1.

1 BACKGROUND:

Generally, matter is found in three different forms: solid, liquid and gas. The main

difference among the three states lies in the arrangements of atoms, molecules or ions

constituting the matter, liquid being at the intermediate state between the other two.

Liquid systems are actually very complicated though apparently look simpler than gases

and solids. In the ideal approximation, gases are characterized by complete randomness at

high temperatures and low densities. On the other hand, all the molecules, atoms or ions

in an ideal crystal are arranged in a completely ordered fashion. As because of the

extremes of perfect chaos and perfect regularity, both are easy to treat mathematically.

But liquids represent a peculiar compromise between the order and disorder.

In liquids, cohesive forces are sufficiently strong to lead to a condensed

state, but to prevent the considerable translational motion of individual molecules

these forces are not strong enough. Consequently, thermal motions introduce a

disordered situation in the liquid without completely destroying the regularity of

its structure. So the concept of partition function is difficult to define a liquid and

the knowledge about the liquid state is a meager.

In this connection, it is obvious that pure liquids and their mixtures have

mysterious characteristics, which are much more complex to understand compared to the

behavior of solids and gases. This may be their existence in between ordered and
completely disordered molecular arrangements. There may be lots of interaction or forces

acting among the liquid molecules. So, it is not easy to define their nature quite simply.

No single interpretation of liquid characteristics generally can be put forward. Therefore,

investigation must be done to get idea about the characteristics of each and every liquid

and their mixtures.

Behavior of liquid-liquid mixtures is much more complicated, mysterious and

interesting. Though a number of studies have been performed, still no certain rule has

been developed that can be used to interpret behavior of completely miscible solutions.

Simple mixing rule is totally failed to explain the real behavior as well as deviation from

ideality of the liquid-liquid mixtures.

In order to understand the nature of molecular interactions of liquid-liquid

mixtures, we have been pursuing volumetric, viscometric and refractometric studies for

the last few decades by measuring properties like density (ρ), viscosity (η ), refractive

index (n) etc. These enabled us further calculating the excess molar volume, partial molar

volume, apparent molal volume, thermal expansivity, excess thermal expansivity from

‘ρ’ values. η gives the excess viscosity, interaction parameter and thermodynamic

properties, such as, free energy, entropy, enthalpy as well as their excess values for the

activation of viscous flow. Likewise, ‘n’ leads to calculate the deviation in refractive

index, molar refractivity, deviation in molar refractivity etc. Our systematic studies

included binary solutions of organic compounds consisting of varieties polar-polar, polar-

nonpolar, nonpolar-nonpolar systems [1-26]. The types of compounds considered are

2
alkanes, alkenes, alkynes, alcohols, amines, amides, ketones, eathers, acids, nitriles,

alkanolamines etc. All the studies revealed that various types of interactions or forces

acting between solute-solute, solute-solvent and solvent-solvent molecules in the

solutions which are considered to be responsible for the anomalous behavior in liquid-

liquid mixtures.

In recent years increasing attention is given to the study of physico-chemical

properties of aqueous solutions of ‘hydrophobic’ organic substances. Water is a

mysterious liquid with very characteristic properties, such as, very high cohesive energy

density due to its 3-dimensional hydrogen bond network reflected by its relatively high

boiling point, high density, high relative permittivity and a low polarisability compared to

other organic solvents. The properties of water and aqueous solutions have been

extensively studied over the past century and comprehensive reviews have been written

[27-29]. Water and its solutions with organic compounds especially biologically

important molecules are indispensable for living systems. Biological processes and the

formation of biological structures, such as, folding of proteins, formation of lipid cell

membranes etc. are uniquely mediated by the solvent water. These processes are brought

about by noncovalent interactions. Particularly, ‘hydrophobic interactions’ between

apolar groups play an important role in the molecular recognition processes of biological

molecules in water.

