Homework #5: Answer Key

4.2 Identify conjugate bases corresponding to the following acids (HSO4-, H2PO4-)

Acid: HSO4- Conjugate Base: SO42-

Acid: H2PO4- Conjugate Base: HPO42-

4.13 Draw the structures and indicate the charges of the tetraoxoanions of X=
Si, P, S, and Cl. Summarize and account for the trends in the pKa values of
their conjugate acids.

Structure of tetraoxoanions of X= Si, P, S, and Cl.

pKa: Compound increases in acidity as you go from 4- to 1- complexes (Si  Cl).

This increase in acidity is due to high oxidation state of the electronegative atom in
the middle of the oxoanion complex. Additionally, as you move from Si to Cl you
increase the number of oxo groups on the element, thereby reducing the pKa of the
complex.

4.14f Which member of the following pairs is the stronger acid? Give reasons
for your choice.

f. H3PO4 or H2SO4  H2SO4 (more oxo groups on sulfur, same as question

4.13 - - reasoning similar just an application)

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 4.15 Arrange the oxides Al2O3, B2O3, BaO, CO2 Cl2O7, SO3 in order from the
most acidic through amphoteric to the most basic.

Strengths of oxoacids usually increase as the charge of the metal ion increases and
with decreasing ionic radius.

Ba = 2+, Al = 3+, B = 3+ (smaller than Al)

Cl2O7 > SO3 > CO2 > B2O3 > Al2O3 > BaO

4.27 Using hard-soft concepts, which of the following reactions are predicated
to have an equilibrium constant greater than 1? Unless otherwise stated,
assume gas-phase or hydrocarbon solution and 250C.

R3PBBr3 + R3NBF3  R3PRBF3 + R3NBBr3 (less than one)

SB:SA + HB:HA

SO2 + (C6H5)3P:HOC(CH3)3  (C6H5)3PSO2 + HOC(CH3)3 (greater than one)

CH3HgI + HCl  CH3HgCl + HI (less than one)

SB:SA + HB:HA

[AgCl2]2- + 2 CN-1  [Ag(CN)2]- + 2Cl- (greater than one)

(if confused see Table 4.5 in the text book)

4.12 Predict whether the equilibrium constants for the following reactions
should be greater than 1 or less than 1:

NH-2 (aq) + H2O (l)  NH3 (aq) + OH- (aq) (greater than one)

Chapter 4 Questions:

A. Give an example of an acidic, a basic, and an amphoteric oxide from

the same family of the Periodic Table.
Al2O3 is amphoteric

Al2O3 + HClO4  2Al3+ + 3H2O + 6ClO4- dissolves in acid

Al2O3 + 3H2O + OH-  2Al(OH)4- dissolves in base

Above Al there is only one acidic oxide: H3BO3 will dissolve in

hydroxide as seen in lab, weakly acidic.

Below there are several options for basic oxides (e.g. Ga2O3

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 In general with the formula M2O3 as the size of the metal decreases
the acidity increases and down a group the basicity increases.

B. Arrange the following binary oxides in order of increasing Bronsted

acidity in aqueous solution. Cite a periodic trend or property that
motivates your answer. Which of the series is most likely to be
amphoteric?

CaO, MgO, Al2O3, SiO2 CO2

C. Predic the thermodynamically favorable direction for each of the

following, and account for your reasoning.

(i) CH3OH (g) + HCl (g)  CH3Cl (g) + H2O (g)

This reaction favors the right because H+ is a harder acid than CH3+
and OH- is a harder base than Cl-.

(ii) 5 PF3 (g) + 3 PCl5 (s)  5 PCl3 (l) + 3 PF5 (g)

This reaction will favor the right because P(V) is a harder acid than
P(III) and F- is a harder base then Cl-.

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 D. Identify the following as Lewis acids or bases and rank them in
order of increasing hardness. Explain your reasoning.

Chapter 5:
5.1 Assigning oxidation states

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 5.6 Balancing reactions

5.9c N2O is bubbled through NaOH (Basic solution)

According to the frost diagram N2O will disproportionate to N2 and NO3-

5.11c

5.16

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 5.17

5.9c (Problem) From class 3/21/11

E. The figure below is part of the modified Latimer diagram for

nitrogen under conditions of 1.0 M OH- (aq). Identify the species in the
Latimer diagram provided that are unstable with respect to
disproportionation in 1.0 M hydroxide. State your reasoning.

NO3-/NO2- will reduce NO2-/N2 therefore NO2- is unstable

NO2-/NO will reduce NO/N2 therefore NO is unstable

Calculate x  x = [2(0.01) + (-0.46) + 2(0.85)]/5 = 0.252 V

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 F. Chlorine reacts with aqueous bromide ion in acid solution to give a
red liquid A and another product B. In base A converts to a mixture of
bromide ion and a second bromine-containing species C. In base
perbromate ion reacts with bromide to generate essentially one
bromine-containing product C. Identify the chemical species A, B, and C.
Hint: Figure 17.14 in the text may be useful.

2 NaBr + Cl2  Br2 + 2 NaCl (aq)

A = Br2; B = NaCl

Br2  BrO3- + Br- ; C = BrO3-

BrO4- + Br-  BrO3-

Cl2 is doing the oxidixing and Br2(l) is the resulting red color of the liquid. The Frost
diagram shows that Br2 is unstable (fully capable of disproportionating) in the
presence of a base. Additionally, the Frost diagram also shows that BrO3- won’t
disproportionate to BrO4- and Br- (therefore conproportionation is expected for
these two molecules back to the bromate ion.

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