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Solution and Diffusion of Helium and Neon in

Tridymite and Cristobalite
BY R. M. BARRERAND D. E. W. VAUGHAN
Physical Chemistry Laboratories, Chemistry Dept., Imperial College, London, S.W.7

Received 8th May, 1967

The solution and trapping of helium and neon has been studied in cristobalite in the range 293857K and in tridymite between 293 and 838K. These temperatures cover regions in which (x- and
P-cristobalite and a-, PI- and P2-tridymite are found. The solubilities are considerable, those in
tridymite being close to solubilities in silica glass and those in cristobalite rather less. Heats of
solution were evaluated from isotherms and had the same signs as those in silica glass. The results
were discussed in terms of an oscillator model for dissolved atoms. For some of the systems approximate diffusion coefficients were obtained which could be represented by the Arrhenius equation :
exp - 12000/RT cm2 sec-',
He in a-tridymite (236-336K) : D = 7.7 x
He in a-cristobalite (244-335K) : D = 2-0x
exp - 13800/RT cm2 sec-I,
exp -22500/RT cm2 sec-',
Ne in a-tridymite (336-366K) : D = 6.7 x
Ne in P,-tridymite (418-474K) : D = 9.9 x lo-' exp -24100/RT cmz sec-',
Ne in p2-tridymite (513-577K) : D = 4.5 x
exp - 19100/RT cm2 sec-I.
Energies of activation are about twice their values in silica glass and diffusion coefficientsare smaller.

There has been interest in the solution and diffusion of inert and of permanent
gases in silica g l a ~ s , land
- ~ also of helium and neon in germanium and silicon crystals,6
which provide relatively open diamond-type lattices. Helium loss from and diffusion
in inaterials have likewise been i n v e ~ t i g a t e d , and
~ ' ~ ~there have been a few studies of
trapping of various gases in mineral structures, such as those of the zeolites l1 or of
cordierite.
Two crystalline forms of silica which have relatively open structures are tridymite
and cristobalite, which therefore might serve as traps for dissolved helium or neon.
As part of a programme on encapsulation of gases in minerals, these two forms of
silica have been investigated as solvent and diffusion media for inert gases. They have
rigid three-dimensional networks of linked SiO, tetrahedra permeated by a channel
system in which the windows leading from one interstice to others have free dimensions
of 2.2-2.6 A. Although tridymite and cristobalite are easy to prepare and have good
thermal stability and large potential capacity for sorption they do not appear to have
been examined from this viewpoint. Moreover, the study of solution and diffusion
in these crystals could help to clarify their relationships with silica glass. The similar
densities of -2.2, 2.28 and 2.32 g C M - ~for silica glass, tridymite and cristobalite,
respectively, suggest that they have comparable free volumes.
The complex structures of the tridymites and cristobalites have been reviewed.l l4
Our investigation covered the temperature range in which three tridymite and two
cristobalite polymorphs could be involved, according to the inversion temperatures
below :
39

-163C

-117C

a-tridymite

P,-tridymite

a-cristobalite

P,-tridymite

2 50-27OOC

2275

P-cristobalite.

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2276

S O L U T I O N A N D D I F F U S I O N IN T R I D Y M I T E

These inversion temperatures can be modified by dissolved impurities, including the

inert gases themselves.
EXPERIMENTAL
MATERIALS

Helium and neon were taken from cylinders with output pressures of 2000 and 1000
lb in.-2 respectively. The purity for helium was 99.99 %, and for neon >98 %, the main
impurity being helium.
Cristobalite and tridymite were prepared from silicas. Syton 2X silica sol was precipitated and the gel dried at 120C for a day. It was then heated at 1490C for 18 h to
yield cristobalite and at 1100C to give tridymite. Samples of pure cristobalite were also
made from powdered Spectrosil and also from a pure natural quartz (99.95 % Si02) by
heating for 18 h at 1490C. Attempts to make tridymite from these materials by heating
them for 24 h at 1100C were unsuccessful, the only crystalline product being cristobalite.
Analysis of the cristobalite and tridymite used for the experiments, and an analysis of
TABLE1 .
polymorph

starting material

tridymite
cristobalite
cristobalite

Syton 2X
Syton 2X
Spectrosil

Fe

wt %of
A1

Na

0.11 0.19 0.73

0.12 0.21 0.83
0.035 0-013 0

cristobalite from Spectrosil are given in table 1. In the original Spectrosil the only impurity
reported by the makers is 0.1 wt % of OH. The Spectrosil was, however, ground to pass
120 mesh, and impurity could have been picked up at this stage.
The Na-impurity in the crystals formed from Syton 2X represents about 5 % filling of
the interstices in tridymite or cristobalite. Attempts to prepare tridymite from Spectrosil
in presence of a high pressure of neon were unsuccessful. It was hoped that dissolved neon
would act as a structural support for the growth of the tridymite lattice. The conditions
and products are given in table 2.
TABLE
2.-cRYSTALLIZATION

