Pharmaceutical Analysis

Laboratory (1216214)

Precipitation titration of K-tablets supplement

(Argentometric titration)

Prof. Saleh Abu-Lafi

Faculty of Pharmacy
Al-Quds University
List of experiments:
•Experiment 1: Preparation of standard solutions, standardization of HCl
•Experiment 2: Determination of Aspirin using back titration
•Experiment 3: Precipitation titration of potassium tablets (argentometric titration)
•Experiment 4: Gravimetric determination of chloride in KCL tablet
•Experiment 5: Oxidation reduction titration of iron supplement (ferrous sulphate tablet)
•Experiment 6: Complexometric titration of calcium supplement tablet with EDTA
•Experiment 7: Potentiometric titration of aspirin tablet
•Experiment 8: Titration of a diprotic acid (maleic acid), identifying an unknown
•Experiment 9: Analysis of commercial vitamin C tablets using iodometric titration
•Experiment 10: Non-aqueous titration of Loratadine
Objective
Using precipitation titration in the analysis of potassium chloride (KCl) tablets.

Intended learning outcomes (ILOs) ‫مخرجات التعلم‬:

Knowledge:
Upon the completion of this experiment, the student will be able to:
1- describe the principle of precipitation titration
2- explain how formation of a colored precipitate can be used to determine end
point
3- explain the application of these analysis principles in other drug substances
 Argentometric Methods
• Titrations based upon silver nitrate AgNO3
• Most useful precipitation titration because of the low
solubility product of halide salts or Pseudohalides
such as (CN, SCN)

Ksp AgCl 1.82 × 10-10 AgNO3

Ksp AgSCN 1.1 ×10-12

Ksp AgBr 5.0 × 10-13
Ksp AgCN 2.2 ×10-16
Ksp AgI 8.3 × 10-17 KCl
• The most common method of determining the halide ion
concentration of aqueous solution is titration with a standard
solution of silver nitrate AgNO3.
• AgNO3 is the titrant (stains skin and can even cause burns!)
• Cl- is the unknown (potassium chloride (KCl) tablets
supplement)
• At equivalent point, all the AgNO3 converts to AgCl (white
ppt) Ksp = 1.82x10-10 pKsp = 9.74
• [Ag+] = [Cl-] = √Ksp = √1.82x10-10 = 1.35x10-5
• pCl- = pAg+ = 4.87
Mohr Method

• Direct titration
• Ag+ + Cl-  AgCl ppt (white)
• Basis of endpoint: formation of a colored secondary
precipitate Ag2CrO4(s)
• Indicator: soluble chromate salt (Na2CrO4) ‫اصفر ليموني‬
• 2Ag+(aq) + CrO42-(aq)  Ag2CrO4(s) (indicator rxn)
• Ag2CrO4(s) has brick red in color
Mohr Method
• Has to be performed at a neutral or weak basic solution of
pH 7-9
• In a lower pH (acid solution)
CrO42-(aq) + H+(aq)  H2CrO4 chromic acid, need
more Ag+ to form Ag2CrO4
• Sometimes 2 CrO42- +2H+  Cr2O72- Ag2Cr2O7 ppt

• In a higher pH (basic solution) > 10

Ag+(aq) + OH-(aq)  AgOH(s) silver hydroxide
may precipitated. It has a brown color
Mohr Method for Cl- determination
• Relies on Ksp differences for two insoluble silver salts.
Ag+(aq) + Cl-(aq)  AgCl(s) (titration rxn)
2Ag+(aq) + CrO42-(aq)  Ag2CrO4(s) (indicator rxn)
• AgCl is less soluble than Ag2CrO4 so it will precipitate first
• Ag2CrO4 is brick red in color so a color change is observed
at the endpoint
• The indicator is used diluted to give in practice an accurate
equivalent point
The endpoint when seeing the slight red-brown
color of silver chromate
Past the equivalent point stronger red-brown is formed
Procedure:
Mohr Method

1. Weigh 10 Potassium Chloride (SlowK®) tablets and determine the average tablet weight.
2. Crush the tablets using a mortar and pestle.
3. Using a clean dry weighing dish, weigh accurately, triplicate ~0.2 g samples of KCl powder.
4. Record the accurate weight and then put each sample in a clean and dry Erlenmeyer flask.
5. Add 50ml distilled water to dissolve the powder.
6. Add 1-2ml of 5% potassium chromate solution as indicator.
7. Clean, rinse, and fill a buret with the standardized 0.1M silver nitrate solution.
8. Titrate the sample with silver nitrate until the color change from yellow to red or orange.
9. Record the volume of AgNO3 added to the flask.
10. Calculate the amount of potassium chloride.
Calculation:
Mohr Method
According to the reaction equation: Ag+ + Cl- → AgCl(s)
Silver nitrate reacts with chloride anion on the (1:1) mole ratio, therefore

