INVESTIGATION ON VISCOUS SYNERGY AND

ANTAGONISM OF SOME LIQUID MIXTURES AND

ION-SOLVENT INTERACTION OF
SOME COMPOUNDS IN VARIOUS
SOLVENT SYSTEMS
BY

Anuradha Sinha
Supervisor : Dr. Mahendra Nath Roy
Department of Chemistry
University of North Bengal
 Contents
 CHAPTER I : Necessity of the Research
Work
 CHAPTER II : General Introduction
 CHAPTER III : Experimental Section
 CHAPTER IV : Viscous Synergy and
Antagonism and Isentropic Compressibility of
Ternary Mixtures Containing 1,3-Dioxolane,
Water and Monoalkanols at 303.15 K
 CHAPTER V : Solute-Solvent and Solute-Solute
Interactions of Resorcinol in Mixed 1,4-
DioxaneWater Systems at Different
Temperatures

 CHAPTER VI : Investigation on Viscous

Antagonism of Binary and Ternary Liquid
Mixtures and its Relation to Concentration at
(303.15, 313.15 and 323.15) K

 CHAPTER VII : Excess Molar Volumes, Viscosity

Deviations and Isentropic Compressibility of
Binary Mixtures Containing 1,3-Dioxolane and
Monoalcohols at 303.15 K
 CHAPTER VIII : Ion-Solvent and Ion-Ion
Interactions of some Tetraalkylammonium,
Alkali Metals and Ammonium Halides in
i-Amyl Alcohol at 298.15 K by Conductometric
Technique

 CHAPTER IX : Studies of Viscous Antagonism,

Excess Molar Volume and Isentropic
Compressibility in Aqueous Mixed Solvent
Systems at Different Temperatures
 CHAPTER X : Densities, Viscosities and
Sound Speeds of some Acetate Salts in
Binary Mixtures of Tetrahydrofuran and
Methanol at (303.15, 313.15 and 323.15) K

 CHAPTER XI : Concluding Remarks

Necessity of the Research Work
 Object and Application of the Work

The molecular interactions play a very

important role in various physico-chemical processes
occurring in nature.

Synergy and antagonism give the mutual

enhancement or decrement of the physico-chemical,
biological or pharmaceutical activity between
different components of a given mixture.
 Applicable in manufacture of pharmaceuticals,
foodstuffs, cosmetics, industrial products.

High-energy primary and secondary batteries,

wet double-layer capacitors and super capacitors,
electro-deposition and electroplating.

Non-aqueous electrolyte solutions are broadly

used in electrochromic displays and smart windows,
photoelectrochemical cells, electromachining,
etching, polishing and electro-synthesis.
 Organic and inorganic synthesis, studies
of reaction mechanisms and extraction.

Energy transport, heat transport, mass

transport and fluid flow.

Non-aqueous systems have been of

immense importance to the technologist and
theoretician as many chemical processes occur
in these systems.
 Main Solvents used

1,3-Dioxolane
1,4-Dioxane (DO)
Tetrahydrofuran (THF)
Ethylene Glycol
N,N-Dimethylformamide (DMF)
Dimethyl Sulphoxide (DMSO)
Benzene, n-Hexane
Monoalcohols viz. Methanol, Ethanol, 1-Propanol, 2-
Propanol, 1-Butanol, 2-Butanol, t-Butanol, i-Amyl
alcohol
Water
 Method of Investigations

Densitometry
Viscometry
Ultrasonic Interferometry
Conductometry
 General Introduction
 Investigation on Viscous Synergy and Antagonism
Viscous synergy is the term used in application to the
interaction between the components of a system that causes the
total viscosity of the system to be greater than the sum of the
viscosities of each component considered separately.
 Investigation on Ion-Solvent Interaction
Density, Viscosity, Ultrasonic Speed, Correlating Equations,
Conductance
 Experimental Section
 Source and Purification of the
Chemicals used
Solvents
1,3-Dioxolane (C3H6O2), M.W. 74.08, LR, India, was
heated under reflux with PbO2 for 2 hrs., then cooled
and filtered. After adding xylene to the filtrate, the
mixture was distilled.
Solutes

Tetraalkylammonium salts viz. Me4NCl, Et4NBr,

Pr4NBr, Bu4NBr, Bu4NI were purified by
recrystallisation. The crystallised salts were dried in
vacuum. The salts were stored in glass bottles in
darkened desiccator over fused CaCl2.

LiBr, NH4Br were dried at ~ 80-100ºC in vacuum

oven for 48 hrs before use.
 Experimental Method
 Measurement of Density

Ostwald-Sprengel type pycnometer

Calibration at different temperatures with doubly distilled
water and THF.
The precision of the density measurement was  0.0003 %.
Thermostatic water bath maintained with an accuracy of
 0.01 K.

 Measurement of Viscosity
Ubbelohde viscometer
The precision of the viscosity measurement was 0.004 %.
 Measurement of Ultrasonic Speed
Ultrasonic speeds were measured, with an accuracy
of ± 0.2 %, using a single-crystal variable-path
ultrasonic interferometer operating at 4 MHz.

 Measurement of Conductance
Systronics Conductivity-TDS meter 308
Dip-type immersion conductivity cell
The entire conductance data was found to be ± 0.3 %
precise.
 Viscous Synergy and Antagonism and Isentropic
Compressibility of Ternary Mixtures Containing
1,3-Dioxolane, Water and Monoalkanols at 303.15 K
calc = ∑ w i i ; ρ calc = ∑ w i ρ i

I S = (exp – calc ) / calc =  / calc

The negative value of IS gives IA.
F = max / 0

KS = 1/ (u2 ρ)
n

KS E = KS –  xi KS,i
i=1
 Experimental (expt.) and literature (lit.) values of densities (ρ) and
viscosities (η) along with the expt. speeds of sound (u) of the pure solvents
at 303.15 K.
x 10-3/ (kg. m-3)  x 102/ (P) u/
Solvents expt. lit. expt. lit. (m. s-1

