Solubility of Solids in Liquids and Partial Molal Volume

Dewi Farra Prasasya*, Daffa Akmal Nugraha ,and Lintang Alivia Anggerta

Physical Chemistry Laboratory, Chemical Engineering Department FTI ITS

ITS Sukolilo Campus, Surabaya 60111

REPORT INFO ABSTRACT

The purposes of this experiment were to determine the solubility of benzoic acid at
Report History: different temperature and with or without glass rod, and relation between heat value of
Experiment 11 October 2018
solution with solubility. In this experiment, solubility was determined using titration
Received 18 October 2018
Revised 25 October 2018
method. Benzoic acid that was dissolved with distilled water as the analytes were in
different temperature variables while the crystal formation process was occured. For each
Keywords:
temperature, solutions were got two different treatment which were with and without
Molal glass rod. Analytes were titrated with NaOH and PP as indicator. Solubility then was
Solubility determined using mass of solvent and volume of titrant that was needed in titration. It
Temperature was obtained that the solubility of benzoic acid at 29°C without glass rod is 0.0005 while
Volume with glass rod it is 0.0007. The solubility of benzoic acid in 39°C without glass rod is 0.0008
while with glass rod it is 0.0006. Solubility is directy proportional to temperature, which
39°C has the highest value of solubility. From the graphic, it was obtained that the heat
value of the solution with glassrod was 0.0091 J/mol, and without glassrod was 0.0058
J/mol.The aim of this experiments two were to determine the partial molal volumes of
sodium chloride and water in a series of solutions from 0.3 to 3.0 m. Start with prepare
25 ml of five solutions of sodium chloride in distilled water ranging in molal concentration
from about 0.3 to 3.0. Measured the solute with electronic balance and measured the
solvent with a milligram balance into dry stoppered flasks Suspend the flasks in the 25°C
bath to reach constant temperature. Measure the density of the sodium chloride
solutions, taking the same procedure used in calibrating the pychnometer. It is obtained
that the total volume of the mixture is lower than the total volume of the pure
component, the dissolved molal volume is smaller than the molal volume of pure
solvent.The attractive force between molecules causes a reduction in the volume of
solution because the attractive force of the pure solvent molecule and the tensile force
between the solvent-soluble molecules are grater

1. Introduction
Solubility is the amount of substance that can dissolve in a number of solvents to form a saturated solution. The way to determine the
solubility of a substance is to take a certain amount of pure solvent, for example 1 liter. Then estimate the amount of substances that can
form a solution through saturation, which is characterized by the presence of insoluble solids. After being shaken or stirred, there will be an
equilibrium between substances that dissolve with substances that are not dissolved (Atkins, 1994).
What is meant by the solubility of a substance in a solvent, is the amount of a substance that can dissolve to the maximum in a solvent
under certain conditions. Usually expressed in units of mol / liter. So, if the solubility limit is reached, then the dissolved substance is within
the equilibrium limit, meaning that if the solute is added, a saturated solution will occur, if the dissolved substance is reduced, a solution that
has not been saturated will occur. And equilibrium depends on the dissolution temperature (Sukardjo, 1997).
The two components in the solution are solute and solvent. Solute is a dissolving substance. An example of a NaCl. NaCl solution is
solute and water is a solvent. Of the three materials, solid, liquid and gas, it is possible to have nine different types
of solutions: solid in solid, solid in liquid, solid in gas, liquid in liquid, and so on. Of these types, the solution we commonly know is solids in
liquids, liquids in liquids, gases in liquids and gases in gases (Sukardjo, 1997).
Molal or molality is a measure of the concentration of a solute in a solution in terms of amount of substance in a specified amount of
mass of the solvent. Means that is the ratio between the number of mol solute and the mass of the solvent in kilograms which can be
expressed as m = n / 1 kg, where m is molality, n is mol solute and 1 kg is the solvent mass. So, if there is a 1 molal solution, it contains 1 mole
of solute for 1 kg of solvent (Brady, 1990).
Dewi Farra Prasasya . Tel: +628811282074
E-mail addres : dewifarraprasasya@gmail.com
 Prasasya,DF and Nugraha,DA / Lintang Alivia Anggerta / Solubility of Solids in Liquids and Partial Molal Volume

