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PHAN 1: TOPIC 7
PRECIPITATION METHOD
-Also called Argentometric titration
❖ Volumetric methods based on reactions that yield
ionic compounds of limited solubility
❖ Analyte is titrated with a standard solution of a
precipitating agent in the presence of a suitable
indicator.
-Official V.S: AgNO3 and KSCN/NH4SCN
It applies the solubility product principle
❖ States that in a saturated solution of an ionic
compound, the product of the molar activities (Ksp), has
a constant value at any particular temperature and
pressure
❖ Ionic product exceeds the Ksp precipitation
[Ag] [Cl] -> AgCl ppt.
>KSP: Solubility Product Constant
>Supersaturated: above max level
>Saturated: Maximum
>Unsaturated: Below max level
ENDPOINT
-Determined by
❖ Cessation (stopping) of precipitation or appearance
of turbidity
❖ Instrumental methods (potentiometry)
❖ Use of internal indicators
(INS TABLE PG 115)
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Indicators
❖ Colored Ion – Volhard Method (Jacob Volhard)
❖ Colored precipitate – Mohr Method (Karl Friedrich
Mohr)
❖ Colored Adsorption product – Fajan Method
(Kazimiers Fajan)
COLORED ION
❖ Volhard’s Method
❖ Ferric alum TS
❖ Slight excess thiocyanate ion reacts with ferric ion
from the indicator producing a faint reddish brown
coloration
❖ Used in thiocyanate titrations
FeNH4(SO4)2 + 3 NH4SCN → Fe(SCN)3↓ + 2 (NH4)2SO4
COLORED SECONDARY PRECIPITATE
❖ Mohr Method
❖ Potassium chromate solution (K2CrO4)
❖ chromate reacts with excess silver ions forming a
secondary precipitate of reddish silver chromate
❖ Used in the titration of halides with standard silver
nitrate solution
AgNO3 + K2CrO4 → AgCrO4 ↓ + KNO
COLORED ADSORPTION PRODUCT
❖ Fajan Method
❖ Dichlorofluorescein, Eosin Y, TEE - fluorescence
❖ used as indicator in the titration of potassium
chloride with standard silver nitrate solution.
❖ silver chloride (ppt)formed is negatively charged due
to adsorbed chloride ion and the indicator exists in the
solution with a greenish yellow
❖ Direct titration with silver nitrate
KCl + AgNO3→ AgCl ↓ + KNO3
Gram Equivalent Weight
-The gram-equivalent weight of a substance in the
precipitation method is obtained by dividing the
molecular weight by the total valence of the
precipitating or precipitated ion
-AgBr | KBr | BaCl2 | Hg
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Compounds assayed Direct titration with ammonium thiocyanate

Substances assayed: ASSAY OF SILVER NITRATE
-mainly used for determination of HALIDES and some -Accurately weighed sample of silver nitrate Dissolved in
compounds that form insoluble products (ppt) with 50 mL of water and
AgNO3. -2 mL of nitric acid
-2 mL of ferric ammonium sulfate T.S.
PRECIPITATION METHOD -Titrate with 0.1-N ammonium thiocyanate T.S.
>STANDARD SOLUTIONS -Calculate the percentage purity of AgNO3
Silver Nitrate, Potassium Thiocyanate,
Ammonium Thiocyanate. Assay -Residual titration method
>SUBSTANCE ASSAYED Volhard Method
Silver compounds, Mercuric compounds, Halide ASSAY OF SODIUM CHLORIDE
compounds, Theophylline compounds -An accurately weighed sample (250 mg) Dissolved in
50mL of water
-Add 50 mL of 0.1-N AgNO3 solution, 3 mL of HNO35 mL
PREPARATION & STANDARDIZATION of nitrobenzene
0.1 N SILVER NITRATE -2 mL of ferric ammonium sulfate of T.S. Titrate the
1 STANDARD SOLUTION: Silver Nitrate excess silver nitrate with 0.1-N NH4 SCN.
2 PRIMARY STANDARD : Sodium Chloride -Calculate the percentage purity of NaCl.
3 INDICATOR: Dichlorofluorescein
NaCl + AgNO3→ AgCl ↓ + NaNO3
PRACTICE PROBLEMS: ASSAY
PREPARATION & STANDARDIZATION
0.1 N AMMONIUM THIOCYANATE >A sample ammonium bromide weighing 0.4128 gram
1 STANDARD SOLUTION: Ammonium Thiocyanate was dissolved in water, acidified with HNO3 and 50 mL
2 PRIMARY STANDARD : 0.1 N Silver Nitrate of 0.1-N AgNO3 solution added. The excess of the latter
3 INDICATOR: Ferric alum required 16.5 mL of 0.05015-N NH4SCN solution for
AgNO3+ NH4SCN → AgSCN↓ + 2 (NH4)NO3 titration. What is the percentage purity of NH4Br in the
FeNH4(SO4)2 + 3 NH4SCN → Fe(SCN)3↓ + 2 (NH4)2SO4 sample?

