Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
NASA
R. R. Bailey and James P. Wightman VirginiaPolytechnic Institute & State University Blacksburg, Virginia
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
vi
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
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.
22
30
on Gamma A l u m i n a . . . . , . . . . . . , . . . . . . . . . . . . .
42
9.
10.
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
51
52
53
54
5000X
55
57
viii
Page
19
20. 21.
Gm a Alumina am
... 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
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
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
. . . . . . .. . . . . . . . . . . . . . . . .
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
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
. . . . . . . . . . . . . . . . .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
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.'
s d .2 oa
and t h e
release hydrogen c h l o r i d e i n t o t h e
a greater environmental concern
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
as a
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 .
i s of two c r y s t a l l i n e
and t h e smaller par-
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
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
at the interface
bulk.
is caused by f o r c e s of
of attraction
adsorption.Adsorption
is usuallyclassified
as e i t h e r p h y s i c a l o r
If
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
solid ( a d s o r b e n t ) a n d t h e
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 ,
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
A studyofthe
fate a n d i n t e r a c t i o n o f
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
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
to
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
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
onad.sorption.Standardreferenceson
13
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
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
are available.l6Typicalexhaustcomposition
24.S
is 3 0 . 8
C , 3.4% CO2' O
2.5% H2,
8.?$ N2 and
3'
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
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
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
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-
and by Werfers
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
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
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
( a ) form.
C02
The
temperature
thetemperatureofthecalcination,but
6
only a s l i g h t dependence on the
Sedzimer concluded
t h e number of micm-
rate o f t h e
slow adsorp-
a t gamma aluminabecause
surface.
Hair25reviews t h e adsorptionandsurface
1967.
sites ony-alumina
for
severaldifferentreactions,includingortho-parahydmgenconversion,
Hz
- D2 exchange,
dehydration. Using
exchangeandolefinisomer-
four types
sites f o r e t h y l e n e a d s o r p t i o n ,
HzS,a928
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.
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.
at
after outgassing
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
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
at
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
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
Dry aluminacould"chemisorb"
22 o f
is l a s e d on t h e p r e f e m d exposure
an area o f 8
22
as shown i n figure 1.
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
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
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
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
Loss.of weight
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 -
ofphysisorbed
amount of chemisorbed
water foundon
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
x 2 on the alumina
Si02,
Al 0 and Si02-A1203 s u r f a c e s .S i l i c a ,
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
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
12
be 16.6f2.
Theamount
ofchemisorbed
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
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.44 l
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
M e , SingandStryker.46Studyingalumina,
oxide, these workers determined
a t 8 O O 0 C ) , only
Figure 3.
Surface
Figure 4.
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
do e x h i b i t
by dehydmxylated silica.
showed t h e
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
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
A l a t e r paper by
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,
temperature on
immersion.The
16
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
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.
seemed t o
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
CH OH adsorotion.
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
i n water.
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
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
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-
on thermal pretreatments and the temperature new hydroxyl p u p s , hydrogen bond i o n s on the alumina surface.
Water canform
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 ,
of H C l adsorption on N a B and K
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
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
of H C l on silica-alumina and
that H C l
2
o f CO
on a-sites
H stated t h a t H C l , NH e
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
a-site was
These
2-
Al+ andonsilica-alumina;
s i t e s chemisorb HQ
of the
a t 8OO0C, P e r i f o u n d t h a t
H C l adsorp-
5OoC gaveanabsorption
groups.
result f r o m
Desorptionof
Using a d e u t e r a t e d
Ti 0 ,
4t
/*
H
Figure 5.
20
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
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
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 -
a m a x i m u m a d s o r p t i o n of 3 x 10
14
a d s o r p t i o n are
as Bronsted acid
the silicasurface
sites.
were c a r r i e d
showed
T h e s es t u d i e s
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
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
to
and 400C
of t h eh e a to f
concentration
at 2OO0C with HQ
- 1 4 mJ/m2 13
f o r 0.001 M I f C l and
-1351
of t h e HC1-A1 0
the system
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
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
v e r s i b l y t o formhydroxyl
wups.
