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III.

RESULTS AND DISCUSSION

A. PREPARATION OF LIQUID SOLUTIONS

Approx Approx. Approx Mass of Flask + Flask + mA, g mB, g nA nB


Volume Vwater Vethanol empty A A+B
% flask (mA*), g (mB*), g
Ethanol (mo), g
100% 0 Pure 116.792 116.792 140.969 0g 24.177 g 0 mol 0.5247
ethanol g g g mol

67% 10 20 117.072 126.901 142.839 9.829 g 15.938 g 0.5454 0.3459


g g g mol mol

50% 15 15 115.482 130.164 141.978 14.682 g 11.814 g 0.815 0.256


g g g mol mol

33% 20 10 122.556 141.781 149.694 19.225 g 7.913 g 1.0669 0.1717


g g g mol mol

17% 25 5 113.776 138.555 142.586 24.779 g 4.031 g 1.375 0.0875


g g g mol mol

0% Pure 0 114.365 144.076 144.076 29.711 0 1.649 0


water
B. DENSITY DETERMINATIONS

Approx, % XB XA Mave Mass of mass of Mass of Density


v/v Ethanol (g/mol) pycnometer
,g
pycnometer
+ liquid, g
liquid, g
ᵨ mix, g/cm3

100% 1 0 46.08 13.349 g 33.868 g 20.519 g 0.8136


g/mol g/cm3
67% 0.388 0.612 28.9086 13.599 g 36.520 g 22.921 g 0.9036
g/mol g/cm3
50% 0.239 0.761 24.7263 13.358 g 37.194 g 23.836 g 0.9498
g/mol g/cm3
33% 0.1386 0.8614 21.9103 13.349 g 37.697 g 24.348 g 0.9655
g/mol g/cm3
17% 0.0598 0.9402 19.6988 13.586 g 38.109 g 24.523 g 0.9772
g/mol g/cm3
0% 0 1 18.02 13.586 g 38.755 g 25.169 g 0.99802
g/mol g/cm3

C. MOLAR VOLUMES OF SOLUTIONS AND ΔVmix

Approx Volume % Vm* VM (cm3/mol) ΔVmix (cm3/mol)


