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Paszczyzna
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maksimum cinienia
chimpik

Strefa uderzeniowej dekompozycji

materiau wybuchowego

x
Kierunek rozprzestrzeniania
si fali detonacyjnej

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linia soniczna
(skraj strefy ksztatowania parametrw detonacji)

koniec strefy
reakcji chemicznych

1
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1
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y N + 2 x N 2 + y NO = bN
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L;1.H<234 "S$K' 52H. C@4 ,;F-8;<; = F287;?') c #'- 0 $'( l *+, !

"S$S'

1GC
'. l *+, !

"S$\'

*+,-./ ."$!#' _ ) c #- 0 $(/0/ /0 $(/1/.<7;1F-; 8=2C2+<; "F27.<?>;: m-CC8;'! FB,@ ?,@5

/0/) c #- 0 .<7;1F-;$
Z;BG<.9 "S$\' =@B;H; 2*D1<J ,;8;+Q 29B.31;<-; 9-.BG<9G FB,.C-.*G FB2?.8G Y,@926?I.5-?,<.*2 2B;,
=;BG<9D= G87;1;<-; 8-Q BD=<2=;*2=.*2 87;<G G9:;+G$ L;F-8 "S$\' >.87 2*D1<-.>8,J e2B5J ,;1.H<23?- "#$S'!
"#$\' 29B.31;>J?@?I 9-.BG<.9 FB,.C-.*G +;<.> B.;9?>- ?I.5-?,<.>$
Z;BG<.9 "S$\' 52H<; =@92B,@87;4 +2 =@,<;?,.<-; BD=<2=;*2=.*2 87;<G 7.B52+@<;5-?,<.*2
- 2+F2=-;+;>J?.*2 5G 89:;+G ?I.5-?,<.*2 FB2+G97D= FB,.5-;<@ =@CG?I2=.>! =3BD+ 97DB@?I =@87QFG>J
89:;+<-9- = e;,;?I 892<+.<82=;<@?I! ?-.9:.> - 87;:.>$
#F#%GH5(0BA53,-.)% 9,4,-.,% 5'()*+)-.,% (23-53,:53):5% 8'A,4B% /(54B'123% /(9)0.,-;% -,%
/5481,3.)%0.-.0,+.9,67.%/51)-67,AB%1)(054;-,0.69-):5%B'A,4B
A27.<?>;: 7.B52+@<;5-?,<@ G9:;+G ,=-.B;>J?.*2 ng *;,2=@?I 2B;, n8 89:;+<-9D= = e;,-. 892<+.<82=;<.>!
52H.5@ ,;F-8;4 ,; F252?J ,;1.H<23?- [%)]

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ng

g (T, p, x) =

i=1
n g +ns

=$

xi H i (T,p ) + f H i (0 K ) T Si (T,p ) + RT ln i
x

xi H i (T,V ) + f H i (0 K ) T Si (T,p )

"S$&'

i=n g + 1

P@5C21;5- 2- 2,<;?,2<. ,287;:@ =-.1923?- 87QH.E 5212=@?I F28,?,.*D1<@?I B.;*.<7D=$ AB,.+ B2,=-J,;<-.5
,;+;<-; 2 =@,<;?,.<-G 87;<G G9:;+G! =-.1923?- 7. 8J <-.=-;+25@5- ",5-.<<. <-.,;1.H<.'$ x _ [2%! 2M! n2ng!
2<*c%! n! 2n]! n _ ng cn8$ R 0 G<-=.B8;1<; 87;:; *;,2=;$ A27.<?>;: g"$! #! x' 2B;, =;B723?- 87QH.E 2- 2+<28,2<. 8J
+2 >.+<2879- 5;8@ ",=@91. % 9*'$ je "N`' 2,<;?,; .<7;1F-Q 7=2B,.<-; = N 872F<- `.1=-<;$ AB,@ G=,*1Q+<-.<-G
=-.1923?- .<7;1F-- 7=2B,.<-;! F27.<?>;: g"$! #! x'! ,;F-8;<@ = F287;?- "S$&' 29B.31; 7,=$ F.:<J "?;:92=-7J!
-<7.*B;1<J' .<7;1F-Q 8=2C2+<J G9:;+G$ d<7;1F-; ?;:92=-7; G=,*1Q+<-; .e.97@ .<.B*.7@?,<. ,5-;<@ 89:;+G
?I.5-?,<.*2 G9:;+G$
Z;BG<9-.5 28-J*<-Q?-; BD=<2=;*- 7.B52+@<;5-?,<.> G9:;+G >.87! ,*2+<-. , "S$\'! 5-<-5;1-,;?>; F27.<?>;:G
7.B52+@<;5-?,<.*2
g"$! #3/x' _ 5-< !

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89:;+G <; =-.19234 F27.<?>;:G 7.B52+@<;5-?,<.*2! =;BG<.9 "S$(' >.87 F2+ =,*1Q+.5 7.B52+@<;5-?,<@5
BD=<2=;H<@ 2+F2=-.+<-.5G ,.87;=2=- ,;1.H<23?- 29B.31;>J?@?I BD=<2=;*2=. 87;<@ B.;9?>- ?I.5-?,<@?I
,;?I2+,J?@?I = 5-.8,;<-<-.! >;9 <F$ BD=<;<-; "#$%K 0 #$%)'$
L;+;<-. 5-<-5;1-,;?>- F27.<?>;:G 7.B52+@<;5-?,<.*2 B.;1-,2=;4 <;1.H@ FB,@ G=,*1Q+<-.<-G 2*B;<-?,.E
=@<-9;>J?@?I , BD=<;E C-1;<8G 5;8@ "<F$ #$M%'$ PG5@ =-.1923?- 87QH.E F28,?,.*D1<@?I 8GC87;<?>- F2=-<<@
2+F2=-;+;4 -123?-25 F-.B=-;879D=! 97DB. =@87QFG>J = 5-.8,;<-<-.$

a11 x1 + a12 x2 + ... + a1n xn =b1

a21 x1 + a22 x2 + ... + a2n xn =b2
!

