Basi s of Permeabi l i ty/Sel ecti vi ty Tradeoff Rel ati ons i n Pol ymeri c Gas

Separati on Membranes
Benny D. Freeman

Department of Chemical Engineering, North Carolina StateUniversity, Campus Box 7905,

Raleigh, North Carolina 27695-7905
Received September 14, 1998; Revised Manuscript Received November 30, 1998
ABSTRACT: Gas separati on properti es of pol ymer membrane materi al s fol l ow di sti nct tradeoff rel a-
ti ons: more permeabl e pol ymers are general l y l ess sel ecti ve and vi ce versa. Robeson
1
i denti fi ed the best
combi nati ons of permeabi l i ty and sel ecti vi ty for i mportant bi nary gas pai rs (O2/N2, CO2/CH4, H2/N2, etc.)
and represented these permeabi l i ty/sel ecti vi ty combi nati ons empi ri cal l y as RA/B ) A/BP
A
-
A/B
, where PA
and PB are the permeabi l i ty coeffi ci ents of the more permeabl e and l ess permeabl e gases, respecti vel y,
RA/B i s sel ecti vi ty ()PA/PB), and A/B and A/B are empi ri cal parameters. Thi s report provi des a fundamental
theory for thi s observati on. I n the theory, A/B depends onl y on gas si ze. A/B depends on A/B, gas
condensabi l i ty, and one adjustabl e parameter.
Introduction and Background
Pol ymer membranes are used commerci al l y to sepa-
rate ai r, to remove carbon di oxi de from natural gas, and
to remove hydrogen from mi xtures wi th ni trogen or
hydrocarbons i n petrochemi cal processi ng appl i cati ons.
2
For a gi ven pai r of gases (e.g., O
2
/N
2
, CO
2
/CH
4
, H
2
/N
2
,
etc.), the fundamental parameters characteri zi ng mem-
brane separati on performance are the permeabi l i ty
coeffi ci ent, P
A
, and the sel ecti vi ty, R
A/B
. The permeabi l i ty
coeffi ci ent i s the product of gas fl ux and membrane
thi ckness di vi ded by the pressure di fference across the
membrane. Gas sel ecti vi ty i s the rati o of permeabi l i ty
coeffi ci ents of two gases (R
A/B
) P
A
/P
B
), where P
A
i s the
permeabi l i ty of the more permeabl e gas and P
B
i s the
permeabi l i ty of the l ess permeabl e gas i n the bi nary gas
pai r.
Pol ymers wi th both hi gh permeabi l i ty and sel ecti vi ty
are desi rabl e. Hi gher permeabi l i ty decreases the amount
of membrane area requi red to treat a gi ven amount of
gas, thereby decreasi ng the capi tal cost of membrane
uni ts. Hi gher sel ecti vi ty resul ts i n hi gher puri ty product
gas. Over the past 25 years, the gas separati on proper-
ti es of many pol ymers have been measured, and a
substanti al research effort i n i ndustri al , government,
and uni versi ty research l aboratori es has resul ted i n
pol ymers that are both more permeabl e and more
sel ecti ve than fi rst generati on materi al s.
3
A rather general tradeoff rel ati on has been recogni zed
between permeabi l i ty and sel ecti vi ty: Pol ymers that are
more permeabl e are general l y l ess sel ecti ve and vi ce
versa.
1,3
On the basi s of an exhausti ve l i terature survey,
Robeson
1,4
quanti fi ed thi s noti on by graphi ng the avai l -
abl e data as shown i n Fi gure 1, whi ch presents hydro-
gen permeabi l i ty coeffi ci ents and H
2
/N
2
separati on
factors for many pol ymers. Materi al s wi th the best
performance woul d be i n the upper ri ght-hand corner
of thi s fi gure. However, materi al s wi th permeabi l i ty/
sel ecti vi ty combi nati ons above and to the ri ght of the
l i ne drawn i n thi s fi gure are excepti onal l y rare. Thi s
l i ne defi nes the so-cal l ed upper bound combi nati ons
of permeabi l i ty and sel ecti vi ty of known pol ymer mem-
brane materi al s for thi s parti cul ar gas pai r. Li nes such
as the one shown i n Fi gure 1 were constructed on an
empi ri cal basi s for many gas pai rs usi ng publ i shed
permeabi l i ty and sel ecti vi ty data. The upper bound
performance characteri sti cs were best descri bed by the
fol l owi ng equati on:
1
whi ch i ndi cates that as the permeabi l i ty of an upper
bound pol ymer to gas A, P
A
, i ncreases, sel ecti vi ty of the
pol ymer for gas A over gas B, R
A/B
, decreases. Robeson
reports val ues for
A/B
and
A/B
for many common gas
pai rs.
1,4
The reason for thi s tradeoff has been wi del y di scussed,
but no theoreti cal justi fi cati on of the form of eq 1 or
fundamental predi cti ons of
A/B
and
A/B
have been
offered. Robeson noted an excel l ent empi ri cal correl ati on

