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PARTIAL MOLAR VOLUME

DETERMINATION OF DIFFERENT NACL


CONCENTRATIONS
Huerto, M.A.a, Mallapre, W.A.b, Mercado, R.c
Department of Mining, Metallurgical and Materials Engineering
Quezon City, Philippines
mauricehuerto@yahoo.coma, womallapre@up.edu.phb

Abstract In the case of many water-ethanol or salt case of the references research) concentration up to
systems, a change of product volume varying accordingly 50% at 20C increases the solubility of organic salts
with the mole fraction of its constituents can be observed. which enhances or hastens the production time of salt
This phenomenon is called Partial Molar Volumes and
derivatives [3].
serves as an important factor in many solution theories
and chemical processes delicate enough where small The preparation of these aqueous mixtures
changes in concentration and volume significantly affects such as the water-ethanol solution used for
the kinetics of the system. Different concentrations of
electrodialysis can be very delicate or specific in the
NaCl solutions were prepared with each of their densities
concentration of its constituents as they can greatly
measured, these parameters were then manipulated into
equations governed by the Raoults Law and Debye- affect what products are formed and their respective
Huckel Theory to finally give the apparent molar volume amounts.
of the solute and solvent.
When mixing two equal amounts of pure
water and ethanol, the volume of the product does not
Index Termspartial molar volume, density simply equate to the sum of the volume of its reactants
but a rather decreased volume due to thermodynamic
processes to be discussed. By setting the temperature
I. Introduction and pressure as state variables of the water-ethanol
solution constant, the excess volume of water-ethanol
Monosodium glutamate or MSG is a
mixture generated is affected by the relative amounts
naturally occurring organic salt found in various dairy
of each component shown in Fig.1. [4]
products, vegetables, and fruits such as cheese,
potatoes, and peas. MSG is a sodium salt derivative of
glutamic acid and is processed vastly in the food
industry as a flavor enhancer. In the Philippines
context, Ajinamoto serves as one of the leading
producers of food seasoning known for its MSG
content. [1]

Organic salts such as MSG may be


synthesized using different methods. One of such
methods is called Electrodialysis, which utilizes
permeable membranes that selectively let ions pass
through electric potentials. A major part in the
conventional way of electrodialysis is the use of an
aqueous mixture as a medium such as water-ethanol Fig. 1. Plot of Excess Volume of Ethanol and
solutions up to 50% v/v [2]. Kameche, Xu, and Water versus the Mole Fraction of Ethanol [4].
Innocent3 found that increasing alcohol (ethanol in the

Huerto, M.A., Mallapre, W.A., Mercado, R. (2017) 1 of 6


This phenomenon observed in the referred
study is called the Partial Molar Volume and is defined
as the change in the volume of an assumed infinite (5)
amount of solution per added molecule of a
constituent. 0 is obtained through extrapolating the
graph at zero concentrations to determine initial
In thermodynamics, partial molar quantities values.
act as an extensive property that defines the mole
fraction of a constituent in the solution that can be Like the study of the Water-Ethanol solution
expressed in Eq. 1 as: previously presented, the experiment will only focus
on solutions of NaCl-Water with varying
concentrations.
II. Methodology
(1) The experiment was conducted at the
By assuming that the solution is homogeneous, University of the Philippines-Diliman where the
the Eulers equation can be used to derive an equation equipment and apparatus needed were available.
that shows that changes between partial molar NaCl solution with different concentrations
quantities can be related with each other as seen in Eq. namely 1.5M, 0.75M, 0.375M, 0.1875M and
2. 0.09375M were prepared by successive volumetric
dilutions. Afterwards, the pycnometer that will serve
as the container of the solution during weighing was
calibrated. It is rinsed with distilled water and dried by
(2) suction using an aspirator. Few rinses of acetone
As the Raoults Law states where the partial helped in drying the pycnometer quickly. The weight
vapor pressure of a constituent is the vapor pressure of of an empty pycnometer was obtained. The
its pure form multiplied by its mole fraction in a pycnometer was then filled with distilled water and the
solution, Eq. 2 can be further manipulated to Eq. 3 to capillary stopper was firmly seated. The pycnometer
show to the overall contribution of each component in was immersed in a water bath maintained at constant
a binary system. temperature just below its cap. After reaching
equilibrium, the pycnometer was removed from water
bath. Excess liquid from capillary tip was wiped off
(3)
before weighing the pycnometer with water. Three
replicates were made.
The calibrated pycnometer was rinsed with
(4) the solution to be used. It was then filled with the
Plugging in Eq. 3 in the apparent molar volume corresponding solution. The procedure for water
equation, Eq. 4, an alternative apparent molar volume calibration was repeated for all concentrations of NaCl
equation that uses the parameters measured in the solutions.
experiment is derived and is presented as Eq. 5.
III. Results and Discussion

(5) It is necessary to calculate the densities of the


solutions to obtain their partial molar volumes. In
With Eq. 5 set, a plot of phi versus sqrt of m calculating for the density of NaCl, it is essential to
(for simple electrolytes) must be made to determine its calibrate the pycnometers volume first. The
slope. The slope can be further manipulated to calibration was done using the density of pure water
determine the final apparent molar volumes of NaCl while considering the temperature of the set-up; since
and H2O with accordance to Eq. 6. an increase in temperature corresponds to a decrease

Huerto, M.A., Mallapre, W.A., Mercado, R. (2017) 2 of 6


in the density of pure water. [3] After calibrating and molar volume () vs. m. The square root of molality
weighing the pycnometer filled with NaCl, the density was used to linearly regress the variables, and this is
of the NaCl solutions was calculated; and as expected, permitted for dilute to moderate electrolytic
the average density of the NaCl solution is solutions per Debye-Huckel theory. Plotting vs. m
proportional with the molarity. and fitting the best line would yield to the equation, y
= 9.65611x + 8.52565, with an R2 value of 0.56792.

