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Valence electron configurations (n 1)d1 8ns1 2 with exceptionPd 4d10 Pt 5d96s1 W 5d46s2 gSSv'lSpe +2vNepev Tvgؚ'lSpe vNlS 'l؏S^ {$)HHHHHHH#l%8=>?E5.4lTyP[0MyP['YY gr$ @] 14-2 TitaniumN14-2-1 General Characteristics 14-2-2 Titanium 14-2-3 Compounds of TitaniumOOGH J K L M NOPQRSTUVWXYZ\r4*14-3 Cr Mo W oRe &B 14-3-1 General properties 14-3-2 Cr and its compounds 14-3-3*C8 ^_ a"b#c$d%e&f'g(h)i*j+k,l-m.n/o0p2q3u7v8w9x:y;z<{=|>}?~@e hKMnO4 +2KF +10HF +3H2O2 = 2K2MnF6 +8H2O+ 3O2 SbCl3+5HF=SbF5+5HCl K2MnF6 + 2 SbF5 =2KSbF6+ MnF3 +1/2 F2iNNN3N33N33NNFNFF3N3F3N33N33F3FF3N3FNFNFNFMNOPQRSTUVWXYZ[\]^_`abcdfghsijklmnopqt   0` r77f3/Ʊ` fff` KfxP` 7_/U<ff` HghXs3q̙` WXcklugti~^ӤO` ־3f3f` 33^` J%xiff3>?" dd@,?nFd@  d nF@ d`nF n?" dd@   @@``PP   @ ` ` p>> .(  6 T ~  "~  c B@CW DEF"d@ W @W @W W @`".~  c B,CW DEF"d@ W ,W ,@`". \ ~  "~  c B CDEF"@   @`"(4  c B C DEF"d@ @`"(W4  c BtC DEF"d@t t tt@`"~   c B CDEF"@ @`"([4W   c B CDEF"d@ @`"(4   c B CDEF"2@  @`"(4[   c BC DEF"d@ @`"_   c BC DEF"@ @`"  c BC DEF"@  @`"\  B$ ?"0F  LUSQdkYkHrh7h_     0踛 "0  8USQdkYkHre,g7h_ ,{N~ ,{ N~ ,{V~ ,{N~    00 "`P  \*   0 ƛ "`p   ^*   0@ț "`0  ^* H  0޽h ? fff80___PPT10. @F$ Shimmerv  0 v(   T ~  "~~b ~ # "~  c B@CW DEF"d@ W @W @W W @`".~  c B,CW DEF"d@ W ,W ,@`".  c B CDEF"2@  @`"(4[  c BC DEF"@ @`"  c BC DEF"d@ @`"_b \~  # "\~   c B CDEF"@   @`"(4   c B C DEF"d@ @`"(W4   c BtC DEF"d@t t tt@`"~   c B CDEF"@ @`"([4W  c B CDEF"d@ @`"(4  c BC DEF"@  @`"\  HȔ ?"p  LUSQdkYkHrh7h_    0f " `   NUSQdkYkHroRh7h_   0P "`P  \*   0 "`@`   ^*   0@ "`0  ^* H  0޽h ? fff80___PPT10. @F$ 0 ~v (      0t^P P   P P*     0paP    P \* d   c $ ?  P   0cP  0 P 8USQdkYkHre,g7h_ ,{N~ ,{ N~ ,{V~ ,{N~     64P _P  P Z*    6dP _  P \* H   0޽h ? 3380___PPT10.gt 0  h4(  h h 0 9  JChapter 14 Elements in d- Block Ǐ!nCQ }R{| d:Sb!B f!B g! ,{VhTg,{NǏ!n| ,{N0mQhTg,{N0 NǏ!n|'`(v= @B +o 0 0l&(  l l 0,dX  Stability ThTg N]S 'lS`GSؚTQMNO Eg, f!B Mn7+ Fe3+ Co3+ Ni2+ Te N N CQ }'lSpevSS'`TNQ\ ؚ'lS`N3z[Np:SvS Cr2O72- 0CrO42- strong oxidizing agent MoO42-0WO42- weak oxidizing agent S_NW0N]xW0T!TvUI{MSOMTe SHTsNO'lS`+1000-10-20-30C C$CKCKCKCK/CKCKKCKK"CKKCKKKC ! +#H l 0޽h ? ̙33y___PPT10Y+D=' >= @B +  0 @p(  p^ p 0{7G_ |2. Atomic radii ThTgN]S JS_Q\ (Wcя`!BeX'Y TeN N N JS_X ,{NhTg H",{mQhTg 2?0C$/C, p 0@7b,$ 0 TV 3. Physical properties of elements ---- similar [^'Y lx^'Y qlpؚ ,{ NǏ!n|ё^\wQ gyr+R'Yv[^ N]Sё^\vqpGSؚS NM O e!B Crqpgؚ lx^g'Y Mn0Tc S8^NO 3385! W0Re qpgؚ B0C1C$zC00H p 0޽h ? ̙33___PPT10+\VD' >= @B D' = @BA?%,( < +O%,( < +D' =%(D' =%(DT' =A@BBB B0B%(D' =1:Bvisible*o3>+B#style.visibility<*p%(D' =-6B'blinds(horizontal)*<3<*pD' =%(D' =%(DT' =A@BBB B0B%(D' =1:Bvisible*o3>+B#style.visibility<*p%(D' =-6B'blinds(horizontal)*<3<*p+p+0+p0 ++0+p0 +) 0 PHPt(  t t 0p  HX4. As central elements to form complexes N.t5"(n 1)d ns np~vя N:NzzhS SNBgSb. O Co(a!) sp3BgS Co(SCN)42 Ni(a!) dsp2BgS Ni(CN)42 CFSE: Fe0Co0Nib_bMTirvRg:_ 0*C$7CK CKKCK CKKCK,      H t 0޽h ? ̙33y___PPT10Y+D=' >= @B +%  0 <4 (  r  S |dF   r  S T0  ^  6j  S A ??"? ^  6j  S A ??"? ^   6$$v  s ,A ??"?&     0,<& 0Figure Visible spectrum of Ti(H2O)6 3+ solution`1 2 KKK H  0޽h ? fff___PPT10i.+D=' >= @B + 0 `x>(  x x 0T,71  P d1-d9yP[ gr dhS N g1~ 5*N*gb[5uP[v4lTyP[ 8^wQ g N Tvr SVbUSd5uP[d-dÍ 8T6eSIQ-NvgNIQ >fr d00d10er , O: Sc3+ La3+ Ti4+ Zn2+ Cd2+ Hg2+ Ag+0C K C K PC K C K  C K C K C K !C K C K C K C K HH x 0޽h ? ̙33y___PPT10Y+D=' >= @B +$  0  $(  r  S $0F   r  S 0  H  0޽h ? fff80___PPT10.(* 0 (     6  1  14-2-1 General Characteristics Valence electron configuration 22 Ti 3d24s2 147pm 0.63% 40 Zr 160pm 72 Hf 158pm b0?0 0  $"C CKCKQC4i  6d 2Due to the lanthanide contraction, the sizes of Zr and Hf are almost similar and these elements have almost identical properties in the element as well as in the combined states. Oxidation numberTi (b!)Ti(H2O)63++} Ti(c!)er0bx Due to the presence of a single electron, the Ti (b!) state forms colored and paramagnetic compounds.0CKKK26$0|0 $e  0\.  U 14-2 Titanium,0 $$H  0޽h ? ̙33y___PPT10Y+D=' >= @B + 0 /'(    64p Q 400 C8  6`:d{  Electrode potential Ti Ti4+/Ti = "0.882 V Zr Zr4+/Zr = "1.529V Hf Hf4+/Hf = "1.70V 1050 0 C K C K C K C 44  6Gd  zReactivity of the elements increases from Ti to Hf, due to higher bond energies, which is reflected in the  values. Dx00 uCC"0F"  0@`@ 0 0H  0޽h ? ̙33y___PPT10Y+D=' >= @B + 0 (  u  6(U7,X  MCN Ti: 4 , 6 TiX4 TiF62 - Zr/Hf: 6-8 ZrF37- Zr[(C2O4)4]4- |0I0 0 C K C K K C K C K K  C K C K C K C K C "'!"  0` @ 0 0LB  c $D H  0޽h ? ̙33y___PPT10Y+D=' >= @B + 0 E(    6hpPP p14-2-2 Titanium D00 C(C  67' s5How does Ti occur in nature and how is it extracted? "606C  6Pd TLD___PPT9&  2Extraction of Titanium Ti is the tenth most abundant element (Al Fe Ca K Mg Ti ) and the seventh most abundant metal (0.63%) in earth s crust. 