 10 protons in their nuclei, and most have 10 neutrons as
well. A very few neon atoms, however, have 11 neutrons and some have 12.
We can

represent these three different types of neon atoms as

Nuclear Stability
One of Becquerel’s students, Marie Curie, suggested the name radioactivity to
describe this spontaneous emission of particles and/or radiation. Since then, any
element that spontaneously emits radiation is said to be radioactive. Three types of
rays are produced by the decay, or breakdown, of radioactive substances such as
uranium. Two of the three are deflected by oppositely charged metal plates.
Alpha (a) rays consist of positively charged particles, called a particles, and
therefore are deflected by the positively charged plate.
Beta (b) rays, or b particles, are electrons and are deflected by the negatively
charged plate.
The third type of radioactive radiation consists of high-energy rays called
gamma (g) rays . Like X rays, g rays have no charge and are not affected by an
external field

Average Atomic Mass

The sum of the masses of its isotopes, each multiplied by its mass abundance
(the decimal associated with percent of atoms that are a given isotopes)

Example:
The mass spectrum of a particular sample of carbon shows that 98.93% of the
carbon atoms are carbon-12 with a mass of exactly 12 u; the rest are carbon-13 atoms
with a mass of 13.0033548378 u.
Mole
In the SI system the mole (mol) is the amount of a substance that contains as
many elementary entities (atoms, molecules, or other particles) as there are atoms in
exactly 12 g (or 0.012 kg) of the carbon-12 isotope. The actual number of atoms in 12
g of carbon-12 is determined experimentally. This number is called Avogadro’s
number (N A ), in honor of the Italian scientist Amedeo Avogadro.

Molar Mass
Molar mass ( m ), defined as the mass (in grams or kilograms) of 1 mole of
units (such as atoms or molecules) of a substance.

II. QUANTUM THEORY AND THE ELECTRONIC STRUCTURE OF ATOMS

Quantum Theory
- Max Plank (1900)- discovered that atoms and molecules emit energy only in
certain discrete quantities, or quanta
- Classical physics places no limitations on the amount of energy a system may
possess, whereas quantum theory limits this energy to a set of specific values.
The difference
between any two
allowed energies of a
system also has a
specific value, called a quantum of energy. This means that when the energy
increases from one allowed value to another, it increases by a tiny jump, or
quantum.
- Physicists had always assumed that energy is continuous and that any amount
of energy could be released in a radiation process.

Quantum Mechanics

Werner Heinsenberg- formulated what is now known as the Heisenberg uncertainty

principle: it is impossible to know simultaneously both the momentum p (defined as
mass times velocity) and the position of a particle with certainty.
* Applying the Heisenberg uncertainty principle to the hydrogen atom, we see that in
reality the electron does not orbit the nucleus in a well-defined path, as Bohr thought.
If it did, we could determine precisely both the position of the electron (from its location
on a particular orbit) and its momentum (from its kinetic energy) at the same time, a
violation of the uncertainty principle.
Erwin Schrödinger (1926)- formulated an equation that describes the behavior and
energies of submicroscopic particles in general, an equation analogous to Newton’s
laws of motion for macroscopic objects.
- specifies the possible energy states the electron can occupy in a hydrogen
atom and identifies the corresponding wave functions. These energy states
and wave functions are characterized by a set of quantum numbers, with
which we can construct a comprehensive model of the hydrogen atom.
Quantum Numbers
describe the distribution of electrons in hydrogen and other atoms. These
numbers are derived from the mathematical solution of the Schrödinger equation for
the hydrogen atom.

The principal quantum number

The principal quantum number n describes the average distance of the orbital from
the nucleus — and the energy of the electron in an atom. It can have only positive
integer (whole number) values: 1, 2, 3, 4, and so on. The larger the value of n, the
higher the energy and the larger the orbital, or electron shell.

The angular momentum quantum number l

The angular momentum quantum number l describes the shape of the orbital, and the
shape is limited by the principal quantum number n: The angular momentum quantum
number l can have positive integer values from 0 to n – 1. For example, if the n value
is 3, three values are allowed for l: 0, 1, and 2. The value of l defines the shape of the
orbital, and the value of n defines the size. Orbitals that have the same value of n but
different values of l are called subshells. These subshells are given different letters to
help chemists distinguish them from each other.

