Chapter 13 The Properties of Mixtures: Solutions and Colloids
Chapter 13 The Properties of Mixtures: Solutions and Colloids
Chapter 13 The Properties of Mixtures: Solutions and Colloids
A heterogeneous mixture has two or more phases, thus seawater has both dissolved and suspended particles. The
composition of the seawater is different in various places where a sample may be obtained.
13.2
When a salt such as NaCl dissolves, ion-dipole forces cause the ions to separate, and many water molecules cluster
around each of them in hydration shells. Ion-dipole forces hold the first shell. Additional shells are held by
hydrogen bonding to inner shells.
13.3
In CH3(CH2)nCOOH, as n increases, the hydrophobic (CH) portion of the carboxylic acid increases and the
hydrophilic part of the molecule stays the same, with a resulting decrease in water solubility.
13.4
Sodium stearate would be a more effective soap because the hydrocarbon chain in the stearate ion is longer than
the chain in the acetate ion. A soap forms suspended particles called micelles with the polar end of the soap
interacting with the water solvent molecules and the nonpolar ends forming a nonpolar environment inside the
micelle. Oils dissolve in the nonpolar portion of the micelle. Thus, a better solvent for the oils in dirt is a more
nonpolar substance. The long hydrocarbon chain in the stearate ion is better at dissolving oils in the micelle than
the shorter hydrocarbon chain in the acetate ion.
13.5
Hexane and methanol, as gases, are free from any intermolecular forces and can simply intermix with each other.
As liquids, hexane is a non-polar molecule, whereas methanol is a polar molecule. Like dissolves like.
13.6
Hydrogen chloride (HCl) gas is actually reacting with the solvent (water) and thus shows a higher solubility than
propane (C3H8) gas, which does not react.
13.7
a) A more concentrated solution will have more solute dissolved in the solvent. Potassium nitrate, KNO3, is an
ionic compound and therefore soluble in a polar solvent like water. Potassium nitrate is not soluble in the
nonpolar solvent CCl4. Because potassium nitrate dissolves to a greater extent in water, KNO3 in H2O will result
in the more concentrated solution.
13.8
b) Stearic acid in CCl4. Stearic acid will not dissolve in water. It is non-polar while water is very polar. Stearic
acid will dissolve in carbon tetrachloride, as both are non-polar.
13.9
To identify the strongest type of intermolecular force, check the formula of the solute and identify the forces that
could occur. Then look at the formula for the solvent and determine if the forces identified for the solute would
occur with the solvent. The strongest force is ion-dipole followed by dipole-dipole (including H bonds). Next in
strength is ion-induced dipole force and then dipole-induced dipole force. The weakest intermolecular interactions
are dispersion forces.
a) Ion-dipole forces are the strongest intermolecular forces in the solution of the ionic substance cesium chloride
in polar water.
b) Hydrogen bonding (type of dipole-dipole force) is the strongest intermolecular force in the solution of polar
propanone (or acetone) in polar water.
c) Dipole-induced dipole forces are the strongest forces between the polar methanol and nonpolar carbon
tetrachloride.
13.10
a) metallic bonding
b) dipole-dipole
c) dipole-induced dipole
13-1
13.11
a) Hydrogen bonding occurs between the H atom on water and the lone electron pair on the O atom in dimethyl
ether (CH3OCH3). However, none of the hydrogen atoms on dimethyl ether participates in hydrogen bonding
because the CH bond does not have sufficient polarity.
b) The dipole in water induces a dipole on the Ne(g) atom, so dipole-induced dipole interactions are the
strongest intermolecular forces in this solution.
c) Nitrogen gas and butane are both nonpolar substances, so dispersion forces are the principal attractive forces.
13.12
a) dispersion forces
b) hydrogen bonding
c) dispersion forces
13.13
CH3CH2OCH2CH3 is polar with dipole-dipole interactions as the dominant intermolecular forces. Examine the
solutes to determine which has intermolecular forces more similar to those for the diethyl ether. This solute is the
one that would be more soluble.
a) HCl would be more soluble since it is a covalent compound with dipole-dipole forces, whereas NaCl is an ionic
solid. Dipole-dipole forces between HCl and diethyl ether are more similar to the dipole forces in diethyl ether
than the ion-dipole forces between NaCl and diethyl ether.
b) CH3CHO (acetaldehyde) would be more soluble. The dominant interactions in H2O are hydrogen bonding, a
stronger type of dipole-dipole force. The dominant interactions in CH3CHO are dipole-dipole. The solute-solvent
interactions between CH3CHO and diethyl ether are more similar to the solvent intermolecular forces than the
forces between H2O and diethyl ether.
c) CH3CH2MgBr would be more soluble. CH3CH2MgBr has a polar end (MgBr) and a nonpolar end
(CH3CH2), whereas MgBr2 is an ionic compound. The nonpolar end of CH3CH2MgBr and diethyl ether would
interact with dispersion forces, while the polar end of CH3CH2MgBr and the dipole in diethyl ether would interact
with dipole-dipole forces. Recall, that if the polarity continues to increase, the bond will eventually become ionic.
There is a continuous sequence from nonpolar covalent to ionic.
13.14
13.15
No, river water is a heterogeneous mixture, with its composition changing from one segment to another.
13.16
Gluconic acid is a very polar molecule because it has OH groups attached to every carbon. The abundance of
OH bonds allows gluconic acid to participate in extensive Hbonding with water, hence its great solubility in
water. On the other hand, caproic acid has a 5carbon, nonpolar, hydrophobic (water hating) tail that does not
easily dissolve in water. The dispersion forces in the nonpolar tail are more similar to the dispersion forces in
hexane, hence its greater solubility in hexane.
13.17
There may be a disulfide linkage (a covalent disulfide bridge) between the ends of two cysteine side chains that
bring together parts of the chain. There may be salt links between ions COO and NH3+ groups. There may be
hydrogen bonding between the C=O of one peptide bond and the N-H of another.
13.18
The nitrogen bases hydrogen bond to their complimentary bases. The flat, N-containing bases stack above each
other, which allow extensive interaction through dispersion forces. The exterior negatively charged sugarphosphate chains form ion-dipole and hydrogen bonds to the aqueous surroundings, but this is of minor
importance to the structure.
13.19
The more carbon and hydrogen atoms present, the more soluble the substance is in non-polar oil droplets.
Therefore, sodium propanoate is not as effective a soap as sodium stearate with the longer hydrocarbon chain.
13.20
Dispersion forces are present between the nonpolar portions of the molecules within the bilayer. Polar groups are
present to hydrogen bond or to form dipole-dipole interactions with the aqueous surroundings.
13-2
13.21
In soluble proteins, polar groups are found on the exterior and nonpolar groups on the interior. In proteins
embedded in a membrane, the exterior of the protein that lies within the bilayer consists of nonpolar amino acid
side chains, whereas the portion lying outside the bilayer has polar side chains.
13.22
While an individual hydrogen bond is not too strong, there are very large numbers of hydrogen bonds present in
the wood. The strength of wood comes from the large number of hydrogen bonds, and to a lesser degree from the
numerous dispersion interactions.
13.23
Amino acids with side chains that may be ionic are necessary. Two examples are lysine and glutamic acid.
13.24
The Hsolvent and Hmix components of the heat of solution combined together represent the enthalpy change
during solvation, the process of surrounding a solute particle with solvent particles. Solution in water is often
called hydration.
13.25
For a general solvent, the energy changes needed to separate solvent into particles (Hsolvent), and that needed to
mix the solvent and solute particles (Hmix) would be combined to obtain Hsolution.
13.26
a) Charge density is the ratio of the ions charge to its volume. An ions charge and size affect its charge density.
b) < + < 2 < 3+
c) The higher the charge density, the more negative is Hhydration. Hhydration increases with increasing charge and
decreases with increasing size.
13.27
The solution cycle for ionic compounds in water consists of two enthalpy terms: the lattice energy, and the
combined heats of hydration of the cation and anion.
Hsoln = Hlattice + Hhyd of ions
For a heat of solution to be zero (or very small)
Hlattice Hhydration of ions, and they would have to have opposite signs.
13.28
a) Endothermic
b) The lattice energy term is much larger than the combined ionic heats of hydration.
c) The increase in entropy outweighs the increase in enthalpy, so ammonium chloride dissolves..
13.29
This compound would be very soluble in water. A large exothermic value in Hsolution (enthalpy of solution)
means that the solution has a much lower energy state than the isolated solute and solvent particles, so the system
tends to the formation of the solution. Entropy that accompanies dissolution always favors solution formation.
Entropy becomes important when explaining why solids with an endothermic Hsolution (and higher energy state)
are still soluble in water.
13.30
Enthalpy
K+(g) + Cl-(g)
Hlattice
Hhydration
K+(aq) + Cl-(aq)
Hsolution
KCl(s)
Hsolution > 0 (endothermic)
13-3
Lattice energy values are always positive as energy is required to separate the ions from each other.
Hydration energy values are always negative as energy is released when intermolecular forces between
ions and water form. Since the heat of solution for KCl is endothermic, the lattice energy must be greater
than the hydration energy for an overall input of energy.
.
