
J. Jpn. Soc. Soil Phys.
¼2uNo. 30, p. 2- 22 ,**.


THF*ῌ*ῌ*Frost Heave of Tetrahydrofuran Clathrate Hydrate on Porous Glass Powder
Kunio WATANABE*, Kousuke YOKOGAWA* and Yoshiko MUTO** Faculty of Bioresources, Mie University, +/+/ Kamihama, Tsu /+.ῌ2/*1, Japan
Abstract
The formation process of clathrate-hydrate in porous glass powder saturated with THF-water
mixture was observed using directional cooling apparatus.

When the cooling rate became lower,THF hydrate grew with excluding glass particles and formed lens -like layer of hydrate in thesame manner as in the phenomenon of ice lens formation in the freezing of soil. The growth rateof hydrate lens was proportional to the supercooling degree of the growth surface and about
one-twentieth the growth rate of hydrate layer in THF-water mixture without glass particles.
When NaCl was added into the system, the growth of hydrate lens was inhibited depending on theNaCl concentration.
Key words : THF clathrate hydrate, frost heave, glass powder, directional growth, in situ
observational., ,*** ; ,**,1+          zS$Wc mnojklO{N |}"& c
higjklmnojkl5? ~( N; -wxMI1  !"#"$%#"& '( )*+I u -'JKakKI THF 1 , -./01

23,445' 6&47"&89:;<= >%#(>"&' -ῌ +330?@;  ,**+1  wxMmnojkl [\]^$A BCDE -FGῌ?H +33+1 IJKLM -Zhe etIYZ +*+,+*+2 m- 5^$al., ,***1  : N4 89:

W<( -Sloan, +33* ; Matsumoto, ,**,1; >OPQ RST468fg5"WWc 6& +TUVW3& - ,***1 54X YZ

fg## $&  mnojk

I[\]^_$`(#"&aJ l"+$%Wc -Uchida,I+331 ; Uchida et al., +3331 $ CFCs -Chlorofluoro-NbO"& 'c d6A

%#"&efghigjklmnojkl
45' -Dallimore and Collett, +3311 "!"ecarbons1  "¡¢£¤ THF &mnojkl '¥¦§()¨*5"W©+Wc

-Iida et_"$   dpqlirostiM -THF1al., ,***1 47"&ª«I¬­,<=mnojk

mnojklu:I -Rue# and Sloan, +32/1 v

l®¯°6(55IwxMmnojklyu: -Chuvilin et± -Mak and McMullan, +30/ ; Gough and Davidson,* ²³´´- µ/+.ῌ2/*1 ¶·..¸ +/+/
 : THF higjklmnojkl ./0 fig/; ¹0º(»1 NbmnojklQ"»+,\

84+31+ ; Sloan, +33* ] 30 ¼ ,**.

8YZ[(+s,RossTHF +et al., +32+ ; Leaist et al., +32, ; Handa et al., +32.

  -t(  ;

YZ[2m+uv-P

<=8 Rue# and Sloan, +32/ w#2m  !"#$%&'() *+&', -+uv1g#!"<xyz(=8 Chuvilin et./0  Uchida et al. +333 12

al., ,*** ; ,**,

+345+/0-6789:;

,, 

<<= <

THF +{># ?@  THF 8E+|}1\ *~... 8A4(8=>% THF ?"$%@A

Hanley et al.,-&'() , +*+B/0CC+323 !HI% THF -B]E8ik + :+1 %|} ?@... p <c+HI%  +333 ; Nagashima et al., ,*** ;Iida et al., ,**+ 8DC  THF E2+ THF E2 NaCl -C THF E2-D

FGHI-J< THF +',E< +* 1P YZ[(8/0+F +E !G% YZ[(+HI( 'K+ THF +LM< *=%!NO% THF E2+H-E8=88( %"+1P#Q $+&',|} <YZ[( D2+ THF NaCl +-%RST+UVWX-() THF E

