j\'f u.

ior Paper - tr

General Chemistry - 1

First - Yerlr
Major Paper - I
General Chemistry- -I

Unit 1: Atomic structure, Pcriodic Propertieso Theories of volumetric And Scmimicro

Qualitative Analyses.
1.1 Atomic Orbitals. quantum numbers - Principal, azimuthal, magnetic and spin quantunl
nuntbtrs and their significance-Plinciples goveming the occupancy of eleclrons in various
quantum levels-Pauli's exclusion principle" Hund's rule, Aufbau Principie' (n+l) rule'
stability of half-filled and fully filled orbitals.

L2 Classification as s, p, d & f block elements, variation of atomic volume, atomic and ronic
radii, ionisation potential, electron affinity and electronegativity along periods and groups -
Factors influencing the periodic properties.

1.3 Inorgilnic Qualitative Anal)'sis: Solubitity Product - Principle of Elimination of

ilterfering anions, ,Common ion Effect - Complexation reactions including spot tests itl
qualitative analysis - Reactions involved in separation and identification of cations and
anions in the analysis - Semi Micro Techniques .

I .4Titrimetry: Definitions of I\4ola[ity, normality, molality and mole fiaction - Primarl and
Secondary standards - Types of titrimetric reactions - acid-base. redox, precipitation and
complexometric titrations - Indicators - Effect of change in pH - theory of neutralizaliotl,
redox, adsorption and metal ion indicators.

Unit 2: Chemical bonding and chemistry of s- block elements

2.1 lonic bond - Lattice Energy - Bom - Haber Cycle - Pauling and Mulliken's scales of
electronegativity - Polarizing power and Polarisability - partial ionic character from electro-
negativity - Transitions from ionic to covalent character and vice versa - Fajan's rules'

2.2 VESPR Theory Shapes of simple inorganic molecules (BeCl2, SiCl+ PCls, SFe, IFr,
-
NH:, XeFa, XeF6, XeO:, XeOF+, BFr, and H2O ) - VB Theory - Principles of hybridizatiou -
MO Theory - Bonding and antibonding orbitals - Application of MO Theory to Hz, Hez, Nz,
Oz, HF and CO - Comparison of VB and MO Theories.

2.3 S-block elements General chalacteristics of Group IA elements - diagonal relationship

between Li and Mg - general methods of extraction. physical, chemical properties and uses
of Lithium, Sodium and Potassium.

L
(ieneral characterislics ol- Irici:renii qrl (iroup llA - diagonal relationship betv,een Be and z\l
- -
Extraction of Be"rylliunr. \launcsiunr and Calcium Ph1'sical. chenticai propeflies and
[-]ses.

Unit 3: Theories of Covalent Bonding and Structure, Chemistrl of Alkanes and

Cycloalkanes

3.1 Covalent bonding - hybridization - Structure of organic molecules based on sp3. sp'?and
sp hybridization -properties of covalent molecules: bond lenglh. bond angle. bond energy.
bond polarity. inductive, mesomeric. electromeric, resonance and hyperconj ugative effects.

3.2 IUPAC nomenclature oforganic compounds (up to l0 carbon systems) - Hydrocarbons -

- -
Mono functional compounds Bifunctional compounds Isomerism Types of isomerism
(structural and stereoisomerisms) with appropriate examples.

3.3 Petroleum- Coal tar distillation- source of alkanes - Methods of preparing alkanes and
cycloalkanes - Chemical properties - Halogenation of alkanes - Mechanism of free radical
substitution - Conformational study of ethane and n-butane - Relative stability of
cycloalkanes (from cyclopropane up to cyclooctane) - Bayer's Strain theory - Limitations -
Conformational study of cyclohexane, mono and disubstituted cyclohexanes.

Unit 4: Chemistry of Alkenes, AlkTnes, Dienes, Benzene and Benzenoid Compounds.

4.1 Chemistry of alkenes, alkynes and dienes: Nomenclature of alkenes - Geometrical
Isomerism General methods of preparation of alkenes - Chemical properties - Uses -
-
Elimination mechanisms (Er,Ez) - Electrophilic, Free radical additions - Ziegler - Natta
Catalytic polymerization of ethylene - polymers of alkene derivatives. Nomenclature of
alkynes- General methods of preparation of alkynes - Physical and Chemical properties -
Uses.

4.2 General methods of preparation of Dienes and types- Physical and Chemical properties -
Uses - Mechanisms of electrophilic and Free radical addition reactions - Rubber as a natural
polymer.

4.3 General methods of preparation of benzene - Chemical properties - Uses - Electrophilic

substitution mechanism - Orientation and reactivity in substituted benzenes. Polynuclear
Aromatic compounds - Nomenclature -Laboratory preparation of Naphthalene, Anthracene
and Phenanthrene -Structure, aromatic character, physical, chemical properties and uses of
Naphthalene, Anthracene and Phenanthrene -Mechanism of Aromatic electrophilic
substitution - Theory of orientation and reactivity

Unit 5: Atomic Structure, Molecular Velocities and Real Gases

5.1 Dualism of light - Wave nature of radiation, classical theory of electromagnetic radiation
and classical expression for energy in terms of amplitude. Particle nature ofradiation - Black
body radiation and Planck's quantum theory, photoelectric effect and Compton effect of
matter - de Broglie hypothesis and Davisson and Germer experiment. Heisenberg's
uncertainty principle. Schrodinger wave equation - arguments in favour of Schrodinger wave
 equalion. Phrsrcal significance of y trnd r,,rl 1i:::r:lrorr:'. 'v\iar,'e picture of electron -.C onec1.rt o1'
atomic orbitals. Shapes of s, p and d or,.ritals \o.1al planes and nodal points in al(]nrie
orbitals- g and u character of alomic orbitals.

5.2 Maxu'ell's distribution of Moleculal vciocities (Derivation not required). '[1'pe-s ol

Molecular velocities - Mean, Most probablc and root mean square velocities. Graphical
representation and its significance - Collision diameler. Mean free path and collisiorl number.
Real gases - r,an der Waals equation ofslales - deril'atiol.Law ofcorresponding states.

Recommended Books:
1. Soni. P.L. Textbook of Inorganic Chemistrl. S. Chand & sons, New Delhi, (2010)
2. Soni. P.L. and Chawla H.M., Textbook of Organic Chemistry, S. Chand & sons, Neu,
Delhi, (2010)
3. Soni. P.L. and Dharmarha O.P. Textbook of Physical Chemistry, S. Chand & sons. New
Delhi, (2010)
4. Puri B.R..,Sharma L.R., Kalia K.K., Principles of Inorganic Chernistry, (23rd edition),
New Delhi, Shoban Lal Nagin Chand & Co., ( I 993).
5. Puri B.R..,Sharma L.R., Pathania M.S., Principles of Physical Chemistry, (23rd edition),
New Delhi, Shoban Lal Nagin Chand & Co., (1993).

Books for reference:

1. Lee J.D., Concise Inorganic Chemistry, UK, Black well science (2006).
2. Glasstone S., Lewis D., Elements of Physical Chemistry, London, Mac Millan & Co. Ltd.
3. Morrison R.T. and Boyd R.N., Organic Chemistry (6th edition), New york, Allyn &
Bacon Ltd., (1976).
4' Bahl B.s. and Arun Bahl, Advanced organic chemistry, (l2th edition), New Delhi, sultan
Chand& Co.,(1997).
5. Frank J. welcher and Richard B. Hahn, semi micro
eualitative Analysis, New Delhi,
Affiliated East-west Press Pvr.Ltd. (1969).

3
[.]nit l:
.'\tomic structure, Perioriic Propcrties, Theorics of volumetric and Semi micro
Qualitativc Analy,ses.

l. t. Atomic orbitals

Atomic orbitals are regions of space around the nucleus of an atom rvhere an electron
is likell ttr be found. Atomic orbitals allou, atoms to make covalent bonds. The n.rosr
comnrcrnll, filled orbitals arc s, p, r/. and I S orbitals have no angular nodes and are
sphericlli. P olbitals have a single angular node across the nucleus and are shaped like
dun-rbbells. D and fhave two and three angular nodes, respectivety. Only tu,o electrons tvill
be found in any orbital space as defined by the Pauli Exclusion Principle. Once a shell of
orbitals is completely filled, a new set of orbitals (2s. 2p, and so on) is available. 2p rvould
have one angular node, like 1p, but also one radial node.

1.1.1. Orbitals

The number oforbitals in a subshell is equivalent to the number of values the

magnetic quantum number ml takes on. A helpful equation to determine the number of
orbitals in a subshell is 2l +1. This equation will not give y.ou the value of ml, but the number
of possible values that ml can take on in a particular orbital. For example, if l=1 and ml can
have values -1, 0, or +1, the value of 2l+1 will be three and there will be three different
orbitals. The names ofthe orbitals are named after the subshells they are found in:

In the figure below, we see examples of two orbitals: the p orbital (blue) and the s

orbital (red). The red s orbital is a 1s orbital. To picture a 2s orbital, imagine a layer similar to
a cross section of a jawbreaker around the circle. The layers are depicting the atoms angular

nodes. To picture a 3s orbital, imagine another layer around the circle, and so on and so on.
The p orbital is similar to the shape of a dumbbell, with its orientation within a subshell
depending on mr. The shape and orientation ofan orbital depends on I and mr.

The shape of the wave funclion

The shape ofthe vravefunction wheol=0(sorbital)
d. whenl=1(porbital)

4
 I.1.2 Principal quantum number

In quantum mechanics. tlre principal quantum number is1mbolized z) is orre ol'

four quant\rm numbers rvhich are assigned to all electrons in irn atont to describe that
electron's state. As a discrcte variable. the principal quantunt number is always an integer.
As'r increases, the number of electronic shells increases and the electron spends

more time farther frorn the nucleus. As n increases. the electron is also at a higher energy and
is, therefore. less tightly bound to the nucleus. The total errergv of an electron, fs described
below, is a negative inverse quadratic function ofthe principal quantunl number r.
The principal quantum nurnber uas first created for use in the semiclassical Bohr
model of the atom, distinguishing between different energy levels. With the development of
modem quantum mechanics. the simple Bohr model was replaced with a more complex
theory ofatomic orbitals. Hou,ever, the modem theory still requires the principal quantum
number.

Apart from the principal quantum number, the other quantum numbers
for bodfid electrons are the azimuthal quantum number t, the magnetic quantum :lrrrber mb
and the spin quantum,number s.

There are a set of quantum numbers associated with the energy states ofthe atom. The
four quantum numbets r, l, m, and s specify the complete and unique quantum state of a
single electron in an atom, called its wave function or orbital. Two electrons belonging to the
same atom cannot have the same values for all four quantum numbers, due to the Pauli
Exclusion Principle. The wave functiolt of the Schrddinger wave equation reduces to the
three equations that when solved lead to the first three quantum numbers. Therefore, the
equations for the first three quantum numbers are all interrelated.

The principal quantum number, n, designates the principal electron shell.

Because z describes the most probable distance of the electrons from the nucleus, the larger

the number n is, the farther the electron is from the nucleus, the larger the size ofthe orbital,
, at t'. k
andCf larger thi6?om isnr can be any positive integer starting at l, n:\6:/ deiilnates
v as
Y,u
the first principal shell (the innermost shell). The first principal shell is also called the ground
state, or lowest energy state. This explains why n cannot be 0 or any negative integer,
because there exists no atoms with zpro or a negative amount of energy levels/principal
shells. When an electron is in an excited state or it gains energy, it may jump to the second
pritlciplc sht'll. rrlir'r,.:r }r.-.J. Ihi' is calleJ uh\(,lpri('r) h((Jrr.\'11'rc electron is "0hsrrplr;11,,'
f
photons" or energ\. Kno,.Lr as enlission- electrons can also "cmit" energy as they.iump to

lower principie sheils. lll.rcre n decreases by rvhole numbers. ;\s the energl, of the eleclron
increases, so does the principal quantum nunber. e.g.. /r = the third principal
--l indicates
shell, r:4 indicates rhe fourrh principal shell, and so on.

n-t.2,3.4.. .

1.1.3 Azimuthal Quantum Number

The azimuthal quantum number is a quantun number for an atomic orbital that
determines its orbital angular momentum and describes the shape of the orbital. The
azimuthal quantum number is the second q[ a set of quantun'r numbers which describe the
unique quantum state of an electron (the others being the principal quantum number,
following spectroscopic notation, the magnetic quantum number, and the spin quantun'r
number). It is also known as the orbital angular momentum quantum numberJ*hilab
quertum
- nu*hgr,,br'gecond
_,L / quantum number, and is symbolized as [.

with the energy states of the atom's electrons are four quantum
Connected
numbers: n,l,m2, and m". These specifu the complete, unique quantum state of a single
electron in an atom, and make up its wave function or orbital. The wave function of
the Schrddinger equation reduces to three equations that when solved, lead to the first three
quantum numbers. Therefore, the equations for the first three quantum numbers are all
interrelated. The azimuthal quantum number arose in the solution of the polar part of the
wave equation as shown below. To aid understanding of this concept of the azimuth, it may
also prove helpful to review spherical coordinate systems, and/or other altemative
mathernatical coordinate systems besides the Cartesian coordinate system. Generally, the
spherical coordinate system works best with spherical models, the cylindrical system with
cylinders, the cartesian with general volumes, etc.

6
 Illustration of quantum mechanical orbital
angular momentum.

Atomic orbitals have distinctive shapes denoted by letters. In the illustration, the
letters s, p, and d describe the shape ofthe atomic orbital.

Their wavefunctions take the form of spherical harmonics, and so are described
by Legendre poll,nomials. The various orbitals relating to different values oflare
sometimes called sub-shells, and (mainly for historical reasons) are referred to by letters,
as follows:

l-ti<r^ri..l

o s 2 spherical

! p 6)

d 10 diffuse

7
 "unique shape #2" (see lbls p1e_tgle_orl5ptbCliga!
f fundamental
ha rmonics, bottom row qe!tgl')

818

5 22

I 2t)

The letters after the f sub-shell just follow letter f in alphabetical order except the letter j and those
a lready used.

Each of the different angular momentum states can take 2(21 + 1) electrons. This is
because the third quantum number rz1 (which can be thought of loosely as
the quantized.[rojection of the angular momentum vector on the z-axis) runs from -t to t in
integer units, and so there are 2l+ 1 possible state. Each distinct n,{, ml orbital can be
occupied by two electrons with opposing spins (given by the quantum ntmber m,:rYz),
giving 2(2t + 1) electrons overall. Orbitals with higher I than given in the table are perfectly
permissible, but these values cover all atoms so far discovered.
For a given value of the principal quantum number n, the possible values ofl range
/subshell
from 0 to n - 1; therefore , the n:1 shell only possesses 6is and can only take
2 electrons, the n :2 shell possesses qa s and 6'p subshell and can take 8 electrons overall,
the n : 3 shell possesses s, p, and d subshells and has a maximum of 18 electrons, and so on.
Generally speaking, the maximum number ofelectrons in the rth energy level is 2n2.

The angular momentum quantum number, /, govems the number of planar nodes going

through the nucleus. A planar node can be described in an .electromagnetic wave as the

midpoint between crest and trough, which has zero magnitude. In an s orbital, no nodes go
through the nucleus, therefore the corresponding azimuthal quantum number / takes the value

of 0. In ap orbital, one node traverses the nucleus and therefore / has the value of
1. Depending on the value ofr, there is an angular momentum quantum number / and the

following series. The wavelengths listed are for a hydrogen atom:

. Lyman series (ultraviolet)
. Balmer series (visible)

8
 Ilitz-l'iischen series (near infrared )

Brackctl series (shor1-wavelength intiared )

I Pfu nd series (mid-wavelength inirared ).

l 1.3.1 The Orbital Angular Momentum Quantum Number (f)

The orbital angular momentum quantum number I determines the shape of an orbital.

and therefore the angular distribution. The number of angular nodes is equal to the value of
the angular momentum quantum numberl. (For more information about angular nodes.

see Electronic Orbitals.) Each value ofl indicates a specific s. p, d, f subshell (each unique in
shape.) The value of I is dependent on the principal quantum number n. Unlike n, the value
ofl can be zero. It can also be a positive integer, but it cannot be larger than one less than the
principal quantum number (n-1):

t:0,t,2,3,4...,(n-1)

1.1.4 The Magnetic Quantum Number (m/)

The magnetic quantum number ml determines the number of orbitals and their
orientation within a subshell. Consequently, its value depends on the orbital angular
momentum quantum number 1. Given a certain 1,@ an interval ranging from -1 -l to +l
+1, so it can be zero, a negative integer, or a positive integer.

m t = -1, (-l+1), (-l+2), ...,-2, -1, 0,t,2,... (l-t), 0-2), +l

1.1.4.1 A Closer Look at Shells and Subshells

Principal Shells
The value of the principal quantum number n is the level of the principal electronic
shell (principal level). All orbitals that have the same n value are in the same principal level.
For example, all orbitals on the second principal level have a principal quantum number of
n:2. When the value ofn is higher, the number of principal electronic shells is greater. This
causes a geater distance between the farthest electron and the nucleus. As a result, the size of

tJle atom and its atomic radius increases.

9
 IJecarrsu il.re alomic ratlius increases- tire c'leclL'ons are farther h'om the nucleus. lhLrs

it is easiel fot the atom 1o expel an electrotr because Ihe nucleus does not have as strong a pull
on it, and the ior.rization energy decreases.
Subshells
The number of values of the orbital angular number I can also be used to identifl, the
number of subshells in a principal electron shell:
. When n: 1. l: 0 (l takes on one value and thus there can only be one subshell)
. When n: 2. l: 0, I (l takes on two values and thus there are two possible subshells)
. When n : 3, l: 0, 1, 2 (l takes on lluee values and thus there are three possible
subshells)
After looking at the examples above, we see that the value of n is equal to the number of
subshells in a principal electronic shell:
. Principal shell with n: t has one subshell

. Principal shell with n = 2 has two subshells

. Principal shell with n:3 has three subshells

To identifz what type of possible subshells n has, these subshells have been assigned letter
names. The value of I detemrines the name of the subshell:

Name of Subshell Value of ll

s subshell U

p subshell t

d subshell 2

f subshell 3

Therefore:
. Principal shell withn: t has one s subshell (l = 0)
. Principal shell with n:2 has one s subshell and one p subshell 0 = 0, l)
. Principal shell with n = 3 has one s subshell, one p subshell, and one d subshell (l:0,
t,2)

10
 We can designale a prircipir: :lLluntunr tlunrtrer, n. ancl a cenair] siitrshcll b! cornbining 1hc
' \'alue ofn and the narne o1'thL'sirhshell (rvhich can he found using l). I;or cxample.3p refels
.- to the third principal quantuln nunrber (n:3) arrd the p subshell (l-l ).

1.1.5 Pauli's Exclusion Principle

The Pauli Exclusion Plinciple says that every electron must be in ils own unique state.
- In other words, no electrons in an atom are permitted to have an identical set of quantum
- numbers.

electron arrangements in atoms and molecules, and helping to rationalize pattems in

_ the periodic table.

In chemistry the Pauli Exclusion Principle is applied solely to electrons, which we are
about to discuss.

- applied to electrons.

- will mention at the end of this page.

numh*r *f
elcctr*ns
1
r3-sf
priicipal orBttat
quentu m angutar
nu m hsr momentum
1.1.5.2 Four Quantum Numbers
Every electron in an atom can be defined completely by four quantum numbers:

r' n: the principal quantum number

/ l: the orbital angular momentum quantum number

 / trtr: tlre ;nagnr'lic r;uarttunr nunrber'

/ m,: the spin tltmnturn number

1.1.5.3 Example of the Pauli Exclusion Principle

Consider argon's electron configuration:

1s' 2s2 2pu 3s' 3pu

The exclusion principle asserts that every electron in an argon atom is in a unique state.

4s-_-
ut
!.-...
(u
E
LIJ 3p-Lr- ti t+
E
(} +t
(J ==
(u
LIJ

E
.,_ ++
-l- px -p,
t+ Et+
\.r,
(tr
(u
&c8 g
(J There a re
E
,* f* three d lfferent
f;#i5;,5,::
to one another

!2
 The ls level ctrn accommodale tw'o eiectr{)ns i.r it}r identical n. l. and mi quarlul)l rLrrrirers.
r\rgon's pair ol'electrons in the ls orbital satisll lhe exclusion principlc because thry hare
opposite spins. r.neaning they have diflerent spi:r quantum numbers. m.. OrrL'spin rs *;.':- the

,e,
other is -7r. (lnstead of saying it/z or -Yz otien the clectrons are said to be spin-up I or spin-
j
-L"
down Y.)
The 2s level electrons have a different principal quantum number to those in the ls orbital.
The pair of2s eiectrons differ from each other because they have opposite spins.

The 2p level electrons have a different orbital angular momentum number from those in the s

orbitals, hence the letter p rather than s. There are three p orbitals of equal energy. the px,
p, and p,. These orbitals are different from one another because they have different
orientations in space. Each of the p", py md pz orbitals can accommodate a pair of electrons
with opposite spins.

The 3s level rises to a higher principal quantum number; this orbital accommodates an
electron pair with opposite spins.

The 3p level's description is similar to that for 2p, but the principal quantum number is
higher: 3p lies at a higher energy than 2p.

.- ,.r.U Hund's Rule

.- Hund's rule states that the lowest energy electron configuration, the ground state, in
._ any electron subshell is the one with the greatest number ofparallel electron spins.

- Example I

, Consider the different ways in which a pair of electrons might be arranged in p

orbitals. Bearing in mind that we need to satisfr the Pauli exclusion principle, the three
,.
possible ways are shown below:

tt
rr- ft-
13
ll:c I:iddie option has the grealesl nunlr.cr ()i parallel electron spins and tllcrelirrc has the
lL)\\'es'i energ\'. i.e. Hund's rule identilies the n',idille option as the electlonic srouitd state. It is
the ground state because:

. accommodating the electrons in the same orbital lthe leftmost option) increasc.s the
electrostatic repulsion betrveen the electrons because on average the) are closer
together

. electrons with opposite spins (the rightmost option) tend to move closer to one
another than if spins are parallel (spin con€lation). If electrons are closer, the
electrostatic repulsion between them increases
Bxample 2

Here arc some ofthe ways three electrons could be placed into p orbitals.

/
r r| t| Ir Ir Ir r /r
Irl
tI I
ir r
t r
r I
r

I
abcde
Options (b) and (e) have the greatest number ofparallel electron spins and therefore the
lowest energy. Options (b) and (e) have the same energy
- they ate said to be degenerate orbitals.
Example 3

Here are some of the ways two electrons could be placed into d orbitals.

L*-__
ri LL__-
r
lt
' (a) r

(b) (c)
Options (b),(c), and (d) have the greatest number ofparallel electron spins and therefore the
lowest energy. Options (b),(c), and (d) have the same energy
- they are said to be degenerate orbitals.

1.1,7 Aufbau Principle

Aufbau (German word) means 'building up' according to Aufbau principle. "The
vacant subshell having lowest energy is filled first. When this subshell is filled completely,
then the filling ofnext sub-shell with higher energy starts."
The energy level diagram is

L4
 5;7;.1
/:'//")

The aulbau principle says that the arrangement of electrons in an atom - the electron
configuration - is best understood if it is built from the ground up. When writing down an
atom's electron configuration, we begin at the lowest energy level and add electrons to higher
energy sublevels until the required number of electrons are present.

We do so in accordance with the Pauli Exclusion Principle and Hund's Rule.

The diagram below shows as many electron energy levels as we need for most purposes in
general chemistry, although higher levels also exist. Energy levels are filled from the bottom

up.
5I 7s
--- --- 6o
5d
**_4f *::* 6s

**--- 4d
5o

s
4D
t.l
----- 3D
3€

s
_2&*
2s

15
l.l.7.l Element I - Hr drogen
lhe simplest ei!'r1rcnt. hydrogen, has one electron.

3s*3pa3d

2set2p

lr'
Hydrogen has a single eleclron. In its ground state, hydrogen's electron occupies the ls
energt level. Note the energt of 2s and 2p are equal for hydrogen - likewise 3s, jp and 3d.
This is not the case for any other element's atoms.

* The aufbau principle places hydrogen's electron in the lowest available energy level.
the ls.
This is hydrogen's ground state. It is written 1sl.
n Hydrogen is unique among the elements - it is the only one whose atoms have just one
electron. As a result of this, hydrogen has unique energy levels.
.:. The lack of electron-electron repulsion in hydrogen means its sublevels are ofequal
energy: in hydrogen 2s and 2p are ofequal energy; likewise,3s, 3p, and 3d are of
equal energy, etc.

1.1.7.2 Element 2 - Helium

Helium's two electrons fill the 1s orbital, giving a ground state electron configuration of 1s'?.

2p

-2s

l-l
rl rs
Helium's ground state.
 One electron is spin-up an,-l tlrc is orher spin-down in accordancc u irl.: lh,: l)auli

exclusion principle. This is callc-d spin pairing.

1'he quantum numbers ol'one ol'hclium's electrons are:
n: 1.1= 0. m, = 0. tns: +y2

And the other electron's quantum numbers are:

n- 1,1-0. mr - 0. m,: -/z
* Helium's first energy shell (rvith principal quantum number, n = l) is full. This is a
pafticularly stable configuration, leading to helium's lack of chen.rical reactivity.

1.1.8 Madelung energy ordering rule

n + { rule, also known as

The order in which subshells are filled is given by the
the Madelung rule (after Erwin Madelung), or the Janet ruleor the Klechkowsky
rule (after Charles Janet or Vsevolod Klechkovsky in some, mostly French and Russian-
speaking, countries), or the diagonal rule.

The states crossed by same red arrow have same n + I value.

The direction of the red arrow indicates the order of state filling.

Orbitals with a lower n + / value are filled before those with higher n + / values. In
this context, n represents the principal quantum number and /the azimuthal quantum
number; the values /: 0, 1,2, 3 correspond to the s,p, d, andflabels, respectively. The
subshell ordering by this rule is 1s, 2s, 2p,3s,3p, 4s,3d,4p,5s, 4d, 5p, 6s, 4f, 5d, 6p,7s, 5f,
6d,7p,8s"...

The rule is based on the total number of nodes in the atomic orbital. n + { which is
related to the energy6ln the case of equal n + / values, the orbital with a lower z value is

L7
illled llrst. 'l'he fact that r.nos1 ol-1hc grountl stale configuratio:-rs t;f rei:rlai aloms lill orbitals
1'ollorving this n + I, r? pattern ,,r,as obtained erperimentally, by ref'ererrcc to the spectroscopic
characteristics of, the elements-

The Madelung energl'oldering rule applies only to neutral atoms in their ground state.
There are 10 elements among transition metalsand 9 elements among
the
the Lanthanoids and Actinoids fbr u,hich the Madelung rute predicts atl electron
configuration that differc from that determined exp:rimentally by one electron orbit (in the
case of Palladium and Thorium by t\,\,o electron orbits).

1,1.9 Stabitity of Half-Filled and Fully Filled Orbitals

The exactly half-filled and fully filled orbitals have greater stability than other
configurations.

The reasons for their stability are symmefty and exchange energy.

(a) Symmetry

The half-filled and fully-filted orbitals are more symmetrical than any other
configuration and symmetry leads to greater stability.

(b) Exchange Enerry

The electrons present in the different orbitals ofthe same sub-shell can exchange their
positions. Each such exchange leads to the decrease in energy known as Exchange Energy.
Greater the number of exchanges, greater the exchange energy and hence greater the stability.
As the number of exchanges that take place in the half-filled and fully-filled orbitals is
maximum, thus exchange energy is maximum and hence maximum stability.

1.2. PERIODIC TABLE

1.2.1 The History of the Periodic Table

The modem periodic table has evolved through a long history of attempts by chemists
to arange the elements according to their properties as an aid in predicting chemical
behavior. One ofthe first to suggest such an arralgement was the German chemist Johannes
Dobereiner (1780-1849), who noticed that many of the known elements could be grouped
in triads, sets of three elements that have similar properties-for example, chlorine, bromine,
and iodine; or copper, silver, and gold. Dobereiner proposed that all elements could be
grouped in such triads, but subsequent attempts to expand his concept were unsuccessful. We
now' kno\\ ihitl )(Jr'tions of the periodic tablc--..rhe r/ biock in parlicular tontain tllarrs o1

elemenls u,ith sirb-stantial sirnilarities. 'l'he micidie three members of most of thc or.her
columns. suclr as sulfur, selenium, and tellurium in group 16 or aluminuni. galliur- and
indium in group I -3. also have remarkably similar chemistry..
81' the rnid- l 9th century, the atomic masses of many of the elements had been
determined. The English chemist John Nevvlands (1833 1898). hypothesizing thal the
chemistry of the elements might be related to their masses. aranged the known elernents ilr
otder of increasing atomic mass and discovered that every seventh element had similar
prope(ies ("The Arrangement ofthe Elements into Octaves as Proposed by Newlands"). (The
noble gases were still unlnown.) Newlands therefore suggested that the elements could be
classified into octaves, corresponding lo the horizontal rows in the main gtoup elements.
Unfortunately, Newlands's "lau, of octaves" did not seem to work for elements heavier than
calcium, and his idea was publicly ridiculed. At one scientific meeting, Newlands was asked
why he didn't anange the elements in alphabetical order instead of by atomic mass, since that
would make just as much sense! Actually, Newlands was on the right track-with only a few
exceptions, atomic mass does increase with atomic nunber, and similar properties occur
every time a sel of ns2np6 subshells is filled. Despite the fact that Newlands's table had no
logical place for the d-block elements, he was honored for his idea by the Royal Society of
London in 1887.
The periodic table achieved its modem form through the work of the German chemist
Julius Lothar Meyer (1830-1895) and the Russian chemist Dimitri Mendeleev (1834-1907),
both of whom focused on the relationships between atomic mass and various physical and
chemical properties. In 1869; they independently proposed essentially identical arangements
of the elements. Meyer aligned the elements in his table according to periodic variations in
simple atomic properties, such as "atomic volume" (Figure 7.2 "Variation of Atomic Volume
with Atomic Number, Adapted from Meyer's Plot of 1870"), which he obtained by dividing
the atomic mass (molar mass) in gams per mole by the density of the element in grams per
cubic centimeter. This property is equivalent to what is today defined as molar
volume (measured in cubic centimeters per mole):

molar mass (g/mol) / density (S/cm3) : molar volume (cm3/mol)

"Variation of Atomic Volume with Atomic Number, Adapted from Meyer's Plot of
1870", the alkali metals have the highest molar volumes of the solid elements. In Meyer's
plot ol'iltomic volunte VerSuS atonlic maSS- tht' :lotl:rletals Occur on the rising portion o1'lile
graph. and mr'tals occur at the peaks, in the vallcl s. aird on the dor.r'nslopes.

One group of elements that is absent tiom \4er,deleev's table is the noble gases. ail ol
rvhich r'vere discovered more than 20 years later. belween 1894 and 1898, b1" Sir \!'illiam
Ramsal'(1852-1916; Nobel Prize in Chemistrv 1904). initially, Ramsay did nol knos'rvhere
to place these elements in the periodic table. Argon. the first to be discovered, had an atonric
mass of40. This was greater than chlorine's and comparable to that of potassium, so Ramsay.

using the same kind of reasoning as Mendeleev, decided to place the noble gases between the

halogens and the alkali metals.

1.2.2 The Role of the Atomic Number in the Periodic Table

Despite its usefulness, Mendeleev's periodic table was based entirely on empirical
observation supported by very little understanding. It was not until 1913, when a you'lg
British physicist, H. G. J. Moseley (1887-1915), while analyzing the frequencies of x-rays
emitted by the elements, discovered that the underlying foundation of the order of the
elements was by the atomic number, not the atomic mass. Moseley hypothesized that the
placement of each element in his serics corresponded to its atomic ntxrtber Z, which is the
number of positive charges (protons) in its nucleus. Argon, for example, although having an
atomic mass greater than that of potassium (39.9 amu versus 39.1 amu, respectively), was
placed before potassium in the periodic table. While analyzing the frequencies ofthe emitted
x-rays, Moseley noticed that the atomic number of argon is 18, whereas that of potassium is
19, which indicated that they were indeed placed correctly. Moseley also noticed three gaps

in his table of x-ray frequencies, so he predicted the existence of three unknown elements:

technetium (Z: 43), discovered in 1937; promethium (Z: 6l), discovered in 1945; and

rhenium (Z = 7 5) , discovered in 1925 .

1.2.3 Atomic Volume Definition

The atomic volume is the volume one mole of an element occupies at room
temperatue.

Atomic volume is typically given in cubic centimetres per mole - cclmol.

20
'rhe
atomic voiume is a calcirlaleti value usilrg the atomic ileight ir;rd tirc ciensitl, using lhc
fonlula:

tu t r t ttt i c t' r t I u nt e= ql o mi c w e i glt t i dc ns i t1,

Another way to calculate atomic volume is to use the alomjc or ionic radius of an
atom (depending on whelher or not vou are dealing with an ion).

This calculates is based on the idea of an atom as a sphere. which isn't precisely
accurate. However, it's a decent approximation.

In this case, the formula for the volume ofa sphere is used:

'polume : (4/3)@)(r3)

where r is the atomic radius

For example, a hydrogen atom has an atomic radius of53 picometers. The volume of
a hydrogen atom would be:

volume = (4 /3)(r.)(533 )

volume = 623000 cubic picometers (approximately)

Units : cm3

Notes: The molar volume is also known as the atomic volume.

The standard SI units are m3. Normally, however, molar volume is expressed in units
of cm3. To convert quoted values to m3, divide by 1000000.

The molar volume depends upon density, phase, allotrope, and temperature. Values
here are given, where possible, for the solid at 298 K.

1.2.4 Atomic Radius

Atomic radius is the distance from the centre of the nucleus to the outermost shell
containing electrons. In other words, it is the distance from the cenhe of the nucleus to th.- ooint
up to which the density of the electron cloud is maximum.

2t
 ,lit*,lrtrc Su,r;:

f
A;

ri--_ -i!-'1._ '* ::.:

:-** lil l,Ll

,.'-._:
*s & hlb ln

&u I
.1r

, ltfl.!\tg,n *

1.2.4.1Types of Atomic Radii

Atomic radii are divided into three types:
. Covalent radius
. Van der Waals radius
. Metallic radius
Therefore, we will study these three tlpes of radius because they are vital for the better

understanding of the subject.

i) Covalent Radius

Covalent radius is one half the distances between the nuclei of two covalently bonded
atoms of the same element in a molecule. Therefore, r covalent: % (intemuclear distance between

two bonded atoms). The intemuclear distance between two bonded atoms is called the bond
length. Therefore,
r covatenr
: %( bond length)

ii) Van der Waals Radius

It is one halfthe distances between the nuclei of two identical non-bonded isolated atoms
or two adjacent identical atoms belonging to two neighbouring molecules of an element in the

22
solrd s1ala. I5e magnitude of the \/an iler \['aals :'rdius is dependent on rhe pacirr-rg (.l il.r!- utol't]s

ri,lren ihe clcment is in the solid state,

Foi example. the intemuclear distance bet$,eerl two adjacent chlorine aiorrs ()l lhi't\ao
treighbouring molecules in the solid state is 'l'herefore, the Van der Waals
-160 pm. radius o1'the
chlorine atom is 180 pm.

iii) Metallic Radius

A metal lattice or crystal consists of positive kemels or metal ions arranged in a definite
pattem in a sea of mobile valence electrons. Each kemel is simultaneously attracted b1' a number
of mobile electrons and each mobile eiectron is attracted by a nunber of metal ions.
Force of attraction between the mobile eleclrons and the positive kemels is called the
metallic bond. It is one halfthe intemuclear distances between the two adjacent metal ions in the
metallic lattice. In a metallic lattice, the vaience electrons are mobile; therefore, they are only
weakly attracted by the metal ions or kemels.

In a covalent bond, a pair of electrons is strongly attracted by the nuclei of two atoms.
Thus, a metallic radius is always longer than its covalent radius. For example, the metallic radius

of sodium is 186 pm whereas its covalent radius as determined by its vapour which exists as

Na2 is 154 pm. The metallic radius of Potassium is 231 pm while its covalent radius is 203 pm.

1.2.4.2 Y anation of Atomic Radii in the Periodic Table

a) Variation with period

The Covalent and Van der Waals radii decrease with increase in atomic number as
we move from left to right in a period. The alkali metals at the extreme left of the
periodic table have the largest size in a period. The halogens at the extreme right ofthe
periodic table have the smallest size. The atomic size of nitrogen is the smallest. After
nitrogen, atomic size increases for Oxygen and then decreases for fluorine. The size of
atoms of inert gases is larger than those of the preceding halogens.
As we move from left to right in a period, nuclear charge increases by I unit in each
succeeding element while the number of shells remains tle sarne. This enhanced
nuclear charge pulls the electrons of all the shells closer to the nucleus. This makes
each individual shel{s smaller and smaller. This result in a decrease of the atomic
mdius as we move from left to right in a period.
 a I'lre atomic rarlius abruptlf it'tcrcascs ils \\e [to\/e 1'rom halogens 1o thc inerl gas 'lhis
is because inefi gases have complclcll, tllled olbitals. Hence. 1he intet'-r'ler:tronic are
ma-rimum. We express the atonric sizc in terrns of Van der Waals radir,rs since they do
not fomr covalent bonds. Van der \tr'aals radius is lalger than the covalent radius.

Therefore, the atomic size of an inefi gas in a period is much higher than that of
preceding halogen

b) Variation within a Group

The atomic radii of elements increase u.ith an increase in atomic number tiom top to
bottom in a grcup. As we move dor.m the group. the principal quantum number increases. A
new energy shell is added at each succeeding element. The valence electrons lie t-arther and
farther away from the nucleus. As a result, the attraction of the nucleus for the electron
decreases. Hence, the atomic radius increases.

A Solved Example for You

Q: Wry is the Van der ll/aals Radius always greater than the Covalent Radius?
Ans: The Van der Waals forces of attraction are weak. Therefore, the intemuclear
distance in case of atoms held by Van der Waal forces is much largff than those between
covalently bonded atoms. Since a covalent bond is formed by the overlap of two half-filled
atomic orbitals, a part of electron cloud becomes common. Therefore, covalent radii are always
smaller than van der Waal radius.