13.31
Na+(g) +Il-(g)
Enthalpy
Hlattice
Hhydration
NaI(s)
Na+(aq) + I-(aq)
Hsolution
Lattice energy values are always positive as energy is required to separate the ions from each other.
Hydration energy values are always negative as energy is released when intermolecular forces between
ions and water form. Since the heat of solution for NaI is exothermic, the negative hydration energy must be
greater than the positive lattice energy.
13.32
Charge density is the ratio of an ions charge (regardless of sign) to its volume. An ions volume is
related to its radius. For ions whose charges have the same sign (+ or ), ion size decreases as a group in
the periodic table is ascended and as you proceed from left to right in the periodic table. Charge density increases
with increasing charge and increases with decreasing size.
a) Both ions have a +1 charge, but the volume of Na+ is smaller, so it has the greater charge density.
b) Sr2+ has a greater ionic charge and a smaller size (because it has a greater Zeff), so it has the greater charge
density.
c) Na+ has a smaller ion volume than Cl, so it has the greater charge density.
d) O2 has a greater ionic charge and similar ion volume, so it has the greater charge density.
e) OH has a smaller ion volume than SH (O is smaller than S), so it has the greater charge density.
f) Mg2+ has the higher charge density because it has a smaller ion volume.
g) Mg2+ has the higher charge density because it has both a smaller ion volume and greater charge.
h) CO32 has the higher charge density because it has both a smaller ion volume and greater charge.
13.33
13-4
13.34
The ion with the greater charge density will have the larger Hhydration.
a) Na+ would have a larger Hhydration than Cs+ since its charge density is greater than that of Cs+.
b) Sr2+ would have a larger Hhydration than Rb+.
c) Na+ would have a larger Hhydration than Cl.
d) O2 would have a larger Hhydration than F.
e) OH would have a larger Hhydration than SH.
f) Mg2+ would have a larger Hhydration than Ba2+.
g) Mg2+ would have a larger Hhydration than Na+.
h) CO32 would have a larger Hhydration than NO3.
13.35
a) I
13.36
a) The two ions in potassium bromate are K+ and BrO3. The heat of solution for ionic compounds is
Hsoln = Hlattice + Hhydr of the ions. Therefore, the combined heats of hydration for the ions is (Hsoln Hlattice) or
41.1 kJ/mol 745 kJ/mol = 703.9 = 704 kJ/mol.
b) K+ ion contributes more to the heat of hydration because it has a smaller size and, therefore, a greater charge
density.
13.37
13.38
13.39
a) Entropy increases
b) Entropy decreases
c) Entropy increases
13.40
13.41
Add a pinch of the solid solute to each solution. A saturated solution contains the maximum amount of dissolved
solute at a particular temperature. When additional solute is added to this solution, it will remain undissolved. An
unsaturated solution contains less than the maximum amount of dissolved solute and so will dissolve added solute.
A supersaturated solution is unstable and addition of a seed crystal of solute causes the excess solute to
crystallize immediately, leaving behind a saturated solution.
13.42
13.43
An increase in temperature produces an increase in kinetic energy; the solute molecules overcome the weak
intermolecular forces, which results in a decrease in solubility of any gas in water. In nearly all cases, gases
dissolve exothermically (Hsoln < 0).
b) Ca2+ c) Br
d) Cl
e) Sc3+
f) ClO4
13-5
g) Fe2+
h) K+
13.44
a) Increasing pressure for a gas increases the solubility of the gas according to Henrys law.
b) Increasing the volume of a gas causes a decrease in its pressure (Boyles Law), which decreases the solubility
of the gas.
13.45
a) increase
13.46
a) Solubility for a gas is calculated from Henrys law: Sgas = kH Pgas. Sgas is expressed as mol/L, so convert
moles of O2 to mass of O2 using the molar mass.
Sgas = kH Pgas
mol
3
Sgas = 1.28 x 103
(1.00 atm ) = 1.28 x 10 mol/L
i
L
atm
1 mol O 2
b) The amount of gas that will dissolve in a given volume decreases proportionately with the partial pressure of
the gas, so
mol
1 mol O 2
13.47
mol
0.93%
Liatm
100%
13.48
13.49
13.50
Solubility of gases increases with increasing partial pressure of the gas, and the goal of these devices is to increase
the amount of oxygen dissolving in the bloodstream.
13.51
Molarity is defined as the number of moles of solute dissolved in one liter of solution. Molality is defined as the
number of moles of solute dissolved in 1000 g (1 kg) of solvent. Molal solutions are prepared by measuring
masses of solute and solvent, which are additive and not changed by temperature, so the concentration in molality
does not change with temperature.
13.52
Refer to the Table 13.5 for the different methods of expressing concentration.
a) Molarity and parts-by-volume (% w/v or % v/v) include the volume of the solution.
b) Parts-by-mass (% w/w) include the mass of solution directly. (Others may involve the mass indirectly.)
c) Molality includes the mass of the solvent.
13.53
13.54
Converting between molarity and molality involves conversion between volume of solution and mass of solution.
Both of these quantities are given so interconversion is possible. To convert to mole fraction requires that the
mass of solvent be converted to moles of solvent. Since the identity of the solvent is not given, conversion to mole
fraction is not possible if the molar mass is not known.
13-6
13.55
13.56
% w/w, mole fraction, and molality are weight-to-weight relationships that are not affected by changes in
temperature. % w/v and molarity are affected by changes in temperature, because the volume is temperature
dependant.
mol of solute
Convert the masses to moles and the volumes to liters and use the definition of molarity: M =
V(L) of solution
32.3 g C12 H 22 O11 1 mL 1 mol C12 H 22 O11
a) Molarity =
= 0.943617 = 0.944 M C12H22O11
3
100. mL
13.57
0.82 g C2 H 5 OH 1 mL 1 mol C 2 H 5 OH
a) Molarity =
= 1.69514 = 1.7 M C2H5OH
3
10.5 mL
10 L 46.07 g C 2 H 5 OH
1.27 g NH 3
b) Molarity =
33.5 mL
1 mL 1 mol NH 3
= 2.2261 = 2.23 M NH3
3
10 L 17.03 g NH3
13.58
= 0.07488 = 0.0749 M
( 0.250 L )
1 mL
b) Mconc = 1.2 M HNO3 Vconc = 38.5 mL Mdil = ? Vdil = 0.130 L
(1.2 M )( 38.5 mL ) 103 L
Mdil = Mconc Vconc / Vdil =
= 0.355385 = 0.36 M
( 0.130 L ) 1 mL
13.59
= 0.31875 = 0.319 M
( 0.500 L )
1 mL
Vconc = 8.25 mL Mdil = ? Vdil = 12.0 mL
b) Mconc = 2.00 x 102 M KI
Mdil = Mconc Vconc / Vdil =
13.60
( 2.00 x 10
M ( 8.25 mL )
(12.0 mL )
= 0.01375 = 0.0138 M
a) Find the number of moles KH2PO4 needed to make 365 mL of this solution. Convert moles to mass using the
molar mass of KH2PO4 (Molar mass = 136.09 g/mol)
103 L 8.55 x 102 mol KH 2 PO 4 136.09 g KH 2 PO 4
Mass KH2PO4 = ( 365 mL )
L
1 mL
1 mol KH 2 PO 4
= 4.24703 = 4.25 g KH2PO4
Add 4.25 g KH2PO4 to enough water to make 365 mL of aqueous solution.
b) Use the relationship MconcVconc = MdilVdil to find the volume of 1.25 M NaOH needed.
Mconc = 1.25 M NaOH Vconc = ? Mdil = 0.335 M NaOH Vdil = 465 mL
( 0.335 M )( 465 mL )
Vconc = Mdil Vdil / Mconc =
= 124.62 = 125 mL
(1.25 M )
Add 125 mL of 1.25 M NaOH to enough water to make 465 mL of solution.
13-7
13.61
a) Find the number of moles NaCl needed to make 2.5 L of this solution. Convert moles to mass using the molar
mass of NaCl (Molar mass = 58.44 g/mol)
0.65 mol NaCl 58.44 g NaCl
Mass NaCl = ( 2.5 L )
1 mol NaCl = 94.965 = 95 g NaCl
L
13.62
a) To find the mass of KBr needed, find the moles of KBr in 1.40 L of a 0.288 M solution and convert to grams
using molar mass of KBr.
0.288 mol KBr 119.00 g KBr
Mass KBr = (1.40 L )
1 mol KBr = 47.9808 = 48.0 g KBr
L
To make the solution, weigh 48.0 g KBr and then dilute to 1.40 L with distilled water.
b) To find the volume of the concentrated solution that will be diluted to 255 mL, use MconcVconc = MdilVdil and
solve for Vconc.
Mconc = 0.264 M LiNO3 Vconc = ? Mdil = 0.0856 M LiNO3 Vdil = 255 mL
Vconc = Mdil Vdil / Mconc = (0.0856 M) (255 mL) / (0.264 M) = 82.68182 = 82.7 mL
To make the 0.0856 M solution, measure 82.7 mL of the 0.264 M solution and add distilled water to make a total
of 255 mL.
