Precipitation Titrations General

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Precipitation Titrations
“If you’re not part of the solution,
then you’re part of the precipitate”
-Anonymous
www.hannainst.com& Copyright Hanna Instruments
Outline
•  What are precipitation reactions?
•  Use of precipitates
–  Gravimetric analysis
–  Presence/absence of an ion
–  Precipitation titrations
•  Argentometric
•  Indicators used in manual titrations
•  Applications
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Precipitation Reactions
•  Ions in solution come
together to form a
precipitate, an insoluble
solid.
•  Precipitate composition
and color are dependent
upon which ionic
compounds are dissolved
in the solution.
•  Based on solubility, you can predict which ions

will come together to form a precipitate.
Na+(aq) + OH-(aq) !" …?...

Pb2+(aq) + 2Cl-(aq) !" …?...
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Solubility Rules
NO3- All nitrates are soluble.
Cl- All chlorides are soluble except AgCl, Hg2Cl2, and PbCl2.
SO42- Most sulfates are soluble. Exceptions include BaSO4, PbSO4, and
SrSO4.
CO32- All carbonates are insoluble except NH4+ and those of the Group 1
elements.
OH- All hydroxides are insoluble except those of the Group 1
elements, Ba(OH)2, and Sr(OH)2, Ca(OH)2 is slightly soluble.
S2- All sulfides are insoluble except those of the Group 1 and Group 2
elements and NH4+.
Based upon the solubility rules…
•  Sodium hydroxide (NaOH) is water soluble, so no
precipitate is formed between the two ions.
•  Lead and chloride will combine to form an insoluble
solid of lead(II)chloride.
Na+(aq) + OH-(aq) !" no precipitation reaction

Pb2+(aq) + 2Cl-(aq)  PbCl2(s)
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•  KSP " Solubility Product Constant
•  Indicates solubility of a substance.
•  Used to predict whether a precipitate will form
when two solutions are mixed (i.e. titration).
•  If ion product concentration greater than KSP., solution is super-

saturated and PRECIPITATES FORM.
•  If ion product concentration equal to KSP , solution is saturated and
NO PRECIPITATES FORM.
•  If ion product concentration less than KSP , solution is unsaturated
and NO PRECIPITATES FORM.
Gravimetric Analysis
•  Precipitates can be used for quantitative analysis
of solutions.
–  Determine the amount of solute or the mass of solute in a
given solution.
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Ionic Presence/Absence
•  Determine if an ion is present in a solution through precipitation
reaction.
•  When an ion is added to solution that is known to react with the
measured ion, the formation/ non-formation of precipitates can
be used as an indicator of its presence/absence.
•  Barium reacts with the sulfate ion to form an insoluble

precipitate.
•  Barium also forms several other insoluble salts, but all except
BaSO4 dissolve in dilute acid.
In the presence of a dilute acid

BaCl2 + SO42- !" BaSO4
white
Precipitation Titrations
•  Precipitation reactions are utilized during a
titration to determine the unknown
concentration of an analyte.
•  The analyte is precipitated out with the titrant.
•  Using an ion-selective electrode, either ion of
the precipitate can be monitored.
–  i.e. titration for chloride with silver nitrate;
precipitate of silver chloride; use either chloride or
silver/sulfide ISE
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Argentometric Titrations
•  A type of precipitation reaction.
•  Reaction involves silver as the precipitating
agent (argentum from the latin word for silver).
–  A precipitate of silver salt forms.
•  Silver rapidly forms precipitates with several
anions.
–  Allows for concentrations of various anions in
solution can be determined.
AgNO3(aq) + Br-(aq) !" AgBr (s)
Argentometric Titrations
•  Silver readily reacts with halides to form silver halide salts.
•  Agl is the least soluble.
Analyte Color of Precipitate Reaction

Iodide Yellow Ag+(aq) + I-(aq) !" Agl (s)
Bromide Cream Ag+(aq) + Br-(aq) !" AgBr (s)
Chloride White Ag+(aq) + Cl-(aq) !" AgCl (s)
I- Br- CI-
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Indicators
•  In manual precipitation titrations, indicators are
used as a way to detect the endpoint.
•  By identifying the indicator, the type of
titration can be determined.
•  Two types of precipitation indicators:

–  Type 1: Colored compound forms with the titrant
when the titrant is in excess.
–  Type 2: Adsorption indicator becomes adsorbed on
the precipitate at the equivalence point, and the
color of the indicator changes.
Indicators
Type 1: Indicators reacting with the titrant
The Mohr method for determination of chloride.
•  Chloride is titrated with silver nitrate + a soluble

chromate salt (indicator).
•  Forms a yellow solution.
•  When precipitation of chloride is complete (there is no
chloride left in solution), the first excess of silver reacts with
the indicator to precipitate red silver chromate.
CrO42- + 2Ag+ " Ag2CrO4

yellow red
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Indicators
Type 1: Indicators reacting with the titrant
The Mohr method for determination of chloride.
•  Indicator concentration must be between 0.002 to 0.005 M.

