1)

(a) What is the pH of a 2.0 molar solution of acetic acid. Ka of acetic acid = 1.8 x 10¯5
(b) A buffer solution is prepared by adding 0.10 liter of 2.0 molar acetic acid solution to 0.1 liter
of a 1.0 molar sodium hydroxide solution. Compute the hydrogen ion concentration of the buffer
solution.
(c) Suppose that 0.010 liter of 0.50 molar hydrochloric acid is added to 0.040 liter of the buffer
prepared in (b). Compute the hydrogen ion concentration of the resulting solution.
2)
H3PO2, H3PO3, and H3PO4 are monoprotic, diprotic and triprotic acids, respectively, and they
are about equal strong acids. HClO2, HClO3, and HClO4 are all monoprotic acids, but HClO2 is
a weaker acid than HClO3 which is weaker than HClO4.
Account for:
(a) The fact that the molecules of the three phosphorus acids can provide different numbers of
protons
(b) The fact that the three chlorine acids differ in strengths.
3)
A comparison of the theories Arrhenius, Brønsted and Lewis shows a progressive generalization
of the acid base concept. Outline the essential ideas in each of these theories and select three
reactions, one that can be interpreted by all three theories, one that can be interpreted by two of
them, and one that can be interpreted by only one of the theories. Provide these six
interpretations.
4)
Give the formulas to show the reactants and the products for FIVE of the following chemical
reactions.
Example: A strip of magnesium is added to a solution of silver nitrate.
Mg + Ag+ ---> Mg2+ + Ag
a) a mixture of solid calcium oxide and solid tetraphosphorus decaoxide is heated.
b) solid barium peroxide is added to cold dilute sulfuric acid.
c) dilute acetic acid solution is added to solid magnesium carbonate.
d) the hydrocarbon hexane is burned in excess oxygen.
e) solid magnesium nitride is added to excess deuterium oxide.
f) gaseous hydrofluoric acid reacts with solid silicon dioxide
g) potassium dichromate solution is added to an acidified solution of sodium sulfite.
h) dilute hydrochloric acid is added to a solution of diamminesilver(I) nitrate
5)
Account for the observation that silver dissolves in 1 molar hydroiodic acid despite the fact that
the standard electrode potential for the change, Ag <===> Ag+ + e¯ is - 0.80 volt.
6)
Why are solutions of thiosulfate for analysis not acidic? Refer to the following standard electrode
potentials and write the balanced equation that would account for this fact.
Equation E°
2
2 S + 6 OH¯ <===> S2O3 ¯ + 3 H2O + 4e¯ + 0.74 V
2 2
S2O3 ¯ + 6 OH¯ <===> 2 SO3 ¯ + 3 H2O + 4e¯+ 0.58 V
S2O32¯ + H2O <===> 2 SO2 + 2 H+ + 4e¯ - 0.40 V
2 S + 3 H2O <===> S2O32¯ + 6 H+ + 4e¯ - 0.50 V
7)
Zn <===> Zn2+ + 2e¯ E° = +0.76 V
Cu <===> Cu2+ + 2e¯ E° = -0.34 V
The solubility of H2S in water is approximately 0.1-molar.
Zn(OH)2(s) + 2 OH¯ <===> Zn(OH)42¯ K = 4.5 x 10¯2
2
Cu(OH)2(s) + 2 OH¯ <===> Cu(OH)4 ¯ K = 1.6 x 10¯3
Ksp of ZnS = 10¯23, Ksp of CuS = 10¯44
A solution is approximately 1 molar in Cu2+ and 1 molar in Zn2+. Based on the data above,
outline three different methods for separating them discussing the theoretical bases for these
separations.
8)
Explain why in aqueous solution,

(a) Ti3+ is colored but Sc3+ is not.

(b) Ti2+ is a reducing agent but Ca2+ is not.

9)
What is meant by the lanthanide contraction? Account for this phenomenon. Give two examples
of its consequences.
10)
What is meant by the lattice energy of an ionic compound? What quantities need to be
determined and how are they used to calculate the lattice energy of an ionic compound.
11)
A 2.000 gram sample containing graphite (carbon) and an inert substance was burned in oxygen
and produced a mixture of carbon dioxide and carbon monoxide in the mole ratio 2.00 : 1.00.
The volume of oxygen used was 747.0 milliliters at 1,092 K and 12.00 atmospheres pressure.
Calculate the percentage by weight of graphite in the original mixture.
12)
Consider the first ionization of sulfurous acid: H2SO3(aq) <===> H+(aq) + HSO3¯(aq)
Certain related thermodynamic data are provided below:
H2SO3(aq) H+(aq) HSO3¯(aq)
H f°
-145.5 0 -151.9
(kcal/mole)
S°
56 0 26
(cal/mole K)
(a) Calculate the value of DG° at 25 °C for the ionization reaction.
(b) Calculate the value of K at 25 °C for the ionization reaction.
(c) Account for the signs of DS° and DH° for the ionization reaction in terms of the molecules
and ions present.