13.63
a) To find the mass of Cr(NO3)3 needed, find the moles of Cr(NO3)3 in 57.5 mL of a 1.53 x 10-3 M solution and
convert to grams using molar mass of Cr(NO3)3.
103 L 1.53 x 103 mol Cr(NO3 )3 238.03 g Cr(NO3 )3
Mass Cr(NO3)3 = ( 57.5 mL )
1 mL
L
1 mol Cr(NO3 )3
= 0.020941 = 0.0209 g Cr(NO3)3
To make the solution, weigh 0.0209 g Cr(NO3)3 and then dilute to 57.5 mL with distilled water.
b) To find the volume of the concentrated solution that will be diluted to 5.8 x 103 m3 use MconcVconc = MdilVdil and
solve for Vconc.
Mconc = 2.50 M NH4NO3 Vconc = ?
Mdil = 1.45 M NH4NO3
Vdil = 5.8 x 103 m3
3
3
Vconc = Mdil Vdil / Mconc = (1.45 M) (5.8 x 10 m ) / (2.50 M) = 3.364 x 103 = 3.4 x 103 m3
To make the 1.45 M solution, measure 3.4 x 103 m3 of the 2.50 M solution and add distilled water to make
5.8 x 103 m3.
13.64
Molality, m =
moles of solute
kg of solvent
1 mol Glycine
85.4 g Glycine
1 mol Glycerol
8.59 g Glycerol
3
92.09 g Glycerol 10 g = 1.2114 = 1.21 m glycerol
b) m glycerol =
( 77.0 g )
1 kg
13-8
13.65
3
36.46 g HCl 10 g = 6.3043 = 6.30 m HCl
a) m HCl =
( 757 g )
1 kg
1 mol Naphthalene
16.5 g Naphthalene
3
128.16 g Naphthalene 10 g
b) m naphthalene =
( 53.3 g )
1 kg
Molality, m =
moles of solute
kg of solvent
0.877 g 1 mol C6 H 6
mL 78.11 g C6 H 6
0.660 g
(167 mL C6 H14 )
mL
( 44.0 mL C6 H6 )
m benzene =
13.67
13.68
mL 153.81 g CCl4
m CCl4 =
1.33 g
( 76.5 mL CH 2 Cl2 )
mL
3
10 g = 4.48214 = 4.48 m C H
6 6
1 kg
3
10 g = 0.2702596 = 0.270 m CCl
4
1 kg
a) The total mass of the solution is 3.10 x 102 g, so masssolute + masssolvent = 3.10 x 102 g.
0.125 mol C2 H 6 O 2 62.07 g C2 H 6 O 2
Mass of C2H6O2 in 1000 g (1 kg) of H2O =
1 kg H 2 O
1 mol C2 H 6 O 2
= 7.75875 g C2H6O2 in 1000 g H2O
Grams of this solution = 1000 g H2O + 7.75875 g C2H6O2 = 1007.75875 g
7.75875 g C2 H 6 O 2
2
Mass C2H6O2 =
3.10 x 10 g solution = = 2.386695 g C2H6O2
1007.75875
g
solution
Masssolvent = 3.10 x 102 g masssolute = 3.10 x 102 g 2.386695 g C2H6O2 = 307.613305 = 308 g H2O
Therefore, add 2.39 g C2H6O2 to 308 g of H2O to make a 0.125 m solution.
b) This is a disguised dilution problem. First, determine the amount of solute in your target solution:
2.20%
100% (1.20 kg ) = 0.0264 kg HNO3 (solute)
Then determine the amount of the concentrated acid solution needed to get 0.0264 kg solute:
52.0%
100% ( mass needed ) = 0.0264 kg
13-9
13.69
1 kg H 2 O
1 mol C 2 H5 OH
= 1.635485g C2H5OH / 1000 g H2O (unrounded)
Grams of this solution = 1000 g H2O + 1.635485 g C2H5OH = 1001.635485 g (unrounded)
Mass C2H6O2 = [1.635485 g C2H5OOH / 1001.635485 g solution] [1.50 kg solution (103 g / 1 kg)]
= 2.449222 = 2.45 g C2H5OH
Masssolvent = 1500 g masssolute = 1500 g 2.449222 g C2H6O2 = 1497.551 = 1498 g H2O
Therefore, add 2.45 g C2H5OH to 1498 g of H2O to make a 0.0355 m solution.
b) This is a disguised dilution problem. First, determine the amount of solute in your target solution:
(445 g) (13.0% / 100%) = 57.85 g HCl (solute) (unrounded)
Then determine the amount of the concentrated acid solution needed to get 57.85 g solute:
(Mass needed) (34.1% / 100%) = 57.85 g
Mass solute needed = 169.6481 = 170. g
Mass solvent = Mass solution Mass solute = 445 g 169.6481 g = 275.35191 = 275 g
Add 170. g of the 34.1% (w/w) HCl to 275 g H2O
13.70
b) Mass percent =
= 22.85043 = 23 m isopropanol
15.317 g Water 1 kg
13.71
13-10
13.72
10 L 1 mL 103 g
moles CsBr
0.400 m CsBr =
0.500 kg H 2 O
Moles CsBr = 0.2000 mol (unrounded)
212.8 g CsBr
Mass of CsBr = ( 0.200 mol CsBr )
= 42.56 = 42.6 g CsBr
1 mol CsBr
Mass H2O = Mass of solution Mass of CsBr =
103 g
( 0.500 kg )
- 42.56 g CsBr = 457.44 g H2O
1 kg
1 mol H 2 O
Moles H2O = ( 457.44 g H 2 O )
= 25.38513 mol H2O
18.02 g H 2 O
0.2000 mol CsBr
mol CsBr
XCsBr =
=
= 7.817 x 103 = 7.82 x 103
+
0.2000
25.38513
mol
mol CsBr + mol H 2 O
(
)
Percent CsBr =
13.73
( 42.56 g CsBr )
mass of CsBr
x 100% = 8.512 = 8.51% CsBr
(100 ) =
mass of solution
( 42.56 + 457.44 ) g
Percent KI =
13.74
( 0.30 g KI )
( 0.30 + 400.) g
The information given is 8.00 mass % NH3 solution with a density of 0.9651 g/mL.
For convenience, choose exactly 100.00 grams of solution.
Determine some fundamental quantities:
8.00% NH 3
Mass of NH3 = (100 g solution )
= 8.00 g NH3
100% solution
Mass H2O = mass of solution mass NH3 = (100.00 8.00) g = 92.00 g H2O
1 mol NH 3
Moles NH3 = ( 8.00 g NH 3 )
= 0.469759 mol NH3 (unrounded)
17.03 g NH 3
1 mol H 2 O
Moles H2O = ( 92.00 g H 2 O )
= 5.1054 mol H2O (unrounded)
18.02 g H 2 O
1 mL solution 10-3 L
Volume solution = (100.00 g solution )
= 0.103616 L (unrounded)
0.9651 g solution 1 mL
13-11
Using the above fundamental quantities and the definitions of the various units:
0.469759 mol NH3 103 g
Moles solute
Molality =
=
= 5.106076 = 5.11 m NH3
kg solvent
92.00 g H 2 O
1 kg
0.469759 mol NH3
Moles solute
=
= 4.53365 = 4.53 M NH3
L solution
0.103616 L
Molarity =
13.75
The information given is 28.8 mass % FeCl3 solution with a density of 1.280 g/mL.
For convenience, choose exactly 100.00 grams of solution.
Determine some fundamental quantities:
Mass of FeCl3 = (100.00 grams solution) (28.8% FeCl3 / 100%) = 28.8 g FeCl3
Mass H2O = mass of solution mass FeCl3 = (100.00 28.8) g = 71.20 g H2O
Moles FeCl3 = (28.80 g FeCl3) (1 mol FeCl3 / 162.20 g FeCl3) = 0.1775586 mol FeCl3 (unrounded)
Moles H2O = (71.20 g H2O) (1 mol H2O / 18.02 g H2O) = 3.951165 mol H2O (unrounded)
Volume solution = (100.00 g solution) (1 mL / 1.280 g) (103 L / 1 mL) = 0.078125 L (unrounded)
Using the above fundamental quantities and the definitions of the various units:
0.1775586 mol FeCl3 103 g
Molality = Moles solute / kg solvent =
= 2.49380 = 2.49 m FeCl3
71.20 g H 2 O
1 kg
0.1775586 mol FeCl3
Molarity = Moles solute / L solution =
= 2.272750 = 2.27 M FeCl3
0.078125 L
Mole fraction = X = moles substance / total moles =
13.76
mass solute
6
ppm =
x 10
mass
solution
1 mL 1.001 g
5
The mass of 100.0 L of waste water solution is (100.0 L solution ) 3
= 1.001 x 10 g.
10 L 1 mL
0.25 g Ca 2+
6
2+
ppm Ca2+ =
x 10 = 2.49750 = 2.5 ppm Ca
5
1.001
x
10
g
solution
0.056 g Mg 2+
6
2+
ppm Mg2+ =
x 10 = 0.5594406 = 0.56 ppm Mg
5
1.001
x
10
g
solution
13.77
The information given is ethylene glycol has a density of 1.114 g/mL and a molar mass of 62.07 g/mol. Water
has a density of 1.00 g/mL. The solution has a density of 1.070 g/mL.
