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NASA Contractor Report 2 9 2 9

Interaction of Hydrogen Chloride With Alumina

R. R. Bailey and James P. Wightman

GRANT NSG- 195 1


FEBRUARY 1978

NASA

TECH LIBRARY KAFB, NY

NASA Contractor Report 2929

Interaction of Hydrogen Chloride With Alumina

R. R. Bailey and James P. Wightman VirginiaPolytechnic Institute & State University Blacksburg, Virginia

Prepared 'for LangleyResearch Center under Grant NSG-1195

National Aeronautics and Space Administration


Scientific and Technical Information Office

1978

"

FOREWORD

The Virginia

Principal

Investigator Institute

was and

on

Research-Study University

Leave the

from Uni-

Polytechnic

State

at

versity of Bristol(U.K.) during the period1 September 1975 to 15 June 1976. During that time, calorimetric studies'weredone by the Principal Investigator in the Physical Chemistry Department at the University of Bristol aas part of .the Grant. A detailed summary of the calorimetric work is given in Appendix 12.

The help of Mr. Frank Mitsianis in taking the SEM photomicrographs is recognized. Mr. W. R. Cofer, 111 of the NASA Langley Research Center is acknowledged for obtaining some of the X-ray powder diffraction patterns. Thanks to Andy Mollick and Mr. Frans vana m e of the University Glassblowing Shop D for the construction and repair of the vacuum system. A special recognition is given to Professor H. Everett, D. Leverhulme Professor of Physical Chemistry at the University
of Bfistol '(U.K.) for the opportunityto conduct studies on the

Calvet

microcalorimeter.

iii

I .

TABLE OF C N E T OTNS

iii
vii viii

I1

H Fc L I uA m
A B
C

....................... ...... ................... . ......... . .................. . . . . .. . . E. .. Chloride ........... . . ...... . F. G. ................... H. ESCA
D Introduction SolidPropellantEkhaustStudies AluminaSystem Surface S t u d i e s of Alumina Adsorption of Water onAlumina Hydrogen Adsorption Hydrogen Chloride Adsorption Studies Studies on Alumina D e s c r l p t i o n of Materials Characterization Techniques Adsorption Measurements S o l u t i o n Measurements Data Reduction m c e d u r e s

4 4 4
6

7 17
18
23 26

. . . D. .
A B C

............. ........... . . . . . . . . . .. .. .. .. .. ............. .......

26

27 29 34
35
41

A B
C

F
G

. . . D. E.

. . H.
I

C h a r a c t e r i z a t i o n of Adsorbents Preliminary Adsorption Studies Water Vapor Adsorptionon Cm a Alumina am Water Vapor AdsorptiononAlphaAlumina Hydmgen Chloride Adsorption on Cm a Alumina am Hydrogen ChlorideAdsorptiononAlphaAlumina Isosterlc Heat of Adsorption for Water Vapor on Alumina Thermodynamic Model of Hydrogen Chloride Adsorption Alumina on ESCA S t u d i e s

.......... ... . . ......... .. ..... . .. . . . . . . . . . . . . . . . . . .. . .............. ................. ..

41
60 60

71
76

a4
92

96 11 1

125

Page APPENDIX 1 APPENDIX 2 APPENDIX 3 APPENDIX 4 APPENDIX 5 APPENDIX 6 APPENDIX 7 APPENDIX 8 APPENDIX 9 APPENDIX 10 APPENDIX 11 APPENDIX 12

................... ................... .................... ................... ................... ................... ................... ................... ...................


.................. .................. ..................

130 131 134 135 138 139 142 145


151

156 159 160

vi

LIST OF TAFiLFS Table

Page
Binding Energy,PeakWidth,andChemical Al 2p ELectrons i n Aluminum Oxides (70)

I.
1. 1 11 1. IV.

h f .S. i.t .of. . . . . E l Nitrogen Surface Area o f Alpha B ! Alumina ....... BET NitrogenSurface Area of Gm a Alumina . . . . . . . am

25
44

45
67
73

b s s - S e c t i o n a l A r e a s o f Water Adsorbed on Gm a am A l u m i n a . . . . . . . . . . . . . . . . . . . . . . . . . Cross-Sectional Areas of Water AdsorbedonAlpha A l u m i n a . . . . . . . . . . . . . . . . . . . . . . . . . Cross-sectional Areas of HyiydrPgen ChlorideAdsorbed on Gamma Alumina

V.

.................... V I I . Cross-Sectional Areas of Hydrogen ChlorideAdsorbed on Alpha Alumina . , . . . . . .. . . . . . .. . . .. VIII. E m f o r F t o f H 0 Adsorption Isotherm on k r i Gm a am Alumina Using t h e b andhreundlichEquations ., ... I X . I s o s t e r i c Heats of Adsorption for Water Vaporon Aluminas . . . . . . . . . . . . . . . . . . . . . . . . a m X. Heats of Immersion of Alphaand Gm a Alumina i n 0.1N HC1 a t 30OC. . . . . . . . . . . . . . . . . . . . . . .
XI.
XIII.

V. I

83
91

95 97
102

... XIV. R e s u l t s of Water Layer Model Treatment . . . . , . . . . xv. ESCA Binding bergy, Range and N 1 PeakWidth a t Half M a x i m u m f o r Gm a Alumina . . . . . . . . . . . . . . . . am XVI. ESCA BindingEnergy, Range and Full PeakWidth a t M a x i m u m for-Alpha-humina . . . . . . . . . . . . . . .
I n t e g r a l Heats of S o l u t i o n f o r H C l i n Water at 25OC
Half

XI1

pH o f S l u r r i e s o f

AlphaAluminaandHydrochloricAcid

..
..

103
104 105 110

pH o f S l u r r i e s o f

Gm a Aluminaand am

Hydmchlorlc Acid

119
120

vii

LIST OF FIGURES

1. Ideal Gm a Alumina Surface am

2.

3.
4.

5.
6.

.... ........... Gm a Alumina Surface After Dehydration . . . . . . . , . am Nature of Water Adsorbed on Alumina Surface . . . . . . . Formation o f Gmupson Alumina Surface by Water Vapor Adsorption a t Elevated Temperatures , . . . . Adsorption of Hydrogen Chloride on T i 0 2 . . . . . . . . .
Hyhxyl

9
10

13
14

19

7.
8.

................. ... ..... Schematic o f Adsorption Apparatus ............


(61-63)
T y p i c a l E' P l o tf o rN i t r o g e nA d s o r p t i o n ! l Typical
Adso

ProbableReactionsthatOccur i n a SystemContaining Aluminum Oxide, Water Vapor and Hydrogen Chloride

22

30

on Gamma A l u m i n a . . . . , . . . . . . , . . . . . . . . . . . . .

42

9.
10.

BET P l o t for NitrogenAdsorptiononAlpha

Alumina.

.............. , .. ...... .
of Nitrogen on Gm a Alumina am

43

a t 7 7 K . . . . . . . . . . . . . . . . . . . . . . . . .
1. 1
Adsorption and Desorption of NitrogenonAlpha

t i o n and Desorption

47
48
50

at

??OK.

12. Photomicrograph

13.
1. 4

15.
16.

17.
18.

... Photomicrograph of Untreated Alpha Alumina at .. Photomicrograph of Untreated Cm a Alumina a t 5OOOX . . . am .Photomicrograph of Untreated Alpha Alumina a t 5OOOX . . . Photomicrograph of Gm a Alumina Outgassed a t MO0C am at 100x. . . . . . . . . . . . . . . . . . . . . . . . Photomicrograph of Cm a Alumina Outgassed a t at . . . . . a. m . . . . . . . . . . . . . . . . EDAX of Untreated Gm a Alumina . . . . . . . . , . . . . am
of Untreated Gm a Alumina a t l O O X am
lOOX
4OO0C

...... ..... .. .. ..,..


Alumina

51

52

53
54

5000X

55
57

viii

Page

19
20. 21.

Wide Scan ESCA Spectrum of Untreated

Gm a Alumina am

Wide Scan ESCA Spectrum of Untreated Alpha

... Alumina . . .

% 59

. . . Water. Vapor. . . . . . .. .. Time on Adsorption Capacity of 2 . Effect of Heating 2 Alumina . . . . . . . . . . . . . . . . . . . . . . . . . 23 The R e p r o d u c i b i l i t y o f HCl Adsorption a t 5OoC on S i x M f f e r e n t Gm a Alumina am Samples ............. 24. I n f l u e n c e of OutgasTemperature on Water Vapor t i o n on Gm a Alumina a t 40C . . . . . . . . . . . . . am 25. TemperatureDependenceof Watgr Vapor Adsorptionon Gm a Alumina Outgassed a t 80 C . . . . . . . . . . . . am Alumina Surface . . . . . . . . . . . . . . 2 . Ideal Alpha 6 a. Readsorption of Water Vaporon Camma Alumina at 5OoC . . 28. Influence of Outgas Temperature t i o n on Alpha Alumina at .on. Water. Vapor.Adsorp- . . .. .. ...
Adsorp40C

Influence of Outgas Temperature on Adsorption on Cm a Alumina am

61
62

63 65
66

69.
70
72

2. 9
30.
31

Comparison of Water Vapor Adsorptign a t 4OoC onAlpha and Gamma AluminaOutgassed a t 200 C TemperatureDependence Alpha Alumina Outgassed Readsorption of
of Water Vapor Adsorption on a t 8OoC

..........

74

............ Water VaporonAlphaAlumina a t 5OoC .

75 77
79
80
81

32.

Influence of Outgas Temperature on Hydrogen Chloride Adsorptionon Gamma Alumina a t 4OoC Readsorption of liyydrogen Chloride on 4OoC after O u t g a s s i n g f o r

33.

3. 4
3. 5

TemperatureDependenceof Hydrogen ChlorideAdsorption on Gm a Alumina Outgassed am 8OoC I d e a l Gamma Alumina S u r f a c e After Hydrogen Chloride Adsorption I n f l u e n c e of Outgas Temperature on Hydmgen Chloride Adsorptionon Alpha Alumina a t 4OoC

.......... Gm a Alumina a t am 18 hours . . . . . . . . . . . at ...........


..........

. . . . . . .. . . . . . . . . . . . . . . . .

85
86

36.

ix

37a

Temperature Dependence of Hydmgen Chloride Adsorption on Alpha Alumina Outgassed at 8OoC Readsorption of Hydmgen Chloride Alumina Outgassed
40C

3. 8
39

. . . . . . . . . . . . 87 at at 2OOOC . . . . . . . . . . . . . . . . 88
onAlpha
Chloride

40.
41.
42.

..................... 89 Comparison of HydrPgen Adsorption at 40C on Alphaand Gamma Alumina Outgassed a t 200C . . . . . . . . 93 Comparison of BET and Freundlich EQuations for F i t t i n g Experimental Data of H C l Adsorption on Alumina . . . 94
80C.......
Cm a a m

TemperatureDependenceofHydmgenChlorideReadsorpt i o n at OC onAlphaAlumina I n i t i a l l y Outgassed a t

Alumina Particle with Surrounding Layers of Water h s s i b l e Mechanism for Wdmgen Chloride Adsorption Alumina

....

98 100

43.
4 4 a

. . . . . . . . . . . . . . . . . . . . . . . . on .
,

Comparison of Experimental Data with Results Calculated Using the Langmuir and Freundlich Equations for HCl Adsorption a t OC on Cm a Alumina Outgassed a t 8OoC am
Isosteric Heat of Adsorption f o r H C l on Cm a Alumina am
Isosteric Heat of Adsorption f o r HCl onAlphaAlumina

. . . 106
. 108

45

. 109 47. ESCA Spectrum of Chlorine 2p Electrons Obtained f r o m Untreated Camma Alumina . . . . . . . . . . . . . . . . . 112 Spectrum of Aluminum 4. Untreated AlphaAlumina .2s. Electrons.Obtained .f r.o m . . . 113 8 .... .... . 4. Untreated AlphaoAlumina .2p. Electrons.Obtained. .fmm. . . . 114 9 ESCA Spectrum f Aluminum . . . . . . . . ESCA Spectrumof Oqygen 1s ELectmns Obtained f r o m 50 Untreated Alpha Alumina . . . . . . . . . . . . . . . . . 115 51 ESCA S p e c t w a of Chlorine 2p Electrons Obtained f r o m Untreated Alpha Alumina . . . . . . . . . . . . . . . . . 116
4. 6
E3CA

52

ESCA Spectrum of Chlorine 2p Electrons Obtained f r o m UntreatedTheta Alumina

. . . . . . . . . . . . . . . . .117

I.

INTRODUCTION
i s t h e s u b j e c t of i n c r e a s i n g as a major a i r

The q u a l i t y o f t h e e n v i r o n m e n t concern.IIydmgenchloride pollutant.

i s generallynotregarded

However t h e r e are s p e c i f i c i n s t a n c e s i n

which i t s envimn-

mental impact i s o f i n t e r e s t .
p r e s e n ti nt h ee n v i r o n m e n t found i n s o l u t i o n i n Andes, which

Hydrogen c h l o r i d e , HQ,

is naturally

as a p r o d u c t o f v o l c a n i c a c t i v i t y .

It i s

some r i v e r s , s u c h

as t h e Vinago FUver i n t h e

o r i g i n a t e f r o m volcanoes.'

Hydrogen c h l o r i d e was first

recognized as an air p o l l u t a n t i n t h e 1 9 t h c e n t u r y when i t was produced


as a byproduct i n t h e Lablanc process for manufacturing washing

s d .2 oa
and t h e

In recent years, the incineration of chlorinated hydmcarbons manufacture of products which

release hydrogen c h l o r i d e i n t o t h e
a greater environmental concern

environment as a bypmduct3 have caused

f o r t h i s d a n g e r o u s gas.
Solid rocket propellants4 whichhavebeendeveloped for use in aluminum

t h e NASA Space S h u t t l e Program producehydrogenchloride, oxide (alumina), carbon

monoxide and water vaporduringcombustion.


solid particles, such

A system consisting of several gases and

as a

rocketexhaust,canundergo of the exhaust components could

many d i f f e r e n ti n t e r a c t i o n s .I n t e l a c t i o n
lead t o c h e m i c a l r e a c t i o n s , a e r e s o l

f o r m a t i o n ,c a t a l y s i s ,a b s o r p t i o na n da d s o r p t i o n .

The problem is have shown

complicated by t h e fact t h a t e l e c t r o n d i f f r a c t i o n s t u d i e s 5 t h a t t h e aluminum oxide produced phases. in the exhaust

i s of two c r y s t a l l i n e
and t h e smaller par-

The l a r g e r p a r t i c l e s are alphaalumina

t i c l e s are g m a alumina. a m

Themain

objective o f t h i s r e s e a r c h

was t o i n i t i a t e a fUndamenta1 r e s u l t s of such a

study of t h e i n t e r a c t i o n o f study form a basis onwhich exhaust cloud

HC1 andalumina.The

t o assess t h e a d s o r p t i o n p m c e s s i n t h e

as a p o s s i b l e s i n k mechanism f o r t h e p o t e n t i a l l y

dangernus hydmgen chloride. When two immisciblephases(gas/solid) usually there thaninthe


are b r o u g h t i n t o c o n t a c t ,

i s a greater concentration of one phase


T h i sc o n c e n t r a t i o ng r a d i e n t

at the interface

bulk.

is caused by f o r c e s of

of attraction

between t h e two phases and

leads t o the concept

adsorption.Adsorption

is usuallyclassified

as e i t h e r p h y s i c a l o r
If

chemicaldependingontheforcesresponsiblefortheadsorption. t h e a d s o r p t i o n i s due t o van der W as i n t e r a c t i o n , t h e p r o c e s s al

is

called p h y s i c a la d s o r p t i o n( p h y s i s o r p t i o n )

Chemical a d s o r p t i o n the

(chemisorption) occurs when a chemical bond is formedbetween

solid ( a d s o r b e n t ) a n d t h e

gas molecule (adsorbate). been u s e d i n d u s t r i a l l y f o r many

Alumina and silica-alumina have

y e a r s as adsorbents, h e t e r o g e n e o u s c a t a l y s t s a n d c a t a l y s t s u p p o r t s . Treatment of alumina catalysts with hydrogen


halides h a s r e s u l t e d

inincreasedactivitytowardsisomerization,alkylation,polymerization
and o t h e r acid c a t a l y z e d r e a c t i o n s . 6 S p e c t r o s c o p i c s t u d i e s

by P d 7 ,a e ,

Tanaka and O h a s a w a r a9 and o t h e r s h a v e a t t e m p t e d t o e x p l a i n t h i s enhanced activity.

While i n f r a r e d s p e c t r o s c o p i c s t u d i e s
c h l o r i d e treated g m a alumina and a m

havebeen

made of hydmgen

g m a alumina of d i f f e r e n t degrees a m

of surface hydration, no systematic quantitative study of hydrogen


chlorideadsorption on g m a aluminahas a m been r e p o r t e d , f u r t h e r , no

Study of hydrogen c h l o r i d e a d s o r p t i o n reported.

on alpha alumina has been

A studyofthe

fate a n d i n t e r a c t i o n o f

HC1, HzO and Al 0 is

2 3

necessaxy t o p a r t i a l l y asses the impact of these exhaust products on theenvimment.Thisreportpresents adsorption of hydrogen chloride and

a q u a n t i t a t i v es t u d y

of t h e

water on alpha and g m a alumina. a m


pressure and pretreatment

S t u d i e s of t h e i n f l u e n c e o f t e m p e r a t u r e , c o n d i t i o n s were made, chloride adsorption

The effect of pre-adsorbed water onhydrogen may g i v e i n s i g h t i n t o t h e p o i s o n i n g

was studied and

of c a t a l y s t s @ water.

D i f f e r e n c e si nt h ea d s o r p t i o np r o p e r t i e so f

alpha and gamma alumina w e r e considered and give added emphasis

to

t h e r o l e which bulk and surface catalysis.

structures p l a y i n adsorption and

Thermodynamic a n a l y s i so fg a sa d s o r p t i o na n ds o l u t i o n

adsorption gave insight into differences of gas phase and liquid phase adsorption, the condition of oxide surfaces in the presence of

water a n d t h e mechanism of hydmgen chloride adsorption


surfaces

on t h e s e

C e r t a i n commercial materials and/or names o f manufactures are i d e n t i f i e d i n this p a p e r i n o r d e r t o s p e c i f y a d e q u a t e l y w h i c h m a t e r i a l s were involved in t h e r e s e a r c h e f f o r t . I n no case d o e s s u c h i d e n t i f i c a t i o n implyrecommendation o r endorsement of t h e materials by NASA.

11.
A.

HISTORICAL

Introduction
A review of the literature pertinent to the adsorption of

hydrogen

chlorideonalumina

is presentedinthissection.

N o a t t e m p t i s made

t o review a l l t h e l i t e r a t u r e adsorption include,

onad.sorption.Standardreferenceson

Young and Crowell ,11 Ross and Oliver," Flood

13

and Hayward and Trapnell. B.

14

S o l i dP r o p e l l a n tJ h h a u s tS t u d i e s S o l i d r o c k e t propellants proposed f o r u s e i n t h e
NASA S p a c e S h u t t l e

Program may pose anenvironmental

pr~blem.~ The p r o p e l l a n t 1 5 is

composed o f an ammonium p e r c h l o r a t e o x i d i z e r d i s p e r s e d i n

a synthetic

rubber b i n d e r f u e l c o n t a i n i n g aluminum and various o.ther additives.


Predictionsoftheexhaustproductconcentrations rocketmotor
f r o m such a s o l i d

are available.l6Typicalexhaustcomposition
24.S

is 3 0 . 8

A1203, 20.9% HCl, 9 . q H20,


0.6% FeCl

C , 3.4% CO2' O

2.5% H2,

8.?$ N2 and

3'

NASA has ongoing an experimental

program t o measure t h e

e f f l u e n t c o n c e n t r a t i o n s 15917'18 e f f l u e n t s . 19'20

and t o s t u d y t h e i n t e r a c t i o n

of the

The data o b t a i n e d in these s t u d i e s will be used i n

t h e v e r i f i c a t i o n of atmosphericmodels,such d i s p e r s i o n model.21

as t h e NASA m u l t i l a y e r

T h i s model will be used t o d e f i n e t h o s e w e a t h e r produce unacceptable effluent

c o n d i t i o n s d u r i n g a launch whichwould concentrations and hence present C. Alumina System

a launch constraint.

Aluminum o x i d e e x i s t s i n s e v e r a l d i f f e r e n t c r y s t a l l i n e f o r m s 4

5
which can

be i n t e r c o n v e r t e d ,u s u a l l y

by h e a t i n g .E a r l ys t u d i e sw i t h

the alumina system

dealt w i t h p r e p a r a t i o n o f v a r l o u s f o r m s

of alumina

based ontemperature-pressurerelationships.Thebulkcrystal

struc-

t u r e was i n v e s t i g a t e d as well as t h e p h y s i c a l a n d c h e m i c a l p r o p e r t i e s o ft h ev a r i o u sf o r m s .E x t e n s i v er e v i e w so ft h e X-ray p a t t e r n s ,

structure,nomenclature,thermaltransistionsandphysicalandchemical properties of the


and B l. el

aluminum o x i d e s are given by Rooksby2'

and by Werfers

23 aluminum o x i d e h a s n o t been as widely

The surface chemistry of

researched as t h eb u l ks t r u c t u r ea n dp r o p e r t i e s .B i e l a n s k ia n d S e d ~ i m i i n v~s t i g a t e d t h e t h e r m a l p r e p a r a t i o n , c h e m i c a l p r o p e r t i e s r~ e and some a d s o r p t i v ep r o p e r t i e so fs e v e r a la l u m i n a s .T h r e es e q u e n c e s of phase transformations


were r e p o r t e d :

Series I:

M i x t u r eo fb a y e r i t e ,h y d r a g i l l i t ea n d amount o f boehmite-Y 8

S e r i e s 11; Boehmite-yS e r i e s I11: Bayerite The rate o f d i s s o l u t i o n

y-

8 -X

--

a small X-a-A1 0 2 3
2 3

e-x-a-Al
a-A1 0 2 3

of t h e d i f f e r e n t

forms of a l u m i n a i n HCl and


,of c a l c i n a t i o n . T h i s

i n NaOH decreased w i t h i n c r e a s i n g t e m p e r a t u r e

was a t t r i b u t e d t o a decrease i n t h e s u r f a c e

area d u r i n g t h e transition

from t h e low temperature gamma ( y ) o r delta (6) forms t o t h e h i g h temperaturealpha

( a ) form.

BET s u r f a c e areas measuredusing

C02

a d s o r p t i o n a t " 7 9 O C confirmed t h i s decrease i n surface area.

The

specific d e n s i t y of t h e alumina was p r o p o r t i o n a l t o t h e of calcination.Adsorptionof


e x h i b i t e d a dependenceon

temperature

water vapor on the dlfferent aluminas

thetemperatureofthecalcination,but

6
only a s l i g h t dependence on the

time of t h e c a l c i n a t i o n was observed.

F r o m t h e amount o f water adsorbed over a given time p e r i o d a n d t h e


change i n t h e rate of adsorption, Bielanski and that increasing calcination temperature decreased pores in the y-alumina and thus decreased the t i o ns t e p .N e g l i g i b l ea d s o r p t i o no f D. S u r f a c eS t u d i e so f Alumina aluminum
of i t s

Sedzimer concluded
t h e number of micm-

rate o f t h e

slow adsorp-

water occurred on alphaalumina.

S t u d i e s of t h e a d s o r p t i o n a n d s u r f a c e p r o p e r t i e s o f oxide have been directed mostly i m p o r t a n tu s ei nc a t a l y s i s . alphaalumina

a t gamma aluminabecause

Few s t u d i e s have been concernedwiththe

surface.

Hair25reviews t h e adsorptionandsurface

properties of alumina prior to

1967.
sites ony-alumina
for

Hightower discussed the nature of active

severaldifferentreactions,includingortho-parahydmgenconversion,

Hz

- D2 exchange,

olefinisomerization,polymerizationandalcohol two test r e a c t i o n s ( D


2

dehydration. Using

exchangeandolefinisomer-

i z a t i o n ) as well as infrared spectroscopy, Hightower found of surface

four types

sites ony-alumina. sites on'I/-aluminawhich

Another review of the chemisorption

stresses i t s c a t a l y t i c i m p o r t a n c e was given by Cvetanovicand


Amenomiya.26 The = v i e w c o n s i d e r s t h e

sites f o r e t h y l e n e a d s o r p t i o n ,

hydrogenexchangeandchanges alumina. Recent s t u d i e s haveused

in active sites during activation of

many a d s o r b a t e s on alumina including

HzS,a928

amines, 29 C' O 2 , '

HF',32

acetylene^,^'

a l c o h o l s , 34

7
S02,35 and pyridine. 36 These s t u d i e s haveemployed a v a r i e t y of
techniques such measurements and E.

as i n f r a r e d s p e c t r o s c o p y , Ranan spectroscopy, kinetic


electron paramagnetic resonance.

Adsorption of Water on Alumina The m s extensive study of the alumina surface ot


was an infrared

s p e c t r o s c o p i c study r e p o r t e d i n a series of papers by P e r i . 37-42 U s i n g transparent aerogel plates of y-alumina, Ped investigated the hydration and dehydration Undried alumina aerogel plates 3300and
and Hannan

37

of alumina up t o 1000C.

showed broad absorption bands

at

1650 cm-l corresponding t o s t r e t c h i n g and bending frequencies


These two bands disappeared

found i n l i q u i d water. t h e sample under

after outgassing

vacuum a t 4OO0C i n d i c a t i n g t h a t a l i q u i d film of


Infrared spectra taken a f t e r o u t g a s s i n g t h e

water hadbeenremoved.

alumina at 650

- 7OO0C

showed a b s o r p t i o n b a n d s c h a r a c t e r i s t i c Even a f t e r e v a c u a t i o n

of

isolatedsurfacehydroxylgroups.

a t 9OO0C, t h e

spectra still revealed the presence of

isolated hydroxyl groups on o f t h e bands was of water

t h e s u r f a c e of a l u m i n a , a l t h o u g h t h e i n t e n s i t y decreased.Rehydrationexperiments

showed t h a ta d s o r p t i o n

vapor on alumina d r i e d a t 8OO0C d i d not produce hydroxyl groups mom temperature b u t r e h y d r a t i o n t o

at

form hydroxyl groups c o u l d o c c u r

a t e l e v a t e da d s o r p t i o nt e m p e r a t u r e s .I n f r a r e d
adsorption of other gases such

spectra taken a f t e r

as NH3, D2, and CC14 showed t h e


gmups i n t h e adsorption process.

importance of the isolated hydroxyl

A quantitative study

by Peri38 on t h e r e h y d r a t i o n o f d r i e d

a l u m i n a showed t h a t t h e e x t e n t of surface hydration i s p r i m a r i l y c o n t r o l l e d by dryingtemperature.

