1、?zAnalytical Chttp:/202.116.83.148?z?z?2510275?zAnalytical Chemistry p.1/614?z?%?z?%?z?A?:?%?L?SA?”eSN?z?z?%?n?z?%?n?z?%?A?zAnalytical Chemistry p.2/64.1?z?4.1.1 V?_?3?A?mU?UdA“XFe3+/Fe2+I2/IFe(CN)36/Fe(CN)46?_?U3?A?m?S?n?UdA“O?(J=?XMnO4/Mn2+Cr2O27/Cr3+?z?X?X?Fe3+e=Fe2+MnO4+8H+5e=Mn2+4H2O?z?X?X?I2+2
2、e=2ICr2O27+14H+6e=2Cr3+7H2O?zAnalytical Chemistry p.3/64.1?z?4.1.2?3?e?z?1 mol/L?lfr?9B?A?K?S?4?3lfr?B?AX?C?e?X?3?M?AFe3+e=Fe2+E=E?+0.059lgFe3+Fe3+Fe2+Fe2+=E?+0.059lgFe3+Fe(II)Fe3+Fe2+Fe(III)Fe2+?z?1molL1?E=E?+0.059lgFe3+Fe(II)Fe2+Fe(III)=E?0?zAnalytical Chemistry p.3/64.1?z?4.1.3?z?ue?z?A?1?d?A?K5?
3、k?IO?O?n2O1+n1R2?n1O2+n2R1?A?k?O1+n1e=R1O2+n2e=R2?4?a?E1=E?1+0.059n1lgcO1cR1E2=E?2+0.059n2lgcO2cR2a?L?zAnalytical Chemistry p.3/64.1?z?4.1.3?z?3?A?=E1=E2?lgK0=lgcn2R1cn1O2cn2O1cn1R2=(E?01 E?02)n0.059?n?Af=n1?n2?zAnalytical Chemistry p.3/64.1?z?4.1.4 zO?:?A?1?d?z/?/?5?6d?A?5?7?zAnalytical Chemistry p
4、.3/64.1?z?4.1.5 K?A?A?O?A?O?3S?ALkO?,?A?A?X?A?K2Cr2O7+6KI+14HCl=8KCl+2CrCl3+7H2O+I2?k4KIL?5?,p?A?O?X?A?2MnO4+5C2O24+16H+=2Mn2+10CO2+8H2O?u75e?A?375e?85e?m?u85e?H2C2O4)?J?xzJ?O?A?zAnalytical Chemistry p.3/64.1?z?4.1.6 xz?A?p?Axz?A?xzJ fl?A?KxzJ?A?p?A du?A?u)r?,?A?1?y?X?AMnO4+5Fe2+8H+Mn2+5Fe3+4H2O?e?A
5、2MnO4+10Cl+16H+2Mn2+5Cl2+8H2O?zAnalytical Chemistry p.3/64.2?z?%?n4.2.1?z?%?Jg?J 3?z?%IOM?%?k?XJ?A?C?f?o%?7,?JX3p?aKMnO4?2 106?w?M?fi?w?J k?k?z?5?U?zJ?J?)A?%“:X?M5Dfi?9M?A)?=?z?I2?I?=?d39?DfiM?J3eDfi?u?105mol L1?9M?g?u)?z?A?J a?J?z?k?3%L?Jd?z?C?d?C?z?C5?“:XK2Cr2O7M?%Fe2+?X?J?z?b?O?:?d?C?z?M?wb?%“:?z
6、Analytical Chemistry p.4/64.2?z?%?n4.2.1?z?%?JInO?InROL?J?z?z?In(O)+ne=In(R)?X%LM?Cz?J?In(O)/In(R)?X?:E=E?ln+0.059nlgIn(O)In(R)?In(O)/In(R)10?M?y?z?In(O)/In(R)110?M?y?z?JC?E?In0.059n3?J?J?A?J?A?zO?:?“:?zAnalytical Chemistry p.4/64.2?z?%?n4.2.2?z?%?1.?z?%?An2O1+n1R2?n1O2+n2R1e?c01?O1%N?V0!?c02?R2?%JN
7、?V?d?c1=c01VV+V0=O1+R1c2=c02V0V+V0=R2+O2?zAnalytical Chemistry p.4/64.2?z?%?n4.2.2?z?%?1.?z?%?Ac01Vc02V0=O1+R1R2+O2=R1(O1R1+1)O2(R2O2+1)3%L?%?mkXeX?O2=n1n2R1%a=c01Vc02V0=n2(O1R1+1)n1(R2O2+1)=n2n1f?zAnalytical Chemistry p.4/64.2?z?%?n4.2.2?z?%?1.?z?%?A?UdA?25C?E=E?01+0.059n1lgO1R1=E?02+0.059n2lgO2R2f
