EXPERIMENT 4

THE DETERMINATION OF PARTIAL MOLAR VOLUME

A Laboratory Report Submitted in Partial Fulfillment of the Requirements for Physical

Chemistry I

Laboratory Course

By

KRIZZIA ANNE B. ASTORGA

with

LUCILE A. BRONZAL

GLAICYL DAME ANN B. ARANIADOR

Bachelor of Science in Chemistry III

Section I

ARNOLD C. GAJE

Laboratory Instructor

Date Performed: October 10, 2016

Date Submitted: November 17, 2016

1
Abstract

Partial molar volume is one of the key elements in the study of the thermodynamics of

a mixture. This quantity can be determined by adding one mole of a component to a very

large volume of a solution. In this experiment the partial molar volumes of the solvent and

solute components of the Na2SO4 salt solution was determined by measuring the density of

the salt solutions at different concentrations with the aid of a pycnometer. This determination

yielded results that were precise but still susceptible to human error.

Introduction

In the study of thermodynamics, we can recognize between variables that are

independent of the quantity of matter in a system and variables that are dependent on the

quantity of matter. These are called intensive and extensive variables respectively. Volume

and heat capacity are examples of extensive variables, while temperature, pressure, viscosity,

concentration, and molar heat capacity are examples of intensive variables (Klotz and

Rosenberg, 2008).

Among the intensive variables in thermodynamics are partial molar quantities. This is

the rate at which property changes with the number of species added to the mixture as the

temperature, the pressure, and the amounts of all other species are kept constant (DeVoe,

2015).

In connection with the development of the thermodynamic concept of partial molar

quantities, it is necessary to be familiar with a mathematical relationship known as Eulers

theorem and Gibbs-Duhem relation. The Eulers theorem and the Gibbs-Duhem equation

may be applied to solutions (Klotz and Rosenberg, 2008).

2
 Partial molar volume, which is the subject of our study, is defined as the increase in

the volume of very large amount of solution when one mole of component is added (Garland

et al., 2009).

The partial molar volume of the components of a solution changes with its

composition. This is due to a variation that happens if the composition of a molecule changes

from A to B. Moreover, it also caused by the molecular environmental changes that occur

when the particles composition is altered. Thus, this phenomenon also affects the

thermodynamic properties of the mixture (Atkins, 2010).

The aim of this experiment is to determine the partial molar volume of the solute and

solvent in aqueous salt solutions from density measurements. The apparent and partial molar

volumes of electrolyte solutions was verified to be a very useful tool in clarifying the

structural interactions occurring in a mixture. These quantities help confirm the presence of

interactions such as ion-ion, ion-solvent and solvent-solvent relations in a particular solution

(Millero, 1971).

Methodology

Materials

The materials used to carry out the experiment were the following:

1. 25 mL Weld Pycnometer

A weld pycnometer is a flask with a close-fitting ground glass stopper with a hole through

it. It is used to measure the density of a fluid. In this experiment, it was used to determine

the density of the Na2SO4.

2. Analytical Balance

3
 Analytical balance is used for weighing samples accurately. In this experiment, it was

used to measure the mass of the pycnometer and the solid Na2SO4 compound.

3. 100 mL Volumetric Flask

Volumetric flask is a laboratory glassware used for precise dilutions and preparation of

standard solutions. In this experiment, it was used to contain the respective Na2SO4

solutions.
4. Stirring Rod
Stirring Rod is a laboratory equipment used to mix chemicals and liquids for laboratory

purposes. In this experiment, it was used to transfer the solid compound from the

weighing cups to the volumetric flask.

5. 250 mL Beaker
A beaker is a glass container used for stirring, mixing, and heating liquids for laboratory

purposes. In this experiment, it was used a temporary container for the washed solutions.
6. Reagent Bottle
A reagent bottle is a container made of either glass, plastic, borosilicate or related

substances. In this experiment, it was used to store the Na2SO4 solutions.

7. Weighing Cups

Weighing cups are used as a container for storing and measuring solid laboratory

compounds. In this experiment, it was used as a vessel in measuring the mass of the

Na2SO4 compound.

8. Kimwipes

Kimwipes are paper fiber optic cleaning wipes for cleaning lab equipment and

instruments. In this experiment, it was used to wipe the pycnometer dry.

