ЗАДАЧНИК ДЛЯ ЗАОЧНИКОВ
.pdfgZc^_ggu_ qbkeZ Zlhfh\ ZahlZ b dbkehjh^Z mfgh`bf gZ IhemqZ_l ky qlh kl_i_gv hdbke_gby baf_gbeZkv m Zlhfh\ dbkehjh^Z b m
Zlhfh\ ZahlZ
5. JZkklZgh\dm dhwnnbpb_glh\ ijh\h^bf \ ke_^mxs_c ihke_^h\Z l_evghklb
Z mjZ\gb\Z_f qbkeZ Zlhfh\ ZahlZ ihklZ\b\ i_j_^ nhjfmehc Fe(NO3)3 dhwnnbpb_gl© ªZ i_j_^ nhjfmehc NO2 – dhwnnb pb_gl© ª
[ mjZ\gb\Z_f qbkeZ Zlhfh\ `_e_aZ ihklZ\b\ i_j_^ nhjfmehc Fe2O3 dhwnnbpb_gl© ª
\ mjZ\gb\Z_f qbkeh Zlhfh\ dbkehjh^Z ihklZ\b\ i_j_^ nhjfm ehc O2 dhwnnbpb_gl© ª
6. Ijh\_jy_f h^bgZdh\h eb h[s__ qbkeh Zlhfh\ dbkehjh^Z \ e_\hc b ijZ\hc qZklyo mjZ\g_gby
4Fe+3(N+5O3−2 )3 :)H +23 O3 + 12N+4O2 + 3O 02 .
We_dljh^gu_ b hdbkebl_evgh-\hkklZgh\bl_evgu_
ihl_gpbZeu b bo bkihevah\Zgb_
Dhebq_kl\_gghc oZjZdl_jbklbdhc hdbkebl_evgh-\hkklZgh\b- l_evguo k\hckl\ \_s_kl\ \ \h^guo jZkl\hjZo y\eyxlky agZq_gby we_d ljh^guo beb hdbkebl_evgh-\hkklZgh\bl_evguo ihl_gpbZeh\ khhl\_l kl\mxsbo ihemj_Zdpbc We_dljh^guc ihl_gpbZe ij_^klZ\ey_l kh [hc jZaghklv ihl_gpbZeh\ \hagbdZxsmx gZ ]jZgbp_ jZa^_eZ we_d ljh^ – jZkl\hj we_dljheblZ :[khexlgu_ agZq_gby ihl_gpbZeh\ wdki_jbf_glZevgh hij_^_eblv g_\hafh`gh ihwlhfm gZ ijZdlbd_ bk ihevamxlky bo hlghkbl_evgu_ agZq_gby baf_j_ggu_ ih hlghr_gbx d klZg^Zjlghfm \h^hjh^ghfm we_dljh^m ihl_gpbZe dhlhjh]h mkeh\gh ijbjZ\gb\Z_lky d Ihl_gpbZeu baf_j_ggu_ \ klZg^Zjlguo mkeh\b yo dhgp_gljZpbb bhgh\ jZ\gu fhev e ^Z\e_gb_ \h^hjh^Z jZ\gh
dIZ l_fi_jZlmjZ – 25 hK gZau\Zxlky klZg^Zjlgufb we_d- ljh^gufb beb klZg^Zjlgufb hdbkebl_evgh-\hkklZgh\bl_evgufb ihl_gpbZeZfb b h[hagZqZxlky kbf\hehf ?h Bo agZq_gby bkihevam xlky ^ey oZjZdl_jbklbdb j_Zdpbc ijhl_dZxsbo \ klZg^Zjlguo mkeh \byo ?keb `_ j_Zdpby ijhl_dZ_l \ ^jm]bo mkeh\byo lh ^ey __ hibkZ gby bkihevamxlky jZ\gh\_kgu_ ihl_gpbZeu ? dhlhju_ jZkkqblu\Z xlky ih mjZ\g_gbx G_jgklZ
E = E0 − 2,303 R T lg c(\hkkl) . |
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n F |
k(hdbke) |
91
< wlhf mjZ\g_gbb
2,303 – dhwnnbpb_gl i_j_oh^Z hl gZlmjZevguo eh]Zjbnfh\ d ^_ kylbqguf
R – mgb\_jkZevgZy ]Zah\Zy ihklhyggZy T – Z[khexlgZy l_fi_jZlmjZ
