Tabulation, bibliography, and structure of binary intermetallic compounds I Compounds of lithium, sodium, potassiu, and rubidium

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Ames Laboratory ISC Technical Reports Ames Laboratory

9-1-1956

Tabulation, bibliography, and structure of binary

intermetallic compounds. I. Compounds of

lithium, sodium, potassiu, and rubidium.

S. G. Epstein

Iowa State College D. M. Bailey Iowa State College R. L. Smythe Iowa State College G. R. Kilp Iowa State College J. F. Smith Iowa State College

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Recommended Citation

(2)

Tabulation, bibliography, and structure of binary intermetallic compounds.

I. Compounds of lithium, sodium, potassiu, and rubidium.

Abstract

The compilation of the material in this report was undertaken to provide a convenient reference source for intermetallic compounds. An adequate bibliography is required for most efficient use. It is in this sense and because of the addition of more compounds that the compilation is considered an extension of the

compilation in Smithell's "Metals Reference Book."

Disciplines

Ceramic Materials | Engineering | Materials Science and Engineering | Metallurgy

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ISC-795

U N I T E D S T A T E S A T 0 M I C E N E R G Y C 0 M M I S S I 0 N

TABULATION, BIBLIOGRAPHY, AIID STRUCTURE OF BINARY INTERMETALLIC COMPOUNDS.

I. COMPOUNDS OF LITHIUM, SODIUM, POTASSIUM, AND RUBIDIUM.

by

S. G. Epstein, D. M. Bailey, R. L. Smythe,

G. R. Kilp and J. F. Smith

September 1, 1956

Physical Scicnc ~s {eudi 1 ":' F.ooro

Ames Laboratory at

Iowa State College F. H. Spedding, Director

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This report is distributed according to the catagory Metallurgy and Ceramics, as listed in TID-4500, July 15, 19.56.,

This report was prepared as an account of Government sponsored work.

Neither the United States, nor the Commission, nor any person acting on behalf of the Commission:

A.. Makes any warranty or representation, express or implied, with

respect to the accuracy, completeness, or usefulness of the infor-mation contained in this report, or that the use of any inforinfor-mation apparatus, method, or process discl~sed in this report may not infringe privately owned rights; or

B. Assumes any liabilities with respect to the use of, or for damages resulting from the use of any information, apparatus,

method, or process disclosed in this report.

As used in the above, 11person,acting on behalf of the Commission" includes any employee or contractor of the Commissio~ to the extent that such employee or contractor prepares, handles or distributes, or provides access to, any information pursuant to his employment or contract with the Commission.

Printed in the USA. Price

25

cents. Available from the

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TABLE OF CONTENTS

Introduction. • • •

. . .

. . . .

. .

. . .

.

Part I~ Tabulation of Compounds.

. . .

.

. . . .

.

. .

Part II~ References • • • • •

Part III: Structure Details.

. .

. . .

.

. . .

. .

. . .

.

. . .

. . . .

. .

6

22

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5

TABULATION, BIBLIOGRAPHY, AND STRUCTURE OF BINARY INTERMETALLIC COMPOONDS. I. COMPOUNDS OF LITHIUM, SODIUM, POTASSIUM, AND RUBIDIUM.

By S. ,G. Epstein, D. M. Bailey, R. L. S~the, G. R. Kilp, and J. F. Smith

INTRODUCTION

The compilation of the material in this report was undertaken to provide a convenient reference source for intermetallic compounds. An adequate

bibliograpny is required for most efficient use. It is in this sense and because of the addition of more compounds that the compilation is considered an exten~ion of the compilation in Smi thell 1 s "Metals Reference Book."

Undoubtedly there are some compounds listed in the compilation which either do not exist or have been assigned the wrong formulae. It seems

o~vious, for instance, that not. all of the reported sodium-mercury compounds should exist. For purposes of evaluation, the experimental basis for the report of a compound is included under "Remarks" after the comp911nd.

The material is, separated into three·sections. The first 1_{part consists}

of a tabulation and includes the crystal class, lattice parameters, and

(8)

COMPOUNDS LiAg CRYSTAL CLASS, cubic cubic hexag-onal hexag-onal hexag-onal

PART I: TABUlATION OF COMPOUNOO

LATTICE 0 PARAMETERS (A)

a=J.l7

a:6.261 c=l0.25

a•2. 788 c=4.J94

a=4.37l

c=2 .515

REJ.<"ER-STRUCTURE REMARKS ENCES

B2 X-ray powder data, numeri-cal intensitief?, thermal

analysis, metallography. 1, 2,3,4

X-r~ powder data, quali-tative intensities, numer-ical intensities; formulae Li₉Ag_1,,_Li10Ag_{1 ,} _{and Li12Ag} also ~eported ~nd are

probably indicative of a region of solid solubility.