1.2.5 Atomic Radius

The atomic radius is the distance from the atomic nucleus to the outermost stable
electron of a neutral atom. In practice, the value is obtained by measuring the diameter of an
atom and dividing it in half. But, it gets trickier from there.

The atomic radius is a term used to describe the size of the atom, but there is no
standard definition for this value. Atomic radius may actually refer to the ionic radius, as well
as the covalent radius, metallic radius, or van der Waals radius.

Atomic radius is the distance from the centre of the nucleus to the boundary of the
electron cloud. The atomic radius is in the Angstrom level. Although we define the atomic
radius for a single atom, it is hard to measure it for a single atom. Therefore, normally the

distance between the nuclei of two touching atoms is taken and divided by two, to get the
atomic radius. Depcndi:rg on the bonding between 1',to at(rurs ine radius call be calegorirrLj ilj
metallic radius. colalenl radius. Van der Waals radius. e'"c. Atomic radii increases as )ou go
down in a column in the periodic table, because neu, lalers ol electrons are adding. From lcti
to right in a row. atomic mdii decrease (except for noble gases).

1.2.6 Ionic Radius

The ionic radius is half the distance between two gas atoms that are just touching each
other. In a neutral atom, the atomic and ionic radiuses are the same, but many elements exist
as anions or cations. If the atom loses its outermost electron (positively charged or cation),
the ionic radius is smaller than the atomic radius because the atom loses an electron energy
shell. If the atom gains an electron (negatively charged or anion), usually the electron falls
into an existing energy shell so the size ofthe ionic radius and atomic radius are comparable.

Atoms can gain or lose electrons and form negative or positive charged particles
respectively. These particles are called ions, When neutral atoms remove one or more
electrons, it forms positively charged cations. And when neutral atoms take up electrons, they
form negatively charged anions. Ionic radius is the distance from the centre of a nucleus to
the outer edge ofthe ion. However, most of the ions do not exist individually. Either they are
bonded with another counter ion, or they have interactions with other ions, atoms or
molecules. Because ofthis, the ionic radius ofa single ion varies in different environments.

Therefore, when ionic radii are compared, the ions in similar environments should be
compared. There are trends in the ionic radii in the periodic table. As we go down in a
column, additional orbitals are added to atoms; therefore, the respective ions also have
additional electrons. Thus, from top to bottom the ionic radii increase. When we go from left
to right across a row, there is a specific pattem of ionic radii change. For example, in the
3td row, sodium, magnesium and aluminum make +1, +2 and +3 cations respectively. The
ionic radii of these three are gradually decreasing. As the numbers of protons are higher than
the number of electrons, nucleus tends to pull the electrons more and more towards the
centre, which result in decreased ionic radii. However, the anions in the 3'd row have
considerably higher ionic radii compared to the cationic radii. Starting from P3- the ionic radii
decrease to 52' and to CL . Reason for having a larger ionic radius in anions can be explained

by addition of electrons into outer orbitals.

25
lVhat is lhe dillerent'e belvteen Atontic Radius unl lonit Ralius?
z Atomic ratlius is an indication ol'the sizt'ol'an atom. Ionic radius is an
indication ofthe size ofan ion.

> A cation ionic radius is smaller'lhan that oltl.re atomic radius. And anionic
radius is larger than the atomic radius.

1.2.7 Ionisation Potential

The ionization energy or ionization potential is the energy necessary to remove an

electron from the neutral atom. It is a minimurn lbr the alkali rnetals which have a single
electron outside a closed shell. It generally increases across a row-on the periodic maximum
for the noble gases which have closed shells.
The ionization energy (IE) is qualitatively det-ined as the amount ofenergy required to
remove the most loosely bound electron, the valence electron, ofan isolated gaseous atom to
form a cation.
The ionization potential or otherwise known as the ionization energy, is the measure
of the amount of energy required to remove an electron from a neutral atom or ground state.
The first electron is removed from the valence shell and can be noted as the first ionization
potential.
The basic equation lor ionization energy is:
X--X*+e-
The amount of energy necessary changes each time an electron is let go, since it
becomes more difricult to remove electrons after one or more has already been removed from
the atom or molecule.

1,2,8 Electron Affinity

The electron affinity is defined as the energy change that occurs when an atom gains
an electron, releasing energy in the process. Let's remember that an electron is negatively

charged, so when an atom gains an electron, it becomes a negative ion.

Since we are talking about a change in energy, when an electron is added to an atom,

there is an equation used to determine the electron affinity:

A+e-A'
Atom electron Nesative ion

26
 ErA -- Ile :t?'aa Al i itlity
h,E : Chan.ge in nergy
[r'q = -dE

This equation shou,s tl.rat electron affinity is equal to the negative change in energy.
I-et's clarify the sign convention for the energy change associated rvith the gain of an
electron. Remember that the definition o1'an electron affinity is the energl released, so that
means that the reaction is exothermic. If a reaction is exothernlic, the chunge in energt is
negative. This means that the electron a/finig, is positive.
For exarnple, the electron affinity of chlorine has the negative sign. which shows us
the energy that is released to add one electron to an atom. The giving off ol energy is shown
with a negative sign.

Cl1s1 + e' ) Cl'661 AE = *349 kl lmol

Era =
-dE'
Ee* * *349 kl /ttrot

Based on this sign convention, this means that a higher electron affinity indicates that

an atom more easily accepts electrons. A lower electron ffinity indicates thdt an atom does
not accept electrons as easily.

1,2.9 Factors that Affect Electron Affinity

There are two factom that can affect electron affinity. These are atomic size and
nuclear charge. With regard to atomic size, let's think about a magnet and a refrigerator.
When a magnet is closer to the surface ofthe refrigerator, you can clearly feel the pull ofthe
attraction between the magnet and the refrigerator. The farther the magnet gets away from the
fiidge, the less you feel the attraction or pull.
When looking at a drawing of a smaller atom side by side with a bigger atom, it can
be seen that a smaller atom's outermost shell is closer to the nucleus than that of a bigger
atom. Just like our magnet and refrigerator analogy, the electron will feel more attraction to
the nucleus if it is closer.

27
 Ou,ie.riost sn,: il

ir''

S,r-:r.&l

S lncoming electron
{$ Nucleus

The smaller the atom is. the closer the outermost shell is; therefbre, it is a stronger
attraction between the nucleus and the incoming electron. That means the electron affinity is
higher for smaller atoms.
When looking at the periodic table the atomic radius increases lrom top to bottom,
moving down a column; therefore, the electron affinity increases from the bottom to the top
of the column.
Nuclear charge also affects electron affrnity. The nuclear charge is also known as the
atomic number, which is the same as the number of protons. Protons are positive subatomic
particles. The more protons there are, the greater the attraction is to electrons.

Trends or pattems can be seen in the periodic table with regard to electron affinity.
We are looking at this in terms of across the period, not down a group. From left to right, the
nuclear charge increases, resulting in a greater attraction to incoming electrons. So, we can
say thatfrotn left to right across a period, the electron afiinity increases upu,ard.

Electron Affinity

Perlodic Trend: Electron Affinlty

28
I.2.10 l'rends in fhe Periodic Table

Atomic numbcr The number ol'prot()ns ilt an atom.

Atomic mass The nurnber ol'protolls . neutrons.
Valence electrons The number oleleclrons in the outermost orbit of
an atom. (e.g. fluorine has 7 valence electrons)

Metallic character : Metals have characteristically weak force of attraction between

the nucleus and the outermost electrons. The weaker this lorce.
the greater the metallic character.
Atomic radius The distance from the center of the atom to the outermost
electrons. Atomic radius indicates the size of an atom.
Ionization enerry : The minimum amount of energy needed to remove the
outennost electron from an isolated atom of a gaseous sample of an
element.

Electron affinity The tendency ofan atom to attract electrons.

1.2.11 Factors Affecting the Properties

Some of the properties of the elements are related to the force of attraction between
the nucleus and the outermost electrons. This force of attraction is dependent on 2 factors.
These are, in order of importance:

a) The distance between the nucleus and the outer electrons

b) The number ofprotons in the nucleus (the nuclear charge)

Factors Affecting Periodicity Periodic Trends: Atomic Radius: the distance from the

center of the nucleus to the outermost electron (how big an atom is) -Ionic Radius:
the size ofpositive or negative ions Ionization energy: the amount of energy required
to remove an electron from an atom or ion Electronegativity: the attraction an atom
has for electrons

Factors Affecting Periodicity Factors Affecting Periodicity: Effective Nuclear Charge:

the total positive force of the nucleus (the more protons, the higher the effective
nuclear charge) Electron Repulsion: result of like- charged electrons electrostatic
repulsion
Factors Affecting Periodicity Stable electron configuration: atoms strive to form s 2 p
6 confrgurations (full valence*, full octet*...*we'll get to this) Number of Energy
1.3 Inorganic Qualit:itir c Analvsis

1.3.1 Solubilitv Product Principle and Qualitative Anal}'sis

Leaming Objective

Describe the application of the solubility product principle in the qualitative analysis of
a solution.

Key Points

In qualitative analysis. a solution is treated with various reagents to test for the
presence ol cerlain ions.

Solubility-product constants can be used to devise rnethods for separating ions in

a solution by selective precipitation.

Cations are usually classified into six groups, where each group has a common
reagent which can be used to separate them from the solution.

Terms

Qualitative analysis Determination of the identity of the chemical species in a sample.

Qualitative inorganic analysis. A method of analytical chemistry which seeks to find
elemental composition of inorganic compounds.
Precipitation a reaction that leads to the formation ofa heavier solid in a lighter liquid;
the precipitate so fomed at the bottom of the container.

1.3.2 Qualitative Analysis

Classical qualitative inorganic analysis is a method of analytical chemistry that seeks

to find the elemental composition of inorganic compounds. It is mainly focused on detecting
ions in an aqueous solution. The solution is treated with various reagents to test for reactions
characteristic of certain ions, which may cause color change, solid forming, and other visible
changes.

1.3.3 Solubility Product Principle and Qualitative Analysis

Solubility-product constants can be used to devise methods for separating ions in a

solution by selective precipitation. Selective precipitation is used to form a solid with one of
the ions in solution without disturbing the other ions. You can continue this method to
effectively separate all of the ions in a solution. The entire traditional qualitative-analysis
scheme is based on the use of these equilibrium constants to determine the correct
precipitating ions and the correct strategy.
l. 3.3. 1 C h emical precipitation :
Prccipitation is the lormation ol'a sr>lid in a solution or inside anoilrr: soliri driring a
chemical reaction or by diffusion in a solid, Precipitation is used in qualitative chenrical
analysis.

The extent to which a solute vvill dissolve in a solvent is called its solubility. The
solubilitl, of a chemical is conventionall)- expressed as the maximum nuniber ol grams of a
chemical that will dissolve in l00g of solvenl but conversion to mol L-l or g L-l is simple and
may be appropriate for some applications (see below). Since solubility is temperature
dependent, is always quoted at a specific temperature. With a very few exceptions. increasing

the temperatue of a solvent increases the solubility of the solute.

1.3.3. 2 S at urated solutions:
For practical purposes, a saturated solution is one in which no more solute will
dissolve. For example, the solubility of sodium chloride in water is 35.69 per l00g at 25"Cand
39.1 g per 1009 at 100'Cand both solutions are satuated solutions at their respective
temperatures. If the 100"C solution is cooled to 25oC, then 3.5 g of NaCl crystals will
precipitate from the solution, because the solution at 25"C requires only 35.6 g of NaCI for
saturation. This process is the basis of purification of compounds by recrystallization.
1.j.3. 3 Sol ubilily product:
In dilute aqueous solutions, it has been demonstrated experimentally for poorly soluble
ionic salts (solubilities less than 0.01 mol L-r) that the mathematical product of the total molar
concentrations of the component ions is a constant at constant temperature. This
product,.rK, is called the solubility product. Thurs for a saturated solution of a simple ionic

compound AB in water, we have the dynamic equilibrium:

AB5q1;6 +-+ A*1uqy * B-1*y

Where AB represents the solid which has not dissolved, in equilibrium with its ions in
the aqueous saturated solution. Then:

K,: [A.] x [B-]

For example, silver chloride is a solid of solubility 0.000 l5g per l00ml of water in
equilibrium with silver cations and chloride ions. Then:
K": tAg+l x tcll
The solubility of AgCl is 0.0015gml-r (10 x solubility per 1009, assuming that the
density of water is 1.0gml r) and therefore the solubility of AgCl is 0.0015 + 143.5 : 1.05 x

33
10 'rrol l- 1. lhus the saturated s()llrti()rr ei)r)tains 1.05 10-5 rnol l, 1 o1',\r ions and I.05 x
"
l0 : rrol I--r olCl ions and the soiuhilitr product Kl is:

K,:(1.05 * I0 :), (1.05 x l0'): l.l x l0 "'mol: L '

If the solid does not have a simple I: I ratio of its ionic componenls. e.g. PbCb. then
tlie solubility product is given b1':

,(.: [Pb*] x [Cl ]2

ln general terms, the solubility product for a compound MyNx. is given br':
K.: tMlr' , [N-]'
The practical effects of solubility products are demonstrated in the detection ofanions
and cations by precipitation and in quantitative gravimetric analysis (p. 139). For example, if
dilute aqueous solutions of silver nitrate (solubility 55.6 g per 1009 of water) and sodium
chloride (solubility 35.6 g per 100g of water) are mixed, an immediate white precipitate of
AgCl is produced because the solubility product of AgCI has been exceeded by the numbers
of Ag* and Cl- ions in the solution, even though the ions come from different 'molecules'. A
saturated solution of AgCl is formed and the excess AgCI precipitates out. The soiubility
product of the other combinations of ions is not exceeded and thus sodium and nitrate ions
remain in solution. Even if the concentration of Ag* is extremely low, the solubility product
foi AgCl can be exceeded by the addition of an excess of Cl- ions, since it is ihe
multiplication ofthese two concentrations which defines the solubility product. Thus soluble
chlorides can be used to detect the presence ofAg* ions and, conversely, soluble silver salts
can be used to detect Cl- ions, both quantitatively and qualitatively.

1,3.4 Principle of Elimination of interfering anions

Renoval of interfering radicals before III'd group analysis

What are the interfering radicals?

How do they interfere in systematic sepaxation ofcationic radicals?
Why is it necessary to remove them before III'd gr analysis?
Why don't they interfere in I't or II'd group analysis?

Interfering radicals are oxalate, tartrate, fluoride, borate and phosphate and they are
anionic radicals. They form complex with III'dgr group reagent ammonium chloride and
ammonium hydroxide. This leads to incomplete precipitation of III'd group cations and causes

34
immature precipilarioir c.f IVrh and Vth group ca1i..,;rs in aikalirre mediun. [-ei's rn Io

understand it.
Oxalate. tar1rale. fluoride, bomte, silicate and phosphate 01'the metals are soluble irl
acidic medium.

If you ren,ember, for l'rand 2"d analysis medium remain acidic (dilute HCI) that's
why they do not interfbre then. But for 3'd group analysis the medium becomes alkaline by'

group reagents ammonium chloride and ammonium sulphide. Here interfering radicals come
into action and disturb the solubility product of cations which causes their premature or
incomplete precipitation.

In acidic medium these salts produce their corresponding acids like oxalic acid,
phosphoric acid, hydrofluoric acid, boric acid and tartaric acid. For example, barium oxalate
reacts with HCI and produces oxalic acid.

BaC2Oa+2HCl + BaClz +HzCzOt

These interfering acids are weak acids so they do not dissociate completely and
remain in solution in their unionised form. Equilibrium is developed between dissociated and
un-dissociated acid.

HzCzOr+2L{ +CzOt2-
Hydrochloric acid is a strong acid and is ionised completely.

HCI+tf+ct
Hydrogen ions acts as common ion among them and higher concentration of
Ff suppresses the ionization of interfering acid. Therefore, ionic product of CzO]- and
Ba2+ doesn't exceed the solubility product of barium oxalate which is why Ba2* remains in
the solution as barium oxalate. That's how interfering radicals do not interfere as long as the
medium remains acidic enough. But when we make the medium alkaline by adding 3'd group
reagent ammonium hydroxide NI{4OH, OH- ions combine with tfand neutralise them. This
decreases the concentration of fions which shifts the equilibrium of dissociation of
interfering acid forward and increases the concentratio n of CzO]- . Thus the ionic product of
C2Oa2- and Ba2* exceeds the solubility product of barium oxalate and Ba2* gets precipitated in
the 3'd group, which actually belongs to the 4fi group.

35
One or rrorc i:ricr'1i:ritrg radicals carr be preseul ir, trtc soltttion. Thel' have to be renlored ilt
the foliorving order: first we rernove oxalate and rarlrrte. then borate and fluoride- theit
silicate and in the Iasl phosphate.
i) Procedure for the removal of oxalate and tartrate: Oxalate and tartrate of metals are

soluble in acid and the)i decompose on heating. Take the t'iltrate of2nd group and boil o11'l{2S
gas from it. Add ,1-5ml concentrated nitric acid FI\IO; and heat it till it is almost dry'. Repeat
this treatment for 2-3 times.
(COO)22- + U+ --+ ((OOH)2
(COOH)2 --+ HCOOH + CO2t
HCOOH-CO1 -H:OI
Tartrate and tartaric acid decomposes in a complex manner; charring takes place on
heating and a smell of bumt sugar develops. Extlact the with dilute HCI and filter. Use this
filtrate for analysis of 3'd group or use for removal ofother interfering radicals.

ii) Procedure for the removal of borate and fluoride: Take the filtrate and evaporate it to
dryness. Add concentrated HCI and again evaporate to dryness.

F- + Ht ---; HF
CaFz + 2HCl -+ CaCl2 + 2HF
On heating with HCl fluoride forms hydrofluoric acid and Borate forms orthoboric
acid which evaporate on heating.
BO33- + 3Hn ---.l HrBO:
Na:BO: + 3HCl ---+ 3Nacl + H3Bo3
Extract the residue u,ith dilute HCl and filter. Use this filtrate for analysis of 3'd group
or use for removal of other interfering radicals.
If fluoride is absent and borate is present then residue use a mixture of 5m1 ethyl
alcohol and l0ml conc. HCI and evaporate to dryness.

BO33- + 3H* ---r H:BO:

H:BO:+ 3CzHsOH ---+ (C2H5O)3Bf + H2O

iii) Procedure for the removal of silicate: Evaporate the filtrate of 2'd group or residue
obtained from removal of interfering radicals with concentrated HCI to dryness. Repeat this
treatment for 3-4 times.

36
 SiOrr'+ ?H' --+ H2SiO3 J

HrSiOr J ----+ SiOzl + H2O

On heating with HCI silicate converts to metasilicic acid (HlSiO;) rvhich is converted
into white insoluble powder silica (SiO2) on repetitive heating with concentrated HCl.

iv) Test for phosphate HP0,r2-: lest 0.5m1 of the filtrate with lml ammonium molybdare
reagent and a few drops ofconcentrated HNO3, and warm gently, yellorv precipitate indicates

the presence ofphosphate. Its composition is not known exactly.

v) Procedure for the removal of phosphate: Ferric chloride is generally used for the
removal of phosphate. Fe(III) combines with phosphate and removes all phosphate as
insoluble FePOa. Fe(III) is also a member of 3'd group so first we have to test its presence in
the filtrate of2nd group then we can proceed for the removal ofphosphate.

HPO+2- + Fe3* --- FePOa J + H*

Test for Fe:To the filtrate of2nd group add ammonium chloride NtI+Cl and a slight excess of
ammonia NH3 solution. If precipitate appears, it indicates the presence of 3'd group. It may
contain hydroxides Fe(OH)r, Cr(OH)3, AI(OH)3, MnO2.xH2O, traces of CaF2 and phosphates
of Mg and IIIA,IIIB and IV group metals. Dissolve the precipitate in minimum volume of
2M HCl. Take 0.5m1 solution and add potassium hexacyanoferrate (II) Ka[Fe(CN)r]
solution. If iron is present, you will get prussian blue coloured precipitate of iron(III)
hexacyanoferrate.

4Fe3* + 3 [Fe(CN)6]a- ---+ Fe+[Fe(CN)oh

Removal of phosphate: To the main solution add 2M ammonia NH3 solution drop wise, with
stirring, nntil a faint permanent precipitate is just obtained. Then add 2-3ml 9M acetic acid
and 5ml 6M ammonium acetate solution. Discard any precipitate if obtained at this stage. If
the solution is red or brownish red, sufflcient iron Fe(III) is present here to combine with
phosphate. If the solution is not red or brownish red in colour then add ferric chloride
FeCl3 solution drop wise with stirring, until the solution gets a deep brownish red coloured.
Dilute the solution to about l50ml with hot water, boil gently for 1-2min, filter hot and wash
thc' residue rvith a little bcil;r,r rrater. Ilcsidue n'ray contain phosphirte crl'I"'e. ;\i and Cr. Kec'p

the filtrate for tesl of lllB grtrup.. Rinse the residue in porcelain dish ivith lOml cold u,ater.
add 1-1.59 sodium pero\oboralr' nnd boil gently utltil the evolutiotr tll'()2 ceasc-s (2-3min).

Filter and wash with hot \\'ater. Ile.ject the residue to remove phosphate in the tbrm of FePO+.
Keep the filtrate and test lor lllA group.

To test the presence ol interfering radicals you need to prepare sodium carbonate
extract and then test them separately. Scheme for the test of anionic ladicals is not as

systematic as cationic radicals. We will study them in coming posts. In the next post we will
discuss the analysis of IIIA group cations.

1.3.5 Common-ion effect

The common-ion effect states that in a chemical solution in which several species

reversibly associate with each other by an equilibrium process, increasing the the
concentration of any one of its dissociated components by adding another chemical that also
contains it will cause an increased amount of association. This result is a consequence ofl-e
Chatelier's principle for the equilibrium reaction ofthe association/dissociation. The effect is
commonly seen as an effect on the solubility ofsalts and other weak electrolytes. Adding an
additional amount of one of the ions of the salt generally leads to increased precipitation of
the salt, which reduces the concentration of both ions of the salt until the solubility
equilibrium is reached. The effect is based on the fact that both the original salt and the other
added chemical have one ion in common with each other.

1,3.6 Uncommon - ion effect

Sometimes adding an ion other than the ones that are part ofthe precipitated salt itself
can increase the solubility of the salt. This "salting in" is called the "uncommon-ion effect"
(also "salt effect" or the "diverse-ion effect"). It occurs because as the total ion concentration
increases, inter-ion attraction within the solution can become an important factor. This
altemate equilibrium makes the ions less available for the precipitation reaction. This is also
called odd ion effect.

1.3.7 Solubility effects

A practical example used vary rvidely in areas drawing drinking

water from chalk or limestone aquifers is the addition of sodium carbonate to the raw water to
reducc i.hi hardness of the rvaler. In ',h,: uaic: lrcarir.iL'nt plocess, highlr sr.rlr.rhlr :,irliur:'r
carbonal,,: salt is added to precipilate or-rt sparingir soluhle calcium carbonate. 'i hc r crr
1..n1-e

and llnclr, divided precipitate of calcium carbonatc rhat is generated is a valuable [r -nioduct
used in the manufacture oftoothpaste.
'l
hc- salting-out process used in the manut'acture of soaps benefits liom the cornmon-
ion eff'ect. Soaps are sodium salts of latty acids. Addition of sodium chloride reduces rhe

solubilit-v of the soap salts. The soaps precipitate due to a combination of common-ion ef'fect
and increased ionic strength.

Sea. brackish and other waters that contain appreciable amount of sodium ions (Na*)
interfere with the normal behavior of soap because of common-ion effect. In the presence of
excess Na+, the solubility ofsoap salts is reduced, making the soap less effective.

Solubility refers to the amount of material that is able to be dissolved in a particular

solvent. For example, table salt (NaCl) placed in water eventually dissolves. However, if
more table salt is continuously added, the solution will reach a point at which no more can be
dissolved; in other words, the solution is saturated, and the table salt has effectively reached
its solubility limit.

1,3.8 Buffering effect

A buffer solution contains an acid and its conjugate base or a base and its conj ugate
acid.S Addition of the conjugate ion will result in a change of pH ofthe buffer solution. For
example, if both sodium acetate and acetic acid are dissolved in the same solution they both
dissociate and ionize to produce acetate ions. Sodium acetate is a strong electrolyte, Ed it-,,
dissociates completely in solution. Acetic acid is a weak acid, so it only ionizes slightly.
According to Le Chatelier's principle, the addition of acetate ions from sodium acetate will
suppress the ionization of acetic acid and shift its equilibrium to the left. Thus the percent
dissociation of the acetic acid will decrease, and the pH of the solution will increase. The
ionization ofan acid or a base is limited by the presence of its conjugate base or acid.

NaCH3CO2 ---, Na* (uq) + CI{:COz-

1,y <"ql

CH3CO2H ruql * fr"ql + CII:COz-t"ql

This will decrease the hydronium concentration, and thus the common-ion solution
will be less acidic than a solution containing only acetic acid.

39
1.3.9 ( ornplexation reactions including sllot tcst in qualitative analysis

Spot'l'esls (Jeneral Proccdures

I jse clean glasswarc and deioniz.'d \\iltL'r 10 avoid contaminating r our sample.

Perfonn tests on "known" solutions and lour unknou'n solution simultaneousll . Keep in
mind that your unknou.n is diluted compared and may be colored by the presence of ser,eml
ions. There[ore, positive results might have slightly different appearances betrveen lhe knor.vn
and your unknown. Some spot test reactions occur slowly. If no reaction is apparc-nt atier the
addition of reagent, heat the reaction mixture in a hot water bath according to instruclions
given. Stir w'ell after addition ofreagent using a clean stining rod or disposable transt'er pipet.
Perform tests in the order given as described in the Laboratory Marual

a) Spot Tests Test I: Carbonate Ion

You will first test the "known" solution by placing 5 drops of the I M Na2CO3
solution in a micro test tube (or spot plate) and add 5 drops of 6 M HCl. The fomration of
bubbles indicates release of carbon dioxide,fas. Repeat the test using 5 drops of your
unl<nown and adding 5 drops of 6 M HCI (do NOT add the I M Na2CO3 solution as this is
the "known" solution).

b) Spot Tests Test 2: Thiocyanate lon

This basis of the thiocyanate spot test is to identi$ the thiocyanate ion, SCN- , by its
reaction with iron(III) to form a blood-red colored complex. Add 5 drops of 6 M HCI to 5
drops of 0.5 M KSCN (the "known") on the spot plate. Add 1 drop of 0.1 M Fe(NO?I,3 th:
10
solution in the spot plate. The solution will turn red if SCN- is present. Repeat the
'teit
on
your unknown solution without adding the 0.5 M KSCN solution.

c) Spot Tests Test 3: Sulfate Ion

Put 5 drops of the "known" 0.5 M Na2so4.solution in a well of a spot plate. Add 5
drops of6 M HCI to the plate. Now add 1 drop of 1 M BaCl2 to the plate. A precipitate of
white BaSO4 indicates the presence of sulfate ion.Repeat the test on your unknown without
using the 0.5 M Na2SO4 !'known" solution.

40
d) Spot Tests T est {: Phosphate lon

Place 5 drops of the "known" 0.5 M Na2HPO4 (soriirrnr rnonohydrogen phosphale)

solution in a medium test lube. Add I mL of 6 M HNO3.. \ior,v add I mL of Ammonium
molybdate solution, (Ntl4)2MoO4 to the test tube. The presence of phosphate ions is
confirned by the formation of a yellow precipitate.This precipirare is often slow to form and
heating in the hot water bath may be required to initiale precipitation.Repeat the test on your
unknown.

e) Spot Tests Test 5: Chromate Ion

Solutions containing chromate ions are yellow when neutral or basic and orange when
acidic. The orange color is due to the formation ofthe dichromate ion lCrZOZZljidd 5 drops
of "known" 0.5 M K2CrO4 to a spot plate. Add 5 drops of 3%o H2O2. Now add 10 drops o16
M HNO3 to the plate. The formation of a blue-green color, which appears but rapidly
disappears, indicates the presence of the chromate ion. Repeat this test on your unknown
without adding the 0.5 MJ(2CrO1 t""*"" solution.
.

',
f) Spot Tests Test 6: Chloride Ion r', ,

Place 5 drops of "known" 0.5 M NaCl on a spot plate. Add 5 drops of 6 M HNO3.
Now add 2 drops of 0.1 M AgNQ3- tg the plate. The presence of chloride ion is indicated by
the formation ofa white precipitate of AgCl. IfTest 2 indicated that your unknown contained
SCN-, follow the lab manual procedure for removing the SCN- ion before you test your
unknown for Cl' because SCN- also forms a white precipitate with Ag*. Repeat this test on
your unknown solution. Remember not to add the "known" NaCl solution.

g) Spot Tests Test 7: Acetate Ion I

Place 5 drops of "known" 0.5 M NaC2H3O2 (sodium acetate) on a spot plate. (The
acetate ion is often abbreviated as OAc-, or as CH3COO-). Add 5 drops of 3 M H2_SO4 to the
spot plate. The presence of acetate ion is indicated by the smell of acetic acid (a vinegar odor)

coming from the plate. If no odor is immediately present, repeat the test in a micro test tube,
warming it in a hot water bath for 20 seconds and check the odor again.Repeat this test on
your unknown solution. Do not add the "known" NaC2H3O2.solution.

47
h) Spot Tests Test 8: Ammonium Ion

This tesl also relics on vour sense of smell io dd(-ct the presence ola substance. Add
5 drops of "knorvrr" 0.5 M NH4CI to a spot plate or a rnicro test tube. Add 5 drops ol'6 M
NaOH to the plate and che'ck for the presence of an arnnronia odor by gentle *afting. If no
odor is immediately apparent. wann the test tube and check again.As an additional test tbr
XH{],. nlace a drop of the unkrown on a spot plate and add a drop oiNessler's Reagent. A
reddish-brown precipitate indicates the presence of the NH4- ion (see lower photo). Repeat
the test on your unknou,n.

i) Spot Tests Interfering lons

If you suspect that an ion is interfering with a particular test, make up a "known"
solution that contains the ions you think you have in our unknorm and repeat the spot tests
which gave you trouble. Test 3 is most likely to have interference problems from the Ba2* ion
which also forms precipitates with the chromium and phosphate ions. Test 6 is most likely to
have interference problems from the Ag* ion which forms precipitates with the phosphate,
sulfate, carbonate, chromate, and thiocyanate ions. Refer to the Laboratory Manual for
specific instructions of how to remove these interfering ions.

1.3.10 Reactions involved in separation and ideniification of cations and anions in the
analysis

Qualitative Analysis of Cation and Anion

Qualitative analysis is used to identify and separate cations and anions in a sample
substance. Unlike quantitative analysis, which seeks to determine the quantity or amount of
sample, qualitative analysis is a descriptive form of analysis. In an educational setting, the
concentrations of the ions to be identified are approximately 0.01 M in an aqueous solution.
The 'semimicro' level of qualitative analysis employs methods used to detect 1-2 mg of an ion
in 5 mL of solution.
While there are qualitative analysis methods used to identify covalent molecules, most
covalent compounds can be identified and distinguished from each other using physical
properties, such as index of refraction and melting point.

42
 l.-1.1I Sample Qualitativc Analysis Protocol

First, ions are removed in groups flonr the initial aqueous soluliotl. ,,\licr each group
hss been separated, then testing is corrducted tbr the individual ions in each groiip. Hene is a
com,non grouping of cations:

Group I: Ag*, Hg22t, Pb2*

PrecipitatedinlMHCl

Group II: Bi3*, cd2*. cu2*, Hg2'. (Pb2u), sb3* and Sbs*, Sn2* and Sna
Precipitated in 0.1 M H:S solution at pH 0.5

Group III: Al3*, (Cd'?), Co2*, Cri*, Fe2* and Fe3*, Mn2*, Ni2*, zn2n
Precipitated in 0.1 M H2S solution at pH 9

- Group IV: B**, ca2' , r., Mg1-, Na*, NH4*

B**, Ci*, and Mg2* are precipitated in 0.2 M (NHr)zCO: solution at pH 10;
the other ions are soluble

Many reagents are used in the qualitative analysis, but only a few are involved in
nearly every group procedure. The four most commonly used reagents are 6M HCI, 6M
HNOr, 6M NaOH, 6M NH3. Understanding the uses of the reagents is helpful when planning
an analysis.

It is the intention of this unit to study the separation and identification of2l of the
most cornmon cations and 8 of the most common anions.
common cations: Ag'*,Hg'*, pb2*, Hg2*, Bi3*, cu2*, cd2*, Al3*, cr3*, Fe2*, Fe3*, Mn2*,
zn2*, co2*, Ni2*, Ba2*, sl*, ca2*, Mg2*, Nal*, Kl*

Common Anions: SO+2-, CO:2", POa3-, Cll-, Br1-, Il-, S1, NOJ-
t t )-
'\ $r tr 5

1.3.12 SEMIMICRO TECHNIQUES

Performing qualitative analysis properly requires knowledge of certain basic laboratory

techniques. In order to speed up procedures, all techniques rvill be on a semimicro scale. This
scale involves volumes of 12 mL of solutions and adding reagents dropwise with eye
droppers. Containers will generally be standard 75 mm test tubes which hold about 3 mL.
Techaiques for working with volumes of this magnitude will be outlined below.

o Water
. Dispensing Reagent Solutions
. Stirring Rods

43
 Adjusting pH
Precipitation
Cerrtrifuging
Washing a Precipitate
Transfering a Precipitate
Heating Solutions
Evaporating a Solution
Spatulas

Cleaning Glassware
Sulfide Ion

i) Water
Whenever it is necessary to use \.\,ater in a procedure, use distilled water. Ordinary tap
water is not completely pure and may introduce substances for which you are trying to test or
it may introduce incompatible contamination.
ii) Dispensing Reagent Solutions
When obtaining reagents from the reagent bottles, always dispense the reagent with the
dropper contained in the reagent bottle. whether dispensing the reagent directly into your
sample, or obtaining a quantity of reagent in another container. Do not touch the dropper to
the solution to which you are adding the reagent or to your sample container. Do not set the
dropper on the reagent bench or lab bench. Return the stopper promptly to the reagent bottle
from which it originated. Do not place anlhing into a reagent bottle other than the dropper
which is contained in it. If you need a volume greater than 2 mL, use a graduated cylinder.
For lesser volumes, you may want to calibrate one of your eye droppers by counting how
many drops of water it takes to deliver 1 mL into a graduated cylinder.
iii) Stirring Rods
When reagents are added to a solution, it is essential that the solution be stirred
thoroughly. Stirring rods can be prepared by cutting short lengths of thin glass rod and fire-
polishing the ends. The stirring rods get wet with each usage, and ifnot properly cleaned, will
contaminate the next solution. A simple way to keep stirring rods clean is to place them in a
beaker ofclean distilled water and swirl them about after each use. The contamination will be
highly diluted and can remain in the water. It is advisable to change the water periodically to
minimize contamination however.

44
iv) Adjusting pIl
Al linres you rvill want to make a soluiio:r ac:.iirr or basic. Add 1he proper reagent
dropwise, stining rvell rvith a stirrir-rg rod after each addition. and test the pH at appropri;.rtc
intervals bl. touching the tip of the stiring rod lo lilmus or other pH indicating paper.

Continue this plocedure until the paper tums the proper color. If litrnus paper is not
sufficientlv sensitive. obtain sone pH indicator paper. r.r'hich is available for various ranges
ofthe pH scale.
v) Precipitation
In order to detect the formation of a precipitate. both the solution being used and the
reagent must be clear (transparent, but not necessarily colorless). Precipitation is
accomplished by adding the specified amount of reagent to the solution and stirring well. Stir
both in a circular direction and up and down. When precipitation appears to be complete,
centrifuge to separate the solid. Before removing the supematant liquid with a dropper or by
decanting (pouring off), add a few drops more of the reagent to check for complete
precipitation. If more precipitation occurs, add a few more drops of reagent, centrifuge, and
test again.

vi) Centrifuging
A centrifuge is used to separate a precipitate from a liquid. Put the test tube containing
the precipitate into one ofthe locations in the centrifuge. Place another test tube containing an
equal volume of water in the centrifuge location directly eppssile your first test tube. This
procedure is extremely important; it must be followed to maintain proper balance in the
centrifuge. Otherwise, the centrifuge will not function properly and may be damaged.
Tum on the centrifuge and let it run for at least 30 seconds. Tum the centrifuge offand
let it come to a complete stop without touching it. Stopping the centrifuge with your hand is
not only dangerous, but is likely to stir up your precipitate. The precipitate should settle to a
compact mass at the bottom of the test tube. The liquid above the precipitate (the supematant)
should not have any precipitate suspended in it. If it does, centrifuge again. The supematant

can then be poued off (decanted) into another test tube without disturbing the precipitate. All
of the liquid should be decanted in a single pouring motion to avoid resuspending the
precipitate. An eye dropper or a dropper with an elongated tip may also be used to draw off
the supematant.

45
Yii) \1'ash ing a l'recipitatc
Afier a precipitate has been centrifuged:Lnd rhc supernatant liquid decanled or dtlitt.l
off, there is still a iittle liquid present in the precipitate. To remove any ions u'hich nrighl
interfere rrilh this liquid should be removed with a wash liquid. usualll
hu'tl.rer testing,

distilled water'. 'fhe wash liquid must be a substance w'hich u'ill not interfere with the
analysis. cause further precipitation. or dissolve the precipitate. Add the wash liquid to the
precipitate. stir well. centrifuge, and decant the rvash tiquid. The wash liquid is usually'
discarded. Precipitates should be washed twice for best results.
viii) Transferring a Precipitate

Sometimes you will want to divide a separated and washed precipitate into two
portions, in order to carry out two additional tests. To transfer part of the precipitate to
another test tube. add a small amount of distilled water to the precipitate, stir the mixture to
form a slurry, and quickly pour halfofthe slurry into another container. Do not use a spatula.
This could contaminate your sample.
ir) Heating Solutions
Test tubes containing reactions mixtures are never to be heated directly over an open
flame. If a solution is to be heated, it should be placed in a test tube and suspended in a
beaker of boiling (or in some cases only hot) water. It will be convenient to keep a beaker of
water hot tluoughout the laboratory period. If hot water is required in a procedure, it should
be distilled water heated in a test tube suspended in the beaker of boiling water. Do not use
water directly from the beaker it may be contaminated.

x) Evaporating a Solution
Sometimes it is necessary to boil a solution to reduce the volume and concentrate a

species or drive off a volatile species. To boil a liquid, place it in a small porcelain casserole
or evaporating dish and heat it on a wire gauze with a small flame. Watch it carefully and do
not overheat it. Generally, you do not want to heat to dryness as this might decompose the
sample. Stir the solution during the evaporation. Do not try to evaporate a solution in a small
test tube. It will take much longer and the contents of the tube may be ejected if the tube is
heated too strongly.

xi) Spatulas
Never place a metal spatula in a solution. It may dissolve and cause contamination. If
you need to manipulate a solid, use a rubber policeman on a stirring rod.