Methods

The class was divided into three clusters and were assigned their respective salts. Our

group was chosen to be a part of Cluster Three and the salt that was assigned to us was

Na2SO4. Before the said date of the experiment, each cluster was assigned to make a

4
 CO2 free distilled water. After that, the steps were followed in accordance to the

laboratory manual. The first step was to make sure that all the glass wares are clean dry

before performing the experiment. Then, 2, 4, 6, 8, 10, and 16 g of Na2SO4 were

accurately weighed per 100 mL solution and were prepared in the volumetric flasks. After

the preparation of the aqueous salt solutions, the pycnometer was allowed to attain

thermal equilibrium with the room. Its temperature was then recorded and its mass was

measured on the analytical balance. The pycnometer was filled with the previously boiled

distilled water and its temperature and mass were recorded. The pycnometer was emptied

and was refilled with the previously boiled distilled water and its temperature and mass

were recorded. This step was repeated four more times. Then the pycnometer was

emptied and was rinsed thoroughly with the most dilute Na2SO4 salt solution and its

constant temperature and mass were recorded. This step was repeated twice for every

Na2SO4 salt solution in order of increasing concentration. Finally, the data and results

(m, W, , , V 2 , and V 1 ) were tabulated in Excel.

Results

Table 1. Temperature and mass readings of empty pycnometer

Empty Pycnometer
We Mass (g) Temperature (C)
33.732 27.4

Table 1 shows the mass and temperature of the empty pycnometer.

Table 2. Temperature and mass readings of pycnometer with water

Pycnometer with Water
Wo Mass (g) Temperature (C)
Trial 1 58.2640 28.0
Trial 2 58.2665 28.2
Trial 3 58.2688 28.0
Average 58.26643333 28.06666667

5
 Table 2 shows the temperature and mass of the pycnometer with water. The
temperature and mass readings were done for three trials and their average were also
determined.

Table 3. Temperature and mass readings of pycnometer with Na2SO4 salt solution
2g
Mass (g) Temperature (C)
Trial 1 58.7215 27.4
Trial 2 58.7044 27.8
Trial 3
Average 58.71295 27.6
4g
Mass (g) Temperature (C)
Trial 1 59.1572 27.2
Trial 2 59.1427 27.6
Trial 3 59.1213 27.8
Average 59.1404 27.53333333
6g
Mass (g) Temperature (C)
Trial 1 59.5621 27.2
Trial 2 59.5635 27.4
Trial 3 59.556 27.4
Average 59.56053333 27.33333333
8g
Mass (g) Temperature (C)
Trial 1 60.006 27.4
Trial 2 59.5671 28.4
Trial 3 59.9835 27.8
Average 59.8522 27.86666667
10 g
Mass (g) Temperature (C)
Trial 1 60.371 27.9
Trial 2 60.3772 27.4
Trial 3 60.3917 27.6
Average 60.37996667 27.63333333
16 g
Mass (g) Temperature (C)
Trial 1 61.5055 28
Trial 2 61.5 27.9
Trial 3 61.5132 27.6
Average 61.50623333 27.83333333

Table 3 shows the mass and temperature readings for the different concentration of
Na2SO4 salt solutions. Three trials were done for each concentration.

Table 4. Calculated Values for W-We, , M, m, (1000/m)(W-Wo)/(Wo-We),m, and

6
Ma Actu W-We Density Molarity Molality (1000/m) Sqrt m (mL
ss al ( (M) (m) (W-Wo)/ mol-1)
(g) Mass (Wo-We)
(g)
2 2.004 1.014368 0.141129 0.141935 128.2246 0.376742 13.61961
24.98095
6 107 259 152 951 819 679
4 4.004 1.031724 0.281955 0.284322 125.2874 0.533218 16.23740
25.4084
9 998 787 488 663 987 217
6 6.026 25.82853 1.048784 0.424295 0.429224 122.8874 0.655152 18.26169
7 333 792 973 417 086 209 822
8 8.041 25.40596 1.031625 0.566164 0.595205 59.68127 0.771495 79.83390
8 111 966 461 761 276 794 297
10 10.04 26.64796 1.082058 0.706955 0.720176 119.6173 0.848632 20.72222
16 667 428 787 479 391 122 753
16 16.00 27.77423 1.127791 1.126936 1.164525 113.3948 1.079131 25.39937
7 333 236 074 519 053 836 694

Table 4 shows the calculated values for W-We, , M, m, (1000/m)(W-Wo)/(Wo-

We),m, and at each concentration. It can be observed that , M, m, m, and

increases as the concentration of the solution increases.

