13
13
13
72
Fig. 13-1 The titration process
*Primary standards:
1. high purity
2. stability in air
3. absence of hydrate water
4. ready availability at modest cost
5. reasonable solubility in the titration medium
6. reasonably large formula weight
*Secondary standard
73
*Calculation of the Molarity of Standard Solutions (SS)
Ex. 13-1. Describe the preparation of 2.000 L of 0.0500 M AgNO3 (169.87 g/mol)
from the primary standard-grade solid.
amount AgNO3 = 0.050 L 2.000 mol/L = 0.1000 mol
mass AgNO3 = 0.1000 mol 169.87 g/mol =16.98 g
dissolving 16.98 g AgNO3 in water and diluting to 2.000 L.
Ex. 13-2. Describe how 500 mL of standard 0.0100 M Na+ solution can be prepared
from primary standard Na2CO3(105.99 g/mol).
amount Na2CO3 = 500 mL 0.0100 mmol/mL = 2.50 mmol
mass Na2CO3 = 2.50 mmol 0.10599 g/mmol = 0.265 g
dissolving 0.265 g Na2CO3 in water and diluting to 500 mL.
Ex. 13-3. How would you prepare 50.0-mL portions of SS that are 0.00500 M,
0.00200 M and 0.00100 M in Na+ from the soln in Ex. 2?
Vconcd Cconcd = Vdil C dil
Vdil Cdil 50.0mL 0.00500mmol Na + / mL
Vconcd = = = 25.0mL
Cconcd 0.0100mmol Na + / mL
0.00500M 0.00200M 0.00100M
+
0.0100 M Na soln 25.0 mL 10.0 mL 5.00 mL
Ex. 13-4. Describe how you would prepare 2.0 L of approximate 0.25 M HClO4
(100.46 g/mol) from the conc. reagent, which has a specific gravity of 1.67
g/mL and contains 71 % (w/w) HClO4.
CHClO4 = 1.67 (g/mL)/0.10046 (g/mmol) 0.71 = 11.8 M
no. mmol HClO4 required = 2000 mL 0.25 mmol/mL = 500 mmol
vol conc. reagemnt = 500 mmol/11.8 (mmol/mL) = 42.4 conc. reagent
diluted about 42 mL of 71 % HClO4 to 2.0 L.
*Calculation of Molarities from Standardization Data
Ex. 13-5. A 50.00-mL of an HCl solution required 29.71 mL of 0.01963 M Ba(OH)2
to reach an end point with bromocresol green indicator. Calculate the molarity
of the HCl. Ba(OH)2 + 2HCl BaCl2 + 2H2O
1 mmol Ba(OH)2 reacts with 2 mmol of HCl
amount Ba(OH)2 = 29.71 mL 0.01963 mmol/mL = 0.5832 mmol
amount HCl = 2 0.5832 = 1.1664 mmol
(29.71 0.01963 2) mmol HCl
C HCl = = 0.023328 M = 0.0233 M
50.0 mL soln
74
Ex. 13-6. Titration of 0.2121 g pure Na2C2O4 (134.00 g/mol) required 43.31 mL
KMnO4. What is the molarity of the KMnO4 soln?
2MnO4- + 5C2O42- + 16H+ 2Mn2+ + 10CO2 + 8H2O
2 mmol KMnO 4
stoichiometric ratio =
5 mmol Na 2C 2O 4
0.2121 g
amount Na2C2O4 =
0.13400 g/ mmol
amount KMnO4 = 0.2121 mmol 2
0.13400 5
0.2121 2
( ) mmol
C KMnO 4 = 0 . 1340 5 = 0.01462 M
43.31 mL
*Calculation the Quantity of Analyte from Titration Data
Ex. 13-7. A 0.8040-g sample of an iron ore is dissolved in acid. The iron is then
reduced to Fe2+ and titrated with 47.22 mL of 0.02242 M KMnO4 solution.
Calculate the results of this analysis in term of (a) % Fe (55.847 g/mol); and
(b) % Fe3O4 (231.54 g/mol).
MnO4- + 5Fe2+ + 8H+ Mn2+ + 5Fe3+ + 4H2O
5 mmol Fe 2 +
(a). stoichiometric ratio =
1 mmol KMnO 4
amount KMnO4 = 47.22 mL 0.02242 mol/L = 1.0587 mmol
amount Fe2+ = 47.22 mL 0.02242 mol/L 5 = 5.2934 mmol
mass Fe2+ = 5.2934 mmol 0.055847 g/mmol = 0.2956 g
(47.22 0.02242 5 0.055847) g
percent Fe2+ = 100% = 36.77%
0.8040 g sample
(b). stoichiometric ratio: = 5 Fe2+ 1 MnO4-
5 Fe3O4 15 Fe2+ 3 MnO4-
amount KMnO4 = 47.22 mL 0.02242 mol/L = 1.0587 mmol
amount Fe3O4 = 47.22 mL 0.02242 mol/L 5/3 = 1.76445 mmol
mass Fe3O4 = 1.76445 mmol 0.23154 g/mmol = 0.4085 g
5
( 47.22 0.02242 ) 0.23154g
percent Fe3O4 = 3 100% = 50.81%
0.8040 g sample
75
Ex.13-8. A 100.0-mL sample of brackish water was made ammonical, and the sulfide
it contained was titrated with 16.47 mL of 0.02310 M AgNO3. The analytical
reaction is 2Ag+ + S2- Ag2S(s) Calculate [H2S] in the water in ppm.