Ethanol (cm3/mol)
100% 56.63464 56.6346375 0

67% 33.02714308 31.9912657 1.03587738

50% 27.28967 26.0434383 1.24623017

33% 23.40444 22.6840333 0.71040376

17% 20.36314 20.1582939 0.20489146

0% 18.05571 15.05571 0

Temperature of water bath : 21 °C


Density of pure ethanol : 0.813636355 g/cm3
Density of distilled water : 0.998022 g/cm3
Molar volume of pure ethanol : 56.635 cm3/mol
Molar volume of distilled water : 18.056 cm3/mol
In this experiment, the density of a liquid was measured using a pycnometer. The partial
molar volume of a binary system of liquids, specifically ethanol-water system, was calculated from
density measurements. The difference between absolute and relative density was also studied.
Absolute density was what one actually measures in the laboratory, expressed in mass per unit
volume of a material. Meanwhile, Relative density or the specific gravity is a dimensionless
quantity. It is the ratio of the density of a given substance to the base or reference material
(Kopecký, F, 1999).
Two main properties of the material were significant in this experiment, the intensive and
extensive properties. Extensive properties depend on the quantity or amount of matter while
intensive properties do not depend on the amount of matter in a system. The ratio of extensive
properties results in the intensive property of the material. Four main intensive properties of the
material were determined and applied in this experiment-density, specific gravity, molar volume
and partial molar volume.
Before preparing the solutions, the Erlenmeyer flasks were properly labeled and weighed.
The solutions of 0%, 17%, 33%, 50%, 67%, 83%, and 100% ethanol (vol/vol) were prepared, each
amounting to 30 mL. The mass of water for each solution was calculated by getting the difference
between the mass of the empty Erlenmeyer flask and the mass of the flask with water. Then, the
specific amount of ethanol was mixed with the water in the flask and weighed. The mass of ethanol
was calculated by subtracting the mass of flask with water to the mass of flask with water and
ethanol.
The masses of the components (ethanol and water) are necessary in the computation for
their respective number of moles and molar fraction. The number of moles of water was calculated
by dividing its mass by molar mass which is 18.02 g/mol. Likewise, the number of moles of ethanol
was calculated in the same manner, using 46.08 g/mol as the molar mass. The molar fractions of
the components were computed next. The moles of ethanol and water were added to get the total
number of moles. The mole fraction of water was calculated by dividing the moles of water by the
total number of moles. Same process was made in getting the mole fraction of ethanol, but using
the moles of ethanol as the dividend.
The solutions were placed in a thermostated bath for about three minutes. The purpose of
this is to equilibrate the temperature of the solutions to that of the reference liquid which is water.
Density varies with temperature. Hence, thermostated bath is used because it allows thermal
equilibrium between the solutions to achieve uniform densities at a fixed temperature. The
temperature of the water bath was recorded to be 21 °C.
Density measurement was the next part of the experiment. A clean and dry pycnometer
was weighed using the analytical balance. The recorded mass of the pycnometer was 13.349 g.
Since there was only one pycnometer for each group, this mass was used for all the calculations
of the solutions assigned.
Distilled water (0% ethanol) was used to fill the pycnometer and the cover was placed so
the excess water ran out of the capillary-like opening. It is necessary to avoid having air bubbles
inside the pycnometer as this would contribute to an error in the volume. For the experiment, a 25-
mL pycnometer was used. The pycnometer filled with water was weighed. Same set of procedures
was made for the other solutions assigned. Before filling the pycnometer with a solution, a small
amount of that solution must be used to rinse the glassware. This is done to ensure that there are
no traces of the previous solution that remained. For example, before transferring the 17% ethanol
in the pycnometer, the pycnometer must first be rinsed with a little amount of the solution to be
transferred. The same goes for the pipet to be used.
Next, the ideal and actual molar volume were calculated. Molar volume is the volume of a
substance for every one mole of it while partial molar volume is the contribution of component to
the total volume of a binary mixture. Partial molar volume is greatly affected by the molecular
interactions between components of a mixture. Atkins (2006) defined partial molar volume as the
contribution that a component of a mixture makes to the total volume of the sample. This can also
be defined as the change in the volume of a solute per moles of solute added. The partial molar
volume of a substance in a mixture is the change in volume per mole of added substance to the
mixture. It’s components for a mixture vary with the composition of the mixture, because the
environment of the molecules in the mixture changes with the composition. It is the changing
molecular environment and the consequent alteration of the interactions between molecules that
results in the thermodynamic properties of a mixture changing as its composition is altered.
For the ideal molar volume calculation, the densities and molar masses of pure ethanol and
pure distilled water (0% and 100% ethanol, respectively) were used. To get the ideal molar volume
of ethanol, the sum of the product of the molar mass of pure ethanol and mole fraction of the
ethanol present in the solution is divided by the density of pure ethanol. The calculation for the
ideal molar volume of water has the same process.
On the other hand, the actual molar volume can be calculated by dividing the average molar
mass of the solution by its density. But first, one must calculate the average molar mass of the
solution by getting the sum of the product of the molar mass and mole fraction of water, and the
product of the molar mass and mole fraction of ethanol.
Then, the ΔVmix was calculated by getting the difference between the ideal molar volume
(Vm*), and the actual molar volume (Vm). The resulting value would be helpful in plotting the
graph of the tangent method.
Many methods were available to get the partial molar volume of water and ethanol such as
curve fitting, tangent-slope method and tangent intercept method. For this experiment, the tangent
method was used to determine the partial molar volume of ethanol and the partial molar volume
of water. In the tangent method graph, the difference molar volume (ΔV mix) was plotted against
the mole fraction of ethanol (XB).