Dry aluminacould"chemisorb"

one a o l e c u l e of water p r 11-16 e


the drying procedure.

22 o f

surface at 100C dependingon

A statistical model f o r t h e s u r f a c e o f proposed by %ri41 to e x p l a i n t h e r e s u l t s o f rehydrationexperiments. The model

y-alumina has been


h i s dehydration-

is l a s e d on t h e p r e f e m d exposure

of a single crystal plane (100) .of s p i n e l a t t h e s u r f a c e of gamma


alumina.The
ideal d q surface is assummed t o c o n t a i n o n l y o x i d e i o n s ,

with one oxide ion occupying

an area o f 8

22

as shown i n figure 1.

EBch aluminum ion i s surrounded

4 oxide During ions. hydration


The dehydration

t h e e n t i r e surface is converted t o hydroxylions.

process was simulated by allowing adjacent OH groups t o combine and

form water molecules which are desorbed.

By randomlyremoving

two

a d j a c e n t h y h x y l g r o u p s at a time f r o m t h e surface one eventually obtains a surface containing five different types of
shown i n figure 2.

OH g m u p s as

The result of this statistical a n a l y s i s r e i n f o r c e s t h e results o f

Peri and H a n n a n ~ ~ ~ i n f r a work,where red


found i n t h e spectrum. The model

t h r e e distinct peaks

were

p r e d i c t s t h a t t h e alumina surface
OH groups i s possible.

w i l l be q u i t e complex u n l e s s m o b i l i t y o f t h e

Only a t extremely high temperatures would mobility of the hydmxly groups be p o s s i b l e , t h u s t h e s u r f a c e p r o p e r t i e s of alumina wl be il showed t h a t

determined by t h e n a t u r e of thehydmxylgroups.PedB h d o y groups ay rxl

still present a t 9OO0C and t h e r e f o r e s i g n i f i c a n t

mobility i s notlikely.Mobilitycausing during tIatlSfoITWtion t o d i f f e r e n t c r y s t a l change t o alpha alumina a t 1200C.

OH removal may be p o s s i b l e
forms, f o r example t h e

0
0
figure 1.

Oxygen

Aluminum

Ideal Gm a Alumina Surface (41) am

10

1 1

De Boer, e t al.43 s t u d i e d t h e a d s o r p t i o n o f

water on four

d i f f e r e n t aluminas ( g i b b s i t e , .\'-y mixture, .\'-y-Kmixtureandboehmite)


dried a t 12OO0C.

Loss.of weight

a t 1200C after s a t u r a t i o n w i t h water


water.
Theamount

vapor was d i r e c t l y r e l a t e d to t h e amount of adsorbed o f t h e adsorbed water physisorbed and chemisorbed mining weight

was found by d e t e r -

loss o f t h e ' a l u m i n a a t 12OoC (physisorbed) and, f u r t h e r water amounted


water.
The

l o s s after i g n i t i o n a t -1200C (chemisorbed).Chemisorbed t o 24.8 mg H20/100m


2 ' and 33mg H20/100m
2

ofphysisorbed

amount of chemisorbed

water foundon

t h e f o u r d u m i n a s was e s s e n t i a l l y no precaution was made t o

t h e same, which i s n o t s u r p r i s i n g s i n c e prevent conversion treatment.

of t h e a l u m i n a s t o a l p h a a l u m i n a

by t h e ,1200C h e a t

D Boer, e t e
coverageof

u s et h e d

BET equation to determine monolayer known surface area. The area of

water on the alumina of

a adsorbed water molecule was determined t o be 12.1 n


using this method.
A further study of

x 2 on the alumina
Si02,

water a d s o r p t i o n on alumina was r e p o r t e d by


study made a comparisonof

Morimoto, Nagao andInai.&Their

Al 0 and Si02-A1203 s u r f a c e s .S i l i c a ,

which has been s t u d i e d 2 3 e ~ t e n s i v e l y ,s ~ o~ s d i f f e r e n t a d s o r p t i o n p r o p e r t i e s t h a n h w alumina.. amountof

AS silica i s h e a t e d a t s u c c e s s i v e l y h i g h e r t e m p e r a t u r e t h e

water adsorption decreases, because

of the formation of Si-0-Si


Alumina, however, showed

linkagesandthedecreaseofhydroxylgroups.

an increase i n a d s o r p t i o n c a p a c i t y w i t h t e m p e r a t u r e o f p r e t r e a t m e n t ,
The

BET equation was u s e d t o calculate the monolayer ,coverage and

t h e area occupied by each adsorbed water molecule was c a l c u l a t e d t o

12

be 16.6f2.

Theamount

ofchemisorbed

water was determined by t h e

amount o f water removed by h e a t i n g a t 3OoC u n l i k e t h a t d e f i n e d by

de Boer, e t al.43 as water removed by h e a t i n g at 12OoC.

A important n

p o i n t e s t a b l i s h e d by Morimoto and coworkers was that t h e area o f t h e adsorbed water w s constant, even though alumina a showed i n c r e a s i n g onecan

water adsorptionwithincreasingheattreatment.Therefore,
p o s t u l a t e that t h e adsorbed area does not change since

H20 can adsorb Figure 3A

i n two ways on analumina

surface as shown i n Figure 3.

shows water adsorption on a dehydroxylated surface and t h e adsorbed species on a hydmxylatedaluminasurface. tions occur through the formation of stmng hydmgen
workx

Figure 3 B shows
Both adsorpbonds. Peri's

a t elevated temperature showed t h a t a t high temperatures H20


as i l l u s t r a t e d

could form new h d o y p u p s o n t h e a l u m i n a s u d a c e y rxl

i n Figure 4. The area of adsorbed

water, 16.682 , found by Morimoto, e t

a.44 l

is i n good agreement with


However,no

Peri's model of t h e g m a alumina surface. a m

precaution was taken by Morimoto t o i n s u r e t h a t the alumina

prepared by hydrolysis o f aluminum isopmpoxide was of a s p e c i f i c c r y s t a l l i n e fonn, i.e., reported. noX-ray powder d i f f r a c t i o n results were

One study of adsorption

on a l p h a alumina was that of Carruthers,

M e , SingandStryker.46Studyingalumina,
oxide, these workers determined

silica and chromium

surface area and porosity using


Showed that

nitmgenandargonadsorptionandor-plots.Thispmcedure of the aluminas studied,

(a, 8 and gibbsite calcined

a t 8 O O 0 C ) , only

Figure 3.

Nature o f Water Adsorbed on Alumina

Surface

Figure 4.

Formation of ydroxyl Croups on Alumina Surface by Water'Vapor Adsorption a t ELevated Temperatun%

t h e g i b b s i t e was porous.

By s t u d y i n g a d s o r p t i o n - d e s o r p t i o n c y c l e s

of

water the workers showed t h a t d e h y d r a t e d a l u m i n a s u r f a c e s


the type of hydraphobic character displayed Qmpaxison of

do e x h i b i t

by dehydmxylated silica.
showed t h e

water adsorption on alpha and theta alumina

alpha dumina adsorbed more water p r unit area t h a n t h e t h e t a a l u m i n a . e


The authors concluded that a l p h a alumina has a h i g h a f f i n i t y f o r water with chemisorption taking place a t low p r e s s u r e t o f o n h y d m q l on this hydroxylated surface.

groups and physical adsorption occurring This high affinity exhibited

by a l p h a a l u m i n a f o r water is a s s o c i a t e d

with a marked tendency for exposed aluminum i o n s t o be rehydrated, thus allowing dissociative chemisorption of sorption.
A comparison of the adsorption properties of

water followed by physi-

eta and gamma alumina

was made by MacIver, and Tobin Studying the hydrationdehydrationcycleofthe two aluminas, the workers found

that eta

and gamma a l u m i n a c o n t a i n e d d i f f e r e n t

amounts of pre-adsorbed water. which

Removal of this w a t e r p r o d u c e d s u r f a c e a c i d i t y i n t h e a l u m i n a s was i n v e s t i g a t e d u s i n g c h e m i s o r p t i o n o f ammonia.

A l a t e r paper by

MacIver, Wilmot and Bridges@ s t u d i e d t h e i n f l u e n c e of t h i s a c i d i t y on t h e catalytic p r o p e r t i e s o f t h e two aluminas.


of water

Several workers have studied the heats of adsorption on a u m i n a u s i n g c a l o r i m e t r i c studied the heat of alumina and the theheatsof methods. Every,

Wade and Hackerman49 amorphous

immersion i n water of a l p h a , gamma and an

effect of particle s i z e and outgassing

temperature on

immersion.The

t r e n d o b s e r v e d was that as particle

16

size decreased the heat of

immersion increased.

A dramatic d i f f e r e n c e
gama aluminas

in t h e h e a t o f immersion f o r t h e a l p h a . a l u n i n a s a n d t h e
was noted k t could be due t o a particle s i z e effect.

The a l p h a

a m aluminas had l a r g e r particle s i z e s t h a n t h e gm a aluminas.


The i n f l u e n c e o f o u t g a s s i n g t e m p e r a t u r e

w s s t u d i e d by Every, a

e t al.w by e v a c u a t i o n f l u m i n a a m p l e s o o r r o r oa s tt f

72 hours.

The results showed t h a t heats of immersion i n c r e a s e d w i t h i n c r e a s i n g o u t g a st e m D e r a t u r e .T h i st r e n da c c o r d i n gt ot h ea u t h o r s indicate the ex3.stence of adsorbed

seemed t o

water above 20OoC.

I n a l a t e r studyEvery,

Wade, and H a c k e n ~ a n ~ ~ i n v e s t i g a t e d t h e

difference i n alpha and gamma alumina toward water, n-hexaneand

CH OH adsorotion.

Alpha alumina adsorbed more H20 than g m a alumina a m


Also

p r u n i t area, k t no e x p l a n a t i o n of t h i s d i f f e r e n c e was given. e


t h e q u a n t i t y of water adsorbed i n c r e a s e d w i t h i n c r e a s i n g o u t g a s temperature. Morimoto,Shiomi
axe3

and Tanaka51 s t u d i e d t h e v a r i a t i o n o f s u r f a c e

of a l p h a and gamma a m a and measued t h e h e a t of immersion l i u n


The s u r f a c e area of gamma alumina began to decrease at

i n water.

6OO0C, whereas the alpha alumina surface

area remained constant.

Heat of immersion data f o r both aluminas showed a dependence on outgas


temperature initially increasing to decreasing. measured t h e heat of immersion of alpha Cochradle and R u d h a ~ n ~ ~ alUmina and gamma alumina i n Hater a f t e r o u t g a s s i n g a t 30OoC. h e a t of immersion f o r a l p h a a l u m i n a
and g m a alumina nea m

a maximum a t 60O-65O0C t h e n

The

-773 and

-648 mJ/m 2 , r e s p e c t i v e l y .

A l a t e r study of heats of
Pearce and R ~ d h a m ~ alpha and on ~ Again a d i f f e r e n c e i n h e a t o f alumina.The heat of

immersion was t h a t of Hendriksen, gamma alumina outgassed from


100-6OO0C.

immersion was found f o r a l p h a and gamma

immersion also increased with increasing outgas

tempemtun?, thus indicating that oCCurr5.ng.

more surface hydration could


of Morimoto,

be

C o n t r a d i c t o r yt ot h er e s u l t s

e t al., 51
of alumina

Hendriksen Pearce and

Rudham5' found that the surface

outgassed at temperatures greater than 6OO0C did not anneal but r e t u r n e d t o i t s initial state when re-exposed t o water. I n summary, measurement of water adsorption on alumina has shown
pro-

that the crystalline phase of alumina influences the adsorption p e r t i e s .S e v e r a l

d i f f e r e n t mechanisms for water adsorption onalumina

can take place depending of the adsorption.

on thermal pretreatments and the temperature new hydroxyl p u p s , hydrogen bond i o n s on the alumina surface.

Water canform

t o two h y m x y l m u p s o r adsorb onoxygen

The existence of two f o n s of adsorbed water (chemisorbed and physisorbed) has F. been r e p o r t e d ,

Hydrogen Chloride Adsorption Studies of hydrogen chloride adsorption on s o l i d adsorbents have

been l i m i t e d due i n part t o t h e e x p e r i m e n t a l d i f f i c u l t y o f h a n d l i n g


t h e c o m s i v e HQ a n d t h e p r e v i o u s l a c k
of t h e i n t e r a c t i o n . S t u d i e s
of recognition of t h e importance

of H C l adsorption on N a B and K

r u t i l e , 55156 silica,40 evaporated metal films,57 metal c h l o r i d e s

supported on aluminas and

a l u m i n d 9 have been reported.

18
The i n f r a r e d s t u d y

by P a r f i t t , e t al.56 showed t h e c h e m i s o r p t i o n
TiOZ t o o c c u r by t h e r e a c t i o n shown i n

of hydrogen chloride on
. F ' i g u r e

5A.

The e x i s t e n c e o f

a surface s p e c i e s as i n Figure 5 B
a titanium ion and in

c o n s i s t i n g of a water molecule coordinated to conjunction with a c h l o r i d e i o n g i v e s bands a t 1565 and 3360 cm'l. Peri,& during adsorption studies not appreciably adsorbed

rise to infrared absorption

on s i l i c a , f o u n d t h a t

H C l was

on t h e s i l i c a s u r f a c e . Alumina

C .

Hydrogen ChlorideAdsorptionStudieson

I n conjunction with his i n f r a r e d s t u d y of t h e h y d r a t i o n a n d


rehydration of the gamma alumina surface, P e r i 4 2 s t u d i e d t h e a d s o r p t i o n gamma alumina. Peri found

of H C l on silica-alumina and

that H C l
2

a d s o r p t i o n on s i l i c a - a l u m i n a preventedadsorption of adsorbent. the

o f CO

on a-sites

H stated t h a t H C l , NH e

and many o t h e r adsorbates

react e x t e n s i v e l y w i t h gamma aluminabut


of HQ a d s o r p t i o n was made.

no q u a n t i t a t i v e measurement

Peri p o s t u l a t e s t h a t t h e a d s o r p t i o n
O aluminathe n Al+O--Si.

site

o r "a-site" i s a " s t r a i n e d "o x i d el i d r a g e .


p o s t u l a t e dt o be A 1 0

a-site was
These

2-

Al+ andonsilica-alumina;

s i t e s chemisorb HQ

t o form Al-OH---Cl-Al. made a n i n f r a r e d i n v e s t i g a t i o n

In another paper Pea7

of the

hydmgen chloride reaction with the alumina aerogel plates outgassed t i o n at

Using s u r f a c e o f gamma alumina.

a t 8OO0C, P e r i f o u n d t h a t

H C l adsorp-

5OoC gaveanabsorption
groups.

band a t 3500 cm-l, a s s i g n a b l e t o Bands which would

hydmgen bonded hydroxyl

result f r o m

Q-0 and Al-Q were n o t i n the frequency nnge of the study.

Desorptionof

H C l removed some of t h e OH groups.

Using a d e u t e r a t e d

Ti 0 ,

4t

/*
H

Figure 5.

Adsorption of Hydrogen Chloride on Ti02

20

alumina surface, Peri o b s e r v e d t h a t HQ deuteroxyl gmups

did n o t react w i t h the o r i g i n a l

i n strong preference to the

bare oxide surface.

perf 7 also s t u d i e d t h e a d s o r p t i o n of HQ

at e l e v a t e d t e m p e r a t u r e s

(6OO0C), t h e effect of preadsorbed HQ on c02 a d s o r p t i o n a n d t h e


catalytic activity of Tanakaand H C l treated alumina toward butene isomerization. of HQ pretreat-

Ogasawam9 i n v e s t i g a t e d t h e i n f l u e n c e
a m a and silica. l i u n

ment on t h e catalytic a c t i v i t y o f

Inagreement

Hith Peri742 they found that chemisorption of procuces new hydmgenbonded a d s o r p t i o n on alumina

H C l . on dry alumina The

hydroxyl groups on t h e s u r f a c e .

o u t s s s e d a t 5OO0C was v e r y r a p i d a n d i m e v e r -

s i b l e a t mom t e m p e r a t u r e , g i v i n g molecules/cm protonic and


2

a m a x i m u m a d s o r p t i o n of 3 x 10

14

The new hydroxyl q u p s formed by HQ

a d s o r p t i o n are

participate i n n-butene isomerization

as Bronsted acid
the silicasurface

sites.

Hydrogen c h l o r i d e was adsorbed minimallyon

and t h e i s o m e r i z a t i o n of n-butenes on NQ-exposed

silica d i d not occur.

Further studies of HCl-treated alumina catalysts o u t by Ogasawara, Takagawa and


Takahashi.

were c a r r i e d
showed

T h e s es t u d i e s

t h a t HCl t r e a t e d gamma a l u m i n a i n c r e a s e d t h e c a t a l y t i c e f f i c i e n c y during diphenylammine s y n t h e s i s . Wightrnan6 used a Calvet microcalorimeter to

measure t h e heats of

immersion o f alpha and gamma alumina i n water and hydrochloric acid. The measurements were performed a t d i f f e r e n t o u t g a s t e m p e r a t u r e s a n d HCl concentrations.

Heats of immersionofaluminas

i n water were The h e a t of

found t o increase withincreasingoutgastemperature. immersionof alphaalumina

was l e s s than t h a t of gamma alumina.In


of immersion i n c r e a s e d f r o m -888 mJ/m
2

h y d m c h l o r i c acid, t h e h e a t

*These c a l o r i m e t r i c s t u d i e s a r e d e s c r i b e d

i n d e t a i l i n Appendix 1 2 .

21

ta -1829 mJ/m 2 as the outgas temperature


400C f o r a l p h a a l u m i n a .

was v a r i e d from 8 0 '

to

Gm a alumina outgassed a t 10 am 0'


r e s p e c t i v e l y .V a r i a t i o n

and 400C

gave -727 and -1728 mJ/m2,

of t h eh e a to f
concentration

immersion of alpha alumina outgassed

at 2OO0C with HQ

was n t as pmnounced, giving o mJ/m 2


f o r 0.1 M H U .

- 1 4 mJ/m2 13

f o r 0.001 M I f C l and

-1351

Tyree, in a series o f r e p o r t s , 61"63 s t u d i e d t h e s o l u t i o n c h e m i s t r y

of t h e HC1-A1 0
the system

system. Measurement of vaporpressurechanges in 2 3 was used t o determine which o f t h e f o u r r e a c t i o n s shown

i n figure 6 would occur.


Using two d i f f e r e n t aluminas, t h e t a alumina and mixed Al(OH),, significant differences in vapor pressure lowering a d d i t i o n of t h e a l u m i n a s t o v a r y i n g c o n c e n t r a t i o n s acid.
J

were found upon

o f hydrochloric

An o b v i o u s d i f f e r e n c e i n t h e r e a c t i v i t y o f t h e

two aluminas was

noted in the

f a c t t h a t a l a r g e r d e c r e a s e i n vapor pressure i n a s h o r t e r
mixed alumina, Al(0H)

time was o b s e r v e df o rt h e

3'

Changes i n p of H

HU/alumina s l u r r i e s were a l s o measured. I n s m a y the following conclusions can u mr HQ/alumina interaction.


be made a b u t t h e

HC1 adsorbs on alumina rapidly and irre-

v e r s i b l y t o formhydroxyl

wups.

Thesehydroxylgroupsareimportant have shown t h a t HC1

in some catalytic r e a c t i o n s .D e u t e r a t i o ns t u d i e s
reacts p r e f e r e n t i a l l y w i t h t h e
bare oxidesurface.

Again, as i n t h e

case of water a d s o r p t i o n , t h e h e a t s
Of

of immersion show the importance

OUtgaSSinC: temperature on hydrogen chloride adsorption.

22

1 .

H20(g)

A1203

2.

A1203(s)

H20(g)

3.
4.

HQ(g) + H20(1)

HCl(aq) + A l ( O H ) 3 ( s ) AlCl+d
AI.(OH)nCl

5.
6.

+ Al(OH)j(s)

Al(OH)3

surface eaction r

A1 0 (s) 2 3

H20(1)

(on the A1203(s))

HQ(aq)

AlC13(aq) A1(OH)nQ3-n(aq)

3-n

(as)

Al(OH)3(gibbsite)

AlCl (aq)

Flgure 6.

Pmbable Reactions that Occur in a System Containing Aluminum Oxide, Water Vapor and Hydrogen Chloride (61-63)

H.

ESCA S t u d i e s
The 1967 monograph by Siegbahn, e t al.& described the analysis The technique

of p h o t o e l e c t r o n s as a probe of surface composition.

was d e s i g n a t e d

EC , SA

e l e c t r o ns p e c t r o s c o p yf o rc h e m i c a la n a l y s i s .

In

EC , SA

a s o l i d sample i s i r r a d i a t e d w i t h X-raysfollowed

by a n a l y s i s
The k i n e t i c

of t h e k i n e t i c energy o f t h ep h o t o - e j e c t e de l e c t r o n .
energy of t h e e l e c t r o n (K.E.)

i s related to the energy level

from

wNch it was e j e c t e d by t h e e q u a t i o n :

hv

i s t h e energy of t h e i n c i d e n t

X-rays,

B.E.

thebindingenergy

of

the photo-ejected electron and

@ t h e work f u n c t i o n of the spectrometer.


a chemical s h i f t
be used as a

Slight changes in the electronic environment produce in electron binding energy and the chemical shift can method o f q u a l i t a t i v e a n a l y s i s . The ESCA technique has found surfacesandadsorbedspecies.

numerous a p p l i c a t i o n i n s t u d y i n g Reviews been have presented by

Hercules 6566 a n d c u r r e n t l y t h e u s e technique i s being studied. 67 ,68 Kishi and Ikeda

of ESCA a s a q u a n t i t a t i v e s u r f a c e

69 r e p o r t e d a n ESCA study of c h l o r i n e g a s a d s o r b e d
N i , Pd, A g , and Au.

on evaporated metal films ofFe,


Q2 g a s t h e

O exposure t o n
( I 2 treated

Q 2p p h o t o e l e c t r o n l i n e

was recorded.For

AU t h r e e peaks were observed i n t h e C1 2p region a t binding energies


197.0, 199.4 and 201.4 eV, t h e Pd s u b s t r a t e showed onlyonepeak, whereas all t h e o t h e r c h l o r i n e t r e a t e d m e t a l a d s o r b e n t s showed two

24

peaks i n t h e Q 2p region.
dependon

The Q 2p binding energy

was found

' o t

t h e amount of adsorbed c h l o r i n e .

Chemical shifts i n t h e

metals v a r l e d f m m +3.3 e f o r t h e Fe V 2p
These chemical

t o -0.3 e for t h e Ag 3d5y2. V 3/2 shifts w e r e compared w i t h t h e c h e m i c a l shifts o f known

metal c h l o r i d e compounds as a means of i d e n t i f y i n g t h e surface species.


A ESCA study of aluminum o x i d e s was reported by Lidsay, e t al. n

70

Theseworkersmeasuredthe

A1 2p e l e c t r o n s p e c t r a of several anhydmus
compounds and t h e r e s u l t s o f t h e

and hydrated aluminum oxides.The

ESCA bindingenergymeasurements

are p r e s e n t e d i n T a b l e

I.

The data

shows a decrease i n binding energy with


positivelychargedionsinthe
solid.

an i n c r e a s e i n t h e m o u n t o f
The t r e n d was explained by t h e

fact that t h e e l e c t r o n e g a t i v i t y of oxygen i s higher than hydroxyl


groups, thus the binding energy

of t h e A l c o r e electrons i s h i g h e r

t a t h o s e of t h e aluminum hydmxides. hn

TABLE I
BINDING ENERGY, PEAK WIDTH, AND CHEMICAL S H I F T

OF AI. (2p) GLECX'RONS I N A L U M I N U M OXIDES(?O)


F l Width ul
Compound

Half Mx a (ev)
2.25

Binding Energy (ev)

Chemical Shift

0
1.0

a-A1203
2 4 '

76.3 2 0 1 .
75.3 5 0.1

2.50 2.26
2.46

a-AlO(0H)
P-AlO(011)

74.8 2 0.1 75.7 2 0.1 74.9


0.1.

1.5
0.6
1.4

a-Al (OH)
8 - f i (OH)

2.35
2.40

74.7 2 0.2

1.6

111.

EXPERIMENTAL

Thissectiondescribesthe

materials, c h a r a c t e r i z a t i o n t e c h n i q u e s ,
used i n t h i s s t u d y .

and theexperimentalprocedures
procedures are also presented.
A.

Data r e d u c t i o n

Description of

Materials
The adsorbates used
were n i t r o g e n , water and

1. Adsorbates:

hydrogen chloride.Reagentgrade(purity c h l o r i d e was obtainedfrom

9%) anhydrous hydrogen


N i t r o g e nu s e di nt h e

Matheson Company.

surface area measurements was of u l t r a h i g h p u r i t y


from
Matheson.

(9%) o b t a i n e d
water
vacuum

Water vapor was produced by u s i n gd i s t i l l e d


degassed by repeated freeze-thaw cycles on the

whichhadbeen

system.
2. Adsorbents: Two aluminas were used as adsorbents. The gamma

alumina was o b t a i n e d from t h e Cabot C o r p o r a t i o n , b s t o n , M a s s a c h u s e t t s


and is a high surface
fumed aluminaproduced

area aluminadesignated
by t h e h y d r o l y s i s o f

Alon-C. Alon-C

is a

aluminum c h l o r i d e i n a

flame p m c e s s , similar t o t h e method d e s c r i b e d by Fricke and Jockers. 71


According t o t h e m a n u f a c t u r e r , Alon-C i s predominantly gamma alumina,

2 having a surface area of approximately 100 m / g and an average

particle s i z e of 0.03 micmns.

X-ray powder d i f f r a c t i o n p a t t e r n s of Alon-C was indeedpre-

Alon-C using Cu K

radiationconfirmedthat

dominantly gamma alumina. The a l p h a a l u m i n a u s e d i n t h e s t u d y

w s obtained from the a

Aluminum

Company of America, Pittsburgh, Pennsylvania and designated

u6z.

A 6 i s produced by h e a t i n g a t r a n s i t i o n a l u m i n a a t 15j7Oc, A c c o f i ~ 1X
26

t o the manufacturer, U6SC i s an alpha alumina with


( micron. 1

a particle size

X-ray powder d i f f r a c t i o n patterns of Al6SG e x h i b i t e d

d i f f r a c t i o n l i n e s characteristic of alpha alumina, confirming that


Al6SC i s an alpha alumina.

B.

Characterization Techniques

1. Surface Area Measurements:

An important property

to consider

when s t u d y i n g t h e a d s o r p t i o n p r o p e r t i e s

of s o l i d a d s o r b e n t s I s t h e
g m a alumina a m

surface area.

