[ ~ UT T I ~ RWORT H

I - ~ E I N E M A N N
Adsorpti on of gaseous p-xyl ene and
m- xyl ene on NaY, KY, and BaY zeolites.
Part 2: Model i ng. Enthalpies and
entropies of adsorption
~
a n - P i e r r e B e l l a t a n d Ma r i e - H6 1 &n e S i mo n o t - G r a n g e
niversit~ de Bourgogne, Laboratoire de Recherches sur la R~activit~ des Solides,
Dijon, France
The a d s o r p t i o n i s o t h e r m s o f x y l e n e s a r e d e s c r i b e d b y Henry's law and Langmuir' s model on N a Y
a n d KY a n d t h e D u b i n i n - R a d u s h k e v i c h m o d e l o n Ba Y. T h e i s o t e r i c e n t h a l p i e s o f a d s o r p t i o n s h o w
o n e a c h z e o l i t e t h a t t h e a d s o r b a t e - a d s o r b e n t i n t e r a c t i o n s a r e n e a r l y t h e s a m e w i t h b o t h i s o m e r s .
They a r e s t r o n g e r o n B a Y than on N a Y a n d KY. T h e a d s o r b a t e - a d s o r b a t e i n t e r a c t i o n s a r e s t r o n -
g e r wi th m-xyl ene than wi th p-xylene a n d e s p e c i a l l y o u t s t a n d i n g on KY. The e n t r o p i e s o f a d -
s o r p t i o n s h o w that the m o b i l i t y o f t h e a d s o r b a t e is l o w e r wi th m-xylene than wi th p-xylene. T h e
i s o s t e r i c f r e e e n t h a l p i e s o f a d s o r p t i o n a r e r e l a t e d t o t h e a c i d i t y o f e a c h z e o l i t e . B a Y h a s a s t r o n g e r
a c i d i t y a n d a g r e a t e r a b i l i t y t o a d s o r b x y l e n e s than NaY and KY.
Keywords: adsorption; Y faujasite; xylenes; modeling; enthalpy; entropy; mobility; acidity
I NT RODUCT I ON
Thi s second par t is devot ed to t he model i ng of ad-
s or pt i on equi l i bri a o f pur e gaseous p- xyl ene and
m-xylene on t he NaY, KY, and BaY zeolites pr esent ed
in Part 1. t The r modyna mi c model s are used to de-
t er mi ne t he ent hal pi es and ent r opi es of adsor pt i on
dependi ng on t emper at ur e, pressure, and adsor bed
amount . Her eaf t er t hey will be usef ul f or t he predi c-
tion of adsor pt i on equilibria of bi nar y xyl ene mix-
t ures f r om t he adsor pt i on equilibria of pur e com-
pounds.
L I T E RAT URE S URVE Y
C u r r e n t r e s u l t s
The r e ar e not many works quot ed in t he l i t erat ure
about t he model i ng of t he adsor pt i on of xyl enes on
faujasite t ype zeolites. The few results ar e t hose of
Santacesaria et al., 2 whi ch show t hat t he adsor pt i on
equilibria of xyl enes on NaY and KY zeolites are de-
scri bed satisfactorily with t he Langmui r and Fowl er
model s and t hose of Rut hven and Goddar d, a which
obt ai n a bet t er correl at i on with t hei r exper i ment al
results by usi ng a model devel oped f r om statistical
t her modynami c principles.
Address repri nt requests t o Dr. Bellat at t he Laboratoi re de Re-
cherches sur la R6activit6 des Sol i des, URA CNRS N 23, B. P. 138,
21004 Di j on, Cedex France.
Received 29 Sept ember 1994; accepted 25 Oct ober 1994
Zeolites 1 5 : 2 1 9 - 2 2 7 , 1995
Elsevier Science Inc. 1995
655 Avenue of t he Amer i cas, N e w York, NY 10010
T h e o r e t i c a l
The t her modynami c model s t est ed in this wor k are
t hose of Langmui r, 4 Fowler, 5 and Dubi ni n- Radush-
kevich 0'7 (DR model). The y ar e selected f or t hei r sim-
plicity and because t hey of t en descri be t he adsor pt i on
of gas on zeolites, s'9 The statistical model of Ruth' ven 3
will be t est ed hereaft er.
At t he t emper at ur e T, t he equi l i bri um const ant f or
t he react i on adsor bat e = adsorpt i ve is:
K r =p/pO
a/ao
a 0 and p0 are t he st andar d activity and pr essur e (a0 =
1 and p0 = 101,325 Pa), and p is t he pr essur e of ideal
gas.
The adsor bat e activity, a, is expr essed as a f unct i on
of t he adsor bed amount , n, by t he fol l owi ng relation:
n
a = ~/n--~ = ~/0
wher e ~ is t he activity coefficient, 0 is t he filling co-
effi ci ent of t he zeolite, and nma,, is t he maxi mum
amount of adsor bat e unde r vapor pr essur e P0 at t em-
per at ur e T.