OF SPECTROSIL IN PRESENCE OF NEON

Ne press. (atm)

(time h)

934f2

15 falling to 7

24

120-mesh powder

1267f2

20 falling to 7

24

1 mmrod

temp. "C

spectrosil

final product

Spectrosil(-90 %)+
cristobalite
Spectrosilf outer layer of
cristobalite

PRESSURE LINE

The pressure line comprised a motorized pumping unit and oil reservoir of an Aminco
hydraulic HP pump, coupled to one side of a Sprague 200 cubic inches intensifier unit
(maximum output pressure 10,OOO lb. in.-2). High-pressure gas cylinders were suitably
connected to this unit. The intensifier was connected to a bank of eight autoclaves, each
with independent pressure and temperature controls. Pressureswere measured with Bourdon
tube gauges (up to 20,000 lb. in. -*), and temperatures with chromel-alumel thermocouples.
Autoclave temperatures were controlled using a Pt-resistance thermometer as part of a
bridge.15 The pressure line was made of stainless steel high pressure tubing, the different
sections being isolated when required with needle valves. The autoclaves were provided
with silver washers for better sealing, and at 6 0 C could be operated at a pressure of about
8000 lb. in.-2

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R . M . BARRER A N D D . E. W . V A U G H A N

2277

METHOD OF EXPERIMENTATION

Weighed samples of cristobalite or tridymite of between 1 and 2 g were placed in capsules

covered with fine wire baffles. They were outgassed overnight at 750C and were then
introduced into the autoclaves, where they were further outgassed for an hour at the desired
experimental temperature. The autoclaves containing the crystals were then exposed at
this temperature to appropriate pressures of gas for suitable periods. The length of time
needed to establish the solution equilibrium was established by trial and differed according
to circumstances (crystal, gas, and temperature). Some experiments lasted several weeks.
The equilibrium period was terminated by quickly lowering the furnaces on their guide
rails and chilling the autoclaves (still under pressure) with ice water. This stage, in the
experiments with helium, was followed at once by further cooling in liquid nitrogen, the
gas pressures in the autoclaves being simultaneously released. The crystal samples in
their capsules were then transferred to silica glass tubes cooled in liquid nitrogen and joined
to an all glass apparatus. This apparatus comprised four units, each provided with manometers and calibrated for measuring volumes of evolved gases, so that four crystal samples
could be degassed simultaneously. Before measuring the amount of dissolved helium or
neon the silica tubes and their contents, still at liquid-nitrogen temperatures, were outgassed
for 3 min to remove the ambient air, introduced during transfer from the high pressure to
the low pressure system. The silica tubes and their contents were raised to 750C and held
at this temperature for 12 h. The evolved gas was passed through a U-tube cooled in liquid
air which condensed traces of water or other vapours collected during the transfer from the
high- to the low-pressure system. A cathetometer was used to read the final manometer
pressures.
DESORPTION KINETICS

Desorption kinetics were studied, after the crystals had been equilibrated with helium
or neon, quenched and transferred to the desorption apparatus as described previously. The
crystals vxre allowed to warm up to the experimental temperature as rapidly as possible,
and were held at this temperature. During the warming process, gas is being evolved at
an increasing rate, so that curves of the amount desorbed against time3 show an initial
period of acceleration. The formal treatment of diffusion, when the diffusion coefficient,
D, thus becomes a function of time, is given in appendix 1, which provides the information
needed to interpret the kinetic runs to give D.
This interpretation requires a knowledge of the surface area of the crystal powder. The
surface area was measured by the projected area method of Kendricks,16 Tooley and
Parmelee,l' and Pidgeon and Dodds.l* The method is described in a British Standards
Monograph.
To carry out the area measurements a Vickers Projection microscope was
used with a 4 mm (0.85 N.A.) achromatic objective lens, and x 6 compensating projecting
lens. A graticule was placed in the projecting lens, and, after adjustments, the system was
calibrated by photographing the graticule superimposed upon a calibrated 0.1 mm grating
in position on the stage. The particles in the photographs were seen in projection, and the
projected areas determined. Then the geometrical area of the particles, in absence of reentrant angles are related to the total area by mean surface area per particle = (4x total
projected area)/(number of particles). This method, which ignores fine-scale surface
roughness, will be somewhat less than an area based upon adsorption measurements. From
it, assuming spherical particles, the average particle radius may be derived. For tridymite
this mean radius was 3.9 x
cm, and the surface area was 7.7 x lo3 cm2 per cm3.
Cristobalite gave values of radius and area respectively equal to 4.1 x loe4 cm and 7.2 x
lo3 cm2 per cm3. If the particles were all assumed to be cubes the above areas should be
multiplied by 1.38, but in the present work they have been treated as spheres.
RESULTS AND DISCUSSION
SOLUBILITY
ISOTHERMS A N D HEATS

