OpenBook
.pdfdhc J_Zdpby ijhl_dZxsZy k ih]ehs_gb_f l_iehlu Q < l _ k ih-
\ur_gb_f wglZevibb kbkl_fu ûH > gZau\Z_lky wg^hl_jfbq_kdhc.
Hkgh\guf aZdhghf l_jfhobfbb y\ey_lky aZdhg =_kkZ l_ieh \hc wnn_dl j_Zdpbb hij_^_ey_lky lhevdh gZqZevguf b dhg_qguf kh klhygb_f kbkl_fu b g_ aZ\bkbl hl imlb i_j_oh^Z kbkl_fu ba h^gh
]h khklhygby \ ^jm]h_.
Ke_^kl\b_ ba aZdhgZ =_kkZ klZg^Zjlguc l_ieh\hc wnn_dl j_ Zdpbb jZ\_g kmff_ klZg^Zjlguo l_iehl h[jZah\Zgby ijh^mdlh\ j_ Zdpbb aZ \uq_lhf kmffu klZg^Zjlguo l_iehl h[jZah\Zgby bkoh^ guo \_s_kl\ k mq_lhf kl_obhf_ljbq_kdbo dhwnnbpb_glh\
∆G0298 j-pbb ∑∆f G0298 ijh^ –∑∆f G0298 bko
Ijbf_j Ihevamykv ^Zggufb h klZg^Zjlguo wglZevibyo h[jZ ah\Zgby \_s_kl\ \ j_Zdpbb0J d + CO ] = 2MgO d + C ]jZnbl \uqbk eblv ∆Gh j_Zdpbb
J_r_gb_
Bkoh^y ba lZ[ebqguo ^Zgguo ih wglZevibyf h[jZah\Zgby&22 b 0J2 b mqblu\Zy qlh klZg^Zjlgu_ wglZevibb h[jZah\Zgby \_s_kl\ jZ\gu gmex gZoh^bf \_ebqbgm klZg^Zjlghc wglZevibb j_Zdpbb
∆ G0298 =2∆f G0298 (MgO) – ∆f G0298 (CO2) = = –601,8 .2 + 393,5 = – d>` fhev
Ijbf_j Bkoh^y ba l_iehlu h[jZah\Zgby ]Zahh[jZagh]h ^bhd kb^Z m]e_jh^Z&22) = – d>` fhev b l_jfhobfbq_kdh]h mjZ\g_ gby K ]jZnbl + 2N2O ] KH ] + 2N ] ; ∆G0298 = – d>` <uqbkeblv l_iehlm h[jZah\Zgby12O ] .
J_r_gb_
∆G0298 j-pbb ∆f G0298 (CO2) + 0) – (2∆f G0298 (N2O) + 0),
hldm^Z
2∆fG0298 (N2O) = ∆f G0298 (CO2) – ∆G0298 j-pbb
–393,5 – (– d>`
Ke_^h\Zl_evgh ∆f G0298 (N22 d>` fhev GZijZ\e_gb_ \ dhlhjhf kZfhijhba\hevgh ijhl_dZ_l obfbq_kdZy
j_Zdpby hij_^_ey_lky kh\f_klguf ^_ckl\b_f ^\mo nZdlhjh\ l_g ^_gpb_c d i_j_oh^m kbkl_fu \ khklhygb_ k gZbf_gvr_c \gmlj_gg_c wg_j]b_c \ kemqZ_ bah[Zjguo ijhp_kkh\ – k gZbf_gvr_c wglZevib_c
l_g^_gpb_c d ^hklb`_gbx gZb[he__ \_jhylgh]h khklhygby l _ khklhygby dhlhjh_ fh`_l [ulv j_Zebah\Zgh gZb[hevrbf qbkehf jZ\gh\_jhylguo kihkh[h\ fbdjhkhklhygbc
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F_jhc i_j\hc ba wlbo l_g^_gpbc ^ey bah[Zjguo ijhp_kkh\ kem `bl baf_g_gb_ wglZevibb \ obfbq_kdhc j_Zdpbb hljbpZl_evguc agZd ∆G mdZau\Z_l gZ mf_gvr_gb_ Z iheh`bl_evguc – gZ \hajZklZgb_ wg lZevibb kbkl_fu
F_jhc \_jhylghklb g_mihjy^hq_gghklb [_kihjy^dZ khklhygby kbkl_fu \ l_jfh^bgZfbd_ ijbgylh kqblZlv wgljhibx S – \_ebqbgm ijhihjpbhgZevgmx eh]Zjbnfm qbkeZ jZ\gh\_jhylguo fbdjhkhklhy gbc q_j_a dhlhju_ fh`_l [ulv j_Zebah\Zgh ^Zggh_ fZdjhkhklhygb_
S = k . ln W.
