CHEM 347

PHYSICAL CHEMISTRY LABORATORY

Experiment 3: Determination of Partial Molar Quantities

Yaren Karakoç

Student ID Number: 2019206204

Partners: Barış Kamilçelebi

Section 2, Group 2

Experiment Date: 14.11.2024

Submission Date: 21.11.2024

1
Introduction

Properties such as volume, internal energy, and Gibbs free energy are dependent on the amount of substance while others
such as temperature, density, colour of a substance do not depend on the amount of it. The first type of properties is called
extensive while the latter is called intensive (Redlich, 1970). For example, heat capacity is extensive because it is altered
when there is more or less substance whereas, specific properties exemplified by specific volume or specific internal energy
are constant over any amount, therefore intensive properties (Silverman, 2021). Another concept in thermodynamics is state
functions which are properties of a system independent of the path taken and are described only by the final and initial states
of the system (Xu et al., 2022). Examples to state functions are volume, energy and entropy of a system (Constales et al.,
2017). Volume, being an extensive state function, can be expressed as partial molar volume. Partial molar volume of a
component in a solution is the change in the volume of the homogeneous mixture upon addition of one mole of the
mentioned component to a large volume of the mixture (Stephanos and Addison, 2023). Followingly, volume is not an
additive property: volume of a substance is dependent on the surrounding molecules and the interactions between the
molecule of that substance and the neighbouring molecules (Lepori and Gianni, 2000). For example, the molar volume of
water is 18cm3mol-1 meaning one mole of water in a pure water sample occupies 18cm3 space whereas one mole of water in a
solution of water with another liquid occupies a different volume (defined as the partial molar volume) either less or more
than 18cm3 dictated by the interactions between molecules in the solution, temperature and pressure (Bahadur et al., 2015).

For a binary mixture of a and b, partial molar volume of a (V¯a) at constant temperature (T) and pressure (P) is expressed by
this equation (Danek, 2006):
∂V
V¯a = ( ) (1)
∂na T,P,nb

In Equation 1, na is the moles of component a. Correspondingly, the volume of the system is:

V = na . V¯a + nb . V¯b (2)

For a 1 mole solution, Equation 2 can be rearranged in mole fractions such as:

V = V¯ = xa . V¯a + xb . V¯b (3)

Since xa + xb = 1, xa = 1-xb:

V = V¯ = (1-xb) . V¯a + xb . V¯b = V¯a - xb . V¯a + xb . V¯b = V¯a + xb . (V¯b - V¯a) (4)

For a 1 mole solution, in Equation 3, if partial derivatives of both sides with respect to xb are taken considering that dxa = -
dxb since xa + xb = 1:
∂V
( ) = V¯b - V¯a (5)
∂xb T,P

If Equation 5 is plugged into Equation 4 and equation is rearranged to leave partial molar volume of a alone, the following
expression is obtained:
∂V ∂V
V¯a = V¯ – xb . ( ) → V¯ = V¯a + xb . ( ) (6)
∂xb T,P ∂xb T,P

Similarly, if partial derivative is taken with respect to xa and plugged in, an expression for partial molar volume of b can be
obtained:
∂V ∂V
V¯b = V¯ – xa . ( ) → V¯ = V¯b + xa . ( ) (7)
∂xa T,P ∂xa T,P

Equations 6 and 7 hints at how partial molar volumes of components in a binary mixture can be calculated. If densities of
mixtures of different compositions are known, then molar volume change with respect to composition (e.g. mole fraction of
b) can be plotted. The graph can be implemented in the following way: V¯a and V¯b at a certain composition are y-intercepts
of the tangent line to molar volume-xb graph at that specific composition for xb = 0 and xb = 1 respectively (Danek, 2006).

The aim of this experiment is to determine the graphs partial molar volume of water against mole fraction of water and partial
molar volume of ethanol against mole fraction of ethanol in ethanol-water binary mixtures and investigate the additivity of
volume utilizing ethanol-water mixtures of different ethanol weight percents. The method to find the partial molar volumes of
water and ethanol with respect to their mole fractions is similar to the described method. Densities of different compositions
of solutions are utilized to obtain a graph of specific volume versus ethanol weight percent which serves the same purpose as
a molar volume versus mole fraction graph. The y-intercepts of the tangent lines to the graph are further implemented to
obtain the partial molar volumes. The partial molar volumes of water and ethanol are expected to decrease as their mole
fractions decrease because as more of the environment comprises of the partner liquid, the added mole of solute fills into the
spaces between the partner liquid in the binary mixture more tightly than it would be in its pure form (Atkins, 2006). Since
the volume is assumed to be additive, error between Vexpected and Vcalculated is anticipated.