The amounts of helium or neon dissolved are shown as functions of pressure in

fig. 1 and 2. The time required to reach equilibrium between neon and the low-

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2278

SOLUTION A N D DIFFUSION IN TRIDYMITE

temperature polymorphs of tridymite and cristobalite was > 50 days, and evaluation
of complete isotherms was accordingly abandoned. Nevertheless a small number
of very long experiments with these materials are included to indicate the approximate sorptions.
Although both tridymite and cristobalite have structures of comparable openness,
and similar total numbers of interstices per g, each potentially able to accommodate
helium or neon, the results in fig. 1 and 2 show that the solubility of these two gases
in tridymite is considerably greater than it is in cristobalite, at comparable temperatures
and pressures. Also, the actual amounts of gas dissolved are much below the
I

pressure X
lb in.-2
FIG.1 .-Tridymite sorption isotherms.
(a) a-,P1-tridymite-helium; (b) P2-tridymite-helium; (c) &-tridymite-neon.

theoretical saturation values, which, assuming one dissolved He or Ne atom per

interstice would be 187 cm3 at s.t.p. per g for tridymite and cristobalite assuming two
sitcs per unit cell for tridymites, and four per unit cell for cristobalites. This indicates
a small affinity, associated with a small heat of solution and a decrease in thermal
entropy when the gas molecules are trapped in the crystals. The isotherms are all
approximately in the Henrys law range, which further indicates that the fraction of
the total available interstices occupied is small. Finally, the amount of gas dissolved
at constant pressure tends to decrease as the temperature is raised, so that the gases
dissolve exothermally in the crystals.
The Clapeyron-Clausius equation in the form
(apIaT), = -AH/TAV

(1)

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R . M . BARRER A N D D. E. W. VAUGHAN

2279

relates the molar enthalpy AH of solution to the rate of change of equilibrium pressure
P with temperature T and the corresponding change AV in volume accompanying
the solution process. Since solution is interstitial in character, AV = - Vg,where
Vg is the molar volume of the gas in the gas phase. The subscript a in eqn. (1)
denotes that the amount sorbed is to be kept constant as the system moves along the
equilibrium P-T line. Because the pressure is high the virial equation is required, i.e.,
PVg = RT(I+BP+CP2+. . .).

pressureX

lb in.-2

FIG.2.-Cristobalite sorption isotherms.

(a)cc-cristobalite-helium; (b) fl-cristobalite-helium;(b) fl-cristobalite-neon.

Eqn. (1) gives, on substituting for A V and integrating,

(3)

wherefdenotes fugacity and where B, are mean values of B and C over the temperature interval (T1--T2)for which the corresponding pressure interval is (Pl-P2). Virial
coefficient values from ref. (20), (21), (22) were used, interpolated where necessary.
Mean values of AH were calculated from each isotherm as follows. If the isotherms
had respectively a and m points, n and m linear slopes were obtained, one for each
point, on the basis of the applicability of Henry's law for isotherms of amount sorbed
against5 and each slope on one isotherm was combined with all slopes for the other,
giving nrn slope ratios and so nm calculations of AH. These were averaged to give

AH,,,,,, = XAH/nm.

(4)

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2280

S O L U T I O N A N D D I F F U S I O N IN T R I D Y M I T E

A t test was applied to these results to obtain a 95 % confidence limit arising from
random but not from systematic errors. The rounded results are given in table 3.
The energies AE of sorption are given by
AH = AE+PAV = AE-PV,,
(5)
where Vgis given by eqn. (2), and are therefore less negative than AH by a term of the
order of magnitude RT. Accordingly some of the energies of sorption are endothermic.
TABLE
3.-HEATS

OF SOLUTION OF

He

AND

Ne

IN CAL MOLE-

helium
-AH

cc-tridymit e
P,-tridymite
&tridymite
a-cristobali te
p-crist obali te

95 %
confidence limit

160
8 10
1230
640
2340

f 120

neon

95 %
confidencelimit

-AH

A400
& 560
f120
f610

1990

f350

2630

k510

EQUILIBRIUM CONSTANTS

The solution process is interstitial in character so that if each interstice is regarded

as a site, Langmuirs isotherm equation should be obeyed :

K = O/f(l -O),
where the fugacity and pressure are related by
In (f/P)= BP+ C P 2 + . . . .
TABLE
4.-vALUES

OF K X

gas

helium

lo7 (Cm Hg)-

polymorph

FOR

He AND Ne
temp. (K)

