Guidance Manual for

Physical Chemistry III

003156.01

Yixuan Che
University of Science and Technology of China
Copyright © 2021 Yixuan Che. All rights reserved.
 Guidance Manual for
Physical Chemistry III
003156.01
by

Yixuan Che
 21

Materials Science and Engineering MSE 20

60

III

III III

[email protected]

2021

i
iii
 ix
xv
0 20 1
1 7
........................................... 7
1.1 .......................................... 7
1.2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
1. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2 37
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
2.1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
2.2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2.3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
2.4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3 49
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
3.1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
3.2 . . . . . . . . . . . . . . . . . . . . . . . . . . 50
3.3 . . . . . . . . . . . . . . . . . . . . . . . . . . 51
3.4 . . . . . . . . . . . . . . . . . . . . . . . . . . . 53

v
− vi −

3.5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
3.6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
3.7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56

4 61
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
4.1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
4.2 . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
4.3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62

5 65
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
5.1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
5.2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
5.3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
5.4 - - . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
5.5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
5.5.1 . . . . . . . . . . . . . . . . . . . . 70
5.5.2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
5.6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
5.6.1 . . . . . . . . . . . . . . . . . . . . . . . . . . 73
5.6.2 . . . . . . . . . . . . . . . . . . . . . . . . . . 74
5.6.3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
5.7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
5. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79

6 83
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
6.1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
6.2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
6.2.1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
 − vii −

6.3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
6.4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
7 89
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
8 91
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
8.1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
8.2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
8.3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
8.3.1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
8.3.2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
8.3.3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
A 113
B 139
C 147
1 . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2 Coll. Code 153491 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3 Coll. Code 15194 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
4 Coll. Code 63356 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
5 Coll. Code 92184 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

1.1 Callister-Fig. 3.20 . . . . . . . . . . . . . . . . . . 7

1.2 Callister-Tab.3.6 . . . . . . . . . . . . . . . 9
1.3 West-Fig.1.3 . . . . . . . . . . . . . . . . . . . 9
1.4 14 Bravais ab West-Fig.1.12 10
1.5 Callister-Fig.3.29 . . . . . . . 11
1.6 fcc Callister-Fig.3.31
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.7 Callister-Fig.3.30 . . . . . . . . . . . . . . . . 11
1.8 Callister-Fig.3.32 . . . . . . . . 12
1.9 West-Fig.1.23 . . 12
1.10 (a) (b) (c) West-Fig.1.28 13
1.11 NaCl Callister-Fig.3.5 West-Fig.1.31 . . 14
1.12 CsCl Callister-Fig.3.6 . . . . . . . . . . . . . . . . . . . . . . 15
1.13 Callister-Fig.3.6 West-Fig.1.33 . 15
1.14 West-Fig.1.35 . . . . . . . . . . . . 15
1.15 NiAs West-Fig.1.35 . . . . . . . . . . . . . 16
1.16 CaF2 Callister-Fig.3.8 Na2 O NaO4
West-Fig.1.34 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.17 TiO2 3D West-Fig.1.37 . . . . . . . . . . . . . 16
1.18 Callister-Fig.3.9 West-
Fig.1.41 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1.19 West-Fig.1.44 . . . . . . . . . . . . . . . . 18
1.20 MgAl2 O4 3D West-Fig.1.44 . . . . . . . . . . . . . 19
1.21 ReO3 Nax WV VI
x W(1−x) O3 West-Fig.1.43 . . . . . . . . 20
1.22 SiO2 West-Fig.1.52 . . . . . . . . . . . . . . . . . . . . . 20
ix
−x−

1.23 SiO2 Callister-Fig.3.11 SiO2

Callister-Fig.3.12 . . . . . . . . . . . . . . . . . . 20
1.24 Callister-Fig.3.13
Callister-Fig.3.14 . . . . . . . . . . . . . . . . . . . . . 21
1.25 Callister-Fig.3.16 . . . . . . . . . . . . . . . . . . . . . 21
1.26 Callister-Fig.3.17 . . . . . . . . . . . . . . . . . . . . 22
1.27 C60 Callister-Fig.3.18 . . . . . . . . . . . . . . . . . . . . 22
1.28 Callister-Fig.3.18 . . . . . . . . . . . . . . . . . 22
1.29 LiF West-Fig.3.1 . . . . . . . . . . . . . . . . . . . . . 23
1.30 LiF Li F P Pauling G Gold-
schmidt M West-Fig.3.2 . . . . . . . . . . . . 24
1.31 S-P West-
Fig.3.3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
1.32 West-Fig.3.8 . . . . . . . . 26
1.33 West-Fig.3.5 . . . . . . . . . . . . . . 27
1.34 1.2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
1.35 1.3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
1.36 1.4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
1.37 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
1.38 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
1.39 . . . . . . . . . . . . . . . . . . . . . . . . . . 33
1.40 . . . . . . . . . . . . . . . . . . . . . . . . 34

2.1 West-Fig.2.1 . . . . . . . . . . . . . . . . . 37
2.2 Callister-Fig.5.8 . . . . . . . . . . . . . . . . . . . . 38
2.3 Callister-Fig.5.9 . . . . . . . . . . . . . . . . . . . . 39
2.4 Callister-Fig.5.10 . . . . . . . . . . . . . . . . 39
2.5 Callister-Fig.5.12 . . . . . . . . . . 40
2.6 Kröger-Vink . . . . . . . . . . . . . . . . . . . . . . . . 41

3.1 Schottky van’t Hoff . . . . . . . . . . . . . . . . . . . . . . . . 50

3.2 MO1−x Brouwer Kofstad-Fig.3.2 . . . . . . . . . . 52
3.3 3 Brouwer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
3.4 5 Brouwer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59

5.1 Ellingham . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
5.2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
5.3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
 − xi −

5.4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
5.5 - . . . . . . . . . . . . . . . . . . . . . . . . . . 69
5.6 - . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
5.7 - . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
5.8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
5.9 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
5.10 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
5.11 . . . . . . . . . . . . . . . . . . . . 72
5.12 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
5.13 Jost Wagner . . . . . . . . . . . . 73
5.14 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78

6.1 γlm ∆Hvap 86

7.1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
7.2 Nyquis . . . . . . . . . . . . . . . . . . . 90

8.1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
8.2 He . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
8.3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
8.4 . . . . . . . . . . . . . . . . 93
8.5 . . . . . . . . . . . . . . . . . . . . . . . . 93
8.6 . . . . . . . . . . . . . . . . . . . . . . . 93
8.7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
8.8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
8.9 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
8.10 . . . . . . . . . . . . . . . . . . . . . . . . 96
8.11 . . . . . . . . . . . . . . . . . . . . . . . . 96
8.12 . . . . . . . . . . . . . . . . . . . . . . . . . 97
8.13 . . . . . . . . . . . . . . . . . . . 97
8.14 . . . . . . . . . . . . . . . . . . . 98
8.15 . . . . . . . . . . . . . . . . . . . . . 98
8.16 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
8.17 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
8.18 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
8.19 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
8.20 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
8.21 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
− xii −

8.22 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
8.23 7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
8.24 8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
8.25 9 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
8.26 11 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
8.27 12 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
8.28 13 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
8.29 14 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
8.30 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
8.31 7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
8.32 9 1 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
8.33 9 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
8.34 10 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
8.35 10 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
8.36 10 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
8.37 11 1-2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
8.38 11 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
8.39 11 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
8.40 12 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
8.41 13 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
8.42 14 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112

A.1 . . . . . . . . . . . . . . . . . . . . . . . . . . 113
A.2 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
A.3 . . . . . . . . . . . . . . . . . . . . . . . . 116
A.4 3 Brouwer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
A.5 5 Brouwer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
A.6 28 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
A.7 29 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
A.8 41 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
A.9 43 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
A.10 44 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
A.11 45 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
A.12 46 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
A.13 47 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
A.14 47 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
A.15 48 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
 − xiii −

A.16 49 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
A.17 49 1 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
A.18 49 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
A.19 50 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
A.20 50 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
A.21 50 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
A.22 51 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
A.23 51 1-2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
A.24 51 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
A.25 51 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
A.26 52 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
A.27 52 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
A.28 53 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
A.29 53 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
A.30 54 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
A.31 54 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138

B.1 18 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
B.2 20 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
B.3 28 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
B.4 29 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144

C.1 29 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
C.2 29 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
1.1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.3 14 Bravais . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.4 32 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.5 . . . . . . . . . . . . . . . . . 13
1.6 Pauling . . . . . . . . . . . . . . . . . . . . . 14
1.7 . . . . . . . . . . . . . . . . . . . . . . . 24
1.8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

5.1 Ni . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76

xv
 0
20

1. ABO3 ( CaTiO3 , FeTiO3 ,

CaCO3 )
ICSD 146.66.193.6
Coll. Code
CaTiO3

FeTiO3 ICSD Coll. Code 153491 R3̄H

CaCO3 ICSD Coll. Code 15194 P mcn

1
−2− 0 20

2 Coll. Code 153491

3 Coll. Code 15194

2.
ABO3
√
√ 2RA−O
a= 2RA−O = 2RB−O , = 1.
2RB−O
A B
√ √
2(RA + RO ) 2RA−O
t= = .
2(RB + RO ) 2RB−O
0.9 < t < 1 t>1 BaTiO3
 −3−

t = 1.06 t 0.85 < t < 0.9

BO6
3. YBa2 Cu3 O7−x
YBa2 Cu3 O6.08 ICSD Coll. Code 63356
Y Ba Cu BaCuO3
BaCuO3 Y Ba 12
Y 8 YBa2 Cu3 O6.08

4 Coll. Code 63356

4. ABO2 AB2 O4 A2 BO4

CuFeO2 ICSD Coll. Code 92184 AB2 O4
MgAl2 O4 AB2 O4
5.

6.

7. n- p- ZnO CoO NbO Nb2 O5

n-
p-
SnO2 Sn 4 5s2 5p2 2 O 2s2 p4
SnO2 Sn
−4− 0 20

5 Coll. Code 92184

n-

8.
9.
ZrO2 n-

10. BaCeO3

Y Nb BaCeO3
11. MO1−x M1+x O
MO

12. M1+y O2−x

13. LaMnO3 SrO

Sr Mn LaMnO3
1 1
La2 O3 + Mn2 O3 = La× × ×
La + MnMn + 3OO ,
2 2
Sr Mn
1 2 × 1
SrO + Mn2 O3 = Sr′Mn + Mn×
••

Mn + OO + VO .
2 5 2
14.
 −5−

s−s s−l s−g

15.
Jander Gingsting Carter
6.5.3
16.

17.

18.

19.

20.
Li+

Charge − Charge
−−−
LiCoO2 ↽ −−−−
−−
⇀ +
− Li1−x CoO2 + xLi + xe ; C + xLi+ + xe− ↽
−−−
−−−−
−−
⇀− CLix .
Discharge Discharge
 1
1. Bravais

2.
3. hcp fcc sc bcc

4.
Pauling

1.1
1.
crystal

2.

lattice

1.1 Callister-Fig.
3.20

7
−8− 1

+ =

3.
cell

1.1
4.
1.1

Schönflies
(mirror plate) m σh , σ v , σ d
(center of symmetry) 1̄ i
(rotation axis) 2, 3, 4, 6 Cn (n = 2, 3, 4, 6)
(inversion axis) n̄(n = 2, 3, 4, 6) −
(alternating axis) − Sn (n = 2, 3, 4, 6)
(screw axis) 21 , 31 , 32 , · · · −
(glide plane) a, b, c, d, n −

5.
1.2

triclinic a ̸= b ̸= c α ̸= β ̸= γ ̸= 90◦ 1̄
monoclinic a ̸= b ̸= c α = γ = 90◦ ̸= β 2 2̄ 2/m
orthorhombic a ̸= b ̸= c α = β = γ = 90◦ 2 2̄ mmm
tetragonal a = b ̸= c α = β = γ = 90◦ 4 4̄ 4/mmm
hexagonal a = b ̸= c α = β = 90◦ , γ = 120◦ 6 6̄ 6/mmm
(a) trigonal(a) a = b ̸= c α = β = 90◦ , γ = 120◦ 3 3̄ 3m
(b) trigonal(b) a=b=c α = β = γ ̸= 90◦ 3 3̄ 3m
Cubic a=b=c α = β = γ = 90◦ 3 m3m

6. 14 Bravais
1.3 14 Bravais

Bravais
P
P, C
P, F, I, A (B C)
P, I
P
R
P, I, C
1.1 −9−

1.2 Callister-Tab.3.6

1.3 West-Fig.1.3
− 10 − 1

1.4 14 Bravais ab West-Fig.1.12

7. 32
1.4 32

1, 1̄
2, m, 2/m
222, mm, mmm
4, 4̄, 4/m, 4mm, 4/mmm, 422, 4̄2m
6, 6̄, 6/m, 6mm, 6/mmm, 622, 6̄m2
3, 3̄, 32, 3m, 3̄m
23, m3, 4̄3m, 432, m3m

8. 230 http://img.chem.ucl.ac.uk/sgp/large/sgp.htm
1.2 − 11 −

1.2
1.