Data points for Tangent-Intercept Method:

XB ΔVmix
(cm3/mol)
1 0

0.388 1.03587738

0.239 1.24623017

0.1386 0.71040376

0.0598 0.20489146

0 0

Figure 1. Graph of delta Vmix vs. mole fraction of ethanol, xB.

The literature values of the molar volumes of pure ethanol and pure water are 18.063
cm /mol and 58.534 cm3/mol, respectively. In the graph above, the tangent line was necessary in
3

order to determine the ΔV of ethanol and water. The molar volume of ethanol and water are 1.45
and 0.60 correspondingly. The partial molar volume of water based on the graph was 17.45571
cm3/mol and for ethanol was 55.18464 cm3/mol.
Originally, the calculated values for the molar volumes of ethanol and water are
56.6346375 cm3/mol and 15.05571 cm3/mol, respectively. Comparing the actual/literature value
of the molar volume of the pure compounds water and ethanol which are : Ethanol=58.534
cm3/mol Water = 18.063 cm3/mol (From Perry’s Handbook) to the experimental values obtained :
Ethanol = 56.6346375 cm3/mol Water = 15.05571 cm3/mol there was a significant difference that
may be due to the errors committed in using the pycnometer and maybe due to the fact that ethanol
was a volatile liquid resulting to less molar volumes obtained experimentally. Another reason is
the interactions between the components of the solution. Since no solution is ideal, the interactions
must always be accounted for. This would also mean that there would be a change in volume.
Water has a fairly open structure wherein there would be open spaces or voids in structure
that may be filled by the nonpolar part (hydrocarbon) of ethanol. This is illustrated in the figure
below. Therefore, the total volume of the mixture would be less than the sum of the volumes of
the mixture when separate. This factor may be accounted for the difference of the total volume.

Figure 2. Water structure


Some possible sources of error in this experiment are the weighing step, cleaning of the
apparatuses, and drying. The weighing step requires close observation, weighing steps includes,
weighing an empty flask and pycnometer, flask + water, pycnometer + water, flask with a certain
percent of ethanol and pycnometer with the same ethanol in the flask. In Weighing an empty flask
and pycnometer, the weigh in the balance must be accumulated precisely, weighing them with bare
hands may lead you to a wrong approximation because the dirt and the finger print in the flask and
pycnometer will also be included in the weight of the empty apparatuses, the experimenter must
weigh them using gloves and wiping them dry before proceeding. After weighing a flask and
pycnometer with water, weighing of ethanol in the same flask and pycnometer must be done, the
possible error in this step was if the water in the flask and pycnometer was not totally dried and
putting an ethanol in it may lead to a wrong outcome after weighing them so before putting another
chemical in the flask or in the pycnometer drying them thoroughly will give you a better result. In
the case of the pycnometer, since the liquid inside the pycnometer must cover all the spaces, an
overflowing of the liquid will occur so before weighing a pycnometer + liquid drying them
precisely must be done to get right results.

IV. SAMPLE CALCULATION

Mass of water (A): mA = mass of flask + A – m empty flask


mA = 141.781 – 122.556 = 19.225 g 33 %
Mass of ethanol (B): mB = mass of flask + A + B – m empty flask +
A
mB = 149.694 – 141.781 = 7.913 g 33 %
Moles of A: nA= mA / MMA
19.225
nA = = 𝟏. 𝟎𝟔𝟔𝟗 𝒎𝒐𝒍 33 %
18.02
Moles of B: nB = mass of B / MMB
7.913
nB = = 𝟎. 𝟏𝟕𝟏𝟕 𝒎𝒐𝒍 33 %
46.08
Mole fraction of B: XB= nB / (nA + nB) = (mB / mmB) / [(mmA /
mmA)+(mB / mmB)]
𝟎.𝟏𝟕𝟏𝟕
XB = (𝟎.𝟏𝟕𝟏𝟕+𝟏.𝟎𝟔𝟔𝟗) = 𝟎. 𝟏𝟑𝟖𝟔 33 %
Mole fraction of A: XA = 1-XB
1.0669
XA = (𝟎.𝟏𝟕𝟏𝟕+𝟏.𝟎𝟔𝟔𝟗) = 0.8614 33 %

