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Partial Molar Volume

J. Cayabyab, J.R.L. Cu, A.M.S. Leron Department of Mining Metallurgical and Materials Engineering University of the Philippines Diliman angela_leron@yahoo.com Abstract
The determination of the Partial Molar Volume of NaCl solutions using a pycnometer yielded results that were precise but still very susceptible to human error. Experimental data showed positive values of partial molar volume of NaCl in each solution. This was due to the weak attraction between the solute (NaCl) and the solvent (H2O) and also causes increase in mixture volumes.

1. Introduction Generally, the volumes of solution components are not additive. Consider two components in one solution: first, the molecules experience different intermolecular forces compared to that of the pure substance. Those is the intermolecular forces between them, say between two water molecules and two ethanol molecules, is different from the intermolecular forces between a water molecule and an ethanol molecule. Second, the example, water and ethanol, have different sizes and shapes, compared to the pure substance counterpart and consequently, the water and ethanol molecule are going to fit together differently. These factors, differences in intermolecular forces and difference in molecular sizes and shapes cause the molecules to pack together differently in a mixture rather than in pure liquids thus, it is true that the volumes are non-additive. [1] For most organic liquids, the average molar volume V/n varies linearly with composition. Aqueous solutions are often anomalous because of an almost 3% volume change when a water-methanol is made up and a volume shrinkage when an electrolyte solution is made. The explanation lies with the reason that the ions attract water molecules so strongly that the resulting compaction more than compensates for the added volume of ions themselves. [2] 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. [1] The volume of a solution is dependent on its temperature and pressure and the component used to form the mixture. [3] For a binary system with components A and B, the partial component of A is given by:

Where V is the total volume nA is the number of moles A. Partial volume of A is, therefore, the change in volume per mole A added when an infinitesimal amount of A is added to the solution of constant P and T.

Where Va and VB are the partial molar volumes of A and B, respectively. [4] In this experiment, the partial molar volumes of water and alcohol solutions will be determined by density measurements using a pycnometer. A pycnometer is a flask with a tight fitting glass stopper with a fine hole. It is used for measuring the density of a solution upon Partial Molar Volume. Page 1 of 5

comparison to a control. It is important to know the specific gravity first. This is done by accurately measuring the mass of the reference liquid. [5] The specific gravity is determined by:

corresponding solution. This procedure was done to all the samples, having two replicates each. 3. Results and Discussion The plots of apparent molar volume vs square root of molality for both replicates were showed in Figure 1 and 2, and were found to be almost linear and with negative slopes. With R2 values of 0.798(replicate1) and 0.9403(replicate 2), the data can be said as almost precise. The partial molar volume of NaCl and water were computed using the slopes and intercepts of the best fit line on each graphs.
20 18 16 14 12 10 8 6 4 2 0

This experiment is intended to have a direct comparison of partial molar volumes by determining the density of the solution.

2. Methodology 2.1 Solution Preparation

Apparent molar volume

200 mL solutions of 1.5M, 0.75M, 0.375M, 0.1875M, and 0.09375M NaCl solutions were prepared. These solutions could be prepared by successive volumetric dilutions wherein each dilution was done with 100mL of solution into a 200-mL volumetric flask and fill it up to the mark with distilled water. 2.2 Pycnometer calibration Use a clean and dry pycnometer. An aspirator was used to dry it by suction. Also, few rinses of acetone were used for drying. The pycnometer was weighed until a reading of weight difference 0.01 grams. The pycnometer was filled with the control, distilled water and then covered. Excess liquid were wiped off around the pynometer joint and then as immersed in water bath just below the cap. The water bath is to let the pycnometer reach equilibrium. After which, the pycnometer was removed from the water bath then wiped off any excess liquid from the capillary tip. Weights were measured using the analytical balance. Two replicates were made. 2.3 Experiment With the 1.5M calibrated pycnometer solution was discarded The pycnometer was NaCl solution, the was rinsed and the before filling it again. then filled with the

y = -0.923x + 19.08 R = 0.798

1.24466 0.87311 0.6152 0.4344 0.30694

Fig 1. Apparent molar volume vs square root of molality (R1)

20 Apparent molar volume 15 10 5 0

1.24465 0.87313 0.61524 0.43439 0.30693

y = -1.116x + 19.53 R = 0.940

Fig 2. Apparent molar volume vs square root of molality (R2)

Values for partial molar volumes of NaCl and water for each solution were shown in Partial Molar Volume. Page 2 of 5

