University of San Carlos

Department of Chemical Engineering

CHE 3214L Chemical Engineering Laboratory Investigations 1

Data Processing & Analysis Report

(Form CHE 3214L-3)

Prepared and submitted by:

JOHN FRITZ V. FESTEJO RIKA B. GUNJI JUN PAUL R. MAYORMITA

Experiment : Partial Molar Volume of Ethanol and Water in Solutions

Objectives of the Experiment

To determine the partial molar volume of ethanol and water in solutions by density measurement using a
pycnometer.

Results & Discussion

Objective 1: To determine the partial molar volume of ethanol and water in solutions by density
measurement using a pycnometer.

The volume produced when liquids are combined to yield a particular solution concentration is
different from the sum of the liquid volumes added. When a species is added to a solution at a constant
temperature, pressure, and other species compositions, how much the volume of the solution changes
depends on the partial molar volume of that species in the solution.

The volume that each component contributes to the mixture's total volume is known as partial
molar volume. Even though the molar volume can only be positive, the partial molar volume may be either
positive or negative. As the composition of a binary mixture changes as a result of changes in the
immediate surroundings around molecules of component 1, the partial molar quantities of component 1 in
the binary mixture will change. As a result, the intermolecular interactions between molecules shift,
changing the partial molar volumes.

The total volume measured following the combination of two real liquids, such as ethanol and
water, differs from the total volume assumed from the individual volumes of the two liquids due to
intermolecular interactions. One generates partial molar quantities that depend on the system's composition
to explain this non-ideal behavior during the mixing phase. These values can be calculated from
experimental data.

1
 In this experiment, a plot of molar volume versus molar compositions is developed using
experimental mass and density data in order to determine the values for the derivative components in
equations (1) and (2) to obtain the partial molar volumes of ethanol and water.

𝑑𝑉
𝑉1 = 𝑉𝑚 + 𝑥2 𝑑𝑥1
(1)

𝑑𝑉
𝑉2 = 𝑉𝑚 − 𝑥1 𝑑𝑥1
(2)

To create a plot of the partial molar volume versus mole fraction, thirteen (13) different solutions
with varied ethanol mole fractions were examined. The computed partial molar concentrations of ethanol
and water are then compared to theoretical values.

Using the masses of ethanol and water prepared in the volumetric flasks, the mole fraction of
ethanol for each solution was recalculated. The recalculated mole fractions and the theoretical values are
presented in Table 1. Each recalculated mole fraction value deviates significantly from its corresponding
theoretical value. This could occur for a variety of errors in the experiment.

Table 1. Theoretical Values and Recalculated Mole Fractions of Ethanol

Theoretical Mole Fraction Recalculated Mole Fraction

0.00 0.00

0.03 0.0120

0.06 0.0245

0.09 0.0372

0.12 0.0506

0.15 0.0645

0.18 0.0790

0.21 0.0941

0.24 0.1098

0.40 0.2064

0.60 0.3695

0.80 0.6098

1.0 1.00

2
 The densities of the solution were determined by subtracting the mass of the pycnometer from the
recorded mass of the solution with the pycnometer. Table 2 shows the mass of the solution in the
pycnometer and their equivalent densities.

Table 2. Mass of the Water-Ethanol Solution and Their Densities

Mole Fraction of Mass of the Solution Density of the Volume of the solution
Ethanol (g) Solution (g/mL) (mL)

0.00 50.0479 1.0010 99.915

0.03 49.7935 00.9959 100.4586

0.06 49.4959 .9899 101.0744

0.09 49.3530 0.9871 101.3648

0.12 49.0726 0.9815 101.9592

0.15 48.8687 0.9774 102.3998

0.18 48.6516 0.9730 102.8226

0.21 48.4558 0.9691 103.221

0.24 48.1996 0.9640 103.7748

0.40 46.6984 0.9340 107.1594

0.60 44.4398 0.8888 112.5454

0.80 42.0732 0.8415 118.8444

1.0 39.3837 0.7877 126.9942

It can be observed that as the mass of solution increases, the density of the solution also
increases. However, when compared to the mole composition of ethanol in the solution, as the mole
composition increases, the mass, as well as the density of the solution, decreases. Subsequently, the
volume of the solution was determined by using the measured mass of the solution and calculated density
of the solution. In contrast to the mass and density of the solution, it can be seen that the volume of the
solution increases as the mole composition of the ethanol increases as well.

From the values in Table 2, we can also distinguish that the density of the solution deviates from
that of water (1 g/mL) and approaches that of ethanol (0.789 g/mL) when the concentration of ethanol in the
solution increases. This exemplifies the idea that each of a solution's constituent species contributes to its
properties, with the amount of each species's contribution varying depending on the presence of the other
species.

