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Bi ging: Ha V C Khoa Cng ngh Ha v Mi trng
CHNG I: MT S KIN THC C BN V PHN NG HA HC
I.1. IU KIN XY RA PHN NG HA HC
Mt phn ng ha hc ch c th xy ra nu c hai iu kin sau:
- iu kin nhit ng: th ng p ca qu trnh phn ng phi gim

(G<0). Ni cch khc, phn ng ha hc i theo chiu c G <0;
- iu kin ng hc: tc phn ng phi ln
Nhng s liu tnh ton G ca cc phn ng ha hc c tng i trong

cc ti liu. Tuy nhin bit c tc ca phn ng ha hc cn phi qua
thc nghim. Chng ta ch bit tng tc ca phn ng ha hc cn phi s
dng mt hoc phi hp cc iu kin sau:
- tng nhit
- dng cht xc tc
- tng nng (hoc tng p sut nu l cht kh)
- dng dung mi thch hp
V d: Phn ng:
Cgr + O2(k) CO2(k)
C G0298 = - 394,38kj/mol <<0, ngha l nhit 298K phn ng l thun li

v mt nhit ng, nhng thc t nhit ny phn ng trn khng xy ra v
tc phn ng qu nh. Cacbon graphit ch chy trong oxi tinh khit nhit
khong 7000C
T nhng iu kin trnh by trn ta thy rng c th d on c

chiu ca cc phn ng ha hc da vo cc s liu nhit ng c trong ti liu,
nhng khng d on c tc ca chng, tr mt s trng hp ngi ta
bit c tc phn ng l ln ngay nhit thng, nh cc phn ng axit
v kim, phn ng to cht kt ta trong dung dch cc cht in li.
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I.2. MI LIN H GIA G CA PHN NG HA HC V CC I

LNG NHIT NG KHC
I.2.1. Cng thc tng qut cho mi phn ng
G ca mi phn ng c th c tnh bng cc cng thc sau:
G=H - TS (I.1)
G = G2,,s - G1,s (I.2)
Trong : G: s bin thin th ng p ca phn ng, J
H: entanpi ca phn ng, J
S: s bin thin entropi ca phn ng, JK-1
G2,,s : tng cc th ng p to thnh ca cc sn phm phn ng, J
G1,s : tng cc th ng p to thnh ca cc cht tham gia phn ng, J
Nu phn ng l hai chiu (thun nghch) th ngi ta thng dng cng thc
sau:

G RT ln (I.3)
K
Trong : K- l hng s cn bng ca phn ng
: c tnh bng phng trnh ging phng trnh tnh K nhng ly iu kin
bt u phn ng
R: hng s kh l tng, R = 8,314J.K-1mol-1
I.2.2. Cng thc tng qut cho mi phn ng iu kin chun
iu kin chun s bin thin th ng p chun G0 ca mi phn ng

c th c tnh bng cc cng thc sau:
G0 = H0 - TS0 (I.4)
2
G0 = G2,,s0 - G1,s0 (I.5)
Nu phn ng l thun nghch th:
G0 = - RTlnKp
Hng s cn bng Kp ca phn ng lin h vi cc hng s cn bng Kc,

Kn, KN bng cc cng thc sau:
P n
K p K c ( RT ) n K n ( ) K N ( P )n (I.6)
ni
Trong R hng s kh l tng, R = 0,082 l.atm.K-1mol-1
P: p sut chung ca h phn ng khi cn bng, atm
ni tng s mol kh c mt trong h phn ng khi cn bng
n- hiu s s mol kh hai v v s mol kh v mt ca phng trnh phn

ng
khi n = 0 th Kp = Kc = Kn = KN
Hai hng s Kp, Kc ch ph thuc vo nhit
I.2.3. Cng thc tnh G cho phn ng oxi ha - kh xy ra trong dung

dch nc
i vi cc phn ng oxi ha - kh trong dung dch nc, ngi ta

thng tnh G bng cc cng thc sau:

G nFE RT ln (I-8)
K
Nu phn ng iu kin chun th:
G nFE 0 RT ln K p (I-9)
Trong n- s electron trao i gia cht kh v cht oxi ha trong phn ng;
F-hng s Faraday, F 96500 C/mol
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0 = 0ox - 0kh - 0ox - th kh chun ca cp oxi ha kh c dng oxi ha

tham gia phn ng, 0kh th kh chun ca cp oxi ha kh c dng tham gia
phn ng, V;
=ox - kh , ca mt cp oxi ha kh lin h vi 0 ca n bng cng thc

Nernst, 250 C cng thc ny c dng:
0, 059 ox
a
ox / kh 0
lg (I.10)
kh
ox / kh b
n
Nu cp oxi ha kh ny lin h vi nhau bng phng trnh:
a ox + ne b kh
trong [ox] v [kh] nng mol/l ca dng oxi ha v dng kh trong dung
dch. Nu dng oxi ha hoc dng kh l cht rn hay cht lng khng tan trong
nc th n khng c mt trong cng thc Nernst (n c coi l hng s). Khi
dng oxi ha hoc dng kh l cht kh th ngi ta thay nng bng p sut
ring phn ca kh , atm. Nu s chuyn bin gia dng oxi ha v dng kh
c c cht trong mi trng phn ng tham gia th chng phi c mt trong cng
thc Nernst
V d: Cu2+ + 2e Cu(r)
0, 059
Cu 2
/ Cu
0Cu 2 / Cu lg Cu 2
2
Nhn xt: th kh ca mt cp oxi ha kh cng ln th tnh oxi ha ca

dng oxi ha cng mnh v tnh kh ca dng kh cng yu v phng din
nhit ng. Do ion H+ c tnh oxi ha d trong mi trng axit v kh trong
mi trng kim, cn H2 c tnh kh kh trong mi trng axit v d hn trong
mi trng kim
I.3.MI LIN H GIA CC I LNG NHIT NG CA PHN

NG HA HC V NHIT
1, Cng thc ca G ph thuc vo nhit :
4
G H
2 (I.11)
T T p T
GT2 GT1 T2
H T
dT
T2 T1 T1
T2
2, Cng thc hng s cn bng K ph thuc vo nhit :
ln K p H T0

T p0 RT
2
T
K PT 2 1 2 H T0
K PT 1 R T1 T 2
ln dT
3, S ph thuc ca entanpi phn ng vo nhit :

T2
H T 2 H T 1 C p dT
T1
Trong C p C p ( sp ) C p (tg )
C p ( sp ) tng nhit dung mol ng p ca cc cht tham gia phn ng, J.K-1
4, S ph thuc ca S phn ng vo nhit :

T2
C p
ST 2 ST 1 dT
T1
T
Thng thng ta c cc gi tr GT1, KPT1, HT1, ST1 nhit T1 = 298K v

p sut P=1atm xut pht t cc s liu trong ti liu, ngha l bit cc gi tr
G2890, Kp298, H2980 v S2980 thay vo cc cng thc trn
1.4. MI LIN H GIA CHIU PHN NG V NNG LNG LIN

KT
Phn ng ha hc xy ra l do s ph v lin kt trong cc cht tham gia

ng v to thnh lin kt trong cc sn phm phn ng, do chiu phn ng
lin quan cht ch vi nng lng lin kt.
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1.4.1. S lin h gia H ca phn ng v nng lng lin kt
thy r mi lin h ny ta xt v d sau:

H
2 Na(r) + Cl2 (k) 2 NaCl (r)
2HaNa ECl-Cl -2UNaCl
2INa
2 Na (k) + 2 Cl (k) 2Na+ (k) + 2Cl- (k)
2ACl
Theo nh lut Hess ta c:
H = 2Ha Na + ECl-Cl + 2INa + 2ACl 2UNaCl
Phn ng ny cho thy H lin h vi entanpi nguyn t ha kim loi natri

(HaNa), nng lng lin kt cng ha tr Cl-Cl trong Cl2 (ECl-Cl), nng lng ion
ha th nht ca natri (INa), nng lng kt hp electron ca clo (ACl) v nng
lng mng li ion ca NaCl (UNaCl)
I.4.2. S lin h gia S ca phn ng v nng lng lin kt
Ta bit S ca phn ng c tnh theo cng thc:
S = S2 + S1
Trong S2 tng entropi ca cc sn phm phn ng, JK-1;
S1 tng entropi ca cc cht tham gia phn ng, JK-1
V entropi l i lng c trng cho hn n ca cc cht nn lin kt trong

cht cng yu th entropi cng ln. Do i vi mt cht ta c:
Skhi >> Slng > Srn
Chng hn S0H2O(k) = 188,72 J.K-1.mol-1; S0H2O(l) = 69,94 JK-1.mol-1v S0H2O(r) =

39,33 JK-1.mol-1 nhit 250C
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T ta c th d on c s bin thin entropi (S) ca cc phn ng. Nhn

vo phng trnh phn ng nu thy s mol kh v hai nhiu hn v mt th
phn ng c S > 0 v ngc li. Nu s mol kh hai v ca phng trnh
phn ng bng nhau hoc c hai v khng c cht kh th S ca phn ng l
nh v trong trng hp ny chiu ca phn ng thng do H quyt nh
I.5. THUYT AXIT BAZO
Trong ti liu ny chng ta dng thuyt axit bazo ca Bronsted:
- Axit l tiu phn (phn t, ion) c kh nng cho proton
- Bazo l tiu phn c kh nng nhn proton
V d:
HCl + H2O Cl- + H3O+
CH3COOH + H2O CH3COO- + H3O+
NH4+ + H2O NH3 + H3O+
HCl, CH3COOH, NH4+ l cc axit
NaOH + HOH Na+.H2O + OH-
NH3 + HOH NH4+ + OH-
CH3COO- + HOH CH3COOH + OH-
NaOH, NH3, CH3COO- l cc bazo
Tuy nhin khi tnh pH n gin hn trong hu ht cc trng hp ta c th b

qua cc phn t dung mi H2O trong phng trnh phn ng:
HCl Cl- + H+
CH3COOH CH3COO- + H+
NH4+ NH3 + H+
NaOH Na+ + OH-

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Tr hai trng hp xt trn l :
CH3COOH + H2O CH3COO- + H3O+
NH3 + HOH NH4+ + OH-
Khng th b qua phn t H2O trong phng trnh
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CHNG II: S BIN THIN TUN HON MT S TNH CHT

CA CC NGUYN T THEO IN TCH HT NHN TNG DN
II.1. CU TO CA BNG DI
II.1.1. Chu k v nhm ca dng bng di
- Theo bng ny th mi hng l mt chu k v mi ct l mt nhm, tr

cc nguyn t h Lantan v h actini c xp vo nhm IIIB v nhm VIIIB
gm ba ct. C 7 chu k, 8 nhm A v 8 nhm B. trnh bng qu di, ngi
ta thng t 28 nguyn t ca hai h lantan v actinin thnh hai hng cui
bng
- Cc nguyn t ca cc nguyn t trong cng mt chu k u c cng s

lp electron. Cu hnh electron ha tr ca cc nguyn t cc nguyn t trong
cng mt nhm A hay nhm B l tng t nhau, iu ny quyt nh tnh cht
ha hc tng t nh nhau cu n cht v hp cht cc nguyn t trong cng
mt nhm
- Cu hnh electron nguyn t ca cc nguyn t trng thi c bn c th

vit c bng cch in electron vo dy cc phn lp e theo th t nh sau:
1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p 7s 5f 6d
S electron nhiu nht phn lp s l 2, phn lp p l 6, phn lp d l10 v

phn lp f l 14. Khi s e phn lp no cha s e ti a th cc e c khuynh
hng chim cc obitan sao cho s e c thn vi cc gi tr s lng t t spin
ms cng du l ln nht
Mt s nguyn t c cu hnh e nguyn t hi khc so vi cu hnh e

c vit theo nhng quy tc trnh by trn. V d, cc nguyn t crom
(Z=24), molipden (Z=42) ng l c hai phn lp e ngoi cng l (n-1)d4ns2
nhng thc t l (n-1)d5ns1. Mt phn lp ngoi ns chuyn vo phn lp
trong (n-1)d. cc nguyn t ng (Z=29) v bc (Z=47) v vng (Z= 79) nu
theo cch in e vo nguyn t nh trn th chng phi c cu hnh e phn lp
ngoi cng l (n-1)d9ns2 nhng thc t l (n-1)d10ns1, ngha l cng c s
chuyn mt e ns vo (n-1)
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Chng ta cng quan st thy s chuyn e tng t mt s nguyn t ca

cc nguyn t khc ang xy dng phn lp (n-1)d hay (n-2)f
Nguyn nhn ch yu ca s chuyn mt vi e t phn lp ny sang phn

lp kia mt s nguyn t nh trn c l l do nng lng ca cc e cc phn
lp ny rt gn nhau v cc cu hnh e na bo ha (d5, f7) hay bo ha (d10, f14)
l cu hnh bn. Mt khi xy dng phn lp ca nguyn t t gn t na
bo ha hay bo ha th mt vi e c nng lng xp x phn lp gn d
chuyn n t trng thi na bo ha hay bo ha bn. Cc hin tng ny
thng c gi l vi na bo ha v vi bo ha
II.1.2. Nguyn t s, p, d v f
Nhng nguyn t m s in vo nguyn t ca chng ang c thc

hin phn lp s c gi l cc nguyn t s. Cng nh ngha tng t cho cc
nguyn t h p, d, f
Vy cc nguyn t ca cc nhm IA v IIA l nhng nguyn t s, cc

nguyn t nhm A t IIIA n VIIIA u l cc nguyn t p. Tt c cc nguyn
t d u nm cc nhm B. Ring nhm IIIB bao gm c cc nguyn t f
II.1.3. Nguyn t chuyn tip v nguyn t khng chuyn tip
Ch c cc chu k ln (cc chu k 4, 5, 6 v 7) mi c cc nguyn t

chuyn tip l cc nguyn t d v f , chng nm gia cc chu k c tnh cht
chuyn tip t cc nguyn t s sang cc nguyn t p. Ngi ta phn bit cc
nguyn t chuyn tip d v cc nguyn t chuyn tip f
C tt c 28 nguyn t chuyn tip f nm hai chu k. Chu k 6 cha 14

nguyn t chuyn tip f t s Z = 58 n s Z =71. Chu k 7 cng cha 14
nguyn t f khc t s Z = 90 n s Z = 103. Dy cc nguyn t chuyn tip f
th nht cn c gi l h lantan hoc cc lantanoit. Dy cc nguyn t chuyn
tip f th hai cn c gi l h actini hoc cc actinoit
Cc nguyn t cn li trong bng tun hon l cc nguyn t s v p c gi l

cc nguyn t khng chuyn tip
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II.2. S BIN THIN NNG LNG CA CC OBITAN NGUYN T

THEO S TNG CA IN TCH HT NHN NGUYN T
Nng lng ca obitan nguyn t c hiu l nng lng ca e trn

obitan nguyn t . Nng lng ny c tnh bng cng thc gn ng sau:
Z '2
Ee C
n2
Trong C l hng s, Nu Ee tnh bng e V th hng s C = 13,6
N l s lng t chnh ca e c nng lng Ee
Z in tch hiu dng ca ht nhn i vi e xt: Z= Z -A
y Z l in tch ht nhn nguyn t , A l h s chn tng cng ca

cc e cn li trong nguyn t i vi e xt:
n 1
A ai
i 1
ai h s chn ca e th i i vi e xt
n: s e trong nguyn t
trong nguyn t, cc obitan u xm nhp vo nhau, nn cc e u chn

ln nhau, ngha l mi e u b cc e cn li chn v bn thn n li chn cc e
cn li. Kh nng xm nhp vo gn nhn ca obitan cng ln th cc e trn
obitan chn cc e khc cng mnh v b chn cng yu. Kh nng xm nhp
ca cc obitan trong cng mt lp gim theo th t ns-np-nd-nf. C th a ra
mt s nhn xt gn ng v cc yu t nh hng n h s chn nh sau:
- Cc e trong cng mt lp chn ln nhau km, trong cng mt phn lp

chn ln nhau cn km hn, c bit cc e trong cng mt phn lp cha mt
na s e vi gi tr ms cng du chn ln nhau km nht
- Trong cng mt lp cc e trn obitan ns chn cc e khc mnh nht, sau

n cc e np, ri n cc e nd, cui cng cc e nf c tc dng chn yu nht.
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Nhng b chn ca cc e trong cng mt phn lp th bin thin ngc li, ngha
l tng theo chiu ns-np-nd-nf
- E no lp e ng vi s lng t chnh n cng ln th b chn cng

nhiu v chn cc e khc cng t
- Tc dng chn cu mt e ny i vi mt e khc c c trng bng

i lng ai. Gi tr ai ln nht bng 1, nhng thng nh hn 1
Da vo cc yu t nh hng n h s chn trn ta c th gii thch

c s bin thin nng lng cc obitan nguyn t, nng lng ion ha nguyn
t, bn knh nguyn t v ion theo s tng ca in tch ht nhn nguyn t.
II.3. S BIN THIN NNG LNG CC OBITAN HA TR CA

CC NGUYN T THEO CHU K V THEO NHM
S bin thin nng lng cc obitan nguyn t theo s tng ca in tch

ht nhn dn n nhng kt qu sau:
- Trong mt chu k i t tri sang phi, nng lng cc obitan ha tr

cng tn gim dn t nguyn t ny n nguyn t khc. V d chu k 2, t liti
n neon nng lng cc obitan ha tr 2s v 2p u gim dn
- Hiu nng lng cc obitan ha tr np v ns (Enp-Ens) trong mt nguyn

t tng dn khi chuyn t nguyn t ny sang nguyn t khc trong mt chu k.
S bin thin ny l h qu kh nng xm nhp ca obitan ns vo gn ht nhn
ln hn so vi cc obitan np, nn nng lng ca obitan ns gim nhanh hn cc
obitan np khi Z tng.
- Hiu nng lng cc obitan ha tr Ens-E(n-1)d trong mt nguyn t tng

dn t nguyn t chuyn tip d u dy n nguyn t chuyn tip d cui dy
trong mt chu k. V d hiu nng lng E4s-E3d nguyn t Sc(Z=21) l nh
v tng dn cho n nguyn t Zn(Z=30)
- Trong phm vi mt nhm A khi i t nguyn t u nhm n nguyn

t cui nhm th nng lng cc obitan ha tr cng dng tng dn
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- Trong phm vi mt nhm B khi i t nguyn t u nhm n nguyn

t th hai trong nhm, nng lng obitan ha tr ns bin thin chm v khng
ging nhau cc nhm, ngha l mt s nhm nng lng ny gim, nhng
mt s nhm khc li tng ln. Cn t nguyn t th hai sang nguyn t th ba
trong nhm nng lng obitan ns gim xung
- Hiu nng lng cac obitan ha tr Ens-E(n-1)d trong mt nguyn t gim

dn t nguyn t u n nguyn t cui trong nhm B
II.4. S BIN THIN NNG LNG ION HA TH NHT CA

NGUYN T THEO S TNG DN CA IN TCH HT NHN
NGUYN T
Nng lng ion ha th nht I1 ca nguyn t l nng lng cn thit

bt mt e ra khi nguyn t trng thi kh, c bn thnh ion mang in tch 1+
trng thi kh, c bn, ngha l ng vi qu trnh sau:
Nguyn t(k, cb) e ion+ (k, cb); I1 > 0
Nng lng ion ha th hai (I2) v nng lng ion ha th ba (I3) ng vi

cc qu trnh:
Ion+(k, cb) - e ion2+ (k, cb); I2 > I1
Ion2 +(k, cb) - e ion3+ (k, cb); I3 > I2
Khi b ion ha th e b bt ra khi nguyn t trc tin l e lin kt vi ht

nhn yu nht, l e lp ngoi cng c nng lng ln nht. bt e khi
nguyn t phi cung cp nng lng cho nguyn t chuyn e ra khi phm
vi nh hng ca nguyn t, ngha l chuyn e ra xa v cng i vi nguyn t.
Vy nng lng ion ha th nht c tnh bng cng thc:
Z '2
I1 E Eemax Eemax C
n2
Trong Eemax l nng lng ca e c nng lng ln nht trong nguyn t
E l nng lng ca e khi n xa v cng i vi nguyn t, E =0
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Ta thy r nng lng e cng nh th nng lng ion ha cng ln
II.5. I LC VI E CA NGUYN T
i lc e ca nguyn t l kh nng kt hp e ca nguyn t. i lng

c trng cho kh nng ny l nng lng kt hp e AX. Nng lng kt hp e
nguyn t l nng lng ta ra hay thu vo khi nguyn t trong trng thi kh,
c bn kt hp e thnh ion m trng thi kh, c bn. V d:
Cl(k,cb) + e Cl- (k,cb); ACl = -348 kJ.mol-1
i lc vi e cng ln th gi tr AX cng m. i lc vi e ln nht (AX

nh nht) cc halogen v nh nht cc nguyn t s v p c phn lp e ngoi
cng s2, p6 v p3.
II.6. S BIN THIN BN KNH NGUYN T V ION THEO CHU K

V THEO NHM
II.6.1. Khi nim bn knh nguyn t v ion
Theo quan im c hc lng t v cu to nguyn t th bn knh

nguyn t v ion khng c gi tr xc nh nghim ngt, v my e trong nguyn
t khuch tn khng c gii hn r rt
Mt trong nhng nh ngha ngi ta tha nhn rng bn knh nguyn t

trng thi t do l khong cch t ht nhn n cc i ca hm phn b theo
bn knh ca obitan ngoi cng c e
Vy bn knh nguyn t ph thuc vo in tch ht nhn v trng thi

ca cc e trong nguyn t. Ni chung Z i vi cc e ha tr cng ln v s
lng t chnh ca cc e ha tr cng nh th bn knh nguyn t trng thi t
do cng nh
Trng thi ca cc e trong nguyn t t do khc vi trng thi ca chng

khi nguyn t to lin kt, nn bn knh nguyn t trng thi t do khc vi
bn knh nguyn t trng thi lin kt v nguyn t trng thi lin kt khc
nhau cng c bn knh nguyn t khc nhau. V vy nn cc bn knh nguyn t
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c dng so snh ch trong trng hp chng c xc nh trong nhng

iu kin ng nht
Trong ti liu ny chng ta dng bn knh cng ha tr, bn knh kim loi
v bn knh ion vi quy c nh sau:
- Bn knh cng ha tr c tnh bng na khong cch gia hai ht nhn

ca hai nguyn t ging nhau lin kt n vi nhau 250C. V d, khong cch
gia hai ht nhn trong phn t Cl2 l 1,988A0 ; nn bn knh cng ha tr ca
clo l 0,994A0; khong cch ngn nht gia hai nguyn t cacbon trong tinh th
kim cng l 1,544A0, nn bn knh cng ha tr ca cacbon l 0,772A0
- i vi kim loi, bn knh nguyn t c xc nh bng na khong

cch gia hai ht nhn nguyn t gn nhau nht trong tinh th kim loi v c
gi l bn knh kim loi
II.6.2. S bin thin bn knh nguyn t v ion trong chu k v trong nhm.
S co d v s co f
Cc chu k ln khc cc chu nh ch, chng c thm cc nguyn t d,

cc chu k 6 v 7 li c thm c cc nguyn t f. S in e vo cc obitan (n-1)d
cc nguyn t d lm cho phn lp e (n-1)d co li khi i t tri sang phi trong
dy cc nguyn t d cng chu k. Hin tng ny c gi l s co d. S d nh
vy v tc dng chn gia cc e trong cng phn lp d km, s in e vo cc
obitan (n-1)d lm Z i vi cc e (n-1)d ny tng ln nhanh theo s tng ca Z
S in y e vo phn lp (n-2)f cc nguyn t ca cc nguyn t f

cng dn n s co f. S co f mnh hn s co d, v tc dng chn ln nhau gia
cc e f km hn so vi gia cc e d. S co d v co f nh hng n bn knh
nguyn t, bn knh ion v nng lng ion ha nguyn t
T tri sang phi trong mt chu k bn knh nguyn t ca cc nguyn t

ni chung gim dn v Z i vi cc e ha tr tng dn, trong khi s lp e
ca cc nguyn t khng i. S bin thin ny c lp i lp li t chu k ny
n chu k khc c gi l s tun hon ca bn knh nguyn t. Ngi ta
cng quan st thy s tun hon ni chu k ca bn knh nguyn t, tng t
nh s tun hon ni chu k ca I1
15
Trong cc chu k ln, cc nguyn t d v c bit cc nguyn t f, khi

i t tri sang phi s gim bn knh nguyn t chm hn nhiu so vi cc
nguyn t s v p cng chu k, v s co d v c bit s co f lm tng tc dng
chn ca e (n-1)d v c bit ca cc e (n-2)f i vi cc e ns, do Z i vi
cc e tng chm
T trn xung di trong cc nhm A bn knh nguyn t v ion ng

dng tng dn, v s lp e tng dn cc nguyn t, trong khi Z i vi cc
e tng ln chm hn
Trong cc nhm B, khi i t nguyn t th nht n nguyn t th hai,

bn knh v ion ng dng tng nhng chm, t nguyn t th hai sang nguyn
t th ba cc bn knh ny khng bin i my v cc nguyn t th ba trong
nhm chu nh hng ca s co f
16
CHNG III
NNG LNG LIN KT HA HC
III.1. NNG LNG MNG LI ION Uion
Uion l nng lng cn thit ph v mt mol hp cht ion th rn

thnh cc ion t do trng thi kh, c bn. V d
LiF (r) Li+ (k,cb) + F- (k,cb)
ULiF =1008 kJ.mol-1
Nng lng mng li ion thng c tnh theo cng thc Born:
Z .Z .e 2 1 -1
U ion (1 )aN , J.mol
4 0 R nB
Trong 0 hng s in mi ca chn khng = 8,85.10-12 SI;
Z+, Z- l s in tch m ion dng v ion m mang, v d CaF2 th Z+ = 2 v Z-

=1
E l in tch ca e, e = -1,602.10-19 C
R: l khong cch ngn nht gia hai ion dng v ion m trong tinh th, m
N l s avogadro
A l hng s Madelung, gi tr ca n ph thuc vo kiu cu trc tinh th , v

d a i vi cu trc tinh th NaCl v CsCl ln lt bng 1,7475 v 1,763
NB h s y Born, gi tr ca nB ph thuc vo cu hnh e ca ion, vi

cc ion c cu hnh e ging He, Ne, Ar, Kr, Xe h s nB c gi tr ln lt l 5,
7, 9, 10, 12. Nu hai ion c cu hnh e khc nhau th ngi ta ly gi tr trung
bnh cng ca nB. Chng hn i vi LiF, ion Li+ c cu hnh ging He (nB = 5),
cn F- ging Ne (nB = 7) nn nB ca LiF l 1/2*(5+7) = 6
Kapustinxki nhn xt rng hng s Madelung i vi cc cht khc

nhau gn nh t l vi s ion trong phn t. ng cng ngh coi h s y
17
Born l nh nhau i vi tt c cc hp cht v coi khong cch R gia cc ion

trong tinh th bng tng s bn knh ca cation v anion c xc nh trong
tinh th c cu trc kiu NaCl. Phng trnh Kapustinxki c dng:
z .z . n
U ion C
r r
Trong n s ion trong mt phn t, v d CaF2 c n =3, NaCl c

n=2
C l hng s, gi tr ca n ph thuc vo n v dng, C = 1,08. 10-7 nu n v

ca r+ v r- l met, khi Uion c tnh bng n v l kJ.mol-1
Ta thy rng Uion cng ln khi s in tch ca ion dng v ion m, s

ion trong mt phn t cng ln, bn knh ca cation v anion cng nh
III.2. NNG LNG LIN KT CNG HA TR E cht
i vi phn t hai nguyn t th nng lng lin kt cng ha tr l nng

lng cn thit ph v lin kt gia hai nguyn t trong phn t trng thi kh,
c bn thnh cc nguyn t cng trng thi kh, c bn. N thng c tnh
cho mt mol lin kt. V d, nng lng lin kt H-H trong phn t H2 l ng
vi qu trnh sau:
H2 (k,cb) H (k,cb) + H (k,cb) , EH-H = 432 kJ/mol
i vi phn t nhiu nguyn t kiu ABn, ngi ta dng khi nim nng
lng lin kt trung bnh A-B, chng hn xt phn t CH4 , ph 4 lin kt C-
H:
CH4 (k,cb) C (k,cb) + 4H (k,cb) cn 1649 kJ
Trong mt mol CH4 c bn lin kt C-H, do nng lng lin kt trung

bnh C-H phi l:
EC-H = 1649/4 = 413 kJ/mol
Cn lu rng y mol l mol lin kt
18
S d c khi nim nng lng lin kt trung bnh v s ph v tng lin

kt mt trong ABn i hi cc nng lng khc nhau, nhng thc t cc nng
lng lin kt ny trong phn t u bng nhau. V d, trong phn t CH4 s
ph v lin tip tng lin kt C-H i hi cc nng lng ln lt l 427, 368,
519, 335 (kJ/mol)
Nu phn t nhiu nguyn t cha s nguyn t khc nhau ln hn hai th

kha nim nng lng lin kt trung bnh khng ph hp na. Chng hn i vi
phn t C2H6
C2H6 (k,cb) 2C (k) + 6H (k,cb), nng lng ca phn ng ny bng

EC-C + 6 EC-H
Nng lng lin kt ph thuc vo bc lin kt ( bi lin kt) v xen

ph cc obitan ha tr. Bc lin kt v xen ph cc obitan ha tr cng ln th
lin kt cng bn, ngha l nng lng lin kt cng ln
III.3. NNG LNG LIN KT KIM LOI
Lin kt trong kim loi c gi l lin kt kim loi. L thuyt hin i

gii thch lin kt kim loi l thuyt vng. N da trn phng php obitan phn
t -t hp tuyn tnh cc obitan nguyn t
Nng lng lin kt kim loi c th c trng bng entanpi nguyn t ha

kim loi Ha. N ng vi qu trnh sau:
Kim loi rn cc nguyn t kim loi kh, Ha > 0
- Ha ca hu ht cc kim loi u ln v ln nht l ca W (Ha = 837

kJ.mol-1), b nht l ca Hg (Ha = 61 kJ.mol-1)
- Nng lng lin kt kim loi ca cc kim loi chuyn tip d ni chung ln
hn so vi cc kim loi khng chuyn tip, c l l do cc kim loi
chuyn tip d c cc obitan ha tr (n-1)d tham gia lin kt kim loi
- T tri sang phi trong dy cc kim loi chuyn tip d nng lng lin kt
kim loi tng theo s e ha tr (n-1)d trong nguyn t v t gi tr cc i
19
khong gia dy, khi m s e ha tr bng hoc gn bng s obital ha

tr c th tham gia lin kt kim loi
Khi s e ha tr vt qu s obital ha tr th ni chung quan st thy Ha

gim dn. Nguyn nhn chnh ca s bin thin ny c th l do s tng s e
trn obital phn t lin kt cng vi s tng s e ha tr (n-1)d trong nguyn
t kim loi lm cho Ha tng, nhng khi s e trn cc obital phn t lin kt
y th s tng s e ha tr (n-1)d trong nguyn t kim loi s dn n s
in cc e vo cc obital phn t phn lin kt lm cho Ha li gim
- T trn xung trong nhm A nng lng lin kt kim loi gim v trong
nhm B nng lng ny tng, tr mt s t trng hp c s sai khc ny
nh nhm IIB, nng lng lin kt kim loi gim dn t trn xung, iu
ny lin quan n cu hnh bn ca phn lp e bo ha (n-1)d10 v hiu Ens
E(n-1)d ln lm cho cc e (n-1)d hu nh khng tham gia lin kt kim loi
cng vi cc e ns2, trong khi cc e ns2 tham gia lin kt kim loi gim dn
t trn xung. Cng v l do ny m Ha ca ba kim loi nhm IIB l cc
tiu so vi cc kim loi khc trong cng chu k
III.4. NNG LNG SONVAT HA ION
Nng lng sonvat ha ion l nng lng ta ra khi mt mol ion th kh

tan vo dung mi to thnh dung dch long v cng, nu dung mi l nc,
nng lng ny c gi l nng lng hidrat ha ion. V d:
Na+ (k) + H2O (l) Na+ trong dung dch
C G298 = - 405,84 kJ/mol
Nng lng sonvat ha ion thng c tnh theo phng trnh Born:
Z 2 .e 2 N 1
G s H s TS s k 1
2r
Trong Gs s bin thin th ng p s sonvat ha cation hay anion (cn

c gi l nng lng sonvat ha ion) vi s in tch dng hay m ca
cation hay anion l Z+ hay Z- v bn knh ca cation hay anion l r+ hay r-
20
Hs nhit sonvat ha ion
Ss s bin thin entropi sonvat ha ion
hng s in mi ca dung mi
k: hng s ph thuc n v dng
t cng thc trn ta thy Gs cng nh (cng m), ngha l kh nng sonvat ha
ion cng ln khi s in tch ca ion cng ln, bn knh ion cng nh v hng s
in mi ca dung mi cng ln
III.5. NNG LNG LIN KT YU
III.5.1. Nng lng lin kt hidro
Nguyn t hidro khi lin kt vi nguyn t ca nguyn t c m

in ln (F, O, N), n cn c kh nng lin kt ph vi nguyn t khc trong
phn t hay trong phn t khc cng c in m ln. Lin kt ph c
gi l lin kt hidro (thng c biu din bng nhng du chm). V d lin
kt hidro gia cc phn t HF nh sau:
....F H...F H ...F H ....
Nng lng lin kt hidro ph thuc ch yu vo m in ca nguyn

t lin kt vi n. m in cng ln, nng lng lin kt hidro cng ln. Tuy
nhin nng lng ny nh hn nhiu so vi nng lng lin kt cng ha tr v
ion v n c gi tr khong 4 - 40kJ/mol. Nng lng lin kt hidro ln nht l F-
...HF, gn bng 113 kJ/mol
III.5.2. Nng lng tng tc vander Waals
y l tng tc gia cc phn t. khong cch ln gia cc phn t,

khi m cc v e cha xen ph nhau, gia cc phn t ch c tng tc ht v
c chia thnh ba loi, l cc tng tc nh hng, cm ng v khuch tn
Tng tc nh hng l tng tc gia cc phn t c momen lng cc

khc s khng, n cng ln khi momen lng cc ca phn t cng ln v gim
21
khi nhit tng v chuyn ng nhit ph v s nh hng gia cc phn t.