Table 5. Calculated Values for V2 and V1

Mass Actual m/2sqrtm slope V2 m/55.51 sqrtm/2 V1
Mass
2 0.188371 16.37 16.70382 0.0025 0.18837
2.0046 41 3 188 57 1 18.06111
4 0.266609 16.37 20.60259 0.0051 0.26660
4.0049 49 3 941 22 9 18.04664
6 0.327576 16.37 23.62510 0.0077 0.32757
6.0267 1 3 178 32 6 18.02753
8 0.385747 16.37 96.59265 0.0107 0.38574
8.0418 89 3 087 22 8 17.39181
10 0.424316 16.37 27.66955 0.0129 0.42431
10.0416 06 3 439 74 6 17.97887
16 0.539565 16.37 34.23368 0.0209 0.53956
16.007 92 3 972 79 6 17.88367

Table 5 shows the calculated values for V2 and V1. It can be observed that as the
concentration of solution increases, V2 increases while V1 decreases.

7
 vs m Na2SO4
90
80
70
60
50
(ml/mol)
40
f(x) = 28.3x + 8.9
30
R = 0.08
20
10
0
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2

sqrt m

Figure 1. Apparent Molar Volume Plotted Against the Square Root of Molality

Figure 1 shows the graph of apparent molar volume for the six Na2SO4 solution as a

function of the square root of each solutions molality. The values obtained were close to

each other except for the solution with 8 g of Na2SO4.

vs m Na2SO4
30

25
f(x) = 16.37x + 7.41
20 R = 0.99

(ml/mol) 15
10

0
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2

sqrt m

Figure 2. Apparent Molar Volume Plotted Against the Square Root of Molality

8
 Grubbs Test was used to identify if the suspected value was really an outlier. It was

confirmed that the value was an outlier, so it was eliminated. The new graph now was shown

in Figure 2 above.

V2 vs molality (m)
40
35
f(x) = - 5.95x^2 + 24.37x + 13.78
30
R = 1
25

V2 (mL) 20
15
10
5
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4

molality
(mol/kg)

Figure 3. Partial Molar Volume (V2) Plotted Against Molality (m)

Based on the graph of Figure 3, a direct relationship between V2 and m can be

observed. As m increases, V2 also increases.

9
 V1 vs molality (m)
18.1
18.05
f(x) = - 0.07x^2 - 0.08x + 18.07
18 R = 1

17.95
V1 (mL) 17.9
17.85
17.8
17.75
0 0.2 0.4 0.6 0.8 1 1.2 1.4

molality
(mol/kg)

Figure 4. Partial Molar Volume (V1) Plotted Against Molality (m)

The graph of Figure 4 shows an inverse relationship between V1 and m. As the value

of V1 increases, m decreases.

Discussion

In this experiment, the partial molar volumes of Na2SO4 salt solution was determined

by measuring the density of the solution. The density of each salt solution was determined

using a Weld pycnometer. The pycnometer was calibrated several times to obtain accurate

results.

The salt assigned to our Cluster was Na2SO4. Dilution at different mass of the salt

was carried out to determine the relationship of each concentration to the solutions partial

molar volume. Other than concentration, density also affects the partial molar volume.

Moreover, the temperature for each concentration was also determined because molarity is

dependent on temperature. Temperature has an effect on the molarity of a solution because it

is based on the volume of the solution.

10
 In table 3, it was observed that as the temperature decreases, the volume of the

solution increases. This implies that these variables have an inverse relationship.

In table 4, it was observed that density, molarity, and molality increases while the

concentration increases. Thus, these variables are considered to be directly proportional with

the solutions concentration.

In table 5, V2 increases while the concentration increases while V1 decreases while

concentration increases. V2 is known to be the partial molar volume of Na2SO4, hence when

its component increases in the solution V2 also increases. V1

In the graph of Figure 1, the solution with 8 g Na2SO4 deviates from the values of the

other five solutions. To identify if this suspected value was an outlier, Grubbs test was used.

It was confirmed that the said value was indeed an outlier. The outlier was eliminated to

support Massons theory of solutions of simple electrolytes of dilute moderate concentrations.

The graph in Figure 2 further approve his statement that a linear relation exists between the

apparent molar volume, , and the square root of the molality, .

