Welcome to 3.091Lecture 8

September 25, 2009

Ionic Crystals; Born-Haber Cycle

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Properties of Ionic Crystals

high melting points & boiling points solid at room temperature

transparent to visible light electrical insulators hard & brittle

soluble in water & other polar solvents melt to form ionic liquids (useful in electrolytic extraction of metals)

where to search for ionicity???

1.00794-259.34-252.870.08992.2013.5981s1

Hydrogen

6.941180.513420.5340.985.392[He]2s1

Lithium

9.012182128724711.84771.579.322[He]2s2

Beryllium

22.98976897.728830.970.935.139[Ne]3s1

Sodium

24.305065010901.741.317.646[Ne]3s2

Magnesium

39.098363.387590.860.824.341[Ar]4s1

Potassium

88.90585152633364.4691.226.38[Kr]4d15s2

Yttrium

87.6277713822.60.955.695[Kr]5s2

Strontium

85.467839.316881.5320.824.177[Kr]5s1

Rubidium

138.905592034556.1461.105.577[Xe]5d16s2

Lanthanum

178.492233460313.311.37.0[Xe]4f145d26s2

Hafnium

180.94793017545816.61.57.89[Xe]4f145d36s2

Tantalum

183.843422555519.352.367.98[Xe]4f145d46s2

Tungsten

186.2073186559620.51.97.88[Xe]4f145d56s2

Rhenium

190.233033501222.612.28.7[Xe]4f145d66s2

Osmium

192.222446442822.652.209.1[Xe]4f145d76s2

Iridium

195.081768.4382521.452.289.0[Xe]4f145d96s1

Platinum

196.966541064.18285619.312.549.225[Xe]4f145d106s1

Gold

200.59-38.83356.7313.5462.0010.437[Xe]4f145d106s2

Mercury

204.3833304147311.852.046.108[Xe]4f145d106s2p1

Thallium

207.2327.46174911.342.337.416[Xe]4f145d106s2p2

Lead

208.98037271.4015649.782.027.289[Xe]4f145d106s2p3

Bismuth

(208.9824)2549629.1962.08.42[Xe]4f145d106s2p4

Polonium

(209.9871)302337-2.2-[Xe]4f145d106s2p5

Astatine

(222.0176)-71-61.79.73-10.748[Xe]4f145d106s2p6

Radon

137.32772718973.5940.895.212[Xe]6s2

Barium

132.9054328.446711.8790.793.894[Xe]6s1

Cesium

(226.0254)700<11405.80.95.279[Rn]7s2

Radium

(227.0278)1051319810.071.16.9[Rn]6d17s2

Actinium

140.11579934246.7701.125.466[Xe]4f15d16s2

Cerium

140.9076593135106.7731.135.422[Xe]4f36s2

Praseodymium

144.24101630667.001.145.489[Xe]4f46s2

Neodymium

(144.9127)104230007.2541.135.554[Xe]4f56s2

Promethium

150.36107217907.5361.175.631[Xe]4f56s2

Samarium

151.96582215965.2441.25.666[Xe]4f76s2

Europium

157.25131432647.9011.206.141[Xe]4f75d16s2

Gadolinium

158.92534135932218.2301.25.842[Xe]4f96s2

Terbium

162.50141125618.5511.225.927[Xe]4f106s2

Dysprosium

164.93032147226948.801.236.018[Xe]4f116s2

Holmium

167.26152928629.0661.246.101[Xe]4f126s2

Erbium

168.93421154519469.3211.256.18436[Xe]4f136s2

Thulium

173.0482411946.9661.16.25394[Xe]4f146s2

Ytterbium

174.967166333939.841.275.42589[Xe]4f145d16s2

Lutetium

232.03811750478811.721.36.08[Rn]6d27s2

Thorium

231.035881572-15.371.55.89[Rn]5f26d17s2

Protactinium

238.02891135413119.05+0.021.386.05[Rn]5f36d17s2

Uranium

(237.0482)644-20.451.366.19[Rn]5f46d17s2

Neptunium

(244.0642)640322819.8161.285.8[Rn]5f67s2

Plutonium

(243.0614)1176250713.671.35.993[Rn]5f77s2

Americium

