# Nathaly Murillo

Kevin Brew
04/20/08
Experiment 2: Partial Molal Volume
Abstract
Densities of a small range of concentrations of aqueous potassium chloride and
aqueous sodium chloride were recorded with a density meter so that the partial molal
volumes, and ultimately, the partial molal volumes at infinite dilution, could be
calculated. For potassium chloride and sodium chloride, the partial molal volumes at
infinite dilution of the salts were calculated to be 25.18 mL/mol and 15.19 mL/mol,
respectively. These differ from literature values by 6.23% and 26.85%, respectively.
Error sources include inadequate mixing of the solutions, evaporation and the small range
of the solutions.
Introduction:
Amagat’s law states that volumes are approximately additive. However, this does
not apply to solutions whose concentrations are to be known to a high degree of accuracy.
Preparation of a solution with accurate molality is generally done by adding an amount of
water to a measured amount of salt and obtaining the weight of water by difference. In
1770 Millero reported that volume decreases when salts are added to a specific volume of
water. This effect was explained as electrostriction: the volume contracts due to
interaction of the polar solvent around the ions. However, this phenomenon occurs in
non-ionic solutions well, reflecting differences in intermolecular forces. Thermodynamics
explains this deviation from ideal behavior through partial molal quantities. The most
important partial molal quantity is chemical potential:

(1)
For this experiment, partial molal volume will be measured:

(2)
In high pressure systems, partial molal volume is related thermodynamically to chemical
potential by the following:

(3)
The partial molal volume considers the change in molal volume with the increase in
moles of material:

Since partial molal volumes are functions of concentration but not the total number of
moles, equation 4 can be expressed as:

where V is total volume. Taking component 1 to be water and component 2 to be the salt,
the volume of solution can be determined with static amounts of solvent (water) and
varying amounts of salt. Since molality is the concentration of solute per kg of solvent, it
is intuitive to take the amount of water fixed at 1000 g. With the molality of the solution
and the molecular weight of the salt used and the measured density of the solution, the
volume can be calculated:

The graph of experimental data for volume as a function of molality can be fit with a
power series, yielding a fit equation whose derivative with respect to molality yields the
partial molal volume as a function of molality or amount of salt added:

Replacing equation 7 into equation 5, taking n1 = 55.508 mol of water
(1000g/18.015g/mol), n2 = m, and rearranging, the partial molal volume of solvent can be
expressed as:

Since both partial molal volumes are functions of concentration, they can be expressed at
infinite dilution for a single value. At infinite dilution for the partial molal volume of
water, the effects of solvated ions on the solvent are null. The partial molal volume of salt
at infinite dilution reflects the effects of electrostriction on water due to the solvated ions.
The values of partial molal volumes at infinite dilution depend on the equation used to fit
the data and how well is extrapolates to m = 0. Thus, it is imperative that density be
measured accurately because slight deviations can result in poor results.
Procedure:
Five solutions of KCl with varying molalities between 0.05 m and 2.00 m were
prepared by weighing salt by difference in a jar with lid. 20 mL of distilled water was
added to the jar and the mass was recorded. This was used to calculate the molality of the

solution. The DMA 4500 was turned on and its temperature was adjusted to 25.00°.
Distilled Water was injected and then the air line was reconnected and the pump was
turned on. The density was then taken. Once the density read that of air (between 0.00110.0014 g/mL), a syringe of distilled water was put into the injection port and distilled
water was injected. The density for water was recorded at least 3 times for different
portions until consistency (within 0.0001g/mL). Then the syringe was rinsed twice with
small portions of the KCl solution and was then filled with the solution. The solution was
injected partially and density was recorded. This was repeated until 3 consistent values of
density were reported for the solution, again using different portions. The syringe was
rinsed with another solution of KCl and the density was measured as before. This was
repeated for the remaining KCl solutions. Then the entire procedure was repeated using

