Chapter 13

Physical Properties of Solutions

 

13.9

In predicting solubility, remember the saying:  Like dissolves like.”  A nonpolar solute will dissolve in a nonpolar solvent; ionic compounds will generally dissolve in polar solvents due to favorable ion-dipole interactions; solutes that can form hydrogen bonds with a solvent will also have high solubility in the solvent.  Naphthalene and benzene are nonpolar, whereas CsF is ionic.

13.10

Strong hydrogen bonding (dipole-dipole attraction) is the principal intermolecular attraction in liquid ethanol, but in liquid cyclohexane the intermolecular forces are dispersion forces because cyclohexane is nonpolar.  Cyclohexane cannot form hydrogen bonds with ethanol, and therefore cannot attract ethanol molecules strongly enough to form a solution.

13.11

The order of increasing solubility is:  O2 < Br2 < LiCl < CH3OH.  Methanol is miscible with water because of strong hydrogen bonding.  LiCl is an ionic solid and is very soluble because of the high polarity of the water molecules.  Both oxygen and bromine are nonpolar and exert only weak dispersion forces.  Bromine is a larger molecule and is therefore more polarizable and susceptible to dipole-induced dipole attractions.

13.12

The longer the C-C chain, the more the molecule "looks like" a hydrocarbon and the less significant the -OH group becomes.  Hence, as the C-C chain length increases, the molecule becomes less polar.  Since “like dissolves like”, as the molecules become more nonpolar, the solubility in polar water decreases.  The -OH group of the alcohols can form strong hydrogen bonds with water molecules, but this property diminishes in importance as the chain length increases.

13.16

a.

The percent by mass is defined by Equation 13.2 as

 

 

Substituting in the percent by mass of solute and the mass of solute, we can solve for the mass of solvent (water).

 

 

(0.162)(mass of water)  =  5.00 g - (0.162)(5.00g)

 

mass of water  =  25.9 g

b.

Similar to part (a),

 

 

mass of water  =  1.72 ´ 103 g

13.17

a.

The molality is the number of moles of sucrose (molar mass 342.3 g/mol) divided by the mass of the solvent (water) in kg.

 

 

molality =0.0610 m

b.

molality =2.04 m

13.18

a.

 

 

molality =2.74 m

b.

100 g of the solution contains 45.2 g KBr and 54.8 g H2O.

 

 

molality =6.93 m

13.19

In each case we consider one liter of solution. 

 

mass of solution = volume ´ density

a.

 

 

b.

 

mass solvent (H2O)  =  1040 g - 35 g  =  1005 g  =  1.005 kg

 

c.

 

mass solvent (H2O)  =  1190 g - 440 g  =  750 g  =  0.75 kg

 

13.20

Let’s assume that we have 1.0 L of a 0.010 M solution.

 

Assuming solution density of 1.0 g/mL, the mass of 1.0 L (1000 mL) of the solution is 1000 g or

1.0 ´ 103 g.

 

The mass of 0.010 mole of urea is:

 

 

The mass of the solvent is:

 

(solution mass) - (solute mass)  =  (1.0 ´ 103 g) - (0.60 g)  =  1.0 ´ 103 g  =  1.0 kg

 

13.21

We find the volume of ethanol in 1.00 L of 75 proof gin.  Note that 75 proof means

 

 

13.22

a.

Convert mass percent to molality, where

 

.

 

We first convert 98.0 g H2SO4 to moles of H2SO4 using its molar mass, then we convert 2.0 g of H2O to units of kilograms.

 

 

 

Lastly, we divide moles of solute by mass of solvent in kg to calculate the molality of the solution.

 

b.

Convert molality to molarity.

 

From part (a), we know the moles of solute (0.999 mole H2SO4) and the mass of the solution (100.0 g).  To solve for molarity, we need the volume of the solution, which we can calculate from its mass and density.

 

First, we use the solution density as a conversion factor to convert to volume of solution.

 

 

Since we already know moles of solute from part (a), 0.999 mole H2SO4, we divide moles of solute by liters of solution to calculate the molarity of the solution.

 

13.23

Strategy:

In this problem, the masses of both solute and solvent are given, and the density is given.

Solution:

In order to determine molarity, we need to know the volume of the solution.  We add the masses of solute and solvent to get the total mass, and use the density to determine the volume. 

 

35.0 g NH3 + 75.0 g H2O = 110.0 g soln

 

Volume of soln = 110.0 g soln

 

We then convert the mass of NH3 to moles, and divide by the volume in liters to get molarity.

 

35.0 g NH3

 

Molarity =18.3 M

 

To calculate molality, we use Equation 13.1.

 

Molality = 27.4 m

Think About It:

Remember in these calculations to express volume of solution in L and mass of solvent in kg.

13.24

Assume 100.0 g of solution.

 

a.

The mass of ethanol in the solution is 0.150 ´ 100.0 g = 15.0 g.  The mass of the water is
100.0 g - 15.0 g = 85.0 g = 0.0850 kg.  The amount of ethanol in moles is:

 

 

Note that we retain an extra digit until the end of the calculation, to avoid rounding error.

 

molality = 3.83 m

b.

The volume of the solution is:

 

 

The amount of ethanol in moles is 0.3256 mole [part (a)].

 

molarity = 3.19 M

c.

solution volume = 0.0784 L or 78.4 mL

13.25

Assuming that N2 and O2 are the only dissolved gases, the mole fractions in the total dissolved gas can be determined as follows:

 

We multiply each partial pressure by the corresponding Henry’s law constant (solubility).

 

For O2, we have

 

0.20 atm ´ 1.3 ´ 10-3 mol/L×atm = 2.6 ´ 10-4 mol/L

 

For N2, we have

 

0.80 atm ´ 6.8 ´ 10-4 mol/L×atm = 5.44 ´ 10-4 mol/L

 

In a liter of water, then, there will be 2.6 ´ 10-4 mol O2 and 5.44 ´ 10-4 mol N2.  The mole fractions are

 

c(N2) = 0.677

 

c(O2) = 0.323

               

Due to the greater solubility of oxygen, it has a larger mole fraction in solution than it does in the air.

13.32

The amount of salt dissolved in 100 g of water is:

 

 

Therefore, the solubility of the salt is 35.2 g salt/100 g H2O.

13.33

At 75°C, 155 g of KNO3 dissolves in 100 g of water to form 255 g of solution.  When cooled to 25°C, only 38.0 g of KNO3 remain dissolved.  This means that (155 - 38.0) g = 117 g of KNO3 will crystallize.  The amount of KNO3 formed when 100 g of saturated solution at 75°C is cooled to 25°C can be found by a simple unit conversion.

 

13.34

The mass of KCl is 10% of the mass of the whole sample or 5.0 g.  The KClO3 mass is 45 g.  If 100 g of water will dissolve 25.5 g of KCl, then the amount of water to dissolve 5.0 g KCl is:

 

 

 

The 20 g of water will dissolve:

 

 

The KClO3 remaining undissolved will be:

 

(45 - 1.4) g KClO3  =  44 g KClO3

13.35

Strategy:

Consider the number of polar groups, and determine whether each molecule is predominantly polar or predominantly nonpolar.  Predominantly polar molecules tend to be water soluble.  Predominantly nonpolar molecules tend to be fat soluble.