(247.0703)1345-13.511.36.02[Rn]5f76d17s2

Curium

(247.0703)1050-14.781.36.23[Rn]5f97s2

Berkelium

(251.0796)900--1.36.30[Rn]5f107s2

Californium

(252.083)860--1.36.42[Rn]5f117s2

Einsteinium

(257.0951)1527--1.36.50[Rn]5f127s2

Fermium

(258.10)827--1.36.58[Rn]5f137s2

Mendelevium

(259.1009)827--1.36.65[Rn]5f147s2

Nobelium

(252.11)1627----[Rn]5f146d17s2

Lawrencium

(261)-----[Rn]5f146d27s2

Rutherfordium**

(262)-----[Rn]5f146d37s2

Dubnium**

(263)-----[Rn]5f146d47s2

Seaborgium**

(262)-----[Rn]5f146d57s2

Bohrium**

(265)-----[Rn]5f146d57s2

Hassium**

(266)-----[Rn]5f146d77s2

Meitnerium**

(272)-----[Rn]5f146d107s1

Unununium

(277)-----[Rn]5f146d107s2

Ununbium

(285)-----[Rn]5f146d107s27p2

Ununquadium

(289)-----[Rn]5f146d107s27p4

Ununhexium

(293)-----[Rn]5f146d107s27p6

Ununoctium

-----

Ununpentium

-----

Ununseptium

-----

Ununtrium

(223.0197)27677-0.7-[Rn]7s1

Francium

40.07884214841.541.006.113[Ar]4s2

Calcium

44.955910154128302.9891.366.54[Ar]3d14s2

Scandium

47.8816 832874.51.546.82[Ar]3d24s2

Titanium

91.224185544096.491.336.84[Kr]4d25s2

Zirconium

92.90638247747448.571.66.9[Kr]4d45s1

Niobium

50.9415191034075.961.636.74[Ar]3d34s2

Vanadium

95.942623463910.22.167.099[Kr]4d55s1

Molybdenum

51.9961190726717.201.666.766[Ar]3d54s1

Chromium

54.93805124620617.471.557.435[Ar]3d54s2

Manganese

55.847153828617.861.837.870[Ar]3d64s2

Iron

58.93320149529278.921.887.86[Ar]3d74s2

Cobalt

58.6934145529138.901.917.635[Ar]3d84s2

Nickel

63.5461084.6225628.941.907.726[Ar]3d104s1

Copper

65.39419.539077.1425%

1.659.394[Ar]3d104s2

Zinc

69.72329.7622046.0951.815.999[Ar]3d104s2p1

Gallium

10.811207540002.312.048.298[He]2s2p1

Boron

12.0114492TP

3825SP

2.252.5511.260[He]2s2p2

Carbon

72.61938.2528335.352.017.899[Ar]3d104s2p2

Germanium

74.92159817TP

614SP

5.72725oC

2.189.81[Ar]3d104s2p3

Arsenic

78.962216854.812.559.752[Ar]3d104s2p4

Selenium

79.904-7.258.63.1192.9611.814[Ar]3d104s2p3

Bromine

83.80-157.36-153.223.74-13.999[Ar]3d104s2p5

Krypton

107.8582961.78216210.51.937.576[Kr]4d105s1

Silver

112.411321.077678.6421.698.993[Kr]4d105s2

Cadmium

114.818156.6020727.301.785.786[Kr]4d105s2p1

Indium

118.710231.9326027.281.967.344[Kr]4d105s2p2

Tin

121.757630.6315876.68425oC

2.058.641[Kr]4d105s2p3

Antimony

127.60449.519886.252.19.009[Kr]4d105s2p4

Tellurium

126.90447113.7184.44.932.6610.451[Kr]4d105s2p5

Iodine

131.29-111.75-108.045.89-12.130[Kr]4d105s2p6

Xenon

106.421554.9296312.022.208.34[Kr]4d10

Palladium

101.072334415012.32.27.37[Kr]4d75s1

Ruthenium

102.905501964369512.42.287.46[Kr]4d85s1

Rhodium

(97.9072)2157426511.51.97.28[Kr]4d55s2

Technetium

1

H1

3

Li1

11

Na1

19

K1

37

Rb1

55

Cs1

56

Ba2

57

La3

72

Hf4

73

Ta5

58

Ce3,4

59

Pr3,4

60

Nd3

61

Pm3

62

Sm2,3

63

Eu2,3

64

Gd3

65

Tb3,4

66

Dy3

67

Ho3

68

Er3

69

Tm2,3

70

Yb2,3

71

Lu3

103

Lr3

102

No2,3

101

Md2,3

100

Fm3

99

Es3

98

Cf3

97

Bk3,4

96

Cm3

95

Am3,4,5,6

94

Pu3,4,5,6

93

Np3,4,5,6

92

U3,4,5,6

91

