1

HA HC V C 1
THI LNG : 60 tit
Ban o to: Ha a
A/ TI LIU THAM KHO
- Ha hc v c 1, Nguyn Th Ngn, NXBHSP, 2004.
- Ha hc v c, L Mu Quyn, NXBKH&KT, 1999.
- Ha hc v c phn 1, ACMETOP. NXBH&THCN,1977.
- Ha hc v c tp 2, Hong Nhm, NXBGD, 2002.
B/ MC TIU MN HC
Nm c kin thc c bn v c h thng v cu to, bn cht lin kt, tnh
cht l- ho hc, kh nng phn ng, phng php iu ch, khai thc v ng dng cc
n cht v hp cht ca cc nguyn t phi kim trn c s l thuyt v cu to cht v
cc qu trnh ho hc.
- Bit vn dng cc kin thc c bn v cc nguyn t phi kim vo gii thch cc th
nghim chng minh cc tnh cht l- ho hc, cc th nghim iu ch cc n cht v
hp cht ca cc nguyn t phi kim trong hc phn thc hnh ho v c 3.
- C kin thc hc tip hc phn kim loi, cc hc phn khc. ng thi c th hc
tip cc hc phn khi chun ho ln trnh i hc.
- Bit vn dng nhng l lun c bn v ho hc cc nguyn t phi kim vo vic tm
hiu v gii thch cc hin tng ho hc c lin quan n thc tin sn xut, i sng
v mi trng. thc c vai tr ca ho hc i vi i sng, cn thit phi bo v
mi trng v trch nhim gio dc hc sinh gp phn bo v mi trng.
- C trnh v bit vn dng nhng kin thc lnh hi c v ho hc cc
nguyn t phi kim v phng php ging dy n vo vic chun b gio n, tin hnh
ging dy chng trnh ho hc v c THCS v hng dn hc sinh hc tp tt b
mn ho hc, gp phn thc hin mc tiu o to mi ca chng trnh THCS.
2

Chng 1: GI THIU BNG TUN HON CC NGUYN
T HO HC. S PHN CHIA PHI KIM- KIM LOI 3(1,2)
A. MC TIU:
Bng tun hon cc nguyn t ho hc
S phn chia phi kim, kim loi, bn kim, bn dn.
So snh tnh cht ca phi kim- kim loi. c im ca phi kim.
B. NI DUNG :
S LC V S PHT MINH RA BNG TUN HON
Thi trung c loi ngi bit cc nguyn t vng, bc, ng,
ch, st, thu ngn...Nm 1649 tm ra nguyn t pht pho.
u th k 19, nhiu nh ho hc bt u tm kim nhng qui tc
chung, mi lin h gia cc nguyn t, hp cht. Nm 1817, - be-rai-
n(c) nhn thy khi lng nguyn t stronti gia khi lng hai
nguyn t bari v canxi. ng tm ra b ba u tin.
Nm 1862, nh a cht Php -sng-cuc-toa sp xp cc
nguyn t ho hc theo chiu tng khi lng nguyn t ln mt bng
giy. ng thy tnh cht cc nguyn t lp li sau mi 7 nguyn t.
Nm 1864 gin Niu-lan, tm ra qui lut : mi nguyn t ho hc
u th hin tnh cht ho hc tng t nh nguyn t th 8 khi xp
chng theo chiu tng dn khi lng nguyn t.
Nm 1860, nh bc hc ngi Nga Men--l-p xut tng xy
dng bng tun hon cc nguyn t ho hc. Nhng mi n nm 1869
ng mi cng b bng tun hon cc nguyn t ho hc u tin.
Tit 1
Bi 1. BNG TUN HON CC NGUYN T HA HC
(t hc)
A. MC TIU:
Cu trc bng tun hon; bng tun hon dng di; bng tun hon
dng ngn; cc nguyn t c xp xung di bng tun hon.
B. NI DUNG:
1. Cu trc bng tun hon
C nhiu dng bng tun hon cc nguyn t ha hc:
Bng tun hon dng di 18 ct.
Bng tun hon dng ngn 8 ct.
Bng tun hon dng cha kho.
Bng tun hon dng xoy c.
Chng ta ch nghin cu bng tun hon dng di v dng ngn.
2. Bng tun hon dng di
- S th t.
- Chu k.
- Nhm.
Bng tun hon cc nguyn t ha hc dng di c 18 ct, chia cc
nguyn t thnh tm nhm A v tm nhm B. Mi nhm A v B u
gm mt ct, ring nhm VIII B gm ba ct.
3. Bng tun hon dng ngn
- Chu k: Trong bng tun hon dng ngn, cc chu k ln c ct
lm hai hng, hng trn c mi nguyn t v hng di c tm nguyn
t.
- Nhm: Bng tun hon dng ngn gm tm nhm, c nh s
La m t I n VIII. Mi nhm li chia thnh hai phn nhm: phn nhm
chnh v phn nhm ph.
3

Ring nhm VIII bao gm phn nhm chnh l nhm cc kh him,
cn phn nhm ph gm ba ct dc vi mi hng ngang c ba nguyn.
y l nhm c bit, v thng ba nguyn t hng ngang c tnh cht
ging nhau nhiu hn l tnh cht ca cc nguyn t trong mt ct dc.
4. Cc nguyn t c xp di bng tun hon
Trong bng tun hon dng di cng nh dng ngn c 14 nguyn
t h lantan (
58
Ce
71
Lu) v 14 nguyn t h actini (
90
Th
103
Lr)
tng ng vi cu hnh electron 4f
1-14
chu k su v
5f
1-14
chu k 7 c ct ra v t xung cui cng trong bng tun
hon. Cc nguyn t ny to thnh 14 nhm, mi nhm gm hai nguyn
t theo ct dc. Nu t cc nhm nguyn t h f ny vo bng chung th
bng c qu nhiu nhm v mt tnh cn i, hn na tnh cht ca cc
nguyn t h f c nhng khc bit vi tnh cht cc nguyn t h s, h p
v h d, nn vic ct ra v t xung di bng tun hon c v hp l
nht.
Tit 2
Bi 2. S PHN CHIA PHI KIM-KIM LOI

A. MC TIU:
Phi kim kim loi bn kim bn dn; so snh tnh cht ca kim
loi v phi kim.
B. NI DUNG:
1. Phi kim kim loi bn kim bn dn
Trong s 109 nguyn t trong bng h thng tun hon c ti trn
80% l kim loi. Cc phi kim ch chim cha y 20% v nm gc trn
bn phi bng tun hon cc nguyn t ha hc (dng bng di). im
khc nhau c bn v mt ha hc gia phi kim v kim loi nhm A l phi
kim c xu hng thu thm electron t lp v electron bn vng ging
kh him ng sau n trong cng chu k; cn kim loi c xu hng
nhng electron ha tr t cu hnh electron bn vng ging kh him
ng trc n. Do tnh kim loi v phi kim bin i dn dn trong mt
chu k cng nh trong mt nhm, v th khng c mt ranh gii tht r
rt gia kim loi v phi kim. Tuy nhin s phn chia ny vn c li khi
kho st tnh cht ca cc nguyn t v ngi ta vn coi ng tip gip
gia mt bn gm cc nguyn t B, Si, As, Te, At vi mt bn gm Be,
Al, Ge, Sb, Po, l danh gii phn chia phi kim v kim loi.
Mt s nguyn t vng gip ranh va th hin tnh cht phi kim
va th hin tnh cht kim loi nh: Be, B, Si, Ge, As, Sb, Te, Po, At nn
chng c gi l cc nguyn t bn kim.
Cc nguyn t bn dn nh B, Si, Ge, As, Sb v Te cng nm
vng tip gip gia kim loi v phi kim, tr Se nm su hn trong vng
phi kim. Nh vy a s nguyn t bn dn cng l nguyn t bn kim.
Cc nguyn t bn dn nhn b ngoi ging kim loi. Chng tn x
nh sng vng trng thy v hng ngoi km hn nhiu so vi kim loi;
thng c mu xm v c nh kim. Cc nguyn t bn dn dn in km
hn nhiu so vi kim loi. Tnh dn in s tng ln trong nhng iu
kin nht nh nh khi tng nhit hoc khi c mt lng nh tp cht,
nhng trong cc trng hp dn in vn thp hn dn in ca
kim loi. Chnh dn in thp v tng ln khi tng nhit nn chng
c gi l cc nguyn t bn dn.
S khc nhau v tnh cht in v quang gia kim loi v cc cht
bn dn l do s khc nhau v lin kt trong n cht ca chng. Trong
cc nguyn t bn dn, cc electron ha tr km linh ng hn so vi cc
electron ha tr ca kim loi. V mt ha hc th cc nguyn t bn dn
4

c c tnh ca phi kim tri hn, chng hn hp cht ca chng vi hiro
v halogen c lin kt cng ha tr. Gi tr ca nng nng lng ion ha
th nht v i lc lelectron ca cc nguyn t bn dn nm trung gian
gia cc gi tr ca kim loi v phi kim.
2. So snh tnh cht ca kim loi v phi kim
Kim loi Phi kim
Tnh cht vt l
Nng lng ion ha thp Nng lng ion ha cao
i lc electron thp i lc electron cao
m in thp m in cao
Bn knh nguyn t tng i ln Bn knh nguyn t tng i nh
Thng l cht rn c nhit
nng chy v nhit si cao
Thng l cht kh hoc cht rn c
nhit nng chy v nhit si
thp
C nh kim, phn x nh sng vi
nhiu bc sng khc nhau
Khng c nh kim, phn x nh
sng t, hp th nh sng nhiu
Khi lng ring ln Khi lng ring nh
th rn d rn, cn, ko si th rn dn, cng hoc mm
Dn in, dn nhit tt Dn in, dn nhit km
Tnh cht ha hc
Hp cht vi hiro khng c
trng (to thnh ion hirua )

Hp cht vi hiro c trng (trong
phn t c lin kt cng ha tr)
Oxt kim loi thng c lin kt
ion, cc oxit in hnh tan trong
nc to thnh cc baz
Cc phn t oxit phi kim c lin kt
cng ha tr phn cc, a s tan
trong nc to thnh cc axit
Kim loi tn ti trong dung dch
nc di dng cation hoc t hp
anion cha oxi hay cha cc phi
kim khc
Phi kim tn ti trong dung dch
nc di dng anion n hay cc
t hp cha c phi kim khc mang
in tch m, rt t khi to thnh
cation

Tit 3
Bi 3. C IM CA PHI KIM
A. MC TIU:
c im v cu to nguyn t phi kim; c im lin kt trong
n cht; c im lin kt trong hp cht; c im ca cc phi kim u
nhm.
B. NI DUNG:
1. c im v cu to nguyn t
Nu nguyn t cng d nhn electron th tnh phi kim ca nguyn
t cng mnh. C ba yu t quyt nh tnh cht ny v mt cu to
nguyn t:
- Bn knh nguyn t nh;
- in tch ht nhn hiu dng ln (t b cc lp electron che chn);
- Cu to electron lp bn ngoi ca nguyn t ca nguyn t
ch cn rt t obitan ha tr t do.
Do vy, cc phi kim mnh tp trung nhiu bn phi, pha trn ca
bng tun hon.
2. c im lin kt trong n cht
Trong bng tun hon cc nguyn t ha hc c 24 phi kim, trong
7 phi kim iu kin thng c n cht tn ti di dng phn t
5

hai nguyn t: H
2
, N
2
, O
2
, F
2
, Cl
2
(kh), Br
2
(lng), I
2
(rn). Cc phi kim
khc cn li c cc phn t n cht hp thnh t nhiu nguyn t v tn
ti di trng thi rn. C phn t n cht phi kim rt rn nh kim
cng, nhng cng c phn t n cht mm nh pht pho, lu hunh.
Tnh cht ca cc phi kim khc nhau nguyn nhn ch yu l do tnh cht
lin kt trong n cht ca cc nguyn t .

3. c im lin kt trong hp cht
Cc phi kim phn ng vi nhau to thnh hp cht lin kt cng
ha tr phn cu. Cc hp cht cng ha tr c xu hng tn ti di
dng cc phn t c lp; gia cc phn t ny ch c cc lc tng tc
yu. V vy nhit bnh thng, cc phn t c khi lng phn t b
thng tn ti th kh, cn cc phn t c khi lng phn t ln
thng l cht lng hoc cht rn d nng chy.
4. c im ca cc phi kim u nhm
Trong cc nhm phi kim, nguyn t u nhm thng c tnh cht
ha hc khc bit vi cc nguyn t cn li. Mt phn s khc bit ny l
do cc nguyn t u nhm vi s th t nh hn, c bn knh nguyn t
nh hn v m in ln hn; mt khc nhng nguyn t u nhm
nm chu k 2 ch c th tham gia nhiu nht l bn lin kt, v chng
ch c mt obitan 2s v ba obitan 2p c th tham gia lin kt ha hc.
Nhng phi kim c s th t c th thm cc obitan d tham gia lin kt, v
vy cc nguyn t ny c th c nhiu hn l bn lin kt.
V d: Xt hp cht ca clo vi nguyn t th nht v th hai ca
phn nhm chnh nhm V: nit v photpho. Mi nguyn t nit ch kt
hp vi ba nguyn t clo to thnh nit triclotrua (NCl
3
). Photpho cng
to ta photpho triclorua (PCl
3
), ngoi ra photpho c kh nng lin kt vi
nm nguyn t clo to thnh photpho pentaclorua (PCl
5
).
Cc nguyn t u nhm chu k 2 c kh nng hnh thnh lin
kt tt hn cac nguyn t cn li ca nhm. Nguyn nhn l do bn
knh nguyn t rt nh do cc obitan p to lin kt c kh nng xen
ph rt tt.
V d: Trong trng hp cacbon v silic: cacbon l nguyn t u
nhm. Trong thin nhin cacbon c hai dng th hnh l kim cng v
than ch; trong kim cng cc nguyn t cacbon ch hnh thnh lin kt
; trong than ch cc nguyn t cacbon hnh thnh c lin kt v lin
kt . Lin kt c hnh thnh do c s xen ph gia obitan p khng
tham gia lai ha to lin kt . Trong khi silic iu kin tng t
ch hnh thnh dng tinh th ging nh kim cng vi cc lin kt . Do
lin kt gia cc nguyn t silic vi nhau km bn nn silic khng th
c dng th hnh ging than ch.
6

Chng 2: HIRO OXI NC 12

A. MC TIU:
Tnh cht vt l, ha hc, trng thi thin nhin, iu ch Hiro, oxi
v nc.
B. NI DUNG:

Tit 4 (th), 5, 6, 7
Bi 1: HIRO
A. MC TIU:
V tr ca hiro trong bng h thng tun hon; trng thi thin
nhin; tnh cht vt l; iu ch hiro; tnh cht ha hc.
B. NI DUNG:
1. V tr ca hiro trong bng h thng tun hon
Hiro c s th t nguyn t Z = 1, thuc chu k 1, chu k c bit
ca bng tun hon cc nguyn t ha hc. Chu k ny ch gm hai
nguyn t l hiro v heli. Hiro va ging li va khc cc kim loi
kim v cc halogen (kim loi in hnh v phi kim in hnh). Thc t
ngi ta khng th t hiro vo mt trong hai nhm trn. Tuy nhin
trong bng tun hon, hiro thng c t trn u nhm kim loi
kim th hin c chu k 1 cng c bt u v kt thc.
Nguyn t hiro c cu hnh el n gin nht: 1s
1
, tng ng vi
ht nhn c mt proton mang in tch dng. Hiro c 3 ng v: hiro
hay cn gi l proti ( ), teri ( ), v triti ( ).
Proti v teri l hai ng v bn, cn triti l ng v phng x, c mt
trn tng cao kh quyn, c l c ngun gc t v tr hoc c hnh
thnh t cc phn ng ht nhn do cc tia v tr tc ng.
V tt c cc ng v ca hiro ch c mt electron nn tnh cht
ha hc ca chng ging nhau tr tc phn ng v hng s cn bng.
thng th proti c tc phn ng nhanh hn v n nh hn hai ng v
kia.
Do cu hnh electron c bit nn hiro c th c cc phn ng
sau:
- Nhng electron ha tr to thnh ion H
+
, ion H
+
rt nh,
mang in tch nn c in trng rt ln. Bi vy proton khng th tn
ti c lp m lun lin kt vi cac nguyn t hay phn t khc.
- Nhn thm mt electron to thnh ion H
-
, c cu trc electron
1s
2
.
- a electron ha tr ra dng chung to lin kt cng ha tr vi
cc nguyn t khc. Lin kt cng ha tr ny c th khng phn cc nh
lin kt trong phn t H
2
hoc phn cc nh trong phn t H
2
O, HCl.
2. Trng thi t nhin
T lu ngi ta xc nh c hiro trn bu kh quyn ca mt
tri v ca cc v sao bng phng php phn tch quang ph. C nhng
v sao vi bu kh quyn cha 70% kh hiro. Trong bu kh quyn ca
Qu t c rt t hiro t do, v n d dng khuch tn vo v tr, cn
phn t oxi c tnh thun t v nng tn ti trong bu kh quyn
ca Qu t.
Hiro c trong thnh phn kh ni la, c l hnh thnh do s phn
hy nc khi tip xc vi cc phn thch nng.
3. Tnh cht vt l
Hiro l nguyn t ha hc nh nht, c khi lng ring nh nht
trong tt c cc cht kh: Mt mol kh hiro cn nng 2,016g, do khi
lng ca mt lt hiro l 2,o16g : 22,4l = 0,09g/l 273K v
7

101,325kPa. cng iu kin nhit , p sut, mt lt khng kh nng
1,293g, do vy hiro nh hn khng kh 14,36 ln.
Hiro c t nhit cao. Thuyt kh ng hc cho thy nhit dung mol
ca tt c cc kh c phn t hp thnh t hai nguyn t c ln
khong 21J/K.mol. Nhit dung mol l nng lng cn thit un nng
mt mol kh ln 1K. V hiro l kh nh nht nn nhit dung ring ca n
ln nht trong tt c cc cht kh. (c =q/M)
Hiro cng l cht dn nhit tt, v phn t nh v b nn chuyn
ng nhanh.
Hiro d tan trong palai: 1 th tch palai ha tan khong 870 th
tch hiro.
Hiro tan t trong nc: mt lt nc ha tan c 18,8cm
3
hiro
291K v 101,325kPa.
Hiro rt kh ha lng, cc th nghim ha lng hiro u tin u
tht bi. l do nhit ti hn ca hiro rt thp, mt khc v hiro c
tnh cht rt c bit l nng ln khi thc hin dn kh; ch nhit
thp hn 203K khi dn kh hiro mi lnh i nh cc kh khc.
Nhit ti hn ca hiro l 32,95K, nhit nng chy l 13,79K
v nhit si l 23,35K. Cao hn nhit 32,95K, khng th ha lng
hiro p sut bt k no.
Khi lng ring ca hiro lng d = 0,071g/cm
3
, l khi lng
ring nh nht trong tt c cc cht lng bit hin nay.
4. iu ch
a. Cc phng php iu ch hiro trong phng th nghim
Thng thng H c iu ch bng cch cho axit tc dng vi
kim loi hot ng. Phng php ny thng c thc hin trong bnh
Kp.
Trong mt s trng hp, ngi ta dng hp cht hirua thay cho
kim loi. Canxi hirua thng l nguyn liu sn xut kh hiro np
cc qu bng thm khng ca ngnh kh tng.
Trong phng th nghim cn iu ch hiro bng in phn nc
vi cc in cc platin c cho thm mt t axt, baz hay mui tng
tnh dn in. Phng php ny cho ta hiro rt tinh khit, nhng t.
b. Phng php iu ch hiro trong cng nghip
Tt c cc phng php iu ch hiro trong cng nghip da vo
s phn hy nc hay hirocacbon. Phng php iu ch kh than t:
Trong l phn ng xy ra phn ng gia hi nc v than cc nung
to ra hiro v cacbon oxit

- Thc t ngi ta nhn c mt hn hp kh gm cacbon
monooxit (CO), cacbon ioxit (CO
2
), hiro v hi nc. Thnh phn c
th thng nh sau: 45% H
2
, 45% CO, 5% CO
2
v 5% H
2
O
(h)
.
c nhiu kh hiro v loi b kh CO cn thc hin chuyn ha
CO thnh CO
2
bng cch cho kh cacbon monooxit tc dng vi hi
nc c cht xc tc ph hp

Kh CO
2
c loi b d dng bng cch ha tan vo nc di p
sut ln.
- Kh thot ra t l ch bin than cc cng l ngun cung cp
hiro. Kh l cc c thnh phn sau: 50% H
2
, 30% CH
4
, 8% CO v mt
s hp cht khc.
8

Bng cch lm lnh hn hp kh, ngi ta c th loi CH
4
v CO
2

ra khi hn hp, cn kh CO c chuyn thnh CO
2
c s tham gia ca
cht xc tc nh trn v loi ra khi hn hp. Cui cng phng php
ny tp ra c ngun kh hiro cng nghip.
- iu ch hiro t kh metan, thnh phn chnh trong kh t thin
nhin. Ngi ta cho kh metan tc dng vi hi nc nhit 1373K.

Sn phm ph ca qu trnh ch bin du m.
Kh hiro cng nghip tinh khit nht c th iu ch bng in
phn nc. Thng ngi ta pha thm baz c th dng in cc
niken thay cho in cc platin rt t tin.
Hiro cng l sn phm ph trong qu trnh in phn dung dch
mui n hay kali clorua iu ch NaOH hay KOH.
5. Tnh cht ha hc
a. Phn ng ca hiro vi oxi
Hiro chy trong oxi hay khng kh gii phng mt nng lng ln

Nu ta t nng mt hn hp hiro v oxi theo t l th tch 2:1
bng tia la in hay bng m la th phn ng s n mnh. Hiro phn
ng n vi oxi khng chit t l th tch 2:1, ta qen gi l hn hp n.
Phn ng n c th xy ra nu trong oxi c cha 5% hiro hoc trong
hiro c cha 6% oxi. Trong khong gii hn trn v gii hn di ny
c nguy c xy ra nhng tai nn n bnh cha kh.
Nu h p sut xung cn 19,46kPa th hn hp kh hiro v oxi,
k c t l 2:1 cng khng gy n v kh nng dn nhit ca hn hp kh
iu kin ny rt km nn phn ng cc b khng th lan truyn n
nhng phn khc ca hn hp kh.
Nng lng ta ra nhng phn ng hiro tc dng vi oxi c
dng hn, ngi ta thng quen gi l hn hi ( phn bit vi hn
in).
b. Phn ng ca hiro vi cc phi kim khc
nhit thng, hiro phn t c tnh th ng ha hc.
Ch c flo phn t phn ng mnh vi hiro nhit thng, c
th chy thnh ngn la hoc n
H
2
+ F
2
2HF
Hiro phn ng mnh vi clo ch khi c tc dng ca nh sng mt
tri, t nng hay a vo h phn ng mt ngun nng lng no y;
phn ng c th gy n.
Hiro tc dng vi brom v iot nhit cao
c. Phn ng ca hiro vi cc kim loi
- Vi cc kim loi kim
Hiro phn ng vi cc kim loi kim nh liti, natri, kali to
thnh cc hirua dng M
(I)
H.
V d: H
2
+ 2Li 2LiH
- Vi cc kim loi kim th
Hiro tc dng vi cc kim loi kim th nh canxi, stroti, bari to
thnh cc hirua dng M
(II)
H
2
.
Hirua ca cc kim loi kim v kim th mang tnh cht ca cc
mui, trong nguyn t hiro ng vai tr anion H
-
.
- Vi kim loi chuyn tip
9

Hiro tc dng vi cc kim loi chuyn tip to thnh cc loi
hirua khc nhau.
Mt s cc nguyn t t him phn ng vi hiro to thnh cc
hirua dng mui.
Cc kim loi chuyn tip nh titan, ziriconi, vanadi, niobi, tantan,
thori, uran v.v tc dng vi hiro to thnh dung dch rn v hp cht
i khi c h s t lng thay i nh: Ti
1,65
, TiH
2
, ZrH
2
, UH
3
v.v cc
hp cht phn no vn cn th hin tnh kim loi.
Nhm, berili v magie hnh thnh cc hp cht (AlH
3
)
n
, (BeH
2
)
n
,
(MgH
2
)
n
c hnh thnh do s phn hy cc hp cht c kim, c tnh
cht khc hn cc hirua dng mui.
d. Hiro nguyn t
Hiro nguyn t c iu ch t hiro phn t bng cch cung
cp nng lng cho phn ng phn li phn t
H
2
2H; H
o
= +430,92kJ/mol
Phn ng c th xy ra theo kiu gia nhit hay phng in qua
hiro phn t di p sut thp.
Nu ta thi hiro qua ngn la n h quang vi hai in cc
vonfam, th c s phn li mt phn hiro phn t thnh hiro nguyn t.
Nu hng dng hiro nguyn t nng ln b mt kim loi gn h
quang in th c s lin kt hiro nguyn t tr li thnh hiro phn t,
nhit phn ng ta ra c th nung kim loi, c trng hp lm nng
chy c kim loi
2H H
2
; H
o
= -430,92kJ/mol
ng dng thc t trong trng hp ny l m hn Lngmuya dng
hn nhng kim loi kh nng chy. M hn ny c ngn la kh. y
l mt u th so vi m hn hi v m hn h quang (hn in), hai loi
m hn ny c ngn la oxi ha.
Hiro nguyn t cn c to thnh qua phng in vo kh hiro
p sut thp t 0,013 n 0,135kPa.
Hiro nguyn t c kh nng phn ng rt ln, v d nhiu oxit
kim loi b hiro nguyn t kh thnh kim loi nhit thng,
Hiro nguyn t phn ng vi oxi to thnh hiro peoxit
2H + O
2
H
2
O
2

Thi gian tn ti ca hiro nguyn t rt ngn; nu khng c mt
cht phn ng th ch sau mt thi gian ngn c s ti kt hp thnh hiro
phn t thnh ng dn.
Khi ha tan kim loi hot ng vo axit cng c s to thnh hiro
hot ng. Hiro loi ny ngay lc va xut hin tng ti di dng
nguyn t hoc t nht cng trng thi kch thch, c kh nng phn ng
tt hn hiro phn t v c gi l hiro mi sinh.
6. ng dng
Hiro c ngha ln trong cng nghip. Sn lng hiro hng nm
ca th gii ln n hng t mt khi; khong 2/3 c dng tng hp
amoniac. Ngoi ra cn dng tng hp hu c, v d tng hp ru
metylic v cc ng ng bng hiro ha cacbon monooxit p sut cao
c mt cht xc tc

Hay dng hiro tng hp xng nhn to.
Ngi ta cn dng hiro trong sn xut b nhn to (magarin).
7. Cc ng v ca hiro ( )
10

teri, ng v c s khi 2, c ngha rt ln trong nghin cu
khoa hc v n c s khi gp i ng v hiro bnh thng. ng v c
trong thin nhin rt t, ch chim 0,02%. Hiro l nguyn t ph bin
c pht hin t lu, nhng ng v nng ca hiro mi c pht hin
ra cha lu lm.
tt c cc qu trnh m khi lng ca nguyn t ng vai tr
quan trng th teri c tnh cht khc vi hiro bnh thng. teri bc
hi km hn, kh khuch tn hn hiro bnh thng. teri phn ng
vi cc nguyn t khc ging nh hiro nh. teri c th dng xc
nh cu trc ca hp cht ha hc v gii thch c ch nhiu phn
ng ha hc.
teri thng c iu ch bng in phn nc nng hay cho
nc nng tc dng vi kim loi nhit cao nh bt km, vonfam;
mt khc c th iu ch teri bng ct phn on hiro lng. H s
phn chia ng v H
2
/D
2
tng i thun li mc d nhit ha lng
ca c hai ng v u thp v s chnh lch nhit si nh, ch cch
nhau 3,28K.
Triti l ng v sii nng ca hiro.
Hiro siu nng c gi l triti, k hiu l T hay l ng v
phng x, c iu ch nhn to trong cc l phn ng ht nhn t
vi ntron chm theo phng trnh

Mt lng nh triti c mt trn tng cao kh quyn, c l c hnh
thnh do cc tia v tr hoc c ngun gc t v tr, c phn ng phn r
phng x to thnh vi chu k bn r 12 nm.
Bom khinh kh c gu n bng phn ng nhit hch, trong
cht n nhit hch l liti terua LiD.
Ngi n l mt qu bom nguyn t bnh thng. Ntron ca qu
bom ny to ra phn ng ban u

Triti mi hnh thnh phn ng vi teri nhit hng triu
do bom nguyn t to ra theo phng trnh

Qua phn ng tng hp ht nhn ny, cc ntron cn lm phn
r ht nhn Li li c sn ra v triti li c tip tc c gii phng.
Qua dy truyn phn ng nhit hch c to ra. Qua cc qu trnh
ny, ton b cht n nhit hch liti terua bin i thnh He v to ra
nng lng v cng ln trong thi gian ngn. Sc tn ph ca loi bom
khinh kh ny rt ln, gp nhiu ln sc tn ph ca bom nguyn t.

Tit 8, 9, 10
Bi 2. OXI (O)
A. MC TIU:
Trng thi thin nhin; iu ch; tnh cht vt l; tnh cht ha hc;
ng dng; vai tr sinh hc ca oxi; chu trnh ca oxi trong t nhin; ozon
(c im chung v iu ch; tnh cht vt l v ha hc; ng dng; ozon
trn tng cao ca kh quyn).
B. NI DUNG:
Nguyn t oxi c xu hng nhn thm hai electron vo lp ngoi
cng t c cu hnh bt t ging kh him ng sau n trong chu
k
O + 2e O
2-
, E = +659,4kJ/mol
hoc to nn hai lin kt cng ha tr hoc mt lin kt i.
11

Nng lng ion ha kh cao: I
1
= 1317,96kJ/mol v I
2
=
3399,06kJ/mol nn vic nhng electron trong phn ng ha hc kh
hn.
1. Trng thi thin nhin
Thnh phn chnh ca khng kh di tng thp thc t mi ni
u nh nhau tr nhng ni qu nhim. trng thi kh, thnh phn
ca cc cht kh trong khng kh nh sau:
Nit chim 78,084% th tch hay 75,521% khi lng;
Oxi chim 20,946% th tch hay 23,139% khi lng;
Agon chim 0,934% th tch hay 1,288% khi lng;
Cacbon ioxit chim 0,033% th tch hay 0,050% khi lng.
Ngoi ra cn c vi lng cc kh him khc nh heli, neon,
kripton, xenon vi 0,003% th tch hay 0,002% khi lng.
Oxi c trong thnh phn ca nc chim 89% khi lng.
Oxi l nguyn t ph bin nht cu to nn v qu t, chim
khong 50% khi lng.\
Oxi c 3 ng v bn:
16
O,
17
O v
18
O.

16
O chim 99,76%,
17
O chim 0,04% v
18
O chim 0,2%. Vic tch
cc ng v oxi kh hn vic tch cc ng v hiro nhiu, v hiu khi
lng gia cc ng v oxi nh hn so vi trng hp hiro. Tuy vy,
ngi ta vn c th tch cc ng v ca oxi bng phng php khuch
tn nhit.
2. iu ch
a. Cc phng php iu ch trong phng th nghim
nhit phn hp cht giu oxi, t bn nh KClO
3
, KMnO
4
.
- Nhit phn kali clorat nhit 773K

- Nhit phn dng hn hp kali clorat v mangan ioxit t l 10:1.
Trong trng hp ny, mangan ioxit l cht xc tc v phn ng xy ra
nhit thp hn (t
0
= 423K).
- Nhit phn kali pemanganat

(nhit tng t nh nhit phn KClO
3
)
b. Cc phng php iu ch cng nghip
Trc y ngi ta dng phng php peoxit ca Brin:

Bari oxit kt hp vi oxi khng kh kh 773K to thnh bari
peoxit. nhit cao 973K, bari peoxit b nhit phn to thnh bari oxit
v oxi.
Hin ti oxi c iu ch trong cng nghip theo cc phng
php:
- Ct phn on khng kh lng;
- in phn nc.
* Phng php ct phn on khng kh lng c dng ph bin
nht.
Khng kh c ha lng dng lm lnh v to nhit thp,
mt khc dng lm nhin liu iu ch oxi v nit trong cng nghip
v sn phm ph l cc kh him.
* iu ch oxi bng phng php in phn nc
12

Oxi c iu ch bng in phn nc ng thi cng l iu ch
hiro. V nc n in km nn cn phi cho thm cht in li vo b
in phn. Cht in li thng dng l hiroxit ca kim loi kim.
Qu trnh in phn din ra nh sauL
Trong b in phn cha cc cht in li t hai in cc gm in
m (catt) v in cc dng (ant).
Cc cation di nh hng ca in trng di chuyn v catt,
trong khi cc anion di chuyn v ant.
Trong dung dch:
NaOH Na
+
+ OH
-

2H
2
O H
3
O
+
+ OH
-

catt c cc ion Na
+
v H
3
O
+
, trong H
3
O
+
d b kh in hn
2H
3
O
+
+ 2e H
2
+ 2H
2
O (catt)
2OH
-
- 2e H
2
O + 1/2 O
2
(ant)
Kt qu in phn dung dch kim l tng ca hai bn phn ng
trn
2H
3
O
+
+ 2OH
-
4H
2
O 3H
2
O + H
2
+ 1/2O
2

3. Tnh cht vt l
iu kin thng oxi l cht kh khng mu, khng mi. Nhit
ti hn ca oxi 154,35K; oxi ha lng 90,22K, ha rn 54,25K.
Khi lng ring ca oxi im si l 1,118g/cm
3
. 293K oxi ha tan
trong nc khong 3% theo th tch. S ha tan oxi trong nc c
ngha rt quan trng i vi cc sinh vt sng trong nc. Oxi nng hn
khng kh 1,106 ln, nhit thng mt lt oxi nng 1,428 gam.
Khong cch gia hai nguyn t oxi trong phn t l 120pm. Cc phn t
oxi phn li nhit cao
; H
0
= +492,66kJ/mol
phn li ca phn t oxi l 6% 3000K. Oxi c tnh thun t.
nhit thp ngi ta xc nh c s tn ti ca cc phn t O
4
nghch
t.
4. Tnh cht ha hc
iu kin thng oxi tng i th ng. Phn ng vi cc cht
chy ch xy ra khi cc cht ny c nung nng mt nhit nht
nh, sau phn ng tip tc t din bin, v sau khi t c nhit
bc chy qu trnh phn ng tip theo gii phng nng lng duy
tr nhit phn ng. nhit cao tng ng, hu ht cc nguyn
t ha hc u phn ng vi oxi.
S chy chm c ngha rt quan trng cho qu trnh sng, v n
l ngun cung cp nng lng cho tt c cc h sinh hc. Khi h hp, cc
c th nhn oxi, dng n t cc cht hu c, qua nhn nng
lng cn thit duy tr thn nhit hoc duy tr cc hot ng cn thit
khc cho s sng. Mi ngi ln dng ht khong 20 lit oxi mi gi;
nhng ngi lao ng nng nhc bng tay chn thng dng lng oxi
nhiu hn.
a. Oxi phn ng vi cc phi kim
Photpho trng dng phn tn nh phn ng vi oxi ca khng kh
ngay nhit phng. Photpho chy trong oxi nguyn cht vi ngn la
sng chi v to ra photpho pentoxit
Lu hunh v cacbon chy mnh trong oxi khi c t nng
b. Oxi phn ng vi cc kim loi
Natri chy trong oxi to thnh natri peoxit
2Na + O
2
Na
2
O
2

13

Kali, rubidi v xesi di cng iu kin phn ng to ra supeoxit
M
(I)
O
2
.
- Tr mt s kim loi qu ra, cc kim loi cn li phn ng vi oxi
to ra cc oxit, cc kim loi nng cng chy trong oxi.
Qu trnh oxi ha cc nguyn t gii phng ra nng lng ln nh
khc nhau, ty thuc vo i lc ca cc nguyn t ny i vi oxi.
Cc oxit c entanpi hnh thnh chun m t s b nhit phn d
dng to thnh nhng cht ban u. Mt s oxit c entanpi hnh thnh
dng, iu ny cho thy cc hp cht ny khng bn.
5. ng dng
Oxi c dng t hiro hay axetilen trong hn hi hn, ct
kim loi. Oxi c dng trong luyn kim. Trong y hc ngi ta dng oxi
thc hin h hp nhn to i vi nhng bnh nhn nng. Bt than g
nhng vo oxi lng c dng lm cht n, c bit trong khai thc than
. Oxi lng cn c dng lm cht oxi hoc cht t ca ng c tn
la.
6. Vai tr sinh hc ca oxi
Oxi c ngha rt to ln v mt sinh hc. Cc hp cht hu c cu
to sinh gii hu ht l hp cht cha oxi. Cc nguyn t oxi chim mt
phn t trong tng s xc loi nguyn t tham gia cu to sinh vt.
Oxi rt cn thit cho s sng ca mun loi. Nu khng c oxi,
nhng ng vt mu nng s cht trong vi ba pht. Nhng ng vt mu
lnh tiu th t oxi hn, nhng cng khng th sng thiu oxi c.
Khi h hp, ng vt thu nhn oxi, gi li mt phn tng hp
cc cht cn thit cho s sng. Phn ln oxi cn li tham gia phn ng
oxi ha chm cc cht dinh dng, bin i chng thnh kh CO
2
, H
2
O
v nng lng. Thc vt li thu nhn kh cacbonic cng vi nc to
ra cc hp cht hu c v gii phng oxi nh nng lng mt tri. Qu
trnh h hp thu nhn oxi v thi ra kh cacbonic ca thc vt tng i
yu v thng th hin r vo ban m, khi khng c nh sng mt tri.
Ch mt s t vi sinh vt, c gi l vi sinh vt ym kh, c th tn ti v
pht trin khng cn n oxi nh mt s men v mt s vi khun ym
kh. ng vt sng trn mt t v mt s ng vt sng di nc thu
nhn oxi t khng kh nh hai l phi. ng vt sng di nc nh cc
loi c thu nhn oxi tan trong nc nh cc mang gi. Mt s sinh vt
khc sng di nc hp th oxi trc tip qua da, qua mng t bo v.v,
ging nh cc ng vt bc thp.
i vi ngi khi ht vo, oxi qua ph nang chuyn vo mu.
Hemoglobin trong hng cu lin kt yu vi phn t oxi to thnh oxi
hemoglobin. Hp cht ny km bn, d b phn hy, c chuyn n
cc t bo. Ti y oxi c gii phng v oxi ha chm cc cht dinh
dng cng c mu a n, nh c mt ca cc cht xc tc sinh hc.
Chng hn qu trnh oxi ha glucoz to thnh kh CO
2
, nc v nng
lng. Nng lng gii phng ra c dng duy tr cc qu trnh sng
nh c ng, thn nhit v.v ...
Ngoi vai tr trc tip duy tr s sng trn qu t, oxi gin tip
bo v cc sinh vt khi s dit vong bng qu trnh hnh thnh tng ozon
trn tng cao ca kh quyn.
7. Chu trnh ca oxi trong t nhin
Cc nguyn t oxi chim khong mt phn t trong tt c cc loi
nguyn t tham gia cu to sinh gii c mt trn qu t. ng vt th
oxi gi li mt phn tng hp cc cht cn thit cho s sng. nng
lng cn thit duy tr qu trnh trao i cht c to ra do s oxi
ha chm cc hp cht hu c bin i thnh kh cacbonic v kh ny
14

c thi ra ngoi qua con ng tun hon v h hp. Oxi cn tham gia
trong qu trnh phong ha cc , qung v c. Ngoi ra, oxi cn c
dng rt nhiu trong qu trnh t chy cc nhin liu nh than , xng
du v.v
V cho n nay lng oxi trong bu kh quyn khng gim i, nn
phi c mt qu trnh no sn xut ra mt lng oxi rt ln b p
vo lng oxi c s dng. Lng oxi khng l b tiu hao c b
p ch yu bng cch bin i kh cacbonic v nc thnh cc hp cht
hu c v gii phng oxi qu trnh quang hp ca thc vt. V qu trnh
ngc li gii phng nng lng , nn thc vt cn n nng lng
thc hin phn ng quang hp. Ngun nng lng ny c mt tri
cung cp. Nh vy cuc sng trn qu t ny ph thuc vo nng lng
mt tri. Nh c nng lng mt tri, chu trnh oxi trong thin nhin mi
c khp kn v cuc sng mun mu, mun v trn mt t mi c
duy tr v pht trin.
Theo tnh ton khoa hc, khong 5 t nm na mt tri s ngui v
tt. Lc loi ngi phi lm g tip tc tn ti? C th du hnh sang
h thi dng khc nh i du lch bay gi hay bn mt tri nhn to ln
v tr. y ch l nhng chuyn tng lai xa vi, nhng vi khi c v
ti nng, con ngi c th vn ti c.
8. Ozon
a. c im chung v iu ch
ozon l mt dng th hnh ca nguyn t oxi. Oxi c tch cht vt l
v ha hc khc hn oxi bnh thng. Ozon c bit n t lu, v n
xut hin khi c s phng in trong khng kh v c th nhn bit qua
mi kht c trng.
Lng ln ozon c iu ch trong thit b sn xut ozon. Khi t
in p cao xoay chiu hai in cc ca thit b sn xut ozon th xy
ra s phng in m gia hai cc; do s phng in m ny, mt phn
oxi c chuyn thnh ozon. Thc t cho thy ozon tng ln khi tn s
in xoay chiu tng. Khi in phn axit pecloric, ozon c to ra
ant. Lng ln ozon tng kh quyn thp, chim khong 10
-6
%.
Lng ozon tng cao kh quyn ln hn nhiu.
b. tnh cht vt l v ha hc
Ph hp th hng ngoi ca ozon cho php chng ta rt ra kt lun
v hnh dng ca phn t:

Gc lin kt ca phn t l 117
0
; di lin kt gia cc nguyn t oxi l
126pm, do vy cu trc c in ca phn t ozon theo hnh tam gic u
vi cc lin kt n ca ba nguyn t oxi l khng ng; cu trc ny
khng phn nh ng tnh cht oxi ha mnh ca ozon. S bin i oxi
thnh ozon l phn ng thu nhit
3O
2
2O
3
;
0
= 289,8kJ/mol
V vy ozon l dng th hnh khng bn ca oxi. c im chung
ca tt c cc phn ng to thnh ozon l hnh thnh cc nguyn t oxi.
V d: Tc dng ca flo vi nc to thnh nguyn t oxi, nguyn
t oxi phn ng vi phn t oxi to thnh ozon
F
2
+ H
2
O 2HF + O
O + O
2
O
3

Trong qu trnh in phn nc c s hnh thnh ozon v c s
xut hin nguyn t oxi ant
15

2OH
-
H
2
O + O (ant)
Ozon cng c hnh thnh khi ri tia t ngoi vo khng kh (mi
kht khi bt n t ngoi).
trng thi rn, ozon rt kh bo qun, v ch cn ng nh cng
c th n.
Khi lng ring ca ozon rn 78,15K l 1,728g/cm
3
, ozon rn
c mu . Ozon ha tan trong freon, v d trong CCl
3
F, dung dch ozon
c tnh cht oxi ha mnh. Mt s cht xc tc cho s phn hy ozon, v
d nit oxit hay cc freon. Khi c mt cc cht ny th bn ca ozon
gim mnh, v th s nhim ca mi trng do nit oxit v freon lm
thng tng ozon (ph v tng ozon), lm hng l chn tia t ngoi ca
qu t e da trc tip n cuc sng trn tri t.
Ozon nguyn cht khng c mt vt cht hu c no c th bt la
ta nh sng xanh chuyn ha thnh oxi phn t
2O
3
3O
2
;
0
= -289,8kJ/mol
Dng ozon t ixian (CN)
2
trong ngn la m hn hi p
sut 101,324kPa s t c nhit 5173K.
Cc phn ng nhn bit ozon
Ozon l mt trong nhng cht oxi ha mnh nht. Mt lng nh
ozon cng c th pht hin c qua mi c trng.
Khi dn ozon qua dung dch kali ioua trung tnh, ozon phn ng
gii phng iot v lng iot c th nhn bit bng h tinh bt
2I
-
+ O
3
+ H
2
O I
2
+ O
2
+ 2OH
-

Trong phn ng ny ch c mt nguyn t oxi trong phn t ozon
tham gia phn ng oxi ha kh
2I
-
+ O + H
2
O I
2
+ 2OH
-

Tuy nhin cng c phn ng c ba nguyn t oxi trong phn t
ozon cng tham gia.
V d nhiu hp cht hu c cha no, di nhng iu kin xc
nh phn ng vi ozon to thnh hp cht ozonua. Cc hp cht ozonua
thng l nhng hp cht snh, d n.
S ph hy cao su di tc dng ca ozon l qu trnh hnh thnh
hp cht ozonua. V vy, khng c dng ng cao su dn ozon.
S oxi ha ch sunfua (en) thnh ch sunfat (trng) l mt loi
thuc th xc nh ozon.
PbS + 4/3O
3
PbSO
4

c. ng dng
Mt lng nh ozon c dng tit trng, ci to khng kh
trong cc phng kn nh nh ht, rp chiu bng, v.v Ngc li, ozon
nng ln l cht c c hi cho sc khe.
Ozon dng ty mu, dng lm cht oxi ha, dng tng hp
mt s cht hu c. Mt thi gian di ngi ta dng ozon kh trng
nc my. Ngy nay nc my c x l bng clo thay cho ozon v tnh
cht dit khun ca clo cao hn v r tin hn ozon. Ozon cn c dng
lm cht oxi ha cho thin liu tn la. i khi ngi ta dng ozon x
l ru vang. Theo quy tc, ru vang phi c lu gi mt thi gian
di t mi thn v cht lng cao, c ngha l cho n khi loi b
c mi v ton b lng anehit. Dng ozon oxi ha nhanh chng
cc anehit s rt ngn c thi gian lu gi ru vang di hm ru.
d. Ozon trn tng cao ca kh quyn
* Tng ozon
Trn cao khong 90 km, phn ln cc tia t ngoi sng ngn b
hp th bi cc thnh phn ca khng kh long v ion ha chng. Khi
16

gim cao th nng cc ion v electron gim nhanh chng. Tuy
nhin cc tia t ngoi c tc dng phn li phn t oxi thnh nguyn t
cao ny ny vn cn rt ln. Qua trnh quang phn cc phn t oxi
cn mnh m cho ti cao khong 30km. Nh vy bt u xy ra phn
ng quang phn phn t oxi cao di 90km. Trong khong cch
ny, nng cc phn t oxi ln hn nhiu so vi nng cc nguyn t
oxi. Khi nguyn t oxi c hnh thnh s va chm thng xuyn vi cc
phn t oxi dn n s hn thnh ozon (O
3
)
O
(k)
+ O
2(k)
O
*
3(k)

