History of Chemistry
A basic chemical hypothesis first emerged in
Classical Greece when Aristotle defined the four
elements of fire, air, earth, and water. It was not
until the 17th and 18th centuries when scientists
such as Robert Boyle (1627-1691) and Antoine
Lavoisier (1743-1794) began to reshape the old
alchemical traditions into a rigorous scientific
discipline.
Antoine-Laurent de Lavoisier  natural synthesis, and therefore, it would be
Antoine-Laurent de Lavoisier is considered the
“father of modern chemistry” for his work on the
principle of conservation of mass and for
developing a new system of chemical
nomenclature.
As one of the natural sciences, chemistry provides
scientists with insight into other physical sciences
and powerful analytical tools for engineering
applications. The biological sciences and their
offshoots, such as psychology, are rooted in
biochemistry, and scientists are only now beginning
to understand how the different levels of
organization influence each other. For example, the
basis of modern medicine is the biochemical
processes of the human body.
Chemistry and the Natural World
Chemistry has the power to explain innumerable
phenomena in the world, from the ordinary to the
bizarre. Why does iron rust? What makes propane
such an efficient, clean-burning fuel? How can soot
and diamond be so different in appearance yet so
chemically similar? Chemistry has the answer to
these questions and many more. Understanding
chemistry is the key to understanding the world as
we know it.
Different Branches of Chemistry
The study of chemistry can be organized into
distinct branches that emphasize subsets of
chemical concepts. Analytical chemistry seeks to
determine the exact chemical compositions of
substances. Biochemistry is the study of chemicals
found in living things (such as DNA and proteins).
Inorganic chemistry studies substances that do not
contain carbon. Organic chemistry studies
carbon-based substances. Physical chemistry is
the study of the physical properties of chemicals.
Biophysical chemistry is the application of physical
chemistry in a biological context.
INTRODUCTION TO ORGANIC CHEMISTRY
1.1  HISTORICAL BACKGROUND OF ORGANIC
CHEMISTRY
Organic chemistry is the area of chemistry that
involves the study of carbon and its compounds.
Carbon is now known to form a seemingly unlimited
number of compounds. The uses of organic
compounds impact our lives daily in medicine,
agriculture, and general life.
- In theory (Oparin, 1923) organic chemistry
may have its beginnings with the big bang
when the components of ammonia,
nitrogen, carbon dioxide and methane
combined to form amino acids, an
experiment that has been verified in the
laboratory (Miller, 1950). Organic chemicals
were used in ancient times by Romans and
Egyptians as dyes, medicines and poisons
from natural sources, but the chemical
composition of the substances was
unknown.
- In the 16th century organic compounds
were isolated from nature in the pure state
(Scheele, 1769) and analytical methods
were developed for determination of
elemental composition (Lavoisier, 1784).
- Scientists believed (Berzelius, 1807) that
organic chemicals found in nature contained
a special "vital force" that directed their
impossible to accomplish a laboratory
synthesis of the chemicals. Fortunately,
later in the century Frederich Wöhler (1828)
discovered that urea, a natural component
in urine, could be synthesized in the
laboratory by heating ammonium cyanate.
His discovery meant that the natural "vital
force" was not required to synthesis organic
compounds, and paved the way for many
chemists to synthesize organic compounds.
- By the middle of the nineteenth century
many advances had been made into the
discovery, analysis and synthesis of many
new organic compounds. Understanding
about the structures of organic chemistry
began with a theory of bonding called
valence theory (Kekule, Couper, 1858)
1.2  THE PRINCIPLES OF ATOMIC
THEORY’LEWIS STRUCTURE
The precise physical nature of atoms finally
emerged from a series of elegant experiments
carried out between 1895 and 1915. The most
notable of these achievements was Ernest
Rutherford's famous 1911 alpha-ray scattering
experiment, which established that