1
(16.47 0.02310 ) 0.034802g
[H 2S] = 2 10 6 ppm = 66.2 ppm H 2S
100.0 mL 1.000g/mL sample
Ex. 13-9. The phosphorus in a 4.258-g sample of a plant food was converted to PO43-
and precipitated as Ag3PO4 through the addition of 50.00 mL of 0.0820 M
AgNO3. The excess AgNO3was back-titrated with 4.06 mL of 0.0625 M
KSCN. Express the results of the analysis in terms of % P2O5.
P2O5 + 9H2O 2PO43- + 6H3O+ 1 mmol P2 O 5 1 mmol KSCN
2PO43- + 6Ag+(excess) 2Ag3PO4(s) and
6 mmol AgNO3 1 mmol AgNO3
Ag+ + SCN- AgSCN(s)
1
(50.00 0.0820 4.06 0.0625) 0.1419g/mm ol
% P2 O 5 = 6 100% = 2.14%
4.258 g sample
Ex. 13-10 The CO in a 20.3-L sample of gas was converted to CO2 by passing the
gas over iodine pentoxide heated to 150, and I2 was distilled and collected to
8.25 mL of 0.01101 M Na2S2O3, then back titration with 2.16 mL of 0.00947 M
I2 solution. Calculate the mg of CO (28.01 g/mol) per liter of sample.
I2O5(s) + 5CO(g) 5CO2(g) + I2(g) [CO : I2 = 5 : 1]
I2(aq) + 2S2O3 (aq) 2I (aq) + S4O6 (aq) [I2 : S2O32- = 1 : 2]
2- - 2-
[CO: S2O32- = 5 : 2]
(8.25 0.01101 - 2.16 0.00947 2) 5 28.01
Mass CO = 2
20.3 L
0.1248 mmol 28.01 3.4956
= = = 0.172 mg/L
20.3 20.3
Ex. 11 The organic matter in a 3.776-g sample of a mercuric ointment is decomposed
with HNO3. After dilution, the Hg2+ is titrated with 21.30 mL of a 0.1144 M
soln of NH4SCN. Calculate the percent Hg (200.59 g/mol) in the ointment.
Hg2+ + 2SCN- Hg(SCN)2(aq)
stoichiometric ratio = 1 mmol Hg2+/2 mmol NH4SCN
amount NH4SCN = 21.30 mL 0.1144 mmol/mL = 2.4367 mmol
amount Hg2+ = 2.4367 mmol 1/2 = 1.2184 mmol
mass Hg2+ = 1.2184 mmol 0.20059 g/mmol = 0.2444 g
( 21.30 0.1144 1 ) 0.20059g
2 100% = 6.472%
percent Hg =
3.776 g sample
76
Ex. 13-12 A 0.4755-g sample [(NH4)2C2O4 and inert ]/ H2O, added KOH to alkaline
[NH4+ NH3], distilled into 50.00 mL of 0.05035 M H2SO4. Then back
titration with 11.13 mL of 0.1214 M NaOH. Calculate (a) the % N (14.007
g/mol) and (b) the % (NH4)2C2O4 (124.10 g/mol) in the sample.
(50.00 0.05035 2 11.13 0.1214) 14.007
(a) % N = 100%
0.4755 g 1000
3.6838 14.007
= 100% = 10.85%
475.5
3.6838 124.10 / 2 228.58
(b) % (NH 4 ) 2 C 2O 4 = 100% = 100%
0.4755 g 1000 475.5
= 48.07 %
Fig. 13-2
Two types of
titration curves.
+
K sp 1.82 10 10
[Ag ] = = = 7.28 10 9 , pAg = -log ( 7.28 10-9) = 8.14
0.02500 0.02500
78
Equivalence point
[Ag+ ] = K sp = 1.82 1010 = 1.35 105 , pAg = -log (1.35 10 ) = 4.87
-5
+ 1.82 10 10
[Ag ] = = 4.16 10 9 ,
0.0438
pAg = 8.38
80
13F-3 Indicators for Argentometric Titrations
*AgNO3 titrations
Method Mohr (Direct) Fajans (Direct) Volhard (Residual)
Titrant AgNO3 AgNO3 AgNO3-KSCN
Indicator Na2CrO4 Fluorescein Fe3+
End point Ag2CrO4 (s) red AgX:Ag+ Fl-(s) Fe(SCN)2+
ppt red ppt red solution
Titration pH 6.5 ~ 10.3 7 Acidic
Indicator pH Sample
Fluorescein 7 Cl-, Br-, I-, SCN-
Dichlorofluorescein 4 Cl-, Br-, I-, SCN-
Eosin 2 Br-, I-, SCN-
82
b. Calculate Krxn [Bn - ] K sp of Ag n B
K rxn = =
[SCN - ]n (K sp of AgSCN) n
if AgSCN solubility < AgnB or Krxn > 1
filter AgnB ppt or adding liquid nitrobenzene
83
*Quantitativeness of AgNO3 titration
Ag+ + X- AgX(s) Krxn = 1/Ksp = 1/[Ag+][X-]
a. 99.9 % reaction: at equivalence point, max % Cl- : 0.1 %
ex: AgCl, Ksp = 1.8 10-10 ; [Cl - ] = K sp = 1.34 10 5 M
K sp of AgCl 100 1.34 10 5 100
%dissolved = = = 0.13%
M of initial Cl - 0.010 M
b. min. theo. Krxn Krxn
Krxn = 1/Ksp
0.10 M sample [X-] 0.1 %
upper limit of [X-] = (0.10 M)(0.1 %) = 10-4 M
equivalence point : [Ag+] = [X-]
1
min theo. K rxn = 4 + 4 -
= 108
(10 M Ag )(10 M X )
84