293
361
410
433
533
670
777

a-tridymite
P,-tridymite
P,-tridymite

helium

a-cristobalite

p-crist obalite
P,-tridymite
neon
/I-cristobalite

(6)
(7)
IN CRYSTALLINE SILICAS
Kexptx lo7

5.1
5.0

4.6
4.2
3-7
4.6
4-1

293
416
537
612
773
857

1-2
0.77
0.6,

675
766
838
673
767
836

3.9
3.3
2.9
1.2
0.83
0.70

0.59

0.71
0.6

Since the non-ideality correction is not large relative to other uncertainties, eqn. (6)
may be approximated by
K = e/[p(i - e)(i 13p)l.
(8)

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R . M . B A R R E R AND D . E . W . V A U G H A N

Equilibrium constants evaluated from eqn. (8) are given in table 4, column 4, assuming
that saturation represents one rare gas atom per interstice. This means that at
saturation there would in tridymite, e.g., be as many helium or neon atoms in a
given number of unit cells as there are Na+ or K+ ions in equilvalent amounts of the
" stuffed tridymite " structures nepheline or kalsilite.
DIFFUSION

The kinetics of desorption, under conditions near to those described above and
in the appendix, are shown in typical instances in fig. 3. If Q, and Q, denote
respectively the quantities desorbed at time t and at infinite time, the curves of
Q f / Q , against J t are sigmoid. The period of acceleration corresponding with
rising temperature is often followed, after the steady temperature has been reached,

FIG.3.-Desorption

kinetics.

(a) a-tridymite-helium ; (b) a-cristobalite-helium ; ( c ) PI-tridyrnite-neon ; ( d ) P2-tridymite-neon.

by an approximately linear section, and then by a period of deceleration as Qf

approaches its final value. Helium escaped rapidly from the higher temperature
polymorphs of tridymite and cristobalite, making it difficult to obtain reliable rate
curves. Neon was well trapped by a-cristobalite but escaped readily from the p-form.
In the latter case the small amount of the dissolved gas and the rapid release again
prevented reliable kinetic measurements from being obtained. Neon was also
firmly trapped in a-tridymite whereas the P-polymorphs released the gas readily.
From the slopes of the linear sections of the curves in fig. 3 the diffusion coefficients
may be obtained in the manner indicated in the appendix, i.e.,
d( Qt / Q),

/dt = 4S2D(T,) In V 2

(9)

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2252

SOLUTION AND DIFFUSION I N TRIDYMITE

where S and V are the surface area and volume of the crystallites and D(T,) is the
value of D when the temperature has reached its final value. Diffusion coefficients
thus obtained are given in table 5, together with values for silica glass 2* for
comparison.
TABLE
5.-DIFFUSION

COEFFICIENTS OF

He and Ne IN

CRYSTALLM SILICAS AND IN SILICA

GLASS
HELIUM

u-tridymi te
temp., OK D, cmz sec-1

336
296
273
235

temp.,

1 . 2 lo-''
~
1~1O-l~
2~ 1043
3 . 9 10-15
~

a-cristobalite
D,cm2 sec-1

silica glass
temp., OK D,cmz sec-1

O
K

335
296
273
244

1.7~
1.3 x
1.6~
8 . 7 10-15
~

351 1x10-7
297 2 . 4 lo-'
~

NEON

temp.,

a-tridymite
O K

D,m z sec-1

/71-tridymite
temp., OK D, c m 2 sec-1

Bz-tridymite
temp., OK D , cmz sec-1

474 7.1 x
444 1-1x10-12
418 2.3 x

366 2 . 2 ~
10-15
354 8 . 7 ~
336 1 . 2 ~

577 3 x 10-l1
543 1.1 x lo-''
513 3 . 9 ~
10-l2

silica glass 2. 3
temp., OK D, cmz sec-*

577
513
418
336

4 . 5 10-7
~
6*1~10-~
2x
5.9 x lo-''

13

a -tridymite-helium
14

7'
'.
L-LFIG.4.-Plots

1313

16

20

2.5

e,
t ridymites -neon

30

3.5

4.0

1O ~ / T O K
of diffusion coefficient ( D ) as a function of temperature.

Slopes of plots of log D against 1/T (fig. 4) were approximately linear

so that estimates were made of the Arrhenius energies of activation E from
D = Doexp (-EIRT). These are given in table 6. Again, for comparison
purposes, values of E for diffusion in silica glass are included. Diffusion coefficients

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R . M . BARRER A N D D . E . W . V A U G H A N

are considerably larger in glass than in either tridymite or cristobalite (table 5), and
energy barriers for diffusion are nearly twice as high in the crystalline silicas as in
the glass. On the other hand, energy barriers and diffusion coefficients are similar
for helium in a-tridymite and a-cristobalite.
TABLE6.-ACTIVATION

