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13 Titrimetric Methods; Precipitation Titrimetry

Titrimetric method: analytical procedures in which the amount of analyte is


determined from the amount of a standard reagent required to react with
the analyte completely.
Three types of quantitative titrimetry
1. volumetric (the most widely used)
2. gravimetric
3. coulometric

13A Some Terms Used in Volumetric Titrimetry


*Standard solution (standard titrant)
1. accurate known conc. : 4 significant figures
2. stable
3. stoichiometric reaction : whole-number ratio
4. rapid and quantitatively complete reaction : 99.9 %
*Titration
*Direct titration
*Back-titration, residual-titration: when the rate of reaction between the analyte
and reagent is slow or when the reagent lacks stability.
*Equivalence point, theoretical point: the point in a titration when the amount of
added standard reagent exactly equivalent to the amount of analyte.
*End point: the point in a titration when a physical change occurs that is
associated with the condition of chemical equivalence.
*Titration error Et: the difference in volume or mass between the equivalence
point and the end point. (Vep Veq)
*Indicator: large changes in the relative conc. of analyte or titrant occur in the
equivalence-point region.
a. appearance or disappearance of a color.
b. change in color
c. appearance or disappearance of turbidity.
Instruments for detect end point: voltmeters, ammeters, ohmmeters,
colorimeters, temperature recorders, refractometers.

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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

13B Standard Solutions


*Standardization, establishing the conc. of standard soln.
1. Direct method: carefully weighed quantity of a primary standard
dissolved diluted to an exactly known volume.
2. Standardized by titrating
a. a weighed quantity of a primary standard
b. a weighed quantity of a secondary standard secondary standard
c. a measured volume of another standard soln solution

*Methods for expressing the conc. of standard solutions


a. molarity C : no. of moles/L soln
b. normality CN : no. of equivalent/L soln.

13C Volumetric calculations


mass A (g) mol
amount A (mol) = = V(L) C A ( )
molar mass A (g/mol) L
mass A (g) mmol
amount A (mmol) = = V(mL) C A ( )
molar mass A (g/mmol) mL

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*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
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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

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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

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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 %

13D Gravimetric Titrimetry


13 E Titration curves in Titrimetric Methods

Fig. 13-2
Two types of
titration curves.

(a) Sigmoidal curve (b) Linear-segment curve

Table 13-1 Concentration changes during a titration of 50.00 mL of 0.1000M AgNO3


with 0.1000M KSCN
0.1000M mL of KSCN to cause a
[Ag+] mmol/L pAg pSCN
KSCN, mL tenfold decrease in [Ag+]
0.00 1.000 10-1 1.00
40.91 1.000 10-2 40.91 2.00 10.00
49.01 1.000 10-3 8.10 3.00 9.00
49.90 1.000 10-4 0.89 4.00 8.00
49.99 1.000 10-5 0.09 5.00 7.00
50.00 1.000 10-6 0.01 6.00 6.00
50.01 1.000 10-7 0.01 7.00 5.00
50.10 1.000 10-8 0.09 8.00 4.00
51.01 1.000 10-9 0.91 9.00 3.00
61.11 1.000 10-10 10.10 10.00 2.00
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Fig. 13-3 Titration curve
for the titration of 50.00 mL
of0.1000 M AgNO3 with
0.1000 M KSCN.

13F Precititation Titrimetry


Silver nitrate titrations : Argentometric methods
for : halides, halide-like anion (SCN-, CN-, CNO-) several divalent anions,
mercaptans, fatty acids and several divalent and trivalent inorganic anions.
End point:
1. A change in color due to the reagent, the analyte or an indicator.
2. A change in potential of an electrode that responds to the conc. of one of the
reactants.
Titration curves: plots of a conc.-related variable as a function of reagent volume.
13F-1 Precipitation titration curves involving silver ion
preequivalence points
equivalence point
post equivalence points
Ex. 13-13. Perform calculations needed to generate a titration curve for 50.00
mL of 0.0500 M NaCl with 0.1000 M AgNO3.
Ag+(aq) + Cl-(aq) AgCl(s), KSP= [Ag+][Cl-] = 1.82 10-10
Initial point: 0.000 M in Ag, and pAg is indeterminate.
preequivalence points , At 10.00 mL
- original no. mmol Cl - - no. mol AgNO3
[Cl ] C NaCl =
total volume of solution
50.00 0.0500 10.00 0.100
= = 0.02500 M
50.00 + 10.0

+
K sp 1.82 10 10
[Ag ] = = = 7.28 10 9 , pAg = -log ( 7.28 10-9) = 8.14
0.02500 0.02500

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Equivalence point
[Ag+ ] = K sp = 1.82 1010 = 1.35 105 , pAg = -log (1.35 10 ) = 4.87
-5

post equivalence point, After Addition of 26.0 mL of Reagent


( 26.00 0.1000 50.00 0.0500)
[Ag + ] C AgNO 3 = = 1.316 10 3
76.00
pAg = -log (1.316 10-3) = 2.88

Tab.13-2 Changes in pAg in the titration of Cl- with AgNO3.