1, 2.,

5

Some evidence for super-lattice, possibly Fe₃Al type below ~420°C; superiattice formulae reported also as Li₁Mg~, cubic with a=9.7,

ana

as Li₂Mg~, cubic with 91,92, a•J.513; still in debate. 6,7

cl4

Thermal analysis and hardness data.

X-ray powder data, numer-8

ical intensities. 9

A3 Numerical intensities,

x-ray powder data. 9,10

X-ray powder data. 6

LD~h--

X-ray powder data, numerical intensities, thermal analysis, P63/mm~ electrical resistance;

formulae Li3zn7, Lin Rzn2, and LiZn2 also report~d with same lattice

(9)

CRYSTAL LATTICE 0

REFER-COMPOUND CLASS PARAMETERS(A) STRUCTURE REMARKS ENCES

Li2Zn3 cubic a:4.27 Thermal analysis, electric resistance, and x-ray

powder data. 3,6,11

LiZn cubic a=6.222 B32 X-ray powder data,

numer-ical intensities. 3,.4

LiCd3 hexag- a:3.089 A3 X-ray powder data, numer-onal c=4.899 ical intensities, thermal

analysis, conductivity and

dilatometric data. 12,13

LiCd3 cubic a=8.62 compli- X-ray powder data, thermal

cated analysis. 3,14

cubic

LiCd2 Phase diagram. 15

LiCd cubic a::6. 701 B32 X-ray powder data,

numer-ical intensities. 4,12

LiCd cubic a:3.33 B2 X-ray powder data, numer-ical intensities, thermal

data. 3,16,14

Li3Cd cubic a::4.259 Al X-ray powder data, numer-ical intensities, thermal

analysis. 3,12,16

LiHg5 Phase diagram--doubtful. 17

LiHg3 hexag- a:6.253 _D019 X-ray powder data, numer-onal c=4.804 ical intensities, thermal

analysis. 3,18,19

LiHg2 II _18,19

LiHg cubic a:3.24 B2 X-ray powder data, numer-ical intensities; parameter

values reported as high 3,4,18,

as 3.294. 19

Li 2Hg X-ray powder data, thermal

(10)

CRYSTAL LATTICE 0

REFER-COMPOUND CLASS PARA.METERS(A) STRUCTURE REMARKS ENCES

Li3Hg cubic a:::6.561

no

₃ X-ray powder data, numer-ical intensities, thermal

analysis. 18,19

Li6Hg Thermal analysis. 19

LiAl cubic a::6.372 B32 X-ray powder data, quali-tative intensities, thermal

analysis, temperature- 20,21 resistance and micrographic 22,23,

data. 24

Li2Al Thermal analysis,

tempera-ture-resistance and

micro-graphic data. 23,24

LiGa cubic a::6.208 B32 X-ray powder data,

Liin cubic a:6.8oo B32 X-ray powder data, numer-ical intensities, thermal

analysis. 3,4,19

Li2T13 Thermal analysis and

tern-perature-resistance data. 25

LiTl cubic a::3.431 B2 Thermal analysis, x-ray pow-der, numerical intensity and

temperature-resistance data.3,4,25

Li2Tl Thermal analysis and

tem-perature-resistance data. 25

Li5T12 II ₂₅

Li3Tl II ₂₅

Li4Tl II ₂₅

Li2Si X-ray powder data; no

intensities given. 26

(11)

CRYSTAL LATTICE 0

REFER-COMPOUND CLASS PARAMETERS (A) STRUCTURE REMARKS ENCES .

----

----Lisn4 Thermal analysiso 27

Li 2sn5 Thermal analysis and

tem-perature-res istcn ce data. 15,28

LiSn2

_"

27,28

LiSn Thermal analysis, temper- 27,2.:3,4

ature-resistance data, x-ray powder data; no intensities given.