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Figure 1. Rel ati onshi p between hydrogen permeabi l i ty and
H2/N2 sel ecti vi ty for rubbery (O) and gl assy (b) pol ymers and
the empi ri cal upper bound rel ati on.
1
R
A/B
)
A/B
/P
A

A/B
(1)
375 Macromolecules 1999, 32, 375-380
10.1021/ma9814548 CCC: $18.00 1999 Ameri can Chemi cal Soci ety
Publ i shed on Web 01/05/1999
between
A/B
and the di fference between the ki neti c
di ameters of the penetrant mol ecul es, d
B
- d
A
.
1
The
theory presented i n thi s arti cl e gi ves excel l ent predi c-
ti ons of
A/B
wi th no adjustabl e parameters and suggests
that the sl ope of the upper bound i s a natural conse-
quence of the strong si ze-si evi ng nature of the sti ff chai n
gl assy pol ymeri c materi al s whose properti es general l y
defi ne the upper bound. Moreover, the theory provi des
good esti mates of
A/B
wi th onl y one adjustabl e param-
eter. The theory i s devel oped for amorphous pol ymers
and does not account for the i nfl uence of penetrant
concentrati on on permeati on properti es.
Theory
As Si r Thomas Graham proposed,
5
the transport of
gases i n dense, nonporous pol ymers obeys a sol uti on
di ffusi on mechani sm. Under the dri vi ng force of a
pressure di fference across a membrane, penetrant
mol ecul es di ssol ve i n the upstream (or hi gh pressure)
face of a membrane, di ffuse across the membrane, and
desorb from the downstream (or l ow pressure) face of
the membrane. Di ffusi on i s the rate-control l i ng step i n
penetrant permeati on. The rate-control l i ng process i n
di ffusi on i s the creati on of gaps i n the pol ymer matri x
suffi ci entl y l arge to accommodate penetrant mol ecul es
by thermal l y sti mul ated, random l ocal segmental
pol ymer dynami cs.
3,6
Based on thi s mechani sm, the
permeabi l i ty coeffi ci ent of a pol ymer to gas A can be
wri tten as
where S
A
i s the sol ubi l i ty coeffi ci ent and D
A
i s the
di ffusi on coeffi ci ent of gas A.
The sel ecti vi ty of a pol ymer for gas A over gas B, R
A/B
,
i s gi ven by
The di ffusi on of smal l mol ecul es i s an acti vated process,
and at temperatures away from thermal transi ti ons i n
the pol ymer (e.g., gl ass transi ti on, mel ti ng, etc.), the
Arrheni us equati on i s obeyed:
7
where D
oA
i s a front factor, E
DA
i s the acti vati on energy
for di ffusi on, R i s the gas constant, and T i s the absol ute
temperature. Barrer
8
and Van Amerongen
9
observed a
si mpl e correl ati on between the front factor and acti va-
ti on energy:
where a and bare i ndependent of gas type. Addi ti onal l y,
a i s i ndependent of pol ymer type and has a uni versal
val ue of 0.64.
10
b has a val ue of -l n(10
-4
cm
2
/s) ) 9.2
for rubbery pol ymers and -l n(10
-5
cm
2
/s) ) 11.5 for
gl assy pol ymers.
11
Equati on 5 i s often referred to as a
l i near free energy rel ati on. Si mi l ar rel ati ons between
front factors and acti vati on energi es are observed for
vi scosi ty of organi c l i qui ds, mol ten sal ts, and metal s
12
and for fi rst-order chemi cal reacti on ki neti cs,
13
whi ch
are al so acti vated processes descri bed by the Arrheni us
equati on.
Two expl anati ons have been proposed to justi fy eq 5.
