First Lesson

Fluorinated Material Fluorinated Material

Fluoropolymer’s MarketFluoropolymer’s Market

Size (tons)

Turnover ($ billion)

EVA

Polyethylene 2 107 28.5

Fluoropolymers 1 105 2.3

PE/Fluoropol. 100:1 10:1 1:1

Fluoropolymers are specialty polymers:

small volumes – high revenues – high technological content

Integration of Fluorine Chemistry

HF

F2

Organic Intermediates

Fluorocarbons Base Monomers

Melts

Elastomers

Fluids

FLUOROCHEMICALS

Fluorspar

Chloro-feedstocks

FLUOROMATERIALS

Special Gases

PTFE

Special Monomers

Atomic RadiusIncreases

Au

men

ta

ElectronegativityIncreases

Decre

ases

Electron affinity Aumenta

Dim

inu

isce

Ionization EnergyAumenta

Dim

inu

isce

Fluoro   9F

18.9984032 Nome: fluoro Simbolo: F Numero atomico: 9 Peso Atomico : 18.998 CAS Registry ID: 7782-41-4 Gruppo : 7 Gruppo : Halogen Periodo : 2 Block: p-block1s2 2(s2p5)

Description   Standard state: gas at 298 K (m.p. -223oC,     b.p. -188oC)

Colour: pale yellow Classification: Non-metallic Availability : 0.08% by mass of Earth's crust

 .  

Cloro 17Cl

35.453 Name: chlorine Symbol: Cl Atomic number: 17 Atomic weight: 35.453 CAS Registry ID: 7782-50-5 Group number: 7 Group name: Halogen Period number: 3 Block: p-block 1s2 2(s2p6) 3(s2p5)

Description 

Standard state: gas at 298 K  (m.p. -102.4oC,    b.p. -34.0oC)

Colour: yellowish green

Classification: Non-metallic

Availability : 0.05% by mass of Earth's crust.

External electronic configuration  

n(s2p5) 

 Obey the octet rule

acquiring an electron transfer from or to factors of a metal (eg Na + Cl) or for the formation of a covalent bond with the non-metallic elements (eg, CCl4).

Strong oxidizers

Oxidation states -1.0, +1, +3, +5, +7.Remarkable range of redox reactions in aqueous media.

Anions are easily formed, but not cations (eg with the exception of iodine. I + ClO4-)

H B C N O F

-73 -27 -122 -7 -141 -328

      800 780  

      1290    

      P S Cl

      -2 -200 -349

        590  

        Se Br

        -195 -325

        420  

        Te I

        -190 -295

(Electron Affinities) Table of Electron Gain Enthalpies (kJ mol-l)

 

X-n(g) + e- X -(n+1) (g)

Raggi atomici degli alogeni e dei relativi anioni

F + Na F- + Na+

Homopolar Single Bonds Table of X-X bond energies (kJ mol-1)

 

H-H 436

B-B 308 C-C 347 N-N 158 O-O 144 F-F 158

-  - Si-Si 226 P-P 198 S-S 266 Cl-Cl 243

Ga-Ga 113 Ge-Ge 188 As-As 178 Se-Se 192 Br-Br 193

In-In 100 Sn-Sn 146 Sb-Sb 141 Te-Te 126 I-I 151

H-H strongest; no core electron repulsion  Down group IV(14), bond strength goes down

 overlap goes down and non-bonded repulsion goes up 

 C-C > N-N > O-O, F-F 

F-F << Cl-Cl non-bonded electron and core replusion important

Table of bond energies (kJ mol-1)Element-Hydrogen Bonds

B-H -389 C-H 411 N-H 386 O-H 456 F-H 565

    Si-H 318 P-H 321 S-H 364 Cl-H 432

    Ge-H 285 As-H 297 Se-H 313 Br-H 366

        Sb-H 257 Te-H -270 I-H 298

Across period, B(E-H) increases, no core electron repulsion,so overlap can increase as covalent radius can be small

 Down group, B(E-H) decreases, as overlap decreases,

as energy match condition is worse