- Almost all of the mass of an atom is
contained within a tiny (and therefore
extremely dense) nucleus which carries a
positive electric charge whose value
identifies each element and is known as
the atomic number of the element.
- Almost all of the volume of an atom consists
of empty space in which electrons, the
fundamental carriers of negative electric
charge, reside. The extremely small mass of
the electron (1/1840 the mass of the
hydrogen nucleus) causes it to behave as a
quantum particle, which means that its
location at any moment cannot be specified;
the best we can do is describe its behavior
in terms of the probability of its manifesting
itself at any point in space. It is common
(but somewhat misleading) to describe the
volume of space in which the electrons of
an atom have a significant probability of
being found as the electron cloud. The latter
has no definite outer boundary, so neither
does the atom. The radius of an atom must
be defined arbitrarily, such as the boundary
in which the electron can be found with 95%
probability. Atomic radii are typically 30-300
pm.
 Figure 1.2.1: The structure of the nuclear atom
with a central nucleus and surrounding electrons.
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The nucleus is itself composed of two kinds of
particles. Protons are the carriers of positive
electric charge in the nucleus; the proton charge is
exactly the same as the electron charge, but of
opposite sign. This means that in any [electrically
neutral] atom, the number of protons in the nucleus
(often referred to as the nuclear charge) is
balanced by the same number of electrons outside
the nucleus. The other nuclear particle is
the neutron. As its name implies, this particle
carries no electrical charge. Its mass is almost the
same as that of the proton. Most nuclei contain
roughly equal numbers of neutrons and protons, so
we can say that these two particles together
account for almost all the mass of the atom.
Because the electrons of an atom are in contact
with the outside world, it is possible for one or more
electrons to be lost, or some new ones to be
added. The resulting electrically-charged atom is
called an ion.
Elements
To date, about 115 different elements have been
discovered; by definition, each is chemically
unique. To understand why they are unique, you
need to understand the structure of the atom (the
fundamental, individual particle of an element) and
the characteristics of its components. Atoms
consist of electrons, protons, and neutrons.
Although this is an oversimplification that ignores
the other subatomic particles that have been
discovered, it is sufficient for discussion of chemical
principles. Some properties of these subatomic
particles are summarized in Table 1.2.1, which
illustrates three important points:
1. Electrons and protons have electrical
charges that are identical in magnitude but
opposite in sign. Relative charges of −1 and
+1 are assigned to the electron and proton,
respectively.
2. Neutrons have approximately the same
mass as protons but no charge. They are
electrically neutral.
3. The mass of a proton or a neutron is about
1836 times greater than the mass of an
electron. Protons and neutrons constitute
the bulk of the mass of atoms.
The discovery of the electron and the proton was
crucial to the development of the modern model of
the atom and provides an excellent case study in
the application of the scientific method. In fact, the
elucidation of the atom’s structure is one of the
greatest detective stories in the history of science.
The atom consists of discrete particles that govern
its chemical and physical behavior. Each atom of
an element contains the same number of protons,
which is the atomic number (Z). Neutral atoms
have the same number of electrons and protons.
Atoms of an element that contain different numbers
of neutrons are called isotopes. Each isotope of a
given element has the same atomic number but a
different mass number (A), which is the sum of
the numbers of protons and neutrons. The relative
masses of atoms are reported using the atomic
mass unit (amu), which is defined as one-twelfth
of the mass of one atom of carbon-12, with 6
protons, 6 neutrons, and 6 electrons.
 
