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I- Nhn xt chung v cc nguyn t nhm VIB Ba nguyn t Cr ( Chromium ); Mo ( Molibdenium ); W ( Wolframium ) l cc nguyn t thuc h d trong cc chu k 4; 5; 6 thuc bng

tun hon. Crom c nh ha hc ngi Php l Vclanh (N. Vauquelin ) tm ra nm 1779; nm 1782 - nh ha hc Thy in l Hienm (P. Hjelm) iu ch c molipen; cn vonfram li do nh ha hc Thy in l Sao (K. Scheele) v cc nh ha hc Ty Ban Nha l anh em luia ( d' Elluyar ) tm ra ng thi vo cui th k 18 vo khong cc nm 1781 - 1783. Nguyn t khi, s th t nguyn t, s phn b electron v trng thi ha tr ca ba nguyn t nh sau:

Lp (n - 1)d cha hon chnh nn c nhiu trng thi ha tr. Bc oxi ha dng cao nht l +6 tng t nh nguyn t nhm VIA. c bit l crom - nguyn t in hnh ca nhm VIB - c nhiu tnh cht ging lu hunh, c hai u to ra oxit XO3 (CrO3 v SO3), u l oxit axit v u c axit tng ng l H2SO4 v H2CrO4; C hai cng u to hp cht SO2Cl2 v CrO2Cl2 u c bn cht cng ha tr. C hai nguyn t u to ra mui dng M2X2O7 l mui isunfat (v d Na2S2O7) v icromat (Na2Cr2O7). Ngoi ra, crom cng c nhiu tnh cht ging nhm v st, chng hn crom v nhm to ra oxit v hiroxit lng tnh; mui Cr(II) tng t mui Fe(II) v d CrCl2 v FeCl2; c crom v st u to ra mui c mu, v d ferat K2FeO4 mu ; cromat K2CrO4 c mu vng. Nhng tnh cht ging nhau, to ra hp cht tng t nhau, u c lin quan n bn knh ca ion trung tm ( = 0,34, =0,35; =0,83, =0,84; =0,62 (hoc 0,57), =0,67, =0,64). Mc d c mt s tnh cht ging vi nguyn t nhm VIA, nhng v c ba nguyn t ny u c mt electron s nm ngoi v d ( c 2e vonfram ) nn c tnh dng in hn v lp v ( n - 1)d cng d bin dng hn so vi cc nguyn t nhm VIA. Mt s c im nguyn t ca ba nguyn t trn nu ra bng 1.

Nguyn Th Ngc Anh 1

Bng 1. Mt s c im ca Cr - Mo - W

T bng trn ta thy bn knh nguyn t tng t Cr - Mo, nhng hu nh khng i khi chuyn t Mo n W. iu c gii thch l do hin tng nn lantanit ca cc nguyn t h lantan pha trc W. Do vy, molipen v vonfram c tnh cht gn nhau hn so vi crom. Cng chnh do s co lp v electron, nn th ion ha khi i t trn ung di tng, c bit tng mnh khi chuyn t Mo n W. Khi so snh th in cc chun c th thy c crom v molipen u l kim loi c hot tnh trung bnh. Crom ng sau mangan v trc st, cn molipen ng trc thic. Di y l s th in cc ca crom v molipen: Trong mi trng axit :

Trong mi trng baz :

Nguyn Th Ngc Anh 2

V mt cu to tinh th, c ba kim loi Cr - Mo - W u kt tinh theo kiu lp phng tm khi. Vi Cr : = 2,8846; Mo : = 3,1464 ; W : = 3,1650 Bi tiu lun ny s tp trung nghin cu v crom, nguyn t in hnh ca nhm VIB, lm r cc tnh cht l ha v ng dng ca n trong thc t II. Trng thi thin nhin v thnh phn cc ng v Crom c 10 ng v, cc ng v thin nhin l 50Cr (4,31%); 52Cr(83,76%); 53 Cr (9,55%); 54Cr (2,38%). Trong cc ng v phng x th ng v 51Cr bn nht c chu k bn hy l 28 ngy m, v ng v km bn nht l 47Cr c chu k bn hy l 0,4 giy. Mc d l nguyn t ph bin trong 21 nguyn t c trong v tri t, nhng cc trm tch crom t nhin (crom nguyn cht) l kh him, ta ch pht hin c mt vi m crom kim loi t nhin, tiu biu l m Udachnaya ti Nga c cha cc mu ca crom kim loi t nhin. Trong v qu t, khong vt ch yu ca crom l qung st cromit [FeCr2O4 hay FeO.Cr2O3; Fe(CrO2)2] v qung croisit hay ch cromat (PbCrO4). Gn mt na qung cromit trn th gii c khai thc ti Nam Phi, bn cnh , Kazakhstan, n v Th Nh K cng l cc khu vc sn xut ng k. Cc trm tch cromit cha khai thc c nhiu, nhng v mt a l ch tp trung ti Kazakhstan v min nam chu Phi. Vit Nam c khong sn cromit C nh (Thanh Ha). Ngoi ra, crom cn c trong lng ln cc khong v cc loi m c mu sc in hnh ca crom, chng hn nh trong ngc lc bo, granit, crisoblie, khong silicat v pyroxen. Nng crom trong cc khong l khc nhau i vi mi loi v trng thi t nhin ca cc loi , v trong cc loi la, nh serpentine, cng nh cc loi khong st v photphat, c th tm thy hm lng crom ln khong 1800 mg/kg cht. Mt khc, trong trm tch, c bit l trong ct, carbonat v granit li ch cha hm lng crom rt thp, ch c tm 1mg/kg cht. Trong c th sng, ch yu l thc vt c cha khong 10 - 4 % crom (theo khi lng). Trong c th con ngi crom cng tn ti nh mt vi lng cn thit cho qu trnh trao i cht trong c th con ngi. Trong nc ca i dng c 5.10-5 mg crom trong 1 lit nc bin. III - Tnh cht l hc ca Crom trng thi n cht, crom cng, mt bng, mu xm thp, khng mi, khng v, d rn. Crm c nhiu trong thin nhin, to thnh nhng hp kim c mu sc rc r, li cun s quan tm ca nhiu ngi nht l nhng nh khong sn nhng do hp cht ca chng kh bn vng, kh ho tan, rt kh tch ring nn n mi cui th k 18 mi c tm ra.

