Investigating the magnitude of partial molar molumes of water and NaCl in

various NaCl-Water solutions concentrations

Darine Caine, Steven Haussman, Jeff Tribble, Brooks Rodibaugh
Rose-Hulman Department of Chemistry
5500 Wabash Avenue
Terre Haute, IN 47803
October 29, 2015

Introduction
In this lab, we investigated how the partial molar volumes of water and NaCl
were affected by the concentration of the overall solution. The only
measurements acquired were of masses of a specific volume of various
concentrations of water-NaCl solutions. Additionally, we massed the volume
of an empty volumetric flask to correct for the actual mass. With these
measurements, we were able to calculate respective partial molar volumes
from the theoretical equations developed in the next section.
Theory
When working with a single, pure substance, both volumes and mass are
perfectly additive. Combining 500 mL of pure water with 250 mL of pure
water will, excluding errors caused by instrumentation, result in 750 mL of
pure water.
At first, it seems reasonable to extend this to solutions of multiple
components, such as a mixture of pure water and saltwater. In a more
general sense, if this is the case, then the volume of a combination of
several solutions is:
V tot = V m ,i ni

(1)

Where Vm,i is the molar volume of solution i and ni is the number of moles of i
In practice, however, this is not the case. For example, combining pure water
and salt water produces a solution whose volume is slightly less than the
sum of its components volumes.
To explain why, it is important to first understand what controls the volume
of a single solution. From this, equations describing the volume of a multicomponent solution can be developed, offering a strictly mathematical view
of the problem.
For a pure substance, changes in volume are entirely described by the
following equation:
(2)

dV =

( VT ) dT +( VP ) dP
P

This behavior is typical for any single component system in which changes to
the composition dont occur. However, with the introduction of multiple
components, one then has to consider the amount of those components, as
they will have an affect on the other parameters affecting volume. Let us

take a two component system to start. The amount of each substance, in

moles, can be factored into Eq. 2 above to derive Eq. 3, which states:
(3)

dV =

( VT )

dP+

P , alln

( VP )

dT +

T ,all n

( Vn )

( Vn )

d na +

a P ,T ,nb

d nb

b P ,T ,na

The first two terms of the equation have remained relatively the same, save
the inclusion of moles being held constant for those terms. Furthermore, this
equation can be simplified in two ways: (1) through the definition and use of
partial molar volume and (2) by observing the presence of a pattern in the
structure of the additional terms beyond these first two. Firstly, each of these
additional terms describes the change in the volume of the system with
respect to the change in moles of individual components, holding pressure,
temperature, and moles of all other components constant. This particular
partial differential is what is defined as partial molar volume:
V
V i=
ni

( )

(4)

P ,T ,n j i

This term will be discussed more in a moment. Before that, however, it is

possible to simplify Eq. 3 by combining those additional partial molar volume
terms into a simple summation, thanks to the congruity of their structure,
which when applied to Eq. 3 provides:
(5)

dV =

( VT )

P , alln

dP+

( VP )

T ,all n

dT + V i d ni
i

This equation accurately describes the change in volume for all

multicomponent systems. This relation, as it stands now though, is still
rather mathematical in nature, but can be clarified and in some cases
simplified through the application of some other key principles regarding
partial molar volumes.
To elaborate, let us first examine the relationship of Eq. 1 and the summation
term of Eq. 4. It is easy to see the highly analogous structures between these
two quantities, and it exists for a reason. Firstly, while obvious, it is important
to keep in mind that molar volume and partial molar volume are both by
definition molar quantities; this relationship is explicit in the notation for
molar volume, whereas with partial molar volume it is part of the definition of
the term. Thus, multiplying them by the number of moles of a given
substance gives an answer simply in units of volume. A very important
concept is that the value of these two quantities can be equal, and this is
one practical definition of what is called a perfect or ideal solution. What this

