Infrared high temperature spectra of aluminium chloride and related species

of Molecular

Journal Elsavler

Sti-ucture, 113 (1981) Science PubIshers B V , tisterdsm

INFRARED

HIGI’

TEMPERATURE

P. KLAEBOE,l E. RYTTER’ 1 Department of Chemistry, ‘) ‘Institute of Inorganic Trondheim (Norway)

213

213-226 - Eknted

in The Netherlands

SPECTRA OF ALUMINIIJM

and

C.E.

CHLORIDE

AND RELATED

SPECIES

SJPGREN’

University

of

Chem stry,

Oslo,

Oslo

University

of

3 (Norway) Trondhelm,

N-7034,

NTH,

ABSTRACT Isothermal melts in

cells

and

the

vapours

860

to

IR vapour emission

below monomer and

spectra

conpared

witn

tetrahedral of

stration

earlier

is

= Cl,

ion

Alk412C17

in

the

(Alk

Al-Cl-Al

and

reflectance

and

Cs)

an

transmission

ratio

above

200

cm-‘,

The

dlmer

and

respectively,

data = Li,

iii,

Pb,

K,

dlstortlon

was

indicate

of

observed

D3d

Raman

of

ZnA12C1B

melts

can

Cs)

were

the

Emission

symmetry

earlier

!Q. spectrum

and

signal/noise

quality

isolation

from

techniques

spectrometer.

T.)3n syrmnetry,

Cs-RbcK
proposed

technique

ln

AlkAlC14 (Alk -1 50 cm . Increasing

113, K, as

D2h

various

obtained

better

IR matrix

and

= Ll.

of

GaCl,

study

reflectance

transform

was

had

terrrs

series

bridge

and

to

-1 . A comiarable

spectra

chloroaluminates

AlCl,

I)

50 cm

used

and

Fourier

Br,

and

spectra in

were

transmission

emission

1500

windows

evacuable

700

Raman

of

between

of

rature

and

melts

a linear

(X

assigned

spectra as

spectra

AlX3

an

transmission

were

diamond

emission,

with

between

transmlsslon

Emission

with

of

the

with

infrared

neasured

cm-l

recorded

nlcke

K range

spectra

the 200

by

300

were

between

of

for

data. at

Al,Cl; As

a demon-

ambient

tempe-

presented.

INTRODUCTIOM Reactive tubes

and

scope

at

and in

very of

the

interest inert

of

the

absence

high

cm-‘),

windows IR

00

0 1984

(ref.1)

be

or

vapours.

a cold

gas

Ehevler

melts done

high

cells

the

lack

of

spectral and

be

windows

have

been

vapours

were

based

B V

been

because suitable

region

with

Science Publishers

silica

comparison,

systems

(ref.4)

curtain

temperature

In

such

temperatures

Vapour

have

(ref.2). on

in

Raman spectro-

studies

the in

enclosed

by

Raman

particularly

transparent

withstand

high

been

be

studied

of

and

has

to

of

be

amount

involved,

melts

studies

and

moisture

work

must

able

with

and

a large

vapours

dlndows

corrosive

previous

0022-286Of.S1/~03

oxygen Thus,

difficulties The

(1500-30

KBr

vapours

spectroscopic

experimental materials.

or

of

temperature

infrared

towards

(ref.3)

inorganic

temparatures.

for

little

window

the

high

reported

corrosive

of

chemically of

slllca

employed. upon

Most

auench-

214 ing

the

vapour

sidlst-able

isolated

of

(ref.6)

were

obtained

high

vapour

using

for

for

studying

employed the

can

for

Our niques shortly

the

equilibrium

can

mesh

by

IR

results

and

data

described

a fine emission

of

the

transform

IR

melts in

the

the

studied

However,

vapour

con-

and

other

hand,

reversibly

as

the for by

least

the designed a func-

when

vapodrs

emission

present

moved

using and

eml,,sion

enclosure

and

cell

emission

transfonn

Improved and

and

from

studied

by

oxygen,

3 abn the

been

and

An emission at

Moreover,

Fourier

have (ref.5),

(refs.7

moisture

complete

radiation. to

sulfates screen

spectroscopy

measurements of

obtained of

K.

the

on

techniques.

require

trapours.

