Course: Principles of Chemistry 2

Lecturer: PhD Ngo Tuan Cuong

 Faculty of Chemistry and Center for
Computational Science
 Hanoi National University of Education
Course: Principles of Chemistry 2
Contents
 Chapter 1: Solids and advanced materials
 Chapter 2: Solution
 Chapter 3: Chemical kinetics
 Chapter 4: Chemical Equilibrium
 Chapter 5: Gibbs energy and thermodynamics
 Chapter 6: Acids and Bases
 Chapter 7: Electrochemistry
Chapter 2: Chemistry of Solution

Contents
 2.1. Solution types. Forming a solution.
 2.2. The Role of Enthalpy in Solution Formation
 2.3. Entropy and Solution Formation.
 2.4. Solution Equilibrium and Factors Affecting
Solubility.
 2.5. Colligative Properties- Freezing Point
Depression, Boiling Point Elevation, and Osmosis.
 2.6. The Colligative Properties of Strong Electrolyte
Solutions.
I. Solution types. Forming a solution
 Solution
Solutions are homogeneous (single-phase) mixtures of two or more
components. They are extremely important in Chemistry because
they allow intimate and varied encounters between molecules of
different kinds, a condition that is essential for rapid chemical
reactions to occur. Several more explicit reasons can be cited for
devoting a significant amount of time to the subject of solutions:
 1. For the reason stated above, most chemical reactions that
are carried out in the laboratory and in industry, and that
occur in living organisms, take place in solution.
 2. Solutions are so common; very few pure substances are
found in nature.
 I. Solution types. Forming a solution
 Solution
Several more explicit reasons can be cited for devoting a significant
amount of time to the subject of solutions:
 3. Solutions provide a convenient and accurate means of
introducing known small amounts of a substance to a
reaction system. Advantage is taken of this in the process of
titration, for example.
 4. The physical properties of solutions are sensitively
influenced by the balance between the intermolecular forces
of like and unlike (solvent and solute) molecules. The
physical properties of solutions thus serve as useful
experimental probes of these intermolecular forces.

That these intermolecular forces can have dramatic effects is made readily apparent by a simple
example. At 0 ◦C and 1 atm pressure, one litre of water will dissolve 1300 litres of ammonia gas;
this corresponds to a solubility of 58 mol L−1. Now if 58 mol of an ideal gas were compressed so
that it would fit into the same 1-liter volume (but without the water), a very high pressure would be
required. (You should be able to estimate this pressure; try it!).
I. Solution types. Forming a solution
 Types of Solution
We usually think of a solution as a liquid; a mixture of a gas, liquid, or
solid solute in a liquid solvent. Actually, solutions can exist as gases
and solids as well. Gaseous mixtures don’t require any special
consideration beyond what you learned about Dalton’s Law earlier in
the course. Solid solutions are very common; most natural minerals
and many alloys are solid solutions.

To see how these considerations are applied to solutions, think about

the individual steps that must be carried out when a solute is
dissolved in a solvent:
 1. The solute must be dispersed; that is, its molecular units
must be pulled apart. This requires energy, and so this step
always works against solution formation.
 I. Solution types. Forming a solution
 Types of Solution
…the individual steps that must be carried out …:
 2. The solute must be introduced into the solvent. Whether
this is energetically favorable or unfavorable depends on the
nature of the solute and solvent. If the solute is A and the
solvent is B, then what is important is the strength of the
attractive forces between A-A and B-B molecules, compared
to those between A-B pairs; if the latter are greater, then the
potential energy will be lower when the substances are
mixed and solution formation will be favored.
If the sum of these two steps is exothermic, this will favor solution formation, but
there is one other factor to consider: Would the formation of a solution lead to an
increase or a decrease in disorder on the molecular scale? The answer varies
from case to case; mixing of different kinds of molecules always creates disorder,
and substantially increasing the volume they occupy (as when a solid dissolves in
a liquid) can have a very large effect. Higher temperatures generally favor
processes in which disorder is created, but tend to work against those in which
disorder is lost.
I. Solution types. Forming a solution
 Types of Solution
In all solutions, whether gaseous, liquid, or solid, the
substance present in the greatest amount is the solvent, and
the substance or substances present in lesser amounts are
the solute(s). The solute does not have to be in the same
physical state as the solvent, but the physical state of the
solvent usually determines the state of the solution. As long as
the solute and solvent combine to give a homogeneous
solution, the solute is said to be soluble in the solvent.
Table 1 lists some common examples of gaseous, liquid, and
solid solutions and identifies the physical states of the solute
and solvent in each.
 I. Solution types. Forming a solution
 Types of Solution

