Organic Precipitating

Agents
By:
Aideth Guadalupe Cardona Morales
Omar Alejandro Macias Franco
Etna Paulina Riva Martínez
Juan Gerardo Rubalcava Rodríguez
 The precipitating agent is a solution that is as dilute as possible, but of an
What are approximate concentration, to which a slight surplus should always be
precipitating added for the following reasons:
agents? 1 .- To ensure that the reaction has been total
2 .- To reduce the solubility of the precipitate.
3 .- Due to the common ion effect, the precipitate is more insoluble in a
solution that contains a common ion than in pure water.
Properties of precipitating
agents
To work well in the precipitation and quantification process:
1 .- It must be specific, that is, it must precipitate only with the
constituent to be determined.
2 .- Fast and stoichiometric reaction.
3 .- The weight of the substance to be determined must increase
sufficiently, so that it can be quantified with good precision.
4 .- Pure and soluble in the medium

Note: Not all substances that precipitate have the composition percentage
indicated by the formula
commonly used, which is why it is said that they are not
stoichiometric. Sulfides often vary widely in composition. For
example, ferrous sulfide, which is usually given with the formula FeS,
can vary its percentage iron content.
Organic precipitating agents

Gravimetric methods have been developed for most inorganic anions

and cations, as well as for neutral species, such as water, sulfur dioxide,
carbon dioxide, and iodine. Various organic substances can also be
determined.

Most inorganic reagents are not very selective. These reagents

normally form slightly soluble salts or hydrated oxides with the analyte.
 Some organic precipitating agents

Reagent Structure Precipitated metals

Dimethylglyoxime Ni(II) in NH, or buffered HOAc: Pd(II) in HC1 (M2+ + 2HR

CH, — C = NOH 1
CH—C= NOH —MR, + 2H)

a-benzoinozyme (cupron) OH NOH

Cu(II) in NHj and tartrate: Mo(VI) and W(VI) in H (M 2 - +

I,, Cc/ H,R — MR + 2H ; M 2 = Cu2+, MoO/. WO?O the metal oxide

is weighed

Examples of Ammonium nitrosophenylhydroxylamine

(cupferron)
N=O

CBo-NM
Fe(III). V(V), Ti(IV). Zr(IV). Sn(IV). U0V)
(M" ' + nNH,R — MR, + «NH. *) the metal oxide is weighed

Organic 8-hydroxyquinoline (oxin)

OH •
Many metals. Useful for Al(III) and Mg(II) (M" + nHR—MR,
+ nH )

Precipitating sodium diethyldithiocarbamate

yes
II
Many metals from an acid solution (M"* + nNaR — - MRn +
nNat)

Agents
(CHs)N — C — S Na-
sodium tetraphenylborate NaB(CH), K\ Rb + , Cst.TI+.Agt. Hg(I), Cu(I). NHj . RNH,+.
R 2 NH 2 '. R,NH+. R;N'. acid solution
(M- + NaR — MR + Nat)

Tetraphenylarsonium chloride (CH,).AsCI Cr,0,2 . MnOj . Convict. . MoO,2-, WO?, ClO, . YO, .
Acid solution (A" + nRCI - R„A + nCl )
Classification

• The formation of insoluble precipitates is characteristic

of organic precipitating agents.

• Depending on the type of precipitate they form, they can

be classified into 3 groups: Complex-forming agents,
salt-forming agents and lacquer-forming agents.
 Complex-forming agents
This type of precipitating agents meet the following characteristics:
They are complexing or binding substances.
In their chemical composition they have an acid group on one side, a basic group
on the other side and between them a considerable number of atoms .
The molecule as a whole produces a ring of 5 to 6 atoms when
attached to the metal (through coordinated ionic and covalent
bonds), which is known as a Chelate. (Examples:
Dimethylglyoxime and 8-
Hydroquinoline).
Chelates are relatively nonpolar , so they do not dissolve in Metal + Ligand = Chelate
water. Its solubility increases in polar solvents. They have low density and are
intense in color.
Sometimes it is necessary to form soluble chelates of compounds that can interfere
with the precipitation of the ion of interest. This procedure is known as Masking.
Salt-forming agents
• These agents cause the precipitation of compounds
crystalline with ions
metallic , in which the following stand out:
1. Sodium Tetraphenylborate: Used to precipitate
Potassium, Ammonium, Cesium and Rubidium.
The ions that co-precipitate and generate
interference are Thallium and Mercury, and must
be eliminated before precipitating the first
mentioned.
2. Tetraphenyl Arsonium Chloride: Are
especially useful in the precipitation of negative
ions formed by metal complexes, such as SnCl6 (-
2) and CdCl4 (-2).
 Applications
Precipitating agents
organic form
AgzCrO CdS B2S3 Ni(OH)2 Al(OH)3 slightly soluble products
called compounds of
coordination and are used to
Cu(OH)2 Ni(DMG) AgBr SnS2 Ag,AsO4 AgCI

analytical separations.

