Experiment 3: Partial Molar Volumes

Introduction
The behavioural of liquid solutions is discussed in terms of departures from the model
of ideal solutions, which holds in the limit of almost negligible differences in properties
between the solution components. Theoretically, due to intermolecular interactions,
the measured total volume is resulting from the mixture of two real liquids deviates
from the total volume calculated from the individual volumes of the components
(volume contraction).

This experiment is about the partial molar volumes of mixture between an alcohol and
distilled water. The alcohol that has been used in this experiment is the ethanol. The
partial molar volumes can be estimated through this experiment. Pycnometer is
an instrument to measure the partial molar volumes of each mixture with different mass.
Nine samples of mixture is tested to determine the partial molar volumes of mixture.
The partial molar properties of the solution is a homogenous mixture which forming a
one phase system with more than one component.

Objectives: i. To measure the densities of different ethanol-water mixtures of

specific composition at 25 C (density determination with
pycnometers)

ii. To calculate the real volume as well as the mean molar mixing
volumes of the investigated ethanol-water and the partial molar
volumes of the both components.

Apparatus and Chemicals: i. Ethyl Alcohol ii.

Distilled Water iii.
Aluminium Foil iv.
Water Bath
 Methodology:
i. The setup of the experiment is shown in Figure 1.

Pcynometers

Water Bath Heater

Figure 1. Experimental Setup

ii. The ethanol-water mixture is prepared in the weighting bottle on the laboratory
balance in the appropriate mass composition. The specification is justify as
Table 1:
m(C2H5OH)/g m(H2O)/g

30.60 1.35
29.35 2.85
27.90 4.70
26.20 6.85
24.15 9.45
21.60 12.65
18.35 16.75
14.15 22.10
8.35 29.40
Table 1. Mass of ethanol-water composition
iii. The dried pycnometeres of known empty mass is filled with the mixtures.
iv. The filled pcynometers is equilibrated in the temperature-controlled bath for
about 30 minutes at 25 C .
v. The pcynometers is removed and sealed individually with stopper. The
pcynometers is later weighted again after drying.
vi. From two weighting one obtain the respective mass of 25mL of the
respective
mixture as the difference of the two weights.
_ _
vii. The weight, density, vr , Vr , xa , xb , Vid , ΔMV , Va and Vb is calculated and

tabulated in Table 2. The formula for each of the calculation is denoted as

below:-
Weight of the mixture, m = m2 m1
where m1 is the mass of empty pcynometer and is the m2 mass of pcynometer +

water + ethanol.

m
Density of the mixture, ρ , given that v is equal to 25mL
v

methanol mwater
Real volume, vr
ρ

vr
Derivated volume, Vr

na nb

Mole fraction for component A and B, xa andxb respectively.

na nb
x xb
a
na nb , na nb

Ideal mixing phase, Vid Va xa Vb xb

given that is 58.277 mm mol-1 for ethanol

Va
Vb is 18.073 mm mol-1 for water

Mean molar mixing volume, ΔM V Vr Vid

_ _
Partial molar volume for both Va and Vb
_
d(Δ V) _
d(Δ V)
Va ΔM V  M
x a Vb Vb Δ M V  M
x b Va
dxa dxa
viii. A graph, ΔMV versus mole fraction of ethanol, xa is plotted and the tangent of

dΔm V
the graph, can be determined.
dxA
Result and Data Processing

+ water + ethanol (g)

Mole fraction, water

pcynometer (g) - m1

Mass of pcynometer

Mass of pcynometer

Mass of mixture left

Ideal mixing phase,

Mass of ethanol (g)

after 20degree -m2

Derivated volume,
+ water + ethanol
Mass of water (g)

Mass of etanol +

Real volume, vr
Mass of empty

Mole of etanol

Mole fraction,
Mole of water
Pcynometers

m= m2 - m1

ethanol xa
Density,ꝓ
water (g)

∆m v
Vid

VA

VB
Vr

xb
1 30.655 1.398 27.387 48.005 47.785 20.618 20.398 0.825 38.865 52.309 0.665 0.078 0.896 0.104 54.078 -1.769 56.297
16.514

2 29.365 2.880 24.420 45.360 45.250 20.940 20.830 0.838 38.497 48.286 0.637 0.160 0.799 0.201 50.215 -1.929 55.944
16.548

3 27.911 4.679 21.801 43.231 43.198 21.430 21.397 0.857 38.019 43.924 0.606 0.260 0.700 0.300 46.213 -2.289 55.383
16.389

4 26.285 6.789 23.452 45.443 45.448 21.991 21.996 0.880 37.599 39.687 0.571 0.377 0.602 0.398 42.285 -2.598 54.878
16.277

5 24.184 9.625 25.915 48.296 48.264 22.381 22.349 0.895 37.765 35.654 0.525 0.534 0.496 0.504 37.998 -2.344 54.916
16.746

6 21.627 12.642 25.913 47.961 47.959 22.048 22.046 0.882 38.857 33.178 0.469 0.702 0.401 0.599 34.188 -1.010 56.059
18.271
7 18.375 16.768 27.437 50.275 50.247 22.838 22.810 0.914 38.470 28.933 0.399 0.931 0.300 0.700 30.133 -1.200 55.666
18.284

