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∆G ° 298 = –79,5 d>`fhev
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(3)
∆G ° 298 = –9,6 d>`fhev
_
KH )_3O4 KH2;
∆G ° 298 = –50,6 d>`fhev
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(5)
)H6 G22
)_3O4 + 3H26 G2;
∆G ° 298 = –75 d>`fhev
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r_gb_f ijh[e_fu ^_kmevnmjbaZpbb fh`_l klZlv kgb
86
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Ij_^eh`_g dZlZebaZlhj k ^h[Z\dZfb KZ FJ <Z
MklZgh\e_gh qlh \\_^_gb_ wlbo ^h[Z\hd k^\b]Z_l ijh
p_kk ^_kmevnmjbaZpbb \ h[eZklv [he__ \ukhdbo l_fi_
jZlmj > 25].
Iheguf j_r_gb_f ijh[e_fu wnn_dlb\gh]h b gZ
^_`gh]h dZlZebaZlhjZ ^ey ijhba\h^kl\Z ZffbZdZ y\ey
_lky ijbf_g_gb_ [_kk_jgbklh]h hdkb^Z `_e_aZ
Dbg_lbdZ ijhp_kkZ dhg\_jkbb fhghhdbkb m]e_jh^Z
Hlf_lbf hkgh\gu_ jZ[hlu ih bkke_^h\Zgbx dbg_lb
db dhg\_jkbb fhghhdkb^Z m]e_jh^Z gZ jZaebqguo `_e_
ahkh^_j`Zsbo dZlZebaZlhjZo BamqZeZkv dbg_lbdZ j_Zd
pbb ijb l_fi_jZlmjZo \ur_ ƒK gZ dZlZebaZlhj_
ba g_ijhfhlbjh\Zggh]h hdkb^Z `_e_aZ b gZ \ukhdhl_f
i_jZlmjghf `_e_ahfZ]gb_\hf dZlZebaZlhj_ G< Dmevdh\Z b FB Lëfdbg Ijb \u\h^_ dbg_lbq_kdh]h mjZ\
g_gby bkke_^h\Zl_eb hkgh\u\Zebkv gZ f_oZgbaf_ ijh
p_kkZ khklhys_]h \ ihi_j_f_gghf hdbke_gbb-\hkklZgh\e_gbb ih\_joghklgh]h fhghfhe_dmeyjgh]h kehy
dZlZebaZlhjZ >@
D*—H KH D* KH2
(7)
*
*
D + H22 D —H G2
(8)
]^_ D — Zdlb\guc mqZklhd p_glj ih\_joghklb dZlZ
ebaZlhjZ
IjbgbfZy \ dZq_kl\_ ebfblbjmxs_c klZ^bb hij_^_eyxs_c kdhjhklv kmffZjgh]h ijhp_kkZ j_Zdpbx Z\lhju ij_^eh`beb ke_^mxs__ dbg_lbq_kdh_ mjZ\g_gb_
 S+ 2
ω = N S &2 
 S+





β
 S+ − N S &2 
 S+ 2





− β
(9)
]^_ ω — kdhjhklv j_Zdpbb k1, k2 — dhgklZglu kdhjhklb
ijyfhc b h[jZlghc j_Zdpbc jKH, jG2H, jG2, jKH2 — iZj
pbZevgu_ ^Z\e_gby khhl\_lkl\mxsbo ]Zah\ β — dhwn
nbpb_gl jZ\guc Ba ZgZebaZ mjZ\g_gby ke_^m_l qlh kdhjhklv j_Zd
pbb aZ\bkbl hl dhgp_gljZpbb fhghhdkb^Z m]e_jh^Z
\h^hjh^ \ h[eZklb l_fi_jZlmj —500 ƒK lhjfhabl
j_Zdpbx dhg\_jkbb ^bhdkb^ m]e_jh^Z g_ \eby_l gZ
kdhjhklv j_Zdpbb ZgZeh]bqgh bg_jlghfm jZa[Z\bl_ex
— Zahlm >bnnmabhggu_ nZdlhju ijb l_fi_jZlmjZo
400—500 ƒK g_ \ebyxl gZ kdhjhklv ijhp_kkZ
Bkke_^h\ZeZkv dbg_lbdZ dhg\_jkbb hdkb^Z m]e_jh^Z
\h^yguf iZjhf gZ `_e_ahojhfh\hf b gbadhl_fi_jZlmj
ghf pbgdojhff_^ghf dZlZebaZlhjZo == Sb[jy
GF Fhjhah\ FB Lëfdbg Ihemq_ggu_ hiulgu_
^Zggu_ \ dbg_lbq_kdhc h[eZklb hibku\Zxlky ke_^mx
sbf mjZ\g_gb_f >@
ω=N
S &2 S + 2 − .S + S &2
$S + 2 − S &2 (10)
! " ]^_ k — dhgklZglZ kdhjhklb ijyfhc j_Zdpbb D — dhg
klZglZ jZ\gh\_kby : — dhwnnbpb_gl aZ\bkysbc hl
l_fi_jZlmju < kemqZ_ `_e_ahojhfh\h]h dZlZebaZlhjZ
OJ $ = −
+ 7
Ihemq_gh lZd`_ ke_^mxs__ dbg_lbq_kdh_ mjZ\g_gb_
dhg\_jkbb fhghhdkb^Z m]e_jh^Z iZjZfb \h^u gZ `_e_
ahojhfh\hf dZlZebaZlhj_ gZg_k_gghf gZ hdkb^ fZ]gby
<B :ljhs_gdh ; ;b[j
−
GS &2
Gτ
′
S &2 − S &2
=N
S+ ⋅ S+
2
(11)
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gb_ fhghhdkb^Z m]e_jh^Z
:\lhju mklZgh\beb aZ\bkbfhklv dhgklZglu kdhjhklb
j_Zdpbb hl l_fi_jZlmju
k = 4, 92 ⋅105 ⋅ e
−
18460
RT
Ijhba\h^bl_evghklv dZlZebaZlhjZ \ aZ\bkbfhklb hl
^Z\e_gby J jZ\gZ
3
] = ] 3 >d]f ‡q@
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kn_jghf ^Z\e_gbb
Ih ^Zgguf ;G @b^dh\Z <B :ljhs_gdh b
:I AZkhjbgZ kdhjhklv dhg\_jkbb fhghhdkb^Z m]e_jh
^Z iZjZfb \h^u gZ `_e_ahojhfh\hf dZlZebaZlhj_ hij_
^_ey_lky mjZ\g_gb_f
−
GS &2
Gτ
=N
S &2
S &2
(12)
BamqZebkv dbg_lbq_kdb_ aZdhghf_jghklb ijhp_kkZ
gZ jZaebqguo Zdlb\guo kj_^g_l_fi_jZlmjguo dZlZebaZ
lhjZo BI Dbjbeeh\ <N KZdkbg IhdZaZgh qlh
baf_g_gb_ kh^_j`Zgby \h^hjh^Z \ bkoh^ghc ]Zah\hc
kf_kb \ ij_^_eZo hl ^h g_ \eby_l gZ kdhjhklv
j_Zdpbb Z ^bhdkb^ m]e_jh^Z lhjfhabl __ Ijbgy\ qlh
lhjfhays_c klZ^b_c y\ey_lky hdbke_gb_ ih\_joghklb
dZlZebaZlhjZ Z\lhju \u\_eb ke_^mxs__ ^bnn_j_gpb
Zevgh_ mjZ\g_gb_ kdhjhklb dhg\_jkbb fhghhdkb^Z m]e_
jh^Z \h^yguf iZjhf
 S

ω = N S + 2  &2 
 S &2 


− N S+  S &2 


 S &2 


(13)
JZaebqb_ lhjfhaysbo nZdlhjh\ khhl\_lkl\mxsbo
^Zgguf BI Dbjbeeh\Z b <N KZdkbgZ \ebygb_ ^bhd
kb^Z m]e_jh^Z b ^Zgguf G< Dmevdh\hc b
FB LëfdbgZ \ebygb_ \h^hjh^Z ih-\b^bfhfm ke_^m
_l h[tykgblv baf_g_gb_f ebfblbjmxs_c klZ^bb \ jZa
ebqguo l_fi_jZlmjguo mkeh\byo ijh\_^_gby j_Zdpbb
GZ hkgh\Zgbb nhjfmeu [ueh ihemq_gh mjZ\g_
gb_ ^ey hij_^_e_gby \j_f_gb dhg\_jkbb fhghhdkb^Z
m]e_jh^Z iZjZfb \h^u
τ=
D
N Q − D [ 0 [
(14)
‹
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bkoh^ghf ]Za_ ^heb _^bgbpu k — dhgklZglZ kdhjhklb
ijyfhc j_Zdpbb n — h[t_fgh_ khhlghr_gb_ \h^yghc
iZjdhg\_jlbjm_fuc ]Za o — kl_i_gv dhg\_jkbb KH,
^heb _^bgbpu M(o) — fgh`bl_ev aZ\bkysbc hl o b
khhlghr_gby \ bkoh^ghf ]Za_ KH2 : CO.
Kujv_ ^ey ijhba\h^kl\Z dZlZebaZlhjh\ dhg\_jkbb
fhghhdkb^Z m]e_jh^Z b ljZ^bpbhggu_ f_lh^u
bo ijb]hlh\e_gby
Ihbkd g_^_nbpblgh]h kujvy b ih\ur_gb_ wnn_d
lb\ghklb _]h bkihevah\Zgby \ ijhba\h^kl\_ ijhfur
e_gguo dZlZebaZlhjh\ y\ey_lky h^gbf ba \Z`g_crbo
gZijZ\e_gbc \ mkh\_jr_gkl\h\Zgbb l_ogheh]bb ijb]h
lh\e_gby dZlZebaZlhjh\ >—30].
Hdkb^ `_e_aZ — hkgh\ghc dhfihg_gl dZlZebaZlhjh\
^ey dhg\_jkbb fhghhdkb^Z m]e_jh^Z fh`gh ihemqblv
l_jfbq_kdbf jZaeh`_gb_f jZaebqguo kh_^bg_gbc `_e_
aZ ]b^jhdkb^Z gbljZlZ dZj[hgZlZ kmevnZlZ oehjb^Z
Zedh]heylZ hdkZeZlZ b ^j L_ogbq_kdb_ hdkb^u `_e_aZ
ihemq_ggu_ l_jfhebahf khe_c jZaebqZxlky fhjnheh
]b_c b ^_n_dlghklvx qZklbp qlh h[mkeh\eb\Z_l jZaebq
gmx Zdlb\ghklv \ obfbq_kdbo j_Zdpbyo b qZklh h]jZgb
qb\Z_l \hafh`ghklv bo bkihevah\Zgby ^ey ijb]hlh\e_
gby dZlZebaZlhjh\ >—33].
GZb[he__ jZkijhkljZg_gguc f_lh^ ihemq_gby Zd
lb\gh]h hdkb^Z `_e_aZ [Zabjm_lky gZ kh\f_klghf hkZ`
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ke_^mxsbf h[jZahf >@
jZkl\hj khe_c `_e_aZ + hkZ^bl_ev → klZj_gb_ hkZ^dZ→
→ ijhfu\dZ → kmrdZ → ijhdZeb\Zgb_
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87
1
400
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350
0,6
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1,5
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200
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(1
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F_lh^ nhjfh\Zgby wdkljmab_c hlebqZ_lky hlghkbl_ev
ghc ijhklhlhc b g_ lj_[m_l ijbf_g_gby ^hjh]hklhys_]h
h[hjm^h\Zgby h[_ki_qb\Zy ihemq_gb_ dZlZebaZlhjh\ k
^hklZlhqgh \ukhdhc f_oZgbq_kdhc ijhqghklvx
Kms_kl\_gguc g_^hklZlhd wdkljmab\ghc l_ogheh]bb
k\yaZg k l_f qlh ih^[hj fZkk ^ey nhjfh\Zgby ]jZgme
dZlZebaZlhjh\ ijh\h^blky dZd ijZ\beh wfibjbq_kdbf
iml_f qlh aZqZklmx aZljm^gy_l \u[hj hilbfZevghc
j_p_ilmju b kihkh[Z ihemq_gby nhjfh\hqghc fZkku
GZ gZr \a]ey^ jZajZ[hldZ gh\uo b mkh\_jr_gkl\h\Zgb_
kms_kl\mxsbo kihkh[h\ ijb]hlh\e_gby dZlZebaZlhj
guo fZkk g_\hafh`gu [_a ]em[hdh]h bamq_gby ijhp_k
kh\ kljmdlmjhh[jZah\Zgby Lhevdh agZy k\hckl\Z dhZ]m
eypbhgghc kljmdlmju fh`gh p_e_gZijZ\e_ggh mijZ\
eylv j_heh]bq_kdbfb k\hckl\Zfb fZkk gZ jZggbo klZ^b
yo bo ijb]hlh\e_gby
< jy^_ jZ[hl > @ ihdZaZgh qlh nhjfh\hqgu_
fZkku hlghkylky d l\_j^hh[jZaguf \yadhieZklbqguf
kljmdlmjbjh\Zgguf kbkl_fZf l_ ^h ^hklb`_gby g_dh
lhjh]h gZijy`_gby J1 hgb \_^ml k_[y dZd l\_j^u_ l_eZ b
ebrv ihke_ ij_\ur_gby ih^ ^_ckl\b_f gZ]jmadb wlh]h
ij_^_eZ bo ih\_^_gb_ klZgh\blky ih^h[guf l_q_gbx
\yadhieZklbqguo `b^dhkl_c > @ >_nhjfZpbhggu_ b
j_eZdkZpbhggu_ k\hckl\Z kljmdlmjbjh\Zgguo kbkl_f k
^hklZlhqghc lhqghklvx fh]ml [ulv hibkZgu fh^_evx
FZdk\_eeZ—R\_^h\Z—D_ev\bgZ >@
ε′ =
!
+
!

 τ  − H[S  −
 η


 +

 
! + ! τ
η
(16)
]^_ ε′ — hlghkbl_evgZy kmffZjgZy ^_nhjfZpby J —
\g_rgyy gZ]jmadZ J1 — mkeh\guc klZlbq_kdbc ij_^_e
l_dmq_klb ?1, ?2 — fh^mev [ukljhc b f_^e_gghc weZ
klbq_kdbo ^_nhjfZpbc khhl\_lkl\_ggh η1 — gZb[hev
rZy ieZklbq_kdZy \yadhklv η2 — \yadhklv mijm]h]h
ihke_^_ckl\by τ — \j_fy ^_ckl\by gZ]jmadb
< nhjfh\hqghc fZkk_ ijbkmlkl\mxl \k_ ljb \b^Z
^_nhjfZpbc [ukljZy weZklbq_kdZy mijm]Zy εmi f_^
e_ggZy weZklbq_kdZy εwe ieZklbq_kdZy εie DZ`^h_ keZ
]Z_fh_ \ mjZ\g_gbb khhl\_lkl\m_l i_j_qbke_gguf
\b^Zf ^_nhjfZpbc l_ ε′ = εmi + εwe + εie Hlkx^Z fh`
gh jZkkqblZlv ^hex dZ`^h]h \b^Z ^_nhjfZpbc \ h[s_f
[ZeZgk_ ijbgbfZy \_ebqbgm ε′ aZ Fh^_ev fh`_l [ulv bkihevah\ZgZ ^ey bamq_gby
kljmdlmjgh-f_oZgbq_kdbo k\hckl\ nhjfh\hqguo dZlZ
ebaZlhjguo fZkk Z ih ihemq_gguf ba g__ ^Zgguf fh`
gh ijh]ghabjh\Zlv ijb]h^gZ eb fZkkZ d wdkljmabhgghfm
nhjfh\Zgbx >@
MklZgh\e_gh qlh fZkkZ `_e_ahojhfh\h]h dZlZebaZ
lhjZ ijb]hlh\e_ggZy ih ljZ^bpbhgghc l_ogheh]bb im
l_f kf_r_gby ojhfh\h]h Zg]b^jb^Z k hdkb^hf `_e_aZ b
\h^hc hlghkblky d gme_\hfm kljmdlmjgh-f_oZgbq_kdhfm
lbim k ij_h[eZ^Zgb_f [ukljuo weZklbq_kdbo ^_nhjfZ
pbc jbk h[jZa_p H[jZ[hldZ wlhc `_ fZkku ih ^\mo
klZ^bcghc l_ogheh]bb \ ^bki_j]bjmxsbo mkljhckl\Zo
baf_evq_gb_ qZklb α-Fe2O3 \ ojhfh\hc dbkehl_ k ihke_
^mxsbf ^h[Z\e_gb_f g_h[oh^bfh]h dhebq_kl\Z hdkb^Z
`_e_aZ b jZkl\hjZ \h^hjZkl\hjbfh]h ihebf_jZ iha\hey_l
kgbablv \_ebqbgm [ukljuo weZklbq_kdbo ^_nhjfZpbc k ^h jbk h[jZa_p Ijb wlhf f_^e_ggu_ weZklbq_
kdb_ b ieZklbq_kdb_ ^_nhjfZpbb \hajZklZxl khhl\_lkl\_g
gh k ^h b k ^h >@
Hkgh\ghc ijbqbghc memqr_gby j_heh]bq_kdbo
k\hckl\ gZjy^m k nZdlhjhf baf_evq_gby qZklbp hdkb^Z
`_e_aZ y\ey_lky \hajZklZgb_ obfbq_kdh]h \aZbfh^_ckl
\by dhfihg_glh\ Z lZd`_ \ha^_ckl\b_ \h^hjZkl\hjbfh
]h ihebf_jZ iheb\bgbeh\uc kibjl beb dZj[hdkbf_
lbep_eexehaZ MklZgh\e_gh qlh dZlZebaZlhjgZy fZkkZ
ihemq_ggZy ba n_jjblh\ dZevpby b f_^b h[eZ^Z_l \u
91
k  jãÒÓ s s väÒ¯Óºm k k jãÒÓ
4. FheqZgh\
εie
< < ;mygh\ J : Mki_ob obfbb
l
‹ k
—492.
5. >abkvdh < : Hkgh\u f_lh^h\ ijb]hlh\e_gby dZlZebaZlh
jh\ Gh\hkb[bjkd GZmdZ
k
6. Ijhba\h^kl\h ZffbZdZ Ih^ j_^ < I K_f_gh\Z F Ob
fby
k
7. HqbkldZ l_ogheh]bq_kdbo ]Zah\ Ih^ j_^ L : K_f_gh\hc
B E E_cl_kZ F Obfby
k
8. K_f_gh\ < I K_f_gh\Z L : Ijhba\h^kl\h ZffbZdZ ih wg_j]h
l_ogheh]bq_kdhc ko_f_ F GBBLWOBF
k
9. H\kb_gdh H E b ^j DZlZeba \ ijhfure_gghklb
‹ k —45.
10. K_f_gh\Z L : b ^j DZlZebaZlhju ZffbZqgh]h ijhba\h^kl
\Z F GBBLWOBF
k
11. KijZ\hqgbd ZahlqbdZ F Obfby
k
12. KijZ\hqgh_ jmdh\h^kl\h ih dZlZebaZlhjZf ^ey ijhba\h^kl
\Z ZffbZdZ b \h^hjh^Z Ih^ j_^ < I K_f_gh\Z E Obfby
k
13. L_ogheh]by dZlZebaZlhjh\ Ih^ j_^ B I Fmoe_gh\Z E
Obfby
k
14. :e_dk__\ : F FboZceh\Z G I ;_kdh\ < K Obf ijhf
‹ k —103.
15. Dhfh\Z A < DZlZeba \ ijhfure_gghklb
‹ k
16. FZjdbgZ F B b ^j Lj =B:I
\ui
k —84.
17. FZjdbgZ F B b ^j Dbg_lbdZ b dZlZeba
l
‹
k
—871.
18. Bevbg : I b ^j <hij dbg_lbdb b dZlZebaZ B\Zgh\h
k —114.
19. Nmj_g W E b ^j Dbg_lbdZ b dZlZeba
l ‹ k
.
20. Nmj_g W E b ^j Obf ijhf-klv
‹ k
—288.
21. Nmj_g W E b ^j Dbg_lbdZ b dZlZeba
l
‹
k
—456.
22. Rbjhdh\ X = Bevbg : I <hij dbg_lbdb b dZlZebaZ
B\Zgh\h
k
—110.
23. :ljhs_gdh < B b ^j L_ogheh]by k\yaZggh]h ZahlZ OZjv
dh\
k
24. Dhfh\Z A < b ^j MdjZbgkdZy gZmqgh-l_ogbq_kdZy dhgn ih
dZlZebam
k —69.
25. DZeZrgbd : < b ^j LZf `_
k —50.
26. Dmevdh\Z G < Lëfdbg F B @ nba obfbb
l
‹ k
27. Sb[jy = = b ^j Dbg_lbdZ b dZlZeba
l
‹
k
—1068.
28. Dhfh\Z A < b ^j <hij dbg_lbdb b dZlZebaZ B\Zgh\h
k 14—119.
29. >abkvdh < : Dbg_lbdZ b dZlZeba
l
‹ k
30. Rbjhdh\ X = >bkk ^hdl l_og gZmd B\Zgh\h
k
31. Kl_iZgh\ ? = Dhl_evgbdh\ = J DZlZeba \ ijhfure_ggh
klb
‹ k —56.
32. Dhl_evgbdh\ = J @ ijbde obfbb
l
‹
k
—282.
33. Kl_iZgh\ ? = b ^j Dbg_lbdZ b dZlZeba
l
‹
k
—944.
34. Dmgbg : < b ^j Ba\ \ukr mq_[ aZ\_^_gbc Obfby b
obfbq_kdZy l_ogheh]by
‹ k —89.
35. Djb\hjmqdh H I Ju`bd B : Dbg_lbdZ b dZlZeba
l
‹ k
—477.
36. ;mjqbgZ ? ; b ^j @ kljmdl obfbb
l
‹
k
—497.
37. QZeuc < I =b^jhhdbkb f_lZeeh\ Db_\ GZmdh\Z ^mfdZ
k
38. :\\Zdmfh\ ? = F_oZgbq_kdb_ f_lh^u Zdlb\Zpbb obfbq_
kdbo ijhp_kkh\ Gh\hkb[bjkd GZmdZ
k
V
2
II
3
1
εwe
I
0
>bZ]jZffZ jZa\blby ^_nhjfZpbc \ fZkk_ dZlZeb
aZlhjZ dhg\_jkbb fhghhdkb^Z m]e_jh^Z gZ klZ^bb wdkljm
abhggh]h nhjfh\Zgby
DZlZebaZlhj b kihkh[ ijb]hlh\e_gby fZkku ^ey wdkljmabb
1 — `_e_ahojhfh\uc dZlZebaZlhj ijhfure_ggZy l_ogheh
]by 2 — `_e_ahojhfh\uc dZlZebaZlhj bkihevah\Zgb_ ^bk
i_j]bjh\Zgby b \h^hjZkl\hjbfh]h ihebf_jZ 3 — gZ hkgh\_
n_jjblh\ dZevpby b f_^b
0, I,...,V — kljmdlmjgh-f_oZgbq_kdbc lbi fZkku
khdbfb j_heh]bq_kdbfb oZjZdl_jbklbdZfb ^Z`_ [_a
^h[Z\hd ihebf_jh\ Ijb wlhf \_ebqbgu [ukljuo b
f_^e_gguo weZklbq_kdbo ^_nhjfZpbc b ieZklbq_kdhc
^_nhjfZpbb khklZ\eyxl khhl\_lkl\_ggh jbk h[jZa_p 3).
LZdbf h[jZahf jZ\ghf_jgh_ jZa\blb_ \k_o \b^h\
^_nhjfZpbc h[_ki_qb\Z_l \hafh`ghklv wdkljmabhggh]h
nhjfh\Zgby dZlZebaZlhjguo fZkk \ ]jZgmeu
:gZeba ijhp_kkZ dhg\_jkbb fhghhdkb^Z m]e_jh^Z
\h^yguf iZjhf \ ^_ckl\mxs_c l_ogheh]bq_kdhc ko_f_
ijhba\h^kl\Z ZffbZdZ b bkke_^h\Zgby ijh\h^bfu_ \
B\Zgh\kdhf ]hkm^Zjkl\_gghf obfbdh-l_ogheh]bq_kdhf
mgb\_jkbl_l_ ^Zxl hkgh\Zgby kqblZlv qlh ^ey klZ^bb
kj_^g_l_fi_jZlmjghc dhg\_jkbb fhghhdkb^Z m]e_jh^Z
i_jki_dlb\gufb y\eyxlky dZlZebaZlhju gZ hkgh\_ n_j
jblh\ dZevpby b f_^b ijb]hlZ\eb\Z_fu_ ih f_lh^m
f_oZghobfbq_kdh]h kbgl_aZ Wlhl f_lh^ iha\hey_l ih
emqZlv \ukhdh^bki_jkgu_ ihjhrdb n_jjblh\ dZevpby b
f_^b Z lZd`_ kms_kl\_ggh kgbablv l_fi_jZlmjm ihke_
^mxs_c l_jfhh[jZ[hldb N_jjbl dZevpby ijhy\ey_l
\ukhdmx dZlZeblbq_kdmx Zdlb\ghklv \ h[eZklb l_fi_
jZlmj — ƒK Z n_jjbl f_^b gZb[he__ Zdlb\_g \
[he__ gbadhl_fi_jZlmjghc h[eZklb — ƒK DZlZ
ebaZlhjgZy fZkkZ ihemq_ggZy ba n_jjblh\ dZevpby b
f_^b h[eZ^Z_l \ukhdbfb j_heh]bq_kdbfb oZjZdl_jb
klbdZfb b g_ gm`^Z_lky \ bkihevah\Zgbb ^h[Z\hd iheb
f_jh\ N_jjblu dZevpby b f_^b fh]ml [ulv bkihevah
\Zgu ^ey kha^Zgby dZlZebaZlhjh\ dhg\_jkbb KH gh\h]h
ihdhe_gby
EBL?J:LMJ:
1. I_ljh\ E : DZlZeba \ ijhfure_gghklb
‹ k
2. Imlbeh\ : < Obfby b jughd
‹ k —35.
3. IZjfhg < G Obfby \ bgl_j_kZo mklhcqb\h]h jZa\blby
l ‹ k
92
Jbk
εmi
III
IV
‹ 39. Eyoh\
G A ;he^uj_\ < < Ba\ KH :G KKKJ l ‹ k —8.
40. F_oZghobfbq_kdbc kbgl_a \ g_hj]Zgbq_kdhc obfbb K[
gZmqg lj Ih^ j_^ ?= :\\Zdmfh\Z Gh\hkb[bjkd GZmdZ
k
41. Rbjhdh\ X = Bevbg : I Ba\ KH :G J:G KKKJ ‹ k —38.
42. ;mly]bg I X Mki_ob obfbb l ‹ k —1780.
43. ;he^uj_\ < < :\\Zdmfh\ ? = LZf `_ l ‹ k —1856.
44. ;mygh\ J : FheqZgh\ < < Obf ijhf ‹ k —158.
45. Rbjhdh\ X = F_oZghobfby \ l_ogheh]bb dZlZebaZlhjh\
B\Zgh\h k
46. :\\Zdmfh\ ? = Obf l_ogheh]by ‹ k —17.
47. :g^jbZgZkmem G L b ^j Ba\ \ukr mq_[ aZ\_^_gbc Obfby
b obfbq_kdZy l_ogheh]by ‹ k —59.
48. Bevbg : I b ^j GZmqgu_ hkgh\u ijb]hlh\e_gby dZlZebaZ
lhjh\ Gh\hkb[bjkd k —185.
49. <Zkbev_\Z G : Rbjhdh\ X = LZf `_ k —75.
50. E_\bg ; ? Lj_lvydh\ X > Nbabdh-obfbq_kdb_ hkgh\u
ihemq_gby b ijbf_g_gb_ n_jjblh\ F F_lZeemj]by 51. ;eykk_
k
@ DjbklZeehobfby n_jjhribg_e_c F F_lZeemj
]by k
52. E_lxd E F @mjZ\e_\ = B Obfby b l_ogheh]by n_jjblh\
E Obfby k
53. Dhkh\Z G < b ^j G_hj]Zg fZl l ‹ k —484.
54. Bkmih\Z E : b ^j Dbg_lbdZ b dZlZeba l ‹ k —139.
55. :[Zdmfh\ : F b ^j Mki_ob obfbb l ‹ k —139.
56. FheqZgh\ < < ;mygh\ J : Dbg_lbdZ b dZlZeba l ‹ k —1423.
57. IZ\exobg X L b ^j >hde :G KKKJ l ‹ k —864.
58. IZ\exobg XL b ^j Ba\ :G KH :G KKKJ l ‹ k —20.
59. Bkmih\Z E: b ^j Dbg_lbdZ b dZlZeba l ‹ k —320.
60. Bkmih\Z E: b ^j LZf `_ l ‹ k —480.
61. Hkljhmrdh :: Rm[_jl W @ ijbde obfbb l ‹ k —1320.
62. Lj_lvydh\ X> L\_j^hnZagu_ j_Zdpbb F Obfby k
k
63. >_evfhg ; Dbg_lbdZ ]_l_jh]_gguo j_Zdpbc F Fbj 64. Ijh^Zg
? : G_hj]Zgbq_kdZy lhihobfby Fbgkd GZmdZ b
l_ogbdZ k
65. He_cgbdh\ G G b ^j G_hj]Zg fZl l ‹ k —486.
66. Bevbg : I Kfbjgh\ G G Bevbg : : GZmqgu_ hkgh\u
ijb]hlh\e_gby dZlZebaZlhjh\ Hfkd k 67. Bevbg : : Kfbjgh\ G G Bevbg : I Wg_j]hk[_j_]Zxsb_
l_ogheh]bb wdheh]bq_kdb [_ahiZkguo ijhba\h^kl\ B\Zgh
\h k 68. IZjn_gh\ < < GZabih\ J : G_hj]Zg fZl l ‹ k —106.
69. Bevbg : : Kfbjgh\ G G Bevbg : I L_jfh^bgZfbdZ
ih\_joghklguo y\e_gbc b Z^khj[pbb B\Zgh\h k —47.
70. IZl_gl JN ‹ 2005.
71. Bevbg : I Ijhdhnv_\ < X DZlZeba \ ijhfure_gghklb
‹ k —51.
72. Bevbg : I Rbjhdh\ X = <hijhku dbg_lbdb b dZlZebaZ
B\Zgh\h BOLB k —55.
73. Djm]ebpdbc G G Hkgh\u nbabdh-obfbq_kdhc f_oZgbdb
Db_\ <ukrZy rdheZ q k
74. Bevbg : I Ijhdhnv_\ < X Nbabdh-obfbq_kdZy f_oZgbdZ \
nhjfh\Zgbb dZlZebaZlhjh\ B\Zgh\h B=OLM k
75. :\l k\b^ KKKJ ‹ 93
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