Ozon va hnh thnh cn cha nng lng d, c m t bng
. Phn ng hnh thnh ozon t oxi nguyn t v oxi phn t gii
phng nng lng 105 kJ/mol. Phn t O
3
hoc phi truyn nng lng
ny cho cc phn t khc ngay trong thi gian cc ngn, hoc li phn
hy thnh O v O
2
. Qu trnh phn hy l phn ng nghch ca phn ng
to thnh ozon trn nn phn ng trn l phn ng thun nghch
O
(k)
+ O
2(k)
O
*
3(k)

Phn ng ny c th chuyn dch theo chiu ny hay chiu kia.
Phn t O
3
c th gii phng nng lng d tha bng nhng va chm
vi cc nguyn t hoc phn t khc, ng thi truyn nng lng sang
cc tiu phn ny. Nu chng ta biu th nguyn t hoc phn t va
chm vi phn t ozon bng X (X c th l phn t N
2
, O
2
ca khng
kh), s chuyn giao nng lng c m t theo cc phng trnh:
O
(k)
+ O
2(k)
O
*
3(k)

O
*
3(k)
+ X
(k)
O
3(k)
+
O
(k)
+ O
2(k)
O
3(k)
+
Cc phng trnh trn m t s cnh tranh gia phn ng thun v
phn ng nghch. Nu c t s va chm (trong vng khng kh rt long)
th phn ng nghch chim u th v phn ln phn t ozon va hnh
thnh t phn hy thnh O v O
2
. Nu s lng va chm trong n v
thi gian ln th s hnh thnh ozon (theo phn ng thun) chim u th,
v mt khng kh tng ln khi cao gim. Mt khc cc tia t ngoi
quang phn phn t oxi gim cng khi cao gim v phn ln
v hp th tng kh quyn bn trn. Cc iu kin tri ngc nhau i
vi s to ra ozon ni trn dn n s tn ti mt vng hnh thnh ozon
cc i trn cao khong 50km xung quanh qu t, c gi l tng
ozon.
Theo quy tc thng thng th phn t ozon va hnh thnh li tip
tc bin i. Bn thn phn t ozon cng hp th nng lng mt tri v
t phn hy thnh O v O
2
. Theo l thuyt, qu trnh phn hy ny ch
cn nng lng 105kJ/mol, v vy bc x mt tri vi bc sng nh hn
1140nm khi ng phn ng phn hy. Tuy nhin qu trnh hp
th mnh v quan trng nht ca ca phn t ozon cng li xy ra trong
vng sng gia 190 n 310nm. Ozon l cht duy nht hp th mnh bc
x mt tri c bc sng ngn, giu nng lng c th xm nhp n b
mt qu t v tiu dit mi s sng. Nh vy lp bo v ny khng th
thiu i vi s tn ti ca loi ngi v sinh gii ni chung trn qu t.
Qu trnh hnh thnh v phn hy ozon l mt chu trnh khp kn
O
2(k)
O
(k)
+ O
(k)

O
2(k)
+ O
(k)
+ X
(k)
O
3(k)
+ (ta nhit)
O
3(k)
O
2(k)
+ O
(k)

O
(k)
+ O
(k)
+ X
(k)
O
2(k)
+
17

Kt qu chung ca cc qu trnh l s bin i tia t ngoi ca mt
tri thnh nhit. Qua nhit tng ln trn khong khng ny.
Cc phn ng trn ca qu trnh hnh thnh v phn hy ozon cha
ni ln c tt c nhng g xy ra trn tng ozon, bi v trn c th
c nhiu phn ng ha hc xy ra vi cc cht khc na. Ngoi ra cn
phi xt n s xo trn ca tng cao kh quyn do nhng xoy khng
kh v gi. Qua chng ra c th d on s xut hin mt cnh tng
rt phc tp.
Bo v tng ozon
Nit oxit (NO) v nit ioxit (NO
2
) c nng rt thp trong tng
ozon. Ozon tc dng vi nit oxit to thnh oxi phn t v nit ioxit.
Ozon tc dng vi nit ioxit to thnh oxi phn t v nit oxit.
O
3(k)
+ NO
(k)
NO
2(k)
+ O
2(k)

NO
2(k)
+ O
3
NO
(k)
+ 2O
2(k)

2O
3(k)
3O
2(k)

Qua cc phn ng trn chng ta thy NO ch ng vai tr xc tc
phn hy ozon ch khng thay i nng ca n.
Ngoi ra chng ta cng bit cc dn xut cloflohirocacbon trc
ht l CF
2
Cl
2
v CFCl
3
(cc freon) c tc dng ph hy tng ozon. Cc
cht ny trc y c dng nhiu trong cc loi my lnh, t lnh v
trong cc loi bnh xt, v chng rt bn v v hi trong bu kh quyn
gn mt t. Tuy nhin bn ca chng b nh hng khi chng khuch
tn ln tng cao ca kh quyn v b tc dng trc tip ca cc tia t
ngoi c bc sng 190 225 nm. Cc lin kt gia cacbon v cc
nguyn t clo v th b ph v
CF
x
Cl
4-x
CF
x
Cl
3-x
+ Cl
(k)

Gc CF
x
Cl
3-x
c th b quang phn tip tc. Nguyn t clo b
quang phn nhiu cao khong 30 km tr ln, c kh nng tc dng
vi ozon to ra O
2
v clo. Clo tc dng vi oxi nguyn t to thnh ClO
v O
2
.
Cl
(k)
+ O
3(k)
ClO
(k)
+ O
2(k)


ClO
(k)
+ O
(k)
Cl
(k)
+ O
2(k)

O
3(k)
+ O
(k)
2O
2(k)

Phn ng ca clo nguyn t trn tng ozon ging vi phn ng ca
NO v dn n phng trnh phn ng tng cng nh nhau. Nh vy c
hai cht ny l nhng xc tc trong phn ng ozon tc dng vi oxi
nguyn t to thnh hai phn t oxi. Bi vy NO v Cl tc dng vi oxi
nguyn t to thnh hai phn t oxi. Bi vy NO v Cl (trong cc freon)
c coi l tc nhn gy ra s ph v tng ozon, c ngha l ph v l
chn chng li cc tia t ngoi giu nng lng ca mt tri. Tng ozon
b ph v nh hng trc tip n s sng ca mi ng thc vt trn
mt t. Va qua v tinh nghin cu kh tng chp c ng l
thng ca tng ozon Nam cc, ko di n tn bu tri cc nam
Acgentina. Vn ny ang c rt nhiu phng th nghim v mi
trng nghin cu. bo v tng ozon v cng l bo v s sng
trn mt t, trm bnh din Quc t c s tha thun hn ch ti a
vic s dng cc hp cht cloflohirocacbon trong cc loi my lnh,
nht l np vo cc loi bnh xt v sau mt thi gian s khng s dng
cc loi hp cht ny na; ngoi ra cng cm x cc kh thi c cha NO
v NO
2
ra khng kh.
Tuy nhin theo mt s nh khoa hc Nga th s ph v tng ozon
do cc freon gy ra l khng chc chn v khng c cn c, v cc phn
18

t ca cc hp cht khuch tn rt chm khi b mt qu t vt ln
tng ozon gy hi. H cho rng s hnh thnh tng ozon l do bc x mt
tri quyt nh dy, mng v c l thng hay khng c ty theo ma
v s pht ra cc bc x vi cng khc nhau theo cc thi im .
Nh vy h khng nh rng cc freon b ln n oan.
S ph v tng ozon c th do mt s nguyn nhn khc na. Bi
vy, cc nh khoa hc vn cn tip tc nghin cu c kt lun xc
ng hn v nguyn nhn ca n.


Tit 11(th), 12, 13, 14
Bi 3. NC
A. MC TIU:
Trng thi t nhin; tinh ch nc; tnh cht vt l; tnh cht ha
hc; s nhim mi trng. Cch x l nc thi; nc nng; hiro
peoxit
B. NI DUNG:
1. Trng thi t nhin
Nc bao ph b mt qu t di dng cc i dng. Mt
phn t mt t cn li cha nhiu nc trong sng, sui, m, h, ti
nc ngm, mch nc ngm, thng l ngun nc ngt. Mt lng
nc ng k tham gia cu to thc vt v c th ng vt, v d c th
ngi hp thnh t 60 70% nc; rau ci, x lch cha hn 90% nc.
Bu kh quyn c th nhn 4% hi nc hoc hn na. Khi thay i p
sut v nhit , hi nc c th chuyn tr thnh th lng nh sng
m, ma hoc th rn nh ma , tuyt. Nhiu hp cht ha hc v
khong sn cha nc di dng lin kt ha hc v nc kt tinh, v d
nh nc tham gia lin kt ha hc trong Ca(HCO
3
)
2
v nc kt tinh
trong CaSO
4
.2H
2
O.
2. Tinh ch nc
Phn ng to nc:
2H
2
+ O
2
2H
2
O
Nc c entanpi hnh thnh chun = -242,8kJ/mol hay
= -87,2kJ/mol.
V nc c sn trong thin nhin nn ngi ta khng phi iu ch
bng phng php ha hc, m ch tinh ch nc t nhin dng.
Trong nc t nhin c nhiu tp cht, v vy khng ph hp cho
cc mc ch s dng khc nhau. Ty theo mc ch s dng xut hin
cc phng php tinh ch nc khc nhau.
Nc dng cho mc ch ha hc phi tinh khit hon ton, trong
nc khng cn cc tiu phn huyn ph v cc cht ha tan. Mun t
c mc ch ny cn phi tin hnh ct nc. Thng thng nc
c ct t cc b ct bng thch anh. bo m cht lng tt hn,
nc c ct trong cc dng c bng bc hoc platin. Trong ha hc
phn tch, nc c ct hai ln nn c gi l nc ct hai ln. i vi
nhng nghin cu quan trng, nc cn c tinh ch loi tr cc kh
tan nh kh cacbonic chng hn, nht l nhng nghin cu v in ha
trong dung dch,
Nc dng trong sinh hot
Nhu cu s dng nc sinh hot rt ln, v vy nc sinh hot
c tinh ch quy m ln trong cc nh my. Tinh ch nc sinh hot
thng gm c nm bc: lc th, lng, lc qua ct si, phun ma v
kh trng.
19

Tch cc tiu phn huyn ph thc t l lc nc qua ct, si hay
c khi bng t nung xp.
Hp cht st v mangan cng nh cc thnh phn hu c c oxi
ha bng khng kh qua phun ma trn gin phun.
Vic kh trng nc sinh hot c ngha c bit i vi cuc
sng con ngi. Hin nay nc c kh trng bng kh clo, thng ha
tan kh clo vo nc (1g/l) tiu dit cc vi sinh vt.
Nc dng cho cc loi ni hi, v d trong nh my nhit in v
cho cc mc ch k thut khc, thng c tinh ch bng s dng nha
trao i ion. Kt hp nha trao i anion v nha trao i cation ngi ta
c th loi tr c hu ht cc cht tan di dng ion. Cht hu c v vi
khun cn tn ti trong nc nhng khng cn tr cho mc ch ny.
3. Tnh cht vt l
Nc l cht lng trong sut, khng mu, khng mi, khng v.
Lp nc su c mu xanh.
Khi lng ring ca nc 277,15K l 1g/cm
3
, cng l khi
lng ring ln nht; di v trn nhit ny khi lng ring ca
nc nh hn 1. Nguyn nhn gy ra hin tng ny l cc phn t nc
c khuynh hng kt hp vi nhau to thnh cc tp hp phn t ln, c
cng thc chung (H
2
O)
x
. Tp hp phn t ny ging nh nc c khi
lc ring b hn nc 277,15K. Gi tr x cho bit s phn t nc kt
hp li vi nhau. Gi tr ny s gim xung khi nhit tng, v vy khi
lng ring tng khi un nc t 273,15K ln 277,15K; tng tip nhit
vt qua 277,15K do gin n nhit ca nc, khi lng ring li
gim.
Nhit nng chy v nhit si ca nc tinh khit, bo ha
khng kh l nhng im mc trong thang nhit bch phn (Celsius).
Nhit nng chy ca nc quy nh bng O
0
C v nhit si ca
nc c quy nh bng 100
0
C p sut 101.32kPa (1atm).
Nc nguyn cht cs th lm lnh xung di 273,15K m vn
khng ha rn, l hin tng chm ng. Khi un nc nguyn cht
thn trng trong cc dng c tht sch, ngi ta cng c th a ln qu
nhit ny khi bt u si c s gii phng t ngt mt lng hi rt
ln lm tung te cht lng ra ngoi, i khi ph v c dng c un.
Trong thc t phng th nghim, khi un nc hoc cht lng, ngi ta
b vo cc un vi vin thy tnh hay min s nh trnh qu trnh si
t ngt nh trn.
Nc c s phn cc trong phn t
Nhng nghin cu chnh xc cho thy phn t nc c cu trc
gc. ng thng ni hai nguyn t hiro vi nguyn t oxi to thnh
mt gc khong 104,5
0
. Cu trc ny ng vi s lai ha sp
3
ca nguyn
t oxi theo thuyt lin kt ha tr (VB). Trong phn t nc, hai obitan
lai ha sp
3
ca oxi xen ph vi cc obitan lai ha cn li cha hai cp
electron t do ca oxi.

Cu trc phn t nc
Cu trc ny gy ra ra s phn cc ca phn t nc. Trong phn
t c s phn b lch cc trng tm in tch dng v m.
Xung quanh nguyn t oxi phn b nhiu in tch m. Xung
quanh cc nguyn t hiro phn b nhiu in tch dng. Qua trng
tm ca in tch dng v in tch m khng trng nhau nn phn t
nc c mt lng cc in. Lng cc in ca nc l nguyn nhn
20

ca s kt hp cc phn t nc thnh nhng tp hp ln bng lc ht
ca cc lng cc ngc du (c lin kt hiro na).
Mmen lng cc ca nc = 1,84D
4. Tnh cht ha hc
Lin k gia hiro v oxi trong phn t nc rt bn; mun ph v
lin kt ny phi dng nng lng kh ln. Nng lng c th l nhit
nng, in nng v ha nng.
- Dng ha nng: v d nc tc dng vi kim loi v phi kim.
- Dng in nng: v d in phn nc.
- Dng nhit nng: ph v lin kt ca nc to thnh cc
nguyn t bng nhit nng ch thc hin c nhit cao v khng
hon ton. 2273K v p sut bnh thng ch c 2% hi nc b phn
hy thnh hiro v oxi. C th ni nc l mt hp cht rt bn.
Nc va c tnh oxi ha va c tnh kh; oxi trong phn t nc
c s oxi ha -2 v hiro c s oxi ha +1. Nhng cht oxi ha mnh v
nhng cht kh mnh khng tn ti trong nc m tc dng vi nc
gii phng hiro hoc oxi. Nhng cht oxi ha trung bnh v cht kh
trung bnh phn ng vi nc nhit cao theo phng trnh phn ng
thun nghch.
Trong cc cht oxi ha dng n cht ch c flo phn ng hon
ton vi nc nhit thng
F
2
+ H
2
O 2HF +1/2O
2

Cc halogen khc cho phn ng thun nghch
Cl
2
+ H
2
O HCl + HClO
Tuy nhin clo cng phn ng vi nc gii phng oxi
Cl
2
+ H
2
O 2HCl + O
Phn ng ny ch xy ra khi c tc dng ca nh sng mt tri. V
vy loi trl tc dng ca nh sng, nc clo thng c bo qun
trong cc chai, l mu. Oxi mi sinh phn ng ny c tnh cht hot
ng ha hc mnh, nn kh clo m oxi ha mnh hn kh clo kh.
Cc cht kh nh photpho, cacbon, silic, bo phn ng thun nghch
vi nc nhit cao.
Cc kim loi kim, kim th phn ng mnh vi nc nhit
thng.
Nhm v magie ang chy c th chy tip trong hi nc.
Cc kim loi chuyn tip nh st, km, niken, coban, mangan,
crom tc dng vi nc nhit cao bng phn ng thun nghch.
Nc cn tham gia cc phn ng hirat ha v cc phn ng thy
phn.
5. S nhim mi trng nc. Cch x l nc thi
a. S nhim mi trng nc
Nh cp trn, nc ngt ch chim mt phn nh ca ton
b lng nc trn qu t. Nc ngt xut hin do s bc hi nc t
cc i dng, t sng sui ao h trn lc a v t s thot hi nc ca
l cy; hi nc tch t li trong khng kh, lu chuyn qua nhng vng
rng ln v ngng t li di dng ma, tuyt ri, ma . Nc di
cc dng trn ri xung b mt qu t chy thnh sng, tch t li trong
cc h ao hoc ti nc ngm. Nc t cc con sng li chy ra i
dng v qu trnh bc hi li lp li nh trn.
Nc ngt trong thin nhin cha nhiu tp cht di dng kh ha
tan nh CO
2
, N
2
, O
2
cng nh nhiu cation v anion nh Na
+
, K
+
,
Mg
2+
, Ca
2+
; Cl
-
, SO
4
2-
, HC ngoi ra cn c huyn ph ca cc
cht rn, v d cc tiu phn t st.
21

Mi trng nc nh trn cha phi l nhim. Tuy nhin mi
trng nc c th b nhim do cc loi nc thi cng nghip, nc
thi t cc phng th nghim, nc thi t cc khu dn c, nh hng,
bnh vin chy vo cc sng sui, knh rch, m h. Ngoi ra cc
cht c hi nh thuc tr su, thuc dit c, thuc kch thch tng
trng c phun trn ng rung cha phn hy ht b nc ma
cun theo chy vo cc sng, h v vo cc i dng gy nhim
mi trng mang tnh ton cu.
Con ngi gy nhim mi trng trc ht l t hi mnh.
chng nhim mi trng nc, ngi ta cn phi thn trng trong vic
dng thuc bo v thc vt v x l nc thi trc khi cho chy vo mi
trng.
b. Cch x l nc thi
X l nc thi c th c tin hnh theo ba bc, ty thuc vo
cu trc, cng sut ca cng trnh x l v kh nng ti chnh ca c s
sn xut, x nghip, bnh vin.
Bc th nht
Ngi ta x l nc thi bng phng php c hc. u tin cho
nc thi chy qua li lc tch cc thnh phn rn th. Sau nc
thi c cho chy vo b lng, trong cc huyn ph rn lng ng li
thnh dng bn. Nu nc thi qua x l bc mt m khng iu
kin x l tip th ngi ta cho chy vo b cha v x l vi clo trc
khi thi vo sng h ha nhp vo ngun nc t nhin. X l nc
thi bc ny c th loi b c 60% cht rn dng huyn ph v
35% cht thi hu c.
Bc th hai
X l nc thi bng phng php sinh hc. V mt k thut, thc
hin bc hai ny l phn hy cc cht hu c nh cc vi khun a kh
trong cc b x l sinh hc.
Nc thi c s l qua bc th nht (cha x l clo) c dn
vo cc b x l sinh hc v c sc khng kh lin tc. Qu trnh sc
khng kh vo b dn n vic tng trng rt nhanh cc vi khun a kh,
v chng c nui dng bng cc cht thi hu c trong nc, c
ngha l chng phn hy, lm tiu tan cc cht hu c.
Cc cht hu c b phn hy tng nc theo mt dy cc phn ng
phc tp do vi khun gy ra. Cc thnh phn cu to hp cht hu c nh
cacbon, hiro, oxi, nit, lu hunh, photpho c oxi ha thnh CO
2
,
H
2
O, N , v cc loi ion photphat.
Nu khng sc khng kh th qu trnh oxi ha vi sinh ny lm cn
kit ngun oxi trong nc v lm cho cc vi khun a kh khng tn ti
c. S tit dit ca vi khun a kh do thiu oxi s chuyn giao vai tr
phn hy cht hu c cho loi vi khun ym kh va xut hin. Qu trnh
ny s hnh thnh cc kh CH
4
, NH
3
, H
2
S, v PH
3
thy v tr ca cc sn
phm oxi ha (CO
2
, H
2
O, N , ). Cc cht kh ny gy ra mi
hi thi ca ngun nc nhim.
Cc vi sinh vt a kh cng vi bn lng to thnh mt khi bn vi
sinh. Khi bn ny lng xung y b cha. Phn nc trong cho chy
vo b x l clo trc khi cho chy vo ngun nc t nhin trong sng,
h nu nh qu trnh x l nc thi dng bc th hai.
Phn ln bn vi sinh chy sang b cha ng thi l b lng sau
bc th hai c a tr li b x l vi sinh. Bng cch ny, cc vi sinh
vt cha trong bn tip tc pht huy tc dng phn hy cc cht hu c
trong nc thi va mi chy ti.
22

Qua hai bc x l trn ngi ta c th loi b c 90% cht rn
dng huyn ph v 90% cht hu c c th phn hy c bng vi sinh.
Bc th ba
Nc thi qua x l bc th nht v th hai vn cn cha mt
lng ln cc hp cht cha nit v photpho. Cc thnh phn ny cn
gy ha ln cho ngun nc t nhin, v chng to ra s pht trin qu
mc ca cc loi to. Ngoi ta qua hai bc x l trn, nhiu ha cht c
hi vn khng b nh hng g. Chng cn tn ti nguyn trng trong
nc x l khi chng ta cho chy vo sng, h. Bi vy ngi ta cn
n bc x l nc thi th ba, l bc dng phng php ha hc. Cc
ha cht c dng loi b nhng cht c hi c ngun gc hu c
v kim loi nng trong nc thi khi pht hin c qua phn tch. Thc
hin bc th ba rt tn km, gi thnh rt cao khi phi dng ha cht
loi b cc cht c hi k trn. Do vy ch nhng trng hp c bit
nc thi mi c x l thm bc th ba.
6. Nc nng (D
2
O)
Hp cht quan trng ca teri l nc nng, c khi lng phn
t M = 20. Nc nng chim 0,01146% nc bnh thng, v vy khi
iu ch hiro bng phng php phn hy nc lun lun c mt lng
rt nh teri. Khi in phn nc, qu trnh kh in tch ion hiro nh
d dng hn kh in tch dng ion teri. Bi vy hiro c gii
phng c thnh phn phn trm hiro nh nhiu hn so vi nc, trong
khi trong bnh in phn tp trung nc nng. Bng cch ny ln u
tin vo nm 1933 Liut (Lewis) iu ch c nc nng vi 20 lit
nc em in phn cho n khi cn li 0,3 cm
3
.
Trong cng nghip iu ch mt lng ln nc nng, ngi ta
s dng phn cht lng cn li ca b in phn nc s dng trong
mt thi gian di, v khi trong b s tch t li mt lng ln nc
nng.
Vic tch ly, lm giu teri cng c th tin hnh bng phng
php khc, qua c th iu ch c nc nng t cc nguyn t
tng ng.
Ngoi nc nng D
2
O trong nc cn c HDO, do c cn bng
H
2
O + D
2
O 2HDO
Hng s cn bng ca phn ng K = 3,87 373K.
Khi ct thnh th hi, HDO thng b phn hy thnh H
2
O v
D
2
O. Ngoi cc ng v ca hiro, oxi cng c cc ng v bn:

Nn trong nc phi tn ti cc phn t:
H
2
16
O, D
2
16
O, H
2
17
O, D
2
17
O, H
2
18
O, D
2
18
O, HD
16
O, HD
17
O,
HD
18
O.
Nh vy trong nc bnh thng tn ti chn loi phn t khc
nhau, c bn gn nh nhau.
Nc nng rt cn trong cc l phn ng ht nhn; n c vai tr
lm cht hm tc cc ntron nhanh xung bng tc chuyn ng
nhit ca cc cht kh. Cc ntron c tc ny c gi l cc ntron
nhit. Ntron nhit mi c tc dng to ra cc phn ng ht nhn iu
ch cc ng v phng x.
7. Hiro peoxit
a. c im chung
Tena (Thnard) pht hin ra hiro peoxit vo nm 1818, l mt
peoxit quen thuc nht v c s dng rng ri nht. Lin kt c trng
trong phn t hiro peoxit l lin kt dy oxi (-O-O-) bi s hnh thnh
23

phn t hiro peoxit theo nguyn tc chung l s kt hp phn t oxi vi
hai nguyn t hiro theo phn ng
2H + O
2
H
2
O
2
b. Cc phng php iu ch hiro peoxit thng dng
- Trong phng th nghim ngi ta iu ch hiro peoxit bng cch
cho axit tc dng ln cc peoxit ca kim loi kim v kim th, phn ln
dng bari peoxit
BaO
2
+ H
2
SO
4
BaSO
4
+ H
2
O
Kt ta bari sunfat c lc ra c th dung dch H
2
O
2
.
Trong cng nghip, ngi ta thng dng phng php in phn
axit sunfuric v phng php oxi ha mt s hp cht hu c bng kh
oxi hoc khng kh.
- Phng php in phn axit sunfuric
Khi in phn dung dch axit sunfuric 50% vi mt dng in
ln, cc ion sunfat s phn ng ant theo phng trnh:
2S S
2
Qu trnh ny to thnh ion peoxitisunfat.
Axit peoxitisunfuric tc dng vi nc cho hiro peoxit v axit
sunfuric
H
2
S
2
O
8
+ 2H
2
O 2H
2
SO
4
+ H
2
O
2

in phn mui hirosunfat ca cc kim loi kim cng cho ra axit
peoxiisunfuric
HS H
2
S
2
O
8
+ 2e
Phng php oxi ha hiroquinon hay ankylhiroquinon bng oxi
khng kh. Phn ng c thc hin trong pha lng, v d

Dung dch H
2
O
2
thu c trong phng php antrahiroquinon ny
c nng khon 20%. Nguyn liu ch yu c dng trong qu trnh
iu ch l oxi trong khng kh, hiro v nc. Bi vy gi thnh H
2
O
2

thp hn so vi phng php in phn.
Quinon li c kh bng hiro c hiroquinon vi cht xc tc
l palai.
- Phng php th ba l dng isopropanol c oxi ha thnh
axeton v H
2
O
2


Cc phng php trn ch c th thu c dung dch long hiro
peoxit. Bng cch ct phn on chn khng c th to ra c dung
dch hiro peoxit c nng cao hn. Dung dch hiro peoxit 30% trn
th trng c tn l pehiron.
- Phng php mi hn dng tng hp hiro peoxit c nng
cao t hiro v oxi da trn c s phng in m cao tn.
c. Tnh cht ca hiro peoxit
- Tnh cht vt l
24

Hiro peoxit tinh khit l mt cht lng, khng mu, snh. Khi
lng ring 273K l 1,47 g/cm
3
, nng chy 272K.
Nhit si ca hiro peoxit khong 428,5K p sut 101,325
kPa. y ch l nhit ngoi suy v trc khi t nhit ny, hiro
peoxit b phn hy v nhit.
Cu trc phn t ca H
2
O
2
trn c s nghin cu bng tia X v cc
loi quang ph khc c a ra hnh sau:

di lin kt O-O- bng 148pm, di lin kt O-H bng
101pm. Momen lng cu ca phn t H
2
O
2
l 2,13D v hng s in
mi l 89 273K. Bi vy, H
2
O
2
l dung mi ion ha i vi nhiu cht.
Mt s tnh cht vt l quan trng ca hiro peoxit v nc
Hp cht Khi lng
Ring (g/cm
3
)
Nhit
nng chy (K)
Nhit si
101,325kPa
H
2
O
2
1,471 272 428,5
H
2
O 1,0000 273 373
Hiro peoxit cng c th hnh thnh peoxihirat vi cc mui
ging nh nc, v d vi K
2
CO
3
to thnh K
2
CO
3
.H
2
O
2
. Mui ny c
dng trong bt git.
S phn li ca hiro peoxit
Trong dung dch long hiro peoxit phn li:
H
2
O
2
H
+
+
Hng s phn li nhit thng l:

H
2
O
2
phn li mnh hn nc, l mt axit rt yu. Cc peoxit ca
kim loi nh Na
2
O
2
, BaO
2
, v.v l mui ca hiro peoxit.
Tnh cht ha hc:
+ Hiro peoxit d dng b phn hy to thnh nc v oxi
H
2
O
2
H
2
O + 1/2O
2
;
Tc phn hy tng ln khi c xc tc. Cc cht xc tc c th l
ion kim loi hay cc ht bi. Platin phn tn nh l mt cht xc tc
mnh trong qu trnh phn hy H
2
O
2
. Than hot tnh v b mt g gh
ca thy tnh cng l cht xc tc phn hy H
2
O
2
.
loi tr s phn hy do xc tc khi lu gi hiro peoxit c nng
cao cn dng chai l c trng parafin; ngy nay ngi ta dng l nha
polietilen hoc cng c th cho thm cht lm n nh dung dch H
2
O
2
;
y l nhng cht c tc dng lm mt hiu lc ca cc cht xc tc phn
hy H
2
O
2
, chng hn nh ur, natri pirophotphat.
+ Hiro peoxit cng c th b phn hy theo phng trnh:
H
2
O
2
H
2
+ O
2
; H
0
= +190,26 kJ/mol
Tuy nhin qu trnh ny l qu trnh thu nhit nn ch xy ra
nhit cao.
+ Hiro peoxit c tnh kh khi tc dng vi cht oxi ha mnh
hn, v d H
2
O
2
tc dng vi dung dch KMnO
4
trong mi trng axit
hay tc dng vi clorua vi
2KMnO
4
+ 5H
2
O
2
+ 3H
2
SO
4
K
2
SO
4
+ 2MnSO
4
+ 8H
2
O + 5O
2
25


CaCl(Ocl) + H
2
O
2
CaCl
2
+ H
2
O + O
2

Phn ng ny c th dng iu ch oxi trong bnh kp.
+ Hiro peoxit c tnh cht oxi ha khi tc dng vi cht kh. V
d H
2
O
2
oxi ha ch sunfua thnh ch sunfat hay oxi ha KI trong mi
trng axit thnh iot
PbS + 4H
2
O
2
PbSO
4
+ 4H
2
O
2KI + H
2
O
2
+ H
2
SO
4
K
2
SO
4
+ 2H
2
O

+ I
2

d. ng dng
Da vo tnh oxi ha, ngi ta dng hiro peoxit ty mu v st
trng. Tnh oxi ha c coi l ca nguyn t oxi mi sinh trong qu
trnh phn hy hiro peoxit. Oxi nguyn t ny c tnh hot ng ha hc
cao ph hp ty mu bng, si, m tng hp, du thc vt.
Dung dch hiro peoxit 3% dng lm thuc st trng; hiro peoxit
m c dng lm thuc phng ng li, lm cht oxit ha trong nhin
liu cc tn la iu khin iu chnh ng bay ca tn la chnh. S
d H
2
O
2
t c dng lm cht oxi ha trong nhin liu tn la chnh v
sn phm oxi ha l nc khng thun li cho lc y ca nhin liu.


Tit 15 KIM TRA
A. MC TIU:
Nm c s khc bit gia phi kim u nhm v cc phi kim cn
li. Nguyn tc chung iu ch hiro trong cng nghip v bng nhng
phng php no ngi ta iu ch c hiro trong cng nghip. Nm
c tnh cht oxi ha kh ca H
2
O
2
, tnh oxi ha mnh ca O
3
. Gii
thch cu trc phn t nc theo phng php MO.
B. NI DUNG:
Cu 1: (2 im)
Cacbon v silic u phn nhm chnh nhm bn trong bng h
thng tun hon cc nguyn t ha hc (C: z = 6; Si: z = 14). Trong thin
nhin cacbon c hai dng th hnh l kim cng v than ch. Trong khi
silic iu kin tng t ch hnh thnh dng tinh th ging nh kim
cng. Anh ch hy gii thch ti sao c s khc nhau .
Cu 2: (3 im)
a. Nguyn tc chung ca phng php iu ch hiro trong cng
nghip?
b. Trong cng nghip hiro c iu ch bng nhng phng
php no v c dng lm g?

Cu 3: (3 im)
Gii thch ti sao H
2
O
2
va c tnh oxi ha va c tnh kh. Mi
tnh cht ly 5 phn ng lm v d?
Cu 4. (2 im)
a. Ly 5 v d chng t O
3
(ozon) c tnh oxi ha mnh hn O
2

(oxi)?
b. Hy trnh cu trc phn t H
2
O theo quan im ca phng
php obitan phn t (MO); phn t nc c t tnh khng?

p n
Cu 1: (2 im)
Cacbon l nguyn t u nhm VIA chu k 2 c kh nng hnh thnh
lin kt tt hn cc nguyn t cn li ca nhm. Chnh v th trong
kim cng cc nguyn t cacbon ch hnh thnh lin kt ; trong than ch
26

cc nguyn t cacbon hnh thnh c lin kt . Lin kt
c hnh thnh do c s xen ph gia cc obitan p khng tham gia lai
ha to lin kt . Trong khi silic iu kin tng t ch hnh
thnh dng tinh th ging nh kim cng vi cc lin kt Do lin kt
gia cc nguyn t silic vi nhau km bn nn silic khng th c dng
th hnh ging than ch.
Cu 2: (3 im)
a. Tt c cc phng php sn xut hiro trong cng nghip u
da vo s phn hy nc v phn hy cc hp cht hu c.
0.5

b. Ph bin nht l phng php iu ch kh than t: Trong l
phn ng xy ra phn ng gia hi nc v than cc nung to ra hiro
v cacbon oxit

- Thc t ngi ta nhn c mt hn hp kh gm cacbon
monooxit (CO), cacbon ioxit (CO
2
), hiro v hi nc. Thnh phn c
th thng nh sau: 45% H
2
, 45% CO, 5% CO
2
v 5% H
2
O
(h)
.
0,25

c nhiu kh hiro v loi b kh CO cn thc hin chuyn ha
CO thnh CO
2
bng cch cho kh cacbon monooxit tc dng vi hi
nc c cht xc tc ph hp



0,25

Kh CO
2
c loi b d dng bng cch ha tan vo nc di p
sut ln.
0,25

- Kh thot ra t l ch bin than cc cng l ngun cung cp
hiro. Kh l cc c thnh phn sau: 50% H
2
, 30% CH
4
, 8% CO v mt
s hp cht khc.
Bng cch lm lnh hn hp kh, ngi ta c th loi CH
4
v CO
2

ra khi hn hp, cn kh CO c chuyn thnh CO
2
c s tham gia ca
cht xc tc nh trn v loi ra khi hn hp. Cui cng phng php
ny to ra c ngun kh hiro cng nghip.
0,25

- iu ch hiro t kh metan, thnh phn chnh trong kh t thin
nhin. Ngi ta cho kh metan tc dng vi hi nc nhit 1373K.
0,25

0,25

Sn phm ph ca qu trnh ch bin du m.
0,25

Kh hiro cng nghip tinh khit nht c th iu ch bng in
phn nc. Thng ngi ta pha thm baz c th dng in cc
niken thay cho in cc platin rt t tin.
0,25

Hiro cng l sn phm ph trong qu trnh in phn dung dch
mui n hay kali clorua iu ch NaOH hay KOH.
0,25

27

ng dng: Hiro c s dng hng t m
3
/nm trong cng nghip.
Khong 2/3 lng ny c dng tng hp NH
3
, phn cn li c
dng trong tng hp hu c nh tng hp cc loi ru, tng hp xng
nhn to, v.v Mt phn nh hiro c dng trong hn hi.
0,25

Cu 3. (3 im)
a. Oxi trong H
2
O
2
mc oxi ha -1. Nn n c th nhn thm 1e
na c mc oxi ha -2 th hin tnh oxi ha. Ngoi ra oxi (-1) cn c
kh nng mt electron tr v mc oxi ha 0 th hin tnh kh. 0,5

5 phn ng H
2
O
2
th hin tnh oxi ha:
H
2
O
2
+ KNO
2
H
2
O

+ KNO
3
0,25

H
2
O
2
+ 2KI I
2
+ 2KOH 0,25

PbS + 2H
2
O
2
PbSO
4
+ 4H
2
O 0,25

2KI + H
2
O
2
+ H
2
SO
4
K
2
SO
4
+ 2H
2
O

+ I
2
0,25

3H
2
O
2
+ 2NaCrO
2
+ NaOH Na
2
CrO
4
+ 4H
2
O 0,25

5 phn ng H
2
O
2
th hin tnh kh:
Ag
2
O + H
2
O
2
2Ag + H
2
O + O
2
0,25

5H
2
O
2
+ 2KMnO
4
+ 3H
2
SO
4
2MnSO
4
+ 5O
2
+ K
2
SO
4
+ 8H
2
O 0,25

CaCl(OCl) + H
2
O
2
CaCl
2
+ H
2
O

+ O
2
0,25

NaClO + H
2
O
2
NaCl + H
2
O + O
2
0,25

2H
2
O
2
O
2
+ 2H
2
O 0,25

Cu 4: (2 im)
a. Cc phn ng chng t O
3
c tnh oxi ha mnh hn O
2
:
2Ag + O
3
Ag
2
O + O
2
0,25

2KI + O
3
+ H
2
O I
2
+ 2KOH + O
2
0,25

PbS + 4/3O
3
PbSO
4
0,25

NaS + 4/3O
3
NaSO
4
0,25

O
3
O

+ O
2
0,25

b. Theo phng php obitan phn t th phn t nc c cu hnh
lectron nh sau:
2H[1s
2
] + O[K2s
2
2p
4
] H
2
O[K ] 0,25

S nng lng: 0,25

Phn t nc c 2 lin kt khng c e c thn nn phn t c
tnh nghch t. 0,25

28

CHNG 3: CC NGUYN T NHM VIIIA (KH HIM) 2(2,0)
A. MC TIU:
1. V tr trong bng tun hon, cu trc electron, bn knh nguyn t, nng lng ion
ho th nht .
2. Trng thi thin nhin v phong php tch ring cc kh him.
3. Tnh cht l- ho hc v ng dng.
B. NI DUNG:
Tit 16, tit 17(t hc)
1. Tnh cht chung
Cc kh him thuc nhm VIIA, i khi cn gi l nhm 0 ca
bng tun hon cc nguyn t ha hc. Cc kh him c xp vo cc
nguyn t phi kim. Nhm VIIIA gm cc nguyn t: heli, neon, agon,
kripton, xenon v raon.
c im ni bt ca cc nguyn t ny l tr v mt ha hc, do
c cu trc c bit ca lp electron ngoi cng, c th l tnh tr ca cu
hnh electron 1s
2
nguyn t heli v cu trc ns
2
np
6
cc nguyn t kh
him khc, bi vy cc kh him trc y c gi l cc kh tr.
Cc kh him tn ti di dng n nguyn t. Cc phn t kh
him gi nh nh He
2
, Ne
2
, v,v theo thuyt obitan phn t (MO)
khng th tn ti, v s electron in vo cc obitan phn t lin kt bng
s electron in vo cc obitan phn t phn lin kt. iu ny cng th
hin nng lng ion ha th nht (I
2
) rt cao. Mt s i lng vt l c
lin quan c cp bng sau:
Mt s i lng vt l ca cc nguyn t nhm VIIIA:
Cc i lng vt l He Ne Ar Kr Xe Rn
Bn knh nguyn t
(pm)
93 112 154 169 190 220
Nng lng ion ha
I
1
(kJ/mol)
2381 2088 1526 1355 1175 1041
2. S pht hin ra cc kh him
Cavenis (Cavendish) l ngi a ra cc ch dn u tin v s
tn ti ca cc kh him. Vo nm 1785 ng cho bit: trong khng kh,
ngoi nit cn c cc kh him khc, phn bit vi nit trong tnh tr ha
hc nh khng tc dng vi oxi trong qu trnh phng in. Nm 1894
Railai (Rayleigh) v Rmxay (Ramxay) pht hin ra agon qua nghin cu
s khc nhau v khi lng ring ca kh nit c iu ch t khng
kh v t amoni nitrit. Nm 1898 Rmxay tm ra neon, kripton v xenon
bng phn tch quang ph. Kh him nh nht l heli c pht hin
trong qung cleveit. Thc ra s tn ti ca heli trn mt tri c xc
nh bng phng php quang ph t nm 1868, nhng khi cha pht
hin c nguyn t ny trn qu t, v vy thi c t tn l
nguyn t mt tri theo ting Hi Lp helios l mt tri. Nm 1882
Panmiri (Palmieri) tm thy heli trong nham thch, c l n c to
thnh do phn r phng x ca rai. Mi n nm 1895, Rmxay mi
khng nh c kh mt tri v kh thu c t qung cleveit l mt.
Kh him cui cng v nng nht c Rudpho (Rutherford) pht hin
vo nm 1899 trong qu trnh phn r phng x thori v rai, do vy
c t tn l raon.
3. Trng thi t nhin
- Trong khng kh
Theo nhng thng tin mi nht th khng kh c cha mt lng
kh him nh sau theo phn trm th tch (% th tch):
Heli 0,00046%
29

Neon 0,00161%
Agon 0,9325%
Kripton 0,000108%
Xenon 0,000008%
Raon c lng rt nh, l nguyn t phng x vi chu k bn r
ngn.
Chng hn, ly mt khng gian c chiu di 10 mt, chiu rng 10
mt v chiu cao 5 mt (cha 500m
3
khng kh) theo s liu trn s c 2
lt heli, 8 lt neon, 4500 lt agon, 0,5 lt kripton v 0,04 lt xenon p sut
kh quyn bnh thng. Nh vy agon khng phi l nguyn t him. Ty
theo cu to t ca tng vng c cha nhiu hay t rai v thori, khi
phn r ht nhn cc nguyn t ny s to ra nhiu hoc t nguyn t
raon phng x. V raon l cht kh phng x ln trong khng kh, n c
th xm nhp vo c th ngi bng con ng h hp nn rt nguy him
cho sc khe ca c dn vng c raon nng cao.
- Trong kh t t nhin
Heli cn c trong cc m kh t. C nhng m kh t ngho heli,
hm lng heli chim t 0,01 n 0,1% nh cc m kh t chu u,
nhng cng c nhng m kh t giu heli, lng heli chim trn 1% tr
ln, v d cc m kh t M. T cc ngun kh t giu heli c th iu
ch hng trm nghn tn heli mi nm.
- Trong cc khong cht
Trong cc khong cht phng x, heli l sn phm ca qu trnh
phn r phng x. Khi nghin nh khong cht, un nng ln hoc ha
tan vo axit heli s thot ra ngoi v c th thu c.
4. iu ch
a. T khng kh
Nu mun tch kh him ra khi khng kh, trc ht phi loi b
nhng thnh phn chnh ca khng kh, ch yu l nit v oxi. Qu trnh
ny c th thc hin bng hai phng php: phng php ha hc v
phng php vt l.
Phng php ha hc c dng iu ch kh him trong phng
th nghim, cn phng php vt l c dng sn xut kh him trong
cng nghip.
- iu ch trong phng th nghim
u tin khng kh c loi b hi nc v kh cacbonic, sau
tch oxi bng cch dn khng kh qua bt ng nung
2Cu + O
2
2CuO
v tch nit bng cch cho tc dng vi magie hay canxi nung nng
3Mg + N
2
Mg
3
N
2

C th loi b oxi v nit bng mt ha cht duy nht l canxi
cacbua (CaC
2
). nhit cao, oxi phn ng vi canxi cacbua to thnh
canxi oxit v cacbon
2CaC
2
+ O
2
2CaO + 4C
V nit phn ng vi canxi cacbua to thnh canxi xyan v cacbon
CaC
2
+ N
2
CaCN
2
+ C
Hn hp kh him c iu ch bng mt trong hai cch trn
c gi l agon th, v trong thnh phn ca c c 99,8% agon v ch c
0,2% th tch hn hp cc kh him khc.
- iu ch trong cng nghip
30

Trong cng nghip kh him c iu ch t khng kh bng
phng php ha lng khng kh v ct phn on khng kh lng.
Da vo nhit si khc nhau ca cc nguyn t, ngi ta tch
khng kh lng thnh cc phn on th nh hn hp heli-nit, hn hp
neon-nit, hn hp agon-nit, oxi tinh khit, hn hp oxi-kripton v hn
hp oxi-xenon. Cc hn hp ny li l nhng cht ban u iu ch
cc kh him tnh khit.
b. T kh t
Heli c th c iu ch t kh t. Kh t dn t m du ln
c nn qua nc di p sut ln v sau sc vo nc vi ra
ht kh cacbonic. Kh c ra sch nh trn, c lm lnh n
68,15K bng phng php nn v dn hi nhiu ln. nhit ny, kh
heli khng ha lng v c a ra ngoi vi tinh khit 97 98%,
trong cn ln t 2 - 3% kh nit.
c. T cc khong cht
iu ch heli trong phng th nghim tt nht l nung nng cc
khong cht c cha heli nh cleveit (U
3
O
8
), monazit (LnPO
4
,
Th
3
(PO
4
)
4
), thorianit (ThO
2
) ln nhit trn 1273K.
5. Tnh cht vt l
Cc kh him l nhng kh khng mu, khng mi. Chng c nhit
ti hn thp v rt kh ha lng, v cc kh him hot ng ha hc
km nn gia cc nguyn t ch c tng tc yu ca cc lc Van ec
Van (Van der Waals).
Mng tinh th ca cc kh him l mng nguyn t, c cu trc lp
phng tm mt. Ngoi ra heli cn c dng th hnh vi cu trc lp
phng tm khi.
Mt s tnh cht vt l ca kh him c tm tt trong bng:

6. Tnh cht ha hc
Cc kh him trc y c coi l tr v mt ha hc. iu ny
c gii thch bng cu hnh electron nguyn t bn ngoi ca chng
s
2
p
6
l cu hnh bn, tr heli c cu hnh s
2
.
Hp cht ha hc u tin ca cc kh him c iu ch vo
nm 1962 do Nai Balit (Neil Bartlett) khi cho platin hexafloro tc dng
vi xenon. Phn ng ny to ra hp cht xenon hexafloroplatinat (V)
Xe[PtF
6
]. Mt thi gian sau, hp cht xenon
hexaflororoiat (III) Xe
3
[RhF
6
] cng c iu ch. Trong nhng nm
1962, 1963 cc nh nghin cu M thnh cng trong vic tng hp cc
cht ca cc kh him trc tip t cc nguyn t, v d t flo v xenon
hay t flo v kripton, hoc flo vi raon di p sut. H iu ch
c cc florua ca cc kh him nh XeF
6
, XeF
4
, XeF
2
; KrF
4
; RnF
x
.
- Xenon hexaflorua (XeF
6
)
Xenon hexaflorua l cht rn, hnh thnh nhng tinh th khng
mu, c nhit nng chy 311K. nhit bnh thng 298K, hp
cht ny c p sut hi l 3,99kPa. Phn t c cu to theo hnh bt
din, ging nh trng hp ca hp cht uran hexaflorua UF
6
.
Xenon hexaflorua thy phn trong nc nhng khng hnh thnh
xenon t do. Khi cho cht kh vo dung dch mi c s xut hin xenon
t do, c th sn phm trung gian l xenon hiroxit:
XeF
6(r)
+ H
2
O
(l)
XeF
4(l)
+ 2HF
(k)

XeF
6(r)
+ 3H
2
O
(l)
XeO
3aq
+ 6Hfaq
- Xenon tetraflorua c iu ch t xenon v flo di p sut
nhit 673K, l cht rn thng hoa khng b phn hy. Hp cht xenon
31

tetraflorua b thy phn khi ha tan vo nc. Phn ng ny dn n
phn hy hp cht v gii phng oxi
XeF
4(n)
+ 2H
2
O
(l)
Xe
(k)
+ 4HF
(k)
+ O
2

Xenon tetraflorua tc dng vi dung dch kali ioua gii phng iot
XeF
4(n)
+ 4I
-
(dd)
Xe
(k)
+ 2I
2
+ 4F
-

- Xenon iflorua (XeF
2
)
Xenon iflorua c iu ch trc tip t xenon v flo, phn t
ny c cu to thng. di lin kt gia Xe v F l 214pm.
- Kripton tetraflorua (KrF
4
)
Kripton tetraflorua c iu ch bng cch cho phng in qua
hn hp kripton v flo nhit thp. Kripton tetraflorua km bn hn
xenon tetraflorua.
- Raon florua
Ngi ta cng iu ch c raon florua c thnh phn RnF
x
, tuy
nhin cha xc nh c chnh xc thnh phn ca hp cht.
Gii thch v lin kt ha hc trong cc hp cht kh him i hi
phi c kin thc v thuyt obitan phn t vi s tham gia lin kt ca
cc electron d.
7. ng dng
Kh him c mt s ng dng hn ch.
Heli c dng np kh cu thay cho kh hiro rt d chy. Heli
cn khuch tc chm hn nhiu so vi hiro qua lp v bc. Sc nng
ca heli khng th tnh bng mt na ca hiro theo khi lng ca
chng. Trong trng hp ny s chnh lch khi lng gia khng kh
v cht kh np vo kh cu lp thnh t l so snh. T l ca hai hiu
s l:

Nh vy sc nng ca kh cu khi np kh heli ch gim i 8% so
vi khi np kh hiro. Heli cn dng np vo cc nhiet k kh; heli
lng dng to nhit thp trong cng ngh v nghin cu khoa hc.
Heli v agon l nhng kh him c nhiu trong khng kh v trong
kh t t nhin. Hai kh ny c iu ch s dng lm mi trng
tr khi nung chy v hn mt s kim loi nh ziriconi, titan v.v v
dng lm bu kh quyn tr trong cc thit b nghin cu vt l v ha
hc.
Neon ch yu c dng trong cng nghip sn xut n ng (n
neon) thp sngv trang tr, qung co, v ch cn mt in p ion ha
thp cng kch thch pht sng.
Agon c dng np cc u o Gaige Mul (Geiger Muller)
trong nghin cu cc ng v phng x v cc phn ng ht nhn.
Agon v kripton dng np vo cc bng n in, v cc kh ny
dn in km hn nit thng c dng trc y. S thay th ny hn
ch c s bc hi ca si vonfram trong bng n, do duy tr c
nhit cao v t hiu qu chiu sng tt.


