STUDY OF MOLAR REFRACTION AND

POLARIZABILITY CONSTANT OF SCHIFF

BASES IN DIFFERENT PERCENTAGE OF
BINARY MIXTURE OF DIOXANE-WATER
AT 304K
A PROJECT SUBMITTED TO
SANT GADGE BABA UNIVERSITY , AMRAVATI

FOR THE DEGREE OF

MASTER OF SCIENCE IN
CHEMISTRY
UNDER THE FACULTY OF SCIENCE
BY
SHRADDHA S. DHOTE
UNDER THE GUIDANCE OF
DR. M.M. MAHAJAN
ASST. PROFFESSOR DEPARTMENT OF CHEMISTRY
BRIJLAL BIYANI SCIENCE COLLEGE, AMRAVATI
 2021-2022

DECLARATION

I hereby declare that the project entitled “study of

Molar Refraction and polarizability constant of Schiff
bases in different percentage of binary mixture of
dioxane-water At 304k”being submitted for the award
of degree of Master of science in chemistry to Sant
Gadge baba Amravati University, Amravati . It has been
carried out by me at department of chemistry, Brijlal
Biyani Science college, Amravati under the supervision
of Dr.M.M. Mahajan Asst. Professor, Department of
Chemistry. The work is original and has not been
submitted earlier in part or full any other university/
institution for any diploma or degree.

Place : Amravati. Shraddha s. Dhote

Date : / /
 CERTIFICATE
entitled “study of Molar Refraction and polarizability
constant of Schiff Bases in different percentage of
binary mixture of dioxane-water at 304K” is the
bonafide research work carried out by Miss shraddha
s .Dhote at Brijlal biyani science college, Amravati. This
work has not been submitted earlier elsewhere for any
diploma or degree.

(Dr. P.B. Raghuwanshi) ( Dr.M.M.Mahajan)

(H.O.D)
 ACKNOWLEDGEMENT
Each step in learning process of life is an opportunity
which adds to our persona. A research project is
usually never a one man show but it is very much the
product of collective efforts. Behind every successful
work there is some sort of impetus provided by
someone.
I would like to express my sincere gratitude to my
guide, Dr. M.M.Mahajan, Asst. Professor, Department
of chemistry, Brijlal Biyani Science College, Amravati ,
For her blessing, patient motivation and optimistic
approch, I could achieve the aim of present task.
It is indeed very important to mention the co-
operation rendered by the non-teaching staff for their
round the clock help during the laboratory
equipments.
I also thank to all my classmate for constant
encouragement and help throughout the project work.
Lastly, acknowledge everyone who helped me directly
or indirectly to complete my work.
 CONTENT
CHAPTER 1: Introduction
1. Refractive index
2. General introduction of Schiff Bases
CHAPTER 2:
1. LITERATURE REVIEW
 Historical Development of Refractrometric Studies
 Previous Experimental Investigation
2. AIM OF PRESENT STUDY
CHAPTER 3: PRINCIPLE OF REFRACTOMETRY
CHAPTER 4: EXPERIMENTAL AND INSTRUMENTAL
CHAPTER 5: RESULT AND DISCUSSION

REFERENCES
CHAPTER 1:
INTRODUCTION
 CHAPTER 1:
INTRODUCTION

The speed of light in a medium depends on the properties of

the medium. In electromagnetic waves, the speed is dependent
on the optical of density the medium. Optical density is the
tendency of the atoms in a material to restore the absorbed
electromagnetic energy. The more optically dense material is,
the slower the speed of light. One such indicator of the optical
density of a medium is the refractive index.