100 0 GCC @`"  00`@ 0 0H  0޽h ? ̙33y___PPT10Y+D=' >= @B + 0 ~(    6 2  8NTiO2 Ores  retile ё~w  ionic compounds Retile is a basic crystallographic lattice for ionic compounds. anatasewbrookitegw. These two forms of TiO2 have distorted rutile lattice. Anataes is more stable by 8-12 kJ/mol. Ilmeaite FeTiO3 contains impurities of iron and other base metals i00 0 G3O3G3G G3GOIGG3O36G V) "<,"  0@ 0 0H  0޽h ? ̙33y___PPT10Y+D=' >= @B +  0    (  t  6<T<l `$Wohler s process 2FeTiO3 +2K2CO3excess ! 2K2TiO3 + Fe2O3 + CO + CO2 K2TiO3 + 6HF ! K2TiF6 + 3H2O K2TiF6 + 2NH4" H2O ! TiO2 + 2KF + 2NH4HF20|0 GOGOGO GOGOGOGO GOGOGO GOGOGOGOGOGOGOGO GOGOG>cT  6!2w  \a$Rose s process FeTiO3 + H2S ! FeS + TiO2 + H2O FeS +2HCl ! FeCl2 + H2S Powered ilmenite is heated to redness in a stream of H2S whereby FeS is formed. Upon cooling, digestion in HCl dissevers FeS as FeCl2 leaving behind TiO2. 00 GOGOGOGOGOGO?GOMGOGOGG G| %1' #"  0`@ 0 0H  0޽h ? ̙33B 0  (    6}<  < b$ Acid digestion FeTiO3 + 3H2SO4 (conc.) ! Ti(SO4)2 + FeSO4 + 3H2O Ti(SO4)2 + 2H2O ! TiO2 + 2H2SO4 Slight dilution with water, followed by crystallization deposits green FeSO4" 2H2O. Upon diluting the mother liquor and boiling, hydrated TiO2 gets precipated.00 GOGOGOGOGOGOGOGOGOGOGOGOGOLGOGO<GOG$ T"  0`@  0 0H  0޽h ? ̙33 0 rj (  "  6|i7  c$ Acid fusion FeTiO3 + 4KHSO4 ! FeSO4 + TiOSO4 + 2K2SO4 + 2H2O TiOSO4 + H2O ! TiO2 + H2SO4 (%) Powered ilmenite is fused with six times its weight of KHSO4. Upon cooling, water extract leaves insoluble TiOSO4 as the residue. Upon boiling the residue with water, hydrolysis of basic sulphate is complete to TiO2. 070 GOGOGOGOGOGOGOGOGOGOGOGOIGO4GOeGOGG G6q"  0@  0 0H  0޽h ? ̙33  0 8 0 (    6H7f Pd$ Kroll s process 2FeTiO3 + 6C + 7Cl2 ! 2FeCl3 + 2TiCl4 + 6CO (1200K) TiO2 + 3C ! TiC + 2CO (600K) TiC +2Cl2 ! TiCl4 + C (600K) TiCl4 + (2+n)H2O ! TiO2" nH2O + 4HCl00 GO GO GOGOGO"GOGOGO GOGOGO G6S@  6(7v bIf the ore is preroasted with coke around 1400K, some carbides are formed. 1.Separation of Ti and Zr 2.Fractional distillation of chlorides Add water to TiSO4 + ZrSO4 / SmH2SO4 ! Zr(SO4)2" 4H2O! rK0y0 0 GOGOGOGO GOGOGOGD JF"  0@  0 0H  0޽h ? ̙33 0 xp0 (  (  67}  e$ Alkali fusion 2FeTiO3 + 2NaOH +Na2O2 ! 2Na2TiO3 + Fe2O3 +H2O TiO2 + 2NaOH ! Na2TiO3 + H2O Na2TiO3 + H2SO4 ! Na2SO4 + TiO2" nH2O 0u0 GO GOGOGOGOGOGOGOGOGOGOGOGOGOGOGOGOGOGOGOG"  0@  0 0H  0޽h ? ̙33 0 VN@ (    6D7  P(2)؏S `$ TiO2 + Al ! Ti + Al2O3 (2500K) C ! Ti + CO a$ TiCl4 + Ca (Mg\Na) ! Ti + CaCl The metal is obtained in a powered form and is pyrophoric. 00 0 G C K C K C K 0C K WC F^1   6  d Z 32Cl" "2e = Cl2 4TiF62" + 4e = Ti + 6F" 0,0 0 C K  C K C K K C K C 4"  0@@  0 0H  0޽h ? ̙33r 0 "P (  h  s ,A ??^I    0('Zw xb$ Electrolysis 32Cl- -2e = Cl2 4TiF62- + 4e = Ti + 6F- <0 0 2C$K$ C$K$C$K$K$C$K$C$> H  0޽h ? ̙33 0 ` N(    627  P(3) Purification `$ TiI2 ! Ti + I2! (1800K) TiI4 ! Ti + 2I2 ! (wzz:_p) a$ zone refining :SWq b$ vacuum arc sublimation of impurities from the melting metal 00 0 G$C$K$ C$K$C$K$ C$K$dC$C$4HC  6C0 H"0 C   6G @  H"0 C "  00@ 0 0H  0޽h ? 3̙331 0 XPp (    0DL7C  Px2.Properties and Uses of Titanium `$ Ti is light metal with good tensile strength(b _:_^). In massive form, it resists corrosion in air due to the formation of a layer of insoluble TiO2 on the surface. In powered form, however, the element is pyrophoric, due to a large surface area, and burns to form dioxide in air.Y00 "CCCKCC,R AH  0޽h ? ̙33y___PPT10Y+D=' >= @B +  0    (    6\  "~a$ stable at low temperature reactive at elevated temperatures. T?00 =CC C,#  6z`  < O2 ! TiO (450-500K) N2 ! TiN (1000K) Ti + H2 ! TiH1.73 TiH2 (1000K,under pressure) C ! TiC(1400K) ! Ti + C (2500K) B ! TiB + TiB2 (red heat) "00 0  CK!CKCK CKCKfCKCP ,4  6l` 2  b$ H+ ! Ti Ti + HNO3(conc.) ! TiO2" n H2O! +NO2 + H2O 6HF(aq.) ! H2TiF6 + 2H2! z$0`0 0 CKCKCKCKCKCK$CKCKCKCn,"  s *@ 0 0L  0|   pc$ Form alloys with base metal ,such as Cu Fe Al Mg. <80 28CC6H  0޽h ? ̙33y___PPT10Y+D=' >= @B + 0 F> (    6`c H"0 C @  6`7-  Usages Ti is used for making filaments in bulbs and vacuum tubes. Ferrotitanium alloy (FeTi) is used as scavenger(QSBR) in metallurgy. ` 00 0 G$GFP"  0@ 0 0H  0޽h ? ̙33y___PPT10Y+D=' >= @B +V  0 } u  (    6  5 }14-2-3 Compounds of Titanium D00 C CB  6|;]G  l1.Titanium Dioxide TiO2 }v~QvTiO2 TiO2 is insoluble in HCl, HNO3 and aqua regia, but dissolves in conc. H2SO4 forming sulphate, or in alkalis forming titanates TiO32", TiO44". TiO2 + H2SO4 (conc.) ! TiOSO4 + H2O Ti(c!)