unit

be

and

towards

pressures

and

lo-20

between cell

platinum

(ref.6)

reactivity

chlorides

contain

below) vapour

thlocyanates

reflectance

transmission

(see

isothermal

at

pressure.

a?d

melts

occur

matrix

our

Fourier

passage

nitrogen

on

metal

diamond

or

nitrates,

or

pressure

chloride-alkali window

and like

supported

reflection

can

In

studies,

salts

transmission

argon

shifts

temperature

Molten

inert

bands.

transmlsslon

tion

of

an

frequency

math-ix for

in

8).

the

in

angle spectra

Because

of

alumlnlum an

fitted

optical

with

proved unit

one

to was

a window

be

suitable

successfully

source

compartment

to

spectrometer. transmission

reflectance

and

emlsslon

spectroscopy

tech-

will

be

review.

EXPERIMENTAL The vapours

infrared (refs.9

Fig. 1. Optlcal measurements of

high and

path, melts

temperature lo),

for

ceils ernlsslon

showing the (E. emission

constructed studies

mission unit,

of

for melts

transmission (refs.9

cell employed for described in refs.9

and

studies 11)

rPlectance and 11).

and

of

vapours the

have

source

been

transmission into 1).

because gold

of

the

the

collecting

so

that

and

carbon

to

spectra

IR

emittance

the

reflectivity

significant clent

of

the

melt

of

as

a thin was

experimental and

emittance

of

a liquid

or

at

the

to

reference

for

representation

the for

the

node1

of

113~

recording

cavity

covered

vapour

emission

strong

torr.

resolution,

a Bruker

methods

0.1 in

S cm

in

Fourier

-ca

employed -1

4 or

it

experiments

edacuable

spectra

vapours,

during

m were

a

transparent

a Bt-uker

A cylindrical

body

a poor

1s also

and

and with

vacuum

with

with

handling

(refs.9-11)

gives

0.5

the

sample

was

piston,

bands

This

depenaence the

The

present

as

of

the

that the

mn path

length

usual

vapours,

the

with

of

lrn

the

shifts

a black

body

emlsslon

of

analysis

(ref.12)

gives

a better with

a black

band

distortions

body

reference

and was

10). used.

as

splittings

the

annoying

sample

as

were

ln

very

the

was

as

representation

Therefore

were

(a

as

the of

opaque

well

body

10,~ in

between forces

C* defined

an opaque

emittance

(refs.9

an

eliminates

parameter

quite

film

false

of

to coeffl-

capillary

and use

dependent

leads

was thin

upon

The

is

absorption

thickness

a lo-20

hoNevet-,

employed

a black

me1 t

dependent

bands.

E’

boay

hhen

low.

melt

a black

except

frequency

strong

by

to

sample.

mostly

a theoretical

of

upon

the

A new Emittance

(ref.11) than

relative

shapes

very

Instead

spectra

E based

melt

dividea in

of

band is

the

splittings.

melts

the

distortions,

for

shown

melt

surface

a nickel band

work

emission the

sample

a reference

and

It

liquids

and

observea

distortions sion

compounds,

a black

23

reflectance

employed.

thickness

However,

frequently

duced.

the

K in

visually

recorded

12 and

cm-’

and

1000

and

inspected

recorded

was

as

since

window

melt

For

changes

piston

1600

melts

above

DTGS detector 6,

nickel

sealed

corrosive

were

were

the below

effectively

heated

be

with

spectra

in

sample

experiments,

diamond

can

3.5,

described

alstortions

or

thick)

the

be

spectra

114C

scans.

been

towards

can

melt

be

the was

(ref.11).

The

the

1300

procedure

spectra

the

the

car

temperature

thickness

functioned

This

melt

inert

sudden

spectrometer

have

black

IS

from

from

above

IR radiation

the

region

be moved

a position

optics

IF

it

and

model

and

preparation

spectra

our

-1

transform

The the

cm

the

could

to

reflected

in

emission

of

500

Fourier

with

by

spectrometer

700-30

and

cell

work)

accessory

strength

diamond

crack

region

of

cell

conductivity,

beamsplltters

region

the

emission

emission

1s transparent

mechanical

transmlsslon

transform

the

high

not

visible

Mylar

of

IIa

thermal

does

The

cavity

The

for

By means

Moreover,

a high

Diamond

on

the

Diamond

gasket.

has

elsewhere.