?^bgbpZ baf_j_gby wgljhibb – >` fhevÜK. Wgljhiby \hajZklZ_l ijb i_j_oh^_ \_s_kl\Z ba djbklZeebq_kdh]h
khklhygby \ `b^dh_ b ba `b^dh]h \ ]Zahh[jZagh_ ijb jZkl\hj_gbb djbklZeeh\ ijb jZkrbj_gbb ]Zah\ ijb obfbq_kdbo \aZbfh^_ckl\byo ijb\h^ysbo d m\_ebq_gbx qbkeZ qZklbp b ij_`^_ \k_]h qZklbp \ ]Z ahh[jZaghf khklhygbb GZijhlb\ \k_ ijhp_kku \ j_amevlZl_ dhlhjuo mihjy^hq_gghklv kbkl_fu \hajZklZ_l dhg^_gkZpby ihebf_jbaZpby k`Zlb_ mf_gvr_gb_ qbkeZ qZklbp khijh\h`^Zxlky mf_gvr_gb_f wgljhibb
Ijbf_j G_ ijhba\h^y \uqbke_gbc hij_^_eblv agZd baf_g_gby wgljhibb \ ke_^mxsbo j_Zdpbyo
NH4NO d = N2O ] G2H ] ; |
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G ] H ] G2H ] ; |
(2) |
G ] H ] G2H ` . |
(3) |
J_r_gb_
< j_Zdpbb fhev \_s_kl\Z \ djbklZeebq_kdhf khklhygbb h[ jZam_l fhev ]Zah\ ke_^h\Zl_evgh ûS1 > < j_Zdpbyo b
mf_gvrZ_lky dZd h[s__ qbkeh fhe_c lZd b qbkeh fhe_c ]Zahh[jZaguo \_s_kl\ lZd qlh ûS2 < b ûS3 < Ijb wlhf ûS3 bf__l [he__ hljbpZ l_evgh_ agZq_gb_ q_f ûS2 lZd dZd S(H2O ` ) < S(H2O ] ).
>ey wgljhibb kijZ\_^eb\h ml\_j`^_gb_ ZgZeh]bqgh_ jZkkfhl j_gghfm \ur_ ^ey ∆G: baf_g_gb_ wgljhibb kbkl_fu \ j_amevlZl_ obfbq_kdhc j_Zdpbb ∆6jZ\gh kmff_ wgljhibc ijh^mdlh\ j_Zdpbb aZ \uq_lhf kmffu wgljhibc bkoh^guo \_s_kl\ DZd b ijb \uqbke_gbb wglZevibb kmffbjh\Zgb_ ijhba\h^yl k mq_lhf kl_obhf_ljbq_kdbo dh wnnbpb_glh\
KlZg^ZjlgZy wgljhiby ijhkluo \_s_kl\ \ hlebqb_ hl wglZev- ibb h[jZah\Zgby ijhkluo \_s_kl\ g_ jZ\gZ gmex
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Nmgdpb_c khklhygby h^gh\j_f_ggh hljZ`Zxs_c \ebygb_ h[_bo mihfygmluo \ur_ l_g^_gpbc gZ gZijZ\e_gb_ ijhl_dZgby obfbq_kdbo ijhp_kkh\ kem`bl wg_j]by =b[[kZ (k\h[h^gZy wg_j]by k\yaZggZy k wglZevib_c b wgljhib_c khhlghr_gb_f
G = H – TS,
]^_ L – Z[khexlgZy l_fi_jZlmjZ
DZd \b^gh wg_j]by =b[[kZ bf__l lm `_ jZaf_jghklv qlh b wg lZeviby b ihwlhfm h[uqgh \ujZ`Z_lky \ >` beb d>`
>ey bah[Zjgh-bahl_jfbq_kdbo ijhp_kkh\ l _ ijhp_kkh\ ijhl_ dZxsbo ijb ihklhygguo l_fi_jZlmj_ b ^Z\e_gbb baf_g_gb_ wg_j]bb =b[[kZ jZ\gh
∆G =∆H – T∆S.