1.5 Callister-Fig.3.29

1 fcc face-centered cubic

1.6 fcc Callister-Fig.3.31

2 hcp hexagonal close-packed

1.7 Callister-Fig.3.30
− 12 − 1

3 Tetrahedral Octahedral

1.8 Callister-Fig.3.32

1.9 West-Fig.1.23
4 74.05% 12
2.
1 sc simple cubic 52.36% 6
2 bcc body-centered cubic 68.02% 8
3 diamond cubic lattice 34.01% 4
1.3 − 13 −

1.3
1. (space-filling polyhedra)

NaCl NaCl6

1.10 (a) (b) (c) West-Fig.1.28

1.5

M-M 2.00M-X(tet.) 1.16M-X(tet.) 0.67M-X(tet.)

M-M 2.00M-X(oct.) 1.41M-X(oct.) 1.16M-X(oct.)

2. ionic bond
100%
Pauling
µ
P IC(P ercent Ionic Character) = × 100%. (1.3.1)
eR
µ eR
− 14 − 1

P IC(P ercent Ionic Character) = (1 − e−1/4(χA −χB ) ) × 100%.

2
(1.3.2)
|χA − χB |
1.6 Pauling

Allred A L. Electronegativity values from thermochemical data[J]. Journal of Inorganic and Nuclear
Chemistry, 1961, 17(3 4):215-221.

3.
1 AX
• NaCl fcc
fcc fcc NaCl6 3D

1.11 NaCl Callister-Fig.3.5 West-Fig.1.31

1.3 − 15 −

• CsCl

1.12 CsCl Callister-Fig.3.6

• ZnS sphalerite fcc 1/2

T+ T− 1/2 (T − T+ ZnS4
3D

1.13 Callister-Fig.3.6 West-Fig.1.33

• ZnS wurtzite hcp 1/2

T+ T− 1/2 (T − T+ ZnS4
3D

1.14 West-Fig.1.35
− 16 − 1

• NiAs hcp NiAs6

3D

1.15 NiAs West-Fig.1.35

2 Am Xp
• CaF2 fcc
A fcc
• Na2 O fcc

1.16 CaF2 Callister-Fig.3.8 Na2 O NaO4 West-Fig.1.34

• TiO2 a = b ̸= c TiO6
3D

1.17 TiO2 3D West-Fig.1.37

1.3 − 17 −

3 Am Bn Xp
• ABO3 perovskite A 12 B 6

1.18 Callister-Fig.3.9 West-Fig.1.41

− 18 − 1

– Tolerance factor
√
√ 2RA−O
a= 2RA−O = 2RB−O , = 1. (1.3.3)
2RB−O
A B (1.3.3)
√ √
2(RA + RO ) 2RA−O
t= = . (1.3.4)
2(RB + RO ) 2RB−O
∗ 0.9 < t < 1
∗ t>1 BaTiO3 t = 1.06
t
∗ 0.85 < t < 0.9 BO6
–
a b c Glazer
a b c
0 + −

• (AB2 O4 , spinel) A 1/8 B 1/2

8 AB2 O4 3:4
+8

1.19 West-Fig.1.44
1.3 − 19 −

–
∗ +2 +3 MgAl2 O4 Fe3 O4
∗ +2 +4 Mg2 TiO4
∗ +1 +3 +4 LiAlTiO4
∗ +1 +3 Li0.5 Al2.5 O4
∗ +1 +2 +5 LiNiVO4
∗ +1 +6 Na2 WO4
–
∗ normal spinel Atet Boct
2 O4
∗ inverse spinel) B A
tet oct
B (A,B) O4 ( A B )
∗ tet
(Bλ A1−λ ) (Aλ B2−λ ) O4 oct
λ λ=0
λ=1
∗

– (norm−, inverse−)
∗
∗ R+ /R− ≤ 0.414 4 R+ /R− >
0.414 6
∗

1.20 MgAl2 O4 3D West-Fig.1.44

− 20 − 1

• ReO3 Nax WV VI
x W(1−x) O3 ReO6
A Na 12

1.21 ReO3 Nax WV VI

x W(1−x) O3 West-Fig.1.43

4 Silicate

1.22 SiO2 West-Fig.1.52

1.23 SiO2 Callister-Fig.3.11 SiO2

Callister-Fig.3.12
1.3 − 21 −

1.24 Callister-Fig.3.13
Callister-Fig.3.14

4.
1 diamond C
C 4

1.25 Callister-Fig.3.16

2 graphite

3 C60 fullerenes 20 12
C
C60
− 22 − 1

1.26 Callister-Fig.3.17

1.27 C60 Callister-Fig.3.18

4 carbon nanotubes

1.28 Callister-Fig.3.18

1.4
1.
1
1.4 − 23 −

2
•
•
•
3

1.29 LiF West-Fig.3.1

5
• Goldschmidt NaCl 6 R(F− ) = 1.33Å R(O2− ) =
1.32Å
• Pauling

Cn
R= (1.4.1)
Z −σ
R Cn Z σ
(Z − σ)

• Shannon-Prewitt R(O2− ) = 1.40 CN=6

X R(F− ) = 1.19Å
R(O2− ) = 1.26Å CN 6
− 24 − 1

1.30 LiF Li F P Pauling G Goldschmidt M

West-Fig.3.2

Cr3+ P>G>S&P
G>S&P>P
•

5
6

1.7

12 8 6 4
1.12 1.03 1 0.94

2. Pauling
1

1.8

2 3 4 6 8 12
R+ /R− <0.155 0.155∼0.225 0.225∼0.414 0.414∼0.732 0.732∼1.0 1.0

5 7 9 11
Al O
1.4 − 25 −

1.31 S-P West-Fig.3.3

2
<1/6
electrostatic bond strength ebs
X mj
|Zi − | = Mj sij , sij = . (1.4.2)
nj
Zi − Mj sij
mj nj
3

SiO4
4
− 26 − 1

6 bond valence

X
Vi = bvij . (1.4.3)
j

 N
R0
bvij = . (1.4.4)
R
R R0 = 1.622 N = 4.290

1.32 West-Fig.3.8

3. U
1 1mol
2
• Born-Haber Hess

•
–
– Born-Lander  
e2 Z+ Z− NA A 1
U =− 1− . (1.4.5)
r0 n
NA Avogadro A Madelung n
Born He Ne Ar Kr Xe n 5
7 9 10 12
 1 − 27 −

1.33 West-Fig.3.5

– Kapustinskii  
125200vZ+ Z− 34.5
U= 1− , (1.4.6)
r0 r0
v r0
4. (Quantitative bond valence method
Na Mg Al Si
P S
 N
R0
sij = , (1.4.7)
R
R R0 = 1.622 N = 4.290 (1.4.7)
dij = Rij − blnsij (1.4.8)

1.1 0.128nm fcc 63.5g/mol

8.94g/cm3

m nM NM
ρ= = = ,
V V V NA
√
fcc Cu N = 4 M = 63.5g/mol V = a3 = (2 2r)3
4 × 63.5g/mol
ρ= √ −1
= 8.89g/cm3 .
16 2 × (0.128 × 10 cm) × 6.02 × 10 mol
−7 3 23

□
− 28 − 1

1.34 1.2

1.2 NaCl 2.16g/cm3 Na+ Cl−

0.102nm 0.181nm
1.34
P P
m N ′ ( M1 + M2 )
ρ= = ,
V V NA
NaCl N ′ = M1 = 23g/mol M2 = 35.5g/mol V = a3 = [2(rNa+ +rCl− )]3
NaCl
4 × (23 + 35.5)g/mol
ρ= = 2.14g/cm3 .
8 × (0.102 × 10−7 + 0.181 × 10−7 cm)3 × 6.02 × 1023 mol−1

1.3 hcp c/a = 1.633

1.35 1.3

√ 1.35√ l = 2r
6 2 6
h= l= r
3 3 √
c 2h 2 6
= = = 1.633.
a l 3
 1 − 29 −

1.4 3 - 0.155

1.36 1.4

1.36 AB = a
√
r+ 3/3a − 1/2a
= = 0.155.
r− 1/2a

1.5
√
1 2 2r r 4

4
4 × πr3
√3 × 100% = 74.05%.
(2 2r)3
2 c = 1.633a a = 2r 2
4
2 × πr3
√3 × 100% = 74.05%.
3
2r × 2r × × 1.633 × 2r
2
√
3 3a = 4r 2
4
2 × πr3
 3 3 × 100% = 68.02%.
4
√ r
3

1.6 4
1.37 90◦

4 + 4 + 8
4 3 3 + 6 3
+ 1.37 4

1.7 Bravais 14
P F I A 7 × 4 = 28
Bravais
− 30 − 1

1.37

1 P F
I A P
2

1.8 aac West-Page 58

Detailed analysis has shown that 15 different tilt systems are theoretically possibly
and classification schemes have been developed by Glazer and Alexandrov.
The widely used Glazer method is as follows:
(1) Starting with the undistorted cubic perovskite, possible rotation about the three
axes of the octahedron is indicated by three letters a, b and c. If the degree of rotation
about all three axes is the same, the letters are the same, i.e. aaa; if rotation about one
axis is different to that about the other two, the labelling is, e.g., aac.
(2) To complete the label, each of the three letters carries a superscript; if there is
no rotation about that axis, the superscript is 0 ; if the rotation between adjacent planes
+
of octahedra is the same, and in-phase, the superscript is ; if the rotation between
adjacent planes is in the opposite sense, the superscript is − .

Pauling
1.9 Mg2 SiO4 Si4+ 1/8 Mg2+ 1/2

4 6 Mg−O Si−O
2/6 = 1/3 4/4 = 1 O Mg x Si y

1
2 = x + y.
3
x y x=1 y = 3.
 1 − 31 −

1.10 ZrO4 Zr 8 Si 4
Zr−O Si−O 4/8 = 1/2 4/4 = 1 O Zr
x Si y
1
2 = x + y.
2
x y x=2 y = 1.

1
1
1 O2−
2
3
a
b
c
d
2. NaCl MgO 4.21Å MnO 4.44Å CaO
4.80Å MgS 5.19 Å MnS 5.21Å CaS 5.68Å, NaCl Ca2+ O2−
Goldschmidt
3. BaTiO3
BaTiO3
a b BaTiO3
c = 4.036Å a = b = 3.992Å

= /

0.061Å

0.036Å Ba2+

Ti4+ O2-
0.12Å

c
a

1.38 3
− 32 − 1

4.
NiAs
5. Bravais

1
2
3
6.

1
2
3
4

1
1. Calculate the radius of a palladium atom, given that Pd has an FCC crystal
structure, a density of 12.0 g/cm3 , and an atomic weight of 106.4 g/mol.
2. Indium has a tetragonal unit cell for which the a and c lattice parameters are
0.459 and 0.495 nm, respectively.
(a) If the atomic packing factor and atomic radius are 0.693 and 0.1625 nm, respec-
tively, determine the number of atoms in each unit cell.
(b) The atomic weight of indium is 114.82 g/mol; compute its theoretical density.
3. Iron oxide (FeO) has the rock salt crystal structure and a density of 5.70 g/cm3 .
(a) Determine the unit cell edge length.
(b) How does this result compare with the edge length as determined, assuming
that the Fe2+ and O2− ions just touch each other along the edges? (R(Fe2+ )=0.077nm,
R(O2− )=0.140nm)
4. Compute the atomic packing factor for the diamond cubic crystal structure
(Figure 1.25). Assume that bonding atoms touch one another, that the angle between
adjacent bonds is 109.5◦ , and that each atom internal to the unit cell is positioned a/4
of the distance away from the two nearest cell faces (a is the unit cell edge length).
5. Sketch a monoclinic unit cell, and within that cell a [101] direction.
6. Sketch a unit cell for the face-centered orthorhombic crystal structure.
Callister Fundamentals of Materials Science and Engineering
 1 − 33 −

1
1

1. 1

1.39

2 4 4 8
3 M
a M2 O M
1/4 2/(1/4)=8
b MO M
2/6=1/3 2/(1/3)=6
c MO M 2/4=1/2,
2/(1/2)=4
d MO2 M 4/6=2/3
2/(2/3)=3
1 (0 0 1/2)
(0 0 1/2) (0 1/2 0) (1/2 0 0) 0 1 (1/2
1/2 1/2)
3

2. MgS MnS
2−
S
√
2 5.19 + 5.21
R(S2− ) = × = 1.84Å.
4 2
CaS Ca2+
1
R(Ca2+ ) = × 5.68 − 1.84 = 1.00Å.
2
S2− O2− CaO O2−
− 34 − 1

1
R(O2− ) = × 4.80 − 1.00 = 1.40Å.
2
3.
X
µ= ql
2e −2e
=8× × 0.061 + 4e × 0.12 + 2 × × (−0.036)
8 2
= 0.674eÅ
= 1.078 × 10−29 Cm,

V = a2 c = 3.9922 × 4.036 = 64.32Å3 = 6.432 × 10−29 m3 .