Over a decade or so, we are pursuing volumetric and viscometric studies of

aqueous solutions of various hydrophobic compounds having similar functional groups as

in biologically important ones. The unique properties of their solutions are that, they

3
exhibit sharp maxima in viscosity in the water-rich region and considerably large volume

contractions occur with minima also in the water-rich region. These properties are found

to be strongly influenced by chain lengths, size and number of alkyl groups, branching,

types of functional groups and other structural features of the solute molecules.

Although quite a significant amount of studies have been made related to

‘hydrophobicity’ in our laboratory and elsewhere in the world, yet more systematic

studies are necessary for better understanding. We may presume that, both ‘hydrophobic

hydration’ and ‘hydrophobic interaction’ play vital role for the observed behavior of

density and viscosity and their derived properties of these solutions. Other interactions or

forces, such as, H-bonding, clathrate formation, interstitial accommodation, complex

formation, van der Waals interaction etc. may also play specific roles in aqueous

solutions of N-containing hydrophobic organic compounds.

In order to substantiate our hypothesis, we wish to extend our studies to as many

N-containing hydrophobic organic compounds as possible. In this study we have selected

particularly some completely water-soluble alkanolamines so that it may lead to

understand the nature of the molecular interactions of these type compounds in aqueous

solutions. The nature of the interaction of these compounds with water would be more

complicated as well as interesting as they have N-substituted alkyl groups, amino- and

alcoholic groups. Many of these types of compounds are regarded as precursors of large

bio-molecules. Actually, it may be presumed that in biological systems, physico-chemical

phenomena in extended form occur continuously in aqueous solutions. Therefore,

4
through understanding of the nature of interactions and development of a new concept for

the aqueous solution of the above mentioned systems would definitely help in

understanding of the biophysical properties of aqueous systems of biological molecules,

such as, proteins, amino acids etc.

1.2 NONCOVALENT INTERACTIONS IN AQUEOUS SOLUTIONS OF

HYDROPHOBIC ORGANIC SOLUTES:

Noncovalent forces, unlike covalent forces, do not involve electron pairing

effects, but are brought about by changes in electron density distribution. The strength of

noncovalent interactions depends on the solvent, molecular structure of the solute and

intermolecular distances between the interacting species. In spite of the fact that

noncovalent forces are much weaker than covalent bonds (e.g. formation of a hydrogen

molecule from the reaction of two hydrogen atoms (–400 kJ/mol) compared with the

formation of the noncovalent H-bond in water (–40 to –10 kJ/mol)), many molecular

recognition processes are governed by noncovalent interactions. The volumetric,

viscometric and thermodynamic properties of aqueous solution are explained in terms of

these properties. Large negative values of excess molar volumes and large excess

viscosities of aqueous solutions of polar organic solutes are often observed due to the

effect of these forces. In biological systems, base-stacking and hydrogen bonding in the

DNA double helix and the H-bonding in the peptide α-helix are the examples where

noncovalent forces determine the shape. In aqueous solutions, noncovalent interactions

are responsible for the stabilization of proteins [30], assembly of lipids in biomembranes

[31] and surfactant aggregation [32]. The most important forces which determine the

5
strength and specificity of noncovalent (bio)molecular associations in aqueous solutions

are electrostatic forces, van der Waals forces (London dispersion force) and hydrophobic

forces. Electrostatic interactions are strong, long-range and directional and comprise ion-

ion, ion-dipole and dipole-dipole interactions, such as, H-bonding interactions. The

importance of H-bonding in biological structures has been extensively described by

Jeffrey and Saenger [33]. A brief description of these interaction is given below.

(i) Hydrophobic hydration and interaction:

The term 'hydrophobic' is derived from hydro- (water) and phobos (fear).

However, it is not so much that hydrophobic molecules 'fear' i.e., 'does not enjoy the

company of' water as water 'fears' the hydrophobic molecules. Hydrophobic molecules in

water generally tend to aggregate, so minimizing their surface contact, and associated

surface energy with water; hence, 'oils and water do not mix' as Fig 1 (1).

6
 Fig. 1(1): Water drop on a hydrophobic leaf.

Smaller hydrophobic materials do, however, dissolve to a small extent in water as water

molecules can arrange around them without breaking hydrogen bonds or losing much

energy and the hydrophobic molecule can interact with these water molecules with

multiple van der Waals interactions, due to the small size of water molecules and

flexibility in their spatial arrangement [34].