Pa4,5

90

Th4

74

W2,3,4,5,6

75

Re-1,2,4,6,7

76

Os2,3,4,6,8

77

Ir2,3,4,6

78

Pt2,4

79

Au1,3

80

Hg1,2

81

Tl1,3

82

Pb2,4

83

Bi3,5

84

Po2,4

86

Rn118

Uuo-

117

Uus-

116

Uuh-

115

Uup-

114

Uuq-

113

Uut-

112

Uub-

111

Uuu-

109

Mt-

108

Hs-

107

Bh-

106

Sg-

105

Db-

104

Rf4

89

Ac3

88

Ra2

87

Fr1

(269)-----[Rn]5f146d97s1

Ununnilium

110

Uun-

38

Sr2

39

Y3

40

Zr4

41

Nb3,5

42

Mo2,3,4,5,6

43

Tc7

44

Ru2,3,4,6,8

45

Rh2,3,4

46

Pd2,4

47

Ag1

48

Cd2

49

In3

50

Sn2,4

51

Sb52

Te-2,4,6

53

I1,5,7

54

Xe

20

Ca2

21

Sc3

22

Ti3,4

23

V2,3,4,5

24

Cr2,3,6

25

Mn2,3,4,6,7

26

Fe2,3

27

Co2,3

28

Ni2,3

29

Cu1,2

30

Zn2

31

Ga3

5

B3

26.981539660.3225192.7021.615.986[Ne]3s2p1

Aluminum

13

Al3

28.0855141432652.331.908.151[Ne]3s2p2

Silicon

14

Si4

39.948-189.35-185.851.784-15.759[Ne]3s2p6

Argon

18

Ar

15.9994-218.79-182.951.4293.4413.618[He]2s2p4

Oxygen

8

O-2

18.9984032-219.62-188.121.693.9617.422[He]2s2p5

Fluorine

9

F-1

20.1797-248.59-246.080.9002-21.564[He]2s2p6

Neon

10

Ne

4,002602-272.226 atm

-268.930.1785-24.5871s2

Helium

2

He

32

Ge4

34

Se-2,4,6

36

Kr33

As3,5-

3,5-

6

C2, 4-

14.00674-210.00-195.791.250463.0414.534[He]2s2p3

Nitrogen

7

N2, 3,4,5-

30.97376244.152771.822.1910.486[Ne]3s2p3

Phosphorus

15

P 3,4,5-

32.066115.21444.602.072.5810.360[Ne]3s2p4

Sulfur

16

S 2,4,6-

35.4527-101.5-34.043.2143.1612.967[Ne]3s2p5

Chlorine

17

Cl 1,3,5,7-

85

At 1,3,5,7-

35

Br1,5-

-

12

Mg2

4

Be2

**

*

*

**

2IIAIIA

3IIIAIIIB

4IVAIVB

5VAVB

6VIAVIB

7VIIAVIIB

8VIIIAVIII

9VIIIAVIII

10VIIIAVIII

11IBIB

12IIBIIB

13IIIBIIIA

14IVBIVA

15VBVA

16VIBVIA

17VIIBVIIA

18VIII

0

1IAIA

Image by MIT OpenCourseWare.

11AH+

Li+

Na+

K+

Rb+

Cs+ Ba2+

Sr2+

Ca2+

Mg2+

Be2+

Al3+

Ga3+

In3+

Tl+

Tl3+ Pb4+

Pb2+

Sn4+

Sn2+

N3- O2-

S2-

Se2-

Te2- I-

Br-

Cl-

F-

H-

Hydride

Nitride Oxide

Sulfide

Selenide

Telluride Iodide

Bromide

Chloride

Fluoride

22A

133A

144A

155A

166A

177A

188A

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Max Born - BiographyMax Born - Biography

Max Born was born in Breslau on the 11th December, 1882, toProfessor Gustav Born, anatomist and embryologist, and his wifeMargarete, nee Kauffmann, who was a member of a Silesian familyof industrialists.

Max attended the Konig Wilhelm's Gymnasium in Breslau andcontinued his studies at the Universities of Breslau (where thewell-known mathematician Rosanes introduced him to matrixcalculus), Heidelber, Zurich (here he was deeply impressed byHurwitz's lectures on higher analysis), and Gottingen. In the latterseat of learning he read mathematics chiefly, sitting under Klein,Hilbert, Minkowski, and Runge, but also studied astronomy underSchwarzschild, and physics under Voigt. He was awarded the Prizeof the Philosophical Faculty of the University of Gottingen for hiswork on the stability of elastic wires and tapes in 1906, and graduatedat this university

`

..

