PHC CHT

Cu to phc cht
Cu ni: vit trong du mc vung Cation: [Co(NH3)6]Cl3 Anion: K2[Zn(OH)4] Trung ha: [Pt(NH3)2Cl2], [Ni(CO)4] Cu ngoi: nhng ion nm ngoi v ngc du vi cu ni.

Phi t
Mt cng: F-, Cl-, OH-, CN-H2O, NH3 Nhiu cng: en, C2O42-, EDTA S phi tr: l s phi t bao quanh cht to phc. Ph bin nht l 4,6.

 S phi t:
1 cng: di, tri, tetra, penta, hexa, Nhiu cng: bis, tris, tetrakis, pentakis, hexakis

Tn phi t:
Anion: tn ca anion + o F-: floro, CO32-: carbonato, CN-: ciano Trung ha: H2O: aquo (aqua), NH3: ammin, CO: carbonyl, NO: nitrozyl

Tn mt s phi t
NO2-: SO32-: SCN-: NH2CH2CH2NH2 : CH3NH2: C5H5N: C6H6: ONO-: S2O32-: NCS-:

Nguyn t trung tm
Nu M nm trong cation, tn M km theo ch s La M trong du ngoc n. Nu M nm trong anion, tn M thm ui at, km theo s La M, nu phc l acid th thay at bng ic. VD: [Co(NH3)6]Cl3: hexaammincobalt (III) clorur

Gi tn
Tn ion dng t trc tn ion m Tn ca ligand t trc tn ca ion kim loi trung tm. Ligand mang in tch m > ligand trung ha in > ligand mang in tch dng S oxh ca KL trung tm trong ngoc n Tn ca phc ion m tn cng bng at

V d
[Cr(NH3)6]Cl3: [Co(H2O)5Cl]Cl2: Na2[Zn(OH)4]: [Cu(NH2CH2CH2NH2)2]SO4 [Co(NH3)4][PtCl4] [Cr(NH3)6][Co(CN)6]: [Pt(NH3)4][PtCl6]: H[AuCl4]

ng phn phc cht

ng phn hnh hc: cis-, transPhc vung phng:

Cl Cl

Pt

NH3 NH3

H3N Cl

Cl Pt NH3

cis-diclorodiamminplatin(II) (mu vng da cam).

trans-diclorodiamminplatin(II) (mu vng nhat)

Phc bt din:
Dng MA4B2 Cis: 2 ligand B v tr 1,2 Trans: 2 ligand B nm v tr 1,6 Dng MA3B3: Cis: 3 ligand B nm v tr 1,2,3. Trans: 3 ligand B nm v tr 1,2,6.

VD: Hy v ng phn cis-trans cho cc phc cht c cng thc sau: a. [CoCl2(NH3)4]+ b. [CoCl3(NH3)3]

 ng phn phi tr: sinh ra do s phi tr khc nhau ca loi phi t quanh 2 nguyn t trung tm [Co(NH3)6][Cr(CN)6] v [Cr(NH3)6][Co(CN)6] [Cu(NH3)4][PtCl4] v [Pt(NH3)4][CuCl4] [Pt(NH3)4][PtCl6] v [Pt(NH3)4Cl2][PtCl4]

 ng phn ion ha: do s sp xp cc anion trong cu ni v cu ngoi. [Co(NH3)5Br]SO4 v [Co(NH3)5SO4]Br ng phn lin kt: [Co(NH3)5NO2]Cl2 v [Co(NH3)5ONO]Cl2 [Mn(CO)5SCN) v [Mn(CO)5NCS]

S phn ly trong dung dch

[Ni(NH3)6]Cl2 = [Ni(NH3)6]2+ + 2Cl[Ni(NH3)6]2+ = Ni2+ + 6 NH3 Hng s cn bng ca qu trnh phn ly:

Kcb =

[Ni2+].[NH3]6 [[Ni(NH3)6]2+]

Hng s bn
= 1/Kcb

Thuyt lin kt ha tr (VB)

Phc cht c to thnh bng cc lin kt cho nhn gia e t do ca phi t v obitan trng ca NTTT. Co3+ + 6 :NH3 = [Co(NH3)6]3+ Acid Lewis Bazo Lewis mui Lewis

 V d:
[Cu(NH3)2]+ [CoCl4]2[PtCl4]2[Co(NH3)6]3+ [CoF6]3-

u im: m t n gin c th cc lin kt trong phc, gii thch c t tnh ca phc cht. Nhc im: khng gii thch c mu sc ca phc cht.