essentially states is that for an ideal solution, volumes are additive. In a

sense, one-component systems are ideal because adding more of a
substance with the same partial and total molar volumes results in the same
change in volume of the system. Another way to view this is, that for any
constant number of moles of any number of particular substances added to
the system, if the sums of the molar volumes and partial molar volumes are
the same, then the solution is ideal and will reflect an additive nature with
regards to changes in volume. For many systems, however, this ideality is
not the case and instead a difference is seen in the values produced by Eq. 1
and Eq. 4.
Having now defined partial molar volume, it is now also important to note
that this value is not a directly measurable parameter of a given system,
though the value for it is experimentally accessible. In order to achieve this,
a relationship must be established that connects measurable features of the
system to this value of partial molar volume. The first step towards doing this
is recognizing that while the volume does change in an additive fashion, it
does still change in a very apparent way. For this reason it is useful to define
what will be referred to as the apparent molar volume, V:
(6)

V n A V m , A
V =
nB

Where V is the volume of the system, V*m,A is the molar volume of pure
substance A, and nA,B are the molar quantities of A and B respectively. In
order to use this equation, a practical equation that expresses the volume in
terms outside of itself must also be developed, and so we will state that for a
solution of density d and a solute of molecular weight MWB:
(7)

V=

mas s A +n B MW B
d

Where volume is expressed in units of cubic centimeters (cm3). The mass of

substance A can be easily be determined either by measuring it or by using
the relation:
(8)

n A V m , A=

mas s A
d0

Where d0 is the density of substance A, the solvent, which in many cases is a

known value. If (6), (7), and (8) are combined they simplify to:

V =

(9)

mas s A ( dd 0 )
1
MW B
d
nB d 0

MWB is the molecular weight of substance B. This expression is a practical

definition of apparent molar volume, entirely in terms of measurable or
otherwise experimentally accessible parameters. To simplify this further, it is
possible to assign a constant volume for the measurements to be taken with,
in which case the densities will simplify to masses and (9) takes the form:
V =

(10)

mas s A ( W W 0 )
1
MW B
d
n B (W 0W e )

Where W is the mass of the flask filled to the mark with solution, W0 is the
mass of the flask filled to the mark with pure water, and We is the mass of
the empty flask. The relationship of mass of solvent to moles of solute is
actually an expression of molality (b), or in its present form molalitys
inverse. If (10) is expressed in terms of molality it becomes:
(10.a)
V =

1000 ( W W 0 )
1
mol solute
MV
MW B
, b=molality =
=
d
kg solvent H O V MW B VM
b(W 0 W e )

With the factor of 1000 being included to account for the fact that molality is
conventionally expressed in mol kg-1 instead of mol g-1. It is important to note
that the density of water and of the solution are still represented in this
equation with:
(10.b)

d 0= H O=
2

W o W e
WW e
, d= NaCl =
10
10

With NaCl representing the density of a solution of NaCl and not the density
of the substance itself. With this, it is possible to use the established
relationship of apparent molar volume to calculate the volume of the system
after addition of a solute. Solving (6) for V yields:
(11)

V =V nB +n A V m , A

Having the volume now expressed in terms of experimentally accessible

values means, partial molar volume can also be expressed as such using the
definition of particular molar volume, (4), which dictates that the partial

derivative of (11) with respect to nB be taken while holding pressure (P),

temperature (T), and moles of solvent A (nA) constant, yielding:
V B = V +n B

(12)

V
nB

( )

T , P , nA

Using our definition of partial molar volume, (5), equation (11), and the fact
that this is a two-component system, the partial molar volume of substance
A can also be expressed, as seen in:
(13)

n 2B V
1

V A = ( V n B V B ) =V m , A
nA
nA nB

( )

T , P , nA

It is then taken that apparent molar volume varies linearly with the square
root of molality, which is directly related to moles of solute (nB) and the
expression below can derived:
(14)

d V d V d V d b
1 d V
=
=
=
d n B db d b db 2 b d b

( )

The direct proportionality of nB and b mean that partial molar volume can
now be expressed directly in molality as well, which takes the form of:
b
3 b V
b V
V A =V m , A
; V B= 0+
(15)
55.51 2 b T , P , n
2 b T , P ,n

( )

55.51 is a value for nA for 1000g of water, and 0 is the apparent molar
volume extrapolated to zero concentration. Both partial molar volumes are
now directly related to the change of the apparent molar volume with
respect to molality, and so a plot of that relationship provides a numerical
value for the slope which can then be substituted into either equation along
with the other appropriate values.

