Kromatografi Agam Pemisahan Kimia

To a first approximation, these rules predict the observed order of affinity for groups
of ions :
The above orders often show inversions due to changes in pH, relative
concentrations, nature of resin, complex formation, ionic strength, etc.
The plate theory, developed by Martin and Synge for partition
chromatography, can be applied directly to an ion exchange column with only a
change of terminology. We will define a distribution ratio, D, as :
D=
quantity of sampleresin of a given plate

quantity of sampleinterstitial solution of same plate
Then the volume of eluent required to move the sample through the column, Ve,
measured to the peak maximum is
Ve = Vm + D.Vm
Where Vm is the interstitial volume of the column. Let us assume the sample
contains cations A+ and B+ which are to be separated from each other. When the
sample is introduced, it is first retained at the top of the column by exchange of
cations :
The corresponding selectivity coefficients are :
A separation factor, A/B, can be derived from equations
In equations 5-7 to 5-9 we have neglected the activity coefficients, but, to a first
approximation, the last equation tells us that the separation factor is independent of
the concentration of other ions (unless they react with A + or B+). Now the cations A+
and B+ can be eluted from the column only if they are replaced by another cation
contained in the eluent. In this case, let us assume that the eluent contains a high
concentration of H+. Equations 5-7 and 5-8 show that increasing [H +] must also
increase [A+] and [B+]. In other words, we can change the distribution ratios for A +
and B+ (equations 5-5) and thus the elution volume (equations 5-6) many fold by
altering the concentration of eluting ion. A high concentration of the latter will lead
to faster elution with sharper but less well resolved peaks as shown in figure 5-4.
Effect of pH of Eluent
The extent of dissociation of weak acids and bases, and the hydrolysis of salts and
metal ions is controlled by the pH of the medium. Thus the electrical charge on a
species may be increased, decreased, or even reversed by a change in pH. In this
manner, we have a delicate but powerful means of influencing the distribution, or of
preventing exchange altogether. This behavior is especially important in the
separation of amino acids which can carry a positive, negative, or no net charge
depending on the pH of the eluent. Buffered eluents are obviously indicated for
separations of this kind, but one must not forget that the ionic constituents of the
buffers are also subject to exchange with the resin so that the pH within the column
may bear no relation to that which was prepared. The effect of pH on the elution of
a typical weak acid is shown in Figure 5-5.
Effect of Complexing Agents
Ligands (defined in Section 22-1) which are neutral molecules have no effect on the
charge of an ion, but do alter the exchange equilibrium constant. Many metal ions
are complexed by anions yielding negatively charged complex ions. Thus, the rare
earth metal cations, which are poorly separated by cationic exchangers, can be
complexed and separated quite well by anionic exchangers.
Most of the useful complexing agents are themselves weak acids, weak bases, or
anions or cations thereof. Thus the pH and complexing effects are often
interdependent. Although there is a sensitive control of the separation, the resulting

multiple equilibria are so complicated that theoretical predictions are of little value
because of the necessary approximations.
Technique of Ion Exchange Chromatography
Selection and preparation of the resin

A wide variety of resins are available commercially from which one must select an
appropriate mesh -size, cross linking and quality. Analytical grade resins are
preferred because they have been more carefully sized and washed to remove
foreign organic and inorganic materials. It may be necessary to convert the resin
from one form to another, for example, the hydrogen form can be converted to the
sodium form by extensive washing in the column with strong sodium chloride
solution until the effluent is neutral. Used resins are regenerated in this way.
If it is important to know the weight of resin used, it must be dried or brought to

known moisture content in a hygrostat (a vessel with controlled, constant humidity).
In any event, before packing it must be equilibrated with water by prolonged
soaking. After the resin has settled, the fins which float in the water are poured off.
Packing the Column
Simple column are constructed from glass tubing with a reservoir at the top for the
eluent and a friend a fritted disk or glass wool plug at the bottom to support the
resin bed. Usually the bottom of the column is drawn to a narrower diameter and
bent in a double U shape so that the outlet is higher than the top of the resin bed.
This prevents air bubbles from leaking into the column. The resin is packed as an
aqueous slurry and allowed to settle with occasional tapping. Once packed, the
level of liquid should never be allowed to drain lower than the top of the resin bed
or air bubbles will be entrapped. The best way to remove air bubbles or channeling
is to back-flush the column with an upflow of water. A paper or glass fiber disk
placed on top of the bed will minimize disturbance of the resin when adding the
sample.
Total capacity of the Column
The total exchange capacity influences the maximum sample size and is used to
check the long term stability of the resin. The capacity of resin in milli-equivalent
per gram of dry resin is normally marked on the bottle by the manufacturer.
Experimentally, it is most readily determined by converting the resin entirely to the
hydrogen form (if it is cationic), and then eluting with a sodium chloride solution
until it is completely converted to the equivalent to the capacity of the columneasily determined by titration with sodium hydroxide. Common resins have a
capacity of 1 to 5 meq/ml or roughly 1 to 5 N in acid or base.
Detection Methods
The difficulty of detecting small amount of sample components in the presence of a
large concentration of eluting ion is one of the major disadvantages of ion exchange
methods. Continuous recording is not common, although in specific applications,
light absorption, refractive index, pH, radioactivity, or polarographic measurements
have been utilized. The most common, practice is to collect numerous small, equal,
volume fractions and analyze each fraction for the species sought.
Sebuah sampel 3,00 gram gula dan potasium nitrat dilarutkan dalam tepat 100 mL
air dan melewati kolom pertukaran kation dalam H-bentuk. limbah membutuhkan
5,30 mL 0,0100N natrium hidroksida untuk titrasi. Hitung persentase KNO3 dalam
sampel
Jelaskan prosedur untuk menganalisis larutan natrium klorida dalam asam klorida
menggunakan resin pertukaran ion dan titrasi asam-basa. Menunjukkan metode
penghitungan konsentrasi masing-masing ion utama yang ada
Satu gram resin pertukaran kation kering memiliki kapasitas 5,0 meq. Setelah
pembengkakan dan kemasan dalam kolom, jumlah yang sama dari resin menempati
7,5 mL. Jika kolom jumlah berisi 25 mL, berapa banyak mg ion kalsium bisa
bertukar?

Kromatografi Agam Pemisahan Kimia

Uploaded by

Document Information

Original Description:

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Kromatografi Agam Pemisahan Kimia

Uploaded by

Copyright:

Available Formats

To a first approximation, these rules predict the observed order of affinity for groups

quantity of sampleresin of a given plate

The corresponding selectivity coefficients are :

A separation factor, A/B, can be derived from equations

interdependent. Although there is a sensitive control of the separation, the resulting

Technique of Ion Exchange Chromatography

Selection and preparation of the resin

If it is important to know the weight of resin used, it must be dried or brought to

You might also like