Chemical Principle S: Chapter 17 Properties of Solutions

Chemical Principle
hapter 17 Properties of Solutions s

2017 Cengage Learning All Rights Reserved
Chapter 17 Properties of Solutions
17.1 Spontaneous Processes
17.2 The Isothermal Expansion and Compression of an
Ideal Gas
17.3 The Definition of Entropy
17.4 Entropy and Physical Changes
17.5 Entropy and the Second Law of Thermodynamics
17.6 The Effect of Temperature on Spontaneity
17.7 Free Energy
17.8 Entropy Changes in Chemical Reactions
Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

2
17.1 Solution Composition
A solute is the substance being dissolved. The solvent is the
dissolving medium.
When liquids are mixed, the liquid present in the largest am
ount is called the solvent.

3
Mass percent (sometimes called weight percent) is the per
cent solute by mass in the solution:

4
The mole fraction (symbolized by the Greek letter chi, x), t
he ratio of the number of moles of a given component to th
e total number of moles of solution.
For a two-component solution, where nA and nB represent t
he number of moles of the two components,
molality (symbolized by m), the number of moles of solute

per kilogram of solvent:

5
4.3 The Composition of Solutions
The nature of the reaction, which depends on the
exact forms the chemicals take when dissolved, and
the amounts of chemicals present in the solutions,
that is, the composition of each solution.
A standard solution is a solution whose concentration

6is accurately known.
17.2 The Thermodynamics of Solution
Formation
Polar solvents dissolve polar solutes; nonpolar solvent
s dissolve nonpolar solutes.
Because the pesticide DDT is fat-soluble, it is retained and c
oncentrated in animal tissues, where it causes detrimental e
ffects.
The solubilities of various vitamins are important in determi
ning correct dosages.
The insolubility of barium sulfate means it can be safely use
d to improve X-ray images of the gastrointestinal tract, even
though Ba2+ ions are quite toxic.
7
Formation
What factors affect solubility? The cardinal rule of solubility

is like dissolves like.
assume that the formation of a liquid solution takes place in
three distinct steps.
Step 1: Breaking up the solute into individual components
(expanding the solute).
Step 2: Overcoming intermolecular forces in the solvent to
make room for the solute (expanding the solvent).
Step 3: Allowing the solute and solvent to interact to form t
he solution.
8
Formation
Figure 17.1 The formation of a liquid solution can be divided into

three steps: (1) expanding the solute, (2) expanding the solvent, and
(3) combining the expanded solute and solvent to form the solution.
9
Formation
the solubility of sodium chloride in water. It is clear that for NaCl

(s) the term H1 is large and positive because of the strong ionic f
orces in the crystal that must be overcome.
Also, H2 is expected to be large and positive because of the hydr
ogen bonds that must be broken in water.
Finally, H3 is expected to be large and negative because of the st
rong interactions between the ions and the water molecules. In fa
ct, the exothermic and endothermic terms essentially cancel in th
is case, as shown from the known values:

10
Formation
The second step shown here combines the terms H2 (for ex
panding the solvent) and H3 (for solventsolute interaction
s) and is called the enthalpy (heat) of hydration (Hhyd). Th
is term represents the enthalpy change associated with the
dispersal of a gaseous solute in water.
Thus the standard enthalpy of solution for dissolving sodiu
m chloride is the sum of H1 and Hhyd:
Note that Hsoln is small but positive; the dissolving proces

s requires a small amount of energy. Then why is NaCl so so
luble in water? Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning
11
Formation
It is an experimental fact that NaCl(s) dissolves in water to f
orm 1.0 M NaCl.
Thus G for this process must be negative. However, the pr

eceding calculations show that Hsoln is positive and thus u
nfavorable.
Therefore, Ssoln must be positive and large enough to mak
e G negative (through the TS term). It is certainly not su
rprising that Ssoln would be positive for this process.