For convenience, choose exactly 1.0000 Liters as the equal volumes mixed. Ethylene glycol will be
designated EG.
Determine some fundamental quantities:
Mass of EG = (1.0000 L EG) (1mL / 103 L) (1.114 g EG/mL) = 1114 g EG
Mass of H2O = (1.0000 L H2O) (1mL / 103 L) (1.00 g H2O/mL) = 1.00 x 103 g H2O
Moles EG = (1114 g EG) (1 mol EG / 62.07 g EG) = 17.94747865 mol EG (unrounded)
Moles H2O = (1.00 x 103 g H2O) (1 mol H2O / 18.02 g H2O) = 55.49389567 mol H2O (unrounded)
Volume solution = (1114 g EG + 1.00 x 103 g H2O) (mL / 1.070 g) (103 L / 1 mL)
= 1.97570 L (unrounded)
Using the above fundamental quantities and the definitions of the various units:
a) Volume percent = (1.0000 L EG / 1.97570 L) 100% = 50.61497 = 50.61% v/v
b) Mass percent = [(1114 g EG) / (1114 + 1.00 x 103) g] 100% = 52.6963 = 52.7% w/w
13-12
17.94747865 mol EC
= 9.08411 = 9.08 M ethylene glycol
1.97570 L
1.00 x 103 g H 2 O 1 kg
17.94747865 mol EG
(17.94747865 + 55.49389567 ) mol
= 0.244378 = 0.244
13.78
Colligative properties of a solution are affected by the number of particles of solute in solution. The density of a
solution would be affected by the chemical formula of the solute.
13.79
A nonvolatile nonelectrolyte is a covalently bonded molecule that does not dissociate into ions or evaporate when
dissolved in a solvent. In this case, the colligative concentration is equal to the molar concentration, simplifying
calculations.
13.80
The strong in strong electrolyte refers to the ability of an electrolyte solution to conduct a large current. This
conductivity occurs because solutes that are strong electrolytes dissociate completely into ions when dissolved in
water.
13.81
Raoults Law states that the vapor pressure of solvent above the solution equals the mole fraction of the solvent
times the vapor pressure of the pure solvent. Raoults Law is not valid for a solution of a volatile solute in
solution. Both solute and solvent would evaporate based upon their respective vapor pressures.
13.82
The boiling point temperature is higher and the freezing point temperature is lower for the solution compared to
the solvent because the addition of a solute lowers the freezing point and raises the boiling point of a liquid.
13.83
Yes, the vapor at the top of the fractionating column is richer in content of the more volatile component.
13.84
The boiling point of a 0.01 m KF solution is higher than that of 0.01 m glucose. KF dissociates into ions in water
(K+ and F) while the glucose does not, so the KF produces more particles.
13.85
A dilute solution of an electrolyte behaves more ideally than a concentrated one. With increasing concentration,
the effective concentration deviates from the molar concentration because of ionic attractions.. Thus, the more
dilute 0.050 m NaF solution has a boiling point closer to its predicted value.
13.86
Univalent ions behave more ideally than divalent ions. Ionic strength (which affects activity concentration) is
greater for divalent ions. Thus, 0.01 m NaBr has a freezing point that is closer to its predicted value.
13.87
Cyclohexane, with a freezing point depression constant of 20.1C/m, would make calculation of molar mass of a
substance easier, since Tf would be greater.
13.88
Strong electrolytes are substances that produce a large number of ions when dissolved in water; strong acids and
bases and soluble salts are strong electrolytes. Weak electrolytes produce few ions when dissolved in water; weak
acids and bases are weak electrolytes. Nonelectrolytes produce no ions when dissolved in water. Molecular
compounds other than acids and bases are nonelectrolytes.
a) Strong electrolyte When hydrogen chloride is bubbled through water, it dissolves and dissociates completely
into H+ (or H3O+) ions and Cl ions. HCl is a strong acid.
b) Strong electrolyte Potassium nitrate is a soluble salt.
c) Nonelectrolyte Glucose solid dissolves in water to form individual C6H12O6 molecules, but these units are not
ionic and therefore do not conduct electricity. Glucose is a molecular compound.
d) Weak electrolyte Ammonia gas dissolves in water, but is a weak base that forms few NH4+ and OH ions.
13-13
13.89
a) NaMnO4
b) CH3COOH
c) CH3OH
d) Ca(C2H3O2)2
13.90
To count solute particles in a solution of an ionic compound, count the number of ions per mole and multiply by
the number of moles in solution. For a covalent compound, the number of particles equals the number of
molecules.
0.3 mol KBr 2 mol particles
a)
1 mol KBr (1 L ) = 0.6 mol of particles
L
+
Each KBr forms one K ion and and one Br ion, 2 particles for each KBr.
0.065 mol HNO3 2 mol particles
b)
1 mol HNO (1 L ) = 0.13 mol of particles
L
3
+
HNO3 is a strong acid that forms H (H3O+) ions and NO3 ions in aqueous solution.
10-4 mol KHSO 4 2 mol particles
4
c)
(1 L ) = 2 x 10 mol of particles
L
1
mol
KHSO
4
Each KHSO4 forms 1 K+ ion and 1 HSO4 ion in aqueous solution, 2 particles for each KHSO4.
strong electrolyte
weak electrolyte
nonelectrolyte
strong electrolyte
2 5
Ethanol is not an ionic compound so each molecule dissolves as one particle. The number of moles of particles is
the same as the number of moles of molecules, 0.06 mol in 1 L.
13.91
a) (0.02 mol CuSO4/L) (2 mol particles/mol CuSO4) (103 L / 1 mL) (1 mL) = 4 x 105 mol of particles
b) (0.004 mol Ba(OH)2/L) (3 mol particles/mol Ba(OH)2) (103 L / 1 mL) (1 mL)
= 1.2 x 105 = 1 x 105 mol of particles
c) (0.08 mol C5H5N/L) (1 mol particles/mol C5H5N) (103 L / 1 mL) (1 mL) = 8 x 105 mol of particles
d) (0.05 mol (NH4)2CO3/L) (3 mol particles/mol (NH4)2CO3) (103 L / 1 mL) (1 mL)
= 1.5 x 104 = 2 x 104 mol of particles
13.92
13-14
13.93
3 8 3
2 6 2
The molality of C2H6O2, in ethanol is 2.45 m whereas the molality of C3H8O3, in ethanol is 1.65 m. Thus,
C2H6O2/ethanol solution has the higher boiling point.
(15 g C2 H6 O2 ) 1 mol C2 H6 O2
b) Molality of C2H6O2 =
= 0.4833253 = 0.48 m C2H6O2
( 0.50 kg H 2 O ) 62.07 g C2 H 6 O2
(15 g NaCl )
1 mol NaCl
= 0.513347 = 0.51 m NaCl
( 0.50 kg H 2 O ) 58.44 g NaCl
Since the NaCl is a strong electrolyte, the molality of particles would be:
(2 particles/NaCl) (0.513347 mol NaCl/kg) = 1.026694 = 1.0 m particles
The molality of C2H6O2 in H2O is 0.48 m, whereas NaCl in H2O is 1.0 m. Therefore, NaCl/H2O solution has the
higher boiling point.
Molality of NaCl =
13.94
To rank the solutions in order of increasing osmotic pressure, boiling point, freezing point, and vapor pressure,
convert the molality of each solute to molality of particles in the solution. The higher the molality of particles, the
higher the osmotic pressure, the higher the boiling point, the lower the freezing point, and the lower the vapor
pressure at a given temperature.
2 mol particles
(I) ( 0.100 m NaNO3 )
= 0.200 m ions
1 mol NaNO3
NaNO3 consists of Na+ ions and NO3 ions, 2 particles for each NaNO3.
1 mol particles
(II) ( 0.100 m glucose )
= 0.100 m molecules
1 mol glucose
Ethanol is not an ionic compound so each molecule dissolves as one particle. The number of moles of
particles is the same as the number of moles of molecules.
3 mol particles
(III) ( 0.100 m CaCl2 )
= 0.300 m ions
1 mol CaCl2
CaCl2 consists of Ca+2 ions and Cl ions, 3 particles for each CaCl2.
a) Osmotic pressure:
II < I < III
b) Boiling point:
bpII < bpI < bpIII
c) Freezing point:
fpIII < fpI < fpII
d) Vapor pressure at 50C:
vpIII < vpI < vpII
13.95
13-15
13.96
The mol fraction of solvent affects the vapor pressure according to the equation: Psolvent = XsolventPsolvent
1 mol C3 H8 O3
Moles C3H8O3 = ( 34.0 g C3 H8 O3 )
= 0.369204 mol C3H8O3 (unrounded)
92.09 g C3 H8 O3
1 mol H 2 O
Moles H2O = ( 500.0 g H 2 O )
= 27.7469 mol H2O (unrounded)
18.02 g H 2 O
mol H 2 O
27.7469 mol H 2 O
Xsolvent =
=
= 0.9868686
mol H 2 O + mol glycerol
27.7469 mol H 2 O + 0.369204 mol glycerol
Psolvent = XsolventPsolvent = (0.9868686) (23.76 torr) = 23.447998 = 23.4 torr
13.97
The mole fraction of solvent affects the vapor pressure according to the equation: Psolvent = XsolventPsolvent
Xsolvent = (5.4 mol toluene) / [(0.39) + (5.4)] mol = 0.93264 (unrounded)
Psolvent = XsolventPsolvent = (0.93264) (41torr) = 38.2382 = 38 torr
13.98
13.99
The change in freezing point is calculated from Tf = iKfm, where Kf is 1.86C/m for aqueous solutions, i is
the vant Hoff factor, and m is the molality of particles in solution. Since urea is a covalent compound and
does not ionize in water, i = 1. Once Tf is calculated, the freezing point is determined by subtracting it from
the freezing point of pure water (0.00C).