µ
Ps = = 0.1676C/m2 .
V

0
0

O
4. 1 fcc
NaCl

2 hcp

NiAs
5. 1

(2)
(3)

1.40
 1 − 35 −

6. 1

√
2(r+ + r− ) = 3 × 2r− ,
√
r+ /r− = 3 − 1 = 0.732
2

√
2 × 2r− = 2(r+ + r− ),
√
r+ /r− = 2 − 1 = 0.414
3
√
109.5◦ 2r− / 3
q √ q √
(r+ + r− ) − (2r− / 3) = (2r− )2 − (2r− / 3)2 − (r+ + r− ),
2 2

r+ /r− = 0.225
4

 q 2
2
(2r− ) = 2
r− + (r+ + r− ) + (r+ + r− )2 − 2
r− ,
√
( 3 − 1)2
r+ /r− = √ = 0.155
2 3
0 1 1

1
1. R = 0.138nm.
2. (a) n = 4 atom/unit cell; (b) ρ = 7.31 g/cm3 .
3. (a) a = 0.437nm; (b) a = 0.434nm.
4. 34.05%.
5.
6.
 2
1.
2.

3.

2.1
1. defects

2.

2.1 West-Fig.2.1

37
− 38 − 2

∆H S = k ln W W
k Boltzman ∆G = ∆H − T ∆S

∆G ∆S
S H

∆H
∆H
3.
1

2
point defect)
/ extended defect)
3

2.2
1. dislocation
1 edge dislocation)

2.2 Callister-Fig.5.8
2.2 − 39 −

edge dislocation line ⊥

⊤

2.3 Callister-Fig.5.9

2 screw dislocation

screw dislocation line 2.3 AB ⟳

3 mixed dislocation

2.4 Callister-Fig.5.10

4 Burgers vectors

5
6
− 40 − 2

2. interfacial defects
1 external surfaces

J/m2 erg/cm2

2 grain boundaries

2.5 Callister-Fig.5.12

3 phase boundaries
4 crystallographic shear structure
5 stacking faults
6 subgrain boundaries
7 antiphase boundaries
2.3 − 41 −

2.3
1. Kröger-Vink

2.6 Kröger-Vink

1 vacancy V
2 interstitial Vi
3 Vi
× ′ •
4
5 e′
•
6 h
P P
7 =
2.
1 Ma Ob M O
a/b

2
3.
1
• Schottky MO VM′′ VO ••

• Frenkel MO VM′′ Mi
••

• Schottky Frenkel

Schottky
2 MO
• M1−y O VM′′
• M1+y O Mi ••

• MO1−y VO••

• MO1+y O′′i
4.
1

2
3 MO
1:1 M2 O3 2:3
− 42 − 2

5. MO
1 Schottky
0 = VM′′ + VO
••

2 Frenkel
M× ′′ ••

M = Mi + VM

3 Frenkel
O× ′′ ••

O = Oi + VO

4
0 = e′ + h
•

5 MO1−x
1
O× ′••

O = VO + 2e + O2 (gas)
2
6 M1+x O
1
M× × ′ ••

M + OO = Mi + 2e + O2 (gas)
2
M(gas) = Mi + 2e′
••

7 M1−x O
1
O2 (gas) = VM′′ + 2h + O×
•

O
2
8 MO1+x
1
O2 (gas) = O′′i + 2h
•

2.4
1. M1−x O
1
Mh2 O3 + 2h = 2MhM + 2O×
• •

O + O2 (gas)
2
Mh2 O3 = 2MhM + VM′′ + 3O×
•

2. M1−x O
1
Ml2 O + O2 (gas) = 2Ml′M + 2O×
•

O + 2h
2
Ml2 O + VM′′ = 2Ml′M + O×
O

3. MO2−x
1
Mh2 O5 = 2MhM + 2e′ + 4O×
•

O + O2 (gas)
2
Mh2 O5 + VO = 2MhM + 5O×
•• •

O
2.4 − 43 −

4. MO2−x
1
Ml2 O3 + 2e′ + O2 (gas) = 2Ml′M + 4O×
O
2
Ml2 O3 = 2Ml′M + VO + 3O×
••

5. M1+x O
1
Mh2 O3 = 2MhM + 2e′ + 2O×
•

O + O2 (gas)
2
Mh2 O3 + Mi = 2MhM + MM + 3O×
×
•• •

6. M1+x O
′
Ml2 O + M× × ••

M = 2MlM + OO + Mi
1
Ml2 O + 2e′ + O2 (gas) = 2Ml′M + 2O×
O
2
7. MO1+x
Mh2 O3 = 2MhM + O′′i + 2O×
•

O
1
Mh2 O3 + 2h = 2MhM + 2O×
• •

O + O2 (gas)
2
8. MO1+x
1
Ml2 O + O2 (gas) = 2Ml′M + 2O×
•

O + 2h
2
Ml2 O + O′′i = 2Ml′M + 2O×
O

9. Mh2 O3 MO
1 Mh2 O3 MO MO M M
M
Mh2 O3 = 2MhM + VM′′ + 3O×
•

2 Mh2 O3 MO Mh2 O3

1
Mh2 O3 = 2MhM + 2O× ′
•

O + 2e + O2 (gas)
2
3 Mh2 O3 MO Mh2 O3
Mh2 O3 = 2MhM + O′′i + 2O×
•

10. Ml2 O3 MO2

1 Ml2 O3 MO2 MO2

Ml2 O3 = 2Ml′M + VO + 3O×

••

2 Ml2 O3 MO2 Ml2 O3 MO2

− 44 − 2

1
Ml2 O3 + O2 (gas) = 2Ml′M + 4O×
•

O + 2h
2
3 Ml2 O3 MO2 M M
M
′
2Ml2 O3 + M× 4 × •

M = 4MlM + Mi + 6OO

11.
1
•
OHO
1
H2 (gas) + 2O× ′
H2 O(gas) + 2O× ′
• •

O = 2OHO + 2e or O = 2OHO + 2e + O2 (gas)

2
2
H2 O(gas) + VO + O×
•• •

O = 2OHO

3
•
•
OHO •
Hi
• H×
i
• HO •

12.
1 A B 1:1
A
2

2.1 MO

O× ′′ •

O + H2 O(gas) = 2OHO + VM

2.2 CeO2 Ce
(Ce +3 +4 )
Ce× × ′
Ce + OO = CeCe + OO
•
Ce× ′
Ce = CeCe + h
•

2
1. M2 O5
M Ml M Mh
 2 − 45 −

2.

1 Mh2 O3 + 3Mi = 2Mhi + 3M×

••• ×
M + 3OO
•••

2 MX M 1 M×
M = Mi + e
• ′

3. M2 O5

4. NaCl Na Cl
5. Mh2 O5 Ml2 O M2 O3+x
6
La
Ba BaTiO3

7. Sc2 O3 CaTiO3 Sc Ti

8 LaMnO3 Schottky
La
9. 1 MO M2 O3
2
3 MO M2 O3

10 CaF2 CaO F O CaO

Schottky

2
1. Write a reaction for a charge transfer between the cation and anion in CeO2 , i.e.
for reduction of the cerium ion and oxidation of the oxygen ion. Write the same process
as an intrinsic ionisation assuming delocalised electronic defects.
2. We have in the text claimed that charges can be associated directly with ideal
point defects, even if the compound is not ideally ionic, and that this normally does not
affect the results of the calculations. Under what conditions will it start to matter that
the charge of the defect actually extends outside the defect itself?
3. Write reactions for dissolution of CaO into the oxide ZrO2−x .
4. Write reactions for dissolution of MfO into M2−x O3 when we assume that the
foreign metal Mf is small and therefore dissolves interstitially.
5. Write reactions for dissolution of CaO substitutionally into the anion- Frenkel
dominated Y2 O3 .
− 46 − 2

6. Write reactions for dissolution of ZrO2 substitutionally into the anion- Frenkel
dominated Y2 O3 .
7. Write a reaction for dissolution of protons in an oxide with water vapour as source
and with oxygen interstitials as compensating defects.
8. Write reactions for dissolution of protons in an oxide M1−x O with water vapour
as source.
9. Consider an oxide M2 O3 which is acceptor-doped by dissolving the oxide MlO.
The dopants are compensated by oxygen vacancies. Write a defect reaction for the
dissolution of MlO. Write a reaction for the dissolution of protons from water vapour
into this acceptor doped oxide, by annihilation of the oxygen vacancies. Finally, write a
reaction for the dissolution of MlO in the presence of water vapour and without forming
oxygen vacancies. Can the latter reaction be constructed as a sum of the two previous
reactions?
10. Hydride ions have been suggested to dissolve in oxides accompanied by protons
by disproportionation of hydrogen gas. Write defect reactions for this in the case that
the hydride dissolves a) interstitially, and b) substitutionally. (Assume in both cases that
the oxide is perfectly stoichiometric and has no defects as a starting point).
11. Write defect reactions for formation of A-site Frenkel, B-site Frenkel, and anion
Frenkel disorders in a perovskite ABO3 (assuming both cations are trivalent).
12. Write a defect reaction for the formation of Schottky disorder in spinel MgAl2 O4 .
Per Kofstad Truls Norby Defects and Transport in Crystalline Solids

2
2

1. VM′′′′′ •••••
Mi O′′i ••
VO ••••
MMl M′Mh e′ h •

2.
1
2
1
3. M2 O5−x O× ′
O = VO + 2e + O2 (gas)
••

2
× × 5
M2+x O5 2MM + 5OO = 2Mi + O2 (gas) + 10e′•••••

2
5 ′′′′′ ×
O2 (gas) = 2VM + 5OO + 10h •

2
1
O2 (gas) = O′′i + 2h •

2
1
4. Cl2 Na Cl2 (gas) = V′Ca + Cl×
Cl + h
•

2
1
Cl2 Cl Cl×Cl = VCl + Cl2 (gas) + e
• ′
2
 2 − 47 −

Na Na Na× ′
Na = VNa + Na(gas) + h
•

Na Cl Na(gas) = VCl + Na×

Na + e
′•

Mh2 O5 = 2MhM +2O′′i +3O× Mh2 O5 +4h = 2MhM +3O×

•• • ••
5. O O +O2 (gas)
Ml2 O + O2 (gas) = 2Ml′′M + 3O×
O + 4h
•
Ml2 O + 2O′′i = 2Ml′′M + 3O×
O
1
6. La2 O3 + 2TiO2 = 2LaBa + 2Ti× × ′
•

Ti + 6OO + 2e + O2 (gas)
2
7. 2CaO + Sc2 O3 = 2Ca× × ′
Ca + 5OO + 2ScTi + VO
••

8. 2La× × ′′′
La + 3OO = 2VLa + 3VO + La2 O3 (solid)
••

9. 1 2MlO = 2Ml′M + VO + 2O×

O
••

2 H2 O(gas) + VO + O× •• •

O = 2OHO
3 2MlO + H2 O(gas) = 2Ml′M + 2OHO + O×
•

O
(1) + (2) = (3)
10. CaF2 = 2FO + Ca×
• ′′
Ca + VCa CaF2 + VO = 2FO + Ca×
••

Ca
•

2
 3
1.
Brouwer
2. TiO2 BaTiO3

3.1
0K

1.
N nV
∆G = nV (∆H − T ∆Svib ) − T ∆Sconf . (3.1.1)
∆H Svib Sconf
Boltzmann
(N + nV )!
∆Sconf = klnW = kln . (3.1.2)
N !nV !
x≫1 lnx! = xlnx + x
 