Fi rst, Barrer noted that eq 5 may be the resul t of a
rather si mpl e compensati on effect.
10
The range of l n
D
A
i n eq 4 i s al ways smal l rel ati ve to that of E
DA
/RT.
10
Therefore, to a fi rst approxi mati on i n many cases, l n
D
A
i s al most constant over the ranges of temperature
typi cal l y expl ored. The parameters E
DA
and D
oA
i n eq 4
are determi ned by curve fi tti ng the data to thi s equa-
ti on. Any uncertai nty i n the val ue of E
DA
(determi ned
from the curve fi t) that acts to i ncrease the apparent
E
DA
i s compensated for by an i ncrease i n the apparent
val ue of D
oA
and vi ce versa. Si mi l ar arguments have
been advanced to account for the rel ati onshi p between
front factors and acti vati on energi es for vi scosi ty.
14
On
thi s basi s, eq 5 i s si mpl y a mathemati cal arti fact.
Second, wi thi n the framework of the Eyri ngs acti -
vated state theory, l n D
oA
i s proporti onal to the entropy
change of acti vati on.
15
I n thi s context, eq 5 i ndi cates
that acti vati on entropy i s di rectl y proporti onal to acti -
vati on energy. A l i near free energy rel ati on i n chemi cal
ki neti cs i s i nterpreted to mean that the reacti on
mechani sm i s si mi l ar among a rel ated seri es of reac-
ti ons.
13
By anal ogy, the mechani sm of smal l mol ecul e
di ffusi on i n pol ymers i s taken to be si mi l ar among a
vari ety of pol ymers when eq 5 i s obeyed. However,
mechani sti c di fferences may exi st between gl assy and
rubbery pol ymers si nce b i s substanti al l y hi gher for
gl assy pol ymers than for rubbery pol ymers. At a fi xed
acti vati on energy and assumi ng the penetrant jump
l ength i s not strongl y di fferent i n rubbery and gl assy
pol ymers, the acti vati on entropy i s an order of
magni tude l ower i n gl assy pol ymers than i n rubbery
pol ymers.
16
I nteresti ngl y, the pol ymers that defi ne the
upper bound rel ati on i n Fi gure 1 and i n rel ated pl ots
for other l i ght gas pai rs are sti ff-chai n, amorphous
gl assy pol ymers.
1
On the basi s of conti nuum mechani cs model s for the
creati on of hol es or vacanci es i n materi al s, Lawson
16
and
Keyes
17
suggested that the rati o of acti vati on entropy
to acti vati on energy shoul d be approxi matel y 4 ti mes
the thermal expansi on coeffi ci ent, whi ch has been
observed i n some cases for di ffusi on of smal l mol ecul es
i n pol ymers. Al ternati vel y, accordi ng to Barrers zone
theory of di ffusi on, a penetrant executes a di ffusi on
jump i n an acti vated regi on (or zone) compri si ng seg-
ments of pol ymer mol ecul es near the di ffusi ng penetrant
mol ecul e. The si ze of the acti vated zone determi nes both
E
DA
and acti vati on entropy or, equi val entl y, l n D
oA
.
8
The
l arger the si ze of the acti vated zone requi red for
di ffusi on, the hi gher i s the energy, E
DA
, requi red to
create i t and the l arger i s the entropy change associ ated
wi th the creati on of the acti vated state.
I n addi ti on to eq 5, the theory requi res a rel ati on
between acti vati on energy and penetrant si ze. Van
Krevel en reports that acti vati on energy of di ffusi on
correl ates best wi th the square of penetrant di ameter
for a wi de range of pol ymers and does not provi de