(position

compartment.

directed (Fig.

described

compartment

f;nls-

lntrothe for

reference. not

observed

a regular

In

216 RESULTS

AND

Yapour

DISCUSSION

spectra

Dimer

molecules.

three

tmnmperarures

Since

the

this are

body

emission

temperature

lt is not quality.

spectra

generally

experiments

aluminiun path)

it was

chloride

having

only

transmittance

IR

compared

of comparable

mission our

black

The are

and one

with will

hale

surprising Below had

easier forms nindow,

spectra

the

the

a-n-1 the

signal/noise moisture

than

in the

3. (top,

Fig. 4. vapour.

right)

(bottom,

IR transmission

right)

IS transmission

ratio

cell

transmission

spectra

spectra

and

of

2mission

in this

small

cell

spectra

our

trans-

region.

In

hydrolyzes

volume

(0.5

of 40 rmn path

of aluminium

bromide

of aluminium

at

K in Fig. 2. -1 900 cm at

immediately

of aluminium

spectrum

508

is low and

(which

emission

in the

at

transmlssiDn emisslvlty

to avoid HCl)

chloride

at approximately

a better

Fig. 2. (left) IR transmission and emission vapour (D, dimer; M, monomer bands). Fig.

spectrum

a maximum

that

200

of aluminium

enllssion

mn

with

chloride

dimer

iodide

vapour.

dimer

217 two

windows.

spectra

The

in

cally

the

favoured

cells,

the

The

therefore

700-200

cell was -1 region. cm

at

temperature

and

operating

Combined of

emission

with

with

A1235C16 Tentative

checked

A1237 Cl6

values

calculations

as

for

aluminium

active

dimer

aluminium

bands

halides

were

and

4)

are

were at

470

monomer

observed.

I9

emission

investigated

spectra

and

of

vlo

of

alumini~~m

and

symmetry

were

using

IR matrix

from

14)

obtained

15

(ref.10).

on A12C16,

shifts and

(refs.13

gzh

analysis

~5

570

reveal

I

I

of

were

constant the

bromide

r<, respectively.

molecules

Force

200

5.

recorded

of

Y

Fig.

transmission

our

spectra.

in

the

1).

spectra

(Fig.

modes

thermodynami-

the

results

isotopic

dimer

(ref.9).

terms

coordinate

are

making

favourable

in

recording

however,

isolation

reported

for

pressure,

assigned

unobserved

concentrations

monomers, low

IR matrix

a normal

(Table

IR

Iodide

small

data

The

vapours,

and

by

the

well

Corresponding

only

data

fundamentals

were and

superheated

Raman

18 A12C16

results

high

favourable

calculations

following

I

At present

relation

(Fig. these

and of

3)

temperatures

a number the

chloride

regarding

I

dimer

and *

monomer

of

three

300 200 500 FREQUENCY (cm-‘)

gallium

and

vapour.

the

IR

218 dimer

fundamentals:

based

upon

the

data

(refr.

Raman well

~8

to

fundamentals analysis. force

A series for

398,

309,

on-1

was

for

mode of

200

emissicn

278,

154

(refs.1,13,17)

dimer

are

5)

Ga2C16

and

120

as

included

ln

at

IR

Table

‘J14.

with

low

‘Lhe aid

in

to

from

coordinate

results

of

K are

from seen

at

a band

transmission spectra for

results

shown

dlmer 475,

at 415

FIN.

of

5.

a force

=

constant

2Allj I

300

lcx

500

200

FREOUEHCYICW-‘1

FREQUENCY

Fig.

6.

II? einission

spectra

of

aluminiun

ommide

Fig.

7.

IF

spectra

ot

aluminlum

Iodide

emission

dimer dimer

LOO

360

and and

ICW’I

monomer monomer

The

chloride

(ref.16).

A1216

to 472,

spectra

gallium of

the

(ref.16).

744

whereas

assigned tne

a normal

K to

The

should

Raman

clearly

emission

with

now seems

frequency

conversion

are

were

and

region

elsewhere

473

(ref.16). the

it

cm-’

the

detail

K spectrum,

fundamentals compared

of

with

a graduaf

473

(ref.13)

280-220

The

1 together

band

assignments

The

results

the

fundamentals

similar

1 and

in

described

in the

active

?

