RADIOCHEMISTRY

Lecturer:
Prof. Resmi Mustarichie MSc, PhD., Apt.
Course Materials:
1. Atomic Nuclei
2. Radioactivity
3. Nuclear Reactions
4. Production of Radionuclides
5. Separation of Radionuclides
6. Isotopic Exchange, Distribution of Miroconcentrations of
Radioisotopes between Two Phases, Adsorption of
Radioisotopes , Electrochemistry of Radioisotopes, and the
State of Radioisotopes in Ultrasmall Concentrations
7. Radiation Chemistry
8. Synthesis of Radiolabeled Compounds
9. Application of Radioisotopes in Studies of the Structure of
Chemical Compounds and the Mechanism of Chemical
Reactions, in Analytical Chemistry, and for Determination of
Physicochemical Constants
References

1. G. F. Friedlander, J. W. Kennedy, E. S. Macias, J. M. Miller, Nuclear

and Radiochemistry, 3rd Edition, John Wiley & Sons, New York,
1981.
2. G. Choppin, J. Liljenzin, J. Rydberg, Radiochemistry and Nuclear
Chemistry, 3rd Edition, Butterworth-Heinemann, Oxford, 2002.
3. A. N. Nesmeyanov, Radiochemistry, Mir Publishers, Moscow, 1974
 Radioactivity
• Much of our understanding of atomic structure
came from studies of radioactive elements.

• Radioactivity - The process by which atoms

spontaneously emit high energy particles or rays
from their nucleus.

• First observed by Henri Becquerel in 1896.

 Discovery of Radiation
• William Roentgen Nov, 1895 - X-RAYS
• Henri Becqueral, Feb 1896
Antoine Henri Becquerel
France (1852-1908)
Structure of the Atom
An atom is the smallest particle of an element and
has properties of the elemen
Z/N

Bohr’s atomic theory:

• An atom is composed of a nucleus at the center and

one or more electrons rotating around the nucleus
along diferent energy orbit.
• The nucleus is primarily composed of protons and
neutrons collectively called nucleons
• the number of electrons moving around the nucleus
equals the number of protons, balancing the electrical
charge of the nucleus.
 Structure of the Nucleus

Atomic nucleus: Berat proton = 1.6724 x 10-27 kg

proton nukleon 1.00727 amu
neutron Berat neutron = 1.6747 x 10-27 kg
1.00866 amu
Number of electrons in the neutral atom = number of protons in the atomic
nucleus.
Z = Atomic number
Example: the stable nucleus of
= the number of protons in the
aluminum consists of 13 protons (Z)
nucleus
A = Mass number and 14 neutrons (N) Aluminum has A
= the number of nucleons or = 27 and Z = 13
the sum of protons and neutrons
=Z+N
Terminology
A nuclide is an atom characterized by the number of protons and neutrons
in its nucleus, either stable nuclides or unstable nuclides, designated by
the atomic number (Z) and the mass number (A):
A
ZX
52
Example:
25 Mn
The unstable nuclide or radioactive nuclide is often termed a radionuclide.

Nuclides of the same atomic number are called isotopes and exhibit the
same chemical propeties. The unstable isotope or radioactive isotope is
termed a radioisotope.
Examples of oxygen isotopes are:158O , 168O , 17 and 18
8O 8O
Terminology
Nuclides having the same number of neutrons but different atomic numbers
are called isotones.
Examples:59 Fe , 60
, 61
and 64 Cu , each having 33 neutrons
26 27 Co 28 Ni 29

Nuclides with the same number of nucleons, i.e, the same mass number (A),
but a diferent number of protons and neutrons, are called isobars.
67 67 67 67
32Ga
Misalnya: 29 Cu, , and
30 Zn 31 Ga
each having mass number of 67

Nuclides having the same number of protons and neutrons but different in
energy states and spins are called isomers.
Examples:99m Tc and 99 Tc are isomers of the same nuclide.
43 43
Nucleus Model
Liquid Drop Model:
• The nucleus is assumed to be spherical and composed of closely packed
nucleons.
• Particle emission by nucleus resembles evaporation of molecules from a
liquid drop.
• This model explains various phenomena, such as the nuclear density,
binding energy, energetics of particle emission by radioactive nuclei, and
fission of heavy nuclei.