1,3-Dioxolane 1.0518 1.0494 0.5487 0.5436 1288.5

Water 0.9957 0.9957 0.7975 0.8007 1505.2
Methanol 0.7824 0.7829 0.5041 0.5100 1088.5
Ethanol 0.7844 0.7807 0.9675 0.9930 1144.3
1-Propanol 0.7958 0.7958 1.6626 1.7843 1182.6
2-Propanol 0.7773 0.7779 1.6142 1.7732 1126.6
1-Butanol 0.8021 0.8019 2.5396 2.2853 1196.6
2-Butanol 0.7992 0.7959 2.3394 2.4170 1168.9
t-Butanol 0.7751 0.7762 3.0986 3.3211 1078.8
i-Amyl alcohol 0.8032 – 3.1111 – 1197.0
 AmOH > BuOH > PrOH > EtOH > MeOH

2.5

2
h x 10 / ( P )

1.5
2

0.5

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

wA

Fig. 1(a): Calculated (…) and experimental (—) viscosity values ( ) for 1,3-
dioxolane + water + monoalkanol mixtures with weight fraction of 1,3-
dioxolane (wA) at 303.15 K. Graphical points: monoalkanols, CH 3OH (■);
C2H5OH (); 1-C3H7OH (●); 1-C4H9OH (+); i-C5H11OH (□).
MeOH > EtOH > 2-PrOH > 1-PrOH > t-BuOH > 2-
BuOH> 1-BuOH > i-AmOH
1

0.8

0.6

0.4
IS

0.2

-0.2

-0.4
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

wA

Fig. 2: Synergic index values (IS) for 1,3-dioxolane + water + monoalkanols

with weight fraction of 1,3-dioxolane (wA) at 303.15 K. Graphical points:
monoalkanols, CH3OH (■); C2H5OH (); 1-C3H7OH (●); 2-C3H7OH (ο); 1-
C4H9OH (+); 2-C4H9OH (▲); t- C4H9OH (); i-C5H11OH (□).
Pure state viscosity ( ), maximum viscosity (max ) and enhancement or
power factor (F) for the monoalkanols at 303.15 K.

x 102 / max x 102 /

Monoalkanols (P) (P) F

Methanol 0.5041 1.2414 2.463

Ethanol 0.9675 1.6259 1.681
1-Propanol 1.6626 2.1641 1.302
2-Propanol 1.6142 2.1474 1.330
1-Butanol 2.5396 2.3109 0.909
2-Butanol 2.3394 2.4546 1.049
t-Butanol 3.0986 3.2107 1.036
i-Amyl alcohol 3.1111 2.5713 0.827
i-AmOH > 1-BuOH > 2-BuOH > t-BuOH > 1-PrOH
> 2-PrOH > EtOH > MeOH
150

100
K S x 10 / ( Pa )

50
-1

0
12

-50
E

-100

-150

-200
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
xA

Fig. 3: Excess isentropic compressibility (KSE ) for 1,3-dioxolane + water +

monoalkanols with mole fraction of 1,3-dioxolane (xA) at 303.15 K.
Graphical points: monoalkanols, CH 3OH (■); C2H5OH (); 1-C3H7OH (●); 2-
C3H7OH (ο); 1-C4H9OH (+); 2-C4H9OH (▲); t- C4H9OH (); i-C5H11OH (□).
 (1,3-dioxolane)

H2O...H-O-R H2O.....H-O-R H2O........H-O-R

Synergy prevails in absence of 1,3-dioxolane

H2O...H-O-CH3 H2O........H-O-C5H11
Lower monoalkanols associate very strongly with water
molecules

CH3
H3C-C-OH…OH2 H2O...H-O-C4H9
CH3
1,3-dioxolane cannot easily disrupt the molecukar package between branched isomers and water
Investigation on Viscous Antagonism of Binary and
Ternary Liquid Mixtures and Its Relation to
Concentration at (303.15, 313.15 and 323.15) K
Calculated (calc) and experimental ( expdensities of ethylene glycol +
tetrahydrofuran and ethylene glycol + 1,4-dioxane against the respective
mass% of glycol at (303.15, 313.15 and 323.15) K.

calcx 10-3/ ( kg. m-3 ) expx 10-3/ ( kg. m-3 )

Mass % 303.15 313.15 323.15 303.15 313.15 323.15
of glycol (K) (K) (K) (K) (K) (K)

ethylene glycol + tetrahydrofuran

10 0.8968 0.8895 0.8817 0.8994 0.8903 0.8825

20 0.9200 0.9128 0.9051 0.9201 0.9128 0.9054
30 0.9433 0.9361 0.9285 0.9434 0.9375 0.9287
40 0.9666 0.9594 0.9519 0.9674 0.9597 0.9525
50 0.9859 0.9827 0.9753 0.9899 0.9837 0.9759
60 1.0132 1.0059 0.9987 1.0141 1.0063 0.9989
70 1.0364 1.0293 1.0221 1.0372 1.0288 1.0223
80 1.0597 1.0526 1.0455 1.0601 1.0539 1.0468
90 1.0829 1.0759 1.0689 1.0853 1.0779 1.0716

ethylene glycol + 1,4-dioxane

10 1.0285 1.0228 1.0122 1.0289 1.0231 1.0133

20 1.0372 1.0313 1.0211 1.0397 1.0326 1.0227
30 1.0458 1.0398 1.0299 1.0487 1.0409 1.0345
40 1.0544 1.0482 1.0389 1.0562 1.0506 1.0431
50 1.0631 1.0567 1.0478 1.0678 1.0600 1.0532
60 1.0717 1.0652 1.0567 1.0756 1.0709 1.0638
70 1.0804 1.0737 1.0656 1.0838 1.0780 1.0684
80 1.0890 1.0822 1.0745 1.0924 1.0858 1.0793
90 1.0976 1.0907 1.0834 1.1007 1.0955 1.0860
 Calculated (ρcalc) and experimental (ρexpdensities of tetrahydrofuran + methanol +
benzene and i-propanol + n-hexane + benzene against the respective mass % of
THF, MeOH, i-PrOH and n-C6H14 at (303.15, 313.15 and 323.15) K.
Mass %
ρcalc x 10-3/ (kg. m-3) ρexp x 10-3/ (kg. m-3)
of Mass % of
THF/ MeOH/ n- 303.15 313.15 323.15 303.15 313.15 323.15
i-PrOH C6H14 (K) (K) (K) (K) (K) (K)