8、=1+10n1(EE?01)/0.0591+10n2(EE?02)/0.0593%?0.50?J?%?2.00?zJ?%?zAnalytical Chemistry p.4/64.2?z?%?n4.2.2?z?%?2.zO?:?O?3zO?:?f=1?z?%?A3zO?:?Esp=n1E?01+n2E?02n1+n2?zAnalytical Chemistry p.4/64.2?z?%?n4.2.2?z?%?3.%?%J?E?01f=n1%?E?02f=n2?%?u0.1%K?(E?02+0.059n2lg103)(E?01+0.059n1lg103)?zAnalytical Chemistr
9、y p.4/64.2?z?%?n4.2.2?z?%?eZ(?zJ?J?E?0?%?%?%?zJ?J?n1=n2?zO?:?%?:X?Ce4+Fe2+=Ce3+Fe3+?0.861.26VEsp=1.06Vn16=n2?zO?:?n?X?2Fe3+Sn2+=2Fe2+Sn4+?0.230.50VEsp=0.32V?E?0Sn4+/Sn2+=0.14VE?00.2V?kw?E?0?0.20.4V?m?(“:E?00.4 V?J?zAnalytical Chemistry p.4/64.2?z?%?n4.2.2?z?%?4.?z?%?A?z?%?A?L?n2O1+n1R2?n1bO2+n2aR1?L
10、aq?%?f=1+aR1a110n1(EspE?01)/0.0591+bO2b110n2(EspE?02)/0.059f=1?zO?:?Esp=n1E?01+n2E?02n1+n2+0.059n1+n2lgbO2b1spaR1a1sp?zAnalytical Chemistry p.4/64.2?z?%?n4.?z?%?AeIO4O?zO?:ukH+?z?%?A3O?“A?k?NH+?XK2Cr2O7%Fe2+IOO?Esp?O?“?Esp=n1E1+n2E2n1+n2+0.059n1+n2lg12cCr3+0.059n1+n2lgH+14?zAnalytical Chemistry p.4/
11、64.2?z?%?n4.2.2?z?%?4.?z?%?A?zAnalytical Chemistry p.4/64.2?z?%?n4.2.3?z?%(J?O?|XL?X?A?Z?%JT5%d?A?O?X?aX m bY cZ m dT?aX m dT?wX=adcTVTMXmsp.152?zAnalytical Chemistry p.4/64.2?z?%?n4.2.4“:?u?A?n2O1+n1R2?n1O2+n2R1“:?t=O1ep R2epcsp2=10n1E/0.059 10n2E/0.05910n1n2E/(n1+n2)0.059?zAnalytical Chemistry p.4
12、/64.3?z?%?n?n?“?k?z?n?|?z?pdG?J%?k?n?|?$dG?zJ%?zAnalytical Chemistry p.5/64.3?z?%?n?n?zJ?J?:?A?1?flL?zJ?Ju?A?k?J5?zAnalytical Chemistry p.5/64.3?z?%?n4.3.1?zJ1.(NH4)2S2O83?50?S2O28?r?zJ?Ce3+?z?Ce4+VO2+?zVO2+33H2SO4H3PO40?3Ag+xze?Mn2+?z?MnO4?Cr3+?z?Cr2O27L?S2O28?7?A?2S2O28+2H2O 4HSO4+O2?zAnalytical C
13、hemistry p.5/64.3?z?%?n4.3.1?zJ2.KMnO43e?5M?MnO4?3Cr3+?3e?VO2+?z?VO3d?zCr3+?3w5M?MnO4N?Cr3+?z?CrO24L?KMnO4?NO2?A?2MnO4+5NO2+6H+=2Mn2+5NO3+3H2O?NO2?k?)?zAnalytical Chemistry p.5/64.3?z?%?n4.3.1?zJ3.H2O23NaOHM?Cr3+?z?CrO243HCO3M?Co(II)?z?Co(III)L?H2O2?7?zAnalytical Chemistry p.5/64.3?z?%?n4.3.1?zJ4.HC
14、lO4a?9?HClO4?Cr3+?z?Cr2O27?kH3PO4?3?Mn2+?/?z?Mn3+)?Mn(H2P2O7)33L?HClO4D”?=?zU?a?9?HClO4?k?u)?zAnalytical Chemistry p.5/64.3?z?%?n4.3.1?zJ5.KIO49?50?Mn2+?z?MnO4?7?L?KIO4?zAnalytical Chemistry p.5/64.3?z?%?n4.3.2?J1.SnCl2?Fe3+?Fe2+L?SnCl2?7HgCl2M?)Hg2Cl2?D?3?A;?L?SnCl2K?Hg2Cl2?Hg?HgU?zJ?A?zAnalytical
15、Chemistry p.5/64.3?z?%?n4.3.2?J2.TiCl33?cTiCl3SnCl2TiCl3?Fe3+?L?TiCl3?LYD”M?l?Y?M)?z?zAnalytical Chemistry p.5/64.3?z?%?n4.3.2?J3.7?J?7?Jk?!c?X3HClM?Sn4+?Sn2+?|C?zAnalytical Chemistry p.5/64.3?z?%?n4.3.2?J4.SO2?f?J?Fe3+?Fe2+?U?Ti4+?Ti3+3?H2SO4?3?A?kSCN?A?1?zAnalytical Chemistry p.5/64.4?z?%?A?z?%?p?
16、a?a9?z?zAnalytical Chemistry p.6/64.4?z?%?A4.4.1 p?a:?zU?r?!m?/?k?Mn2+Cu?I,?J:?IOM?A?E,u)B?A%?J5?I?%?3r?M?A?MnO4+8H+5e=Mn2+4H2O3?5!5fw5M?A?MnO4+2H2O+3e=MnO2+4OH3rw5?MnO4+e=MnO24?zAnalytical Chemistry p.6/64.4?z?%?A4.4.1 p?aKMnO4M?un?KMnO4M)35N?2Y?KMnO4M?9C?1h,?23UM?U?3?5?z?L?D?L?KMnO4M?;?3k?3V?I?zAn
17、alytical Chemistry p.6/64.4?z?%?A4.4.1 p?aKMnO4M?IH2SO4M?2MnO4+5C2O24+16H+=2Mn2+10CO2+8H2O?37085ea?30.51mol/L%?m%?flxzJ?%cA%MnSO4?xzJ?J?KMnO4g?J%“:?fi?30.51min.S?a?pu90e?u)?zAnalytical Chemistry p.6/64.4?z?%?A4.4.1 p?a%?“?%?%m?%?zAnalytical Chemistry p.6/64.4?z?%?A4.4.1 p?a%?“?%:?%N?5?XFe2+!NO2!As3+
18、!Sb3+!H2O2!C2O24?2MnO4+5H2O2+6H+5O2+2Mn2+8H2O?zAnalytical Chemistry p.6/64.4?z?%?A4.4.1 p?a%?“?%?z5?%X?MnO2?3H2SO4M?L?Na2C2O4IOM?MnO2?.?KMnO4IOM?%L?C2O24MnO2+C2O24+4H+Mn2+2CO2+2H2O2MnO4+5C2O24+16H+=2Mn2+10CO2+8H2O?zAnalytical Chemistry p.6/64.4?z?%?A4.4.1 p?a%?“m?%?,?z5?m?%?1?X?Ca2+?k?Ca2+?D?CaC2O42
19、DH2SO4?DM)KMnO4IOM?%M?C2O24m?Ca2+?CaC2O4+2H+=H2C2O4+Ca2+2MnO4+6H+5H2C2O4=2Mn2+10CO2+8H2O?zAnalytical Chemistry p.6/64.4?z?%?A4.4.1 p?ak?k?+MnO4+OH CO23+MnO24+H2O?A?M?zd?MnO24?z?3MnO24+4H+?2MnO4+MnO2+2H2OO(L?FeSO4IOM?kpd?lf?Mn2+KMnO4IOM?%L?Fe2+d?gKMnO4?9FeSO4?O?k?zAnalytical Chemistry p.6/64.4?z?%?A4
20、.4.2?a?aNJX3140250eZH?IOM?aIOM?a?zU?vkKMnO4r31 mol/LHClM?e?Cl?5?Z6?KMnO4?Cr2O27+14H+6e=2Cr3+7H2OE?=1.33V?zAnalytical Chemistry p.6/64.4?z?%?A4.4.2?aAc?c?9?HCl)SnCl2?Fe3+?Fe2+312molL1H2SO4 H3PO4?0?X?J?a%Fe2+?“:?u?H3PO4Fe3+)?Fe(HPO4)2?$Fe3+/Fe2+?%?Od?du)?Fe(HPO4)2?Fe3+?k|u*?“:?zAnalytical Chemistry p.