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*+,-./
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75 6 -1234 521- 567.*2 F-.B=-;879; = B2,F;7B@=;<.> -123?- 5-.8,;<-<@ ">.+<287?. 5;8@'o
8 6 -1234 F-.B=-;879D= =@87QFG>J?@?I = ,=-J,9;?I 7=2B,J?@?I 5-.8,;<-<Q$
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, BD=<;<-; 87;<G! <F$
p = xi RT !

"S$%N'

>.H.1- >.87 B2,F;7B@=;<; 5-.8,;<-<; *;,2=; 8F.:<-;>J?; BD=<;<-. 87;<G *;,G -+.;1<.*2$
b.72+@ G=,*1Q+<-.<-; =F:@=G <-.-+.;1<@?I =:;3?-=23?- 8GC87;<?>-! >;9 =F:@= 2C>Q723?- =:;8<.> 521.9G:!
=F:@= ?I;B;97.BG 2++,-;:@=;E 5-Q+,@521.9G1;B<@?I <; F287;4 BD=<;<-; 87;<G! G=,*1Q+<-2<. ,287;<J
= FG<9?-. \$
fD=<;<-. 87;<G 29B.31; <-.892E?,2<@ ,C-DB F;B;5.7BD= "#! 9'! +1; 97DB@?I 52H. C@4 ,B.;1-,2=;<@ =;BG<.9
5-<-5;1<.> =;B723?- F27.<?>;:G g"$! #! x'$ X1; 29B.31.<-; >.+<2,<;?,<23?- B2,=-J,;<-;! <-.,CQ+<@5 >.87

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8FB.?@,2=;<-. =;BG<9D= Y,@?,<@?I! +1; 97DB@?I 29B.312<@ 5; C@4 92E?2=@ 87;< FB2+G97D= FB,.5-;<@
=@CG?I2=.>$
Z FB,@F;+9G ;<;1-,@ 89:;+G FB2+G97D= 8F;1;<-; FB,@ ,;+;<@5 ?-3<-.<-G "?2 +27@?,@4 52H. <F$ C;+;<-;
=:;3?-=23?- F;1-= B;9-.72=@?I'! =;BG<.9 Y,@?,<@ 5; F287;4
#/0/:;<=> !

"S$%%'

AB,@ C;+;<-G =@CG?IG = 87;:.> 2C>Q723?-! FB,@>5G>. 8-Q

9/0/:;<=> !

"S$%M'

W;725-;87 = FB,@F;+9G 29B.31;<-; F;B;5.7BD= +.72<;?>-! F;B;5.7B@ 7.B52+@<;5-?,<. FB2+G97D= F2=-<<@

2+F2=-;+;4 ;+-;C;?-. +.72<;?@><.>

0 =

p + p0
(0 ) + Q !
2

"S$%K'

T-.F:2 =@CG?IG Q9! =@,<;?,;<. >.87 = =@<-9G B2,=-J,;<-; ,;+;<-;$

n

Q = f H MW (298,15) f H i (298,15 K ) !

i=1

"#$%&'

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903.@, .+)3:01;5 :1 );16 -,-1<;0$
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.+)3:01;5$ F.$ .+)5>:7>B9 / )1?34;,E90 "#$%G' H I J! ,<+)5:7>3 20= /1+7;36 ,-.,/01-1>B95 2<1;,/0 76@1-7
;1 1-01C1903 7-3+)3;0,/3>$
!"!#$%&'()&*+(,# &*-*+(*# %./,01,+(*# 2.3*-4# 5/%-4.67'# 5/&,8(*+9# 8,6%-)# 8(+(8*1(&*:;(# 5%<
6,+:;*34#6,/8%-9+*8(:&+,=%#4.3*-4
K+)3-:0,<3: )1-1;01 >32< /5);19)3;03 )C0,+7 2<=43L :,?367?1+;59M y I Ny%! yO! Pyng! y;8Q%! P! ynR -?1 6<*+38,
S7;69>1 g"!!"! ' ,20B81 :0;0:7:! )8,-;03 ) /1+7;603: "#$T'! .+)5 ,8+1;09)3;019M ,6+3E?,;59M +*/;1;01:0
"#$U'$
K,- /)8?=-3: :1<3:1<59);5:! >32< <, )181-;03;03 ,.<5:1?0)19>0 /1+7;6,/3> NOJVOOR$ W38, +31?0)19>1
,-.,/01-1 ,6+3E?3;07 :0;0:7: S7;69>0
m
n

"#$%#'
Q( p, T , x) = g ( p.T , x) + i bi aij x j !