n – qbkeh we_dljhgh\ ijbgbfZxsbo mqZklb_ \ ihemj_Zdpbb F – ihklhyggZy NZjZ^_y jZ\gZy ijbf_jgh De fhev
k \hkkl – dhgp_gljZpby \hkklZgh\e_gghc nhjfu we_f_glZ \ dh lhjhc hg gZoh^blky \ [he__ gbadhc kl_i_gb hdbke_gby
k hdbke – dhgp_gljZpby hdbke_gghc nhjfu we_f_glZ \ dhlhjhc hg gZoh^blky \ [he__ \ukhdhc kl_i_gb hdbke_gby
?keb \ mjZ\g_gb_ G_jgklZ ih^klZ\blv qbkeh\u_ agZq_gby R (8,314), F b ijbgylv l_fi_jZlmjm jZ\ghc D lh hgh ijb gbfZ_l \b^
E = E0 − 0,059 lg c(\hkkl) . n k(hdbke)
Ba mjZ\g_gby G_jgklZ ke_^m_l qlh \_ebqbgZ ihl_gpbZeZ aZ\bkbl hl dhgp_gljZpbc \hkklZgh\e_gghc b hdbke_gghc nhjf we_f_glZ ?keb \ j_ Zdpbb ijbgbfZ_l mqZklb_ f_lZee lh \_ebqbgZ _]h we_dljh^gh]h ihl_g pbZeZ aZ\bkbl ebrv hl dhgp_gljZpbb bhgh\ wlh]h f_lZeeZ _]h hdbke_g ghc nhjfu \ jZkl\hj_ Dhgp_gljZpby kZfh]h f_lZeeZ \hkklZgh\e_gghc nhjfu dZd \_ebqbgZ ihklhyggZy \ mjZ\g_gb_ G_jgklZ g_ ih^klZ\ey_lky Djhf_ lh]h _keb \ ihemj_Zdpbb ijbgbfZxl mqZklb_ bhgu H+ beb HG– bo dhgp_gljZpbb lZd`_ \ebyxl gZ \_ebqbgm ihl_gpbZeZ
Bkihevamy agZq_gby we_dljh^guo beb hdbkebl_evgh- \hkklZgh\bl_evguo ihl_gpbZeh\ ihemj_Zdpbc fh`gh \uihegblv ke_ ^mxsb_ hi_jZpbb
1.Hp_gblv hdbkebl_evgh-\hkklZgh\bl_evgu_ k\hckl\Z khhl\_lkl \mxsbo \_s_kl\
2.Ij_^kdZaZlv ijbgpbibZevgmx \hafh`ghklv hkms_kl\e_gby j_ Zdpbb \ mdZaZgghf gZijZ\e_gbb
3.Hij_^_eblv gZijZ\e_gb_ ijhl_dZgby j_Zdpbb
4.<u[jZlv gZb[he__ \_jhylgmx j_Zdpbx ba g_kdhevdbo \hafh`
guo
5.JZkkqblZlv agZq_gb_ dhgklZglu obfbq_kdh]h jZ\gh\_kby ^Zgghc j_Zdpbb
Knhjfmebjm_f khhl\_lkl\mxsb_ ijZ\beZ b jZkkfhljbf bo ijb f_g_gb_ gZ dhgdj_lguo ijbf_jZo
92
;he__ kbevgufb \hkklZgh\bl_evgufb k\hckl\Zfb h[eZ^Z_l \_s_kl\h dhlhjhfm khhl\_lkl\m_l ihemj_Zdpby k [he__ gbadbf agZq_gb_f ihl_gpbZeZ ;he__ kbevgufb hdbkebl_evgufb k\hckl \Zfb h[eZ^Z_l \_s_kl\h dhlhjhfm khhl\_lkl\m_l ihemj_Zdpby k [he__ \ukhdbf agZq_gb_f ihl_gpbZeZ
Ijbf_j Hij_^_ebl_ dZdhc ba \hkklZgh\bl_e_c ijhy\ey_l gZb [he__ kbevgu_ \hkklZgh\bl_evgu_ k\hckl\Z ijb klZg^Zjlguo mkeh\b yo \ j_Zdpbyo
Z) FeSO4 + O2 + H2SO4 :)H2(SO4)3 + H2O; [) HI + O2 :,2 + H2O;
\) H2SO3 + O2 :+2SO4.
