3.1.

NHN XT CHUNG

3.2. N CHT 3.3. HP CHT

3.3. HP CHT
3.3.1

Hidr Halogenua HX Halogenua ca cc nguyn t Oxy ca Halogen Axit Hipohalogen HXO Axit Halogen HXO2 Axit Halogenic HXO3 Axit Pehalogenic HXO4 Cc Halogen Gi

3.3.2

3.3.3

3.3.4

3.3.5

3.3.6

3.3.7

3.3.8

3.3.1. Hidr Halogenua (HX)

Tnh cht vt l v mt s c im: Hiro halogenua l hp cht ca hiro vi cc halogen. - iu kin thng, tt c cc hyr halogenua u l cht kh khng mu, mi xc, c v tan nhiu trong nc

Mt s hng s vt l c trng:

 HF phn hu r rt thnh n cht nhit trn 35000C.

bn nhit trong dy HF - HCl - HBr - HI ph thuc vo 2 yu t ch yu: di lin kt tng v nng lng lin kt gim r rt, lm cho bn nhit ca phn t gim mnh xung.

00C, HF tan v hn trong nc, nh HF c momen lng cc ln, to lin kt hiro mnh vi nc.

Cc HX cn li u tan nhiu trong nc

 T HCl n HI nhit nng chy v nhit si tng dn theo chiu tng ca khi lng phn t. Ring HF c nhit nng chy v nhit si cao mt cch bt thng l do hin tng t hp phn t (HF)n nh lin kt hyr.
nHF (HF)n (n = 2 6)

Lin kt hiro trong HF lng

Nng lng lin kt hiro trong (HF)n l ln nht v lin kt hiro l c trng nht cho HF. Ngay c trng thi kh, lin kt hiro vn cn tn ti. n 900C, kh hiro florua mi gm c hon ton nhng phn t n.

Trong HF lng, lin kt hiro kh bn vng gia cc phn t HF, lm cho HF lng c hng s in mi ln (e = 40 00C) L dung mi ion ho tt (sau nc) i vi nhiu cht v c v hu c. Bn thn HF lng tinh khit c kh nng t ion ho: HF + HF H2F+ + FK ~ 10-10 v F- + HF HF2-

Mui florua khi tan trong HF lng lm tng nng ca F- l cht baz,nhng axit mnh nh HNO3 cng l baz trong HF lng. HNO3 + HF H2NO3+ + F-

Nhng cht d nhn ion F- nh BF3, AsF3, SbF5 v SnF4 l axit trong HF lng. V d: SbF5 + 2HF H2F+ + SbF6-

Tnh cht ha hc

Cc dung dch HX l nhng axit, c gi l axit halogenhiric: HX + H2O H3O+ + XT phn ly trong dung dch 0,1N cho thy HCl, HBr, HI u l nhng axit mnh nht. Ring axit HF l axit yu, c in ly b nht do 3 nguyn nhn:
S t hp to (HF)n lm gim phn t t do. Nng lng lin kt H - F rt ln: HF + H2O H3O+ + Fvi K = 7.10-4 Qu trnh kt hp ca ion F- vi phn t HF: F- + HF HF2- vi K = 5

Tnh cht ha hc
Do , khi tc dng vi cc cht kim, axit HF khng to mui florua trung tnh m to mui hiro florua HF2- T HCl n HI tnh axit tng l do s gim bn ca lin kt H - X trong dy. Khc vi mi axit khc, HF l axit duy nht tc dng vi SiO2 (n mn thu tinh, thnh phn ch yu ca thu tinh l: Na2O.CaO.6SiO2) : SiO2 + 4HF 2H2O + SiF4 Nu HF d th SiF4 tc dng vi HF d to axit H2SiF6 (axit hexaflosilixic) tan trong nc: SiF4 + HF H2SiF6