Nng lng tng tc ny c tnh bng cng thc sau:
2 4 1
U h .
3kTR (4 0 ) 2
6
Trong - momen lng cc ca phn t, C.m;
k- hng s Boltzman, k = 1,3805.10-23 J.K-1
T nhit tuyt i, K
R khong cch gia hai phn t, m
0 :Hng s in mi ca chn khng, 0 = 8,85.10-12SI
Nu phn t c =0 th gia cc phn t ny khng c tng tc nh hng
Khi cc phn t phn cc tng tc nh hng vi nhau s lm bin dng phn

t v dn n s tng tc b sung, c gi l tng tc cm ng m nng
lng ca n c tnh bng cng thc sau:
2 2 1
U cu .
R 6
(4 0 ) 2
phn cc ( bin dng) ca phn t
Hai loi tng tc trn cha gii thch c hin tng ha lng v ha rn ca
cc cht gm nhng phn t khng phn cc, nh cc kh him, hidro, kh
cacbonic, metan... ngha l gia cc phn t ny cng phi tn ti tng tc,
l tng tc khuch tn. Tng tc ny xut hin l do s chuyn ng khng
ngng ca cc e trong phn t, gy nn s bt i xng tm thi v s phn b
in tch dng v m trong phn t, to nn momen lng cc tm thi v do
xut hin tng tc gia chng. Nh vy tng tc ny cng phi th hin
gia cc phn t phn cc. Nng lng tng tc khuch tn c tnh gn ng
theo phng trnh :
3h 0 2 1
U kt .
4R 6
(4 0 ) 2
22
Trong h-hng s Planck, h = 6,626.10-34 J.s
0 : Tn s dao ng ng vi nng lng khng, ngha l nng lng nhit

T = 0K, thc t h0 gn bng nng lng ion ha I1 ca phn t
Nng lng tng tc vander Waals cng nh nng lng lin kt hidro
l rt nh so vi nng lng lin kt cng ha tr v ion, nn chng nh hng
rt t n tnh cht ha hc m ch yu l nh hng n tnh cht l hc ca cc
cht
23
CHNG IV
CHIU MT S PHN NG HA HC V C
C th chia cc phn ng ha hc ra lm hai loi: phn ng c s bin i

s oxi ha v phn ng khng c s bin i s oxi ha ca cc nguyn t.
Trong phm vi chng ny ta ch xt chiu phn ng oxi ha kh xy ra trong
dung dch nc v phn ng trao i ion trong dung dch nc
IV.1. MT S KHI NIM
IV.1.1. Cht in li mnh v yu
Nhng cht khi ha tan trong nc, phn t ca chng phn li nhiu hay t
ra ion c gi l nhng cht in li. Kh nng phn li ca cc cht in li khc
nhau l khng ging nhau v c nh gi bng in li
= s mol phn li ra ion/s mol ha tan
Kh nng phn li ra ion ca cht in li cn ph thuc vo nng , nng

cng nh in li cng ln, ngha l cng gn tin ti 1. Trong chng
ny chng ta ch xt dung dch long, nn c th coi cht in li mnh l cht c
=1, ngha l 100% phn t ha tan trong nc in li ra ion, cn cht in li
yu c <1, ngha l ch mt phn cc phn t ha tan phn li thnh ion, cn
phn ln chng vn dng phn t. Phng trnh phn li ca cht in li mnh
c vit mt mi tn, cn phng trnh phn li ca cht in li yu vit hai mi
tn tri chiu nhau gia phn t v cc ion do n phn li ra. V d, phng
trnh phn li cht in li mnh HCl v cht in li yu CH3COOH c vit:
HCl Cl- + H+
CH3COOH CH3COO- + H+
Vy s phn li cht in li yu l qu trinh thun nghch, ngha l n tun

theo mi nh lut ca cn bng ha hc v s chuyn dch cn bng
24
V mt phng din no ngi ta c th chia cc cht in li thnh

cht in li mnh, cht in li kh mnh, cht in li trung bnh, cht in li yu
v cht in li rt yu
IV.1.2. Phng trnh ion ca phn ng xy ra trong dung dch nc
Xt v d phn ng sau:
BaCl2 + Na2SO4 BaSO4 + 2NaCl
Trong phn ng ny BaCl2 , Na2SO4 , NaCl l cc cht d tan v in li

mnh, nn trong dung dch chng phn li hon ton ra cc ion:
Ba2+ + 2Cl- + 2Na+ + SO42- BaSO4 + 2Na+ + 2Cl-
T ta thy thc cht phn ng ny ch l:
Ba2+ + SO42- BaSO4
iu c ngha l to kt ta BaSO4 ch cn trn hai dung dch, mt

dung dch c cha cc ion Ba2+, cn dung dch kia c cha cc ion SO42-
y l phng trnh ion ca phn ng xt
vit phng trnh ion ca phn ng ngi ta quy c nh sau: cn c

vo phng trnh phn ng y di dng phn t chuyn tt c nhng cht
va d tan, va in li mnh hoc kh mnh ra ion, nhng cht cn li
nguyn di dng phn t, sau n gin nhng ion ging nhau hai v ca
phng trnh phn ng. Phng trnh rt gn c gi l phng trnh ion ca
phn ng
IV.1.3. Ha tr v s oxi ha ca nguyn t
Ha tr ca nguyn t l s cp e lin kt m mt nguyn t nguyn t

lin kt trc tip vi cc nguyn t xung quanh n trong phn t. V d, ha tr
ca nito, oxi v hidro trong cc phn t N2, NH3, H2O ln lt l 3, 2, 1
S oxi ha ca nguyn t c gi tr i s khc vi ha tr, v d s oxi

ha ca nito trong N2 l s 0, cn trong NH3 l III
25
Phng php xc nh s oxi ha ca cc nguyn t nh sau:
+ i vi hp cht ion, s oxi ha ca nguyn t bng in tch m mt

ion nguyn t mang
+ i vi cc cht c lin kt cng ha tr, s oxi ha ca nguyn t l

in tch c ion nu gi thit rng cc cp e dng chung to lin kt c
chuyn hn sang nguyn t c m in ln hn
Trong trng hp khng bit cng thc cu to phn t, ngi ta xc nh s oxi

ha ca nguyn t da vo cc quy tc sau:
- S oxi ha ca nguyn t trong n cht bng 0
- Trong hp cht, s oxi ha ca cc nguyn t sau lun lun khng i:

cc kim loi kim c s oxi ha +I, cc kim loi nhm IIA l +II, nhm +III, flo
I;
- S oxi ha ca hidro trong hu ht cc hp cht l +I
- S oxi ha ca oxi trong hu ht cc hp cht l II, tr hp cht vi flo
- Tng i s s oxi ha ca cc nguyn t trong phn t bng 0, ngha l

phn t trung ha v in, cn tng i s ny trong mt ion nhiu nguyn t
bng in tch ion mang
IV.2. PHNG PHP CN BNG PHNG TRNH PHN NG OXI

HA KH
cn bng phng trnh phn ng oxi ha kh ngi ta c th dng

nhiu phng php. Tuy nhin i vi phn ng oxi ha kh xy ra trong dung
dch nc ch c phng php ion-electron mi cho php tnh c th kh ca
cc cp oxi ha-kh ph thuc vo nng v mi trng. V d xt phn ng
sau:
H3AsO4 + 2I- +2H+ H3AsO3 + I2 + H2O
Trong mi trng axit iu kin chun: nng cc phn t v ion

trong phn ng u bng 1 mol v 250C phn ng i theo chiu thun v:
26
H0 AsO / H AsO 0,56V I0 / I 0,54V

3 4 3 3

2
Nhng nu ta ch gim nng H+ trong phn ng xung, v d [H+]=10-2

M th th kh ca cp I2/I- khng bin i, trong khi th kh ca cp H3AsO4/
H3AsO3 bin i theo nng H+
H3AsO4 + 2e +2H+ H3AsO3 + H2O
Theo cng thc Nernst 250C ta c
0, 059 [H 3 AsO4 ][H ]2

H AsO / H AsO H0 AsO / H AsO lg
3 4 3 3 3 4 3 3
2 [H 3 AsO3 ]
0, 059
V ch nng H+ bin i nn 0,56 lg102 0.442V
2
By gi ta c H AsO / H AsO 0, 442V I0 / I 0,54V nn phn ng i theo

3 4 3 3 2

chiu nghch
Nh vy ch c cn bng qu trnh trao i e theo phng php ion

electron nh lm mi tnh c th kh bin i theo cng thc Nernst
cn bng phng trnh phn ng oxi ha kh xy ra trong dung dch

nc theo phng php ion-electron trc ht cn vit ng nhng ion tn ti
trong dung dch nc, v d khi K2Cr2O7 tan trong nc ta phi vit l 2K+ +
Cr2O72-; nhng cht in li yu, kt ta, bay hi trong phng trnh phn ng
c gi nguyn di dng phn t
Cn bng mt phng trnh phn ng oxi ha kh xy ra trong dung dch nc

gm 6 bc :
1- xc nh nhng nguyn t c s oxi ha bin i trc v sau phn ng
2- vit qu trnh oxi ha v qu trnh kh trong phn ng mt cch ring

bit km theo s e trao i ca tng cp oxi ha v kh
3- cn bng in tch ca tng qu trnh qu trnh oxi ha v qu trnh kh
4- cn bng s nguyn t ca tng qu trnh
27
5- cn bng s e trao i gia cht kh v cht oxi ha hai qu trnh
6- cng hai qu trnh li ta thu c phng trnh ion ca phn ng oxi

ha kh
T phng trnh ion d dng chuyn sang phng trnh di dng phn t
IV.3. CHIU V GII HN CA PHN NG OXI HA KH XY RA

TRONG DUNG DCH NC
xt chiu ca phn ng oxi ha kh trong dung dch nc ngi ta

thng dng cng thc sau:
G = - nFE
Nu phn ng iu kin chun th
G0 = - nFE
G0 lin h vi hng s cn bng K ca phn ng thun nghch bng

phng trnh G0 = - RTlnKp
T RTlnKp = nFE RTlnKp/F = nE0
250C cng thc trn tr thnh
lgKp = nE0/0,059
vy hng s cn bng K l i lng c trng cho gii hn ca phn ng

thun nghch
lu rng phn ng c n= 0 th c hng s Kp = Kc = Kn = KN
IV.4. GIN TH KH V NG DNG CA N
Nu vit tt c cc phn t v ion ca mt nguyn t c s oxi ha khc

nhau theo chiu s oxi ha gim dn km theo th kh ca tng cp, ta c
gin c gi l gin th kh ca nguyn t
28
VD: gin th kh chun ca mangan
+VII +VI +IV

0=0,56V 0
=2,26V 0=0,95V 0=1,51V 0=-1,18V
2- 3+
MnO4 MnO4 MnO2(r) Mn Mn2+ Mn
T gin ny ta c th bit c phn t hay ion khng bn v phng

din nhit ng trong dung dch. Ion hay phn t khng bn v tr trong gin
m th kh trc n b hn th kh sau n. Vy ion MnO42- v ion Mn3+
khng bn, chng s phn hy thnh ion v phn t ng trc v sau chng:
3MnO42- + 4H+ 2MnO4- + MnO2 (r) + 2H2O
2Mn3+ + 2H2O MnO2 + Mn2+ + 4H+
Tnh cht ny c thy r khi so snh th kh ca cc cp tng ng:
MnO
0

/ MnO42
0,56V MnO
0

/ MnO
2, 26V
4 4 2
V MnO
0
/ Mn
0,95V Mn
2
3
0
3
/ Mn 2
1,51V
ng dng th hai ca gin th kh l tnh th kh ca cp cha bit

th kh. Chng hn tnh th kh ca cp MnO2-/MnO2:
G0
MnO4- MnO2
G20
G10
MnO42-
G0 = G01 + G02 - nF0 = - n1F01 - n2F02
n1 01 n 2 0 2 0,56 2* 2, 26
0 1, 69
n 3
MnO
0

/ MnO2
1, 69V
4
Da vo gin th kh ta cn c th d on c sn phm phn ng.
29
V d, xt phn ng:
MnO4- + Tl+ + H+ ???
Nu da vo th kh ca cc cp:
MnO
0
2 1,51V Tl0 3 /Tl 1, 25V
4 / Mn
Th ta c th ni rng sn phm phn ng l Mn2+ v Tl3+, nhng thc t l

MnO2 v Tl3+. iu ny c th gii thch da vo gin th kh ca mangan
v tali khi loi b nhng phn t v ion khng bn
0=1,25V 0=-0,34V
Tl3+ Tl+ Tl
0=1,69V 0=1,23V 0=-1,18V

MnO4- MnO2 Mn2+ Mn
T gin th kh ca mangan ta thy rng trn ng t MnO4- n

Mn2+ c MnO2; Tl+ c th kh MnO4- n MnO2 v
+ 2+
MnO
0

/ MnO2
1, 69V Tl0 3 /Tl 1, 25V , nhng Tl khng th kh MnO2 n Mn v
4
MnO
0
/ Mn
1, 23V Tl0
2 3
/ Tl
1, 25V
2
Vy sn phm ca phn ng l MnO2 v Tl3+
2MnO4- + 3Tl+ + 8H+ 2MnO2 (r) + 3Tl3+ + 4H2O
Cn lu rng th kh ch cho bit c chiu ca phn ng, nhng khng bit

c tc ca n.
IV.5. MI LIN H GIA TH KH V NNG LNG LIN KT
Xt cp oxi ha kh Mn+/M. Mn+ l ion kim loi, n c to thnh trong

dung dch nc t kim loi M nh sau:
M(r) - ne (trong kim loi rn) +aq Mn+.aq
Th kh ca cp Mn+/M ng vi s bin thin th ng p ca qu trnh:

30
Mn+.aq + ne (trong kim loi rn) M(r) + aq
Ta c th phn tch qu trnh ny thnh cc giai on trung gian nh sau:
Mn+ .aq + ne (trong kim loi rn) M(r) + aq
Mn+ (k) + aq + ne (k) M(k) + aq
G0 = -(G0h + G01 + G0a ) + G0e
Mt khc
G0 = - nF0Mn+/M
G 0 h G 01 G 0 a Ge0
T ta c M0 n
/M

nF nF
Trong G0h l s bin thin th ng p chun hidrat ha ion Mn+
G01 l s bin thin th ng p chun ion ha nguyn t M
G0a l s bin thin th ng p chun nguyn t ha kim loi M(r)
G0e l s bin thin th ng p chun khi chuyn n electron trong kim loi rn
thnh n electron th kh
M0 n
/M
th kh chun tuyt i ca cp Mn+.aq/M(r)
Ta c th lm tng t i vi mi cp oxi ha kh, chng hn xt cp

H+.aq/H2(k) ta c:
G 0 h G 01 G 0 a Ge0
H0
/ H2

nF nF
i vi hidro G0a ng vi qu trnh sau:
H2 (k) H(k) + H (k)
Thay cc gi tr G0 250C ta c
Ge0
0
H / H2
4, 44
nF
31
G0e i vi hidro cng nh i vi cc cp oxi ha kh khc khng xc nh

c nn khng th tnh c th kh chun tuyt i 0. Do ngi ta phi
dng th kh chun so snh vi quy c ly cp H+/H2 lm chun v tha nhn
G0e /n i vi mi cp oxi ha kh u bng nhau
Th kh chun so snh ca cp Mn+/M c nh ngha nh sau:
M0 n
/M
M0 n / M H0 / H
2
G 0 h G 01 G 0 a
250C c M0 n
/M
4, 44
nF
V khng c th kh chun tuyt i, nn th kh chun so snh c gi l th

kh chun
IV.6. CHIU PHN NG KHNG I S OXI HA TRONG DUNG

DCH CHT IN LI
Chiu ca phn ng loi ny l chiu lm gim nng ion trong dung

dch. Mun vy phn ng to thnh t nht mt trong cc cht sau: cht kt ta ,
cht in li yu hoc bay hi
Phn ng to cht kt ta. Xt phn ng sau:
Pb(NO3)2 + 2KI PbI2 + 2KNO3
Bn cht ca phn ng ny l
Pb2+ + 2I- PbI2
Thc ra phn ng trn l thun nghch, nhng chiu nghch l khng

ng k v ha tan ca PbI2 rt b, nn c th coi phn ng trn l hon ton.
phn ng xy ra phi c iu kin:

G RT ln 0 ngha l < K
K
32
Hoc
1 1
( 2 2
)bd ( )cb
[Pb ][I ] [Pb ][I 2 ]2
2
[Pb 2 ]bd [I ]2 bd [Pb 2 ]cb [I ]2 cb

[Pb 2 ]bd [I ]2 bd Tt PbI 2
y bd: ban u; cb: cn bng; Tt: tch s tan
tch s tan cng nh phn ng xy ra cng hon ton
Phn ng to cht in li yu. Gi thit c phn ng:
CH3COONa + HCl CH3COOH + NaCl
Phng trnh ion l:
CH3COO- + H+ CH3COOH
Phn ng c G < 0 kh < K, ngha l
[CH 3COOH ] [CH 3COOH ]

(
)bd ( )cb
[CH 3COO ][H ] [CH 3COO ][H ]
a > Ka
Ka l hng s in li axit. Ka cng b, cn bng cng dch chuyn theo

chiu thun. Nc c hng s in li rt nh, nn cc phn ng to thnh nc
loi ny thng rt d xy ra, v d cc phn ng trung ha
Phn ng to cht bay hi. Phn ng ny c S > 0, thun li cho phn

ng. Ngoi ra sn phm bay ra khi mi trng phn ng ngn tr phn ng
nghch, to iu kin thun li cho phn ng thun xy ra hon ton. V d cc
mui cacbonat rt d tan trong cc axit, mc d a s chng rt t tan trong
nc, v phn ng ny to cht bay hiCO2, ngoi ra cn to cht in li yu l
H2O, v d:
BaCO3 + 2H+ Ba2+ + CO2 + H2O
33
CHNG V
MT S TNH CHT L HC CHUNG CA CC CHT
V.1. S HA TAN
S ha tan l qu trnh ph v cc lin kt trong cht ha tan (k hiu l t)

v trong dung mi (k hiu l dm) to lin kt gia cc phn t cht tan v
dung mi. Qu trnh ny c th minh ha bng s sau:
t - t + dm dm t dm
s ha tan ch xy ra khi:
Ght = Hht - TSht < 0
Trong Hht = (Et-t + Edm-dm) - Et-dm ;
Sht = Sdd - (St + Sdm )
Cc k hiu: ht- ha tan; dd: dung dch
Hin nay cha c thuyt no d on c chnh xc s ha tan ca cc

cht, ngi ta ch c th a ra c nhng nhn xt nh tnh nh sau: cc cht
tng t nhau v phn cc v kch thc phn t thng d tan trong nhau v
khi Hht gn nh bng s khng, cn khi trn ln cc nguyn cht entropi
tng (Sht > 0)
C th thng gp cc trng hp sau:
- Cht lng gm cc phn t khng phn cc (momen lng cc phn t

=0) hay phn cc nh d ha tan cc cht gm cc phn t khng phn cc
hay phn cc nh v lin kt vander Waals gia cc phn t loi ny (t-t, dm-
dm, t-dm) khc nhau t. V d benzen =0D v toluen =4D tan ln trong nhau
theo t l bt k. Benzen d ha tan cc halogen = 0
34
- Cht lng gm cc phn t phn cc ln d ha tan cc cht cng cu

to t cc phn t phn cc ln. V d, kh HCl ( = 1,03D) d tan trong nc
( = 1,84D). 00C mt lt nc ha tan khong 500 lit kh HCl
Ngoi ra nu cht ha tan v dung mi u c lin kt hidro th cng hnh

thnh lin kt hidro gia cht tan v dung mi, trong nhng trng hp ny
ha tan s tng ln nhiu, c trng hp chng tan trong nhau theo t l bt k.
V d, 00C mt lt nc (c lin kt hidro) c th ha tan ti 1200lit NH3 (
=1,5D v c lin kt hidro). Cc axit HF, H2SO4, HNO3 tan trong nc theo cc
t l bt k
- Nu lin kt trong cht tan hay trong dung mi ln hn nhiu so vi lin

kt gia cht tan v dung mi th s ha tan thng c Hht >> 0 v cc gi tr
ny thng ln hn TSht , do trng hp ny rt kh tan. V d cc hp cht
ion (nng lng lin kt ln) khng tan trong benzen. Metan khng tan trong
nc (nng lng lin kt H2O-H2O ln hn nhiu so vi nng lng H2O-CH4)
V.2. NHIT NNG CHY V SI CA CC CHT
V.2.1. Nhit nng chy
Nhit nng chy ca mt cht rn tinh th l nhit tn ti cn

bng gia trng thi rn v trng thi lng ca cht :
R L
Bc t do ca h cn bng ny l:
C=K - +2 =1- 2 +2 =1
Nh vy nhit nng chy ca cht rn tinh th (cht nguyn cht) ch

ph thuc vo mt thng s l p sut ca mi trng bn ngoi. Ni cch khc,
mi cht tinh th c nhit nng chy xc nh nu p sut bn ngoi l xc
nh
trng thi cn bng nng chy ta c:
Gnc = Hnc - TncSnc = 0
35
H nc
Tnc
S nc
S khc nhau v gi tr Hnc ca cc cht khc nhau ln hn nhiu so vi

s khc nhau v gi tr Snc, nn Tnc ca cc cht ph thuc ch yu vo Hnc.
Ni chung nhng cht m nng lng lin kt trong cht cng ln th c nhit
nng chy cng cao.
V.2.2. Nhit si
Nhit si ca cht lng l nhit p sut hi ca n bng p sut

mi trng bn ngoi trn mt cht lng, khi c cn bng gia trng thi
lng v hi
L H
Bc t do ca h cn bng ny l:
C=12+2=1
Vy nhit si ca cht lng nguyn cht l xc xc nh nu p sut

bn ngoi l xc nh
nhit si ta c:
Gbh = Hbh - TsSbh = 0
H bh
Ts
Sbh
Sbh nhit si ca a s cc cht lng gn nhau v bng khong

90 J. K-1.mol-1 ,nn nhit si ca cc cht khc nhau ph thuc ch yu vo
Hbh.
V.2.3. Nhn xt v nhit nng chy v nhit si ca cc cht
V mt nh tnh ta c th a ra mt s nhn xt v nhit nng chy

v si ca cc cht nh sau:
36
- Cc kim loi chuyn tip ni chung c nhit nng chy v si cao

hn cc kim loi khng chuyn tip, v nng lng lin kt trong kim loi
chuyn tip ln hn trong kim loi khng chuyn tip
- Trong cc phi kim nh kim cng v graphit cc nguyn t cacbon lin

kt vi nhau bng lin kt cng ha tr rt bn, khi nng chy hay si cc lin
kt ny b ph nn chng c nhit nng chy v si cao
- Cc kh him hay phi kim cu to t cc nguyn t hay phn t Xn khi

nng chy hay si ch cc lin kt vander Waals gia cc phn t b ph, nn
chng c nhit si v nhit nng chy thp v tng dn theo kch thc v
khi lng phn t. V d nhit nng chy v si ca XH4 tng dn t trn
xung trong nhm.
- Hp cht cng ha tr c nhit nng chy v si thp, v khi nng

chy hay si ch lin kt vander Waals b ph. Nng lng lin kt vander Waals
tng theo phn cc, kch thc v khi lng phn t, nn nhit nng
chy v si tng theo. Nu trong cht c lin kt hidro th nhit nng chy v
si s cao hn bnh thng
- Hp cht ion c nhit nng chy v si cao, v nng lng lin kt

trong tinh th ion rt ln. Thng quan st thy nhit nng chy v si ca
cc hp cht ion tng theo nng lng mng li ion.
V.3. TNH DN IN CA KIM LOI, THUYT VNG
V.3.1. Thuyt vng
Trong tinh th kim loi ch c mt loi nguyn t, nn khng th tn ti

lin kt ion. Mi nguyn t kim loi trong tinh th thng c bao quanh bi
tm hoc mi hai nguyn t gn nhau nht, s ny l qu ln c th to
thnh lin kt cng ha tr thng thng bng cch dng chung cc cp electron
ha tr. Do lin kt trong tinh th kim loi l lin kt kim loi. Thuyt hin
i gii thch lin kt kim loi l thuyt vng. N da trn c s ca phng
php MO-LCAO (phng php obitan phn t)
37
Theo thuyt ny th c n AO ca cc nguyn t t hp vi nhau s to

thnh n MO, trong cc MO lin kt c nng lng thp v cc MO phn lin
kt c nng lng cao hn cc AO t hp. Vy s AO tham gia t hp cng
nhiu th s MO to thnh cng ln
Trong trng hp nh tinh th liti kim loi c cu trc lp phng tm

khi vi s phi tr l tm c th coi rng 2s ca mi nguyn t liti vi mt e
ha tr c nht xen ph vi tm AO tng ng ca tm nguyn t bao quanh
v mi nguyn t bao quanh ny li dng AO ha tr 2s ca mnh xen ph vi
cc nguyn t ln cn khc ... nh vy s AO tham gia t hp rt ln v to
thnh rt nhiu MO. Cc MO ny hnh thnh nhng vng nng lng. C th c
hai trng hp sau:
- Mt s MO c nng lng thp v cch xa cc MO khc c nng lng

cao th gia hai vng ny tn ti mt vng gi l vng cm vi khong cch
nng lng gia hai vng MO ny l E
- Nu nng lng cc MO gn nhau th khng c vng cm
Da vo thuyt vng c th gii thch c tnh dn in, cch in v

bn dn ca kim loi v mt s cht rn khc
V.3.2. Gii thch tnh dn in, cch in v bn dn
Tnh dn in ca kim loi l do s di chuyn ca cc e ha tr qua mng

li kim loi theo mt hng xc nh di tc dng ca mt s hiu s in th
ca dng in t vo
Cc kim loi dn in tt v cc e t cc MO b chim c nng lng cao

(vng ha tr) d chuyn ln cc MO trng c nng lng cao hn (vng dn)
di tc dng ca dng in v tham gia dn in. iu ny c ngha l trong
kim loi gia vng ha tr v vng dn khng c vng cm
Cht cch in l cht di tc dng ca dng in cc e trn cc MO b

chim khng th chuyn ln cc MO trng c nng lng cao hn tham gia
dn in, ngha l gia vng ha tr v vng dn c vng cm vi E > 3eV. V
d trong kim cng E = 5,7 eV
38
Trong cht bn dn gia vng ha tr v vng dn c E = 0,1 3 eV.

Khi c kch thch khng ln cc e trn cc MO b chim c th chuyn ln cc
MO c nng lng cao hn tham gia dn in.
dn in ca kim loi ph thuc vo s e tham gia dn in trong mt

n v th tch v trong mt n v thi gian v s e ny c gi l s e hiu
dng
dn in ca hu ht cc kim loi gim xung khi nhit tng, v s

chuyn ng nhit ca cc nguyn t v cc e trong mng tinh th ngn tr s
chuyn ng c hng ca cc e
Tri li i vi a s cht bn dn v cch in, dn in tng theo

nhit v nng lng nhit cng ln cng kch thch s e trn cc MO vng
ha tr ln cc MO vng dn
V.4. TNH CHT T CA CC CHT
Hin nay chng ta bit mt s tnh cht t khc nhau ca cc cht,

nhng ph bin hn c l tnh nghch t v thun t
Cht nghch t l cht cho cc ng lc t i qua kh hn trong chn

khng, b t trng ngoi y
Cht thun t cho cc ng lc t i qua d hn trong chn khng, b t

trng ngoi ht
Nguyn nhn s khc nhau v cc tnh cht ny ca cc cht l do e. S

chuyn ng ring ca e to nn momen t spin, cn s chuyn ng ca e xung
quanh ht nhn to nn momen t obitan. Momen t ca mt cht l s t hp
ca hai loi momen t ny. Nu t trng ca cc e c b tr ln nhau th
momen t tng cng bng khng v cht l nghch t. Nu t trng ca cc
e khng c b tr ln nhau th cht s c momen t ring v n l cht
thun t
Cht nghch t l cht c cha nguyn t, ion hay phn t c cc e u

ghp i. V d cc cht kh nh He, H2, CO2 cc cht lng nh nc, benzen,
ru, cc cht rn nh NaCl, C, S, polietilen...
39
Cht nghch t cha nguyn t, ion hay phn t c e c thn, v d, hidro

nguyn t, O2, CO2 , nhiu hp cht ca cc kim loi chuyn tip...
Ngi ta thy rng nhiu cht nh a s cc cht ca cc kim loi chuyn

tip nh, c momen t c xc nh gn ng ch bng momen t spin v c
tnh bng cng thc:
n(n 1) , B
Trong l momen t ca cht c n v l manhetong Bo (B)
n: s e c thn trong nguyn t , ion hay phn t trong cht kho st
momen t c th xc nh bng thc nghim, t c th tnh c s e c

thn trong nguyn t, ion hay phn t trong cht
C nhng cht gm cc nguyn t hay ion thun t rt gn nhau tc

dng hp lc vi nhau th quan st thy nhng dng t tnh phc tp hn v
mnh hn, c bit l hin tng st t v phn st t, tuy nhin cc tnh cht t
ny khng cho nhng h qu ha hc trc tip nn ta khng xt y
40
CHNG VI. HYDRO
VI.1. CU TO NGUYN T
Nguyn t hydro c cu trc n gin nht (1s1), gm mt electron v

mt ht nhn mang in tch +1 gi l proton.
Hydro c 3 ng v:
ng v 1
1 H (H) 2
1 H (D) 3
1 H (T)
Hm lng (%) 99.984 0.016 0.0001
H v D l 2 ng v bn, T l ng v phng x.
Do c cu trc c bit nn H c 3 kh nng:
+ Mt electron ha tr bin thnh ion H+:
H - e H+ H = 313,5 kcal/ntg
Kh nng ny th H ging kim loi kim nhng nng lng ion ha ca H

ln gp vi ba ln kim loi kim. Proton c kch thc ( 1,5.10-13) b hn nhiu
so vi nguyn t (10-8cm) v mang in tch nn c kh nng lm nhiu lon
m my electron ca cc nguyn t xung quanh. V th, khc vi ion kim loi
kim, proton khng th tn ti mt mnh m lun kt hp vi phn t hay
nguyn t khc.
Chng hn: H+ + H2O H3O+
+ Kt hp vi electron bin thnh ion H- c cu trc ca He (1s2)
H + e H- H = - 16 kcal/ntg
Ion H- t do c kh nng tn ti trong cc hydrua mui nh KH, CaH2. V

kh nng ny, H ging nh halogen, nhng i lc i vi electron ch bng 1/5
i lc electron ca halogen.
41
+ To nn cp electron chung cho lin kt cng ha tr. Lin kt ny c th

khng phn cc nh trong phn t H2, hoc c cc nh trong phn t HCl.
Do c cc kh nng nh trn nn H c mt v tr c bit trong Bng

HTTH, n va ging, va khc vi kim loi kim v halogen. Nu phi xp H
vo mt trong 2 nhm th xp vo nhm halogen hp l hn.
Do bn cht ca proton v do khng c lp electron no chn in tch ht

nhn, H c nhng c im m nhng nguyn t khc khng c c nh to
lin kt hydro, cu hydro v cc hp cht khng hp thc vi kim loi.
VI.2. TNH CHT L HC
+ Dng tn ti bnh thng trng thi t do l phn t H2. Nng lng

lin kt H H l 103Kcal/ptg, di lin kt l 0,74 A0. Phn t H2 c bn
ln, kh b phn cc ha, nhit nng chy v nhit si rt thp.
+ Kh H2 khng mu, khng mi v khng v; n nh nht trong tt cc

cc kh nn n c tc khuch tn ln (3,5 ln so vi khng kh). Do H2 c
dn nhit ln, dng lm ngui rt tt. Mt khc v rt nh nn trc y H2
thng c dng bm vo cc kh cu.
VI.3. TNH CHT HA HC
Nguyn t hidro c c nht 1 e 1s1 , nn n ch c th to c mt

lin kt trong phn t. Khi hidro lin kt vi nguyn t c m in ln hn,
v d cc phi kim th n c s oxi ha +I, cn khi lin kt vi nguyn t c
m in b hn v d cc kim loi th n th hin s oxi ha I. Nh vy hidro
va th hin tnh kh ( H2 2 e 2H+) va th hin tnh oxi ha (H2 + 2 e
2H- ) ty theo cht phn ng vi n. Tuy nhin tnh kh ca hidro c trng hn
V hidro vi s oxi ha bng 0 va c th chuyn thnh s oxi ha +I

ging kim loi kim, va c th chuyn thnh s oxi ha I ging halogen khi
tham gia phn ng, nn hidro thng c xp vo nhm kim loi kim hoc
nhm halogen
* Tnh bn nhit ca hidro:
42
+ Phn t H2 c bn ln nn kh phn hy thnh nguyn t. N ch bt

u phn hy thnh nguyn t nhit khong 20000K:
H2 (k) 2H (k) H2980 = 432 kJ
p sut 1 atm v 2000K s phn hy t khong 0,1 % cn 5000K l 95%
V th nhit thng H2 rt km hot ng. Ch khi un nng n mi kt

hp vi nhiu nguyn t.
* Tnh oxi ha ca hidro:
- khi cho mt dng kh hidro i qua kim loi kim hoc kim th nhit
cao s thu c hydrua kim loi:
H2 + Na NaH (t = 4000C)
H2 + Ca CaH2
* Tnh kh ca hidro:
H2 c th kt hp vi cc nguyn t khng kim loi nh O, S, N...
H2 + O2 H2O H = - 63kcal/mol
- H2 c th kh cc oxit kim loi nh: CuO, Fe 2O3 , HgO, PbO...
H2 + CuO Cu + H2O
H2 + Fe3O4 Fe + H2O
- Khi c mt Pt lm xc tc, H2 c th kh cc hp cht hu c khng no

thnh hp cht no, andehyd thnh ru...
- Hydro mi sinh c kh nng kh rt mnh. nhit thng hydro

nguyn t c th kt hp vi O, S, P, As, kh c nhiu oxit kim loi, y
c mt s kim loi nh Cu, Ag, Pb ra khi dung dch mui ca chng, tham
gia vo nhng phn ng m iu kin H2 khng th phn ng c.
VI.4. IU CH V NG DNG
43
VI..4.1. iu ch
a. Trong cng nghip
Hydro c iu ch theo cc phng php khc nhau:
Phng php i t than
Ngi ta cho hi nc i qua than cc t nng n 1000 0C v thu c

mt hn hp 2 kh CO v H2 gi l kh than
o
C + H2 O 1000
C
CO + H2 H0 = 130kJ/mol
Phng php i t kh thin nhin
Cho hn hp kh thin nhin v hi nc c t nng n 1000 0C

i qua cht xc tc Ni
o
CH4 + H2O 1000

C , Ni
CO + 3 H2 H0 = 209kJ/mol
Kh thin nhin cng c th c t chy khng hon ton trong oxy hay
khng kh to thnh kh than
2CH4 + O2 2CO + 4 H2 H0 = - 71kJ/mol
Phng php in phn
Phng php in phn nc cho hydro rt tinh khit. Trong cng nghip
ngi ta in phn dung dch NaOH 25%, H2 bay ra cc m v O2 bay ra
cc dng. Dteri c dng lm cht lm chm ntron trong l phn ng
ht nhn. Trong ho hc teri c dng cho vic nghin cu c ch ca cc
phn ng. iu ch teri ngi ta in phn nc nng.
b. Trong phng th nghim
Trong phng th nghim hydro c iu ch bng cch cho Zn tc dng

vi axit H2SO4 long hoc axit HCl trong bnh kp:
Zn + H2SO4 ZnSO4 + H2
44
Trong trng hp dng Zn tinh khit, phn ng xy ra rt chm, cn phi cho

thm vo mt lng mui ng phn ng xy ra nhanh hn.
VI.4.2. ng dng
Hydro c s dng rng ri trong nhiu ngnh cng nghip:
- Nguyn liu cho nhiu ngnh: Cng nghip ho hc (tng hp NH3,