 NaCl   ῍2  JA4(2%&'YZ[(+ FGHI-J\ *=%Ea*+2 d+ +.+ K+EL8, 2, a*+2+ NaCl  Cintd LL 82

d+ +.+ K+E LL+.+ <E w -t(,+  !HI% THF Aldrich, 33.3ῌ NaCl ]E Y

a*-Mn 1.// mm  +/* mm +NYZ[Z[( ^)4'_` P0** -a*< THFk) O-P) k-Zzzk

+"?#$<ῌb+-&'(%DE 67 ¡¢£k8YZ[(Gough and Davidson, +31+ c-)#k-  #kQI- /< 2d, -.,!CDR k$S-2T5¤U¥¦R-

+'e&'-/0(  THF EP-.,J\ k-%fg=1h%) +ij

kl8CC

FGVW%$S1gG§ + kRS+# +* $S+#¨. %fg kM+#©XG-)1g , ª«

Devarakonda et al.,,.,

1* ¬\ !HI­®#

 -.- nm +4oQ-5(©X *.+.¯*.*+/ mm¨+ °\ a*+G, +7p =+YZ[( Hq+"67%R -5(m-j±²k³j´µ¶Z-<YZ/0=8 r8< 9: ,***

THF +',+333 !HI%<YZ[(+2m 2nmm 3\g+  THF ῌ+Table +a*+s,

Physical properties of sample+ : +1 sol4 Hydrate Water

Ice

Thermal cond4 Wm¨+ K¨+*4/0,a*4/,/a*4/0+,4+.
Speciﬁc heatkJ kg¨+ K¨+.4,+b,4+,-c.4,+1,4++
Densitykg m¨331d331d+***3+1Melting point
Latent heatkJ kg¨+Di#usion coef4 m, s¨+.4.e,0*c¨+7m-£·¸²-+4*+*¨3 fMean diameter
mm,4,
Mean pore size
nm-4Speciﬁc pore volume m- kg¨+ *4-+*¨Speciﬁc surface area m, kg¨+ +,3+*Density
kg m¨- ,+,**--¨

Glass powder¨Hydraulic cond4m s¨++43+*¨2ik + : +1 + THF E2 + : +1sol. ¹º6ik+ THF hydrate Hydrate  .4. + E Water ¹º; Ice  * +[a Ross and Anderson (+32,), b Iida et al. (,**+), c Leaist et al. (+32,), d Gough andDavidson (+31+), e Hanley et al. (+323), f Gillen et al. (+31,)

¢£ : $%&NOF THF ¤%&HH! ¥¦ῌ,

85! NaCl <,

Table ,NaCl concentration in solution andthe ratio of solution to glass powder

Name

Cint (῍)

LL (῍)

LL+4+w (῍)

S*
S**S**-w
S*S-**4**4**4-++/+,/+,/+.+2/+,04/+-14/+-14/+/14,*-4/+,04,+-04,+//4/+//4/,*-41- -+ 



ῌ+Fig. +!"YZ!

Schematic illustration of directionalcooling experiment.



#$%&'()*+,-./!01234 5 ,  ,. 6789:!

;S*NaCl < *῍= !/>?@AB!C(DE 5F

&GHI + mm DE JKLM1$%&NO P
QR! S14/TU VW X

YZ[\YZ]^ YZ1ab_/!4`W\.VK#c@1adEe ;YZe

= 1fg. h]!/14$%&NOijXk4.1Wl +** mm -T>? ;5 ,=!/!>?1m- n\ijTo!

/14ῌ>?
\_4ῌ>?123[#4/$%&NO!pqr.0stu

1v>[\ 4/!w[ :v>x!)ῌ,Fig. ,!/>?@AB!C(Crystallization in glass powder
saturated with + : +1 THF solution.

+wg.Khxij ;h:= 4/ .2 67T -.+0mm -T>? -..*.y zK!"!>?@!