i =1
j =1

8-)03X Y#%! #O! P! #:Z 2B :;,4;061:0 [18+1;83\1$ (.+,/1-)3;03 :;,4;06*/ [18+1;83\1 .,)/1?1 ;1
7/)8?=-;03;03! / .+,93203 :0;0:1?0)19>0 S7;69>0 g"!!"!x'! ,8+1;09)3L /5;061>B959M ) +*/;1L "#$U'$
]1-1;03 :0;0:1?0)19>0 S7;69>0 Q"!!"!x' :,43 C5D +,)/0B)1;3 :3<,-B ;1>2)5C2)38, 2.1-67 "$%&&"&$%'(&$)&*%'
NOG! O&R$ ^2<,<1 :3<,-5 ;1>2)5C2)38, 2.1-67 .,?381 ;1 /5);19)3;07 +,)/0B)1;01 .,.+)3) 0<3+195>;5 -,C*+
6,?3>;59M .+)5C?043L y"6' = Ny%"6'! yO"6'! Pyng"6'! y;8Q%"6'! P! yn"6'R .,2)760/1;38, E902@38, +,)/0B)1;01 .+,C?3:7$
( /5;067 +31?0)19>0 -1;38, 6+,67 0<3+195>;38, /5);19)1;3 >32< 6,?3>;3 +,)/0B)1;03 "6' = N+%"6'! +O"6'! P+ng"6'!
+;8Q%"6'! P! +n"6'R! 6<*+3 >32< ?3.2)5: .+)5C?043;03: .,2)760/1;38, +,)/0B)1;01 E902@38,! / 2<,27;67 -, )C,+7
/5>E90,/38, y"6'$ _<+)5:1;3 +,)/0B)1;03 >32< .+)5>:,/1;3 >16, .,-2<1/1 -, 6,?3>;38, 6+,67 0<3+195>;38,
y"6Q%' = "6'$!
( 93?7 +31?0)19>0 6,?3>;38, 6+,67 0<3+195>;38,! ;03)C=-;3 >32< ,6+3E?3;03 :3<,-5 -,C,+7 6,?3>;59M .+)5C?043L!
<>$ :3<,-5 /5);19)1;01 )C0,+*/ "6'! 6<*+3 ?3.03> C=-B .+)5C?041D .,2)760/1;3 +,)/0B)1;03 E902@3! ;0`?0
-1;5 )C0*+ /5>E90,/5 y"6'$ aC5 <, 7)5261D +,)6@1-1 20= S7;69>= g"!! "! x' / 2)3+38 b15?,+1 /,6*@ )C0,+7 y"6'$
K,:0>1>B9 9)@,;5 +)=-*/ /542)59M ;04 -+780! ,<+)5:7>3 20=

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g
1 n n 2g
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( xi y ( k ) i ) ( xk y ( k ) k ) !

x
2
x
x
i
k
i
i =1k =1
i =1
x=y
x=y

>

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"#$%c'

A,4;1 )1.021D
m
n

"#$%d'
( p, T , x) = Y ( p, T , x) + i bi aij x j !

i =1
j =1

e7;69>1 f ""!!! x' >32< .+)5C?043;03: S7;69>0 Q"!! "! x'! / ,<,9)3;07 .7;6<7 y"6'$(1+7;603: :0;0:1?0)19>0
S7;69>0 f ""!!! x' >32< )3+,/1;03 20= .,9M,-;59M

( p, T , x)
=0!
xi

"#$%T'

8-)03 i I %! $$$ ! n
]1?34;,E90 "#$%T' ,6+3E?1>B n +*/;1L! +*/;5 0?,E90 ;03/01-,:59M! >160:0 2B 2<=43;01 :,?,/3 .,2)9)38*?;59M
+3183;<*/ +0$ (03?6,E90 "! ! .3@;01 +,?= .1+1:3<+*/$ ]181-;03;03 :0;0:1?0)19>0 S7;69>0 Q"!! "! x' +,)/0B)5/1;3
>32< -?1 -1;3> 6,:C0;19>0 .1+1:3<+*/ <3+:,-5;1:09);59M "! !$ K03+/2)3 .,9M,-;3 S7;69>0 ,""! !! x' /5+141>B
20= ;12<=.7>B9,
g (T , p, x)

= H i (T , p ) + f H i (0K) - T Si (T , p ) + RT
xi
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k

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xi

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n

x = xi !

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[18+1;83\1

k = k !
RT

"#$O#'

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Bi =

H i (T , p) + f H i (0 K ) TSi (T , p)
RT

"#$%&'

