VOLUMETRIC PRECIPITIMETRY METHODS

: These are class of reactions that deal with the formation of relatively insoluble ADSORPTION INDICATORS used in the official volumetric
substance (or precipitates). precipitation assays:

: The completion (endpoint) of the reaction is determined through the following: Dichlorofluorescein (DCF) TS (test Solution 10%)
The formation of these precipitates is the product of
chemical reaction (between the analyte/ sample and the
titrant). These precipitates serve as the basis for the
completion of a certain chemical reaction Eosin Y TS

; Formation of colored precipitate (the color depends on

the species).
Complex: Metallochromic indicators Tetrabromophenolphthalein ethyl ester
; Formation of a soluble colored compound.
Acid base: Acid base indicators
Then after adding an excess titrant, precipitate dissolves
These indicators are weak organic acids used in the analyses
which will result to a different colored soluble compound .
of halides by direct titration with silver nitrate (AgNO3)
; Use of adsorption indicators
solution .
At the equivalence point, the indicator is ‘adsorbed‘ by the
precipitate . The endpoint of the titration is indicated when color of the
During the process of adsorption, a change occurs in the silver halide precipitate changes abruptly (because the
indicator which leads to a substance of different color.
adsorbed indicator anion reacts with silver ions, displacing the
; Turbidity method
halides
Appearance of turbidity is sometimes utilized to mark the Halides are halogens with negative sign
endpoint of the reaction
Without the negative signs they are halogens
OTHER INDICATORS used in the official volumetric precipitation assays

Why does precipitation occur?

- Ferric ammonium sulfate (NH4Fe(SO4)2 . 12H2O) TS (aka Ferric Alum)
Used both in direct and residual titrations employing standard ammonium
thiocyanate(NH4SCN) solution.
Direct – AgNO3
It is because the precipitate has low solubility product constant (Ksp)
value than the other species in the solution.
Ksp is the product of the concentration of ions in a solution.

Residual – excess – AgNO3 AgNO3 + NaCl --- AgCl + NaNO3

Silver nitrate Sodium chloride Silver chloride (precipitate) Sodium nitrate

- Back titrant – NH4SCN
After precipitation, thiocyanate ion (SCN-) reacts with ferric ammonium
sulfate to form red ferric thiocyanate.
SCN- + Fe3+ ------ Fe(SCN)3
Examples of analytes are: Mercury and Silver
The Ksp expression of each species is the product of the molar
concentration of Cations and anions.
Silver chloride precipitates out because its Ksp value is achieved (which
is low). It has low Ksp value as compared to other species. High Ksp of s
substance means high solubility.

- Potassium Chromatee (K2CrO4 TS) – Used in the analysis of
Chloride (and other halides). Yellow solution
It is seen as a red precipitate of silver chromate against the
background of silver chloride.
CrO4 -2 + Ag+ ------ Ag2CrO4
(Yellow to red)
Ksp can have different values, because solubility of a compound is
affected by different factors:
- Common ion effect The addition of the common ion shifts the
equilibrium of a slightly soluble ionic compound toward the
undissolved compound, causing more to precipitate. Thus, the
solubility of the compound is reduced.
AgCl ------ Ag+ + Cl-
AgCl salt dissociates to form silver and chloride ion If we add more
either Ag or Cl in the solution, the equilibrium shifts to form more AgCl

- Complex Formation the addition of a complexing agent
can solubilize the solid precipitate.
AgCl ------ Ag+ + Cl-
- If we add ammonia (NH3) ( which acts as complexing
agent) to a solution of AgCl, it dissolves the precipitate
forming a soluble complex of [Ag(NH3)2]+
- Temperature- generally, higher temperature
dissolves a precipitate (increase solubility). However,
there are salts that are more soluble in cold
temperature such as Calcium hydroxide.
Standardization of 0.1 N Silver Nitrate
Any titration that uses silver nitrate as standard is termed as Argenometry
Procedure
Dissolve about 17.5 g of silver nitrate in 1000 mL of water and standardize. Transfer
about 100 mg , accurately weighed, of a reagent – grade sodium chloride, previously
dried at 100 C for 2 hours, to a 150-mL beaker dissolve in 5 mL of water, and add 5
mL of acetic acid, 50 mL of methanol, and about 0.5 mL of eosin Y TS. Stir,
preferably with a magnetic stirrer, and titrate with the silver nitrate soln.
Preparation: 17.5 g of silver nitrate in 100 mL of water
Dissolve Dissolve about 17.5 g of silver nitrate in 1000 mL of water and standardize.