Shell Model:
Nucleons are arranged in discrete energy shells similar to the electron shells of
the atom in the Bohr theory. Nuclei containing 2, 8, 20, 50, 82, or 126
protons or neutrons are very stable, and these nucleon number are called
magic numbers. The shell model explains various nuclear characteristics such
as the angular momentum, magnetic moment, and parity of the nucleous.
Stability of the Nucleus

❖More stable nuclei if they contain an even number of protons and neutrons
Less stable nuclei if they contain an odd number of protons or neutrons

❖The ratio of the number of neutrons to the number of protons:

N An approximate index of the stability of a nuclide
Z
= 1 in the stable nuclei with a low atomic number ,
12 16 14
such as 6 C , 8O and 7N

Z>20, the ratio of N/Z increases with increasing aomic number of

127 208
the nucleus. Examples: N/Z = 1.40 for 53 I and 1.54 for 82Pb
 100

90

80

70

60

Z 50

40

30

20

10

0
0 10 20 30 40 50 60 70 80 90 100 110 120 130

N
Nuclei with N/Z diferent from the stable nuclei nuclei are unstable and
decay by β-particle emission or electron capture.
Stability of the Nucleus
The classical electrostatic theory a nucleus should not hold as a single
entity because of the electrostatic repulsive forces among the protons in the
nucleus.

However, the stable existence of the nucleus has been explained by the
postulation of a binding force, referred to as the nuclear force, which is much
stronger than the electrostatic force and binds equally protons and neutrons
together in the nucleus.

The nuclear force exists only in the nucleus and has no influence outside
the nucleus.

The size of a nucleus is of the order of 10-13 cm and the nuclear force is short
range resulting in the very small size of the nucleus.
Stability of the Nucleus
The mass M of a nucleus is always less than the combined masses
of the nucleons A in the nucleus.

Mass Defect = M - A
This mass defect has been utilized as energy in binding all the nucleons
in the nucleus. This energy is called the binding energy of the
nucleus and need to be supplied to separate all nucleons completely from
each other.

The stability of a nuclide is governed by the structural arrangement and

binding energy of the nucleons in the nucleus.
Radioactive Decay
• emission and propagation) of energy through space
Radiation ⇨
• can be particulate or electromagnetic

An unstable or radioactive nuclide decays by spontaneous

fission, or α−particle, β-particle or γ-photon emission

Radioactive decay by particle emission or electron capture changes the

atomic number of the radionuclide, whereas decay by photon emission
does not.
Radioactive decay
Radionuclides may decay by any one or a combination of five
processes:
- +
➢ α decay, β decay, β decay, electron capture, or isomeric
transition.

In all decay processes, the energy, mass, and charge of

radionuclides must be conserved.
α Decay
It is usually happened in the heavy nuclei , higher than Pb, such as
radon, uranium, neptunium, dst.

The α particle is a helium nucleus containing two protons and two

neutrons bond together, 4He
2
In α decay, the atomic number of the parent nuclide is therefore reduced
by 2 and the masss nmber by 4:
235 231 4
U Th + 2He
92 90

An α transition may be followed by γ-ray emisssion.

The α particles are monoenergetic, dan their range in matter is very
short (on the order of 10-6 cm).
β− Decay
This decay occurs when a nucleus is “neutron rich” (N/Z >> compared to
the stable nucleus).

In β− decay, a neutron (n) essentially decays into proton (p), and β−

particle along with antineutrino (ν-)

n p + β − + ν−
An antineutrino is an entity almost without mass and charge and is primaly
needed to conserve energy in the decay.

The β− particle is emitted with variable energy from zero up to the decay
energy. The decay energy is the difference in energy between the parent and
daughter nuclides..
β− Decay
An antineutrino carries away the difference in energy between the parent
and daughter nuclides.

