ABSTRACT

The experiment shows how the partial molar volumes (𝑉̅1 and 𝑉̅2) were obtained by
experimentally measuring the density of six solutions in varying concentrations. Apparent
molar volumes of the solute and the molality of the solution were calculated experimentally
using the density and the composition of the solution. The apparent molar volume of the
solute was graphed against the square root of the molality. The graph was then fitted to the
equation of linear relationship of the two variable giving the values for the the apparent molar
volume extrapolated to zero concentration ϕo and the change in apparent molar volume with
𝑑𝜙 𝑑𝜙
respect to square root of molality . The values of and ϕo were used to calculate the
𝑑√ 𝑚 𝑑 √𝑚

partial molar volumes. The partial molar volumes were graphed against the molality and their
relationship were determined. The results suggests the relationship of the partial molar
volumes of solute and solvent. The partial molar volume of the solute is directly proportional
with the molality while the partial molar volume of the solvent is inversely proportional to
the molality.
INTRODUCTION

Partial molar quantity is the rate at which an extensive property changes as a certain
amount of species is added to a mixture or solution as temperature, pressure and other factors
were kept constant.[1]

𝑉 = 𝑉 (𝑛1 , 𝑛2 ) 𝑇,𝑃 [1]

Partial molar volume is the contribution of a component to the total volume of the
solution. It can also be defined as the change in volume for every mole added or removed to
the mixture/solution.[2] Partial molar volume is used to calculate the overall volume of the
solution since volume is not an additive property. An example is when 50mL of water is
added to the same amount of alcohol. The alcohol solution volume would not be equal to
100mL however lower. This is because of the intermolecular forces of attraction of the
molecules and by the environment of the solution.

The partial molar volume can be calculated from

𝜕𝑉 𝜕𝑉
𝑑𝑉 = (𝜕𝑛 ) 𝑑𝑛1 + (𝜕𝑛 ) 𝑑𝑛2 [2]
1 𝑇,𝑃 2 𝑇,𝑃

Partial molar volume of each component 𝑉̅1 and 𝑉̅2 can also be defined by taking the
volume changes of each component where component 1 is the solvent and component two is
the solute.

𝜕𝑉 𝜕𝑉
𝑉̅1 = (𝜕𝑛 ) and 𝑉̅2 = (𝜕𝑛 ) [3]
1 𝑛2 ,𝑇,𝑃 2 𝑛1 ,𝑇,𝑃

As the partial molar values became known, the total molar volume of the solution can
calculated from

V = 𝑉̅1 𝑛1 + 𝑉̅2 𝑛2 [4]

On this experiment, in order to simplify the calculation for the partial molar volume a related
quantity apparent molar volume of the solute Φ was used. Apparent molar volume assumed that the
partial molar volume contributed by the solvent is the same as that of the pure solvent. Because of this
assumption, all the volume changes in the solution was assumed to be due to the apparent molar
volume of the solute.

V = 𝑉̅1𝑜 𝑛1 + Φ 𝑛2 where 𝑉̃10 is the molar volume of pure water [5]

[1]
 Rearranging the equation, apparent molar volume can be taken as

̅1𝑜 𝑛1
𝑉−𝑉
Φ= [6]
𝑛2

Relating the partial molar volume of the solute to the apparent molar volume,
equation [5] was partially derived with respect to n2 at constant n1. This gives the equation

𝜕𝑉 𝜕𝜙
𝑉̅2 = (𝜕𝑛 ) = ϕ + 𝑛2 (𝜕𝑛 ) [7]
2 𝑝,𝑇,𝑛𝑗 2 𝑛1

Now, relating the equation to the experimental data taken, molality m and density ρ,
the volume of the solution can be expressed as

1000+𝑚𝑀2
𝑉= [8]
𝜌

where M1 and M2 are molar masses of solute and solvent

The volume of the solvent in equation [5] is the term 𝑉̅1𝑜 𝑛1 . 𝑉̃10 is the molar volume
of pure water (= 18.016 g mol-1/density of water at specific temperature). If the concentration
that will be used is the molality m with mass of the solvent equal to 1000g, the volume of the
solvent is

1000
n1 𝑉̃10 = 𝑐𝑚3 [9]
𝜌0

Substituting equation [8] and [9] to equation [6] we can get the working equation to
experimentally measure the apparent molar volume Φ with n2 is equal to m.
1 1000 𝜌−𝜌0
Φ = 𝜌 (𝑀2 − ( )) [10]
𝑚 𝜌0

where 𝜌 is the density of the solution and 𝜌0 is the density of the solvent

Substituting m to n2 in equation [7] then changing the variable m to √m since Φ is a

linear function of √m not m.