1.3. OVERVIEW OF THE NATURE AND
STRUCTURE OF ORGANIC COMPOUNDS
Scientists of the 18th and early 19th centuries
studied compounds obtained from plants and
animals and labeled them organic because they
were isolated from “organized” (living) systems.
Compounds isolated from nonliving systems, such
as rocks and ores, the atmosphere, and the
oceans, were labeled inorganic. For many years,
scientists thought organic compounds could be
made by only living organisms because they
possessed a vital force found only in living systems.
The vital force theory began to decline in 1828,
when the German chemist Friedrich Wöhler
synthesized urea from inorganic starting materials.
He reacted silver cyanate (AgOCN) and ammonium
chloride (NH4Cl), expecting to get ammonium
cyanate (NH4OCN). What he expected is described
by the following equation.
AgOCN+NH4Cl→AgCl+NH4OCN
Instead, he found the product to be urea
(NH2CONH2), a well-known organic material readily
isolated from urine. This result led to a series of
experiments in which a wide variety of organic
compounds were made from inorganic starting
materials. The vital force theory gradually went
away as chemists learned that they could make
many organic compounds in the laboratory.
Today organic chemistry is the study of the
chemistry of the carbon compounds, and inorganic
chemistry is the study of the chemistry of all other
elements. It may seem strange that we divide
chemistry into two branches—one that considers
compounds of only one element and one that
covers the 100-plus remaining elements. However,
this division seems more reasonable when we
consider that of tens of millions of compounds that
have been characterized, the overwhelming
majority are carbon compounds.
Organic compounds, like inorganic compounds,
obey all the natural laws. Often there is no clear
distinction in the chemical or physical properties
among organic and inorganic molecules.
Nevertheless, it is useful to compare typical
members of each class, as in Table 1.3.1
Table 1.3.1 General Contrasting Properties and
Examples of Organic and Inorganic Compounds
Keep in mind, however, that there are exceptions
to every category in this table. To further illustrate
typical differences among organic and inorganic
compounds, Table 26.1.126.1.1 also lists
properties of the inorganic compound sodium
chloride (common table salt, NaCl) and the organic
compound hexane (C6H14), a solvent that is used to
extract soybean oil from soybeans (among other
uses). Many compounds can be classified as
organic or inorganic by the presence or absence of
certain typical properties, as illustrated in
Table 1.3.1.
1.4. ELECTRONEGATIVITY AND BOND
POLARITY
ELECTRONEGATIVITY
Electronegativity is defined as the ability of an atom
in a particular molecule to attract electrons to itself.
The greater the value, the greater the
attractiveness for electrons.
Electronegativity is a function of:
1. the atom's ionization energy (how strongly
the atom holds on to its own electrons) and
2. the atom's electron affinity (how strongly
the atom attracts other electrons).
Both of these are properties of the isolated atom.
An element will be highly electronegative if it has a
large (negative) electron affinity and a high
ionization energy (always endothermic, or positive
for neutral atoms). Thus, it will attract electrons
from other atoms and resist having its own
electrons attracted away.
Figure 1.4.1 The electronegativity values derived
by Pauling follow predictable periodic trends with
the higher electronegativities toward the upper right
of the periodic table.
BOND POLARITY
The polarity of a bond—the extent to which it is
polar—is determined largely by the relative
electronegativities of the bonded atoms.
Electronegativity (χ) was defined as the ability of an
atom in a molecule or an ion to attract electrons to
itself. Thus there is a direct correlation between
electronegativity and bond polarity. A bond
is nonpolar if the bonded atoms have equal
electronegativities. If the electronegativities of the
bonded atoms are not equal, however, the bond
is polarized toward the more electronegative atom.
A bond in which the electronegativity of B (χB) is
greater than the electronegativity of A (χA), for
example, is indicated with the partial negative
charge on the more electronegative atom:
 