If hydrophobic molecules are inserted into water, water molecules order around a

solute molecule to build a quasi crystalline surface. This is done in order to maximize the

hydrogen bonding of the water molecules around a hydrophobic surface. If two

hydrophobic molecules meet, they will associate with their hydrophobic surfaces towards

each other. The water molecules, which were attached to these surfaces, are distributed

back into the bulk solvent as in Fig. 1(2). This generates favorable entropy. The entropic

gain is responsible for almost all associations in the medium of water and hence of

extreme importance for life, e.g., formation of membranes, micelles, and for protein

folding where folding starts often with tryptophane residues forming a hydrophobic core.

Fig. 1(2a). Hydrophobic hydration Fig. 1(2b). Hydrophobic interaction

Fig. 1(2). Hydrophobic proces [http://www.bio.miami.edu/~cmallery/255/255chem/p2x7x5.jpg].

7
The interpretation of the thermodynamic observations of hydrophobic hydration and

hydrophobic interactions has been reconsidered in the last decade. The negative entropy and

enthalpy change, and the positive change in heat capacity upon dissolution of apolar solutes

in water led to the introduction of the concept of the ‘iceberg’ model in 1957 [35]. This

model explained the large entropy loss upon dissolution of apolar gases in terms of

structuring of water molecules in the near vicinity of the solute. The enthalpy gain was

explained by increased water-water hydrogen bonding interactions. A few years later, the

concept of ‘hydrophobic interactions’ was introduced [36]. The entropy-driven interaction

between apolar moieties was explained by a release of structured water molecules as a result

of destructive overlap of hydrophobic hydration spheres. For several decades, researchers

have been inspired by these interpretations. However, in the last ten years, serious doubts

about these interpretations have developed, due to the use of more advanced experimental

and computational techniques. Recent opinions and facts about these new developments have

been reviewed [37]. Computational techniques have shown that water does not undergo a

substantial structural enhancement (i.e. increased H-bonding) in the hydration shell of apolar

solutes [38-41], but largely maintains its original structure by accommodating the apolar

solutes in its 3-D H-bond network, without sacrificing a significant number of hydrogen

bonds.

Kolomeisky and Widom [42] proposed a model of the hydrophobic interaction by

which the potential of mean force between interstitial solute molecules in Ben-Naim’s

[43] one-dimensional, many-state lattice model (related to the one-dimensional q-state

Potts Model [44]) was calculated. They found that the magnitude of the effective

attractive force between solutes and the range of that attraction vary inversely with each

other; the strength of the attraction, as expected, increases with increasing magnitude of

8
the (entropically unfavorable) free energy of ‘hydrogen-bond’ formation, but at the same

time the range decreases. Conversely, when the unfavourable entropy and favourable

energy of ‘hydrogen-bond’ formation are nearly in balance, the attraction between

hydrophobes, while then weak, is of very long range. The solubility of the hydrophobe, as

so defined, is calculated with the model. It was found to decrease with increasing

temperature, as expected for a hydrophobic solute.

(ii) H-bonding:

H-bonding is another important interaction in aqueous-organic as well as other

organic-organic solutions containing –NH, –OH etc groups. Some abnormal behaviors of

aqueous organic solutions can be interpreted successfully in terms of H-bonding.

Hydrogen bonds are different from van der Waals interactions, but this difference

is blurred in some instances. The key to the difference is that, hydrogen bonding involves

a mutual penetration of atoms within their van der Waals radii. The IUPAC (tentatively)

proposed definition is: “hydrogen bond is an attractive interaction between the hydrogen

from a group X–H and an atom or a group of atoms Y, in the same or different

molecule(s), where there is evidence of bond formation”. The most important criteria for

a hydrogen bond are: (i) the H in the X–H group is more electropositive than X and (ii)

the physical forces involved in hydrogen bonding should include attractive electrostatic

forces, i.e., it should not be primarily dispersive forces [45].