8 14.152 22.137 25.228 48.587 48.561 23.359 23.333 0.934 38.838 25.286 0.307 1.229 0.200 0.800 26.114 -0.828 55.836
18.858

9 8.450 29.580 25.959 50.087 50.058 24.128 24.099 0.965 39.404 21.587 0.183 1.642 0.100 0.900 22.113 -0.526 55.938
19.361

Table 2. Experimental Data and the Calculated Value

 The graph of ΔMV vs mole fraction, xa

Graph 1. The graph of ΔMV vs mole fraction, xa

Discussion
The partial molar volume is not only a component of a mixture that makes the overall
volume of the solution. Generally, the partial molar volume of a substance X in
a mixture is the change in volume per mole of X added to the mixture. The
partial molar volumes of the components of a mixture varies with the composition
of the mixture as the environment of the molecules in the mixture changes with
the composition. It is the changing of molecular environment that results in the changing
of thermodynamic properties of a mixture as its composition is changing. For an
example one mole of water is added to a water at 25ºC, the volume increases
by
18 cm3 . The molar volume of pure water would thus be reported as 18 cm3mol1
. However, addition of one mole of water to a large volume of pure ethanol resulting in
an increase in volume of only 14 cm3 . This is caused by the partial molar volume of
water in ethanol is different by partial molar volumes water in water.

In this experiment, our aim is to measure the densities of the different ethanol-water
mixed at specified composition at 25°C and to calculate the real volume, mean molar
mixing volumes of the investigated ethanol-water and the partial molar volume
of both component. For this experiment, different amount of water (g) and different
amount of ethanol (g) are mixed to estimate the partial molar volume between water and
alcohol. The mixture is heated at steady temperature of 25ºC for 30 minutes.

In this experiment, the error is caused by the apparatus itself which is the pycnometer.
When we fill-in the mixture into the pcynometers, the mixture might spill and causes
error to the weighting instrument to yield inaccurate reading. Also, the size of
pycnometer which is small (or maybe too small) makes the process of transferring of the
mixture difficult.

There are few precautionary steps that we have to alert to prevent error such as wiping
the pycnometers with tissue paper or dry towel before weighting to prevent extra
weight from the water or the accumulated dusk at the pycnometers. Also, the
pycnometer must be ensured that no bubbles are presence before the heating process.
The pcynometer must be dried after the heating process.
From the graph, the result of the mean molar mixing volume is decreasing by
increasing of water mole until the addition of water with 0.377 mol to a large volume of
pure ethanol with 0.571 mol. This resulting in the increasing of mean molar
volume which due to the increases in the difference that the volume occupied by
a given water molecule depends on upon the identity of the surrounding molecules.
From the result, the partial of molar volumes of each components of a mixture was vary
for different mixture. This is because the environment of the molecule changes with its
composition (changing molecular environment) that results in the
thermodynamic properties of mixture changing as its composition. The tangent of the
dΔ V
graph, is equal to -2.016.
dxA

Conclusion
From the experiment conducted, we are able to determine the density of different mixture
of ethanol-water with a specific composition at 25ºC for 30 minutes. The calculation is
based on the experimental data and given data on the laboratory sheets. From the graph, the
result of the mean molar mixing volume is decreasing by increasing of water mole
until the addition of water with 0.377 mol to a large volume of pure ethanol
with
dΔ V
0.571 mol. The tangent of the graph, is -2.016.
dxA
References
http://www.everyscience.com/Chemistry/Physical/Mixtures/a.1265.php

https://chem.libretexts.org/Textbook_Maps/Physical_and_Theoretical_Chemistry_Te
xtbook_Maps/DeVoe's_%22Thermodynamics_and_Chemistry%22/09%3A_Mixtures
/9.2_Partial_Molar_Quantities

https://www.colby.edu/chemistry/PChem/lab/PartMolalV.pdf

http://www.ssu.ac.kr/web/pchem/20;jsessionid=0ncit6K55kwEVc1pFA5LB590zHxC
cMSmHnF3m4WjzA9JkcxdeIT85tW4VjsKvkRb?p_p_id=EXT_BBS&p_p_lifecycle
=1&p_p_state=exclusive&p_p_mode=view&p_p_col_id=column-1&p_p_col_count=
1&_EXT_BBS_struts_action=%2Fext%2Fbbs%2Fget_file&_EXT_BBS_bbsMessag
eId=14650684&_EXT_BBS_extFileId=14650299
 Sultan Idris Education University
Department of Chemistry Faculty of
Science and Mathematics
Laboratory Report
SKF 3013 Physical Chemistry I
Name and Index Number Muhamad Fathul Aqil bin Ishak D20162075580

Adrian Jimmy Kiu D20162076383

Lecturer Dr. Aisyah binti Mohamad Sharif
Group A
Experiment Experiment 3: Partial Molar Volumes
Experimental Date 16th October 2018
Submission Date 23rd October 2018