The magnetic quantum number ml

The magnetic quantum number ml describes how the various orbitals are oriented in
space. The value of ml depends on the value of l. The values allowed are integers from
–l to 0 to +l.
For example, if the value of l = 1, you can write three values for ml: –1, 0, and +1. This
means that there are three different p subshells for a particular orbital. The subshells
have the same energy but different orientations in space.
The spin quantum number ms
The fourth and final quantum number is the spin quantum number ms. This one
describes the direction the electron is spinning in a magnetic field — either clockwise
or counterclockwise.
Only two values are allowed for ms: +1⁄2 or –1⁄2. For each subshell, there can be only
two electrons, one with a spin of +1⁄2 and another with a spin of –1⁄2.

Atomic Orbitals

s orbitals
All s orbitals are spherical in shape but differ in size, which increases as the principal
quantum number increases. Although the details of electron density variation within
each boundary surface are lost, there is no serious disadvantage. For us the most
important features of atomic orbitals are their shapes and relative sizes, which are
adequately represented by boundary surface diagrams.

p orbitals
It should be clear that the p orbitals start with the principal quantum number n = 2. If n
= 1, then the angular momentum quantum number / can assume only the value of
zero; therefore, there is only a 1 s orbital. As we saw earlier, when / = 1, the magnetic
quantum number m/ can have values of -1, 0, 1. Starting with n = 2 and / = 1, we
therefore have three 2 p orbitals: 2 p x , 2 p y , and 2 p z.

d Orbitals and Other Higher-Energy Orbitals

When / = 2, there are five values of m/, which correspond to five d orbitals. The lowest
value of n for a d orbital is 3. Because / can never be greater than n - 1, when n = 3
and / = 2, we have five 3 d
orbitals (3dxy, 3dyz, 3dxz, 3dx2 2 y2, and 3dz2). Orbitals having higher energy than d
orbitals are labeled f , g , . . . and so on.

Electronic Configurations
The electron configuration of an atom is a designation of how electrons are
distributed among various orbitals in principal shells and subshells.

Rules for Assigning Electrons to Orbitals

1. Electrons occupy orbitals in a way that minimizes the energy of the atom.
2. Aufbau principle, the total energy of an atom depends not only on the orbital
energies but also on the electronic repulsions that arise from placing electrons
in particular orbitals. With only a few exceptions, the order in which orbitals fill
is
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p
3. Only two electrons may occupy the same orbital, and these electrons
must have opposite spins. Pauli exclusion principle, this principle states
that no two electrons in an atom can have the same set of four quantum
numbers. If two electrons in an atom should have the same n, /, and m/ values
 (that is, these two electrons are in the same atomic orbital), then they must have
different values of ms. In other words, only two electrons may occupy the same
atomic orbital, and these electrons must have opposite spins.
4. When orbitals of identical energy (degenerate orbitals) are available,
electrons initially occupy these orbitals singly and with parallel spins.
Hund’s Rule, a simplified statement of Hund’s rule is that, for a given
configuration, the arrangement having the maximum number of parallel spins
is lower in energy than any other arrangement arising from the same
configuration. This behavior can be rationalized as follows.

Here are a couple of electron configurations you can use to check your conversions
from energy level diagrams:
Chlorine (Cl): 1s22s22p63s23p5
Iron (Fe): 1s22s22p63s23p64s23d6

Electron Configurations and the Periodic Table

 The group 1 atoms (alkali metals) have one outer-shell (valence) electron in an
s orbital, that is,
 The group 17 atoms (halogens) have seven outer-shell (valence) electrons, in
the configuration ns2np5.
 The group 18 atoms (noble gases)—with the exception of helium, which has
only two electrons—have outermost shells with eight electrons, in the
configuration ns2np6.

Four blocks of elements according to the subshells being filled:

s block. The s orbital of highest principal quantum number (n) fills. The s block
consists of groups 1 and 2 (plus He in group 18).
p block. The p orbitals of highest quantum number (n) fill. The p block consists of
groups 13, 14, 15, 16, 17, and 18 (except He).
d block. The d orbitals of the electronic shell n - 1 (the next to outermost) fill. The d
block includes groups 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12.
f block. The f orbitals of the electronic shell n - 2 fill. The f-block elements are the
lanthanides and the actinides.