2
Methodology

Glassware and Materials

• Laboratory Balance ±0.01g • Beakers • Tissue

• Pycnometer • Distilled Water • Pasteur Pipettes
• Weighing Bottles • Ethanol

Procedure

1. Roughly 25mL ethanol and water solutions with 20%, 40%, 60%, 80% ethanol weight percent were prepared by
weighing correct amount of ethanol and water. Required masses of water and ethanol were calculated beforehand. These
calculated values are presented in Table 1 and calculations are explained in Calculations section.
2. Solutions were mixed by shaking and inverting to generate homogenous ethanol-water solutions.
3. Pycnometer was dried thoroughly with tissues and its empty weight was measured.
4. The pycnometer was filled to the brim with 100% ethanol. It was let to overflow to mitigate any air bubbles trapped
inside and at top of the capillary lid. The outside was wiped and dried with tissue.
5. Pycnometer with ethanol inside was weighed.
6. Ethanol was decanted. Pycnometer was dried again detailly. It was filled to the brim with 100% distilled water. The
outside was dried with tissue.
7. Pycnometer with water inside was weighed.
8. Distilled water was decanted. Pycnometer was dried with tissue. It was filled with ethanol-water solutions and weighed
like in steps 4-5. 20%, 40%, 60%, 80% ethanol solutions were weighed respectively. Between each measurement, the
pycnometer was rinsed with solution to be weighed to remove residual previous solution.
9. Calculations are done to find densities of solution, partial molar volume graphs of water and ethanol. Detailed
explanations of calculations are given in the Calculations section.

Table 1. Calculated masses of ethanol and distilled water in different ethanol-water solutions.

Calculated Mass Values / g±0.01

Weight Percent of Ethanol / % Mass of Ethanol / g±0.01 Mass of Water / g±0.01
20 4.73836496321596 18.95345985286380
40 9.02960741803234 13.54441112704850
60 12.93416312933890 8.62277541955929
80 16.50204562460140 4.12551140615035

Results

In the experiment, the volume of the pycnometer must be calculated for further calculations. For this purpose, the pycnometer
was weighed empty. Then, it was filled with ethanol and weighed. Continuously, it was filled with water and weighed. The
mass values are presented in Table 2.

Table 2. Mass of empty pycnometer and pycnometer filled with ethanol and distilled water.

Material Mass / g±0.01

Empty Pycnometer 19.78
Pycnometer + Ethanol 27.96
Pycnometer + Water 29.79

Calculated amounts of ethanol and water (Table 1) were weighed to prepare solutions of ethanol and water of 20%, 40%,
60%, 80% ethanol weight percent. The weighed amounts are given in Table 3.

3
Table 3. The masses of ethanol and water weighed to prepare ethanol-water solutions of different concentrations (ethanol
weight percent).

Measured Mass Values / g±0.01

Weight Percent of Ethanol / % Mass of Ethanol / g±0.01 Mass of Water / g±0.01
20 4.74 18.94
40 9.03 13.55
60 12.92 8.62
80 16.50 4.13

Lastly, pycnometer was filled with 20%, 40%, 60%, 80% ethanol weight percent solutions respectively, and it was weighed.
These values are presented in Table 4.

Table 4. Mass of pycnometer filled with different ethanol weight percent solutions.

Weight Percent of Ethanol / % Mass of Pycnometer + Solution / g±0.01

20 29.51
40 29.24
60 28.84
80 28.43

Calculations

To obtain the specific volume (1/d) of ethanol-water solutions, the mass and the volume of the pycnometer was measured.
This was achieved by filling the pycnometer with pure ethanol and pure water, weighing them, subtracting the pycnometer
tare, finding the volume values to average from the density of ethanol and water.

The calculations for ethanol to represent the operations are as follows:

The mass of empty pycnometer from Table 1 = 19.78 g

The mass of pycnometer filled with ethanol from Table 1 = 27.96 g

The mass of ethanol = 27.96 g – 19.78 g = 8.18 g

Density of ethanol (NCBI, 2024) = 0.791 g/mL

Density of water (NCBI, 2024) = 0.997044 g/mL

density = mass / volume (8)

volume = mass / density (9)

Volume of pycnometer (ethanol) = massethanol / densityethanol = 8.18 g / 0.791 g/mL = 10.3413400758533 mL ≈ 10.3413 mL

By the same calculations, the volume of pycnometer measured via water is found approximately 10.0397 mL (Table 5). Then,
taking average of these values, the volume of pycnometer is found:

(10.3413400758533 mL + 10.0396772860576 mL) / 2 = 10.1905086809555 mL ≈ 10.1905 mL

Table 5. Calculations for pycnometer volume.