Tnh cht ha hc

Do , HF c ng trong cc chai l bng nha. Khi s dng axit HF phi thn trng v HF c, gy lot trn da kh cha. Tnh kh : Tnh kh ca HX l do ion X- th hin HF khng th hin tnh kh, do flo c m in ln. HCl ch th hin tnh kh khi tc dng vi nhng cht oxy ho mnh, HBr v nht l HI c tnh kh mnh. 2KMnO4 + 16HCl c 2HBr + H2SO4 c 8HI + H2SO4 c

2MnCl2 + 5Cl2 + 2KCl + Br2 + SO2 + 2H2O 4I2 + H2S + 4H2O

8H2O

 Do tnh kh cao m trong khng kh, dung dch HBr v HI b oxi khng kh oxi ho, t t gii phng X2 t do nn dung dch lu c mu vng nu. Cn HF v HCl khng h bin i, HCl ch b oxi ho trng thi kh v khi un nng, c xc tc CuCl2

O2 + 4HCl 2H2O + Cl2

H0 = -117 kJ/mol

Phn ng ny lm gim entropi ca h nn khi tng nhit th G > 0 v qu trnh xy ra theo chiu nghch. Thc t th khi di nhit 6000C, cn bng chuyn dch sang phi nhng khi trn 6000C th cn bng chuyn dch sang tri.

iu ch

Hiro halogenua c iu ch trc tip hay gin tip tuz thuc vo mc hot ng ca X2 tng ng

HF: khng th iu ch trc tip t H2 v F2 v

phn ng gy n mnh. iu ch HF l cho mui florua (thng l CaF2) tc dng vi axit H2SO4 c 2500C : CaF2 + H2SO4 c

CaSO4 + 2HF

Trong cng nghip, tng hp HCl trc tip t H2 v Cl2 bng cch t H2 d v Cl2 trong l bng thch anh c ng knh khong 0,4m, cao khong 3 - 4m. Kh HCl c chuyn qua thp hp th ngc dng: nc t trn xung v kh clo i t di ln H2 + Cl2 2HCl HCl cn c th iu ch bng cch cho mui clorua tc dng vi axit V d: NaClrn + H2SO4 NaHSO4 + HCl NaCl + NaHSO4 Na2SO4 + HCl

Cc phng php trn u khng p dng c iu ch HBr v HI v phn ng gia Br2 v I2 vi H2 l phn ng chm, thun nghch do HBr v HI d phn hu do tc dng nhit, hiu sut thp. Nu dng phn ng trao i nh: NaXrn + H2SO4 c HX + NaHSO4 (X = Br, I) th khi to ra cc HBr v HI, chng s tip tc phn ng vi H2SO4, nn khng thu c HBr v HI. Do , ngi ta thng dng phng php thu phn mui bromua v ioua ca photpho.

Trn thc t, ngi ta cho brom hay iot tc dng trc tip vi phtpho v nc.

PBr3 + 3H2O H3PO3 + 3HBr PI3 + 3H2O H3PO3 + 3HI

3.3.2. Halogenua ca cc nguyn t

Halogenua l tn gi chung ca hp cht ca halogen vi mt nguyn t no . Ty thuc m in ca cc nguyn t, bn cht ca lin kt trong cc halogenua c th bin i t hon ton ion n gn nh hon ton cng ha tr. Ngi ta chia cc halogenua lm 2 loi:

Halogenua ion c mng li tinh th bao gm cc ion. Chng c nhit nng chy v nhit si cao, c tnh dn in khi nng chy hoc khi tan vo dung dch. Cc halogenua tan trong nc to nn nhng ion hidrat ha ca cation kim loi v anion halogenua: MXn + (x + ny) H2OMn+.xH2O + nX-.yH2O

Tnh cht ha hc

3.3.3. Oxy ca halogen

Nhn xt chung:
Cc oxit ca halogen ni chung u km bn vi nhit cho nn km hot ng v mt ha hc Trong cc oxit ca halogen, oxit ca flo c tnh cht hi khc vi cc halogen khc.