46
xii) CleaningGlassware
Cleanliness is essenlial tbr a suocessful procedure. All appiratu:; rnust i:,e cleaned well
with soap and a brush. rinsed u,ith tap water, and finally rinsed vrirh ti;stillcd rvater.
xiii) Sullide Ion
In any procedures involving sulfide ion, thioacetarnide (Cl{lcs}ifi2) should be used as
the source of sulfide ion. Upon heating in water (or acidic or basic solution). thioacetamide
decomposes to CHrCOz, NHq*, and H2S (or 52 in basic solution):

CHTCSNII2 + 2 HzO > CHTCOz + NHr- + HrS

1.4 I Molarity (M):

Molarity is defined as the number of moles of solute per liter of solution. That is,

M
.r/,l-l'
-Y' rnolla

Here,
W : weight of solute.
M : molecular mass of solute
V : volume of solution

1.4.2 Molality (m):

It is defined as the number of moles of solute per kg ofsolvent. That is,

fi' - 1000 molkg'

=
'' -l-I i
Here,
b : weight <if solvent

1.4.3 Normality (N):

It is defined as the number of gram equivalents of the solute dissolved per litter of the
solution at a specific temperature.

equivalents of solute
volunes of solution

1.4.4 Mole-fraction (x):

 Mole fraction is rhc llLlio ol'the numbel ol moles o1'soit-tl,,: and the total number of

moles of solute arld sol\ent. lhc. trole liaction of an,v constilt-len1 of a solution is defined as

the number of moles o1'thai constituer-rt per mole of the solution. Il the solution contained

i).', of A and
mc,les 'ts moles of B- then

,lr + t:r,

t'-i
irl + iij

and

-r, +ri =I

Example Question 1 : Molarity, Molality' Normality

A solution of hydrogen peroxide is 15.2%o by mass. what is the molarity of the solution?
Assume that the solution has a density of 1.01g/ml-.

Possible Ansrvers:

5.00M
4.95M
6.02M
3.72M
Correct answer:
4.95M

Explanation:

Start by assuming that we have 1.00L of this solution. Recall that hydrogen peroxide has a
molecular formula of HzOz. .: |
i ) ) ) lr
Use the given density to find the mass of t}le solution.
\ r
1.00lei000m!1lr1.01gml:1010g
Next, find the'rnass of the hydrogen peroxide present in the solution.
1010g(0.1s2)=153.529
Convert the mass of hydrogen peroxide into moles of hydrogen peroxide'
153.529 of H2O2.l mole HzO 23l.04eEbOz=4.95 moles of HzOz
Recall how to find the molarity of a solution:
Molarity : ,ro1.s of soluteliters of solution
Since we have 1.00L of solution, the molarity is 4'95M.

Example Question 2 : Molarity, Molality, Normality

what is the molarity of a solution in which 2119 sodium hydrogen carbonate is dissolved in
a 10.0L solution?
Possible .Anslve rs:

0.2 I i IV{
0.3 ji Nr
0.251 lv't
2.131\t
2.51NI
Correct anslver:
0.251M

Explanation:

2l lg sodium hydrogen carbonate dissolved in a 10.0L solution has 0.251M.

The first step is to calculate how many moles oiNaHCO3 are present. 211g NaHCO3 lmot
NaHCO: 84.0069 NaFICO: = 2.5lmol NaHCO:
We calculate molarity with the following equation:
M : molesofsolutelitersofsolution
M = 2.51moles NaHCOrl0L= 0.251M

Example Question 3 : Molarity, Molality, Normality

How many milliliters of a 5.0 M CuS04 solution needed

prepare 0.350L of 0.500MCuSO4?

Possible Answers:

0.0714mL
0.035mL
7.l4mL
3.5mL
35mL
Correct answer:
35mL

Explanation:

35mL of 5.0M CuSO4 solution are needed to prepare 0.350 L of0.500M CuSO4.
We can use the formula MlVl=M2V2
Therefore, (5.00M 1 )(v 1 )=(0.350M2X0.s00L)
Vl = 0.035L = 35 mL
Example Question 4 : Molarity, Molality, Normality
What are the concentrations of aluminum and sulfate in a 3.0 M solution of aluminum
sulfate?

Possible Answers:

2.2M Al3*
4.lM SOz{
2.0M Al3*

49
 l
i.0I,1 S(),
6.0\1 .,\1''
9.0\1 SOr r
L51r.1 ;\lr-
1.0N4 so2't
i.0N,1 Alr-
3.01\,r sor
l
Correct anslver:
6.0lvLAlr*
9.0M SO2-4
Explanation:
The relative concentrations of aluminum sulf-ate 1At2(SOa)3) are
6.0M At3*
9.oM SO2 I
3.0 mol Al2(Soa)3 i.ol.2molAl3*1mol Al2(SOa)3:6.0M Al3*
3.0 mol Al2(Soa)3 1.ol.3mol So2 41mol Al2(SO4r:9.0M Al3*

Example Question 5 : Molarity, Molality, Normality

Which of the following choices is characteristic of molality?

Possible Answers:

Moles of solute per liter of solution

Equivalents per liter
Useful in experiments with significant temperature changes
Useful in experiments without significant temperature changes
Correct answer:
Useful in experiments with significant temperature changes

Explanation:

Molarity, molality, and normality are all units of concentration in chemistry. Molarity (M) is
defined as the number of moles of solute per liter of solution. Molality (m) is defined as the
number of moles of solute per kilogram of solvent. Normality (N) is defined as the number of
equivalents per liter of solution. Molality, as compared to molarity, is also more convenient
to use in experiments with significant temperature changes. This is because the volume of a
solution increases with temperature, and heating causes molarity to decrease; however, since
molality is based on masses rather than volumes, molality remains unchanged.

Expressions of Concentration of Solutions:

The concentration or strength of solution means the amount of solute present in a
given amount of the solution. The concentration may be expressed in physical or chemical
units.

50
Normalitv (N): ll is ;.lclir.recl as number of graut equirricr:.. ol'llte solute present in 1 lite
(1000mL.) ol'the solulion. l1'\tr/ g of solute ol'equiralenr ui,rght I-- is present in V mL o1'thc
solution. the r.rormalitl of tl.re solution is given by:

: V/ i: Iij[ ,

i'Jornralit!'
t-,f

Molarity (M): It is defined as the number of moles of the solute present in I litre (or 1000
mL) of the solution. A one molar solution contains I mole olthe solute dissolved in 1 litre of
the solution.
Molality (m): It is defined as the number of moles of solute dissolved in 1000 g of the
solvent. One molal solution contains one mole of the solute dissolved in 1000 g of the
solvent.

Normal solution:
A solution containing one gram equivalent weight of the solute dissolved per litre is
called a normal solution; e.g. when 40 g of NaOH are present in one litre of NaOH solution,
the solution is known as normal (N) solution of NaOH. Similarly, a solution containing a
fraction of gram equivalent weight of the solute dissolved per litre is known as subnormal
solution. For example, a solution of NaOH containing 20 g (U2 of g eq. wt.) of NaOH
dissolved per litre is a sub-normal solution. It is written as N 12 or 0.5 N solutions.

Formulae used in solving numerical problems on volumetric analysis;

1. Strength of solution = Amount of substance in g litre-r.

2. Strength of solution = Amount of substance in g moles litre-I.

J. Strength of solution = Normality x Eq. wt. of the solute = molarity x Mol.

wt. of solute.

4. Molarity = 1461"s of solute/Volume in litre.

5. Number of moles: Wt.in gMol. wt: M x V (initial): Volume in litresl22.4

at NTP (only for gases).

6. Number of milli moles: Wt. in I x 1000/mol. wt. = Molarity x Volume in

mL.

7. Number of equivalents: Wt. in g/Eq. wt : x x No. of moles x Normality x

Volume in litre (Where x: Mol. wt/Eq. wt).

51
 8. rr-unth:i o1'nrill equivalents (nleq.) = \l't. in g ,, 1000 / Eq. u,t : nonr]alit)
Volunlc in lnl-,

9. Nornralitr' : x x No. of mill moles (\\'here x = r'alenc! or change in ori'

number).

10. Nomality fomlula' NrVr N:Vz' (Where \1' N: .- Normality o1'titrant antl
:
titrate respectively, V1, V2 --- Volutne of tilrant and titrate respectively)'

I 1 . 7o by rueight = Wt. of solvent/Wt. of solution ' 100 '

A solution is a homogeneous mixture of tu'o or more components, the composition of

which may be changed. The substance which is preseut in smaller proportion is called
the

solute, while the substance present in large proportion is called the solvent.

1.4.5 Standard

Standards are materials containing a precisely known concentration ofa substance for
use in quantitative analYsis.

A standard provides a reference that can be used to determine unknown

concentrations or to calibrate analytical instruments'

a) Primar Standards
r'
A primary standards is a reagent that is extremely pure and stable; it rrot a hydrate/it
has no water ofhydration, and it has a high molecular weight'

Example
(i) Primary standards for titration of acids are:

Sodium carbonate: Na2CO3, molecular weight = 105'99 g/mol

(ii) Primary standards for titration ofbases are:

r r j-'t.' ,t .

Potassium hydrogen iodate: K (I3)2, molecular weight

: 389.92 glmol

(iii) Primary standards for titration ofredox are:

Sodium carbonate: NazCuO+, molecular rveight = 134'00 g/mol

b) Secondary standards i r

A secondary standard is a standard that is prepared in the laboratoly for a specific

analysis. It is usually standardized against a primary standard. It is usually standardized

against a primary standard.

52
 --l
I he base NaOH is an exanrple ol .r s:r','.::dan slatrdard. Courrnercralir ar ail.rblu \aOll contains
rnpurilies of NaCl, Na2CO:, auLl NarSOr. and readily absorbs H2O lionr the rtnrr:spherc. 1'o

tletelmine the concentralion ofNaOll il a iolulion- it is titrated against a prinrarl slandard weak acid,
such as potassium hydrogen phthalate. KHCnHrOr.

1.4.6 Chemical indicator

Chemical indicator. any substance that gives a visible sign. usually by a colour
change, ofthe presence or absence ofa threshold concentration ofa chemical species, such as
an acid or an alkali in a solution. An example is the substance called nethyl yellow, which
imparts a yellow colour to an alkaline solution. If acid is slowly added. the solution remains
yellow until all the alkali has been neutralized, whereupon the colour suddenly changes to
red.

Like most indicators, methyl yellow is visible even if its concentration is as low as a
few parts per million parts of solution. Used at such low concentrations, indicators do not
have any influence on the conditions for which they are recommended. The common
application of indicators is the detection ofend points oftitrations.

The colour of an indicator alters when the acidity or the oxidizing strength of the
solution, or the concentration of a certain chemical species, reaches a critical range ofvalues.
Indicators are therefore- classified as acid-base, oxidation-reduction, or specific-substance
indicators, every indicator in each class having a characteristic transition range. Methyl
yellow, an acid-base indicator, is yellow if the hydrogen ion (acid) concentration of the
solution is less than 0.0001 mole per litre and is red if the concentration exceeds
0.0001. Ferrous 1,10-phenanthroline, an oxidation-reduction indicator, changes from red to
pale blue when the oxidation potential of the solution is increased from 1.04 to 1.08 volts;
and diphenylcarbazone, an indicator for mercuric ion, changes from yellow to violet when the

mercuric ion concentration is increased from 0.000001 to 0.00001 mole per litre. Each of
these indicators thus has a relatively narow transition range, and each is capable of giving a
sensitive, sharp indication ofthe completion ofa reaction, that is, the end point.

Although the visible change ofthe indicator is usually a colour change, in some cases
it is a formation or disappearance ofturbidity. If, for example, a soluble silver salt is added to
a solution of cyanide that contains a trace of iodide, the solution remains clear until all the
cyanide has reacted to form the soluble silver cyanide complex ion. Upon the addition of

53
inore silve[, the solution bec.rr]'rc' t'.irbid because insoluble silrer ir:didc tonrrs. Iodide is
iherefote an indicator fol excess siiler ion in this reaction.

Anothel kind ofindicator is tl.re adsorption indicator. the best-knonn representative of

u'hich is the dye fluorescein. FIuorescein is used to detect the completion ol the reaction of
silver ion rvith chloride ion. the colour change occuning in the following manner. After a

quantity of silver large enough to precipitate all the chloride has been added. additional silver
ion is partially adsorbed on the surlace of the particles of silver chloride. Fluorescein also is
adsorbed and, in combining with the adsorbed silver ion, changes from yellovrgreen to red.

It is a chemical reagent used to recognize the attainment of end point in a titration.

After the reaction between the substance and the standard solution is complete, the indicator
should give a clear colour change.

When a titration is canied out, the free energy change for the reaction is always
negative. That is, during the initial stages ofthe reaction between A & B, when the titrant A
is added to B the following reaction takes place.

A+B :+ C+D
Equilibrium constant,

..
K:-
dc.ao tcl.tDl
de.irs tAl.tBl
a= activity co-efficient.
Large values of the equilibrium constant K implies that the equilibrium concentrations
ofA & B are very small at the equivalence point. It also indicates that the reverse reaction is
negligible and the product C & D are very much more stable than the reactants A& B.
Greater the value of K the larger the magrritude of the negative free energy change for the
reaction between A & B. Since,

Free Energ, Change : AG : -RTln K

Where,
R = Universal gas Constant = 8.314 JK-lmol-r,

T : Absolute Temperature.

54
 I he teaction of the concentration ol' A &. ]:t ir,.:iis to the rcducrion oi'1hc toitl lrtc
energl chauge. It'the concentrations of A & B arc too lotv lhe magnitude of the tolai rice
energr change becomes so small and the use olth,.. rcaction lbr titration rvill not be teasibl.'.

1.4.7 Titration:

To determine the amount of substance in a solution of unknown concentration using

various titrimetric methods.

The word titmtion comes from the Latin word "titulus", which means inscription or
title. The French word title means rank. Therefore. Titration means the detemrirration of
concentration or rank ofa solution with respect to water with a pH of7.

The standard solution is usually added from a graduated vessel called a burette. The
process of adding standard solution until the reaction is just complete is termed as titration

and the substance to be determined is said to be titrated.

All chemical reactions cannot be considered as titrations. A reaction can serve as a

basis ofa titration procedure only if the following conditions are satisfied:

The reaction must be a fast one.

a It must proceed stoichiometrically.
The change in free energy (AG) during the reaction must be sufficiently large for
spontaneity of the reaction.
There should be a way to detect the completion ofthe reaction.

1.4.7.1 Volumetric Analysis:

It involves the estimation of a substance in solution by neutralization, precipitation,

oxidation or reduction by means of another solution of accurately known strenglh. This
solution is known as standard solution.

Volumetric analysis depends on measurements of the volumes of solutions of the

interacting substances. A measured volume of the solution of a substance A is allowed to
react completely with the solution of definite strength of another substance B. The volume of
B is noted. Thus we know the volume ofthe solutions A and B used in the reaction and the
strength of solution B; so the strength of the other solution A is obtained. The amount (or

55
 corcentlaii{ln ) of ihe dissolved substance iri \olur))etnc ana[]sis is usually erplesserl ir) 1'rnrs
of normalitv. 'l he rveight in grams o1' the substarce per litre of the sohrtion is rc-late'tl to

nomrality of the solution as,

Weight of the substance (g per litre) = Norrnality x gram equivalenl weight of'the
subslance.

Conditions of Volumetric Analysis:

i) The reaction between the titrant and tilrate rnust be expressed.
ii) The reaction should be practicalll, i1s1rr,un.ou..
iii) There must be a marked change in some physical or chernical property olthe
solution at the end point.
iv) An indicator should be available u,hich should sharply define the end point.
Different methods to determine the endpoint include:

o pH indicator:

A pH indicator is a substance that it changes its colour in response to a chemical change. An

acid-base indicator changes its colour depending on the pH (e.g., phenolphthalein). Redox
indicators are also frequently used. A drop of indicator solution is added to the titration at the
starfi at the endpoint has been reached the colour changes.

. A potentiometer

It is an instrument that measures the electrode potential ofthe solution. These are used
for titrations based on a redox reaction; the potential of the rvorking electrode will suddenly
change as the endpoint is reached.

. pH meter:

It is a potentiometer that uses an electrode whose potential depends on the amount of

H+ ion present in the solution. (It is an example of an ion-selective electrode.) This allows
the pH ofthe solution to be measured throughout the titration. At the endpoint, there will be a

sudden change in the measured pH. This method is more accurate than the indicator method
and is very easily automated.
. Conductance:

56
 The conductir itr i:l a solur.ion depends on the ioi.is pr'!\i:)t in it. During rrarrl'
titrations. the cor-rductir';t1 changes significantly. (i.e.. during ar: acid-base titration. the
H* and OH- ions reacl to lirnr neullal HzO, this changes the conduclivily of the solution.)
The total conductance ol the solution also depends on the olher ions present in the solution,
such as counter ions. lhis also depends on the mobilily ol each ion and on the total
concentration ofions that is the ionic strength.
. Colour change:

In some reactions. the solution changes colour without any added indicator. This is

often seen in redox titrations. for instance, when the different oxidation states ofthe product
and reactant produce different colours.

. Precipitation:

In this type of titration the strength of a solution is determined by its complete precipitation
with a standard solution of another substance.
AgNO, + NoC,l -+ AgCl + ,VoNOr
eg:

1.4.7.2. Acid base titration:

The chemical reaction involved in acid-base titmtion is known as neutralisation

reaction. It involves the combination of H3O* ions with OH-ions to form water. In acid-base
titmtions, solutions of alkali are titmted against standard acid solutions. The estimation of an
alkali solution using a standard acid solution is called acidimetry. Similarly, the estimation of
an acid solution using a standard alkali solution is called alkalimetry.

The Theory of Acid-Base Indicators:

Ostwald developed a theory ofacid base indicators which gives an explanation for the
colour change with change in pH. According to this theory, a hydrogen ion indicator is a
weak organic acid or base. The undissociated molecule will have one colour and the ion
formed by its dissociation will have a different colour.

Let the indicator be a weak organic acid of formulae HIn. It has dissociated into
H* and In-. The unionized molecule has one colour, say colour (1), while the ion, In- has a
different colour, say colour (2). Since HIn and In- have different colous, the actual colour of

57
the indicalor r.r'ill dep.:nclcnt upon the hydroger: ion conccntlation lll l. \\'hen the solr-rtion is

acidic, that is the []- ions present in excess, the indicator u'iil sho"i predominantly colorLr ( [ ).

On other hand. nhen thc solulion is alkaline, that is. when OII-ions presenl in excess, the
H* ions fumished by Lhe indicator u,ill be laken out to lbrm undissociated u,ater. Therefbre
there will be larger concenlration ofthe ions, In-. thus the indicator u,ill show predominantli,
colour (2).

Some indicators can be used to determine pH because of their colour changes

somervhere along the change in pH range. Some common indicators and their respective
colour changes are given below.

Indicator Colour on Acidic Range of Co Colour on Basic

Side Change Side l

Methyl Violet Yellow 0.0 - 1.6 Violet

Bromophenol Blue Yellow 3.0 - 4.6 Blue

Methyl Orange Red 3.1 - 4.4 Yellow

Methyl Red Red 4.4 - 6.2 Yellow

Litmus Red 5.0 - 8.0 Blue

Bromothymol BIue Yellow 6.0 - 7.6 Blue

Phenolphthalein Colourless 8.3 - 10.0 Pink

Alizarin Yellow Yellow 10.1 - 12.0 Red

i.e., at pH value below 5, litmus is red; above 8 it is blue. Between these values, it is a
mixture of two colous.

1,4.7.3 Precipitation Titration:

A titrimetric method based on the formation ofa slightly soluble precipitate is called a
precipitation titration. The most important precipitation process in titrimetric analysis utilizes
silver nitrate as the reagent (Argentimetric process).

58
 :-- -r Ci-- n -+ AlCi,.,
tsq

Manr methods are utilized in determining end points of these reactions. brrl the most
importanl method, the formation of a coloured precipitate will be considered hele.

1. In the titration of a neutral solution of chloride ions with silver nitrate. a small quantity of
potassium chromate soiution is added to ser\e as the indicator. At the end point the chromate
ions combine with silver ions to form the sparingly soluble brick-red silver cll'ornate. This is
a case of fractional precipitation, the two sparingly soluble salts being AgCI (Ksp : 1.2 x 10-
ro)
and Ag2CrOa (Ksp : 1.7x10-r2).

AgCl is the less soluble salt and initially chloride concentration is high. lrence AgCi
will be precipitated. Once the chloride ions are over and with the addition of small excess of
silver nitrate solution brick red colour silver chromate becomes visible. The titration should
be carried out in neutral solution or in very faintly alkaline solution. i.e. within the pH range
6.5-9.

In acid solutions following reaction occurs.

+ 2H+ { ----------} ZHCrO,

lf
Ilr
+
Consequently the chromate ions concentration is reduced and the solubility product of silver
chromate may not be exceeded. In markedly alkaline solution, silver hydroxide (Ksp:2.3 x
108) might be precipitated.

The titration can be carried out with dichlorofluorescein as the indicator. Dichlorofluorescein
is an example of an adsorption indicator. Adsorption indicators have the interesting property
of changing colour when they stick (adsorb) to the surface of a precipitate. During the
titration the dichlorofluorescein molecules exist as negatively charged ions (anions) in
solution. As the AgCl precipitate is forming, the excess Cl- ions in the solution form a layer
of negative charge on the precipitate surface. As the equivalence point is reached and passed,
tirc cxcess Cl'ions on lhe preciprt.Lte sulliLcr are replaced by escess,{q- i()r-i. giring the
sur'f'ace a posilive charge. The negativelr charged indicator rvill be allracted to the positi\,'elv
chargc-d precipitate surface r.vhere it absorbs and changes colour. The suspcudcd precipitate
u,ill have a pink tinge because of some premature displacement of chloride ion by the

dichloroi'luorescein ion. When the pink colour starts to persist for slightll, longer peliods of
time. the drip rate is lou,ered. The end poir.rt is reached when the entire solution tums pink. It
is impor-tant that the AgCl precipitate be prer,'ented frotn coagulation during the titration. For
this reason a small amount ofdextrin is added to the solution.

1.4.7.4 Complexometric Titration :

This type of titration depends upon the combination of ions (other than H* and OH)
to form a soluble ion or compound as in the titration of a solution of a cyanide with AgNO3.

Princip le of C omplexometric Titration :

Complexometric titrations are parlicularly useful for determination of a mixture of

different metal ions in solution. Ethylene diamine tetra acetic acid (EDTA), is a very
important reagent for complex formation titrations. EDTA has been assigned the formula II in
preference to I since it has been obtained lrom measurements of the dissociation constants
that two hydrogen atoms are probably held in the form of zwitter ions.
clr2-c0oH

-{:H2-CHI-

HOOC-{rrr2

/
:0oc:ct-I:

60
EDTA behar,cs ris ;i .iicalboxylic acid u.ith two s1r:ongl\ acitlic grorqrs. Fol simpiicily [1i) l;\
may be given the lbrntula H+Y. the disodium salt is rherefbrc Na2H2Y and it has the cornplcx

forming ion HlYr'in aqueous solution. The reactions rvith cationsmay be represented as:

M2' - H:Y t----- MY:'+ 2H

M3* + HrY 2'--* MY- + 2H*

Ma*+ HzY 2---- MY + 2lf

One gram ion of the complex-forming ion H2Y2-reacts in all cases with one gram ion
of the metal. EDTA forms complexes with metal ions in basic solutions. In acid-base
titrations the end point is detected by a pH sensitive indicator. In the EDTA titration metal
ion indicator is used to detect changes ofpM. It is the negative logarithm ofthe free metal ion
concentration, i.e., pM: - log [M2*]. Metal ion complexes form complexes with specific
metal ions. These differ in colour from the free indicator and a sudden colour change occurs
at the end point. End point can be detected usually with an indicator or instrumentally by
potentiometric or conductometric (electrometric) method.

Ehd Point

volume of EDIA

There are three factors that are important in determining the magnitude of break in titration
curve at end point.

The stability of complex formed: The greater the stability constant for complex formed,
larger the charge in free metal concenfoation (pM) at equivatent point and more clear would
be the end point.

61
The number of rteps involved in complex formalion: |L'\\er the number of steps reqLriicJ
in the formatiorr ot'1he complex, greater r,,'oulcl be the break in titration curve a1 equivai!'u1

point and clealer u'ould be the end point.

Effect of pH: During a complexornetric titration. the pH must be constant by use of a butll'r
solution. Control of pH is important since the H- ion plays an important role in chelalion.
Most ligands are basic and bind to H* ions throughout a wide t'ange of pH. Some of thc"se

H*ions are frequently displaced from the ligands (chetating agents) by the metal during
chelate formation.

Equation below shows complexation between metal ion and H* ion for ligand:

M2* + H2-EDTA --+ M-EDTA + 2Ff

Thus, stability of metal complex is pH dependent. Lower the pH ofthe solution, lesser
would be the stability of complex (because more H* ions are available to compete with the
metal ions for ligand). Only metals that form very stable complexes can be titrated in acidic
solution, and metals forming weak complexes can only be effectively titrated in alkaline
solution.

Mecltanism of action of indicator:

During an EDTA titration 2 complexes are formed: D M-EDTA complex and ii) M-
indicator complex. The metal-indicator complex must be less stable than the metal-indicator
complex.

M-In + EDTA--- M-EDTA + In

Erichrome black T is a metal ion indicator. In the pH range 7-11 the dye itself has a
blue colour. In this pH range addition of metallic salts produces a brilliant change in colour
from blue to red.

M2* + HIn2- ---+ MIn' + ff

(Blue) (Red)
This colour change can be obtained with the metal ions. As the EDTA solution is
added, the concentration of the metal ion in the solution decreases due to the formation of
metal-EDTA complex. At the end point no more free metal ions are present in the solution.
At this stage, the free indicator is liberated and hence the colour changes from red to blue.

6Z
lndicators used in complexometric riirations are as follorvs:

S.No. Name o{ Colour pH range !l etals detected

indicator change
I Mordanl biack Red to Blue 6-7 Cc.Ba
II Mg"Zn.Cd,Mn,Pb,Hg
Eriochrome
black T i
Solochrome I

black T
2 Murexide 0r Violet 12 Ca,cu,Co
Ammonium Blue
pulpurate
3 Catechol-r,ioletViolet to 8-10 Mn.Mg,Fe,Co,Fb
Red
4 Methyl Blue Blue to 4-5 Pb,Zn"Cd,Hg
Yellow
Thymol Blue Blue to Grey 10-12
5 Alizarin Red to 4.3 Pb,Zn,Co,Mg,Cu
Yellow
6 Sodium Blue to Red 4 Al, Thorium
Alizarin
sulphonate
7 Xylenol range Lemon to 1-3 Bi, Thorium
Yellow
4-5 Pb,Zn

5-6 Cd, Hg

Aliain fiuorine btu(sli?arin cospl e.ose) Eriodlrome Blue Btack R

63
 Hrl

H,-r l'ii{lH
\/
-
\/ /,l...::,
N---(,
.,\
,)
,4

/\i\
/\
\\ //
\\ ,7
\__i,
Cdcon cutoxylic acrd Catechol - \,rolet

Metal-EDTA complex

Applications of Complexometric titrdtior, :

Complexometric titration is widely used in the medical industry because of the

micro litre size sample involved. The method is efficient in research related to the
biological cell.
Ability to titrate the amount of ions available in a living cell.
Ability to introduce ions into a cell in case of deficiencies. Complexometric
titration involves the treatment of complex ions such as magnesium, calcium,
copper, iron, nickel, lead and zinc with EDTA as the complexing agent.
Complexometric titration is an efficient method for determining the level of
hardness of water.

Types of Complexometric Titratio n :

As mentioned earlier, EDTA is a versatile chelating titrant that has been used in
innumerable complexometric determinations. The versatility of EDTA can be ascribed to the

64
 l
diilclent uars in w.hich the complexomelric iiir'irliou can be' executed. Let us leatn.tht,itt
dilferent rial's in rvhich we can use EDTA tirrarions.

l. Dircct Titration: It is the simplest and th!- rxosl convenient method in rvhich the slandard
solution ol F-l)TA is slowly added to the meral ion solulion till the end point is achieved. It is
similar to simple acid-base titrations. For this melhod to be useful the fomration constanl
must be largc' and the indicator must provide a veD' distinct colour change as ntentioned
earlier. Furlher we need standardized solution of EDTA and sometimes auxiliary conrplexing
agents may be required. Some important elements which could be determined directly by tlie

complexometric titration are Cu, Mn, Ca, Ba, Br, Zn. Cd.Hg, Al, Sn, Pb, Bi, Cr, Mo. Fe, Co,
Ni, and Pd, etc. However, the presence of other ions may cause interference and need to be
suitably handled.

2. Back Titration: In this method, an excess of a standard solution of EDTA is added to the
metal solution being determined so as to complex all the metal ions present in the solution.
The excess of EDTA left after the complex formation with the metal is back titrated with a
standard solution of a second metal ion. This method becomes necessary if the analyte
precipitates in the absence of EDTA or reacts too slowly with EDTA, or it blocks the
indicator. For example, determination of Mn is done by this method because a direct titration
is not possible due to precipitation of Mn(OH)2. The excess EDTA remaining after
complexation, is back titrated with a standard Zn solution using Eriochrome black T as

indicator. However, one has to ensure the standard metal ion should not displace the analyte
ion from their EDTA complex.

3. Replacement Titration: When direct or back titrations do not give sharp endpoints or
when there is no suitable indicator for the anallte the metal may be determined by this
method. The metal to be analyzed is added to a metal-EDTA complex. The analyte ion (with
higher K1) displaces EDTA from the metal and the metal is subsequently titrated with
standard EDTA. For example, in the determination of Mn an excess of Mg EDTA chelate is
added to Mn solution. The Mn ions quantitatively displace Mg from Mg-EDTA solution
because Mn forms a more stable complex with EDTA. The freed Mg metal is then directly
titrated with a standard solution of EDTA using Eriochrome black T indicator. Ca, Pb and Hg
may also be determined by this method.

65
-1. lndircct Iitration: Cerlain anions lhat lrr|rri precipitate n'ith rnetal calion: ilr!i Jr) IrL)t

leaci riith IID]'A can be analyzed indirectly. lhe anion is first plecipitatc'tl uitlr a irretal
cation and lhe precipitate is washed and boiled uilh an excess ol'disodium ED I'.,\ solution 1o

fbrm the rnelal complex. The protons lionr disodium EDTA are displaced bv a lrearl nrelal
and titrated r.vith sodium alkali. Therefore. this ruethod is also called alkalimetric litration. For

example. barbiturates can be deternined b1, this method.

1.4.7.5 Redox titration:

A reaction in which one or more electrons are lost is known as oxidution and a
reaction in r.l'hich one or more electrons are gained is known as reduction. Accordingly, a
substance which can accept one or more electrons is known as oxidizing agent and a
substance which can donate one or more electrons is called reducing agent. Titrations ofthis
type are called redox titrqlrors. Thus, redox titrations are those involving transfer olelectrons
from the reducing agent to the oxidizing agent.

Potassium permanganate, potassium dichromate, ceric sulphate, etc., are the common
oxidizing agents used in redox titrations. Oxalic acid, Mohr's salt and arsenious oxide are

reducing agents commonly used in redox titrations.

1.4.7.6 Iodometry and Iodimetry:

Iodine is a mild oxidizing agent. In the presence of a suitable reducing agent, it is

reduced to iodine ion, I-. In addition to this, all oxidizing agents having electrode potential
greater than 0.54 V can oxidize I-to Iz. When iodine solution is directly used for the
estimation of reducing agents, the titration is called iodimetric titration (iodimetry). The
titrations involving the iodine liberated in a chemical reaction are called iodometric titration
(iodometry).

66
 i/ hri l
2.1 Ionic Bonding

Deftnition of lonic Bonding

Chemical bonds lbrm rvhen the total energy ofthe bonded aloms is lou,er than the total
energy of the separate atoms. 'Ihe form the bonding lakes is determined by the electron
anangement that minimizes the energy.

In some instances. electrons are shared between atoms - this is termed covalenl
bonding.
In other instances, there is a complete transfer of one or more electrons from one atom
to another. The atom that loses electrons becomes a positivety charged ion. The atom that
receives electrons becomes a negatively charged ion.
This leads to ionic bonding - the mutual electrostatic attraction of positive and negative
charges. In its purest form. ionic bonding is not directional. It can be regarded as
simple Coulombic attraction between point charges. This is different from covaient bonding,
in which the sharing ofelectrons results in directional bonds.

Electron Transfer

Li transfers an electron to F. The result is that both the resulting ions become electrically
charged and have complete, stable electron shells.

E I e c t ro s tat ic Att ra ct io n

67
The positive and nogalire itxs are electrostaticalll altrac:rd 1o onr-'-another. resulting in an
ionic bond.
The coulombic lbrce has no preferred direction. rvith rhe result that ionic compounds tend
exist as giant crvslal iattice structures of ions packed 1oB.elher.

A Sample of Lithium Fluoride's Crystal Lattice

2.1.1 Lattice Energy

Introduction

The ionic stability of a solid is related to the lattice energy which is a form of
potential energy. It takes a large amount of energy to break the bond between ionic solids as
they are extremely stable. The effects ofthis can be seen when rve consider the melting point.
Sugar melts easily and we have seen many recipes that require sugar. Although salt which has

a similar look does not melt at the temperature food cooks. This is because ofthe fact that salt
or sodium chloride is an ionic solid that has very strong bonds. So, due to these strong bonds
melting salt is difficult.

68
The ionic solids have their ions arranged in a crystal lattice (as shown in the image). And
because of this arrangement, they get their strength.

Lattice energy is also called as lattice enthalov. An ionic solid is formed when
gaseous ions combine together and release energy. In the same way, a certain amount of
energy will be required to change the ionic solid into the gaseous ions (which it was made up
of). The ions are held together by this energy and thus lattice energy is a measure of it.

Lattice dissociation enthalpy is the energy required to break the ionic bonds of the
solid state aad form the gaseous ion. Lattice formation enthalpy is the energy that is released
when the gaseous ionic components bind together to create ionic solid. The energy state ofan
ionic solid is lower than the gaseous ions and thus they are more stable. From here tve get the
conclusion that lattice dissociation enthalpy will always be positive and lattice
formation enthalpy will be negative. The lattice energy will be larger with a stable ionic solid
and bonds that are more stable are harder to break. Just like a chair that has been nailed
together is better protected against breakage than a chair stuck together with gum.

2.1.2 Factors that Influence Lattice Enerry

There are two factors that affect the lattice energy.
.i. Ionic Charge
- Lattice energy is greater in ions that have greater charge.
.!. Ionic Radius - As we know by now, the ionic radius is the measuement of the size of
the ion. Lattice energy is higher in compounds that have smaller ions because the ions
are packed closer together.

2.1.3 Definition

69
 I-attice Energr- is a t1'pe ol'pr)ldnlial energy that may be detined ir.r 1r.\{) \\a\s. In one

dellnition. "the lattice energt' is the energ)' required to breok port n ionic solid and
conrtert ils componefit atoms irrto gaseous lans ". This definition causcs th!, r'alue for the
lattice energy to alu,ays be positive. since this rvill alrvays be an endothermic rc'action.
Tl-re other definition says that "lattice energy is te reverse process, meoning it is tlte
energ), released when gaseous ions Lintl to form an ionic solid". As implied in the
definition, this process will always be exothermic, and thus the value for lattice energy will
be negative. Its values are usually expressed with the units kJ/mol.

Lattice Energy is used to explain the stability of ionic solids. Some might expect such
an ordered structure to be less stable because the entropy of the systen.r would be low.
Horvever, the crystalline structure allows each ion to interact with multiple oppositely charge
ions, which causes a highly favorable change in the enthalpy ofthe system. A lot ofenergy is
released as the oppositely charged ions interact. It is this that causes ionic solids to have such
high melting and boiling points. Some require such high temperatures that they decompose
before they can reach a melting and/or boiling point.

2.1.4 Born-haber Cycle

Bom-Haber Cycle is a methodology to analyze the reaction energy, which was
introduced by German scientist Bom and Fi(z Haber. It explains about the formation of ionic

compounds,

There are various processes involved in Bom-Haber Cycle.

1 Electron affinity
2. Ionization energy
3. Sublimation energy
4. Heat of formation
5. Dissociation energy

Process 1: Electron affinity

Energy released when an electron is added to the neutral atom. The trend of electron affrnity
in the periodic table; electron affinity increases along the period (from left to right in the
periodic table) and electron affinity decreases down the group.

Process 2: Ionization energ)

Ionization energy is the energy required to remove an electron form a neutral atom or form an
ion. In this process- e rrcr,rrr is lequired to rel'r:()\'c irir cicclrrrrr liom an atom; hence. thc r,i.,r"
'[-hr'lrcnd
of ionization energy uill airvays be positive !alur's. of ionization energf in thc
periodic table is thal ionizalion energy decreases liurr lhe top lo bottom in the group and
increases liom left to right in the period.

Process 3: Sublimation Energy

It is the energy required to change the phase ofthe reactants f'rom solid to gas. Since. energ)
is utilized for the conversion ofone phase to another. sublimation energy is positive.

Process 4: Heat of formation

It is the energy change when a compound is formed from elements. The energy may be
positive or negative since it depends on the interaction ofthe atoms in the molecule.

