On the temperature-dependence of viscosity and excess molar

volume in formamide + N,N-dimethylacetamide liquid mixtures

Z. Barhoumi (1),* N. Ouerfelli (1), Debashis Das (2), N. Amdouni (1).

(1) Unit de Recherche Physico-Chimie des Matriaux, Dpartement de Chimie, Facult des Sciences de Tunis, (FST), Campus
Universitaire, 2092 El Manar Tunisie.
(2) Department of Chemistry, Dinhata College, Dinhata, 736135 Cooch-Behar, West Bengal, India.
* e-mail : barhoumi.zina@yahoo.com (Barhoumi Zina ).
Socit Chimique de Tunisie

Laboratoire de Chimie des

matriaux

41mes Journes de Calorimtrie et dAnalyse

Thermique
14 - 16 Mai 2010 - Htel Eldorador Ksar
Rouge, Tozeur Tunisie.

INTRODUCTION

Dynamic viscosity ( = . ) were obtained from the density ()and kinematic viscosity( ) measurements using DMA-4500 digital vibrating tube densitometer and
an Ubbelohde-type viscometer in the temperature range (298.15 to 318.15 K) in dimethylacetamide (DMA) + formamide (FA) binary liquid mixtures over the entire
range of mole fraction.
Deviation properties of mixtures surplus is the difference between the actual value of a large property and the value which it would have if the system behaved
linearly, and are therefore useful in the study of molecular interactions and arrangements. For the case where the property, including various methods of correlation
equations Arrhenius equations Redlich-Kister equation and Herrez were applied to evaluate the experimental data, polynomials excess mole fraction for each fixed
temperature and the Arrhenius equation as-cons reciprocal absolute temperature (1/T) at each fixed composition. We note that the reduction of the Redlich-Kister
function Q,T (x1) = /(x1x2) gives more information than the difference in viscosity. Similarly, the reduced molar volume on Redlich (V Ex), as well as viscosity
deviations in viscosity () and derived properties of liquid mixtures containing amide which constitute an important tool in the interpretation of complex molecules
biological interest.
The results were fitted with Redlich-Kister polynomials against mole fraction for each fixed temperature and the Arrhenius equation, as the temperature at each
fixed composition using KaleidaGraph 4.1 soft.

-1.0

0.2
298.15
308.15
318.15

0.0

1.6

-1.5

1.2
1.0

-2.0

-0.2

298.15
308.15
318.15

1.4

QV 298.15
QV308.15
QV 318.15

0.8
-0.4

-2.5

-0.6

-3.0

0.6
0.4

x1

x1
-3.5

-0.8
0.0

0.2

0.4

0.6

0.8

0.0

1.0

Excess molar volume for DMA (1) + FA (2) mixtures

versus molar fraction in DMA.

0.2

0.4

0.6

0.8

0.0
0.0

1.0

0.2

0.4

0.6

0.8

1.0

Excees viscosities for DMA (1) + FA (2)

mixtures at different temperatures against
mole fraction x1 in DMA.

Redlich-kister function of excess molar volume for

DMA (1) + FA (2) mixtures in the temperature
range versus molar fraction x1 in DMA.

V ex=x1M1(1/mix-1/1)+x2M2(1/mix-1/2)

x1

0.2

QV=Vex/(x1x2)

=mix-(x11+x22)

Measurement cell

10

Quartz
Thermometer

318.15
308.15
298.15

hp

(0.002C)
20.589C

Schott Gerate
4

0.9876

x1
0
0.0

0.2

0.4

Ap

0.6

0.8

1.0

The experimental Redlich-kister Q for the ratio

/x1,(1-x1) of the viscosities deviations for DMA (1)
+ FA (2) mixtures against mole fraction x1 in DMA.

Mercury
Thermometer

Thermostated bath

Densitometer
Logarithm of viscosity versus 1/T
for DMA (1) + FA (2) mixtures

DENSITY AND VISCOSITY MEASUREMENTS

Q=/x1x2
20

x
40

-4

0.2

0.4

0.6

Ea

18

-4.5

16

-5

14

-5.5

12

-6

10

8
0.0

x1
0.2

0.4

0.6

0.8

Energy activation and B for viscous flow

Ea against mole fraction x1 of DMA. for
DMA (1) + FA (2) mixtures

QEa=Ea/x1x2

Correlation between energy of activation(Ea)

and of viscosity for DMA (1) + FA (2) mixtures
versus molar fraction x1 in DMA..

298.15 K
308.15 K
318.15 K

30

25

-1

-1

20

-2

-2

10
0.0

-7
1.0

35

-3

15

-6.5

0.8

x1
0.2

0.4

-4
0.6

0.8

1.0

-3

298.15 K
308.15 K
318.15 K

0.2

0.4

0.6

0.8

-4

Redlich-Kister function Q for the ratio Ea/x1(1x1) of the deviation energy for DMA (1) + FA (2)
mixtures against mole fraction x1 in DMA.

The experimental Herraz exponent

polynomials Pexp,T(x1) for DMA (1) + FA (2)
mixtures versus mole fraction x1 of DMA.

Pexp,T(x1)=ln(exp-2/1-2)/lnx1

VEx excess molar volume is negative for the entire composition with a minimum of approximately 55% (mole) of dimethylacetamide in the range of temperature,
viscosity deviations are positive over the entire range of composition with a maximum around 30% (mole) in the temperature range, the V Ex and indicate a strong
molecular interaction between formamide and dimethylacetamide due to hydrogen bonds,
It is found that the temperature dependence of viscosity can be fitted with an Arrhenius equation as =B.exp (Ea/RT), Redlich Kister can not represent appropriately
composition dependence of viscosity,
We note that Q function reduction Redlich-Kister, T (x 1) = / (x1x2) gives more information than the difference in viscosity, the same way, the reduced relative
Qrel, Redlich-Kister function Qrel,,T(x1) = Q,T(x1) / has opportunity to eliminate the effect of the temperature of the possible release of other phenomena
log (viscosity), 1/T, where T is in degrees Kelvin, is linear, the slope of such a plot gives a kind of activation energy for viscous flow, the flow of energy Ea activation
increases with the mole fraction x1 in dimethylacetamide and rises to a maximum of 20 kJ.mol -1 x1 (formamide) = 0.66 showing a mutual preferential solvation (2FA and
1DMA), over the polynomial Herrez used in the viscosity can be used as a test-type interaction potential predominant at infinite dilution, B 0 as shown in the equation at
infinite dilution (in dimethyl formamide or formamide in dimethylacetamide) limit the exponent values Herrez polynomial can be calculated by P(x i = 0) = B0 ; far from
universal exponent 0.5 and it describes the inter-dominated solute-solvent at infinite dilution,