+ OH" ! TiO2 TiO2 +NaOHconc. ! Na2TiO3" nH2O TiO2 + BaCO3 ! BaTiO3 + CO2! (%) 0^0#0 0 G3O3 G3O3G3GOGO,GOGO6GOOGOOGOGOGOGOGOGO GOGOGOGOGOGOGOGO GOGOG* S0L8X"  0@ 0 0H  0޽h ? ̙33y___PPT10Y+D=' >= @B +Q 0 xp (  (  6Pj7  Usages `$ }vre: kPb(OH)2" 2PbCO3 cENnv a$ ~kXEQBR:Tb~~mIQBR b$IQPSBRIQPSmdsXalgvgt`vPSBR   ~s|~  6RYagN &060 0 C K C K >C Z    "  0@@ 0 0H  0޽h ? ̙33y___PPT10Y+D=' >= @B + 0 . &  (    6B B\2. TiX 4/ TiX3 `$ TiF4 /TiF3 Ionic, others are covalent. TiF4 TiCl4 TiBr4 TiI4 er er Ğr hr rSm 1uN5uwy00 GOGOGOGO GOGOGOGO8GG3$l<  6 ,;P  ZTiCl4 + 4HX ! TiX4 + 4HCl (X = F Br) 2TiCl4 + Zn (Al \ H2) ! 2TiCl3 + ZnCl2 Ti3+؏S'`:_NSn2+  TiO2+/Ti3+ = 0.1V Ti3+ + Fe3+ = Ti4+ +Fe2+ (uhQFe3+mn[ KSCN:Nc:yBRe(SCN)]2+ ~'00 GO GOGO GO GOGOGG3O3G3O3G O GOGOGOGOGOGOGjS. "  0@ 0 0  00B; ,$D 0 ^a$ TiX4 are similar to SnX4. These are volatile liquids which fume in moist air due to hydrolysis giving HX. Partial ! polymeric or polynuclear species Complete ! TiO2" nH2O GOGOGOGOGG$  H  0޽h ? ̙33___PPT10f+(ED' >= @B D' = @BA?%,( < +O%,( < +D' =%(D' =%(DT' =A@BBB B0B%(D' =1:Bvisible*o3>+B#style.visibility<*%(D' =-6B'blinds(horizontal)*<3<*+8+0+0 +  0   6 (    6`;  3. Ti(c!) complexes TiF62- TiCl62- [Ti(NH3)6]4+ colorless Ti4+ Z/r 'Y gSR:_ TiO2+pyP[ [Ti(H2O)6]4+ = [Ti(OH)2(H2O)4]2+ + 2H+ [Ti(OH)2(H2O)4]2+ +OH- ![Ti(OH)4(H2O)2] + 2H+ ! TiO2" 4H2O bvH2O2krRg Ti(c!) +H2O2 ![Ti(O2)OH(H2O)4]+ mononucleus/red, pH < 1 ! binuclei /orange, pH 1-3B0K0 CKKCKKCKCKCKCKCK CKCKCK CKCKCKCKCKCKCKCKCKCK CKCKCKCKCKCKCGOO GOGOGOGOGOG$OQGtKeF (H  0޽h ? ̙33y___PPT10Y+D=' >= @B +$  0 ` 8$(  8r 8 S `d;0F  ; r 8 S 8e;  ; H 8 0޽h ? fff80___PPT10. 0  {(    6؝;  L8 14-3-1 General properties Chromium [Ar]3d54s1 118pm +6 +3 +2 Redox 'lSS^ Molybdenum[Kr]4d55s1 130pm +6 +5 +4 +3 Iso poly acids /hetero poly acids Tungsten [Xe]4f145d46s2 130pm TYx / BgYx Cr, Mo,and W have the highest melting point and boiling point in their period.vc00 S0%C$C$CKCK:CKCKCKCKCK*CCQCz M0Q  6ܷ;Pp R "0C   6; @ c 400 C H  0޽h ? ̙33y___PPT10Y+D=' >= @B +) 0 PH (    6; Z  4 Note that whereas Cr and Mo have a d5s1 configuration, W is d4s2 due to the intervention of the lanthanons between the 6s and 5d element. As a result of this lanthanide effect, the energy difference between 6s and 5d orbitals increases to more than the extra stability of the half-filled d5s1 configuration.50%CKCKCKCKCKCKCC6` oS  6h;0 P  H"0 C H  0޽h ? ̙33y___PPT10Y+D=' >= @B +7 0   @ & (  F  6; P ,$D  0  A large number of iso and hetero poly acids are formed by Moe! and We! in acidic solutions. For Cre! only CrO42 and Cr2O72 are known. They get interconverted by a pH change and not by heating. No hetero poly acid is known for Cre! .0sGOOGOGOOoG'  G  6;0 V"0C   0;/,A ,$D 0 & Reducing agent Cre! ! CrIII , Cra! Strong reducing agent, eg. Zn Sn SnCl2 Moe! ! Mod! , Moc! ! Mo(III We! $- (3O33->      0< In fact except for stoichiometric similarities in the same oxidation states the 4d and 5d elements are quite different from the 3d element. <0 2CC$H *@H  0޽h ? ̙33I A ___PPT10! +bD' <= @B DP' = @BA?%,( < +O%,( < +D' =%(D' =%(DT' =A@BBB B0B%(D' =1:Bvisible*o3>+B#style.visibility<*%(D' =-6B'blinds(horizontal)*<3<*D{' =%(D#' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+B#style.visibility<*%(D' =+4 8?\CB#ppt_xBCB#ppt_xB*Y3>B ppt_x<*D' =+4 8?dCB1+#ppt_h/2BCB#ppt_yB*Y3>B ppt_y<*+p+0+0 ++0+0 +[  0  z P  (    6< a 14-3-2 Cr and its compounds Electron configurationCr [Ar]3d54s1 Oxidation number: +6 +3 +2 c00 $CC "CKCK"CC  6_<^ n5uRV 1.33 0.41 DA(v) Cr2O72 (Yj)  Cr3+Cr(H2O)63++}~   Cr2+ 0.91 0.74 Cr(H2O)42+݄   Cr}v   Cr3+ 0.13 1.1 DB(v) CrO42 Ğ   Cr(OH)3pp~   Cr(OH)2 1.4 Ğ   Cr 00 0 qGO GOGOO GOGOGOO GOBGOGOOGOGO GOO GO GOGO GJ;.  *  ! H  0޽h ? ̙33y___PPT10Y+D=' >= @B +  0 F>` (    6XU<`  8S `$ CrkH2;ml VS 3z[ NnNs4l0HNO3 a$ Cr2+:_؏SBR Cr2+ + H2O ! Cr3+ + H2! b$ (Wx-N Cr3+3z[ S g:_'lSBRMb\KN'lS Cr(e!):_'lSBR Cr3+ + MnO4- + H+ ! Cr2O72- + Mn2+ + H2O (%) K2Cr2O7 + HCl (conc.) ! Cr3+ + Cl2 + H2O OH--N Cr(III)f'lS Cr3+ + H2O2 + OH- ! CrO42- + H2O 6 00 0  CKCKCKCKCKCKCK CK(CKCKKCKCKCKKCKCKCKCKCKCKCKCKCKCKCKCKCKCKKCKC 8#!H  0޽h ? ̙33y___PPT10Y+D=' >= @B +5  0 \Tp (    0<  Tv14-3-2-1 Physical and Chemical Property of Cr 4Cr + 3O2 = 2Cr2O3 green(combustion) 2Cr + 3Cl2 = 2 CrCl3 purple (combustion) Cr + I2 = CrI2 Cr +2HCl = CrCl2 + H2! Cr + 2HI = CrI2 + H2! 2Cr + 6 H2SO4(conc.) = Cr2(SO4)3 + 3 SO2!+ 6 H2O Cr + HNO3 ! Cr + HNO3 + HCl ! 4"Cr0Fe0AlSNvSmHNO30SmH2SO4Q Cr NnNx*<0(27GOGOGOGO GOGOGOGOGOGGOGOG GOGO GOGOGOGOGGO GO GOGOGOGOG H  0޽h ? ̙33y___PPT10Y+D=' >= @B + 0   ~ (  F   6P8=dwc 14-3-2-2 Cr(b!) occurrence : Cr3+ ; Cr(OH)63 Cr(OH)4 CrO2 `$ ؏S'`:N;NG:_؏SBRe HT'lS'` 2Cr3+ + 3H2O2 + 10OH = CrO42 + 8H2O CrO2 + Na2O2 + H2O ! CrO42 + Na+ Cr3+ + MnO4 + H+ ! Cr2O7 + Mn2+ 2Cr3+ + Zn = 2Cr2+ + Zn2+ a$ Cr2O30Cr(OH)3:N$N'`ir( Cr3+ +3OH = Cr(OH)3 ! Cr(OH)3 +OH = Cr(OH)4 Cr(OH)4 + H+ = Cr(OH)3 !; Cr(OH)3 + H+ = Cr3+ W00 0b0 0 go gooogoogoogogogogogoogogoogogogogoogogogoogogogogogo gogogogogogogo go gogo googoogogogggogogocc- 7  'H  0޽h ? ̙33y___PPT10Y+D=' X= @B + 0  L(    6!