Analysis and Results
Weights, molalities, and densities for water, sodium chloride and potassium
chloride were recorded in Table 1. It must be noted that instead of using 0.5 to 2.0 molal
solutions as the procedure indicated, 0.01 to 0.5 molal solutions for sodium chloride and
0.06 to 0.5 molal solutions for potassium chloride were used. With the data obtained,
Figure 1, which shows the relationship between density and molality for each salt, was
produced. The graphs indicate a quadratic relationship between density and molality; as
molality increases, density increases as well. R-squared values of 0.99872 for sodium
chloride and 0.99346 for potassium chloride indicate that the data obtained is precise.
Table 2 contains the calculated volume as a function of molality, V{m}, partial
molal volume of water, V1, the partial molal volume of the salts, V2, and the apparent

partial molal volume, φ. The volume as a function of molality was calculated using
equation 6, the partial molal volume of water using equation 8, the partial molal volume
of the salts using equation 7 and the apparent molal volume using equation 11. It is to be
noted that the partial molal volume of water is somewhat constant across different
molalities but the partial molal volume of the salts decreases greatly with increasing
molality.
Figure 2 represents the relationship between the partial molal volume of the salt
and molality; both graphs show a quadratic relationship. As molality increases, partial
molal volume of the salt increases as well. R-squared values for figure 2 are not as high
as those for figure 1 but still show about 90% reliability.
Table 3 is a summary of the values for an infinite dilution using three different
methods of calculation. By taking the derivative of the fit equation for volume versus
molality in the form V = A + B*m+C*m2. An expression for the partial molal volume is
obtained. This is V2 = B + 2*C*m. The infinite dilution can be found as a limit of
molality approaching 0. This results in the infinite dilution of V2 being equal to the fit
parameter B. A second method to find V2 at infinite dilution is to take the limit of m  0
again, but use the fit equation obtained in figure 3. A third method is to do the same but
use figure 4. This data shows that method 2 is the most reliable with only a 8.6%
deviation from the literature value for NaCl and a 6.2% deviation for KCl.
In figure 3, φ is plotted against m1/2 for both salts. It was found that there is a
linear relationship between φ and m1/2 for NaCl but a quadratic relationship for KCl. This
could be due to the small range of molalities used. The values for R-squared are not as
desirable as those in previous graphs, values of 0.5847 for NaCl and 0.96381 for KCl

were acquired. The quadratic relationship for KCl, although more accurate, does not fit
the mason equation (12) which is clearly linear.
φ =φº + am1/2 + bm

(12)

If the salt solutions followed the Debye-Huckel theory, the equation for φ{m} would
provide a single slope of 1.868 for all 1,1-electrolites at 25ºC. This slope changes
depending on charge and temperature. The relationship between φ-1.86m1/2 and m1/2 is
shown in figure 4. φº is the intercept at m=0. The value φº for NaCl was found to be
14.24 and 25.18 for KCl. This means a deviation from the literature value of 14.3% and
6.2% respectively. The graph for NaCl is linear whereas KCl is quadratic. Once again,
KCl does not fit the equation (13) provided.
φ =φº + 1.868m1/2 + bm

(13)

Table 4 presents information on the differences between the partial molal values of KCl
and NaCl, and between KBr and NaBr at an infinite solution. It is noted that the
difference between the partial molal volumes and the apparent molal volumes of KCl and
NaCl decreases with decreasing molality. We determined that since both KCl and KBr,
and NaCl and KBr are 1,1 electrolytes the difference between them would be equal. The
literature indicates a difference of 6.9 between the partial molal volumes of ions of Cl and
Br. The reason for the disparity between the literature value and the experimental values
may be due to the low molality solutions used.

Data and Figures
Table 1: Salt Solutions Molalities and Densities
Salt

Salt
wt.(g)

H2O
wt(g)

Molality(m)

m2

Water
0.0151

19.8885

0.01299122

0.00016877

0.1568

19.5541

0.13720918

0.01882636

0.2995

19.7263

0.25979221

0.06749199

0.4416

19.6673

0.38420167

0.14761093

0.5849

19.20197

0.52120763

0.27165739

0.0919

19.8768

0.0620102

0.00384527

0.2013

19.9749

0.13516158

0.01826865

0.3813

19.9664

0.25613041

0.06560279

0.5641

19.6936

0.38417145

0.1475877

0.7457

19.5996

0.51028292

0.26038866

NaCl

Water

KCl

Density
0.99808
0.99708
0.99708
0.99765
0.99765
0.99765
1.00278
1.00267
1.00267
1.00269
1.00271
1.00758
1.00757
1.00758
1.00757
1.01260
1.01259
1.01258
1.01259
1.01692
1.01693
1.01694
1.01694
0.99609
0.99589
0.99668
0.99709
0.9971
0.9971
0.99766
0.99769
0.99764
1.00342
1.00345
1.00343
1.00891
1.00894
1.00895
1.00895
1.01475
1.01471
1.01474
1.0202
1.02022
1.02023
1.02022

