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PROBLEMS 363
A B C D E F G H
1 Calculation of % Fe.
2 g. sample: 2.287 g. Fe2O3: 0.8792
3 % Fe: 26.88797
4
5 %Fe = {[g Fe2O3 × 2Fe/Fe2O3 (g Fe/g Fe2O3)]/g sample} × 100%
6 = {[0.8792 g Fe2O3 × 2(55.845/159.69)g Fe/g Fe2O3]/2.287 g sample} × 100%
7 B3 = (D2*2*(55.845/159.69)/B2)*100
8
9 The answer is 26.89% Fe.
Questions
1. Describe the unit operations commonly employed in gravimetric analysis, and briefly indicate
the purpose of each.
2. What is the von Weimarn ratio? Define the terms in it.
3. What information concerning optimum conditions of precipitation does the von Weimarn ratio
give us?
4. What is digestion of a precipitate, and why is it necessary?
5. Outline the optimum conditions for precipitation that will obtain a pure and filterable precipitate.
6. What is coprecipitation? List the different types of coprecipitation, and indicate how they may
be minimized or treated.
7. Why must a filtered precipitate be washed?
8. Why must a wash liquid generally contain an electrolyte? What are the requirements for this
electrolyte?
9. What advantages do organic precipitating agents have?
Problems
GRAVIMETRIC FACTOR
10. Calculate the weight of sodium present in 50.0 g Na2 SO4 .
11. If the salt in Problem 10 is analyzed by precipitating and weighing BaSO4 , what weight of
precipitate would be obtained?
12. Calculate the gravimetric factors for:
Substance Sought Substance Weighed
As2 O3 Ag3 AsO4
FeSO4 Fe2 O3
K2 O KB(C6 H5 )4
SiO2 KAlSi3 O8
13. How many grams CuO would 1.00 g Paris green, Cu3 (AsO3 )2 · 2As2 O3 · Cu(C2 H3 O2 )2 , give?
Of As2 O3 ?
QUANTITATIVE CALCULATIONS
14. A 523.1-mg sample of impure KBr is treated with excess AgNO3 and 814.5 mg AgBr is
obtained. What is the purity of the KBr?
15. What weight of Fe2 O3 precipitate would be obtained from a 0.4823-g sample of iron wire that
is 99.89% pure?
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364 CHAPTER 10 GRAVIMETRIC ANALYSIS AND PRECIPITATION EQUILIBRIA
16. The aluminum content of an alloy is determined gravimetrically by precipitating it with
8-hydroxyquinoline (oxine) to give Al(C9 H6 ON)3 . If a 1.021-g sample yielded 0.1862 g of
precipitate. what is the percent aluminum in the alloy?
17. Iron in an ore is to be analyzed gravimetrically by weighing as Fe2 O3 . It is desired that the
results be obtained to four significant figures. If the iron content ranges between 11 and 15%,
what is the minimum size sample that must be taken to obtain 100.0 mg of precipitate?
18. The chloride in a 0.12-g sample of 95% pure MgCl2 is to be precipitated as AgCl. Calculate the
volume of 0.100 M AgNO3 solution required to precipitate the chloride and give a 10% excess.
19. Ammonium ions can be analyzed by precipitating with H2 PtCl6 as (NH4 )2 PtCl6 and then igniting
heat
the precipitate to platinum metal, which is weighed [(NH4 )2 PtCl6 −−−→ Pt + 2NH4 Cl(g) +
2Cl2 (g)]. Calculate the percent ammonia in a 1.00-g sample that yields 0.100 g Pt by this
method.
20. A sample is to be analyzed for its chloride content by precipitating and weighing silver chloride.
What weight of sample would have to be taken so that the weight of precipitate is equal to the
percent chloride in the sample?
21. Pyrite ore (impure FeS2 ) is analyzed by converting the sulfur to sulfate and precipitating BaSO4 .
What weight of ore should be taken for analysis so that the grams of precipitate will be equal to
0.1000 times the percent of FeS2 ?
22. A mixture containing only BaO and CaO weighs 2.00 g. The oxides are converted to the
corresponding mixed sulfates, which weigh 4.00 g. Calculate the percent Ba and Ca in the
original mixture.
23. A mixture containing only BaSO4 and CaSO4 contains one-half as much Ba2+ as Ca2+ by
weight. What is the percentage of CaSO4 in the mixture?
24. A mixture containing only AgCl and AgBr weighs 2.000 g. It is quantitatively reduced to silver
metal, which weighs 1.300 g. Calculate the weight of AgCl and AgBr in the original mixture.