Nguyn Th Ngc Anh 3

Mt s hng s l hc quan trng ca Cr, Mo, W

- Crom c khi lng ring rt ln (7,2 g/cm3), rt kh nng chy v kh bay hi. Cc nguyn t nhm V u dn in km, trong crom dn in km nht ch bng 10% dn in ca Au v 6,8% dn in ca bc. - Crom c nhit nng chy cao (1875oC), cng ln, kh nng d lin kt vi nhiu nguyn t khc to thnh hp kim, c bit l vi st, khin cc nh luyn kim n crom trc tin. Cho n ngy nay, ngnh luyn kim vn l ngnh tiu th crom nhiu nht mc d nguyn t ny tm c kh nhiu cng vic c ch khc. IV- Tnh cht ha hc ca Crom Hot tnh ha hc ca cc kim loi nhm ny gim t crom n vonfram, do kh nng phn ng vi cc cht gim dn. Ta s tp trung xt cc phn ng ca Crom i din cho c ba kim loi - iu kin thng crom khng phn ng vi oxi, nhng khi t trong khng kh th to ra Cr2O3. - Khi nung hn hp gm bt crom vi bt lu hunh trong ampun thu cc sunfua c thnh phn khc nhau nh CrS, Cr2S3, Cr3S4, Cr5S6, Cr7S8. - Vi cc halogen, phn ng xy ra c mc khc nhau ph thuc vo hot tnh ca cc halogen; crom phn ng trc tip vi flo ngay c khi ngui; vi clo phi un nng. - Khi nung bt crom trong kh quyn nit s to ra Cr2N 900oC v CrN 1200oC. - Photpho cng phn ng trc tip vi crom khi nung trong chn khng, trong ampun bng thch anh to ra cc hp cht nh CrP, Cr3P, CrP2. - Phn ng trc tip vi cacbon to ra Cr2C3 khi nung crom vi cacbon nhit cao; vi silic to ra CrSi, Cr3Si, CrSi2 cng nhit cao. - V trn b mt c lp oxit c hot tnh ha hc km rt mng v bn vng che ch cho kim loi, nn nhit thng, crom rt bn v mt ha hc. Khi nung n nhit nng , crom kh c H2O to ra hiro:

Nguyn Th Ngc Anh 4

- Crom ha tan trong HCl v H2SO4 long nng to mui Cr(II) mu xanh lam, sau mui Cr(II) b oxi ca khng kh oxi ha to ra mui crom(III) mu xanh l cy:

H2SO4 c ha tan crom to ra mui Cr(III) v SO2 : HNO3 c hoc long v nc cng thy - khi ngui - khng tc dng vi crom, khi un nng tc dng yu, khi un si phn ng xy ra mnh to ra mui crom(III):

Nguyn nhn gy ra tnh bn ca crom trong cc loi axit trn l do to ra lp oxit bo v b mt kim loi nn gy ra " tnh th ng " ca crom. Crom c th tc dng vi dung dch mui ca nhng kim loi c th tiu chun cao hn to thnh mui Cr(II): V - iu ch Crom - Trong thc t, iu ch crom cng nh cc kim loi nguyn t nhm ny ta thng luyn thnh cc hp kim vi st c giu cc kim loi , nh hp kim ferocrom (cha 30-60% crom); hp kim feromolipen (cha 50-75% Mo) v hp kim ferovonfram (cha 50-80% W). iu ch kim loi tinh khit, th nguyn tc chung l chuyn cc loi qung trn thnh oxit, sau dng Al hoc H2 kh nhit cao. - iu ch hp kim cacbon - ferocrom ngi ta dng cacbon kh trc tip qung cromit trong l in hoc l Xi men Mactanh (Siemens - Martin): - iu ch crom tinh khit ngi ta nung nng chy qung cromit st - (sau khi lm giu) - vi NaOH hoc K2CO3 v oxi ha bng oxi chuyn Cr(III) thnh CrO42- 1000 - 1300oC:

Ha tan hn hp trong nc ri axit ha to ra bicromat, sau dng cacbon kh natri bicromat to thnh Cr2O3: oxit to thnh c kh n crom bng phng php nhit nhm; H2 khng kh c Cr2O3:

Nguyn Th Ngc Anh 5

VI- Cc hp cht ca crom Nh nu trn, crom - molipen - vonfram c cc bc oxi ha t 1 n 6, trong crom to ra nhng hp cht bn v c nhiu ng dng thc t l cc dn xut Cr(III) v Cr(VI), ngoi ra ta cn tm thy mt s t cc hp cht ng vi bc oxi ha +2 nh CrO mu en; Cr(OH)2 mu vng; CrS mu en, CrCl2 mu trng.... Hai s oxy ha cn li ca crom l Cr(V) v Cr( V) c tm thy trong cc trng thi chuyn tip c thi gian tn ti ngn trong qu trnh kh Cr(V ), nhng khng c tm thy c trong dung dch lng v dng bn, chng d b phn hy to thnh Cr(III) v Cr(VI). Ion CrO43- tn ti trong mt s hp cht kim hoc kim th nhng nhng cht rn ny ht m v d b thy phn thnh Cr(III) v Cr(VI). 1, Cc hp cht v i s oxi ha +2 - Trong dung dch, ion Cr2+ c mu xanh nht. Cc hp cht ca Cr(II) u c tnh kh, d b oxi ha thnh Cr(III), do u l tc nhn kh tt. Ion Cr2+ c tnh kh mnh n mc c th kh c ion H+ theo phng trnh: Trong dung dch ion Cr2+ dng [ Cr(H2O)6]2+ vi cu trc tm mt. a, it v hydro it ca Cr( ) Crom(II) oxit (CrO) c iu ch bng cch phi hn hng crom trong khng kh, nhng khng th thu c khi nung crom (II) hiroxit Cr(OH)2. Hiroxit ny to ra khi cho mui Cr(II) tc dng vi dung dch kim trong iu kin khng c khng kh:

trong khng kh dn dn chuyn thnh Cr(OH)3 mu xanh ru: - Khi un nng CrO vi lng oxi d to thnh Cr2O3, cn khi nung Cr(OH)2 to ra Cr2O3 v H2: - CrO v Cr(OH)2 u tan trong axit khng c tnh oxi ha to thnh mui Cr(II); khng tan trong kim, chng t ch c tnh baz. b, Cc mui ca Cr( ) * Crom(II) clorua (CrCl2) khan c iu ch bng cch un nng crom trong kh quyn hiro clorua: hoc nung CrCl3 trong lung kh hiro 600oC : - CrCl2 dung dch c iu ch bng CrCl3 bng hiro mi sinh (hn hp gm Zn + HCl). Nguyn Th Ngc Anh 6

- Khi cho dung dch CrCl2 c tc dng vi natri axetat to ra kt ta Cr(II) axetat: - CrCl2 d b oxi ca khng kh oxi ha, nn ngi ta thng dng dung dch CrCl2 trong HCl hp th oxi: - Khi khng c mt cht oxi ha, CrCl2 b H2O phn hy : - CrCl2 khan l cht kt tinh mu trng, Tnc = 824oC, rt ht m v tan trong nc thnh dung dch mu xanh da tri. T dung dch, CrCl2 c th tch ra dng hirat kt tinh CrCl2.4H2O mu xanh c cu hnh tm mt, trong bao quanh Cr(II) l 4 phn t H2O v 2 nguyn t clo:

- Ngi ta cng iu ch c CrF2 mu xanh (Tnc = 1100oC); CrBr2 mu vng nht (Tnc = 842oC); CrI2 mu (Tnc = 195oC ), bng phng php kh (t crom trong kh hiro halogenua ). Tr CrF2 t tan, cn li u d tan trong nc. * Crom(II) sunfat (CrSO4) Crom(II) sunfat c iu ch bng cch ha tan crom hoc Cr(II) axetat trong H2SO4 long trong iu kin khng c khng kh: Ta thu c hai dng hirat ha CrSO4.4H2O v CrSO4.7H2O ng hnh vi FeSO4.7H2O. Trong tinh th CrSO4.4H2O th nhm (SO4) ng vai tr cu ni gia 2 nguyn t Cr(II); cn trong tinh th CrSO4.7H2O th c mt phn t H2O ng vai tr cu ni do to ra lin kt hiro:

Nguyn Th Ngc Anh 7

Khi kt tinh vi sunfat ca kim loi kim, CrSO4 cng c kh nng to ra dng mui kp K2SO4.CrSO4.6H2O. - V c tnh kh, nn dung dch CrSO4 trong H2SO4 long cng dng hp th oxi, theo phng trnh tng qut: hay 2, Hp cht v i s oxi ha +3 Nh nu nhn xt trn, cc hp cht ca Cr(III) c nhiu gi tr thc t. Trong cc hp cht Cr(III) c s phi tr l 6, ng vi dng lai ha d2sp3:

a, it v hydro it ca Cr( ) Crom(III) oxit (Cr2O3) l cht bt mu xanh thm, cn trng thi tinh th c mu en v c nh kim. Cr2O3 l cht rt kh nng chy (Tnc=265oC). Cr2O3 c cu trc ion dng corinon ( - Al2O3). - Cr2O3 c iu ch bng nhiu cch khc nhau. + t bt crom trong khng kh, crom chy theo phng trnh : + Nung (NH4)2Cr2O7 ( hay hn hp K2Cr2O7 + NH4Cl ): + Dng than g hoc lu hunh kh K2Cr2O7 nhit cao:

- Cr2O3 khng tan trong nc, tan rt chm trong axit to thnh mui Cr(III), v khi nung vi kim trong khng kh hoc vi cht oxi ha khc nh KNO3 to ra cromat :

hay - Ngi ta c th chuyn Cr2O3 khng tan thnh mt cht d tan hn bng cch nung vi kali isunfat to ra Cr2(SO4)3 d tan hn: - Cr2O3 cng c th thnh cht tan c trong nc bng cch nu nng chy vi Na2CO3 v NaNO3 to ra natri cromat :

Nguyn Th Ngc Anh 8

Ngoi ra, natri peoxit, kali pemanganat, ch(IV) oxit, bt ty... u c th oxi ha Cr2O3 thnh cromat. - Crom hiroxit (Cr(OH)3) l kt ta keo mu xanh nht, to ra khi cho dung dch kim tc dng vi dung dch mui Cr(III). Thc cht ca kt ta keo l dng hirat ha Cr2O3.xH2O.Cr(OH)3 l mt polime a nhn trong nhm OH v H2O ng vai tr phi t v ng vai tr cu ni l nhm -OH. Thnh phn v cu trc ph thuc vo iu kin iu ch, v d c cu trc lp nh sau:

Khi x = 3 ta c dng Cr2O3.3H2O tc l dng Cr(OH)3 - Kt ta thu c khng tan trong nc (Tt = 1.10-32) nhng d tan trong axit v kim, lc c xy ra s ct t lin kt gia cc lp,v d : hay hay Qu trnh to ra cation v anion phc c th tm tt nh sau:

- Cr(OH)3 cng b oxi ha to ra cromat mu vng khi cho tc dng vi Na2O2, Br2 trong dung dch kim, bt ty, nc Javen, PbO2...

b, Cc mui ca Cr( ) Nguyn Th Ngc Anh 9

* Crom(III) clorua (CrCl3) dng khan c iu ch bng cch cho kh Cl2 qua crom nung nng :

hoc cho kh clo qua hn hp gm Cr2O3 v Cacbon nung nng : - Dng hirat ha CrCl3.6H2O c iu ch bng cch cho Cr(OH)3 tan trong dung dch HCl, sau cho kt ta t dung dch nc. - Ph thuc vo cc nhit , nng v pH ca dung dch m thnh phn ca cation phc aquo thay i, do mu sc ca CrCl3.H2O s thay i t tm n xanh. V d :

- CrCl3 khan c cu trc ca polime, c mu tm , khc vi mu ca dng hirat ha nu trn. S khc nhau v cu trc gy ra s khc nhau v tnh cht, v d CrCl3 khan khng tan trong nc, cn CrCl3.6H2O li d tan trong nc. Trong dung dch, c ba dng hirat ha u dn dn bin thnh hn hp dng mu xanh thm v dng xanh tm. Bc chuyn ko di t 10 - 40 ngy ph thuc vo iu kin bn ngoi, v d 25oC sau 15 ngy trong dung dch c cha khong 42% dng xanh tm v 58% dng xanh thm. Khi nung nhit cao trong lung kh clo, CrCl3 thng hoa nhng khng c clo th phn hy: Khi nung trong khng kh chuyn thnh oxit :

v khi tc dng vi hp cht cha hiro th clo trong phn t c thay th:

* Crom (III) sunfat (Cr2(SO4)3) c iu ch bng cch khuy bt nho Cr(OH)3 trong H2SO4 c. Tinh th thu c c mu tm Cr2(SO4)3.18H2O hoc Cr2(SO4)3.6H2O c mu lc.