Thuyt trng tinh th

S to phc l tng tc tnh in gia cht to phc v phi t. Phi t l nhng in tch im hay lng cc. Sp xp phi t sao cho nng lng y gia chng l nh nht. i vi NTTT c spt 6: bt din i vi NTTT c spt 4: t din.

Thng s tch nng lng

L hiu nng lng ca d cao v d thp. Yu t nh hng ln
Cu hnh phc: vung phng> bt din>t din in tch ion trung tm: =Kz2r2

 Kch thc ion trung tm: Phi t. I-<Br-<Cl-<SCN-<F-<OH-<C2O42<H2O<NCS-<py<NH3<en<dipy<NO2-<CN<CO

Gii thch t tnh ca phc cht

P> : phc cht c spin cao P< : phc cht c spin thp. V d: P ca Co3+ l 251kJ/mol ca [CoF6]3-l 156kJ/mol, ca [Co(NH3)6]3+ l 265kJ/mol. Xc nh t tnh ca 2 phc cht trn.

Mu ca phc cht
Mu l kt qu ca s hp ph mt phn nh sng trng thy. S chuyn di e t obitan c nng lng thp n cao gy nn ph hp th. Gii thch ti sao Cu+ khng c mu?

Zn, Cd, Hg
Gii thiu:
Cu hnh e ha tr: (n-1)d10ns2 C 2 e ha tr ging vi cc nguyn t nhm IIA Khc vi nhm IIA: in tch ht nhn ln, bk nh, c kh nng to ni i,

iu ch
Nhit luyn: 2ZnS + 3O2 2ZnO + 2SO2 ZnO + C Zn + CO Zn c iu ch t qung aphalerit ((ZnFe)S). Thy luyn ZnSO4 Zn

 Cd: lm tng t nh Zn Hg: t qung cinnabar (HgS), em nung thu c oxid HgO, nung n khong 500oC oxid phn hy thu Hg

Tnh cht:
Zn, Cd, Hg: kim loi c mu trng bc Lin kt Hg-Hg: lin kt kim loi + Vanderwaals Hg c kh nng bay hi RT, v rt c Zn, Cd, Hg: d to hp kim Tnh kh gim dn: Zn > Cd > Hg Phn ng vi O2 Phn ng vi phi kim
X + S XS (X: Zn, Cd, Hg)

 H2O
Zn, Cd khng phn ng v c lp oxid bo v

Zn, Cd phn ng vi HCl, H2SO4 (l) Zn, Cd phn ng vi H2SO4 () SO2 hoc H2S

Hg phn ng tt vi HNO3
Hg + 4HNO3 () Hg(NO3)2 + 2NO2 + 2H2O 6Hg + 8HNO3(l) 3Hg2(NO3)2 + 2NO + 4H2O 4Zn + 10HNO3 (l) 4Zn(NO3)2 + NH4NO3 + 3H2O Dung dch kim Zn + 2NaOH + 2H2O Na2[Zn(OH)4] + H2 Cd v Hg khng phn ng.

 Cc hp cht
Oxid: ZnO, CdO, HgO
To thnh t phn ng chy kim loi tng ng

Hydroxid ca Zn, Cd, Hg: to thnh t mui tng ng

Zn(OH)2 v Cd(OH)2 tan c trong dd NH3 do to phc Zn(OH)2 l hydroxid lng tnh Hg(OH)2: khng tn ti v qu km bn

Phc
C th to phc vi ligand: NH3, I-, CN-, Ion Hg2+ to phc t din (HgCl42-, Hg(CN)42-,) Hg(II) to phc vi cc tiol (RSH) Hg(SR)3 Zn (II) to phc s phi tr 6 vi ligand NH3, s phi tr 4 vi ligand: OH-, CN-

Ti, V, Cr, Mn, Fe, Co, Ni, Cu

Gii thiu
Kim loi thng cng, d cho e, dn nhit, in tt Ring Cu th mm d dt mng, ko si C th phn ng vi halogen, sulfur, v cc phi kim khc Electron ha tr nm vn o d Nhiu s oxy ha