J_r_gb_
Hij_^_ey_f dZdb_ \_s_kl\Z \ ^Zgguo j_Zdpbyo y\eyxlky \hk klZgh\bl_eyfb < j_Zdpbb ©Zª \hkklZgh\bl_e_f y\ey_lky FeSO4 ih kdhevdm m `_e_aZ kl_i_gv hdbke_gby ih\urZ_lky hl ^h \ khhl \_lkl\bb k mjZ\g_gb_f ihemj_Zdpbb
Fe+2 – • :)H+3
< j_Zdpbb ©[ª \hkklZgh\bl_e_f y\ey_lky HI ihkdhevdm m bh^Z kl_i_gv hdbke_gby ih\urZ_lky \ khhl\_lkl\bb k mjZ\g_gb_f ihemj_ Zdpbb:
I– – • : I0
< j_Zdpbb©\ª\hkklZgh\bl_e_f y\ey_lky H2SO3 ihkdhevdm m k_ ju kl_i_gv hdbke_gby m\_ebqb\Z_lky \ khhl\_lkl\bb k mjZ\g_gb_f ih emj_Zdpbb
H2SO3 + H2O – • :+2SO4 + 4H+
GZoh^bf agZq_gby klZg^Zjlguo ihl_gpbZeh\Fhhl\_lkl\mxsbo ihemj_Zdpbc
Z E0 |
3+ |
Fe |
2+ |
= 0,77B [ E00 |
2I |
− |
= 0,54< \ E0 2− |
= 0,17<. |
Fe |
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I2 |
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SO4 |
H2SO3 |
GZoh^bf gZb[he__ kbevguc \hkklZgh\bl_ev Ihkdhevdm kZfh_ gbadh_ agZq_gb_ ihl_gpbZeZ m ihemj_Zdpbb hdbke_gby k_jgbklhc db kehlu lh wlh \_s_kl\h b [m^_l y\eylvky gZb[he__ kbevguf \hkklZgh \bl_e_f
Ijhl_dZgb_ hdbkebl_evgh-\hkklZgh\bl_evghc j_Zdpbb \ ^Zg- ghf gZijZ\e_gbb \hafh`gh ebrv lh]^Z dh]^Z ihl_gpbZe \hkklZ- gh\e_gby bkihevam_fh]h hdbkebl_ey [hevr_ ihl_gpbZeZ hdbke_gby bkihevam_fh]h \hkklZgh\bl_ey
93
Ijbf_j Hij_^_eblv fh`gh eb bkihevah\Zlv \ klZg^Zjlguo mkeh\byo kheb `_e_aZ III ^ey hdbke_gby bhgh\)–, Br– b I– ^h ijhkluo \_s_kl\"Hl\_l ih^l\_j^blv jZkq_lZfb
J_r_gb_
GZoh^bf agZq_gby ?h ihemj_Zdpbc
E00 |
2I |
− = 0,53 <; |
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E0 0 |
2Br |
− = 1,08 <; |
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I2 |
− = 2,85 <; |
Br2 |
2+ = 0,77 <. |
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E00 |
2F |
E0 3+ |
Fe |
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F |
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Fe |
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Ihkdhevdm agZq_gb_ E0 |
3+ |
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2+ [hevr_ agZq_gby E00 |
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− lh bhgu |
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Fe |
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Fe |
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I2 |
2I |
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Fe3+ kihkh[gu hdbkeblv bhgu,– ^h ijhklh]h \_s_kl\Z I2 Ke_^h\Zl_ev gh ba mdZaZgguo Zgbhgh\ lhevdh bhgu ,– [m^ml hdbkeylvky bhgZfb `_e_aZ,,,
Ex[Zy H<J \k_]^Z ijhl_dZ_l \ lhf gZijZ\e_gbb dhlhjhfm khhl\_lkl\m_l iheh`bl_evgh_ agZq_gb_ jZaghklb ihl_gpbZeh\ hdbkebl_ey b \hkklZgh\bl_ey.
H^gZdh g_h[oh^bfh ihfgblv qlh \ ^Zgghf gZijZ\e_gbb j_Zdpby ijhl_dZ_l ijZdlbq_kdb g_h[jZlbfh ijb jZaghklb ihl_gpbZeh\ û?, [hevr_c eb[h jZ\ghc < ?keb `_ jZaghklv ihl_gpbZeh\ û? hdZau \Z_lky f_gvr_ < lh H<J ijhl_dZ_l h[jZlbfh b gZijZ\e_gb_ j_Zd pbb hij_^_ey_lky mkeh\byfb __ ijh\_^_gby
Ijbf_j MklZgh\blv \ dZdhf gZijZ\e_gbb \hafh`gh kZfhijh ba\hevgh_ ijhl_dZgb_ j_Zdpbb
SnCl4 + 2FeCl2 <6Q&O2 + 2FeCl3.