The t her modynami c model s are expr essed in Table
1. 8 Each model is t est ed by dr awi ng its l i near plots.
The equi l i br i um cons t ant Kr and t he ma xi mum
amount s of ads or bat e nma x ar e der i ved f r om t he
slopes and t he ordi nat es at t he ori gi n of t he straight
lines fitting well on plots.
0144- 2449/ 95/ $10. 00
SSDI 0144- 2449( 94) 00048- W
Ads or pt i on o f gaseous p- xyl ene and m- xyl ene: J.-P. Bel l at and M.-H. Si monot - Gr ange
T a b l e 1 T h e r m o d y n a m i c mo d e l s o f a d s o r p t i o n
A c t i v i t y o f t h e
Mo d e l a d s o r p t i o n t y p e a d s o r b a t e E q u i l i b r i u m c o n s t a n t L i n e a r f o r m t e s t p l o t
He n r y s a = 0
D n
mo b i l e ; t w o - d i m e n s i o n a l g a s n ma x = n L KT = ~ p = KH ~ -
l i r a ~/ = 1
Fr y
I I L
0 --* 0 KH = PKT p = f ( n )
Lang mu i r 4 0 p( 1 - O) npo Po Po
l o c a t e d a n d h o m o g e n e o u s ; a = ~ KT - - - -- KL n
no i n t e r a c t i o n b e t w e e n 1 -- 0 pO0 P EL nL - - - -
nmax = nL KL = P K( T) npo f ( n)
t h e mo l e c u l e s l i m ~/ = 1 - - =
O'-'* 0 P
Fowl er S - Zo~ Z~o L n ( Pen P0 +
l o c a t e d a n d h o m o g e n e o u s ; ~ p( 1 - O) ~-~O = - -
i n t e r a c t i o n s b e t w e e n a = KT = - - ~ \ r ( . . , n,
t h e mo l e c u l e s
nmax = nL K F = P Kr L n ( pen__ /
f i n)
l i m " y = 1 \ P ( ~ L n ) ~
/
0 - - ~ 0
Du b i n i n - Ra d u s h k e v i c h 8,7
i n mi c r o p o r o u s v o l u m e
n pn
a = ~0 = ~-~n K T - -
p~n o
nma x = n o
l i r a ~/ = 1
0 - - , 1
DR e q u a t i o n
o 0 , n , = , ( ,
The accuracy of t he fit of a model with t he exper-
i ment al dat a is given by t he average relative er r or :
100 ~ Inexp -- ncall
Erm(%) - Nexp nexp
0
wher e ne, ,_ is t he exper i ment al amount of adsorbat e,
E
nca I t hat calculated with t he model , and nex p t he num-
ber of exper i ment al data.
The ent hal pi es and ent r opi es of adsorpt i on are de-
t er mi ned f r om t he t emper at ur e dependence of t he
equi l i bri um const ant following t he relation:
AH o AS o
Ln(Kr) = R T R
The values AH and AS ar e t hen assumed i ndepen-
dent of t he t emper at ur e. For each model t hey are
def i ned with t hei r st andar d states in Tabl e 2.
T a b l e 2 S t a n d a r d s t a t e a n d n o t a t i o n o f t h e r m o d y n a m i c v a l u e s
o f mo d e l s
Mo d e l K r AH AS S t a n d a r d s t a t e 1
He n r y KH A/'F=H AS=H i n f i n i t e d i l u t e d s o l u t i o n
p--6 ( l i m ~/ = 1 )
e x t r a p o l a t e d t o 0 = 1
pO = 101, 325 Pa
Langmuir KL A/'~LL AS~L 0 = 0 . 5
p-'6 pO = 101, 325 Pa
F o wl e r KF AHF ASF O = 0. 5
p.._~ pO = 101, 325 Pa
The isosteric ent hal pi es and ent ropi es of adsorp-
tion are given by t he relation:
Ln (pP-) - AadsHm(n) R T AadsS,~(n) R
with
AadsHm(n) = Hm( a d s , T , n ) - H ( g , T )
AadsSm(n) = S m( a d s , T, n ) - Sm(g,T)
Hm( a d s , T , n ) and S , , ( a d s , T , n ) are t he mol ar ent hal py
and e nt r opy of t he ads or bat e f or t he a ds or be d
2
~J
E
--......
0 .
(a) pX/NaY
L:r : m: i r l l
250C t ~ ,
0 1 2
(b) pX/KY
200C ~ 150 q
150C .250C \
3 0 1 2 3
n/(molec.oc- 1)
F i g u r e I L a n g mu i r ' s p l o t f o r t h e a d s o r p t i o n o f p - x y l e n e on Na Y
(a) a n d KY ( b) z eol i t es .