HCl), cng nghip thc phm (hydro ho du m, sn xut margarin...), cng
nghip luyn kim (hydro dng lm cht kh kh cc qung)
- Hydro lng c s dng trong k ngh tn la, hydro nguyn t c

s dng ch to cc hp kim siu cng.
- Cc ng v nng ca hydro (D2, T2) ng vai tr quan trng trong vic

iu ho cc phn ng ht nhn.
VI.5. HYDRUA
Hydrua l hp cht ca hydro vi mt nguyn t khc. Hydro to hydrua

vi hu ht cc nguyn t khc. Da vo bn cht ca lin kt ho hc trong
hp cht, ngi ta phn chia cc hydrua ra lm 3 loi: hydrua ion, hydrua cng
ho tr v hydrua kiu kim loi
Li C O F
N
Si S Cl
a
M C C G G
K Ca Sc Ti V Cr Fe Ni Zn As Se Br
n o u a e
R N M R R A C
Sr Y Zr Tc Pd In Sn Sb Te I
b b o u h g d
45
A H
Cs Ba La Hf Ta W Re Os Ir Pt Tl Pb Bi Po At
u g
Hydrua Hydrua cng

Hydrua kiu kim loi
ion ha tr
VI.5.1.Hydrua ion
Hydrua ion l cc cht dng tinh th khng mu, ging vi mui nn c

gi l hydrua mui. Hydro c i lc electron rt b v xu hng to thnh ion
m ca n rt yu so vi cc halogen l nguyn t m in hn.
1/2H2 (k) = H(k) H0 = 218 kJ/mol 1/2Br2 (k) = Br(k) H0 = 113 kJ/mol
H(k) + 1e = H-(k) H0 = - 66 kJ/mol Br(k) + 1e = Br-(k) H0 = - 326kJ/mol
1/2H2 (k) + 1e = H-(k) H0 = 152 kJ/mol 1/2Br2(k)+1e = Br-(k) H0 = 213 kJ/mol
Do tnh thu nhit ca ion H- cho nn ch nhng kim loi hot ng mnh
nh kim loi kim, kim loi kim th mi c th to nn cc hydrua ion.
L tnh
Cc hydrua c mng tinh th ion, chng c cc c tnh sau:
- C nhit nng chy cao, iu kin thng chng l cc cht kt tinh mu

trng.
- Khi nng chy c dn in kh cao
- Khi in phn nng chy hydro thot ra anot.
Ho tnh
Nhit to thnh ca cc hydrua ion khng cao, do chng km bn, nhit

cao chng b phn hy cho cc n cht.
Nhit to thnh ca cc hydrua ion
Cht Nhit to thnh (Kcal/mol) Cht Nhit to thnh

46
(Kcal/mol)
LiH 21.7 CaH2 46.6
NaH 14.4 SrH2 42.2
KH 14.2 BaH2 41.0
RbH 20.3
CsH 19.9
- LiH v NaH b phn hu nhit khong 350 - 600 0C
2NaH 2Na + H2
Trong kh quyn hydro, chng bn hn v c th nng chy, phn ly thnh ion:
MH M+ + H-
- Anion H- c tnh baz rt mnh, nn ch tn ti trong mng tinh th. Khi tip
xc vi cc cht c kh nng cho H+ n phn ng rt mnh lit. Do cc
hydrua ion b phn hu hon ton trong nc cho mi trng kim mnh
NaH + H2O NaOH + H2
- Cc hydrua ion c tnh baz nn chng phn ng vi cc hydrua axit (trong

dung mi khng nc) to thnh cc phc hydrua:
LiH + AlH3 Li[AlH4]
LiH + BH3 Li[BH4]
Thc t l phn ng: H- + BH3 [BH4]-
- H- rt d mt electron, cc hydrua ion l cc cht kh rt mnh, l mt trong

cc cht kh mnh nht c bit:
H2 + 2e 2H- E0 = -2,25V
47
VI.5.2. Cc hydrua cng ho tr
Xp vo loi ny l cc hp cht gia hydro vi cc nguyn t km m in hn

n nhng khng c kh nng to thnh hydrua ion. Lin kt trong loi hydrua
ny c bn cht cng ho tr hoc ion cng ho tr. Tu thuc vo cu trc
electron ca nguyn t dng in m cc cht c cu trc phn t v cu to
trng thi rn khng ging nhau.
Cc hydrua cng ho tr d bay hi
c to thnh gia hydro vi cc kim loi hoc mt s khng kim loi

c s electron ho tr bng hoc ln hn s phi tr ca nguyn t
V d: Hydrua ca cc nguyn t m in km phn nhm IVA v VA ca

bng h thng tun hon: SiH4, GeH4, SnH4, AsH3, PH3, SbH3 ...
trng thi rn chng c mng tinh th phn t, do nhit nng

chy v nhit si thp. Cc hydrua loi ny c bn cht axit. Do nguyn t H
c s oxyho (-1) nn n cng c cc tnh cht ging hydrua ion:
- Khng bn, nhiu hydrua b phn hu ngay khi va to thnh.
2SbH3 2Sb + 3H2
- B thu phn mnh, gii phng H2
SiH4 + 4 H2O H4SiO4 + 4 H2
- C tnh kh mnh, nhiu cht t bc chy khi tip xc vi oxy ca khng kh:
2PH3 + 4 O2 2H3PO4
Cc hydrua cng ho tr kh bay hi
c to thnh bi cc kim loi hoc khng kim loi c s electron ho tr nh

hn s obitan ho tr c kh nng tham gia lin kt (thng l cc nguyn t
thuc phn nhm IIA hoc IIIA). V d: BeH2, B2H6, AlH3, ZnH2, InH3 ...
Cc hydrua loi ny thng c cu trc lp, mch vi cc nguyn t hydro

ng vai tr cu ni.
48
H H H H H
Be Be Be B B
H H H H H
Do vy cc hydrua loi ny c nhit nng chy cao hn, bn ln hn so

vi loi hydrua d bay hi.
Cc hydrua c tnh cht trung gian gia hydrua ion v hydrua cng ho tr d
bay hi. Chng thng c tnh cht lng tnh. Trong dung mi khng nc n
phn ng c vi cc hydrua ion v hydrua cng ho tr.
V d: BeH2 + 2NaH Na2[ BeH4]
BeH2 + 2BH3 Be [BH4]2
Nhn chung cc hydrua cng ho tr km bn hn nhiu so vi hydrua ion v

thng c iu ch bng phng php gin tip.
VI.5.3. Cc hydrua kiu kim loi
Cc nguyn t chuyn tip cng to thnh hp cht bc hai vi hydro v

cng thng gi l hydrua. Mc d c gi l hydrua nhng y l cc hp
cht c lin kt kim loi, c thnh phn khng hp thc gn vi cc cng thc l
tng MH, MH2, MH3.
Thng cc hp cht ny l cc cht rn c mu xm dn in v dn nhit tt.
Hin nay c 2 thuyt gii thch tnh dn in kim loi ca cc hp cht

ny. Thuyt th nht cho rng H xm nhp vo mng tinh th kim loi di
dng ion H+ v nhng electron ho tr cho vng dn ca kim loi. Thuyt th
hai cho rng H nhn electron ca vng dn ca kim loi v tn ti trong mng
tinh th di dng ion H-.
Do c tnh kh mnh, cc hydrua ion, hydrua phc, hydrua kim loi v

hydrua cng ho tr khng bay hi thng c s dng rng ri lm cht kh
trong nhiu qu trnh tng hp khc nhau. c bit cc hydrua kiu kim loi do
49
c tnh gin, d nghin thnh bt mn, thng c s dng iu ch kim

loi dng bt.
VI.6. NC
Hidro v oxy to nn cc hp cht nh nc (H2O), hydropeoxit (H2O2).

Nc l hp cht quan trng nht trong tt c cc oxit. Do hm lng ln v do
c nhng tnh cht l ho hc c bit, nc ng vai tr v cng quan trng
trong cc qu trnh sng, nc l dung mi quan trng nht tin hnh cc
phn ng ho hc.
Cu to phn t
Cc phn t nc c cu to dng gc
H 104,50 H
Gc HOH l 1050 v di lin kt O-H bng 0,994 A0. Cu hnh

electron ca phn t nc l (Slk)2 (Zlk)2(X)2(Y)2
Gia cc phn t nc hnh thnh cc lin kt hidro kh bn vng c

trng thi lng v trng thi rn. Khi trng thi rn, nc c mng tinh th
phn t vi lc gi cc phn t cc nt mng l lin kt hidro. Trong nc
mi phn t nc c lin kt vi 4 phn t nc khc nh lin kt hidro.
Cu trc ny rt rng nn nc c t khi nh. trng thi lng do lin

kt hidro nn cc phn t nc b t hp 2, 3 hoc 4 phn t. Chnh do s tn ti
ca lin kt hidro nn nc c nhng tnh cht l ho hc khc nhiu so vi cc
hp cht cng kiu.
Do c cu to khng i xng. H2O l phn t c cc di lng cc l

0,39 A0 v cc tnh ln = 1,84D. Phn t H2O rt bn i vi nhit, bt u
phn hu 10000C v n 20000C th phn hu khong 2%.
2 H2O 2H2 + O2 H = 135 Kcal/mol
Tnh cht vt l
50
Nc l mt cht lng trong sut, khng mu, khng mi v khng v.

Lp nc dy c mu xanh lam nht
Nc c nhit nng chy v nhit si cao hn hn hn cc hp cht cng

kiu. t0(s) = 100 0C t0(nc) = 0 0C
T khi ca nc cng thay i mt cch bt thng:
Nhit 0 4 10 15 20
(0C)
d (g/cm3) 0,9999866 1 0,999727 0,999127 0,99823
t khi cc i 4 0C. Ngi ta gii thch tnh cht bt thng nh sau: bng
lin kt hidro, cc phn t nc trong nc lng trng hp vi nhau to thnh
cc tp hp phn t ln hn.
nhit 0,010C v p sut hi 0,006 atm, nc c th tn ti ng thi

3 trng thi: nc , nc lng v hi nc. Nhit gi l im ba ca
nc trn gin trng thi ca nc.
L
K
R
t0
Gin trng thi ca nc
Nc c nhit dung ring ln nht so vi mi cht lng v rn. Lng nhit cn

thit un nng 1ml nc t 14,50C ln 15,50C c dng lm n v nhit
gi l calo. Nh c nhit dung ln, nc c vai tr rt quan trng trong vic iu
ho kh hu ca qu t.
51
Nc l dung mi tt nht v quan trng nht. N c kh nng ha tan nhiu

cht, phn li cc axit, bazo, v mui thnh ion, l mi trng cho rt nhiu phn
ng ha hc khc nhau, c bit l cc phn ng xy ra trong c th sinh vt
Tnh cht ho hc
Nc rt bn i vi nhit, ch phn hy thnh hidro v oxi nhit cao.

10150C c 0,03% b phn hy, 17000C c 0,7% b phn hy, 20000C c 8
9% b phn hy
Cc phn t nc c cc nn chng bao quanh cc ion hoc phn t ha tan

trong nc, hin tng ny gi l s hidrat ha. V d:
Na+ (k) + aq Na+.aq : s hidrat ha ion
CO2 (k) + aq CO2.aq : s hidrat ha phn t
CaCl2 (r) + 6H2O CaCl2.6H2O : s hidrat ha tinh th
S hidrat ha l qu trnh ta nhit, gi l nhit hidrat ha. Nhit hidrat ha

ng vai tr quan trng trong s ha tan cc cht trong nc.
Cng do s hidrat ha m nhiu cht khi kt tinh t dung dch nc thng km

theo mt s t phn t nc v nhng tinh th to thnh gi l cc tinh th hidrat,
nc nm trong tinh th hidrat gi l nc kt tinh. V d, khi kt tinh t dung
dch ng sunfat ta thu c cc tinh th mu xanh CuSO4.5H2O
Kh nng phn ng ca nc cn th hin phn ng thy phn v phn ng

oxi ha kh
Cc mui cha gc axit yu hoc gc bazo yu u b thy phn khi tan trong
nc. Sau khi thy phn, pH ca nc thng bin i, v d NaCH3COO,
NH4Cl khi tan trong nc b thy phn nh sau:
CH3COO- + HOH CH3COO- + OH- : pH ca nc tng
NH4+ + H2O NH3 + H3O+ : pH ca nc gim
52
Mui NH4CH3COO to bi cc ion CH3COO- v NH4+ u b thy phn khi tan

trong nc. Mc thy phn ca hai ion ny gn bng nhau, nn pH ca nc
bin i khng ng k
Nc c tnh oxi ha (do hidro c s oxi ha +I) v c tnh kh (do oxi c s oxi
ha II). iu kin thng cc tnh cht ny th hin yu v ch nhng cht
kh mnh, nh cc kim loi kim, kim th v nhng cht oxi ha mnh nh flo
mi phn ng d dng vi nc.
Nc c kh nng phn ng rt mnh. N c th phn ng vi rt nhiu n

cht v hp cht. Khi phn ng, nc th hin cc khuynh hng ch yu sau
y:
2 H+ + 2e H2
2Na + 2H2O 2NaOH + H2
2F2 + 2H2O 4HF + O2
nh gi kh nng oxi ha kh v phng din nhit ng ca nc ta da

vo th kh ca cp sau:
2H+ + 2e H2 (k)
O2(k) + 4e + 4H+ 2H2O (l)
250C ta c
0, 059 [H ]2
H
/ H2
H0 / H lg
2
2 pH 2
0, 059
O / H O O0 / H O lg pO2 .[H ]4
2 2 2 2
4
Xt trng hp pH2 = pO2 = 1atm v thay H0

/ H2
0, 00V
+
O0 / H O = 1,23 V , pH = -lg[H ] ta c:
2 2
H
/ H2
0,059 pH
53
O / H O = 1,23 0,059pH
2 2
V nc c pH = 7 nn H
/H2
0, 413V v O2 / H 2O = 0,817V
Da vo th kh ta c th coi rng nc b kh khi tc dng vi cht c th kh

b hn 0,143 V v b oxi ha khi phn ng vi cht c th kh ln hn 0,817
V. Tuy nhin iu kin thng tc ca phn ng oxi ha kh thng b,
nn nhiu phn ng loi ny thc t khng xy ra.
54
CHNG VII: CC NGUYN T NHM VIIA
(CC HALOGEN)
Cc nguyn t flo (F), clo (Cl), brm (Br), iod (I) v atatin (At) thuc
phn nhm chnh nhm VII, c gi chung l halogen (ting Hy lp ngha l
"to mui").
Cu hnh lp in t ha tr ca cc halogen l: ns2 np5, cn thiu mt

in t t c cu hnh bn vng ca kh him. Do , cc halogen c i
lc ln vi in t, chng d dng kt hp thm 1 in t to thnh ion X-:
X2 + 2e 2X-. V th cc halogen l nhng nguyn t khng kim loi rt in
hnh.
Bng 2.1: Mt s c im v tnh cht ca cc halogen.
Nguyn t F Cl Br I At
S th t nguyn t 9 17 35 53 85
Khi lng nguyn t 18,99 35,45 79,904 126,9 210
Cu hnh lp e ngoi cng 2s2 2p5 3s2 3p5 4s2 4p5 5s2 5p5 6s2 6p5
Nng lng ion ha (eV) 17,42 12,97 11,84 10,45 9,2
i lc ca ngt vi in t 3,45 3,61 3,37 3,08 2,8

(eV)
m in tng i 4,0 3,0 2,8 2,6 2,2
Bn knh nguyn t (A0) 0,064 0,099 0,114 0,133 ......
Bn knh ion (A0) 0,133 0,181 0,196 0,22 0,23
Khong cch gia cc ht

0,142 0,199 0,228 0,267 ......
nhn trong phn t X2 (nm)
55
NL lin kt X-X (kJ/mol) 159 243 192 151 109
Trng thi vt l iu kin kh mu kh mu lng tinh th -----

thng mu
lc nht vng lc tm en xanh
nu
Nhit nng chy (0C) -219,6 -101,0 -7,3 113,6 227
Nhit si (0C) -118,1 -34,1 59,2 185,5 317
phn ly nhit ca phn t

X2 1000K
0,043 0,00035 0,0023 0,28
2000K
0,99 0,37 0,72 0,89
Th in cc chun X2/2X-(V) 2,87 1,36 1,07 0,54 -
Trong dy F - At, theo s th t nguyn t tng dn, bn knh nguyn t

tng, m in gim, tnh khng kim loi v kh nng oxy ha ca cc nguyn
t yu dn. Flo lun lun c mc oxy ha -1 trong cc hp cht ca n, v flo c
m in ln nht trong tt c cc nguyn t. Cc halogen cn li th hin
nhng mc oxy ha khc nhau t -1 +7.
VII.1. L tnh
n cht halogen cu to t cc phn t X2. T trn xung di trong

nhm kch thc v khi lng phn t X2 tng dn n nhit nng chy v
si tng dn
iu kin thng flo v clo l cht kh khng mu (flo), vng lc (clo), brom
l cht lng nng, mu nu , d bay hi; cn iod l cht rn mu tm sm, c
p sut hi ln, khi un nng p sut thng n thng hoa to hi mu tm,
tnh cht ny c s dng tinh ch iod
Cc halogen u c, mi xc, t tan trong nc, tr flo phn hy hon ton

nc nhit thng. 200C ha tan trong nc ca clo l 0,73 %, brom
3,6 %, iod 0,03 % v c phn ng mt phn vi nc. Halogen d tan trong
56
cc dung mi hu c. Iod cn d tan trong dung dch nc cha I- to thnh ion

I3-, dung dch ny thng c dng trong chun th tch
Iod to vi h tinh bt mu xanh sm khi ngui, nn h tinh bt c dng

trong ha hc phn tch nhn bit iod
VII.2. Ha tnh
Tnh cht ha hc in hnh ca cc halogen l tnh oxy ha mnh, kh

nng oxy ha gim dn t flo n atatin. Flo tuy c i lc in t b hn clo
nhng do c nng lng lin kt F-F b nn vn hot ng mnh hn clo.
Flo c th tc dng vi tt c cc nguyn t tr N2; clo tc dng rt mnh

lit vi cc kim loi v a s cc kim (tr O2, N2, v cc kh tr); brm cng
ging nh clo nhng phn ng xy ra t mnh lit hn; iod tc dng trc tip
vi s cc nguyn t t hn.
V d: * Vi H2 : H2 + X2 2HX
Flo cho phn ng n -2520C. Cl2, Br2 tc dng vi hydro khi c nh

sng, cn I2 cho phn ng thun nghch.
* Vi kim loi: clo cho phn ng rt mnh: Fe + Cl2 FeCl3 . Phn

ng xy ra yu vi I2 : Fe + I2 FeI2
Mt halogen hot ng c th tc dng vi mui halogenua gii phng

ra mt halogen khc t hot ng hn:
F2 + 2NaCl = 2NaF + Cl2
Cl2 + 2NaBr = 2NaCl + Br2
Tnh cht ny ph hp vi s gim in th cc chun t flo n iod.
* Vi nc: flo tc dng mnh lit vi nc gii phng oxy:
2F2 + 2H2O = 4H+ + 4F- + O2
Vi clo v brm, qu trnh oxy ha nc gii phng oxy i hi nng lng

hot ha cao nn phn ng xy ra theo hng khc:
57
X2 + 2H2O H3O+ + X- + HOX.
Iod khng tc dng vi nc.
Flo khng c tnh kh, nhng tnh kh tng dn t clo n atatin khi
chng tc dng vi cht oxy ha mnh. V d:
5Cl2 + Br2 + 6H2O 2HBrO3 + 10HCl
5HOCl + 2At + H2O 2HAtO3 + 5HCl
VII.3. TRNG THI T NHIN, PHNG PHP IU CH V NG

DNG
Trng thi t nhin
Do hot tnh ha hc mnh nn cc halogen ch tn ti trong thin nhin trng

thi lin kt, ch yu dng mui ca axit halogenhydric.
Flo gp khong florit CaF2 (c tn gi florit v thm n vo qung st s

to thnh x d nng chy khi luyn gang). Ngoi ra flo cn c trong qung
crylit Na3AlF6, floapatit Ca5F(PO4)3.
Hp cht quan trng ca clo l NaCl (c trong nc bin, mui m), l

nguyn liu ch yu iu ch cc hp cht khc ca clo. Ngoi ra clo cn c
trong KCl dng khong cacnalit KCl.MgCl2.6H2O v xirin KCl. Brm tn ti
trong t nhin dng mui KBr, MgBr2 (c nhiu trong nc bin).
Iod c trong nc bin, trong mt s loi rong c kh nng tch cp iod,

ngoi ra iod cn c trong cc mui KIO3, KIO4 trong mt s ging khoan.
Atatin: thc t khng gp trong t nhin. N c iu ch nhn to khi thc

hin phn ng ht nhn. ng v tn ti lu nht ca atatin l 210At c chu k
bn r ch bng 8,3 gi. Lng rt nh ca atatin thy trong sn phm phn hy
phng x t nhin ca uran v thori.
iu ch
58
Flo c tnh oxi ha mnh nht trong tt c cc cht nn phng php duy
nht iu ch flo l in phn mui florua nng chy, hn hp c in
phn l KF + 3HF (nng chy 66oC ). Trong cng nghip, clo cng c iu
ch bng phng php in phn dung dch NaCl c hay khng c mng ngn.
Trong PTN th dng cht oxi ha mnh oxi ha HCl. Br2, I2 c iu ch ch
yu bng cch dng clo y brm, iod ra khi cc mui brmua, iodua.
Clo c iu ch bng phng php in phn dung dch mui n c mng

ngn
2 NaCl + 2 H2O 2 NaOH + Cl2 + H2
Trong phng th nghim thng iu ch mt lng nh clo bng cch un nh

hn hp MnO2 vi axit clohidric c
MnO2 + 4 HCl MnCl2 + Cl2 + 2H2O
Brom c iu ch bng phn ng:
Cl2 + 2 Br- 2Cl- + Br2
Ngi ta iu ch iod ch yu t iodat nh phn ng sau:
2IO3- + 5HSO3- 3HSO4- + 2SO42- + H2O + I2
ng dng
Flo c dng iu ch cc freon (ch yu l CFCl3 v CF2Cl2) dng

trong t lnh v lm nh lnh trong cng nghip. Flo lng v mt s hp cht
ca n c dng lm nhin liu tn la. Clo c dng ty trng vi, bt
giy, st trng v dng trong cng nghip ha cht. Brm c dng ch yu
cho thm vo etxng chy ng c. Iod c dng lm dc phm v dng
trong phn tch.
VII.4. CC HYDRO HALOGENUA (HX)
Ha tnh v l tnh
59
iu kin thng tt c cc hydro halogenua u l kh khng mu. Mt

s tnh cht ca chng th hin trong bng sau:
Bng 2.2: Mt s tnh cht ca hydrohalogenua
Tnh cht HF HCl HBr HI
Nng lng lin kt H-X 135 103 87 71

(kcal/mol)
di lin kt H-X (Ao) 0,92 1,28 1,41 1,60
Mmen lng cc (D) 1,91 1,07 0,79 0,38
t0nc (0C) -83 -114,2 -88 -50,8
t0 si (0C) +19,5 -84,9 -66,7 -35,8
phn ly ca dung dch 0,1N 9 92,6 93,5 95

(%)
L hp cht c cc cc hydro halogenua tan rt nhiu trong nc: HF tan

v hn trong nc, cc HX cn li c tan ln v xp x nhau.
Axit flohydric l axit duy nht tc dng c vi silic dioxyt:
4HF + SiO2 = SiF4 + 2H2O
SiF4 + 2HF = H2SiF6
Dung dch nc ca cc hydro halogenua c gi l axit halogenhydric.

mnh ca cc axit tng ln trong dy HF - HCl - HBr - HI. HCl, HBr, HI l
cc axit mnh. HF l axit yu v nng lng lin kt HF ln v c s kt hp ca
F- vi phn t HF: F- + HF HF 2
Trong dy HF - HCl - HBr - HI bn ca cc phn t gim i, cn tnh

kh tng dn ln. V d: trong khi HF, HCl khng tc dng vi H2SO4 c th
HBr kh H2SO4 n SO2 , cn HBr kh H2SO4 n H2S.
2HBr + H2SO4 = Br2 + SO2 + 2H2O

60
8HI + H2SO4 = 4I2 + H2S + 4H2O
Cc dung dch HBr, HI khi lu tr nn c mu vng v b oxy ca

khng kh oxy ha dn, gii phng halogen t do. Tng tc ca HCl v oxi ch
xy ra trong pha kh, khi c un nng:
O2 + 4HCl 2H2O + 2Cl2
ng dng
Trong cc axit HX, HCl c dng nhiu hn c. Sn lng ca HCl

ng hng th ba sau H2SO4 v HNO3. HCl c dng trong cng nghio ha
cht iu ch vinyl clorua t C2H2, iu ch mui clorua kim loi, NH4Cl,
phm nhum v dc phm. Axit flohydric c dng ch yu iu ch
cryolit nhn to (dng trong sn xut Al), dng trong sn xut uran v khc thy
tinh.
iu ch
Phng php duy nht dng iu ch HF trong cng nghip v trong

phng th nghim l cho mui florua (thng l CaF2) tc dng vi H2SO4 c
250oC:
CaF2 + H2SO4 CaSO4 + 2HF
Phng php ny cng c dng iu ch HCl:
NaCl + H2SO4 NaHSO4 + HCl
NaCl + NaHSO4 Na2SO4 + HCl
Ngy nay, trong cng nghip HCl c iu ch bng phng php tng hp:
H2 + Cl2 2HCl
HBr v HI ch c th iu ch bng phng php thy phn mui brmua v

iodua pht pho
PBr3 + 3H2O H3PO3 + 3HBr
61
PI3 + 3H2O H3PO3 + 3HI
*CC HALOGENUA
Halogenua l tn gi chung ca hp cht ca halogen vi mt nguyn t

no . Ty thuc m in ca cc nguyn t, bn cht ca lin kt trong cc
halogenua c th bin i t hon ton ion n gn nh hon ton cng ha tr.
Tuy vy ngi ta vn thng chia halogenua lm 2 loi:
1. Halogenua ion:
L halogenua c mng li tinh th bao gm cc ion. Halogenua ion c

nhit nng chy v nhit si cao. Halogenua ion dn in khi nng chy
v khi tan vo dung dch. Cc halogenua tan trong nc to nn nhng ion
hydrat ha ca cation kim loi v anion halogenua:
MXn + (x + ny) H2O Mn+ .xH2O + nX- .yH2O
2.Halogenua cng ha tr: l halogenua c mng li phn t. Lc tng tc

gia cc phn t trong tinh th l lc Van der Waals. Cc nguyn t khng
kim loi v cc kim lai c mc oxy ha cao to nn cc halogenua cng ha tr.
Cc Halogenua cng ha tr u d bay hi, tan trong dung mi khng

cc v khng dn in khi nng chy cng nh khi tan trong dung mi khng
phn cc.
Tnh cht ha hc chung ca halogenua cng ha tr l d b thy phn to axit

halogen hydric. V d:
BiCl3 + 3H2O Bi(OH)3 + 3HCl
PBr3 + 3H2O H3PO4 + 3HBr
Mt hin tng thng xy ra trong cc halogenua cng ha tr l s to

thnh cu halogen gia 2 nguyn t. V d: (BeCl2)n , Al2Br6
Cl Cl Cl Cl
Be Be Be
62
Cl Cl Cl Cl
Br Br Br
Al Al
Br Br Br
Cc halogenua cng ha tr d b thy phn c th c iu ch theo cc

phng php sau y:
1) Cho cc nguyn t tc dng trc tip vi nhau:
Sn + 2Cl2 SnCl4
S + 3F2 SF6
2) un nng cc oxyt hay sulfua vi cacbon v Cl2; vi S2Cl2 v Cl2; vi

CCl4 hoc phtgen:
Cr2O3 + 3C + 3Cl2 2CrCl3 + 3CO
4Lu2O3 + 3S2Cl2 + 9Cl2 8LuCl3 + 6SO2
BeO + CCl4 = BeCl2 + CO2
3) iu ch florua ngi ta cho clorua tc dng vi HF hay un nng

oxyt vi hn hp CaF2 v H2SO4.
TiCl4 + 4HF TiF4 + 4HCl
GeO2 + 2CaF2 + 2H2SO4 = GeF4 + 2CaSO4 + 2H2O
Cc halogen nua cng ha tr khng khng b thy phn c th iu ch

bng cch cho kim loi, oxit hay hydroxit kim loi tc dng vi axit
halogenhydric, hoc kt ta cc halogen t tan bng phn ng trao i ion:
AgNO3 + NaCl AgCl + NaNO3
63
VII.5. HP CHT CHA OXI CA HALOGEN
VII.5.1. OXYT CA HALOGEN
Cc oxyt ca halogen u km bn i vi nhit cho nn rt hot ng v

mt ha hc. Trong cc oxit ca halogen, oxit ca clo v iod c nghin cu
nhiu nht. Oxit ca flo c tnh cht hi khc vi oxyt ca cc halogen khc.
1. Oxit ca flo
Flo to nn mt s oxit c cng thc chung l F2On (n = 1,2,3,4)
Diflo oxit F2O c cu to i xng nh H2O, gc HF = 1030, dO-F = 1,41A0
L mt kh khng mu c mi ging ozon v rt c, ha lng -1450C,

ha rn -2240C. L mt cht oxy ha mnh, n tc dng vi hu ht cc kim
loi v khng kim loi to thnh oxit v florua.
F2O + 2Mg MgO + MgF2
N khng tc dng vi nc lnh nhng tc dng vi hi nc:
F2O + H2O = 2HF + O2
F2O c to nn khi cho F2 tc dng vi NaOH 2%
2F2 + 2NaOH 2NaF + H2O + F2O
F2O l oxit bn nht trong cc oxit ca flo, n ch phn hy chm 250oC to flo
v oxy.
Diflo dioxit F2O2 c cu to nh H2O2
F
0
O1,27A O 1,575A0
F
64
-950C l cht lng mu anh o, -1600C l mt cht rn mu da cam, rt

km bn, -570C b phn hy:
F2O2 F2 + O2
F2O2 c iu ch bng cch phng in m qua hn hp flo v oxy nhit

thp.
Flo cn c cc oxit F2O3 (cht lng mu mu), F2O4 (rn, nu) cha c
nghin cu nhiu.
2. Oxit ca clo: Clo c 5 oxit: Cl2O, Cl2O3, ClO2, Cl2O6, Cl2O7.
Diclo oxit Cl2O
O 1,71 A0
Cl 1110 Cl
L mt cht kh mu vng da cam, nng hn khng kh, c mi ging clo;

ha lng 20C to thnh cht lng mu nu v ha rn -1210C. Cl2O khng
bn, d b phn hy, tc dng mnh vi nhiu nguyn t v cc hp cht c cha
hydro.
c iu ch theo phn ng
2HgO + 2Cl2 HgO.HgCl2 + Cl2O
Clo dioxyt ClO2 c cu to gc
65
L phn t c s l in t nhng ClO2 khng c kh nng trng hp nh

cc phn t c s l in t khc, c l v trong phn t ClO2 cc in t c
thn l khng nh c.
ClO2 l cht kh mu vng lc, c mi kh chu. 110C ha lng, to ra

cht lng mu nu, -590C ha thnh cht rn mu da cam. ClO2 l hp cht
km bn v l cht oxy ha mnh.
4S + 6ClO2 + 4H2O 4H2SO4 + 3Cl2
Zn + 2ClO2 = Zn(ClO2)2
ClO2 tc dng vi dung dch kim to hn hp clorit v clorat:
2ClO2 + 2KOH 2KClO2 + KClO3 + H2O
ClO2 c iu ch theo 2 phn ng sau:
2KClO3 + H2C2O4 + 2H2SO4 = 2KHSO4 + 2H2O + 2ClO2 + 2CO2
2NaClO3 + SO2 + H2SO4 = 2ClO2 + 2NaHSO4
Diclo hecxa-oxyt Cl2O6 l hp cht rt khng bn, c cu to cha xc nh, l

cht lng nh du c mu thm, ha rn 30C. Phn ng mnh vi H2O to
thnh hn hp axit HClO3 v HClO4
Cl2O6 + H2O HClO3 + HClO4
Cl2O6 c to nn khi cho ClO2 tc dng vi O3 c tia t ngoi:
6ClO2 + 2O3 3Cl2O6
Diclo hepta-oxit Cl2O7
66
L mt cht lng khng mu,

ging du, si 830C, ha rn -900C.
Cl2O7 l hp cht bn nht trong cc
oxit ca clo, phn hy nhit ln
hn 120oC; kh nng oxy ha km hn
cc oxit khc ca clo: vi cc cht nh
S, P, C, iu kin thng phn ng khng xy ra, nhng vi I2 th gy ra phn
ng n. N tan v hn trong dung mi CCl4 nhng tan chm trong nc to
thnh axit HClO4
Cl2O7 + H2O 2HClO4
i vi Br2 v I2 ta cng gp cc oxit nh Br2O, BrO2, Br3O8, I2O4, I4O9, I2O5...
VII.5.2. AXIT HYPOHALOGEN (HXO)
Axit hypohalogen HXO l phn t c cu trc gc. Chng khng bn, d

b phn hy to HX v O2.
Trong cc axit HXO th axit HFO c tnh cht khc bit vi HClO,
HBrO v HIO.
Khi cho F2 p sut thp i qua nc 00C, axit HFO c to

nn, v c th tch ra trng thi t do. Khi tc dng vi nc HFO khng gii
phng O2 m to H2O2
HFO + H2O HF + H2O2
Cc axit HXO khc ch tn ti trong dung dch long, chng l cc axit rt yu:
HXO + H2O H3O+ + XO-
Tnh axit gim dn t HClO n HIO:
KHClO = 3,4.10-8 , KHBrO = 2.10-9 , KHIO = 10-11
67
Mui ca chng c gi l hypohalogenit. Cc mui ny ch tn ti trong

dung dch. Ring KClO, NaClO, Ca(ClO)2 c th tch ra trng thi rn. Trong
mi trng kim ion XO- phn hy theo phn ng:
3XO- 2X- + XO3-
Vi ClO- tc phn ng xy ra mnh nhit trn 750C. V vy nhit

thng clo tc dng vi dung dch kim theo phn ng:
Cl2 + 2KOH KCl + KClO + H2O
Khi un nng: 3Cl2 + 6KOH 5KCl + KClO3 + 3H2O
Ion BrO- phn hy chm, IO- phn hy nhanh, v vy I2 tc dng vi kim

theo phn ng:
3I2 + 6KOH 5KI + KIO3 + 3H2O
Cc axit HXO v mui XO- l cc cht oxy ha mnh
2HClO + 2H+ + 2e = Cl2 + 2H2O, E0 = +1,63V
2HBrO + 2H+ + 2e = Br2 + 2H2O, E0 = +1,59V
2HIO + 2H+ + 2e = I2 + 2H2O, E0 = +1,45V
chng c th oxy ha Mn2+, Fe2+ ,..., NH3, H2O2,....
3NaClO + 3NH3 = N2 + 3NaCl + 3H2O
NaClO + H2O2 = H2O + O2 + NaCl
Hai mui XO- quan trng l nc Javel
NaOH + Cl2 = NaClO + NaCl + H2O
v clorua vi
Ca(OH)2 + 2Cl2 = CaCl + Ca(ClO)2 + 2H2O
Ca(OH)2 + Cl2 = CaOCl2 + H2O
68
c dng ty trng vi si, st trng.
VII.5.3. AXIT HALOGEN (HXO2)
Trong cc axit halogen, ngi ta ch mi bit c HClO2. l mt

hp cht khng bn, ch tn ti trong dung dch, rt d b phn hy.
4HClO2 = 2ClO2 + HClO3 + HCl + H2O
HClO2 l axit c mnh trung bnh, K = 10-2. Mui ClO 2 gi l clorit c cu

to gp khc, gc lin kt bng 1,64A0 < 1,71A0 (lin kt n Cl-O). Mui clorit
bn hn axit clor. Mui quan trng l NaClO2 c dng ty trng vi v
giy. NaClO2 c iu ch theo phn ng
2ClO2 + Na2O2 2NaClO2 + O2
Khi un nng NaClO2 b phn hy
3NaClO2 NaCl + 2NaClO3
Dung dch HClO2 c iu ch theo phn ng
Ba(ClO2)2 + H2SO4 = BaSO4 + 2HClO2
VII.5.4. AXIT HALOGENIC (HXO3)
HClO3, HBrO3 ch tn ti trong dung dch, chng d phn hy khi nng

m c
3HClO3 HClO4 + 2ClO2 + H2O
4HBrO3 2Br2 + 5O2 + 2H2O
HIO3 kh bn. C 3 axit u c tnh oxy ha mnh, tnh oxy ha gim t HClO3 n
HIO3
2HClO3 + 10H+ + 10e = Cl2 + 6H2O, E0 = +1,47V
2HBrO3 + 10H+ + 10e = Br2 + 6H2O, E0 = +1,52V
2HIO3 + 10H+ + 10e = I2 + 6H2O, E0 = +2,1V