The surface areas of alphaaluminaand

were determined by t h e BET method described by Gregg and Sing. 72


The system and experimental procedure has been previously described

by Hendley, O'Neal andWight~nan.'~Prior


ments, the aluminas

tothesurface

area measure-

w e r e o u t g a s s e d f o r 2 h r s a t 100, 200 and 400C

at

(lo+
2.

t o r r ) , which corresponded t o t h e t h e r m a l p r e t r e a t m e n t u s e d
water vapor adsorption studies.

i n t h e hydrogen chloride and

Nitrogen Adsorption-Desorption Measurements: Adsorption and

d e s o r p t i o ni s o t h e r m s

of n i t r o g e n w e r e measured on bothaluminas. as t h a t described by Hendley,


Desorptionmeasurements

The

Same system and adsorption procedure


O'Neal and Wightrnan7'

was employed.

were made

by s u c c e s s i v e l y i n c r e a s i n g t h e amount u s i n g a gas buret.

volume of the system

by a p r e c a l i k a t e d

The i n i t i a l p r e s s u r e of t h e n i t r o g e n
SO

adsorbate was a p p r o x i m a t e l y 1 2 0 0 t o r r
desorptioncyclecould

that t h e a d s o r p t i o n

The

be measured a t r e l a t i v e p r e s s u r e

('/Po) v a l u e s
pores.

up t o 0.95, t h u s c a u s i n g c a p i l l a r y c o n d e n s a t i o n i n t h e methodof calculating pore size distribution

f r o m nitrogenadsorption

d e s o r p t i o n data i s d e s c r i b e d by GreggandSing.

74

28

3.

Scanning ELectron Microscopy

(SEM)I

P a r t i c l es i z ea n d

topography were s t u d i e d u s i n g an Advanced Metals Research Corporation Model 900 scanning electron microscope operating micrographs of alumina samples

a t 20 kV.

Photo-

after v a r i o u s t r e a t m e n t s were taken


X-ray

a t lOOX, l O O O X and 5000X m a g n i f i c a t i o n .b e r g yd i s p e r s i v e

a n a l y s i s (EDAX) of t h e alumina particles was p r f o m e d u s i n g a n I n t e r n a t i o n a l Model

707A u n i t attached t o

t h e microscope.
and

Photomicrographs were taken of both aluminas, untreated

after outgassing, exposure to

hydrogen c h l o r i d e , washing w i t h

d i s t i l l e d water, and after c o n t a c t w i t h 0.1M hydrochloric acid. The samples were mounted on t h e SEN sample s t u b s w i t h copper conductive

tape.

The aluminasamples

were subsequently vacuum c o a t e d n i t h

a thin

f i l m o f Au/Pd a l l o y .

4.

QectronSpectroscopy

for Chemical Analysis (ESCA)

Qualitative analysis of both adsorbents before and

a f t e r exposure
was made with an AEI

to hydrogen chloride and solution measurements


E S l O O photoelectronpectronleter

using A l Kq r a d i a t i o n (1486.6 keV)

Data a c q u i s i t i o n was accomplished w i t h a n AI Ds-100 data system E


and a Digital PDP-8/e computer. The aluminasamples a p p l y i n gf i n g e rp r e s s u r e .

were mounted on coppersampleprobes,


The s t i c k i n g d i f f i c u l t y e n c o u n t e r e d i n

by
the

i n f r a r e d disk p r e p a r a t i o n as described i n Appendix 1 was used as an advantage i n mounting t h e alumina samples on t h e ESCA probe. Studies to insure
t h a t t h e two aluminas were pure and d i d not

contain a s u r f a c e c o a t i n g

were accomplished by wide scan FSCA spectra.

Wide scan spectra f r o m 0 e t o V

743 e binding energy w e r e o b t a i n e d V


which had beenwashed

on u n t r e a t e d alumina and on alumina w i t h d i s t i l l e d water.

three times

The n a t u r e of t h e a d s o r b e d h y d m g e n c h l o r i d e s p e c i e s i n v e s t i g a t e d using narrow scan ESCA spectra.

was

ESCA spectra f o r

Al 2s1/2'

Al 2p, 0 Is

1/2

and C l 2p peaks were o b t a i n e d on alumina


The same peaks

before and after treatmentwithhydmgenchloride. o ft h e model compound, A l C l

3' were a l s os t u d i e d .C a l i b r a t i o no ft h e
was performed by monitoring the C Is 1/2

binding energy of the samples

peak.
C. Adsorption Measurements

1.

System:

Gas adsorption measurements nene performed

i nt h e

vacuum system shown schematically i n figure 7.

The pyrex vacuum

system could be evacuated t o a base p r e s s u r e f o ot

loe6 t o r r by

use of a mechanical pump (MP) and a mercury d i f f u s i o n pump (DP) Pressure was measured u s i n g an i o n i z a t i o n gauge ( I G ) .

The pumps

were i s o l a t e d from thesystemwith


r e s e r v o i r bulbs

a liquidnitrogentrap

( K ) The LT.

(a), , (RB)

(RC) , (RD) , and (RE) were used f o r s t o r i n g


(VG).

gases introduced into the system through valve


The s e c t i o n o f t h e s y s t e m

below valve (V6) was used t o i n t r o d u c e Thissectionconsisted

and remove gases f r o m t h e system.

of a gas

tank (C)

, mercury

manometer ( M )

, helium

i n l e t (HE), l i q u i d n i t r o g e n

t r a p (Kp), a t r a p c o n t a i n i n g s a t u r a t e d

sodium hydroxide

( I ) potassium E',

sulfate t r a p s (ST1, ST2) immersed i n l i q u i d n i t r o g e n , T e f l o n v a l v e s

(V6).

(V7), (V8).

(V9) and valves

(V10) and

PC)

and a mechanical pump (SP)

r
v5
v4
2

vc

VD

3
LNT

lv6
M

IC

3
GB
Figure 7.

0
C M

Schematic of Adsorption Apparatus

--

Thesystem

below v a l v e s (V2) and V4) was t h e c r i t i c a l s e c t i o n


w e r e performed.Thissection

when? theadsorptionmeasurements consisted of Teflon stopcocks volumemanometer


(Vl)

, (V2). (V4),

and (VW),

a constant

(cM), a
(Bl

g a s buret (GB) c o n s i s t i n g of a series of bulb containing degassed

precalihted bulbs andthe

- B6), a

water ( W )

sample bulb (SB).

The sample M b could be surrounded by

e i t h e r a constanttemperaturebathor

a furnace.Thebath

temperature
a Fischer

was c o n t r o l l e d u s i n g a mercury thermoregulater connected to


Model

51 Unitized Bath Control.

The sample heater was a tubefurnace

(Hoskins n e c t r i c Company) p l a c e d i n a v e r t i c a l p o s i t i o n , t h e a t u r e was c o n t r o l l e d by use of


a powerstat and stabilized

temper-

by connection
was

t o a c o n s t a n tv o l t a g et r a n s f o r m e r . measured using

The temperature o f t h e h e a t e r

a chromel-alumel thermocouple attached to the

wall of

t h e sample bulb and connected to couplecontroller.


2.

a Themo Electric MiniMitethermo-

Introductionand

Removal of Gases from the System;

Gases

were introduced into the pre-evacuated system


with stopcocks

by the following procedure:

( V 8 ) and @lo) opened and a l l t h e o t h e r s t o p c o c k s c l o s e d between stopcocks (V6) and (V9) The pressure was measuredon mano-

g a s was i n t r o d u c e d i n t o t h e s e c t i o n by opening (VG) t o t h e g a s t a n k .

meter (N), then (V6) was openedandthe


main manifold.Typically
reservoir bulbs

gas was t r a n s f e r r e d t o t h e

760 t o r r o f gas would be s t o r e d i n t h e


(VA

by opening valves

VE). a series

Hydrogen c h l o r i d e was removed from t h e systemthrough of traps.Valves were closedexcept

(VI), (VZ), (v6), (v9),and

(v8).

The hydrogen c h l o r l d e was condensed into tray

(T) I "surrounded

by l i q u i d

nitrogen, (V9) was then closed and helium

was i n t r o d u c e d i n t o t h e Valve (VT)

system between (V9) , (VT) , (VlO) , t o a t m o s p h e r i c p r e s s u r e .

was t h e n o p e n e d a n d t h e l i q u i d n i t r o g e n s l o w l y

removed f r o m ( W ) , t h e

condensed hydrogen chloride expanded and flowed into trap t a i n i n g a s a t u r a t e d N d H solution. not neutralized

(l) conB'
was

Any h y d r o g e n c h l o r i d e t h a t

was t h e n t r a p p e d i n t h e p o t a s s i u m s u l f a t e t r a p
After a l l thehydrogenchloridehad

(S2)

s u r r o m d e d by l i q u i d n i t r o g e n . evaporated, the system

was purgedwithhelium

forseveralminutes, pump was opened.

valve (VT) was closedandvalve

(V10) to the secondary

3 . Sample OutgassingandPretreatment;In
determination approximately 0.lg of

a t y p i c a la d s o r p t i o n

gamma alumina o r approximately

1.O of alpha alumina was weighed i n t o t h e quartz sample bulb (SB) g


Thesample

was p r e t r e a t e d b e f o m t h e a d s o r p t i o n
between The e n t i r e system to

measurement by t h e v a l v e s (V6) and ( V l )


(SB) was placed

followingprocedure.

was evacuated t o
on thesystemandvalve

loe6

torr.

The sample bulb

( V l ) openedslowly

u n t i l t h e H a s t i n g s vacuum

gauge (PG) measured c0.5 t o r r .


sample bulb a n d h e a t e d f o r

The h e a t e r was thenplacedaroundthe

2 hrs under vacuum at the outgas temperature

measured by thethermocouple.

After h e a t i n g ,t h e

sample was immersed

i n the constant temperature bath


Preliminary experiments using

a t thedesiredadsorptiontemperature. water v a p o r adsorption on g m a alumina a m

e s t a b l i s h e d this pretreatment procedure.

4.

G s Adsorption Measurementt a The

gas adsorption measurements

were performed i n t h e c o n s t a n t

volume system below v a l v e s (V2) and ( V 4 ) .

After Pretreatment of the

sample the following adsorption procedure

was

33
used.With

a l l s t o p c o c k sc l o s e dt h e

volume ofthesystem

was

adjusted using the gas f i x e d between bulbs systemthroughvalves closed and the manometer (CM) r e a dt h e

buret (GB), u s u a l l y t h e

mercury l e v e l was

(B5)

and

(%. I)

Helium was i n t r o d u c e di n t ot h e

(VHE) , (V9) , (V6) and (V2).

Valve (V2) was t h e n volume

i n i t i a l pressure measured using the constant

A cathetometer(GaertnerScientific)

was used t0

manometer ( p r e c i s i o n intothe

2 O.O5mm).

Valve (Vl) was openedand f i n a lp r e s s u r e

heliumexpanded and by useofthe

samplebulb.The

was measured
The

ideal g a s law t h e f i n a l

volume was c a l c u l a t e d .

i n i t i a l volume was known from previouscalibrationwithhelium. this volume c a l i b r a t i o n , v a l v e tto r r . o (V2) was openedand

After

t h e systemevacuated

in The a d s o r p t i o n measurement was performed t h e

same manner. The


through valve measured. Valve

adsorbate was introduced f r o m a r e s e r v o i r b u l b


(Vl) closed,theinitial

(V2) with valve

Dressure was

(Vl) was openedand

a f t e r equilibrium was e s t a b l i s h e d

the experimental pressure The samplebulbstopcock

was read u s i n g t h e manometer and cathetometer.

(Vl) was then closed and another dose of


was measured. Valve (Vl) was

adsorbateintroducedandthepressure then opened, the equilibrium pressure tionpoint

measured andthesecondadsorp-

was obtained.Thisprocedure

was c o n t l n u e d u n t i l an e n t i r e

isotherm was obtained.


l y this procedure, the initial and final 3

volumes are known f r o m


axe

t h eh e l i u mc a l i b r a t i o n . determined. calculate the

The i n i t i a l . and e q u i l i b r i u m p r e s s u r e s

Using t h e s e p a r a m e t e r s a n d t h e i d e a l g a s

law onecan

ideal pressure assuming that only gas expansion occurred.

The d i f f e r e n c e between t h e e q u i l i b r i u m p r e s s u r e a n d t h e i d e a l p r e s s u r e

can be related t o t h e amount of gas adsorbed by use of


gas law.

the i e l da

A sample c a l c u l a t i o n of an adsorption isotherm using t h e

experimental data is p r e s e n t e d i n Appendix 2.

5.

Readsorption Procedure;

The r e v e r s i b i l i t yo ft h e

hydrogen

c h l o r i d e and water vapor adsorption

was tested by performing

readsorptionexperiments.Thereadsorptionexperimentconsisted

of e v a c u a t i n g t h e sample bulb after the i n i t i a l adsorption isotherm


was obtained.
The e v a c u a t i o n t y p i c a l l y
l a s t e d 18 t o 20 hrs and
Has

c a r r i e d o u t a t the adsorption temperature, then another adsorption isotherm was measured,

D.

Solution Measurements I n c o n j u n c t i o n with calorimetric studies performed by Wightman60

some s o l u t i o n p r o p e r b i e s of thealuminas

were measured.

p changes H

o f hydrochloric acid s o l u t i o n s upon addition of alumina

were determined

as well as s o l u b i l i t i e s of the a l p h a a n d g a m a a l u m i n a i n h y d r o c h l o r i c
a c i d a n d d i s t i l l e d water.

1. S o l u b i l i t y Measurement:
prepaxed by d i l u t i o n o f

A s t o c ks o l u t i o n

of 0.W HC1 was


acid s o l u t i o n

a Hellige standard hydrochloric

R1193C t o 1000 cc withdouble aliquots of this stock solution of alumina

distilled, deionized water.

40cc

o r water were placed i n a f l a s k , 0.lg

was i n t r o d u c e d , t h e s o l u t i o n

was heated t o n e a r b o i l i n g f o r
The alumina/O.lN
filtered.

15 m i n u t e s a n d t h e n s t i r r e d
d u m i n a / w a t e rs o l u t i o n

f o r two hours.

H or a
The concen-

was thencentrifugedand

t r a t i o n of aluminum i n t h e s e f i l t e r e d s o l u t i o n s

was determined using

a Perkin Elmer Model 503 Atomic Absorption spectrometer equipped w i t h

35
automatic Cugltal readoutofconcentration.

A singleelementhollow

cathode lamp (Perkin Elmer) was employed i n t h e d e t e r m i n a t i o n o f t h e aluminum. Standards w e r e prepared by d i l u t i o n o f

a stock1000 ppm
To i n s u r e that no

s o l u t i o n , as d e s c r i b e d by SmithandParsons.75

aluminum contamination was p r e s e n t i n t h e HCl s o l u t i o n s a n d d i s t i l l e d

water t h e aluminum c o n c e n t r a t i o n o f b l a n k s o l u t i o n s o f

water and 0.1N

Ha, treated in the


measured.

same manner but containing

no alumina, w s a

The r e s u l t s of t h e s o l u b i l i t y

measurements axe presented

i n Appendix 3.
2.

pH Measurement;

The change i n p of d i l u t eh y d r o c h l o r i c H

acid s o l u t i o n s a n d water upon a d d i t i o n of alumina was recorded using

an Orion Research

Model 701 p Meter and Thomas Universal Combination H


0.1 g of gamma alumina o r 1.0 g of a l p h a

Electrode.Approximately

alumina was weighed and h e a t e d i n a l a b oven a t 100C f o r one


Theseweighedaluminasamples

hu. or

were p l a c e d i n

5 c c of solution and
The p was measured H

s t i r r e dc o n s t a n t l yt h m u g h o u tt h ee x p e r i m e n t .

before a d d i t i o n of the alumina and


minutes. E. Data Reduction Procedures

a t time i n t e r v a l s of 10, 60 and 180

1.

Adsorption Isotherms: Experimental w a s reduced to the


based on t h e i d e a l

data o b t a i n e di nt h e
by
adsorbed

adsorption system

amount of gas adsorbed


gas law.

employingequations

The amount

was c a l c u l a t e d by t h e f o l l o w i n g e q u a t i o n s :

36

5Rz

Ro

P1

R0

PExp
P2 X VSB

- PI P

X VI

VT

Pm

Pap

XVT N i = RPX T X W

N =CNi
s i

where:

Ro = Zero point

s e t t i n g of cathetometer.
samplestopcock

%=

Initial cathetometer reading before

was opened.

R2 = Cathetometer reading a f t e r equilibrium i s e s t a b l i s h e d .


P2 = Pressure i n sample bulb after V 1 was c l o s e d f o r next dose of gas. P2 i s e q u a l t o PED i n p r e v i o u s d e t e r mination and P2 i s z e r o i n i n i t i a l a d s o r p t i o n .

VI, VSB and VT

= The i n i t i a l volume,sample h l b volume and t o t a l volume, r e s p e c t i v e l y , which were determined using helium expansion.

R = I d e a l g a s law c o n s t a n t in a p p r o p r i a t e u n i t s . T = Adsorption temperature.


W = Sample weight. 1 - 6:

The following parameters are c a l c u l a t e d u s i n g e q u a t i o n s

P1 = I n i t i a l p r e s s u r e o f a d s o r b a t e .
= E q u i l i b r i u m pressure(experimental).

pCAL = Calculated pressure

i f only expansion occurred.

37

Ni

= N u m b e r of moles

on the sample adsorbed.

of adsorbate/gram adsorbent adsorbed a f t e r each dose.

NS = T o t a l number of moles adsorbate/parn adsorbent


A t y p i c a l data t a b l e andsample

c a l c u l a t i o n i s g i v e n i n Appendix 2. The monolayer volume

2.

Monolayer volume and Adsorbate Area:

i s d e f i n e d as t h e q u a n t i t y of adsorbate r e q u i r e d t o c o v e r t h e a d s o r b e n t w i t h a monomolecular l a y e r . The monolayer volume i s used t o andporoussolids.The

determine surface areas of f i n e l y d i v i d e d

adsorbate area is d e f i n e d as t h e area occupied by a n a d s o r b a t e molec u l eo nt h ea d s o r b e n t using the monolayer surface. The a d s o r b a t e area u a s c a l c u l a t e d

volume of t h e a d s o r b a t e a n d t h e n i t r o g e n s u r f a c e

area of the adsorbent. Several methods


volume fmm a d s o r p t i o n data havebeen method and Langmuir t r e a t m e n t . TheBrclnauer,

11*14*74 of c a l c u ~ a t ~ n g monolayer
describedincludingthe

BET

Fhmett , and T e l l e r method (BET) was u s e d t o calculate

t h e monolayer volume of water adsorbed on g m a alumina ( Alon-C) and a m alphaalumina form : X


=-

(A16SG).

The BET e q u a t i o n was used in t h ef o l l o w i n g

I C

L)X

NmC

where

X = P

and P = Equilibrium pressure of water vapor

Po N

= Vapor pressure of water at t h e a d s o r p t i o n t e m p e r a t u r e .


=

N u m b e r of moles

H,O/grm

a d s o r b e n t a t each pressure.

38

c = A c o n s t a n tr e l a t e dt ot h eh e a t

of adsorptionand c h a r a c t e r i s t i c of t h e gas/solid system.


H,O/pam

is

Nm = Monolayer c a p a c i t y i n m o l e s
N z -

adsorbent.

1 m + Y
of a p l o t of x/N (1-X)vs.

uhere Y and m are t h e y - i n t e r c e p t a n d s l o p e

P/Po.

The slope andy-intercept

were e v a l u a t e d u s i n g

a l i n e a r least

squares computer program on

a Digital PDP 8/1 computer.

The area of the adsorbed water on t h e alumina was c d l c u l a t e d by the following equation :

c
Nm ' No

where:

Nm = Monolayer c a p a c i t y of t h e adsorbate

Avogadro's number.

C = BEl' n i t r o g e ns u r f a c e units.

area of t h e a d s o r b e n t i n a p p r o p r i a t e

and t h e r e f o r e , A i s t h e area occupied by each adsorbed water molecule

in

square angstroms.

Themonolayer

c a p a c i t y of adsorbed hydrogen chloride on the

alumina was calculated u s i n g t h e f o l l o w i n g


equation I

form of t h e Langmuir

where : P = Equilibrium pressure of hydrogen chloride.

N = N u m b e r of moles of H C l / q a m adsorbent.

39

b = Constant characteristic

of the system.

N, = Monolayer capacity i n moles HCL gram adsorbent.


The monolayer capacity

is equal to the reciprocal

of t h e slope of t h e

l i n e obtained by p l o t t i n g P/N v s P.

The adsorbate area of H C l is

c a l c u l a t e d f r o m the monolayer capacity in the

same way as t h e area

of the adsorbed water molecule (see equation 9 ) .

3.

I s o s t e r i c Heat Calculation:

The thermodynamic

p r o p e r t i e s of

a gas/solid system

can be d e t e r m i n e d e i t h e r d i r e c t l y

f r o m gas phase

calorimetry o r i n d i r e c t l y by mathematical analysis of several a d s o r p t i o ni s o t h e r m s .I nt h i ss t u d ya d s o r p t i o ni s o t h e n s

at three
at

temperature s were used t o c a l c u l a t e i s o s t e r i c h e a t s o f a d s o r p t i o n varioussurfacecoverages. The i s o s t e r i c h e a t i s a d i f f e r e n t i a l

quantity calculated using the isotherm equation in the following form


c

data and the Clausius Clapeyron

where :

qst = I s o s t e r i c h e a t R P T
N
= Ideal gas
= I

of adsorption.

constant.

Equilibrium pressure.
Adsorption temperature.

= Moles adsorbate/grarn adsorbent

The isosteric heat was c a l c u l a t e d from a p l o t o f I n coverage. The slope o f t h i s l i n e a r p l o t

P v s 1/T a t c o n s t a n t

i s equal t -qSt/R. o

Accurate determination of values of In facilitated by computer f i t t i n gt h ei s o t h e r m

P a t constant coverage

was

data.

Clark, Holm, and

40
Bla~kkUn'~ used a F r e u n d l i c h p l o t

(log P vs log N) t o f i t isotherm

data of ammonia a d s o r p t i o n on s i l i c a - a l u m i n a i n . t h e c a l c u l a t i o n o f
thermodynamic p r o p e r t i e s .
A comparisonofhydrogenchlorideand

water v a p r isotherm data by t h e B T Langauir and Freundlich E,


e q u a t i o n s showed that t h e F'reundlich equation gave the

best f i t ,

that i s t h e least d e v i a t i o n from l i n e a r i t y , of the experimental


A "Focal" computer

data.

program for c a l c u l a t i n g N v s I n P from experimental


The compu-

data u s i n g t h e Freundlich equation i s shown i n Appendix 4 .

t e r program used t o c a l c u l a t e t h e isosteric h e a t o f a d s o r p t i o n u s i n g


the Freundlich pmameters
i s described i n Appendix 5.

IV.
A.

RESULTS AND DISCUSSION

Characterization Adsorbents of

1. C r y s t a l l i n ep h a s e

X-ray powder d i f f r a c t i o np a t t e r n s

of

Alon-C u s i n g Cu Ka r a d i a t i o n e x h i b i t e d d i f f r a c t i o n

l i n e s a t 1.98 and
a t 2.087,

1.39

51

characteristicof

gamma a l u m i n a .I n t e n s el i n e s

2.555 and 1.601

were o b s e r v e d i n t h e

X-ray powder p a t t e r n of A16SC. The e n t i r e p a t t e r n

Severalotherlessintenseline

were also seen.

was c h a r a c t e r i s t i c o f a l p h a a l u m i n a .
2.

Surface areas:

A t y p i c a l BE! p l o tf o rt h e

low temperature

nitrogen adsorption on

gamma alumina outgassed a t 100C i s shown i n on alphaalumina show a The

figure 8.

A similar p l o t f o r n i t r o g e n a d s o r p t i o n

outgassed a t 100C is shown i n Figure 9. reasonable f i t of t h ea d s o r p t i o n

T h e s ef i g u r e s

data t o t h e BET equation.

r e s u l t s of t h e BE! s u r f a c e area determination f o r alpha alumina given i n Table 1 . 1

are

The s u r f a c e areas were determined a f t e r o u t g a s s i n g The alphaalumina


has a surface

t h e sample a t 100, 200 and 4OO0C.

area of 8.1 2 1.8 m 2/g.

The s u r f a c e area i s c o n s t a n t between 100-4OO0C


of Morimoto, Shiomi
and Tanaka.l

i n agreement w i t h t h e r e s u l t s

This

lack of outgas temperature dependence

is reasonable since alpha alumina


and does not undergo

is the high temperature modification of alumina


a phasetransistioninthetemperaturerangestudied

(100-400C).

The s u r f a c e area of gamma alumina shows a s i g n i f i c a n t dependence on o u t g a s temperature as seen i n T a b l e 1 1 1.


A 10% l o s s

i n surface

area is s e e n f o r gamma aluminaoutgassed area was a l s o o b s e r v e d


by Morimoto,Shiomi

a t 4OO0C.

T h i s l o s s of suzface decrease

and Tanaka.The

4 1

42

0.10

0.06

0.10
P/Po

0.15

0.20

F ' i g u ~8.

Typical Alumina

B m

P l o t for Nitrogen Adsorption on Gamma

43

0.3

0.2

I
n

I d
W

2
0.1

s-

02 .

0.3

04 .

Figure 9.

T y p i c a l BET P l o t f o r NitrogenAdsorption Alumina

on Alpha

44

TABLE I1
EET NITROGE24 SURFACE AREA OF ALPHA ALUMINA
Outgas Temperature

Surface Area

( c)
100
200

(m

2,

g)

8.1

200

8.4

200

7.4.

400
4-00

6.3
8.4

400
Average

9.1
8.1

5 1.8

45

TABLE I11

BET NITROGEN SURFACE


OutgasTemperature
(OC)

AREA OF GAMMA ALUMINA

Surface Area (m 2/ g )

100 100
100 200
200

94.0

97.1
92.9

400 400
400

81.3 87.1 82.9 88.7 87.8 Average 85.6

400 400

5 3.9

46

i n s u r f a c e area may be due t o s i n t e r i n g accompanying t h e o n s e t p h a s et r a n s i t i o n .

of a

Gm a alumina i s a low t e m p e r a t u r e t r a n s i t i o n a l am

alumina, capable of undergoing phase changes

a t e l e v a t e d temperature.