tetrahydrofuran + methanol + benzene

10 10 0.8569 0.8528 0.8439 0.8599 0.8545 0.8496
20 15 0.8542 0.8493 0.8404 0.8570 0.8523 0.8459
30 30 0.8436 0.8375 0.8284 0.8452 0.8404 0.8349
35 35 0.8402 0.8337 0.8245 0.8415 0.8361 0.8296
40 40 0.8367 0.8299 0.8207 0.8390 0.8336 0.8257
45 45 0.8335 0.8261 0.8168 0.8352 0.8310 0.8230
50 50 0.8301 0.8222 0.8129 0.8306 0.8263 0.8166
55 40 0.8387 0.8309 0.8216 0.8375 0.8353 0.8269
60 30 0.8472 0.8396 0.8304 0.8491 0.8397 0.8345
65 20 0.8557 0.8482 0.8391 0.8576 0.8504 0.8430
70 10 0.8642 0.8569 0.8479 0.8658 0.8610 0.8527
75 00 0.8727 0.8656 0.8566 0.8752 0.8670 0.8634
80 00 0.8733 0.8659 0.8569 0.8743 0.8667 0.8596
90 00 0.8745 0.8666 0.8576 0.8743 0.8664 0.8607

i-propanol + n-hexane + benzene

00 65 0.7246 0.7190 0.7097 0.8798 0.8715 0.8686

05 80 0.6886 0.6818 0.6726 0.8950 0.8843 0.8813
10 10 0.8345 0.8296 0.8212 0.8585 0.8494 0.8430
20 15 0.8159 0.8098 0.8016 0.8517 0.8437 0.8390
30 25 0.7867 0.7790 0.7711 0.8552 0.8488 0.8427
40 35 0.7575 0.7482 0.7406 0.8637 0.8543 0.8496
50 45 0.7282 0.7175 0.7101 0.8688 0.8584 0.8556
60 40 0.7311 0.7194 0.7123 0.8565 0.8460 0.8397
70 20 0.7661 0.7539 0.7474 0.8257 0.8164 0.8114
80 00 0.8011 0.7884 0.7824 0.8128 0.8029 0.7988
90 05 0.7825 0.7685 0.7628 0.7946 0.7847 0.7408

exp > calc , volume contraction

 0.8

0.7

0.6

0.5
IA

0.4

0.3

0.2

0.1

0
0 10 20 30 40 50 60 70 80 90 100
Mass % of ethylene glycol

Fig. 1: Antagonic index values (IA) for ethylene glycol + tetrahydrofuran

against mass% of ethylene glycol at different temperatures. Graphical
points: 303.15 K (■); 313.15 K (●); 323.15 K (▲).
 0.6

0.5

0.4
IA

0.3

0.2

0.1

0
0 10 20 30 40 50 60 70 80 90 100
Mass % of ethylene glycol

Fig. 2: Antagonic index values (IA) for ethylene glycol + 1,4-dioxane against
mass% of ethylene glycol at different temperatures. Graphical points:
303.15 K (■); 313.15 K (●); 323.15 K (▲).

The trend observed in the binary mixtures for IA is:

Ethylene glycol + THF > Ethylene glycol + DO
 0.25

0.2

0.15

0.1

0.05

0
IA

-0.05

-0.1

-0.15

-0.2

-0.25
0 10 20 30 40 50 60 70 80 90 100
Mass % of tetrahydrofuran

Fig. 3: Antagonic index values (IA) for tetrahydrofuran + methanol +

benzene against mass% of tetrahydrofuran at different temperatures.
Graphical points: 303.15 K (■); 313.15 K (●); 323.15 K (▲).
 1

0.5

-0.5
IA

-1

-1.5

-2

-2.5
0 10 20 30 40 50 60 70 80 90 100
Mass % of i-propanol

Fig. 4: Antagonic index values (IA) for i-propanol + n-hexane + benzene

against mass% of i-propanol at different temperatures. Graphical
points: 303.15 K (■); 313.15 K (●); 323.15 K (▲).

The trend observed in ternary mixtures for IA is:

i-PrOH + n-C6H14 + C6H6 > THF + MeOH + C6H6
 CH2O..H CH2O..H…….…..
+ > +
CH2O..H ………. CH2O..H……..….
(THF) (DO)
Less interaction-decrease in molecular package-favourable
antagonism

+ CH3OH + < CH2-CH2OH + C6H14 +

CH3
C6H6 favours antagonism
 Studies of Viscous Antagonism, Excess Molar
Volume and Isentropic Compressibility in Aqueous
Mixed Solvent Systems at Different Temperatures

Δη = η – Σ xi ηi
i =1

VE = Σ xi Mi (1/ρ –1/ρi )
i=1
 water + ethylene glycol +
DMSO > DO > DMF > THF
1

-1
Δ η x 1 02 / ( P )

-2

-3

-4

-5

-6

-7
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
xA

Fig.1: Viscosity deviations (Δη) of : (■), water (A) + ethylene glycol (B) +
tetrahydrofuran (C); (▲), water (A) + ethylene glycol (B) + 1,4-dioxane
(C); (∆), water (A) + ethylene glycol (B) + N,N-dimethylformamide (C);
and (□), water (A) + ethylene glycol (B) + dimethylsulphoxide (C)
mixtures with mole fraction of water (xA) at 298.15 K.
 water + ethylene glycol +
THF > DMF > DO > DMSO
0.8

0.7

0.6

0.5
IA

0.4

0.3

0.2

0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
xA
Fig.2: Antagonic Index (IA) values of : (■), water (A) + ethylene glycol (B)
+ tetrahydrofuran (C); (▲), water (A) + ethylene glycol (B) + 1,4-
dioxane(C); (∆), water (A) + ethylene glycol (B) +N,N-dimethylformamide
(C); and (□), water (A) + ethylene glycol (B) + dimethylsulphoxide (C)
mixtures with mole fraction of water (xA) at 298.15 K.
 water + ethylene glycol +
THF > DMF > DO > DMSO
0.1

