Nitro
Nitro
Nitro
!"
#$%&'()& * +, -./01234, 5.67,/8349.6 23:7 ;.8,/696; 74,30 36< 694/.;,6 96=,549.6 96 3
.6,><90,679.632 ?./.17 0,<910 5.6439696; :34,/ .0?/,779@9294AB C,34 5.6<1549894A 36<
53?9223/94A 3/, 6,;2,54,< +, 741<A 4C, 5.6<,67349.6 -/.64 36< 7C.5D :38,7 3/9796; 96 4C,
E.:
+, F6< 4C34 4C,/, 3/, -.1/ ?.779@2, 4A?,7 .- 7.2149.67 -./ 4C, 9694932 36< @.16<3/A 5.6>
<949.67 .- 964,/,74 +, <,75/9@, 3 790?2, 5.674/1549.6 96 4C, 4,0?,/341/, 7341/349.6 ?236,
4C34 <,4,/096,7 4C, 5.0?2,4, 7.2149.6 -./ 4C, ;98,6 5.6<949.67
??295349.67 .- 4C, 4C,./A <,8,2.?,< C,/, 3/, 96 52,36 1? .- 7.92 5.64309634,< :94C 6.6>
3G1,.17 ?C37, 29G19<7 +, 7C.: 4C34 3 71@74364932 5.2< ;37,.17 H.6, <,8,2.?7 96 322 7.2149.67
.- ?/3549532 964,/,74B 4C17 5.164,/35496; <.:6:3/< 09;/349.6 .- 4C, ?.2214364
IJ KLMNOPQRMSOL
TUV WXYZ[Y\[Y] ^[_V`abVc_ XWW\bbVYWV Xd WXYZce[YcZ[XY _\V ZX `a[ff` cY_ fVcg` Xd Xb]cY[W
e cZVb[cf` `\WU c` aVZbXfV\e abX_\WZ` ^U[WU XWW\b _\b[Y] ZUV[b ZbcY`aXbZh `ZXbc]V cY_ _[`i
aX`cf Wc\`V` abXjfVe` dXb X\b U[]Uik\cf[Zl ]bX\Y_i^cZVb bV`X\bWV`J mY `a[ZV Xd [YWbVc`V_
c^cbVYV`` Xd ZUV VYn[bXYeVYZcf [eacWZ` Xd X[f `a[ff` [Z caaVcb` ZX jV [e aX``[jfV ZX cnX[_
ZUV`V cWW[_VYZ`J ob]cY[W aXff\ZcYZ` cbV bVdVbbV_ ZX c` YXYick\VX\` aUc`V f[k\[_` pqrstuh
^U[WU e cl UcnV c _VY`[Zl `ecffVb ZUcY ^cZVb ptqrstu Xb fcb]Vb ZUcY ^cZVb pvqrstuJ
Tbc_[Z[XYcf WfVcY \a eVZUX_` Xd ZUV`V `a[ff` `\WU c` a\e aicY_iZbVcZ cbV `fX^ jVWc\`V _[w\i
`[XYx_[``Xf\Z[XY cbV ZUV e c[Y bVeXncf eVWUcY[`e `J tXY] WfVcY \a Z[eV` acbZ[W\fcbfl XWW\b
dXb U[]Ufl UVZVbX]VYVX\` WXY_[Z[XY` yIz{hy|z{J
}VeXncf Xd WXYZce[YcYZ` ^[ZU `ZVce [` cY cfZVbYcZ[nVJ ~ZVce [YVWZ[XY [` ^[_Vfl `Z\_[V_
[Y sVZbXfV\e Y][YVVb[Y] yzz{hyzI{h yI|{J ~ZVce [YVWZ[XY fVc_` ZX cY VacY_[Y] UVcZV_ XYVh
`VacbcZV_ dbXe ZUV Xb[][Ycf WXf_ XYV jl c `UXbZ ZbcY`[Z[XY XYVh ^UVbV eX`Z Xd ZUV `ZVce
WXY_VY`V`J TUV ZbcY`[Z[XY XYV [` XdZVY WXY`[_VbV_ c` c dbXYZh ZUV `XiWcffV_ `ZVce WXY_VY`ci
Z[XY dbXYZJ ~ZVce WcY cf`X WfVcY acbZ` ZUcZ cbV [Y_[bVWZfl UVcZV_ jl WXY_\WZ[XYJ TUVbVdXbV
ZUV VwVWZ Xd UVZVbX]VYV[Zl [` `e cffVb jVWc\`V ZUV WXY_\WZ[n[Zl [` e\WU fV`` UVZVbX]VYVX\`
ZUcY ZUV aVbeVcj[f[ZlJ XY`Vk\VYZfl `ZVce [` cjfV ZX bVWXnVb Xb]cY[W aXff\ZcYZ` dbXe U[]Ufl
[eaVbeVcjfV acbZ` cY_ [` cjfV ZX bV_\WV ZUV ceX\YZ Xd X[f fVdZ ZX n[bZ\cffl VbXJ qXYV Xd
ZUV XZUVb ZVWUY[k\V` gYX^Y ZX_cl [` cjfV ZX WXeaVZV ^[ZU ZUV`V Z^X c_ncYZc]V` Xd `ZVce J
TUVbV [` cY cj\Y_cYZ f[ZVbcZ\bV XY VaVb[e VYZcf yI{ cY_ ZUVXbVZ[Wcf yI{ e X_Vf[Y] Xd `ZVce
[YVWZ[XY dXb WfVcY \a cY_ X[f bVWXnVblJ
"4,30 96=,549.6B 4C,/032 /,5.8,/AB ?./.17 0,<93B 01249?C37, E.: B CA?,/@.295
7A74,07B @9-1/5349.6
C97 :./D :37 71??./4,< 96 ?3/4 @A G 16<,/ /364 >B ! 16<,/ !
/364 B 16<,/ /364 >B /3H92 + 16<,/ ,22.:7C9? /364 >
B C, ,4C,/236<7 698 .- 966,7.43B 9,4H 3@./34./A ,2-4B C, ,4C,/236<7B
/3H92 "1??./4 .- 4C, 74,30 /,5.8,/A /,7,3/5C :./D @A ,2-4 698,/794A .- ,5C6.2.;A 36< @A "C,22 97 327.
35D6.:2,<;,< 37 :,22 37 @A 4C, 674 92,69.> 36<
TUVbV cbVh UX^VnVbh c Y\ejVb Xd abXjfVe` ^[ZU `ZVce ZUcZ cbV `Z[ff YXZ XaZ[e cffl `XfnV_J
oYV abXjfVe [` ZUcZ `ZVce cZ YXbecf jX[f[Y] ZVeaVbcZ\bV` WXe afVZVfl _V`ZbXl` ZUV VWX`l`i
ZVe J rYXZUVb [` ZUV _X^Y^cb_ e []bcZ[XY Xd vqrst c` [Z cWW\e\fcZV` YVcb ZUV `ZVce
WXY_VY`cZ[XY dbXYZ y|{h j y|{J mY jXZU Wc`V` `[e\fZcYVX\` [YVWZ[XY Xd `ZVce ^[ZU Y[ZbX]VY
Xb c[b [` cjfV ZX cffVn[cZV ZUV abXjfVe J ~[e\fZcYVX\` [YVWZ[XY Xd c YXYibVcWZ[nV ]c` fX^Vb`
ZUV ZVeaVbcZ\bV Xd ZUV `ZVce cZ c ][nVY ZXZcf abV``\bVh jVWc\`V ZUV ^cZVb abV``\bV jVWXe V`
fX^VbJ r fX^Vb ^cZVb abV``\bV fVc_` ZX c fX^Vb jX[f[Y] aX[YZJ TUVbVdXbV fV`` VYVb]l [` bVk\[bV_
ZX UVcZ \a ZUV `X[f ZX c fX^Vb ZVeaVbcZ\bVJ TUV [eaXbZcYZ dVcZ\bV ZUcZ fVc_` ZX c bV_\WZ[XY
Xd _X^Y^cb_ e XnVeVYZ [` ZUV aX``[jfV dXbe cZ[XY Xd c WXf_ ]c`VX\` XYV _X^Y`ZbVce Xd ZUV
`ZVce WXY_VY`cZ[XY dbXYZJ ~\WU c ]c`VX\` XYV _XV` YXZ XWW\b ^UVY a\bV `ZVce [` [YVWZV_ J
TUV eVWUcY[`e ZUcZ WX\YZVbcWZ` _X^Y^cb_ _[`afcWVeVYZ [` ZUcZ ZUV WXY_VY`[Y] qrst ` cbV
`abVc_ X\Z [Y ZUV ]c`VX\` XYVh ^U[WU bV_\WV` [Z` bVfcZ[nV aVbeVcj[f[Zl cY_ UVYWV ZUV bcZV
cZ ^U[WU [Z eXnV` _X^Y^cb_J TU[` eVWUcY[`e Uc` jVVY [YnV`Z[]cZV_ jXZU ZUVXbVZ[Wcffl cY_
VaVb[eVYZcffl yI {h y|{J X^VnVbh [Z Uc` YXZ jVVY [YnV`Z[]cZV_ ^UVZUVb c _X^Y`ZbVce WXf_
]c`VX\` XYV ^[ff cf^cl` V[`Z dXb cff aX``[jfV WXY_[Z[XY`J TUV V[`ZVYWV Xd `\WU c XYV [` c
abVbVk\[`[ZV ZX WX\YZVbcWZ _X^Y^cb_ eXnVeVYZJ mY ZUV `ce V ^cl ZUVbV WcY jV WXY_[Z[XY`
`\WU ZUcZ c _X^Y`ZbVce WXf_ ]c`VX\` XYV V[`Z`h j\Z [Z [` nVbl `UXbZJ mZ [` cf`X [eaXbZcYZ
ZX gYX^ ZUcZ XaZ[ecf WXY_[Z[XY` ZX WX\YZVbcWZ _X^Y^cb_ eXnVeVYZ WcY jV e c[YZc[YV_ VnVY
cdZVb UVcZ fX`` VwVWZ`J
mY Xb_Vb ZX [YnV`Z[]cZV ^UVZUVb c `\ W[VYZfl fcb]V WXf_ ]c`VX\` XYV ^[ff jV abV`VYZ dXb cff
aX``[jfV WXY_[Z[XY` [Z [` \`Vd\f ZX XjZc[Y c WXeafVZV `VZ Xd `Xf\Z[XY` dXb c bVabV`VYZcZ[nV `l`ZVe
Xd eX_Vf Vk\cZ[XY`J ~\WU c bVabV`VYZcZ[nV `l`ZVe WcY WXY`[`Z Xd ZUV WXe aXYVYZ e c`` jcfcYWV
Vk\cZ[XY` cY_ ZUV VYVb]l jcfcYWV Vk\cZ[XY `\aafVeVYZV_ ^[ZU vcbWl ` fc^ Xd e\fZ[iaUc`V
X^ J Xb c _[`Zb[j\Z[XY Xd WXeaXYVYZ` ce XY] ZUV aUc`V` ^V ecl c``\eV ZUVbeX_lYce[W
Vk\[f[jb[\e J mY c Iiv `VZZ[Y]h _[w\`[XYcf abXWV``V` `\WU c` e XfVW\fcb _[w\`[XYh _[`aVb`[XY h
ZUVbecf WXY_\WZ[XY cY_ Wca[ffcbl VwVWZ` cbV \`\cffl `ecff cY_ WcY jV _[`bV]cb_V_J TUVbVdXbV