N + nV N + nV
∆Sconf = k N ln + nV ln , (3.1.3)
N nV
 
N + nV N + nV
∆G = nV (∆H − T ∆Svib ) − kT N ln + nV ln . (3.1.4)
N nV
49
− 50 − 3

∂∆G
=0
∂nV
   
nV ∆Svib ∆H
Kv = = exp exp − . (3.1.5)
N + nV R RT
2.
∆G⊖ = ∆H ⊖ − T ∆S ⊖ = −RT lnK
     
⊖ ∆H ⊖ ∆S ⊖ ∆H ⊖
K = K exp − = exp exp − . (3.1.6)
RT R RT
 
⊖ ∆S ⊖
K = exp
R
1 ∆S ⊖ ∆H ⊖
lnK −
T R R

3.2
1. Schottky
0 = VM′′ + VO . ••

:
[VM′′ ] [VO ]
••

KS = aVM′′ aVO = XVM′′ XVO =

•• ••
(3.2.1)
[M] [O]
MO [M] = [O] =1 KS = [VM′′ ][VO ] ••

[VM′′ ] = [VO ]••

   
∆SS⊖ ∆HS⊖
[VM′′ ]
1/2
exp −
••
= [VO ] = KS = exp . (3.2.2)
2R 2RT
van’t Hoff

3.1 Schottky van’t Hoff

3.3 − 51 −

2. Frenkel
M× ′′
M = Mi + VM
••

:
[Mi ] [VM′′ ]
••

KF = × , (3.2.3)
[M×M ] [Vi ]

MO [M× ×
M ] = [Vi ] =1 KF = [Mi ][VM′′ ]
••

[Mi ] = [VM′′ ]
••

   
∆SF⊖ ∆HF⊖
[VM′′ ]
1/2
exp −
••
[Mi ] = = KF = exp . (3.2.4)
2R 2RT
3.
0 = e′ + h . •

:
n p
Ki = , (3.2.5)
NC NV
 
′ −Eg
Ki = np = NC NV exp . (3.2.6)
RT
n=p
 
′1/2 1/2 −Eg
n=p= Ki = (NC NV ) exp . (3.2.7)
2RT

   
∆SF⊖ ∆HF⊖
[ ] ∝ exp exp − (3.2.8)
nk nkT
∆H ⊖

3.3
1. MO1−x
1
O× ′
O = VO + 2e + O2 (gas)
••

2
 2  1/2 ••
[VO ] n pO2
KVO = × , (3.3.1)
[OO ] NC p⊖
O2

KV′ O = NC2 KVO = [VO ]n2 pO2 ,

•• 1/2
(3.3.2)

[O×
O] = 1 p⊖
O2 = 1bar
••
n = 2[VO ]

−1/6 −1/6
n = 2[VO ] = (2KV′ O )1/3 pO2 ∝ pO 2 .
••
(3.3.3)
− 52 − 3

Brouwer log[ ]−logpO2

3.2 MO1−x Brouwer Kofstad-Fig.3.2

2. M2+x O3
3 × 3
M× ′
M + OO = Mi + 3e + O2 (gas)
•••

2 4

′ 3/4
= [Mi ]n3 pO2 .
•••
KM i
(3.3.4)
•••
n = 3[Mi ]

−3/16
n = 3[Mi ] ∝ pO2
•••
. (3.3.5)
Brouwer −3/16
3. M1−x O
1
O2 (gas) = VM′′ + 2h + O×
O
•

2
−1/2
KV′ M = [VM′′ ]p2 pO2 . (3.3.6)

p = 2[VM′′ ]

p = 2[VM′′ ] ∝ pO2 .
1/6
(3.3.7)
Brouwer 1/6
4. MO1+x
1
O2 (gas) = O′′i + 2h •

2
−1/2
KO′ i = [O′′i ]p2 pO2 . (3.3.8)

p = 2[O′′i ]

p = 2[O′′i ] ∝ pO2 .
1/6
(3.3.9)
Brouwer 1/6
3.4 − 53 −

3.4
1.
2.
1 n
n‐1
2
3
4

5
6

3.5

1
2

3.6

3.7
σ n Q u
σ = nQu. (3.7.1)
− 54 − 3

1. TiO2
•••• ••••
TiO2 VO ••
Tii Tii
1 lgn ∼lgpO2 ‐1/5
••••
VO ••
Tii ‐1/6
2

3
4
2. BaTiO3
BaTiO3

BaTiO3
BaTiO3

3.1 MO2−x
MO2−x
1
O× ′ ••

O = VO + 2e + O2 (gas) (3.7.2)
2
VO× VO VO •
e′ ••

1
O× × × 1/2
O = VO + O2 (gas) ⇒ K1 = [VO ]pO2 , (3.7.3)
2
•
[V ]
VO× = VO + e′ ⇒ K2 = O× n,
•
(3.7.4)
[VO ]
••
[V ] ′
VO = VO + e ⇒ K3 = O n,
• ••

•
(3.7.5)
[VO ]
  ••
•
[VO ] •• •
Electrostatic neutrality : n = VO + 2VO or n = 1 + 2 [VO ]. •
(3.7.6)
[VO ]
(3.7.5) (3.7.6)
n2 = (n + 2K3 )[VO ].
•
(3.7.7)

(3.7.7) (3.7.4)
n3
[VO× ] = . (3.7.8)
(n + 2K3 )K2
(3.7.8) (3.7.3)
−1/2
n3 = K1 K2 (2K3 + n)pO2 . (3.7.9)
 3 − 55 −

−1/6
1 2K3 ≫ n VO ≫ VO
•• •
n = (2K1 K2 K3 )1/3 pO2
−1/4
2 n ≫ 2K3 VO ≫ VO
• ••
[VO ] = n = (K1 K2 )1/2 pO2
•

−1/2
3 VO× [VO× ] = K1 pO2

3.2 Mh2 O3 MO Schottky Frenkel

1 Schottky 0 = VM′′ + VO ••
KS = [VM′′ ][VO ] ••

Mh2 O3 = 2MhM + VM′′ + 3O×

• •

O [MhM ]
2[VO ] + [MhM ] = 2[VM′′ ]
•• •

[MhM ] ≫ [VO ]
• ••

[MhM ] ≈ 2[VM′′ ],
•
(3.7.10)
KS 2KS
[VO ]S = [VM′′ ]S = ′′ =
••
. • (3.7.11)
[VM ] [MhM ]
2 Frenkel M× ′′
M = Mi + VM
••

2[VM′′ ] = [MhM ] + 2[Mi ]

• ••

[MhM ] ≫ [Mi ]
• ••

2[VM′′ ] ≈ [MhM ],
•
(3.7.12)
••
KF 2KF
[Mi ]F = ′′ = . • (3.7.13)
[VM ] [MhM ]

3.3 M1+x O

1
M× × ′ 2 1/2
M + OO = Mi + 2e + O2 (gas) ⇒ K1 = [Mi ]n pO2 ,
•• ••
(3.7.14)
2
1
H2 O(gas) + 2O× ′ 2 2 1/2 −1
O = 2OHO + 2e + O2 (gas) ⇒ K2 = [OHO ] n pO2 pH2 O .
• •
(3.7.15)
2
• ••
n = [OHO ] + 2[Mi ]
1 n ≈ 2[Mi ] ••

−1/6
n ≈ 2[Mi ] = 2(K1 )1/3 pO2 ,
••
(3.7.16)
−1/12 1/2
[OHO ] = K2 (2K1 )−1/3 pO2
• 1/2
pH2 O . (3.7.17)

n ≈ [OHO ]
•
2
1/4 −1/8 1/4
n ≈ [OHO ] = K2 pO2 pH2 O ,
•
(3.7.18)
•• −1/2 −1/4 −1/2
[Mi ] = K1 K2 pO2 pH2 O . (3.7.19)
− 56 − 3

3
1. M2 O5 Schottky Frenkel
2. M2 O5

3. MO MO1‐x M1‐x O

4. Ml2 O Mh2 O3 M1+x O

5. M2 O3 (MhO2 )
Ki Schottky
Ks Ki ≫ Ks
6. Mh2 O3 MO

7. MO1‐x

3
1. Sketch a full Brouwer diagram (log defect concentrations vs log pO2 ) for an oxide
ABO3 dominated by fully ionised oxygen and metal vacancies at under- and overstoi-
chiometry, respectively. Assume that Schottky defects predominate close to stoichiomet-
ric conditions. You may assume that both cations are trivalent, but discuss also the effect
it would have if A was divalent and B tetravalent. (Hint: the main goal is in any case to
obtain and illustrate the pO2 -dependencies. Use the rules we listed for such constructions
of Brouwer diagrams.)
2. Sketch a full Brouwer diagram (log defect concentrations vs log pO2 ) for an ox-
ide AB2 O4 dominated by fully ionised metal interstitials and vacancies at under- and
overstoichiometry, respectively. Assume that Frenkel defects predominate close to stoi-
chiometric conditions. You may assume that A is divalent and B trivalent. (Hint: the
main goal is to obtain and illustrate the pO2 -dependencies. Use the rules we listed for
such constructions of Brouwer diagrams.)
3. In the text we considered an oxide MO2 that had oxygen deficiency by both fully
charged oxygen vacancies and doubly charged metal interstitials. The figure illustrating
the case was drawn assuming that the ratio between the concentrations of the two defects
was 105 at 1 atm. prmO2 . Calculate the exact prmO2 at which the concentrations are equal.
Per Kofstad Truls Norby Defects and Transport in Crystalline Solids
4. 3
 3 − 57 −

3
3
1. 1 Schottky
0 = 2VM′′′′′ + 5VO ••

KS′ = [VM′′′′′ ]2 [VO ]5 ••

5[VM′′′′′ ] = 2[VO ] ••

 1/7  
5 ′′′′′ 25 ′ ′⊖ ∆HS⊖
••
[VO ] = [VM ] = K = KS exp −
2 4 S 7RT
2 Frenkel
M× ′′′′′
M = VM + Mi
•••••

KF′ = [VM′′′′′ ][Mi ] •••••

[VM′′′′′ ] = [Mi ] •••••

 
∆HS⊖
[VM′′′′′ ] = [Mi ] = •••••
(KF′ )1/2 = KF′⊖ exp −
2RT
2. (1)
5 × 5
M× ′
M + OO = Mi + 5e + O2 (gas)
•••••

2 4
K ′ = [Mi ]n5 pO2
5/4
•••••

•••••
n = 5[Mi ]
−5/24
n = 5[Mi ] = (5K ′ )1/6 pO2
•••••

(2)
5 5
O2 (gas) = VM′′′′′ + O× + 5h + 5h· •

4 2 O
−5/4
K ′ = [VM′′′′′ ]p5 pO2
p = 5[VM′′′′′ ]
p = 5[VM′′′′′ ] = (5K ′ )1/6 pO2
5/24

3.
1
O× ′ 2 1/2
O = VO + 2e + O2 (gas) ⇒ K1 = [VO ]n pO2 ,
•• ••

2
1 ′′ 2 −1/2
O2 (gas) = VM′′ + 2h + O×
O ⇒ K2 = [VM ]p pO2 ,
•

2
0 = VM′′ + VO ⇒ K3 = [VM′′ ][VO ],
•• ••

n + 2[VM′′ ] = p + 2[VO ].
••

−1/6 −1/6
1 n = 2[VO ] ∝ pO2 ••
p ∝ pO2 1/6 [VM′′ ] ∝ pO2
−1/6 −1/6 −1/6
2 p = 2[VM′′ ] ∝ pO2 n ∝ pO 2 [VO ] ∝ pO2
••

−1/4
[VM′′ ] = [VO ] ∝ pO2
1/2 1/4
3 ••
n ∝ pO2 p ∝ pO 2
4. M× × ′ 1
M + OO = Mi + 2e + 2 O2 (gas),
••
K1 = [Mi ]n2 pO2 1/2
••

1 Ml2 O M1+x O Ml′M

−1/6
n = 2[Mi ] ∝ pO2
••
Ml′M
− 58 − 3

3.3 3 Brouwer

−1/4
Ml′M = 2[Mi ] ••
n ∝ pO2
•
2 Mh2 O3 M1+x O MhM
−1/6
n = 2[Mi ] ∝ pO2
••
MhM •