Mass / Mass of Liquid / Volume of Pycnometer Average Volume of

Material
g±0.01 g±0.01 / mL Pycnometer / mL
Pycnometer + Ethanol 27.96 8.18 10.3413*
10.1905*
Pycnometer + Water 29.79 10.01 10.0397*
*Values are given rounded off to 4 significant figures after the decimal point. In further calculation, exact values are used.
For exact values, please refer to the supplementary Excel file.

4
The 20%, 40%, 60%, 80% (w/w) ethanol solution were prepared by measuring the corresponding mass of ethanol and water
to obtain a hypothetical volume of 25mL of total solution. This value is hypothetical because it assumes that volume is
additive, and one of the experiment’s objectives is to investigate if volume is additive or not. Masses of ethanol and water to
be mixed were calculated. The calculated values are presented in Table 1 in Methodology section because they were done
prior to experiment and included in the preparations. The calculations done for 20% (w/w) ethanol solution are given below
to represent the logic behind the calculations:

Volumewater + Volumeethanol = 25mL

Since 20% ethanol solution is 20% ethanol, 80% water by weight:

masswater / massethanol = 80/20 = 4

masswater = 4 * massethanol

From the Equation 8:” density = mass / volume” and therefore: “volume = mass / density”

Volumewater + Volumeethanol = 25mL = masswater / densitywater + massethanol / densityethanol = 25 mL

If 4 * massethanol is plugged in for masswater and density values are plugged in:

4 * massethanol / 0.997044 g/mL + massethanol / 0.791 g/mL = 25 mL

4 * 0.791 g/mL * massethanol + 0.997044 g/mL * massethanol = 25mL * 0.997044 g/mL * 0.791 g/mL

3.164 g/mL * massethanol + 0.997044 g/mL * massethanol = 19.7165451 g2/mL

4.161044 g/mL * massethanol = 19.7165451 g2/mL

massethanol = 19.7165451 g2/mL / 4.161044 g/mL

Mass of ethanol in mixture = massethanol = 4.7383649632 g

Mass of water in mixture = masswater = 4 * massethanol = 4 * 4.7383649632 g = 18.9534598529 g

The measured values to prepare the solutions were done as close as possible to the calculated values and they are given in
Table 3 in Results section. After the solutions are prepared, the pycnometer was filled with each solution, and they were
weighed. From Results, the mass of the empty pycnometer was 19.78 g. The mass of the pycnometer was subtracted from
each value mass value and mass of the solution was found. The masses are given in Table 6. As an example:

Mass of the pycnometer with 20 % ethanol solution inside = 29.51 g (Table 6)

Mass of the empty pycnometer = 19.78 g (Table 2)

Mass of the 20% ethanol solution = 29.51 g – 19.78 g = 9.73 g (Table 6)

Table 6. Mass of the pycnometer with solutions inside and tared mass of each solution for different solutions.

Weight Percent of Ethanol / % Mass of Pycnometer + Solution / g±0.01 Mass of Solution / g±0.01
20 29.51 9.73
40 29.24 9.46
60 28.84 9.06
80 28.43 8.65

The volume of the pycnometer was calculated as approximately 10.1905mL (Table 5). Densities of the ethanol-water
solutions are found by diving the mass values in Table 6 to approximately 10.1905mL. By taking the reciprocal of density,
the specific volumes of the solutions were found. Also, the specific volumes of 0% ethanol which is 100% distilled water, and
100% ethanol were found by taking reciprocal of 0.997044 g/mL for water and 0.791 g/mL for ethanol. A representative
calculation for 20% ethanol solution and 0% ethanol solution is as follows:

Density of 20% ethanol solution = mass / Volume = 9.73 g / 10.1905086809555 = 0.95481004 g/mL

Specific volume of 20% ethanol solution = 1/density = 1 / 0.95481004 g/mL = 1.047328744 mL/ g ≈ 1.0473 mL/g

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Specific volume of 0% ethanol (100% distilled water) = 1 / densitywater = 1 / 0.997044 g/mL = 1.002964764 mL/g ≈ 1.0030
mL/g

Table 7. Specific volumes and densities of different ethanol weight percent ethanol-water solutions.