L cht oxi ha mnh, F2O tc dng hu ht nguyn t kim loi v khng kim loi to thnh oxit v florua N khng tc dng vi nc lnh nhng tc dng vi hi nc : F2O + H2O 2HF + O2 Tc dng vi NaOH: 2F2 + 2NaOH 2NaF +H2O + F2O iflo trioxit F2O3 l cht lng mu mu , phn hy -1630C : 2F2O3 2F2O2 + O2 iflo tetraoxit F2O4 l cht rn mu nu, phn hy -1830C : 2F2O4 2F2O3 + O2

 Gm Cl2O, Cl2O3, ClO2 ,Cl2O6 , Cl2O7 iclo c cu to :

 N khng bn, d phn hy thnh Cl2 v O2 .Tan trong nc to thnh dd vng cam cha HClO .Cn trong dd kim ,n to nn hipocloric

Cl2O c to nn t Hg(II)oxit tc dng vi Cl2 : 2Cl2 + 2HgO HgO.HgCl2 + Cl2O

Clo dioxit (ClO2) rt km bn .Do , n rt hot ng v ha hc . L cht oxi ha mnh ClO2 + 4H+ + 5e Cl- + 2H2O ng dng : ty trng xenluloz v bt giy.

 Trong dd kim, ClO2 to thnh cloric v clorat : 2ClO2 + KOH KClO2 + KClO3 +H2O Phng php tt nht iu ch ClO2 l : KClO3 + H2C2O4 + 2H2SO4 2KHSO4 + 2H2O + 2ClO2 + 2CO2

Trong cng nghip, ClO2 iu ch bng NaClO3 v SO2 dd H2SO4 4M: 2NaClO3 + SO2 + H2SO4 2ClO2 + 2NaHSO4

iclo Hexaoxit (Cl2O6)

L mt cht lng nh du, mu thm, ha rng 30C. N khng bn ,d b phn hy thnh ClO2 v O2. Gy phn ng vi cc cht hu c v cht kh khc ,c bit l nc: Cl2O6 + H2O HClO3 +HClO4

iclo heptaoxit Cl2O7

L cht lng khng c mu, ging nh du. N ha rn 900C v si 1200C L hp cht bn nht trong cc oxit ca clo N tan trong CCl4 nhng tan chm trong nc to thnh axit pecloric: Cl2O7 + H2O 2HClO4

 ibrom oxit (Br2O) l cht lng mu nu Phn hy 500C thnh brom v oxi, tan trong CCl4 cho dd mu lc .

iu ch bng cch cho brom i qua thy ngn(II) oxit

 Brom dioxit (BrO2) l cht rn mu vng di 400C. N phn hy thnh Br2O . Tan trong nc , n to thnh dd axit c cha cc anion Br-, BrO-, BrO2- v BrO3-

BrO2 c to nn khi phng in qua hh brom v oxi nhit ca khng kh lng

 Tribrom octaoxit (Br3O8) hay (BrO3) l cht rn mu trng,khng bn nhit 800C nhng bn trong O3. Tan trong nc to thnh dd c tnh axit v tnh oxi ha. N c to nn khi cho brom tc dng vi O3 nhit thp.

 iiot tetraoxit (I2O4) l cht rn mu vng phn hy trn 850C thnh I2O5 v I2 cho nn c tnh oxi ha. N khng tan trong nc lnh nhng tan trong nc nng to thnh axit iodic v I2: 5I2O4 + 4H2O 8HIO3 + I2 iu ch : un nng axit iodic vi H2SO4 c trong vi ngy

 Tetraiot nonaoxit (I4O9) l ch rng mu da cam dng polime, ht m mnh . N tc dng vi H2O to thnh axit iodic v iot

iu ch : cho iot tc dng vi hh O3 v O2 nhit thng hay un nng axit iodic vi axit orthophotphoric.