III. PERIODIC TRENDS OF THE ELEMENT

Modern periodic Table

In the mid-1800s, Dmitri Mendeleev, a Russian chemist, noticed a repeating pattern
of chemical properties in the elements that were known at the time. Mendeleev
arranged the elements in order of increasing atomic to form something that fairly
closely resembles the modern periodic table. He was even able to predict the
properties of some of the then-unknown elements. Later, the elements were
rearranged in order of increasing atomic number, the number of protons in the nucleus
of the
atom.
Arrangement of Elements
Metals
you can see a stair-stepped line starting at boron (B), atomic number 5, and going all
the way down to polonium (Po), atomic number 84. Except for germanium (Ge) and
antimony (Sb), all the elements to the left of that line can be classified as metals. These
metals have properties that you normally associate with the metals you encounter in
everyday life. They’re solid at room temperature (with the exception of mercury, Hg, a
liquid), shiny, good conductors of electricity and heat, ductile (they can be drawn into
thin wires), and malleable (they can be easily hammered into very thin sheets). All
these metals tend to lose electrons easily. As you can see, the vast majority of the
elements on the periodic table are classified as metals.

Non Metals
Except for the elements that border the stair-stepped line the elements to the right of
the line, along with hydrogen, are classified as nonmetals. Nonmetals have properties
opposite those of the metals. The nonmetals are brittle, aren’t malleable or ductile,
and are poor conductors of both heat and electricity. They tend to gain electrons in
chemical reactions. Some nonmetals are liquids at room temperature.

Metalloids
The elements that border the stair-stepped line in the periodic table are classified as
metalloids. The metalloids, or semimetals, have properties that are somewhat of a
cross between metals and nonmetals. They tend to be economically important
because of their unique conductivity properties (they only partially conduct electricity),
which make them valuable in the semiconductor and computer chip industry. (The
term Silicon Valley doesn’t refer to a valley covered in sand; silicon, one of the
metalloids, is used in making computer chips.)

Arrangement by Families and Periods

Periods: The seven horizontal rows are called periods. The periods are numbered 1
through 7 on the left-hand side of the table. Within each period, the atomic numbers
increase from left to right.
Families: The vertical columns are called groups, or families. The families may be
labeled at the top of the columns in one of two ways. The older method uses roman
numerals and letters. The newer method simply uses the numbers 1 through 18.

Effective Nuclear Charge

The effective nuclear charge (Zeff ) is the nuclear charge felt by an electron
when both the actual nuclear charge (Z) and the repulsive effects (shielding) of the
other electrons are taken into account. In general, Zeff is given by

where sigma is called the shielding constant (also called the screening constant).
The shielding constant is greater than zero but smaller than Z.
Atomic Properties
Atomic Radius. which is one-half the distance between the two nuclei in two adjacent
metal atoms or in a diatomic molecule. Within a group we find that atomic radius

increases with atomic number.

Ionic radius. the radius of a cation or an anion

- Cations are smaller than the atoms from which they are formed.
- For isoelectronic cations, the more positive the ionic charge, the smaller the
ionic radius.
- Anions are larger than the atoms from which they are formed. For

isoelectronic anions, the more negative the charge, the larger the ionic radius.

Ionization Energy
- The ionization energy, Ei, is the quantity of energy a gaseous atom must
absorb to be able to expel an electron. The electron that is lost is the one that
is highest in energy, and therefore, is most loosely held.
- With relatively few exceptions, ionization energies increase from left to right
across a period and decrease from top to bottom within a group.
- Ionization energies decrease as atomic radii increase.

Electron Affinity
- Electron affinity, Eea, can be defined as the enthalpy change, that occurs
when an atom in the gas phase gains an electron. According to this definition,
the electron affinity of fluorine is a negative quantity.
- The overall trend is an increase in the tendency to accept electrons (electron
affinity values become more positive) from left to right across a period. The
 electron affinities of metals are generally lower than those of nonmetals. The
values vary little within a given group.

Electronegativity
- The electronegativity (EN) of an element is a measure of the relative tendency
of an atom to attract electrons to itself when it is chemically combined with
another atoms
- Elements with high electronegativities (non metals) often gain electrons to
form an ions. Elements with low electronegativities (metals) often lose
electrons to form cations.
- Electronegativities usually increases from left to right across periods and
decrease from to bottom within groups

Magnetic Properties
- In a diamagnetic atom or ion, all electrons are paired and the individual
magnetic effects cancel out. A diamagnetic species is weakly repelled by a
magnetic field.
- A paramagnetic atom or ion has unpaired electrons, and the individual
magnetic effects do not cancel out. The unpaired electrons possess a
magnetic moment that causes the atom or ion to be attracted to an external
magnetic field. The more unpaired electrons present, the stronger is this
attraction

Polarizability
- The polarizability of an atom provides a measure of the extent to which its
electron cloud can be distorted, for example, by the application of an
externally applied electric field or by the approach of another atom, molecule,
or ion. It is often expressed in units of volume. The polarizability of an atom
depends on how diffuse or spread out its electron cloud is, and in general,
polarizability increases with the size of the atom.
- polarizability decreases from left to right across a period and increases from
top to bottom within a group.