Chng 4: CC NGUYN T NHM VIIA ( HALOGEN) - 13

A. MC TIU:
1. V tr trong bng tun hon, cu trc electron, bn knh nguyn t, nng lng ion
ho, i lc electron, m in, trng thi oxi ho, th in cc chun ca cc halogen.
2. Trng thi thin nhin v thnh phn cc ng v.
32

3. Phng php iu ch.
4. Tnh cht l- ho hc v ng dng cc halogen.
5. Cc hiro halogen v cc axit tng ng. Tnh cht v ng dng.
6. Cc halogenua ion v halogenua cng ho tr.
7. Oxit ca cc halogen.
8. Oxiaxit ca cc halogen v cc mui tng ng.
B. NI DUNG:

Tit 18 (t hc)

Bi 1. TNH CHT CHUNG CA CC HALOGEN

A. MC TIU:
Tnh cht chung ca cc halogen.
B. NI DUNG:
Cc halogen thuc nhm VIIA trong bng tun hon cc nguyn t
ha hc gm flo; clo; brom; iot; atatin.
Nguyn t nng nht l atatin. Atatin c trong t nhin l thnh
phn trung gian ca cc dy phng x t nhin v cng c th iu ch
nhn to bng phn ng ht nhn.
Trong bng tun hon cc nguyn t ha hc, halogen ng ngay
trc cc kh him. V tr ny quyt nh tnh cht ha hc ca cc
nguyn t halogen. Tt c cc nguyn t halogen u c by electron
lp ngoi cng (ns
2
np
5
). Do vy cc nguyn t ny th hin tnh m in,
chng d dng nhn mt electron to lin kt ha hc c cu hnh
electron cc kh him (ns
2
np
6
). iu ny th hin qua i lc electron ca
chng. i lc electron v mt s i lng vt l khc ca cc halogen
c a ra bng sau:
Mt s i lng vt l c trng ca cc nguyn t nhm VIIA
i lng c trng F Cl Br I At
Bn knh nguyn t (pm) 72 100 115 140
Bn knh ion X
-
(pm) 133 181 196 217
Nng lng ion ha I (kJ/mol) 1,68.10
3
1,25.10
3
1,14.1
0
3

1,01.10
3


i lc electron (kJ/mol) +332 +349 +325 +295
m in 4 3.2 3,0 2,7
Nng lng phn li lin kt X-X
(kJ/mol)
155 242 193 151
Th in cc chun (V)
Qua trnh: 1/2X
2
(aq) + e = X
-
(aq)
2,87 1,36 1,07 0,54
Xu th to thnh ion m n l c im ni bt cho ton nhm
halogen. i lc electron l hiu ng nng lng xut hin khi hnh thnh
anion halogen v t nguyn t halogen trung ha in kt hp vi mt
electron. i lc electron ca cc halogen ln hn i lc electron ca tt
c cc nguyn t cn li v tr s tuyt i. Cng v tr s tuyt i, i
lc electron ca nhm halogen gim khi in tch ht nhn tng (ng
ngha vi khi lng nguyn t tng). iu ny ph hp vi nguyn tc
tng tnh dng in trong phm vi mt nhm t trn xung di. Tuy
nhin nguyn t u nhm flo l mt ngoi l ging nh cc nguyn t
u nhm khc.
Tt c cc nguyn t halogen u c tnh hot ng ha hc mnh,
trong flo l nguyn t hot ng ha hc mnh nht. trng thi kh
cc halogen tn ti di dng phn t F
2
, Cl
2
, Br
2
, I
2
.
33

T clo tr xung trong nhm, khi in tch ht nhn tng th nng
lng phn li lin kt ca cc nguyn t trong phn t gim. Chng ta c
th thy qua nng lng phn li (D) ca cc phn t halogen:
155kJ/mol; 242kJ/mol;
193kJ/mol v 151kJ/mol.
Nng lng phn li l nng lng cn thit tch mt mol phn
t thnh cc nguyn t.
nhit bnh thng flo v clo l cht kh, brom l cht lng, iot
v atatin l nhng cht rn.
Do hot ng ha hc mnh nn trong thin nhin cc halogen
khng tn ti trng thi t do.
Thnh phn ca cc halogen tham gia cu to v qu t rt b,
trong nguyn t ph bin nht l clo chim 0,2%, cn flo ch ch
chim 0,03%, iot ch chim 7.10
-6
% khi lng. Thnh phn brom cha
xc nh c chnh xc, tuy nhin c th on brom ng sau clo
khong 1:300 v ph bin hn iot khon 100 ln.

Tit 19
Bi 2. FLO (F)

A. MC TIU:
Trng thi t nhin; iu ch; cc tnh cht v ng dng ca flo;
hiro florua (tnh cht, s phn li ca axit flohiric, ng dng ca hiro
florua); cc hp cht ca flo vi oxi.
B. NI DUNG:
FLO
Z = 9
Khi lng nguyn t: 18,9984
Khi lng ca ng v: 19
Cu hnh electron: [He]2s
2
2p
5

1. Trng thi t nhin
Flo l mt trong s hai nguyn t c cu to t mt loi ng v
( ). Tn ca nguyn t c t theo tn ca qung quan trng nht
ca flo, l florit (CaF
2
). T lu florit c dng lm cht tr dung
trong luyn kim. M florit ln c tm thy Nga, c, M. Ngoi ra
flo cn c trong qung criolit (Na
3
AlF
6
) cng nh trong qung apatit
(3Ca
3
(PO
4
)
2
.Ca(F,Cl)
2
= 2Ca
5
(PO
4
)
3
.(F,Cl).
Ngoi cc khong cht ni trn, mt s thc vt cng tichws ly
flo, chng hn mt s loi c c hm lng flo rt cao. Flo cn tham gia
cu to xng v c trong men rng. Thiu flo trong rng d dn n su
rng, v vy mt s nc ngi ta cho thm mt lng nh cc mui
florua vo nc ung hoc cho vo kem nh rng.
2. iu ch
V khng c mt nguyn t ha hc no c th kh c in tch
m ca ion florua gii phng flo nn vic iu ch flo v sau ny mi
c tin hnh bng phng php in phn (Moaxng [Moissan] 1886).
Khi in phn mt dung dch florua trong hiro florua, flo c
gii phng ant
2F
-
- 2e F
2

Hin ti ngi ta in phn mui florua nng chy nh KHF
2
(KF-
HF) c nhit nng chy 490K hay KF.2HF c nhit nng chy
345K. Phng php in phn ny c ngha rt ln trong phng th
nghim cng nh trong cng nghip.
34

Thay cho cc thit b bng platin m Moaxng dng, ngy nay
ngi ta dng cc b in phn bng niken, ng, magie hay nhng hp
kim ca ba nguyn t ny. Thc ra flo c tc dng vi cc kim loi ny,
nhng lp florua c hnh thnh ngn cn phn ng tip theo. Thnh b
in phn ng vai tr catt. Ant c ch to bng cc thanh than ch.
nhit in phn t 373 n 490K, than ch tng i bn trc tc
dng ca flo. Catt v ant phi c ngn cch bng mng ngn
trnh n do s kt hp gia hiro c to ra catt v flo c to ra
ant.
3. Cc tnh cht v ng dng ca flo
Flo l cht kh c mu vng nht, trng thi lng c mu vng
m. Flo l mt trong nhng nguyn t c tnh m in mnh nht.
Ngoi phn ng vi oxi v nit, flo cn phn ng vi hu ht cc nguyn
t khc to thnh cc hp cht florua tng ng.
Flo tc dng vi nc to thnh oxi nguyn t, qua c th to
thnh ozon. Ngoi ra, oxi nguyn t kt hp vi nhau to thnh phn t
O
2
sau khong thi gian ngn. Phn ng xy ra hon ton:
F
2
+ H
2
O 2HF + O
2F
2
+ 2H
2
O 4HF + O
2

Flo c dng iu ch cc cht chuyn ti flo dng trong phn
ng vi hirocacbon c clo ha to ra cc sn phm c ngha
rt ln trong cng nghip (phn ng trao i clo-flo), chng hn nh cc
freon c dng thay th amoniac trong cc my lnh. S trng hp
tetraflo etilen (C
2
F
4
) cho ta nha nhn to c bit tr vi cc ha cht v
chu nhit cao, c gi l teflon. Cc hp cht flo cn c dng
iu ch mt s cht c ha hc nh DEP, sarin, soman
4. Hiro florua
Hp cht quan trng ca flo l hiro florua (HF). Hp cht ny
c hnh thnh t phn ng ca hai n cht (hn hp n).
H
2
+ F
2
2HF; kJ/mol
Do entanpi hnh thnh ca hiro florua rt ln nn ngn la n hn
hiro florua t ti 4273K.
Trong cng nghip, hiro florua c iu ch bng cch cho lorit
(CaF
2
) tc dng vi axit sunfuric c trong thit b bng platin, ch hay
gang nhit cao
CaF
2
+ H
2
SO
4
CaSO
4
+ 2HF
a. Tnh cht
nhit thp hiro florua l mt cht lng linh ng, bc khi
mnh trong khng kh, si 292,54K. Hiro florua tan v hn trong
nc to thnh dung dch axit flo hiric. Axit flo hiric l mt axit yu.
Axit ny thng c cha trong cc bnh bng platin hay bnh nha
nhn to nh polietilen, v hiro florua an mn thy tinh.
Hiro florua cng nh cc hiro halogenua khc nh hiro clorua,
hiro bromua v hiro ioua trng thi lng thc t khng dn in. S
in li ca cc hp cht ny ch xy ra trong dung dch nc.
Nhit ha rn ca hiro florua l 190K. So vi cc gi v nhit
si v nhit ha rn ca cc hiro halogenua khc th cc gi tr
ny ca hiro florua cao mt cch bt bnh thng. iu ny c lin quan
n trng thi phn t ca hiro florua khc vi trng thi phn t ca
cc hiro halogen cn li. Nguyn nhn l do hiro florua lng, ging
nh nc, c s lin hp mnh gia cc phn t. Lc lin kt c hnh
thnh qua cc cu hiro. S to thnh cc lin kt cu hiro l nhng cn
bng ph thuc vo nhit v p sut.
35

H
4
F
4
2H
2
F
2
4HF
Cng vi nguyn nhn trn, hiro florua l axit yu so vi hiro
clorua hay hiro hay hiro bromua trong dung dch nc.
Hiro florua bc khi trong khng kh l do hi nc trong khng
kh to vi hiro florua cc ht sa m nh.
b. S phn li ca axit flohiric
Trong dung dch nc hiro florua phn li nh sau:
HF + H
2
O H
3
O
+
+ F
-

Hng s phn li axit

Ngoi ra cn c s phn li ca cc phn t lin hp
H
2
F
2
+ H
2
O H
3
O
+
+ H
Trong dung dch axit flohiric nng 1M ch c 1% ion F
-
,
ngc li c 10% ion H , v vy dung dch hiro florua c coi nh
mt axit hai nc. Axit flohiric to ra nhng mui trung tnh hoc mui
axit, v d cho axit flohiric tc dng vi kali hiroxit to ra mui kali
florua v kalihiroflorua (KF v KHF
2
). Cc mui florua c th kt hp
vi nhiu phn t hiro florua to thnh cc hp cht c dng
KF.2HF, KF.3HF S hnh thnh ion H c gii thch trn c s
lin kt cu hiro, mt dng c bit ca lin kt cng ha tr.
Nhiu mui ca axit flohiric kh tan nh CuF
2
, PbF
2
, CaF
2
, SrF
2
,
BaF
2
. Natri florua cng tng i kh tan, trong khi kali florua v bc
florua li d tan trong nc.
c. ng dng ca hiro florua
Mt lng ln hiro florua c dng trong tng hp hu c
iu ch cc dn xut hu c cha flo. Mt lng ng k c dng
khc thy tinh. Thnh phn chnh ca thy tinh l silic ioxit (SiO
2
) tc
dng vi axit flohiric to thnh silic tetraflorua d bay hi.
SiO
2
+ 2H
2
F
2
SiF
4
+ 2H
2
O
Axit flohiric cn dng trong phn tch ph v cc mu silicat.
Dung dch long ca axit flohiric c th dng lm cht kh trng,
c ngha quan trng i vi cc nh my sn xut cc loi men vi sinh.
Cc mui florua tan trong nc v hexafloro silicat c dng
x l g.
5. Cc hp cht ca flo vi oxi
C bn hp cht ca flo vi oxi, c gi l oxi florua, v flo c
tnh m in hn oxi.
Oxi iflorua (O
2
F)
Oxi iflorua c Lb (Lebeau) v aming (Damien) iu ch
vo nm 1928 bng cch cho flo tc dng natri hiroxit
2F
2
+ 2 + OF
2
+ H
2
O
Entanpi hnh thnh chun ca hp cht kJ/mol. OF
2

l cht kh khng mu, c nhit si 128,2K v ha rn nhit
49,2K. Kh ny c th ngng t thnh mt cht lng mu vng. Cu trc
phn t ca OF
2
ging cu trc phn t ca nc nhng gc lin kt b
hn:

36

OF
2
tc dng vi nc ging nh flo
OF
2
+ H
2
O O
2
+ 2HF
ioxi iflorua (O
2
F
2
)
ioxi iflorua c hnh thnh do phng in m qua hn hp flo
v oxi nhit khng kh ha lng. trng thi rn O
2
F
2
c nhit
si 216K (nhit ngoi suy) v nhit ha rn 109,5K. nhit cao
O
2
F
2
b phn hy thnh cc n cht. Entanpi hnh thnh chun ca O
2
F
2

l kJ/mol. nhit 116K, O
2
F
2
c khi lng ring d =
1,736g/cm
3
.
Ozon iflorua (O
3
F
2
)
Ozon iflorua c iu ch bng cch phng in qua hn hp
nguyn t nhit 73K di p sut 1,6kPa.
nhit thp ozon iflorua l cht lng mu , c khi lng
ring d = 1,75g/cm
3
90K. Entanpi hnh thnh chun ca hp cht
kJ/mol. O
3
F
2
t phn hy t nhit 268K tr ln
2 O
3
F
2
O
2
+ 2 O
2
F
2

Kh nng oxi ha ca hp cht ny cao hn flo v oxi iflorua.
Tetraoxi iflorua (O
4
F
2
)
O
4
F
2
c iu ch t cc nguyn t qua phng in nhit 60
n 70K. nhit trn 100K, O
4
F
2
b phn hy, to thnh ozon
iflorua v oxi.

Tit 20, 21, 22
Bi 3. CLO (Cl)

A. MC TIU:
Trng thi t nhin; iu ch; tnh cht vt l; tnh cht ha hc;
ng dng; hiro clorua (iu ch, tnh cht, ng dng); hp cht c oxi
v oxiaxit ca clo (c im chung, hp cht ca clo vi s oxi ha +1,
cc hp cht ca clo vi s oxi ha +3, cc hp cht ca clo vi s oxi
ha +4, cc hp cht ca clo vi s oxi ha +5, cc hp cht ca clo vi
s oxi ha +6, cc hp cht ca clo vi s oxi ha +7).
B. NI DUNG:
CLO
Z = 17
Khi lng nguyn t: 35,453
S khi ca cc ng v bn: 35; 37
Cu hnh electron: [Ne]3s
2
3p
5

3.1. Trng thi t nhin
Clo l nguyn t halogen ph bin nht c Sel (Scheele) pht
hin vo nm 1774 v c avi (Davy) xc nh l mt nguyn t ha
hc vo nm 1810. Clo c t tn theo ting Hi Lp chloros l mu
vng lc.
Ngi ta ch tm thy clo trng thi t do trong kh thot ra t ni
la. Bnh thng clo ch tn ti dng hp cht. Lng ln clo c trong
nc bin l cc mui natri clorua v magie clorua.
Do s bc hi nc cc vng bin cht t nhng thi k a cht
xa xa xut hin nhiu m mui ln. Trong qung apatit cng c mt
lng ng k clo. Clo l mt nguyn t ca hai ng v bn vi t l 3:1
( : 75,5%, :24,5%).
3.2. iu ch
37

Trong phng th nghim, clo c iu ch t hiro clorua. Mt s
cht oxi ha mnh tc dng vi hiro clorua gii phng clo. Cht oxi ha
r tin thng c dng l mangan (IV) oxit (MnO
2
)
MnO
2
+ 4HCl MnCl
4
+ 2H
2
O
MnCl
4
MnCl
2
+ Cl
2

Tng cng: MnO
2
+ 4HCl MnCl
2
+ 2H
2
O + Cl
2

Ban u phn ng hnh thnh mangan (IV) clorua. Sau mangan
(IV) clorua t phn hy thnh mangan (II) clorua v clo. Thay cho phn
ng trc tip gia axit clohiric v mangan (IV) oxit. Axit sunfuric c
gii phng hiro clorua t mui natri clorua, sau hiro clorua tc dng
vi mangan (IV) oxit
H
2
SO
4
+ NaCl NaHSO
4
+ HCl
MnO
2
+ 4HCl MnCl
2
+ 2H
2
O + Cl
2

Ngoi mangan (IV) oxit ngi ta cn dng cc cht oxi ha khc
nh: kali pemanganat (KMnO
4
), kali icromat (K
2
Cr
2
O
7
) hay clorua vi
(CaCl(OCl).
Trong cng nghip, mt lng ln clo c iu ch bng phng
php in phn cc mui clorua trng thi nng chy hoc trong dung
dch. V d in phn natri clorua.
- trng thi nng chy:
NaCl Na
+
+ Cl
-

ant: 2Cl
-
-2e Cl
2

catt: 2Na
+
+ 2e 2Na
Tng cng: 2NaCl 2Na + Cl
2

- in phn dung dch natri clorua:
Phng php in phn dung dch natri clorua ph bin l phng
php mng ngn xp. Mng ngn xp c dng trnh n do cc kh
clo v hiro tip xc vi nhau v ngn cn cho tc dng vi dung dch
NaOH c to thnh vng catt.
Cc ion trong dung dch NaCl khi in phn:
2NaCl 2Na
+
+ 2Cl
-

Phn ng catt:
2H
+
+ 2e H
2

Phn ng ant:
2Cl
-
-2e Cl
2

Phn ng tng cng:
2H
2
O + 2NaCl 2NaOH + Cl
2
+ H
2

3.3. Tnh cht vt l
Clo l cht kh mu vng lc, c mi xc, lm nght th, c kh
nng phn hy ng h hp. Clo nng gp hai ln ri khng kh. Khi
nn di p sut ln, clo d ha lng, v nhit ti hn ca n cao
(nhit ti hn 416,5K, p sut ti hn 7710kPa). Clo thng c bo
qun di dng lng trong cc bnh thp chu p lc hoc trong cc bnh
bng hp kim titan. Clo c nhit si 239K v nhit ha rn 170,6K.
Clo ha tan tt trong nc, mt th tch nc 293K v p sut kh
quyn ha tan c 2,3 th tch clo. Dung dch cha khong 1/10 mol clo
c gi l nc clo. V clo d tan trong nc nn khi iu ch clo trong
phng th nghim, ngi ta cho kh clo li qua dung dch bo ha natri
clorua hay thu kh vo mt bnh thy tinh bng mt ng dn cm xung
y. Clo nng hn khng kh li pha di v y khng kh ra khi
bnh.
38

3.4. Tnh cht ha hc
Clo l mt trong nhng nguyn t hot ng ha hc mnh nht,
thc t thng coi l mt phi kim in hnh, c kh nng phn ng vi
hu ht cc nguyn t khc nhit bnh thng v rt mnh lit
nhit cao, ng thi ta nhit mnh. i vi kh him cng nh i
vi oxi, nit, cacbon th clo tng i tr trong cc phn ng trc tip;
nhng bng con ng vng quqa cc hp cht khc cng c th iu
ch c cc hp cht clo ca cc nguyn t trn. Di y l mt s
phn ng ca clo vi kim loi v phi kim:
Trong s cc kim loi, nhm kim loi kim c phn ng vi clo
mnh nht.
Nu un nng mt mu natri ln nhit 373K trong dng kh clo,
hai nguyn t s phn ng mnh vi nhau, ta ra nh sng vng cng
ln v to thnh natri clorua
2Na + Cl
2
2NaCl; kJ/mol
Cc kim loi kim th phn ng vi clo gn mnh bng cc kim loi
kim
Ca + Cl
2
CaCl
2
; kJ/mol
Cc kim loi na pha phi ca bng tun hon cng phn ng
mnh vi clo nu chng trng thi phn b nh.
Cc kim loi qu nh ng dng bt tc dng vi clo
Cu + Cl
2
CuCl
2
; kJ/mol
Trong tt c cc phn ng trn, m ca clo ng vai tr quan
trng. Kh clo kh phn ng chm hn kh clo m nhiu. Chng hn clo
hon ton kh khng phn ng vi st v ng. Bi vy c th dn kh
clo kh qua ng dn bng st, thp v cha clo lng trong cc bnh thp
di p sut khong 607,95kPa.
Cc phn ng ca clo vi cc phi kim nhit bnh thng nh
vi photpho, lu hunh, hiro khng mnh. Hn hp gia clo v hiro
ngoi nh sng hay un nng cc b s gy n to ra kh hiro clorua
H
2
+ Cl
2
2HCl; kJ/mol
V vy hn hp clo-hiro c gi l hn hp n.
Ngi ta dn kh clo v hiro theo hai ng ng tch bit v cho
tip xc vi nhau ngi t, hiro s chy m du trong kh clo.
Clo cn c xu hng kt hp vi cc nguyn t hiro trong cc
hp cht hnh thnh hiro clorua.
V d: Mt bng giy lc nh tm du tecpentin (C
10
H
16
) a vo
mt bnh thy tinh ng clo; du tecpentin chy trong clo, to ra m
mui than dy c
C
10
H
16
+ 8Cl
2
10C + 16HCl
Kh hiro sunfua rd vi nc clo to kt ta lu hunh
H
2
S

+ Cl
2
2HCl + S
Nc cng c th b clo phn hy
H
2
O + Cl
2
2HCl + O
Phn ng ny ch xy ra khi c tc dng ca nh nng mt tri.
Phn ng clo tc dng vi nc thng thng l:
H
2
O

+ H
2
O HCl + HClO
3.5. ng dng
Clo c s dng ty mu v kh trng. Qu trnh ph v cc
cht mu bng phn ng oxi ha ca clo c dng lm trng lanh,
bng, ay, bt giy v.v Tuy nhin khi bng, vi, si, bt giy c
ty mu bng clo phi quy kh clo d tha cn ng li trnh s ph
hy tip theo ca clo. Bi vy phm vi ty mu ca clo ngy cng b hp
39

li v c thay th bng ty mu hiro peoxit. Hiro peoxit t ph hy
vi si v tc dng nhanh hn. Tc dng tiu dit vi khun ca clo c
dng trong x l nc ung, kh trng nc trong cc b bi cng cng
v x l nc thi.
Clo cn c dng tng hp axit clohiric v tng hp hu c
nh tng hp vinyl clorua (C
2
H
3
Cl). T vinyl clorua ngi ta sn xut
cht do polivinyl clorua (PVC) hoc sn xut 1,2 icloetan (C
2
H
4
Cl
2
)
lm dung mi.
3.6. Hiro clorua
3.6.1. iu ch
- Hiro clorua c th c iu ch trc tip t cc n cht:
H
2
+ Cl
2
2HCl; kJ/mol
Trong cng nghip, hiro clorua c tng hp trong l t bng
thch anh. Clo c t chy trong hiro v to thnh hiro clorua. Kh
hiro clorua c ha tan vo nc trong cc bung hp th bng tantan
v cho ra axit clohiric rt tinh khit. nh my giy Bi Bng, Ph Th
qu trnh tng hp hiro clorua c tin hnh trong l t bng than ch
(graphit) cng thu c axit clohiric tinh khit. nh my Ha cht
Vit Tr, Ph Th sn xut axit clohiric bng l thp nn c ln hp cht
st lm cho axit clohiric c mu vng, gy phin phc cho qu trnh tinh
ch.
- Hiro clorua cn c iu ch t cc mui clorua. Cho axit
sunfuric c tc dng ln cc mui clorua ngi ta thu c hiro clorua.
Phn ng xy ra theo hai nc
NaCl + H
2
SO
4()
NaHSO
4
+ HCl
NaCl + NaHSO
4
Na
2
SO
4
+ HCl
3.6.2. Tnh cht
- Tnh cht vt l
Hiro clorua l mt cht kh khng mu, mi xc, d ha lng
(nhit ti hn 324K). Hiro clorua lng l cht lng khng mu, c
nhit si 188K v nhit ha rn 158,93K. c bit l hiro clorua
ha tan rt nhiu trong nc. Mt th tch nc c th ha tan 507 th
tch kh hiro clorua 273K v p sut bnh thng. Hiro clorua trong
dung dch nc c gi l axit clohiric. Axit ny c iu ch rt
nhiu trong cng nghip.
Mt dung dch nc bo ha hiro clorua 288K c nng
42,7% v c khi lng ring 1,12g/cm
3
. Dung dch axit clohiric long
hn c khi lng ring nh hn. y c mi quan h nh lng tnh
c gia nng phn trm v khi lng ring ca dung dch axit
clohiric nh sau: ly hai s u sau du phy ca khi lng ring nhn
i ln ta c nng phn trm ca dung dch [nng % = 200(d-1)].
Khi lng ring d (g/cm
3
) 1,06 1,12 1,16 1,19
Nng phn trm (%) 12% 24% 32% 38%
Axit clohiric m c trn th trng c khi lng ring 1,19.
Axit ny bc khi mnh trong khng kh m, v vy cn c gi l axit
clihiric bc khi.
- Tnh cht ha hc
Hiro clorua lng khng tc dng vi a s kim loi, cc oxit,
sunfua v cacbonat ca chng.
Kh hiro clorua tc dng vi nhiu kim loi to thnh mui clorua
v gii phng hiro nhit cao, v d:
2Al + 6HCl 2AlCl
3
+ 3H
2

40

Fe + 2HCl FeCl
3
+ H
2

Kh hiro clorua tc dng vi flo nhit thng
F
2
+ 2HCl 2HF + Cl
2

Kh hiro clorua tc dng vi oxi khi c cht xc tc hay nhit
cao

Dung dch kh HCl trong nc l mt axit mnh. Axit clohiric tc
dng vi cc kim loi c th in cc chun m (E
0
<0) to thnh cc
mui clorua v gii phng hiro, v d:
Zn + 2HCl ZnCl
2
+ H
2

Sn + 2HCl SnCl
2
+ H
2

Axit clohiric tc dng vi cc baz to thnh cc mui clorua v
nc.
Nhiu mui clorua d tan. Mt s mui kh tan nh bc clorua
(AgCl), ng (I) clorua (CuCl) v ch (II) clorua (PbCl
2
). Bc clorua c
ngha ln trong ha phn tch v tnh kh tan ca n.
3.6.3. ng dng
Axit clohiric c s dng rng ri bn cnh axit sunfuric v axit
nitric l nhng axit v c mnh v quan trng. Axit clohiric c mt
trong nhiu ngnh cng nghip ha cht, c dng tng hp cht,
iu ch cc mui clorua cng nh dng lm dung mi.
Con ngi cng t sn xut mt lng nh axit clohiric cn thit
cho qu trnh tiu ha. Trong dch d dy lun c 0,4% axit clohiric,
nng ny c gi c nh c chua cn thit gip chuyn ha
cc loi thc n.
3.7. Hp cht oxi v oxiaxit ca clo
3.7.1. c im chung
Cc hp cht clo oxit c entanpi hnh thnh chun dng, v vy
khng th iu ch trc tip t clo v oxi.
Cc oxit c nghin cu:
Cl
2
O, ClO
2
, Cl
2
O
6
(ClO
3
), Cl
2
O
7

Mt s tnh cht vt l ca cc clo oxit c trnh by bng sau:
Mt s tnh cht vt l ca cc clo oxit
S oxi
ha
Oxit Entanpi hnh thnh
chun (kJ/mol)
Nhit nng
chy (K)
Nhit si
(K)
+1 Cl
2
O

76,02 157 275
+4 ClO
2
105 214 284
+6 Cl
2
O
6
155,4 276
+7 Cl
2
O
7
265,86 181,5 354
Trong hp cht vi oxi, clo l thnh phn dng in, v oxi c
tnh m in mnh hn.
S oxi ha ti a ca clo i vi oxi l +7, tng ng vi v tr ca
clo trong nhm VII ca bng tun hon cc nguyn t ha hc v cng
ph hp vi s tn ti by electron lp ngoi cng ca nguyn t clo.
Trong s cc clo oxit bit ch c Cl
2
O v Cl
2
O
7
l anhirit ca
axit hipoclor (HClO) v axit pecloric (HClO
4
). Axit clor (HClO
2
) v
axit cloric (HClO
3
) khng c anhirit. Cc oxit ClO
2
v Cl
2
O
6
c coi
l hn hp anhirit.
3.7.2. Hp cht ca clo vi s oxi ha +1
41

iclo oxit c iu ch bng cch dn kh clo qua thy ngn (II)
oxit kh 273K
2Cl
2
+ 2HgO HgO. HgCl
2
+ Cl
2
O
iclo oxit l cht kh c kh nng n mnh.
Cu trc phn t ca iclo oxit ging OF
2
, nhng gc lin kt gia
nguyn t oxi v hai nguyn t clo l 115
0
v di lin kt Cl-O l
168pm.
T Cl
2
O c th to ra c axit yu hipoclor (HClO vi K
a
=
3.10
-8
). Axit ny c mt lng nh trong nc clo do
Cl
2
+ H
2
O HClO + HCl
Ngi ta c th iu ch axit hipoclor bng cch khuy nc clo
vi thy ngn oxit; qua c th loi caxit clohiric c trong cn
bng do kt ta thy ngn oxiclorua

Dung dch long HClO c iu ch nh trn c th c c c
cht t bng ct chn khng. Ngc li axit hipoclor tinh khit khng
th iu ch c, v nng cng cao qu trnh phn hy cng nhanh:
HClO HCl + O
Tc dng oxi ha mnh ca clo m l qu trnh phn hy axit
hipoclor lm xut hin nguyn t oxi mi sinh. Oxi nguyn t mi sinh
hot ng ha hc mnh, c tnh kh trng v ty mu cao, v vy cc
mui hipoclorit c dng rt pht bin.
Cc mui hipoclorit c iu ch bng cch cho clo tc dng vi
dung dch kim. Qu trnh phn ng ny c s t oxi ha t kh ca clo.
Phn ng t oxi ha kh c coi l qu trnh ca mt nguyn t vi
mc oxi cho trc chuyn thnh mt mc oxi ha thp hn v mt mc
oxi ha cao hn, trong tng s oxi ha ca cc cht ban u phi bng
tng s oxi ha ca cc sn phm phn ng.
V d: Cl
2
+ 2NaOH NaCl + NaClO + H
2
O
Hay dng ion: Cl
2
+ 2OH
-
Cl
-
+ ClO
-
+ H
2
O
0 -1 +1
Cc mui hipoclorit d dng thy phn trong nc to thnh axit
hipoclor t do, v axit ny l mt axit yu
ClO
-
+ H
2
O

HClO + OH
-

Cc mui hipoclorit trong nc l nhng cht oxi ha mnh. Ngi
ta thng dng cc dung dch mui hipoclorit ty mu vi, si, bt
giy v kh trng.
Mt s dung dch hipoclorit bit t lu nh:
- Dung dch kali hipoclorit c sn xut mang tnh cht cng
nghip t nm 1792, c gi l nc javen.
- Dung dch natri hipoclorit c sn xut t nm 1820, c gi
l nc Labarc.
- Trong cng nghip cn sn xut mt lng ln clorua vi. Clorua
vi c iu ch bng cch cho clo bo ha vo vi ti v c coi l
mui hn hp ca axit clohiric v axit hipoclor
Ca(OH)
2
+ Cl
2
CaCl(OCl) + H
2
O
3.7.3. Cc hp cht ca clo vi s oxi ha +3
i din cho hp cht c s oxi ha +3 l HClO
2
. n nay cha
iu ch c anhirit thun ty ca axit ny. Axit clor ch bn trong
dung dch long, khi un nng b phn hy. Hng s phn li axit nhit
42

bnh thng ca axit clor K
a
= 1.10
-2
. Axit clor nguyn cht c
to thnh khi cho hiro peoxit tc dng vi clo ioxit
2Cl
2
+ H
2
O
2
2HClO
2
+ O
2

Clo ioxit tc dng vi nc to thnh hn hp axit clor v axit
cloric
2ClO
2
+ H
2
O HClO
2
+ HClO
3

Mui ca clorit c iu ch bng cch dn clo ioxit vo dung
dch kim c thm hiro peoxit loi mui clorat, trong hiro peoxit
kh clorat thnh clorit
2ClO
2
+ 2KOH KClO
2
+ KClO
3
+ H
2
O
KClO
3
+ H
2
O
2
KClO
2
+ H
2
O + O
2

Tng cng: 2ClO
2
+ 2KOH + H
2
O
2
KClO
2
+ 2H
2
O + O
2

Tng t nh vy ngi ta c th iu ch natri clorit. Cc clorit
bn hn cc mui hipoclorit nhng vn l nhng cht oxi ha mnh.
m bo an ton khi s dng, natri clorit bn trn th trng c pha vi
mt lng nc t 10 15%. Khi s l dung dch natri clorit vi axit c
s hnh thnh clo ioxit l cht ty mu t ph hy bng, vi, si, bt
giy so vi clo. Vi nhng cht c th oxi ha c nh hp cht hu
c, than, lu hunh hay bt kim loi, natri clorit rn to thnh hn hp n
ging nh clorat.
Mui bc clorit v ch clorit (AgClO
2
v Pb(ClO
2
)
2
) u c mu
vng, rt kh tan trong nc, khi h nng hay p mnh s phn hy v
n mnh.
3.7.4. Cc hp cht ca clo vi s oxi ha +4
Clo c s oxi ha +4 trong hp cht ClO
2
clo ioxit. Trong thc t
khng c axit tng ng vi oxit ny. Di tc dng ca dung dch kim
ln clo ioxit, ngi ta nhn c mui clorat v clorit (phn ng t oxi
ha t kh). Nh vy clo ioxit l hn hp anhirit ca axit cloric v axit
clor. Trng thi oxi ha ca clo ioxit nm gia trng thi oxi ha ca
hai axit ny.
Clo ioxit c iu ch bng cch kh hp cht clo c s oxi ha
cao hn nh axit cloric (HClO
3
). Cht kh c th l axit cloric. Trong
phn ng axit cloric chuyn thnh axit pecloric HClO
4
.
Qu trnh phn ng cn thit phi loi nc ra khi cn bng.
Trong thc t ngi ta tin hnh iu ch clo ioxit bng cch cho axit
sunfuric c tc dng vi kali clorat. Phn ng ny gii phng axit cloric
v xy ra phn ng t oxi ha kh ca axit cloric nh trn.
HClO
3
+ HClO
3
HClO
2
+ HClO
4

HClO
2
+ HClO
4
2ClO
2
+ H
2
O
2HClO
3
+ HClO
3
2ClO
2
+ H
2
O + HClO
4

Tt hn l dng axit oxalic lm cht kh. Sn phm oxi ha axit
oxalic l kh cacbonic. Kh ny s pha long kh clo ioxit v hn ch
c tnh d n ca clo ioxit nguyn cht. Trong thc t phn ng c
tin hnh nh sau: Trn ln hp cht rn kali clorat v axit oxalic, sau
cho axit sunfuric c tc dng ln hn hp, ta s c cc phn ng:
H
2
SO
4()
+ 2KClO
3
2HClO
3()
+ K
2
SO
4


2HClO
3
+ H
2
C
2
O
4
2ClO
2
+ 2CO
2
+ 2H
2
O
Trong cng nghip, ngi ta iu ch clo ioxit t natri clorat v
axit sunfr:
2NaClO
3
+ H
2
SO
3
2HClO
3
+ Na
2
SO
3

+
+
43

2HClO
3
+ H
2
SO
3
2ClO
2
+ 2H
2
SO
4
+ H
2
O
Tnh cht
Clo ioxit l mt cht kh mu vng, c mi xc, ha lng 283K.
Clo ioxit lng mu nu, ha rn 197K, to thnh nhng tnh th mu
da cam. Cht rn ny rt d n khi un nh, p bng vt rn hay cho tip
xc vi cc cht d oxi ha gy ting n mnh to thnh clo v oxi
ClO
2
1/2Cl
2
+ O
2
; kJ/mol
Clo ioxit tr nn bn hn khi cng hp vi piriin
ClO
2
+ C
5
H
5
N C
5
H
5
N.ClO
2

Hp cht ny c ha vo nc dng ty mu, oxi ha v clo
ha.
Clo ioxit ha tan d dng trong nc. Dung dch nc trong
bng ti v nhit phng bo qun c lu, tuy nhin dn dn cng c
s bin i thnh axit clor v axit cloric. Axit clor phn hy nhanh
trong dung dch nc nn cui cng ch cn li axit clohiric v axit
cloric. Trong dung dch kim, mui clorat v mui clorit tn ti sng
song.
Cu to phn t ClO
2
ging phn t Cl
2
O, nhng gc lin kt
khong 137
0
v di lin kt Cl-O l 153pm.
3.7.5. Cc hp cht ca clo vi s oxi ha +5
i din ca cc hp cht ny l axit cloric HClO
3.
Cc mui clorat ca axit cloric c hnh thnh t phn ng t oxi
ha kh ca cc mui hipoclorit tng ng nhit t 323K n 33K
3KClO KClO
3
+ 2KCl
Trong cng nghip ngi ta iu ch kali clorat bng in phn
dung dch kali clorua khng c mng ngn. Kali hiroxit hnh thnh
catt kt hp vi clo sinh ra ant to thnh kali hipoclorit. nhit
t 323K n 333K xy ra qu trnh thy phn mnh ca mui hipoclorit
KClO + H
2
O KOH + HOCl
Mui hipoclorit c oxi ha bng axit hipoclor c trong dung
dch to thnh kali clorat v axit clohiric. Kali clorat l mui kh tan,
kt ta, trong khi kali clorua c in phn tip tc
KOCl + 2HOCl 2HCl + KClO
3

Tng t nh vy, ngi ta c th nn kh clo vo nc vi nng
iu ch canxi clorat dng trong sn xut clo ioxit:
6Ca(OH)
2
+ 6Cl
2
Ca(ClO
3
)
2
+ 5CaCl
2
+ 6H
2
O
Axit cloric tng i bn, c iu ch bng phn ng gia dung
dch bari clorat v mt lng tng ng axit sunfuric long
Ba(ClO
3
)
2
+ H
2
SO
4(l)
BaSO
4
+ 2HClO
3

Sau khi tch kt ta bari sunfat, dung dch axit cloric long c
c chn khng ( trnh phn ng n do t phn hy) ln nng 40-
50%; nu c c hn na s c s phn hy thnh oxi clo v axit
pecloric. HClO
3
l cht oxi ha mnh. Ion clorat ClO
3
-
c cu trc hnh
chp tam gic. Dung dch cc mui clorat cng c tnh oxi ha nhng
yu hn dung dch cc mui hipoclorit; khi c mt cht xc tc, v d
hp cht osmi th tnh oxi ha ca dung dch clorat tng ln r rt.
nhit cao, clorat b phn hy theo hai cch
4KClO
3
3KClO
4
+ KCl

44

Phn ng sau mui clorat b phn hy to thnh oxi v kali clorua.
Qu trnh ny nu dng mangan (IV) oxit lm xc tc th phn ng xy ra
nhanh nhit thp hn. y l mt phng php iu ch oxi trong
phng th nghim.
Cc mui clorat trng ln vi cc cht d chy to thnh nhng
hn hp n mnh, v d mui kali clorat trn vi bt lu hunh s n
mnh ngay khi nghin trong ci. Hn hp kali clorat v ng bc chy
khi cho tc dng vi axit sunfuric c. Trong trng hp ny thc ra clo
ioxit l cht oxi ha. Oxit ny c to ra do phn ng gia ion clorat
v axit sunfuric c.
Kali clorat c dng sn xut dim, pho sng, pho hoa, cht
n. Natri clorat c dng lm cht dim c v dng lm cht ban u
sn xut cc clorat khc.
3.7.6. Hp cht ca clo vi s oxi ha +6
Oxit Cl
2
O
6
iclo hexaoxit c iu ch bng cch oxi ha clo
ioxit pha long trong kh cacbonic vi ozon (di dng kh oxi c
ozon ha mt phn) nhit 273K
ClO
2
+ O
3
ClO
3
+ O
2

2ClO
3
Cl
2
O
6

Tnh cht
iclo hexaoxit l cht lng mu nu, ha rn 276,6K v si
476K (im si ngoi suy v cha t c nhit ny hp cht b
phn hy). Hp cht dng tinh khit v nhit bnh thng kh bn.
Khi cho tip xc vi cht hu c Cl
2
O
6
nt rt mnh. un nng Cl
2
O
6
c
s phn li thnh hn phn t ClO
3

Cl
2
O
6
2ClO
3

n phn t ClO
3
d dng b phn hy thnh clo ioxit v oxi
nguyn t:
ClO
3
ClO
2
+ O
iclo hexaoxit tc dng vi nc to thnh axit cloric v axit
pecloric
Cl
2
O
6
+ H
2
O HClO
3
+ HClO
4

3.7.7. Hp cht ca clo vi s oxi ha +7
Clo c s oxi ha +7 trong phn t iclo heptoxit Cl
2
O
7
, trong axit
pecloric HClO
4
v trong cc mui peclorat ClO
4
-
.
a. iclo heptoxit Cl
2
O
7

- iu ch
L anhirit ca axit pecloric, iclo heptoxit c iu ch bng
cch tch nc ca axit pecloric vi iphotpho pentoxit
2HClO
4
Cl
2
O
7
+ H
2
O
H
2
O + P
2
O
5
2HPO
3

2HClO
4
+ P
2
O
5
2HPO
3
+ Cl
2
O
7

Oxit c th c ct trc tip ra khi h phn ng nu c nhng
bin php an ton y v bn cht d n ca oxit ny.
Tnh cht
iclo heptoxit l mt cht lng khng mu, d bay hi, snh c
nh du, c nhit si 356K v ha rn 181K, khi tip xc vi
ngn la hoc p mnh s n. Di cc iu kin thng, Cl
2
O
7
bn
hn cc oxit khc ca clo. Cl
2
O
7
khng phn ng vi lu hunh, photpho
v cht hu c trong mi trng lnh.
b. Axit pecloric HClO
4

- iu ch
45

Khi nung nng clorat, chng hn kali clorat ln nhit 673K s
xy ra phn ng t oxi ha kh. Phn ng to thnh kali clorua v kali
peclorat
4KClO
3
KCl + 3KClO
4

Sau ngi ta cho axit sunfuric c tc dng ln kali peclorat v
thu c axit pecloric
KClO
4
+ H
2
SO
2()
KHSO
4
+ HClO
4
Axit pecloric c tch ra khi h bng ct chn khng vi qu
trnh gia nhit phi tht cn thn trnh n.
- Tnh cht
Axit pecloric tinh khit l mt cht lng khng mu, linh ng, bc
khi trong khng kh, ha rn 161K, c khi lng ring 1,764g/cm
3

295K. Khi un nng c s phn hy v chuyn mu ca axit pecloric
sang nu , nu phn hy mnh s gy ra n. nhit bnh thng
cng c qu trnh phn hy chm, c khi xy ra n m khng h c
nguyn nhn bn ngoi no.
Cht d chy nh bt g, bt than g, giy, cc hp cht hu c
khi tip xc vi axit pecloric b oxi ha gy n mnh.
Axit pecloric lm bng da, to ra cc vt thng au n v kh
lnh.
Trong dung dch nc axit pecloric bn hn v kh nng oxi ha
km hn axit cloric, v d un nh dung dch long axit pecloric viaxit
clohiric khng c s gii phng clo. Dung dch axit pecloric cng khng
tc dng vi axit sunfur to thnh axit sunfuric.
Axit pecloric nguyn cht khc vi dung dch m c. Dung dch
axit pecloric m c l cht lng snh c ging nh axit sunfuric m
c. Dung dch 72% si nhit khng i 476K khng b phn hy.
Trong s cc hirat ng ch nht l monohirat H
3
O
+
[ClO
4
]
-
.
c. Mui peclorat Cl
Cc mui peclorat l nhng mui cha oxi bn nht ca clo. Phn
ln cc mui ny d ha tan trong nc, mt s mui kh tan trong nc
lnh nh kali-, rubii- v xesi peclorat. Trong t nhin c mt lng nh
mui kali peclorat ln trong mui natri nitrat. Kali peclorat l cht c
i vi thc vt, v vy khi khai thc natri nitrat lm phn bn phi tch
kali peclorat ra khi mui ny; nu c nguyn em bn cho cy trng
th cy s li tn.
Anion peclorat c cu to hnh t din u.