()*+, i - ! .! ng! ng/ ! .! ng+ n

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n

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6=*73>*,7+3 4;*6+G*37+3 @123)@ 456738 *36+,43IG>,(; n 456738 "+ n 7+,6+3);L=>M' I,ED :4;:;4>I;73<73 );
n%$ N4*= ;14,H<37+@ E123)@ :4;)@1D56 :4*,L+37= L3D,4+3256 6=E;1;,7,4(,D=>*7=>M * (4@:= YZ[Z\Z]! 73<,F=
*6=1<, ?43O :;) @63(K 6=EDK:;637+, B# U %# E@?ED37>I+$ 0123) "#$%9' *36+,43 656>*3E ;) %^ZD@ ); _^ZD@
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:4*,L+37= + ;) E123)@ >M,L+>*7,(; 6=IH>+;6,(; L3D,4+32@$ aDKF37+3 E@?ED37>I+ 6=EDK:@IG>=>M 6 6=E;1+>M
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:;) >+H7+,7+3L+ ?<+E1+L+ >+H7+,7+@ 3DL;EP,4=>*7,L@$ W 1;<,+ 6 :4;)@1D3>M :4*,L+37= @123)56 ; @I,L7=L
?+<37E+, D<,7;6=L! 6 *6+K1E*;7,I +<;H>+ 6=EDG:+G *6+G*1+ 6K(<;6;);4;6,! I31 Y[_! Y[9! Y%[9! Y[]! Y[%]!
+ +77,$ Q @123)3>M ; *2;F;7=L E123)*+, >M,L+>*7=L! 7:$ :4*= 373<+*+, :4;)@1D56 :4*,L+37= :4;>M@ >*347,(;
A%&C! ()*+, 6=EDK:@IG 4567+,F *6+G*1+ :;D3E@ + E+341+! <+>*?3 456738 I,ED 4*K)@ &^Z>+@$
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EDKF,7+3 7+,1D54=>M * 7+>M L;(G ;E+G(3O ?34)*; L32, 634D;H>+$ Q+,<1;H>+ 6E:52>*=77+156 6 456737+@ "#$%9'
L;(G E+K 656>*3E 45F7+O ; 1+<1373H>+, 4*K)56 6+,<1;H>+$ b,(; D=:@ 45F7+>, 6 634D;H>+3>M 6E:52>*=77+156
<+7;6,(; @123)@ 456738! L;(G 6:2=63O 73 );123)7;HO ;?<+>*,8$
Q >,<@ @:4;E*>*,7+3 :4;>,E@ 6=*73>*37+3 4;*6+G*37+3! 6=:4;63)*;7= *;ED32 *4,)@1;637= @123) 456738 ABcC!
4567;63F7= @123);6+ "#$%9'$ W4,)@1;637= @123) 456738 L;F73 ;D4*=L3O :;:4*,* ,<+L+73>IK :;E*>*,(5<7=>M
*L+,77=>M! L,D;)G D6;4*,7+3 1;L?+73>I+ <+7+;6,I :;E*>*,(5<7=>M 456738 @123)@ "#$%9'$
Q >,<@ 6=,<+L+7;637+3 *L+,77,I !B 73<,F= :+,46E*, ' 456738 "#$%9' :;L7;F=O 1;<,I7; :4*,* "U(+B' ()*+,
i - B! .! '! *3H 456737+,)')/ B :4*,* "UB'$ ]D4*=L@I, E+K 656>*3E

x1 a11 +

y
x
y1 a11 ( 1a11 y1 + 2 a21 y1 + K + m am1 y1 ) a11 = B1 y1 a11 + ln 1 y1 a11
y
y

y
x
x1 a2 1 + y1 a2 1 ( 1a1 1 y1 + 2 a2 1 y1 + K + m am1 y1 ) a2 1 = B1 y1 a2 1 + ln 1 y1 a2 1
y
y
!
y
x
x1 a m1 + y1 a m1 ( 1a11 y1 + 2 a 21 y1 + K + m am1 y1 ) am1 = B1 y1 am1 + ln 1 y1 am1
y
y

x1

x
+ y1
y

1a11 y1 2 a21 y1 + K m am1 y1

= B1 y1

"#$%d'

y
+ ln 1 y1
y

0123) "#$%d' *36+,43 L /B 456738$ R;)3IG> :;E*>*,(5<7, 456737+3 "#$%d' ); 1;<,I7=>M ng + n / i 456738
@123)@ "#$%9'! ()*+,T i - B! '/B ;D4*=L@I, E+K

Bn g +1

K m amn
1a1n
2 a 2n
B
n g + ns

y
x2 a12 + x3 a13 K+ xng a1ng + xng +1a1n g +1 K+ xn a1n y1a11 1a11 y1 a11 2 a 21 y1 a11 K m am1 y1 a11
1
b1 B1 y1 a11 + ln y1 a11
y
y

x
x2 a 22 + x3 a 23 K+ xng a1ng + xng +1a 2n g +1K+ xn a 2n y1a 21 1a11 y1 a 21 2 a 21 y1 a 21 K m am1 y1 a 21 = b2 B1 y1 a21 + ln y1 y1 a21

y
y

M
M
M
M
M
M

y
x

x2 am 2 + x3 am3K+ xng a1ng + xng +1amng +1K+ xn amn y1am1 1a11 y1 am1 2 a 21 y1 am1K m am1 y1 am1 bm B1 y1 am1 + ln 1 y1 am1

y
y

y
x

B1 y1 ln 1 y1
+ x3
x + y1
1a11 y1
2 a21 y1
K+ xn g
K m am1 y1
x2
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1a1n g +1

2 a 2 n g +1

K m amn g +1
M

! "#$%c'

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);1;73O ,<+L+73>I+ 1;<,I7=>M *L+,77=>M !+! i - B! %! .! ng$

?A

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*B! *%! . *LT
1 a1ng +1
M
1 a1ng + ns

x ng +1a1ng +1 K + x n a1ng + ns

x n +1a 2 n +1 K + x n a 2 n + n
g
g
s
g
M

x ng +1a mng +1 K + x n a mng + ns

+ x

+ x

+ x

y
y
M
x
y

ng

y j a1 j
j =1
ng

y j a2 j
j =1
ng

y j a mj
j =1

+ 2 a 2ng +1 +
M
+ 2 a 2 n g + ns +

K + m a mng +1
M
K + m a mng + ns

Bng +1

B n g + ns

ng
ng
ng
ng
yj

+ 1 a1 j y j ( a1 j ) + 2 a 2 j y j ( a1 j ) + K + m a mj y j ( a1 j ) b1 B j y j + ln
y j a1 j

y
j =1
j =1
j =1

j =1

ng
ng
ng
ng

+ 1 a1 j y j ( a 2 j ) + 2 a 2 j y j ( a 2 j ) + K + m a mj y j (a 2 j ) = b2 B j y j + ln j y j a 2 j

y
j =1
j =1
j =1

j =1

M
M

ng
ng
ng
ng
y

y j a mj
+ 1 a1 j y j (a mj ) + 2 a 2 j y j (a mj ) + K + m a mj y j (a mj ) bm B j y j + ln
y

j
=
1
j =1
j =1
j =1

ng
ng
ng
ng

yj

y j
B j y j + ln

K + m a mj y j
+ 1 a1 j y j
+ 2 a2 j y j +
y

j =1
j =1
j =1
j =1

! "#$_^'