−1/2
[Mi ] ∝ pO2
• ••
n = [MhM ]
•
5. MhO2 M2 O3 MhM

1
O× ′ 2 1/2
O = VO + 2e + O2 (gas) ⇒ K1 = [VO ]n pO2 ,
•• ••

3 ′′′ 6 −3/2
O2 (gas) = 2VM′′′ + 6h + 3O×
O ⇒ K2 = [VM ]p pO2 ,
•

0 = e′ + h ⇒ K3 = np,
•

Schottky
0 = 2VM′′′ + 3VO ⇒ K3 = [VM′′ ]2 [VO ]3 .
•• ••

−1/6
[VM′′′ ] ∝ pO2
1/6 1/4
n = 2[VO ] ∝ pO2
••
p ∝ pO2
−1/2
[VM′′′ ] ∝ pO2
3/4
[VO ] ∝ pO2
• ••
n = [MhM ] = const
−1/4
[MhM ] = 3[VM′′′ ] = const
1/4
p ∝ pO 2 n ∝ pO2
•

−3/16 −1/8
p = 3[VM′′′ ] ∝ pO2
3/16
n ∝ pO2 [VO ] ∝ pO2
••

6.
1
Mh2 O3 = 2MhM + 2e′ + 2O× 2 1/2 2
O + O2 (gas) ⇒ K1 = [MhM ] pH2 O n ,
• •

2
Mh2 O3 = 2MhM + VM′′ + 2O× ′′
O ⇒ K2 = [VM ][MhM ] .
2
• •

−1/8
[VM′′ ] ∝ pO2
1/4
n = [MhM ] ∝ pO2
•
K1
−1/4
[MhM ] = 2[VM′′ ] = const n ∝ pO2
•
K2
7.
1
O× ′ 2 1/2
O = VO + 2e + O2 (gas) ⇒ K1 = [VO ]n pO2 ,
•• ••

2
 3 − 59 −

3.4 5 Brouwer

1
H2 O(gas) + 2O× ′ 2 2 1/2 −1
O = 2OHO + 2e + O2 (gas) ⇒ K2 = [OHO ] n pO2 pH2 O
• •

2
−1/6 1/2
n = 2[VO ] ∝ pO2 [OHO ] ∝ pO2
•• •

1/4 −1/2
n = [OHO ] ∝ pO2 [VO ] ∝ pO2
• ••

3
 4

4.1
1.

0.1%∼1%

2.
1
•

•
H B C N Fe‐C C
fcc−γ‐Fe

2
61
− 62 − 4

•
MgO−CoO MgO CoO NaCl rCo = 0.74 rMg = 0.72
Mgx Co1‐x O x =0∼1
• MgO
◦
CaO 2000 C 3% CaO MgO

4.2
1.

2.
r1 r2
∆r
r1 − r2
∆r = . (4.2.1)
r1
1 ∆r < 0.15
2 0.15 ⩽ ∆r ⩽ 0.30
3 ∆r > 0.30

∆r
3.

4.
Darkon
±15% ±0.4 65%
85% 5% ±0.4

5.

4.3
1. X
1 X
4.3 − 63 −

2 Vegard

2. X
m
ρ= . (4.3.1)
V
1 2 3
3.
 5
1.
2. Ellingham
Ellingham
3.
4. - -
5. Jost Wagner
Kirkendall
6.

Jander Gingsting
Carter
7.

5.1
1. solid state reactions

2. solid state reaction route

3.
1
2
65
− 66 − 5

3
4. -
1
2

5.2
1.
1

 
∂G
µi = , (5.2.1)
∂ni p,T,nj ̸=ni

ηi = µi + zi ϕF. (5.2.2)

2 demix
3 :
4
2. van’t Hoff
∆H < 0
van’t Hoff
3. Ellingham
1 T K
2 ∆G = RT lnpO2 kJ/mol O2
3
∆G = ∆H − T ∆S ∆S 0K
∆H Ellingham 1

4
5 ∆G > 0
6 Ellingham
7 (0K, 0kJ)
8 H C
(0K, 0kJ)
5.3 − 67 −

5.1 Ellingham

5.3
1.
1 Frenkel

2
Schottky
2.

1 ∆G = 0, ∆V ̸= 0, ∆S ̸= 0, ∆H ̸= 0
− 68 − 5

5.2


 µ1 = µ2 ,

    


 ∂µ1 ∂µ2
̸= (V1 ̸= V2 ),
∂p T ∂p T (5.3.1)

    

 ∂µ1 ∂µ2

 ̸= (S1 ̸= S2 ).
 ∂T ∂T p
p

2 ∆G = 0, ∆V = 0, ∆S = 0, ∆H = 0

5.3


 µ1 = µ2 ,



 α1 ≠ α2 ,
(5.3.2)

 β1 ̸= β2 ,




Cp,1 ̸= Cp,2 .
-- --

Cp α β Curie λ
3
(exsolution)
5.4 - - − 69 −

devitrification
CaF2

5.4

AB
BC
topochemical factors
CD
DE

5.4 - -
1. -
1
2
3
2. - A B

5.5 -
− 70 − 5

3. -

5.6 -

4. BaSiO3
5. - A B B AB − B
1 - A AB AB − B B AB
AB − A 2

5.7 -

5.5
5.5.1
1.
AO(s) + B2 O3 (s) −−→ AB2 O4 (s)
1

2 Wagner MgAl2 O4

3 ∆x = 2kt
4 Kirkendall 1:3
MgO/MgAl2 O4
2 Al3 + (4 MgO − 3 Mg2+ ) −−→ MgAl2 O4 (s)
MgAl2 O4 /Al2 O3
3 Mg2+ + (4 Al2 O3 − 2 Al3+ ) −−→ 3 MgAl2 O4 (s)
5.5 − 71 −

5.8

5.9

4 MgO(s) + 4 Al2 O3 (s) −−→ 4 MgAl2 O4 (s)

2.
2 CaO(s) + SiO2 (s) −−→ Ca2 SiO4 (s)

3.
1
2
3
4
− 72 − 5

5.10

5.11

5.12

5.5.2

1. 1+ 2= 1+ 2
2. Jost Wagner
- AX + BY −−→ AY + BX Jost Wagner

1 Jost
Jost AX B X
5.6 − 73 −

BX AX BY A Y
AY BY AX BY A BX
BX B AY AY Jost
Wagner
2 Wagner
Wagner

5.13 Jost Wagner

5.6
5.6.1

1.
1
2 M-O MO O2 MO
MO
3
VR = kC, (5.6.1)
 
dC D(C0 − C)
VD = D = . (5.6.2)
dx x=δ δ

V = VR = vD , (5.6.3)
D(C0 − C)
kC = , (5.6.4)
δ
C0
C= , (5.6.5)
kδ
1+
D
C0
V = kC = k , (5.6.6)
kδ
1+
D
1 1 1
= + . (5.6.7)
V kC0 DC0 /δ
− 74 − 5

2. -
A C δ

dm
r= . (5.6.8)
dt
1 Ci = 0
 
D D
r= A(C − Ci ) = k1 AC k1 = , (5.6.9)
δ δ

dm
= k1 AC, (5.6.10)
dt
∆m = −k1 AC∆. (5.6.11)

2 Ci = C

r = k2 ACin = k2 AC n . (5.6.12)

3 Ci ̸= 0
r = k1 A(C − Ci ) = k2 ACin (5.6.13)

i
 2/3
3
A = 4π m2/3 . (5.6.14)
4πρ
ii

iii
iv
v r∝A

5.6.2

1.
 
1 1 1
− = kn t (5.6.15)
n − 1 (C − x)n−1 C n−1
2.

G
1
f0 (G) = 1 − (1 − G)1/3 = k0 t, (5.6.16)
f1 (G) = (1 − G)−2/3 − 1 = k1 t. (5.6.17)
5.7 − 75 −

2
f0 (G) = 1 − (1 − G)1/2 = k0 t, (5.6.18)

f1 (G) = (1 − G)−1/2 − 1 = k1 t. (5.6.19)

3
f0 (G) = G = k0 t, (5.6.20)

f1 (G) = ln(1 − G) = k1 t. (5.6.21)

5.6.3

1.
 
2 2DC0 M 2DC0 M
x = t = kt k= . (5.6.22)
ρ ρ
2.
1 Jander Jander

 √ 2 2kt
1− 3
1−G = 2. (5.6.23)
R
2 Gingsting

2 2DC0
1 − G − (1 − G)2/3 = t = kt. (5.6.24)
3 εR2
3 Carter
2DC0
[1 + (z − 1)G]2/3 + (z − 1)(1 − G)2/3 = z + (1 − z) t. (5.6.25)
εR2

5.7
1.

2.

3.
4.

5.
− 76 − 5

6.
1 ,
1∼3%

7. Tammann
8. Hedvall

5
5.1 1atm 1000◦ C 1000m3 20%CO 80%N2
◦
1000 C FeO Fe 2 Fe + O2 −−→ 2 FeO
1000◦ C ∆G⊖
1 = −368.82kJ 2 CO + O2 −−→ 2 CO2 , ∆⊖
2 = −307kJ
CO + FeO −−→ CO2 + Fe, ∆⊖ = 30.91kJ
pCO
∆⊖ = RT ln ,
pCO2
pCO n(CO)
= 18.54 = ,
pCO2 n(CO2 )
pV
n = 0.2 ×
= 1908.26mol,
RT
1
n(CO2 ) = n(Fe) = n = 97.65mol.
1 + 18.54
5.2 Ni 0.1atm µg/cm2
5.1 Ni

/h /h
/◦ C /◦ C
1 2 3 4 1 2 3 4
550 9 13 15 20 650 29 41 50 65
600 17 23 29 36 700 56 75 88 108

1
2
1 x2 ≈ kt x
 
∆E
D = D0 exp − ,
kT

k1
ln = −Ea (T1−1 − T2−1 ).
k2
2
 5 − 77 −

5
1. Bond Valence Na2 O
2. Ellingham
(1) The Ellingham diagram shows values of which thermodynamic quantity as a
function of temperature?
a. Standard electrode voltage;
b. Standard free energy change of reaction;
c. Partial pressure of gas;
d. Enthalpy change of reaction.
(2) For a closed system at equilibrium at a temperature T, which of the following
statements are true?
a. ∆G = 0;
b. ∆G⊖ = 0;
c. ∆H = T ∆S;
d. ∆S = 0.
(3) Why are the slopes of many of the lines on the Ellingham diagram almost
identical?
a. Most reactions involve the elimination of one mole of gas, so there is a similar
standard enthalpy change of reaction.
b. Most reactions involve the elimination of one mole of gas, so there is a similar
standard entropy change of reaction.
c. The activity of most of the metals is the same.
d. The partial pressure of the reacting gas is the same for all reactions.
(4) What thermodynamic quantity does the intercept at T=0 K for any standard
free energy vs T line signify?
a. The approximate value of the standard entropy change;
b. The approximate value of the standard enthalpy change;
c. The equilibrium constant for the oxidation reaction;
d. Heat capacity of the oxide.
(5) What is the decomposition temperature (to the nearest 50 K) for Ag2O? (This
question should be completed with the help of the interactive Ellingham diagram included
with this TLP).
a. 460K b. 500K
c. 540K d. 620K
(6) What is the decomposition temperature (to the nearest 50 K) for PdO? (This
question should be completed with the help of the interactive Ellingham diagram included
− 78 − 5

with this TLP).

a. 1050K b. 1100K
c. 1150K d. 1200K
(7) Which of the following elements can be used to produce Cr from Cr2O3 at
1200K? (This question should be completed with the help of the interactive Ellingham
diagram included with this TLP).
a. Mg b. Fe
c. Co d. Al
3. Ellingham T H2 −H2 O
H2 /H2 O p(H2 )/P (H2 O)
4. 1 - Fe-H2 SO4

2
5. BaCO3 + SiO2 −−→
BaSiO3 + CO2 XB BaCO3 BaO
BaSiO3

5.14 5

6. AgCl + Cu −−→ CuCl + Ag

7. 1400◦ C 3600h 20%
360h
8. SrO + TiO2 −−→ SrTiO3
Kirkendall SrO/TiO2
A) 1:1
B) 2:1
C) 1:2
D) 1:3
9.
A
B Jander
 5 − 79 −

C Carter
D) Ginstling
10. Fe2 O3

A)
B)
C)
D)