21、6/64.4?z?%?A4.4.3 9?9?EI2/I$?5?I2IOM?%?9?Dfi?J?As2O3Sb3+Sn2+?5?U3w5M?1Ku)?z?AXgc1?3C1300e?-?+O2-?gc?1=z?SO22I2%?A?I2+SO2+2H2O=2I+SO24+4H+?zAnalytical Chemistry p.6/64.4?z?%?A4.4.3 9?m?9?EI2/Ip?z5?3?eI?,?Na2S2O3IOM?%”?I2,?m?9?XKMnO43?5M?L?KI?I22Na2S2O3M?%2MnO4+10I+16H+=2Mn2+5I2+8H2OI2+2S2O23=2I+2S4O2
22、6?zAnalytical Chemistry p.6/64.4?z?%?A4.4.3 9?9?5?I2?u?A3e?1L?II2)I3O?M)?I?z?;1)I2?=Na2S2O3%?fl?zAnalytical Chemistry p.6/64.4?z?%?A4.4.3 9?Na2S2O3M?#?CO2?k?e%?2Y?Na2CO3M?fw5?)?M?IM?CZ?1AL?2I?,?M?zAnalytical Chemistry p.6/64.4?z?%?A4.4.3 9?Na2S2O3M?ICr2O27+6I+14H+=2Cr3+3I2+7H2OIO3+5I+6H+=3I2+3H2OM?A
23、?fl?IN?O2?z?0.20.4 mol/LK2Cr2O7?KI?A?M?;?u9I/X3V?m?A?2?1%KIO3?KI?I?9?%KIM?kKIO3I2XJKIM?w?KAflkNa2S2O3M?%?2?zAnalytical Chemistry p.6/64.4?z?%?A4.4.3 9?I2M?I?I2+KIL?+H2O?D”k?I?fiI?Na2S2O3IOM?As2O3I?A?As2O3+6OH=2AsO33+3H2OAsO33+I2+H2O?AsO34+2I+2H+?zAnalytical Chemistry p.6/64.4?z?%?A4.4.3 9?9?AS2H2S?3
24、?5M?I2U?zS2?H2S+I2=S +2I+2H+5%?U3w5M?1K?S2?z?SO24S2+4I2+8OH=SO24+8I+4H2O?zAnalytical Chemistry p.6/64.4?z?%?A4.4.3 9?9?A?7?H2O2?HCl)?Cu+2HCl+H2O2=CuCl2+2H2O?L?H2O2N!M?3pH=3.2 4.0L?KII2?2Cu2+4I=2CuI +I2)?I2Na2S2O3IOM?%Dfi?J3?I2?Na2S2O3M?%?NH4SCNCuI=z?M)?CuSCN?CuII2?NCuI+SCN=CuSCN +I?zAnalytical Chemistry p.6/64.4?z?%?A4.4.4?z?%1?Fe2+?a?-?g!$?7gMn?zAnalytical Chemistry p.6/6
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