ZUV e X_Vf Vk\cZ[XY` XYfl WXYZc[Y cY cWW\e\fcZ[XY ZVbe cY_ c WXYnVWZ[XY ZVbe J V ^[ff bVdVb
ZX ZUV eX_Vf Vk\cZ[XY` ^[ZU XYfl cWW\e\fcZ[XY cY_ WXYnVWZ[XY ZVbe` c` Vk\cZ[XY` [Y ZUV
UlaVbjXf[W dbceV^XbgJ
l c WXeafVZV `VZ Xd `Xf\Z[XY` ^V \Y_Vb`ZcY_ cff ZlaV` Xd `Xf\Z[XY` ZUcZ cbV k\cf[ZcZ[nVfl
_[wVbVYZJ r ^Vff gYX^Y VceafV Xd `Xf\Z[XY` ZUcZ cbV k\cf[ZcZ[nVfl _[wVbVYZ dXb `ZVce [YVWi
Z[XY [Y X[f bV`VbnX[b` [` abV`VYZV_ [Y ZUV Wfc``[Wcf acaVb jl cY_f cY_ XfVg yI {h ^UX `UX^
ZUcZ jVfX^ c Wb[Z[Wcf pYXYiVbXu `ZVce k\cf[Zl ZUV `ZVce WXY_VY`cZ[XY dbXYZ WVc`V` ZX V[`Z
cY_ c `ZVce _b[nV [` WXYnVbZV_ ZX c UXZ ^cZVb _b[nVJ
}VWVYZ _VnVfXaeVYZ` [Y ZUV ZUVXbl Xd j[d\bWcZ[XY` XWW\bb[Y] [Y `l`ZVe` Xd UlaVbjXf[W
WXY`VbncZ[XY Vk\cZ[XY` UcnV fV_ ZX c eVZUX_XfX]l ZX Y_ cff k\cf[ZcZ[nVfl _[wVbVYZ `Xf\Z[XY`J
r bVn[V^ Xd ZUV ZUVXbl [` `\ee cb[V_ dXb c aVZbXfV\e VY][YVVb[Y] c\_[VYWV [Y cY caaVY_[
Xd yI {J mY Xb_Vb ZX gVVa ZUV abXjfVe ZbcWZcjfV ^V WXY`[_Vb `ZVceiY[ZbX]VY X^ [Y ZUV d\ffl
`cZ\bcZV_ XYV cY_ []YXbV ZUV abV`VYWV Xd ZUV qrst WXYZce[YcYZJ V fVcnV ZU[` dXb d\Z\bV
^XbgJ TUV `Xf\Z[XY` Xd ZUV `ZVceiY[ZbX]VY X^ abXjfVe WcY jV WXYnVY[VYZfl [ff\`ZbcZV_
]bcaU[Wcffl [Y ZUV ZVeaVbcZ\bVh ^cZVb `cZ\bcZ[XY p u `acWVJ mY ZU[` aUc`V _[c]bce cff
ZlaV` Xd `Xf\Z[XY` WcY jV `UX^Y cY_ j[d\bWcZ[XY WXY_[Z[XY` cbV W\bnV` [Y ZU[` `acWVJ TUV`V
W\bnV` cbV fXW[ ^UVbV ^cnV `aVV_` jVWXeV Vk\cf Xb cZZc[Y ec[e\e ncf\V`J UVYVnVb c
`Xf\Z[XY acZU WbX``V` `\WU c j[d\bWcZ[XY W\bnV c YV^ ZlaV Xd `Xf\Z[XY [` VaVWZV_J VWc\`V
ecYl eX_Vf acbceVZVb` cbV V_ VJ]J ZUV ZVeaVbcZ\bV _VaVY_VYWV Xd ZUV _VY`[Z[V` cY_
n[`WX`[Z[V` cY_ XZUVb acbceVZVb` `\WU c` aXbX`[Zl cY_ bV`[_\cf `cZ\bcZ[XY` `UX^ XYfl `e cff
ncb[cZ[XY` ZUV ZXaXfX][Wcf `Zb\WZ\bV Xd ZUV aUc`V _[c]bce [` [Y ZU[` Wc`V bVabV`VYZcZ[nV dXb cff
WXY_[Z[XY`J mY_VV_ VnVY ncb[X\` VabV``[XY` Xd bVfcZ[nV aVbeVcj[f[Z[V` ^[ff fVc_ ZX ZUV `ceV
ZlaV Xd _[c]bce J
mY ~VWZ[XY | ^V ^[ff _V`Wb[jV ZUV eX_Vf dXb `ZVceiY[ZbX]VY [YVWZ[XY J V ^[ff dXbe\fcZV
ZUV Vk\cZ[XY` [Y ZUV UlaVbjXf[W dbceV ^XbgJ V ^[ff abXnV `XeV [eaXbZcYZ abXaVbZ[V` Xd
ZUV `Xf\Z[XY Xd ZUV Vk\cZ[XY`J mY ~VWZ[XY z ^V ^[ff dXbe\fcZV ZUV \]XY[XZ WXY_[Z[XY` cZ
ZUV `ZVce WXY_VY`cZ[XY dbXYZJ mY ~VWZ[XY ^V _[`W\`` ZUV bcbVdcWZ[XY` cY_ `UXWg` c^cl
dbXe WXY_VY`cZ[XYJ mY ~VWZ[XY ^V _VZVbe[YV ZUV `Zb\WZ\bV Xd ZUV }[Ve cYY `Xf\Z[XY` cY_
[Y ~VWZ[XY ^V `UX^ ZUV aUc`V _[c]bce` Xd c `Xf\Z[XY dXb cY [Y[Z[cffl ^cZVb `cZ\bcZV_ WXbVJ
raaVY_[ r WXYZc[Y` c ZcjfV Vafc[Y[Y] cff ZUV `lejXf`J XbVXnVb raaVY_[ r `\ee cb[V`
cff bVfVncYZ _VaVY_VYW[V` Xd aUl`[Wcf abXaVbZ[V` XY ZVeaVbcZ\bVJ ~XeV WcfW\fcZ[XY` bVfVncYZ
dXb ZUV e c[Y WUcY]V [Y ^cnV `Vk\VYWV caaVcb [Y raaVY_[ J
|J
OP
ON M N PS R LM S P M SN SL RMSOL
|JIJ !" # V WXY`[_Vb ZUV [YVWZ[XY Xd ^cZVbh `ZVce h cY_ Y[ZbX]VY Xb
XZUVb YXYibVcWZ[nV ]c` [Y c f[YVcb WXbV Xb[][Ycffl ffV_ ^[ZU ^cZVb p`VV []J |JIuJ TUV WXbV
WXY`[`Z` Xd `cY_ ^[ZU WXY`ZcYZ aXbX`[Zl $ cY_ aVbeVcj[f[Zl % & TUV WXbV [` UXb[XYZcf cY_ ^V
_[`bV]cb_ ZUV VwVWZ` Xd ]bcn[ZlJ TbcY`nVb`V Wca[ffcbl abV``\bV _[w\`[XY [` `\ W[VYZfl fcb]V
ZX ]\cbcYZVV c \Y[dXbe `cZ\bcZ[XY XnVb ZUV WbX``i`VWZ[XYJ TUV _[`afcWVeVYZ [` WXY`[_VbV_ ZX
XWW\b cZ WXY`ZcYZ abV``\bVh [Y ZUV `VY`V ZUcZ ^V _[`bV]cb_ cYl VwVWZ XY ZUV ZUVbeX_lYce[W
abXaVbZ[V` Xb \[_ n[`WX`[Z[V` _\V ZX X^ [Y_\WV_ abV``\bV ncb[cZ[XY`J
mY ZUV WXbV ^V Y_ Z^X ^[_V bV][XY` n[J c UXZ bV][XY cY_ c WXf_ bV][XY c` ^Vff c` c
`UXbZ `ZVce WXY_VY`cZ[XY XYVh ^U[WU ^V Wcff `ZVce WXY_VY`cZ[XY dbXYZJ }V][XY` cbV d\bZUVb
`\j_[n[_V_ [YZX XYV` cWWXb_[Y] ZX ZUV aUc`V` abV`VYZJ mY VcWU Xd ZUV bV][XY` ZUVbV WcY jV Z^Xi
aUc`V Xb `[Y]fV aUc`V X^ J V ^[ff c``\eV fXWcf ZUVbeX_lYce [W Vk\[f[jb[\e [Y VcWU Xd ZUV
^[_V bV][XY`J TU[` eVcY` ZUcZ [Y ZUV Z^XiaUc`V XYV` ZUV ZVeaVbcZ\bV [` _VZVbe[YV_ jl ZUV
acbZ[cf abV``\bV Xd ZUV `ZVce cY_ [` ][nVY jl cY Vea[b[Wcf bVfcZ[XY J qXYiVk\[f[jb[\e VwVWZ`
WcY XWW\b [Y ZUV ZbcY`[Z[XY XYV` jVZ^VVY ZUV ^[_V bV][XY`h j\Z cY Vaf[W[Z ecZUVe cZ[Wcf
_V`Wb[aZ[XY Xd ZUV ZbcY`[Z[XY XYV WcY jV cnX[_V_ [Y ZUV W\bbVYZ ZbVcZeVYZJ md c `\aVbUVcZV_
]c`VX\` e [Z\bV ^VbV [YVWZV_ cZ ZUV jV][YY[Y] Xd ZUV UXZ XYVh ZU[` jV][YY[Y] XYV ^X\f_
jV Xd c `[Y]fV aUc`V bV][XYJ TUV ZVeaVbcZ\bV [Y ZUV ZUV UXZ XYV ^[ff f[V jVfX^ ZUV [YVWZ[XY
ZVe aVbcZ\bVJ TUV WXf_ XYV ^[ff jV cZ ZUV Xb[][Ycf bV`VbnX[b ZVeaVbcZ\bVJ
mY Z^XiaUc`V X^ bV][XY` ZUV ]c`VX\` aUc`V WXY`[`Z` Xd Y[ZbX]VY cY_ `ZVce h ^UVbVc` ZUV
f[k\[_ aUc`V WXY`[`Z` XYfl Xd ^cZVbJ TUV ]c`V` VU[j[Z [_Vcf jVUcn[XbJ XY`Vk\VYZfl ^V
_[`bV]cb_ cYl UVcZ Xd e [[Y] VwVWZ jVZ^VVY ZUV ]c`V` cY_ c``\e V ZUcZ ZUV nXf\eV` Xd ZUV
]c`V` cbV c__[Z[nVh [JVJh ZUVbV [` YX nXf\eV WXYZbcWZ[XY VwVWZ \aXY e[[Y]J V _[`bV]cb_ cYl
_[``Xf\Z[XY Xd Y[ZbX]VY [Y ZUV ^cZVbJ V c``\eV ZUcZ ZUV n[`WX`[Zl Xd ZUV ]c`VX\` aUc`V [`
[Y_VaVY_VYZ Xd WXeaX`[Z[XYh j\Z ^V ZcgV ZUV ]c`VX\` aUc`V ZVeaVbcZ\bV _VaVY_VYWV [YZX
cWWX\YZJ TUV f[k\[_ ^cZVb n[`WX`[Zl _VaVY_` XYfl XY ZUV ZVeaVbcZ\bV cY_ ^V _V`Wb[jV [Z
jl c WXbbVfcZ[XY dXb a\bV ^cZVb n[`WX`[ZlJ mY ZUV Z^XiaUc`V bV][XY` ^V caafl vcbWl ` fc^
dXb e\fZ[aUc`V X^ J V \`V aX^Vb fc^ bVfcZ[nV aVbeVcj[f[Z[V`J ca[ffcbl dXbWV` cbV []YXbV_ J
TUV _VY`[Zl Xd ^cZVb _VaVY_` XY ZVeaVbcZ\bVh j\Z [Z [` [Y_VaVY_VYZ Xd ZUV ZXZcf abV``\bVJ