 Diiot pentaoxit (I2O5) l cht rn mu trng, bn n nhit 3000C. Trn nhit , n phn hy thnh cc n cht. N tan trong nc v phn ng chm vi nc to thnh axit iodic: I2O5 + H2O 2HIO3 iu ch : lm mt nc ca axit iodic nhit 2400C

3.3.4. Axit Hipohalogen HXO

Axit hypoclor HClO : khng tch ra c trng thi
t do, ch tn ti trong dung dch long (nng cc i ch 20 - 25%) v in ly to mi trng axit (cng nh HBrO, HIO): HClO + H2O H3O+ + ClO Dung dch HClO c mu vng lc, tnh axit yu v l cht oxy ho mnh. HClO phn hu tuz iu kin : Khi c cht ht nc mnh (CaCl2) : 2HClObh Cl2Odd + H2O Khi un nng : 3HClO 2HCl+ HClO3

 V vy khi cho Cl2 phn ng vi dung dch kim nng th tuz nhit m cho sn phm khc nhau.
Cl2 + 2KOHngui KCl + KClO + H2O 3Cl2 + 6KOHnng 5KCl + KClO3 + 3H2O

 Thc hin phn ng trung ho: HClO + NaOH long NaClO + H2O HClO + NH3.H2O c NH4ClO + H2O Axit HClO v mui cha ClO- u l cht oxy ho mnh: HClO + 2HI HCl + I2 + H2O 3ClO- + 2NH3 N20 + 3Cl- + 3H2O

 Li dng tnh oxi ho ca hypoclorit, trong thc t ngi ta thng dng 2 ho phm cha mui hypoclorit l nc Javen v clorua vi ty trng vi v st trng.

 L dung dch nc ca NaCl + NaClO c to nn khi cho kh Cl2 phn ng vi dung dch NaOH ngui: Cl2 + 2NaOH ngui NaCl + NaClO + H2O Trong cng nghip, nc Javen c iu ch bng in phn dung dch NaCl 15 - 20% khng c mng ngn vi in cc m l Fe, in cc dng l titan: NaCl + H2O NaClO + H2 Kh H2 thot ra khi b in phn, thu c nc Javen:

NaCl + NaClO + H O
2

ng dng : Ch yu c dng lm cht ty ra

CaCl(OCl) l cht bt mu trng, c mi xc

gn nh mi clo, c xem l mui canxi hn hp ca HCl v HClO. Cng thc cu to:

Ca

Cl

-1

O - Cl

+1

Nh vy clorua vi l mui ca kim loi canxi vi 2 loi gc axit clorua Cl- v hipoclorit ClO -. Mui ca mt kim loi vi nhiu loi gc axit khc nhau c gi l mui hn tp

 Trong khng kh m : 2CaCl(OCl) + CO2 + H2O CaCO3 + CaCl2 + 2HClO Tc dng vi HCl: CaCl(OCl) + 2HCl CaCl2 + Cl2 + H2O B nh sng tc dng mnh: 2CaCl(OCl) 2CaCl2 + O2

 Clorua vi c iu ch

t kh Cl2 v huyn ph c ca Ca(OH)2 un nng nh: Cl2 + Ca(OH)2 CaOCl2 + H2O

Clorua vi khng bn, d phn hu.

 Sn phm phn hu u c O2, Cl2 c tnh oxy ho mnh, nn ty trng vi si, ph hu mu. Ngoi ra, clorua vi cn c dng tinh ch du m v dng iu ch Cl2, O2 trong phng th nghim.

3.3.5. Axit Halogen HXO2

HClO2 l hp cht khng bn, ch tn ti
trong dung dch v b phn hy : 4HClO2 2ClO2 + HClO3 + HCl + H2O

Mui cloric bn hn axit clor. Natri clorit iu ch t ClO2 v Na2O2: 2ClO2 + Na2O2 2NaClO + O2

 Khi un nng, Natri clorit phn hy thnh clorua v clorat : 3NaClO2 NaCl + 2NaClO3 Axit clor c iu ch t Bari clorit v H2SO4 : Ba(ClO2)2 + H2SO4 2HClO2 + BaSO4

3.3.6. Axit Halogenic HXO3

HClO3 ch tn ti trong dung dch, trong
dung dch c nng trn 50% th b phn hu: 3HClO3 HClO4 + 2ClO2 + H2O Trong dung dch nc, HClO3 l axit mnh, mt nc (tnh axit gim t HClO3 n HIO3). HClO3 + H2O ClO3- + H3O+