220 Z e o l i t e s 1 5 : 2 1 9 - 2 2 7 , 1 9 9 5
3
~ J
2
m
E
= 1
~ P
Adsorption of gaseous
(a) mX/NaY
~ 2oooc
2 5 0 C ~ o
Langmuir / 150 C
0 1 2
(b)
250c 200
= ~ ~ , Henry
350C
3 0 1
n/(molec.cx- l)
mX/KY
150C
2 3
F i g u r e 2 L a n g m u i r ' s p l o t f o r t h e a d s o r p t i o n o f m - x y l e n e o n
N a Y ( a) a n d K Y ( b) z e o l i t e s .
amount n, at t he t emper at ur e T, and unde r t he equi-
l i bri um pr essur e ~0.
/-/~(g,T) and S~(g,T) are t he mol ar ent hal py and
ent r opy of t he adsor pt i ve unde r t he st andar d pres-
sure p " = 101,325 Pa.
The isosteric ent hal pi es and ent r opi es of adsorp-
tion are der i ved f r om t he slopes and t he i nt ercept s of
t he isosteric st rai ght lines Ln( p/ p ) = f ( 1 / T) n (on t he
assumpt i on t hat t hey are const ant bet ween 150 and
400C).
R E S U L T S A N D D I S C U S S I O N
The exper i ment al dat a and t he physical feat ures of Y
zeolites and xyl enes are given in Part 1.1 The inves-
tigated ranges of t emper at ur e and pr essur e are 150-
400C and 10- 1, 014 Pa. The ads or bed amount (n) is
expr essed in mol ecul es of xyl enes per a-cage of zeo-
lite (molec a - x). 1
Mo d e l i n g o f a d s o r p t i o n i s o t h e r m s
N a Y a n d K Y zeolites
Adsor pt i on i sot herms of p-xyl ene and m-xylene on
NaY and KY zeolites and Langmui r ' s pl ot (Figures 1
p-xylene and m-xylene: J .-P. Bellat and M.-H. Simonot-Grange
and 2; Table 3) show t hat t he adsor pt i on follows Hen-
ry' s law f or t emper at ur e hi gher t han 250C and rel-
ative pressures of p-xyl ene and m-xylene l ower t han
10 - 4 and 0.4 10 -a, respectively. Thi s law is ob-
served in a filling r ange gr eat er with p-xyl ene (0-1
mol e c , a - l at 250C) t han wi t h m-xyl ene ( 0- 0. 7
mol ec or- 1 at 250C) and which decreases as t emper -
at ur e increases (0-0. 45 mol ec a - 1 with p-xyl ene and
0- 0. 25 mol ec, a - 1 wi t h m-xyl ene at 350C). 1'11'12
The adsor pt i on i sot herms of p-xyl ene ar e descr i bed
by Langmui r' s model (Erm = 2%) (Figures 1 and 3,
Table 4) bet ween 200 and 350C f or relative pr essur e
r angi ng f r om 10 - 4 to 10 - 2 . The validity of this
model is conf i r med on Fowler' s pl ot (Figure 4) show-
ing straight lines of slopes equal to zero (Zc0 -- 0, no
adsor bat e- adsor bat e interaction, Table 1). However ,
above 2.75 mol ec ~- 1 at 150C (P/Po = 10-3) Lang-
mui r' s model does not pr ovi de an adequat e r epr esen-
tation of i sot herms (Figure 3) .
With m-xylene, f or relative pr essur es hi gher t han
0.4 10 -4, Langmui r s pl ot shows two lines of neg-
ative slopes (Figure 2) . Fowler' s pl ot also shows two
lines, but t he second line has a sl ope equal to zero
(Figure 5). I n this case, Zto = 0, and Fowler' s model
becomes equi val ent to Langmui r ' s (Table 1). Ther e-
fore, on Langmui r' s pl ot t he first and second lines
account f or t he ads or pt i on accor di ng t o Fowl er' s
model and Langmui r' s model , respectively (Figure 2,
Table 4). The l ower t he t emper at ur e, t he gr eat er t he
filling range of validity of Fowler' s model and t he
l ower t hat of Langmui r ' s model are (Figures 2 and 5).
Nevert hel ess, t he model i ng of adsor pt i on i sot herms
(Figure 6) with Fowler' s model (Erm > 5%) is not
bet t er t han with Langmui r ' s model (Erm < 2%). As
with p-xylene, Langmui r' s model becomes i nadequat e
at 150C f or filling hi gher t han 3 mol ec cx- 1 f or t he
NaY zeolite and 2.5 mol ec, a - x for t he KY zeolite
(Figure 6).
What ever t he i somer is, t he DR model is not valid
with t he two zeolites at low filling because it is incon-
sistent with Henr y' s law. However , at hi gh relative
pressure, i.e., at high filling of t he zeolite, t he DR pl ot
(Figure 7) converges to a finite value, charact eri zi ng a
steric hi ndr ance for t he adsorpt i on, l l - l s
T a b l e 3 E q u i l i b r i u m c o n s t a n t s , e n t h a l p i e s , a n d e n t r o p i e s o f a d s o r p t i o n o f x y l e n e s o n N a Y , KY, a n d B a Y z e o l i t e s f r o m H e n r y ' s l a w
K .