# moles of KCl = # moles of AgNO3

Wt of KCl in the sample (grams)
= M AgNO3 x Volume AgNO3
MWt of KCl 74.5g/mole

1 mole 𝐾𝐶𝑙
= M 𝐴𝑔𝑁𝑂3 x V𝐴𝑔𝑁𝑂3 ml x (1 mole 𝐴𝑔𝑁𝑂3) x MWt of KCl
% KCl x 100
Wt sample in (mgs)
 Volhard Method
• Indirect method, requires a back-titration of the excess Ag+
• First, Cl- is precipitated as AgCl by excess addition of AgNO3
Ag+ (aq) + Cl-(aq)  AgCl(s) white ppt (filter out or add
nitrobenzene organic solvent to coat the AgCl precipitate, thus protecting it
from liberating Ag+ before the back titration).
• Excess Ag+ is back titrated with KSCN in the presence of indicator of ferric
alum indicator NH4Fe(SO4)2 notice the iron oxidation state is (Fe3+ )
• (KSCN is not 1o std, it should be standardized with AgNO3)
Ag+(aq) excess + SCN-(aq)  AgSCN(s) (white ppt)
• When Ag+ has been consumed, one extra drop of SCN- forms an orange-red
complex with the ferric alum NH4Fe(SO4)2 indicator

Fe3+(aq) + SCN-(aq)  FeSCN2+(aq) orange-red complex

 Volhard Method
1. Using a clean dry weighing dish, weigh accurately, triplicate ~0.2 g samples of KCl
powder. Record the accurate weight and then put each sample in a clean and dry
Erlenmeyer flask.
2. Add 50 ml distilled water to dissolve the powder.
3. Add 5 ml nitric acid solution to decrease the pH of the medium.
4. Add 50 ml of the standardized of 0.1M silver nitrate solution
5. Add 2 ml of the organic solvent nitrobenzene.
6. Add 1 ml of FeIII Ferric alum solution as indicator.
7. Clean, rinse, and fill a buret with the standardized 0.1M potassium thiocyanate solution.
8. Titrate the sample with potassium thiocyanate solution until the color darkens.
9. Record the volume of KSCN added to the flask.
Calculate the amount of potassium chloride.
 Calculation:
Volhard Method
Ag+ + Cl- → AgCl(s)
Ag+ excess + SCN- → AgSCN(s)

moles of KCl = Total moles of added AgNO3 − excess moles of AgNO3

= Total moles of added AgNO3 − moles of KSCN
Wt of KCl in the sample (grams)
= MAgNO3 x Volume AgNO3 − MKSCN x Volume KSCN
MWt of KCl 74.5g/mole

1 mole 𝐾𝐶𝑙
= MAgNO3 x Volume AgNO3 − MKSCN x Volume KSCNx (
1 mole 𝐴𝑔𝑁𝑂3
) x MWt of KCl
% KCl x 100
Wt sample in (mgs)
Fajans Titration
• Uses adsorption indicator (In-)
Since fluorescein and its derivatives
-O O O
are weak acids, the pH of the
solution should be slightly alkaline
Cl Cl
to keep the indicator in the anion
form but, at the same time, is not
CO 2-
alkaline enough to convert Ag+ into
AgOH.

Dichlorofluorescein is green in solution

but pink when absorbed on AgCl
Fajans Method
Fluorescein and its derivatives are adsorbed to the surface
of colloidal AgCl. After all chloride is used, the first drop
of Ag+ will react with fluorescein (In-) forming a reddish
color.
Ag+ + In- (Yellowish green) = AgIn (Red)
Fajans Titration
• Prior to the equivalence point, there is
excess Cl- in solution. Some is adsorbed on
the surface of the crystal, giving a partial
negative charge. Repulsion with
the –ve charge of the In-

• After the equivalence point, there is excess

Ag+ in solution. Some adsorbs to the surface
imparting a partial positive charge to the
precipitate. Attract In-
In-
In-
Fajans Titration
Statistical measurements

SD, RSD, CL, etc.