Weight Percent of Ethanol / % Specific Volume* / mL/g Density* / g/mL

0 1.0030 0.9970
20 1.0473 0.9548
40 1.0772 0.9283
60 1.1248 0.8891
80 1.1781 0.8488
100 1.2642 0.7910
*Values are given rounded off to 4 significant figures after the decimal point. In further calculations, exact values are used.
For exact values, please refer to the supplementary Excel file.

Based on the specific volume values in Table 7, a scatter plot of specific volume against weight percent of ethanol was
drawn. The plot is presented in Figure 1. The trend of this plot was explained by the second order polynomial: “y = 10-5x2 +
0.0011x + 1.0091” with an R2 value of 0.9944.

Specific Volume - Ethanol Weight Percent Graph

1.3
y = 1E-05x2 + 0.0011x + 1.0091
Specific Volume / mL/g

1.25 R² = 0.9944
1.2

1.15

1.1

1.05

1
0 20 40 60 80 100
Weight Percent of Ethanol / %

Figure 1. Specific volume of 0, 20, 40, 60, 80, 100 weight percent ethanol solutions (ethanol-water mixtures) graphed against
weight percent of ethanol in the solution. The trend line is a second order polynomial with the equation: “y = 10-5x2 +
0.0011x + 1.0091”. The R2 value of regression is 0.9944.

To obtain partial molar volume graphs of ethanol and water, the specific volumes of ethanol and water at 0, 20, 40, 60, 80,
100% (w/w) ethanol concentration must be known. To acquire this value, firstly the slopes of the tangent lines to the trend
line in Figure 1 at the mentioned concentrations needed. This is done via taking the derivate of the equation (Figure 1)
manually and solving for y at x equals 0, 20, 40, 60, 80 and 100. After calculating the slopes of the tangent lines, the y-
intercepts of each tangent line at x equals 0 and x equals 100 were calculated. This is done because the specific volume of
water at a certain concentration is the y-value at which the tangent line at that concentration at cuts x = 0 vertical line (which
is y-axis), namely when ethanol concentration is zero and 100% of the solution is water. This is the reverse for ethanol in
which the specific volume of ethanol at a certain concentration is the y-value at which the tangent line cuts x=100 vertical
line. To calculate these y-values/y-intercepts, the following equation is used:
y−y0
=m (10)
x−x0

In this Equation 10, m is the slope of the tangent line, y is the specific volume to be found, y0 is the specific volume of the
solution at given concentration, x is 0 for water and 100 for ethanol, x0 is the concentration. If Equation 10 is rearranged to
leave the y alone:

y = m*(x - x0) + y0 (11)

6
Using Equation 11, the specific volume of water and ethanol at a certain concentration can be found. The tangent line slopes,
specific volumes of water and ethanol are given in Table 8 and these values for 20% (w/w) ethanol is given below as a
representative calculation:

The equation from specific volume versus ethanol weight percent plot = y = 10-5x2 + 0.0011x + 1.0091

Derivative of the equation = 2*10-5x + 0.0011

Slope of the tangent line at 20% ethanol concentration (m) = 2*10-5*20 + 0.0011 = 0.0015 mL/g

Specific volume of water at 20% ethanol concentration = 0.0015 * (0 – 20) + y0 mL/g

y0 = specific volume of 20% ethanol solution = 1.002964764 mL/g

Specific volume of water at 20% ethanol concentration = 0.0015 mL/g * (0 – 20) + 1.002964764 mL/g = 1.017328744 mL/g
≈ 1.0173 mL/g

Specific volume of ethanol at 20% ethanol concentration = 0.0015 mL/g * (100 – 20) + 1.002964764 mL/g = 1.167328744
mL/g ≈ 1.1673 mL/g

Table 8. Slopes of tangent lines to the specific volume-ethanol weight percent graph at certain ethanol-water compositions
and specific volumes of water and ethanol at these concentrations.

Weight Percent of Ethanol Slope of the Tangent Line / Specific Volume of Water* / Specific Volume of Ethanol*
/% mL/g mL/g / mL/g
0 0.0011 1.0030 1.1130
20 0.0015 1.0173 1.1673
40 0.0019 1.0012 1.1912
60 0.0023 0.9868 1.2168
80 0.0027 0.9621 1.2321
100 0.0031 0.9542 1.2642
*Values are given rounded off to 4 significant figures after the decimal point. In further calculations, exact values are used.
For exact values, please refer to the supplementary Excel file.