 Table 1. Types of Solution

Solution Solute Solvent Examples
gas gas gas air, natural gas
liquid gas liquid seltzer water (CO2 gas in water)

alcoholic beverage (ethanol in water),

liquid liquid liquid
gasoline
liquid solid liquid tea, salt water
solid gas solid H2 in Pd (used for H2 storage)
solid solid liquid mercury in silver or gold (amalgam)

solid solid solid alloys and other "solid solutions"

 I. Solution types. Forming a solution
 Forming a Solution

The formation of a solution from a solute and a solvent is a physical

process, not a chemical one. That is, both solute and solvent can be
recovered in chemically unchanged forms using appropriate separation
methods. For example, solid zinc nitrate dissolves in water to form an
aqueous solution of zinc nitrate:

Zn(NO3)2 (s)+H2O(l) → Zn2+(aq)+2NO3-(aq)

Because Zn(NO3)2 can be recovered easily by evaporating the water, this

is a physical process. In contrast, metallic zinc appears to dissolve in
aqueous hydrochloric acid. In fact, the two substances undergo a
chemical reaction to form an aqueous solution of zinc chloride with
evolution of hydrogen gas:

Zn(s)+2H+(aq)+2Cl−(aq) → Zn2+(aq) + 2Cl−(aq) + H2(g)

 I. Solution types. Forming a solution
 Forming a Solution

Zn(s)+2H+(aq)+2Cl−(aq) → Zn2+(aq) + 2Cl−(aq) + H2(g)

When the solution evaporates, we do not recover metallic zinc, so we
cannot say that metallic zinc is soluble in aqueous hydrochloric acid
because it is chemically transformed when it dissolves. The dissolution
of a solute in a solvent to form a solution does not involve a chemical
transformation (that it is a physical change).
Dissolution of a solute in a solvent to form a solution does not
involve a chemical transformation.
Substances that form a single homogeneous phase in all proportions are
said to be completely miscible in one another. Ethanol and water are
miscible, just as mixtures of gases are miscible. If two substances are
essentially insoluble in each other, such as oil and water, they
are immiscible. Examples of gaseous solutions that we have already
discussed include Earth’s atmosphere.
 II. The Role of Enthalpy
in Solution Formation

Energy is required to overcome the intermolecular interactions in a

solute, which can be supplied only by the new interactions that
occur in the solution, when each solute particle is surrounded by
particles of the solvent in a process called solvation (or hydration
when the solvent is water). Thus all of the solute–solute
interactions and many of the solvent–solvent interactions must be
disrupted for a solution to form. In this section, we describe the role
of enthalpy in this process.
Because enthalpy is a state function, we can use a thermochemical
cycle to analyze the energetics of solution formation. The process
occurs in three discrete steps, indicated by ΔH 1, ΔH2, and ΔH3 in
Figure 1. The overall enthalpy change in the formation of the
solution (ΔHsoln) is the sum of the enthalpy changes in the three
steps:
 II. The Role of Enthalpy
in Solution Formation ΔHsoln=ΔH1+ΔH2+ΔH3
Figure 2: Enthalpy Changes
That Accompany the
Formation of a Solution.
Solvation can be an
exothermic or endothermic
process depending on the
nature of the solute and
solvent. In both cases, step
1, separation of the solvent
particles, is energetically
uphill (ΔH1 > 0), as is step
2, separation of the solute
particles (ΔH2 > 0). In
contrast, energy is released
in step 3 (ΔH3 < 0) because
of interactions between the
solute and solvent.
a) Exothermic solution formation
 II. The Role of Enthalpy
ΔHsoln=ΔH1+ΔH2+ΔH3
in Solution Formation

(a) When ΔH3 is larger in

magnitude than the sum
of ΔH1 and ΔH2, the
overall process is
exothermic (ΔHsoln < 0), as
shown in the
thermochemical cycle. (b)
When ΔH3 is smaller in
magnitude than the sum
of ΔH1 and ΔH2, the
overall process is
endothermic (ΔHsoln > 0).

a) Endothermic solution formation

 II. The Role of Enthalpy
in Solution Formation
A positive value for ΔHsoln does not
mean that a solution will not form.
Whether a given process, including
formation of a solution, occurs
spontaneously depends on whether
the total energy of the system is
lowered as a result. Enthalpy is only
one of the contributing factors. A
high ΔHsoln is usually an indication
that the substance is not very
soluble. Instant cold packs used to Figure 3: Commercial Cold Packs for
treat athletic injuries, for example, Treating Injuries. These packs
take advantage of the large contain solid NH4NO3 and water in
positive ΔHsoln of ammonium nitrate separate compartments. When the
during dissolution (+25.7 kJ/mol), seal between the compartments is
which produces temperatures less broken, the NH4NO3 dissolves in the
 II. The Role of Enthalpy
in Solution Formation
Solutions of ionic solids in water

