Химия дефектов: Методические указания

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Author: Семенова Г.В. | Сушкова Т.П.

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1

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4

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8

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(1)

]^_∆S, ∆H -baf_g_gb_wgljhibbbwglZevibb\ijhp_kk_d\Zabobfbq_kdhcj_Zd pbbMjZ\g_gb_ mdZau\Z_lgZk\yavhldehg_gbyhlkl_obhf_ljbbkhkgh\gufb l_jfh^bgZfbq_kdbfbiZjZf_ljZfbJZkkfhlj_ggZyko_fZkZfhijhba\hevgh]hhl dehg_gby hl kl_obhf_ljbb fh`_l [ulv iheh`_gZ\hkgh\mbkdmkkl\_ggh]hijb gm^bl_evgh]h ^_n_dlhh[jZah\Zgby ijb baf_g_gbb \g_rgbo mkeh\bc \ jZkkfhl j_gghfijbf_j_-\mkeh\byoih\ur_ggh]h^Z\e_gbyiZjZdhfihg_glZ:
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11

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12

§L_jfh^bgZfbdZlhq_qguo^_n_dlh\ Klhqdbaj_gbyl_jfh^bgZfbdbdjbklZeeij_^klZ\ey_lkbkl_fm\dhlhjhc ijhbkoh^blwg_j]_lbq_kdbcbfZl_jbZevguch[f_gbk\g_rg_ckj_^hcbf_`^m jZaebqgufbih^kbkl_fZfbdjbklZeeZ_ckl\bl_evgh mkeh\b_ fbgbfmfZ wg_j]bb =b[[kZ ijb obfbq_ kdhfjZ\gh\_kbbijb\h^bld\ujZ`_gbx ∏ xiν = K (T) ]^_.7 -aZ\bkysZyhll_fi_jZlmjudhgklZglZjZ\gh\_kbyd\Zabobfbq_kdhcj_ Zdpbb Ijb lZdhf ih^oh^_ g_h[oh^bfh agZgb_ dhgklZgl jZ\gh\_kby dhlhju_ fh`ghhp_gblvdZdl_hj_lbq_kdblZdbgZhkgh\_wdki_jbf_glZ
13

(W - l_jfh^bgZfbq_kdZy \_jhylghklv kbkl_fu iha\hey_l ihemqblv l_fi_jZlmj gmxaZ\bkbfhklvjZ\gh\_kghcdhgp_gljZpbb^_n_dlh\lh]hbebbgh]hlbiZ >eyjZamihjy^hq_gbyihRhlldbfheyjgZy^hey\ZdZgkbc[VjZ\gZ xV = exp [ ∆Sdhe / k] exp [ - ∆HV / kT ] ,

(2)

]^_ ∆HV - wglZeviby h[jZah\Zgby \ZdZgkbc ∆Sdhe - dhe_[Zl_evgZy wgljhiby Ih ke_^gxx oZjZdl_jbklbdm fh`gh mijhs_ggh hij_^_eblv k ihfhsvx hlghr_gby qZklhldhe_[Zgbcj_r_ldbb^_Zevgh]hν b^_n_dlgh]hν′)djbklZeeZ ∆Sdhe = k z ln ν / ν′ (z -dhhj^bgZpbhggh_qbkehj_r_ldb >ey ^_n_dlh\ Nj_gd_ey l_fi_jZlmjgZy aZ\bkbfhklv jZ\gh\_kghc dhgp_g ljZpbblZd`_hij_^_ey_lkywglZevib_cijhp_kkZ^_n_dlhh[jZah\Zgby∆HFbaZ\b kbl hl baf_g_gby dhe_[Zl_evghc wgljhibb ∆Sdhe ?keb 1 - qbkeh maeh\ Z 1′ qbkehf_`^hmaebcdjbklZeeZlhdhebq_kl\h^_n_dlh\Nj_gd_eyQ n= √ N N′ exp [ ∆Sdhe / 2k] exp [ - ∆HF / 2kT ].

(3)

Ihkdhevdm baf_g_gb_ dhe_[Zl_evghc wgljhibb ijb h[jZah\Zgbb ^_n_dlh\ dZdijZ\beh^Z_lf_gvrbc\deZ^\\_ebqbgmQq_fkhhl\_lkl\mxsb_wglZevibb h[jZah\Zgbylhbodhgp_gljZpbyhij_^_ey_lky\i_j\mxhq_j_^v\_ebqbghc∆H. LZd\f_lZeeZo∆SdhekhklZ\ey_l\_ebqbgm-N^eyihemijh\h^gbdh\bbhg guodjbklZeeh\-^hNIjbihemq_gbbhp_ghqguo^Zgguohq_gvqZklhiheZ ]Zxli_j\uckhfgh`bl_ev\mjZ\g_gbyo jZ\guf_^bgbp_
14

2. Ijbgbadhcdhgp_gljZpbb^_n_dlh\^eyZgZebaZjZ\gh\_kbcihke_^gboijbf_ gy_lky aZdhg ^_ckl\mxsbo fZkk K dZdbfb ljm^ghklyfb fh]ml [ulv k\yaZgu ihiuldbijbf_g_gbywlh]hf_lh^ZdjZ\gh\_kbyfk[hevrbfbdhgp_gljZpbyfb ^_n_dlh\" 3. Fh`ghebijbl_jfh^bgZfbq_kdhfhibkZgbb^_n_dlhh[jZah\Zgby\djbklZee_ \xkpblZkhklZ\ZFe0,88Oijbf_gylvijb[eb`_gb_b^_ZevguojZkl\hjh\" 4. Ihq_fm\f_lZeeZohkgh\guf\b^hflhq_qguo^_n_dlh\\khklhygbbl_ieh\h]h jZ\gh\_kbyy\eyxlky\ZdZgkbb"
15

7.
§JZ\gh\_kb_lhq_qguo^_n_dlh\>bZ]jZffu;jhmwjZ < djbklZee_ l\_j^h]h \_s_kl\Z ij_^klZ\e_g p_euc ZgkZf[ev kh[kl\_gguo ^_n_dlh\ dZd we_dljhgguo lZd b lhq_qguo djhf_ lh]h \hafh`gh ijbkmlkl\b_ ihklhjhggbo ijbf_k_c Dhgp_gljZpby ex[h]h \b^Z ^_n_dlh\ hij_^_ey_lky \g_rgbfb mkeh\byfb gh lZd`_ aZ\bkbl b hl ijbkmlkl\by ^jm]bo ^_n_dlh\ < aZ\bkbfhklbhlmkeh\bcijb]hlh\e_gbybebh[jZ[hldbdjbklZeeZjZaebqZxlihe gh_bqZklbqgh_jZ\gh\_kb_^_n_dlh\\djbklZee_ < ijhkluo \_s_kl\Zo dhgp_gljZpby g_cljZevguo ^_n_dlh\ g_ aZ\bkbl hl ijbkmlkl\by ^jm]bo \b^h\ ^_n_dlh\ \ lhf qbke_ b ijbf_kb Z hij_^_ey_lky ebrvl_fi_jZlmjhceykh_^bg_gbclhq_qgu_^_n_dlufh]ml\hagbdZlv\ h[_bo ih^j_r_ldZo \ \b^_ dhf[bgZpbc - iZjguo ^_n_dlh\ k mq_lhf ijbgpbiZ khojZg_gbyqbkeZmaeh\ Djhf_lh]hjZ\gh\_kb_\^\modhfihg_glghckbkl_f_ ^b\ZjbZglgh b dhgp_gljZpby dZ`^h]h \b^Z ^_n_dlh\ hij_^_ey_lky g_ lhevdh l_fi_jZlmjhcghb^Z\e_gb_fiZjZdhfihg_glh\ >ey\uqbke_gbydhgp_gljZpbc^_n_dlh\ijbkmlkl\mxsbo\djbklZee_ijb hij_^_e_gguomkeh\byobkihevamxljZaebqgu_ih^oh^uH^bgbagZb[he__qZk lh ijbf_gy_fuo jZa\bl Dj_]_jhf b hkgh\Zg gZ aZdhg_ ^_ckl\mxsbo fZkk d\Zabobfbq_kdbo j_Zdpbc < dZq_kl\_ ^hihegbl_evgh]h mkeh\by ijb wlhf

16

obfbq_kdboj_Zdpbch dZ`bl_kihfhsvxd\Zabobfbq_kdh]hih^oh^Zqlhh^ghdhfihg_glgZy^\mo nZagZykbkl_fZbf__lh^gmkl_i_gvk\h[h^u 5.
17

18

e_]bjh\Zggh]h ba ]Zah\hc nZau ^hghjghc ijbf_kvx _keb ba\_klgu ke_ ^mxsb_wg_j]_lbq_kdb_iZjZf_ljuZ ∆E0 w<∆HV w<∆EA = 0,2 w< ∆ED w<∆HG w<[ ∆E0 w<∆HV w<∆EA w< ∆ED w<∆HG w<L@ - ln PM ( i- lbi lhq_qguo ^_n_dlh\ Ihkljhcl_ aZ\bkbfhklv hldehg_gby hl kl_obhf_ljbb kh_^bg_gby FOhl^Z\e_gbyiZjZdhfihg_glZFijbihklhygghcl_fi_jZlmj_ 10.DZdh\h q_j_^h\Zgb_ h[eZkl_c ZiijhdkbfZpbb ijb bkihevah\Zgbb f_lh^Z ;jhmwjZ Z ijb \oh`^_gbb Zdp_ilhjghc ijbf_kb \ ihemijh\h^gbdh\h_ kh _^bg_gb_FO"[ ^hghjghcijbf_kb-\rbjhdhahggucfZl_jbZeFO"DZdh\ f_oZgbaf\oh`^_gbyijbf_kb\dZ`^hfkemqZ_" 11.Ihkljhblv^bZ]jZffu;jhmwjZko_fZlbqgh ^eykemqZy\oh`^_gbyZdp_ilhj ghcijbf_kb\ihemijh\h^gbdFOb\rbjhdhahggucfZl_jbZeFO

§E_]bjh\Zgb_l\_j^hnZaguofZl_jbZeh\ Ijb\\_^_gbb\djbklZeebghjh^ghcijbf_kb__Zlhfufh]mlaZgbfZlvj_ ]meyjgu_ maeu djbklZeebq_kdhc j_r_ldb nhjfbjmy l\_j^uc jZkl\hj aZf_s_ gby beb jZkiheZ]Zlvky \ f_`^hmaebyo h[jZamy l\_j^uc jZkl\hj \g_^j_gby < aZ\bkbfhklb hl obfbq_kdhc ijbjh^u dhfihg_glh\ \ djbklZee_ j_Zebam_lky lhl beb bghc lbi jZkl\hjZ >ey h[jZah\Zgby l\_j^h]h jZkl\hjZ \g_^j_gby hkgh\gh_ agZq_gb_ bf__l jZaf_jguc nZdlhj Ijb [ebahklb `_ Zlhfguo jZaf_jh\ b h^gh lbighklbdjbklZeebq_kdboj_r_lhdhkgh\gh]h\_s_kl\Zbijbf_kbnhjfbjmxlky l\_j^u_jZkl\hjuaZf_s_gbyijbq_fq_f[hevr_hlebqZxlkyihk\h_cobfbq_ kdhcijbjh^_dhfihg_glul_ff_gvr_dhgp_gljZpbhggucbgl_j\Zekms_kl\h\Z gbyl\_j^hnZaghcjZkl\hjbfhklb

19

< aZ\bkbfhklb hl khhlghr_gby qbkeZ \Ze_glguo we_dljhgh\ hkgh\gh]h b ijbf_kgh]hZlhfh\jZaebqZxlbah\Ze_glgh_b]_l_jh\Ze_glgh_we_dljhgghZd lb\gh_ e_]bjh\Zgb_ Ijb e_]bjh\Zgbb ]_l_jh\Ze_glghc ijbf_kvx ijbf_kgu_ p_glju fh]ml \uihegylv nmgdpbb ^hghjh\ beb Zdp_ilhjh\ \ebyy lZdbf h[jZ ahf gZ we_dljhnbabq_kdb_ k\hckl\Z fZl_jbZeZ Ihkdhevdm ijhp_kku bhgbaZpbb ^_n_dlh\bijbf_kbk\yaZgumjZ\g_gb_fwe_dljhg_cljZevghklbdjbklZeeZlhgZ ebqb_ijbf_kbkdZau\Z_lkygZ\_ebqbg_dhgp_gljZpbblhq_qguo^_n_dlh\<\_ ^_gb_ijbf_kbijb\h^bldm\_ebq_gbxdhgp_gljZpbbkh[kl\_gguo^_n_dlh\ijh lb\hiheh`gh]h agZdZ b d mf_gvr_gbx dhgp_gljZpbb ^_n_dlh\lh]h`_agZdZK ^jm]hcklhjhgukh[kl\_ggu_^_n_dlulZd`_\ebyxlgZjZkl\hjbfhklvijbf_kb Zf_oZgbaf__\oh`^_gby\djbklZeehij_^_ey_lkyijhlb\hiheh`ghaZjy`_ggu fb kh[kl\_ggufb ^_n_dlZfb ^hfbgbjmxsbfb ijb ^Zgghc l_fi_jZlmj_ \ qbk lhf g_e_]bjh\Zgghf djbklZee_ Ijb \\_^_gbb \ djbklZee ^\mo ihklhjhggbo ijbf_k_c ih\_^_gb_ fZl_jbZeZ hij_^_ey_lky ij_\Zebjmxs_c ijbf_kvx Ijb wlhfkjhklhf^heb^hfbgbjmxs_cijbf_kb-^hghjZm\_ebqb\Z_lkydhgp_gljZpby we_dljhgh\bhljbpZl_evghaZjy`_gguolhq_qguo^_n_dlh\bgZh[hjhlIjbf_kb hdZau\Zxlb\aZbfgh_\ebygb_^jm]gZ^jm]ZlZdm\_ebq_gb_dhgp_gljZpbbZd p_ilhjh\ klbfmebjm_l ijhp_kk bhgbaZpbb ^hghjh\ Z e_]bjh\Zgb_ ijbf_kvx^hghjhf\_^_ldjhklmdhgp_gljZpbbZdp_ilhjh\ Ijbnhjfbjh\Zgbbl\_j^h]hjZkl\hjZaZf_s_gby\djbklZeeZokh_^bg_gbc Zlhfuijbf_kbjZkiheZ]Zxlky\ih^j_r_ld_lh]hdhfihg_glZdhlhjuc[eb`_bf ihk\h_cijbjh^_?keb`_jZaghklvhlghkbl_evghcwe_dljhhljbpZl_evghklbdhf ihg_glh\kh_^bg_gbyg_\_ebdZlhhkgh\gufijb\u[hj_f_klhiheh`_gbyijbf_ kby\ey_lkyjZaf_jgucnZdlhjHq_\b^ghqlh\\_^_gb_we_dljhgghZdlb\guo]_ l_jh\Ze_glguoijbf_k_c\hafh`ghebrvijbmkeh\bbdhfi_gkZpbbboaZjy^h\eb[himl_fbaf_g_gbyqbkeZk\h[h^guoghkbl_e_ceb[haZkq_lkh[kl\_gguoaZ jy`_gguo ^_n_dlh\ ijhlb\hiheh`gh]h agZdZ GZijbf_j ijb e_]bjh\Zgbb oeh jb^Z k_j_[jZ KG&O2 \\_^_gb_ ijbf_kb \e_q_l aZ kh[hc lZdmx jZamihjy^hq_g ghklvijbdhlhjhch[jZamxlkylhq_qgu_^_n_dlukijhlb\hiheh`gufagZdhf

20

CdCl2 ↔ Cd•Ag + V′Ag + 2Cl×Cl ( → 2 AgCl ) LZdhckihkh[e_]bjh\ZgbygZau\Z_lkyf_lh^hfdhgljhebjm_fuoZlhfguo ^_n_dlh\D:> ihkdhevdmdhebq_kl\h\\_^_gghcijbf_kbhij_^_ey_lmjh\_gv ^_n_dlghklbdjbklZeeZ Ihkdhevdm \ kh_^bg_gbyo \ hlebqb_ hl ijhkluo \_s_kl\ dhgp_gljZpby b ijbjh^Zkh[kl\_gguo^_n_dlh\aZ\bkblg_lhevdhhll_fi_jZlmjughbhliZjpb Zevguo^Z\e_gbciZjZdhfihg_glh\\h\g_rg_cnZa_lhboZjZdl_jdhfi_gkZpbb aZjy^Zijbf_kb[m^_lhij_^_eylvkymkeh\byfb\\_^_gbyijbf_kb\djbklZee>ey g_kl_obhf_ljbq_kdbonZa\hafh`ghbaf_g_gb_f_oZgbafZe_]bjh\Zgby\mkeh \byoih\ur_ggh]hbebihgb`_ggh]hihkjZ\g_gbxkhkl_obhf_ljbq_kdbf ^Z\ e_gby iZjZ GZijbf_j ba\_kl_g wnn_dl dhgljhebjm_fhc \Ze_glghklbe_]bjh \Zgb_\xkpblZZdp_ilhjghcijbf_kvxijb\ukhdhf^Z\e_gbbdbkehjh^Zkhijh \h`^Z_lkyh[jZah\Zgb_f^ujhddhlhju_nhjfbjmxldhfie_dkukj_]meyjgufb maeZfb j_r_ldb qlh wd\b\Ze_glgh baf_g_gbx kl_i_gb hdbke_gby `_e_aZ k gZ3: Na2O + 1/2 O2(g) ↔ 2 Na′Fe + 2 O×O + 2 h• ( → 2 FeO ) Fe×Fe + h• → Fe•Fe a^_kv)H×Fewd\b\Ze_glgh)H2+Z)H•Fe - Fe3+ Kmffbjmywlb^\Zijhp_kkZihem qbf Na2O + 3/2 O2(g) ↔ 2 Na′Fe + 4 O×O + 2 Fe•Fe ( → 4 FeO ) Ih^h[guckihkh[e_]bjh\ZgbygZau\Zxlf_lh^hfdhgljhebjm_fuowe_d ljhgguo ^_n_dlh\ DW> >_ckl\bl_evgh \ dbkehjh^kh^_j`Zs_c Zlfhkn_j_ \xkpbl y\ey_lky ijh\h^gbdhf j-lbiZ gh fZdkbfZevgZy dhgp_gljZpby iheh`b l_evguo aZjy^h\ h]jZgbq_gZ dhgp_gljZpb_c \ZdZgkbc - jZamihjy^hq_gb_f nZau ?keb `_ dhfi_gkbjh\Zlv iheh`bl_evguc aZjy^ bhgh\ )H3+ Zdp_ilhjghc ijbf_

21

kvxlhkjhklhfkh^_j`Zgbyijbf_kbjZkl_lbijh\h^bfhklvJZkl\hj_gb_`_Zd p_ilhjghcijbf_kbihf_oZgbafmdhgljhebjm_fuoZlhfguo^_n_dlh\ Na2O ↔ 2 Na′Fe + O×O + V••O ( → 2 FeO ) y\ey_lkyg_[eZ]hijbylguf\mkeh\byoba[uldZdbkehjh^Zihkdhevdm\ZdZgkbb dbkehjh^ZZggb]bebjmxl9••O + 1/2 O2(g) ↔ O×O + 2 h•. >eyijbf_kb-^hghjZf_oZgbafdhgljhebjm_fuowe_dljhgguo^_n_dlh\j_Z ebam_lky\mkeh\byoihgb`_ggh]h^Z\e_gbyiZjZ Cr2O3 + 2 h• ↔ 2 Cr•Fe + 2 O×O + 1/2 O2 (g) ( → 2 FeO ) <\_^_gb_\djbklZee^\moihklhjhggbo]_l_jh\Ze_glguoijbf_k_cjZaebq gh]hagZdZfh`_lijb\_klbdwnn_dlmdhfi_gkZpbbaZjy^h\dh]^ZdjbklZeehdZ `_lky\j_amevlZl_e_]bjh\Zgbyg_ijh\h^ysbfGZijbf_jh^gh\j_f_ggh_e_]b jh\Zgb_kmevnb^ZdZ^fby^hghjghcbZdp_ilhjghcijbf_kyfbijb\h^bldlhfm qlhdjbklZeeijbh[j_lZ_lk\hckl\ZbaheylhjZ Ga2S3 + Cu2S ↔ 2 Ga•Cd + 2 Cu′Cd + 4 S×S ( → 4 CdS )
22

4. DZdbaf_gblkyiehlghklvdjbklZeeh\ijbe_]bjh\ZgbbdjbklZeeZNaCl –oeh jb^hf fZ]gby djbklZeeZ ZrO2 –hdkb^hfdh[ZevlZII djbklZeeZGa2O3 –hd kb^hfpbjdhgbyIV) ? 5. Knhjfmebjmcl_dZdmxijbf_kvgZ^h\\_klb\[bgZjgucdjbklZeebijbdZdbo mkeh\byoqlh[ujZamihjy^hq_gb_ijhbahreh\dZlbhgghcih^j_r_ld_"\Zgb hgghcih^j_r_ld_"Hl\_lijhbeexkljbjmcl_ijbf_jZfb AZ^ZqbbmijZ`g_gby 1. GZibrbl_mjZ\g_gbyhljZ`Zxsb_\\_^_gb_ijbf_kb \fZljbpm ihf_ lh^mD:>bf_lh^mDW> 1 2 Z ZnO → Ga2O3; [) Ga2O3 → ZnO; \) CuCl → Cu2S; ]) Cu2S → CuCl;

^) _) `) a)

1 As2O5 ZrO2 Ag2S AgCl

→ → → →

2 ZrO2; As2O5; AgCl; Ag2S.

2. DZdh\f_oZgbaf\oh`^_gbyijbf_kb\kl_obhf_ljbq_kdbcdjbklZee^eydhlh jh]hD0= 10-30D′s= 10-20ijbihklhygghcl_fi_jZlmj_"D0 –dhgklZglZjZ\gh \_kby ijhp_kkZ we_dljhggh-^ujhqgh]h jZamihjy^hq_gby D′s – dhgklZglZ jZ\ gh\_kbyijhp_kkZjZamihjy^hq_gbyihRhlldb 3.
^ZDZdbaf_gblkybgl_gkb\ghklvk\_q_gbyijbe_]bjh\Zgbb
4. Ijb hdbke_gbb gbd_ey h[jZam_lky nZaZ NiO bf_xsZy ijh\h^bfhklv j-lbiZ M\_ebqblkybebmf_gvrblkydhjjhabyNiO\ijbkmlkl\bbLi2O? Cr2O3 ? 5. H[gZjm`_ghqlhjZajmr_gb_ZrO2ijbgZ]j_\ZgbbgZ\ha^mo_ihl_jydbkehjh ^Z m\_ebqb\Z_lky\ijbkmlkl\bbP2O5H[tykgbl_wlhy\e_gb_ 6. DZd h[tykgblv lhl nZdlqlhjZajmr_gb_Fe2O3ijbgZ]j_\ZgbbgZ\ha^mo_aZ f_^ey_lkyijbaZ]jyag_gbbbkoh^gh]hhdkb^Z^bhdkb^hflblZgZ" 7. Kdhjhklvl\_j^hnZaghcj_ZdpbbZnO + CuSO4 → ZnSO4 + CuOmf_gvrZ_lky ijbe_]bjh\Zgbbbkoh^gh]hZnOhdkb^hfojhfZIII). H[tykgbl_wlhlnZdl

23

mqblu\ZyqlhZnO -fZl_jbZen-lbiZZiehlghklv_]hih\ur_gZihkjZ\g_ gbxkhkl_obhf_ljbq_kdbfkhklZ\hf 8. DZdbaf_gblkykdhjhklvl\_j^hnZaghcj_Zdpbb)H&X&O2 → Cu + FeCl2ijb e_]bjh\Zgbb&X&O2kmevnb^hff_^bII)? 9. PbCl2 - nZaZ k jZamihjy^hq_gb_f ih Nj_gd_ex \ dZlbhgghc ih^j_r_ld_ DZd baf_gblky bgl_gkb\ghklv ijhp_kkh\ ^bnnmabb ijb e_]bjh\Zgbb wlhc nZau kmevnb^hfk\bgpZ" 10.H[jZah\Zgb_ ribg_eb MgAl2O4 b^_l iml_f h^ghklhjhgg_c ^bnnmabb bhgh\

Mg2+ b _′ < dZdhf kemqZ_ [m^_l gZ[ex^Zlvky [he__ bgl_gkb\guc jhkl kehy ijh^mdlZ _keb ribg_ev bf__l kl_obhf_ljbq_kdbc khklZ\ beb _keb kehc MgAl2O4 ihemq_gjZkl\hj_gb_fB2O3\kl_obhf_ljbq_kdhcribg_eb\hdbkeb l_evghcZlfhkn_j_" EBL?J:LMJ:

1. L_jfh^bgZfbdZbfZl_jbZeh\_^_gb_ihemijh\h^gbdh\Ih^j_^<F=eZah\Z FF_lZeemj]byk 2. Gh\bdh\ BB Jhabg DF DjbklZeeh]jZnby b ^_n_dlu djbklZeebq_kdhc j_ r_ldbFF_lZeemj]byk 3. Nbklmev<NbabdZbobfbyl\_j^h]hl_eZ<-olFF_lZeemj]by 4. =hgqZjh\?=K_f_gh\Z=<M]ZcY:Obfbyihemijh\h^gbdh\Mq_[ihk
KhklZ\bl_eb K_f_gh\Z=ZebgZ<eZ^bfbjh\gZ Kmrdh\ZLZlvygZIZ\eh\gZ J_^ZdlhjDmag_ph\ZA?

24

IJBEH@?GB? ` ⋅ D-1 = 8,62 ⋅10-5w<⋅D-1 IhklhyggZyIeZgdZh = 6,62 ⋅10-34>`⋅k We_f_glZjgucwe_dljbq_kdbcaZjy^e = 1,60 ⋅10 –19 De :lhfgZy_^bgbpZfZkkuZ_f ⋅10-27d] FZkkZihdhywe_dljhgZm0=9,11 ⋅10-31d] Kdhjhklvk\_lZ\\Zdmmf_ c = 3 ⋅108f⋅k-1 FheyjgZy]Zah\ZyihklhyggZyR >`⋅fhev-1 ⋅ D-1 >` ⋅1018w< w< ⋅10-19>`

LZ[ebpZ OZjZdl_jbklbdZf_`^hmaebc\j_r_ldZojZaebqgh]hlbiZ Lbi j_r_l Qbkeh imklhl db we_f_glyq_cd_

\ Dhwnn Hlghkbl_evguc jZa dhfiZdl f_jf_`^hmaebc∗ ghklb HdlZw^j L_ljZw^j HdlZw^j L_ljZw^j =PDD 4 8 0,74 0,41 0,225 =_dkD 4 8 0,74 0,41 0,225 HPDD 6 12 0,68 0,154 0,291 :efZaD 8 0,364 1,000 ∗ -jZaf_juf_`^hmaebc^ZgugZhkgh\Zgbbfh^_eb`_kldborZjh\

25

LZ[ebpZ

WglZevibybwgljhibyh[jZah\Zgby\ZdZgkbc \djbklZeeZoijhkluo\_s_kl\ DjbklZee

TF, K

∆HV, w<

∆SV / k

Al Ag Au Cu α-Fe K Li Mo Na Nb Ni Pb Pt W Zn

Lbij_r_l db =PD =PD =PD =PD HPD HPD HPD HPD HPD HPD =PD =PD =PD HPD ]_dk

934 1235 1338 1357 1808 337 454 2890 371 2741 1726 601 2045 3680 693

0,67 1,13 0,95 1,28 1,4 0,39 0,40 3,2 0,39 2,6 1,6 0,59 1,51 3,6 0,53

0,7 1,5 0,7 2,4

CZefZa C]jZnbl Ge Si Te

ZefZa ]_dk ZefZa ZefZa ]_dk

~3820

4,16 3,3 2,10 2,32 0,8

1211 1683 723

2

7,5 8,0

26

LZ[ebpZ WglZevibyh[jZah\Zgby\w< ^_n_dlh\Rhlldb∆HSbNj_gd_ey\ dZlbhgghc∆HF bZgbhgghc∆H′F ih^j_r_ldZobhgguodjbklZeeh\ DjbklZee NaF NaCl NaBr NaI KF KCl KBr KI AgCl AgBr AgI CuCl CaF2 SrF2 BaF2 MgO CaO SrO CeO2 ThO2 UO2

Lbij_ r_ldb =PD =PD =PD =PD =PD =PD =PD =PD =PD =PD =_dk =PD =PD =PD =PD =PD =PD =PD =PD =PD =PD

LFD

∆GS

∆HF

∆H′F

1253 1077 1028 924 1153 1049 1003 1046 728 707 825 695 1633 1463 1553 3073 2845 1703 2223 >3073 2449

2,49 2,26 2,11 1,77 1,92 2,20 2,13 2,00 1,98 2,27 7,0-8,6 6,9-8,1 6,3-6,9 4-9 5,5-8 5-7 2,0 1,9 ~7

3,53 2,88 2,56 2,00 4,27 3,46 3,16 2,73 0,6-0,8 1,05 6,0 4,2 5,2 ~10

3,39 4,60 4,84 5,14 2,57 3,73 4,17 4,26 2,6-2,7 2,2-2,4 1,6-2,0 20 16 ~9

27

LZ[ebpZ WglZevibyh[jZah\Zgby\w< \ZdZgkbcbZglbkljmdlmjguo ^_n_dlh\\ZefZahih^h[guoihemijh\h^gbdh\uokh_^bg_gbyo DjbklZee GaP GaAs GaSb InP InAs InSb ZnO ZnS ZnSe ZnTe CdS CdSe CdTe

TF, K 1740 1511 985 1343 1216 798 >2073 2123 1710 1512 2023 >1623 1248

∆H (VA) 2,98 2,59 2,03 3,04 2,61 2,12 5,41 3,47 3,09 2,54 3,56 3,18 2,75

∆H (VB) 2,64 2,59 2,56 2,17 2,07 2,12 3,00 3,13 3,09 3,60 2,69 2,65 2,75

∆H (AB) 0,38 0,35 0,08 0,42 0,33 0,27 5,98 1,45 1,25 0,96 1,48 1,25 0,94

∆H (BA) 0,68 0,35 0,32 0,89 0,57 0,27 5,43 1,74 1,25 0,78 1,86 1,42 0,94

Химия дефектов: Методические указания

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