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Module 6:
Solutions
Definitions (solutions: solvent, solute, solubility,
concentration; interactions between solvent phase and
solute molecules; properties of polar and non-polar
solvents; properties of colloid).
Chemical equilibrium for solutions (self-ionisation of
water, solvation, pH; Acids and Bases; solution
equilibrium with precipitation).
Solution
A solution is defined as a homogeneous mixture of
substances in which no settling occurs.
A solution consists of a solvent and one or more solutes,
whose proportions vary from one solution to another.
The solvent is the medium in which the solutes are
dissolved. The fundamental units of solutes are usually ions
or molecules.
Water is the most important solvent, and compounds
dissolved in water are said to be in aqueous solution.
Solution
In reality, any combination of the three states can be
considered a solution.
Usually a solution is formed by dissolving a solid
(e.g., sugar) in a liquid (e.g., water).
Air is a solution which is a mixture of various gases.
Carbonated water (soda) is a mixture of a gas (CO2)
dissolved in a liquid (H2O).
Even alloys such as gold-silver alloys are solutions
containing two solids.
A true solution is a solution which has only one solvent
with one or more solutes.
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Determinants of solubility
Many combinations display solubility that is between the two
extremes of miscible and insoluble. In other words, the
substance dissolves, but there is a limit to the amount of
solute that will dissolve in a given amount of solvent.
Concentrations of solutions are expressed in terms of either
the amount of solute present in a given mass or volume of
solution, or the amount of solute dissolved in a given mass or
volume of solvent.
Percent by mass
Concentrations of solutions may be expressed in terms of
percent by mass of solute, which gives the mass of solute per
100 mass units of solution. The gram is the usual mass unit.
percent sulute =
mass of solute
x 100%
mass of solution
Molarity =
Molality =
moles of solute
kilograms of solvent
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Normality
The normality, N, of a solution is the number of
equivalents of solute per liter of solution.
The equivalent is usually defined in terms of a chemical
reaction. For acid-base reactions, an equivalent is the
amount of substance that will react or form 1 mole of
hydrogen (H+) or hydroxide (OH-) ions. For redox
(oxidation-reduction) reactions, an equivalent is the amount
of substance that will react or form 1 mole of electrons.
Normality =
number of equivalents
1 liter of solution
N = nM
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Exercise
How many grams of H2O must be used to dissolve 50
grams of sucrose to prepare a 1.25 m solution of sucrose,
C12H22O11?
Ans:
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Exercise
Hydrogen peroxide disinfectant typically contains 3.0%
by mass. Assuming that the rest of the contents is water,
what is the molality of this disinfectant?
Ans:
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Dissolution of liquids
Water and methanol are alike in that both substances contain
O-H groups that form hydrogen bonds readily. When these
liquids are mixed, H2O... H2O hydrogen bonds and CH3OH...
CH3OH hydrogen bonds break, but H2O...CH3OH hydrogen
bonds form.
The net result is that the degree of hydrogen bonding in the
solution is about the same as in either of the pure liquids,
making these two liquids miscible.
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Dissolution of liquids
The intermolecular interactions of
octane and cyclohexane are alike.
Octane and cyclohexane have low
polarities, so these molecules in the
pure liquids are held together by the
dispersion forces caused by their
polarizable electron clouds.
Dispersion forces in solutions of
octane and cyclohexane are about
the same as in the pure liquids. So
these two liquids are miscible.
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Dissolution of liquids
Water and octane are not alike and nearly insoluble in each other.
Octane does not form hydrogen bonds, so the only forces of
attraction between water molecules and octane molecules are
dispersion forces.
Because hydrogen bonds are stronger than dispersion forces, the
cost of disrupting the hydrogen-bonding network in water is far
greater than the stability gained from octanewater dispersion
forces.
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Dissolution of liquids
Some liquids can interact with other
substances in multiple ways. Acetone, for
instance, has a polar CO bond and a
three-carbon bonding framework.
The bonding framework is similar to that
of a hydrocarbon, so acetone mixes with
cyclohexane and octane.
The polar CO group makes acetone
miscible with other polar molecules such
as acetonitrile .