Figure 1: Density vs Molality for NaCl and KCl Solutions

Density versus Molality for NaCl Solutions
1.020

Density (g/mL)

1.015

NaCl Data
Polynomial Fit

1.010
Data: Data1_B
Model: Parabola
Equation: y = A + B*x + C*x^2
Weighting:
y
No weighting

1.005

Chi^2/DoF
= 7.3015E-8
R^2
= 0.99872

1.000

A
B
C

0.99719
0.04246
-0.00829

±0.00011
±0.00107
±0.00202

0.995
0.0

0.1

0.2

0.3

0.4

0.5

0.6

Molality (mol NaCl/kg H2O)

Density versus Molality for KCl Solutions
1.020

1.015

Density (g/mL)

KCl Data
Polynomial Fit

1.010
Data: Data1_D
Model: Parabola
Equation: y = A + B*x + C*x^2
Weighting:
y
No weighting

1.005

Chi^2/DoF
= 5.9627E-7
R^2
= 0.99346

1.000

A
B
C

0.99619
0.05073
-0.00683

±0.00028
±0.00314
±0.00612

0.995
0.0

0.1

0.2

0.3

0.4

Molality (mol KCl/kg H2O)

0.5

0.6

Table 2: Volumes as a function of molality, V{m}, partial molal volumes of water, V1, the
partial molal volumes of the salts, V2, and the apparent partial molal volumes, φ for
KCl and NaCl
Salt
Water

NaCl

Water

KCl

m1/2

m

m2

d(g/ml)

V{m}

V1

V2

0
0
0
0.113979
0.113979
0.113979
0.370418
0.370418
0.370418
0.370418
0.370418
0.509698
0.509698
0.509698
0.509698
0.61984
0.61984
0.61984
0.61984
0.721947
0.721947
0.721947
0.721947
0
0
0
0
0
0
0.249018
0.249018
0.249018
0.367643
0.367643
0.367643
0.506093
0.506093
0.506093
0.506093
0.619816
0.619816
0.619816
0.714341
0.714341
0.714341
0.714341

0
0
0
0.012991
0.012991
0.012991
0.137209
0.137209
0.137209
0.137209
0.137209
0.259792
0.259792
0.259792
0.259792
0.384202
0.384202
0.384202
0.384202
0.521208
0.521208
0.521208
0.521208
0
0
0
0
0
0
0.06201
0.06201
0.06201
0.135162
0.135162
0.135162
0.25613
0.25613
0.25613
0.25613
0.384171
0.384171
0.384171
0.510283
0.510283
0.510283
0.510283

0
0
0
0.000169
0.000169
0.000169
0.018826
0.018826
0.018826
0.018826
0.018826
0.067492
0.067492
0.067492
0.067492
0.147611
0.147611
0.147611
0.147611
0.271657
0.271657
0.271657
0.271657
0
0
0
0
0
0
0.003845
0.003845
0.003845
0.018269
0.018269
0.018269
0.065603
0.065603
0.065603
0.065603
0.147588
0.147588
0.147588
0.260389
0.260389
0.260389
0.260389

0.99808
0.99708
0.99708
0.99765
0.99765
0.99765
1.00278
1.00267
1.00267
1.00269
1.00271
1.00758
1.00757
1.00758
1.00757
1.0126
1.01259
1.01258
1.01259
1.01692
1.01693
1.01694
1.01694
0.99609
0.99589
0.99668
0.99709
0.9971
0.9971
0.99766
0.99769
0.99764
1.00342
1.00345
1.00343
1.00891
1.00894
1.00895
1.00895
1.01475
1.01471
1.01474
1.0202
1.02022
1.02023
1.02022

998.08
997.08
997.08
1003.117
1003.117
1003.117
1005.224
1005.335
1005.335
1005.314
1005.294
1007.546
1007.556
1007.546
1007.556
1009.731
1009.741
1009.751
1009.741
1013.315
1013.305
1013.295
1013.295
996.09
995.89
996.68
997.09
997.1
997.1
1006.98
1006.95
1007
1006.635
1006.605
1006.625
1010.097
1010.067
1010.057
1010.057
1013.692
1013.732
1013.702
1017.493
1017.473
1017.463
1017.473