-0.1
V x 1 0 / ( m. m o l )
-1

-0.2
3

-0.3

-0.4
3

-0.5
E

-0.6

-0.7

-0.8
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
xA

Fig.3: Excess molar volumes (VE) of : (■), water (A) + ethylene glycol (B) +
tetrahydrofuran (C); (▲), water (A) + ethylene glycol (B) + 1,4-dioxane
(C); (∆), water(A) + ethylene glycol(B) + N,N-dimethylformamide (C); and
(□), water (A) + ethylene glycol (B) + dimethylsulphoxide (C) mixtures
with mole fraction of water (xA) at 298.15 K.
 water + ethylene glycol +
THF > DO > DMF > DMSO
0

-20

-40
K S x 1 0 / ( P a)
-1

-60
12

-80

-100
E

-120

-140

-160
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
xA

Fig.4: Excess isentropic compressibility (KSE) of : (■), water (A) +

ethylene glycol (B) + tetrahydrofuran (C); (▲), water (A) + ethylene glycol
(B) + 1,4-dioxane (C); (∆), water (A) + ethylene glycol (B) + N,N-
dimethylformamide (C); and, (□), water (A) + ethylene glycol (B) +
dimethylsulphoxide (C) mixtures with mole fraction of water ( xA) at
298.15 K.
 H2O + CH2OH +
CH2OH

Δη CH3
< N-C-H < < H3C-S-CH3
CH3 O O
(THF) (DMF) (DO) (DMSO)
IA and VE (weakest molecular interaction with THF)
CH3
> N-C-H > > H3C-S-CH3
CH3 O O
Excess Molar Volumes, Viscosity Deviations and
Isentropic Compressibility of Binary Mixtures
Containing 1,3-Dioxolane and Monoalcohols
at 303.15 K
n
G*E = R T [ ln  V – ( Σ xi ln i Vi ) ]
i=1

n n
ln η = Σ xi ln ηi + d1 Π xi
i=1 i=1

k
YE = x1 x2 ∑ A J -1 (x1 – x2 ) J – 1
J=1

σ = [ ( YEexp. – YEcal. )2/ ( n – m ) ] 1 / 2

MeOH < EtOH < 1-PrOH < 2-PrOH < 1-BuOH < i-
AmOH < 2-BuOH < t-BuOH
0.6

0.5

0.4
V x 10 / ( m . mol )

0.3
-1

0.2
3

0.1

0
3

-0.1
E

-0.2

-0.3

-0.4
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x1

Fig.1: Excess molar volumes (VE) for 1,3-dioxolane + monoalcohols with

mole fraction of 1,3-dioxolane (x1) at 303.15 K. Graphical points:
monoalcohols, methanol (); ethanol (□); 1-propanol (▲); 2-propanol (x);
1-butanol (o); 2-butanol (●); t-butanol (■); i-amyl alcohol (∆).
MeOH > EtOH > 1-PrOH > 2-PrOH > i-AmOH > 1-
BuOH > 2-BuOH > t-BuOH
0.2

-0.2
D h x 10 / ( P )

-0.4
2

-0.6

-0.8

-1

-1.2

-1.4
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x1

Fig.2: Viscosity deviations ( η) for 1,3-dioxolane + monoalcohols with

mole fraction of 1,3-dioxolane (x1) at 303.15 K. Graphical points:
monoalcohols, methanol (); ethanol (□); 1-propanol (▲); 2-propanol (x);
1-butanol (o); 2-butanol (●); t-butanol (■); i-amyl alcohol (∆).
 MeOH > AmOH > EtOH > PrOH > BuOH

0.4

0.2

0
G * x 10 / ( J. m ol )
-1

-0.2

-0.4

-0.6
-3

-0.8

-1
E

-1.2

-1.4

-1.6
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x1

Fig.3: Gibbs excess energy of activation for viscous flow (G*E) for 1,3-
dioxolane + monoalcohols with mole fraction of 1,3-dioxolane (x1) at
303.15 K. Graphical points: monoalcohols, methanol (); ethanol (□); 1-
propanol (▲); 2-propanol (x); 1-butanol (o); 2-butanol (●); t-butanol (■); i-
amyl alcohol (∆).
 MeOH < EtOH < PrOH < BuOH < AmOH

40

20

0
K S x 10 / ( Pa )
-1

-20

-40
12

-60

-80
E

-100

-120

-140

-160
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x1

Fig.4: Excess Isentropic compressibility (KSE) for 1,3-dioxolane +

monoalcohols with mole fraction of 1,3-dioxolane (x1) at 303.15 K.
Graphical points: monoalcohols, methanol (); ethanol (□); 1-propanol
(▲); 2-propanol (x); 1-butanol (o); 2-butanol (●); t-butanol (■); i-amyl
alcohol (∆).
 CH3OH…….
(1,3-dioxolane)
 most favorable intermolecular complexation through H-bonding

 alcohols as Lewis acids and the cyclic diether as a Lewis base

 The negative VE and KSE values indicate the presence of strong donor-
acceptor interaction between the oxygen and hydrogen atoms of the
cyclic diether and the alcohols.

 The branched isomers fit into the structure of cyclic diether more easily
compared to the linear isomer.

 ∆η and G*E and d1 values are found to be positive where charge-transfer

and hydrogen-bonding interactions lead to the formation of complex
species between unlike molecules.
 Ion-Solvent and Ion-Ion Interactions of some
Tetraalkylammonium, Alkali Metals and
Ammonium Halides in i-Amyl Alcohol at 298.15 K
by Conductometric Technique

d = ( M / N.  ) 1/3 = 1.183 ( M / ) 1/3

 = p [ 0 (1 + RX ) + EL ]
p = 1 – a (1 -  )
 = 1 – KA c  2 f 2
– ln f = k /2 (1 + k R )
 = e2/ε kB T
KA = KR / (1 – a ) = KR (1 + KS)

0  = 1 / 6 П r T
 Me4 N+ > Et4 N+ > Bu4 N+ > Pr4 N+
However, in case of alkali metal and ammonium halides the trend
is:
Li+ > NH4+ > Na+