Assay – Direct Titration

- Direct titration with silver nitrate

ASSAY OF SODIUM LAURYL SULFATE FOR SODIUM
CHLORIDE CONTENT
-Accurately weighed sample (around five grams)
Dissolved in 50 mL of water.
-Neutralize the solution with dilute nitric acid. Add 2 mL
of potassium chromate T.S.
-Titrate with 0.1-N silver nitrate.
Each mL of 0.1-N AgNO3 ≈ 5.844 mg of NaCl. Calculate
the percentage of NaCl in sodium lauryl sulfate.

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A 0.5 gram sample of SrCl2 required 45.6 mL of AgNO3 GRAVIMETRY

. AgNO3 was prepared by dissolving 5 grams of pure Ag -Prepare AgNO3 solution
to make 500 mL of solution. Excess AgNO3 consumed -Measure accurately AgNO3 soln
16 mL of 0.015N of KSCN. Calculate the percentage -Treat with dil HCl
purity of SrCl2 AgNO3 + HCl→ AgCl +HNO3
-AgCl precipitate is purified and dried
-Weigh the precipitate
-Compute for the N

Formula:

SAMPLE COMPUTATION GRAVIMETRY

A 0.2182 g sample of sodium chloride was assayed by Calculate the HgCl2 (MW= 271.50) content of a sx of
Volhard method using 50.0 ml of 0.0985N AgNO3 and Mercuric Cl if 0.2551 g of which yields 0.1815 g of HgS.
11.75ml of 0.1340N NH4SCN. Calculate the % NaCl in (MW = 232.65)
the sample.

If a 0.4600g of potassium iodide (KI) yielded a 0.715g of

What volume of 0.05015-N thiocyanate solution would silver iodide precipitate by gravimetric assay, what
be required to titrate the excess from 50 mL of 0.1-N would be the percentage purity of KI?
AgNO3 that was added to a solution of 0.2215 gram of (At.wt.: Ag = 107.87; K = 39.1; I = 126.9)
NH4Cl (53.5) which is 99.5% pure?

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TOPIC 8: Complexometry or Compleximetric titrations

COMPLEXATION METHOD
❖ These titrations are used in the estimation of metal
salts.
❖ Complexometry (complex-formation method) is the
process based on the formation of a complex substance
in the course of analysis.
❖ Uses: Calcium, copper, mercury, magnesium, zinc,
aluminum and bismuth
❖ EDTA will react with metal ions to form a water
soluble stable complex or a chelate compound
Complexometry cont
❖ When a metal ion combines with a molecule which
donate electrons, the resulting compound is termed a
complex.
❖ If the combining molecule contains two or more
groups that donate electrons, this complex is called a
chelate.
❖ The groups bound to the central ion are calld ligands.
Complexometric Method
❖ Uses: Complexometric method is used to determine
hardness of water which is due to calcium and
magnesium salts, calcium compounds and their
preprations e.g. calcium gluconate and its tablets,
calcium panthothenate and its tablets, calcium chloride
injection and calcium gluconate injection.
Complexometry
❖ Stability constant - measure of the strength of the
interaction between the reagents that come together to
form the complex.
❖ Stability constants should be greater than 8.
❖ Li, Na → forms very weak complex
❖ Ag and Ba → Ks is below 8
❖ Fe and Cu → colored metals
Factors affecting EDTA reaction
❖ Stability constant
❖ pH ( NaOH or ammonia-ammonium chloride
buffer TS)
❖ Interfering ions (cyanide, citrate, tartrate,
fluoride and other complex-forming agents)
❖ Neutral salts – NaCl
Indicators
❖ Organic compounds which form colored complex
ions with metal ion in high dilutions.
❖ Qualities of a good indicator are
❖ sharpness of color change at the endpoint
❖ specificity of the indicator for the metal ion under
the conditions of the analysis
❖ stability constant smaller than that of the metalEDTA
complex –i.e. the indicator must give up the metal ion
to the titrant EDTA for complexing and not compete
with it.