Setup:

Polar groups include those containing O atoms or N atoms (atoms with lone pairs).  Vitamin C contains six polar groups (six O atoms) making it predominately polar.  Vitamin E contains only two polar groups and is therefore predominately nonpolar.

Solution:

a.

Water soluble.

b.

Fat soluble.

13.36

Strategy:

Consider the number of polar groups, and determine whether each molecule is predominantly polar or predominantly nonpolar.  Predominantly polar molecules tend to be water soluble.  Predominantly nonpolar molecules tend to be fat soluble.

Setup:

Polar groups include those containing O atoms or N atoms (atoms with lone pairs).  Vitamin D contains only one polar group and is therefore predominately nonpolar.  Vitamin B2 contains 10 polar groups (six O atoms and four N atoms) making it predominately polar.

Solution:

a.

Fat soluble.

b.

Water soluble.

13.37

Strategy:

The given solubility allows us to calculate Henry's law constant (k), which can then be used to determine the concentration of CO2 at 0.0003 atm. 

Solution:

First, calculate the Henry's law constant, k, using the concentration of CO2 in water at 1 atm.

 

 

For atmospheric conditions we write:

 

c  =  kP  =  (0.034 mol/L×atm)(0.00030 atm)  =  1.0 ´ 10-5 mol/L

13.38

We first find the value of k for Henry's law

 

 

Next, we can calculate the concentration of N2 in blood at 4.0 atm using k calculated above.

 

c  =  kP

 

c  =  (7.0 ´ 10-4 mol/L×atm)(4.0 atm)  =  2.8 ´ 10-3 mol/L

 

From each of the concentrations of N2 in blood, we can calculate the number of moles of N2 dissolved by multiplying by the total blood volume of 5.0 L.  Then, we can calculate the number of moles of N2 released when the diver returns to the surface.

 

The number of moles of N2 in 5.0 L of blood at 0.80 atm is:

 

(5.6 ´ 10-4 mol/L )(5.0 L)  =  2.8 ´ 10-3 mol

 

The number of moles of N2 in 5.0 L of blood at 4.0 atm is:

 

(2.8 ´ 10-3 mol/L)(5.0 L)  =  1.4 ´ 10-2 mol

 

The amount of N2 released in moles when the diver returns to the surface is:

 

(1.4 ´ 10-2 mol) - (2.8 ´ 10-3 mol)  =  1.1 ´ 10-2 mol

 

Finally, we can now calculate the volume of N2 released using the ideal gas equation.  The total pressure pushing on the N2 that is released is atmospheric pressure (1 atm).

 

The volume of N2 released is:

 

 

13.39

Strategy:

The mass of CO2 liberated from the container is given by the difference of the two mass measurements. Assume that, at the time of the second mass measurement, all the CO2 has been released and that the amount of CO2 in the vapor phase of the unopened soda is negligible. Then, we can use the following conversions to calculate the pressure of CO2 in the unopened soda.

 

Solution:

Mass of CO2 lost = 853.5 g – 851.3 g = 2.2 g CO2

 

moles CO2 =

 

Using Henry’s law for the final conversion:

 

 

This pressure is only an estimate since we ignored the amount of CO2 that was present in the unopened container in the gas phase.

13.56

The first step is to find the number of moles of sucrose and of water.

 

 

 

The mole fraction of water is:

 

 

The vapor pressure of the solution is found as follows:

 

13.57

Strategy:

From the vapor pressure of water at 20°C and the change in vapor pressure for the solution
(2.0 mmHg), we can solve for the mole fraction of sucrose using Equation 13.5 of the text.  From the mole fraction of sucrose, we can solve for moles of sucrose.  Lastly, we convert form moles to grams of sucrose.

Solution:

Using Equation 13.5 of the text, we can calculate the mole fraction of sucrose that causes a
2.0 mmHg drop in vapor pressure.

 

 

 

4

 

From the definition of mole fraction, we can calculate moles of sucrose.

 

 

moles of water = 552 g30.63 mol H2O

               

 

nsucrose  =  3.94 mol sucrose

 

Using the molar mass of sucrose as a conversion factor, we can calculate the mass of sucrose.

 

mass of sucrose =3.94 mol sucrose1.3 ´ 103 g sucrose

13.58

Let us call benzene component 1 and camphor component 2.

 

 

 

 

13.59

For any solution the sum of the mole fractions of the components is always 1.00, so the mole fraction of
1-propanol is 0.700.  The partial pressures are:

 

 

Think About It:

Is the vapor phase richer in one of the components than the solution?  Which component?  Should this always be true for ideal solutions?

13.60

a.

First find the mole fractions of the solution components.

 

 

 

 

 

The vapor pressures of the methanol and ethanol are:

 

Pmethanol  =  (0.489)(94 mmHg)  =  46 mmHg

 

Pethanol  =  (0.511)(44 mmHg)  =  22 mmHg

b.

Since n = PV/RT and V and T are the same for both vapors, the number of moles of each substance is proportional to the partial pressure.  We can then write for the mole fractions:

 

 

Xethanol  =  1 - Cmethanol  =  0.32

c.

The two components could be separated by fractional distillation. 

13.61

This problem is very similar to Problem 13.57.

 

 

2.50 mmHg  =  Xurea(31.8 mmHg)

 

Xurea  =  0.0786

 

The number of moles of water is:

 

nwater = 658 g H2O36.51 mol H2O

 

 

0.0786 =

 

nurea  =  3.11 mol

 

mass of urea = 3.11 mol urea187 g urea

13.62

DTb  =  Kbm  =  (2.53°C/m)(3.12 m)  =  7.89°C

 

The new boiling point is 80.1°C + 7.89°C = 88.0°C

 

DTf  =  Kfm  =  (5.12°C/m)(3.12 m)  =  16.0°C

 

The new freezing point is 5.5°C - 16.0°C = -10.5°C

13.63

13.64

We want a freezing point depression of 20°C.

 

 

The mass of ethylene glycol (EG) in 6.5 L or 6.5 kg of water is:

 

 

The volume of EG needed is:

 

 

Finally, we calculate the boiling point:

 

DTb  =  mKb  =  (10.8 m)(0.52°C/m)  =  5.6°C

 

The boiling point of the solution will be 100.0°C + 5.6°C = 105.6°C.

13.65

We first find the number of moles of gas using the ideal gas equation.

 

 

molality =

 

DTf   =  Kfm  =  (5.12°C/m)(2.13 m)  =  10.9°C

 

freezing point  =  5.5°C - 10.9°C  =  -5.4°C

13.66

p  =  MRT  =  (1.57 mol/L)(0.0821 L×atm/K×mol)(27.0 + 273) K  =  38.7 atm

13.67

CaCl2 is an ionic compound and is therefore an electrolyte in water.  Assuming that CaCl2 is a strong electrolyte and completely dissociates (no ion pairs, van't Hoff factor i = 3), the total ion concentration will be 3 ´ 0.35 = 1.05 m, which is larger than the urea (nonelectrolyte) concentration of 0.90 m.

a.

The CaCl2 solution will show a larger boiling point elevation.

b.

