Announcements:

Third Online Assessment is cancelled Office Hours this week: Friday 4-5 pm (PP 104) (or by appointment)

7. Green Inorganic Chemistry

Chem 281 Dr. Audrey H Moores

What is Mercury?

What on earth is Mercury?

Its YOUR way to express yourself! Please fill the questionnaire before April 16th.

I. Green Chemistry: introduction and definitions

5 Key elements of a chemical process

!! Applicable

From Last Class

!! !! !! !!

to science popularisation Reagents: what the company buys and puts in the process Products : what the company sells, what we buy The rest: catalysts, additives, solvents, energy Synthetic strategy
Products Catalysts Additives Solvents Energy

Reagents

I. Green Chemistry: introduction and definitions

From Last Class

What we will cover in this chapter

!! In !! !!

this class we will specifically talk about:

Energy
!!

Hydrogen use and storage Hydrogen chemistry

Food
Phosphorus peak !! Nitrogen chemistry
!!

!!

Chemical process
Transition metal catalysis (phosphorus chemistry) !! Metal free catalytic: hydrogenation (phosphorus and boron chemistry)
!!

!!

Materials
Chemistry of glass !! 2 guest lectures from Sam Sewall April 12th and 15th
!!

CHEM 281: Main group chemistry Silicon chemistry

SILICA CHEMISTRY
!! Silicon:

ID

!!

!!

Silicon is the second most abundant element of the earth crust. It is mostly present in the form of silicates (n cation m +,SiO -), e.g (Fe,Mg) SiO : olivine 4 2 4 29 Si NMR NMR active (spin of !), routinely used especially for silica containing materials

CHEM 281: Main group chemistry Silicon chemistry

SILICA CHEMISTRY
I H Li Na K Be Mg Ca B Al Ga C Si Ge N P As O S Se F Cl Br II XIII XIV XV XVI XVII XVIII Ne Ar Kr Xe

"! Silicon

is more electropositive and bigger than C "! Silicon is mostly tetravalent like C

CHEM 281: Main group chemistry Silicon chemistry

SILICA CHEMISTRY
!! SiO2 is
!! !!

the major form of silicon

Quartz: crystalline form of SiO2 Sand is mostly composed of small pieces of quartz

Hexagonal prismatic crystal lattice

http://www.espaceterreetmateriaux.be/verre_et_cristal.htm

CHEM 281: Main group chemistry Silicon chemistry

SILICA CHEMISTRY
!! SiO2 is
!!

the major form of silicon

Glass chemistry !! Pure silica "glass melting point: 2300 C !! Soda-lime glass: 1500 C (+ Na2CO3)

Def: Glass: ! Non crystalline material (glassy phase) ! Non crystalline silica (glass panel)

http://www.espaceterreetmateriaux.be/verre_et_cristal.htm

CHEM 281: Main group chemistry Silicon chemistry

SILICA CHEMISTRY
!! Float
!! !! !! !!

Glass Production

Raw materials melted (sand, Na2CO3, and additives) - 1500 C Viscous liquid poured onto a molten tin bath
!!

bath about 3-4 m wide, 50 m long, 6"cm deep

Glass is slid on the tin bath and goes through a gradient of temperature (from 1100 to 600 C) Glass annealing to easy tension in glass

http://en.wikipedia.org/wiki/Float_glass Corning Museum of Glass (Corning NY, USA)

CHEM 281: Main group chemistry Silicon chemistry

SILICA CHEMISTRY
!! Tension
!!

in Glass

Cooling of glass creates tensions inside the glass matrix. These comes from the inhomogeneity of the temperature in glass as it is cooling

!!

These tensions are visible using polarized light.

!!

E.g. glass and plastic objects both show tensions

Corning Museum of Glass (Corning NY, USA)

CHEM 281: Main group chemistry Silicon chemistry

SILICA CHEMISTRY
!! Tension
!!
!!

in Glass

Cooling causes tensions inside the matrix

when the glass breaks it does so in more pieces

!! !!

The same tensions causes a hardened surface After any glass fabrication process (float glass process, glass blowing process or molding): reheating (annealing) is performed to ease the tensions and afford a more robust glass

Corning Museum of Glass (Corning NY, USA)

CHEM 281: Main group chemistry Silicon chemistry

SILICA CHEMISTRY
!! Tempered
!! !!

