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Chapter 12
Chapter 12
12-1 (a) A colloidal precipitate consists of solid particles with dimensions that are less than 10-
4
cm. A crystalline precipitate consists of solid particles with dimensions that at least 10-4
which is then filtered, washed free of impurities, and then converted into a product of
composition.
(c) Precipitation is the process by which a solid phase forms and is carried out of solution
process in which normally soluble compounds are carried out of solution by precipitate
formation.
form larger aggregates. Peptization refers to the process by which a coagulated colloid
reverts to its original dispersed state. Heating, stirring and adding an electrolyte can
coagulate colloidal suspensions. Washing the coagulated colloid with water often
removes sufficient electrolyte to permit the re-establishment of repulsive forces that favor
associate to give a stable solid. Particle growth is a process by which growth continues
12-2 (a) Digestion is a process in which a precipitate is heated in the presence of the solution
from which it was formed (the mother liquor). Digestion improves the purity and
(b) Adsorption is the process by which ions are retained on the surface of a solid.
Because the concentration of the impurity in the new solution is lower, the second
agent is generated in a solution of the analyte by a slow chemical reaction. Local reagent
excess does not occur and the resultant solid product is better suited for analysis than
(e) The counter-ion layer describes a layer of solution containing sufficient excess
negative ions that surrounds a charged particle. This counter-ion layer balances the
(g) Supersaturation describes an unstable state in which a solution contains higher solute
excess solute.
Fundamentals of Analytical Chemistry: 8th ed. Chapter 12
12-3 A chelating agent is an organic compound that contains two or more electron-donor
groups located in such a configuration that five- or six-membered rings are formed when
12-5 (a) There is positive charge on the surface of the coagulated colloidal particles.
-
(c) NO 3 ions make up the counter-ion layer.
12-6 CH 3CSNH 4 H 2 O
CH 3CONH 2 H 2S
sulfide gas. Hydrogen sulfide gas is then involved in the equilibria below:
H 2S H 2 O
H 3O HS
HS H 2 O
H 3O S 2
The S2- generated can then be used to precipitate Ni2+ in the form of NiS.
12-7 Peptization is the process by which a coagulated colloid returns to its original dispersed
contact with the precipitate. Peptization can be avoided by washing the coagulated
12-8 Chloroplatinic acid, H2PtCl6, forms the precipitate K2PtCl6 when mixed with K+ but does
not form analogous precipitates with Li+ and Na+. Thus, chloroplatinic acid can be used
12-9 Note: M stands for molar or atomic mass in the equations below:
M SO2
(a) mass SO 2 mass BaSO 4
M BaSO4
2 M Mg
(b) mass Mg mass Mg 2 P2 O 7
M Mg2 P2O7
2 M In
(c) mass In mass In 2 O 3
M In2O3
2MK
(d) mass K mass K 2 PtCl 6
M K 2 PtCl6
2 M Cu
(e) mass Cu mass Cu 2 (SCN ) 2
M Cu2 (SCN )2
3 M MnCl2
(f) mass MnCl 2 mass Mn 3O 4
M Mn3O4
M Pb3O4
(g) mass Pb 3O 4 mass PbO 2
3 M PbO2
Fundamentals of Analytical Chemistry: 8th ed. Chapter 12
M U 2 P2O11
(h) mass U 2 P2 O11 mass P2 O 5
M P2O5
M Na 2 B4O7 10 H 2O
(i) mass Na 2 B2 O 7 10 H 2 O mass B2 O 3
2 M B2O3
M Na2O
(j) mass Na 2 O mass NaZn( UO 2 ) 3 (C 2 H 3O 2 ) 9 6H 2 O
2 M NaZn( UO2 )3 ( C2 H 3O2 )9 6 H 2O
12-10
143.32 g 74.55 g
M AgCl M KCl
mole mole
1 mole AgCl 1 mole KCl 74.55 g KCl
0.2912 g AgCl
143.32 g 1 mole AgCl mole
100% 60.59%
0.2500 g impure sample
101.96 g 237.15 g
12-11 M Al2O3 M NH 4 Al ( SO 4 ) 2
mole mole
(a)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 12
0.2001 g Al 2 O 3
(b) 0.910 g impure sample 100% 22.0% Al 2 O 3
(c)
12-12
12-13
12-14 (Note: In the first printing of the text, the answer in the back of the book was in error.)
12-15 The precipitate V2O52UO3 gives the greatest mass from a given quantity of uranium.