Tf = iKf m = (1) (1.86C/m) (0.251 m) = 0.46686C (unrounded)
The freezing point is 0.00C 0.46686C = 0.46686 = 0.467C.
13.100 The boiling point of a solution is increased relative to the pure solvent by the relationship Tb = iKbm. Vanillin is
a nonelectrolyte so i = 1. The molality must be calculated, and Kb is given (1.22C/m).
1 mol Vanillin
( 6.4 g Vanillin )
Molality of Vanillin =
=
kg of solvent (ethanol)
( 50.0 g Ethanol )
1 kg
= 0.841330354 m Vanillin (unrounded)
Tb = iKb m = (1) (1.22C/m) (0.841330354 m) = 1.02642C (unrounded)
The boiling point is 78.5C + 1.02642C = 79.52642 = 79.5C.
13.101 Moles C10H8 = (5.00 g C10H8) (1 mol C10H8 / 128.16 g C10H8) = 0.0390137 mol C10H8 (unrounded)
C10H8 is a nonelectrolyte so i = 1
Mass = (444 g benzene) (1 kg / 103 g) = 0.444 kg benzene
Molality = (0.0390137 mol C10H8) / (0.444 kg) = 0.08786869 m (unrounded)
Tf = i Kf m = (1) (4.90C/m) (0.08786869 m) = 0.43056C (unrounded)
Freezing point = (5.5 0.43056)C = 5.06944 = 5.1C
13.102 The molality of the solution can be determined from the relationship Tf = iKfm with the value 1.86C/m inserted
for Kf and i = 1 for the nonelectrolyte ethylene glycol (ethylene glycol is a covalent compound that will form one
particle per molecule when dissolved). Convert the freezing point of the solution to oC and find Tf:
.
C = (5/9) (F 32.0) = (5/9) ((12.0)F 32.0) = 24.44444C (unrounded)
Tf = (0.00 (24.44444))C = 24.44444C
Tf
24.44444o C
m=
=
= 13.14217 m (unrounded)
Kf
1.86 o C/m
Ethylene glycol will be abbreviated as EG.
13-16
Multiply the molality by the given mass of solvent to find the mass of ethylene glycol that must be in solution.
13.14217 mol EG
62.07 g EG
Mass ethylene glycol =
(14.5 kg H 2 O )
1 kg H 2 O
1 mol EG
1 kg H 2 O
1 mg 10 g 1 mol GLY
= 0.0081693 = 0.0082 g glycerol
To prevent the solution from freezing, dissolve a minimum of 0.0082 g glycerol in 11.0 mg water.
13.104 Convert the mass percent to molality and use T = iKbm to find the vant Hoff factor.
a) Assume exactly 100 grams of solution.
1.00% NaCl
Mass NaCl = (100 g solution )
= 1.00g NaCl
100% solution
1 mol NaCl
Moles NaCl = (1.00 g NaCl )
= 0.0171116 mol NaCl
58.44 g NaCl
Mass H2O = 100.00 g solution 1.00g NaCl = 99.00 g H2O
0.0171116 mol NaCl 103 g
mole NaCl
=
Molality NaCl =
i=
Tf
0.593 C
=
= 1.844537 = 1.84
Kf m
1.86o C/m ( 0.172844 m )
The value of i should be close to 2 because NaCl dissociates into 2 particles when dissolving in water.
b) For acetic acid, CH3COOH:
Assume exactly 100 grams of solution.
0.500% CH3 COOH
Mass CH3COOH = (100 g solution )
= 0.500 g CH3COOH
100% solution
1 mol CH3COOH
Moles CH3COOH = ( 0.500 g CH3COOH )
= 0.0083264 mol CH3COOH
60.05 g CH3COOH
Mass H2O = 100.00 g solution 0.500 g CH3COOH = 99.500 g H2O
Molality CH3COOH =
99.500 g H 2 O
kg H 2 O
1 kg
i=
Tf
0.159 C
=
= 1.02153 = 1.02
Kf m
1.86o C/m ( 0.083682 m )
Acetic acid is a weak acid and dissociates to a small extent in solution, hence a vant Hoff factor that is close to 1.
13-17
13.105 Convert the mass % to molality and use T = iKbm to find the vant Hoff factor.
a) Assume exactly 100 grams of solution. Thus, the solution contains 0.500 grams of KCl in 99.500 grams of
water.
0.500 g KCl 103 g 1 mol KCl
Molality KCl =
= 0.067406 m KCl (unrounded)
99.500 g H 2 O 1 kg 74.55 g KCl
Calculate T = (0.000 (0.234))C = 0.234C
Tf = i Kf m
i = Tf / Kf m = (0.234C) / [(1.86C/m) (0.067406 m)] = 1.866398 = 1.87
The value of i should be close to 2 because KCl dissociates into 2 particles when dissolving in water.
b) For sulfuric acid, H2SO4:
Assume exactly 100 grams of solution. Thus, the solution contains 1.00 grams of H2SO4 in 99.00 grams of water.
1.00 g H 2SO 4 103 g 1 mol H 2SO 4
Molality H2SO4 =
= 0.10297696 m H2SO4 (unrounded)
99.00 g H 2 O 1 kg 98.09 g H 2SO 4
Calculate T = (0.000 (0.423))C = 0.423C
Tf = i Kf m
i = Tf / Kf m = (0.423C) / [(1.86C/m) (0.10297696 m)] = 2.2084 = 2.21
Sulfuric acid is a strong acid and dissociates to give a hydrogen ion and a hydrogen sulfate ion. The hydrogen
sulfate ion may further dissociate to another hydrogen ion and a sulfate ion. If ionization in both steps were
complete, the value of the vant Hoff factor would be 3.
13.106 Osmotic pressure is calculated from the molarity of particles, gas constant and temperature. Convert the mass of
sucrose to moles using the molar mass, and then to molarity. Sucrose is a nonelectrolyte so i = 1.
T = (273 + 20.)K = 293 K
1 mol sucrose
( 3.55 g sucrose )
moles of sucrose
342.30 g sucrose = 1.0371 x 102 M sucrose
Molarity =
=
1.0 L
volume of solution
= i MRT = (1) (1.0371 x 102 mol/L) (0.0821 Latm/molK) (293 K) = 0.2494778 = 0.249 atm
A pressure greater than 0.249 atm must be applied to obtain pure water from a 3.55 g/L solution.
13.107 Use the osmotic pressure equation ( = i MRT) to find the molarity of the solution (assuming i = 1).
0.272 atm
M = / i RT =
= 0.01111756 M (unrounded)
Liatm
(1) 0.0821
( ( 273 + 25) K )
moliK
Moles = (0.01111756 mol/L) (100.0 mL) (103 L / 1 mL) = 0.001111756 mol (unrounded)
Molar mass = (6.053 g) / (0.001111756 mol) = 5.4445 x 103 = 5.44 x 103 g/mol
13.108 The pressure of each compound is proportional to its mole fraction according to Raoults law: PA = XA PA
moles CH 2 Cl2
1.60 mol
= 0.592593
X CH Cl =
=
1.60 + 1.10 mol
moles CH 2 Cl2 + mol CCl4
2
moles CCl4
1.10 mol
= 0.407407
=
moles CH 2 Cl2 + mol CCl4 1.60 + 1.10 mol
PA = XA PA
= (0.592593) (352 torr) = 208.593 = 209 torr CH2Cl2
= (0.407407) (118 torr) = 48.0740 = 48.1 torr CCl4
X CCl =
4
13.109 The fluid inside a bacterial cell is both a solution and a colloid. It is a solution of ions and small molecules and a
colloid of large molecules, proteins, and nucleic acids.
13-18
1 sphere
1 mL = 3.2 M
-3
25 mL
10 L
(8 spheres )
Solution A: M =
1 sphere
1 mL = 2.0 M
-3
50 mL
10 L
(10 spheres )
Solution B: M =
1 sphere
1 mL = 1.2 M
-3
100 mL
10 L
(12 spheres )
Solution C: M =
b) Molarity of compound:
1 sphere
2 moles of ions 1 mL = 1.6 M
-3
25 mL
10 L
(8 spheres )
Solution A: M =
1 sphere
(10 spheres )
Solution B: M =
1 sphere
3
1 sphere
25 mL
1.0 g 1 kg
(12 spheres )
3
1 sphere
50 mL
1.0 g 1 kg
(10 spheres )
Solution B: m =
13-19
3
1 sphere
100 mL
1.0 g 1 kg
Solution C has the lowest molality.
d) Osmotic pressure: assume a temperature of 298 K
Solution A: = i MRT = (2) (1.6 mol/L) (0.0821 Latm/molK) (298 K) = 78.29056 = 78 atm
Solution B: = i MRT = (2) (1.0 mol/L) (0.0821 Latm/molK) (298 K) = 48.9316 = 49 atm
Solution C: = i MRT = (3) (0.40 mol/L) (0.0821 Latm/molK) (298 K) = 29.35896 = 29 atm
Solution A has the highest osmotic pressure.