Mass of liquid = m pycnometer + liquid – m empty pycnometer

mliquid = 37.697 – 13.349 = 24.348 g 33 %

Density of mixture: ρmix= (mmix / m H2O) x ρH2o


24.348
ρmix = × 0.99802 = 𝟎. 𝟗𝟔𝟓𝟓 𝒈/𝒄𝒎𝟑 33 %
25.169
Average molar mass: MMave = (XH2O)(MMH2O) + (Xethanol
)(MMethanol)
MMave = (0.8614x18.02) + (0.1386x46.08) = 21.9103 g/mol 33 %
Ideal molar volume: VM* = (MMethanol / ρethanol) x Xethanol +
(MMH2O / ρH2O) x XH2O
46.08 18.02 𝒄𝒎𝟑
VM* = (0.1386) + (0.8614) = 𝟐𝟑. . 𝟒𝟎𝟒𝟒𝟒 33 %
0.8136 0.99802 𝒎𝒐𝒍
Actual molar volume: VM = (MMave / ρmix)
21.9103 𝒄𝒎𝟑
VM = = 𝟐𝟐. 𝟔𝟖𝟒𝟎𝟑𝟑 33 %
0.9655 𝒎𝒐𝒍

ΔVM = Vmix* - Vm

𝒄𝒎𝟑
VM = 23.40444 − 22.684033 = 𝟎. 𝟕𝟏𝟎𝟒𝟎𝟑𝟕𝟔 33 %
𝒎𝒐𝒍

Partial molar volume water (0% ethanol) : (tangent-intercept method)


Vm* = 18.05571 cm3/mol
ΔVmix = Vm* - VmH2O
0.60 = 18.05571 – VmH2O
VmH2O = 17.45571 cm3/mol
Partial molar volume of ethanol (100% ethanol) : (tangent-intercept method)
Vm* = 56.63464 cm3/mol
ΔVmix = Vm* - VmEthanol
1.45 = 56.63464 - VmEthanol
VmEthanol = 55.18464 cm3/mol

V. CONCLUSION
Partial molar volumes of ethanol-water system at different concentrations were determined
by utilizing the density and specific gravity measurement. Every concentration had been evaluated
individually; using a pycnometer by means that of the moles of every compound, the mole fraction
of water, the average molecular weight and also the density. These had been determined to get the
molar volume of every concentration and also the change in molar volume because of mixing.
From the information obtained, the various graphs and tables had been made. It was observed that
as the quantity of ethanol is increased, the density is decreased, as proven by the definition of
density giving an inverse proportion relationship with volume. Also, it had been showed that the
partial molar volume once mixed was lesser than the molar volume of pure components. This can
be caused by an ordering effect of solvation that tends to reduce the volume of the solvent. The
decrease in volume of the solution was also because of the intermolecular forces occurring between
ethanol and water molecules. Also, the partial molar volume of water and ethanol had an indirect
relationship due to the contraction that happened after they had been mixed. In this experiment,
the objectives had been effectively met as the partial molar volume of ethanol-water system at
various concentrations had been determined by familiarizing the use of pycnometer for the
measurement of density and specific gravity.

VI. RECOMMENDATION
The group recommends that the volumes of the components in the solution be accurately
measured, in order to clearly observe the changes in the volume of a system or solution.
Additionally, use more values of concentration so that the graph would be more accurate.

VII. REFERENCES
Atkins P. & De Paula J. (2006). Atkins physical chemistry 8th ed. Oxford University Press, Oxford,
New York.
Cooksy, A. (2014). Physical chemistry; Thermodynamics, statistical mechanics, & kinetics.
Pearson Education Inc. New Jersey.
Perry R. (2007). Perry’s Chemical Engineers’ Handbook, 8th ed. New York: McGraw-Hill
Education.