102 p--5 I~'/=HI/(kJ m o l - 1)
IASTA/(J K- 1 . m o l - 1 )
A d s o r b e n t
a n d T/C p - x y l e n e m- x y l e n e p - x y l e n e m- x y l e n e p - x y l e n e m- x y l e n e
N a Y
1 5 0
2 0 0
2 5 0 0 . 2 7 3 0 . 1 1 8
3 0 0 0 . 8 5 3 0 . 3 7 7
3 5 0 1 . 6 9 7 0 . 9 8 6
KY
1 6 0
2 0 0
2 5 0 0 . 1 5 8 0 . 0 8 1
3 0 0 0 . 5 6 2 0 . 3 8 3
3 5 0 1 . 0 5 6 0 . 1 0 4
5 0 - + 1 0 5 8 + - 1 0 4 6 _ + 1 0 5 4 _ + 1 0
5 2 - + 1 0 6 9 - + 10 4 6 _ + 1 0 7 4 _ + 10
Z e o l i t e s 1 5 : 2 1 9 - 2 2 7 , 1 9 9 5 2 2 1
Adsorption of gaseous p-xylene and m-xylene: J.-P. Bellat and M.-H. Simonot-Grange
Tabl e 4 Equi l i br i um constants, ent hal pi es (k J- mo l - 1), and ent ropi es (J- K- 1. mo l - 1) of adsor pt i on of xyl enes on NaY and KY zeol i tes
f r om t he Langmui r and Fowl er model s
Langmui r Fowl er
102 102
nt/(mol ec. ~- ' ) p O I A ~ I l a , ~ l p0 I ~ H o A I A S o A
Z e o l i t e
and T/C p-X rn-X p-X m-X p-X m-X p-X m-X m- xyl ene
NaY
150 2.75 3.05 0.005 0.003
200 2.70 2.75 0.020 0.015
250 2.60 2.55 0.158 0.108
300 2.50 2.50 0.543 0.493
350 1.50 1.50 1.332 0.937
KY
150 2.77 2.60 0.004 0.002
200 2.62 2.30 0.024 0.014
250 2.37 2.04 0.083 0.069
300 2.26 1.85 0.325 0.296
350 1.72 1.70 0.789 0.937
64 +- 10 67 -+ 10 67 +- 10 71 z 10 89 -+ 10 103 +- 10
58 -+ 10 69 -+ 10 53 +- 10 72 -+ 10
4. 9 10 - 7
2.9 10 - 3
0.069
0.213
0.735
1.6 10- *
3.6 10 - 3
0.030
0.207
0.809
98 + - 10 118+- 10
'~. 2
c.o
E
o o O o o o : : _150o C
0 2 4 6 8 10 12
p/ mba r
Fi gure 3 Model i ng of adsor pt i on i sot her ms of p- xyl ene on NaY
and KY zeol i t es wi t h Langmui r ' s model [ exper i ment al : (O) NaY,
(Q) KY; t heor et i cal : sol i d l i ne].
12
(a) mX/NaY
~ 150C
~-. 11 200oc ~ _
1 0 [enry Fowler
~. ~ Langmuir
~ . 2s ooc
e .
_~. _--~. ~.~ 300C
8 50oc
7 ! , , ,
0 1 2 3 0 i
n/(molec.cx" 1)
(b) mX/KY
200C
/ " ~ % - . ~ * * ~ 250oc
~ .'~'.~ 300oc
350C
Fi gure 5 Fowl er' s pl ot f or t he adsor pt i on of m- xyl ene on NaY
(a) and KY (b) zeolites.
11
10
9
=.=
8
(a) pX/NaY
l s ooc - - . r -
200C ~ f f
Langmuir
H T ) f f ~ 250C
, ~ p . , ~ ^ 300C
~aa=-- 350C
(b) pX/KY
150C
200oC m ~__
~ 3 5 -*-'`~"~-~ 150C
~C 300 C
7
0 i 2 3 o i 2 S
n/(molec.c~" l)
Fi gure 4 Fowl er' s pl ot f or t he adsor pt i on of p- xyl ene on NaY (a)
and KY (b) zeol i tes.
3
- ~ 2
E
i -
. - - 6 - - - c - o
. . . . o ..... o ..... o ..... o - . . o . . . . o 150C
200C
0 ~ 350C
0 2 4 6 8 10 12
p/ mba r
Figure 6 Modeling of adsorption isotherms of m-xylene on
NaY and KY zeol i tes wi t h t he Langmui r and Fowl er model s [ex-
per i ment al : (O) NaY, (O) KY; t heoret i cal : Langmui r (sol i d line),
Fowl er (dashed l i ne)].
222 Ze o l i t e s 15: 219- 227, 1995
'~. 0
~J
"5
E
==- 1
- 2
0
Figure 7
zeolite.