12-16 Al 2 ( CO 3 ) 3 6 HCl
3CO 2 3H 2 O 2 AlCl 3
12-17 CdS 2O 2
CdSO 4
34.08 g H 2S
mass H 2S 5.61 10 4 mole 0.0191 g
1 mole H 2S
0.0191 g H 2S
100% 0.025% H 2S
75.0 g impure sample
12-18
12-19
12-20 (Note: In the first printing of the text, the answer in the back of the book was in error.)
mol Hg 2
1 mole Hg 5 ( IO 6 ) 2 5 mole Hg 2
0.4114 g Hg 5 ( IO 6 ) 2 1.4198 10 3 mol Hg 2
1448.75 g Hg 5 ( IO 6 ) 2 1 mole Hg 5 ( IO 6 ) 2
1 mole Hg 2 Cl 2 472.09 g Hg 2 Cl 2
1.4198 10 3 mol Hg 2
2 mole Hg 2 1 mole Hg 2 Cl 2 100% 41.16% Hg Cl
2 2
0.8142 g sample
12-21
487.13 g 166.00 g
M Ba ( IO3 )2 M KI
mole mole
1 mole Ba ( IO3 ) 2 2 mole KI 166.00 g KI
0.0612 g Ba ( IO3 ) 2
487.13 g 1 mole Ba ( IO 3 ) 2 mole
100%
1.97 g impure sample
2.12% KI
Fundamentals of Analytical Chemistry: 8th ed. Chapter 12
12-22
17.0306 g 195.08 g
M NH 3 M Pt
mole mole
1 mole Pt 2 mole NH 3 17.0306 g NH 3
0.4693 g Pt
195.08 g 1 mole Pt mole
100% 38.74% NH 3
0.2115 g impure sample
12-23
86.94 g 133.34 g
M MnO 2 M AlCl3
mole mole
1 mole MnO 2
mol MnO 2 (0.6447 g 0.3521 g MnO 2 ) 3.366 10 3 mol
86.94 g
2 mole Cl 1 mole AlCl 3 133.34 g AlCl3
3.366 10 3 mol MnO 2
1 mole MnO 3 mole Cl mole
2
100%
1.1402 g impure sample
26.24% AlCl 3
Fundamentals of Analytical Chemistry: 8th ed. Chapter 12
2
1 mole BaSO 4 1 mole SO 4 2
0.200 g BaSO 4 8.57 10 4 mole SO 4
233.39 g 1 mole BaSO 4
2
4 96.064 g SO 4
2
8.57 10 mole SO 4
mole 100% 20% SO 4
2
S w g sample
2
4 96.064 g SO 4
2
8.57 10 mole SO 4 100%
S w g sample mole 0.412 g sample
20%
2 2
55 g SO 4 1 mole SO 4 1 mole BaSO4 233.39 g BaSO4
0.412 g sample 2
100 g sample 96.064 g 1 g SO 4 1 mole
0.550 g BaSO4
The higher percentage of Ni in the alloy sample is selected because this corresponds to
12-26
(a)
(b)
(c)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 12
12-27
A B C D
1 Problem 12-27
2
3 Coefficient Matrix Constant Matrix
4 1.823 1.578 1.505
5 1 1 0.872
6
7 Inverse Matrix Solution Matrix
8 4.0816327 -6.4408200 0.526465306
9 -4.0816300 7.4408160 0.345534694
10
11 Mass of Sample % KBr % NaBr
12 0.872 39.6 60.4
13
14 Spreadsheet Documentation
15 A8:B8=MINVERSE(A4:B5)
16 D8:D9=MMULT(A8:B9,D4:D5)
17 C12=100*D9/A12
18 D12=100*D8/A12
12-28
A B C D
1 Problem 12-28
2
3 Coefficient Matrix Constant Matrix
4 1 1 0.443
5 1 0.6104698 0.3181
6
7 Inverse Matrix Solution Matrix
8 -1.5671952 2.5671952 0.122357321
9 2.5671952 -2.5671952 0.320642679
10
11 Mass of Sample Mass AgCl % Cl %I
12 0.6407 0.1223573 4.72 27.05
13
14 Spreadsheet Documentation
15 A8:B8=MINVERSE(A4:B5)
16 D8:D9=MMULT(A8:B9,D4:D5)
17 B12=D4-D9
18 C12=100*D9/A12
19 D12=100*D8/A12
Fundamentals of Analytical Chemistry: 8th ed. Chapter 12
12-29
12-30
12-31
M Mg2 P2O7 222.55 g / mole M NaCl 58.44 g / mole M MgCl2 6 H 2O 203.32 g / mole
1 mole Mg 2 P2 O 7 2 moles MgCl 2 6H 2 O
0.1796 g Mg 2 P2 O 7
222.55 g 1 mole Mg 2 P2 O 7
1.61402 10 3 mole MgCl2 6 H 2 O
1 mole AgCl
0.5923 g AgCl 4.13268 10 3 mole AgCl
143.32 g
2 moles AgCl
1.61402 10 3 mole MgCl2 6H 2 O 3.22804 10 3 mole AgCl
1 mole MgCl 2 6H 2 O
1 mole NaCl
( 4.13268 10 3 3.228 10 3 ) mole AgCl 9.0464 10 4 mole NaCl
1 mole AgCl
203.32 g MgCl 2 6 H 2 O 500.0 mL
1.61402 10 3 mole MgCl 2 6 H 2 O
1 mole 50.0 mL
100%
6.881 g sample
47.69% MgCl 2 6 H 2 O
12-32
(a)
1.516 10 3 mole
moles Ba ( IO 3 ) 2 7.580 10 4 mole
2
487.13 g Ba ( IO 3 ) 2
mass Ba ( IO 3 ) 2 7.580 104 mole 0.369 g Ba ( IO 3 ) 2
1 mole
(b)
12-33
(b)