The freezing point of the urea solution will be higher because the CaCl2 solution will have a larger freezing point depression. 

c.

The CaCl2 solution will have a larger vapor pressure lowering.

13.68

Boiling point, vapor pressure, and osmotic pressure all depend on particle concentration.  Therefore, these solutions also have the same boiling point, osmotic pressure, and vapor pressure.

13.69

Assume that all the salts are completely dissociated.  Calculate the molality of the ions in the solutions.

 

                                0.10 m Na3PO4:                                    0.10 m ´ 4 ions/unit  =  0.40 m

 

                              0.35 m NaCl:                                        0.35 m ´ 2 ions/unit  =  0.70 m

 

                                0.20 m MgCl2:                                      0.20 m ´ 3 ions/unit  =  0.60 m

 

                                0.15 m C6H12O6:                                   nonelectrolyte, 0.15 m

 

                                0.15 m CH3COOH:                              weak electrolyte, slightly greater than 0.15 m

 

The solution with the lowest molality will have the highest freezing point (smallest freezing point depression):  0.15 m C6H12O6 > 0.15 m CH3COOH > 0.10 m Na3PO4 > 0.20 m MgCl2 > 0.35 m NaCl.

13.70

The freezing point will be depressed most by the solution that contains the most solute particles.  Classify each solute as a strong electrolyte, a weak electrolyte, or a nonelectrolyte.  All three solutions have the same concentration, so comparing the solutions is straightforward.  HCl is a strong electrolyte, so under ideal conditions it will completely dissociate into two particles per molecule.  The concentration of particles will be 1.00 m.  Acetic acid is a weak electrolyte, so it will only dissociate to a small extent.  The concentration of particles will be greater than 0.50 m, but less than 1.00 m.  Glucose is a nonelectrolyte, so glucose molecules remain as glucose molecules in solution.  The concentration of particles will be 0.50 m.  For these solutions, the order in which the freezing points become lower is:

 

0.50 m glucose  >  0.50 m acetic acid  >  0.50 m HCl

 

The HCl solution will have the lowest freezing point (greatest freezing point depression).

13.71

a.

NaCl is a strong electrolyte.  The concentration of particles (ions) is double the concentration of NaCl.  Note that because the density of water is 1 g/mL, 135 mL of water has a mass of 135 g.

 

The number of moles of NaCl is:

 

 

Next, we can find the changes in boiling and freezing points (i = 2)

 

 

DTb  =  iKbm  =  2(0.52°C/m)(2.70 m)  =  2.8°C

 

DTf  =  iKfm  =  2(1.86°C/m)(2.70 m)  =  10.0°C

 

The boiling point is 102.8°C;  the freezing point is -10.0°C.

b.

Urea is a nonelectrolyte.  The particle concentration is just equal to the urea concentration.

 

The molality of the urea solution is:

 

 

 

DTb  =  iKbm  =  1(0.52°C/m)(3.84 m)  =  2.0°C

 

DTf  =  iKfm  =  1(1.86°C/m)(3.84 m)  =  7.14°C

 

The boiling point is 102.0°C;  the freezing point is -7.14°C.

13.72

Using Equation 13.5 of the text, we can find the mole fraction of the NaCl.  We use subscript 1 for H2O and subscript 2 for NaCl.

 

 

 

 

Let’s assume that we have 1000 g (1 kg) of water as the solvent, because the definition of molality is moles of solute per kg of solvent.  We can find the number of moles of particles dissolved in the water using the definition of mole fraction.

 

 

 

 

 

Since NaCl dissociates to form two particles (ions), the number of moles of NaCl is half of the above result.

 

 

The molality of the solution is:

 

13.73

Both NaCl and CaCl2 are strong electrolytes.  Urea and sucrose are nonelectrolytes.  The NaCl or CaCl2 will yield more particles per mole of the solid dissolved, resulting in greater freezing point depression.  Also, sucrose and urea would make a mess when the ice melts.

13.74

We want to calculate the osmotic pressure of a NaCl solution.  Since NaCl is a strong electrolyte, i in the van't Hoff equation is 2.

 

p = iMRT

 

Since, R is a constant and T is given, we need to first solve for the molarity of the solution in order to calculate the osmotic pressure (p).  If we assume a given volume of solution, we can then use the density of the solution to determine the mass of the solution.  The solution is 0.86% by mass NaCl, so we can find grams of NaCl in the solution.

 

To calculate molarity, assume that we have 1.000 L of solution (1.000 ´ 103 mL).  We can use the solution density as a conversion factor to calculate the mass of 1.000 ´ 103 mL of solution.

 

 

Since the solution is 0.86% by mass NaCl, the mass of NaCl in the solution is:

 

 

The molarity of the solution is:

 

 

Since NaCl is a strong electrolyte, we assume that the van't Hoff factor is 2.  Substituting i, M, R, and T into the equation for osmotic pressure gives:

 

 

13.75

The temperature and molarity of the two solutions are the same.  If we divide Equation 13.11 of the text for one solution by the same equation for the other, we can find the ratio of the van't Hoff factors in terms of the osmotic pressures (i = 1 for urea).

 

13.76

From Table 13.3 of the text, i = 1.3 for MgSO4.  Using Equation 13.11,

 

p  =  iMRT

 

 

p  =  1.6 atm

13.77

For this problem, we first need to calculate the pressure necessary to support a column of water 105 m high.  We use the equation P = hdg, where h, d, and g are the column height in m, the density of water in kg/m3, and the gravitational constant, respectively.

 

P = 105 m ´ 1.00 ´ 103 ´ 9.81= 1.03 ´ 106 kg/m×s2 = 1.03 ´ 106 Pa ´10.16 atm

 

Because atmospheric pressure contributes 1 atm, the osmotic pressure required is only 9.16 atm.

13.78

Convert both glucose levels to molar concentrations and use molarity to calculate osmotic pressure.

 

 

p = MRT = (0.00971 M)(0.0821 L×atm/mol×K)(310 K) = 0.247 atm

 

 

p = MRT = (0.0047 M)(0.0821 L×atm/mol×K)(310 K) = 0.120 atm

 

Because of its higher glucose concentration, the blood plasma of a diabetic patient has a much higher osmotic pressure.  The water in the body moves via osmosis into the plasma to dilute the concentrated glucose.  The need to replenish the water used to dilute the plasma makes the patient thirsty.

13.82

METHOD 1:

 

Assume 100 g of compound.

 

 

 

 

Thus, we arrive at the formula C3.33H6.6O3.3, which gives the identity and the ratios of atoms present.  Dividing each subscript by the smallest subscript gives whole numbers.

 

                   

 

This gives us the empirical formula, CH2O.

 

Now, we can use the freezing point data to determine the molar mass.  First, calculate the molality of the solution.

 

 

Multiplying the molality by the mass of solvent (in kg) gives moles of unknown solute.  Then, dividing the mass of solute (in g) by the moles of solute, gives the molar mass of the unknown solute.

 

=  0.00542 mol solute

 

 

Finally, we compare the empirical molar mass to the molar mass above.