Adsorpt i on of gaseous p-xyl ene and m-xyl ene: J.-P. Bel l at and M.-H. Si monot-Grange
/ 2 0 0 C
250oc
no=3.6 molec.a" ~l i ~ / 300C
. %
~mX/NaY) " /
3 5 0 C
2 4 6 8 10 12
10- 6(Tlogpo/p)2/K" z
DR pl ot f or t he adsorpti on of m-xyl ene on the N a Y
3
'~ 2
O
E
~ 1
150C
~
250C
300C
350C
4 0 0 C
; ( B a Y z e o l i t e )
0 ' 2 ' ' ~ ' / ' 8 ' 1 ' 0 ' 12
p/ mbar
Figure 9 Model i ng of adsorpt i on i sotherms of xyl enes on the
BaY zeol i te wi t h the DR model [ experi ment al : () p-xyl ene, ( 0)
m-xyl ene; theoreti cal : sol i d line)].
B a Y zeolite
As r egar ds t he BaY zeolite, t he adsor pt i on of xy-
lenes at low pr essur e is much t oo gr eat even at 400C
t o o b s e r v e He n r y ' s l aw wi t h t he e x p e r i me n t a l
set up. 1'11'12 I n t he i nvest i gat ed filling r ange 1- 3
mol ec- or - 1, t he Langmui r and Fowl er model s are
not valid. The adsor pt i on is descr i bed onl y by t he DR
model (Erm < 3%, Figures 8 and 9, Table 5).
Ad s o r p t i o n c a pa c i t i e s
The adsor pt i on capacities, no (at P/Po = 1) of NaY,
KY, and BaY zeolites ar e der i ved f r om t he i nt ercept s
of t he DR plots (Figures 7 and 8). The value n o (Table
I) denot es t he maxi mum ads or bed amount accessible
to mi cropores. The amount s n o of p-xyl ene and m-xy-
l ene ads or bed on each zeolite at 150C are given in
Table 6. W o is t he vol ume of t he ads or bed amount n o
and n~, is t he t heoret i cal maxi mum amount of xylenes
which can be ads or bed into t he cryst al l ographi c vol-
ume V~, of 0t-cages. 1 Bot h of t hese values ar e calcu-
lated by t aki ng t he adsor bat e densi t y equal to t hat of
a pressuri zed gas accor di ng to t he assumpt i on of Ni-
0.5
0.4-
'
0.3
~ 0.2
0. 1
0 12
0C 200 C ~mX/BaY)
2
K
o
2 4 6 1 0
10" 6(Tlog(pJp))2/K 2
Figure 8 DR pl ot f or t he adsorpt i on of m-xyl ene on the BaY
zeolite.
kolaev et al. m4 Results show t hat t he average adsor p-
tion capacity is 3.5 mol ec. 0t-x f or t he NaY zeolite
and 3 mol ec or- 1 f or t he KY and BaY zeolites (Table
6). They conf i r m t he concl usi ons dr awn f r om adsor p-
tion equilibria in t he Part 1.1
Ent hal pi e s and e nt r o pi e s o f a ds o r pt i o n
The ent hal pi es and ent ropi es of adsor pt i on are ex-
pr essed in absol ut e value.
The ent hal pi es of adsor pt i on of xyl enes on NaY
and KY zeolites deduced f r om Henr y' s law and Lang-
mui r' s model (Tables 3 and 4) lie bet ween 50 and 70
1
k J - mo l - and ar e sl i ght l y l ower t han t hos e o f
s
Rut hven and Goddar d (Table 7). The ent hal pi es of
ads or pt i on of m-xyl ene (especi al l y t hose de duc e d
f r om Fowler' s model ) are gr eat er t han t hose of p-xy-
lene (Table 4).
The st andar d ent r opi es of adsor pt i on of xyl enes on
NaY and KY zeolites are of t he same or de r of mag-
ni t ude (Tables 3 and 4). However , t hey are gr eat er
with m-xylene t han with p-xyl ene in accor dance with
t he results of Gut h et al. 1~
The isosteric ent hal pi es and ent r opi es of adsor p-
tion [Aad~/,,(n)[ and IAadsS,,(n)[ (Figures 10- 12) are de-
ri ved f r om t he isosteres Ln(p/p ) = f ( 1/ T) , , pl ot t ed
f or each value of n by calculating t he p/pO ratio at a
given t emper at ur e with Langmui r' s equat i on f or NaY
and KY zeolites and t he DR equat i on f or t he BaY
zeolite. Ther ef or e t hese isosteric val ues (relative er r or
Table 5 Parameters of the DR equat i on f or t he adsorpt i on of
xyl enes on the BaY zeol i te
n o / ( mo l e c c= - 1 ) D/ K - 2
TIC p-xyl ene m-xyl ene p-xyl ene m-xyl ene
150 3.04 3.00
200 3.00 2.84
250 2.98 2.71
300 2.91 2.69
350 2.84 2.60
400 2.80 2.53
3.5 10 -8 4.09 10 - 8
Z e o l i t e s 1 5 : 2 1 9 - 2 2 7 , 1 9 9 5 2 2 3
Adsorption of gaseous p-xylene and m-xylene: J.-P. Bellat and M.-H. Simonot-Grange
Tabl e 6 Adsor pt i on capaci t i es of NaY, KY, and BaY zeol i tes at 150C f r om t he DR model
nod(molec. ~-1)
V~
Zeol i t e (cm 3 . g - 1 ) p- xyl ene rn- xyl ene
no/(molec. ~-1)
Wo/(cm 3 . g - 1)
p-xylene m-xylene m-xylene m-xylene
NaY 0. 284 3. 16 3. 22
KY 0. 271 3. 20 3. 25
BaY 0. 238 3. 18 3. 23
3. 43 3. 60 0. 307 0. 318
3. 10 2. 95 0. 262 0. 245
3. 04 3. 00 0. 227 0. 221
= 10%) are det ermi ned only in the filling range of
validity of the models (0 < n < n L and 0 < n < no).