Nguyn Th Ngc Anh 10

- Khi ng kt tinh vi mt mui sunfat ca kim loi ha tr 1 (Na+, K+, NH4+, Rb+, Cs+, Tl+) tch ra tinh th phn crom mu tm thm c thnh phn [M2SO4.Cr2(SO4)3.24H2O] trong phn kali d tan trong nc v c nhiu ng dng thc t nh dng trong cng nghip dt, cng nghip thuc da. - Phn crom - kali l nhng tinh th hnh tm mt, mu tm thm, khi cho nh sng truyn qua c mu ta. Phn crom - kali c iu ch bng cch kh K2Cr2O7 trong dung dch c axit ha bng H2SO4. Tc nhn kh tt nht l SO2 hoc C2H5OH; phn ng xy ra theo phng trnh:

hoc

ngoi khng kh, phn b ln hoa, ph mt mng mng mu tm. Khi un nng n 100oC, phn c mu xanh lc do mt mt phn H2O kt tinh. Nc kt tinh mt hon ton 350oC, v khi nung qu 350oC mui c mu vng lc khng cn c kh nng ha tan c na. Bng phng php phn tch tia X cho thy rng cu trc ca phn gm [MI(OH2)6][Cr(OH2)6].(SO4)2. Nh vy phn l mt mui kp. * Crom(III) nitrat (Cr(NO3)3) c iu ch bng cch ha tan Cr(OH)3 trong axit nitric. Dung dch trong nh sng phn chiu c mu tm - xanh da tri, cn trong nh sng i qua li c mu . Khi un nng, dung dch c mu xanh lc, ngui tr li mu tm ban u. - Khi kt tinh t dung dch nc, hm lng nc kt tinh thay i ph thuc vo iu kin iu ch. - Cr(NO3)3 c dng lm cht cm mu trong k thut in hoa vo vi. * Crom(III) sunfua (Cr2S3) l cht rn mu en, khng tan trong nc v b nc phn hy chm. Tng t nh nhm sunfua, Cr2S3 khng th to ra khi cho dung dch mui Cr(III) tc dng vi mt sunfua tan m to ra hiroxit do qu trnh thu phn: - C th iu ch Cr2S3 bng cch nung hn hp bt crom vi bt lu hunh trong ng kn : hoc bng cch cho hi H2S qua CrCl3 nung : - Cr2S3 b thy phn to ra Cr(OH)3:

Nguyn Th Ngc Anh 11

- Cng tng t, khng th iu ch Cr(III) cacbonat bng cch cho xoa tc dng vi dung dch mui Cr(III) : * Crom (III) xianua (Cr(CN)3) to ra khi cho dung dch mui Cr(III) tc dng vi dung dch xianua ca kim loi kim. Kt ta Cr(CN)3 tan trong axit v tan trong dung dch xianua d to ra M3[Cr(CN)6]:

K3[Cr(CN)6] l cht mu vng ti, ng hnh vi K3[Fe(CN)6] mu mu. 3, Cc hp cht v i s oxi ha +6 Kh nng phn ng ca Cr(V ) c c nh bi s o i ha cao nht ca n. Th o i ha kh ca Cr(V ) mnh hay khng ph thuc vo gi tr pH ca mi trng, E0 l 1.33 V trong mi trng a it theo phn ng sau: v -0.13 V trong mi trng trung tnh qua phn ng kh cromat thnh Cr( ) hydro it theo phn ng sau: Do , s tn ti ca Cr(V ) v cc dng ion ha ca n l Cr 42- v Cr2O72- ph thuc vo th o i ha v gi tr pH. a, Crom(VI) oxit Crom(VI) oxit (CrO3) mu thm, c iu ch bng cch cho axit H2SO4 c tc dng vi dung dch bo ha kali icromat hoc kali cromat : CrO3 tch ra dng tinh th hnh kim (Tnc = 196oC). - CrO3 l mt anhirit axit in hnh, ht m mnh v d tan trong nc to ra axit cromic : - CrO3 rt c v l cht oxi ha mnh. Khi nung nng n 196oC to ra cht lng mu thm; n 250oC to ra crom(IV) ioxit v cui cng 420oC to ra crom(III) oxit:

- Anhirit cromic oxi ha c rt nhiu cht gy ra hin tng n, phn ng mnh vi nhiu cht hu c, chng hn ru, giy u b bc chy khi tc dng vi CrO3. Tuy nhin, CrO3 li tan trong axit axetic m khng gy ra hin tng g. b, Axit cromic( H2CrO4) v mui cromat ( CrO42-).

