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Kromatografi Agam Pemisahan Kimia
Kromatografi Agam Pemisahan Kimia
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=
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 :
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
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?