The β− decay may be followed by γ-ray emission. After β− decay, the

atomic number of the daughter nuclide is one more than that of the
parent nuclide. Some example of β− decay are

+ β − + ν−
131 131
I Xe
53 54

+ β − + ν−
59 59
Fe Co
26 27

+ β − + ν−
99 99m
Mo Tc
42 43
Bremsstrahlung Continuous X-rays result from deceleration
of β− rays or electrons in the Coulomb field of atomic nuclei. The
probability of producing bremsetrahlung increases with increasing
electron energy and increasing atomic number of medium.
Decay scheme of 131I
131
I (8 days) β−
53

723 keV
1,6%
6,9% 637

90,4%
364

80

131
Xe (stable)
54
Positron or β+ Decay
Nuclei that are “neutron deficient” or “proton rich” will decay by emitting
β+-particle accompanied by the emission of a neutrino (ν)

i.e., have an N/Z ratio less than that of the stable nuclei

At the end of the path of β− −particles, positrons combine

with electrons and thus are annihilated giving rise to two
photons of 511 keV emitted in opposite directions. These
photons are referred to as annihilation radiations.

511 keV + - 511 keV

ee
Positron emission takes place when the energy difference between parent
and daughter nuclides is larger than 1,02 MeV
Isomeric Transition (IT)
▪ A nucleus can remain in several excited states above the ground state that
are defined by quantum mechanics.
▪ A nucleus can become excited in several ways; the most common way is
through a radioactive decay process (α, β−, β+, EC decays) in which
some of the transition energy remains in the nucleus after particle
emission. This excess nuclear energy can be emitted either promptly or
in a delayed manner.
▪ Prompt de-excitation occurs when gamma rays are emitted immediately
after particle emission (α, β−, β+ particles) usually within 10-13 seconds.
▪ Delayed de-excitation occurs when the excited nucleus persists for a
measurable period of time, with half-life in the range of 10-9 seconds to
several months. These nuclei are called metastable states and are
designating by writing a lower case m after the mass number (99mTc).
Positron or β+ Decay

In β+ decay, a proton transforms into a neutron by emitting a β+

particle and a neutrino as illustrated below:

p n + β+ + ν

Since a β+ particle can be emitted with an energy between zero and decay
energy, the neutrino carries away the difference between decay energy and
β+ energy. Some examples of β+ decay are 18
F (110 min)
18 18
F O + β+ + ν
9 8 β+ 97%
64 64 EC 3%
29
Cu
28
Ni + β+ + ν
52 52
26
Fe
25
Mn + β+ + ν 18
O (stable)
 Electron Capture (EC) x-ray

As an alternative to β+ decay
An electron is captured from the extranuclear
electron shells. Usually the K shell electrons
are captured because their proximity to the
nucleus; the process is then called K capture.

transforming a proton into a neutron and emitting a neutrino

p + e+ → n + ν
The vacancy created in the K shell after electron capture is filled by the transition
of electrons from an upper level (probably the L shell and possibly the M or N
shell). The difference in energies of the electron shells will appear as an x-ray
that is characteristic of the daughter nucleus.
The probability of electron capture increases with increasing atomic number,
because electron shells in these nuclei come closer to the nucleus
Electron Capture (EC)
For the electron capture to occur, the energy difference between the parent
and daughter nuclides is usually, but not necessarily, less than 1.02 MeV.
Nuclides having an energy difference greater than 1.02 MeV may also decay
by electron capture.
Several radionuclides used in nuclear medicine decay by EC:
51
Cr, 57Co, 67Ga, 111In, 123I, 125I, and 201Tl

EC is a desirable decay mode for diagnostic radiopharmaceuticals because

no particular radiation produced , lowering the patient’s radiation adsorbed
dose. 51
Cr (27.704 d)
The decay equation for 51Cr is EC1 (9%)

EC2 (91%)
γ
51
V (stable)
Isomeric Transition (IT)
Isomeric transition occurs when an excited nucleus loses its excess energy
by emission of only a gamma ray, with no change in the atomic number or
neutron number