J_r_gb_
GZoh^bf agZq_gby ?h ihemj_Zdpbc
E0 |
4+ |
Sn |
2+ = 0,15 <, |
E0 |
3+ |
Fe |
2+ = 0,77 <. |
Sn |
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Fe |
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Ihkdhevdm agZq_gb_ Eh ihemj_Zdpbb k mqZklb_f bhgh\ `_e_aZ [hevr_ agZq_gby ?h ihemj_Zdpbb k mqZklb_f bhgh\ heh\Z lh bhgu Fe3+ [m^ml hdbkeylv bhgu6Q2+ k h[jZah\Zgb_f bhgh\)H2+ b6Q4+ Wlh khhl\_lkl\m_l ijhl_dZgbx mdZaZgghc j_Zdpbb kijZ\Z gZe_\h
Ba \k_o \hafh`guo H<J gZb[he__ \_jhylghc [m^_l lZ j_Zd pby dhlhjhc khhl\_lkl\m_l fZdkbfZevgh_ agZq_gb_ jZaghklb ihl_gpbZeh\ bkihevam_fuo hdbkebl_ey b \hkklZgh\bl_ey
Ijbf_j Bkihevamy agZq_gby E0 ihemj_Zdpbc hij_^_eblv gZb[h- e__ \_jhylguc ijh^mdl \hkklZgh\e_gby bh^Zl-bhgh\ k_jgbklhc dbkehlhc
Z IO3− + 6H+ • : Iæ H2O, E0 = 1,08 <; [ IO3− + 6H+ + 5• : I2 + 3H2O, E0 = 1,19 <;
94
\ IO3− + 5H+ • : HIO + 2H2O, E0 = 1,14 <; ]) SO 24− + 4H+ • :+2SO3 + H2O, E0 = 0,17 <.
J_r_gb_
Ihkdhevdm agZq_gb_ ihl_gpbZeZ ihemj_Zdpbb©]ªf_gvr_ agZ q_gbc ihl_gpbZeh\ ihemj_Zpbc©Zª ©[ªb©\ªlh kmevnbl-bhgu [m^ml y\eylvky \hkklZgh\bl_eyfb ih hlghr_gbx d bh^Zl-bhgZf
>ey dZ`^hc ba ihemj_Zdpbc ©Zª ©[ª b ©\ª gZc^_f jZaghklv f_`^m __ ihl_gpbZehf b ihl_gpbZehf ihemj_Zdpbb©]ª
E0 Z – E0 ] < – 0,17 < = 0,91 <;
E0 [ – E0 ] < – 0,17 < = 1,02 <;
E0 \ – E0 ] < – 0,17 < = 0,97 <.
<b^gh qlh fZdkbfZevgh_ agZq_gb_ ûE0 khhl\_lkl\m_l jZaghklb f_`^m ihl_gpbZeZfb ihemj_Zdpbc©[ªb©]ªKe_^h\Zl_evgh k_jgbklZy dbkehlZ [m^_l \hkklZgZ\eb\Zlv bh^Zl-bhgu ^h k\h[h^gh]h bh^Z
Q_f [hevr_ agZq_gb_ û? j_Zdpbb l_f [hevr_ agZq_gb_ dhg klZglu obfbq_kdh]h jZ\gh\_kby b l_f kbevg__ hgh kf_s_gh \ klhjhgm h[jZah\Zgby ijh^mdlh\.
Ijbf_j JZkkqblZlv agZq_gb_ dhgklZglu obfbq_kdh]h jZ\gh\_ kby ^ey j_Zdpbb hdbke_gby kmevnZlZ `_e_aZ II i_jfZg]ZgZlhf dZeby \ k_jghdbkehf jZkl\hj_ \ dhlhjhf dhgp_gljZpbb \k_o ihl_gpbZeh ij_^_eyxsbo bhgh\ jZ\gu fhev e
J_r_gb_
KhklZ\bf mjZ\g_gb_ ^Zgghc H<J jZkklZ\bf dhwnnbpb_glu f_lh^hf we_dljhggh]h [ZeZgkZ b gZc^_f agZq_gb_ n.
2KMnO4 + 10FeSO4 + 8H2SO4 :)H2(SO4)3 + 2MnSO4 + K2SO4 + 8H2O
Mn+7 • :0Q+2 |
1 |
2 |
Fe+2 – • :)H+3 |
5 |
10 |
Ba mjZ\g_gbc we_dljhggh]h [ZeZgkZ \b^gh qlh qbkeh we_dljhgh\ hl^Zgguo \hkklZgh\bl_e_f b ijbgyluo hdbkebl_e_f l _ qbkeh n jZ\gh
GZc^_f agZq_gby ihl_gpbZeh\ ihemj_Zdpbc hdbke_gby bhgh\ `_ e_aZ Z b \hkklZgh\e_gby i_jfZg]ZgZl-bhgh\ \ dbkehc kj_^_ [
= 0,77< ;
Mn 2+ = 1,51< .