separate correl ati ons for rubbery and gl assy pol ymers.
11
Meares found that the acti vati on energy of gas di ffusi on
coeffi ci ents i n pol y(vi nyl acetate) i ncreased l i nearl y wi th
penetrant col l i si on di ameter squared both above and
bel ow the gl ass transi ti on temperature.
18
Meares
P
A
) S
A
D
A
(2)
R
A/B
)
P
A
P
B
)
S
A
S
B
D
A
D
B
(3)
D
A
) D
o
A
exp
(
-
E
D
A
RT
)
(4)
l n D
o
A
) a
E
D
A
RT
- b (5)
376 Freeman Macromolecules, Vol. 32, No. 2, 1999
devel oped a qual i tati ve macroscopi c expl anati on of these
resul ts based on the noti on that the acti vati on energy
i s proporti onal to the vol ume of the acti vated state,
whi ch i s proporti onal to the product of penetrant
di ameter squared and penetrant jump l ength.
18
Other
more recent model s, such as Brandts model , al so
provi de support for the noti on that acti vati on energy
depends on the penetrant di ameter squared for sti ff-
chai n gl assy pol ymers such as those that defi ne the
upper bound rel ati ons.
19
I n gl assy pol ymers, acti vati on
energy vs penetrant di ameter squared pl ots usual l y
extrapol ate to acti vati on energi es of zero for fi ni te
si zed penetrants.
6,20
Brandts model ascri bes thi s
observati on to the exi stence of a fi ni te i nterchai n
separati on i n the nonacti vated or equi l i bri um state.
19
Therefore, the effect of penetrant si ze on acti vati on
energy i s model ed as fol l ows:
where c and f are constants whi ch depend on the
pol ymer, and d
A
i s the penetrant di ameter. For l i ght
gases, the ki neti c di ameter, whi ch characteri zes the
smal l est zeol i te wi ndow through whi ch a penetrant
mol ecul e can fi t,
21
i s the most appropri ate measure of
penetrant si ze for transport property correl ati ons.
6,11
Therefore, i n thi s work, d
A
i s taken to be the ki neti c
di ameter of the penetrant. Van Krevel en reports c
val ues from 250 for extremel y fl exi bl e pol y(di methyl -
si l oxane) to approxi matel y 1100 cal /(mol
2
) for sti ff-
chai n, gl assy pol y(vi nyl chl ori de).
11
Pol ymers that
have hi gh di ffusi vi ty sel ecti vi ty shoul d have hi gh val ues
of c. I n thi s regard, for a hi gh-performance gl assy
pol yi mi de (synthesi zed from 3,3,4,4-bi phenyl tetra-
carboxyl i c di anhydri de and 4,4-di ami nodi phenyl ether),
the val ue of c may be as hi gh as 2400 cal /(mol
2
).
22
The val ue of f ranges from 0 for rubbery pol ymers and
low-performance glassy polymers to approximately 14 000
cal /mol for the pol yi mi de prepared by Haraya et al .
22
The rati o f/c i s a crude measure of the average
di stance between pol ymer chai ns. For the pol yi mi de just
descri bed, f/c i s 2.5 .
Equati on 6 shoul d appl y to pol ymers wi th i nterchai n
spaci ngs on the order of or smal l er than the si ze of the
penetrant mol ecul es so that thermal l y acti vated moti on
of pol ymer chai n segments control s penetrant di ffusi on.
The theory i s not expected to be val i d i f the i nterchai n
spaci ngs are si gni fi cantl y l arger than the si ze of the
penetrant mol ecul es because, i n thi s case, the rate-
l i mi ti ng step for penetrant di ffusi on woul d not neces-
sari l y be control l ed by pol ymer chai n moti on. The theory