mY ZUV `[Y]fV aUc`V XYV` XYfl ^cZVb X^`J TUV ^cZVb Uc` ZUV `ceV abXaVbZ[V` c` _V`Wb[jV_
cjXnV dXb ZUV Z^XiaUc`V bV][XYJ
|J|J " " # TUV WXY`VbncZ[XY Xd ec`` Xd VcWU WXei
aXYVYZ [Y VcWU aUc`V [` ][nVY jl ZUV dXffX^[Y] Vk\cZ[XY`h ^U[WU VabV`` f[k\[_ ^cZVb e c``
jcfcYWVh `ZVce e c`` jcfcYWV [Y ZUV ]c`VX\` aUc`Vh cY_ Y[ZbX]VY ec`` WXY`VbncZ[XY [Y ZUV
]c`VX\` aUc`V p`VV dXb YXZcZ[XY y {u
p
$
u
p
u
p$ u
p u
p
$ u
p
u &
p|JIu
mY ZUV`V Vk\cZ[XY` [` ZUV ^cZVb `cZ\bcZ[XY h [JVJh ZUV dbcWZ[XY Xd ZUV aXbV` ffV_ ^[ZU
^cZVb cY_ [` ZUV ]c` `cZ\bcZ[XYJ \bZUVbeXbV
[` ZUV vcbWl nVfXW[Zl Xd ^cZVbh cY_
[` ZUV WXY_VY`cZ[XY bcZVJ V \`V ZX _VYXZV ZUV WXYWVYZbcZ[XY Xd `ZVce [Y ZUV
]c`VX\` aUc`Vh [JVJh ZUV e c`` Xd `ZVce aVb \Y[Z nXf\eVJ mY ZUV `ce V ^cl ^V _V YV ZUV
WXYWVYZbcZ[XY Xd Y[ZbX]VY & V cf`X _V YV ZUV X^ bcZV Xd `ZVce c`
& TU[` X^ bcZV
WXY`[`Z` Xd c WXYZb[j\Z[XY _\V ZX ZUV vcbWl nVfXW[Zl Xd ZUV ]c`
cY_ c WXYZb[j\Z[XY _\V
ZX _[w\`[XYJ TUV X^ bcZV Xd Y[ZbX]VY [` ][nVY c`
h cY_ [Z cf`X WXY`[`Z` Xd c WXYZb[j\Z[XY
_\V ZX ZUV vcbWl nVfXW[Zl cY_ c WXYZb[j\Z[XY _\V ZX _[w\`[XY J TU[` _[w\`[XY WXYZb[j\Z[XY
[` []YXbV_ UVbV c` [Z ^[ff jV d\bZUVb VfcjXbcZV_ [Y cYXZUVb acaVbJ VYWV [Z [` c``\eV_ ZUcZ
[` ZUV nXf\eV cnVbc]V_ vcbWl nVfXW[ZlJ
|J|JIJ ! " # $ % vcbWl ` fc^ Xd e\fZ[aUc`V X^ bVfcZV` abV``\bV ]bc_[VYZ
[Y c \[_ ^[ZU [Z` vcbWl nVfXW[Zl py {u
&
'
&
'
^UVbV ZUV ^cZVb cY_ ]c` e Xj[f[Z[V` cbV & % % ( ) * cY_ & % % ( ) * &
md Wca[ffcbl abV``\bV [` YV]fVWZV_h ZUV abV``\bV _[wVbVYWV jVZ^VVY ' cY_ ' WcY jV []YXbV_ J
mY ZU[` Wc`V ZUV X^ d\YWZ[XY` + h + _VYXZV ZUV dbcWZ[XYcf X^` cY_ cbV _V YV_ jl py {u
+
&
& &
cY_
+
+
&
& & ,
+
p|J|u
p|Jzu
fractional volume ()
nitrogen
0.8
0.6
0.4
steam
0.2
300
310
320
330
340
350
360
370
Temperature /K
^UVbV
p|Ju
p$ u
p$ u
p
+ u
p|Ju
p + u
p|J u
p + u &
p|J u
|J|J|J " $ % q[ZbX]VY cY_ `ZVce [Y ZUV ]c`VX\` aUc`V cbV c``\eV_
ZX jVUcnV c` [_Vcf ]c`V`J mY acbZ[W\fcb ZUV ec`` _VY`[Z[V` Xd ZUV`V ]c`V` WcY jV ^b[ZZVY c`
p|J u
^UVbV
cbV ZUV eXfVW\fcb ^V[]UZ` Xd ^cZVb cY_ Y[ZbX]VY bV`aVWZ[nVfl cY_
[` ZUV
]c` WXY`ZcYZJ TUV Wca[Zcf cY_ c` `\j`Wb[aZ Xd VeaUc`[V ZUcZ ZUV`V cbV _VY`[Z[V` Xd
ZUV a\bV WXeaXYVYZ`J ~[YWV [Y [_Vcf ]c` jVUcn[Xb c``\eV_ [Y ZU[` ^Xbgh ZUVbV cbV YX nXf\eV
VwVWZ` _\V ZX e[[Y] , `[e[fcbflh ZUV VYZUcfal WUcY]V` _\V ZX e[[Y] Xd ZUV ]c` WXe aXYVYZ`
cbV VbXJ TUVbVdXbV ZUV nXf\eV` Xd ZUV WXe aXYVYZ` cbV c__[Z[nV
I&
p|J u
'
'
`[Y] kJ p|J uh ZUV WXYWVYZbcZ[XY Xd `ZVce cY_ Xd Y[ZbX]VY [Y ZUV e[Z\bV WcY jV
VabV``V_ [Y ZVbe` Xd ZUV a\bV aUc`V _VY`[Z[V`
h c`
&
p|JI u
TU[` Vk\cZ[XY WcY jV bV]cb_V_ c` _V Y[Y] ZUV nXf\eV dbcWZ[XY` cY_ Xd `ZVce cY_
Y[ZbX]VY [Y ZUV ]c`VX\` aUc`VJ p~VV []J |J|Ju TUV VYZ[bV Z^XiaUc`V ZUVbeX_lYce[W jVUcn[Xb
[` `aVW[ V_ jl ZUV Vk\[f[jb[\e WXY_[Z[XY jVZ^VVY ^cZVb cY_ `ZVce ][nVY jl kJ pr J u cY_
ZUV _VY`[Z[V` h cbV WXea\ZV_ \`[Y] pr J uJ
rff XZUVb abXaVbZ[V` bVfVncYZ ZX ZUV WXea\ZcZ[XY cbV `\e ecb[V_ [Y raaVY_[ r J
|JzJ ! " " # TUV WXY`VbncZ[XY Xd VYZUcfal [` ][nVY c`
(
$
$
p
u
p
u &
p|JIIu
TUV jc`[` Xd \`[Y] ZU[` Vk\cZ[XY WcY jV dX\Y_ [Y yz{ pac]V z|zh TcjfV I JiIh kJ }u cY_ yI{
ac]V Ih dXXZYXZVuJ mZ \`V` ZUV c``\eaZ[XY p`VV `VWZ[XY |JIu ZUcZ c` ZX ZUV ZUVbeX_lYce[W
k\cYZ[Z[V` ZUV `l`ZVe [` cZ WXY`ZcYZ abV``\bVJ a`Wcf[Y] [``\V` bV]cb_[Y] ZUV Vk\cZ[XY` [Y
aXbX\` eV_[c WcY jV dX\Y_ [Y y| {J
TUV VYZUcfa[V` cbV cff aVb \Y[Z ec`` cY_ _VaVY_ XY ZVeaVbcZ\bV cY_ abV``\bV p`VV
raaVY_[ ruJ TUV VYZUcfal Xd ^cZVb [Y ZUV ]c`VX\` aUc`V [`
h cY_
[` ZUV VYZUcfal Xd
^cZVb [Y ZUV f[k\[_ ck\VX\` aUc`V ^U[fV [` ZUV VYZUcfal Xd Y[ZbX]VY [Y ZUV ]c`VX\` aUc`VJ
mY k\cZ[XY p|JIIu ZUVbecf WXY_\WZ[n[Zl Uc` jVVY _[`bV]cb_V_h c` ^V cbV [Y ZUV UlaVbjXf[W
dbce V^XbgJ
! # # TUV nXf\eV dbcWZ[XY` )
cY_ ) c__ \a ZX XYV p`VV
k\cZ[XY p|J uu `X ZUcZ ZUV dX\b Vk\cZ[XY` p|Ju p|J uh p|JIIu Wcbbl dX\b \YgYX^Y`h YceVflh
ZUV WXY_VY`cZ[XY bcZV ZUV ^cZVb `cZ\bcZ[XY ZUV ZVeaVbcZ\bV cY_ ZUV ZXZcf
nVfXW[Zl
& fVcbfl ^V UcnV I h cY_ p uh p u dXb c ][nVY ZXZcf
abV``\bV ' J
|JzJIJ
" # % mY kJ p|JIIuh ^V `af[Z ZUV VYZUcfal Xd
`ZVce
[YZX c `VY`[jfV acbZ
cY_ c fcZVYZ acbZ
Vncf\cZV_ cZ ZUV bVdVbVYWV ZVeaVbcZ\bV
&
V `\j`Z[Z\ZV k J p|JI|u [YZX kJ p|JIIuJ TUV ZVbe ` ZUcZ WXYZc[Y ZUV dcWZXb
bV`\fZ[Y] Vk\cZ[XY cbV
p$ u
p|JI|u
[Y ZUV
p u
^UVbV ^V UcnV \`V_ ZUV `ZVce jcfcYWV k\cZ[XY p|J u ZX XjZc[Y ZUV b[]UZ UcY_ `[_V Xd ZU[`
Vk\cZ[XYJ VYWV k J p|JIIu WcY jV bV^b[ZZVY c` ZUV Ycf Vk\cZ[XY
(
$
$
u & p|JIzu
abV``\bVJ mZ WcY jV `UX^Y ZUcZ dXb Z^XiaUc`V X^ ZUV ZVeaVbcZ\bV [` WXY`ZcYZ abVW[`Vfl
^UVbV [_VYZ[WcfflJ
|JJ " " ! ! ! # TUV Vk\cZ[XY` [Y UlaVbjXf[W dbceVi
^Xbg _[`bV]cb_ _[w\`[XYh Wca[ffcbl ZVbe`h c` ^Vff c` UVcZ WXY_\WZ[n[ZlJ TUVl cbV caabXab[cZV
dXb ZUV `Z\_l Xd bcbVdcWZ[XY ^cnV` c` ^Vff c` dXb ZUV WXY_VY`cZ[XY cY_ `UXWg ^cnV` dXb `UXWg
^cnV` cY_ dXb WXY_VY`cZ[XY ^cnV` yz|{J bXe k`J p|Ju p|J uh ^V XjZc[Y
p$
u
p$ u
p
+ u
p
+ u
p|JIu
p|JIu
p
$ u
p
+ u
^UVbV ^V UcnV [YZbX_\WV_ W\e\fcZ[nV WXY_VY`cZ[XY bcZV p u c`
p|JI u
p u `\WU ZUcZ
bXe k`J p|JI u cY_ p|JIzu ^V XjZc[Y
u &
p|JI u
p
( $ p
uu
p
+ + u
&
p|JI u
mY ZUV UlaVbjXf[W dbceV^Xbgh ZUV Vk\cZ[XY` dXb `ZVce cY_ c[b [YVWZ[XY cbV p|JIu p|JI uJ
! # # j l e cY[a\fcZ[Y] kJ p|JIuip|JI u cY_ p|JI uh [Z WcY jV `UX^Y ZUcZ ZUV
ZUVbe cf nVfXW[Zl dXb VbX [`
&
p|JI u
+ +
(