0123) 456738 "#$_^' L;F73 *3:+E3O 6 :;ED3>+

Yf0 - " !

"#$_B'

()*+,T Y U L3>+,4* 6E:52>*=77+156g U U 6,1D;4 "1;<@L7;6=' *L+,77=>M 7+,*3<,F7=>Mg " U L3>+,4*

"1;<@L7;63' 6=43*56 6;<7=>M$
]):;6+,)7+;
0

M
0

a
1ng +1

C = a2n +1
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a
m ng +1

a1ng +1
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K a1ng + ns

1
y j a1 j
y j =1
ng

K a2ng + ns
M

1
y j a2 j
y j =1
M
ng

K am ng + ns
K

xn g +1

M
x

n g + ns
x

U=
1

a1ng + ns

ng

1
y j am j
y j =1
0

a2ng +1
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ng

ng

j =1
ng

j =1
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j =1

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a1 j y j (a1 j ) a2 j y j (a1 j )
a1 j y j (a2 j ) a2 j y j (a2 j )
M

ng

ng

j =1
ng

j =1
ng

a1 j y j (am j) a2 j y j (am j)
a1 j y j
j =1

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j =1

B n g +1

Bn g + n s

ng

yj

b B y + ln
y j a1 j
1
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j =1

ng
W = b B y + ln y j y a
2 j j
j 2j !
y

j =1

ng
y

b B y + ln j y a

mj
m
j
j
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j =1

n
g

yj

yj
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j =1

K am ng + ns

ng

K am j y j (a1 j )

j =1

ng

K am j y j (a2 j ) ,
j =1

ng
K am j y j (am j)
j =1

ng

K am j y j

j =1

K am ng +1
M

(5.32)

"#$__'

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x
y

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(k )

y j (k )
y

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yi ( k ) = xi ( k )
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y

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); @123)@ 7;6=>M :+,46+3ED156 + ;):;6+3)3IG>=>M +L *6+G*156 >M,L+>*7=>M! L;F, ?=O :4*,6+)*+373 I31;
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@C

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;14,H<373 I,ED *3<,F7;H>+G ABZ_C
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k +1
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) Va + V nb+1 RT1 ,

pV
= 1 + xe x
RT

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RT

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6A'@+ G'@>+ 7=5'5I7+ 8(2;+ ?)+ 0()1=7H:+ K+ >7?)+ C@:+ 79A'@>545+ <5=7+ 83>7054()+ =70713>)4B0+ 0I5HG(0@GK+
678'G')%B14@GK+ 8=I5&4(=B0+ >()8'54(4@+ <5=J+ 907A'J+ 6A7&3=9@+ &)9745G<("+ U589264()+ &7=74547+ >7&@V=5G<(+
86787C3+ 30'%12&4()4(5+ 9)>6)A593A@+ (+ 3HG(H1747+ >)97&2+ 7=A)H154(5+ =70713>)4B0+ >7170@GK"+ W=93514()+
AB0454()+89543+XOF+89787054)+<)89+0+67895G(+PTR

pV
= 1 + x exp ( x) ,
nRT
%&'()+

!"Y$

!"#$%&'(#)*!+&,-)./#0(.1'#23)()4&"&0#5"67)5#"03,8'&0(.1'8./)4"3,-!567)999

x=

k
V (T + )

!"!$

6A'@+G'@>+!+<)89+=70713>)4)>+0@65&=70@>+79A'@>@054@>+<5=7+83>5+=70713>)4B0+>7170@GK+!(
ng

k = ni k i ,

!"Z$

i =1

[B0454()+ !"Y$+'50()A5+G'9)A@+65A5>)9A@+&7C()A54)+&7H0(5&G'514()*+#;+$;+%+(+&+"+F5A97HG(+9@GK+65A5>)9AB0+
67'0515<J+ &765870@05:+ 67895:+ AB0454(5+ &7+ 0I5HG(07HG(+ 9)A>7&@45>(G'4@GK+ >()8'54(4@+ A)5=9@04)<;+ &7+
76(83+ =9BA)<+ AB0454()+ <)89+ 6A')'45G'74)"+ F5A97HG(+ !(+ 8J+ =70713>)45>(+ GK5A5=9)A@'3<JG@>(+ (4&@0(&3514)+
0I5HG(07HG(+ 678'G')%B14@GK+ 8=I5&4(=B0+ >()8'54(4@"+ F()1=7HG(+ n(+ 7'45G'5<J+ 7&670()&4(7+ (17HG(+ >71(+
ng

678'G')%B14@GK+8=I5&4(=B0;+n = ni\+ng+]+(17H:+8=I5&4(=B0+%5'70@GK+0+>()8'54(4()"
i =1