𝑑𝜙 𝑑𝜙 𝑑 √𝑚 1 𝑑𝜙
= = [11]
𝑑𝑚 𝑑 √𝑚 𝑑𝑚 2√𝑚 𝑑√𝑚

[2]
 The linear relationship between Φ and √m for solutions of simple electrolytes of
dilute to moderate concentrations was showed by Masson (1929)

𝑑𝜙
ϕ = ϕ𝑜 + 𝑑 √𝑚 [12]
√𝑚

where ϕ𝑜 is the apparent molar volume extrapolated to zero concentration.

𝑑𝜙
The plot 𝜙 of versus m yields the values ϕ𝑜 and .
𝑑√𝑚

Combing equation [7] and [11] we get the working equation for the partial molar
volume of solute

1 𝑑𝜙 √𝑚 𝑑𝜙 3√𝑚 𝑑𝜙
𝑉̅2 = 𝜙 + 𝑚 2 𝑚 𝑑 𝑚 = 𝜙 + 2 𝑑 𝑚 = ϕ𝑜 + 2 𝑑 𝑚 [13]
√ √ √ √

To calculate the 𝑉̅1, equation [4] was rewritten as

̅2 𝑛2
𝑉− 𝑉
𝑉̅ = [14]
𝑛1

Substituting the equation [7] and [5] to equation [14] and m to n2 and n1 = 55.51,
working equation for 𝑉̅1.

𝑚 √𝑚 𝑑𝜙
𝑉̅1 = 𝑉̃10 − 55.51 2 𝑑 𝑚 [15]
√

[3]
MATERIALS AND METHODS

Materials

• Sodium Chloride was the salt assigned for the preparation of the salt solution.
• Weld pycnometer, consist of pycnometer and thermometer, was used to measure the
density of the liquids during the experiment.
• Analytical balance was used to measure the mass of the salts for the preparation of
the solution.
• Volumetric flasks that can hold 100mL of liquid was used to measure accurate
amount of prepared salt solution.
• Stirring rod was used to mix the solute and solvent during the preparation of the salt
solution.
• Weighing cups were used as a container for salt when weighing.
• Wash bottle was used to transfer water to the volumetric flask.
• Pasture pipet was used to transfer small amounts of water to adjust the volume of the
salt solution.

Methodology

The experiment were conducted per cluster consisting of two groups. Each cluster
were given a salt for the experiment. The salt was dried in the oven and placed in the
desiccator to assure that the anhydrous salt used will maintain a 99.9% purity. Before the
experiment, CO2 free water was prepared by boiling 1L of water and then immediately
transferred in a plastic bottle for storage ensuring that there was no air space in the bottle.

Preparation of Pycnometer

The pycnometer was washed using water and liquid soap and then it was rinsed with
distilled water. It was dried using kimwipes and acetone.

[4]
Calibration of the Analytical Balance

Before weighing anything, the analytical balance was calibrated. The balance was
first cleaned and wiped with kimwipes and acetone to remove dirt that remained in the pan
for long periods. The dust particles was removed using a brush. Next, to calibrate the
analytical balance, “cal” button was pressed with the pan of the balance cleared up. 200g of
standard weight was then placed in the pan as instructed and was left to calibrate. The 200g
was then removed from the pan and the balance then calibrated with empty pan. The
calibration was completed when the balance flashed a text that says so.

Preparation of Aqueous Salt Solution

Six (6) aqueous solutions of different concentrations were prepared by adding varying
masses (2, 4, 6, 8, 10 & 16g) of salts to 100mL of CO2 free water in volumetric flask. The
volumetric flasks were numbered 1 to 6 with increasing concentration to identify the
solutions. The anhydrous salt was weighed in analytical balance using the weighing cups then
dissolved with small amount of water for easy transfer. The remaining salts in weighing cups
were again washed with water and transferred to the volumetric flask. The weighing cups
finally were washed with water three times so that all the salts were transferred in the
volumetric flask. The volumetric flask was then filled with water near the 100mL line and
mixed occasionally. The water was then slowly adjusted to 100mL with small amounts of
water using pasture pipet.