 

empirical molar mass  =  12.01 g + 2(1.008 g) + 16.00 g  =  30.03 g/mol

 

The number of (CH2O) units present in the molecular formula is:

 

 

Thus, there are four CH2O units in each molecule of the compound, so the molecular formula is (CH2O)4, or C4H8O4.

 

METHOD 2:

 

We use the freezing point data to determine the molar mass.  First, calculate the molality of the solution.

 

 

Multiplying the molality by the mass of solvent (in kg) gives moles of unknown solute.  Then, dividing the mass of solute (in g) by the moles of solute, gives the molar mass of the unknown solute.

 

=  0.00542 mol solute

 

 

Next, we multiply the mass % (converted to a decimal) of each element by the molar mass to convert to grams of each element.  Then, we use the molar mass to convert to moles of each element.

 

                                                      

 

 

                                           

 

Since we used the molar mass to calculate the moles of each element present in the compound, this method directly gives the molecular formula.  The formula is C4H8O4.

13.83

First, from the freezing point depression we can calculate the molality of the solution.  See Table 13.2 of the text for the normal freezing point and Kf value for benzene.

 

DTf  =  (5.5 - 4.3)°C  =  1.2°C

 

 

Multiplying the molality by the mass of solvent (in kg) gives moles of unknown solute.  Then, dividing the mass of solute (in g) by the moles of solute, gives the molar mass of the unknown solute.

 

=  0.0058 mol solute

 

 

The empirical molar mass of C6H5P is 108.1 g/mol.  Therefore, the molecular formula is (C6H5P)4 or C24H20P4.

13.84

The experimental data indicate that the benzoic acid molecules are associated together in pairs in solution due to hydrogen bonding.

 

 

13.85

Strategy:

We are asked to calculate the molar mass of the polymer.  Grams of the polymer are given in the problem, so we need to solve for moles of polymer.

 

want to calculate

 

given

 
 

 

 

 


need to find

 
 

 

 

 

 


From the osmotic pressure of the solution, we can calculate the molarity of the solution.  Then, from the molarity, we can determine the number of moles in 0.8330 g of the polymer.  What units should we use for π and temperature?

Solution:

First, we calculate the molarity using Equation 13.8 of the text.

 

p  =  MRT

 

 

Multiplying the molarity by the volume of solution (in L) gives moles of solute (polymer).

 

? mol of polymer  =  (2.80 ´ 10-4 mol/L)(0.170 L)  =  4.76 ´ 10-5 mol polymer

 

Lastly, dividing the mass of polymer (in g) by the moles of polymer, gives the molar mass of the polymer.

 

13.86

Method 1:  First, find the concentration of the solution, then work out the molar mass.  The concentration is:

 

 

The solution volume is 0.3000 L so the number of moles of solute is:

 

 

The molar mass is then:

 

The empirical formula can be found most easily by assuming a 100.0 g sample of the substance.

 

 

 

 

 

The gives the formula:  C3.48H4.7O2.33N1.16.  Dividing through by the smallest subscript (1.16) gives the empirical formula, C3H4O2N, which has a mass of 86.0 g per formula unit.  The molar mass is five times this amount (430 ¸ 86.0 = 5.0), so the molecular formula is (C3H4O2N)5 or C15H20O10N5.

 

METHOD 2:  Use the molarity data as above to determine the molar mass.

 

molar mass  =  430 g/mol

 

Multiply the mass % (converted to a decimal) of each element by the molar mass to convert to grams of each element.  Then, use the molar mass to convert to moles of each element.

 

 

 

 

 

Since we used the molar mass to calculate the moles of each element present in the compound, this method directly gives the molecular formula.  The formula is C15H20O10N5.

13.87

We use the osmotic pressure data to determine the molarity.

 

 

Next we use the density and the solution mass to find the volume of the solution.

 

mass of soln  =  6.85 g + 100.0 g  = 106.9 g soln

 

 

Multiplying the molarity by the volume (in L) gives moles of solute (carbohydrate).

 

mol of solute  =  M ´ L  =  (0.192 mol/L)(0.1044 L)  =  0.02004 mol solute

 

Finally, dividing mass of carbohydrate by moles of carbohydrate gives the molar mass of the carbohydrate.

 

molar mass =342 g/mol

13.88

Use the osmotic pressure to calculate the molar concentration of dissolved particles in the HNO2 solution.

 

M =

 

% ionization = 5.6%

13.89

Use the osmotic pressure to calculate the molar concentration of dissolved particles in the HB solution.

 

M =

 

When an HB molecule ionizes it produces one H2B+ ion and one OH- ion.

 

HB(aq) + H2O(l) H2B+(aq) + OH-(aq)

               

The concentration of HB is originally 0.100 M.  It decreases by x and the concentrations of H2B+ and OH- each increase by x.  Thus, the concentration of dissolved particles is 0.100 - x + 2x = 0.100 + x.  We solve for x and determine what percentage x is of the original concentration, 0.100 M.

 

% ionization = 15.7%

13.90

Strategy:

Use the osmotic pressure and Equation 13.8 to determine the molar concentration of the particles in solution.  Compare the concentration of particles to the nominal concentration (0.15 M) to determine what percentage of the original HF molecules are ionized.

Setup:

R = 0.08206 L · atm/K · mol, and T = 298 K.

Solution:

Rearranging Equation 13.8 to solve for molarity,

 

 

The concentration of dissolved particles is 0.159 M.  Consider the ionization of HF:

 

 

According to this equation, if x HF molecules ionize, we get x H+ ion and x F ions.  Thus, the total concentration of particles in solution will be the original concentration of HF minus x, which gives the concentration of intact HF molecules, plus 2x, which is the concentration of ions (H+ and F):

 

(0.15 – x) + 2x = 0.15 + x

 

Therefore, 0.159 = 0.15 + x and x = 0.009.  Because we earlier defined x as the amount of HF ionized, the percent ionization is given by

 

percent ionization =

 

At this concentration HF is 6 percent ionized.

13.94

For this problem we must find the solution mole fractions, the molality, and the molarity.  For molarity, we can assume the solution to be so dilute that its density is 1.00 g/mL.  We first find the number of moles of lysozyme and of water.

 

 

 

 

Vapor pressure lowering:           

 

 

Freezing point depression:        

 

Boiling point elevation:             

 

Osmotic pressure:                          As stated above, we assume the density of the solution is 1.00 g/mL.  The volume of the solution will be 150 mL.

 

 

With the exception of osmotic pressure, these changes in colligative properties are essentially negligible.

13.95

Convert each concentration to moles glucose per mL and to total moles and total grams in 5.0 L.

 

Levels before:

 

7.77 ´ 10-6 mol glucose/mL blood

 

3.89 × 10–3 mol glucose

 

7.00 g glucose

 

Levels after:

 

1.33 ´ 10-5 mol glucose/mL blood

 

6.66 × 10–2 mol glucose

 

12.0 g glucose

13.96

DTf = Kfm

 

m =

 

This is an extremely high molal concentration. 

13.97

Water migrates through the semipermiable cell walls of the cucumber into the concentrated salt solution.

Think About It:

When we go swimming in the ocean, why don't we shrivel up like a cucumber?  When we swim in fresh water pool, why don't we swell up and burst?

13.98

a.

We use Equation 13.4 of the text to calculate the vapor pressure of each component.

