Partial Molar Volume of a Substance

OBJECTIVES
A. Generate a plot of molar volume versus mole fraction of methanol using experimental
data obtained using a pycnometer.
B. Determine the partial molar volume of methanol and water in a mixture of different
concentrations from the obtained experimental data.
C. Compare the obtained experimental values to available literature values.

INTRODUCTION
Partial properties are thermodynamic properties of individual species as they exist in
solution. They are composition-dependent and different from the molar properties of pure
species. They are denoted by an overbar, with a subscript to identify the species. Partial
molar properties are defined as

𝜕(𝑛𝑀)
̅≡[
𝑀 ]
𝜕𝑛𝑖 𝑃,𝑇,𝑛
𝑗

It is a response function, or in other words, a measure of the response of total property 𝑛𝑀 to

the addition at constant 𝑇 and 𝑃 of a differential amount of species 𝑖 to a finite amount of
solution. From this definition, we can see that it is possible to calculate partial properties from
solution-property data (i.e. given 𝑀, we can calculate 𝑀 ̅ ). The reverse is also true, such that
it is possible to calculate solution (mixture) properties from partial properties, and it is thus
shown in the summability relations

̅𝑖
𝑀 = ∑ 𝑥𝑖 𝑀
𝑖
̅𝑖
𝑛𝑀 = ∑ 𝑛𝑖 𝑀
𝑖

This implies that a solution property is a sum of the partial properties of its constituent species.
This is because the constituents in the solution are intimately intermixed, and owing to
molecular interactions, cannot have properties of their own.

For binary solutions (mixture of 2 constituents), it can be derived that

𝑑𝑀
̅1 = 𝑀 + 𝑥2
𝑀
𝑑𝑥1
𝑑𝑀
̅2 = 𝑀 + 𝑥1
𝑀
𝑑𝑥2

where 𝑥1 + 𝑥2 = 1.

MATERIALS

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Reagents: methanol, distilled water
Materials & Equipment: 25 mL pycnometers, 5mL pipette, 10mL pipette, 10 (50mL)
volumetric flasks, stopwatch, 2 (250mL) Erlenmeyer flasks, 250mL beaker, 150mL beaker,
hotplate, thermocouple, thermometer

PROCEDURE

A. Wet Bulb Temperature Determination

1. Wrap a small piece of cotton around the bulb of an alcohol thermometer. Secure it in
place with a rubber band or a small piece of thread
2. Dip the cotton wick in water.
3. Swing the thermometer rapidly in a circular fashion for 10 to 20 seconds. Caution: Be
careful in handling and swinging the thermometer.
4. Record the wet bulb temperature reading. Perform 3 trials by repeating procedure
A3.

B. Solution Preparation
1. Record the room pressure and temperature.
2. Prepare six (6) 50mL volumetric flasks with the following labels:

Mixture Mole Fraction

Methanol
A 0
B 0.2
C 0.4
D 0.6
E 0.8
F 1

3. Weigh and record the mass of each flask with its corresponding cover.
4. Transfer the appropriate amount of methanol into each flask using your predetermined
volume from your solution preparation calculations.
5. Weigh and record the mass of each flask with the appropriate amount of methanol
(still with its corresponding cover).
6. Fill the remainder of the flask with distilled water until the mark. Weigh and record
the mass of the filled flask (still with its corresponding cover). Mix the solution
thoroughly.
7. Recalculate the actual mole fraction of the mixtures using the mass of the methanol
and the water.
C. Experiment Proper
1. Weigh and record the mass of the dry and empty pycnometer. Perform 3 trials.
2. Place the volumetric flasks from Part B in a tap water bath at room temperature.
Record the temperature of the bath. Allow 10 minutes for the mixtures to reach the
temperature of the water bath.
3. Using the first mixture, fill the dry, clean pycnometer until the mark using a pipette.
Slowly insert the capillary stopper while making sure that there are no spaces inside
the capillary space.
4. Place again the pycnometer in the water bath and allow an additional 5 minutes for
the mixture to reach the temperature of the water bath.