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
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)
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
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.)
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
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.
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.
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
24
peaks i n t h e Q 2p region.
dependon
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
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
ESCA bindingenergymeasurements
are p r e s e n t e d i n T a b l e
I.
The data
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
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
Half Mx a (ev)
2.25
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)
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:
Matheson Company.
(9%) o b t a i n e d
water
vacuum
whichhadbeen
system.
2. Adsorbents: Two aluminas were used as adsorbents. The gamma
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
Alon-C using Cu K
radiationconfirmedthat
Aluminum
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
a particle size
B.
Characterization Techniques
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.
tothesurface
area measure-
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.
d e s o r p t i o ni s o t h e r m s
The
was employed.
were made
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.
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.
(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-
707A u n i t attached t o
t h e microscope.
and
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
a thin
f i l m o f Au/Pd a l l o y .
4.
QectronSpectroscopy
a f t e r exposure
was made with an AEI
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
three times
was
ESCA spectra f o r
Al 2s1/2'
Al 2p, 0 Is
1/2
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
peak.
C. Adsorption Measurements
1.
System:
i nt h e
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
a liquidnitrogentrap
( K ) The LT.
(a), , (RB)
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',
(V6).
(V7), (V8).
(V10) and
PC)
r
v5
v4
2
vc
VD
3
LNT
lv6
M
IC
3
GB
Figure 7.
0
C M
--
Thesystem
, (V2). (V4),
and (VW),
a constant
(cM), a
(Bl
- B6), a
water ( W )
e i t h e r a constanttemperaturebathor
a furnace.Thebath
temperature
a Fischer
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
wall of
Introductionand
Gases
( 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-
gas was t r a n s f e r r e d t o t h e
by opening valves
VE). a series
(v8).
(T) I "surrounded
by l i q u i d
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)
was purgedwithhelium
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
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
followingprocedure.
was evacuated t o
on thesystemandvalve
loe6
torr.
( V l ) openedslowly
u n t i l t h e H a s t i n g s vacuum
measured by thethermocouple.
After h e a t i n g ,t h e
4.
were performed i n t h e c o n s t a n t
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
A cathetometer(GaertnerScientific)
was used t0
manometer ( p r e c i s i o n intothe
2 O.O5mm).
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
Dressure was
a f t e r equilibrium was e s t a b l i s h e d
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
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
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
the i e l da
5.
Readsorption Procedure;
The r e v e r s i b i l i t yo ft h e
hydrogen
readsorptionexperiments.Thereadsorptionexperimentconsisted
D.
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
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
40cc
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
35
automatic Cugltal readoutofconcentration.
A singleelementhollow
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
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
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
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
an Orion Research
Electrode.Approximately
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 .
1.
data o b t a i n e di nt h e
by
adsorbed
adsorption system
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
%=
was opened.
= 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.
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).
37
Ni
= N u m b e r of moles
2.
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
11*14*74 of c a l c u ~ a t ~ n g monolayer
describedincludingthe
BET
(A16SG).
I C
L)X
NmC
where
X = P
Po N
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
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.
P/Po.
were e v a l u a t e d u s i n g
a l i n e a r least
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
in
square angstroms.
Themonolayer
form of t h e Langmuir
N = N u m b e r of moles of H C l / q a m adsorbent.
39
b = Constant characteristic
of the system.
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.
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
at three
at
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.
P v s 1/T a t c o n s t a n t
i s equal t -qSt/R. o
P a t constant coverage
was
data.
40
Bla~kkUn'~ used a F r e u n d l i c h p l o t
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
best f i t ,
data.
IV.
A.
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
were o b s e r v e d i n t h e
Severalotherlessintenseline
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
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
T h e s ef i g u r e s
are
i n agreement w i t h t h e r e s u l t s
This
(100-400C).
i n surface
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
43
0.3
0.2
I
n
I d
W
2
0.1
s-
02 .
0.3
04 .