17.98083
17.96282
17.96282
18.06369
18.06369
18.06369
18.03806
18.04004
18.04004
18.03968
18.03932
18.03782
18.038
18.03782
18.038
18.05556
18.05574
18.05592
18.05574
18.12084
18.12066
18.12049
18.12049
17.94498
17.94138
17.95561
17.963
17.96318
17.96318
18.07704
18.07649
18.0774
18.01499
18.01444
18.0148
18.03206
18.03152
18.03134
18.03134
18.11275
18.11347
18.11293
18.26113
18.26077
18.26059
18.26077

34.13482
34.13482
34.13482
33.64091
33.64091
33.64091
28.91832
28.91832
28.91832
28.91832
28.91832
24.25789
24.25789
24.25789
24.25789
19.52803
19.52803
19.52803
19.52803
14.31926
14.31926
14.31926
14.31926
64.29841
64.29841
64.29841
64.29841
64.29841
64.29841
57.4027
57.4027
57.4027
49.26805
49.26805
49.26805
35.81597
35.81597
35.81597
35.81597
21.57744
21.57744
21.57744
7.553479
7.553479
7.553479
7.553479

φ
(ml/mol)

11.66608
11.66608
11.66608
16.46577
17.26951
17.26951
17.12336
16.97722
17.63171
17.6702
17.63171
17.6702
17.61029
17.63625
17.6622
17.63625
19.85797
19.83885
19.81973
19.81973

64.7444
64.25611
65.06995
27.15236
26.9297
27.07814
27.84565
27.72839
27.6893
27.6893
27.92209
28.0261
27.94809
28.47113
28.43204
28.41249
28.43204

Figure 2: Volume vs Molality for NaCl and KCl Solutions
Volume versus Molality for NaCl
1014
1012

NaCl Data
Polynomial Fit

1010

Volume (mL)

1008
Data: Data1_B
Model: Parabola
Equation: y = A + B*x + C*x^2
Weighting:
y
No weighting

1006
1004
1002

Chi^2/DoF
= 2.44104
R^2
= 0.90637

1000

A
B
C

998

1000.2363
34.13482
-19.00948

±0.63684
±6.20282
±11.6541

996
0.0

0.1

0.2

0.3

0.4

0.5

0.6

Molality (mol NaCl/kg H2O)

Volume versus Molality for KCl
1020

KCl Data
Polynomial Fit

1015

Volume (mL)

1010
Data: Data1_D
Model: Parabola
Equation: y = A + B*x + C*x^2
Weighting:
y
No weighting

1005

Chi^2/DoF
= 5.07679
R^2
= 0.91877

1000

A
B
C

995

0.0

0.1

0.2

0.3

998.41765
64.29841
-55.60144

0.4

Molality (mol NaCl/kg H2O)

±0.82639
±9.15573
±17.87097

0.5

0.6

Table 3: Values for Infinite Dilutions via 3 different methods
NaCl
KCl
% Deviation from literature for
NaCl
% Deviation from literature for
KCl

V2{Method 1}
34.13
64.30

V2{Method 2}
15.19
25.18

V2{Method 3}
14.24
25.18

105.26049

8.64396

14.37589

139.47266

6.23039

6.23099

Literature
16.63
26.85

Figure 3: φ vs m1/2 for NaCl and KCl Solutions
1/2

φ versus Molality

for NaCl

Data: Data1_B
Model: Line
Equation: y = A + B*x
Weighting:
y
No weighting

20

φ (ml/mol)

Chi^2/DoF
= 0.25021
R^2
= 0.58474
A
B

15.19251
4.71179

±0.59586
±1.14624

18

Data
Linear Fit
16
0.3

0.4

0.5

0.6
1/2

Molality

0.7

(mol/kg)

1/2

φ versus Molality

0.8

1/2

for KCl

28.6
28.4

Data

28.2

φ ( ml/mol)

28.0
27.8

Data: Data1_D
Model: Parabola
Equation: y = A + B*x + C*x^2
Weighting:
y
No weighting

