TA-Rayner-Canham6e ArtPPT Chapter07

Descriptive
Inorganic
Chemistry
Sixth Edition
ART
POWERPOINT
PRESENTATIONS
Chapter 7
PHYSICAL CHEMISTRY:
DESCRIPTIVE INORGANICQUANTA, MATTER,
CHEMISTRY AND CHANGE
6E| GEOFF 2E| PETER ATKINS|
RAYNER-CANHAM| JULIO DE PAULA | RONALD FRIEDMAN
TINA OVERTON
©2014
©2014 W. H.
W. H. FREEMAN
FREEMAN AND
D COMPANY
COMPANY
CHAPTER 7: Solvent Systems and Acid-Base Behavior
7.1 Solvents
7.2 Brønsted-Lowry Acids and Bases
7.3 Trends in Acid-Base Behavior
7.4 Acid-Base Reactions of Oxides
7.5 The Lewis Theory
7.6 Pearson Hard-Soft Acid-Base Concepts
7.7 Applications of the HSAB Concept
7.8 Biological Aspects
PHYSICAL CHEMISTRY:
TINA OVERTON
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CHAPTER 7: CONTEXT 7.1
In ionic liquids (IL), the cation-anion attraction is very weak and the
lattice energy is so low that they are liquid at room temperature.
Due to the ionic nature of IL, they have high vaporization energies.
Combination of these properties make ILs potentially recyclable

(green).
1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6)
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CHAPTER 7: TABLE 7.1
ability to distort
7.1 Solvents electrostatic field
polar protic
dipolar aprotic
nonpolar
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CHAPTER 7: FIGURE 7.1
Representation of the dissolving process for sodium chloride in water.
solvent-solute
interaction
solute-solute
interaction
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CHAPTER 7:
Polar Protic Solvents

Contain one of the three very polar bonds H—F, O—H, or N—H.
Solubility depends on the ion-dipole attractions being stronger
than the lattice energy.
Autoionization
A small proportion of the solvent molecules undergo hydrogen
ion exchange reactions to give their conjugate acid and base.
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CHAPTER 7:
Polar Protic Solvents contd.
Acid-Base Reactions
An acid is a solute that, either by direct dissociation or by

reaction with the solvent, gives the cation characteristic of the
solvent.
Similarly, a base is a solute that, either by direct dissociation or

by reaction with the solvent, gives the anion characteristic of
the solvent.
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CHAPTER 7:
Polar Protic Solvents contd.
Dissociation
The term dissociation means “separation” and is used when a
solvent such as water separates the ions that are present in
ionic compounds.
Ionization
Inorganic acids contain covalent bonds. Solution in water results
in ionization, the breaking of the covalent bonds resulting in ion
formation.
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CHAPTER 7:
Dipolar Aprotic Solvents

Aprotic solvents function by being strong Lewis acids or bases.
Lewis acid
Lewis base
Nonpolar Solvents
They will not dissolve ionic compounds but will dissolve a wide
range of covalently bonded uncharged species.
The dispersion-force interaction between solute and solvent is
greater than that between molecules of the elements
themselves.
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7.2 Brønsted-Lowry Acids and Bases

An acid is a hydrogen ion donor and a base is a hydrogen ion acceptor.
The stronger the acid, the more negative the pKa.
Acid ionization constants of various inorganic acids
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Strengths of Acids
In water, all the strong acids seem equally strong, undergoing close to 100
percent ionization; that is, water acts as a leveling solvent.
A weaker base (often a weak acid) will function as a differentiating solvent
for acids.
Correlation between the acid strengths of the hydrohalic (binary)
acids and the energies of the hydrogen-halogen bonds.
Note: O—H bond energy is 459 kJ/mol

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Oxoacids
Ternary acids containing oxygen. For all the common inorganic acids, the
ionizable H atoms are covalently bonded to O atoms.
(HO)nXOm, then when m=0, the value of pKa for the first ionization is
about 8; for m=1, about 2; for m=2, about -1; and for m = 3, about -8.
Nitric acid (a) is a stronger acid

than nitrous acid (b) because the
electron flow away from the H—O
bond is greater in nitric acid.
Polyprotic Acids
Several acids, including sulfuric acid and phosphoric acid, have more
than one ionizable hydrogen atom. The successive ionizations always
proceed to a lesser and lesser extent.
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Brønsted-Lowry Bases
Hydrogen ion acceptor. After the hydroxide ion itself, ammonia is
the next most important Brønsted-Lowry base.
Base ionization constants of various inorganic bases
6.79<7
base
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7.3 Trends in Acid-Base Behavior

The Acidity of Metal Ions
As the charge density increases, that is, with smaller ions and more highly
charged ions, the lone pairs on the oxygen become strongly attracted to the
metal ion, essentially forming a covalent bond.
A comparison of sodium, magnesium, and aluminum species.
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CHAPTER 7: TABLES 7.6 and 7.7
The Basicity of Nonmetal Anions

The halide ions (with the exception of fluoride) are neutral, just as the
alkali metals (except lithium) are neutral.
A comparison of fluoride and chloride aqueous species.
A comparison oxide and sulfide aqueous species.
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The Basicity of Oxoanions