Werfers and

report the ' t r a n s i t i o n from gamma t o delta alumina

o c c u r r i n g n e a r 900C under c o n d i t i o n s o f moist atmosphere, pressure

greater than one atmosphere, heating

rate greater t h a n 1C/min and


t h e g m a alumina a m

particle s i z e greater than 100 microns.Although was outgassed a t only 400C,


particle size

conditions of pressure, atmosphere and may favor formation of delta alumina

are different and

a t lower temperatures. 77 178


The s u r f a c e area of t h e two aluminas g i v e n i n T a b l e

I1 and Table If one

I11 i s related t o t h e p a r t i c l e s i z e o f

t h e two aluminas.

assumes s p h e r i c a l non porous p a r t i c l e s h a v i n g a d e n s i t y o f 3.6 g/cc

for gamma alumina, an average particle s i z e of 0.02 microns is calculated. The manufacturer'svalue
i s given as 0.03 microns. A calcu-

lated p a r t i c l e s i z e of 0.18 microns i s o b t a i n e d f o r a l p h a a l u m i n a


using a d e n s i t y o f 3.9 g/cc.

3.

Nitrogen Adsorption

and Desorption on Alumina: The

results

of nitrogen adsorption shown i n figure 10.

- desorption measurements

on g m a alumina are a m

No hysteresis was seen i n t h e d e s o r p t i o n c y c l e


was due t o an absenceof

of n i t r o g e n . T h i s ' l a c k o f h y s t e r e s i s
pores (<200

micro-

2) i n t h e

gamma alumina i n which nitrogen could condense.

Figure 11 shows t h e low temperature nitrogen adsorption-desorption


isotherm on alphaalumina. Again t h e desorptioncycle shows no hystere-

sis, i n d i c a t i n gt h ea b s e n c eo fm i c r o p o r e s .

The lack of micropores i s

47

8 -

6 -

4 -

Figure 1 . Adso t i o n and Desorption o f Nitrogenon 1 rg at 77 K

Alpha Alumina

49
not unexpected since alpha alumina hadbeen h e a t e d t o 1537OC and

g m a alumina i s prepared i n a high temperature a m

flame.

The results

of t h e a d s o r p t i o n - d e s o r p t i o n s t u d i e s r e i n f o r c e s t h e v a l i d i t y o f t h e
calculation of relative particle size

u s i n g surface axeas a n d d e n s i t y

where it was assumed that both adsorbents did not contain micropores.

4.

SurfaceTopographyand

SEM S t u d i e s :

A 100X scanning electron

photomicrographofuntreated

g m a alumina i s shown i n Figure 12. a m


i s reproduced i n figure

A
A

lOOX photomicrographofalphaalumina
cursorycomparison

13.

of t h e particle s i z e i n t h e s e two figures might


gamma a l u m i n a c o n s i s t s o f l a r g e r p a r t i c l e s

lead to the conclusion that thanalphaalumina.

However, i n s p e c t i o n of thephotomicrographstaken

a t 5OOOX magnification shown i n FIgure 14 and figure 15 l e a d s t o a d i f f e r e n tc o n c l u s i o n . The g m a a l u m i n ac o n s i s t so f a m

small primary

particles clustered together to give the

larger secondary particles

observed a t lowermagnification.Excessivechargingoftheparticles l e a d t o a loss of r e s o l u t i o n a t m a g n i f i c a t i o n s g r e a t e r t h a n prevented studies of the topography


5000X and

of t h e i n d i v i d u a l a l u m i n a p a r t i c l e s .

The r e s u l t s of a n S M experiment to a c c o u n t f o r t h e o b s e r v e d E

decreaseinsurface a t u r ea r e

area of gamma alumina a t hiEh pretreatment temper-

shown i n Figure 16 andFigure

17.

N s i g n i f i c a n td i f f e r e n c e s o

axe seen on comparing the photomicrographs of u n t r e a t e d g m a alumina, a m


Figure 1 2 and FSigure 14 with those
gassing a t 40OoC.
of g m a alumina taken a m

after outgamma

These r e s u l t s show t h a t thechangesin

alumina a s s o c i a t e d w i t h t h e measured lO$ decrease i n surface area cannot


be observed using scanning electron microscopy.

Figure 12.

Photomicrograph o f Untreated Gm a Alumina at lOOX am

Figure

13.

Photomicrograph of Untreated Alpha Alumina at l O O X

F'igure 14.

PhotomicmgraphofUntreated

Gm a Alumina a t 5000X am

53

Figure 15.

Photomicrograph of Untreated Alpha Alumina at 5OOOX

Figure 16.

P h o t o m i c r o g r a p h of Gamma Alumina Outgassed a t 4OO0C at lOOX

55

Ngure 17.

Photomicrograph of Gamma Alumina Outgassed at 4OO0C at 5000X

The r e s u l t s of e n e r g y d i s p e r s i v e a n a l y s i s

of X-rays (EBAX) of

untreated gamma alumina i s shown i n Hgure 18. The only peaks seen

are t h o s e r e s u l t i n g from t h e Au-Pd coating and aluminum.


elements of interest such detected. as c h l o r i n e , sodium a n d s i l i c o n

Other

were not

The same r e s u l t s were obtained on a sampleofuntreated

alpha alumina.

5.

ESCA SurfaceAnalysis

A q u a l i t a t i v es t u d y

of t h e s u r f a c e

composition of alpha and

gamma alumina was c a r r i e d o u t u s i n g wide

scan

EC. SA

Figure 19 shows t h e wide 'scan ESCA spectrumofanuntreated


sample. The

alphaalumina t o t h e 0 1%/2

largest peaks i n t h e spectrumcorrespond

(532 eV), C

isll2 (284 eV),


of

A l 2p (74 eV) and A 1 2%j2 A mall peak a t 200 e V

(118 eV) l e v e l s a n d t o a n

Auger peak

C. u

may be due to chlorine contamination.

The C 1s peak i s a r e s u l t 1/2 of contamination fmm t h e oil d i f f u s i o n pumps of t h e spectrometer. The Auger peak f o r copper i s n o t s u r p r i s i n g s i n c e t h e c o p p e r probe may nothave been completely covered. gamma sample

Figure 20 shows a w i d e scan ESCA spectrum of untreated


alumina.

Again the observed peaks can be a s s i g n e d t o an Auger t r a n s i -

Zp, Al 2 ~ , / ~ and C 1s levels. 1/2 A s a peak a t 200 e i s a g a i n a s s i g n a b l e t o c h l o r i n e ml l V which i s not unexpectedsince of gamma alumina.

t i o n f o r Cu and t o t h e 0

1s112, Al

AlCl

i s t h e s t a d i n g material f o r t h e p r e p a r a t i o n
axe notobserved

The fact t h a t o t h e r i n t e n s e p e a k s

i s evidence for the absence

of any s u r f a c e c o a t i n g on bothalumina

surfaces ,

57

Flgure 18.

EDAX of Untreated Gm a Alumina am

371.5
BindingEnergy

(eV)

Figure 19.

Wide Scan EA Spectrum of Untreated Gamma Alumina C

371 5
Binding Energy (eV)

0.0

figure 20.

Wide Scan ESCA Spectrum of Untreated Alpha Alumina

60

B.

Preliminary Adsorption Studies The r e p r o d u c i b i l i t y o f

t h e adsorption properties of gama alumina


t h e time o f h e a t i n g

was s t u d i e d as a function of temperature and

of

t h e sample i n t h e c o n s t a n t volume adsorptionapparatus.Resultsof

water a d s o r p t i o n a t room temperature on gamma alumina o u t g a s s e d f o r


2 hr a t t h r e e d i f f e r e n t t e m p e r a t u r e s
temperature of the pretreatment

are shown i n figure 21.

The

is c r i t i c a l i n d e f i n i n g t h e a d s o r p t i o n

capacity

.
o f gamma alumina outgassed
a t 6ooc for time p e r i o d s
t h i s range

F'igure 22 shous t h e effect o f t h e pretreatment time on t h e


adsorption capacity from 2 t o 19 hours. ofpretreatment

N change i n adsorptioncapacityover o

time i s observed,

After these p r e l i m i n a r ys t u d i e so f
t h e adsorption

t h e effects of pretreatment time and temperature on

c a p a c i t y of alumina, a l l samples were e v a c u a t e d f o r 2 h r s at a s p e c i f i e d outgas temperature and then cooled for


2 hrs t o t h e a d s o r p t i o n

temper-

ature.

The good r e p r o d u c i b i l i t y of t h i s t e c h n i q u e

i s s e e n i n figure

23, i n which s i x s e p a r a t e HC1 a d s o r p t i o n isotherms (50C) are shown


a m on g m a alumina samples outgassed a t 8OoC for two hrs.

The amount of both bulb was determinedto

HC1 and H20 adsorbed on t h e walls of t h e sample

be n e g l i g i b l e . T h i s r e s u l t

is r e a s o n a b l e s i n c e

t h e sample b l s (15cc)have u b

a small surface area compared t o t h e


gamma alumina.

surface areas of alpha and C.

Water Vapor Adsorption on Gm a Alumina am


The r e s u l t s of t h e p r e v i o u s s e c t i o n showed t h a t o u t g a s temperature

w s critical indefiningtheadsorptioncapacityof a

g m a alumina. a m

0
0

6 C 0 ' 10 0'

0 2oooc
5
10 P (torr)

15

Cl torr = 133.32 Pa)

figure 2 . 1

Influence of Outgas Temperature on Water Vapor on Gm a Alumina a m

Adsorption

2 hrs 2 hrs
hrs

0 19

10 P (torr)

15

Figure 22.

Effect o f Heating Time on Adsorption

Capacity of Alumina

"-A I %
3

on
-

.
0

__17_Lz

CQ

U I

0 l-i

P( t o r r )

Figure 23.

G m a Alumina a m

R e p r o d u c i b i l i t yo f H C l Adsorption a t 50C on S i x D i f f e r e n t Samples

matrix of experimental parameters

based on outgassing temperature and

adsorption temperature was developed t o f u r t h e r s t u d y influence.

t h i s temperature

Water vapor adsorption was rneasumdon


Adsorptionisotherms

gamma alumina out-

gassed a t 80, 200 and 400C.

were measured a t
on gamma alumina

30, 4 0 , and 5OoC.

The data f o r water vapor adsorption

is presented i n Appendix 6.
The results of the outgas temperatum study 24 f o r H20 adsorption a t 40C on gamma alumina.
are shown i n Figure

Theamount

of water

a d s o r p t i o n i n c r e a s e s w i t h increasing outgas temperature t o removal ofphysisorbed

dueprobably

water.

S i m i l a r r e s u l t s were obtained a t

30 and 5OoC.
The t e m p e r a t u r e dependenceof

water adsorption on gamma alumina


A inverserelationship n

outgassed a t 80C is shown i n Flgure 25.

between H20 adsorption capacity and adsorption temperature S i m i l a r r e s u l t s were obtained after outgassing a t 400C. The adsorption data was l i n e a r i z e d u s i n g t h e use of the

i s observed.

BET equation.

The

BET equation allows

t h e c a l c u l a t i o n o f t h e average area

occupied by an adsorbed water molecule.Table

I V g i v e s t h e cross-

s e c t i o n a l area ( U) of t h e adsorbed water molecule calculated f r o m t h e water vaporisothenus. gmups.


~n average

The

v a l u e sa p p e a rt o

f a l l i n t o two

U . valueof16.2

512/molecule

is o b t a i n e d f o r gamma

alumina outgassed a t 8OoC o r 200C.

Water adsorbed on gamma alumina


Feri's

outgassed a t 4OO0C g i v e s an average area of 12.4 R2/molecule. i d e a l i z e d mode141 of the gama alumina surface

(see F'igure 1) would

y i e l d an adsorbed area of 16 %2/molecule assuming that each adsorbed

1. 60

12.0

8.0

0
0

8OoC

20oOc
4OO0C

0
40 .
4 0 12

16

P torr) (

f i g u r e 24.

Influence of OutgasTemperature on Gm a Alumina at 4Ooc am

on Water Vapor

Adsorption

..,,. .

66

(3

0
d

Kl

0.5

10 P( t o r r )

15

25.

Temperature Dependence of Water Vapor Adsorption on m Alumina Outgassed at 8OoC

67

TABLE I V
CROSS-SECTIONAL AREAS OF WATER ADSORBED ON
GAMMA ALUMINA

Outgas Temperature
(OC)

I soth e m Temperature
(OC)

H20 Area
('A2/molecule) 15.2 16.0

80 80

30
40

80
200

50
40 Average

17.9
15.8 16.2 11.9 13.8 11.5 Average 12.4

1.2

(s)

400

27
40

400
400

50

2 1 . 2 (10%)

water molecule requires two oxygen i o n s o r two surface h~dro~~l SOUPS

as an adsorption site.

The smaller area f o r water adsorbed on t h e

4oOC outgassed g m a alumina i s consistent with a m

a phase transition
l@

occurring a t 4OO0C as was p r e v i o u s l y p o s t u l a t e d t o e x p l a i n t h e l o s s i n surface area.

The t r a n s i t i o n fmm gamma alumina t o h i g h e r oxygen i o n s

temperature m o d i f i c a t i o n s r e s u l t s i n a closer packing of


i n t h e alumina lattice.

Flgure 26 shows an ideal alphaaluminasurface

between alternate l a y e r s . 2 I n t h i s surface each oxygen ionoccupies an area of 6.5 The area 2 o f an adsorbed water moleculeon t h i s surface would then be 13 assuming fracture of alpha alumina to occur

De Boer e t al.43 found an area of12.2R2/molecule


adsorbed on alumina of an alpha alumina

f o r water model

p r e t r e a t e d a t 12OO0C i n agreement with the

surface.

The valueof12.4

A /molecule f o r gamma

alumina heated a t 4OO0C i n t h i s study i s i n good agreement with the value obtained alpha alumina by de Boer e t al.43 and t h a t c a l c u l a t e d f o r t h e
ideal

surface model.

The s i g n i f i c a n c e of t h e area of the adsorbed t h a t i t supports I R e v i d e n c e r e p o r t e d i n adsorbed states similar t o t h o s e

water molecule is

t h e l i t e r a t u r e 259 37 for

shown i n Figure 3.

Here an adsorbed

water molecule i s hydmgen bonded t o e i t h e r two surface hydroxyl groups


o r t o two oxygen ions.
The r e s u l t of a readsorption study

of water adsorption on

gamma and t h e torr

alumina i s shown i n Figure readsorption isotherms the

2. 7

Between t h e o r i g i n a l i s o t h e r m

sample was outgassed i n vacuum a t


f a l l on t h e originalisotherm.

for 18 hrs.

The readsorptionpoints

Figure 26.

Ideal Alpha Alumina Surface

10

0
0

Adsorption Readsorption

.L

10

15

P torr) (

figure

2. 7

Readsorption of Water Vapor on Gamma Alumina a t 50C

71
\ l a t e r a d s o r p t i o n on gamma alumina outgassed a t 80C i s thus completely r e v e r s i b l e .T h i sr e v e r s i h i l i t yi n d i c a t e s
t h a t water a d s o r p t i o n on

alumina can be c h a r a c t e r i z e d as a physlsorptlonprocess.Formation


o f h d x l @ups yr y o

by r e a c t i o nw i t h

t h e bare oxide surface to form


this reverslbility.

new hydroxyl groups i s r u l e d o u t becauseof D.


Water Vapor Adsorption on Alpha Alumina
The dependence of adsorption capacity

on o u t e s temperatme f o r

water adsorption on alpha alumina

at 4OoC is shown i n Figure 28.

S i m i l a r r e s u l t s were obtained a t 30 and 5OoC and are presented In Appendix 7. The influenceofoutgastemperature seems t o be more

uniform f o r t h e a l p h a a l u m i n a t h a n f o r

gamma alumina, possiblybecause

of t h e stability of t h e a l p h a a l u m i n a i n t h e o u t g a s studied. The BEP e q u a t i o n a p p l i e d t o H20/alphaalumina

temperature ran&-

isotherms again

gave good l i n e a r fits.

The result o f t h e

E T a n a l y s l s i s g i v e ni n &
The r e s u l t s may i n d i c a t e

Table V f o r a l l t h e i s o t h e r m s

i n thematrlx.

a dependence of t h e c r o s s - s e c t i o n a l

area on outgas temperature, but


The average
This

f u r t h e r s t u d i e s are needed t o e s t a b l i s h t h l s dependence. c r o s s - s e c t i o n area

(a)

is 12.4 A /molecule on a l p h a alumina.


of de Boer e t aL.43 and the

area agrees w i t h t h e r e s u l t s
o fa l p h a

model surface

alumina (see F1gu-z 26).

The consequence of t h e differences

i n t h e a d s o r t e d area of the water molecule can be seen i n FIgure 29


which shows t h a t t h e m o u n t for alpha alumina than of water a d s o r t e d per unit area is greater

f a r gamma alumina.
of water

The r e s u l t of the study of the temperature dependence adsorption on alpha alumina outgassed

a t A00 C Is shown i n F i g u r e 30.

72

0
0

80C

2oooc
MOC

8
P( t o r r )

12

16

Figure 28.

Influence of Outgas Temperature on Water Vapor Adsorption on Alpha Alumina at bOC

TABLE V
CFOSS-SECPIONAL AREAS OF WATB ADSORBED ON ALPHA ALUMINA

Outgas Temperature 0 ( c)

Isotherm Temperature
(OC)

H20 Area
2 ( A /molecule)

80
80

12.4

12.8

80
200 400
400

19.8
13.0
9.0

10.1
10.0

400
Average

12.4

3.3 (26%)

r
2. 0 -

1 5.

1.(3 -

0
0. f>

Camma
Alpha

5
P(t0l-r)

10

15

Figure

29.

Comparison of Water Vapor A d s o r p t i o n a t Camma A l u m i n a O u t g a s s e d a t 2OO0C

40C onAlphaand

75

20

0
0

0
15

50'C

p/

0 0
5

Figure 30.

Temperature Dependence of Water Vapor Adsorptionon Alumina Outgassed at 8OoC

Alpha

Resultsobtained

after o u t g a s s i n g a t 4OO0C were s i m i l a r .

As i n t h e

case of water adsorption on gamma alumina, an i n v e r s e r e l a t i o n s h i p


i s seen between adsorption
on alpha alumina. This

temperature and the amount o f water adsorbed

temperature dependence was u s e d t o c a l c u l a t e

t h e i s o s t e r i c heat of a d s o r p t i o n f o r water vapor on both aluminas.

Water adsorption on alpha alumina,


alumina, was c o m p l e t e l y r e v e r s i b l e readsorption experiment

l i k e water a d s o r p t i o n on g m a a m the

as seen by t h e r e s u l t s o f

on alpha alumina

shown i n F i g u r e

31.

As t h e above r e s u l t s i n d i c a t e , similar behaviortowards

a l p h a and gamma alumina show

water vapor adsorption.

The water a d s o r p t i o n

c a p a c i t y of both aluminas is i n c r e a s e d u i t h i n c r e a s i n g o u t g a s ature.Reversibilityof

temper-

water vaporadsorption

onbothalphaand

g m a i s observed. a m

The Same adsorptiontemperaturedependence

is

exhibited by t h e two aluminas.Themostnotabledifferencebetween


t h e two aluminas I s t h e i r a d s o r p t i o n c a p a c i t y

for water vapor.Alpha

e alumina adsorbs more water p r u n i t area than gamma alumina (see

Figure 29). Carruthers, Payne,Singand


water a d s o r p t i o n on alpha alumina than

S t ~ y k e had ~ r ~ found greater

on t h e t r a n s i t i o n a l t h e t a
be explained on t h e

a l u m i n a .D i f f e r e n c e si na d s o r p t i o nc a p a c i t yc a n

basis of t h e packing of oxygen i o n s i n t h e i d e a l i z e d


alpha and
Of

surfaces of
and t h e amount

g m a alumina.This a m

same p a c k i n g d i f f e r e n c e

?=-adsorbed

Hater on t h e two aluminas may i n f l u e n c e t h e a d s o r p t i o n


two aluminas. o r i d e m

of hydmgen chloride on the


E.
Hydrogen C h l

Outgas temperature had a s t r o n g i n f l u e n c e o n

water a d s o r p t i o n

77

z i

ul

0
2 -

Adsorption Readsorption

1
5
P torr) (
Figure 31.

10 j

%adsorption of Water Vapor on Alpha Alumina at 5OoC

on m

a alumina.

Increasing the outgas temperature

of gamma alumina

also increased t h e amount- of hydrogen c h l o r i d e adsorbed on gm a a m

alumina as shown i n Figure 32.


removal of water molecules from adsorption.

T h i si n c r e a s e

is p r o b a b l y . d u et ot h e

s i t e s needed f o r hydrogen chloride

A readsorption study of the reversibility

of hydrogen .chloride
Here t h e sample was

adsorption was c a r r i e d o u t o n

gamma alumina.

evacuated a t t h e d s o r p t i o ne m p e r a t u r e o r a t f t o r r .F i g u r e

18 hours a t

- loe6
on g m a a m

33 shows t h e r e s u l t s

of t h er e a d s o r p t i o ns t u d y

alumina i n i t i a l l y o u t g a s s e d at 8OoC and the adsorption measured


40C.

at
on

Hydrogen c h l o r i d ea d s o r p t i o n

is o n l y p a r t i a l l y r e v e r s i b l e

gamma alumina,whereas

water adsorption was c o m p l e t e l y r e v e r s i b l e ,


may c o r r e s p o n d t o a s o l u t i o n

The r e v e r s i b l e part of t h e a d s o r p t i o n

process of the hydrogen chloride in the physisorbed alumina.

water on t h e g m a a m

A t e s t of t h i s h y p o t h e s i s b a s e d
is g i v e n i n

on a thermodynamic a n a l y s i s The i r r e v e r s i b l e part

of t h e a d s o r p t i o n

a later section.

of t h e a d s o r p t i o n may be due t o t h e formation of a bond between t h e


hydrogen c h l o r i d e a n d t h e a l u m i n a The temperaturedependence

surface.

of hydrogen c h l o r i d e a d s o r p t i o n on

g m a alumina outgassed a t 8OoC i s summarized by t h e r e s u l t s p r e s e n t e d a m

i n Figure

9 Isothermson .

g m a alumina outgassed at 200 and 400C a m

showed similar temperature behavior

as t h e a d s o r p t i o n d a t a i n

Appendix

8 indicates.
Hydrogen chlorideadsorption irreversibility indicates formationofbondsbetween

was p r i m a r i l yi r r e v e r s i b l e .T h i s

a chemisorption process and thus the probable


t h e hydrogen chloride and alumina surface,

79

8OoC
20oOc

35

4OO0C

10

P torr) (

Figure 32.

Influence of Outgas T e m p e r a t u r e on Hydmgen Chloride Adsorption on Gamma Alumina at 4OoC

80

7 Initial Adsorption
b

'

Irreversible

0 Sample 2
Reversible

15

10 P(torr)

Flgure 33.

Regdsorption of Hydmgen Chloride on Gm a Alumina a t am 40 C after Outgassing f o r 18 hours

0
0

ooc
4OoC

5OoC

10

15

P torr) (
Flgure

3. 4

Temperature Dependence of Hydrogen Chloride Adsorption on Gm a Alumina Outgassed at 8OoC am

82
i.e., l o c a l i z e d a d s o r p t i o n .
The Lanepluir e q u a t i o n which i s basedon

l o c a l i z e d a d s o r p t i o n was t h u s a p p r o p r i a t e t o l i n e a r i z e t h e a d s o r p t i o n

data.
Table V I s h o w s t h e c a l c u l a t e d surface area of gamma a m a f r o m l i u n t h e Iangnlulr model and t h e area of each adsorbed HQ molecule on
gamma alumina surface calculated from t h e data given i n Appendix

the

8 .

Using 16.6

g2 as t h e

area o f t h e hydrogen chloride molecule obtained


surface area of Qm a alumina am
Comparison of t h i s s u r f a c e

f r o m liquid density calculations, the


based on HCl a d s o r p t i o n was 48.2 m /g.
2

area with t h e EEL' n i t r o g e n s u r f a c e area of 95.4 m 2/g shows that t h e a m hydrogen c h l o r i d e a d s o r b s on appmximately h a l f t h e g m a alumina
surface.
T h i sg i v e sa d d e d

support t o a chemisorption process occurring

on d i s t i n c t sites on t h e gamma alumina. The n a t u r e o f t h e hydrogen chloride adsorption

s i t e can be

e l u c i d a t e d by c o n s i d e r i n g t h e area occupied by t h e adsorbedhydrogen chloride molecule and the

ideal gamma alumina surface i n Figure 1 .

In

a m t h e ideal g m a surface each aluminum i o n is surrounded by four oxide

ions,thus

t h e area o f t h i s

group I s 32

12 .

Assuming that t h e adsorp-

t i o n s i t e f o r hydrogen chloride

is an aluminum i o n i n t h e

surface,

t h e area of t h e adsorbed HC1 would be 32

5. 1 '

Work by P a x f i t t 5 6 on

HCl a d s o r p t i o n on Ti02 and by P e r i 37-42 on alumina showed t h a t t h e


metal i o n was t h e a c t i v e s i t e inthesesystems.Adsorption
of hydrogen

c h l o r i d e a t every aluminum i o n i n t h e ideal surface would g i v e an m a of16


A

The area of t h e HC1 molecule is 16.6 A

02

and hence would

be

expected t o a d s o r b on everyotheraluminunion.

The average HC1

83

TABLE V I
CROSS-SECI'IONAL
AFUUS OF HYDROCEN CHLORIDE ADSORBED ON

GAMMA ALUMINA

Outgas

Isotherm
Temperature (OC)

Temperature (OC)
80 80

HC1 Surface Area


(rnZ/R)

HCl
Area

(A /molecule)
29.8
9.1

53-1
46.5
41.0

40
50
0 40

80
200
200

38.7
26.5

59.7
44.7
44.1
Average

35.4

200

50

3. 59
33.4 5 4 5 .

48.2

adsorbed area i s

33 22

i n Table V I i n good agreement with the

descrip-

t i o n that a l t e r n a t i n g aluminum i o n s are t h e a d s o r p t i o n a d s o r p t i o n on g m a alumina. a m

sites f o r HQ

Figure 35 i s a r e p r e s e n t a t i o n o f t h e

gamma alumina Surface a f t e r exposure t o hydrogen chloride.


F.

Bdrogen ChlorideAdsorptionon

Alpha

Alumina

The effect of outgas temperature on hydrogen chloride adsorption on alphaalumina

i s shown i n Figure 36.

The.po1nts on t h e 8OoC isotherm may be due t o non The

are f r o m two d i f f e r e n t samples, t h e l o w e r p o i n t s


e q u i l i b r a t i o no ft h es y s t e mb e f o r et h e amount of hydrogen chloride adsorption

measurement was taken.

on a l p h a a l u m i n a i n c r e a s e s
The d i f f e r e n c e between

s i g n i f i c a n t l y between 80 and 2OO0C outgas.