12
Formation

13
Formation
A nonpolar solute does not dissolve in large quantities in a
polar solvent.
What causes G to be positive for the dispersal of a materia
l containing large nonpolar molecules in a polar solvent suc
h as water?
Hsoln is expected to be positive (unfavorable) because H
3, the only exothermic component of H
soln, is not expecte
d to have a very large magnitude. We expect Ssoln to be p
ositive (favorable).
Thus we can explain the incompatibility of nonpolar and pol
ar substances on the basis of the expected large, positive he
at of solution that overwhelms the positive entropy change,
thus
14 giving a positive value for G . Therefore, the solution
Formation

15
Formation
Water as a Solvent
note that Ssoln for KCl(s) is positive, but the value for LiF(s)
is negative. This probably results from the smaller sizes (an
d thus larger charge densities) of Li+ and F- as compared wit
h K+ and Cl-.
The smaller ions presumably are able to bind the hydrating
water molecules more firmly and thus show a more negativ
e value for Ssoln. The charges on the ions are also importa
nt. Note that CaS(s) exhibits a value of Ssoln that is more n
egative than that for LiF(s), as might be expected for the mo
re highly charged Ca2+ and S2- ions.
16
17.3 Factors Affecting Solubility
Structure Effects
Vitamins can be divided into two classes: fat-soluble (vitamins A,
D, E, and K) and water-soluble (vitamins B and C).

17
Vitamin A, composed mostly of carbon and hydrogen atoms
that have similar electronegativities, is virtually nonpolar. T
his causes it to be soluble in nonpolar materials such as bo
dy fat, which is also largely composed of carbon and hydrog
en, but not soluble in polar solvents such as water.
Vitamin C has many polar -OH and C-O bonds, making the
molecule polar and thus water-soluble. We often describe n
onpolar materials like vitamin A as hydrophobic (water-feari
ng) and polar substances like vitamin C as hydrophilic (wate
r-loving).
The fat-soluble vitamins can build up in the fatty tissues of t
he body. This buildup has both positive and negative effect
s. Since these vitamins can be stored, the body can tempora
rily
18 tolerate a diet deficient in vitamins A, D, E, and K.
Conversely, if excessive amounts of these vitamins are cons
umed, their buildup can lead to the illness hypervitaminosi
s.
In contrast, the water-soluble vitamins are excreted by the
body and therefore must be consumed regularly.
This fact was first recognized when the British navy discover
ed that scurvy, a disease often suffered by sailors, could be
prevented if the sailors regularly ate fresh limes (which are
a good source of vitamin C) when aboard ship (hence the na
me limey for the British sailor).

19
Pressure Effects
Although pressure has little effect on the solubilities of solids or li
quids, it does significantly increase the solubility of a gas.
Carbonated beverages, for example, are always bottled at high pr
essure of carbon dioxide to ensure a high concentration of carbo
n dioxide in the liquid. The fizzing that occurs when you open a b
ottle of soda results from the escape of gaseous carbon dioxide b
ecause the atmospheric pressure of CO2 is much lower than that
used in the bottling process.
Henrys law states that the amount of gas dissolved in a solution i
s directly proportional to the pressure of the gas above the soluti
on.

20
Figure 17.4 (a) A gaseous solute in equilibrium with a solution. (b) The
piston is pushed in and causes an increase in the rate at which the gas
enters the solution, so the concentration of dissolved gas increases. (c) The
greater gas concentration in the solution causes an increase in the rate of
escape. A new equilibrium is reached.
21

22
Temperature Effects for Aqueous Solutions
Figure 17.5
The solubilities of several solids
as a function of temperature.
Note that although most
substances become more soluble
in water with increasing
temperature, sodium sulfate and
cerium sulfate become less
soluble.
23
Temperature Effects for Aqueous Solutions
Figure 17.6
The solubilities of several gases in
water as a function of
temperature at a constant
pressure of 1 atm of gas above
the solution.
24
The decreasing water solubility of gases with increased tem
perature is also responsible for the formation of boiler scal
e. The bicarbonate ion is formed when carbon dioxide is dis
solved in water containing the carbonate ion:
When the water also contains Ca2+ soluble in water, but calci
um carbonate is insoluble. When the water is heated, the ca
rbon dioxide is driven off. For the system to replace the lost
carbon dioxide, the reverse reaction must occur:

25
This reaction, however, also increases the concentration of
carbonate ions, causing solid calcium carbonate to form. Th
is solid is the boiler scale that coats the walls of containers s
uch as industrial boilers and tea kettles.
Boiler scale reduces the efficiency of heat transfer and can l
ead to blockage of pipes
Figure 17.7
A pipe with accumulated mineral
26 deposits. Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning
17.4 The Vapor Pressures of Solutions
Figure 17.8 An aqueous solution and pure water in a closed

environment. (a) Initial stage.(b) After a period of time, the water is
transferred to the solution
27
The presence of a nonvolatile solute lowers the vapor press
ure of a solvent.
Figure 17.9
The presence of a nonvolatile solute inhibits the escape of
solvent molecules from the liquid and so lowers the vapor
pressure
28 of the solvent. Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning
Figure 17.10
For a solution that obeys Raoults law,
a plot of Psoln versus Xsolvent yields a
straight line.
29
Nonideal Solutions
for liquidliquid solutions where both components are volat
ile, a modified form of Raoults law applies:
where PTotal represents the total vapor pressure of a solution

containing A and B, xA and xB are the mole fractions of A and
B, P0A and P0B are the vapor pressures of pure A and pure B,
and PA and PB are the partial pressures resulting from molec
ules of A and B in the vapor above the solution.

30
Figure 17.11 Vapor pressure for a solution of two volatile liquids. (a) The
behavior predicted for an ideal liquidliquid solution by Raoults law. (b) A
solution for which PTotal is larger than the value calculated from Raoults law.
This solution shows a positive deviation from Raoults law. (c) A solution for
which PTotal is smaller than the value calculated from Raoults law. This
solution shows a negative deviation from Raoults law.
31
Large negative heats of solution indicate especially strong s
olutesolvent interactions, and such solutions are expected
to show negative deviations from Raoults law. Both compo
nents have a lower escaping tendency in the solution than i
n the pure liquids.
This behavior is illustrated by an acetonewater solution wh
ere the molecules can hydrogen-bond effectively:

32
if two liquids mix endothermically, this indicates that the sol
utesolvent interactions are weaker than the interactions a
mong the molecules in the pure liquids. More energy is req
uired to expand the liquids than is released when the liquid
s are mixed. In this case the molecules in the solution have
a higher tendency to escape than expected, and positive de
viations from Raoults law are observed.
An example of this case is provided by a solution of ethanol
and hexane, whose Lewis structures are as follows:

33
for a solution of very similar liquids, such as benzene and to
luene,
the enthalpy of solution is very close to zero; thus the soluti

on closely obeys Raoults law (ideal behavior).
34

35
17.5 Boiling-Point Elevation and
Freezing-Point Depression
Boiling-Point Elevation
a nonvolatile solute elevates the boiling point of the solvent.
where T is the boiling-point elevation, or the difference bet

ween the boiling point of the solution and that of the pure s
olvent, Kb is a constant that is characteristic of the solvent a
nd is called the molal boiling-point elevation constant, a
nd msolute is the molality of the solute in the solution.

36
Figure 17.12 Phase diagrams for pure water (red lines) and for
an aqueous solution containing a nonvolatile solute (blue lines).
Note that the boiling point of the solution is higher than that of
pure water. Conversely, the freezing point of the solution is lower
than
37 that of pure water. Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

38
When a solute is dissolved in a solvent, the freezing point of
the solution is lower than that of the pure solvent.
where T is freezing-point depression, or the difference bet

ween the freezing point of the pure solvent and that of the s
olution, and Kf is a constant that is characteristic of a particu
lar solvent and is called the molal freezing-point depressi
on constant.

39
Figure 17.13
(a) Ice in equilibrium with liquid water. (b) Ice in equilibrium
with liquid water containing a dissolved solute (shown in
pink).
40
17.6 Osmotic Pressure
Osmotic Pressure
A solution and pure solvent are separated by a semiperme
able membrane, which allows solvent but not solute molec
ules to pass through. As time passes, the volume of the solu
tion increases, whereas that of the solvent decreases. This fl
ow of solvent into the solution through the semipermeable
membrane is called osmosis.
Eventually the liquid levels stop changing, indicating that th
e system has reached equilibrium. Because the liquid levels
are different at this point, there is a greater hydrostatic pres
sure on the solution than on the pure solvent. This excess p
ressure is called the osmotic pressure.

41
Figure 17.14
A tube with a bulb on the end is covered by a semipermeable
membrane. The solution inside the tube is bathed in the pure
solvent. There is a net transfer of solvent molecules into the
solution until the hydrostatic pressure equalizes the solvent flow
in both directions.
42
Figure 17.15
The normal flow of solvent into
the solution (osmosis) can be
prevented by applying an
external pressure to the solution.
The minimum pressure required
to stop the osmosis is equal to
43 the osmotic
Zumdahl/Decoste |pressure
Chemical Principles, of the
8e, 2017 Cengage Learning
solution.
Figure 17.16 (a) A pure solvent and its solution (containing a

nonvolatile solute) are separated by a semipermeable membrane
through which solvent molecules (blue) can pass but solute
molecules (green) cannot. The rate of solvent transfer is greater
from solvent to solution than from solution to solvent. (b) The
system
44 at equilibrium, where the rate of solvent
Zumdahl/Decoste | Chemicaltransfer isCengage
Principles, 8e, 2017 theLearning
same in both directions.
Osmotic Pressure
where is the osmotic pressure in atmospheres, M is

the molarity of the solute, R is the gas law constant,
and T is the Kelvin temperature.