Experimental Procedure

A stock solution of 2.000 M NaCl was provided, from which a set of serial
dilutions was produced with approximate molarities of 1.0, 0.5, and 0.25 M.
An additional solution of 1.5 M NaCl was prepared from the 2.000 M stock. All
solutions were prepared in clean 250 mL Erlenmeyer flasks using aliquots of
the previous solution in the series, drawn using a volumetric pipet of
appropriate volume, either 50 0.05 mL and 75 0.05 mL. This pipet was
cleaned between runs to minimize residue left on the pipet, and ensure
accuracy in the preparation of the solutions.
All measurements of mass were taken using an Explorer balance (Chemistry
Department #11, OHAUS, item# = E01140). In order to minimize the
presence of factors affecting the mass, and potential loss or transfer of
solution, no glass stopper was used. Measurements of the mass of each
solution were done from a single 10 mL volumetric flask. Each measurement
of mass, regardless of the sample identity was done in at least triplicate.
To start, the mass of the empty flask, was taken in triplicate. Next, the mass
of a 10 mL aliquot of water was taken, again in triplicate. A cursory
examination of the datapoints suggested that one was a serious outlier,
however, and this was confirmed by a fourth measurement. The second
spurious value was dropped from the final dataset.
Once these initial measurements were completed, 10 mL aliquots of the
serial dilutions were massed and then returned to their original flasks. The
flasks were mixed between each measurement to ensure the consistency of
the solution. The dilutions were massed in order of increasing concentration
from 0.25 M up to 2 M. This was done in order to minimize the potential for
excess solution left in the flask to affect the concentration, and thereby the
mass and density, of the next solution in the series. All of these
measurements were completed in triplicate.
As each measurement was collected, the masses were entered into a
Microsoft Excel spreadsheet containing equations for the determination of
average mass, standard deviation of the mass measurements, density,
molality, and apparent molar volume.
After completion of the experiment, all of the salt solutions were discarded
into a sink.

Data and Calculations

Table 1: Summary of the masses taken with calculated averages and
standard deviation.
Trial
(Mass)

Empty

1 (g)

9.3122

0.0001

2 (g)

9.3124

0.0001

Water

0.25 M

0.5 M

1M

1.5 M

2M

19.2703
0.0001

19.3802

0.0001

19.4881
0.0001

19.6918

0.0001

19.8708

0.0001

20.0654

0.0001

19.2799
0.0001

19.391

0.0001

19.4848
0.0001

19.6876

0.0001

19.8878

0.0001

20.074

0.0001

3 (g)

9.3120

0.0001

19.2731
0.0001

19.3865

0.0001

19.4859
0.0001

19.685

0.0001

19.8756

0.0001

20.0672

0.0001

Averag
e (g)

9.3122

0.0002

19.2744
0.0049

19.3859

0.0054

19.4863
0.0017

19.6881

0.0034

19.8781

0.0088

20.0689

0.0045

Table 2. Summary of calculated values.

Water .25 M 0.5 M 1 M

1.5
M

2M

1.06

1.0
8

0.996

1.01

1.02

1.0
4

Molality (mol/kg)

0.000

0.25
2

0.50
6

1.0
2

1.55

2.0
9

Square root of Molality (mol/kg)1/2

0.000

0.50
2

0.71
1

1.0
1

1.24

1.4
4

Apparent Molar Volume (mL/mol)

0.000

13.9

16.1

17.
1

18.3

18.
8

Partial molar volume-water

18.1

18.0

18.0

17.
9

17.7

17.
5

Partial molar volume-NaCl

12.0

15.7

17.3

19.

