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In analytical chemistry, argentometry is a type of titration involving the silver(I) ion. Typically, it is
used to determine the amount of chloride present in a sample. The sample solution is titrated
against a solution of silver nitrate of known concentration. Chloride ions react with silver(I) ions
to give the insoluble silver chloride:

Ag+ (aq) + Cl− (aq) → AgCl (s) (K = 5.88 × 109)

Contents

Volhard method

Mohr method

Fajans method

See also

References

Volhard method[edit]

An example of back titration, the Volhard method, named after Jacob Volhard, involves the
addition of excess silver nitrate to the analyte; the silver chloride is filtered, and the remaining
silver nitrate is titrated against ammonium thiocyanate,[1] with ferric ammonium sulfate as an
indicator which forms blood-red [Fe(OH2)5(SCN)]2+ at the end point:

Ag+ (aq) + SCN− (aq) → AgSCN (s) (Ksp = 1.16 × 10−12)

Fe(OH)(OH2)2+

5 (aq) + SCN− (aq)→ [Fe(OH2)5(SCN)]2+ + OH−

Mohr method[edit]

In the Mohr method, named after Karl Friedrich Mohr, potassium chromate is an indicator, giving
red silver chromate after all chloride ions have reacted:

2Ag+ (aq) + CrO2−

4 (aq) → Ag2CrO4 (s) (Ksp = 1.1 × 10−12)

The solution needs to be near neutral, because silver hydroxide forms at high pH, while the
chromate forms H2CrO4 at low pH, reducing the concentration of chromate ions, and delaying
the formation of the precipitate. Carbonates and phosphates precipitate with silver, and need to
be absent to prevent inaccurate results.

The Mohr method may be adapted to determine the total chlorine content of a sample by
igniting the sample with calcium, then ferric acetate. Calcium acetate "fixes" free chlorine,
precipitates carbonates, and neutralizes the resultant solution. Ferric acetate removes
phosphates. All chlorides are dissolved out of the residue, and titrated.[1]

Fajans method[edit]

In the Fajans method, named after Kazimierz Fajans, typically dichlorofluorescein is used as an
indicator; the end-point is marked by the green suspension turning pink. Prior to the end-point
of the titration, chloride ions remain in excess. They adsorb on the AgCl surface, imparting a
negative charge to the particles. Past the equivalence point, excess silver(I) ions adsorb on the
AgCl surface, imparting a positive charge. Anionic dyes such as dichlorofluorescein are attracted
to the particles, and undergo a colour change upon adsorption, representing the end-point.
Eosin (tetrabromofluorescein) is suitable for titrating against bromide, iodide, and thiocyanate
anions, giving a sharper end-point than dichlorofluorescein. It is not suitable for titrating against
chloride anions because it binds to AgCl more strongly than chloride does.[2]

See also[edit]

Silver halide

Titration

References[edit]

Jump up to:
a b Yoder, Lester (1919). "Adaptation of the Mohr Volumetric Method to General Determinations
of Chlorine". Industrial & Engineering Chemistry. 11 (8): 755. doi:10.1021/ie50116a013.

^ Harris, Daniel Charles (2003). Quantitative chemical analysis (6th ed.). San Francisco: W.H.
Freeman. pp. 142–143. ISBN 0-7167-4464-3. Mohr method of determination of chlorides by
titration with silver nitrate is one of the oldest titration methods still in use - it was researched
and published by Karl Friedrich Mohr in 1856.

The idea behind is very simple - chlorides are titrated with the silver nitrate solution in the
presence of chromate anions. End point is signalled by the appearance of the red silver
chromate.

Intense yellow color of chromate may make detection of first signs of formation of red silver
chromate precipitation difficult. As some excess of silver must be added before precipitate starts
to form, if concentration of titrant is below 0.1M, we may expect singificant positive error. To
correct for this error we can determine a blank, titrating a solution of the indicator potassium
chromate with standard silver nitrate solution. To make result more realistic we can add small
amount of chloride free calcium carbonate to the solution to imitate the white silver precipitate.

Solution during titration should be close to neutral. In low pH silver chromate solubility grows
due to the protonation of chromate anions, in high pH silver starts to react with hydroxide
anions, precipitating in form of AgOH and Ag2O. Both processes interfere with the determination
accuracy.

Exactly the same approach can be used for determination of bromides. Other halides and
pseudohalides, like I- and SCN-, behave very similarly in the solution, but their precipitate tends
to adsorb chromate anions making end point detection difficult.

reaction

Reaction taking place during titration is

Ag+ + Cl- → AgCl(s)

sample size

Assuming 0.1M titrant concentration and 50 mL burette, aliquot taken for titration should
contain about 0.12-0.16 g chloride anion (3.5-4.5 millimoles).

end point detection

Before titration small amount of sodium or potassium chromate is added to the solution, making
its slightly yellow in color. During titration, as long as chlorides are present, concentration of Ag+
is too low for silver chromate formation. Near equivalence point concentration of silver cations
rapidly grows, allowing precipitation of intensively red silver chromate which signalls end point.
See precipitation titration end point detection page for more detailed, quantitative discussion.
solutions used

To perform titration we will need titrant - 0.1 M silver nitrate solution, indicator - potassium
chromate solution, and some amount of distilled water to dilute sample.

procedure

Pipette aliquot of chlorides solution into 250mL Erlenmeyer flask.

Dilute with distilled water to about 100 mL.

Add 1 mL of 5% potassium chromate solution.

Titrate with silver nitrate solution till the first color change.

result calculation

According to the reaction equation

Ag+ + Cl- → AgCl

silver nitrate reacts with chloride anion on the 1:1 basis. That makes calculation especially easy -
when we calculate number of moles of AgNO3 used it will be already number of moles of Cl-
titrated.

To calculate chlorides solution concentration use EBAS - stoichiometry calculator. Download

determination of chlorides concentration reaction file, open it with the free trial version of the
stoichiometry calculator.

Click n=CV button above Ag+ in the input frame, enter volume and concentration of the titrant
used. Click Use button. Read number of moles and mass of chlorides in the titrated sample in the
output frame. Click n=CV button in the output frame below Cl-, enter volume of the pipetted
sample, read chlorides concentration.

sources of errors

This is relatively easy titration, with no other problems then those listed on general sources of
titration errors page.

Page was last modified on December 13 2009, 10:45:50.

Categories: Analytical chemistryTitration