Process 5: Dissocialion energt

It is the energy required to break a chemical bond. It is an endothermic process since it needs
energy.

Reprcren(ntion of Born-I{abcr Cycle;

aHr'|
M(s) * I /2 X:(g) MX (s)

an*o I

+ |"*
M(B) x(c) t^atticc Energy (U)
ronisation Energy (lE) | I Eto,ron
(EA)
I lAffiniry
Mi' +X-

aHro- al{qib + lE + AIIdks + E.A l-U

2. 1.4 Electronegativity
Inlroduction

The term "electronegativity" was introduced by JiirJs Jacob Berzelius in 1811, though
-'was
the concept was known even before that and studied by many chemists
including Avoeadro. In spite of its long history, an accurate scale of electronegativity was not
developed until 1932, when Linus Pauline proposed an electronegativity scale, which
depends on bond energies, as a development ofvalence bond theory. It has been shown to
correlate with a number of other chemical properties. Electronegativity cannot be directly.
measured and must be calculated from other atomic or lnolecular properties. Several methods

of calculation have been proposed, and although there may be small differences in the

7L
nurnericai \ alucs of the electronegali\ it) . r-.)elhods shorv the san-re pgdrr,l ic

trends betrec;r clcments.

The t.r.rost commonll, used method o1'calculation is tliat originally proposed b1' I.inus
Pauling. This gives a dimensionless quantit.r. conrmonlr rel-erred to as the Pauling scale (/,).
on a relative scale running from around 0.7 to i.98 (hydrosen - 2.20). When other methods
of calculation are used, it is conventional (although not obligatory) to quote the results on a

scale that covers the same range of numerical values: this is known as electronegalivilv
in Pauling units.

As it is usually calculated, electronegativity is not a property of an atom alone. but

rather a property of an atom in a molecule. Properties ofa free atom include ionization
enersy and electron afhnitv. It is to be expected that the electronegativity ofan element will
vary with its chemical environment, but it is usually considered to be a transferable propertv,
that is to say that similar values will be valid in a variety ofsituations.

Electronegativity, symbolg, is a chemical property that describes the tendency of

an atom to attract a shared pair ofelectrons (or electron density) towards itself. An atom's

electronegativity is affected by both its atomic number and the distance at which its valence
electrons reside from the charged nucleus. The higher the associated electronegativity
number, the more an element or compound attracts electrons towards it.

On the most basic level, electronegativity is determined by factors like the nuclear
charee (the more plel!q!! an atom has, the more "pull" it will have on electrons) and the
number/location of other electrons present in the atomic shells (the more electrons an atom
has, the farther from the nucleus the valence electrons will be, and as a result the less positive
charge they will experience-both because of their increased distance from the nucleus, and

because the other electrons in the lower energy core orbitals will act to shield the valence
electrons from the positively charged nucleus).
The opposite of elechonegativity is electropositivity: a measure of an element's ability
to donate electrons.
Mainly, this is an attribute of metals, meaning that, in general, the greater the metallic
character of an element the greater the electropositivity. Therefore, the alkali metals are most
electropositive of all. This is because they have a single electron in their outer shell and, as
this is relatively far t'ronr the iluck'irs of the atom. it is easily lost: in olhel uords. these metals
have low ionization enerIies.

While electronegalivil) irlcreases along pg11ads in the pg!14[9___14!,!9" and decreases

down groups. electropositivitl'decreases along periods (frnm lefi right)

and increases down groups.

2, 1.5 Pauling electronegativity

Paulins first proposed the concept of electronegativity in 1932 as an explanation of

the fact that the covalent bond between two different atoms (A-B) is stronger than would be
expected by taking the average of the strengths of the A-A and B-B bonds. According to
valence, of which Pauling rvas a notable proponent, this "additional stabilization" of
the heteronuclear bond is due to the contribution oflqnis canonical forms to the bonding.

The difference in electronegativity between atoms A and B is given by:where

the dissociation energies, Eo, ofthe A-B, A-A and B-B bonds are expressed in electronvolts,

the factor (eV)-vz being included to ensure a dimensionless result. Hence, the difflerence in
Pauling electronegativity between hydrogen and bromine is 0.73 (dissociation energies: H-
8r,3.79 eV; H-H, 4.52 eY; Br-Br 2.00 eV)

As only differences in electronegativity are defined, it is necessary to choose an

arbitrary reference point in order to construct a scale. Hydrogen was chosen as the reference,
as it forms covalent bonds with a large variety of elements: its electronegativity was fixed
first at 2.1, later revised to 2.20. It is also necessary to decide which of the two elements is
the more electrcnegative (equivalent to choosing one ofthe two possible signs for the square
root). This is usually done using "chemical intuition": in the above example, hvdroeen
bromide dissolves in water to form H* and Br- ions, so it may be assumed that bromine is
more electronegative than hydrogen. However, in principle, since the same electronegativities
should be obtained for any two bonding compounds, the data are in fact over determined, and
the signs are unique once a reference point is fixed (usually, for H or F).

To calculate Pauling electronegativity for an element, it is necessary to have data on

the dissociation energies ofat least two types of colalent bond formed by that element. A. L.
Allred updated Pauling's original values in 1961 to take account of the greater availability of

73
thennodynamic data" iiird it is 'tlrcse "rc'vised Pauling" values o1'1hc c. tetronegativitl that are

rlost often used-

2. 1.6 Mulliken electronegativity

Robert S. Mulliken proposed that the arithmetic mean ol the first ionization
enerev (Ei) and the electron affinity (E"u) should be a measure of the lendency of an atom to
attract electrons. As this det'inition is not dependent on an arbitrary relative scale, it has also
been termed absolute electronegativity, with the units ofkiloioules per rnole or electron volts.

However, it is more usual to use a linear transfomration to transform these absolute

values into values that resemble the more familiar Pauling values. For ionization energies and
electron affinities in electron volts, and for energies in kilojoules per mole,

The Mulliken electronegativity can only be calculated for an element for which the
electron affinity is known, fifty-seven elements as of 2006. The Muliiken electronegativity of
an atom is sometimes said to be the negative of the9h9!SiSel_pqlgl[i41. By inserting the
energetic definitions of the ionization potential aud electron affinity into the Mulliken
electronegativity, it is possible to show that the Mulliken chemical potential is a finite
difference approximation of the electronic energy with respect to the number of electrons.,
i.e.,
2,1.7 P olaring p ower and Polarisability
Chemical bonds are broadly classed as covalent and ionic. In both cases the energy of
the bonded atoms is lower than the energy of the separated atoms due to an electrostatic
(positive to negative) attraction between the bonded atoms.

In covalent bonds the electrostatic attraction is between the bonding electrons and the nuclei
and core electrons of both atoms. In ionic bonds it is the attraction ofthe positive ion for the
negative ion. In fact, very few bonds are purely covalent or purely ionic.
For example the covalent OH bond in water is polarised due to the difference in
electronegativity of hydrogen and oxygen.

Ionic bonds may have considerable covalent character if

the cation is small and/or highly charged (high charge density). These cations are said to

74
 l
be polarising lor have high polalising por,rcr) heeause they diston the elcciron e.t,Lii ... rhe
anion. and the electron density betr,r,een the nuciei is l-righer than in the corresponding iLuic
bond.

polarizing power of cotions

Be2* Alr'
Na* Mg'* high

K- Ca2*

Rb* S12*

Cs* Ba2*

polarizability of anions

02- F
s2- cl
se2- Br

high I
The cartoon is an to show that how the distortion ofthe electron cloud is greater for
smaller catici-ns.
Bonds between polarising cations and polarizable anions have significant covalent
covalent character. The polarizability of the anion depends both on its size and charge.

Anions of lower charge density are more polarizable. For anions having the same charge,
the larger anion is polarised to a greater extent (F < Cf < Ba < I). For anions of similar
size, the more polarizable anion has a greater negative charge (S2- > Cf. This is because a
larger charge indicates a larger excess ofelectrons over protons.

2.1.8 Partial Ionic Character from Electronegativity

When two atoms with different electro-negativities combine to form a covalent bond,
the electron density between atoms is shared in such a way that it is displaced more towards
the more electronegative atom.

As a result, the more electronegative atom gets a partial negative charge, while the
less electronegative atom gets a partial positive charge. The partial positive and negative
charges on the dipole are indicated by the + 6 and - 6, respectively.

75
 lheret'ore. in hetero-alomic nrr.ler:ulc' in rrliich the t\\'o atoms ciillcr consi<-lcrabil in
c'iecl rc-n egatil'ily. tw-o electric poles clerekrp. \\/e say that the molecule has developed
polaritl .

The covalent molecule rvith the 1uc. opposilely charged poles is called a dipole.
For example, the dipole in h1'drogen chloride.is represented as
-5
H*6 - cl
Hence. the bond is called a polar covalent borrd. and the molecule is called a polar covalent
molecule.
When two atoms of different elements are linked by a covalent bond, the shared
electrons are not attracted equally by the lwo nuclei of bonding atoms. Due to unequal
distribution of electron cloud, one end of the molecule acquires partial positive charge and
the other end acquires equal partial negative. The polarity of bond gives partial ionic
character. The percentage of partial ionic character depends upon the difference of E.N. of
two atoms join with each other through a covalent bond.
Example:
1. HCI molecule:
E.N.ofH=2.1
E.N of Cl = 3.0
Due to difference of E.N., the ability Cl-atom to attract shared pair ofelectron is greater
than that of
H-atom. Therefore, covalent bond in HCI has ionic character.
In HCl, covalent bond is 17% to 18% ionic.
2. HF molecule:
E.N.ofH=2.1
E.N.ofF=4.0
In this example difference of E.N. is greater as compare to HCl. Therefore, ionic
character ofHF is 64010.

Ionic character of covalent compound affects properties ofthese compounds. For

example viscosity, M.P., B.P. of compounds having ionic character are higher than that of
non-polar compounds.

76
2.1.9 Ionic vs Coralent Bonding
Chemical contpounds are frequently classilied b1 the bonds betq,een constitueni
atoms. There are nrultiple kinds of aftractive forces. including colalent, ionic, and metallic
bonds. Ionic bonding models are generally presented as the complete loss or gain of one or
more valence electroirs l}crm a metal to a noruretal, resuiting in cations and anions that are
held together by altractive electrostatic forces.

The formation of atr ionic bond between lithium and fluorine to fomr LiF. In reality, the
bond between these aloms is more complex than this model illustrates. The bond formed
between any two atoms is not a purely ionic bond. All bonding interactions have some
covalent character because the electron density remains shared between the atoms. The
degree of ionic versus covalent character of a bond is determined by the difference in
electronegativity between the constituent atoms. The larger the difference, the more ionic the
nature of the bond. In the conventional presentation, bonds are designated as ionic when the
ionic aspect is greater than the covalent aspect ofthe bond. Bonds that fall in between the two
extremes, having both ionic and covalent character, are classified as polar covalent bonds.
Such bonds are thought ofas consisting of partially charged positive and negative poles.

Example of a polar covalent bond

When a carbon atom forms a bond with fluorine, they share a pair of electrons.
However, because fluorine is more highly electronegative than carbon, it attracts that shared
electron pair closer to itself and thus creates an electric dipole. The lowercase geek delta
written above the atoms is used to indicate the presence of partial chargos. This bond is
considered to have characteristics ofboth covalent and ionic bonds.
Though ionic and covalent character represent points along a continuum, these
designations are frequently useful in understanding and comparing the macroscopic
properties of ionic and covalent compounds. For example, ionic compounds tlpically have
higher boiling and melting points, and they are also usually more soluble in water than
covalent compounds.

2.1.10 Fajans' rules

Eemulet€c.*y Kazimierz Fajans in 1923 are used to predict whether a chemical

bond will be covalent or ionic, and depend on the charge on the cation and the relative sizes

of the cation and anion. They can be summarized in the following table:

77
 Ionic Covalent

Lou positir,e charge High positive charge

Large cation Small cation

Small anion Large anion

Thus sodium chloride (with a low positive charge (+'l ). a fairly large cation (-1 A) and
relatively small anion (0.2 A) is ionic; but aluminiun iodide (AlI3) (with a high positive
charge (+3) and a large anion) is covalent.

Polarization will be increased by:

. high charge and small size ofthe cation

. Ionic potential A Z+h+ (= polarizing power)
. High charge and large size of the anion
. The polarizability ofan anion is related to the deformabiiity of its electron cloud
(i.e. its "softness")
. An incomplete valence shell elechon configuration
. Noble gas configuration of the cation produces better shielding and less
polarizing power
. e.g. Hg2* (r+: 102 pm) is more polarizing than Caz* 1r+ = 100 pm)

The "size" of
,. ,the. charge in an ionic bond depends on the number of electrons
a:,
transferred. An aluminium atom, {or exarrple, with a +3 charge has a relatively large positive
charge. That positive charge then exerts an attractive force on the electron cloud of the other
ion, which has accepted the electrons from the aluminium (or other) positive ion.

Two contrasting examples can illustrate the variation in effects. In the case of aluminium
iodide an ionic bond with much covalent character is present. In the All:bonding, the
aluminium gains a +3 charge. The large charge pulls on the electron cloud of the iodines.
Now, if we consider the iodine atom, we see that it is relatively large and thus the outer shell
electrons are relatively well shielded from the nuclear charge. In this case, the aluminium
ion's charge will "tug" on the electron cloud of iodine, drawing it closer to itself. As the
electron cloud of the iodine nears the aluminium atom, the negative charge of the electron
.](rud ".illlcels" oilt the posiii\e charge ol'1lre alunrinium cation.'Ihis pr)iiLi!:..i rlt ionic bond
r'r'itlr col'aient character. A cation har ing inerl gas like configuralion has less 1;r,lar-ising pora,er
in comparison to cation l'raving pseudo-inert gas like configuration.

Nor'v, if we take a different example. for example AlF3. We see that a similar situation
occurs. but instead of iodine we now have fluorine, a relatively small highly clecrronegative
atom. The fluorine's electron cloud is definitely less shielded frorn the nuclear charge and will
thus be less polarisable. Thus, we get an ionic compound (metal bonded to a non metal) with
slight covalent character.

2.2 VSEPR Theory

Valence sltell electron pair repulsion (VSEPR) theory

VSEPR theory is used to predict the arrangement of electron pairs around non-
hydrogen atoms in molecules, especially simple and symmetric molecules, where thesddrey,
central atoms participate in bonding to two or more other atoms; the geometry of these key
atoms and their non-bonding electron pairs in tum determine the geometry of the larger
whole.

The number of electron pairs in the valence shell ofa centml atom is determined after
drawing the Lewis structue cf the molecule, and expanding it to shou, all bonding groups
and lone pairs of electrons. In VSEPR theory, a double bond or lriple bond are treated as a
single bonding group. The sum of the number of atoms bonded to a central atom and the
number oflone pairs formed by its nonbonding valence electrons is known as the central
atom's steric number.

The electron pairs (or groups if multiple bonds are present) are assumed to lie on the
surface ofa sphere centered on the central atom and tend to occupy positions that minimize
their mutual repulsions by maximizing the distance between them. The number of electron
pairs (or groups), Ih€reforc, determines the overall geometry that they will adopt. For
example, when there are two electron pairs surrounding the central atom, their mutual
.:t/
repulsion is minimp:l when they lie at opposite poles of the sphere. Therefore, the central
atom is predicted to adopt a linear geometry. If there are 3 electron pairs sunounding the
central atom, their repulsion is minimized by placing them at the vertices of an equilateral
triangle centered on the atom. Therefore, the predicted geometry is trigonal. Likewise, for 4
elechon pairs, the optimal arrangem ent is tetrahedral.
A.toms Ideal bond
Electron
bonded angle
domains
to Shape Flxample Image
(Steric
central bond
number)
angle)

)n.) linear c02

trigonal
,o
Dlanar

13 Angular

{
tetrahedral 109.5' Jf-r+,

2 Angular (104.48')[10] H2O

II II

5 0 5
trigonal 90",120", pcl5
t:::!!!
bjpylarxidql 180'

1 5 SF4

3 2 5 T-shaped CIF3

2 3 5 1800 XeF2

6 0 6 octahedral SF6

80
 Atoms Itleal bond
Electron
bonded angle
to
Lone domains
Shape (cxample's Examplc Inragc
central
pairs (Steric
bond
I number)
atom angle)
I

square
90'(84.8") BrF5
5 6
pyramidal ;a'"
2 6 square planar 90', 180" XeF4 :4,
'.. I
,,t , l

'7
0 7
bipyramidal lov dJl
710 ono
oentagonal ..* }
't- Pwamidal 144"
XeOF5

'o't
-._ _ __--_'.-' t'

<. -' oentagonal

JZ
Planar
72".144" XeF5-

8 0 8 XeFS2-
:

{
9 0 9 ReH92*
rrtd
3',

-:14
2.1.11 Valence bond (VB) theory

In chemistry, valence bond (VB) theory is one of two basic theories, along
with molecular orbital (MO) theory, that were developed to use the methods of quantum
mechanics to explain chemical bonding. It focuses on how the atomic orbitals of the
dissociated atoms combine to give individual chemical bonds when a molecule is formed. In
contrast, molecular orbital theory has orbitals that cover tie whole molecule.
According to this theory a covalent bond is formed between the two atoms by the
overlap of half filled valence atomic orbitals of each atom containing one unpaired electron.
A valence bond structure is similar to a Lewis structure, but where a single Lewis structure
cannot be written, several valence bond structures are used. Each of these VB structues
represents a specific Lewis structure. This combination of valence bond structures is the main

81
poinl () I' rcsonancr' theor). Valence boncl ihl'orr considers thal the overlappinu a1(\)ric

orbitaJs o1'thc participatirrg atonls tbrm a cherrricll nond. Because of the overlap.pin-u. it is

most probable that electrons should be ir.r the bond rcgion. Valence bond theorl r'ieus bonris
as u'eakl1'coupled orbitals (small overlap). Valence hond theory is typically easier Io emplov
in ground staternolecules. The inner-shell orbitals and electrons remain essentially unchanged
during the lbnnation of bonds.

I
a i
o bond between two atoms: localization
of electron density

Two p-orbitals forming a n-bond.

2.1.7 Important aspect ofthe Valence Bond theory

An important aspect of the Valence Bond theory is the condition of maximttm

overlap, which leads to the formation of the strongest possible bonds. This theory is used to
explain the covalent bond formation in many molecules.

For example, in the case of the Fz molecule, the F-F bond is formed by the overlap
ofp orbitals ofthe two F atoms, each containing an unpaired electron. Since the nature of the
overlapping orbitals are different in Hz and Fz molecules, the bond strength and bond lengths
differ between Hz and Fz molecules.

In an HF molecule the covalent bond is formed by the overlap of the ls orbital of H and the
2p" orbital ofF, each containing an unpaired electron. Mutual sharing of electrons between H
and F results in a covalent bond in HF.

2.1.8 Molecular orbital theory

Molecular orbital theory is concemed with the combination of atomic orbitals to form
new molecular orbitals. These new orbitals arise from the linear combination of atomic
orbitals to form bonding and ar.rtibondinq orbitals. Tht bonding ortriirls arl a1 a lowet'encrgy
than the antibonding orbirrls. so they are the first to fill up. 81 liguring out the molecular
olbitals, it is easy to calculare bond order.

2.I.9 Antibonding vs, Bonding Orbitals

Electrons that spend most of their time between the nuclei ol trvo atoms are placed
into the bonding orbitals, and electrons that spend most oftheir time outside the nuclei of two
atoms are placed into antibonding orbitals. This is because there is an increasing iq electron
density between the nuclei in bonding orbitals, and a decreasing in electron density in
antibonding orbitals LCha4-459). Placing an electron in the bonding orbital stabilizes the
molecule because it is in between the two nuclei. Conversely, placing electrons into the
antibonding orbitals will decrease the stability of the molecule. Electrons wili filI according
to the energy levels ofthe orbitals. They will first fill the lou,er energy orbitals, and then they
will filI the higher energy orbitals. If a bond order of zero is obtained, that means that the
molecule is too unstable and so it will not exist.

Bonding orbitals.'place most of the electron density between the nuclei of the bonded atoms.
Antibonding: orbitals place most ofthe electron density outside the nuclei.
Explanation:
' Electrons in bonding orbitals stabilize the molecule because they are between the nuclei.
They also have lower energies because they are closer to the nuclei.
Antibonding orbitals place less electron density between the nuclei.
The nuclear repulsions are greater, so the energy of the molecule increases.
Antibonding orbitals are at higher energy levels than bonding orbitals.

83
 aa
a a

a a

sond,ng

Antibonding sigma orbitals have higher energy levels and less electron density between the
nuclei.
Antibonding pi orbitals have higher energy levels and less electron density between the
nuclei.

A6tlbonding Mo

'Ta
i
'l 2Pz
(AO)
-L_
2p,
(AO)

n
ffi,
T
Eondirg MO

2.1.9.a. Linear Combination of Atomic Orbitals (LCAO)

As per this method the formation of orbitals is because of Linear

Combination (addition or subtraction) of atomic orbitals rvhich combine to form
molecule. Consider two atoms A and B which have atomic orbitals described by the wave
functions Ya and Yg .If electron cloud of these two atoms overlap, then the wave function for

84
tlrc tr:oiecule can be obtained b1' lr Iinear tombinatiorr of thc atomic orhir;llr \]/ and
r
Y3 i.e. by subtraction or addition of H,ate functions of atomic orbitals
Y/Yr1=' \/1 + \/g
The above equation fomls two molecular orbitals

Bonding Molecular Orbitals

When addition of wave function takes place, the type of molecular orbitals lbrmed are
called Bonding Molecular orbitals and is represented by Yyo = Yl + Yn
They have lower energy than atomic orbitals involved. It is similar to constructive
interference occurring in of which electron probability density increases
phase because
resulting in formation of bonding orbital. Molecular orbital formed by addition of
overlapping of two s orbitals shown in figure no. 2. It is represented by s.

Anti-Bonding Molecular Orbitals

When molecular orbital is formed by subtraction of wave function, the type of

molecular orbitals formed are called Antibonding Molecular Orbitals and is represented by
Ynro= Yr - Yr
They have higher energy than atomic orbitals. It is similar to destructive
interference occurring out of phase resulting in formation of antibonding orbitals. Molecular
Orbital formed by subtraction of overlapping of two s orbitals ar-e,
"s_he$d1_in-
figure.no,.2. It is
represented by s* (*) is used to represent antibonding molecular orbitat) called Sigma
Antibonding.

Anlibonding M0, ol5

@@
lsolated ll aloms

+ 1s)
BondlrU MQ a*
tr'ormation of Bonding and Anti-Bonding Orbital

85
 I herefbre. Combination of tlr o aturnic orbitals results in fornr:rtion of fir'o
molccular orbitals, bonding molecular orbital (BMO) lvhereas other is anti-bonding
molecular orbital (ABMO).
IIMO has low-er energy and hence greater stability than ABMO. First BMO are fiIled
then ABMO starts filling because BMO has lor,r'e'r energy than that olABMO.
Formation of molecular orbitals occurs by the combination ol atorric orbitals of
proporlional symmehy and compamble energy. Therefore, a molecular orbital is polycentric
and atomic orbital is monocentric. Number of molecular orbitals formed is equal to the
number of atomic orbitals.

2.1.9.b Differences between Molecular Orbital and Atomic Orbital

Molecular Orbital Atomic Orbital

1. An electron Molecular orbital is 1. An electron in atomic orbital is

under the influence oftwo or more under the influence ofonly one
nuclei depending upon the number positive nucleus of the atom.
of atoms present in the molecule. 2. Atomic orbitals are inlerent
2. Molecular orbitals are formed by property of an atom.
combination of atomic orbitals 3. They have simple shapes.
J. They have complex shapes.

2.1.9.c Relative Energies of Molecular Orbitals

Bonding Molecular Orbitals (BMO) - Energy of Bonding Molecular Orbitals is less than
that of Anti Bonding Molecular Orbitals because the atraction of both the nuclei for both the
electron (ofthe combining atom) is increased.
Anti-Bonding Molecular Orbitals (ABMO) - Energy of Anti Bonding Molecular Orbitals is
higher than Bonding Molecular Orbitals because the electron try to move away from the
nuclei and are in repulsive state.
The Energies of Bonding Molecular Orbitals and Anti-Bonding Molecular Orbitals are shown
in figure below:

86
 -l
nodl:

Ir

6{ antibonding mole(ular orbal.1l

l
EI . ',.;] ti r

1s atomi(
orbilal orbital

Energies of BMO and ABMO

Energt Level Diagram

The factors upon which relative energies of molecular orbitals depend are:
(D Energies of the Atomic orbitals combining to form Molecular Orbitals.
(iD The extent of overlapping between the atomic orbitals. The greater the
overlap, the more the bonding orbital is lorvered and the anti-bonding orbital is
raised in energy relative to AOs
ls Atomic Orbitals (AOs) of two atoms form two Molecular Orbitals (MOs) designated as
sls and s * ls.
The 2s and 2p orbitals (eight AOs of two atoms) form four bonding MOs and four anti-
bonding MOs as:
Bonding MOs: c 2s, a 2pz, a 2p*, n 2p"

Anti - Bonding MOc c *2s, o *2p2, tt *2py tc *2p,

Using Spectroscopy, the energy levels of these molecular orbitals are determined
experimentally. The order of increasing energy of molecular orbitals obtained by combination
of ls, 2s and 2p orbitals of two atoms is --r

cls, c *1s, o 2s, o *2s, a 2prrtt2p*= n2prrn *2p*= t *2py o *2p,

@nergy Increases from left to right)

The molecular orbital diagram representing this order ofenergy levels is shown in fig.

87
 it
zp**
m
at #4A

E*ui.!

'1 ..., \.!

,,
1 .' ".:.1

3.r

co o
t2*2d' Bond order = (4 * 1l 3 3 t?'#ait
Order of Energy
But experimental evidence for some diatomic molecules have shown that the above
sequence of energy levels of MOs is not correct for all the molecules. For example,
homonuclear diatomic molecules of second row elements like Liz, Bez, Bz , Cz, Nz , the o
2p. MOs is higher in energy than n 2p* and a 2prMOs
For these atoms, the order is: ---+ ols, o *ls, o 2s , c *2s,ltt 2p*= n 2p"1, a 2p,ltr *2p,= n *2prl, c*2p.

At At
lt. lt
IT:- IIr-
x 'I I
lv D'r d.f 'li
azp"

,l
It,
v2s
ii -. ' ':i
'-,j-i-
2s 2s
4t
_)_v_
O3
iAos)
F F? i,vio5, F {AOs)

The molecular orbital diagram representing this order of energy levels is shown in fig.
 \
I \

2p
a
$
,lt
im-
t, zp

E
I
u.t I
r24rf2*

t'
.F-u-
?s

Atomla AtomL
olbltalr on!8ali

Order of Enerry Levels for Boron, Carbon, Nitrogen etc.

This kind of energy reversal is due to mixing of 2s and 2p orbitals where the energy
difference is very close, that is, for B, C, and N atoms. According to the symmetry
interactions, the two orbitals of the same symmetry repel each other and the lower energy
orbital lowers down more while the higher energy orbital is energized more. Accordingly, o
2s and o 2p* have same symmetry and similarly for o *2s and o *2p*'t)e energy of o 2s is
lowered and that of the o 2p* becomes higher. Similarly, the energy of o *2s lowered while
that of o *2p* becomes higher. Finally, the energy of the o *2p* becomes higher than
n2p, and zr2p, which remain unchanged in the symmetry interaction. This kind of mixing of
orbitals or symmetry interaction is not applicable for Oz and Fz molecule formation because
of larger energy gap between 2s and 2p orbitals for these atoms.

Rules for Filling of Molecular Orbitah

Certain rules are to be followed while filling up molecular orbitals with electrons in
order to write correct molecular configurations:

1. Aulbau Principle - This principle states that those molecular orbital which have the
lowest energy are filled first.

89
 ) Pauli's Exclusion Principle .\ccurdin_{:l to this principle each nlolecular olbilal can
accommodate maximum crl'tuo electrons having opposite spins.
J. Hund's Rule - This rule states ti.rrrl in tw'o rnolecular orbilals of'the same energy. the
pairing ofelectrons vvill occur u,hen each orbital of same enersv consist one electron.

Order of energy of various Molecular Orbitals

Order of energ|, of various moleculor orbitals is as follotus:

For 02 and lrigher molecules ----) ols, o *ls, o 2s, 6 *2s,a 2p,,ltt2p, = tr2prl,lx*2p,= a*2p,-1, c *2p,

oozo
-+--
,'%, '.
,'r-ll-ll.l.-.\
i,' f,rt,*ta" 'lt
-m.l 2p \\
i1I@
b l'=m---|l
&

HIH
."--JTU..---
, -at \
-{u---*1 '>-{Tll--
z
2t
Hl}H
lvoLcria, Alon|.
o,bilalr 6'tlt'lt ooittir

Fig. no. 6 Order ofEnergy for 02 and Higher molecules

ForN,andlowermolecules---+ols,o*ts,o2s,o*2s,[r2p,=rzp,l,azpxln*2p-x*2p"1,6*2p,

90
 :\- N

--f1-, oip,

l;ffi-i
I
,
riffi
b
$\rs tt
2p ir 2P

b '.t-qlfP-"i
,.6!
I
trl -{[EE-i
azortz*

..-.....{iil-*-
,'q'.

Abrnlc l'aoL61irr Alott{c

ortllilt otbltrlt ortlhlti

Order of Enerry for N2 and lower molecules

Bond Order

It may be defined as the half of difference between the number of electrons present in
the bonding orbitals and the antibonding orbitals that is,
Bond order (8,O.) = (No. of electrons in BMO - No. of electrons in ABMO)/ 2
Those with positive bonding order are considered stable molecule while those with negative
bond order or zero bond order are unstable molecule.
Magnetic Behavior: If all the molecular orbitals in species are spin paired, the substance is
diamagneti. But if one or more molecular orbitals are singly occupied it is paramagnetic. For
i)
Example, if we look at 60 Molecute, it is diamagnetic as all the electron in CO are paired
as in the figure below:

91
 ':i I I

fr.,,. n,,,,

2D- 2o.. 2D. .-. ,| 2pr zpy 2pr

, rl
i
n-lp, fl:p,
r: 1l
it
or,,

Itli
oi.
'1 !
,l
-:-'
2J 2s

II,
o2i
r {A$s) F. iir4{}s} | (AO5}

Molecular Orbital Diagram fo. @ F;-

Analysis done by Bond Order

If value of bond order is positive, it indicates a stable molecule and if the value is

negative or zero, it means that the molecule is unstable.

The stability ofa molecule is measured by its bond dissociation energy. But the bond
dissociation energy is directly proportional to the bond order. Greater the bond order,
greater is the bond dissociation energy.

Bond order is inversely proportional to the bond length. The higher the bond order
value, smaller is the bond length. For Examplethe bond length in nitrogen molecule
is shorter than in oxygen molecule
Magnetic character - If all the electrons in the molecule ofa substance ale paired, the
substance is diamagnetic (repelled by the magnetic field). On the other hand, if there
are unpaired electrons in the molecule, the substance is paramagnetic (attracted by the

magnetic field).

A dihydrogen molecule (H2) forms from two hydrogen atoms. When the atomic orbitals
of the two atoms combine, the elechons occupy the molecular orbital of lowest energy, the
or, bonding orbital. A dihydrogen molecule, H2, readily forms because the energy of a

Hz molecule is lower than that of two H atoms. The or, orbital that contains both electrons is

lower in energy than either ofthe two ls atomic orbitals.

 A molecular orhitai cirn holti tq,o electrons. so boih cicct:L;n:, rr: ihe l{1 molecule alc in

the ol.bonding orhilal: thr electron configuration is i":- -. $c refresenl tiris configuration
by a molecular orbilal encrgl diagrarn in u,hich a single uplvard arrorr indicates one electron
in an orbital, and tu.o (upward and downrvard) arrows indicate l\r,o r'l!'clrons of opposite spin.

Atomrc orbitals l\lolecular orbilals Atomic orbitals

0i.

E
r
I
I
l-
1s

... ,1f
,.-'"

HH2H "^-
The molecular orbital energy diagram predicts that Hz will be a stable molecule with
lower energy than the separated atoms.

A dihydrogen molecule contains two bonding electrons and no antibonding electrons so we

have

bond order in H2 : eP : 1

Because the bond order for the H-H bond is equal to l, the bond is a single bond.
A helium atom has two electrons, both of which are in its ls orbital. Two helium
atoms do not combine to form a dihelium molecule, Hez, with four electrons, because the
stabilizing effect of the two electrons in the lower-energy bonding orbital would be offset by
the destabilizing effect of the two electrons in the higher-energy antibonding molecular
orbital. We would write the hypothetical electron configuration of Hez as (rlr"i' ("i")'. m"
net energy change would be zero, so there is no driving force for helium atoms to form the
diatomic molecule. In fact, helium exists as discrete atoms rather than as diatomic molecules.
The bond order in a hypothetical dihelium molecule would be zero.

Lpnd order irr IIc2 - ef = 0

A bond order ofzero indicates that no boncl is formeil tretween two atoms.

93
 Atonrc orb:lals Molecular orbitals Atonlic orbitals

iltr
.,"ffi
E 4t
|t, -i;
IV
1s

%
Hee

The molecular orbital energy diagram predicts that He: will not be a stable molecule, since it
has equal numbers ofbonding and antibonding electrons.

2.1.10 Difference Between Valence Bond Theory and Molecular Orbital Theory

i) Definition

VB Theory: Valence bond theory is a basic theory that is used to explain the chemical
bonding of atoms in a molecule.

MO Theory: Molecular orbital theory explains the chemical bonding of a molecule

using hypothetical moleculai orbitals.

ii) Molecular Orbitals

W Theory: The valence bond theory does not give details about molecular orbitals. It
explains the bonding of atomic orbitals.
MO Theory: The molecular orbital theory is developed based on the molecular
orbitals.

iii) Types of Orbitals

VB Theory: The valence bond theory describes hybrid orbitals.

MO Theory: The molecular orbital theory describes bonding molecular orbitals and
antibonding molecular orbitals.

iv) Hybridization

W Theory: The valence bond theory explains the hybridization of molecular orbitals.

94
 ,\,IO Theory: The molecular or[.i1al lheorv does not explain about tirc h1 brdization of
orbitals.

2.3 S-Block Elements

If the periodic table were a citv. the s-block would be a small neighborhood filled
rvith extremely similar houses and properlies. Within the periodic table. the s-block is located
to the far left and includes all of the elements in the first two columns (columns 1 and 2) plus
helium. which is located in the top right corner in column 8A (column 18 on some versions of
the periodic table). In the periodic table below. the s-block is colored pink.
The s-block elements are the 14 elements contained within these columns. All of the
s-block elements are unified by the fact that their valence electrons (outermost electrons) are
in an s orbital. The s orbital is spherical and can be occupied by a maximum of two electrons.
Elements in column I have one electron in the s orbital, and elements in column 2 (plus

helium) have two electrons in the sorbital.

The s-block elements include hydrogen (H), helium (He), lithium (Li), beryllium
(Be), sodium (Na), magnesium (Mg), potassium (K), calcium (Ca), rubidium (Rb), strontium
(Sr), cesium (Cs), barium (Ba), francium (Fr) and radium (Ra). The periodic table shows
exactly where these elements are within the s-block.

NO F lle
PS cl Ar
Kr
Xe

2.3.1 Properties of S-Block Elements

Ifthe elements were houses in our hypothetical s-block neighbourhood, they would be
very uniform, each one only slightly different than the other. This is markedly different

95
colllllaiecl to the other nc'ighbourhor.rcl-. or': thc periodic table. u'hich har e I rr iclcr i,arietl, of
houses in many shapes, sizes and colors.

All of the s-block elements .re metals. ln general. they are shinr'. silr err'. good
conductors of heat and electricity and lose their valence electrons easil1,. In fact. they lose
their trademark s orbital valence electrons so easily that the s-block elements are considered
to be some of the most reactil'e elements on the periodic table.
The elements in column l. known collectively as the alkali metals (except hydrogen),
always lose their one valence electron to rnake a +1 ion. These metals are characterized by
being silvery, very soft. not very dense and having low melting points. These metals react
extremely vigorously with water and even oxygen to produce energy and flammable
hydrogen gas. They are kept in mineral oil to reduce the chance of an unwanted reaction or
worse, an unwanted explosion.
The elements in column 2, known as the alkaline earth metals (except helium), always
lose their two valence electrons to make a +2 ion. Like the alkali metals, the alkaline earth
metals are silvery, shiny and relatively soft. Some of the elements in this column also react
vigorously with water and must be stored carefully.
S-block elements are famous for being ingredients in fireworks. The ionic forms of
potassium, strontium and barium make appearances in firework displays as the brilliant
purples, reds and greens.

2.3.2 Diagonal Relationship between Li and Mg

A Diagonal Relationship is said to exist between certain pairs of diagonally adjacent

elements in the second and third periods of the periodic table. These pairs (Li & Mg, Be &
Al, B & Si etc.) exhibit similar properties; for example, Boron and Silicon are both
semiconductors, form halides that are hydrolyzed in water and have acidic oxides. Such a
relationship occurs because crossing and descending the periodic table have opposing effects.
On crossing a period of the periodic table, the size ofthe atoms decreases, and on descending
a group the size of the atoms increases. Similarly, on moving along the period the elements
become progressively more covalent, less reducing and more electronegative, whereas on
descending the group the elements become more ionic, more basic and less electronegative.
Thus, on both descending a group and crossing by one element the changes cancel each other
out, and elements with similar properties which have sirnilar chemishy are often found - the

96
 l
atomic sizc. clee ironegtrtir it1', properties ol' coir.ipound.; iirnti sr.r forlh) clf tite Ciag.rl:ri
members are similar'.

A diauonal relationship is said to exist bet,ureen cefiain pairs of diagonalll'

adjacent elements in the second and third periods ol- the periodic table. These pairs
(lithium (Li; and magnesium (Mg), beryllium (Be) and aluminium (Ai). boron (ll)
and silicon (Si) etc.) exhibit similar properties: fbr example. boron and silicon are

both semiconductors, forming halides that are h1'dlolysed in rvater and have acidic oxides.
The organization of elements on the periodic table in to horizontal rows and veflical
columns makes certain relationships more apparent (periodic lavr). Moving rightrvard and
descending the periodic table have opposile eflects on atomic radii of isolated atoms. Ir4or,'ing
rightward across the period decreases the atomic radii of atoms, while moving down the
group will increase the atomic radii.