=, b$ CrCl3 +}r Cr2O3 + 3C + 3Cl2 ! 2CrCl3 + 3CO C+Cl2,COCl2,CH3Cl Cr2O3 + 3COCl2 ! 2CrCl3 + 3 CO2 CrCl3" 6H2O + 6SOCl2 ! CrCl3 + 6SO2 + 12HCl c$ Cr(III)MTirCN=6,d2sp3BgS0kQbSO0zx'`ir( [Cr(H2O)4Cl2] " 2H2O f~ CrCl3 Snm ! Ny4lT_gSO [Cr(H2O)6]Cl3 +}r [Cr(H2O)5Cl]Cl2" H2O m~ [Cr(H2O)4Cl2] " 2H2O (QtSHCl,T0 273 K 0) = [Cr(H2O)6]Cl3 (YN HCl) = [Cr(H2O)5Cl]Cl2" H2O SS^ CrCl 3 + NH3" H2O ! [Cr(NH3)6]3+ Ğ  00 $00 a0%0 0 GO GOGO GOGO GOGOGOGOGOGOGOGOGOGO GOGOGOGOGO8GOGOGOGO GOGOGOGO2GOGOGOGO GOGOGOGOGOGOGOGOGOGOGOGOGOGO GOGOGOGC 3)TH  0޽h ? ̙33y___PPT10Y+D=' X= @B + 0   (  |   68>   *14-3-2-3 Cr(e!) X[(Wb__ Cr2O72  NYCrO42 3z[ 4"'lS'`:_ CrO42 Cr(e!) sp3BgS VbSO M. 00000000M. 5uwy `$ NvlS nmvx^ lmBR Ag+ Ba2+ Pb2+ 2CrO42 + 2H+ = Cr2O72 + H2O K = [Cr2O72 ] / ( [CrO42 ]2 [H+]2 ) 0= 1.21014 S_[H+]=10 7 Me,[Cr2O72 ]H"[CrO42 ],0[H+]!,[Cr2O72 ]!Zm0 (00  $C(C(C(CKCKKCKKCKK CKC GCcCKCKCKCKKCKCKCKKCKCCCKCKK CKKCKCKCK CKCKCKCKCKKCKKCKCKCKKC`  !    T  6<=p (  `$Ag+ `$Ag2CrO4 !x~ Cr2O72 a$Ba2+ a$BaCrO4 !Ğ H+ CrO42 ! ! Cr2O72 Yj~ b$Pb2+ b$PbCrO4 !Ğ 8.00 0 CK CKCKCKCKK CKCKCKCKKACKCKKCKCKCz @H  0޽h ? ̙33y___PPT10Y+D=' = @B +  0    P (      6@?>P@ xva$ :_'lSBR S2 S I I2 Cr2O72 + Cl ! 2Cr3+ + Cl2 + 7H2O 6Fe2+ 6Fe3+ SO32 SO42 8040 0 CK>CK$CKCKCKK CK CK CKCKCK"CKCKK CKKC!   u2   6@>` b$ H2CrO4xmm TCrO3 / CrO2Cl2 /lSx K2Cr2O7 + 2H2SO4 ! 2KHSO4 + 2CrO3! + H2O (~rrvfSO xP) CrO3 + H2O ! H2CrO4 (Ğ) K1 = 4.1 CrO3(%) ! CrO2(hў) ! Cr2O3~ +O2! V$00 0 CKCK CKCKCK CKCKCKCKCKCKCKCKBCKCKCKCK CKCK CK CKCKCKC V ! H   0޽h ? ̙33y___PPT10Y+D=' = @B +  0   _ (  P   6HF?d H CrO3 + 2HCl ! CrO2Cl2 + H2O CrO2Cl2 ~rl.,NCCl40CS20CHCl3Nn K2Cr2O7 + 4KCl + 3H2SO4 ! CrO2Cl2!+ 3K2SO4 + 3H2O Cr(e!)vSdCr2O7 + 4Cl + 6H+ ! 2CrO2Cl2 + 3H2O (SQp) CrO2Cl2 + H2O ! H2Cr2O7 + 4HCl c$ Cr(e!)vt[0h Cr2O72 + 4H2O2 + 2H+ ! 2CrO(O2)2 + 5H2O (YNB\) [CrO(O2)O(C2H5)2] ݄rMTir 0X0 0>0 0N0 0 CCK CKCKCKCKCK CKCKCKCKCKCK CKCKCKCKCKCKCKCKCKCKCKCKCKCKCKCKCKCKCKCKCKCKKCKCKCK CKCKCKCKCKCKCK C'9 qI #  6\>0P i "0CH  0޽h ? ̙33y___PPT10Y+D=' = @B +m 0  $(  :  6>,/ " 14-3-2-4 Crv6RY r00 C(C(C(C    6P? 7 D w :Fe(CrO2)2 FeO" Cr2O3 4Fe(CrO2)2 + 8Na2CO3 + 7O2 ! 8Na2CrO4+ 2Fe2O3+8CO2! % Q + H2O ! Fe2O3 !\ Na2CrO4 \ Na2CO3 Na2CrO4 + H2SO4 ! Na2SO4 + Na2Cr2O7 + H2O Na2CrO4 + S ! Na2SO4 + Cr2O3 Cr2O3 + Al (H2) ! Cr + Al2O3 (H2O) (1800K) ~SCrI2 ! Cr + I2! (1500K) 5uH2Cr2O7 Cr2(SO4)3 5ugPge P Pd 4Cr3+ + 3e = Cr 34OH- 4e = O2 + 2H2O R0%0 *0d0 0'0  GOGOGOGOGGOGOGOGOGOGOGOGOGOGOGGOGOGOGOGOGOGOGOGOGOGOGOGOGOGOGOGOGOGO GOGOGOGOGOGOGO GOGOGOGO GOGOGOGOGOGOGOGOGOGOGOGGJ H  0޽h ? ̙33y___PPT10Y+D=' = @B +  0    (    6T?  c 400 C   6?Z 2  ,14-3-3 Mo0W 14-3-3-1 Extraction of Mo0W ܔwMoS2  MoO3 (OH ) ! MoO42 (H+) ! H2MoO4 (%) ! MoO3 (H2) ! Mo MoS2 + O2 ! MoO3 + SO2! MoO3 + NH3" H2O(Sm) ! (NH4)2MoO4! (NH4)MoO4 + 2HCl ! H2MoO4!+ 2NH4Cl H2MoO4 ! MoO3 + H2O (%) MoO3 + 3H2 ! Mo + 3H2Ol00  G(G GOGOGOGOOGOGOGO GOGO GOGOGOGOGOGOGO GOGOGOGOGO GOGOGOGOGOGOGO GOGO GOGGl  LbH  0޽h ? ̙33y___PPT10Y+D=' = @B +  0  B(  2  6@PI  xql ўw(FeWO4 + MnWO4) + Na2CO3 + O2 ! Na2WO4 + (Fe2O3 + Mn3O4) + CO2! 0D0 0  C K C K C K C K C K C K C K C K C K C K C K C K C CA  6< @ / Na2WO4 + 2HCl ! H2WO4 + 2NaCl H2WO4 ! WO3 (Ğ) + H2O (%) WO3 + 3H2 ! W + 3H2O0/0 C K C K C K C K C K C K C K C K C K C K C K C +!  6Tz?7 lP}vw CaWO4 ! H2WO4 (%) ! WO3 (H2) ! W (00 C K C K C K C K C K C $H  0޽h ? ̙33y___PPT10Y+D=' = @B + 0 :2  (      6K@<[  ,MoO30WO3 x'`'lSir NnN4l nNxm OH ! MoO42 \ WO42 H+ ! H2MoO4(MoO3" H2O) \ H2WO4(WO3" H2O) 0?0 0 G O G O G O G O O G O O G O G O G O G O G O G O G O G O G O G Cv(H   0޽h ? ̙33y___PPT10Y+D=' = @B +g  0    $ (  $ $ 65@,    14-3-3-2 H2MoO40H2WO4 / v `!A+0Be2+0Mg2+0Tl+0NH4+Sn vQYOn O1 (NH4)2MoO4 + H2S ! MoS42 ( H+ )! MoS3! h WO42 + H2S ! WS42 ( H +) ! WS3! Nh O2 NH4 2MoO4 + 3Zn + 16HCl(conc.) =2MoCl3 + 3ZnCl2 + 4NH4Cl + 8H2O tl010 P00  G O G O G O G O G GOGOGOGOGOOGOGOGOGOGOOGOGOGOOGOGOOGOGO GOGOGO(GOGOGOGOGC   HH $ 0޽h ? ̙33y___PPT10Y+D=' = @B +  0   (N (  (~ ( 6@   14-3-3-3 Iso and hetero poly acids Yx: +T'lxǏ O 0 OH~T bvwQ gN*NN N-N_SP[v+T'lx. TYx Ty{US+T'lx14l b BgYx$Nyb$NyN N+T'lx14l b 2H3PO4 H2O ! H4P2O7 &qxx 2H2CrO4 H2O ! H2Cr2O7 ͑x 4H2MoO4 3H2O ! H2[Mo4O13] Vx PO43 +12MoO4+24H+ ![PO4(Mo3O9)4]3 ASNxx9h +12H2OX00 0p0 #GKGOGOGOGOGOGOGOGOGOGOGOGOGOGOGOGOGOGO GOOGOGOGOGOGOGOGO GOGC $  ( 6@0 6  v 4 00  C  ( 0@9 d,% LR O.1_ x'`1_ nmpH'Y fb_bYx p:SS P Si B Al d :SCr Mo W Nb TaCCG3    H ( 0޽h ? ̙33y___PPT10Y+D=' = @B +{  0   @ 02 (  0 0 6$@jV .|Yx:1_x'`"l'lSirǏ O 0 OH~T bvZTir. f4l㉄v$N'`ё^\yP[ SX[(WNؚx^0znm-N4l㉧Nir:NYx.6?0>GCX 0 0 6A   H OH OH 2[Cr(H2O)6]3+ ! 2[Cr (H2O)5 (OH) ]2+ ! [ ] ! Cr2O3" n H2O pH>13 pH 8-12 ! [Al(OH)4] ! [ ] [Fe(H2O)6]3+ + OH ! [ ] ! Fe2O3" n H2O! m+} Ğh hr @00 0 CK"CKCKCKCK CKCKCKCKCKCK3CKCKCKCKCKCK CKCKCK3Cn u.