SOLUBILITY PRODUCT CALCULATIONS
25. Write solubility product expressions for the following: (a) AgSCN, (b) La(IO3 )3 , (c) Hg2 Br2 ,
(d) Ag[Ag(CN)2 ]; (e) Zn2 Fe(CN)6 , (f) Bi2 S3 .
26. Bismuth iodide, BiI3 , has a solubility of 7.76 mg/L. What is its Ksp ?
27. What is the concentration of Ag+ and CrO4 2− in a saturated solution of Ag2 CrO4 ?
28. Calculate the concentration of barium in the solution at equilibrium when 15.0 mL of 0.200 M
K2 CrO4 is added to 25.0 mL of 0.100 M BaCl2 .
29. What must be the concentration of PO4 3− to just start precipitation of Ag3 PO4 in a 0.10 M
AgNO3 solution?
30. What must be the concentration of Ag+ to just start precipitating 0.10 M PO4 3− ? 0.10 M Cl− ?
31. At what pH will Al(OH)3 begin to precipitate from 0.10 M AlCl3 ?
32. What weight of Ag3 AsO4 will dissolve in 250 mL water?
33. What is the solubility of Ag2 CrO4 in 0.10 M K2 CrO4 ?
34. Compounds AB and AC2 each have solubility products equal to 4 × 10−18 . Which is more
soluble, as expressed in moles per liter?
35. The solubility product of Bi2 S3 is 1 × 10−97 and that of HgS is 4 × 10−53 . Which is the least
soluble?
36. A student proposes to analyze barium gravimetrically by precipitating BaF2 with NaF. Assuming
a 200-mg sample of Ba2+ in 100 mL is to be precipitated and that the precipitation must be
99.9% complete for quantitative results, comment on the feasibility of the analysis.
DIVERSE ION EFFECT ON SOLUBILITY
37. Write the thermodynamic solubility product expressions for the following:
(a) BaSO4 Ba2+ + SO4 2−
(b) Ag2 CrO4 2Ag+ + CrO4 2−
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RECOMMENDED REFERENCES 365
38. Calculate the solubility of BaSO4 in 0.0125 M BaCl2 . Take into account the diverse ion effect.
39. You are to determine fluoride ion gravimetrically by precipitating CaF2 . Ca(NO3 )2 is added to
give an excess of 0.015 M calcium ion after precipitation. The solution also contains 0.25 M
NaNO3 . How many grams fluoride will be in solution at equilibrium if the volume is 250 mL?
EXCEL EXERCISES
Compare your answers with those on the text website.
40. Prepare a spreadsheet to calculate the percent P2 O5 in Example 10.2. Use it to calculate the %
P2 O5 for the sample given in the example. Do a second calculation for a 0.5267 g sample that
gives a precipitate of 2.0267 g.
41. Prepare a spreadsheet to calculate the solubility of BaSO4 as a function of concentration
of excess Ba2+ concentration, as in Figure 10.3. Prepare a graph of solubility versus Ba2+
concentration, using the Chart function of Excel, and compare it with Figure 10.3.
42. Prepare a spreadsheet to calculate the solubility of BaSO4 as a function of ionic strength, as
in Figure 10.4. Prepare a graph of solubility versus ionic strength using the Chart function of
Excel, and compare it with Figure 10.4.
43. Solve Example 10.9, using Solver to calculate the solubility, s, of PbI2 .
Recommended References
GENERAL AND INORGANIC
1. F. E. Beamish and W. A. E. McBryde, “Inorganic Gravimetric Analysis,” in C. L. Wilson and
D. W. Wilson, eds., Comprehensive Analytical Chemistry, Vol. 1A. New York: Elsevier, 1959,
Chapter VI.
2. C. L. Wilson and D. W. Wilson, eds., Comprehensive Analytical Chemistry, Vol. 1C, Classical
Analysis: Gravimetric and Titrimetric Determination of the Elements, New York: Elsevier,
1962.
ORGANIC REAGENTS
3. K. L. Cheng, K. Ueno, and T. Imamura, eds., Handbook of Organic Analytical Reagents. Boca
Raton, FL: CRC Press, 1982.
4. R. G. W. Hollingshead, Oxine and Its Derivatives. London: Butterworth Scientific, 1954–56.
5. F. Holmes, “Organic Reagents in Inorganic Analysis,” in C. L. Wilson and D. W. Wilson, eds.,
Comprehensive Analytical Chemistry, Vol. 1A. New York: Elsevier, 1959, Chapter II.8.
PRECIPITATION FROM HOMOGENEOUS SOLUTION
6. L. Gordon, M. L. Salulsky, and H. H. Willard, Precipitation from Homogeneous Solution. New
York: Wiley, 1959.