Li3Sn2 Thermal analysis. 15,27

Li2Sn Thermal analysis and

tern-perature-resistance data. 27,28

Li5Sn2 II _27,28

Li7Sn2 II _27,28

Li4Sn

_"

27,28

LiPb cubic a=3.529 B2 Thermal analysis, tem

pera-ture-resistance and x-ray

powder data. 4,29,30

Li5Pb2 Thermal analysis and

tem-perature-resistance data. 30

Li10Pb3 cubic a=lO.OlO _D83 X-ray powder data,

numer-ical intensities. 31

Li3Pb hexag- a:4.27 _D018 Thermal analysis and

tem-onal c=7

.59

perature-resistance data. 30

Li7Pb2 II ₃₀

Li4Pb II ₃₀

Li3N hexag- a=3 .. 665 X-ray powder data,

numer-onal c=3.890 ical intensities. 32

Li3N cubic a=5 .51 X-ray povrder data, q1

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COMPOUND

Li3P

Li3As

o<-Li3Sb

fJ

-Li3Sb

LiBi

Li3Bi

Li₂S

Li2Se Li2Te NaAu CRYSTA.L CLASS hexag-onal hexag-onal hexag-onal cubic tetrag-onal cubic cubic cubic cubic

· hexag-onal

LATTICE o PARAMETERS (A)

a•4.273 c:7 .594

a=4.396 c:7 .. 826

a::4.no c:8.J26 a:6.572 a:3.368 c::4.256 a=6. 722 a:5. 720

a:6 •. 0l7

a::6.517

a=7 .5ot2 c=l2. 29

REFER-STRUC'IURE REMARKS

_{- -}

ENCES

n~s X-ray powder data, numer-ical intensities. 34

Do-18 It ₃₄

DO:J.s It 34

no

₃ It ₃₄

110 X-ray powder data, numer-ical intensities, thermal analysis and electrical

resistances. 3,4,3.5

D03 Thermal analysis and

electrical resistances.

3,35,36

Cl X-ray powder data,

Cl

_"

37

Cl

_"

37

Cl4

X-ray powder data,

Debye-Scherrer. 38.

Thermal analysis.

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CRYSTAL LATTICE 0 REFER-COMPOOND ClASS PARAMETERS (A) STRUCTURE REMARKS ENC&S

NaAu2 cubic a=7. 7872

±

.0023 Cl5 X-ray powder data. 40,41,

59

Na2Au tetrag- a:7 .402 Cl6 Rotation, Weissenberg,

onal c:5.511 and x-ray powder data. 41

Nazn13 cubic a=l2.2836 _D23 X-ray powder data, compar-! 0.0003 ison of F0 and F~; F

obtained by multlple0_film

technique. 61,40

NaCd2 cubic X-ray powder data, thermal,

micrographic, and

electri-cal investigations. 42,53

NaCd5 Thermal, microbTaphic, and

electrical investigations.

₅₃

Nacd6 II

₅₃

NaHg or tho- a=7 .19 _{- 2h--}/i517 Weissenberg and precession rhombic b:l0 •. 79 x-ray data, visual

estima-c=5.21 Cmc_!!!7 tion of intensities, least squares refinement of data;

R

=~I

F0 - Fe J

~ iFol

=

20.3't.62

NaHg2 hexag- a=5 .0290 C32 X-ray powder data. 62 onal :!: .0005

c=3.2304 ! .0016

NaHg₄ hexag- a:61.5 ~230 NaHg_{4 per cell;}

onal c=9. 7 Weissenberg data. 62

NaHg5 Thermal preparation (grown

from melt); existence

doubtful. 64

NaH~ It ₆₄

(14)

COMPOUND NaHg8 NaHg9 NaHg10 NaHg12 NaH;gl4

Na₃Hg

Na₃_Hg2

Nain NaTl NaSi CRYSTAL CLASS tetrag-anal rhombo-hedral cubic cubic

LATTICE 0

PARAMETERS(A)

a:S.52 c:7 .80

a=7 .312

REFER-STRUCTURE REMARKS ENCES

Thermal preparation{grown from melt); existence 64 doubtful.

It ₆₄

"

64

II ₆₄

Thermal analysis. 46

LOG~--

Weissenberg and precession

x-ray data, visual

estima-P42/mn~tion of intensities refined

B32

by electron density maps, least squares refinement

of data. 62

Precession x-ray data. 62

Thermal analysis. 46

X-ray powder data. 43,59

II _44,59

Thermal analysis and tem -perature-resistance data. 54

II 54

Thermal analysis; existence

cp. estionable. 47

Thermal analysis and

tem-perature-resistance data. 54,47

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COMPOUND NaSi2 NaGe NaSn NaSn2 NaSn3 NaSn4 Nasn6 Na2Sn Na3sn Na4sn Na4sn3 Na4sn9

Na₁~n4

NaPb

Na Pb _2.