–  If it is higher than this, the yellow color of the chromate ion
obscures the red silver chromate precipitate color.
•  Titration must be performed at a pH of about 8.

–  If the solution is too acidic, less than pH 6, then part of the
indicator is present as HCrO4-, and more Ag+ is required to form
the proper precipitate.
–  If the solution is too alkaline, more than pH 10, AgOH will
precipitate out.
Indicators
Type 2: Adsorption indicators
•  The indicator reaction occurs on the surface (adsorption) of
the precipitate.
•  The dye indicator exists in solution as an anion (negatively
charged ion).
•  Color of indicator is different when it is adsorbed, so the
change signals the completion of the titration.
•  pH is an important factor and can affect the titration.
Color change of
dichlorofluorescein indicator at
the equivalence point.
University of Wisconsin-Madison Chemistry Department
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Indicators
Determination of chloride.
Before equivalence point… After equivalence point…
Cl- is in excess Ag+ is in excess
Primary adsorbed layer is Cl- Primary adsorbed layer is Ag+
Surface of precipitate (-) charged Surface of precipitate (+) charged
AgCl:Cl-::Na+ AgCl:Ag+::In-
Indicators
Indicator Titration Solution
Fluorescein Cl- with Ag+ pH 7 - 8
Dichlorofluorescein Cl- with Ag+ pH 4
Bromcresol green SCN- with Ag+ pH 4 – 5
Eosin Br-, I-, SCN- with Ag+ pH 2
Methyl violet Ag+ with Cl- Acid solution
Rhodamine 6 G Ag+ with Br- HNO3 (≤&0.3 M)
Thorin SO42- with Ba2+ pH 1.5 – 3.5
Bromphenol blue Hg2+ with Cl- 0.1 M solution
Orthochrome T Pb2+ with CrO42- Neutral, 0.02 M solution
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Applications:
Food industry
•  Salt concentrations in condiments,
meats, dairy products, etc.
–  % Daily Value, % sodium, % chloride, mg/L, g/L, etc.
of sodium or chloride
Sodium chloride is used as a preservative and flavor enhancer in

food.
Sodium can have adverse health effects and are monitored in the
daily diet.
Titrate with silver nitrate, silver chloride precipitate, infer sodium

content.
Applications:
Environmental & Water Quality
•  Chloride, sulfate, bromide and heavy metals in
potable, fresh, marine and waste water.
Chloride, sulfate and bromide occur naturally and

synthetically in all types of water environments.
Heavy metals are removed from wastewater through

precipitation reactions with hydroxide and sulfide.
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Applications:
Archeological Restoration
•  Antique iron objects buried in the soil collect
chloride ions.
•  Post excavation, chloride enhances corrosion.
•  Use of a deoxygenated alkaline wash bath, rids
the object of these ions.
•  Titration of wash bath for chloride
determination with silver nitrate identifies
process completion.
Questions?
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Precipitation Titrations General

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www.hannainst.com& Copyright Hanna Instruments

• Based on solubility, you can predict which ions

Na+(aq) + OH-(aq) !" …?...

Na+(aq) + OH-(aq) !" no precipitation reaction

• If ion product concentration greater than KSP., solution is super-

• Barium reacts with the sulfate ion to form an insoluble

In the presence of a dilute acid

AgNO3(aq) + Br-(aq) !" AgBr (s)

Analyte Color of Precipitate Reaction

• Two types of precipitation indicators:

• Chloride is titrated with silver nitrate + a soluble

CrO42- + 2Ag+ " Ag2CrO4

• Indicator concentration must be between 0.002 to 0.005 M.

• Titration must be performed at a pH of about 8.

University of Wisconsin-Madison Chemistry Department

Before equivalence point… After equivalence point…

Cl- is in excess Ag+ is in excess

Primary adsorbed layer is Cl- Primary adsorbed layer is Ag+

Surface of precipitate (-) charged Surface of precipitate (+) charged

Sodium chloride is used as a preservative and flavor enhancer in

Titrate with silver nitrate, silver chloride precipitate, infer sodium

Chloride, sulfate and bromide occur naturally and

Heavy metals are removed from wastewater through

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•  Based on solubility, you can predict which ions

•  If ion product concentration greater than KSP., solution is super-

•  Barium reacts with the sulfate ion to form an insoluble

•  Two types of precipitation indicators:

•  Chloride is titrated with silver nitrate + a soluble

•  Indicator concentration must be between 0.002 to 0.005 M.

•  Titration must be performed at a pH of about 8.