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nolphthalein end point. The titrated solution was evaporated to dryness.

Calculate the molar mass of the


acid if the sodium salt was found to weigh 0.2110 g. Assume the acid contained a single titratable
proton.

* 12-29. A 3.00-L sample of urban air was bubbled through a solution containing 50.0 mL of 0.01 16 M
Ba(OH)2, which caused the CO2 in the sample to precipitate as BaCO3. The excess base was back-titrated
to a phenolphthalein end point with 23.6 mL of 0.0108 M HCI. Calculate the parts per million of CO2 in
the air (that is, mL CO2/10^6 mL air); use 1.98 g/L for the density of CO2.

12-30. Air was bubbled at a rate of 30.0 L/min through a trap containing 75 mL of 1% H2O2 (H202 + SO2
-> H2SO4). After 10.0 min, the H2SO4 was titrated with 11.1 mL of 0.00204 M NaOH. Calculate the parts
per million of SO2 (that is, mL SO2/10^6 mL air) if the density of SO2 is 0.00285 g/mL.

*'12-31. The digestion of a 0.1417-g sample of a phosphoruscontaining compound in a mixture of HNO3


and H2SO4 resulted in the formation of CO2, H2O, and H3PO4. Addition of ammonium molybdate
yielded a solid having the composition (NH4)3PO4 12MoO3 (1876.3 g/mol). This precipitate was tiltered,
washed, and dissolved in 50.00 mL of 0.2000 M NaOH:

(NH4)3PO4 12MoO3 + 26OH- ->.......

After the solution was boiled to remove the NH3 the excess NaOH was titrated with 14.17 mL of 0.1741
M HCI to a phenolphthalein end point. Calculate the percentage of phosphorus in the sample.

* 12-32. A 0.8160-g sample containing dimethylphthalate, C6H4(COOCH3)2 (194.19 g/mol), and


unreactive species was refluxed with 50.00 mL of 0.1031 M NaOH to hydrolyze the ester groups (this
process is called saponification).

C6H6(COOCH3)2 + 2OH- ->.......

After the reaction was complete, the excess NaOH was back-titrated with 24.27 mL of 0.1644 M HCI.
Calculate the percentage of dimethylphthalate in the sample.
* 12-33. Neohetramine, C16H21ON4 (285.37 g/mol), is a common antihistamine. A 0.1247-g sample
containing this compound was analyzed by the Kjeldahl method. The ammonia produced was collected
in H3BO3; the resulting H2BO3- was titrated with 26.13 mL of 0.01477 M HCI. Calculate the percentage
of neohetramine in the sample.

12-34. The Merck-lndex indicates that 10 mg of guanidine, CH5N3, may be administered for each
kilogram of body weight in the treatment of myasthenia gravis. The nitrogen in a 4-tablet sample that
weighed a total of 7.50 g was converted to ammonia by a Kjeldahl digestion, followed by distillation into
100.0 mL of 0.1750 M HCI. The analysis was completed by titrating the excess acid with 11.37 mL of
0.1080 M NaOH. How many of these tablets represent a proper dose for a 48-kg patient?

* 12-35. A 1.047-g sample of canned tuna was analyzed by the Kjeldahl method; 24.61 mL of 0.1180 M
HCI were required to titrate the liberated ammonia. Calculate the percentage of nitrogen in the sample.

12-36. Calculate the grams of protein in a 6.50-oz can of tuna in 12-35 (1 oz = 28.3 g).

* 12-37. A 0.5843-g sample of a plant food preparation was analyzed for its N content by the Kjeldahl
method, the liberated NH3 being collected in 50.00 mL of 0.1062 M HCI. The excess acid required an
11.89-mL back-titration with 0.0925 M NaOH. Express the results of this analysis in terms of percent

*(a) N. *(c) (NH.)‚SO..

