X-RAYS: ORIGIN AND INTERPRETATION

1. Formation of X-rays: High-energy electron beam is directed onto a target containing elements with relatively high atomic number (e.g. transition metals).

X-RAYS: ORIGIN AND INTERPRETATION

2. Energy distribution: continuous deceleration K discrete (lines) characteristic K... L L

3. Laws describing different series: Lines of the same type for different elements vary systematically with increasing atomic number

Moseley law (1913)

Henry Moseley (1887-1915) X-ray fluorescence Lines are characteristic of elements

X-ray fluroescence

f = k 1 (Z k 2 )
f: frequency of line k1, k2: constants depending on line type Z: atomic number K lines

Analysis for elemental composition

f (Hz ) = 2,48 1015 (Z 1)2

Introduction of the concept Atomic Number Systematic research for missing elements

APPLICATIONS OF X-RAYS
Imaging: Different atoms absorb Xrays differently, elements with high atomic numbers absorb strongly (eg. Ca > C) contrast agents: BaSO4 vagy organoiodine compounds X-ray diffraction: molecule structure determination (X-ray) ~ internuclear distance in molecules Biological effect: E(X-ray) > E(outer electrons) Tissue damage, ionization, sterilization,...

X-ray diffraction determination of crystal and molecule structure Bragg equation:

d=

n 2 sin

X-ray diffraction

CHEMICAL BONDING
1. Primary chemical bonding forces (E > 100 kJ/mol) a/ Ionic bonding (Kossel 1916) x > 2 occurence: ionic solids b/ Covalent bonding (Lewis 1916) x < 0,5 occurence: - molecules - covalent network solids c/ Metallic bonding x ~ 0 occurence: metallic solids 2. Secondary chemical bonding forces (E < 100 kJ/mol) - disspersion forces - dipoledipole (induced dipole) interaction - hydrogen bonding X-ray diffraction

IONIC BONDS AND IONIC SOLIDS

An electron affinity never provides enough energy to compensate for an ionization energy. M (g) M+ (g) + e X(g) + e X (g) No matter what M and X are Ei(M) > Eea(X) Ei(M) + Eea(X) > 0 endothermic Ions cannot form in exothermic processes??? Ei(M) Eea(X)

IONIC BONDS AND IONIC SOLIDS

2Al + 3Br2 2AlBr3 2Na + Cl2 2NaCl extremely exothermic highly exothermic

Electron affinities and ionization energies are gasphase properties. Ions are unlikely to form in gas phase at not very high temperatures!!! Ionic compounds: solids (sometimes liquids) in a well-ordered crystal structure Crystal lattice: held together by large forces

NO!!!!!

LATTICE ENERGY MX (s) M+ (g) + X (g)

U, kJ/mol

LATTICE ENERGY
charges Origin: interaction between charges, Coulomb's law (for force)

the energy required to break up an ionic solid into individual gaseous ions always high positive value e.g. LiF 1036 kJ/mol, CaO 3401 kJ/mol Depends on: lattice geometry (distance and number of close neighbor ions) charge of ions in the lattice

F =k

z1z2 d2
distance

Coulomb's constant Like charges: repulsion Unlike charges: attraction for energy

E=k

z1z2 d

Like charges: positive energy (high) Unlike charges: negative energy (low)

need to be summed for every possible pairs of ions in a lattice

LATTICE ENERGY (U)

The energy released during the formation of 1 mol ionic solid from 1 mol gaseous ions. Calculation:

Born-Haber cycle for NaCl

Na+ (g) + e + Cl (g) electron affinity ionization Na+ (g) + Cl (g) Na (g) + Cl (g) bond dissociation vaporization Na (g) + Cl2 (g) Na (s) + Cl2 (g) -lattice energy

U = Mk

M: Madelung constant (depends on lattice type) zi: ionic charge r: distance between ions

z1z2 d

M = ()i
for NaCl:

M=

i , j ,k =

d0 d (1)i + j + k
2 2

net chemical reaction

2

i + j +k

M = 6 + 12 / 2 8 / 3 + 6 / 2 24 / 5 + ...... = 1.74756

NaCl (s)

Structure of NaCl Na+ and Cl ions in lattice points every Na+ has 6 Cl as closest neighbors in octahedral geometry ClClClNa+ ClClClevery Cl has 6 Na+ as closest neighbors in octahedral geometry Na+

ball & stick

Na+
+

Na

ClNa+

Na+

Na+

spacefill

sticks

wireframe

Sodium Chloride

Common salt (NaCl)

known and used for millenia very important commercial material the human body needs ~ 5 g a day crystalline common salt: HALITE two sources: salt in seas and oceans (evaporation) salt in mines: left from ancient seas Salt production by evaporation: SALT PAN e.g. Seovlje (Slovenia)

Salt production by mining: SALT MINES e.g. Wieliczka (Poland)

Lattice energies (kJ/mol) Structure of CsCl Cs+ and Cl ions in lattice points every Cs+ has 8 Cl as closest neighbors in cubic geometry

F Li+ Na+ K+ Be2+ Mg2+ Ca2+ Al3+ 1036 923 821 3505 2957 2630 5215
z1z2 d

Cl 853 787 715 3020 2524 2258 5492

Br 807 747 682 2914 2440 2176 5361

I 757 704 649 2800 2327 2074

O2 2925 2695 2360 4443 3791 3401

ClCl- Cl+ Cl Cs ClCl- Cl Cl-

Cl- ClCl- Cl-- + Cs Cl Cl ClCl-

every Cl has 8 Cs+ as closest neighbors in cubic geometry

5218 15916

reminder E = k

Octet rule
A simple rule (not law) useful for interpreting and predicting electronic structure of main group elements in compounds: Main-group elements tend to undergo reactions that leave them with eight outer-shell electrons. or Main group elements react so that they attain a noble gas electron configuration with filled s and p sublevels in their valence electron shell.

Octet rule
Alkali metals tend to lose their ns1 valence-shell electron, thereby adopting the electron configuration of the noble gas element in the previous row of the periodic table. Alkali earth metals tend to lose both of their ns2 valenceshell electrons and adopt a noble gas configuration. Boron group elements tend to lose all three of their ns2np1 electrons and adopt a noble gas configuration. Halogens tend to gain one electron, changing from ns2np5 to ns2np6, thereby adopting the configuration of the neighboring noble gas element in the same row. Noble gas elements are essentially inert; they rarely gain or lose electrons. More consequences in covalent bonding..........

CRYSTAL STRUCTURES UNIT CELL PARAMETERS

CRYSTAL SYSTEM: TRICLINIC

abc

REMINDER !! unit cell: the smallest repeating unit of a crystalline solid from which the whole lattice can be constructed

Only seven different classes of unit cells are possible

CRYSTAL SYSTEM: MONOCLINIC

abc

CRYSTAL SYSTEM: ORTHORHOMBIC

abc

= = = 90

= = 90

simple

base-centered

simple

base-centered body-centered face-centered

CRYSTAL SYSTEM: TETRAGONAL

a=bc

CRYSTAL SYSTEM: TRIGONAL

a=b=c

= = = 90

= = 90

simple

body-centered

simple

CRYSTAL SYSTEM: HEXAGONAL

a=bc

CRYSTAL SYSTEM: CUBIC

a=b=c

= = 90 = 120

= = = 90

simple

body-centered

simple

face-centered