!YZ{|: h:4/}I~zA S /U  ;5 -=  ! VW 4/
THF HTU 1V -_NOF!4H n!vsVW H E-,5 . hxij4H!>? ;

= !67 5 / n!6!H!>?@!n\\DE 5 ./ ! hxij!H14

VW!8967TU \!

x H!>?e]^eg ofg

ῌFig. -4/¡C(The crystal burns readily in air.

±²³´ µ 30 ¶ #,**.%

86   i{HNm)   = |i{}'  THF S* S**- S**-w S*- 7 *.*-- mm sf+Kf+ *.*,* mm!" #...$% &'$ () *+,

sf+Kf+ *.*,. mm sf+Kf+ *.*-, mm sf+Kf+-*+./012)

T NaCl U~4hi&L

 .2 * NaCl 34

 56S}

/56 #S*% 7 89:*+  Z 0  X   S* S**- S**-w S*- 7, ..+-$ 7;  !"

*.,1 +..1 *.3+ ,.1/& *.,1$ (<  => ?@ABCDE&a89:*+, #...f!"F(GHI JKL>M

X  %  ..+-$ ,.3-$ -..3$ +.0/$  =>L<L 56el>MHN& .2 OP

P]^ +K ;hWXa*+QR ST NaCl U *.*-ῌ 56 #S**-% 7 ,./+m #*./ mm sf+Kf+% uhav*+m #+,.- mmmm *.-ῌ 56 #S*-% 7 ,.*- mmsf+Kf+%  +ῌ,/    =>ST NaCl UF2/VKWXY)  #Z .%  [v:/ # +% &M >M=\]^_`7 ST NaCl U -ῌ 56 #S-% a7 BCazA*+m *+,

bcdF*+H h #Hh% & uhav*eL><  .2 OP

+m +ῌ,*+ῌ-*  M #Watanabe, ,**,% w*+, S* 7 ..*.$ S**- 7 ,.1-$

xy7R>*+mlhW

S*- 7 +.02$ S- bcd*+,

Xa*+m +ῌ,* 7; v

 VKWXSTUF2/jk *+,7h

f*.-/$() #Z /%

FN/M JKL>MS**-w  VKWXST NaCl UF S**-g.

H) #*.*-ῌ% 4hiF2/567;M jkST
NaCl U7; Nl 4hiF2)M Q) *+,2)  #Z . /%
-- 



==7 Z . <L*+m3
Z / <L*+,P]^ #nTo...fT% 3pI Z WX ¡G¢nTms nTmsoi KC 7
R>M ==7 i !"}' K W£¤ ¡G¢ C W¤U7;M  ?@ABC&MWX ¡G¢3nTmpt>¥ ¦§¨H©

 THF *+, Tgs  Tgs o...fn0a *+m P]^qr3st Z 0b  uTmsfnTmp 7ª7|M JKL>M / Z 0  X

ha7*+tMv wxy jk?@ABCa7*+

tMzA #Watanabe, ,**,% + : +1THF hW

THF hWXa7!"­' i 3 , THF hWX¤

Xa7*+tM THF *+mlsH ¡G¢3h jk +.20 $ kg molf+ *+m*+,P]^**- S*- S- ®¯M*+, NaCl

ῌ. 8l2°H*+¢ῌ/Fig. . Growth amount of the warmest hydrate lens.

3 Tgs S *  « ¬ < L n Tmp 3 *.,1$ NaCl tM  S

8l2°H*+,
Fig. /

Temperature at growth surface ofthe warmest hydrate.

 : QRSkl8%w¼

THF sRS ! !xbyz

87

et al., ,**+3  nij4JCa/    oh-pqrl8sRS ! !t"uvw\xbyz{|}~ 4 %:jKL4.

DE THF 79CQRSkl8%XY !& * G THF 7 NaCl &,-  !XY"*  !&"#>

&J*

 THF !XY"#<XY"#u%C G NaCl
&,-   !XY"#W
,- "#<M,-

&%-.

