CHEM 252

LECTURE 6
 Actinides
The 15 elements from Ac-Lr or the 14 from Th-Lr

Revised Medium-Block Format Periodic Table

 Actinides
ELEMENT SYMBOL ATOMIC ELECTRONIC OXIDATION
NUMBER STRUCTURE STATE
Actinium Ac 89 6d17s2 III
Thorium Th 90 6d27s2 III, IV
Protactinium Pa 91 5f26d17s2 III, IV, V
Uranium U 92 5f36d17s2 III, IV,V,VI
Neptunium Np 93 5f46d17s2 III, IV, V, VI,
VII
Plutonium Pu 94 5f67s2 III, IV, V, VI,
VII
Americium Am 95 5f77s2 II,III,IV,V,VI
Curium Cm 96 5f76d17s2 III, IV
Berkelium Bk 97 5f97s2 III, IV
Californium Cf 98 5f107s2 II, III
Einsteinium Es 99 5f117s2 II, III
Fermium Fm 100 5f127s2 II, III
Mendelevium Md 101 5f137s2 II, III
Nobelium No 102 5f147s2 II, III
Lawrencium Lr 103 5f76d17s2 III
 ELECTRONIC STRUCTURE
• In the actinide series, the 14 5f electrons are
added formally from thorium onwards and the
5f shell is complete at element 103.
• The electronic structure of the actinides do
not follow the simple pattern found in the
lanthanides.
• Immediately after lanthanum, the 4f orbitals
become appreciably lower in energy than the
5d orbitals.
 ELECTRONIC STRUCTURE
• However, for the first four actinide elements
namely Th, Pa, U, and Np, the difference in
energy between the 5f and 6d orbitals is
small.
• Thus in this element, electrons occupy the 5f
or 6d levels or sometimes both.
 ELECTRONIC STRUCTURE
• Later in the actinide series, the 5f orbitals
become appreciably lower in energy than 6d
from plutonium onwards.
• The 5f shell fill in a regular way and the
elements become very similar.
 Periodicity
• Actinides is taken here to mean the 15
Elements from Actinium (Ac) to Lawrencium
(Lr)
• Electronic subshells are filled in a manner
analagous to the lanthanide series
– i.e. the Actinides are the second row of the f-block
(5f series)
 Periodicity
• The Actinide Concept of Seaborg - proposed
only in 1944
– prior to the synthesis of trans-uranium elements
only the chemistries of Th and U were much
studied ~ leading to assignment as a 4th transition
series elements.
 Naturally Occurring Actinides
• Only Actinium, Thorium, Protactinium &
Uranium occur naturally (i.e. Z = 92)
– Actinium & Protactinium occur only in trace
amounts
– Neptunium & Plutonium occur in uranium
minerals in minute amounts
• ~ not appreciated until after they had been
synthesised that the synthesis route might
occur naturally!
 Naturally Occurring Actinides
• All isotopes of all the actinides are radioactive
• Most of the longer-lived isotopes decay by α-
emission
• Half-lives - Only quantities of 232Th, 235U, 238U
{and possibly 244Pu} could have survived since
the formation of the solar system
• Both Thorium and Uranium are far from rare
 Thorium
– Widely dispersed, accounts for >3 ppm of the
earth's crust
– Natural Thorium is essentially 100% 232Th
– Occurs in monazite [with the rare earths] and in
uranothorite [a mixed Th,U silicate]
– Obtained as ThO2, thoria, from mineral extraction
process
– Used as 99% ThO2 / 1% CeO2 in thoria gas mantles
 Uranium

– Widely distributed - found scattered in the faults

of old igneous rocks
– Natural Uranium is 99.27% 238U & 0.72% 235U
– Obtained usually as UO2
– Used for nuclear fuel, and on a smaller scale for
colouring glass/ceramics
Basic Features of Nuclear Structure &
Chemistry and Radiochemistry
• 3 Decay series explain features of the
occurrence, distribution & discovery of
actinide elements
Basic Features of Nuclear Structure &
Chemistry and Radiochemistry
Uranium Decay Series (from 238U)

Actinium Decay Series (from 235U)

Thorium Decay Series (from 232Th)

Basic Features of Nuclear Structure &
Chemistry and Radiochemistry
Uranium Decay Series (from 238U)

Actinium Decay Series (from 235U)

Thorium Decay Series (from 232Th)

Basic Features of Nuclear Structure &
Chemistry and Radiochemistry
• All Radon isotopes are short half-life α-
emitters (but give rise to short-lived β-
emitters)
• Radon gas is derived from Thorium content in
Granite minerals.
• Actinium and Protactinium occur in uranium
ores in trace amounts, because of their
participation in Actinium Decay series (from
235U)
 Synthesis of Trans-Uranium Elements
• 1932 Chadwick discovers the neutron
• 1930s Fermi realises that neutron capture by
heavy elements is often followed by
β-emission (& γ-ray production) leading to
(Z+1) element.
• However neutron-bombardment of 238U yields
mainly fission products
 Synthesis of Trans-Uranium Elements
• 1940 McMillan & Abelson identify tiny
amounts of a short-lived isotope of element
93
 The Golden Age of Element Synthesis through
various "bombardment" techniques

Neutrons Deuterons α-particles, Carbon nuclei,

, ,

•Production of elements beyond Pu requires successive

neutron capture

* reasonable yields need high neutron fluxes

 Principal Difficulties associated with Heavy
Element Isolation & Characterization

1. Powerful accelerators needed for appropriate

velocities.
2. Products are produced only an atom at a
time!
3. Individual elements are not produced cleanly
in isolation
– separation from other actinides and from
lanthanide fission products.
 Principal Difficulties associated with Heavy
Element Isolation & Characterization

4. Radioactivity
– remote-handling often necessary (Actinides are
also highly toxic)
– damage to solutions
• e.g. generation of radicals, H•, OH• in H2O leads to
reduction of higher Actinide oxidation states
– heating problems (e.g. 242Cm gives out 122 Wg-1)
– problems with crystallography
• Fogging of X-ray film
• Creates defects in crystals
 Principal Difficulties associated with Heavy
Element Isolation & Characterization

• 5. Instability of most nuclides

• e.g. No (T1/2 = 1 hr) & Lr (T1/2 = 3 min)
– Heavier elements are produced only in the
minutest amounts
• e.g. typical yields of 258Md (T1/2 = 3 m) are 1 to 3 atoms
per experiment!
• only a few atoms of No and Lr have ever been isolated
– Timespan available for experiments can be very
limited
 Principal Difficulties associated with Heavy
Element Isolation & Characterization

• 6. Difficulty in identification of a few atoms

– Separation by ion-exchange techniques
• even after purification cumulative daughter product
contamination may be a problem
– Using nuclear decay statistics to detect and count
the atoms
• prediction of behaviour from utilization of decay
systematics