Precipitation Titration

Dr. Cherrie Pascual

Institute of Chemistry
UP Diliman
IMPORTANT DISCLAIMER: THE MATERIALS HERE ARE
SOLELY FOR THE PURPOSE OF INSTRUCTION FOR CHEM
28 CLASSES OF DR. PASCUAL AT IC-UPD AND NOT
INTENDED TO BE REPRODUCED/COPIED FOR ANY
OTHER PURPOSE.
 PRECIPITATION TITRATION
∙ based upon rxns. that form sparingly soluble
salts; usually Ag salts
∙ most impt. precipitating titrant: AgNO3
used for detn. of halides (X-) & halide-like anions
like CN- & SCN-
∙ sometimes termed argentometric methods due
to Ag+
∙ not as numerous as redox or acid-base titrns.
 PRECIPITATION TITRATION
Titration Curves: plot pX vs. Vtitrant
Example: titration of 50.00 ml 0.0500 M NaCl with 0.1000 M
AgNO3
a) ); soln: 0.0500 M in Cl-,
0.00 M in Ag+
pCl = 1.30
pAg is indeterminate
at eq. pt. = 25.00 ml
b) Before equiv. pt. e.g. = 10.00 ml ; Cl- in excess

pCl = 1.60
 NaCl vs. AgNO3
To get pAg: = [Ag+][Cl-]
= pAg + pCl
pAg = - pCl = 9.74 - 1.60
= 8.14
c) at equiv. pt. ( = 25.00 ml) – no x’s Cl- nor
Ag+
[Ag+] = [Cl-] = = 1.35 × 10-5 M
or pAg = ½ = 4.87
d) after equiv. pt. (w/ x’s AgNO3)
e.g. = 30.00 ml

= 6.25 × 10-2 M
pAg = 2.20
 PRECIPITATION TITRATION
Effect of Concn. on Titration Curves:
∙ increase in concn. enhances ΔpX at equiv. pt. region
(same trend as in acid-base titrn)

Effect of Rxn. Completeness on Titration Curves:

greatest ΔpX in titration of ion w/c forms the least soluble Ag+ salt
(represents most nearly complete rxn)
Ag+ + X- AgX

The smaller the , the larger the K for titrn.

 PRECIPITATION TITRATION
Endpoints for Argentometric Titrations
1) Chemical
2) Potentiometric
3) Amperometric

Chemical Indicators for Precipitation Titrations

Analyte A & Titrant B & Indicator In
Titrn. Rxn: A + B → AB
Endpt. Rxn: In + x’s B → InB
(InB – w/ significantly diff. appearance in
soln. than In at endpt)
 Types of Argentometric Titrations
1) The Mohr Method (formation of a 2nd ppt)
widely applied for titrn. of Cl-, Br- or CN- w/
std. AgNO3
indicator: Na2CrO4
Titration rxn: Ag+ + Cl- AgCl(s)
Endpt. rxn: 2 Ag+ + CrO42- Ag2CrO4(s)

solub. Ag2CrO4 greater than AgCl so all X- ppt’ed when

Ag2CrO4 will start to ppt.
Mohr Titrn. at pH 7-10; pH < 7 dec. [CrO42-]
pH > 10; Ag2O ppts.
MOHR TITRATION
 Types of Argentometric Titrations
2) The Volhard Method (formation of a colored
complex); Ag+ titrated w/ std. KSCN
Titration rxn: Ag+ + SCN- AgSCN(s)
Endpt. rxn: Fe3+ + SCN- Fe(SCN)2+ (blood red
complex) K ×
 Types of Argentometric Titrations
3) The Fajans method (Adsorption Indicators)
adsorption indicator – an organic cpd. that tends
to be adsorbed onto the surface of the solid in a
pptn. titration e. g. fluorescein
e.g. titration of Cl- w/ AgNO3
Ag+ + Cl- AgCl(s) colloidal ppt.
(titrant) (analyte)
before equiv. pt: (AgCl) ∙ Cl- | M+ (w/ x’s Cl)
1° layer 2° layer
adsorption layers
 The Fajans method

after equiv. pt: (AgCl)∙Ag+|X- (w/ x’s Ag+)

Fluorescein – adsorption indicator (HFl)

after equiv. pt.: (AgCl)∙Ag+|Fl- (pinkish red)

color change: yellow green → pinkish red
adsorption process not precipitation
Fajans Method
 Sample Problems
1. Given: titration of 50.00 ml 0.0400 M KBr with
0.0500 M AgNO3. Calculate pAg after addition of a)
15.00 ml, b) 25.00 ml, c) 30.00 ml, d) 40.00 ml and
e) 50.00 ml
2. What is % Ag in a coin, if a 0.2000 g sample requires
39.60 ml of 0.0422 M KSCN for precipitation of Ag?
3. A 0.500 g sample of NaCl is dissolved in H2O and
added with 50.00 ml of 0.2100 M AgNO3. After
filtering out the precipitate, the filtrate requires
25.50 ml of 0.2800 M KSCN to titrate the Ag. What
is % NaCl in the sample?