Figure 1: Trend of Density vs. Molarity of NaCl


Figure 1: Graph of the apparent molar volume against the square root of
A tabulated form of the molarity, average dry molality.

weight and average calibrated volume of pycnometer,


Assessing the table above, one can infer that
and the average density of the NaCl is provided.
there is no particular trend in the partial molar volume
Table 1: Average density of NaCl solutions calculated from the calibration. of H2O in relation to the molar fraction of NaCl,
Molarity Average Average Average however, an increase in molar fraction of NaCl
(mol/L) Weight of calibrated density of corresponds to an increase in the partial molar volume
Pycnometer volume of NaCl soln of NaCl.
(g) pycnometer (g/mL)
(mL) An R2 value closer to 1 means that the data
1.5 21.0097 24.9903 1.0562 points are close to the best fit line [4], for our case an
0.75 22.9886 25.1319 1.0280 R2 value of 0.56792 indicates that the calculated
0.375 22.3502 24.9581 1.0146 apparent molar volume and molality have deviated
0.1875 22.68793 24.9153 1.0053 from the best fit line. This may signify low to medium
0.09375 21.2118 24.9079 1.0015
accuracy in the measurement and calculation of the
With the density of NaCl solutions being density.
available, the molality, the apparent molar volume
Several factors may be attributed to this
(), and partial molar volumes (V1 and V2) can already
deviation- temperature variations, limitation of the
be determined; since all of them are a function of
instruments, pooling of the data, etc. Difference in the
NaCls density. A table containing all the quantities is
temperature of the water bath and the room
provided to clearly see the trends.
temperature may have caused density deviations in the
Table 2: Derived values of Molality, Density, V1 of H2O, and V2 of NaCl. H2O and NaCl solution. Additionally, the
Molarity Molality V1 V2 thermometers used were already malfunctioning
(mol/L) (mmol/g) (mL/mol) (mL/mol) (mL/mol)
showing erroneous readings (i.e., reading the room
1.5 1.5488 19.1483 17.9014 26.5512
temperature as 58C). Pooling the data did save time
0.75 0.7620 16.7269 18.0111 21.1695
0.375 0.3778 18.2227 18.0488 17.4280 and energy but this did not help in preserving the
0.1875 0.1886 14.9045 18.0619 14.8153 accuracy of the density measurement due to the
0.09375 0.0941 7.1627 18.0664 12.9694 difference in handling the pycnometer. These
While and molality are both dependent to problems could be alleviated and minimized if only
the density, V1 and V2 are dependent on d/dm and one person conducted the experiment, if the
pycnometers used were all placed in a single water
0 which can be derived from the plot of apparent

Huerto, M.A., Mallapre, W.A., Mercado, R. (2017) 3 of 6


bath, and if finer and more precise instruments are [10]"Mass, Weight, Density or Specific Gravity of
provided. Water at Various Temperatures." Mass, Weight,
Density, or Specific Gravity of Water at Various
IV. Conclusion Temperatures. Accessed February 23, 2017.
The partial molar volume of the different https://www.simetric.co.uk/si_water.htm.
[11 Business, Fuqua School of. "What's a good value
concentrations of NaCl solution is inversely
for R-squared?" What's a good value for R-squared?
proportional with the mole fraction of NaCl. It is also
Accessed February 23, 2017.
a function of concentration, but does not depend on
https://people.duke.edu/%7Ernau/rsquared.htm.
the total number of moles. The values for each partial
molar volume vary depending on the method of
analyzing the data. In this experiment, the plot of
vs. m and its best line was used. It yielded an
equation, y = 9.65611x + 8.52565, with an R2 value of
0.56792. The value of R2 indicates that calculated
apparent molar volume and molality have deviated
from the best fit line which signifies low to medium
accuracy in the measurement and calculation of the
density.

References
[1] "Monosodium glutamate." Wikiwand. Accessed
February 22, 2017.
http://www.wikiwand.com/en/Monosodium_glutamat
e.
[2] "Water Treatment Solutions." Electrodialysis.
Accessed February 22, 2017.
http://www.lenntech.com/electrodialysis.htm.
[3] Kameche, Mostfa, Feina Xu, Christophe
Innocent, and Grald Pourcelly. "Electrodialysis in
water-ethanol solutions: Application to the
acidification of organic salts." Desalination 154, no. 1
(2003): 9-15. doi:10.1016/s0011-9164(03)00203-0.
[4] "The Basics of General, Organic, and Biological
Chemistry, v. 1.0." Flat World Knowledge. Accessed
February 22, 2017.
http://catalog.flatworldknowledge.com/bookhub/read

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Appendix:
Table 3:

Table 4:

Table 5:

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