Similarly, on moving rightward a period, the elements become progressively

more covalent, less basic and more electronegative, whereas on moving down a group the
elements become more ionic, more basic and less electronegative. Thus, on both descending a

period azd crossing a group by one element, the changes "cancel" each other out, and

elements with similar properties which have similar chemistry are often found - the atomic
size, electronegativity, properties of compounds (and so forth) of the diagonal members are
similar.
It is found that the chemistry of a first-rcw (second period) element often has similarities
to the chemistry ofthe second-row (third period) element being one column to the right of it
in the periodic table. Thus, the chemistry of Li has similarities to that of Mg, the chemistry of
Be has similarities to that of Al, and the chemistry of B has similarities to that of Si. These
are called diagonal relationships. (It is not as noticeable after B and Si.) The rcasons for the
existence ofdiagonal relationships are not fully understood, but charge density is a factor. For
example, Li* is a small cation with a +1 charge and Mg2* is somewhat larger with a +2
charge, so the charge density on each ion is roughly the same. Using the Li-Mg pair: (under
room temperature and pressure)
1. Li and Mg form only normal oxides whereas Na forms peroxide and metals below Na,

in addition, form superoxides.

2. Li is the only Group 1 element which forms a stable nitride, Li3N.a Mg, as well as

other Group 2 elements, also form nitrides.E

3. Lithium carbonate, phosphate and fluoride are sparingly soluble in water. The
corresponding Group 2 salts are insoluble. (Think lattice and solvation energies).
 4. tloth Li and \,lg lbrm coi,alcnt oruanonretallic compounds. t.i\4e i.tli"l

MgMe:1cf. Grignard reagents) are both r,aluable s),r'lthetic reagents. The other (iroutr.r

I and Group 2 analogues are ionic and extrernelv reactive (and hence dil'licult to
manipulate).
5. Chlorides of bothLi and Mg are deliquescent labsorb moisture from sunoundings)
and soluble in alcohol and pyridine. Lithium chloride, like magnesium chloride
(MgCl2.6H2O) separates out from hydrated crystal LiCl.2H2O.

2.3.3. Extraction, physical, chemical properties and uses of Lithium

a) Extration
Lithium was discovered from a mineral, while other coflrmon alkali metals were

discovered from plant material. This is thought to explain the origin of the element's name;
from'lithos' (Greek for'stone'). The image is based on an alchemical symbol for stone.

b) Properties

A soft, silvery metal. It has the lowest density of all metals. It reacts vigorously with
water.

i 80.50'c, 356.90"F,
Group 1 Melting point
453.65 K
Period 2 Boiling point 1342'C,2448"F,7615 K
Block s Density (g cm-3) 0.s34
Atomic Relative atomic
3 6.94
number mass

c) Uses

The most important use of lithium is in rechargeable batteries for mobile phones,
laptops, digital cameras and electric vehicles. Lithium is also used in some non-rechargeable
batteries for things like heart pacemakers, toys and clocks.

Lithium metal is made into alloys with aluminium and magnesium, improving their
strength and making them lighter. A magnesium-lithium alloy is used for armour plating.
Aluminium-lithium alloys are used in aircraft, bicycle frames and high-speed trains.

Lithium oxide is used in special glasses and glass ceramics. Lithium chloride is one of
the most hygroscopic materials known, and is used in air conditioning and industrial drying
s)slems (as is lithiunr bro;liticj. I-ilhium stear.ate is used as ar; uli-pur.pose and high-
temperature lubricant. l,ilhium carbonale is used in drugs to treal manic depression, although

its action on the brain is still not illll understood. Lithium h.vdricle is used as a means of
storing hydrogen for use as a luel.

Biological role: Lithium has no knou,n biological role. It is toxic. except in very small doses.

2.3.4. Extraction, physical, chemical properties and uses of Sodium

a) Extraction:

The name is derived from the English word 'soda'. Salt (sodium chloride, NaCl) and
soda (sodium carbonate. Na2CO3) had been known since prehistoric times, the former used

as a flavouring and preservative, and the latter for glass manufacture. The most common
compound is sodium chloride. This very soluble salt has been leached into the oceans over
the lifetime of the planet, but many salt beds or'lakes' are found where ancient seas have
evaporated. It is also found in many minerals including cryolite, zeolite and sodalite.

b) Properties:

Sodium is a soft metal that tamishes within seconds ofbeing exposed to the air. It
also reacts vigorously with water.

97.794"C,208.029"F,
Group I Melting point
370.944K
882.940oC, 1621.2920F.,
Period J Boiling point 1156.090 K

Block S Density (g cm-3) 0.97

Atomic Relative atomic 22,990
11
number mass

Uses:

Sodium is used as a heat exchanger in some nuclear reactors, and as a reagent in

the chemicals industry. But sodium salts have more uses than the metal itself. The most
common compound of sodium is sodium chloride (common salt). It is added to food and used
to de-ice roads in winter. It is also used as a feedstock for the chemical industry. Sodium
carbonate (washing soda) is also a useful sodium salt. It is used as a water softener.

99
2.3.5. Extraction, phl'sical, chcmical properties and uses ol'Potassium:

a) Extraclion:
The narne is derirccl liorn the English uord 'potash'. Potassium is essential to
life. Potassium ions are lound in all cells. It is important lor maintaining f'luid and electrol]te
balance.Plant cells are pa(icularlv rich in potassium. u'hich the)- get tiom the soil.
Agricultural land, from w'hich harvests are taken every year. needs to lrave its potassium
replenished by adding polassiunr-based fertilisers.The average human consumes up to 7

grams ofpotassium a day. and stores about 140 grams in the body cells.

b) Properties:

A soft, silvery metal that tamishes in air within minutes.

Group 1 Melting point 63.5oC, 146.3oF, 336.7 K

759oC, 1398oF, 1032 K
Period 4 Boiling point

Block S Density (g cm-3) 0.89

Atomic Relative atomic 39.098

19
number mass

c) Uses:

The greatest demand for potassium compounds is in fertilisers. Many other

potassium salts are of great importance, including the nitrate, carbonate, chloride, bromide,
in the manufacture of glass. Potassium
cyanide and sulfate. Potassium carbonate is used
hydroxide is used to make detergent and liquid soap. Potassium chloride is used in
pharmaceuticals and saline drips.

100
 -l

Lnit lll
3.1.('olrlent bond

A covalenl bond, also called a molecular Lronil. is a chemical bond that inrolres the
sharing o1'electron pairs between atoms. These c-lectron pairs are knou'n as shared

pairs or bonding pairs. and the stable balance of' atlractive and repulsive lbrces betu,eerr

atoms. \\,hen they share electrons, is know'n as covalent bonding. For rnany molecules. Ihe
sharing of electrons allows each atom to attain the equivalent of a full outer shell.
conesponding to a stable electronic configuration.
Covalent bonding includes many kinds of inleractions. including o-bonding, n-
bonding, metal-to-metal bonding, agostic interactions, bent bonds, and three-center two-
electron bonds. The term covalent bond dates from 1939. The prefix co- means.iointly,
associated in action, partnered to a lesser degree, etc.; thus a "co-valent bond", in essence,

means that the atoms share "valence", such as is discussed in valence bond theory.

bonding.
In the molecule H2, the hydrogen atoms share the two electrons via covalent
^
Covalency is greatest between atoms of similar electronegativities. Thus, covalent bonding
does not necessarily require that the two atoms be ofthe same elements, only that they be of
comparable electronegativity. Covalent bonding that entails sharing of electrons over more
than two atoms is said to be delocalized.

3.1.1. Hybridization

Scientist Pauling introduced the revolutionary concept of hybridization in the year

1931. He described it as the redistribution of the energy of orbitals of individual atoms to
give new orbitals of equivalent energy and named the process as hybridisation. In this
process, the new orbitals come into existence and named as the hybrid orbitals.

Rales for Cakulating Hybridisation

The following rules are observed to understand the tlpe of hybridisation in a compound or an
ion.
Calculate the total number ofvalence electrons.
Calculate the number of duplex or octet or Number of lone pairs of electrons
Number ofused orbital = Number ofduplex or octet + Number oflone pairs ofelectrons
If there is no lone pair ofelectrons then the geometry of orbitals and molecule is different.
3.1.2 Types of Hybridisation

101
i'he iolloling re the types o1'hybr:itiisat io;r:

l) sp - H1'bridisation

In such hybridisatioll one s- ancl onc p-orbital are mixed to form nro sp h,r'brid

orbitals. having a linear structure wilh bond angle 180 degrees. For example in thc fbnnation
of BeCl:- first be atom comes in excited slate 2s12pr. then hybridized to lbrm I\ o sp - hyblid
orbitals. These hybrid orbitals overlap rvith the trvo p-orbitals of two chloline atoms to
lorm BeCl:

2) sp2 - Hl,bridisation ,)i

In such hybridisation one s- and tow p-orbitals are mixed form three sp2- hybrid

orbitals, having a planar lriangular structure with bond angle 120 degrees.

3) sp3 - Hybridisation
In such hybridisation one s- and three p-orbitals are mixed to form four rp3-hyb.id
orbitals having a tetrahedral structure with bond angle 109 degrees 28', that is, 109.5 degrees.

109.5"

Studying the Formation of Various Molecules

l) Methone

4 equivalent C-H o bonds can be made by the interactions of C-sp3 with an H-1s.

2) Etlune
6 C-H sigma(o) bonds are made by the interaction of C-sp3 with H-ls orbitals and

1 C-C o bond is made by the interaction of C-sp3 with another C-sp3 orbital.

102
3) Formatiott oJ NH j a**tg rnolecules
N t'
In NH:rtnolecule nilrogen atonr is sp3Jrybridised anil one' hvbrid orbital contains two
electrons. Nor.r, three ls- orbitals of thlee hydrogen atoms overlap with three sp-r h1,$1i6
orbitals to form NH,; molecule. The angle betvveen H-N-tl should be 109.50 but due to the
presence of one occupied spr- hybrid orbitat the angle decreases to 107.80. Hence, the bond
angle in NH3 n-rolecule is 107.80.

4) Fonnation of C2Ha and CzIIz Molecules

In C2FIa molecule carbon atoms are sp2-hybridised and one 2p-orbital remains out to
hybridisation. This fonns p-bond while sp2 -hybrid orbitals form sigma- bonds.

5) Formation ofNIIT*nd-H2O Molecules by sp2 hybridization

In H2O molecule, the oxygen atom is sp3 - hybridized and has two occupied orbitals.
Thus, the bond angle in the water molecule is 105.50.

3.1.3. Properties of covalent molecules

Bond angle

The chemical bonding in acetvlene (ethyne) (C2H2) consists of sp_sp overlap between

the two carbon atoms forming an o bond and two additional n bonds formed by p-p overlap.

Each carbon also bonds to hydrogen in an o s-sp overlap at 180o angles.

Polarity of bonds.

In a molecule ofhydrogen fluoride (HF), the more electronegative atom (fluorine) is

shown in yellow. Because the electrons spend more time by the fluorine atom in the H-F
bond, the red represents partially negatively charged regions, while blue represents partially
positively charged regions.
Not all atoms attract electrons with the same force. The amount of "pull" an atom
exerts on its electrons is called its electronegativity. Atoms with high electronegativities -
such as fluorine, oxygen, and nitrogen - exert a greater pull on electrons than atoms with
Iou,er electronegativ iti.s such as alkali metals an{.1 alkaline carrh m!-tals. Lr a bond, this leads
to rnequal sharing o1'eiectrons betvveen the atonrs. as elect:'ons u,ill lre drawn closer to tl.re

atom with the highcr electronegatir it1.

Because electrons harre a negative charge. the unequal sharing of electrons rvithin a

bond leads to the fonnatioll ofan electric dipole: a separation ofpositive and negative electlic
chalge. Because the amount of charge separated in such dipoles is usually smaller than
a fundamental charge, they are called partial charges. denoted as 6+ (delta plus) and 5- (delta
minus). These synibols were introduced by Christopher Kelk Ingold and Edith Hilda
Ingold in 1926. The bond dipole moment is calculated by multiplying the amount of charge
separated and the distance betu,een the charges.

These dipoles within molecules can interact u'ith dipoles in other molecules,

creating dipole-dipole intermolecular forces.

3.1.3 Classilication

Bonds can fall between one of two extremes - being completely nonpolar or
completely polar. A completely nonpolar bond occurs when the electronegativities are
identical and therefore possess a difference of zero. A completely polar bond is more

con'ectly called an ionic bond, and occurs when the difference between electronegativities is
large enough that one atom actually takes an electron from the other. The terms "polar" and
"nonpolar" are usually applied to covalent bonds, that is, bonds where the polarity is not
complete. To determine the polarity of a covalent bond using numerical means, the difference
between the electronegativity ofthe atoms is used.
Bond polarity is typically divided into three groups that are loosely based on the
difference in electronegativity between the two bonded atoms. According to the Pauling

scale:

Nonpolar bonds generally occur when the difference in electronegativity between the two
atoms is less than 0.5
Polar bonds generally occur rvhen the difference in electronegativity between the two
atoms is roughly between 0.5 and 2.0 Ionic bonds generally occur when the difference in
elechonegativity between the two atoms is greater than 2.0.
Pauling based this classification scheme ot the partial ionic character of a bond,
which is an approximate function of the difference in electronegativity between the two

LO4
hondetl aloms. He estimated tlrat a drllcre ::e I ol' i.7 corresponds lc 5t)9,, i(r,'rir character. so

lira1 a greater difference correspollCs lc. a borrtl u'hich is predominanlll ionrc.

As a quantum-mechanical descriprion. Pauling proposed that the r,vtrr e tlnction tbr a
polar molecule AB is a linear combination ol' wave functions fbr covalenl and ionic
molecules: y: a1(A:B) + bV(A+B ). The amount of covalent and ionic characrcr depends on
the values oflhe squared coefficients a2 antl bl.

-i,1.4 Electronic factors that influence organic reactions

Inductive Effect, Electromeric Effect, Resonance Effects, and Hyper conjugotion

These electronic factors involve organic molecules, most of which are made from a
combination of the following six elements: carbon, hydrogen, nitrogen. oxygen. phosphorus,
and sulfur (known collectively as CHNOPS). Yet, the limited number of building blocks does

not prevent organic compounds from taking on diverse properties in their physical
characteristics and chemical reactivity. The subtle differentiation of various compounds in
organic chemistry is essential for the biological functions ofthe molecules and creates a wide
variety of reactions.

HHHH
lltt tt
HH
c-c-o-H
HHO
t 1il,.
llrt
HHHH
H-C
tt H-C-G-
tl
Propane {C3Hs) Propanol (CrHsO) hopanoic Acid (C1H6O2)

Part of this variety in organic chemistry stems from differences in electron behavior
when elements other than carbon and hydrogen participate in molecular bonds. For example,
the three compounds pictured above have similar formula units and structures, but react very

differently from one another because of these electronic factors.

Varying electronegativity can catse delocalization effects, where the electron cloud for a
given bond expands to more than two atoms within the molecule.

105
-3.1.;1. Polarig of Organic Moleculos (llond polarity)

Partial polarity r.,uithin a molecule leads to electron transler arnong thc atoms ilr a
molecule. Ieading to different behavior than what would be expecled in a non-polar version
olthe compound, where no sectiolrs uere electron-rich or electron-deficien1.
Saturated hydrocarbons are nonl'eactive because there is no polarity in C-C bond and
practically no polarity in C-ll bonds. Carbon and hydrogen are ahnost identical
in electronegativity, so the electrons involved in a bond between the two atoms are equally
attracted to each nucleus and spend roughly the same amount of tir-ne orbiting one as the
other.

Electron density is evenly distributed between the two atoms in a non-polar bond,
which prevents charged species from attacking or altering the bond. In contrast, charged
species (electrophiles and nucleophiles) react with polar organic molecules because there is
an imbalance in electron density or polarity.

Elements with higher electronegativity, including oxygen and the halide group, can
change the electron density around an organic molecule and make the molecule more
reactive.
Electronic effects complicate chemical reactions, and they can stabilize a molecule, make a
compound less volatile, and make a molccule more likely to react in a desired fashion, or
affect the acidity or basicity. Understanding the factors involved in electronic imbalance is
vital for understanding the underiying mechanisms of a chemical reaction, predicting the
products of a reaction and predicting organic molecules' behavior.

3.1.4.a. Inductive Effect

The inductive effect is a permanent state of polarization. The electron density in

a bond between two unlike atoms is not uniform. The electron density is denser toward the
more electronegative of the two atoms.

The inductive effect is a distance-dependent phenomenon:

The atom above acquires a slightly negative charge and the carbon atom a slightly
positive charge which means the bond is polarized:

106
 {'riir:r:- . C*t* C"'1 , - [''.1---------*--yi
-
a.i'*ji; .
C"n: -.._ r-.ii' . C",- . I-i-
If the electronegative atom is connecled to a chain of carbon atoms, then the positrr,e
charge is related 1o the other carbon atoms. , ivith its positive charge, exefis a pull on the
electrons of" bu1 the pull is weaker than it is between on. The eflect rapidly dies out and is
usually not significant after the carbon atom, or.at most the inductive effect is pemanent, bu1
relatively u,eak. and can be easily overshadow'ed by the electronic effects discussed later.
There are two categories of inductive effects: the electron-withdrawing (-I effect)
and the electron-releasing (+I effect). The latter is also called the electron-donating elfect. In

the image above, is electron-withdrawing and is electron-donating.

These relative inductive effects are measured with reference to hydrogen:

-I effect:

The -I effect is seen around a more electronegative atom or group, and electron
density is higher there than elsewhere in the molecule. Electron-withdrawing groups include
halogen, nitro, cyano, carboxy, ester and aryloxy

+I effect:

The +I effect is observed among the less electronegative atoms of the molecule by
electron-releasing (or electron-donating) groups. The alkyl groups are usually considered
electron-releasing (or electron-donating) groups.

3.1.2.b. Resonance

Sometimes, there are several correct Lewis structures for a given molecule. Ozone is
one example. The compound is a chain of three oxygen atoms, and minimizing the charges
while giving each atom an octet of electrons requires that the centual oxygen atom form a
single bond with one terminal oxygen and a double bond with the other terminal oxygen.

When drawing the Lewis structure, the choice of placernent for the double bond is
arbiffary, and either choice is equally correct. The multiple corect ways of drawing the
Lewis structure are called the resonance forms.
Based on the resonance u beginning chemistry student might wonder if ozone
P*1,
has bonds oftwo different lengths, since single bonds are generally longer than double bonds.

to7
I{ou'er er- thc ozort.: molecule is perfectlr s1mnretrical. u'ith bonds thal are the same ir:rS:l'r.
None of tl.re resonance fbrms represent the tlue stn-lclure olthe molecule. Rather" the nclilii\ e

charge 01'the electrons that rvould form a doutrlc- bond are delocalized, or distributed ei er:)1
across the three oxvgen atoms. The lrlle structure is a composite. with bonds shorler thun
r,r,hat rvould be expected for single bonds. but longer than the expected double bonds.

@
9.
v rr
_ (J-.1
u-irro\5u-
-________1
:o- -o:
ilr I II
The resonance fu'brid.fbr ozone is .found by identifying
the nxultiple resonance structures for the molecule.

Thus for the two structures (I and II) shown above constitute the canonical struclures
or resonance structures and their hybrid (i.e. the III structure) represents the structure
of more accurately. Resonance is represented by a double-headed arrow between the
resonance structures, as illustrated above.

(l)
2* 2- 2-
:0: :0: Q:
I
+ il e I

t\.0'
'o:
. z,C.-
.p,
.
:0. ,,,Cf
.0: ,{

(2)

,9 o-
+
-lrl+o- -J{
b

.-
-o
108
 The resonance hlbrid is u',o,'. slanle than its canonical lirrnrs. i.c. the actr.lal compound

ihybrid) is at a low,er energv state than its canonical fom.rs. I{esonance stabilitf incteases with
increased number of rcsonance struclules.

The diiference in the experirnental and calculated energies is the arnount of energy by
which the compound is stable. 'fhis difl'erence is known as resonance energy or delocalization
energy. All resonance structures are not equivalent. The follon'ing rules help determine
whether or not a resonance structure will contribute significantly to the hy'brid structure.

Rules of Resonance

Rule 1: The most significant resonance conhibutor has the greatest number of full
octets (or if applicable, expanded octets).
Rule 2: The most significant resonance contributor has the fewest atoms with formal
charges.
Rule 3: If formal charges cannot be avoided, the most significant resonance
contributor has the negative formal charges on the most electronegative atoms,
and the positive formal charges on the least electronegative atoms.
Rule 4: The most significant resonance contributor has the greatest number of covalent
bonds.
RuIe 5: If a pi bond is present, the most significant resonance contributor has this pi
bond between atoms of the same row of the periodic table (usually carbon pi
bonded to boron, carbon, nitrogen, oxygen, or fluorine).
Rule 6: Aromatic resonance contributors are more significant than resonance
contributors that are not aromatic.
3.1.4.c. Mesomeric Effect

The permanent polarization of a group conjugated with abond or a set of

altemate bonds is transmitted through the electrons of the system, resulting in a different
distribution of electrons in the unsaturated chain. This kind of electron distribution in
unsaturated compounds conjugated with electron-releasing or withdrawing groups or atoms is

called mesomeric effect.

oo o oo
A", ' Ao' A*'
l-
' A"'-
acid chlaride ester carbaxylic
amde cataaxylale

tt
acid

l
t I t
b .O -o -o.o
,Jo.,. Aotn A,i- I
,&.

109
 As shou,n abor ,"-- a pol:rrity is indtrced in contp()u:)ds due ro lranstbr of electr ons
through bonds. This etllcr is a consequence of resonance and is seen in compounds that
cotrtain a double bond thtrt is separated lrom another double hcud or a lone pair of electrons
by a single bond.

3. l.4.d.Electromeric Effect

The electromeric effect is an intramolecular movement of eleclrons frorn a pi bond to

another atom in the molecule due to attack by a reagent. It is temporary and reversible.
There are two distinct types of electromeric effects:

(i) Positive Electromeric Effect (+E effect): In this effect the -electrons of the multiple bond
are transferred to that atom to which the reagent gets attached. For example:

\ 3,/ \*
..c:c,. +
.J_

H' (-
'/
\_/ t\
H

(ii) Negative Electromeric Effect (-E effect): In this effect the -electrons of the multiple
bomd are transferred to that atom to which the attacking reagents do not get attached. For
example:

aro
\rn
.c-o +CN -\/-----------+ 'c'
,,/\ 'CN

3.1.4.e. Hyperconjugation

Hyperconjugation helps explain the stability of alkyl radicals. It involves the

delocalization of-electrons belonging to the c-H bond of the alkyl group attaching to an
atom with an unshared orbital. The more the hyperconjugative hydrogen, the more is the
stability.

110
 Eclipsed Staggclcd
Brrrrrling rrrbitrls -\ jr tr b( )ndi ng
( )r't)rrlll

.ffi_.
HH

Pauli Exchange Weakened Strengthenod

(repulsive) Hypercon-jugati on Hyperconj ugation
(attractive)

3.2.1. Horv to name organic compounds using the IUPAC rules

In order to name organic compounds you must first memorize a few basic names.
These names are listed within the discussion of naming alkanes. In general, the base part of
the name reflects the number of carbons in what you have assigned to be the parent chain.
The suffix of the name reflects the type(s) of functional group(s) present on (or within) the
parent chain. Other groups which are attached to the parent chain are called substituents.

Alkanes - saturated hydrocarbons

The names of the straight chain saturated hydrocarbons for up to a 12 carbon chain
are shown below. The name of the substituents formed by the removal ofone hydrogen fron
the end ofthe chain is obtained by changing the suffix -ane to -yl.

Number of Carbons Name

1 methane
2 ethane
J propane
4 butane

5 pentane

6 hexane

7 heptane

8 octane

9 nonane

10 decane

11 undecane

12 dodecane

71!
 3.?.2. Ilvdrocarbon

In organic chemistry,. a hldrocarbon is an organic con-rpound consisting entirely

ofhvdrogen and carbon. Hydrocarbons are examples ofgroup l4 hydrides. lllclrocarbons
fionr which one hy'drogen alom has
groups called hydrocarbyls. Because carbon has 4 electrons in its outermost shell (and
because each covalent bond requires a donation of I electron. per atom, to the botld) carbon
has exactly four bonds to make. and is only stable if all 4 ofthese bonds are used.

Aromatic hydrocarbons (arenes), alkanes, cycloalkanes and alkyne-based compounds

are different types of hydrocarbons. Most hydrocarbons found on Earth naturally occur
in crude oil. where decomposed organic matter provides an abundance ol carbon and
hydrogen which, when bonded, can catenate to fomr seemingly limitless chains.

Ball-and-stick model of the methanemolecule, CHa. Methane is part of a homologous

series known as the alkanes, which contain single bonds only.

Hydrocarbons can
gases (e.g. methane and propane), liquids (e.g. hexane and benzene), waxes or
ll
louirnelting solids (e.g. paralfinwax and naphthalene)
t-

Polymers (e.g. polyethylene, polypropylene and polystyrene). General property; This

inherent ability of hydrocarbons to bond to themselves is known as catenation, and allo'*,s
hydrocarbons to form more complex molecules, such as cyclohexane, and in rarer cases,
arenes such as benzene. This ability comes from the fact that the bond character between

carbon atoms is entirely non-po1ar, in that the distribution of electrons between the two
elements is somewhat even due to the same electronegativity values of the elements (-0.30),
and does not result in the formation ofan elechophile.
Generally, with catenation comes the loss of the total amount ofbonded hydrocarbons
and an increase in the amount of energy required for bond cleavage due to strain exerted upon

LLz
the molecule; in molccules srrch as cyclohexane. thjs is rei('rred to as ring strain. ar'Id cccurs
due to the "destabilized" spalial electron configuration ollhe atorl.
In simple chemistry. as per valence bond theory. Ihe carbon atom must follow,the "J-
hydrogen rule", .vrhich states that the maximum numbel of atoms available to bond rvith
carbon is equal to the number of electrons that are attracted into the outer shell of carbon. ln
terms of shells, carbon consists of an incomplete outer shell, '*,hich comprises 4 electrcns,
and thus has 4 electrons available for covalent or dative bonding.

Hydrocarbons are hydrophobic like lipids.

3.2.3 Monofunctional compounds: In chemistry, functionality is the presence of functional

groups in a molecule. In organic chemistry (and other fields of chemistry) functionality of a

molecule has a decisive influence on its reactivity.

In polymer chemistry., the functionality of a monomer means its number
of polymerizable groups, and affects the formation and the degree
of crosslinking of polymers. A monofunctional molecule possesses one function, a
difunctional two, a trifunctional three.
SH

Thiophenol Ethylamine H3CANH,

3.2.4 Bifunctional Compounds

When a single organic molecule has two different functional groups, it is

called bifunctional. A bifunctional molecule has the properties of two different tlpes of
frrnctional groups, such as an alcohol (-OH), amide (CONHr, aldehyde (-CHO), nitrile (
CI.D or carboxylic acid (-COOH). Many bifunctional molecules are used to
produce medicinesfnd catalysts, while others are used in condensation
I
polymerization like polyester and polyamide. In organic molecules, functional groups
are atoms or molecules that are responsible for the characteristic properties of that molecule,

with the exceptions of double and triple bonds, which are also functional groups.

113
3.2.5 Isomerism:

It is a phenomenon ',vhere tq,o or more compounds har,e 1he same chemical fbmrula but
possesses dilTerent struclural formulas, that is. diflbrent propeflies. This is mainly because of
different structural or spatial amangements. Isomers are the compounds exhibiting isomerism.

T1,pes of Isomerisnt

Basically. there are two types. They are:

Structural Isomerism
Stereoisomerism
However. these are again ofmany su6types as shown in the figure:

3.2.6. Structural Isomerism

Isomers are structwal isomers when they have the same molecular formula but different

structures, as in how they are linked to each other. Structural isomerism is further of the

following types. Let's leam about these tlpes one-by-one.

Leam the different Chamcteristics of Organic Compounds here.

1) Chain Isomerism

Isomers are chain isomers when two or more compourds have the same molecular
formula but differ in the branching of carbon aaoms. For example, we can represent CsHrz as
three compounds: CFI:CFIzCHzCH2CH3- pentane

2) Position Isomerism

Isomers are position isomem when the two or more conpounds differ in the position of
the functional group or substituent atoms. For example, we can represent C3H7OH in two

arrangements:

CH3CH2CH2OH - Propan-l-ol. ,
irlj -0ropatr l'Ol
o 11

3) Functional Isomerism

Isomers are functional isomers when the two or morc compounds have an identical
moleculff formula but differ in the frrnctional goup present. These isomers are the functional
isomers. For example, we can represent C3[I6O as a ketone and as an aldehyde.

/'i^ !.I .
r iLl
-) /,
. .t
- i r-
.. ( d-
tr4
d) Metamerism

This is exhibited by compounds due to the presence of different alkyl chains on either
side of the frurctional group. Iror example, \l,e can represenl C"rI{roO as ethoxyethane
(CrHsOC2Ils) and methox)?r opane (CHjOCjH).

3.2,7. Stereo Isomerism

Stereoisomerism is a phenomenon in which compounds have the same molecular

lormula but differ in the relative positioning or orientation of atoms in space. Stereoisomers are
the compounds exhibiting stereoisomerism. We can frrther classifu stereoisomerism into:

Geometric Isomerism: it is shown by molecules in which their spatial positions are

locked to each other due to the presence ofa ring structure or a double bond.

Optical Isomerism: Two or more compounds which have the same molecular
arrangement but differ in the optical activity are optical isomers.

3.3 Petroleum

Petroleum is a naturally occurring, yellow-to-black liquid found in geological

formations beneath the Earth's surface. It is commonly refined into various types offuels.
Components of petroleum are separated using a technique called fractional distillation, i.e.
separation of a liquid mixture into fractions differing in boiling point by means of distillation,

typically using a fractionating column.

It consists ofhydrocarbons of various molecular weights and other organic
compounds. The naln.rc petroleum covers both naturally occuffing unprocessed crude

oil and petroleum products that are made up of refined crude oil. A fossil fuel, petroleum is
formed when large quantities of dead organisms, usually zooplankton and algae, are buded

undemeathsedimentary rock and subjected to both intense heat and pressure.

Petroleum has mostly been recovered by oil drilling (natural peholeum springs are
rare). Drilling is carried out after studies
of structural geology (at the reservoir scale),
sedimentary basin analysis, and reservoir characterisation (mainly in terms of
theporosity and permeability of geologic reservoir structues) have been completed.It is
refined and separated, most easily by distillation, into a large number of consumer products,
from gasoline (petrol) and kerosene to asphalt and chemicalreagents used to

115
llal(e plastics and pharmaceuticals. iret:olount is used in rranulacturins a ri,ide variety o1'

materials,and it is estimated thal the urrld consumes about 95 n.rillior.r barrels euch day.

Concern over the depletion ill' the earth's finite reserves of oil. and the ell-ec1 this
r.vould have on a societ."- dependent on it. is a concept knowr as peak oil. The use of fossil
fuels. such as petroleum, has a negative impact on F-arrh's biosphere.
damaging ecosystems through er,'ents such as oil spills and releasing a range of pollutants into

the air including ground-level ozone and sulfur dioxide from sulfur irnpurities in fossil fuels.
The buming of fossil fuels plays a major role in the current episode of global warming.

3.3.1 CoaI tar distillation:

Distillates are made up of crude coke oven tar components, which are produced
during the high temperature coking of bituminous coal.

Carbon pitch boils between 100'C and 400'C during the distillation process. Refined
chemical oil distills between 210"C and 315"C. Distillates that distill above 315'C are high
molecular weight aromatic hydrocarbons (middle and heavy distillates). The Refined
Chemical Oil is further refined by distilling to obtain naphthalene leaving a lightweight, low
naphthalene material (rlSR). This material is blended with the heavier distillates to produce
Creosote with an American Wood Protection Association specification. The balance of the
heavier distillates is used as feedstock in the production of carbon black feedstock.
BtTulltilous coAL
I

il
COl(E,

OILS LIOHTER THAN IYATER. OIL$ HEAYEB PIICII,

THAX WATER.
cRE0s0?E

DI$TIIIATIOtI IIIiIIS AI{D CENEFAT NATURE OF ]HE AFOTATIC CONSTITUENTS,

Lt6
3.3.2 Sources and Importance of Alkanes

Major Sources:
Natural Gas
Petroleum
Coal
These substances constitute 8570 ofthe energy consumed by the United States

A. Natural Gas
- 90%-957o Methane, 5%-10% Ethane, and trace amounts of low boiling
alkanes (propane, butane, 2-methyipropane)
- The ethane from natural gas can be "cracked" into ethylene (most commonly
produced organic compound produced by the U.S.). Cracking is a plocess that
converts saturated hydrocarbons to unsaturated hydrocarbons and H2.
CH:CH: ) CH2:CH2 +H2 ,,

- viscous fluid ofdecayed marine life

- used to create auto, ffansport, and synthetic fibers
REFINING TECHNIQAES
- Separation: Fractional distillation (separation ofa liquid mixture into fractions
differing in boiling point, and hence chemical composition)
- Reforming (changing the substance): Most common practices are cracking
(mentioned earlier) and Catalytic Reforming
C. Coal
- Synthesis gas (comprised of Carbon Monoxide and Hydrogen) is prepared by
passing steam over hot coal(and sometimes natural gas and petroleum).
Synthesis gas can also be prepared by the partial oxidation of methane with
oxygen.
- These substances can be used to produce methanol and acetic acid, two very
important industry compounds

3.3,3 Preparation of Alkanes

Some ofthe general methods of prepamtion of alkanes are:

a) FROM ALKYL IIALIDES @y Wurtz Reaction)

Alkyl halides are halogen derivatives of alkanes with general formula R-X. They can
be used to prepare alkanes by Wurtz reaction:

It involves the chemical reaction between alkyl halides (usually bromides and iodides)
and metallic sodium in the presence of dry ether. The product is the symmetrical alkane
containing twice the number of carbon atoms present in the alkyl halide.

tt7
 I * .i. ,r - l,ri l
'TJ l\r'.
l':i ,:i;i;Ipk.
?CF{r* I + ji\:: , l r, -{iil . - -''1 r!
1,{*, r,h-l'i iatii*i: ll i l::+:*

,'r].. ,... i.: , .. -.CH,''.f\i:rl

:""' "){l}{--*l * 13a ... ) ,: tl---'{.}l:
-
i ii "{]H1

b) FROMUNSATURATEDHYDROCARBONS

Unsaturated hydrocarbon can be converted into alkanes by catalltic hydrogenation. The

catalyst used may be nickel, platinum or palladium. These metals absorb dihydrogen gas on
their surface and weaken the hydrogen-hydrogen bond. Platinum and palladium catalyse the
reaction at room temperatue while nickel requires higher temperature and pressure. The
reaction is called Sebatier and Senderen's reaction.

l\:
C!"!,. =fH. + l-1.
,-
c$. *cllr
5:.t -_i?_1 K
f;ti:::r:il
fi.*:e**
Ni
CH=Cl I ,lli, -_ ;;.;Cl t.-C!{-,
[.thr.rrc l;ih;.ru'

c) FROM CARBOXYLIC ACIDS

(i) SodaJime Decarboxylation. It involves the treatment of sodium salt of carboxylic acids
with scda lime (NaOH and CaO in the ratio 3 : 1).
Ca0
ItCC{}l{a + IaOII ;-:*
of
-SH {
rte:tr AiKan*
Na?C*:
$ndiu*l lall
calir*x}'li+ acid

CIS3CS0lrx t Nd$X - i"tl

Heat
cn. + N;:-(_0-
- :
Merhane
Ca*
CrltrCOONa + NaOH -------r C3H5 + l{axf$,
fle&r
r So<liurr,
.{orIr c':\propon.nlc
ELtsu:nc

The alkane famed has one carbon less than the sodium salt of carboxylic acid. In this
reaction CaO does not participate in the reaction but helps in fusion ofthe reaction mixture.
(b) Electrolytic Decarboxylation. This reaction is also called Kolbe's reaction. In this
reaction an aqueous solution of sodium or potassium salt of a carboxylic acid is electrolysed.
Alkane is formed at anode.

118
In general. the electroll'1ic dccarborylation can be represenletl as
lr" ' l

li..__ft ..'..;t ,l .-i:.,;:1

..ili rt:i

3.3.4. Preparation of Cl,cloalkanes:

(i) When l, 5-dihalogen derivatives of alkanes are treated by sodium or zinc, the
analogous cycloalkane is formed, for exanple 1, 5-dibromopentane u,ould shape the
cyclopentane.
CHrCH:Br
//t
.CHTCH:
CH: *Zn .--+ CHr I +ZnSrt
\\rCH:CH:Br tCHrCH,

l. s{ribrsropcrtrne cyclorerlt8re

(ii) Whenever the calcium or barium salt of a dicarboxylic acid is distilled, a cyclic
ketone is formed, for example, barium adipate gives cyclopentanone

Bn+4
--^--)
Salt of dicarboxvlic acid cyclopentanone

A cyclic ketone can be decreased into the analogous cycloalkane using zinc amalgam

and concentrated hydrochloric acid (Clemmenson reduction).

ruo
v
flt* HCr

cyclope$t8nono cyclopafilsn€

3.3.5. Chemical properties;

Alkanes are comparatively unreactive to most of the general reagents. It is hard to

describe the terms 'reactive' and 'unreactive', because a compound might be reactive under

779
one set olcoirditions ald unlcactive under the other. 'l-!ris t.cntlir i1,. t)r unrcacri\ ity might be

illustrated via consideiing rhe nature o1'C - C and C - Il bonds pr.c-sent in their molecules.
Since the electroncgativities ol
carbon and hydrogen dcn't dil'ier noticeably. the bor-rded
electrons in C -H are more or less similarly shared betu,een them. 'firerefore. C - H bonds
encountered in alkanes are approximately nonpolar and sirnilar is true of C - C bonds.
Therefore, polar and ionic reagents discover no sites to attack an alkane molecule. Alkanes
undergo mostly substitution reactions that can be illustrated using firee radical chain
mechanism. Such rcactions occur in the presence of UV light or at a high temperature or in
the plesence of certain free radical initiators such as peroxide. The chemical reactions that
occur in the presence of light are termed photochemical reactions. In substitution reactions,
one or mor€ of the H atom(s) of alkanes are substituted via halogen or some another groups.
Several significant reactions of alkanes are following in Table.

