Inorganic Chemistry Graded Problem Set 8

Acids & Bases Due: Mon. Oct. 27, 2014

1. a. Using Pauling’s Rules estimate the pK1 values for each of the following acids. List the
following acids in order of acid strength in aqueous solution:
HReO4 H3SbO4 H2SeO3 H2SeO4
Pauling’s Rules for oxoacids OpE(OH)q pKa ≈ 8 – 5p
acid HReO4 H3SbO4 H2SeO3 H2SeO4
pKa = 8 – 5(3) = –7 8 – 5(1) = 3 8 – 5(1) = 3 8 – 5(2) = –2
So in order of decreasing acid strength
HReO4 > H2SeO4 > H3SbO4 ~ H2SeO3
b. Which of the following oxides are likely to be acidic, basic or amphoteric? Write
balanced equations for their reaction with water (and acid or base if amphoteric).
i) As2O3 ii) TeO2 iii) VO
i) As2O3 is a post transition metal/metalloid which means it is a amphoteric oxide
As2O3 (s) + 3 H2O  2 As(OH)3 (s)
Reaction with base
2As(OH)3 (s) + 3OH– (aq)  2[As(OH)4]2– (aq)
Reaction with acid
2As(OH)3 (s) + 6 H3O+ aq)  2[As(OH2)6]3+ (aq)
ii) TeO2 is a nonmetal oxide which means it is an acidic oxide (acidic anhydride)
TeO2 (s) + H2O  H2TeO3 (aq)  H+ (aq) + HTeO3– (aq)
iii) VO is a transition metal oxide which means it is an basic oxide
VO (s) + H2O  V(OH)2 (s)  V2+ (aq) + 2 OH– (aq)
2. Choose and explain each of the following:
a. Strongest Brønsted acid: SnH4 SbH3 TeH2
b. Strongest Brønsted base: NH3 PH3 SbH3
c. Strongest base to BMe3: pyridine 2-methylpyridine 4-methylpyridine
For binary hydrogen compounds (compounds containing H and one other element) the trends
in acidity are as follows:
1. Within each group (column in periodic table) acidity  on going down the series. The
strongest acid is the largest, heaviest member of the group (as it contains nonmetals of the
lowest ).
2. In any period (row), the strongest acid is the smallest, but heaviest member containing the
nonmetal of highest .
Acidity  with ing number of electrons in the central atom going across or down the table.
Acidity  as  down a column or as  across a row in the periodic table.
 For 1, the lower charge density of the larger atoms means less affinity for H+, so it gives up
H+ readily making it more acidic.
For 2, the stronger acid is the one with more lone pairs over which to spread the negative
charge of the conjugate base.
Using this we see that
a. TeH2 > SbH3 > SnH4
Strongest  Weakest Bronsted base
b. NH3 > PH3 > SbH3
Strongest  Weakest Bronsted base
c. The methyl group on pyridine pushes more electron density into the ring, making N more
negative, a better electron pair donor and thus a stronger base. Donation at the 4-position
is more effective than at the 2-position, so one would expect the basicity to be

N > N > N

4-methylpyridine 2-methylpyridine pyridine

However, with sterically bulky acids such as BMe3, the methyl groups in the 2-position on
pyridine interfere with the approach of the acid. This makes 2-methylpyridine as worse base
than pyridine with respect to BMe3. So for B(CH3)3

N > N > N
~

Strongest  weakest base

3. For each of the following reactions, identify the acid and base. Also indicate which acid-
base definition (Lewis, solvent system, Brønsted) applies. In some cases more than one
definition may apply.
a. HF + HF + SbF5  [H2F]+ + [SbF6]
base adduct acid super acid adduct
Lewis, Bronsted & Solvent system
b. XeO3 + OH  [XeO4H]
acid base adduct
Lewis Acid Base – Adduct formation
c. PtF5 + ClF3  [ClF2]+ + [PtF6]
acid adduct acid adduct
Lewis Acid Base – Single Displacement reaction
Also Solvent system where ClF3 is the solvent.
d. 2 CH3HgI + CaCl2  CaI2 + 2 CH3HgCl
 adduct adduct adduct adduct
SA—SB HA—HB HA—SB SA—HB
Lewis Acid Base – Double Displacement reaction
e. [AgCl2] (aq) + 2CN (aq)  [Ag(CN)2] (aq) + 2 Cl (aq)
adduct base adduct base
SA—HB SB SA—SB HB
Lewis Acid Base – Single Displacement reaction
4. Consider each of the following solvents individually: i) NH2CH3 ii) CF3COOH iii) H2SO4.
a. Give the equation for the autoionization of the pure solvent.
i) 2 :NH2CH3  NH3CH3+ + NHCH3–
ii) CF3COOH  2 CF3COOH2+ + CF3COO–
iii) 2 H2SO4  H3SO4+ + HSO4–
b. Discuss what will happen if H2O is dissolved in each of the solvents, i.e., what ions will
form. Give appropriate equations. Will the solution be acidic or basic with respect to the
pure solvent? Will the solute act as a weak or a strong acid or base with respect to the
solvent?
i) :NH2CH3 + H2O  NH3CH3+ + OH–
base acid conj acid conj base
The solvent is NH2CH3. The solution of H2O in NH2CH3 will be acidic relative to the
pure solvent. The solute, H2O, acts as a weak acid in NH2CH3.
ii) CF3COOH + H2O  H3O+ + CF3COO–
acid base conj acid conj base
The solvent is CF3COOH. The solution of H2O in CF3COOH will be basic relative to
the pure solvent. The solute, H2O, acts as a weak base in CF3COOH.
iii) H2SO4 + H2O  H3O+ + HSO4–
acid base conj acid conj base
The solvent is H2SO4. The solution of H2O in H2SO4 will be very basic relative to the
pure solvent. The solute, H2O, acts as a strong base in H2SO4.
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Recommended Problems
5. Using Pauling’s Rules estimate the pK1 values for each of the following acids. List the
following acids in order of acid strength in aqueous solution:
HClO HClO4 HClO2 HClO3
Pauling’s Rules for oxoacids OpE(OH)q pKa ≈ 8 – 5p
acid HClO HClO4 HClO2 HClO3
pKa = 8 – 5(0) = +3 8 – 5(3) = –7 8 – 5(1) = 3 8 – 5(2) = –2
So in order of decreasing acid strength
HClO4 > HClO3 > HClO2 > HClO
 Or acidity  as the oxidation state of the central atom . More electron density is
pulled from the O’s toward the central atom and thus away from the H, so it
becomes more acidic.
6. Using HSAB theory, choose the better acid or base in the following pairs and explain your
choice:
a. CH3NH2 or NH3 in reaction with H+
H+ is a hard acid as it is a bare proton so not polarizable. NH3 and CH3NH2 are both
listed as hard bases, however the CH3 group makes CH3NH2 a little softer than NH3. The
result is that NH3 is better base for H+
b. Which end of SCN will coordinate to Cr3+; Pt2+?
Cr3+ is a hard acid so it will prefer the harder N end of SCN– (NCS– is an intermediate
base). [Cr—NCS]2+
Pt2+ is a soft acid so will prefer the soft S end of SCN– (SCN– is a soft base). [Pt—SCN]+
c. Boric acid, B(OH)3, acts as an acid in water, but does not do so via ionization of a proton.
Rather, it serves as a Lewis acid towards OH–. Explain with the use of a balanced
equation.
B(OH)3 is a Lewis Acid, thus it accepts a pair of electrons from a Lewis base to form an
adduct. In water this translates to