$ p
&
u&
[` _[wVbVYZJ
V ^[ff Y_ [Z \`Vd\f ZX
zJ
L SL
Q OLSOM ROLPSMSOL
ON M
M ROLP L MSOL
NOLM
TUV }cYg[YVi \]XY[XZ WXY_[Z[XY` cbV ZUV ecZUVe cZ[Wcf VabV``[XY` dXb c jcfcYWV Vk\cZ[XY
pVJ]J e c`` jcfcYWV Xb VYVb]l jcfcYWVu cZ c `UXWg [JVJ aX`[Z[XY [Y `acWV ^UVbV ^V UcnV
c _[`WXYZ[Y\X\` WUcY]V Xd ncb[cjfV` p`VV kJ |JI [Y bVdVbVYWV yz|{uJ rY VceafV [` ZUV
`UXWg [Y ZUV \WgfVlitVnVbVZZ abXjfVe J TUV }cYg[YVi \]XY[XZ WXY_[Z[XY` bVfcZV ZUV `ZcZV
\a`ZbVce cY_ _X^Y`ZbVce Xd cYl `UXWg p[YWf\_[Y] ZUV `ZVce WXY_VY`cZ[XY dbXYZu ^[ZU [Z`
`aVV_ J
zJIJ ! " " " " # TUV \]XY[XZ Vk\cZ[XY` cZ
ZUV `ZVce WXY_VY`cZ[XY dbXYZ cbV XjZc[YV_ dbXe k`J p|JIu p|JI uJ TUV nVfXW[Zl [` ZUV
nVfXW[Zl Xd ZUV `ZVce WXY_VY`cZ[XY dbXYZJ VbV p u _VYXZV` ZUV `ZcZV cZ b[]UZ p_X^Y`ZbVce u
Xd ZUV `UXWgh ^U[fV p u _VYXZV` ZUV `ZcZV cZ ZUV fVdZ pXb \a`ZbVce uJ
$ p
u p
u p
+ u p
+ u
pzJIu
$ p u p u p
+ u p
+ u
pzJ|u
$ p u p u p
+ u p
+ u &
pzJzu
mY k`J pzJIu cY_ pzJ|u ^V UcnV \`V_ ZUV dcWZ ZUcZ jl ZUV _V Y[Z[XY [Y kJ p|JI uJ
TUV \]XY[XZ WXY_[Z[XY dXb ZUV VYVb]l [` _Vb[nV_ [Y ZUV `ce V ^cl dbXe kJ p|JI u
p
(
$ p
uu p ( $ p
uu
p
u
p
u
pzJu
TUV dX\b Vk\cZ[XY` pzJIuh pzJ|uh pzJzu cY_ pzJu cbV cff f[YVcb [Y ZVbe` Xd
&
TUVbVdXbV ^V WUXX`V ZUbVV Vk\cZ[XY` pZ^X caabXab[cZV WXej[YcZ[XY` Xd ZUV ec`` jcfcYWV
Vk\cZ[XY` cY_ ZUV VYVb]l Vk\cZ[XYu ZX XjZc[Y ZUV ncf\V` Xd
[Y ~VWZ[XY zJ|J
TUVY [Y ~VWZ[XY zJzJI ^V \`V ZUV bVe c[Y[Y] e c`` jcfcYWV Vk\cZ[XY c` c YXYif[YVcb Vk\cZ[XY
dXb J
! # # k\cZ[XY pzJu WcY jV `[eaf[ V_ jl ZUV \`V Xd WXY`ZcYZ UVcZ WcacW[Z[V`
$ ( )$
+ + ) pzJu
^UVbV ZUV cjjbVn[cZ[XY p u [` ][nVY jl
p
up
u &
pzJ u
[ZUX\Z fX`` Xd ]VYVbcf[Zl [Z WcY jV c``\eV_ ZUcZ
h cbV VbX cY_ h cbV
VYZUcfa[V` ^[ZU bV`aVWZ ZX J
TUV ZVbe caabX[e cZV` ZUV UVcZ bVk\[bV_ ZX WXYnVbZ f[k\[_ ^cZVb cZ ZVeaVbcZ\bV ZX
`ZVce cZ ZUV `ceV ZVeaVbcZ\bVJ mZ [` c aX`[Z[nV k\cYZ[Zl p`VV ZUV dXffX^[Y] bVe cbguJ
! # # V cbV XYfl [YZVbV`ZV_ [Y ZVeaVbcZ\bV` cY_ jVfX^ ZUV Wb[Z[Wcf ZVeaVbi
cZ\bV [JVJ ZUV ZVeaVbcZ\bV cZ ^U[WU ZUV aUl`[Wcf _[wVbVYWV jVZ^VVY ZUV f[k\[_ cY_ [Z` ncaXb
WVc`V` ZX V[`ZJ VfX^ ZUV Wb[Z[Wcf ZVeaVbcZ\bV ZUV UVcZ Xd VncaXbcZ[XY p u p
u
[` aX`[Z[nVh ^U[fV cZ ZUV Wb[Z[Wcf aX[YZ [Z ncY[`UV` p u h cY_ & p u & p uh
[JVJh ZUV `aVV_ Xd ZUV `ZVce WXY_VY`cZ[XY dbXYZh ZUV ZUVbe cf WUcbcWZVb[`Z[W `aVV_` cZ ZUV fVdZ
cY_ b[]UZ jVWXeV Vk\cfJ Tcg[Y] ZUV f[e[Z` ^[ZU [Y kJ pzJuh
ZUcZ [` ZUV `ceV c` [Y kJ pzJuh cY_ ^V Xj`VbnV ZUcZ dXb `\jWb[Z[Wcf ZVeaVbcZ\bV`
&
p u & p u cY_ &
p u & p u & VbV & [` _V YV_ c`
& p u
f[e &
pzJ u
+ +
+ +
&
+
+
+
cY_ WXYWVYZbci
+
pzJ u
+
pzJI u
+ &
pzJIIu
V c__ Vk\cZ[XY` pzJ u cY_ pzJI uh c` ^Vff c` pzJ u cY_ pzJIIuh XjZc[Y[Y]
I I
+ +
I
I
+
+ &
pzJI|u
pzJIzu
V `\aafVeVYZ ZUV Z^X f[YVcbfl [Y_VaVY_VYZ Vk\cZ[XY` cjXnV jl ZUV dXffX^[Y] bV^b[ZZVY
nVb`[XY Xd ZUV VYVb]l WXY`VbncZ[XY Vk\cZ[XY pzJuJ V e\fZ[afl k`J pzJIuh pzJ|uh pzJzu jl
ZUV[b bV`aVWZ[nV VYZUcfa[V`
h
h h cY_ `\jZbcWZ dbXe kJ pzJuh XjZc[Y[Y]
pzJIu
^UVbV ZUV UVcZ Xd VncaXbcZ[XY cZ ZVeaVbcZ\bV [` _V YV_ jl
pzJIu
&
cY_ ^V cjjbVn[cZV_ ZUV VYZUcfal WXYZVYZ Xd ZUV eV_[\e h ZUV VYZUcfal \
c` dXffX^`
p ( ( u ) $
p
p
u
pzJI u
p
u + p
&
pzJI u
qXZ[WV ZUcZ dXb ZUV WXV W[VYZ Xd [` VbXh `X ZUV `Xf\Z[XY _V`Wb[jV_ [Y ZU[`
~VWZ[XY zJz [` XYfl ncf[_ dXb J mY raaVY_[ ^V abXnV ZUcZ ZUV WXV W[VYZ` Xd
[Y kJ pzJI u cY_ pzJI u cbV aX`[Z[nV [Y X\b Wc`Vh ^UVbV &
TUV WXV W[VYZ Xd [Y kJ pzJI u [` Vc`[fl `VVY ZX jV ZUV _VZVbe [YcYZ Xd ZUV `l`ZVe
pzJI|u pzJIuJ md ZU[` WXV W[VYZ [` c``\e V_ ZX jV YXYiVbXh [` _VZVbe[YV_J ~\j`Z[Z\Z[XY
[YZX pzJI u abXn[_V` ZUV ncf\V Xd J [Ycffl ^V XjZc[Y dbXe kJ pzJIzu ZUV ncf\V Xd
&
UVbV ZUV WXV W[VYZ Xd [` VbX c j[d\bWcZ[XY ^[ff XWW\b p[JVJ cZ uJ ~X c^cl
dbXe ZUV j[d\bWcZ[XY ZUV `l`ZVe WcY jV `XfnV_ \Y[k\VflJ
zJzJIJ $ " % V UcnV dX\Y_ ZUV k\cYZ[Z[V` h
h & V _[n[_V kJ pzJ u
jl
cY_ ^V bVcbbcY]Vh XjZc[Y[Y]
p u
+
+
&
pzJI u
TUV ]bcaU Xd ZUV b[]UZ UcY_ `[_V [` c `Zbc[]UZ f[YV [Y c h + afXZh ^U[WU Uc` cZ e X`Z ZUbVV
[YZVb`VWZ[XY` ^[ZU ZUV ]bcaU Xd + p uJ cWU [YZVb`VWZ[XY Xd ZUV Z^X ]bcaU` [` c aX[YZ [Y ZUV
\]XY[XZ W\bnV [Y ZUV p
u afcYVJ r` ncb[V` VcWU [YZVb`VWZ[XY ]VYVbcZV` c acbZ Xd
ZUV \]XY[XZ W\bnVJ TcY]VYWl Xd ZUV Z^X ]bcaU` e cgV` Z^X acbZ` WXcfV`WV ZUV Y\ejVb Xd
[YZVb`VWZ[XY` WUcY]V` jl Z^Xh Xb[][YcZ[Y] c dXf_ [Y ZUV \]XY[XZ W\bnVJ
rZ ZUV VY_ Xd ZU[` abXWV_\bVh ^V UcnV WXeafVZV_ ZUV WcfW\fcZ[XY Xd ZUV k\cYZ[Z[V` h
^[ZU aX``[jfl `VnVbcf ncf\V` Xd ZUV k\cYZ[Zl
h WXbbV`aXY_[Y] ZX c ][nVY ncf\V dXb
h
J md ^V afXZ cff ncf\V` Xd
cY_
dXb [Y ZUV bcY]V Xd ZVeaVbcZ\bV` Xd
[YZVbV`Zh ^V XjZc[Y ZUV YXYi[`XZUVbecf jbcYWU Xd ZUV \]XY[XZ W\bnVJ
ce afV` Xd YXYi[`XZUVbe cf \]XY[XZ W\bnV` cbV `UX^Y [Y []J zJIJ
zJzJ|J # $ " $ # % UVY ^V `\j`Z[Z\ZV
[YZX k J pzJIu ^V XjZc[Y ZUV `[eafV Vk\cZ[XY & TUVbVdXbV J VYWV ^V
XjZc[Y dbXe pzJIzu ZUcZ
IJ ~VZZ[Y] [Y c__[Z[XY ZX
I [Y k`J
pzJIuh pzJ|uh cY_ pzJzu ^V XjZc[Y ZUV Vk\[ncfVYZ dXbe` Xd ZUV }cYg[YVi \]XY[XZ WXY_[Z[XY dXb
ZUV \WgfVlitVnVbVZZ Vk\cZ[XY ^[ZU YX WXY_VY`cZ[XY
+ + &
pzJ| u
+ +
TU[` Vk\cZ[XY `UX^` ZUcZ dXb h cYl p u f[V` [Y ZUV } fXW\` Xd p uJ
Xb c ][nVY
h kJ pzJ| u d\bY[`UV`
J V Wcff ZU[` ZUV [`XZUVbecf Xb \WgfVlitVnVbVZZ
jbcYWU Xd ZUV \]XY[XZ W\bnV , Xjn[X\`flh [Z _XV` YXZ [YnXfnV WXY_VY`cZ[XY cY_ [Z WXYZc[Y`
p uJ
! #
