4.

5
ORGANIC PRECIPTANTS
Many inorganic ions can be
ganic precipitants. A numberprecipitated with certain organic reagents
by precipitation, but also by of these reagents are useful not only for called or
Chapter 16. solvent extraction. The latter will be separations
discussed in
Most of the organic precipitants on
combine with cations to form chelate rings.which
We
our discussion will be
centered
tral metal chelate shall be concerned here with
compounds which are insoluble in water. In Chapter 8 we neu
discuss reagents which form soluble 1:1complex ions with wil!
which can be employed as titrants various cations
for metals. In this chapter we shall also men and
tion a fewexamples of organic
metal ions. precipitants which form saltlike precipitates with

4.5a. Reagents Forming Chelate Compounds

Generally speaking, most of the better-known organic precipitants which
form chelate compounds with cations contain both an acidic and a
tional group. The metal, interacting with both of these groups, itself basic func -
becomes one
member of a heterocyclic ring. 8-Hydroxyquinoline (often called 8-quinolinol, or
Oxine) forms insoluble compounds with a number of metal ions, aluminum for
one. The formation of this compound may be formulated as follows:

3 + A!3*
+ 3H

OH

Aluminum replaces the acidic hydrogen of the hydroxyl group. At the same time,
the unshared pair of electrons on the nitrogen is donated to the aluminum,
thereby forming a five-membered ring. From the strain theory of organic chem

Sec. 4.5/ Organic Precipitants 81

 would be mainly five
rings of this type
organic andmolecule
sixmem.
expected that the
istry itis
inthe
Hence
be situated acidic and
positions
basic functional groups in
with respect to cach other which permit the closure of
bered.
must
Aneutral
such rings. chelate compound of the (ype described is essentially organic in
of the members of an organic
nature. The metal ion becomes simply one

demonsitnrag
no longer
and its usual properties and reactions are readily
structure,
mind that exceptions can be found. we may state
crallyWitlh
ble. suchreservation
thatthe in
chclate compounds gen.
are insoluble in water but soluble in less polar
solventssuch as chloroform and carbon tetrachloride. We shall see in Chapter 16
that this differential solubility may be utilized in effecting separations by extrac-
tion processes, and in Chapter 14 we shall nention briefly the use of chelates in
colorimetric analysis. At this point, we wish to consider only the precipitation of
metal ions by these organic reagents.

Precipitants
4.5b. Advantages and Disadvantages of Organic
Let us consider first the advantages offered by organic precipitants.
1. Many of the chelate compounds are very insoluble in water, as noted above
so that metal ions may be quantitatively precipitated.
2. The organic precipitant often has a high molecular weight. Thus a smal
amount of metal may yield a large weight of precipitate, minimizing weighing
errors.
3. Some of the organic reagents are fairly selective, yielding precipitates with
only a limited number of cations. By controlling such factors as pH and the
concentration of masking reagents, the selectivity of an organic reagent can
often be greatly enhanced.
4. The precipitates obtained with organic reagents are often coarse and bulky
and hence easily handled.
5. In some cases a metal can be precipitated with an organic reagent, the precipi
tate collected and dissolved, and the organic molecule titrated, furnishing an
indirect titrimetric method for the metal.

There are some disadvantages in the use of organic precipitants.

1. Many of the chelate compounds do not have good weighing forms
and are
used only for separations, not determinations.
2. There is a danger of contaminating the precipitate with the
self because of the latter's limited solubility in water. chelating agent it
A list of a few organic precipitants which have
cedures is given in Table 4.1. found use in analytical pro

4.5c. Reagents Forming Saltlike

Precipitates
Some organic precipitants form salts rather than chelate
organic ions. Oxalic acid is well known in complexes with in
analytical processes for its use in

Chapter 4|Gravimetric Methods of Analysis

 TABLE 4.1 Some Common Organic Precipitants
Chelate with metal
Compound of valence n Comments

CH-ÇN--OH CH,-CN
M/n Principally used for
CH,--C-N--OH CH,-CN
determination of nickel

Dimethylglyoxime OH

Precipitates many
elements but can be used
OH for group separations
-M/n by controlling pH
8-Hydrox vquinoline

NO N-M/n
OH Principally used for
precipitation of obalt
in presence of large
amounts of nickel
a-Nitroso-B-naphthol
NO N=0
N
Mainly used for
ONH, 0-M/n
separations, such as iron
and titanium from
aluminum
Cupferron
H

HO 0, N Good reagent for copper;

M/n also precipitates bismuth
OH OH and zinc
a-Benzoin oxime

H O

N-C--CH, N-C
Used for precipitation
H SH
M/n-s
CH and determination of
elements of H,S group
Thionalide

-C=0 Used for determnination

OH
of cadmium, copper,
Mn and zinc
Quinaldic acid

precipitation of calcium; calcium oxalate is a typical insoluble salt. There are a

number of such organic compounds which form precipitates with both cations and
anions. A few of these are listed in Table 4.2.

Sec. 4.5 /Organic Precipitants /83

 SaltlikePrecipitates
Comments
Reagents
Forming
TABLE 4.2
M HCI only NH,, Hg
Reagent K´;in 0.i
principallyfor
Used interfere
Na B(CsHs)a Rb, and Cs

Sodium tetraphenylboron 2
principallyfor SO,
Used

Benzidinc

other
TI; metals which form preciptates inciude
(CçHs)4As CI Used for cadmium
mercury, and
tin, goid, zinc,
Tetraphenylarsonium
chloride

OH Acids precipitate quadrivalent metal ions such as tin

thorium, and zirconium from acid media
R-As=0
OH

Arsonic acids, R = phenyl,

n-propyl, etc.

SOF GRAVIMETRIC ANALYSIS