20000
Me4NCl
18000

16000
K A / ( dm. m ol )

14000
Et4NBr
-1

12000
3

10000

8000
Bu4NI
6000 Bu4NBr

4000 Pr4NBr
LiBr NaI NH4Br
2000

Electrolytes

Fig.1: The electrolytes; tetraalkylammonium, alkali metals and

ammonium halides with their association constant (KA) values in pure i-
amyl alcohol at 298.15 K.
Me4 NCl > Et4 NBr > Bu4 NI > Pr4 NBr > Bu4 NBr
and, LiBr > NaI > NH4 Br

18

16
Me4NCl Et4NBr
Bu4NI
Λ o x 1 0 / ( S . m. m o l )

14
-1

Pr4NBr
12 LiBr
Bu4NBr
2

10 NaI
NH4Br
8
4

Electrolytes

Fig.2: The electrolytes; tetraalkylammonium, alkali metals and

ammonium halides with their limiting molar conductance ( ) values in
pure i-amyl alcohol at 298.15 K.
 0.7

0.6 Et4NBr
Me4NCl
Λ o η x 10 / ( S. m . mol . P )

Bu4NI
-1

0.5 Pr4NBr
LiBr
Bu4NBr
2

0.4
NaI
NH4Br
0.3
6

0.2

0.1

Electrolytes

Fig.3: The electrolytes; tetraalkylammonium, alkali metals and

ammonium halides with their Walden’s product ( ) in pure i-amyl
alcohol at 298.15 K.
 KA Ion-dipole interaction
R4N+……HO-CH-CH2-CH2-CH3
CH3
(i-amyl alcohol)

Bu4NI > Bu4NBr NH4+ > Na+ Li+ > Na+

size of I- > Br – size of Li+ < Na+

increase of the Walden product indicates the weak solvation of the ions
in the pure solvent OR higher is the limiting molar conductance value,
lower is the solvation

Walden’s product decreases in the increasing order of the radii:

Me4 N+ > Et4 N+ > Pr4 N+ > Bu4 N+ and Li+ > Na+ > NH4+
 Densities, Viscosities and Sound Speeds of some
Acetate Salts in Binary Mixtures of Tetrahydrofuran
and Methanol at (303.15, 313.15 and 323.15) K

Vφ = M /  0 – 1000 (  -  0 ) / (c  0 )

Vφ = Vφ0 + SV* √c

E2 = Eφ+ [(1000 – c Eφ )( 2000 + SE c3/2 )-1]SE c1/2

Eφ = α0 Vφ + (α - α0 ) 1000 c -1

Eφ= Eφ0+ SE √c

α0 = - 1/ ρ0 ( δρ0 / δT ) and α = - 1/ ρ ( δρ / δT )
 (η / η0 –1) / c1/2 = A + B c1/2

∆μ0*2 = ∆μ0*1+ ( R T / V10 ) 1000 B – (V10 - V20 )

∆μ0*1 = 2.303 RT log ( η0 V10 / h N )

KS = 1/ (u2 ρ)

KS,φ = M KS / ρ0 + 1000 (KS ρ0 - KS0 ρ) / (m ρ ρ0 )

KS,φ = K0S,φ + S*K m1/2

 Z=uρ
b = (M /ρ) – ( R T / ρ u2) {[1 + ( M u2 /3 R T )] 1/2 -1 }

r = (3 b /16 π N ) 1/3
Lf = K / (u ρ1/2)
B΄ = (4/3)π r3 N
Y = (36 π N B΄ 2 ) 1/3
Va = V – V0 = V ( 1 – u / u ∞ )
R΄ = M u 1/3/ρ
S = u V / u ∞ B΄
r΄= 1 - ( u / u ∞ ) 2
rf = B΄/ V
RA = ρS / ρ0 ( u0 / uS ) 1/3
Limiting apparent molar volumes (Vφ0) and experimental slopes (SV*) for the acetate salts in different mass % of THF +
MeOH mixtures along with standard errors at (303.15, 313.15 and 323.15 ) K.

Mass CH3COONH4 CH3COOK CH3COONa.3H2O CH3COOLi.2H2O

% of
Vφ0 x 106 SV* x 106 / Vφ0 x 106 / SV* x 106 / Vφ0 x 106 SV* x 106/ Vφ0 x 106/ SV* x 106/
THF T/K
/(m3.mol-1) (m9.mol-3)1/2 (m3.mol-1) (m9.mol-3)1/2 /(m3.mol-1) (m9.mol-3)1/2 (m3.mol-1) (m9.mol-3)1/2

10 303.15 33.4  0.02 63.8  0.01 21.2  0.01 86.5  0.04 3.2  0.03 135.6  0.07 -12.9  0.01 141.4 0.01
313.15 18.2  0.05 75.8  0.02 -5.5  0.02 68.8  0.02 -12.7  0.06 121.4  0.04 -26.2  0.02 159.7 0.02
323.15 8.4  0.01 86.5  0.03 -11.9 0.07 75.6  0.04 -26.2  0.04 128.3  0.07 -57.1  0.02 169.5 0.02
20 303.15 20.8  0.02 68.1  0.03 3.0  0.09 84.9  0.07 -21.4  0.02 215.9  0.01 -34.5  0.02 210.7 0.01
313.15 12.2  0.04 76.9  0.01 -14.7 0.02 113.6  0.09 -44.4  0.08 230.8  0.02 -102.8  0.05 328.2 0.02
323.15 4.3  0.04 63.1  0.02 -23.5 0.03 99.0  0.03 -63.2  0.05 233.1  0.02 -161.9  0.01 438.2 0.04
30 303.15 17.5  0.02 84.2  0.06 -6.3  0.01 109.3  0.09 -35.9  0.02 233.5  0.08 -85.5  0.02 289.9 0.02
313.15 10.6  0.08 88.9  0.06 -19.0 0.07 107.5  0.02 -94.4  0.02 339.3  0.08 -137.6  0.02 394.1 0.07
323.15 1.5  0.03 99.6  0.03 -31.2 0.02 126.1  0.06 -131.6  0.02 408.4  0.04 -227.1  0.03 572.4 0.02
 0