CRYSTAL LATTICE 0

CLASS PARAMETERS (A) STRUCTURE REMARKS

REl<"'ER-ENCES

tetrag- a=4.98 X-ray powder data; possi-onal c:l6~ 7 bility of different cell. 60

Reported as formed by method used above for NaSi. ₅₅

fhase diagram. 66

It ₆₆

II ₆₆

It ₆₆

II ₆₆

Reported on basis of for-mation of precipitate~ and discontinuity in potentia-metric titration curve \men Na was titrated with Sni 2 in aqueous NH3 • 67 or tho- a=9.82 """D86 Powder, rotation, and

rhombic b=22.82 Weissenberg x~ray data. 45 c:5.59

tetrag- a:lo.58o fj520 Crude single crystal data anal ±o.oo5 4h- plus x-ray powder data;

c::l7 .. 746 ~/acE_? least s~ares refinement of

:0.015 Pb positions; (FQ-FC) refine-ment of Na posit~ons; powder intensities gotten by compar-ison with calibrated film. 63,59 H298: -11.& kcal/mol.

(16)

CRYSTAL LATTICE REFER-COMPOUND CLASS PARAMETERS(A) STRUCTURE REMARKS ENCES

Na2Pb5 a=4.88 Ll2. Conflicting x-ray evidence l about compound's existence. 17,65

Na!J'b Phase diagram. 17

Na4Pb7 cubic a.=4.873 Reported on basis of precip-itation during potentiometric titraticn, and discontinuity

in potentiometric titration

curve. 67,3

Na4Pb9 lti ₆₇

Na5Pb2: Phase diagram. Ji.7

Na15Pb

4

cubic a=l3 .31 D86 Powder, rotation, and Weissenberg x-ray data; visual estimation of

inten-sities. 45,33

Na3;1Pba ~.=13.2.7 78 atoms per cell. _69,94

NaJJ hexag- a:4 .• 99 DOJ.B

J4

onal c=8.81

Na₃~s hexag- ~=5.089 DO~e X-ray powder data. 34,59

anal c=8.99 67

Na₃!ts₃~ Reported on basis of precip-itation during potentiometric titration, and discontinuity in potentiometric titration

curve 67

Na~s5

_"

_'

67

Na_t.s 7 Ill ₆₇

NaSb Analog of NaBi 44,67

Na3Sb hexag- a.=5 .367 _D018 34

(17)

CRYSTAL LATTICE

REFER-COMPOUND CLASS PARAMETERS(£) STRUCTURE REMARKS ENCES

NaBi tetrag- a=3 .47 LlO Superlattice; x-ray powder

onal c=4.81 data. 44,59,3

Na3Bi hexag- a=5.459 D018 X-ray powder data. 34,59 onal c=9.674

N_a3Bi5 Reported on basis of

precip-itation during potentiometric titrAtion, and discontinuity ip potentiometric titration

curve. 67

Na2

o

f.c.cubic a=5.56 Cl X-ray powder data, visual

estimation of in_{tensities. 37,49}

Na2S f.c.cubic a::6.526 (Cl X-ray powder data. 37,59,)

Na~2 Reported on basis of

precip-itation during potentiometric titration, and discontinuity in potentiometric titration

curve. 67

Na2S3

_"

67

Na2s4

"

67

Na2s5 II ₆₇

Na2s6

_"

67

Na2S7 It ₆₇

Na2se f.c.cubic a:6.81 Cl II _37,67,3_~

Na2se2 It ₆₇

Na2se3 II ₆₇

Na2se4 It ₆₇

Na2Se5 II ₆₇

(18)

16

COMPOUND

CRYSTAL LATTICE CLASS P ARA:Mh'TERS (

j)

NaTe

f.c.cubic a=7 .32

N01 K-Li compounds

No K-Rb compounds

KCs

STRUCTURE REMARKS

REFER-ENCES

Cl

Reported on basis of pre-cipitation during titration, and discontinuity in poten-tiometric titration curve;

thermal analysis.

57,6

7

Phase diagram; thermal

analysis.

Thermal analysis.

57

Reported on basis of pre-cipitation during titration,

m d discontinuity .in poten-tiometric titration curve.

67

II

Phase diagram; thermal

analysis.

67

Complete solid insolubility .)9·

Complete solid solubility. 39

Very doubtful thermal analy-sis; later work (39) dis-putes evidence of CsK

compound. 50,39

Both Au2K and AuhK were pos-tulated on grounas of their x-r~- powder spectra, which were distinctly different from both pure K and Au. No struc-tures or parameters were deter-mined from the x-ray patterns.