 

 

First, you must calculate the mole fraction of each component.

 

 

Similarly,

 

CB  =  0.500

 

Substitute the mole fraction calculated above and the vapor pressure of the pure solvent into
Equation 13.4 to calculate the vapor pressure of each component of the solution.

 

 

 

The total vapor pressure is the sum of the vapor pressures of the two components.

 

PTotal  =  PA + PB  =  38 mmHg + 66 66 mmHg  =  104 mmHg

b.

This problem is solved similarly to part a.

 

 

Similarly,

 

CB  =  0.714

 

 

 

PTotal  =  PA + PB  =  22 mmHg + 94 mmHg  =  116 mmHg

13.99

DTf  =  iKfm

 

13.100

From the osmotic pressure, you can calculate the molarity of the solution.

 

 

Multiplying molarity by the volume of solution in liters gives the moles of solute.

 

(1.58 ´ 10-3 mol solute/L soln) ´ (0.262 L soln)  =  4.14 ´ 10-4 mol solute

 

Divide the grams of solute by the moles of solute to calculate the molar mass.

 

13.101

One manometer has pure water over the mercury, one manometer has a 1.0 m solution of NaCl and the other manometer has a 1.0 m solution of urea.  The pure water will have the highest vapor pressure and will thus force the mercury column down the most; column X.  Both the salt and the urea will lower the overall pressure of the water.  However, the salt dissociates into sodium and chloride ions (van't Hoff factor i = 2), whereas urea is a molecular compound with a van't Hoff factor of 1.  Therefore the urea solution will lower the pressure only half as much as the salt solution.  Y is the NaCl solution and Z is the urea solution.

 

X = water, Y = NaCl, Z = urea

 

Assuming that you knew the temperature, could you actually calculate the distance from the top of the solution to the top of the manometer?

13.102

Solve Equation 13.7 of the text algebraically for molality (m), then substitute DTf and Kf into the equation to calculate the molality.  You can find the normal freezing point for benzene and Kf for benzene in Table 13.2 of the text.

 

DTf  =  5.5°C - 3.9°C  =  1.6°C

 

 

Multiplying the molality by the mass of solvent (in kg) gives moles of unknown solute.  Then, dividing the mass of solute (in g) by the moles of solute, gives the molar mass of the unknown solute.

 

=  2.5 ´ 10-3 mol solute

 

 

The molar mass of cocaine C17H21NO4 = 303 g/mol, so the compound is not cocaine.  We assume in our analysis that the compound is a pure, monomeric, nonelectrolyte.

13.103

The pill is in a hypotonic solution.  Consequently, by osmosis, water moves across the semipermeable membrane into the pill.  The increase in pressure pushes the elastic membrane to the right, causing the drug to exit through the small holes at a constant rate.

13.104

The molality of the solution assuming AlCl3 to be a nonelectrolyte is:

 

 

 

The molality calculated with Equation 13.7 of the text is:

 

 

The ratio  is 4.  Thus each AlCl3 dissociates as follows:

 

AlCl3(s)  ®  Al3+(aq) + 3Cl-(aq)

13.105

Reverse osmosis involves no phase changes and is usually cheaper than distillation or freezing.

 

To reverse the osmotic migration of water across a semipermeable membrane, an external pressure exceeding the osmotic pressure must be applied.  To find the osmotic pressure of 0.70 M NaCl solution, we must use the van’t Hoff factor because NaCl is a strong electrolyte and the total ion concentration becomes 2(0.70 M)  =  1.4 M.

 

The osmotic pressure of sea water is:

 

p  =  iMRT  =  2(0.70 mol/L)(0.0821 L×atm/mol×K)(298 K)  =  34 atm

 

To cause reverse osmosis a pressure in excess of 34 atm must be applied.

13.106

First, we tabulate the concentration of all of the ions.  Notice that the chloride concentration comes from more than one source.

 

        MgCl2:                 If [MgCl2] = 0.054 M,                   [Mg2+] = 0.054 M                   [Cl-] = 2 ´ 0.054 M

 

        Na2SO4:               if [Na2SO4] = 0.051 M,                  [Na+] = 2 ´ 0.051 M              [SO] = 0.051 M

 

        CaCl2:                  if [CaCl2] = 0.010 M,                     [Ca2+] = 0.010 M                    [Cl-] = 2 ´ 0.010 M

 

        NaHCO3:             if [NaHCO3] = 0.0020 M              [Na+] = 0.0020 M                   [HCO] = 0.0020 M

 

        KCl:                      if [KCl] = 0.0090 M                       [K+] = 0.0090 M                     [Cl-] = 0.0090 M

 

The subtotal of chloride ion concentration is:

 

[Cl-]  =  (2 ´ 0.0540) + (2 ´ 0.010) + (0.0090)  =  0.137 M

 

Since the required [Cl-] is 2.60 M, the difference (2.6 - 0.137 = 2.46 M) must come from NaCl.

 

The subtotal of sodium ion concentration is:

 

[Na+] =  (2 ´ 0.051) + (0.0020)  =  0.104 M

 

Since the required [Na+] is 2.56 M, the difference (2.56 - 0.104 = 2.46 M) must come from NaCl.

 

Now, calculating the mass of the compounds required:

 

NaCl:                    

 

MgCl2:                  

 

Na2SO4:                

 

CaCl2:                   

 

KCl:                       

 

NaHCO3:              

13.107

Using Equation 13.8 of the text, we find the molarity of the solution.

 

M = 0.295 M

 

This is the combined concentrations of all the ions.  For dilute solutions, M » m.  Therefore, the freezing point of blood can be calculated using Equation 13.7.

 

DTf = Kf m =   (1.86°C/m)(0.295 m) = 0.55°C

 

Thus, the freezing point of blood should be about -0.55°C.

13.108

               

In order to increase the concentration in the intracellular volume by 8.0 ´ 10-3 M, the antibiotic must transport 1.6 ´ 10-15 mol Na+ ions.

 

 

 

time =19 s

13.109

a.

Using Equation 13.8 of the text, we find the molarity of the solution.

 

 

This is the combined concentrations of all the ions.  The amount dissolved in 10.0 mL (0.01000 L) is

 

 

Since the mass of this amount of protein is 0.225 g, the apparent molar mass is

 

b.

We need to use a van’t Hoff factor to take into account the fact that the protein is a strong electrolyte.  The van’t Hoff factor will be i = 21 (why?).

 

 

This is the actual concentration of the protein.  The amount in 10.0 mL (0.0100 L) is

 

 

Therefore the actual molar mass is:

 

13.110

Solution A:  Let molar mass be M.

 

 

(760 - 754.5)  =  CA(760)

 

CA  =  7.237 ´ 10-3

 

 

 

M  =  124 g/mol

 

Solution B:  Let molar mass be M

 

 

CB  = 7.237 ´ 10-3

 

 

 

M  =  248 g/mol

 

The molar mass in benzene is about twice that in water.  This suggests some sort of dimerization is occurring in a nonpolar solvent such as benzene.

13.111

2H2O2  ®  2H2O + O2

 

 

a.

Using the ideal gas law:

 

b.