(12 spheres )
31.1 g Au
x 109
mass seawater
31.1 g
100%
12
Mass of seawater = 2.827273 x 1012 g
= 3.46905 x 10 g seawater (unrounded) (81.5% efficiency)
81.5%
1 mL 10-3 L
9
9
Volume seawater = 3.46905 x 1012 g
= 3.384439 x 10 = 3.4 x 10 L
1.025
g
1
mL
13-20
13.118 Xe is a much larger atom than He, so it is much more polarizible. This would increase the dipole-induced dipole
forces when Xe is placed in water, increasing the solubility relative to He.
13.119 C. The principal factor in the solubility of ionic compounds in water is ion-dipole forces. Virtually all of the ionic
compounds ions would become separated and surrounded by water molecules (the number depending on the
sizes of the ions) interacting with the ions via H-bonding or other forces.
13.120 a) Solution A has a vant Hoff factor of 3, Solutions B and C have a vant Hoff factor of 2 and Solution Ds vant
Hoff factor is 1. Since Solution A has the largest vant Hoff factor, Solution A would have the highest boiling
point.
b) Solution A also has the lowest freezing point since it has the largest vant Hoff factor.
c) No, the solution with the highest osmotic pressure cannot be determined. Osmotic pressure is determined by
the molarity, not the molality, of the solution. Since we do not know the identity of the solutes and the density of
the solutions, the 0.50 m value cannot be converted to molarity.
13.121 Convert mass of O2 dissolved to moles of O2. Use the density to convert the 1 kg mass of solution to
volume in L.
0.0C
14.5 mg O 2 103 g 1 mol O 2 1 kg 0.99987 g 1 mL
3
3
mL
10 L
1 kg H 2 O 1 mg 32.00 g O 2 10 g
4
4
= 4.53066 x 10 = 4.53 x 10 M O2
20.0C
9.07 mg O 2 103 g 1 mol O 2 1 kg 0.99823 g 1 mL
3
3
mL
10 L
1 kg H 2 O 1 mg 32.00 g O 2 10 g
4
4
= 2.829358 x 10 = 2.83 x 10 M O2
40.0C
6.44 mgO 2 103 g 1 mol O 2 1 kg 0.99224 g 1 mL
3
3
mL
10 L
1 kg H 2 O 1 mg 32.00 g O 2 10 g
4
4
= 1.996883 x 10 = 2.00 x 10 M O2
13.122 Pyridine has non-polar aromatic qualities like organic solvents but also has the potential to associate with water by
hydrogen bonding through its lone pair of electrons (localized on the nitrogen atom).
13.123 a) First, find the molality from the freezing point depression and then use the molality, given mass of solute and
volume of water to calculate the molar mass of the solute compound. Assume the solute is a nonelectrolyte (i = 1).
Tf = iKf m = (0.000 (0.201) ) = 0.201C
o
m=
Tf
0.201 C
=
= 0.1080645 m (unrounded)
Kf i
1.86o C/m (1)
m=
moles solute
kg solvent
1.00 g 1 kg
3 = 0.0250 kg water
1 mL 10 g
( 25.0 mL )
13-21
b) Assume that 100.00 g of the compound gives 53.31 g carbon, 11.18 g hydrogen and 100.00 53.31 11.18 =
35.51 g oxygen.
1 mol C
4.43880
=2
Moles C = ( 53.31 g C )
= 4.43880 mol C (unrounded) ;
2.219375
12.01 g C
1 mol H
Moles H = (11.18 g H )
= 11.09127 mol H (unrounded);
1.008 g H
11.09127
=5
2.219375
1 mol O
2.219375
=1
Moles O = ( 35.51 g O )
= 2.219375 mol O (unrounded);
16.00
g
O
2.219375
Dividing the values by the lowest amount of moles (2.219375) gives an empirical formula of C2H5O with molar
mass 45.06 g/mol.
Since the molar mass of the compound , 89.9 g/mol from part (a), is twice the molar mass of the empirical
formula, the molecular formula is 2(C2H5O) or C4H10O2.
c) There is more than one example in each case. Possible Lewis structures:
Forms hydrogen bonds
Does not form hydrogen bonds
H
H
H
H
H
H
H
H
HO
OH
C
H
C
H
13.124 Mass CO = (4.0 x 10 6 mol/L) (11 L/min) (60 min/1 h) (8.0 h) (28.01 g CO/mol) = 0.59157 = 0.59 g CO
13.125 No, both are the same because masses are additive.
moles of N 2
total moles
3 moles N 2
= 0.38
Mixture A: X N2 =
3 + 2 + 3 moles
13.126 a) X N 2 =
Mixture B: X N2 =
4 moles N 2
= 0.33
4 + 3 + 5 moles
Mixture C has the smallest mole fraction of N2.
2 moles Ne
= 0.25
b) Mixture A: X Ne =
3 + 2 + 3 moles
3 moles Ne
Mixture C: X Ne =
= 0.25
4 + 3 + 5 moles
Mixtures A and C have the same mole fraction of Ne.
3 moles Cl2
= 0.38
c) Mixture A: X Cl2 =
3 + 2 + 3 moles
5 moles Cl2
Mixture C: X Cl2 =
= 0.42
4 + 3 + 5 moles
Mixture B < Mixture A < Mixture C
4 moles N 2
= 0.40
4 + 4 + 2 moles
Mixture C: X N2 =
3.127
Mixture B: X Ne =
Mixture B: X Cl2 =
19.00 g F
( 2.0 L )
1 mol F
= 0.0017 g F
13-22
4 moles Ne
= 0.40
4 + 4 + 2 moles
2 moles Cl2
= 0.20
4 + 4 + 2 moles
13.128 a) To shorten the settling time, lime (CaO) and cake alum (Al2(SO4)3) are added to form a fluffy, gel-like
precipitate of Al(OH)3.
b) Water that contains large amounts of divalent cations (such as Ca2+, Mg2+, and Fe2+) is called hard water.
During cleaning, these ions combine with the fatty-acid anions in soaps to produce insoluble deposits.
c) In reverse osmosis, a higher pressure is applied to the solution, forcing the water back through the membrane
and leaving the ions behind.
d) Chlorine may give the water an unpleasant odor, and can form toxic chlorinated hydrocarbons.
e) The high concentration of NaCl displaces the divalent and polyvalent ions from the ion-exchange resin.
13.129 a) The solution in U-tube B is the most concentrated since it has the highest osmotic pressure.
b) Solution C has the smallest number of dissolved ions and thus the smallest osmotic pressure.
13.130 Calculate the individual partial pressures from P = X P. Assign the equal masses as exactly 1 g.
Liquid:
1 g pinene
136.23
g
pinene/mol
= 0.53100 (unrounded)
X (pinene) =
1 g pinene
1 g terpineol
1 g terpineol
154.24 g terpineol/mol
= 0.4689985 (unrounded)
X (terpineol) =
1 g pinene
1 g terpineol
4.5961855 torr
= 0.0794425 = 0.079
( 53.2593 + 4.5961855) torr
13.131 a) Use the boiling point elevation of 0.45C to calculate the molality of the solution. Then, with molality, the
mass of solute, and volume of water calculate the molar mass.
T = iKbm
i = 1 (nonelectrolyte)
T = (100.45 100.00)C = 0.45oC
o
m=
Tb
0.45 C
=
= 0.878906 m = 0.878906 mol/kg (unrounded)
K bi
0.512o C/m (1)
m=
moles solute
kg solvent
0.997 g 1 kg
3 = 0.0249250 kg water
1 mL 10 g
( 25.0 mL )
13-23
d) Use the molar mass of CaN2O6 to calculate the molality of the compound. Then calculate i in the boiling point
elevation formula.
25.0 mL
mol C2 H5 OH ( g )
=
mol CH3OH ( g )
mol CH3OH ( l )
mol CH3OH ( l ) 126.0 torr
A 97:1 mass ratio gives 97 grams of C2H5OH for every 1 gram of CH3OH. (This limits the significant figures.)
1 mol C2 H5 OH
97 g C2 H5 OH ( g )
32.04 g CH3OH
mol C2 H5 OH ( l )
( 2.10549/0.03121)
=
= 140.4994
mol CH3OH ( l )
0.4801587
46.07 g C2 H5 OH
1 mol C2 H5 OH
32.04 g CH3OH
(1 mol CH3OH )
1 mol CH3OH
= 202.0227 = 2 x 102
13.133 Convert from ppb to pph (part per hundred = mass percent)
100. ppb 100 pph
5
= 1.00 x 10 %
9
1
10
Determine the molarity of CH3Cl in 1.00 L corresponding to 100. ppb. (Assume the density of the solution is the
same as for pure water, 1.00 g/mL.)
