CHAPTER 1

GENERAL INTRODUCTION
The majority of reactions that are of chemical or biochemical interests occur in
solution phase. This leads to chemical investigation and prediction of the properties of solutions.
Because of the overall complexity of solution phase, the behavior of solutes is not yet completely
understood. This has lead to systematic and comprehensive investigations in the field.
Hence an understanding of the solution state in respect of thermodynamic and
kinetic properties is very essential to formulate reaction conditions profitably. In a solution there
shall be a minimum of two components namely a solute and a solvent. Hence behavior and
properties of a solution largely depends on the different interactions chemical or physical!
operating in it, besides the chemical and physical properties of the solute and the solvent. These
interactions relate solute"solute, solvent"solvent and solute"solvent interactions. #ach one of
these in turn is dependent on the nature of the component namely, neutral molecule, dipole or
ion. Hence, investigations of thermodynamic and physico"chemical properties of solutions
provide useful and profitable information in understanding the behavior of solutions.
$olute"solvent interaction studies have been a subject of interest among the
physical chemists for the last few decades.
%"&
The nature of the interactions and their influence on
the solution behaviour for various thermodynamic or other properties such as viscosity, or molar
volume, or conductance, or molar refraction, or ultrasonic velocities, or enthalpy or adiabatic
compressibilities etc. 'iterature is full of such studies in pure solvents but investigations in
mixed solvents are much less in number than in pure solvents. The studies relating to ionic
solutes in polar, covalent or ionic solvents are still less. $tudies in salt solutions in mixed
solvents where the salt has an ion common with that of the solvent as metal acetates in
water"acetic acid mixtures( metal sulphates in water"sulphuric acid mixtures( metal formats in
water"formic acid mixtures etc. are of recent interest in solution chemistry.
In case of a)ueous solutions, solute"solvent interactions are explained on the basis
of changes brought about by the solute in water structure. *ccording to the +lickering cluster
model of +rank and ,en
-
, the water molecules are considered to be in dynamic e)uilibrium
between the bulky tetrahedrally hydrogen bonded clusters and the denser monomer molecules
represented by the e)uation
.... %.%!
The statistical degree of ice likeness or whatever its structure in water! is
considered to be proportional to the half life of the clusters, which is of the order of %/
"%%
s in pure
water
-
. ,hen a solute is put into water, it is assumed that the former may shift the above
mentioned e)uilibrium in either direction. * solute which causes the shift such that the number
and the average half life of the clusters increase is termed as a structure maker and a solute which
has an effect in the opposite direction is called a structure breaker
-
. *lthough the concept of
structure breaking and structure making effects of solutes is not entirely satisfactory, it has
proved useful in discussing the effects of solutes on water structure. These effects are detected
experimentally by observing the changes brought about by the solutes in the properties of water
such as density, viscosity, refractive index, ultrasonic velocity and conductance. +or instance,
structure"makers are shown to decrease the fluidity of water and cause an increase in viscosity
and the reverse is true for structure"breakers.
It has been shown by these methods that cations of simple electrolytes such as 'i+
and 0g1l
2
, having high charge density, act as net structure makers and cations with low charge
density such as 1sI and 3Br, behave as net structure breakers. +rank and ,en in order to explain
these phenomenon visuali4ed
-
a picture +ig %.%! in which an ion is surrounded by concentric
regions of water molecules.
+ig %.%!
The inner most region 5*6 consist of water molecules which are polari4ed,
immobili4ed and electrostricted by the central ion. The water molecules in region 516 have the
normal li)uid structure which is polari4ed in the usual way by the ionic field which at this range
will be relatively weak. The intermediate region 5B6 is the region in which water is less ice"like,
i.e. more randomly ordered than the normal water. The decreased structure in this region is
presumably due to the approximate balance of two competing forces, namely, the normal
structure orienting influence of the neighbouring water molecules, and the radially orienting
influence of the electric field of the ion, which acts simultaneously on any water molecule in this
region. The latter influence predominates in the region 5*6 and the former in region 516.
Between 5*6 and 516 there should be a region of finite width in which more orientational
disorder should exist than in 5*6 or 516. 7ow it was assumed in the cluster model
-
of water that
the life time of the cluster is essentially dependent on the fluctuations of energy produced in the
li)uid water. *n ion with its first layer of water molecules will be a disturbing centre which
would both interfere with the initiation of clusters and hasten their disruption. Ions with low
charge density have relatively weak electrostatic fields, which make the region 5*6 very small
thereby causing net decrease in structure. In the case of structure making ions of high charge
density, the region 5*6 exceeds region 5B6, which results in net structural increase around these
ions.