69
Chng tc dng mnh vi S, P, As; giy bc chy ngay khi tip xc vi

dung dch HClO3 40%
Cc axit ny kh mnh, mnh gim t HClO3 n HIO3 . Chng c

iu ch bng cc phn ng trao i:
Ba(ClO3)2 + H2SO4 2HClO3 + BaSO4
NaIO3 + H2SO4 HIO3 + NaHSO4
ring HIO3 c th iu ch bng phn ng:
3I2 + 10HNO3 6HIO3 + 10NO + 2H2O
Mui halogenat XO3- bn hn axit rt nhiu. Ion XO3- c cu

to hnh chp tam gic u. Cc gc OClO, OBrO, OIO ln
lt bng 1070, 1020, 990; di ca cc lin kt Cl-O, Br-O,
I-O bng 1,57; 1,68; 1,82A0; tan ca cc mui gim t clorat n iodat.
trng thi rn cc halogenat u c tnh oxy ha mnh v kh nng gim t
ClO3- IO3-. Cc XO3- c th c iu ch theo phng php chung l cho
halogen tc dng vi dung dch kim nng, hoc in phn dung dch MX nng.
t0
3Cl2 + 6KOH KClO3 + 5KCl + H2O
Ring IO3- c th iu ch theo phn ng:
I2 + 2KClO3 2KIO3 + Cl2
Trong cc mui halogenat, quan trng nht l KClO3 . N c dng lm

pho v dim.
VII.5.5. AXIT PEHALOGENIC (HXO4)
Hai axit quan trng l axit HClO4 v HIO4
1. Axit pecloric HClO4
HClO4 c cu to nh sau:
70
HClO4 l mt cht lng khng mu rt linh ng, bc khi mnh trong

khng kh, ha rn -1120C, d tan trong nc v to vi nc nhng hydrat
HClO4.nH2O (n= 1;2;3). HClO4 km bn nhit, v vy HClO4 khan l cht oxy
ha mnh cc cht hu c nh than, g; giy bc chy v n khi tip xc vi
axit khan.
Trong dung dch nc, HClO4 l axit mnh nht trong mi axit bit.
N cng l axit trong cc dung mi nh H2SO4, HNO3, CH3COOH. Mui ca
axit HClO4 gi l peclorat ClO4-. Cc ClO4- u tan tt, tr KClO4, RbClO4,
CrClO4 t tan trong nc lnh nhng tan tt trong nc nng.
KClO4 c tnh oxy ha mnh, nht l khi un nng. V vy hn hp

KClO4 vazlin c dng lm cht n.
So snh tnh cht ca cc oxy axit ca clo ngi ta nhn thy trong dy
HClO - HClO2 - HClO3 - HClO4 tnh axit tng dn. HClO l mt axit yu (yu
hn c H2CO3), HClO2 l axit trung bnh, HClO3 l axit mnh, HClO4 l axit
mnh nht trong tt c cc axit. iu ny c gii thch bng s gim bn
ca lin kt O-H khi s nguyn t oxy tng, do mt electron b ko v pha
lin kt ClO tng dn theo chiu tng mc oxy ha ca clo.
Trong dy ClO-, ClO2-, ClO3- ClO4- bn ca cc ion tng dn ln. iu

ny c gii thch ch s electron tham gia to thnh cc lin kt v tng
ln khi i t ClO- ClO4-. Do bn trong dy ClO- ClO4- tng ln m hot
tnh oxy ha gim xung. Chng hn cc hypoclorit tham gia vo phn ng oxy
ha kh trong bt k mi trng no.
NaClO + 2KI + H2O NaCl + I2 + 2KOH
Trong khi ClO3- ch oxy ha trong mi trng axit mnh:
71
NaClO3 + KI + H2SO4 NaCl + 3I2 + 3K2SO4 + 3H2O
Kh nng oxy ha kh ca cc oxit v oxy axit ca clo c trnh by tm

tt trong s th in cc sau y:
+1,15 ClO2 +1,27
ClO4- +1,19 ClO3- +1,21 HClO2 +1,64 HClO +1,63 Cl2 +1,36 Cl- (mt
axit)
+0,5 ClO2 +1,16
ClO4- +0,36 ClO3- +0,33 ClO2 +0,66 ClO- +0,4 Cl2 +1,36 Cl- (mt
baz)
+0,5 +0,89
Axit HClO4 c dng trong ha phn tch y mt axit d bay hi hn ra

khi mui, n c iu ch bng tng tc ca mui KClO4 vi axit H2SO4
c
KClO4 + H2SO4 = KHSO4 + HClO4
2. Axit peiodic HIO4
Trong dung dch, axit peiodic tn ti di dng ion t din IO4-. Axit ny
d b hydrat ha to ra cc axit H5IO6 (HIO4.2H2O), H3IO5 (HIO4.H2O). Dng
axit quan trng l axit parapeiodic H5IO6, c cu trc bt din.
Axit H5IO6 l cc cht dng tinh th khng mu, nng chy 1220C v
d tan trong nc. trong nc axit parapeiodic phn ly kh yu
H5IO6 + H2O H3O+ + H4IO6- K = 5,1.10-4
72
Mui ca axit peiodic gi l peiodat v hu ht cc mui u t tan trong

nc. Chng c to nn khi cho clo tc dng vi iodat trong mi trng
kim:
NaIO3 + 3NaOH + Cl2 Na2H3IO6 + 2NaCl
c im ch yu ca axit peiodic v mui peiodat l c tnh oxy ha

mnh (mnh hn axit iodic v mui iodat) nn c dng trong ha phn tch
lm cht oxi ha, chng hn chuyn ion Mn2+ v MnO4-
ta c s th in cc
H5IO6 + 0,7 IO3- +1,14 HIO+1,45 I2 +0,53 I- (mt axit)

1,2
H3IO62- +0,7 IO3- 0,14 IO- 0,45 I2 0,53 I- (mt baz)
10,29
Axit parapeiodic c th c iu ch bng phn ng:
Ba5(IO6)2 + 5H2SO4 5BaSO4 + 2H5IO6
VII.6. CC HALOGEN GI (tham kho)
Mt s nhm nguyn t v nguyn t c tnh cht ging halogen c

gi l halogen gi. Hin nay ngi ta tch c trng thi t do nhng
halogen gi sau y: xyanogen (CN2), oxyxanogen (OCN)2, thioxyanogen
(SCN)2, selenxyanogen (SeCN)2, azit cacbon isulfua (SCSN3)2.
Cc halogen gi c nhng tnh cht ha l ging nh halogen:
- Tt c u d bay hi.
73
- Chng u l cht oxi ha. Khi oxi ha, chng to mui ging
halogenua. Cc mui halogen gi l xyanua cha CN-, xianat cha OCN-,
thioxianat SCN-...
- Cc halogen gi mnh c th y halogen gi hay halogen tht yu hn

ra khi mui. V d: 2SCN- + Br2 (SCN)2 + 2Br-
2I- + (SCN)2 I2 + 2SCN-
Trong mt s trng hp ion halogen gi c th b nhng cht oxy ha

khc oxy ha thnh halogen gi t do:
MnO2 + 4H+ + 2SCN- = Mn2+ + (SCN)2 + 2H2O
Halogen gi ca ion Ag+, Hg22+, Pb2+ u t tan trong nc ging nh

halogenua tng ng. Cc hp cht vi hydro cng ging nh HX, dung dch
ca chng c tnh axit nhng yu hn dung dch HX.
Cc halogen gi c th c iu ch nh sau:
-Xianogen c th iu ch bng cch un nng AgCN hay hn hp HgCl2 -

Hg(CN)2
2AgCN 2Ag + (CN)2
Hg(CN)2 + HgCl2 Hg2Cl2 + (CN)2
Tioxyanogen c iu ch theo phn ng
Br2 + 2AgSCN 2AgBr + (SCN)2
74
CHNG VIII. CC NGUYN T PHN NHM VIA
Nhm VI A Gm cc nguyn t : O, S, Se, Te v Po.
c im ca nguyn t
Nguyn Cu hnh e nguyn Nng lng ion ha (kcal/ntg) m

Z
t t I1 I2 I3 I4 in
O 8 [He] 2s2 2p4 314 810 1267 1785 3.5
S 16 [Ne] 3s2 3p4 239 540 807 1091 2.5
Se 34 [Ar] 3d10 4s2 4p4 225 496 738 989 2.4
Te 52 [Kr] 4d10 5s2 5p4 208 429 720 880 2.1
Po 84 [Xe] 4f14 4d10 6s2 194

6p4
- Cu hnh electron ha tr ns2 np4 gn vi cu hnh bn ca kh tr, cc

nguyn t phn nhm VIA tr P o v Te th hin r tnh cht ca mt nguyn t
khng kim loi. Chng d dng kt hp thm electron ca kim loi kim, kim
th v mt s kim loi khc to nn hp cht ion, trong chng c mc oxy
ha -2. Mc ion ca nhng hp cht ny gim theo chiu gim ca m
in.
- t c cu hnh bn ca kh tr, chng cn c th to nn hai lin

kt cng ha tr cho nhng hp cht trong chng c mc oxy ha +2 (i vi
nguyn t m in hn) hoc -2 (i vi nguyn t km m in hn). Vi oxy
v cc nguyn t m in hn chng cn c th to nn 4 hoc 6 lin kt cng
ha tr chi nhng hp cht trong chng c mc oxy ha +4 hoc +6.
75
- Ngoi kh nng chung ca cc nguyn t nguyn t nhm VIA (tr O)

c th dng orbital d lai ha vi cc orbital s v p to nn hn 4 lin kt vi
cc nguyn t khc v cho nhng hp cht trong chng c s phi tr cao.. Se
v c bit l S cn dng nhng orbital d trng to nn lin kt (chng hn
ion SO42-).
VIII.1. OXI
VIII.1.1. Tnh cht l hc
- Nguyn t O c cu hnh electron: 1s2 2s2 2p4. L nguyn t u tin ca phn

nhm VIA, thuc chu k 2 v l nguyn t c s electron ho tr ln hn s
obitan ho tr nn oxy c nhiu c tnh khc hn cc nguyn t cng phn
nhm.
Tnh cht ca nguyn t
Bn knh CHT (nm) NL ion ha th nht I1 m in

(eV)
0.066 13.61 3.5
- Do c bn knh nh, c 2 electron c thn v l nguyn t c m in ln

(ch km F), s oxyho c trng nht ca oxy l -2, s oxyho +2 ch gp trong
cc hp cht vi F.
- Trong cc hp cht c s to thnh lin kt gia cc nguyn t O- O n c th

c s oxyho +1.
- Oxy c kh nng to lin kt vi nhau to thnh cc mch O-O-, [O-O]-,

[O-O-O]- Tuy nhin kh nng to mch cha cao, mch km bn v thng ch
cha ti a 4 nguyn t.
- Ho tr v s phi tr cc i ca oxy trong cc hp cht cng ho tr l 4,

nhng mun t n ho tr v s phi tr ny, nguyn t oxy phi s dng cp
electron cha lin kt ca mnh to lin kt cho nhn vi nguyn t ca nguyn
t khc. Chnh v vy, ho tr v s phi tr thng gp ca oxy l 2
76
Oxygen tn ti 2 dng th hnh: oxy (O2) v ozn (O3). Dng bn nht l O2.
Oxy tn ti dng phn t 2 nguyn t (O2). Theo phng php MO, cu hnh
electron ca phn t l: (S)2 (S*)2 (Z)2 (X , Y)4 (X* , Y*)2 ng vi bi
lin kt l 2, c th biu din cu trc phn t nh sau:
:O - O: hoc : O - O:
Ngha l trong phn t c mt lin kt 2 electron v 2 lin kt c bit, mi lin

kt gm 3 electron. Cc cng thc ny ph hp vi tnh cht thun t ca oxy,
cn cng thc Lewis :O:: O: khng ph hp vi iu ny. Khong cch gia cc
oxy trong phn t oxy l 0,1207nm, ngn hn so vi lin kt n O - O
(0,148nm) do phn t O2 rt bn vng v c phn cc nh.
O2 2O Hpl =118 kcal/mol.
Oxy ch phn ly thnh nguyn t nhit ln hn 20000C hoc khi chiu tia
t ngoi.
Oxy c nhit nng chy v nhit si thp (t0nc = - 218,9 0C, t0s = -183 0C)
trng thi rn c mng tinh th phn t. nhit bnh thng, oxy l mt
cht kh khng mu, khng mi v, t tan trong nc( 900C, 100 th tch nc
ho tan c 5 th tch oxy).
VIII.1.2. Tnh cht ha hc
Oxy l mt trong nhng khng kim loi hot ng mnh nht. Kh nng
phn ng ca oxy tng rt mnh khi c xc tc v nhit cao.
- Ngay nhit thng, oxy c kh nng phn ng vi nhiu n cht v

hp cht gy ra cc hin tng thng c gi l s oxy ho hoc s r. Oxy
tc dng trc tip vi tt c cc kim loi to thnh oxyt, peoxit tr Au, Pt (i
vi Ag th Ag2O ch to thnh khong 200 - 2500C, nu nhit cao hn th
Ag2O li b phn hu).
4Na + O2 2Na2O
2Na + O2 Na2O2
77
- i vi cc phi kim, tr halogen, kh tr, oxy tc dng trc tip nhng thng
thng cn c nhit .
C + O2 CO2
N2 + O2 2NO ( 20000C hoc tia la in)
Phn ng ca oxy vi nhiu hp cht, n cht, nhiu phn ng to ra nhit

lng ln v pht sng, thng c gi l s chy.
VIII.1.3. Trng thi t nhin, phng php iu ch v ng dng
Trng thi t nhin
Oxy l nguyn t ph bin nht. N chim 47% khi lng v 55%NT

ca cc nguyn t to thnh v tri t. Oxy c 3 dng ng v bn 16O
(99,759%), 17O (0,03%) v 18O (0,204%). Ngoi ra cn c cc ng v phng x
nhn to 14O, 15O c chu k bn phn hu vi chc giy.
Trong t nhin, oxy tn ti di dng t do hoc dng hp cht ca cc

nguyn t. Do c hm lng rt ln, li l nguyn t c hot tnh ho hc rt cao
nn oxy quyt nh dng tn ti ca hu ht cc nguyn t trong t nhin.
iu ch
- Trong cng nghip, ch yu oxy c iu ch bng phng php ho lng

khng kh, sau chng ct phn on khng kh lng. i khi ngi ta cng
iu ch bng cch in phn nc
- Trong phng th nghim: thng s dng oxy c nn trong cc bnh thp.

Khi mun iu ch lng nh oxy, c th phn hu nhit cc hp cht giu oxy
nh KMnO4, KClO3, HgO:
2HgO 2Hg + O2
o
2KClO3 MnO
,t
2KCl + 3O2
2
2KMnO4 K2MnO4 + MnO2 + O2
78
ng dng
ng dng ch yu ca oxy l d to nhit cao cn thit cho qu trnh

luyn kim, nu chy Pt, thch anh. Oxy lng c dng cho k ngh tn la.
Oxy cng c dng trong y hc cha cc bnh trong h hp.
VIII.1.4. Ozon:
a. Cu to phn t L tnh
Phn t ozn O3 trc y mt thi gian di c coi c cu to vng kn
O O
Nhng cu to khng ph hp vi l thuyt hin i. V mt nhit ng hc,

phn t c cu to nh vy khng th c c. V nng lng phn hy ca
phn t O2 ch khong 118 kcal v nng lng lin kt cng ha tr O O
l 30 kcal nn entanpy ca phn ng 3 O2 2 O3 c tnh theo chu trnh
sau:
3 x 118
3 O2 6O
H 6 x 30
2 O3
phi l: H = 354 - 180 = 174kcal. Nhng gi tr thc nghim xc nh c

l 68 kcal. Mt khc momen lng cc phn t xc nh c cng khng ph
hp vi cu to i xng .
Phn t ozon c cu to dng gc
O
1,278 A0
1170
O O
79
Ngha l trong mi phn t O3 c 2 lin kt v mt lin kt khng nh ch.
iu kin thng ozn l mt cht kh c mu xanh da tri v c mi

c bit. Phn t O3 c khi lng tng i ln, c cc v d b phn cc ho
nn ozn c nhit nng chy v nhit si cao hn oxy (t 0s = -111,9 0C ,
t0nc = - 192,7 0C). Ozon lng c mu tm v t khi l 1,71. Ozon rn c mu
tm en. L phn t c cc (momen lng cc = 0,52D), ozon tan trong nc
nhiu hn oy 15 ln
b. Ha tnh
- Ozon km bn d b phn hu
2O3 3O2 H = - 285kJ
Do d phn hu cho oxy nguyn t nn ozon hot ng hn oxy nhiu. Trong

cc phn ng n s gii phng ra O2
- iu kin thng, ozon c th oxy ho c nhiu n cht v hp cht c

hot tnh rt km bn l cc cht m O2 ch tc dng nhit cao
2Ag + O3 Ag2O + O2
2KI + O3 + H2O 2KOH + I2 + O2
PbS + 4 O3 PbSO4 + 4 O2
Nhiu cht hu c phn ng mnh lit vi ozon (bng, este, du thng...

bc chy khi tip xc vi ozon).
C th thy r tnh oxy ho ca ozon khi so snh th oxyho - kh ca n

vi oxy
O3 (k) + H2O + 2e O2 (k) + 2OH- (dd) 0 = 1,24V
O2 (k) + 2 H2O + 4e 4OH- (dd) 0 = 0,4V
O3 (k) + 2 H+ + 2e O2 (k) + H2O 0 = 2,07V
O2 (k) + 4 H+ + 4e 2 H2O 0 = 1,229V

80
Ozon tc dng vi cc kim loi km to ra ozonua
K + O3 KO3
c. iu ch
- Trong t nhin, ozon c hnh thnh tng kh quyn cao (10 - 30km) nh
tc dng ca tia t ngoi ln oxy. Phn ng xy ra theo s chui:
O2 + h O2*
O2* + O2 O3 + O
O + O2 O3
Phn ng ny c ngha rt ln v phn ln nhng tia t ngoi c hi cho

s sng u b gi li.
- iu ch ozon trong k thut, thng dng phng php phng in

m qua kh quyn oxy c p sut thp.
- Trong phng th nghim, iu ch mt lng nh ozon ta c th s

dng phn ng ca (NH4)2S2O8 vi HNO3 hoc H2SO4 m c
d. ng dng
Ozon c s dng trong thc t do tnh oxy ho mnh ca n, n thng

c dng st trng nc ung v khng kh hoc trong tng hp ho hc
khc nhau.
VIII.1.5. Oxit ca cc nguyn t
Oxit theo ngha rng l hp cht ca oxy vi mt nguyn t khc. Oxit

ca cc nguyn t c bn cht rt khc nhau. Kiu lin kt ho hc trong cc
oxit bin i tng thun tu ion n thun tu cng ho tr
S to thnh ion O2- t O2 tiu tn mt nng lng kh ln
1/2O2 (k) O (k) H = 59kcal/mol
81
O + 2e O2- (k) H = 157kcal/mol
1/2O2 (k) + 2e O2- (k) H = 216kcal/mol
Mun to thnh oxy ion cn tiu tn mt nng lng ln lm cho

nguyn t kim loi bay hi v ion ho, nhng mt khc nh nng lng mng
li ca oxit cha ion O2- tng i b (1,4 A0) l rt cao cho nn nhiu oxit
thun tu ion v rt bn.
Da vo tnh cht ho hc ngi ta phn chia oxit ca cc nguyn t ra

lm oxit baz, oxit axit, oxit lng tnh, oxit trung tnh.
Oxit baz
l cc oxit ca kim loi nh kim loi kim, kim th. Thng l

cc cht rn c nhit nng chy cao, nhiu cht tan trong nc cho mi
trng kim
Na2O + H2O 2NaOH
BaO + H2O Ba(OH)2
Mt s khng tan trong nc nhng tan c trong cc axit
MgO + 2HCl MgCl2 + H2O
Oxit axit
L cc oxit ca cc khng kim loi v cc khng kim loi s oxiho cao.

Lin kt trong cc oxit ch yu mang tnh cht cng ho tr, in tch m hiu
dng trn nguyn t oxy rt nh. trng thi rn, chng thng c mng tinh
th phn t hoc cu trc phn lp, mch, nn nhit nng chy khng cao.
Oxit axit gi l anhydrit l oxit tan c trong nc to thnh axit tng

ng
V d: SO3, N2O5, Cl2O7
SO3 + H2O H2SO4
82
N2O5 + H2O 2HNO3
Nhng oxit axit khng tan trong nc c th tan trong dung dch kim
hoc trong kim nng chy.
SiO2 + 2NaOH (r) Na2SiO3 + H2O
Sb2O5 + 2NaOH + 5H2O 2Na [Sb(OH)6]
Oxit lng tnh
Cc kim loi km hot ng cc s oxit ho khng cao to cc oxit c

tnh cht trung gian gia oxit axit v oxit baz. Lin kt trong hp cht c tnh
ion cng ho tr
V d: Al2O3 , Cr2O3, ZnO ... thng l cc cht rn, khng tan c trong
nc, nhng tan c trong c axit v kim.
ZnO (r) + 2H+(dd) Zn2+ (dd) + H2O
ZnO (r) + 2OH- (dd) + H2O Zn(OH)42-
Cch phn chia ra oxit baz, oxit axit v oxit lng tnh l da vo tnh
axit - baz ca oxit trong dung dch nc, cch phn chia nh vy cng ph hp
vi cch phn chia oxit da vo kiu lin kt ho hc
Ta c bng sau:
Tnh axit tng, tnh cng ha tr tng
Li2O BeO B2O3 CO2 N2O5 F2 O
Na2O MgO Al2O3 SiO2 P4O10 SO3 Cl2O7
K2O CaO Ga2O3 GeO2 As2O3 SeO3 Br2O
Rb2O SrO In2O3 SnO2 Sb2O5 TeO3 I2O5
83
Cs2O BaO Tl2O3 PbO2 Bi2O5
Oxit baz Oxit Oxt axit

lng
tnh
Tnh baz tng, tnh ion tng
Nhn vo bng ta thy trong mt chu k, t tri sang phi tnh axit tng
ln cng vi tnh cng ho tr ca lin kt trong phn t oxit v ngc li tnh
baz gim xung cng vi tnh ion ca lin kt.
Oxit tr
Ngoi cc oxit thuc ba loi trn cn tn ti mt s oxit c nhng tnh

cht kh c bit, chng kh tr v phng din ho hc, khng tan trong nc
v khng tan c trong axit v baz.
V d: N2O, CO, MnO2, PbO2
Nu cc oxit ny phn ng vi axit hoc baz th phn ng khng phi l

phn ng axit - baz.
V d: MnO2 khng tan trong HNO3, H2SO4 nhng phn ng vi axit c.
MnO2 + 4HCl MnCl2 + Cl2 + 2H2O
l phn ng oxyho kh.
Peoxit
L cc oxit c cha ion O22-. Ion O22- c cu to [:O - O:]2-, cc kim loi
kim, kim th to nn peoxit. y l cc peoxit ion
V d: Na2O2, BaO2 cc oxit ny khi tc dng vi nc gii phng H2O2
Na2O2 + 2H2O 2NaOH + H2O2
84
Vy c th coi peoxit l mui ca H2O2, cng nh H2O2 peoxit l cht oxiho

mnh nhng vi cht oxiho mnh hn, n th hin tnh kh.
Supeoxit
L oxit c cha ion O2- trong mng li tinh th. Ion ny c cu to [:O
O ]. Cc kim loi kim cho supeoxit v d: KO2, RbO2.
Khc vi peoxit, khi tc dng vi nc ngoi H2O2, supeoxit cn gii phng O2
4KO2 + 6H2O 4KOH + 4H2O2 + O2
V vy supeoxit l cht oxit mnh.
Ozonit
L oxit c cha ion O3- trong mng li tinh th ion ny c cu to

tng t ozon:
Ngi ta bit c ozonit ca kim loi kim nh KO3, RbO3. Khi tc dng vi
nc chng khng gii phng H2O2 m gii phng oxy vi lng nhiu hn
4KO3 + 2H2O = 4KOH + 5O2
VIII.1.6. Hidroxit
Hu ht cc hidroxit c cng thc tng qut OmX(OH)n trong m l s
nguyn t oxi trong phn t lin kt trc tip vi cc nguyn t trung tm X m
khng lin kt trc tip vi nguyn t hidro. C ba loi hidroxit l hidroxit bazo,
hidroxit axit v hidroxit lng tnh
Hidro bazo l hidroxit tng ng vi oxit vi
VIII.2. LU HUNH
VIII.2.1. n cht
Tnh cht vt l
- Lu hunh thng tn ti di mt s dng th hnh khc nhau, hai

dng ph bin l t phng v n t.
85
- S t phng (S) c mu vng, nng chy 112,8 0C v c t khi l

2,06. N bn nhit thng v trn 95 0C n chuyn sang dng n t. V
th S tn ti trong t nhin dng t do l S t phng)
- S n t (S) c mu vng nht, nng chy 119,2 0C v c t khi l

1,96. N bn trn 950C. Di nhit n chuyn sang dng t phng. Nh
vy 2 dng th hnh chuyn ha cho nhau:
S S H = 0,096 kcal/ptg
- S v S u khng tan trong nc, tan nhiu trong dung mi hu c.
- C 2 dng S v S u gm
nhng phn t 8 nguyn t . Khi un n
nng chy, S bin thnh cht lng trong
sut, linh ng, mu vng. n trn 160
0
C, S nhanh chng c mu nu v
nht dn, n 200 0C th n c qunh li
ging nh nha v c mu nu en.
Tnh cht bt thng ny ca S khc vi bt k cht lng no (khi un nng,

nht lun gim xung. iu ny c gii thch l cc phn t vng S8 b t ra
v ni li vi nhau thnh mch polyme di.
Tnh cht ha hc
- S l nguyn t tng i hot ng, nhit thng hi km hot ng,

nhng khi un nng th c th tc dng vi nhiu nguyn t (tr kh tr, N2 , I2,
Au v Pt).
- Khi un nng 3000C, n tng tc vi H2 to dihydrosunfua, phn ng xy

ra kem mnh lit hn so vi phn ng gia H2 v O2:
S + H2 H2S
- S tc dng vi kim loi to sunfua kim loi: vi cc kim loi kim v kim th,
Ag, Hg, phn ng xy ra nhit thp; vi Cr, Co, Ni xy ra nhit cao.
86
- S chy trong O2 cho ngn la mu xanh lam nht, ng thi to nn SO3 mt

t l b:
S + O2 SO2
- Tnh kh ca S th hin khi tng tc vi cctttt oxy ha mnh nh KNO3,

KClO3, K2Cr2O7, HNO3 , H2SO4 c:
KClO3 + S KCl + SO2
H2SO4 + S SO2 + H2O
- S tuy khng tan trong nc, nhng c th tan tt trong dung dch kim hoc
kim nng chy
S + NaOH Na2S + N2SO3 + H2O
Tan trong dung dch sunfua, dung dch sunfit:
S2- + nS Sn+12- (poly sunfua)
SO32- + S S2O32- (tiosunfat)
Trng thi t nhin v phng php iu ch
- Lu hunh c th tn ti trng thi t do, cc khong vt ph bin l

saufua nh pyrit (FeS2), chancopyrit (FeCuS2).
- Ngi ta khai thc S trng thi t do bng cch ha lng ri bm ln

khi m. Ngi ta ha lng S bng cch dng h thng ng gm 3 ngd ng
tm vi nhau, ng ngoi cng cha nc nng n 170 0C, ng trong cng ht S
lng ln. tinh ch S, ngi ta s dng phng php ha hi S ri cho ngng
t li.
VIII.2.2. CC HP CHT QUAN TRNG CA LU HUNH
VIII.2.2.1. Dihydro sunfua
87
- S to nn vi H mt s hp cht c cng thc chung l H2Sn (n= 1 6)

gi l sunfan trong hp cht n gin nht l H2S.
- Phn t H2S c cu to tng t phn t H2O vi gc lin kt HSH bng

92,2 , di lin kt S - H bng 1,33A0. Tuy nhin v nhiu tnh cht H2S rt
0
khc so vi H2O. S c m in b hn oxy nn lin kt hydro gia cc phn

t H2S vi nhau rt nh nn iu kin thng n l cht kh, khng mu, c
mi trng thi v rt c. trng thi lng n phn ly ging nh H2O nhng
mc km hn nhiu:
H2S + H2S H3S+ + HS- KH2S = 3.10-33
- Trong dung dch nc , H2S l mt axit 2 nc v yu hn c axit

cacbonic:
H2S + H2O H3O+ + HS- K1 = 10-7
HS- + H2O H3O+ + S2- K2 = 10-14
N to thnh 2 mui tng ng l hydrosunfua cha ion HS- v mui

sunfua cha ion S2-.
- Tnh cht ha hc c trng ca H2S l cht kh mnh. N chy trong

O2 cho ngn la khng mu:
D O2 : H2S + O2 SO2 + H2O
Thiu O2 H2S + O2 S + H2 S
Phn ng ny dng thu hi S t kh thi c cha H2S. Ngi ta trn kh

thi vi mt lng xc nh khng kh v cho hn hp i qua bt boxit un nng
ta s thu c S t do.
- Dung dch nc ca H2S lu trong khng kh cng s b O2 khng kh

oxy ha to S t do lm dung dch vn c.
- Vi cc cht oxy ha mnh nh Cl2, KMnO4, K2Cr2O7H2S tng tc

d dng to S t do
88
KMnO4 + H2S + H2SO4 MnSO4 + S + K2SO4 + H2O
I2 + H2S S + HI
Phn ng sau c dng nh lng H2S trong hn hp vi cc kh

khc.
VIII.2.2.2. Sunfua kim loi
Sunfua kim loi l hp cht gia S vi kim loi. Do S c m in b

hn O nn trong sunfua kim loi lin kt mang tnh cht cng ha tr nhiu hn
so vi lin kt gia kim loi v O trong oxit.
- Cc kim loi kim v kim th to nn sunfua ion. Tt c chng u tan

trong nc (tr BeS). Dung dch ca chng c mi trng baz do phn ng
thy phn:
S2- + H2O HS- + OH-
Nh vy nhng sunfua ny tng ng vi oxit baz.
- Al2S3 cng c xem l sunfua ion v chng b thy phn hon ton
trong nc:
Al2S3 + H2O H2S + Al(OH)3
- Ngoi sunfua kim loi kim, kim th v mt vi kim loi khc, cc

sunfua kim loi u c cu trc phn t cng ha tr khng l. Chng c th c
cu trc mch thng nh Sb2S3, Bi2S3, cu trc lp nh TiS2, SnS2, MoS2, FeS2,
ZnS, HgS, PtS Hu ht chng u khng tan trong nc.
- Da vo tan, ngi ta chia sunfua kim loi lm 3 loi:
Sunfua tan trong nc: Na2S, K2S, BaS, Al2S3, Cr2S3,
Sunfua khng tan trong nc nhng tan c trong axit long: MnS, FeS,
CoS, NiS, ZnS
89
Sunfua khng tan trong nc v trong axit long: CuS, Ag2S, CdS, HgS,
SnS, PbS, As2S3
Ha hc phn tch da vo s khc nhau v tan ca cc sunfua kim loi

phn chia cc ion kim loi bng H2S .
VIII.2.2.3. Sunfu dioxit

S
1,43 A0 Lu hunh to nn mt s oxit c cng thc nh S2O,

1200 SO, S2O3, SO2 , SO3 nhng quan trng nht trong thc
O O t l SO2 v SO3 . Phn t SO2 c cu to gp khc nh
cc phn t O3, NO2 .
Trong phn t SO2 , nguyn t S trng thi lai ha

sp2, 2 orbital lai ha c dng to 2 lin kt vi
2 nguyn t O., mt orbital lai ha cha cp in t
ghp i.
Ngoi ra nguyn t S cn c 1 orbital 3p khng lai ha cha 1 electron

c thn, orbital ny s to lin kt khng nh ch vi orbital 2p cha 1
electron c thn ca O.
iu kin thng SO2 l mt kh khng mu, mi kh chu, d ha lng.