Refractive Index Formula

The refractive index is dimensionless. It is a number that
indicates the number of times slower than a light wave would
be in the material than it is in a vacuum. The refractive index,
represented by symbol n, is the velocity of light in vacuum
divided by the velocity of light in a medium. The formula of the
refractive index is as follows:

n=c/v
Where,
 n is the refractive index
 c is the velocity of light in a vacuum ( 3 × 108 m/s)
 v is the velocity of light in a substance
The vacuum has a refractive index of 1. The refractive index of
other materials can be calculated from the above equation.
Higher the refractive index, the higher the optical density and
slower is the speed of light.
Refractive index of substance = speed of light in vacuum
Speed of light in substance
The studies of refractive indices are being increasingly used as tools
for investigation of the physical properties of pure components and
the nature of intermolecular interaction between the liquid mixture
constituents. Refractive index measurements of binary liquid
mixtures are essential for determination of composition of binary
mixtures usually for non-ideal mixtures where experimental
measurements are performed directly over the entire range of
composition. a few ternary, mixtures have also been studied
employing refractive index measurements. The review of literature
on acoustical studies of solution reveals that refractive indices
measurements are also used to estimate the different elastic
properties of the molecule from which the type of molecular
interactions can be very well understood. Pandey et a have made
refractive indices measurements in liquid mixtures and have
suggested that such studies are very much helpful for understanding
of the molecular interactions in the components of the mixture. In
addition to binary liquid mixture afew ternary, havealso been
studiesemploying refractiveindex measurements.
1. The refractive index is an important additive property of
molecular structure of liquid. For pure hydrocarbon, one can
get an idea of aromatic content of liquid using refractive index.
When a beam of light passes from less dense to denser medium
it is refracted toward normal to form angle of refraction and it
 depends on the temperature and wave length of light oflight.
The extent of refraction and it depends on
1. The relative concentration of atom or molecule
2. The stucture of atom or molecule. So refractive index gives
idea about geometry and structure arragement of atom in
molecule. However , there are are times when the
experimental values are not available, and it is desirable to
estimate the refractive index of binary or multi-component
liquids from the pure components by mixing rules. The most
commenly used mixing rules are Lorentz – Lorentz equation,
Weiner relation, Heller’s and Gladstone-dalee quations. These
mixing rules apply the concept of excess molar properties, a
measure of thermodynamic interaction changes with physical
forces in polar molecules. wasreported by vural et al

Instrumental method of chemical analysis was studies by

satinder Ahuja et al. The result obtained during this
investigation directly through light on the dipole association of
ligand, intermolecular attraction between solute and solvent,
dielectric constant of medium, polarizability and mutual
compensation of dipoles. These interaction have been studied
in aqueous and non- aquous solutions by many researches.
This project has been aimed at the study of molar refraction
polarizability constant of Schiff bases in binary mixture at
different concentration.
General Introduction of Schiff bases
A Schiff bases is a nitrogen analog of an aldehyde or ketone in which
the C = O group is replaced by C =N-R group. It is usually formed by
condensation of an aldehyde or ketone with primary amine
according to the following scheme:

The reaction of aldehydes and ketones with ammonia or 1º-amines forms

imine derivatives, also known as Schiff bases (compounds having a C=N
function). Water is eliminated in the reaction, which is acid-catalyzed and
reversible in the same sense as acetal formation. The pH for reactions which
form imine compounds must be carefully controlled. The rate at which these
imine compounds are formed is generally greatest near a pH of 5, and drops
at higher and lower pH's. At high pH there will not be enough acid to
protonate the OH in the intermediate to allow for removal as H 2O. At low pH
most of the amine reactant will be tied up as its ammonium conjugate acid
and will become non-nucleophilic.

The formation of a Schiff base from an aldehyde or ketones is a

reversible reaction and generally takes place under acid and base
catalysis, or upon heating given by S.P.Kolapkar et al
Typically the dehydration of the carbinolamine is the rate-
determining steps of Schiff base formation and that is why the
reaction
catalyzed by acids. Yet the acid concentration cannot be too high
because amines are basic compounds. If the amine is protonated and
becomes non-neucleophilic , neucleophilic, equilibrium is pulled to
the left and carbinolamine formation cannot occur. Therefore, many
Schiff bases synthesis are best carried out at middly acidic.
hydration of is also catalyzed by base. This reaction is some what
analogous to the E2 elemination of alkyl halides except that it is not a
concerted reaction. It proceeds in two steps through anionic
intermediate . The schiff base formation is really of two types of
reaction, i.e addition followed by elimination.

