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# 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

NaCl instead of KCl.

**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

Quadratic Fit

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

Quadratic Fit

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.