Dung dch SO2 trong nc c mi trng axit yu:
SO2 + n H2O SO2.nH2O
SO2.nH2O H3O+ + HSO3- + (n - 2) H2O
Nh vy, tuy H2SO3 khng tn ti nhng ngi ta bit r 2 mui ng vi

axit 2 nc l hydrosunfit cha ion HSO3- v mui sunfit cha ion SO32-
NaOH + SO2 NaHSO3
NaOH + NaHSO3 Na2SO3
- Cc hydrosunfit v sunfit ca cation khng mu u khng c mu. Ch

c sunfit ca kim loi kim v hydrosunfit ca kim loi kim v kim th mi
tan. Khi tan mui sunfit b thy phn cho mi trng kim, cn mui
90
hydrosunfit cho mi trng axit. Mui sunfit bn hn mui hydrosunfit. Mui

sunfit ca kim loi kim b nhit phn 600 0C to thnh sunfat v sunfua:
K2SO3 K2SO4 + K2S
- Mui hydrosunfit kim loi kim mt dn nc to thnh disunfit:
KHSO3 K2S2O5 + H2O
- Cc cht oxy ha nh HNO3 , KMnO4 , K2Cr2O7 oxy ha SO2 ,

hydrosunfit v sunfit n axit sunfuric hay sunfat:
HNO3 + SO2 H2SO4 + NO2
Cl2 + Na2SO3 + H2O Na2SO4
- Vi cc cht kh mnh hn SO2 th hin tnh oxy ha:
SO2 + H2S S + H2O
SO2 + H2 S + H2O
SO2 + C S + CO
Nhng phn ng ny trong cng nghin c s dng thu hi S t SO 2
- SO2 c dng ch yu iu ch H2SO4, Ca(HSO3)2 dng trong vic

ty trng si, ng, sn xut xeluloz...
- Trong cng nghip n c iu ch bng cch t cc qung sunfua

kim loi trong oxy:
FeS2 + O2 Fe2O3 + SO2
VIII.2.2.4. Sunfu trioxit (SO3 )
O Phn t SO3 c cu to hnh tam gic u, gc lin kt

OSO = 1200, di lin kt S O bng 1,43A0 . Trong
phn t SO3 nguyn t S trng thi lai ha sp3, 3 AO
S
1,43 A0
lai ha sp3 to thnh lin kt vi orbital 2p ca 3
1200 91
O O
nguyn t O, mt orbital 3p cn li ca S khng lai ha

cha electron c thn tham gia to lin kt vi
orbital 2p c electron c thn ca O, lin kt ny
khng nh ch. Ngoi ra trong phn t SO3 ngoa lin
kt kiu p - p cn c mt phn lin kt theo kiu p
d.
- SO3 tng tc mnh lit vi to thnh axit H2SO4 , do SO3 l

anhydrit sunfuric, phn ng ny pht ra nhiu nhit nn khi cho mt t SO3 vo
nc ta nghe thy ting xo xo, ngc li cho tng git nc vo SO3 th phn
ng pht n:
SO3 + H2O H2SO4 H = -21,3 kcal/mol
- SO3 kt hp vi HF, HCl to thnh axit halogensunfonic:
SO3 + HCl HSO3Cl
y l mt cht oxi ha mnh, n tng tc vi halogenua ca cc kim

loi v khng kim loi gii phng halogen:
SO3 + HCl HSO3Cl
- SO3 l sn phm trung gian ca qu trnh iu ch H2SO4, trong cng

nghip n c iu ch bng cch oxy ha SO2 bng O2 khng kh vi xc tc
l V2O5
VIII.2.2.5. Axt sunfuric (H2SO4 )
H O O - Phn t H2SO4 c cu to hnh t din lch vi

nguyn t S tm vi ds - OH = 1,53 A0 , dS - O = 1,46
O
A0 .
H O O
- Axit H2SO4 l cht lng nng, snh nh du, khng
c mu v mi, ha rn 10,40C. Khi un si axit,
mi u axit cho hi giu kh SO3 , n khi dung
dch c nng 98,2% th si 3380C , l hn
hp ng si ca H2SO4 v nc.
92
- Axt H2SO4 tinh khit l dung mi ion ha, bn thn axit cng t ion ha
theo s :
H2SO4 + H2SO4 H3SO4+ + HSO4-
Trong axit H2SO4 nhiu axit thng thng s l baz:
CH3COOH + H2SO4 CH3COOH2+ + HSO4-
Nhng axit mnh nh HClO4 th vn l axit
HClO4 + H2SO4 H3SO4+ + ClO4-
- Axit H2SO4 tinh khit c th ha tan kh SO3 vi bt k t l no do to

thnh mt lot cc axit polysunfuric: H2S2O7, H2S3O10, H2S4O13, H2Sn +1 O3n +4 .
O O O O O
HO O OH HO O O OH
S S S S S
O O O O O
(Axit disunfuric) (Axit trisunfuric)
Hn hp ca cc axit gi l oleum, l mt cht lng rt nht v khng

c mu. iu kin thng oleum gii phng ra kh SO3 nn bc khi mnh
trong khng kh . Khi un nng, kh SO3 tan s bay ra l nhit si ca axit
s tng ln lin tc cho n khi t nng 98,2% axit sunfuric th nhit si
khng bin i na.
- Axit sunfuric tan v hn trong nc, qu trnh ha tan pht ra nhiu

nhit, c 1 mol axit sunfuric tinh khit vo vo mt lng ln nc th pht
ra mt lng nhit l 19,5 kcal. V th khi pha long H2SO4 th phi thm dn
H2SO4 vo nc, tuyt i khng c lm ngc li v nh th nc s si ln
t ngt s lm bn tung te axit v c th gy n. Lng nhit pht ra nhiu khi
axit sunfuric tan trong nc l do qu trnh hydrat mnh ca phn t H2SO4 .
93
- Axit sunfuric c hp th mnh hi nc nn thng c dng lm

kh nhng kh khng tng tc vi n. N c th ly nc ca nhiu hp cht
hu c nh xenlulozo, ng v bin chng thnh cacbon.
C12H22O11 12C + 11H2O
- Axit sunfuric l mt axit mnh 2 nc:
H2SO4 + H2O H3O+ + HSO4-
HSO4- + H2O H3O+ + SO42-
Trong dung dch long, nc 1 thc t xy ra hon ton, nc 2 vi hng s K =

10-2.
- H2SO4 l axit mnh v kh bay hi nn n c dng vo vic iu ch

nhng axit khc d bay hi hn.
- Axit sunfuric tuy khng phi l cht oxy ha mnh lm nhng dung dch
m c c tnh oxy ha nht l khi un nng. N oxy ha HI thnh I2, H2S
thnh S v mt phn HBr thnh Br2 , ha tan nhng kim loi km hot ng nh
Cu, Hg, Ag v mt s phi kim nh C, S...
Cu + H2SO4 CuSO4 + SO2 + H2O
C + H2SO4 CO2 + SO2 + H2O
- Dung dch H2SO4 long ha tan cc kim loi hot ng nh kh nng

oxy ha ca H3O+
Fe + H2SO4 FeSO4 + H2
- Axit sunfuric c (> 75%) ngui khng tc dng vi Fe, Al (s th ng

ha)
- Trong cng nghip axit sunfuric c iu ch theo 2 phng php:

bung ch v tip xc:
94
+ Phng php bung ch: kh SO2 c oxy ha bng O2 khng kh vi

cht xc tc l hn hp kh NO + NO2 , phn ng to ra nitrozoni hydrosunfat:
SO2 + O2 + NO + NO2 + H2O NOHSO4
Ha tan sn phm ny trong bung bng Pb thu c axit sunfuric
NOHSO4 + H2O H2SO4 + NO + NO2
+ Phng php tip xc: kh SO2 c oxy ha bng O2 khng kh to

thnh SO3 . y l phn ng thun nghch v pht nhit. Theo nguyn l CDCB,
mun cn bng chuyn dch v pha to thnh SO3 th phi h nhit , nhng
nu h nhit n mt gii hn nht nh th vn tc phn ng s qu b. V
th cn phi dng cht xc tc: phn ng gia cc cht kh SO2 v O2 trn b
mt cht xc tc rn l V2O5 (nn gi l phng php tip xc
V2O5
SO2 + O2 500 0C SO3
V nc d to nn vi SO3 nhng ht sng m kh lng xung m ngi ta

khng dng nc m dng dung dch H2SO4 hp th SO3 to thnh oleum.
VIII.2.2.6. Mui sunfat
Axit sunfuric to nn 2 loi mui: sunfat (SO42-) v hydrosunfat (HSO4-).
- Ion SO42- c cu to t din u vi nguyn t S trung tm, dS O =

1,49A0. Trong ion SO42-, nguyn t S trng thi lai ha sp3, 4 AO sp3 tham gia
to 4 lin kt vi 4 nguyn t O. Ngoi ra cn c s to thnh lin kt theo
kiu p d do s xen ph ca AO 2p cha cp in t ghp i ca O vi AO
3s trng ca S. Lin kt ny khng nh ch trong ton ion SO42-
- 2-
- Ion HSO4- cng c O O
cu to hnh t din.
S S
- Hin nay ngi ta
HO O O O
bit c sunfat v v
O O
hydrosunfat ca tt c cc
95
kim loi. Ch c cc
hydrosunfat ca kim loi
hot ng mnh nht mi
tch ra trng thi rn nh
hydrosunfat ca Na+, K+
- Hu ht cc mui sunfat khng c mu, d kt tinh, tr CaSO4 hi t tan,

PbSO4, SrSO4 t tan v BaSO4 thc t khng tan.
- Ch c cc mui sunfat ca Na, K, Ca, Ba bn vi nhit, khng phn hy

1000 0C, cn cc mui sunfat khc u c th b phn hy nhit nhit
thp hn nhiu, bin thnh oxit kim loi v SO3. Hydrosunfat ca kim loi kim
nng chy nhit thp hn so vi sunfat. trn nhit nng chy,
hydrosunfat mt nc bin thnh disunfat:
2 NaHSO4 Na2S2O7 + H2O
nhit cao hn na, mui disunfat phn hy gii phng SO3 , li dng
tnh cht ny ngi ta nu chy hydrosunfat hay disunfat ca Na, K vi nhng
hp cht kh tan trong axit nh Al2O3 , Cr2O3, TiO2 chuyn chng thnh
nhng hp cht tan c
Al2O3 + Na2S2O7 Al2(SO4)3 + Na2SO4
- Cc mui sunfat tan thng to nn nhng mui kp. Cc sunfat ca

kim loi ha tr II to nn vi sunfat kim loi kim v amoni nhng mui kp c
cng thc chung: Me2SO4.MSO4.6H2O (Me: Na, K, Rb, NH4 ; M: Fe, Be, Mg,
Zn v Cd). Cc sunfat ca kim loi ha tr III to nn vi sunfat kim loi kim
v amoni nhng mui kp c cng thc chung: Me2SO4.M2(SO4)3.24H2O cn
gi l phn (Me: Na, K, Rb, NH4, Tl ; M: Al, Cr, Fe, Mn, Ti, V).
VIII.2.2.7. Axit tiosunfuric (H2S2O3)
- Axit H O O H O O
tiosunfuric c cu O hay O
to phn t tng
H S O H O S
t axit sunfuric.
96
Trong mt
nguyn t O c
thay bng nguyn
t S nn c gi
l axit tiosunfuric
(tio l lu hunh)
- L hp cht km bn, axit tiosunfuric phn hy d dng theo phn ng :
H2S2O3 S + SO2 + H2O
- nhit -780C, n tch ra trng thi t do khi cho kh H2S tc dng

vi axit closunfonic:
HSO3Cl + H2S H2S2O3 + HCl
- Axit tiosunfuric l mt axit mnh, mui tiosunfat ca kim loi kim

khng b thy phn khi tan trong nc.
- Ion S2O32- c cu to t din tng t SO42-, O

2-
dS - S = 1,99A0, dS = O = 1,48A0 . Qua ta thy rng

trong ion S2O32- lin kt S - S yu v lin kt S = O S
mnh, nn ion S2O32- km bn hn ion SO42-.
O O
- a s mui tiosunfat d tan trong nc. Cc O

mui tiosunfat ch, bc, tali (I) v canxi t tan.
- Trong ion S2O32-, ngoi mt nguyn t S vi

ha tr ging nh nguyn t S trong SO42-, cn c
mt nguyn t S vi ha tr ging nh nguyn t O
trong ion SO42- nn mui tiosunfat c tnh kh.
- Trong dung dch nc, mui tiosunfat b phn hy d dng bi axt to

thnh S v SO2 , tuy nhin phn ng khng xy ra ngay tc khc m mt lc sau
mi thy S kt ta
S2O32- + 2 H+ SO2 + S + H2O
97
Trong cc tiosunfat th quan trng nht l natri tiosunfat Na2S2O3.5H2O

(thng c gi khng ng l natri hyposunfit. 2200C n phn hy theo
phn ng :
4Na2S2O3 3Na2SO4 + Na2S5
Na2S5 Na2S + 4S
- Na2S2O3 b oxy ha d dng bi cc cht oxy ha mnh nh Cl2, HClO,

KMnO4 to thnh mui sunfat hay axit sunfuric:
Cl2 + Na2S2O3 + H2O Na2SO4 + HCl
Trong cng nghip ngi ta li dng phn ng ny loi ht phn t Cl 2

cn li sau khi vi c ty trng.
- Vi nhng cht oxy ha yu nh I2 n bin thnh natri tetrationat:
I2 + Na2S2O3 Na2S4O6 + NaI
Phng php phn tch nh lng da vo phn ng ny gi l phn ng

chun id.
- Dung dch Na2S2O3 c kh nng ha tan cc cht t tan nh AgCl, AgB,

AgI, HgI2 nh kh nng to phc:
AgBr + Na2S2O3 Na[Ag(S2O3)2] + NaBr
- Trong cng nghip , Na2S2O3 c iu ch bng cch dng O2 khng

kh hay cc cht oxy ha yu khc oxy ha Na2S2:
Na2S2 + O2 Na2S2O3
Ngoi ra n cn c iu ch bng cch cho S tc dng vi dung dch

Na2SO3 hay S d tc dng vi dung dch NaOH:
Na2SO3 + S Na2S2O3
VIII.2.2.8. Axit peoxysunfuric
98
C 2 axit peoxysunfuric thuc dn xut ca axit sunfuric l axit

peoxymonosunfuric H2SO5 (cn gi l axit Caro) v axit peoxydisunfuric
H2S2O8.
HO O O OH HO O
S S S
HO O O O O O O
H2SO5 H2S2O8
- Trong nc cng nh trong dung dch H2SO4 long, c 2 axit u thy

phn to thnh axit sunfuric v H2O2
H2S2O5 + H2O H2SO4 + H2O2
H2S2O8 + H2O H2SO4 + H2O2
- C 2 axit v mui ca chng u l cht oxy ha mnh:
MnSO4 + (NH4)2S2O8 + H2O HMnO4 + (NH4)2SO4 + H2SO4
Phn ng ny xy ra nhanh chng nh xc tc Ag+.
- Axit peoxydisunfuric c iu ch trong cng nghip bng cch in

phn dung dch H2SO4 m c (50%) 0 0C vi in cc bng Platin.
- Trong dung dch H2SO4 long, axit peoxydisunfuric thy phn to nn

axit peoxymonosunfuric:
H2S2O8 + H2O H2SO5 + H2SO4
- C 2 axit tinh khit c th c iu ch bng cch cho axit closunfonic

tng tc vi H2O2 :
HSO3Cl + H2O2 H2SO5 + HCl
HSO3Cl + H2O2 H2S2O8 + HCl
99
VIII.3. CC NGUYN T SELEN, TELU V POLONI
VIII.3.1. n cht
Tnh cht ha hc
- Tnh kim loi ca cc nguyn t nhm VIA th hin r nht poloni.

Trong khi O, S, l cht cch in, Se v Te l cht bn dn th Portland l cht
dn in. S bin i nh vy cng th hin tnh cht ha hc.
- Ging vi S, Se v Te tc dng vi nhiu kim loi to thnh cc selenua

v telurua ging vi cc sunfua
Se + Mg MgSe
Te + Na Na2Te
- Vi H2 , Se tc dng nhit cao cn Te khng tc dng
Se + H2 H2Se
- Se v Te khng tc dng vi axit nhng Portland tc dng nh mt kim

loi:
Po + HCl PoCl2 + H2
Vi axit sunfuric c v axit nitric tc dng nh S cn Po tc dng nh

mt kim loi
Se + HNO3 H2SeO4 + NO + H2O
P o + HNO3 Po(NO3)4 + NO + H2O
- Se v Te cng tan trong dung dch kim nh S:
Se + KOH K2SeO3 + K2Se + H2O
100
- Trong t nhin Se v Te thng chung vi cc kim loi nh Cu, Pb,

Hg, Ag v Au. Nhng khong vt ring ca chng rt t khi gp m chng
thng ln trong nhng khong vt ca lu hunh di dng tp cht.
- Ngun ch yu khai thc Se v Te trong cng nghip l bi khi ca

l t pyrit trong sn xut axit sunfuric hoc bn anot trong qu trnh tinh ch
Cu bng phng php in phn. Ngi ta dng MnO2 oxy ha Se v Te
trong cc hp cht thnh ioxit EO2. Sau khi tc EO2 ra v cho tc dng vi
SO2 thep phn ng:
EO2 + SO3 SO3 + E
VIII.3.2. Mt s hp cht quan trng
Hp cht vi hydro
- Cc nguyn t Se, Te, Po to vi hydro c cng thc chung H2E ging

vi phn t H2O v H2S. H2Se (dihydro selenua) v H2Te (dihydro telurua) l
nhng kh c mi trng thi v rt c.
Mt s c im ca H2E
Phn t H2O H2S H2Se H2Te
Gc HEH 104,50 92,20 910 900
di lin kt E - H (A0 ) 0,96 1,33 1,46 1,69
Sinh nhit H0 (kcal/mol) - 63,8 - 4,8 + 18,5 + 34,5
S gim gc lin kt t H2O n H2Te l do gim kh nng lai ha sp3 t

O n Te. Lin kt E - H c di tng ln v nng lng gim dn t H2O n
H2Te lm cho bn nhit ca phn t gim dn: H2O rt bn, H2S bn, H2Se
tng i bn ch phn hy r rt trn 3000C cn H2Te km bn.
- Trong nc, H2Se v H2Te tan nhiu hn so vi H2S. Dung dch ca

chng l nhng axit yu v lc axit tng ln t H2O n H2Te. Kh nng kh
cng tng ln theo trt t .
101
- H2Se v H2Te c th iu ch bng cch cho selenua v telurua ca mt

s kim loi tc dng vi nc hay axit:
Al2Te3 + 6 H2O Al(OH)3 + H2Te
Dioxit:
Khc vi S, trng thi lai ha sp2 ca Se, Te v Po khng c trng cho

nn cc dioxit EO2 l nhng polyme.
- Trong dy SeO2 - TeO2 - PoO2 tnh axit gim v tnh baz tng ln.
SeO2 tan d dng trong nc to thnh axit selen:
SeO2 + H2O H2SeO3
- TeO2 khng tan trong nc nhng tan trong kim to thnh mui telurit:
TeO2 + KOH K2TeO3 + H2O
- TeO2 v PoO2 c th tan c trong cc axit:
TeO2 + HCl TeCl4 + H2O
PoO2 + H2SO4 Po(SO4)2 + H2O
- Khc vi SO2 , SeO2 v TeO2 l nhng cht oxy ha mnh, d dng b

kh n Se v Te:
SeO2 + SO2 Se + SO3
Oxyaxit ca selen v telu
- Axt selen H2SeO3 l cht dng tinh th khng mu, chy ra khi
trong khng kh m nhng b vn dn trong khng kh kh.
- Axt telur H2TeO3 khng tch ra trng thi t do v ngay khi tch ra
t dung dch n mt mt phn nc to thnh hydrat xTeO2.yH2O (>y).
- So vi H2SO3 th 2 axit ny bn hn nhiu, tuy nhin chng vn km

bn vi nhit, khi un nng nh chng d mt nc bin thnh anhydrit EO2.
102
- Axit selen l axit yu (K1 = 2.10-3, K2 = 5.10-9) n cho 2 loi mui:

hydroselenit cha anion HSeO3- v selenit SeO32-.
- Axit telur l cht lng tnh: n tan trong kim cho mui telurit v tan
trong axit cho mui Te(IV)
- Axit selen c th iu ch bng cch ha tan selen bt trong axit nitric

long:
Se + HNO3 + H2O H2SeO3 + NO
103
CHNG IX. CC NGUYN T NHM VA
Nhm VA bao gm cc nguyn t nit (N), pht pho (P), asen (As),
antimoan (Sb), bitmut (Bi). Sau y l mt s c im nguyn t ca chng.
Mt s c im ca nguyn t
Nguyn t N P As Sb Bi
STT nguyn t 7 15 33 51 83
Cu hnh e ha tr 2s22p3 3s23p6 4s24p3 5s25p3 6s26p3
Bn knh nguyn t () 0,71 1,3 1,48 1,61 1,82
Bn knh cng ha tr
0,77 1,1 1,21 1,41 1,82
()
Bn knh ca ion X3-

1.48 1,86 1,92 2,08 2,13
()
Bn knh ca ion X5-

0,15 0,35 0,47 0,62 0,71
()
NL ion ha (kcal/mol)
335,1 254 226 199,2 168,1
I1
452,2 466 380 384,7

I2
1094 695,5 653 583 589,5

I3
1786 1184 1160 1020 1040

I4
m in 3 2,1 2 1,9 1,9
104
IX.1. NIT
IX.1.1. n cht
Nit thin nhin l hn hp ca hai ng v 14N v 15N vi t l 271:1.

ng v 15N thng c dng trong phng php nh du nguyn t v c th
a vo axit nitric vi t l 99,8%. Axit H15NO3 l cht u iu ch nn bt
c hp cht no ca nit nh du. Nit tn ti trong thin nhin ch yu dng
phn t N2.
Phn t N2 c cu hnh electron: ( 2sk ) 2 ( 2s* ) 2 ( zlk ) 2 ( xlk ) 2 ( ylk ) 2
Ngha l trong phn t c 1 lin kt ba N N, lin kt ba ny c nng lng

225,8kcal; d=1,095 Ao. Nng lng lin kt ln gii thch tnh tr ca phn
t N2.
1. L tnh, ha tnh
Nit l mt cht kh khng mu, khng mi, khng v nh hn khng kh,

khng duy tr s sng (t Hy Lp gi l azot ngha l khng duy tr s sng, kh
ha lng v kh ha rn (tos = -195,8oC ; tonc = -210oC) nn c dng to
nhit thp trong phng th nghim.
Do c nng lng lin kt rt ln, phn t N2 rt bn vi nhit, 3000oC

cha phn hy r thnh nguyn t. V vy nhit thng n rt tr, phn
ng ch xy ra nhit cao v khi c mt xc tc.
nhit thng nit ch c th tng tc vi liti kim loi:
6Li + N2 2Li3N
nhit cao nit c th tng tc vi hydro, oxy v mt s kim loi:

3Mg + N2 2Mg3N2
2B + N2 2BN
3H2 + N2 2NH3
N2 + O2 2NO
105
Li dng tnh tr ca nit ngi ta thng dng nit lm kh quyn tr

trong luyn kim, trong cng nghip in t, v cng nghip thc phm.
2. Trng thi thin nhin v phng php iu ch
Nit chim 78,03% th tch khng kh, ngoi ra nit cn c nhiu trong
khong dim tiu KNO3, v c nhiu trong hp cht hu c protit. Nit dng
iu ch NH3 v t hp cht ny ngi ta iu ch ra cc loi phn m, axit
nitric, thuc n...
Trong cng nghip nit c iu ch bng cch chng ct phn on

khng kh lng. Trong phng th nghim N2 c iu ch theo phn ng:
o
NH4NO2
t
N2 + 2H2O
o
2NaN3
t
2Na + 3N2
Natri azotua
IX.1.2. Hp cht
XI.1.2.1. Amoniac (NH3)
NH3 c cu to hnh chp vi y l mt tam gic u:

0
N dN-H = 1,014 A
H H HNH = 1070
Phn t NH3 c cu hnh electron trng thi c bn l:
( lk 2 lk 2 lk 2 lk 2
s ) ( x ) ( y ) ( z )
Gin nng lng cc MO trong phn t NH3:
AO(N) MO AO(H)
*z
106
1sa
1sb
*x *y
2p
1sc
lk
z
2s lk
x lk
y
slk
- NH3 l mt cht kh khng mu, mi khai, nh hn khng kh, ha lng

-33,35oC, ha rn -77,5oC, l phn t c cc nn d tan trong nc. NH3
lng c hng s in mi ln nn l mt dung mi ion ha tt i vi nhiu
cht. NH3 lng t phn ly theo qu trnh:
2NH3 NH4+ + NH2-
Tng t vi nc, cht no khi tan trong NH3 lng lm tng nng
NH4+ l axit, lm tng nng NH2- l baz.
Phn ng trung ha gia axit v baz trong NH3 lng l:
KNH2 + NH4Cl NH4NH2 + KCl

107
Cc cht Zn(NH2)2, Al(NH2)3 va tan trong axit va tan trong baz l

hp cht lng tnh:
Zn(NH2)2 + 2NH4Cl [Zn(NH3)4]Cl2
Zn(NH2)2 + 2KNH2 K2[Zn(NH2)4]
- NH3 lng ha tan c kim loi kim, kim th to nn dung dch c

mu lam thm. - NH3 kh hot ng v mt ha hc. Vi cp electron t do trn
nit, NH3 c kh nng kt hp vi nhiu cht. V d khi tan trong nc:
NH3 + H2O NH4+ + OH- (1)
Hng s phn ly ca NH3 250C l:
[NH 4 ][OH ]
K 1,8.10 5
[NH 3 ]
nn NH3 trong nc l mt baz yu.
Khi thm axit mnh nh HCl, HNO3, H2SO4 vo dung dch NH3, cn bng
trn y chuyn dch hon ton sang phi to ra cc mui amni NH4Cl,
NH4NO3, (NH4)2SO4. Kh NH3 tc dng d dng vi kh HCl to ra khi trng
NH4Cl, y l phn ng dng nhn bit kh HCl.
NH3(k) + HCl(k) NH4Cl(r)
- NH3 c th kt hp vi nhiu mui kim loi to thnh cc amniatcat dng tinh

th nh CaCl2.8NH3, CuSO4.4NH3...
- Kh NH3 c th chy trong oxy:
4NH3 + 3O2 2N2 + 6H2O
4NH3 + 5O2
Pt
4NO + 6H2O
- Clo v brrm oxy ha mnh NH3 trng thi kh v dung dch:
2NH3 + 3Cl2 N2 + 6HCl
108
- Khi un nng n kh c oxyt ca mt s kim loi:
2NH3 + 3CuO N2 + 3Cu + 3H2O
- nhit cao NH3 tng tc c vi kim loi hot ng to amiua NH2-,

imiua NH2- v nitrua N3-.
0
2 Na + 2 NH3
300 400 C
2 NaNH2 + H2
0
Al + NH3
800 900 C
AlN + H2
NH3 c dng sn xut axit HNO3, mui amni, ur.
Trc y NH3 c iu ch theo phn ng:
CaCN2 + 3H2O CaCO3 + 2NH3
Cyanamit
Ngy nay: N2 + 3H2 2NH3 , H0 = -22 kcal
IX.1.2.2. Mui amni v gc amni t do
Ion NH4+ c cu hnh t din u:
H +
H H
Bn knh ca NH4+= 1,43Ao gn vi bn knh ca cc ion lim loi kim

(K+ = 1,44Ao Rb+= 1,48 Ao) do mui amni ging mui ca kim loi kim.
Hu ht cc amni u tan v b thy phn trong dung dch cho mi trng axit:
109
NH4+ + H2O NH3 + H3O+ K = 5,5.10-10
Ty thuc vo bn cht ca axit to nn mui m phn ng nhit phn

xy ra khc nhau. Mui vi gc axit c tnh oxy ha mnh nh HNO2, HNO3
khi b un nng axit gii phng s oxy ha NH3 thnh N 2 hay N2O
NH4NO2 N2 + 2H2O
NH4NO3 N2O + 2H2O
Mui ca axit d bay hi khi un nng s phn hy theo phng trnh

ngc vi phn ng kt hp:
NH4Cl NH3 + HCl
(NH4)2CO3 NH3 + NH4HCO3
NH4HCO3 NH3 + H2O + CO2
Mui amni quan trng trong thc t l cc mui NH4Cl, (NH4)2SO4,

NH4NO3...
Gc amni t do : Qua s ging nhau ca mui amni v mui kim loi

kim, cu hi c t ra l liu c gc NH4+ ging nh ion kim loi kim hay
khng?
Hin nay ngi ta cha tch ring c gc NH4+ t do nhng khi in

phn dung dch mui ammi trong NH3 lng nhit -950C vi cc m bng
thy ngn ta thu c hn hng NH4+ tan trong thy ngn. Hn hng ny cng
c iu ch khi cho hn hng natri tc dng vi dung dch NH4Cl c:
Na(Hg) + NH4Cl NH4(Hg) + NaCl
Khi tc dng vi mui ng, hn hng amni gii phng ng kim loi
(tc y ng ra khi mui):
2NH4(Hg) + CuSO4 Cu(Hg) + (NH4)2SO4
110
Nh vy gc NH4+ c tnh cht ca mt kim loi; v mc hot ng n

km kim loi kim v mnh hn Cu.
IX.1.2.3. Hydrazin (N2H4)
H
o o
H N dN-N = 1,47 A , dN-H = 1,04 A

N H H N H = N N H = 1100
H
- Hydrazin l mt cht lng khng mu, c mi kh chu, bc khi mnh

trong khng kh, rt c, ha rn 20C, si 1140C.
- N2H4 c nhng tnh cht tng t NH3, tan trong nc v ru theo mi

t l. Vi nc n to nn hydrat N2H4.H2O trong N2H4 lin kt vi H2O
bng lin kt hyr.
H2 - N: ........ H O
H2 - N: ........ H
N2H4 l mt dung mi ion ha rt tt i vi nhiu cht ( 220C hng s

in mi = 53), n ha tan c kim loi kim v gii phng dn H2:
2Na + 2N2H4 2NaN2H3 + H2
N2H4 c iu ch theo phn ng:
N2(k) + 2H2(k) = N2H4 H0 = 12 kcal/mol
N2H4 kh bn, ch b phn hy khi c mt xc tc, l mt baz 2 nc yu

hn NH3
N2H4 + H2O N2H5+ + OH- K1 = 8,5.10-7
N2H5+ + H2O N2H62+ + OH- K2 = 8,9.10-16
do hydrazin to nn 2 mui N2H5Cl v N2H6Cl2
111
N2H4 l mt cht kh mnh, mnh hn NH3, n c th chy trong khng kh v

pht ra nhiu nhit.
N2H4(l) + O2(k) N2(k) + 2H2O(l) H0 = -169,2 kcal/mol
do hydrazin c dng lm cht t cho tn la. Trong dung dch n c th

kh c halogen, MnO4-, Fe3+, IO3- v mt s ion kim loi:
N2H4 + 2Cl2 N2 + 4HCl
N2H4 + 4AgNO3 N2 + 4Ag + 4HNO3
N2H4 dng nhiu trong tng hp hu c, trong cng nghip...
Phn ng iu ch
NaClO + 2NH3(dd)
Gelatin
N2H4 + NaCl + H2O
IX.1.2.4. Axit hydrazoic (HN3)

o
N N N dNN = 1,24 A
H
o
dNN = 1,13 A
o
dN-H = 1,01 A
HNN = 110,50
Axit hydrazoic l mt cht lng khng mu, c mi kh chu v rt c,

ha rn -800C, si 370C, km bn, d phn hy, d gy n.
2HN3(k) 3N2(k) + H2(k) H0 = 71,04 kcal/mol
Trong dung dch bn hn, l axit yu tng ng CH3COOH.
Mui ca HN3 gi l azotua. Mui ca azotua ca kim loi nng rt d n,

azotua ch v thy ngn n khi va p, c dng lm ngi n. Azotua kim loi
kim, kim th bn, phn hy m 3000C:
2NaN3 2Na + 3N2

112
Ion N3- tng t X- nn c gi l ion halogenua gi, tuy nhin khng c phn
t (N3)2 gi. Azotua kim loi kim, kim th tan; azotua ch, bc, thy ngn cng
t tan nh halogenua. Axit HN3 c iu ch theo phn ng:
0
NaNH2 + N2O
190 C
NaN3 + H2O
IX.1.2.5.Hydroxyl amin (NH2OH)
Hydroxil amin l cht dng tinh th khng mu, nng chy 330C, km
bn, phn hy dn nhit thng, phn hy nhanh nhit cao gy n:
11NH2OH 5NH3 + N2 + 2N2O + 9H2O
Ht m mnh, tan nhiu trong nc to ra dung dch baz yu hn NH3. Khi

tng tc vi axit to ra mui hydroxil amni km bn. V d: (NH3OH)Cl,
(NH3OH )2SO4.
Trong dung dch kim, NH2OH l mt cht kh mnh, nhng yu hn

N2H4
NH2OH + HNO3 2NO + 2H2O
Ngoi ra n cng th hin tnh oxy ha:
NH2OH + 2Fe(OH)2 + H2O 2Fe(OH)3 + NH3
Trong phng th nghim c th iu ch NH2OH bng cch in phn axit

HNO3 vi cc m bng Pb, axit HNO3 s c kh theo phng trnh:
HNO3 + 6Ho NH2OH + 2H2O
IX.1.2.6. Nitrua kim loi
Nitrua kim loi c chia lm 2 nhm: nitrua ion v nitrua xm nhp. Cc

kim loi kim, kim th, Zn, Cd, Tl to nn nitrua ion, trong cha cation kim
loi v anion N3-. Nitrua ion d b thy phn:
Ca3N2 + 6 H2O 3Ca(OH)2 + 2NH3
Cc nitrua ion c th iu ch trc tip t cc nguyn t. V d:

113
3Mg + N2 Mg3N2
hoc nhit phn amiua kim loi:
3Ba(NH2)2 Ba3N2 + 4NH3
Cc kim loi chuyn tip to nn nitrua xm nhp c cu to v tnh cht

tng t borua, cacbua xm nhp, nhng nguyn t nit chim cc l trng
trong mng li kim loi. Cc nitrua ny thng c cng thc khng hp thc
Fe4N, Mn4N, Mo2N... c cng v dn in nh kim loi. Ging nh borua
v nitrua xm nhp, chng rt cng v kh nng chy. Cc nitrua xm nhp
thng c th iu ch bng cch t nng bt kim loi trong kh N2 hay NH3
12000C.
IX.1.2.7. Oxyt ca nit
Nit to nn 8 oxyt: N2O, NO, N2O3, NO2, N2O4, N2O5, NO3 v N2O6. Hai
oxyt NO3 v N2O6 rt km bn khng c trng.
a/ init oxyt (N2O)
Cng thc cu to tng t nh CO2 nhng khng i xng
o
Vi di lin kt N - N l 1,26 Ao , N - O l 1,186 A
di lin kt N - N y khng ph hp vi lin kt ba N -N (1,10 Ao)

hay lin kt i N = N (1,25Ao) v di lin kt NO cng khng ph hp vi
lin kt i N = O (1,14A0) hay lin kt n N - O (1,36Ao). iu ny cho thy
N2O tn ti 2 dng phn t c cu to nh sau:
N2O l mt cht kh khng mu, c mi tng i d chu ha lng -

890C, ha rn -910C. Khi ngi phi N2O vi lng t th say v hay ci nn
gi l kh vui, nu ngi vi lng nhiu th b m nn c dng lm thuc gy
m trong y hc. nhit thng N2O km hot ng, b phn hy 5000C.
114
2N2O 2N2 + O2 H0 = -39 kcal
Khi un nng n tr nn hot ng hn.
N2O + H2 N2 + H2 O H0 = -77,3 kcal
3N2O + 2NH3 4N2 + 3H2O H0 = -180 kcal
N2O c iu ch theo phn ng
250 0C
NH4NO3 N2O + 2H2O
b/ Nit oxyt (NO)
Phn t NO thun t, c cu hnh electron nh sau:
( lk 2 * 2 lk 2 lk 2 lk 2 * 1
2s ) ( 2s ) ( x ) ( y ) ( z ) ( x )
Cng thc cu to ca NO l:
3 chm dng k hiu lin kt to thnh bi cp e lin kt v mt e phn lin

kt, n c gi l lin kt 3 electron hay lin kt 1 electron.
bi lin kt trong NO l (8 - 3)/5 = 2,5. Nh vy gia nit v oxy c

2,5 lin kt, iu ny ph hp vi di lin kt l 1,14 Ao (d N = O = 1,18 Ao
, d N O = 1,06Ao).
L phn t c s l electron nhng trng thi kh NO khng th hin

khuynh hng trng hp. trng thi rn n tn ti dng dime:
N ........ O
o
1,10 A
O ........o N
2,33 A
NO kh bn, trn 5000C cha b phn hy.