& 0 6A @ <Yx0YxGW:NY8hMyP[ MRMOM4yP[ T:NM3yP[. D00 CCH 0 0޽h ? ̙33y___PPT10Y+D=' = @B + 0 6.P 4(  4.B 4  ((.B 4  o.B 4@  o(.B 4  `` .B 4   .B 4   .B  4   .B  4   H .B  4      4 t@AB$ CDEFKcjc$ @ #"  q .B  4     4 t@AB,CDEFGY@  Z,@ #" ) x .B 4    4 t@ABpCDEFpbZ@ #"  X= .B 4  F   4 6?Az<  , +10 CrO5(݄) H+ SmHCl +6 CrO42 R" Cr2O7 ! CrO3(s.) ! CrO2Cl2(l.) % OH Snm H2O +3 Cr2O3 R" Cr(OH)3! R" [Cr(H2O)6]Cl3 ! [Cr(H2O)4Cl2]Cl" 2H2O R" CrCl3 (s.) OH H+ +2 qp [Cr(H2O)4]2+ 500 0 G /GOaGO0GOOGOGO GO GOGORGOGO GOGO GO GOGOGO GOGOGOGO GOGOGO#GOGOGOG1j&okP, 4 6BA H+ H2O YN x 00 CKCKC  4 6IA .OH [O] H+ [R]f0CKCKC 4 68QA/  LrH2O H+ H2O HCllAm% 900 CK CKCKC2L 4 6$8A5   Cr(OH)4 O2 Zn/HCl [Cr(H2O)5OH]2+ C00 C CKKCKCKCKCKC< t 4 6pAO   H Al H+ Cl2 H00  C CK!CKC > 4 6A /  $0 Cr D$00 $C CH 4 0޽h ? ̙33y___PPT10Y+D=' = @B +  0 : 2 D (  D B D   ] B D  @ B D   B D P B D  B D z B D   B  D  8  B  D p p  B  D :    B  D :   B  D : XX  B D P D 6A, N 0.56 2.26 0.95 1.51 A/V MnO4   MnO42   MnO2   Mn3+  1.18 1.51 Mn2+   Mn  MnO4 0.56 0.60 0.2 B /V: MnO4   MnO42   MnO2   Mn(OH)3 0.11 1.55   Mn(OH)2   Mn `00 0 ]G$OGOOGOOGOGO(GG3GOG3G33O3O3IG$O GOOGOOGO GO&GOGB  + $ )| D 6 20 < 0 0 *CCP[n< H 6A  l 400 Cx H 6` BqE  1u5uRSw Mn(III)fgkS Mn3+ (1j~)SX[(WNSmx-N MnO42-gkSNirMnO4-0MnO2 MnO42-~ SX[(WNSmx-N MnO4- :_'lSBR$020 GOGOOGOOGOGOOGOOG  (H H 0޽h ? ̙33y___PPT10Y+D=' = @B + 0  Lk(  LL L 6`BZd z14-4-2 Manganese 3Mn + 2O2 = Mn3O4 Mn + 2 HCl = MnCl2 + H2! 0+0 0 C$ CKCKCKCKCKC4$ Q L 6L+BP7  ]High temperature: Mn + Cl2 = MnCl2 3Mn + N2 = Mn3N2 3Mn + C = Mn3C Mn + S = MnS $*030 0 CCKCKCKCKCKCKCF3  L 6(EB 7  .2Mn + 4 KOH + 3O2 = 2K2MnO4 + 2H2O (melting) .00 CKCKCKCKC.H L 0޽h ? ̙33y___PPT10Y+D=' = @B +  0 1 ) P (  Pv P 6PjB`  14-4-3 Compounds 14-4-3-1 Mn(a!)salts MnSO4" 5H2O MnCl2" 4H2O |~rvfSO Mn(NO3)2 " 3H2O MnS !r MnCO3 !}vr ,nNHCl YfnN4lh00;0 0 C(C K C K C K C K C K C K C K C K C   | P 6|aB` ? "0C^ P 6eB v Mn2+vt[: 2 Mn2+ + 5IO4- + 3H2O = 5IO3- + 2MnO4- + 6H+ (%) Mn2+ + S2O82 + H2O = SO42 + H+ + MnO4 (%,Ag+) 2 Mn2+ + 5NaBiO3 + 14H+ ! 5Bi3+ +2 MnO4- + 5Na++7H2O (%) 2 Mn2+ + 5PbO2 + 4H+ = 5Pb2+ + 2MnO4 + 2H2O (Ag+) 020 0 GO GOGOOGOGOOGOOGOGOGOGOOGOGOOGOGOOGOGO GOGOGOGOOGOGO GOGOGOGOGOOGOGOGZA  e H P 0޽h ? ̙33y___PPT10Y+D=' = @B +  0   Tn (  T6  T 6B2  a$Mn2+ + 2OH = Mn(OH)2! (O2) ! MnO(OH)2 brown ! MnO2! black 2MnO2 + C(coal) + 2H2SO4(conc.) ! 2MnSO4" H2O + CO2 MnO2 + HCl(conc.) ! MnCl2 + Cl2 + H2O MnCO3 + HNO3(conc.) ! Mn(NO3)2 + CO2 + H2O Mn(NO3)2" 6H2O(298K) ! Mn(NO3)2" 3H2O(%) ! MnO2 + NO2 + H2Ox00 GOGO GOGO GORGOGOGOGOGOGOGOGOGOGOGO GOGOGOGOGOGO GOGOGO GG3O3G3O3G3O3G38GOGOGOGD /H T 0޽h ? ̙33y___PPT10Y+D=' = @B +  0   X(  Xp X 6B7i 8 14-4-3-2 MnO2 o0w Mn(c!)v3z[ v00 C C$K$ CC8^ X 6 C/  MnO2 + 4 HCl (conc.) = MnCl2 + Cl2!+ 2H2O 2MnO2 + 2H2SO4 = 2Mn2(SO4)3 + O2!+ 2H2O (383K) ,010 0 CKCKCKCKCKCKCKCKCKCKCKCK CC* O X 6 C i . 2MnO2(s) + 4KOH + O2 = 2K2MnO4 + 2H2O (%) Mn(c!)SLb3z[vMTir MnO2 + 2KHF + 2HF ! K2[MnF6] + 2H2O ,0>0 0 CKCKCKCKCKCCG CC G O G O G O G O G D2 $H X 0޽h ? ̙33y___PPT10Y+D=' = @B + 0  \<(  \ \ 6MCjd  ^(u `$ 0r^5u`l mdgS\O(u'lS5ug NNuvH2 a$ PSBR: KClO3 ! KCl + O2 (MnO2) H2O20loI{v'lS؏SS^ b$ 6RMn(a!)v60d0 GOGO GOGO GOGOGdH \ 0޽h ? ̙33y___PPT10Y+D=' = @B +  0   ` (  `  ` 6\BC/  14-4-3-3 KMnO4 V00 C(K(C( ` 63CT  `$ ꁫ'lS؏SR 4 MnO4 + 4H+ = 4MnO2!+ 3O2!+ 2H2O 2KMnO4 ! K2MnO4 + MnO2 + O2! (473K) 0G0 0 CKKCKCKCKCKCKCKCKCKCK C*? ` 6_Cp\B  a$ EMnO4 / Mn2+ = 1.51 V EMnO4 / MnO2 = 1.69 V EMnO4 / MnO42 = 0.56 V b080 0 CKKKKKCKKKCKKKKK CZ  ` 6DCV B  H+ Mn2+ MnO4 + SO32 + H2O ! MnO2! + SO42 OH MnO42- 00U0 GO GOGOOGOOGOGOGOO!GO GOOGfH ` 0޽h ? ̙33y___PPT10Y+D=' = @B +G  0 n f  d(  dF d 6C@ ` MnO4 + I + H2O ! MnO2 + IO3 + 2OH KMnO4a little + H2SO4 (conc.)! K+ + MnO3N~ + H3O+ + 3HSO4 Z&0=0 0 CKKCKCKCKCKKCKCK CKCK CKCKCKCKCKKC d 6TC   b Mnvuir\O(u iir|T8T0IQT\O(u Rir ,Mn(a!)/fYy'lSvv~bR H 0'0 0 2CB  d 6D`  j o0w:MnO2 ў0w:Mn3O4 4l0w:Mn2O3" H2O 0w:3Mn2O3 " MnSiO3  0+0 0 CCKCKCKCKCKCK CKCKCKCCP H d 0޽h ? ̙33y___PPT10Y+D=' = @B +=  0 d \ h (  h h 6(D`N rMnO2! K2MnO4 ! KMnO4 ( `$gkSa$5u ) 2MnO2 + 4KOH + O2 ! 2K2MnO4 + 2H2O z/0#0 0 CKCKCKCKCK CKCKCKCKC"%'B h 6Cd N3K2MnO4 + 2CO2 ! 2KMnO4 + MnO2 + K2CO3 r'00 GOGOGOGOGOGOGOGG h 6tDd  ,5uK2MnO4 42H2O + 2e = H2!