200 and 400C does not a p p e a r t o be s i g n i f i c a n t .


y p i c a l results f o r t h e temperature dependence of HCl adsorption on a l p h a alumina are shown i n Figure 37. increasing adsorption temperature c h l o r i d e a d s o r b e d on alphaalumina. n o t e d f o r HQ
As the r e s u l t s d e m o n s t r a t e ,

decreased t h e amount of hydrogen

T h i s i s similar t o t h e behavior

adsorption on gamma alumina. on alpha alumina was only p a r t i a l l y shown i n

Hydrogen c h l o r i d e a d s o r p t i o n

r e v e r s i b l e as t h e r e s u l t s o f t h e r e a d s o r p t i o n e x p e r i m e n t

Figure 38.

A studyof

t h e temperaturedependenceof

this reversibility
the

was performed by h e a t i n g t h e sample during t h e o u t g a s s i n g s t e p i n


readsorptionexperiment

a f t e r t h e i n i t i a la d s o r p t i o n .

As Figure

39

i n d i c a t e s more of t h e adsorbed hydrogen chloride temperature. Even a t t h e highesttemperature

is removed a t e l e v a t e d

(34loC), some of t h e
at

hydrogen c h l o r i d e r e m a i n s on t h e a l p h a a l u m i n a o r i g i n a l l y o u t g a s s e d 8OoC.

nnnn

*
Figure 35.

Oxygen

Hydrogen Chloride

Ideal Gamma Alumina Surface After Hydrogen Chloride Adsorption

86

0
0

ii
0

0 8OoC
0 20oOc

0 4OO0C
10

15

P (torr)

Mgure 36.

A d s o r p t i o n on AlphaAlumina

I n f l u e n c e of Outgas Temperature on H y d r o g e n h l o r i d e C at 4OoC

87

0
0

ooc
4OoC
50C

10
P( t o r r )

13

Flgure 37.

Temperature Dependence of Hydrogen Chloride Adsorption Alpha Alumina Outgassed at 80C

on

88

10

Adsorption Readsorption

a
V

10

15

P torr) (

F'igure 38.

Readsorption of Hydrogen Chloride a t 4OoC on Alpha Alumina Outgassed a t 2OO0C

0 ooc

173OC

______a_
A

0
0
0

10

15

P torr) (

Flgure 39.

Temperature Dependence o f Hydmgen Chloride Readsorption at OC on Alpha Alumina I n i t i a l l y Outgassed at 80C

90

The i r r e v e r s i b i l i t y o f

hydrogen c h l o r i d e a d s o r p t i o n

on alpha

a l u m i n a i n d i c a t e s that alpha alumina could

act as an e f f e c t i v e sink

for hydrogen chloride since

it h a s t h e a b i l i t y t o

adsorb H C 1 and
of H a

not release it. T h i s i r r e v e r s i b i l i t y , as i n t h e a d s o r p t i o n

on gamma au i a i n d i c a t e s that chemisorption of hydrogen chloride l mn , on alpha alumina is occurring. Analysis of t h e H C l adsorption isotherms on alpha alumina using t h e L a n o u i r equation gave t h e r e s u l t s
2

shown i n T a b l e VII.

The H C l

surface area of 7.9 m / g was appmximately t h e same as t h e BET n i t m g e n

surface area (8.1 m2/g) on alphaalumina.Thisagreement


hydrogen c h l o r i d e s u r f a c e

of t h e

area and t h e BFT n i t r o g e n surface area


surface i s accessible for adsorp-

showed t h a t most of the alpha alumina

t i o no ft h e

hydrogenchloride.

The c r o s s - s e c t i o n a l areas of hydrogen


which are shown i n T a b l e VII, may

c h l o r i d e adsorbed on alphaalumina,

i n d i c a t e a dependence on outgas temperature and adsorption temperature. The areas i n c r e a s e w i t h i n c r e a s e d a d s o r p t i o n t e m p e r a t u r e a n d d e c r e a s e


with increased outgas temperature.

F u r t h e r s t u d i e s u s i n g a wider range

of temperatures

axe needed t o e s t a b l i s h if t h i s dependence a c t u a l l y


area of an adsorbed hydrogenchloridemolecule

exists.

Theaverage

was 17.5

x2.

The s i g n i f i c a n c e o f t h i s area i s seen on r e f e r r i n g t o surface i n Figure 26.

t h e i d e a l alphaalumina
d.uminUm

If, a g a i n , surface

i o n s are t h e a d s o r p t i o n

s i t e , t h e n t h e ideal H C l adsorbed
t h e area obtained from the

a n a would be 19.5

'A2

i n agreementwith

hydrogen c h l o r i d e a d s o r p t i o n

d a t a on a l p h a alumina.

Hydrogen c h l o r i d e a d s o r p t i o n

on alpha alumina i s i n f l u e n c e d by

outgas temperature and adsorption temperature

in similar ways to that

91

TABLE VI1
CROSS-SECI'IONAL AREAS OF HYDROGEN CHLORIDE ADSORBED ON

ALPHA ALUMINA
Outgas

Temperature
(OC)

Isotherm Temperature
(OC)

HC1 Surface Area (m2/g )

HC1
(12,-molecule)

80 80

8.0 6.4

16.9
21.1 22.3

40
50

80

6.1
9.1 76 . 7.6 9.9
8.1
8.0

200
200
200

14.7

40
50
0

17-5 17.7

400
400 400

13.6
16.6

40

50
Average

Average

16.8

7.9

17.5 5 2.8

of hydrogen chlorideadsorptionon

g m a alumina. a m

Increased'outgas

temperature and t h u s decreased amounts of pre-adsorbed water increased

hydmgen c h l o r i d e a d s o r p t i o n . T h i s
vapor and hydrogen chloride compete
t h e two aluminas.

trend seems t o i n d i c a t e t h a t water


for similar a d s o r p t i o n sites on

The most s i g n i f i c a n t d i f f e r e n c e i n t h e a d s o r p t i o n chloride on alpha

of hydrogen

and g m a alumina i s t h e amount adsorbed per u i a m nt

area,

Alpha aluminaadsorbs

more hydrogenchloride

per u n i t area than

g m a alumina as shown i n figure 40. a m

The difference i n a d s o r p t i o n

capacity can again

be e x p l a i n e d on t h e b a s i s of t h e p a c k i n g of aluminum ideal s u r f a c e s of alphaand

m-d o x i d e i o n s i n t h e

g m a alumina. a m

On

a mass basis, however, gamma alumina has a greater a d s o r p t i o n c a p a c i t y


than alpha alumina for hydrogen chloride because of
area.

i t s greater surface

G.

I s o s t e r i c Heat of A d s o r p t i o nf o r

Water Vapor on Alumina

Uater vapor adsorption on alpha and gamma alumina was temperature


dependent as shown i n Figure 25 and Figure 30. dependence was u s e d t o c a l c u l a t e t h e Thistemperature

isosteric heat of adsorption for

water vapor on both aluminas.


E? Although t h e 3 3 equation was p r e v i o u s l y u s e d t o l i n e a r i z e t h e experimental data t o o b t a i n s u r f a c e the experimental axeas, i t did not adequately
fit

data a t low surface coverage as s e e n i n Fpe 41 ' r i

where u s e of a F'reundlich p l o t ( I n N v s I n P) gave a better f i t of - t h e experimental data. Table VI11 shows t h e e r r o r s p r o d u c e d i n f i t t i n g

a m t h e H20 a d s o r p t i o n data on g m a alumina outgassed a t 8OoC by u s e o f t h e BFT and the Freundlich equations.

93

1
10

\o

0
d

>*
2

0
0

Y-l

a41 0

2 3

Figure

4. 0

Alpha and

Comparison of H y h g e nC h l o r i d eA d s o r p t i o n a t 40C on Gm a Alumina Outgassed a t 200C am

94

6.13 -

0
0

Experimental

Freundllch

o m
6.1> -

z
d

7.c I

7.5

1
In P

Figure 41.

Comparison o f Ei X a n d F'reundlich E q u a t i o n s f o r F i t t i n g E E x p e r i m e n t a l Data of HC1 A d s o r p t i o n on Camma Alumina

95

TABLE VI11

ERROR FOR

FLT OF H20

ADSORETION ISXHERM ON G k " A ALUMINA

USING THE BFP AND FFWNDLICH EQUATIONS

Slope

Y-Intercefl

. "

E m
Freundllch

3.7
0.9

242

0.06

The r e s u l t s o f t h e a r a l y s i s o f t h e i s shown in Table IX.

t e m p e r a t u r e deoendence data

k s t h e i s o s t e r f c he?.t;

i n d i c a t e , water a d r o r p t i o n

on alun?ina is a n exothermicprocess.
s t e r i c neat ofadsorptionthan
conclusion, llightman"

Alpha aluminahad

a hi$her isothis

mmqa alumina.

In supportof

found higher heats


alumina.

of immersion i n H a t e r f o r also

a l p h aa l u n i n at h a nf o rg a m a reported higher alumina.The

Evel-1. Wade and Hackeman"

heats ofimmersion

f o r a l p h a alumina t h a n f o r gamma

l a r g e r heat of Immersion f o r a l p h a alumina resttlts f r o m molecules a d w r k d p e r unit area on alpha


L

t h e l a r g e r numher of H,O

alumina t h m on gama alumina.


H.

Thermodynamic Yodel

of flydrogenChlorldeAdsorotion

on Alumina

In o r d e r t o c o r r e l a t e t h e e x p e r i m e n t a l d a t a f o r t h e a d s o r p t t o n
of water vaporandhydroqenchloride on a l u m i n a , a water l a y e r model
data."

was t e s t e d using Wichtran'scalorlmetric

The model c o n s l s t s

of d e s c r i b i n g t h e a d s o r t e n t
l a y e r so fp r e - a d s o r k d

as m almlna p a r t i c l e surrounded by s e v e r a l

water as shoun i n F i g u r e 42.

T h i sd e s c r i p t i o n

i s consistent with
w a t e rt o

peri's I n f r z r e d results j7-" which showed molecular

te p r e s e n t on thesurface

of a?w.ina up t o 400 C.

Since wa+.er
as shown
?E

vapor adsorotion increased

w i t h increasing outga; temperature

i n Figures 24 a?d 2 8 , successive water l a y e r s a r e p o s t u l a t e d t o


removed from the alumina

particle as t h e o u t g a s temperature l.s r a i s e d .


t h e thickness alumina
by t h e

A u n t r e a t e d a l u m i n a p a r t i c l e c o n t a i n s a water l a y e r o f n

represented by t h ed i s t a n c e

El

- T3

i n Figure 42.Outgassingthe

a t a temperature T 1 removes part ofthe


dlstance N

water l a y e r r e p r e s e n t e d

T1 in Figure 42.

The temperature T

a t which no water

97

TAHLE IX

ISOSTERIC HEAT OF A S R TO FUR WATER V A P O R ON ALUHINAS DO P I N Outgas TemperatureAdsorbent


("C)
Camma
80
80 400

0.58
0.98
1.03 0.52

Isosteric

Heat
ikcal/mole)

13.9
14.5

+_
+ -

2.8 1.2

Gamma
Gamma

11.0 2 4.8

Alpha Alpha Alpha


Alpha

80 80
400

16.7 & 2.3 19.6 2 2.4

0.86 0.81

17.2
19.2

7.4

400

1.04

5 5.6

N,r

= N - T

N.r

N - T

Figure 42.

A l u m i n aP a r t i c l e

with S u r m u n d l n g Layers of Water

99
surrounds the alumina p a r t i c l e was taken as 4OO0C since P e r i ' s i n f r a r e d

work3742
400C.

indicated the absence of molecular

water on g m a alumina a t a m gamma alumina a f t e r

The amount

o f water p r e s e n t on alphaand

a glven outgas temperature was taken as t h e difference i n t h e amount

of water adsorbed on alumina outgassed at 4OO0C and t h a t a d s o r b d on

alumina outgassed a t any l o n e r t e m p e r a t u r e .


The adsorption of hydrogen c h l o r i d e on alumina can be described

as a t n o s t e p p r o c e s s

as shonn I n FI&ure 43, The i n i t i a l s t e p i n t h e


1) is the solution
of t h e hydrogen c h l o r i d e
The second

adsorption process (Reaction

gas i n t h e l a y e r o f
step(Reaction

water surrounding t h e alumina particle.

2 ) i s theadsorption

of t h e d i s s o l v e d hydrogen c h l o r i d e

on t h e alumina particle. The e n e r g e t i c s o f following equation:

t h e two s t e p p r o c e s s a e r e p r e s e n t e d by t h e r

where:

.Ern

= the

integral heat o f a d s o r p t i o nf o r

HCl(g) on

A1203

Qst = t h e i s o s t e r i c h e a t of a d s o r p t i o n
dB
= the incremental = the

c h a n g e i n surface coverage

-\Hsol

i n t e g r a l heat o f s o l u t i o n f o r HC1 i n water


HC1 and

"c~/Av~
A test o f t h e

= t h e i n t e g r a l h e a t of i n t e r a c t i o n b t w e e n

alumina

water l a y e r model I s a comparison of the integral

isosteric h e a to fa d s o r p t i o n

ments and theheatof

immersion o f alumina i n hydrochloric acid.


h e a t of s o l u t i o n ,

QstdO determined by g a s phase measure-

two v a l u e s d i f f e r only by t h e i n t e g r a l

-\HSol.

The Each

100

1.

HCl(g)

+ H20

(1)

HC1 i n X moles HZ0

2.

H(Sl(aq)

Al,U
L 3

(s)

___c_

HC1

---

A1 0

2 3

Figurr 43.

P o s s i b l e Mechanism f o r Hydrogen Chloride Adsorption


on Alumina

101

of the parameters in equation ( I ) was determined experimentally as


described below. The h e a t s o f immersion of alpha and has teen measured by Wightman"
A study of the

gamma alumina i n 0.1 Pi HC1

and t h e results are shown i n Table X.


a c i d solutions of varying

change i n pH of hydmchloric

concentration upon a d d i t i o n of alumina was used tn e s t a b l i s h i f Vightman's results were d e t e m i n e d a t monolayercoverage chloride.Table

of hydmgen

X andTable I

XI1 sn0.i the Lhange i n p ofhydrochloric H

a c i d s o l u t i o n s upon a d d i t i o n of a l p h a and gamma a l u m i n a , r e s p e c t i v e l y .

pH

is t h e p beforeaddition H

of t h e alluninum and pHlo. pH60 and p-%80

i s t h e p of t h e s o l u t i o n H

a f t e r 10, OO and 180 minutes, respectively.


alumina t o

N s i g n i f i c a n t p change is o b s e r v e d a f t e r a d d i t i o n o f o H 0.1 N HC1 solutions.Thisabsence

of change i n pH i s a good i n d i c a t i o n
HC1 f o r

t h a t a 0.1 IJ HC1 s o l u t i o n h a s a s u f f i c i e n t c o n c e n t r a t i o n o f
s a t u r a t i o n o f the alumina surface. The i n t e g r a l heat of s o l u t i o n of HC1 i n water l i n e a re x t r a p o l a t i o n of t h ed a t a
Has

determined t y

i n Tabla XIII.

The number of moles

of adsorbed water was determined as described atove.


The i s o s t e r i c h e a t o f a d s o r p t i o n temperaturedependence
(,QSL,

was determined fmm t h e shown i n

of the hydmgen cnloride adsorption 'The e x p e r i m e n t a l r e s u l t s

Figure 34 and Figure 37.

were l i n e a r i z e d

on a I n N vs I n P p l o t .

Figure 44 shows a comparisonoftheexperimental


t h e Pkeundlich

data with results c a l c u l a t e d using t h e Langmuirand


e q u a t i o n s t o f i t t h e data.

After f i t t i n g and e x t r a p o l a t i n g t h e data

t h e i s o s t e r i c heat was c a l c u l a t e d using hydrogen chloride isotherms

102

TABLE X

HEATS OF IMMERSION OF ALPHA AND GAMMA ALUMINA I 0.1N HC1 AT 3OoC N


Outgas Temperature

-AwH
(mJ/m2

-A,H

("C)
80 100
200

0
7.23 7.73
11.0 - 0.1 +

088

949 17(1.%) 1351

300

1732
1829

B(2.296)

+ 14.1 - 0.3

400

2 60(3.3%)

14.9 -+ 0.5 -

Camma

TAELE XI
p OF SLURRIES OF ALPHA ALUMINA AND HYDROCHLORIC ACID H
Outgas

0
100 1.49 200 200 01 . 0.001 0.01 5.17 0.016 0.032

PHO 1.43

PHlO

DH60

p1 0 !8

3.37
2.30
2. Og

10.03 9.39

9.76
5.76
6.03 4.14 2.33 1.36 2.62 1.32

200
200

3.95
2.11 1.33

1.74 1.25

200

01 .

104

TABLE XI1

pH OF SLURRIES OF GAMMA ALUMINA AND HYDROCHLORIC ACID

PHlO -

PH60 1.41

'580
1.36

100

0.1

1.42 3.16 2.14 2.01 1.68 1.26

1.42 4.51

200

001 .0 00 .1

4.65

4.69
4.00

200
200

3.38
2.38

3.93
3.54
1.95 1.29

0.016
0 032

3.93
2.10 1.29

200 200

1.82
1.27

01 .

105

TAHLE XI11

INTEGRAL HEATS

OF SOLUTION FOR HQ

I WATER AT 25OC N

Moles of H20 per mole HC1

Integral Heat (kcal/mole)


-18.003

20,000
5.000

-17 978
-17 952 -17.940 -17 893 -17.839 -17 778 -17 693 -17 557 -17 315 -17.01 -16.651 -16.35

3,000

1.000 400
200

100

50

25
15 10 8

6 4

-15.79
-14.67 -13.63 -11.71 - 6.31

3
2 1

106

-8.0

-8.2
0

0 Experimental
0 Langmuir Freundlich

-8.4

-. 1

In P

Figure

4. 4

Comparison of Ekperimental Data with Results Calculated Using t h e Langmuir and Freundlich Equations for HC1 Adsorption a t OC on Cm a Alumina Outgassed a t 8OoC a m

dstennined a t 0, 40 and 50C andEquation


t h e isosteric h e a t c u m e s adsorption on

1. 1

Figures

45 and 46 show
HCl
.

as a f u n c t i o no fs u r f a c ec o v e r a g ef o r

gamma alumina a n d a l p h a a l u m i n a , r e s p e c t i v e l y . h r a l u a t i o n

of t h e i n t e g r a l isosteric h e a t of a d s o r p t i o n ( J Qstd8) was facilitated


by obtaining a q u a d r a t i c e q u a t i o n d e s c r i b i n g t h e . h e a t

curve using a

non,-linear least square f i t of t h e Qst v s 0 data as d e s c r i b e d i n Appendix 1 0 . I n t e g r a t i o n of t h e e q u a t i o n between 8 = 0 and 8 = 1 t h e n

gave t h e i n t e g r a l isosteric h e a t of adsorption. The r e s u l t s o f t h e r i d ea d s o r p t i o n

water l a y e r model a n a l y s i s f o r hydrogen chloTheagreementbetueenthe


A

are shown i n T a b l e XIV.

h e a t of a d s o r p t i o n d e t e r m i n e d c a l o r i m e t r i c a l l y ,

%,
A

and t h e h e a t o f

adsorption determined f r o m t h e gas phaseadsorption, ably good f o r a l p h a a l u m i n a o u t g a s s e d

HG, i s reasonThe d i f f e r e n c e

a t 80 and 200C.

i n A H,, and A HG on a l p h a alumina outgassed a t 4OO0C may be an i n d i cation that not

a l l the pre-adsorbed

water was removed a t 40OoC.


of a d s o r p t i o n on gamma alumina

The poor agreement f o r t h e h e a t s may be attributed t o t h e p r e s e n c e

of water on gamma alumina a t 40OoC.

Further there i s considerable uncertainty integral heat of solution curve to very heat of solution
i s not reported.

i n t h e e x t r a p o l a t i o n of t h e
low c o n c e n t r a t i o n s where t h e

A comparison of the calorimetric heat

and i n t e g r a l isosteric

h e a t of a d s o r p t i o n f o r hydrogen chloride adsorption on alpha alumina s u g g e s t s t h a t hydrogen chloride adsorption process with initial solution thealumina
particle.

may involve a two s t e p

i n pre-adsorbed water layers surrounding

However, f u r t h e r work i s needed t o e s t a b l i s h

t h e thermodynamic v a l i d 3 t y o f t h i s model.

108

20

20oOc

4oooc

10

-10

-20
*
1

J "

0.2

0.4
8

0.6

0.8

10 .

figure 45.

Isosterlc Heat of Adsorption f o r H C 1 on Camma Alumina

1: 2

0
D
100

8OoC
20oOc

4OoOc

75

50

\a

figure

4. 6

Isosteric Heat of Adsorption f o r HC1 on Alpha, Alumina

TABLE XIV
RESULTS OF WATER LAYER MODEL TREATMEKT

X
kcal kcal
Adsorbent Gamma-80 Gamma-200 Gamma-400 -2.3

IHS0l

+ L

Hz0 HC1

mole mole
0.23

-33.4

kcal mole

-%
mole kcal

3.8
3.1

6.13

-8.5

0.0

0.0

-79.9

-8.5

Alpha-80 Alpha-200 Alpha400

-31.0

0.69
0.44

-4.7
-3.4
0.0

-28.3 -32.2'

-26

-29.5

-26.2

-76.3

0.0

d . 9

-76.3

11 1

I.

ESCA S t u d i e s :

In order to elucidate the nature of the adsorption


s t r u c t u r e of t h e adsorbed species, narrowscan obtained on both alpha and t o hydrogen chloride.

s i t e and

ESCA spectra were

g m a alumina before and a f t e r exposure a m

N g u r e 47 shows t h e C 1 2p ESCA peak f o r untreated g m a alumina. a m Untreated g m a alumina contains some chlorine contamination as Seen a m i n Figure 47, which i s not unexpected since The n a m ws c a n

it i s prepared from

Alcl3'

and 1/2 peaks are shown i n Figures 48 through 51 f o r u n t r e a t e d a l p h a a l u m i n a .

ESCA spectra o ft h e

Al 2slI2,

Al Zp, 0 1s

One sees a s i g n i f i c a n t s i g n a l f o r c h l o r i n e i n s i g n a l , however, was o b t a i n e d by c o u n t i n g t h e 6:3:3:2;2 forthe


C 1 2p, Al 2s1j2,

Figure 51.

T h i sl a r g e

spectra i n a r a t i o of

the chlorine signal and Al 2p signals.

, and C 1s1i2, t h u s 1/2 was counted twice t h e time as l o n g as t h e A 1 2 s 1/2 The s e n s i t i v i t y o f p h o t o e l e c t r o n s p e c t r o s c o p y for
Al s p , 0 Is
greater

c h l o r i n e i s approximately three times greater than i t s s e n s i t i v i t y


~ ~ f o r aluminum as shown by Y a ~ e r . Thus, because o f t h e

sensitivityandlongercounting

time, t h e c h l o r i n e s i g n a l d o e s n o t
An ESCA spectra of an

r e p r e s e n t a large c h l o r i n ec o n c e n t r a t i o n .

u n t r e a t e d t h e t a alumina p r e p a r e d i n an independent laboratory79

by

a p r e c i p i t a t i o n method a l s o gave a s i g n i f i c a n t c h l o r i n e
i n Figure 52.

peak as shown

N a r r o w scan ESCA spectra of t h e two aluminas after o u t g a s s i n g a t

4OO0C and exposure t o 20 t o r r of hydrogen chloride showed no i n c r e a s e i n t h e c h l o r i n e s i g n a l n o r

at OC,

surprisingly

any s i g n i f i c a n t change

205.6

185.6

Figure 47.

ESC4 Spectrum of Chlorine 2p Electrons Obtained from Untreated Gm a am

Alumina

126.4

116.4

106.4

Binding Energy (ev)

figure

4. 8

ESCA Spectrum of Aluminum 2s Electrons Obtained f m m Untreated Alpha

Alumina

80.4

70.4
Binding Energy (ev)

60.4

Flgure

4. 9

ESCA Spectrum of Aluminum 2p Electrons Obtained f r o m Untreated Alpha Alumina

535.4

525.4
Binding Energy (ev)

515.4

Mgure 5 . 0

ESCA Spectrum of Oxygen 1s Electrons Obtained From Untreated A l p h a Alumina

. . ..

2W.4

194.4
BindingEnergy

1W.4
(ev)

Flgure 51.

ESCA Spectrum of Chlorine 2p ELectmnsObtained Alumina

f m m Untreated Alpha

Flgure 52.

ESCA Spectrum of Chlorine 2p Electrons Obtained f r o m UntreatedTheta


Alumina

i n the binding energy


peaks.

o r shape of the chlorine,

aluminum o r oxygen

T a b l e s XV and X V I show t h e e l e c t r o n b i n d i n g ' e n e r g y , f u l l

peak

width a t h a l f maximum, range of t h e ESCA peaks and work f u n c t i o n

(8)

f o r gamma and alpha alumina, respectively, before


w i t hh y d m g e nc h l o r i d e .F a i l u r et oo b s e r v ec h a n g e si nt h e

and after treatment

ESCA spectra
adsorbed hydro-

a f t e r exposure t o h y d r o g e n c h l o r i d e i n d i c a t e s t h a t t h e

gen c h l o r i d e is b e i n g l o s t i n t h e s p e c t r o m e t e r .
under vacuum i s u n l i k e l y s i n c e i s o t h e n n
c h l o r i d ea d s o r p t i o n

A simpledesorption

data showed t h a t t h k

hydrogen

is i r r e v e r s i b l e .

A photodesorptionprocess

is a

possible e x p l a n a t i o n for the loss of the adsorbed hydrogen chloride,


Photodesorption of gases has been observed from solids such

80 as M o

CdS81 a n d s t a i n l e s s steel.

82

TAELE X V
ESCA BINDING ENERGY, RANGE AND FULL PEAK

W H AT I m

HALF

MAXIMUM FOR GAMMA A U I A L MN

Untreated Ae, v

HQ 'Ekposed
Ave

c1 2p

102 Range FH W M (eV)

B E (ev) . .

198 9

197 3

198.1

37 .
38 . 118.7 12.8

43 .
4.1 118.1 13.3 118.4

198.1 196.1 897 12.3

197 5

3.7
119.0 120.9 10.7 38 . 74.0 16.8

Al 2 s

B E (eV) . . 102 EWHM (ev)


Range (eV)2 10 Fbnge WHM (ev)

34 .

34 .

9*6 5.4
74.2 15.4 32 . 531.5 28.9

119.9

B. E .

73.9
16.6 30 . 531.1

73.3
21.2, 30 . 530e 7

73.6

74.1

Al 2 P

34 .
531.0 12 . 531.3 25.9

0 1s

B. E. (eV) Range 102

37.3 34 .
-0.2

46.7 3.4
06 .

531 2

3.7
18 .

36 .