Figure 9.
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
Surface Area (m 2/ g )
100 100
100 200
200
94.0
97.1
92.9
400 400
400
400 400
5 3.9
46
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
a t e l e v a t e d temperature.
Werfers and
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.
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-
3.
Nitrogen Adsorption
results
- desorption measurements
on g m a alumina are a m
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
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 .
47
8 -
6 -
4 -
Alpha Alumina
49
not unexpected since alpha alumina hadbeen h e a t e d t o 1537OC and
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 :
photomicrographofuntreated
A
A
lOOX photomicrographofalphaalumina
cursorycomparison
13.
However, i n s p e c t i o n of thephotomicrographstaken
small primary
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
17.
N s i g n i f i c a n td i f f e r e n c e s o
after outgamma
Figure 12.
Figure
13.
F'igure 14.
PhotomicmgraphofUntreated
Gm a Alumina a t 5000X am
53
Figure 15.
Figure 16.
55
Ngure 17.
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
Other
were not
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
scan
EC. SA
alphaalumina t o t h e 0 1%/2
(532 eV), C
(118 eV) l e v e l s a n d t o a n
Auger peak
C. u
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
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
of any s u r f a c e c o a t i n g on bothalumina
surfaces ,
57
Flgure 18.
371.5
BindingEnergy
(eV)
Figure 19.
371 5
Binding Energy (eV)
0.0
figure 20.
60
B.
of
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
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
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
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
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
figure 2 . 1
Adsorption
2 hrs 2 hrs
hrs
0 19
10 P (torr)
15
Figure 22.
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
t h i s temperature
were measured a t
on gamma alumina
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
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
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
t h e c a l c u l a t i o n o f t h e average area
I V g i v e s t h e cross-
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
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
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.
on Water Vapor
Adsorption
..,,. .
66
(3
0
d
Kl
0.5
10 P( t o r r )
15
25.
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%)
as an adsorption site.
a phase transition
l@
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
f o r water model
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.
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
of water adsorption on
2. 7
Between t h e o r i g i n a l i s o t h e r m
for 18 hrs.
The readsorptionpoints
Figure 26.
10
0
0
Adsorption Readsorption
.L
10
15
P torr) (
figure
2. 7
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
by r e a c t i o nw i t h
on o u t e s temperatme f o r
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
temperature ran&-
isotherms again
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
(a)
area agrees w i t h t h e r e s u l t s
o fa l p h a
model surface
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
72
0
0
80C
2oooc
MOC
8
P( t o r r )
12
16
Figure 28.
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.
40C onAlphaand
75
20
0
0
0
15
50'C
p/
0 0
5
Figure 30.
Alpha
Resultsobtained
As i n t h e
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.
The water a d s o r p t i o n
temper-
water vaporadsorption
onbothalphaand
g m a i s observed. a m
is
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
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
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
on m
a alumina.
of gamma alumina
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
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
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
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
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
of t h e a d s o r p t i o n
a later section.
surface.
of hydrogen c h l o r i d e a d s o r p t i o n on
i n Figure
9 Isothermson .
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
79
8OoC
20oOc
35
4OO0C
10
P torr) (
Figure 32.
80
7 Initial Adsorption
b
'
Irreversible
0 Sample 2
Reversible
15
10 P(torr)
Flgure 33.
0
0
ooc
4OoC
5OoC
10
15
P torr) (
Flgure
3. 4
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 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
s i t e can be
In
ions,thus
t h e area o f t h i s
group I s 32
12 .
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,
5. 1 '
Work by P a x f i t t 5 6 on
02
be
expected t o a d s o r b on everyotheraluminunion.
83
TABLE V I
CROSS-SECI'IONAL
AFUUS OF HYDROCEN CHLORIDE ADSORBED ON
GAMMA ALUMINA
Outgas
Isotherm
Temperature (OC)
Temperature (OC)
80 80
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
descrip-
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
Bdrogen ChlorideAdsorptionon
Alpha
Alumina
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
T h i s i s similar t o t h e behavior
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
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
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
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
87
0
0
ooc
4OoC
50C
10
P( t o r r )
13
Flgure 37.
on
88
10
Adsorption Readsorption
a
V
10
15
P torr) (
F'igure 38.