99m
Tc (6.02 h) 142 keV
43

140 keV

γ−ray

99
Tc (2.12 x 105 y)
43
Internal Conversion
In some isomeric transition the energy released
l
hel

from the nucleus may be transferred to inner-shel

Ls

x-ray
Ks

electron instead of being emitted as a gamma ray

e-
hell

conversion electron

γ−ray
There is probability that the photon may knock out an
electron from the extranuclear electron shell of its own
atom, particularly the K shell

The conversion electron will have the kinetic energy:

E c= E γ- E B
Eγ and EB are the photon energy and the binding energy of the ejected electron,
respectively
Internal Conversion
Internal conversion is an alternative to isomeric transition .
The ratio of the conversion electrons (Ne) to the observed photons (Nγ)
is referred to as the conversion coefficient (α):

α = Ne
Nγ
The larger the conversion coefficient, the smaller the number of observed
photons. The probability of internal conversion is higher for the low energy
photons γ (82%)
1%

4%
203
Hg 13%
Radioactive Decay Equations
Radionuclides unstable nuclides
dec
ay
-particle emission
-photon emission
-electron capture

The decay of radionuclides is a random process one cannot tell which

atom from a group of atoms will decay at a specific time . One can only
talk about the average number of radionuclides disintegrating during a period
of time.
The number of disintegrations per unit time (disintegration rate), -dN/dt, of
a radionuclide at any time is proportional to the total number of
radionuclide present at time. Mathematically,
− d = λN
Nd
Radioactive Decay Equations
d
− = λN (1)
Nd
t
N is the number of radionuclides. λ is a decay constant that is defined as
the probability of disintegration per unit time for a single radionuclide. It
has value which is characteristic of the nuclei under consideration.
By integration, Eq. (1) becomes
d = λ
∫ NN ∫ d
−
t
− l N = λ t + constant of integration (2)
n
To evaluate the constant, let N be the number of radionuclides present at
0
some arbitrary zero time, and N the number at time t. When t = 0,
− l N 0 = constant of integration
n
Radioactive Decay Equations
By rearrangement, Eq. (2) becomes :

− l N = λt − l N 0
n N n
−l = λt
n N0
N = − λt
N0
e
− λt
N = N 0e (3)
Equation (3) represents the exponential decay of any radionuclides.

The time for any quantity of radionuclides to decrease to half of its original
quantity is referred to half-life (t1/2)
N 1 (ln 2 ) 0 . 693
= = e − λt 1/ 2
t1 / 2 = = (4)
N0 2 λ λ
 A0
100

log Activity (arbitrary unit)

Activity

A0/2 50

A0/4 25
t1/2

1 2 3 4 6 7
1 2 3 4 5 6 Time (half-lives)
Time (halve-lives)
The half-life of a radionuclide can be determined experimentally by measuring the
activity of a sample over time, assuming that the half-life is reasonably short.
Radionuclides with very short or very long half-lives require special techniques.
Radioactive Decay Equations
Another relevant quantity of a radionuclide is its mean life , τ, which is the
average life of a group of the radionuclides and denoted by the following
relations:
1 t
τ = = 1 / 2 = 1 . 44 t1 / 2 (5)
λ 0 . 69
3
The rate of decay of a radionuclide is described by its activity (radioactivity),
A, or the number of nuclear transformations or disintegration per unit time;
therefore, A is equivalent to λN, and may be written
d
A=− = λN (6)
Ndt
The radioactivity of a radionuclide at time t
− λt
At = A 0 e
Units of Radioactivity
Radioactivity can be expressed in three ways:
▪ as nuclear transformations per second, frequently referred to as decays or
disintegrations per second (dps);

▪ as curies (Ci), millicuries (mCi), microcuries (μCi), or nanocuries (nCi);

▪ as becquerels (Bq)

The curie was originally defined as the number of disintegrations per second
occuring in 1 gram of 226Ra.
Experiments determined that 1 gram of “pure” radium had a disintegration
rate close to 3.7 x 1010 dps
Units of Radioactivity
The International System of Units has adopted the becquerel (Bq) as the
official SI unit of radioactivity. One Bq is defined as one nuclear
transformation per second or one disintegration per second.
1 dps = 1 dis s-1 = 1 becquerel = 1 Bq
1 Bq = 1 x 10-3 kBq (kilobecquerels) = 1 x 10-6 MBq (megabecquerels)
1 Ci = 3.70 x 1010 dps = 3.7 x 1010 Bq or 37 GBq (gigabequerels)
= 2.22 x 1012 dpm (disintegrations per menit )
1 milicurie (mCi) = 3.7 x 107 dps = 3.7 x 107 Bq = 37 MBq
= 2.22 x 109 dpm