# TUV `ZcZV p u [` cf`X WXYZc[YV_ [Y ZUV \]XY[XZ jbcYWU ZUcZ _V`Wb[jV`
ZUV `ZVce WXY_VY`cZ[XY dbXYZJ r` ^V `VV [Y []J zJI jl _bc^[Y] ZUV [`XZUVbe cf jbcYWU c` c
nVbZ[Wcf f[YV ZUbX\]U VcWU aX[YZ p uh jV`[_V` [YZVb`VWZ[Y] cZ ZU[` aX[YZ ZUV`V Z^X jbcYWUV`
XdZVY [YZVb`VWZ cZ cYXZUVb XYVJ mY VceafV` mim [Y ZU[` ]\bVh ZUVbV cbV Z^X [YZVb`VWZ[XY`J
VIII
VII
0.9
VI
watersaturation Sw
0.8
0.7
0.6
IV
0.5
III
II
0.4
0.3
EI
coincidence curve
0.2
0.1
EII
280
300
320
340
Temperature T+ /K
360
380
&
+
p u &
pzJ|Iu
pzJ||u
md ZUVbV cbV Z^X `Xf\Z[XY` `cZ[`dl[Y] ZUV \]XY[XZ WXY_[Z[XY` pzJIuh pzJ|uh pzJzuh pzJuh [Z
Z\bY` X\Z ZUcZ XYfl XYV Xd ZUVe `cZ[` V` pzJ|IuJ oYV WcY nVb[dl ZUcZ [Y X\b Wc`V ZUV XZUVb tc
VYZbXal [YVk\cf[Zl WXY_[Z[XY dXb c_e[``[j[f[Zl [` n[XfcZV_J qceVflh ZUV dXffX^[Y] [` n[XfcZV_
`Xe VZ[eV`
&
pzJ|zu
p u &
zJJIJ # " # $ $ % mY []J zJI ^V `UX^ \]XY[XZ W\bnV`
dXb V[]UZ _[wVbVYZ p u `ZcZV` p[Y_[WcZV_ jl `Xf[_ W[bWfV`Ju TUV \]XY[XZ W\bnV` cbV YXZ _bc^Y
jVfX^ ZUV WXYYcZV ^cZVb `cZ\bcZ[XY jVWc\`V `\WU `ZcZV` cbV [YcWWV``[jfV \Y_Vb
YXbe cf X^ J
cYl YXYi[`XZUVbecf \]XY[XZ W\bnV` UcnV c " h c aX[YZ ^UVbV ZUVl UcnV c nVbZ[Wcf
ZcY]VYZ [Y c p u afcYV , XYV WcY `UX^ ZUcZ p u [` c dXf_ aX[YZ [d cY_ XYfl [d [Z jVfXY]`
ZX ZUV WX[YW[_VYWV W\bnVJ
a`ZbVce `ZcZV` [Y ZUV ZU[Y acbZ` Xd ZUV W\bnV UcnV ZUV c__[Z[XYcf abXaVbZl ZUcZ ZUV `ZVce
WXY_VY`cZ[XY dbXYZ nVfXW[Zl [` fcb]Vb ZUcY ZUV `cZ\bcZ[XY ^cnV nVfXW[Zl cY_ _X YXZ `cZ[`dl ZUV
VYZbXal WXY_[Z[XY pzJ|zuJ TUcZ [`h ZUVl _X YXZ fVc_ ZX c_e[``[jfV `Xf\Z[XY`h c` [Z [` ^Vff
Vafc[YV_ Vf`V^UVbV yz|{J
~ZcZV` XY ZUV \]XY[XZ W\bnV ^U[WU `cZ[`dl ZUV VYZbXal WXY_[Z[XY e cb][Ycffl [JVJh ZUX`V
`cZ[`dl[Y] ZUV dXffX^[Y] VYZbXal Vk\cf[Zl ^[ff jV `UX^Y ZX UcnV [eaXbZcYZ bXfV [Y }[Ve cYY
`Xf\Z[XY`
&
pzJ|u
p u &
oYV WcY abXnV ZUcZ aX[YZ` ZVY_` ZX aX[YZ` p u c` ZUV fcZZVb ZVY_` ZX ZUV WX[YW[_VYWV
W\bnVJ TU\`h dXb aX[YZ` p u XY Xb cjXnV ZUV WX[YW[_VYWV W\bnVh ZUV [Yc_e[``[jfV acbZ Xd ZUV
\]XY[XZ W\bnV dbXe p u ZX _[`caaVcb`J TU[` [` WXY`[_VbV_ ZUV eX`Z [eaXbZcYZ dVcZ\bV Xd
ZUV WX[YW[_VYWV W\bnVJ
J OL ROLP L MSOL LM N
XY`[_Vb[Y] [jj` ` aUc`V b\fV cY_ ZUV WXY`ZcYZ abV``\bV WXY_[Z[XY` ZUVbV cbV Z^X _V]bVV`
Xd dbVV_Xe dXb `[Y]fV aUc`V ]c` X^ pZVeaVbcZ\bVh WXeaX`[Z[XYu cY_ XYV _V]bVV Xd dbVV_Xe
pZVeaVbcZ\bVu ^UVY Z^X aUc`V` cbV abV`VYZJ bXe ZUV Ul_bX_lYce[W aX[YZ Xd n[V^ ZUV
`cZ\bcZ[XY [` cY c__[Z[XYcf _V]bVV Xd dbVV_Xe J
JIJ # r` _[`W\``V_ [Y ~VWZ[XY |JzJ|h [d ZUV ZVeaVbcZ\bV WUcY]V` ZUVbV [`
c YXYiVbX `X\bWV ZVbe J ~Vfdi`[e[fcb `Xf\Z[XY` [Y ZU[` Wc`V cbV `UXWg ^cnV` pZUV `ZVce WXYi
_VY`cZ[XY dbXYZ` cbV `Z\_[V_ [Y cYXZUVb `VWZ[XYu Xb bcbVdcWZ[XY ^cnV`h ^U[WU WXbbV`aXY_ ZX
VncaXbcZ[XY h `X ZUVl cbV YXZ `Z\_[V_ [Y ZU[` ^XbgJ
md ZUV ZVe aVbcZ\bV _XV` YXZ WUcY]Vh cff WXYWVYZbcZ[XY` cbV WXY`ZcYZ cY_ ZUV X^ bV_\WV` ZX
ZUV Wfc``[Wcf Z^XiaUc`V \WgfVlitVnVbVZZ abXjfVe ^[ZU c ]c` aUc`V Xd WXY`ZcYZ WXe aX`[Z[XY J
TUV [`XZUVbecf \WgfVlitVnVbVZZ X^ c_e[Z` `UXWg`h bcbVdcWZ[XY`h Xb bcbVdcWZ[XYi`UXWg`J
TUV `UXWg `aVV_ [`
p$ )
u
h ^UVbV
^c` cfbVc_l _V YV_ [Y kJ pzJ| uJ TUV
p`WcfV_u bcbVdcWZ[XY `aVV_ ^c` cfbVc_l _V YV_ [Y kJ pzJ||uJ
J|J " " ! " ! # V _V`Wb[jV `UXWg` ZUcZ `VacbcZV bV][XY` ^[ZU
Z^XiaUc`V X^ dbXe bV][XY` ^[ZU `[Y]fV aUc`V f[k\[_ X^ h jXZU cZ U[]U ZVeaVbcZ\bVJ ~\WU
`UXWg` cbV c f[e[Z[Y] Wc`V Xd Z^XiaUc`V X^ h `X ZUVl UcnV
ZX XWW\b cZ WXY`ZcYZ ZVeaVbcZ\bV c` Vafc[YV_ jVdXbVJ TUV[b `aVV_ [`
+
+
+ I
&
pJIu
$ I
$
JzJ # rY cWW\bcZV _V`Wb[aZ[XY Xd ZU[` X^ WcY jV dX\Y_ [Y y {J Xb
`[e af[W[Zlh ^V _V`Wb[jV f[k\[_ X^ \Y_Vb ZUV ]XX_ caabX[e cZ[XY ZUcZ ZUVbe cf VacY`[n[Zl
Xd ^cZVb [` YV]f[][jfV pZUV `ceV [` Zb\V dXb bXWguJ TU\`h ZUV jcfcYWV Vk\cZ[XY` p|JIuh p|JI uh
p|JI u bV_\WV ZX
$
p
u
p ( $
u
pJ|u
p
u &
pJzu
c`V_ XY pJ|uh XYV WcY `UX^ ZUcZ
) J V cf`X []YXbV ZUV ZVeaVbcZ\bV _VaVY_VYWV
Xd ZUV ^cZVb cY_ bXWg UVcZ WcacW[Z[V` aVb \Y[Z nXf\eV
( cY_ _[`bV]cb_ f[k\[_ ^cZVb
cY_ bXWg VacY`[n[Zlh `X ZUcZ ZUV ^cnV Xd [YZVbV`Z [Y ZUV ^cZVb jVWXeV` c ZUVbecf WXYZcWZ
_[`WXYZ[Y\[Zl y {J pTU[` dXffX^` dbXe kJ pJzuJu
Tla[Wcffl ZU[` ^cnV V[`Z` c` c $ jVZ^VVY UXZ ^cZVb ^[ZU ZVeaVbcZ\bV
cY_ ^cZVb cZ [Y[Z[cf bV`VbnX[b `cZ\bcZ[XY ^[ZU ZVeaVbcZ\bV [Z` `aVV_ WcY jV ^b[ZZVY c`
,
(
$
&
pJu
oY ZUV XZUVb UcY_h ^V UcnV nVb[ V_ Y\eVb[Wcffl ZUcZ [Y ZUV WXY_VY`cZ[XY \]XY[XZ W\bnV
ZUV dXffX^[Y] [YVk\cf[Zl [` cf^cl` `cZ[` V_ dXb c `Vk\VYWV Xd `ZcZV` p uh p uh
p u p u
pJu
^UVbV _VYXZV` ZUV [Y[Z[cf `ZcZVJ
J M N SL MSOL O
M
MNQRMQN O
M
S LL O QMSOL
~aVV_ Vk\cf[Zl Xd _[wVbVYZ ^cnV` Zla[Wcffl bVabV`VYZ` bV`XYcYWV cY_ ]VYVbcZV` j[d\bWcZ[XY`J
VYWV ZUV fXW[ ^UVbV `\WU Vk\cf[Z[V` XWW\b cbV WcffV_ " $ J md ZUVl cbV W\bnV`h ZUVl
cbV WcffV_ " $ $ J
UVYVnVb c `Xf\Z[XY acZU WbX``V` c j[d\bWcZ[XY W\bnVh fXWcffl ZUV }[Ve cYY `Xf\Z[XY jVi
WXe V` k\cf[ZcZ[nVfl _[wVbVYZJ UVY c `Xf\Z[XY acZU WbX``V` ZUV `ceV `VZ Xd W\bnV` ZUV XnVbcff
k\cf[ZcZ[nV jVUcn[Xb ^[ff jV `[e[fcbJ TUVbVdXbV [Z [` [eaXbZcYZ ZX `Z\_l ZUV j[d\bWcZ[XY W\bnV`J
JIJ " !! ! # mZ [` aX``[jfV ZX `UX^ ZUcZ ZUVbV [` cZ eX`Z XYV WXY_VY`cZ[XY
dbXYZJ UVZUVb ZUVbV [` XYV Xb YXYV _VaVY_` XY ZUV [YVWZ[XY WXY_[Z[XY`J UVY ZUVbV [` YX
WXY_VY`cZ[XY dbXYZ ZUV _X^Y`ZbVce f[k\[_ bV][XY [` `VacbcZV_ dbXe ZUV \a`ZbVce Z^XiaUc`V
bV][XY jl cY [`XZUVbecf ^cnVh ZUV #