^89794@>+ &15+ 0@<5H4()4(5+ 0I5847HG(+ (+ '585&47HG(+ 89787054(5+ AB04(5+ 89543+ XOF+ <)89+ A7'659A')4()+ <)%7+
(49)A6A)95G<(+V'@G'4)<+P#_R"
L5=+0(&5:+'+67895G(+AB0454(5+ !"Y$;+6A'@+&3?@GK+05A97HG(5GK+7C<297HG(+3=I5&3;+9<"+&15+%5'B0+A7'A')&'74@GK;+
AB0454()+89543+XOF+6A')GK7&'(+0+AB0454()+89543+%5'3+(&)514)%7"+`15+&3?@GK+V+65A5>)9A+ +895<)+8(2+C70()>+
C1(8=(+')A3"+/+=71)(+6A'@+&3?@GK+%2897HG(5GK+>5870@GK;+05A97H:+676A50=(+45+4()(&)5147H:;+7=A)H1545+6A')'+
6A505+89A742+AB0454(5+ !"Y$;+'45G'JG7+0'A5895"+a'I74+0@89263<JG@+67+6A50)<+89A74()+AB0454(5;+=9BA@+7=A)H15+
06I@0+4()(&)5147HG(+7HA7&=5;+>5+C70()>+67895:+0@=I5&4(G'J"+
/%7&4()+'+0I5847HG(5>(+S34=G<(+0@=I5&4(G')<;+6A50J+89A742+AB0454(5+ !"Y$+>7?45+6A')&8950(:+0+67895G(

pV
( x) 2 ( x) 3
= 1 + x 1 + x +
+
+ .... ,
nRT
3
!
2
!

!"Q$

13C
pV
x3
x4
= 1+ x + x2 + 2
+3
+ .. ,
nRT
2!
3!

!"_$

30'%12&4(5<JG+8678BC+7=A)H1)4(5+ + 0'BA+ !"!$$;+79A'@>3<)+8(2

pV
K (T )
K (T ) 2 2 K (T ) 3 3 K (T ) 4
= 1+
+
+
+
+ ....... ,
2! V 3
3! V 4
nRT
V
V2

!"bc$

%&'()*
ng

ni k i
K (T ) =

i =1

(T + )

!"bb$

L5=+0(&5:+'+67895G(+AB0454(5+ !"bc$+>5+747+S7A>2+54517%(G'4J+&7+0(A(514)%7+AB0454(5+89543"+d7&+0'%12&)>+
67895G(;+ 0(A(514)+ AB0454()+ 89543+ 7&670(5&5+ '585&4(G'@>+ 0@>7%7>+ 676A5047HG(+ AB0454(5+ 89543+ %5'B0+
A')G'@0(89@GK;+0@4(=5<JG@>+'+6A50(&)I+9)A>7&@45>(=(+8959@89@G'4)<+PMc;+MbR+

pV
B (T ) C (T ) D(T )
= 1+
+
+
+ ....... ,
RT
V
V3
V2

!"b#$

d78'G')%B14)+G'I74@+AB0454(5+0(A(514)%7+67'0515<J+45+30'%12&4()4()+06I@03+0()17=A794@GK+7&&'(5I@05D+
>(2&'@>71)=315A4@GK"+ `A3%(+ 086BIG'@44(=+ B '$+ 7=A)H15+ 3&'(5I@+ 0478'74)+ 6A')'+ '&)A')4(5-7&&'(5I@054(5+
&0BGK+>71)=3I;+C '$+]+9A')GK;+( '$+]+G'9)A)GK;+(9&"+
d7AB043<JG+A7'0(4(2G()+AB0454(5+XOF+ !"bc$+'+AB0454()>+0(A(514@>+ !"b#$+>7?)>@+'5305?@:;+?)+AB0454()+
XOF+ >7?)+ C@:+ '(49)A6A)97054)+ <5=7+ 86)G<5145+ S7A>5+ AB0454(5+ 0(A(514)%7"+ d78'G')%B14)+ 086BIG'@44(=(+
0(A(514)+>7%J+C@:+0@A5?74)+<5=7+7&670()&4()+=7>C(45G<)+895I@GK+AB0454(5+XOF+P#_R

"

!"#$%&'()*'

ng

ni ki
,
B(T ) = K (T ) = i =1
(T + )

C (T ) = K (T ) 2 ; D(T ) =

!"bM$
2
K (T ) 3 ; itd. ,
2!

!"bT$

eC)G47H:+0@?8'@GK+G'I74B0+0+A7'0(4(2G(3+AB0454(5+XOF+0+8')A)%+f5@17A5+ !"bc$+08=5'3<);+?)+AB0454()+
67'0515+ 45+ 30'%12&4()4()+ 06I@03+ <)&47G')84)%7+ 7&&'(5I@054(5+ &0BGK;+ 9A')GK;+ G'9)A)GK;+ 6(2G(3+ (+ 0(2G)<+
>71)=3I"+g9J&+AB0454()+89543+XOF+<)89+6A)&)89@47054)+&7+76(83+8954B0+>59)A((+7+%289@>+365=7054(3;+%&'()+
')+0'%12&3+45+C1(8=7H:+>71)=3I;+0@89263<)+45=I5&54()+8(2+6B1+7&&'(5I@05D+67GK7&'JG@GK+7&+8J8(5&3<JG@GK+
')+87CJ+G'J89)G')="+`15+3'@8=54(5+676A504)%7+76(83+0I5HG(07HG(+>()8'54(4@+7+&54@>+8=I5&'()+GK)>(G'4@>;+
086BIG'@44(=(+0(A(514)+670(44@+C@:+&7CA54)+95=;+5C@+7&670(5&5I@+67895G(+679)4G<5IB0+>(2&'@+>71)=315A4@GK+
678'G')%B14@GK+ 83C8954G<(+ GK)>(G'4@GK;+ 0GK7&'JG@GK+ 0+ 8=I5&+ >()8'54(4@"+ L5=+ 0(&5:+ '+ 67895G(+ '51)?47HG(+
!"bT$;+086BIG'@44(=(+0(A(514)+<5=()+0@4(=5<J+'+0I5HG(07HG(+AB0454(5+89543+XOF;+670895<J+<5=7+7=A)H174)+
=7>C(45G<)+895I@GK;+=9BA)+65A5>)9A@'3<J+AB0454()"+
g9J&;+ =5?&5+ 67895:+ AB0454(5+ XOF;+ 7&670(5&5<JG5+ 7=A)H174)<+ =7>C(45G<(+ 0()1=7HG(+ 65A5>)9A@'3<JG@GK+
AB0454()+7&670(5&5:+C2&'()+7=A)H174)<+%A36()+>()8'54(4+7+67&7C4@>+8=I5&'()+GK)>(G'4@>;+95=(>;+=9BA)%7+
0I5847HG(+%A3670)+76(8@054)+8J+6A')'+')86BI+65A5>)9AB0+3?@9@GK+0+AB0454(3"+U51)?@+8(2+AB04()?+867&'()05:;+
?)+676A5047H:+AB0454(5+'51)?):+C2&'()+7&+'5=A)83+G(H4()4(5+ %2897HG($+>()8'54(4@"
F+ 0@4(=3+ &79@GKG'5870@GK+ C5&5D+ 76A5G7054@GK+ '7895I7+ 8')A)%+ 65A5>)9A@'5G<(+ AB0454(5+ XOF"+ U5+
678'G')%B14)+ 65A5>)9A@'5G<)+ 8=I5&5<J+ 8(2+ 05A97HG(+ 895I@GK+ 65A5>)9A@'3<JG@GK+ #;+ $;+ %+ (+ &+ 7A5'+ 0()1=7HG(+
=70713>)4B0+ >7170@GK+ !i"+ L5=+ 0@4(=5+ '+ 0I5847HG(+ AB0454(5+ XOF;+ =9BA@GK+ (1389A5G<J+ <)89+ A7'0(4()G()+
0+8')A)%+f5@17A5;+678'G')%B14)+65A5>)9A@'5G<)+AB0454(5+XOF+7&670(5&5:+C2&J+>()8'54(47>+7+&54@>+9@6()+
8=I5&3+GK)>(G'4)%7+7A5';+'5GK703<J+676A5047H:+0+7=A)H174@>+6A')&'(51)+'>(54+%2897HG(+>5870@GK;+G(H4()D+
(+9)>6)A593A+A7'659A@054@GK+>()8'54(4+ 6A7&3=9B0+&)9745G<(+(+0@C3GK3$"+
dA50(&I70)+ 7=A)H1)4()+ '5=A)83+ 05?47HG(+ &54)<+ 65A5>)9A@'5G<(+ XOF+ <)89+ 67&8950J+ &7+ 3'@8=54(5+ 0@87=()<+
&7=I5&47HG(+0@4(=B0+7C1(G')D+0@=7454@GK+6A'@+<)<+0@=7A'@8954(3"
6.2. #$%$&'(%)*$+,'-%./0$01$-BKW
d7895:+ AB0454(5+ XOF+ !"Y+ h+ !"Z$+ '56)04(5+ <)%7+ 7=A)H174J+ )1589@G'47H:+ (+ 8905A'5+ >7?1(07H:+ 95=()%7+
&76587054(5+ 65A5>)9AB0+ AB0454(5;+ 7C@+ 79A'@>@054)+ '51)?47HG(+ 67>(2&'@+ G(H4()4()>;+ %2897HG(J+ >5870J+
7C<297HG(J+0I5HG(0J$+(+9)>6)A593AJ+7&670(5&5I@+GK5A5=9)A@89@=7>+V'@G'4@>+(+GK)>(G'4@>+A7'659A@054)<+
>()8'54(4@+A)5=9@04)<"
F+0@4(=3+&79@GKG'5870@GK+C5&5D+76A5G7054@GK+'7895I7+8')A)%+65A5>)9A@'5G<(+AB0454(5+XOF"+F+0(2=8'7HG(;+
G)1)>+6A5G+45&+&7C7A)>+086BIG'@44(=B0+XOF+C@I7+'56)04()4()+'%7&47HG(+7C1(G'54@GK+65A5>)9AB0+&)9745G<(+
'+&54@>(+&7H0(5&G'514@>(;+'0@=1)+'+67>()A'74@>(+05A97HG(5>(+6A2&=7HG(+&)9745G<("+i7?45+0@AB?4(:+9A'@+
86787C@+&7C7A3+05A97HG(+65A5>)9AB0+AB0454(5+XOF*
j$+]+%)7>)9A@G'4@\+6A'@+7=A)H154(3+05A97HG(+=70713>)4B0+>7170@GK+0@=7A'@89@054)+8J+&54)+&79@G'JG)+
%)7>)9A((+>71)=3I+678'G')%B14@GK+8=I5&4(=B0+>()8'54(4@\
W$+]+5&(5C59@G'4@\+05A97H:+=70713>)43+7&670(5&5<JG)%7+&54)<+83C8954G<(+GK)>(G'4)<+0@'45G'545+<)89+45+
67&8950()+6A')C()%3+5&(5C59@+3&)A')4(70)<+9)<+83C8954G<(\+
`$+ ]+ &)9745G@<4@\+ 65A5>)9A@+ AB0454(5+ XOF+ &7C()A54)+ 8J+ 95=;+ 5C@+ 3'@8=5:+ '%7&47H:+ 0@4(=B0+ 7C1(G')D+
'+)=86)A@>)49514()+7=A)H154@>(+05A97HG(5>(+65A5>)9AB0+&)9745G<(;+'0I58'G'5+'+6A2&=7HG(J+&)9745G<("
F+ 1(9)A593A')+ 6A')&8950(74@GK+ '7895I7+ 8')A)%+ >)97&+ 7=A)H154(5+ ')8950B0+ 65A5>)9AB0+ AB0454(5+ XOF"+
L5=7+ 45<C5A&'()<+ GK5A5=9)A@89@G'4)+ (+ >5<JG)+ 45<0(2=8')+ '45G')4()+ 6A5=9@G'4)+ 0@AB?4(>@+ 4589263<JG)+
65A5>)9A@'5G<)*
XOFki*+65A5>)9A@'5G<5+76A5G70545+6A')'+i5&)A5+PTR;
XOFk[*+A)65A5>)9A@'5G<5+76A5G7054(5+i5&)A5;+6A')&8950(745+45+.^h9@>+g@>67'<3>+`)9745G<(+PM#R

