Äîêóìåíò âçÿò èç êýøà ïîèñêîâîé ìàøèíû. Àäðåñ îðèãèíàëüíîãî äîêóìåíòà : http://chem.msu.ru/rus/journals/jvho/2006-3/104.pdf
Äàòà èçìåíåíèÿ: Mon Oct 2 16:13:10 2006
Äàòà èíäåêñèðîâàíèÿ: Sun Apr 10 19:24:31 2016
Êîäèðîâêà:
< N @bebg < E A[Zjkdbc


M>D

547.532+547.533:542.958.1

Kbgl_abl_ogheh]bygbljhijhba\h^guo[_gaheZblhemheZ

HJHB F_g^_e__\Z JOLM bf >B F_g^_e__\Z H[eZklv gZmqguo bgl_j_ kh\ obfby b l_ogheh]by gbljhkh_^bg_gbc EVB F_g^_e__\Z H[eZklv gZmqguo bgl_j_kh\ obfby b l_ogheh]by gbljhkh_^bg_gbc


Fhkd\Z FbmkkdZy ie ^ JOLM bf >BF_g^_e__\Z (-mail zbarsky@rctu.ru

Ihke_^gb_ ^_kylbe_lby OO \_dZ \ ijhba\h^kl\_ gbljhkh_^bg_gbc fh`gh hoZjZdl_jbah\Zlv q_ldhc l_g ^_gpb_c -- f_klh \aju\qZluo \_s_kl\ dhlhju_ \ l_q_ gb_ p_eh]h klhe_lby [ueb ]eZ\gufb ijh^mdlZfb wlhc hljZkeb aZgyeb kh_^bg_gby gZr_^rb_ rbjhdh_ ijbf_ g_gb_ \ ijhba\h^kl\_ ihebf_jguo fZl_jbZeh\ b e_dZj kl\_gguo \_s_kl\ Hkgh\ghc h[t_f \uimkdZ (4-- feg l \ ]h^ ijboh^blky gZ gbljhijhba\h^gu_ [_gah eZ b lhemheZ \ i_j\mx hq_j_^v gZ gbljh[_gahe b kf_kb bahf_jh\ ^bgbljhlhemheZ Wlb kh_^bg_gby klZeb ]eZ\ ghc kujv_\hc [Zahc ^ey ihemq_gby i_ghihebmj_lZgh\ -- h^ghc ba gZb[he__ [ukljh jZa\b\Zxsboky h[eZkl_c ijhfure_gghklb ihebf_jguo fZl_jbZeh\ Kbgl_a ZjhfZlbq_kdbo gbljhkh_^bg_gbc Hkgh\guf f_lh^hf ihemq_gby ZjhfZlbq_kdbo gbl jhkh_^bg_gbc \ ijhfure_gghklb y\ey_lky gbljh\Zgb_ m]e_\h^hjh^h\ Zahlghc dbkehlhc beb k_jgh-Zahlgufb dbkehlgufb kf_kyfb Gbljmxsbf Z]_glhf y\ey_lky gbljhgbc-bhg NO2+ dhlhjuc h[jZam_lky \ dhgp_gljb jh\Zgguo Zahlghc dbkehl_ b k_jgh-Zahlguo dbkehlguo kf_kyo>@
HNO3 + HNO3 HNO3 + H2SO
4

< jZa[Z\e_gguo \h^guo jZkl\hjZo Zahlghc dbkehlu b k_jgh-Zahlguo kf_k_c ]^_ dhgp_gljZpby gbljhgbcdZlbhgZ gbadZy b \ jy^_ kemqZ_\ hg ^Z`_ g_ h[gZjm`b \Z_lky ki_dljZevgufb f_lh^Zfb NO2+ hklZ_lky gbl jmxsbf we_dljhnbehf >@ _]h h[jZah\Zgb_ hibku\Z_l ky mjZ\g_gb_f KijZ\_^eb\hklv ihke_^g_]h mjZ\g_gby ih^l\_j`^Z _lky ohjhr_c dhjj_eypb_c f_`^m dhgklZglhc kdhjhklb gbljh\Zgby b nmgdpb_c dbkehlghklb ­HR ­ lga/20 \ 50--85%-ghc +123 b \ k_jgh-Zahlguo kf_kyo kh^_j `Zsbo f_g__ +2SO4 [3]. ;ueb ijh\_^_gu dbg_lbq_kdb_ bkke_^h\Zgby gbljh \Zgby [_gaheZ lhemheZ b gbljh[_gaheZ \ Zahlghc dbkeh l_ b k_jgh-Zahlguo kf_kyo lZ[e Ba ijb\_^_gguo \ lZ[e ^Zgguo \b^gh qlh ohly jZagbpZ \ \_ebqbgZo dhgklZgl kdhjhklb gbljh\Zgby [_gaheZ \ -ghc +123 b \ k_jgh-Zahlghc kf_kb k lZdbf `_ kh^_j`Zgb_f k_j ghc dbkehlu \_ebdZ gh hgZ agZqbl_evgh f_gvr_ q_f ijb gbljh\Zgbb \ -guo dbkehlZo Ke_^h\Zl_evgh \ Zahlghc dbkehl_ p_e_khh[jZagh ijh\h^blv gbljh\Zgb_ kh_^bg_gbc dhlhju_ e_]dh j_Z]bjmxl ijb dhgp_gljZ pbb +123 gb`_ Ijb gbljh\Zgbb gbljh[_gaheZ \ Zahlghc dbkehl_ \ dhgp_gljZpbb [ebadhc d b \
LZ[ebpZ


H3O+ + HNO3

NO2+ + 2H2O

NO2+ + NO3­ + H2O NO2+ + HSO4­ + H2O

DhgklZglu kdhjhkl_c gbljh\Zgby
;_gahe
4 4

[_gaheZ lhemheZ b gbljh[_gaheZ \ Zahlghc dbkehl_ ijb b k_jgh-Zahlguo dbkehlguo kf_kyo ijb °K > @ Lhemhe
4 2

°K

Gbljh[_gahe
HNO3, k 1· 105, H2SO4, k2· 105, ­1 efhevk % k % 100 99,5 99,0 98,3 97,5 96,2 468 354 276 204 157 77 98,0 95,0 90,3 86,7 83,7 81,8 2041 2917 4955 2042 299 77

HNO3, k1· 10 H2SH4, k2· 10 , HNO3,, k1· 10 H2SO4, k2· 10 ­1 % , % efhevk % k % efhevk ­1 k 65,3 67,1 68,1 69,0 70,0 70,9


2,76 7,45 12,5 20,5 36,6 58,4

63,2 65,5 68,2 70,6

12,7 61 480

65,3 67,1

55,8 132

63,2 65,5 7 5 ,3

2,1 11 2100 160000 1200000

4700

77,7 8 0 ,0
· 10 --5· 10
­4 ­2

Dhgp_gljZpby Zahlghc dbkehlu

fheve

104


Jhk obf ` @ Jhk obf h[-\Z bf >B F_g^_e__\Z
dhgp_gljbjh\Zgguo k_jgh-Zahlguo kf_kyo ^hklb]Zxlky kjZ\gbfu_ kdhjhklb gbljh\Zgby h^gZdh ^Z`_ ijb g_ agZqbl_evghf kgb`_gbb dhgp_gljZpbb +123 kdhjhklv j_Zdpbb j_adh iZ^Z_l ;he__ \ukhdZy kdhjhklv j_Zdpbb \ kj_^_ k_jghc dbkehlu hij_^_ebeZ ijbf_g_gb_ \ ijh fure_gghklb bkdexqbl_evgh k_jgh-Zahlguo dbkehlguo kf_k_c >@ H^gZdh \ -o ]h^Zo klZgh\blky ykgh qlh ijh fure_ggu_ ijhp_kku gbljh\Zgby \ dbkehlguo kf_kyo y\eyxlky bklhqgbdhf g_^himklbfh]h aZ]jyag_gby hdjm `Zxs_c kj_^u ijbf_kyfb h[jZamxsbfbky ijb gbljh \Zgbb b hkh[_ggh gZ klZ^bb j_]_g_jZpbb k_jghc dbkeh lu Djhf_ lh]h lj_[mxlky [hevrb_ wg_j]_lbq_kdb_ aZljZlu gZ klZ^bb j_]_g_jZpbb Qlh dZkZ_lky dZq_kl\Z ijh^mdlh\ ihemqZ_fuo ijb gbljh\Zgbb k_jgh-Zahlgufb dbkehlgufb kf_kyfb lh ih bahf_jghfm khklZ\m hgh g_ m^h\e_l\hjy_l ihlj_[ghklyf ijhfure_gghklb LZd ijb gbljh\Zgbb lhemheZ h[jZam _lky kf_kv D-, B- b E-bahf_jh\ \ khhlghr_gbb -- 65:4--5:35-- ba wlbo kh_^bg_gbc rbjhdh_ ijbf_g_ gb_ gZoh^bl lhevdh -gbljhlhemhe < l_ogbq_kdhf ^b gbljhlhemhe_ kh^_j`blky ^h ©f_lZ-bahf_jh\ª dh lhju_ g_h[oh^bfh m^Zeylv ^h klZ^bb nhk]_gbjh\Zgby \ ijhba\h^kl\_ bahpbZgZlh\ >@ :gZeh]bqgh_ iheh`_gb_ gZ[ex^Z_lky b \ ijhba\h^kl\_ ^bgbljh[_gaheZ l_ogb q_kdbc ijh^mdl kh^_j`bl --9% D-bahf_jZ b --2% E-bahf_jZ gZoh^ysbo h]jZgbq_ggh_ ijbf_g_gb_ LZd dZd khhlghr_gb_ bahf_jh\ hij_^_ey_lky \ i_j \mx hq_j_^v jZkij_^_e_gb_f aZjy^h\ \ bkoh^ghc ZjhfZ lbq_kdhc fhe_dme_ l_ l_jfh^bgZfbq_kdbfb iZjZf_l jZfb lh baf_g_gb_ mkeh\bc gbljh\Zgby ijb khojZg_



l L 3

gbb ijbjh^u gbljmxs_]h Z]_glZ g_ kbevgh \eby_l gZ _]h \_ebqbgm Bamq_gb_ khklZ\Z ijh^mdlh\ gbljh\Zgby lhemheZ ijb bkihevah\Zgbb jZaebqguo gbljmxsbo kbk l_f lZ[e ihdZaZeh qlh g_kfhljy gZ djZcgb_ jZaeb qby \ ijbjh^_ iheyjghklb jZkl\hjbl_e_c b gbljmx sbo Z]_glh\ -- hl kheb gbljhgby ^h gbljhwnbjh\ kh ^_j`Zgb_ B-bahf_jZ baf_gy_lky keZ[h Ijb wlhf ^ey [hevrbgkl\Z bamq_gguo j_Zdpbhgguo kbkl_f g_ lhevdh kh^_j`Zgb_ B-bahf_jZ gh b hlghr_gb_ D-/E-bahf_jh\ khojZgy_lky \ madbo ij_^_eZo Iheh`_gb_ baf_gy_lky ijb i_j_oh^_ d ijbgpbib Zevgh bguf gbljmxsbf j_Z]_glZf LZd ijb gbljh\Z gbb lhemheZ [_a\h^gufb gbljZlZfb i_j_oh^guo f_lZe eh\ \ kj_^_ KK4 kh^_j`Zgb_ B-bahf_jZ kgb`Z_lky ^h Z lZd`_ ihemqZ_lky kms_kl\_ggh bgh_ khhlghr_gb_ D- b E-bahf_jh\ -- hgh \ ljb jZaZ gb`_ q_f \ [hevrbg kl\_ hklZevguo ijb\_^_gguo ijbf_jh\. G_h[uqgh_ ijhl_dZgb_ gbljh\Zgby gbljZlZfb f_ lZeeh\ hkh[_ggh q_ldh ijhy\ey_lky \ j_Zdpbb k gbljZ lhf iZeeZ^by < wlhf kemqZ_ hlghr_gb_ bahf_jh\ fh ghgbljhlhemheZ D- : B- : E- = 1 : 4,3 : 5. :ghfZevgh_ ih\_^_gb_ JG1H3)2 ijb gbljh\Zgbb h[tykgyxl \ha fh`ghklvx ijhl_dZgby j_Zdpbb iZeeZ^bjh\Zgby Kbevgh_ \ebygb_ ohly b g_h^ghagZqgh_ hdZau\Zxl g_iheyjgu_ jZkl\hjbl_eb &&O4, C6H14 gZ gbljh\Zgb_ lhemheZ Zp_lbegbljZlhf < KKO4 ijb K \uoh^ D-, Bb E-bahf_jh\ khklZ\ey_l khhl\_lkl\_ggh b \j_fy j_Zdpbb q < kj_^_ ]_dkZgZ \uoh^ B-bahf_jZ ^hklb]Z_l >@ ?s_ h^ghc ijbf_kvx ihemqZ_fhc ijb gbljh\Zgbb [_gaheZ b lhemheZ \ agZqbl_evguo dhebq_kl\Zo y\eyxl

LZ[ebpZ
Bahf_jguc khklZ\ fhghgbljhlhemheZ \ aZ\bkbfhklb hl mkeh\bc gbljh\Zgby Gbljmxsbc Z]_gl
HNO3 HNO3, 13,7% NO2 BF HNO3 CH3COONO2 CH3ONO2 NNN+ ­ 4
>@

DZlZebaZlhj Zdlb\bjmxs__ \ha^_ckl\b_
-- --

Kj_^Z

Bahf_jguc khklZ\ hjlh-



f_lZ4 ,3 3,9

iZjZ-

-- H2SO4, 64,4% -- H2SO4 -- BF
3

CH3NO2

66 62 61 63 58 58 66 64 46 43 42 37 62--64

3 3 2 3 3 3 5 2 2 2,3 39 38 3,1--4,5

31 35 37 34 39 39 29 34 52 55 19 25 32--34,5

KmevnheZg
CH3CN CH3NO2

GbljhibjZahe GbljhibjZahe Gbljhibjb^bgby cheb
4 4

KH3
[8] -- BF --
3

SO3H

CH2Cl CH2Cl

2 2

FSO3H

CH3CN CH3NO2 CCl CCl
4 4

C(NO2)

Zr(NO3)

Cu(NO3)2 [9]

(CH3CO)2O


KaS

O4· 1/2H2O: HNO3 7 : 1
4

fhe

-- 300 °C

Lhemhe
CH2Cl
2

C(NO2) N2O4

N2O4 [10]

H[emq_gb_ We_dljhobfbq_kdh_ h[emq_gb_

CH3CN

105


< N @bebg < E A[Zjkdbc


ky ihebgbljhn_gheu Bo h[jZah\Zgb_ y\ey_lky kdhj__ \k_]h j_amevlZlhf bikh-ijbkh_^bg_gby bhgZ gbljhgby Ih ^Zgguf R_nbev^Z ijb gbljh\Zgbb lhemheZ \_jhyl ghklv h[jZah\Zgby -f_lbe-1-gbljh[_gahehgb_\h]h bhgZ \ur_ q_f B-gbljhlhemheZ :lZdZ ihemq_ggh]h bhgZ ­ gmde_hnbevgufb Z]_glZfb G2H, NO3 k ihke_^mxsbf hls_ie_gb_f 122 ijb\h^bl d h[jZah\Zgbx dj_aheZ e_]dh gbljm_fh]h \ wlbo mkeh\byo M^Ze_gb_ gbljhdj_ aheh\ lZd`_ lj_[m_l [hevrbo aZljZl LZdbf h[jZahf ljZ^bpbhggu_ f_lh^u g_ iha\heyxl j_rblv aZ^Zqb jZajZ[hldb \ukhdhijhba\h^bl_evguo ijhp_kkh\ ihemq_gby gbljhkh_^bg_gbc [_a bkihevah\Z gby k_jghc dbkehlu b f_lh^h\ kbgl_aZ gbljhkh_^bg_gbc k ij_bfms_kl\_gguf h[jZah\Zgb_f lj_[m_fh]h bahf_jZ

DZlZeblbq_kdh_ gbljh\Zgb_ [_gaheZ b lhemheZ
Gbljh\Zgb_ ZjhfZlbq_kdbo m]e_\h^hjh^h\ \ ijbkml kl\bb ]_l_jh]_gguo dZlZebaZlhjh\ iha\hey_l hldZaZlvky hl ijbf_g_gby k_jghc dbkehlu \ ijhfure_gguo ijh p_kkZo b h[_ki_qb\Z_l \hafh`ghklv j_]mebjh\Zgby bah f_jgh]h khklZ\Z ihemqZ_fuo gbljhijh^mdlh\ AZ ih ke_^gb_ e_l him[ebdh\Zgh fgh`_kl\h jZ[hl ih wlhfm gZijZ\e_gbx Z[khexlgh_ [hevrbgkl\h ba dhlhjuo ihk\ys_gh gbljh\Zgbx gZ l\_j^hnZaguo dZlZebaZlhjZo 12].

Gbljh\Zgb_ hdkb^Zfb ZahlZ

< ihke_^gb_ ]h^u hkh[h_ \gbfZgb_ m^_eyxl gbljh \Zgbx [_gaheZ hdkb^Zfb ZahlZ :\lhju fgh]bo jZ[hl ml\_j`^Zxl qlh ^ey lZdbo ijhp_kkh\ bkdexqZ_lky g_ h[oh^bfhklv \ klZ^bb j_]_g_jZpbb dbkehl wlhl ihklm eZl g_ \iheg_ kljh] lZd dZd \ oh^_ gbljh\Zgby h[jZam _lky ZahlgZy dbkehlZ < --50-_ ]h^u OO \_dZ :< Lhiqb_\ mklZgh\be qlh [_gahe gbljm_lky ^bhdkb^hf ZahlZ \ kj_^_ m]e_db keh]h ]ZaZ dZd [_a h[emq_gby lZd b ijb h[emq_gbb mevl jZnbhe_lh\uf k\_lhf \uoh^ gbljh[_gaheZ gbadbc H[emq_gb_ mevljZnbhe_lh\uf k\_lhf ijb gbljh\Zgbb lhemheZ kihkh[kl\m_l aZf_s_gbx \ [hdh\hc p_ib -- h[jZam_lky n_gbegbljhf_lZg Iha`_ \ gZqZe_ -o ]h^h\ [ueh ihdZaZgh qlh gbljh\Zgb_ [_gaheZ ^bhdkb ^hf ZahlZ [he__ mki_rgh ijhl_dZ_l \ ijbkmlkl\bb db kehjh^Z ijbq_f ^ey h[_ki_q_gby \ukhdh]h \uoh^Z gbljh[_gaheZ g_h[oh^bf [hevrhc ba[ulhd ^bhdkb^Z ZahlZ b dbkehjh^Z >13@ Jy^ klZl_c b iZl_glh\ Kmamdb b ^j ihk\ys_g gbljh\Zgbx ZjhfZlbq_kdbo m]e_\h^hjh

^h\ ^bhdkb^hf ZahlZ \ kj_^_ hj]Zgbq_kdh]h jZkl\hjbl_ ey k bkihevah\Zgb_f hahgZ \ dZq_kl\_ hdbkebl_ey gbl jhkh_^bg_gby ihemqZxlky k ohjhrbf \uoh^hf >14]. J_axfbjmy j_amevlZlu jZ[hl ih gbljh\Zgbx ZjhfZ lbq_kdbo m]e_\h^hjh^h\ hdkb^Zfb ZahlZ ,9 b 9 [_a jZkl\hjbl_ey \ kj_^_ hj]Zgbq_kdbo jZkl\hjbl_e_c b \ kj_^_ \h^guo dbkehl fh`gh aZdexqblv qlh j_Zdpbb ijhl_dZxl ^\hydh < dhgp_gljbjh\Zgghc k_jghc b Zahl ghc dbkehlZo Z lZd`_ \ iheyjguo jZkl\hjbl_eyo hdkb^u ZahlZ h[jZamxl gbljhgbc- beb gbljhgbc- b gbljhahgbcbhgu Z \ g_iheyjguo jZkl\hjbl_eyo lbiZ KK4 hdkb^u ZahlZ gZoh^ylky \ dh\Ze_glghc nhjf_ b j_Zdpby b^_l k mqZklb_f k\h[h^guo jZ^bdZeh\ < h^ghc ba i_j\uo jZ[hl FZd-.b ih gbljh\Zgbx ZjhfZlbq_kdbo kh_^bg_gbc hdkb^Zfb ZahlZ k bkihevah \Zgb_f l\_j^hnZaguo dZlZebaZlhjh\ [ueh mklZgh\e_gh qlh kbebdZ]_ev dZlZebabjm_l gbljh\Zgb_ [_gaheZ hdkb ^Zfb ZahlZ ijb l_fi_jZlmj_ ^h K \uoh^ gbljh[_g aheZ hq_gv \ukhdbc ^h ijb l_fi_jZlmj_ \ur_ 330 K hkgh\guf ijh^mdlhf j_Zdpbb klZgh\blky gbljh n_ghe Ij_^iheh`_gb_ h lhf qlh dZlZeba hij_^_ey_lky ^_]b^jZlbjmxsbfb k\hckl\Zfb kbebdZ]_ey [ueh hijh \_j]gmlh \ hiulZo k ^jm]bfb ^_]b^jZlbjmxsbfb dZlZ ebaZlhjZfb hdkb^u f_^b Zexfbgby fZ]gby k bo mqZklb_f dZlZeba g_ gZ[ex^Zeky J_amevlZlu wlbo bk ke_^h\Zgbc kms_kl\_ggh hlebqZebkv hl ^Zgguo ihem q_gguo II Rhju]bguf b :< Lhiqb_\uf ih gbljh \Zgbx ZjhfZlbq_kdbo m]e_\h^hjh^h\ \ ZgZeh]bqguo mkeh\byo hdkb^Zfb ZahlZ [_a dZlZebaZlhjZ dZd ih kdh jhklb ijhp_kkZ lZd b ih ^he_ ih[hqguo j_Zdpbc >Zevg_crb_ jZ[hlu ih gbljh\Zgbx [_gaheZ hdkb^Z fb ZahlZ gZ l\_j^uo dZlZebaZlhjZo gZreb hljZ`_gb_ ]eZ\guf h[jZahf \ iZl_glghc ebl_jZlmj_ Hkgh\guf h[t_dlhf bkke_^h\Zgbc [ueb aZf_s_ggu_ [_gaheu lZd dZd dZlZeblbq_kdh_ ^_ckl\b_ kdZau\Zehkv ij_bfms_kl \_ggh gZ bahf_jghf khklZ\_ ijh^mdlh\ gbljh\Zgby \ i_j\mx hq_j_^v gZ khhlghr_gbb D- b E-bahf_jh\ < jy^_ jZ[hl ihdZaZgh qlh ijb jZaf_j_ ihj dZlZebaZlhjZ 0,52--0,56 gf \ ijh^mdlZo j_Zdpbb kgb`Z_lky kh^_j`Z gb_ D- b B-aZf_s_gguo >15]. L_f g_ f_g__ qZklv bkke_^h\Zgbc [ueZ ihk\ys_gZ gbljh\Zgbx [_gaheZ Ijb gbljh\Zgbb [_gaheZ ^bhdkb ^hf ZahlZ 12O4 \ iZjh\hc nZa_ k bkihevah\Zgb_f \ dZq_kl\_ dZlZebaZlhjZ p_heblZ +-ZSM- h[jZam_lky gbljh[_gahe k k_e_dlb\ghklvx ijb kl_i_gb dhg \_jkbb Gbljh\Zlv [_gahe ]Zahh[jZaguf ^bhdkb^hf ZahlZ p_e_khh[jZagh \ ijbkmlkl\bb dbkehjh^Z b g_hj]Zgbq_ kdbo hdkb^h\ dZd dZlZebaZlhjh\ Bkihevah\Zebkv jZa ebqgu_ p_heblu kbebdZ]_ev -hdkb^ Zexfbgby b ^jm ]b_ ijbjh^gu_ b kbgl_lbq_kdb_ hdkb^u k m^_evghc ih 2 \_joghklvx [he__ f ] b jZaf_jhf ihj [he__ gf Ihke_^g__ lj_[h\Zgb_ h[mkeh\e_gh kihkh[ghklvx Zjh fZlbq_kdbo fhe_dme khj[bjh\Zlvky \gmljb ihj Ijhp_kk ijh\h^beb ijb ih\ur_gghf ^Z\e_gbb dbkehjh^Z q_f j_Zdpbhgghkihkh[g__ kh_^bg_gb_ l_f gb`_ ^Z\e_gb_ Gbljh\Zgb_ [_gaheZ ^bhdkb^hf ZahlZ ba jZkq_lZ gZ 1 fhev K6G6 2 fhev NO2 ijb ^Z\e_gbb dbkehjh^Z

106


Jhk obf ` @ Jhk obf h[-\Z bf > B F_g^_e__\Z




l



L





3

0,28 FIZ b l_fi_jZlmj_ K aZ q ijhl_dZ_l [he__ q_f gZ >16]. Ohjhrbf dZlZebaZlhjhf iZjhnZagh]h gbljh\Zgby hdZaZeky kbebdZ]_ev ijhiblZgguc [_gahekmevnhgh\hc dbkehlhc
IZjhnZagh_ gbljh\Zgb_ Zahlghc dbkehlhc

G_ f_gvrbc bgl_j_k ij_^klZ\ey_l dZlZeblbq_kdh_ gbljh\Zgb_ iZjZfb Zahlghc dbkehlu jZaebqghc dhgp_g ljZpbb Ijb bkihevah\Zgbb \h^guo jZkl\hjh\ +123 fh`gh h`b^Zlv agZqbl_evgh]h kgb`_gby \aZbfh^_ckl \by f_`^m fhe_dmeZfb \h^u b Zahlghc dbkehlu ijb i_j_oh^_ \ ]Zah\mx nZam Ke_^h\Zl_evgh ^he`_g h[e_] qZlvky ijhp_kk ij_\jZs_gby +123 \ Zdlb\guc gbl jmxsbc Z]_gl gZ dbkehlguo p_gljZo dZlZebaZlhjZ b \hafh`gh [he__ ihegh_ bkihevah\Zgb_ dbkehlu I_j\u_ im[ebdZpbb ih gbljh\Zgbx ZjhfZlbq_kdbo m]e_\h^hjh^h\ iZjZfb +123 gZ l\_j^uo dZlZebaZlhjZo ihy\bebkv \ k_j_^bg_ -o ]h^h\ ijhreh]h klhe_lby G_kfhljy gZ [hevrh_ qbkeh im[ebdZpbc b hkh[_ggh iZl_glh\ ih wlhc l_fZlbd_ k\_^_gby h ijhfure_gghf bkihevah\Zgbb f_lh^Z hlkmlkl\mxl ohly _klv khh[s_ gb_ h ^_fhgkljZpbhgghc mklZgh\d_ nbjfu ©6XPLWRPRª \ Yihgbb < dZq_kl\_ dZlZebaZlhjh\ \ wlhf ijhp_kk_ [ueb bk ihevah\Zgu jZaebqgu_ fZl_jbZeu ijbjh^gu_ Zexfh kbebdZlu fhglfhjbeehgbl [_glhgbl p_heblu k gba dbf kh^_j`Zgb_f $O2O3 6L $O ! kf_rZggu_ hdkb ^u f_lZeeh\ ij_bfms_kl\_ggh ,9 b 9, ]jmii gZijb f_j :23--ZrO2 Hkh[uc bgl_j_k m^_ey_lky hdkb^Zf ijhiblZgguf dbkehlZfb -- SiO2/H2SO4, TiO2/H2SO4, ZrO2/H2SO4 dhlhju_ y\eyxlky k\_jodbkehlZfb nmgd pby =Zff_lZ /0 ^h ­16). < ijbkmlkl\bb ZexfhkbebdZlguo dZlZebaZlhjh\ kdhjhklv gbljh\Zgby j_adh \hajZklZ_l M\_ebq_gbx kdhjhklb gbljh\Zgby aZf_s_gguo ZjhfZlbq_kdbo kh _^bg_gbc lhemhe dkbeheu kihkh[kl\m_l \\_^_gb_ \ j_Zdpbhggmx kbkl_fm g_[hevrh]h dhebq_kl\Z [_a\h^gh ]h &D624 beb &D2 >@ ;hevrb_ mki_ob ^hklb]gmlu ijb bkihevah\Zgbb hdkb^guo dZlZebaZlhjh\ h[jZ[hlZgguo dbkehlZfb :dlb\ghklv dZlZebaZlhjZ khklZ\Z 10% H2SO4 gZ 6L22 ijb iZjhnZaghf gbljh\Zgbb [_gaheZ jZa[Z\e_g ghc Zahlghc dbkehlhc ih^^_j`b\ZeZkv \ l_q_gb_ ^eb l_evgh]h \j_f_gb [he__ ^\mo f_kyp_\ iml_f \\_^_gby ke_^h\uo dhebq_kl\ +2SO4 \ bkoh^gmx Zahlgmx dbkehlm (H2SO4 : HNO3 ih fZkk_ :gZeh]bqgu_ dZlZ ebaZlhju gZ hkgh\_ hdkb^h\ 6L22 b $O2O3 ijhiblZgguo H2SO4 beb +3PO4 b kh^_j`Zsb_ ^h[Z\db khe_c wlbo dbkehl iha\heyxl \_klb gbljh\Zgb_ lhemheZ Zahlghc

dbkehlhc \ iZjh\hc nZa_ ijb --180 K b ihgb`_gghf ^Z\e_gbb 18]. Wnn_dlb\guf dZlZebaZlhjhf gbljh\Zgby y\ey_lky kf_kv hdkb^h\ :23 b 0R23 gZg_k_ggZy gZ fhglfhjbe ehgbl DZlZebaZlhj kh^_j`Zsbc kf_kv hdkb^h\ 7L22 b FR22 h[jZ[hlZggmx k_jghc dbkehlhc ijb K ^Z_l \uoh^ gbljh[_gaheZ ijb \j_f_gb jZ[hlu [he__ 528 q :dlb\ghklv dZlZebaZlhjZ gZ hkgh\_ kf_rZgguo hdkb^h\ 7L22 b =U22 h[jZ[hlZgguo k_jghc dbkehlhc ijb K ijb iZjhnZaghf gbljh\Zgbb [_gaheZ keZ[hc Zahlghc dbkehlhc fh`gh ih\ukblv iml_f qZklbqghc g_cljZebaZpbb ]_l_jhihebdbkehl kheyfb &V beb 7O Wnn_dlb\guf dZlZebaZlhjhf gbljh\Zgby [_gaheZ y\ey _lky lZd`_ kf_kv hdkb^h\ :23/ZrO2 = 15/85 fZkk Ijb 170 K b \j_f_gb dhglZdlZ k \uoh^ gbljh[_gaheZ ih Zahlghc dbkehl_ \aylhc \ g_^hklZld_ khklZ\be G_h`b^Zgguf hdZaZehkv qlh kmevnZlbjh\Zgb_ wlh]h dZlZebaZlhjZ kgb`Z_l _]h dZlZeblbq_kdbc wnn_dl Ijh ba\h^bl_evghklv dZlZebaZlhjZ :23/ZrO2 ijb K khklZ\beZ ] [_gaheZ] dZlZebaZlhjZ Z khklZ\Z 5%SO4/15%WO3/80%ZrO2 -- 0,32Â0,52 ]] Ijb gbljh \Zgbb gZ G-fhj^_gbl_ [ueZ ^hklb]gmlZ ijhba\h^bl_ev ghklv ]] dZlZebaZlhjZ Z gZ ^_Zexfbgbjh\Zgghf p_hebl_ +< -- 0,91 ]] GZ \k_o dZlZebaZlhjZo ijhp_kk b^_l ijZdlbq_kdb [_a ih[hqguo j_Zdpbc >19]. DZd ij_^iheZ]Z_l [hevrbgkl\h bkke_^h\Zl_e_c ih^h[gh gbljh\Zgbx \ `b^dbo kj_^Zo j_Zdpby \ ]Zah\hc nZa_ ijhl_dZ_l k mqZklb_f gbljhgbc-bhgZ dhlhjuc h[jZam_lky gZ dbkehlguo p_gljZo dZlZebaZlhjZ dZlZeb lbq_kdhc Zdlb\ghklvx h[eZ^Zxl dZd evxbkh\kdb_ lZd b [jzgkl_^h\kdb_ p_glju dbkehlghklb

@b^dhnZagh_ gbljh\Zgb_ Zahlghc dbkehlhc

H^ghc ba i_j\uo jZ[hl ih dZlZeblbq_kdhfm gbljh \Zgbx \ `b^dhc nZa_ [ue iZl_gl >20@ \ dhlhjhf ij_^ eh`_gh ijh\h^blv gbljh\Zgb_ ZjhfZlbq_kdbo m]e_\h^h jh^h\ Zahlghc dbkehlhc k dZlZebaZlhjhf gZ hkgh\_ ZexfhkbebdZlh\ beb $O2O3 ijhiblZgguo +2SO4 beb H3PO4 =hlh\uc dZlZebaZlhj kh^_j`Ze ^h +2SO4. Ijhp_kk gbljh\Zgby \_eb ijb K \ jZkl\hj_ K+2Cl2, bkihevamy \ dZq_kl\_ gbljmxs_]h Z]_glZ --90% HNO3 < \u[jZgguo mkeh\byo [_gahe b lhemhe ij_\jZ sZebkv \ khhl\_lkl\mxsb_ gbljhkh_^bg_gby k \uoh^hf 98-- f_g__ q_f aZ q ij_[u\Zgby \ j_Zdlhj_ < ijh^mdlZo g_ [ueb h[gZjm`_gu dZdb_-eb[h ^bgbljhkh_ ^bg_gby < jZ[hlZo ijh\h^bfuo \ Gh\hkb[bjkdhf bgklblml_ hj]Zgbq_kdhc obfbb >21], ZjhfZlbq_kdb_ kh_^bg_gby gbljh\Zeb Zahlghc dbkehlhc gZg_k_gghc gZ p_hebl lbiZ i_glZkbeZ J_Zdpbx ijh\h^beb \ kj_^_ ]_dkZgZ ijb 25 K IhdZaZgh qlh \ wlbo mkeh\byo ijhoh^bl gbljh\Z gb_ lhemheZ [_gaheZ b oehj[_gaheZ dhlhjh_ \ hlkmlkl \b_ dZlZebaZlhjZ ijhl_dZ_l hq_gv f_^e_ggh Hlghr_gb_ kdhjhkl_c j_Zdpbc jZ\gh H[rbjgh_ bkke_^h\Zgb_ ih gbljh\Zgbx lhemheZ b D-dkbeheZ -ghc +123 \ kj_^_ KK4 ijh\_^_gh Kdm ibgkdbf k khlj >@ < dZq_kl\_ dZlZebaZlhjh\ bkihev

107


< N @bebg < E A[Zjkdbc


ah\Zeb hdkb^u f_lZeeh\ :23, V2O5, TiO2, MoO3 gZg_ k_ggu_ gZ kbebdZ]_ev DZlZebaZlhj \\h^beky \ j_Zdpb hggmx kbkl_fm \ -djZlghf ba[uld_ ih fZkk_ MklZ gh\e_gh qlh dZlZebaZlhj 0R23/SiO2 dbkehlghklv dhlh jh]h khhl\_lkl\h\ZeZ -ghc +2SO4 mkdhjy_l gbljh \Zgb_ ih kjZ\g_gbx k kbkl_fhc [_a dZlZebaZlhjZ \ lh \j_fy dZd hklZevgu_ dZlZebaZlhju dbkehlghklv dhlh juo [ebadZ d -ghc +2SO4 aZf_^eyxl ijhp_kk Kbevgh_ \ebygb_ gZ ijhp_kk hdZau\Z_l dZlZebaZlhj 15% TiO2/SiO2 k ^h[Z\dZfb :23. Ijb bkihevah\Zgbb dZlZebaZlhjh\ m\_ebqb\Z_lky ^hey gbljh\Zgby \ ijhkljZgkl\_ggh f_g__ aZljm^g_ggh_ iheh `_gb_ \ E-iheh`_gb_ \ lhemhe_ b \ -iheh`_gb_ \ D-dkbehe_ Wlh kem`bl hkgh\Zgb_f ^ey ml\_j`^_gby qlh j_Zdpby ijhl_dZ_l gZ ih\_joghklb dZlZebaZlhjZ Ke_^m_l hlf_lblv kbevgh_ \ebygb_ 0R23/SiO2 gZ \uoh^ ijh^md lh\ bikh-aZf_s_gby ijb gbljh\Zgbb D-dkbeheZ h[jZam _lky --8,5% D-gbljhlhemheZ \ _]h hlkmlkl\b_ -- 4%. P_heblgu_ dZlZebaZlhju ij_^klZ\eyxl hkh[uc bg l_j_k ^ey k_e_dlb\gh]h ihemq_gby E-gbljhlhemheZ Ijb gbljh\Zgbb lhemheZ Zahlghc dbkehlhc khklZ\ ijh^mdlh\ j_Zdpbb hij_^_ey_lky ]_hf_ljbq_kdhc kljmdlmjhc dZlZ ebaZlhjZ :dlb\ghklv p_heblh\ k madbfb b ^ebggufb h^ghf_jgufb dZgZeZfb G-fhj^_gbl [ukljh iZ^Z_l ihkdhevdm gZdhie_gb_ ijh^mdlh\ j_Zdpbb \ dZgZeZo ijb\h^bl d aZljm^g_gbx ^hklmiZ j_Z]_glh\ \h \gmlj_g gxx ih\_joghklv p_heblZ P_heblu k jZa\_l\e_gghc lj_of_jghc kbkl_fhc dZgZeh\ gZijbf_j p_hebl H-;_lZ ijhy\eyxl klZ[bevgmx Zdlb\ghklv b k_e_dlb\ ghklv gZ ijhly`_gbb --10 q jZ[hlu Kj_^gbc ^bZf_lj ihj p_heblZ G-;_lZ --0,8 gf qlh [hevr_ jZaf_jZ fhe_dmeu E-gbljhlhemheZ gh f_gvr_ jZaf_jh\ fhe_dme D-gbljhlhemheZ B-gbljhlhemheZ b ^bgbljhlhemheZ Ih\ur_gb_ k_e_dlb\ghklb gbljh\Zgby lhemheZ gZ p_h ebl_ G-;_lZ ^h b [he__ ijhbkoh^bl aZ kq_l m^_j`b \Zgby h[t_fguo ijh^mdlh\ \ ihjZo dZlZebaZlhjZ qlh d kh`Ze_gbx \uau\Z_l _]h ^_aZdlb\Zpbx KjZ\g_gb_ kdhjhkl_c j_Zdpbb \ ijbkmlkl\bb dZlZeb aZlhjh\ b [_a g_]h ihdZaZeh qlh b ijb bkihevah\Zgbb [hevrh]h ba[uldZ Zahlghc dbkehlu --16 fhev gZ 1 fhev lhemheZ dh]^Z ijh^mdlhf j_Zdpbb klZgh\blky ^bgbljhlhemhe 0R23/SiO2 lZd`_ kbevgh \eby_l gZ ijh p_kk gbljh\Zgby Ijb dhfgZlghc l_fi_jZlmj_ \ _]h ijbkmlkl\bb ^bgbljhlhemhe h[jZam_lky k \uoh^hf m`_ q_j_a fbg Z [_a dZlZebaZlhjZ \uoh^ wlh]h ijh ^mdlZ q_j_a q jZ\_g Bahf_jguc khklZ\ ^bgbljh lhemheZ baf_gy_lky g_agZqbl_evgh < >23@ ijh\_eb gbljh\Zgb_ jy^Z kh_^bg_gbc k ihgb `_gghc j_Zdpbhgghc kihkh[ghklvx gbljh[_gahe 9,10-ZgljZobghg ijb & \ kj_^_ KKO4 dhgp_gljbjh \Zgghc Zahlghc dbkehlhc \ ijbkmlkl\bb =U22 fh^bnb pbjh\Zggh]h kmevnZl-bhghf :\lhju ml\_j`^Zxl qlh 2­ 2­ kbkl_fu =U22/SO4 b 6Q22/SO4 y\eyxlky gZb[he__ kbevgufb ba l\_j^uo dbkehl /0 f_g__ ­ b wlbf h[tykgyxl bo dZlZeblbq_kdh_ ^_ckl\b_ Ijb gbljh\Zgbb lhemheZ Zahlghc dbkehlhc ^ey ih 2­ \ur_gby E-k_e_dlb\ghklb dZlZebaZlhjZ =U22/SO4 _]h

ghc dbkehlu \ dZlZebaZlhj_ ijbq_f k jhklhf kh^_j`Z gby +2SO4 \_ebqbgZ kgZ[e mf_gvrZ_lky :gZeh]bqgh_ y\e_gb_ gZ[ex^Z_lky ijb ih\ur_gbb dhgp_gljZpbb k_jghc dbkehlu hl ^h \ k_jgh-Zahlguo db kehlguo kf_kyo Ijb wlhf hlghr_gb_ dhgklZgl j_Zdpbc gbljh\Zgby aZf_s_ggh]h b g_aZf_s_ggh]h ZjhfZlbq_ kdbo kh_^bg_gbc k l\_j^uf dZlZebaZlhjhf [ebadh d bo hlghr_gbx ijb gbljh\Zgbb k_jgh-Zahlghc dbkehlghc kf_kvx
k
gZ[e
ArX

ih\_joghklv ihdju\Zeb keh_f iheb\bgbeh\h]h kibjlZ h[eZ^Zxs_]h fhe_dmeyjgh-kblh\uf ^_ckl\b_f >24]. Dhg\_jkby lhemheZ gZ lZdhf dZlZebaZlhj_ ijb K khklZ\beZ -- ijb k_e_dlb\ghklb ih E-gbljhlhemhem --46%. Ijb gbljh\Zgbb lhemheZ gbljmxs_c kf_kvx [_a dZlZebaZlhjZ ihemqZ_lky kf_kv bahf_jh\ k khhlghr_gb _f E-/D-bahf_ju -- < kemqZ_ bkihevah\Zgby bh ghh[f_gguo kfhe gZ hkgh\_ nlhjZedbekmevnhdbkehl khhlghr_gb_ E-/D-bahf_ju \hajZklZ_l ^h >@ Z ijb gbljh\Zgbb \ ]Zah\hc nZa_ -- ^h AZf_gZ k_jghc dbkehlu gZ nhknhjgmx lZd`_ ijb\h^bl d m\_ebq_gbx khhlghr_gby E-/D-bahf_ju ^h Dbg_lbq_kdb_ bkke_^h\Zgby gbljh\Zgby ZjhfZlbq_ kdbo kh_^bg_gbc Zahlghc dbkehlhc gZ l\_j^hnZaghf dZlZebaZlhj_ 6L22/H2SO4 \ kj_^_ K+2Cl2 >@ ihdZaZeb qlh gZ lZdhf dZlZebaZlhj_ k jZaebqguf kh^_j`Zgb_f k_jghc dbkehlu fh`gh gbljh\Zlv kh_^bg_gby jZaeb 11 qZxsb_ky ih j_Zdpbhgghc kihkh[ghklb \ jZa hl f_ablbe_gZ ^h E-gbljhoehj[_gaheZ IjhiblZgguc 100%-ghc k_jghc dbkehlhc 6L22 kh^_j`Zsbc --50% H2SO4 \_^_l k_[y ih^h[gh k_jghc dbkehl_ k dhgp_gljZ pb_c \ur_ GZ[ex^Z_lky q_ldZy aZ\bkbfhklv dhg gZ[e klZglu kdhjhklb gbljh\Zgby k hl kh^_j`Zgby k_j

/k

gZ[e

ArH k

=k

gZ[e

ArX

l\_j^hnZaguf dZlZebaZlhf / kgZ[eArH \ +2SO4)

-- aZf_s_gguc ZjhfZlbq_kdbc m]e_\h^hjh^ Ihgb`_ggh_ kh^_j`Zgb_ h-bahf_jZ \ kf_kb fhgh gbljhlhemheh\ gZ[ex^Z_lky ijb gbljh\Zgbb lhemheZ dhgp_gljbjh\Zgghc G1H3 \ ijbkmlkl\bb ZjhfZlbq_kdbo kmevnhdbkehl hkh[_ggh _keb bkihevamxlky dbkehlu gZ ghkbl_e_ \ dZq_kl\_ dhlhjh]h ijbf_gyxl p_ebl < lZdbo j_Zdpbhgguo kbkl_fZo khhlghr_gb_ f_`^m h- b ifhghgbljhlhemheZfb f_gy_lky gZ h[jZlgh_ ih kjZ\g_ gbx k gbljh\Zgb_f \ kj_^_ G26H4. :gZeh]bqgh_ y\e_gb_ gZ[ex^Zeb HeZo k khlj ijb gbljh\Zgbb lhemheZ kbkl_fZfb gbljhwnbj-Nafion-H kfheZ gZ hkgh\_ i_jnlhjbjh\Zgghc kmevnhdbkehlu H^gh\j_f_ggh ijhbkoh^bl kgb`_gb_ dhgp_gljZpbb f-bahf_jZ ^h
$U;

]^_

GZjy^m k hdkb^Zfb ZahlZ b Zahlghc dbkehlhc \ dZq_ kl\_ gbljmxsbo j_Z]_glh\ rbjhdh bkihevamxlky Zedbeb ZpbegbljZlu, dhlhju_ \ jy^_ kemqZ_\ iha\heyxl ih emqZlv gbljhijh^mdlu k \ukhdbf kh^_j`Zgb_f i-bahf_jZ LZd ijb gbljh\Zgbb lhemheZ gZ p_hebl_ ZSM- b i_glZkbe_ [_gahbegbljZlhf h[jZam_lky gbljh-

Gbljh\Zgb_ ^jm]bfb gbljmxsbfb kbkl_fZfb

108


Jhk obf ` @ Jhk obf h[-\Z bf >B F_g^_e__\Z
lhemhe k khhlghr_gb_f bahf_jh\ i- : h- Ijhibl dZ p_heblZ =60- jZkl\hjhf ljb[mlbeZfbgZ \ ]_dkZg_ fZkkh\h_ khhlghr_gb_ p_hebl Zfbg k ihke_ ^mxs_c kmrdhc b hlfu\dhc ba[uldZ ZfbgZ ih\urZ_l wnn_dlb\ghklv ^_ckl\by dZlZebaZlhjZ bahf_jguc kh klZ\ ijh^mdlZ j_Zdpbb h- : f- : i- Ih\u r_gb_ iZjZ-k_e_dlb\ghklb gbljh\Zgby lhemheZ h[tyk gyxl l_f qlh ihke_ h[jZ[hldb p_heblZ ljb[mlbeZfb ghf dhlhjuc \u[hjhqgh \aZbfh^_ckl\m_l k dbkehlgu fb p_gljZfb jZkiheh`_ggufb gZ \g_rg_c ih\_joghklb dZlZebaZlhjZ gZb[he__ Zdlb\gufb hklZxlky dbkehlgu_ p_glju \ dZgZeZo p_heblh\ LZdbf h[jZahf bkdexqZ_l ky \hafh`ghklv h[jZah\Zgby gbljhlhemheZ gZ \g_rg_c ih\_joghklb dZlZebaZlhjh\ Ijb wlhf aZ kq_l jZaebqby dbg_lbq_kdbo ^bZf_ljh\ bahf_jh\ gbljhlhemheZ ijhbk oh^bl bo jZa^_e_gb_ \ ihjZo p_heblh\ b ih\ur_gb_ dhgp_gljZpbb i-gbljhlhemheZ \ ijh^mdlZo j_Zdpbb >27]. < bkke_^h\Zgbyo ijh\_^_gguo \ JOLM bf >B F_g^_e__\Z mklZgh\e_gh qlh ijb gbljh\Zgbb lh emheZ gZ p_heblguo dZlZebaZlhjZo \ kj_^_ oehjhnhjfZ k bkihevah\Zgb_f \ dZq_kl\_ gbljmxs_]h Z]_glZ -ghc HNO3 j_Zdpby ijhl_dZ_l \ agZqbl_evghc f_j_ \ h[t_f_ jZkl\hjbl_ey ihwlhfm gZ bahf_jguc khklZ\ ijh^mdlh\ j_Zdpbb kbevgh_ \ebygb_ hdZau\Z_l fZkkh\h_ khhlghr_ gb_ p_hebl ZahlgZy dbkehlZ < >28@ ih^l\_j`^_gh qlh bahf_jguc khklZ\ ijh^mdlZ j_Zdpbb kbevgh aZ\bkbl hl khhlghr_gby 6L22 : Al2O3 k _]h jhklhf m\_ebqb\Z_lky ^hey i-bahf_jZ Ijb khhlghr_gbb 6L22 : Al2O3 jZ\ghf \uoh^ i-bahf_jZ ^hklb]Z_l >29] Ijh\_^_gb_ gbljh\Zgby gZ p_heblZo iha\hey_l ba f_gblv khhlghr_gb_ h[jZamxsboky bahf_jh\ ^bgbljh lhemheZ LZd ijb gbljh\Zgbb lhemheZ Zahlghc dbkehlhc \ jZkl\hj_ &G3CO)22 gZ nh`Zabl_ q_j_a q \uoh^ ^bgbljhlhemheZ >GL khklZ\be khhlghr_gb_ 2,4->GL ->GL hdheh Z gZ p_hebl_ G-;_lZ \ l_o `_ mkeh\byo \uoh^ ijh^mdlZ ^hklb] ijb khhlghr_gbb 2,4->GL ->GL hdheh >himkdZxl qlh gZ[ex^Z_fuc wnn_dl k\yaZg k mqZklb_f \ j_Zdpbb Zp_lbegbljZlZ @ Bamq_gh gbljh\Zgb_ ZjhfZlbq_kdbo m]e_\h^hjh^h\ gbljZlZfb f_lZeeh\ gZg_k_ggufb gZ fhglfhjbeehgbl \ ijbkmlkl\bb &G3CO)22 MklZgh\e_gh qlh ijbjh^Z dZlbhgZ kbevgh \eby_l gZ gbljmxsmx Zdlb\ghklv GZb [he__ Zdlb\gufb hdZaZebkv gbljZlu &X $O %L &U 0J Q_j_a q ihke_ gZqZeZ j_Zdpbb \uoh^ gbljhlhemheZ khklZ\be hdheh Z q_j_a q ^hklb]Ze ijZdlbq_kdb < aZ\bkbfhklb hl mkeh\bc j_Zdpbb fh]ml [ulv ihemq_gu eb[h fhgh- eb[h ^baZf_s_ggu_ gbljhkh_^b g_gby Ih\ukblv \uoh^ ^bgbljhkh_^bg_gbc m^Z_lky dZd aZ kq_l m\_ebq_gby dhebq_kl\Z dZlZebaZlhjZ lZd b iml_f \\_^_gby \ gbljmxsmx kf_kv g_[hevrhc ^h[Z\db Zahl ghc dbkehlu GZ kdhjhklv b bahf_jguc khklZ\ fhghgbljhlhemheZ h[jZamxs_]hky ijb gbljh\Zgbb lhemheZ kheyfb gbljh gby \ qZklghklb [hjnlhjb^hf gbljhgby kbevgh_ \eby gb_ hdZau\Zxl ^h[Z\db djZmg-wnbjh\ LZd ijb bkihev



l L 3

ah\Zgbb jZkl\hjh\ -djZmg- K b 122BF4 \ayluo \ fhevghf khhlghr_gbb b khhlghr_gb_ h- b i-bahf_jh\ baf_gy_lky hl ^h DjZmg-wnbju K b K hdZau\Zxl keZ[h_ \ebygb_ gZ bahf_jguc khklZ\ fhghgbljhlhemheZ Hij_^_eyxsmx jhev ih\b^bfhfm b]jZxl ijhkljZgkl\_ggu_ nZdlhju h[m keh\e_ggu_ mqZklb_f \ j_Zdpbb dhfie_dkZ djZmg-wnbjZ k khevx gbljhgby < aZdexq_gb_ ke_^m_l hlf_lblv qlh d gZklhys_fm \j_f_gb jZajZ[hldb ih dZlZeblbq_kdhfm gbljh\Zgbx [_gaheZ g_ ijb\_eb d kha^Zgbx ijhp_kkh\ kjZ\gbfuo beb ij_\hkoh^ysbo kms_kl\mxsb_ \ ijhfure_gghklb ih l_ogheh]bqghklb ;he__ mki_rgh jZajZ[Zlu\Zxlky f_lh^u iha\heyx sb_ agZqbl_evgh m\_ebqblv kh^_j`Zgb_ i-gbljhlhemheZ b kgbablv kh^_j`Zgb_ f-bahf_jZ ijb gbljh\Zgbb lh emheZ Bf__lky khh[s_gb_ h ij_^iheZ]Z_fhf d ] aZ\_jr_gbb ijh_dlZ ih ihemq_gbx fhghgbljhlhemheZ k kh^_j`Zgb_f i-bahf_jZ b [_a f-bahf_jZ ^ey bk ihevah\Zgby \ ijhba\h^kl\_ ^b- b ljbgbljhlhemheZ h^gZdh hlkmlkl\b_ dZdbo-eb[h iZjZf_ljh\ ij_^eZ]Z_fh]h ijhp_kkZ ^_eZ_l wlm i_jki_dlb\m g_hij_^_e_gghc >29].
Gh\u_ j_r_gby \ l_ogheh]bb ijhba\h^kl\Z gbljhijhba\h^guo [_gaheZ b lhemheZ

DZd [ueh m`_ hlf_q_gh \ gZklhys__ \j_fy hkgh\gh_ f_klh \ ijhba\h^kl\_ gbljhkh_^bg_gbc ijbgZ^e_`bl g_ \aju\qZluf \_s_kl\Zf Z lh\ZjZf ^ey gZjh^gh]h ohayc kl\Z < k\yab k wlbf dZq_kl\_ggh baf_gbeky ih^oh^ d ijhba\h^kl\m gbljhkh_^bg_gbc hl gh\uo l_ogheh]bc lj_[m_lky \ukhdZy wdhghfbqghklv b j_adh_ khdjZs_gb_ \j_^guo \u[jhkh\ \ hdjm`Zxsmx kj_^m ijb khojZg_ gbb \ukhdhc [_ahiZkghklb ijhp_kkh\ Hkgh\guf gZijZ\e_gb_f jZajZ[hlhd klZe iheguc beb qZklbqguc hldZa hl bkihevah\Zgby k_jghc dbkehlu Ijb hlkmlkl\bb ijbgpbibZevgh gh\uo obfbq_kdbo j_ r_gbc hkgh\gZy aZ^ZqZ fh^_jgbaZpbb ijhba\h^kl\Z gbljhkh_^bg_gbc j_rZeZkv l_ogheh]bq_kdbfb f_lh^Z fb aZ kq_l kh\_jr_gkl\h\Zgby mkeh\bc ijhp_kkh\ b ZiiZjZlmjgh]h hnhjfe_gby WlZ jZ[hlZ hkms_kl\ey_lky ih ^\mf gZijZ\e_gbyf gbljh\Zgb_ \ k_jgh-Zahlguo dbkehlguo kf_kyo [_a ljZ^bpbhgghc klZ^bb j_]_g_jZ pbb dhgp_gljbjh\Zgghc k_jghc dbkehlu b gbljh\Zgb_ \ kj_^_ h^ghc Zahlghc dbkehlu < ^Zgghc klZlv_ jZkkfZljb\Z_lky djmighlhggZ`gh_ ijhba\h^kl\h gbljhkh_^bg_gbc f_lh^hf gbljh\Zgby gZ ijbf_j_ kh_^bg_gbc \uimkd dhlhjuo \ fbj_ baf_jy_l ky khlgyfb lukyq -- fbeebhgZfb lhgg \ ]h^ >ey ijh fure_ggh]h ijhba\h^kl\Z wlbo ijh^mdlh\ bkihevamxl ky g_ij_ju\gu_ ijhp_kku b hlghkbl_evgh g_[hevrb_ ih _fdhklb j_Zdpbhggu_ ZiiZjZlu LZdh_ l_ogheh]bq_kdh_ hnhjfe_gb_ \u[jZgh k mq_lhf ki_pbnbq_kdbo k\hckl\ ijhp_kkh\ gbljh\Zgby Ij_`^_ \k_]h wlh agZqbl_evguc l_ieh\hc wnn_dl ijhp_kkZ --120 d>`fhev ijb \\_ ^_gbb h^ghc gbljh]jmiiu >Ze__ ba-aZ \ukhdhc hdbk ebl_evghc kihkh[ghklb Zahlghc dbkehlu ^hklZlhqgh \_ebdZ \_jhylghklv ijhl_dZgby gZjy^m k j_Zdpb_c gbl jh\Zgby hdbkebl_evguo ijhp_kkh\ L_ieh\hc wnn_dl

109


< N @bebg < E A[Zjkdbc


9,,,

,9

,

,,

,,

,,,

,9

9

9,

9 9,,





,;





Jbk



L_ogheh]bq_kdZy ko_fZ ijhba\h^kl\Z ^bgbljhlhemheZ

1 -- hlklhcgZy dhehggZ hljZ[hlZgghc dbkehlu -- k_iZjZlhj wdkljZdlhjZ-jZa[Z\bl_ey -- dhl_e lh]h `_ ZiiZjZlZ 4 -- gbljZlhj i_j\hc klZ^bb -- gbljZlhj \lhjhc klZ^bb -- ZiiZjZl \h^ghc ijhfu\db -- ZiiZjZl kh^h\hc ijhfu\db 8 -- ZiiZjZl aZdexqbl_evghc ijhfu\db I -- lhemhe ,, -- ZahlgZy dbkehlZ ,,, -- k_jgZy dbkehlZ ,9 -- dbkeZy ijhfu\gZy \h^Z 9 -- \h^Z 9, -- kh^h\uc jZkl\hj VII -- ^bgbljhlhemhe 9,,, -- hljZ[hlZggZy dbkehlZ ,; -- hkgh\ghc fZlhqguc jZkl\hj gZ hqbkldm

j_Zdpbc hdbke_gby \ur_ q_f gbljh\Zgby ihwlhfm jZa\blb_ hdbke_gby fh`_l ijb\_klb d Z\Zjbb \u[jhkm b \hkieZf_g_gbx Z \ kemqZ_ ihebgbljhkh_^bg_gbc b d dZlZkljhn_ \aju\ Ihl_gpbZevgmx hiZkghklv ij_^ klZ\eyxl g_ lhevdh kZfb gbljhkh_^bg_gby gh b bo kf_ kb k dbkehlZfb hgb lZd`_ fh]ml h[eZ^Zlv ^_lhgZpbhg gufb k\hckl\Zfb Ijb \ukhdbo l_fi_jZlmjZo \ur_ 200 K \ dZq_kl\_ hdbkebl_ey fh`_l \uklmiZlv g_ lhev dh ZahlgZy gh b k_jgZy dbkehlZ b hkh[_ggh he_mf GZ dhg_p hlghkbl_evgh \ukhdZy jZkl\hjbfhklv gbljhkh _^bg_gbc \ dhgp_gljbjh\Zgguo dbkehlZo b hkh[_ggh \ Zahlghc dbkehl_ aZljm^gy_l \u^_e_gb_ bo ba j_Zdpbhg guo kf_k_c Hlf_q_ggu_ hkh[_gghklb j_Zdpbb gbljh\Zgby mqb lu\Zxlky dZd \ l_ogheh]bq_kdhf lZd b ZiiZjZlmjghf hnhjfe_gbb ijhp_kkh\ < g_ij_ju\guo ijhp_kkZo bk ihevamxl dZd ijZ\beh ZiiZjZlu ij_bfms_kl\_ggh]h kf_r_gby Ijb \\_^_gbb h^ghc gbljh]jmiiu \_kv ijh p_kk fh`_l hkms_kl\eylvky \ h^ghf ZiiZjZl_ \ dhlh juc ^habjmxl gbljm_fh_ kh_^bg_gb_ b dbkehlu \ aZ ^Zgghf khhlghr_gbb Ijb \ukhdbo kdhjhklyo gbljh\Z gby ^Z`_ \ hlghkbl_evgh jZa[Z\e_gghc k_jghc dbkehl_ ijhp_kk aZ\_jrZ_lky \ l_q_gb_ g_kdhevdbo ^_kyldh\ k_dmg^ b j_Zevgh_ \j_fy ij_[u\Zgby j_Zdpbhgghc kf_ kb \ ZiiZjZl_ hij_^_ey_lky \hafh`ghklvx l_iehhl\h^Z L_f g_ f_g__ \h fgh]bo kemqZyo \ l_ogheh]bq_kdmx ko_fm \\h^yl [mn_jguc ZiiZjZl qlh[u bkdexqblv ijh kdhd g_ijhgbljh\Zggh]h ijh^mdlZ Jhev [mn_jgh]h ZiiZjZlZ fh`_l b]jZlv ZiiZjZl-jZa[Z\bl_ev \ dhlhjhf j_ZdpbhggZy kf_kv jZa[Z\ey_lky \h^hc ^ey jZaeh`_gby gbljhabek_jghc dbkehlu b mf_gvr_gby jZkl\hjbfhklb gbljhkh_^bg_gby \ hljZ[hlZgghc dbkehl_ beb wdkljZd lhj \ dhlhjhf gbljhkh_^bg_gb_ jZkl\hj_ggh_ \ hljZ [hlZgghc dbkehl_ ba\e_dZ_lky gbljm_fuf ijh^mdlhf < ijhba\h^kl\_ ^bgbljhkh_^bg_gbc l_ogheh]bq_ kdb_ ijh[e_fu k\yaZgu \ i_j\mx hq_j_^v k wnn_dlb\ ghklvx bkihevah\Zgby dbkehl Ijb \\_^_gbb \ fhe_dmem dZ`^hc ke_^mxs_c gbljh]jmiiu kdhjhklv gbljh\Zgby mf_gvrZ_lky \ 5--106 jZa Ke_^h\Zl_evgh ijb ihem q_gbb ihebgbljhkh_^bg_gbc ^ey \\h^Z \lhjhc gbljh ]jmiiu g_h[oh^bfh bkihevah\Zlv [he__ dhgp_gljbjh \Zggmx k_jgmx dbkehlm < oh^_ ijhp_kkZ dbkehlZ jZa

[Z\ey_lky j_Zdpbhgghc \h^hc __ dhgp_gljZpby kgb`Z _lky gh hklZ_lky ^hklZlhqghc ^ey gbljh\Zgby gZ i_j\hc klZ^bb Ihwlhfm p_e_khh[jZagh bkihevah\Zlv gZ i_j\hc klZ^bb hljZ[hlZggmx dbkehlm \lhjhc klZ^bb < l_o kemqZyo dh]^Z kdhjhklv j_Zdpbb g_\ukhdZ ijb ihemq_gbb ^bgbljhlhemheZ b ^bgbljh[_gaheZ \j_fy ij_[u\Zgby gbljhijh^mdlZ \ ZiiZjZlZo m\_ebqb\Z_lky Ijhp_kk ijh\h^yl \ dZkdZ^_ ZiiZjZlh\ \ j_`bf_ ijhlb \hlhdZ qlh iha\hey_l mf_gvrblv kmffZjgmx _fdhklv j_Zdlhjh\ J_Zdpby gbljh\Zgby fZehj_Zdpbhgghkihkh[ guo kh_^bg_gbc ijhl_dZ_l \ fbg_jZevghc nZa_ b ^hey __ \ hj]Zgbq_kdhc nZa_ hq_gv fZeZ Qlh[u ih \ukblv kdhjhklv j_Zdpbb g_h[oh^bfh m\_ebqblv h[t_f fbg_jZevghc nZau l_ fh^mev hlghr_gb_ h[t_fh\ fbg_jZevghc b hj]Zgbq_kdhc nZa \ ZiiZjZl_ LZd dZd m\_ebq_gb_ jZkoh^Z k\_`bo dbkehl ijb\h^bl d agZqb l_evghfm m^hjh`Zgbx p_e_\h]h ijh^mdlZ \ ijhfur e_gghklb bkihevamxl j_pbjdmeypbx hljZ[hlZgghc db kehlu \gmljb klZ^bb beb \gmljb ZiiZjZlZ < ijhba\h^ kl\_ gbljh[_gaheZ qZklv hljZ[hlZgghc dbkehlu ihke_ hl^_e_gby hj]Zgbq_kdh]h kehy gZijZ\eyxl \ ojZgbebs_ b hllm^Z \ha\jZsZxl \ gbljZlhj < ijhba\h^kl\_ ^b gbljhlhemheZ qZklv hljZ[hlZgghc dbkehlu \ha\jZsZ_l ky \ j_Zdlhj g_ihkj_^kl\_ggh ba k_iZjZlhjZ kh\f_s_g gh]h k j_Zdlhjhf LZdbf h[jZahf ^hihegbl_evguc jZkoh^ dbkehlu g_h[oh^bf lhevdh ijb imkd_ kbkl_fu Lbibqguf ijbf_jhf l_ogheh]bq_kdh]h ijhp_kkZ ihemq_gby ZjhfZlbq_kdbo ihebgbljhkh_^bg_gbc y\ey _lky ijhba\h^kl\h kf_kb bahf_jh\ ^bgbljhlhemheZ >GL kh^_j`Zs_c ->GL b ->GL ijh ba\h^kl\h -- ]h^h\ >@ Ijhp_kk ijh\h^blky \ ijhlb\hlhd_ \ ZiiZjZlZo k kh\f_s_ggufb k_iZjZlh jZfb Ba-aZ `_kldbo h]jZgbq_gbc ih kh^_j`Zgbx ljb gbljh- b fhghgbljhlhemheZ \ ]hlh\hf ijh^mdl_ f_g__ dZ`^h]h dhgp_gljZpbx +2SO4 ih^^_j`b\Zxl \ madbo ij_^_eZo NZdlhj gbljmxsbc Zdlb\ghklb gZ i_j \hc klZ^bb -- gZ \lhjhc klZ^bb -- Ijbg pbibZevgZy l_ogheh]bq_kdZy ko_fZ wlh]h ijhp_kkZ ij_^ klZ\e_gZ gZ jbk Dhebq_kl\h k_jghc dbkehlu jZkoh ^m_fhc ^ey ihemq_gby lhggu ^bgbljhlhemheZ ij_\urZ_l d] b aZ\bkbl hl dhgp_gljZpbb bkihev am_fhc +123.

110


Jhk obf ` @ Jhk obf h[-\Z bf >B F_g^_e__\Z



l L 3

Hkgh\guf g_^hklZldhf ^Zgghc l_ogheh]bb y\ey_lky bkihevah\Zgb_ [hevrh]h dhebq_kl\Z +2SO4 ^ey gbljh \Zgby < oh^_ ijhp_kkZ hgZ jZa[Z\ey_lky \h^hc qlh ijb\h^bl d g_h[oh^bfhklb \\h^blv klZ^bx __ dhgp_g ljbjh\Zgby Wlh lj_[m_l agZqbl_evguo wg_j]_lbq_kdbo aZljZl b ijb\h^bl d j_adhfm m\_ebq_gbx \j_^guo \u [jhkh\ \ hdjm`Zxsmx kj_^m Ba gh\uo ijhp_kkh\ gZb[he__ jZajZ[hlZg Z^bZ[Zlb q_kdbc f_lh^ ihemq_gby gbljhkh_^bg_gbc \ kj_^_ k_j gh-Zahlguo dbkehlguo kf_k_c >ey hkms_kl\e_gby wlh]h f_lh^Z g_h[oh^bfh qlh[u dhebq_kl\h l_ieZ \u^_eyx s_]hky ijb gbljh\Zgbb [ueh ^hklZlhqgh ^ey bkiZj_gby \h^u h[jZamxs_cky \ j_Zdpbb b hljZ[hlZggZy dbkehlZ fh]eZ kem`blv kj_^hc ^ey ih\lhjgh]h ijh\_^_gby ijh p_kkZ < wlhf kemqZ_ bkdexqZxlky aZljZlu gZ j_]_g_jZ pbx k_jghc dbkehlu qlh ^_eZ_l ijhp_kk \ukhdhwdhgh fbqguf >hihegbl_evguf mkeh\b_f hkms_kl\e_gby ijhp_kkZ y\ey_lky \hafh`ghklv bkiZj_gby \h^u ba k_j ghc dbkehlu ihkdhevdm \h-i_j\uo l_iehlZ aZljZqb \Z_fZy gZ bkiZj_gb_ \h^u ba lZdhc kbkl_fu [hevr_ q_f l_iehlZ bkiZj_gby qbklhc \h^u \h-\lhjuo l_fi_ jZlmjZ dbi_gby k_jghc dbkehlu j_adh ih\urZ_lky k mf_gvr_gb_f kh^_j`Zgby \ g_c \h^u Ijb kh^_j`Zgbb k_jghc dbkehlu \ jZkl\hj_ gb`_ \ iZjZo __ g_l JZkq_lu ihdZau\Zxl qlh ijb bk ihevah\Zgbb -ghc +2SO4 b -ghc +123 ^ey ijb ]hlh\e_gby dbkehlguo kf_k_c k nZdlhjhf gbljmxs_c Zdlb\ghklb jZ\guf \u^_eyxs_]hky l_ieZ ^hklZ lhqgh ^ey bkiZj_gby \k_c h[jZamxs_cky \h^u b gZ]j_ \Zgby j_Zdpbhgghc fZkku ^h 200 & Ijb bkihevah\Z gbb -ghc +123 l_iehlu j_Zdpbb m`_ g_ o\Zlbl ^ey j_]_g_jZpbb k_jghc dbkehlu Ihwlhfm \u[hj dhgp_g ljZpbb +123, bkihevam_fhc \ ijhp_kk_ hij_^_ey_lky wdhghfbq_kdbfb nZdlhjZfb D fhf_glm kha^Zgby Z^bZ[Zlbq_kdh]h ijhp_kkZ gbl jh[_gahe ihemqZeb ih g_ij_ju\ghfm f_lh^m \ j_Zdlhj ^habjmxl dbkehlgmx kf_kv khklZ\Z +123, 50% H2SO4 b +22 ijb l_fi_jZlmj_ --70 K ihke_ hl^_e_gby hj]Zgbq_kdh]h kehy gbljh[_gahe wdkljZ]bjm xl ba hljZ[hlZgghc dbkehlu [_gahehf JZkoh^ +123 0,95--0,98 fhevfhev [_gaheZ \uoh^ gbljh[_gaheZ ih HNO3 khklZ\ey_l I_j\hgZqZevgh [ueZ ij_^eh`_gZ l_ogheh]by k bk ihevah\Zgb_f ba[uldZ [_gaheZ < ijhp_kk_ k ijbf_g_ gb_f k_jghc dbkehlu \h^Z \f_kl_ k Zahlghc dbkehlhc b hj]Zgbq_kdbfb \_s_kl\Zfb ij_bfms_kl\_ggh [_gah ehf hl]hgy_lky g_ij_ju\gh ijb l_fi_jZlmj_ \ur_ 120 K ba \_jog_c qZklb ZiiZjZlZ Z gbljh[_gahe b hl jZ[hlZggZy dbkehlZ hl\h^ylky kgbam :evl_jgZlb\gh_ j_r_gb_ k\yaZgh k ijbf_g_gb_f k_jgh-Zahlguo kf_k_c ba dhlhjuo hlghkbl_evgh e_]dh fh`gh m^Zeylv \h^m ijb l_fi_jZlmj_ gb`_ K dh]^Z ^hey hdbkebl_evguo ijhp_kkh\ kjZ\gbl_evgh fZeZ Wlhfm mkeh\bx m^h\e_l\hjyxl dbkehlgu_ kf_kb (65--70% H2SO4 f_g__ --10% HNO3), [ebadb_ ih
:^bZ[Zlbq_kdb_ ijhp_kku gbljh\Zgby

nZdlhjm gbljmxs_c Zdlb\ghklb d kf_kyf bkihevam_ fuf ijb fhghgbljh\Zgbb \ ljZ^bpbhgguo ijhp_kkZo < ] [ue ihemq_g iZl_gl gZ h^ghklZ^bcgh_ gbl jh\Zgb_ [_gaheZ \ k_jgh-Zahlguo kf_kyo ijb l_fi_jZ lmj_ --120 K k hl]hghf Za_hljhiZ kh^_j`Zs_]h, gZjy^m k \h^hc b [_gahehf g_[hevrb_ dhebq_kl\Z gbl jh[_gaheZ b Zahlghc dbkehlu >@ G_^hklZldhf ijhp_k kZ y\ey_lky g_h[oh^bfhklv hl]hgdb \ dhgp_ ijhp_kkZ [_gaheZ hl ihemq_ggh]h ijh^mdlZ Ijb mkh\_jr_gkl\h\Zgbb ijhp_kk [ue jZa^_e_g gZ ^\_ klZ^bb GZ i_j\hc klZ^bb \ Z^bZ[Zlbq_kdhf j_Zdlh j_ [hevrmx qZklv [_gaheZ gbljmxl k_jgh-Zahlghc kf_ kvx khklhys_c ba j_pbjdmebjmxs_]h ihlhdZ -ghc k_jghc dbkehlu b ^habjm_fhc \ j_Zdlhj -ghc +123. L_fi_jZlmjZ \ j_Zdlhj_ gb`_ K b hgZ ih^^_j`b \Z_lky aZ kq_l l_iehlu j_Zdpbb jm]hc \ZjbZgl g_ij_ju\gh]h Z^bZ[Zlbq_kdh]h ijh p_kkZ ijhba\h^kl\Z gbljh[_gaheZ jZajZ[hlZg \ eZ[hjZ lhjbb \aju\qZluo \_s_kl\ nbjfu &,/ &KHPHWLF ,QWHUQDWLRQDO /WG \ DZgZ^_ b aZiZl_glh\Zg nbjfhc ©$PHULFDQ &\DQDPLG &Rª Ijhp_kk lj_[m_l f_gvrbo dZiblZevguo \eh`_gbc gZ f_gvr_]h dhebq_kl \Z fZl_jbZeh\ b wg_j]bb hl kms_kl\mxs_c l_o gheh]bb >@ \uoh^ ijh^mdlZ >@ < ] [ueb kha^Zgu ^\Z ijhfure_gguo ijhba\h^kl\Z fhsghklvx 173 luk l]h^ ^ey nbjfu ©Rubicon Chemical Incª b 50 luk l]h^ ^ey ©American Cyanamid Coª Bkihevah\Z gb_ gh\hc l_ogheh]bb iha\hebeh ih\ukblv fhsghklb ih ijhba\h^kl\m gbljh[_gaheZ \ fbj_ ^h feg l]h^ >@ IjbgpbibZevgZy ko_fZ wlh]h ijhba\h^kl\Z ij_^ klZ\e_gZ gZ jbk 2.
111


< N @bebg < E A[Zjkdbc
IX 1 I 7 2 3 VII VIII

II 6 5 4

III

V 8 IV

VI

Jbk Ko_fZ Z^bZ[Zlbq_kdh]h ijhp_kkZ ihemq_gby gbljh [_gaheZ
1 -- l_iehh[f_ggbd
-- gbljZlhju -- k_iZjZlhj -- ijb_fgbd j_]_g_jbjh\Zgghc k_jghc dbkehlu -- kf_kbl_ev dbkehl -- gZkhk -- dhg^_gkZlhj -- dhgp_gljZlhj k_j ghc dbkehlu

I -- [_gahe ,, -- ZahlgZy dbkehlZ ,,, -- k\_`Zy k_jgZy dbkeh lZ ,9 -- j_]_g_jbjh\ZggZy k_jgZy dbkehlZ 9 -- hljZ[hlZggZy dbkehlZ 9, -- iZj 9,, -- dhg^_gkZl 9,,, -- d \Zdmmfghfm gZkhkm ,; -- kf_kv dbkehl gZ gbljh\Zgb_

< ihke_^g__ \j_fy ihy\bebkv iZl_glu ih bkihevah \Zgbx \ wlbo ijhp_kkZo j_Zdlhjh\ [_a f_oZgbq_kdbo i_j_f_rb\Zxsbo mkljhckl\ >@ :evl_jgZlb\hc Z^bZ[Zlbq_kdbf ijhp_kkZf y\ey_lky f_lh^ gbljh\Zgby k_jgh-Zahlgufb kf_kyfb k gh\uf \ZjbZglhf j_]_g_jZpbb hljZ[hlZgghc dbkehlu >@ Gbljh\Zgb_ ijh\h^yl \ bahl_jfbq_kdhf j_Zdlhj_ ijb dhgp_gljZpbb hljZ[hlZgghc dbkehlu [ebadhc d ljZ^bpbhgghfm ijhp_kkm 70% H2SO4, 1% HNO3 < j_Zdlhj ih^Zxl j_pbjdmebjm_fmx k_jgmx dbkehlm dhgp_gljbjh\Zggmx --99%-gmx +123 b [_gahe \ ba[uld_ hdheh qlh[u bkihevah\Zlv iheghklvx Zahlgmx dbkehlm Ihke_ hl^_e_gby \ k_iZjZlhj_ gbljh [_gahe gZijZ\eyxl gZ klZ^bx \u^_e_gby Z hljZ[hlZg gZy dbkehlZ \ dhlhjhc kh^_j`blky [_gaheZ gbljh[_gaheZ b hdheh hdkb^h\ ZahlZ ih^Z _lky gZ j_]_g_jZpbx Q_j_a l_iehh[f_ggbd gZ]j_lZy hljZ[hlZggZy dbkehlZ ihklmiZ_l \ kdhjhklghc bkiZjb l_ev ]^_ ih^ jZaj_`_gb_f ijb --110 K hl]hgyxlky gbljh[_gahe [_gahe b qZklv \h^u >Ze__ hljZ[hlZggZy dbkehlZ ihklmiZ_l \ ]hjbahglZevgu_ bkiZjbl_eb J_`bf \ bkiZjbl_e_ hij_^_ey_lky dhgp_gljZpb_c dbkehlu dhlhjmx ohlyl ihemqblv ?keb ihemqZxl --85%-gmx

< i_j\uc ba gbljZlhjh\ ih^Zxl ih^h]j_luc \ l_i ehh[f_ggbd_ [_gahe b dbkehlgmx kf_kv khklZ\Z -- 7,5% HNO3, 58,5--66,5% H2SO4, 28--37% H22 ihem q_ggmx \ kf_kbl_e_ dbkehl ;_gahe bkihevamxl \ ba [uld_ hl l_hj qlh[u h[_ki_qblv ihegh_ bkiev ah\Zgb_ Zahlghc dbkehlu < ihke_^h\Zl_evgh jZkiheh `_gguo gbljZlhjZo l_fi_jZlmjZ ihkl_i_ggh \hajZklZ_l hl ^h K Ih\ur_gb_ l_fi_jZlmju kihkh[kl\m_l m\_ebq_gbx kdhjhklb j_Zdpbb b iha\hey_l bkihevah\Zlv [he__ jZa[Z\e_ggu_ dbkehlgu_ kf_kb q_f \ h[uqguo ijhp_kkZo Ihke_^g__ mf_gvrZ_l kh^_j`Zgb_ ^bgbljh [_gaheZ Gbljh[_gahe-kuj_p ba k_iZjZlhjZ ihklmiZ_l \ l_ieh h[f_ggbd ]^_ hl^Z_l qZklv l_ieZ [_gahem b^ms_fm gZ j_Zdpbx AZl_f _]h ijhfu\Zxl hl dbkehl b hl]hgyxl g_ ijhj_Z]bjh\Z\rbc [_gahe dhlhjuc \ha\jZsZxl \ pbde Dhgp_gljbjh\Zgb_ hljZ[hlZgghc dbkehlu ijh\h^yl ih^ jZaj_`_gb_f \ kdhjhklghf kl_deygghf dhgp_gljZ lhj_ k lZglZeh\uf rludh\uf gZ]j_\Zl_e_f < dhgp_g ljZlhj ih^Zxl iZj gbadh]h ^Z\e_gby \ dhebq_kl\_ 85 d]l gbljh[_gaheZ Hlh]gZggZy \h^Z bkihevam_lky ^ey ijhfu\db gbljh[_gaheZ-kujpZ Z j_]_g_jbjh\ZggZy dbkehlZ kh^_j`ZsZy +2SO4 ihklmiZ_l \ ijb_fgbd @ G_`_eZl_evgu_ \lhjbqgu_ hdbkebl_evgu_ ijhp_kku gZqbgZxlky ijb l_fi_jZlmj_ k\ur_ K b wlZ l_f i_jZlmjZ j_dhf_g^h\ZgZ ^ey Z\Zjbcgh]h k[jhkZ

G2SO4, lh ijhp_kk \_^ml ijb l_fi_jZlmj_ ^h K b hklZlhqghf ^Z\e_gbb dIZ ijb ihemq_gbb [he__ dhg p_gljbjh\Zgghc +2SO4 l_fi_jZlmjm ih\urZxl ^h K ijb jZaj_`_gbb --5 dIZ
112


Jhk obf ` @ Jhk obf h[-\Z bf >B F_g^_e__\Z




l L 3










Kh^_j`Zgb_ gbljh[_gaheZ

fZkk JZkl\hjbfhklv

























L_fi_jZlmjZ °K








L_fi_jZlmjZ °K







Jbk AZ\bkbfhklv jZkl\hjbfhklb gbljh[_gaheZ b [_gaheZ \ -ghc Zahlghc dbkehl_ hl l_fi_jZlmju
------

Jbk AZ\bkbfhklv jZkl\hjbfhklb gbljh[_gaheZ \ Zahlghc dbkehl_ hl __ dhgp_gljZpbb b l_fi_jZlmju
HNO3: 1 -- 69,98%; 2 -- 66,46%; 3 -- 63,48%; 4 -- 61,5%; 5 -- 59,27%; 6 -- 57,15%

gbljh[_gahe



_____

[_gahe

Dhgp_gljZpby

gbljh\Zgby y\eyxlky --70%-gZy b --100%-gZy
HNO3.

>jm]Zy ijh[e_fZ k\yaZggZy k ijh\_^_gb_f gbljh\Z gby \ Zahlghc dbkehl_ \ua\ZgZ k \ukhdhc jZkl\hjbfh klvx gbljhkh_^bg_gbc \ wlhc kj_^_ Ba\_klgh qlh k jhklhf dhgp_gljZpbb dbkehl lZdbo dZd k_jgZy b Zahl gZy jZkl\hjbfhklv \ gbo iheyjguo kh_^bg_gbc j_adh \hajZkl_l Kgb`_gb_ jZkl\hjbfhklb ijb agZqbl_evghf jZa[Z\ e_gbb Zahlghc dbkehlu \h^hc \e_q_l aZ kh[hc [hevrb_ wdhghfbq_kdb_ aZljZlu gZ \uiZjb\Zgb_ \h^u ihwlhfm wnn_dlb\ghc ij_^klZ\ey_lky wdkljZdpby gbljh[_gaheZ ba hljZ[hlZgghc dbkehlu [_gahehf b^msbf gZ gbljh \Zgb_ >Zggu_ ih jZkl\hjbfhklb [_gaheZ b gbljh[_gah eZ \ Zahlghc dbkehl_ jbk b k\b^_l_evkl\mxl \ ihevam wlh]h \u[hjZ QZklbqgh_ \u^_e_gb_ gbljhkh_^bg_gby ba Zahlghc dbkehlu fh`_l [ulv ^hklb]gmlh aZ kq_l hoeZ`^_gby j_Zdpbhgghc fZkku kf jbk H^gZdh hklZlhqgZy jZkl\hjbfhklv gbljh[_gaheZ ^Z`_ ijb gbadbo l_fi_jZ lmjZo hklZ_lky \ukhdhc b lZdZy dbkehlZ g_ fh`_l [ulv j_]_g_jbjh\ZgZ Ihkdhevdm jZkl\hjbfhklv [_gaheZ \ Zahlghc dbkehl_ gb`_ q_f gbljh[_gaheZ hljZ[hlZggZy dbkehlZ ihke_ wdkljZdpbb kh^_j`bl agZqbl_evgh f_gv r__ dhebq_kl\h jZkl\hj_gguo hj]Zgbq_kdbo \_s_kl\ Fgh]hqbke_ggu_ Z\Zjbb ijhbkoh^b\rb_ ijb ihemq_ gbb gbljhkh_^bg_gbc dZd \ ijhba\h^kl\_ \aju\qZluo \_ s_kl\ lZd b \ obfbq_kdhc ijhfure_gghklb aZklZ\eyxl m^_eylv hkh[h_ \gbfZgb_ \hijhkZf l_ogbdb [_ahiZkghklb < ijhp_kkZo ijhl_dZxsbo \ kj_^_ Zahlghc dbkehlu j_Zd pbhggu_ kbkl_fu ij_^klZ\eyxl kh[hc kf_kb ]hjxq_]h b hdbkebl_ey >ey oZjZdl_jbklbdb hiZkghklb lZdbo kbkl_f bkihevamxl jZaebqgu_ iZjZf_lju

H^bg ba gbo -- wlh djblbq_kdbc ^bZf_lj ^_lhgZpbb l_ fbgbfZevguc jZaf_j aZjy^Z ijb dhlhjhf _s_ ijh bkoh^bl wlhl ijhp_kk Bkke_^h\Zgby \ebygby khklZ\Z jZkl\hjh\ jy^Z gbljhkh_^bg_gbc \ Zahlghc dbkehl_ gZ djblbq_kdbc ^bZf_lj ^_lhgZpbb ijh\_^_gu \ JOLM bf >B F_g^_e__\Z ihdZaZeb qlh gZb[he__ hiZkgufb y\eyxlky kbkl_fu k dbkehjh^guf [ZeZgkhf [ebadbf d gmex ijbq_f k m\_ebq_gb_f dhgp_gljZpbb +123 hiZk ghklv \hajZklZ_l < wlhc h[eZklb jZkl\hju gbljhkh_^bg_ gbc \ Zahlghc dbkehl_ ijb[eb`Zxlky ih hiZkghklb d `b^ dbf \aju\qZluf \_s_kl\Zf Ijb kf_s_gbb khklZ\Z hl gme_\h]h [ZeZgkZ djblbq_kdbc ^bZf_lj ^_lhgZpbb m\_eb qb\Z_lky l_ kbkl_fu klZgh\ylky f_g__ hiZkgufb >@ Mqblu\Zy hiZkghklv jZ[hlu k dhgp_gljbjh\Zgghc HNO3 b __ \ukhdmx klhbfhklv Z\lhju i_j\uo l_ogheh ]bq_kdbo ijhp_kkh\ gbljh\Zgby ZjhfZlbq_kdbo m]e_\h ^hjh^h\ Hlf_j --1942 ]] bkihevah\Zeb ^ey gbl jh\Zgby jZa[Z\e_ggmx --70%-gmx +123 Ijhp_kk \_eb \ j_`bf_ dbi_gby ijb [hevrhf ba[uld_ m]e_\h^h jh^Z Hl]hgdZ Da_hljhiZ [_gaheZ k \h^hc k g_[hevrbfb ijbf_kyfb gbljh[_gaheZ b Zahlghc dbkehlu \ oh^_ ijhp_kkZ iha\heyeZ ih^^_j`b\Zlv dhgp_gljZpbx dbkeh lu ihklhygghc Ihke_ jZa^_e_gby Za_hljhiZ \ k_iZjZlh j_ [_gahe \ha\jZsZeky gZ gbljh\Zgb_ >ey j_ZebaZpbb ^Zggh]h ijhp_kkZ [ueZ kha^ZgZ mdjmig_ggZy mklZgh\dZ dhlhjZy ^_ckl\h\ZeZ \ ]h^u @ ijh\h^blv klZ^bx hl ]hgdb Za_hljhiZ ih^ \Zdmmfhf ^ey kgb`_gby l_fi_jZ lmju \ j_Zdlhj_ ey kha^Zgby lZdh]h l_ogheh]bqgh]h ijh p_kkZ g_h[oh^bfh [ueh gZclb mkeh\by \ dhlhjuo ^hey hdbkebl_evguo j_Zdpbc [m^_l k\_^_gZ d fbgbfmfm l_ ijb[eb`_gZ d ijhp_kkZf k bkihevah\Zgb_f k_jghZahlguo kf_k_c b h[_ki_qblv \ukhdb_ kdhjhklb gbljh\Z gby g_ lhevdh lhemheZ gh b bahf_jh\ fhghgbljhlhemheZ
113


< N @bebg < E A[Zjkdbc


iheghc j_]_g_jZpbb hljZ[hlZgghc Zahlghc dbkehlu [_a bkihevah\Zgby k_jghc Ij_^eh`_ggZy l_ogheh]bq_kdZy ko_fZ ^ZgZ gZ jbk 5. < ijhlhqguc j_Zdlhj _fdhklgh]h beb pbjdmeypbhggh]h lbiZ ih^Zxl h^gh\j_f_ggh lhemhe b dhgp_gljbjh\Zg gmx +123 Lhemhe bg`_dlbjmxl \ j_Zdpbhggmx fZkkm ]^_ [ukljh ijhl_dZ_l ij_\jZs_gb_ _]h \ fhghgbljhkh _^bg_gb_ ihke_^mxs__ h[jZah\Zgb_ ^bgbljhlhemheZ lj_[m_l agZqbl_evgh [hevr_]h \j_f_gb Ijb aZimkd_ \ j_Zdlhj \\h^blky k\_`Zy ZahlgZy dbkehlZ Z ijb g_ij_ ju\ghc jZ[hl_ -- j_]_g_jbjh\ZggZy ba dhehggu dhg p_gljbjh\Zgby +123 Ijb l_fi_jZlmj_ K j_Zdpby aZ\_jrZ_lky aZ q b \j_fy __ fh`_l [ulv mf_gvr_gh ijb m\_ebq_gbb fh^mey ih Zahlghc dbkehl_ ^h fbg Dhgp_gljZpby +123 gZ \uoh^_ ba ZiiZjZlZ ^he`gZ [ulv qj_a\uqZcgh \ukhdhc -- ^ey kgb`_gby kh^_j `Zgby dj_aheh\ \ j_Zdpbhgghc kbkl_f_ J_ZdpbhggZy fZkkZ jZkl\hj ^bgbljhlhemheZ \ Zahl ghc dbkehl_ ihklmiZ_l \ dhehggm dm^Z h^gh\j_f_ggh ih^Zxl jZkl\hj khe_c Zahlghc dbkehlu \ jZa[Z\e_gghc (63%) HNO3 bkihevamxl ljb]b^jZl gbljZlZ fZ]gby beb _]h kf_kv k ljb]b^jZlhf gbljZlZ pbgdZ Ijb kf_r_gbb wlbo ^\mo ihlhdh\ h[jZamxlky fbg_jZevgZy nZaZ ij_^ klZ\eyxsZy kh[hc jZkl\hj gbljZlh\ b Zahlghc dbkehlu \ \h^_ b hj]Zgbq_kdbc kehc -- jZkieZ\e_gguc ^bgbljh lhemhe GbljZlu f_lZeeh\ \ wlhc kbkl_f_ h[jZamxl
,,, , ,, ,9 9 9,

IhgZ^h[behkv [he__ e_l ^ey j_r_gby wlhc aZ^Zqb nbjfhc 2/,1 KR: [ueZ jZajZ[hlZgZ l_o gheh]by ihemq_gby ^bgbljhlhemheZ hkgh\ZggZy gZ gbl jh\Zgbb lhemheZ h^ghc Zahlghc dbkehlhc > @ Ijb jZajZ[hld_ l_ogheh]bb [ueh ihdZaZgh qlh gbljh\Zgb_ lhemheZ dhgp_gljbjh\Zgghc +123 g_ khijh\h`^Z_lky m\_ebq_gb_f ^heb hdbkebl_evguo ijhp_kkh\ _keb ijh \h^blv _]h ijb l_fi_jZlmj_ gb`_ K \ukhdb_ kdhjh klb ijhp_kkZ ^hklb]Zxlky aZ kq_l bkihevah\Zgby \ukh dhdhgp_gljbjh\Zgghc Zahlghc dbkehlu dhgp_gljZpby HNO3 \ hljZ[hlZgghc dbkehl_ \ur_ ijb bkihev ah\Zgbb gbljZlh\ fZ]gby b pbgdZ ^ey \u^_e_gby ijh ^mdlZ ba dhgp_gljbjh\Zgghc +NO3 g_ lj_[m_lky jZa[Z\ e_gb_ ihke_^g_c \h^hc qlh ijb\h^bl d khdjZs_gbx h[t_fZ klhqguo \h^ H^gh\j_f_ggh [ueZ j_r_gZ aZ^ZqZ <
]

\ukrb_ ]b^jZlu b h[e_]qZxl bkiZj_gb_ Zahlghc dbkeh lu >ey kgb`_gby l_fi_jZlmju \ dhehgg_ mf_gvr_gby hdbkebl_evguo ijhp_kkh\ hl]hgdm Zahlghc dbkehlu ijh\h^yl ih^ jZaj_`_gb_f @ bkihevamxl dbkehlgmx kf_kv khklZ\Z HNO3, 62% H2SO4 b +22 l_fi_jZlmjZ ijhp_kkZ -- 85 K Ijh^mdl kh^_j`bl B-, 11% D-, 2% E-^bgbljh[_gaheZ b B-gbljhn_gheh\ N_gheu m^Zeyxlky ijb kh^h\hc ijhfu\d_ Z D-^bgbljh[_gahe -- ijb kmev nblghc hqbkld_ @
AZdexq_gb_

Jbk L_ogheh]bq_kdZy ko_fZ ihemq_gby ^bgbljhlhemheZ \ kj_^_ Zahlghc dbkehlu:

< ihke_^gb_ ^_kylbe_lby \ l_ogheh]bb gbljhkh_^b g_gbc ijhbahr_e dZq_kl\_gguc kdZqhd iha\heb\rbc j_adh ih\ukblv wdheh]bq_kdmx [_ahiZkghklv ijhba\h^ kl\Z b kgbablv ijhba\h^kl\_ggu_ aZljZlu AZ^ZqZ p_e_gZijZ\e_ggh]h baf_g_gby bahf_jgh]h khklZ\Z ijb gbljh\Zgbb j_r_gZ lhevdh \ eZ[hjZlhjguo mkeh\byo b `^_l ijb_fe_fh]h l_ogbq_kdh]h j_r_gby
EBL?J:LMJ:
1. Olah G.A., Malhorta R., Narang S.C. Nitration. Methods and Mechanisms. VCH. N.Y., Weinheim, Cambridge, 1989, 330 p. 2. Marziano N.C., Sampoli M., Pinna F., Passerini A. J. Chem. 6RF 3HUNLQ 7UDQV ,, 7, p. 1163--1166. 3. Belson D.J., Strachan A.N. Ibid., 1989, p. 15--19.

j_Zdlhj -- dhehggZ j_]_g_jZpbb +12 ; 3 -- k_iZjZlhj kbkl_fZ j_]_g_jZpbb jZkl\hjZ khe_c lhemhe ,, -- 98%-gZy +12 ; III -- j_]_g_jbjh\ZggZy gZy +12 ; IV -- 63%-gZy +12 ; V -- ^bgbljhlhemhekuj_p9, -- \h^Z
1 4 I 9 -- -- -- 8%3 3 3 3



114


Jhk obf ` @ Jhk obf h[-\Z bf >B F_g^_e__\Z
4. Coombes R.G., Moodie R.B., Schofield K. J. Chem. Soc. (B), 1968, j. 800 5. Hughes E.D., Ingold C.K., Reed R.I. J. Chem. Soc., 1950, p. 2400--2440. 6. =hj_ebd F< Wnjhk EK Hkgh\u obfbb b l_ogheh]bb ZjhfZlbq_kdbo kh_^bg_gbc F Obfby k 7. A[Zjkdbc _fu]bg KK DZlZeba \ ijhfure_gghklb k --9. 20. IZl_gl KR: 3928476. 21. GZ]b RF Am[dh\ W: Rm[bg <= Ba\ :G KKKJ K_j obf k --1934. 22. Milczak T., Jacniacki J., Zawadzki J., Malesa M., Skupinski W. Synth. &RPPXQ Y 2, p. 173--187. 23. GZ]b R.F., Am[dh\ W.:., Rm[bg <.=. Ba\. :G KKKJ K_j obf 7, c. 1650--1652. 24. Yadav J.J. Nair Microporous and Mesoporous Materials, 1999, v. 33, p. 1--48.



l L 3

25. Kameo T., Hirashima O, Manabe O. J. Chem. Soc. Japan, Chem. Ind. ChHP 3, p. 413--419. 26. Marzianj N.C., Tortato C. e. a. Catalysis Letters, 1999, v. 58, p. 81--87. 27. Attina F., Cacace F. Gazz. &KLP ,WDO Y 4, p. 241--248. 28. Kwok T.J., Jayasuriya K., Damavarapu R., Brodman B.W. J. Org. Chem., 1994, v. 59, p. 4939--4942. 29. Strategic Environmental Research and Development Program (SERDP), Pollution Provention PP-1409, Picatini Arsenal, USA, 2005, www.Serdp.org. 30. Vassena D., Kogelbayer A., Prince R. Stud. Surf. Sci. Catal., 1999, v. 125, p. 501--506. 31. @bebg B F_g^_e__\Z k 32. IZl_gl KR: 3928475 33. PEP Review 78-1-2, May 1979. 34. Evropian Chemical News, 1997, 13-19.10. 35. Frank H.G., Stadelhofer J.W. Industrial Aromatic Chemistry. Berlin: Springer-Verlag., 1988, 466 p. 36. Guenkel A.A., Maloncy T.W. «Nitration». ACS Symposium VHULHV 623. Am. Chem. Soc. Washinton, 1996, j. 223--233 37. AZy\dZ KR: aZy\dZ KR: 20020193642. 38. IZl_gl KR: 4772757, 1988. 39. Kozak G.D., Raikova V.M., Potapov V.V. Proc. of VII Sem. «New Trends in Research of Energetic Materials. Pardubice. Chech. Repub., 2004, j. 124--129. 40. IZl_gl KR: 2370558. 41. Quakenbush A.B., Pennington B.T. «Nitration». ACS Symposium VHULHV $P &KHP 6RF :DVKLQJWRQ j. 214--222. 42. IZl_gl KR: 43. Ullmanns Encycl. der tech. Chemie. 4-te Aufl. Bd.17. Weinheim, Verlag Chemie, 1979, S. 383--416. 44. Guenkel A.A., Prime H.C., Rae J.M &KHP (QJ j. 50-- 86 3DWHQW

115