# ! _V`Wb[jV_ [Y
~VWZ[XY J|J po\b \a`ZbVce WXY_[Z[XY` cbV cf^cl` Z^X aUc`V cY_ ^V cbV VWf\_[Y] VncaXbci
Z[XYJ TU\`h YXYi[`XZUVbe cf WXY_[Z[XY` WXYZbc_[WZ ZUV cj`VYWV Xd c WXY_VY`cZ[XY dbXYZJ
bXe ZUV [YVk\cf[Zl pJuh ZUVbV [` YX ZUVbe cf ^cnV _X^Y`ZbVce Xd ZUV `ZVce WXY_VY`ci
Z[XY dbXYZJ TU\`h ^UVY ZUVbV [` c WXY_VY`cZ[XY dbXYZh [Z` _X^Y`ZbVce ZVeaVbcZ\bV [` ZUV
[Y[Z[cf ZVe aVbcZ\bV Xd ZUV bV`VbnX[bJ TUV \a`ZbVce pfVdZu ZVeaVbcZ\bV [` ZUV [YVWZ[XY
ZVe aVbcZ\bV jVWc\`V ZUVbV [` YX WXY_VY`cZ[XYJ
JIJIJ " # " % mY ZUV abV`VYWV Xd c `ZVce WXYi
_VY`cZ[XY dbXYZ [Z [` \`Vd\f ZX `VacbcZV ZUV `Xf\Z[XY [Y ZUbVV acbZ` Z^X [`XZUVbecf Z^XiaUc`V
bV][XY` `VacbcZV_ jl ZUV `ZVce WXY_VY`cZ[XY dbXYZJ TUV [`XZUVbe cf acbZ` WcY jV _V`Wb[jV_
VcWZfl c` ZUV \WgfVlitVnVbVZZ ZUVXbl Xd Z^XiaUc`V X^ ZUV `Xf\Z[XY` WXY`[`Z Xd WXY`ZcYZ
`ZcZV`h bcbVdcWZ[XY` cY_ `UXWg`J
tVZ \` WXY`[_Vb ZUV Wc`V ^UVY ZUV `aVV_ [` `X fcb]V ZUcZ [Z Vk\cf` ZUV WXXf[Y] WXYi
ZcWZ _[`WXYZ[Y\[Zl `aVV_J V VaVWZ ZU[` j[d\bWcZ[XY ZX bVabV`VYZ ZUV jX\Y_cbl jVZ^VVY
WXY ]\bcZ[XY` WXYZc[Y[Y] V[ZUVb `UXWg` Xb WXXf[Y] _[`WXYZ[Y\[Z[V`J V ^[ff `UX^ ZUcZ
ZUV bVe cbgcjfV `aVV_ Vk\cf[Z[V` pJIu pJ|u UXf_ cfXY] ZU[` j[d\bWcZ[XY W\bnVJ VlXY_ ZU[`
j[d\bWcZ[XY W\bnV ZUV [` cj`VYZJ
TU[` j[d\bWcZ[XY ^c` cfbVc_l `Z\_[V_ dXb ZUV Wc`V Xd a\bV `ZVce [YVWZ[XY [Y y{J
JIJ|J
$ % V ^[ff WXY`[_Vb `ZcZV` p u cY_ p u bVfcZV_ jl } WXY_[Z[XY` dXb
^U[WU ZUV ZXZcf ceX\YZ Xd ec`` ZbcY`dVb cY_ Xd UVcZ ]VYVbcZV_ [` VbXJ V `VZ ZX VbX [Y
k`J pzJI u cY_ pzJI u , bXe ZUV b`Z XYV ^V XjZc[Y ZUV b`Z Xd ZUV Vk\cf[Z[V` [Y pJIuJ TUV
`VWXY_ XYV dXffX^` dbXe pzJI u cY_ dbXe }Ve cbg JI
+
&
pJIu
Tcg[Y] ZUV f[e[Z c` [YZX pJIuh ^V `VV ZUcZ p u `cZ[`dl ZUV dXffX^[Y] Vk\cZ[XY
[Y p u `acWV p`VV k`J pzJI u cY_ p|JI uu
+
&
p u &
pJ|u
V `VV ZUcZ ZUV p u `ZcZV` Xd ^[ZU jVfXY] ZX ZUV fXW\` _V YV_ jl kJ pJ|uJ
V XjZc[Y
dbXe kJ pzJIzu `VZZ[Y] & V bVafcWV \`[Y] ZUV b`Z Vk\cf[Zl
pJIu [YZX k J pzJI uJ V `VV ZUcZ `cZ[` V`
+
&
pJzu
c` ZUVl caabXcWU VcWU XZUVb ZUVbecf bcbVdcWZ[XY W\bnV` ^[ZU cf`X jVfXY] ZX ZUV
\]XY[XZ jcbb[VbJ TUVbVdXbV ZUVbecf bcbVdcWZ[XY W\bnV` _X YXZ WbX`` ZUV jcbb[VbJ
V UcnV dX\Y_ c W\bnV [Y p u `acWV dXb ^U[WU ZUV W\e\fcZ[nV WXY_VY`cZ[XY [` VbXJ
TU[` W\bnV cWZ` c` c jcbb[Vb dXb ZUVbecf \]XY[XZ W\bnV`J rfXY] [Z Vk\cf` + ) jXZU
\a`ZbVce cY_ _X^Y`ZbVce J
XYnVb`Vflh b`Z WXY`[_Vb c ZUVbecf `UXWg ^[ZU `aVV_ + ) J `[Y] ZU[` Vk\cf[Zl
[YZX pzJI u ^V `VV ZUcZ & ~X ZUV ZUVbe cf `UXWg jVfXY]`
ZX ZUV \]XY[XZ jcbb[VbJ
~VWXY_h WXY`[_Vb c ZUVbe cf `UXWg ^[ZU `aVV_ ) J `[Y] ZU[` Vk\cf[Zl
[YZX pzJIu ^V `VV ZUcZ & ~X c]c[Y ZUV ZUVbecf
`UXWg
jVfXY]` ZX ZUV \]XY[XZ jcbb[VbJ
TU[b_ h c``\eV
ZUV Vk\cf[Zl Xd + ) cY_ ) J TU[` WXY_[Z[XY ][nV` +
cY_ ^[ZU & ~\j`Z[Z\Z[XY [YZX kJ pzJI u fVc_` ZX + )
) & c`V_ XY ZUV`V Z^X dcWZ` cY_ kJ pzJI uh ^V WXYWf\_V ZUcZ ZUV Vk\cf[Zl Xd
cYl Z^X Xd ZUV ZUbVV k\cYZ[Z[V` + ) cY_ ) [eaf[V` ZUcZ ^V cbV XY ZUV
\]XY[XZ jcbb[VbJ
p u
&
f[e
f[e
p u &
pJu
TU\` ^V `VV ZUcZ ZUV ]VXeVZb[W aX``[j[f[Zl Xd [`XZUVbe cf bcbVdcWZ[XY ^cnV abVWV_[Y] cY [Yi
Y[ZV`[e cf WUcY]V` cZ ZUV \]XY[XZ jcbb[VbJ
1
0.9
Welge
0.7
c+r+s
water saturation Sw
0.8
0.6
0.5
0.4
Hugoniot
curve
SCF
0.3
0.2
()
entropy curve
c+r
0.1
0
290
300
310
320
330
340
350
Temperature T+ /K
360
370
+
+
&
J
S LL O QMSOL
ON L SLSMS M N MQN M P RON
! # # [ZU V_ h c` _VWbVc`V` ZX VbXh [YWbVc`V` ZX ZUV `aVV_ Xd ZUV
ZUVbe cf ^cnV [Y ZUV a\bV f[k\[_h & , ZU[` dcWZ dXffX^` dbXe ZUV WXYnV[Zl Xd p uJ mZ [`
\`Vd\f dXb ZUV b`Zh `VWXY_h cY_ ZU[b_ Wc`V`J
JIJ !"
V Wfc[e ZUcZ dXb nVbl fX^ ^cZVb `cZ\bcZ[XY cZ ZUV [YVWZ[XY aX[YZh ^V UcnV
p u &
&
p JIu
pTU[` dXffX^` dbXe ZUV dcWZ ZUcZ cZ h ^V UcnV &
p u p u h ^U[fV
uJ kJ p JIu dXb ZUV [YVWZ[XY `cZ\bcZ[XY _V YV` ZUV b`Z Wc`VJ TUV [Y[Z[cf WXY_[Z[XY
_VYXZV_ c` [Y []\bV p JIuh ^U[WU _V YV` ZUV [Y[Z[cf `cZ\bcZ[XY I cY_ ZUV [Y[Z[cf
ZVeaVbcZ\bV p[Y X\b VceafV ^V WUXX`V zz & I uJ mZ WcY jV `UX^Y ZUcZ ZUV
_X^Y`ZbVce pb[]UZu `UXWg ZVeaVbcZ\bV &
[b`Z ^V _bc^ ZUV VYZbXal W\bnV c``XW[cZV_ ^[ZU ZUV ][nVY [YVWZ[XY ZVeaVbcZ\bV
pUVbV z uJ mZ Uc` jVVY `UX^Y cjXnV ZUcZ ZUV \a`ZbVce pfVdZu `UXWg
ZVeaVbcZ\bVJ qX^ ^V ^cYZ ZX _VZVbe[YV ZUV `cZ\bcZ[XY Xd ZUV \a`ZbVce pfVdZu `UXWg `ZcZV
p u J V _bc^ c nVbZ[Wcf f[YV ZUbX\]U & TUV [YZVb`VWZ[XY Xd ZU[` f[YV ^[ZU ZUV VYZbXal W\bnV
_VZVbe[YV` ZUV `cZ\bcZ[XY & r UXb[XYZcf f[YV ZbcY`aXbZ` ZU[` `cZ\bcZ[XY ncf\V ZX _VZVbe[YV
ZUV `ZcZV p u p uJ mY X\b Vce
afV p u pz &|uJ TUV b`Z Wc`V bVk\[bV` ZUcZ
ZUV [YVWZ[XY `cZ\bcZ[XY `cZ[` V` & mY_VV_ `cZ[` V` cff \]XY[XZ WXY_[Z[XY` cY_
ZUV VYZbXal ZcY]VYWl WXY_[Z[XY pJuJ TUV \]XY[XZ W\bnV `ZcbZ[Y] cZ `ZcZV p u [YZVb`VWZ`
ZUV nVbZ[Wcf f[YV cZ ZUV `ZcZV & a`ZbVce Xd aX[YZ p u ^V UcnV [`XZUVbe cf WXY_[Z[XY` cY_
^V WcY caafl ZUV Wfc``[Wcf \WgfVlitVnVbVZZ ZUVXblJ
TUV `Xf\Z[XY
p`VV []\bV JIu [` c ^cnV `Vk\VYWV WXY`[`Z[Y] Xd c WXY`ZcYZ `ZcZVh c bcbVdcWZ[XY
acbZ cZ cY_ `\j`Vk\VYZfl ZUV `ZVce WXY_VY`cZ[XY dbXYZJ vX^Y`ZbVce Xd ZUV `ZVce WXYi
_VY`cZ[XY dbXYZ ZUVbV ^[ff jV ZUV WXY`ZcYZ `ZcZV h dXffX^V_ jl c \WgfVlitVnVbVZZ
bcbVdcWZ[XY
(
(
&
cY_ `UXWg \a ZX ZUV `ZcZV J rff Xd ZU[` [` [Y_[WcZV_ jl ZUV acZU
p u
md ZUV [YVWZ[XY `cZ\bcZ[XY [` Vk\cf ZX ZUV WXYYcZV ^cZVb `cZ\bcZ[XY ZUV acZU p u Uc`
YX WXY`ZcYZ `ZcZVJ
(
ZUVbV [` c WXY`ZcYZ `ZcZV dXffX^V_ jl c \WgfVli
vX^Y`ZbVce Xd ZUV ~ h [JVJh [Y