5
1.
2.
van’t Hoff
3.
4. 1 + 2 = 3 1 + = 2 1 = + 2
∆G0 ∼ T
5. 500◦ C 1000◦ C

6. Ellingham

7.
8. MgO SiO2 Mg2 SiO4

5
5

1. sij = (R0 /R)N = 1/4 R = 2.24 dij = Rij − blnsij = 2.75Å Na

1/8 a = 6.36Å
2. 1 b 2 ac 3 b 4 b 5 a 462K 6 c 1139K 7 ad

3. ∆G = ∆G⊖ + RT + lnK
M + O2 −−→ MO2 , ∆G1 ,
2 H2 + O2 −−→ 2 H2 O, ∆G2 ,

2 H2 + MO2 −−→ M + 2 H2 O, ∆G3 = ∆G2 − ∆G1 .

− 80 − 5

∆G = 0
p(H2 )
∆G⊖ ⊖ ⊖
3 = ∆G2 − ∆G1 = RT ln
p(H2 O)
p(H2 )
∆G⊖
3 ∼ T
p(H2 O)
3. 1 H+ H2 SO4 H+
C δ Fe - H+ Ci

k1 A(C − Ci ) = k2 ACi2 ,
p
−k1 + k12 + 4k1 k2 C
Ci = .
2k2
i k1 ≫ k2 C Taylor

−k1 + k1 (1 + 2k2 C/k1 )

Ci = C = ,
2k2
Fe
r = k2 AC 2 .
ii k1 ≪ k2 C
r
k1
Ci = C = 0,
k2 C

D
r = k1 A(C − Ci ) = k1 AC = AC.
δ
iii
p
(−k1 + k12 + 4k1 k2 C)2
r = k2 Ci2 = .
4k2
2 i m = kt
ii
 2/3
3
A = 4π m2/3 ,
4πρ
m0 − m1/3 = k ′ t
1/3

5. 5.14  
∆E
Jander D D = D0 exp −
kT
Ea
Jander r
6. 5.13 Wagner
7. Gingsting
2 2DC0
1 − G − (1 − G)2/3 = t = kt,
3 εR2
 5 − 81 −

2
1− × 0.2 − (1 − 0.2)2/3 = k × 3600,
3
k = 1.36 × 10−6 h−1 360h
2
1 − G − (1 − G)2/3 = 1.36 × 10−6 × 360,
3
Mathematica

6.54% G=1
2
1 − = 1.36 × 10−6 t,
3
t = 2.45 × 105 h
Jander
8. C Sr Ti 1:2 1:1 Kirkendall 1:2
9. C Carter
10. A Fe Fe′Fe = Fe×
Fe + e
′

5
 6
1.
2.
3.
4.

6.1
1.
inter-
face surface

interface phenomena surface phenomena

2.
1

83
− 84 − 6

6.2
6.2.1

1. ideal surface

2. clean surface

1
2
3

3. adsorption surface

4.

1
2
3

4
5.

6.

1
2 van der Waal

i
ii
iii
6.3 − 85 −

6.3
1.

0.5∼2nm 0.5∼2nm
2.
1
2
3
4
5
6
3.

4.

5.

5∼100nm

6.4
1.
erg/cm2
2. γ A
3.

4.
5. γlm ∆Hvap
γlm = 0.15∆Hvap . (6.4.1)

γsm = 0.16∆Hsubl . (6.4.2)

6.
− 86 − 6

6.1 γlm ∆Hvap

6
1.
A) 0∼10 nm
B) 2∼50 nm
C 0.5∼2 nm
D) 5∼20 nm
2.
A)
B)
C)
D)
3.
A)
B)
C)
D)
4.
 6 − 87 −

A) Ag>Na>W>
B) Na>Ag>W>
C) W>Ag>Na>
D) >Ag>Na>W
5.
A) PbI2 >SrSO4 >PbF2 >CaF2
B) PbI2 <SrSO4 <PbF2 <CaF2
C) PbI2 <SrSO4 <PbF2 <CaF2
D) PbI2 <PbF2 <SrSO4 <CaF2
6.
A) O in CoO > Co in CoO > Ba in BaO > Si in SiO2
B) Ba in BaO > O in CoO > Co in CoO > Si in SiO2
C) Ba in BaO > Si in SiO2 > O in CoO > Co in CoO
D) Co in CoO > O in CoO > Ba in BaO > Si in SiO2 .

6
6
1. C 0.5∼2nm
2. B
3. C

4. C 6.1
5. D F−
I− < F− ≈ SO2−
4 Pb2+ > Sr2+

6. D Si4+ O2− CoO BaO NaCl

2+ 2+ 2+
Co < O2− < Ba Co
 7
Nyquis

1. Ohm
V = IZ, (7.1)

Z
Z = Z ′ + Z ′′ j. (7.2)

Z′ Z ′′
2. Nyquis
1 −Z ′′ Z′
2
1
ωc = ; (7.3)
RC
3
τ = RC; (7.4)

4
5
3.
4. Nyquis
89
− 90 − 7

7.1

7.2 Nyquis

A) Z ′′ Z′
B) −Z ′′ Z′
C) Z ′′ f
D) −Z ′′ f

7
7
B −Z ′′ Z′
 8

8.1
1.
F = C − P + n. (8.1)

F P C n
n=2
2.

8.1

91
− 92 − 8

1 I gas II liquid III solid

2 OA OB OC
3 O
4 M F =2 N F =1
3. He

8.2 He

1 He
2 He λ

8.2
1.

8.3

A B M G M M1 M2
G1 G2 8.3
G1 b2 − b MM2
= = . (8.1)
G2 b − b1 M1 M
8.2 − 93 −

2.
1

8.4

8.5

8.6
− 94 − 8

3.

8.7

1
2
4.
1 1
2
3 2
4
5

8.3
8.3.1

Gibbs

1.

8.8
8.3 − 95 −

2.

8.9

8.3.2
1.
2.

3.
4.

5.

6.

7.

8.3.3
1.
1

2
3
4
2.
− 96 − 8

8.10

8.11

1 E1 L=A+B+D E2
L=A+C+D eAD

3
8.3 − 97 −

M’(熔体)
1. 由于M在C的初晶区内， Φ=1
L
因此从C出发连接CM并延 f=3
D 长到e3E线的F点上； M[C, (C)]
Φ=2 L→C
2. 沿着温度下降的方向移 f=2
M 动到E点； F[C, C+(A)]
Φ=3 L→A+C
3. 连接EM并延长交到AC f=1
F 边的D点上； E(到达)[D, A+C+(B)]
Φ=4
L→A+B+C
4. 连接CD，完成作图。 f=0
E(结束)[M, A+B+C]

8.12

8.13

3.
4.
1 P P+A=C+D
2

3
4
− 98 − 8

8.14

8.15

8.16
8.3 − 99 −

8.17

4. PPT

8.18
− 100 − 8

8
1. CO2

8.19 1

1 CO2
( ) ;
2 CO2 ?
2. ∆H > 0

(1)
(2) α−Fe 912◦ C 912◦ C 912◦ C
a = 0.290nm γ−Fe 912◦ C 912◦ C 912◦ C
a = 0.3646nm α−γ 912◦ C
912◦ C? ?
3.

8.20 3
 8 − 101 −

4. Na(A) K(B) 372.7K 336.9K

Na2 K(s) 280K Na(s) K
XB =0.42 258K , Na(s) K(s)
K XB =0.68 Na(s) K(s)

5.

8.21 5

6. PbO−Bi2 O3 α−Bi2 O3 γ−Bi2 O3 ; ββss

(∼30-65mol%PbO) 6:1 6Bi2 O3 :PbO 3:2
4:5 1:3

8.22 6
− 102 − 8

1 Bi2 O3
2 Bi2 O3 PbO ( )
3:2
3 725◦ C 20∼30mol%PbO
0 725◦ C
4) 70mol%(PbO) 800◦ C 635◦ C
635◦ C
5 1:3 Bi2 O3 :3PbO
7. ZrO2 −La2 O3

8.23 7

1 ;
2 ;
3 La2 O3 35% La Zr ?
8. Pb−Sn

8.24 8
 8 − 103 −

1 Sn 50wt%
?
2 α β ?
9.
TB > TC > TA > TE1 > TE2 > TE3 > TE

8.25 9

1
2 T1 T2
10. A B C tA = 1050◦ C tB = 980◦ C tC = 1300◦ C
tE = 800◦ C 35% A 40% B 25% C)
A-B B-C C- A tE1 = 850◦ C
40% A 60% B) tE 2 = 910◦ C 35%B 65%C tE3 = 1000◦ C 70%A 30%C

1 A-B
2 A-B-C
3 T1 = 1200◦ C T2 = 1000◦ C T3 = 850◦ C
11.

8.26 11
− 104 − 8

1
2
3 S S1 S2
4
5 M1 M2 M1 SO
12. 1 3 4 5 (
)

8.27 12

13.
1
2
3 6

8.28 13

14. MgO−Al2 O3 −SiO2

1 MS M2 S M4 A5 S2 M2 A2 S5 �
 8 − 105 −

8.29 14

2 4
3 3 4 5 7 8
4
5

8
8

1. 1 101.325kPa CO2

2 CO2

2. 1
−S1 dT + V1 dT = −S2 dT + V2 dT,
(V1 − V2 )dp = (S1 − S2 )dT,
dp ∆S ∆H
= = .
dT ∆V T ∆V
2 α−Fe bcc 2 1mol Fe n1 = 3.01 × 1023
V0,1 = 0.293 = 0.0244nm3 V1 = n1 V0,1 = 7.341 × 10−6 m3
− 106 − 8

γ−Fe fcc 4 1mol Fe n2 = 1.505 × 1023

V0,2 = 0.36463 = 0.0485nm3 V2 = n2 V0,2 = 7.294 × 10−6 m3
dp
∆V < 0 ∆H > 0 <0 912◦ C
dT
3. 1 f =0
2 β
3
4-6
4. L+Na→Na2 K L→K+Na2 K

8.30 4

5. I L+ → α + β
II L+γ →β
III L+δ →γ
IV L+ε→δ
V L + ζ2 → ε
VI L + η1 → ζ1
VII L + θ → η1
VIII L + λ(Mn) → θ
IX λ(Mn) + K → β(Mn)
X θ → η1 + λ(Mn)
XI λ(Mn) → η1 + β(Mn)
XII η1 → η2 + β(Mn)
XIII η1 → η2 + ζ1
XIV L1 + L2 → λ(Mn)
6. 1 730◦ C
2 575◦ C∼610◦ C
3 γ−Bi2 O3 ss+Liquid→ βss
4 Liquid→ βss+γ−PbOss
 8 − 107 −

5 Bi2 O3 PbO 1:3 635◦ C

580 605◦C
7. 1

8.31 7

2 1 C1 →T+P
2 L→C1 +P
3 L+P→C2
4 L→C2 +X
5 C2 →P+X
6 X→P+H
7 H→P+A
3 La:Zr=(0.35×2):0.65=14:13
8. 1
ws (50 − 19) = wl (61.9 − 50),
ws
= 0.384.
wl
2
wα (50 − 19) = wβ (97.5 − 50),
wα
= 1.532.
wβ
− 108 − 8

9. 1

8.32 9 1 1

8.33 9 2

10. 1

8.34 10 1

8.35 10 2
 8 − 109 −

8.36 10 3

11. 1-2

8.37 11 1-2

3 S S1 S2
4 u Lu +A→S+C
v Lv →B+C+S
y Ly +A→S+S1
o Lo +S1 →S+S2
w Lw +S2 →S+B
5-6
12.
13. 1

2
3
1 L→CS+CAS2 +C2 AS 2 L+A→CAS2 +A3 S2
14.
− 110 − 8

8.38 11 5

8.39 11 6
8 − 111 −

8.40 12

8.41 13 2
− 112 − 8

8.42 14
 A
1
1 O2−
2
3
a
b
c
d
1

A.1

2 4 4 8
3 M
a M2 O M
1/4 2/(1/4)=8
113
− 114 − A

b MO M
2/6=1/3 2/(1/3)=6
c MO M 2/4=1/2,
2/(1/2)=4
d MO2 M 4/6=2/3
2/(2/3)=3
1 (0 0 1/2)
(0 0 1/2) (0 1/2 0) (1/2 0 0) 0 1 (1/2
1/2 1/2)
3

2. NaCl MgO 4.21Å MnO 4.44Å CaO

4.80Å MgS 5.19 Å MnS 5.21Å CaS 5.68Å, NaCl Ca2+ O2−
Goldschmidt
MgS MnS
S2−
√
2 5.19 + 5.21
R(S2− ) = × = 1.84Å.
4 2
CaS Ca2+
1
R(Ca2+ ) = × 5.68 − 1.84 = 1.00Å.
2
S2− O2− CaO O2−

1
R(O2− ) = × 4.80 − 1.00 = 1.40Å.
2
3. BaTiO3
BaTiO3
a b BaTiO3
c = 4.036Å a = b = 3.992Å

= /

X
µ= ql
2e −2e
=8× × 0.061 + 4e × 0.12 + 2 × × (−0.036)
8 2
= 0.674eÅ
= 1.078 × 10−29 Cm,
 − 115 −

0.061Å

0.036Å Ba2+

Ti4+ O2-
0.12Å

c
a

A.2 3

V = a2 c = 3.9922 × 4.036 = 64.32Å3 = 6.432 × 10−29 m3 .