115
NO kt hp rt d vi O2 to thnh NO2:
2NO + O2 2NO2
tng tc c vi F2, Cl2, Br2 to thnh nitrzni halogenua
V d: 2NO + Cl2 2NOCl
Cc cht oxy ha mnh nh KMnO4, HClO, CrO3 oxy ha NO HNO3
6KMnO4 + 10NO + 9H2SO4 10HNO3 + 3K2SO4 + 6MnSO4 + 4H2O
Khi gp cc cht kh mnh NO ng vai tr cht oxy ha
2NO + 2H2S N2 + 2S + 2H2O
2NO + SO2 N2O + SO3
Ngoi tnh cht oxy ha kh NO cn c kh nng kt hp vi mui ca

nhiu kim loi, v d tc dng vi dung dch FeSO4 cho hp cht mu nu thm,
khng bn khi un nng: FeSO4 + NO [Fe(NO)]SO4
NO khng tc dng vi nc, axit, baz v c gi l oxyt khng to

mui.
Kh NO c th tng hp trc tip t cc nguyn t nhit cao
N2 + O2 2NO H0 = 21,6 kcal/mol
Trong phng th nghim, kh NO c iu ch bng cch cho Cu tc

dng vi axit HNO3 long: 3Cu + 8HNO3(l) 3Cu(NO3)2 + 2NO + 4H2O
NO tinh khit c iu ch theo phn ng:
2NaNO2 + 2NaI + 4H2SO4 I2 + 4NaHSO4 + 2NO + 2H2O
c/ Nit ioxyt (NO2) v init ttraoxyt (N2O4)
NO2 l mt cht kh mu nu , c, mi kh chu.C cu hnh electron:
116
(2s a ) 2 (2s b ) 2 ( lk 2 lk 2 lk 2 2 2 2
s ) ( z ) ( y ) (2Pxa ) (2Pxb ) ( y ) ( x )
1
Cng thc cu to:
Gin nng lng
AO MO AO ca nguyn t O
ca nguyn t N
*s
x 2pa
*z
s
*y
2p
- 2sa
- 2sb
2pb
2Pxa 2Pxb
2s
lk
y
117
lk
z
lk
s
2sa 2sb
Theo phng php VB, trong phn t NO2 nit trng thi lai ha sp2,
hai obitan lai ha c dng to lin kt gia N v O, obitan lai ha cn li
c 1 e c thn; mt obitan 2p khng lai ha c 1 e c thn ca N c dng
to lin kt vi 1 trong 2 nguyn t oxy, ngha l lin kt khng
nh ch.
NO2 l phn t c s l electron, ngoi tnh c mu n cn kt hp to

nn N2O4 nh s ghp 2 electron c thn hai nguyn t nit.
2NO2 N2O4 H = -14,7 kcal
N2O4 khng mu v nghch t. NO2 km bn vi nhit, bt u phn hy

1500C v phn hy hon ton 6000C:
2NO2 2NO + O2
v vy S, C, P chy c trong NO2 :
2NO2 + C 2NO + CO2
NO2 tc dng c vi H2O v baz:
2NO2 + H2O HNO3 + HNO2
2NO2 + NaOH NaNO3 + NaNO2 + H2O
Vy NO2 c th xem l 1 anhyric hn tp ca axit nitr v axit nitric.
NO2 va c tnh oxy ha, va c tnh kh.
Tnh oxy ha:

118
0
Cl2 + 2NO2
t
2ClNO2 Cloruanitrni
7H2 + 2NO2 2NH3 + 4H2O

0
2Cu + NO2
t
Cu2O + NO
0
CO + NO2
t
CO2 + NO
0
SO2 + NO2
t
SO3 + NO
Vi cc cht oxy ha mnh, NO2 th hin tnh kh
2NO2 + O3 N2O5 + O2
2NO2 + H2O2 2HNO3
Trong cng nghip NO2 c iu ch theo phn ng
2NO + O2 2NO2
Trong phng th nghim:
Cu + 4HNO3 Cu(NO3)2 + 2NO2 + 2H2O
d/ init trioxit (N2O3)
Ch tn ti dng rn, c mu lam nht, khng bn, d b phn hy:
N2O3 NO + NO2
c iu ch khi trn NO, NO2 nhit di 1000C.
e/ init pentaoxit (N2O5)
Cng thc cu to:
119
trng thi rn n tn ti dng ion nitrni nitrat NO2+ NO3-. Cng thc ca
N2O5 trng thi rn ph hp vi s phn ly ca n trong cc axit khan nh
HNO3, H2SO4, H3PO4
N2O5 NO2+ + NO3-
iu kin thng l cht rn trong sut khng mu, chy lng 300C, si
450C, km bn, phn hy chm nhit thng, v mnh nhit cao.
2N2O5 4NO2 + O2
N2O5 l cht oxy ha mnh, tan trong nc to ra axit nitric
N2O5 + H2O 2HNO3
Trong phng th nghim c iu ch theo phn ng
P2O5 + 2HNO3 2HPO3 + N2O5
IX.1.2.8. Cc axit
a/ Axit nitr (HNO2)
C 2 cu to c th chuyn ha cho nhau:
Axit HNO2 ch tn ti trng thi kh v trong dung dch nc, d b phn hy,
nht l khi un nng:
Trong pha kh: 2HNO2 NO + NO2
Trong dung dch: 3HNO2 HNO3 + 2NO + H2O
Trong dung dch, do khng bn axit HNO2 rt hot ng v mt ha hc,

n va th hin tnh kh va th hin tnh oxy ha.V d v tnh oxy ha:
2HI + 2HNO2 2NO + I2 + 2H2O
120
H2SO4 + FeSO4 + HNO2 Fe2(SO4)3 + NO + H2O
SO2 + HNO2 H2SO4 + 2NO
Tnh kh th hin khi tng tc vi cc cht oxy ha mnh nh KMnO4,

K2Cr2O7, MnO2 ...
2KMnO4 + 3H2SO4 + 5HNO2 = 2MNSO4 + 5HNO3 + K2SO4 + 3H2O
Trong dung dch nc, HNO2 l mt axit yu:
HNO2 H+ + NO2- Ka = 4,5.10-4 (hi mnh hn axit

cacbonic)
Mui ca HNO2 gi l mui nitrit NO2-, bn hn axit.
Cng thc cu to:
Trong N trng thi lai ha sp2 .
Nitrit kim loi kim bn vi nhit ch phn hy trn 500oC. Nitrit cc kim
loi khc km bn hn, d b phn hy khi un nng. Trong mi trng axit,
mui NO2- va c tnh kh, va c tnh oxy ha nh HNO2
KNO2 + KMnO4 + H2SO4 KNO3 + MnSO4 + K2SO4 + H2O
Axit HNO2 c iu ch theo phn ng:
Ba(NO2)2 + H2SO4 BaSO4 + 2HNO2
b/ Axit nitric (HNO3)
Cng thc cu to:
121
Axit HNO3 tinh khit l mt cht lng khng mu, bc khi mnh trong khng
kh, ha rn -410C, si 860C.
HNO3 tinh khit km bn, d b phn hy di tc dng ca nh sng v

nhit
4HNO3 NO2 + O2 + 2HNO2
NO2 sinh ra tan tr li trong axit HNO3 lm cho axit c mu vng. Axit HNO3
tinh khit t ion ha nh sau:
2HNO3 NO 2 + NO3- + H2O
Khi tan trong dung mi c kh nng cho proton mnh hn nh H2SO4, HClO4
th axit HNO3 phn ly cho ion NO2+. Axit c tan nhiu trong nc theo bt k
t l no. Trong H2O, mt dung mi c kh nng cho proton km hn, HNO3
phn ly theo kiu axit:
HNO3 + H2O NO3- + H3O+
axit HNO3 tc dng vi kim loi khng gii phng H2 , do ion NO3- oxy ha
mnh hn nhiu so vi ion H3O+
NO3- + 2H+ + e = NO2 + H2O Eo = +0,8V
NO3- + 3H+ + 2e = HNO2 + H2O Eo = +0,94V
NO3- + 4H+ + 3e = NO + 2H2O Eo = +0,96V
NO3- + 6H+ + 5e = 1/2N2 + 3H2O Eo = +1,25V
NO3- + 10H+ + 8e = NH4+ + 3H2O Eo = +0,88V
Axit HNO3 tc dng hu ht cc kim loi tr Pt, Au v mt s khng kim loi

nh C, S, P. Trong cc phn ng ny axit HNO3 b kh v HNO2, NO2, NO,
N2O, NH3... ty thuc vo nng ca axit, v bn cht ca cht kh.
V d: Cu + HNO3 Cu(NO3)2 + NO2 + H2O
Cu + HNO3(l) Cu(NO3)2 + NO + H2O

122
Zn + HNO3(l) Zn(NO3)2 + N2 + H2O
vi cc kim
S + HNO3(l) H2SO4 + 2NO
S + HNO3() H2SO4 + 6NO2 + H2O
Fe, Cr, Al b th ng trong axit HNO3 m c, ngui, c ch cha r, nhng

thng c gii thch l do s to thnh mt lp oxit dy c bao quanh bo v
kim loi bn trong.
HNO3 cn oxy ha Fe2+ Fe3+ :
6FeSO4 + 3H2SO4 + 2HNO3 Fe2(SO4)3 + 2NO + 4H20
HNO3 long khng oxyha HI thnh I2 nhng c HNO3 oxy ha c c HI v

HCl v X2
HNO3 + 3HCl NO + 3/2 Cl2 + 2H2O
Hn hp gm mt th tch HNO3 vi 3 th tch HCl m c gi l

nc cng thy, n ha tan c Au, Pt:
3Pt + 4HNO3 + 12HCl 3PtCl4 + 4NO +8H2O
Ta c s th in cc ca axit HNO3 nh sau:
NO3- +0,94 HNO2 +1,0 NO +1,59 N2O +1,77 N2 +0,27 NH4+
+0,11
Axit HNO3 l mt trong nhng ha cht c bn rt quan trng, n c

dng vo vic iu ch thuc n, phn bn, phm nhum, ha cht v dc
phm...
Trong cng nghip HNO3 c iu ch t NH3

0
3NH3 + 5/2O2
250 C
2NO + 3H2O
123
2NO + O2 2NO2
4NO2 + O2 + 2H2O 4HNO3
IX.1.2.9. Nitrat
Nitrat l mui ca axit nitric
N 1,28Ao
O 1200 O
Ion NO3- khng c mu nn cc mui ca cathion khng c mu u

khng c mu, hu ht cc mui nitrat u tan trong nc.
Nitrat kh bn nhit, bn nhit ca mui nitrat ph thuc vo bn cht

ca cathion kim loi:
- Nitrat ca kim loi hot ng ng trc Mg: khi un nng phn hy

to ra nitrit NO2- v oxy.
o
2KNO3 2KNO2 + O2
400 C
- Nitrat ca kim loi t Mg Cu: khi un nng b phn hy to ra oxit kim

loi, NO2 v O2
Hg(NO3)2 Hg + 2NO2 + O2
Do d mt oxy cho nn cc mui nitrat khan khi un nng l cht oxy ha

mnh. Ion NO3- trong mi trng axit c kh nng oxy ha nh axit HNO3,
trong mi trng trung tnh hu nh khng c tnh oxyha, nhng trong mi
trng kim c th b Al, Zn kh n NH3.
NaNO3 + Zn + 7NaOH + 6 H2O 4 Na[Zn(OH)4] + NH3
Nitrat quan trng l KNO3 (dim tiu) dng lm thuc n en.
124
2KNO3 + S + 3C K2S + 3CO2 + N2
IX.2. PHT PHO
IX.2.1.n cht
1. L tnh
Pht pho c 3 dng th hnh: pht pho trng, pht pho v pht pho en
Pht pho trng: l khi trong sut nh sp, c mng li lp phng gm cc

phn t P4 cu to t din u, d nng chy (tonc = 440C), d bay hi (ts =
2870C), mm, d tan trong cc dung mi khng cc nh CS2, C6H6. Cc lin kt
P - P kem bn nn P trng rt hot ng, c th t chuyn thnh P . P trng
rt c, liu cht 0,1g.
Pht pho : L mt cht bt mu , nng chy 6000C, nu p sut cao

thng hoa nhit to hi gm cc phn t P 4, hi ngng t li to ra P
trng. P l cht dng plyme, gm mt s dng khc nhau. Ty theo cch
iu ch P c nhng tnh cht khc nhau nh t khi bin i t 2 n 2,4;
mu sc bin i t nu n hoc tm.
Pht pho en: Pht pho en c to ra khi un pht pho trng 220 - 370oC
trong 8 ngy hay p sut cao (12000 atm), hay c Hg xc tc.
P en cng dng plyme. P en l cht bn dn, nng chy gn 10000C

p sut 18.000 atm, P en bn hn P trng v P . P en v P khng c,
khng tan trong dung mi.
2. Ha tnh
P hot ng hn nit v lin kt P - P trong phn t P4 km bn hn lin kt N -

N trong phn t N2. P trng hot ng hn P v P en.
P va c tnh oxy ha va c tnh kh:
Tnh oxy ha: Khi un nng, P c th tng tc vi nhiu kim loi to ra pht
phua
125
3Mg + 2P Mg3P2
Ty thuc vo bn cht ca kim loi m kiu lin kt trong phtphua thay

i trong gii hn rng. V d: Pht phua ca cc nguyn t thuc nhm II
(M3P3) c th xem l cc hp cht cng ha tr ion, chng ging mui, d b
thy phn.
Mg3P2 + H2O 3Mg(OH)2 + 2H3P
Pht phua ca cc nguyn t d thng kiu MP, MP2, M3P c mu xm

en, nh kim v dn in; cc pht phua loi ny km hot ng v mt ha hc.
Pht pho thc t khng tc dng vi hydro. Hydro phtphua H3P c

iu ch bng con ng gin tip.
Tnh kh: l tnh cht quan trng nht
Tc dng vi oxy: khi P chy trong iu kin oxy th to ra P4O10 ,

khng d th to hn hp P4O6 v P4O10. P trng b oxy ha dn v pht ra nh
sng mu lc nhn thy trong bng ti. Hin tng ny c gi l s pht
quang ha hc.
Pht pho cng tng tc vi halogen, S:
P + Cl2 PCl3
P + Cl2 PCl5
P + S P2S5
P tc dng vi cc axit c tnh oxy ha mnh nh HNO3, H2SO4 .
P + HNO3 H3PO4 + NO2 + H2O
P + H2SO4 H3PO4 + SO2 + H2O
Khi tng tc vi dung dch kim, pht pho th hin kh nng t oxy ha kh:
P4 + 3KOH + 3H2O PH3 + 3KH2PO2
126
3. Trng thi thin nhin, iu ch
Pht pho l nguyn t rt ph bin trong thin nhin, n chim khong

0,04% tng s nguyn t ca v tri t. P c nhiu trong ng vt chim
khong 1,16% khi lng ngi. Trong thin nhin P tn ti hai khong vt
chnh l: phtphorit [Ca3(PO4)2] v apatit [Ca5X(PO4)3] X = F- hay Cl- hoc OH-
. Trong cng nghip ngi ta sn xut P bng cch nung Phtphorit 1500 0C
trong l in vi in cc bng than vi C v ct.
2Ca3(PO4)2 + 6SiO2 6CaSiO3 + P4O10
P4O10 + 10C 10CO + P4
Hi pht pho bay ln c ngng t li trong bung c hi nc to ra

pht pho trng.
IX.2.2.Hp cht
IX.2.2.1. Phtphin
PH3 c cu to ging phn t NH3, c gc HPH = 93,70. Phtphin l mt

cht kh khng mu, mi trng thi ha lng -1330C, si -87,40C, ht sc
c. PH3 t tan trong nc. Cp e t do trn P km hot ng so vi nit nn
PH3 khng tc dng vi H2O m ch kt hp vi ion H+ ca axit nh HClO4, HX
to nn ion phtphoni PH4+.
Khc vi NH3, PH3 l cht kh mnh, bc chy trong khng kh:

o
PH3 + 2O2 150
C
H3PO4
d dng tng tc vi halogen
PH3 + Cl2 PCl5 + 3HCl
N gii phng kim loi khi tng tc vi mt s mui
6AgNO3 + PH3 + 3H2O 6Ag + 6HNO3 + H3PO3
Phtphin c iu ch bng cch cho phtphua tc dng vi H2O:
127
Ca3P2 + H2O 3Ca(OH)2 + 2PH3
Ngoi PH3 cn c P2H4 (iphtphin) c cu to ging hydrazin N2H4, l

mt cht lng khng mu, ha rn -990C, si 630C. Tuy c cu to ging
N2H4 nhng c tnh cht khc vi N2H4 nh khng to mui khi tng tc vi
axit, l cht kh mnh, t bc chy trong khng kh (ma tri), c iu ch khi
thy phn canxi pht phua khi c ln Ca2P2
Ca2P2 + 4H2O 2Ca(OH)2 + P2H4
IX.2.2.2. Cc oxit
a/ Phtpho (III) oxit:
Phtpho (III) oxit l cht dng tinh th mu trng, mm nh sp, nng

chy 23,80C, si 1750C, d tan trong CS2, CHCl3, C6H6, c. trng thi hi
cng nh trong dung dch n tn ti dng P4O6, tuy nhin trong thc t
thng dng cng thc kinh nghim P2O3.
Cng thc cu to gm t din u P4 v cc cu oxy
POP = 1280
OPO = 990
Khi un nng lu trong bnh kn P4O6 phn hy theo phng trnh:
nP4O6 3(PO2)n + nP
Oxit (PO2)n l oxit trung gian dng tinh th khng mu thng hoa 1800C.
nhit thng P4O6 bn vi oxy nhng 50 - 600C n tng tc vi

oxy
P4O6 + 2O2 P4O10
tc dng vi H2O to ra axit phtphor
128
P4O6 + 6H2O 4H3PO3
vi dung dch HCl n cng tng tc to ra axit H3PO3
P4O6 + HCl 2H3PO3 + 2PCl3
P4O6 c iu ch khi oxy ha chm P trng nhit thp trong iu kin

thiu oxy:
P4 + 3O2 P4O6
b/ Phtpho (V) oxit
c to nn khi t chy P trong iu kin d khng kh
4P + 5O2 P4O10
L cht rn kt tinh trong h lc phng, thng hoa 3590C, hi gm cc

phn t P4O10 . C cng thc cu to tng t P4O6
Pht pho(V) l mt cht ht m mnh v tng tc vi nc
P4O10 + 2H2O 4HPO3 axit mtaphtferic
d H2O: P4O10 + 6H2O 4H3PO4 axit otphtphoric
N cn ly nc ca HNO3, H2SO4 bin chng thnh anhydrit
12HNO3 + P4O10 6N2O5 + 4H3PO4
6H2SO4 + P4O10 6SO3 + 4H3PO4
129
IX.2.2.3. Cc axit
Pht pho to nn rt nhiu axit, ngy nay ngi ta bit c 11 oxit axit sau:
HPO2, H3PO2, H4P2O5, H3PO3, H4P2O6, HPO3, H4P2O7, H5P8O10, H3PO4, H3PO5,
H4P2O8,.
Tt c oxy axit ca P u c nhm P-O-H c kh nng phn ly cho H+,

cn lin kt P-H khng phn ly. Quan trng l cc axit H3PO2, H3PO3 v H3PO4.
Chng c CTCT
axit hypophotphor axit photphor axit photphoric
cc anion ca chng u c hnh t din:
130
H2PO2- HPO3- PO43-
Axit hypophotphor H3PO2 l mt cht rn khng mu, nng chy 270C, d

tan trong nc , phn hy 1300C
3H3PO2 2H3PO3 + PH3
H3PO2 l axit mnh v mt nc.
Axit H3PO3 v mui ca n (hypophtphit H2PO2-) l cht kh mnh (do

c lin kt P-H):
H3PO2 + 2CuSO4 + 2H2O 2Cu + 2H2SO4 + H3PO4
H3PO2 c iu ch theo phn ng:
2P4 (trng) + 3Ba(OH)2 + 6H2O 3Ba(H2PO2)2 + PH3
Ba(H2PO2)2 + H2SO4 BaSO4 + 2H3PO2
a/ Axit phtphor H3PO3 hay P(OH)3
L mt cht rn t0nc = 740C, d tan trong nc v phn hy 2000C
4H3PO3 3H3PO4 + PH3
L mt axit bc 2, phn ly theo 2 nc
H3PO3 H+ + H2PO3- K1 = 10-2
H2PO3- H+ + HPO32- K2 = 3.10-7
Mui ca n HPO32- gi l pht phit. H3PO3 l mt cht kh mnh
CuSO4 + H3PO3 + H2O Cu + H3PO4 + H2SO4
c iu ch khi cho P4O6 tc dng vi H2O

131
P4O6 + 6H2O 4H3PO3
hay thy phn PCl3 : PCl3 + H2O H3PO3 + HCl
b/ Axit phtphoric H3PO4
Axit pht phoric hay axit octhophtphoric H3PO4 l mt cht rn tinh th

khng mu, nng chy 42,50C. H3PO4 tan c trong nc do to lin kt
hydro.
P O H O
Dung dch axit H3PO4 m c bn trn th trng c nng n 85%.

Khi un nng n n 2600C th n mt bt H2O to ra axit iphtphoric hay
axit pyrophtphoric.
H4P2O7 dng thy tinh, mm, nng chy 61oC v d tan trong nc.
TRong nc chuyn chm thnh H3PO4. Khi un nng n 300oC chuyn thnh
axit metaphtphoric (HPO3)n, l cht polime, cng dng thy tinh, nng chy
40oC. Tan trong nc chuyn thnh axit ortho.
Axit H3PO4 l mt a axit c mnh trung bnh, phn ly theo 3 nc:
H3PO4 H+ + H2PO4- K1 = 7,6.10-3
H2PO4- H+ + HPO42- K2 = 6,2.10-8
HPO42- H+ + PO43- K3 = 4,4.10-13
to nn 3 loi mui ihyro phtphat H2PO4- , hydro phtphat HPO42- v

phtphat PO43-
Mt dng axit khc ca P(V) l axit mta pht phoric HPO3 c iu ch

theo phn ng:
P4O10 + 2H2O(thiu) 4HPO3

132
phn bit axit H3PO4 v HPO3 ngi ta cho mui ca chng tc dng
vi dung dch AgNO3 th HPO3 cho kt ta Ag3PO4 mu vng sng, HPO3 cho
kt ta trng AgPO3. Axit H3PO4 c iu ch bng cc phn ng sau:
Ca3(PO4)2 + 3H2SO4 3CaSO4 + 2H3PO4 (dng trong cng nghip)
P4O10 + 6 H2O 4H3PO4
PCl5 + 4H2O H3PO4 + 5HCl
Cc mui phtpht ni chung khng mu. Trong cc ihydro phtphat

H2PO4- v PO43- ch mui kim loi kim l tan, cn li khng tan.
Cc mui pht phat tan thy phn mnh:
Na3PO4 + H2O = NaOH + Na2HPO4 (mi trng kim mnh)
Na2HPO4 + H2O = NaOH + NaH2PO4 (mi trng kim yu)
NaH2PO4 c mi trng axit yu.
Khi c mt Mg2+ v NH4+ trong dung dch NH3, ion PO43- to nn kt ta

mu trng NH4MgPO4 : NH4+ + Mg2+ + PO43- NH4MgPO4
Khi c mt mui amni molypdat (NH4)2MoO4 trong dung dch HNO3 th

PO43- to nn kt ta amni phtphomolypdat (NH4)3[PMo12O40] c mu vng,
khng tan trong axit HNO3 nhng tan trong kim v dung dch NH3; phn ng
ny dng nhn bit PO43- trong dung dch
3NH4+ + PO43- + 12MoO42- + 24H+ (NH4)3[PMo12O40] + 12H2O
Cc mui phtphat thng c s dng lm phn bn. Cc mui

phtphat c trong phn t hoc ion ca n hn mt nguyn t P v c lin kt P-
O-P c gi l phtphat ngng t, c 2 loi phtphat ngng t l phtphat
ngng t mch h v phtphat ngng t mch vng.
-
( n+2)
Phtphat ngng t mch h cha anion c cng thc chung Pn O 3n+1
V d: M4P2O7 , M5P3O10 (M=kim loi kim)

133
O O O O O
O P O P O O P O P O P O
O O O O O
anion P4O74- anion P3O105-
Phtphat ngng t mch vng cha anion c cng thc chung (PO3)nn- nh
M4P4O12, M3P3O9 (M=kim loi kim)
O O
O P O P O
O O
O P O P O
O O
anion (PO3)33- anion (PO3)44-
Cc mui ngng t c nhng cng dng khc nhau trong cng nghip. V
d: Na4P2O7 dng lm cht ty ra, lm cht ti kim loi khi rn. Na4P2O7 c
iu ch theo phn ng:
0
2Na2HPO4
600 C
Na4P2O7 + H2O
Mui Na5P3O10 dng lm bt git (t l 45%), lm mm nc, c to

nn khi un nng hn hp mui Na2HPO4 v NaH2PO4 4200C.
2Na2HPO4 + NaH2PO4 Na5P3O10 + 2H2O
c/ Phn bn ha hc, phn ln
134
Mun sinh trng bnh thng hu ht cy trng u cn mt s nguyn

t chnh nh: C, H, O, N, P, K, Mg, Fe, B, Zn, Cu, Mo, Mn... Cy ci ng ha
c C, H, O t khng kh v H2O. i vi cc nguyn t cn li ngun cung
cp l t. Nhng ha cht cha cc nguyn t dinh dng cn b sung cho t
nui cy trng l phn bn ha hc. C 3 loi phn bn chnh l phn m,
phn ln v phn kali.
Phn m cung cp Nit cho cy di dng NO3-, NH4+ .
Phn ln cung cp P cho di dng PO43-
Phn kali cung cp K cho cy di dng K+
Ngoi 3 loi phn bn chnh trn, ngi ta cn dng cc phn vi lng

cung cp cho cy trng nhng lng rt b cc nguyn t B, Zn, Cu, Mo...
Nhng phn m chnh thng dng l ur (CO(NH2)2), NH4Cl, (NH4)2SO4,
Ca(NO3)2, NaNO3.
Nhng phn kali chnh thng dng l: KCl, K2SO4 , KNO3.
Phn ln gm c cc loi sau y:
-Apatit nghin (30-38% P2O5) & phtphorit nghin (16-18% P2O5):
C hm lng phtpho cao nhng khng tan trong nc. Cy ch hp th

v ng ha c chng khi chuyn ha t mui trung tnh thnh mui axit.
Qu trnh xy ra trong mi trng axit cho nn dng phn ny thch hp cho
t chua.
Dng ny c sn xut mt cch n gin: Sy kh apatit hay phtphorit

ri nghin thnh bt cng mn cng tt.
-Prexipitat (33-40% P2O5)
C thnh phn chnh l CaHPO4, mui monohydro ny c th tan khng

nhng trong mi trng axit mnh mm c trong axit yu nh axit citric.
Prexipitat c th dng lm phn bn cho c t chua v c t c mi trng
trung tnh v n c th tan c nh axit do r cy tit ra. c sn xut theo
phn ng:
135
Ca(OH)2 + H3PO4 CaHPO4 + 2H2O
-Supephtphat n (14 - 20% P2O5)
Gm 2 cht chnh l: Ca(H2PO4)2 v CaSO4 trong Ca(H2PO4)2 tan, cy

ci hp th trc tip, CaSO4 khng tan v khng c tc dng g vi cy, c
sn xut theo phn ng:
Ca3(PO4)2 + 2H2SO4() Ca(H2PO4)2 + 2CaSO4
nc ta Lm Thao (Vnh Phu) sn xut loi phn ny.
-Supephtphat kp (40 - 50% P2O5)
L loi phn ln dng rng ri, trong thnh phn khng c CaSO 4. c
iu ch theo 2 giai on phn ng:
Ca3(PO4)2 + 3H2SO4 2H3PO4 + 3CaSO4
4H3PO4 + Ca3(PO4)2 3Ca(H2PO4)2
-Phn ln nung chy (12 - 14% P2O5)
L hn hp silicat, pht phat ca Ca v Mg. Phn ln nung chy khng

tan trong nc nhng tan trong dung dch axit citric nng 20%, nn rt ph
hp vi rung chua. Phn ln nung chy c sn xut bng cch nung chy hn
hp apatit + x vn (thnh phn chnh l silicat magi 3MgO.2SiO2.2H2O)
nhit cao trong l in ri lm lnh t ngt bng nc, sn phm c sy
kh v nghin mn.
IX.2.2.4. Phtpho halogenua
P to vi halogen hai loi hp cht chnh: pht pho trihalogenua PX3 v

phtpho pentahalogenua PX5
a/ Phtpho trihalogenua PX3
Ngoi PF3, PCl3, PBr3, PI3 cn c cc halogenua hn hp PF2Cl, PF2Br,

PFCl2 ...
136
Phn t PX3 c cu to:
Gc XPX ca PF3 l 1040, PCl3 l 1020, PBr3 l 1000 v PI3 l 960. Nh

vy trong cc hp cht PX3, P trng thi lai ha sp3 v trng thi lai ha gim
t PF3 n PI3
Mt s tnh cht vt l :
Cht PF3 PCl3 PBr3 PI3
Mu K, khng mu L. khng mu L, khng mu Rn,
t0nc (oC) -152 -94 -40 -61
t0s (oC) -101 75 173 120
Tt c cc hp cht PX3 u d b thy phn
2PX3 + 6H2O 2H3PO3 + 6HX
PX3 c iu ch trc tip:
2P + 3X2 2PX3
b/ Phtpho pentahalogenua PX5
Ch c PF5, PCl5, PBr5. iu kin thng PCl5 l cht rn, c.
trng thi kh PF5, PCl5 c cu to hnh tam gic i.
dP-F = 1,52Ao
137
dP-Cl = 2,04Ao
trng thi rn, PBr5 c mng li ion.
Cc phtpho pentahalogenua b thy phn d dng
PX5 + H2O POX3 + 2HX
PX5 + 4H2O H3PO4 + 5HX
PX5 c iu ch trc tip
2P + 5X2 2PX5
IX.3. CC NGUYN T ASEN, ANTIMON, BITMUT (As, Sb, Bi)
IX.3.1. n cht
1. L tnh
Ging P, cc nguyn t As, Sb c mt vi dng th hnh: dng khng kim

loi v dng kim loi. Ring Bi ch c dng kim loi.
Dng khng kim loi ca As, Sb - c to nn khi ngng t hi ca

chng, l nhng cht rn mu vng gi l asen vng, antimoan vng. Dng kim
loi ca As c mu trng bc, ca antimoan trng bc pht . Sau y l mt s
thng s vt l:
Tnh cht As Sb Bi
t0nc (0C) 817(36 at) 630 271
t0s (0C) 610 1440 1627
d (g/cm3) 5,7 6,7 4,8
Hi ca As, Sb, Bi u gm cc phn t t din E4 nh P4, phn t As

bt u b phn hy hon ton 17000C. 20000C trong hi ca As, Sb, Bi c
cn bng:
E4 = 2E2 = 4E v trn nhit ch c phn t mt nguyn t

138
2. Ha tnh
Trong khng kh iu kin thng Sb khng b bin i, As v Bi b oxy ha

trn b mt. Khi un nng, chng u chy to thnh oxit
4Bi + 3O2 2Bi2O3
dng bt, khi un nng chng tc dng vi halogen v S:
2 Bi + 3S Bi2S3 2As + 3Cl2 2AsCl3
Vi cc kim loi kim, kim th, v mt s kim loi khc As, Sb, Bi
tng tc to nn asenua, antimoanua, bitmutua. V d:
3Mg + 2As Mg3As2 3 Na + As Na3As
Vi cc kim loi cn li chng to nn cc hp kim. V d: cho thm Sb

vo Sn v Pb s lm tng cng v bn axit ca hp kim. Hp kim Sb dng
lm ch in, Bi to nn cc hp kim d nngchy, dng trong thit b cu ha t
ng.
As, Sb, Bi c in th cc dng nn khng tan trong dung dch HCl

nhng tan trong axit nitric HNO3. As, Sb to ra axit, Bi to ra mui
3As + 5HNO3 + 2H2O 3H3AsO4 + 5NO
axit asenic
3Sb + 5HNO3 3HSbO3 + 5NO + H2O
axit antimoanic
Bi + 4HNO3 Bi(NO3)3 + NO + 2H2O
Sb, Bi khng tan trong kim, ring As tan c trong kim nng chy
2As + 6NaOH = 2Na3AsO3 + 3H2
3. Trng thi thin nhin, phng php iu ch
139
C 3 nguyn t As, Sb, Bi u tng i ph bin trng t nhin, As

chim 10-4%, Sb 5.10-6%, Bi 2.10-6% tng s nguyn t trong v tri t.
Chng tn ti ch yu dng khong vt sulfua: As4S4 reanga, As2S3 oripimen,
Sb2O3 antimonit, Bi2S3 bimutin.
iu ch ngi ta t chy qung sulfua thnh oxit, ri dng than

kh
2E2S3 + 9O2 6SO2 + 2E2O3
E2O3 + 3C 3CO + 2E
IX.3.2.Hp cht
IX.3.2.1. Hydrua ca asen, antimon, bitmut
Ba nguyn t As, Sb, Bi ch to nn hydrua kiu EH3 c cu to ging

NH3 v PH3
Asin AsH3 l cht kh khng mu c mi ti.
Stibin SbH3 l cht kh khng mu c mi trng thi. Tt c u rt c. Sau

y l mt s c im:
c im NH3 PH3 AsH3 SbH3
0
di lk E-H ( A ) 1,01 1,4 1,52 1,7
Nng lng trung bnh 93 78 71 61

ca lin kt (kcal/mol)
Gc HEH 107 93 92 91
t0nc (0C) -78 -133 -116 -88
t0s (0C) -33 - 88 -62 -18
Nhit to thnh Ho
-11 +3 +43 +35
(kcal/mol)
140
Nng lng trung bnh ca lin kt E - H gim dn, di lin kt E - H tng

dn lm cho bn nhit ca cc hydrua gim xung t NH3 n BiH3.
S gim gc HH ca hydrua cho thy s gim kh nng lai ha sp3 ca

cc nguyn t t N n Bi. V vy tnh cht cho cp e ca cc hydrua yu dn,
NH3 c kh nng kt hp vi mi axit v nc, cn cc hydrua cn li phn ng
vi cc axit yu dn
Tnh kh tng t NH3 n BiH3, PH3, AsH3, SbH3 l cc cht kh mnh.