Nguyn Th Ngc Anh 12

- Khi ha tan CrO3 vo nc to ra axit cromic l mt axit trung bnh, ch tn ti trong dung dch, khng tch c trng thi t do; trong dung dch nc tn ti cn bng :

Nh vy trong dung dch tn ti c hai dng ion CrO42- v Cr2O72-: - Nhng cromat tan quan trng l kali cromat K2CrO4 v natri cromat Na2CrO4.10H2O. Nhng cromat khng tan quan trng l ch (II) cromat PbCrO4; bc cromat Ag2CrO4; v bari cromat BaCrO4. Kali cromat (K2CrO4): l nhng tinh th t phng, mu vng, bn ngoi khng kh; Tnc = 968oC. Tan trong nc cho dung dch mu vng m, c phn ng trung ha vi qu. Khi cho thm axit, dung dch c mu vng da cam do phn ng: Khi un nng n 670oC, K2CrO4 chuyn thnh mu , ngui tr li mu vng ng hnh vi K2SO4. - Ngi ta iu ch K2CrO4 bng cch cho Na2CO3 hoc KOH tc dng vi dung dch K2Cr2O7:

- Natri cromat (Na2CrO4) c iu ch bng cch cho natri icromat tc dng vi Na2CO3: Trong cng nghip iu ch bng cch nung hn hp gm Fe (II) cromit vi Na2CO3 trong khng kh : - Khi kt tinh t dung dch nc, ta thu c tinh th ngm nc. S phn t H2O kt tinh ph thuc vo nhit . 19,5oC to ra tinh th Na2CrO4.10H2O; khong 19,5-25,9oC l Na2CrO4.6H2O; khong 25,9-62,8oC to ra Na2CrO4.4H2O. Khi kt tinh trn 62,8oC to ra mui khan. Tt c cc dng tinh th u c mu vng. Mui khan c Tnc = 792oC. - Amoni cromat ((NH4)2CrO4) l nhng tinh th hnh kim vng nh, d tan trong nc. ngoi khng kh hay phi kh b mt mt phn amoniac v bin thnh (NH4)2Cr2O7. (NH4)2CrO4 khi un nhanh, b phn hy v bc chy : - Dng tinh khit c iu ch bng cch cho dung dch (NH4)2Cr2O7 tc dng vi dung dch amoniac sau cho kt tinh +5oC :

Nguyn Th Ngc Anh 13

- Bc cromat (Ag2CrO4) l cht bt v nh hnh mu t tan trong nc, Tt=1,1.10-12; nhng li tan c trong axit nitric v trong dung dch amoniac: - Dng tinh khit c iu ch bng cch cho dung dch AgNO3 tc dng vi K2CrO4: - Ch cromat (PbCrO4) khi mi kt ta l cht bt mu vng chanh; tinh th , trong sut hay nu thm. Tnc = 844oC, khng tan trong nc, tan trong dung dch HNO3 v dung dch kim (Tt = 8,3.10-12). - Dng tinh khit c iu ch bng cch cho ch axetat tc dng vi dung dch Na2Cr2O7: - PbCrO4 tan trong dung dch kim l do to ra hp cht hiroxoplombit: - Nhng nu lng kim t li to ra cht kh tan l ch(III) cromat baz PbCrO4.Pb(OH)2: - Nu lng cromat Pb(II) nhiu hn th to ra hp cht mu PbCrO4.PbO: thm

- Bari cromat (BaCrO4) l cht bt mu vng, khng tan trong nc, Tt = 1,2.10-10 - Dng tinh khit c iu ch bng cch cho dung dch K2Cr2O7 tc dng vi hn hp gm natri axetat v BaCl2 : c, Axit icromic (H2Cr2O7) v mui icromat ( Cr2O72-) - Axit icromic ch bit c trong dung dch c cu to tng t H2SO7. Trong cc mui ca axit H2Cr2O7 th c bit l mui K2Cr2O7 v Na2Cr2O7.2H2O l nhng mui quan trng, thng lm cht u iu ch cc hp cht khc ca nguyn t . - Kali icromat (K2Cr2O7) c iu ch bng cch cho KCl tc dng vi dung dch c Na2Cr2O7 : ( tan ca Na2Cr2O7.2H2O l 180g/100 g H2O 20oC). Lm bay hi dung dch thu c tinh th khan mu da cam. K2Cr2O7 tan trong nc; un si dung dch c mu thm; nng chy 395oC. Khi nung nhit nng trng K2Cr2O7 phn hy theo cc giai on:

cui cng l: Nguyn Th Ngc Anh 14

- Amoni icromat ((NH4)2Cr2O7) c iu ch bng cch cho dung dch amoniac tc dng vi dung dch CrO3. (NH4)2Cr2O7 l cht rn kt tinh mu da cam, tan nhiu trong nc t bc chy 168oC to thnh Cr2O3: - Bc icromat (Ag2Cr2O7) c iu ch bng cch un si dung dch K2Cr2O7 v HNO3 sau cho tc dng vi dung dch nng AgNO3: ngui, tinh th mu tch ra. Khi un si vi H2O to thnh Ag2CrO4, ngui li tr li tinh th Ag2Cr2O7 ban u. N t tan trong nc Tt = 2.10-7, 25oC tan nhiu trong HNO3. - Cc hp cht cromat u c tnh oxi ha mnh. Khi tc dng vi cht kh ty theo mi trng m to ra sn phm khc nhau, t Cr(VI) chuyn thnh Cr(III). - Trong mi trng trung tnh to ra Cr(OH)3: - Trong mi trng axit to ra ion [Cr(OH2)6]3+: - Tnh oxi ha ca icromat th hin mnh trong mi trng axit. Trong mi trng axit, cc mui icromat oxi ha c Fe2+ Fe3+; I- 2; SO32-S 42-..v.v... Trong dung dch, v tr ca cn bng: s chuyn dch ph thuc vo pH ca dung dch: + pH > 6 trong dung dch tn ti ion CrO42-. + 2 pH 6 ion HCr 4- v ion Cr2O72- nm cn bng vi nhau. + pH < 1 ch yu tn ti cc phn t H2CrO4 (hng s axit ca H2CrO4: K1=1,8. 10-1; K2 = 3,2. 10-7; ca H2Cr2O7: K2 = 2,3.10-2). - Ch c axit HNO3 v HClO4 mi lm thay i cn bng. Nu s dng HCl s to thnh clorocromat: cn trong H2SO4 s to ra phc cht sunfat: - Cn bng trn cng thay i khi cho thm cc cation c kh nng to ra cromat khng tan nh ion Ag+, Pb+, Ba2+, th s kt ta cromat m khng phi l icromat. - Vi Cr(VI) c kh nng to ra mt dy hp cht gi chung l policromat c cng thc tng qut K2[CrO4(CrO3)n-1], V d K2Cr2O7 - icromat; K2Cr3O10 tricromat; K2Cr4O13 - tetracromat.

Nguyn Th Ngc Anh 15

- Cromyl clorua (CrO2Cl2) l mt trong nhng hp cht c trng ca Cr(VI). L cht lng mu to ra khi cho CrO3 kh tc dng vi kh HCl: hoc khi un nng icromat vi hn hp gm mui clorua kim loi kim trong H2SO4 c: - Cromyl clorua c Tnc = -95,6oC v Ts = 117oC, l cht oxi ha mnh lit cc hp cht hu c. CrO2Cl2 b thy phn to ra CrO4: - Cc hp cht ca Cr(VI) c tnh cht tng t nh S(VI). + CrO3 c cu to tng t SO3 v u c tnh oxi ha, u phn ng vi H2O to ra axit tng ng. + Cc mui cromat kt tinh ng hnh vi mui sunfat: Na2CrO4.10H2O v Na2SO4.10H2O u tan; K2CrO4 v K2SO4 u tan PbCrO4 v PbSO4 du khng tan; BaCrO4 v BaSO4 u khng tan + Cc axit icromic v axit isunfuric c cu to tng t v u to ra mui tng ng: H2Cr2O7 v H2S2O7; K2Cr2O7 v K2S2O7 + Crom v S u to ra ion policromat v ion polisunfat tng ng: [Crn+1O3n+4]: Cr2O72- hoc Cr3O102- v [Sn+1O3n+4]: S2O72- hoc S3O102+ Crom to ra cromyl clorua v lu hunh to ra sunfuryl clorua c tnh cht tng t nhau.

VI- c tnh v ng dng ca Crom c tnh ca crom v hp cht c tnh ca crom cn ph thuc vo trng thi tn ti ca n. Crom kim loi t c hoc ch c tc dng d ng trn da. Crom ha tr ba (Cr(III) hay Cr3+) l nguyn t vi lng cn thit cho qu trnh trao i cht trong c th ngi v s thiu ht n c th sinh ra bnh gi l thiu ht crom. Trong c th ngi trng thnh cha trung bnh t 1-5mg crm. Trong mu ngi bnh thng t l crm l 10mcg/l nhng nhng ngi lm vic trong mi trng c crm th t l ny tng ln, nht l trong hng cu c th ln n 40-60mcg/l mu. Crm cn cho s chuyn ho cc glucid v lipid. Ring i vi insulin, crm to thun li cho s lin kt insulin lin kt vi c quan th cm ca n, do gip cho s ng ho ng glucose ca cc t bo, to s iu tit t l insulin trong mu, lm tng tnh nhy cm ca cc m i vi insulin, bnh thng v n nh glycemic (t l ng trong mu).

