Experiment 2: Partial Molar Volume

Yipei Wang and Stephen Tereniak CHEM445-024L Due Date: 10/17/07 Submitted: 10/17/07

Abstract Densities of a range of concentrations of aqueous potassium chloride and aqueous sodium chloride were recorded with a density meter so that the partial molar volumes, and ultimately, the partial molar volumes at infinite dilution, could be calculated. For potassium chloride and sodium chloride, the partial molar volumes at infinite dilution of the salts were calculated to be 0.0261 ( 0.0001) L/mol and 0.0176 ( 0.0001) L/mol, respectively. These differ from literature values by 1.14% and 6.02%, respectively. Theories explaining the percent error include inadequate mixing of the solutions and leaving the caps off the jars containing the sodium chloride solutions as their densities were being measured Introduction When considering the volume of a solution with two components, a useful approximation is that the volume of the solution is equal to the sum of the volumes of the two components. However, due to attractions between the two components, this approximation is not correct; the total volume of the solution is less than the sum of the volumes of its two components. If the molality of an aqueous salt solution is known, then the volume of the solution is mol salt g 1000 g + kg{H O} (1 kg H 2 O ) MW {salt}, mol 2 V = g d, mL

(1)

In order to determine the density of a solution, an aliquot of the solution is injected into an instrument that records the density. The density of a solution can then be fit to a power series with molality: d {m} = a 0 + a1 m + a 2 m 2 + ... (2)

where m is molality and a0, a1, a2, are constants acquired from a curve fitting program.

Likewise, the volume of a solution can be fit to a power series with molality in the following manner: V {m} = b0 + b1 m + b2 m 2 + ... (3)

where b0, b1, b2, are constants acquired from a curve fitting program. The partial molar volume of the salt is the partial derivative of the total volume of the solution with respect to molality (Equation 3) at constant temperature and pressure: V V2 = m T , P Then, the partial molar volume of the solvent (water) can be calculated: V1 = 1 V mV2 n1 (4)

(5)

where n1 is the number of moles of water in the solution. By extrapolating a curve of V2 against molality to a molality of 0, the partial molar volume of the salt at infinite dilution can be obtained ( V2o ) and compared to literature values. The partial molar volume of a salt at infinite dilution provides a quantitative measure of the properties of the solvated ions and how they affect the structure of water. Experimental Sodium chloride and potassium chloride solutions were prepared by weighing the salt in a capped jar, adding approximately 20 milliliters of distilled water, and weighing the solution. The solutions were stirred to ensure that all of the salt dissolved. The density meter was cleaned with distilled water multiple times until the density of air stopped changing at 0.00134 g/mL. Once the density meter was cleaned, ~4 mL of the lowest concentration solution was injected into the instrument so that all of the water was removed, and only the solution remained. The

density of the solution was recorded once the temperature stabilized to 25.00C. Then, a 2 mL aliquot of the solution was injected into the instrument, and the density was recorded again. A total of at least four density measurements was recorded for each solution concentration; typically, the first aliquots density was lower than the following aliquots densities for a given concentration, indicating that some mixing with the previous concentration solution analyzed occurred during the measurement of the first aliquot. The syringe was rinsed twice before analyzing a new solution concentration. A total of five concentrations were measured for both potassium chloride and sodium chloride. The density meter was cleaned with distilled water and pumped with air twice before analyzing a different salt. Results and Discussion The density data for pure water, potassium chloride, and sodium chloride are given in Table 1. One clear trend evident from observing the data is that the density of the first trial for a given concentration was usually much lower (>0.0001 g/mL) than the subsequent trials. One theory is that mixing occurred between the previous trial (of a solution of lower concentration) and the first trial of a new concentration, resulting in a density intermediate between the two solutions. This problem was resolved (in almost all cases) with the second trial of a new concentration. In addition, the 0.4973 molal sodium chloride trials were excluded from the data analysis since they were far off the best-fit curve. Possible reasons for this include a misread analytical balance (for either the salt itself or the total aqueous solution) or an incompletelymixed aqueous solution.

