Professional Documents
Culture Documents
Ph.D. Seminar
Ph.D. Seminar
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-
DioxaneWater Systems at Different
Temperatures
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
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
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
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
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
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 ( expdensities 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.
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
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 (▲).
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
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
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
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
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
-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
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
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.
= 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
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
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
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
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
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
KS = 1/ (u2 ρ)
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.
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 )
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 )
Φ0E = ( δV0/ 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 )
( 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.
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.