i s restri cted to l i ght gas mol ecul es, such as He, H
2
, N
2
,
O
2
, CO
2
, CH
4
, and the l i ke, where gas ki neti c di ameter
provi des a good measure of penetrant si ze as i t rel ates
to transport properti es. For l arger penetrants (e.g., d
A
> 4.4 for pol y(vi nyl acetate)
20
) the acti vati on energy
versus penetrant di ameter squared rel ati on becomes
concave to the penetrant si ze axi s. Moreover, for l arger
penetrants, ki neti c di ameter i s not a good esti mate of
penetrant si ze i mportant for transport properti es.
23
I n
these cases, eq 6 i s not stri ctl y obeyed, and the theory
wi l l not be val i d.
Combi ni ng eqs 4, 5, and 6 gi ves the fol l owi ng expres-
si on for the di ffusi on coeffi ci ent:
Thus, wi thi n the scope of thi s theory, the l ogari thm of
gas di ffusi vi ty decreases i n proporti on to penetrant
di ameter squared. Thi s scal i ng of di ffusi on coeffi ci ent
wi th penetrant si ze i s consi stent wi th the empi ri cal
correl ati ons of Van Krevel en
11
and Tepl yakov and
Meares.
24
Based on eqs 2 and 7, the permeabi l i ty
coeffi ci ent i s
and sel ecti vi ty i s
Combi ni ng eqs 8 and 9 yi el ds
Equati on 10 i s the pri mary resul t of thi s theory and can
be used to gauge sel ecti vi ty changes as one expl ores
vari ous pol ymers wi th di fferent permeabi l i ty coeffi -
ci ents. Thi s equati on i s based on the four hypotheses
embodi ed i n eqs 2, 4, 5, and 6.
For a wi de range of pol ymers, sol ubi l i ty and sol ubi l i ty
sel ecti vi ty change much l ess than ei ther sel ecti vi ty
or permeabi l i ty coeffi ci ents.
1
Therefore, for a parti cul ar
gas pai r and a fi xed val ue of the parameter f, the term
i n curl y brackets i n eq 10 changes l i ttl e from one
pol ymer to another. I n thi s case, the l ogari thm of
sel ecti vi ty shoul d decrease l i nearl y as the l ogari thm of
permeabi l i ty i ncreases, consi stent wi th the empi ri cal
upper bound l i ne i n Fi gure 1. Equati on 10 has the
same mathemati cal form as the empi ri cal rel ati on
reported by Robeson i f
A/B
and
A/B
i n eq 1 are i denti fi ed
as fol l ows:
and
Usi ng ki neti c di ameters for d
A
and d
B
i n eq 11, the
sl opes of the l n R
A/B
vs l n P
A
pl ots were cal cul ated and
compared wi th the empi ri cal l y determi ned sl opes from
Robeson
1,4
i n Fi gure 2. The ki neti c di ameters used for
thi s cal cul ati on are gi ven i n Tabl e 1. I n general , the
agreement between the cal cul ated and observed sl opes
i s stri ki ngl y good gi ven the approxi mate nature of the
sl opes and the fact that the predi cti ons are based on a
theory wi th no adjustabl e parameters.
Robeson observed an excel l ent empi ri cal correl ati on
of
A/B
wi th the di fference between the ki neti c di ameters
(i n angstroms) of the gas mol ecul es:
1
I f the expressi on for
A/B
i n eq 11 i s rewri tten as fol l ows
E
D
A
) cd
A
2
- f (6)
l n D
A
) -
(
1 - a
RT
)
cd
A
2
+ f
(
1 - a
RT
)
- b (7)
l n P
A
) -
(
1 - a
RT
)
cd
A
2
+ f
(
1 - a
RT
)
- b + l n S
A
(8)
l n R
A/B
) l n(S
A
/S
B
) + l n(D
A
/D
B
) ) l n(S
A
/S
B
) +
(
1 - a
RT
)
c(d
B
2
- d
A
2
) (9)
l n R
A/B
) -
[(
d
B
d
A
)
2
- 1
]
l n P
A
+
{
l n
(
S
A
S
B
)
-
[(
d
B
d
A
)
2
- 1
]