Raman fundamentals

diners.

lllustratlng

cm-l

u18

temperatures

djmer

quite

and

bands

assigned

are

Y.

IR matrix

the

a combination

were

‘J9

the

weak

ln Table

and

(Fig.

chloride

Raman

calculation

were shown

spectra

IR active

interpreted

gallium

cmare

chloride The

(Bjg)

calculations, of

gallium

monomer.

the

w6

>

Concerning that

results

constant

> v,7

(refs.l5,i6),

(refs.lO.14)

below The

> “,3

data

1,13,17,18).

established

be attributed

> V,6

IR vapour

vapour. vapour.

219 TABLE

1

Observed

and

(X = Cl,Br,I)

calculateda and

fundamental

Ga2C16

ln terms

A1235C16

A

g

"1 ;2 L';

Au

b

for

the

A12Y6

dimers

sLructure.

Alp6

Ga2C'6

A'216

obs.b'c

calc.b

obs.b'c

calc.b

obs

510

409d

412

34gd

344

416

409

341 219 100

203 139 59

205 139 61

145 93 42

143 93 44

310 168 E9

312 168 89

82

227 83

23ge -

237 143

423 75

420 84 14

475 201

474 201 45

obs.a

talc.

511 337 219 9E

v5

-

819

frequencies

of D2h

5s

38

"c

talc.

29

61

x6 7 "8 v9 viO

281 168

282 168

241 114

249 116

626 178 -

623 178 33

507 li0

501 117 20

829

"11 Y2

514 115

617 115

48gd 76

494 79

408d 54

413 57

472 113

468 110

B2u

"13 v14

418 123

415 125

342 89

340 85

288 64

291 64

309 120

310 120

839

v15

Blu

63u ?6 "1 7 v18

105

105

483 320

483 318

378 198

377 196

315 137

315 137

143

142

89

a8

64

63

molecules.

alumlnlum

conversion tures

ln the

concentration

with

far

low

frequency

In spite

of great

ture, ride

leading spectra.

to the

the

51

cm-' and

formation

of

117d

118

398 278

407 277 154

‘54

increasing

5. The

of HCl

in the

iodide

spectra

baking

monomer

i

The

of riC1

(curve

the cell totally

Itigh temperature

the

appearance

with

of

the 7) in

covering

spectrum

not

by

(Fig.

8 (alumlnlum The

8 marked

A

tempera-

increasing

lodlde).

we could

monomers

kJ/mol.

is illustrated

the monomer

handling,

(ref.10)

to 126

ln Figs.

B of Fig.

and

with

transmission

etc.

divers

84

alumlnium

presented

giving

the

from

halides

6) and

10 (alum~niun

in curve

In sample box

in Fig.

aluminlum

are

ln the computer

glove

between range

to monomer

(Fig.

series

-ca 250 bromide)

precautions

In the

dlmer

chloride

for

is apparent

subtracted

chloride

bromide

below

lines

was

atmosphere

gallium

Corresponding

range

spectrum

dry

from

temperature

9 (alumlnlum

rotational

for

difference

gallium

of alumlnlum

IR region.

chloride),

enthalpy

ard

equlllbrlum shown

spectra

the

The

halides

1s clearly

emission

HCl

54d

ref.17. Fref.13. ref.18.

Monomer the

72

d

tref.10. ref.16. 'ref. 1.

of

78f

_

b

A).

in vacuum,

avoid

alunlnlum

IIO~Schlo-

220

Al2Br6

FREQUENCY

(cm-')

=

2 AIBrs

FREQUENCY

km-')

I

I

D

D

(cm-l)

FREQUENCY

Fig. 3. (left) IR transmission spectra of alumlnlum chloride vapour (curve A, 843 K; curve 6. B43 K, IiCl bands (x) are not subtracted. curve C, 473 K; D, dlmer; M, monomer bands). Fig. 9. vapour.

(middle)

Fig. 10 vapour.