the partial molar volume of a substance A in a mixture is the change in volume per mole of A added to a large volume of the mixture.
(Atkins,1994)
The partial molar volume, VJ, of a substance J at some general composition is defined formally as follows:
𝜕𝑉
𝑉𝑗 = ( )
𝜕𝑛
(1)
The definition in eqn 5.1 implies that, when the composition of the mixture is changed by the addition of dnAof A and dnBof B, then
the total volume of the mixture changes by
𝜕𝑉 𝜕𝑉 𝛿𝑉
dV = ( ) 𝑑𝑇 + ( ) 𝑑𝑃 + ∑ (
𝜕𝑇 𝜕𝑃 𝛿𝑑𝑛𝑖
) 𝑑𝑛𝑖 (2)
Partial molar volumes can be measured in several ways. One method is to measure the dependence of the volume on the composition
and to fit the observed volume to a function of the amount of the substance. Once the function has been found, its slope can be determined
at any composition of interest by differentiation. (Atkins ,1994)

2. Materials, Equipment, and Experiment Method

2.1 Material and Equipment

The equipment that were used in experiment one were beaker glass, graduated cylinder, heater, thermometer, test tubes,graduated
pipette, glass rod, erlenmeyer flask, burette
The material that were used in experiment one were 1 gram ofbenzoid acid, distilled water, filter paper, 0.05 M NaOH solution,
phenolphthalein.
The equipment that were used in experiment three were10 ml-pycnometer, 100 ml-graduated cylinder, a glass rod, watch glass, 10ml-
graduated pipette, beaker glass, electronic balance
The material that were used in experiment three were sodium chloride and pure water.

2.2 Experiment Method

In the experiment one first ,1 gram of benzoic acid was put into beaker glass, then 125 ml of distilled water were added into it. After
that the beaker glass was heated on the heater while stirring gently with a glass rod up to 70-75. Then, after all benzoic acid dissolved, pipette
20 ml of solution into 4 separate test tubes. After that, two of the tubes were kept in water bath at room temperature, and place a glass rod
into one of them and two of the another tubes were kept in water bath at 39°C and place a glass rod into one of them. After that, observed
crystal formation, then starting from the higher temperature sample test tubes, filter each sample that are waited at the same temperature
into seperate beakers. Then 5 ml sample from this beaker was pipetted to graduated cylined into a 50 ml. After that the erlenmeyer and the
solution were weighed in electronic balance. Then, the weighed solution is titrated with the standardized 0.05 M NaOH soluction using
phenolphthalein as the indicator.

In the experiment three First, the empty pycnometer was measured by electronic balance and then record the mass. After that, the
aquadest was added to the pychnometer by pipette and the pyhnometer was measured by the elecronoc balance and the mass was recorded
. Then, Prepare about 10 ml of four solutions of sodium chloride in distilled water ranging in molal concentration from about 0.3, 0.975,1.65
,2.325,3. then, the pynometer filled with solution of sodium chloride by pipette. After that, the sodium chloride in pycnometer was measured
by electronic balance and the mass was record .

3. Result and Discussion

3.1 Experiment Result

Table 1. Results of Experiments and Calculation of Solubility of Solids in Liquids

No T (°C) Solubility (X) 1/T (°C) ln X RT Information
1 39 0.000611111 0.003205128 -7.400231765 2593.968 Without Glassrod
 Prasasya,DF and Nugraha,DA / Lintang Alivia Anggerta / Solubility of Solids in Liquids and Partial Molal Volume

2 39 0.000833333 0.003205128 -7.090076837 2593.968 With Glassrod

3 29 0.000555556 0.003311258 -7.495541945 2510.828 Without Glassrod
4 29 0.000722222 0.003311258 -7.233177681 2510.828 With Glassrod

Table 2. Results of Experiments and Calculation of Enthalphy of Solution

∆𝐻𝑓
No ∆𝐻𝑓 Information
𝑅
1 -0.0007 0.0058198 Without Glassrod
2 -0.0011 0.0091454 With Glassrod