3
 A. Experimental Determination of the Partial Molar Volume Ethanol (1) - Water (2) Mixture
through Graphical Methods

As can be seen in Figure 1, a plot of the molar volume (mL/mol) versus the mole fraction of ethanol
in the solution (xethanol) was generated. The molar volume can be calculated by using the mole fractions and
molecular weight of the substance, and the density of the solution, or by using the average molecular
weight of solution, and its density.

Figure 1. Molar Volume of Solution versus Mole Fraction of Ethanol

It can be distinguished that as the concentration of ethanol in the solution increases, the molar
volume approaches 58.4887. Whereas, when the concentration of ethanol nears zero, the molar volume of
the solution approaches that of pure liquid water (18.02 mL/mol), which is approximately 18.0028 mL/mol].

The partial molar volume of the binary mixtures was determined by taking the quadratic equation
of the best fit curve of the molar volume graph and substituted on to equations (1) and (2), and are listed
below as such.

Table 3. Partial Molar Volume Obtained Through Graphical Methods

Partial Molar Volume (mL/mol)
Mole Fraction of Ethanol
Ethanol Water

0.00 54.105 17.946

0.0120 54.21043 17.94536

0.0245 54.31889 17.94335

4
 0.0372 54.42768 17.93988

0.0506 54.54092 17.93469

0.0645 54.6567 17.92761

0.0790 54.77567 17.91842

0.0941 54.89758 17.90687

0.1098 55.0222 17.89272

0.2064 55.74102 17.75773

0.3695 56.76749 17.34263

0.6098 57.85143 16.30266

1.00 58.5243 13.5267

The plot of the partial molar volume of ethanol-water solution obtained though graphical method is
presented in Figure 3.

Figure 3. Partial Molar Volume of Ethanol (1) - Water (2) Mixture Through Graphical Method

The partial molar volume obtained when the components were mixed was found to be less than the
molar volume of the pure components. This is the consequence of the ordering effect of solvation, which
tends to decrease the volume of the solvent. The interactions between the molecules of ethanol and water

5
had an impact on the solution's volume reduction as well. The contraction that occurred when water and
ethanol were combined was also indirectly related to the partial molar amounts of each substance. The
differences in the intermolecular forces' behavior when the two components are mixed and when they are
pure substances caused the partial molar volume to differ from the molar volume of the components when
they were considered separately. The partial volumes of each component could display a different trend for
the partial molar volumes of each component in the concentrated solutions due to the fact that it varies with
composition (the greater the contribution).

The experimental results may be found to be reasonably consistent with the theoretical values
(Figure 6).

B. Analytical Method for the Experimental Determination of the Partial Molar Volume of the
Ethanol - Water Mixing

For any component or substance in a binary mixture, the partial molar volume of a substance is
defined by the equations,

δ(∆𝑚𝑖𝑥𝑉𝑢
𝑉1 = ∆𝑚𝑖𝑥𝑉𝑚 + 𝑥2 δ𝑥1
+ 𝑉𝑚.1 (3)
δ(∆𝑚𝑖𝑥𝑉𝑢
𝑉2 = ∆𝑚𝑖𝑥𝑉𝑚 − 𝑥1 δ𝑥1
+ 𝑉𝑚.2 (4)

Redlich-Kister Equation,
𝑛
𝑖
∆𝑚𝑖𝑥 𝑉𝑚 = 𝑥1𝑥2 ∑ 𝑎𝑖(𝑥1 − 𝑥2) (5)
𝑖=0

Utilizing the Redlich-Kister Equation, a predicted value for the molar volume of mixing is
determined, as opposed to the molar volume of mixing obtained from the molar volume and mole fraction of
the substances, with the help of MS Excel and Solver function, the square of the residuals was minimized
to provide the optimal values for the parameters used in the equation.Figure 4 portrays the change in the
molar volume of mixing. Compared to the calculated molar volume of mixing, it is not far off from what was
predicted using the Redlich-Kister Equation.