The molar entropies of the adsorbate Sm(ads,T,n)
are calculated by subtracting the absolute entropies of
gaseous xylenes (Table 8) from the isosteric entropies
of adsorption.
Ad s o r p t i o n p r o c e s s
Fi l l i ng range 0 - 1 molec oL- 1
With the NaY zeolite the isosteric enthalpies of ad-
sorption in this range (Table 9) are rat her low and
invariant with the filling (Figure 10). This means that
the xylene molecules are adsorbed on sites (cations on
site II) with the same energy. The adsorption follows
Henry' s law and Langmuir' s model. The adsorbate-
adsorbate interactions are insignificant. At low filling,
the isosteric ent ropy of adsorption of m-xylene is
greater t han that of p-xylene (Table 9). It increases
with the filling, whereas that ofp-xylene remains con-
stant (Figure 11). It follows from this that the molar
entropy of the adsorbate Sm(ads,T,n) lies between the
standard entropy of the liquid and that of the gas
(Table 8) and is slightly greater with p-xylene than
with m-xylene (Figure 12). Then the adsorbate is like a
pressurized gas whose mobility would be greater with
p-xylene t han with m-xylene.
The adsorption process on the KY zeolite is of a
similar type. However, the isosteric enthalpies and
entropies of adsorption show that the aromatic ring-
cation interactions are lower, and the mobility of the
adsorbate is greater t han with the sodium cation. This
agrees with the fact that the K + cation has a lower
polarizing power t han the Na + cation.
With the BaY zeolite, the isosteric enthalpies of ad-
sorption at low filling are much higher than those of
the other zeolites (Table 9). They decrease as filling
increases (Figure 10). This characterizes an aromatic
ring-cation interaction stronger with Ba 2 + than with
Na* or K + and an energetic inhomogeneity of ad-
sorption sites. The isosteric entropies of adsorption at
low filling are also higher t han with the other zeolites
Tabl e 7 Ent hal pi es of adsor pt i on f r om l i t erat ure
AH(n ~ 0)/(kJ t ool -l )
Zeol i t e p- xyl ene m- xyl ene Ref erence
NaY 76 84
KY 76 78
NaY 76 86
KY 65 51
Ruthven and Goddard 3
(Henry's law)
Sant acesari a et al. 2"16
( cal ori met ry)
(Table 9, Figure I I ) . They are close to the standard
entropies of vaporization of xylenes (Table 8) and are
greater with m-xylene than with p-xylene. Such results
show that the adsorbate is analogous to a liquid whose
mobility would be greater with pxylene than with
m-xylene (Figure 13).
At low filling the isosteric enthalpy of adsorption of
p-xylene is equal to that of m-xylene on the BaY zeo-
lite (Table 9, Figure 12). It is greater with m-xylene
than with p-xylene on the NaY zeolite, whereas a re-
verse result is observed on the KY zeolite. This result
is in contradiction with that of Ruthven and God-
dard ~ but agrees with that of Santacesaria et al. 2'16
(Table 7). Such a result is not significant because the
di fference bet ween these isosteric ent hal pi es (5
kJ mol - l) is of the same order of magni t ude as the
experi ment al error ( - 6 kJ. mol -1). However, it
shows that the dipolar moment of the m-xylene mol-
ecule causes no promi nent specific interaction with
the adsorbent. 1
On the ot her hand, the m-xylene adsorbed in
oL-cages is more ordered than the p-xylene. Such a
result agrees with the neut ron diffraction experi-
ments carried on NaY, YbNaY, 17-19 and BaX 2 zeo-
lites. These results show that the first molecule of
m-xylene adsorbed on site II is not as mobile as that of
p-xylene. This stability of the adsorbed m-xylene is
attributed to its methyl groups, which are better di-
rected toward the oxygen atoms of the framework
than those of p-xylene to give optimal methyl-oxygen
interactions.