The key factor here turns out to be the interaction of the ions with
the solvent. The electrically-charged ions exert a strong coulombic
attraction on the end of the water molecule that has the opposite
partial charge. As a consequence, ions in solution are always
hydrated; that is, they are quite tightly bound to water molecules
through ion-dipole interaction. The number of water molecules
contained in the primary hydration shell varies with the radius and
charge of the ion.
The dissolution of an ionic solid in water can be thought of as a
sequence of two steps:
(1)
(2)
H1 > 0: lattice energy; H2 < 0: hydration energy
 II. The Role of Enthalpy
in Solution Formation
Solutions of ionic solids in water

Figure 1: Energetics of dissolution of ionic solids

 II. The Role of Enthalpy
in Solution Formation
Solutions of ionic solids in water

The first reaction is endothermic, but the second is exothermic;

whether the overall dissolution process is energetically favorable or
unfavorable depends on the actual number of kilojoules associated
with the two processes.
As you can see from the examples in Table 3, the net energy (the
heat of solution) is the sum of two quantities having large
magnitudes and opposite signs; the sign of the result is therefore
rather hard to predict.
The balance between the lattice energy and hydration energy is a
major factor in determining the solubility of an ionic crystal in water,
but there is another factor to consider as well. We generally
assume that there is a rather large increase in disorder when a
solid is dispersed into the liquid phase.
 II. The Role of Enthalpy
in Solution Formation
Solutions of ionic solids in water

Table 3. Energy terms associated with the dissolution of some ionic

solids
substan LiF NaI KBr CsI LiCl NaCl KCl AgCl
ce
Lattice 1021 682 669 586 846 778 707 910
energy
(kJ/mol)
Hydratio 1017 686 649 552 884 774 690 844
n energy
(kJ/mol)
Heat of +3 -4 +20 +34 -38 +4 +17 +66
solution
(kJ/mol)
 II. The Role of Enthalpy
in Solution Formation
Solutions of ionic solids in water

However, in the case of ionic solids, each ion ends up surrounded

by a shell of oriented water molecules. The ions themselves have
become more disordered, but the water molecules are now more
ordered than before. In some cases the latter effect predominates,
and dissolution of the salt leads to a net increase in order. Recall
that any process in which the net disorder diminishes becomes less
probable as the temperature increases; this explains why the
solubilities of some salts decrease with temperature.
 III. Entropy and Solution Formation

The enthalpy change that accompanies a process is important

because processes that release substantial amounts of energy tend to
occur spontaneously. A second property of any system, its entropy, is
also important in helping us determine whether a given process
occurs spontaneously. We will discuss entropy in more detail
elsewhere, but for now we can state that entropy (S) is a
thermodynamic property of all substances that is proportional to their
degree of disorder. A perfect crystal at 0 K, whose atoms are regularly
arranged in a perfect lattice and are motionless, has an entropy of
zero. In contrast, gases have large positive entropies because their
molecules are highly disordered and in constant motion at high
speeds.
III. Entropy and Solution Formation
The formation of a solution disperses molecules, atoms, or ions of
one kind throughout a second substance, which generally increases
the disorder and results in an increase in the entropy of the system.
Thus entropic factors almost always favor formation of a solution. In
contrast, a change in enthalpy may or may not favor solution
formation. The London dispersion forces that hold cyclohexane and
n-hexane together in pure liquids, for example, are similar in nature
and strength. Consequently, ΔHsoln should be approximately zero, as
is observed experimentally. Mixing equal amounts of the two liquids,
however, produces a solution in which the n-hexane and
cyclohexane molecules are uniformly distributed over approximately
twice the initial volume. In this case, the driving force for solution
formation is not a negative ΔHsoln but rather the increase in entropy
due to the increased disorder in the mixture.
III. Entropy and Solution Formation
All spontaneous processes with ΔH≥0 are characterized by
an increase in entropy. In other cases, such as mixing oil with water,
salt with gasoline, or sugar with hexane, the enthalpy of solution is
large and positive, and the increase in entropy resulting from
solution formation is not enough to overcome it. Thus in these cases
a solution does not form.
All spontaneous processes with ΔH ≥ 0 are characterized by an
increase in entropy.
Table 1 summarizes how enthalpic factors affect solution formation for four
general cases. The column on the far right uses the relative magnitudes of
the enthalpic contributions to predict whether a solution will form from each
of the four. Keep in mind that in each case entropy favors solution
formation. In two of the cases the enthalpy of solution is expected to be
relatively small and can be either positive or negative. Thus the entropic
contribution dominates, and we expect a solution to form readily. In the
other two cases the enthalpy of solution is expected to be large and
positive.
 III. Entropy and Solution Formation
Table 1. The entropic contribution, though favorable, is usually too small to
overcome the unfavorable enthalpy term. Hence we expect that a solution
will not form readily.
Table 1. Relative Changes in Enthalpies for Different Solute–Solvent
Combinations*
ΔH1 (separation ΔH2 (separation ΔH3 (solute–
ΔHsoln (ΔH1 + ΔH2 +Δ Result of
of solvent of solute solvent Mixing Solute
H3)
molecules) particles) interactions) and Solvent†
small; positive or
solution will
large; positive large; positive large; negative
negative usually form
solution will
small; positive large; positive small; negative large; positive
not form
solution will
large; positive small; positive small; negative large; positive
not form
small; positive or solution will
small; positive small; positive small; negative
negative usually form
*ΔH1, ΔH2, and ΔH3 refer to the processes indicated in the thermochemical cycle
shown in Figure 1.
†
In all four cases, entropy increases.
III. Entropy and Solution Formation
In contrast to liquid solutions, the intermolecular interactions in gases
are weak (they are considered to be nonexistent in ideal gases).