..

..

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Fritz Haber - BiographyFritz Haber - Biography

Fritz Haber was born on December 9, 1868 in Breslau, Germany,in one of the oldest families of the town, as the son of SiegfriedHaber, a merchant. He went to school at the St. Elizabeth classicalschool at Breslau and he did, even while he was at school, manychemical experiments.

From 1886 until 1891 he studied chemistry at the University of Heidelberg under Bunsen, at the University of Berlin under A.W.Hoffmann, and at the Technical School at Charlottenberg underLiebermann. After completing his University studies he voluntarilyworked for a time in his father's chemical business and, beinginterested in chemical technology, he also worked for a while underProfessor Georg Lunge at the Institute of Technology at Zurich. Hethen finally

Image by MIT OpenCourseWare.

Image by MIT OpenCourseWare.

Mn1.171.277.352.96/9.4144

14.644219.7280.330.4790.0781

Crystal Structure12

Acid/Base Properties11

Enthalpy of Fusion20, kj/molEnthalpy of Vaporization21, kl/mol (at boiling point)

Atomic Volume16 cm 3/mol

Enthalpy of Atomization22, kl/mol (at 25oC)

Specific Heat Capacity23 J/g/K (at 25oC & 100 kPa)

Terminal Conductivity24 W/cm/K (at 25oC)

Zeff 17/Polarizability18

Metallic Radius[Van der Waals Radius]15, A

Covalent Radius14,A

SymbolAllotropic Form13

VIIAVIIB

7Group Classifications

HSublimation∆

Ωm at 25oC

Na1.541.9023.701.84/23.64.88

2.59480.04108.371.2281.42

= ∆Hsublimation

Image by MIT OpenCourseWare.

Image by MIT OpenCourseWare.

Na(s) + Cl2(g) NaCl (s)_21

3.

4.

5.Cl2(g) Cl(g)_212.

Na(g) Na(g)1.

Na(g) Na+(g) + e_

495.8 kJ/mol

122 kJ/mol

107.3 kJ/mol

-411 kJ/mol

Na+(g) + Cl_(g) NaCl (s)

-787 kJ/mol

Cl(g) + e_ Cl

_(g)

-348.6 kJ/mol

Net reaction

A Born _ Haber Cycle for NaCl

F _

Cl _

Br _

I _

O 2_

Anion Cation

Li+

Na+

K+

Be2+

Mg2+

Ca2+

Al3+

1036 853 807 757 2925

923 787 747 704 2695

821 715 682 649 2360

3505 3020 2914 2800 4443

2957 2524 2440 2327 3791

2630 2258 2176 2074 3401

5215 5492 5361 5218 15916

Lattice energies of some Ionic solids (kj/mol)

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Cs+ 1.67 Ba2+ 1.31 La3+ 1.22

Te2- 2.22 I- 2.19

Ionic Radii (A) for Ions with Noble-gas Electron Configurations

Li+ 0.68 Be 2+ 0.30

Na+ 0.98 Mg2+ 0.65 Al3+ 0.45

02- 1.45 F- 1.33

K+ 1.33 Ca2+ 0.94 Sc3+ 0.68

S2- 1.90 CI- 1.81

Se2- 2.02 Br- 1.96

Rb+ 1.48 Sr 2+ 1.10 Y3+ 0.90

[Ar]

[Kr]

[He]

[Ne]

[Xe]Cs+1.67 Ba2+ 1.31 La 3+ 1.22

Te 2- 2.22 I- 2.19

o

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Image by MIT OpenCourseWare.

2 Al3+ + 6 e- 2 Al

3 O2- 1.5 O2 + 6 e-

3 O2- + 1.5 C 1.5 CO2 + 6 e-

consumable carbon anode

0.45 kg C / kg Al

aluminum produced by electrolytic reduction of Al2O3

world capacity: ~40 million tonnes/year

decompose Al2O3 dissolved in Na3AlF6 (T = 960°C)

liquid Al (-) and CO2 (+)

Charles Martin Hall, USA Paul L.T. Héroult, France

1886

© source unknown. All rights reserved. This image is excluded from our Creative Commons license. For more

find an inert anode information, see http://ocw.mit.edu/fairuse.

2 Al3+ + 6 e- 2 Al

3 O2- 1.5 O2 + 6 e-

3 O2- + 1.5 C 1.5 CO2 + 6 e-

inert anode

no CO2; no CF4

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3.091SC Introduction to Solid State Chemistry Fall 2009

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