Fi l l i ng range 1 - 2 molec ot - 1
The isosteric enthalpies of adsorption of xylenes on
I SO-
~. 100
~ 50
(a) p-xylene
. . . . . v-a P- ~ iz a t i nnL~nn ~
o
0
0 i 2 3
(b) m-xylene
K_ y . . . . . . . . . /
n no
o i 2
n/(molec.a l)
Fi gure 10 I sosteri c ent hal pi es of adsor pt i on of p- x y l e ne (a) and
m- xyl ene (b) on NaY, KY, and BaY zeol i tes.
224 Zeol i tes 1 5 : 2 1 9 - 2 2 7 , 1 9 9 5
Adsorption of gaseous p-xylene and m-xylene: J.-P. Bellat and M.-H. Simonot-Grange
200
(a) p-xylene
E. 150 ~
~I~ vaporization E
100 . . . . . . .
E NaY~/ ~ L n /
KY
(b) m-xylene
NaY nL
N ~ nL n /
KY ,,
o i 2 3 , i S 6
n/(molec.~ l)
Figure 11 Isosteric entropi es of adsorpti on of p- xyl ene (a) and
m- xyl ene (b) on NaY, KY, and BaY zeolites.
150
. 1 0 0
0
NaY KY
pX
, , , , , . ,
0 1 2 0 1 2 0
n/(molee.a" l)
1 2 3
Figure 12 Compari son of isosteric enthal pi es of p- xyl ene ( )
and m- xyl ene ( O) on NaY, KY, and BaY zeolites.
Tabl e 8 Absol ut e entropi es of xyl enes
S O (298 K)/(J K - 1 . mol - 1)
Solid Liquid Gas
p- xyl ene 192 248 352
m-xylene 215 254 357
t he NaY zeolite do not vary f or filling r angi ng f r om 0
to 2 mol ec a - 1. The second mol ecul e is ads or bed by
t he same process as t he first (Figure 10). The mol ar
ent ropi es of t he adsor bat e (Figure 13) show t hat t he
ads or bed p-xyl ene r emai ns like a pr essur i zed gas,
whereas t he adsor bed m-xylene becomes anal ogous to
a liquid.
The isosteric ent hal pi es and ent r opi es of adsor p-
tion on t he KY zeolite i ncrease dur i ng t he adsor pt i on
of t he second mol ecul e so t hat t hey become gr eat er
t han t hose of t he NaY zeolite. The y are gr eat er with
m-xylene t han with p-xyl ene (Figure 12). Such a be-
havi or shows t hat t he adsor bat e- adsor bat e interac-
tions become mor e pr omi nent , especially with m-xy-
lene. They i nduce a mol ecul ar r ear r angement of t he
adsor bat e in such a way t hat it becomes like a liquid
with p-xyl ene and a solid with m-xylene. Thi s phe-
nomenon may be at t r i but ed to a steric effect caused
by t he bi g size o f K + cat i ons, x Th e a ds or ba t e -
adsor bat e i nt eract i ons ar e s t r onger wi t h m-xyl ene
( + k i n e t i c = 0.74 nm) t han with p-xyl ene ( + k i n e t i c = 0.67
nm). Thi s may expl ai n why Fowler' s model descri bes
t he adsor pt i on of m-xylene in this filling range.
As r egar ds t he BaY zeolite, t he isosteric ent hal pi es
of adsor pt i on (Figure 10) show t hat t he adsor pt i on of
t he second mol ecul e is less energet i c t han t he first.
The adsor bat e- adsor bat e i nt eract i ons ar e also st ron-
ger with m-xylene t han with p-xyl ene (Figure 12). The
adsor bed p-xyl ene is like a liquid, wher eas t he ad-
sor bed m-xylene is like a solid (Figure 13).
Fi l l i n g range 2 - 3 molec oL-1
Wi t h t he t hr ee zeolites, t he isosteric ent hal pi es and
ent ropi es of adsor pt i on of t he t hi rd mol ecul e rise to a
maxi mum and are gr eat er with m-xylene t han with
p- xyl e ne (Figures 1 0 - 1 2 ) . T h e n t he a d s o r b a t e -
adsor bat e interactions are maxi mum, and t he mobil-
ity of t he adsor bat e decreases greatly. The adsor bed
m-xylene is mor e or der ed in or-cages t han t he p-xy-
lene. Thi s behavi or is similar to t hat of benzene on
t he NaY zeolite ~I-2~ within t he cavities of which t he
benzene mol ecul es aggregat e to f or m a cl ust er at sat-
uration. It is in agr eement with t he i.r. spect roscopy
and neut r on di ffract i on results on NaY, KY, 15 and
BaX 2 zeolites which show t hat at hi gh filling ( 2- 3
mol e c , a - l ) t he a ds or ba t e - a ds or ba t e i nt er act i ons
l ead to a r ear r angement of m-xylene mol ecul es in
a-cages. The physical state of t he adsor bat e is t hen
like a solid. Wi t h p-xyl ene t he adsor bat e- adsor bat e
interactions are low. The adsor bat e is mor e mobi l e in
a-cages, and its physical state is close to a liquid. The n
Tabl e 9 Isosteric enthal pi es and entropi es of adsorpti on at l ow fi l l i ng
A o d , H m( n ~ 0) / ( kJ mo 1 - 1 )
A a a s S m( n ~ 0) / ( J K - 1 . mo l - 1 ) Sm(ads,n - 0 ) - / ( J K - 1 mo1- 1)
Zeol i te p - x y l e n e m- x y l e n e p - x y l e n e m- x y l e n e p - x y l e n e m- x y l e n e
NaY 70 75 70 78 282 279
KY 65 60 42 50 310 307
BaY 150 150 90 98 262 259
Z e o l i t e s 1 5 : 2 1 9 - 2 2 7 , 1 9 9 5 2 2 5
Adsorption of gaseous p-xylene and m-xylene: J.-P. Bellat and M.-H. Simonot-Grange
4 0 0
- - 3 5 0
O
"2.
