Many minerals contain aluminum and silicon oxides. For example, three minerals andalusite, sillimanite, and kayanite all have the same chemical composition of Al2O(SIO4). Topaz is closely related in chemical composition, Al2O(SIO4)(OH,F)2.
Beryl, Be3Al2(Si6O18, contains rings of (SiO3)6 type. It is usually found in cavities of granite. This mineral is also known as aquamarine, a precious stone. This is the main source of Be metal. A closely related mineral is cordierite, Al3(Mg, Fe)2(SI5AlO18).
Layer aluminum silicates such as kaolinite goup of minerals of Al4(Si4O10)(OH)8 is resulted from weathering of feldspar group of minerals, (K, Na)(AlSi3O8, or Ca(Al2Si2O8. The koalinite group is an important clay mineral. The picture shown here is the structure of kaolinite. Two layers are shown here, the bottom octahedral layer represent the oxygen atoms and the 6-coordinated Al atoms or ions. Some of these oxygen atoms are shared with 4-coordionated silicon on the top layer, each tetrahedron represent a SiO4 group.
Zeolites are the most important group of aluminum silicates. About 40 natural zeolites are known and 150 zeolites have been synthesized.
Jadeite is often confused with nephrite. These are aluminum silicates.
For example, the following minerals belong to the feldspar group.
However, the bonding between Al and Si can be different. Silicon atoms or ion tend to be bonded to 4 oxygen atoms in a tetrahedral fashion, but aluminum ions tend to be bonded to 6 oxygen atoms in an octahedral fashion.
Jaujasite is a representative zeolite. This link represented its
structure using large polyhedra.
All lines in the structure shown are oxygen bridges -O-, the oxygen atom
is located not on the line but somewhere next to it. The angle -O- of the two
bonds is about 110ø. Points where lines meet are the locations of
Si4+ that are surrounded tetrahedrally by four oxygen atoms.
They can be substituted by Al3+. As a result, the frame work
is negatively charged. Thus, zeolites can trap positive ions:
H+, Na+, K+, Ca2+, Cu2+
or Mg2+.
The name 'zeolite' is said to have its origin in the two Greek words zeo and lithos which mean 'to boil' and 'a stone'. The phenomena of melting and boiling at the same time is a novel property. The name 'zeolite' was first used by the Swedish mineralogist Cronstedt to describe stilbite, the first recognized mineral zeolite, which was discovered in 1756. Over 100 years later, the reversible desorption/adsorption of water in this mineral was recognized.
A Faujasite elementary cell is shown in ball-and-stick model below.
While you are admiring this beautiful picture of faujasite, remember that the oxygen atoms have two unshared electron pairs in addition to the (Al,Si)-O-Si(or Al) bonds. Thus the oxygen atoms are sites to interact with positive site of molecules that passes by these structures.
At present over 150 synthetic zeolites & zeotypes and 40 natural zeolites are known. Synthesis of zeolite is a very active field of study.
Aluminosilicates have three major minerals: Andalusite, sillimanite, and kyanite. Zeochem has been developing and manufacturing molecular sieve adsorbents since 1977. Simply put, their adsorbents are used to "screen" out impurities from a variety of applications by attracting and trapping the targeted contaminants. For example, in natural gas processing, Zeochem sieves are used to remove specific molecules from the gas stream to allow for more efficient downstream processing.
A rather large model of zeolite (faujasite) is brought to the class on Nov. 12. This is a typical zeolite, and spaces within the cage and channels through the structures cannot be appreciated without the model.
Example 1
Solution
We have discussed the solution of this problem type in class.
The formula for the proton form zeorlite A is
H12[(AlO2)12(SiO2)12]
.27H2O, and its formula (molecular) weight is
(1+27+32+28+32)*12+27*18 = 1926 g/mol. Note the following:
1 mol CaCO3 2 mol H+ 1 mol z-A 1926 g z-A 100
123 g CaCO3 ----------- ----------- ---------- ---------- ---
100 g CaCO3 1 mol CaCO3 12 mol H+ 1 mol z-A 80
= 494 g zeolite A
That 80 % of protons of the zeolite A is used means that we
require a little more zeolite A than stoichiometric quantities.
Discussion
Zeolites are aluminosilicates, and their structures consist of open frames
as discussed above. Replacement of each Si atom by an Al atom in silicates
results in having an extra negative charge on the frame. These charges must
be balanced by trapping positive ions: H+, Na+,
K+, Ca2+, Cu2+ or Mg2+.
Water molecules are also trapped in the frame work of zeolites.
In this example, we assume that when we soak the zeolite in water containing Ca2+, and Mg2+ ions, these ions are more attrative to the zeolite than the small, singly charged protons. We further assumed that 80 percent of the protons in zeolite are replaced by other ions.
Example 2
Solution
The molar mass of Na-zeolite A is
(23+27+32+28+32)*12+27*18 = 2190 g/mol = 2.19 kg/mol, and the molar
mass of NaCl is 58.5 g/mol.
1 mol 0.8*12 mol NaCl 100 58.5 g NaCl
10 kg z-A -------- --------------- --- -----------
2.190 kg 1 mol z-A 20 1 mol NaCl
= 12822 g NaCl = 12.8 kg NaCl
Discussion
How much salt is required if 60% of the sodium ions are effectively
used to replace all the divalent ions?
Skill - Describe the bonding of silicon from its electronic configurations (atomic orbitals).
Skill - Describe the formation of aluminosilicates.
Skill - Apply the principle of charge conservation to the chemical problems.
Skill - Explain zeolite properties in based on electronic structures of atoms.