ENERGIES E FOR DIFFUSION I N CRYSTALLLNE SILICAS AND

IN SILICA GLASS (kcal/mole)
tridymite

gas

helium
neon

12
22.5

81

silica glass ?,

cristobalite
82

13.8

24.1

19.1

5-6 to 6.6

11.3

DISCUSSION

Comparisons of interest include relations between solution and diffusion in

crystalline silicas and silica glass, between experimental and theoretical heats of
solution, and between experimental and calculated equilibrium constants.
C R Y S T A L L I N E SILICAS A N D SILICA G L A S S

The solubilities of helium and neon in tridymite, cristobalite, and also in silica
glass,2* are shown as functions of temperature in fig. 5. The solubilities, in
atoms/cm3 atm, are much closer between tridymite and glass than between cristobalite and glass. Previous hypotheses on the glassy state assume that it is the
cristobalite structure which approximates the more nearly to that of glass, but at
least as far as the solubility measurements are concerned the reverse is the case.

Neon

.z
4 tridyntles

--lo141

,I

2bo

cristobalites
silica glass

3bo

4bu

5b0

ti,',

A
400

500

600

temperature, "C
FIG.5.-Solubilities of helium and neon in silica polymorphs.

The random network of silica glass should contain, inter alia, 5, 6-, 7- and 8membered rings of SiO, tetrahedra as units in the structure and the diffusion path
of helium and neon in silica glass must take them through those rings which are wide
enough to permit transit (i.e., 6-, 7- and 8-rings). However, diffusion paths involving
as many as possible of the widest rings will be statistically favoured and so will
contribute most to the transport. In cristobalite and tridymite the rings defining
the d.iffusion paths are all 6-membered ones so that the average energy barrier in
these crystals would be expected to exceed that in silica glass where the larger, more

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2284

SOLUTION A N D DIFFUSION I N TRIDYMITE

open rings also occur. We have also made some measurements with quartz powder
(density 2-65), and although very small amounts of helium were dissolved, we were
unable to measure diffusion or solution equilibria of helium or neon. Here the
interstices are probably too small to accommodatethe rare gas and the energy barriers
for migration correspondingly high. If the diffusion coefficients are expressed in
terms of the Arrhenius equation [D = Do exp (- E/RT)] their values are as follows :
He, a-tridymite (235-335K): D = 7.7 x
exp - 12,000/RTcm2 sec-l,
exp - 13,800/RTcm2 sec-',
He, a-cristobalite (244-335K): D = 2.0 x
Ne, a-tridymite (336-366K): D = 6.7 x
exp -22,50O/RT cm2 sec-l,
Ne, p,-tridymite (418-474K): D = 9.9 x lo-' exp -24,10O/RT cm2 sec-l,
exp - 19,100/RT cm2 sec-l.
Ne, P,-tridymite (513-577K): D = 4.5 x
These expressions are approximate. Uncertainties in E strongly influence the
magnitudes of the pre-exponential constants, but these are often comparable in order
of magnitude with values of Do for diffusion of He and Ne in fused quartz 2 * which
varied from 2.1 to 7.4 x
cm2 sec-' .
C A L C U L A T E D B I N D I N G ENERGIES O F D I S S O L V E D G A S

The Lennard-Jones 12 : 6 potential was used, with the lattice positions of oxygen
26 and Pi-tridy~nite,~~
to calculate the
in a-cristobalite 2 3 * 24 P-crist~balite,~~*
energy of binding of inert gas molecules within the interstices of these crystals.
The dispersion energy 4Dand repulsion energy & are then,

where ri denotes the distance between the centres of the rare gas atom and the ith
oxygen atom. ro is the distance between these centres for an isolated rare gasoxygen atom pair when (a+/&) = 0. A is the dispersion energy constant, which
has previously been evaluated for rare gas oxygen pairs,28according to the approxi32
mations of London,29 Slater and Kirkwood 30 and Kirkwood and M~ller.~',
In the present work, these values have been used taking the polarizability a as
1.65A3 for framework oxygens.28 The radius of oxygen was taken as 1-35A, and
those of rare gases, except helium, are given elsewhere.33 The summations required
in eqn. (10) were made using an Atlas computer.
For all crystalline silicas referred to above the energy contours were evaluated
for movement of the rare gas atom within a cavity and in transit from one cavity,
through a ring of six tetrahedra (a 6-ring) to an adjacent cavity. In a-cristobalite
the sums in eqn. (10) were evaluated for the 38 nearest oxygens. The first axis
considered was the line running from Si (-2, -j,
-25) through the centre (-25, '5, -625)
of a 6-ring and thence to the Si (*3,1.3, 1) (fig. 6a). Due to the configuration of the
lattice these two paths though joined are not collinear. The energy contours were
also found along each of two new axes normal to, and passing through the energy
minimum on the first axis. The two additional axes were chosen by trial calculation
to give the greatest and the least vibration frequencies.
For /?-cristobalite 4 was evaluated for 38 oxygen atoms along the [ l l l ] axis
passing through (OOO) and (1 11). It was also found for two additional axes normal
to the first chosen just as for a-cristobalite (fig. 6b). Finally, in /?,-tridymite 4 was
calculated for 57 oxygen atoms along [OOl], and along two other axes normal to
[OOl] and chosenjust as for the cristobalites (fig. 6c).