+ 2OH 32MnO42 2e = 2MnO4 2MnO42 + H2O = 2MnO4 + 2OH + H2 2K2MnO4 + H2O = 2KMnO4 + 2KOH + H2p 0v0 G 3O 3G 3O 3G 3GO GOGOGOO GOOGOOGOGOOGOGOGOGOGO GO GOG  (H h 0޽h ? ̙33y___PPT10Y+D=' = @B +V  0 pV(  r  S OD0F  D   s *xPDS" <% D H  0޽h ? fff80___PPT10.tʝ  0  c(    6UD7 ,14-5 Fe Co Ni (g!) T00 C(C(C   6HD l 14-5-1 General properties D00 C$C   6DmT  ;Valence electron configuration Fe Co Ni 3d64s2 3d74s2 3d84s2 CN +2 +3 +6 +2 +3 +4 +2 +3 +4 b0{0 0 uCKCKCKCKCKCK=C 8,d  6(DF ' Redox reactions Easy to form complexesFe2+0Fe3+0Co3+0Ni3+ 6 Co2+0Ni2+ 48>180 )GOGOGOGO2GOGOG!" H  0޽h ? ̙33y___PPT10Y+D=' = @B +  0    (    0DA :A 2.20 0.771 0.44 FeO42 Fe3+ Fe2+ Fe 1.09 1.808 0.227 Co3+ Co2+ Co 0.418 1.678 0.25 NiO2 Ni2+ Ni 0.714 Dn0 2CKVCKKCKCKCKCKCKCKVCLB  c $D` LB  c $D LB  c $DLB  c $DpP P LB  c $DP LB   c $DpppLB   c $D ` LB   c $D @     rBCSDEFS@`  LB   c $D    rBC:DEF:@v | LB  c $D 0 LB  c $D P LB  c $D LB  c $DLB  c $D H  0޽h ? ̙33y___PPT10Y+D=' = @B +  0   H(    6D  ^ B 0.72 0.56 0.887 FeO42 Fe(OH)3 Fe(OH)2 Fe 0.17 0.73 Co(OH)3 Co(OH)2 Co 0.49 0.72 NiO2 Ni(OH)2 Ni R0CKvCKKCKCKjCKCKpCK!CKCCLB  c $DPPLB  c $D pLB  c $DLB  c $Dp0 LB  c $D0 `LB  c $D@ @ LB   c $D@ @ H  0޽h ? ̙33y___PPT10Y+D=' = @B + 0  L(    6Fp`  Fe, Co, NiGW:N-NI{;mlё^\ M + 2H+ ! M2+ + H2 Fe2+ + O2 ! Fe3+ Fe + Cl2 ! FeCl3 M (Co Ni) + Cl2 ! MCl2 ؚN`FeO42 0Co3+0NiO2 :_'lSBR $0R0 0 CKCKCKCKCKCKCKCKCKCKCKKCKCKCCV SH  0޽h ? ̙33y___PPT10Y+D=' = @B +S  0 z r 0  (    04F@ rSeveral of the first-row transition elements--- Fe,Ti,Mn---are among the most abundant metals in the crust and occur together in many ores. Extraction methods vary depending on the source, but all include a reduction step with either carbon or more active metals(Mg or Al).Alloying provides most of their uses. Fe3O4 (Hematite) / Fe2O3 (magnetite) + C Co0NiNNAs0SvSTvb__X[(W: CoAs2(Smaltite),many sulfides with Ni ,Cu, Pb , Roasting in O2, leaching with H2SO4,precipitating Co(OH) 3 with ClO-, heating to form CoO,and reducing with C. (Ni , Fe)9S8 (Pentlandite), NiAs (~Mw), NiAsS (7xMw) Roasting in O2 to NiO, reducing with C Vc0000 :CKCKCKCKCCGCK:CKCKCKCK CK5CKCK6CKC0.-E! H  0޽h ? ̙33y___PPT10Y+D=' = @B +  0   @   (  ~  0SF0 Reactions of Fe 1400! Fe3O4 Fe2O3 230! Fe3C FeO(OH) C H2O~p H2O FeS S,% Fe X2 FeX3 (X=F0Cl0Br) CO,230! l`HX Fe(CO)5 FeX2 (X=F0Cl0Br) H+ I2 Fe2+ FeI2 D0(20 2CTCKCKCKCKXCK^CKCK3CK CKHCK7CK-CKCKCKCKC )>3HtRB @ s *D  P RB  s *Dpp`RB  s *D RB  s *D P RB @ s *D p RB @ s *D p RB  @ s *D P@RB   s *D ` 0 RB   s *D 0 RB   s *Dp RB   s *DP0 H  0޽h ? ̙33y___PPT10Y+D=' = @B + 0   P < (    6hF p 14-5-2 compound of Iron B00 $C  6DF 14-5-2-1 Fe(a!)salts FeSO47H2O~w ,e4le:N}vr +T~vf4le:Nm~r vQznm:Ner Smnm:Nm~r N00 C c C CKCK0C6  + PJ  6+ l  6$G0   Cl20Br20ClO 0Na2O2 ^f_ Fe(OH)2 + Cl2 + 2OH ! 2Fe(OH)3 + 2Cl Fe2+ + Br2 + H+ ! Fe3+ + Br 2Fe2+ + 2OH + Na2O2 + 2H2O ! 2Fe(OH)3 + 2Na+ 40q0 0 CKCKCKCKCK CKCKCK CKCKCKCKCKCKCKCKCKCKCKCK CKCKC !   6BG ` >(3) Usages`$ e a$ 6R݄ўX4l b$ (gPg2P 400  C  8H  0޽h ? ̙33y___PPT10Y+D=' G= @B +  0 6 . p  (    6NGZ'R L" 14-5-2-2 Fe(b!) salts 8^HTĞrbhr vnm8^:NmĞhr [Fe(H2O)6] 3+m+} FeCl3 + H2O ! FeCl36H2O (FeCl3)2qQN'` S(uGSNSlc~ *0g0 0  C$ C'CKCKCKCKCKCKCKCKCK CP / T  6 ZG7  Z(1)Prparation: 2Fe(powder) + 3Cl2 ! 2FeCl3 x-00 "CKCKCf  6aGS 7?  Z(2)Properties 'lS'`:N;N(WOH -NG:_'lSBR MbhsQ؏S'` V-00 CKC,   6TG /  Sn2+ Sn4+ Fe3+ + H2S ! Fe2+ + S I I2 620W0 0 CKCKCKCK CKCKCKC*ZH  0޽h ? ̙33y___PPT10Y+D=' G= @B +  0 < 4 (    6GLE 0 % Fe2O3 + 3KNO3 + 4KOH ! 2K2FeO4 + 3KNO2 + 2H2O K2FeO4 +BaCl2! BaFeO4! ~hr 50J0 0 5CCKCKCK CKCKCKCKCKCKCKCKC$4F  6lG"T  FeO42 + H+ ! Fe3+ + O2!+ H2O 2Fe3+ + 10OH + 3ClO ! 2FeO42 + 3Cl + 5H2O ClO3 0U0 CKKCKCKCKCKCKCKCKCKKCKCK&CKKCj$,  6GV 7v  2(3)Usages`$ bk@BR a$ g:gS^PSBR"0C  8H  0޽h ? ̙33y___PPT10Y+D=' G= @B +B 0 i a  (    6xGZd { 14-5-2-3 Complexes20CC   6HM7 .CN=6 Fe(H2O)62+ m~ Fe(H2O)63+ m+}r FeF63 er FeCl63 Ğr [Fe(PO4)2]3 er Fe(SCN)x3-x @~r Fe(C2O4)33 ~r n0z0 0  CKCKK CKCKK CKKCKK CKCKCKCKKCKCKCKKC       6HCdI  v8Fe3+ + H3PO4 ! [Fe(PO4)2]3 00 CKCKCK CKCKCKCC X  6$H db D Fe3+ + x SCN = Fe(SCN)x3-x Fe(SCN)x3-x + Na2C2O4 ! Fe(C2O4)33 K4[Fe(CN)6] 3H2O(aq) + Cl2 ! K3[Fe(CN)6] + Cl Ğ@v d@v000 GfGOGOO GOOGOGOGOGOGOGOOGOGOGO GOGOGOGO.GF?.& H  0޽h ? ̙33y___PPT10Y+D=' G= @B +5  0 \ T (    6NH<   K+ + Fe3+ + [Fe(CN)6]4 ! KFe[Fe(CN)6] ! nfX݄ K+ + Fe2+ + [Fe(CN)6]3 ! KFe[Fe(CN)6] ! nX݄ K3[Fe(CN)6] + 3H2O ! Fe(OH)3 + 2KCN + 3HCN -N'` K3[Fe(CN)6] + KOH ! K4[Fe(CN)6] + O2!+ H2O (x'`) 4" K3[Fe(CN)6]g}Ys(usM 100 0 gGOGO GOGO GOGOGO GOGO GO GOGOGO GOGOGO GOGOGOGOGOGO G,/   6(H P Q 400 C  6H `  m 400 CH  0޽h ? ̙33y___PPT10Y+D=' G= @B + 0   (  r  6rH<T$   _SIUs N N N Fe2+ N N O2 or H2O CO0CN 0CKuCKCKCKC4y LB  c $D LB  c $D` LB  c $D` LB @ c $Dp` LB  c $D  LB  c $Dp  ^   6p   c &A m??"?  mH  0޽h ? ̙33y___PPT10Y+D=' G= @B + 0   x (    6pCH   Fe3+vdS f 00 CKCCR  6H` [Fe(H2O)6]3+ + H2O = [Fe(OH)(H2O)5]2+ + H3O+ [Fe(OH)(H2O)5] = [Fe(OH)2(H2O)4]+ [Fe(H2O)6]3+ +[Fe(H2O)5OH]2+ = [(H2O)5Fe-O(H)-Fe(H2O)5]5+ + H2O 2[Fe(H2O)5OH]2+ = [(H2O)4Fe(OH)2Fe(H2O4)] + 2H2O -00 0 CKCKCKCK CKCKCKCKCK CKCK CKCKCKCKCKCKCKCKCKCKCKCK CKCKCKCKCKCKCKCKCKCKCKCKCKC  6J@  lOverall2[Fe(H2O)6]3+ = [Fe(H2O)4(OH)2Fe(H2O)4] + 2H+ 600 CGOGOGOGOGOGOGOGOGOGC".  