120

TABLE X I V

ESCA BINDING ENERGY, RANGE AND FULL PEAK WIDTH AT HALF

MAXIMUM FOR ALPHA ALUMINA


Untreated

B E. ( V , . e)
Q 2P

Range 10 FWHM(ev)
117.8 15.4 26 . 7. 31 20.0 21 . 530 3 5. 00 24 . -2.6 -3.0

198.2 0.4

198.0 1.3

Ave 198.1

3.3

3.3
117 9

B. . 118.1 E (eV)2 Al 2s Range 10 17.1 FWHM (ev) 26 .


Al 2P

B E (eV) . . Range 102 FWHM (ev) B E. (eV)2 . Range 10

73.2

0 1s

530.6 61.1

530.4

26 .

-0.6
HQ Exposed

B E. (eV), .
Q

2P

Range 10 WHPI (ev)

198.9 14 . 41 . 118.2 16.6 31 .

198.3 16 . 40 . 118.0 17.6 29 . 73.2 2. 81 23 . 530.5 53.2 26 . -0.9

198.4 07 . 38 . 118.0 18.3 27 . 73.2 31.4 23 . 530 4 71.8 2.5 -3.0

Ave 198 5

Al 2s

B. E. (eV), Range 10 FWHM (eV)


B E (eV)2 . . Range 10 WHM (ev)

118.1

73.4
2. 58 26 . 530.8 62.3 31 . -0.9

73.3

2P

0 1s

B E. (eV)2 . Range 10

530.6

V.

SUMMARY AND CONCLUSIONS


two adsorbents, alpha and gamma alumina,

Characterization of the using

BET n i t r o g e n surface area measurements, after o u t g a s s i n g at


showed t h a t t h e s u r f a c e

100, 200 and @O0C

area of alpha alumina

was

independent of outgas temperature but


surface area a t 40OoC.

gamma alumina showed a l o s s i n

The s u r f a c e area of alphaalumina

was 8.1 5

1.8 m2/g.

Gm a alumina outgassed a t 100 and 200C had a s u r f a c e am

2 area of 95.4 2 3.4 m /g which decreased to


o u t g a s s i n g a t 40OoC.

85.6 5 3.9 m 2/g after

Adsorption and desorption isotherms of nitrogen onbothaluminas showed no h y s t e r e s i s .

a t 77OK o b t a i n e d

It was concluded t h a t n e i t h e r

a m a contained micropores. l i u n

Scanning electron photomicrographs of alpha and showed t h e particle s i z e a n d t e x t u r e

g m a alumina a m Gm a alumina am
be l a r g e r

of thealuminas.

consisted of clusters of secondary particles appearing to t h a nt h ep a r t i c l e so fa l p h aa l u m i n a . o f gamma alumina studied

However, t h ep r i m a r yp a r t i c l e s

a t 5OOOX magnification showed that t h e y w e r e


of alphaalumina.Thisconclusion gamma

smaller t h a n t h e p r i m a r y p a r t i c l e s

was c o n s i s t e n t w i t h c a l c u l a t e d p a r t i c l e s i z e s o f a l p h a a n d
alumina based on Adsorption of

BET n i t r o g e n surface areas.


water vapor on a l p h a and gamma alumina at 30, 40

and 5OoC showed d e c r e a s i n g water v a p o r a d s o r p t i o n w i t h i n c r e a s i n g a d s o r p t i o n temperature. The isosteric h e a t of a d s o r p t i o n f o r water

vapor was larger f o r a l p h a alumina t h a n f o r gamma alumina, based on

a Clausius-Claperyon analysis of the temperature dependence.


121

122

Water vapor adsorption on alpha and


dependenceon outgastemperature.

g m a alumina showed a a m

Alumina outgassed a t 80, 200 and

4OO0C showed i n c r e a s i n g a d s o r p t i o n o f

water vapor. This increase

was

a t t r i b u t e d t o s u c c e s s i v e removal of physisorbed water f r o m t h e alumina. Readsorption experiments of water vapor adsorption on alpha and

g m a alumina showed t h a t water vapor adsorption was completely a m


reversible.

It was concluded that water vaporadsorption

onboth

alpha and gamma alumina involved a physisorption process.


A significant d i f f e r e n c e i n t h e

water adsorption capacity of the


more water vapor per

two aluminas was found.

Alphaaluminaadsorbed

unit area than gm a alumina. a m

The d i f f e r e n c e i n a d s o r p t i o n c a p a c i t y

was explained by ideal surface models of alpha and gama alumina.


Differences i n a d s o r b a t e areas, determined using the
w e r e explained on t h e basis o f t h e i d e a l s u r f a c e .
E T equation, E

O alphaalumina n

each adsorbed water moleculeoccupiedan w i t h t h e calculated value of 13.5

area of12.4

(d2 c o n s i s t e n t
area on t h e

82

for the adsorbate

ideal alpha alumina surface assuming each adsorbed r e q u i r e d two s u r f a c e oxygen ions. alumina surface would be 16 t i o n site. moleculeon Theadsorbed

water molecule

area on t h e i d e a l gamma

22

assuming two oxygen i o n s as t h e adsorpwas 16.2

The area obtained f r o m the adsorption isotherms gamma alumina.

22/

O t h e basis o f t h i s agreement, i t was n

concluded that t h e s i t e f o r water vapor adsorption on alumina i s two oxygen i o n s w i t h hydrogenbonding


s i t e and t h e adsorbate.

o c c u r r i n g between t h e a d s o r p t i o n

Hydrogen chloride adsorption on alpha and gamma alumina showed a dependenceon outgas temperature and adsorption temperature.

Alumina outgassed at 80, 200 and 4oOC showed increasing hydrogen

chloride adsorptionwithincreasingoutgastemperature.Higher
outgas temperatures removed water molecules which were blocking sites on t h e alumina necessary f o r hydrogen chloride adsorption. Readsorption experiments of hydmgen chloride on alpha alumina showed t h a t hydrogen chloride adsorption
and gamma

was approximately
of t h e

6046 i r r e v e r s i b l e .

A study of thetemperaturedependence

i r r e v e r s i b i l i t y showed t h a t hydrogen chloride desorbed from alpha alumina even

was not completely

a t temperatures as high as

NlC.

Eecause of t h i s i r r e v e r s i b i l i t y , it was concluded that hydrogen chloride adsorption on alumina involved Hydrogen c h l o r i d e a d s o r p t i o n
a chemisorption .process.

on alpha and

gamma alumina showed

a dependenceonadsorptiontemperature.
isotherms obtained

Hydrogen c h l o r i d ea d s o r p t i o n

a t 0, 40 and 5OoC showed a decrease i n t h e amount temperature.


I s o s t e r i c h e a t s of a d s o r p t i o n

a d s o r b e dw i t hi n c r e a s i n g

obtained from t h i s t e m p e r a t u r e dependence showed a n i n c r e a s i n g h e a t


of adsorptionwithincreasingoutgastemperature.

The isosteric

h e a t of a d s o r p t i o n decreased with increasing surface coverage.


A comparison of t h e isosteric h e a t s o f a d s o r p t i o n w i t h c a l o r i -

metric h e a t s of a d s o r p t i o n was made u s i n g a water l a y e r model.

Because

of t h e agreement of t h e isosteric h e a t s a n d t h e c a l o r i m e t r i c h e a t s
adsorption for Wdrogen chloride on alpha alumina o u t g a s s i n g it was c o n c l u d e d t h a t t h e
described theadsorptionprocess.

of

a f t e r 80 and 200C

water l a y e r model adequately


Hydrogen chlorideadsorptionon
of t h e g a s i n t h e

alumina may involve an i n i t i a l s o l u t i o n p r o c e s s

124

pre-adsorkd water surrounding the alumina


adsorption on the alumina surface'.

particle followed by t h e

A s i g n i f i c a n t difference i n t h e amount of hydrogen c h l o r i d e


adsorption on alpha and gamma alumina was observed.
Alpha alumina

adsorbed more hydrogen c h l o r i d e p e r u n i t

area than gamma alumina,


was explained on t h e basis of
g m a alumina. a m

T h i s difference in adsorption capacity


t h e i d e a l surface models f o r a l p h a a n d

Agreement n a s

observed between t h e hydrogen c h l o r i d e adsorbed area on g m a alumina a m

(33.4 22/molecule) and the (32 2 /molecule)assuming


2

area c a l c u l a t e d for t h e ideal gamma surface

that an aluminum i o n i s the adsorption site.

For t h e ideal alphaalumina surface, using t h e same assumption,the 2 adsorbed area was 19.5 8 /molecule in agreement with 17.5 X2,hnolecule
from t h e hydrogen chlorideadsorption agreementbetween
isotherms.

On t h e b a s i s

of t h e
from

t h e ideal adsorbate areas and those obtained

the adsorption isotherms

i t was concluded t h a t t h e s i t e f o r hydmgen


i s a surface aluminum ion.

chloride adsorption onalumina

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APPE3DIX 1
Preparation of Alpha and
Gm a Alumina Samples f o r am

Infrared Spectroscopx Attempts to prepare infrared transparent nereunsuccessful.Varioustechniques Themain source of problemswith
d i s k s of t h e t n o a l u m i n a s

were t r i e dw i t h o u ts u c c e s s .

gamma alumina was s t i c k i n g t o t h e

faces of t h e s t a i n l e s s

steel press.

To p r e v e n ts t i c k i n gt h ep r e s s
was a p p l i e d , p r e s s i n g

was p o l i s h e d . s e v e r a l times, heated before pressure


under vacuum was a t t e m p t e d , v a r i a t i o n o f t h e p r e s s u r e

from 1200 t o
(;amma alumina

20000 p s ia n dt h em o u n to f

alumina was a l s o v a r i e d .

was pressed between f i l t e r paper, polycarbonate film and Teflon


l t t h e s et e c h n i q u e s m
w e r e u n s u c c e s s f u l .A t t e m p t st or e l e a s et h e

film

gm a a m

alumina f r o m t h e face o f t h e p r e s s u s i n g a c e t o n e a n d t h e disk, F i n a l l y ,t h e

water only cracked

g m a alumina was pressed between a s h l e s s f i l a m


a t 5OO0C a n d s u i t a b l e t r a n s p a r e n t
of t h e alumina, however,

t e r paper, the paper


d i s k s were obtained.

was ashed off

The c r y s t a l l i n ep h a s e

nas questionable because of the thermal treatment. Alpha alumina could t h es t i c k i n g be p r e s s e d i n t o

disks without encountering


press alphaaluminainto w e r e unsuccessful.

problem. Honever,

a t t e m p t st o

d i s k s t h i n enough f o r good transmission propelcties


Becauseof the difficulty in preparing suitable

disks of t h e

alumina samples no i n f r a r e d measurements were performed.

APPENDIX 2 Sample Calculation of Isotherm from Experimental Data

Data "abler
Weight Sample; Alon Rn 1 u: Pretreatment
'

15.8768

2 hrs 2OOzC 2 hrs 50 C Ro = 526.25

Helium Volume C a l i b r a t i o n I

R1
648.10

R2 634.80

VI

1 '

p2

V T

VB S

113.43

121.8

108.5

127.3

13.9

Volume Calculation; The system volume is c a l c u l a t e d by first f i n d i n g t h e pressure of Helium: P = 1

5-

Ro

= 648.10
a

526.25 = 121.8 t o m 526.25 = 108.5 t o r r

( 2 4

P2 = R2

- Ro
x
p2

634.8

(2-B)

The t o t a l volume is then:

vT=

('I

' 1 )

- ~. - 113.43 cc

X 121.8 torr 108.25 torr

127.3 cc
( 2 4

HQ Adsorption Calculation t The first point on t h e isothexm in moleHCl/gram is calculated by t e following procedure: h adsorbent

then :

and t h e n u s i n g t h e ideal gas law:

- PXVT N1 - R X T X Y
= 35.52

6.44 torr X 12'7.3 cc


6.24 X

lo4

( 2 4

cc-torr mole- K
0

323OK

0.1145g

lo"
is:
VT

mole-gram

-1

The second point


pcATJ
=

(P1 X V I + P2 X VSB),

- u.55 x

113.43)

18.3

(1.80 X 13.9)

and then:

Thenumber of moles adsorbed is t h e n :

by t h e second dose, using equation 2 4 ,


-1

N =

0.39 X .6.24 X

127.3
X 323 X 0.1145

lo4

2.15

mole-gram

T h i s pmcedure i s c o n t i n u e d u n t i l all t h e NI's havebeen

calculated.

To f i n d t h e number of moles on t h e surface a t each

pressure a summation i s made of the number of moles deposited

by

133
each

dose.

Thus, the last column in the table

is calculated b: y

etc.

The isotherm i s obtained by plotting N s

vs. Pmp,

APPENDIX 3 R e s u l t s of S o l u b i l i t y Measu.rernenJs of A l p t ~ .and G q a Al-yina ~

in Water and 0.1 N Hydrochloric Acid


Concentration of Aluminum ( ppm)
0.0

Solution

Type of Alumina
alumina) (no Blank

HQ

Y
HCI.
HC1

0.9
60. b

Y
Y

52.5
72.8
0.3

HCl

Y
a

HC1
HC1

a a

3.7
4.1

APPENDIX 4

"F'0.l"

~ e p g r a mto Fit Isotherm b t a t o Freundlich

Equation

W A

C-8K MODV 1 1 -219


0 1 . 0 5 T I I !I " L NP VS. V(MOLE/Pl*M) FROM FREUNDLICH" I 01.06 T N * I0t5-CALC . " I I 0.1 7 A I I " T E N P E R A T U 3 E " T A , ' * @ SYSTEM"SY, I Q 1 .@8 A " SURFACE AREA"SA , I 01 .I5 A " NUMBER OF DETERMINATIONS" N , 1 1 01.20 T " P rhIP)t5",! I 9 1 . 2 5 S P = Q ; S Q = 0 ; S R - 0 ; S S=8; S W=a 01.30 F I = I , N ; D 2 . 0 8 01.35 D 3.00 0 1 .48 G 7,635

02.05 02.07

02.15 02.20
83.85 03.18 03 .I 5 03.70 03.26 03.28 93.30 03.35

A S S S

" " X(11," ".Y ( I 1 I X(I)=FLOG(X(I>>; S Y(I)=FLOG(Y(I)/SA> P = P + X ( I > ; S Q=Q+Y I ) ( R = R + X ( I > * X ( I ) ; S S = S + X ( I ) * Y ( I > ; S W=W+Y(I>*Y(I>

S NSZ(N* S-P*Q) S D=N* R -P*P

S NI=R*Q-P*S S SL=NS/D; S I N=NI/D DO 6.DR S IN=IN-(5*FLOG(10>> T Z, ! '' I N T E R C E P T " 1 N," ERROR"DB, I T " SLOPE" SL ," E R R O R " D M, I 03.48 T E R R O R I N INTERCEPT I N C O R R E C T " , I !

0 6 . 0 5 S RS=SL*( W / N > 06.10 S TS:=W-(Q*Q> / N 0 6 . 1 5 S SS=TS-RS 06.20 S S Q = S S / ( N - 2 ) Q6.25 S D M = F S Q T ( S Q / ( D / N > > 0 6 . 3 5 S DY = F S Q T ( S Q ) / 0 6 . 4 5 S CB =FSQT ((SQ*R> D 1

135

07.p15 07.10 0. 5 71 07.20 07.25

A " NUMBEFi OF POINTS"NP,I A " I NCREMENT M O L E / # P l " I C , I A " I NITIAL M O L E / : ~ N " N M , ! ! !

F I = l ,NP;
G 9.01

D 8.00

09.01

G 1.!35

output :
LIJP VS. V ( M O L E / M * M ) W 10 75-CALC.
FROM FREUNDLICH

TEMPERATURE:D SYSTEM: H C L G Z O Q SU,SFACE AREh:95.4 NUMBER OF DETERFIINATIONS: 6

: 1 .e5 :4.85
:9.08 :12 .c10

:1 5 . 6 5 :10.25

r45.77 :4 9 . 9 9 : 53.40 : 55.14 :56.44 :58.61

INTERCEPT~-9.1231 (53Ei-02 E R R O R - 0.5691F7E-32 E R R O R = 0.3R7512E-32 SLOPE= 0.1832 12 E + 3 m E R R O R IN INTERCEPT INCORRECT

137
PJUOIBER O F POI NTS: 2 0

I NCREMENT FlOLE/iNrM: 5 .OE-7 I N I T I A L MOLE/PW M: 5 .BE -7


L I I P = - O .2 I 2 4 1 6E+82 L N P = - B 14525RE+flZ LNP =-4. I 0 5 9 74.E+R2 LNP=-3.7810fl5E+al LNP= -3.5648m5E+O 1 LFlP Z-9 .3 88 1 57E+O 1 LNP=-3.23RRfl4E+Dl LNP=-9,1\39427E+O1 LNP= PI .4 6982 1 E-L: 1 L N P = 0.106774E+91 L N P = 8.1991 IRE+.F)I

L N P = B .283422?E+PI I
LPIP- 0.3 609 73E+O I LFJP= O.432775E+O1 L NP = 0.490 62@E+a 1 LNP= @ . 5 6 2 1 4 9 E + a l LNP= LNP= LNP= LNP=

B,62C?RF7E+L31 6.676266E+Bl 91.722652E+01

0.77834RE+gI

"

program t o Calculate Isosteric Heats of ~ "

Adsorption Using mundlich Parameters

W A C-3K MODV 1 1 -219


0 1 . 0 5 T ! ! I I " H E A T FROM FREUNDLICH"! 0 1 . 8 6 T " L N P VS l / T " I ! 01.07 A " NM*lPIE-5" N M , ! 0 1 . 1 5 A " NUMBER OF DETERMINATIONS" N , I ! .20 01 T " T LNP" ! ! 01 .25 S P=0; S Q=P,; S R=0; S S=8; S W = O 01.30 F 1 = 1 , N ; D 2.0cI 01.35 D 3.60 0 1 . 4 0 G 1.l35

02.05 02.07

A "

" X (1) ,"

" Y(I>,I

02.15
02.20 0 3 .1 p5 03.10 03.1 5 03.20 03.26 03.27 03.30 03.35 03.4El 06.G15 06.10 06.15 06.20 06.25 06.35 06.45

S X(J)=I/(X(I)+273) S P=P+X(I>; S Q=Q+Y(I) S R = R + X ( I ) * X ( I ) ; S S=S+X(I>*Y(I);

S W=W+Y(I>*Y(I>

S NS=( fJ*S-P*Q) S D=N*R-P*P


S NI;,*Q-P*S S SL=NS/D; S IN=NI/D D O 6.00 S HT=SL*l .9FJ7/10pI0; S H E = D M * l .987/10BW

ERR OR"HE, ! I T " H EAT KCAL/MOLE"HT," T " SL0PE"SL ," ERR OR" D M, I T " E R R O R I N Y"DY, ! I
S RS=SL* ( N S / N ) S TS=W-(Q*Q) / N S SS=TS.-RS S SQ=SS/(N4?!) S I)M=FSQT (SQ/(D / N ) 1
S DY=FSQT(SO) S CB=FSQT((SQ*R> /Dl

APPENDIX

A t l e g t A g n Data for Watervapor Adsorption on Gm a Alumina am

Outgas Temperature: 8OoC Adsorption Temperature : 3OoC

R l U 1

0.70

3.55 6.40 9.35 14.25


Run2

118.99 140.31 161.63

9.9 79

61. a9

1.20

5.05 9 045 15.05


Outgas Temperatures 8OoC Adsorption Temperature : 4OoC
pEXP (torr)

62 ;84 110.84 140.69 167.30

Rn u1

2.30 5.50 9.15


15.20

Run2

1.35 3.30 6.90


11.10

16.60

139

140

Outgas Teapestu=:

8OoC

Adsorption Temperature I 50C

Itorr)
R 1 W l

pEXP

1.10

1.95 2.30 5.25 7 995 10.85 14.95 16.50


1.10

34.98 42.81 49.93 65.47 71.46 80.38 91.60 99.47


44.40

3.20 7.00
11.20

63.71 79 59 91.81
1 05 0.6

15s 30 17 -65
Outgas Temperature I 2OO0C Adsorption Temperature I 40C

1N.70

*ED (torr)
Rn u1
1.10

N~

x 105

mole/g )

3.55 5.95
FmI2
2.20

63.71 86 .41 104.80 70.76 91 67


9

5.05 8.40 13.35 16.45 1975 4.90 8.50 11.60 16.05

1 1 G . 82

126.54 134.76 65.39 90.16 107.46


122.25

133.48

141

Run4

66.69
107.29 126.96 141.07

84.84

Outgas Temperature I bOOC Adsorption Temperature I 2 7 O C


pEXP

0
Run1
035

2.10 6.15 10.80 16.70


O t a Temperature, @OoC ug s Adsorption Temperature : 4OoC

79 15 121.95 163.01 194.21 222.89

Rn u1

Outgas Temperature I 4 0 0 C Adsorption Temperature I 5OoC

0
Rn u1

pExp

3.05

94.74
117.81 133.69 146.50

7 e70
11.70 16.85

APPENDIX 7

AdsorptionData for Water Vapor Adsorption onAlphaAlumina Outgas Temperature : 8OoC Adsorption Temperature : 27OC

Run 1

0.80 1.55 3.20

5.50
7.24 9.80 13.18 16.14 18.72

6.65
11.00 15.05
Outgas Tempemturn : 8OoC Adsorption Temperature : 40C
pExP

N~

105

(torr)
Run1 1.65

(mole/g)

5.49
7.02 8.70 10.18 11.42 12.67

3.55
5.90 8.65 11.40 17 35 2.15

5.73
6.87 8.64

3.65
6.20 8.55 '11.65 15.20 18.20

9.73
11.10 12.25 13.09

142

Outgas Temperature: 8OoC Adsorption Temperature x 50C

4.12 5.05 5.65 6.44


7.02

7.25 7.22
Run2

3.99 5.76 6.82 7.43 7.66


8.85

3.35

12.50 16.60
20.10

4.78 6.66 7.62 6-36 8.66

Outgas Temperature : 2OO0C

Adsorption TemperatureI 4OoC

N~ x 105
(torr)
Rn u1
(mole/R)

1.35 6.65 11.65 15.95 2.70 5-05 8.30 13.75 16.70

7.73 10.96 12.72 13.96 8.30


10.20

b n 2

11.88

14.02 14.94

Outgas Temperature : 4OO0C Adsorption Temperature : 3OoC

N~ x 105
(mole/g) 0.20

1.85 4.95
8.00 12.70 16.00

9.74 13.35 17 7.3


a

20.46 24.42

27.73

mtgas

Temperature : lioooc
:

AdsorptionTemperature

4OoC

N~
(torr)

x 105
9.30

Run 1

1.60
7.20 11.05

11.69

15.54
17.2i

15.80
Run2

0.45 3.60
7.30 12.45 19 80

8.84
13.21

15.99 1a,61
21.10

Outgas Temperature : 4OO0C AdsorptionTemperature I 5OoC

N~

105

torr)

lmole/g)

Rn u1

0.40

4.15
9.10
14.40

APPENDIX 8

AdsorptLon Data f o r H y h g e _ Chloride Adso ~. ... ~. ~ n _ _


~

tion

on Gamma Alumina

8OoC Outgas Temperature: AdsorptionTemperature I OC


'EXP (torr) Rn u1

1.05 3.00 5.35 9.20 13.20 16.80 18.50


8OoC
I

38.46 42.42 44.92 47.08


4.80

50.80
51 70

Outgas Temperature t

AdsorptionTemperature

40C
*EXP (torr)

N~

105 (rnole/p) 24.35 30.63 38.90


42.47

Rn u1

0.50 0.60

4.85
11.70
38.10

17.10
Run2
15 . 0

43.74 46.65 36 39 41 43 98 59 53 33 78

4.41 7.20
12.20

19 05 Run3 0.30 5.30 9.10


12.80

4. 4
w

16.50
23.30

31 03 37 85 39 57 41.25 46.46 45 95
rn
9

16 4

0.50 0.85 2.70 3.90 7.40 10.05 13.40 19.40


0.40

32.03 9.70

37.18

39.86 41.41 42.42 43.58

38.58

0.90 1.40 2.65 6.70 13.20 20.70


Outgas Temperature: 8OoC Adsorption Temperature : 5OoC

31.21 33.80 34.74 39.79 42.82 44.74 47.20

N~

105

torr)
Run1

imole/g)

4.25 6.00 10 95 15.80


20.70
0.10

37 -95 38.47
40.40

41.92 42.23

Run 2

4.95 9.70 16.90 20.95 Run3 0.65 2.60 5.75 12.65


18.50
y C * 25 35.49 36 85 39.25 40.68

Run4

0.85 1.50 6.80 11.35 17.55

31.46 33.20 35-75 37.78 39.31

147

Run5

0.80

1.90 4.05 9.15 13.35 18.85


1.25

3.25 8.35 14.20 19 50


Outgas Temperature : 20O0CO Adsorption Temperature I 0 C

N~
(torr)
Rn u1

x 105

(mole/g)

1.85 4.85 9.00


12.00

45.77 49.99 53.40 55 14

15.65 19.25
Run2

56.44
58.61 39.65 50.74 53.93 55.74 57.91

0.65 5.55 9.05 12.90 17.75

Outgas Temperature : 2OO0C Adsorption Temperature : 4OoC

1t o r r )
Rn u1
0.80

'X EP

4.25 8.15 12.95 19 50

35.75 39.69 41 97 42.78 U.65

148

Run2

0.95
4.20

9.95 15.90 20.70 Outgas Temperature t


2OO0C

Adsorption Temperature I

5OoC
(torr)

N~ x 105 (mole/g]

ml

1.80

4.75 9-70
13.10 18.20

35.52 37.67 39.60 41.47 43.07 37.92 40.27 41.70 43.28

Run 2

2.15 7.55 13.40 19.40

Outgas Tempemture : 400C Adsorption Temperature I OOC

1t o r r )
Run 1

'X EP

1-95 3.85
7-70

11.95 17. i o
Run2
1.10

44.68 46 .?5 47.04


48.77

41 57

4.55 7-30 13.60 19 35


9

41.87 45.49
48.20

50.06 51.35

OutgasTemperature c 400C Adsorption Temperature I 4OoC

'X EP (tom) Run 1

N~ x 105
(mole/g)

10.05 14.10 18.20 5.15 7.70 10.70 16.60 21.50 1.25 2.60 5.40 7.45 10.65 16.95 19 95 1.95 4.10 6.80 9-70 13.10 15.95 19.YO

41.30 42.08 42.73 40.83 42.35 W . 08


44.08
44.54,

Run 2

Run 3

38 59 39.24 39.63 40.74 41.13 41.14 41.08 36.67 37.95 38.80 38 .76 38.79 38.91
38.79

Run4

Outgas Temperature I 4OO0C Adsorption Temperature jOC

pEXP

N~ X 105
(mole/q)

tom)

Run 1

0.25
1.20

5.85 10.30 15.25 19.60

26.54 32.56 350 83 37.22 38.58 40.16

APPENDIX 9

m Data o p r i n t
Outgas

for-.&~dm@n Chloride Adsorption on Alpha Alumina


8OoC
OC

Temperature:

Adsorption Temperature :

pEXP
(torr)
Rn u1

N~

105

imole/txl

0.55 5.75 9.30 14.30 19.85 0.65 4.95 11.60 17.60 8OoC
N~
itom)

5.80 7.09 7.42 7.59 7.81 6.67 7.39 7.90


8.10

Run 2

Outgas Temperature :

Adsorption Temperature : 4OoC

x 105
4.89 5.98 6.44 6.69 6.87

imole/&

Rn u1

1.15 2.95 7.30 12.95 19.35 0.65 6.60 12.55 17.65 20.05

Run2

4.33 5.71 5.88 6.03 6.03

Outgas Temperatun I

Adsorption TemperatureI

8OoC g0C

torr)
Rn u1

N~ x 105 Jmole/g)

14 .5 2.70 7.8Q 11.60 16.50 19. 0 4 0.50 1.15


20 .0

4.28 53 .0 56 .6 5.74 5.85 6.20 2.95 35 .9 4.55 5.35 55 .7 5.72 57 .6

Run 2

58 .0

10.50 15a.35
2.0 14
Outgas Temperature I

20O0CO Adsorption Temperature; 0 C

'X EP itorr)
Run1

N~

x 105

0.75 34 .0 6.55
20

8.53 8.67 8.77


8.85
86 .4 8.83

55

Run2

1.30 4.20
11

8.20 55

15.80

19.50

9.04 9.27 9.35 9.33

" "

.. .... . . . .