Table: Reactions of Alkanes

RH -r Xr .-.----.-r
dA
Rx+ t{x
Nitration
Rll -i- lll\io3 -----r Rt\lo: + H'ol
IsorTrerisation ctt:
AlCr:*l.lcl 1

crtrcllcta.
CI{: CH:Cll: C}I:
Aro rBati sati orr

4*lz

----> CH4 * C!l2 : cH:

cia3 cr{ : cl.l2 + I{t
Cort1b1rstion
C!1, CHTCrIZCH2CIIT -f 80: -"_"-'> 5CO:+6FI2G2549 kJ rrrot_l

3.3.6 Halogenation of alkanes:

Halogenation of alkane is one of the most important reactions of alkanes. It is defined

as the replacement ofhydrogen atom(s), from an alkane molecule, by halogen atom(s)
A/hv
RH+X2'-"-"+RX+HX
The reaction does not occur in dark but a vigorous reaction takes place whenever the
mixture of alkane and halogen is depiction to light or heated to a high temperature. But in
most cases, the reaction is of limited synthetic value because a mixture of products is
obtained. Multiple substitutions may occur. For example, chlorination of methane produces a
mixture of chloromethane, dichloromethane, trichloromethane and tetrachloromethane.
 i.r\

CHq + Cl', ('lt:('l Chloromethane)

-* {

hv
iA
CH3CI + Cl: * CI{:Clu (dichloroethane)
A
hv
il
CHCI2+Clz- CHCI: (Trichloromethan)

hv
1,"-
**--*
CHC13-+ C12 CCl4 (tetra chloromethane)

The yield of the monosubstituted ploduct may increase by using an excess of alkane.
Similarly, a cycloalkane reacts with halogen to give halocyclalkane, for example:-

+ xt x
cyclopertarle
--* Halocvclopentane

The mechanism ofhalogenation is supposed to involve the following

Steps:

In the first step, the halogen molecule undergoes homolysis forming free radicals.
This step it called chain initiation:
hv/A
(i) Y,z * 2X
In the next step, the halogen atom abstracts a hydrogen atom from the alkane
molecule thereby producing an alkyl radical.
(iD RH+X' .-'-+ HX+R'
The alkyl radical on collision with another molecule of halogen abstracts a halogen
atom from it generating a molecule of the alkyl halide and a halogen atom. These two
steps are called propagation. They are repeated in sequence till the reactants are
consumed.
(iiD X2 + ft' ........* RX + X
Finally, the above chain might be terminated via coupling of any 2 radicals. This step
is recognized as termination.

!27
(ir) X-X .....".*XX
R + X --"""'* *'

R +R+ RR
'Ihe an'ay ofreactivity ofhalogen in halogenation
ofalkanes is:
F2 > Cl2 > Br >I2
Though, the fluorination reaction is as rvell violent to be practical, and iodine actually
doesn't react at all.

Nitration:

Alkanes mainly the higher member, can be nitrated by nitric acid at a temperature of
675-775 K. Like halogenation, it is as well a free radical reacrion.
RH + HNO3 ""'--""r RNOz + HuO
In this reaction, the product it generally a mixture ofnitroalkanes including those
through smaller carbon chain than the parent alkane.

HN03
CH:CHzCHI + CH:CHzCHzNOz + CHzCHCH: + CH3CH2NO2 + CHTNOz

Propane l-nitropropane 2-nitropropane nitroethane nitromethane.

3.3.7 Substitution reaction in free radical:

Chain initiatiott ,,.

,1

The chairr is initiated (started) by tIV light breaking a chlorine molecule into free radicals.

cl: r< 2c1

Ch ain propagation reactions

These are the reactions which keep the chain going.

CH4 + CI CH3 + HCI

cH3 + Cl2 -----.--> CH3C1 + Cl

C h ain te rlnination r eaction s

These are reactions which remove free radicals from the system without replacing them by new ones.

2Cl Clz

tzz
 CH3 + CI *-'+ CHr('l
,t
CH3 + 611, + CI{r('H-l

3.3.8. Conformational isomerism of Ethane and n-butane;

Conformational isomerism involves rotation about sigma bonds, and does not
involve any differences in the connectivity or geometry of bonding. Two or more structures
that are categorized as conformational isomers. or conformers, are really just two of the
exact same molecule that differ only in terms of the angle about one or more sigma bonds.

Ethane Conlormations

Although there are seven sigma bonds in the ethane molecule, rotation about the six
carbon-hydrogen bonds does not result in any change in the shape of the molecule because
the hydrogen atoms are essentially spherical. Rotation about the carbon-carbon bond,
however, results in many different possible molecular conformations.
rotating bond

,',,', il ,'
'.lt-.U..;I,i " r'H)
rsoorohrion'--r.r.-r-.rH
.!-l I
eS'rotariop .l;.:C
n.) ..F-t-
+H
-
',
H;l-vilH *;r ',:I) -
HH
C

In order to better visualize these different conformations, it is convenient to use a

drawing convention called the Newman projection. In a Newman projection, we look
lengthwise down a specific bond of interest - in this case, the carbon-carbon bond in ethane.
We depict the 'front' atom as a dot, and the 'back' atom as a larger circle.
H
HH H- ---- -H
<- - - - - - - - (' h1'j"ffi*'. Tl{\H
n";b-ciH
HH
n^J
H

'staggered' conformation
(Newman projection)

The six carbon-hydrogen bonds are shown as solid lines protruding from the two
carbons at l20oangles, which is what the actual tetrahedral geometry looks like when viewed
from this perspective and flattened into two dimensions.

L23
 l'hc lo*est enctgr confonnation oi ethanc. sh()\\r) i;r ihe figure above. is call.'d ih.'
'staggered' conlbrnration. in rvhich all ofthc Cl-[] bonds on thc'fiont carbon are positioned at

dihedral angles of'60'relative to the C-H bonds on the back cirrbon. In this conformtrtion. the
distance betn'een the bonds (ard the electrons in them) is ntaximized.
If u'e norv rotate the fiont CH: group 60" clock'uvise. the molecule is in the highest
energy 'eclipsed' contbrmation, rvhere the h1'drogens on the front carbon are as close as
possible to the hydrogens on the back calbon.

HHta.-a.' ... -.
H:" --_-H <--. 1.

HH
'eclipsed' conformation

This is the highest energy conformation because of unfavorable interactions between

the electrons in the front and back C-H bonds. The energy of the eclipsed conformation is
approximately 3 kcal/mol higher than that of the staggered conformation. Another
60orotation retums the molecule to a second eclipsed conformation. This process can be
continued all around the 360ocircle, with three possible eclipsed conformations and three
staggered conformations, in addition to an infinite number of variations in between.

33.9. Relative stability of cycloalkanes (from cyclopropane up to cyclooctane)

The stability ofthe cycloalkanes can be explained using thermochemistry. The heat of
combustion per methylene group was determined experimentally for cycloalkanes ofdifferent
ring sizes and this data was compared with that of n-alkane.
Thus, higher the value ofheat of combustion per methylene group in comparison with
the n-alkane lower is the stability of that cycloalkane. The following table gives the data for
small and common ring compounds:

Alkanes tleat of combuition per metiylene

drouD lkaal/mol)
n-alkane t57.4
cvaloDro Den€ t 56.6
cycloburane 163.95
cvclooentene I S8.7
cyclohexane r 57.4
I S8.3

Thus the heat of combustion per methylene group is high in cyclopropane, drops to a
minimum in cyclohexane which has about the same heat of combustion per methylene group

124
as an n-alkane and then again ii:jcs ii:r cl cloheptane. So. clclopl.ollatle has lllr' tlaximum
instabilitv and then the stabilitl" graduulil increases and it is maximized fbr clcllliexane.

3.3.10. Baeyer Strain Theory

In 1885, Adolf von Baey'er published a paper on polyacetylene compounds in the

joumal of the German Chemical Society. At the end of the paper, a discussion appeared on
the strain in small ring compounds. Baeyer reasoned that since the bond angle itr a perfect
tetrahedron (the tetrahedral carbon had been proposed independently by van't
Hoff and LeBel in 1874) is 109" 28' [109 degrees, 28 minutes; ], then the amount of strain in
a small ring compound would be the half the difference between the tetrahedral value and the

internal angle of a regular polygon. Why halfl Because the strain would be distributed
equally to "each bond" connected to a carbon.
CHr rrLr

L J1.r QI{a clIr.'-cIIr CHS CI{I ClIs CLlr

ln
;i 1l
I CH, CH*-."CIIs OIlr'"-Cll* dgr-."crn 0llz CHr
+ s,f,' {'{' + g4{, 4{f +.llr,:}4' + 0{r 44'
CHr
5n 16'
-
Baeyer considered ethylene to be a special polygon with an intemal angle of 0o, thus
its value of +54o 44'. The intemal angle of the equilateral triangle (cyclopropane) is 600 and
for a square (cyclobutane) is 90o. Try the calculation. What is the intemal angle of a regular
pentagon or hexagon? The sum of all supplementary angles about any polygon is equal to
360o. Thus, the supplementary angle for each internal angle ofa regular hexagon is 120o. Do
the calculation for each of these cyclic hydrocarbons. You can see why Baeyer reached the
conclusion that cyclopentane, with its minimum value, is less strained than cyclohexane.
Although Baeyer used the value 109o 28' for the tetrahedral carbon, he nonetheless viewed
the cycloalkanes as planar species. He reasoned that the equatorial and axial positions on
cyclohexane would be unique. Thus, there should be an axial cyclohexanecarboxylic acid and
an equatorial one. Of course, with the benefit of over 100 years of hindsight, we realize that
these two carboxylic acids interconvert rapidly at ambient temperature.

3.3.10.a Limitations of Baeyer strain theory

* Baeyar was not able to explain the effect ofangle strain in larger ring systems.
* According to Baeyer cyclopentane should be much stable than cyclohexane but
practically it is reversed.

125
 Largel ring s)'slerrs al nr)t possible trccordit-rg to Bae-'-et as lhcr Irar,r, neuative strain
but they exist and much stahle.
Larger ring s)'stems arc nol planar but puckered to eliminate angle strain.

3.3.I I. CYCLOHEXANE CONFORMATIONS

'j j1.
The simplest imaginable conformation for cyclohexane. the planar, gne, is not
only-Do+ the ground state confonnation. it is so high in energy thal it plays no part in the
conformational a nalys i s o-l' cyc I o hexane.

IIYCLCH€*A.l€ CONFOTMATIOT':S

Ensrly $anlma

€_1 . i-5

ttlaxifira
,\
/\

F6 boal
Er*i=55
tral, clraf
€Bi - 10 kcetl/rt1oi

plrnar
Eer c vqy la.gq t>2O l?at/mol:

This is mainly because ofthe large amount of torsional strain which is present in this
forrn. Thus, all six C-C bonds in the planar form are eclipsed, so that we could crudely
estimate the torsional strain as being at least 6 times that in eclipsed ethane, which has one
eclipsed C-C bond, or 18 kcal/mole.
The ground state conformation of cyclohexane is a fully staggered conformation
which is shaped somewhat like a "chair". In this conformation there is no torsional strain at
all, and as-rcreshallsee-1ater, no strain of any kind. Cyclohexane is unique in being the only

126
cyclic 11)drocarbon rvhich is completely slrain-lice. So the six membered rin,u is thc :r rrrsl

stable of all.So rve see that torsional efiects. although individually small (per C]-C btud).
exert a tremendously ilrpoftant effecl on the shapes of n.roleoules, and shapes oflen cjiect
reactivity.
In the chair confomration, four carbon atoms are coplanar, and the other tu'o are

puckered out of this plane, one being puckered up above this plane(the carbon at the exlreme

righl ofthe depicted chair form) and one being puckered down out of this plane(the one a1 the

extreme left of the illustration). Another conformation which is important in any

conformational analysis is the transition state, or maximum energy conformation on the
rotational path.For cyclohexane this is the so-called "half-chair conformation", in which rrow
5 carbons are co-planar, and only one is puckered out of the plane.

In the illustration above, starting from the chair conformation, the half-chair fonn
depicted arises from moving the left-hand-most carbon of the chair form , which is puckered
down, upward into the plane of the four coplanar atoms. This creates considerable torsional
strain, especially around the two carbon-carbon bonds involving the left-most carbon. The
energy of this conformation is about 10 kcal/mol. The importance of this is that in any
conformational changes in cyclohexane, l0 kcal is the energy barrier, and the pathway for
such conformational changes must proceed through this relatively high energy
conformation.Because this barrier is so much larger than that in ethane or butane,
cyclohexane conformational changes can be "frozen out" at, e.g., -78 degrees. However, they

are rapid at or near room temperature. For all pmctical pu{poses, only the chair form is
oooulated.
\'..
Ther+is;.as-ipr.the case of butane, another energy minimum structue which can be
populated to a certain extent. This is the so- called "twist boat" conformation. However, since

this conformation is 5.5 kcal/mol higher in energy than the chair conformation, it is not a
highly populated state.Again, most of the strain energy results from bonds which are eclipsed
or partially eclipsed, i.e., from torsional strain.
3.3.12 Cyclohexane Conformational Energr Diagram

127
 cox.oBraaTroN4( tla.rcr DrATrtru,

Axial and Equalorial Bonds in Cyclohexone

Npte that in chair cyclohexane, there are two different types of C-H bonds, and thus
two chemically different types of hydrogens. The C-H bonds which point vertically upward
or downward are called axial. There are 6 of these, 3 upward and 3 downward bonds, and
they altemate up/down/up, etc., around the ring. The other six bonds, which radiate away
from the "equator" of the ring are called equatorial, and again there are six, 3 of which are
"slant up" and 3 of whicdh are "slant down", again altemating around the ring.
You should be able to quickly draw cyclohexane rings in which the axial and

equatorial bonds are readily identifiable and distinguishable..

AXIAL ANO E*UATORIAL BO!.IOS IN CI{AIN CYCLOHEXANE

sHe{$6 Hs H 6 i$t SHort N

.I.ID IABELIIII€

Chair/Chair Interconversion or Ring Flip

Understand that the best path (the lowest energy path) available proceeds via the half
chair and requires an energy input of 10 kcal/mol. These transition state proceeds to a twist
boat energy minimum, but this is not highly popupulated and generally plays little or no role
in cyclohexane's structure or chemistry. However, the twist boat can interconvert with
anolher equivalen! twist hoai llia tlle true boet contbrn',atiori as .r lransitiol'r stale) to gi\e
another chair slructure. in rvhich the sense of the ring lruckering is reversed. This is
significant in cyclohexane itsell. because in this process the arial and equatorial hydrogens
are interconverted.Since this interconversion or ring flip occrus rapidll,at room temperature.
all hydrogens spend 50% oftheir time as axial hydrogens and 509/o of their time as equatorial
hydrogens, so that on the time average all C-H bonds of cyclohexane are equivalent.
However, at any given instant, there are alu'ays two types ofhydrogen.

(:!-iA,R Cr'iAr R NTEFTCONVERTONS ()t]'t:l|a.ja.;

r r. r || )'
IN CYCIC)I{FXANE

.-.J- i
=#fia-
I

I t i.
+ \\.-----\
t----J \\\-^-I
is-rrie ._r:i &tlove, lr(rt C-t"l boods nO! st$wnJ

.,ECHANISM OF

*X .=*tdrF* -,!!.*.- Lr/ -,

{grck r qrffF}rl

=,.= V:a
oooo5ll€ 6€ose firaia
rsr..Bt
lFr.,.r.r ..e'..r)

Met hy I Cyc lo hexane C o nfo rmat io ns

729
 r:.: L'r r,l li:{):11*{ATl C}}tS {}f : l!!l E iH Y L i:l'i C L. C} t{ E.XAr:t E

'-.-\

;ir:,,r !r1!rlI:yl.',:l,rh;riira
I r. j, ij,IIn,L!.tlrir!(}l

\r
rr
! -r't
..--L I
t "5 <1i;:xi*: ir1l*tac1i!rt $lli.d'h

,r'*-'i -----J .

L-.r..___/
3

Since axial and equatorial bonds are non-equivalent. thers are two non-equivalent
posilions in which to place any substituent. We use the simple methyl group as an example.
but the same concept applies to any substituent.
Equatorial methyl cyclohexane is the more stable conformation. When the ring flip
occurs, horxever, it converts to axial methylcyclohexane. These two conformations are in
rapid equilibrium at room temperature, but can be frozen out as distinct compounds at -
T8degtees.

The equatorial conofrmation is favored in the equilibrium by a modest amount because the
axial isomer has about 1.8 kcal/mol of steric strain. This strain arises from the interaction of
one ofthe hydrogens ofthe axial methyl group with each of the two other axial hydrogens on
the same side of the ring, as illustrated above. Each of these steric intelacgions is
approximately equivalent to one gauche butane interaction of 0.9 kcal/mole, so the total is 1.8
kcal/mol. The point of the gauche butane comparison is that the H/H distance ofthe sterically
hindered hydrogens is almost exactly the same in gauche butane as with axial methyl
cyclohexane, except that there are two such H/H interactions in the latter case.

The steric interactions in axial methylcyclohexane are referred to as "l,3-diaxial

interactions", because the interactions involve two axial atoms or groups (one H and one
CH)@ the carbons bearing these atoms or groups are 1,3 related. The "equatoriality
principle" provides that any substituent prefers to occupy the less sterically hindered
equatorial position, if at all possiblefn the case of di- or poly-substituted cyclohexanes not all
substituents can occupy all equatorial positions in every isomer, but that isomer will be the
most stable in which all of the substituents occupy equatorial positions.

130
-1.-3.1 -l Disubstitutcd c).clopentanc

Conjornation ond stereo isot lers oJ I ,4-Dimeth!lc),cloherane

THAr,lE t50MEff

e.*- 1,4-dj&*thtfuYtlshs,(ane

E'0.0
{
,! . .l

E=O.O E * 4,6 kealr{nol

e.a"1,4-dir.lelhylcyclotr€xafl 6

cofrrPAfirsohr oF c1$ AN' rHANs,soMERs

dr llerrEri!4r!.cqda.rFr$ equaiy #rlsl
f4
I
p.g
Eq6:O E*r.A
*

131
 \ote that-x,itlr the 1..{<iisubsiiiirii()n pattern., tJ:e diequatoril) lniosts stable)
alran-qr'ment is what -l,e call the "trans" ison:or. in it, one iubstituent is "sianl up" and one
"slanl dorvn". Ring flipping gir.es a conlirlrnation in rvhich the melhyl substituenis are anti
(dihedral angle of 180) to each other. bu1 this is srill trcrns. and thisfonfbnnat ion is less stable
I
because it has two axial substituents.
T.here--is another isomer of I .4-dimethylcl'clohexane, thp,cl,r isomer. Recall
that crs andf, ralrs isomers are diastereoisomers. they are not different conformations of the

same isomer and cannot be readily intelconverted by a simple rotational process (a bond

would have to be broken).ln the cis isomer, hrrr, one methyl group is equatorial and one
axial, and ring flipping simply gives another equivalent confornation. Since one methyl is
axial, this costs 1.8 kcal of steric strain. Consequently, the cis isomer is less

thermodynamically stable than the trans, which has no steric strain in the more stable

conformation. The energy difference is again, 1.8 kcal/mol.

In the cis isomer, one substituent is vertically up (or down) and the other slant up (or down).
So they both point, in a general sense, in the same direction, i.e., both up or both down.

1 13-Dimethylcyclohexane
GONFOBUATIONS OF l,3.DIMETHYLCYCLOHEXANE

C'S DIASTEREO'SOMEH

1ff3*. =: cHs m0 H.C

a,a conform6i
E*0-o E = very larg€ {}d6/M€ dlaxial
i.'ae raction)

Trans

e,a contorrEr a,e cofilorner

€ = t.8 kcaumol E = 1.4 kcaYmol

Nqte thal lhc ris aBd lraoa diaElsreoi5om€rs are eot readrly interconvaried, tn t the
cif, iaomer i3 r/1{)16 eiabb,iontlooatArrrcally than th6 trana (hs head ol coitbugtiofl is
t -a kcavitrol less lhen lhe lrani

Ths mote stable oontomer and Ble more slablo irynor aro d6ls.mi.rgd by the
pdnciple ot maIjrn(,'r equatodarty,

732
 In the l.-l-Jisubstitution patiern ($l1r'lircr- it i.; din:ethyl or an)' olhel !..1-
di{substitution 1. b\)1h groups can only be equatorial uhen ihel'are both cis. So the cis isotrter
I
is the more stable isomer in this case. Ring llipping gir'es a confbrmation of the cis isontcr
which has both methl,ls axial. WprseJhae,that. the) are both on the sarne side of the rirrg. so
it is not an axial methyl/axial hydrogen interaction any longer, it is an axial methy/a\ial
methyl interaction. which is sterically much worse. Consequently this ring flip is too
energetically difficult, and this conformer can be neglected in Erconformational analysis.
The trans- 1,3-dimethylcyclohexane isomer, oo-&e-ether*eqd, has one methyl axial
in both ring-flip conformers, so that it is less stable than the cis isomer by 1.8 kcal/mol.
Both trans-l.4-dimethylcyclohexane and cis-1,3-dimethylcyclohexane have
essentially the same energy, since neither one ofthem has any strain at all.

CONFOBMATIONS OF 1,2-DliI ETI{YLCYCLOHEXAT'IE

Taent isorner

eHr
€,e a,a
E = 0.9 kcal*nol E - 3-6 kcEt.mot
Two axlal metlyl Oroupsi
21 1,4 kcafmole * 3.5
nq axial ffelhyls-
bst 1 grucho-butrno
typs interaclion b€lv/€eri
ths two ,netrf grgws.

lnore ee even
ms a siBric ds'labilizalion.

cts ,soMEB

g,a a,a
E * 1.8 kcaUmols C . I3 kcal/rtol

The l,2-disubstitution pattem is very much like the 1,4 pattem, in that the two groups
can only be equatorial if they are trans, so the trans isomer is more stable than the cis. The

133
diaxiai ilans c(rr'rli)nr1er has i.6 kcal of steric slrain. €+d ?se and is much les.-r liroletl than

the diequatorial conlbrmer.

'l-he cis isorrrer is less stable than the llans lrecause in it. one meth]'l musl be axial.

The cis isomer is (herefore less stable than the trans b1' 1.8 kcal.
The kei, ditlerence between the 1,2 and 1.4 patterns. is that in the diequalorial 1.2

conformation. the methyl groups are gauche as in gauche butane (remember that gauche
essentially implies a 60 degree dihedral angle ). Consequently, this diequatorial conformatiot.t
no longer is strain free. as was the 1,4-trans diequatorial conformation, where the methyls are
very far apart. The 1.2-diequatorial isomer is 0.9 kcal/mol less stable than the [,4-diequatorial
isomer. because ofthis gauche butaneJike interaction (recall that the gauche isomer in butane
is destabilized by exactly this amount).

Unit-IV
Chemistry of alkenes, alkynes, dienes ,benzene and benzenoid compounds.
4.1. Chemistry of alkenes, alkynes, dienes:

4.1.1. Alkene:
By now, we know that alkenes are important components of rubber and plastic products
but what are alkenes. They are organic compounds containing double bonds in their chemical
structure. They are interchangeably known as olefins. Alkenes are class of unsaturated

hydrocarbons containing carbon and hydlogen atoms having one or more carbon-carbon double
bonds in its chemical structure.

The unsaturation is because of the presence ofone or more double bonds in its structure.

The general chemical structure of alkene is RC=CR'. Acyclic alkenes are the subdivision of
alkene containing only 1 double bond. However, it lacks any other functional groups, also refers

to as mono-enes.
The general formula of the homologous series of hydrocarbon is CnH:n. Hence, alkene
contains 2 hydrogen atoms less than its corresponding alkane. Ethylene having the formula
CzFI+ is the simplest alkene. The IUPAC name of ethylene is ethane and it has the largest

industrial production among all the alkenes.

4.1.1.a. Nomenclature of Alkenes

We have to select the longest chain of carbon atoms having the double bond in order to
name an alkene according to the IUPAC system. We start numbering from the carbon chain near

to the double bond. "Ene" replaces "ane" suffix present in the alkanes. Even though the first
compound ofethane is methene but it has a short lifecycle.

734
 Therefole. the first stahie contpound is eIh)'lene ol' ethene ((-'ll;t \omenclalure or
r.raming alkenes is veq; similar 1o alkanes according to the IL]PAC' s\-s1cn]. L-et us once go
through the summar)'ol'the rules tbr nomenclature of alkenes with an c-xanrpi,--.

Rule I
Identification ofthe longest continuous chain containing the carbon-carbon double bond
is necessary. The parent name of the alkene compound will be sirnilar to its corresponding
alkane. Just the suffrx "ene" u,ill replace the suffix "ane", in case of the alkene. Suffix "ene"
represents the double of the alkene. For instance, if an organic compound continuous cluin
having a double-bond containing five carbon atoms, the compound will be pentene.

Rule 2
The numbering of the carbon atom starts on the side nearest to the double bond of the
continuous chain. Refer to the example below:

cltl*e}ll*CH*CI{-*L

Numbering of Carbon Atcms

Nomenclature of Alkena

Hence, the numbering starts from right to left because only in this arrangement the

double bonds remain in between the second and third carbon atom ofthe chain. On the contrary,
if numbering begins from left to right, the placement of double bond will be in between the third
and fourth carbon ofthe chain.

Hence, the nrle of nurnbering from the nearest side of the double bond will not be
possible. Therefore, the numbering starts from right to left in the above example. Moreover, it is
important to indicate the position ofthe double bond. Thus, it is necessary to place the lower of
the parr of numbers to the double containing carbon atoms before the name of the alkene.
Therefore, in the above example, the name ofthe compound can be written as 2-pentene.

Rule 3
It is important to speciff the location as well as the name of any substituent molecule
present in the compormd. For example, the below example can be written as 5-chloro-2-hexene.

135
 ( ri ,r i llj ( l{,,...{ il i ii

Rule 4
Another important rule 10 note in the nomenclature ofan alkene is to correctly indicate
the three-dimensional relationship of the organic compound, in this case of the given alkene.
This means that whether the compound containing double bonds is present in cis or trans
conformation. Therefore, to complete the nomenclature the comporutd, assigiring the
conformation is important. For example, the below example is cis-5-chloro-2-hexene.

cllf,txci;gHra
C*C
./c*'
1'

Confor,r-:.:tion of the Co*".r;:ou rrd

Nonre nclaturc of Aikcrrc

IUPAC Rules for Alkene and Cycloalkene Nomenclature

1 . The ene suffix (ending) indicates an alkene or cycloalkene.

2. The longest chain chosen for the root name must include both carbon atoms of the
double bond.
3. The root chain must be numbered from the end nearest a double bond carbon atom. If
the double bond is in the center of the chain, the nearest substituent rule is used to
determine the end where numbering starts.
4. The smaller of the two numbers designating the carbon atoms of the double bond is
used as the double bond locator. If more than one double bond is present the
compound is named as a diene, triene or equivalent prefix indicating the number of
double bonds, and each double bond is assigned a locator number.
5. In cycloalkenes the double bond carbons are assigned ring locations #1 and #2. Which
of the two is #1 may be determined by the nearest substituent rule.
6. Substituent groups containing double bonds are:

136
 t lr( -( i l - Vinyl group
Hrtl:('l t -CH2 - Allyl group

4.l.l.b.Geometric Isomers of Alkenes

Only positional isomers are possible fbr alkanes. but an additional lorm of isomer is
possible for alkenes and other similar molecules. The kind of isomerism which we have
already studied is called STRUCTURAL ISOMERISM. The new type is
called GEOMETRIC ISOMERISM. Geometric isomers are a result of the rigidity of a

molecule, which prevents rotation of atoms about a bond. This rigidity is usually due to a
ring structure or a double bond. Such rigidity is usually not present in singly bonded, open-
chained molecules.

These two compounds can be separated physically and are separately identifiable,
even though they have the same name, 2-butene. Most cases of geometric isomerism are a
result of molecule rigidity which prevents rotation about a double bond. In those molecules
in which the substituent groups are on the same side ofthe double bond, the name is preceded
by the prefix cis-. In those molecules in which the groups are on opposite side of the double
bond, the name is preceded by the prefix trans-.

A compound with methyl groups on the same (cis) side of the double bond is called
cis-2-butene, while the compound with the two methyl groups across (trans) the double bond
is called trans-2-butene. The other positional isomer of butene, l-butene, has no geometric
isomers because both methyl groups are on the same carbon. One geometric isomer cannot
be converted into the other without breaking the double bond.

137
 {.1.1.c, I'reparation of Alkenes
Prepfiration of Alkenes front Alkl:nes
r\lkynes r"urdergo partial reduction uith a parlicular quantity of dihl,drogen to produce
alkenes. The reaction takes place in the plesence ofpatladised charcoal that has been deactiyate,l
rvith poisonous compounds such as quinolone ot sulfur compounds. also knorvn as Lir.rdlar's
catalyst.

The reaction leads to the formation of compounds having cis-geometric conformation.

However, ifthe same alkynes reduction takes ptaced with sodium present in liquid arnmonia, the
resultant product will be trans alkenes.

li
tl
tl

I *:
til i. 1i: i: i
';' 1.,,; r.!',,ii t .,
.tri9,,-t'l;i' l1

M*th*S rf Alken** Pr*paratiCIn fr*nn Atky$e$

. ...l'*1
:t
{i9{:;fft'fi-${, ... . ....,-.,".:* {:!'tr-, {:}{.
*i t l e,lugrq" Ii* * *r'r l*"

{J1{* *#*fi}{. }"!* i31#t*f f*, *ff*{,,fl}{*

*'Yn.4*{*:r" tinllx*lte'

f urmple uf Alkrnm frcm Alkynex

Preparation otAlkenes from Alful Halides

R-X or Alkyl Halides undergo heating with alcoholic potash to form alkenes. Dissolving
potassium hydroxide in an alcohol such as ethanol leads to the formation of alcoholic potash. In
this reaction, the heating of alkyl halides with alcoholic potash will remove one molecule from

138
 halogen acid leacling ttr the tirlnration of alkenes. Tirus- it is a l1'.'lirrination reaction example
because removal ol'h1'drogen atom takes place from the B calbou atonr.

I ..
:, ".
. !.,,,
:.. ll
1"

I : iii;trritc.:r:1t {1, Sr. I

Fr*p.rrxii*n *{ Alkenes {r*m &lky: !"ln:1det

.- The rate of reaction is dependent on the alkyl group and natue of halogen atom. The

- order, in this case, is iodine > bromine > chlorine. The rate of reaction according to the alkyl

.- group is tertiary > secondary > primary.

, .l.Ld. Physical Properties of Alkenes

Physical properties of alkenes are quite similar to those of alkaaes. Let us take a look
at few physical properties
- Alkenes exist naturally in all three states. The first three alkenes are gases, and the next
' fourteen are liquids. Alkenes higher than these are all solids.

' All alkenes are insoluble in water, due to the weak van der Waal forces.
.* But alkenes are soluble in organic solvents like benzene or acetone because here the

* van der Waal forces will be replaced by new ones, making alkenes fully soluble.

boiling points of alkenes depend on their molecular structure. The bigger their
molecular chain the higher the boiling points. So the higher alkenes have very high boiling
points
\- The polarity of alkenes will depend on their functional groups

Chemical Properties of Alkenes

- are unsaturated compounds, which makes them highly reactive. Most of

"lkenes
these chemical reactions occur at the Carbon-Carbon double bonds. This makes alkenes far
more reactive than alkanes. Alkenes undergo tfuee types of main reactions, which are as

follows
' Addition Reactions
Addltion of Hydrogen:
:

139
 In the presencc ol nick.'l or platinum alkencs vrirl relri to add Io its ntcrlecular chain
one dialornic molecule ol'lldrogen (dihl,dlogen). Anci rn tirr; process, they become alkanes
due to the rean'angemenl ot'atonts.

.4ddition of Haloge ns:

Halogens r.vill reacl u,itl.r alkenes to fbm vicinal dihalides. From the halogens. iodir.re
rvill not react with alkenes. Bu1 Bromine reacts with alkenes and will attach at the unsaturaled
site. In fact. the reaction is used to as proof of unsaturation.
+ Brz C2fIaBr2
C2Ha 1"y taq) - luqy

Additiott of Halides:
These reactions follorv a certain rule. the Markovnikov rule. This rule states that the
negative portion ofthe reactant (the molecule which gets added to the chain) will attach itself
to the carbon with the least number of hydrogen atoms aftached. So when a hydrogen halide
will react with an alkene, the hydrogen will attach at the double bond to the atom with more
hydrogen atoms attached. The halide ion, on the other hand, will attach to that carbon atom
that has the lesser hydrogen atoms attached.

CH3-CH=CH2+ HBr -r CH:-CH(Br)-CH3

Addition of Water: According to the Markovnikov rule. water will react with an alkene
to form alcohols. This happens in the presence of sulphuric acid.
CHz:CHz + HzO CH3CH2OH
-
Oxidation Reactions
F Combustion Reaction: The combustion of alkenes is very exothemric; it will give out
huge amounts of thermal energy. A practical example of this reaction is seen in
welding of metals. It is knoun as oxy-ethylene welding.
CHz:CHz + 3Oz + 2CO2 + 2H2O t
I

F Oxidation by Pottasium Permanganate: When alkenes are reacted with cold

dilute KMnO+ also known as Baeyer's reagent, it forms vicinal glycols. It will also

decolourize the pink colour ofKMnOq. So it is used for testing unsaturation in

compounds.
4.1.1.e. Uses of alkenes
Alkenes are extremely important in the manufacture of plastics. All plastics are in
some way related to alkenes. The names of some plastics (Poly'thene or Poly Ethene,
Polypropene), relate to their alkene partners. Plastics are used for all kinds of tasks, from
packaging and wrapping, to clothing and outdoor apparel.

740
 I-orver alkenes are used as tuel anJ illunriirant. These may be obiainc,.i b1 thc cracking
- ol'kerosene or petrol.
- For the manufacture of a u'ide varietv ol' polymers. e.g., polyethene. poll'r'in1-lchloride

- (PVC) and teflon etc..

Elimination reactions

ll
H-C-C-lrl
\C=C/
---------t> H-I-{.-;
ll / \
Elimination reactions are important as a method for the preparation ol alkenes.

_ The term "elimination" describes the fact that a small molecule is lost during the process.
I,2-elimination indicates that the atoms that are lost come from adjacent C atoms.

The two most importafi methods are:

Dehydration (- H2O) ofalcohols, and Dehydrohalogenation ( HX) ofalkyl halides.
- There are threefundamental events in these elimination reactions:
- Removal ofa proton

- Formation of the CC z bond

- Breaking ofthe bond to the leaving group

Ir\
_ Depending on the relative timing of these events, different mechanisms are possible': Loss of
the LG to form a carbocation thon r6moval of H* with formation of C:C bond (two steps)
. 1 El reaction
- Simultaneous H* removal, C:C bond formation and loss ofthe LG (one step) 6E2 reaction
' Removal of H+ to form a carbanion then formation of C=C bond with loss of the LG (wo
- steps) : Elcb reaction

L4t
 -1. l. l.f. Elimination Mechanisrn:
E1 MECHANIS4V FOR ALKYL HALIDES

lt
H_C_C_X
B\/ H-.t
C=C
tt , : I Hf L'I
€)
,/\

Step 1: TJ I-
H - (1-!T1r '
Cleavage ofthe polarised C-X bond allows the loss ofthe
}LC
good leaving group, ahalide ion, to give a carbocation
I

intermediate. This is the rate determining step (bond ilov\J I

t
I

breaking is endothermic)
crr3
H -uf t((J.
JtI " I
(C]L
\t _ ]
,/
tr -f
Step 2: L---/

An acid/base reaction. Deprotonation by a base (here an I

rast
I
alkoxide ion) from a C atom adjacent to the carbocation T

center leads to the creation ofthe C:C H_c_Cr+

ROEI
rr-c'I{

E2 mechanism

E2 indicates an elimination, bimolecular reaction, where mte : k tB]tR-LG].

