OBJECTIVE

• The objective of this practice is to obtain the graph of molar

volume-vs-molar fraction of mixture and hence the partial molar
volumes of solvent and solute at a given mole fraction.
 Theoretical Framework
• In a given solution constituted by molecules A and B, where molecular size and
interaction strengths for the like neighbors A-A, B-B and unlike neighbors A-B are
equal; under these conditions the simplest possible behavior by the solution is
expected, which is considered an ideal solution since there is total consistency on
intermolecular forces as consequence of molecular size and similar molecular
structure.
• Analyzing volume property of the solution, for an ideal solution, we have:
• Vm= Va + Vb
• Where:
• Vm is the volume of the mixture
• Va is the volume of pure A component
• Vb is the volume of pure B component
• When studying real solutions, deviations from ideal behavior occur due to
different molecular sizes between molecules in the system that are not the
same. For instance, when mixing 50ml of water with 50ml of methanol,
volume of the solution is 95ml.

• When studying cases like this, there is no way to determine which part of the
concentration is due to water and which part is due to alcohol, similar
difficulties are observed in other thermodynamic properties. In order to
solve this problem and to employ a method to handle variable compositions,
Lewis invented partial molar property.
• Taking an extensive property, such as volume (V), enthalpy (H), free energy
(G), etc., you can define a property associated with each of them that will be
independent of the amount of matter in the system and therefore it will be
intensive.

• When the system is a mixture, the intensive properties acquire different

values for each component and the contribution of each component to the
total property is called partial molar property.

• Then it will be "partial molar volume of a given component in a mixture the

contribution made by a mole of said component to the total volume of the
mixture".
• To characterize mathematically the non-additive properties of the mixtures, a
partial property is defined. Thus, for example, the molar partial volume of
component i is the variation of the total volume of solution that occurs in
the addition of component i, for specified concentration, temperature and
pressure conditions:
Where:
𝑣ഥ𝑖 = 𝑀𝑜𝑙𝑎𝑟 𝑝𝑎𝑟𝑡𝑖𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒
𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖
• The partial derivative:

• It can be measured experimentally by observing the volume variation of a system

so large that the addition of 1 mole of component i does not produce
composition variation.
• There are a number of methods to obtain molar partial properties:
• 1. Analytical method. If the data can be expressed in the functional form it
can be obtained by partial differentiation.

• 2. Method of the slopes. A tangent of curve V, total volume, versus the

component, represents the partial molar volume at the corresponding point.

• 3. Method of ordinates. If the molar volume v is plotted against the molar

fraction of component 2 of a binary mixture, a tangent to the curve at a
point cuts the ordinate.
Materials and procedure
Materials
• Analytical balance
• Pycnometer
• 50 ml volumetric flask
• Dropper
• 50 ml beaker

• Ethanol
• Distilled water
 Procedure
• The first thing we have to do is to calculate the mass of ethanol and distilled
water. The total solution must be of 25 grs.

• Prepare the solution.

• Weigh the empty pycnometer. (Wpic)

• Fill the pycnometer with the solution and weigh it. (Wpic+soln).

• Repeat the process 4 times for the different solutions.

Practice Calculation
• 1. First Step, obtaining data for:

• Second step, our base data will be: 25 grams of sample. And then, let’s
pretend theorical molar fractions of 0.2, 0.4, 0.6 y 0.8.
• With those data, we proceed to make a relation between the molar fractions
in order to establish a function of those.

• Now, lets replace the previous data in the formula:

• But, this formula can be expressed as:

• Considering 25 grams of the simple, and the relation between molar
fractions that we established, we have:

• With this, we can solve the equation for “n1” (number of moles):
• Now lets obtain each theorical weight (W) from the “number of moles”
formula:

• After this, we use the analytic balance scale to obtain the real weight:
• Then, we can obtain the real molar number of each substance with the
“molar number” formula:

• Now, lets obtain the real molar number, in order to obtain the real molar
fraction.
• After this, we can get the “medium molar mass”:

• Now, lets get the solution’s weight:

• Then, in order to obtain the density:

• And finally, we get the molar volume:

• Let’s do the same for the remaining samples in order to obtain all the data:
• Now, in order to satisfy the objective of the practice, let’s to the graph
between “real molar fraction of etanol” and “solution molar volume”.
• Now we can apply a second-order regression for the previous data:

• As you can see, we got a good cooperating factor.

• As we saw in the begining, we can also apply the “ordinates metod” in order
to determine molar volumen of the solution.

• 1. First, we have the function that we obtained previously.

• Now, lets derive the function.

• After this, we can replace the 0.2 value in order to obtain the “y” value.

• Then, we replace the derivative for 0.2 in order to obtain the slope.
• With this, we obtained the “tangent line” equation.
• Finally, by replacing extreme values, we get:
 To conclude…
• In the elaboration of this practice we could know the partial molar volume
of an ethanol-water mixture to different compositions, without having to
analyze it deeply, by means of the ordinate method, where the partial molar
volume of the mixture vs the fraction molar of the solute. The graph that we
made and the regression that we obtained is accepted since the regression
gave close to the unit, and the curve can be appreciated.
• This practice can be done with other substances such as methanol, benzene,
etc. That are soluble among themselves.

• It is important to calibrate the pyknometer first in order to obtain more

accurate calculations and know correctly the volume of this.
 Bibliografía
• https://quimica.unam.mx/wp-content/uploads/2016/12/12etanol.pdf