Table 3. Results of Experiments and Calculation of Partial Molal Volume and Apparent Molal Volume
Molality V1kg (mL) V2 (mL/mol) V1 (mL/mol) φ
0.3 1005.764555 47.841977 17.84541531 19.2151
0.975 1020.15153 32.40601456 17.79400198 20.6682
1.65 1061.399806 12.74121425 18.72678244 37.212
2.325 1036.191388 -11.1524239 19.11817393 15.566
3 1032.068844 -39.2749 20.69808379 10.6896

3.1 Discussion
From the experiment, it was obtained that the higher the temperature the higher the required of Volume NaOH. Because the higher
the temperature of solution, so the collision of the molocules in solution got faster so the reaction will faster. (Kirk Othmer, 1983). The
reaction betweeen NaOH and Benzoic Acid was :
C6H5COOH (aq) + NaOH (aq)→ C6H5COONa (aq) + H2O (l)
(Svehla, 1985)
The volume of required NaOH to react with benzoic acid was increasing which means mol of benzoic acid in solution was increasing
too according to the temperature.
From the volume NaOH obtained, it can be determined the mol value of benzoic acid. After that, it can be determined the solubility
of benzoic acid solution for each temperature and condition. It was obtained that the solubility of solution in room temperature with glassrod
was 0.0007 molal and without glassrod was 0.0005 molal, and the solubility of solution in 39°C with glassrod was 0.0008 molal and without
glassrod was 0.0006 molal.
Based on the data, it can be known that the value of solubility tends to increase according to the temperature. In room temperature,
the crystal of benzoic acid formed more than in 39°C.
From Van’t Hoff equation :
∆𝐻𝑓 1
ln 𝑥 = − +𝐶 (1)
𝑅 𝑇

Based on Van’t Hoff equation, it can be determined the heat value from each condition, with or without glassrod using graphic ln x vs 1/T.
(Morand, 2004).
 Prasasya,DF and Nugraha,DA / Lintang Alivia Anggerta / Solubility of Solids in Liquids and Partial Molal Volume

Grafik ln X vs 1/T
0.00335
0.0033
With glassrod
1/T

0.00325
y = -0.0011x - 0.005 y = -0.0007x - 0.0021 Without glassrod
0.0032
0.00315 Linear (With glassrod)
-7.6 -7.5 -7.4 -7.3 -7.2 -7.1 -7 Linear (Without glassrod)
ln X

∆𝐻𝑓
In this graphic it can be known the slope is the value of . The with glassrod linear equation is y = -0.0011x – 0.005 and without
𝑅

glassrod linear equation is y = -0.0007x – 0.0021. So it can be determined ∆𝐻𝑓 of first condition (with glassrod) was 0.0091454 J/mol and
second condition (without glassrod) was 0.0058198 J/mol using R = 8.314 J/mol.K. A positive enthalpy means the solid will absorb heat when

it goes into solution to dissolve it selves. ∆𝐻𝑓 required for first condition which is with glass rod is bigger than the second condition which
is without glassrod, The first condition is bigger because when glassrod was placed in the test tube, the crystal of benzoic acid was formed
more than without glassrod, which means the solubility is greater than the other one. (Bauer et al, 1960).

From the experiment three the partial volume results was obtained in the data that the volume of solution containing 1 kg of

solvent (v1 kg) , partial molal volume of solute (V2) , partial molal volume of solvent (V1) , and the apperent volume (φ) from each molality.

In this experiment it can be identified the paragraph relation between each of the results .

