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Lecture 2 (9/11/2006) Lecture 2 (9/11/2006)

Crystal ChemistryCrystal Chemistry

Part 1:Part 1:

Atoms, Elements, andAtoms, Elements, and

IonsIons

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Mineralogy WebsiteMineralogy Website

www.d.umn.edu/~mille066/Teaching/Mineralogy06.htwww.d.umn.edu/~mille066/Teaching/Mineralogy06.ht

mm

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What is Crystal Chemistry?What is Crystal Chemistry?

study of the atomic structure, physicalstudy of the atomic structure, physical

properties, and chemical composition ofproperties, and chemical composition of

crystalline materialcrystalline material basically inorganic chemistry of solidsbasically inorganic chemistry of solids

the structure and chemical properties ofthe structure and chemical properties of

the atom and elements are at the core ofthe atom and elements are at the core of

crystal chemistrycrystal chemistry

there are only a handful of elements thatthere are only a handful of elements that

make up most of the rock-forming mineralsmake up most of the rock-forming minerals

of the earthof the earth

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Fe 86%Fe 86%

S 10%S 10%

Ni 4%Ni 4%

Chemical Layers of the EarthChemical Layers of the Earth

SiO2 45%SiO2 45%

MgO 37%MgO 37%

FeO 8%FeO 8%

Al2O3 4%Al2O3 4%

CaO 3%CaO 3%

others 3%others 3%

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Composition of the Earths CrustComposition of the Earths Crust

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Average composition of the EarthsAverage composition of the Earths

CrustCrust

(by weight, elements, and volume)(by weight, elements, and volume)

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The AtomThe Atom

The Bohr Model The Schrodinger Model

Nucleus

- contains most of the weight (mass) of the atom- composed of positively charge particles (protons) andneutrally charged particles (neutrons)Electron Shell

- insignificant mass- occupies space around the nucleus defining atomic

radius- controls chemical bonding behavior of atoms

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Elements and IsotopesElements and Isotopes

Elements are defined by the number of protons inElements are defined by the number of protons inthe nucleus (atomic number).the nucleus (atomic number).

In a stable element (non-ionized), the number ofIn a stable element (non-ionized), the number of

electrons is equal to the number of protonselectrons is equal to the number of protons Isotopes of a particular element are defined by theIsotopes of a particular element are defined by the

total number of neutrons in addition to the numbertotal number of neutrons in addition to the numberof protons in the nucleus (isotopic number).of protons in the nucleus (isotopic number).

Various elements can have multiple (2-38) stableVarious elements can have multiple (2-38) stableisotopes, some of which are unstable (radioactive)isotopes, some of which are unstable (radioactive) Isotopes of a particular element have the sameIsotopes of a particular element have the same

chemical properties, but different masses.chemical properties, but different masses.

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Isotopes of Titanium (Z=22)Isotope Half-life SpinParity DecayMode(s) or Abundance38Ti 0+39Ti 26 ms (3/2+) EC=100, ECP+EC2P ~ 1440Ti 50 ms 0+ EC+B+=100

41Ti 80 ms 3/2+ EC+B+=100, ECP ~ 10042Ti 199 ms 0+ EC+B+=10043Ti 509 ms 7/2- EC+B+=10044Ti 63 y 0+ EC=10045Ti 184.8 m 7/2- EC+B+=10046Ti stable 0+ Abundance=8.0 147Ti stable 5/2- Abundance=7.3 1

48Ti stable 0+ Abundance=73.8 149Ti stable 7/2- Abundance=5.5 150Ti stable 0+ Abundance=5.4 151Ti 5.76 m 3/2- B-=10052Ti 1.7 m 0+ B-=10053Ti 32.7 s (3/2)- B-=10054Ti 0+55Ti 320 ms (3/2-) B-=10056Ti 160 ms 0+ B-=100, B-N=0.06 sys57Ti 180 ms (5/2-) B-=100, B-N=0.04 sys58Ti 0+59Ti (5/2-) B-=?60Ti 0+ B-=?