(right)

TABLE

IR transmlsslon

IR transmission

spectra

spectra

of alumlnlum

of alumlnlum

bromide

iodide

dlmer

dimer

2

Infrared

and

Paman

spectral

data

for A1X3

(X = Cl,Br,I)

AlC13

AlBr3

AlI3

GaC13

37sa

230b

15SC

3B?

and

GaC13_

R

w1 "2

Al' A2'

214

176

147

143

IR

"3

E'

616

503

427

464

R,

IR

v4

E'

148

83

66

131

R,

IR

“ref. b

10. ref.19. 'ref. 1.

and monomer

and

monomer

221

0

ZQiJ

4.m

6c4J

800

loo0

val

WAVEMJHBEP km'1

Fig 11. IR cmlsslon spectra of AlkAlCl, melts (Alk; Li, Na, K, Rb, Cs). The numbers divided by a sias are the lowest and the highest einittances observed in the region 700-100 cm ;' with a 3.5, m beamsplltter. Thick melts are references (for meaning of E , see text and ref.l2), dashed line, expanded plot.

W?th

E3h

listed

in

Table

apparent

from

monomer lari fields

were

where

(refs.10

%a1 t

v

between

for

ano

that

are

the

Alk+

The

four

AlkCl)

and

modes

Raman

of

species

results

2 the

coincide

with

“4

terminal

metal

-halogen

molecules

-E’

for

‘J,

J8 overlaps

band

(d imer)

monomer

and

(refs.l,lg)

dimer

and

the

%I’

(monomer)

(4,‘).

As

strongly

due

bond

described

are

to

the

(ref.

in

the slml-

16).

detail

Force else-

are

bands

(vc2)

The

IR emission

shown

which

should

IR

around

(ref.11)

being

475

IS

cm-l

TABLE

in

and

molten

21 ) and

AlkAlC14

potentlometrlc

(AUK

= LI,

studies

ha,

K,

IR

quite

11.

with

and

inactive broac

of

550

with (Fig.

was cm

are

AlkAlC14

349

(wlA1),

in

experimertal = Ll,

Na,

LlA12C17 K

168 m 305 w,sh 334 w 381 m 442 w,sh 514 vs 570 s,sh 683 k 791 w

aRef. 11. bAborevlatlons: %certain wave

Rb,

three

IR active (refs.20-22).

tetrahedral

as

a weak

assigned &

zo

suggesting

splitting

(in

cm -’

of

Al kAl2C17

(&)

50 i, A1C13 modes

and

of

K.

results

)

species

However,

v1

350

cm

2vl,

2\J1’u2

and

2vl-\J2

‘J3

Yoreover, the

trlply

around degenerate

0.1 *Cl 7

CsAl 2C1 7

473

513

K

K

Assignment

K

97 w,shb 158 w,sh 179 m

64 w 165 w,sh ial m

Al k+--Al Y2

Eu

J7 ;2 V; Y

ATg A2U A2u A AZU lg

Yl

Eu

179 310 333 391 440

m W,Sh m m w,sh

308 331 381 439

w,sh m m w

304 326 381 439

w,sh m m w,sh

517

vs

525

vs

517

vsc

689 791

w w

690

w

Xi

w

687 78?

w w

s

me1 ts

Cs).’

473

medium too tgl:l;

weak; me1 t.

v,

;2;;5;:2u 2 5

very;

-1

around

of

NaAl 2C1 7

50

band

symmetry.

11)

a tetrahedral

of

Raman

observed were

around with

(mixture

the

-1

situated

?n agreement

observed

(Al)

680

melt

As apparent

those

inactive

the (045-2)

spectra

Fig.

800,

in

18@ cm-’

3

Infrared (Alk

and

in well

be

(refs.20

species

observed

485

5-2 agreed

bands

spectroscopic

AlCli.

g and

:73

the 1 and

four

dominant

Raman

(v&),

srructure.

and

the

active

16).

Raman

120

with Tables

while b,* 3the monomer

derived

IR

spectra

indicate Cs)

three

2 together comparing

band

ty

the

SyrriiIetry,

sh,

shoulder.

2C1 ;

gEu

_’

E2

mode

radius

into of

AlCl;

close

the

ion,

lying

alkali

ion

increasing

situated

at

Rb,

respectively,

Cs+,

300,

and

reveal

In the

140,

These

components.

108,

order

86 and

are

bands

are

tetrahedral

enhanced

distortion

with

(refs

Cs ' < Rb' < KT < !:a+ < Ll-1 with the counterlons 64 cm

interpreted

as

ion

pair

decreasing

22,23)

Broad

of

IR bands

Li +, ha+.