(19)

COMPOOND

KAu

CRYSTAL CLASS

No K-Mg compounds

KCd 13 KCd7 KHg cubic cubic tri-clinic

LATTICE 0 PARAMETERS (A) a=l2 .38 a•l3.81 a::6.62 b::6.91 c::6.94 cx:lo6°, fi= 102°191 ' ~=92°481

KHg2

KHg3

KHg4

KHg8 or 9

KHgll cubic

No K-Al compounds

a::9.65

STRUCTURE REMARKS

REFER-ENCES D23 D23

/C~---

~

Pfl

Determined by vacuum fusion~-doubtful.

Complete solid immisci-bility.

X-ray powder data.

tt

Thermal analysis.

Viscosity measurements in liquid amalgam indicated

51

82

71,72

82.

solid stable compound K2Hg. 73

Determined AHform., llF,

and AHsoln. from emf. cells. 81

Precession x-ray data, single crystal; Patterson and elec-tron density refinemen~s.

Thermal analysis.

n n II 80,93

52

52.

5-2

(Same structure as BaHg11 .) 80,68

Complete solid

immisci-bility. 82

(20)

18

COMPOUND

KTl

KSi

KGe

KSn

KSn ₂

KSn4

CRYSTAL LATTICE ₀

CLASS PARAMETERS (A) STRUCTURE REMARKS

RE.F'ER-ENCES

Thermal analYsis; structure of KTl not isomorphous w.i. th NaTl, as determined by

Debye-scherrer method.

4,58

X-ray powder data and thermal analyses indicated

exis-tence of these compounds.

55

II

55 "

55

II

55

Thermal analysis and phase diagram; (work done in

1907). 69

" 69

II 69

" 76

11 76

Thermal analysis, phase diagram; compound checked with hardness tests and electrical resistivity by

(83). 76,83

II 76 J 83

(21)

CRYSTAL LATTICE 0

REBER-COMPOUND ClASS PARAMETERS(A) STRUCTURE REMARKS ENCES

K3As hexag- a=5. 793 ₀₀₁₈ X-ray powder, De bye -Scherrer

onal c:l0.242 data. 34

K3Sb hexag- a=6.037

onal c=lO. 717 ₀₀₁₈ II _34,74

KSb Thermal analysis. 48

K3Bi hexa.g- a=6.180 oo·l8 Debye-Scherrer x-ray powder

on&l c:l0.955 data.. 34,84

K9Bi? Thermal analysis.

_lh

K3Bi2

_"

84

KBi 2 cubic a=9.52 Cl5 Debye-Scherrer x-ray powder

data. 75,84

K2Se cubic a:7 .691 Cl De bye-S c herrer x-ray powder

data. 37,77

K2se2 Phase diagram constructed

from thermal analysis; com-pounds determined by Debye-Scherrer x-ray powder method, but structures not

deter-mined. ₁₇

K2se3 II ₇₁

K2Se4

_"

77

K~se₅

_"

77

K2Te cubic a=8.168 Cl Debye-Scherrer x-ray powder

data. 37,77

K2Te2 Phase diagram by thermal

analysis and Debye-Scherrer x-ray powder data for com-pound determination, but

(22)

COMPOUND

CRYSTAL LATTICE

CLASS ~ETERS(~) STRUCTURE REMARKS

REFER-ENCES

KRe

No K-Fe compounds

RbAu2

RbAu

RbHg5

Rb2Hg₉

Rb5Hgl8

Rb₂Hg₇

RbHg2

cubic a.=l3 .88

Phase diagram by thermal

analysis and Debye-3cherrer x-ray poVIder data for com-pound determination, but structures not determined.

77

n

77

Paramagnetic properties of alloy of composition ReK indi-cates probable compound

for-mation by Re with K. 78

Solid and liquid

immisci-bility. 79

Both gold compounds made by vapor diffusion; no struc-ture details.

X-ray powder data. 71

Compounds postulated by

magnetic susceptability

meas-urer:1ents and thermal

analysis. 86,90

II

86,90

(23)

CRYSTAL LATTICE 0 REFER-COMPOUND CLASS PARAMETERS(!) STRUCTURE REMARKS ENCES

RbJH% Compounds postulated by

magnetic susceptability meas-urements and therm~

analysis. 86,90

Rb₇HgB II _86,90

RbHg₁₁ cubic _{Similar to}_KHg~~;no

param-eters determin • 87

RbHgl2 cubic a=lO. 71 87

RbC_,1 hexag- a=4.95 Method of preparation not

onal c=22. 70 given. 88

RbC16 hexa.;;- a=4.95

onal c=l7 .99 II ₈₈

RbSi X-ray patterns of RbSi,

RbSi , RbGe, and RbGe4 were

RbSis

take~,

but only shown, not

worked out; samples prepared by direct union and

subse-H.bGe quent volatilization of one

component~

Rb_Ge4 55

a=6. 29 4 X-ray powder data; sample

Rb3Sb hexag- _ffi_s

h--onal c=ll. 23 prepared by addition of C6/mmE_7 alkaline metal vapor to

(24)

PART II: REFERENCES

1. Pastorello, S., Gazz. chim. ital. 60, 493 (1930).

2. }reeth and Raynor, J. Inst. Metals 82, 569 (1954).

