Radio chromatography

Seaborg and collaborators are separate a mixture of radioactive six 5f

elements (americium, curium, berkelium, californium, einsteinium and fermium)

using chromatographic method. The mixture was placed on a column of a cation

exchanger Dowex 50 of 2mm diameter and 5-6 cm length and eluted with a solution

of ammonium citrate or ammonium acetate at 87°C. An automatic drop fraction

collector received the eluent and fission activity was recorded for each fraction.

The identity of each element of 5f series was established unmistakably by the

sequence of their appearance similar to the sequence of the corresponding six 4f

elements (europium, gadolinium, terbium, dysprosium, holmium and erbium).

Fig. 1 shows, the similar positions for the six elements of the 4f series (rare

earths) Z = 63 to 68 and of the 5f series (actinides) Z = 915 to 100 all in decreasing

order of atomic numbers with increase in the time of elution or the drop number.

There are many other examples of the use of radio chromatography in

analytical work. A complete separation of the alkali metal ions Li+, Na+, K+, Rb+ and

Cs+ was shown to be possible using an acid washed asbestos paper and dilute

hydrochloric acid as solvent by labelling the ions with their radioisotopes (22Na, 86Rb

and 137Cs)* (Fig. 2; Table 1).

(Figure: 1. Radio chromatography of (a) Lanthanides: Eu to Er; (b) Actinides: Am to Fm)

 (Figure: 2. Radio chromatography of alkali ions on asbestos paper)

Table: 1. Rf values of alkali metal ion is,

Ions Li+ Na+ K+ Rb+ Cs+

Rf 0.99 0.86 0.77 0.72 0.45

Similarly, the alkali earth metal ions were separated using their radioisotopes
90
Sr and 131
Ba as tracers. The Rf values found were, Y3+ - 0.18; Sr2+ - 0.76; Ba2+ - 0.90.

Figure 3 is a chromatogram on Whatman Paper No. 1 of different anions containing

sulphur labeled with 35S. The solvents employed were,

(A) Dioxan + n-butyl alcohol + 1 N ammonia (1:1:1)

(B) Acetone + isopropyl alcohol liquor ammonia (d = 0.888) (2:1:1)

(Figure: 3. Radio chromatography on Whatman Paper No. 1 of different anions containing 35S)
The Rf values of values oxyanions containing sulphur is,

Solvent SO42- S2O32- SO32- S4O62- S2-

(A) 0.12 0.43 - 0.54 0.77
(B) 0.00 0.14 0.61 - -

Neutron activation analysis (NAA)

NAA is the most common form of activation analysis. The activation reaction

is induced by the interaction of a neutron with the nucleus of an analyte element.

This reaction is commonly followed by the measurement of a radioactive decay.

Gamma-ray decay is commonly used in the detection and determination of the

element of interest.

Figure 1 show a typical NAA spectrum obtained with a multichannel

analyzer equipped with scintillation (a flash or sparkle of light) (upper curve) or

semiconductor detectors (lower curve). Each peak can be attributed to a certain γ-

energy. A number of nuclides can be identified simultaneously with semiconductor

detectors, but with NaI (TI) scintillation detectors the poor resolution limits

simultaneous multi-element analysis.

(γ-spectrum of neutron-activated sea water)

 (a) Neutron Sources

The neutron source for NAA is a nuclear reactor, which produces neutrons

via the nuclear fission process. When a reactor is not available, or a portable

neutron source is required, isotopic sources, small mobile reactors, or neutron

generators are possible alternatives.

(b) Thermal Neutron Activation Analysis (TNAA)

Thermal neutrons also called as slow neutrons because their most probable

speed is low (v ≈ 2,200 m/s) with a mean energy of 0.038 eV.