 Thc hin phn ng trung ho vi dung dch kim:

HClO3 + NaOHlong NaClO3 + H2O

HClO3 c tnh oxi ho mnh (gim dn t HClO3 n HIO3). 2HClO3 + 10H+ + 10e- Cl2 + 6H2O E0 = +1.47V

2HBrO3 + 10H+ + 10e- Br2 + 6H2O

2HIO3 + 10H+ + 10e- I2 + 6H2O

E0 = +1.52V
E0 = +1.20V

 Mt s phn ng th hin tnh oxi ho ca HClO3:

2HClO3c + I2 Cl2 + 2HIO3 2HClO3c + 3Cgr 2HCl + 3CO2

 KClO3

l cht kt tinh thnh tinh th hnh vy khng mu, thuc h n t, nng chy 3560C, t tan trong nc lnh, tan nhiu trong nc nng: Ho tan 00C l 5,3g, 1000C l 56g trong 100g nc. Khng tan trong ru tuyt i.

Khi un nng n 4000C, khng c xc tc th phn hu theo phn ng : 4KClO3 3KClO4 + KCl.

 Khi c xc tc MnO2 th phn hu theo phn ng: 2KClO3 2KCl + 3O2 KClO3 rn c tnh oxy ho rt mnh nn nhng cht d chy nh P, S, C, bt nhm ... khi trn vi KClO3 s gy n khi va p, tnh cht ny c ng dng vo sn xut dim, thuc pho: 2KClO3 + S + 2C 2KCl + SO2 + 2CO2

 Trong cng nghip, KClO3 c iu ch t Cl2, huyn ph Ca(OH)2 v KCl, qu trnh gm 2 giai on:
5Cl2 + 6Ca(OH)2 Ca(ClO3)2 + 5CaCl2 + 6H2O Ca(ClO3)2 + KCl KClO3 + CaCl2

 ngui th ch KClO3 kt tinh. Ngoi ra cn dng phng php in phn dung dch KCl 25% 70-750C khng mng ngn. Ant : 2Cl- 2e- Cl2 Catt : 2H2O + 2e- H2 + 2OHV 3Cl2 + 6OH- ClO3- + 5Cl- + 3H2O

3.3.7. Axit Pehalogenic (HXO4)

Cu to: Gc peclorat ClO4- c cu to t din, nguyn t Cl tm t din, 4 nguyn t O trn 4 nh ca t din u, nn c tnh i xng cao.

 Trong lin kt Cl - O, ngoi lin kt s cn mt phn lin kt p khng nh ch theo kiu p d. HClO4 l cht lng khng mu, phn hu khi un nng va phi, tan v hn trong nc, L axit mnh nht trong tt c cc axit, c tnh oxy ho mnh trong dung dch c, cn trong dung dch long th oxy ho yu.

Phn hu: 3HClO4 khan Cl2O7 + HClO4.H2O in ly: HClO4 long + H2O ClO4- + H3O+ Trung ho: HClO4 + NaOHlong NaClO4 + H2O Tnh oxi ho: 2HClO4 c + I2 + 4H2O 2H5IO6 + Cl2 4HClO4 khan + 7Cgr 7CO2 + 2Cl2 + 2H2O

2KClO4 + H2SO4 c K2SO4 + 2HClO4 3HClO3 c HClO4 + Cl2 + 2O2 + H2O (un si)
Chng ct sn phm p sut thp (22mmHg) c HClO4 khan.

 Gc ClO4 to ra mui peclorat khng mu hoc c mu tuz thuc vo cation kt hp vi n. Hu ht cc mui peclorat d tan trong nc. Khi un nng mui ClO4- phn hu thnh clorua v O2.

Tnh cht ha hc

Tnh cht ha hc

Tnh cht ha hc

 iu ch Axit parapeiodic t mui parapeiodic :

Ba5(IO6)2 + 5H2SO4 5BaSO4 + 2H5IO6

Tnh cht ha hc