(b) urea‚ H;NCONH‚. (d) (NPL)‚PO.._

12-38. A 0.9092-g sample of a wheat flour was analyzed by the Kjeldahl procedure. The ammonia formed
was distilled into 50.00 mL of 0.05063 M HCI; a 7.46-mL back-titration with 0.04917 M NaOH was
required. Calculate the percentage of protein in the flour.

* 12-39. A 1.219-g sample containing (NH4)2SO4, NH4NO3, and nonreactive substances was diluted to
200 mL in a volumetric flask. A 50.00-mL aliquot was made basic with strong alkali, and the liberated
NH3 was distilled into 30.00 mL of 0.08421 M HCI. The excess HCI required 10.17 mL of 0.08802 M
NaOH. A 25.00-mL aliquot of the sample was made alkaline after the addition of Devarda’s alloy, and the
NO3- was reduced to NH3. The NH3 from both NH4+ and NO3- was then distilled into 30.00 mL of the
standard acid and back-titrated with 14.16 mL of the base. Calculate the percentage of (NH4)2SO4 and
NH4NO3 in the sample.

*12-40. A 1.217-g sample of commercial KOH contaminated by K2CO3 was dissolved in water, and the
resulting solution was diluted to 500.00 mL. A 50.00-mL aliquot of this solution was treated with 40.00
mL of 0.05304 M HCI and boiled to remove CO2. The excess acid consumed 4.74 mL of 0.04983 M NaOH
(phenolphthalein indicator). An excess of neutral BaCl2 was added to another 50.00mL aliquot to
precipitate the carbonate as BaCO3. The solution was then titrated with 28.56 mL of the acid to a
phenolphthalein end point. Calculate the percentage KOH, K2CO3, and H2O in the sample, assuming that
these are the only compounds present.

12-41. A 0.5000-g sample containing NaHCO3, Na2CO3 and H2O was dissolved and diluted to 250.0 mL.
A 25.00 mL aliquot was then boiled with 50.00 mL of 0.01255 M HCI. After cooling, the excess acid in the
solution required 2.34 mL of 0.01063 M NaOH when titrated to a phenolphthalein end point. A second
25.00-mL aliquot was then treated with an excess of BaCl2 and 25.00 mL of the base; precipitation of all
the carbonate resulted, and 7.63 mL of the HCI were required to titrate the excess base. Calculate the
percent composition of the mixture.

* 12-42. Calculate the volume of 0.06122 M HCI needed to titrate

(a) 20.00 mL of 0.05555 M Na3PO4 to a thymolphthalein end point.

(b) 25 .00 mL of 0.05555 M Na3PO4 to a bromocresol green end point.

(c) 40.00 mL of a solution that is 0.02102 M in Na3PO4 and 0.01655 M in Na2HPO4 to a bromocresol
green end point.

(d) 20.00 mL of a solution that is 0.02102 M in Na3PO4 and 0.01655 M in NaOH to a thymolphthalein
end point.

12-43. Calculate the volume of 0.07731 M NaOH needed to titrate

(a) 25.00 mL of a solution that is 0.03000 M in HCI and 0.01000 M in H3PO4 to a bromocresol green end
point.
(b) the solution in (a) to a thymolphthalein end point.

(c) 30.00 mL of 0.06407 M NaH2PO4 to a thymolphthalein end point.

(d) 25.00 mL of a solution that is 0.02000 M in H3PO4 and 0.03000 M in NaH2PO4 to a thymolphthalein
end point.

* 12-44. A series of solutions containing NaOH, Na2CO3, and NaHCO3, alone or in compatible
combination, was titrated with 0.1202 M HCI. Tabulated below are the volumes of acid needed to titrate
25.00-mL portions of each solution to a (1) phenolphthalein and (2) bromocresol green end point. Use
this information to deduce the composition of the solutions. In addition, calculate the number of
milligrams of each solute per milliliter of solution.

