(Midterm) Pharmaceutical Analysis 1 Flashcards
3 DETERMINATION OF THE END POINT
- Cessation of precipitation or the appearance of turbidity
- Use of internal indicators
- Instrumental methods, i.e. potentiometer (by using pH meter) or amperometric
Analyte + titrant →
precipitate
The approach assumes that under the
experimental conditions used, the product is
virtually insoluble
Precipitation
As with other types of reactions, the formation of a precipitate can be used as the basis of a titration.
Precipitation
Just enough titrant has been added to react with all of our analyte.
The equivalence point
Three indicator methods applied to
the titration of Cl- with AgNO3
- Volhard Method
- Fajan’s Method
- Mohr Method
The point where sufficient titrant has been added to be stoichiometrically equivalent to the amount of analyte.
The equivalence point
Now, either the amount of Cl- or Ag+ is in excess.
The equivalence point
At this point, [Cl-] = [Ag+]
The equivalence point
formation of soluble colored complex at the end point
VOLHARD METHOD
Indicator of VOLHARD METHOD
Ferric ammonium sulfate TS
[Fe(NH4)(SO4)2]
Adsorption of a colored indicator at the end point.
FAJANS METHOD
Indirect method for chloride determination.
VOLHARD METHOD
Titrant of VOLHARD METHOD
0.1 N AgNO3 VS and 0.1 N NH4SCN VS
Titrant of FAJANS METHOD
0.1 N AgNO3 VS
Adsorption Indicators in FAJANS METHOD
a. Dichlorofluorescein TS (DCF)
b. Tetrabromofluorescein TS (Eosin Y)
c. Tetrabromophenolphthalein ethyl ester TS (TEE)
It forms a red precipitate of silver
chromate which is seen against the
background of white silver chloride
potassium chromate TS (K2CrO4)
Titrant in MOHR METHOD
0.1 N AgNO3 VS
Uses potassium chromate TS (K2CrO4
MOHR METHOD
Standard Solutions
- 0.1 N AgNO3 VS
- 0.1 N NH4SCN VS
compounds of silver and mercury that can be
readily converted in to soluble mercury of silver salts, may be estimated by direct titration with standard ammonium thiocyanate solution, using ferric ammonium sulfate as indicator.
Direct Titration Method
is based on the complete precipitation of insoluble silver salts from nitric acid solution by the addition of excess standard silver nitrate solution to a soluble salt, and the determination of the amount of silver nitrate solution in excess by residual titration with standard ammonium thiocyanate solution, using ferric ammonium sulfate as the indicator.
Residual Titration Method (Volhard
Method)
Substances other than chlorides that produce slightly soluble silver salts are bromides, iodides, cyanides, thiocyanate, sulfides,
phosphates, arsenate, carbonates, etc.
Residual Titration Method (Volhard
Method)
the second reagent is used to ________ the excess
back titrate
the first reagent is ________ in excess
added
when two reagents are listed, the analysis is by ________
back titration
direct titration with
standard ammonium thiocyanate solution, using ferric ammonium sulfate as indicator
Eosin Y TS
Fajans Method
USP Requirement in Assay of Sodium Chloride
99% - 100.5%
Can be analyzed using either Fajans Method or Volhard Method.
Assay of Sodium Chloride
Indicators in Assay of Sodium Chloride
- FAS TS – Volhard Method
- Eosin Y TS – Fajans Method
FAS TS
Volhard Method
a volumetric procedure for metal determination employing metal-ion indicators in the same manner that pH indicators are used in acid-base titrations.
Complexometric/EDTA Titrations
a.k.a EDTA complexometric titration
disodium ethylenediaminetetraacetate
With the introduction of the analytical reagent
disodium ethylenediaminetetraacetate, a.k.a
EDTA complexometric titration involved.
Complexometric/EDTA Titrations
preferred over the free acid in preparing
the standard solution of EDTA
Disodium salt
has a molecular weight of 372.24
EDTA (C10H14N2Na2O8 with 2H2O)
are best stored in polyethylene containers or in glass containers previously prepared by boiling the container in an alkaline 2% solution of EDTA to remove any metal ions.
Solutions
should be metal-free, therefore glass-distilled
water is preferred.
water
Reagent
▸ Disodium salt
▸ EDTA (C10H14N2Na2O8 with 2H2O)
▸ glass-distilled water
▸ Solutions
indicator used, end point of blue
color
Hydroxynaphthol blue
Preparation and Standardization of
0.05 M EDTA
▸ Hydroxynaphthol blue
▸ Hydrochloric acid
▸ Sodium Hydroxide
alkalinizes the solution to a pH of about 13, so that the Ca-EDTA complex would be stable and any magnesium which might be present as a
contaminant would not react.
Sodium Hydroxide
solubilizes the calcium carbonate by
converting it to calcium chloride
Hydrochloric acid
The formation of a stable, soluble complex
is the driving force in the reaction.
Complexometric Titration
For successful titration with EDTA, Kf must
be greater than 8
Complexometric Titration
The equilibrium constant for the reaction of
a metal ion with a ligand is called Kf or
stability constant.
Complexometric Titration
The formation of a stable, soluble complex
is the ______________
driving force in the reaction
For successful titration with EDTA, __________
Kf must be greater than 8
The equilibrium constant for the reaction of
a metal ion with a ligand is called ___________
Kf or stability constant.
Factors Influencing EDTA Titration
- Activity of the metal ion
- The pH at which the titration is run
- Presence of interfering ions
- Organic solvents
- NaCl
decreases the stability of the complex
NaCl
increases the stability of the complex
Organic solvents
are compounds whose color changes
when they bind to a metal ion.
Metal ion indicators
_____________ must bind metal less strongly than EDTA does
Useful indicators
MgIn(Red) + EDTA(Colorless) →
MgEDTA(colorless) + In(blue)
Metal Ion indicators
▸ Azo dyes
▸ Phthaleins
▸ Tripheylmethane dyes
▸ Xylenol orange
▸ Hydroxynaphthol blue
▸ Hydrocathechol violet
▸ Eriochrome black TS
the colored forms are red (pK 6.3), blue (pK 11.6), yellow orange
Eriochrome black TS
Color of Metal-ion Complex
▸ Calmagite
▸ Murexide
▸ Xylenol (zyleenol) orange
▸ Pyrocatecol violet
Calmagite
wine red
Murexide
yellow (Co +2, Ni, +2, Cu +2); Red (Ca +2)
Xylenol (zyleenol) orange
red
Pyrocatecol violet
blue
EDTA Titration Techniques
- Direct Titration
- Residual Titration
- Displacement Method
- Indirect Titration
Ca 2+, Mg 2+, Zn 2+
Direct Titration
used to indicate the determination of a metal in the presence of another metal.
Masking
Can be accomplished by adjusting the solution a pH of the titration medium so that it will be favorable for complexation of the metal being determined and not of the other metal
Masking
releases metal ion from masking agent (e.g.
formaldehyde)
Demasking Agent
metal ions which are determined by
direct titration with EDTA
Ca 2+, Mg 2+, Zn 2+
cyanide complex can be demasked with
formaldehyde
Demasking Agent
also serve as a masking agents.
Auxiliary Complexing Agent
prevent the precipitation of the metal ion in the absence of EDTA.
Auxiliary Complexing Agent