The graph of Figure 3 shows a linear relationship between the partial molar volume of

Na2SO4, V2, and the molality, m. V2 increases as the value of m increases same way when

V2 decreases m decreases. This is due to the dependence of molality, m, to V2.

In the graph of Figure 4, an inverse relationship between the partial molar volume of

water, V1, and the molality, m. As the value of V1 increases, m decreases.

Conclusion

This experiment confirmed the following relationships. First, the concentration of the

solution is directly proportional to the density of the solution. It implies that the partial molar

volume of the solution is greatly affected by the concentration of the solution. Second, there

11
exists a linear relationship between the apparent molar volume of a salt solution and its root

of molality, supported by Massons theory.

We learned that the partial molar volume of the solute and solvent will not be equal to

the volume of the solution. This is because the partial molar volume of the solute is directly

proportional to its molality while the partial molar volume of the solvent is not. Thus, there is

no chance that the actual volume of the solution will be equal to the estimated volume for it

will always be lesser.

We also learned that the volumes of solution components are not additive. In a

solution with two components, molecules experience different intermolecular forces

compared to that of the pure substance. Differences in molecular sizes and shapes cause the

molecules of the substances to fit together differently. These factors cause the molecules to

pack together differently in contrast to pure substances thus it is true that the volumes are not

additive.

Since the partial molar volume of a substance is an intensive property, it depends on

the composition of the solution and not on the amount of solution. Also, the partial molar

volume depends on the mole fractions and not on the number of moles. It follows that the

partial molar volume of a substance is the molar volume of the substance in a solution at a

particular composition.

References

1. The Determination of Partial Molar Volume. Physical Chemistry I Laboratory

Manual. University of the Philippines-Visayas, (2016)
2. Garland C.W., Nibbler J.W., Shoemaker, D.P., Experiments in Physical Chemistry, 8 th

ed., McGraw-Hill Higher Education, 2009, 172-178.

3. Klotz, I.M., Rosenberg, R.M., Chemical Thermodynamics, 7th ed., John Wiley &

Sons, 2008, 10, 18-21.

4. DeVoe, H., Thermodynamics and Chemistry, 2nd ed., Howard DeVoe, 2015, 225-234

12
 5. Mortimer, R., Physical Chemistry, 3rd ed., Elsevier Inc., 2008, 188-192
6. Homogeneous Functions, Euler's Theorem and Partial Molar Quantities

https://www.e-education.psu.edu/png520/m15_p2.html (accessed Oct 12, 2016).

7. Atkins, D.W; de Paula, J, Physical Chemistry, 9th Ed.; W.H. Freeman; San Francisco,
2010
8. Riedel, M. & Ujvri M. Determination of the partial molar volume by density

measurement. [Online] 2016. Foundation01.chem.elte.hu/Chemistry_BSc_

MSc_English_Group/04_BLOCK/partialmolarvolume_2016.pdf

Appendices

Appendix A Calculations

Volume
m WoWe
Formula: V = =

58.26643333 g33.732 g
V= 0.996237 g /ml = 24.62710513 mL

Density
m wowe
Formula: = =
V V
2g 24.98095 g
= = 1.014368107 g / mL
24.62710513 ml
4g 25.4084 g
= = 1.031724998 g / mL
24.62710513 ml
6g 25.82853333 g
= = 1.048784792 g / mL
24.62710513 ml
8g 25.40596111g
= = 1.031625966 g / mL
24.62710513 ml
10 g 26.64796667 g
= = 1.082058428 g / mL
24.62710513 ml

13
16 g 27.77423333 g
= = 1.127791236 g / mL
24.62710513 ml

Molarity
mol solute
Formula: M = L solution
2g 0.014112926
M 0.1 = 0.141129259 mol / L
4g 0.028195579
M 0.1 = 0.281955787 mol / L
6g 0.042429597
M 0.1 = 0.424295973 mol / L
8g 0.056616446
M 0.1 = 0.566164461 mol / L
10 g 0.070695579
M 0.1 = 0.706955787 mol / L
16 g 0.112693607
M 0.1 = 1.126936074 mol / L

Molality
M
Formula: m = ( molar mass)(M )(0.001)