3. Taylor, A., "X-Ray Metallography," pp. 373-375 (John Wiley & Sons Inc., New York, 1952).

4. Zintl and Brauer,

z.

physik. Chern. B20, 245-252 (1933).

5. Perlitz, H.,

z.

Krist. 86, 155 (1933).

6. Baroni, A., Congr. intern. quim pura y apl.--Frao,o IX~' 75 (1934).

7. Grube, V. Zeppelin, and Bumm,

z.

E1ektrochem. 40, 160 (19.34).

8. Zamatorin, M., Metallurgist

1'

96 (1938).

9. Hellner and Laves,

z.

Krist. 105, 134 (1943).

10. Zint1 and Schneider,

z.

Elektrochern. h1, 764 (1935).

11. :}rube and VosskU.hler, Z. anorg. Chern. 215, 211 (1933).

12. Zint1 and Schneider,

z.

E1ektrochem. 41, 294 (1935).

13. Grube, VosskUhler, and Vogt,

z.

E1ektrochem. 38, 869 (1932).

14. Baroni, A., Atti accad. naz. Lincei, Rend. 6 18, 41 (1933).

15. Masing and Tamrnann,

z.

anorg. Chern. 67, 183 (1910).

16. Baroni, A.,

z.

Elektrochem. 40, 565 (1934).

17. Hansen, M., 11Aufbau der Zweistofflegierungen, 11 p. 919 (Edwards Brothers,

Inc., Ann Arbor, Michigan, 1943).

18. Zintl and Schneider,

z.

E1ektrochem~ 41, 771 (1935).

19. Grube and Wolf,

z.

Elektrochern. 41, 675 (1935).

20. Pastorello, S., Gazz.chirn. ital. 61, 47 (1931).

21. Komovsky and Maxirnow,

z.

Krist. A92, 275 (1935).

22. Zintl and Woltersdorf,

z.

Elektrochern~ 41, 876 (1935).

(25)

24. Shamray and Saldau, Izvest. Akad. Na1~ S.S.S.R. (khirn.)

l,

631 (1937). 2.5. Grube and Schaufler,

z.

Elektrochem. 40, .593 (1934).

26. Klemm and Struck,

z.

anorg. Chern. 278, 117 (19.5.5).

27. Baroni, A., Rend. reale accad. nazl. Lincei 16, 153 (1932).

28. Grube and Meyer, Z. Elektrochem •. 40 771 (1934).

29. Nowotny, H., Z. Metallkunde 33, 388 (1941).

30. Grube and Klaiber,

z.

Elektrochem. 40, 745 (1934).

31. Rollicr and Arreghini,

z.

Krist. 101, 470 (1939).

z.

Elektrochem. 41, 102 (193.5).

33.

Brill, R.,

z.

Krist. 6.5, 94 (1927).

34. Brauer and Zintl,

z.

physik. Chern. B37, 323 (1937).

3.5. Grube, Vossklihler, and Schlecht,

z.

Elektroche~. 40, 270 (1934).

z.

Elektrochem. 41, 297 (193.5).

37. Zintl, Harder, and Dauth,

z.

Elektrochern. 40,

588

(1934).

38. Laves and Wallbaum, Z. anorg. Chern. 250, 110-120 (1942).

39. B5hm and Klemm,

z.

anorg. Chern. 243, 69-85 (1939).

40. Perlitz and An1ja,

z.

Krist. AlOO, 1.57-166 (1938).

hl. Haucke, W.,

z.

Elektrochem. 43, 712-719 (1937).

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-.

43. Zintl and Neumayr, Z. physik. Chern. 20, 272-27.5 (1933).

44.

Zintl and Dullenkopf, Z. physik. Chern. Bl6, 193 (193c).

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z.

physik. Chern. B34, 238-254 (1936).

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M.,

op. cit., p. 792.

47. Hansen, M., op. cit., p. 933.

(26)

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z.