Continuing, partial molar volumes of water and ethanol at the certain weight percentages were found utilizing the specific
volume values in Table 8 via the relation:

Partial molar volume = V¯ = Molecular weight / density = Molecular weight * specific volume (12)

Molecular weight of water and ethanol were taken as 18.02 g/mol and 46.07 g/mol respectively. Therefore, for water, 18.02
g/mol was multiplied with the specific volumes of water in Table 8 and for ethanol, 46.07 g/mol was multiplied with specific
volumes of ethanol in Table 8. Calculated values are presented in Table 9. The calculation for 20% ethanol solution is:

V¯water at 20% ethanol solution = 18.02 g/mol * 1.0173228744 mL/g = 18.33226397 mL/mol ≈ 18.3322 mL/mol

V¯ethanol at 20% ethanol solution = 46.07 g/mol * 1.167328744 mL/g = 53.77883524 mL/mol ≈ 53.7788 mL/mol

Table 9. Partial molar volumes of water and ethanol at different ethanol weight percent concentrations.

Weight Percent of Partial Molar Volume of Partial Molar Volume of

Ethanol / % Water* / mL/mol Ethanol* / mL/mol
0 18.0734 51.2743
20 18.3323 53.7788
40 18.0420 54.8795
60 17.7818 56.0571
80 17.3369 56.7625
100 17.1951 58.2427
*Values are given rounded off to 4 significant figures after the decimal point. In further calculations, exact values are used.
For exact values, please refer to the supplementary Excel file.

7
One of the aims of the experiment was to determine the partial molar volume graphs of water and ethanol with respect to
changing mole fractions. Therefore, mole fractions corresponding to the partial molar volumes in Table 9 was calculated.
This was achieved by firstly finding the moles of water and ethanol in each solution. For the 20, 40, 60, 80% solutions this
was done by diving the measured mass of ethanol and water in Table 3 to molecular weight of each and finding the total
moles of matter in solution by adding moles of ethanol and water. Finally dividing moles of ethanol by total moles produced
the mole fraction of ethanol(xethanol) and dividing moles of water by total moles gave the mole fraction of water(x water). For
example:

Moles of ethanol in 20% ethanol solution = mass of ethanol in solution / Mwt.ethanol

Moles of ethanol in 20% ethanol solution = 4.74 g (Table 3) / 46.07 g/mol = 0.102886911 mol ≈ 0.1029 mol

Moles of water in 20% ethanol solution = mass of water in solution / Mwt.water

Moles of water in 20% ethanol solution = 18.94 g / 18.02 g/mol = 1.051054384 mol ≈ 1.0510 mol

Total moles in 20% ethanol solution = 0.102886911 mol + 1.051054384 mol = 1.153941295 mol ≈ 1.1539 mol

xethanol = 0.102886911 mol / 1.153941295 mol = 0.089161305 ≈ 0.08916

xwater = 1.051054384 mol / 1.153941295 mol = 0.910838695 ≈ 0.9108

Other mole fraction values for different concentrations were calculated via same equations and the final values are presented
in Table 10.

Table 10. Mole fractions of ethanol and water in different solutions and corresponding mole values.

Weight Percent of Moles of Ethanol* Moles of Total Moles* / Mole Faction of Mole Fraction of
Ethanol / % / mol Water* / mol mol Ethanol* Water*
0 0.0000 1.3832 1.3832 0.0000 1.0000
20 0.1029 1.0510 1.1539 0.08916 0.9108
40 0.1960 0.7519 0.9479 0.2068 0.7932
60 0.2804 0.4783 0.7588 0.3696 0.6304
80 0.3582 0.2292 0.5873 0.6098 0.3902
100 0.4292 0.0000 0.4292 1.0000 0.0000
*Values are given rounded off to 4 significant figures after the decimal point. In further calculations, exact values are used.
For exact values, please refer to the supplementary Excel file.

The partial molar volume graph for water was acquired by plotting the partial molar volume values in Table 9 versus mole
fractions of water in Table 10. And the same values for ethanol in the same tables were used to draw the partial molar volume
of ethanol graph. These graphs are presented in Figure 2 and Figure 3.

Partial Molar Volume of Water

18.4
Partial Molar Volume mL/mol

18.2 y = 0.442x2 + 0.6804x + 17.15

R² = 0.8922
18
17.8
17.6
17.4
17.2
17
0 0.2 0.4 0.6 0.8 1
Mole Fraction of Water

Figure 2. Partial molar volume of water graphed versus mole fractions of water from 0 to 1. The trend line equation is a
second order polynomial: “y = 0.442x2 + 0.6804x + 17.15” and the R2 value for the trend line is 0.8922.