Hence mixing gases is

usually a thermally neutral
process (ΔHsoln≈0), and
the entropic factor due to
the increase in disorder is
dominant (Figure 3).
Consequently, all gases
dissolve readily in one
another in all proportions
to form solutions.
III. Entropy and Solution Formation

Figure 3: Formation of a
Solution of Two Gases. (top)
Pure samples of two different
gases are in separate bulbs.
(bottom) When the
connecting stopcock is
opened, diffusion causes the
two gases to mix together and
form a solution. Even
though ΔHsoln is zero for the
process, the increased
entropy of the solution (the
increased disorder) versus
that of the separate gases
favors solution formation.
IV. Solution Equilibrium and Factors
Affecting Solubility
Effect of Temperature on the Solubility of Solids

Experimentally it is found that the solubility of most compounds

depends strongly on temperature and, if a gas, on pressure as well.
As we shall see, the ability to manipulate the solubility by changing
the temperature and pressure has several important
consequences.
Figure 4 shows plots of the solubilities of several organic and
inorganic compounds in water as a function of temperature.
Although the solubility of a solid generally increases with increasing
temperature, there is no simple relationship between the structure
of a substance and the temperature dependence of its solubility.
Many compounds (such as glucose and CH3CO2Na) exhibit a
dramatic increase in solubility with increasing temperature. Others
(such as NaCl and K2SO4) exhibit little variation, and still others
(such as Li2SO4) become less soluble with increasing temperature.
IV. Solution Equilibrium and Factors
Affecting Solubility
Effect of Temperature on the Solubility of Solids
IV. Solution Equilibrium and Factors
Affecting Solubility
Effect of Temperature on the Solubility of Solids

Notice in particular the curves for NH 4NO3 and CaCl2. The

dissolution of ammonium nitrate in water is endothermic
(ΔHsoln=+25.7kJ/mol), whereas the dissolution of calcium chloride is
exothermic (ΔHsoln=−68.2kJ/mol), yet Figure 4 shows that the
solubility of both compounds increases sharply with increasing
temperature. In fact, the magnitudes of the changes in both
enthalpy and entropy for dissolution are temperature dependent.
Because the solubility of a compound is ultimately determined by
relatively small differences between large numbers, there is
generally no good way to predict how the solubility will vary with
temperature.
The variation of solubility with temperature has been measured for a
wide range of compounds, and the results are published in many
standard reference books.
 IV. Solution Equilibrium and Factors
Affecting Solubility
Effect of Temperature on the Solubility of Solids

Chemists are often able to use this information to separate the components
of a mixture by fractional crystallization, the separation of compounds on the
basis of their solubilities in a given solvent. For example, if we have a
mixture of 150 g of sodium acetate (CH3CO2Na) and 50 g of KBr, we can
separate the two compounds by dissolving the mixture in 100 g of water at
80°C and then cooling the solution slowly to 0°C. According to the
temperature curves in Figure 4, both compounds dissolve in water at 80°C,
and all 50 g of KBr remains in solution at 0°C. Only about 36 g
of CH3CO2Na are soluble in 100 g of water at 0°C, however, so
approximately 114 g (150 g − 36 g) of CH 3CO2Na crystallizes out on cooling.
The crystals can then be separated by filtration. Thus fractional
crystallization allows us to recover about 75% of the original CH 3CO2Na in
essentially pure form in only one step.
 IV. Solution Equilibrium and Factors
Affecting Solubility
Effect of Temperature on the Solubility of Solids