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nat. 78, 145 (1942-3).

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z.

Elektrochem. 42, 201-209 (1936).

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z.

anorg. Chem. 257, 113-126 (1948).

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Elektrochem. 48, 418 (1942).

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637 (1952).

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1,

277 (1954).

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(27)

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(28)

A l: oh--Fm3m

s

PART III: STRUCTURE DETAILS

A=4: atoms at 000;~!; ~;0~}

Reported compounds: _Li3Cd

Remarks: Implied in this structure is a random distribution

of the atomic species on the lattice sites. This probably is not true at low temperatures.

A 3:

D~h--P6

3 /mmc

B 2:

B 32:

A=2: atoms at l/3,2/3,1/4; 2/3,1/3,3/4

Reported compounds: _{LiCd3 and LiZn}₉

Remarks: See Remarks under A 1 structure.

1

Oh--Pm3m

A :2: ordered ,1.9 -brass or CsCl structure

with Cs (Oh): 000

Cl (Oh): ~~g

Reported compounds: LiAg, LiCd, LiHg, LiTl, and LiPb

Remarks: LiAl was originally reported in this structure, but

more recent work indicates the B 32 structure. LiCd has

also been reported in both B 2 and B 32 structures, but

which is the correct structure for LiCd is less clear.

7

Oh--Fd3m

A:16: NaTl structure

with 8 Na (Td): 000;

tH;

+F. C.

8 Tl (Tq): ~~~; fH; +F. C.

IF.

C. - add 000 • .wL l.~ • 0--4..· and o~11 to all coordina te_s7

LJ: - ' 2 2'22 , 22' 22

Reported compounds: LiZn, LiCd, LiAl, LiGa, Liin, NaTl, and Nain

(29)

C 1:

0~

--Fm.3m

A:l2: fluorite structure, Ca}2

with 4 Ca (0 ): 000 +F. C.

8

F

(Td~: ±(

!

~

)+F.

C.

Reported com_{pounds: Li2S, LizSe, LizTe, Na2}

o,

_{Na2s, Na2se, Na2Te,}

K2Se, and K2_Te.

C 14:

D~h--

r

6

3 /mmc

A=l2: Laves Phase--MgZn2 structure

with 4 Mg (C3v): ~(l/3,2/3,z; l/3,2/3,1/2-z); z-:::d./16

2 Zn (n_{3d): OOO;OO!}

6 Zn ( C2v): !(x, 2x,. ~; 2x,i, :};

x,x,

;j); x~-1/6

Reported compounds: _{Li2Ca, Na2K.}

C 15:

O~--Fd3m

c

16:

A:24: Laves Phase--MgCu2 structure with 8 Mg ( T d) : 000; -~ 11

+

_F'. _C.

16 Cu (D3d):

5/B,SJB,5/8; 7/8,7/8,5/8; 7/8,5/8,7/8;

5/8,7/8,7/B

,

+F.

c.

Reported compounds: _{KBi2, NaAu2·}

nt~--I4/mcm

A=l2: _{CuAl2 structure}

with 4 cu (D4): :!:(oat) B. c.

8 _{Al (C2v):}₁ ~(x,tTx,O;

t

+x,x,O)

+B. C.

LB·

C.

=

add 000 and 2~J to all coordinate~?

Reported compounds: Na2Au with x=O.l60.

C 32: Dgh--P6/mmm

A:3: AlB2 structure

with l A1 (D6h): 000

2 B (D3h): 1/3,2/3,1/2; 2/3,1/3,1/2

(30)

28

D ~9:

<{-Fm3m

A=l.6: Biti3 structure with 4 Bi (Oh):

4

Li (Oh): 8 Li (Td):

000 t-F. C •

.1.il ' 221_ +F,.

c •

.±( 4U) +F.

c.

Reported compounds: Li3Hg, Li3Sb, Li3Bi

Remarks,:· _{Li3Sb exists also in tm hexagonal D o18 structure.}

D~h

--P63/llll00

A=8: Na3As structure with 2 As (n_3h):

· 2 Na (DJh):

4

_{Na (C3v):}

!(1/3,2/3,1/4) :t( 00t)

±(l/3,2,.13,z; 2/3,1/3,1/2+z);,z-o.583

Reported compounds: Li3Pb, Li3Sb, Li3P, Li3As, Na3As, Na3P, Na3Sb, Na3Bi, K3!s, K3Sb, K3Bi, Rb3Sb

Remarks: See also D 03.