DZd b \ kemqZ_ ∆H b ∆S, baf_g_gb_ wg_j]bb =b[[kZ ∆G \ j_amev lZl_ obfbq_kdhc j_Zdpbb (wg_j]by =b[[kZ j_Zdpbb jZ\gh kmff_ wg_j]bc =b[[kZ h[jZah\Zgby ijh^mdlh\ j_Zdpbb aZ \uq_lhf kmffu wg_j]bc =b[[kZ h[jZah\Zgby bkoh^guo \_s_kl\ kmffbjh\Zgb_ ijhba \h^yl k mq_lhf qbkeZ fhe_c mqZkl\mxsbo \ j_Zdpbb \_s_kl\
Wg_j]bx =b[[kZ h[jZah\Zgby \_s_kl\Z hlghkyl d fhex wlh]h \_s_kl\Z b h[uqgh \ujZ`Zxl \ d>` fhev ijb wlhf ∆G0 h[jZah\Zgby gZb[he__ mklhcqb\hc fh^bnbdZpbb ijhklh]h \_s_kl\Z ijbgbfZxl jZ\ghc gmex.
Ijb ihklhygkl\_ l_fi_jZlmju b ^Z\e_gby obfbq_kdb_ j_Zdpbb fh- ]ml kZfhijhba\hevgh ijhl_dZlv lhevdh \ lZdhf gZijZ\e_gbb ijb dhlh- jhf wg_j]by =b[[kZ kbkl_fu mf_gvrZ_lky ∆G < 0) Wlh _klv mkeh\b_ ijbgpbibZevghc \hafh`ghklb hkms_kl\e_gby ^Zggh]h ijhp_kkZ
< ijb\_^_gghc lZ[ebp_ ihdZaZgZ \hafh`ghklv b mkeh\by ijhl_ dZgby j_Zdpbb ijb jZaebqguo khq_lZgbyo agZdh\ ∆G b ∆S.
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AgZd baf_g_gby nmgdpbb |
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IjbgpbibZevgZy \hafh`ghklv |
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b mkeh\by ijhl_dZgby j_Zdpbb |
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<hafh`gZ ijb ex[hc l_fi_jZlmj_ |
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IjbgpbibZevgh g_\hafh`gZ |
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<hafh`gZ ijb gbadbo l_fi_jZlmjZo |
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<hafh`gZ ijb \ukhdbo l_fi_jZlmjZo |
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Ijbf_j . Ihevamykv kijZ\hqgufb ^Zggufb mklZgh\blv \ha fh`gh eb ijb l_fi_jZlmjZo b D \hkklZgh\e_gb_ hdkb^Z lblZ gZ,9^h k\h[h^gh]h f_lZeeZ ih ko_f_
TiO d K ]jZnbl = Ti d KH ] ?
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AZ\bkbfhklvx ∆Gh b ∆Sh hl l_fi_jZlmju ij_g_[j_qv
J_r_gb_
AgZq_gby ûG 0h[j \ d>` fhev ijb D ^ey TiO2 (– b CH
(– Lh]^Z ^ey jZkkfZljb\Z_fhc j_Zdpbb ûG0298 = –137,1·2 – (–888,6) =
d>` Ihkdhevdm ûG 0298 !\hkklZgh\e_gb_ TiO2 ijb D g_ \hafh`gh
>ey jZkq_lZ ûG 02500 \hkihevam_fky mjZ\g_gb_f ûG = ûHo – TûSo.
Ijb wlhf \ khhl\_lkl\bb k mdZaZgb_f \ mkeh\bb aZ^Zqb bkihevam_f agZq_gby ûGh b ûSo ijb D >ey jZkq_lZ ûHo b ûSo j_Zdpbc g_h[oh
^bfh gZclb \ lZ[ebp_ agZq_gby ûG0h[j ^ey TiO2 (– b KH –110,5),
Z lZd`_ agZq_gby So ^ey TiO2 K Ti b KH
Lh]^Z ^ey jZkkfZljb\Z_fhc j_Zdpbb
ûHo = –110,5 · 2 – (– d>`
ûSo = 30,6 + 197,5 · 2 – 50,3 – 5,7 · 2 = – >` D L_i_jv gZoh^bf ûG 02500 j_Zdpbb \ujZ`Zy ûSo \ d>` D
ûG 02500 = ûG02500 – TûS 02500 = 722,9 – 2500 · 363,9/1000 = = 722,9 – 909,8 = – d>`
LZdbf h[jZahf ûG 02500 < lZd qlh \hkklZgh\e_gb_ TiO2 ]jZnb lhf ijb D \hafh`gh
<hijhku ^ey kZfhklhyl_evghc ih^]hlh\db
1.>Zcl_ hij_^_e_gb_ ihgylbyf kbkl_fZ nZaZ kj_^Z fZdjh- b fbdjhkhklhygb_.
2.DZdb_ kbkl_fu gZau\Zxlky ]hfh]_ggufb Z dZdb_ – ]_l_jh]_ggufb"
3.DZdb_ ^\Z nZdlhjZ hij_^_eyxl kZfhijhba\hevgh_ ijhl_dZgb_ ob fbq_kdbo j_Zdpbc \ ^Zgghf gZijZ\e_gbb"
4.GZah\bl_ hkgh\gu_ l_jfh^bgZfbq_kdb_ \_ebqbgu oZjZdl_jb amxsb_ khklhygb_ kbkl_fu Ihq_fm hgb ghkyl gZa\Zgb_ nmgdpbc khklhygby?