61Ti (1/2-) B-=?, B-N=? Source: R.B.Firestone

http://ie.lbl.gov/education/glossary/glossaryf.htm?Isotopehttp://ie.lbl.gov/education/glossary/glossaryf.htm?HalfLifehttp://ie.lbl.gov/education/glossary/glossaryf.htm?Spinhttp://ie.lbl.gov/education/glossary/glossaryf.htm?Parityhttp://ie.lbl.gov/education/glossary/glossaryf.htm?Decayhttp://ie.lbl.gov/education/glossary/glossaryf.htm?Decayhttp://ie.lbl.gov/education/glossary/glossaryf.htm?Decayhttp://ie.lbl.gov/education/glossary/glossaryf.htm?Abundancehttp://ie.lbl.gov/toi/nuclide.asp?iZA=220038http://ie.lbl.gov/toi/nuclide.asp?iZA=220039http://ie.lbl.gov/toi/nuclide.asp?iZA=220040http://ie.lbl.gov/toi/nuclide.asp?iZA=220041http://ie.lbl.gov/toi/nuclide.asp?iZA=220042http://ie.lbl.gov/toi/nuclide.asp?iZA=220043http://ie.lbl.gov/toi/nuclide.asp?iZA=220044http://ie.lbl.gov/toi/nuclide.asp?iZA=220045http://ie.lbl.gov/toi/nuclide.asp?iZA=220046http://ie.lbl.gov/toi/nuclide.asp?iZA=220047http://ie.lbl.gov/toi/nuclide.asp?iZA=220048http://ie.lbl.gov/toi/nuclide.asp?iZA=220049http://ie.lbl.gov/toi/nuclide.asp?iZA=220050http://ie.lbl.gov/toi/nuclide.asp?iZA=220051http://ie.lbl.gov/toi/nuclide.asp?iZA=220052http://ie.lbl.gov/toi/nuclide.asp?iZA=220053http://ie.lbl.gov/toi/nuclide.asp?iZA=220053http://ie.lbl.gov/toi/nuclide.asp?iZA=220052http://ie.lbl.gov/toi/nuclide.asp?iZA=220051http://ie.lbl.gov/toi/nuclide.asp?iZA=220050http://ie.lbl.gov/toi/nuclide.asp?iZA=220049http://ie.lbl.gov/toi/nuclide.asp?iZA=220048http://ie.lbl.gov/toi/nuclide.asp?iZA=220047http://ie.lbl.gov/toi/nuclide.asp?iZA=220046http://ie.lbl.gov/toi/nuclide.asp?iZA=220045http://ie.lbl.gov/toi/nuclide.asp?iZA=220044http://ie.lbl.gov/toi/nuclide.asp?iZA=220043http://ie.lbl.gov/toi/nuclide.asp?iZA=220042http://ie.lbl.gov/toi/nuclide.asp?iZA=220041http://ie.lbl.gov/toi/nuclide.asp?iZA=220040http://ie.lbl.gov/toi/nuclide.asp?iZA=220039http://ie.lbl.gov/toi/nuclide.asp?iZA=220038http://ie.lbl.gov/education/glossary/glossaryf.htm?Abundancehttp://ie.lbl.gov/education/glossary/glossaryf.htm?Decayhttp://ie.lbl.gov/education/glossary/glossaryf.htm?Decayhttp://ie.lbl.gov/education/glossary/glossaryf.htm?Decayhttp://ie.lbl.gov/education/glossary/glossaryf.htm?Parityhttp://ie.lbl.gov/education/glossary/glossaryf.htm?Spinhttp://ie.lbl.gov/education/glossary/glossaryf.htm?HalfLifehttp://ie.lbl.gov/education/glossary/glossaryf.htm?Isotope

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Properties of ElectronsProperties of Electrons

Occur in discrete (quantized) energy levels orOccur in discrete (quantized) energy levels ororbitals around the nucleusorbitals around the nucleus

Behave as particles with wave-like propertiesBehave as particles with wave-like properties Position of an electron in space around the nucleusPosition of an electron in space around the nucleus

is a probability function defined by 4 quantumis a probability function defined by 4 quantumnumbersnumbers

nn principle quantum number (= 1, 2, 3, 4...) principle quantum number (= 1, 2, 3, 4...)

defines the energy level of the primary electron shelldefines the energy level of the primary electron shell

ll azimuthal quantum number (= azimuthal quantum number (= nn -1)-1)

defines the type and number of electron subshells (s, p,defines the type and number of electron subshells (s, p,d, f, ...)d, f, ...)

mm magnetic quantum number (= + magnetic quantum number (= +ll to -to -ll ))

defines orientation and number of orbitals in eachdefines orientation and number of orbitals in eachsubshellsubshell

ss spin quantum number (= +1/2 or -1/2) spin quantum number (= +1/2 or -1/2)

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Electron Shells, Subshells, andElectron Shells, Subshells, and

OrbitalsOrbitals

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Filling up theFilling up the

OrbitalsOrbitals

Controlled by theenergy of the orbitals

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Structure of the Periodic TableStructure of the Periodic Table

# of Electrons in Outermost Shell NobleGases

Anions

--------------------TransitionMetals------------------

Primary Shell being filled

i i i l d lI I i ti P t ti l d V l

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Ions, Ionization Potential, and ValenceIons, Ionization Potential, and Valence

StatesStatesCationsCations elements prone to give up one or more elements prone to give up one or more

electrons from their outer shells; typically a metalelectrons from their outer shells; typically a metalelementelement

AnionsAnions elements prone to accept one or more elements prone to accept one or moreelectrons to their outer shells; always a non-metalelectrons to their outer shells; always a non-metal

elementelement

Ionization PotentialIonization Potential measure of the energy measure of the energynecessary to strip an element of its outermostnecessary to strip an element of its outermostelectronelectron

ElectronegativityElectronegativity measure strength with which a measure strength with which anucleus attracts electrons to its outer shellnucleus attracts electrons to its outer shell

Valence StateValence State (or oxidation state) the common(or oxidation state) the common

ionic configuration(s) of a particular elementionic configuration(s) of a particular elementdetermined b how man electrons are t icalldetermined b how man electrons are t icall

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1st Ionization Potential

Electronegativity

Elements with a singleouter s orbital electron

Anions

Cations

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Valence States of Ions commonValence States of Ions common

to Rock-forming Mineralsto Rock-forming MineralsCationsCations generallygenerallyrelates torelates tocolumn in thecolumn in theperiodic table;periodic table;

mostmost transitiontransitionmetalsmetals have ahave a+2 valence+2 valencestate forstate fortransitiontransitionmetals, relatesmetals, relatesto having twoto having two

electrons inelectrons inouterouter

AnionsAnions relates relateselectronselectronsneeded toneeded tocompletely fillcompletely fill

outer shellouter shellAnionic Groups Anionic Groups

+1 +2+3 +4 +5 +6 +7

-2 -1

-----------------TransitionMetals---------------

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Next LectureNext Lecture

Crystal Chemistry IICrystal Chemistry II

BondingBonding

Atomic and Ionic RadiiAtomic and Ionic Radii

Read p. 56-69Read p. 56-69