D~h--P6

₃

/mmc

A::8: Mg3Cd structure with 2 Cd (Djh) :

6 Mg (C2v):

±(1/3,2/3,1/4)

:t( 2x,x,

i;

x,x,

i;

x,

Zx, i); x -::::::1/6

Reported compounds: LiHg3•

6

oh--Fm3c

A:llZ: NaZn13 structure

with B Na (0): ±(~H) +F.

c.

8 Zn (Th): 000;~~~ +F. C.

96 zn (C8 ): ±(o,y,z;~; f,z,y; ~; o,y,z;

?;

f,z,y;

~)+F. C.

~~ = permutation!?

Reported compounds: NaZn13 with y=O.l8o6 and z:O.ll9Z, RbCd13 with y:O.l78 and z:O.l22,

(31)

L 10:

L 12:

Oh--Im3m;

T~--I43m;

and

T~--P43m

A=$2: a-brass structures. The basic structure consists of a cubic unit cell whose edge is three times the edge of a simple body-centered cubic cell. From this large cell of 54 atomic sites is abstracted 2 atomic sites with small attendant shifts in parameters of some of the 52 occupied sites. The space group depends upon the formula of the compound and the atomic species occupying the various atomic sites.

Reported compounds: L~~Ag _{(reported formula varies from Li1zAg to} Li3Ag), Li10Pb3 •. (Li5P!>2)

Remarks: l-brass structures usua],.ly exhibit extensive compo-sition variation.

T~--I43d

A=7~: c~

₅

~a type

w~th

1~

Cu (S4): O,l/4,3/8;

~l

0,3/4,1/8i

~

+

~·

C. 48 Cu (C_{1 ):} x,y,z; ? ; x,y,~z; 'i); ;a-x,y,z; j) ;

i,!-y,z; Yi); -!+y,i+x,~; ~; ~y,-l-tx,3/4-z; ~;

i-t-y,3/4-x,~z; Q; 3/4-y,-}-x,~z; ';);+B. Ca x:O.l2, y=O.l6, z-o.o4

16 Si (c_3):

xxx;x,x,!-x;

~;

:l+x, i-tx,

i.,.x;

~x, :t+x,3/4-x; ~ : x:0.208

Reported compounds: Na15Sn4, Na15Pb4 (Na31Pb8).

1

n

_4h--P4/mmm

A=2: CuAu type superlattice with 1 Cu (D4h): 000 1 Au (D

₄

h): ~~~

Reported compounds: LiBi, NaBi, NaSb

(?).

1

Oh--Pm3m

A=4: _{Cu3Au type superlattice} with 1 Au (Oh): 000

3 Cu (D _{4h •}) • 1;{).l. _{2 2J 22J22}o.:u • ~

Reported compounds: Na2Pb5

(32)

2.0 .

n

_4h-I4/acd

A::64: NaPb structure

with 3 2 Pb (

c

_{1 ) :}

Remarks:

14 4 ;

· n

₄

_{h--P 2 mnm}

A:20: Na₃Hg₂ structure

with

a

Hg

(Cs):

(x,x,z; ~x,~-x,~z; x,x,z; !-x,~~x,

~+Z): x=0.12.5

:t

0.0005, z:0.190 ± 0.001

4

Na (c_{2v): !:(x,x,O;}

t+-x,rx,t):

x-0.210 ±0.010 4Na (C2v): ±(x,x,O; 2+x,2-x,2): x:0.368±0.010

4

Na _(C2h): 0~;~0;0~~;~~

Remarks: R(hko)=

~JFo-

Fcl

=

8.4~

~IFol

A:16: NaHg structure

with

8

Hg

(Cs):

4

Na (c2v):

.

4

Na (c2v):

Remarks : R

··

=

ill

o- F c

I

~I

Fo/

(33)

Oh--Pm3m

A=36: _{KHg11 structure} with 3 K (Dhh):

1 Hg (Oh):

8 Hg (c₃v):

12 Hg (

c

₂v) :

12

Hg

_(C2

v):

A~3: Li

₇

zn₁

R

structure

with 2 Zn (~3tJ:

±(l/3,2/3il/2)

~.8 L~ tD

₃

d):

000;002

Reported compounds: Li

₇

_{zn18 (and formula variations)}

Remarks: Evidently a high percentage of the Li sites are unoccupied, and the symmetry would indicate that the vacancies are random.

1

-C. --Pl

~

A=8: KHg structure

with 2 Hg (

c

_{1 ) :}

2 _{Hg (C1 ):} 2 K (C1J:

2_ K (C1):

t(xyz):

x=O.l98, y:O.lOl,