Self-Study Homework #1 (due by Tuesday, October 29, 2013)

Show all your work! Problems are taken from 5

th
edition.

7-2. An organic compound with a molecular mass of 417 was analyzed for ethoxyl (CH3CH2O

) groups by
the reactions
ROCH2CH3 + HI ROH + CH3CH2I (R: remainder of molecule)
CH3CH2I + Ag
+
+ OH

AgI(s) + CH3CH2OH
A 25.42-mg sample of compound produced 29.03 mg of AgI (FM 234.77). How many ethoxyl groups are
there in each molecule?

7-7. Twenty dietary iron tablets with a total mass of 22.131 g were ground and mixed thoroughly. Then
2.998 g of the powder were dissolved in HNO3 and heated to convert all the iron to Fe
3+
. Addition of NH3
precipitated Fe2O3xH2O, which was ignited to give 0.264 g of Fe2O3 (FM 159.69). What is the average mass
of FeSO47H2O (FM 278.01) in each tablet?

7-11. Write a balanced equation for combustion of benzoic acid, C6H5CO2H, to give CO2 and H2O. How many
milligrams of CO2 and of H2O will be produced from 4.635 mg of benzoic acid?

7-12. Combustion of 8.732 mg of an unknown organic compound gave 16.432 mg of CO2 and 2.840 mg of
H2O. (a) Find the wt% C and H in the substance. (b) Find the smallest reasonable integer mole ratio of C:H
in the compound.

7-16. A mixture of Al2O3(s) and CuO(s) weighing 18.371 mg was heated under H2(g) at 1 000C to give
17.462 mg of Al2O3(s) + Cu(s). The other product is H2O(g). Find wt% Al2O3 in the original mixture.

8-1. Identify the conjugate acid-base pairs in the following reactions:
(a) CN

+ HCO2H HCN + HCO2

(b) PO4
3
+ H2O 4
2
+ OH

(c) HSO3

+ OH

SO3
2
+ H2O

8-3. Find the pH of a solution containing
(a) l0
4
M H
+
(b) l0
5
M OH

(c) 5.8l0
4
M H
+
(d) 5.8l0
4
M OH

8-6. An acidic solution containing 0.010 M La
3+
is treated with NaOH until La(OH)3 precipitates. Use the
solubility product for La(OH)3 to find the concentration of OH

when La
3+
first precipitates. At what pH does
this occur?

8-14. Hypochlorous acid has the structure HOCl. Write the base hydrolysis reaction of hypochlorite, OCI

.
Given that Ka for HOCI is 3.010
8
, find Kb for hypochlorite.

8-16. Find the concentration of H
+
in a solution whose pH is 11.65.

8-17. Find the pH and fraction of dissociation of a 0.010 0 M solution of the weak acid HA with Ka =
1.0010
3
.

8-19. Calculate the pH of 0.085 0 M pyridinium bromide, C5H5NH
+
Br

. Find the concentrations of pyridine

(C5H5N), pyridinium ion (C5H5NH
+
), and Br

in the solution.

8-21. A 0.100 M solution of the weak acid HA has a pH of 2.36. Calculate pKa for HA.

8-31. Find the pH and fraction of association of 0.026 M NaOCl.

9-3. A solution contains 63 different conjugate acid-base pairs. Among them is acrylic acid and acrylate ion,
with the ratio [acrylate]/[acrylic acid] = 0.75. What is the pH of the solution?

H2C=CHCO2H H2C=CHCO2

+ H
+
pKa = 4.25
Acrylic acid Acrylate

9-4. Table 91 shows the relation of pH to the quotient [A

]/[HA]. (a) Use the Henderson-Hasselbalch

equation to show that pH = pKa + 2 when [A

]/[HA] = 100. (b) Find the quotient [A

]/[HA] when
pH = pKa 3. (c) Find the pH when [A

]/[HA] = 10
4
.

9-6. Given that pKb for iodate ion (IO3

) is 13.83, find the quotient [IO3

]/[HIO3] in a solution of sodium

iodate at (a) pH 7.00; (b) pH 1.00.

9-11. (a) Write the chemical reactions whose equilibrium constants are Kb and Ka for imidazole and
imidazole hydrochloride, respectively. (b) Calculate the pH of a 100-mL solution containing 1.00 g of
imidazole (FM 68.08) and 1.00 g of imidazole hydrochloride (FM 104.54). (c) Calculate the pH of the
solution if 2.30 mL of 1.07 M HCIO4 are added to the solution. (d) How many milliliters of 1.07 M HClO4
should be added to 1.00 g of imidazole to give a pH of 6.993?