0 ooc
173OC
______a_
A
0
0
0
10
15
P torr) (
Flgure 39.
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
act as an e f f e c t i v e sink
it h a s t h e a b i l i t y t o
adsorb H C 1 and
of H a
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
of t h e
t i o no ft h e
hydrogenchloride.
c h l o r i d e adsorbed on alphaalumina,
F u r t h e r s t u d i e s u s i n g a wider range
of temperatures
exists.
Theaverage
was 17.5
x2.
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
91
TABLE VI1
CROSS-SECI'IONAL AREAS OF HYDROGEN CHLORIDE ADSORBED ON
ALPHA ALUMINA
Outgas
Temperature
(OC)
Isotherm Temperature
(OC)
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
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.
of hydrogen
area,
Alpha aluminaadsorbs
more hydrogenchloride
The difference i n a d s o r p t i o n
m-d o x i d e i o n s i n t h e
g m a alumina. a m
On
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
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
94
6.13 -
0
0
Experimental
Freundllch
o m
6.1> -
z
d
7.c I
7.5
1
In P
Figure 41.
95
TABLE VI11
ERROR FOR
FLT OF H20
Slope
Y-Intercefl
. "
E m
Freundllch
3.7
0.9
242
0.06
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
of immersion i n H a t e r f o r also
heats ofimmersion
f o r a l p h a alumina t h a n f o r gamma
t h e l a r g e r numher of H,O
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."
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
T h i sd e s c r i p t i o n
i s consistent with
w a t e rt o
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
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
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
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
80 80
400
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
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.
The amount
o f water p r e s e n t on alphaand
as a t n o s t e p p r o c e s s
gas i n t h e l a y e r o f
step(Reaction
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
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
"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
isosteric h e a to fa d s o r p t i o n
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)
2.
H(Sl(aq)
Al,U
L 3
(s)
___c_
HC1
---
A1 0
2 3
Figurr 43.
101
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
pH
is t h e p beforeaddition H
i s t h e p of t h e s o l u t i o n H
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.
were l i n e a r i z e d
on a I n N vs I n P p l o t .
102
TABLE X
-AwH
(mJ/m2
-A,H
("C)
80 100
200
0
7.23 7.73
11.0 - 0.1 +
088
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
PHlO -
PH60 1.41
'580
1.36
100
0.1
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
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
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
curve using a
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
HG, i s reasonThe d i f f e r e n c e
a t 80 and 200C.
a l l the pre-adsorbed
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
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.
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.
1: 2
0
D
100
8OoC
20oOc
4OoOc
75
50
\a
figure
4. 6
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
-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 :
s i t e and
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'
ESCA spectra o ft h e
Al 2slI2,
Al Zp, 0 1s
Figure 51.
T h i sl a r g e
spectra i n a r a t i o of
, 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
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 .
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
at OC,
surprisingly
any s i g n i f i c a n t change
205.6
185.6
Figure 47.
Alumina
126.4
116.4
106.4
figure
4. 8
Alumina
80.4
70.4
Binding Energy (ev)
60.4
Flgure
4. 9
535.4
525.4
Binding Energy (ev)
515.4
Mgure 5 . 0
. . ..
2W.4
194.4
BindingEnergy
1W.4
(ev)
Flgure 51.
f m m Untreated Alpha
Flgure 52.
aluminum o r oxygen
peak
(8)
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
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
Untreated Ae, v
HQ 'Ekposed
Ave
c1 2p
B E (ev) . .
198 9
197 3
198.1
37 .
38 . 118.7 12.8
43 .
4.1 118.1 13.3 118.4
197 5
3.7
119.0 120.9 10.7 38 . 74.0 16.8
Al 2 s
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
37.3 34 .
-0.2
46.7 3.4
06 .