µ
Ps = = 0.1676C/m2 .
V

0
0

O
4.
NiAs
1 fcc
NaCl

2 hcp

NiAs
5. Bravais

1
2
3
1
− 116 − A

(2)
(3)

A.3

6.

1
2
3
4
1

√
2(r+ + r− ) = 3 × 2r− ,
√
r+ /r− = 3 − 1 = 0.732
2

√
2 × 2r− = 2(r+ + r− ),
√
r+ /r− = 2 − 1 = 0.414
3
√
109.5◦ 2r− / 3
q √ q √
(r+ + r− ) − (2r− / 3) = (2r− )2 − (2r− / 3)2 − (r+ + r− ),
2 2

r+ /r− = 0.225
4

 q 2
2
(2r− ) = 2
r− + (r+ + r− ) + (r+ + r− )2 − 2
r− ,
 − 117 −
√
( 3 − 1)2
r+ /r− = √ = 0.155
2 3
0 1 1

7. M2 O5
M Ml M Mh
VM′′′′′ Mi•••••
O′′i VO •• ••••
MMl M′Mh e ′
h •

8.

1 Mh2 O3 + 3Mi = 2Mhi + 3M×

••• ×
M + 3OO
•••

2 MX M 1 M×
M = Mi + e
′
•

1
2
9. M2 O5

1
M2 O5−xO× ′
O = VO + 2e + O2 (gas)
••

2
× × 5
M2+x O5 2MM + 5OO = 2Mi + O2 (gas) + 10e′ •••••

2
5 ′′′′′ ×
O2 (gas) = 2VM + 5OO + 10h •

2
1
O2 (gas) = O′′i + 2h •

2
10. NaCl Na Cl
1
Cl2 Na Cl2 (gas) = V′Ca + Cl×
Cl + h
•

2
1
Cl2 Cl Cl×Cl = VCl + Cl2 (gas) + e
• ′
2
Na Na Na× ′
Na = VNa + Na(gas) + h
•

Na Cl Na(gas) = VCl + Na×

Na + e
′ •

11. Mh2 O5 Ml2 O M2 O3+x

Mh2 O5 = 2MhM + 2O′′i + 3O× Mh2 O5 + 4h = 2MhM + 3O×
•• • ••

O O+
O2 (gas)
Ml2 O + O2 (gas) = 2Ml′′M + 3O×
O + 4h
•
Ml2 O + 2O′′i = 2Ml′′M + 3O×
O
12
La
Ba BaTiO3

1
La2 O3 + 2TiO2 = 2LaBa + 2Ti× × ′
•

Ti + 6OO + 2e + O2 (gas)
2
13. Sc2 O3 CaTiO3 Sc Ti
− 118 − A

2CaO + Sc2 O3 = 2Ca× × ′

Ca + 5OO + 2ScTi + VO
••

14 LaMnO3 Schottky
La
2La× × ′′′
La + 3OO = 2VLa + 3VO + La2 O3 (solid)
••

15. 1 MO M2 O3
2
3 MO M2 O3

1 2MlO = 2Ml′M + VO + 2O×

O
••

2 H2 O(gas) + VO + O× •• •

O = 2OHO
3 2MlO + H2 O(gas) = 2Ml′M + 2OHO + O×
•

O
(1) + (2) = (3)
16 CaF2 CaO F O CaO
Schottky
CaF2 = 2FO + Caו ′′
Ca + VCa CaF2 + VO = 2FO + Ca×
••

Ca
•

17. M2 O5 Schottky Frenkel

1 Schottky
0 = 2VM′′′′′ + 5VO ••

KS′ = [VM′′′′′ ]2 [VO ]5 ••

5[VM′′′′′ ] = 2[VO ] ••

 1/7  
5 ′′′′′ 25 ′ ′⊖ ∆HS⊖
••
[VO ] = [VM ] = K = KS exp −
2 4 S 7RT
2 Frenkel
M× ′′′′′
M = VM + Mi
•••••

KF′ = [VM′′′′′ ][Mi ] •••••

[VM′′′′′ ] = [Mi ] •••••

 
∆HS⊖
[VM′′′′′ ] = [Mi ] = •••••
(KF′ )1/2 = KF′⊖ exp −
2RT
18. M2 O5

(1)
5 × 5
M× ′
M + OO = Mi + 5e + O2 (gas)
•••••

2 4
K ′ = [Mi ]n5 pO2
5/4
•••••

•••••
n = 5[Mi ]
−5/24
n = 5[Mi ] = (5K ′ )1/6 pO2
•••••

(2)
5 5
O2 (gas) = VM′′′′′ + O× O + 5h + 5h
· •

4 2
−5/4
K ′ = [VM′′′′′ ]p5 pO2
 − 119 −

p = 5[VM′′′′′ ]
p = 5[VM′′′′′ ] = (5K ′ )1/6 pO2
5/24

19. MO MO1‐x
M1‐x O

1
O× ′ 2 1/2
O = VO + 2e + O2 (gas) ⇒ K1 = [VO ]n pO2 ,
•• ••

2
1 ′′ 2 −1/2
O2 (gas) = VM′′ + 2h + O×
O ⇒ K2 = [VM ]p pO2 ,
•

2
0 = VM′′ + VO ⇒ K3 = [VM′′ ][VO ],
•• ••

n + 2[VM′′ ] = p + 2[VO ].
••

−1/6
[VM′′ ] ∝ pO2
1/6 1/6
1 n = 2[VO ] ∝ pO2
••
p ∝ pO2
−1/6 −1/6 −1/6
2 p = 2[VM′′ ] ∝ pO2 n ∝ pO 2 [VO ] ∝ pO2
••

−1/4
[VM′′ ] = [VO ] ∝ pO2
1/2 1/4
3 ••
n ∝ pO2 p ∝ pO 2

A.4 3 Brouwer

20. Ml2 O Mh2 O3 M1+x O

M× × ′ 1
M + OO = Mi + 2e + 2 O2 (gas),
••
K1 = [Mi ]n2 pO2 1/2
••

1 Ml2 O M1+x O Ml′M

−1/6
n = 2[Mi ] ∝ pO2
••
Ml′M
−1/4
Ml′M = 2[Mi ] ••
n ∝ pO2
•
2 Mh2 O3 M1+x O MhM
−1/6
n = 2[Mi ] ∝ pO2
••
MhM •

−1/2
[Mi ] ∝ pO2
• ••
n = [MhM ]
21. M2 O3 (MhO2 )
Ki Schottky
Ks Ki ≫ Ks
− 120 − A

•
MhO2 M2 O3 MhM

1
O× ′ 2 1/2
O = VO + 2e + O2 (gas) ⇒ K1 = [VO ]n pO2 ,
•• ••

3 ′′′ 6 −3/2
O2 (gas) = 2VM′′′ + 6h + 3O×
O ⇒ K2 = [VM ]p pO2 ,
•

0 = e′ + h ⇒ K3 = np,
•

Schottky
0 = 2VM′′′ + 3VO ⇒ K3 = [VM′′ ]2 [VO ]3 .
•• ••

−1/6
[VM′′′ ] ∝ pO2
1/6 1/4
n = 2[VO ] ∝ pO2
••
p ∝ pO2
−1/2
[VM′′′ ] ∝ pO2
3/4
[VO ] ∝ pO2
• ••
n = [MhM ] = const
−1/4
[MhM ] = 3[VM′′′ ] = const
1/4
p ∝ pO 2 n ∝ pO2
•

−3/16 −1/8
p = 3[VM′′′ ] ∝ pO2
3/16
n ∝ pO2 [VO ] ∝ pO2
••

A.5 5 Brouwer

22. Mh2 O3 MO

1
Mh2 O3 = 2MhM + 2e′ + 2O× 2 1/2 2
O + O2 (gas) ⇒ K1 = [MhM ] pH2 O n ,
• •

2
Mh2 O3 = 2MhM + VM′′ + 2O× ′′
O ⇒ K2 = [VM ][MhM ] .
2
• •

−1/8
[VM′′ ] ∝ pO2
1/4
n = [MhM ] ∝ pO2
•
K1
−1/4
[MhM ] = 2[VM′′ ] = const n ∝ pO2
•
K2
 − 121 −

23. MO1‐x

1
O× ′ 2 1/2
O = VO + 2e + O2 (gas) ⇒ K1 = [VO ]n pO2 ,
•• ••

2
1
H2 O(gas) + 2O× ′ 2 2 1/2 −1
O = 2OHO + 2e + O2 (gas) ⇒ K2 = [OHO ] n pO2 pH2 O
• •

2
−1/6 1/2
n = 2[VO ] ∝ pO2 [OHO ] ∝ pO2
•• •

1/4 −1/2
n = [OHO ] ∝ pO2 [VO ] ∝ pO2
• ••

24. Bond Valence Na2 O

sij = (R0 /R)N = 1/4 R = 2.24 dij = Rij − blnsij = 2.75Å Na
1/8 a = 6.36Å
25. Ellingham
(1) The Ellingham diagram shows values of which thermodynamic quantity as a
function of temperature?
a. Standard electrode voltage;
b. Standard free energy change of reaction;
c. Partial pressure of gas;
d. Enthalpy change of reaction.
(2) For a closed system at equilibrium at a temperature T, which of the following
statements are true?
a. ∆G = 0;
b. ∆G⊖ = 0;
c. ∆H = T ∆S;
d. ∆S = 0.
(3) Why are the slopes of many of the lines on the Ellingham diagram almost
identical?
a. Most reactions involve the elimination of one mole of gas, so there is a similar
standard enthalpy change of reaction.
b. Most reactions involve the elimination of one mole of gas, so there is a similar
standard entropy change of reaction.
c. The activity of most of the metals is the same.
d. The partial pressure of the reacting gas is the same for all reactions.
(4) What thermodynamic quantity does the intercept at T=0 K for any standard
free energy vs T line signify?
a. The approximate value of the standard entropy change;
b. The approximate value of the standard enthalpy change;
c. The equilibrium constant for the oxidation reaction;
d. Heat capacity of the oxide.
− 122 − A

(5) What is the decomposition temperature (to the nearest 50 K) for Ag2O? (This
question should be completed with the help of the interactive Ellingham diagram included
with this TLP).
a. 460K b. 500K
c. 540K d. 620K
(6) What is the decomposition temperature (to the nearest 50 K) for PdO? (This
question should be completed with the help of the interactive Ellingham diagram included
with this TLP).
a. 1050K b. 1100K
c. 1150K d. 1200K
(7) Which of the following elements can be used to produce Cr from Cr2O3 at
1200K? (This question should be completed with the help of the interactive Ellingham
diagram included with this TLP).
a. Mg b. Fe
c. Co d. Al
1 b 2 ac 3 b 4 b 5 a 462K 6 c 1139K 7 ad

26. Ellingham T H2 −H2 O

H2 /H2 O p(H2 )/P (H2 O)
∆G = ∆G⊖ + RT + lnK
M + O2 −−→ MO2 , ∆G1 ,
2 H2 + O2 −−→ 2 H2 O, ∆G2 ,

2 H2 + MO2 −−→ M + 2 H2 O, ∆G3 = ∆G2 − ∆G1 .

∆G = 0
p(H2 )
∆G⊖ ⊖ ⊖
3 = ∆G2 − ∆G1 = RT ln
p(H2 O)
p(H2 )
∆G⊖
3 ∼ T
p(H2 O)
27. 1 - Fe-H2 SO4

2
1 H+ H2 SO4 H+
C δ Fe - H+ Ci

k1 A(C − Ci ) = k2 ACi2 ,
 − 123 −
p
−k1 + k12 + 4k1 k2 C
Ci = .
2k2
i k1 ≫ k2 C Taylor

−k1 + k1 (1 + 2k2 C/k1 )