This implies that the rate determining step involves an interaction between these two species,
the base B, and the organic substrate, R-LG
This pathway is a concerled process with the follorting characteristics:

,.F* L-{.
-..,------\ rC \ /
B:' H . C-[IG _...........:I- B_H C=C LG-
ll /\

Simultaneous removal ofthe proton, H*, by the base, loss of the leaving group, LG,
and fomation of the n-bond
Let's look at how the various components ofthe reaction influence the reaction pathway:
Effects of R-

742
Reactivi1' ortlcr : tt.ll.rl_rc- > (CI{3)rCH- ;' C'llr( ll,- ' ('}{:-

4.1.1.g. Ilectrophilic Addition to Alkenes Mechanism

Electrophilic addition to alkenes starts wilh the pi electrons attacking an electrophile.
forming a carbocation on the most stable carbon. A nucleophile then attacks the carbocation
to form the product.
There ore many dffirent kinds of such addition, including:
r' Hydroxylation
r' Hydrogenation
r' Halogenation
/ Oxidative Cleavage
/ Hydration
/ Epoxidation
/ Cyclopropanation
/ Halohydrin Formation

Electophilic addition to alkerres:

First, formation ofthe carbocation on the most highly substituted carbon

Hla
I
I cu""
",b:i
H^c +
H

-H.c -c-
I
C_CH^
I

H.C H CH. H

Followed by attack ofchloride on the carbocation to give the addition product

ct-
\. T
H3C-C-C-CH. ...............
?, I
HSC-C-C-CH3
cH3 H cH3 H

743
 Free Bacical Additiol ot H Br To Alkcncs

H tt
---\rH .."-? /rJr'
ll
\Ac,r.
"
H-Br
Ro-oR
(peroxt6esr
l-
L-l",,, t1
' eH.
heat or lighl , i r.
',
aoti s./rt

R€giochemistry: anti-Mrrkv,rrikov
Slereoclremistyr syn + ardi
Slep l: ,nflrlrlion

heatat tighr
*S.-t* > z '6n
' noe unpaired erecrron
(lr€e radical)

lnitation (step 2) - aormation of bromine radical

.An1i
BO.,' ' H-ll! ---------------r> FOH *ii,:
l.t J.n. Zi"gl"r-natta catalyst
A !leEhdnism f0r Zieqler-Ndttd Cdtalysit
F:'

"' I .' .il td:.t,.- I

n H-C-R
Lrn,;.nL r

r'tel,lr,^t R' F' CH,

I

Cl,,.J.'\Cl H2C=CJR 61'"J+Cl rearrange

,*_..,
* -........* -
:di2]ti --t""""""* o.J:.ll-ci
-,t-,
LI/,.+."'LI

i ct/i'q
Zn-. ' + !+Cl
:

14 = Al. Li, MS, tt'c'tt

L is an unspedfied Iig.nd
H2C=CHR

R, R'
.I ,l\ H-C-R
R,
I

/,-{" IH-!-R ]
\ I

cttr / \ CH2 /z cHz

repeat cl,"J.,ncl rearrange
rinar nrouuct.- !f}{r$l
L
trnes cl/'r'S ,
9dr:fl.-,*
i'',,\
,C
H-'H
-many
4.1.1.i. Polymer of alkene Derivatives;

One of the most important technical reactions ofalkenes is their conversion to higher-

molecular-weight compounds ot polymers (Table 10-a). A polymer is defined as a long-

chain molecule with recurring structural units. Thus polymerization of propene gives a long-

f''
chain hydrocarbon with recurring -CH-CH!- units:

L44
 i ( il,
/r ti ('ll,( tJ ( li.
lrlr rr I

ri lti
{ -c u.J-,. -tl/'' kq:rl ,
. ': t, ,, ^- t:.,:lypropenc
i:r.:1, - . rrjlvpr+0ylenc;

4.1.2. Alkynes;

The preparations of alkl'nes are very similar to those ol the alkenes. The main
preparative reactions involve the elimination of groups or ions frorn molecules" resulting in
the formation ofn bonds.

4.1.2.a. Nomenclature of Alkynes

Common system: According to the common system, different mernbers of alkynes are
named in the form ofderivatives of acetylene.

IUPAC System: According to the IUPAC system, the nomenclature of alkynes is very similar
to the nomenclature ofalkanes. Hence, the naming is similar just the suffix "yne" replaces the
suffix "ane" of the corresponding alkanes. Moreover, the numbering ofposition starts with the
first carbon having the triple bond.
4.1.2.b. Preparation of Alkynes
Alkynes from Calcium Carbide
This is the industrial method for the preparation of ethyne. In this method, calcium
carbide undergoes treatment with water to form ethyne. Preparation of calcium carbide is
possible by heating quicklime and coke. We can obtain quicklime by heating limestone.

('()"

{'rifi - it(' -' ('.r(l ('(J

( .r1, !,rr n
r'.rrlrtrL'

Cirf. *21 1,0 ------+(:a(Ol lL +C-l l-

Preparation of Alkynes from

Calcium Carbide

Alkynes from Vicinal Dihalides

Treatrnent of vicinal dihalides with potassium hydroxide (alcoholic) results in the
dehydrohalogenation reaction. In this reaction, removal of a hydrggen halide molecule takes

145
place thereby fbrming aikcnr I halide. Ful1hernore. trealnlenr ot' ,,\lken1'l halide u,ith
sodamide produces alk]'ne.

, I , ;l
t,rr'l-.rra::on'Ji /t Ikynei I.$r'n VrcinaI
D;italrd* >

4.1.2,c. Physical Properties of Alkynes

) The properties of alkynes pretty much follow the same pattem of those of
alkanes and alkenes.

D Alkynes are unsaturated carbon that shares a triple bond at the carbon site
D All alkynes are odourless and colourless with the exception of ethylene which
has a slight distinctive odour.

F The first three alky,nes are gases, and the next eight are liquids. All alkynes
higher than these eleven are solids
F Alkyr,es are slightly polar in nature
F The boiling point and melting point of alkynes increases as their molecular
structure gows bigger. The boiling point increases with increase in their
molecular mass, Also, the boiling points of allTnes are slightly higher than
those of their corresponding alkenes, due to the one extra bond at the carbon
site.

4.1.2.d. Chemical Properties of Alkynes

Acidic nature
Coming to the chemical properties of alkynes, we begin with their slightly acidic
nature. Now Alkynes are slightly electronegative in nature. The triply bonded carbon atoms
in alkynes are sp hybridized, whereas like in alkanes the single bond,. atoms are sp3
hybridized, causing the difference in the electronegativity. This makes it easier for them to
attract the shared electron pair of the C-H bond.
So when we react a strong base like NaNH2 with ethyne, we will get sodium acetylide
and liberated hydrogen (H2) gas. But such reactions will not happen in alkanes and alkenes.

746
['he cgirclusion being that tfie hl,drogen a1o;ns i]1tlel'lcd 10 the carbon-cart,'t-'tl triple borl.l itr
alk)'nes are slighlly acidic in nature. It is to be no1t.d the other hydrogen atonrs baring these

ones are nol acidic.

HC = CH + Na----) IIC = C Na-+ l/2Hz

Adtlition Reactions
Under suitable conditions (temperature and pressure) alkynes will undergo hy'dration
reactions quite easily. Alkynes'nill leact with halogens, hydrogen and other such elements to
give a saturated compound as a product. Since thel' have a triple bond, two atoms of H2 or
halides or halogens can be added to its structure.
1l Addition of Dihydrogen
The reaction occurs in presence ofa catalyst such as Nickel or Platinum or Palladium.
Here the addition of hydrogen to the alkyne gives us an alkene.
C:H+(g) +2Hz(g -------r C3H(g)

2l Addition of Halogens
When alkynes and halogens like Bromine react, halogen will add itself to the structure
of the alkynes and result in halogen substituted alkenes. The resulting product will be

tetrabromopropane.

celu
*L"e =e H*{:C._H
-H+&& ---'--*
Ilrhl'ae -L Br Br "1"

t,z-Dibr$r}{-
elhene

Sr 3r
-D,II
- "'', H C-C-t{
1I Br Br

4.2. Dienes:

Dienes have two or more carbon-carbon double bonds which may be

either isolated (R'-C:C-R-C=C-R'), cumulated (R-C:C=C-R), or conjugated (R-C:C-C=C-
R). Each state represents a different stability due to electron delocalization, and the

conjugated form is generally favored in organic molecules.

Isolated Dienes

!47
 lsolated dienes typically shou rru "special" stabilit],. Their tuo ;r-bonds inleract
independenl o1'one another and thev cL',I'r'rpetc as intermolecular reaclion sites depentling ol
steric. kinetic. and thermodynamic f'actors. often. these types ofdienes can be trealed merely
as larger. more complex alkenes, because the tr.i,o bonds are said to have "communication"
(proximal electron delocalization due to location).

Isolated dienes are not considered to be especially useful in conlmon synthesis

reactions, although intermediates may often take the lorm ofan isolated diene.bb
Cumulated Dienes

Cumulated dienes are typically less stable than other alkenes. The main reason for the
instability is the fact that this sort of diene is a probable transition state for an alkyne's triple
bond to move down the carbon chain towards the most stable position. As you may recall,
rotation does not occur around any zr-bond, which means that cumulated double bonds can
lead to a less stable, higher energy compound being formed.

Typically, cumulated dienes are discussed only in advanced courses in organic

chemistry, and so they will not be discussed in detail here. Beginning organic chemistry
students should merely remember that cumulated dienes are 1) high ener gy and 2) most likely
found as transition states.

Conjugated Dienes
Conjugated dienes are dienes which have at least two double bonds separated by a
single carbon-carbon bond, and for this reason conjugated dienes are observed to have a
special stability due to the overlap of electron orbitals. The areas of concentration of negative
charge (electron density) overlap across the three bonds (two double bonds and one single
bond) forming what behaves essentially as a single, continuous zr-bond across three carbon
atoms. This delocalization of electron density stabilizes the molecule, resulting in the
arrangement of lowest energy.
Atoms other than carbon which are capable of multiple bonds may also participate in
conjugation. The heteroatoms most often associated with conjugation in dienes and other
molecules are nitrogen and oxygen, but theoretically the majority of atoms in the Periodic
Table of Elements could participate in conjugation chemistry. Most often, in organic

r48
 molecules. heteroatours parricipating in conjugation u,iil l-.c nitrogen atoms u,ithin a ring
structure or a double-honded oxygen attached to fomr a ketotre or aldehyde.

Conjugation ot'double bonds is the largest part ol r.rhat makes aromaticity relevant in
organic chemistry. and conjugated double bonds have many other significant impacts on
other types of dienes as u'ell.
4.2.l.Prepartion:

i) Dehydrotion of diols

I{OC1t,6t{eHrCt{G{ 4"r }i$-Cttr *Ctl:,*{r

tE@t",t$d !,&**d#$arc
Itffitc}t{r{r{l{,*&gil -HL &g * gff *Ct{r- CHl'o CI{,
pfiH*.i"+<tol rt+#Frtr
ii) De hydrhalogenation of dihalides

xfftclq$Lct{$ # n c *e*r - cH,* $Ir

l,{d!shar.*Ftr 1"}hfirdfii.
XCtt #"
Ol Clf.fif*Cll# UrC- eH - CH, - Ctl e CH,
t'rl{sr&da,E
f
"!"dh&pqst
' 4.2.2. Physical property of Dienes : l,3-butadiene is a gas.

- Chemical properties of Dienes

- (i) Addition of halogens t

' Cff?8dff8lCH=CH:
5l-0fr,rmo-I -! aeae (1. J-rUdjtua)
prrdora;aa ur fEJ SJ ia aon.ronisiag
Cll, = 511511 = CHr+ 8rr
rol*nt(hemneJ
1,3-Butadiene
1|
CHzSICH=CH.CHsEr
r{.EltrcmrLhtsrEtr, +*afiti:o 1
ptEdonitEtEr (7orJ in an imi=irg :o},rerrt
[aett rcil]

(ii) Adtlition of water:

L49
 ;* d,frrir1t-,r'tl,l=r!,1
!9ul-l-61.?.0/
iHz =lr!-f,N=f 11' 1L.lrp

[H3lr1=CH[H30H
m n-arl}ol

! ia: a.i-t:e:

Diels-alder reaction :

h-(
/"\ r
I r-x HC
,," CH

lJ -\ "r:)c , ,. ll I
ff - c,../----\ ,! \t . r*.
., '\ \ Eth.r cH /
rDieroPfiile' c'rr;hs€n'
,. o*r*u,i''
i.AJdoti

Stabitity of conjugated dienes : It is illustrated on the basis of delocalization of electron

cloud between carbon atoms.
The four fI electrons of 1, 3-butadiene is delocalized over all the four atoms. This
delocalization of the fI elechons makes the molecule more stable.

Q.==--fi-..,f+.-.=fl
.V V V V,
'n..-../l
,/ t-

A A'
UU UTJ --\

c_ a:
----- -i
-c_
I
x- Delocalised

(iv) Ozonolysis :

CEz:CHCH: CH2 + 2Or--vE----y2HCEO+ OECC1IO

l"
. t.. ,
\
ch.icH - cH:p+H _*-/
).,
I ii I ljil
"f.{- 7,? 1oi.=onli"1
"
"
150
{.2.3. Lscs: Elastomers ( rubber }

tsut1'l: radiation (poor); EO (erceilent): stcam (fair to excellent): tlrl heat (poor to good);
H1O2 (good, but only one cycle): ozone (pc\)r).

Applicuions: tubing. closures (but not implantables).

Ethylene propylene diene monomer (EPDM): radiation (good to excellent); EO

(excellent); steam (good to excellent); dn' heat (fair to good); H2O2 (fail to good); ozone
(l'air).

Applications: tubing, other uses (but not implarrtables).

Polyketones, polyether ether ketone (PEEK), polyaryletherketone:radiation (excellent);
EO (excellent); steam (excellent); dry heat (excellent); (excellent); ozone (excellent).
Applications : cardiovascular, orthopaedic, dental implants and tubing.
Nitrile: radiation (good to excellent); EO (excellent); steam (fair to good); dry heat (poor to
fair); H2O2 (fair); ozone (unknown).
Appl ic ations : surgical gloves.
Polyacrylic: radiation (fair to good); EO (fair, but only one cycle); steam (poor); dry heat
(poor); H2O2 (fair); ozone (good).
Polychlorophrene: radiation (good); EO (good); steam (fair to good); dry heat (poor to fair);
H2O2 (excellent); ozone (poor).

Applications: tlbing.
Silicone: radiation (fair to good); EO (excellent); steam (fair to excellent); dry heat (fair to
excellent, up to 200'C); HzOz (excellent, but surface steri- lant); ozone (excellent, but surfact
sterilant).

4.2.4. Electrophilic and Free Radical addition mechanism of diene:

The reactions of 1,3 -butadiene are reasonably typical of conjugated dienes. The
compound undergoes the usual reactions of alkenes, such as catalytic hydrogenation or
radical and polar additions, but it does so more readily than most alkenes or dienes that have
isolated double bonds. Furthermore, the products frequently are those of L,2 and 1,4 addition:

frr
I
BTCH:-CH_CH:CHT
lZ34Br. 3,,t-d ibro.rE 1 -bqtene
H'C:CH-CH:CH,r
BrCH*-CH:CH-CH3Br
1l-dibromcz-buterE

l.51
 F-ormation of both 1.1- ancl l.{-acidition products occurs llol oitlr * itit halogens. br"r1

also rvith other electrophiles such as the hydrogen halides. l'he mechanistic course of the
[eaction of 1 .3-butadiene u,ith h)'droge-n chloride is show.n in Equation I .]- ] . I'he first step. as
rvith alkenes. is formation ola carbocation. Ho*,ever. with 1.3-buladiene. if the proton is
added to C1C1 (but not C2C2). the resulting cation has a subslantial delocalization energy.
rvith the charge distributed over tu,o carbons (review Sections 6-5 and 6-5C iithis is not clear
to you). Attack of CIOCIO as a nucleophile at one or the other of the positive carbons yields
the 1,2- or the 1,4- addition product:

u-crr 1.1.+drlizi,;n
('H,.-Cl1 (lll*.r H- t . lcu,-i'tr*t l
'- '
(.ll '
t l
*. .. 1,,r, -.n1.,,.-i'n,j
-*,,___:_--.-.-........-
l-4-addition
1.H,.
.,'
CH.*qH*-911:49.
I
{r":, elBrtrqn *aioinlitalieE: CI
i

CHr*CH*CfI-CH"
{r3-il
CH" CI-l*Cl'{ * l-l,Ct
- C

A,n important feature of reactions in which 1,2 and 1,4 additions occur in competition

with one another is that the ratio of the products can depend on the temperature, the solvent,
and also on lhe total time ofreaction The reason for the dependence on the reaction time is
that the formation of the carbocation is reversible, and the ratio of products at equilibrium
need not be the same as the ratio of the rates of attack of CIOCIO at ClCl and C3C3 of the
carbocation. This is another example of a difference in product ratios resulting from kinetic
control verszs equilibrium control.

CHg*CH-CH-{-lH,

iin*
eH,eH:cHeH,r,
* [*rf8r;;JB*,J *.r*cHcH:cH!
{ri":}

Piedsminanl Brsds&inent
sq!iiibrluFr froducl kineli* fisdu6{
{1,4 additlo*} {U additlon}

t52
 'l
he lircr is rhat al lo\ temperatures
the l'2 prtrdtrct preclominates becausc js
more rapidl-1,. and the b, ir iirr.nrcJ
(Equation r3.2) Iror.rever ;:";:ilffi,il:'ll':::,::: I;"o:"::": I
stable, not because
it is formed more rapidly.
il
undergo addition reactions
,*",,r,1ffi:i.],j]::"1- bv radicar-chain mechanisms.
bromide to r .3-buradiene
r;":::1l:rlil,l, i"11.,,#, ;Hl,:ffi:*.::,
HB1 lrt',lnH ,Br.
ittitixtitn
{In. = initi&tor)

pr(,pt,lutitttt r-
cH,, _cH_-cH:cH,l
.. .,-_\ ---\ I*,
Hr -(.H"-CHTCH_(:H.-.---l r
" -l

h,.-.,r,-,lr:, r_.r,/
lr
BrCH,-tlH,.=gg-'CH,
* Ht,Br * g1_Cl.l.*CH*C11*CH., .Br
-
4.2.5. Rubber polymers

Natural Rubber:

Rubber is an exar
abliry to retum where the porvmer has
ro the
" "r-;;:i:;: rfiL:fi.lorrmer,
coired when in the ":
restin! state. rhe erastic properrie,
*::[1T"r;Jffii: f.ffi:
chains apart' but when
the tension is released the
chains snap back to
position'Natural rubber
is an addition poryner
the originar
that is obtained as a milky
as Iatex from a tropical white fluid known
rubb
,,3-butadiene) r,*" *;;" :". JT#:T:i:J:lff H:]::::ffJr;"fl:
polymerization reaction'
Natural rubber has the cis configuration for the
groups'charres Goodyear methyr
accidentalry discovered
that by mixing sulfur and
properties of the
rubber improved in being rubber, the
tougher, resista to
in elasticity. Thi, pro""r, heat and cord, and increased
was later ca,ed wrcanizatittt
vurcanization causes
shorter chains to cross , 0."
rink thro"* *Jri,H,lri"rll]#rr"o

153
 fiiat*ral F{nlrhsr
r: i,i:llne m0fr,:rUlel Llllll
i**----]
,f,I1 ].{.
. r'E- a
li 1_H (-)T^ ,_H- .. r :r .-l-l
- - - -.'tr'-
,_J:
- --r1-L-(la-,Jt!-tlit--\. - Ll'ii-r
IIr
CII L-tl '
1

\ Ll*rt ',;th .,i

UtCaflrzAtt0n
\,Sulphar
rlllr \ ctl,

-,IlE- C
rl:: ffl *}]{ - Cgr-':
::::.x{-S{r*
\,i cr,lss link
*rfts-C::-i (f{
-'jl -C{z-C:C}l -G{r
QIr r
{fl r

4.3 Benzene

4.3.1. Structure

Main article : Aromqticity

lr l{H t-\-H
,*.a-.t\".*
JI
' '\-/-
n../(...azr
CuHu lt
r'c\./'v
tt.t " \ _ -:.\r,
' -'
r'\.r(\ h
r:,.$

BcnzEnc J, *.krl, o.our.. J, Flanrr Huagon

It! olcculcr lormula (lsomen! aond lrnqrh rro sm

c-{.* -/A\.
_1
teEde
s
''
Sigma Eondr
:p'Hybndird oditalr
w-
6 F !6it.lr
dc lo: o lizcd
!ln!m
p i
tUJ
Bcn=ne nng
Eimplifi!d d.Firtion

The various representations of benzene. (N.8.: There is an etor in the label of the
secondJigure; the word "isomer" should be replaced by "resonance forms" or "mesomers".)

154
 X-ray dilliaction shous thal lll six carbon-carbon bo:rrl-i in l.rcnz-ene are of the samc
lengh, at 140 picometres( p n1) \ttt'tt rt""re'1|. 16. C-C bond lenglhs are gr.eater than a double
L

bond (135 pm) but shorter than a single bond (147 pnr).
.l'his
inlermediate distance is
consistent with electron delocalization: the electrons for C-C honding are distributed equally

between each of the six carbon atoms. Benzene has 6 hydrogen atorrs - fewer than the
corresponding parent alkane. hexane. The molecule is.planar. The MO description involves
the formation of three delocalized r orbitals ,pJn-,ing a[] bix carbon aloms. while the VB
description involves a superposition of.".onur!" structures. It is likely that this stability
contributes to the peculiar molecular and chemical properties known as aromaticity. To
accurately reflect the nature of the bonding, benzene is often depicted with a circle inside a
hexagonal arrangement of carbon atoms.

4.3.2. Preparation of Benzene

Benzene and its homologues may be prepared by the following methods.

By the decarborylation of sodium benzodte

This method is used in the laboratory to obtain benzene. Sodium benzoate is heated
with soda-lirne and when it gets decarboxylated (removal of carbon dioxide) benzene is
obtained.
COONa

;.-
+ NaoH + cao .-- * Na,co.
O O
sodium benzoate sodalime Benzene
By heating phenol with zinc
When phenol vapours are passed over heated zinc dust, benzene is formed.

A
OH

* zn heat> + ZnO
(/
phenol benzene
By the polymerization of ethyne (acetylene)
When ethyne (acetylene) is passed through a red hot copper tube, it polymerises to benzene.

155
 r-ttr
CH
-. I@l
cH '".
:,,

;-aj . -...::"

:h l- en: e4:

By the reduction oJ'benzene diazonium chloride

Benzene is formed on the reductiolr of benzene diazoniunr chloride r.l,ith sodium stannite or
hypophosphorus acid.
+
C6H5N 2 Cl- + H3PO2 + H2O ----------------+ C6H6 + N: + H:pO: + HCI
benzenediazoniumchloride
B)t the hydrolysis of sulphonic acid

Benzene sulphonic acid on hydrolysis with superheated steam gives benzene.

C6Hs.SO:H + HzO+ C6H6 + []156o

benzene sulphonic acid benzene.

4.3.3. Physical and chemical properties of benzene:

Benzene belongs to the family of aromatic hydrocarbons which are nonpolar

molecules and are usually colorless liquids or solids with a characteristic aroma.

Benzene being non-polar is immiscible with water but is readily miscible with organic
solvents.
Upon combustion ofbenzene sooty flame is produced.

ELECTROPHLIC SUBSTITUTION REACTIONS

1. Halogenation

Chlorine or bromine react with benzene in the presence of Lewis acids like ferric or
aluminium salts ofthe corresponding halogen, rvhich act as catalysts.

C}
I

,4,
ll i]
V
' --
Lt.
'
.u.br'. n icr,
--------------+
3oi) l2o l(
fA
V
Chlo.abgnz t}e

Br
I

it'A) ]l + ..ttr- _=--

Antqr. fcBr.
rAr
\r' 300 3:oK ' \r'
Brrn$Isrzano
+ IIBr

156
2. Sulphonation

'l-h,.:
replacement of hydrogen atonl tl1'henzene b1' a sulphonic acid gfi)up ( -SOrU) is

knorvn as sulphonation. The reaction is carried out by treating benzene rvith concentrated
letraoxosulphate (VI) acid containing dissolved sulphur(Vl) oxide or with chlorosulphonic
acid.

.It{i K
17
l"
+-?
lt
lt + Cbnc. ll,SO, + ll,*
)t jl
Be;lae*e tienriBe-
sdphonir
s{:id

+ cls{}3}t _****
fi}i*rmqtshanie
ocid ,l$1{$1e-
saipixni*
tci{i

3. Nitration

A nitro group ( - N02) can be introduced into a benzene ring using a nitrating mixture
(a mixture of concentrated tetraoxosulphate(Vl) aciC and concentrated trioxonitrate(V) acid).

l.t-so"
It )t + IINO, .'- '**r
' - =330K
+ Hro
Beria:r:c Nikrrbsn]zr$e

4. Friedel-Crafts AlMation

On treatnent with an alkyl halide in the presence of Lewis acids, such as anhydrous
aluminium chloride as catalys! benzene forms an alkylbenzene.

157
 l. :i,
l

''ir.:. ., :':.,.
,r l -lir'
' t.. ':..,

il 'r, rr : r...l'..'

..'ft;lr:r.rr...t

This reaction is called Friedel-Craft's alkvlation.

4.3.4. Orientation Effects in Substituted Benzenes

Substituted rings are divided into t\l,o groups based on the type of the substituent that
the ring carries:
Activoted rings: the substituents on the ring are groups that donate electrons.
Deactivated ringsj the substituents on the ring are groups that withdraw electrons.
4.3.5. Polycyclic aromatic hydrocarbon

./.\
-... J

Three representations of hexabenzocoronene, a polycylic aromatic hydrocarbon. Top:

standard line-angle schematic, where carbon atoms are represented by the vertices of the
hexagons and hydrogen atoms are inferred. Middle: ball-and-stick model showing all carbon
and hydrogen atoms. Bottom: atomic force microscopy image.

Polycyclic aromatic hydrocarbons (PAHs, also polyaromatic

hydrocarbons or polynuclear aromdtic hydrocarbons) are hydrocarbons----organic

compounds containing only carbon and hydrogen-that are composed of multiple aromatic
rings (organic rings in which the elechons are delocalized). The simplest such chemicals
are naphthalene, having two aromatic rings, and the three-ring
compounds anthracene and phenanthrene.
PAHs are uncharged, non-polar molecules found in coal and in tar deposits. They are
also produced by the incomplete combustion of organic matter (for example, in engines and
incinerators or when biomass bums in forest fires).

158
 PAHs are irbundani in the universe, and har,c rr:ccltil)' been forurd to have lirr:led
possibly as early as the lirst couple of billion years alier the Big Bang, in association
"r'ith
formation of neu, stars and exoplanets. Some studies suggest that PAHs account for a

significant percentage o1'all carbon in the universe.

4.3.6. Uses of Benzene

Moving on. Benzene has a lot of uses in different tlelds. Benzene is a widely used
industrial chemical and is a major part ofgasoline. Some of the other uses ofBenzene include
making plastics, synthetic fibers, rubber lubricants, dyes. resins, detergents, drugs and more.
Some ofthe popular one are mentioned and discussed below.
* As a solvent
* As an Intermediate / Production of rubber
.!. As fuel
.1. Printing Industry
As a Solvent
Benzene is commonly used as a solvent in many industrial, commercial and research.
Manufacturers use products which contain benzene as solvents in various production stages
and it is used in manufacturing chemical and plastic products. Few examples include resins,
synthetic products such as nylon, Styrofoam and others. Benzene is also used in the
production of asphalt that is used by roofing and paving companies.
Benzene as an Intermediate
Benzene is also used in the production oftires and rubber and it is found in adhesives
that are used to glue soles to shoes. Further chemical compounds that are manufactured using
Benzene include detergents, pesticides jnsecticides, herbicides, and dyes.

Printing Industry
If you didn't know, Benzene is found in most products that is used in the printing
industry. There are products that contain this chemical and are further used specially for
cleaning printing equipments which also makes them last longer and functional. Additionally,
ink and variety of painting products, such as spray paints, sealers, lacquers and stains also
contain some portion ofbenzene. It keeps the paints in liquid form.
As a Fuel
Due to the its high octane number and natural availability, Benzene is used as a fuel by a lot
of people and manufacturers. Some have used it as an gasoline additive to help bum fuel
more efficiently.
Health Hazurds.' ll()\\ever. the chemical als() c(),:t!'s r.r ith health risks associaterl irith
exposure to henzcne. It has both several etlecls like heirdache. instability, convulsitrns.
unconsciousness and ilrilations. Depending on the e\posure it can have bolh acute as \\eil as

cl-ronic effects. And this can happen u,hen Be'nzene is taken in through mouth or inhaled
througll air or absorbed by the skin. People ale usualll' exposed to benzene when thel' fill
their car rvith gasoline or while using household items that contain b.-"n"'J,fontaminated

4.3.7 Prepartion of naphthalene, Anthracene and Phenanthrenc

Polynuclear Aromaticri

(-\/ \ L)
Z\Z\
Naphthalene
..\..'-\..-\
Anthracene

ryo
Phenanthrene
Nomenclature
These compounds have two or more benzene rings fused together

891
Ja'\ \./ -.'\.\\,
'? //,'

titl
(;\\.,/'/''
/'/3
ir{
Naphtlralene Anthracene Phenantht.cne
CutrI" c,orilD

160
 l\romatic character of naphthalene, anthracene
and phenanthrene
L)..,r
(A,
ii

{B}

),. Resonance energy of A= 61 kcal mol-1

> Resonance energy of B = 84 kcal mol-1
i Resonance energy of C = 92 kcal moll
i, Resonance energy of benzene = 36 kcal mol-1

Aromatic character of naphthalene, anthracene

and phenanthrene
Naphthalene, anthracene and phenanthrene are classified as
aromatic because of their properties, which resemble those
of benzene.
(i) Experimental point of view
> Undergo electrophilic substitution reactions.
F Like benzene, they are unusually stable as indicated from
their low heats of hydrogenation and combustion.

c, tr_
i_{ I
r' "Ji--l>/"->: r
I\ ('\r2\---.rl 3{1
iJ
ax ca

eo*=-re*-*re
{. Shows aromatic properties
.i satisfy Huckel's ..,*jii!rr]r,*,
o

161
 Structure and Reactivity
A naphthErlL,ic .'-..l(..'l]le is derived by the fusion.-r; I i'-1r crl
benzene rin(r!i.
Unlike tlenzene. :l1FJ (--i:rrllcn -ca rbon bonds in naphrr,.ri()11€-, are not of
the same le nstth
Like benzene. naptrihale.-re can undergo electroplrri:. aronratic
substiiution-
Fo r many electropl-r ilic aromatic su trstitution rea cti or-rs r"rap hthalene
reacts under rnilder conditions than does benzene
For exarnple, whereas both benzene and naphthale.lq react with
chlorine in the presence of a ferric chloride or aluminirlrn chloride
catalyst, naphthelene and chlorine can react to fomr 1-
chloronaphthalene even without a catalyst.
Similarly, whereas both benzene and naphthalene can be alkylated
using Friedel-Crafts re actions,
naphthalene can also be alkylated by reaction with alkenes or
alcohols, with sulfuric or phosphoric acid as the catalyst.

1- Molecular Formula: CIoHB

-COOH
2. \irl)lrll*rl('rr. 'l - f' \-
!\--lA
\v, -CooH
So naphthalene contains the skeleton

(-(}(,lI
3. \rpt lI1$\tr l ()l
tl,nl"uc ron,rphr h.rtene >
co{)ll

+ Ss nitro grsup is pre$enl in be$zene rin$

4. Nsphth!tenell!:31193->Niiroraphth&tcnc -:SgI+..minon.pt[haterlc
lr"r
.l acid
The benzerle ring i.r phlhalic V
pr$duced by axidation o{ -__..
aminonaphthalene i$ rot the eame
ring is lhat obtained by oxida:ion
Pbrhnlir rcid
st .itronaphthalene.

L62
 h6ri Cr -c rLi e ' l
l-l *rqd €r l,t F: rna:thcd

!-i {::} d
(:l

ffi{
(.r,.( I r -{ ,, r,--\*1-^>
_,+--=rr_
c
)_)
/.u-ll'.' ll< I ,- -^r1- ---\ :'.
. ::_-\r_ *,---\--*-':\-
r

Preparation of Naphthalene

Naphthalene is the most abundant (about 10 %) single chemical compound present in

coal-tar. The middle oil fraction (170-230"C) of coal-tar is chilled when naphthalene forms
crystals. These are separated by centrifuging.

The crude crystals are melted and treated with sulfuric acid to remove basic

impurities. The crystals are then washed with aqueous sodium hydroxide to remove phenols
and excess sulfuric acid. Finally the naphthalene is distilled to get the pure product.

Properties of Naphthalene

F Naphthalene is a colourless solid which forms shining flaked-crystals.

F Its melting point 80.2oC and boiling point 217.9oC
) It has a familiar odor of moth balls.
F It is very volatile and sublimes slowly at room temperature.

! Naphthalene is insoluble in water, moderately soluble in alcohol, very soluble in ether

and benzene.

F It bums with a smoky flame.

F Naphthalene gives the usual aromatic elechophilic substitution reaction.

Reactions of Naphthalene

i) Naphthols and Naphthylamines

163
 OH

FeCl-.
HO OH
l........: . cr-Blnaphthol

Violet-blue ppt

,. oH
:,. .OH P'BinaPhthol
'.:
G.een ppt

ii) Halogenation

X2, Fe _*

B. 1 *n".
'"' . :: I'',
I cct.,A
Brr. _ Mg
....................* .,_".',-
u. r-"*i"
:
il-.,.,t . .l
""la ""-"a"4*
I -

lntroduction of NO2 and X groups opens the way to the

prepaaation of a series of 1-substituted naphthalenes.

iiD Friedel-Crafts reactions

cocH! 9o.x
z \. /-, Nrocr -\.'!..
f..L" --a* \)'-)

Acetylation affords access to the preparation ofa series of2-substituted naphthalenes.

Electrophilic Substitution reactions
Naphthalene undergoes ES molstly at alpha-position
Resonance forms determine higher reactivity at C- I
/ C-l attack has 2 resonance structures with benzene rings
/ C-2 altackhas only 1 resonance structure with a benzene ring
r' The most stable intermediate (C-1 attack) gives faster reaction

764
 Attark at C'1
I. tl I r ,t II:
t-

Attaek at C-2

!l }I
;- ,l) ll.1 !

,.,j

/ Like benzene, naphthalene can undergo electrophilic aromatic substitution

H..

. ..: -
-...
:'

I
I.ia. '
./-
(\ +!
,:t
\ ./) \"
i . .:
^,i/

il :,:
+,
-:

Anthracene (C1aH1s)

o Anthracene is a solid polycyclic aromatic hydrocarbon of formula C1aH16, consisting

of three fused benzene rings.

. It is a component ofcoal tar.

r Aathracene is used in the production ofthe red dye alizarin and other dyes.
o Anthracene is colorless but exhibits a blue (400-500 nm peal) fluorescence under
ultraviolet light.

165
 "* Ir. i {* i-

rA -n

. CrCz bond to have more double bond character (shorter bond length)
. Cz-C: bond to have more single bond character (longer bond length)
. From x-ray diflraction study. C1-C2: 1.37 A
Cz-Q- 1.42 S
I Resonance energy 84 Kcal mol-1 average 28.

Less aromatic than benzene

.\tlthr'rrcono

CEDA,,
,trllhrilccrrc

Preparation of Anthracene

166
 ..'. Coal tar- rvhich conlains arounc Li') i, ,\nthracene- remains a nta jr::r solrrtc t:r ;lri:
material. Common impurities arc phenanthrene and carbazole.

'!. A classic labomtory method for the prcparation of Anthacene is b1' c1'clodehl'.1ration
of 0-methvl- or O-methylene- substituted diary ketones.

* It may also occur in the interstellar medium. More than 20Yo of the carbon in the
universe may be associated with PAHs. including anthracene.

Properties of Anthracene

Anthracene is a colourless solid.

Its melting point 217 oC and boiling point 340 oC.

When crystallized from benzene, it forms a lustrous plate which exhibits a fine blue
fluorescence.

It is insoluble in water, soluble in alcohol and ether.

Resonance energy of anthracene is considerably lower than that ofbenzene; it is much

less aromatic than benzene.

Uses of Anthracene

Anthracene is used for manufacfure of anthmquinone.

Anthracene is used for making dyes (alizarin)

It is also used in smoke screens

Anthracene glycosides are oxygenated derivatives of pharmacological importance that are

used as laxatives or cathartics, anti-inllammatory, antibacterial, antifungal and also as natual
dyes.

ooHo

r4ff;:cl-x)#ry*el
oxomhrona

c*x7oy'/
o -4/ o*aan
lll
():X)
:r:
JII
I

o
Anrhraqtinone

167
Phenauthrene

{. The name phenanthene is a composite ofphenyl and anthracene.

.i. It is a polycyclic aromatic sy'stem cornprising three fused benzene rings.
.i An important skeletal nucleus in bile acids, sex hormones & cardiac glycosides.
.i. Codeine is used as analgesic & cough suppressant.

li l0

.1. Monosubstitution (Cr+HqX) - 5 isomers.

.i. Disubstitution (CraHrXz) = 25 isomers.

Preparation of phenanthrene

(i) Haworth synthesis of phenanthrene

@.4 o
Atct3

succinic anhydride
#"*.o&' zntrsr, rcr
I

HF
r-l
OtO
coou.
OQI
HOOC
-
:--:)

Zn(Hg).HCl
Pd, CO2, heat

168
(ii) Preparation of I -alkyl phenanthrene
.l
-,
,.,
:n !i
: .1-'il
.r..1/
./:. ./. , -,
(.,.l
t,l
,,-,-+ ',
li
\ ,,\ r.
: il'i , |-.,),
.--,

(iii) Preparation of 2-alkyl phenanthrene

li

.''\-'\ csfi
liii: , i _-}'_ ,a:t,1,"t:!ll
***-"-|}, ,

\'/ -,.,1'
\.1!,rt i,rl,. r.

_-:-r"

(iv) Posher synthesis

( ,(J ( Il.l (l()\x

J.t
(i\_J/)+\,), fli\_1,
1-\ \ ___+ \i.Ll /.!-11. irl l
_l ---_t,

\:\t)1,tl1S{}.1
----..*..-.}
1.,,

m
t

Phrntllllllr(.Ie

169
 Phl sical properries of Phenanthrene

c'olorless. Ilammable liquid (burns with a soorl tla,c due to incomplete conrbuslion).
Insoluble in r.l'ater-
i Good solvents lor rronpolar rnaterial.
i Less dense than lvater.
) Volatile
.. P Several aromatic hydrocarbons are toxic.

)' .J

5.1.1 Dualism of tight

Duality is the concept in quantum mechanics that every particle or quanta entity ,ray
be partly described in terms not only ofparticles, but also ofwaves. It expresses
the inabitity
of the classical concepts "particle" or "wave" to fully describe the behaviour ofquantum-
scale objects.

It seems as though we must use sometimes the one theory and sometimes the other.
while at times we may use either. we are faced with a new kind of difficulty. we have two
contradictory pictures of reality; separately neither of them fully explains the phenomena of
light, but together they do.

Through the work of Max planck, Albert Einstein, Louis de Broglie, Arthur
Compton, Niels Bohr and many others, current scientific theory holds that all particles exhibit
a wave nature and vice versa. This phenomenon has been verified not only for elementary
particles, but also for compound particles like atoms and even molecules.
For macroscopic particles, because of their extremely short wavelengths, wave properties
usually caru:rot be detected.

Although the use of the wave-particle duality has worked well in physics, the meaning
or interpretation has not been satisfactorily resolved; see Interpretations of quantum
mechanics.