531 2
3.7
18 .
36 .
120
TABLE X I V
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
73.2
0 1s
530.6 61.1
530.4
26 .
-0.6
HQ Exposed
B E. (eV), .
Q
2P
Ave 198 5
Al 2s
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.
was
was 8.1 5
1.8 m2/g.
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
g m a alumina a m Gm a alumina am
be l a r g e r
of thealuminas.
However, t h ep r i m a r yp a r t i c l e s
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
122
g m a alumina showed a a m
4OO0C showed i n c r e a s i n g a d s o r p t i o n o f
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
onboth
Alphaaluminaadsorbed
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
O alphaalumina n
area of12.4
(d2 c o n s i s t e n t
area on t h e
82
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
22/
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.
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
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
a dependenceonadsorptiontemperature.
isotherms obtained
Hydrogen c h l o r i d ea 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
The isosteric
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
124
particle followed by t h e
Agreement n a s
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
LITERATURE CITED
1. A Procko, "Encyclopedia of I n d u s t r i a l Chemical Analysis," F.D. S n e l l a n d S.L. E t t r e , I n t e r s c i e n c e , N w York, N.Y., e 1971, P. 389403.
Ed.,
2.
H. Bassow, "Air Pollution Chemistry An Experimenter's Sourcebook," Hayden Book Company, Inc. , Rochelle P a r k , N w J e r s e y , 1976, e Chapter 3.
A.C. N.Y.,
3.
4.
S t e r n , "Air P o l l u t i o n , " Vol. 11, Academic Press, N e w York, 1968, Chapter 38.
Program ,I1 N A S A ,
5.
6.
Dobbins and
L.D.
Strand, A I A A J o u r . , 8,
1w (1970).
J.W. Hightower, " C a t a l y t i cS i t e s on Gm a Alumina," Awards am Symposium on C a t a l y t i c S i t e s on Oxides,MvisionofPetroleum Chemistry Meeting, American Chemical Society, Callas, Texas, April 1973-
7.
8.
9.
10.
K. Takahashi, J.
Catal., 2 9 , 67
(1973).
1 . D.M. Young and A.D. Crowell,"PhysicalAdsorption 1 k t t e m o r t h s , London, 1962.
12.
S. R s and J .P. O l i v e r , "On PhysicalAdsorption, os N e w York, 1964.
'I
of'Cases,"
Interscience,
13.
14.
Ed.,
D.O. Hayward and B.M.U. T r a p n e l l , "Chemisorption," 2nd ed., B u t t e m o r t h s , London, 1964. Gregdry and August, 1975.
15. C.L.
16.
126
17
18.
19.
20.
W.C.
Hulten, R.W.
Storey, G.L.
Gregory, D.C. Woods and F.S. Harris, J u l y , 1974. Wightman, Anal. Chem.,
4, 8
1818
(1976)
Nadler, AFRPL Report 5730-73-6, Calif.,September1973. Edwards A i r Force Base,
21. 22.
H.R. Rooksby i n 'X-ray I d e n t i f i c a t i o n and Crystal Structures of Clay Minerals," C. BMwn, Ed., MineralogicalSociety, London, 1961, Chapter X.
K. Werfers .and G.M. B l , Technical Paper No, 19, Aluminum e l Company o f America, East St. Louis, I l l i n o i s , 1972.
A. Blelanskiand
23. 24.
A. Sedzimir,"4thInternational Symposium on t h e R e a c t i v i t y of S o l i d s , " J.H. De Boer, Ed., Elsevier Publishing Company, N w York, 1961, p. 301. e
25.
26.
Marcel
161 (1972).
2. 7
28.
T.L. Slagerand
J.H.
C.H.
Lunsford, L.W.
179 (1975)
2. 9
30
31.
32
J. Phys. Chem.,
C.N.
Cochran, Environ.
S i Technol., 8, c.
63 (1974).
74,
33.
M.M.
J.B.
3973 (1970).
34.
35.
36.
A.V.
D 0 e
and I.C.