The polar oxygen atom in acetone has
lone pairs of electrons that can form
hydrogen bonds with hydrogen atoms of
ammonia or water.
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Exercise
Give a molecular explanation for the following trend in alcohol
solubilities in water:
n-Propanol
n-Butanol
n-Pentanol
n-Hexanol
CH3CH2CH2OH
Completely miscible
CH3CH2CH2CH2OH
1.1 M
CH3CH2CH2CH2CH2OH
0.30 M
0.056 M
CH3CH2CH2CH2CH2CH2OH
Strategy
Solubility limits depend on the stabilization generated by
solutesolvent interactions balanced against the destabilization
that occurs when solventsolvent interactions are disrupted by
solute.
Intermolecular interactions involving water and alcohol
molecules must be examined.
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Dissolution of gases
The only gases that dissolve appreciably in water are:
(1) those that are capable of hydrogen bonding (such as HF),
(2) those that ionize (such as HCl, HBr, and HI),
(3) those that react with water (such as CO2).
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Colloids
Particles whose dimensions are between 1 nanometer and 1
micrometer, called colloids, are larger than the typical
molecule but smaller than can be seen under an optical
microscope.
When a colloid is mixed with a second substance, the colloid
can become uniformly spread out, or dispersed, throughout
the dispersing medium. Such a dispersion is a colloidal
suspension that has properties intermediate between those of
a true solution and those of a heterogeneous mixture.
Mixture
suspension
colloidal dispersion
solution
Example
sand in water
starch in water
sugar in water
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Types of colloids
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AcidBase
The Arrhenius theory (1884)
An acid is a substance that contains hydrogen and produces
H in aqueous solution.
A base is a substance that contains the OH (hydroxyl) group
and produces hydroxide ions, OH, in aqueous solution.
Neutralization is defined as the combination of H ions with
OH ions to form H2O molecules.
H+ (aq) + OH- (aq) H2O (l) (neutralization)
The hydronium ion (hydrated hydrogen ion)
The hydrated hydrogen ion is the species that gives aqueous
solutions of acids their characteristic acidic properties.
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AcidBase
The BrnstedLowry theory (1923)
An acid is defined as a proton donor and a base is defined as a
proton acceptor.
An acidbase reaction is the transfer of a proton from an acid to
a base.
The ionization of hydrogen chloride, HCl, in water is an acid
base reaction in which water acts as a base or proton acceptor.
We can describe BrnstedLowry acidbase reactions in terms
of conjugate acidbase pairs. These are two species that differ
by a proton.
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AcidBase
The Lewis theory (1923)
An acid is any species that can accept a share in an electron
pair. A base is any species that can make available, or
donate, a share in an electron pair.
These definitions do not specify that an electron pair must
be transferred from one atom to anotheronly that an
electron pair, residing originally on one atom, must be
shared between two atoms. Neutralization is defined as
coordinate covalent bond formation.
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Chemical equilibrium
Reactions that do not go to completion and that can occur in
either direction are called reversible reactions.
rate f = k f [C ] [D ]
c
rate r = k r [A ] [B ]
a
[C ]eq [D ]eq
kf
=
a
b
k r [A ]eq [B ]eq
c
Kc
[C ] [D ]
=
[A ] [B ]
c
eq
a
eq
b
eq
eq
(For any pure liquid or pure solid, the activity is taken as 1.)
Both kf and kr are constant, so kf/kr is also a constant and
given a special name and symbol the equilibrium constant, Kc
or simply K.
G o = RTlnK
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Exercise
Ans:
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Exercise
Calculate [H3O+ ], pH, [OH -], and pOH for a 0.015 M
Ca(OH)2 solution.
Ans:
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[H O ][A ]
=
+
Ka
[HA]
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Exercise
Find the degree of ionization of 0.1 M solution of acetic
acid (CH,COOH). Also find the pH of the solution.
(The acid-ionization constant of acetic acid is 1.8 x 1 0-5)
Ans:
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Just like the acid-ionization constant, there is also the baseionization (Kb)
[NH ][OH ]
+
Kb =
[NH ]
3
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Common-ion effect
When a salt is added to a solution containing either the same
cation or anion, there will be changes in the solubility
because of what is commonly known as common-ion effect.