Chemistry and Biological Importance of schiff bases.

Schiff bases have a large number of synthetic uses in organic
chemistry . Acylation of Schiff bases by acid anhydrides, acid
chlorides and acyl cyanides is initiated by attack at nitrigen atom and
leads to net addition of the acylating agent to the carbon-nitrogen
double bond. Reaction of this type has been put to good use in
nature product synthesis.
An interesting application of Schiff bases is their use as an effective
corrosion inhibitor, which is based on their ability to spontaneously
form a monolayer on the surface to be protected. Many commercial
inhibitors include aldehydes or amines, but presumably due to the
C=N bond the Schiff bases function more efficiently in many cases .
The principal interaction between the inhibitor and the metal surface
is chemisorption . The inhibitor molecule should have centers
capable of forming bonds with the metal surface by electron
transfer. In such cases the metal acts as an electrophile and the
inhibitor acts as a Lewis base. Nucleophilic centers, such as oxygen
and nitrogen atoms, of the protective compound have free electron
pairs which are readily available for sharing. Together with the atoms
of the benzene rings they create multiple absorption sites for the
inhibitor thus enabling stable monolayer formation . Imines also
have biological importance. An imine linkage between the aldehyde
derived from vitamin A and the protein opsin in the retina of the eye
plays an important role in the chemistry of vision. Vitamins are also
called coenzymes, meaning that they are to the functioning of many
enzymes, which are large proteins that catalyze chemical changes in
cell. An example of a biologically important aldehyde is pyridoxal
phosphate, which is the active form of the vitamin B6. Vitamin B6
serves as a coenzyme by forming an imine with an amino acid
grouping an enzyme. The coenzyme, bound to the enzyme, is
involved in transamination reaction, the transfer of the amino group
from one amino acid to another, which is important in the
metabolism and the biosynthesis of amino acids. In the last step,
enzyme-catalyzed hydrolysis cleaves the imine to pyridoxal and the
modified amino acid. Schiff bases have been reported in their
biological properties, such as, antibacterial, antifungal activities .
Their metal complexes have been widely studied because they have
anticancer and herbicidal applications . They serve as modals for
biologically important species. O-phenylenediamine Schiff bases
show clinical properties . Isatin Schiff bases were reported to possess
antiviral, anti-HIV, antiprotozoal and anthelmintic activities [47].
They also exhibit significant anticonvulsant activity, apart from other
pharmacological properties . Certain cobalt Schiff base complexes
are potent antiviral agents . Schiff bases derived from 4-
dimethylamine benzaldehyde shows antibacterial activity. In
medicines used as antibodies and anti-inflammatory agents This
paper presents a series of new Schiff bases with a potential biological
activity resulted from the acidcatalyzed condensation of aryl
aldehydes with aromatic and heteroaromatic amines. These
compounds could also act as valuable ligands. The structures of the
Schiff bases synthesized from 2-amino-Benzthiazole, 4-aminophenol
In this respect pyridoxal schiff bases derived from pyridoxal and
amino acid have been prepared and studied from the biological
media.
Chelating ability of Schiff bases
The chelating capability is enhanced when nitrogen atom are hereby
in the neighborhood of one or more donar atom group. The
azomethine group carrying ligands i.e., Schiff bases have achieved an
important arrangement and become with better formation of the
complex or chelate.