Nguyn Th Ngc Anh 16

Crm c trong thc phm nh gan b, lng trng, men bia, t l thp di 10mcg/100g, c nhiu hn mt t trong ng, khoai ty, bnh m en, u xanh, nm, tht b. Crm c a vo c th qua thc phm, h hp, da. Khi n, crm hp thu rut non vi t l 0,4-3%. Ch n ung v mt s cht cng nh hng n s hp thu crm, c cht lm hn ch (cht phytat), c cht lm tng (histidin, acid glutamic...). Cn qua ng h hp, cc dn cht crm tan trong nc xuyn qua mng cc ph nang cn cc dn cht khng tan c tch t m phi. Qua ng tip xc, crm khng xuyn qua da m to thnh mt phc hp bn vi protein cc lp b mt ca da. Tuy nhin, nu lng crm cao vo c th qua ng tiu ho s gy ng c nng c th dn n t vong, cn qua ng tip xc lu di s b lot da, vim kt mc, vim mi v nh hng n h hp. Ngc li, crom ha tr su (Cr(VI) hay Cr6+) li rt c hi v gy t bin gen khi ht phi. trng thi dung dch hp cht cCr(VI) c xc nhn l gy ra vim da tip xc d ng (ACD). Hp cht Cr(VI) cn l cht c cnh bo gy ung th khi tip xc lu di. 2, ng dng ca crom v hp cht Crom tinh khit ch cn ln mt lng tp cht khng ng k cng lm cho crom tr nn rt gin, v th m trong thc t ngi ta khng s dng n lm vt liu kt cu, cn vi vai tr l mt nguyn t iu cht th t lu crom c cc nh luyn kim qu trng. Ch cn pha thm mt lng nh crom vo cng lm cho thp c cng v chng mn cao hn. Nhng tnh cht nh vy rt cn cho loi thp dng lm bi m trong thnh phn ca n, ngoi crom (n 1,5%) ra, cn c cacbon (gn 1%). Crom cacbua to thnh trong loi thp c cng rt cao, cho php thp chng chi rt tt vi mt trong nhng k th nguy him nht - l s mi mn. Crom khng nhng c cng cao, m cn chng li c s oxi ha trong khng kh v khng tng tc vi cc a it. Dng phng php in phn vi axit cromic (trong , crom c ha tr su) lm cht in phn, c th m mt lp mng kim loi ny ln b mt cc sn phm lm bng cc th vt liu khc gi cho chng khi b n mn, khi b xy xt,. B dy ca cc lp m c th t n 1 milimet (chng hn, trn mt s chi tit bn ngoi ca t, m t, e p). Cng c khi lp m crom c s dng vo mc ch trang tr: m ng h, tay nm ca v cc vt khc khng nm trong vng nguy him. Trong nhng trng hp nh vy, ch cn m nhng lp crom cc mng (0,0002 - 0,0005 milimet). Crom c dng m cc dng c bng kim loi cn c sc chu ng tt, thng dng phng php in phn vi lp m c chiu dy khong 0,5mm. Thp crom ch to bng cch cho hp kim ferocrom vo thp; loi thp ny cng hn v do hn so thp thng, dng ch to cc dng c quay nhanh; thp khng g (stainless - steel) cha 12% crom v 0,7% niken. Thp crom-niken (nichrome) cha 6% ni ken, 25% st v 15% crom c nhit nng chy cao, dn in cao, khng b oxi ha bi khng kh, c dng trong cng nghip in. Nguyn Th Ngc Anh 17

Hin nay, khng ch m crom cho kim loi, cc nh bc hc bit cch to nn lp v crom ngay c trn cc sn phm bng cht do. Polistirolen - mt loi cht do rt quen thuc v kinh qua nhiu th thch, nu c m crom th s bn vng hn v khng s nhng k th mun tha ca cc vt liu kt cu nh s mi mn, s un v s va p. L ng nhin, thi hn s dng cc chi tit lm bng vt liu ny s tng ln. Lp v crom thm ch cn c ch cho loi vt liu mu mc v cng l kim cng. S d nh vy l v khng phi tt c kim cng khai thc c u c th dng ch to dng c ct gt: thng thng, kim cng thin nhin c rt nhiu vt nt cc nh lm cho n khng th dng gn ln dng c ct gt hoc mi khoan, v th dng c nh vy h chm vo kim loi hoc cng th kim cng lin v ra tng mnh nh. Ngoi ra, cc tinh th kim cng thin nhin thng khng bm cht vo thn dng c ct gt. khc phc nhc im ny, cc nh bc hc ngh bc kim cng bng mt mng crom mng va bm chc vo vi kim cng va bm chc vo vi ch gn bng ng. Do sau khi kt hp vi cc nguyn t cacbon ca kim cng, cc nguyn t crom to ra nhng nguyn t crom cacbua cng trn b mt kim cng, ngoi ra, crom cn xm nhp vo k nt c thnh cng c bao ph bng mt lp crom cacbua. Cn lp crom nguyn cht st vi ch gn th to thnh hp kim vi ng, nh vy nn kim cng c gn chc vi dng c ct gt. Nh vy, dng c ct gt bng kim cng tr nn bn hn. Kt lun Bi tiu lun trn cho chng ta thy nhng c im khi qut v nguyn t Crom bao gm v tr, thnh phn khong vt, tnh cht l ha v cc ng dng ca crom v cc hp cht ca n trong i sng con ngi. Trong qu trnh lm tiu lun khng th trnh khi nhng sai st v ni dung v hnh thc, mong c thng cm v gip em c th hon thin bi lm ca mnh hn. Em in chn thnh cm n c

Nguyn Th Ngc Anh 18

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