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R. M . BARRER A N D D . E. W . V A U G H A N
[ii)

FIG.6.-Views

of cavities with argon atoms (diam.

3.8 8,) on sorption sites.
(a)P2-tridymite: (i) [Ool] axis vertical in the plane of
the paper, (ii) [Ool] axis normal to the plane of the
paper. (b) P-cristobalite: (i) [lll] axis vertical in
the plane of the paper, (ii) 11111 axis normal to the
plane of the paper.

(ii)

10

energy contours. V, helium; m, neon; 0, argon; 0 , krypton (using the

London A constant).
(a) a-cristobalite contour following a line from (-2,
-25) through (-25, -5, -625) to (-3, 1-3, 1):
abscissa in 8, units from (-2, -3, -25). (b) fkristobalite contour parallel to the [l 111 axis ; abscissa in
A units from (OOO). (c) P,-tridymite contour parallel to c axis: abscissa in A units from (000).
( d )P2-tridymitecontour along an axis from the cavity centre through a six-ring side window : abscissa
in 8, units from (0, 0, -25).
FIG. 7.-Potential

*z,

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2286

SOLUTION A N D DIFFUSION I N TRIDYMITE

Some of the energy contours are shown in fig. 7a-c for movements of dissolved
atoms along the first axes. In these calculations the positions of lattice atoms are
necessarily assumed to be fixed, whereas thermal vibrations must cause perturbations
of the curves from moment to moment. According to the energy contours helium
could move freely along the [OOl] axis. However, thermal vibrations and collisions
would soon terminate such flights. Moreover, the centre of the helium atom must
move exactly along the [OOl] axis to be transported with such a low energy of activation,
and the chance of this is very small. Glancing passages, in which helium strikes
peripheral oxygens of the 6-ring, and in which considerable activation energies may
thus be required, will be much more frequent. It is still more probable that the
helium would be reflected back from oxygen atoms in its cavity and perform many
oscillations before escaping to another cavity. For the reasons given above, it is
most unlikely that the energy contours give any true picture of the activation energy
for diffusion. They may, however, give reasonable approximations to the energy
minima relative to the least energy of the gaseous molecules.
The energy contours for Ne in P,-tridymite also give an activation energy (- 3 kcal
mole-') much below the experimental value ( 19.1 kcal mole-') for movement
precisely along the [Ool] axis. Clearly the arguments presented in the previous
paragraph apply here, and to all such calculated energy barriers. A series of
additional paths leads off from any [OOl] axis, at appropriate points along it for which
the calculated energy barriers are likewise small (- 0.5 and 4.5 kcal mole-'). These
paths lead, e.g., from (0, 0, 025)along an axis through (-5,
-25) (fig. 7d).
The trapped gas atoms can vibrate with many possible frequencies in any cavity,
according to the different energy contours associated with movement in different
directions. Some specimen calculations were made by a procedure already
described 33 of frequencies vl, v2, v3 of the rare gas atom when it moves along any
one of the three axes described, except where the barriers were less than RT in height.
These calculations ignore effects of lattice vibrations upon the energy contours. They
are, however, of interest in connection with the oscillator model for the dissolved
atoms. Their values, and those of &, are given in table 7, using both the London
and Slater-Kirkwood approximations for the dispersion energy constant, A .
N

a
%
,

O S C I L L A T O R M O D E L FOR D I S S O L V E D GASES

If the dissolved atoms are considered as a set of Einstein oscillators of frequency v,

then allowing for zero-point energy the equilibrium constant, K of Langmuir's
isotherm in cm-1 (see table 4) is given by
1
h3
( 2 s i n h g ) - 3 exp-RT.
Sm
K=-koT (2nmkT)+
Here ko is the value of the Boltzmann constant k when p in p = ckT is expressed in
cm Hg and c in molecules cm3 and $+, is the value of 4 (eqn. (10)) at the minimum
in the energy well. Similarly the heat of solution is given by
5RT 3 R h v
hv
AH = +,,,--+- coth -.
2
2 k
2kT
Accordingly we have used the experimental values of K to calculate mean frequencies,
using & evaluated in table 7 according to the London and Slater-Kirkwood approximations for the dispersion energy. The frequencies calculated for each K and then
averaged for all K are given in table 8. They were used in eqn. (12) to calculate AH,
which is also tabulated.