The phenomenon can be best explained in terrns of Le
Chatelier's principle.
For ex. adding magnesium fluoride (MgF2) to a solution of
sodium fluoride (NaF).
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Solubility guidelines
for common ionic compounds in water
Compounds whose solubility in water is less than about 0.02
mol/L are usually classified as insoluble compounds.
No gaseous or solid substances are infinitely soluble in water.
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Solubility guidelines
for common ionic compounds in water
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Ksp = [Mz+]y[Xy-]z
In general, the solubility product expression for a compound is
the product of the concentrations of its constituent ions, each
raised to the power that corresponds to the number of ions in
one formula unit of the compound. The quantity is constant at
constant temperature for a saturated solution of the compound.
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Ion product
Ion product (reaction quotient, Qsp) is the product of the
concentrations of the ions from the compound (solute) in a
solution, each concentration raised to a power equal to its
coefficient in the balanced equation. In other words, the
expression for the ion product is the same as that of Ksp.
By comparing the ion product of a compound against its Ksp,
we can predict whether or not precipitation is likely to occur.
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Exercise
If 100 mL of 0.00075 M sodium sulfate, Na2SO4, is mixed
with 50 mL of 0.015 M barium chloride, BaCl2, will a
precipitate form? (Ksp for BaSO4 = 1.1 x 10-10).
Ans:
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Buffers
A solution which resists changes in pH when small amounts of
acid or base are added to it is called a buffer solution.
A buffer solution is usually a mixture of a weak acid and its
conjugate base or a weak base and its conjugate acid. A buffer
solution contains equilibrium amounts of acid and base species.
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Buffers
Buffers do not have unlimited capacity to resist pHchange. The buffer capacity of a buffer depends on the
nature of the buffer and the amount of acid and conjugate
base present in the solution.
The Henderson-Hasselbalch equation can be used to relate
the pH of a buffer and the concentrations of base and acid.
For a weak acid-conjugate base buffer:
pH = pK a + log
[conjugate base]
[weak acid]
[conjugate acid]
[weak base]
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Exercise
Calculate the concentration of H3O+ and the pH of a buffer
solution that is 0.10 M in CH3COOH and 0.20 M in
NaCH3COO.
Ans:
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Indicator
Methyl red is red at pH 4 and below; it is yellow at pH 7
and above. Between pH 4 and pH 7 it changes from red to
redorange, to orange, to yellow.
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Indicator
Bromthymol blue is yellow at pH 6 and below; it is blue at
pH 8 and above. Between pH 6 and 8 it changes from yellow
to yellowgreen, to green, to blue-green, to blue.
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Indicator
Phenolphthalein is colorless below pH 8 and bright pink above
pH 10. It changes from colorless to pale pink, to pink, to
bright pink in the pH range 8 to 10.
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Indicator
The pH at which the color change occurs is characteristic of
each indicator. For an acid-base reaction, the indicator is
chosen based on the pH at which the equivalence point is
expected to occur.
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Summary
After you have studied this module 6, you should be able to
Describe the solution.
Express concentrations of solutions in terms of molality and
mole fractions.
Describe the factors that favor the dissolution process.
Describe the dissolution of solids in liquids, liquids in
liquids, and gases in liquids.
Describe how temperature and pressure affect solubility.
Recognize and describe colloids: the Tyndall effect, the
adsorption phenomenon, hydrophilic and hydrophobic
colloids.
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Summary
Recognize strong electrolytes and calculate concentrations
of their ions.
Recognize and classify acids (strong, weak), bases (strong,
weak, insoluble), and salts (soluble, insoluble); use the
solubility guidelines.
Understand the autoionization of water.
Understand the pH and pOH scales and how they are used.
Use ionization constants.
Describe how polyprotic acids ionize in steps.
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Summary
Explain the common ion effect.
Understand the solution equilibrium with precipitation.
Recognize buffer solutions and describe their chemistry.
Describe how to prepare a buffer solution of a specified
pH.
Carry out calculations related to buffer solutions and their
action.
Explain what acidbase indicators are and how they
function.
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