[- 2 5 0
E 200
150
N a Y K Y B a Y
g a s
s o l i d
0 1 2 0 1 2 0 1 2 3
n / ( mo l e c . o ( l )
Figure 13
m-xylene.
Mol ar entropi es of t he adsorbate () p-xyl ene, ( 0 )
the isosteric enthalpies and entropies of adsorption
decrease to the enthalpies and entropies of vaporiza-
tion of xylenes as the adsorbate amount tends to the
upper limit of the validity range of the thermody-
namic model (n L and no) (Figures 10 and I1). The
0t-cages are almost filled, and the adsorption process
comes close to a condensation on the external surface
of the adsorbent.X
G i b b s e n e r g y a n d a c i d i t y o f t h e z e o l i t e
The cations and the oxygen atoms of the frame-
work of faujasites constitute Lewis conjugate acid-
base pairs. The acid strength of the zeolite can be
calculated by using the Sanderson electronegativity
equalization principle. 24-26 The greater the Sander-
son intermediate electronegativit~, Sint, 24 t h e stronger
2 5 2 6
the acid sites of the zeolite are. ' The calculation of
Sin t shows that the acid feature of NaY and KY zeo-
lites is similar and lower t han that of the BaY zeolite
(Figure 14).
Whatever may be the zeolite, the isosteric enthalp-
ies and entropies of adsorption of p-xylene and m-xy-
lene at low filling are nearly the same (Table 9). They
increase according to the sequence KY < NaY < BaY.
Those of NaY and KY zeolites are of the same order
of magni t ude (deviation ~10 kJ. mo1-1) and are
much lower t han those of the BaY zeolite. Therefore
the isosteric free enthalpies (Gibbs energy) of adsorp-
tion of p-xylene and m-xylene at low filling,
KY NaY BaY
J i m ~ Si nt
3.41 3.55 3.85
Basicity Acidity ~-
NaY, KY BaY iAadsG(423K,n~0) I
I I b .
y
-40 -110 (kJ.mol- I )
Figure 14 Isosteric free enthal pi es of adsorption at low filling
and acid feature of NaY, KY, and BaY zeolites at 150C.
AadsGm(T,n ~0) = AadsHm(n ~0) -- TAadsSm(n ~0) ,
on NaY and KY zeolites at 150C are equivalent and
much lower than those of the BaY zeolite (Figure 14).
Thus, at low filling the stronger the acid feature of
the zeolite, the greater the Gibbs energy of adsorp-
tion is. Among the NaY, KY, and BaY zeolites, that
exchanged with barium has the greatest ability to ad-
sorb xylenes. This result is confirmed on adsorption
isotherms that show at low pressure that the NaY and
KY zeolites (same acid feature) adsorb xylenes in the
same way, whereas the BaY zeolite (strong acid fea-
ture) adsorbs much more xylene t han the two others.
C O N C L U S I O N S
For relative pressure ranging from 10 -4 to 10 -2, the
adsorption isotherms of xylenes on NaY and KY ze-
olites are described accurately by Henry' s law and
Langmuir' s model. With moxylene Fowler's model is
valid too, but the fit with the experi ment is not as
accurate as with Langmuir' s model. The adsorption
isotherms of xylenes on the BaY zeolite are described
only by the DR model.
The isosteric enthalpies of adsorption at low filling
show that the adsorbate-adsorbent interactions are
the same with both isomers. They are much stronger
on the BaY zeolite than on the two others. The dipo-
lar moment of the m, xylene molecule does not cause
promi nent specific interactions with the adsorbent.
The adsorbate-adsorbate interactions increase with
the filling of the zeolite. They are especially strong on
the KY zeolite because of the steric hi ndrance caused
by the four big K + cations in the tx-cage.
The isosteric entropies of adsorption show that the
adsorbate is more mobile in oL-cages with p-xylene
than with m-xylene.
The isosteric free enthalpies of adsorption are re-
lated to the acid feature of the zeolite by using the
Sanderson intermediate electronegativity. The stron-
ger the acid feature of the Y faujasite, the greater is
its ability to adsorb xylenes.
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