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5. Dry the outside of the pycnometer. Handle the pycnometer by the neck with one or
two layers of paper between the fingers and the bottle.
6. Weigh and record the mass of the pycnometer with the mixture.
7. Empty the pycnometer and repeat procedure C3 -C6 to do 2 more trials for that same
mixture.
8. Repeat procedure C3-C7 for the rest of the mixtures.
9. Clean all glassware and dispose your waste in the appropriate waste jar.

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 DATA TABLES
Name:______________________________________________Date:_________________
Section:___________________________________Group Name:____________________

Pre-Determined Data

Water Methanol
Density (g/mL) 1 0.7808

Molecular 18 32
Weight (g/mol)

Solution Preparation
Mixture Volume Methanol (mL) Volume Water (mL)

A 0
50

B 16.20 33.80

C 24.47 25.53

D 29.49 20.51

E 32.86 17.14

F
0
50

Part A. Pressure & Temperature Readings

Wet Bulb Temperature(deg 𝐶)

Trial 1 Trial 2 Trial 3

25 23 23

Room Pressure = 101 KPa

Room Temperature = 27 deg C

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Part B. Mole Fraction Recalculation Data

Mixture Mass of Empty Mass of Volumetric Mass of Volumetric

Volumetric Flask (g) Flask with Methanol Flask with Methanol
(g) & Water (g)

A 33.4010 33.401 83.0539

B 36.0833 48.7235 83.2949

C 36.6659 55.772 82.5269

D 39.6127 62.4251 84.552

E 37.185 62.8402 81.357

F 36.8307 75.8737 75.8737

Water Bath Temperature = 28.5 deg C

Part C. Experiment Proper

Mass of Dry Pycnometer

Mixture Mass of Dry Pycnometer (g)

Trial 1 Trial 2 Trial 3
A 14.5318 14.5323 14.5319

B 15.032 15.0318 15.0319

C 14.5670 14.5672 14.5673

D 14.6430 14.6438 14.6435

E 15.2360 15.2358 15.2344

F 15.4569 15.4567 14.456

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 Mass of Pycnometer w/ Mixture

Mixture Mass of pycnometer w/ Mixture (g)

Trial 1 Trial 2 Trial 3
A 39.8055 39.8056 39.8055

B 39.0543 39.0542 39.0543

C 37.6695 37.6698 37.6697

D 37.7533 37.7519 37.7553

E 38.003 38.042 38.0500

F 35.0642 35.0643 35.0647

Part D. Additional Data

Mass of Pycnometer w/ Water

Mixture Mass of pycnometer w/ water (g)

Trial 1 Trial 2 Trial 3
A 39.5135 39.0425 39.8606
B 40.5386 39.6686 39.7563
C 39.567 39.2551 40.0499
D 40.1135 39.6405 39.1573
E 39.6863 39.5401 39.5966
F 39.892 39.1891 39.63754

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GUIDE QUESTIONS
Note: In writing your formal report, you must still find references for discussion points
that are related to the answers given below. These are just shown to serve as a guide for
understanding the experiment.

1. How is the volume of the pycnometer determined? How will the wet bulb temperature
data be used in accomplishing this?

The volume of the pycnometer is usually assumed to be constant. But the wet bulb
temperature is used to correct the volume of the pycnometer using the formula 𝑉𝑝𝑦𝑐 =
(𝑚𝑝𝑦𝑐+𝑤𝑎𝑡𝑒𝑟 − 𝑚𝑒𝑚𝑝𝑡𝑦 𝑝𝑦𝑐(𝑝𝑦𝑐+𝑎𝑖𝑟) )/(𝜌𝑤𝑎𝑡𝑒𝑟 − 𝜌𝑎𝑖𝑟 )where the density of air is determined
using the wet bulb temperature.

2. What is the significance of partial molar properties?

Partial molar properties are significant because they are the properties of the individual
components of a mixture when they are in the mixture. Please refer to other references.

3. What are the sources of error in the experiment?

Because the experiment involves a small range of data involving small differences
between data points, it is very important to maintain the accuracy of the data. Sources
of error would include measuring the pycnometer when it is wet. Another would be not
completely filling the pycnometer. Another one would be not bringing the temperature of
the solution inside the pycnometer to the solution of the temperature bath (thermal
equilibrium is not reached). Another one would be not correcting the volume of the
pycnometer.