 Tnh cht
Ti V Cr Mn Fe Co Ni Cu

Mp. oC Eo (V) Tan trong acid

1668

1890

1875

1244

1537

1493

1453

1083

-1,19

-0,91

-1,18

-0,44

-0,28

-0,24

+0,34

HCl, HF nng

HNO3, HCl, HCl, HCl, HCl HCl, HNO3, HF, H2SO4 H2SO4 H2SO4 (chm) H2SO4 H2SO4 H2SO4 (, n) () M2+ + 2e M

Trng thi oxy ha

Ti 2 d2 3 d1 4 do

V 0 d5 1 d4 2 d3 3 d2 4 d1 5 do

Cr 0 d6 1 d5 2 d4 3 d3 4 d2 5 d1 6 do

Mn 0 d7 1 d6 2 d5 3 d4 4 d3 5 d2 6 d1 7 do

Fe 0 d8 2 d6 3 d5 4 d4

Co 0 d9 1 d8 2 d7 3 d6 4 d5 5 d4

Ni

Cu

0 d10 1 d9 1 d10 2 d8 2 d9 3 d7 3 d8 4 d6

6 d2

Trng thi oxh thng gp ca cc nguyn t khi to phc vi cc ligand nh CO,

 S oxy ha +2
Hnh thnh cc hp cht ion Oxid c tnh baz Ion M2+ thng dng hydrat ha (M(H2O)62+) tr Ti2+ cha tm thy V2+, Cr2+, Fe2+ b oxy ha bi O2 trong dd acid Ligand H2O trong M(H2O)62+ c th b thay th bi cc ligand khc nh NH3, EDTA, CN-, Phc to thnh c th trung tnh, mang in tch dng hoc m

S oxy ha +3
Cc mui florur v oxid c tnh ion Cc mui clorur, sulfur, bromur, iodur c tnh cng ha tr

 Ti3+, V3+ c th b oxy ha trong khng kh C kh nng b thy phn trong nc VD: Ti(H2O)63+ + H2O [Ti(H2O)5OH]2+ + H3O+ C th hnh thnh phc trung tnh, mang in tch dng hay m Cc MX3 c th p. ng nh acid Lewis: MX3 + 2NMe3 MX3(NMe3)2

S oxy ha >= +4
S oxh +4 thng gp Ti (TiCl4, TiO2,), V (VO2+) VO2+ c th hot ng nh ion M2+: to phc, Cc hp cht c s oxh >+4 thng c to thnh t cc nguyn t V, Cr, Mn,

 Titanium
iu ch
C 4 e ha tr (3d24s2) Nng lng mt 4 e l ln Ti4+ khng tn ti, hp cht Ti(IV) c tnh cng ha tr Ti c nhiu trong qung ilmenit (FeTiO3) iu ch: 2FeTiO3 + 3C + 7Cl2 2TiCl4 + 3CO2 + 2FeCl3 TiCl4 + 2Mg Ti + 2MgCl2 (800 oC, Ar) Ti bn trong khng kh do c lp TiO2 bo v t nng: Ti + O2 TiO2 Ti + 3HCl (, n) TiCl3 + 3/2H2 Ti + 6HF H2[TiF6] + 2H2 3Ti + 4HNO3 + 18HF 3H2[TiF6] + 4NO + 8H2O

Tnh cht

 Hp cht ca titanium
TiO2
iu ch: Ti + O2 TiO2 TiCl4 + O2 TiO2 Tnh cht: + Cl2 (HT)

TiO2 l mt cht kh tr TiO2 kch thc nh (nanomet) c tnh dit khun v bn

TiCl4
iu ch: Ti + Cl2 hoc t qung ilmenit Tnh cht L cht lng, rt ht nc mnh TiCl4 + 3H2O H2TiO3 + 4HCl

 TiCl4 phn ng vi cc cht c hydro t do (ROH, NHR2 ) TiCl4 + 4ROH + 4RNH2 Ti(OR)4 + 4RNH3Cl