Important types of neutron sources used in NAA

Source Usable neutron flux or production rate

Thermal Epithermal or fast

Large research reactor (>10 MW) (1014 – 1015) cm–2 s–1 (1011 – 1012) cm–2 s–1

Small research reactor (>100 kW) (1012 – 1013) cm–2 s–1 (1011 – 1012) cm–2 s–1

Neutron generator (109 – 1012) s–1

Alpha sources 106 s–1

252
Cf fission source 2.34 × 109 s–1 mg–1

(c) Epithermal Neutron Activation Analysis (ENAA)

Neutrons with slightly higher energies (1 eV to 100 keV) than thermal

neutrons are called epithermal neutrons. This type of NAA is based on the

selective activation of nuclides the cross sections, exhibit the strong resonances in

the lower part of the energy range.

(d) Fast Neutron Activation Analysis (FNAA)

Neutrons with energies greater than 0.1 MeV are called fast neutrons. The

fission spectrum of a light-water-moderated reactor provides as many fast

neutrons as thermal neutrons. Therefore, fast neutron activation of certain

elements via (n,p) reactions is a very selective technique, complementary to

thermal and epithermal NAA.

A typical example is Fe, for which the 56

Fe(n,p)56Mn activation reaction

produces a better gamma-ray emitter than the thermal capture reaction.

(e) Neutron-Induced Prompt Gamma Activation Analysis (PGAA)

PGAA is an instrumental procedure that makes use gamma-ray emissions

that occur immediately after neutron capture during the de-excitation of the

newly formed compound nucleus.

The capture can produce nuclear states with energies up to about 11 MeV

above the ground state, which usually decay through a cascade of gamma rays.

The main advantage of PGAA is the ability to obtain gamma-ray spectra from

the neutron capture of nuclides that do not produce radioactive isotopes through

the (n,γ) reaction.

(f) Comparison of NAA Methods

NAA procedures are applicable to most element analysis problems, but are

most broadly used to determine trace elements in biological, environmental,

geological, and industrial materials.

Thermal NAA is the most sensitive, ENAA the most selective, while PGAA is

the most universal of the neutron activation techniques.

(g) In Vivo Neutron Activation Analysis

The successful establishment of nondestructive NAA as an analytical

technique is used for determining some elements in living subjects by in vivo

NAA. It is possible to measure total-body H, N, O, Na, P, Cl, K, and Ca and to

determine most of the same elements in parts of the body, such as a limb or an

organ.
Neutron absorptiometry

Boron and cadmium are the elements that have high neutron capture

cross section. Due to this property these are used as control rods in nuclear reactors.

Neutron absorptiometry is used for the analysis of rare earth series such as Sm, Eu,

Gd, Dy, Yb and Lu.

The technique consists in placing a known amount of the sample of the

element or one of its compounds in a definite position between a source of thermal

neutrons and the detector. The neutron flux reaching the detector is proportional to

the amount absorbed by the element in the sample. It is also possible to standardize

the method for determine the amount of the element in the sample if the thickness of

the sample and its position with respect to the neutron source and the detector can

be precisely controlled. The extent of neutron absorption is readily measured by

decrease in activity induced in an Ag or In foil embedded in the sample itself. The

reactions involved are,

 (1.65 MeV)
107
Ag (n,γ) → 108
Ag 108
Cd (stable); σ = 35 b, f = 5l.4 %
2.4 Min

γ (1.28 MeV)  (1 MeV)

11
In (n,γ) → 116
In 116
Sn (stable); σ = 155 b, f = 95.8%
54.1 Min

Where, f indicates the abundance of the isotope in the naturally occurring

element. Actually employed the method for the determination of boron and

cadmium in their compounds (in dissolved and solid states) dispersed in paraffin in

the concentration range of 10–4 M to 10–2 M.

Radiometric titrations

Radiometric titration is based on the formation of slightly soluble or readily

removable compound by the ion being determined with a reagent (titrant).

Radiometric titration is a quantitative method for the determination of an element.

In this titration titrant is radioactive. During the titration, radioactive ion

formed as a compound. As a result the activity of the titrant is reduced. The end

point of the reaction is determined by plotting the changes in the radioactivity

against the amount of titrant added. The titration curve is linear, because of the

linear relationship between concentration of the labelled substance and radioactivity.

The point of intersection of the two linear reactions of the titration curve represents

the end point.