5.JZkkfhljbl_ kfuke ihgylbc \gmlj_ggyy wg_j]by kbkl_fu b wg lZeviby Ijb\_^bl_ ijbf_ju j_Zdpbc m dhlhjuo ∆Η > ∆U b
∆U > ∆Η.
6.DZdb_ nZdlhju hij_^_eyxl \_ebqbgm baf_g_gby wglZevibb j_Zd pbb"DZd aZ\bkbl wlZ \_ebqbgZ hl wg_j]bb Zdlb\Zpbb imlb b mkeh \by ijhl_dZgby ijhp_kkZ ijbkmlkl\by dZlZebaZlhjh\"
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7.Fh]ml eb [ulv wdahl_jfbqgufb ijhp_kku ^bkkhpbZpbb fhe_dme gZ Zlhfu bhgu wg^hl_jfbqgufb – ijhp_kku h[jZah\Zgby fhe_ dme ba Zlhfh\ jZ^bdZeh\ ba ^jm]bo fhe_dme"
8.H[tykgbl_ kfuke ihgylby wglZeviby h[jZah\Zgby \_s_kl\Z.
Knhjfmebjmcl_ mkeh\by klZg^ZjlbaZpbb wlhc oZjZdl_jbklbdb Q_f hlebqZxlky klZg^Zjlgu_ mkeh\by hl ghjfZevguo"
9.Knhjfmebjmcl_ aZdhg =_kkZ DZdZy k\yav f_`^m l_ieh\uf wnn_d lhf wglZevib_c j_Zdpbb b wglZevibyfb h[jZah\Zgby bkoh^guo \_s_kl\ b ijh^mdlh\ j_Zdpbb"
10.Q_f h[tykgy_lky kZfhijhba\hevgh_ ijhl_dZgb_ g_dhlhjuo j_Zd pbc k ih]ehs_gb_f l_ieZ ∆Η>0)?
11.>Zcl_ h[tykg_gb_ ihgylby wgljhiby.
12.G_ ijh\h^y jZkq_lZ hij_^_ebl_ agZd baf_g_gby wgljhibb \ oh^_ ke_^mxsbo ijhp_kkh\
Z+2 ] + O ] = 2H2O ] ;
[+2S ] + 3O ] = 2 H2O ` + 2 SO ] ; \ MgO d + CO ] = MgCO d ;
] e_^ → \h^Z → iZj
^) CH3COOH (j-j) = CH3COOØ ++.
13.>Zcl_ hij_^_e_gb_ ihgylby wg_j]by =b[[kZ.
14.DZdh\h khhlghr_gb_ f_`^m \_ebqbghc baf_g_gby wg_j]bb =b[[kZ b \_ebqbgZfb baf_g_gby wglZevibb b wgljhibb kbkl_fu"
15.Ihq_fm ∆G fh`_l jZkkfZljb\Zlvky dZd djbl_jbc kZfhijhba\hev
ghklb ijhl_dZgby obfbq_kdhc j_Zdpbb"<hafh`gu eb kemqZb dh ]^Z j_Zdpbb k ∆G < ijZdlbq_kdb g_ b^ml">Zcl_ h[tykg_gb_
16.Mqblu\Zy jhev wglZevibcgh]h b wgljhibcgh]h nZdlhjh\ b l_fi_ jZlmju \ hij_^_e_gbb \_ebqbgu ∆G \u^_ebl_ q_luj_ h[sbo lbiZ j_Zdpbc jZaebqZxsboky \hafh`ghklvx b l_fi_jZlmjgufb mkeh \byfb ijhl_dZgby
AZ^Zqb ^ey j_r_gby
106.Qlh gZau\Zxl l_ieh\ufb wnn_dlZfb j_Zdpbc" < dZdbo kemqZyo mjZ\g_gby obfbq_kdbo j_Zdpbc gZau\Zxl l_jfhobfbq_kdbfb"
107.DZdb_ mkeh\by khklhygby kbkl_fu ijbgbfZxl \ l_jfh^bgZfbd_ \ dZq_kl\_ klZg^Zjlguo"DZdbfb kbf\heZfb bo h[hagZqZxl"
108.Qlh gZau\Zxl \gmlj_gg_c wg_j]b_c kbkl_fu"Ihq_fm \ l_jfh^b
gZfbq_kdbo jZkq_lZo bkihevamxl g_ Z[khexlgu_ agZq_gby \gml j_gg_c wg_j]bb U Z __ baf_g_gb_ ∆U ijb i_j_oh^_ kbkl_fu ba h^gh]h khklhygby \ ^jm]h_"