Table 4. Change in Molar Volume of Mixing of Solution

Molar Volume of Mixing
Mole Fraction of Percent Error
Ethanol Calculated Predicted (%)
[Vm - (x1Vm.1 + x2Vm.2)] (Redlich-Kister Equation)

0.00 0 0 0

0.0120 0.762979 0.760651 0.306

0.0245 1.547363 1.5408184 0.425

0.0372 2.325456 2.3203488 0.220

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 0.0506 3.136893 3.1280675 0.282

0.0645 3.956594 3.9494017 0.182

0.0790 4.792522 4.7877114 0.101

0.0941 5.637565 5.6400462 0.044

0.1098 6.498351 6.5032185 0.075

0.2064 11.2397 11.25664 0.151

0.3695 16.79909 16.788496 0.063

0.6098 18.1222 18.124636 0.014

1.00 0 0 0

Figures 4a and 4b is a scatter plot of the calculated and predicted molar volume of mixing versus
the molar fraction of ethanol.

Figure 4a. Calculated Molar Volume of Mixing

7
 Figure 4b. Predicted Molar Volume of Mixing against the Mole fraction of Ethanol

It is observed that both graphs are similar in shape and magnitude, with minute differences in the
polynomial equation for the best fit curve. However, both graphs exhibit strong correlation as depicted by
the Pearson's correlation coefficient which has a high value of 0.997 for both graphs.

The expansion of the Redlich - Kister Expansion provides an expression for the partial derivative of
the molar volume of mixing with respect to the mole fraction of ethanol which can be subsequently
substituted to equations 3 and 4 to obtain the partial molar volume of both components.

Table 5. Determination of Partial Molar Volume of Mixture through Analytical Methods

Partial Molar Volume
Mole Fraction of Ethanol
Ethanol Water

0.00 63.85492 18.002

0.0120 63.4762 17.88272

0.0245 63.07054 17.78198

0.0372 62.6422 17.63315

0.0506 62.18233 17.5379

0.0645 61.68966 17.4255

0.0790 61.16422 17.32975

8
 0.0941 60.60298 17.24029

0.1098 60.01431 17.19069

0.2064 56.30253 17.50011

0.3695 50.60755 20.97644

0.6098 46.38306 34.4922

1.00 58.48673 80.78025

The graph of the partial molar volume of the Ethanol-Water mixture against the molar fraction of
ethanol is plotted below in Figure 5.

Figure 5. Partial Molar Volume of Ethanol-Water Mixture through Analytical Methods

Compared to Figure 3, where the partial molar volumes were determined through graphical
methods, Figure 5 exhibits a much different trend and exhibits a totally different behavior for the partial
molar volume of ethanol and water than that of Figure 3, and what was expected by the theoretical value
and partial molar volume graph of the ethanol-water mixture at 25 degrees Centigrade as shown in Figure
6.

9
Figure 6. Theoretical Values of Partial Molar Volumes of Water and Ethanol in a Solution at 25 °C (298 K)
and 1 atm (water on the left, ethanol on the right)
Source: Atkins P., de Paula J., and Keeler, J. 2018. Physical Chemistry. 11th ed. Oxford: Oxford University
Press.

Moreover, fluid quantities, like liquids and gases, are not always additive. Alcohol and water are
polar liquids. This implies that the molecules in both liquids are fundamentally neutral but have two ends
that carry a small electric charge: one positive and one negative. The reason for this is that the covalent
bond has an unbalanced distribution of electrons, which causes a slight polarization of the negatively
charged electrons. The water electrons are usually closer to the oxygen atom than the region around the
hydrogen atoms. A negative pole forms close to the oxygen, while a positive pole forms close to the
hydrogens.

Depending on the charges and hydrogen bonds they carry, they arrange themselves into
intermolecular lattices. These liquids do not form lattices that preserve space due to the requisite forms of
these lattices. Hence, there are spaces between the molecules. Due to the electrostatic attraction between
the poles of two polar types of molecules, when two liquids are polar, the molecules of one liquid can slip
between the molecules of the other and form hydrogen bonds. When ethanol and water are mixed, ethanol
can slip through the space that water leaves behind because its molecules are smaller than those of water.
They can execute this because they mix easily because they are both polar. The resulting intermolecular
lattice of the two liquids can be more efficiently organized to conserve space because the molecules in the
two liquids have different sizes. The total molar volume is decreased as alcohol molecules slip into the
gaps between the water molecules. The combined liquid's volume reduces as the molecules grow more
compact as the ethanol molecules slip in the water molecules.

Additionally, the hydrogen bond forms between the molecules of ethanol and water. Hydrogen
bonds can be formed by the ethanol molecules' -OH groups. The molecules draw closer to one another as
hydrogen bonds form, and the volume is lesser than expected.

10
Possible Sources of Anomalies in the Experiment

Due to instrument limitations and material loss caused by the volatilization of the ethanol-water
mixture, there were variations in the results. Any of these errors could have an influence on how accurate
the findings are. As it is assumed that the moles of ethanol and water in the liquid mixture remained
constant for the duration of the experiment, the material loss would have the greatest influence on the
experiment's accuracy.

