PRECIPITIMETRY

Detection of the End Point

I – No Indicator Methods

a) Appearance of ppt (turbidity) determination of CN- with St. Ag+

b) Disappearance of ppt (turbidity) determination of Ag+ with St. CN-

II- Using Indicator methods:

A- Mohr’s Method.

B- Volhard’s Method.

C- Adsorption Indicator (Fajan’s methods).

II- Using Indicator methods
These methods include:
• Formation of colored 2ry ppt
e.g. Mohr’s method.
• Formation of colored complex.
e.g. Volhard’s Method.
• Using Adsorption Indicators
e.g. Fajan’s Method

Blank Titration: A titration which is carried out without analyte (e.g., a distilled
water sample) & is used to correct titration error.

Back titration: A titration in which a ………..

 Mohr’s method:
• Principle: a direct argentometric titration method.
(Argentometric titratn.: titrimetric reactn. that use AgNO3 as a pptating agent/titrant; Titration must be carried out in indirect light as AgX is photo sensitive)

• Sample: soluble chloride & bromide salts.

• Titrant: st. AgNO3.
• Medium: neutral or slightly alkaline (pH 7–9).
• Indicator: K2CrO4 solution.
• At E.p.: after complete pptn of halide with AgNO3, the 1st xss dp of AgNO3
will ppt CrO42- as brick red Ag2CrO4 ppt.
NaCl + AgNO3 AgCl + NaNO3 During titn
K2CrO4 + 2AgNO3 Ag2CrO4 ↓+ 2KNO3 At E.p.

According to fractional precipitation theory: when the medium contains two

different ions, the titrant is expected to react with both ions but the less
soluble will be completely precipitated first
• Notes:

• Mohr’s titration must be carried out in neutral or slightly

alkaline medium (pH 7 - 9) because:

- In acidic medium, the equilibrium is shifted towards

formation of dichromate leading to dissolution of the ppt.

2CrO42- + 2H+ ⇌ Cr2O72- + H2O

- In strong alkaline medium, silver (Ag+) precipitates as

hydroxide (AgOH) black ppt.
• Notes:

Mohr’s titration not suitable for titration of:

• NH4Cl & NH4Br samples because in slightly alkaline medium NH4OH

will be formed which cause dissolution of AgCl or AgBr ppt giving
soluble silver ammine complex [Ag(NH3)2]+.

• I- & SCN-, because they adsorb CrO42- ion, also the yellow color of AgI
ppt render the E.P. difficult (Adsorption error).

• Halides in presence of carbonates, phosphates & oxalates which are

precipitated in neutral medium as the molar solubility of their silver
salts equals or slightly greater than that of chromate.
 Volhard’s Method
• It is a direct method for determination of Ag+ sample by st.
SCN- in acidic medium.
• It is an indirect (back) titration for determination of halides in
acidic medium (HNO3).
• A kn. xss st. AgNO3 is added to the halide soln., filter & acidify
the filtrate with HNO3.
NaCl + AgNO3 AgCl ↓ + NaNO3
• The xss st. AgNO3 is back titrated with st. SCN- in presence of
Fe3+ (ferric alum) as indicator.
AgNO3 + KSCN AgSCN ↓ + KNO3
• E.p.: detected by 1st appearance of red color as 1st xss. SCN-
reacts with Fe3+ giving [Fe(SCN)6]-3 complex.
Fe3+ + 6 SCN- [Fe(SCN)6]-3 red color (at E.p.)
 Volhard’s Method

XXXXX
AgCl E.p.
ppt St. AgNO
Kn. Xss 3
NaCl Sample Fe3+ indicator
St. KSCN
• A kn. xss st. AgNO3 is added to the halide soln., filter & acidify
the filtrate with HNO3.
NaCl + AgNO3 AgCl ↓ + NaNO3
• The xss st. AgNO3 is back titrated with st. SCN- in presence of
Fe3+ (ferric alum) as indicator.
AgNO3 + KSCN AgSCN ↓ + KNO3
• E.p.: detected by 1st appearance of red color as 1st xss. SCN-
reacts with Fe3+ giving [Fe(SCN)6]-3 complex.
Fe3+ + 6 SCN- [Fe(SCN)6]-3 red color (at E.p.)
Important points to be noticed:
1- Titration must be carried out in acidic medium to prevent pptn of
iron(III) indicator as Fe(OH)3.
2- When determining Cl-, AgCl ppt. must be filtered or add
nitrobenzene to coat the AgCl ppt before titration. (Why?)
- AgCl has higher Ksp than AgSCN, thus at the E.p., the following
reaction will occur:
AgCl (s) + SCN- (aq) ⇌ AgSCN (s) + Cl- (aq)
- As a consequence:
• When titrating with SCN-, 1st all xss Ag+ are ppitated as AgSCN.
• Then the 1st xss SCN- will attack the ppt AgCl & displace Cl- in AgCl
ppt to form the less soluble AgSCN (lower Ksp).
• This consumes an xss amount of the titrant, SCN- resulting in an
error in the E.p.
• While with Br- & I- (lower Ksp) the E.p. is distinct as the error is
negligible.
 Adsorption Indicators
• Adsorption Indicators: are dyes change their color
when adsorbed to the surface of the ppt at E.p. Such
compounds are called adsorption indicators.

• They are either:

A- Weak acids e.g. fluorescein & eosin (the anionic part
is the active part) or,
B- Weak bases e.g. Rhodamine 6G (the cationic part is
the active part).
Examples of Adsorption Indicators:

• Fluorescein: used for Cl-, Br- & I-, color change from yellowish
green to pink.

• Eosin (tetrabromofluorescein) : used for Br- & I-, color change

from orange red to bluish red. (Eosin cannot be used for detn. of
chloride: Because eosinate anion is strongly adsorbed by AgCl
ppt. Before the E.p.)

• Chromotrope: used for Br-, color change from pink to grayish

green.

• Rhodamine 6G: used for Ag+, from orange red to violet.

 Theory of adsorption indicators:
(Fajan’s Method)
• It is a direct method for determination of soluble Cl-, Br-, I-
& SCN- by titration diluted sample with st. AgNO3 in
presence of an adsorption indicator.
• The E.p. is detected by sudden change of color of the ppt.
• The method is used for determination of Ag+ by titration
with st. Br- in acidic medium using Rhodamine 6G ind.
 Determination of chloride ions by Fajan’s
method
Principle:-
Secondary adsorbed
layer

Na+ Na+ NO3- NO3-

Primary adsorbed
layer Ag+ Ag+
Cl- Cl-
AgCl AgCl

Ag+
Cl-
Na+ NO3-
1- During titration 2- At the end point
 Determination of chloride ions by Fajan’s method

3- Competition bet.
Fluorescein and nitrate Fl- Fl-
ions at the end point
Ag+ Ag+
AgCl
 Pink complex

Ag+

Fl-
Notes
1) Anionic part of indicator competes with NO3- in forming the 2ry adsorbed layer, & so
it is preferentially adsorbed & forms a colored complex on the surface of the ppt.
2) Eosin cannot be used for detn. of chloride: Because eosinate anion is strongly
adsorbed by AgCl ppt. Before the E.p.
 Denieg’s Method

• It is a direct method for determination of CN- with st. Ag+.

• KI soln is used as indicator.

• At E.p. the yellow turbidity (sharper E.p.) is produced

instead of appearance of white turbidity in Liebeg’s.

2CN- + Ag+ → [Ag(CN)2]- soluble complex

At E.P: [Ag(CN)2]- + Ag+ → 2AgCN ↓ (white ppt)
At E.p.: I- + Ag+ → AgI ↓ yellow ppt