Table 1 (see appendix). The positive values of partial molar volume of NaCl in each solution are because of the weak attraction between the solute (NaCl) and the solvent (H2O) which causes increase in mixture volumes. Also, positive partial molar volume indicates that interactions between the solvent molecules (H2O-H2O) are stronger compared to the interactions of unlike molecules (NaCl-H2O) in the solutioni. Based on Table 1, increase in the concentration of NaCl increases the partial molar volume of water while decreases the partial molar volume of the NaCl. Errors in the experiment include; inaccurate preparation of solution, pycnometer was not exactly cooled to room temperature, which may affect the actual density of the water/solutions when weighing was conducted; hand moisture when handling the pycnometer contributed to higher measured weight compared to the actual weight. These errors may be prevented if the pycnometer was place in the bath for longer time for it to reach its equilibrium. Also, use of tissue when handling the pycnometer is recommended for more precise measurements. 4. Conclusion and Recommendation The use of pycnometer is the traditional way of determining the partial molar volume of a solution. [8] Therefore, this method can only be reliable at a laboratory scale. Using this method on a large amount of sample might result to erroneous data. However, this method of measuring is very prone to human error. Machines for density determination have been developed such as the DMA 4500 Density Meter which can accurately give data for the concentration and density of the sample and uses and oscillating U-tube. [7] Density meters have high precision than that of pycnometers since such apparatus involves a hollow glass tube which vibrates at a certain

frequency. Reading of the frequency fluctuates when sample is introduced into the system. The measured data, frequency, is then converted to density. [9] 5. References


Perona (Spring 2010) Partial Molar Volumes. Chem 4012 Adamson, A.W., A Textbook of Physical Chemistry. 1980: J. Chem Educ. Jaltig Measurement of Partial Molar Volumes. Physical Chemistry Laboratory. Anonymous Experiment 5Determination of Partial Molar Quantities. Chem 356, 1-9. Anonymous Experiment 1: partial Molar Volumes. ChE 121 Physical Chemistry 1 Laboratory. J.P. OConnell, J.M. Haile (2005). Thermodynamics: Fundamentals for Applications. Cambridge University Press Anton Paar. (n.d.). Density Meter. sterreich. Stabinger, H. (1994). Density Measurement using modern oscillating transducers. University of Delaware. (2006). Physical Chemistry Laboratory. Newark.









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Appendix Table 1. Derived values for molarity, molality, density, partial molar volume of water and partial molar volume of NaCl
1.5 M NaCl R1 d (g/cm) m (kg/mol) V NaCl V water 1.05592 1.54917 17.35878 18.08503 R2 1.05593 1.54915 17.45196 18.08840 0.75 M NaCl R1 1.02767 0.76232 17.87318 18.07453 R2 1.02763 0.76235 18.07434 18.07570 0.375 M NaCl R1 1.01274 0.37847 18.23026 18.07094 R2 1.01261 0.37852 18.50635 18.07134 0.1875 M NaCl R1 1.00457 0.18870 18.48057 18.06968 R2 1.00461 0.18870 18.80930 18.06982 0.09375 M NaCl R1 1.00059 0.09421 18.65704 18.06924 R2 1.00067 0.09420 19.02284 18.06929

Table 2. Experimental data for weight of pycnometer at 27 degree Celsius

Empty pycnometer Trial 1 Trial 2 Trial 3 Mean 22.3128 22.3129 22.3129 22.31287 Pycnometer with water 47.6305 47.6310 47.6305 47.6307

Table 3. Experimental data for weight of each solution

1.5 M NaCl R1 Trial 1 Trial 2 Trial 3 Mean 49.1401 49.1400 49.1403 49.1402 R2 49.1406 49.1406 49.1399 49.1404 0.75 M NaCl R1 48.4246 48.4215 48.4211 48.4224 R2 48.4215 48.4215 48.4211 48.4214 0.375 M NaCl R1 48.0440 48.0433 48.0420 48.0431 R2 48.0399 48.0396 48.0395 48.0397 0.1875 M NaCl R1 47.8355 47.8356 47.8355 47.8355 R2 47.8365 47.8362 47.8365 47.8364 0.09375 M NaCl R1 47.7338 47.7346 47.7344 47.7343 R2 47.7293 47.7292 47.7394 47.7326

Sample Calculations:

Volume of pycnometer:


Density of each solution:

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Molality of each solution:


Apparent molar volume each solution:

where: W = weight of pycnometer filled to mark with solution W0 = weight of pycnometer filled to mark with pure water We = weight of empty pycnometer M = solute molecular weight


Partial Molar Volume of NaCl:


Partial Molar Volume of water:

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