(
b - f
(
1 - a
RT
)
- l n S
A)}
(10)

A/B
) (d
B
/d
A
)
2
- 1 (11)

A/B
)
S
A
S
B
S
A

A/B
exp
{
-
A/B[
b - f
(
1 - a
RT
)]}
(12)

A/B
) d
B
- d
A
(13)
Macromolecules, Vol. 32, No. 2, 1999 Pol ymeri c Gas Separati on Membranes 377
then eq 13 wi l l provi de as good a correl ati on for
A/B
as
eq 11 i f the term i n square brackets i s constant. For
the penetrant pai rs i n Fi gure 2, the term i n square
brackets i s approxi matel y 0.8 and exhi bi ts l i ttl e
vari ati on. For exampl e, the l owest val ue of the term i n
square brackets i s 0.60 for O
2
/N
2
, and the hi ghest val ue
i s 0.95 for He/N
2
. I n contrast,
A/B
val ues for these gas
pai rs vary by more than a factor of 7. Thus, the good
agreement that Robeson observed usi ng eq 13 i s
consi stent wi th theory si nce the term i n square brackets
i n eq 14 vari es l i ttl e among the gas pai rs consi dered.
To esti mate
A/B
, sol ubi l i ty and sol ubi l i ty sel ecti vi ty
val ues for di fferent gases are requi red. Addi ti onal l y, the
parameter f i s not prescri bed by thi s treatment and i s
treated as an adjustabl e parameter. Li ke gas di ssol uti on
i n l i qui ds, penetrant di ssol uti on i n pol ymers i s regarded
as a two step thermodynami c process: (1) condensati on
of the gaseous penetrant to a l i qui dl i ke densi ty and (2)
mi xi ng of the pure compressed penetrant wi th the
pol ymer segments.
6
The fi rst step i s governed by
penetrant condensabi l i ty, and the second depends
on pol ymer -penetrant i nteracti ons. For l i ght gas
penetrants that do not undergo speci fi c i nteracti ons
wi th the pol ymer, the fi rst effect i s often domi nant, and
as a resul t, penetrant sol ubi l i ty i n pol ymers typi cal l y
scal es wi th conveni ent measures of penetrant condens-
abi l i ty, such as penetrant boi l i ng poi nt, cri ti cal temper-
ature, or Lennard-Jones temperature, /k.
6
For the
l atter, k i s Bol tzmanns constant, and i s the potenti al
energy wel l depth parameter i n the Lennard-Jones
potenti al energy functi on. A model of penetrant
sol ubi l i ty i n pol ymers, devel oped from cl assi cal
thermodynami cs, gi ves the fol l owi ng rel ati on between
penetrant Lennard-Jones temperature and gas
sol ubi l i ty i n amorphous pol ymers where strong speci fi c
pol ymer-penetrant i nteracti ons (e.g., hydrogen
bondi ng) are not i mportant:
24,25
where M and N are parameters. For a vari ety of l i qui ds,
rubbery pol ymers, and gl assy pol ymers, N i s 0.023
K
-1
.
6,11
M i s sensi ti ve to pol ymer-penetrant i nter-
acti ons and, consequentl y, vari es somewhat from
pol ymer to pol ymer. However, for si mpl i ci ty, M i s
constrai ned to a constant val ue. Accordi ngl y, Van
Krevel en recommends a val ue of -9.84 (wi th sol ubi l i ty
i n uni ts of cm
3
(STP)/(cm
3
cmHg)).
11
Equati on 15 can
be used to cal cul ate sol ubi l i ty sel ecti vi ty: l n(S
A
/S
B
) )
N(
A
/k -
B
/k). As the parameter N has the same val ue
for many materi al s, predi cti ons of sol ubi l i ty sel ecti vi ty
shoul d be more accurate than predi cti ons of sol ubi l i ty.
Equati on 15 was used i n eq 12 to esti mate
A/B
as
shown bel ow:
These val ues are compared i n Fi gure 3 wi th the
A/B
val ues reported by Robeson. The Lennard-Jones
temperatures are recorded i n Tabl e 1. Equati on 16
contai ns one adjustabl e parameter, f. For si mpl i ci ty, thi s
parameter was constrai ned to be a constant for al l gas
pai rs, and i ts val ue was determi ned by a l east-squares
mi ni mi zati on procedure assumi ng that the experi ment
temperature, T, was 298 K. I f some of the data were
determi ned at other temperatures, then the val ue of f
woul d be adjusted accordi ngl y. The best val ue of f was
approxi matel y 12 600 cal /mol .
(
d
B
d
A
)
2
- 1 )
[
d
B
+ d
A
d
A
2
]
(d
B
- d
A
) (14)
l n S
A
) M + N(
A
/k) (15)

A/B
) N
(

A
k
-

B
k
)(
M + N

A
k
)

A/B

exp
{
-
A/B[
b - f
(
1 - a
RT
)]
}
(16)
Figure2. Compari son of sl opes of l n RA/B vs l n PA pl ots, A/B,
reported by Robeson
1,4
wi th theoreti cal predi cti on (sol i d l i ne).
Gas pai rs are l i sted as A/B (i .e., O2/N2 i mpl i es that O2 ) A
and N2 ) B). dA and dB are the ki neti c di ameters of penetrants
A and B, respecti vel y, taken from the tabul ati on by Breck.
21
Figure3. Compari son of front factors of l n RA/B vs l n PA pl ots,
A/B, reported by Robeson
1,4
wi th theoreti cal predi cti on (sol i d
l i ne). The best fi t of the data to the theory i s obtai ned wi th
the parameter f set to 12 600 cal /mol . The uni ts of A/B are
[cm
3
(STP) cm/(cm
2
s cmHg)]