- Interference ions What is the actual normality produced when 17.5 g of silver nitrate is used?

N = EW / Liter of soln. N = Molarity X Factor

- Solvent- This also depends on the nature and quality
of the solvent. Polar solvents usually dissolves salts
than non-polar solvents.

Weight given is 17.5 g, and MW of silver nitrate is 169.87 g/mol

What are the substances analyzed in VP methods ?
1000 mL (volume solution) = 1 L
- Halides
The factor of silver nitrate is 1 since silver ion and nitrate ion share one electron
- Halogenoids (Pseudohalides)
(Ag+ and Cl-). This is how the factor is derived for salts. (How is this different form
- Mercaptans redox?)
- Fatty Acids
- Divalent inorganic compounds
Accurately weigh about 100 mg of a reagent-grade sodium chloride, previously dried at
100 c for 2 hrs.
How much volume of 0.1n AgNO3 is required to react with 100 mg of NaCl?
NaCl is used as the primary standard (analyte). In this case, reagent-grade
(estimated to have 5% moisture and to used primarily for analytical purpose) is used
instead of analytical grade (with high purity) because the moisture can be removed by
drying. Nitric acid my also be used to standardize silver nitrate. The reaction
between silver nitrate and sodium chloride is given below:
This must be protected from sunlight of UV irradiation because UV decomposes silver
halides, which turn to graysh or black owing to the formation of silver metal, although
the reaction is slow though
Cried at this temperature to remove any moisture.Nacl is deliquescent,
so use weighing bottle
Dissolve in 5 mL of acetic acid, 50 mL of methanol, and about 0.5 ml of
eosin YTS, in a 150 mL beaker. Stir, preferably with a magnetic stirrer,
and titrate with the silver nitrate soln.
Eosin Y is the adsorption indicator used. It provides a sharp endpoint in
acidic media( the color change is sharpest in an acetic soln.) Hence,
acetic acid is used to sharpen the endpoint.
Eosin Y, however can compete with the chloride ions to react with the
silver ions. If eosin Y reacts first with silver, there will be a premature
determination of the endpoint. All chloride ions (from sample NaCl) must
react first with silver ions (from AgNO3) before Eosin Y. Methanol is
added to prevent this competition. Alcohol is used in the assay to help keep
the precipitated silver chloride in a colloidal state and thus give
sharpness to the color change which occurs on the precipitate surface.
The color of the precipitate of eosin Y with silver is magenta. So the
color of the precipitate of AgCl(white) changes to magenta (endpoint)
If all Nacl is consumed already , then eosin Y reacts with AgNO3.
A disadvantage of adsorption indicators is that silver halides are sensitized to the
reaction of light by a layer of adsorbed dyestuff. For this reason, titrations should
be carried out with a minimum exposure to sunlight.

Rules on the use of Adsorption Indicator

- The precipitate should separate as far as possible in the solution. Large

quantities of neutral salts (with different charges) should be avoided owing to
their precipitating effect. (This is another reason why methanol is added, to
prevent other ions that can be precipitated).
- The indicator ion must have an opposite charge to the ion of the precipitating
agaent (AgNO3).( Eosin Y is negatively charged complex ion, hence it can be
precipitated by silver.)
- The indicator ion should not be adsorbed before the particular compound has
been completely precipitated, but it should be strongly adsorbed immediately
after the equivalence point.

You would expect that 8 g is an excess amount. But since ammonium

thiocyanate is deliquescent, a slight amount in excess of the theoretical
quantity required is used in preparation of the solution . If desired,
potassium thiocyanate may be used in place of ammonium thiocyanate.
Standardization of 0.1 N NH4SCN Methods of Volumetric Precipitimetry
- Dilute with 50 mL of water , then add 2mL of nitric acid and 2 Ml of - Gay-Lussac Method
ferric ammonium sulfate Ts, and titrate with ammonium thiocyanate soln. ; Based in the cessation of precipitation
to the first appearance of a red-brown color ;employs direct titration with silver nitrate VS as titrant
; Analyte: Halides (X-)
The soln. must be acidified with nitric acid to prevent the hydrolysis that ferric
salts undergo in neutral soln.

