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A study of modern inorganic chemistry with emphasis on the principles and trends in the chemistry of the elements and on the essentials of structure, bonding, and reactivity of inorganic systems. Key points in this lecture are: Main Group Elements, Group Iva, Compound, Inorganic Carbon Compounds, Carbon Monoxide, Silanes, Compounds, Hydrides, Nitrogen Oxides and Oxyions, Nitric Acid, Chemistry of Noble Gases
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The Elements1)^
Sn and Pb are metals known since antiquitya)^
Sn alloy with Cu is Bronze (5000 yrs ago) b)^
Pb used in Egyptian pottery glazes and Roman plumbing systems
2)^
Si is a metalloid with long-known oxide: Flint = SiOThe free element was identified by Berzelius in 1823 3)^
Ge is metalloid that was identified as “missing” by Mendeleev in 1871Discovered in 1886 by Winkler
Main Group Elements continued
C is a nonmetal known as charcoal and diamond, not as an element until 1700’sa)^
Isotopes:i.^
12 C 98.9% is main component of “organic compounds” ii.^
13 C 1.1% is an NMR active isotope iii.
14 C 1.2 x 10
-10^ % is formed in the atmosphere and is radioactive
iv.
Radiocarbon dating
-^
14 C is incorporated into living things at the same ratio as it exists
-^
When dead, no more
14 C incorporated and that present begins to decay
Assign a date to the object based on how much
14 C is left
b)^
Allotropesi.^
Diamond is the densest form
-^
Tetrahedral single bonds at all C
-^
Hardest of all natural substanceii.^
Graphite is the thermodynamically most stable form
-^
Layers of fused 6-membered rings with all C sp
2 hybridized
Pi-bonding between layers allows lubrication and electrical conduction
1 1
146
(^10)
147
147
146
5730 year half-life
c)^
Fullerenes = spherical or tubular C oligomers of 5- and 6 membered ringsi.^
Buckminsterfullerene = C
discovered in 1985 (Nobel Prize) 60
ii.^
Found in nature at meteorite impact sites iii.
, Carbon Nanotubes prepared soon after by Laser vaporization of 80
graphite: Kroto, Curl, Smalley 1996 Nobel Prize in Chemistry iv.
Easily functionalized and used to trap small molecules v.^
Hard to synthesize in large amounts vi.
Non-fullerene –C—C
≡C— also identified in nature
d)^
Si and Ge also have diamond structures, but much weaker bondsGe(mp) = 945
o C while C(mp) = 4100
o C
Compounds1)^
“Inorganic” Carbon Compoundsa)^
Carbon can be 5- or 6-coordinate (or even more) when bridging metals
Crystalline C
60
b)^
Silanes = molecules with Si—Si bondsi.^
Unstable because Si—Si (340 kJ/mol) weaker than C—C (368 kJ/mol) ii.^
Si less electronegative than H (1.90 vs. 2.20) so attacked by Nu iii.
Si larger than C, which also makes it more easily attacked by Nu iv.
Empty d-orbitals act as e-pair acceptors
c)^
Ge, Sn, Pb all exhibit the Inert Pair Effect: PbX
, SnX 2
, etc… 2
The Elements1)^
As, Sb (metalloids) and Bi (metal) known since antiquitya)^
Variety of allotropes for all of them b)^
Bi is the heaviest nonradioactive element
2)^
P is a nonmetal first isolated from urine by Brandt in 1669a)^
Glowed when exposed to air: “light bringing” = name b)^
Has many solid allotropesi.^
White P
has cubic and hexagonal forms that react with air--store in H 4
ii.^
Red P has an amorphous structure and can be formed by heating white P iii.
Black P has 6-membered rings, converts to other forms at high Pressure
c)^
tetrahedron in liquid and gas phases
P^
P P P
white
white
black
black
red
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b)^
Hydrazine = N
used as rocket fuel 4
H = -622 kJ/mol
c)^
Phosphine = PH
= poisonous gas 3
i.^
Weaker intermolecular attraction than NH
(little H-bonding) 3
ii.^
mp, bp < NH
3
iii.
Phosphine derivatives (PR
) important Lewis Base Ligands 3
Nitrogen Oxides and Oxyionsa)^
Nitrous Oxide = N
O = dental anesthetic 2
i.^
Decomposes to N
and O 2
(nontoxic) 2
ii.^
Suspected greenhouse gas
b)^
Nitric Oxide = NOi.^
Coordinating Ligand forms metal complexes ii.^
Biological functions (Viagra helps regulate it)
c)^
and NO
Equilibrium 2
i.^
(g)
(g) 2
H = 57.3 kJ/mol
ii.^
= colorless and diamagnetic
iii.
= brown and paramagnetic 2
d)^
Pollutionx^ i.^
NO formed from atmospheric N
during fossil fuel combustion 2
ii.^
Can be oxidized to NO
; collectively they are known as NO 2
x
iii.
Acid Rain: 3 NO
e)^
Nitric Acid = HNO
is an Industrially Important Acid 3
i.^
Used in the synthesis of ammonium nitrate fertilizer (much N content) ii.^
Ammonium Nitrate is also an explosive
iii.
Synthesis of nitric acid
2
f)^
Phosphoric Acid = H
is also Industrially Important 4
10
10
4
Ca
4
f)^
Liquid oxygen has a blue color due to absorption of light g)^
Diamagnetic, red, O
allotrope discovered 2006—unpaired O 8
e- form 2
bonding MO’s Excited states^ Ground state
S = yellow solid nonmetala)^
Known biblically as Brimstone b)^
Makes gunpowder with KNO
and charcoal 3
c)^
Many allotropes:
orthorhombic is most stable 8
d)^
Viscosity of solid varies unexpectedly with temperature e)^
Sulfuric Acid is the #1 Industrial Chemical (43.25 x 10
9 kg/yr in US)
i.^
Dense (d = 1.83 g/cm
3 ), viscous, colorless liquid that burns skin
ii.^
Exothermic reaction with water (chars sugar by removing H
iii.
Synthesis: S + O
2
or^
M^ x
S^ y^
----> ySO 2
Ox
y
3
4
S S
S
S
S S S S
ring----------->S
chain---->S 8
chain---->S 16
chain 24
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5)^
Polyatomic Ionsa)^
I^2
-^3 + other polyiodides
b)^
I^2
+^2
2+ 4
6)^
Interhalogens: multiple possibilities and ways to synthesize thema)^
Cl^2
----> 2 ClF 2
b)^
I^2
7)^
Pseudohalogens = dimeric compounds with properties similar to X
2
The Elements1)^
Discovery in 1766 by Cavendisha)^
Nonreactive, leftover fraction of air (after N
all reacted) 2
b)^
Not separated from each other
2)^
He discovered in 1868 by Locklear and Franklanda)^
New emission line observed during a solar eclipse b)^
Helios = Greek for “sun” c)^
Rare on Earth (Dexter, Kansas); used as NMR coolant (bp = 4.2 K) d)^
Second most abundant in Universe ( H = 76%, He = 23%)
3)^
Ar discovered in 1890 by Rayleigh and Ramsaya)^
density discrepancies must be accounted for by a contaminant
b)^
Argon = “no work” because does not react c)^
Used as chemically inert atmosphere, and for filling light bulbs