Calibration of Pycnometer

The pycnometer, with the temperature, was calibrated by letting it in stand in the
room for a couple of minutes to attain the same temperature with the room. The temperature
was then recorded and pycnometer was weighed on analytical balance. After weighing the
empty pycnometer, the pycnometer was filled with CO2 free water then thermometer was
attached so that the excess water will flow out of the overflow tube then the tube was covered
making sure that no bubbles was present. The pycnometer was then wiped with kimwipes to
dry. The temperature was then taken and was weighed. The pycnometer was then emptied
and refilled with CO2 free water and weighed five times.

[5]
Measuring the Densities of Salt Solutions

The pycnometer was rinsed with the salt solution that will be measured. The
pycnometer was filled with the salt solution with the same technique that was used in filling
the pycnometer with water. The temperature was measured and was weighed. This process
was repeated in three trials. The procedure was then used when measuring the densities of the
salt solution with the different concentrations.

Treatment of Data

All the data obtained was tabulated in an MS Excel worksheet. Calculations such as
the density, molarity, molality and the apparent molar volumes were calculated. Using the
calculated information the square root of molality was graphed against the apparent molar
volume to estimate the value of the partial molar volumes.

RESULTS

The experiment gives the necessary data to calculate the partial molar volume of NaCl
salt solution – the densities and the composition of the salt in every solution. To measure the
densities of the solution, the pycnometer needs to be calibrated. Calibration of the
pycnometer gives will give the mass of the pycnometer that will be used in later calculations.
The mass of the empty pycnometer (We) obtained was 33.8478g. The mass of the pycnometer
with water (Wo) is 58.43434g. The value for pycnometer with water used was the mean of all
the trials that were conducted. Values for such are listed at appendix a – table 1. Using this
mass and the literature value for the density of water at 28°C, which is 0.996237 g ml-1, the
volume was calculated to be 24.6794mL. The values for densities of water at 1atm in
different temperatures was listed at appendix a – table 2. The formula for the calculation of
the volume can also be found at the appendix b – equation 1.

[6]
Table 1. Different NaCl salt solution Molarity at 28 OC and 26 OC

Solution Mass of Sample Actual Mass of Sample No. of Moles (n) Molarity (M)
No. g g mol mol L-1
1 2 2.0559 0.0352 0.3520
2 4 4.1261 0.0706 0.7060
3 6 6.0325 0.1032 1.0320
4 8 8.0475 0.1377 1.3770
5 10 10.0383 0.1718 1.7180
6 16 16.0477 0.2746 2.7460

Table 1 shows the concentration for each of the solution given the mass of the sample,
molar mass of anhydrous sodium chloride, 58.44g mol-1, and the volume of the solution,
100mL or 0.1 L. Molarity is the amount of the solute for every liter of solution. The formulas
that were used in the MS Excel were shown in appendix b – equation 2 and 3.

Table 2. Tabulated Data of the quantities obtained from different NaCl salt solution
concentrations

Soln W W-We ρ Molality (m) (1000/m)(W- Φ

sqrt m
No. (g) (g) (g ml-1) mol kg-1 W0)/(W0-We) (mL mol-1)
1 58.7737 24.9259 1.0010 0.3556 38.8168 0.5963 19.4298
2 59.1142 25.2664 1.0238 0.7186 38.4820 0.8477 19.4943
3 59.4250 25.5772 1.0364 1.0576 38.0977 1.0284 19.6283
4 59.7691 25.9213 1.0503 1.4199 38.2337 1.1916 19.2382
5 60.0705 26.2227 1.0625 1.7853 37.2753 1.3361 19.9191
6 61.0228 27.1750 1.1011 2.9193 36.0634 1.7086 20.3217

The data gathered at the course of the experiment was tabulated in table 2. The
weight of the pycnometer with the solution (W) used in data calculation was the mean value
obtained using the three trials that was performed. The masses of the pycnometer and
solution in three trials was tabulated in appendix a - table 3. The W-We column shows the
weight of the solution. The weight of the empty pycnometer was subtracted to the weight of
the pycnometer and solution to obtain the value. Using the weight of the solution, density
can be calculated with the volume of the pycnometer known. The density was then used to
calculate the molality of the salt solution. For more convenient solving for apparent molar
volume Φ at the next column, (1000/m)(W-W0)/(W0-We) was calculated. Square root of molality
m was also calculated for graphing purposed. All the formulas used in the MS Excel was listed in
appendix b – formula 4 – 6.