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R . M . BARRER A N D D . E . W . V A U G H A N

The frequencies are higher in cristobalite than in tridymite, reflecting a smaller

thermal entropy in accordance with the smaller equilibrium constants. The calculated
heats are not significantly different, where the comparison can be made, between
tridymite and cristobalite. The mean frequencies in table 8 are in general of the
TABLE
7.-VALUES

OF # m AND OF V IN CRYSTALLINE SILICAS

- dm, cal mole-1

gas

He

Ne

polymorph

London Slater-Kirkwood

vibration frequency, v (sec-1 X 10-12)

London
v1

y2

Slatcr-Kirkwood
vj

v1

v2

v3

P,-tridymite
a-cristobalit e
p-cristobalite

2060
2040
2000

3190
3160
3090

4.0

3-7 1.9
2.0 7.1 6.1

- 9-0 9.0
4.5 4.4 1.9
1.9 7.8 5.5

P2-tridymite
P-cristobalite

2040
1360

3810
2540

0.94 2.8 0.9

3.1 3.1 2.6

1-3 2.9 1-2

3.4 3.7 3.3

- 6.3 6.3

same order as those in table 7 calculated from the energy contours of fig. 7, although
the frequencies in table 7 refer only to specimen calculations and are not mean values
over all possible energy contours. The largest difference is for helium in a-cristobalite.
The experimental heats of solution in table 3 and those calculated in table 8 all
correspond in sign, and sometimes in magnitude. In some cases AH calculated
TABLE
8.-FREQUENCIES
AND
gas

He

Ne

polymorph

HEATS OF SOLUTION CALCULATED FROM #m AND

mean v x 10-12 (sec-1) from

dm
dm (Slater(London) Kirkwood)

P,-tridymite
a-cristobalite
P-cristobalite

4-8
11.2
9.4

P,-tridymite
p-crist obalite

- A H (cal mole-1) from

dm
dm (Slater(London) Kirkwood)

temp. OK
for calc
AH

6.3
15.8
11.7

1250
1300
1080

2360
2100
2100

770
41 5

2.1

3.4

3.5

4.8

1290
600

3060
1700

750
750

800

using the London approximation is nearer the experimental values (He in P,-tridymite,
a-cristobalite, and Ne in P,-tridymite) while in others the Slater-Kirkwood value is
better (He and Ne in P-cristobalite). Thus, no choice between these two approximations can be based upon the calculations.
CONCLUSION

The main interest in this study centres upon the solubility and diffusion measurements, and on the considerable capacity which tridymite and to a lesser extent
cristobalite can show for encapsulating neon and helium. When argon was heated
under pressure with these crystals there was evidence of solution but under the
conditions employed here equilibrium times were in excess of three months. To
trap the heavier rare gases more open crystals will therefore be needed. The
theoretical calculations are also of considerable interest since they lead despite some
unavoidable limitations to an encouraging measure of correspondence with
experimentally determined heats. This is seen in the limiting case hv-4kT for which
eqn. (12) gives AH = #,++RT and so AE = +,+$RT; i.e., at T"K both AH and
AE are less negative than &.

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2288

SOLUTION A N D D I F F U S I O N I N T R I D Y M I T E

APPENDIX
The sigmoid kinetic curves of fig. 3 must be representable by an appropriate solution of
the diffusion equation, from which it may be possible to derive D, the diffusion coefficient.
The solution required is that for a system in which the temperature is allowed to rise from
an initial temperature (77, 273 or 293K) to a selected final temperature, during and after
which dissolved gas is being desorbed.
Since D depends on temperature T, and temperature on time t, D must also be a function
of time. Considering the crystal particles to be spheres, the diffusion equation in a sphere
of radius a can be written

aulat = D(tp2Upr2,

(13)

where u = cr, c being the concentration at a surface of radius, r within the sphere. If we
set dz = D(t)dt then this equation reduces to

auld7 = a2Ujar2,

(14)

while the boundary conditions in our experiments are

(i) for z = 0, C = Co for O<r<a

(ii) for z>O, C = 0 at r = a

(15)

An appropriate solution of the above equation and boundary conditions gives for the amount
Qt desorbed in time t,

In this expression Q , is the total amount of desorbed gas after infinite time. For smaller
values of z only the first term need be retained, so that

This latter solution does not require all the spheres to be of the same radius, only the total
area S and volume V of all the particles being required for a powder composed of spheres
of varying radii, or else an average radius, ii = 3S/ V.
We next require an expression for z. The diffusion coefficient can be assumed to obey
the Arrhenius equation, D = Do exp (-E/RT), where E is the energy of activation and
Do is a constant. Since T = 4(t)

D(t) = Do exp (-E/R$(t)).