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109.DZdbf mjZ\g_gb_f hij_^_ey_lky wglZeviby b __ baf_g_gb_" DZ dhc aZdhg y\ey_lky hkgh\guf aZdhghf l_jfhobfbb" >Zcl_ _]h nhjfmebjh\dm
110.DZdhc nmgdpb_c khklhygby oZjZdl_jbam_lky l_g^_gpby kbkl_fu d ^hklb`_gbx lZd gZau\Z_fh]h gZb[he__ \_jhylgh]h khklhygby dh lhjhfm khhl\_lkl\m_l fZdkbfZevgZy [_kihjy^hqghklv jZkij_^_ e_gby qZklbp"
111.DZd baf_gy_lky wgljhiby kbkl_fu k ih\ur_gb_f l_fi_jZlmju \ j_Zdpbyo kbgl_aZ b jZaeh`_gby \_s_kl\"
112.DZd baf_gy_lky wgljhiby kbkl_fu ijb bkiZj_gbb dhg^_gkZpbb m\_ebq_gbb ^Z\e_gby nZah\uo i_j_oh^Zo"
113.DZdbfb h^gh\j_f_ggh ^_ckl\mxsbfb nZdlhjZfb hij_^_ey_lky gZijZ\e_gghklv obfbq_kdh]h ijhp_kkZ"
114.Ijb kh_^bg_gbb ] `_e_aZ k k_jhc \u^_ebehkv d>` JZk kqblZlv l_iehlm h[jZah\Zgby kmevnb^Z `_e_aZ
115.Hij_^_eblv klZg^Zjlgmx wglZevibx ∆G0298 h[jZah\Zgby JG3, bkoh^y ba mjZ\g_gby
2PH ] H ] J2H d G2H ` ; ∆Gh = – d>`
116. Bkoh^y ba l_ieh\h]h wnn_dlZ j_Zdpbb
KZH d J2H d KZ3 JH4) d ; ∆Gh = – d>` hij_^_eblv ∆G0298 h[jZah\Zgby hjlhnhknZlZ dZevpby
117.KjZ\gblv ∆G0298 j_Zdpbb \hkklZgh\e_gby hdkb^Z `_e_aZ III jZa ebqgufb \hkklZgh\bl_eyfb ijb D
Z)H2O d + 3H2 = 2 Fe d + 3H2O ] ;
[)H2O d K ]jZnbl = 2 Fe d KH ] ; \)H2O d KH ] = 2 Fe d KH ] .
118.<uqbkeblv agZq_gb_ ∆Gh ^ey ijhl_dZxsbo \ hj]Zgbaf_ j_Zdpbc ij_\jZs_gby ]exdhau
Z K6G12H d K2G5HG ` KH ] ;
[ K6G12H d H ] KH ] G2H ` .
DZdZy ba wlbo j_Zdpbc ihklZ\ey_l hj]Zgbafm [hevr_ wg_j]bb"
119.G_ ijhba\h^y \uqbke_gbc mklZgh\blv agZd ∆Sh ke_^mxsbo ijhp_kkh\
Z1+ ] = N ] + 3H ] ; [ KH d KH ] ; \12 ] + O ] = 2NO ] ;
]+2S ] + 3O ] = 2H2O ` + 2SO ] ; ^ K+3OH ] + 3O ] = 4H2O ] KH ] .
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120.G_ ijhba\h^y \uqbke_gbc mdZaZlv ^ey dZdbo ba i_j_qbke_gguo ijhp_kkh\ baf_g_gb_ wgljhibb iheh`bl_evgh
Z0J2 d + H ] = Mg d + H2O ` ;
[ K ]jZnbl KH ] KH ] ;
\ KG3KHHG \h^g KG3KHH- \h^g G+ \h^g ;
] G&O ] H ] = 2Cl ] G2H ] ; ^1+4NO d = N2O ]) G2H ] .
121.MklZgh\blv ijhl_dZgb_ dZdbo ba gb`_ke_^mxsbo j_Zdpbc \ha fh`gh \ klZg^Zjlguo mkeh\byo
Z1 ] + ½ H ] = N2O ] ;
[+&O ] H ] = 2Cl ] G2H ` ; \)H2O d KH ] = 2Fe d KH ] .