Cc alkoxid (Ti(OR)4) d b thy phn trong nc nROH + Ti(OH)n(OR)4-n

TiCl4 phn ng vi cc litium dialkilamin (LiNR2) TiCl4 + 4LiNR2 Ti(NR2)4 + 4LiCl

 Crom (chromium) (3d54s1)

iu ch
Crom c nhiu trong qung cromit (chromite, FeCr2O4) FeCr2O4 + C Fe + 2Cr + 4CO Cr2O3 + 2Al Al2O3 + 2Cr 2Cr2O3 + 3Si + 3CaO Cr + 3CaSiO3

Tnh cht:
4Cr + 3O2 2Cr2O3 (bn) 2Cr + 3Cl2 2CrCl3 Cr + 2HCl CrCl2 + H2 4Cr + 12HCl + O2 4CrCl3 + 2H2O + 4H2 Cr + H2SO4 CrSO4 + H2

 Cr(II)
Mi trng acid: Cr2+ Mi trng baz: Cr(OH)2, Cr(OH)42-

Cr(III)
Oxid: Cr2O3 Mi trng acid: Cr3+ Mi trng baz: Cr(OH)3, Cr(OH)4Thng to phc bt din (6 phi t) pH ~ 6, Cr(VI) CrO42- (cromat) pH t 2 -6: HCrO4- v Cr2O72pH < 1: H2CrO4 Trong mi trng baz: Cr2O72- + OH- HCrO4- + CrO42HCrO4- + OH- CrO42- + H2O

Cr(VI)

K2Cr2O7 K2Cr2O7 K2Cr2O7 K2Cr2O7 K2Cr2O7

+ + + + +

HCl = SO2 + H2SO4 = FeSO4 + H2SO4 = SnCl2 + HCl = C2H5OH + H2SO4 =

 Mangan (Mn) (3d54s2)

iu ch
c iu ch t qung pyroluzit MnO2 + 2C Mn + 2CO 3Mn3O4 + 8Al 9Mn + 4Al2O3

Tnh cht (th hin tnh kh ca Mn)

Mn phn ng vi O2 nhit cao, Mn phn ng vi O2, halogen, S, P, C, N,) Mn + H2O Mn(OH)2 + 2H2 Phn ng vi acid: Mn + HNO3 =

 Hp cht ca Mn
Mn(II)
Mui ca Mn(II) thng d tan trong nc Khi thm OH- vo dung dch Mn2+ hydroxid (trng), nu lu en Oxid: MnO Mi trng baz: Mn(OH)2 Mi trng acid: Mn2+

Mn(III)
Oxid: Mn2O3 Mi trng acid: Mn3+ Mi trng baz: Mn(OH)3

 Mn(III)
Ion Mn(III) thu c bng cch kh MnO4- hoc oxy ha Mn2+ Tuy nhin, khi nng Mn3+ ln kh bi khng kh 2Mn3+ + H2O Mn2+ + MnO2 + 4H+ Mn2+ + O2 hoc Cl2 trong dm acetilaceton tinh th nu m (Mn(acac)3)

Mn(IV), Mn(V)
Hp cht Mn(IV) ph bin nht l MnO2 Mn + O2 MnO2 Nung Mn(NO3)2.6H2O trong khng kh MnO2 Kh KMnO4 trong mi trng kim

 MnO2 khng tc dng vi acid nhit thng nhit cao th hin tnh oxy ha MnO2 + 4HCl MnCl2 + Cl2 + 2H2O

Mn(VI), Mn(VII)
MnO42-, hnh thnh t MnO2 + O2/OH MnO42- bn trong mi trng baz ln, trong mt trung tinh hoc acid Mn(VII): MnO4 Dung dch MnO4- km bn, phn hy chm 4MnO4- + 4H+ 3O2 + 2H2O + 4MnO2 MnO4- trong dd baz c tnh oxy ha mnh MnO4- + 2H2O + 3e MnO2 + 4OH- , Eo = +1,23 V Trong mt acid, MnO4- c tnh oxy ha mnh MnO4- + 8H+ + 5e Mn2+ + 4H2O, Eo = +1,51 V

KMnO4 + Na2SO3 + H2SO4 = KMnO4 + PH3 + H2SO4 = KMnO4 + H2C2O4 + H2SO4 = KMnO4 + Zn + H2SO4 = KMnO4 + K2SO3 + KOH = KMnO4 + Na2SO3 + H2O =

