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116 Astorga-Bronzal-Araniador Report #4
116 Astorga-Bronzal-Araniador Report #4
116 Astorga-Bronzal-Araniador Report #4
Chemistry I
Laboratory Course
By
with
LUCILE A. BRONZAL
Section I
ARNOLD C. GAJE
Laboratory Instructor
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
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).
theorem and Gibbs-Duhem relation. The Eulers theorem and the Gibbs-Duhem equation
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
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
(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
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.
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
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
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
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
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
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.
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 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
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)
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)
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
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
concentration increases. V2 is known to be the partial molar volume of Na2SO4, hence when
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
The graph in Figure 2 further approve his statement that a linear relation exists between the
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
In the graph of Figure 4, an inverse relationship between the partial molar volume of
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
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
We also learned that the volumes of solution components are not additive. In a
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.
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
12
5. Mortimer, R., Physical Chemistry, 3rd ed., Elsevier Inc., 2008, 188-192
6. Homogeneous Functions, Euler's Theorem and Partial Molar Quantities
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
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)
18
10 g V1 = 18.069 (0.012974) (0.424316) (16.373) = 17.97887 mL
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
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
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
3. Discuss qualitatively whether the curves of V1 and V2 versus m behave in accord with
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
[ ( G
p ]
2)
= V 2
)=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
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
20
The intermolecular forces specifically the solute-solvent interactions in the solution cause
21