What is EDTA? 6 Indicators:

• Calmagite
❖ usual titrant used.
• Hydroxynapthol blue (CALCIUM)
❖ it forms stable 1 : 1 complexes with all metals except • Eriochrome Black (ZINC)
alkali metals such as sodium and potassium.
• Murexide
• Pyrocatechol Violet
• Dithizone (ALUMINUM, BISMUTH)
INS EDTA PIC 143
Standard Solution
❖ EDTA – disodium EDTA solution 0.05M
❖ Primary Standard: calcium carbonate
❖ Indicator: hydroxynaphthol blue (endpoint -
appearance of a deep blue color)
❖ Hexadentate ligand
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Complexometry cont Hardness of Water

Molarity – no. of moles per liter of solution rating Concentration of calcium
carbonate (mg/L)
Ins formula pg 151 Soft 0-75
Medium hard 75-150
Hard 150-30
Very hard 300 and greater

MASKING
Direct Titration/ Residual Titration ❖ Masking – the term used to indicate the
>Used for assay Ca, Mg and Zn determination of a metal in the presence of
❖ Calcium chloride another metal
❖ Zinc sulfate
❖ Ca in water or water hardness MASKING AGENT ELEMENTS MASKED
Triethanolamine Al, Fe, Mn
> Used for assay of Al, Bi compounds Thioglycol (2,3 Hg, Cu, Bi
❖ Residual EDTA is determined using Metal-ion dimercaptopropanol)
solution (Zinc sulfate) and stable indicator Cyanide Zn, Cu, Ni, Co
(dithiazone) Ammonium Fluoride Mg, Al, Ca

❖ Insoluble metal salts are estimated by back titration; SAMPLE PROBLEMS: COMPLEXOMETRY
the sample is heated with excess EDTA to form the
soluble EDTA complex of the metal and then the excess A 50 mL water sample was determined for hardness in
EDTA is titrated with salt solutions containing Mg2+ terms of CaCO3 . It required 40 mL of a 0.01-M EDTA
or Zn2+ of known concentration. solution for titration. Calculate the total hardness in
❖ Back titration with EDTA is used in the ppm. (mg/million)
pharmacopoeial assays of aluminium glycinate,
aluminium hydroxide, aluminium sulphate and calcium
hydrogen phosphate.

Hardness of water
❖ Metal ions(minerals) that are dissolved in the ground
water
❖ Temporary and Permanent
A 50 mL water sample was titrated with 4.0 mL of
(Ca2+ , Mg+2 , Fe3+ and SO4-.)
disodium edetate [42.5 mL EDTA were used to titrate
❖ Measure of the capacity of the water to precipitate 0.08275 gram of MgO]. Find the hardness in ppm due to
soap calcium. CaCO3 = 100
>Soap scum, clog pipe
❖ Parts per million (ppm)

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Calculate the calcium carbonate content of a sample of

chalk weighing 0.2545g and consuming 16.67mL of
0.1150M of EDTA solution in titration. The percentage
of CaCO3 is:

What volume of 0.05 M EDTA solution would be

equivalent to 100 ml of a 0.025 M solution of titrable
divalent cations?

Masking
In a solution containing the following metals:
Magnesium, Zinc, Mercury, Aluminum and Copper
I. Mg III. Hg V. Mn II. Zn IV. Al

1. Which of these metals may form complex with

EDTA if the above solution is treated with KCN?

2. If the sample will be treated with triethanolamine,

which of these metal/s will be precipitated?

3. Which of these metals will not form complex with

thioglycol?