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CHM170L Physical Chemistry 1 Laboratory

4th Quarter SY 2009-2010

Measurement of Density and Determination of Partial Molar Volume and Ethanol-Water System
Nieva, Aileen D.1, Arceo, Mary Anne V., Cuales, Jelline C., Kim, Sung Min, Ngan, Emil Joseph T., Rivera, Jainie Lynne
B.2
Professor, School of Chemical Engineering, Chemistry and Biotechnology, Mapua Institute of Technology; 2Student (s), CHM170L/A41, School of Chemical Engineering,
Chemistry and Biotechnology, Mapua Institute of Technology
1

ABSTRACT
Due to intermolecular interactions, the total volume measured when two real liquids (e.g. ethanol and water) are
mixed deviates from the total volume calculated from the individual volumes of the two liquids (volume
contraction). To describe this non-ideal behavior in the mixing phase, one defines partial molar quantities which are
dependent on the composition of the system. This experiment intends to measure the density of a liquid, having
different concentrations of ethanol-water solutions with the use a pycnometer. Molecules that are mixed with
different molecules would interact differently, that is why in this experiment, partial volumes are also considered
due to ethanol and water mixture. It prepared with different solutions having 10% of increment of concentrations.
Densities have been calculated using the mass of each sample and the known volume of the pycnometer. As the
volume of water increased (volume of ethanol decreased), the density of the ethanol-water system has been
observed to increase. The values of these can be experimentally determined.

INTRODUCTION
Density
The density of a material is defined as its mass per unit
volume. The symbol of density is (the Greek letter rho).
Mathematically: Density = Mass Divided By Volume

where:
(rho) is the density,

which case it is expressed in multiples of the density of


some other standard material, usually water or air/gas.
Pycnometer
A pycnometer (from Greek: (puknos) meaning
"dense"), also called pyknometer or specific gravity bottle,
is a device used to determine the density of a liquid. A
pycnometer is usually made of glass, with a close-fitting
ground glass stopper with a capillary tube through it, so that
air bubbles may escape from the apparatus. This device
enables a liquid's density to be measured accurately by
reference to an appropriate working fluid, such as water or
mercury, using an analytical balance.

m is the mass,
V is the volume.

If the flask is weighed empty, full of water, and full of a liquid


whose specific gravity is desired, the specific gravity of the
liquid can easily be calculated.

Different materials usually have different densities, so


density is an important concept regarding buoyancy, metal
purity and packaging.

Partial Molar Property

In some cases density is expressed as the dimensionless


quantities specific gravity (SG) or relative density (RD), in

Experiment 02 Group No. 4 15 June 2010

A partial molar property is a thermodynamic quantity which


indicates how an extensive property of a solution or mixture
varies with changes in the molar composition of the mixture

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CHM170L Physical Chemistry 1 Laboratory


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at constant temperature and pressure, or for constant


values of the natural variables of the extensive property
considered. Essentially it is the partial derivative with
respect to the quantity (number of moles) of the component
of interest. Every extensive property of a mixture has a
corresponding partial molar property.
The partial molar volume is broadly understood as the
contribution that a component of a mixture makes to the
overall volume of the solution. However, there is rather
more to it than this:
When one mole of water is added to a large volume of
water at 25 C, the volume increases by 18 cm3. The molar
volume of pure water would thus be reported as 18 cm3
mol-1. However, addition of one mole of water to a large
volume of pure ethanol results in an increase in volume of
only 14 cm3. The reason that the increase is different is that
the volume occupied by a given number of water molecules
depends upon the identity of the surrounding molecules.
The value 14 cm3 is said to be the partial molar volume of
water in ethanol.

Ethanol (C2H6O)- also known as ethyl alcohol or grain


alcohol, is a flammable, colorless chemical compound, one
of the alcohols that is most often found in alcoholic
beverages. In common parlance, it is often referred to
simply as alcohol.
Distilled water- is water that has many of its impurities
removed through distillation. Distillation involves boiling the
water and then condensing the steam into a clean
container.
Experimental Procedure
A.
1.
2.
3.
4.
5.
6.

In general, 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
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.
METHODOLOGY
The materials used are the following:

25 mL pycnometer
Chain Balance
Analytical Balance
250 mL beaker
Stirrer
10 or 25 mL graduated cylinder

The Reagents used are the following:

Experiment 02 Group No. 4 15 June 2010

7.