Tit 23, 24, 25
Bi 4. BROM (Br)

A. MC TIU:
Trng thi t nhin; iu ch; tnh cht vt l; tnh cht ha hc;
ng dng; hiro bromua (iu ch; tnh cht vt l; tnh cht ha hc v
ng dng); cc oxit v oxiaxit ca brom.
B. NI DUNG: BROM
Z = 35
Khi lng nguyn t: 79,909
S khi ca cc ng v: 79; 81
Cu hnh electron: [Ar]3d
10
4s
2
4p
5

4.1. Trng thi t nhin
Ging nh flo v clo, trong t nhin brom khng tn ti trng
thi t do m dng hp cht. Brom hay i km vi clo trong nhng hp
46

cht tng t nhau theo t l Br : Cl 1 : 300. Brom c nh ha hc
Php Bala pht hin. Do c mi hc nn nguyn t ny c t tn l
brom (theo ting Hi Lp bromos l hc).
4.2. iu ch
- Brom khng hot ng ha hc bng clo, v vy c th dng clo
y brom ra khi hp cht ca n, v d phn ng gia clo v dung
dch kali bromua to thnh kali clorua v gii phng brom
2KBr + Cl
2
2KCl + Br
2

Phng php ny c dng iu ch brom trong cng nghip.
Tuy nhin cht ban u c dng l mui kp KBr.MgBr
2
.6H
2
O (brom
canalit) v hp cht ny c nhiu trong nc lc khi ch bin kali clorua
qu trnh khai thc mui m. Nh vy ngoi phn ng trn, clo cn
tham gia phn ng
MgBr
2
+ Cl
2
MgCl
2
+ Br
2

Qu trnh iu ch c tin hnh trn thp phn ng. Dung dch
mui bromua c phun t nh thp xung. Trong lng thp c nhiu
a sp xp ging nh thp ct phn on. Kh clo c dn t di i
ngc ln. Trong lng thp, clo c trn ln vo dung dch mui
bromua v y brom ra khi hp cht ca n. Brom th thu c c ln
clo, v vy cn phi tinh ch bng phng php ct. Brom th c ct
qua mt ct ct cha mui kali bromua rn. Clo b loi do tham gia phn
ng y brom ra khi mui kali bromua trong cng ct
Cl
2
(d) + 2KBr 2KCl + Br
2

Brom cn c iu ch bng phng php in phn mui
bromua.
- Trong phng th nghim, brom c iu ch bng phng php
ha hc: cho axit sunfuric c tc dng vi hn hp gm kali bromua rn
trn vi mangan (IV) oxit. Thc t xy ra phn ng
4HBr + MnO
2
MnBr
2
+ Br
2
+ 2H
2
O
4.3. Tnh cht vt l
nhit bnh thng brom l cht lng, c nhit si 331,9K
v nhit ha rn 265,9K. Brom c mu nu, ngay nhit thng
cng bc hi mu nu. Hi brom c mi xc, lm ngt th, tc dng vo
cc mng nhy ca ng h hp gy vim lot nguy him. Brom c
khi lng ring d = 3,119g/cm
3
293K. Nhit cng thp mu ca
brom cng nht i. 20K brom c mu da cam, nhit di im si
v trng thi hi brom tn ti di dng phn t hai nguyn t. Cc
phn t ny phn li thnh nguyn t nhit cao. 1200K 2,1% brom
phn t phn li thnh nguyn t. Brom d ha tan trong nc. Mt lt
nc ha tan c 35,5 gam brom 293K. Dung dch cha 0,25mol/l
brom c gi l nc brom. Ging nh nc clo, nc brom c dng
lm cht oxi ha trong phng th nghim.
4.4. Tnh cht ha hc
Tnh cht ha hc ca brom ging tnh cht ha hc ca clo, nhng
brom phn ng khng mnh m bng clo. Khi c nh sng clo phn ng
vi hiro nhit thng. Trng hp ny khng xy ra i vi brom.
Xu th to hp cht trng thi lng ca brom vn rt mnh, chng hn
cho mt antimon vo brom lng phn ng xy ra mnh pht thnh ngn
la. Brom cng c th kt hp vi hiro trong cc hp cht, v d phn
ng gia brom v hiro sunfua hay phn ng vi nc
H
2
S

+ Br
2
2HBr + S
H
2
O + Br
2
HBr + HBrO; K
cb
= 7,2.10
-4

47

Phn ng th nht c dng iu ch hiro brpmua. Brom
phn ng vi natri 473K khng ng k, trong khi vi kali phn
ng gy ni rt mnh.
4.5. ng dng
Brom c dng trong tng hp cc dn xut hu c cha brom,
dng trong tng hp cc cht mu, v cc nguyn t brom lm tng
cng ca mu. Brom cn c dng sn xut mt s cht c v
hi c, chng hn brom axeton l hi cay lm chy nc mt. Brom
c dng ph bin lm cht oxi ha. Ngoi ra, cc hp cht ch brom
c dng sn xut qun o chng chy.
4.6. Hiro bromua
4.6.1. iu ch
C nhiu cch iu ch hiro bromua. Hiro bromua khng th
iu ch nh hiro florua hay hiro clorua bng cch cho axit sunfuric
m c tc dng ln mui halogenua tng ng, v hiro bromua c
hnh thnh d b oxi ha hn hiro florua v hiro clorua. Cht oxi ha
trong trng hp ny l axit sunfuric m c
2HBr + H
2
SO
4()
H
2
O + Br
2
+ H
2
SO
3

- Tuy nhin ngi ta c th dng axit khng c tnh oxi ha cho tc
dng vi natri hay kali bromua iu ch hiro bromua tinh khit,
chng hn s dng axit photphoric c
3KBr + H
3
PO
4()
K
3
PO
4
+ 3HBr
- Hiro bromua c th c iu ch t cc n cht
H
2
+ Br
2(hi)
2HBr; kJ/mol
nhit cao c s phn hy hiro bromua thnh cc n cht.
Do vy, trong thc t phi dng cht xc tc phn ng c th thc
hin c nhit thp to thun li cho s chuyn dch cn bng v
pha to thnh hiro bromua. Cht xc tc c dng l bt platin xp
hay than hot tnh.
Hiro bromua cng c th c iu ch bng cch cho brom tc
dng vi cc hp cht ca hiro. Trong phng th nghim ngi ta
thng dng phn ng brom tc dng vi hiro sunfua
H
2
S + Br
2
2HBr + S
4.6.2. Tnh cht vt l
Hiro bromua l cht kh khng mu. Khi lm lnh hiro bromua
s ngng t thnh cht lng khng mu, c nhit si 206,4K. Tip tc
lm lnh su hn na hiro bromua lng s ha rn thnh nhng tinh th
khng mu, c nhit nng chy 186,33K. Hiro bromua bc khi
mnh ngoi khng kh m, ha tan trong nc nhiu hn hiro clorua.
Mt th tch nc c th ha tan 612 th tch hiro bromua 273K. Cc
mng nhy ng h hp b tn thng khi ngi ta hit th phi kh
hiro bromua.
4.6.3. Tnh cht ha hc v ng dng
Trong dung dch nc, hiro bromua th hin tnh axit, c gi l
axit bromhiric. Lin kt gia hiro v brom trong hiro bromua khng
bn bng lin kt gia hiro v clo trong hiro clorua. Do vy clo y
c brom ra khi hiro bromua.
Phn ng cho thy hiro bromua l cht kh mnh hn hiro
clorua v clo l cht oxi ha mnh hn brom.
Cc mui ca axit bromhiric l cc bromua. Phn ln cc mui
bromua d tan trong nc. Mui bc bromua thc t khng tan v mui
ch bromua kh tan trong nc.
48

Cc bromua ca kim loi kim l nhng mui quan trng trong ha
hc. Cc mui ny c dng lm thc an thn v thuc ng. Bc
bromua c dng trong sn xut phim v giy nh.
4.7. Cc oxit v oxiaxit ca brom
4.7.1. Cc oxit ca brom
Brom rt kh hnh thnh cc hp cht vi oxi.
Cc oxit c th tn ti: Br
2
O, BrO
2
, BrO
3
. Tuy nhin tt c cc hp
cht ny khng bn v khng c ngha thc t.
- ibrom oxit Br
2
O: c iu ch bng cch cho brom tc dng
vi thy ngn oxit
2Br
2
+ HgO HgBr
2
+ Br
2
O
Br
2
O c nhit si 255,65K, nhng ch bn di 233,15K hoc
bn khi ha tan vo tetraclocacbon. ibrom oxit l anhirit ca axit
hipobrm (HBrO). Cho dung dch ibrom oxit trong tetraclocacbon tc
dng vi dung dch kim ta c dung dch mui hipobromit.
- Brom ioxit BrO
2

Brom ioxit ch bn nhit di 233,15K.
Brom ioxit c hnh thnh khi phng in qua hn hp hi brom
v kh oxi di p sut. entanpi hnh thnh chun ca hp cht l +
52,5kJ/mol.
- Brom trioxit BrO
3

Brom trioxit c iu ch bng cch phng in m qua hn hp
brom v lng oxi hoc ozon. Hp cht ny khng bn, t phn hy
nhit trn 203K.
4.7.2. Cc oxiaxit ca brom
Ngi ta ch mi iu ch c ba oxi axit ca brom vi s oxi
ha +1, +5 v +7. l axit hipobrm (HBrO), axit bromic (HBrO
3
), v
axit pebromic (HBrO
4
).
- Axit hipobrm HBrO: c hnh thnh mt lng h qu trnh
t oxi ha kh ca brom ha tan trong nc
H
2
O + Br
2
HBr + HBrO
loi tr axit bromhiric ng thi xut hin trong phn ng
ngi ta cho thm thy ngn (II) oxit vo dung dch nc brom
H
2
O + 2Br
2
+ HgO HgBr
2
+ 2HBrO
Axit hipobrom c c c trong chn khng nhit thp hn
303K, c th t ti nng 6%.
Cc mui ca axit hipobrom c iu ch bng cch ha tan
brom vo cc baz tng ng
2KOH + Br
2
KBr + KBrO + H
2
O
- Axit bromic HBrO
3
:
+ iu ch: nguyn tc chung iu ch axit bromic v cc mui
bromat l un nng dung dch cha ion hipobromit s xy ra qu trnh t
oxi ha kh theo phng trnh.
3BrO
3
2Br
-
+ Br
Nh vy t dung dch axit hipobrom un nng ta nhn c dung
dch axit bromic bng phn ng t oxi ha kh
3HBrO 2HBr + HBrO
3

Mui ca axit bromic l cc bromat c iu ch t cc mui
hipobromit tng ng, v d:
3NaBrO NaBrO
3
+ 2NaBr
49

Axit bromic bn hn axit hipobrom. Dung dch axit bromic c th
c c ln 50% m khng b phn hy. Axit bromic khng c ngha
thc t, ngc li cc mui ca n c dng lm cht oxi ha.
- Axit pebromic HBrO
4
v mui pebromat:
+ iu ch: Nguyn tc chung iu ch mui pebromat v sau
l axit pebromic l oxi ha ion bromat bng flo trong mi trng kim
Br + F
2
Br + 2F
-
+ H
2
O
Mt s mui pebromat kh tan trong nc lnh nhng tan tt trong
nc nng, v d KBrO
4
c tch ra khi dung dch mt cch d dng.
Axit HBrO
4
c iu ch t mui pebromat v axit mnh, bn trong
dung dch long di 6M, c tnh oxi ha mnh
( ).



Tit 26,27
Bi 5. IOT (I) V ATATIN

A. MC TIU:
Trng thi t nhin; iu ch; tnh cht vt li, tnh cht ha hc;
ng dng; hiro ioua (iu ch; tnh cht vt li; tnh cht ha hc); cc
oxi v oxiaxit ca iot v atatin.
B. NI DUNG: IOT
Z = 53
Khi lng nguyn t: 126,9044
S khi ca ng v: 127
Cu hnh electron: [Kr]4d
10
5s
2
5p
5

5.1. Trng thi t nhin
Iot c Becna Cuctoa (Bernad Courtois) pht hin nm 1811.
Tuy nhin tnh cht nguyn t ca iot mi n nm 1815 mi c Gay
Luyxc cp n v ng t tn theo mu tm ca hi nguyn t ny l
iot.
Iot l nguyn t lun i km vi cc nguyn t hologen khc
nhng l mt nguyn t tng i him. Lng ln iot c trong nc
bin khon 2 3mg trong mt lit. Lng t nhin ca cc halogen clo,
brom, iot so snh vi nhau c t l sau:
Cl : Br : I = 300 : 10 : 0,01
Mt lng nh iot c trong mt s to l bin di dng hp cht
hu c, v cc loi to l tch ly iot c trong nc bin. Khi t cc loi
to ny ngi ta nhn c tro c cha mui ioua. Nu nghin cu tm
thy mt ni no tch t nhiu iot th y c th l mt ch dn cho
bit ni ny tng tn ti cc sinh vt trong cc thi k a cht xa xa,
bi v iot l mt trong cc nguyn t c tch ly trong thc vt v ng
vt qua din bin ca cc qu trnh sinh hc. Iot l mt thnh phn quan
trng ca c th ngi. Khong mt phn t lng iot c trong c th tp
trung tuyn gip. Thiu iot c th c nhng s thay i bnh hon. Bi
vy nhiu nc quy nh trong mui n phi trn mt lng mui iot
ti thiu no y. Ngun nguyn liu chnh sn xut iot l nc lc
khi ch bin natri nitrat ca cc m t nhin (Chil sanpt), trong iot
tn ti di dng natri ioat (NaIO
3
). Ngun nguyn liu khc na l
nc bin v cc loi to. Iot l nguyn t thun khit ch mt ng v
bn .
5.2. iu ch
50

+ Xut pht t cc iotua ly ra t nc bin hay tro mt s loi
to l, iot c iu ch theo cc phng php sau:
- in phn
- Oxi ha bng mangan (IV) oxit trong axit sunfuric c.
- Oxi ha bng clo (clo y iot ra khi mui ioua).
+ iu ch iot t natri ioat trong nc lc ca qu trnh ch bin
natri nitrat.
Natri ioat c kh bng axit sunfur
NaIO
3
+ 3H
2
SO
3
NaI + 3H
2
SO
4

Sau natri ioua tc dng vi dung dch ng (II) sunfat. Qua
mt na s ion ioua b oxi ha thnh iot, cn mt na to thnh ng (I)
ioua, c hai cng kt ta:
2NaI + CuSO
4
CuI + 1/2I
2
+ Na
2
SO
4

Kt ta ny c oxi ha bng mangan ioxit v axit sunfuric c:
CuI + MnO
2
+ 2H
2
SO
4()
1/2I
2
+ CuSO
4
+ MnSO
4
+ 2H
2
O
Bng cch ny ton b lng iot c gii phng v ng (I) tr
li ng (II) nh ban u. Iot c thng hoa khi h phn ng.
5.3. Tnh cht vt l
Iot nhit thng l cht rn kt tinh mu tm en, c nh kim,
c khi lng ring 4,942g/cm
3
. Iot nng chy 386,85K
Iot ha tan d dng vo dung dch nc ca kali ioua, do c s
hnh thnh ion poliioua
I
2
+ I
-
I
3
-

Tip tc kt hp iot vo I
3
-
ngi ta c th t c n KI
9
. Cc
hp cht poliioua cung cp d dng cc nguyn t iot d.
5.4. Tnh cht ha hc
Tnh cht ha hc ca iot ging tnh cht ha hc ca clo v brom,
ch khc nhau v mc .
5.5. ng dng
SGT
5.6. Hiro ioua HI
5.6.1. iu ch
Hiro ioua d b oxi ha hn hiro bromua, v vy khng th iu
ch hiro ioua t mui ioua v axit sunfuric c.
- Hiro ioua c iu ch bng chch cho nc tc dng vi
photpho triioua
PI
3
+ 3H
2
O 3HI + H
3
PO
3

Trong trng hp ny khng cn n hp cht PI
3
m c th xut
pht t nguyn t photpho v iot. Ngi ta cho huyn ph photpho
trong nc nh git ln iot hoc cho dung dch iot ha tan trong kali
ioua nh git ln photpho c phn ng trn.
- Hiro ioua cng c th iu ch bng cch dn kh hiro sunfua
vo bt iot ngm trong nc.
I
2
+ H
2
S 2HI + S
- Phng php tt nht l iu ch hiro ioua t cc nguyn t
bng cch dn kh hiro v hi iot qua mt thp c cha bt platin xp
lm xc tc.
H
2
+ I
2
2HI; H
0
= -10,5 kJ/mol
Phn ng ny to ra sn phm hiro ioua tinh khit.
5.6.2. Tnh cht vt l
SGT
5.6.3. Tnh cht ha hc
51

th kh hay trong dung dch khng tip xc vi oxi ca khng
kh v nhit bnh thng th hiro ioua bn. Khi tip xc vi oxi c
s oxi ha chm hiro ioua gii phng iot
2HI + 1/2O
2
H
2
O

+ I
2

V vy dung dch hiro ioua, c bit l dung dch m c s
chuyn mu nu trong khng kh; nh sng mt tri lm tng tc
phn ng ny.
Tng t nh vy, hiro ioua chuyn thnh iot khi phn ng vi
brom, clo cng nh nhiu cht oxi ha khc.
Hiro ioua l cht kh mnh hn hiro bromua v hiro clorua.
Hiro ioua trong nc l mt axit mnh nn phn ng c vi
nhiu kim loi to thnh mui ioua v kh hiro. V d hiro ioua phn
ng vi kim loi kim th
M + 2HI MI
2
+ H
2

Cc mui kim loi kim ioua l nhng mui quan trng trong ha
hc c iu ch bng cch cho iot tc dng vi dung dch baz tng
ng. un nng dung dch s c s chuyn ha t cc ion hipoioit thnh
ion ioat v io ioua. em c cn dung dch ngi ta thu c hn hp
mui ioua v ioat
Trn ln hn hp mui ny vi bt than g ri em nung.
2IO
3
-
+ 3C 2I
-
+ 3CO
3

y cng l phng php iu ch cc mui kim loi kim ioua
trong cng nghip.
5.7. Cc oxit v oxiaxit ca iot
5.7.1. Axit hipoio (HIO)
2I
2
+ H
2
O + 2HgO HgO.HgI
2
+ 2HIO
Axit ny rt khng bn v t phn hy
3HIO 2HI + HIO
3

HIO
3
+ 5HI 3H
2
O + 3I
2

Mui ca axit hipoio c gi l hipoioit, bn hn axit. Mui
hipoioit lu t oxi ha kh to thnh iot v mui ioat
5.7.2. Axit ioic (HIO
3
)
Axit ioic c iu ch bng phn ng oxi ha iot vi axit nitric
c hoc vi clo trong dung dch nc
3I
2
+ 10HNO
3()
6HIO
3
+ 10NO + 2H
2
O
Trong trng hp dng clo lm cht oxi ha cn phi loi b axit
clohiric c hnh thnh trong phn ng bng cch cho bc oxit vo
dung dch, nu khng s xy ra phn ng nghch.
Axit ioic cng c th c iu ch t mui ioat v axit
sunfuric.
5.7.3. Axit peioic (H
5
IO
6
)
Ion peioat c to thnh khi oxi ha ion ioat bng ion
hipoclorit trong mi trng kim
IO
3
-
+ ClO
-
IO
4
-
+ Cl
-

Axit peioic c iu ch bng cch cho mui bari orthopeioat
tc dng vi axit sunfuric
Ba
5
(IO
6
)
2
+ H
2
SO
4
2H
5
IO
6
+ 5BaSO
4

Cc mui peioat c iu ch bng cch cho kh clo tc dng
vi ion ioat trong mi trng kim
NaIO
3
+ 3NaOH + Cl
2
Na
2
H
3
IO
6
+ 2NaCl

ATATIN
Z=85
Cc tnh cht ca atatin
52

Cc ng v phng x ca atatin c thi gian bn r rt ngn, nm
gia 10
-4
giy v 8,3 gi. Cc hp cht ca atatin mi c nghin cu
trong thi gian gn y. Ngi ta chng minh c s tn ti ca cc
anion atatinua (At
-
). Ion atatinua c hnh thnh bng phn ng kh
n cht At
2
vi km hay axit sunfur. Cc anion atatinua c th c
kt ta bng ion bc di dng AgAt. Kt ta bc atatinua trong dung
dch khng hon ton nh i vi cc halogenua khc. Atatin d bay hi
tuy khng mnh bng iot nhng c th thc hin qu trnh thng hoa
tinh ch. Hi atatin c i lc ln vi bc v c th phn ng trc tip vi
bc.



Tit 28

Bi 6: Cc halogenua ion v halogenua cng ha tr

A. MC TIU:
Phn bit c halogenua ion v halogenua cng ha tr v cc
tnh cht ca chng.
B. NI DUNG:
Halogenua l tn gi chung hp cht ca nguyn t c m in
b hn halogen vi cc nguyn t halogen. Hu ht cc nguyn t ha
hc u to ra halogenua. y l nhng hp cht quen thuc v quan
trng trong nghin cu l thuyt cng nh trong ng dng thc t. Cc
halogenua c cp ri rc trong cc chng. V s bin thin
m in ca cc halogen trong mt khong kh rng nn tnh cht ca
cc halogenua khc nhau. Theo bn cht lin kt trong phn t,
halogenua chia thnh hai nhm: halogenua dng ion v halogenua c lin
kt cng ha tr, gi tt l halogenua ion v halogenua cng ha tr.
7.1. Halogenua ion
Halogenua ion l halogenua th rn c mng tinh th bao gm
cc ion l tng (l tng ha). Thc ra trong lin kt gia cc nguyn t
v halogen c coi l lin kt ion vn lun c mc no l lin kt
cng ha tr. Cc kim loi kim, kim th (tr nguyn t u nhm Li v
Be), cc nguyn t h lantan v h actini to nn hp cht halogenua ion.
Mc cng ha tr tng ln theo t s ca in tch tng v bn knh ca
kim loi. V d lin kt cng ha tr trong hp cht halogenua sau: KCl
CaCl
2
ScCl
3
TiCl
4
. KCl c coi l hp cht ion thun ty, trong khi
TiCl
4
thc cht l hp cht cng ha tr. Trong cc halogenua ca
cng mt kim loi c nhiu mc oxi ha khc nhau, halogenua c s oxi
ha thp mang tnh cht lin kt ion cao hn halogenua c oxi ha cao.
V d cc hp cht PbCl
2
, PbCl
4
v UF
4
, UF
6
, trong PbCl
2
v UF
4
l
hp cht ion, cn PbCl
4
v UF
6
l hp cht cng ha tr. Trong mt dy
halogenua ca cng mt kim loi mc cng ha tr ca lin kt tng
ln t flo n iot. V d AlF
3
, c coi l hp cht ion, AlCl
3
mang
nhiu tnh cht cng ha tr, cn AlBr
3
v AlI
3
tn ti di dng ime vi
cc lin kt cng ha tr. Paulinh xut quan h nh lng gia hiu
s m in ca hai nguyn t tham gia lin kt v tnh cht ion (tnh
bng %) ca lin kt:
Tnh cht ion = 1 -
l hiu m in ca nguyn t A v B.
Halogenua ion c nhit nng chy v nhit si cao. Nhit
nng chy l thc o lc tng tc gia cc tiu phn trong cht rn,
53

nhit ny gim dn theo chiu tng ca mc cng ha tr.
Halogenua ion dn in khi nng chy v khi tan trong nc.
7.2. Halogenua cng ha tr
Halogenua cng ha tr c mng li phn t. Tng tc gia cc
phn t trong tinh th l lc Van ec Van. Cc nguyn t phi kim, kim
loi c s oxi ha cao hnh thnh cc halogenua cng ha tr.
Cc halogenua cng ha tr u d bay hi, tan trong dung mi
khng phn cc; khng dn in khi nng chy cng nh khi tan trong
dung mi khng phn cc. Tnh cht ha hc chung nht ca cc
halogenua cng ha tr l d b thy phn to thnh axit halogenhiric,
chng hn nh phn ng
BiCl
3
+ H
2
O

BiOCl + 2HCl
Cc halogenua cng ha tr thng hnh thnh cu halogen gia
hai nguyn t halogenua cng loi, v d Be
2
Cl
4
, Al
2
Br
6

Tit 29
Bi 7: Hp cht gia cc halogen
A. MC TIU:
SV nm c gia cc halogen hnh thnh cc hp cht cng ha
tr; mt s hp cht gia cc halogen c th in li; mt s tnh cht l
ha ca cc hp cht gia cc halogen.
B. NI DUNG:
Cc hp cht gia halogen c cc dng phn t sau: AX, AX
3
, AX
5

v AX
7
trong A l nguyn t halogen xc nh, X l cc nguyn t
khc. Entanpi hnh thnh chun ca cc hp cht ny c tr s tuyt i
nh, v vy hp cht thng khng bn. Lin kt trong tt c cc hp
cht l lin kt cng ha tr. S lng ln nht nguyn t halogen X
trong phn t AX
n
(n = 1, 3, 5, 7) tng ln theo hiu s th tch nguyn t
ca cc nguyn t tham gia vo cu to phn t. Quyt nh thnh phn t
lng ca hp cht khng ch ring i lc ca cc nguyn t vi nhau m
cn c th tch nguyn t ca chng (hoc bn knh nguyn t). V d iot
l nguyn t halogen c th tch nguyn t ln nht so vi flo, clo v
brom, c th lin kt vi by nguyn t flo; trong khi iot ch lin kt
c vi ba nguyn t clo. Brom c th lin kt ti a vi nm nguyn t
flo, ngc li cho ch lin kt c vi ba nguyn t flo. Cc hp cht
ny thng c tng hp trc tip t cc nguyn t, v d clo chy
trong bu kh flo to thnh ClF v ClF
3
Clo triflorua c dng cho
mc ch chin tranh.
Mt s hp cht gia cc halogen c th in li.
V d: 2BrF
3
BrF
2
+
+ BrF
-
4

Hay 2IBr I
+
+ IBr2
-

Iot (I) bromua tc dng vi kalibromua to thnh hp cht
K[IBr
2
].
Cc hp cht florua c dng lm cht flo ha, kh nng flo ha
tng theo dy:
BrF<IF
5
<ClF<IF
7
<BrF
5
<ClF
3

Momen lng cc ca cc hp cht gia cc halogen tng ln khi
hiu s m in ca hai nguyn t tng. ClF c momen lng cc 0,88D;
IF
5
c momen lng cc 2,18D v c hng s in mi cao = 36,1.
Cu trc phn t ClF
3
v BrF
3
c dng ch T. Nguyn t clo v
nguyn t brom trong tm c lai ha sp
3
d to thnh dng chp kp chung
y tam gic, nhng v hai nh chp ch c cc cp electron t do, do
hnh khng gian co li thnh dng mt phng. BrF
5
v IF
5
c dng chp
y vung. IF
7
c dng chp kp chung y hnh nm cnh. Tt c cc
lin kt u l lin kt .
54

Bn cnh cc hp cht trn cn c cc axit phc hp halogen
c iu ch v tinh ch, v d: H(ICl
4
).4H
2
O.
Mt lot cc mui ca cc axit khc cng c iu ch nh
kali hexafloro ioat (K(IF
6
)), kali trtrafloro bromat (K(BrF
4
)) nng chy
603K.


Tit 30
KIM TRA GIA K
A. MC TIU:
Tnh cht ho hc ca halogen. Vit cc phn ng minh ha?
Ti sao tnh kh ca cc hyro halogenua tng ln t HF n HI.
Ti sao cc dung dch axit HBr v axit HI khng th lu trong
khng kh.
Nguyn tc, phng php iu ch halogen (F
2
, Cl
2
, Br
2
, I
2
) trong
phng th nghim, trong cng nghip vit cc phn ng minh ho.
Tnh cht ho hc c bn ca cc hp cht hyr halogenua HX v
vit cc phn ng minh ha? So snh tnh axit
Phng php iu ch cc hp cht hyro halogenua HX
Vit cc phng trnh phn ng khi cho oxi tc dng vi dung dch
axit halogen hyric
B. NI DUNG:
Bi kim tra gia k
l
Cu 1. Tnh cht ho hc ca halogen. Vit cc phn ng minh ha?
Cu 2. a/ Ti sao tnh kh ca cc hyro halogenua tng ln t HF n
HI.
b/ Ti sao cc dung dch axit HBr v axit HI khng th lu trong
khng kh.
Cu 3. Nguyn tc, phng php iu ch halogen (F
2
, Cl
2
, Br
2
, I
2
) trong
phng th nghim, trong cng nghip vit cc phn ng minh ho.

chn
Cu 1. Tnh cht ho hc c bn ca cc hp cht hyr halogenua HX
v vit cc phn ng minh ha? So snh tnh axit?
Cu 2. Phng php iu ch cc hp cht hyro halogenua HX?
Cu 3. Vit cc phng trnh phn ng khi cho oxi tc dng vi dung
dch axit halogen hyric?
P N
l
Cu 1. Tnh cht ho hc in hnh ca cc halogen l tnh oxi ho
mnh: tnh oxi ho gim t F At do m in, v th in cc chun
gim dn, c th:
- Flo tc dng trc tip vi hu ht tt c cc nguyn t tr: N, O, C
dng kim cng, khi trong phn ng th F thng a nguyn t ln s
oxy ho (+) cao nht.
- Clo tc dng vi hu ht cc nguyn t tr O, Ir, N, C.
55

- Brm tc dng vi s nguyn t ging nh Cl nhng phn ng xy ra
km mnh lit hn.
- It tc dng trc tip vi s nguyn t t hn.
- Phn ng vi hyr: H
2
+ X
2

0
t
= HX | (hyro halogenua)
(phn ng xy ra theo mc d mnh lit gim dn t flo n iot)
F
2
+ H
2

0
252 C
2HF (hn hp n)
Cl
2
+ H
2

0
t
2HCl (hn hp n)
Br
2
+ H
2

0
t
2HBr (khng n )
I
2
+ H
2
0
t
2HI (khng n)
Tc dng vi cc phi kim .
3F
2
+ S SF
6

3Cl
2
+ 2P 2PCl
3
PCl
3
+ Cl
2
PCl
5
Tc dng vi kim loi
Cl
2
+ Na 2NaCl
3Cl
2
+ 2Fe 2FeCl
3

- Tc dng vi hp cht:
V d: Clo oxi ho dung dch FeCl
2
thnh FeCl
3
2FeCl
2
+ Cl
2
2FeCl
3

Cl
2
+ 2H
2
O + SO
2
2HCl + H
2
SO
4

Hay khi thm dung dch H
2
S trong nc vo dung dch it th cht
lng b mt mu v dung dch tr nn c mu c.
H
2
S + I
2
S + 2HI
Hoc cho dung dch nc brm tc dng vi dung dch Na
2
SO
3

dung dch mt mu brm
Br
2
+ Na
2
SO
3
+ H
2
O Na
2
SO
4
+ 2HBr.
+ Oxi ho c hp cht khc: v d tc dng vi nc khi
ngoi nh sng
2F
2
+ 2H
2
O 4HF + O
2
|
trong khi it khng tc dng nh vy v: I
2
+ H
2
O = 4H
+
+ I
-
+ O
2
nhng vi clo v brm qu trnh oxi ho nc gii phng oxi i hi
nng lng hot ho cao hn nn phn ng xy ra theo hng khc:
X
2

+ 2H
2
O H
3
O
+
+ X
-
+ HOX (X: Cl,
Br v I).
* Cc halogen hot ng mnh (c m in ln hn) s y cc
halogen hot ng yu ra khi mui hoc axit halogen hyric:
Cl
2
+ 2NaBr 2NaCl + Br
2

Br
2
+ 2KI 2KBr + I
2

56

* Ngoi ra cc halogen c tnh kh tr Flo : Flo v Clo th hin kh nng
kh khng c r nhng tnh kh tng ln t Br n At khi tc dng vi
nhng cht oxi ho mnh.
Cl
2
+ F
2

0
t
2ClF
Br
2
+ 5Cl
2
+ 6H
2
O 2HBrO
3
+ 10HCl
Iot cn c kh nng to nn nn hp cht trong iot dng cation, v
d iot to nn iot nitrat I(NO
3
)
3
do: I
2
+ AgNO
3
= AgI + INO
3

3INO
3
I
2
+ I(NO
3
)
3
- Va c tnh oxi ho - va c tnh kh :

Cl
2
+ NaOH dd NaCl + NaClO + H
2
O
(nc gia ven)
3Br
2
+ 6KOH
()

5KBr + KBrO
3
+ 3H
2
O
Cu 2. a/ Tnh kh tng theo dy t HF-HCl-HBr-HI, v di lin kt H
X tng, nng lng lin kt H-X ca dy gim dn theo chiu .
b/ Dung dch axit HBr v axit HI khng th lu trong khng kh.v oxi
ca khng kh oxi ha cc dung dch ny.
HBr v HI u l cht kh mnh. Dung dch ca hai hp cht ny
l khng mu, nhng khi lu trong khng kh dung dch s vng dn
do to ra cc n cht Br
2
v I
2
.
2HBr +
2
1
O
2

a/s
Br
2
+ H
2
O
2HI +
2
1
O
2

a/s
I
2
+ H
2
O
Cu 3. a/ Cho axit HX tc dng vi cht oxi ha
0
t
halogen X
2
| (cht
oxi ho thng dng l: MnO
2,
KMnO
4
, K
2
Cr
2
O
7
, HClO
3
, H
2
SO
4
c,
PbO
2
)
MnO
2
+ 4HX MnX
2
+ X
2
| + 2H
2
O (X: Cl, Br, I)
2KMnO
4
+ 16HCl 2MnCl
2
+ 2KCl + 5Cl
2
| + 8H
2
O
K
2
Cr
2
O
7
+ 14HCl 2KCl + 2CrCl
3
+ 3Cl
2
| + 7H
2
O
H
2
SO
4
+ HBr Br
2
+ SO
2
+ 2H
2
O
b/ Phng php in phn
- in phn mui halogen nng chy: 2MXn
nc phan din
2M +
nX
2
Flo l phi kim mnh nht, nn khng th c 1 nguyn t ho hc no c
th kh c in tch (-) ca ion F gii phng flo, phi dng dng
in in phn nng chy:
2KF
nc phan din
2K + F
2
|
CaF
2

nc phan din
Ca + F
2
|
- Trong cng nghip in phn dung dch axit HX, hoc dung dch
cc mui halogenua c mng ngn:
HCl
dd phan din
H
2
| + Cl
2
|

57

2NaCl + 2H
2
O
p
ngg mng
H
2
| + Cl
2
| + 2NaOH
c/ Ngoi ra dng hot ng ca cc halogen:
HBr + Cl
2
Br
2
+ 2HCl
NaBr + Cl
2
2NaCl + Br
2

2NaI + Br
2
2NaBr + I
2

chn
Cu 1. 1. Dung dch nc ca cc axit HX u l nhng axit, c gi l
axit halogen hyrc, tnh axit tng theo chiu t HF HI.
- Trong dung dch nc phn ly:
HX + H
2
O H
3
O
+
+ X
-

- Tc dng vi baz, oxit baz to mui v nc.
V d: 2HCl + CuO CuCl
2
+ H
2
O
HCl + NaOH NaCl + H
2
O
- Tc dng vi kim loi hot ng ng trc hyro to mui v
gii phng H
2
|

V d: 2HCl + Fe FeCl
2
+ H
2
|.
- Tc dng vi mui ca axit yu hn.
V d: 2HCl + CaCO
3
CaCl
2
+ CO
2
| + H
2
O
c bit:

4HF + SiO
2
SiF
4
+ 2H
2
O (y l im khc vi
cc axit khc, axit HF l axit duy nht tc dng vi SiO
2
).
Thu tinh SiO
2
tan trong axit HF nn khng th cha axit HF trong
bnh bng thu tinh, m ng dung dch HF bng bnh bch kim, cao su,
ebnit, nha PE.
2. Tnh kh: c trng thi kh cng nh dng dung dch, tnh
kh tng theo chiu t HF HI; HF hon ton khng th hin tnh kh;
HCl ch th hin tnh kh khi tc dng vi nhng cht oxi ho mnh:
4HCl + MnO
2
MnCl
2
+ Cl
2
+ 2H
2
O
HBr v HI th hin tnh kh mnh:
v d axit H
2
SO
4
c b HBr kh n SO
2
v b HI kh n H
2
S.
2HBr + H
2
SO
4
() SO
2
+ 2H
2
O + Br
2

(Cht oxh)
8 HI + H
2
SO
4
4 I
2
+ H
2
S + 4H
2
O
- Cc dung dch HBr, HI khi lu tr nn c mu vng nu v b
oxi khng kh oxi ho gii phng ra halogen t do.
2HI +
2
1
O
2

a/s
I
2
+ H
2
O.
2.3. Tnh bn: gim t HF HI
Dung dch HI m c s chuyn dn thnh mu nu trong khng
kh. Khi c nh sng mt tri lm cho phn ng xy ra nhanh hn.
HI
S A/
I
2
+ H
2

Cu 2. Phng php iu ch cc hp cht hyro halogenua HX:
* HF: trong cng nghip HF c iu ch bng cch:
CaF
2
+ H
2
SO
4
() CaSO
4
+ 2HF|
* HCl: c 2 Phng php:
- i t mui n: 2NaCl + H
2
SO
4
()
0
t
Na
2
SO
4
+ 2HCl|
Phn ng xy ra theo 2 nc:
58

NaCl + H
2
SO
4
()

0
t
NaHSO
4
+ HCl|
NaCl + NaHSO
4
0
t
Na
2
SO
4
+ HCl|
- C th iu ch trc tip bng cch cho tc dng trc tip hyro
vi clo:
H
2
+ Cl
2

0
t
2HCl
* HBr: HBr khng th iu ch ging nh HF v HCl bng cch
cho axit
H
2
SO
4
() tc dng ln mui halogenua tng ng v HBr c hnh
thnh d b oxy ho hn HF v HCl, HBr s tc dng vi cht oxy ho l
H
2
SO
4
()
Vy ngi ta c th dng axit khng c tnh oxi ho tc dng vi
NaBr hay KBr iu ch HBr tinh khit
V d: 3NaBr + H
3
PO
4
Na
3
PO
4
+ 3HBr
Hoc cho Brm tc dng vi hp cht ca hyr
H
2
S + Br
2
2HBr + S
* HI: HI c iu ch bng cch cho nc tc dng vi phot pho
(III) ioua
PI
3
+ H
2
O HI + H
3
PO
3

hoc I
2
+ H
2
S 2HI + S (dn kh H
2
S vo bt it ngm trong
nc).
Phng php tt nht l dn kh hyro v hi it qua thp c cha bt
Platin xp lm cht xc tc.
H
2
+ I
2
2HI
Phn ng ny thu c HI tinh khit
Cu 3. HF khng phn ng, HCl ch phn ng trng thi kh
khi c xc tc hay nhit cao:

2HBr +
2
1
O
2

a/s
Br
2
+ H
2
O
2HI +
2
1
O
2

a/s
I
2
+ H
2
O


Chng 5: CC NGUYN T NHM VIA -10
A. MC TIU:
V tr cc nguyn t nhm VIA, cu hnh electron, tnh cht c
trng, quy lut bin i tnh cht trong nhm, tnh cht ca cc hp cht
ca cc nguyn t nhmVIA
B. NI DUNG:





59

Tit 31

Bi 1: C IM CHUNG

A. MC TIU:
c im v cu to v tnh cht chung nht ca cc nguyn t
nhm VIA.
B. NI DUNG:
Cc nguyn t nhm VIA c m in nh hn nhm halogen
(tr oxi c m in ln hn clo).
C 6 electron lp ngoi cng ns
2
np
4
. Tr oxi cn tt c cc
nguyn t khc u hnh thnh ion m X
2-
trong dung dch nc. Ngc
li chng khng hnh thnh ion dng t do (tr pololi).
trong cc hp cht vi oxi, cc nguyn t nhm VIA c s oxi ha
cao nht l +6 tng ng vi s nhm, tuy nhin cc nguyn t ny c
cc hp cht th hin s oxi ha +4 cng tng i bn. Vi oxi l ngoi
l, nh cc nguyn t u nhm khc, t mang nhng c trng in hnh
ca nhm, chng hn oxi tn ti di trng thi kh iu kin thng,
trong khi cng iu kin cc nguyn t cn li trong nhm l nhng
cht rn.
Nguyn t ph bin nht ca nhm l oxi chim 49,5% khi lng
cc cht cu to v qu t. Lu hunh tham gia cu to v qu t ch
c 0,06%; trong khi selen v telu l nhng nguyn t him, chim
8.10
-5
% thnh phn cu to v qu t. Pololi l sn phm phn r phng
x t nhin ca dy urani v c th iu ch nhn to bng cc phn ng
ht nhn.