(1) (2)

(a) 22.42 - 22.44

(b) 15.67 - 42.13

(c) 29.64 - 36.42

(d) 16.12 - 32.33

(e) 0.00 - 33.33

12-45. A series of solutions containing NaOH, Na3AsO4, and Na2HAsO4 alone or in compatible
combination, was titrated with 0.08601 M HCI. Tabulated below are the volumes of acid needed to
titrate 25.00-mL portions of each solution to a (1) phenolphthalein and (2) bromocresol green end point.
Use this information to deduce the composition of the solutions. In addition, calculate the number of
milligrams of each solute per milliliter of solution.

(1) (2)

(a) 0.00 18.15

(b) 21.00 28.15

(c) 19.80 39.61

(d) 18.04 18.03

(e) 16.00 37.37


CHAPTER 13

PRECIPITATION TITRIMETRY

Precipitation titrimetry, which is based on reactions that yield ionic compounds of limited solubility, is
one of the oldest analytical techniques, dating back to the mid-1800s. The slow rate of formation of most
precipitates, however, limits to a handful the number of precipitating agents that can be used in
titrimetry. By far the most widely used and important precipitating reagent is silver nitrate, which is used
for the determination of the halogens, the halogen-like anions (SCN-, CN-, CNO-), mercaptans, fatty
acids, and several divalent inorganic anions. Titrimetric methods based on silver nitrate are sometimes
termed argentometric methods. In this book, we will limit our discussion of precipitation titrimetry to
argentometric methods.

{The term argentometric is derived from the Latin noun argentum, which means silver}

13A TITRATION CURVES

Titration curves for precipitation reactions are derived in a completely analogous way to the methods
described in Section 10B-1 for titrations involving strong acids and strong bases. The only difference is
that the solubility product of the precipitate is substituted for the ion-product constant for water. The
example that follows illustrates how p-functions are derived for the pre-equivalence-point region, the
equivalence point, and the post-equivalence-point region for a typical precipitation titration. Compare
these calculations with those for a strong acid/base system shown in Example 10-1.

Example 13-1

Calculate the pAg of the solution during the titration of 50.00 mL cf 0.0500 M NaCl with 0.1000 M
AgNO3 after the addition of the following volumes of reagent: (a) 0.00 mL; (b) 24.50 mL; (c) 25.00 mL; (d)
25.50 mL.
(a) Because no AgNO3 has been added, [Ag+] = 0 and pAg is indetenninate.

(b) At 24.50 mL added, [Ag+] is very small and cannot be computed from stoichiometric considerations,
but [Cl-] can be obtained readily.

[Cl-] = ......

{A useful relationship can be derived by taking the negative logarithm of both sides of a solubility-
product expression. Thus, for silver chloride

-log Ksp = .....

(c) This is the equivalence point where [Ag+] = [Cl-] and

[Ag+] = ....

{Compare this expression with the one in Example 10-1 on page 172.

(d) [Ag+] = .....

{ This titration curve can also be derived from the charge-balance equation as shown in Feature 10-1}

Figure 13-1 shows titration curves for chloride ion that have been derived employing the techniques
shown in Example 13-1. Note the effect of analyte and reagent concentrations on the magnitude of the
change in pAg in the equivalence-point region. The effect here is analogous to that illustrated for
acid/base titrations in Figure 10-3. As shown by the shaded region in the figure, an indicator with a pAg
range of 4 to 6 should provide a sharp end point in the titration of the 0.05 M chloride solution. In
contrast, for the more dilute solution the end point would be drawn out over a large enough volume of
reagent to make accurate establishment of the end point impossible. That is, the color change would
begin at about 24 mL and be complete at about 26 mL.

{curve}

{Figure 13-1

Effect of titrant concentration on titration curves : A, 50.00 mL of 0.0500 M NaCl with 0.1000 M AgNO3;
B, 50.00 mL of 0.00500 M NaCl with 0.1000 M AgNO3.}

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