A/B.
Table 1. Penetrant Size and Condensability Parameters
penetrant
ki neti c
di am ()
21
/k
(K)
11
penetrant
ki neti c
di am ()
21
/k
(K)
11
He 2.69 10.2 O2 3.46 107
H2 2.8 60 N2 3.64 71
CO2 3.3 195 CH4 3.87 149
378 Freeman Macromolecules, Vol. 32, No. 2, 1999
The agreement of the theory wi th Robesons val ues
i s i mpressi ve consi deri ng that onl y one adjustabl e
parameter i s used to descri be the upper bound
permeabi l i ty/sel ecti vi ty behavi or of these 11 gas pai rs.
However, for some gas pai rs, there are si gni fi cant
devi ati ons between the cal cul ated front factors and
those reported by Robeson. The assumpti on that M and
f are constant for al l pol ymers that mi ght l i e on the
upper bound for al l of these gas pai rs i s cl earl y a strong
approxi mati on whi ch coul d be rel axed i f one were
i nterested i n predi cti ons rel ated to speci fi c gas pai r/
pol ymer combi nati ons. Al so, the upper bound l i nes were
drawn somewhat subjecti vel y, and some di sagreement
wi th the theory i s not surpri si ng.
Implications and Conclusions
Equati on 10 can be wri tten as
Thi s form of eq 10 hi ghl i ghts the i mpact of changes i n
penetrant di ffusi on coeffi ci ents from pol ymer to pol ymer
on the upper bound sel ecti vi ty. The sol ubi l i ty sel ecti vi ty
term i n eq 17 shoul d change l i ttl e from pol ymer to
pol ymer, and the term
A/B
b i s a constant for a gi ven
gas pai r and a gi ven pol ymer cl ass (i .e., rubbery or
gl assy). Thi s resul t, that di ffusi vi ty shoul d pl ay a more
i mportant rol e than sol ubi l i ty i n determi ni ng upper
bound sel ecti vi ty val ues, i s consi stent wi th the
concl usi ons of Robeson.
1
The theory al so provi des a
rati onal e for the fol l owi ng heuri sti c that has emerged
as a resul t of many years of systemati c experi mental
structure/property studi es:
3,6
for these l i ght gas pai rs,
the most producti ve route di scovered to i mprove
permeabi l i ty/sel ecti vi ty properti es i s to modi fy pol ymer
chemi cal structure to i ncrease pol ymer backbone
sti ffness (i .e., i ncrease c, whi ch i ncreases R
A/B
(cf. eq 9))
whi l e si mul taneousl y di srupti ng i nterchai n packi ng to
i ncrease f, thereby i ncreasi ng di ffusi vi ty and, i n turn,
permeabi l i ty (cf. eq 8).
Based on the agreement of the theory wi th the
experi mental data for many gas pai rs, the fundamental
characteri sti cs of pol ymers wi th outstandi ng gas
separati on properti es for one pai r of gases are shared
by pol ymers havi ng excel l ent separati on properti es for
other gas pai rs. I ndeed, Robeson noted that some hi gh
gl ass transi ti on temperature, ri gi d backbone, amor-
phous pol ymers wi th rel ati vel y l arge i nterchai n spaci ngs
(i .e., hi gh fracti onal free vol ume) l i e on or near the upper
bound l i nes for many gas pai rs.
1
Of course, the vast
majori ty of pol ymers do not l i e on the upper bound l i nes.
Rubbery pol ymers general l y si eve penetrants weakl y
based on si ze, so the parameter c i n eq 6 i s l ow or the
acti vati on energy i s proporti onal to onl y the fi rst power
of penetrant di ameter. Both of these characteri sti cs
move pol ymers away from the upper bound l i nes.
Addi ti onal l y, i f i nterchai n spaci ng i s l ow, f wi l l be l ower,
thereby decreasi ng di ffusi on coeffi ci ents (cf. eq 7) and,
i n turn, permeabi l i ty coeffi ci ents.
Wi thi n the scope of thi s si mpl e theory, there i s no
i nfl uence of pol ymer structure on the sl ope of the upper
bound or tradeoff curves,
A/B
, as thi s parameter
depends onl y on penetrant si ze rati o. I f thi s i s true, then