0.141129259
2g m= 1.014368107(142.04)( 0.141129259)(0.001) =

0.141935152 mol/kg

0.281955787
4g m= 1.031724998(142.04)(0.281955787)( 0.001) =

0.284322488 mol/kg

0.424295973
6g m= 1.048784792(142.04)(0.42429573)(0.001) =

14
 0.429224417 mol/kg

0.566164461
8g m= 1.031625966(142.04)( 0.566164461)(0.001) =

0.595205761 mol/kg

0.706955787
10 g m= 1.082058428(142.04)(0.706955787)( 0.001) =

0.720176479 mol/kg

1.126936074
16 g m= 1.127791263(142.04)(1.126936074)( 0.001) =

1.164525519 mol/kg

Formula: m

2g m= 0.141935152mol /kg = 0.376742819

4g m= 0.284322488 mol/kg = 0.533218987

6g
m= 0.429224417 mol/kg = 0.655152209

8g
m= 0.595205761mol /kg = 0.771495794

10 g
m= 0.720176479 mol/kg = 0.848632122

16 g
m= 1.164525519mol /kg = 1.079131836

15
 (1000/m)(W-W0)/(W0-We)

2g (1000/0.141935152)(58.71295 - 58.26643333)/(58.26643333-
33.732) = 128.2246951

4g (1000/0.284322488)(59.1404 - 58.26643333)/
(58.26643333-
33.732) = 125.2874663

(1000/0.429224417)(59.56053333 - 58.26643333)/
6g (58.26643333-
33.732) = 122.8874086

8g (1000/0.595205761)(59.13796111
- 58.26643333)/(58.26643333-
33.732) = 59.68127276

(1000/0.720176479)(60.37996667
10 g - 58.26643333)/(58.26643333-
33.732) = 119.6173391

16 g (1000/1.164525519)(61.50623333- 58.26643333)/
(58.26643333-
33.732) = 113.3948053

16
 1
Formula: = ( )(molar mass - (1000/m)(W-W0)/(W0-We))

2g 1
= ( 1.014368107 )( 142.04 - 128.2246951)

= 13.61961679 mL/mol

4g 1
=( 1.031724998 )( 142.04 - 125.2874663)

= 16.23740217 mL/mol

6g 1
= ( 1.048784792 )( 142.04 - 122.8874086)
= 18.26169822 mL/mol

8g 1
=( 1.031625966 )( 142.04 -59.68127276)

= 79.83390297 mL/mol

10 g 1
= ( 1.082058428 )( 142.04 - 119.6173391)

= 20.72222753 mL/mol

16 g 1
=( 1.127791236 )( 142.04 - 113.3948053)

= 25.39937694 mL/mol
V2

m
Formula: V2 = + ( 2 m )(slope)

17
2g 0.1419352
V2 = 13.61961679 + ( (2)(0.376742819) ) (16.373) =

16.70382188 mL

4g 0.2843225
V2 = 16.23740217 + ( (2)(0.533218987) ) (16.373) =

20.60259941 mL

6g 0.4292244
V2 = 18.26169822 + ( (2)(0.655152209) ) (16.373) =

23.62510178 mL

10 g 0.7201765
V2 = 20.72222753 + ( (2)(0.848632112) ) (16.37) mL=

27.66955439 mL

16 g 1.1645255
V2 = 25.39937694 + ( (2)(1.079131835) ) (16.373) =

34.23368972 mL

V1

m m
Formula: V1 = 18.069 - ( 55.51 ) ( 2 ) (slope)

2g V1 = 18.069 (0.002557) (0.188371) (16.373) =18.06111 mL

4g V1 = 18.069 (0.005122) (0.266609) (16.373) = 18.04664 mL

6g V1 = 18.069 (0.007732) (0.327576) (16.373) = 18.02753 mL

18
 10 g V1 = 18.069 (0.012974) (0.424316) (16.373) = 17.97887 mL

16 g V1 = 18.069 (0.020979) (0.539566) (16.373) = 17.88367 mL

Appendix B Answers to 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 information about the solute-solvent interactions and the solute structure in a

solution. It is also vital quantity in the analysis of the pressure effect on chemical reactions. It

has various applications in the field of biochemistry, oceanography and aquatic

environmental science.

2. The density of NaCl (s) is 2.165 g cm -3 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 NaCl is solid and the effects of pressure changes on the solubility of solids and

liquids are negligible.

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

the Gibbs-Duhem equation:

1 X 1
dQ
=
2
dQ 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

19
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

[ ( G
p ]
2)
= V 2

which was differentiated from the equation

)=V d p
d (G 2 2

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.

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.

20
 The intermolecular forces specifically the solute-solvent interactions in the solution cause

the differences in question 4 and 5.

21