1 mikrocurie (mCi) = 3.7 x 104 dps = 3.7 x 104 Bq = 37 kBq

= 2.22 x 106 dpm
1 nanocurie (nmCi) = 37 dps = 37 Bq
= 2.22 x 103 dpm
Units of Radioactivity
Although the becquerel is the official unit of radioactivity, the traditional
curie units are routinely used in practice.

The radioactive concentration of a radionuclide is defined as the radioactivity

per unit volume of a sample, i.e. mCi/ml, mCi/ml, Bq/ml, kBq/ml, etc.
A 10 ml solution containing 45 mCi radioactivity will have a concentration
of 4.5 mCi/ml
Specific activity is defined as the radioactvity per unit mass of a radionuclide
or a labeled compound, i.e. mCi/g, mCi/g, Bq/g, kBq/mol, etc.
A 100 mg 131I-labeled albumin contains 150 mCi 131I radioactivity. Its specific
activity would be 1.5 mCi/mg.

The specific activity of a carrier-free radionuclide sample is related to the

half-life of the radionuclide: the shorter the half-life, the higher the specific
activity
 DASAR-DASAR
RADIOFARMAKA (2)

PENGUKUR RADIASI
Geiger-Müller Window tipis dari mika
memungkinkan partikel β dan sinar γ
Detector energi rendah untuk lewat yang
biasanya akan tertahan oleh casing
Cathod Thin tabung yang terbuat dari logam.
e Window

+ + ++ ++
- - - - - --
- - - --
+ + ++ Sumber Radiasi
β, γ

Karena tegangan kerja tabung GM cukup tinggi,

Anod radiasi yang memasuki tabung akan
e menghasilkan ionisasi primer dan ion primer
ini selanjutnya akan mengionisasi seluruh gas
yang ada di dalam tabung
GM Counter cocok untuk mendeteksi keradioaktifan rendah, karena itu paling umum
digunakan untuk memantau daerah kerja bila terjadi kontaminasi.
Geiger-Müller Detector
Metoda Scintilasi
Ada dua jenis detektor • Detektor scintilasi kristal padat
scintilasi: • Detektor scintilasi cair

Detektor sendiri merupakan medium primer untuk terjadinya

interaksi dengan radiasi. Prinsip kerja kedua jenis detektor
adalah sama, kecuali material detektor yang berbeda.

Detektor scintilasi kristal padat yang paling umum adalah

kristal natrium iodida, NaI(Tl), yang dibungkus dengan suatu
casing logam, sehingga sinar γ dengan energi yang memadai
mampu menembus casing logam dan selanjutnya berinteraksi
dengan kristal. Hal ini tidak dapat terjadi bila radiasi
merupakan radiasi partikel.
Metoda Scintilasi

Karena itu pencacahan radionuklida pemancar

partikel β murni, seperti 3H dan 14C, paling baik
dilakukan dengan menggunakan scintilasi cair.
Disini cuplikan yang diukur terlebih dahulu
dilarutkan atau disuspensikan dalam suatu
“cocktail” scintilasi yang merupakan campuran
pelarut dan senyawa-senyawa scintilator.
Semakin intim cuplikan dan “cocktail”
bercampur, semakin efisien deteksi radiasi β
Detektor scintilasi kristal padat
Sinar-
γ

Kristal
NaI(Tl) Scaler

Tabung Photomultiplier
(PM)
Rate
Meter
Pulse
Pre-Amp Linear
Height
lifier Amplifier
Analyzer
High
Oscillosco
Voltage
pe