The ratio of the volumes:                                 

Think About It:

Could we have made the calculation in part (a) simpler if we used the fact that 1 mole of all ideal gases at STP occupies a volume of 22.4 L?

13.112

As the chain becomes longer, the alcohols become more like hydrocarbons (nonpolar) in their properties.  The alcohol with five carbons (n-pentanol) would be the best solvent for iodine (a) and n-pentane (c) (why?).  Methanol (CH3OH) is the most water-like and is the best solvent for an ionic solid like KBr.

13.113

a.

At reduced pressure, the solution is supersaturated with CO2.

b.

As the escaping CO2 expands it cools, condensing water vapor in the air to form fog.

13.114

I2 - H2O:  Dipole - induced dipole. 

 

I - H2O:  Ion - dipole.  Stronger interaction causes more I2 to be converted to I.

13.115

a.

Runoff of the salt solution into the soil increases the salinity of the soil.  If the soil becomes hypertonic relative to the tree cells, osmosis would reverse, and the tree would lose water to the soil and eventually die of dehydration. 

b.

Assuming the collecting duct acts as a semipermeable membrane, water would flow from the urine into the hypertonic fluid, thus returning water to the body.

13.116

20.3 mL O2

 

20.3 mL O2 ´ 0.95 = 19 mL O2 in 100 mL blood in the lungs

 

20.3 mL O2 ´ 0.74 = 15 mL O2 in 100 mL blood in the capillaries

 

The volume of O2 released by hemoglobin when 100 mL of blood flows from the lungs to the capillaries is 19 - 15 = 4 mL.

13.117

At equilibrium, the concentrations in the 2 beakers are equal.  Let x L be the change in volume.

 

 

 

 

 

                               

The final volumes are:

 

(50 - 16.7) mL  =  33 mL

 

(50 + 16.7) mL =  67 mL

13.118

a.

If the membrane is permeable to all the ions and to the water, the result will be the same as just removing the membrane.  Eventually, the concentrations will become uniform throughout the sample.

b.

This part is tricky.  The movement of one ion but not the other would result in one side of the apparatus acquiring a positive electric charge and the other side becoming equally negative.  This has never been known to happen, so we must conclude that migrating ions always drag other ions of the opposite charge with them.  In this hypothetical situation only water would move through the membrane from the dilute to the more concentrated side.

c.

This is the classic osmosis situation.  Water would move through the membrane from the dilute to the concentrated side.

13.119

First, we calculate the number of moles of HCl in 100 g of solution.

 

 

Next, we calculate the volume of 100 g of solution.

 

 

Finally, the molarity of the solution is:

 

13.120

a.

Seawater has a larger number of ionic compounds dissolved in it; thus the boiling point is elevated.

b.

Carbon dioxide escapes from an opened soft drink bottle because gases are less soluble in liquids at lower pressure (Henry’s law).

c.

As you proved in Problem 13.20, at dilute concentrations molality and molarity are almost the same because the density of the solution is almost equal to that of the pure solvent.

d.

For colligative properties we are concerned with the number of solute particles in solution relative to the number of solvent particles.  Since in colligative particle measurements we frequently are dealing with changes in temperature (and since density varies with temperature), we need a concentration unit that is temperature invariant.  We use units of moles per kilogram of mass (molality) rather than moles per liter of solution (molarity).

e.

Methanol is very water soluble (why?) and effectively lowers the freezing point of water.  However in the summer, the temperatures are sufficiently high so that most of the methanol would be lost to vaporization.

13.121

Let the mass of NaCl be x g.  Then, the mass of sucrose is (10.2 - x)g.

 

We know that the equation representing the osmotic pressure is:

 

p  =  MRT

 

p, R, and T are given.  Using this equation and the definition of molarity, we can calculate the percentage of NaCl in the mixture.

 

 

Remember that NaCl dissociates into two ions in solution; therefore, we multiply the moles of NaCl by two.

 

 

mol solute  =  0.03422x + 0.02980 - 0.002921x

 

mol solute  =  0.03130x + 0.02980

 

 

Substitute molarity into the equation for osmotic pressure to solve for x.

 

p  =  MRT

 

 

0.0753  =  0.03130x + 0.02980

 

x  =  1.45 g  =  mass of NaCl

 

13.122

                                DTf  =  5.5 - 2.2  =  3.3°C                                   C10H8: 128.2 g/mol

 

                                                       C6H12: 84.16 g/mol

 

Let x = mass of C6H12 (in grams).

 

Using,

 

 

 

 

x  =  0.47 g

 

 

13.123

a.

Solubility decreases with increasing lattice energy.

b.

Ionic compounds are more soluble in a polar solvent.

c.

Solubility increases with enthalpy of hydration of the cation and anion.

13.124

The completed table is shown below:

 

    Attractive Forces                     Deviation from Raoult’s                            DHsolution

                        A « A, B « B > A « B                            Positive                                 Positive (endothermic)

 

                       A « A, B « B < A « B                           Negative                                 Negative (exothermic)

 

                       A « A, B « B = A « B                               Zero                                                     Zero

 

The first row represents a Case 1 situation in which A’s attract A’s and B’s attract B’s more strongly than A’s attract B’s.  This results in positive deviation from Raoult’s law (higher vapor pressure than calculated) and positive heat of solution (endothermic).

 

In the second row a negative deviation from Raoult’s law (lower than calculated vapor pressure) means A’s attract B’s better than A’s attract A’s and B’s attract B’s.  This causes a negative (exothermic) heat of solution.

 

In the third row a zero heat of solution means that A-A, B-B, and A-B interparticle attractions are all the same.  This corresponds to an ideal solution which obeys Raoult’s law exactly.

Think About It:

What sorts of substances form ideal solutions with each other?

13.125

Let's assume we have 100 g of solution.  The 100 g of solution will contain 70.0 g of HNO3 and 30.0 g of H2O.

 

 

 

 

To calculate the density, let's again assume we have 100 g of solution.  Since,

 

 

we know the mass (100 g) and therefore need to calculate the volume of the solution.  We know from the molarity that 15.9 mol of HNO3 are dissolved in a solution volume of 1000 mL.  In 100 g of solution, there are 1.11 moles HNO3 (calculated above).  What volume will 1.11 moles of HNO3 occupy?

 

 

Dividing the mass by the volume gives the density.

 

13.126

 

Pethanol  =  (0.62)(108 mmHg)  =  67.0 mmHg

 

P1-propanol  =  (0.38)(40.0 mmHg)  =  15.2 mmHg

 

In the vapor phase:

 

13.127

NH3 can form hydrogen bonds with water; NCl3 cannot.  (Like dissolves like.)

13.128

Since the total volume is less than the sum of the two volumes, the ethanol and water must have an intermolecular attraction that results in an overall smaller volume.

13.129

We can calculate the molality of the solution from the freezing point depression.

 

DTf  =  Kfm

 

0.203  =  1.86 m

 

 

The molality of the original solution was 0.106 m.  Some of the solution has ionized to H+ and CH3COO-.

 

                                                                                CH3COOH    CH3COO-  +  H+

 

                                                Initial                         0.106 m                  0                    0

    Change                      -x                            +x              +x

                                                Equil.                          0.106 m - x           x                    x

 

At equilibrium, the total concentration of species in solution is 0.109 m.