27.6
27.4

Chi^2/DoF
= 0.01125
R^2
= 0.96381

27.2

A
B
C

27.0

25.17714
±0.60707
5.88164
±2.31566
-1.9165 ±2.11332

26.8
0.35

0.40

0.45

0.50

0.55
1/2

Molality

0.60
1/2

(mol/kg)

0.65

0.70

0.75

Figure 4: φ-1.86m1/2 vs m1/2 for NaCl and KCl Solutions
φ – 1.86m1/2 vs. m1/2 for NaCl

19

Data
Linear Fit

φ – 1.86m

1/2

18

Data: Data1_B
Model: Line
Equation: y = A + B*x
Weighting:
y
No weighting

17

Chi^2/DoF
= 0.3561
R^2
= 0.58821
A
B

16

0.3

0.4

0.5

0.6

14.23929
5.00133

0.7

±0.60596
±1.08048

0.8

1/2

m (mol/kg H2O)

1/2

φ – 1.86m1/2 vs. m

for KCl

27.2

Data

φ – 1.86m

1/2

27.0

26.8
Data: Data1_D
Model: Parabola
Equation: y = A + B*x + C*x^2
Weighting:
y
No weighting

26.6

Chi^2/DoF
= 0.01126
R^2
= 0.87445

26.4

A
B
C

25.17698
4.02248
-1.91707

26.2
0.3

0.4

0.5
1/2

m (mol/kg H2O)

0.6

0.7

±0.60723
±2.31626
±2.11387

Table 4: Differences between partial and infinite molal volumes for KCl-NaCl and KBr-NaBr
m {KCl}

V2{NaCl}

V2{KCl}-V2{NaCl}

V2{KBr}-V2{NaBr}

φ{KCl}

V2{KCl}

0.06201

0.012991

57.40269698

33.64091262

23.76178435

23.76178435

64.69015192

11.66608

53.02406807

0.135162

0.137209

49.26805297

28.91832471

20.34972827

20.34972827

54.2057591

17.02108

37.18468228

0.25613

0.259792

35.81597116

24.2578943

11.55807685

11.55807685

27.73816096

17.65096

10.08720568

0.384171

0.384202

21.57743825

19.52802562

2.049412634

2.049412634

27.96542569

17.63625

10.32917607

0.510283

0.521208

7.553479211

14.31925645

-6.765777243

-6.765777243

28.43692338

19.83407

8.602852776

V2{NaCl}

V2{KCl}

Theoretical:
m

V2{KCl}V2{NaCl}

φ{NaCl}

φ{KCl}φ{NaCl}

φ{KCl}

0

34.13482

64.29841

30.16359

9.37781

142.98282

133.60501

0.1

30.33296

53.178122

22.845158

15.58444855

45.90652811

30.32207956

0.5

15.12554

8.69697

-6.42857

19.09436622

30.30297781

11.20861159

1

-3.88374

-46.90447

-43.02073

18.70873

94.2506

75.54187

1.5

-22.893

-102.50591

-79.61289

16.66103396

187.2577965

170.5967626

2

-41.9023

-158.10735

-116.20505

13.75299244

295.3073356

281.5543432

φ{NaCl}

φ{KCl}φ{NaCl}

m{NaCl}

Conclusion
The sodium chloride partial molar volume at infinite dilution, 15.19 mL/mol, is
significantly different than a literature value of 16.63 mL/mol by 8.64%. Running more
determinations at greater range of molalities might have lead to the better results than
those obtained. The potassium chloride partial molar volume at infinite dilution, 25.18
mL/mol, is significantly different than a literature value of 26.85mL/mol. The percent
error between the literature and experimental values for the partial molar volume of
sodium chloride at infinite dilution is 6.23%. This error is smaller than the error in the
potassium chloride measurements. Reasons for these errors include evaporation of water
from the salt chloride solutions during density measurements, not mixing the solutions
thoroughly could have lead to errors, and also the small range of molalities may not
reflect the behaviors at a larger range of molalities.
References:
A. Poisson and J. Chanu, Limnology and Oceanography, Vol. 21, No. 6. (Nov., 1976), pp.
853-861.
Coulture, A.M., Laidler, K.J.. "Partial Molal Volume of Ions in Aqueous Solutions."
Canadian Journal of Chemistry 34(1956): 1209-16.