the sl opes of the upper bound l i nes are unl i kel y to
change wi th further pol ymer devel opment efforts. I n
contrast,
A/B
contai ns vari abl es that can be systemati -
cal l y tuned by rati onal pol ymer structure mani pul ati on
to si mul taneousl y i mprove permeabi l i ty and sel ecti vi ty
characteri sti cs. I n thi s regard, the most frui tful pathway
for devel opment of hi gher performance pol ymeri c
membranes for the separati ons di scussed i n thi s paper
i s to systemati cal l y i ncrease
A/B
, ei ther through sol ubi l -
i ty sel ecti vi ty enhancement and/or i ncreases i n chai n
sti ffness (i .e., i ncreasi ng c), whi l e si mul taneousl y
i ncreasi ng i nterchai n spaci ng (i .e., fracti onal free
vol ume), to i ncrease sel ecti vi ty whi l e mai ntai ni ng or
i ncreasi ng permeabi l i ty. I ncreasi ng i nterchai n
separati on to i ncrease permeabi l i ty wi thout sacri fi ci ng
sel ecti vi ty shoul d onl y be effecti ve as l ong as the
i nterchai n separati on i s not so l arge that penetrant
di ffusi on coeffi ci ents are no l onger governed by
thermal l y sti mul ated pol ymer segmental moti ons.
Materi al s that are beyond thi s l i mi t may al ready exi st.
Pol y(1-tri methyl si l yl -1-propyne), the most permeabl e
pol ymer known and the pol ymer whi ch has the hi ghest
free vol ume of al l hydrocarbon-based pol ymers, al so has
the l owest sel ecti vi ti es for permanent gases (e.g., O
2
/
N
2
) of al l pol ymers and exhi bi ts many permeati on
characteri sti cs si mi l ar to those of mi croporous
materi al s.
26-28
Si mpl y i ncreasi ng pol ymer backbone sti ffness (to the
extent that thi s i ncreases c i n eqs 7 and 9) resul ts i n
i ncreased sel ecti vi ty but l ower di ffusi vi ty and, therefore,
permeabi l i ty. So backbone sti ffness i ncreases shoul d be
coupl ed wi th i ncreases i n i nterchai n separati on to
achi eve both hi gher permeabi l i ty and hi gher sel ecti vi ty.
These si mpl e consi derati ons suggest that si mul taneous
chai n sti ffness and i nterchai n separati on i ncreases can
be used to systemati cal l y i mprove separati on perfor-
mance unti l the i nterchai n separati on becomes l arge
enough that the pol ymer segmental moti on no l onger
governs penetrant di ffusi on. As i ndi cated above, unl ess
si gni fi cant enhancement i n sol ubi l i ty sel ecti vi ty coul d
be achi eved, thi s l i mi t woul d represent the asymptoti c
end poi nt i n the performance of pol ymeri c membranes
whose separati on properti es are di ctated by the hypoth-
eses embodi ed i n eqs 2, 4, 5, and 6. To achi eve sti l l
hi gher sel ecti vi ty/permeabi l i ty combi nati ons, materi al s
that do not obey these si mpl e rul es woul d be requi red.
References and Notes
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Separation Membranes; CRC Press: Boca Raton, FL, 1994.
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C.; Ti en, C. F. Polymer 1994, 35, 4970.
(5) Graham, T. Philos. Mag. 1866, 32, 401.
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Di ffusi on of Gases i n Pol ymers. I n PolymericGas Separation
Membranes; Paul , D. R., Yampol ski i , Y. P., Eds.; CRC
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(7) Barrer, R. M. Trans. Faraday Soc. 1939, 35, 644.
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l n R
A/B
) -
A/B
l n D
A
+
{
l n
(
S
A
S
B
)
-
A/B(
b - f
(
1 - a
RT
))}
(17)
Macromolecules, Vol. 32, No. 2, 1999 Pol ymeri c Gas Separati on Membranes 379
(18) Meares, P. J . Am. Chem. Soc. 1954, 76, 3415.
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MA9814548
380 Freeman Macromolecules, Vol. 32, No. 2, 1999