 

(0.106 - x) + 2x  =  0.109 m

 

x  =  0.003 m

 

The percentage of acid that has undergone ionization is:

 

13.130

Strategy:

Consider the number of polar groups, and determine whether each molecule is predominantly polar or predominantly nonpolar.  Predominantly polar molecules tend to be water soluble.  Predominantly nonpolar molecules tend to be fat soluble.

Setup:

Polar groups include those containing O atoms or N atoms (atoms with lone pairs).  Pantothenic acid contains 7 polar groups (five O atoms and two N atoms) making it predominantly polar.  Nicotinic acid is a small molecule containing 3 polar groups (two O atoms and one N atom) making it predominately polar.  Vitamin K is a large molecule that contains only two polar groups and is therefore predominately nonpolar.

Solution:

Pantothenic acid:  water soluble

 

Nicotinic acid:  water soluble

 

Vitamin K:  fat soluble

13.131

Egg yolk contains lecithins which solubilize oil in water (See Figure 13.18 of the text).  The nonpolar oil becomes soluble in water because the nonpolar tails of lecithin dissolve in the oil, and the polar heads of the lecithin molecules dissolve in polar water (like dissolves like).

13.132

First, we can calculate the molality of the solution from the freezing point depression.

 

DTf  =  (5.12)m

 

(5.5 - 3.5)  =  (5.12)m

 

m  =  0.39

 

Next, from the definition of molality, we can calculate the moles of solute.

 

 

 

mol solute  =  0.031 mol

 

The molar mass (M) of the solute is:

 

 

The molar mass of CH3COOH is 60.05 g/mol.  Since the molar mass of the solute calculated from the freezing point depression is twice this value, the structure of the solute most likely is a dimer that is held together by hydrogen bonds.

 

13.133

192 mg  =  192 ´ 10-6 g  or  1.92 ´ 10-4 g

 

 

Safety limit:  0.050 ppm implies a mass of 0.050 g Pb per 1 ´ 106 g of water.  1 liter of water has a mass of 1000 g.

 

 

Yes, the concentration of lead calculated above (7.4 ´ 10-5 g/L) exceeds the safety limit of 5.0 ´ 10-5 g/L.  (Don’t drink the water!)

13.134

a.

DTf  =  Kfm

 

2  =  (1.86)(m)

 

molality  =  1.1 m

 

This concentration is too high and is not a reasonable physiological concentration.

b.

As soon as a microscopic ice crystal begins to form, the protein binds to it, blocking the addition of other water molecules to the crystal and thus halting its growth.

13.135

As the water freezes, dissolved minerals in the water precipitate from solution.  The minerals refract light and create an opaque appearance.

13.136

If the can is tapped with a metal object, the vibration releases the bubbles and they move to the top of the can where they join up to form bigger bubbles or mix with the gas at the top of the can.  When the can is opened, the gas escapes without dragging the liquid out of the can with it.  If the can is not tapped, the bubbles expand when the pressure is released and push the liquid out ahead of them.

13.137

At equilibrium, the vapor pressure of benzene over each beaker must be the same.  Assuming ideal solutions, this means that the mole fraction of benzene in each beaker must be identical at equilibrium.  Consequently, the mole fraction of solute is also the same in each beaker, even though the solutes are different in the two solutions.  Assuming the solute to be non-volatile, equilibrium is reached by the transfer of benzene, via the vapor phase, from beaker A to beaker B.

 

The mole fraction of naphthalene in beaker A at equilibrium can be determined from the data given.  The number of moles of naphthalene is given, and the moles of benzene can be calculated using its molar mass and knowing that 100 g - 7.0 g = 93.0 g of benzene remain in the beaker.

 

 

Now, let the number of moles of unknown compound be n.  Assuming all the benzene lost from beaker A is transferred to beaker B, there are 100 g + 7.0 g = 107 g of benzene in the beaker.  Also, recall that the mole fraction of solute in beaker B is equal to that in beaker A at equilibrium (0.112).  The mole fraction of the unknown compound is:

 

 

 

n  =  0.1728 mol

 

There are 31 grams of the unknown compound dissolved in benzene.  The molar mass of the unknown is:

 

 

Temperature is assumed constant and ideal behavior is also assumed.  Both solutes are assumed to be nonvolatile.

13.138

a.

or

          (1)

 

If we assume 1 L of solution, then we can calculate the mass of solution from its density and volume (1000 mL), and the mass of solute from the molarity and its molar mass.

 

 

 

Substituting these expressions into Equation (1) above gives:

 

or

          (2)

 

From the definition of molality (m), we know that:

 

         (3)

 

Assuming 1 L of solution, we also know that mol solute (n) = Molarity (M), so Equation (3) becomes:

 

 

Substituting back into Equation (2) gives:

 

 

Taking the inverse of both sides of the equation gives:

 

or

b.

The density of a dilute aqueous solution is approximately 1 g/mL, because the density of water is approximately 1 g/mL.  In dilute solutions, .  Consider a 0.010 M NaCl solution.

 

 

With , the derived equation reduces to:

 

 

Because d » 1 g/mL. m » M.

13.139

To solve for the molality of the solution, we need the moles of solute (urea) and the kilograms of solvent (water).  If we assume that we have 1 mole of water, we know the mass of water.  Using the change in vapor pressure, we can solve for the mole fraction of urea and then the moles of urea.

 

Using Equation 13.5 of the text, we solve for the mole fraction of urea.

 

DP  =  23.76 mmHg - 22.98 mmHg  =  0.78 mmHg

 

 

 

Assuming that we have 1 mole of water, we can now solve for moles of urea.

 

 

 

0.033nurea + 0.033  =  nurea

 

0.033  =  0.967nurea

 

nurea  =  0.034 mol

 

1 mole of water has a mass of 18.02 g or 0.01802 kg.  We now know the moles of solute (urea) and the kilograms of solvent (water), so we can solve for the molality of the solution.

 

13.140

The desired process is for (fresh) water to move from a more concentrated solution (seawater) to pure solvent.  This is an example of reverse osmosis, and external pressure must be provided to overcome the osmotic pressure of the seawater.  The source of the pressure here is the water pressure, which increases with increasing depth.  The osmotic pressure of the seawater is:

 

p  =  MRT

 

p  =  (0.70 M)(0.0821 L×atm/mol×K)(293 K)

 

p  =  16.8 atm

 

The water pressure at the membrane depends on the height of the sea above it, i.e. the depth.  P = hdg where h, d, and g are the height of the sea above the membrane, the density of the solution, and the gravitational constant, respectively;  and fresh water will begin to pass through the membrane when P = p.  Substituting  p = P into the equation gives:

 

p  =  hdg

 

and

 

 

Before substituting into the equation to solve for h, we need to convert atm to pascals, and the density to units of kg/m3.  These conversions will give a height in units of meters.

 

 

1 Pa = 1 N/m2 and 1 N = 1 kg×m/s2.  Therefore, we can write 1.70 × 106 Pa as 1.70 × 106 kg/m×s2

 

 

h =168 m

13.141

The total vapor pressure depends on the vapor pressures of A and B in the mixture, which in turn depends on the vapor pressures of pure A and B.  With the total vapor pressure of the two mixtures known, a pair of simultaneous equations can be written in terms of the vapor pressures of pure A and B.  We carry 2 extra significant figures throughout this calculation to avoid rounding errors.