-0.5
E2 x 1 0 / ( m . m o l . K )
-1 -1

-1
3

-1.5
6

-2

-2.5
0 0.05 0.1 0.15 0.2 0.25 0.3
-3
c / ( mol. dm )

Fig.1(a): Variation of partial molar expansibility (E2) with concentration

(c) of acetate salts in 10 mass % THF at 303.15 K. Graphical points:
CH3COONH4 (■); CH3COOK (); CH3COONa.3H2O (▲); CH3COOLi.2H2O ().
 Jones-Dole coefficients, (A) and (B) with standard errors along with the free energy of activation for viscous flow of
solution for solvent mixture (∆μ0*1) and salts, (∆μ0*2) in different mass % of THF + MeOH at (303.15, 313.15 and
323.15 ) K.
303.15 K 313.15 K 323.15 K
A/ B/ ∆μ0*1 / A/ B/ ∆μ0*1 / A/ B/ ∆μ0*1 /
(m3/2. (m3. (kJ. ∆μ0*2 x 10-3 / (m3/2 . (m3. (kJ. ∆μ0*2 x 10-3 / (m3/2 . (m3. (kJ. ∆μ0*2 x 10-3 /
mol-1/2) mol-1) mol-1) (kJ. mol-1) mol-1/2) mol-1) mol-1) (kJ. mol-1) mol-1/2) mol-1) mol-1) (kJ. mol-1)
10 mass % THF
CH3COONH4
0.14 0.46 0.21 0.37 0.31 0.06
 0.01  0.03 33.48 27.19  0.06  0.01 34.23 21.48  0.02  0.03 35.03 3.49
CH3COOK
0.29 0.50 0.28 0.43 0.45 0.19
 0.03  0.06 33.34 29.41  0.01  0.01 34.23 25.05  0.02  0.05 34.96 10.96
CH3COONa.3H2O
0.51 0.71 0.41 0.62 0.58 0.49
 0.04  0.01 33.48 41.96  0.07  0.02 34.23 35.97  0.03  0.04 35.03 28.28
CH3COOLi.2H2O
0.06 1.08 0.15 0.84 0.44 0.60
 0.11  0.01 33.34 63.49  0.08  0.03 34.23 48.89  0.02  0.02 34.96 34.54

Contd…
 303.15 K 313.15 K 323.15 K
A/ B/ ∆μ0*1 / A/ B/ ∆μ0*1 / A/ B/ ∆μ0*1 /
(m3/2. (m3. (kJ. ∆μ0*2 x 10-3 / (m3/2 . (m3. (kJ. ∆μ0*2 x 10-3 / (m3/2 . (m3. (kJ. ∆μ0*2 x 10-3 /
mol-1/2) mol-1) mol-1) (kJ. mol-1) mol-1/2) mol-1) mol-1) (kJ. mol-1) mol-1/2) mol-1) mol-1) (kJ. mol-1)
20 mass % THF
CH3COONH4
0.05 0.50 0.07 0.42 0.30 0.15
 0.01  0.06 33.39 28.03  0.02  0.12 34.27 23.29  0.09  0.01 35.04 8.23
CH3COOK
0.11 0.60 0.19 0.57 0.31 0.29
 0.01  0.04 33.39 33.63  0.05  0.02 34.27 31.6  0.02  0.07 35.04 15.88
CH3COONa.3H2O
0.26 0.82 0.20 0.76 0.41 0.51
 0.01  0.07 33.39 45.95  0.03  0.03 34.27 42.12  0.04  0.01 35.04 27.91
CH3COOLi.2H2O
0.11 1.12 0.23 0.88 0.44 0.72
 0.03  0.04 33.39 62.75  0.03  0.01 34.27 48.77  0.08  0.02 35.04 39.38

Contd…
 303.15 K 313.15 K 323.15 K
A/ B/ ∆μ0*1 / A/ B/ ∆μ0*1 / A/ B/ ∆μ0*1 /
(m3/2. (m3. (kJ. ∆μ0*2 x 10-3 / (m3/2 . (m3. (kJ. ∆μ0*2 x 10-3 / (m3/2 . (m3. (kJ. ∆μ0*2 x 10-3 /
mol-1/2) mol-1) mol-1) (kJ. mol-1) mol-1/2) mol-1) mol-1) (kJ. mol-1) mol-1/2) mol-1) mol-1) (kJ. mol-1)
30 mass % THF
CH3COONH4
0.03 0.62 0.02 0.59 0.25 0.27
 0.04  0.02 33.47 32.98  0.01  0.06 34.32 31.05  0.06  0.04 35.14 14.06
CH3COOK
0.01 0.76 0.02 0.68 0.19 0.49
 0.01  0.05 33.47 40.42  0.10  0.01 34.32 35.78  0.04  0.05 35.14 25.49
CH3COONa.3H2O
0.11 0.94 0.12 0.86 0.27 0.68
 0.01  0.01 33.47 49.98  0.04  0.07 34.32 45.25  0.04  0.02 35.14 35.37
CH3COOLi.2H2O
0.02 1.17 0.06 1.01 0.12 0.79
 0.05  0.11 33.47 62.21  0.03  0.01 34.32 53.13  0.04  0.05 35.14 41.08
Derived values of specific acoustic impedance (Z), intermolecular free length (Lf), relaxation strength (r΄) and relative association
(RA) for the acetate salts in different mass % of THF + MeOH mixtures at 303.15 K.
Z x 10-3 / Lf / Z x 10-3 / Lf / Z x 10-3 / Lf / Z x 10-3 / Lf /
(m3mol-1) (nm) r΄ RA (m3mol-1) (nm) r΄ RA (m3mol-1) (nm) r΄ RA (m3mol-1) (nm) r΄ RA
CH3COONH4 CH3COOK CH3COONa.3H2O CH3COOLi.2H2O
10 mass % THF
881.58 0.066 0.52 1.02 835.20 0.069 0.57 1.02 874.54 0.067 0.53 1.02 830.29 0.070 0.57 1.02
750.54 0.078 0.65 1.08 722.72 0.081 0.68 1.08 739.50 0.079 0.67 1.09 714.35 0.082 0.68 1.08
722.22 0.081 0.68 1.10 703.72 0.083 0.69 1.09 723.06 0.081 0.69 1.11 709.53 0.083 0.69 1.09
736.35 0.079 0.67 1.09 739.00 0.079 0.67 1.07 761.26 0.078 0.65 1.10 772.02 0.076 0.64 1.06
812.28 0.072 0.59 1.06 827.75 0.071 0.58 1.04 889.19 0.067 0.53 1.05 959.47 0.061 0.44 0.99
1050.13 0.056 0.33 0.97 1171.41 0.050 0.17 0.93 985.30 0.060 0.43 1.01 1304.12 0.045 0.12 0.89
20 mass % THF
906.21 0.065 0.50 1.01 890.72 0.066 0.52 1.01 909.18 0.065 0.49 1.01 876.24 0.067 0.53 1.02
866.54 0.068 0.55 1.02 814.48 0.072 0.60 1.05 883.31 0.066 0.53 1.02 772.82 0.076 0.64 1.07
851.98 0.069 0.56 1.03 796.46 0.074 0.62 1.07 880.46 0.067 0.54 1.03 759.80 0.078 0.66 1.08
851.67 0.070 0.57 1.04 811.75 0.073 0.61 1.06 892.96 0.066 0.53 1.03 787.95 0.075 0.63 1.07
864.72 0.068 0.55 1.03 863.75 0.069 0.56 1.04 918.51 0.065 0.51 1.02 872.12 0.068 0.55 1.04
901.19 0.066 0.52 1.02 941.28 0.063 0.48 1.02 986.14 0.060 0.43 1.00 1051.82 0.056 0.34 0.97