 ObDE oQRSkl8mSXY
"# 2xbyz3 ij4JCar40>  XYD"ῌ0Fig. 0"#<"#u
2a3  !QRSkl8
 !XY 2b3 º78» QRSkl8mSXY 78 THF  !
Growth rate and degree of supercoolingat the growth surface.
(a) THF hydrate in glass powder. (b) icein water, ice lens in glass powder, andTHF hydrate in solution.

xbt}~-eoxb%> &o
h-pqrl8 !t"uv4> %9(   !XY"#+7~ ¡¢r^_£  K¤o
4KL4h¥&¦ )§h¨©4ª/ %¦¯-°±4)

«I¬#1­%®
%²Ca³´µ4¶>- w  ¨ ©  ¨ © ·  : ¸  ¹ ¬ ¨ © ·2+.10*+/03 %

 +.3ῌ -.3ῌ 1.*ῌ  NaCl  ,.- 0-  !"#$% NaCl &Chuvilin, E.M., Perlova, E.V., Makhonina N.A. and!"#'()*  "#+ NaCl &

Yakushev, V.S. (,***) : Research of hydrate and,-./0

ice formation in soils during cyclic ﬂuctuations#12+3333  -ῌ  NaCl 456 + : +1THF 7

89:;< 2/ mm s=+3 9"#>

THF !"#+ NaCl 4?@A9B;CDE

of temperature. Ground Freezing. pp. 3ῌ+.,Balkema, Rotterdam.
Chuvilin, E.M., Makhonina, N.A., Titenskaya, O.A.

 !"#+9 NaCl & ../ῌF/.0ῌ

and Boldina, O.M. (,**,) : Petrophysical investi-G9HI>

4JC KL9 #1 KL

gations on frozen sediments artiﬁcially saturat-

!"#<&M 2N 0 ;*.*/ mmed by hydrate. Proceedings of the Fourth Inter-=+OP3 "#+ NaCl HI,-.

national Conference on Gas Hydrates : 1-.ῌ1-3.

 G QRSTU&V S**-w 9 S**-

Dallimore, S.R. and Collett, T.S. (+331) : Gas hydratess"#W&,-. 

2N /3 associatedwithdeep!XY"#+9QRST% NaZ [Mackenziedelta,N.W.T.,\ Cl= ]X^_& `* a 0"#+9 NaCl bc &Vdefg%f permafrost

intheCanada : Regional

overview. Proceedings of the Seventh International Conference on Permafrost : ,*+ῌ,*0.

hCij QRSkl8m

Devarakonda, S., Groysman, A. and Myerson, A.S.

SXY"#+ NaCl bc 2Watanabe(+333) : THF-water hydrate crystallization : anmn opq v 30 w ,**.

88

experimental investigation. Journal of Crystal

interface of tetrahydrofuran clathrate hydrate.

Growth, ,*. : /,/ῌ/-2.

Science and Technology of High Pressure, + :Gillen, K.T., Douglass, D.C. and Houch, M. J.R. (+31,) :Self-di#usion in liquid water to -+. The Journal of Chemical Physics, /1 : /++1ῌ/++3.
Gough, S.R. and Davidson, D.W. (+31+) : Compositionof tetrahydrofuran hydrate and the e#ect of pressure on the decomposition. Canadian Journal ofChemistry, .3 : ,03+ῌ,033.

/1-ῌ/10.
Ross, R.G. and Andersson, P. (+32,) : Clathrate andother solid phases in the tetrahydrofuran gashydrate. Canadian Journal of Physics and Chemistry, 0* : 22+ῌ23,.
Ross, R.G., Andersson, P. and Bäckström, G. (+32+) ;Unusual PT dependence of thermal conductivity

Handa, Y.P., Hawkins, R.E. and Murray, J. J. (+32.) :Calibration and testing of a Tian-Calvet heat-

for a clathrate hydrate. Nature, ,3* : -,,ῌ-,-.
Rue#, R.M. and Sloan E.D. (+32/) : E#ect of granularﬂow calorimeter : Enthalpies of fusion and heatsediment

capacities for ice and tetrahydrofuran hydrate in

tetrahydrofuran hydrate. Industrial and Engi-the range 2/ to ,1*K. Journal of Chemical Ther-neering Chemistry Process Design Development,modynamics, +0 : 0,-ῌ0-,.

on

somethermalpropertiesof,. : 22-ῌ22/.