Tetra dentate bis-Schiff bases

The condensation of diamino compound with salicyldehyde to get
schiff-base compound , which pocesses such a structural set up that,
two nitrogen and two oxygen atoms are available for the formation
of the bonds . These chelates are acknowledge as’ Salen Chelates’
and are comparable to the porphyrin structure, but this can be
simply synthesized. While the tetra-dentate ligandsobtained by
condensation of salicydehyde and diamino ethane were initially
termed as salen chelates but one more term salen type is now
engaged to fight the class (O , N, N,O) tetradentate di schiff bases.
However, the artificial drawing of schiff bases may hold stereogenic
centers and other elements of chirality.

Structure of Schiff base macro-cyclic compounds

Structure of Schiff base macro-cyclic compounds

 The metal-free ligands have been prepared and structurally
characterised for the first time, and this has led to the synthesis
of novel cubane and platinum-group metal complexes. The
synthesis of related dithiophenolato-bridged compartmental
complexes of NiII, CuII and ZnII has been achieved and the
relevance of these species to metalloproteins is discussed.

The inhibitor molecule should have centers capable to the forming

bonds with the metal surface by electron transmit. In this way metal
ions perform as an electrophile and the inhibitor act as lewis base. A
Nucleophlic axes of the oxygen and nitrogen atoms of the shielding
ligands has free electron pairs, Which are passionately obtainablr fpr
allocation .both of the atom are benzene ring, they generate several
absorption sites in the inhibitor, therefore it has permit stable
monolayer formation.

Schiff Bases Used As Catalysts

The oxidation of organic ligands are an essential and commonly used
reaction in laboratory level in an organic preparation, hence hundred
of different reagents and methods were accessible for the oxidation
of organic ligands. The selection of solvent ,oxidation reaction
condition such as temperature , pressure and number of reaction
steps are curical in affecting the speed of the recation and the type
and quantity of alcohols, either the subsquents carbonyl compounds
or carboxylic acids, the oxidation of sulfides to sulfoxides, alkenes to
epoxide, diols and activation of hydrocarbons.
polymerization  process Many Schiff base complexes of metal
ions show high catalytic activity. Chiral Schiff base complexes are
more selective in various reactions such as
oxidation, hydroxylation, aldol condensation and epoxidation. The
catalytic activity of metal complexes of binaphthyl, binaphthol and
their combinations with salen Schiff base is presented in this review.
The pyridyl bis(imide) and pyridine bis(imine) complexes of cobalt(II),
iron(II) ions have been used as catalysts in the polymerization of
ethylene and propylene. The phenoxy-imine (FI) complexes
of zirconium, titanium and vanadium and Schiff base complexes of
nickel(II) and palladium(II) were also used as catalysts in the
polymerization of ethylene. Schiff base complexes of metal ions were
catalytic in ring openingocesses at low temperature. Schiff base
complexes also catalyzed the oxidation
of sulfides, thioanisoles, aldehydes, phenol and styrene. Schiff base
complexes in super critical carbon dioxide (ScCO2) and in the
presence of polar solvents were active catalysts. Schiff base
complexes showed significant activity in catalyzing allylic
alkylations, hydrosilation, the decomposition of hydrogen
peroxide, isomerization, and annulation and carbonylation reactions.
The high thermal and moisture stabilities of many Schiff base
complexes were useful attributes for their application as catalysts in
reactions involving at high temperature.

Anti-fungal and Anti-Viral action

Twelve new bis-Schiff bases of isatin, benzylisatin and 5-
fluoroisatin 3a-3l were prepared by condensation of isatin,
benzylisatin and 5-fluoroisatin with primary aromatic amines. The
chemical structures of the products were confirmed by ¹H- and 13C-
NMR, IR and mass spectral data. The compounds were screened for
antiviral activity against a panel of DNA and RNA viruses. Minimum
cytotoxic and minimum virus-inhibitory concentrations of these
compounds were determined. Compounds 3c and 3i were the most
cytotoxic in HEL cells. These newly synthesized bis-Schiff bases were
also tested for their antibacterial and antifungal activities. They did
not display activity against S. cerevisiae (ATCC 28383) or C.
albicans (CIP 1180-79).
Wadher et al studied the synthesis and biological evolution of Schiff
Bases of dapone and their derivatives as anti microbial agents
 CHAPTER 2:
REVIEW OF
LITERATURE