[7]
 Figure 1. Apparent Molar Volume Φ versus square root of molarity √m

In figure 1, the square root of molality was graphed. A point deviated from the trend
of values in the graph. The said point, (1.1916, 19.2382) was removed since it is a bad point
and it deviates greatly to the set of points. To improve the quality of the graph it was
removed.
Linear regression equation show the relationship of √m and ϕ through the equation
[12]. The equation of the line gives the values for the apparent molar volume extrapolated to
𝑑𝜙 𝑑𝜙
zero concentration ϕ𝑜 and the . The value for the is the slope of the equation which
𝑑 √𝑚 𝑑 √𝑚

is equal to 0.8312 while the value for ϕ𝑜 is the y – intercept which is equal to 18.842.
Using the same equation, the apparent molar volumes ϕ were recalculated. The values
were tabulated at table 3.

𝒅𝜱
Table 3. Recalculated values of Φ using the slope (𝒅 ) and the y-intercept(𝜱𝒐 )
√𝒎

Solution No. Φ Recalculated value of Φ

1 19.4298 19.3376
2 19.4943 19.5466
3 19.6283 19.6968
5 19.9191 19.9526
6 20.3217 20.2622

[8]
Table 4. Partial Molar Volumes of Solute and Solvent
Partial Molar Volume of Solvent 𝑉̅1 Partial Molar Volume of Solute 𝑉̅2
Sol’n No.
mL mol-1 mL mol-1
1 18.0824 19.6776
2 18.0794 19.8466
3 18.0756 20.0557
5 18.0661 20.4744
6 18.0467 21.0318

𝑑𝜙
Table 4 was generated by solving for 𝑉̅1 and 𝑉̅2 using the values for ϕ𝑜 and and
𝑑 √𝑚

equation [13] and [15]. Sample calculations were shown at appendix c – calculation 2.

Figure 2. The graphical representation of 𝑉̅1 versus Molality

[9]
 Figure 3. The graphical representation of 𝑉̅2 versus Molality

Figures 2 and 3 shows the relationship of the partial molar volumes to the molality of
the solution. It can be observed that the curve of the partial molar volume of the solvent
decreases as the molality increases. The partial volume of the solute of the other hand, has an
increasing trend as the molality increases.

DISCUSSION

In this experiment, partial molar volume of the solute and solvent in the aqueous salt
solution. The relationship for their partial molar volumes were also investigated. Component
1 of the solution is the solvent, water and components 2 is the solute, the Sodium Chloride.

To be able to get the values for the partial molar volume, the experimental data of
solution that was easy to measure and related to the partial molar volume must be obtained.
Since density is directly related to the volume of a solution as well as the solution’s molality
it is sufficient to determine the partial molar volume of the aqueous salt solution. Density is
also easy to measure through the pycnometer. The density of the pure solvent used was

[10]
0.996237 g mL-1 instead of the standard 1 g mL-1 because density changes with temperature.
When temperature increases, the density decreases because at higher temperature the liquid
expands increasing the volume. Likewise, when temperature decreases the density
increases.[4] The room temperature during the calibration was 28°C therefore the density used
was 0.996237 g mL-1. With the increase in concentration of the solutions the mass of the
solution increases. In relation to this, the density of the solution varies directly to the
concentration of the solution. This is because as the amount of the solute present in the
solution increases the mass of the solution increases with the density of the solution.

One important variable in determining the partial molar volume is the molality of the
solutions. Since the apparent molar volume and the square root if the molality have a direct
linear relationship, the values for square root of molality was also solved.

Plotting the apparent molar volume against the molality in figure 1 shows that indeed
the two variables have a linear relationship. The equation of the line is an important step in
determining the values needed to calculate the partial molar volumes since both values of ϕ𝑜
𝑑𝜙
and can be generated by just fitting the equation. The equation of the line
𝑑 √𝑚

y = 0.8312x +18.842 can be interpreted to fit the linear equation for the relationship of
apparent molar volume and square root of the molality presented in equation [12]. The
apparent molar volume is the dependent variable y while square root of molality is the
dependent variable x. The slope of the equation, 0.8312 is value for the derivative of the
𝑑𝛷
apparent molar volume with respect to the square root of molality and the y intercept,
𝑑 √𝑚

18.8042, is the value for the apparent molar volume extrapolated to zero concentration ϕ𝑜 .
Apparent molar volume of the solute was also recalculated to estimate the values that would
the fit the line.
𝑑𝜙
As both values for ϕ𝑜 and 𝑑 were known partial molar volumes can be solved. The
√𝑚

partial molar volumes were calculated and was graphed against the molality. In figure 2, both
the partial molar volumes of the solute and the solvent depends on the concentration given by
molality. Both values change with molality however opposite. Partial molar volume of the
solvent decreases as the molality increases while the partial molar volume of the solute
increases. In a solution, low molality means that the solution contains small amount of solute
dissolved in the solvent. As the amount of solute was increased the partial molar volume of
the salt increases. With an increasing molality the contribution of the salt to the total volume