Alk'-AlCli

KI,

interactions

(ref.11). Al2C17 AlkCl A12Cl;

A corresponding

ions.

with

a molar

has

previously

(refs.20-22)

The

sents

a puzzling

Ions

in the melts

symmetry). and

certain

been

inferred

results

of

lead

!R and

spectra

The

the

Raman

spectra

A12C1;

ions

bent

bridge

structure

IR and

Raman

bands

(refs.11,?0,22)

these

for

the

repre-

the A12Cl;

broad

in the

3 and

4 seem

(C_

melt-cands

iow

far

ion

melts

fundamentals

of

particularly

of Tables

of

of an

in the melts

active

overlap

of AlC13-

existence

the

considerable

Raman

melt

11)

of

to 21

for

(ref

from

structure

allow

IR emission

recorded

A permanently

should if we

series

3 1 were

molecular

unobserved

the

of

problem.

Even

regions,

ratio

frequency

away

from

this

predlcclon. Since

only

tentatively possible

D3d

relatively bands (ref

four

spectra

the

data

although

crystal

around

the molecular to

principle

less

be observed

G6

will

6 Raman

syrrametry and

the

v14

species

fundamentals KA12C17 modes action ions.

WB

between A bent

(ref.11).

from Alkf

bridge

A high

lad

of

ring

force

and

G.

of

mode

of

of A12C16

and

listed and

be classified rules

for &

the &d

are

in

might Since

subgroup

(one

in Table

The

Raman

at 439

and

305

as

of

for

An

~1~~

heavier

exist

IS expected

amplitude

03d

and

ilg

unsymmetrical

the

with

active -1 cm for

IR activated

possibly

bridge large

4

the

bands

might

inactive)

so were

IS favoured

the

bridge) rotation

E and $ modes -9 respectively (ref.25)

Interpreted

the Al-Cl-Al

(ref.10)

(bent free

since

the LIJd symmetry.

or Cs)

Raman

of A12C1;

are

Weak

A12C1;

(C2v

should

be discussed,

a

of C13d symmetry

possess

fundamentals

were

with

reveal

!R and

symmetry

selection

Raman,

unobserved

spectra)

a linear

constant

puckering

KA12C17

left

perturbation

flexibility

and will

7 IR active

species

structure

functions

20,22)

structure

(ref.11)

in terms

has C+

The

(refs

between

probably

fundamentals

for

other

and

would -

for l13d smetry,

the

were of

"1o

In the

resulting

by the the

and

(close

KAl,Br7

the melt

assignments E+

that A12C1;

in infrared

rather

of AlkA12C17

interpreted

the wave

ago

41-Cl-Al

coincidences

(ref.25).

c?&

than

to classify

expect

of

bands

but

be used

modes

Hence,

group

long

a linear

lines

few

known

A linear

axis.

as weak

very

it was

have

tentatively

restrlctlve

species

We would

were

the double

observed,

might

IR emlsslon with

(ref.24)

according

were

A12Cl;

it is well

in the

no vapour

bands

that

syrrunetry. The

simple

Thus, 11)

Raman

suggested

for and

lnter-

alkali LiA12C17 supported

of vibration

(ref.26)

224

TABLE

4

'Jibrational

Alg

klu A

fundamentals

ul v2 v3

432 311 161

AlCl AlClal AlCi 3

v4

1.a.

torr~on

381 L" V5 331 :67 179

AlCi AlClal AlC13

a,b

of KAi*r17

stretch stretch

in terms

E

g

def

vlo

E" Stretch stretch def

v8 v9

vll

of D

3d

97

525

structure.

AlCl stretch A1C13 def ske13bend AlC13

stretch

AiC13 def skel bend AiClAl bend

aIR active tundamentals ref.11. bRaman active fundamentiis, refs.20,22.

Fig.12. IR reflectance spectrum (upper curve) and Raman spectrum (lower curve) nf ZnAl Cl at room temperature. The reflectance spectrum was recorded using the emi G s.1 -8 n cell mounted as shown ln Fog. 1.

225 ZnA12C1, have

Certain

melt.

recently

been

(refs.9-11)

to a position

reflectance

spectra

Fig

12 together

seems

well

scopy that

would the

appears

split

reduction Fig.