21.2

22.

Density (g/mL)
a

Error calculations were performed for density and molality, but the error was
insignificant. Refer to the Error analysis section for details.
In Figure X, we fit a line of best fit to the apparent molar volume versus the
square root of molality. We obtained the following values:
Slope: 6.5058 mL kg1/2 mol3/2
Intercept: 9.7132 mL/mol

Sample Calculations
Density
=

W 0W e
V

19.2744( g)9.3122(g)
=.996223 g /ml
10( ml)

Molality
MV
b=
V CM MW NaCl
0.25(
b=

1.00737

( mlg )10.00(ml))

mol
)10.00(ml)
L

0.25

Apparent Molar Volume

=

( )(

1000 ( W W 0 )
1
MW NaCl

m ( W 0W e )

))

))

10.00 ( ml )
g
)58.44 (
( molL )( 1000
mol )
ml
(L)

=0.2518232 mol / kg

1
g
1.00737
ml

( )

)(

58.44

1000( 19.3859 ( g )19.27443 ( g ) )

( molg ) 0.2518232
mo l
( 19.27443 ( g )9.3122 ( g ) )

sol

K g sov

=13.9086(L)

Partial Molar Volume of NaCl

V NaCl = y intercept +

3 b
2slop e fit

V NaCl =9.7132mL /mol+

3 0.2518232

( mol
kg )

( 26.5058 mL kg

1
2

mol

3
2

=12.07387 c m 3

Partial Molar Volume of water

V water =V pure water

m
(( 55.51
)( 2m slop e ))

g
V water =18.064( )
ml

fit

0.2518232
55.51(

( mol
kg )

mol
)
kg

((

( ))

mol
0.2518232
26.5058 mL kg 2 mol 2
kg

=18.04163901c m 3

Figure 1. The Debye-Huckel linear relationship between apparent molar

volume and square root of molality. Linear fit: y=6.5058x + 9.7132

Figure 2. Relating the partial molar volumes of the solute and solvent to the
molality of the overall solution

Figure 3. A better scale for demonstrating the partial molar volume of water
as molality of the solution varies

Error Analysis

In this section, we demonstrate our process for error analysis by using partial
differentiation of each term that contributes to a calculated value. Basically,
this method examines the change of when variable when all variables are
held constant. If appropriate, the standard deviation of a measurement was
also considered. The greatest value between the methods was reported and
used in subsequent calculations. Specifically, in order to calculate the error
of density, we first averaged the masses from each trial. All measurements
were done in triplicate. Moreover, we calculated the uncertainty of the
masses using partial differentiation and standard deviation. In this case, the
standard deviation was greater and was thus used to calculate the
uncertainty of density. Although the partial differentiation method should
capture this error, the greater standard deviation likely indicates some errors
in our experimental technique. For example, we may have filled the
volumetric flasks inconsistently. Because we only had one value of density,
we used the partial differential method to obtain an uncertainty. By doing it
this way, we still accurately captured the uncertainty and made efficient use
of our time instead of calculating uncertainties for multiple trials of density.
In many cases, the error was insignificant and we report it in scientific
notation. For calculations not explicitly shown, the Maple worksheets have
been included in the appendix that were used to propagate error. All
uncertainties of glassware were obtained from Harris.
Table 3. The error associated the average masses of each solution
concentration. Both the standard deviation and error were calculated.
Concentrati Average
Error
Standard
on (mol/L)
Mass (g)
(g)
deviation(g)
Empty
9.3122
5.774E0.0002
05
0.0000
19.2699
5.774E0.0049
05
0.2500
19.3859
5.774E0.0054
05
0.5000
19.4863
5.774E0.0017
05
1.000
19.6881
5.774E0.0034
05
1.500
19.8781
5.774E0.0088
05
2.000
20.0689
5.774E0.0045
05