Disadvantages of Gay-Lussac’s Method:

Ferric Ammonium thiocyanate serves as the indicator. After (ammonium)
thiocyanate reacts with silver (nitrate), as soon it has all been precipitated, the
thiocyanate ion reacts with ferric ammonium sulfate to form a red ferric
thiocyanate.
; not indicated for fluorides
; It is difficult to observe cessation of precipitation (therefore,
there is a tendency for over titration
- Mohr Method
; Based on the formation of a second highly colored precipitate
; employs direct titration with silver nitrate VS as titrant.
; Analyte: Halides (X-, but not for iodide)
; Indicator: Potassiium Chromate (K2CrO4)- Difference from gay-Lussac.
The use of an indicator remedies its disadvantgaes.
 - Important considerations in Mohr’s Method
; Temperature
The higher the temp. , the higher solubility of the red Ag2CrO4
resulting to increased addition of titrant
When complete precipitation occurs, (no more halides are precipitated), the
; Remedy:
silver nitrate will now react with chromate (indicator) to form silver
Control temp. at 25 C
chromate precipitate indicating the endpoint of titration
- Concentration of the indicator K2CrO4
- At lower concentration, the titrating soln. would be so yellow as to
make the detection of the appearance of read AgCrO4 difficult.

; Remedy

This is usually computed, depening on he amount of anayte. It is

usually prepared though by dissolving 10g of potassium chromate in 100
; Important considerations in mohr’s Method
mL water. In practice, a lower concentration is used.
; required ph condition: neutral (pH 8)

If titrated in acidic (pH< 6) condition, chromate reacts with acid to form

- Volhard Method
dichromate:
; Based on the formation of a soluble, colored complex
; Employs Residua titration with silver nitrate VS as excess titrant
and ammonium thiocyanate VS as Back titrant
; Analyte: Halides (X-)

When dichromate reacts with AgNO3 instead of chromate, it will not form a
precipitate because silver dichromate is soluble
Based on the complete precipitation of insoluble silver salts from HNO3 by the
addition of excess AgNO3 to a soluble salt and the determination of the amount of
AgNO3 in excess by residual titration with standard NH4SCN solution, using ferric
Ammonium sullfate NH4Fe(SO4)2 . 12H2O as the indicator
; Also employs direct Titration with ammonium Thiocyanate Vs as titrant.
; Analyte: Mercury (Hg) compounds
;Indicator: Ferric Ammonium Sulfate (aka Ferric Alum)

Nitric acid- used to prevent the precipitation of silver as carbonate, phosphate,

etc., and to prevent hydrolysis of the indicator, ferric alum.

; Indicator; Ferric Ammonium Sulfate (aka Ferric Alum)

- Based on the appearance of turbidity

; Employs direct titration with silver nitrate VS as titrant
; Analyte: Cyanides (CN-)
There are now two precipitates. AgSCN and AgX. However, AgX becomes soluble
when AgSCN is formed and therefore must not happen since it will liberate again
the halide being titrated. Filtering off AgX before addition off the backtitrant
may be done, or to avoid filtration, nitrobenzene is added in the solution, so that
When AgNO3 is added into the soln. containing CN-, a White precipitate
AgX will remain undissolved.
of AgCN forms.

Further addition of silver nitrate yields the insoluble Ag[ Ag(CN)2]

; There is addition of NH3 the soln. - Fajans Method
; Employs Direct titration with silver Nitrate VS as titrant
This is made because of difficulty in obtaining a sharp endpoint since silver Analyte: Halides (X-)
cyanoargentate formed close to the endpoint is slow to redissolve, making the
titration time consuming , Ammonia solution is added to prevent the precipitation
by dissolving silver cyanoargentate.

; Based on the adsorption of the indicator on the surface of the

precipitate

Ex: Chloride
When Ag+ is added to Cl, (forming a white precipitate), there is still excess
Potassium Iodide is used as indicator. It reacts with [Ag(NH3)2]+ to form Agl
Cl- in soln. prior to the equivalence point..
yellow precipitate.
After the equivalence point, there is excess Ag+ in the solution
Adsorption of Ag+ onto the AgCl surface places positive charge on the
precipitate.

Common adsorption indicators are anionic dyes, which are attracted to

positively charged particles produced immediately after the equivalence
point.
Also, ammonia prevents the formation of toxic HCN (Hydrogen cyanide) gas
resulting from the reaction of CN- with water.
The most common indicator for Cl- is dichlorofluorescein. This dye is
greenish yellow in soln. but turns pink when adsorbed into AgCl