JZkkqblZ_f agZq_gb_ ûE0 j_Zdpbb
ûE0 = E0 − 2+ − E0 3+ 2+ = 1,51 < – 0,77 < = 0,74 <
MnO4 Mn Fe Fe
95
<uqbkebf agZq_gb_ dhgklZglu jZ\gh\_kby
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∆E n |
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0,74 5 |
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= 10 |
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≈ 51062 . |
KjZ\g = 100,059 |
0,059 |
LZdh_ h]jhfgh_ agZq_gb_ dhgklZglu jZ\gh\_kby k\b^_l_evkl\m_l h lhf qlh ^ZggZy j_Zdpby ijhl_dZ_l ke_\Z gZijZ\h ijZdlbq_kdb g_h[ jZlbfh
<ebygb_ jZaebqguo nZdlhjh\ gZ gZijZ\e_gb_ ijhl_dZgby hdbkebl_evgh-\hkklZgh\bl_evguo j_Zdpbc
Hdbkebl_evgh-\hkklZgh\bl_evgZy j_Zdpby ijhl_dZ_l \ lhf gZ ijZ\e_gbb \ dhlhjhf hkms_kl\ey_lky ihemj_Zdpby k [he__ \ukhdbf agZq_gb_f ihl_gpbZeZ Ihwlhfm nZdlhju \ebyxsb_ gZ \_ebqbgm ih l_gpbZeZ hdZau\Zxl \ebygb_ b gZ gZijZ\e_gb_ ijhl_dZgby H<J D lZdbf nZdlhjZf hlghkylky
dhgp_gljZpby ihl_gpbZehij_^_eyxsbo bhgh\
\_ebqbgZ jG jZkl\hjZ
l_fi_jZlmjZ jZkl\hjZ
\_ebqbgZ IJ fZehjZkl\hjbfh]h ijh^mdlZ j_Zdpbb
<_ebqbgZ dhgklZglu g_klhcdhklb h[jZamxs_]hky dhfie_dkgh ]h bhgZ
JZkkfhljbf oZjZdl_j \ebygby dZ`^h]h ba wlbo nZdlhjh\ gZ gZ ijZ\e_gb_ ijhl_dZgby H<J
<ebygb_ dhgp_gljZpbc ihl_gpbZehij_^_eyxsbo bhgh\
Baf_gyy agZq_gby dhgp_gljZpbc bhgh\ \ jZkl\hj_ fh`gh baf_ gblv gZijZ\e_gb_ ijhl_dZgby H<J
Ijbf_j Hij_^_eblv gZijZ\e_gb_ ijhl_dZgby j_Zdpbb
Sn0 + Pb2+ <6Q2+ + Pb0
ijb ke_^mxsbo agZq_gbyo dhgp_gljZpbc bhgh\ Z k(Pb2+ fhev e k(Sn2+ fhev e
[ k(Pb2+ fhev e k(Sn2+ fhev e
J_r_gb_
JZkkqblZ_f agZq_gby jZ\gh\_kguo we_dljh^guo ihl_gpbZeh\ ^ey kemqZy©Zªb hij_^_ebf gZijZ\e_gb_ j_Zdpbb
EPb2+ Pb0 |
= EPbo |
2+ Pb0 |
− |
0,059 |
lg |
1 |
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= −0,13 − |
0,059 |
lg |
1 |
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= −0,13B |
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c(Pb |
2+ |
) |
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n |
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2 |
1 |
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96
:gZeh]bqgh kqblZ_f agZq_gb_ ihl_gpbZeZ heh\Z
E |
2+ |
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0 = −0,14 − |
0,059 |
lg |
1 |
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= −0,14B . |
Sn |
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Sn |
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2 |
1 |
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Ihkdhevdm agZq_gb_ we_dljh^gh]h ihl_gpbZeZ k\bgpZ [hevr_ q_f m heh\Z lh bhgu k\bgpZ [m^ml y\eylvky hdbkebl_eyfb ih hlghr_ gbx d heh\m b mdZaZggZy j_Zdpby [m^_l ijhl_dZlv ke_\Z gZijZ\h.