Lewis Theory
1. Electrons, especially those of the outermost (valence) electronic shell, play a
fundamental role in chemical bonding.
2. In some cases, electrons are transferred from one atom to another. Positive and
negative ions are formed and attract each other through electrostatic forces called
ionic bonds.
3. In other cases, one or more pairs of electrons are shared between atoms. A bond
formed by the sharing of electrons between atoms is called a covalent bond.
4. Electrons are transferred or shared in such a way that each atom acquires an
especially stable electron configuration. Usually this is a noble gas configuration, one
with eight outer-shell electrons, or an octet.
Lewis Symbol
A Lewis symbol consists of a chemical symbol to represent the nucleus and core
(inner-shell) electrons of an atom, together with dots placed around the symbol to
represent the valence (outer-shell) electrons.

Lewis Structure
Lewis structure is a combination of Lewis symbols that represents either the transfer
or the sharing of electrons in a chemical bond

IONIC COMPOUND AND COVALENT BONDING

Ionic bonding is the complete transfer of valence electron(s) between atoms. It

is a type of chemical bond that generates two oppositely charged ions. In ionic bonds,
the metal loses electrons to become a positively charged cation, whereas the
nonmetal accepts those electrons to become a negatively charged anion. Ionic bonds
require an electron donor, often a metal, and an electron acceptor, a nonmetal.
Ionic bonding is observed because metals have few electrons in their outer-
most orbitals. By losing those electrons, these metals can achieve noble gas
configuration and satisfy the octet rule. Similarly, nonmetals that have close to 8
electrons in their valence shells tend to readily accept electrons to achieve noble gas
configuration. In ionic bonding, more than 1 electron can be donated or received to
satisfy the octet rule. The charges on the anion and cation correspond to the number
of electrons donated or received. In ionic bonds, the net charge of the compound must
be zero.
This sodium molecule donates the lone electron in its valence orbital in order to
achieve octet configuration. This creates a positively charged cation due to the loss of
electron.
This chlorine atom receives one electron to achieve its octet configuration, which
creates a negatively charged anion.

Covalent Bonding
Covalent bonding is the sharing of electrons between atoms. This type of
bonding occurs between two atoms of the same element or of elements close to

each other in the periodic table. This bonding occurs primarily between nonmetals;
however, it can also be observed between nonmetals and metals.

REPRESENTING
MOLECULES
Octet Rule
- Octet rule, formulated
by Lewis: An atom other
than hydrogen tends to form
bonds until it is surrounded
by eight valence electrons.
- Single bond: In a
single bond, two atoms are held together by one electron pair.
- Double bond: two atoms share two pairs of electrons, the covalent bond is
called a double bond.
- A triple bond arises when two atoms share three pairs of electrons, as in the
nitrogen molecule (N2):

Electronegativity
- A property that helps us distinguish a nonpolar covalent bond from a polar
covalent bond
- Polar covalent bond: A polar covalent bond exists when atoms with different
electronegativities share electrons in a covalent bond. Consider the hydrogen
 chloride (HCl) molecule. Each atom in HCl requires one more electron to form
an inert gas electron configuration.
- Nonpolar covalent bonds are a type of bond that occurs when two atoms
share a pair of electrons with each other. These shared electrons glue two or
more atoms together to form a molecule. An example of a nonpolar covalent
bond is the bond between two hydrogen atoms because they equally share
the electrons.

Formal Charge

Formal charge is the electrical charge difference between the valence electrons in
an isolated atom and the number of electrons assigned to that atom in a Lewis
structure.
To assign the number of electrons on an atom in a Lewis structure, we proceed as
follows:
- All the atom’s nonbonding electrons are assigned to the atom.
Ex. Ozone molecule (O3)

- We break the bond(s) between the atom and other atom(s) and assign half of
the bonding electrons to the atom.

The formal charge on each atom in O3 can now be calculated according to the
following scheme:

Resonance
-
- Resonance structure: one of two or more Lewis structures for a single
molecule that cannot be represented accurately by only one Lewis structure.
The double-headed arrow indicates that the structures are resonance
structures.
- Resonance: the use of two or more Lewis structures to represent a particular
molecule.