 St (Fe)
Fe2O3 + C Fe + CO Oxid st + H2 Fe Khi un nng, phn ng vi O2, halogen, nit, lu hunh, Phn ng vi acid nhit ~ 800oC, Fe + H2O Fe3O4 + H2

Oxid, hydroxid
Fe2+ + OH- Fe(OH)2 2Fe(OH)2 + 1/2O2 + H2O 2Fe(OH)3 Fe(OH)2 + 4NaOH (bo ha) Na4[Fe(OH)6] FeO c mu en

 Fe3+ + 3OH- Fe(OH)3 200oC, 2Fe(OH)3 Fe2O3 + 3H2O Fe3O4 l hn hp ca oxid Fe(II) v Fe(III), tn ti trong t nhin di dng st t.

Fe(II)
Mi trng acid: Fe2+, baz: Fe(OH)2 Phn ng: th hin tnh oxy ha hoc kh 2Fe2+ + 1/2O2 + 2H+ 2Fe3+ + H2O Fe2+ + Zn Zn2+ + Fe

Fe(III)
Mi trng acid: Fe3+, baz: Fe(OH)3 Phn ng thng th hin tnh oxy ha Fe3+ + cht kh Fe2+

 Fe3+ c tnh acid Fe3+ + H2O Fe(OH)2+ Fe3+ i lc mnh vi F Fe3+ + F- FeF2+, K1 = 105 FeF2+ + F- FeF2+, K2 = 105 FeF2+ + F- FeF3, K3 = 103

+ H+

Vi ion Cl- K1 = 10, K2 = 3, K3 = 0,1 Vi HCl c FeCl4-

 Cobalt (Co)
Co(II)
Co(OH)2, CoCO3 tan trong acid to dd c mu hng ([Co(H2O)6]2+) Co2+ + 2OH- Co(OH)2 Co(OH)2 + O2 (kk) CoO(OH) (en) + H2O Co(OH)2 + 2OH- (m c) Co(OH)42 Ion Co2+ c th to phc t din hoc bt din Co(H2O)62+ Co(H2O)42+ + 2H2O Co(H2O)62+ + 4Cl- CoCl42- + 6H2O Cc phc t din thng to thnh vi cc ligand halogeno v OH-

 Co(III)
Co3+ i lc mnh vi N to phc tt vi NH3, EDTA, NCS Phc Co(III) thng l phc bt din Phc Co(III) c th iu ch t s oxy ha dd Co2+ vi s hin din ca ligand tng ng. 4Co2+ + 4NH4+ + 20NH3 + O2 4[Co(NH3)6]3+ + 2H2O Khi c mt nhiu ligand to phc phc a ligand: [Co(NH3)5NO2]Cl2, K[Co(NH3)2(NO2)4] S to phc lm gim tnh oxy ha ca Co(III) Co3+ + e Co2+, Eo = +1,8 V Co(NH3)63+ + e Co(NH3)62+, Eo = +0,1 V

 ng (Cu)
iu ch
Cu c nhiu trong cc qung: chancopyrit CuFeS2, cuprit Cu2O, kovelin CuS Nhit luyn t chancopyrit Cu: 2CuFeS2 + 5O2 + 2SiO2 2Cu + 2FeSiO3 + 4H2O

Tnh cht
Nng lng ion ha I1 kh cao tnh kh yu. Khng phn ng vi cc acid c tnh OXH. Tan c trong H2SO4 v HNO3 c nng. Tan trong H2SO4, HNO3 vi s hin din ca O2 Tan trong NH3, CN- vi s hin din ca O2 Cu + 2NH3 [Cu(NH2)2]+ [Cu(NH3)4]2+

 Cu(I):
Cu+ + e Cu, Eo = 0,52 V Cu2+ + e Cu+, Eo = 0,153 V ion Cu+ km bn. Hp cht Cu(I) in hnh: CuCl, CuCN,(c T nh)

Cu(II)
Mi trng acid: Cu2+, baz: Cu(OH)2, Cu(OH)42 Phn ng thng th hin tnh oxy ha Cu2+ + e Cu+ , Eo = 0,153 V Cu2+ + 2e Cu, Eo = 0,3419 V

Cc nguyn t cn li
Paladium (Pd) v Platinum (Pt)
Kim loi rt km hot ng Pt2+ + 2e Pt, Eo = 1,188 V Pd2+ + 2e Pd, Eo = 0,987 V Pd, Pt c ng dng lm xc tc hoc in cc

