Mineral Chemistry: But Not Independent: WT% Oxides
Mineral Chemistry: But Not Independent: WT% Oxides
Mineral Chemistry: But Not Independent: WT% Oxides
Mineral properties = f(structure + chemistry) But not independent: structure = f(chem, T, P) Compositions are conventionally given as wt% oxides (unless sulfides, halides, etc.) I'd prefer mole % actually, but inherited this system Difference between Fo = Mg2SiO4 and Fo= 51.5% SiO2 and 48.5% MgO
Mineral Chemistry
Homework Problem Handout 1) 2 Pyroxenes
Convert wt% oxides to formula. COOKBOOK
Mineral Chemistry
Method of Scientific Analysis
Write single equation to get from what have to what want. Have: u. c. Volume (in A3) & formula A = 10-8 cm. Want Z = # formula units/ u.c. Example 8 mi/hr = ? in ft/sec? If do all on one line with #'s and units, If units work # must! Want formula units/mole (Avocados #)
Most common silicates are from these O alone = 94 vol. % of crust Perhaps good to think of crust as a packed O array with interspersed metal cations in the interstices! Analogy works for minerals too (they make up the crust)
Chemistry Review
Bohr model for the atom
Nucleus = p + n Z (Atomic #) Gives elements their identity (properties) (~ all mass)
p + n (variable) atomic weight (isotopes) At. Wt. is real # due to average of isotopes
e- spin around atom and give it it's size (statistical size) Atomic radii in the range 0.5-2.5 A
e- in special shells w/ particular Energy levels Quantized
Chemistry Review
Quantized energy levels
f f d p s
(Fig. 4.12)
d p s
Relative Energy
f d d p s p s s p s
d p s
Note that the energy does not necessarily increase K L M N etc. 4s < 3d
n= 1K
2L 3M
4N
5O
6P
7Q
Chemistry Review
Shells and Subshells innermost
(lowest E)
K L M N
(n = 1) (n = 2) (n = 3) (n = 4)
2e 8e
s s, p
18e s, p, d 32e s, p, d, f
outer
(generally higher E)
Chemistry Review
Shells and Subshells 1s 2s and 3s orbitals
px
z x
py
pz
x x y
d orbitals z d xz
d xy
d yz
x y
d x2-y2
d z2
Shell K Subshell s 1. H 1 2. He 2 3. Li 2 4. Be 2 5. B 2 6. C 2 7. N 2 8. O 2 9. F 2 10. Ne 2 11. Na 2 12. Mg 2 13. Al 2 14. Si 2 15. P 2 16. S 2 17. Cl 2 18 Ar 2 19. K 2 20. Ca 2 21. Sc 2 22. Ti 2 23. V 2 24. Cr 2 25. Mn 2 26. Fe 2 27. Co 2 28. Ni 2 29. Cu 2 30. Zn 2 31. Ga 2 32. Ge 2 33. As 2 34. Se 2 35. Br 2 36. Kr 2 37. Rb 2 38. Sr 2 39. Y 2 40. Zr 2 41. Nb 2 42. Mo 2 43. Tc 2 44. Ru 2 45. Rh 2 46. Pd 2 47. Ag 2 48. Cd 2 49. In 2 50. Sn 2 51. Sb 2 52. Te 2 53. I 2
1 2 3 4 5 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6
1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2
1 2 3 4 5 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6
Table 3.6 p. 51-52 shows the progressive filling of orbitals as energy increases
1 2 2 2 2 1 2 2 2 2 1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2
1 2 3 5 5 6 7 8 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10
1 2 3 4 5 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6
1 2 4 5 5 7 8 10 10 10 10 10 10 10 10
1 2 2 2 1 1 2 1 1 1 2 2 2 2 2 2
1 2 3 4 5
It is the outermost shell or valence e- s that are fundamental Similar outermost shell configurations Groups in the Periodic Table (Table 4.8 p.188) alkali metals (Ia) have a lonely e- in outer shell halogens (VIIa) have 7 einert gases (VIIIa) have 8e- a magic #... filled s & p (He only has s with 2 e-)
Other elements try to gain this stable inert gas config. If have one extra (alkalis) will readily lose it if it can find another way to attain charge balance This results in an ion with a +1 valence Group II metals will lose 2 e- +2 valence Halogens will capture an e- inert gas config. -1 Ionization Potential (T 3.7) Electronegativity is the ability of an atom in a crystal structure to attract electrons into its outer shell In general, electronegativity increases
Chemical Bonds
Electrical in nature- responsible for most mineral properties 1) Ionic Na: low 1st IP e- Na+ (Ne config) Cl: high e-neg takes e- & = Cl- (Ar config) Now they have opposite charges & attract bond (really a very unequal sharing) Bonding is strong (high melting point) But easily disrupted by polarized solvents (water) Poor electrical conductors. Strength (1/bond length) & valence Also non-directional (more later), so symm. is a packing function and thus rather high (isometric common). If e-neg of 2 atoms differs by 2.0 or more will ionic
Chemical Bonds
2) Covalent
Consider 2 Cl atoms each trying to steal each other's e= 1s2 2s2 2 p6 3s2 3p5 Can't do, but if draw close until overlap an outer orbital, perhaps can share whereby 2 e- "fill" the remaining 3p shell of each Cl