Bohr regarded the "duality paradox" as a fundamental or metaphysical fact of nature.

A given kind of quantum object will exhibit sometimes wave, sometimes particle, character,
in respectively different physical settings. He saw such duality as one aspect of the concept
of complementarily. Bohr regarded renunciation of the cause-effect relation, or
complementarity, ofthe space-time picture, as essential to the quantum mechanical account.

)-tu
 Wemer Heisenberg collsia'lered the question lurlher'. Ile sar,t ihc tiualit-r'as present fbt'
aLl quantic entities. but not quire in the usual quantum mechanical acc,.)unl considered by
Bohr. IIe sau, it in what is called second quantization, which generates an entirely new
concept of fields which exist in ordinary space-time, causalitl slill being visualizable.
Classical field values (e.g. tl-re electric and magnetic field strengths of Maxwell) are replaced
by an entirely new kind of field value. as considered in quantum lield theory. Tuming the
reasoning around, ordinary quanturll mechanics can be deduced as a specialized co[sequence
of quantum field theory.

5.1.2 Wave nature of radiation

A charge is placed in an electric or a magnetic field, it experiences a certain fbrce

acting on it or if multiple charges are placed, they experience an interaction due to another. In
the year 1870, James Maxwell became the first scientist to explain the interaction between
the charges in the presence of the electric and magnetic fields. He proposed that when
electrically charged particles perform an accelerating motion, altemating electrical and
magnetic fields are produced and transmitted. These fields traverse in the forms of waves
known as electromagnetic radiation.A light wave is an example of the electromagnetic
radiation.

Properties of electromagnetic radiation :

1. The oscillating charged particles produce oscillating electric and magnetic flelds
which are perpendicular to each other and both are perpendicular to the direction of
propagation of the wave.
2. Electromagnetic waves do not require a medium i.e., they can travel in a vacuum too.

3. There are many kinds of electromagnetic radiation, differing from one another in
terms of wavelength or frequency. This electromagnetic radiation as a whole
constitutes the electromagnetic spectrum. For example radio frequency region,
microwave regioq infrared region, ultraviolet region, visible region etc.
4. The electromagnetic radiation is characterized based on various properties like
frequency, wavelength, time period etc.

Frequency is defined as the number of waves that pass through a given point in one
second. Mathematically it is equal to the reciprocal of the time period of electromagnetic

171
radiation. A general equa:io:: r'ciating the speed o1'light. liequencl. and rlavelength of an
electromagnetic radiation is given beloru:

c=1, I
Where,
c : speed of light,
v = fi'equency ofthe electromagnetic wave and
/ : wavelength of the electromag,nelic wave.

Apart from frequency and wavelength, some other paran'Ieters are also used to
categorize the electromagnetic radiation. One of these parameters is the r,l'ave number. Wave
number is defined as the number of wavelengths per unit length. Mathematically, it is equal
to the reciprocal ofthe wavelength. It is expressed in SI unit as m-r.

5.1.3 Classical theorl' of electromagnetic radiation

In classical electronagnetic theory, atoms and molecules are considered to contain
electrical charges (i.e. electrons, ions) which are regarded as oscillating about positions of
equilibrium, each with its appropriate natural frequency, ro . When placed in a radiation field
of frequency u , each oscillator in the atom or molecule is set into forced vibration with the
same frequency as that of the radiation. If v 11 voor v* vo, the amplitude of the forced
vibration is small, but as r approaches ruo, the amplitude of the forced vibration increases
rapidly.
To account for the absorption of energy from the radiation field, it is necessary to
assume that the oscillator in the atom or molecule must overcome some frictional force
proportional to its velocity during its forced motion. For small amplitudes of forced
oscillation, when y is very different from 16, the frictional force, and therefore the
absorption of energy, is negligible. Near resonance (i.e u is approx. equal to uo), the
amplitude of oscillation becomes large, with a correspondingly large absorption of energy to
overcome the frictional force. Therefore, the radiation of frequencies near the natural
frequency ofthe oscillator corresponds to an absorption band.

Classical expression lor energt in terms of omplitude (tltis is internel copy please check
and this is not a correct definition)
The amplitude ofa periodic variable is a measure of its change over

a single period (such as time or spatial period). There are various definitions of amplitude

L72
 (se!'bclo\\ ). *hich are all functions.t'the i:ragnilude ol'the difference
betu,een thc,
variable's exireme values. In older texts the phase is s.melimes
called the ampritud,.,.

You should already be faniliar with the formulae for potential and kinetic
energ"v.-, As a
refresher. the potential energy is

Er, .= lkri,

and the kinetic energy is

flp *
|mrt,
Recall that energy is measured here in Joules (J). Since the total mechanical
energy E is equar
to the sum ofkinetic and potential energy, we also have

Et * Ep* E* * |*# + lmuz,

where r is the displacement of the mass tn, which has a velocity v at that point. The
symbol refers to the spring constant defined earlier. Since there is no friction or
&
damping,
the total mechanical energy is a constant throughout the motion. This
fact allows us to derive
some a useful relationship. To do so, consider the total energy when
the mass is at its
maximum displacement, that*is*when the mass is changing directions from
moving rightward
to moving leftward. At this exact time, the verocity is equar to 0, and alr the energy is
potential energy.
. We car see this by inserting u= 0 and
x = .,4 into equation (6). Doing so, we get

e: f,*tz + |m(o), = l*Az.

Thus, if we know the amplitude and spring constant of the system,
we can find the total
mechanical energy.

5.1.4 Particle nature of radiation

Particle radiation is the radiation of energy by means of fast-moving subatomic

particles. Particle radiation is referred to as a particle beam
if the particles are all moving in

773
llrc sanic tlircction. similar to a ligJrt bearn. 1)',:e to the wave pa(icle duaiitr. all nror ing
paniclcs also have wave character. Higher erelur parlicles more easih.' erhihit particle
characteristics. u,hile lower energy particles morr eilsil),exhibit lvave characteristics.

TStpes trul production

Parlicles can be eleclrically charged or unchdrged:

Particle radiation can be emitted b1,an unstable atomic nucleus (r,ia radioactive decay).
or it can be the product from some other kind of nuclear reaction. Many types ofparlicles
may be emitted:

protons and other hydrogen nuclei stripped oftheir electrons

positively charged alpha particles (c)
helium ions at high energy levels
HZE ions, which are nuclei heavier than helium
positively or negatively charged beta particles (P* o. 9-; the latter being more
common)
high-speed electrons that are not from the beta decay process, but others such
as intemal conversion and Auger effect
photons (called a gamma ray, T, and acting in some ways like a particle.)

neutrons, subatomic particles which have no charge; neutron radiation

neutrinos
mesons

Mechanisms thal produce particle radiation include:

. alpha decay
. Auger effect
. beta decay
. cluster decay
. intemal conversion
. neutron emission
. nuclear fission and spontaneous fission
. nuclear fusion
. particle colliders in which streams of high energy particles are smashed
o proton emission
. solar flares
774
 . soltu' pariiclc evenis
. supernoYa e\plosions
. Additionall). galactic cosmic rays include these particles. but many ate 1i'om
unknon n urcchanisms
Charged parlicles (electrons, mesons. protons, alpha particles. heavier HZE ions. etc.)
can be produced by particle accelerators. Ion inadiation is w,idely used in the semiconductor
industry to introduce dopants into materials, a method kr.rou,n as ion implantation.Particle
accelerators can also produce neutrino beams. Neutron beams are mostly produced by nuclear
reactols. For the production of electromagnetic radiation, there are many methods, depending
upon the wave lenglh.

5.1.5 Black body radiation

Black-body radiation is the thermal electromagnetic radiation within or sunounding a

body in thermodynamic equilibrium with its environment, or emitted by a black body (an
opaque and non-reflective body). It has a specific specfum and intensity that depends only
on the body's temperature, which is assumed for the sake of calculations and theory to be
uniform and constant.

The thermal radiation spontaneously emitted by many ordinary objects can be

approximated as black-body radiation. A perfectly insulated enclosure that is in thermal

equilibrium intemally contains black-body radiation and will emit it through a hole made in
its wall, provided the hole is small enough to have negligible effect upon the equilibrium.

A black-body at room temperature appears black, as most of the energy it radiates

is infia-red and cannot be perceived by the human eye. Because the human eye cannot
perceive light waves at lower frequencies, a black body, viewed in the dark at the lowest just
faintly visible temperatue, subjectively appears grey, even though its objective physical
spectrum peak is in the infrared range. When it becomes a little hotter, it appears dul1 red. As
its temperature increases further it becomes yellow, white, and ultimately blue-white.

Although planets and stars are neither in thermal equilibrium with their surroundings
nor perfect black bodies, black-body radiation is used as a first approximation for the energy
they emit. Black holes zre near-perfect black bodies, in the sense that they absorb all the
radiation that falls on them. It has been proposed that they emit black-body radiation
(called Hawking radiation), with a temperature that depends on the mass of the black hole.

L75
 irllrltci(lcrlt r t'rlr.r r i., r

bla.:k
bo.IJ'

)- 2
-z)
crrrits a.ll t\
p<)ssiblc radiati()n

5.1.6 Plancks quantum thoery

A black body is heated, it emits thermal radiations of different wavelengths

or frequency. To explain these radiations, Max Planck put forward a theory kno*n as

Planck's quantum theory. The main points of quantum theory are

(i) Substances radiate or absorb energy discontinuously in the form of small packets
or bundles of energy.

(ii) The smallest packet ofenergy is called quantum. In case oflight, the quantum is
known as a photon.

(iii) The energy ofa quantum is directly proportional to the frequency ofthe radiation.
:
i;;".** -
E v (or) E hv were v is the frequency ofradiation and ..
h is Planck's constant havino
tt iiri" a.izs"lg'' 10-
" ";s;;;;.#"
(iv) A body can radiate or absorb energy in whole number multiples ofa quantum hv,
2hv,3hy . . ... nhv. where n is the positive integer.

Thus energy associated with each quantum or photon or light of a given radiation or
light is proportional to the frequency of emitted radiation or light.
This equation is applicable to all types ofradiation and is called plancks equation. This
shows that the energy associated with a quantum or a photon, E is equal to hv.

v= c/?" (c - velocity ofradiation, )"- wavelength ofradiation)

5.1.7 Photoelectric effect

The photoelectric effect is the emission of electrons or other free caniers
when light shines on a material. Electrons emitted in this manner can be called photo
electrons. This phenomenon is commonly studied in electronic physics, as well as in fields
of chemistry, such as quantum chemistry or electrochemistry.

176
 According to classical eicctrtrmagnetic theory. tl-ris effecl cau be anlrbLrted t"o the
transf'er ofenergy from the light to an electron. Ftom this perspecti\,d. an altcration in
the intensily of light would induce clranges in the kinetic energy of the electron-. cmilted from
the metal. Furlhermore, according to this theory, a sufficiently dim lighl would be expected to
shorv a time lag between the initial shining of its light and the subsequent enrission of an

electron. However, the experimental results did not corelate rvith either ol- the two
predictions made by classical theory.

5.1.8 Experimental observations of photoelectric emission

The theory of the photoelectric effect must explain the experimental observations of
the emission of electrons from an illuminated metal surface.

For a given metal surface, there exists a certain minimum frequency of

incident radiation below which no photoelectrons are emitted. This frequency is called
lhe threshold frequency. lncreasing the frequency of the incident beam, keeping the number
of incident photons fixed (this would result in a proportionate increase in energy) increases
the maximum kinetic energy of the photoelectrons emitted.
Thus the stopping voltage increases. The number of electrons also changes because of
the Fobability that each photon results in an emitted electron are a function ofphoton energy.
Ifthe intensity ofthe incident radiation ofa given frequency is increased, there is no efflect on
the kinetic energy of each photoelectron.

t77
 Above the threshold flequcncr.. t;tc nraximunr kinetic cnelgl of ihe emitted
photoelectron depends on the flecluenc) ol the incident light. but is independent of the
intensity ofthe incident light so long as the Lrtter is not too high.
For a girren metal and tiequencl, o1- incidenl radiation, the rate aI which photoelectrons
are ejected is directly proportional lo the intensity of the incident light. An increase in the
intensity of the incident beam (keeping the fi'equency fixed) increases the magnitude of the
photoelectric current, although the stopping voltage remains the same.
The time lag between the incidence of radiation and the emission of a photoelectron is
very small, less than 10-9 second.
The direction of distribution of emitted electrons peaks in the direction
ofpolarization (the direction of the electric field) of the incident light, if it is linearly
polarized.

5.1.9 Compton effect (scattering of x rays)

When a beam of x rays is allowed to strike a solid matter like carbon block. Electrons
are ejected from the solid matter like and x -rays are scattered from their original path. The
scattered x rays possess longer wavelength than the incident x rays. This phenomenon is
called Compton effect.

Scdtelrd

Photon

Etplanaliott
Ifa photon ofenergy hv strikes a solid matter a part ofthe energy is used to impart
kinetic energy to the loosely borurd electron in the solid. To conserve the energy ofthe
colliding photon the scattered x rays should posses lower energy and frequency.
hv=h\l +%mf
or V"mv2:hv -hl
or = h(v-l)
u2<u

L78
sigrtiJicanca
i) ( ornptorl effect is an prcof tor the L.a icle nalure of the light.

ii) it may be used to determine the value olplancks constant.

5.1.10 De - Broglies hypothesis

According to max planck quantum theory of radiation some phenomenon like

photoelectric effect and black body radiation can be explained, if light radiations is supposed
to behave as a malerial particle in particular point is space according to the maxwells rvave
theory of radiation certain other phenomenon like diffraction and interference and

polarisation can be explained. In 1924 a French physicist Lonius De Broglie idea of dual
character ofa light to matter particles and suggested that all matter particles in motion have a

dual character. The wave associated with matter particles is called De Broglie matter wave.
De Broglie equation
The help of plancks equation E = hu and Einstein mass energy relationship, E:mc2 1E:
energy of photon, h= plancks constant, D= frequency of radiation, m= mass of photon, c=
velocity of lighQ de Broglie derived a mathematical equation which gives the magnitude of
wavelength, X of a moving electron in terms of its mass, m and velocity v, the equation is,

l. = h/mv
Deriuation
We have seen that energy ofa photon, E is related to its fiequency u by plancks equation as,

E= hu (plancks equation)
or E = h. c/). [o=c/I]

1, is the wavelength ofphoton.

Again the energy of a photon E v/ith mass m and velocity c is also given by einsteins mass
energy relationship as,
E = mc2 (einsteins mass energy relationship)

h. c/), = mc2
or h/1.= mc

or X=h/mc
if the above equations is applied to a moving electron of mass m and moving with a velocity
v, then the above equation reduces to,

r: h./mv

179
This is tic Bloglir-'cqualiorl \uhicl'r gives the raiuc ol uarcler:gth (1") of a moving eleclr'r'n !n
temrs of ils mass (rn) and velocity (v).

5.1,11 Davisson and Germer experiment:

The first eridence for the wave nature ol'electron came from Davisson and Gerrner
experiment. ln these experiment electrons and produced fiom a heated tungsten (W) filament
and u'as accelerated by the action of an electric field. A beam of such accelerated electrons
u,hen allowed to fall on a nickel crystal was found to get diffracted, since diffraction is a
characteristic property of waves, electrons in motion could be assigned wave character.
Consider an electron of charge e and mass m, let us to be accelerated through potential V
volts and acquires a velocity v.
: eV
Electrical force applied on the electron
Kinetic energy acquired by the electron : % mv2

Movable
Detector/\ - ; ../'
\\ *
Vacr:um ,' * Diffracted
Chamber .,j
J.
'. electron bearn
-, \\\\

Electron Beam] Target

Y" mv2 = eY
n :2eYtm
(or) v =,lzev 1m
Substitude the value of v in de broglies equation, so we have write the equation
7r : h,/mv

l" =h/mx{rnl2ev
180
 (or) )" "= h rlmeV
On putting the values of h.m,e the above eqtrilii()r) hecomes
). = 12.26,i !V A0

If the accelerating polential is 5.1 volts, the electron rT'ave is lbund to possess a u/ave

lenglh of 1.66 A0. This rvavelength lies in the X ray range. Thus, therc is simitarity betrveen
electron waves and X rays. Further the braggs equation ofX ray diflraction can be applied to
electron diffraction. It's fbund that a maximum appeared in the inrensitl' of the diffracted
beam of electrons at an angle of500. Applying braggs equation for the llrst order reflection of
a beam ofelectrons on a nickel crystal.

n]. = 2d sin0

lx ),=2 >< 1.075 x sin 500

),:2"1.075x0.7660
: 1.65 A0

The value of}" calculated from braggs equation is in close agreement with that found from de
Broglie equation. This conformation the debroglie concept of wave nature of electrons in
motion.

5.1.12 Heisenberg uncertainity principle

In 1927 Wemer Heisenberg of Germany says this principle. He assumes that according

to a material the position and momentum of a moving electron can be determined accurately.
Wave material however treats that the electrons as a wave can spread out a region of space
around the nucleus. This is not possible to known as the exact place of impossible for
measure simultaneously the exact position and exact velocity of sub atomic particle like
electron and neutron.

AxxAp>W2n
Ax - uncertainity principle measurement of place
Ap - uncertainity principle measurement ofvelocity
> - this sign indicates to equal to or greater than
The relation given above is called uncertainity relation. From this equation is an evident
that if Ax is small and Ap is large and vice versa.
S ignijicance of uncertainity principle
D The uncertainity principle is a proof for the dual nature of electrons.
greatest accuracy on account of its small size.

181
 , At the l'llaxintunl tl:c pmbabilitl ol'locatir-rg L-lecuolls in I de llnite region of
space around the nucleus ma1, be predicted.

} The principle helps to knorvn as limit upto rvhich ue can measure accurately the
frequency o1'radiation en-ritted by an atom.
5.1.13 SCHRODINGER WAVE EQUATION
Schrodinger proposed that if the electron has war.e like nature.it should obey th. .urr. - ll.
'
equation of motion as all other knonn types of lvave obey. On the basis olthe simple idea-his
derived an equation n'hich describes the wave motion of an electron wave along any of the
thlee axis x,y and z axis and is called schrodinger wave equation. This equation can be
described by the equation,

v: A sin zvxlL ---- 1

v - represents the amplitude of the r.lave it is called as wave function.

A - is an constant, x - is the displacement of the wave in a given direction,

), - is a wave lengh

on differenting equation 1 with respect to x we get,

dv/dx : I A cos 2nxl]") [2nl)' ]
dv/dx: ZnNj" . cos 2tx/j" ---- 2
by differenting again equation 2,

dzv I dx2 : 2nNl" l-sin 2n</1,1 l2nl?., )

or d2v/ dx2 = - 4n2 N * . sin Zrx/?."

=- +./"tx21t.sinz*x1
= - 4n2/ ),2. v [v:Asinsir2:r:J]')
or d2v/dx2 + 4t? v /L2:0 -------- 3

This is a classical wave equation which describes the wave motion of any particle
vibrating along x- axis. We have seen the bohs theory that the total energy E ofan electron is
the sum ofthe kinetic energy K.E and potential energy V,

E=K.E+V
or E=Yrml + V ---------- 4

in equation(4) m is the mass ofan electron and v is the velocity with which the electron is
moving, now from de Broglie equation we have,
1. = h/mv

t82
 of mv : h,/L

or m'i - h2 n,2

or tl2 m2y2 = *12L2

or 1/2 rnv2 :h2/2t,2m ----- 5
the value % mr,: fi'om equation(5) in equation (4) we get,

E=*l2l"2m+v
or 1/ *:2ffi/ h2 + (E-v) ------- 6
Putting the value of 1/ ),2 from equation (3 ) we get.

d2vldx2 + 4n2 et x 2tt/ h2 (E-v) : O

or dv/dj + 8i m / h' (o-t7 v : o.

5.1.14 Physical significance ofv and I function

According to wave mechanics, an electron is treated a a three dimensional wave

characterised by the wave function v. The magnitude of v will give the amplitude of the
electron wave. Since the wave function v of electrons is very often an imaginary quantity,it
hass no physical significance by itself. But the square of the wave function v2 gives the
probabilityof finding an electronin a given region of space aound the nucleus. This region in
space is called atomic orbital and v2is termed probability. The probability function may be

large,small,zero but it cannot imaginary. Thus v2 will be real quantified if y is real. If y is

imaginary, y2 will also become imaginary quantity. In such a case the probability function
must be equal to v v* and not to be I where v* is the complex conjugate ofv thus,

Probability function = v2 (where v is real)

: v v. (where v is imginary)
5.1.15 Wave picture of electron

The electron is a subatomic particle, symbol e- or p-, whose electric charge is

negative one elementary charge. Electrons belong to the first generation of the lepton particle
family, and are generally thought to be elementary particles because they have no known
components or substructure. The electron has a mass that is approximately 1/1836 that of
proton. Quantum mechanical properties of the electron include an intrinsic angular
the

momentum (spin) of a half-integer value, expressed in units of the reduced Planck

constant, ft. As it is a fermion, no two electrons can occupy the same quantum state, in
accor(lirrcL'\\,ith the Pauli exclusio:r prinurplc. l.ike all elementar)' panicles. clccuons eslribit
propellies o1'both particles and r\'aves: the) can collide ll,ith other particles and can
be dilliacted like light. The rvave properlies of electrons are easier ro observe \\,ith
erperiments than those of other particles like neutrons and protons because eleclrorls have a
lolvc'r mass and hence a longer de Broglie r.r,avelength for a given energt,.

PROTON
NUCTIUS
NEUTRON

ETECIRON

Electrons play an essential role in numerous physical phenomena, such

as electricity. magnetism, chemistry and thermal conductivity, and they also participate
in gravitational, electromagnetic and weak interactions. Since an electron has charge, it has a
surrounding electric field, and if that electron is moving relative to an observer, it will
generate a magnetic field. Electromagnetic fields produced from other sources will affect the
motion of an electron according to the Lorentz force law, Electrons radiate or absorb energy
in the form of photons when they are accelerated. Laboratory instruments are capable of
trapping individual electrons as well as electron plasma by the use of electromagnetic fields.
Special telescopes can detect electron plasma in outer space. Electrons are involved in many
applications such as electronics, welding, cathode ray tubes, electron microscopes, radiation
therapy, lasers, gaseous ionization detectors and particle accelerators.
Interactions involving electrons with other subatomic particles are of interest in fields
such as chemistry and nuclear physics. The Coulomb force interaction between the
and the negative electrons without, allows the
positive protons within atomic nuclei
composition of the two known as atoms. Ionization or differences in the proportions of
negative electrons versus positive nuclei changes the binding energy of an atomic system.
The exchange or sharing of the electrons between two or more atoms is the main cause
of chemical bonding. In 1838, British natural philosopher Richard Laming first hypothesized
the concept of an indivisible quantity of electric charge to explain the chemical properties of

784
atonts. Irish phlsicist (ic'orBe .lollnstone Stone)taured this chuigc 't'lectron' in 1891, and .1. .1.

Thomson and his leanr of'Urilish ph),sicists identified it as a particie :n 1897.

Electrons can also participate in nuclear reactions. such as nucleosynthesis in stars.

where they are knor.r'n as beta particles. Electrons can be created through beta
decay ofradioactive isotopes and in high-energy collisions. fbr instance when cosmic
rays enter the atmosphere. The antiparticle of the electron is called the positron; it is identical
to the electron except that it carries electrical and other charges of the opposite sign. When
an electron collides u,ith a positron, both particles can be annihilated, producing gamma
ray photons.

5.1.16 Concept of atomic orbitals

In atomic theory and quantum mechanics, an atomic orbital is a mathematical

function that describes the wave-like behaviour of either one electron or a pair of electrons in
an atom. This function can be used to calculate the probability of finding any electron of an
atom in any specific region around the atom's nucleus. The term atomic orbital may also refer
to the physical region or space where the electron can be calculated to be present, as defined
by the particular mathematical form ofthe orbital.

Each orbital in an atom is characterized by a unique set ofvalues ofthe three quantum
numbers n,l, andn, which respectively. correspond to the electron's energy, angular
momentum, and an angular momentlrm vector component (the magnetic quantum number).
Each such orbital can be occupied by a maximum of two electrons, each with its own spin
quantum number s. The simple names s orbital, p orbital, d orbital and f orbital refer to
orbitals with angular momentum quantum number / = 0, 1, 2 and 3 respectively. These
names, together with the value ofz, are used to describe the electron configurations of atoms.

They are derived from the description by early spectroscopists of certain series ofalkali
metal spectroscopic lines as sharp, principal, diffuse, and fundamental. Orbitals for I > 3

continue alphabetically, omitting j (g, h, i, k, ...) because some languages do not distinguish
between the letters "i" and "j".

Atomic orbitals are the basic building blocks of the atomic orbital
model (altematively known as the electron cloud or wave mechanics model), a modem
framework for visualizing the submicroscopic behavior of electrons in matter. In this model
the electron cloud of a multi-electron atom may be seen as being built up (in approximation)
in an electron configuration that is a product of simpler hydrogen-like atomic orbitals. The
repeating periodicity of the blocks of2, 6, 10, and 14 elements within sections of the periodic
 table arises naturally ll'onr ihe total number o1- ertclr'ons that occupy a compiele ser
of s, p. d and 1'atomic orbitals. respectivell,. althoLrgh tbr higher. vaiues of the quantunl
number r. particularl)' *hen the atom in question bcars a pclsitive charge, the energic's of
certain sub-shells become verl.similar and so the order in which they are said to be populated
by electrons.

5.1.17 Shapes of atomic orbitals

According to quantum atomic rnodel, an atom can have many possible numbers ol
orbitals. These orbitals can be categorized on the basis of their size, shape or orientation. A
smaller sized orbital means there is a greater chance of getting an electron near the nucleus.
The orbital wave function or (r is a mathematical fuirction used for representing the
coordinates of an electron. The square of the orbital r.l,ave function or represents the
probability of finding an electron. This wave function also helps us in drawing boundary
surface diagrams. Boundary surface diagrams ofthe constant probability density for different
orbitals help us understand the shape of orbitals. Let us represent the shapes of orbitals with
the help of boundary surface diagrams:
S-orbital:
Boundary surface diagram for s orbital looks like a sphere having the nucleus as its
center which in two dimensions can be seen as a circle. Hence, we can say that s-orbilals are
spherically symmetric having the probability of finding the electron at a given distance equal
in all the directions. The size ofthe s orbital is also found to increase with the increase in the
value ofprincipal quantum number (n), thus,4s > 3s> 2s > is.

P-orbitals: Each p orbital consists of two sections better known as lobes which lie on either
side of the plane passing through the nucleus. The three p orbitals differ in the way the lobes
are oriented whereas they are identical in terms of size shape and energy. As the lobes lie
along one of the x, y or z-axis, these three orbitals are given the designations 2p*,2pr, and
2p,. Thus, we can say that there are three p orbitals whose axes are mutually perpendicular.
Srnrilar 1o s orbitals, size, anti ericr.li ol- p orhitals incrcase r,vith an incr.'iLsl in ili.: plincipal
quantunl number (4p > 3p > 2p').

*,.J, =#
}t.
D orhital:
fl{\e
Magnetic orbital quantum number for d orbitals is given as G2,-1,0, 1,2). Hence, we
can say that there are five d-orbitals. These orbitals are designated as d,r, dy,, d*,, d*2 ,2 and
d,2. Out of these five d orbitals, shapes of the first four d-orbitals are similar to each other,
which is different from the d,2orbital whereas the energy ofall five d orbitals is same.

5.1.18 Nodal plane in atomic orbitals

A nodal plane is a plane in which the probability of finding a electron is zero. The 2s
orbital has a nodalshell, whereas the 2p, orbital or 2p orbitals have anodal plane.

2p orbitals

L87
 Iror any atom, therc arc thr..e J7r orbitals. These orbitcls ha\ c lhc sanre shape but are
aligned differentll, in space. The three 2p orbitals nomlallJ- used ar.' labelled 27r,. 2p,., and
27r-, since the fuirctions are "aligned" aiong the x. -t', and z axes respectivel),.

Note that it is common to denote the shapes of 2p orbitals in books and papers as shown
below. These "figure-of-eight" s1)le pictures are used only tbr graphic convenience. These
pictures make the orbitals appear much "thinner" than they are really and also that there are

sharp "points" in the region of the nucleus, u,hich there are not.

ar
A OrJ
U

Each 2p orbital has two lobes. There is a planar node normal to the axis of the orbital
(so the 2p* orbital has ayz nodal plane. for instance). The higher p-orbitals (3p,4p,5p,6p,
and 7p) are more complex still since they have spherical nodes as well.

The origin of the planar node becomes clear if we examine the wave equation which,
for instance, includes an x term in the case of the 2p,orbital. Clearly When x : 0, then we
must have a node, and this by definition is the yz plane.

g tnd u character of atomic orbitals

The p orbital has two lobes one of which is +ve and -ve. On transversing equal
distances in a straight line in opposite directions from the centre of symmetry, the sign ofthe
function changes. This is called a ungerade orbital. In the case of d orbitals the sign of the
wave fi.rnction does not change under similar conditions. This type of orbitals are termed
gerade orbitals.

z axis perpendicular y axis perpendicular

to screen to screen
a2
ux -y 2 d.2

188
5.2.1 l\lasrell's distribution of molecular vclncitics

The nroiecules of gases collide with one anolhcr and also with vander rralls (,1'thc
container. Fherc occurs a change in momenlum lionr lime to time during such collisions.
,.
Thus all molecules present pres€nt in given santple ol'gas do not possess the same r elocirl .

Hou'ever fraction olmolecules may move with a parlicular r.elocity given time. Therefore the
gaseous molecules distribute intp different fractions moving with a definite velocity. 1'his is

results ol an certin std integrals J.C.N{axwell shou,ed the fraction of molecule having the

velocity bet\r,een c and c+dc can be expressed an.

dNAl = 4z[m/2rkT]3D C e-M'2t2kr dc -------- 1

m : mass of a single molecule

k : specific gas constant
for I mole ofan gas the above expression can be written as

dNA{ = 4z[IW2nRT]32 c2 e-Mc2/2Rr dc --------- 2

M : molecular weight of the gas
R : molar gas constant

Equation I and 2 are the mathematical forms of the maxwells law of distribution of
molecular velocities.
5.2,2 Types of molecular velocities
Three types ofmolecular velocities are reckoned with in the study ofgases. These are i) the

most probable velocity co ii) the average velocity < c > iii) the root mean square velocity
< c2>ln.
The most probable velocity cn defined as the velocity possessed by maximum number of
molecules ofa gas at a given temperature.
The average velocity < c > is given by arithmetic mean of diff. Velocities possessed by the
molecules ofa gas at a given temperature. If cr cz c: ..... c, are the individual velocities of the
gas molecules and n is their total number then average velocity is given by

cL+ c2+ c3+ .....+ cn

<c> -

189
 The root mean square velocity < c2>112 i-s de llr;ed rs the square root of the mean ol the
squares ol dif)-. Velocities possessed by molecules of'gas at given temperalure. Ei,identl) the

root mean square Yelocity is given by

c1+ c2+ c3+.....+ cn

<c>l/2:I l'
Where c1 c2 c-r..... cf are the velocities possessed by n molecules of the gas,

nlc1.+ n2c2+ n3c3 + .....+ cn

<cr>l/2:l 1'
n1+n2+n3+.....
5.2,3 Graphical representation
The Maxwell distribution of molecular velocities is plotted on the following figure.

.f{r'}
7rlX3>11

We can see that the fraction of the molecules having velocities graeter than zero increases
with an increase an velocity reaches a maximum and then falls off towards zero agin at high
velocities.
The importantfeatures of curves are follows,
as

D the fraction of the molecules with too low or too high velocities is very small.

iD there is acertain velocity for which the fraction of molecules is maximum. This

is called as most probable velocity.

The most probable velocity ofa gas is the velocity possessed by maximum number of
molecules ofthe gas at a given temperature. It corresponds to the peak ofthe curve. Its value
at a given temperature depends on the volume ofthe gas.

Significance

190
 i) The malhenraticai lirrm of maxwells
larv is usecl rLr c.Llcuiatc average velocity
the rool ,tcan squar.e l.elocity and the mosl probable reiocrt),of
the molecules
present in a giren sample ofa gas.
ii) It explains lhe effect of temperature on the l,elocity
molecules ofgases.

In a maxwells distribution law the exponential

factor is ternieci Boltzmann factor. .l-he
exponent is negative and temperatue
is in the denominator. r-he ractors therefore increase
markedly with temperature.

c0T
5.2.4 Collision diameter

The K'E of gases treat as morecules as point

masses. when two such morecures
approach each other a point is reached
at which the mutual repulsion between the molecules
becomes so strong that it causes reversel of
the direction of their motion. The distance
between them centres of the rwo
morecures at the point of their closest
approach is known as
collision diameter. It's denoted bv d.

o -+ d ) diameter of a two molecule

It can be easily if the distance between the centres of two molecures

seen that
is ress
than d' there would be a collision
between than the colision is an event
in which are the
centres oftwo identical molecules
come within a distance d fiom each other.

5.2.5 Mean free path

The distance travelled by the gas molecure

between two successive co,isions or
the
average distance travelled by a gas
molecule between colrisions. Evidentry
that equation,
)':<c>/Zr::e---
' ,,t2t dz<c>p/kT kr
./MP

797
 The above equation we see that ), c l/P the mean free path of a gas molecule is
inversely proportionl to the pressure. This fact is on tremendous importance in vacuum
systems. It should be I atm pressure, l. is very small compared with the macroscopic
dimension of the container which impies that molecule collide with one another far more
frequently tahn they collide with the walls of the container and that a molecule moves a
distance of several molecular distance before colliding with another molecule.

5.2.6 Collision number - Z

The below expression evidently gives the number of collisions suffered by a single
molecule per unit time and per volume of the gas. This is known as collision number.
The total number of molecules colliding per unit volume of the gas is therefore given
by
Z-"'l2n d'."rp
<c> - average velocity ofthe molecule
p - number density
Such asg an collision involves two molecules,the number ofcollision of like
molecules occurring per unit time per unit volume of the gas is given by

zv: % 1"12r d2 <c>P2 )

= ll.Jz (nd2 <c>p2).

5.2.7 Real gas

Real gases are non-hypothetical gases whose molecules occupy space and have interactions;
consequently, they adhere to gas laws. To understand the behaviour of real gases, the
following must be taken into account:

792
 cun i)ressibi lity effects;

\,ariahle specific heat capacity;

v a1r der Waals forces;
non-equilibrium thermodynamic effects:
issues with molecular dissociation and elementary reactions with variable composition

5.2.8 Vander waals equation of the state

Thought the equation PV:RT was arrived at first experimentally and then theoretically,
yet it f'ails to explain the behaviour ofreal gases. van der Waals attributed the deviation of
real gases from gas equation to the following faulty assumptions ofthe kinetic theory:

(i) The actual volume ofthe gas molecules is negligible as compared vvith the total
volume ofthe gas.

(ii) The gas molecules do not exert any appreciable attruction on each other.

Both these assumptions are not true at high pressure and low temperature. At high
pressure the volume is reduced to a great extent and the actual volume of the molecules
cannot be supposed as negligible under such conditions. Moreover, the molecules come
closer and the attractive force between them should also be taken into consideration.

Van der Waals introduced the necessary corrections as follows:

(a) Volume correction: At higher pressue, the volume is much reduced and at this state

the volume of gas molecules no longer remains negligible in comparison with the total
volume V occupied by the gas. Thus the free space available for motion of molecules is
reduced. If v be the volume of the molecules at rest, effective volume when they are in
motion must be greater. It has been calculated to be approximately four times the actual
volume of the molecules.

4G

4v and is generally denoted by b. Therefore the actual volume available in which the
molecules are free to move will be

: Total volume Effective volume.

-
i.e., correct volume(V - b)

193
 (h) Pressure cor"rection: The pressirrc r)l a gas is due to the hits ol'the :loiecules on the
u'alls o1'the containing vessel. lhe atrraclivL' lbrce betu,een the nrolecules comes into play
u'hen the rnolecules are brougl-rt close logeth!-r by compressing the gas. A niolecule in the
body of the gas is attracted in all the directions w-hen forces acting in opposite directions
cancel out. but a molecule. the boundary of the gas is subjected to an inrvard pull due to
unbalanced molecular attraction.

In this way some ofthe enelgy of the molecule about to strike the wall o1'the vessel is
used up in overcoming this inward pull. Therefore, it will not strike the opposite wall rvith the
same force. The observed pressure consequently will be less than the ideal pressure.
Therefore the ideal pressure, Pi will be equal to observed pressure p plus a pressure
correction, Pa depending upon the attractive forces,

I.e.Pi=P+Pa

Now, force of attraction * number of molecules in the interior which are attracting (i.e. ,
density)

c. ldcllsitti]
Total force of attraction i\rl.lulur.)r

Or, pressure due to force of attraction

- Irir,ilry
rI
. I'r:-
r.e., I'r
(where V is the volume ofthe gas and'a' is the coefficient of attraction)

.'. ideal urssure :P+:-

- lr2

Introducing, both these corrections, the equation becomes It is known as van der
waals equation. This equation explains the behaviour of real gases with great accuracy and
also the deviations ofgas laws from ideal behaviour.

Law of corresponding states

Real gases made by van der Waals were that all gases at corresponding states should
behave similarly. The corresponding state that van der waals chooses to use is called the

L94
 reducr'!l sia1.r. which is based on the devialion ol'thr curditions ofa substar:ee ikrnr its r>un

critical clrrditiorrs. We can define reduced quantities

PR=P/Pc

VR=V/Vc
TR='ti'tc

By substirution into the van der Waals equation we find

(Pr+3/V2.XVR- I /31=373r*

Which means the critical parameters for a gas can be expressed in terms
of aa and bb parameters
Vc:3b
P"=al27b2

]*o
c=8al27bR
We can rewrite the universal expression to express the compressibilily Z in reduced
- variables and plot measured values as Z versus the reduced pressure. As you can see very
- different gasesfliquids like nitrogen and water can be made to coincide if their properties are
- plotted relative to their critical points rather than in absolute terms. The compressibility factor

- Z can also be cast into the form of corresponding states showing that Z also can be expressed
as a universal function of Vn and Tn..
-

195
 9ir

(t

\-

\-