Some of the compounds

most used are:
 DIMETHYLGLYOXYME
Removal of heavy metals from industrial effluent or process/human water

TAERSA (Water, Effluent and Reuse Treatment)

precisely determines the metals present and thus
develops the corresponding treatment.

Complex of
.1 CHj—=N—OH
Example of reaction with nickel Not 1 +2 dimethylglyoxime with
CH,--C=N--OH
Nickel
reddish precipitate
 The most used technique is conventional chemical precipitation for
most heavy metals (Cd, Cr, Cu, Pb, Hg, Ni, Zn, among others)

.H
o'fo
Yo Yo
H, C ¿ N. N, CH,
c \ and c
Nor | +2H+
c . / \ c - -8 * ' --~g
H,CNN CHj

°°
“PH”"
 8- Hydroxyquinoline
Detection of aluminous cement in concrete

A direct, rapid and cheap gravimetric method used in the determination of aluminum in cements,
mortars and concretes is "oxin" (8-hydroxyquinoline), which forms an insoluble yellow complex
with aluminum.

However, the results of its application are falsified by a series of interfering

factors (cement carbonation, presence of sulfates, existence of "aluminous"
aggregates, low cement dosage, among others).

The reaction that takes place is the following:

Aluminum Tris(8-
hydroxyquinolinate)
 Cupferron
Chelating agent for pre-concentration in atomic spectrophotometry

For this, chelating

agents such as
cupferron are used.

Cupferron N-nitrosophenylhydroxylamine V, Ti, Cu, Mn, Fe, Ni

ammonium salt
Example of reaction with titanium:
Organic Precipitating Agents 1
Properties of precipitating agents 3
Organic precipitating agents 4
Complex-forming agents 8
Salt-forming agents 9
DIMETHYLGLYOXYME 11
8- Hydroxyquinoline 12
Cupferron 13

signals transmitted in the presence and

absence of the element to be determined
in drinking and wastewater samples.
During sample extraction prior to analysis,
there may be interferences that require
pretreatment to increase the concentration
of the element of interest of the interfering
species.
 • The cupferron complex with
titanium is used for the
Cupferron determination of this in hair.

Determination of traces of titanium ( ) IV

• The complex is formed with
titanium as in the previous example and the
following is immediately carried out:

• The catalytic differential pulse. Adsorption disassembly voltammetry

behavior of titanium( IV )-cupferron system on glass covered with
bismuth carbon electrode (BiFE) has been investigated.
 ORGANIC PRECIPITANTS REAGENTS

ADVANTAG DISADVANTAG
ES 1 Organic precipitants are ESto adsorption
Significantly, coprecipitation due
selective or can be made rarely causes errors, because organic
selective by masking precipitates are easy to wash away
interfering or by adjustment of
the solution. 1 The precipitates, because they are almost
the always sticky, adhere strongly to the glass
ions
pH and it is difficult to transfer them from one
Precipitates are
usually non-ionic in container to another 2 Organic reagents are
nature with the advantage of almost never pure, it is almost always
not adsorbing impurities. necessary to test the effectiveness of the
analyzed reagent with a standard sample.

Entrapment
 ORGANIC PRECIPITANTS REAGENTS

3 The precipitates are easily dried at necessary to add enough precipitating agent
temperatures slightly above 100 o 4 The so that the reaction is complete with the ions
precipitated ion is usually a small fraction of to be precipitated.
the weight of the precipitate and the
precipitate is usually voluminous. 4 Precipitates obtained with organic
compounds are more sensitive to heat than
5 Precipitates obtained with organic inorganic ones.
precipitants are generally soluble in organic
solvents.

DISADVANTAGES

3 The precipitating agents are poorly soluble

in water and slightly soluble in the solution, so
a small excess of reagent can cause
contamination of the precipitate; however, it is
 • Cabrera, N. R. (2007). Fundamentals of basic analytical chemistry. Quantitative analysis. Caldas University. P.. 130-132.
• D.Christian, G. (2009). Analytic chemistry. d. F.: McGraw-Hill/Interamericana Editores. Q. 326
• Miguel Angel Osejos Merino, M. c. (2018). CHEMICAL ELEMENTS AND THEIR EFFECTS IN NATURE. 3Science. Q. 44

Bibliographies
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Caldas).: Exact and natural sciences. Manizales-Colombia: University of Caldas. PP. 132-133
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bismuth film electrode. ROYAL SOCIETY OF CHEMISTRY, 7, Pp 1631.
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https://www.taersa.com/tecnologias-processes/tratamiento-de-efluentes/pre-tratamiento/precipitacion-de-metales-pesados/
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Research Scientific Place Web:
materconstrucc.revistas.csic.es/index.php/materconstrucc/article/download/589/635
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