Compute
r
Detektor scintilasi kristal padat
Kristal photocatho photomultiplier
NaI(Tl) de tube

scintila
si

Sinar-γ Foton dynode elektron

cahaya s
• Foton energi tinggi (sinar-γ) yang berinteraksi dengan kristal akan memindahkan
energinya ke molekul natrium iodida melalui hamburan Compton dan interaksi
fotolistrik.
• Energi elektron yang dilepaskan dari proses ionisasi hampir seluruhnya diserap
dalam bentuk panas. Bila kristal dalam bentuk natrium iodida murni, maka proses
scintilasi tidak berlangsung dengan baik.
• Karena itu jika kristal diaktifkan dengan 0.1% thallium, maka beberapa elektron
tereksitasi terperang-kap disekitar atom thallium, dimana pada saat kembali ke
Detektor scintilasi kristal padat

Well Counter
Larutan radiofarmaka di dalam tabung
reaksi

Kristal NaI(Tl) berbentuk sumur

Electron photomultiplier tube

Perisai dari Pb
Detektor scintilasi kristal padat
Sinar-γ
window

Linear
ABC Amplifier ABC ABC
Pulsa B
Pulse yang
Height tercacah
Analyzer
Awal LLD dinaikan Window dinaikan
UL
D UL
LL
UL D D
height
Pulse

D
LL LL
D D
1 2 3 4 1 2 3 4 1 2 3 4
Pulsa 2 yg Pulsa 3 yg Pulsa 1 dan 2 yg
tercacah tercacah tercacah
Spektrum Energi Gamma
Bila suatu radionuklida dicacah dengan pencacah scintilasi, kemudian laju cacahan
(count rate) diplotkan terhadap energi, maka akan diperoleh spektrum gamma.

123 51
I C
r
A : 27 ~ 31 keV Te x-rays A : 320 keV
gamma
B : 159 keV gamma

A B A

131
I 99m
Tc
A : ~ 30 keV Xe x-rays
A : 140 keV
B : 80 keV gamma
gamma
C : 364 keV gamma
D : 638 keV gamma

AB C D A
0 Energi 102 0 Energi 102
(keV) 4 (keV) 4
Detektor scintilasi cair
14
CH2NH2CO
β− OH

S* F1

R β S
−
F
F
S F1* F2

PM
Tube e
Foton -e
F1 F2* e -e
Cacah
cahaya - puls an
S = pelarut e-
e- a
-
F = material yang mengandung
fluor Photocath Anod
ode e
Efisiensi Pencacahan (Counting Efficiency)
Cacahan (counts) per menit yang tercatat suatu instrument
dibagi oleh disintegrasi per menit (dpm) yang terjadi di dalam
cuplikan yang sedang dicacah.

Efisiensi = cp
dpm
m

• Efisiensi diri detektor yang

Detektor NaI bidang dipenga-ruhi oleh jenis
Faktor utama yang
datar radiasi dan energinya, dan
mempengaruhi efisiensi:
ukuran serta komposisi
detektor.
• Faktor geometri
 Efisiensi diri (intrinsic) adalah jumlah
radiasi yang berinteraksi di dalam detektor
dibagi dengan jumlah radiasi yang datang
ke detektor

Net
Efisiensi cpm
Detektor NaI tipe = (Source (2.26 x 106 (kelimpahan
sumur μCi) dpm/μCi) foton)
Contoh:
1.0 μCi (37 kBq) gas 133Xe yang berada di
dalam vial 3 ml dicacah dengan
menggunakan pecacah scintilasi sehingga
diperoleh hasil cacahan bersih sebesar
486508 cpm. Diketahui kelimpahan foton
gamma energi 81 keV dari 133Xe adalah 36%.
Hitung efisiensi pencacahan dengan
meggunakan pencacah scintilasi tersebut.
JAWAB:
486508 cpm
Efisiensi = =
0.61
(1.0 μCi) (2.26 x 106 dpm/μCi) (0.36)

Jika kita mengetahui efisiensi detektor suatu radionuklida

tertentu dalam geometri tertentu, maka keradioaktifan
sumber dapat ditentukan sebagai berikut:

Net
Aktivitas (μCi) = cpm
(2.26
(Efisiensi) x 106 (kelimpahan
dpm/μCi) foton)