Bi 2: LU HUNH (S)
A. MC TIU:
Trng thi t nhin; iu ch; tnh cht vt l; tnh cht ha hc ca
lu hunh; ng dng ca lu hunh; hiro sunfua; hp cht oxi v
oxiaxit ca lu hunh; cc hp cht ca lu hunh vi halogen.
B. NI DUNG:

Tit 32

2.1. Trng thi t nhin
Lu hunh l nguyn t phi kim c bit sm nht. Trong thin
nhin lu hunh tn ti di dng t do v hp cht.
Cc dng tn ti ca lu hunh?
2.2. iu ch
Lu hunh c khai thc t ngun t nhin hoc iu ch t cc
hp cht nh oxi ha hiro sunfua hay kh lu hunh ioxit.
2.2.1. Khai thc t ngun t nhin
- : m lu hunh ln . Hm lng lu hunh t 8 40%,
trung bnh l 25%. T lu hunh, ngi ta em nung chy trong cc l
nung ly lu hunh. Trc y ngun nhit c to ra bng cch rt
th s l t i mt phn lu hunh. L n chic (Calcaroni) khi nung
ch tn dng c 3% lng nhit v thu c 50% lu hunh. L lin
hon (Foni) xy dng t 4 6 l thnh mt vng trong tn dng c
ngun nhit v thu hoch n 80% lu hunh. Bng phng php ny,
ngi ta ch thu c lu hunh th. Mun c lu hunh tinh khit cn
phi ct li trong cc thit b bng gang v hi lu hunh c dn vo
phng ngng t. Nu gi nhit phng ngng t di nhit nng
60

chy ca lu hunh ngi ta iu ch c bt mn mu vng, cn nu
gi nhit cao hn nhit nng chy th lu hunh lng ng li di
cc khun bng g lu hunh ng rn thnh lu hunh thi. Ty theo
mc ch s dng, ngi ta c th tin hnh sn xut bng cch ny hay
cch khc.
- Inonesia: Ti Ioonesia cng nhn khai thc lu hunh rt
n gin bng cch dng cuc chim hay x beng b v cc khi lu
hunh ln va mi ng rn gn ming ni la ang phun v xp lu
hunh vo st gnh v ni tiu th. Loi lu hunh ny tng i tinh
khit.
- M : Lu hunh dng n cht trong t nhin M (Louisiana,
Texas) phn b su di lng t t 150 n 240m trong cc va dy t
25 n 60 mt ln trong cc lp ct xp, d di ng. Bi vy khng th
khai thc theo kiu hm l m phi dng hi nc qu nng lm chy lu
hunh di lng t v dng khng kh nn y lu hunh lng ln mt
t.
2.2.2. Thu hi lu hunh t hiro sunfua
Qu trnh bin i hiro sunfua thnh lu hunh c thc hin
bng cch t kh ny vi oxi di tc dng ca mt s cht xc tc. Cc
cht xc tc quan trng cho phn ng ny l boxit, than hot tnh, st (III)
hiroxit. Hiro sunfua c th c t vi khng kh trc tip chuyn
thnh lu hunh
3H
2
S + 3/2O
2
3S + 3H
2
O
Cch trc tip ny c mt bt li l nhit phn ng ta ra nm
trong khi cht xc tc rt kh loi tr khng ch nhit .
Phng php mi hn (phng php Claus) c th loi b c
bt li trn bng cch t hiro sunfua theo hai giai on
H
2
S + 3/2O
2
SO
2
+ H
2
O
SO
2
+ 2H
2
S 3S + 2H
2
O
Ch c giai on 2 cn n xc tc v phn ln nhit lng c
gii phng ra giai on 1.
Lu hunh c iu ch bng phng php ny rt tinh khit (t
nht 99,5%) nn khng cn phi tinh ch li.
2.2.3. Thu hi lu hunh t kh sunfur
Mt s kh cng nghip nh kh nung oxi ha qung sunfua c
cha kh sunfur. T kh sunfur, ngi ta c th iu ch lu hunh
bng cch dn kh sunfur qua mt l phn ng cha than cc c
nung nng, trong kh sunfur b kh thnh lu hunh
SO
2
+ C CO
2
+ S

Tit 33

2.3. Tnh cht vt l
2.3.1. Lu hunh rn
Lu hunh l mt nguyn t c nhiu dng th hnh rn. ng ch
l hai dng th hnh kt tinh in hnh: lu hunh hay lu hunh trc
thoi v lu hunh hay lu hunh mt nghing (ngoi ra cn c lu
hunh , lu hunh , lu hunh v nh hnh).
Trng thi cn bng gia lu hunh v lu hunh cng nh
trng thi nng chy c th rt ra t gin pha ca lu hunh. Gin
p sut hi gm ba on. Lu hunh bn cho n nhit 368,75K v
bt u t nhit ny v di p sut hi ca n bin i sang dng th
hnh th hai l lu hunh . 392,35K, lu hunh trng thi cn
61

bng vi th hi ca n v nng chy. Khi tng p sut im bin i t
lu hunh trc thoi sang mt nghing (n t) chuyn dch theo hng
nhit cao hn. p sut trn 121590kPa s khng c khong tn ti ca
lu hunh mt nghing v ch c s tn ti ca lu hunh trc thoi. Nu
un lu hunh tht nhanh ln 368,75K th n vn gi nguyn trng thi
bn tm thi. Trong trng hp ny khng c s bin i sang dng th
hnh . iu ny c trnh by bng ng chm trn gin . Tng t
nh vy, khi ngi ta lm lnh lu hunh lng xung di 392,35K m
khng ha rn. ng biu din ny c v bng nhng chm. Trn
gin pha chng ta thy hai ng ct im A (386K). y l im
si l tng ca lu hunh . Qu trnh chuyn lu hunh sang lu
hunh gn vi mt hiu ng nhit b
S S ; H
0
= +0,44kJ/mol
y c s thay i tnh cht vt l nh khi lng ring, dn
nhit v.v
Lu hunh c cu to theo vng sng khp kn gm 8 nguyn
t; khong cch gia hai nguyn t lu hunh l 204pm v gc gp khc
l 107,5
0
. Trong lu hunh c l cng tn ti dng phn t S
8
, nhng
do c s sp xp cc vng ny khc nhau ph hp vi h tinh th
tng ng.
Lu hunh ha tan tt trong mt s dung mi hu c, v d trong
cacbon isunfua, toluen
T dung dch toluen lu gi nhit trn im bin i lu hunh
v lu hunh , lu hunh s kt ta dng mt nghing.
2.3.2. Lu hunh trng thi lng
Trn nhit nng chy ca S, lu hunh l mt cht lng linh
ng mu vng. nhit cao hn lu hunh tr thnh cht lng snh
c mu nu. 460K lu hunh lng t nht ti a, gp khong
mi nghn ln nht ban u, snh n mc khng th ra khi cc
un khi ta dc ngc. Tip tc un ln nhit cao hn, lu hunh lng
li tr nn linh ng v gim dn nht cho n khi t nhit si
717,75K.
Nu lm lnh nhanh lu hunh lng, v d lu hunh lng vo
nc lnh ra s nhn c lu hunh do c tnh cht ging nh cao su.
Khi ko dn lu hunh do ra c cu trc hnh si. Nguyn nhn ca
tnh cht ny l do s thay i trong cu trc phn t ca lu hunh. Lu
hunh lng linh ng trn nhit nng chy, c gi l lu hunh
(ha tan trong cacbon isunfua) vn gi nguyn cu trc phn t vng
tm nguyn t. Khi a nhit ln qu 433K bt u c hin tng
polime ha keo theo s tng nht. S polime ha xut hin do c s
ph v cu trc vng v hnh thnh mch thng di n khong 10
6

nguyn t lu hunh. Lu hunh do c gi l lu hunh (khng
ha tan trong cacbon isunfua). Mi y mt s nh nghin cu a ra
cc ngh khc vi cu trc ca lu hunh do ni trn. Nu tip tc
tng nhit s c s gim nht. y l quy lut chung v nht
ca mt s cht lng ph thuc vo nhit . Nhit cng tng nht
cng gim, v th n thi im ny chm dt hnh thnh lu hunh
do.
2.3.3. Lu hunh trng thi kh
Lu hunh si nhit 717,75k. nhit cao hn im si
cht t trong hi, lu hunh tn ti dng phn t S
8
. Tng nhit ln s
xut hin phn t lu hunh S
4
v cui cng l phn t S
2
. S phn li
phn t S
2
thnh nguyn t lu hunh cn n mt nng lng ln,
62

nhng nh hn nng lng phn li ca phn t oxy. phn li ca
phn t lu hunh S
2
2000K l 3,7% v 3000K l 72,6%.
2.3.4. Lu hunh dng keo
Nu lm lnh nhanh hi lu hunh th hi ny ngng t di dng
ht mn mu vng gi l lu hunh hoa. Lu hunh hoa c thnh phn
ch yu l lu hunh v nh hnh. Nu tng
0
t ln, lu hunh v nh
hnh chuyn dn thnh lu hunh tinh th. Lu hunh v nh hnh cng
c hnh thnh qu trnh phn hy mt s hp cht lu hunh trong
dung dch nc.
V d: Na
2
S
2
O
3
+ H
2
SO
4
Na
2
SO
4
+ SO
2
+ S + H
2
O
y xut hin mt huyn ph lu hunh. Cc tiu phn lu
hunh nh n mc chng i qua c tt c cc mng lc ca phng th
nghim. Cc dung dch ny th hin nhng tnh cht c trng ring ca
n, c gi l dung dch keo. Dung dch keo lu hunh cn c to ra
khi cho kh hirosunfua tc dng vi dung dch SO
2

SO
2
+ 2H
2
S 3S + 2H
2
O

Tit 34

2.4. Tnh cht ha hc
Lu hunh l nguyn t hot ng, nhng iu kin thng li t ra tr v
phn t S dng trng hp mch khp kn, khi un nng S tng tc vi hu ht cc
nguyn t tr kh him, N
2
, Au, Pt, Ir.
+ Tnh cht ho hc ch yu ca S l tnh oxy ho.
- Tc dng vi kh hyro nhit cao : S + H
2

C 300
0
H
2
S (phn ng
xy ra km mnh lit hn so vi phn ng ca oxi vi hyro).
- Tc dng vi kim loi: nhit thng tc dng vi KLK, kim th, Cu, Ag,
Hg, khi un nng th tc dng vi Fe, Al, Pb, Zn.
S
o
+ Hg
o
Hg
+2
S
-2

S + Fe
0
t
FeS
S + 2P P
2
S
5
S + C CS
2
+ Tnh kh: Th hin tnh kh khi tc dng vi phi kim mnh hn nh: F, Cl,
O
2
, Br, P (tr N
2
, I
2
)
V d: S + 3F
2
F
6
S
S + O
2
SO
2

S + 2Cl
2

0
t
SCl
4

Ngoi ra lu hunh kh c cc cht oxy ho
V d: S + 6HNO
3
()
0
t
H
2
SO
4
+ 6NO
2
| + 2H
2
O
S + 2H
2
SO
4
()
0
t
3SO
2
| + 2H
2
O
3S + 2KClO
3
2KCl + 3SO
2
|
S t oxi ho - t kh ca S:
63

3S + 6NaOH 2Na
2
S + Na
2
SO
3
+ 3H
2
O
2.5. ng dng ca lu hunh
Lu hunh v nhiu hp cht ca n c trong thin nhin l nhng
nguyn liu qu gi sn xut ra axit sunfuric v cc hp cht cn thit
khc. Mt lng ln lu hunh c dng lu ha cao su.
Do im bt la tng i thp ca lu hunh nn ngi ta dng
lu hunh sn xut thuc n en, pho hoa Trong y hc, dung dch
keo lu hunh c dng iu tr bnh ngoi da. Lu hunh cn c
dng dit cn trng k sinh trn cy trng.

Tit 35, 36

2.6. Hiro sunfua
Cu trc phn t
- Gc lin kt HSH = 92,2
0
, di lin kt S - H l 1,33
- H
2
S l phn t c cc, momen lng cc = 1,02 D
cng l dung mi tt ging vi cc dung mi hu c
Gc ho tr ca HSH nh hn gc ho tr ca HOH l do tng tc y ca 2 ion H
+

trong phn t H
2
O mnh hn trong phn t H
2
S.
2.6.1. Trng thi thin nhin v iu ch
Trng thi thin nhin: Hirosunfua c trong kh thot ra t ni
la, c trong mt s ngun sui khong, v c hnh thnh trong qu
trnh phn hu cc protein: v d: trng thi.
iu ch hiro sunfua:
Dng axit HCl tc dng vi mui sunfua trong bnh kp
Mui sunfua thng dng l st sunfua.
2HCl + FeS H
2
S| + FeCl
2

Mun iu ch H
2
S tinh khit tt nht l dng CaS, BaS.
hoc cho H
2
+ S
0
t
H
2
S
2.6.2. Tnh cht vt l
Hiro sunfua l cht kh khng mu, c mi trng thi v rt c, d ho lng
to thnh cht lng khng mu,
t
0
s = - 60,75
0
C
t
0

nc = - 85,6
0
C.
Ch cn 0,1% kh H
2
S vo khng kh th khng kh nhim c nng, nu
nhim nng cao hn s dn n cht ngi.
Kh H
2
S t tan trong nc, 1 lt H
2
O 20
0
C ho tan c 2,67 lt kh H
2
S,
nhng tan nhiu trong dung mi hu c: 1 lt ru etylic ho tan gn 10 lt kh H
2
S.
2.6.3. Tnh cht ha hc v ng dng
* Trong dung dch nc, hiro sunfua l mt axit 2 nc v rt yu, yu hn axit
H
2
CO
3
. v trong dung nc axit H
2
S phn ly nh sau:
H
2
S + H
2
O

H
3
O
+
+ HS
-
K
1
S

92
0

H H
64

HS
-
+ H
2
O

H
3
O
+
+ S
2-
K
2
do axit H
2
S to nn 2 loi mui: hiro sunfua (cha ion HS
-
); Sunfua ( cha ion S
2-
).
- Tc dng vi baz to mui v nc
H
2
S + 2NaOH Na
2
S + 2H
2
O
H
2
S + CaO CaS + H
2
O
- Tc dng vi mui tan to thnh mui khng tan
H
2
S + 2AgNO
3
Ag
2
S+ + 2HNO
3

H
2
S + Pb(NO
3
)
2
PbS + + 2HNO
3

* Hiro sunfua khng bn, b phn hu nhit cao 400
o
C, 1700
o
C phn
hu hon ton (km bn hn so vi H
2
O) do tnh kh rt mnh l tnh cht c
trng ca hiro sunfua..
H
2
S
0
t
S + H
2
|
- Hiro sufua th kh cng nh dng dung dch l mt cht kh mnh (H
2
S
chy trong khng kh cho ngn la mu xanh nht
2H
2
S + O
2
(thiu) 2S + + 2H
2
O (chy khng hon ton to S +)
2H
2
S + 3O
2
(d) 2SO
2
|+ 2H
2
O (chy hon ton to SO
2
|)
- Tc dng vi cc cht oxi ho khc: cc halogen X
2
, KMnO
4
, K
2
Cr
2
O
7
,
5H
2
S
-2
+ 2KMn
+7
O
4
+ 3H
2
SO
4
2Mn
+2
SO
4
+ 5S
0
+ K
2
SO
4
+ 8H
2
O.
H
2
S + X
2
2HX + S + (X: Cl, Br, I)
Hiro sunfua c th chuyn cc hp cht vi oxi c s oxi ho cao xung cc
hp cht c s oxi ho thp hn.
H
2
S + H
2
SO
4
() H
2
SO
3
+ H
2
O + S +
ng dng:
Dng H
2
S kt ta cation kim loi m mui sunfua ca n khng tan.
H
2
S c dng nhiu trong ho phn tch tch cc nhm kim loi (cation KL) trong
dung dch, da vo tnh cht khc nhau ca cc sunfua.
2.6.4. Mt s mui sunfua thng dng
S kt hp ca lu hunh vi kim loi to ra sunfua kim loi, cc
sunfua kim loi kim nh Na, K, kim th nh Ca, Mg to nn sunfua
ion, tan trong nc tr BeS +. Trong dung dch chng b thu phn mnh
cho mi trng ba z:
S
2-

+ H
2
O

HS
-

+ OH
-

v d: Na
2
S

+ H
2
O

H
2
S

+ 2NaOH
Nhm sunfua (Al
2
S
3
) cng c coi nh l sunfua ion v b thu
phn hon ton to thnh nhm hiroxit v hiro sunfua:
Al
2
S
3
+ 6 H
2
O = 2Al(OH)
3
+ 3H
2
S
- Cc sunfua kim loi khc c cu to phn t cng ho tr, chng u t
tan trong nc, nhng tan trong dung dch axit.
65

ZnS + H
2
SO
4
(l) ZnSO
4
+ H
2
S|
- Mt s sunfua khc trong axit cng khng tan nh: CuS, SnS, SnS
2
,
Ag
2
S, PbS, CdS, HgS, As
2
S
3
, As
2
S
5
....
- Nhiu sunfua kim loi khng tan trong nc c mu c trng nh PbS,
CuS, CoS, NiS mu en, CdS vng, HgS , MnS mu hng.
Do trong phn tch c ng dng tch cc cation kim loi
trong dung dch.
iu ch:
Cho kim loi tc dng trc tip vi lu hunh nhit cao.
Fe + S
0
t
FeS
hoc: BaSO
4
+ 4C
0
t
BaS + 4CO (dng than kh sunfat
nhit cao).
Na
2
SO
4
+ 4C Na
2
S + 4CO
hay: Cho kh H
2
S tc dng vi kim d to thnh sunfua tan
H
2
S + 2KOH K
2
S + 2H
2
O
- Cho dung dch amoni sunfua tc dng vi mui kim loi to thnh cc
sunfua t tan.
(NH
4
)
2
S + Pb(CH
3
COO)
2
PbS + 2CH
3
COONH
4


Tit 37, 38

2.7. Hp cht oxi v oxiaxit ca lu hunh
2.7.1. Cc lu hunh oxit
Lu hunh to nn mt s oxit nh S
2
O, SO, S
2
O
3
, SO
2
, SO
3
, SO
4
,
S
2
O
7
. Quan trng trong thc t l 2 oxit SO
2
, SO
3
l sn phm trung gian
trong qu trnh sn xut axit H
2
SO
4
.
SO
2
lu hunh (IV) oxit: (kh sunfur)
SO
3
lu hunh (VI) oxit: (kh sunfuric hay Sunfutrioxit)
1.1. Lu hunh (IV) oxit (kh sunfur) SO
2

Cu trc phn t SO
2






Gc lin kt gia nguyn t S v 2 nguyn t
oxi l 119,5
0
, khong cch S O = 1,43
0
A
momen lng cc = 1,59D
S

119,5
o

O O
66

phn b lin kt i trong phn t.
* Tnh cht l hc
nhit iu kin thng SO
2
l cht kh khng mu, c mi hc
kh chu, khng chy v khng duy tr s chy, d ho lng thnh cht
lng khng mu.
t
0
s
l -10
0
C
t
0
nc l - 75
0
C
Kh SO
2
d ho tan trong nc, 1 lt nc 20
0
C ho tan c 40
lt kh SO
2

* Tnh cht ho hc: dung dch SO
2
trong nc l axit yu
SO
2
+ H
2
O H
2
SO
3
(axit sunfur)
SO
2
l anhyrit axit.
- Tc dng vi dung dch kim to 2 mui
SO
2
+ NaOH NaHSO
3
(mui hiro sunfit)
SO
2
+ 2NaOH Na
2
SO
3
+ H
2
O (mui sunfit)
* Th hin tnh kh mnh nht l trong mi trng kim
- Cc cht oxi ho mnh nh: HNO
3
, KMnO
4
, K
2
Cr
2
O
7
, X
2
...oxi ho
SO
2
n axit sunfuric v c xu hng t ti s oxi ho +6 l s oxi ho
ti a ca S.
5SO
2
+ 2KMnO
4
+ 2H
2
O 2MnSO
4
+

K
2
SO
4
+

2H
2
SO
4
SO
2
+ PbO
2
PbSO
4

SO
2
+ 2HNO
3
() H
2
SO
4
+ 2NO
2
|
SO
2
+ H
2
O + Cl
2
H
2
SO
4
+ 2HCl
2SO
2
+ O
2

0
450
2SO
3

x/t V
2
O
5

* Ngoi tc dng kh, kh SO
2
cn c tc dng oxi ho khi tc dng vi
mt s cht kh mnh: Mg, Al, Ca ... khi un nng.
SO
2
+ 2Mg
0
t
2MgO + S
Hoc tc dng vi mt s cht kh khc:
SO
2
+ 2H
2
S + 2H
2
O
SO
2
+ 2H
2
S 3S + 2H
2
O
* Tnh bn: Kh bn, kh b nhit phn tch.
- iu ch:
Trong cng nghip iu ch SO
2
bng cch: t chy lu hunh
trong khng kh hoc nung qung cha lu hunh trong khng kh hay
trong dng kh oxi
S + O
2
SO
2

67

4FeS
2
+ 11O
2

0
t
8SO
2
+ 2Fe
2
O
3

(qung pirit)
Ngoi ra c th nung qung khc nh: PbS, ZnS, CaSO
4

4CaSO
4
+ 2C
0
t
4SO
2
+ 4CaO + 2CO
2
|
Trong phng th nghim iu ch kh SO
2
bng cch: cho axit tc
dng ln mui sunfit
H
2
SO
4
+ Na
2
SO
3
Na
2
SO
4
+ H
2
SO
3

H
2
SO
3
H
2
O + SO
2
|
hay kh axit H
2
SO
4
c nng vi Cu
Cu + 2H
2
SO
4
(n)
0
t
CuSO
4
+ 2H
2
O + SO
2
|
C th dng than hoc S kh axit H
2
SO
4
() nhit cao cng
thu c kh SO
2
: C + 2H
2
SO
4
()
0
t
CO
2
+ H
2
O + 2SO
2
|
S + 2H
2
SO
4
()
0
t
2H
2
O + 3SO
2
|
- ng dng:
Kh SO
2
c dng ty mu, nh ty mu t tm, bng, nhng
cht m khng th ty bng Clo .
1.2. Axit sunfur: H
2
SO
3

- iu ch:
Ho tan lu hunh (IV) oxit vo nc to thnh H
2
SO
3

SO
2
+ H
2
O H
2
SO
3

axit H
2
SO
3
khng bn d b phn hu ngay khi c thnh:
H
2
SO
3
SO
2
+ H
2
O
- Tnh cht:
+ Tnh axit: trong dung dch nc axit sunfur phn ly thnh 2
nc.
H
2
SO
3

H
+
+ HSO
3
-

HSO
3
-

H
+
+ SO
3
2-

Axit H
2
SO
3
to ra 2 loi mui ng vi axit 2 nc l:
- mui sunfit (Me
2
I
SO
3
)
- mui hirosunfit (M
e
I
HSO
3
) hirosunfit
+ iu ch mui sunfit bng cch dn kh SO
2
vo dung dch hiroxit
hoc dung dch mui cacbonat tng ng:
2KOH + SO
2
K
2
SO
3
+ H
2
O
Na
2
CO
3
+ SO
2
Na
2
SO
3
+ CO
2
|
68

Cc mui sunfit kh tan trong nc tr mui sunfit kim loi kim,
amonisunfit cn mui hirosunfit d tan .
+ Tnh kh: tnh cht quan trng nht ca axit H
2
SO
3
v cc mui
ca n l tnh kh, trong lu hunh t trng thi c s oxi ho +4
chuyn ln s oxi ho cao nht + 6.
+ Tnh oxi ho: axit sunfur c tnh oxi ho khi tc dng vi cc cht
kh mnh, trong lu hunh t trng thi s oxi ho +4 b kh xung
trng thi oxi ho 0 hoc -2.
H
2
SO
3
+ 6H H
2
S
-2
+ 3H
2
O
H
2
SO
3
+ 3SnCl
2
H
2
S
-2
+ 3SnOCl
2

Kh H
2
S kh axit sunfur thnh S t do.
H
2
SO
3
+ 2H
2
S 3S
0
+ H
2
O.
1.3. Lu hunh (VI ) oxit: SO
3
( tit 34, 35)
Cu trc phn t dng tam tc u




Gc lin kt OSO = 120
0
, di lin kt S O = 1,43
0
A
+Tnh cht l hc
Phn t SO
3
tn ti trng thi hi. Khi lm lnh hi
SO
3
ngng t thnh cht lng d bay hi, gm ch yu nhng phn t
trime mch vng (SO
3
)
3
.
t
0
s l 44,8
0
C;
Lu hunh (VI) oxit c 3 dng th hnh: o, |, .
Nu h nhit n 16,8
0
C th cht lng ny bin thnh khi rn ging
nh nc gi l dng th hnh . Nu lu nhit di 16,8
0
C
th SO
3
- bin thnh dng SO
3
-| c cu to hnh kim long lanh (hnh si
ging nh aming, v nng chy 32,5
0
C). trong dng th hnh | thng
c ln c dng o cng gm nhng phn t polime mch thng (SO
3
)
n
c
di khc nhau do cc nhm t din SO
4
lin kt vi nhau qua nguyn
t O chung.
trng thi kh lu hunh (IV) oxit tn ti di dng phn t SO
3

c cu trc phn t dng tam gic u, c momen lng cc = 0
+Tnh cht ho hc
L mt oxit axit mnh, phn ng vi nc rt mnh to thnh axit
sunfuric (phn ng to nhiu nhit). Do khng th ho tan SO
3
trc

O
O O
S
69

tip vo nc c v hi SO
3
kt hp mnh vi hi nc to thnh
nhng ht sa m axit H
2
SO
4
nh trong kh quyn.
SO
3
+ H
2
O H
2
SO
4

do SO
3
c gi l anhirit sunfuric
- Tc dng mnh vi baz v oxit baz to thnh mui sunfat.
SO
3
+ CaO CaSO
4

SO
3
+ 2NaOH Na
2
SO
4
+ H
2
O
Cng thc chung:
SO
3
+ Me
II
O MeSO
4

SO
3
l cht oxy ho mnh, tng tc vi cc halogen

(nht l ioua) ca
cc KL v khng KL gii phng ra halogen.
2SO
3
+ 2KI I
2
+ K
2
SO
4
+ SO
2

hoc tc dng vi cht kh khc: 3SO
3
+ H
2
S 4SO
2
+ H
2
O
Thm ch kh SO
3
kt hp c vi H
2
SO
4
c 98% to thnh axit
isunfuric ( olium)
SO
3
+ H
2
SO
4
() H
2
S
2
O
7
.
Thm ch chng kt hp vi nhau to thnh trime (SO
3
)
3

iu ch:
Trong PTN: Tch nc t axit sunfuric
H
2
SO
4

4 10
2
P O
H O

SO
3
+ H
2
O
Cng c th iu ch bng cch nhit phn cc mui sunfat
2NaHSO
4

0
t
Na
2
SO
4
+ SO
3
+ H
2
O
Na
2
S
2
O
7

0
t
Na
2
SO
4
+ SO
3

Na
2
SO
4

0
t
Na
2
O + SO
3

1.4. Axit sunfuric: H
2
SO
4

Cu to phn t: c cu to hnh t din lch, vi nguyn t S
tm
+Tnh cht l hc: axit H
2
SO
4
nguyn cht l mt cht lng nng,
sch nh du, khng mu, khng bay hi.
H
2
SO
4
98%, d = 1,84 g/ml
0
t nc l 10,4
0
C;
0
t s l 296
0
C (b phn hu)
Khi un si H
2
SO
4
nguyn cht mi u cho ch yu l kh SO
3
,
n khi tng ng vi thnh phn ca axit H
2
SO
4
98,2% th si 338
0
C,
ngi ta nhn c axit c cng thnh phn v cng im si gi l hn
hp ng si.
Axit H
2
SO
4
c tan v hn trong nc v khi tan to ra lng nhit
ln. Do khi pha ch H
2
SO
4
() vo nc ngi ta tin hnh pha long
70

bng cch cho axt H
2
SO
4
t t vo nc v khuy u, ch khng c
lm ngc li.
+Tnh cht ho hc
* Axit H
2
SO
4
long c tnh cht ca mt axit thng thng:
- L mt axit mnh, hai ln axit: Qu trnh phn ly theo 2 nc:
H
2
SO
4
H
+
+ HSO
4
-

HSO
4
-

H
+
+ SO
4
2-

- Tc dng vi baz v oxit baz to thnh mui v nc (to 2 loi
mui)
H
2
SO
4
+ NaOH NaHSO
4
+ H
2
O ( mui hiro sunfat)
H
2
SO
4
+ 2NaOH Na
2
SO
4
+ 2H
2
O ( mui sunfat)
- Tc dng vi kim loi ng trc hiro trong dy th in cc gii
phng H
2
: M
e
II
(M
e
II
= Fe, Zn) v ion H
+
trong H
2
SO
4
long ng vai tr
cht oxi ho nn sau phn ng c s to thnh kh H
2
|

Me
(II)
+ H
2
SO
4
(l) MeSO
4
+ H
2
|
- Tc dng vi nhiu mui k c mui NaCl (li dng tnh axit nh hn
nhau).
H
2
SO
4
() + NaCl NaHSO
4
+ HCl |
H
2
SO
4
() + NaNO
3
NaHSO
4
+ HNO
3
|
H
2
SO
4
() + CaCO
3
CaSO
4
+ CO
2
+ H
2
O
H
2
SO
4
+ Ca
3
(PO
4
)
3

0
t
CaSO
4
+ H
3
PO
4

* Axit H
2
SO
4
c:
- Khng bn, d b phn hu 296
0
C to thn SO
3
v H
2
O
H
2
SO
4
()

0 0
337 296
SO
3
+ H
2
O
- C tnh ht nc mnh: H
2
SO
4
+ v bo, ng n ... C +
H
2
SO
4
.H
2
O
C tnh oxi ho mnh (nht l c nng):
+ phn ng vi phi kim C, P, S to thnh kh SO
2
, CO
2
, P
2
O
5
cn bn
thn H
2
SO
4
to thnh SO
2
+ Phn ng vi kim loi:
nhit thng khng phn ng vi Al, Fe
Khi un nng phn ng vi cc kim loi (tr Au, Pt) v khng gii
phng H
2
.
2H
2
SO
4
() + Zn
0
t
ZnSO
4
+ SO
2
| + 2H
2
O
2H
2
SO
4
() + Cu
0
t
CuSO
4
+ SO
2
| + 2H
2
O
71

6 H
2
SO
4
() + 2Al
0
t
Al
2
(SO
4
)
3
+ 3SO
2
| + 6H
2
O
2H
2
SO
4
() + 2Ag
0
t
Ag
2
SO
4
+ SO
2
| + 2H
2
O
- Axit H
2
SO
4
() c tc dng ho than v ph hu nhiu cht hu c:
C
12
H
22
O
11

( )
2 4
H SO d
12C + 11H
2
O
Nhn xt: Lu hunh trong gc axit ng vai tr cht oxi ha nn sau
phn ng khng c s to thnh kh H
2
. Sau phn ng c th to ra SO
2
,
S, hc H
2
S tu hot ng ca kim loi, kim loi c tnh kh cng
mnh th S c s oxi ho cng thp v vi kim loi ng sau H
2
ch to ra
SO
2
.
* Axit H
2
SO
4
i khi th hin tnh kh:
H
2
SO
4
() + 2HI I
2
+ SO
2
+ 2H
2
O
Axit H
2
SO
4
tinh khit c th ho tan kh SO
3
to thnh cc axit
polisunfuric
Hn hp cc axit polisunfuric: H
2
S
2
O
7
, H
2
S
3
O
10
, H
2
S
4
O
13
, H
2
S
n+1
O
3n+4

gi l lum.
+ Phng php iu ch v ng dng
- Trong cng nghip axit H
2
SO
4
c iu ch theo 2 phng
php:
* Phng php tip xc: Trc ht iu ch SO
3
bng cch dng
oxi khng kh oxi ho SO
2
c cht xc tc l V
2
O
5
hoc Platin gn ln
cht aming hay s lm tng din tch b mt tip xc v phn ng
thc hin
0
t l 425
0
C 500
0
C v hiu sut l 98%
2SO
2
+ O
2

5
O

2
xc t c V
2SO
3

Sau cho qua axit H
2
SO
4
c hp th kh SO
3
to thnh axit
H
2
S
2
O
7
(axit isunfuric). Pha long axit H
2
S
2
O
7
vi nc c dung
dch axit H
2
SO
4
theo nng tu
SO
3
+ H
2
SO
4
(98%) H
2
S
2
O
7

H
2
S
2
O
7
+ H
2
O 2H
2
SO
4
(98%).
* Phng php bung ch
Kh SO
2
c oxi ho bng oxi khng kh vi cht xc tc l kh
NO v NO
2

qu trnh phn ng to ra sn phm trung gian l
2SO
2
+ O
2
+ NO + NO
2
+ H
2
O 2NOHSO
4

nitrozoni hirosunfat
Sau dng nc ho tan sn phm thu c axit H
2
SO
4

2NOHSO
4
+ H
2
O 2H
2
SO
4
+ NO + NO
2

72

iu ch axit ly t bung ch ra c nng khong 60 - 70%.
Lu : Nu c nng c hn th ch tan
Pb + H
2
SO
4
(l) PbSO
4
+ + H
2
|
Nu H
2
SO
4
() + PbSO
4
Pb (HSO
4
)
2
tan.
Nu c trong chu thu tinh, s hay chu platin th s t n nng
cao hn.
ng dng: axit H
2
SO
4
l mt ho cht rt c bn c dng iu ch
mui sunfat, phn ln, dng ph cc m qung apatit, phn ng tch
nc ht m, sn xut c quy...
nh gi mt quc gia c pht trin cng nghip mnh hay km th
cng c th cn c vo kh nng tiu th axit sunfuric.
1.5. Axit peoxiiunfuric ( H
2
S
2
O
8
)
iu ch bng cch oxi ho ion SO
4
2-
2SO
4
2-


S
2
O
8
2-
+ 2e
Qu trnh oxi ho kh nn phi dng cht oxi ho mnh nh
F
2
+ 2e 2F
-

Trong CN ngi ta iu ch bng cch in phn axit sunfuric hay mui
vi mt dng ln.
peoxiiunfuric l cht rn kt tinh mu trng, nng chy 333K. Khng
bn, u l nhng cht oxi ho mnh.
2Mn
2+
+ 5S
2
O
8
2-
+ 8H
2
O 2MnO
4
-
+ 10SO
4
2-
+ 16H
+

Dung dch nc khng bn:
H
2
S
2
O
8
+ H
2
O H
2
SO
5
+ H
2
SO
4
( peoximonosunfuric)
H
2
SO
5
+ H
2
O H
2
SO
4
+ H
2
O
2

1.6. Axit thiosunfuric ( H
2
S
2
O
3
)
iu ch: H
2
S + SO
3

195K
H
2
S
2
O
3

iu ch mui: Na
2
SO
3
+ S
0
t
Na
2
S
2
O
3

2Na
2
S
2
+ 3O
2

0
t
2Na
2
S
2
O
3

Hp cht S
2
O
3
2-
khng b v th hin tnh kh mnh.
S
2
O
3
2-
+ 4Cl
2
+ 5 H
2
O 2SO
4
2-
+ 8Cl
-
+ 10H
+

c dng lm cht nh hnh trong k thut ra phim nh, trong dd
Na
2
S
2
O
3
ho tan bc halogenua cn li sau khi hin hnh.
Na
2
S
2
O
3
cn c dng chun it.
I
2
+ 2 Na
2
S
2
O
3
2NaI + Na
2
S
2
O
4
( natri tetrathionat)




73

Tit 39 (t hc)

2.8. Cc hp cht ca lu hunh vi halogen
2.8.1. Cc hp cht ca lu hunh vi flo
S + 3F
2
SF
6

Sunfua tetraflorua c iu ch bng hai cch:
3SCl
2
+ 4NaF SF
4
+ S
2
Cl
2
+ 4NaCl
S + 2Cl
2
+ 4NaF SF
4
+ 4NaCl
2.8.2. Cc hp cht ca lu hunh vi clo
a. isunfu iclorua (S
2
Cl
2
)
isunfu iclorua c hnh thnh khi sc kh clo vo lu hunh
nng chy
S
8
+ 4Cl
2
4S
2
Cl
2

isunfu iclorua l cht lng mu da cam, c mi kh chu, c t
khi d = 1,709 g/cm
3
273K S
2
Cl
2
b phn hy trong nc
S
2
Cl
2
+ 2H
2
O H
2
S
2
O
2
+ 2HCl
Axit thiosunfur (H
2
S
2
O
2
) khng th tch ra khi dung dch, t
phn hy theo phng trnh
H
2
S
2
O
2
H
2
S + SO
2

2H
2
S + SO
2
3S + 2H
2
O
b. Sunfu iclorua (SCl
2
) v sunfu tetraclorua (SCl
4
)
Nu ngi ta cho isunfu iclo tc dng vi clo th s nhn c
sunfu iclorua v mt s hp cht lu hunh clorua vi s oxi ha cao
hn:
S
2
Cl
2
+ Cl
2
2SCl
2
v S
2
Cl
2
+ 2Cl
2
2SCl
4

SCl
2
l cht lng mu , c t khi d = 1,662g/cm
3
288K, c
nhit si, t
si
= 332K v c nhit nng chy = 193K. SCl
4
l cht
lng, nhit ha rn 303K tr ln, l hp cht khng bn, d b phn
hy thnh S
2
Cl
2
v Cl
2
.
2.8.3. Cc hp cht ca lu hunh vi brom v iot
- Lu hunh ch hnh thnh mt hp cht vi brom. l isunfu
ibromua (S
2
Br
2
). S
2
Br
2
l mt cht lng mu sm, c khi lng
ring 2,635 g/cm
3
, c nhit nng chy 227K v nhit si = 330K.
Khi si b phn hy. S
2
Br
2
hu nh khng ha tan lu hunh. S
2
Br
2
km
bn hn S
2
Cl
2
.
- Lu hunh khng to thnh hp cht vi iot.
2.8.4. Thionyl halogenua, sunfuryl halogenua v axit halogensunfonic
- Cc thionyl halogenua c cu to hnh chp tam gic vi nguyn
t lu hunh nh, trong nguyn t lu hunh trng thi lai ha
sp
3


Ba obitan lai ha tham gia lin kt vi obitan p ca cc nguyn
t halogen v oxi, cn li mt obitan lai ha cha cp electron t do ca
lu hunh. Lin kt S-O c di 145pm cho thy s c mt ca lin
kt p-d (c s xen ph gia obitan p ca oxi v obitan d ca lu hunh).
- Thionyl florua (SOF
2
)
Thionyl florua l cht kh khng mu, c nhit nng chy =
163K v nhit si = 243K.
- Thionyl clorua (SOCl
2
)
Thionyl clorua c iu ch bng phn ng gia SO
2
v PCl
5

74

SO
2
+ PCl
5
SOCl
2
+ POCl
3

Thionyl clorua l cht lng khng mu, c mi kh chu. Cc hp
cht ion kh tan trong SOCl
2
, nhng cc hp cht cng ha tr khng
phn cc hoc cng ha tr phn cc t, d tan hn.
- Thionyl clorua c nhit nng chy = 169K v nhit si =
343K.
Nc d dng tc dng vi thionyl clorua to thnh sunfu ioxit v
axit clohiric
SOCl
2
+ H
2
O SO
2
+ 2HCl
Li dng tnh cht ny thionyl clorua c dng iu ch mui
clorua khan ca kim loi t cc tinh th ngm nc.
V d: CuCl
2
.2H
2
O + 2SOCl
2
CuCl
2
+ SO
2
+ 4HCl
Thionyl clorua cn c dng trong tng hp hu c nh sn xut
thuc nhum, dc phm v.v
- Thionyl bromua (SOBr
2
)
Thionyl bromua l cht lng mu da cam, c nhit nng chy
t
(nch)
= 221K v nhit si t
(si)
= 441K.
- Cc sunfuryl halogenua SO
2
X
2
(X = F, Cl)
Phn t ca cc sunfuryl halogenua c cu to hnh t din lch
vi nguyn t lu hunh trung tm.
Cc hp cht ny c coi nh l sn phm th hai nhm -OH trong
phn t axit sunfuric.

- Sunfuryl florua (SO
2
F
2
)
Sunfuryl florua c th iu ch trc tip t sunfu ioxit v flo
SO
2
+ F
2
SO
2
F
2

SO
2
F
2
l cht kh khng mu, khng mi; si 221K, ha rn
153K.
Sunfuryl florua rt tr v mt ha hc. Ngi ta c th un vi
nc trong ni p sut n 423K m vn khng b phn hy, un vi
dung dch kim ch b phn hy rt chm
- Sunfuryl clorua (SO
2
Cl
2
)
- Cc axit halogensunfonic HSO
3
X (X = F, Cl, Br)

Tit 40

Bi 3: SELEN (Se)
A. MC TIU:
Trng thi t nhin, iu ch, tnh cht v ng dng ca selen
Hiro selenua, cc oxit v oxiaxit ca selen.
B. NI DUNG:
3.1. Trng thi t nhin
Selen l nguyn t lun i km vi lu hunh trong cc qung
sunfua nh pirit, ng, st km sunfua v.v
3.2. iu ch
Nguyn liu iu ch selen thng dng l cn b bung ch
ca qu trnh sn xut axit sunfuric. Selen c un vi axit nitric
chuyn ha thnh axit selen H
2
SeO
3

3Se + 4HNO
3
+ H
2
O 4NO + 3H
2
SeO
3

75

Axit selen c kh bng cac hs sc kh sunfur vo dung dch
v selen kt t dng v nh hnh mu
H
2
SeO
3
+ 2SO
2
+ H
2
O Se + 2H
2
SO
4

3.3. Tnh cht v ng dng
Selen c hai dng th hnh mu mang tnh phi kim v mt dng
th hnh mu xm mang tnh cht kim loi.
Selen xm c tnh bn dn v dn in khi c chiu sng. Trong
bng ti, kh nng dn in gim xung gi trin rt b. S tng dn
in ca selen xm khi chiu sng c gii thch bng hiu ng quang
in, cc lng t nh sng c selen hp th gii phng cc electron t
do trong selen. Hiu ng ny c p dng trong thc t lm cu dao
in selen. Cu dao ny t ng khi c chiu sng. Selen xm cn
c dng trong cc t bo quang in, c th pht ra dng electron sau
khi c chiu sng. Cc thit b tng t c dng nhiu cho cc loi
tn hiu v my o.
Mt s phn ng ca selen
Se + H
2
SO
4()
SeSO
3
+ H
2
O
Se + O
2
SeO
2

3.4. Hiro selenua H
2
Se
Se + H
2
H
2
Se
ZnSe + 2HCl H
2
Se + ZnCl
2

3.5. Cc oxit v oxiaxit ca selen
- Selen ioxit
Se + O
2
SeO
2

S

eO
2
+ H
2
O H
2
SeO
3

- Axit selen H
2
SeO
3

H
2
SeO
3
+ 4HI Se + 2I
2
+ 3H
2
O
H
2
SeO
3
+ 2H
2
S Se + 2S + 3H
2
O

- Selen trioxit, axit selenic (SeO
3
, H
2
SeO
4
)
SeO
3
l cht rn khng mu, tn ti di mt vi dng tinh th.
+ iu chm SeO
3

Se + 3O SeO
3

Hoc bng cch cho sunfu trioxit tc dng vi mui kali selenat
SO
3
+ K
2
SeO
4
K
2
SO
4
+ SeO
3

+ Tnh cht ca SeO
3

SeO
3
SeO
2
+ 1/2O
2

SeO
3
tc dng vi nc to axit selenic
SeO
3
+ H
2
O H
2
SeO
4

2SeO
3
+ 3S 3SO
3
+ 2Se
+ Axit selenic (H
2
SeO
4
): dng tinh th khng mu, t
0
nc l 58
0
C,
ht nc mnh ging nh axit H
2
SO
4
l kh nng to thnh hyrat, bin
nhiu cht hu c thnh than, l axit mnh, to ra 2 loi mui.
Hyr selenat HSeO
4
-

mui selenat SeO
4
2-

Mui selenat ging mui sunfat: c tan nh nhau, nhng mui
tan thng ngm nc v c kh nng to phn ging nh mui sunfat.
Tuy nhin axit selenic km bn hn axit H
2
SO
4
, b phn hu
nhit trn 200
0
C
H
2
SeO
4

C
0
200
SeO
2
+ O
2
+ H
2
O
+ C th tc dng vi cht kh yu hn.
76

H
2
SeO
4
+ HCl H
2
SeO
3
+ Cl
2
+ H
2
O
(cht kh yu)
Do axit H
2
SeO
4
l cht oxy ho mnh hn axit H
2
SO
4
, hn hp
axit H
2
SeO
4
v HCl c th ho tan khng nhng Ag m c Au na.
Au + 6H
2
SeO
4
(n) Au
2
(SeO
4
)
3
+ SeO
2
+ H
2
O


Bi 4: TELU (Te)

A. MC TIU:
Trng thi t nhin, iu ch, tnh cht v ng dng ca Te; Hiro
telurua v cc mui telurua; cc oxit v oxiaxit ca telu.
B. NI DUNG:
4.1. Trng thi t nhin, iu ch, tnh cht v ng dng
Telu c Klaprt (Klapproth) pht hin nm 1817. Telu c trong
thin nhin t hn selen khong 80 ln. Tng lng trong v qu t c
tnh khong 10
-6
%. Trong mt s trng hp, telu tn ti trng thi t
do. Mui telurua trong t nhin thng t i km vi mui sunfua, tn ti
trong qung c lp nh bc telurua (Ag
2
Te), bc vng telurua
(AgAuTe
2
). Mt lng nh telu l sn phm ph khi ch bin cc qung
sunfua v trong cht cn b ant khi tinh ch ng bng in phn.
Trong 8 ng v bn ch c ng v l ph bin nht, chim 34,5%.
Telu ch c mt dng th hnh kt tinh vi mng tnh th lc
phng.
Nu kh dung dch axit telur bng axit sunfur s thu c telu
di dng bt mu nu. Sau khi nung chy, telu c mu trng bc v nh
kim, hp thnh t cc du telu vi hai lin kt cng ha tr. Telu mm, d
nghin thnh bt, dn in rt km. Kh nng dn in tng khi chiu
sng nhng t hn selen. Telu nng chy 725K, si 1663K. th hi
mu vng tn ti dng phn t Te
2
, trn 2273K phn t Te
2
phn li thnh
nguyn t.
Te + 2Na Na
2
Te Telunua natri
Te + O
2
TeO
2

- Vi nc Te tc dng 100 n 150
0
C
Te + 2H
2
O TeO
2
+ 2H
2
.
Vi axit H
2
SO
4
c v axit HNO
3
, Te tc dng ging nh lu hunh
Te + H
2
SO
4
() TeSO
3
+ H
2
O
- Vi dung dch kim Te tc dng ging nh S.
3Te + 6KOH = K
2
TeO
3
+ 2K
2
Te + 3H
2
O.
4.2. Hiro telurua v cc mui telurua
H
2
Te l cht kh khng mu c mi nh H
2
S v rt c. Khi so snh vi H
2
O,
th bn nhit gim xung t H
2
O n H
2
Te
V d: H
2
O rt bn
H
2
S bn
H
2
Se tng i bn (phn hu trn 300
0
C).
H
2
Te km bn (phn hu dn nhit thng).
H
2
Po khng bn (phn hu ngay khi c to thnh).
77

Hiro telurua c iu ch t cc n cht, nhng khng phi
bng hiro bnh thng m bng hiro mi sinh. y l phn ng thu
nhit mnh
Te + H
2
H
2
Te; H
0
= 143,64kJ/mol
Ngi ta cng c th iu ch hiro telurua bng cch cho axit tc
dng vi cc mui telurua
Al
2
Te
3
+ 6HCl 3H
2
Te + 2AlCl
3

H
2
Te + 1/2O
2
Te + H
2
O
4.3. Cc oxit v oxiaxit ca telu
- Telu ioxit (TeO
2
)
TeO
2
l cht dng tinh th khng mu, t tan trong nc, nng chy 733
0
C.
+ i t SeO
2
TeO
2
PoO
2
tnh axit gim v tnh baz tng
V d: SeO
2
tan trong nc to thnh axit selen
S

eO
2
+ H
2
O H
2
SeO
3

TeO
2
khng tan trong nc m li tan trong dung dch kim to mui telurit.
TeO
2
+ KOH K
2
TeO
3
+ H
2
O
PoO
2
ch tan trong kim nng chy.
PoO
2
+ 2NaOH
nc t
0
Na
2
PoO
3
+ H
2
O
+ Tnh baz tng: Telu ioxit v poloni ioxit cn c th tan trong cc dung
dch axit:
TeO
2
+ 4HCl TeCl
4
+ 2H
2
O
PoO
2
+ 2H
2
SO
4
Po(SO
4
)
2
+ 2H
2
O
+ Tnh oxi ho: Khc vi SO
2
, SeO
2
v TeO
2
l cht oxi ho mnh, d dng b
kh n selen v telu.
SeO
2
+ 2SO
2
Se + 2SO
3

TeO
2
+ 2SO
2
Te + 2SO
3

- Axit teluric
Axit teluric (H
6
TeO
6
): axit teluric khc hon ton vi axit H
2
SO
4

v H
2
SeO
4
v thnh phn v tnh cht. L cht dng tinh th khng
mu, t tan trong nc lnh, tan trong nc nng.
c iu ch bng cch oxi ha telu hay axit telur vi nhng
cht oxi ha mnh nh axit cloric, axit cromic v.v...
Axit orthoteluric l axit su nc nn c s hnh thnh cc mui axit
dng , v d Na
2
H
4
TeO
6
, Na
4
H
2
TeO
6
v mui trung ha
dng M
6
(I)
TeO
6
, v d Ag
6
TeO
6
, Hg
3
TeO
6
Khi nung nng axit
orthoteluric b tch nc v nhit trn 573K chuyn thnh anhirit
TeO
3
. Telu trioxit l cht rn mu vng, khng tan trong nc.
CU HI LUYN TP
Cu 1: Tnh cht ho hc ca S, H
2
S, SO
2
, SO
3

Cu 2: Tnh cht l, ho hc ca axit H
2
SO
4
, phng php iu ch.
Cu 3: Trnh by nhng hiu bit v nguyn t Se, Te, Po.
Cu 4: So snh tnh cht ho hc ca cc ixit ca Se, Te, Po.
Cu 5: Tnh cht ho hc ca H
2
SeO
4
v so snh vi axit H
2
SO
4
.
cu 6. a/ Trnh by tnh axit ca H
2
SO
3
, H
2
SeO
3
v H
2
TeO
3
.
b/ Tm dn chng chng minh rng H
2
SeO
4
c tnh oxi ho mnh hn H
2
SO
4
.
c/ Ti sao Te to ra axit H
6
TeO
6
nhng S v Se khng c kh nng ?
Cu 7. a/ Tnh cht ho hc ca SO
2
v ca cc mui sunfit.
b/ Vit phng trnh phn ng ca SO
2
vi cc cht: HI, CO, H
2
, H
2
S, C.
78

Cu 8. Vit cc phng trnh phn ng:
1. Zn + H
2
SO
4
()
2. Hg + H
2
SO
4
()
3. Zn + H
2
S
2
O
7
H
2
S ...
4. Cl
2
+ Na
2
S
2
O
3
+ H
2
O
5. I
2
+ Na
2
S
2
O
3

6. Al + Na
2
S
2
O
3
+ HCl
Cu 9. Nhn xt v bn ca cc hp cht H
2
X t oxi n poloni (X = O, S, Se, Te,
Po) ? gii tch nguyn nhn.
Cu 10. a/ Nhn xt v s thay i nhit si t H
2
O H
2
Te, gii thch nguyn
nhn?
b/ Gii thch s thay i tnh axit trong dy ?