30 mass % THF
938.41 0.063 0.48 1.00 936.56 0.063 0.48 1.00 949.63 0.062 0.47 0.99 941.55 0.063 0.47 1.00
983.26 0.060 0.43 0.99 973.29 0.061 0.44 0.99 1046.43 0.057 0.36 0.97 996.73 0.060 0.42 0.99
1005.33 0.059 0.41 0.98 991.62 0.060 0.43 0.99 1096.69 0.054 0.30 0.96 1017.51 0.058 0.40 0.98
1011.65 0.058 0.40 0.98 995.29 0.059 0.43 0.99 1105.33 0.054 0.29 0.96 1011.15 0.059 0.41 0.99
1000.14 0.059 0.41 0.99 989.84 0.060 0.44 1.00 1063.75 0.056 0.35 0.98 985.13 0.060 0.44 1.00
981.44 0.060 0.44 0.99 971.54 0.061 0.46 1.01 995.20 0.060 0.44 1.01 939.94 0.063 0.49 1.02
 18

16

14
KS x 1 0 / ( P a )

12
-1

10
10

0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35
-1
m / ( mol. kg )

Fig.2(a): Variation of isentropic compressibility (KS) with concentration

(m) of acetate salts in 10 mass % THF at 303.15 K. Graphical points:
CH3COONH4 (■); CH3COOK (); CH3COONa.3H2O (▲); CH3COOLi.2H2O ().
 CH3OH…….
(THF)
CH3COONH4, CH3COOK,
CH3COONa.3H2O, CH3COOLi.2H2O

Vφ0 - ion-solvent interactions

Sv* - ion-ion interactions
strong ion-solvent interactions between NH4+ ion and THF +
MeOH molecules and Strong ion-ion interactions between
Li+ ion and THF + MeOH molecules
 The smaller ions show a stronger affinity towards the
ionic association while the larger ions seems to be
responsible for the inability to ion-pair formation.

SV* values is found to increase as mass % of THF

increases along with the rise in temperature. This is
reflected to accommodation of more and more solute
molecules in the empty space left in the packing of
associated solvent molecules resulting in an increased
ion-pairing.

Rise in temperature is attributed to violent thermal

agitation resulting in increasing the force of ion-ion
interactions.
 A–coefficients - the ion-atmosphere effects

 B–coefficients -solvation of the ions and their effects

on the structure of the solvent in the near
environment of the solute particles

 small A values indicate weak ion-ion interactions and

positive B values suggest the presence of strong ion-
solvent interactions

 B–coefficients decreases from NH4+ to Li+ as mass %

of THF increases and decreases with rise in
temperature, thus, indicating weakest ionic solvation
for Li+-salt
 ∆μ0*2 i.e. the contribution per mole of the solute to free energy of activation
for viscous flow of solution followed the order:

CH3COOLi.2H2O > CH3COONa.3H2O > CH3COOK > CH3COONH4

 The change observed in Z (acoustic impedance) with conc. is attributed to

change of ultrasonic speed. This behavior is due to association of
molecules and formation of molecular aggregates.

 The increase in Lf (intermolecular free length) implies increase in number

of free ions showing the occurrence of ionic dissociation.

 The change of r΄ (relaxation strength) with conc. may be interpreted in

terms of increase in intermolecular forces due to increase in conc. and
subsequent decrease in the relaxation of the molecules.

 RA (relative association) is used to understand the interaction influenced by

the breaking of the solvent structure on addition of solute and the solvation
of the solute simultaneously produced.
 Solute–Solvent and Solute–Solute Interactions of
Resorcinol in Mixed 1,4-Dioxane–Water Systems at
Different Temperatures

Vφ0 = a0 + a1.T + a2. T2

Φ0E = ( δV0/ δT ) P = a0 + 2 a2 T

( δ cP / δ P ) T = – ( δ 2 Vφ0/ δ T 2 ) P
 140

120
Vφ x 10 / ( m . mol )
-1

100

80
3

60
6

40

20

0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5
-3 1/2
√ c / ( mol. dm )

Fig.1(a): Apparent molar volumes (Vφ) against square root of molar

concentration (√c) of resorcinol in 1,4-dioxane + water mixtures and pure
1,4-dioxane at 303.15 K. Graphical points: 10 mass % DO (▲); 20 mass %
DO (○); 30 mass % DO (●); 100 mass % DO (Δ).
 0.4

( h / h 0 – 1 ) ÷ √ c / ( mol. dm- 3 ) - 1 / 2
0.3

0.2

0.1

-0.1

-0.2
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5
-3 1/2
√ c / ( mol. dm )

Fig. 2(a): (/0 –1) /√c against square root of molar concentration (√c) of
resorcinol in 1,4-dioxane + water mixtures and pure 1,4-dioxane at 303.15
K. Graphical points: 10 mass % DO (▲); 20 mass % DO (○); 30 mass % DO
(●); 100 mass % DO (Δ).
Limiting apparent molar expansibilities (Φ0E) for resorcinol in 1,4-dioxane
+ water mixtures and pure 1,4-dioxane at (303.15, 313.15 and 323.15) K.
Standard errors are given in parenthesis.