[11]
increases. In contrast, the partial molar volume of water decreases with the molality.
Increasing the molality means increasing the amount of the solute dissolved in the solvent. In
the experiment molality was increased by adding more solute to the solution with the same
final volume as the other solutions. The increase in solute in the solution leads to the decrease
in the amount of solvent. The contribution of the solvent to the total volume of the solution
decreases with molality. Partial molar volume of the solute and solvent has opposite effect to
the total volume of the solution when molality is changed.

SOURCES OF ERROR
In the data gathered, the experimental measurement of the apparent molar volume
graphed in figure 1 shows a point that deviates from the trend. This point was considered as
an outlier since it greatly deviates from the linear regression. The experiment was conducted
again to the solution where the error was found but same results were collected. The error
was not cause by the error done during the measurement in density. Since the error was not
due to the process the density was obtained it must be caused by some factors during the
preparation of the solution. This error however did not affect the final data that was graphed
in figure 2.

CONCLUSION

Using the methods stated in the lab manual the experiment was conducted and
performed. Using a simple experiment in measurement of density of the solutions in different
concentrations, values that are essential in obtaining the partial molar volumes were
calculated. The students successfully calculated and generated the values for partial molar
volumes for both solute and solvent. The relationship of the partial molar volumes of each
component to the concentration if the solution was also attained. The partial molar volumes
were dependent on the concentration. The partial molar volume of the solute is directly
proportional with the concentration while the partial molar volume of the solvent varies
indirectly with the concentration.

[12]
LITERATURE CITED

[1] Ceder G. Thermodynamics of Materials: The Solution Theory (2011). https://ocw.mit.edu

(accessed on October 20, 2016)

[2] Atkins P, De Paula J. Physical Chemistry 9th Edition. Great Britain: Oxford University
Press (2010)

[3] Levine I N. Physical Chemistry 6th Edition. New York: McGraw-Hill Companies Inc.
(2002)

[4] Kurtus R. Factors Affecting Density of Matter (2014). http://www.school-for-

champions.com/ (accessed on November 9, 2016)

AKNOWLEDGEMENT

This experiment was made possible for all the people who helped me finish this
report. For Brienz for consolidating and finalizing the data and results and my groupmates in
the cluster for staying up all night with me while doing the experiment. For Gwen for
recalculating the partial molar volumes and the linear regression.

APPENDICES

Appendix A. Tables

Table 1. Mass of Pycnometer with CO2 Free Water.

Trials W0 mass (g) Temp (°C)

1 58.4663 28.6
2 58.3805 28.6
3 58.4093 28.6
4 58.4565 28.5
5 58.4591 28.4
ave 58.43434 28.54

[13]
Table 2. Densities of Water at 1 atm[1]
Temperature (°C) Density (g ml-1) Temperature (°C) Density (g ml-1)
15 0.999103 22 0.997774
16 0.998946 23 0.997542
17 0.998778 24 0.997300
18 0.998599 25 0.997048
19 0.998408 26 0.996787
20 0.998207 27 0.996516
21 0.997996 28 0.996237

Table 3. Mass of Pycnometer with Salt Solution in Three Trials

Sol’n Mass of Pycnometer with Salt Solution Temperature

No. 1 2 3 Ave 1 2 3 Ave
1 58.7773 58.7742 58.7695 58.7742 26.9 27.4 27.2 27.2
2 59.1332 59.1134 59.0961 59.1142 28.7 28.4 28.2 28.4
3 59.4309 59.4116 59.4324 59.4250 28.2 28.6 28.5 28.5
4 59.7710 59.7682 59.760 59.7691 27.2 27.1 27.1 27.2
5 60.0341 60.0894 60.0880 60,0705 27.6 27.5 27.7 27.6
6 61.0164 61.0378 61.0142 61.0228 27.6 27.2 28.5 27.8

Appendix B. Equation

1. Volume the Pycnometer can Hold

(𝑊𝑜 − 𝑊𝑒 )
𝑉=
𝜌𝐻2 𝑂(28°𝐶)
2. Number of Moles (n)
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒
𝑛=
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑁𝑎𝐶𝑙
3. Molarity (M)
𝑛𝑜. 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 (𝑛)
𝑀=
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑉)
4. Density (𝝆)