If some of the solutions adhered to the interior and external surfaces of the pycnometer, the
measured masses and, subsequently, the solution densities may be altered. If the pycnometer had not
been fully cleaned and dried before use, the analytical balance would read inaccurately for the sample
mass and solution density. Moreover, water vapor may condense on the surface of the pycnometer if the
solutions were at a lower temperature and the surrounding air was humid.

Despite the fact that the temperature in the experiment remained constant (𝑇 = 31°𝐶)The
theoretical values of the partial molar volumes were maintained at a temperature of 25°C. When water is
subjected to high temperature, it expands, thus there will be an increase in volume. When water increases
in volume, it becomes less dense. It would be better to follow the maintained temperature in the theoretical
values. This may be replicated by employing a constant temperature bath.

Conclusions

The partial molar volumes of ethanol and water at different concentrations, with the mixture of
ethanol-water solution were established using the pycnometer to acquire the density. By acquiring the
density, we were able to determine the molar volume of the different concentrations of ethanol-water
solution. The partial molar volume obtained when the components were mixed was found to be less than
the molar volume of the pure components. This results from the ordering effect of solvation, which is an
interaction of a solute with the solvent that leads to the stabilization of the solute species in the solution,
which tends to reduce the volume of the solvent. With the difference of the behavior of the intermolecular
forces between ethanol and water, the calculated partial molar volumes were not equal to the molar
volumes of the particular components. The experiment has proven that the volume property is not additive.
Due to the fact that it varies with composition, the larger the contribution, the partial volumes of each
component may show a different trend than the molar volumes of each component.

11
 References

Chem LibreTexts. (2023, January 30). Introduction to Non-ideal Solutions. Chemistry LibreTexts.
https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/Sup
plemental_Modules_(Physical_and_Theoretical_Chemistry)/Physical_Properties_of_Matter/Solution
s_and_Mixtures/Nonideal_Solutions/Introduction_to_Non-ideal_Solutions#:~:text=Non%2Dideal%2
0solutions%20are%20identified,molecules%20in%20that%20particular%20solution.

Hynĉica, P., Hnědkovský, L. Cibulka, I. Partial Molar Volumes of Organic Solutes in Water. XII. Methanol
(aq), Ethanol (aq), 1 Propanol (aq) and 2-propanol (aq) at T = 298-573 K and at Pressures Up to 30
MPa. Journal of Chemical Thermodynamics

Petek, A., Pecar, D. & Dolecek, V. (2001). Volumetric Properties of Ethanol-Water Mixtures Under High
Pressure. Acta Chim. Slov., 48, 317-324. Retrieved from http://acta-arhiv.chem-soc.si/48/48-3-317.pdf

Sandler SI. (2017). Chemical and Engineering Thermodynamics. 5th ed. New York: John Wiley & Sons,
Inc.

Smith, J.M., Van Ness, H.C., and Abbott, M. M. (2005). Introduction to Chemical Engineering
Thermodynamics . 7th ed. New York: McGraw-Hill.

Tan ML, Miller BT, Te J, Cendagorta JR, Brooks BR, Ichiye T. (2015, February 14). Hydrophobic hydration
and the anomalous partial molar volumes in ethanol-water mixtures. J Chem Phys. doi:
10.1063/1.4906750. PMID: 25681917; PMCID: PMC5848694.

12
 ANNEX 1: Raw Data

Table 1. Preparation of the Solutions By Volume

Density Ethanol: 789 kg/m3 Molecular Weight EtOH: 46.07
g/mol

Density Water: 997 kg/m3 Molecular Weight H2O: 18.02

g/mol

Mol Fraction of Ethanol Calculated Volume (mL)

Ethanol Water

0.00 — 200.00

0.03 18.168 181.832

0.06 34.191 165.809

0.09 48.428 151.572

0.12 61.163 138.837

0.15 72.620 127.380

0.18 82.983 117.017

0.21 92.402 107.598

0.24 101.00 99.00

0.40 136.583 63.417

0.60 165.788 34.212

0.80 185.635 14.365

1.00 200.00 —

Total Mass of Solution: 100g

Table 2. Preparation of the Solutions By Mass
Mol Fraction of Calculated Mass Measured Mass