Table 1: Salt Solution Molalities and Densities Type of Salt Wt. salt (g) Wt. H2O (g) Molality Density (g/mL) (mol salt/kg H2O) 0.0000
0.99664 0.99657 0.99657 0.99659 0.00004 0.99953 1.00004 1.00004 1.00004 0.99991 0.00026 1.02021 1.02030 1.02030 1.02031 1.02028 0.00005 1.04252 1.04277 1.04277 1.04276 1.04027 0.00012 1.06110 1.06116 1.06114 1.06117 1.06116 1.06115 0.00003 1.07681 1.07683 1.07682 1.07685 1.07684 1.07683 0.00002

0.1574

20.3483

0.1038

0.7732

20.3797

0.5089

KCl

1.5265

19.8383

1.0321

2.2287

20.1984

1.4801

2.9716

21.1648

1.8833

1.00170 1.00138 1.00139 0.1243 20.4087 0.1042 1.00140 1.00140 1.00145 0.00014 1.00133 1.00129 1.00136 1.00134 0.1309 21.2776 0.1053 1.00135 1.00134 1.00134 0.00002 1.01130 1.01128 1.01131 0.6004 20.6574 0.4973 1.01130 1.01130 0.00001 1.02400 1.02428 1.02413 NaCl 1.02412 0.8206 20.5879 0.6820 1.02407 1.02406 1.02411 0.00010 1.03511 1.03538 1.03541 1.2569 21.9746 0.9787 1.03542 1.03542 1.03535 0.00013 1.05834 1.05841 1.05842 2.0849 22.1803 1.6084 1.05844 1.05847 1.05842 0.00005 1.09053 1.09065 2.8600 19.2407 2.5434 1.09066 1.09066 1.09063 0.00006 *Temperature at 25.00C; red indicates data excluded from the calculations. The density data excluded from the subsequent data analysis were included in calculating the average and standard deviation of the densities at each concentration.

In Figure 1, density is plotted as a function of molality for both potassium chloride and sodium chloride. Each curve is a quadratic function that increases with increasing molality and

has a decreasing rate of increase with increasing molality. The R-squared values for each curve are rather good, indicating that the data used in the data analysis is precise. Also of note is that the two curves cross around 0.15 molal; the potassium chloride curve lies above the sodium chloride curve except for below ~0.15 molal. Tabulated in Table 2 are the data for the volume of the salt solutions as a function of molality as well as the partial molar volumes of the salt and water at a given molality; the mass of water is assumed to be 1.000 kg in these calculations. The volume of solution was calculated from Equation 1; the partial molar volume of salt was calculated with Equation 4, and the partial

Figure 1: Density of Salt Solutions vs. Molality

1.14 1.12 1.1 d = -0.0029(0.0003)m + 0.0484(0.0006)m + 0.9960(0.0002) 2 R = 0.9998
2

Density (g/mL)

1.08 1.06 1.04 1.02 1 0.98 0 0.5 1 1.5 2 2.5 d = -0.0016(0.0001)m + 0.0408(0.0001)m + 0.9970(0.0001) 2 R =1 KCl NaCl Poly. (NaCl) 3
2

Molality (mol/kg)

molar volume of water was calculated with Equation 5. Note that the partial molar volume of water barely changes across a wide range of molalities (the change is a very slight decrease). On the other hand, the partial molar volumes of the salts do increase by a fairly large amount. Table 2: Volumes of Solution and Partial Molar Volumes as a Function of Molality Type of Salt Molality V{solution} Vsalt ( L) Vwater ( L) (mol/kg) (L) 1.0034 0.0261 0.0181 0.0000 1.0034 0.0261 0.0181 1.0034 0.0261 0.0181 1.0077 0.0265 0.0181 0.1038 1.0077 0.0265 0.0181 1.0077 0.0265 0.0181 1.0173 0.0278 0.0181 0.5089 1.0173 0.0278 0.0181 1.0173 0.0278 0.0181 1.0328 0.0296 0.0181 KCl 1.0321 1.0328 0.0296 0.0181 1.0328 0.0296 0.0181 1.0463 0.0311 0.0180 1.0464 0.0311 0.0180 1.4801 1.0463 0.0311 0.0180 1.0463 0.0311 0.0180 1.0591 0.0325 0.0180 1.0590 0.0325 0.0180 1.8833 1.0590 0.0325 0.0180 1.0590 0.0325 0.0180 1.0590 0.0325 0.0180

0.0000

0.1042

0.1053

NaCl 0.6820

0.9787

1.6084

2.5434

1.0034 1.0034 1.0034 1.0047 1.0047 1.0047 1.0047 1.0048 1.0049 1.0048 1.0048 1.0048 1.0048 1.0154 1.0154 1.0154 1.0154 1.0211 1.0210 1.0210 1.0210 1.0336 1.0336 1.0336 1.0336 1.0532 1.0532 1.0532

0.0176 0.0176 0.0176 0.0178 0.0178 0.0178 0.0178 0.0178 0.0178 0.0178 0.0178 0.0178 0.0178 0.0187 0.0187 0.0187 0.0187 0.0192 0.0192 0.0192 0.0192 0.0202 0.0202 0.0202 0.0202 0.0217 0.0217 0.0217