I.D.M.
mlla
P.J. Hendra,
9
Turner, E.J.
37.
38.
39. 40. 41.
J .B. J.B.
Peri,
, 69,
220 (1965).
4. 4
45.
4, 4
Wcel
M.L.
46.
47.
Hair, "Infrared Spectroscopy in Surface Chemistry," Dekker Inc. , New York, 1967, Chapter 4.
J.D. Carruthers, D.A. Payne, K.S.W. S i n g and L. J. S t r y k e r , J. Colloid Interfac. Sci. , 3 6 , 205 (1971).
D.S.
4. 8 49.
50.
D.S.
Catal., 3 , 502
(1964.).
R.L. R.L.
1196 (1960).
, W.H.
937 (1963.
51. T. Morimoto, K. Shiomi and H. Tanaka, B l. Chem. SOC. JaE., ul 37, 392 (1964) 52.
53.
54.
L.C.
(1972).
128
55
56.
57
0
-0
Rochester, T -
68,
269 (1972).
58.
59.
60.
W S Lassiter, SurfaceSci., ..
D.H. Everett and J.P. Wightman, 1976 EUCHEM Conference, Collioure, France, April, 1976.
61.
62.
s.Y. Tyree, Jr., "1st S t a t u s Report N S Grant NSG1204," NASA AA LangleyResearchCenter, Hampton, V i r g i n i a , December, 1975.
S.Y. m e , Jr., "2nd S t a t u s Report NASA Grant NSG1204," N S AA LangleyResearchCenter, Hampton, Virginia, March, 1976.
S.Y. Tyree, Jr., "3rd Status Report N S Grant NSG1204," NASA AA LangleyResearchCenter, Hampton, Virginia,June, 1976.
63.
6. K. 4 J.
65.
66.
Siegbahn, C. Nordling, A. Fahlman, R. flordberg, . K. Hamrin, Hedman, G. Johansson, T. Bergnark, S Karlsson, I. Lindgren, . and B. Lindberg, "ESCA Atomic Molecular and Solid State Structure S t u d i e s by Means of Electron Spectroscopy," Almquist and Wiksells, Uppsala, Sweden, 1967.
D.M.
4, 4
106R (1972).
67.
68.
69.
70.
Anal.
(1974).
Watts, J r . ,
J.R. Lindsay, H. J. Rose, Jr., W.E. Swartz, Jr., P.H. and K.A. Rayburn, A w l . Spec. , 2 7 , 1 (1973).
71
72.
73.
G E Hendley, S.V. O'Neal and J.P. Wightman, f i n a l Report .. NASI-13175-7, B l a c k s h g ,V i r g i n i a , June, 1975.
74.
S.J. Gregg and K.S.W. Sing, "Adsorption,Surface Academic Press, Nw York, 1967, Chapter 3 . e
M.L.
Parsons, J. Chem. M.,50, 679 (1973). Blackburn, J. %atal., 1, 244 Newsome and C.M. Tucker,
77.
78.
79.
80.
m.
W.R.
Kirst, SurfaceSci.,
5,
81.
82.
F'abel,
S.M.
83.
P.E. Field, Chemistry Department, Virginia Polytechnic Institute and StateUniversity,Blacksburg, Virginia.
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 .
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
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 .
film
gm a a m
The c r y s t a l l i n ep h a s e
problem. Honever,
a t t e m p t st o
disks of t h e
Data "abler
Weight Sample; Alon Rn 1 u: Pretreatment
'
15.8768
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
5-
Ro
= 648.10
a
( 2 4
P2 = R2
- Ro
x
p2
634.8
(2-B)
vT=
('I
' 1 )
- ~. - 113.43 cc
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 :
- PXVT N1 - R X T X Y
= 35.52
lo4
( 2 4
cc-torr mole- K
0
323OK
0.1145g
lo"
is:
VT
mole-gram
-1
(P1 X V I + P2 X VSB),
- u.55 x
113.43)
18.3
(1.80 X 13.9)
and then:
N =
0.39 X .6.24 X
127.3
X 323 X 0.1145
lo4
2.15
mole-gram
calculated.