The apparent molal volume of the solute, φV, is closely related to the partial molal volume of the solute. The apparent molal
volume is often more useful in conjunction with other experiments than the partial molal volume itself. For example, in pressure perturbation
calorimetry and analytical ultracentrifugation the apparent molal or specific volume is used. The apparent molal volume is commonly quoted
in the literature and tabulated. The experimental determination of partial molal volumes is, in principle, quite simple and involves the careful
measurement of the densities of solutions of known concentrations. The calculations in the past were simplified by the use of the apparent
molal volume. Currently, polynomial curve fitting allows the calculation of the partial molal properties more directly. So we should also
determine the apparent molal volume .(Klotz, 1950)

From the graph two it can be inferred the relationship between molality and apparent molal volume, from the regression that
found was 0.5824 that it has no pattern in the graph it caused of this experiment influenced by several factors and it was dilution of NaCl is
not perfectly mixed and in this experiment shown that volume of solution does not equal the volume of the solvent and solute because of
the attraction between the molecules so that the fluid is not ideal (Bauer et al, 1960).

40
30
20
φ

10
y = -7.9716x2 + 23.024x + 11.647
0 R² = 0.5824
0 1 2 3 4
Molality

Graph 2. Molality vs Apparent Molal Volume

The difference between the ideal and non-ideal solution is caused by the gravity force of the larger molecules that pull the smaller
molecules closer into them. This results in the total space occupied by the two reduced by certain point. Thus, the total of the solution is
less than the sum of the water and the NaCl. (Atkins, 2010)
 Prasasya,DF and Nugraha,DA / Lintang Alivia Anggerta / Solubility of Solids in Liquids and Partial Molal Volume

Based on the paragraph below it could be conclude that the partial molal volume of solvent (V1) increases with increasing molality
,and partial molal volume of solute (V2) decreases . In every addition of 1 mole of solute (NaCl) in the water (solvent) causes a change in the
total volume of the solution, where the total volume of the solution is not the same as the sum of the volume of the pure components and
the solution. Partial molal volume is an extensive quantity because the value of the partial molal volume is influenced by the concentration
of the substance dissolved in the solvent or the concentration of the solute , intensive property is a bulk property, meaning that it is a physical
property of a system that does not depend on the system size or the amount of material in the system . (Maron Lando, 1974)

60
21
40 y = -4.6407x2 - 16.951x + 53.345 y = 0.4266x2 - 0.3664x + 17.891
R² = 1 20 R² = 0.9723
20

V1
19
V2

0
-20 0 1 2 3 4 18

-40 17
0 1 2 3 4
-60
a. Molality b . Molality

Graph 1. a) Molality vs Partial Molal Volume of Solute b) Molality vs Partial Molal Volume of Solvent
In theorical the partial molar quantities are not always potisive ,but Molar volumes are always positive. The example of the
limiting partial molar volume of MgSO4 in water (its partial molar volume in the limit of zero concentration) is −1.4 cm³ /mol and The mixture
contracts because the salt breaks up the open structure of water as the Mg2+ and SO42- .(Atknis, 2010)

4. Conclusion
In this experiment, it was obtained that the solubility value or benzoic acid at room temperature was 0.0007 molal (with glassrod) and
0.0005 (without glassrod), and at 39°C was 0.0008 (with glassrod) and 0.0006 (without glassrod). Solubility is directly proportional to
temperature, where the greatest value of solubility was in 39°C temperature. From the graphic data experiment, it can be known that the
value of ΔHf without glassrod is 0.0058 J/mol and with glassrod is 0.0091 J/mol
From the experiment of partial molal volume it could be concluded that the total volume of the mixture is lower than the total volume
of the pure component,the dissolved molal volume is smaller than the molal volume of pure solvent, the tensile force between the solvent-
soluble molecules is greater and the pulling force between molecules causes a reduction in the volume of solution because the attractive
force of the pure solvent molecules

5. Refferences

Atkins,P. 2010. Physical Chemistry Ninth Edition. New York : W. H. Freeman and Company
Bauer,N, and S.Z Levin.1972 . Techniques of Chemistry.New York: Willey-Intersience
Klotz, I.M., Chemical Thermodynamics, chap. 13, Prentice-Hall, Englewood Cliffs, New Jersey, 1950.
Maron, S.H. , and Lando, J.B., Fundamental of Physical Chemistry, International edition, Collier Macmillan publishers, London, 1974.
Setyawan,H.2013. Kimia Fisika. Surabaya : ITS Press

Svehla,G. 1985. Buku Teks Analisis Kuantitatif Anorganik Mikro dan Semimikro. Jakarta : PT.Kalman Media Pustaka

Oxtoby, Parid W. 1999. Kimia Modern Edisi 4 Jilid 1. Jakarta: Erlangga.