122.MdZaZlv dZdb_ ba j_Zdpbc h[jZah\Zgby hdkb^h\ ZahlZ b ijb dZdbo l_fi_jZlmjZo \ukhdbo beb gbadbo fh]ml ijhl_dZlv kZfhijhba \hevgh
Z1 ] H ] = 2N2O ] ; ∆Gh298 |
> 0 |
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[1 ] H ] = 2NO ] ; ∆Gh298 |
> 0 |
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\12 ] + O ] = 2NO d ; |
∆Gh298 < 0 |
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]12 ] + NO ] = N2O d ;∆Gh298 |
< 0 |
123. |
Hij_^_ebl_ agZq_gby ∆Gh298, ∆Ηh298 b ∆Sh298 ^ey gb`_ijb\_^_gguo |
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j_Zdpbc b mklZgh\bl_ l_fi_jZlmjgu_ mkeh\by bo hkms_kl\e_gby |
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\ ijyfhf gZijZ\e_gbb |
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Z1L2 d +Pb d =Ni d + PbO d ; |
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[1+ ] = 3H ] + N ] ; |
124. |
\&D&2 d = CaO d KH ] . |
Ih baf_g_gbx klZg^Zjlghc wglZevibb b wgljZibb j_Zdpbb \u |
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qbkeblv baf_g_gb_ wg_j]bb =b[[kZ |
125. |
H ] + F ] = 2HF ] |
Hp_gblv l_jfh^bgZfbq_kdmx \hafh`ghklv ijhl_dZgby \ klZg |
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^Zjlguo mkeh\byo j_Zdpbb N ] + 2H2O ` = NH4NO l . |
126.Bkihevamy kijZ\hqgu_ ^Zggu_ hij_^_eblv dZdZy ba j_Zdpbc l_jfh^bgZfbq_kdb \hafh`gZ \ klZg^Zjlguo mkeh\byo
a) CaCO3(l) = CaO(l) + CO2(]); [) CO2(]) + CaO(l) = CaCO3(l);
\) Ca(OH)2(l) + CO2(]) = CaCO3(l) + H2O(`).
127.Hp_gblv ijbgpbibZevgmx \hafh`ghklv hkms_kl\e_gby j_Zdpbb f_`^m dhfihg_glZfb Zlfhkn_ju Z ijb klZg^Zjlguo mkeh\byo [ ijb ih\ur_gghc l_fi_jZlmj_
1)N ] + O ] : NO ] ; NO ] ;
2)N2(]) +H2O(`) :1+4NO2(l);
3)N2(]) + H2O(`) + O2(]) :1+4NO3(l);
4)N2(]) + H2O(`) + O2(]) :+123(`).
47
= E : < : I V
HKGH<U OBFBQ?KDHC DBG?LBDB
OBFBQ?KDH? J:<GH<?KB?
NZdlhju \ebyxsb_ gZ kdhjhklv obfbq_kdhc j_Zdpbb
Kdhjhklv ]hfh]_gghc j_Zdpbb – wlh \_ebqbgZ qbke_ggh jZ\gZy baf_g_gbx dhgp_gljZpbb h[uqgh fheyjghc ex[h]h mqZklgbdZ j_Zd pbb \ _^bgbpm \j_f_gb
Kj_^gyy kdhjhklv j_Zdpbb vkj \ bgl_j\Ze_ \j_f_gb hl t1 ^h t2 hi
j_^_ey_lky khhlghr_gb_f v |
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Hkgh\gu_ nZdlhju \ebyxsb_ gZ kdhjhklv ]hfh]_gghc obfbq_ kdhc j_Zdpbb
– ijbjh^Z j_Z]bjmxsbo \_s_kl\
– dhgp_gljZpby ^Z\e_gb_ _keb \ j_Zdpbb mqZkl\mxl ]Zau
– l_fi_jZlmjZ
– dZlZebaZlhj
<k_ obfbq_kdb_ j_Zdpbb ih klZ^bcghklb ih^jZa^_eyxlky gZ we_ f_glZjgu_ b keh`gu_ ;hevrbgkl\h obfbq_kdbo j_Zdpbc ij_^klZ\ eyxl kh[hc keh`gu_ ijhp_kku ijhl_dZxsb_ \ g_kdhevdh klZ^bc l _ khklhysb_ ba g_kdhevdbo we_f_glZjguo ijhp_kkh\
>ey we_f_glZjguo j_Zdpbc kijZ\_^eb\ aZdhg ^_ckl\mxsbo fZkk kdhjhklv we_f_glZjghc obfbq_kdhc j_Zdpbb ijb ^Zgghc l_f i_jZlmj_ ijyfh ijhihjpbhgZevgZ ijhba\_^_gbx dhgp_gljZpbc j_Z]b jmxsbo \_s_kl\ \ kl_i_gyo jZ\guo kl_obhf_ljbq_kdbf dhwnnbpb _glZf