Actually fill it only 1/2 the time for each, but better than nothing
In fact this compulsion to stay overlapped & share results in a strong bond Cl2 This is the covalent or shared e- bond (the Socialist bond)
Double bonds when 2 orbitals shared Triple bonds when 3 orbitals shared
Chemical Bonds
Hybrid orbitals
Carbon: | |
1s 2s
Fig 8-8 of Bloss, Crystallography and Crystal Chemistry. MSA
2p
|
1s
2(sp3)
Chemical Bonds
Hybrid orbitals 2(sp3) is tetrahedrally shaped (energy is identical) Larger overlap stronger Directional: each C is tetrahedrally coordinated with 4 others (& each of them with 4 others...) C-C-C bond angle fixed at 109o 28' (max. overlap) Note Face-centered Cubic lattice The directional character lower coordination & symmetry, density
Chemical Bonds
Hybrid orbitals
Alternatively: Carbon: | |
1s 2s
2p
|
1s
|
2p
2(sp2)
As most organic chemists know, C is a flexible element In fact, many atoms in the center of the Periodic Table with partially filled valence shells are variable in how they attain stability (this includes Si)
Chemical Bonds
The 3 2(sp2) orbitals are coplanar & 120o apart Graphite structure
Fig 8-8 of Bloss, Crystallography and Crystal Chemistry. MSA
Chemical Bonds
The 3 2(sp2) orbitals are coplanar & 120o apart Graphite structure Overlap similar to diamond w/in sheets (strong too!) Must Hexagonal Crystal Class Note p-bonding between remaining 2p's This results in delocalized e- 's in 2p which results in electrical conductivity only within sheets
Chemical Bonds
There are other hybrids as well 2 (dsp in CuO- planar X) e- may resonate in bonds of non-identical atoms & give a partial ionic character if one much more e-neg than other In fact most ionic crystals share to some extent while covalent may share unequally This is a result of De-neg
Chemical Bonds
3) Metallic Bonding
Metals are on the left of the P.T. Have few, loosely held valence eIf closely pack them can get up to 12 "touching" nearest neighbors This a high density of valence e- around any given atom & also a high density of neighbor atoms around the loose valence eThe effect is to show such a general attraction for these e- that they become free to maintain an electrical neutrality in the xl as a whole... a sea of mobile electrons Let's call it the left-side equivalent of the covalent bond (On the right side the e-neg is high & atoms are trying to take e-)
Chemical Bonds
3) Metallic Bonding Let's call it the left-side equivalent of the covalent bond On the right side the e-neg is high & atoms are trying to take eIf can't, must share tightly On left, w/ low e-neg & low I.P. they aren't trying to take, but to give, so loosely share Metallic crystals thus conduct electricity and heat
Chemical Bonds
4) Van der Waals Bonds
Weakest bond Usually between neutral molecules (even large ones like graphite sheets) Aided by polar or partial polar covalent bonds.
Even stable A-A bonds like O2 or Cl2 will get slightly polar at low T & condense to liquid & ordered solid as vibration slows & polarity
Condensed Cl
a a
2a 4
Crystal Chemistry
Crystals can be classified into 4 types: 1. Molecular Crystals
Neutral molecules held together by weak van der Waals bonds Rare as minerals Mostly organic Weak and readliy decompose, melt, etc
Example: graphite
Crystal Chemistry
2. Covalent Crystals
Atoms of similar high e-neg and toward right side of PT Also uncommon as minerals (but less so than molecular) Network of strong covalent bonds with no weak links Directional bonds low symmetry and density Example: diamond
Crystal Chemistry
The diamond structure
All carbon atoms in IV coordination
hard-sphere model
Crystal Chemistry
3. Metallic Crystals
Atoms of similar e-neg and toward left side of PT Metallic bonds are directionless bonds high symmetry and density Pure metals have same sized atoms Closest packing 12 nearest mutually-touching neighbors Cubic Closest Packing (CCP) abcabcabc stacking = FCC cell Hexagonal Closest Packing (HCP) ababab = hexagonal cell Also BCC in metals, but this is not CP (VII coordination)
More on coordination and closest packing a bit later
Crystal Chemistry
4. Ionic Crystals
Most minerals First approximation: Closest-packed array of oxygen atoms Cations fit into interstices between oxygens Different types of interstitial sites available Occupy only certain types where can fit Occupy only enough of them to attain electric neutrality