ChE 203 EXPERIMENT 4 DETERMINATION OF PARTIAL MOLAL VOLUMES Object Determination of the density and specific volume of a non-ideal

solution, and partial molal volumes of its components by using a pycnometer. Theory Thermodynamics is concerned only with the macroscopic properties of a body and not with its atomic properties, such as the distance between the atoms in a particular crystal. These macroscopic properties form a large class and include the volume, pressure, surface tension, viscosity, temperature etc. They may be divided into groups as follows: The extensive properties, such as volume and mass, are those which are additive, in the sense that the value of the property for the whole of a body is the sum of the values for its constituent parts. The intensive properties, such as pressure, temperature, density, temperature, etc., are those values can be specified at each point in a system and which may vary from point to point, when there is an absence of equilibrium. Such properties are not additive and do not require any specification of the quantity of the sample to which they refer. Both properties can be expressed by means of homogenous functions: f(kn1,.......kni,...) = kNf(n1,..........,ni,....) (1)

Where ni represent for our purposes the number moles of component in a phase. The component N equates to either 1 or 0 for the case of extensive variables, respectively. Among intensive variables, important in thermodynamics are molar quantities, defined by the equation.
i = (/ n1)P,T, nj = 1

(2)

Where is a thermodynamic property and i is the corresponding partial molar property of component i in the solution. The partial molar properties are very important in dealing with the problems of the solution thermodynamics. For ideal gaseous or liquid solutions, the partial molal volumes, internal energies and enthalpies (V, U, H) are equal to their respective molar

quantities for the pure components while Si , A i , G i are not. For non-ideal solutions, all partial molar quantities of components differ in general from their corresponding molar quantities in pure, and the difference are frequently of interest. An important property of partial molal quantities is obtained from Eulers theorem for homogeneous functions. For a homogeneous function of degree N;

n1

f f f + n2 +.........+ ni +........ = Nf n1 n2 ni

(3)

Applied to an extensive thermodynamic variable , for which N=1, eq (1) becomes

n11 + n2 2 +.......+ ni i =

(4)

if the variable is written in a different form,

d =

dn1 +........+ dni +.....+ dP + dT n1 ni P T

(5)

and by differentiating eq(4),

d = 1dn1 +.....+i dni +.......+ n1d 1 +.....+ ni d i

(6)

in addition by comparing the equations (5) and (6); the final relation can be achieved;
n1 d 1 +......+ ni d i dP dT = 0 P n ,T T n , P

(7)

At constant pressure and temperature, eq(7) reduces to;

n1 d 1 + ......+ ni d i = 0

(const P & T)

(8)

The eq (8) shows that changes in partial molal quantities of the respective species are interdependent. For a binary solution eq (8) becomes;

d 2 d 1

x1 x2

(9)

Where xi is the mol fraction of component i, xi = ni/

. In application to free energy this

equation is commonly known as the Gibbs-Duhem equation and is valid for any thermodynamic property M in a homogenous phase. For a binary system if volume V is taken as extensive variable, the following equations can be written: In ideal solutions, Vk = n1V1 + n2V2 In non ideal solutions, Vk = n1
+ n2

(10a)

(10b) is partial

where Vk is the volume of the solution, V is the molal volume of component i, molal volume of component i.

If equations (10a) and (10b) are divided by # of moles of solutions, the above equations may be written as In ideal solutions, Vm = x1V1 + x2V2 = V1 + (V2 V1)x2 In non ideal solutions, Vm = x1
+ x2

(11a)

+(

)x2

(11b)

is obtained, with Vm, molal volume of the solution and xi mol fraction of component i.. The equations above can be written in terms of specific volume ( (P1), ) and % concentration

or V=V1w1+V2w2 (12)

where V is the specific volume of the solution (ml/g), Vi and wi, partial specific volume and weight fraction of component i, respectively.

Experimental Work Equipment and Materials: Pycnometer (4), 250 ml round bottom flask, oven, balance, pipette (4), HCl solutions in various concentrations, distilled water. Procedure: 1. 25 ml samples of solutions of HCl and water containing approximately 20, 40, 60 and 80 % (wt/wt) of HCl are prepared by accurately weighing the two components into a stoppered bottle. 2. The density of each solution is determined at room temperature (~250C) as following: 3. The weight of the previously oven-dried and cooled pycnometers, Wp, is determined and they are filled with distilled water making sure the water level in the pycnometer reaches the top of the capillary and free of air bubbles. 4. The pycnometer filled with water (Wg), is weighted making sure that the outside of the pycnometers is completely dry. 5. From the density of water at 250C, (V= (Wg-Wp)/ ) = 0.997 g/ml, volumes of pycnometers are calculated.

6. Subsequently, the pycnometers filled with different mixtures of HCl + H2O are weighed and their densities are calculated. Calculations: 1. Calculate the specific volume (ml/g) (i.e. reciprocal density) of each solution and plot the percentage weight of HCl (abscissa) against specific volume. 2. Draw a smooth curve through points, and draw tangents to the curve at different concentrations. The intercept of these lines on 0 % and 100 %ordinates gives the partial specific volumes of water and HCl respectively at various concentrations. 3. Calculate the partial molal volume (ml/gmol) of components in solution, from partial specific volume (ml/g) and molecular weight (g/gmol). 4. Calculate the molal volumes of HCl solutions at different concentrations. 5. Calculate the specific volume of HCl solutions using partial specific volumes and weight fractions of components within the solution. Compare the results with your experimental data.

6. Finally, draw two plots showing the variation of the partial molal volume of HCl, and the partial molal volume of water with mole fraction (abscissa) on the same graph. (Do not draw a curve!)