One way of estimating the ionic character of a bond
—that is, the magnitude of the charge separation in
a polar covalent bond—is to calculate the
difference in electronegativity between the two
atoms: Δχ = χB − χA.
To predict the polarity of the bonds in Cl 2, HCl, and
NaCl, for example, we look at the
electronegativities of the relevant atoms: χCl = 3.16,
χH = 2.20, and χNa = 0.93. Cl2 must be nonpolar
because the electronegativity difference (Δχ) is
zero; hence the two chlorine atoms share the
bonding electrons equally. In NaCl, Δχ is 2.23. This
high value is typical of an ionic compound (Δχ ≥
≈1.5) and means that the valence electron of
sodium has been completely transferred to chlorine
to form Na+ and Cl− ions. In HCl, however, Δχ is
only 0.96. The bonding electrons are more strongly
attracted to the more electronegative chlorine atom,
and so the charge distribution is
 
Remember that electronegativities are difficult to
measure precisely and different definitions produce
slightly different numbers. In practice, the polarity of
a bond is usually estimated rather than calculated.
Bond polarity and ionic character increase with an
increasing difference in electronegativity.
As with bond energies, the electronegativity of an
atom depends to some extent on its chemical
environment. It is therefore unlikely that the
reported electronegativities of a chlorine atom in
NaCl, Cl2, ClF5, and HClO4 would be exactly the
same.
1.5. RESONANCE AND FORMAL CHARGE
RESONANCE: A property of a compound that can
be visualized as having multiple structures differing
only in the distribution of electrons.
RESONANCE STRUCTURE: A way of describing
delocalized electrons within certain molecules or
polyatomic ions where the bonding cannot be
expressed by a single Lewis structure.
Lewis dot structures can be drawn to visualize the
electrons and bonds of a certain molecule.
However, for some molecules not all the bonding
possibilities cannot be represented by a single
Lewis structure; these molecules have several
contributing or “resonance” structures. In chemistry
terms, resonance describes the fact that electrons
are delocalized, or flow freely through the molecule,
which allows multiple structures to be possible for a
given molecule.
Each contributing resonance structure can be
visualized by drawing a Lewis structure; however, it
is important to note that each of these structures
cannot actually be observed in nature. That is, the
molecule does not actually go back and forth
between these configurations; rather, the true
structure is an approximate intermediate between
each of the structures. This intermediate has an
overall lower energy than each of the possible
configurations and is referred to as a resonance
hybrid. It is important to note that the difference
between each structure lies in the location of the
electrons and not in the arrangement of the atoms.
MORE THAN ONE VALID LEWIS STRUCTURE
For example, the nitrate ion, NO3–, has more than
one valid Lewis structure. The structure contains
two N-O single bonds and one N=O double bond.
But the question then remains as to which oxygen
should be involved in the double bond. Therefore,
three valid resonance structures can be drawn.
Double-ended arrows are used to indicate that the
structures are chemically equivalent. Again, in
reality, the electronic configuration does not change
between the three structures; rather, it has one
structure in which the extra electrons are distributed
evenly. These fractional bonds are sometimes
depicted by dashed arrows, which show that the
electron density is spread out throughout the
compound.
Resonance structures of the nitrate ion: The
nitrate ion has three valid contributing structures
that vary according to the placement of the
electrons.
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DRAWING RESONANCE STRUCTURES
When you are drawing resonance structures, it is
important to remember to shift only the electrons;
the atoms must have the same position.
Sometimes, resonance structures involve the
placement of positive and negative charges on
specific atoms. Because atoms with electric
charges are not as stable as atoms without electric
charges, these resonance structures will contribute
less to the overall resonance structure than a
structure with no charges.
FORMAL CHARGE: The charge assigned to an
atom in a molecule, assuming that electrons in a
chemical bond are shared equally between atoms.
This helps determine which of a few Lewis
structures is most correct.
DETERMINING FORMAL CHARGE
Although we know how many valence electrons are
present in a compound, it is harder to determine
around which atoms the electrons actually reside.
To assist with this problem, chemists often
calculate the formal charge of each atom. The
formal charge is the electric charge an atom would
have if all the electrons were shared equally.
The formal charge of an atom can be determined
by the following formula:
FC=V−(N+B2)FC=V−(N+B2)
In this formula, V represents the number of valence
electrons of the atom in isolation, N is the number
of non-bonding valence electrons, and B is the total
number of electrons in covalent bonds with other
atoms in the molecule.
For example, let’s calculate the formal charge on
an oxygen atom in a carbon dioxide (CO 2)
molecule:
FC = 6 valence electrons – (4 non-bonding valence
electrons + 4/2 electrons in covalent bonds)
FC = 6 – 6 = 0
The oxygen atom in carbon dioxide has a formal
charge of 0.
1.6. DIFFERENCES BETWEEN INORGANIC AND
ORGANIC COMPOUND
TYPES OF COMPOUNDS
Compounds are said to be of two types namely:
1.    Organic compounds
2.    Inorganic compounds
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content/uploads/2018/07/Organic-vs-Inorganic-
Compounds-700x327.png
DIFFERENCE BETWEEN ORGANIC AND
INORGANIC COMPOUNDS
Organic and inorganic compounds form one of the
primary basis for chemistry. The study of organic
compounds is termed as organic chemistry and the
study of inorganic compounds is inorganic
chemistry. These are said to be one of the large
class of members. The primary difference that lies
between these organic compounds and inorganic
compounds is that organic compounds always have
a carbon atom while most of the inorganic
compounds do not contain the carbon atom in
them. Almost all the organic compounds contain
the carbon-hydrogen or a simple C-H bond in them.
The most common fact that differentiates organic
compounds from inorganic compounds is that the
organic compounds mainly result from activities of
a living being. Whereas, inorganic compounds are
obtained from the natural processes which are not
related to any of the life forms on earth or any result
of human experiments which are conducted in
laboratories.
The difference between organic and inorganic
compounds does not end with the presence or the
absence of carbon atoms in them. These have
characteristics of both the types of compounds
which are said to be different.
 - Enzymes