>ey j_Zdpbb \ h[s_f \b^_ Z: bB : __ kdhjhklv kh]eZkgh aZ dhgm ^_ckl\mxsbo fZkk \ujZ`Z_lky khhlghr_gb_f
v = kca (A)cb (B) ,
]^_ k : b k < – fheyjgu_ dhgp_gljZpbb j_Z]bjmxsbo \_s_kl\ : b < k – dhgklZglZ kdhjhklb ^Zgghc j_Zdpbb Nbabq_kdbc kfuke dhg klZglu kdhjhklb – hgZ qbke_ggh jZ\gZ kdhjhklb obfbq_kdhc j_Zd pbb ijb dhgp_gljZpbyo j_Z]bjmxsbo \_s_kl\ F: b F< fhev e DhgklZglZ kdhjhklb ]hfh]_gghc j_Zdpbb aZ\bkbl hl ijbjh^u j_Z]b jmxsbo \_s_kl\ l_fi_jZlmju b dZlZebaZlhjZ
;hevrbgkl\h obfbq_kdbo j_Zdpbc y\eyxlky keh`gufb ijhl_ dZxsbfb q_j_a fgh`_kl\h ijhf_`mlhqguo klZ^bc < lZdhf kemqZ_ aZ dhg ^_ckl\mxsbo fZkk ijbf_gbf lhevdh d dZ`^hc hl^_evghc klZ^bb
48
>ey ]_l_jh]_gguo j_Zdpbc \ mjZ\g_gb_ aZdhgZ ^_ckl\mxsbo fZkk \oh^yl dhgp_gljZpbb g_ \k_o j_Z]_glh\ Z lhevdh ]Zahh[jZaguo beb jZkl\hj_gguo LZd ^ey j_Zdpbb ]hj_gby m]ey K d H ] : KH ]
mjZ\g_gb_ kdhjhklb bf__l \b^ v = k c(O2 ) .
Ijbf_j >ey j_Zdpbb 12 ] + O ] <12 ] ijhl_dZxs_c \ ]Zah\hc nZa_ dhgklZglZ kdhjhklb jZ\gZ JZkkqblZcl_ Z gZqZev gmx kdhjhklv j_Zdpbb _keb bkoh^gu_ dhgp_gljZpbb \_s_kl\ jZ\gu c12 fhev e c(O2 fhev e [ kdhjhklv wlhc j_Zdpbb \ fh f_gl dh]^Z ijhj_Z]bjm_l12
J_r_gb_
Z < khhl\_lkl\bb k aZdhghf ^_ckl\mxsbo fZkk kdhjhklv ^Zgghc j_Zdpbb hibku\Z_lky mjZ\g_gb_f v = k c 2 (NO) c(O2 ). Ke_^h\Zl_ev- gh kdhjhklv j_Zdpbb \ gZqZevguc fhf_gl \j_f_gb [m^_l jZ\gZ
vo = 0,8 0,42 0,3 = 0,0384 fhev e k
[ Kdhjhklv wlhc j_Zdpbb \ fhf_gl dh]^Z ijhj_Z]bjm_l12
hibku\Z_lky mjZ\g_gb_f v1 = k c12 (NO) c1(O2 ), ]^_ c112 b c1(O2) – gh\u_ dhgp_gljZpbb12b22 ihke_ lh]h dZd ijhj_Z]bjh\Zeh12
Bkoh^y ba mjZ\g_gby j_Zdpbb jZkkqblZ_f \_ebqbgu c112b c1(O2).
12 khklZ\ey_l ∆c(NO Â fhev e lh]^Z c1(NO) = c0(NO) – ∆c(NO) = 0,4 – fhev e < khhl\_lkl\bb kh kl_obhf_ljbq_kdbfb dhwnnbpb_glZfb mjZ\g_gby j_Zdpbb mf_gvr_ gb_ dhgp_gljZpbb H2 jZ\gh ∆c(O2) = ∆c(NO fhev e
LZdbf h[jZahf c1 H2) = c0(O2) – ∆c(O2) =0,3 – fhev e Ke_ ^h\Zl_evgh v1 = 0,8 · 0,32 · fhev e k
Ijbf_j DZd baf_gblky kdhjhklv j_Zdpbb 12 ] + Cl ] < <12&O ] _keb Z m\_ebqblv ^Z\e_gb_ \ j_Zdpbhgghf khkm^_ \ ^\Z jZaZ [ mf_gvrblv h[t_f khkm^Z \ jZaZ"
J_r_gb_
Z < khhl\_lkl\bb k aZdhghf ^_ckl\mxsbo fZkk kdhjhklv ^Zgghc j_Zdpbb hibku\Z_lky mjZ\g_gb_f v = k c 2 (NO) c(Cl2 ). Ihkdhevdm m\_ebq_gb_ ^Z\e_gby ijb\h^bl d ijhihjpbhgZevghfm m\_ebq_gbx dhgp_gljZpbc ]Zahh[jZaguo \_s_kl\ dhgp_gljZpbb j_Z]_glh\ \ gh \uo mkeh\byo [m^ml jZ\gu c1(NO) = 2c0(NO), c1(Cl2) = 2c0(Cl2 Dhg klZglZ kdhjhklb j_Zdpbb ijb m\_ebq_gbb ^Z\e_gby g_ baf_gy_lky b kdhjhklv j_Zdpbb \ gh\uo mkeh\byo [m^_l jZ\gZ
v1 = k c12 (NO) c1(Cl2 ) = k (2c0 (NO))2 (2c0 (Cl2 ))= = 8 · k · c 02 (NO) · c0(Cl2).