13
 Ethanol Ethanol Water Ethanol Water

0.00 — 199.4 100.0107

0.03 14.334 181.286 3.0065 97.0371

0.06 26.977 165.312 6.0345 94.0209

0.09 38.21 151.117 9.0023 91.0508

0.12 48.257 138.42 12.0012 88.0668

0.15 57.297 126.993 15.0086 85.0742

0.18 65.474 116.666 18.0006 82.049

0.21 72.905 107.276 21.0091 79.0240

0.24 79.688 98.704 23.9996 76.0384

0.40 107.764 63.226 39.9933 60.0900

0.60 130.807 34.109 60.0136 40.0163

0.80 146.46 14.32 79.999 20.0042

1.00 157.8 — 100.03 0

Table 3. Determination of Density Using the Pycnometer

Mass of the Dry 32.0316 g
Pycnometer

Volume of the 50 mL
Pycnometer (mL)

Mole Fraction of Mass of the Pycnometer with Temperature (°C)

Ethanol Solution (g)

Trial 1 Trial 2 Trial 1 Trial 2

1.0 71.4396 71.3910 31 °C 31 °C

0.8 74.1022 74.1073 31 °C 31 °C

0.6 76.4713 76.4715 31 °C 31 °C

0.4 78.7308 78.7291 31 °C 31 °C

14
 0.24 80.2320 80.2303 31 °C 31 °C

0.21 80.4880 80.4868 31 °C 31 °C

0.18 80.6835 80.6828 31 °C 31 °C

0.15 80.9015 80.8990 31 °C 31 °C

0.12 81.1045 81.1038 31 °C 31 °C

0.09 81.3857 81.3835 31 °C 31 °C

0.06 81.5295 81.5255 31 °C 31 °C

0.03 81.8262 81.8239 31 °C 31 °C

0.00 82.0799 82.0791 31 °C 31 °C

Table 4. Observations During the Actual Conduct of Experiment

Determination of Density Using the ● The temperature remained constant throughout the
Pycnometer experiment.
● The smaller the mole fraction of the ethanol in water,
the larger the corresponding mass.

15
16
17
 ANNEX 2: Processing of Data
`
Table 1. Preparation of Solutions by Mass

Table 2. Experimental Values

18
Table 3. Processed Data
Moles (mol) Recalculated mol. frac Avg.
Density Volume of
Molecular
of Soln Soln Ethanol Water Solution Ethanol Water weight

1.001 99.915 0 5.55 5.55 0 1 18.02

0.9959 100.4586 0.0652 5.385 5.4502 0.012 0.988 18.35553

0.9899 101.0744 0.1309 5.2176 5.3484 0.0245 0.9755 18.70627

0.9871 101.3648 0.1952 5.0528 5.248 0.0372 0.9628 19.06338

0.9815 101.9592 0.2602 4.8872 5.1474 0.0506 0.9494 19.43813

0.9774 102.3998 0.3255 4.7211 5.0466 0.0645 0.9355 19.82895

0.973 102.8226 0.3903 4.5532 4.9436 0.079 0.921 20.23477

0.9691 103.221 0.4556 4.3853 4.8409 0.0941 0.9059 20.65973

0.964 103.7748 0.5204 4.2197 4.7401 0.1098 0.8902 21.09963

19
 Moles (mol) Recalculated mol. frac Avg.
Density Volume of
Molecular
of Soln Soln Ethanol Water Solution Ethanol Water weight

0.934 107.1594 0.8672 3.3346 4.2019 0.2064 0.7936 23.8093

0.8888 112.5454 1.3014 2.2207 3.522 0.3695 0.6305 28.38426

0.8415 118.8444 1.7347 1.1101 2.8448 0.6098 0.3902 35.12436

0.7877 126.9942 2.1691 0 2.1691 1 0 46.07

Table 4. More Processed Data

Molar Volume Partial Molar Volume

Ethanol Water Total Ethanol Water

0 18.002 18.00200 54.105 17.946

0.555116 17.87706 18.43217 54.21043 17.94536

1.140231 17.75786 18.89810 54.31889 17.94335

1.736201 17.57639 19.31259 54.42768 17.93988

2.375081 17.43066 19.80574 54.54092 17.93469

3.040224 17.2475 20.28773 54.6567 17.92761

3.740524 17.05696 20.79748 54.77567 17.91842

4.473416 16.84482 21.31824 54.89758 17.90687

5.247392 16.64046 21.88785 55.0222 17.89272

10.18078 15.31121 25.49199 55.74102 17.75773

19.15264 12.78309 31.93573 56.76749 17.34263

33.38501 8.355798 41.74081 57.85143 16.30266

58.48673 0 58.48673 58.5243 13.5267

Table 5. Redlich-Kister Equation

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21
Table 6. Partial Molar Volume Determination through Analytical Methods

22