DIFFERENCE BETWEEN ORGANIC AND

INORGANIC COMPOUNDS ORGANIC COMPOUNDS LACKING C-H BONDS

There are a few organic compounds containing

carbon, but no C-H bond. Examples include:
- Carbon tetrachloride, CCl4
- Urea, CO(NH2)2

EXAMPLES OF INORGANIC COMPOUNDS

Inorganic substances include all pure elements,

salts, many acids and bases, metals and alloys,
and minerals. Compounds in which a non-carbon
atom forms a chemical bond with hydrogen are
inorganic.

Examples of inorganic compounds include:

- Sodium chloride (table salt) (NaCl)
- Brass
- Glass and quartz (SiO2)
- Hydrochloric acid (HCl)
- Sulfuric acid (H2SO4)

INORGANIC MOLECULES CONTAINING

CARBON

A few inorganic compounds contain carbon. These

include the oxides, carbides, some carbonates, and
some cyanides, Examples include:
- Carbon dioxide (CO2)
- Cyanides (C-N bond)
- Carbides (e.g., boron carbide, B4C)
- Carbon disulfide (CS2)
- Phosgene (COCl2)

Note the hydrogen cyanide, HCN, contains both

carbon and hydrogen. It is usually considered to be
an inorganic compound because of the bond
between carbon and nitrogen. Diamond, graphite,
and graphene consist of pure carbon. They are
inorganic.

NEITHER ORGANIC NOR INORGANIC

Pure elements are not compounds, so they are

neither organic nor inorganic compounds:
- Argon (Ar)
- Silver (Ag)
- Sulfur (S)
- Carbon (C)
Not All Organics Come From Life

EXAMPLES OF ORGANIC COMPOUNDS
Compounds made within living organisms are
organic molecules. The main classes of organic
compounds are carbohydrates, fats, proteins, and
nucleic acids.
Examples of organic substances include:
- Sucrose (table sugar), C12H22O11
- Methane, CH4
- DNA
- Benzene, C6H6
- Ethanol (grain alcohol), C2H6O
- Coal
- Hair and fingernails (keratin protein)
- Cellulose
- Butter
Most organic compounds are made within living
organisms, but the molecules may form via other
processes. For example, organic compounds found
on Mars or within a nebula aren’t necessarily signs
of extra-terrestrial life. Solar radiation can supply
the energy needed to convert inorganic compounds
into organics.
1.7. REACTION MECHANISM
Reaction mechanism, in chemical reactions, the
detailed processes by which chemical substances
are transformed into other substances. The
reactions themselves may involve the interactions
of atoms, molecules, ions, electrons, and free
radicals, and they may take place in gases, liquids,
or solids—or at interfaces between any of these.