 

For the solution containing 1.2 moles of A and 2.3 moles of B,

 

 

CB  =  1 - 0.3429  =  0.6571

 

 

Substituting in Ptotal and the mole fractions calculated gives:

 

 

Solving for ,

 

         (1)

 

Now, consider the solution with the additional mole of B.

 

 

CB  =  1 - 0.2667  =  0.7333

 

 

Substituting in Ptotal and the mole fractions calculated gives:

 

          (2)

 

Substituting Equation (1) into Equation (2) gives:

 

 

 

 

Substitute the value of  into Equation (1) to solve for .

 

13.142

Starting with n = kP and substituting into the ideal gas equation (PV = nRT), we find:

 

PV  =  (kP)RT

 

V  =  kRT

 

This equation shows that the volume of a gas that dissolves in a given amount of solvent is dependent on the temperature, not the pressure of the gas.

13.143

To calculate the freezing point of the solution, we need the solution molality and the freezing-point depression constant for water (see Table 13.2 of the text).  We can first calculate the molarity of the solution using Equation 13.8 of the text: p = MRT.  The solution molality can then be determined from the molarity.

 

 

Let’s assume that we have 1 L (1000 mL) of solution.  The mass of 1000 mL of solution is:

 

 

The mass of the solvent (H2O) is:

 

mass H2O  =  mass soln - mass solute

 

 

The molality of the solution is:

 

 

The freezing point depression is:

 

DTf  =  Kfm  =  (1.86°C/m)(0.396 m)  =  0.737°C

 

The solution will freeze at 0°C - 0.737°C = -0.737°C

13.144

Strategy:

Because the solutes are all ionic, each solute concentration will have to be multiplied by the appropriate van’t Hoff factor.  (Because we are assuming no ion pairing, we can use calculated van’t Hoff factors.)  Sum the concentrations for all solutes to determine the total concentration of dissolved particles, and use Equation 13.8 to calculate osmotic pressure.

Setup:

Because the volume of the solution described is 1 L, the number of moles is also the molarity for each solute.  R = 0.08206 L · atm/K · mol, T = 310 K, and the van’t Hoff factors for the solutes in Ringer’s lactate are as follows:

 

NaCl(s) → Na+(aq) + Cl(aq)                             i = 2

 

KCl(s) → K+(aq) + Cl(aq)                 i = 2

 

CaCl2(s) → Ca2+(aq) + 2Cl(aq)                        i = 3

 

NaCH3CH2COO(s) → Na+(aq) + CH3CH2COO(aq)             i = 2

Solution:

The total concentration of ions in solution is the sum of the individual concentrations.

 

total concentration = 2[NaCl] + 2[KCl] + 3[CaCl2] + 2[NaCH3CH2COO]

 

= 2(0.102 M) + 2(4 × 10–3 M) + 3(1.5 × 10–3 M) + 2(2.8 × 10–2 M)

 

= 2.73 × 10–1 M

 

π = MRT = (0.273 M)(0.08206 L · atm/K · mol)(310 K) = 6.94 atm

13.145

Strategy:

From the figure, note that the normal boiling point of the solution is elevated by about 1°C. Use the boiling point elevation equation (Equation 13.6) with Kb = 2.53 °C/m (Table 13.2).

Solution:

 

 

 

The solution concentration is about 0.4 molal.

13.146

The interior of the molecule is lined with polar C=O and NH functional groups, and a K+ ion readily “dissolves” into this polar environment. One the other hand, the exterior of the molecule has a large number of non-polar CH3 groups (one at the end of each “Y”), making the entire molecule (and its K+ “cargo”) soluble in the non-polar cell membrane. As the molecule incorporates a K+ ion into its interior, it deforms slightly, presenting even more non-polar groups to the exterior side, thus enhancing the “loaded” molecule’s solubility in non-polar environments.

13.147

Strategy:

Use Equation 13.2 and the definition of ppm to calculate the percent F by mass.

 

Use the molar mass of NaF to determine the mass of NaF in a gram of solution.  Subtract the mass of NaF from the mass of the solution to determine the mass of the solvent (water).  Use Equation 13.1 to determine the molality. 

Setup:

The molar mass of NaF is 41.99 g/mol.

 

 

Consider the ionization of NaF:

 

 

According to this equation, if 1.0 mol NaF molecules ionize, we get 1.0 mol Na + ion and

1.0 mol F ions.

Solution:

To calculate percent mass by F,

 

1.0 ppm F =

 

To calculate molality, first determine the number of moles and mass of NaF per gram of solution.

 

 

 

Finally, calculate the molality.

 

13.148

a.

Strategy:

Use Equation 13.9 to calculate the van’t Hoff factor of fluorosilicic acid.

Setup:

Kf for water (Table 13.2) is 1.86°C/m.

 

The normal freezing point of water is 0°C.  Therefore, ∆Tf is 0°C – (–15.5°C) = 15.5°C.

Solution:

Solve Equation 13.9 for the van’t Hoff factor:

 

b.

Strategy:

Use Equation 13.11, p  =  iMRT, to calculate the molarity of the solution.  Then, determine the grams of acid in the solution using the density.  Multiply the grams of acid by one over the molarity to determine the molar mass.

Setup:

The van’t Hoff factor (calculated in part a) is 5.22.

 

The density of 23% fluorosilicic acid is 1.19 g/mL.

 

Converting to g/L gives:

 

 

 

Since the solution is 23% fluorosilicic acid, there are 23/100 or 0.23 g acid for every gram of solution.

 

Solution:

The molarity is given by:

 

 

The molar mass is:

 

13.149

a.

Strategy:

The mole fraction of a component is the number of moles of the component divided by the total number of moles in the mixture:

 

Setup:

The solution is prepared by mixing equal masses of A and B.  Assume a mass of 1.00 g for each component.

 

The molar mass of A is 100 g/mol and the molar mass of B is 110 g/mol.

 

 

Solution:

 

b.

Strategy:

According to Raoult’s Law, the vapor pressure of the solution is the sum of the individual partial pressures exerted by the solution components.  Use Equation 13.4 to calculate the partial pressures of A and B. 

 

Setup:

At 55°C, = 98 mm Hg and = 42 mm Hg.

 

The mole fractions of A and B were calculated in part (a):  χA= 0.52 and  χB =0.48.

Solution:

 

c.

Strategy:

The total pressure is given by Dalton’s law of partial pressures, PT = PA + PB.  The mole fraction is then equal to the partial pressure of a component divided by the total pressure according to Equation 11.16:

 

Setup:

Use the partial pressures of A and B (calculated in part (b)) to determine the total pressure, PT. 

 

PT = 51 mm Hg + 20 mm Hg = 71 mm Hg

Solution:

 

d.

Strategy:

Use Equation 13.4 to calculate the partial pressures of A and B. 

 

Setup:

The mole fraction of each component above the condensed liquid was calculated in part (c):  χA = 0.72 and χB = 0.28

Solution: