Анализ, классификация и прогноз свойств гумусовых кислот (1098260), страница 29
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3&P =>+J ⋅ 3&P @>+J 2+ @ ⋅ >3&P @(7.2)]^_DJKP–dZ`msZykydhgklZglZmklhcqb\hklbdhfie_dkh\]mfmkh\uodbkehl k Hg(II) e/fhev JKP >+JJKP@ – jZ\gh\_kgZy dhgp_gljZpby +J,,k\yaZggh]h k ]mfmkh\ufb dbkehlZfb \ dhfie_dku fhev/e >JKP@ –dhgp_gljZpbyJKPfhevJKP/e< lZdhf ij_^klZ\e_gbb jZaf_jghklv dhgklZglu khhl\_lkl\m_ljZaf_jghklb dhgklZgl mklhcqb\hklb dhfie_dkh\ Hg(II) ih i_j\hc klmi_gbe/fhev) k gbadhfhe_dmeyjgufb eb]Zg^Zfb Wlh ^Z_l \hafh`ghklvkhihklZ\eylv ihemqZ_fu_ \_ebqbgu k dhgklZglZfb ^ey gbadhfhe_dmeyjguoeb]Zg^h\H[hkgh\Zgb_ ^himklbfhklb bkihevah\Zgby dZ`ms_cky dhgklZglu ^ey l_jfh^bgZfbq_kdhc oZjZdl_jbklbdb \aZbfh^_ckl\by f_lZee-=NDZ[[j_\bZlmjm =ND bkihevah\Zeb ^ey h[hagZq_gby ]mfmkh\uo dbkehl ijbaZibkbj_Zdpbckhhlghr_gbcdhgp_gljZpbcbl^\ebl_jZlmj_hlkmlkl\m_lIhwlhfm g_h[oh^bfh [ueh ihdZaZlv \aZbfhk\yav f_`^m dZ`ms_ckydhgklZglhc \ujZ`_gghc q_j_a JKP b fbdjhdhgklZglhcoZjZdl_jbamxs_cijbkh_^bg_gb_+J,,ddZ`^hfmJKPN L M K => O L M @>+J 2 + @ ⋅ >O L −1 K @(7.3)219]^_ Ni,j,h, – fbdjhdhgklZglZ oZjZdl_jbamxsZy h[jZah\Zgb_ M-cdhf[bgZpbb +Ji=ND ba K-c dhf[bgZpbb +Ji-1=ND Oi,j – j-Zy dhf[bgZpbyk\h[h^guobaZgyluop_gljh\\dhfie_dk_+Ji=NDIh^ JKP [m^_f ihgbfZlv dhf[bgZpbx fhe_dmeyjguo njZ]f_glh\]mfmkh\uodbkehlmqZkl\mxsbo\k\yau\Zgbbh^gh]hZlhfZjlmlbHgfh`_l\dexqZlv \ k_[y hl h^ghc ^h q_luj_o nmgdpbhgZevguo ]jmii Lh]^Z³kj_^gxx´fhe_dmem]mfmkh\uodbkehlbf_xsmxPp_gljh\k\yau\Zgbykhklmi_gqZlufb dhgklZglZfb .1...Km fh`gh ij_^klZ\blv dZd gZ[hj Pg_\aZbfhk\yaZgguo JKP Ijb \ur_ijb\_^_gghf hij_^_e_gbb JKP bodhebq_kl\h \ fhe_dme_ ]mfmkh\uo dbkehl khhl\_lkl\m_l fZdkbfZevghfmdhebq_kl\m Hg(II) dhlhjh_ fh`_l [ulv k\yaZgh ^Zgghc fhe_dmehc Djhf_lh]hqbkehJKPfh`ghlZd`_jZkkqblu\ZlvgZfZkkm]mfmkh\uodbkehllh]^Zwlh [m^_l fZdkbfZevgh_ dhebq_kl\h jlmlb dhlhjh_ fh`_l [ulv k\yaZgh k^ZgghcfZkkhc]mfmkh\uodbkehl>ey mklZgh\e_gby \aZbfhk\yab f_`^m dZ`ms_cky dhgklZglhc bfbdjhdhgklZglhc jZkkfhljbf ^\Z djZcgbo \ZjbZglZ jZkij_^_e_gby JKP \]mfmkh\uodbkehlZoihkbe_k\yau\Zgby1.
<k_JKPh^bgZdh\uh^ghjh^gh_jZkij_^_e_gb_1. Kms_kl\m_lg_kdhevdhlbih\JKPjZaghckbeuIjbwlhfhgbjZaebqZxlkygZklhevdh qlh aZiheg_gb_ p_gljh\ k\yau\Zgby L-]h lbiZ gZqbgZ_lky g_jZgvr_q_faZihegylky\k_[he__kbevgu_p_glju<ZjbZglJKP\]mfmkh\uodbkehlZojZ\ghp_ggu<wlhfkemqZ_\k_.JKPib^_glbqgubjZ\gu.JKPQlh[uk\yaZlvex[mxbawlbodhgklZglkfbdjhdhgklZglhc g_h[oh^bfh \ujZablv >+J.JKP@ b >JKP@ q_j_adhgp_gljZpbb]mfmkh\uodbkehl=NDbbodhfie_dkh\kHg(II):P>+J ⋅ 3&P @ = ∑ L ⋅ >+J L =N. @(7.4)L =1]^_i= 1… .m – qbkehJKP\fhe_dme_]mfmkh\uodbkehlP>3&P @ = ∑ P − L + 1 ⋅ >+J L −1=N.
@(7.5)L =1Ih^klZ\eyyb\ihemqZ_fP. 3&P =1>+J 2+ @⋅∑ L ⋅ >+J L =N.L =1P@∑ P − L + 1 ⋅ >+J L −1=N.L =1.(7.6)@<ujZabf>+Ji=ND@q_j_afbdjhdhgklZglm>eywlh]h\hkihevam_fky\ujZ`_gb_f ^ey h[s_c dhgklZglu mklhcqb\hklb dhfie_dkh\ ]mfmkh\uodbkehlkHg(II):βL =>+J L =N. @>+J 2 + @L ⋅ >=N. @(7.7)220>ZggZy dhgklZglZ y\ey_lky ijhba\_^_gb_f klmi_gqZluo dhgklZgl hl D1^hDiBkoh^ybawlh]hnZdlZfh`ghaZibkZlvqlh(7.8)βi = Cmi.ki]^_P–h[s__qbkehJKP\fhe_dme_Z& LP =P P − L ⋅ L (7.9)BamjZ\g_gbcbke_^m_lqlh[Hgi=ND@ &mi.ki.[Hg2+]i.>=ND@Ih^klZ\eyy\ihemqZ_f(7.10)P.
3&P =1>+J2+@⋅∑ L ⋅ & LP ⋅ N L ⋅ >+J @L ⋅ >=ND@L =1P∑ P − LL =1(7.11)P+ 1 ⋅ & L⋅NL⋅ >+J L@⋅ >=ND@Qlh[umijhklblvmjZ\g_gb_gm`ghkhdjZlblv>=ND@\qbkebl_e_bagZf_gZl_e_ \ug_klb N b >+J2+@ ba-ih^agZdZkmffu\qbkebl_e_bijh\_klbke_^mxs__ij_h[jZah\Zgb_(7.12)(m – i + 1).Cmi–1 = i.Cmi.Lh]^ZmjZ\g_gb_ijbh[j_lZ_lhq_gvijhklhc\b^.JKP = k(7.13)LZdbf h[jZahf ijb mkeh\bb jZ\ghp_gghklb \k_o JKP dZ`msZykydhgklZglZmklhcqb\hklbdhfie_dkh\]mfmkh\uodbkehlkHg(II)jZkkqblZggZygZ JKP hdZau\Z_lky b^_glbqghc fbdjhdhgklZgl_ oZjZdl_jbamxs_ck\yau\Zgb_ _^bgbqgh]h p_gljZ k Hg(II).
;he__ lh]h \_ebqbgZ ^ZgghcdhgklZglu g_ aZ\bkbl hl fheyjghc fZkku ]mfmkh\uo dbkehl Z agZqblhliZ^Z_l g_h[oh^bfhklv \ bkihevah\Zgbb ³kj_^g_c´ fhe_dmeyjghc fZkku]mfmkh\uodbkehlhijh[e_fZohij_^_e_gbydhlhjhc]h\hjbehkv\=eZ\_<ZjbZgl JKP \ =ND g_jZ\ghp_ggu < wlhf kemqZ_ jZkij_^_e_gb_+J,, k\yaZggh]h k ]mfmkh\ufb dbkehlZfb hij_^_ey_lky ke_^mxsbfijhp_kkhfHgi–1=ND + Hg2+ 4 Hgi=ND(7.14)Ijb wlhf fbdjhdhgklZglu jZaebqZxlky ^ey jZaguo lbih\ JKPIhwlhfm\h[s_fkemqZ_dZ`msZykydhgklZglZg_fh`_l[ulv\ujZ`_gZq_j_a fbdjhdhgklZglm L_f g_ f_g__ kms_kl\mxl kblmZpbb dh]^Z wlh\hafh`ghH^bg ba lZdbo kemqZ_\ – fZeZy kl_i_gv aZiheg_gby JKP ijb dhlhjhcqZklbqgh aZiheg_gu ebrv gZb[he__ kbevgu_ p_glju k\yau\Zgby L = 1).Wdki_jbf_glZevgh wlhl kemqZc ijhy\ey_lky \ lhf qlh dZ`msZyky dhgklZglZijZdlbq_kdbg_aZ\bkblhlkl_i_gbaZiheg_gbyJKPLh]^Z\aZbfh^_ckl\by\kbkl_f_=ND-+J,,k\h^ylkydj_Zdpbb221Hg2+ + JKP1 4+JJKP1(7.15)>Zgghcj_Zdpbbkhhl\_lkl\m_ldhgklZglZ.
3&P =1>+J ⋅ 3&P 1 @>+J 2+ @ ⋅ >3&P 1 @(7.16)<khhl\_lkl\bbk\udeZ^dZfb^ey\ZjbZglZh^bgZdh\uoJKPkf\ur_(7.17).JKP1) = k1,1lh_klv\_ebqbgZ.JKP y\ey_lkyl_jfh^bgZfbq_kdhcoZjZdl_jbklbdhcgZb[he__ kbevguo p_gljh\ k\yau\Zgby D kh`Ze_gbx gZ ijZdlbd_hij_^_e_gb_ >+JJKP1@ b >JKP1@ aZljm^g_gh ihwlhfm wdki_jbf_glZevgh^hklmighc \_ebqbghc fh`_l hdZaZlvky lhevdh dZ`msZyky dhgklZglZ K\y`_f__k.JKP1).Ba hij_^_e_gby .JKP mjZ\g_gby fZl_jbZevgh]h [ZeZgkZ bhij_^_e_gbykl_i_gbaZiheg_gbyJKP(7.18)θ = i/m]^_i – dhebq_kl\haZgyluoJKPm – h[s__dhebq_kl\hJKP\fhe_dme_]mfmkh\uodbkehlke_^m_lqlh. 3&P =θ>+J 2+ @ 1 − θ1⋅(7.19):gZeh]bqgh_mjZ\g_gb_fh`ghaZibkZlv^ey.JKP1<ujZ`Zybah[hbomjZ\g_gbc>+J2+@bijbjZ\gb\ZyboihemqZ_f.
3&P 1 θ 1 1 − θ=⋅. 3&P θ 1 − θ1(7.20)]^_θ1 –kl_i_gvaZiheg_gbyJKP1.DZd ijZ\beh wdki_jbf_glZevgh_ hij_^_e_gb_ θ1 aZljm^g_gh H^gZdh ba ke_^m_l qlh ijb ihklhygghc .JKP1 \ ^bZiZahg_ θ1< .JKPmf_gvrZ_lky\k_]hgZihjy^hdihke_q_]hijbθ1>gZqbgZ_lj_adhiZ^ZlvWlh hagZqZ_l qlh \ kemqZ_ _keb ijb fZeuo θ dZ`msZyky dhgklZglZmklhcqb\hklb]mfZlh\jlmlbmf_gvrZ_lkyf_gvr_q_fgZihjy^hdlhθ1 < 0.9.(7.21)K^jm]hcklhjhguijbfZeuoθ < kl_i_gyoaZiheg_gbyJKP1 – θ ≈ 1.(7.22)1Djhf_ lh]h _keb aZihegy_lky lhevdh JKP lh θ1 k\yaZgZ k θkhhlghr_gb_fθ1 = θ/δ1,(7.23)]^_δ1 –^heyJKP1\h[s_fdhebq_kl\_JKP(7.24)δ1 = KJKP1KJKP1< kemqZ_ _keb \ ^Zgghf ^bZiZahg_ θ aZihegy_lky lhevdh JKP fh`ghaZibkZlvqlh222(7.25)δ1 > θ,Ih^klZ\eyyb\bmqblu\ZyihemqZ_f(7.26).JKP1) < (10/θ)..JKP1Ijb wlhf \ dZq_kl\_ gb`g_c ]jZgbpu agZq_gby .JKP hklZ_lky\_ebqbgZ.JKPLZdbf h[jZahf dZ`msZyky dhgklZglZ iha\hey_l hp_gblv ]jZgbpuagZq_gby dhgklZglu k\yau\Zgby gZb[he__ kbevgh]h JKP b l_f kZfufhoZjZdl_jbah\Zlv_]hIjbwlhfg_h[oh^bfhkh[ex^_gb_ke_^mxsbomkeh\bc1.
θ < 0.12. < bkke_^m_fhf ^bZiZahg_ kl_i_g_c aZiheg_gby JKP dZ`msZykydhgklZglZ^he`gZbaf_gylvkyg_[he__q_fgZihjy^hdLh]^Z ]jZgbpu ^ey dhgklZglu k\yau\Zgby kZfh]h kbevgh]h JKPhij_^_eyxlkyke_^mxsbfg_jZ\_gkl\hf(7.27).JKP < .JKP1) < (10/θ)..JKP<ur_baeh`_ggh_ h[mkeh\eb\Z_l ieZgbjh\Zgb_ wdki_jbf_glZ ihhij_^_e_gbx dZ`msboky dhgklZgl <h-i_j\uo g_h[oh^bfh dhgljhebjh\ZlvoZjZdl_jaZ\bkbfhklbdZ`ms_ckydhgklZgluhlkl_i_gbaZiheg_gbyJKP<h\lhjuoqlh[ubkdexqblvmqZklb_[he__keZ[uof_lZeek\yau\Zxsbop_gljh\`_eZl_evgh bkihevah\Zlv lZdhc bgl_j\Ze θ qlh[u baf_g_gb_ dZ`ms_ckydhgklZglu \ wlhf bgl_j\Ze_ [ueh dZd fh`gh f_gvr_ D kh`Ze_gbxmf_gvr_gb_ bgl_j\ZeZ θ ijb\h^bl \ khhl\_lkl\bb k d m\_ebq_gbx^bZiZahgZ agZq_gbc .JKP1 qlh mom^rZ_l dZq_kl\h oZjZdl_jbklbdbk\yau\Zgby gZb[he__ kbevguo p_gljh\ k +J,, Baeh`_ggu_ iheh`_gbyfh`ghjZkijhkljZgblvbgZ^jm]b_f_lZeeu< k\yab k l_f qlh ijhlheblbq_kdb_ k\hckl\Z JKP2– gZfb g_bkke_^h\Zebkvlh\^Zevg_cr_fhij_^_eyebjG-mkeh\gmxdhgklZglmKJKPbkihevamyaZjy^JKPlhevdhijbdhjj_dlbjh\d_agZq_gbcdhgklZglgZbhggmxkbemjZkl\hjZihmjZ\g_gbx>w\bkZ7.1.1 Hij_^_e_gb_kh^_j`Zgbyjlmlv-k\yau\Zxsbop_gljh\\]mfmkh\uodbkehlZo>ey bkke_^h\Zgby dhfie_dkhh[jZamxsbo k\hckl\ ]mfmkh\uo dbkehl ihhlghr_gbx d Hg(II) bkihevah\Zeb \u[hjdm ba ij_iZjZlh\ jZaebqgh]hijhbkoh`^_gbybnjZdpbhggh]hkhklZ\ZdhlhjZy\dexqZeZ\k_[yJH<\h^5 =ND\h^=ND^hgguohleh`_gbc=Dm]ey=NDlhjnZ=Dihq\b=ND ihq\ >ey hij_^_e_gby kh^_j`Zgby JKP \ ]mfmkh\uo dbkehlZo [ueZbkihevah\ZgZ kihkh[ghklv jlmlb (II) h[jZah\u\Zlv g_jZkl\hjbfu_ ]mfZlu[Hgmnjb_ghdbKheh^h\gbdh\Z, 1961]Ij_^iheZ]Zehkvqlhkh^_j`Zgb_jlmlb\ gZkus_gguo ]mfZlZo khhl\_lkl\m_l kh^_j`Zgbx JKP Ihwlhfm ^ey223mklZgh\e_gby kh^_j`Zgby JKP \ jZkl\hjZo ]mfmkh\uo dbkehl gm`gh [uehkgZqZeZmklZgh\blvmkeh\byh[jZah\ZgbygZkus_gguo]mfZlh\jlmlbMkeh\byh[jZah\ZgbygZkus_gguo]mfZlh\+J,,Bamq_gb_mkeh\bch[jZah\Zgby g_jZkl\hjbfuo ]mfZlh\ hibkZgh \ khhl\_lkl\mxsboim[ebdZpbyo [@bebg b ^j @bebg b ^j 2000].
GZ i_j\hf wlZi_ijh\h^beb dZq_kl\_gguc wdki_jbf_gl p_ev dhlhjh]h [ueZ mklZgh\blvkhhlghr_gby Hg(II)f_lZee ijb dhlhjuo aZf_lgh \uiZ^_gb_ hkZ^dZg_jZkl\hjbfuo ]mfZlh\ >ey wlh]h d dhgp_gljbjh\Zgguf jZkl\hjZf =NDlhjnZ b ]e khhl\_lkl\_ggh ^h[Z\eyeb gZkus_gguc jZkl\hjHg(NO3)2 ^h ihegh]h \uiZ^_gby hdjZr_ggh]h \_s_kl\Z \ hkZ^hd Ijb wlhfgZ[ex^Zehkvihgb`_gb_jG^h-<h[hbokemqZyohkZ^dbbf_ebl_fghdhjbqg_\uc p\_l b juoemx kljmdlmjm :gZeba hkZ^dh\ ihdZaZe qlh \ gbokh^_j`blky fZkk b fZkk Hg Wlh ]h\hjbl h lhf qlh hkZ^dby\eyebkv]mfZlZfbjlmlbZg_=D\uiZ\rbfbijbaZdbke_gbbkj_^uaZkq_l]b^jhebaZ+J2+.<ukhdh_ kh^_j`Zgb_ jlmlb \ ihemq_gguo ]mfZlZo iha\hebehij_^iheh`blv qlh \ mdZaZgguo mkeh\byo h[jZamxlky ]mfZlu \ dhlhjuo \k_JKP aZiheg_gu Qlh[u ih^l\_j^blv wlh ij_^iheh`_gb_ [ueh ijh\_^_ghdhebq_kl\_ggh_bamq_gb_h[jZah\Zgbyg_jZkl\hjbfuo]mfZlh\jlmlb>ey wlhc p_eb ]hlh\beb jZkl\hju k jZaebqgufb khhlghr_gbyfb+J,,=ND ijb jG b bamqZeb jZkij_^_e_gb_ +J,, b =ND f_`^mjZkl\hjhf b h[jZamxsbfky hkZ^dhf Wdki_jbf_glu ijh\h^beb gZ ^\moij_iZjZlZo =ND lhjnZ Dhgp_gljZpbx jlmlb hij_^_eyeb f_lh^hf ::KOIIjbeh`_gb_dhgp_gljZpbx=ND–ki_dljhnhlhf_ljbq_kdb;ueh mklZgh\e_gh qlh ijb khhlghr_gbb Hg:=ND f_gvr_ 0.6 ffhev] \ aZ\bkbfhklb hl dhgp_gljZpbb =ND Hg(II) b ]mfmkh\u_dbkehlu hklZ\Zebkv \ jZkl\hj_ lh]^Z dZd ijb ij_\ur_gbb mdZaZggh]hkhhlghr_gby \ kbkl_f_ h[jZah\u\Zeky hkZ^hd ijb wlhf qZklv ]mfmkh\uodbkehl hklZ\ZeZkv \ jZkl\hj_ Ijb ^\mdjZlghf ij_\ur_gbb wlh]hkhhlghr_gby \k_ hdjZr_ggh_ \_s_kl\h iheghklvx \uiZ^Zeh \ hkZ^hd oh^khhl\_lkl\mxs_c aZ\bkbfhklb ihdZaZg gZ jbk Ke_^m_l aZf_lblv qlhg_kfhljy gZ rbjhdbc ^bZiZahg bkke_^h\Zgguo dhgp_gljZpbc ]mfmkh\uodbkehl -0.2 ]e oZjZdl_jgu_ khhlghr_gby Hg:=ND gZqZeZ \uiZ^_gbyhkZ^dZbihegh]h\uiZ^_gbyhdjZr_ggh]h\_s_kl\Zbaf_gyebkvg_[he__q_f\^\ZjZaZDhgp_gljZpby=ND\kmi_jgZlZgl_]e224:gZeblbq_kdZydhgp_gljZpby=ND]e&+Jf0Jbk 7.1.
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