Calibration of Pycnometer and Density


Measurement using Pycnometer
Prepare different concentration (10% by volume
increments) of ethanol-water solutions.
Weigh and clean, dry pycnometer and label it as
empty.
Fill the pycnometer with the sample to the brim
and wipe dry the outside.
Re-weigh the pycnometer and label it as
pycnometer with sample.
Remove the sample and dry the pycnometer in the
oven.
Repeat procedure 3 to 5 for the remaining
samples.
Determine the total volume of the pycnometer.

Calculations
The initial calculation should include:
1.
2.

mass of the solution inside the pycnometer


volume of the solution, based on the volume of the
pycnometer

3.
4.
5.
6.

density of the solution inside the pycnometer


mole fraction of ethanol in the solution
average molar mass of the solution
molar volume of the solution

B.

Specific Gravity Measurement using Chain


Balance
1. Prepare different concentration (10% by volume
increment) of ethanol-water solutions.
2. Measure the specific gravity of the solution using
the chain balance.

C.

Evaluation of partial molar volume of ethanol-water


system

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CHM170L Physical Chemistry 1 Laboratory


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Plot the molar volume versus mole fraction and get


the equation of the curve. Use the equation to evaluate the
partial molar volumes of the component (1 and 2) of the
binary mixture using partial differential equation.
Set up of Apparatus

Thermometer
Pycnometer
Liquid sample
Digital balance

water is 32 C, and its surface tension was 98.18


dynes/cm. The surface tensions literature value was
computed using interpolation.
The instrument used to get the surface tension of
the liquids was Du Nuoy tensiometer. It consists of a
platinum-iridium ring supported by a stirrup attached to the
upper part of the instrument. The ring is placed at the
surface of a liquid with air. It is then pulled upward until it
breaks free of the liquid and moves into the second liquid or
into the air. The force that is just required to break the ring
free of the liquid/air interface is proportional to the surface
tension.
Doing three trials, we obtained 85.967 dynes/cm.
This gives us a difference of 12.133 dynes/cm.
The n-butanol solutions surface tension with
different concentration was also measured. Different values
of surface tension were recorded due to the difference in its
concentration.
Addition of more n-butanol lowered the surface
tension of the solution.
CONCLUSION AND RECOMMENDATION
Density determination by pycnometer is a very
precise method. It uses a working liquid with well-known
density, such as water. We used distilled water, for which

Drying of Pycnometer inside the oven


RESULTS AND DISCUSSION
Measured Surface Tension of Water:
Trial 1

85.9 dynes/cm

Trial 2

85.3 dynes/cm

The first thing to do is to get the Erlenmeyer flask and


measure 5 mL of n-butanol and dilute it to the mark with
water.

temperature dependent values of density H2O.The


pycnometer is a glass flask with a close-fitting ground glass
stopper with a capillary hole through it. This fine hole
releases a spare liquid after closing a top-filled pycnometer
and allows for obtaining a given volume of measured and/or
working liquid with a high accuracy.
First we filled pycnometer with distilled water. According to
equation

= m /V, the volume of water that is filling the

pycnometer and the stopper is V=

; where mH2O is

experimentally determined weight of water (empty


pycnometer weight subtracted).
We repeated the procedure for the liquid with ethanol and
determine its weight mL (measured weight minus weight of
empty pycnometer). Volume V obtained in this

Water surface tension was 72.0 dynes/cm at 25C and 67.9


dynes/cm at 50C temperature. The temperature of the

Experiment 02 Group No. 4 15 June 2010

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CHM170L Physical Chemistry 1 Laboratory


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measurement is the same as the volume of water it follows


alternated equation V=

Combining yields a relation that provides the density of


measured liquid

Sample table
A. Calibration of the pycnometer
Weight of empty pycnometer:
29.5359g
30.3821
Weight of pyhnometer + water:
57.4688g
58.1792
Temperature of water, T:
28C
28C
Density of water at T:
0.966g/cm3 0.966g/cm3
Volume of pycnometer:
28.045cm3 27.909cm3
B. Molar volumes of ethanol-water mixture at different
concentrations
Temperature, C: 28C
28C

Once the y intercepts have been found, they can then


be used to calculate the partial molar volume of a
binary mixture
Sample Computation
Plot of Molar Volume VS Mole Fraction

