Chapter 7 Acids, bases and ions in aqueous solution
7.1 Introduction Liquid water is approximately 55 molar H2O, 7.2 Properties of water structure Part of the structure of ordinary ice; it consists of a 3-dimensional network of hydrogen-bonded H2O molecules.
The variation in the value of the density of water between 283 and 373 K.
The self-ionization of water If a pure liquid partially dissociates into ions, it is self ionizing. Water as a Brønsted acid or base A Brønsted acid can act as a proton donor, and a Brønsted base can function as a proton acceptor.
Brønsted base Brønsted acid
Activity When the concentration of a solute is greater than about 0.1 mol/dm3, interactions between the solute molecules or ions are significant, and the effective and real concentrations are no longer equal. The relative activity, ai, of a component i is dimensionless i is the activity coefficient of the solute, and mi is the molality
7.4 Some Brønsted acids and bases Carboxylic acids: examples of mono-, di- and polybasic acids
Inorganic acids Each of the hydrogen halides is monobasic and for X = Cl, Br and I, the equilibrium lies far to the right-hand side, making these strong acids Hydrogen fluoride, on the other hand, is a weak acid (pKa = 3.45).
oxoacid Examples of oxoacids include hypochlorous acid (HOCl), perchloric acid (HClO4), nitric acid (HNO3), sulfuric acid (H2SO4) and phosphoric acid (H3PO4). • oxoacids may be mono-, di- or polybasic; • not all the hydrogen atoms in an oxoacid are necessarily ionizable.
It is not possible to isolate pure H2SO3 - sulfurous acid Dr. Said M. El-Kurdi
Inorganic bases: hydroxides Many inorganic bases are hydroxides, and the term alkali is commonly used. The group 1 hydroxides NaOH, KOH, RbOH and CsOH are strong bases, being essentially fully ionized in aqueous solution; LiOH is weaker (pKb = 0.2). Inorganic bases: nitrogen bases
7.5 The energetics of acid dissociation in aqueous solution Hydrogen halides
H2S, H2Se and H2Te the explanation of the trend in values is not simple the decrease in the XH bond strength with the increasing atomic number of X plays an important role as group 16 is descended and X becomes more metallic, its hydride becomes more acidic.
7.6 Trends within a series of oxoacids EOn(OH)m empirical methods for estimating Ka Bell’s rule Which relates the first acid dissociation constant to the number of ‘hydrogen-free’ O atoms in an acid of formula EOn(OH)m.
The increase in acid strength with increase in the number of O atoms attached to atom E is generally attributed to the greater possibility in the conjugate base of delocalization of negative charge onto the O atoms.
7.7 Aquated cations: formation and acidic properties When a metal salt dissolves in water, the cation and anion are hydrated. ion–dipole interaction
Hexaaqua ion each H2O molecule acts as a Lewis base while the metal ion functions as a Lewis acid. the MO interaction is essentially covalent the first hydration shell
Periodic trends in amphoteric properties some elements that lie next to the line ‘diagonal line’ (e.g. Si) are semi-metals
Be(OH)2 and BeO are amphoteric Al2O3, Ga2O3, In2O3, GeO, GeO2, SnO, SnO2, PbO, PbO2, As2O3, Sb2O3 and Bi2O3 are amphoteric. 7.9 Solubilities of ionic salts Solubility and saturated solutions
Sparingly soluble salts and solubility products The energetics of the dissolution of an ionic salt: solGo
7.11 Coordination complexes: an introduction Definitions and terminology The word ligand is derived from the Latin verb ‘ligare’ meaning ‘to bind’. In a coordination complex, a central atom or ion is coordinated by one or more molecules or ions (ligands) which act as Lewis bases, forming coordinate bonds with the central atom or ion; the latter acts as a Lewis acid. Atoms in the ligands that are directly bonded to the central atom or ion are donor atoms.
In a complex: • a line is used to denote the interaction between an anionic ligand and the acceptor; • an arrow is used to show the donation of an electron pair from a neutral ligand to an acceptor.
When a Lewis base donates a pair of electrons to a Lewis acid, a coordinate bond is formed and the resulting species is an adduct. The centred dot in, for example, H3BTHF indicates the formation of an adduct.
Investigating coordination complex formation 7.12 Stability constants of coordination complexes
Stepwise stability constants for the formation of [Al(OH2)6xFx](3x)+ (x = 1–6).
The stabilities of complexes of the non-d-block metal ions of a given charge normally decrease with increasing cationsize . Thus, for a complex with a given ligand, L, the order of stability is Ca2+ > Sr2+ > Ba2+. For ions of similar size, the stability of a complex with a specified ligand increases substantially as the ionic charge increases, e.g. Li+ < Mg2+ < Al3+.
The principle of hard and soft acids and bases (HSAB) • hard, metal ions and ligands containing particular donor atoms exhibit trends in stabilities as follows: • soft, metal ions and ligands containing these donor atoms are:
Pearson’s classification of hard and soft acids comes from a consideration of a series of donor atoms placed in order of electronegativity: A hard acid is one that forms the most stable complexes with ligands containing donor atoms from the left-hand end of the series. The reverse is true for a soft acid.
Polarizability The polarizability, of an atom is its ability to be distorted by an electric field (such as that of a neighboring ion) Fajan’s rules • Small, highly charged cations have polarizing ability. • Large, highly charged anions are easily polarized. • Cations that do not have a noble-gas electron configuration are easily polarized.
Which would be the more polarizable, an Fion or an I ion? Which would be more polarizing, Na+ or Cs+?