Hp cht clorur
Clo ha Pd PdCl2 ( nhit cao) Trn 550oC dng Di 550 oC dng (bn hn)

Dng Cisplatin
NH3 Pt Cl NH3

Dng

Cl

Cisplatin: c hot tnh khng ung th rt mnh (ung th tinh hon, bung trng, bng i,... Cisplatin ch c hot tnh vi mt s loi t bo ng dng lm sn cn hn ch do c c tnh cao Khc phc nhc im --> tng hp cc dn xut vi cc cht hu c

Cl Pt Cl

NH3

+ HOH Cl Pt H2O NH3

++ H2O NH3 Pt H2O NH3

+
NH3

NH3

O N H N N H3N Pt H3N N H N N N N O N

DNA

Guanin
N

Cross-linked DNA

Kt qu: c ch t bo ung th P388 cy trn chut

Mixing sugardiamine ligand and potassium tetrachloropalladate(II) in water. Several hours later, appeared precipitates were collected as yellow powders (2449% yield)

 Vng (Au) v Bc (Ag)

Au v Ag l hai kim loi kh qu Thng c trong cc khong sn cng vi cc kim loi khc nh ch, Cu, Pt, Qung m cha Au, Ag c trch bng dung dch cyanur vi s c mt ca khng kh M(CN)2- M (kh bng Zn,) Ag c mu trng, c cho l kim loi dn nhit v in tt nht Au c mu vng, mm, d b dt hay ko mng nht. Au rt bn, khng phn ng vi O2

 Ag + 2HNO3 AgNO3 + NO2 + 2H2O Au + HNO3 + 4HCl H[AuCl4] + NO + H2O Au + 6H2SeO4 Au2(SeO4)3 + 3SeO2 + 6H2O 4Au + O2 + 8CN- + 2H2O 4[Au(CN)2]- + 4OH Au + 8NH3 + O2 + H2O 4[Cu(NH3)2]+ + 4OH Au + 3/2Cl2 + HCl H[AuCl4]

Cc hp cht ca Ag
AgNO3, AgClO3, AgClO4 tan c trong nc Cc mui vi halogen thng t tan Ag+ + 2OH- Ag2O + H2O Ag2O + H2O 2AgOH 2Ag+ + CO2 + H2O Ag2CO3 + 2H+ Ag2O b phn hy khi un nng > 160oC

Bi tp
1. Co(OH)2, Ni(OH)2 tan c trong dung dch NH3 hay khng? Vit ptpu. 2. Vit phng trnh nh tnh Fe3+, Fe2+ (dng ch th c trng). 3. Xc nh cu hnh ca [Ni(CN)4]2- v [NiCl4]2-, xc nh t tnh. 4. Gii thch to sao ngi ta dng CoCl2 lm cht ch th m.

5. Vit pt iu ch [Co(NH3)6]Cl3 t Co2+. 6. iu ch CuCl t Cu2+. 7. Hon thnh cc phng trnh phn ng sau: a. [Cu(NH3)2]+ + H2O + NH3 + O2 b. AgCl + NH3 c. AgI + KCN d. AgBr + Na2S2O3

8. thu c vng t qung ngta dng phng php cianua ha. Vit cc ptp ca phng php ny. 9. B tc: a. FeSO4 + Hg(NO3)2 = b. FeSO4 + NaNO2 + H2SO4 =

10. Th oxy ha kh ca cc hp cht ca Fe trong mi trng acid v kim c Fe3+ +0.77 nh gi tr Fe2+ -0.44 FeO42- +2.2 sau: Mi trng acid:

Fe

FeO422FeO4

+2.2

Fe

3+ +0.77

Fe

2+ -0.44

Fe Fe

Mi trng bazo:
+0.72

Fe(OH)3

-0.56

Fe(OH)2

-0.887

a. oxy ha cc hp cht Fe(II) ln Fe(III) phn ng trong mi trng no d thc hin hn? b. C th oxy ha Fe(II) ln Fe(III) trong mi trng acid bng oxy khng kh hay khng? Trong mi trng bazo? c. oxy ha cc hp cht ca Fe(III) ln Fe(VI) nn tin hnh trong mt no?