CHAPTER 2
REVIEW OF LITERATURE
Litrature survey of the refractometer consists of two parts. First the
historical development in the refractometer and second is
Experimental work has been done in past corelate in refractometric
studies.
Historical development of Refractometric studies
Since the late nineteenth century refractometry was one of the main
techniques used in chemical analysis to determine concentration of
solution and as an aim in the identification of unknown substance. In
practice it is not possible to determine refractive index with sufficient
precision for the unique identification of the substance that’s not
different from boiling and melting points but similarly to phase
transition temperatures refractive index is an important property of
the substance the facilitates final identification.
Detection of liquid cocentration by optical means was already known
in antiquity . The law of refraction was mathematically formulated
first by Ibn Sahi in 1984. His discovery was not known in Europe and
usually the discovery is atteibuted to dutch astronomer and
mathematician Willebrord Snellius, (snell), who rediscovered the law
and published it in 1621. The first laboratory instrument to
accurately measure the refractive index of liquids was develop by
Ernst Abbe in 1874.
The most versatile refractometer in 1869, but it didn’t become
commercially available from Carl Zeiss before 1881. For the next
almost 40 years Carl Zeiss was the general principle was (and is up to
today )still the same , new models were fine tuned to increase
accuracy of the measurements.One of the important changes was
introduction of the temperature jacketed prisms, which took place
around 1893.
In 1874, Erbst Abbe published booklet”Neue Apparate Zur
Bestimmong des Brechungs zwrstreuugsvrmogens and fester koper
and fluddiger” Which described the construction and principle of
operation of the refractometer, is designed five year earlier. Basic
build of the original apparatus was identical with the modern
versions of abbe rerctometer, the only major difference that one
having no connection with the instrument optics and were the lack
of water jacket allowing for measurements at constant temperature .
Refractometer was initially produced only on request,for special
customers and product did not appears in Carl Zeiss catalogs before
1881 (but even then it landed between microscopes).In 1888 Carl
Pulfrich designed and described another device, also making use of
the critical angle, however his design was significantly different from
the Abbé refractometer. Initially, the refractometer designed by
Pulfrich was made by Max Wolz in Bonn, but after Pulfrich joined Carl
Zeiss his refractometer became one of the Zeiss products. Since that
time the device is known as the Pulfrich refractometer.
Although the two main refractometers - Abbé and Pulfrich - were
able to meet needs of majority of analytical laboratories, work on
better devices never stopped. New designs included devices suitable
for use outside the laboratory (such as immersion refractometers,
offered by Zeiss since around 1900) and devices providing better
precision than typical value of 0.0001 attainable with Abbé
refractometers.
As a result of the First World War the Germans were forced to pay
war reparations. Some of them have telescope both for positioning
of the border between light and dark areas, and for reading the
refractive index, which made it much easier to usebeen paid by the
transfer of patents and designs of equipment produced by German
industry to US and UK firms. That happened to optical devices
produced in factories Carl Zeiss Jena, in effect Abbé and Pulfrich
refractometers became available from Bausch & Lomb (US) and
Adam Hilger (UK). At the same time many firms that during war were
involved in production of optical instruments for army were looking
for new markets, and refractometers fit their manufacturing profile.
That led to production of many new refractometers, mostly based on
similar designs.
Zeiss factory in Jena produced refractometers until the destruction
by the Allied bombings during World War II. Up to this moment Abbé
refractometer was modified many times, small changes slowly
improved user experience with the device, its resistance to the
laboratory environment and accuracy of the measurements.
At the end of World War II Germany was split, same happened to
Carl Zeiss. Factory in Jena was in the Russian zone, the occupying
Russians relocated most of the existing Zeiss factories and tooling to
the Soviet Union, together with documents and designs. The western
part of the company therefore began work on a new device. New
refractometer used a single .