Chng 6: CC PHI KIM NHM VA -13

A. MC TIU:
1. V tr ca nhm nit- pht pho trong bng HTTH cc nguyn t ho hc
2. Hiu c tnh cht l, ho hc, iu ch, ng dng ca nit.
3. Hiu c cu to phn t, tnh cht ca amoniac
4. Bit v hiu cc oxit ca nit
5. Hiu cu tp phn t v tnh cht ca axit nitro, axit nitric, cc mui nitrat
6. Bit vn dng l thuyt gi thch mt ss hin tng t nhin c lin quan.
7. Bit gii cc bi tp trong sch gio khoa ho hc pht thng v sch gio trnh
8. Bit v hiu tnh cht ca pht pho, so snh tnh cht cuat nit vi pht pho.
9. Bit v hiu mt s hp cht quan trong ca pht pho: Pht phin, oxit, axit, mui.
B. NI DUNG:

Tit 41 (t hc)
Bi 1: C IM CHUNG
A. MC TIU:
Cc nguyn t trong nhm VA(v tr, bn knh, i lc, nng lng
ion ha, m in, nng lng lin kt; thnh phn %; cc mc oxi ha
c th c.
B. NI DUNG:

Cc i lng c trng N P As Sb
Bn knh nguyn t (pm) 75 110 122 143
Nng lng ion ha I
1
(kJ/mol) 1402 1012 947 834
i lc electron (kJ/mol) +6,8 -72 -77 -101
m in 3,0 2,2 2,2 2,0
Nng lng lin kt X-X
(kJ/mol)
163 200 150 120
Nng lng lin kt XX
(kJ/mol)
941 480 380 295
Z 7 15 33 51
Cu hnh e

[He]
2s
2
2p
3

[Ne]
3s
2
3p
3

[Ar]3d
10
4s
2
4p
3

[Kr]4d
10
5s
2
5p
3

KLNT 14,0067 30,973 74,921 121,75
79

Nguyn t ca nhng nguyn t nhm nit c lp electron ho tr l
ns
2
np
3
, c kh nng kt hp thm 3 electron t cu hnh bn ca
nguyn t kh him, (nguyn t N c kh nng kt hp thm 3 e ca kim
loi hot ng mnh to nn ion N
3-
), nit v nguyn t khc cng nhm
to nn nhng cp e v cho hp cht trong chng th hin mc s oxi
ho +3 hoc -3; 2 electron cn li thng to lin kt cho nhn vi nhng
nguyn t c m in ln, cc nguyn t P, As, Sb, Bi cn c kh
nng to nn 2 lin kt cng ho tr na. Nh vy s oxi ho cao nht ca
cc nguyn t nhm VA l +5. So vi cc nguyn t nhm oxi - lu
hunh th cc nguyn t nhm nit c dng in mnh hn, trong
nhm tnh dng in tng cng vi s th t, v d: pht pho c
dng th hnh bn dn, asen, stibi c coi l nhng cht bn dn, bitmut
c coi l kim loi.
Theo chiu tng ca in tch ht nhn: tnh phi kim gim, m in
gim, tnh kim loi tng.

Bi 2: NIT (N)
A. MC TIU:
Pht hin v trng thi t nhin; iu ch; tnh cht vt l v tnh
cht ha hc; ng dng ca nit.
B. NI DUNG:
NIT (N)
Z = 7
Khi lng nguyn t: 14,0067
S khi ca cc ng v bn: 14, 15
Cu hnh electron: [He]2s
2
2p
3

2.1. Pht hin v trng thi t nhin
Nit c pht hin nm 1772.
Khng kh l ngun cung cp nit ln nht. Trong khng kh c
78,08% th tch, bng 75,52% khi lng nit. Nit hp thnh t hai
ng v bn, tuy nhin ng v c lng nh ch chim 0,365%.
Nit trong khng kh ch tn ti di dng t do, dng hp cht
cc m nh natri nitrat.
Nit c trong c th sinh vt, nit chim gn 3% khi lng c th con ngi
ch yu di dng hp cht hu c phc tp: protein, axit nucleic, cht mu ca mu,
clorophin... ngoi ra trong nc ma nit c lng nh axit HNO
3
v HNO
2
.
2.2. iu ch
+Trong cng nghip: iu ch nitc ch yu t khng kh. Vic
tch oxi i km nit trong khng kh c tin hnh bng phng php
vt l hoc bng phng php ha hc.
Phng php vt l: Nit c iu ch bng cch chng ct phn
on t khng kh lng ( c cp phn iu ch oxi trong cng
nghip).
Phng php ha hc iu ch nit xut pht t khng kh v
cacbon l cht kh loi b kh oxi. Nu t cacbon vi khng kh
trong mt l chuyn dng:
80

4N
2
+ O
2
+ C
0
t
4N
2
+ CO
2

Hn hp kh ny c x l vi dung dch kali cacbnic hay vi
nc di p sut cao loi b kh cacbonic.
+Trong phng th nghim:
loi tp cht oxi, ngi ta cn cho kh nit thu c i qua
ng kim loi t nng.
4N
2
+ O
2
+ 2Cu
0
t
4N
2
+ 2CuO
Nit tinh khit c iu ch bng cch:
- Nhit phn dung dch bo ho mui amoni nitrit
NH
4
NO
2

0
t
N
2
+ 2H
2
O
- Hoc c th thay NH
4
NO
2
bng hn hp mui NH
4
Cl v NaNO
2

nhit phn hn hp mui.
NH
4
Cl + NaNO
2

0
t
N
2
+ NaCl + 2H
2
O
- Hoc c th thay NH
4
NO
2
bng hn hp mui NH
3
v HNO
2

NH
3
+ HNO
2
N
2
+ 2H
2
O
- Nung nng hn hp gm KNO
3
vi bt st kh:
6KNO
3
+ 10Fe 3K
2
O + 5Fe
2
O
3
+ 3N
2
- Cho kh NH
3
qua oxit ng nung nng:
2NH
3
+ 3CuO 3Cu + N
2
+ 3H
2
O.
- Cho dung dch NH
3
tc dng vi cloruavi
2NH
3
+ 3CaCl
2
O 3CaCl + N
2
+ 3H
2
O.
2.3. Tnh cht vt l
Ni t l cht kh khng mu, khng mi, khng v, hi nh hn
khng kh, rt kh ho lng v kh ho rn.
Nit lng c t
0
s l - 195
0
C; t
0
nc l - 210
0
C.
Nit lng c dng trong cc thit b lm lnh.
Nit rt t tan trong nc v trong cc dung mi khc (v d:1000 ml nc ch
ho tan c 23,5 ml kh N
2
), kh nit khng duy tr s sng.
2.4. Tnh cht ha hc
Do cu to phn t N
2
rt bn, v hai nguyn t ca phn t nit lin kt vi
nhau rt bn vng: :N:::N: hay . Trong phn t nit c mt lin kt v hai lin
kt ( )
2
( )
2
( )
2
( )
2
( )
2
. ph v c lin kt ca phn t nit phi
cn n mt nng lng ln:
N
2
2N; H
0
= 948kJ/mol
Nng lng ny b p bng nng lng lin kt ca nit v i cc nguyn t
khc hoc a t bn ngoi vo di dng nhit hay nng lng in. Vy nhit
thng nit l mt cht tr nht, ch hot ng nhit cao, nht l khi c cht xc
tc v th hin nh mt phi kim in hnh.
- Tc dng vi kim loi: nitrua ( iu kin thng ch c Li phn ng vi N
2
)
6Li + N
2
2Li
3
N
3Mg + 2N
2

0
600 C
Mg
3
N
2

- Tc dng vi hp cht ca kim loi:
CaC
2
+ N
2

0
t
CaCN
2
+ C
81

Tc dng vi H
2
nhit cao.
N
2
+ 3H
2

0 0
450 t
2NH
3

500
0
C, XT, P
- Th hin tnh kh: s oxi ho trc tip nit bng O
2
i hi
0
t rt cao khong
3000
0
C - 4000
0
C
N
2
+ O
2

C 4000 3000
0
2NO
H quang in (tia la in)
2.5. ng dng:
Nit l nguyn t dinh dng chnh ca thc vt bi vy nhng lng ln hp
cht ca Nit c thng xuyn cung cp cho t di dng phn m nui cy
trng. Nit dng tng hp NH
3
, dng sn xut axit HNO
3
, trong cng nghip sn
xut thuc n, nit lng c dng trong cc thit b lm lnh.
Nit t do khng c tc dng nhng khng c hp cht ca nit th khng c s sng.




Tit 42
Bi 3: AMONIAC V MUI AMONI
A. MC TIU:
iu ch; tnh cht vt l v tnh cht ha hc; ng dng ca
amoniac v mui amoni.
B. NI DUNG:
3.1. Amoniac (NH
3
)
3.1.1. iu ch
+ Trong phng th nghim iu ch amoniac bng cch:
- Cho baz tc dng vi mui amoni
NH
4
Cl + NaOH NaCl + H
2
O + NH
3
|
- un dung dch NH
3
m c ( NH
3
.aq)
NH
3
.aq
0
t
H
2
O + NH
3
|
- Thu phn amiua KLK bng nc:
NaNH
2
+ H
2
O NaOH + NH
3

- Phn hy nitrua bng nc, v d iu ch amoniac nng
Mg
3
N
2
+ 6D
2
O 3Mg(OD)
2
+ 2ND
3

Kh amoniac iu ch trong phng th nghim bng cc phng php trn cha
nhiu hi nc nn cn c lm kh. Ngi ta dng CaO m khng dng CaCl
2

lm kh amoniac (CaCl
2
to phc vi NH
3
).
+ Trong cng nghip: Tng hp amoniac t khng kh v nc c xc tc l bt
st c hot ho bng K
2
O, Al
2
O
3
, nhit t 450 - 550
0
C, p sut t 200 - 300 atm
N
2
+ 3H
2
2NH
3

3.1.2. Tnh cht vt l
iu kin thng NH
3
l cht kh khng mu, c mi khai, xc, nh hn
khng kh.
t
0
nc: -77,75
0
C ; t
0
s :

- 33,35
0
C.
82

kh NH
3
rt d tan trong nc, 1 lt nc 0
0
C ho tan c 1200 lt kh NH
3
, 20
0
C
ho tan 700 lt kh NH
3
, NH
3
l dung mi ion ho tt i vi nhiu cht.
3.1.3. Tnh cht ha hc
V mt ho hc NH
3
l cht kh hot ng vi cp electron t do
nit, amniac c kh nng kt hp d dng vi nhiu cht.
- Trong trong nc: NH
3
tc dng vi ion H
+
ca nc to ion
NH
4
+

NH
3
+ H
2
O

NH
4
+
+

OH
-

Nh vy dung dch amoniac trong nc c tnh baz nhng l
baz yu
- Tc dng vi axit:
NH
3
+ HNO
3
NH
4
NO
3
NH
3
+ HCl NH
4
Cl
2NH
3
+ H
2
SO
4
(NH
4
)
2
SO
4

Kh NH
3
tc dng vi kh HCl to thnh mui NH
4
Cl dng khi
trng, cho nn ngi ta da vo phn ng ny nhn ra kh HCl.
- Tc dng vi nhiu mui kim loi to thnh nhng amoni acat
dng tinh th nh: CaCl
2
.8NH
3
, CuSO
4
.4NH
3
.
k thch hp NH
3
o phc vi ion kim loi chuyn tip (nh
cp e t do trong nguyn t N).
Ag
2
O + NH
3
+ H
2
O [Ag(NH
3
)
2
]OH
Cu(OH)
2
+ 4NH
3

[Cu(NH
3
)
4
](OH)
2

- Tnh kh mnh nhit cao nhng th hin tnh kh khng c
trng bng kh nng kt hp).
2NH
3
+ O
2
N
2
+ 3H
2
O
2NH
3
+ O
2
2N
2
O + 3H
2
O
3CuO + 2NH
3

0
t
N
2
+ 3Cu + 3H
2
O (khi un nng kh c oxit
ca mt s KL)
2NH
3
+ 3Cl
2
6HCl + N
2

4NH
3
+ 3F
2
NF
3
+ 3NH
4
F (Nit triflorua).
- Tnh oxi ho: khi tc dng vi KL hot ng mnh:
2NH
3
+ 2Na
0
t
NaNH
2
+ H
2
| (Natri amiua)
NH
3
+ Ca CaNH + H
2
| (canxi imiua)
2NH
3
+ 2Al
C
0
900 800
2 AlN + 3H
2
(Nhm nitrua).
3.1.4. ng dng
Amoniac l mt trong nhng cht quan trng trong cng nghip ho cht, phn
ln NH
3
sn xut axit HNO
3
, sn xut phn m, c bit dng trong my lm lnh,
dung dch NH
3
dng lm sch b mt kim loi.
3.2. Mui amoni, cu to ion amoni, tnh cht v ng dng ca cc mui amoni
Nguyn t nit trong phn t amoniac c cc obitan lai ha sp
3
nhng cn mt
obitan lai ha cha tham gia lin kt cha cp electron t do, bi vy phn t amoniac
83

c kh nng nhn thm mt proton to thnh ion amoni (NH
4
+
). Nh vy ion amoni c
cu to khi t din u vi
bn nguyn t hiro nh v nguyn t nit
tm.
di lin kt N-H l 143pm, gn ging
Bn knh ion K
+
(144pm). Do cc mui
amoni ging cc mui kali tng ng v mt s
tnh cht vt l v ha hc, nhng khc mui kali
ch d b nhit phn, d b thy phn trong dung dch kim gii phng
amoniac.
Ion amoni khng mu nn ni chung cc mui amoni thng
khng c mu, tr trng hp ion amoni to mui vi cc anion c mu.
Hu ht cc mui amoni u d tan v phn li mnh trong nc, nhng
d b thy phn trong dung dch to mi trng axit
NH
4
+
+ H
2
O NH
3
+ H
3
O
+
; K = 5,5.10
10
Sn phm trong qu trnh nhit phn ty thuc vo axit to mui
vi ion amoni.
+ Mui ca axit c tnh oxi ha nh axit nitr, axit nitric
NH
4
NO
2
N
2
+ 2H
2
O
NH
4
NO
3
N
2
O + 2H
2
O
Khi nhit phn, axit c gii phng s oxi ha amoniac thnh nit
hay nit oxit.
+ Mui ca axit d bay hi: Khi nhit phn s c phn ng theo
qu trnh ngc vi phn ng hnh thnh hp cht
NH
4
Cl NH
3
+ HCl
(NH
4
)
2
CO
3
NH
3
+ NH
4
HCO
3

NH
4
HCO
3
NH
3
+ CO
2
+ H
2
O
Cc mui amoni cacbonat nhit phn nhit tng i thp. +
Mui ca axit kh bay hi v nhiu nc:
Khi nhit phn mui dng ny c s to thnh mui axit v
amoniac
(NH
4
)
2
SO
4
NH
3
+ NH
4
HSO
4

nhit cao mui axit cng phn hy
NH
4
HSO
4
NH
3
+ H
2
SO
4

H
2
SO
4
SO
3
+ H
2
O
v c th 2NH
3
+ 3SO
3
3SO
2
+ N
2
+ 3H
2
O
Mui amoni clorua; mui amonisunfat; mui amoni nitrat;


Bi 4: HRAZIN V HIROXYAMIN
(c thm)

84


Tit 43:
Bi 5: CC OXIT CA NIT
A. MC TIU:
iu ch, tnh cht vt l, ha hc ca N
2
O, NO, N
2
O
3
, NO
2
, N
2
O
5
.
B. NI DUNG:
I. Cc oxit ca Nit.
Nit hnh thnh 6 oxit dng N
2
O
n
(n = 1, 2, 3, 4, 5, 6)
V d: N
2
O, NO , N
2
O
3
, NO
2
, N
2
O
4,
N
2
O
5
, N
2
O
6
, NO
3
.
Trong ch c 3 oxit: N
2
O, N
2
O
3
, N
2
O
5
thc s l anhyrit ca
axit cn cc oxit khc khi hp nc khng to axit cng s oxi ho ca
chng.
1. Nit (I) oxit N
2
O hay (init oxit)
Cng thc cu to c in
N N = O
Phn t c cu trc ng thng v c cc di lin kt:
N
1,26 A
N
1,186 A
O
Cu hnh electron ca phn t N
2
O
:
. .
N = N =
. .
O: :N N
.
.
.
.
O:
C tng s electron ging phn t CO
2
nhng khng i xng, c
2 oxit ny trng thi rn u c mng li tinh th ging nhau.
+ N
2
O l mt cht kh khng mu, c mi hi ngt ngo, tng i
d chu (trong y hc dng cho mc ch gy m v nu ht phi mt lng
t kh N
2
O th c cm gic say, nhiu th b m).
t
0
nc

l - 91
0
C.
t
0
s l - 89
0
C.
nhit thng N
2
O bn, km hot ng. Nhng khi un nng khong
500
0
C b phn hu. Cho nn khi un nng, n c th tng tc vi tt c
cc cht, thc cht tng tc vi oxi, v d nh cc kim loi kim, C, P
2N
2
O
0
t
2N
2
+ O
2

- Hn hp nit (I) oxit vi hiro khi t s gy n nh hn hp ca oxi v hiro.
N
2
O + H
2

0
t
N
2
+ H
2
O
- c bit gy n mnh khi t hn hp nit (I) oxit vi amoniac
3N
2
O + 2NH
3

0
t
4N
2
+ 3H
2
O
* iu ch: Nhit phn mui NH
4
NO
3

NH
4
NO
3

0
0
250
t
C
N
2
O + 2H
2
O
Lu : Nu nhit trn 300
0
C th phn ng phn hu s gy n
2NH
4
NO
3

0
0
300
t
C
2N
2
+ 4H
2
O + O
2

b. Nit (II) oxit (hay nit oxit NO)
L cht kh khng mu, rt c, kh ho rn v kh ho lng
t
0
nc l - 163
0
C
t
0
s l - 150
0
C.
ho tan t trong nc, 1 lt nc 0
0
C ho tan 0,074 lt kh NO.
Cu trc electron ca phn t NO.
85

:
.
N: :
. .
O : :
. .
N : :
.
O: :N:
.
.
.
.
O: :
. .
N :
.
.
.
.
O:
Hoc : N O :
Vch chm gia nguyn t N v O ch lin kt ba electron hay cn gi
l lin kt 1e. di lin kt l 1,14
0
A, phn t NO c 1 electron
c thn, nn nhit thp phn t NO c xu hng to thnh ime
N
2
O
2

- Phn t NO kh bn, nhit 530
0
C cha phn hu r rt.
- Phn t NO bn hn N
2
O v khng duy tr s chy nh N
2
O
* Kh NO th hin tnh oxi ho.
2NO + 2H
2
S
(K)
N
2
+ 2S + 2H
2
O
(kh H
2
S kh c NO N
2
)
2NO + SO
2
N
2
O + SO
3
(kh SO
2
kh NO n N
2
O).
* Th hin tnh kh khi tc dng vi cht oxi ho mnh hn.
(KMnO
4
, axit HClO, anhiric cromic (CrO
3
) oxi ho NO n HNO
3

6KMnO
4
+ 10NO + 9H
2
SO
4
10HNO
3
+ 3K
2
SO
4
+ 6MnSO
4
+
4H
2
O
- Ging nh Nit (I) oxit, hn hp NO v H
2
th gy n khi un
nng.
- Kt hp d dng vi oxi to thnh NO
2
.
2NO + O
2
2NO
2
(P/ thun nghch, khi c nng lng
tia t ngoi th cn bng dch chuyn v pha tri).
NO
2
->NO + O
- Tc dng vi clo, brm to thnh nitrozoni halogen
2NO + Cl
2
2NOCl
Nitrozoni clorua (mu nu, rt c).
* Ngoi tnh cht oxi ho - kh, NO cn tc dng vi mui ca
nhiu kim loi.
FeSO
4
+ NO [Fe(NO)] SO
4
(hp cht c mu nu thm)
khi un nng dung dch ny li cho kh NO bay ra.
iu ch: Trong CN: Tng hp trc tip t N
2
v O
2
nhit cao.
N
2
+ O
2

0
t
2NO
4000
0
C (ngn la h quang in)
Sau lm ngui nhanh n di 1200
0
C kh NO khng b
phn hu (phng php ny hiu sut thp, t c dng trong cng
nghip).
- Trong phng th nghim: Cho ng kim loi tc dng vi HNO
3

long
3Cu + 8HNO
3
(l) 3Cu(NO
3
)
2
+ 2NO | + 4H
2
O
- Hoc phng php sn xut cng nghip hin nay l t NH
3

bng oxi khng kh c cht xc tc
4 NH
3
+ 5 O
2

xt t ,
0
4NO + 6 H
2
O
* Kh NO c to nn khi c sm st v khi t cc nhin liu du,
xng v than m. Mt khc kh NO vi hirocacbon cha chy ca
nhin liu di tc dng ca nh sng mt tri, gi l hin tng khi
86

m quang ho, sng m quang ho rt c hi n sc kho con
ngi.
Kh NO gy tc hi i vi kh quyn, n kt hp vi oxi v hi nc
trong khng kh to hin tng ma axit ph hoi ma mng, cy ci.
c. Nit ioxit (NO
2
) v nit (IV) oxit N
2
O
4
(hay i nit tetraoxit)
Cu to phn t c cu trc gc. Phn t NO
2
d trng hp li thnh
phn t N
2
O
4
khng mu nh s ghp i ca 2 e c thn nguyn t
N
gc lin kt gia nguyn t N v 2 nguyn t O l 134
0
, di lin kt N
O l 1,19
0
A. Khc vi phn t NO
2
, phn t N
2
O
4
khng mu
2NO
2

N
2
O
4

(mu nu) (khng mu)
NO
2
l mt cht kh mu nu, c mi c trng, rt c, d ho
lng, trng thi lng c t
0
nc l - 11,2
0
C ; t
0
s l 21,15
0
C.
150
0
C kh NO
2
phn hu r rt
2NO
2

0
0
150
t
C
2NO + O
2

Phn t N
2
O
4
trng thi rn c cu trc 2 A gic ni nh hai
nguyn t N.
* Tnh cht ho hc
+ L cht oxi ho mnh, duy tr s chy tt hn N
2
O v NO.
- Cc oxit NO
2
v N
2
O
4
tc dng vi nc to thnh 2 axit HNO
2

v HNO
3

NO HNO
3

2NO
2
+ H
2
O HNO
2
+ HNO
3

hoc NO
2
+ O
2
+ H
2
O 4 HNO
3
Hai oxit NO
2
v N
2
O
4
c th coi l mt anhyrit hn hp ca 2 axit
nitr v axit nitric, nn n tc dng vi dung dch kim to mui nitrit v
mui nitrat.
2NO
2
+ 2NaOH NaNO
2
+ NaNO
3
+ H
2
O
+ Kh NO
2
va th hin tnh oxi ho va th hin tnh kh.
- Tc dng vi mt s nguyn t khng kim loi, H
2
, v kim loi:
2NO
2
+ Cl
2
2NO
2
Cl (Nitroni clorua)
2NO
2
+ 7 H
2
2NH
3
+ 4H
2
O
2Cu + NO
2
Cu
2
O + NO
- Oxi ho CO thnh CO
2
v SO
2
thnh SO
3

CO + NO
2
CO
2
+ NO
SO
2
+ NO
2
SO
3
+ NO.
- Th hin tnh kh khi tc dng vi nhng cht oxi ho mnh hn
V d: O
3
+ NO
2
N
2
O
5
+ O
2

H
2
O
2
+ 2NO
2
2HNO
3

* iu ch
- Trong cng nghip iu ch NO
2
bng

cch: Cho kh NO tc dng vi
oxi
2NO + O
2
2NO
2

87

- Trong phng th nghim: Cho ng kim loi tc dng vi axt HNO
3

c
Cu + HNO
3
() Cu(NO
3
)
2
+ NO
2
+ 2H
2
O.
Kh NO
2
cng l nhng cht gy nhim mi trng khng kh, v n c
th bo mn tng ozn.
d. Nit (V) oxit (N
2
O
5
).
Cu to phn t


iu kin thng N
2
O
5
l cht dng tinh th, khng mu trong
sut, d chy ra trong khng kh
t
0
nc l 30
0
C
t
0
s l 45
0
C (c phn hu)
* L cht km bn, phn hu chm nhit thng to thnh
NO
2
v O
2

2N
2
O
5
4NO
2
+ O
2
(nu un nng phn ng phn hu
c th gy n).
* N
2
O
5
l cht oxi ho mnh
* Tan trong nc to axit nitric HNO
3
N
2
O
5
+ H
2
O 2HNO
3

do N
2
O
5
l anhyrit axit
- Tc dng vi H
2
O
2
nhit - 80
0
C to axit penitric HNO
4
,


(HNO
4
l hp cht d n): N
2
O
5
+ H
2
O
2 khan

C t
0 0
80

2HNO
4
+ H
2
O
+ iu ch N
2
O
5
bng cch: Cho pht pho pentaoxit tc dng vi HNO
3

2HNO
3
+ P
2
O
5
2HPO
3
+ N
2
O
5



N O N
1,3
0
A 1,4
0
A
O
O
O
O
88


Tit 44
Bi 6: AXIT NITR V MUI NITRIT
A. MC TIU:
iu ch, tnh cht v ng dng ca axit nitr v mui nitrit.
B. NI DUNG:
Ni t hnh thnh 4 oxi axit :
H
2
N
2
O
3
: axit hiponitric
HNO
2
: axit nitr
HNO
3
: axit nitric
HNO
4
: axit penitric.
Trong cc axit ny quan trng i vi thc t l axit nitr v axit ntric
6.1. iu ch
iu ch axit HNO
2
bng cch : axit ho dung dch mui nitrit
H
2
SO
4
+ Ba(NO
2
)
2
2HNO
2
+ BaSO
4

AgNO
2
+ HCl AgCl + HNO
2
iu ch mui NaNO
2
c th bng tc dng ca C, Pb hay Fe vi NaNO
3

NaNO
3
+ Pb PbO + NaNO
2

Hoc tng tc ca N
2
O
3
vi dung dch NaOH.
N
2
O
3
+ 2NaOH 2NaNO
3
+ H
2
O
6.2. Tnh cht v ng dng
HNO
2
v NO
2
-


Axit HNO
2
khng bn ch tn ti trng thi kh v trong dung
dch nc.
(ch bn trong dung dch long v ngui, nhanh chng b phn hu, nht
l khi un nng th phn hu rt nhanh).
3HNO
2
HNO
3
+ H
2
O + 2NO
Vy m khi kh NO
2
tan trong nc th thc t to nn HNO
3
v
NO.
3NO
2
+ H
2
O 2HNO
3
+ NO
- Do khng bn nn axit HNO
2
rt hot ng v mt ho hc ngoi
tnh cht ca mt axit cn c tnh oxi ho v tnh kh.
+ Tnh oxi ho:
axit HNO
2
oxi ho c axit HI n I
2

2HI + 2HNO
2
2NO + I
2
+ 2H
2
O
axit HNO
2
oxi ho c dung dch SO
2
thnh H
2
SO
4
:
2HNO
2
+ 9SO
2
+ 8H
2
O 7H
2
SO
4
+ 2NO + 2H
2
S
+ Tnh kh: Vi cht oxi ho mnh nh KMnO
4
, MnO
2
, PbO
2
th
axit HNO
2
li c tc dng nh mt cht kh.
2KMnO
4
+ 3H
2
SO
4
+ 5HNO
2
2MnSO
4
+ 5HNO
3
+ K
2
SO
4
+ 3H
2
O
+ Axit HNO
2
trong dung dch nc l mt axit yu (K = 4,5.10
-4
).
Nhng hi mnh hn axit H
2
CO
3
.
89

* Mui ca axit HNO
2
c tn l nitrit, mui nitrit bn hn axit nhiu.
Hu ht mui nitrit d tan trong nc, mui t tan l AgNO
2
. Cng nh
ion NO
2
-
, a s mui Nitrit khng c mu.
Mui nitrit ca KLK bn vi nhit, khng b phn hu khi nng chy m
ch phn hu trn 500
0
C. Nitrit ca kim loi khc km bn hn, b phn
hu khi un nng.
- Trong mi trng axit: mui nitrit c tnh oxi ho v tnh kh nh axit
nitr. Ngoi ra N trong NO
2
-

cn c cp electron khng tham gia lin kt
do NO
2
-
c kh nng to phc.
- phn bit mui nitrit v nitrat: cho axit sunfuric c vo mui nitrit
s c khi mu nu (NO
2
) bc ln
NaNO
3
+ H
2
SO
4(c)
NaHSO
4
+ HNO
2

2HNO
2
N
2
O
3
NO + NO
2

* ng dng: axit nitr v mui nitrit c dng rng ri trong cng
nghip ho hc (c bit l trong cng nghip phm nhum azo).

Bi 7: AXIT NITRIC V MUI NITRAT
A. MC TIU:
iu ch, tnh cht vt l, tnh cht ha hc v ng dng ca axit
nitric v mui nitrat.
B. NI DUNG:
Phn t axit HNO
3
c cu to phng

0
A
0
A

7.1. iu ch
- Trong phng th nghim:
NaNO
3
+ H
2
SO
4
()
0
t
NaHSO
4
+ HNO
3

KNO
3
+ H
2
SO
4

0
t
KHSO
4
+ HNO
3

- Trong cng nghip: axit nitric c iu ch bng ba phng php
+ Tc dng ca natri nitrat vi axit sunfuric c.
+ t chy khng kh.
+ t chy amoniac c xc tc.
7.2. Tnh cht vt l
HNO
3
tinh khit l cht lng khng mu, bc khi mnh trong kk
v c d = 1,52. N ho rn -41
0
C v t
0
s

= 86
0
C.
HNO
3
km bn d b phn hu di tc dng ca nh sng v nht.
4HNO
3
= 4NO
2
+ O
2
+ H
2
O.
Bn thn t ion ho t
0
= -10
0
C.
2HNO
3

NO
2
+
+ NO
3
-
+ H
2
O
Khi tan trong dung mi c kh nng cho proton mnh hn nh
H
2
SO
4
, HClO
4
th HNO
3
phn li cho ion NO
+
2

4HNO
3
+ 4H
2
SO
4

2NO
+
2
+ 4HSO
4
-
+ 4H
2
O
Axit HNO
3
tan trong H
2
O theo bt k t l no. N to vi hn hp
ng si cha 69,4% axit v t
0
s
= 121,8
0
C p sut thng. Khi lng
ring v t
0
s

ph thuc vo % HNO
3
trong dung dch
90

%HNO
3
100 94,1 86,0 68,4 65,3 47,5 24,8
D g/cm
3
1,52 1,49 1,47 1,41 1,40 1,30 1,15
t
0
s

0
C 86 99 115 122 115 113 104
7.3. Tnh cht ha hc
V mt ho hc axit HNO
3
c 2 tnh cht c trng l tnh oxi ho v tnh axit.
- Tnh axit: l mt axit mnh phn ly hon ton 1 nc
HNO
3
H
+
+ NO
3
-

- Tc dng vi nhiu baz, oxit baz, mui
3HNO
3
+ Fe(OH)
3
Fe(NO
3
)
3
+ 3H
2
O
2HNO
3
+ CuO Cu(NO
3
)
2
+ H
2
O
2HNO
3
+ CaCO
3
Ca(NO
3
)
2
+ CO
2
| + H
2
O
Tc dng vi hu ht kim loi tr Au, Pt, Rh, Ta, Ir v tc dng vi mt s
nguyn t khng kim loi nh C, P, As, S tu nng ca dung dch axt HNO
3
v
mnh ca kim loi v phi kim, c th xy ra cc phn ng vi sn phm kh khc nhau
(N
2
O, NO, NO
2
).
4Zn + 10HNO
3
(l) 4Zn(NO
3
)
2
+ NH
4
NO
3
+ 3H
2
O
3Cu + HNO
3
(l) 3Cu(NO
3
)
2
+ 2NO + 4H
2
O
4Cu + 10 HNO
3
(rl) 4Cu(NO
3
)
2
+ N
2
O + 5H
2
O.
Cu + 4HNO
3
(, nng) Cu(NO
3
)
2
+ 2NO
2
+ 2H
2
O.
Tc dng vi phi kim:
2HNO
3
(l) + S H
2
SO
4
+ 2NO
6HNO
3
()

+ S H
2
SO
4
+ 6NO
2
+ 2H
2
O
HNO
3
()

+ C
0
t
CO
2
| + NO
2
| + H
2
O
5HNO
3
(l) + 3P + 2H
2
O 3H
3
PO
4
+ 5NO|
5HNO
3
() + P H
3
PO
4
+ 5NO
2
| + H
2
O
Tnh oxi ho mnh mi nng (cng c cng mnh) sn phm oxi ho ca
HNO
3
tu thuc vo nng , nhit v cht tham gia phn ng.
- Cc phn ng trn u do tnh xi ho ca NO
-
3
trong mi trng axit.
Nhng khi un si trong mi trng kim vi bt Zn hay bt Al:
8Al + 3NaNO
3
+ 5NaOH +2H
2
O 8NaAlO
2
+ 3NH
3
|
4Zn + NaNO
3
+7NaOH 2H
2
O + 4Na
2
ZnO
2
+ NH
3
|
Ti sao HNO
3
khng phn ng vi Au, Pt ?
NO
-
3
+ 2H
+
+e NO
2
+ H
2
O E
0
= 0,80
v

NO
-
3
+ 3H
+
+2e HNO
2
+ H
2
O E
0
= 0,94
v

NO
-
3
+ 4H
+
+ e N
2
O + H
2
O E
0
= 0,96
v

NO
-
3
+ H
+
+ e N
2
O + H
2
O
NO
-
3
+ 6H
+
+ 5e 1/2 N
2
+ 3H
2
O

E
0
= 1,25
v

NO
-
3
+ 8H
+
+ 6e NH
3
OH
-
+ 2H
2
O
NO
-
3
+ 10 H
+
+ 8e NH
4
+
+ 3H
2
O E
0
= 0,88
v

V th kh ca E
0
(Au) = 1,42, ca E
0
(Pt) = 1,60 ln hn 0,95).
- HNO
3
phn ng vi cc hp cht
6FeSO
4
+ 3H
2
SO
4
+ 2HNO
3
3Fe
2
(SO
4
)
3
+ 2NO + 4H
2
O
Khc vi axit nitr, axit HNO
3
long khng oxi ho c HI n I
2
, nhng axit
HNO
3
c th oxi ho c HI v c HCl
2HNO
3
+ 6HCl 2NO + 3Cl
2
+ 4H
2
O
91

- Hn hp 1 th tch axit HNO
3
c v 3 th tch axit HCl c c tnh oxi ho
mnh c gi l nc cng thu.
HNO
3
+ 3HCl NOCl + 2Cl + 2H
2
O (nc cng thu c tnh
oxi ho mnh hn HNO
3
nhiu: v d hn hp ny c th ho tan hu ht cc kim loi
k c Au, Pt.
Au + HNO
3
+ 4HCl H[AuCl
4
] + NO + 2H
2
O
3Pt + 4HNO
3
+ 12HCl 3PtCl
4
+ 4NO + 8 H
2
O
3Pt + 4HNO
3
+ 18HCl 3H
2
[PtCl
6
] + 4NO + 8H
2
O
7.4. Mui nitrat
iu ch mui nitrat bng cch: cho tc dng HNO
3
vi kim loi, oxit kim
loi, hay hyroxit hoc cacbonat kim loi.
V d: 2HNO
3
+ Na
2
CO
3
2NaNO
3
+ H
2
O + CO
2

Cho bit cc cch phn hy khc nhau ca mui nitrat kim loi ph thuc vo
ion kim loi nh th no?
Mui nitrat ca kim loi kim kh bn vi nhit, nitrat ca kim loi
khc d phn hu khi un nng.
- bn nhit ca mui nitrat ph thuc vo bn cht ca cation kim
loi.
K Na, Ca Mg Al Zn Fe Ni Sn Pb H Cu HgAgPtAu
t
0
t
0
t
0

C cc kiu phn hu sau:
Nitrat ca kim loi hot ng ng trc Mg, phn hu thnh nitrit
v O
2
NaNO
3

0
t
NaNO
2
+ O
2

Nitrat ca kim loi t Mg n Cu, phn hu thnh oxit, NO
2
v O
2
Cu(NO
3
)
2

0
t
CuO + 2NO
2
| + O
2

2Pb(NO
3
)
2

0
t
PbO + 4NO
2
| + O
2

Nitrat ca kim loi km hot ng hn Cu, phn hu n kim loi.

Hg(NO
3
)
2

0
t
Hg + 2NO
2
+ O
2

Cch phn hu khc nhau ca nhng mui nitrat kim loi ny l do
bn khc nhau ca mui nitrit v oxit ca cc kim loi quyt nh.
V d: NaNO
2
v PbO bn trong khi Pb(NO
2
)
2
, Hg(NO
2
)
2
v HgO
khng bn.
7.5. ng dng
Axit HNO
3
l mt trong nhng ho cht c bn rt quan trng,
dng nhiu vo vic iu ch thuc n, phn bn, phm nhum, ho cht,
dc phm.
Quan trng v gi tr thc t l mui kali nitrat KNO
3
(cn gi l
dim tiu kali) dng lm phn bn, cht bo qun tht v dng trong cng
nghip thu tinh.

92

Tit 45:
KIM TRA

A. MC TIU:
Tnh cht ha hc ca SO
2
, H
2
SO
4
, gii thch c nhit si v
tnh axit ca dy H
2
X (X:O, S Se, Te).
B. NI DUNG:
BI KIM TRA S 3
Cu 1.(3 im) Trnh by tnh cht ha hc ca SO
2
, ly cc phn ng
minh ha?
Cu 2.(4 im) H
2
SO
4
c nhng tnh cht ha hc g, ly cc phn ng
minh ha?
Cu 3.(2 im) a/ Nhn xt v s thay i nhit si t H
2
O H
2
Te,
gii thch nguyn nhn?
b/ Gii thch s thay i tnh axit trong dy ?
P N
Cu 1. Tnh cht ho hc: dung dch SO
2
trong nc l axit yu
SO
2
+ H
2
O H
2
SO
3
(axit sunfur)
SO
2
l anhyrit axit.
- Tc dng vi dung dch kim to 2 mui
SO
2
+ NaOH NaHSO
3
(mui hiro sunfit)
SO
2
+ 2NaOH Na
2
SO
3
+ H
2
O (mui sunfit)
* Th hin tnh kh mnh nht l trong mi trng kim
- Cc cht oxi ho mnh nh: HNO
3
, KMnO
4
, K
2
Cr
2
O
7
, X
2
...oxi ho
SO
2
n axit sunfuric v c xu hng t ti s oxi ho +6 l s oxi ho
ti a ca S.
5SO
2
+ 2KMnO
4
+ 2H
2
O 2MnSO
4
+

K
2
SO
4
+

2H
2
SO
4
SO
2
+ PbO
2
PbSO
4

SO
2
+ 2HNO
3
() H
2
SO
4
+ 2NO
2
|
SO
2
+ H
2
O + Cl
2
H
2
SO
4
+ 2HCl
2SO
2
+ O
2

0
450
2SO
3

x/t V
2
O
5

* Ngoi tc dng kh, kh SO
2
cn c tc dng oxi ho khi tc dng vi
mt s cht kh mnh: Mg, Al, Ca ... khi un nng.
SO
2
+ 2Mg
0
t
2MgO + S
Hoc tc dng vi mt s cht kh khc:
SO
2
+ 2H
2
S + 2H
2
O
SO
2
+ 2H
2
S 3S + 2H
2
O
* Tnh bn: Kh bn, kh b nhit phn tch.
Cu 2. Axit H
2
SO
4
long c tnh cht ca mt axit thng thng:
- L mt axit mnh, hai ln axit: Qu trnh phn ly theo 2 nc:
H
2
SO
4
H
+
+ HSO
4
-

HSO
4
-

H
+
+ SO
4
2-

- Tc dng vi baz v oxit baz to thnh mui v nc (to 2 loi
mui)
H
2
SO
4
+ NaOH NaHSO
4
+ H
2
O ( mui hiro sunfat)
H
2
SO
4
+ 2NaOH Na
2
SO
4
+ 2H
2
O ( mui sunfat)
93

- Tc dng vi kim loi ng trc hiro trong dy th in cc gii
phng H
2
: M
e
II
(M
e
II
= Fe, Zn) v ion H
+
trong H
2
SO
4
long ng vai tr
cht oxi ho nn sau phn ng c s to thnh kh H
2
|

Me
(II)
+ H
2
SO
4
(l) MeSO
4
+ H
2
|
- Tc dng vi nhiu mui k c mui NaCl (li dng tnh axit nh hn
nhau).
H
2
SO
4
() + NaCl NaHSO
4
+ HCl |
H
2
SO
4
() + NaNO
3
NaHSO
4
+ HNO
3
|
H
2
SO
4
() + CaCO
3
CaSO
4
+ CO
2
+ H
2
O
H
2
SO
4
+ Ca
3
(PO
4
)
3

0
t
CaSO
4
+ H
3
PO
4

* Axit H
2
SO
4
c:
- Khng bn, d b phn hu 296
0
C to thn SO
3
v H
2
O
H
2
SO
4
()

0 0
337 296
SO
3
+ H
2
O
- C tnh ht nc mnh: H
2
SO
4
+ v bo, ng n ... C +
H
2
SO
4
.H
2
O
C tnh oxi ho mnh (nht l c nng):
+ phn ng vi phi kim C, P, S to thnh kh SO
2
, CO
2
, P
2
O
5
cn bn
thn H
2
SO
4
to thnh SO
2
+ Phn ng vi kim loi:
nhit thng khng phn ng vi Al, Fe, Cr.
Khi un nng phn ng vi cc kim loi (tr Au, Pt) v khng gii
phng H
2
.
2H
2
SO
4
() + Zn
0
t
ZnSO
4
+ SO
2
| + 2H
2
O
2H
2
SO
4
() + Cu
0
t
CuSO
4
+ SO
2
| + 2H
2
O
6 H
2
SO
4
() + 2Al
0
t
Al
2
(SO
4
)
3
+ 3SO
2
| + 6H
2
O
2H
2
SO
4
() + 2Ag
0
t
Ag
2
SO
4
+ SO
2
| + 2H
2
O
- Axit H
2
SO
4
() c tc dng ho than v ph hu nhiu cht hu c:
C
12
H
22
O
11

( )
2 4
H SO d
12C + 11H
2
O
Axit H
2
SO
4
tinh khit c th ho tan kh SO
3
to thnh cc axit
polisunfuric. Hn hp cc axit polisunfuric: H
2
S
2
O
7
, H
2
S
3
O
10
, H
2
S
4
O
13
,
H
2
S
n+1
O
3n+4
gi l lum.
Cu 3. a. S thay i nhit si t H
2
O H
2
S gim. Nguyn nhn l
do s hnh thnh lin kt hiro gia cc phn t H
2
O cn H
2
S n H
2
Te
kh nng hnh thnh lin kt hiro yu.
T H
2
S n H
2
Te nhit si tng dn do khi lng phn t tng
dn.
b. S thay i tnh axit t H
2
O H
2
Te tng dn, v nng lng
lin kt H-X ca dy gim dn theo chiu .
Hp cht H
2
X c nng lng lin kt b hn trong trong dung dch
nc d tch ion H
+
hn hp cht c nng lng lin kt ln hn.