8
 Partial Molar Volume of Ethanol
59
Partial Molar Volume mL/mol

58
57
56 y = -7.1845x2 + 13.204x + 52.026
55 R² = 0.9459
54
53
52
51
50
0 0.2 0.4 0.6 0.8 1
Mole Fraction of Ethanol

Figure 3. Partial molar volume of ethanol graphed versus mole fractions of ethanol from 0 to 1. The trend line equation is a
second order polynomial: “y = -7.1845x2 + 13.204x + 52.026” and the R2 value for the trend line is 0.9459.

As the next step, by using the trend line equations, partial molar volumes of water and ethanol were found at mole fractions
of 0.2, 0.4, 0.6 and 0.8. To find these partial molar volumes, 0.2, 0.4, 0.6 and 0.8 were plugged into the equations presented in
Figure 2 and Figure 3. Resulting partial molar volumes are presented in Table 11 together with corresponding mole fraction
of ethanol. For example, xethanol = 0.2 corresponds to partial molar volume of ethanol at xethanol = 0.2 in trend line equation in
Figure 3 while partial molar volume of water at this concentration can be found by plugging in xwater = 0.8 into trend line
equation in Figure 2. This is because xethanol and xwater adds up to 1. A representative operation is as follows:

Partial molar volume of ethanol at 0.2 xethanol = -7.1845*(0.2)2 + 13.204*0.2 + 52.026 (from Figure 3) = 54.37942

Partial molar volume of water at 0.2 xethanol = Partial molar volume of ethanol at 0.8 xwater = 0.442*(0.8)2 + 0.6804*0.8 +
17.15 (from Figure 2) = 17.9772

Table 11. Partial molar volumes of ethanol and water at different mole fractions of ethanol in ethanol-water binary solution.

Partial Molar Volume of Ethanol / Partial Molar Volume of Water /

Mole Fraction of Ethanol
mL/mol mL/mol
0.2 54.37942 17.9772
0.4 56.15808 17.7174
0.6 57.36198 17.4929
0.8 57.99112 17.3038

Lastly, the volumes of the ethanol-water solutions were calculated from the partial molar volume data, and they were
compared with the expected volumes given volume is additive. The volume values and the precent error is presented in Table
12. In the experiment, solutions of 20, 40, 60, 80 % (w/w) ethanol solutions were prepared via measuring calculated amount
masses of ethanol and water. These measured mass values are presented in Table 3. The Vexpected for these values were find by
dividing the measured mass of each component by the density of that component and adding the resulting volumes. As an
example, the Vexpected for 20% ethanol solution was calculated in the following way:

Vexpected = Vethanol + Vwater (13)

Volume = mass / density (9)

Vexpected = massethanol / densityethanol + masswater / densitywater = 4.74 g / 0.791 g/mL + 18.94 g / 0.997044 g/mL = 5.992414665
mL + 18.9961526272 mL = 24.98856729 mL ≈ 24.9886 mL

In the experiment, mass measurements for 0 and 100 % ethanol were not done. Thus, the Vexpected for pure water and ethanol
respectively couldn’t be calculated and simply assumed as 25mL.

Vcalculated at concentrations 0, 20, 40, 60, 80 100 percent ethanol was found using the corresponding (at desired ethanol weight
percent) moles of each component from Table 10 and corresponding partial molar volume of each component from Table 9
via the Equation 2:

V = na . V¯a + nb . V¯b (2)

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Vcalculated of 20% ethanol solution = molethanol * V¯ethanol + molwater * V¯water = 0.102886911 mol * 53.77883524 mL/mol +
1.051054384 mol * 18.33226397 mL/mol = 24.80134466 mL ≈ 24.8013 mL

Finally, the calculated and expected volumes if volume is assumed to be additive were compared and percent error was
calculated from the following expression:

Percent error = [|expected value-experimental value| / expected value] * 100

Table 12. Comparison of expected volumes of ethanol-water solutions with calculated volumes of the solutions and the
precent error in each value.

Weight Percent of Calculated Volume* / Difference in Volumes*

Expected Volume* / mL Percent Error* / %
Ethanol / % mL /mL
0 25 25.0000 0.0000 0
20 24.9886 24.8013 0.1872 0.7492
40 25.0061 24.3233 0.6828 2.7307
60 24.9793 24.2268 0.7525 3.0123
80 25.0019 24.3030 0.6989 2.7955
100 25 25.0000 0.0000 0
*Values are given rounded off to 4 significant figures after the decimal point. In further calculations, exact values are used.
For exact values, please refer to the supplementary Excel file.

