Introduction

Some property of a pure chemical species changes when it is made a

solution with other species. These properties that are affected are called the partial
molar quantities. Partial molar quantities tell us how the extensive properties of
solutions change with molar composition. Essentially it is the partial derivative of
the extensive property with respect to the number of moles of the component of
interest. Every extensive property of a mixture has a corresponding partial molar
property (5). The objective of this experiment is to determine the partial molar
volume of the components or the solution.

Theory
Partial molar properties are important because they can denote the degree of non-
ideality of a system. In a solution, the constituents are intimately mixed. Due to
molecular interactions between the species in the solution, their individual
properties are modified to some degree. This implies that substances in a solution
cannot have private properties, or ones that remain truly unaffected despite being
in the presence of another material (6).

The partial molar volume of a substance is an intensive property. It depends on

the composition of the solution, but not on the amount of the solution. Also, the
partial molar volume depends on the mole fractions and not on the number of
moles. Hence it follows that the partial molar volume of a substance is the molar
volume of the substance in a solution at a particular composition (7).

The volume of the mixture V, V= V(p, T, nA, nB) obeys two equations. First,
because V is extensive, we get: V= nAVA + nBVB. This allows us to calculate the total
volume V if we know the partial molar volumes and composition. The partial molar
volumes are:
𝜕𝑉 𝜕𝑉
𝑉𝐴 = ( ) 𝑉𝐵 = ( )
𝜕𝑛𝐴 𝑃,𝑇,𝑛 𝜕𝑛𝐵 𝑃,𝑇,𝑛
𝐵 𝐴

VA may be measured by finding the slope of the plot of the total volume V vs. nA,
while p, T and nB are kept fixed.The second equation results from the fact that V is
a state function. When we change the system composition at p,T=const: the
change in the system volume will be:
𝑑𝑉 = 𝑉𝐴 𝑑𝑛𝐴 + 𝑉𝐵 𝑑𝑛𝐵 (2)
(𝑝, 𝑇, 𝑛𝐴 , 𝑛𝐵 ) → (𝑝, 𝑇, 𝑛𝐴 + 𝑑𝑛𝐴 , 𝑛𝐵 + 𝑑𝑛𝐵 )

We can use the values of the partial molar volumes to predict changes in the
system volume upon small changes in composition. We can say that the partial
molar volume VA represents the volume change when 1 mol of A is added to a large
amount of the mixture. For finite changes of composition equation (2) may be
written
∆𝑉 ≈ 𝑉𝐴 ∆𝑛𝐴 + 𝑉𝐵 ∆𝑛𝐵
where the approximation comes in because VA and VB themselves vary with
composition, so the formula works best when the changes are in composition are
small.
Experimental Procedure
The materials for this experiment were Pycnometer, three 100-ml beakers,
one pipet and aspirator, 250 ml round bottom flask and 100-ml cylinder. The
pycnometer were dried using the blower and was then weighed, W p, in an analytical
balance. The data gathered was recorder in the lab notebook. It was filled with
distilled water until the water level reaches the top of the capillary. The researchers
then checked that there were no air bubbles and that the outside surface of the
pycnometer was completely dry. After, the pycnometer containing water was
weighed, W g. The researchers calculated the volume of pycnometer using the
obtained data. In each beakers, three solutions of HCl were prepared with varying
concentrations (wt./wt.) of 10%, 20%, and 30% from a HCl solution with 37.25%
average concentration. For the solution to be made the researchers solved for the
initial volume of the HCl to be diluted with water, up to 30 ml of the pycnometer
(solution shown below). The pycnometer was filled consecutively with the 10%, 20%
and 30% wt./wt HCl solution. It was weighed, W 10, W 20 and W 30 respectively, after
making sure that there was no air bubbles and the outside surface was completely
dry. The obtained data were recorded on lab notebook.

Results and Discussion

Solution weight of solution (g), A Mass of HCl (g), B Mass of H2O (g), C
1 26.869 2.6869 24.1821
2 28.13 5.626 22.504
3 29.343 8.8029 20.5401
Table 1 - Weight and Mass

mole of H2O (mol), mole of HCl (mol), mole fraction of mole fraction of
Solution D E H2O, xH20 HCl, xHCl
1 1.3419 0.0717 0.9493 0.0507
2 1.2488 0.1501 0.8927 0.1073
3 1.1398 0.2349 0.8291 0.1709
Table 2 – Mole and Mole Fraction for H2O and HCl

Solution density (g/mL), F specific volume (mL/g), G

1 1.045811926 0.956194871
2 1.094893352 0.913330963
3 1.142106492 0.875575095
Table 3 - Density and Specific Volume