49
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Hlkx^Z ke_^m_l qlh |
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k c0 |
2 (NO)c0 (Cl2 ) |
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Kdhjhklv j_Zdpbb m\_ebqblky \ jZa
[ Mf_gvr_gb_ h[t_fZ khkm^Z \ jZaZ ijb\h^bl d khhl\_lkl \mxs_fm m\_ebq_gbx dhgp_gljZpbc j_Z]_glh\ LZdbf h[jZahf c2(NO) = 4 · c0(NO), a c2(Cl2) = 4 · c0(Cl2 J_rZy aZ^Zqm ih ZgZeh]bb k
ij_^u^msbf imgdlhf ihemqbf v2 = 64 l _ mf_gvr_gb_ h[t_fZ kh v
km^Z \ jZaZ ijb\_^_l d m\_ebq_gbx kdhjhklb \ jZaZ
<ebygb_ l_fi_jZlmju gZ kdhjhklv obfbq_kdhc j_Zdpbb
AZ\bkbfhklv kdhjhklb j_Zdpbb hl l_fi_jZlmju ijb[eb`_ggh hi j_^_ey_lky wfibjbq_kdbf ijZ\behf <Zgl-=hnnZ ijb ih\ur_gbb l_fi_jZlmju gZ dZ`^u_ ]jZ^mkh\ kdhjhklv obfbq_kdhc j_Zdpbb m\_ebqb\Z_lky \ - jZaZ \ jZa
v T2 −T1
T2 = γ 10 , vT1
]^_ vT2 b vT1 – kdhjhklb j_Zdpbb khhl\_lkl\_ggh ijb l_fi_jZlmjZo L2 b
L1; – l_fi_jZlmjguc dhwnnbpb_gl kdhjhklb j_Zdpbb dhlhjuc \u qbkey_lky gZ hkgh\_ wdki_jbf_glZevguo ^Zgguo b ijbgbfZ_l agZq_ gby ^ey [hevrbgkl\Z j_Zdpbc hl ^h >ey ^Zgghc j_Zdpbb – \_eb qbgZ ijZdlbq_kdb ihklhyggZy ijb¨L ” § 100h.
K ihfhsvx ijZ\beZ <Zgl-=hnnZ \hafh`gh ebrv ijbf_jgh hp_ gblv \ebygb_ l_fi_jZlmju gZ kdhjhklv j_Zdpbb ;he__ lhqgh_ hibkZ gb_ aZ\bkbfhklb kdhjhklb j_Zdpbb hl l_fi_jZlmju hkms_kl\bfh \ jZfdZo l_hjbb Zdlb\guo klhedgh\_gbc :jj_gbmkZ
< l_hjbb Zdlb\Zpbb \ebygb_ l_fi_jZlmju b dZlZebaZlhjZ gZ kdhjhklv obfbq_kdhc j_Zdpbb hibku\Z_lky ke_^mxsbf mjZ\g_gb_f ^ey dhgklZglu kdhjhklb obfbq_kdhc j_Zdpbb
− Ea
k = Ae RT ,
]^_ : – ihklhygguc fgh`bl_ev g_ aZ\bkysbc hl l_fi_jZlmju hij_ ^_eyxsbcky ijbjh^hc j_Z]bjmxsbo \_s_kl\ R – mgb\_jkZevgZy ]Z ah\Zy ihklhyggZy ?Z – wg_j]by Zdlb\Zpbb _ – hkgh\Zgb_ gZlmjZevgh]h eh]ZjbnfZ DZd ke_^m_l ba mjZ\g_gby :jj_gbmkZ dhgklZglZ kdhjhklb j_Zdpbb l_f [hevr_ q_f f_gvr_ wg_j]by Zdlb\Zpbb
50