The simplest form for $(t) which has the required properties is

T = T,(l - A exp -kt),

(1 9)

where Tis the temperature at time t and A and k are constants. Then the initial temperature
is T,(1 - A ) and the final temperature is T,. Also
z =

ex(

)dt.
RT,[ 1 - A exp ( - kt)]

If we set

B = EIRTo and Z = -B/[1 - A exp ( - k t ) ] , then

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2289

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R . M . BARRER A N D D . E . W . V A U G H A N

The integrals in the square bracket can be obtained by expanding the exponentials as series
and integrating term by term. Then if the first and second integrals are denoted by I ,
and I,

"-l

(-B~(B+Z)"-~]"

ln(B+Z)exp-B+
m = l s=o (m-S)!S!(m--)

zo'

(23)

In these expressions, 2, = - B / ( l - A ) , and, making all substitutions to obtain z in terms

of A , B and t , one obtains
t

= (Doexp-B)t+- DO

In

(1-Aexp-Bt)

'

(m-1)
s=o

(l-exp-B)+
1
[l-Aexp(-kt)]"-(=}A"--"
Am-s
[cxp (kt)-A]"-" - (1 -A)"-'

.]I

(24)

When the final temperature T , has been achieved all the terms exp ( - k t ) have decayed to
zero, so that
z = D(T,)t

+constant.

(25)

Accordingly,

4S2

36

This last relationship should be valid not only for the particular example taken above for
4 ( t ) , but for any 4(t) which changes from an initial to a final value during only part of the
interval in QJQ, over which the d t law applies under isothermal conditions.
F. J. Norton, Gen. Elect. Co. USA, Res. Lab. Reprint, no. 4142, 1962.
D. E. Swets, R. W. Lee and R. C . Frank, J. Chem. Physics, 1961, 34, 17.
R. C. Frank, D. E. Swets and R. W. Lee, J. Chem. Physics, 1961,35, 1451.
E. 0. Braaten and G. Clark, J. Amer. Chem. SOC.,1935,57, 2714.
W. H. Urry, J. Amer. Chem. SOC.,1932, 54, 3887.
A. van Wieringen and N. Warmoltz, Physica, 1956, 22, 849.
' N. B. Keevil, Proc. Amer. Acad. Arts Sci., 1940, 73, 311.
W. H. Urry, J. Amer. Chem. SOC.,1933, 55, 3242.
Lord Rayleigh, Proc. Roy. SOC.A , 1936, 156, 350.
l o A. Holmes and F. Paneth, Proc. Roy. SOC.A , 1936, 157,412.
l 1 G. A. Cook, Helium and the Rare Gases (Interscience, N.Y., 1961), vol. 1, p. 228.
l 2 W. Schreyer, H. S . Yoder and L. T. Aldrich, Carnegie Inst., Washington, Year Book, 1959-60,
59,94.
l 3 W. Eitel, Bull. Amer. Ceram. SOC.,1957, 36, 142.
l4 R. B. Sosman, The Phases of Silica (Rutgers Univ. Press., N.J., 1965).
l 5 M. H. Roberts, Electronic Eng., 1951, 23, 51.
l 6 F. 3. Kendrick, J. Amer. Chem. SOC.,1940, 62, 2838.
l 7 F. V. Tooley and C . W. Parmelee, J. Amer. Ceram. Soc., 1940, 23, 304.
F. D. Pidgeon and C. G. Dodd, Anal. Chem., 1954, 26, 1823.
l 9 Optical Microscope Methods (British Standards Monograph 3406, part 4 ; 1963).
2 o R. Wiebe, V. L. Gaddy and C . Heims, J. Amer. Chem. SOC.,1931, 53, 1724.
2 1 W. G. Schneider and J. A. H. Duffie, J. Chem. Physics, 1949, 17, 751.
2 2 G. Nicholson and W. G . Schneider, Can. J. Chem., 1955, 33, 589.
2 3 W. Nieuwenkamp. 2. Krist., 1935, 92, 82.
2 4 W. ,4. Dollase, 2. Krist., 1965, 121, 369.

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2290

S O L U T I O N A N D D I F F U S I O N I N TRIDYMITE

W. Nieuwenkamp, 2.Krist., 1937, 96, 454.

W. G. Wyckoff, 2. Krist., 1925, 62, 189.
27 R. E. Gibbs, Proc. Roy. SOC.A , 1927, 113, 351.
28 R. M. Barrer and D. L. Peterson, Pro-oc. Roy. SOC.A , 1964, 280, 466.
2 9 F. London, Z. physik. Chern. B, 1930, 11, 222.
30 J. C. Slater and J. G. Kirkwood, Physic. Rev., 1931, 37, 682.
3 1 J. G. Kirkwood, Physik. Z., 1932, 33, 57.
32 H. R. Muller, Proc. Roy. SOC.
A , 1936, 154, 624.
33 R. M. Barrer and D. J. Ruzicka, Trans. Furuduy SOC.,1962, 58, 2263.
25

26