by
133
each
dose.
is calculated b: y
etc.
vs. Pmp,
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"
Equation
W A
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 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
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
: 1 .e5 :4.85
:9.08 :12 .c10
:1 5 . 6 5 :10.25
137
PJUOIBER O F POI NTS: 2 0
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=
0.77834RE+gI
"
02.05 02.07
A "
" 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 W=W+Y(I>*Y(I>
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
R l U 1
0.70
9.9 79
61. a9
1.20
Rn u1
Run2
16.60
139
140
Outgas Teapestu=:
8OoC
Itorr)
R 1 W l
pEXP
1.10
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
1 1 G . 82
133.48
141
Run4
66.69
107.29 126.96 141.07
84.84
0
Run1
035
Rn u1
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
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
7.25 7.22
Run2
3.35
12.50 16.60
20.10
N~ x 105
(torr)
Rn u1
(mole/R)
b n 2
11.88
14.02 14.94
N~ x 105
(mole/g) 0.20
1.85 4.95
8.00 12.70 16.00
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
N~
105
torr)
lmole/g)
Rn u1
0.40
4.15
9.10
14.40
APPENDIX 8
tion
on Gamma Alumina
50.80
51 70
Outgas Temperature t
AdsorptionTemperature
40C
*EXP (torr)
N~
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
4. 4
w
16.50
23.30
31 03 37 85 39 57 41.25 46.46 45 95
rn
9
16 4
32.03 9.70
37.18
38.58
N~
105
torr)
Run1
imole/g)
37 -95 38.47
40.40
41.92 42.23
Run 2
Run4
147
Run5
0.80
N~
(torr)
Rn u1
x 105
(mole/g)
15.65 19.25
Run2
56.44
58.61 39.65 50.74 53.93 55.74 57.91
1t o r r )
Rn u1
0.80
'X EP
148
Run2
0.95
4.20
Adsorption Temperature I
5OoC
(torr)
N~ x 105 (mole/g]
ml
1.80
4.75 9-70
13.10 18.20
Run 2
1t o r r )
Run 1
'X EP
1-95 3.85
7-70
11.95 17. i o
Run2
1.10
41 57
41.87 45.49
48.20
50.06 51.35
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
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
pEXP
N~ X 105
(mole/q)
tom)
Run 1
0.25
1.20
APPENDIX 9
m Data o p r i n t
Outgas
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)
Run 2
Outgas Temperature :
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
Outgas Temperatun I
Adsorption TemperatureI
8OoC g0C
torr)
Rn u1
N~ x 105 Jmole/g)
Run 2
58 .0
10.50 15a.35
2.0 14
Outgas Temperature I
'X EP itorr)
Run1
N~
x 105
0.75 34 .0 6.55
20
55
Run2
1.30 4.20
11
8.20 55
15.80
19.50
" "
.. .... . . . .
.. .
..- . ..
..
" "
... . -
~~~
153
(torr)
Run 1
2.25
4.40
N~ (torr1
Run 1
105
(mole/g)
0.50 4.00
9.20 13.30
18.40
Run 2
N~
&!?Ed
Run1
x 105
irnole/g)
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
7.46 7.75
7.98 8.15 8.22
'X EP
0
Run 1
Ns X 105 (molejg)
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)
S AB=FLOG(CIM);
0R.BR 08.10
Nf'l"NP1," S NtQ=Nt'ttIC
''
APPENDIX 1 1
.
CalculationPoofthe
30.s A1203,
2 0 . H HQ,
9.4% HzO,
2. CO, 4s
3.W
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
of
firisto],
INTRODUCTION
Heats of immersionhavebeenwidelyrcDortedor
a number o f
systems ( 1 ) .
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
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)
tic1
(7)
f o r thealuminn/llCl
(3s)
system*
EXPERIXNTAL
Calorimeter. The -~ h e a t s
Calvet
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:
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
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
( 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
use.1 a n d a r e
in each
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.
prenared f r o n a s t a n d a r d
- CVY).