1)JZkkqblZ_f agZq_gby jZ\gh\_kguo ihl_gpbZeh\ ^ey kemqZy©[ªb hij_^_ebf gZijZ\e_gb_ j_Zdpbb
E |
2+ |
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0 |
= Eo |
2+ |
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0 |
− |
0,059 |
lg |
1 |
= −0,13 − |
0,059 |
lg |
1 |
= −0,15B ; |
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c(Pb2+ ) |
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0,15 |
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Pb |
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Pb |
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Pb |
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Pb |
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n |
2 |
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E |
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2+ |
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0 = −0,14 − |
0,059 |
lg |
1 |
= −0,13B . |
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Sn |
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Sn |
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1,5 |
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< ^Zgghf kemqZ_ we_dljh^guc ihl_gpbZe [hevr_ m heh\Z ihwlh fm _]h bhgu [m^ml y\eylvky hdbkebl_eyfb ih hlghr_gbx d k\bgpm b mdZaZggZy H<J \ ^Zgguo mkeh\byo ijhl_dZ_l kijZ\Z gZe_\h.
<ebygb_ \_ebqbgu jG jZkl\hjZ
Baf_gyy agZq_gb_ jG jZkl\hjZ fh`gh baf_gblv gZijZ\e_gb_ ijhl_dZgby H<J _keb \ g_c ijbgbfZxl mqZklb_ bhgu G+ beb HG–.
Ijbf_j Baf_gblky eb gZijZ\e_gb_ ijhl_dZgby j_Zdpbb \ kbk
l_f_ K3AsO4 + KI + H2SO4 < K3AsO3 + I2 + K2SO4 + H2O
ijb baf_g_gbb jG jZkl\hjZ hl ^h _keb dhgp_gljZpbb bhgh\ AsO34 , AsO33− , I– b fhe_dme I2 \ jZkl\hj_ jZ\gu fhev e"
J_r_gb_:
1. >ZggZy H<J hkms_kl\ey_lky [eZ]h^Zjy ijhl_dZgbx ^\mo ihem
j_Zdpbc
Z AsO4 3– + 2H+ • : AsO33– + H2O; E0 = 0,57 <; [) I2 • :,–; E0 = 0,54 <.
Ihkdhevdm \ ihemj_Zdpbb©ZªijbgbfZxl mqZklb_ bhgu \h^hjh^Z __ ihl_gpbZe aZ\bkbl hl \_ebqbgu jG jZkl\hjZ < ihemj_Zdpbb©[ªbhgu G+ g_ mqZkl\mxl ihwlhfm __ ihl_gpbZe g_ aZ\bkbl hl \_ebqbgu jG
JZkkqblZ_f agZq_gb_ ihl_gpbZeZ ihemj_Zdpbb©Zªijb jG jZ\ ghf b hij_^_ebf gZijZ\e_gb_ H<J
?keb jG jZkl\hjZ jZ\gh lh dhgp_gljZpby bhgh\ \h^hjh^Z jZ\gZfhev e Lh]^Z
E 3- |
3- |
= 0,57 − |
0,059 |
lg |
1 |
= 0,57B . |
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1 1 |
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AsO4 |
AsO3 |
2 |
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97
Ihkdhevdm ijb jG jZ\ghf ihl_gpbZe ihemj_Zdpbb©Zª[hevr_ ihl_gpbZeZ ihemj_Zdpbb ©[ªZjk_gZl-bhgu [m^ml ijhy\eylv hdbkeb l_evgu_ Z bh^b^-bhgu – \hkklZgh\bl_evgu_ k\hckl\Z b mdZaZggZy j_ Zdpby \ p_ehf ijhl_dZ_l ke_\Z gZijZ\h.