6 J   jFe2(SO4)3 b FeCl3 ! Fe2O3nH2O!SO lm^ba ! Fe2O3nH2O !n}r `$%a$QZBR D00 CKCKCKCKCKCKCKCKCKCKC6   H  0޽h ? ̙33y___PPT10Y+D=' G= @B +  0 x p  (    6JE  j[Fe3+]'Y [H+]'Y 4lba Nnm-NRyFe(OH)3V dkeSǑSub Yvs\ |'Y lm^_0fǏn Ğw M2Fe6(SO4)4(OH)12 M = K+0Na+0NH4+ H2O Fe2(SO4)3 ! Fe(OH)SO4 ! Fe2(OH)4SO4 2Fe(OH)SO4 + 2Fe2(OH)4SO4 + Na2SO4 + 2H2O ! Na2Fe6(SO4)4(OH)12 (EmĞr) !+ H2SO4e00 GOGOGO$GOGOGOGOGOGOGOGOOGOGOGOGO GOGOGOGO GOGOGOGOGOGOGOGOGOGOGOGO GOGOG   H  0޽h ? ̙33 0 wo (    67J7k 114-5-3 Compounds of Co and Ni 14-5-3-1 Reactions B100 0$C1  6?J R "0C H  0޽h ? ̙33  0 0(  (    6HDJp  H Co3O4 Air(5oo!) air CoO CoS Co(OH)S H2O(~p ) S,% H2S NH3,470! X2=Cl Br I % OH ,Co(OH)Cl [ O ] CoN Co CoX2 Co(OH)2 Co(OH)3! CO,200! F2,330! HF H+ Co2(CO)8 CoF3 CoF2 Co2+ O0CKCKKKK<KKmKKKCDI]RB  s *DppRB  s *Dp@RB  s *D@` @  rBCDEF@_ ,RB  s *D RB  s *D RB   s *D0RB  @ s *D@RB  @ s *D @p RB   s *D  p RB   s *D RB  s *D p RB  s *D0` H  0޽h ? ̙33y___PPT10Y+D=' G= @B +  0    Z (    6J0> NNivS^ Ni2+ H+ % Ni3N NiO Ni(OH)2 NH3 450! H2O~p OH X2=Cl Br I% H2S Ni NiX2 NiS H+ CO, 50! HF Air Ni2+ Ni(CO)4 NiF2 Ni(OH)S W0ACK>CK1CK3CK CK CKCKCK"CK=CK"CKOCKCKCKC71tRB  s *D `RB @ s *D0 RB  s *Dp   rB9CEDEFE9@  RB  s *D 0` RB  s *DP RB   s *DP P    rBLCcDEFLc@  RB   s *D pP RB   s *D P RB   s *D P H  0޽h ? ̙33y___PPT10Y+D=' G= @B +v  0 &  (  B  6JZ ! @14-5-3-2 Co(a!)salts/ Ni(a!)salts B 00  $C 6  4  6(K Co(a!)ve4lr`e 8^/f݄r0Ğrb~r (W~vfr`b4lnm /fm~r FO4O gvxv4lnmRb݄rS^ H+-N3z[ OH -N gN[؏S'` CoCl26H2O |~! CoCl2 m݄ + 6H2O Rp N4l Co2+ + 2OH ! Co(OH)2!~ ! Co(OH)3!(H2O) GHCl ! Co2+ + Cl2! Co(OH)2 + OH (conc.) ! Co(OH)42 Co2+ + 7NO2 + 3K+ + 2H+ ! K3[Co(NO2)6] + NO!+ H2O :00 0 ;CKCK CKCK CKCK CKCK CK CKCK CKCKCKCK CKKCKCKKCKCKCKCKCK CKC5    &H  0޽h ? ̙33 0 nf (    6J<   Ni(a!)ve4lr`eY:NĞr ~vfv04lnmGW:N~r NiSO47H2O ~ ! NiSO4 Ğ + 7H2O (%) Ni2+ + 2OH ! Ni(OH)2 N~ ! Ni(OH)3! ў (Cl2 Br2) ! Ni2+ + Cl2 (HCl) 0i0 0 $CKCK CKCK CKCK CK CKCKCKCKCK C    6JP  H"0 C H  0޽h ? ̙33  0   0 (    6Jp 14-5-3-3 complexes B00 $C  60K`@L F~ (1)Complexes of Co(b!) or Co(a!) Co (b! :_'lSBR FOCo(b!)MTirkCo(a!)3z[ \!00 0 !CGH%  6l=K@ bB Co(b!)MTirdCoF63- Y GWNOe d2sp3BgS !00 C CKK CKCKC@  6`K0 @ &zDCo(NH3)63+/Co(NH3)62+ = 0.1V Co(a!)؏SRX:_ DCo(CN)63 / Co(CN)64 =-0.83 V 2Co(NH3)62+ + 1/2 O2 + H2O ! Co(NH3)63+ + 2OH 2Co(CN)64 + 2H2O ! 2Co(CN)63 + 2OH + H2! (%) ;00 0 CKK KK%CKK KKKCKCKKCKCK CKCKKCK CKKCK CKKCKCKC2  7   :B @ 3 C   6tbKy  *. DCo3+/Co2+ = 1.84V 00 CCKKKKKCCH  0޽h ? ̙33  0   @6 (    6KJ Bt[Co2+ Nnb bn Hg2+ Co2+ + SCN ! Co(SCN)42 ݄ (W4l-N N3z[ ! Hg[Co(SCN )4] ݄ Fe3+r^pb (u NaFc= vY0I0 GOPGOGOGO GOOGOGO G3  P  6\KZ zCo2+ CoHg(SCN)4! ݄ Zn2+ ZnHg(SCN)4 }v Cu2+ + Hg(SCN)42 ! CuHg(SCN)4! Ğ~ Ni2+ Ni[Hg(SCN)4] ZnCu[Hg(SCN)6] ! +} Co2+ + 4NO3 ! [Co(NO3)4]2 CN = 8 j800 0 CK/CKCK0CKCK CKKCKCK3CK>CK CKCKK CKCKCK C66 {  PH  0޽h ? ̙33/ 0 VNP(  *  6KPp t(2) Complexes of Ni(a!) Ni(H2O)22+ ~ Ni(CN)42 dsp2  Na2[Ni(CN)4] 3H2O Ğ  K2[Ni(CN)4] H2O Yj 00 0 .CKCKKCKKCKCKCKCK;CKCKCKC^58 B  M   \@ABCE F@#" 4  X@ABxCEFx@P @   X@ABCEF@#" &  X@ABCEF@P  X@ABCxEFx@ ,P    X@ABCEF@P  t   6\L` 0L  X C H3C N OH j00 0 CKC ,4   6Ly :t[ CH3 N  OH V00 CKC   6PK0  xNi2+ + 2 ! ~lm + 2H+f=0CK7CKC2   6| L   C 400 C z  6$Ls +  Ni(NH3)42+ m݄0 K3[Fe(CN)6] Ni(NH3)62+ +}~ 0[Ni(en)3]2+ +}~ Ni2+ + NH3H2O ! [Ni(NH3)6]2+ Ni2+ + en ! [Ni(en)3]2+ @0:0 0 CKCKKCKCKCKCKKCKCK CKCKCK CKCKCKCKCKCKCN  8LB  c $D`gLB  c $DS LB  c $D  LB  c $D J LB  c $D6  LB  c $D2JLB  c $D_x-H  0޽h ? ̙33y___PPT10Y+D=' G= @B + 0 `r(  :  0;Ld! |Use -----Co: Colbalt blue glass and pottery; for paints and inks; catalysts for organic reactions; specialty alloys with Cr and W for drill bits ,lathe tools, and surgical instruments; magnetic alloys(Alnico) Ni: Nickel steels for armor(v2u 2u) Stainless steel and AlnicoݔMTё ; Nonferrous alloys (tablewares) with Ag; Monelm3Tё NyM0ܔ000vTё with Cu for handling F2; Undercoat for chrome chromium plating; Nichrome; Hydrogenation catalyst0 CG(CGCKLC   . H  0޽h ? ̙33y___PPT10Y+D=' G= @B + 0 H(    6$PLp,  14-6 Pt Ru Rh Pd { 12g / cm3 Os Ir Pt ͑ 22g /cm3 DM2+ / M > 0 , N;mlё^\,QNNNUS(`X[(W  0n0 0  $CC!CK&CKCC  CC~ H  0޽h ? ̙33 0 6(    6uLP` .14-6-1 Valence Electron Configurations Ni 3d84s2 +2 Pd 4d10 +2 Pt 5d96s1 +2 +4 ؚ'lS`3z['`X 0(00R0 0 &CC CKCKCKCKCK"C  .B   0 h  6xpL  @ "0CL  6iL27  4yrp 8^'lSpe +2 +4 fb_bMTir `00 $C $C.   6L@?S  T00 CCC  6LV d  JbH2PtCl6 + 3Zn ! Pt + 3ZnCl2 + H2 (Cd Mg Al )20CKCKCKCKC% H  0޽h ? ̙33 0 PH(  F  0lL   hPt vS^ Pt(CO) 2Cl2 H2PtCl6 CO OH HCl 527! PtO2nH2O PtCl4 PtCl2 % PtS2 H2 Cl2 F2 % S F2427! PtO2 PtO ؚ)n Pt PtF4 NNaNO3 s4l Br2\I2 NaOH\Na2O2 H2S% qQq Zn (127!) PtS2 H2PtCl66H2O PtX2 Na2[Pt(OH)6] s4l (NH4)2S NH4Cl PtCl62 PtS32 (NH4)2PtCl6F0 2.0(2fCKCKECKCKACK8CKCK)CKCK7C KCKCK+KC KWCKCKXCKCKCKCKCKCK CKFCKCKCKCK+CKCKCKCKCKCKCKKCKKCKCKCK N 4 D 1 # RB  s *D0PPRB @ s *D0 RB  s *DRB  s *DP 0 RB  s *D P RB   s *D RB  @ s *D RB   s *D P RB   s *DP  RB  @ s *D  RB  s *DP RB  s *DP RB @ s *D P ` RB  s *D pP ` RB  s *D  RB  s *D p@ RB  s *D0 p0 RB  s *D 0 RB @ s *D0 0 RB  s *D ` RB  s *D3 3 H  0޽h ? ̙33D  0   @ (  @z @ 6$ B Pt + O2 = PtO ( % ! ؚ)n ! ) f!00  CKCCH  @ 6X L Pt + 2S (Se \ Te) ! PtS2 (ўh) PtS2 + HCl +HNO3 ! PtCl62 + NO PtS2 + (NH4)2S ! PtS32 Q0"0 0 CCKC$ CK CKCKKCKCKCK CKKCCz @ 6HX@ F  lP Pt + NaOH + Na2O2 ! Na2[Pt(OH)6] (00 CCKCKCKCKC,6 @ 6PX R  Pt + HCl + HNO3 ! H2PtCl66H2O + NH4+ ! (NH4)2PtCl6 + H2S ! PtS2 + Zn ! Pt ;00 0 CKCKCKCKCKKCKCKCKHCK CKUC,<H @ 0޽h ? ̙33H 0  (   d   6DM\ b14-6-2 Compounds of Platinum PtNё{|6(    6dM  0 (2) Pt(a!)