50.00 mL of 0.0500 M NaCl 50.00 mL of 0.00500 M NaCl
AgNO3, mL
with 0.1000M AgNO3 with 0.01000M AgNO3
10.00 8.04 7.14
20.00 7.59 6.59
24.00 6.87 5.87
25.00 4.87 4.87
26.00 2.88 3.88
30.00 2.20 3.20
40.00 1.78 2.78
The shapes of titration curves

Fig. 13-4 Titration curve for A,


50.00 mL of 0.0500 M NaCl with
0.1000 M AgNO3, and B, 50.00 mL Fig. 13-5 Effect of reaction completeness on
of 0.00500 M NaCl with 0.01000 precipitation titration curve, 50.00 mL of a
M AgNO3. 0.0500 M solution of the anion was titrated
with 0.1000 M AgNO3.

*Factors influencing end-point sharpness


Satisfactory end points require a change of 2 in p-function within 0.1 mL of the
equivalence point
79
a. reagent conc. : conc. sharpness
b. reaction completeness : product ppt Ksp sharpness
*Chemical indicators for precipitation titration
A + R AR(s) analyte A with titrant R,
In + R InR indicator In
For a color change to be seen, [InR]/[In] must change by a factor of 10 to 100.
13F-2 Titration curves for mixtures of anions
Titration of 50.00 mL of a solution ([I-] = 0.0500M and [Cl-]=0.0800 M) with
0.1000 M AgNO3.
[Ag + ][I - ] 8.3 10 17
+
= 10
= 4.56 10 7 [I - ] = (4.56 10 7 )[Cl - ]
[Ag ][Cl ] 1.82 1
-

after added 25.00 mL AgNO3 ,


50.00 0.0800
cCl = = 0.0533 M , [I-] = 4.56 10-7 0.0533 = 2.43 10-8 M
50.00 + 25.00
no. mmol I- = 75.00mL (2.43 10-8 mmol I-/mL) = 1.82 10-6
1.82 16
I unprecipitated =
-
100% = 7.3 10 5 %
50.00 0.0500
10
1.82 10
[Ag + ] = = 3.41 10 9 pAg = log(3.41 10 9 ) = 8.47
0.0533
after added 30.00 mL AgNO3 ,
50.00 0.0800 (30.00 0.100 50.00 0.0500)
cCl = [Cl - ] = = 0.0438 M
50.00 + 30.00

+ 1.82 10 10
[Ag ] = = 4.16 10 9 ,
0.0438
pAg = 8.38

Fig. 13-6 Titration curves for 50.00


mL of a solution 0.0800 M in Cl-
and 0.0500 M in I- or Br-.
AgI: Ksp = 8.3 10-17
AgBr: Ksp = 5.2 10-13
AgCl: Ksp = 1.8 10-10

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

1. Chromate Ion; The Mohr method


1865 K. F. Mohr, a German pharmaceutical chemist
sample: Cl-, Br-, CN-
AgNO3 + X- AgX(s) + NO3-
white
AgNO3 + CN Ag(CN)2-(aq) + NO3-
-

End point: 2AgNO3 + CrO42- Ag2CrO4(s) + 2 NO3-


yellow red (Ksp = 1.1 10-12 M3)

not for arsenate, I-, SCN-


Solubility: Ag2CrO4 > AgX
*Choice of indicator:
if indicator- I- anion (AgI Ksp = 8.3 10-17 M2)
AgCl Ksp = 1.82 10-10 M2
[Ag+]ep = (Ksp) = (1.82 10-10 M2) = 1.35 10-5 M
if indicator- I- anion conc. = 0.0025 M
AgI ppt formation
[Ag+]min = 8.3 10-17 M2/0.0025 M I- = 3.3 10-14 M
pre-equivalence point : Ag+ AgI (s)

