Introduction Theoretically, any extensive property that defines a system, when varied with respect to the amounts (ni)

of the components that comprise the system at constant temperature and pressure give rise to interesting intensive properties called partial molar properties. A partial molar property is a thermodynamic quantity which indicates how an extensive property (such as V, G, H, S, and A) of a solution or mixture varies with changes in the molar composition of the mixture at constant temperature and pressure, or for constant values of the natural variables of the extensive property considered. It is the partial derivative with respect to the quantity (number of moles) of the component of interest. (Atkins and de Paula, 2006 )

Experimentally, the property that is easiest to measure is the partial molar volume. (Atkins, 2006) We can then generalize the form of the partial molar volume Vi of component i as (based from Eq. 1):

Though it is a nave expectation that volumes of components ion a mixture are additive. However, it would actually hold true only for ideal solutions those that are formed from components that have very similar structures and therefore, similar forces of attraction existing within the molecules. Hence, it should be emphasized that the partial molar and pure component property, in general, are not equal. (Sandler, 2006) In this experiment, we establish the relationship of the partial molar volumes of ethanol/water solutions with different compositions. (Objective 1) From Figure 1 (left), it is observed that the partial molar volume of both ethanol and water varies with composition and that it does not have a linear relationship with the mole fraction. There is a simple reason why such analogy fails for real mixtures. One contribution to the volume (and the other thermodynamic properties) of a fluid is the interaction between the molecules and for pure substances, this contribution to the thermodynamic property is simply based upon the interaction between molecules with the same species. However, in a binary fluid mixture such as water-ethanol solution, the interaction energy is not only based upon the interaction between water-water and ethanol-ethanol molecules, instead, it is also based on the effect of the water-ethanol molecule interaction which is not accounted on the previous analogies. (Sandler, 2006) That is, the intermolecular forces between two water molecules, or between two ethanol molecules, are different from the intermolecular forces between a water molecule and an ethanol molecule. Secondly, water and ethanol molecules have different sizes and shapes, and, consequently, the molecules in pure water, or in pure ethanol, are going to fit together differently, than the molecules in a solution of ethanol and water. These two factors: differences in intermolecular

forces and differences in molecular sizes and shapes, compared to the pure substances, cause the molecules to pack together differently in the mixture than in the pure liquids, and result in the non-additivity of the volumes. Fig. 1 The partial molar It can now be concluded that the partial molar property is broadly understood volumes of water and ethanol as the contribution that a component of a mixture makes to the overall across the full composition property of the solution and can be written as, range at 25C. (P. Atkins and (Eq. 3) J. de Paula, "Atkins' Physical N N i i Chemistry", chap.5) so that, d ( N ) = i d i + i d (i ) N (Eq. 4) where: = overall extensive property of the mixture = the partial molar property of component i i N = the total number of moles in mixture NI = the number of moles in component i Since the extensive property is considered to be a function of T, P and each of the mole fractions, by partial differentiation, we would yield the generalized Gibbs-Duhem equation:
C dT dP + xi d i 0 T P , N i P T , N i i =1

(Eq. 5)

where: C = the total number of components in the mixture xi = the mole fraction of component i The Gibbs-Duhem equation for binary mixtures at constant T and P would equivalently be

x1 1 + x 2 2 x x 1 T , P 1

=0 T , P

(Eq. 6)

The Gibbs-Duhem equation is a thermodynamic consistency relation that expresses the among the C+2 state variables (T, P and C partial molar properties) in a C-component system, only C+1 of these variables are independent. (Sandler, 2006) Equation 6 tells us that a change in the partial molar property of one component in a binary mixture would bring a negative (or inverse) change of the partial molar property of another. Experimental values for the partial molar volumes can be obtained by laboratory measurements, specifically density measurements. In this experiment, we measure the densities of the solutions using two equipments: (a.) pycnometer and (b.) densitometer. (Objective 2) The density measurements are used to calculate the change of volume due to mixing, mixV ,
ix V =x1V1 +x 2 V2 x1V1 x 2 V m
2

= - x1V1 x 2 V V

(Eq. 7)

which is then plotted as a function of x1. To accurately calculate for the partial molar volumes, the data of mixV vs. x1 is fitted with a polynomial of the Redlich-Kister form:

mix V = x1 x2 ai ( x1 x2 )
i =0

(Eq. 8)

Differentiating Eq. 7 with respect to x1 and using the facts that the pure component molar volumes are independent of mixture composition and that for binary mixture x2 = 1 - x1 and using the Gibbs-Duhem equation,we would get:

mix V x1
mix V x2

( mix V ) = V2 V 2 x1 T ,P

) )

(Eq. 9) (Eq. 10)

( mix V ) = V1 V 1 x2 T ,P

In this experiment, we use Eqs. 9 and 10 to calculate for the partial molar volumes of both ethanol and water. (Objective 3)

Methodology: Ethanol-water solutions are prepared with varying mole fractions of ethanol (0.0, 0.03, 0.06, 0.09, 0.12, 0.15, 0.18, 0.21, 0.24, 0.27, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80, 0.90, 1.00). The following were used to calculate the

Information Flow Diagram Sample Calculations: