РАСЧЕТ СТАНДАРТНЫХ ТЕПЛОЕМКОСТЕЙ

Ba\_klbyQ_ey[bgkdh]hgZmqgh]hp_gljZ\ui
NBABQ?KD:YOBFBYBL?OGHEH=BYG?HJ=:GBQ?KDBOF:L?JB:EH<
M>D
J:KQ?LKL:G>:JLGUOL?IEH?FDHKL?C
G?KL?OBHF?LJBQ?KDBOHDKB>H<Cr, Mo b W
:=Jy[mobg0:Kl_ggbdh\
e–mail: vic@fizchim.susu.ac.ru
X`gh±MjZevkdbc]hkm^Zjkl\_ggucmgb\_jkbl_l]Q_ey[bgkdJhkkby
KlZlvyihklmibeZfZjlZ]
F_lZeeuCr, MobWgZoh^ylrbjhdh_ijbf_g_gb_\l_ogbd_bf_lZeemj]bbHgby\eyxlky
\Z`gufb khklZ\eyxsbfb g_j`Z\_xsbo b ki_pbZevguo klZe_c Z lZd`_ bf_xl kZfhklhyl_evgh_ agZq_gb_ Jm^Zfb wlbo f_lZeeh\ y\eyxlky keh`gu_ hdkb^gu_ fbg_jZeu LZd m ojhfZ ²
wlhojhfblFeCr2O4, ojhfhribg_eeb^uMg, Fe)(Cr, Al, Fe)2O4mfheb[^_gZb\hevnjZfZ²gh\_eeblCaMoO4br__eblCaWO4Ijbihemq_gbbf_lZeeh\\dZq_kl\_ijhf_`mlhqguoijh^mdlh\\k_]^Zbf_xlkyhdkb^ujZaguokhklZ\h\L_jfh^bgZfbq_kdb_k\hckl\Zwlbof_lZeeh\bbo
kh_^bg_gbcg_bamq_gu^hklZlhqghih^jh[ghqlh[um^h\e_l\hjblvihlj_[ghklbijZdlbdbIhwlhfm hij_^_e_gb_ l_jfh^bgZfbq_kdbo k\hckl\ bo kh_^bg_gbc b \ qZklghklb hdkb^h\ iml_f
l_hj_lbq_kdh]hjZkq_lZij_^klZ\ey_lg_khfg_ggucbgl_j_k
<jZ[hlZo>@ij_^eh`_gZfZl_fZlbq_kdZyfh^_ev^eyhij_^_e_gbyklZg^Zjlguol_ieh_fdhkl_cg_kl_obhf_ljbq_kdbokh_^bg_gbcWlZfh^_evhkgh\ZgZgZgZ^_`ghijh\_j_gghcf_lh^bd_ jZkq_lZ bgl_]jZevghc \_ebqbgu h[uqgh wdki_jbf_glZevgh baf_j_gghc bkoh^y ba
^bnn_j_gpbZevguoagZq_gbcdhfihg_glh\kbkl_fu>@
Fh^_evhkgh\ZgZgZij_^klZ\e_gbbhlhfqlh^ey\k_oiZjZee_evghijhl_dZxsboijhp_kkh\ \klj_qgu_ ijhp_kku lZd`_ y\eyxlky iZjZee_evgufb kijZ\_^eb\Z Z^^blb\ghklv h[jZlguo\_ebqbgBgufbkeh\Zfbwlhebg_cgZydhf[bgZpbyh[jZlguo\_ebqbglh_klv]bi_j[hebq_kdZy\aZbfhk\yav
Ojhf fheb[^_g b \hevnjZf gZoh^ylky \ VIB ]jmii_ I_jbh^bq_kdhc kbkl_fu b y\eyxlky
ihegufbwe_dljhggufbZgZeh]Zfbd5s1Wlbf_lZeeu\klZg^Zjlguomkeh\byodjbklZeebamxlky \ HPD kljmdlmj_ lbiZ α–Fe bo gbarb_ hdkb^u MeO ² \ =PD kljmdlmj_ NaCl), Me2O3 —
\]_dkZ]hgZevghckljmdlmj_lbiZα–Al2O3ZMeO3²\fhghdebgghckljmdlmj_MoO3).
DZ`^hc ijhklhc djbklZeebq_kdhc kljmdlmj_ k\hckl\_ggZ bg^b\b^mZevgZy ]_hf_ljbq_kdZy
oZjZdl_jbklbdZ ² kljmdlmjgZy ihklhyggZy keh`guf h[jZah\Zgbyf ² ijhba\h^gZy dhf[bgZpby qZklguo dhgklZgl > @ < wlhf kemqZ_ ^ey i_j\hc h[eZklb l\_j^uo jZkl\hjh\ Me—O
h[h[s_ggZy kljmdlmjgZy ihklhyggZy y\eyykv dhf[bgZpb_c dhgklZgl ^ey kljmdlmj HPD b =PD
3 3
⋅ 2 = 0,91856 .
khklZ\ey_l k =
8
< wlhc h[eZklb l\_j^uo jZkl\hjh\ djbklZeehh[jZah\Zl_e_f y\ey_lky f_lZee ke_^h\Zl_evghmjZ\g_gb_^eyjZkq_lZl_ieh_fdhklbijbgbfZ_l\b^
[
=
−
&S 0H2 [ &S 0H & 0H + & 2 + N& 0H S
S S
(1)
Ihke_ih^klZgh\dbqbkeh\uoagZq_gbc\gZoh^bfmjZ\g_gby^eyl_ieh_fdhkl_chdkb^h\
\i_j\hch[eZklbl\_j^uojZkl\hjh\
JZkq_ll_ieh_fdhkl_cg_kl_obhf_ljbq_kdbohdkb^h\Cr, MobW
85
= − [ ,
&S &U2 [ (2)
= − [ ,
&S 0R2 [ (3)
= − [ .
&S :2 [ (4)
<h\lhjhch[eZklbl\_j^uojZkl\hjh\djbklZeehh[jZah\Zl_e_fy\ey_lkygZb[he__mklhcqb\uchdkb^MeO3<_ebqbgZihklhygghc N ^eyl\_j^uojZkl\hjh\\wlhch[eZklbkhklZ\ey_l
8
= 1,5396007 MjZ\g_gb_^eyl_ieh_fdhklb\wlhch[eZklbbf__l\b^
3 3
[ −
.
=
−
&S 0H2 [ &S 0H2 & 0H2 + & 2 + N & 0H2 S
S S
(5)
Ihke_ih^klZgh\dbqbkeh\uoagZq_gbc\ihemqbfmjZ\g_gby^eyjZkq_lZl_ieh_fdhkl_c
\h\lhjhch[eZklbl\_j^uojZkl\hjh\
= − [ ,
&S &U2 [ (6)
= − [ ,
&S 0R2 [ (7)
= − [ ,
KS :2 [ (8)
Kh\f_klgh_j_r_gb_mjZ\g_gbcbbbiha\hey_lhij_^_eblvkhklZ\u
hdkb^h\ khhl\_lkl\mxsbo ]jZgbpZf h[eZkl_c l\_j^uo jZkl\hjh\ Z mjZ\g_gby ²
b ² ² \_ebqbgu l_ieh_fdhkl_c wlbo hdkb^h\ Dhhj^bgZlu lhq_d jZ\gh\_kby x± khklZ\eyxlCr — 1,500; Mo — 1,226; W — 1,181.
J_amevlZlu jZkq_lh\ ijb\_^_gu \ lZ[e < \_jogbo kljhdZo ^Zgu wdki_jbf_glZevgh hij_^_e_ggu_ agZq_gby >²@ \ gb`gbo kljhdZo ² jZkkqblZggu_ l_hj_lbq_kdb GZ jbkmgd_ j_amevlZlujZkq_lh\ihmjZ\g_gbyfb^eykbkl_fuCr—Oij_^klZ\e_gu]jZnbq_kdb>ey
kbkl_fMo—ObW—Ohgbbf_xlZgZeh]bqguc\b^<lZ[e²ijb\_^_guj_amevlZlujZkq_lh\l_ieh_fdhklbhdkb^h\^eydhlhjuo\ebl_jZlmj_bf_xlkyk\_^_gbyhkljmdlmj_bebhl_jfbq_kdbodhgklZglZo
LZ[ebpZ
L_ieh_fdhklb hdkb^h\ & U 0 R b : >`fhev ÂD
Cr
Mo
Me
MeO
24,159 ±
± 0,126
39,984 ±
± 0,419
39,986
MeO1,5
51,273
59,453 ±
± 0,209
59,460
67,155
49,631
55,940 ±
± 0,419
55,944
49,022
55,308 ±
± 0,419
55,249
24,075 ±
± 0,209
39,823
W
MeO1,333
24,325 ±
± 0,209
47,832
40,303
47,247
MeO2
MeO2,5
MeO3
MeOx(1–2)
77,137
90,60 ±
± 0,42
90,604
60,271
64,096
75,027 ±
± 0,209
75,030
46,745
63,287
74,064 ±
± 0,126
74,063
45,730
:=Jy[mobg0:Kl_ggbdh\
86
LZ[ebpZ
L_ieh_fdhklb hdkb^h\ &U >`fhev ÂD
x
0,333
0,5
1,98
2,4
2,5
2,625
2,667
&S
27,831
30,120
66,809
74,910
77,137
80,114
81,116
LZ[ebpZ
L_ieh_fdhklb hdkb^h\ 0R >` fhev ÂD
x
0,333
2,75
2,765
2,8
2,875
2,889
&S
27,726
69,133
69,461
70,237
71,961
72,292
LZ[ebpZ
L_ieh_fdhklb hdkb^h\ : >`fhev ÂD
x
0,333
2,722
2,900
2,960
&S
28,025
67,658
71,624
73,068
&S
[
AZ\bkbfhklvklZg^ZjlghcD_e^`bh[jZlghc\_ebqbguklZg^Zjlghcfheyjghcl_ieh_fdhklb
hlkhklZ\Zhdkb^Zhlg_k_gghcdh^ghfmfhexojhfZ
AZdexq_gb_
FZl_fZlbq_kdZyfh^_evjZkq_lZl_ieh_fdhklbijh\_j_gZgZhdkb^ZoojhfZfheb[^_gZ
b\hevnjZfZGZ[ex^Z_lkyohjhr__kh]eZkb_wdki_jbf_glZevguobjZkq_lguo\_ebqbg
Ihemq_gumjZ\g_gby^eyjZkq_lZl_ieh_fdhkl_cg_kl_obhf_ljbq_kdbohdkb^h\\i_j\hc
b\lhjhch[eZklyol\_j^uojZkl\hjh\
Hij_^_e_gu khklZ\u hdkb^h\ khhl\_lkl\mxsbo ]jZgbpZf h[eZkl_c l\_j^uo jZkl\hjh\
gZ^bZ]jZff_ &S — xbgZc^_gubol_ieh_fdhklb
Bkihevah\Zgb_fh^_ebiha\hebehij_^kdZaZlvg_ba\_klgu_\_ebqbguklZg^Zjlguol_ieh_fdhkl_c\kbkl_fZoCr, Mo, W²dbkehjh^
JZkq_ll_ieh_fdhkl_cg_kl_obhf_ljbq_kdbohdkb^h\Cr, MobW
87
Kibkhdebl_jZlmju
1. Jy[mobg := Fh^_ev jZkq_lZ klZg^Zjlguo l_ieh_fdhkl_c &S g_kl_obhf_ljbq_kdbo kh_^bg_gbc Ba\Q_ey[bgkdh]hgZmqp_gljZ<uiK²
2. Jy[mobg := JZkq_l fheyjguo l_ieh_fdhkl_c &S g_kl_obhf_ljbq_kdbo [bgZjguo kh_^bg_gbc [_jlheeb^h\<_klgbdXMj=M<i_qZlb
3. Jy[mobg:=Kl_ggbdh\F:JZkq_lklZg^Zjlguol_ieh_fdhkl_cg_kl_obhf_ljbq_kdbohdkb^h\Ti, Zr
bHf // Ba\Q_ey[bgkdh]hgZmqp_gljZ<uiK²
4. Jy[mobg:=Kl_ggbdh\F:JZkq_lklZg^Zjlguol_ieh_fdhkl_cg_kl_obhf_ljbq_kdbohdkb^h\V, Nb
bTa // Ba\Q_ey[bgkdh]hgZmqp_gljZ<uiK²
5. L_jfh^bgZfbq_kdb_k\hckl\Zbg^b\b^mZevguo\_s_kl\Ih^j_^<I=emrdhFGZmdZL
dgk
6. L_jfh^bgZfbq_kdb_k\hckl\Zbg^b\b^mZevguo\_s_kl\Ih^j_^<I=emrdhFGZmdZL
dgk
7. L_jfbq_kdb_dhgklZglu\_s_kl\Ih^j_^<I=emrdhF:GKKKJ<BGBLB<uiVIq
369 k
8. L_jfbq_kdb_dhgklZglu\_s_kl\Ih^j_^<I=emrdhF:GKKKJ<BGBLB<uiVIIq
343 k