[14]
 𝑊𝑠𝑜𝑙𝑛 𝑊 − 𝑊𝑒
𝜌= =
𝑉 𝑉
5. Molality (m)
M
𝑚=[ 𝑘𝑔 ] where M2 is the molar mass of the salt
𝜌𝑠𝑜𝑙𝑛 ( )−M𝑀2 (10−3 )
𝐿

6. Apparent Molar Volume (Φ)

1 1000 𝑊 − 𝑊0
Φ= (𝑀2 − )
𝑑 𝑚 𝑊0 − 𝑊𝑒

Appendix C. Calculations

̅𝟏 & 𝑽
1. Partial Molar Volumes (𝑽 ̅ 𝟐)
̅𝟏)
a. Partial Molar Volume of Solvent (𝑽
𝑚 √𝑚 𝑑𝜙 18.016 g mol−1
𝑉̅1 = 𝑉̃10 − 55.51 2 𝑑 √𝑚
where 𝑉̃10 = 0.996237 g ml−1
= 18.0840 𝑚𝐿 𝑚𝑜𝑙 −1

0.35555587 √0.35555587
𝑉̅1 = 18.0840 𝑚𝐿 𝑚𝑜𝑙 −1 − ( )( ) (0.7734)
55.51 2
𝑉̅1 = 18.0825230536 𝑚𝐿 𝑚𝑜𝑙 −1
̅𝟐)
b. Partial Molar Volume of Solute (𝑽

3√𝑚 𝑑𝜙
𝑉̅2 = ϕ𝑜 +
2 𝑑√𝑚

3√0.35555587
𝑉̅2 = 18.8070 + ( ) (0.7734)
2

𝑉̅2 = 19.4987503 𝑚𝐿 𝑚𝑜𝑙 −1

Appendix D. Post-lab Questions

1. What is the chemical significance of this experiment? Why is this experiment
important?

- The chemical significance of the determination of the partial molar volume is that it
contains important information about the solute-solvent interactions as well as the
solute structure in solution. And it is the most essential quantity in the analysis of the
[15]
 pressure effect on chemical reactions. And it has many applications kin the field of
biochemistry, oceanography and aquatic environmental science.

-3
2. The density of NaCl(s) is 2.165 g cm at 25 oC. How will the solubility of NaCl in
water be affected by an increase in pressure?

- The increase in pressure will not significantly affect the solubility of NaCl in
water because the NaCl is solid and the effects of pressure changes on the
solubility of solids and liquids are negligible. It only affects greatly the solubility
of the gases.

3. Discuss qualitatively whether the curves of V1 and V2 versus m behave in accord

with the Gibbs-Duhem equation:
𝑑𝑄̅1 𝑋1
=−
𝑑𝑄̅2 𝑋2

- The Gibbs-Duhem equation above is for a binary solution where the 𝑋𝑖 are mole
fractions. Partial molar volumes are of the interest in part through their
thermodynamic connection with other partial molar quantities such as the partial
molar Gibbs free energy which is also known as chemical potentials. The
chemical potential for any component is equal for all phases that are in
equilibrium with each other. The chemical potential of the solute is the same in
the two phases. Given the equation
𝜕(∆𝐺2̅ )
[ ] = ∆𝑉̅2 (24)
𝜕𝑝

which was differentiated from the equation

𝑑(𝐺̅2 ) = 𝑉̅2 𝑑𝑝 (25)
we can conclude that if the partial molar volume of solute in aqueous solution is
greater that the molar volume of solid solute, the pressure will increase as well as
the chemical potential of solute in solution relative to that i the solid phase which
then the solute will leave the solution phase until a lower, equilibrium solubility is
attained. On the other hand, if the partial molar volume in the solution is less than
the in the solid, the solubility increases with pressure.

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4. Is the total volume greater or less than the sum of the volume of the pure components?
- The total volume is less than the sum of the volume of the pure components.

5. Are the partial molar volumes of the solute and solvent greater or less than the pure
molar volumes?

- If the solution is ideal, the partial molar volume of the solution is just the sum of
the volumes of the pure solute and pure solvent. If the solution is not ideal, the
partial molar volume of the solution might increase or decrease depending on the
solute-solvent interactions.

6. What forces in solution cause the differences that you see in questions 4 and 5? Draw
a model of the solution using solute ions as spheres and water molecules as stick
structures to aid in your explanation.
- The intermolecular forces specifically the solute-solvent interactions in the
solution cause the differences in question 4 and 5.

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