The angular momentum quantum number ll takes integral values of zero up

to (n - 1) where n is the principal quantum number. So if n = 3 then ll has

values of 0,1 and 2. These correspond to the s, p and d orbitals. If you look at
the normalised electron probability function plotted against distance from the
nucleus you see that the lower the value of ll the greater the "penetrating
power" of the electron hence the greater shielding ability which is in the order
s > p> d.

shielding effect is the reduction in effective nuclear charge on electron

cloud due to differences in attaraction between electrons and nucleus. It
depends on many factors like size of atom , charge density , orbitals
involved , effective nucleus charge . Size of s and porbitals are very lesser
than d and f , due to that electrons of d and f orbitals are spreaded in large
area and thus there are less effective shielding or poor shielding. structures
of orbitals are also responsible for that.

% of Ln as:

Th

Y La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

monazite

ca 6 3

22 45 5

17

4 0.1 2 0.2 1 0.1 0.4

xenotime

ca 5 61 0.5 5 0.7 2.2 1.9 0.2 4

1 8.6 2 5.4 0.9 6.2 0.4

basnaesite

0.05 0.1 32 49 4.4 13.5 0.5 0.1 0.3

- 0.1

0.2

Even though they are called "rare earths", these elements are not really rare, with the
exception of promethium which is radioactive and does not occur naturally. For example,
cerium, which is the most abundant in the lanthanide series, is more abundant than that of
cobalt, tin and zinc; thalium, which is tha least abundant, occurs in similar quantities to
mercury and is more abundant than silver. Although lanthanides are found in many ores,
bastnaesite, monazite and xenotime are the major sources for industrial production.
These deposits are located mainly in China, the USA, India, Australia and Brazil; China
has the most important reserves.

ORES AND MINERALS OF LANTHANIDES

MONAZITE
XENOTIME
GADOLINITE
ALLANITE
CERITE
EUXENITE
BASTNASITE
POLYCRASE
FLUOROCERITE

CePO4
YPO4
FeBe2Y2Si2O10
(Ce,Ca)2FeAlO(Si2O7)(SiO4)(OH)
Ce3CaSi3O13H3
Y3(Nb,Ta)3Ti2O15
CeFCO3
Ce, Y, Th, U)(T, Nb, Ta)2O6
CeF3

The table above lists some of the principal ores; these are generally found
worldwide tough most of the commercial extraction is carried out in the USA,
especially from the Californian bastnasite. Monazite and bastnasite are the
principal ores worked. Monazite is rare but because it is very heavy it is
accumulated on the form of sand deposits by weathering process. It often
occurs together with similarly heavy weathering products like ilmenite
(Fe3TiO3) and Cassiterite (SnO2). The abundance of individual lanthanides
varies from one mineral to another,; some, like monazite, are richer in the
lighter elements, others, such as xenotime, contain more of the heavy ones,
while a third class, such as euxenite, has a fairly even distribution. In all ores
the atoms with even atomic number are more abundant reflecting an enhanced
nuclear stability.

EXTRACTION OF LANTHANIDES
Before chemical treatment, the minerals are concentrated by processes like
floatation to increase the lanthanide oxide content from about 7-10 percent to
60 percent.
Monazite needs pre-treatment because of the 5-10% thorium dioxide, 3%
yttrium earth, and phosphate contents:

Traditionally this was achieved through digestion with H 2SO4, turning the
phosphates into soluble sulfates. Nowadays digestion with caustic soda is
employed instead as it affords a better separation of the lanthanides and
recovery of the phosphates, as well as eliminating corrosion problems and
wastes To do this ,the concentrated ore is heated with 65 percent NaOH at 140
degrees for some hours. On cooling, sodium phosphate is dissolved out with

hot water and the hydroxides of thorium and the lanthanides are filtered off.
The lanthanides are selectively dissolved out of this mixture with dilute HCl.
Monazites can also be extracted through a different route such as the acid route:

Bastnasite, on the other hand, contains 20-30 percent lanthanum, 50% cerium,
5% praseodymium, and 5-20% neodymium the remainder are at the other
lanthanides. The extraction of bastnasite can be done by acid dissolution:

Acid leaching (dilute HCl) of bastnasite concentrates, to remove associated

calcite, yields 70 percent oxides. Some of this concentrate is mixed with
carbon, then chlorinated forming mixed "rare earth" chlorides - on electrolysis
this forms the mixture of lanthanides called mischmetal. Otherwise concentrate
is treated with NaOH to turn it into a mixture of lanthanide hydroxides, which
on dissolution in hydrochloric acid affords mixed lanthanide chlorides.
Monazites has roughly the same sequence of relative abundances: Ce> La>
Nd> Pr.
SEPARATING LANTHANIDES
From the time that Gadolin obtained "yttria", a mixture of lanthanide oxides,
from Gadolinite, chemists were faced with problem of separating 15 very
similar elements. Selective reduction( Eu3+ to Eu2+) or oxidation (Ce3+ to Ce4+)
could be exploited - thus EuSO4 is insoluble unlike Ln3+ sulfates, for example
- but until around 1950 most separation revolved around hundreds of tedious
fractional cystallisations of compounds like the bromates, double sulphates
(NaLn( SO4)2*xH2O) or double nitrates (such as Mg3Ln2( NO3)12*24H2O. The
difficulty in separating lanthanides can be observed from the similarity of their
ionic radii. The ionic radii of the lanthanides ions are longer than those of the dblock transition elements. They decrease monomerically with increasing atomic
number. This is the well-known "lanthanide contraction", which arises from
the ineffective shielding of the 4f electrons, resulting in an increase in effective
nuclear charge and a concomitant decrease in ionic radius. Ionic radii are
affected by oxidation state; the dipositive ion has ionic radii about 10% larger
than those of the tripositive ion, and the ionic radius of the tetrapositive ion is
smaller than that of the tripositive one. The relatively large ionic radii of the
lanthanides allow the accomodaiton f up to 12 ligands in the coordination
sphere, and coordination numbers of 7, 8, and 9 are common. In general,
"light" lanthanides, whose ionic radii are large, tend to have higher
coordination number than the "heavy" lanthanides
Lanthanum (Ln)
Cerium (Ce)