9
 H-bonding occurs when an atom of hydrogen is attracted by rather strong forces

to two atoms instead of only one, so that it may be considered to be acting as a bond

between them. Typically, hydrogen bonding occurs where the partially positively charged

hydrogen atom lies between partially negatively charged oxygen and nitrogen atoms, but

is also found elsewhere, such as, between fluorine atoms in HF 2- and between water and

the smaller halide ions F-, Cl- and Br- (for example, HO-H····Br- [46,47]. Even very weak

C-H····OH2 hydrogen bonds (~ 4 kJ mol-1) are being increasingly recognized [48].

Extremely Strong Hydrogen Bond (>155 kJ/mol or 40 kcal/mol) is found in F—H ...:F

[49]. In theoretical studies, strong hydrogen bonds even occur to the hydrogen atoms in

metal hydrides (for example, LiH····HF; [50]. H-bonding energy of HO—H...:OH3+ in

water is 18 kJ/mol or 4.3 kcal/mol [51]. Hydrogen bonding is characterized by its

preferred dimensions, molecular orientation, approximate linearity and changes in

infrared frequency and intensity.

In the aqueous solutions of polar organic compounds, H-bond is formed between

different groups such as: HO–H···OH, HO–H···NH, OH···OH, NH···NH, NH···OH etc. Pal

and Singh [52] suggested that, volume contraction in water+organic solute was due to the

ability of the -OH group to form hydrogen bonds with water molecules.

(iii) van der Waals force:

In physical chemistry the van der Waals force (or van der Waals interaction) is the

attractive or repulsive force between molecules (or between parts of the same molecule)

10
other than those due to covalent bonds or to the electrostatic interaction of ions with one

another or with neutral molecules. The term includes:

• permanent dipole–permanent dipole forces,

• permanent dipole–induced dipole forces,

• instantaneous induced dipole-induced dipole (London dispersion forces).

van der Waals forces are relatively weak compared to normal chemical bonds, but

play a fundamental role in fields as diverse as supramolecular chemistry, structural

biology, polymer science, nanotechnology, surface science, and condensed matter

physics. van der Waals forces define the chemical character of many organic compounds.

They also define the solubility of organic substances in polar and non-polar media. For

the lower alcohols, properties of the polar hydroxyl group dominate over the weak

intermolecular forces of van der Waals. For higher alcohols, properties of the non-polar

alkyl group (R) dominate and define the solubility. van der Waals forces grow with the

length of the non polar part of the substance.

(iv) Interstitial accommodation:

Water molecules exist in three dimensional structural networks in which localized

void spaces are available. The solute molecules are trapped in to these void spaces in

aqueous organic solution, resulting into a volume contraction. In our present systems, we

may also account the interstitial accommodation to interpret observed phenomena.

Interstitial accommodation of the non-aqueous molecules occupying in the structured

water lattices, void spaces are formed to be related to causes for marked change in excess

molar volumes.
11
1.2 IMPLICATION OF THE PRESENT SYSTEMS IN CHEMICAL INDUSTRY:

Alkanolamine and their mixtures with water are used in different chemical

applications, such as, gas purification, detergents and personal-care products, textiles,

agricultural products, concrete, in households as alkanolamine salts, as non-ionic

surfactants, adhesives, cements, coatings, corrosion inhibitors, electroplating, electroless

plating, stripping, metal working, cleaning and lubricating, polymers as an additive as a

cross-linking agent, textiles to facilitate the dyeing process, a dyestabilizer in fabrics,

such as, cotton, pharmaceuticals, plasticizers, insecticides and herbicides.

1.3 ENVIRONMENTAL IMPORTANCE OF THE PRESENT SYSTEMS:

Concerns about suppressing high concentrations of greenhouse gases in the

atmosphere have encouraged research into different strategies to capture and store acid

gases, such as, carbon dioxide (CO2), sulfur dioxide (SO2), carbonyl sulfide (COS), and

hydrogen sulfide (H2S) from industrial and natural gas streams. Solutions of

alkanolamines are the most commonly used reactive compounds to remove such acidic

gases.