It was shown in recent studies
8"%/
that solvent takes part in the reactions and in
bringing about interactions in the medium. *ll solvents critically influence the properties of
many solutes. It can, therefore, be concluded that the solvent nature is also an important
parameter in studying solute"solvent interactions. The behaviour of the solute in a particular
solvent is known from a study of some of the properties mentioned earlier. The two inseparable,
namely, ion"solvent and solvent"solvent interactions occurring in solutions can be studied
together by studying the properties of ionic solutions at infinite solution since ion"ion
interactions are eliminated at this solution. $ome significant applications of solute solvent
interaction studies are9
%. 1hoosing proper media for reactions in synthetic
%%
and analytical chemistry.
2. Biological processess
%2
.
:. ;evelopment of novel battery systems
%:, %<
.
<. ;evelopment of ion exchangers
%2
.
=. >rocessing of materials
%=,%&
to recover metals from non a)ueous baths with low
consumption of energy and
&. >rocesses involving salting in and salting out phenomena.
In the present investigations, physico"chemical properties like ;ensities, viscosities, ?ltrasonic
velocities, refractive index and conductivities of amino acids such as @lycine, *lanine, Aaline
and *rgenine in water and its binary mixtures with tertiary"Butyl alchohol at different moles
/.//%, /.//=, /./%, /./=, /.%! in different B like 2/B, </B, =/ B, &/B, 8/B wCw! at :/
/
1
have been carried out. These studies on the amino acids with a)ueous t"Butyl alcohol provides
useful information in understanding the behavior of li)uid systems, intramolecular and
intermolecular associations, complex formation and related structural changes. $ince amino acids
are 4witterions in a)ueous solutions, their volume and compressability properties should reflect
structural interactions with water molecules as in the case of electrolytes.
*mino acids, the monomer units of protein molecule play an important role in all biological
species. *n interesting classes of solute i.e. the amino acids whose interactions we are
considering here lies in between electrolyte and non"electrolyte. *mino acids nature influence
the primary structure has a tremendous impact on the design and functional properties of proteins
at supramolecular level. +or the past few decades, a considerable study has been carried out to
investigate the hydration of proteins through volumetric and ultrasonic measurements, since
these properties are sensitive to degree and nature of hydration
%-"22
.
>roteins are biomolecules which play a vital role in all the biochemical processes occurring in
living organisms. They play vivid vital roles as principal building materials of skin, muscle,
nerves, blood, en4ymes, antibodies, hormones etc. Their behavior can be governed by the
interactions with the surrounding environment. Investigation of the physicochemical properties
of the denatured states of the proteins are re)uired to identify and characteri4e the contribution of
various non"bonding interactions between different functional groups of protein and protein"
solvent interactions which are driving forces for a biological process
2:
. ;ue to the complex
molecular structure of proteins, direct study is some what difficult. Therefore, the useful
approach is to study simpler model compounds, such as amino acids which are building blocks
of proteins.
The investigation of volumetric and thermodynamic properties of amino acids and
peptides in a)ueous and mixed a)ueous solvents has been the area of interest of a number of
researchers. 0ost of the studies on amino acids
2<"2&
and biomolecules
2-"28
have been carried out in
pure and mixed a)ueous solutions. *)ueous solutions of electrolytes and non"electrolytes with
amino acids provides useful information in understanding the behaviour of li)uid systems,
because of intermolecular and intramolecular association, complex formation and related
structural changes affect the compressibility of the system which in turn produces corresponding
variation in the densities, viscosities, ultrasonic velocities etc. 0ixed a)ueous solvents are used
extensively in chemistry and other fields to control factors like stability, reactivity and stability
of system.
*mino acids form 4witterions in a)ueous solutions. Thus the volume and compressibility
properties reflect the structural interactions of amino acids with water molecules as in the case of
electrolytes. ,ater and Tertiary"butyl alcohol mixtures have proved to be the most interesting
owing to the strong hydrogen bond interactions. Hence an attempt is been made to study the
interactions between the water soluble amino acids in ,ater and Tertiary"butyl alcohol mixtures.
Tertiary butyl alcohol is selected as it is a bulky tertiary alcohol which behaves like polyhydroxy
alcohol. In biological systems bulkier polyydroxyl compounds are known for stabili4ing the
native conformation of globular proteins
2D":%
.



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