Solution Partial Specific Volume of H2O (mL/g), H Partial Specific Volume of HCl (mL/g), I
1 1.001 0.545
2 0.999 0.558
3 0.998 0.663
Table 4 – Partial Molar Volume
 Theoretical Specific
Volume of HCl solution Experimental Specific Volume
solution (mL), J of HCl solution (Ml), K % difference, L
1 0.961 0.956194871 0.005000134
2 0.9567 0.913330963 0.045331908
3 0.9405 0.875575095 0.069032329
Table 5 – Specific Volume of HCl Solution

Partial Molar Volume of Partial Molar Volume of H2O Molar Volume

Solution HCl (mL/mol), VM-HCl (mL/mol), VM-H20 (mL/mol), VM
1 18.9592 18.2002 18.174
2 21.3291 17.98396 18.363
3 22.9698 17.5695 18.688
Table 6 – Partial Molar Volume and Molar Volume of HCl and H2O

% Weight of HCl vs Mole Fraction

y = -0.601x + 1.0106
1
R² = 0.9989
0.9
0.8
0.7
Mole Fraction

0.6
0.5
0.4 y = 0.601x - 0.0106
0.3 R² = 0.9989
0.2
0.1
0
0% 5% 10% 15% 20% 25% 30% 35%
% Weight of HCl Solution

mole fractionFigure
of HCl, xHCl mole
1 - Mole Fraction of HClfraction
and HofOH2O, xH20
2
Linear (mole fraction of HCl, xHCl) Linear (mole fraction of H2O, xH20)

Figure 1 – Molar Fraction of HCl and H2O

 % Weight of HCl vs Density
1.16
y = 0.4815x + 0.998
1.14 R² = 0.9999

1.12
Density, g/ml

1.1

1.08

1.06

1.04
0% 5% 10% 15% 20% 25% 30% 35%
% Weight of HCl

Density Linear (Density) Linear (Density)

Figure 2 – Linearity of Density with increasing % Weight of HCl

% Weight of HCl vs Specific Volume

1
Specific Volume off HCL solution (mL)

0.95
0.9
0.85
0.8
0.75
0.7
0.65
0.6
0.55
0.5
0.45
0.4
0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%
% Weight of HCl

Figure 3 – Plotting % Weight of HCl vs Specific Volume to obtain the

value of the Partial Specific value of HCl and H2O
 Partial Specific Volume of HCl and H2O
1.12
1.05
0.98
0.91
Partial Specific Volume, mL/g

0.84
0.77
0.7
0.63
0.56
0.49
0.42
0.35
0.28
0.21
0.14
0.07
0
0% 5% 10% 15% 20% 25% 30% 35%
% Weight of HCl

Partial Specific Volume of H2O (mL/g), H Partial Specific Volume of HCl (mL/g), I

Figure 4 – Comparison of the Partial Specific Volume of HCl and H2O

% Difference of Specific Volume of HCl Solution

0.98
0.96
0.94
0.92
0.9 y = -0.4031x + 0.9957
R² = 0.9987
0.88
0.86
0% 5% 10% 15% 20% 25% 30% 35%

Theoretical Specific Volume of HCl solution (mL), J

Experimental Specific Volume of HCl solution (Ml), K
Linear (Experimental Specific Volume of HCl solution (Ml), K)
Linear (Experimental Specific Volume of HCl solution (Ml), K)

Figure 5 – Comparison of the Theoretical and Experimental Specific Volume

 25
Partial Molar Volume (ml/mol) y = -5.1646x + 18.498
R² = 0.9785
20

y = 32.538x + 17.434
15
R² = 0.9813

10

0
0 0.05 0.1 0.15 0.2
Mole Fraction of HCl

Partial Molar Volume of HCl Partial Molar Volume of H2O

Linear (Partial Molar Volume of HCl) Linear (Partial Molar Volume of H2O)

Figure 6 – Comparison the Partial Molar Volume of HCl and H2O

Discussion and Conclusion

The HCl masses are calculated by multiplying the weight of the solution and
the weight percent of HCl then the obtained values are subtracted by the weight of
the solutions to acquire the weight of the H2O. These values were converted to
moles by multiplying the inverse molar mass and its respective mass. The mole
fractions of HCL and H2O is obtained by getting the quotient of the moles of the
components of the solution with the total moles. Observed from figure 1, the mole
fraction of H2O is inversely proportional with HCl. Increasing the % weight of HCl
also increases the mole fraction of HCl and otherwise for H2O which means as the %
weight increase with the molecules of HCl that dissociates with H2O also increases.