Fractional crystallization is a common technique for purifying

compounds as diverse as those shown in Figure 4 and from
antibiotics to enzymes. For the technique to work properly, the
compound of interest must be more soluble at high temperature than
at low temperature, so that lowering the temperature causes it to
crystallize out of solution. In addition, the impurities must be more
soluble than the compound of interest (as was KBr in this example)
and preferably present in relatively small amounts.
IV. Solution Equilibrium and Factors
Affecting Solubility
Effect of Temperature on the Solubility of Gases

The solubility of gases in liquids decreases with increasing

temperature, as shown in Figure 5. Attractive intermolecular
interactions in the gas phase are essentially zero for most
substances. When a gas dissolves, it does so because its
molecules interact with solvent molecules. Because heat is
released when these new attractive interactions form, dissolving
most gases in liquids is an exothermic process (ΔHsoln<0).
Conversely, adding heat to the solution provides thermal energy
that overcomes the attractive forces between the gas and the
solvent molecules, thereby decreasing the solubility of the gas. The
phenomenon is similar to that involved in the increase in the vapor
pressure of a pure liquid with increasing temperature. In the case
of vapor pressure, however, it is attractive forces between solvent
molecules that are being overcome by the added thermal energy
when the temperature is increased.
IV. Solution Equilibrium and Factors
Affecting Solubility
Effect of Temperature on the Solubility of Gases

Figure 5: Solubilities of
Several Common Gases
in Water as a Function of
Temperature at Partial
Pressure of 1 atm. The
solubilities of all gases
decrease with increasing
temperature.
 IV. Solution Equilibrium and Factors
Affecting Solubility
Effect of Temperature on the Solubility of Gases

The decrease in the solubilities of gases at higher temperatures has

both practical and environmental implications. Anyone who routinely
boils water in a teapot or electric kettle knows that a white or gray
deposit builds up on the inside and must eventually be removed. The
same phenomenon occurs on a much larger scale in the giant boilers
used to supply hot water or steam for industrial applications, where it
is called “boiler scale,” a deposit that can seriously decrease the
capacity of hot water pipes. The problem is not a uniquely modern
one: aqueducts that were built by the Romans 2000 years ago to
carry cold water from alpine regions to warmer, drier regions in
southern France were clogged by similar deposits. The chemistry
behind the formation of these deposits is moderately complex and will
be described elsewhere, but the driving force is the loss of
dissolved CO2 from solution.
IV. Solution Equilibrium and Factors
Affecting Solubility
Effect of Temperature on the Solubility of Gases

Hard water contains dissolved Ca2+ and HCO3− (bicarbonate) ions.

Calcium bicarbonate (Ca(HCO3)2 is rather soluble in water, but
calcium carbonate (CaCO3) is quite insoluble. A solution of
bicarbonate ions can react to form carbon dioxide, carbonate ion,
and water:
2HCO3−(aq)→CO32−(aq)+H2O(l)+CO2(aq)

Heating the solution decreases the solubility of CO 2, which escapes

into the gas phase above the solution. In the presence of calcium
ions, the carbonate ions precipitate as insoluble calcium carbonate,
the major component of boiler scale.
 IV. Solution Equilibrium and Factors
Affecting Solubility
Effect of Temperature on the Solubility of Gases

In thermal pollution, lake or river water that is used to cool an industrial reactor or a
power plant is returned to the environment at a higher temperature than normal.
Because of the reduced solubility of O2 at higher temperatures, the warmer water
contains less dissolved oxygen than the water did when it entered the plant. Fish and
other aquatic organisms that need dissolved oxygen to live can literally suffocate if
the oxygen concentration of their habitat is too low. Because the warm, oxygen-
depleted water is less dense, it tends to float on top of the cooler, denser, more
oxygen-rich water in the lake or river, forming a barrier that prevents atmospheric
oxygen from dissolving.
Eventually even deep lakes can be suffocated if the problem is not corrected.
Additionally, most fish and other nonmammalian aquatic organisms are cold-
blooded, which means that their body temperature is the same as the temperature
of their environment. Temperatures substantially greater than the normal range can
lead to severe stress or even death. Cooling systems for power plants and other
facilities must be designed to minimize any adverse effects on the temperatures of
surrounding bodies of water.