94

Tit 46:
Bi 8: CHU TRNH NIT TRONG THIN T NHIN
A. MC TIU:
Chu trnh ca nit trong t nhin.
B. NI DUNG:
Nit hnh thnh mt vng tun hon qua ng vt v thc vt. Nit
l thnh phn quan trng trong cc protein ng vt v thc vt, v vy
ng vt v thc vt u cn c cung cp nit. Nit ca khng kh
khng c ng vt v phn ln thc vt thu nhn v tnh tr v mt ha
hc ca nit. ng vt v phn ln thc vt khng th ng ha c
nit, tr mt s vi khun hay vi sinh vt, v d cc vi khun sng trong
nt sn ca r cy h u v mt s loi cy khc cng nh mt s vi
sinh vt sng t do trong t c kh nng ng ha c nit n cht.
Ni chung thc vt nhn c nit cn thit t t di dng mui
nitrat, mui amonia v ure. Thc vt thu nhn cc hp cht v c ny
xy dng t bo. ng vt v con ngi khng c kh nng ny nn ch
nhn nit di cc dng protein thc vt. Bng cch ny nit n c
vi c th ng vt; tuy nhin c nhng ng vt khng th sng bng
thc n thc vt, m phi n tht cc ng vt khc c lng nit cn
thit cho s tn ti.
Nh qu trnh phn gii protein trong c th ng vt, nit xut
hin di dng ure v mt s hp cht nit khc cung cp cho t. Khi
thc vt hay xc ng vt b phn hy, nit c chuyn sang thnh dng
nitrat, mui amoni v mt s hp cht nit khc b sung cho t, qua
thc vt li c cung cp ngun nit. Mt phn hp cht nit c
chuyn thnh nit n cht do hot ng ca cc vi khun kh nitrat
trong t; mt khc qu trnh t chy cht hu c nh than, g v.v
gii phng nit n cht b sung tr li cho kh quyn. Chu trnh ca nit
gm c vng tun hon ca hp cht v n cht l chu trnh t nhin
iu tit nit v cc hp cht nit. Thin nhin to ra mt cn bng l
tng nh lng nit c chuyn ha thnh nitrat qua axit nitric do sm
chp to ra t nit, oxi, hi nc v do cc vi khun to nitrat sng trong
t tng hp c cn bng vi lng nit gii phng trong qu trnh ln
men v trong qu trnh hot ng ca vi khun kh nitrat sng trong t.
Tuy nhin qu trnh thm canh trong nng nghip cy trng ly ra t t
nhiu hp cht nit l c tr li nn nng sut gim dn. Vo nm
1840, nh ha hc c Libich (Liebig) bit c ngha vic bn cho
t nhng hp cht nit cn thit. T thi im , nhu cu v cc hp
cht nit ngy cng tng. Cho n chin tranh th gii ln th nht, cc
nc nhp khu natri nitrat ca Chi L l ch yu. T chin tranh th gii
th nht n nay, ngi ta pht trin cc phng php tng hp cc
hp cht nit t nit ca khng kh. Bng con ng vng, qua cng
nghip ha hc, nit ca khng kh thc s tham gia vo chu trnh t
nhin ca nit. Mi nm ngnh ha cng nghip ch bin s dng hng
triu tn kh nit nhng lng nit ca khng kh vn hng nh do qu
95

trnh chy cc hp cht hu c v cc qu trnh phn hy hp cht nh
trnh by trn b p li.
V s biu din chu trnh ca nit trong thin nhin?



Tit 47:

Bi 9: PHOTPHO (P)
A. MC TIU:
Trng thi t nhin, iu ch, tnh cht vt l, tnh cht ha hc ca
photpho.
B. NI DUNG:
9.1. Trng thi t nhin
Pht pho l nguyn t rt ph bin, chim 0,04% tng nguyn t ca v
qu t.
9.2. iu ch
P
2
O
5
+ 5C 2P + 5CO
Ca
3
(PO
4
)
2
+ 3SiO
2
3CaSiO
3
+ P
2
O
5

Ca
3
(PO
4
)
2
+ 3SiO
2
+ 5C 3CaSiO
3
+ 5Co + 2P
9.3. Tnh cht vt l
Phtpho trng: c mng li lp phng bao gm nhng phn t P
4
lin kt
vi nhau bng lc VaneVan. C cu to hnh t din u, mi nguyn t P lin kt vi
3 nguyn t khc bng 3 lin kt n, nn nng lng lin kt nh, di lin kt P -
P l 2,18
0
A (ln) nn P trng khng bn, khi c nhit th to thnh P .
P trng c t
0
nc l 44
0
C, t
0
s l 257
0
C,
mm v trong sut nh sp khng tan trong nc,
nhng tan trong dung mi khng cc nh CS
2
,
benzen, P trng rt c (ch cn n phi 0,1 g P trng cht).
iu ch bng cch:
P
2
O
5
+ 5C
Cao t
0
2P + 5CO
P
P P
P
96

* Pht pho (tm): l cht bt mu , t
0
nc: 600
0
C, thng hoa v ngng t li thnh P
trng, khng tan trong bt k dung mi hu c no, l cht v nh hnh c cu to phn
t dng polime, khng gy c.
* Pht pho en: c to thnh khi un nng P trng t
0
220
0
- 370
0
C trong thi gian
khong 8 ngy di p sut cao 12.000 atm, c Hg lm xc tc.
P en l cht bn dn, t
0
nc: 1000
0
C di p sut 18.000 atm, P en bn hn P
v P trng.
P en cng ging P kh nng chy v khng tan trong dung mi no c, v P
en cng l cht polime, P en khng gy c.
9.4. Tnh cht ha hc
So vi nit, phtpho hot ng ho hc mnh hn bi do lin kt P
- P trong phn t P
4
km bn hn nhiu so vi lin kt N - N trong phn
t N
2
, to thnh cc hp cht cng ho tr.
- Pht pho l phi kim, va c tnh oxi ha va c tnh kh: Tuy nhin
tnh cht c bn l tnh kh.
+ Tnh oxi ho: 2P + 3Ca Ca
3
P
2
(phtphua)
+ Tnh kh mnh c bit l P trng
4P + 5O
2
(d)
0
0
40
t
P
4
O
10
(phn ng chy), trong khi P
nhit trn 250
0
C v P en nhit trn 400
0
C mi bc chy.
P
4
O
10
ngm hi nc trong khng kh to thnh cc ht sng lm P
4
O
10
bc hi.
Axit H
2
SO
4
() un nng vi P trng, S
+6
b kh xung lu hunh
(IV) oxit
2P + 5H
2
SO
4
2H
3
PO
4
+ 5SO
2
| + 2H
2
O
axit HNO
3
vi P trng, N
+5
b kh xung nit (II) oxit
3P + 5HNO
3
+ 2H
2
O 3H
3
PO
4
+ 5NO|
Thm ch P trng kh c c ion kim loi yu ra khi dung dch
mui ca Au, Ag, Pb v Cu.
P + 5AgNO
3
+ 4H
2
O H
3
PO
4
+ 5Ag+ + 5HNO
3
P + CuSO
4
+ 8H
2
O H
3
PO
4
+ 5Cu + 5 H
2
SO
4
P trng phn ng vi halogen v lu hunh rt mnh
P + Cl
2(d)
PCl
5

P + Cl
2 (thiu)
PCl
3

P trng khi tc dng vi dung dch kim th hin kh nng t oxi ho
kh:
P
4
+ 3KOH + 3H
2
O PH
3
+ 3KH
2
PO
2

97

* P hot ng km P trng nhiu, P t bc chy khi va chm
vi nhng cht oxi ho mnh nh KClO
3
, K
2
Cr
2
O
7
, KNO
3
. nhit
cao P
* P en tnh cht ho hc gn ging tnh cht ho hc ca P , P en b
oxi ho ngoi khng kh m nhanh hn.
9.5. ng dng
So vi nit, phtpho hot ng ho hc mnh hn bi do lin kt
P - P trong phn t P
4
km bn hn nhiu so vi lin kt N - N trong
phn t N
2
, to thnh cc hp cht cng ho tr.
- Pht pho l phi kim, va c tnh oxi ha va c tnh kh: Tuy
nhin tnh cht c bn l tnh kh.
+ Tnh oxi ho: 2P + 3Ca = Ca
3
P
2
(phtphua)
+ Tnh kh mnh c bit l P trng
4P + 5O
2
(d)
0
0
40
t
P
4
O
10
(phn ng chy), trong khi P
nhit trn 250
0
C v P en nhit trn 400
0
C mi bc chy.
P
4
O
10
ngm hi nc trong khng kh to thnh cc ht sng lm P
4
O
10
bc hi.
Axit H
2
SO
4
() un nng vi P trng, S
+6
b kh xung lu hunh
(IV) oxit
2P + 5H
2
SO
4
2H
3
PO
4
+ 5SO
2
| + 2H
2
O
axit HNO
3
vi P trng, N
+5
b kh xung nit (II) oxit
3P + 5HNO
3
+ 2H
2
O 3H
3
PO
4
+ 5NO|
Thm ch P trng kh c c ion kim loi yu ra khi dung dch
mui ca Au, Ag, Pb v Cu.
P + 5AgNO
3
+ 4H
2
O H
3
PO
4
+ 5Ag+ + 5HNO
3
P + CuSO
4
+ 8H
2
O
3
PO
4
+ 5Cu + 5 H
2
SO
4
P trng phn ng vi halogen v lu hunh rt mnh
P + Cl
2(d)
PCl
5

P + Cl
2 (thiu)
PCl
3

P trng khi tc dng vi dung dch kim th hin kh nng t oxi ha
kh:
P
4
+ 3KOH + 3H
2
O PH
3
+ 3KH
2
PO
2

* P hot ng km P trng nhiu, P t bc chy khi va chm
vi nhng cht oxi ho mnh nh KClO
3
, K
2
Cr
2
O
7
, KNO
3
. nhit
cao P
* P en tnh cht ho hc gn ging tnh cht ho hc ca P , P en b
oxi ho ngoi khng kh m nhanh hn.
Tit 48
98

Bi 10: CC HP CHT HIRO CA PHOTPHO
A. MC TIU:
iu ch, tnh cht vt l, tnh cht ha hc ca photphin.
iphotphin.
B. NI DUNG:
Photpho hnh thnh hai hp cht vi hiro: mt hp cht tng t
amoniac l photphin v mt hp cht tng t nh hirazin l iphotphin
(P
2
H
4
).
10.1. Photphin
10.1.1. iu ch
Cho phtphua kim loi tc dng vi nc:
Ca
3
P
2
+ 6H
2
O 3Ca(OH)
2
+ 2PH
3

hoc cho baz tc dng vi P trng :
P
4
+ 3 KOH + 3H
2
O PH
3
+ 3KH
2
PO
2
Nhit phn axit hipophophor, axit photphor v mui ca axit
ny:
2H
3
PO
2
PH
3
+ H
3
PO
4

4H
3
PO
3
PH
3
+ 3H
3
PO
4

Tng hp t cc n cht
P + 3/2H
2
PH
3

Cho baz tc dng vi mui photphoni
PH
4
+
+ OH
-
PH
3
+ H
2
O
10.1.2. Tnh cht vt l
Phn t PH
3
c cu to ging vi phn t NH
3

PH
3
l cht kh khng mu, rt c, c mi kh chu
t
0
s l - 87,4
0
C; t
0
nc l - 133
0
C.
Phn t PH
3
km bn hn NH
3
, tan t trong nc.
10.1.3. Tnh cht ha hc
kh nng cho cp e t do ca PH
3
km hn nhiu NH
3
. N khng kt
hp vi ion H
+
ca axit mnh nh HclO
4
v HX (X = Cl, Br, I) to ion
photphoni PH
4
+
.
- Khc vi NH
3
, phn t NH
3
c tnh kh mnh. N bc chy trong
khng kh khi un nng n 150
0
C.
PH
3
+ 2O
2
H
3
PO
4
.
Hn hp ca n vi khng kh s n khi lm gim p sut.
- N c th tc dng vi halogen to photpho pentahalogen
PH
3
+ 4Cl
2
PCl
5
+ 3HCl
- N c th gii phng kim loi t dung dch mui bc, mui ng
- 6AgNO
3
+ PH
3
+ 3 H
2
O 6 Ag + 6 HNO
3
+ H
3
PO
4

10.2. iphotphin (P
2
H
4
)
P
2
H
4
c cu to phn t ging nh N
2
H
4
.P
2
H
4
l cht lng khng mu, ho rn 99
0
C
v si 63
0
C. P
2
H
4
cu to ging N
2
H
4
nhng c tnh cht khc N
2
H
4
chng hn nh n
khng to mui vi axt; khi un nng v di tc dng ca nh sng, n phn hu
thnh PH
3
v P.
P
2
H
4
l cht kh mnh, n bc chy khi tip xc vi khng kh. Chnh s c mt mt
lng nh P
2
H
4
trong PH
3
lm cho PH
3
bc chy trong khng kh nhit thng.
(iu ch ny gii thch hin tng ma tri).
99

iu ch: ifotfin thng c to nn cng vi fofin. N c th iu ch bng cch
thu phn canxi fotfua c ln Ca
2
P
2
: Ca
2
P
2
+ 6H
2
O = 2 Ca(OH)
2
+ P
2
H
4
ng vo nhit
khc nhau, ngi ta tch P
2
P
4
khi PH
3

3P
2
H
4
4PH
3
+ 2P



Tit 49: T hc
Bi 11: CC OXIT CA PHOTPHO
A. MC TIU:
Tnh cht ca iphotpho trioxit; iphotpho tetraoxit; iphotpho
pentaoxit.
B. NI DUNG:
Pht pho hnh thnh 3 oxit:
+ Pht pho (III) oxit: P
2
O
3

+ Pht pho (IV) oxit: P
2
O
4
+ Pht pho (V) oxit: P
2
O
5

1. Pht pho (I I I ) oxit: P
2
O
3

- L cht kt tinh mu trng, mm ging nh sp, c gn nh P trng.
- t
0
nc l 23,8
0
C
- t
0
s l 175
0
C
- d tan trong ete, cc bon isunfua (CS
2
), ben zen.
- Trong dung dch, cng nh trng thi hi, n tn ti di dng P
4
O
6

(trong thc t ngi ta thng dng cng thc P
2
O
3
v khi lng phn
t khng nh hng nhiu n tnh cht ha hc ca cht).
- nhit t 200 250
0
C (un nng vi ngy trong bnh kn), P
2
O
3
b
phn hu thnh P v phtpho (IV) oxit.
4P
2
O
3

0
t
= 3P
2
O
4
+ 2P
- nhit thng, P
2
O
3
bn vi oxi khng kh, nhng khi nhit t
50 60
0
C, n b oxi ho to thnh P
2
O
5
.
P
2
O
3
+ O
2

0
t
P
2
O
5
(th hin tnh kh)
- P
2
O
3
kt hp vi nc lnh rt chm to thnh axit phtphor (nu vi
nc nng th phn ng xy ra mnh lit hn).
P
2
O
3
+ 3 H
2
O 2H
3
PO
3

iu ch: t pht pho vi lng thiu oxi khng kh.
4P + 3O
2
2P
2
O
3

2. Pht pho (IV) oxit: P
2
O
4

- L cht rn khng mu, kt tinh thnh nhng tinh th long lanh, khi tan
trong nc to nhit mnh to thnh axit pht phorc v axit phtphor.
P
2
O
4
+ 3 H
2
O H
3
PO
3
+ H
3
PO
4

P
2
O
4
l anhyrit hn hp ca axit H
3
PO
3
v H
3
PO
4


iu ch:
100

un nng pht pho (III) oxit.
4P
2
O
3

0
t
3P
2
O
4
+ 2P
3. Pht pho (V) oxit P
2
O
5

- L cht bt mu trng nh tuyt, khng mi, thng hoa 359
0
C
di psut 1 atm. Hi ca pht pho (V) oxit khong 670 1400
0
C
gm nhng phn t P
4
O
10
.
- Pht pho (V) oxit ht m rt mnh v l mt trong nhng cht lm kh
tt nht i vi cc kh. (tnh cht c trng ca P
2
O
5
l tnh

ho nc).
- Khi tc dng vi mt t nc lnh to thnh axit metaphtphoric.
P
2
O
5
+ H
2
O = 2HPO
3

- Vi nc nng th to thnh axit orthophtphoric.
P
2
O
5
+ 3 H
2
O = 2H
3
PO
4

Phtpho (V) oxit l anhydrit ca axit phtphoric.
- Khi un nng vi oxit kim loi, n to nn mui pht pht.
iu ch:
- t pht pho trong iu kin d oxi khng kh. 4P + 5O
2
(d) =
2P
2
O
5
Tit 50
Bi 12: CC OXI AXIT CA PHOTPHO
A. MC TIU:
Axit hipophotphor; axit photphor; axit photphoric (iu ch, tnh
cht vt l, tnh cht ha hc, cc mui).
B. NI DUNG:
Phtpho to nn rt nhiu oxiaxit, hin nay bit 11 oxiaxit:
H
3
PO
3
, HPO
2
, H
4
P
2
O
5
, H
4
P
2
O
6
, HPO
3
, H
4
P
2
O
9
, H
5
P
8
H
10
, H
3
PO
4
, H
3
PO
5

& H
4
P
2
O
8
, H
3
PO
3
.
Cu to ca mt s oxiaxit cng cha c xc nh mt nhm P-
O-H c khi nin phn li cho H
+
, cn nhng nguyn t hir ca lin kt
P-IIi khng th phn li c.
Quan trng hn vi thc t l cc oxiaxit: H
3
PO
2
, H
3
PO
3
& H
3
PO
4
;
Cc ion H
2
PO
2
-
& HPO
3
-2
l t din lch cn PO
3-
4 l
t din u lin
kt P-O trong cc anion u c mc lin kt cho mui & axit tng
ng u c tnh kh.
12.1. Axit hiphotphor
L tinh th khng mu, t
0
nc =27
0
C, d tan trong nc khi un nng n
103
0
C, n phn hu theo phn ng.
3H
3
PO
2
2H
3
PO
3
+ PH
3
N l axit mnh v l axit 1 nc. Mui ca n gi l hiphophatphit. cc
hiphophot u d tan trong nc.
Axit H
3
PO
2
v mui ca l cht kh mnh, nhng phn ng ca n vi
cht oxi ho thng xy ra chm. Chng tng tc vi halogen bin
thnh axit phopphoric
Chng kt ta khi lng t mui ca cc KL qu nh Au, Ag, Dd & mt
s Kl nng nh Cu, Hg, Bi.
101

H
3
PO
2
+ 2CuSO
4
+ 2H
2
2Cu + 2H
2
SO
4
+ H
3
PO
4
.
Tuy nhin H
3
PO
2
c th b Zn trong H
2
SO
4
kh n phtpin.
iu ch:
Tc dng ca Barihipopot vi dd H
2
SO
4
H
3
PO
2
.
Mui ca n iu ch bng tc dng ca Ptr vi dd Ba (OH)
2

2P
4
+ 3Ba(OH)
2
+ 6H
2
0 2Ba(H
2
PO
2
)
2
+ 2PH
3

12.2. Axit photphor
L tinh th khng mu, t
0
nc
= 74
0
C, chy ra trong khng kh v d
tan trong nc. 200
0
C n phn hu thnh H
3
PO
4
photpin
4H
3
PO
3
3H
3
PO
4
+ PH
3

L axit 2 nc v l axit trung bnh (K
1
= 1.10
-2
& K
2
=3.10
-7
).
Mui ca n gi l phophit, v khng c mu, thng kh tan trong
nc.
Trong cc dn xut hu c nguyn nhn ta thng gp nhng ete
P(OR)
3
ng vi axit P(OH)
3
. Axit H
3
PO
3
l cht kh mnh, phn ng ca
n vi cht oxi ho xy ra chm v phc tp. N tng tc vi halogen,
lm kt ta kim loi t dd mui ca khi lng nng v bn thn n bin
thnh H
3
PO
4
:
H
3
PO
3
+ 2AgNO
3
+ H
2
O H
3
PO
4
+ 2Ag +2HNO
3

Tuy nhin Zn trong dd H
2
SO
4
, n cng b kh n photpin.
iu ch:
Bng phn ng P
4
O
6
vi H
2
O hoc thu phn mui PCl
3
PCl
3
+ 3H
2
O H
3
PO
3
+ 3HCl
12.3. Axit photphric
a. iu ch: + Trong cng nghip:
iu ch t cc qung t nhin bng phng php x l kh hay
t.
- Phng php x l t c tin hnh bng cch: un nng qung
pht pht c nghin nh vi axit H
2
SO
4
c nng trung bnh
(hoc axt H
2
SO
4
long).
Ca
3
(PO
4
)
2
+ 3H
2
SO
4
(l)

3CaSO
4
+ 2H
3
PO
4
Sau tch mui CaSO
4
t tan ra v c dung dch n 150
0
C ri lm lnh
axit kt tinh.
- Phng php x l kh c tin hnh bng cch : Nung qung pht
pht kh vi than cc v Si lic (IV) oxit trong l cao hay trong l in
Ca
3
(PO
4
)
2
+ 3SiO
2
+ 5C

3CaSiO
3
+ 5CO +2P
4P + 5O
2
2P
2
O
5

Sau cho tc dng vi nc hay dung dch axit H
2
SO
4
50% chuyn
thnh axit
H
3
PO
4

m c.
P
2
O
5
+ 3H
2
O 2H
3
PO
4
- Axit photphoric tinh khit c iu ch bng cch t photpho tinh
khit vi khng kh v cho iphotpho pentoxit c tinh khit cao ny
hp nc.
- Phng php oxi ha photpho bng axit nitric m c (trc y dng,
cn hin nay khng dng).
b. Tnh cht vt l
Axit H
3
PO
4
tn ti di 3 dng:
+ Axit ortho pht phoric H
3
PO
4
.
+ Axit meta pht phoric HPO
3
.
+ Axit i pht phoric H
4
P
2
O
7
.
OH
O
OH
P OH


102

Cu to phn t ca axit phtphoric H
3
PO
4

- axit phtphoric H
3
PO
4
l cht dng tinh th, khng mu.
- t
0
nc l 42,5
0
C, d tan trong nc.
- axit phtphoric H
3
PO
4
trn th trng c nng 85%.
- Khi un nng n 260
0
C, n mt bt nc to thnh axit iphtphoric
H
4
P
2
O
7
.
2H
3
PO
4

C
0
260
H
4
P
2
O
7
+ H
2
O
- Axit iphtphoric H
4
P
2
O
7
l cht dng thu tinh, mm , nng chy
61
0
C, d tan trong nc.





c. Tnh cht ha hc
Axit orthophotphoric H
3
PO
4
l axit phn ly 3 nc, c mnh axit trung
bnh:
H
3
PO
4
= H
+
+ H
2
PO
4
-
H
2
PO
4
-
= H
+
+ HPO
4
2-

HPO
4
2-
=

H
+
+ PO
4
3-
Axit pht phoric tc dng vi baz, oxit baz tu thuc vo lng baz
m cho cc loi mui khc nhau:
NaOH + H
3
PO
4
NaH
2
PO
4
+ H
2
O
2NaOH + H
3
PO
4
Na
2
HPO
4
+ 2H
2
O
3NaOH + H
3
PO
4
Na
3
PO
4
+ 3H
2
O (mui pht pht)
Nhn xt: axit H
3
PO
4
rt bn, c trng thi tan, rn, lng u khng c
kh nng oxi ho di
0
t 350 - 400
0
C, nhng
0
t cao hn l cht oxi
ho yu, chng c th tng tc vi kim loi nhit cao, cc axt
phtphoric cn tc dng vi thch anh v thu tinh.
d. Cc mui
Cc mui pht pht ni chung u khng c mu,
C 3 loi pht pht:
H
2
PO
4
-
Mui axit (ihyrophtpht)
HPO
4
2-
Mui axit (monohyrophtpht)
PO
4
3-
Mui trung tnh (pht pht)
Tt c cc mui ihyrophtpht u d tan trong nc, cn cc
mui monohyropht pht v pht pht th ch mui ca kim loi kim l
d tan.
Trong cc mui pht pht tan th mui pht pht trung tnh ca kim
loi kim b thu phn rt mnh trong dung dch cho mi trng kim:
Na
3
PO
4
+ H
2
O NaOH + Na
2
HPO
4
Mui monohyro pht pht b thu phn yu hn cho mi trng
kim yu

Na
2
HPO
4
+ H
2
O NaOH + NaH
2
PO
4
Cn mui ihyro pht pht b thu phn yu hn na cho mi trng
axit yu
NaH
2
PO
4
+ H
2
O H
3
O
+
+ Na
2
HPO
4
2-
H
3
PO
4
+ NaOH NaH
2
PO
4
+ H
2
O
2H
3
PO
4
+ Na
2
CO
3
2NaH
2
PO
4
+ H
2
O + CO
2

NaH
2
PO
4
+ NH
4
Cl NaNH
4
HPO
4
+ NaCl
HPO
4
2-
+ 3Ag
+
Ag
3
PO
4
+ H
+

(phn ng ny dng nhn ra ion PO
4
3-
c trong dung dch )
2K
2
HPO
4
K
4
P
2
O
7
+ H
2
O
Axit phtphoric H
3
PO
4
.
Axit iphtphoric H
4
P
2
O
7

Axit metaphtphoric
HPO
3
.

Trong nc lnh
300 C
0

103

2KH
2
PO
4
K
2
H
2
P
2
O
7
2KPO
3

+ng dng:
- Mui pht pht c dng lm phn bn ho hc nh mui amni
phtpht v mui canxi phtpht.
- Mui Ca
3
(PO
4
)
2
cn c dng lm thc n cho gia sc, mui Na
3
PO
4

c dng lm mm nc, dng cho cc ni hi cao p v lm cht
ty ra.
Mui NaH
2
PO
4
cng c dng lm mm nc cng.
- Hn hp 2 mui Na
2
HPO
4
v NaH
2
PO
4

0
t 420
0
C to nn mui
Na
5
P
3
O
10
dng lm bt git.
2Na
2
HPO
4
+ NaH
2
PO
4

0
t
= Na
5
P
3
O
10
+ H
2
O


Tit 51 (t hc)
Bi 13: PHN BN HA HC
A. MC TIU:
Phn m, phn ln (cc mui canxi photphat; cc mui amoni
photphat), phn kali.
B. NI DUNG:
Mun sinh trng v pht trin bnh thng hu ht cc cy trng
u cn mt s cht dinh dng di dng mui. Nhng ha cht cha
nhng nguyn t dinh dng cn b sung cho t nui cy trng gi
l phn ha hc. Cht dinh dng thit yu ca cy trng cha mi
nguyn t a lng C, O, H, N, P, S, K, Ca, Mg, v Fe; ngoi ra cy
trng cng cn mt s nguyn t khc vi lng rt nh c gi l cc
nguyn t vi lng hay phn vi lng nh: B, Mn, Cu, Zn, Mo v Co
(tng cy trng cn cc loi phn vi lng khc nhau). Trong nng
nghip, ngoi phn ha hc, ngi ta cn bn phn chung, phn xanh.
Loi phn ny cung cp khng cc nguyn t cn thit cho cy trng
nhng cng rt hu ch bi v n cung cp cho t thm nhng cht to
bn lm xp t, ci to ng k cu trc vt l ca t nng nghip.
C 3 loi phn bn ha hc chnh l: Phn m, phn ln v phn kali.
13.1. Phn m
Cung cp Nit cho cy trng di dng ion NO
3
-
v ion NH
4
+
, c tc dng kch
thch qu trnh sinh trng ca cy v xc tin tc dng tng hp cc cht cha N trong
cy. Do cy trng pht trin nhanh, cho nhiu ht, c, qu, nhiu l.
Hin nay c nhng loi phn m ph bin thng dng:
- Amoni : NH
4
Cl, NH
4
NO
3
, (NH
4
)
2
SO
4
(cc mui ny u b thu phn, ion NH
4
+

y ng vai tr axit , to ra mi trng axit, lm tng nng ion H
+
, lm gim pH
ca t lm cho t chua thm.
- Nitrat: NaNO
3
, Ca(NO
3
)
2
KNO
3
.
- Ure: (NH
2
)
2
CO l loi phn m tt nht hin nay v t l N cao, khi bn khng b
thu phn, khng lm thay i pH ca t nh phn amoni. N thch hp vi nhiu
loi t.
13.2. Phn ln:
Cung cp pht pho di dng ion PO
4
3-
, cn thit cho cy thi k sinh trng
(Qu trnh sinh l ca cy trng). C tc dng lm cho cy trng cng cp, ht chc
my.
- C cc loi phn ln t nhin: qung pht pht Ca
3
(PO
4
)
2
(haymui canxi phtphat)
c dng bn trc tip cho cy. Loi phn ny khng tan trong nc, khng tan
trong axit hu c. N c sn trong t hoc c tit ra t r ca mt s loi cy. Do
ch nn bn vng t chua v thch hp vi mt s loi cy.
104

Ngi ta cn bin i can xi pht pht thnh hp cht d tan trong nc :
Ca
3
(PO
4
)
2
+ H
2
SO
4
Ca(H
2
PO
4
)
2
(tan) + 2CaSO
4

- Phn ln nung chy (phn ln thu tinh):
c sn xut bng cch trn hn hp bt pht pht vi bt qung nung chy
trn 1000
0
C. Sau lm lnh t ngt bng nc s thu c nhng ht vn trong sut
nh thu tinh. Tip theo, ngi ta sy kh v nghin thnh bt mn. Loi phn ny thch
hp vi t chua, thng c sn xut mt s nh my nh nh nh my phn ln
nung chy Vn in, Sn ty,...
- Supephtpht n: gm hai cht chnh l Ca(H
2
PO
4
)
2
(cht ny tan trong nc nn
cy trng c th ng ha c) v c thm CaSO
4
(khng tan trong nc nn khng c
tc dng i vi cy trng).
c sn xut bng cch cho qung apatit hay phtphorit nghin nh tc
dng vi axit H
2
SO
4
c:
Ca
3
(PO
4
)
2
+ 2H
2
SO
4
Ca(H
2
PO
4
)
2
+ 2CaSO
4
- Supepht pht kp: ch yu gm Ca(H
2
PO
4
)
2

S d c gi l supe pht pht kp v qu trnh sn xut gm hai giai on:
iu ch H
3
PO
4
trc, sau mi cho qung tc dng vi H
3
PO
4
.
Ca
3
(PO
4
)
2
+ 3H
2
SO
4
2H
3
PO
4
+ 3CaSO
4

Ca
3
(PO
4
)
2
+ H
3
PO
4
3Ca(H
2
PO
4
)
2

- Cc mui amoni photphat: Axit photphoric c th to thnh ba mui amoni photphat,
tuy nhin hp cht chnh dng lm phn bn l iamoni hirophotphat. Hp cht
(NH
4
H
2
PO
4
) cha qu t m, cn hp cht (NH
4
)
3
PO
4
ngoi khng kh chuyn thnh
iamoni hirophotphat v amoniac trc khi s dng.
iamoni hirophotphat c iu ch bng cch sc kh amoniac vo dung dch
axit photphoric
H
3
PO
4
+ 2NH
3
(NH
4
)
2
HPO
4

13.3. Phn kali
Cung cp cho cy trng kali di dng ion K
+
. Phn kali c nh hng n s
v tng hp nhng cht cha N trong cy, c kali cy s ht c N nhiu hn. Ngoi
ra kali cn c tc dng to ra du, xenlulz trong cy, tng cng sc chng bnh v
chng rt ca cy.
Nhng loi phn kali chnh thng dng l KCl, K
2
SO
4
.
Trong thc t, cho nng sut cy trng cao, ngi ta kt hp c 3 loi phn trn.

Tit 52
Bi 14: HP CHT HALOGEN CA PHOTPHO
A. MC TIU:
iu ch, tnh cht ca photpho triclorua v photpho penta clorua.
B. NI DUNG:
Photphat to nn vi halogen 2 hp cht chnh PX
3
v PX
5

1. PX
3
. (X = F,Cl,Br,I)
Ngoi ra cn cc photphotrihalogenua hn tp: PF
2
Cl, PF
2
Br, PFCl
2
,PFBr
2
.
trng thi rn tt c cc photphotrihalogenua n hay hn tp u c mng li
phn t.
Phn t PX
3
c cu to chp tam gic u gc XPX trong PF
3
l 104
0
, PCl
3
l 102
0

v trong PBr
3
l 100
0
v PI
3
l 96
0
.
dp-x trong PF
3
l 1,52A
0
; PCl
3
l 2,00A
0
; PBr
3
l 2,23A
0
v PI
3
l 2,47A
0
.
So vi lin kt n P-X bnh thng th di lin kt P-F v P-Cl ngn hn l do
c lin kt kp, l lin kt IIp d.
Cc photphotrihalogenua n hay hn tp u c t
0
nc
v t
0
s
thp.
PF
3
PCl
3
PBr
3
PI
3
PF
2
Cl PF
2
Br PFCl
2
PFBr
2

T
0
nc
(C) - 152 -94 -40 61 -165 -134 -144 -115
105

T
0
s
(
0
C) - 101 75 173 120 -47 -16 14 78
iu kin thng, PF
3
l cht kh khng mu, PI
3
l cht rn mu cn cc
trihalogenua khc l cht lng khng mu.
Tt c cc PX
3
u b thu phn:
2PX
3
+6H
2
O = 2H
3
PO
3
+ 6HX
Cc PX
3
c th iu ch bng cho P
4
tc dng vi halogen
Ring PF
3
iu ch gin tip.
PCl
3
+ A
s
F
3
= PF
3
+ A
s
Cl
3

* PHOTPHOTRICLORUA - PCl
3

L cht lng khng mu, d=1,57, c mi ngt th. Hi ca n lm chy nc mt
v c; dng lng n gy bng. PCl
3
tan trong CS
2
, Bengen, CCl
4
. N bc khi mnh
trong khng kh v n tc dng mnh lit vi nc to thnh axit photphor v axit
clohiric.
2PCl
3
+ 6H
2
O = 2H
3
PO
3
+ 6HCl
PCl
3
c th kt hp vi Clo to thnh PCl
5
, vi oxi to thnh POCl
3
v vi lu
hung khi un nng to PSCl
3
.
2PCl
3
+ O
2
2POCl
3

PCl
3
c dng lm cht ban u iu ch nhiu hp cht khc ca photpho. N
l cht Clo ho tt c dng vo vic sn xut phm nhum, thuc tr su, dc phm
v cht hot ng b mt.
PCl
3
c iu ch bng t chy P d trong kh Clo kh hoc cho kh Clo kh i
vo dung dch ca P trng trong CS
2
.
2. PX
5
:
Ngi ta bit c nhng hp cht vi F, Cl v Br, Ngoi ra cn c 1 s photpho
pentahalogenua hn tp: PF
4
Cl, PF
3
Cl
2
, PF
3
Br
2
, PFCl
4

trng thi kh, cc phn t PF
5
v PCl
5
c cu to hnh chp kp tam gic.

dp - F = 1,57 A
0
dp - Cl = 2,04A
0
Trong PCl
5
v PBr
5
nguyn t P c dng lai ha dsp
3

Cc PX
5
b thu phn d dng
PX
5
+ H
2
O t POX
3
+ 2HX
PX
5
+ 4H
2
O
nhiu
H
3
PO
4
+ 5HX
iu ch PX
5
bng cho P tc dng vi halogen.
* PCl
5
: l nhng tinh th mu trng nu tinh khit.
Trong tinh th PCl
5
c nhng ion t din PCl
4
+
v ion bt din PCl
-
6
sp xp theo
kiu C
s
Cl. dP-Cl trong PCl
4
+
l 1,98A
0
hi ngn hn dP-Cl = 2,07 A
0
trong PCl
-
6
.
PCl
5
thng c mu lc nht v b phn hu mt phn thnh PCl
3
v Cl
2
.
Trong nc b phn hu hon ton:
PCl
5
+ H
2
O POCl
3
+ 2 HCl
POCl
3
+ 3H
2
O H
3
PO
4
+ 3HCl.
N c kh nng kt hp vi cc cht to hp cht kt hp: PCl
5
. 8NH
3
, PCl
5
.
AlCl
3

PCl
5
l cht Clo ho tt nht c dng vo vic sn xut phm nhum, thuc tr
su, dc phm; dng lm cht xc tc.
iu ch: cho Clo kh tc dng vi PCl
3
45
0
.

106


Tit 53
Bi 15: ASEN V ANTIMON
A. MC TIU:
Trng thi thin nhin, iu ch, tnh cht vt l, tnh cht ha hc v ng dng
ca asen. Hiro asenua; cc oxit v oxiaxit ca asen. Trng thi t nhin, iu ch, tnh
vt l, tnh cht ha hc v ng dng ca antimon. Hiro antimonua; cc oxit v oxiaxit
ca antimon.
B. NI DUNG:
1. Tnh cht l hc: Ging vi pht pho, cc nguyn t As, Sb v Bi c mt vi dng
th hnh, dng khng kim loi v dng kim loi.
- Dng khng kim loi ca As v Sb c
to nn khi lm ngng t hi ca chng l
nhng cht rn mu vng gi l asen vng,
atimon vng. Chng c mng li phn t
ging nh P trng, cng tan c trong CS
2
.
So vi P trng th Asen vng km bn hn
nhiu,
0
t thng di tc dng ca nh
sng n chuyn sang dng kim loi. Atimon
vng cn km bn hn na, ch tn ti
0
t thp.
- Dng kim loi ca Asen c mu trng bc,
ca Atimon c mu trng bc pht . C
kin trc ging nh P en. Gin d nghin
thnh bt, dn in v dn nhit, khng tan
trong CS
2
.
As Sb
0
t s 610
0
C 635
0
C
0
t nc 817
0
C 630
0
C
2. Tnh cht ho hc:
- trong khng kh thng, Sb khng b bin i, cn As b oxi ho trn b mt, khi
un nng chng chy to thnh oxit.
4As + O
2
2As
2
O
3

- dng kim loi c 2 nguyn t As, Sb bc chy trong kh clo to thnh triclorua
2As + Cl
2
2AsCl
3
2Sb + 5Cl
2
2SbCl
5
( dng bt mn Sb chy trong clo cho ngn la).
Khi un nng chng tc dng vi Br, I, v S.
- Khng tan trong dung dch axit HCl, nhng cc cht oxi ho mnh nh HNO
3
c,
nc cng thu th oxi ho: As thnh axit asenic H
3
AsO
4
Sb thnh axit meta antimonic HSbO
3
3As + 5HNO
3
+ 2H
2
O 3H
3
AsO
4
+ 5NO
3Sb + 5HNO
3
3HSbO
3
+ 5NO + H
2
O
Ring As cn c th tan trong kim nng chy gii phng H
2

2As + 6NaOH 2Na
3
AsO
3
+ 3H
2

3. Trng thi t nhin, ng dng v phng php iu ch
2 nguyn t As, Sb u tng i ph bin trong thin nhin, chng ch tn ti
ch yu di dng khong vt sunfua nh: As
4
S
4
, As
2
S
3
, Sb
2
S
3
, Bi
2
S
3
, ngoi ra cn
ln trong cc khong vt ca kim loi khc.
* iu ch: ngi ta thng t chy khong vt sunfua trong khng kh chuyn
chng thnh oxit sau dng than kh oxit thnh kim loi.
2E
2
S
3
+ 9O
2
6SO
2
+ 2E
2
O
3
E
2
O
3
+ 3C 3CO + 2E
* ng dng: ng dng ca asen n cht rt hn ch. Ngi ta cho vo ch
0,5-1% to sc cng b mt ln v d dng to thnh nhng git hnh cu ch to
cc loi ph k. Asen cn c dng trong hp kim ch to cc bi.
Antimon c dng sn xut cc hp kim, v antimon c tnh cht lm rn cc kim
loi mm nh thic, ch v.v chng hn nh hp kim ch-antimon dng c ch in.
4. Hyrua ca As, Sb
107

2 nguyn t As, Sb ch to nn hyrua kiu EH
3
c cu to ging NH
3
v PH
3
.
- AsH
3
(asin) : c mi ging ti
- SbH
3
(stibin) : l cht kh khng mu, c mi trng thi, rt c.
So snh vi NH
3
v PH
3

NH
3
PH
3
AsH
3
SbH
3

- di lin kt:(
0
A) 1,01 1,4 1,52 1,7 tng dn
- NL trungbnh lin kt (kJ/mol): 380 323 281 256 gim dn
-
0
t nc -78 -133,8 -116 -88
-
0
t s - 33 - 87,7 - 62 -18
- Momen lng cc (D): 1,47 0,58 0,22 0,12 gim dn
Nhn xt:
* Tnh bn: Nng lng trung bnh ca lin kt E H gim dn, di lin kt
tng ln, lm cho bn nhit ca cc hyrua gim t NH
3
BiH
3

V d: NH
3
v PH
3
kh bn.
As H
3
tng i bn (phn hu 300
0
C). SbH
3
rt km bn.
* S gim momen lng cc ca cc hyrua lm cho tnh cht cho cp e ca
hyrua yu dn.
V d: NH
3
c kh nng kt hp d dng khng nhng vi axit m c vi nc.
PH
3
kt hp vi axit mnh nht nh HClO
4
, HNO
3
.
AsH
3
ch kt hp vi HI nhit thp.
SbH
3
th khng c nhng kh nng .
* Tnh kh tng t NH
3
n SbH
3

V d: NH
3
khng phi l cht kh c trng, trong khi d PH
3
, AsH
3
v SbH
3
l cht
kh mnh: chng d bc chy trong khng kh v kh c kim loi nh Cu, Ag ra
khi mui ca n.
6AgNO
3
+ AsH
3
+ 3H
2
O 6Ag + 3HNO
3
+ H
3
AsO
3

* iu ch: Cho mui ca chng tc dng vi axit
V d: Mg
3
Sb
2
+ 6 HCl 3 MgCl
2
+ 2 SbH
3
.
Zn
3
As
2
+ 3H
2
SO
4
(l) 3ZnSO
4
+ 2AsH
3

Cho hiro mi sinh kh cc hp cht tan ca asen v antimon
As(OH)
3
+ 6H AsH
3
+ 3H
2
O
Sb(OH)
3
+ 6H SbH
3
+ 3H
2
O
5. Oxit ca As, Sb
* Oxit ca As, Sb vi s oxi ho + 3
V d: i vi As v Sb tn ti di dng phn t kp As
4
O
6
, Sb
4
O
6
.
C 2 oxit u c mt vi dng tinh th: oxit ca As(III) v Sb(III) c mu trng.
- C 2 oxit ny u rt t tan trong nc tr oxit ca As (III) tan nhiu hn mt
cht.
As
4
O
6
+ 6 H
2
O 4H
3
AsO
3
(l axit yu).
Trong cc oxit trn tnh axit gim v tnh baz tng t As Sb.
V d:
- As
4
O
6
tan trong dung dch kim mui.
- Sb
4
O
6
tan c trong axit HCl, axit hu c v cn tan c trong dung dch
kim.
Lu : Asen(III) oxit rt c, ch cn lng nh 0,1 g l c th gy cht ngi. Ngi ta
dng ch thuc tr su trong nng nghip.
+ iu ch: oxit ca As, Sb, Bi. mc oxi ho +3 bng cch t chy nguyn t
As, Sb, Bi trong khng kh hoc nung qung c cha nguyn t asen, antimon...
* Oxit ca As, Sb vi s oxi ho + 5
V mt cu trc ca chng cha c bit r v ngi ta thng gn cho chng
cng thc kinh nghim l As
2
O
5
, Sb
2
O
5
.
Cc oxit phn hu nhit cao hn (trn 400
0
C).
108

As
2
O
5

0
t
As
4
O
6
+ O
2

Sb
2
O
5

0
t
Sb
2
O
4
+ O
2

As
2
O
5
d tan trong nc to thnh axit asenic:
As
2
O
5
+ 3H
2
O 2H
3
AsO
4

Cn Sb
2
O
5
rt t tan trong nc.
Khc vi P
4
O
10
, cc oxit ca As, Sb v Bi vi s oxi ho + 5 c tnh oxi ho mnh, tc
dng vi axit HCl gii phng Cl
2
.
As
2
O
5
+ 10HCl 2AsCl
3
+ 2Cl
2
+ 5H
2
O

* Oxi axit ca As, Sb vi s oxi ho +5:
Quan trng l axit asenic:H
3
AsO
4
v axit antimonic xSb
2
O
5
. yH
2
O c coi nh
l axit.
Khc vi H
3
PO
4,
tnh cht ho hc c trng ca cc oxi axit ca As, Sb v mui
ca chng c kh nng oxi ho, tnh oxi ho tng t As S.
V d: axit H
3
AsO
4
v axit antimonic ch th hin tnh oxi ho trong mi trng
axit. v axit H
3
AsO
4
ch oxi ho c nhng cht kh mnh nh HI n It,
axitantimonic oxi ho c nhng cht kh mnh nh HCl n Cl
2
.
H
3
AsO
4
+ 2HI H
3
AsO
3
+ I
2
+ H
2
O
Nhn xt: So snh hot tnh oxi ho kh ca cc nguyn t As, Sb cc s oxi ho
+3 v +5 th:
Tnh kh tng
As (III), Sb(III)
As(V), Sb(V)
Tnh oxi ho tng



Chng 7: CC NGUYN T PHI KIM NHM IVA
A. MC TIU:
c im chung ca cc nguyn t nhm IVA; trng thi t nhin, tnh cht ha
hc ca cacbon; iu ch, tnh cht v ng dng ca cacbon oxit; iu ch, tnh cht v
ng dng ca cacbon ioxit; hiu ng nh knh, axit cacbonic; cc hp cht ca cacbon
vi nit v halogen (ixian,hiro xianua, cc mui xianua, cc hp cht cacbon
tetrahalogenua; trng thi t nhin, tnh cht vt l, tnh cht ha hc ca silic; silan;
silic ioxit, axit silixic v mui silicat; silicat k thut (thy tinh, gm s, xi mng).
B. NI DUNG:
Tit 54, 55
Bi 1: C IM CHUNG
Nhm IVA bao gm cc nguyn t:
Kh hiu C Si Ge Sn Pb
STT 6 14 32 50 82
Tn gi Ccbon Silic Gecmani Thic Ch
KLNT 12,0046 32,064 78,96 127,6 210
Cu hnh
e

BKNT
m
in
NL ion
[He]2s
2
2p
2

0,77
0
A
2,5
11,26
eV
[Ne]3s
2
3p
2

1,17
0
A
1,8
8,15 eV
[Ar]3d
10
4s
2
4p
2

1,22
0
A
1,8
7,88 eV
[Kr]4d
10
5s
2
5p
2

1,40
0
A
1,8
7,33 eV
[Xe]4f
10
5d
10
6s
2

6p
2

1,75
0
A
1,8
7,42 eV
109

ho (I)
Nhn xt chung:
- Nguyn t ca nhng nguyn t ny u c cu hnh electron lp ngoi
cng ns
2
np
2
(4e).
|+

| |

ns
2
np
2
S e ho tr bng s obitan ho tr, tng nng lng ion ho kh ln,
chng khng th mt 4 e ho tr bin thnh cation +4 v cng khng
th kt hp thm 4e ho tr bin thnh ion - 4 do m in ca chng
nh. Do vy mun t c cu hnh bn ca nguyn t kh him, nhng
nguyn t ca chng phi to nn nhng cp e chung
ca lin kt cng ho tr.
- Trong hp cht, chng c s oxi ho - 4, +2 v +4, theo chiu tng ca
in tch ht nhn nguyn t t C Pb, bn knh nguyn t tng, nng
lng ion ho gim, tnh phi kim gim, tnh kim loi tng. Khuynh
hng th hin s oxi ho - 4 gim
m khuynh hng th hin s oxi ho +2 tng, do kh nng to lin kt
cng ho tr ln.
- Cc nguyn t ca nguyn t nhm IV A cn c kh nng lin lin kt
vi nhau to thnh mch di, khuynh hng ny mnh nht C to nn
nhng mch C - C di n hng trm nguyn t v khuynh hng to
thnh nhng mch di gim t C n Pb v gim dn theo chiu tng
bn knh nguyn t. (Do bn ca lin kt trong phn t gim t C
Pb, nng lng lin kt gim t C n Pb: V d: NLLK trong C-C l
347 kJ/mol; Si Si l 219,5 kJ/mol; Ge Ge l 167 kJ/mol; Sn Sn l
154,8 kJ/mol; Pb khng cho hp cht c lin kt Pb Pb).