JZkkqblZ_f agZq_gb_ ihl_gpbZeZ ihemj_Zdpbb©Zªijb jG jZ\ ghf b hij_^_ebf gZijZ\e_gb_ H<J
?keb jG jZkl\hjZ jZ\_g lh dhgp_gljZpby bhgh\ \h^hjh^Z kh klZ\ey_l 0-8 fhev e Lh]^Z
E 3- |
3- |
= 0,57 − |
0,059 |
lg |
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= 0,098B . |
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AsO4 |
AsO3 |
2 |
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Ihkdhevdm ijb jG jZ\ghf ihl_gpbZe ihemj_Zdpbb ©Zª f_gvr_ ihl_gpbZeZ ihemj_Zdpbb©[ªlh Zjk_gbl-Zgbhgu AsO33− [m^ml ijhy\eylv \hkklZgh\bl_evgu_ Z fhe_dmeu I2 – hdbkebl_evgu_ k\hckl\Z Wlh agZqbl qlh \ ^Zgguo mkeh\byo mdZaZggZy j_Zdpby ijhl_dZ_l kijZ\Z gZe_\h
<ebygb_ l_fi_jZlmju gZ gZijZ\e_gb_ ijhl_dZgby H<J
Ba mjZ\g_gby G_jgklZ \b^gh qlh \_ebqbgZ we_dljh^gh]h ihl_gpbZeZ aZ\bkbl b hl agZq_gby l_fi_jZlmju Ihwlhfm baf_gyy l_fi_jZlmjm jZk- l\hjZ fh`gh baf_gblv gZijZ\e_gb_ ijhl_dZgby g_dhlhjuo H<J
Ijbf_j IhdZaZlv dZd \eby_l baf_g_gb_ l_fi_jZlmju hl oK ^h oK gZ gZijZ\e_gb_ ijhl_dZgby j_Zdpbb
Na2Cr2O7 + 14HCl <&O2 + 2CrCl3 + 2NaCl + 7H2O,
_keb dhgp_gljZpbb bhgh\ Cr2O 72− b Cr3+ jZ\gu fhev e dhgp_gljZpby kheyghc dbkehlu jZ\gZ fhev e Z iZjpbZevgh_ ^Z\e_gb_ oehjZ –
dIZ
J_r_gb_
1.MdZaZggZy j_Zdpby khklhbl ba ^\mo ihemj_Zdpbc
Z&U2O 72− + 14H+ • : Cr3+ + 7H2O ?0 = 1,333 <;
[ Kl2 • : Cl– ?0 = 1,359 <.
2.JZkkqblZ_f agZq_gby ihl_gpbZeh\ ihemj_Zdpbc ©Zªb ©[ªijb l_fi_jZlmj_ hK b hij_^_ebf gZijZ\e_gb_ ijhl_dZgby H<J
Z E 2− |
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= Eo |
2− |
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2,303RT |
lg |
c2 (Cr3+ ) |
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Cr |
Cr |
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14 |
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Cr2O7 |
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2,303 8,314 298 |
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c(Cr2O7 |
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= 1,333 − |
lg |
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= 1,350B ; |
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6 96500 |
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98
[ E 0 |
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= Eo 0 |
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2,303RT |
lg |
c2 |
(Cl− ) |
= |
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Cl |
Cl |
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Cl2 |
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nF |
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= 1,359 − |
2,303 |
8,314 298 |
lg |
1,322 |
= 1,352B . |
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2 |
96500 |
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Ihkdhevdm \ ^Zgghf kemqZ_ jZaghklv ihl_gpbZeh\ ûE hdZaZeZkv f_gvr_ < \ kbkl_f_ mklZgZ\eb\Z_lky obfbq_kdh_ jZ\gh\_kb_ Gh mqblu\Zy [he__ \ukhdh_ agZq_gb_ ihl_gpbZeZ ihemj_Zdpbb©[ª^_eZ _f \u\h^ qlh ijb oK [he__ kbevgufb hdbkebl_evgufb k\hckl\Zfb h[eZ^Z_l oehj b qlh mdZaZggh_ jZ\gh\_kb_ kf_s_gh \e_\h
3. JZkkqblZ_f agZq_gby ihemj_Zdpbc ijb oK b hij_^_ebf gZ
ijZ\e_gb_ kf_s_gby jZ\gh\_kby |
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Z E |
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3+ = Eo |
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3+ − |
2,303RT |
lg |
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c2 (Cr3+ ) |
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2− |
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2− |
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Cr |
Cr |
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Cr2O7 |
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Cr2O7 |
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2,303 8,314 363 |
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c(Cr2O7 |
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= 1,333 − |
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= 1,353B . |
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6 96500 |
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(Cl− ) |
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[ E 0 |