0.0181 0.0181 0.0181 0.0181 0.0181 0.0181 0.0181 0.0181 0.0181 0.0181 0.0181 0.0181 0.0181 0.0181 0.0181 0.0181 0.0181 0.0181 0.0181 0.0181 0.0181 0.0180 0.0180 0.0180 0.0180 0.0180 0.0180 0.0180

In Figure 2, the volume of aqueous salt solution is plotted against molality. The curves for both sodium chloride and potassium chloride in Figure 2 are quadratic functions that increase with increasing molality. The potassium chloride curve remains greater than the sodium chloride curve for all molalities from 0 to 3 molal. Both R-squared values are above 0.999, further reinforcing the notion that the data are accurate. For Figure 3, the partial molar volume of each salt is plotted as a function of molality. For both potassium chloride and sodium chloride, these curves are linear functions that increase with increasing molality. Both R-squared values are excellent (each is 0.99995, carried out to

five decimal places). This information means that the partial molar volume of each salt at infinite dilution (at a molality of 0 on the curve of Figure 3 and in Table 2) can be considered precise calculations. Tabulated in Table 3 are the partial molar volumes for potassium chloride and sodium chloride at round molality values. Note that the difference between the two solutions partial molar volumes increases by 0.0009 L/mol between two successive fixed values of molality; the difference between the two solutions partial molar volumes, if plotted as a function of molality, would itself be a linear function.

Figure 2: Volumes of Salt Solutions vs. Molality

1.1000

1.0800

V = 0.0017(0.0003)m2 + 0.0261(0.0006)m + 1.0040(0.0002) R2 = 0.9995

1.0600

V (L)
1.0400 KCl NaCl 1.0200

V = 0.0008(0.0001)m2 + 0.0176(0.0001)m + 1.0030(0.0001) R2 = 0.9999

1.0000 0 0.5 1 1.5 2 2.5 3

Molality (mol/kg)

Table 3: Calculated Partial Molar Volume Differences Between KCl and NaCl m (mol/kg) V 2{KCl} (L/mol) V2 {NaCl} (L/mol) V 2{KCl} - V2 {NaCl} (L/mol) 0.0 0.0261 0.0176 0.0085 0.5 0.0278 0.0184 0.0094 1.0 0.0295 0.0192 0.0103 1.5 0.0312 0.0200 0.0112 2.0 0.0329 0.0208 0.0121 2.5 0.0346 0.0216 0.0130 3.0 0.0363 0.0224 0.0139

From the V 2{KCl} - V2 {NaCl} data at infinite dilution, an estimate for V 2{KBr} V2 {NaBr} at infinite dilution can be calculated. Several assumptions must be made: at infinite dilution, it must be assumed that the interionic distances are infinite; i.e., no attractions between ions in solution exist (so that ion pairing is neglected). Also, one assumes that the ions are not solvated by water, for the extent of solvation varies between ions (and the increase in ionic size is not easy to quantify). Using these assumptions, the difference in partial molar volumes of the bromides at infinite dilution can be calculated from Pauling ionic radii (1): V2o {KBr} - V2o {NaBr} =

3 3 rK r3 + r Na + Br V {KCl} V {NaCl} 3 r + r3 + r3 Na Cl K o 2 o 2

( (

) )

3 rBr = r3 Cl

3 0.0085 (195 pm ) = 0.0106 L/mol (181 pm ) 3

Examining partial molar volume data for copper(II) sulfate demonstrates that partial molar volumes are not directly proportional to ionic size. In Table 4, density, volume of solution, and partial molar volume of copper sulfate data is presented as a function of molality. The densities steadily increase, but the volumes of solution first decrease, reach their minimum

Figure 3: Partial Molar Volume {Salt} vs. Molality

0.0375 0.0355

Partial Molar Volume {salt} (L/mol)

0.0335 0.0315 0.0295 0.0275 0.0255 0.0235 0.0215 0.0195 0.0175 0

PMV = 0.0034(0.0001)m + 0.0261(0.0001) R2 = 1

PMV = 0.0016(0.0001)m + 0.0176(0.0001) R2 = 1

KCl NaCl 0.5 1 1.5 2 2.5 3

Molality (mol/kg)