.. .

..- . ..

..

" "

... . -

~~~

153

Outgas Temperature t 2OO0C Adsorption Temperature I 4OoC

(torr)
Run 1

2.25

5.50 8.60 13.10 18.45


Run 2

7.31 7.43 7.52 7.55 7.61 7.43 7.57 7.65 7-70

4.40

7.85 12.30 16.60


Outgas Temperature : 200C Adsorption Temperature : 5OoC

N~ (torr1
Run 1

105

(mole/g)

0.50 4.00

9.20 13.30
18.40
Run 2

6.36 7-07 7.33 7.48


7.53

0.65 4.90 10.50 16.90 18.60

6.67 7.21 7.37 7-49 7.57

Outgas Temperature I 400Co Adsorption Temperatures 0 C

N~
&!?Ed
Run1

x 105

irnole/g)

2.05 6.25 9.80

9.40 9. yt 9.70 9.93 10.03 8.98 9.05 9.25 9.38 9.49

Run2

1.10

3.55 7.15
11.80

17 55
Outgas Temperature I

4OO0C
40C

Adsorption TemperaturnI

(torr) Run 1

N~ x 105 Jmole/g)

2.30 6.75 12.55 21.05 0.15 1.65 3.80 11.60 18.75 0.15 0.90 3.55
14.00

7.73 7.96 8.09 8.41 5.60 6.85 7.11 7.47 7.65 6.67 7.23 7.60 7.95 8.04

Run 2

Run3

19.95

. ._

155

m 4

04 .0 29 .8 8.50 14.00 19-05

7.46 7.75
7.98 8.15 8.22

Outgas Temperaurea 40OoC Adsorption Temperature I W0C

'X EP

0
Run 1

Ns X 105 (molejg)

0.10 0.20 0.85 6.05 11.70 1.15 8.60 13.20 18.05

45 .7
5.62 6.85 7.62 7.87

Run2

7.45
7.81

7.93
8.04

I It

APPENDIX 10
"FOCAL" Program t o Flt Isosteric Heats of Adsorption
Surface Coverage t o a Quadratic Equation
VS.

(83)

07.65 I (1-9)7.18,7.15,7.18 07.18 S A(I+3* R ) = Q 07.15 R 0 7 . 2 0 F I = I , N P ; D 8.80 0 7 . 2 5 G 9.61


OR.@)

S AB=FLOG(CIM);

0R.BR 08.10

Nf'l"NP1," S NtQ=Nt'ttIC
''

S LMP=(AD-IN>/SL LNP" LNP, I

APPENDIX 1 1
.

CalculationPoofthe

Amount o f I i y ~ t x e n Chloride Adsorbed

on Alumina i n Exhaust Cloud


Exhaust

30.s A1203,

2 0 . H HQ,

9.4% HzO,

2. CO, 4s

3.W

C02, 2 s HZ, 8.7% N2 and 0.6% FeQ3 .

T&-Amount
Wc
=

Adsorbed f r o m t h e Exhaust
Ns X MW X Rev X WAl

is:

2 3 where:

Ns

= mole adsorbed/galumina

MW = moleculaz weight of HQ
Rev wA1203
= I

percent of H C l adsorbed t h a t is i r r e v e r s i b l e

= I

w of t .

Al 0 i n exhaustcloud
2 3

Assuming that a l t h e A l 0 i s g m a alumina and u s i n g t h e l a m 2 3 data f o r HQ adsorption a t OC on gamma alumina, outgassed a t MO0C which were t h e c o n d i t i o n s f o r m a x i m u m adsorption. For a lOOg cloud:

or

APPENDIX 12
Heats of Immersion of Aluminas i n !.later

and Hydrochloric A c i d

J . P . IJightman

Visiting Professor

Department o f PhysicalChemistry,llnivcrsity Enp,land. U r i s t o l BSC lTS,

of

firisto],

INTRODUCTION
Heats of immersionhavebeenwidelyrcDortedor
a number o f

systems ( 1 ) .

There have been

a number o f s u c h s t u d i e sr e p o r t e d
(2-6).

f o rt h ew a t e r / a l u n i n as y s t e m
of pre-treatment temperature

I np a r t i c u l a r ,t h ee f f e c t s
( 2 ) and

( ? , 3 , 6 ) , p a r t i c l es i z e

c r y s t a l l i n ep h a s e examined.
HC1

( 2 , 5 )o n

t h e h e a t o f imrucrsion h a w been

The enhanced c a t a l y t i c a c t i v i t y
(7-9).

O F alumina exposed

to

(SI

has noted been

In c o n j u n c t i o n i t he c e nitn f r a r e d w r
o r chemicalanalysis
(ESCA)

s p e c t r o s c o p i c ,e l e c t r o ns p e c t r o s c o p y and a d s o r p t i o n t u d i e s s heat of immersion d a t ar e p o r t e d


of

tic1

(7)

o n alrmina i n ollr l a b o r a t o r y , a i s n o h e a t o f immersion

study was a l s o bcoun. Thcrc

f o r thealuminn/llCl

(3s)

system*

EXPERIXNTAL

Calorimeter. The -~ h e a t s

o f immersion were deten<lined in


I I S ~

Calvet

microcalorimeter (10). There been has infreqllent


o f c a l o r i m e t e ri nh e a t

o f t l ~ i stvpe

o f immersion s t u d i e s ( 1 1 , 1 ? ) .

A hloclc d i a ~ r n m
.-. .. .. .

. .

From:

Department o f Chevistry, V i r e i n i nP o l y t e c l l n i cI n s t i t u t e a n d S t a t eU n i v e r s i t y , Blacksburg,VirSinla 2 4 0 6 1 , U . S . A .


160

161 o ft h ec a l o r i m e t e r
i s shown i nF i g u r e
1.

The Calvetmicrocalorimeter
Tlle

model MS 70 was manufactured by SETARAV (Lyons, France).. c a l o r i m e t c rh a s


a ncasurenenttllrc-shold(cbtectionlimit)
%

of

200 pJ an3 a s e n s i t i v i t y of

60 pV/nlk!.

O t h e r S E T A R M components

i n c l u d e dt h et e m p e r a t u r er e p l a t o r a m p l i f i e r ( ? model N V 724 and I) tlle


A 10 m V Graphispotrecorder

(D) motlcl 3OOOR, tlle DC nanovolt


I T C i n t e g r a t o r (G) withcounter.

( F ) was used t oo b t a i nt h et h e r m o p , r m

forvisualinspectiononly. The d e t e c t o r ( A ) c o n s i s t e d of n p i l e of: 1?4chromcl-almcl thermocouples. One detector surrounded mcasurinp, tlle (sample! c e l l
The p a i r

and a s e c o n dd e t e c t o rs u r r o u n d e dt h er e f e r e n c ec e l l . c o n s t i t u t e s one s a n p l es y s t e n l a b e l l e d "I" and "11".

Two s i m p l e syste-ns were

use.1 a n d a r e
in each

The measuring and r e f e r e n c ec e l l s

system were e l e c t r i c a l l y opposed s o t h a t any e f f e c t f l u c t u a t i o n i n t h et e m p e r a t u r eo ft h ec a l o r i m e t e r


was minimized. This arrangment resulted

on t h eo u t p u to ft h es a n p l cc e l l
11 .1

p.ood h a s e l i n e s t a b i l i t y
Tile

oververylong

times n e c e s s a r yi n

t h i s study.

output from t h e and i n t e g r a t e d .

sample c e l l was a m p l i f i e d and simllltaneouslyrecorded Materials.


A s t o c ks o l u t i o n O F 0 . 1 N \IC1
[JJS

prenared f r o n a s t a n d a r d

H C 1 s o l u t i o n (BDH Chemicals Ltd.

- CVY).

Solutions of specified by d i l u t i o n o f t h e
0.1 N

c o n c e n t r a t i o n s were prepared volumetrically s t o c ks o l u t i o n .

Alon-C was o b t a i n e d from Cnbot A X-ray n powder


of

Co. and u s e d wi.thout

f u r t h e rp r e t r e a t m e n t . l i n e sc h a r a c t e r i s t i c and 85.6 m p,
2 -1

d i f f r a c t i o np a t t e r ne x h i b i t e d
o f 95.4

y-A1 0

2 3'

Average I3ET s u r f a c e r e a s a
0

f o rs a m p l e so u t s a s s e da t

100-200 and 400 C, r e s p e c t i v e l y ,

were obtainedby

low t e n p c r a t u r e n i t r o g e n a d s o r p t i o n b a s e d
of 0.164 nm- (13). Reactivealumina
7

on a c r o s s -

s e c t i o n a l area o fn i t r o g e n

A16SC vas o b t a i n e d fromAlcnn

and u s e d w i t h o u t f u r t h e r p r e t r e a t m e n t .
of

An X-ray powder d i f f r a c t i o n n a t t e r n e x h i b i t e d l i n e s c h m a c t e r i s t i c

162
a-A1 0
2 3

An average EET s u r f a ca r eo f e a

8.14 m

2 -1

was obtained
100 t o 400 C (13)
(%

independent of outgassingtemperatureintherange Procedurp_. Samples of were weighed i n t op y r e x


)A1203

(W.05 g) and of a-A1 0 2 3


tips.

0.5 E)

ampoules with break-oEf


Shop.

The ampolllcs

werepreparedintheUniversityClass -5 evacuated t l0 orr or ad T f

The samples were then The


was

1 h r at he necified emperature. s t

ampouleswerethensealedoffinvacuo. alignedcarefullyinthe 2.5


c1n3

The sasnple ampoulc

sample h o l d e r of t h ec a l o r i m e t e r
NC1

and

o f e i t h e rd i s t i l l e dw a t e ro r

(aq>

v a s added t o a pyrex

i n s e r t in t h es t a i n l e s ss t e e lv e s s e l . possible reaction between a s s e m b l e dc e l l


steady llCl

The i n s e r tp r e v e n t e d and s t a i n l e ss t e e l . s The come t o by

(aq>

was p l a c e d i n t h e c a l o r i m e t e r

andallowedto

S t a t e typically 2 hrs. in

T h e amFou1e t i p was thenbroken

depressingtheplungerassembly

and t h e a r e a u n d e r t h e

thermogram

( p r o p o r t i o n a lt ot h ee n t h a l p yc h a n g e ) counter.Typical

was o b t a i n e d v i a t h e i n t c g r a t o r ill

thermograms a r c shown

7i::urcs

?a a n d 211 w i t h

and w i t h o u tP e l t i e rc o m p e n s a t i o n ,r e s p e c t i v e l y . condition was r e - e s t a b l i s h e da tt i m e sr a n g i n g The heat of empty bulb breakin? in both water determinedalso.

The s t e a d ys t . a t e from 50 t o 1 4 0 minutes. and 0 . 1 ?I l I C 1


(as)

was

Calibration.

The s e n s i t i v i t y , S , of t h e c a l o r i m e t e r

I J ~ Sdetermined

p e r i o d i c a l l y by p l a c i n g r e s i s t a n c e h e a t e r s i n t h e s a m p l e c e l l p o s i t i o no ft h e h e a t e r sa r e two systems.
I.

The measured r e s i s t a n c e ( R ) of t h e
11

Riven i nT a b l e

The s e n s i t i v i t y i s t h e r a t i o
t h e integratedcollnts

of t h e

measured e l e c t r i c a l i n p u t t o c a l c u l a t e d by t h e e q u a t i o n
c

(C) and was

s = - SI?2 RH
RSR
where E

r.

t/C

SR

i s the otential p

in v o l t s c r o s s a

a 10

standardesistor r

I163
w h i l ec u r r e n t
i s p a s s e dt h r o q ht h er e s i s t a n c eh e a t e rf o r
a r e g i v e ni nT a b l e
t seconds.

Values of S d e t e r m i n e d f o r b o t h s y s t e m

I.

Heats of immersionwereobtainedwithandwithout

Peltier

cornpensation. Since the

f i r s t 1 4 rrms were marlc. r s i n r ,P e l t i e r

compensation, tlle c a l c u l a t i o n of t h e e r f c c t i v r P e l t i e r c o c f f i c i c n t , P e f f , i s described. In P e l t i e r colnpcnsntion, t h ee x o t h e r n i cw e t t i n y .


smple cell (viathePeltier

process i s compensated by cooliny,the e f f e c t )t h u s making t h ec a l o r i m e t e r

more n e a r l yi s o t h e r m a l . P
efi"

Two

i n d e p e n d e n tc i r c u i t s

were u s e d t o d e t e r n i n e
(PC).

nmelv, a Joule a

c i r c u i t ( J C ) and a P e l t i e r c i r c u i t

The i d e a i s t oa c h i e v e
i s i ne x c e s s

s t e a d y s t a t e i n which theJoulehentiny: cooling.The value


of P

of t h e P e l t i e r

eff
RHt

was c a l c u l a t e d I I V

the equation,

- sc

%E

s t a n d a r dr e s i s t o r so f

1 9 were used

i nb o t hc i r c u i t s .

Wlen steady

s t a t e hasbeenestablished,the

number o f corlnts ( C ) over t jmc ( t )


w i t h 3 ma flowin,? i n the P c l t i e r

is

noted.

Values of Peff determined

c i r c u i ta r eg i v e ni n

T a b l e I f o rb o t hs v s t c m s .

There a r e a number o f r e f e r e n c e s t o i n e a t s e t e r m i n e dnh e a l v em i c r o c a l o r i m e t e r h d it C t


used P e l t i e r c o o l i n g i n t h e h e a t s

use of Pelti-ercompensation

12)

Thorne

of immersion of Craphon i n o r g a n i c

liquids('*).

On t h eo t h e r

hand, t h e r e i s n od i s c r l s s i o na st o

what

d i f f e r e n c e i t makes i n t h e measuredheatwhether
u s e d o rn o t .

P e l t i e r cooling i s

The o p e r a t i o n o t h ec a l o r i n e t e r
A s e r i e s of
o-

i s o b v i o u s l ys i m p l i f i e d

i f P e l t i c r cool.ing i s not used.


t o assess whethertheaccur:~ry

experiments were done

t h e measrlretl h e a t i s inproved b y

theuse

of P e l t i e r c o o l i n g .

The experimenthere

i s t o u s et h eJ o u l eh e a t e ra n di n t r o d u c e

... . .

164
a measured quantity
2 of h e a t (I R t )i n t ot h es y s t e m .

The h e a ti n p u t

can a l s o becheckedbyusingtheintegratorandthedetermined sensitivity. The r e s u l t sa r e shown i n a h l e T


11.

The agreement

betweentheheatcalculatedinboth

ways i s > 9 9 % , f o rb o t hs y s t e m s .
same

Now i n a s e p a r a t ee x p e r i m e n t ,n e a r l yt h e i n p u ti n t ot h es y s t e m .

q u a n t i t y of heat i s
i s used

B u t . i nt h i sc a s e ,P e l t i e rc o o l i n c

t o compensate f o r > 80Z of t h eh e a ti n p u t .

S o t h e compensated heat

tj

canbecalculated

from t h ee q u a t i o n

where P

eff

i s t h e e t e r m i n e d e l t i ec o e f f i c i e n t , d P r

i s the
oE r e s i s t a n c e R
SR

measured p o t e n t i a l a c r o s s t h e s t a n d a r d r e s i s t o r i nt h eP e l t i e rc i r c u i td u r i n g

a time, t , o f P e l t i e rc o o l i n p , .

The

the non-compensated h e a t , LI H i s simply product NC counts and


(A,It>
tlle d e t e n i n c ds e n s i t i v i t y .

of t h ei n t e g r a t e d t h e compensated

The

s t u : ~o f

and non-compensated (ArJcII)

heatsshould

e q u a l t h e heat :qgllt.

The r e s u l t s a r e shown i n T a b l e 11. gained by u s i n g P e l t i e r c o o l i n g . The conclusionrcachedhere

N improvement i na c c u r a c y o

is

i s t h a tt h e

u s e o fP e l t i e rc o o l i n r ,
(%?.l) obtained

d o e s notincreasetheaccuracyofthemeasuredheat

d i r c c t l y from t h es e n s i t i v i t y .T h i ss i m p l i f i e st h eo p e r a t i o no f t h ec a l o r i m e t e rc o n s i d e r a b l yi nt h ef o l l o w i n g
1.
2.

ways:

t h eP e l t i e rc o e f f i c i e n td o e sn o t

have t o be determined; drlriny. a run

measurements of p a r a m e t e r si nt h eP e l t i e rc i r c u i t
are eliminated;

3.

concern bout tability a s cumulative rrorsnhe eat e it h A H arereduced.


C

of t h e P e l t i e r c i r c u i t i s rcmoved; and

4.

of inunersion c a l c u l a t i o n i a v

DataReduction.

The ca1oriml:tric d a t a a r e c o l l e c t e d i n

Appendix .4 i n

I
165 c h r o n o l o g i c a lo r d e r . i nt h e
f i r s t column.

The run number and thesystem The operating temperattire

u s e d a r eg i v e n

of t h ec a l o r i m e t e r

is

denoted by "T".
(Essn)

The p o t e n t i a l( i n

mV) a c r o s s a 1 0 s t a n d a r dr e s i s t o r
i s passedFor

i nt h eP e l t i e rc i r c u i ti s

mcasurcdwhilecurrent

t seconds.Thesedataarenecessary

For P e l t i e r compensation which The n e t number of counts, C


timc, t
ss

was not used a f t e r u n r

?lo.

73.

net'

we re

r e c o r d e da ts t e a d ys t a t ea f t e r

.
A

Thc l a s t column i s t h e
ss'

d e v i a t i o n from b a s e i n e t t e a d y t a t e , l as s The c a l o r i m e t r i cr e s u l t sa r ec o l l e c t e di n sampleweight respectively.

expressedn i Appendix B .

m.

The prey

i n a i r and theoutgassin;:tcn~pcratureare The molar concentration


C

I J and T
HC1'

of i l C l

(aq)

is C

The

compensated h e a t , A H ( i nJ o u l e s ) The non-compensated h e a t , A


A
lI
S.C

was calculatedusingcquntion

[3]

NC

H was c a l c u l a t e d b y theequation

NC

net
s y s t e m s wc1-c g i v f \ l l i n Tnhle I.

I 41
The h e a t s or

Thc values O F S orboth

wcttinp,wcrccnlculatcd and u n i t a r e a b a s i s

by cquntions

[SI

and [ h ] on both u n i t weight

151
A H + A
H

(mJm

-2

. )

- A !J 1 1

.I:'

NC

where 1 i s t h e s p e c i f i c s u r f a c e a r e a . The weight l o s s on outgassin2 & A 1 2 0 3 f o r 1 h r up t o 40O0C a t

6 10-5 T o r r was measured


notcorrected systems)heat

as

1.22.

Hence, t h e e a t s f h o

immersion were

for weiglltloss

on outgassing.

The average(orboth and

of evacuatedbulbbreakingdeterminedinwater
J and 0.062

0 . 1 N H C 1 was 0.035 20.035

20.024 J , respectively.These

v a l u e sr e p r e s e n t

3 . 0 % and 3.9:: i nt h ew o r s tc a s e s

(No.26,

No.

l Q 8 )f o r

a-A1203 and y-A1203,

r e s p c c t i v e l y .T h e r e f o r e ,t h e

heats of immersion

166
werenotcorrectedforheatsofbulbbreaking. ErrorAnalysis. The equation f o r c a l c u l a t i n gt h es e n s i t i v i t y ,
[l] )
S,

was given above (see equation

.
[I]

T y p i c a lv a l a e so ft h ep a r a m e t e r si ne q u a t i o n Value Parameter 15.033 m V


994.7 R 480 sec 4 8 2 counts
10

a r eg i v e n
?E r r o r :

below

A fi).00?

ESR
RJll
t

-+O.O13Z
i0 .O 307
2 0 .O42Z

f0.3
k0.7
22

frt.3072

RSR

n
of S i n v o l v e so n l ym u l t i p l i c a t i o n

S i n c et h ec a l c u l a t i o n d i v i s i o nt h ep e r c e n te r r o r parameters e r r o r s ' of the


+ 0.30'7Z)

and

in S i s given by a
(0.0132
+ 0.013%

sum o f

tllepercent

+ 0.030:
S

+ 0.041
and t h e J o u l e s cc:':lt
-1

or0.3067.

Thus t h ec a l c u l a t e dv a l u eo f would be
2 . 2 5 6 x 10"(+0.007)

e x p e c t e de r r o rl i m i t s The average value errorrange.

-3 of S was 2 . 2 5 8 x 10 which i s withintheexpected

The e q u a t i o n f o r c a l c u l a t i n g t h e h e a t givenabove(seeequation Typicalvalues run No. 81. Value Parameter


S
C

O F immersion ( A H) was
W

[5]). [ 5 ] aregiven

of t h ep a r a m e t e r si ne q u a t i o n

below o r

-3 -1 2 . 2 5 8 x 1 J count f0.007 0 1886 counts


0.5894 g
+25
f O .0003

0.31%

1.333
0.05x

IJ

Again t h e p e r c e n t e r r o r i n

A ]!.is given by t h e sum O F theparameters


11

(0.31% + 1..322 + 0.05%) o r 1.682.

Thus the calctllatedvalue

of

167

A H and t h ee x p e c t e de r r o r w

limits wot~lcl be 7.23 20.12

J 8

-1

The larxest s o u r c e of e r r o r i s t h eu n c e r t n i n t y
of countswhichinturndepends

in thenunher

upon t h e c r i t e r i a selectell f o r

reaching steady

state.

Tllac i s , a t what p o i n t i s t h e themlogram


As

tobeconsideredcomplete? an asymptoticapproach

can be seen fro21 FiCurc 2 , t h e r e i s The i m e r s i o n oE Craphon

t os t e a d ys t a t e .

a g r a p h i t i z e dc a r b o nb l a c k ,i n
a well defined steady

a v a r i e t y o o r a a n i cl i q u i d sr e a c h e s

s t a t e i n %50 minutes

(14)

The r a t i o n a l e o r f

thelongerand

less w e l l definedsteady

s t a t e i nt h ea l u m i n a

systems are due t o diusion,re-hydroxylation and chemicalprocesses a b s e n ti nt h e chosen when Graphon system. In
tile

most c a s e s , ste.?tly s t a t e was over a 10 min p e r i o d ,

c o u n tr a t e

was < 2 counts Inin-'

which correspondsto Appendix A).

a 1.5 nun d e f l e c t i o n

from the b a s e l i n e ( s e e
i s seen i n 'rd)lc 1 1 1 .

The e f f e c to ft h ei l l - c ! e f i n e ds t c a ( l vs t a t e

the heats of immersion c a l c u l a t e da td i f v e r c n tt i m e si n

The t i m ef i g u r e si np a r e n t : l c s i s
state.

were a ~ - i ~ i : - , ' . ~ t sclcctccl a s s t e a d y -ily


tllis

The low

count r a t es t l g g e s t st h a t

i s a valid assumption.

Note t h a t a s i g n i f i c a n tp e r c e n te r r o rc a n thethemogramtoosoon.
A

be

obtained t)v t e r m i n a t i n g

secondsource

o f e r r o r i s t h eh e a t

of bulbbreaking

whicll

although i t i s s m a l l , i t i s non-reproducil)lc. and h e n c ep a r t i c u l a r l y i nt h o s ec a s e s deviation.


RESULTS o f smaller h c n t s ofimmersionwouldbeexpected

t o cause

a-A1s3

The h e a t s of immersion o f a - h l 0 i n a t e r t w a 2 3

30

as.3

functionofoutgassingtemperaturearegiven Figure 3. The h e a t s o immersion i nT a b l e

i n Table I V and shown i n


I V areaveragevalues

of

t h eh e a t sg i v e ni n

Appendix R and a r e expressed on both a u n i t weight


The Ile:,t measured i s independent tlle of
sample

and u n i t area b a s i s .

168
weight 3s shown on comparison of run Nos .S9 and101. There i s a marked i n c r e a s e i n t h e h e a t s
of immersion of CY-A1 0

2 3

i n water as t h e outgassingtemperature
4000C.

i s increased from 100 t o i nt h es u r f a c ea r e a

There i s no measured decrease over temperature this range

OF
the i n c r e a s e

a-Al 0
1

2 3

( 3 y1 3 ) .T h e r e f o r e

i nt h eh e a t

of immersion p e ru n i ta r e a

i s a t t r i b u t e dt o " r c - h y d r a t i o n "
oE w a t e r a s t h e

of t h es u r f a c ef o l l o w i n g

removal o f s u c c e s s i v el a y e r s
i s i n c r e a s e dr a t h e rt h a r !t o
0
1.J

outgassingtemperature s u r f a c ea r e a .
of

a d e c r e a s ei nt h e

l'lle value of A 11 a f t e r 100