Petrucci dan Suminar.1992. Prinsip-Prinsip Kimia. Jakarta : Balai Pustaka Goenawan

6. Appendix

𝑛𝑎𝑠𝑎𝑚 𝑝𝑖𝑘𝑟𝑎𝑡 𝑀𝑁𝑎𝑂𝐻 × 𝑉𝑁𝑎𝑂𝐻

𝑀𝑎𝑠𝑎𝑚 𝑝𝑖𝑘𝑟𝑎𝑡 = =
𝑉𝑎𝑠𝑎𝑚 𝑝𝑖𝑘𝑟𝑎𝑡 𝑉𝑎𝑠𝑎𝑚 𝑝𝑖𝑘𝑟𝑎𝑡
 Prasasya,DF and Nugraha,DA / Lintang Alivia Anggerta / Solubility of Solids in Liquids and Partial Molal Volume

0,05 × 0,55
= = 0,00055 𝑀
50
1000
𝑚𝑜𝑙𝑎𝑙 = 𝑀𝑎𝑠𝑎𝑚 𝑝𝑖𝑘𝑟𝑎𝑡 × 𝑉𝑎𝑠𝑎𝑚 𝑝𝑖𝑘𝑟𝑎𝑡 ×
𝑔 𝑝𝑒𝑙𝑎𝑟𝑢𝑡
50 1000
= 0,00055 × × = 0,0006111 𝑚𝑜𝑙𝑎𝑙
1000 45 × 1
Table 1. Results of Experiments and Calculation of mass of NaCl

Molality (m) Mass of NaCl (g) Volume of Aquades (mL)

0.3 0.8775 50
0.975 2.851 50
1.65 4.826 50
2.325 6.8 50
3 8.775 50

Table 2. Result of Calibration of Picnometer ( T : 29° C, 𝜌 = 1 𝑔𝑟𝑎𝑚/𝑚𝐿 )

Picno Mass of pychnometer Mass of Pychometer + Mass of Aquadest Volume of

meter (gram) Aquadest (gram) (gram) Pychnometer (mL)
I 11.2734 21.5364 10.2630 10.2630
II 11.8480 20.0737 10.2619 10.2619
III 9.84195 20.2844 10.4425 10.4425
IV 11.0781 20.9513 9.87320 9.87320
V 10.5114 20.8967 10.3835 10.3835
Table 3. Results of Experiments and Calculation of Density of NaCl

Molality of Nacl (m) Mass of NaCl + Mass of Nacl (g) Volume of Density of NaCl (g/mL)
pychnometer (g) Pychnometer (mL)
0.3 21.6567 10.3836 10.2630 1.0117
0.975 22.4129 10.6011 10.2619 1.0330
1.6 20.6620 10.8200 10.4425 1.0361
2.325 21.2018 10.8237 9.87320 1.0962
3 22.3385 11.8275 10.3835 1.1388

a. Determine V1kg

(1000 + molality 58.44) (1000 + 0.3 × 58.44)

V1kg = = = 1005.764555
ρ solution 1.0117
b. Determine partial molal volume
V2 = -4.6407x²-16.9512x + 53.345= -4.6407(0.3)² - 16.9512(0.3) + 53.345 = 47.841977 cm³/mol
18 18
𝑉1 = (V1kg − mV2) ( ) = (1005.764555 − (0.3 × 47.841977) ( ) = 17.84541531 cm³/mol
1000 100

1000 1000
( V1kg−0.996787) (1005.764555−0.996787
φ= = = 19.2151 cm³/mol
molality (1kg) 0.3
 Prasasya,DF and Nugraha,DA / Lintang Alivia Anggerta / Solubility of Solids in Liquids and Partial Molal Volume

Table 2. Result of Calibration of Picnometer ( T : 29° C, ρ=1 gram/mL )

Picno