tVnVbVZZ bcbVdcWZ[XY ^cnV \YZ[f ^V cZZc[Y ZUV # ! ! ^[ZU
`aVV_
+
+
p J|u
ZX ZUV [Y[Z[cf `ZcZV ^UVbV ZUV ]c` `cZ\bcZ[XY ]XV` ZX VbXJ TU[` W[]^ `UXWg caaVcb` [Y Wc`V`
XYV ZX ZUbVVJ
TUV `VacbcZ[XY jVZ^VVY ZUV b`Z cY_ `VWXY_ Wc`V` [` ZUV WX[YW[_VYWV fXW\` _V`Wb[jV_ [Y
~VWZ[XY J|JIJ
J|J # TUV ^cZVb `cZ\bcZ[XY cZ ZUV [YVWZ[XY aX[YZ [` U[]U VYX\]U `X ZUcZ ZUV
nVfXW[Zl Xd ZUV `ZVce WXY_VY`cZ[XY dbXYZ `cZ[` V` ZUV dXffX^[Y] [YVk\cf[Z[V` dXb
_V YV_
[Y k\cZ[XY pJu
&
p Jzu
p u &
[]\bV J| `UX^` c Y\ejVb Xd Wc`V` ZUcZ _[wVb [Y ZUV fVdZ `ZcZV XYfl c` ZX ZUV [YVWZ[XY
`cZ\bcZ[XYJ mY cff Xd ZUV`V Wc`V` ZUVbV [` c WXY`ZcYZ `ZcZV dbXe ZUV [YVWZ[XY WXY_[Z[XY [Y_[WcZV_
jl ZX ZUV fVdZ aX[YZ p u p\`Z \a`ZbVce u Xd ZUV `ZVce WXY_VY`cZ[XY dbXYZJ pod WX\b`Vh
cY_ p u WX[YW[_VJu mY c`V |h ZUV fVdZ `ZcZV p u f[V` jVfX^ ZUV VYZbXal W\bnVJ pTU[` eVcY`
ZUcZ acbZ Xd ZUV \]XY[XZ W\bnV _XV` YXZ bVabV`VYZ c_e[``[jfV `Xf\Z[XY` cY_ UVYWV [Z [`
bVabV`VYZV_ jl c ZU[Y f[YVuJ Xb c`V | ZUV `Xf\Z[XY acZU pXb ^cnV `Vk\VYWVu Zla[Wcffl [`
(
p u
J c`V | WXeab[`V` cff `Xf\Z[XY` ^[ZU \]XY[XZ W\bnV` `\WU c` ZUV
p u
XYV` jVfXY][Y] ZX h `ZcbZ[Y] jVfX^ ZUV WX[YW[_VYWV W\bnVh cY_ ZX h `ZcbZ[Y] cjXnV ZUV
WX[YW[_VYWV W\bnVJ rff `Xf\Z[XY` dXb ZU[` Wc`Vh ^U[WU _X YXZ [YZVb`VWZ ZUV W\bnV ZX ZUV
b[]UZ Xd ZUV nVbZ[Wcf `Zbc[]UZ f[YVh dXffX^ ZUV `ce V acZZVbYJ
TUV`V `Xf\Z[XY` UcnV c WXY`ZcYZ `ZcZV
p uh ZUV `ZVce WXY_VY`cZ[XY( dbXYZ p u
J
p uh c WXY`ZcYZ `ZcZVh c bcbVdcWZ[XY cY_ c `UXWg ZX ZUV [Y[Z[cf `ZcZV h p u
TUV `VWXY_ cY_ ZU[b_ Wc`V` cbV `VacbcZV_ jl ZUV Vf]V W\bnV _V`Wb[jV_ [Y ~VWZ[XY J|J|J
JzJ ! # []\bV J| `UX^` cf`X ZUV Wc`V ^[ZU \]XY[XZ W\bnV`h `\WU c` ZUV XYV
jVfXY][Y] ZX ZUcZ _X [YZVb`VWZ ZUV W\bnV fVdZ Xd cY_ ZX ZUV b[]UZ Xd ZUV nVbZ[Wcf
`Zbc[]UZ f[YVJ VWc\`V ^V WbX``V_ ZUV W\bnV c j[d\bWcZ[XY Uc` XWW\bbV_J mY_VV_ dXb
c+s
0.9
(+)4
Welge
B ,()
4
(+)
watersaturation Sw
0.8
c+r+s
0.7
0.6
B3,()3
0.5
(+)2
0.4
SCF
0.3
E2
B ,()
2
0.2
coincidence curve
0.1
0
300
310
320
330
340
T+ /K
350
360
370
XY`Zb\WZ[XY Xd `Xf\Z[XY dXb [YVWZ[XY WXY_[Z[XY`
p u pz &|uh p u pz & uh p u
pz & u bVabV`VYZV_ jl `Xf[_ W[bWfV`J TUVbV [` c WXY`ZcYZ `ZcZV jVZ^VVY ZUV
[YVWZ[XY WXY_[Z[XY cY_ ZUV fVdZ `ZcZV Xd ZUV `ZVce WXY_VY`cZ[XY dbXYZ p u
_VYXZV_ jl p u J TUV [` dbXe p u ZX p u h [JVJ ZUV b[]UZ `ZcZV Xd ZUV
J Xb ZUV [Y[Z[cf WXY_[Z[XY ZUVbV dXffX^` c WXY`ZcYZ `ZcZVh c bcbVdcWZ[XY
cY_ c `UXWgJ
S QN
JJ !" # TUV ^cZVb `cZ\bcZ[XY cZ ZUV [YVWZ[XY aX[YZ [` `X U[]U ZUcZ cZ ZUV [YVWZ[XY
ZVe aVbcZ\bV ZUV [`XZUVbe cf ]c`i^cZVb pU[]^ u `UXWg `aVV_ `cZ[` V`
p u & p u &
p Ju
md ZUV [YVk\cf[Zl p Ju [` `cZ[` V_ ^V ^[ff UcnV YX `ZVce WXY_VY`[Y] cZ ZUV dbXYZ ^UVbV ZUV
ZVe aVbcZ\bV [` bV_\WV_J mY`ZVc_ ^V UcnV c U[]^ `UXWg dXffX^V_ jl c WXXf[Y] _[`WXYZ[Y\[Zl
c` ][nVY jl kJ pJuJ VZ^VVY ZUV [YVWZ[XY aX[YZ cY_ ZUV dbXYZ ^UVbV ZUV ZVeaVbcZ\bV [`
bV_\WV_ YX^ ZUVbV [` c UXZ Z^X aUc`V XYV cY_ c UXZ `[Y]fV aUc`V XYVJ
rY Vce afV Xd ZUV dX\bZU Wc`V [` ZUV `Xf\Z[XY ^[ZU [Y[Z[cf WXY_[Z[XY [` XY ZUV XZUVb
`[_V Xd ZUV \]XY[XZ jcbb[Vb W\bnVJ p~VV []\bV JzJu TU[` eVcY` ZUcZ ZUV \WgfVlitVnVbVZZ
]c`i^cZVb `UXWg [` `fX^Vb ZUcY ZUV `aVV_ Xd c ZVeaVbcZ\bV ^cnV Wcbb[V_ jl a\bV f[k\[_ ^cZVb
`X ZUVbV [` YX `ZVce WXY_VY`cZ[XY dbXYZJ TUV `Xf\Z[XY acZU [`
p u
pu
J
cool.disc.
barrier
s
B ,()7
7
(+)
0.99
c+s
0.995
B6,()6
(+)
0.985
S
SC
0.98
0.975
B5,()5
300
310
320
330
340
350
360
370
Temperature T+ /K
XY`Zb\WZ[XY Xd `Xf\Z[XY dXb [YVWZ[XY WXY_[Z[XY`
p u pz & uh p u pz & uh p u
pz & uJ TUV W\bnV` `ZcbZ cY_ bVe c[Y jVfX^ ZUV W\bnVJ Xb
ZUVbV cbV c WXY`ZcYZ `ZcZVh ZUV `ZVce WXY_VY`cZ[XY dbXYZh c WXY`ZcYZ
`ZcZV cY_ c `UXWg ZX mJ Xb ^V UcnV c WXY`ZcYZ `ZcZVh c UXZ [`XZUVbecf ]c`
^cZVb `UXWg cY_ c ZUVbecf WXYZcWZ _[`WXYZ[Y\[Zl ZX mJ
S QN
mY ZU[` Wc`V ZUVbV ^[ff jV c `UXWg dbXe p u dXffX^[Y] ZUV nVbZ[Wcf cbbX^ cf`X WcffV_ ZUV
# ! `UXWg cY_ c UXb[XYZcf cbbX^ bVabV`VYZ[Y] ZUV WXXf[Y] _[`WXYZ[Y\[ZlJ
J OLR Q SOL
IJ r eVZUX_ [` abV`VYZV_ ^[ZU ^U[WU cff k\cf[ZcZ[nVfl _[wVbVYZ `Xf\Z[XY` WcY jV dX\Y_ J r
j[d\bWcZ[XYh [JVJ c k\cf[ZcZ[nVfl _[wVbVYZ `Xf\Z[XY h WcY XWW\b ^UVY ZUV `Xf\Z[XY WbX``V`
j[d\bWcZ[XY fXW[ p^UVbV ^cnV nVfXW[Z[V` jVWXeV Vk\cfuJ
|J Xb cY [Y[Z[cf `ZcZV ^UVbV ZUV aXbX\` e V_[\e [` d\ffl `cZ\bcZV_ ^[ZU ^cZVb dX\b _[wVbVYZ
ZlaV` Xd `Xf\Z[XY` cbV dX\Y_h _VaVY_[Y] XY ZUV [YVWZ[XY WXY_[Z[XY`J TU[` ]VYVbcf acZZVbY
[` [Y_VaVY_VYZ Xd bVcf[`Z[W ncb[cZ[XY` Xd ZUV aUl`[Wcf k\cYZ[Z[V`J
zJ TUbVV Xd ZUV`V `Xf\Z[XY` WXYZc[Y c WXf_ ]c`VX\` XYV _X^Y`ZbVce Xd ZUV `ZVce WXYi
_VY`cZ[XY dbXYZJ ~\WU c XYV [` WXY`[_VbV_ c abVbVk\[`[ZV dXb ZUV cnX[_[Y] _X^Y^cb_
eXnVe VYZ Xd ZUV aXff\ZcYZ` pvqrst `uJ
J TUV dX\bZU `Xf\Z[XYh dXb ^U[WU ZUV ]c` `cZ\bcZ[XY _[`caaVcb` \a`ZbVce Xd ZUV ZVeaVbi
cZ\bV ^cnVh XYfl XWW\b` dXb [eabcWZ[Wcf [YVWZ[XY WXY_[Z[XY`J XbVXnVbh ZUV abV`VYWV
Xd [YVWZV_ Y[ZbX]VY ]bVcZfl bV_\WV` ZUV bV][XY [Y aUc`V `acWV ^UVbV ZUVbV [` YX `ZVce
WXY_VY`cZ[XY dbXYZJ TU[` bV][XY WXbbV`aXY_` ZX fV`` ZUcY J I Y[ZbX]VY `cZ\bcZ[XYh c`
`UX^Y [Y []J JzJ
" TU[` ^Xbg ^c` acbZ[cffl _XYV cZ m r h Y[nVb`[Zl Xd [YYV`XZch cY_
ZUVbVdXbV acbZ[cffl d\Y_V_ jl q~ J V cf`X ZUcYg VcZc \Y_VfcWU dXb WcbVd\f cY_ VaVbZ
ZlaV`VZZ[Y] Xd ZU[` acaVbJ
N LR
$
* *(
&(
* * .C6 +92,A ".67 B " >>>
$ & * ('$(' ( * 36< %) & '*B
.64309634,< ".92 C.037 ,2-./<B .6<.6B ??