!"#$%&'(#)*!+&,-)./#0(.1'#23)()4&"&0#5"67)5#"03,8'&0(.1'8./)4"3,-!567)999

XOFkl*+34(0)A85145+ %)7>)9A@G'45$+>)97&5+&7C7A3+=70713>)4B0+PMMR
XOFka*+')8950+086BIG'@44(=B0+(+=70713>)4B0+XOF+'454@+<5=+aK))95K+PMTR
)*"+"!,-+./,.!"01"+"2-,+.3"4560789:;
d5A5>)9A@'5G<5+76A5G70545+6A')'+i5&)A5+<)89+45<895A8'J+867HAB&+65A5>)9A@'5G<(+XOF"+g678BC+&7C7A3+05A97HG(+
678'G')%B14@GK+ 65A5>)9AB0+ AB0454(5+ XOF+ 0+ 65A5>)9A@'5G<(+ XOFki+ 7=A)H1(:+ >7?45+ <5=7+ >()8'54@"+
F+6()A08'@>+6A'@C1(?)4(3;+05A97HG(+=70713>)4B0+7=A)H154)+C@I@+45+67&8950()+%)7>)9A@G'4)<+(49)A6A)95G<(+
0@>(5AB0+ >71)=3I+ <$"+ d7&8950J+ &7+ 7=A)H1)4(5+ 05A97HG(+ =70713>)43+ C@I+ 0@65&=70@+ 6A7>()D+ >71)=3I@"+
U589264()+05A97H:+=70713>)43+0@'45G'547+')+0'7A3+

4
k = 10,46 (R A )3 ,
3

!"bY$

%&'()*+RA+]+6A7>()D+>71)=3I@+0+m4%89A)>5GK"+
`15+8')A)%3+83C8954G<(;+05A97HG(+=70713>)4B0+7=A)H174)+>)97&J+%)7>)9A@G'4J+C@I@+4589264()+0)A@V=7054)+
676A')'+67AB0454()+'+&54@>(+0@4(=5<JG@>(+3&)A')4(70)%7+86A2?54(5+678'G')%B14@GK+83C8954G<(+GK)>(G'4@GK"+
[7'659A@0547+5&(5C59@+3&)A')4(70)+%IB04@GK+8=I5&4(=B0+6A7&3=9B0+&)9745G<(+(+0@C3GK3*+l#e;+ae;+U#;+l#"+
F+ 95C)1(+ !"b+ 6A')&8950(74)+ '7895I7+ 67AB0454()+ 05A97HG(+ =70713>)4B0+ 0@'45G'74@GK+ 45+ 67&8950()+
%)7>)9A@G'4)<+(49)A6A)95G<(+0@>(5AB0+>71)=3I+7A5'+05A97HG(+79A'@>54@GK+676A')'+67AB0454()+'+5&(5C595>(+
&7H0(5&G'514@>("+
!"#$!%&'('% !"#$%&%'() $&"*!+,') -!$!./0(%#$) 1(!0(*"2,3%2,4) ') $23%&,3!%2,4) 5!5"3(3) 6!5&7!$&%'()
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B
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MG
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HIJ
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KLL
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5"R6-!+,')6(*!%&,;')$2%!73D,D)OHJ>)0Y7)!"&3),'+%'(%'()$)5/%-,'()E4&50&%&Z[!/1/(*&)!EZ[)\)I>VH)] &U)
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;(7*)$),(./)3&5!<'(_(%'&)$27*D5'(%'/)!7!<.'$!+,')$)"#$%&%'/V)162)*(05("&*/"&)$%6D_2)6!)3("&U)
@*&S()"#$%&%'&)89:)5"32;R*()$)5&"&0(*"23&,;')89:WX)3(7*&$'!%!)$)*&<(.')KUGU
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