Glass, Safety Glass

Tempered glass (St Gobain process) Hot glass (between 500 and 700 C) are subjected to air jets at room temperature: fast cooling. Tensions are trapped and the surface of glass is contracted. These tensions create a tougher glass 2 to 5 times tougher than ordinary glass), but also will make glass breaking into small piece when broken. These pieces will not cut the skin. Application: Public phones, side windows of cars, bus, trains

Corning Museum of Glass (Corning NY, USA)

CHEM 281: Main group chemistry Silicon chemistry

SILICA CHEMISTRY
!! Tempered
!! !!

Glass, Safety Glass

Safety glass May be tempered glass too. It is made of pieces of glass trapping a layer of polymer. Armored glass are made by multiple layers of this kind. Application: one layer, car windshields; multiple layers, armored glass for banks, armored cars, bullet proof vests

Tempered safety glass Non tempered safety glass Ordinary glass

CHEM 281: Main group chemistry Silicon chemistry

SILICA CHEMISTRY
!! Functionalization
!!

of glass surface

Fluoride chemistry: how to dissolve glass !! Glass has good chemical resistance apart from HF, F- can attack Si centers and form very strong Si-F bonds

HF is hazardous: it can dissolve your bones too!

CHEM 281: Main group chemistry Silicon chemistry

SILICA CHEMISTRY
!! SiO2 is
!!

the major form of silicon

Glass chemistry !! Hydrophilicity of glass !! Fabrication of hydrophobic glass

Hydrophilic

Hydrophobic

CHEM 281: Main group chemistry Silicon chemistry

SILICA IN NATURE
!! SiO2 in
!!

diatoms algeas

Diatomeous earth, fossilised diatoms, are used for filtration (celite)

CHEM 281: Main group chemistry Silicon chemistry

SILICA IN NATURE
!! Diatoms !! !! !!

applications

Sensing Catalysis Remediation

!!

E.g. Sugar ribose sensing: The biosensor, described in a paper published this week in the scientific journal PLoS ONE, includes fluorescent proteins embedded in a diatom shell that alter their glow when they are exposed to a particular substance.

http://www.sciencedaily.com/releases/2012/03/120323094036.htm

CHEM 281: Main group chemistry Silicon chemistry

SILICA CHEMISTRY
!! Mesoporous !!

structures - array of pores with sizes between 1 and 10 nm

Used in catalysis, sensing
! Polymer precursor (Si (OEt)4) ! Solvent (EtOH/H2O) ! Soap = surfactant

CHEM 281: Main group chemistry Silicon chemistry

SILICA CHEMISTRY
!! Mesoporous !!

structures - array of pores with sizes between 1 and 10 nm

Used in catalysis, sensing

CHEM 281: Main group chemistry Silicon chemistry

SILICA CHEMISTRY
!! Mesoporous !!

structures - array of pores with sizes between 1 and 10 nm

Used in catalysis, sensing

CHEM 281: Main group chemistry Silicon chemistry

ELEMENTAL SILICON
!! Semi

conducting properties silicon is a key element to the fabrication of transistors !! Silicon technology: highly pure monocrystalline Si wafers
!!

more on semi-conductors Friday with Dr. Sewall!

ORGANOSILICON COMPOUNDS
!! Organic

compounds containing Si-C bonds !! Si-C polarized towards C !! Si mostly tetravalent, tetrahedral

Silole

Brook Silenes Adrian Brook - UofT

Poly(dimethylsiloxane) PDMS

23

ORGANOSILICON COMPOUNDS
!! Silicones

vs.

!! Reactivity !!

of Si-Cl

reactive bond, forms Si-OH with water

24

CHEM 281: Main group chemistry silicon chemistry

ORGANOSILICON COMPOUNDS
!! Silicon

!! !! !!

Enantiomers of Si can not be vs. Carbon conserved in the presence of Lewis base solvents (water, THF) Berry pseudorotaion Occurs because Si can be hypervalent And bipyramidal structures are more flexible

CHEM 281: Main group chemistry silicon chemistry

SILICON IN ORGANIC SYNTHESIS

!! Alcohol

!!

Protection In organic transformations, it is desirable to protect alcohols - preventing their reactivity as proton provider.

!!

Deprotection: acid catalysed methanolysis

CHEM 281: Main group chemistry silicon chemistry

SILICON IN ORGANIC SYNTHESIS

!! Applications
!!

of silicon in organic chemistry

For further reading:

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