*Concentration of indicator [CrO42-]


equivalence point : [Ag+] = [Cl-] = 1.35 10-5 M
[CrO42-] = Ksp/[Ag+]2 = 1.2 10-12/(1.35 10-5)2 = 6.6 10-3 M

*pH : 6.5 10.3 (7~10)


pH < 6.5 Ag2CrO4(s) 2Ag+ + CrO42-
CrO42- + H+ Cr2O72- + H2O
pH > 10.3 Ag+ + OH- AgOH(s)
81
2. Adsorption indicators: The Fajans method
1926, Polish chemist, K. Fajans
Advantages: rapid, accurate and reliable
AgNO3 + X- AgX(s) + NO3-
End point: Ag+ + AgX(s) + Fl- AgX:Ag+ Fl-(s)
Yellow-green red
Indicator: Fluorescein anion O O OH

* avoid ppt coagulation ppt surface


a. adding dextrin or polyethylene glycol COOH

b. quick titration and avoid excessive stirring


c. halide ion conc. : 0.005 ~ 0.025 M fluorescein
*Fluorescein dyes: weak ionized acids
pH [Fl-] weak end point
pH 7, (dichlorofluorescein: pH 4)
*Photochemical decomposition : ppt black

Indicator pH Sample
Fluorescein 7 Cl-, Br-, I-, SCN-
Dichlorofluorescein 4 Cl-, Br-, I-, SCN-
Eosin 2 Br-, I-, SCN-

3. Iron(III) Ion; The Volhard method


1874 Jacob Volhard, a German chemist, (back titration): Iron(III) ion as indicator
sample: halide ion, C2O42-, AsO43-, SCN-
nAgNO3 (excess) + Bn- AgnB(s) + nNO3-
KSCN + unreacted AgNO3 AgSCN(s) + K++ NO3-
End Fe3+ + SCN- Fe(SCN)2+ [Fe(SCN) 2 + ]
Kf = = 1050
point: red [Fe 3+ ][ SCN ]
*pH : in acidic soln to prevent Fe(III) Fe(OH)3(s)
*advantage: carbonate, oxalate & arsenate do not interfere.
*For Cl- ion in blood serum, urine. (sample: HNO3 digestion)
*Quantitativeness of the back titration
n SCN- + AgnB(s) n AgSCN(s) + Bn-
a. compare AgSCN and AgnB : molar solubility AgSCN: 1.0 10-6 M

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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

Table 13-3 Typical Argentometric Precipitation Methods


Analyte End point Remarks
3- - -
AsO4 , Br , I , Volhard Removal of Ag salt not required
- -
CNO , SCN
CO32-, CrO42-, CN-, Volhard Removal of Ag salt required before
- 2- 3-
Cl , C2O4 , PO4 , back-titration of excess Ag+
S2-, NCN2-
BH4- Modified Titration of excess Ag+ following BH4- + 8Ag+
Volhard + 8OH- 8Ag(s) + H2BO3- + 5H2O
Epoxide Volhard Titration of excess Cl- following
hydrohalogenation
+
K Modified Precipitation of K+ with known excess of
Volhard B(C6H5)4-, addition of excess Ag+ giving
AgB(C6H5)4(s), and back-titration of the excess
- -
Br , Cl Mohr method In neutral solution
- - - 2-
Br , Cl , I , SeO3 Adsorption
indicator
+
V(OH)4 , fatty Electroanalytical Direct titration with Ag+
acids, mercaptans
Zn2+ Modified Precipitation as ZnHg(SCN)4, filtration,
Volhard dissolution in acid, addition of excess Ag+,
back-titration of excess Ag+
F- Modified Precipitation as PbClF, filtration, dissolution in
Volhard acid, addition of excess Ag+, back-titration of
excess Ag+

Ex. The As in a 9.13-g sample of pesticide was converted to AsO43- and


precipitated as Ag3AsO4 with 50.00 mL of 0.02015 M AgNO3. The excess
Ag+ was then titrated with 4.75 mL of 0.04321 M KSCN. Calculate the % of
As2O3 in the sample.
no. mmol AgNO3 = 50.00 mL 0.02015 mmol = 1.0075
no. mmol KSCN = 4.75 mL 0.04321 mmol = 0.2052
no. mmol AgNO3 consumed by AsO43- =0.8023
As2O3 2 AsO43- 6 AgNO3
% As2O3 = 0.8023 (1/6) 0.1978/9.13 100 % = 0.2987 %

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 )

for 0.1 M X-, actual Krxn 108


for 0.01 M X-, actual Krxn 1010

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