Solutions of specified by d i l u t i o n o f t h e
0.1 N
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
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
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)
(%
0.5 E)
The ampolllcs
1 h r at he necified emperature. s t
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
(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
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.
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
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
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
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
is
noted.
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 .
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
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
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
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
of t h ei n t e g r a t e d t h e compensated
The
s t u : ~o f
heatsshould
e q u a l t h e heat :qgllt.
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
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.
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.
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
?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'
expressedn i Appendix B .
m.
The prey
I J and T
HC1'
of i l C l
(aq)
is C
The
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
wcttinp,wcrccnlculatcd and u n i t a r e a b a s i s
by cquntions
[SI
151
A H + A
H
(mJm
-2
. )
- A !J 1 1
.I:'
NC
as
1.22.
Hence, t h e e a t s f h o
immersion were
for weiglltloss
on outgassing.
of evacuatedbulbbreakingdeterminedinwater
J and 0.062
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
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,
.
[I]
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
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)
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
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
of
167
A H and t h ee x p e c t e de r r o r w
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.
tobeconsideredcomplete? an asymptoticapproach
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
c o u n tr a t e
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 t i m ef i g u r e si np a r e n t : l c s i s
state.
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
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
of
t h eh e a t sg i v e ni n
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.
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
outgassing i s i n t h e rnngc
valuesreported
However, t h ev a l u e thereportedrange
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
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
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
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.
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
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
out;:assin?
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)
a f t e r 1 Inin (Table V ) . 0
2 3
additi0n.wa.s
1.43.
a slightte:npernturc
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
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
any d i s s o l u t i o n whichoccurs. 4.
A
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
170
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
3-5 b u t
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
; 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
at 4 m 0
of
by a f a c t o r O F 2 .
inunersion i s a t t r i b u t e dt o
times l e s s y-A1 0
2 3
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
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
n1-? anrl a t
400
-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
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
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
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.
? 3
ant1 - ; - A l ? l J 3
wi t1l
? 3
wns
consit1cral)lv
? 3'
Tllc
IISC
o r tlle Calvet
the
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
"
OF
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
? 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'
2 3
slurry.
N lICl
t h a nt h a t
f o r y-A1 0 2 3
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
tnkc
y-A1203 a longertime
0 . 1 N I!C 1 compared t o w a t e r .
I would l i k e t o
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 .
on-strean i s appreciated.
?.!r. ? . E .
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,
pp.145-175.
6 4 , 1136 (1960).
"
3.
Tnnnkn, U1111.Cl1em.Soc..Tapan,
4.
Vncle,
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 ) .
"
16, ._ -
157 (1370).
??,
67 (1973).
10.
E . Calvet a n d
M.
PcrrnnonPress
11.
I,.
P.
12.
13.
1974. 1976.
R.R.
S.U.,
14.
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
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
9.99
3.7?
-
? .4n
100 200
200
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
..
..
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
P =e
(OC)
-A H(m.J m ')
W
-3
- A H(.T
I.1
T,
-1 )
80 100
200 300
888 349
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
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.
184
t (min)
20
40
60
I
3
Figure 2b.
)! .
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
ESR
(mv)
18 T
2.994 2.395
2.99s
55
19 1 1
2 4 I1 25 I 2 8 I1 29 1
.
55
60
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
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
0 0
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
49 I1 5 4 I1
55 I
60 I1
0.1
0.1
0. 1
0.1
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
80
0.1
88 I1
0.1
89 I
101 I
0.01
0.01 0 .os
0.001
1138
12 39
1333
1134 1329 1222
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)
100
100
1.662 1.931 3.790 3.184 3.839 3.897 7.000 1.770 1.827 4 .O42 3.989
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
70.7 148
0.1
0
.c)
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
7. Author(s)
R. R. Baileyand
James P. Wightman
&
StateUniversity
"~.
-.
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.
11. ContractorGrantNo.
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,
1978