at 0.194 molal (using more significant figures than are displayed in the table), and then steadily increase with increasing molality. The partial molar volume of copper sulfate actually is a negative value until 0.128 molal; this requires that partial molar volumes not be proportional to ionic size, for then negative partial molar volumes would not be possible since ionic radii cannot have negative values. A negative partial molar volume merely indicates that the volume of solution decreases with increasing copper sulfate concentration in solution. Table 4: CuSO4 Solution Volumes and Partial Molar Volumes as a Function of Molality2 V2 {m} (L/mol) Molality (mol/kg) Density (g/mL) V{m} (L) 0.000 0.99823 1.0018 -0.0015 0.031 1.00332 1.0016 -0.0011 0.095 1.01370 1.0015 -0.0002 0.128 1.01899 1.0014 0.0002 0.194 1.02957 1.0014 0.0011 0.261 1.04026 1.0014 0.0020 0.329 1.05104 1.0015 0.0028 0.400 1.06202 1.0017 0.0038 0.472 1.07310 1.0021 0.0047 0.544 1.08428 1.0024 0.0057 0.620 1.09556 1.0031 0.0067 0.697 1.10704 1.0037 0.0077 0.854 1.13040 1.0053 0.0098 1.020 1.15455 1.0072 0.0120 1.106 1.16693 1.0082 0.0131 1.193 1.17961 1.0091 0.0142 1.375 1.20586 1.0113 0.0167 Note: Measurements taken at 20.0C. Using the Table 4 data, density against molality is plotted in Figure 4. The curve has a positive slope; the change in the slope decreases with increasing molality. With a R-squared value of 1, the data are precise. Depicted in Figure 5 is the volume of solution versus molality. Note the minimum in the parabola around 0.100 molal; this occurs at a slightly lesser concentration than the minimum solution volume in the data at 0.194 molal. The R-squared value for this chart is not terribly good. In Figure 6, the partial molar volume of copper sulfate is

plotted against molality. The crossover from negative partial molar volumes to positive partial molar volumes can clearly be seen in Figure 6; it occurs at a molality a little above 0.100 molal. Excluding the y-intercept of the data (the partial molar volume at infinite dilution), the linear curve in Figure 6 is not notably different from the linear curves in Figure 3.

Figure 4: Copper Sulfate Density vs. Molality

1.25

1.2

d = -0.0082(0.0004)m2 + 0.1617(0.0005)m + 0.9984(0.0002) R2 = 1

1.15

Density (g/mL)

1.1

1.05

0.95 0.000

0.200

0.400

0.600

0.800

1.000

1.200

1.400

Molality (mol/kg)

Figure 5: Volume of Copper Sulfate Solution vs. Molality

1.014

1.012

V = 0.0066(0.0004)m2 - 0.0015(0.0006)m + 1.0015(0.0001) R2 = 0.9939

1.01

Volume (L)

1.008

1.006

1.004

1.002

1 0.000

0.200

0.400

0.600

0.800

1.000

1.200

1.400

Molality (mol/kg)

Figure 6: Partial Molar Volume of CuSO4 vs. Molality

0.018 0.016

PMV = 0.0132(0.0001)m - 0.0015(0.0001) R2 = 1

Partial Molar Volume CuSO4 (L/mol)

0.014 0.012 0.01 0.008 0.006 0.004 0.002 0 0.000 -0.002

0.200

0.400

0.600

0.800

1.000

1.200

1.400

Molality (mol/kg)

Conclusions The potassium chloride partial molar volume at infinite dilution, 0.0261 ( 0.0001) L/mol, is significantly different than a literature value, 0.0264 L/mol, at the 95% confidence interval since tcalc is greater than ttable for 20 degrees of freedom (3). Running more determinations might have lead to the conclusion that the literature and the experimental values are not significantly different at the 95% confidence interval; the two values differ by only 0.0003 L/mol (or 1.14%). The sodium chloride partial molar volume at infinite dilution, 0.0176 ( 0.0001) L/mol, is significantly different than a literature value, 0.0166 ( 0.0001) L/mol, at the 95% confidence interval since tcalc is greater than ttable for 25 degrees of freedom (4). The percent error between the literature and experimental values for the partial molar volume of sodium chloride at infinite dilution is 6.02%. This error is much larger than the error in the potassium chloride measurements. Reasons for these errors include waters evaporation from the sodium chloride solutions during density measurements since the lid was sometimes left off of the jar of the solution whose density was being measured. Also, not mixing the solutions enough could have been a culprit. References 1. Winter, M. Ionic Radius (Pauling) for M(I) Ion. WebElements. 2007. WebElements, Ltd. 17 Oct 2007 <http://www.webelements.com/webelements/properties/text/definitions/radius-ionicpauling-1.html>. 2. Munson, B. Partial Molar Volume, pg. 6. 8/23/07. 3. Gucker, F. T.: Chem. Rev. 13, 126 (1933). 4. Redlich, O., and Bigeleisen, J.: Chem. Rev. 30, 175 (1942).