In modified radiometric titrations, radioactive indicators have been used

which liberate its radioactivity at the end point. Radioactive indicators should meet

the following important requirements,

 Radioactive indicator with a half life ranging from a week to several months

has proved to be most suitable.

 Radioactive indicator emitting γ rays are most common in radiometric

titrations.

 The chemical form of radioactive indicator and the substance to be labelled

should mostly be the same.

The equivalence point can be determined from the break on the titration curve

plotted in the coordinates of the solution activity against the volume of reagent

added. The point of equivalence is either determined graphically from the titration

curve or from the following equation,

Vo = Vi {Io / (Io – It)}

Where, Vo = equivalent volume of reagent; Vi = Volume of reagent added; Io

= Initial activity of the solution; It = activity of solution after addition of reagent.

Types of radiometric titration

There are four types of radiometric titration

 Titration based upon Precipitate Formation.

 Titration based upon Complex Formation.

 Titration based upon Redox Reaction.

 Titration in Non-aqueous Media.

1. Based upon precipitate formation

In these titrations the radioactive indicator is precipitated during the titration

and the end point is obtained by following the changes in the radioactivity of one

of the phases. Three types of titration curves are usually obtained during

radiometric precipitation titrations and the shapes of these curves depend, on

whether the titrant, the test solution or both are labelled.

For example, the determination of chloride ion with Ag 110 NO3, the solution is

taken in the burette. When Ag110 NO3 solution is added, it forms the precipitate of

Ag110 Cl. The Ag110 activity in the supernatant liquid will not be observed so long as

there are chloride ions. As soon as all the chloride ions are precipitated as Ag110 Cl,

the Ag110 activity will start increasing in the solution which is indicative of the end

point. A modification (the precipitate formed emits  or γ radiation of high energy)

of the above procedure is made by counting the radioactivity of Ag110 Cl precipitate

which increases so long the chloride ions are completely precipitated. The end

point can also be located by adding a small amount of radionuclide to the

unknown solution and titrate with the inactive reagent. At the end point, the

radioactivity of the solution falls to a constant.

In some cases, no appropriate radioisotopes of the element to be determined. In

these cases, radioactive isotopes of other elements can be used for the identification

of the element to be determined and this technique is called non-isotopic labelling.

2. Based on complex formation

In complex formation reaction, the reacting species and the products of the

reaction are in the same shape, before and after the reaction. Thus the separation of

compounds is most difficult in radiometric location of the end point of complex

formation reactions. Therefore such titrations are carried out by using auxiliary

methods of separation, such as solvent extraction, ion exchange, chromatography

etc.

In radiometric titration, the indicator remains as insoluble solid till the end

point is reached, when it starts dissolving and releasing activity into the solution.

For example, the complexometric titration of calcium by EDTA with solid 110Ag IO3

as the indicator, the added EDTA is all removed by Ca2+ ions and after the end

point, EDTA reacts with Ag+ ions to form Ag-EDTA complex, which is soluble.

Consequently activity is released in the solution.

In radiometric complexometric titration, ion exchangers are used to fix the

cations that have not reacted with the reagent or have been formed as a result of the

reaction of the anions. With complex III or complex IV, the following reaction

occurs,

M2+ + H2Y2- → MY2- + 2H+

An ion-exchanger is introduced into the titrant in the form of a membrane,

which is withdrawn from the solution and washed after the radioactive ions of

interest are fixed. The content of the active ions on the membrane is then

determined.
 In radiometric titrations, substances have also been used (as indicator of

equivalence point) into radioactive isotope of krypton, 85

Kr may be introduced.

Such a substance must be sensitive to the reagent but must not react with the

solution under examination. After equivalence point, the radioactivity of the

substance containing 85Kr undergoes change.

3. Based on rectos reaction

The separation of components is also difficult in these titrations also. This

difficulty is again solved by auxilary separation methods. Solid indicators have also

been used.

4. Radiometric titrations in non-aqueous media

Non aqueous titration is those titration in which titration of weak acidic or

basic substance carried out using non aqueous substance, to get end points. Such

titrations can also be used for the titration of those substances which are not soluble

in non aqueous solvents.