9-12. (a) Calculate the pH of a solution prepared by mixing 0.080 0 mol of chloroacetic acid plus 0.040 0
mol of sodium chloroacetate in 1.00 L of water. (b) Using first your head and then the Henderson-
Hasselbalch equation, find the pH of a solution prepared by dissolving all of the following compounds in a
total volume of 1.00 L: 0.180 mol CICH2CO2H, 0.020 mol CICH2CO2Na, 0.080 mol HNO3, and 0.080 mol
Ca(OH)2. Assume that Ca(OH)2 dissociates completely.

9-14. How many milliliters of 0.626 M KOH should be added to a solution containing 5.00 g of HEPES
(Table 9-2) to give a pH of 7.40?

9-17. Which buffer system will have the greatest buffer capacity at pH 9.0: (i)
dimethylamine/dimethylammonium ion, (ii) ammonia/ammonium ion, (iii)
hydroxylamine/hydroxylammonium ion, (iv) 4-nitrophenol/4-nitrophenolate ion?

10-6. Consider the titration of 100.0 mL of 0.100 M NaOH with 1.00 M HBr. What is the equivalence
volume? Find the pH at the following volumes of HBr: Va = 0, 1.00, 5.00, 9.00, 9.90, 10.00, 10.10, and 12.00
mL.

10-8. A 50.0-mL volume of 0.050 0 M weak acid HA (pKa = 4.00) was titrated with 0.500 M NaOH. Write the
titration reaction and find Ve. Find the pH at Vb = 0, 1.00, 2.50, 4.00, 4.90, 5.00, 5.10, and 6.00 mL.

10-11. What is the pH at the equivalence point when 0.100 M hydroxyacetic acid is titrated with 0.050 0 M
KOH?

10-12. When 16.24 mL of 0.064 3 M KOH were added to 25.00 mL of 0.093 8 M weak acid, HA, the
observed pH was 3.62. Find pKa for the acid.

10-13. When 22.63 mL of aqueous NaOH were added to 1.214 g of CHES (FM 207.29, structure in Table 9-
2) dissolved in 41.37 mL of water, the pH was 9.13. Calculate the molarity of the NaOH.

10-14. (a) When 100.0 mL of weak acid HA were titrated with 0.093 8 I M NaOH, 27.63 mL were required
to reach the equivalence point. Find the molarity of HA. (b) What is the formal concentration of A

at the
equivalence point? (c) The pH at the equivalence point was 10.99. Find pKa for HA. (d) What was the pH
when only 19.47 mL of NaOH had been added?

10-20. Would the indicator bromocresol green, with a transition range of pH 3.85.4, ever be useful in the
titration of a weak acid with a strong base? Why?

11-3. The base association constants of phosphate are Kb1 = 0.024, Kb2 = 1.58l0
7
, and Kb3 = 1.41l0
12
.
From the Kb values, calculate Ka1, Ka2, and Ka3 for H3PO4.

11-7. From the Ka values for citric acid in Appendix B, find Kb1, Kb2, and Kb3 for trisodium citrate.

11-8. Write the chemical reactions whose equilibrium constants are Kb1 and Kb2 for the amino acid serine
and find their numerical values.

11-9. Abbreviating malonic acid, CH2(CO2H)2, as H2M, find the pH and concentrations of H2M, HM

, and
M
2
in each of the following solutions: (a) 0.100 M H2M; (b) 0.100 M NaHM; (c) 0.100 M Na2M. For (b), use
the approximation [HM

] = 0. 100 M.

11-11. Calculate the pH of a 0.300 M solution of the dibasic compound piperazine, which we will designate
B. Calculate the concentration of each form of piperazine (B, BH
+
, BH2
2+
).

11-13. Draw the structure of the amino acid glutamine and satisfy yourself that it is the intermediate form
of a diprotic system. Find the pH of 0.050 M glutamine.

11-15. The acid HA has pKa = 7.00. (a) Which is the principal species, HA or A

, at pH 6.00? (b) Which is the

principal species at pH 8.00? (c) What is the quotient [A

]/[HA] at (i) pH 7.00; (ii) at pH 6.00?

11-16. The acid H2A has pKa1 = 4.00 and pKa2 = 8.00. (a) At what pH is [H2A] = [HA

]? (b) At what pH is
[HA

] = [A
2
]? (c) Which is the principal species, H2A, HA

, or A
2
at pH 2.00? (d) Which is the principal
species at pH 6.00? (e) Which is the principal species at pH 10.00?

11-23. Find the pH and concentration of each species of arginine in 0.050 M arginineHCl solution. The
notation "arginineHCl" refers to a neutral arginine molecule that has taken on one extra proton by
addition of one mole of HCl. A more meaningful notation shows the salt (arginineH
+
)(Cl

) formed in the
reaction.