- Generally, the chemical reactions whose
mechanisms are of interest to chemists are
those that occur in solution and involve the
breaking and reforming of covalent
bonds between atoms—covalent bonds
being those in which electrons are shared
between atoms.
- There are a number of techniques by which
the mechanisms of such reactions can be
investigated.
- Chemical reactions involve changes in
bonding patterns of molecules—that is,
changes in the relative positions of atoms in
and among molecules, as well as shifts in
the electrons that hold the atoms together in
chemical bonds. Reaction mechanisms,
therefore, must include descriptions of these
movements with regard to spatial change
and also with regard to time. The overall
route of change is called the course of the
reaction, and the detailed process by which
the change occurs is referred to as the
reaction path or pathway.
GENERAL CONSIDERATIONS
DETERMINANTS OF THE COURSE OF
REACTION
THE REACTANTS
In analyzing the mechanism of a reaction, account
must be taken of all the factors that influence its
course. After the bulk chemical constituents have
been identified by ordinary methods of structure
determination and analysis, any prereaction
changes involving the reactants, either individually
or together, must be investigated.
THE TRANSITION STATE
The transition state, or activated complex, is the
fleeting molecular configuration that exists at the
top of the energy barrier that the reactants must
surmount to become the products. It is not strictly a
component of the reaction system, and it cannot be
examined directly in the way that an intermediate
(however unstable) can, because it lasts no longer
than the duration of a molecular collision. The
transition state may have properties of its own, not
reflected in those of the starting materials or of the
products and of the reaction, and so it is of vital
importance in determining the course of
reaction. Inference concerning the nature of the
transition state is the essence of mechanistic study.
Catalysts are substances that speed up a reaction
by facilitating a particular mechanism—sometimes
by influencing an existing prereaction and
sometimes by making a new process energetically
favourable. Their presence or absence frequently
determines the course a reaction may take, simply
because one of a number of competing reactions
is, or is not, favoured. (Most catalysts are changed
chemically while they speed up a reaction;
sometimes—but not always—they are consumed,
and sometimes they are reformed and so appear to
be unchanged in concentration during a reaction.)
 
THE PRODUCTS
All reactions are reversible in principle, and the
nature of the products of the reaction can affect the
reaction course in a number of ways. When the
position of equilibrium is unfavourable, for example,
the accumulation of products may cause a reversal
of the reaction. In such circumstances, the physical
removal of the products (through their volatility or
insolubility, for example) facilitates the completion
of the forward process. Sometimes too, one of the
products acts as a catalyst or as an inhibitor,
behaviour that strongly influences the course of the
reaction.
 
THE REACTION CONDITIONS
The conditions under which some reaction occurs,
including such variables as the temperature and
concentrations of reactants, also are important in
determining the course of the reaction. For
reactions that have a high energy barrier between
reactants and products, the rate is highly
responsive to change in temperature, and such
reactions become more likely at increased
temperatures, so the minor products of a reaction
often appear in larger proportions at higher
temperatures.

THE SOLVENT

The solvent, or medium in which the reaction

occurs, may perform the mechanical—but often
vital—role of allowing otherwise immiscible
reactants to come together rapidly. Among the
important groups of solvents, each with its own
special type of behaviour, are hydroxylic solvents
(the molecules of which contain hydroxyl [―OH]
groups, such as water and alcohols), dipolar aprotic
solvents (the molecules of which show a separation
of electrical charge but do not easily give up
a proton, or positive hydrogen ion; e.g., acetone),
and nonpolar solvents (the molecules of which do
not show charge separation; e.g., hexane).

CATALYSTS