0.446
3
0.580
1
0.682
5

V 1,
cm3

V 2,
cm3

m1

M2

X1

Mavg

mix,
g/cm3

V,
cm3/mol

Vmix,
cm3/mol

30

0.5152

46

0.7520

63.1702

2.9404

27

0.1661

0.4637

0.2637

38.62

0.7800

49.5137

1.8796

24

0.3322

0.411

0.4463

33.51

0.8040

41.6834

1.3825

21

0.4984

0.359

0.5801

29.77

0.8250

36.0820

1.1617

Density of pure ethanol: 0.966g/cm3


Density of distilled water: 28.045g/cm3

0.966
28.909

-2.3125

15.7489

1.3125

59.5367

-1

17.0578

0.9688

59.1889

-0.4844

17.5743

0.6563

58.8899

The partial molar volume of the ethanol at this same mole


fraction can then be determined for the y intercept of the
tangent line at XB = 1 (yXB=1).

For the partial molar volumes of each component


(VPM, i) as a function of the mole fraction of the ethanol.
The partial molar volume of the solvent (water) at a given
mole fraction of the solute can be obtained from the y
intercept at XB = 0 (yXB=0) of the slope of a line tangent to
the curve of the plot, VMIX/nT vs. XB, using equation

Calculating the partial molar volume

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http://www.everyscience.com/Chemistry/Physical/Mixtures/
a.1265.php
http://www.colby.edu/chemistry/PChem/lab/PartMolalV.pdf
http://en.wikipedia.org/wiki/Partial_molar_property

APPENDICES

Appendix 1: Problem Solving using Computers


Excel can be very useful in the exploratory analysis of data:

The figure illustrates the volume contraction that


occurs on mixing of ethanol and water. From the
corresponding polynomial and its first derivate, e.g. for
xA = xB = 0.5, one obtains the partial molar volumes
VA = 63.17 ml / mol (ethanol) and VB = 15.75 ml /
mol(water) by substitution in equations These values
are definitely less than the molar volumes of the pure
substances at 273.15 K
Dependence of the mean molar mixing volumes MV
on the composition of different ethanol-water mixtures
described by the mole fraction xA of ethanol (T
=293.25 K)
The partial molar volumes of the components of 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.

Use a spreadsheet to do the calculations in the


next 5 parts
viewing your data in graphs to detect errors,
unusual values, trends and patterns
summarising data with means and standard
deviations

REFERENCES
1. Masterton, W. and Hurley, C. 2001. Chemistry Principles
and Reactions, 4th ed. New York: Harcourt.
{Accessed: 06-11-10}
2. Knight, S.B, Crockford, H.B., Fundamentals of Physical
Chemistry 2nd ed., Wiley International, 1964, {Accessed: 0611-10}
Online References: {Accessed: 06-011-10}

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Appendix 2: Useful Information


A partial molar property is a thermodynamic quantity which
indicates how an extensive property of a solution
or mixture varies with changes in the molar
composition of the mixture at constant temperature
and pressure, or for constant values of the natural
variables of the extensive property considered.
Essentially it is the partial derivative with respect to
the quantity (number of moles) of the component of
interest.

Ethanol has a specific gravity of 0.78, so it is 0.78


times as dense as water.
Temperature dependence
The density of substances varies with temperature and
pressure so that it is necessary to specify the temperatures
and pressures at which the densities or weights were
determined. It is nearly always the case that measurements
are made at nominally 1 atmosphere (101.325 kPa the
variations caused by changing weather patterns) but as
specific gravity usually refers to highly incompressible
aqueous solutions or other incompressible substances
variations in density caused by pressure are usually
neglected at least where apparent specific gravity is being
measured.
Measurement of concentration
If the pycnometer is weighed empty, full of water, and full of
a liquid whose specific gravity is desired, the specific gravity
of the liquid can easily be calculated.
Partial molar properties are useful because chemical
mixtures are often maintained at constant temperature and
pressure and under these conditions; the value of any
extensive property can be obtained from its partial molar
property. They are especially useful when considering
specific properties of pure substances (that is, properties of
one mole of pure substance) and properties of mixing.
Appendix 3: Further Reading
Masterton, W. and Hurley, C. 2001. Chemistry Principles
and Reactions, 4th ed. New York: Harcourt.
MsExcel: For more information on how to use MsExcel to
calculate and plot data.

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