Discussion

The objective of this experiment was to understand the relationship between partial molar volume water and mole fraction of
water and between partial molar volume of ethanol and mole fraction of ethanol in binary mixtures of ethanol and water to
consequently apply these relationship in investigation of additivity property of volume. This was achieved by firstly, plotting
the specific volume of ethanol-water solutions against increasing ethanol weight percent. Then, the y-intercepts of the tangent
lines at x=0 and x=100 were used to calculate the partial molar volumes of water and ethanol with respect to their
corresponding mole fractions. From these partial molar volume graphs, the total volume of ethanol-water solutions was
calculated via Equation 2 and the calculated values were compared with the expected volume values.

The first observation of this experiment is the decrease in densities or increase in specific volumes of solutions as weight
percent of ethanol increased (Table 7). This trend can be easily explained by increase of ethanol in the solution as its density
is lower than that of water. Since specific volume is the reciprocal of density, it is the ratio of volume to mass. The graph of
specific volume versus weight percent of ethanol is explained by a trend line of second order (Figure 1). This is also expected
as the mass is in the y-axis has a reciprocal relation to the mass in the x-axis. This logic can be demonstrated better if density
versus mass percent graph is drawn in which the relationship would be linear (This graph is included in the Excel file but
could not be added to the report due to space constrictions). This is because the mass is the numerator in density formula
therefore it has a linear relationship with the x-axis which is mass percent of ethanol. The effect of partial molar volumes also
cements itself in the Figure 1. If there was no effect coming from partial molar volumes, omitting the random errors, the
relationship in Figure 1 must be perfectly fitting to the trend line. But this is not the case since partial molar volumes have a
peculiar effect on the density of the solutions which can explain some of the deviation in Figure 1. The R 2 value of the graph
is 0.9944. This is a good value considering that maximum is 1 one R2 value (Lewis-Beck, 1990). Therefore, the correlation
between the specific volume and mass percent of ethanol can be strongly explained with the trend line. There is an obvious
deviation from the trend line: data points at 20%. This might be caused by a gross error, and it is discussed in Error Sources
subsection.

The partial molar volume of water shows an increasing trend with increasing mole fraction of water which does not fully
trace the second order trend line (Figure 2). This is also demonstrated by the relatively low R2 value of 0.8922. The
increasing trend is explained by the following logic: when the water presence is very low, added water molecules are mostly
surrounded by ethanol molecules which disturb the H-bonding between water molecules that restrains them in a certain
ordered distance and water molecules fill less space that they would in a higher water concentration (Atkins, 2006).
Therefore, at lower water mole fractions partial volume is low and it increases getting closer to molar volume of water (18
mL) as water mole fraction gets closer to 1. The unusual sudden shoulder visible in data between mole fractions 0.8-1 (Figure
2) is also present in literature reported graph (Atkins, 2006). This sudden behavior is observed in low ethanol concentrations
(or high water concentrations) and reported to be caused by water-water interactions and hydrations shells (Tan, 2015). The
existence of this bump also explains the low R2 value as it causes deviation from the trend line. This deviation results in an
increasing rate of increase in the trend line while the reported trend line prominently follows a decreasing rate of increase
(Atkins, 2006).

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The partial molar volume of ethanol graph also correlates with an increasing second order trend line with an R2 of 0.9459
(Figure 3). This fashion is similar to literature values (Atkins, 2006). Again, the behavior is explained by the packing of
ethanol molecules in between water molecules when the ethanol concentration is low. The high R2 value and the absence of
unusual deviations suggests that the trend line explains the dependence of the partial molar volume of ethanol to its mole
fraction successfully. The dip observed in literature value at small concentrations of ethanol is not observed. The absence of
this behavior can be attributed to loss of sensitivity when specific volumes were multiplied by molecular weights of each
liquid. Ethanol’s molecular weight is 2.5 times water’s molecular weight. Thus, the sensitivity might be conserved in Figure 2
while it is lost in Figure 3. Partial molar volume graphs predict the literature maxima correctly but not minimum values:
water: 18-16 mL/mol, ethanol: 58-56 mL/mol (Atkins, 2006) while the graphs predict 18-17.2 and 58-52 mL/mol. This is an
interesting finding which might stem from the lack of sensitive equipment. It might be that the laboratory balance used was
not sensitive enough to pick up the unusual behavior at small ethanol concentrations.

Lastly, calculated volumes were compared with expected volumes. The expected volumes were based on assuming volume is
an additive property, but it is not which is nicely shown by the error between the Vcalculated and Vexpected. The error is not very
big because the experiment was not done by very sensitive equipment which caused loss of sensitivity in measurement and
the effect of partial molar volumes are limited to values even smaller than milliliters because the experiment vastly included
moles ≤ 1.4 mol (Table 10).