100. g CH3Cl 1 mol CH3Cl 1.00 g Solution 1 mL
9
3
mL
10 L
10 g Solution 50.48 g CH3Cl
= 1.98098 x 106 = 1.98 x 106 M CH3Cl
If the density is 1.00 g/mL then 1.00 L of solution would weigh 1.00 kg. The mass of CH3Cl is insignificant
compared to 1.00 kg, thus the mass of the solution may be taken as the mass of the solvent. This makes the
molarity equal to the molality, in other words: 1.98 x 106 m CH3Cl
Still using 1.00 L of solution:
Moles CH3Cl = (1.98098 x 106 mol/L) (1.00 L) = 1.98098 x 106 mol CH3Cl (unrounded)
Moles H2O = (1.00 kg) (103 g/1 kg) (1 mol H2O / 18.02 g H2O) = 55.49389567 mol H2O (unrounded)
Xchloroform = (1.98098 x 106 mol CH3Cl) / [(1.98098 x 106 + 55.49389567) mol]
= 3.569726 x 108 = 3.57 x 108
13.134 a) Yes, equilibrium is a dynamic process. Solid Na2CO3 and solid Na214CO3 both dissolve in the equilibrium
process.
Na214CO3(s) + H2O(l) Na214CO3(aq)
b) Radioactivity would be found in all of the solid as some of the Na14 that dissolves will also precipitate back
out of solution.
Na214CO3(aq) + H2O(l) Na214CO3(s)
13-24
13.135 a) From the osmotic pressure, the molarity of the solution can be found. The ratio of mass per volume to moles
per volume gives the molar mass of the compound.
= MRT
1 atm
( 0.340 torr )
5
M=
=
= 1.828546 x 10 M (unrounded)
Liatm
760
torr
RT
(M)(V) = moles
103 L
7
Moles = 1.828546 x 10-5 M ( 30.0 mL )
= 5.48564 x 10 mol
1
mL
103 g
1 mg
(10.0 mg )
103 g 1 kg
0.997 g
10.0
mg
Mass solvent = ( 30.0 mL )
(
)
3 = 0.0299 kg
1 mL
1 mg 10 g
Molar mass =
L
1
mL
Molality =
13.136 Henrys law expresses the relationship between gas pressure and the gas solubility (Sgas) in a given solvent. Use
Henrys law to solve for pressure (assume that the constant (kH) is given at 21C), use the ideal gas law to find
moles per unit volume, and convert moles/L to ng/L.
Sgas = kHPgas
0.65 mg/L 103 g 1 mol C2 H 2 Cl2
Pgas = Sgas / kH =
0.033 mol/Liatm 1 mg 96.94 g C2 H 2 Cl2
= 2.3446799 x 10-4 atm (unrounded)
PV = nRT
n / V = P / RT =
( 2.3446799 x 10
atm
Liatm
96.94 g C2 H 2 Cl2
1 mol C2 H 2 Cl2
1 ng
5
5
9 = 9.41578 x10 = 9.4 x 10 ng/L
10
g
23
2.50 mg
10 g mol 6.022 x 10 molecules
= 2.19973 x 1016 = 2.20 x 1016 cm2/molecule
13-25
13.138 a) Looking at the data for CaCl2, K2CO3, and Na2SO4, the average conductivity is 7.0 0.7 units for the
5.00 x 103 ppm solutions and 14 1.7 units for the 10.00 x 103 ppm solutions. This represents a relative error of
about 10% if you assume that the identity of the solute is immaterial. If your application can tolerate an error of
this magnitude, then this method would be acceptable.
b) This would be an unreliable estimate of the concentration for those substances which are non-electrolytes, or
weak electrolytes, as their conductivity would be much reduced in comparison to their true concentration.
c) Concentration (ppm) = (14.0 / 16.0) (10.00 x 103 ppm) = 8.75 x 103 ppm
Assume the mass of CaCl2 present is negligible relative to the mass of the solution.
8.75 x 103 g CaCl2 1 mol CaCl2 103 g
Molality CaCl2 =
= 0.0788430 = 0.0788 m CaCl2
6
13.139 The vapor pressure of H2O above the pure water is greater than that above the sugar solution. This means that
water molecules will leave the pure water and enter the sugar solution in order to make their vapor pressures closer to
equal.
13.140 a) Assume a concentration of 1 mol/m3 for both ethanol and 2-butoxyethanol in the detergent solution. Then,
from Henrys Law, the partial pressures of the two substances can be calculated:
Sgas = kH Pgas
Pgas = Sgas/ kH
-6
3
1 mol 5 x 10 atmim
6
Pethanol = 3
= 5 x 10 atm
mol
m
-6
3
1 mol 1.6 x 10 atmim
P2-butoxyethanol = 3
mol
m
6
= 1.6 x 10 atm
mol
10 m
0.64 Pa im3
1 atm
6
3
c) kHethanol =
= 6.3 x 10 atmm /mol
5
mol
1.01325
x
10
Pa
Considering the single significant figure in the measured value of 5 x 106, the agreement is good.
13.141 The fraction remaining in the water (fw) is related to the volume of water (Vw), the volume of dichloromethane
(Vd), and the distribution ratio for the solubility (D = 8.35 / 1).
fw = Vw / (Vw + DVd)
Mass remaining in water = fw (original mass)
(100.0 mL )
a) Mass in water =
(10.0 mg ) = 1.66389 = 1.66 mg remaining
(100.0 + 8.35 ( 60.0 ) ) mL
13-26
b) Perform a similar calculation to part (a), then take the result and repeat the procedure. Combine the results to
get the total removed.
(100.0 mL )
Mass in water =
(10.0 mg ) = 2.853067 mg remaining after first extraction
(100.0 + 8.35 ( 30.0 ) ) mL
Mass in water =
(100.0 mL )
( 2.853067 mg )
(100.0 + 8.35 ( 30.0 ) ) mL
12.6015 g NaHCO3
13.143 To determine the molecular formula, both the empirical formula and the molar mass are needed. First, determine
the empirical formula assuming exactly 100 grams of sample, which makes the percentages equal to the mass of
each element present:
Moles C = 32.3 g C (1 mol C / 12.01 g C) = 2.6894 mol C (unrounded)
Moles H = 3.97 g H (1 mol H / 1.008 g H) = 3.93849 mol H (unrounded)
Moles O = (100 32.3 3.97) g O (1 mol O / 16.00 g O) = 3.9831 mol O (unrounded)
Dividing each mole value by the smallest value (moles C) gives: C = 1, H = 1.5, and O = 1.5 leading to an
empirical formula of: C2H3O3.
The molar mass comes from the freezing point depression:
Tf = iKfm
(Assume the compound is a nonelectrolyte, i = 1.)
m = Tf / iKf = (1.26C) / [(1) (1.86C/m)] = 0.677419 m (unrounded)
kg Solvent 103 g
0.981 g
Molar mass =
= 128.953 g/mol (unrounded)
0.677419 mol 1 kg 11.23 g Solvent
The empirical formula mass is approximately 75 g/mol.
The ratio of the molar to the empirical formula mass normally gives the conversion factor to change the empirical
formula to the molecular formula. In this case, 129 / 75 = 1.72; this is not near a whole number. (This result is
low due to dissociation of the weak acid; the assumption of i = 1 is too low. If i = 1.2, then the molar mass would
increase to about 154 g/mol.) The 1.72 value implies the molecular formula is twice the empirical formula, or
C4H6O6.
13.144 The range has to fall between the point where the number of moles of methanol is just greater than the number of
moles of ethanol, to the point where the mass of methanol is just less than the mass of ethanol.
The first point is the point at which the mole fractions are just becoming unequal. The methanol mole fraction is
greater than 0.5000.
Point 2: where the mass percents are just beginning to become unequal.
First, find where they are equal.
(1.000 g methanol / 2.000 g solution) = (1.000 g ethanol / 2.000 g solution)
Moles methanol = (1.000 g ethanol) (1 mol ethanol / 32.04 g ethanol) = 0.031210986 mol methanol (unrounded)
Moles ethanol = (1.000 g ethanol) (1 mol ethanol / 46.07 g ethanol) = 0.021706 mol ethanol (unrounded)
13-27
5.0 g
2
Molar mass =
= 251.5 = 2.5 x 10 g/mol
0.198807
mol
1
kg
100.0
g
Solvent
b) The molar mass, based on the formula, is 122.12 g/mol. The molar mass determined in part (a) is double the
actual molar mass. This is because the acid dimerizes (forms pairs) in the solution. These pairs are held together
by relatively strong hydrogen bonds, and give a molecule that is double the mass of a normal molecule.
13.146 Molarity is moles solute/L solution and molality is moles solute/kg solvent.
Multiplying molality by concentration of solvent in kg solvent per liter of solution gives molarity:
mol of solute mol of solute kg solvent
=
L of solution
kg solvent L of solution
kg solvent
M = m
L of solution
For a very dilute solution, the assumption that mass of solvent mass of solution is valid. This equation then
becomes
M = m (kg solvent/L solution) = m x dsolution
Thus, for very dilute solutions molality x density = molarity.