Ci = C = ,
2k2
Fe
r = k2 AC 2 .
ii k1 ≪ k2 C
r
k1
Ci = C = 0,
k2 C

D
r = k1 A(C − Ci ) = k1 AC = AC.
δ
iii
p
(−k1 + k12 + 4k1 k2 C)2
r= k2 Ci2 = .
4k2
2 i m = kt
ii
 2/3
3
A = 4π m2/3 ,
4πρ
m0 − m1/3 = k ′ t
1/3

28. BaCO3 + SiO2 −−→

BaSiO3 + CO2 XB BaCO3 BaO
BaSiO3

A.6 28

 
∆E
Jander D D = D0 exp −
kT
Ea
− 124 − A

Jander r
29. AgCl + Cu −−→ CuCl + Ag
Wagner

A.7 29

30. 1400◦ C 3600h 20%

360h
Gingsting
2 2DC0
1 − G − (1 − G)2/3 = t = kt,
3 εR2

2
1− × 0.2 − (1 − 0.2)2/3 = k × 3600,
3
k = 1.36 × 10−6 h−1 360h
2
1 − G − (1 − G)2/3 = 1.36 × 10−6 × 3600,
3
Mathematica

6.54% G=1
2
1− = 1.36 × 10−6 t,
3
t = 2.45 × 105 h
Jander
31.
A) 0∼10 nm
B) 2∼50 nm
C 0.5∼2 nm
D) 5∼20 nm
C 0.5∼2nm
32.
A)
B)
C)
D)
 − 125 −

B
33.
A)
B)
C)
D)
C

34.
A) Ag>Na>W>
B) Na>Ag>W>
C) W>Ag>Na>
D) >Ag>Na>W
C γlm ∆Hvap
6.1
35.
A) PbI2 >SrSO4 >PbF2 >CaF2
B) PbI2 <SrSO4 <PbF2 <CaF2
C) PbI2 <SrSO4 <PbF2 <CaF2
D) PbI2 <PbF2 <SrSO4 <CaF2
D F−
I− < F− ≈ SO2−
4 Pb2+ > Sr2+

36. SrO + TiO2 −−→ SrTiO3

Kirkendall SrO/TiO2
A) 1:1
B) 2:1
C) 1:2
D) 1:3
C Sr Ti 1:2 1:1 Kirkendall 1:2
37.
A) O in CoO > Co in CoO > Ba in BaO > Si in SiO2
B) Ba in BaO > O in CoO > Co in CoO > Si in SiO2
C) Ba in BaO > Si in SiO2 > O in CoO > Co in CoO
D) Co in CoO > O in CoO > Ba in BaO > Si in SiO2 .
D Si4+ O2− CoO BaO NaCl
Co2+ < O2− < Ba2+ Co2+
− 126 − A

38.
A) Z ′′ Z′
B) −Z ′′ Z′
C) Z ′′ f
D) −Z ′′ f
B −Z ′′ Z′
39.
A
B Jander
C Carter
D) Ginstling
C Carter
40. Fe2 O3

A)
B)
C)
D)
A Fe Fe′Fe = Fe×
Fe + e
′

41. CO2

A.8 41

1 CO2
( ) ;
2 CO2 ?
1 101.325kPa CO2
 − 127 −

2 CO2

42. ∆H > 0

(1)
(2) α−Fe 912◦ C 912◦ C 912◦ C
a = 0.290nm γ−Fe 912◦ C 912◦ C 912◦ C
a = 0.3646nm α−γ 912◦ C
912◦ C? ?
1
−S1 dT + V1 dT = −S2 dT + V2 dT,
(V1 − V2 )dp = (S1 − S2 )dT,
dp ∆S ∆H
= = .
dT ∆V T ∆V
2 α−Fe bcc 2 1mol Fe n1 = 3.01 × 1023
V0,1 = 0.293 = 0.0244nm3 V1 = n1 V0,1 = 7.341 × 10−6 m3
γ−Fe fcc 4 1mol Fe n2 = 1.505 × 1023
V0,2 = 0.36463 = 0.0485nm3 V2 = n2 V0,2 = 7.294 × 10−6 m3
dp
∆V < 0 ∆H > 0 <0 912◦ C
dT
43.

A.9 43
− 128 − A

1 f =0
2 β
3
4-6
44. Na(A) K(B) 372.7K 336.9K
Na2 K(s) 280K Na(s) K
XB = 0.42 258K , Na(s) K(s)
K XB = 0.68 Na(s) K(s)

L+Na→Na2 K L→K+Na2 K

A.10 44

45.

A.11 45
 − 129 −

I L+ → α + β
II L+γ →β
III L+δ →γ
IV L+ε→δ
V L + ζ2 → ε
VI L + η1 → ζ1
VII L + θ → η1
VIII L + λ(Mn) → θ
IX λ(Mn) + K → β(Mn)
X θ → η1 + λ(Mn)
XI λ(Mn) → η1 + β(Mn)
XII η1 → η2 + β(Mn)
XIII η1 → η2 + ζ1
XIV L1 + L2 → λ(Mn)
46. PbO−Bi2 O3 α−Bi2 O3 γ−Bi2 O3 ; ββss
(∼30-65mol%PbO) 6:1 6Bi2 O3 :PbO 3:2
4:5 1:3

A.12 46

1 Bi2 O3
2 Bi2 O3 PbO ( )
3:2
3 725◦ C 20∼30mol%PbO
0 725◦ C
− 130 − A

4) 70mol%(PbO) 800◦ C 635◦ C

635◦ C
5 1:3 Bi2 O3 :3PbO
1 730◦ C
2 575◦ C∼610◦ C
3 γ−Bi2 O3 ss+Liquid→ βss
4 Liquid→ βss+γ−PbOss
5 Bi2 O3 PbO 1:3 635◦ C
580 605◦C
47. ZrO2 −La2 O3

A.13 47

1 ;
2 ;
3 La2 O3 35% La Zr ?
1
2 1 C1 →T+P
2 L→C1 +P
3 L+P→C2
4 L→C2 +X
5 C2 →P+X
6 X→P+H
7 H→P+A
3 La:Zr=(0.35×2):0.65=14:13
 − 131 −

A.14 47

48. Pb−Sn

A.15 48

1 Sn 50wt%
?
2 α β ?
1
ws (50 − 19) = wl (61.9 − 50),
ws
= 0.384.
wl
− 132 − A

2
wα (50 − 19) = wβ (97.5 − 50),
wα
= 1.532.
wβ
49.
TB > TC > TA > TE1 > TE2 > TE3 > TE

A.16 49

1
2 T1 T2
1

A.17 49 1 1

A.18 49 2
 − 133 −

50. A B C tA = 1050◦ C tB = 980◦ C tC = 1300◦ C

tE = 800◦ C 35% A 40% B 25% C)
A-B B-C C-A tE1 = 850◦ C 40%
A 60% B) tE2 = 910◦ C 35%B 65%C tE3 = 1000◦ C 70%A 30%C

1 A-B
2 A-B-C
3 T1 = 1200◦ C T2 = 1000◦ C T3 = 850◦ C
1

A.19 50 1

A.20 50 2

A.21 50 3
− 134 − A

51.

A.22 51

1
2
3 S S1 S2
4
5 M1 M2 M1 SO
1-2

A.23 51 1-2

3 S S1 S2
4 u Lu +A→S+C
v Lv →B+C+S
y Ly +A→S+S1
o Lo +S1 →S+S2
w Lw +S2 →S+B
5-6
 − 135 −

A.24 51 5

A.25 51 6

52. 1 3 4 5 (
)

A.26 52
− 136 − A

A.27 52

53.
1
2
3 6

A.28 53
 − 137 −

A.29 53 2

3
1 L→CS+CAS2 +C2 AS 2 L+A→CAS2 +A3 S2
54. MgO−Al2 O3 −SiO2

A.30 54

1 MS M2 S M4 A5 S2 M2 A2 S5 �
− 138 − A

2 4
3 3 4 5 7 8
4
5

A.31 54
 B
20 1.5 30
1. Bravais ( )
A. B. C. D.
2. ( )
A. 34.01% B. 52.36% C. 68.02% D. 74.05%
3. % ( )
A. hcp 50% B. hcp 100% C. fcc 50% D. fcc 50%
4. BaTiO3 t = 1.06 ( )
A. B. C. D.
5. Pauling 0.85
( )
A. 12 B. 8 C. 6 D. 4
6.
1 Frenkel
2
3
4 ( )
A. (1)(2) B. (3)(4) C. (1)(4) D. (2)(3)
7. ( )
1
A. Ml2 O + O2 (gas) = 2Ml′M + 2O×
O + 2h
•

×
2
′
B. MM = Mi + e •

C. 2MlO + H2 O(gas) = 2Ml′M + 2OHO + O×

•

O
3 ′′′ ×
D. O2 (gas) = 2VM + 6h + 3OO
•

2
139
− 140 − B

8. Brouwer ( )
A. log[ ] logpO2 B. [ ] pO2
C. log[ ] 1/T D. log[ ] log(1/T )
9. r1 r2
r1 − r2
0.15 ⩽ ⩽ 0.30
r1
( )
A. B. C. D.
10. van t Hoff
( )
A. B. C. D.
11.
( )
A. B. C. D.
12. TiO2 + SrO −−→ SrTiO3 Kirk-
endall TiO2 /SrO ( )
A. 1:1 B. 1:2 C. 2:1 D. 4:1
13. ( )
A. B.
C. D.
14. ( )
A. B. C. D.
15. nm ( )
A. 0.1∼0.25 B. 0.25∼0.5 C. 0.5∼0.1 D. 0.5∼2
16. ( )
A. O in CoO > Co in CoO > Ba in BaO > Si in SiO2
B. Ba in BaO > O in CoO > Co in CoO > Si in SiO2
C. Ba in BaO > Si in SiO2 > O in CoO > Co in CoO
D. Co in CoO > O in CoO > Ba in BaO > Si in SiO2
17. ( )
A. Z ′′ Z′
B. −Z ′′ Z′
C. Z ′′ f
D. −Z ′′ f
18. M ( )
A. A: 30%, B: 20%, C: 50% B. A: 25%, B: 35%, C:40%
C. A: 50%, B: 30%, C: 20% D. A: 20%, B: 50%, C: 30%
 − 141 −

B.1 18

19. ( )
A. B. C. D.
20. ( )
A. L+A=B+C B. L=A+B+C C. L+B+C=A D. L+B=A+C

B.2 20

9 21 4 22 8 23 12
24∼26 2 27 4 28 8 29 12 54
21.

22. M2 O3
1 Schottky

2 Frenkel
− 142 − B

3 Frenkel

5 M2 O3−x

6 M2+x O3

7 M2−x O3

8 M2 O3+x

23.
1 M2−x O3

2 M2−x O3

3 M2 O3−x

4 M2 O3−x

5 M2+x O3

6 M2+x O3

7 M2 O3+x

8 M2 O3+x

24. Sc2 O3 CaTiO3 Sc Ti

 − 143 −

25. CaF2 CaO F O CaO Schottky

26. LaMnO3 Schottky

La

27.

28.
XX XXX 8 25 20 10
XXX (
XXX
20

B.3 28

1 20 3
2 20 18 18
3
3 18
XXX 2
− 144 − B

29. D

B.4 29

1 M1 M2 M1 AD M2 AD
( 8
2 BC 4

2 30 6 31 10 16
◦
30. 800 C 3000h 30%
 − 145 −

31. M2 O3 M2 O3‐x
M2‐x O3 Brouwer
 C
1–5 DADCB
6–10 DBABC
11–15 BCACD
16–20 DBCBA
21. CaF2 fcc
A fcc
Na2 O fcc
22-23.
24. 2CaO + Sc2 O3 = 2Ca× × ′
Ca + 5OO + 2ScTi + VO
••

25. CaF2 = 2FO + Ca×

• ′′
Ca + VCa CaF2 + VO = 2FO + Ca×
••

Ca
•

• × × ′ 1
26. La2 O3 + 2TiO2 = 2LaBa + 2TiTi + 6OO + 2e + O2 (gas)
2
27.
28. 1 273.15K
253K

2
3
L−−→B L+B−−→D
29. 1 M1 −−−−−→ I −−−−−−−→ K (L + B −−→ D + A)
A D
L−−→A L−−→A+C L−−→A+D
M2 −−−−−→ I −−−−−−−→ K (L + B −−→ D + A) −−−−−−−→ E (L −−→ A + C + D)
A C D
2
30. Gingstling 86021h
147
− 148 − C

C.1 29 1

C.2 29 2

31.