Hanley, H. J.M., Meyers, G. J., White, J.W. and Sloan,Sloan, E.D. (+33*) : Clathrate hydrates of natural

E.D. (+323) : The melting curve of THF hydrate ingases. p. 0.+, Marcel Dekker Inc, New York.

D,O. International Journal of Thermophysics,

Uchida, T. (+331) : Physical property measurements+* : 3*-ῌ3*3.

ῌon CO, clathrate hydrates. Review of crystallog+33+ : . He  +2 : ,+1ῌ,,-.
Iida, T., Mori, H., Mochizuki, T. and Mori, Y.H. (,**+) :Formation and dissociation of clathrate hydrate

raphy, hydration number, and mechanical properties. Waste Management, +1 : -.-ῌ-/,.

GHI ,**+ : JKLMNOP,-./01QRD  ,2 : 1*ῌ10.

in stoichiometric tetrahydrohuran-water mixture

Uchida, T., Ebinuma, T., Kawabata, J. and Narita, H.

subjected to one-directional cooling or heating.

(+333) : Microscopic observation of formation

Chemical Engineering Science, /0 : .1.1ῌ.1/2.

processes of clathrate-hydrate ﬁlms at an inter-Leaist, D.G., Murray, J. J., Post, M.L. and Davidson, D.

face between water and carbon dioxide. JournalW. (+32,) : Enthalpies of decomposition and heat
capacities of ethylene oxide and tetrahydrofuran
hydrates. Journal of Physical Chemistry, 20 :of Crystal Growth, ,*. : -.2ῌ-/0.

GH I STU +330 : ,-./01+ OPVWXBC Y Z[ +2 : 013ῌ02..
\]^_ ,*** : `-P/ab.+1/ῌ.+12.

c23

defMak, T.C.W. and McMullan, R.K. (+30/) : Polyhedral

ghNi _jkl mn opq 2. : .3ῌ/0.

clathrate hydrates. X. Structure of the double

Watanabe, K., Muto, Y. and Mizoguchi, M. (,**+) :hydrate of tetrahydrofuran and hydrogen sulﬁde.

Water and solute distributions near an ice lens in

The Journal of Chemical Physics, ., : ,1-,ῌ,1-1.

a glass-powder medium saturated with sodium

Matsumoto, R. (,**,) : Comparison of marine and per-chloride solution under unidirectional freezing.

mafrost gas hydrates : Examples from Nankai

Crystal Growth & Design, + : ,*1ῌ,++.

Trough and Mackenzie Delta. Proceedings of theWatanabe, K. (,**,) : Relationship between growth

Fourth International Conference on Gas Hy-rate and supercooling in the formation of icedrates : +ῌ0.

lenses in a glass powder. Journal of Crystal

ῌ!ῌ"#$% +333 : &'()*+

THF ,-./0123456789:;<=;> ?@ABCD EF 0+ : +.3ῌ+/..
Nagashima, K., Yamamoto, Y. Takahashi, M. and

Growth, ,-1ῌ,-3 : ,+3.ῌ,+32.
Zhu, D.M., Vilches, O.E., Dash, J.G. and Wettlaufer, J.
S. (,***) : Frost heave in argon. Physical Review
Letters, 2/ : .3*2ῌ.3++.

Komai, T. (,***) : Non-equilibrium salt concen-rstu : ,**- t ++ u +- 

tration distribution near growing and melting

rptu : ,**. t + u ,0 