11)

for

require

triply

on

from

L

to 52v

top of

a Raman low

a cooled

the

585,

symmetry or Cs

of molten

the

melt

detector_

482 (or

at of

The

room

the

391

slightly

perturbed

are

1). The

shown

in

This

for

emlsslon

which data

This

technique

might

AlCl;

technique cell

(Fig.

compound.

ln the

bands.

cm-'

emission

ccmpartment

preliminary F2

reflection

the

temperature

same

stuoies

u3 of species and

using

moving

transmission

obtained spectrum

mode

salts

laboratories

temperature

degenerate into

spectra

in these

of ZnAl2Cl8

with

suited

IR

recorded

spectro-

indicate

&

structure

feature

indicates

T+, symmetry

a

in AlkAlC14,

syrranetry in ZnAl2C18.

ACKNOWLEDGEMENT The help

authors

with

the

are

grateful

IR recordings.

to C J. Nielsen Financial

and

support

J. from

Hvistendahl NAVF

and

for

valuable

IITNF is acknow-

ledged.

REFERENCES

: 3 4 5 ; 8 9 10 11

12 13 14 15 16 ;: 19

1-R. Beattie and J.R Horder, J. Chem. Sot. A (1969) 2655-2659. R.E. Hester in J. Braunstein, G. Mamantov and G-P Smith (Eds.), Advances ln Molten Salt Chemistry, Vol. 1, Plenum, New York, 1971, pp. 1-61 P L.D. Polyachenok, Russ. J. Phys. Chem. 50 (1976) 227-229. W. Klemperer, J. Chem. Phys. 24 (19561 353-355. J. Greenberg and L.J. Hallgren, J. Chem. Phys. 33 (1960) 900-902. J.K blilmshurst, J. Chem. Phys. 36 (1962) 2415-2419, 39 (1963) 2565-2548. J-B. Bates and G.E. Boyd, Appl. Spectrosc. 27 (1973) 204-208. and L.E. McCurry, J. Inorg. Nucl. Chem. 40 (1978) N-h. Smyrl, G. Mamantov 1459-1492. E. Rytter, J. Hvistendahl and T. Tomlta, J. Mol. Struct. 79 (1982) 323328. T. Tomita, C.E. Sjogren, P. Klaeboe, G N. Papatheodorou and E Rytter, J Raman Spectrosc., ln press. J. Hvistendahl, P. Klaeboe, E. Rytter and H.A. Oye, !norg Chem , in press. J. Hvistendahl, E. Rytter and H.A. Dye, Appl. Spectrosc. 37 (1933) 182187. 1-R. Beattie, H.E. Blayden, S.M. Hall, S N. Jenny and J.S. Ogden, J. Chem. Sot. Dal-con (1976) 666-676. M. Tranqullle and M. Fouassler. J. Chem. Sot. Faraday II 76 (1980) 26-41. P. Klaeboe, E. Rytter, C.E. Sjogren and T. Tomita, Proc. Sot. Photo-Opt Instrum. Eng. 289 (1981) 283-286. C E. Sjogren, P. Klaeboe and E. Rytter, Spectrochim. Acta, submltted. I R. Beattie, T. Gilson and G.A. Ozin, J. Chem- Sot. (A) (1968) 813-815. 1-R. Beattie and T.R. Gilson, Proc. Roy. Sot. A 307 (1968) 407-429. G.N. oapatheodorou, L.A. Curtiss and V.A. Maroni, J. Chem. Phys. 78 (1983) 3303-3315.

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S.J. Cyvin, P. Klaeboe, c. Rytter and H.A. 2276-2278; H.A. Bye, E. Rytter, P. Klaeboe Stand. 25 (1971) 559-576. G. Torsi, G. Mamantov and G. degun, Inorg. 560.

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E. Rytter, h.A. Dye, S.J. Cyvln, B.N. Cyvin and P. Klaeboe, J. Inorg. Nucl. Chen. 35 (1973) 1185-1198. Chem. 19 (1980) L240-2242. R.J. Gale and R.A. Osteryoung, Inorg. E. Rytter, B.E.D. Rytter, H-A. Dye and J. Krogh-Moe. Acta Cryst. (1973) 1541-1543. P.R. Bunker, Molecular Synmietry and Spectrosccpy, Pcademlc Press, York, 7979. Q. Shen, Thesis, Oregon State University (1954).

829 Yew

553.