Table 4. Error values for the calculated density and molality of each solution.
Additionally, the error associating in making each concentration is included.
Concentration
Density (g/mL)
Molality (mol/kg)
(mol/L)
0.0000 0.0000
0.2500 5.580E-04

0.99577 2.051E03
1.00737 2.074E-03

0.5000 9.141E-04

1.01741 2.094E-03

1.000 1.305E-03

1.03759 2.133E03
1.05659 2.170E03
1.07567 2.207E03

1.500 1.738E-03
2.000 5.000E-04

0.000 0.000
0.2518 3.626E13
0.5060 4.229E12
1.0213 4.822E11
1.5481 2.512E10
2.0860 5.477E10

Derivations with Sample Calculations

Average mass for Mass of the empty volumetric flask, pure water, and NaClwater solutions
m
1
( 1+m 2+ m3 )
3
av gmass =
av g mass 1
=
m1
3
av g mass 1
=
m2
3
av g mass 1
=
m3
3
m1 =.0001
m2 =.0001
m3 =.0001

2
2
av g mass
av g mass
av gmass
avg mass=
m1 +
m2 +
m 3
m1
m2
m3

((

)(

)(

2
2
1
1
1
avg mass= .0001 + .0001 + .0001
3
3
3

((

)(

)(

2 1
2

))

avg mass=.00005773502692

Molality
b=

mol solute
MV
=
kg solven V MV MW NaCL

b=

M
CMW NaCl

M MW NaCl
b
1
=
+
M M MW NaCl + (M MW NaCl + )2
b
=.9926839195
M
b
M
=
(M MW NaCl + )2

m
=0

b
M2
=
MW NaCl (M MW NaCl + )2
b
=0
MW NaCl

((

b=

b
b
b
M +
+

MW NaCl MWNaCl

)(

)(

2 1
2

))

2 1
2

))

M =0.000 .0005580119163

mol
L

=1.00737 =.002074353859

MW NaCl =

g
mL

58.44277
kg
=.05844277000 0.00
1000
mol
14

m =9.41494615310

Density
massmas s empty
=
V

1
=
mas s empty V

1
=
mass V

mas s avgmas s empty

=
2
V
V

=
mass +

mass
mas sempty mas s

((

)(

mass=20.0689 0.00493693562175427 g

mas s empty =9.3122 0.00005773502692 g

V =10.00 mL 0.02 mL

=0.002207261149

empty

V V

)(

2 1
2

))

Discussion
In this experiment, our overall goal was to elucidate a relationship between
the partial molar volumes of NaCl and water at various molalities of a NaClwater solution, and this relationship is nicely demonstrated by Figures 2 and
3. In brief, partial volume is the change in total volume when a mole of that
particular substance is added to the homogeneous mixture. In general, the
partial molar volume of NaCl seems to always have a positive but ever
decreasing slope. As compared to the partial molar volume in Figure 2, the
partial molar volume of NaCl is much more greatly affected by the molality of
the solution. Moreover, the graph of NaCl puts water off scale to the point
where it appears linear. However, Figure 3 demonstrates that the partial
molar volume of water also follows a similar form but with a decreasing
slope. Because slope is indicative of sensitivity, the partial molar volume of
NaCl is much more sensitive to a change in the molality of solution as
compared to water. These observations can be explained molecularly. As the
molality is increased, there is more NaCl dissolved in solution. Subsequently,
when more NaCl is added, it will raise the volumes solution more than if it
had a smaller molality (less ions in solution). In terms of packing, there is
less space for ions to organize because too many are already
present.Therefore, at higher molalities, the addition of more NaCl has a more
profound effect on the overall volume of the solution. The curve begins to
level off because of the practical limit of NaCl solubility in water. The solution
reaches a point where it becomes completely saturated and can no longer
pack more ion into the solution. Although, the partial molar volume of water
is not greatly affected by the molality, it demonstrates fundamentally
different behavior. As the molality increases, the partial molar volume of
water decreases. At higher molarities, the addition of water has a less

