Determination of Partial Molar Enthalpy Of Glycerol-Water Mixtures

Cesar Ian A. Caermare College of Science and Mathematics Western Mindanao State University 7000, Zamboanga City, Philippines

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Abstract
Simple calorimetry was employed to determine the empirical molar enthalpy of mixing of glycerol and water in the series of glycerol-water mixtures. Partial molar enthalpies, H 1 and H2 at 0.45 mole fraction of glycerol were determined by plotting molar enthalpy of mixing, H against mole fraction of glycerol, x1, then sketching a tangent line at 0.45 mole fraction of glycerol. Theoretical heat capacities of glycerol and water were utilized for the determination of mean heat capacity of various glycerol-water mixtures, which were further utilized for the determination of enthalpy of mixing of these mixtures. At x1=0.010, 0.100, 0.200, 0.301, 0.499, 0.694, 0.799, and 0.948, empirical enthalpy of mixing for these systems were found to be 26.818, 247.824, 834.028, 287.589, 331.991, 250.530, 135.724, -2557.290 J.mol-1. At 0.45 fraction of glycerol, empirical partial molar enthalpy of glycerol, H1 was found to be 40 J.mol-1 and that of water, H2 is 320 J.mol-1. The experiment shows that calorimetry is efficient in establishing the enthalpy of mixing of various glycerol-water mixtures and determining the partial molar enthalpies of the components of these mixtures.

_____________________________________________________________________________ _ Keywords: Partial molar enthalpy, Partial molar quantity, Glycerol-H2O system,, calorimetry

Introduction
Quantities of solution that tell us how properties of the solution change with the concentration are often referred to as partial molar quantities. One of the collectively known partial molar quantities is the molar enthalpy of mixing. It is defined as a variation in enthalpy per mole of solute added when an infinitesimal amount of substance is added to a solution at constant temperature, pressure and mole of glycerol (N1)[3]. Mathematically it is defined as: __ H1= (H/n1) T, P (1) Partial molar enthalpy can be obtained from heat released/absorbed during a mixing process. These measurements are usually carried out in isothermal calorimeter systems. Enthlapies determined are usually reported as enthalpy change in mixing as a function of mole fraction. A vacuum flask/Dewar flask can be used as an adiabatic calorimeter. However, minute heat leaks are not uncommon. In order to reduce heat flow to or from the surroundings, Dewar flask itself should be placed in a constant temperature container such as a large thermostat or

insulated box whose temperature should be regulated as close to the temperature of the calorimeter system as possible. Care should be taken so that heat leaks do not occur through either the lid of the Dewar flask or openings in the lid. This study was carried out to determine the molar enthalpy of mixing of various glycerolwater mixtures and determine the partial molar enthalpies of these components via graphical method (plotting H against x1)

Methodology
A. Determination of Partial Molar Enthalpy For mixture (1) of glycerol and water, a specific volume of glycerol (provided in table 1) was pipetted to Dewar flask and temperature was noted after two minutes. A specific volume of H2O was pipetted and added to Dewar flask. The system was mixed thoroughly and then constant temperature was noted. Dewar flask was rinsed with distilled water and dried. The entire procedure was repeated for other mixtures (2-8) glycerol-water mixtures. All determinations were done in two trials. B. Treatment of Data For all mixtures, the raw data were utilized to calculate for the change in temperature of trials one and two. The average of the change in temperature for trials one and two was also obtained. Number of moles of glycerol and water as n1 and n2 were also calculated and total moles were calculated. From this, mole fractions of glycerol and water were also obtained. The mean heat capacity for the mixtures were calculated using the mole fractions of a certain mixture and the theoretical heat capacities of components (Cglycerol = 207.15 J.mol-1.K-1 and Cwater = 75.3 J.mol-1K-1) was calculated. Molar enthalpy of mixing was calculated. A plot of molar enthalpy of mixing, H against mole fraction of glycerol, x1 was constructed and a tangent line was sketched at x1 = 0.45, and the partial molar enthalpy of glycerol and water, H1 and H2 was determined.