Bi 2: CACBON
Z = 6
Khi lng nguyn t: 12,01
S khi ca cc ng v bn: 12, 13 (C
14
c ngun gc t v tr)
Cu hnh e: [He] 2s
2
2p
2

| +

| |

ns
2
np
2
Trong cu hnh e 1s
2
2s
2
2p
2
ca nguyn t C, c 2 electron 2p c xp trn 2
obitan 2p v c coi l c spin nh nhau.
2.1. Trng thi t nhin
Trong thin nhin C khng phi l nguyn t ph bin nht, ch chim 0,14%
tng s nguyn t ca v qu t, m ch yu di dng khong vt nh vi,
lmt CaMg(CO
3
)
2
, tt c nhng nhin liu nm di t nh: du m, kh than bn,
phin... v c th sinh vt. ( u c C , c s sng).
2.2. Tnh cht vt l
Cacbon gm mt s dng th hnh khc nhau nh: Kim cng, than ch, cc bon
v nh hnh.
a) Kim cng:
110

Tinh th kim cng thuc h lp phng, mi nguyn t C trong
tinh th trng thi lai ha sp
3
, c lin kt cng ho tr vi 4 nguyn t C
4 nh ca hnh t din. Khong cch gia cc nguyn t C l 1,545
0
A
Kim cng c mng li tinh th nguyn t in hnh, cng nht
trong tt c cc cht. Nh bc hc Mox ly thang cng ca kim
cng bng 10, kim cng khng dn in, khng mu v trong sut, c
ch s khc x nh sng ln trng lp lnh v rt p do dng lm
trang sc qu.
b) Than ch: graphit
Mng tinh th ca than ch c cu trc nhiu lp C phng chng
ln nhau, mi nguyn t C trng thi lai ho sp
2
c lin kt cng ho tr
vi 3 nguyn t C nm trong 1 lp xung quanh to thnh nhng vng 6
cnh lc gic u.
- Khc vi Kim cng, than ch dn in, nhit c, cho nn trong thc
t c dng lm in cc bi v mi nguyn t C cn c 1 e c thn
cha lin kt, s to lin kt vi 1 trong 3 nguyn t C bao quanh, e ny
linh ng gn nh e trong mng kim loi.
- Cc lp trong tinh th than ch lin kt vi nhau bng lc Vanecvan yu nn than ch
rt mm. Bt than ch trn vi t st c dng lm rut bt ch en.
- Ging vi kim cng than ch c nhit nng chy rt cao, d
ngi ta dng than ch lm chn nung v ni nu chy kim loi.
Qu trnh chuyn kim cng sang than ch xy ra rt chm nhit
thng, cho nn kim cng tn ti lu di trong iu kin thng. Khi
un nng khong 1500
0
C, trong iu kin khng c khng kh th kim
cng chuyn sang than ch.
1500
0
C
Kim cng than ch
Khng c khng kh
c. Ccbon v nh hnh (Cacbin)
Cc bon c nhiu dng v nh hnh nh: than g, than mui, than
cc... chng dng tinh th ca than ch. L cht bt mn c b mt pht
trin, c khi n 1000m
2
/g. Do c kh nng hp ph ln cc phn t
kh v phn t cht tan t dung dch.
* Than mi iu ch c cha hp ph cc cht cn c kh nng
hp ph rt cao c gi l than hot tnh, than hot tnh c dng
tr cc cht c (trong mt n phng c), loi cc cht bn trong lc
ng v lc du thc vt, lm cht xc tc cho cc phn ng gia cc
cht kh.
- iu ch bng cch: Nung nh cc cht hu c nh g, s da,
cc cht ph thi trong cng nghip thc phm nh xng, mu, hay
ng ma. Trc khi nung ngi ta cho thm cc ph gia nh ZnCl
2

tng din tch tip xc.
* Than g: L vt liu xp, nh, mu en, cn gi c cu to ca
g. c sn xut bng cch nung g trong cc l nung th cng, n
cng l cht hp ph quan trng.
* Than mui: L cht bt mn c mu en v nh, n khng phi l
C tinh khit m cn cha nhng cht bay hi do than hp ph hoc lin
kt vi than, than mui dng lm mc in , giy than, mc tu, sn
en, xi en lm mi o da, gng tay da, giy da v ch yu c dng
lm cht n cho cao su ch to lp t. V than mui lm cho cao su
bn hn, ko di thi gian s dng.
111

* Than cc: L cht c dng khi rn, mu en xm, cng v nng
hn than g, l sn phm rn cn li khi nung than nhit cao
trong l chu nhit.
* Tm li: Tt c cc dng v nh hnh ca C nhit cao
u chuyn thnh than ch, tnh cht l hc chung ca nhng dng th
hnh ny l khng mi, khng v, kh nng chy, kh bay hi, khng tan
trong cc dung mi thng thng nhng tan nhiu trong kim loi nng
chy: Fe, Co, Ni...
2.3. Tnh cht ha hc
nhit thng C rt km hot ng ho hc, nhng nhit
cao tr nn hot ng mnh, trong C dng v nh hnh hot ng
mnh hn sau n than ch, kim cng.
V d: C ch phn ng vi H
2
to thnh kh axetilen khi pht la h
quang gia 2 in cc than ch t trong bu kh hyro.
2C + H
2
C
2
H
2
; H
0
= +226,38 kJ/mol
Nguyn t hot ng mnh nht ca halogen l Flo phn ng vi C
nhit thng.
V d: than mui chy trong Flo d to thnh tetrafloruacacbon
C + 2F
2
CF
4

CCl
4
ch c iu ch k nh vi hiro to thnh C
2
Cl
6
v
C
6
Cl
6
. CCl
4
ch c iu ch gin tip:
CS
2
+ 2Cl
2
CCl
4
+ 2S
+ Tnh oxi ho: Cc bon tc dng vi nhiu kim loi to thnh ccbua
kim loi
2C + Ca CaC
2
(t n)
3C + 4Al Al
4
C
3

C + 3Fe Fe
3
C
- Hi lu hunh tc dng vi than t nng to nn cacbonisuafua
C + 2S CS
2

- Trong cc nguyn t ca nhm Nit, ch Nit phn ng vi C di cc iu kin
ging nh tng hp axetylen to thnh kh xian
2C + N
2
C
2
N
2
(kh xian tn ti di dng ixian C
2
N
2
hay (CN)
2
).
+ Tnh kh mnh: nhit cao C kh c nhng hp cht nh: O
2
, H
2
O, axit HNO
3
,
H
2
SO
4
thnh kh CO
2
. c bit kh c oxit kim loi gii phng KL.
C + O
2
CO
2
C +ZnO

Zn + CO

C + H
2
O

CO

+ H
2
2.4. iu ch v ng dng
- iu ch kim cng nhn to trn quy m cng nghip bng cch nung nng
than ch
0
t l 1800 - 3800
0
C di p sut 60000 -120000 atm, c cht xc tc l kim
loi: Fe, Ni, Co.
- Than ch cng c iu ch nhn to bng cch kt tinh C v nh hnh
nhit cao khong 2500 3000
0
C trong l in c bit.
- Than cc c iu ch bng cch nung than 1000-1200
0
C trong iu
kin thiu khngkh. Trong qu trnh nung, than tch ra nhng hp cht d bay hi
v sn phm cn li l khi rn kt dnh vi nhau gi l than cc.
- Than mui c to nn khi nhit phn mt s hp cht hu c d bay hi
trong pha kh (tt nht l iu ch t kh mtan CH
4
)
ng dng: Kim cng dng lm dao ct kinh, mi khoan, than
ch dng lm in cc, rut bt ch...
112


Tit 56 (t hc)
Bi 3: CACBON OXIT
Phn t CO c cu to:
Lin kt C O c nng lng 1070 kJ/mol (ln nht trong tt c cc lin kt), di
lin kt l 1,12
0
A(b) do phn t CO rt bn vi nhit, 6000
0
C cha phn hu.
Cu trc ca phn t CO ging cu trc ca phn t N
2
nn c mt s tnh cht l ho
ging vi nit, l cht kh khng mu, khng mi, rt c, kh ho lng v kh ho rn;
t
0
nc l -204
0
C ; t
0
s l -195,5
0
C ; t tan trong nc.
3.1 Tnh cht ho hc:
- Tnh kh mnh: Ging vi nit, CO km hot ng nhit thng, nhng
khc nit l nhit cao kh nng kh tng ln rt mnh.
- Kh c phi kim:
CO + O
2
CO
2
CO + Cl
2

0
t
COCl
2
(photgen) rt c.
- Kh oxit kim loi:
3CO + Fe
2
O
3

0
t
2Fe + 3CO
2
CO + ZnO
0
t
Zn + CO
2

- Trong dung dch kh CO kh c mui ca kim loi qu nh : Ag, Pt, Pd
PdCl
2
+ H
2
O + CO Pd + 2HCl + CO
2

(Nh phn ng ny ngi ta dng nhn bit kh CO trong hn hp kh).
- Kh c I
2
O
5
n I
2
:
5CO + I
2
O
5
I
2
+ 5CO
2

(Nh phn ng ny ngi ta dng nh lng kh CO trong ho hc phn tch).
nhn xt: Kh CO c tnh kh tng ng vi hyro phn t.
Vi cc cht oxi ho khc trong dung dch, thng ch xy ra khi c mt ca
cht xc tc.
V d: Kh KMnO
4
c mt ca bt mn bc kim loi
Kh K
2
Cr
2
O
7
c mt ca mui thu ngn.
- 300
0
C, xc tc Ni, kh CO tc dng c vi H
2
to thnh kh mtan
CO + 3H
2

0
, t xt
CH
4
+ H
2
O
- 350
0
C, vi cht xc tc l ZnO c hot ho bng Cr
2
O
3
v 250 atm, kh CO tc
dng vi H
2
to thnh ru mtylic:
CO + 2H
2
CH
3
OH
Ngoi kh nng oxi ho - kh, CO cn c th kt hp vi mt s cht nh cp e t do
cacbon
- Tc dng vi Niken: CO + Ni
0
50 C
Ni(CO)
4
(Niken tetracacbonyl)
- Tc dng vi hemoglobin: CO + Hb HbCO
113

Lu : hp cht HbCO bn lm cho hng cu khng lm c nhim v chuyn ti oxi
t phi n cc mao qun trong c th con ngi. Vy kh CO rt c i vi con
ngi.
Kh CO v NO u c hi, gy nhim mi trng. Do bo v mi
trng trong sch ca khng kh cc th, ngi ta lp vo t mt thit b gi l
thit b chuyn ho xc tc (cht xc tc y thng l: Pt, Pd, Al
2
O
3
), qua thit b
nhng kh c c chuyn ho thnh kh khng c hi (vi iu kin bo v cho
hot tnh ca cht xc tc l t chy bng etxng khng cha ch v ch l cht c cho
cht xc tc).
2CO + 2NO CO
2
+ N
2

- iu kin thng kh CO khng tc dng vi H
2
O v kim, nhng nhit
cao v p sut cao th phn ng xy ra:
H
2
O + CO
0
t
H
2
+ CO
2

CO + NaOH
atm
C
150
200
0
HCOONa (Fomiat natri).
vy c th coi CO l anhyrit axit ca axit fomic: HCOOH
3.2. iu ch:
Trong PTN: ngi ta iu ch CO bng cch lm mt nc ca axit fomic c mt ca
axit H
2
SO
4
c v nhit cao.
HCOOH
0
t
= CO + H
2
O
3.3. ng dng: - Kh CO c s dng lm cht ban u trong nhiu phn ng tng
hp hu c nh tng hp ru mtylic...v c dng lm cht kh.
Bi 4: CACBON IOXIT
Ccbon i oxit : CO
2

(kh cacbonic).
Phn t CO
2
c cu to dng ng thng O = C = O, di lin
kt C O l 1,162
0
A, nng lng lin kt l 803 kJ/mol.
4.1. Tnh cht l hc:
CO
2
l mt cht kh khng mu, c mi v v hi chua, nng hn
khng kh , d ho lng, d ho rn,
t
0
nc l -37
0
C 5 atm; 60 atm, ngay nhit thng kh CO
2
bin
thnh cht lng khng mu, khi c lm lnh t ngt cht lng bin
thnh khi rn mu trng gi l tuyt cacbonic.
Kh CO
2
rt bn vi nhit v tan tng i nhiu trong nc, 1 lt
nc 0
0
C ho tan 1,7 lt kh CO
2
. Kh CO
2
khng duy tr s h hp,
khng duy tr s chy (do ngi ta dng kh CO
2
cha chy).
Nng kh CO
2
trn 3% trong khng kh c th lm ri lon thn
kinh; 10% c th lm mt tr v i n cht v ngt.
4.2. Tnh cht ho hc:
- CO
2

rt bn vi nhit, nhit 2000
0
C mi phn hu 75% thnh CO
v O
2

2CO
2
2CO + O
2

- CO
2
l mt oxit axit yu, tc dng vi nc to thnh axit H
2
CO
3

CO
2
+ H
2
O

H
2
CO
3

- Tc dng vi baz:
CO
2
+ NaOH NaHCO
3

114

CO
2
+ 2 NaOH Na
2
CO
3
+ H
2
O
CO
2
+ CaO CaCO
3

- Tnh oxi ho: tc dng vi kim loi:
CO
2
+ 2Mg 2MgO + C
3CO
2
+ 4Al 2Al
2
O
3
+3C
- Phn ng quang hp : Cy xanh hp th lin tc kh CO
2
ca kh quyn
gii phng O
2

6 CO
2
+ 6 H
2
O
h0
C
6
H
12
O
6
+ 6O
2

(Glucoz)
4.3. iu ch v ng dng: Trong PTN iu ch kh CO
2
bng cch: Cho
CaCO
3
tc dng vi axit HCl trong bnh kp.
CaCO
3
+ 2HCl CaCl
2
+ H
2
O + CO
2
|
Trong CN: - qu trnh nung vi CaCO
3
CO
2
| + CaO
- Ln men ru ca ng glucozo
C
6
H
12
O
6

men
2CO
2
| + 2C
2
H
5
OH
ng dng: CO
2
dng sn xut sa, phn m, ur, bia, nc
hoa qu c ga, nc khong c ga.
4.4. Axit Cacbonic v mui cacbonat
4.4.1. Axit H
2
CO
3
: L axit yu, khng bn, ngay nhit thng phn
ly thnh nc v kh cacbonic (do khng th tch axt H
2
CO
3
ra
iu kin thng).
H
2
CO
3
H
2
O + CO
2

Trong dung dch nc axt H
2
CO
3
phn ly hai nc:
H
2
CO
3


H
+
+ HCO
3
-
HCO
3
-


H
+
+ CO
3
-2

4.4.2. Mui cacbonat: axit H
2
CO
3
to nn 2 loi mui: Hyrocacbonat
v cacbonat
- Hyrocacbonat v cacbonat ca cc kim loi kim v amoni d tan
trong nc tr NaHCO
3
hi t tan. Hyrocacbonat ca kim loi kim th
tan, cn cacbonat cc kim loi khc khng tan c bit l cacbonat ca
kim loi nng khng tan.
- Cacbonat kim loi kim bn vi nhit, khi un nng chng nng chy m khng
phn hu.
V d: Na
2
CO
3
nng chy 853
0
C
K
2
CO
3
nng chy 894
0
C
Nhng mui cacbonat khc phn hu gii phng CO
2
khi un nng:
Ca(HCO
3
)
2

0
t
CaCO
3
+ CO
2
+ H
2
O
* ng dng: Mui cacbonat c s dng nhiu trong sn xut
thu tinh, x phng
4.5. Hiu ng nh knh
Nhng cht c tc dng iu tit nhit gia ban ngy v ban m
l kh cacbonic v hi nc. Chng lm cho nhit trn mt t ch
thay i trong mt bin hp, c th ni tng i hng nh trong cc
ma.
Nng lng mt tri ch yu l cc sng ngn, d xuyn qua bu
kh quyn trong khi bc x ca qu t l sng di d b kh quyn gi
li. Kt qu c s trao i khng cn bng v nng lng gia qu t v
khng gian v tr dn n s gia tng nhit ca kh quyn v b mt
qu t. Hin tng ny din ra theo c ch tng t nh nh knh trng
cy v c gi l hiu ng nh knh.
115

Cc tc nhn gy hiu ng nh knh l CO
2
, hi nc, CFC, CH
4
,
NO
2
(vi mc CO
2
> hi nc > CFC > CH
4
> NO
2
).



Tit 57
Bi 5:
CC HP CHT CA CACBON VI NIT V HALOGEN

5.1. ixian (CN)
2

trng thi kh, xian gm nhng phn t kp (CN)
2
c cu to ng thng.
Xian l kh khng mu, mi xc, d ho lng v ho rn (t
0
nc
= -34,4
0
C, t
0
s
= -
20,7
0
C) tan trong nc v rt c Xian (TK) kh bn vi nhit; trn 1000
0
C mi phn
hu:
(CN)
2
2CN. V gc CN cng rt bn vi nhit.
Khi chu tc dng lu ca tia t ngoi hoc khi un nng n gn 500
0
C, xian trung
hp thnh mt khi rn, v nh hnh, mn en, khng tan trong nc v c thnh phn
(CN)
n
v gi l paraxian c cu to vng:
Trong khng kh xian d bc chy cho ngn la hng vin xanh v c nhit cao
(~ 4500
0
C). vng hng c phn ng.
(CN)
2
+O
2
2CO +N
2
. Vng xanh phn ng chy ca CO.
Khi lu trong nc, xian b thu phn theo 2 c ch sau:
(CN)
2
+H
2
O HCN + HNCO (axitxianic)
Ri axit ny b thu phn tip cho pominat amoni v ur.
C ch 2 l: (CN)
2
+ 2H
2
O
Ri oxavini dua b thu phn to nn amoni oxilat. C ch ny xc nhn cu to N-
C-C-N ca phn t xian.
S thu phn ca xian cho thy s ging nhau ca xian vi halogen, nht l trong
mi trng kim.
(CN)
2
+ 2NaOH NaCN + NaOCN +H
2
O.
Bi vy xian c gi l halogen gi. V tnh cht n nm gia Brom v iot.
iu ch: Hg(CN)
2
+ HgCl
2
Hg
2
Cl
2
+(CN)
2

dd 2CuSO
4
+ NaCN
dd
2Na
2
SO
4
+ CuCN +(CN)
2

5.2. Hiro xianua
HCN l hp cht CHT, phn t c cu to thng H- C N:
Mt phn t khc ng phn vi n l hiro zoxiama H-N C:
Trong hioxinua bnh thng c c 2 dng ng phn trng thi
cn bng vi nhau
HCN HNC
iu kin thng, HCN chim 99,5%, khi un nng t l HNC
tng ln, hin nay ngi ta cha tch ring c HNC tinh khit.
Hiroxiama l cht lng khng mu, c mi kh chu, d ho rn v d
bay hi (t
0
nc
= - 15
0
C, t
0
s
= 25,6
0
C)
trng thi lng v rn c hot ng trng hp phn ng nh lin kt
H.
H-C N:H- C N: H- C N:
Hin tng trng hp cn c mt phn trng thi hi. Do hot ng
trng hp , HCN lng c hng s in mi rt ln (~ 120). So vi
nc (~ 80) do vy HCN lng l 1 dung mi ion ho tt vi nhiu cht.
HCN tan trong nc, rn, ete theo bt c t l no. Trong dung dch
nc HCN l 1axit rt yu (K = 2,1.10
-9
), yu hn CaH
2
CO
3
. Trung
dung dch, cn xy ra phn ng thu phn:
HCN + 2H
2
O HCOONH
4
(fomiat amoni)
116

trng thi khan v dung dch, HCN ch bn khi c 1 lng nh axit v
c lm cht n nh. Nu khng n s trng hp thnh sn phm rn mu
en.
Khi t nng trong khng kh, HCN chy cho ngn la mu tm:
4HCN + 5O
2
2H
2
O + 6CO
2
+ 2N
2

HCN dng ch yu trong tng hp hu c.
iu ch: un hn hp CO v NH
3
500
0
C di p sut vi xc tc
ThO
2
: CO + NH
3
HCN + H
2
O
PTN: NaCN + H
2
SO
4
NaHSO
4
+ HCN
Mui ca axit HCN gi l xianua: [:CN:]
-

- Ion CN
-
khng mu nn cc mui ni chung khng mu. Phn ng
ca ion CN
-
ging nhiu vi ion halogen, VD: phn tch da vo phn
ng ny nhn ra CN
-
:
- Do c s e bng s e ca CO v c cp ion t do C,ion CN
-
cng
to nhiu phc bn vi ion kim loi chuyn tip
VD: K
2
[M(CN)
4
] vi M = Ni
2+
, pd
2+
, Pt
2+

K
4
[M(CN)
6
] vi M= Mn
2+
, Fe
2+
, CO
2+

- Khi c mt oxi, ion CN
-
c th ha tan Au, Ag nh to phc tan:
4Au+ 8NaCN + H
2
O + O
2
4 Na[Au(CN)
2
] +4NaOH
Mui xianua v HCN u rt c. Trong cc xinua, ch c xianua kim
loi kim v kim th l d tan, cn cc xiamua khc u t tan. Ring
mui ca Hg tan nhiu trong nc v hu nh khng b ion ho.
- Mui xianua b thu phn manh trong dung dch
CN
-
+ H
2
O HCN + OH
-

Nhng mui NaCN v KCN
(rn)
trong k k cng c mi HCN v n
b phn hu chm bi. CO
2
(kk).
KCN +CO
2
+H
2
O HCN + KHCO
3

- Nhiu mui xiama kim loi nng khng tan trong nc, nhng tan
trong xiama kim loi kim to phc
Mn(CN)
2
+ 4KCN K
4
[Mn(CN)
6
]
Mui CN
-
v HCN u c tnh kh. Khi un nng dung dch mui
CN
-
b oxi kk oxiho.
2NaCN + O
2
2NaCNO (Natri xianat)
Khi un si, dung dch xianua kt hp vi S to thi oxiat.
KCN + S KCNS
Trong cc xianua, ch c NaCN v KCN c dng nhiu vo vic
khai thc vng t qung.
iu ch: Dng C kh Cacbonat khi un nng.
Na
2
CO
3
+ C + 2NH
3
2NaCN +3H
2
O
Na
2
CO
3
+ C + CaCN
2
2NaCN + CaCO
3

5.4. Cc hp cht cacbon tetrahalogenua
Cacbon to hp cht vi tt c cc halogen. Cc hp cht n gin
nht l cacbon tetrahalogenua.
5.4.1. Cacbon tetraflorua (CF
4
)
Cacbon tetraflorua l cht kh khng mu, c tng hp trc tip t cc
n cht hay cho bc florua tc dng vi cacbon tetraclorua nhit
573K. Cacbon tetraflorua tan rt t trong nc.
Nu cho hirocacbon, nh metan tc dng vi flo hay coban
triflorua, hoc dn xut clo ca metan vi cht cho flo (HF, SbF
5
,
SbCl
2
F
2
), ngi ta iu ch c cc hp cht freon. y l nhng
hp cht cacbon c cha flo, clo v hiro, c dng lm dung mi v
np vo cc my lnh. Freon chim sn lng chnh l CF
2
Cl
2
, c gi
l freon 12, chim khong 85%. y l cht kh bn, khng chy, khng
n.
117

5.4.2. icacbon tetraflorua (cn gi l etilen tetraflorua C
2
F
4
)
icacbon tetraflorua polime ha di p sut ln to thnh cht
do c gi tr cao teflon, chu c nhit cao v khng b cc ha cht
nh axit mnh, baz mnh hoc cht oxi ha mnh tc dng.
Teflon c dng sn xut cc dng c th nghim cao cp v
ch to cc b in phn xt clo trong cng nghip.
- Cacbon tetraclorua (CCl
4
)
Cacbon tetraclorua c to thnh khi cho clo tc dng vi cacbon
sunfua vi cht xc tc mangan (II) clorua
CS
2
+ 3Cl
2
CCl
4
+ S
2
Cl
2

Sn phm ph ca phn ng S
2
Cl
2
tip tc tc dng vi cacbon
sunfua
S
2
Cl
2
+ CS
2
CCl
4
+ 6S
Phn ng cui cng c S kt ta.
Ngi ta cng c th iu ch cacbon tetraclorua bng clo ha kh
metan, l thnh phn chnh ca kh t t nhin
CH
4
+ 4Cl
2
CCl
4
+ 4HCl
Cacbon tetraclorua l cht lng c mi thm, khng mu, khng
chy. Do tnh cht khng chy, n c dng lm cht khng in li in
hnh v khng phn cc. Cacbon tetraclorua ch tc dng vi nc
nhit cao hay khi c cc kim loi lm xc tc
CCl
4
+ 2H
2
O CO
2
+ 4HCl
Cacbon tetraclorua c dng lm dung mi cho cc cht c lin
kt cng ha tr.
Cacbon tetrabromua v cacbon tetraioua l nhng cht rn CBr
4

c mu vng v CI
4
c mu thm. Hai hp cht ny c iu ch
bng tng tc gia cacbon tetraclorua v nhm bromua hoc nhm
ioua 337K.
Cacbon tetrabromua v cacbon tetraioua t c ng dng.

Tit 58
Bi 6: SILIC

Z = 14
KLNT: 28 vc
Cu hnh e [Ne] 3s
2
3p
2

1. Tnh cht l hc
Silic tn ti mt s dng th hnh tng t nh kim cng, c thang cng
bng 7, rt kh nng chy
0
t s l 3280
0
C;
0
t nc l 1428
0
C
Silic l tinh th c mu xm, c nh kim v l cht bn dn, chu
c nhit cao (250
0
C) hn Gecmani.
Silic khng tan trong cc dung mi m ch tan trong mt s kim loi nng chy
nh : Al, Ag, Zn, Sn, Pb (nhng khng c tng tc ho hc).
2. Tnh cht ho hc
iu kin thng Silic kh tr v mt ho hc v c mng li
tinh th rt bn, nhng
0
t cao th hin tnh kh kh mnh:
Si + 2F
2
SiF
4
Si + O
2

0
t
SiO
2
(Thch anh o)
Si + S
2
0
t


SiS
2
(isunfua silic)
118

Si + C
0
t
SiC Silic cacbua)
Kh oxit kim loi thnh kim loi
Si + 2CuO SiO
2
+ 2Cu
- Tc dng mnh lit vi dung dch kim gii phng H
2

Si + 2NaOH + H
2
O Na
2
SiO
3
+ 2H
2

Tnh oxi ho: khong
0
t t 800 900
0
C, Si tc dng vi mt s kim
loi nh: Mg, Ca, Fe, Pt, Cu to thnh xilixua
Si + 2Mg Mg
2
Si
iu kin thng Si khng tc dng vi axit v cng thu,
nhng tan trong hn hp 2 axit HF v HNO
3

3Si + 4HNO
3
+ 18 HF 3H
2
SiF
6
+ 4NO + 8H
2
O
Tc dng vi HCl, HBr nhit trn 500
0
C to SiX
4
v silan
halogenua (SiHX
3
, SiH
2
X
2
, SiH
3
X) X: l cc halogen
iu kin thng Si khng tc dng vi nc nhng 800
0
C tc dng
vi nc to thnh SiO
2

Si + 2H
2
O SiO
2
+ 2H
2
|
3. Trng thi t nhin, phng php iu ch v ng dng
3.1. Trng thi t nhin:
Silic l nguyn t ph bin ng th ba sau hyro v oxi, chim
16,7% tng s nguyn t trong v qu t.
Trong thin nhin Silic thng gp dng ct (SiO
2
)
3.2. iu ch :
- Trong PTN: t chy mt hn hp gm bt Mg v ct nghin mn:
2Mg + SiO
2
Si + 2MgO
Sau cho hn hp sn phm thu c qua dung dch HCl v HF khi
MgO v SiO
2
d s tan, cn li Si dng bt.
- Trong cng nghip: Dng than cc hoc cacbuacanxi kh thch anh
trong l in
0
t cao.
SiO
2
+ 2C Si + 2CO
3SiO
2
+ 2CaC
2
3Si + 2CaO + 4CO
3.3. ng dng: Silic c dng to cc hp kim v Silic nguyn
cht rt gin. Silic pha vo thp sn xut tn silic lm li bin th, hp
kim nhm Silic dng c cc vt dng. Silic siu tinh khit dng
trong sn xut cc pin in mt tri cung cp in cho cc my thu pht
ca v tinh nhn to.
4. Hp cht hyro ca Silic
Silic tc dng vi hyro to cc hp cht ging hyro cacbonno
gi l silan, c cng thc chung l Si
n
H
2n+2
, hin nay ngi ta bit c
nhng silan sau:
SiH
4
, Si
2
H
6
, Si
3
H
8
Si
4
H
10

monosilan isilan trisilan tetrasilan
- Khi un nng trong iu kin thiu khng kh: SiH
4
phn hu thnh Si
v H
2
.
- Cc silan t bc chy v gy n trong khng kh, ring SiH
4
bc chy
trong oxi tinh khit.
SiH
4
+ 2O
2
SiO
2
+ 2H
2
O
- Silan l cht kh mnh: nhng cht oxi ho chuyn Silan thnh SiO
2
v
H
2
O
SiH
4
+ 4MnO
2
+ 4H
2
SO
4
H
2
SiO
3
+ 4MnSO
4
+ 5H
2
O
* iu ch : Cho magisilixua tc dng vi dung dch axit H
2
SO
4
long.
Mg
2
Si + 2H
2
SO
4
(l) SiH
4
+ 2MgSO
4

5. Oxit ca Silic
5.1 Silic (I V) oxit :(SiO
2
)
119

SiO
2
l hp cht ph bin nht ca silic, trong thin nhin tn ti
di dng thch anh v ct.
* Tnh cht l hc: Silic (IV) oxit tn ti nhiu dng th hnh bn nh:

573
0
C 870
0
C 1470
0
C
Thch anh o Thch anh | Triimit | Cristobalits |
* Tnh cht ho hc:
SiO
2
trng thi kt tinh l mt cht tng i tr, khng b cc
axit ho tan, tr axit HF.
SiO
2
+ 6 HF H
2
SiF
6
+ 2H
2
O
SiO
2
tc dng vi kim chm, nhng khi nung chy SiO
2
vi hyroxt
KLK v cacbonat KLK thu c mui silicat.
SiO
2
+ 2NaOH
0
t
Na
2
SiO
3
+ H
2
O
SiO
2
+ Na
2
CO
3

0
t
Na
2
SiO
3
+ CO
2

5.2. Axit silixic v mui silicat
a/ Axit silic:
Cu to ca phn t axit silixic cha c xc nh, n c th ng
vi 2 cng thc : H
4
SiO
4
(axit orthosilixic), H
2
SiO
3
(axit metasilixic).
Thc t ion SiO
3
2-
khng tn ti m ngc li ion SiO
4
2-
rt ph bin.
Trong dung dch nhng phn t t do H
4
SiO
4
d ngng t vi nhau mt
bt nc to thnh nhng ht ln hn gi l dung dch keo, dung dch
keo ca axit l cht lng trong sut c bit. Axit H
4
SiO
4
l axit rt yu.
* iu ch : Cho silicat tc dng vi axit k c axit H
2
CO
3
. hoc thu
phn hp cht SiH
4
, SiCl
4
.
b/ Silicat:
* Silicat l mui ca axit silixic: v d: Na
2
SiO
3
, K
2
SiO
3
.
Silicat KLK trong sut nh thu tinh, khng tan trong nc lnh, ch tan
trong nc nng gi l thu tinh tan.
Silicat ca cc kim loi khc M
2
(SiO
3
)
n
khng tan trong nc.
* Silicat k thut:
- Thu tinh : + thu tinh thng l hn hp ca Na
2
O.CaO.6SiO
2
, c
dng lm chai l v ca knh, gng..
iu ch bng cch nu chy hn hp ct thch anh, vi v sa
1400
0
C.
6SiO
2
+ CaCO
3
+ Na
2
CO
3
Na
2
O.CaO.6SiO
2
+ 2CO
2

- Thu tinh pha l : thay th CaO v Na
2
O trong thu tinh thng bng
K
2
O v PbO c thu tinh pha l. Thu tinh pha l d nng chy, c
tnh khc x nh sng mnh cho nn c dng sn xut cc vt dng
pha l mi v nhng dng cao sang.
* Gm, s, men:
Nguyn liu dng sn xut gm, s l t cao lanh, bt thch anh.

CU HI LUYN TP
1. Tnh cht ho hc ca cacbon? silic?
2. Ti sao nguyn t cacbon li c kh nng to thnh mch di (mch
cacbon) ?
3. a/ c im cu to phn t ca CO.
b/ So snh cu trc electron ca phn t CO v N
2
t gii thch tnh
cht l ho tng t nhau ca hai cht ?
4. Nhng axit no c kh nng ho tan c silic? Vit phng trnh phn ng khi cho
Silic tc dng vi dung dch kim. So snh vi cacbon c g khc ?
120

5. Gii tch ti sao PH
3
si nhit thp hn so vi NH
3
, nhng silan li si nhit
cao hn CH
4
.

Tit 59
KIM TRA
(bi s 3)
A. MC TIU:
Mt s phn ng c bn ca cc hp cht ca nit; gii thch c
mt s hin tng khi cho dung dch NH
3
vo mt s mui ca kim loi.
B. NI DUNG:
Cu 1. Hon thnh cc phn ng ha hc sau: (7 im)
a. NH
4
NO
2

0
t
; NH
4
Cl + NaNO
2

0
t

NH
3
+ HNO
2
; KNO
3
+ Fe

NH
3
+ CuO
b. Ag
2
O + NH
3
+ ; Cu(OH)
2
+ 4NH
3

NH
3
+ O
2
; NH
3
+ O
2

NH
3
+ Cl
2
; NH
3
+ Na
0
t

NH
3
+ Ca ; NH
3
+ Al
C
0
900 800

c. NH
4
NO
2
; NH
4
NO
3

NH
4
Cl ; (NH
4
)
2
CO
3

NH
4
HCO
3

d. KMnO
4
+ NO + H
2
SO
4
; NO + Cl
2

HNO
3
+ P
2
O
5
; NaNO
3
+ Pb
HNO
2
+ + ... ; NO
2
+ H
2
O
HI + HNO
2
; HNO
2
+ SO
2
+ H
2
O ...
Cu 2. Cho bin hin tng v cc phn ng ha hc xy ra trong cc
trng hp sau: (3 im)
a. Cho t t dung dch NH
3
vo dung dch FeCl
3.
b. Cho t t dung dch NH
3
vo dung dch AlCl
3.
c. Cho t t dung dch NH
3
vo dung dch CuCl
2
.





P N
Cu 1: 7 im
a. NH
4
NO
2

0
t
N
2
+ 2H
2
O
NH
4
Cl + NaNO
2

0
t
N
2
+ NaCl + 2H
2
O
NH
3
+ HNO
2
N
2
+ 2H
2
O
6KNO
3
+ 10Fe 3K
2
O + 5Fe
2
O
3
+ 3N
2
2NH
3
+ 3CuO 3Cu + N
2
+ 3H
2
O
121

b. Ag
2
O + NH
3
+ H
2
O [Ag(NH
3
)
2
]OH
Cu(OH)
2
+ 4NH
3

[Cu(NH
3
)
4
](OH)
2

2NH
3
+ O
2
N
2
+ 3H
2
O
2NH
3
+ O
2
2N
2
O + 3H
2
O
2NH
3
+ 3Cl
2
6HCl + N
2

2NH
3
+ 2Na
0
t
NaNH
2
+ H
2
| (Natri amiua)
NH
3
+ Ca CaNH + H
2
| (canxi imiua)
2NH
3
+ 2Al
C
0
900 800
2 AlN + 3H
2

c. NH
4
NO
2
N
2
+ 2H
2
O
NH
4
NO
3
N
2
O + 2H
2
O
NH
4
Cl NH
3
+ HCl
(NH
4
)
2
CO
3
NH
3
+ NH
4
HCO
3

NH
4
HCO
3
NH
3
+ CO
2
+ H
2
O
d. 6KMnO
4
+ 10NO + 9H
2
SO
4
10HNO
3
+ 3K
2
SO
4
+ 6MnSO
4
+ 4H
2
O
2NO + Cl
2
2NOCl
2HNO
3
+ P
2
O
5
2HPO
3
+ N
2
O
5

NaNO
3
+ Pb PbO + NaNO
2

3HNO
2
HNO
3
+ H
2
O + 2NO
3NO
2
+ H
2
O 2HNO
3
+ NO
2HI + 2HNO
2
2NO + I
2
+ 2H
2
O
2HNO
2
+ 9SO
2
+ 8H
2
O 7H
2
SO
4
+ 2NO + 2H
2
S
Cu 2: 3 im
a. Dung dch FeCl
3
lc u c mu nu, khi cho t t dung dch NH
3

vo mu dung dch nht dn n khng mu v ng thi xut hin kt
ta nu tng dn n cc i ca Fe(OH)
3
. Nu thm dung dch NH
3

th thy lng kt ta khng tng na
FeCl
3
+ 3NH
3
+ 3H
2
O Fe(OH)
3
+ 3NH
4
Cl
b. Dung dch AlCl
3
khng mu. Khi cho NH
3
t t vo dung dch AlCl
3

thy dung dch xut hin kt ta trng nhy tng dn n cc i. Nu
cho thm dung dch NH
3
th thy kt ta khng tng ln na
AlCl
3
+ 3NH
3
+ 3H
2
O Al(OH)
3
+ 3NH
4
Cl
c. Dung dch CuCl
2
mu xanh. Khi cho NH
3
vo dung dch CuCl
2
thy
mu xanh nht dn cho n khng mu v ng thi thy xut hin kt
ta xanh. Nu thm tip dung dch NH
3
vo n d thy kt ta xanh tan
dn v ng thi thy dung dch xanh m dn n c i.
CuCl
2
+ 2NH
3
+ 2H
2
O Cu(OH)
2
+ 2NH
4
Cl
Cu(OH)
2
+ 4NH
3
[Cu(NH
3
)
4
](OH)
2



Tit 60
Chng 8: NGUYN T PHI KIM NHM IIIA (B)
A. MC TIU:
122

Trng thi t nhin, phng php iu ch , cc dng th hnh; tnh cht l ha
hc v ng dng ca bo; iu ch, cu to v tnh cht ca boran; ibo trioxit, axit boric
v mui borat.
B. NI DUNG:
Bo (B)
Z = 5 ; Cu hnh electron : [He]2s
2
2p
1

Khi lng nguyn t: 10,811; S khi ca cc ng v: 10 v 11
I. Trng thi t nhinm, phng php iu ch, cc dng th hnh
1. Trng thi t nhin
Bo trong t nhin thng gp ch yu dng borac. Bo l nguyn t khng ph bin,
chim 3.10
-4
% v khi lng v qu t.
Qung quan trng nht ca bo l kecnit (Na
2
B
2
O
7
.4H
2
O), c nhiu Califocnia (M).
Bo c dng sn xut axit Boric v mui ca n.
2. iu ch
- Bo kt tinh nguyn cht c iu ch bng cch: kh bo clorua vi kh H
2

trong ngn la n h quang vi in cc Vonfram.
2BCl
3
+ 3H
2
2B + 6HCl
- Bo dng bt c iu ch bng cch: kh bo (III) oxit vi kim loi Na hay Mg.
B
2
O
3
+ 3Mg 2B + 3MgO
II. Tnh cht li ha hc v ng dng
1. Tnh cht vt l
Bo tinh khit kt tinh c mu xm en, c nh kim, b ngoi ging kim loi,
cng gn bng kim cng. Bo rt kh nng chy,
0
t nc l 2072
0
C;
0
t s l 3700
0
C.
2. Tnh cht ho hc:
iu kin thng Bo rt tr v mt ho hc, ch kh trc tip c Flo :
2B + 3F
2
2BF
3
nhng
0
t cao n c th kh c nhiu phi kim v nhiu hp cht oxi ho khc
V d: B chy trong khng kh 700
0
C:
4B + 3O
2

0
t
2B
2
O
3
B + 3HNO
3
(c) H
3
BO
3
+ 3NO
2

dng bt mn, B tan trong kim c v nng,hoc kim nng chy.
2B + 2NaOH + 2H
2
O 2NaBO
2
+ 3H
2
3. ng dng:
Bo v hp kim st ca bo c dng trong luyn kim lm cht chng oxi ho,
ngi ta cho vo gang, thp tng kh nng rn ca gang v thp. Ngoi ra Bo cn
c dng lm vt liu trong cc ngnh k thut hin i.
III. Boran (Bohirua)
Trn thc t khng c nhng hp cht bohyrua nh: BH
3
,
B
2
H
4
, m bohyrua ny c gi vi tn chung l Boran: B
2
H
6
, B
4
H
10

, n gin nht l B
2
H
6
(iboran). L cht kh, c
0
t nc l- 1165,5
0
C;
0
t s l - 92,5
0
C. Kh iboran c mi kh chu v rt c, gy nhc u,
bun nn. Tt c Boran c th bc chy khi tip xc vi khng kh
B
2
H
6
+ 3O
2
B
2
O
3
+ 3 H
2
O
Boran tc dng mnh vi cc halogen
123

B
2
H
6
+ Cl
2
B
2
H
5
Cl + HCl
- Tt c cc boran b nc v dung dch kim phn hu thnh axit Boric
hay mui borat gii phng H
2
.
B
2
H
6
+ 6H
2
O 2H
3
BO
3
+ 6H
2

IV. ibo trioxt axit boric v mui borat
1. Bo (I I I ) oxit (B
2
O
3
)
Bo (III) oxit l cht rn dng thu tinh, khng mu, nung nng s
mm ra,
t
0
nc l 450
0
C ; t
0
s l 2250
0
C. Rt ho nc to thnh axit boric
B
2
O
3
+ 3H
2
O 2H
3
BO
3

B
2
O
3
l anhyrit axit.
trng thi nng chy, oxit boric ho tan c nhiu oxit kim loi to
thnh borat
B
2
O
3
+ CaO CaB
2
O
4

B
2
O
3
tc dng vi hyro florua to Boflorua
B
2
O
3
+ 6HF 2BF
3
+ 3H
2
O
iu ch: nhit phn axitboric
2H
3
BO
3
B
2
O
3
+ 3H
2
O
2. Axit Boric (H
3
BO
3
)
H
3
BO
3
l cht dng tinh th trong sut c mu trng.
- Tan va phi trong nc, 1 lt nc 0
0
C ho tan 1,95 gam H
3
BO
3
.
un nng, - H
2
O un nng t
0
cao hn
H
3
BO
3
HBO
2
B
2
O
3
tc dng vi nc tc dng vi nc
axit H
3
BO
3
tc dng vi dung dch baz tu theo bn cht ca cation
trong baz m thu c kiu mui borat khc nhau nh: Ca(H
2
BO
3
)
2
,
AgBO
2
, Na
2
B
4
O
7
.
* iu ch: cho mui borat tc dng vi dung dch axit HCl:
Na
2
B
4
O
7
+ 2 HCl + 5H
2
O = 4 H
3
BO
3
+ 2NaCl
3. Borat: borat l mui ca axit boric, ch c borat kim loi kim tan cn
cc borat khc u kh tan.