102 pm

Terbium

92 pm

Praseodymium (Pr)

99 pm

Dysprosium (Dy)

91 pm

Neodymium (Nd)

98 pm

Holmium (Ho)

90 pm

Promethium (Pm)

97 pm

Erbium (Er)

89 pm

Samarium (Sm)

96 pm

Terbium (Tm)

88 pm

Europium (Eu)

95 pm

Ytterbium (Yb)

87 pm

Gadolinium (Gd)

94 pm

Lutetium (Lu)

86 pm

The two currently use methods of separation require an aqueous solution of the
Ln3+ cations. To this end, the minerals are hydrolyzed through subsequent
reaction with NaOH and HCl. The present method of separation includes ionexchange chromatography and solvent extraction.
SEPARATION OF LANTHANIDES BY ION-EXCHANGE
CHROMATOGRAPHYTo perform an ion-exchange separation, a
solution of lanthanide ions is induced at the top of the a cation-exchange
column in the sodium form. The Ln3+ ions readily undergo ion exchange
displacing Na+ ions, thus forming a band of the lanthanide ions bound to the
top of the cation exchange column. To remove these ions down the column and
effect a separation, a solution consisting ligands such as citrate, lactate or
(NH4)3 EDTA-H . These ligands form complexes with the lanthanides.
Moreover, because the complexes possess lower positive charge than the initial
Ln3+, they are less tightly held by the resin Ln3+, and are displaced from the
ion exchange material into the surrounding solution. The equilibria that are
established between cations on the ion exchange resin (res) and neutral or
anionic complexes in solution can be summarized as follows. Initial ion
exchange displacement of the Na+ and La3+ in a band at the top of the
column:Ln3+ (aq) + 3Na+ (res) <----> Ln3+ (res) + 3Na+ (aq)Subsequent
elution with a solution of a complexing agent leads to formation of neutral or
negatively charged lanthanide complexes. To maintain electroneutrality with
the ion exchange resin sodium cations take place of the neutral or negative
lanthanide complex: 3Na+ (aq ) + Ln3+ (res) + 3 RCO2-(aq) <----> 3Na+ (res) +
Ln(RCO2)3(aq)The heavier, smaller lanthanide ions form stronger EDTA

complexes so that they are removed from the resin first, thus the lanthanides are
eluted in order of decreasing atomic number; with long columns, complete
separations can be achieved (see figure below

SEPARATION OF LANTHANIDES USING SOLVENT

EXTRACTION
Since the 1960's, solvent extraction has been the favoured process, employing
complexing agents like tributylphosphate or bis(2-ethylhexyl)phosphenic acid
in a covalent solvent:

di(2-ethylhexyl)phosphenic acid (DEHPA)

Ln3+ (aq) is extracted in a continuous counter-current process into a non-polar
organic liquid such as kerosene which contains ca. 10% of the DEHPA. If the
two phases are moved with respect to each other (which can be done in a
continuous or discontinuous way) the ions move depending of the distribution
constant in the two phases. Solvent extraction today is the largest industrial
scale of industrial separation of lanthanides.

Lanthanides Separation

/3 of world production is actually used mixed in the proportions occuring naturally in the
ore
2

1. Cerium & Europium may be extracted Chemically:

Oxidize only Ce to M4+ by HClO or KMnO4, then precipitate as CeO2 or Ce(IO3)4

On action of Zn/Hg only Eu forms a stable M2+ that doesn't reduce H2O, then isolate by
precipitation as EuSO4

2. Separation by Fractionation:
Small Scale methods used originally:
Fractional Crystallization of e.g. Ln(NO3)3.2NH4NO3.4H2O or Ln(BrO3)3
Fractional Thermal Decomposition of e.g. Ln(NO3)3
Current Small Scale Lab. Separation:
Ion-Exchange Displacement Column

Ln3+(aq) are strongly adsorbed by a cation-exchange resin

add an eluant ligand

typically chelating ligands

e.g. EDTA

, or 2-hydroxy-EDTA

e.g. HIB{[[alpha]]-hydroxyisobutyric acid}

Ligand binds most strongly to smallest ion

e.g. the binding constants of the Ln(EDTA) complexes

Elution order is Lu La

The process of separation is indicated graphically

greater detail on these columns may be found in:

Greenwood & Earnshaw, p. 1427-1428

Open University S304 Unit 27, p. 20-22

Current Large Scale Industrial Separation:

Solvent Extraction

Ln3+(aq) is extracted in a continuous counter-current process into a non-polar organic

liquid(e.g. kerosene)

the kerosene contains ca. 10% of

o bis(2-ethylhexyl)phosphinic acid (DEHPA)

or

o tri-n-butylphosphine oxide (TBPO) (nBu3O)3PO

1. solubility of Ln3+ in organic solvent increases with its RAM
2. separation factor for adjacent rare earths = 2.5
3. automatic multistep, counter-current conditions 99.9% purity Ln