Just as the acidity of oxyacids depends on the number of oxygen atoms
and on the number of hydrogen atoms, so the basicity of the
corresponding anion depends on the number of oxygen atoms and on
the ion charge.
As n decreases, the basicity increases.
Basicity of some common XOn- oxyanions
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As the charge increases, the basicity increases.
Basicity of some common XO4- oxyanions
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As the charge increases, the basicity increases.
A comparison of phosphate, sulfate, and perchlorate aqueous species
A comparison of carbonate and nitrate aqueous species
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7.4 Acid-Base Reactions of Oxides

Acid-base properties of the highest oxides of the Period 3 elements
Acid-base properties of the highest oxides of the Period 3 elements contd.
Acid-base properties of the highest oxides of the Group 15 elements
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Lux-Flood Theory
Lux-Flood theory is a special theory that is devoted to solventless

acid-base reactions, such as those of oxides. Oxides are classified as
acids or bases according to their location in the periodic table.
Lux-Flood assignment of
acidity and basicity of oxides
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CHAPTER 7: UN FIGURE 7.1
7.5 The Lewis Theory

Lewis theory is much broader than Brønsted-Lowry theory. A
Lewis acid is an electron-pair acceptor, while a Lewis base is an
electron-pair donor.
Main Group Reactions
Metal Ion Complex Formation: interaction seems to become less

electrostatic and more covalent as the charge density increases or when
the cation does not have a noble gas electron configuration.
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7.6 Pearson Hard-Soft Acid-Base Concepts

1. Hard acids are characterized by low electronegativities and often high
charge densities.
2. Soft acids have low charge densities and tend to have among the
highest electronegativities of the metallic elements (lower-right
metals).
3. Borderline acids are found on the divide between soft and hard acids.
4. Hard bases have comparatively high charge densities.
5. Soft bases are less electronegative nonmetals (low charge density).
6. Borderline bases, the categories are not rigidly divided.
Common hard, borderline, and soft bases
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Classification of the HSAB acid ions into hard (white), borderline (mauve),
and soft (black).
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7.7 Applications of the HSAB Concept

The most important application of the HSAB concept is in the
prediction of chemical reactions.
We can also use the HSAB concept in the interpretation of

solubility patterns.
Solubilities of sodium and silver halides (mol/L)
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The modified geochemical classification of the chemical elements into lithophiles (oxides,
white), chalcophiles (sulfides, mauve), and siderophiles (metallic phase of the Earth’s core,
black) according to their common surface combinations. The atmophiles and those
elements that do not have stable isotopes have been deleted from the table.
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7.8 Biological Aspects

The environmentally toxic nonmetals and semimetals arsenic, selenium,
and tellurium are very soft bases. Their preferential binding to borderline
acids such as iron(II) and zinc, may prevent the metals from performing
their essential roles in enzymes.
Elements that are regarded as particularly toxic (black).

PHYSICAL CHEMISTRY:
TINA OVERTON
©2014
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CHAPTER 7:
Suggested Study Problems
7.11, 7.12, 7.16, 7.18, 7.19, 7.26, 7.27, 7.31,

7.32, 7.50
PHYSICAL CHEMISTRY:
TINA OVERTON
©2014
©2014 W. H.
W. H. FREEMAN
FREEMAN AND
D COMPANY
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Descriptive

Combination of these properties make ILs potentially recyclable

1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6)

Representation of the dissolving process for sodium chloride in water.

Polar Protic Solvents

An acid is a solute that, either by direct dissociation or by

Similarly, a base is a solute that, either by direct dissociation or

Dipolar Aprotic Solvents

7.2 Brønsted-Lowry Acids and Bases

The stronger the acid, the more negative the pKa.

Acid ionization constants of various inorganic acids

Note: O—H bond energy is 459 kJ/mol

Nitric acid (a) is a stronger acid

7.3 Trends in Acid-Base Behavior

A comparison of sodium, magnesium, and aluminum species.

The Basicity of Nonmetal Anions

A comparison of fluoride and chloride aqueous species.

A comparison oxide and sulfide aqueous species.

The Basicity of Oxoanions

Basicity of some common XOn- oxyanions

As the charge increases, the basicity increases.

Basicity of some common XO4- oxyanions

As the charge increases, the basicity increases.

A comparison of phosphate, sulfate, and perchlorate aqueous species

A comparison of carbonate and nitrate aqueous species

7.4 Acid-Base Reactions of Oxides

Acid-base properties of the highest oxides of the Period 3 elements contd.

Acid-base properties of the highest oxides of the Group 15 elements

Lux-Flood theory is a special theory that is devoted to solventless

7.5 The Lewis Theory

Metal Ion Complex Formation: interaction seems to become less

7.6 Pearson Hard-Soft Acid-Base Concepts

7.7 Applications of the HSAB Concept

We can also use the HSAB concept in the interpretation of

7.8 Biological Aspects

Elements that are regarded as particularly toxic (black).

Suggested Study Problems

7.11, 7.12, 7.16, 7.18, 7.19, 7.26, 7.27, 7.31,

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