i n t h el i t e r a t u r e

outgassing i s i n t h e rnngc

valuesreported

o f 370-656 m.J rn-2(7'B'6).


0

However, t h ev a l u e thereportedrange

oE 1467 mJ m-? a r t c r 400

outc,assin;: i s o u t s i d e The l a r g e rh e a t
in t h e
of

oE 503-1076 rn.J rn - 2 ( 2 9 3 ' 6 ) .

present work may be due water with

t os e v e r a lf a c t o r si n c l u d i n qi n t e r a c t i o n

a surfacecoating.
a-A1 0 ( o u t g a s s e da t 2 3
tlldL

an The measured pH of
2

100 C ) s l u r r y

( l g / 5 c c H 0 - anequivalentloadingto s t u d i e s ) was 9.93 a f t e r 10 min asnoted before n-A1 0 a d d i t i o n was 5.70. 2 3 The k i n e t i c s of thewettingprocess o ft h ei n d i v i d u a l thermograms.

u s e d i n t h ec a l o r i m e t r i c

i n Table V .

The i n i t i a l pIl

were obtained from :in a n a l y s i s

A l t h o u ~ l lnot a p a r t of t h eo r i g i n a l were a bonus s i n c es u c h' s t u d i e sa r c which a r c usually

p r o p o s a l ,t h e s ek i n e t i cs t u d i e s notpossiblewith

more c o n v c n t i o n n lc n l o r i n e t e r s For longtime

s t i r r e d andnotdesigned

s t a b i l i t y and k i n e t i c p r o c e s s e s
steady s t a t e a f t e r

a r e masked.

The average time required reach to

imnersion i n water o f a-Al 0 o u t g a s s e da td i f f e r e n tt e m p e r a t u r e sa r e 2 3 giveninTable


VI.

There i s a s l i z h t ternpcrnL:ure dependence on t h e

s t e a d ys t a t et i m e ,t h eh i g h e ro u t g a s s i n gt e m p e r a t u r e sr e q u i r i n gt h e 1on.ger times. The h e a t s of immersion


L.f

a-AL 0

2 3

in0.1

i.l I l C l a s a function of

169
outp,assingtemperature S t r i c t l ys p e a k i n gt h e i m e r s i o ns h o u l d
be

are g i v e n i n

T:lble V T T and shown i n F i g u r e 3 .


of

term Ileat o f i n t e r a c t i o n r a t h e r t h a n h e a t
IISE~

in t h i s c a s e s i n c e

t!lerc i s p a r t i a l

d i s s o l u t i o n of n " A 1 0 i n 0 . 1 N H C 1 ( I 3 ) . The hcat oE iinvcrsion .of ? 3 ~ h 0 l i n 0.1 X l l C l a l s o i n c r e a s e sw i t h


2 3
ah i n c r e a s ei n

out;:assin?

t e n l p e r a t u r e .F u r t h e r ,t h eh e a t i n 0.1 1.J H C 1 t h a ni nw a t e r i n c r e a s e dh e a t temperature.


l l e n t oE

of immersion i s s i g n i f i c a n t l yh i $ c r a t any p,iven


40r) rnJ in

outgassingtemperature.
-2

The

amounts t oa b o u t

inulcpcndent of o u t g a s s i n g
T11e

TheYc i s no comparable l i t e r a t u r e l a t a v a i . l a b l c . , a
b c r e l a t e dt ot h eh e n t

i.ntcrnctionshould

of a d s o r p t i o n a s

tlccluced from l i C 1
T;

(s)

adsorption dat;l

(13)

easurcd pH o f an c i - A l , O s l u r r y ( l g / 5 c c 0 . 1 ! HC1) was 1.59 I - 3

a f t e r 1 Inin (Table V ) . 0

The i n i t i a l pll b e l o r c Cx-'Il 0

2 3

additi0n.wa.s

1.43.

The k i ~ e t i c r e s u l t sin:-TaSlc V I aeninsuggcst dependence on

a slightte:npernturc

s t e a d ys t a t et i m e ,t h eh i ~ h c ro u t E a s s i n gt e n p e r n t u r e Yote t h a t 652 15 n i na r er e q u i r e dt o immersion 01 a-A1 0


7 3

r e q u i r i n gt h el o n e e rt i m e . reachsteadystateafter

in

both water

and 0 . 1 N i l C 1 .

T h e eEfcct o f H C 1 c o n c e n t r a t i o n on t h eh e a t
u-A1203 o u t z a s s e da t

of i n t e r a c t i o n of

200 C i s shown i nT a b l e

VI11 and p l o t t e d i n

Figure 4 .

The h e a t i s f a i r l yc o n s t a n t

from 0.1 E! t o 0 . 0 3 2 N followed .


0.001 N.

by a s h a r pd r o pt o

0.01 N and a g a i n a c o n s t a n tv a l u et o

The
of

value f o r t h e 0.001 N s o l u t i o n i s s t i l l considerablyabovetheheat immersion i c water,presumal~lyrelated f o r c e s of adsorptioncoupledwith


to t h e s t r o n g e l e c t r o s t a t i c The

any d i s s o l u t i o n whichoccurs. 4.
A

i n i t i a l H C 1 c o n c e n t r a t i o n s were p l o t t e d i n F i g u r e p l o t i s o b t a i n e d bycombining rncasurments Table (see

more i n s t r u c t i v e
pH
of

thecalorimetricdatawiththe Fi,q:ure 5.

V ) a s shown i n
I?)

Here t h eh e a t s
pi:

imnersion(leEt-handordinat

a r e plotted ap,ainst equilibrium

170

whilethechangein right-hand ordinate.

pll on a d d i t i o n of a-Al 9

2 3

i s p l o t t e di nt h e

E The s a l e b a s i c c a t u r e

i s s e e n ,t h a t

is, n

s h a r pd e c r e a s ei nt h eh c a t

of immersion i n tilt? p11 ran;:e

3-5 b u t

tlle constant heat of immersion f o r tlle 0.01 sn\l 0.001 N H C 1

s o l u t i o n s i s presumably dl16 o n i n t e r a c t i o n w i t h alumina.


y-A120j.

t ot h ed e p l e t i o n

o f 11

i o n si ns o l u t i o n

The h e a t s o f inmersion of y-P.l 0 . ia \ . ~ n t e r s a


2 3

; 1

function o f
3.

outgassingtemperature Again, as i nt h e

i s g i v e ni nT a b l e

I V and shovn i n F i r u r e

case of U - A 1 O the heat of irnaersion of -(-A1 0 2 3' 7 3


i s incrc3sed. lthorl~h A
0

increases the as outgassing temperature t h cs u r f a c ea r e ad e c r e a s e s t h el l t a ti n c r e a s e s

from 9 5 . 4 a t Inn C f o r C 5 . G n~'?:;-~

at 4 m 0
of

by a f a c t o r O F 2 .

,\gain, increased the lieat

inunersion i s a t t r i b u t e dt o
times l e s s y-A1 0

rernovnl oE adsorbed water. Although ten


C k A l 0 (Appendix B ) ,

2 3

was used than

2 3

t h ew e i z h t s

usedcorrespond

t o e q u i v a l c r l ts u r f a c ea r e a s .

Tlmt a s u r f a c e
!)y ijrltcr i s

pllenomena and n o t a bulkprocess

i s involve.; i n \!ctti.n:,

ofinmersion

of -(-A1

2 3

i s l e s s t h a nt h a tf o r

cl.-:l12f13 on a unit a r e a

b a s i s which a g r e e s w i t h t h e r e s u l t s w i t ht h er e s u l t s

of !.!or.i;rloto e t a l . ( 3 ) b u t n o t

of 1lt.nclrikse.n e t a l . ( 6 )

The reported v a l u e s o f
n1.T

A H f o r y-A1 0
\I

2 3

o u t g a s s e da t

100Orange froin '00 t o 4 7 0


m

n1-? anrl a t

400

range from GOO t o 762 m J

-2(2,3,G)

Tllc p r e s e n t r e s u l t s F a l l

withintlwreportedrange

i n bothcases.
T a b l e V) a r e p a r t i c u l a r l y

The ptl measurements(see

il1StrllCtiVe

171 obscrvcdrntk,erthan
a llccrense fro;n 5.272 t o 4..'tG

f o r .;-Al?03.,

'Chesc

a s was o b s e r v e d f o r a-A1 0

2 3'
0

The neasurctl pli of a y-.41 0 (out,qnsscc! ; ~ t109 C ) s 1 1 1 r r yi n 2 3

thc i n i t i a l p l i .

s i m i l a ri n v n r i n n t

p;l w1 o l ~ t n i n c df o r a-.41 0 ;s

3 3

ill

0.1 N I I C 1 .

The immersion i n w a t e r
SO l n i n

o f .j'-Al,O3

outr.,?sscc! a t 19Q C rcrluircd


mill

t or e - c s t a b l i s l l

s t c a d v s t n t c whrrc't:, 1?5

IIcrcrequi

reg?
.

f o r 0.1 N IIC1.

Tor botll CY-A1

? 3

ant1 - ; - A l ? l J 3

(O o l ' out!;..ls), nl)ntlC )

tllc same t i n c (s 5 0 min) was require<! t o r e n c h s t e a d y s t a t e water ut n b i lonyer than


0.1 N I-IC1 t h e t i m c ( 1 ? 5 min) with -{-AI.

wi t1l

? 3

wns

consit1cral)lv

thc time ( 5 5 min) Fnr cx-Al 0

? 3'

Tllc

IISC

o r tlle Calvet
the

microcalorinwter has nllowcrl t h eI ~ . i n e t i c s of ther:nnlprocessesin alumina/IICI system


(ad

t o h c prohcli n t a l e v en oh e r c t o E o r n o s s i h l c . l t c
S 1I
T 1ARY

D c f i n i t cd i f f e r e n c e si n y-A1203 i n b o t h w a t e r
"

the immersion process

OF

a-A1 9 and 3' 3

and aqueous i l C l s o l u t i o n werenoted.


n r r n ) o f a-A1 0

IJater - The h e a t o f w e t t i n y ( p c r u n i t g r e a t e rt h a nt h a tf o r y-Al,Og.

2 3

in water al~~~~inas

The h e a t of w e t t i n yf o rb o t h

i n c r e a s e w i t h incrensin: s t e a d y s t a t e on immersion

o ~ ~ t r a s tc
o f cc-A1

~ ~ ~ p c r a t ~ ~~rce . T l time t o reach


was l e s st h a nt h a tf o r

? 3

)I1 "2

? 3'

172
There was no markeddependence outgassing temperature increased whereas
". . 1 "0

of the t i m e t o r e a c h s t e a d y s t a t e
The plf of an a-A1 0 s l u r r v 2 3 .
-{-A1

on

f o r a-A1 n 2 3'

a decrease was noted f o r a

2 3

slurry.

N lICl

The h e a t of w e t t i n g o f a - A 1 0 i n 0.1 N 1IC1 was c r e a t e r 2 3

t h a nt h a t

f o r y-A1 0 2 3

The heat of vettiny: f o r h o t ha l w l i n a si n c r e a s e The heat o f immersion oE or-A1 The time t or e a c h


y-AI ? 3'
0

w i t h increasingoutgastemperature.

? 3

decreasedwithdecreasing steadystate

l l C l concentration.

on immersionof

a-A1 0

2 3

l e s st h a nt h a tf o r

Samples of a - A 1 0 outKassc(1 a t hi.gllertcxperaturestendedto 2 3 longer t o r e a c hs t e a d ys t a t e .


a-A1 0 was aboutthe 2 3

tnkc

The time t o r e a c l ls t e a d ys t a t ef o r and


. 1 N t1C1 whereas f o r

same i nb o t hw a t e r was rcquirctlin

y-A1203 a longertime

0 . 1 N I!C 1 compared t o w a t e r .

The pH of s l u r r i e s of b o t h cc-Al2o3 and y-A1 0 remained unchanr,ctl 2 3 compared t o t h e i n i t i a l


ptl o f 0.1 ! 11C1. J

'I'l~e al~ovcsuanlnry i s shown i n al)l)rcviatcal


AC:(I.II)I.II,ED(;'ll::STC;

I would l i k e t o

thank r r o f e s s o r T?.li. 17verett f o r t h eo p p o r t u n i t y


Che;nistrv Depnrtnlent a t tlle

t oc a r r yo u t

t h i s research i n tllePhysical

University o f f i r i s t o l .

The help o f P . . J . ' i a n n i n y i n Itecpint m e

on-strean i s appreciated.

?.!r. ? . E .

(Red G;1rrartl in Chcrlistry the

Department G l a s s Shop was r e s p o n s i h l cf o r g l a s s sample b u l b s .

t!lc n r e m r n t i o n of tlle

REFERENCES

1.

A.C.

Zcttlemoycrand

K . Knravnn,

i n "Thc Solid-GasInterfaccll
Vol.1,

1967) Ed. 1S.A. Flood (Xarcel nekker. New York,


2.
IJ.1i.

pp.145-175.

\J:ldc and N. Ilnckcnnan, .T.Pl~vs.Cl~cn.,

6 4 , 1136 (1960).
"

3.

T . Morimoto, K. Slliolni nntl 11.

Tnnnkn, U1111.Cl1em.Soc..Tapan,

37, 392 (1964).


"

4.

N . Hackerman and !J.11.


H . Cochrane and
E.A.

Vncle,

J.Pl~ys.Cl~em., 6 8_ 1592 ( 1 9 6 4 ) . - , h "_ l ,


2 2 4 6 (19G5).

5.
6.

R. Rucihnln, Trans.Farnday S O C . ,

Hendriksen, D . X .
82 (1972).

Pearce and R . R u t l h n m , J . C a t n l y s i s ,

?4-,

7.
8.
9.

J.E.

P e r i , .J.Phys.Chem.,

70, 1 4 8 2 ( 1 3 6 6 ) .
"

?l. Tanaka and S . O.;asnx.~nra,, .J.CaLalvsis,

16, ._ -

157 (1370).

S . Ogasawarn, PI. Talcap.arJa a n d R . T a k a h . l s h i ,J . C n t a l v s i s ,

??,

67 (1973).
10.
E . Calvet a n d

M.

P r n t , "Recent P r o 7 r e s si n' , c i c r o c ~ l o r i m c t r v " ,


(1Q63).
"309 (1967).

PcrrnnonPress
11.
I,.
P.

Robert, Ilull.Soc.Cl~irn., Frnncc

12.
13.

Thorne, P11.n. T h e s i s ,n r i s t o lI l n i v c r s i t y , Bailey, Ph.D. T h e s i s , V.P.I.


&

1974. 1976.

R.R.

S.U.,

14.

D.H. E v e r e t t and J . P . Vi~htnlnn. EI!CtII?! FranceApril, , 197h.

r n n r c r c n c e ,C o l l i o u r e ,

174
TAiI1.E I

CALTRRATION PARAMETERS

System

RH

I
I1

994.7 9 9 2 .O

175

TABLE I1

EFFECT OF PELTIER COMPENSATION

N (;

S x C
=

f
AHrneasd

s x c

176
TABLE I11

STEADY STATE C R I T E R I A

Run No. 73 TI

-A ti
w

53

324

1296

98.3

72
79

7AH
35 h

99.1 1 307
1710

93.3

K I I ~No. 1 7 6 I1

30
40

302

331

94.3
56.6
98.3

922
9!t 6

3 39 34 7
350

67 82

954

99.7
1130

(30)

956

351

. P re

( ' C >

529

* * *

2 5 ( 4 . 4 . 3) 0 7Z

f 0.20

0 7 0 f 55 ( 5 . 7 %8 8 7. )

f 0.47

1266
14E4

42 (3.35)
7 .(0.5%) 12.0

10.3

f 0.3 f 0.1

-A1 0

2 3

100 400

372 f 2 6 ( 7 . 0 7 )

35.6
70.8

+_

2.4
0.1

1126 f 1

(0.17)

Ci-Al

0 2 3
........

100

n
0.1
0

5.70 1.43 6.15 3.37 2.30


2.09

9.99

3.7?
-

? .4n

100 200
200

1.49 10.22 12.03 5.17 3.35


2.11

1.47 3.36 9.39 6.03

9.93 3.76 5.76

0.001
0.01

200
2 00
200
200
r .

0.016 0.032

2.33

4.14
2.62 1.32

1.74
1.25
-.
.

0.1
I

...

.... ...

1.33 - 1.36

100
100

4.72 1.41
~- . . .
. . . . .

4.63

4.46

5.82

0.1

1 . 41 . 3 61 . 4 2 2
__

179
TABLE VI

AVERACE TI?IES TO RE-ESTABLISH STIXDY STATE

..

..

a-A1 0
-.. .
"

2 3

a-Al 0
-.
..____

2 3

-{-A1 0 2 3

-. .- .

65
50

55 65
pn
70

125

55
70

60

120

180
TAI3T.E V I I

HEATS OF IMMERSION OF

O-Al

2 3

AND Y-A1203 I N

0.1 N HC1 AT 30'

P =e

(OC)

-A H(m.J m ')
W

-3

- A H(.T
I.1

T,

-1 )

80 100
200 300

888 349

7.23 7.73 17(1.2%)


11.0 f 0.1 14.1 14.3
? ?

1351

1732 2 35(2.22)
1529 f h 0 ( 3 . 3 % )

0.3
0.5

400

*{-AI

2 3
6 9 . 3 f 3.C
14 p.

100
400

727 f 4@(5.5%) 172E

181

TA1:l.E VI1 1

-7

-AwH(mJ m - )
0 .001

1134
1188
?

9.23
9.68 ? 9 . 4 2

0.01
0.016

50(4.27)

1222

3.95
10.2
10.S

0.032
0.05
0 1

132')

1333
1 3 5 1 i 17(1.2%)

11.0 ! 0.1

182
TABLE IX

SUMMARY OF RESIJLTS

183

"

1
A

.I -1L
L

1 ".

Microcalorimetric element (detector) Temperature regulator probe Temperature regulator heater Temperature regulator Amplifier Recorder Integrator Potentiometer Insulation

Figure 1.

Block diagram of Calvet microcalorimeter

184
t (min)

20

40

60

I
3

Figure 2b.

Typical thcrnograrn f o r i.nmersinn O F a-A1 0 i n 0.1 2 3 Pcltier compensation ( N o . E l ) .

)! .

H C 1 uithoilt

-.--.-._. -. "".

" -

U-AI

2 3

i n 0.1 M HCL w i t 1 1

Peltier compensation ( N 0 . 5 5 ) .

185

350

450

5 50

1040

f-"
5
2
cHc

>5 2

188

APPEM3IX A CALORItIETRIC DATA

ESR
(mv)

18 T

2.994 2.395
2.99s

117.3 179.7 179.7 195.7 125.3 119.3 120.3 2h0.7


(119.8

55

1.5 1.5 1.2 1.2


0.8
0.6

19 1 1
2 4 I1 25 I 2 8 I1 29 1
.

55
60

2 .907 2.994 2.993


2 .?94

65 50
50

35 I
48 I

55
20

0.9

2.996
? .399

1.7
1.7
1.2
-

149 1 1
5 4 TI

65

2 .?99 2.939 2.395 2.932


2.992

353.4
160. .o

nn

I;5 T
60 IT

cn70
70

2.7 (r01.2
3/15. ?

1 .?

72 T 7 3 I1
X1 T
$ 8 11
RC!

0.3

7 r)

6
60

1 .0
2.5

p.5 70
80

0.4
1, D

101 1

lQ6 T

0.6
-

1 0 7 I1 131 I
1 3 2 II

90

1.0
0.3

90

189

APPENDIX A (conti.nlJcd)

T
(OC)

ESR

t
(scc)

C"et

tSS

SS

(mv)

(counts)

(min)

(md

Y-A1*Q3
10s I

30.72

736
1008

90

109 I1

30.38
30.28
30.2Q

120
120

1.2

115 I 1
116 I
171 I 1 7 2 I1 1.73 I 175 1 176 t 1 177 I
17::

1978
14 10

30.38
30.50
30 .3')

I700
30 34

120
65
80
140

2 .o

31 00
784

3') .3 0

0.2

7n . x

954
1790
2082

0.3
1 .o

m.??
30.73

I1

120

190
APPENDIX B

CALORINETRIC RESULTS

w
(E)

T Pr=
(OC)

HC 1

ACH

ANCH
(J)

-A H
W

-A H
W

moles

-1

(J)

(Jg-

(IllJTIl-2)

a-A1203

18 I

0.6279 0.5244 0.4625 0.4608 0.4764 0.4735 0.4736 0.4906 0.4772 0.4590 0.4371. 0.5530 0.5907 0.5323 0.5894 0.4552 0.4733 0.1567 0.4904 0.4825 0.4864 0.4986

200 200 400 400


100 100

0 0

1.626 2.607 2.609 2.701 1.817 1.645


7. .486

3.026 1.772 2.951 3.132 0.333 0.298 1.219 4.213 0.774


1.111 1.310

7.41 8.35 12 .o 12.1 4.51 4.10 7.73 15.4 14.4


13.8

9 15 1026 1477 1490 554 504 349


1888
.

19 I1 24 I1 25 I 2 8 I1 29 I 35 I
4c I.

0
0

100

0.1
0.1

4 00 400
300

3.322 6.097 5.220 4.964 5.116 5.529 4.996

49 I1 5 4 I1
55 I
60 I1

0.1
0.1
0. 1
0.1

1769 1694 1769 1368 1224 1307 888 1334

300 200 300


300

14.4
11.1

1.042 0.357 0.667 4 .?59 4.943 4.385 1.581 5.320 4. h53 5.261 4.959

72 I 7 3 I1
81 I

0
0

9.96 10.6 7.23 10.9 9.26


10.1
10.8

80

0.1

88 I1

200 200 2 00 200 200


200

0.1

89 I
101 I

0.01
0.01 0 .os
0.001

1138
12 39

106 I 107 11 131 I 1 3 2 11

1333
1134 1329 1222

9.23 10.8 3.95

0.032 0.016

200

191
APPENDIX E (continued)

W
(R)

P =e

CRC 1

ACH
(J)

ANCH (J)

-A H w
(J.3

-A H
W

(OC)

-1 moles 9 ,

(TllJlIl-2)

~-A1203 108 I 1 0 9 I1 0.0457 0.0488 0.0493 0.0492


0 .OS42

100
100

1.662 1.931 3.790 3.184 3.839 3.897 7.000 1.770 1.827 4 .O42 3.989

36.4 39.6 76.9 64.7


70.8

38 1
4 15
806

115 I1
116 I 171 I 172 I1 173 I 175 I 1 7 6 I1 177 I 178 I1

100
100

0.1
0.1
0 0

678 827 826 1728 344 350 703 720

400 400 400


100

0.0551 0..0473 0.0539 O.nq47


0 .Oh03

70.7 148

0.1
0

.c)

32.8 33.4 67 .o f8.7

100
100

0.1
0.1

0.0581

100

I II

11 .1

I .

1. Repat No.

2. Government A c c a i o n No.

NASA CR-2929
4. Title and Subtitle

Interaction of Hydrogen Chloride w i t h Alumina

7. Author(s)

R. R. Baileyand

James P. Wightman

9. Performing Organization Name and Address

Chemistry Department VirginiaPolytechnicInstitute Blacksburg, Virginia 24061


12. Sponsoring Agency Name and Address

&

StateUniversity
"~.

-.

- - N a t i o n a l . A B ~ o n a u t i c& Space Administration s Washington, DC


15. Supplementary Notes

20546

1
~

3. Recipient's C a t a l o g

No.

5. R e m r t P8te

February 1978

6. PerformingOrganization Coda
8. PerformingOrganlzation Report NO.

10. Work UnitNo.

11. ContractorGrantNo.

NSG-1195 Contractor Report

13. Type of Report and Period Covered

14. Sponsoring Agency Code

Langley Technical Monitor: Gerald

L. P e l l e t t
."

Final Report
16. Abstract

The i n f l u e n c e oftemperature,pressure, and outgasconditions on t h e a b s o r p t i o n of hydrogen c h l o r i d e and water vapor on both alpha and gamma alumina has been s t u d i e d . C h a r a c t e r i z a t i o n of the adsorbents was performed using x-ray powder d i f f r a c t i o n , s c a n n i n g e l e c t r o n microscopy (SEMI, low-temperaturenitrogenadsorption-desorption measurements, BET n i t r o g e n s u r f a c e a r e a measurementsand e l e c t r o n s p e c t r o s c o p y f o r chemical analysis (ESCA). a t 30, 4 0 , and 5 O o C weremeasured on alpha and gamma Water vapor adsorption isotherms alumina a f t e ro u t g a s s i n g a t 8 0 , 200, and 400OC. Both outgastemperature and adsorption temperatureinfluencedtheadsorptionofwatervapor on thealuminas. The watervapor adsorption w a s completelyreversible. Alpha aluminaabsorbed more w a t e r p e r u n i t a r e a of t h e than gamma alumina.Differencesintheadsorptioncapacityforwatervapor two aluminas was explained on t h e b a s i s of i d e a l s u r f a c e models. of alpha and gamma alumina. I s o s t e r i c h e a t s of adsorptionforwatervapor on thealuminas were determined over a limited range of surface coverage. a t 0 , 40, and 5 O o C were measured on t h e two Hydrogen chloride adsorption isotherms aluminas a f t e r o u t g a s s i n g a t 8 0 , 200, and 400OC. Alpha aluminaadsorbed more hydrogen c h l o r i d ep e ru n i ta r e at h a n gamma alumina.Again, i d e a l a l p h a and gamma aluminasurfacc models e x p l a i n e d t h e d i f f e r e n c e i n a d s o r p t i o n f o r hydrogen c h l o r i d e and d e s c r i b e d t h e n a t u r eo ft h ea b s o r p t i o ns i t e . The absorption w a s o n l y p a r t i a l l y r e v e r s i b l e i n d i c a t i v e of a chemisorption process. I s o s t e r i c h e a t s ofadsorptionfor hydrogen c h l o r i d e on the aluminas were determined for a rangeofsurfacecoverages. These i s o s t e r i c h e a t s of a d s o r p t i o n were compared with c a l o r i m e t r i c h e a t s of adsorption using a water l a y e r model which d e s c r i b e d t h e mechanisn The f i r s t s t e p i n v o l v e s a soluof hydrogen c h l o r i d ea d s o r p t i o n as a two-stepprocess. t i n n of t h e hydrogen c h l o r i d e i n p r e a d s o r b e d water and t h e second i s t h e a d s o r p t i o n on t h e a l u m i n a . surf ace. 1 7 . Key Words (Suggested by A u t h o r ( s ) ) 18. D i s t r i b u t i o n t a t e m e n t S Adsorption,Chemisorption, Hydrogen Chloride, Unclassified - Unlimited Water, Gamma A l u m i n a , Alpha Alumina, Heat ( I s o s t e r i c ) of Adsorption,Surface Star Category 25 R S C a , sm 21. NO. of pages 22. Rice' 20. Security Classif. iof this pagel 19. Security arrrif.iof this report1 Unclassified
*

Unclassified

199
Vlrglnla 22161

$9.00
NASA-Langley,

For sale by the National Technical information Service. Springfleld.

1978