B(OH)3 O [B(OH)4] H+
H H
Or
B(OH)3 + OH–  [B(OH)4] –
7. The hydroxoacid Si(OH)4 is a weaker acid than H2CO3. pKa[Si(OH)4] = 10 and pKa[H2CO3]
= 3.6. Metal silicates M2SiO4 (where M = Mg2+, Ca2+, etc) form the basis of many minerals
and ocean sediments. Write balanced equations for the dissolution of M2SiO4 in water
containing dissolved CO2. Given these equations, explain how silicates dissolved in ocean
sediments might limit the increase in CO2 in the atmosphere that lead to the greenhouse
effect.
pKa [Si(OH)4] = 10 pKa [H2SO4] = 3.6

CO2 (g) + H2O (l) H2CO3 (aq) H+ (aq) + HCO3– (aq)

M2SiO4 (s) + H2CO3(l) 2 M2+ (aq) + [HSiO4]3– (aq) + HCO3– (aq)

[HSiO4]3– (aq) + HCO3– (aq) [H2SiO4]2– (aq) + CO32– (aq)

M2+ (aq) + CO32– (aq) MCO3 (s) M = Mg2+, Ca2+, etc.

Silicates dissolved in ocean water, might limit the  of CO2 in atmosphere, by precipitating
out the CO2 as metal carbonate salts.
8. Using Brønsted acid-base theory, identify the acids and bases in the following reactions.
a. H2SO4 + [ClO2]–  HClO2 + [HSO4]–
acid base acid base
b. AgNO3 + CH3SH  HNO3 + CH3SAg
base acid acid base
c. CdCl2 + H2Te  2 HCl + CdTe
base acid acid base
d. 2 HF + PF5  H2F+ + PF6–
acid base acid base
9. For each of the following reactions, identify the acid and base. Also indicate which acid-
base definition (Lewis, solvent system, Brønsted) applies. In some cases more than one
definition may apply.
a. HNO2 + 2 HF  [H2NO2]+ + [HF2]
base acid adduct acid base
HA—HB HA—HB SA—SB HB
Solvent system, Bronsted and Lewis Acid Base
b. Li3N + 2 NH3  3 Li+ + 3 NH2–
adduct acid acid base
HA—HB HA HA HB
Solvent system, Lewis Acid Base, Bronsted
Bronsted: N = base (proton acceptro) and NH3 is the acid (Proton donor)
c. Al2Cl6 + 2 NH3  2 H3NAlCl3
acid base adduct
HA HB HA—HB
Lewis Acid Base – Adduct formation
10. a. Aluminum trifluoride (AlF3) is insoluble in HF, but dissolves when NaF is present.
When BF3 is passed into the solution, AlF3 is precipitated. Account for these observations
using equations. (Is this Autoionization, Bronsted-Lowry or Lewis acid/base?)
AlF3 (s) + 2 HF X AlF4– + H2F+
Acid base conj base conj acid
This reaction does not go to any appreciable extent because H2F+ is an extremely strong
Bronsted acid. So AlF3 (s) is insoluble in pure HF solvent.
However, if NaF (s) is added then a Lewis Acid/Base adduct can form
AlF3 (s) + F– (in HF)  AlF4– (in HF)
LA LB adduct formation
When BF3 is added to the AlF4– (in HF) a Lewis Acid/Base displacement reaction occurs.This
occurs because BF3 is a harder acid than AlF3. Al is below B so more polarizable than B.
The harder acid reacts preferentially with the very hard base, F–.
AlF4– (in HF) + BF3 (in HF)  AlF3 (s) + BF4– (in HF)
A—B A' A A'—B