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Eo 0 |
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2,303RT |
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c2 |
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Cl |
Cl |
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p(Cl2 ) |
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= 1,359 − |
2,303 |
8,314 363 |
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lg |
1,322 |
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= 1,350B . |
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96500 |
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LZdbf h[jZahf ijb l_fi_jZlmj_ oK [he__ \ukhdh_ agZq_gb_ ihl_gpbZeZ m ihemj_Zdpbb ©ZªWlh agZqbl qlh [he__ kbevgu_ hdbk
ebl_evgu_ k\hckl\Z ijhy\eyxl bhgu Cr2O 72− b jZ\gh\_kb_ j_Zdpbb \ p_ehf kf_s_gh \ijZ\h
<ebygb_ \_ebqbgu IJ fZehjZkl\hjbfh]h ijh^mdlZ gZ gZijZ\e_gb_ ijhl_dZgby H<J
?keb \ j_amevlZl_ H<J h[jZam_lky fZehjZkl\hjbfuc ijh^mdl lh dhgp_gljZpby h[jZamxsbo _]h bhgh\ \ jZkl\hj_ j_adh mf_gvrZ_lky <ke_^kl\b_ wlh]h baf_gy_lky ihl_gpbZe khhl\_lkl\mxs_c ihemj_Zd pbb qlh fh`_l ijb\_klb d baf_g_gbx gZijZ\e_gby H<J
Ijbf_j Hij_^_eblv gZijZ\e_gb_ ijhl_dZgby j_Zdpbc ijb 25 oK \ kbkl_fZo
Z $J +&O<+2 + 2AgCl;
[) 2Ag + 2HI <+2 + 2AgI,
_keb dhgp_gljZpbb oehjh\h^hjh^Z b bh^h\h^hjh^Z \ jZkl\hj_ jZ\gu 1 fhev e Z ^Z\e_gb_ \h^hjh^Z jZ\gh dIZ
99
J_r_gb_
JZkkqblZ_f dhgp_gljZpbx bhgh\ k_j_[jZ \ jZkl\hj_ gZ^ hkZ^ dhf AgCl ^himklb\ qlh dhgp_gljZpby oehjb^-bhgh\ \ jZkl\hj_ jZ\gZ dhgp_gljZpbb GCl b khklZ\ey_l fhev e
c(Ag+) = IJ(AgCl) = 1,8 10−10 = 1,810−10 fhev e c(Cl− ) 1
JZkkqblZ_f agZq_gb_ jZ\gh\_kgh]h ihl_gpbZeZ k_j_[jZ \ ^Zg ghf jZkl\hj_
E |
+ |
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0 |
= Eo |
+ |
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0 |
− |
0,059 |
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lg |
1 |
= |
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n |
c(Ag+ ) |
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Ag |
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Ag |
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Ag |
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Ag |
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= 0,8 − |
0,059 |
lg |
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= 0,225B. |
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Hij_^_ebf gZijZ\e_gb_ j_Zdpbb©Zª
Ihkdhevdm \ mdZaZgguo mkeh\byo ihl_gpbZe \h^hjh^Z jZ\_g Z ihl_gpbZe k_j_[jZ jZ\_g < lh bhgu k_j_[jZ ijhy\eyxl hdbkeb l_evgu_ k\hckl\Z ih hlghr_gbx d \h^hjh^m b jZ\gh\_kb_ j_Zdpbb©Zª kf_s_gh \e_\h Ihwlhfm f_lZeebq_kdh_ k_j_[jh g_ jZkl\hjy_lky \ kh eyghc dbkehl_
JZkkqblZ_f dhgp_gljZpbx bhgh\ k_j_[jZ \ jZkl\hj_ gZ^ hkZ^ dhf AgI ^himklb\ qlh dhgp_gljZpby bh^b^-bhgh\ \ jZkl\hj_ jZ\gZ dhgp_gljZpbb HI b khklZ\ey_l fhev e
c(Ag+) = IJ(AgI) = 8,310−17 = 8,310−17 fhev e . c(I− ) 1
JZkkqblZ_f agZq_gb_ jZ\gh\_kgh]h ihl_gpbZeZ k_j_[jZ \ ^Zg ghf jZkl\hj_
E |
+ |
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0 |
= Eo |
+ |
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0 |
− |
0,059 |
lg |
1 |
= |
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c(Ag+ ) |
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Ag |
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Ag |
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Ag |
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Ag |
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n |
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= 0,8 − |
0,059 |
lg |
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1 |
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= −0,14B. |
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8,310−17 |
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Hij_^_ebf gZijZ\e_gb_ j_Zdpbb©[ª
Ihkdhevdm \ jZkl\hj_ HI ihl_gpbZe k_j_[jZ f_gvr_ ihl_gpbZeZ \h^hjh^Z jZ\gh]h lh k_j_[jh [m^_l hdbkeylvky bhgZfb \h^hjh^Z b jZ\gh\_kb_ j_Zdpbb©[ªijZdlbq_kdb iheghklvx kf_s_gh \ijZ\h
LZdbf h[jZahf f_lZeebq_kdh_ k_j_[jh \ul_kgy_l \h^hjh^ ba jZkl\hjZ bh^h\h^hjh^ghc dbkehlu
100