1.5 OBJECTIVE OF THE WORK:

As the aqueous alkanolamine solutions are very important in industrial purpose,

environmental significance, bio-molecular aspect as well as understanding the nature of

12
liquid and their mixture, huge research work on their physico-chemical properties along

with other research have to be done. These data are required for better understanding and

comparing the structures of aqueous alkanolamine solutions and for the development of

the proper design of the absorption and stripping operations. Literature survey shows that

a number of studies have been performed but these are still not sufficient.

In literature survey, it has been found that aqueous solutions of different

alkanolamines were reported by some authors [53-97] which included different types of

physico-chemical properties such as, volumetric properties, viscometric properties,

thermodynamic properties, refractometric properties etc.

As we have mentioned previously, the present study involves nine different

alkanolamines (N-containing hydrophobic organic compounds) and their binary solutions

with water which are selected as a continuation to our recent attention given on aqueous-

organic systems. Moreover, our studied alkanolamine posses different groups and atoms

such as, –OH, –NH2, =NH, =N–, –R, –H etc. and also some possess poly functional

groups. Also, we have aimed to get idea about the interaction and effect of the above

groups and atoms in the water-alkanolamine solutions. The effects of the structural

formulation of the alkanolamines in their aqueous solutions that we have aimed could be

summarized as followes:

(a) presence and absence of an alkyl group,

(b) number of multifunctional groups,

(c) length and number of N-substituted alkyl groups,

(d) number and position of –OH groups

13
The above mentioned effects could be studied from the behaviors of the aqueous

solutions of these alkanolamines by observing following:

(a) variational pattern of density, partial molar volumes, viscosity, free energy,

entropy, enthalpy for the activation of viscous flow, refractive index and

molar refractivity each as a function of concentration of different

alkanolamines,

(b) deviation from ideality through variation of depth in minima or height of

maxima for the excess properties,

(c) disparity in heights of maxima / depth of minima,

(d) position of minima for excess properties,

(e) limiting values of partial molar quantities with respect to length of alkyl

groups,

(f) temperature dependency of different properties.

1.6 SERIES OF SOLUTES AND SYSTEMS UNDER INVESTIGATIONS:

Our selected systems are summarized as the following series

(a) Monoalkanolamine series.

i) Methylethanolamine (MEA),

14
 ii) Ethylethanolamine (EEA),

iii) Dimethylethanolamine (DMEA),

iv) Dimethylpropan-1-olamine (DMPA-1),

v) Dimethylpropan-2-olamine (DMPA-2).

This includes the following binary systems of monoalkanolamines and water (W):

i) MEA + W,

ii) EEA + W,

iii) DMEA + W,

iv) DMPA-1 + W,

v) DMPA-2 + W,

(b) Diethanolamines series.

i) Diethanolamine (DEA),

ii) Methyldiethanolamine (MDEA),

iii) Ethyldiethanolamine (EDEA),

vi) n-Butyldiethanolamine (BDEA).

This includes the following binary systems of diethanilamines and water (W):

i) DEA + W,

ii) MDEA + W,

iii) EDEA + W

iv) BDEA + W

For the above density (ρ), viscosity (η ) and refractive index (n) are to be

measured experimentally. The measured ρ data are used to calculate the excess molar

volumes ( VmE ) and partial molar volumes ( V2 ). Excess viscosity (η E) may be

15
calculated from η data and deviation in refractive index (∆ n), molar refractivity (R) as

well as deviation in molar refractivity (∆ R) may also be calculated from ‘n’ data.

Different thermodynamic parameters for viscous flow such as, ΔH ‡, ΔS‡, ΔG‡ and their

excess values such as, ΔH‡E, ΔS‡E, ΔG‡E may also be calculated. All the measured

properties can be fitted to the polynomial equations of different degrees whereas excess

properties / deviation from ideality can be fitted to the Redlich-Kister type polynomial

equations. A through analysis of the above results may be useful to have a deeper insight

into the probable molecular interactions relevant to these alkanolamines + water systems

and others.

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