Results and Discussion

Molar enthalpy of mixing were evaluated using simple calorimetric method. The commonly known parameters that affect the partial molal quantities in general are temperature, pressure and composition of the solution[3]. In this experiment, the molar enthalpy of mixing of various water-glycerol systems were evaluated keeping the temperature and pressure constant. Table 1 shows the molar enthalpy of mixing of various glycerol-water systems. Table 1: Molar Enthalpy of Mixing of eight varied mixtures of water and glycerol
Solutio n 1 2 3 4 5 6 7 8 Mole Fraction [glycerol] 0.010014 0.099912 0.199779 0.300572 0.499036 0.693796 0.799283 0.947594 Mole fraction [water] 0.989986 0.900088 0.800221 0.699428 0.500964 0.306204 0.200717 0.052406 Mean Heat Capacities (J.mol-1.oC) 76.62041 88.47344 101.6408 114.9304 141.0979 166.777 180.6855 200.2403 Molar Enthalpy of Mixing (H, J.mol-1) 26.81714 247.7256 833.4546 287.326 331.58 250.1655 135.5141 -2553.06

The partial molar quantities are close to the pure component value, when the mole fraction of that component is close to unity. Thus, it is possible to determine the partial molar enthalpies (enthlpies of components) in the solution. To better understand this behavior, empirical data in table 1 will be constructed as a plot of molar enthalpy of mixing, H against mole fraction of glycerol.

H2 = 315 J.mol-1.oC

H1= 40 J.mol-1.oC

Fig. 1: Graphical representation of enthalpy of mixing as a function of mole fraction of glycerol.

Figure 1 illustrates the relationship of the enthalpy of mixing and mole fraction of glycerol in water-glycerol mixtures.From the constructed plot, partial molar enthalpies (enthalpies of water and glycerol) can be estimated with high mathematical certainty by sketching a tangent line to the point where 0.45 mole fraction of glycerol lies. The plot reveals that for a mixture of 45% glycerol and 55% water, the enthalpy of glycerol as H1 = 40 J.mol.oC is while enthalpy of water as H2 = 315 J.mol-1.oC. is. At x=0.45 glycerol, agood estimation of the enthalpies of both components can be achieved. This is because partial molar enthalpy is an example of a partial molar properties. The partial molar quantities are close to the pure component value, when the mole fraction of that component is close to unity. In contrast, partial molar properties are most different (farthest apart) form the pure component propeties at infinit dilutions (this is when the mole fraction of glycerol approaches zero).[4] At molecular level, the molecules of concentrated species are interacting most frequently with the like molecules. Consequntly, their environment, and thus their molar properties are similar to those of the pure fluid. Meanwhile, the dilute species is interacting mostly with the molecules of the concentrated species. Consequently, its molar environment, thus its partial molar properties, will be farthest from being similar to the pure component.[4] Inherent errors in the detrminations cannot be ignored. Radical cause of this may be accounted to heat leaks from the calorimeter system while doing calorimetric measurements. The impurities present in the glycerol (since it is labeled used) cannot also be ignored. The heat leaks may cause temperature fluctuations and the impurities in glycerol can affect the actual enthalpies of the mixtures and their water-glycerol components.

Conclusion
Molar enthalpy of mixing and partial molar enthalpy for the components of various water-glycerol systems were determined using simple calorimetric method. The enthalpies of mixing of glycerol-water mixtures were successful in determining the partial molar enthalpies of a mixture containing 0.45 mole fraction of glycerol. A good approximation of the partial molar enthalpies can be found at a point of the graph where glycerol contributes 0.45 mole fraction in the mixture because at this point, glycerol is in close unity with water, making it interact with other glycerol molecules more frequently. Errors arising from this activity caused mainly by uncontrollable temperature fluctuations due to heat leaks and impurity of glycerol since the glycerol is pre-used.

References
(1). Atkins, P.W. Physical Chemistry, 7th edition, Oxford University Press. (2). Determination of Partial Molar Enthalpies by adiabatic calorimetry and the partial molar enthalpies of the components [laboratory activity] (3). Levine, I. Physical Chemistry, 5th edition, McGraw Hill companies Inc., 1978 edition. (4). Dr. Ali Khalaf Al-Matar Chemical Engineering Thermodynamics II Experimental Determination of Partial Molar Properties