Mass % of Φ0E x 106 / ( m3. mol-1. K-1 )

1,4-Dioxane 303.15 K 313.15 K 323.15 K ( δΦ0E / δT ) P

10 1.00 (± 0.03) 0.79 (± 0.02) 0.59 (± 0.01) Negative

20 0.29 (± 0.02) 0.27 (± 0.04) 0.24 (± 0.03) Negative
30 0.25 (± 0.01) 0.19 (± 0.03) 0.14 (± 0.02) Negative
100 0.28 (± 0.02) 0.18 (± 0.03) 0.09 (± 0.02) Negative
 3

2.5
ΦK x 10 / ( m . mol . Pa )
-1

2
-1

1.5
3

1
10

0.5

-0.5
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5
-1 1/2
√ m / ( mol. kg )
Fig. 3: Apparent molal adiabatic compressibility (ΦK) against square root
of molal concentration (√m) of resorcinol in 1,4-dioxane + water mixtures
at 303.15 K. Graphical points: 10 mass % DO (▲); 20 mass % DO (○); 30
mass % DO (●).
 O-H
…………….
H
O
O-H …………...... H
(Resorcinol) (DO)
Vφ0 values indicates the presence of strong solute-solvent
interactions, and these interactions are strengthened with a rise in
temperature and weakened with an increase in the amount of 1,4-
dioxane in the mixed solvent under investigation, suggesting
larger electrostriction at higher temperature and lower amount of
1,4-dioxane in the mixture.
 SV* results indicate the presence of weak
solute-solute interactions which decrease with
a rise in temperature attributing to more
violent thermal agitation that decreases the
ionic dissociation and it increases with an
increase in the amount of 1,4-dioxane in the
mixture which results in a decrease in
solvation of ions.

 Negative ( δ2Vφ0/ δT2 )P values suggested that

resorcinol acts as a structure breaker in these
solvent mixtures
 Concluding Remarks
 Most of the present day knowledge on non-aqueous solutions
have come from studies on various thermodynamic properties, e.g.,
density, transport properties, e.g., viscosity, conductance as well as
acoustic properties, e.g., ultrasonic speed.

 Molecular interactions are very complex in nature, if careful

judgement is used, valid conclusions can be drawn in many cases
relating to degree of structure and order of the system.

 Extensive studies of the different physico-chemical, biological

or pharmaceutical activity between different components of a
given mixture will be of sufficient help in understanding the nature
of the different interactions prevailing in systems.
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 Symposium/Seminar/Convention
Attended
 The National Symposium on Current Trends in Chemical
Research, organized and hosted by the Department of
Chemistry, Gauhati University, Guwahati, Assam, India
from 27th to 28th February, 2004 on the topic “Studies on
Viscous Synergy and Antagonism of Liquid Mixtures at
Various Temperatures”.

 The 42nd Annual Convention of Chemists, organized by

the Indian Chemical Society, Kolkata, and hosted by Visva-
Bharati University, Santiniketan, India during 9th to 13th
February, 2006 on the topic “Viscous Synergy and
Antagonism and Isentropic Compressibility of Ternary
Mixtures containing 1,3-Dioxolane, Water and
Monoalkanols at 303.15 K”.
 List of Publications
 Investigations of Viscous Antagonism of Binary Liquid Mixtures in
the Temperature Range, 303.15 K to 323.15 K, Journal of Teaching
and Research in Chemistry, 2004, 11, 12-20.

 Excess Molar Volumes, Viscosity Deviations and Isentropic

Compressibility of Binary Mixtures Containing 1,3-Dioxolane and
Monoalcohols at 303.15 K, Journal of Solution Chemistry, 2005, 34,
1311-1325.

 Investigation on Viscous Antagonism of Ternary Liquid Mixtures

and its Relation to Concentration, Journal of the Indian Chemical
Society, 2005, 82, 814-818.

 Solute-Solvent and Solute-Solute Interactions of Resorcinol in Mixed 1,4-

Dioxane-Water Systems at Different Temperatures, International
Journal of Thermo-physics, 2005, 26, 1549-1563.

 Ion-Solvent and Ion-Ion Interactions of some Tetraalkylammonium,

Alkali metals and Ammonium Halides in Isoamyl Alcohol at 298.15 K by
Conductometric Technique, Journal of the Indian Chemical Society,
2006, 83, 160-164.
 Viscous Synergy and Antagonism and Isentropic Compressibility of
Ternary Mixtures containing 1,3-Dioxolane, Water and Monoalkanols at
303.15 K, Fluid Phase Equilibria, 2006, 243, 133-141.

 Studies of Viscous Antagonism, Excess Molar Volume and Isentropic

Compressibility in Aqueous Mixed Solvent Systems at Different
Temperatures, Physics and Chemistry of Liquids, 2006, 44, 303-314.

 Densities, Viscosities and Sound Speeds of some Acetate Salts in Binary

Mixtures of Tetrahydrofuran and Methanol at (303.15, 313.15 and
323.15) K, Journal of Chemical and Engineering Data, 2006, 51, 1415-
1423.

 Electrical Conductances of Some Ammonium and

Tetraalkylammonium Halides in Aqueous Binary Mixtures of 1,4-
Dioxane at 298.15 K, Pakistan Journal of Scientific and Industrial
Research, 2006, 49, 153-159.

 Conductivity Studies of Sodium Iodide in Pure Tetrahydrofuran and

Aqueous Binary Mixtures of Tetrahydrofuran and 1,4-Dioxane at
298.15 K, Physics and Chemistry of Liquids, in press.
Acknowledgement
THANK YOU