45
Reverse Osmotic
Figure 17.18
Reverse osmosis. A pressure
greater
than the osmotic pressure of the
solution is applied, which causes a
net flow of solvent molecules (blue)
from the solution to the pure
solvent. The solute molecules
(green) remain behind.
46
Reverse Osmotic
Figure 17.20
A desalination plant that
can supply 132,000
gallons of drinkable
water per day, one-third
of the islands daily
needs.
47
17.7 Colligative Properties of Electrolyte Soluti
ons
Electrolyte Solutions

48
17.7 Colligative Properties of Electrolyte Soluti
ons
Electrolyte Solutions
Figure 17.21
In an aqueous solution, a few ions aggregate, forming ion
pairs that behave as a unit.

49
17.7 Colligative Properties of Electrolyte Solutio
ns

50
17.8 Colloids
The scattering of light by particles is called the
Tyndall effect and is often used to distinguish
between a suspension and a true solution.
Figure 17.22
The Tyndall effect. The solution on the left does not show the path
of the light beam, whereas the suspension on the right clearly
shows
51 the light path. Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning
17.8 Colloids

17.8 Colloids
What stabilizes a colloid? Why do the particles remain suspe
nded rather than forming larger aggregates and precipitatin
g out?
The answer is complicated, but the main effect that stabilize
s the colloid seems to be electrostatic repulsion.
A colloid, like all other macroscopic substances, is electricall
y neutral. However, when a colloid is placed in an electric fie
ld, the dispersed particles all migrate to the same electrode;
thus they must all have the same charge.
The center of a colloidal particle (a tiny ionic crystal, a group
of molecules, or a single large molecule) attracts from the m
edium a layer of ions, all of the same charge. This group of i
ons in turn attracts another layer of oppositely charged ion
53
s.
17.8 Colloids
Figure 17.23
A representation of two colloidal particles. In each the center
particle is surrounded by a layer of positive ions, with negative
ions in the outer layer. Thus, although the particles are
electrically
neutral, they still repel each other because of their outer
negative Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning
layer of ions.
17.8 Colloids
The destruction of a colloid, called coagulation, can usually
be accomplished either by heating or by adding an electroly
te.
Heating increases the velocities of the colloidal particles, ca
using them to collide with enough energy so that the ion ba
rriers are penetrated. This allows the particles to aggregate.
Adding an electrolyte neutralizes the adsorbed ion layers. T
he high salt content of the seawater causes the colloidal cla
y particles to coagulate.
The removal of soot from smoke is another example of the
coagulation of a colloid. When smoke is passed through an
electrostatic precipitator, the suspended solids are remove
d. Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning
55
17.8 Colloids
Figure 17.24
The Cottrell precipitator installed
in a smokestack. The charged
plates attract the colloidal
particles because of their ion
layers and thus remove them
from the smoke.
56

Chemical Principle S: Chapter 17 Properties of Solutions

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Chemical Principle

hapter 17 Properties of Solutions s

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

molality (symbolized by m), the number of moles of solute

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

A standard solution is a solution whose concentration

What factors affect solubility? The cardinal rule of solubility

Figure 17.1 The formation of a liquid solution can be divided into

the solubility of sodium chloride in water. It is clear that for NaCl

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

Note that Hsoln is small but positive; the dissolving proces

Thus G for this process must be negative. However, the pr

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

Figure 17.8 An aqueous solution and pure water in a closed

where PTotal represents the total vapor pressure of a solution

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

the enthalpy of solution is very close to zero; thus the soluti

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

where T is the boiling-point elevation, or the difference bet

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

where T is freezing-point depression, or the difference bet

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

Figure 17.16 (a) A pure solvent and its solution (containing a

where is the osmotic pressure in atmospheres, M is

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

Zumdahl/Decoste | Chemical Principles, 8e, 2017 Cengage Learning

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