Error Sources

There are two measuring devices used in this experiment: laboratory balance and pycnometer. Yet, the uncertainty of the
pycnometer is not relevant because its volume is calculated from the mass measurement. Consequently, the balance is the
only uncertainty source. Hence, mass measurements must be done diligently in this experiment. The balance used had two
decimal digits. This is not a very high sensitivity for a laboratory balance for which a standard is 4 decimal digits. This is
especially important in this experiment because the calculations involve small numbers (densities volumes of water and
ethanol) in which small errors can cause substantial differences in the resulting specific volume values. These values scatter
between 1 and 1.4 suggesting the differentiating digits are decimal digits. Also, the balance measures until hundredths but the
calculated mass values prior to experiment have numerous significant figures. The sensitivity of the significant figures is
considerably lost during the measurements. Therefore, the balance introduces both random and systematic error in this
experiment, affecting the final accuracy of the calculated values. Another systematic error source for mass measurements is
change in environment such as moving something on the bench during measuring. This error can be minimized simply by
doing taking careful measurements by being steady in a stable environment. The random errors are due to heat, pressure,
electrical fluctuations, small currents of air, moisture in the air and small variations in the last significant digit. These random
errors can be diminished via replication of the experiment.

Humidity in the air is an important systematic error source for this experiment since all the measurement are mass
measurements. The pycnometer must be removed from all moisture in an oven and dried in a desiccator. Also, this must be
done several times until acquiring a consistent dry mass value. This was not done in this experiment. It might be postulated
that the effect of moisture would be constant for each measurement. Even if the amount of moisture on the pycnometer might
be constant, its ratio to the measured value will be more significant for small masses causing systematic error. Apart from
humidity, not filling the pycnometer fully to the brim and not drying it completely after overflow can create systematic error.

The experiment done in an environment assumed to have constant temperature and pressure. Fluctuations of these values
introduces random error. As density of water and ethanol changes with temperature and pressure, this can also introduce
systematic error. The solutions prepared might behave differently in different conditions. Therefore, keeping temperature and
pressure constant is a very important parameter. To eradicate these errors, the experiment can be done in an isolated
environment. Moreover, the density values for water an ethanol used in calculations were densities at 25 C o but the
temperature of the room was not measured. Density values changes with temperature and a big difference such as 5 to 10
degrees can cause a substantial deviation. The calculations done in the experiment involves very small numbers. For
example, the equation of the trend line in Figure 1 involves values in order of 10-5. Deviations from correct densities can
cause drastic changes in data in this order: not measuring the room temperature can create systematic errors. This can explain
the low R2 values in the data.

It can be deducted from Figure 1 that the specific volume of 20% (w/w) ethanol solution particularly deviates from the trend.
It appears above the trend line, meaning its specific volume is higher than expected, therefore its density is lower than
expected. There are possible reasons: an air bubble was present on top of the pycnometer, pycnometer was not dried properly
in other measurements and dried rigorously in this measurement, the experimenter disturbed the balance by a sudden change
in environment. These might cause the mass measurement to be less that it was. It might also be a recording mistake. All
these reasons cause a gross error which might be the case for this measurement.

The main limitations of this experiment are the lack of sensitive equipment and repetition is particularly important because R2
values partial molar volume graphs are not very high and the unusual deviation in small ethanol concentrations is observed in
water graph but not in ethanol graph. The repetition is useful in validating the presence of the bump in Figure 2 by showing

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that it is not caused by an error and investigating the reason of absence of the dip in ethanol graph. In general, repetition is
implemented to reduce the random error. A general minimum for graphs would be working with triplicates.

Conclusion

In conclusion, the partial molar volume graphs for water and ethanol followed the anticipated behaviour of increase with
increasing mole fraction with confident R2 values. Compared with the literature findings, the graph for water was successful
in predicting the anomaly in small ethanol concentrations while graph for ethanol couldn’t which sheds doubt on the first
claim. Therefore, the presence of the bump in Figure 1 must be demonstrated in repeated experiments. The results also
showed that volume is not additive via the error between Vexpected and Vcalculated. The main error sources were lack of decimal
digits in laboratory balance, not measuring the temperature of the room therefore the possibility of using wrong density
values for water and ethanol, humidity or water on the pycnometer. The limitations were the lack of repetition and absence of
sensitive equipment. For more certain results, the experiment must be conducted with replicates, in a stable environment of
known temperature.

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