>
$ ' '*$*B %& ('& * *B 36< & & * *B B .C6 + 92,A ".67 B
" >>
$' % '* *B 36< ) ' ( *&*B B // /396 98B
/.5B 0 ".5 98 !6; 16, B >
$'
*B 36<
)* *B
B .0?14349.632 ,.759,65,7 B >
$'
*B (') % *B 36<
)* *B B .0>
?14349.632 36< ??29,< 34C,034957B 355,?4,<B B 36< ?/,?/964 6. B
) (&% * *B B ".5 ,4 !6; B ,5 B ??
) (&% * * & (% * * (
'% '* *B "! ,7,/8.9/
!8321349.6 !6;96,,/96;B 1;174 B > 7,, 327. ($ ( ( ( ( ( ) (&% * *B
B 4C 66132
322 ,,496; .- 4C, ".59,4A .- ,4/.2,10 !6;96,,/7 .- !B 4. @, C,2< 96 ,: /2,367B 3B 54 >B
"!
(
* *B B !27,89,/ "59,65, 1@297C,/7B 074,/<30 B
*( * *B B 53<,095 /,77B
* ( *B B 5C3?4,/ B C, 3/3@.295 /,77B "436-./<B
' '*'* * * $'
*(
(('
B
"! .1/632 B ,5,0@,/ B >
)* * 36<
*%*B
.1/632 .- .643096364 A</.2.;A >
%) & '*
$ ' * %
$ ' &* * 36< %
* *B
.1/632 .- .643096364 A</.2.;A >
#
'
"
$$
$$
#
#
3"
+
$
%
1
'
#$
$
3"
# #
-
'
6 )
"
5
.
5
:
.
-
$
#
;<
+
==
+
>
/
?,
+
> %
//
?,
-
$
-
)
1
:
<4:%@ A
"
BB
'
H
1$1
>
1$
)
E: F
(
?I
+
8 $
$J
K
8
"
&
#
'
#
>
#
)
$
=?
'
"
#
BB
?I
"
"
4:%@ A
%) & '* $ & )* 36< ( '$ ' (*B
64,/6349.632 77.59349.6 .- A</.2.;9532 "59,65,7 1@295349.6 B >
% & ' * B B
".5 ,4 !6; B >
%
' *B
B "?/96;,/> ,/23;B ,: ./D
%& ('& * * 36<
*%*B B "!
,7,/8.9/ !6;96,,/96;B .8,0@,/> >
& '&
*%*B 36< (' ( %* *B
B "!! .8,0@,/ >
(%& '*)*B
B ,<949.6B /,77B 65 >
(' *%* 36< '' * B B "! <8365,<
,5C6.2.;A ",/9,7B >
& ( *$*B B .C6 + 92,A 36< ".67B B
'&% % * *B B ".5
,4 !6; B >
$
.
#
@4 : %@
<4:%@
)
?BI
< (
3+
+
2 2 C
'$
#
@
<
r J
SR
Q LMSMS O LP Q
mY ZU[` raaVY_[ ^V `\ee cb[V ZUV ncf\V` cY_ \Y[Z` Xd ZUV ncb[X\` k\cYZ[Z[V` \`V_ [Y ZUV
WXea\ZcZ[XY cY_ Vea[b[Wcf VabV``[XY` dXb ZUV ncb[X\` acbceVZVb d\YWZ[XY`J Xb WXYnVY[VYWV
^V VabV`` ZUV UVcZ WcacW[Zl Xd ZUV bXWg ( [Y ZVbe ` Xd VYVb]l aVb \Y[Z nXf\e V Xd $
# $ # aVb \Y[Z ZVeaVbcZ\bV % % ZUV dcWZXb I $ [` cfbVc_l [YWf\_V_ [Y ZUV bXWg _VY`[ZlJ rff
XZUVb _VY`[Z[V`h WXYWVYZbcZ[XY` cbV VabV``V_ [Y ZVbe ` Xd e c`` aVb \Y[Z nXf\eV Xd ZUV aUc`VJ
rff VYZUcfa[V` aVb \Y[Z e c`` cbV ^[ZU bV`aVWZ ZX ZUV VYZUca[V` cZ ZUV bVdVbVYWV ZVeaVbcZ\bV
Xd ZUV WXeaXYVYZ` [Y ZUV[b `ZcY_cb_ dXbe J rff UVcZ WcacW[Z[V` cbV cZ WXY`ZcYZ abV``\bVJ rff
VYZUca[V` aVb \Y[Z e c`` cbV VbX dXb ZUV WXeaXYVYZ [Y [Z` `ZcY_cb_ dXbe cZ ZUV bVdVbVYWV
ZVeaVbcZ\bVJ
LPS
#
h
(
+ +
}XWg VYZUcfal
cZVb VYZUcfal
sXbX\` bXWg aVbeVcj[f[Zl
cZVbh `ZVce bVfcZ[nV aVbeVcj[f[Z[V`
sbV``\bV
c`` WXY_VY`cZ[XY bcZV
\e\fcZ[nV e c`` WXY_VY`cZ[XY
cZVbh `ZVce `cZ\bcZ[XY`
XYYcZV ^cZVb `cZ\bcZ[XY
cZVb [YVWZ[XY `cZ\bcZ[XY
TVeaVbcZ\bV
}V`VbnX[b ZVeaVbcZ\bV
mYVWZ[XY ZVeaVbcZ\bV
cZVbh `ZVce aUc`V nVfXW[Zl
TXZcf vcbWl nVfXW[Zl
TXZcf [YVWZ[XY nVfXW[Zl
nVfXW[Zl
cZVbh `ZVce n[`WX`[Zl
~ZVce h Y[ZbX]VY WXYWVYZbcZ[XY`
s\bV ^cZVbh `ZVce h Y[ZbX]VY _VY`[Z[V`
}XWg aXbX`[Zl
cZVb VncaXbcZ[XY UVcZ
(
%
%( %(
'
h *
h
h
*
$
)
| &|
I
y xpg] u{
y xpe u{
y xpe u{
y xpe u{
kJ p|J|uJ
ye xe {
kJ &z &
y xg]{
p u
p u
y xe {
p u p u
y xe {
p u
p u
y xe {
p u p u
y xe {
( p
u
y xe {
p u
p u
y xe {
ye {
I &
I
kJ pr JIIu J
ye xe {
ysc{
I & Iz
I
kJ |JI
yg] xpe `u{
kJ p|JI uJ
yg] xe {
vVaVY_VYZ ncb[cjfV`J
ye xe {
& I
ye xe {
ye xe {
vVaVY_VYZ ncb[cjfVJ
y {
y {
| zJ
y {
| z z zJ
kJ p|JzuJ
ye xpe `u{
J
ye xpe `u{
ye xpe `u{
J
ye x`{
J
kJ pr J uh kJ pr J uJ
ysc `{
kJ pr J u
yg]xe {
yg]xe {
I k`Jp|J u J
&z
ye xe {
kJ p|JI|uhpr JuJ
y xg]{
pr J|u
I &||I z
I &
I &
TUV `ZVce VYZUcfal
y ) % { c` c d\YWZ[XY Xd ZVeaVbcZ\bV [` caabX[e cZV_ jl
p u | &| |
I z & zI
I | &| z
I &z |
I &zzz
I I &| Iz
I &
I &
pr Jzu
TUV Y[ZbX]VY VYZUcfal y ) % { c` c d\YWZ[XY Xd ZVe aVbcZ\bV [` caabX[ecZV_ jl
p u & & z &
I &
pr Ju
TUV VYZUcfa[V` p u p u ncY[`U cZ c bVdVbVYWV ZVeaVbcZ\bV | z & Xb ZUV fcZVYZ
UVcZ p uy ) % { Xb VncaXbcZ[XY UVcZ ^V XjZc[Y
I
I
p u
I & I
I
&
I
&
I & |
I
V c``\eV ZUcZ ZUcZ ZUV n[`WX`[Zl Xd ZUV ]c` [` [Y_VaVY_VYZ Xd ZUV WXeaX`[Z[XYJ
*
I & |
I
pr J u
&
I &Iz I
I u
TUV WXbbV`aXY_[Y] WXYWVYZbcZ[XY` cbV WcfW\fcZV_ ^[ZU ZUV [_Vcf ]c` fc^
'
p'
' u
|z |
&
pr J u
pr J u
^UVbV c` ZUV a\bV aUc`V _VY`[Z[V` cbV ][nVY [Y k`J p|J u ^UVbV ZUV ]c` WXY`ZcYZ
&zIy )
) {
TUV f[k\[_ ^cZVb _VY`[Zl c` c d\YWZ[XY Xd ZUV ZVeaVbcZ\bV y { [` ][nVY c`
pr J u
pr JI u
| z
I z &
I &
% (
%(
cbV WXY`[_i
I
pr JIIu
I
Xb ZUV WXea\ZcZ[XY` ^V ZcgV | cY_ |J TUV VY_ aX[YZ aVbe Vcj[f[Z[V` % ( % ( cbV
& cY_ & bV`aVWZ[nVflJ TUV WXYYcZV ^cZVb `cZ\bcZ[XY [` ][nVY [Y ZUV ZcjfVJ
%(
LPS
%(
&
J P
Q SMS M M
Q OLSOM
mYZbX_\W[Y] ZUV dXffX^[Y] cjjbVn[cZ[XY`
p
NNS N
p ( ( u
V \`V k J pzJI u
)$
( )$
p JIu
&
+ +
( ) $
&
p J|u
V Vk\cZV dbXe k J p JIu cY_ ZUV `aVV_ Xd ZUV UXZ [`XZUVbe cf ]c` ^cZVb `UXWg ][nVY
jl pJIu cY_ XjZc[Y ZUV `VWXY_ Vk\cf[Zl jVfX^
+
+ +
I + +
&
I ( ) $
( ) $
( ) $
TUV ZU[b_ Vk\cf[Zl [` XjZc[YV_ jl e\fZ[afl[Y] ZUV `VWXY_ dbcWZ[XY jl cY_ c__[Y] [Z ZX ZUV
ZU[b_ dbcWZ[XYJ Xb ZUV dX\bZU Vk\cf[Zl ^V e\fZ[afl ZUV b`Z dbcWZ[XY jl
h c__ ZUV dX\bZU
dbcWZ[XY cY_ `[eaf[dlJ
! # # l abXWV_\bV` `[e[fcb ZX ZUV XYV cjXnV ^V bVcWU ZUV dXffX^[Y] WXYWf\`[XY J
XY`[_Vb ZUV ^cnV `aVV_`
cY_ , [d cYl Xd ZUV Z^X cbV Vk\cfh ZUVY ZUV ZUbVV
cbV Vk\cfJ
I
&
p Jzu
^UVbV ^V \`V []\bV |J| ZX `VV ZUcZ [` c e XYXZXYV d\YWZ[XY Xd ZVe aVbcZ\bVJ TUV Ycf
k\cYZ[Zl [` aX`[Z[nV dXb X\b Wc`V ^[ZU J
D
3
K
'
$
L$
$
D $
D
3
$
1
$