Previous Experimental Investigations

The properties of liquid such as refractive index polarisability
constant, molar refraction density in binary mixture are studied by
many refractometers.
The properties of liquid such as refractive index, ultrasonic velocity of
binary mixture are studied by many workers. Refractive index can be
measured easily with high degree of accuracy. The values of
refractive index depends on the temperature as well as on
wavelength of light used.
N.Yadevet al measured Refractive indices for the binary liquid
mixtures of n- butylethanoate and 3-methylethanoate with
cyclohexane, benzene,1,4-dimethylbenzene and 1,3,5-
trimethykbebzene over the entire composition range at 308.15K.
M.M.Kalaskar et al has studied molar fraction and polarizability
constant of some different substituted aminopyrimidine drugs in
same cocentration of ligand in different percentage pf solvent
concentration.
k.Anil Kumar e al has measured the refractive indices of 1,4-dioxane
with 1-butabol over the entire composition vary are measured at
398.15,303.15,308.15,313.15K using Anton paar Abbemat.
S.Balyuja et al has measured the density and refractive
index(RI)liquid mixture diethyl malonate + dimethylformamide,
diethyl malonate + hexane , diethyl malonate + tetrahydrofuran,
diethyl malonate + 1, 4 -dioxane
R. Talegaonkar et has studied molar fraction and polarizability
constant of substituted thiazolyl Schiffs’s bases such as 2-(3-phenyl-
1-(4-phenyl-thiazol-2-ylimino)-alkyl)-methylphenol(L1),2-(3-(4-
methoxy-phenyl)-1-(4-phenyl-thiazol-2-ylimino)-allyl)-methyl-phenol
(L2) amd 2-(3-(4-methoxy-phenyl)-1-(4-phenyl-thiazol-2-ylimino)-
allyl)-4-methyl-phenol(L3)in non -aqueous solvent such as 1,4-
dioxane, acetone and ethanol with different percentage.
P.krishnamurthi et al has been measured the refractive index
measurd for the binary mixture of n-heptanol with dimethylktone ,
ethyl methyl ketone, methyl metacrylate 301K. The molar refraction ,
atomic polarization ,polarizability and atomic radii and molar
volume evaluated.
A.W.Wakode et al measured refractive indices of benzothiazolyl and
benzimidazolyl substituted derivatives in different percentage of
binary liquid mixture such as acetone-wate , dioxane water and
DMSO-water at 35+_ 0.1degree celcius and observed that solvent-
solvent interaction was stronger than solute-solvent interaction.
V.S. Jagtap et al studied the refractive index, density , molar
refraction and polarisibility constant of substituted 1-phenyl-3-aryl-
1H pyrazol-4-carboxylic acid.
A.S. Chandami et al determined the refractive index, density, molar
refraction and polarisibility of substitutedN,Nbis (salicyliden)aryl
mrthane diamine in different binary mixture refractometrically .
R.T.Sawal et al studied the moar refraction and polarisibility of
antiemetic drug 4- amino -5- Chloro-N(2 diethylamino)ethyl-2
methoxybenzamide Hydrochlorid monohydrates in (Aqueous-sodium
and lithium Chloride) solution at 30 degree celcious
HK Patel et al verified the specific refraction and molar refraction for
homologous alcohol serial series at 30 degree celsius by suggested
formula.
Carl Zeiss was the first and for many years the only manufacturer of
Abbe refractometer.

AIM OF PRESENT STUDY:

Refractometry have found broad application in physical chemistry in
the determination of the composition and structure of substance .It
is also used in monitoring the quality and composition of various
product such as in the chemical, pharmaceutical and food industries .
The advantages of refractometery methods of quantitive