In an aqueous solution, the liters of solution have approximately the same value as the kg of solvent because the
density of water is close to 1 kg/L, so m = M.
1 mol NH 4 NO3
13.147 Moles = ( 5.66 g NH 4 NO3 )
80.05 g NH 4 NO3
1 mol NH 4 +
= 7.07058 x 102 mol NH4+ (unrounded)
1
mol
NH
NO
4
3
149.10 g (NH 4 )3 PO 4 1 mol (NH 4 )3 PO 4
= 8.89336 x 102 mol NH4+ (unrounded)
149.10 g (NH 4 )3 PO 4 1 mol (NH 4 )3 PO 4
M
M
x 103 M NH4+
13.148 a) M SO2 = P kH = (2.0 x 103 atm) (1.23 mol/Latm) = 2.46 x 103 = 2.5 x 103 M SO2
b) The base reacts with the sulfur dioxide to produce calcium sulfite. The reaction of sulfur dioxide makes room
for more sulfur dioxide to dissolve.
13-28
13.149 a) Assume a 100 g sample of urea. This leads to the mass of each element being equal to the percent of that
element.
1 mol C
Moles C = ( 20.1 g C )
= 1.6736 mol C (unrounded)
12.01 g C
1 mol H
Moles H = ( 6.7 g H )
= 6.6468 mol H (unrounded)
1.008 g H
1 mol N
Moles N = ( 46.5 g N )
= 3.31906 mol N (unrounded)
14.01 g N
1 mol O
Moles O = ( (100 - 20.1 - 6.7 - 46.5) g O )
= 1.66875 mol O (unrounded)
16.00 g O
Dividing all by the smallest value (1.66875 mol O) gives: C = 1, H = 4, N = 2, O = 1. Thus, the empirical
formula is CH4N2O. The empirical formula weight is 60.06 g/mol.
b) Use = MRT to solve for the molarity of the urea solution. The solution molarity is related to the
concentration expressed in % w/v by using the molar mass.
( 2.04 atm )
M = / RT =
= 0.0833817 M (unrounded)
L atm
0.0821
273
+
25
K
(
)
(
)
mol K
5.0 g
L
Because the molecular weight equals the empirical weight, the molecular formula is also CH4N2O.
3
100. mL 10 L 0.30 mol Glucose 180.16 g Glucose
13.150 a) Mass glucose = ( 2.5 h )
1 mL
h
1L
1 mol Glucose
= 13.512 = 14 g glucose
b) At low concentrations sodium chloride dissociates completely, forming twice as many dissolved particles per
mole as glucose, so a sodium chloride solution would have to have a molarity that is one-half of glucose to be
isotonic: 0.15 M
3
150. mL 10 L 0.15 mol NaCl 58.44 g NaCl
c) Mass NaCl = (1.5 h )
h
1L
1 mL
1 mol NaCl
= 1.97235 = 2.0 g NaCl
13.151 a) There is a positive deviation since benzene molecules are held together only by weak dispersion forces
while methanol molecules are held together by relatively strong hydrogen bonding. The two components
will not interact with each other since the intermolecular forces are so different.
b) There is a positive deviation since ethyl acetate will have weaker hydrogen bonding to water than water
has with itself.
c) Since hexane and heptane are very similar compounds with weak dispersion forces, they will obey Raoults
Law. The behavior will be nearly ideal.
d) The behavior will be nearly ideal since the hydrogen bonding in methanol and water is very similar.
e) There is a negative deviation because HCl exists as ions in solution and water is in the hydration shells around
the H3O+ and Cl ions.
13-29
1 mol O 2
mass of solute
0.00128 g
1 x 106 =
pm =
1 x 106 = 1.2165 = 1 ppm
mass of solution
0.00128 g + 1052.176 g
13-30
13.154 The lower the boiling point the greater the volatility. acetic acid < water < benzene < ethanol
< carbon tetrachloride < chloroform < carbon disulfide < diethyl ether
13.155 Use the equation:
H vap 1
P
1
ln 2 =
R T2 T1
P1
T1 = (273 + 100) K = 373 K
P1 = 1.00 atm
P2 = ?
T2 = (273 + 200.)K = 473 K
Hvap = 40.7 kJ/mol
P2
40.7 kJ/mol 1
1 103 J
=
ln
J 473 K 373 K 1 kJ
1.00 atm
8.314
moliK
P2
= 2.774689665 (unrounded)
ln
1.00 atm
P2
= 16.03365
1.00 atm
P2 = 16.03365 = 16.0 atm
mol CaCl2
13.157 a) Find the molarity of C6H14 so that the molarity of O2 can be found from its mole fraction. Then Henrys
Law can be used to find kH.
1 mL 1.674 g C6 F14 1 mol C6 F14
Molarity of C6H14 = (1 L ) 3
338 g C F = 4.9527 mol/L
1 mL
10 L
6 14
X O2 =
mol of O 2
mol of O 2 + mol of C6 F14
x mol O 2
4.9527 mol
Moles of O2 = 0.021198 (The moles of O2 is small enough to ignore in the denominator.)
Sgas = kH Pgas
kH = Sgas/ Pgas
kH = 0.021198 mol/L(101,325 Pa)(101,325 Pa/1 atm) = 0.021198 = 0.0212 mol/Latm
1
b) Sgas = kH Pgas
kH =
= 1.322 x 103 mol/Latm
756.7 Liatm/mol
PO2 = 0.2095 x 1 atm = 0.2095 atm since O2 is 20.95% of air
4.28 x 103 =
O
L
1
mol
2
13-31
1 kg
m 1 Pa
1 atm
1.00 g 1 mL 1 cm 2.54 cm 12 in
Pwater =
( 50.0 ft ) 3 9.80665 2
3
2
5
2
s 1kg/mis 1.013 x 10 Pa
mL 1 cm 10 m 1 in 1 ft
10 g
= 1.47535 atm (unrounded)
This is the pressure due to the 50. ft of water, and it must be added to the atmospheric pressure pressing
down on the surface of the water (1.00 atm). This gives an unrounded total pressure of 2.47535 atm.
Molarity of N2 = (2.47535 atm) (78% N2 / 100%) (7.0 x 104 mol/Latm)
= 1.35154 x 103 = 1.4 x 103 M N2
c) Moles of N2 per liter at the surface = 5.56 x 104 mol N2.
Moles of N2 per liter at 50. ft = 1.35154 x 103 mol N2.
Moles N2 released per liter = (1.35154 x 103 5.56 x 104) mol = 7.9554 x 104 mol (unrounded)
Liatm
PV = nRT so V = nRT / P =
3
(1.00 atm )
10 L
= 19.4635 = 19 mL N2
13.159 a) Yes, the phases of water can still coexist at some temperature and can therefore establish equilibrium.
b) The triple point would occur at a lower pressure and lower temperature because the dissolved air solute
lowers the vapor pressure of the solvent.
c) Yes, this is possible because the gas-solid phase boundary exists below the new triple point.
d) No, the presence of the solute lowers the vapor pressure of the liquid.
13.160 a) Assuming 100 g of water, the solubilities (in g) of the indicated salts at the indicated temperatures would be:
KNO3 KClO3 KCl
NaCl
50C
85
18
42
36
0C
12
4
28
35
Difference
73
14
14
1
% recovery
86
78
33
3
(The difference is the number of grams of the salt, which could be recovered if a solution containing the amount
of salt in the first line were cooled to 0C. The % recovery is calculated by dividing the difference by the
original amount, then multiplying by 100.)
The highest percent recovery would be found for KNO3 (86%), and the lowest would be for NaCl (3%).
b) If you began with 100. g of the salts given above, then the % recovery line above gives the number of grams
which could be recovered by the process described.
28 mL 40% 0.789 g 22% 103 L
4
4
13.161 a) Concentration =
28 mL
b)
8.0 x 10-4 g/mL = 80.6545 = 81 mL
2.77728 x 104 g/mL
13-32
b) If it is completely flat there is no CO2 remaining or 0.00 moles CO2, however a small amount will remain in
solution:
103 L 3.3 x 102 mol
4
6
6
Moles CO2 = ( 355 mL )
3 x 10 atm = 3.5145 x 10 = 4 x 10 mol CO2
1 mL
i
L
atm
c) The difference in the moles will determine the number of moles entering the gas phase.
0.04686 3.5145 x 106 mol 0.0821 Liatm ( ( 273 + 25 ) K )
moliK
PV = nRT so V = nRT / P =
(1.00 atm )
= 1.14638 = 1 L CO2
13.163 a) Scene C represents the system at the higher temperature of 298 K. At the higher temperature, the solubility
of oxygen decreases so more oxygen leaves the solution to go into the vapor phase.
b) Scene B represents the system when the pressure of oxygen is increased by half. The increase in pressure
would result in 4 + (4) = 6 moles of oxygen in the vapor phase. The increased pressure results in increased
solubility of oxygen in the water. Of the 6 moles of oxygen in the vapor phase, 1 mole dissolves in the water to
bring the dissolved moles to 3.
13-33