profound effect on the volume of the solution. This can also be explained by
molecular interactions. Normally, water organizes because of hydrogen
bonds, and these are geometry specific. The addition of salt as ions better
organizes the water because water coordinates around the positive and
negative ions. Therefore, better packing can be achieved and thus the
addition of water has less of an effect on overall volume.
The partial molar of volume of water begins at approximately its molar
volume. Theoretically, this makes sense because the partial molar volume of
pure substance is its molar volume. At 0 molal, the solution is pure water. On
the other hand, the partial molar volume of NaCl is approximately 26.99
mL/mol. Although not quite enough data was collected, it is evident from the
graph that the partial molar volume of NaCl is leveling off around 25 mL/mol.
Unlike the water, the partial molar volume of NaCl will never be equal to its
molar volume in a solution. Contextually, this also make sense. It is perfectly
possible to have a pure solution of water with a zero molality in terms of
NaCl. However, it does not make sense to have pure solid of NaCl in water
because of its solubility. Practically speaking, there is also a limit on the
molality term because an infinite amount of NaCl cannot be dissolved in
water. Additionally, NaCl is unable to solvate water as salt-water solutions
are categorically type II.

Overall, we obtained good results that make sense practically and

theoretically, but there are a few discrepancies between our observations
and the theory. Specifically, in salt solutions, the square root of molality and
the apparent molar volume should be related linearly. In Figure 1, this linear
trend is clearly defined for all the data points except at .5. The deviation of
the first point greatly affected the slope and intercept of the line and further
affected partial molar volume calculations. Assuming the right-hand points
are representative of the linear trend, the main source of error is likely the
dilution process. To repeat this experiment, we would perform a much more
careful and conscientious dilution. Overall, the dilutions seem successful
except for the last dilution. Additionally, the lowest concentration is also
affected the most by any error in the masses. Alternatively, we could have
also measured the density of the solutions with an instrument instead of
relying on the concentration calculations.
The other source of error involved measuring the mass of the solutions. One
possible bias was that by drying the flasks with paper towel, lint was
introduced into the volumetric flask. Instead, we should have washed the
volumetric flasks with acetone to displace the water and let them quickly dry.
Another error involves filling the volumetric flasks. Mainly, a positive mass
bias likely occurred every time because not all the solution wicked into a

coherent unit. Some adsorbed into the neck of the flask. To combat this, a
volumetric pipette may have yielded more consistent and accurate readings.
Conclusions
The main results of this experiment are demonstrated in Figures 2 and 3 with
numerical values in Table 2. Although it is not necessarily specific literature
to our chemical system and set-up, the general trend agrees well with data
in Atkins Physical Chemistry. On page 184, he presents a similar graph to
Figure 2 that exhibits the same overall behavior (Atkins). The main difference
between the curves is that Atkins are much smoother. This likely arises with
our issues with dilution and fitting the curve in Figure 1 with a linear fit.
Because the first data point affected our slope greatly, our results would
likely vary from the literature. However, the overall goal of the lab was met
because we were able to obtain representative graphs that capture the
behavior of partial molar volumes of the solvent and solute in salt solutions.
Not only do the graphs agree with the literature, the make sense in terms of
molecular interactions and considerations. With this data, more salt solution
systems could be studied and compared. Additionally, mixtures of liquids
could also be explored like ethanol and water. The concept of partial molar
volume is extremely practical and useful in everyday laboratory work. In
particular, partial molar volume explains why volumes are not necessarily
additive. In closing, our results demonstrate how partial molar volume can
change with the variation of molality.

References
[1] Atkins P., de Paula, J.. Physical Chemistry: Thermodynamics, Structure,
and Change, Tenth Edition.; Great Britain: Oxford university, 2014.
[2] Harris, Daniel. Quantitative Chemical Analysis, Eight Edition.; W.H.
Freeman, 2010.
[3] Luanne Tilstra. Physical Chemistry: Partial Molar Volumes Laboratory.
October 2015.