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Partial Molar Volume Measurement Discussion

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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]

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

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

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

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: Graph of the apparent molar volume against the square root of

A tabulated form of the molarity, average dry molality.

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

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

Appendix:

Table 3:

Table 4:

Table 5:

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

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