The density is obtained with the quotient of the mass of the solution and the
volume of the pycnometer on the other hand, the inverse of the density is the
specific value of the HCl solution. See in figure 2 that the linearity of the density of
HCl increases as the % weight of HCl increases this is due to increases of mass
of the solution as more HCl is added to the solution, the mass of the component of
the solution increases per molecule. Also observe that the r-square is close to 1
and is fitted with the regression line which means that the data are normally
distributed.

The partial specific volume of the components of the solution are obtained by
graphing the percent weight of the HCl and the specific volume. Values that
intersect 100% is the partial specific volume of HCl and values that intersects the
0% is the partial specific volume of the H2O. Refer to table 4 and figure 2 for the
values and graph. See that the partial specific volume of HCl increases as the
concentration of HCl increases and as concentration of HCl approaches zero the
partial molar volume of H2O also increases. This signifies that the partial specific
volume is being ruled by the concentration of HCl which means that both depends
on the number of molecules present of the components in the solution.
 The theoretical values of the specific volume of the HCl solutions is calculated
by adding the product of the partial specific volume of the HCl and H2O and the
percent weight of HCl and H2O. The percent difference of the experimental and the
theoretical was also calculated, the values are shown in table 5 which tells us that
there is a small percent of error with the experimental values that was gathered
and the experimental values are close with the theoretical values of the specific
volume of the HCl solution. See in figure 5 that there is a discrepancy between 20%
and 30% the possible factor that might cause this is the temperature of the
laboratory surroundings, the fluctuation of the temperature affected the density
since increasing the temperature also increases the density. Heating a substance
causes molecules to speed up and spread slightly further apart, occupying a larger
volume that results in a decrease in density. Cooling a substance causes
molecules to slow down and get slightly closer together, occupying a smaller
volume that results in an increase in density (8).

Observe in figure 6 that with increasing mole fraction of HCl the partial molar
volume of HCl is also increasing approaching the value of 22.9698 mL/mol. The
same for the partial molar volume of H2O, as the mole fraction approaches zero
the partial molar volume increases to 18.2002 mL/mol. Different concentration of
HCl with H2O results in a change of the partial molar volume of each component
due to the molecular interactions, dipole – dipole interaction, between HCl and H2O.
Dipole-dipole interaction is the intermolecular attraction between two molecules.
After addition of HCl to water, the molecules of HCl gets surrounded by the
molecules of H2O. Even though the intramolecular interaction is stronger than the
intermolecular one, overcoming of the intramolecular covalent bond becomes
possible due to the large presence of H2O molecule. Also the dissociation of HCl
in water is a reaction which forms new bonds. The factors that affect the partial
molar volume of a solution are the composition and mole fraction since the
molecular environment changes with accordance to these to parameters (8). The
equations and the R-squared of each line is also shown in figure 6. It can be
observed that the regression line is close with the experimental values and the R-
squared values is almost near to 1 which means that the data gathered from the
experiment are precise and are normally distributed. Also the significance of the
intersection in the graph signifies that at 10% of HCl the partial molar volume of
HCl and H2O have almost the same values in 1 mole hence the partial molar
volume of the solution is almost proportionate in 10% weight of HCl solution.

The reasons for errors in the experiment are due to human error of inaccurately
recording of data. Failure to completely remove water which can adhere to the
internal surface while drying the pycnometer, adhesion of water vapor from the air
and touching the pycnometer and failure to completely dry the pycnometer after
disposal of the solution could also be a source of error of the experiment.

The researchers recommend to have more trials with each concentration to

have a bigger picture and a bigger curves in your data. Also, a water bath should
be prepared to attain constant temperature.

Reference
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https://chem.libretexts.org/Textbook_Maps/Physical_and_Theoretical_Chemi
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http://www.faculty.ku.edu/~chem510/lect/pmolar/pmolar.html
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https://www.sciencedirect.com/science/article/pii/S1359027898000169
(4) Gagen, Walter L. (1 May 2002). The Significance of the “Partial Specific
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https://pubs.acs.org/doi/pdf/10.1021/bi00872a010
(5) http://cbc.chem.arizona.edu/~salzmanr/480a/480ants/mixpmqis/mixpmqis.ht
ml
(6) K.A. Cruz, D.L.C. Fernando, R.A. (Sep 26, 2014). Formal Report on Partial
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https://www.scribd.com/doc/241094676/Formal-Report-on-Partial-Molar-
Volume-Experiment
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Volume
(8) American Chemical Society. Temperature affects density. Retrieved from
http://www.middleschoolchemistry.com/lessonplans/chapter3/lesson6

Appendix

Left: the materials used in the experiment Right: Preparation of 10%, 20%, and 30%
HCl solutions