-YNpMTir 1827t^,,{N*N NqTpvё^\MTir. [PtCl4]2 +C2H4 ![Pt(C2H4)Cl3] +Cl 2[Pt(C2H4)Cl3] ![Pt(C2H4)Cl2]2 + 2Cl Pt(a!) 5d8 ǑSdsp2BgS, Pt(a!)N3Cl (W TNs^b N YNpvS.WvNُ*Ns^b $N*NCN Pt2+vݍyvI{. "5uP[MMO Nd[5uP[[MMO N T. $'00 0 -GOGOGOGOGG3O3G3O3G3O3G3O3GOG3O3G3O3G3O3G3O3GOGOGOGOGO GOGO GOGOGG3 GV   H  0޽h ? ̙33  0 / ' (  -  6uP  % 14-6-3 Extraction and Application b%00 C ! C C!  6|M7 (1) Extraction s4l NH4+ ”w ! H2PtCl6 ! (NH4)2PtCl6 N TvQN”|CQ } vMTirRy 1073 K (NH4)2[PtCl6] ! Pt + Cl2 + NH4Cl 3(NH4)2[PtCl6] ! 3Pt + 2NH4Cl +16HCl+2N2 qp wm~rё^\”! PtWW 00 0 C CCCKK0CKCKCKCKCK8CKCKCK CKCKCKCKCK CK CKHC$CC .KH  6x0 P  ` "0C H  0޽h ? ̙33x 0 ( (    6O,  0(2) ^(u `$ Sf[3z['`ؚ ؚ)n (uZPTyS^hVv OPtiWW , ”5ug, ”Q  NGx0s4l ( ) Pt (C) | H2 , KOH (aq) || O2 , H2O| (C) Pt (+) NYT[x:NWSO Nb^n”| gb5ug ( ) 2H2 (g) + 4OH = 4H2O(l) + 4e ( ) O2 + 2H2O(l) + 4e = 4OH (aq) ;`2H2(g) + O2(g) = 2H2O(l) <0e0 `0 0 CACK CCKCKC)CK CKCKCKCKCK CKCKCKC ,  6lO   Ta$ ”Nv5u;)n^vGSؚ gĉ_vSS 6Rbp5uvPKm)n^ 1473K-2023K 4*00 +C   6OP  H"0 C H  0޽h ? ̙33N 0  (   V   0 .OZ   b$ PSBR @b gv”|ё^\ gN*Nyr'` sSPS;m'`_ؚ ё^\~N”ў vPS;m'`$\vQ'Y. O1: NH3 + O2 ! NO + H2O (Pt-Rh) CH4 + N2 ! HCN (Pt-Rh) H2 + O2 ! H2O (Pt| Nrpb_b) d.0X0 0 25CKCK CK CKCKCKCKCKCCb,H   0޽h ? ̙33 0 tl$(  $ $ 6 wOP R fO2. }llf>\lQSBR NCQPSBRTWC 5ё^\/fvQ;Nv;m'`bR CO + 1/2 O2 ! CO2 (Pt-PdvSTir) HC + O2 ! CO2 + H2O (Pt) NO + CO ! CO2 + 1/2 N2 (Rh) NO + CH ! CO2 + H2O + N2 (Rh) Pt-Rh:N;N, (ϑk = 5^7: (WzzlqekA/F :NSf[ϑke Te\CO0HCTNOXlS:Nek[vCO20H2OTN2, NHePSBR }SO;m'`Al2O3|b g;m'`mB\vteSO'`z kGS}SOO(uvPSBR;`ϑ:N1.0^2.0g0mRCeO20La2O30NiOI{~R NcؚPSBRp3z['`TPS'`$00 .CKCKCKCKCKCKCKCKCKCK;CK CKCKCKGOCCKCK,CKCKCKC; H $ 0޽h ? ̙33F 0  ((  ( ( 6`O N c$ oir 1969t^ V[l[]'Yf[Rosenberg B T Camp LV ZSX!kbSz_[PtCl2(NH3)2]wQ gbLvR uS]Lv0~w8N$v0;TLv gHe 2urzLv0ߘSLv0U4YޜLv0m]$vTzLv 0h0 0 6CKCKCKC)CR   0 ( 6XjOP`Z ^\ϑP[uirf[[:N LvirTuirSO~RKNv5uwy/f~ހLvSv,{N6k0S_DNANLvirce 5uwNDNATLviry ODNA&^ck5uw01uNY5uce\O(u DNAxWQv"l.4xOWv^ODNASe~gce DNATbck8^S:N_8^ N [LvS,{Nek0 N5uP[Lvir Lvir_0R5uP[ ~N5uP[DNA DNA1YS5uP[ ! e~g_ ! LvSRg H~000 0 C%  ( H ( 0޽h ? ̙33  0 0,L(  , , 6HOP@  Xz”bLvǏ z z” ! NSO~ހYؚNaCl Sm^SOm ! ǏDNA ~ހۏeQNaCl Sm^:S ! 1 NCl ODNA 5uMOGSؚ ! ~ހY5uwTDNA Qy ! DNA SeS'} ! _8^DNA b` Y:Nck8^DNA 1 1 sNNxN(lT”a! x” X0Y:Nx9hMSOCl }YA:N-N'`MSONH30NH2R SOyN\:N}Y 00 0 7CKYCK CKCK CT   H , 0޽h ? ̙33  0   D( (  D D 6X> c 400 C  D 6Pp v q 400 C  D 6P0 H"0 C  D 6 M  Pt + 2X2 ! PtX4 (Br2 0I2 127!Cl2230!F2427! ) 4"Pt4+ox [PtX6]2 3z['`PtF62 < PtCl62 < PtBr62 < PtI62 60;0  GOGOGOGO GOGO GOGOGOGOOGOOGOOGOOC D 6,>}  " 527! HCl PtCl4 ! PtCl2 ! H2PtCl6 OH % PtCl4 ! PtO2nH2O ! PtO2 H2 PtCl4 ! 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Valence electron configurations (n 1)d1 8ns1 2 with exceptionPd 4d10 Pt 5d96s1 W 5d46s2 gSSv'lSpe +2vNepev Tvgؚ'lSpe vNlS 'l؏S^ {$)HHHHHHH#l%8=>?E5.4lTyP[0MyP['YY gr$ @] 14-2 TitaniumN14-2-1 General Characteristics 14-2-2 Titanium 14-2-3 Compounds of TitaniumOOGH J K L M NOPQRSTUVWXYZ\r4*14-3 Cr Mo W oRe &B 14-3-1 General properties 14-3-2 Cr and its compounds 14-3-3*C8 ^_ a"b#c$d%e&f'g(h)i*j+k,l-m.n/o0p2q3u7v8w9x:y;z<{=|>}?~@e hKMnO4 +2KF +10HF +3H2O2 = 2K2MnF6 +8H2O+ 3O2 SbCl3+5HF=SbF5+5HCl K2MnF6 + 2 SbF5 =2KSbF6+ MnF3 +1/2 F2iNNN3N33N33NNFNFF3N3F3N33N33F3FF3N3FNFNFNFMNOPQRSTUVWXYZ[\]^_`abcdfghsijklmnopqtrq1  !"#$%&'()*+,-./01234՜.+,D՜.+,     NĻʾ Microsoftb mArialTahomaTimes New Roman Wingdings DotumCheSymbolShimmerVisio.Drawing.11Microsoft Word ĵMicrosoft Word ͼƬ õƬ 1 õƬ 214-1 General Property õƬ 4 õƬ 5 õƬ 65.ˮӡӴɫ õƬ 814-2 Titanium õƬ 10 õƬ 11 õƬ 12 õƬ 13 õƬ 14 õƬ 15 õƬ 16 õƬ 17 õƬ 18 õƬ 19 õƬ 20 õƬ 21 õƬ 22 õƬ 23 õƬ 24 õƬ 25 õƬ 26 õƬ 27 õƬ 28 õƬ 2914-3 Cr Mo W õƬ 31 õƬ 32 õƬ 33 õƬ 34 õƬ 35 õƬ 36 õƬ 37 õƬ 38 õƬ 39 õƬ 40 õƬ 41 õƬ 42 õƬ 43 õƬ 44 õƬ 45 õƬ 46 õƬ 47 õƬ 48 õƬ 49 õƬ 50 õƬ 51 õƬ 52 õƬ 53 õƬ 54 õƬ 55 õƬ 56 õƬ 57 õƬ 58 õƬ 59 õƬ 60 õƬ 61 õƬ 62 õƬ 63 õƬ 64 õƬ 65 õƬ 66 õƬ 67 õƬ 68 õƬ 69 õƬ 70 õƬ 71 õƬ 72 õƬ 73 õƬ 74 õƬ 75 õƬ 76 õƬ 77 õƬ 78 õƬ 79 õƬ 80 õƬ 81 õƬ 82 õƬ 83 õƬ 84 õƬ 85 õƬ 86 õƬ 87 õƬ 88 õƬ 89 õƬ 90 õƬ 91 õƬ 92 õƬ 93 õƬ 94 õƬ 95 õƬ 96 õƬ 97 õƬ 98  õʾĸģǶ OLE  õƬb  8@ _PID_HLINKSA` -1,-1,PREV -1,-1,PREV -1,-1,PREV -1,-1,PREV -1,-1,PREV -1,-1,PREV -1,-1,PREV -1,-1,PREV -1,-1,PREV -1,-1,PREV -1,-1,PREV -1,-1,PREV