Separation

Techniques
Hanandayu Widwiastuti, S.Si., M.Si.
Politeknik Kesehatan Kemenkes Malang
 Why We Need Separation Techniques?

 Deal with separation of mixtures to

enhance purity of subtances

 Are important because most subtances are

needed in their pure state.
SEPARATION TECHNIQUES CLASSIFICATION

 Mass and density

 Complex formation
 Change in physical state
 Change in chemical state
 Partitioning between phases
Separations Based on Mass or Density
CENTRIFUGATION

 If there is a difference in the mass or density of

the analyte and interferent, separation using
CENTRIFUGATION may be possible.

 Particles experiencing a greater centrifugal force

have faster sedimentation rates and are
preferentially pulled toward the bottom of the
tube.
Separations Based on Mass or Density
 For particles of equal density, the
separation is based on mass, with heavier
particles having greater sedimentation
rates.

 When the particles are of equal mass,

those with the highest density have the
greatest sedimentation rates.
Separations Based on Mass or Density

 Illustration showing
separation by equilibrium-
density-gradient
centrifugation.

 The homogenous mixture

in (a) separates into three
bands (b) after applying
centrifugal force.
https://www.youtube.com/w
atch?v=gmNw6CWtN5k
Separations Based on Mass or Density

DECANTATION
 It is simply to pour off of upper liquid layer

 Used to separate a liquid from an

insoluble solid. The solid stays in the
bottom.
Separations Based on Mass or Density
DECANTATION
Separations Based on Complex Formation

MASKING

 One of the most widely used techniques

for preventing an interference.

 The interferent is binded as a soluble

complex  prevented from interfering in
the analyte determination.
Separations Based on Complex Formation

in Analytical Chemistry, the technique of

masking is mainly used to improve selectivity
in a wide variety of methods such as
complexometric titrations,
spectrophomometry, gravimetry, solvent
extraction, ion-exchange, chromatography,
etc.

Apart from this, the technique possesses

extensive industrial applications
 Separations Based on Complex Formation

MASKING
In complexation reactions, several ligands react with a metal
atom to form a coordination complex. This is achieved by
providing lone pairs od the ligand into empty orbitals of the
metal atom and formng dipolar bonds. The ligands are Lewis
bases, they can be both ions and neutral molecules.
In chemistry, a coordination complex, consists of an atom or
ion (usually metallic), and a surrounding array of bound
molecules or anions, that are in turn known as ligands or
complexing agents.
Coordination refers to the "coordinate covalent bonds" (dipolar
bonds) between the ligands and the central atom. Originally, a
complex implied a reversible association of molecules, atoms,
or ions through such weak chemical bonds.
Separations Based on Complex Formation

MASKING

 MASKING AGENT  the reagent used to

bind the species to be masked in an
unreactive complex.

A wide variety of ions and molecules

have been used as masking agents, and,
as a result, selectivity is usually not a
problem
 MASKING by Precipitation

 This technique was employed in the

determination of calcium in presence of
magnesium (pH 12), wherein Magnesium is
precipitated as its hydroxide.
 Similarly metal ions such as Fe(III), Ti(IV),
Sn(IV), can also be masked by precipitating as
their hydroxides.
 The use of fluoride ion as a masking agent for
Ca, Mg, and Al in the titration of Zn.
 Sulfate ions can be used to mask Pb when Bi is
to be titrated.
 MASKING by Redox

 This technique can be applied to avoid the

interference of Cr, Mo, W, and V in their
lower oxidation states which form stable
complexes with EDTA.
 The above metal ions can be masked by
their oxidation into stable oxyanions such
as CrO42-, MoO42-, WO42-, and VO42-
repectively.
INDIRECT MASKING
Masking Agents, especially those operating
through the formation of soluble complexes may
be added after the metal ions mixture has been
reacted with the principal masking agents. This
approach is called INDIRECT MASKING.

This technique is particularly useful when the ion

to be determined is present in a substantially
smaller amount than the interfering ions.
INDIRECT MASKING
For example, Al(III) can be determined in the
presence of other cations which interact with
EDTA by complexing all the cations including
aluminium with known excess of EDTA under
optimum conditions and back titrating the excess
EDTA followed by the addition of fluoride ion to
mask Al(III) and release the EDTA from Al-EDTA
complex and determining the EDTA so released
by using standard Zn(II) or Pb(II) solution.
Separations Based on Complex Formation

MASKING
in Analytical Chemistry,
the technique of masking
is mainly used to improve
selectivity in a wide
variety of methods such
as complexometric
titrations,
spectrophomometry,
gravimetry, solvent
extraction, ion-exchange,
chromatography, etc.

Apart from this, the

technique possesses
extensive industrial
applications
Separations Based on Complex Formation

MASKING

EXAMPLE

 Suggest a masking agent for the

analysis of Al in the presence of Fe.
Repeat for the analysis of Fe when Al is
an interferent.
To find a suitable masking agent, we look
for a species that binds with the interferent
but does not bind with the analyte.

Oxalate, for example, is an inappropriate

choice because it binds with both Al and Fe.
From the Table we find that thioglycolic acid
is a selective masking agent for Fe in the
presence of Al and that F– is a selective
masking agent for Al in the presence of Fe.
Example 2

Show that CN- is an appropriate masking agent

for Ni2+ in a method where nickel's
complexation with EDTA is an interference.
HINTS
Cyanide is an appropriate masking agent because the
formation constant for the Ni(CN)42– is greater than that for
the Ni–EDTA complex. In fact, the equilibrium constant for
the reaction in which EDTA displaces the masking agent is
very small, indicating that Ni(CN)42– is relatively inert in
the presence of EDTA.

As shown in the example, we can judge a masking agent's

effectiveness by considering the relevant equilibrium
constants.
TERIMA KASIH