Chng t bc chy trong khng kh
PH3 + O2 H3PO4
AsH3 + O2 H3AsO4
Chng kh c mui Cu2+, Ag+ to ra kim loi:
6AgNO3 + AsH3 + 3H2O 6Ag + 3HNO3 + H3AsO3
AsH3, SbH3 c iu ch bng cch cho mui ca chng tc dng vi axit
V d: Mg3Sb2 + 6HCl 2SbH3 + 3MgCl2
IX.3.2.2. Oxit ca As, Sb, Bi mc oxy ha +3
As4O6, Sb4O6, Bi2O3 l cc cht rn, t tan trong nc, As4O6 tan mt phn
to ra axit asen.
As4O6 + 3H2O = 2H3AsO3 (v c HAsO2)
Trong cc oxit trn, t asen n bitmut, tnh axit gim dn, tnh baz tng
dn. As2O3 d tan trong kim:
As2O3 + 2NaOH 2NaAsO2 + H2O
Bi2O3 d tan trong axit to ra mui ca Bi3+ v hu nh khng tan trong

dung dch kim
Bi2O3 + 6HCl 2BiCl3 + 3H2O
141
Khi un nng, cc axit b C, H2 kh d dng

0
Bi2O3 + H2
t
2Bi + 3H2O
As2O3 th hin tnh kh khi tc dng vi cc cht axy ha mnh nh O3,

H2O2, KMnO4, K2Cr2O7, HNO3
2As2O3 + 4HNO3 6H3AsO4 + 4NO
As2O3 rt c, liu cht ngi l 0,1 gam. N c dng ch thuc tr su,

ch thy tinh trong sut v cht mu. Cc oxit c iu ch bng cch t chy
nguyn t hay mui sulfua.
Sb + O2 Sb2O3
IX.3.2.3. Oxit ca As, Sb, Bi mc oxy ha +5
As2O5 l cht dng khi v nh hnh nh thy tinh.
Sb2O5 l cht dng bt mu vng nht.
Bi2O5 l cht dng bt mu nu thm.
Cc oxit ny d b phn hy to thnh O2 v oxit thp hn:

o
2As2O5
t
As4O6 + 2O2
Trong khng kh As2O5 n rt d b chy ra to axit asenic. Cn Sb2O5

v Bi2O5 rt t tan trong nc, Sb2O5 tan c trong dung dch kim:
Sb2O5 + 2KOH + 5H2O 2K[Sb(OH)6]
Kali hecxa hydroyl antimonat
Cc oxit As2O5, Sb2O5 c th c iu ch bng cch lm mt nc ca

oxy axit tng ng, ring Bi2O5 c th iu ch bng cch dng cht oxy ha rt
mnh nh Cl2, KMnO4, O3 oxy ha Bi2O3 trong kim c
Bi2O3 + 4KOH + 2Cl2 Bi2O5 + 4KCl + 2H2O
IX.3.2.4. Hydroxit ca As, Sb, Bi mc oxy ha +3

142
As(OH)3 ch bit trong dung dch; Sb(OH)3, Bi(OH)3 l kt ta mu trng

dng bng t tan trong nc v d mt nc bin thnh antimonyl hydroxyt
SbO(OH) v bimutyl hydroxyt BiO(OH). T As(OH)3 n Bi(OH)3 tnh axit
gim, tnh baz tng. As(OH)3 l axit yu, Sb(OH)3 lng tnh, tan c trong
baz v trong axit
Si(OH)3 + 3HCl SbCl2 + 3H2O
Sb(OH)3 + NaOH Na[Sb(OH)4]
Bi(OH)3 l hydroxyt baz ch tan trong axit
Bi(OH)3 + 3HCl BiCl3 + 3H2O
As(OH)3 c iu ch bng cch ha tan As2O3 vo nc. Sb(OH)3 v

Bi(OH)3 c iu ch t mui clorua tng ng.
BiCl3 + 3NaOH Bi(OH)3 + 3NaCl
Sb(OH)3 cn iu ch theo phn ng
Na[Sb(OH)4] + HCl Sb(OH)3 + NaCl + H2O
IX.3.2.5. Sulfua ca As, Sb, Bi
As, Sb, Bi to nn cc sulfua c thnh phn tng t nh oxit: As v Sb

to nn hai loi sulfua As2S3, As2S5, Sb2S3, Sb2S5; Bi ch to nn sulfua Bi2S3.
Nhng loi M2S3 ca c 3 nguyn t tn ti t do trong t nhin di dng
khong vt.
Cc sulfua As2S3, As2S5 l cht dng bt mu vng, Sb2S3 v nh hnh

mu da cam, Bi2S3 c mu nu en.
Khi un nng trong khng kh cc sulfua ca As,Sb, Bi d chy to thnh

oxyt
Bi2S3 + O2 Bi2O3 + SO2
143
Tt c cc sulfua ca As, Sb, Bi u t tan trong nc v dung dch axit

long. Ging nh oxyt, sulfua ca As, Sb c th tan trong dung dch kim:
2As2S3 + 12NaOH 2Na3AsO3 + 2Na3AsS3 + 6H2O
Natri asenit Natri thiasenit
Chng tan trong dung dch sulfua kim loi kim, hay amni to ra mui
thio.
As2S3 + 3(NH4)2S 2(NH4)3AsS3
amni thio asenit
As2S5 + 3(NH4)2S 2(NH4)3AsS4
amni thio asenat
Khi axit ha dung dch ca cc mui thio , sulfua tng ng s lng xung.
2(NH4)2AsS4 + 6HCl As2S5 + 6NH4Cl + 3H2S
Sulfua ca asen khng tan trong axit HCl c nhng sulfua ca Sb, Bi tan c
Sb2S3 + 6HCl SbCl3 + 3H2S
Sb2S5 + 6HCl 2SbCl3 + 3H2S + 2S
Tt c cc sulfua ca As, Sb, Bi u tan trong axit HNO3.
3As2S5 + 40HNO3 + 4H2O 6H3AsO4 + 15H2SO4 + 40NO
3As2S3 + 28HNO3 + 4H2O 6H3AsO4 + 9H2SO4 + 28NO
Sulfua asen c dng lm rng lng da th, lm thuc n v cht mu v

c, Sb2S3 dng lm thuc n, dim v thy tinh.
Cc sulfua c iu ch theo mt phng php chung l sc kh H2S vo

dung dch hp cht mc oxy ha tng ng ca As, Sb, Bi trong mi trng
axit.
144
2Bi(NO3)3 + 3H2S Bi2S3 + 6HNO3
2Na2AsO4 + 5H2S + 6HCl As2S5 + 6NaCl + 8H2O
IX.3.2.6. Trihalogenua MX3 ca As, Sb, Bi
C 3 nguyn t to nn trihalogenua MX3 vi tt c cc halogen, chng c

cu to phn t v tnh cht l ha ging PX3. Ngha l trong phn t nguyn
t As, Sb, Bi u trng thi lai ha sp3.
Tr BiF3 l cht kh nng chy, tt c cc trihalogenua cn li l hp cht

cng ha tr ngha l cht lng hay cht rn d nng chy, d tan trong cc dung
mi hu c.
Sau y l bng nhit nng chy v nhit si:
Cht AsF3 SbF3 BiF3 AsCl3 SbCl BiCl3

3
t0nc -6 292 730 -16 73 234
t0s 57 319 730 130 221 441
Cht AsBr3 SbBr3 BiBr3 AsI3 SbI3 BiI3
t0nc 31 97 218 144 171 403
t0s 221 288 461 403 401 439
Cc halogenua u tan trong nc v thy phn mnh
AsCl3 + H2O = As(OH)3 + 3HCl
SbX3 v BiX3 thy phn mnh to ra mui baz:
SbCl3 + H2O = Sb(OH)2Cl + 2HCl
Sb(OH)2Cl = SbOCl + H2O
Cc trihalogenua MF3 c iu ch bng cch cho oxit tc dng vi HF
145
M2O3 + 6HF 2MF3 + 3H2O
Nhng trihalogenua khc c iu ch trc tip t cc nguyn t
2M + 3X2 2MX3
IX.3.2.7. Pentahalogenua MX5 ca As, Sb, Bi
Ngy nay ngi ta bit c 4 pentahalogenua AsF5, SbF5, BiF5 v SbCl5.

Trong cc phn t As, Sb, Bi trng thi lai ha dsp3. iu kin thng
AsF5 l cht kh, SbF5 l cht lng nht, SbCl5 l cht lng mu vng bc khi,
BiF5 l cht rn dng tinh th
Cht AsF5 SbF5 BiF5 SbCl5
t0nc -90 8 151 3
t0s -53 143 230 140
T AsF5 n SbF5 nhit nng chy v nhit si tng ln t ngt, do

trong antimoan pentaflorua c hin tng trng hp phn t.
Tnh cht ha hc c trng ca cc penta halogenua MX5 l d kt hp

vi mt s cht to nn cc sn phm nh SbF5.NO2, SbF5.SO2. Chng cng kt
hp vi halogenua kim loi kim MX to nn phc cht c cng thc chung
M[MX6].
Khi tng tc vi nc, cc pentahalogenua to axit. Cc pentahalogenua

SbF5, BiF5, SbF5 c th iu ch bng cch cho d halogen tc dng vi kim
loi:
2Bi + 5F2 2BiF5
Ring AsF5 c th iu ch bng tc dng ca AsF3 vi hn hp SbF3 v Br2
2SbF3 + AsF3 + Br2 2SbF2Br + AsF5
146
CHNG X. CC NGUYN T IVA
Phn nhm IVA gm cc nguyn t cacbon (C), silic (Si), gecmani (Ge),
thic (Sn), ch (Pb).
Mt s c im ca cc nguyn t
Nguyn t C Si Ge Sn Pb
S th t 6 14 32 50 82
Khi lng nguyn t 12,01 28,08 72,59 118,69 207,19
R kim loi ca ngt (A0) ---- 1,34 1,39 1,58 1,75
R cng ha tr (A0) 0,77 1,17 1,22 1,40 ----
R ion M2+ (A0) ---- ---- 0,65 1,02 1,26
R ion M4+ (A0) ---- 0,34 0,44 0,67 0,76
NL ion ha (kcal/mol) I1 259,6 187,9 182 169,3 171
I2 562,2 376,8 367,4 337,4 346,6
I3 1104 771,7 789 703,2 736,4
I4 1487 1041 1050 939,1 975,9
Nguyn t ca cc nguyn t ny c lp eclectron ha tr l ns2np2. Do

tng nng lng ion ha kh ln, chng khng th mt 4 eclectron ha tr to
nn ion 4+, mt khc m in cng khng ln chng t rng chng khng th
kt hp thm eclectron bin thnh ion 4-. t c cu hnh eclectron bn,
nhng nguyn t ca nguyn t nhm IVA to nn nhng cp eclectron chung
ca lin kt cng ha tr v trong cc hp cht chng c mc oxy ha t -4 n
+2 v +4.
147
X.1. CACBON
X.1.1. n cht
1. L tnh
Cacbon thin nhin l mt hn hp ca hai ng v 12C (98,89%) v 13C

(1,11%). Ngoi ra trong cacbon cn c nhng vt ca ng v phng x14C.
ng v 14C c trong kh quyn dng kh CO2 vi nng khng i. Nh c
chu k bn hy kh ln (5570 nm) cho nn 14C trong kh CO2 ca kh quyn
c pht hin trong mi cht c cha cabon nm cn bng vi CO2 ca kh
quyn. Khi sinh vt cht n thi ng ha nhng lng mi 14C v lng 14C
gim xung do s phn hy phng x. Nh vy bit 14C trong mt vt c ngun
gc hu c (tnh c khi cn c vo phng x) v bit hng s nng 14C
trong kh quyn, ngi ta c th tnh c thi im m sinh vt cht. Phng
php ny cho php xc nh tui ca cc ng vt v thc vt thi c xa vi sai
s khong 5%.
Cacbon c 3 dng th hnh c trng l kim cng, than ch (graphit) v

cacbin, ng vi cc trng thi lai ha c trng ca cacbon.
- Kim cng:
Kim cng c mng nguyn t phi tr lp phng, trong tinh th mi

nguyn t cacbon trng thi lai ha sp3 lin kt cng ha tr vi 4 nguyn t C
bao quanh kiu hnh t din u, khong cch gia cc nguyn t cacbon l
0
1,545 A .
Mng li tinh th kim cng l kiu mng li nguyn t in hnh.

Ton b tinh th c cu trc rt u n cho nn thc t tinh th l mt phn t
148
khng l. Kin trc nh vy gii thch nhiu tnh cht vt l ca kim cng: kim
cng c t khi ln (3,51) v cng nht trong tt c cc cht. Thang cng
ca Mox ly cng ca kim cng bng 10, ca tan bng 1.
1. tan 2 Thch cao 3 Can xi 4 Florit 5 Apatit
6 Phenspat 7 Thch anh 8 Topaz 9 Corunum 10 Kimcng
Kim cng khng dn in. Tinh th kim cng hon ton trong sut,
khng mu v c ch s khc x ln nht nn trng lp lnh v p
C C C
C C C C
C C C C
C C C C
C C C
C C C C
C C C C
149
C C C C
C C C C
C C C C
C C C
Cu trc ca mt lp than ch
- Than ch:
Than ch c kin trc lp, trong mi nguyn t cacbon trng thi lai
ha sp2 lin kt vi 3 nguyn t cacbon xung quanh cng nm trong mt lp to
thnh vng 6 cnh, nhng vng ny lin kt vi nhau to thnh mt lp v tn.
Sau khi to thnh lin kt, mi nguyn t cacbon cn c 1 eclectron trn obital
nguyn t 2p cha lai ha s to thnh lin kt vi mt trong 3 nguyn t C
bao quanh. Nn lin kt trong than ch khng nh ch trong ton b tinh th.
Nh than ch khc vi kim cng: c mu xm, c nh kim, dn nhit v dn
in (c dng lm in cc).
Ty theo s sp xp ca cc lp i vi nhau, than ch c 2 dng tinh th:

lc phng v mt thoi. Than ch tng i mm, d tch thnh lp, v mt ha
hc hot ng mnh hn kim cng mt t, khi lng ring d = 2,2.
- Cacbin:
Cacbin l bt mu en, cha 99% cacbon, c mng lc phng, c cu

trc mch thng (=C=C=)n, trong mi nguyn t cacbon to thnh 2 lin kt
v 2 lin kt . Cacbin l cht bn dn. N c tng hp cch y khng lu.
- Cacbon v nh hnh:
Nhiu dng v nh hnh ca cacbon nh than g, mui than, than cc...

thc t l cc dng vi tinh th ca than ch. Than dng bt mn c b mt tip
xc rt ln nn hp ph c mt lng ln kh v dung mi t dung dch. Than
mi iu ch c kh nng hp ph rt cao gi l than hot tnh. Li dng tnh
150
cht ny ngi ta dng than hot tnh tr cht c (dng trong mt n phng
c), loi cht bn khi lc ng v lc du thc vt.
2. Ha tnh
nhit thng C kh tr v mt ha hc nhng nhit cao C tr

nn hot ng. nhit cao n c th tng tc vi nhiu khng kim li v
kim loi. Cacbon v nh hnh hot ng mnh nht.
Khi chy trong khng kh cacbon tng tc vi oxy theo phn ng:
C + O2 = CO2 H = - 94,32 kcal/mol
Ngoi kh CO2, trong sn phm lun lun c CO v khi nhit cng cao. V
nhit cao lng ny nhiu:
CO2 + C 2CO H = +41,3 kcal/mol
Thc t di 5000C sn phm t chy C ch l CO2, v trn 900oC ch c

CO. V vy ngi ta cho rng trong phn ng chy ca cacbon trong khng kh
cn c phn ng ph:
2C + O2 = 2CO H = - 53,04 kcal
Hi lu hunh tng tc vi than to ra isulfua cacbon:
C + 2S CS2 H = +26 kcal
Cacbon cn tng tc c vi H2 nhit cao khi c mt xc tc niken:
C + 2H2 CH4
Cacbon cn tng tc vi nhiu kim loi to thnh cc hp cht cacbua kim

loi:
o
Ca + 2C
t
CaC2 (Cacbua canxi)
Al + C Al4C3 (Cacbua nhm)
151
Khi tc dng vi cc hp cht, cacbon th hin tnh kh. nhit cao n kh

c nc, clorat, nitrat, axit HNO3, axit H2SO4 c... to nn kh CO2 :
o
C + H2O
t
CO + H2 (Kh than t)
o
C + H2O
t
CO2 + 2H2
o
2C + 4NaNO3
t
4NaNO2 + 2CO2
C + 4HNO3 CO2 + 4NO2 + 2H2O
C + 2H2SO4 CO2 + 2SO2 + 2H2O
2KClO3 + 3C 2KCl + 3CO2
c bit n kh c oxyt ca nhiu kim loi:

o
C + CuO
t
Cu + CO
o
Fe2O3 + 3C
t
2Fe + 3CO
Nn trong luyn kim ngi ta dng phn ng ny iu ch mt s kim loi.
c bit, cu trc lp v xp ca than ch cho php nhiu phn t i vo

khong khng gian gia cc lp tinh th to nn vi than ch nhng hp cht
kiu xm nhp. V d: Khi tng tc vi flo 4500C, than ch to nn mt sn
phm mu trng gi l florua than ch vi t l C:F = 1:0,99. Trong trng hp
l tng hp cht c cng thc (CF)n, trong mi nguyn t C to nn mt
lin kt C-F v 3 lin kt C-C. y C chuyn t trng thi lai ha sp2 sang
trng thi sp3. V vy cc lin kt C-C trong tinh th (CF)n khng cn nm trong
mt mt phng nh trong tinh th ca than ch v khng cn lin kt khng
nh c nn florua than chi l cht cch in. Florua than ch khng tan trong
cc dung mi thng thng.
152
Khi un nng trn 5000C n phn hy mnh (c th gy n) to thnh cc

florua d bay hi ca cc cacbon nh CF4, C2F6, v than mui. Florua than ch
rt bn v mt ha hc, n khng tng tc vi axit v vi kim.
3. Trng thi thin nhin
Trong thin nhin, C chim 0,14% tng s nguyn t, khng nhiu lm

nhng c vai tr c bit ln v hp cht ca cacbon l c s ca mi sinh vt.
Mt lng rt ln cacbon nm trong khong vt canxit (CaCO3), lmit
(CaCO3.MgCO3). Than m, du m l cc khong vt ca cacbon. Cacbon cn
c trong cc hp cht hu c. Chnh than mo v du m l sn phm phn hy
ca cc hp cht trong iu kin thiu khng kh.
Than m hay cn gi l than gm c nhiu loi:
- Than antraxit: l loi than gi nht v a cht. N cha trn 90% cacbon c
mu t en n xm.
- Than (vi ngha hp) tr hn antraxit, n cha t 75 n 90% cacbon.

Ngi ta chia than ra lm nhiu loi: than bo (hay than m), than gy, than
dnh... Than cng c mu en nhng khc antraxit ch trng n c v bo,
khi chy cho nhiu khi v t nhit hn than antraxit. Khi c nhit phn, than
tch ra mt s cht d bay hi v li than cc.
- Than nu: L loi than tr hn nhiu. N cha t 60 n 70% C. N c mu

nu, mm hn than v antraxit. Nhn vo than nu ngi ta cn nhn thy cu
to ca g.
- Than bn: Tr nht trong cc loi than m. N cha t 55 n 60% C. N l

vt liu mu hung, xp v cha mt lng ln nc. Thnh phn nguyn t ca
than bn rt gn vi thnh phn nguyn t ca g.
4. Phng php iu ch cc dng th hnh ca cacbon

153
- Kim cng: Khai thc cc m c cha kim cng; iu ch kim cng

nhn to ngi ta un nng than ch nhit 1800 - 3800 0C di p sut
60000 - 120000atm. khi c cc kim loi (Fe, Cr, Ni...) lm cht xc tc:
Cgr
60000 - 38000xtCKLCT
1800- 120000at, Ckc
Kim cng nhn to v phm cht k thut khng nhng t m cn vt kim

cng thin nhin. Tuy nhin kim cng nhn to c tinh th nh, mu khng
p, khng th dng lm trang sc c.
- Than ch: iu ch bng cch un nng than antraxit hay than cc nhit
2500- 30000C trong l in c bit.
X.1.2. Cc hp cht ca cacbon
X.1.2.1. Cacbon oxit (CO)
CO c cu hnh in t
(slk)2 (*s*)2 (xlk)2 (y lk)2 (zlk)2
Cng thc cu to: :C O:
Cacbon oxyt c khi lng phn t, tng s eclectron v cu to phn t ging

nit, nn c mt s tnh cht ha l ging nit.
a. L tnh: ging nit, CO l cht kh khng mu, khng mi, kh ha lng

(nhit si l -191,50C), kh ha rn (nhit nng chy -2040C) v t tan
trong nc. N rt bn vi nhit: 60000C vn cha phn hy.
b. Ha tnh: ging nit, CO km hot ng nhit thng nhng nhit

cao kh nng kh tng mnh c l do s bin i cu trc eclectron bn ca
phn t.
* Tc dng vi oxy: khong 7000C CO chy trong khng kh cho ngn

la mu xanh lam v pht nhiu nhit:
154
2 CO + O2 = 2 CO2 Ho = -67,9 kcal/mol
v vy n c dng lm nhin liu.
* Tc dng vi S: khi t nng, CO b S oxy ha:
CO + S = COS
* Khi chiu sng hoc c xc tc, CO tc dng vi clo to thnh

oxclorua:
CO + Cl2 COCl2
Oxclorua cn gi l photgen (phot = nh sng, gen = sinh ra). Photgen l mt

cht c nng hn khng kh c dng lm bom hi ngt trong chin tranh th
gii ln th nht.
Photgen kh hot ng nn c dng nhiu trong tng hp hu c.
* CO c th kh c oxyt ca mt s kim loi:
V d phn ng xy ra trong l cao:
Fe2O3 + 3CO = 2Fe + 3CO2
Cacbon oxyt cn kh c I2O5 n I2
I2O5 + 5CO = I2 + 5CO2
Phn ng ny c dng nh lng CO trong ha hc phn tch.
* trong dung dch, kh CO c th kh cc mui ca kim loi qu nh

vng, platin, n kim loi t do.
V d: PdCl2 + H2O + CO = Pd + 2HCl + CO2
Nh phn ng ny ngi ta pht hin c nhng vt CO trong hn hp kh.
* Nhng tng tc ca CO vi cc cht oxy ha khc trong dung dch

thng ch xy ra khi c cht xc tc. V d: n kh c KMnO4 khi c mt
Ag bt, kh c K2Cr2O7 khi c mt mui thy ngn.
155
* Kh nng kh ca CO tng ng H2 phn t. thy r hot tnh

tng i ca CO v H2 , ta so snh cc hng s cn bng di y cc nhit
khc nhau.
H2 + CO2 CO + H2O ; Ho = 9,87 kcal
Hng s cn bng l:
C CO .C H 2 O
K
C H 2 .C CO
2
t0 C 700 800 830 1000 1200 1400
K 0,6 0,9 1 1,7 2,6 3,45
nhit 8300C, trong hn hp cn bng c lng CO v H2 nh nhau,

ngha l 2 kh c i lc nh nhau i vi oxy, di 8300C CO kh mnh hn,
trn 8300C H2 kh mnh hn.
Tuy vy khi tc dng vi H2, CO c th th hin tnh oxy ha to nn cc

sn phm khc nhau ty theo cc iu kin khc nhau.
V d: 3000C, xc tc Ni
CO + 3H2 CH4 + H2O
Trong nhng iu kin nhit , p sut thch hp, vi s c mt ca cc

cht xc tc nh Fe, Co, Ni, Ru... CO c th b kh to ra cc hydro cacbon
nng hn, to nn exng tng hp.
n CO + (2n + 1) H2 CnH2n + 2 + n H2O
2n CO + (n + 1) H2 CnH2n + 2 + n CO2
n CO + 2n H2 CnH2n + n H2O
156
2n CO + n H2 CnH2n + n CO2
3500C, 250atm, vi xc tc ZnO c hot ha bng Cr2O3 , CO kt hp vi

H2 to ra ru mtylic.
CO + H2 CH3OH
Phn t CO cn ng vai tr phi t trong nhiu phc cht khc nhau.

Cc hp cht cacbonyl ca nhng nguyn t d nh Ti(CO)7, Cr(CO)6, Ni(CO)4...
l nhng hp cht rt l th v phng din l thuyt v thc t. Cacbonyl l cc
hp cht nghch t.
Nh vy khi chng c to thnh th xy ra s ghp i cc eclectron

ha tr ca nguyn t d, lin kt trong cacbonyl c to thnh theo c ch
cho nhn nh cc obital t do ca nguyn t d v cc cp eclectron t do ca
nhng phn t CO.
V d: Crm c 6 obital t do kt hp c vi 6 phn t CO.
Cr:
3d 4s 4p
CO kt hp vi cht hmglbin (Hb) trong mu to thnh hp cht bn:
Hb + CO HbCO
Lm cho Hb khng lm c nhim v ti oxy t phi n cc mao qun

ca cc c quan ng vt. V th CO l cht kh ht sc c. N li khng c
mu v mi nn ht sc nguy him i vi con ngi.
CO khng tc dng vi nc v kim iu kin thng nhng nhit

cao v p sut cao tng tc xy ra. Chng hn 2000C, p sut 15at, CO
tc dng vi kim to ra mui focmiat.
CO + NaOH HCOONa (focmiat natri)
157
Trong phng th nghim, ngi ta iu ch CO bng cch cho H2SO4 m c

vo axit HCOOH lng v un nng:
HCOOH H2SO4 CO + H2O
hoc cho HCOOH tc dng vi axit closulfomic nhit thng.
HCOOH + HSO3Cl = H2SO4 + HCl + CO
Trong cng nghip kh CO c sn xut lng ln lm nhin liu dng:
Kh than t: hn hp CO, H2 (cho hi nc i qua than t nng )
Kh l ga: 25% CO, 70% N2, 4% CO2 (t chy than antraxit trong l ga)
X.1.2.2. Cacbon ioxit (CO2) v axit cacbonic (H2CO3)
CO2 c cu to: O=C=O, vi di lin kt C-O l 1,162 A0. Nng lng

trung bnh ca lin kt l 192 Kcal/mol. CO2 dng kh gi l kh cacbonic. N
khng mu, khng mi v v hi chua, nng hn khng kh, d ha lng v d
ha rn. (t0nc = -570C 5at). p sut 60 atm, ngay nhit thng n bin
thnh cht lng khng mu linh ng. Khi c lm lnh t ngt, cht lng
bin thnh khi rn nh tuyt gi l tuyt cacbonic. Tuyt cacbonic khng nng
chy di p sut thng m thng hoa -780C.
CO2 rt bn vi nhit, 15000C ch mi phn hy thnh CO v O2 vi t

l 1,5% v 20000C vi t l 75%.
2CO2 2CO + O2 ; H0 = 135,8 kcal
Kh CO2 khng chy v khng duy tr s chy, khng duy tr s sng, v vy

ngi ta dng kh CO2 hay CO2 lng cha chy.
Nhng c mt s kim loi hot ng mnh nh K, Mg, Al, Zn vn chy

c trong CO2:
4Al + 3CO2 = 2Al2O3 + 3C
158
CO2 tan c trong nc (1 lt H2O ha tan c 1,7 lt CO2). Khi tan trong
nc phn ln CO2 dng hydrat ha, mt lng nh tc dng vi nc to axit
cacbonic.
CO2(kh) + H2O CO2.H2O(dd) H2CO3
Nh vy CO2 l anhydrit ca axit cacbonic nn dc gi l kh cacbonic.
H2CO3 l mt axit yu khng bn, khng th tch ra iu kin thng.

Trong nc n phn ly theo 2 nc:
H2CO3 + H2O H3O+ + HCO3- K1 = 4,16.10-7
HCO3- + H2O H3O+ + CO32- K2 = 4,84.10-11
y hng s th nht K1 a c tnh vi gi thit l ton b kh CO2 tan trong

nc u di dng H2CO3, ngha l:
C H 3O .C HCO 3
K1 = = 4,16.10-7
C CO 2 C H 2CO 3
Nu tnh nng tht ca axit cacbonic, hng s phi l:
C H 3O .C HCO 3
K1 = = 2.10-4
C H 2CO 3
gi tr ny ph hp vi cng thc (HO)2CO ca axit cacbonic. Tuy vy axit

cacbonic vn l axit yu.
iu kin thng CO2 kt hp c vi NH3 kh to amni cacbamat:
ONH4
CO2 + 2NH3 O=C
NH2
159
amoni cacbonat
Mui ny khng bn, khi un 1800C, P = 200atm mt nc to ra ur.
ONH4 NH2
O=C O=C + H2 O
NH2 NH2
CO2 cn tc dng c vi cc hp cht baz.
CO2 + CaO CaCO3
2KOH + CO2 K2CO3 + H2O
2KNH2 + CO2 K2CN2 + H2O
CO2 c iu ch khi t chy hon ton than cc, l sn phm ph ca qu

trnh ln men ru:
C6H12O6 2C2H5OH + 2CO2
CaCO3 + 2HCl = CaCl2 + H2O + CO2
X.1.2.3. Cacbonat (CO32-), bicacbonat (HCO3-)
Axit cacbonic to nn hai loi mui: cacbonat (mui trung tnh) v

bicacbonat (mui axit). Anion CO32- c cu to tam gic u tng t phn t
BF3
2-
O
C dC-O = 1,29A0
O O OCO = 1200
160
ion HCO3- v CO32- khng mu nn cc mui cacbonat v bicacbonat ca cation

khng c mu u khng mu.
Cc mui cacbonat kim loi kim v amni tan, cc mui cacbonat kim
loi khc khng tan, mui bicacbonat d tan hn nhng khng bn nhit, d b
phn hy.
Ca(HCO3)2 CaCO3 + H2O + CO2
X.1.2.4. Cacbon isulfua (CS2)
Cacbon to vi S cc hp cht CS, CS2, C2S3 (tng t CO, CO2, C2O3)

quan trng nht l cacbon isulfua CS2. trng thi lng CS2 c cu to:
S=C=S dC-S = 1,56A0
iu kin thng CS2 l mt cht lng khng mu, d bay hi (nhit nng
chy l -1110C, si 46,20C) c mi thm d chu, rt c, c dng lm
thuc tr su.
Trong khng kh, hi CS2 d bc chy khi tip xc vi vt nng:
CS2 + 3 O2 = CO2 + 2SO2
nhit thng, n khng tc dng vi nc, nhng 150 0C b thy phn:
CS2 + 2 H2O CO2 + 2H2S
ging nh CO2 d chuyn thnh CO32-, CS2 d kt hp vi S2- to ion

thiocacbonat CS32-
CaS + CS2 CaCS3 canxi thiocacbonat
CS2 cn tc dng vi halogen nh Cl2 :
CS2 + 3Cl2 CCl4 + S2Cl2
Trong cng nghip, CS2 c iu ch bng cch cho hi S qua than cc nhit
900 -10000C:
C + 2S CS2
161
X.1.2.5. Cacbua kim loi
Cacbua kim loi l hp cht ca cacbon vi kim loi to thnh khi hai
nguyn t tng tc trc tip vi nhau nhit trn 20000C hay khi than
tng tc vi oxyt kim loi hoc kim loi tng tc vi hydro cacbon nhit
cao.
Cacbua kim loi c chia lm 2 loi:
a. Cacbua ion
Cacbua ion c to nn ch yu bi cc kim loi thuc cc nhm IA,

IIA, IIIA. Nhng cacbua ny thng l cc hp cht ion nn c gi l cacbua
ion. Tinh th ca chng khng c mu, trong sut, khng dn in nhit
thng, d b nc v axit long phn hy. Da vo sn phm c to nn khi
b phn hy ngi ta chia ra cc nhm sau y:
a1. Cacbua to nn mtan khi b thy phn
Nhm ny bao gm Be2C, Al4C3. Chng l cht dng tinh th v kh

nng chy, trong tinh th ca chng c cation kim loi v anion C4-, khi tng
tc vi nc anion C4- b thy phn gii phng mtan.
Al4C3 + 12H2O 4Al(OH)3 + 3CH4
V vy nhm cacbua ny gi l mtanit.
a2. Nhm cacbua to nn axtylen khi b thy phn
Nhm ny bao gm nhng cacbua c cng thc chung l M2C2 (M = kim

loi kim, Au, Ag, Cu), MC2 (M = kim loi kim th, Zn, Cd) v M2 (C2)3 (vi
M=Al, Fe). Trong tinh th ca nhng cacbua nhm ny c cha ion C22- , khi
tng tc vi nc, ion C22- b thy phn gii phng axtylen.
CaC2 + 2H2O Ca(OH)2 + C2H2
V vy nhm cacbua ny c gi l axtylenit. Cu2C2 v Ag2C2 khng b thy

phn nhng phn ng vi axit clohydric cho axtylen.
162
a3. Nhm cacbua to nn axtylen v hydro cacbon khc khi b thy phn
Nhm ny bao gm YC2, LaC2, TbC2, YbC2, LuC2, Ce2C3, Tb2C3.
Trong cc hp cht c cng thc MC2 ngi ta ch yu tm thy kim loi

ha tr 3, trong cc hp cht M2C3 kim loi cng trng thi ha tr 3. Nhng
cacbua ny khng th coi mt cch n gin l c cha ion C 22 v nguyn t
kim loi vi s oxy ha bnh thng. Khi b thy phn chng ch cho 50-70%
C2H2 cng vi C2H4, CH4, H2 c l theo phn ng:
2 C 32 + 6 H2O C2H2 + C2H4 + OH-
v nhng phn ng khc na.
b. Cacbua xm nhp
c to nn ch yu bi cc kim loi chuyn tip, nhng cacbua xm

nhp in hnh c cng thc chung l MC (M = Ti, Zn, Hf, V, Nb, Ta) v M2C (
M= Mo, W). Trong tinh th ca nhng cacbua xm nhp in hnh , nhng
nguyn t cacbon xm nhp vo nhng l trng bt din ca kim loi, n khng
lm bin i kin trc eclectron t do v nhng c tnh khc ca kim loi tinh
khit m cn lm bn thm mng li tinh th ca kim loi.
Do kin trc nh vy, cacbua xm nhp c nhng c im nh: c nh

kim, dn in, rt cng v kh nng chy. cng cacbua xm nhp t 9 - 10,
nhit si (3000-4000oC ) cn cao hn nhng kim loi kh nng chy nh Be,
W v hn c C. Cc cacbua xm nhp in hnh cn rt bn v mt ha hc,
chng ch b phn hy khi un nng vi hn hp HF v HNO3.
V d: 3WC + 9HNO3 + 18HF = 3H[WF6] + 3CO2 + 9NO + 12H2O
Trong s cc cacbua quan trng nht l canxi cacbua.
Cacbua Canxi (CaC2 )
CaC2 tinh khit l cht dng tinh th khng mu thuc h lp phng,

c t khi d = 2,22, nng chy 23000C. Canxi cacbua k thut l khi mu
xm thng gi l t n.
163
Canxi cacbua tng tc mnh vi nc gii phng C2H2 :
CaC2 + 2H2O Ca(OH)2 + C2H2
Khi un nng vi H2, N2, S, P phn ng c th xy ra. V d: n c th kt hp

vi N2 to ra canxi xyanamit:
CaC2 + N2 = CaCN2 + C
Khi un nng n c th kh c oxyt v clorua ca cc kim loi:

0
MgO + CaC2 1440 C Mg + CaO + 2C
Vi nhng tnh cht ha hc nh trn, canxi cacbua c dng sn xut

axtylen, canxi xyanamit v dng lm cht kh trong luyn kim
CaC2 tinh khit c sn xut t cc nguyn t nhit 10000C trong

kh quyn argon.
Ca + 2C CaC2
trong k thut:
CaO + 3C CaC2 + CO
X.1.2.6. Xyan (hay xianogen)
trng thi kh, xyan gm nhng phn t kp (CN)2 c cu to thng:

164
:N C C N: dC-C = 1,37A0; dC-N = 1,13A0
Xyan l mt cht kh khng mu, mi xc, d ha lng v ha rn (ha

lng -20,70C, ha rn -34,40C).
Xyan bn vi nhit, trn 10000C n mi b phn hy to ra CN:
(CN)2 2CN
Cc gc CN cng rt bn vi nhit, di tc dng ca tia t ngoi hoc

khi un nng gn 5000C, CN trng hp to thnh mt khi rn v nh hnh mu
en khng tan trong nc c thnh phn (CN)n c gi l paraxyan, c cu to
dng mch vng cha no.
N N N N
C C C C
C C C C
N N N N
Trong khng kh, xyan d bc chy cho ngn la mu hng.
(CN)2 + O2 = 2CO + N2
Khi lu trong nc n b thy phn theo hai c ch sau y:
(CN)2 + H2O HCN + HCNO
axit xyanhydric axit xyanic
(CN)2 + H2O H2N C C NH2
O O oxamidua
165
S thy phn ca xyan cng cho thy s ging nhau gia xyan v halogen, nht
l trong mi trng kim.
(CN)2 + NaOH NaCN + NaOCN + H2O
V vy CN cn c gi l halogen gi. Xyan c iu ch bng cch un

nng hn hp gm 2 mui Hg(CN)2 v HgCl2 4000C:
Hg(CN)2 + HgCl2 Hg2Cl2 + (CN)2
hoc trn dung dch CuSO4 vi NaCN:
2CuSO4 + 4NaCN 2Na2SO4 + 2CuCN + (CN)2
X.1.2.7. Hydro xyanuav xyanua
Hydro xyanua HCN l hp cht cng ha tr
H C N: dC-H = 1,05A0 dC-N = 1,15A0
mt dng phn t khc ng phn vi n l hydro izo xyanua HNC c cu to:
H N C
Trong hydro xyanua bnh thng c c hai dng ng phn nm cn

bng vi nhau
HCN HNC
iu kin thng dng HCN chim 99,5% , khi un nng dng HNC tng ln.
hin nay cha tch c HNC tinh khit.
HCN l mt cht lng khng mu, c mi kh chu v ht sc c, d

ha rn v d bay hi (ha rn -150C, si 25,60C), tan nhiu trong nc,
ru, te theo bt k t l no, trong dung dch nc. HCN l mt axit rt yu
(K=2,1.10-9), yu hn c axit cacbonic. Trong dung dch HCN, b thy phn:
HCN + 2H2O HCOONH4 Focmiat amn
166
trng thi khan hay trng thi dung dch, HCN bn khi c axit v c lm cht
n nh. Nu khng n s trng hp thnh nhng sn phm rn mu en v i
khi c th gy n.
Khi c t nng trong khng kh:
4HCN + 5O2 2H2O + 4CO2 + 2N2
HCN c dng trong tng hp cht hu c. N c iu ch theo phn ng:

0
500
CO + NH3 ThO 2
C HCN + H O
2
NaCN + H2SO4 = NaHSO4 + HCN
Mui ca axit HCN gi l xyanua cha ion CN- c cu to:
[:C N:]-
nhng phn ng ca ion CN- ging cc phn ng ca ion X- , v d to kt ta

AgCN (TAgCN = 1.10-5) ging nh AgCl; ion CN- khng mu nn cc mui
xyanua khng mu.
Do c s eclectron bng s electron ca phn t CO, c cp electron t do C,

ion CN- cng to nn cc phc cht bn vi cc ion kim loi chuyn tip
KCN + Fe(CN)3 K3[Fe(CN)6]
KCN + Fe(CN)2 K4[Fe(CN)6]
Cng nh HCN, mui CN- ht sc c. Tt c mui CN- u kt ta, tr xyanua

kim loi kim v kim loi kim th. Ring Hg(CN)2 tan nhiu trong nc v hu
nh khng b ion ha. Cc xyanua b thy phn mnh:
KCN + H2O KOH + HCN
Cc mui rn KCN, NaCN trong khng kh b thy phn chm bng kh CO2
KCN + CO2 + H2O HCN + KHCO3
167
Nhiu mui xyanua kim loi nng khng tan trong nc nhng tan trong dung
dch xyanua kim loi kim to phc cht:
Mn(CN)2 + 4KCN K4[Mn(CN)6]
CN- c tnh kh, khi un nng trong khng kh th b oxy ca khng kh oxy
ha:
2NaCN + O2 = 2NaCNO Natri xyanat
Khi un si, dung dch xyanua s kt hp vi S to thnh thi xyanat:
KCN + S = KCNS Kali thixyanat
Trong cc mui xyanua th ch KCN v NaCN c dng nhiu vo vic khai

thc vng, nh to vi vng mt phc cht tan cho php tch vng ra khi
qung.
4Au + O2 + 8NaCN + 2H2O 4Na[Au(CN)2] + 4NaOH
2Na[Au(CN)2] + Zn Na2[Zn(CN)4] + 2Au
Phng php thng dng iu ch mui xyanua l dng C kh cacbonat

khi un nng.
Na2CO3 + C + 2NH3 = 2NaCN + 3H2O
Na2CO3 + C + CaCN2 = CaCO3 + 2NaCN
X.1.2.8. Axit xyanic v axit thixyanic .. ..
Axit xyanic HNCO c cu to: N C O:
dH-N = 0,99A0, dN-C = 1,21A0, dC-O = 1,17A0 H
l mt cht lng d bay hi (t0s = 240C, t0nc = -840C), tan trong nc to dung
dch axit, nhng trong dung dch long axit d b thy phn:
HCNO + H2O CO2 + NH3
sau axit kt hp vi NH3 to ra ur:

168
NH3 + HCNO CO(NH2)2
Trong dung dch m c, axit trng hp thnh cht rn dng tinh th

khng mu ng vi cng thc (HCNO)n v c gi l axit xyanuric.
Xyanat: L mui ca axit xyanic. Mui amni xyanat c mt vai tr rt c bit

trong ha hc, v ln u tin ngi ta tng hp c mt hp cht hu c t
mt cht v c l sn xut ur t amni xyanat:
NH2
NH4 - N = C = O nhit
O=C
NH2
Xyanat kim loi kim kh bn vi nhit, chng ch b phn hy nhit cao:
3KNCO KCN + K2CO3 + CO + N2
D b nc thy phn:
KCNO + 2H2O NH3 + KHCO3
c iu ch bng cch oxy ha xyanua trong dung dch nng bng oxy khng
kh hoc bng PbO:
PbO + KCN Pb + KCNO
Axit thixyanic (HCNS)
.. .. dN-H = 0,99A0
N C S: dN-C = 1,22A0
H dC-S = 1,56A0
HCNS l mt cht kh km bn, ch tn ti nhit thp v trong dung

dch long di 5%. Trong ding dch long n l mt axit mnh, phn ly gn
nh hon ton. Khi tng tc vi cc cht oxy ha mnh nh KMnO4, H2O2...
axit HCNS chuyn thnh HCN v H2SO4.
169
Thixyanat: L mui ca axit HCNS, a s khng mu v d tan trong nc,

tr mui ca bc, thy ngn v ng. V d: AgSCN rt t tan (TAgSCN = 10-
13
). Ion SCN- to vi Fe3+ mt hp cht mu thm:
Fe3+ + 3SCN- Fe(SCN)3
St (III) thio xyanat
Phn ng ny dng pht hin ion Fe3+ cng nh ion SCN-.
Ging CN-, SCN- to ra nhiu hp cht phc loi M2[E(SCN)6] hay

M3[E(SCN)6]. V d: Fe(SCN)3 + 3KSCN K3[Fe(SCN)6]
mu mu
Khi AgSCN tng tc vi Br2 trong dung dch CS2 s to mt tinh th rn

khng mu, bn nhit thp l thioxyan (SCN)2. Thixyan c 2 cng thc
cu to l:
N C-S - S - C N v N C- S - C N
Thioxyanat c iu ch khi cho xyanua tng tc vi S:
KCN + S KSCN
NH4SCN c iu ch khi un di p sut dung dch amoniac m c vi

cacbon isulfua v vi ti 110oC:
2NH3 + CS2 + Ca(OH)2 = NH4CNS + CaS + 2H2O
Mui thixyanat khng c vi ngi.
X.2. SILIC
X.2.1. n cht
170
Silic l nguyn t tng t C v s eclectron ha tr (1s2 2s2 2p6 3s2 3p2).

Si chim 20% nguyn t trong v tri t. V rn tri t gm qu na l SiO2,
nham thch silicat v alumino silicat. Silic t nhin gm 3 ng v bn:
28 29 30
Si(92,27%), Si(4,68%) v Si(3,05%)
L tnh
Si tinh khit to nn nhng tinh th lp phng c cu trc tng t kim

cng; khng c dng tinh th ging than ch. Silic v nh hnh l cht bt mu
hung thc t l nhng vi tinh th silic lp phng. Silic khng tan trong cc
dung mi m ch tan trong mt s kim loi nng chy nh Al, Ag, Zn... khi
ngui Si s kt tinh v tnh cht ny c s dng iu ch silic tinh th. Silic
tinh th cng ( cng bng 7), kh nng chy, kh bay hi (t0nc = 14280C, t0s =
26000C). Trong tinh th silic c mt phn no d cc lin kt khng nh c nn
silic tinh th c mu xm, c nh kim v l cht bn dn. T bo quang in silic
c th chuyn 15% nng lng nh sng mt tri thnh in nng nn c ng
dng lm pin mt tri.
Ha tnh
iu kin thng, Si kh tr v mt ha hc v c mng li tinh th rt

bn. Silic v nh hnh hot ng mnh hn silic tinh th. nhit thng, Si
ch tc dng vi F2; 5000C tc dng vi Br2, Cl2 v 6000C chy trong oxy.
Si + 2F2 SiS4 (Ttra floruasilic)
Si + O2 SiO2 (thch anh - ) ; H = -171,7 kcal
6000C, Si tng tc c vi S:
Si + 2S SiS2 (isulfua silic)
Tng tc vi N2 10000C v vi C 20000C:
3Si + 2N2 Si3N4 (Silic nitrua)
C + Si SiC (Silic cacbua)
171
Ngoi ra nhit cao (800 - 10000C) Si cn tc dng vi mt s kim loi to

thnh silixua. V d: Si + 2Mg Mg2Si
iu kin thng Si khng tc dng vi H2O, nhng 8000C c phn ng:
Si + 2 H2O SiO2 + 2H2
Si bn vi cc axit, ch tan trong hn hp HF v HNO3 :
3Si + 18HF + 4HNO3 3H2SiF6 + 4NO + 8H2O
Tuy nhin Si tc dng mnh lit vi kim gii phng hydro:
Si + 2KOH + H2O ?? K2SiO3 + 2H2
iu ch
Dng than cc kh SiO2 trong l in s thu c Si k thut (95 - 98%):
SiO2 + 2C Si + 2CO
Trong phng th nghim dng Mg lm cht kh:
SiO2 + 2Mg Si + 2MgO
Si iu ch c c ln nhiu tp cht. Si tinh khit dng trong k thut c

iu ch bng cch dng hi km kh SiCl4 1000oC:
SiCl4 + 2Zn Si + 2 ZnCl2
hay nhit phn SiH4 hoc SiI4
SiH4 Si + 2 H2
(mono silan)
SiI4 Si + 2 I2
Ngoi k thut bn dn, silic cn c dng rng ri trong luyn kim loi
oxy trong thp v lm tng tnh chng r.
X.2.2.Cc hp cht ca silic

172
X.2.2.1. Silan
Silan l dy hp cht hydro silixua c cu to phn t tng t dy hydro

cacbon dy mtan. Chng c cng thc chung l SinH2n+2. Hin nay ngi ta
bit c nhng silan sau y: monosilan SiH4, disilan Si2H6, trisilan Si3H8,
tetrasilan Si4H10, pentasilan Si5H12, hexasilan Si6H14, quan trng l 4 silan u.
Tt c cc silan u khng mu, c mi c trng v rt c. Chng

khng tan trong nc, nhng tan trong cc dung mi hu c.
SH4 Si2H6 Si3H8 Si4H1

0
t0nc (0C) -185 -129 -117 91
t0s (0C) -112 -14 53 107
Do nng lng lin kt Si-Si v Si-H nh hn nng lng ca cc lin kt C-C

v C-H nn cc silan km bn hn cc hydrocacbon no. Cc silan t bc chy
ngoi khng kh, ring SiH4 ch bc chy trong oxi tinh khit:
SiH4 + 2O2 SiO2 + 2 H2O ; H = 309 kcal/mol
Silan khng tng tc vi nc v axit nhng d thy phn trong nc c vt

OH-:
Si2H6 + (4 + 2n) H2O 2 SiO2.nH2O + 3 H2
Silan l cht kh mnh, tng tc mnh lit vi halogen gy n. Khi c mt

AlCl3, HCl tng tc c vi silan to cc sn phm th:
SiH4 + HCl AlCl3 SiH3Cl + H2
Hn hp silan c th iu ch bng cch cho Mg2Si tc dng vi dung dch

H2SO4 long: Mg2Si + 2H2SO4 SiH4 + 2 MgSO4
Vi hiu sut phn ng 25%, tng tc ca Mg2Si v H2SO4 cho hn hp silan

c thnh phn gn ng l 40% SiH4, 30% Si2H6, 15% Si3H8, 10% Si4H10, 5%
Si5H12 v Si6H14 .
173
nng cao hiu sut, ngi ta cho Mg2Si tc dng vi NH4Cl trong NH3
long:
Mg2Si + 4NH4Cl = SiH4 + 2MgCl2 + 4NH3
X.2.2.2. Silic ioxit (SiO2)
Tuy c cng thc phn t l SiO2 nhng silic ioxit khng tn ti tng
phn t ring r m di dng tinh th, ngha l mt phn t khng l.
Ba dng tinh th ca SiO2 p sut thng l thch anh, tridymit v

crystobalit. Mi mt dng hnh th ny li c dng bn nhit thp v
dng bn nhit cao. Sau y l s bin i cc dng th hnh:
8700C 14700C
Thch anh Tridimit Crystobalit
5730C 120 - 1600C 200 - 2750C

l
Thch anh Tridimit Crystobalit
Tt c cc dng tinh th ny u bao gm cc nhm t din SiO4 ni vi

nhau qua nhng nguyn t oxy chung; trong t din SiO4 nguyn t Si nm
tm t din, lin kt cng ha tr vi 4 nguyn t oxy nm cc nh ca t
din. Nh vy mi nguyn t oxy lin kt vi 2 nguyn t Si 2 t din khc
nhau v tnh trung bnh minuyn t Si c hai nguyn t oxi v cng thc kinh
nghim ca silic ioxit l SiO2.
V mt ha hc, SiO2 rt tr. N khng tc dng vi oxy, Cl2, brm v

cc axit k c khi un nng. N ch tc dng vi F2 v HF iu kin thng:
SiO2 + 4HF SiF4 + 2H2O
N cn tan trong kim hay cacbonat kim loi kim nng chy:
SiO2 + NaOH Na2SiO3 + H2O
SiO2 + Na2CO3 Na2SiO3 + CO2
174
Trong phng th nghim c th iu ch SiO2 v nh hnh dng bt trng

bng cch nung nng kt ta axit silicic.
X.2.2.3. Axit silicic
Cu to phn t ca axit silicic cha c xc nh r, n c th ng vi

2 cng thc: H4SiO4 (axit orthosilicic), H2SiO3 (axit mtasilicic).
Trc y ngi ta dng cng thc th 2 v n ging cng thc axit cacbonic
H2CO3, cng thc ny khng ng tin cy v thc t ion n gin SiO32- khng
tn ti, m ngc li ion SiO42- rt ph bin. Ngoi ra trong mi hp cht vi
oxy, silic lun c s phi tr bng 4 ch khng bng 3. V vy cng thc H4SiO4
ngy nay c cng nhn l ng tin cy hn.
Axit silicic tn ti dng dung dch keo l do cc phn t mt bt nc

to nn:
OH OH OH OH
nH O Si OH H O Si [ O Si ]n-2O Si OH +
(n+1)H2O
OH OH OH OH
Khi kch thc ht keo vt gii hn no th dung dch keo ng t.

Ty theo nhng iu kin xy ra qu trnh ng t, axit silicic hoc lng xung
di dng tinh th khng tan c cng thc chung SiO2.nH2O hoc ng thnh
khi ging nh thch gi l gel. Gel axit silicic sau khi c sy kh trong
khng kh tr thnh vt liu xp gi l silicagen Do c b mt ln, silicagen c
kh nng hp ph ln, ngi ta dng silicagen ht m, lm kh cc kh.
Axit silicic l axit rt yu :
H4SiO4 H3SiO4- + H+ ; K1 = 10-10
V vy n d dng to thnh khi cho mui natri silicat tc dng vi axit, k c

axit yu nh axit cacbonic hoc thy phn SiH4, SiCl4:
175
SiCl4 + 4H2O H4SiO4 + 4HCl
Na2SiO3 + 3H2O + 2CO2 H4SiO4 + 2NaHCO3
X.2.2.4. Silicat
Silicat l mui ca axit silicic. Silicat kim loi kim c to nn khi nu

thch anh trong hydroxit hay cacbonat kim loi kim. Chng trong sut nh
thy tinh, khng tan trong nc lnh nhng tan trong nc nng gi l thy tinh
tan, dung dch m c gi l thy tinh lng. Dng tm vi v g chng chy.
Silicat ca cc kim loi khc c to nn khi nu chy cc thch anh vi

oxyt kim loi tng ng. Chng khng tan trong nc.
Silicat thin nhin ng hng u trong cc loi khong vt: chng c n

hng trm cht v chim phn ln khi lng v tri t. Nghin cu cu trc
tinh th ca cc silicat thin nhin bng phng php nhiu x tia X, ngi ta
nhn thy tt c cc silicat u c cu to nn t nhng n v cu trc chung
l nhm t din u SiO4 lin kt vi nhau qua cc nguyn t oxy chung.
Nhng nhm t din lin kt vi nhau to thnh mch thng, mch vng, lp
hoc mng li. Da vo c im cu trc ngi ta chia silicat ra lm cc
nhm: octo silicat, silicat mch thng, silicat mch vng, silicat lp, silicat mng
li.
THY TINH
Thy tinh thng l mt hn hp ca natri silicat v canxi silicat c thnh

phn gn ng l Na2O.CaO.6SiO2. Thy tinh c to thnh khi nu hn hp
thch anh, vi v x a 1400oC:
6 SiO2 + CaCO3 + Na2CO3 Na2O.CaO.6SiO2 + 2CO2
176
Thy tinh l cht "v nh hnh", khi un nng n mm dn ri mi nng

chy nn t thy tinh ngi ta c th to ra cc vt c hnh th rt khc nhau
theo cch thi, p, cn.
Thy tinh thng c mu xanh lc gy ra bi s c mt ca st (II) silicat,

mun lm mt mu ngi ta cho vo thy tinh mt t MnO2, st (II) b oxy
ha thnh st (III) c mu vng, mu ny l mu ph i vi mu tm gy nn
bi mangan (III). Cho thm selen vo thy tinh cng c th lm mt mu xanh
lc ca st (III) silicat v mu hng ca dung dch selen trong thy tinh l mu
ph i vi mu xanh lc. Thay Na trong thy tinh bng K s c thy tinh c
nhit nng chy v nhit ha mm cao hn, dng lm cc loi thy tinh
chu nhit.
Thay Ca trong thy tinh kali bng Pb s c loi thy tinh trong sut v
d nng chy hn dng lm phal. Loi thy tinh cha nhiu ch hn c
dng lm lng knh v thu knh. Loi thy tinh cha rt nhiu ch c th trong
sut nh kim cng nn c dng lm trang sc (mt ngc).
Thy tinh loi thng khng bn vi nc. Khi nghin nh vi nc,

thy tinh thng cho mi trng kim. Dung dch kim n mn mnh thy tinh
thng. tng tnh chu nhit v tnh bn ha hc ca thy tinh ngi ta gim
kim loi kim, kim th trong thy tinh v tng bo, nhm. Hai loi thy tinh ni
ting trn th gii l thy tinh Ina (c) v thy tinh Pyrec (Php).
GM : Nguyn liu ch yu lm gm l t st v cao lanh.
- t st: l sn phm phn hy ca cc silicat thin nhin di tc dng

ca cc tc nhn kh quyn, ch yu l nc v kh cacbonic. N gm ch yu
cc khong st nh caolinit (Al2O3.2SiO2.2H2O), montmorilonit
(AlSi2O5(OH).xH2O) v galoazit (Al2O3.2SiO2.4H2O) v cc tp cht khc nh
ct, oxyt st... t st thng c mu t xm xanh (gy nn bi cc tp cht hu
c) n nu (gy ra bi oxit st). C loi t st mu trng. Mt s loi khc c
mu m do cc oxit ca st v mangan, lm cht nu v c, v d nh son.
- Cao lanh: gm ch yu khong caolinit v c to nn do qu trnh

phong ha ca phenspat octhoclaz:
177
2K[AlSi3O8] + 2H2O + CO2 Al2O3.2SiO2.2H2O + 4SiO2 + K2CO3
Cao lanh tinh khit c mu trng, s thy mn. t st dng lm gm khc

vi cao lanh ch do v cha nhiu tp cht hn. Loi t st c nhit nng
chy trn 16500C gi l t st chu la.
Qu trnh sn xut gm gm cc giai on:
- Tinh ch t st hay cao lanh
- Lm hn hp nguyn liu
- To hnh bng mt trong cc phng php nn, p v c
- Lm kh, sy, nung
- Nung nhit cao
- Trng men v trang tr
- Nung li sau khi trng men.
Ngoi ra ngi ta cn sn xut gch ngi, gch chu la, snh, s, men t t
st.
XI MNG: Xi mng l sn phm thu c khi nung vi trn k vi t st

nhit cao ri em nghin thnh bt. N c kh nng ng cng sau khi
nho trn vi nc. C nhiu loi xi mng, thng dng nht l loi xi mng
Pooclng.
Xi mng l vt liu dng bt mu lc xm l hn hp gm ch yu

canxi aluminat Ca3(AlO3)2 v cc silicat khc ca canxi nh Ca3SiO5, Ca2SiO4.
Khi trn vi nc xi mng s ng cng sau vi gi. Qu trnh ng cng ca
xi mng ch yu l do s hydrat ha ca cc hp cht c trong xi mng to nn
nhng hydrat dng tinh th:
Ca3SiO5 + 5H2O CaSiO4.4H2O + Ca(OH)2
Ca2SiO4 + 4H2O Ca2SiO4.4H2O
178
Ca3(AlO3)2 + 6H2O Ca3(AlO3)2.6H2O
Sau thi gian ng cng ban u, qu trnh ng cng tip tc tng ln do

s hydrat ha cn lan su vo bn trong xi mng.
X.2.2.5. Silic tetrahalogenua
Silic to nn cc halogenua n gin c cng thc chung l SiX4 (X = F, Cl, Br,

I) v nhng silic cha mch c cng thc chung l Si2X6. Ring vi clo, silic c
th to ra Si6Cl14. Quan trng nht l SiX4.
SiX4 l hp cht cng ha tr, phn t ca chng c cu to t din u:
Si
X X
X
iu kin thng SiF4: cht kh, SiCl4, SiBr4: cht lng, SiI4: cht rn
SiF4 SiCl4 SiBr4 SiI4
t0nc (0C) -77 -70 5 122
t0s (0C) -65 57 155 290
Lin kt Si-X c nng lng lin kt ln hn lin kt C-X do SiX4 bn nhit

hn CX4. Tuy vy chng li d dng b nc thy phn, trong khi CX4 khng
tc dng vi nc.
SiX4 + (2 + n)H2O SiO2.nH2O + 4HX
i vi Cl, Br, I phn ng hu nh hon ton theo chiu thun, cn i vi flo

phn ng l thun nghch. Ring SiF4 cn c kh nng tc dng vi HF to nn
axit flosilic H2SiF6. V vy sn phm thy phn ca SiF4 khng phi l HF m l
H2SiF6
3SiF4 + (2 + n)H2O Si O2.nH2O + 2H2SiF6

179
Cc SiX4 c iu ch bng tng tc ca halogen vi hn hp thch anh v

than nhit gn 7000C:
SiO2 + 2C + 2Cl2 SiCl4 + 2CO
ring SiF4 c th iu ch bng cch un hn hp bt CaF2 (florit) v thch anh

vi H2SO4 :
2CaF2 + 2H2SO4 = 2CaSO4 + 4HF
SiO2 + 4HF = SiF4 + 2H2O
X.2.2.6. Cacbua silic (SiC)
dng tinh khit, tinh th cacbua silic (cn gi l cacborunum) khng

mu, t khi d = 3,2. Khi c ln mt t tp cht th c mu xm. Cacbua silic c
cu trc nh kim cng, v vy n c cng rt cao, c dng lm da mi.
Cacborunum dn nhit tt v l cht bn dn (10000C vn cn dn in) nn
c dng lm thanh t trong cc l in. Cacborunum bn v mt ha hc,
nhit cao vn khng chy mc d 2 nguyn t C, Si d b oxy ha. N cng
khng b mui clorat hay nitrat kim loi kim oxy ha, khng tc dng vi c
HNO3 bc khi v vi c HF m tc dng vi hn hp hai axit ny, tc dng
chm vi kim nng chy khi c mt khng kh.
SiC + 4KOH + 2O2 K2SiO3 + K2CO3 + 2H2O
Trong cng nghip c iu ch bng cch un nng hn hp bt thch

anh v than cc 20000C.
SiO2 + 3C SiC + 2CO
Qu trnh ny tiu tn nhiu nng lng, trung bnh sn xut 1 tn

cacborunum cn phi dng 8000kWh. Gn y Nht Bn sn xut c SiC
dng si rt mnh khng nhng chu c nhit cao m cn rt bn, c th
dt c loi vi dng trong cng nghip.
X.3. GECMANI, THIC, CH
X.3.1.n cht
180
1. L tnh
Gecmani (Ge), thic (Sn), ch (Pb) l cc kim loi. Tnh kim loi tng t
Ge n Pb. Gecmani c mu trng bc, b ngoi ging kim loi nhng c kin
trc ging kim cng. Dng th hnh (thic trng) bn trn 13,20C, l kim
loi mu trng bc, c cu trc t phng vi s sp xp cc nguyn t theo
hnh bt din u. Khi lm lnh thic trng chuyn thnh dng (thic xm) c
cu trc kiu kim cng. S chuyn dng th hnh thnh c km theo s
gim th tch ring (25,6%) v thic nt vn ra thnh bt. Ch l kim loi mu
xm sm, c cu trc lc phng din tm in hnh i vi kim loi
Mt s tnh cht vt l
CCK Si Ge Sn Pb
khi lng ring g/cm3 3,51 2,33 5,32 7,3 11,34
t0nc (0C) 3900 1412 937,1 231,9 327,4
t0s (0C) 5000 2480 2700 2200 1740
dn in Hg = 1 ----- ----- 0,001 8 5
cng (kim cng = 20 7 6 ----- -----

10)
2. Tnh cht ha hc
S tng tnh kim loi ca cc n cht trong dy Ge - An - Pb th hin r

trong tnh cht ha hc.
iu kin thng Ge, Sn, Pb bn vi khng kh v nc. Khi un nng

thic bt u b oxy ha, Ge b oxy ha 7000C.
Sn + O2 SnO2 Ge + O2 = GeO2
ring Ch tng tc vi oxy theo phn ng
2Pb + O2 = 2PbO
181
C ba nguyn t u tng tc vi Halogen v nhiu nguyn t khng

kim loi khc
V d: Ge + 2Cl2 = GeCl4
Sn + 2Cl2 = SnCl4
Pb + Cl2 = PbCl2
Trong dy in th Ge nm sau Hydro, cn Sn v Pb nm ngay trc

Hydro. Do Gecmani khng tc dng vi axit long kiu HCl, H2SO4. Khi oxy
ha bng axit HNO3, H2SO4 c Ge chuyn thnh axit Gecmanic H2GeO3
(xGeO2.yH2O)
Ge + 2H2SO4 + (x - 2)H2O = GeO2.xH2O + 2SO2
Ge + 4HNO3 + (x - 2)H2O = GeO2.xH2O + 4NO2
Sn, Pb c th in cc m chng c th tan c trong axit
Sn + 2HCl t0C SnCl + H

2 2
Sn + 2H2SO4 t0C SnSO4 + H2
nhng vi axit H2SO4
Sn + H2SO4 Sn(SO4)2 + 2SO2 + 4H2O
vi axit Nitric thic tan d dng
3Sn + 16HNO3(l) 3Sn(NO3)2 + 4NO + 8H2O
Sn + 4HNO3 + (x - 2)H2O SnO2.xH2O + 4NO2
Ch ch tng tc trn b mt vi dung dch HCl, H2SO4 long v to ra

PbCl2, PbSO4 kt ta khng tan to thnh lp bo v.
Nhng vi axit HCl, H2SO4 m c th Ch tan v mui kh tan ca lp

bo v chuyn thnh hp cht tan.
182
PbCl2 + HCl H2PbCl4
PbSO4 + H2SO4 Pb(HSO4)2
Vi axit HNO3 bt k nng no ch u tan
3Pb + 8HNO3(l) 3Pb(NO3)2 + 2NO + 4H2O
Pb + HNO3 Pb(NO3)2 + 2NO2 + 2H2O
Ring ch khi c mt oxy c th tc dng vi nc
2Pb + 2H2O + O2 = 2Pb(OH)2
cng nh tan trong axit hu c khi c mt oxy
2Pb + 4CH3COOH + O2 = 2Pb(CH3COO)2 + 2H2O
Sn, Pb tan c trong kim khi un nng
M + 2KOH + 2H2O K2[M(OH)4)] + H2
Gecmani ch tan trong kim khi c mt cht oxy ha
Ge + 2KOH + 2H2O2 K2[Ge(OH)4]
3. Trng thi thin nhin - iu ch
Ge chim 2.10-4% tng s nguyn t ca v tri t, Ge l nguyn t phn

tn, Thic tn ti cc khong Canxiterit SnO2, Ch qung chnh l Galen
(PbS).
Ge cha c sn xut vi quy m ln, l sn phm ph ca cc qu trnh iu

ch cc kim loi khc ngi ta tch GeO2 ri dng H2 kh 10000C
GeO2 + 2H2 Ge + 2H2O
Trong cng nghip Sn c iu ch bng cch dng than kh Canxiterit

13000C
SnO2 + 2C Sn + 2CO
183
Qu trnh iu ch Ch gm 2 giai on
g1: t chy qung Galen
2PbS + 3O3 = 2PbO + 2SO2
Sau dng than cc kh axit thnh Pb

0
PbO + C t C Pb + CO
X.3.2. Hp cht
X.3.2.1. Cc hp cht mono oxit ca Ge, Sn, Pb
Cc nguyn t Ge, Sn, Pb to nn hai loi oxyt l Mn oxyt MO v i

oxyt MO2
Cc Mn oxyt MO u l cht rn, GeO v SnO c mu en cn PbO c 2

dng PbO = mu , Pb = mu vng. Cc oxyt SnO v GeO hu nh khng
tan trong nc, ring PbO c tan cht t nn ch c th tng tc vi nc khi c
mt oxy. Khi un nng trong khng kh chuyn thnh oxyt cao hn.
0
2Sn + O2 550 C 2SnO2
0
3PbO + 1/2 O2 500 C 2SnO2
Khi in nng chng b kh d dng bi Hydro Cacbon, Cacbon mono oxyt

0
V d: SnO + H2 183 C Sn + H2O
Tt c cc oxyt u tan trong axit v tan trong kim mnh. Ngi ta iu ch

GeO bng cch un nng Ge vi GeO2
8000C
Ge + GeO2 2GeO
SnO c iu ch bng cch un
Sn(OH)2 SnO + H2O
184
cn PbO
2Pb + O2 = 2PbO
IOXYT MO2:
Tt c cc ioxyt MO2 u l cht rn, GeO2, SnO2 c mu trng v PbO2

c mu nu en. Khc vi SnO2, GeO2, SnO2 - PbO2 c cu trc theo kiu
Rutin, trong mi nguyn t kim loi c 6 nguyn t oxy bao quanh kiu
bt din v mi nguyn t oxy c ba nguyn t kim loi bao quanh kiu tam
gic.
Ging vi SiO2 cc ioxyt GeO2 v SnO2 rt bn vi nhit v d chuyn

sang trng thi thy tinh. Cn PbO2 khi nng mt dn oxy bin thnh cc oxyt
trong Ch c mc oxy ha thp hn
Cn PbO2 khi nng mt dn oxy bin thnh cc oxyt trong ch c mc

oxy ha thp hn.
0 0 0
PbO2 240 - 320 C Pb2O3 390 - 400 C Pb3O4 530 - 550 C PbO
nu en vng vng
Tt c cc ioxyt u km bn v mt ha hc GeO2 t tan trong nc,

cn SnO2 v PbO2 khng tan chng lng tnh nhng tan trong kim d hn
trong axit, to nn nhng hp cht kiu N2[M(OH)6]
MO2 + 2KOH + 2H2O K2[M(OH)6]
Khi nu chy vi kim hay oxyt tng ng, cc ioxyt to nn nhng hp

cht c thnh phn l N2MO3 v N4EO4 ( y N l kim loi ha tr 2)
2CaO + PbO2 Ca2PbO4
2PbO + PbO2 = Pb2PbO4[Pb3O4] octho PlumbatCanxi
Tt c cc oxyt c th b kh d dng bi cc cht C, CO, H2, Al, Mg...

n kim loi.
185
PbO2 + 2H2 Pb + 2H2O
Tnh oxy ha khng c trng i vi GeO2 v SnO2 nhng rt c trng

i vi PbO2. PbO2 l mt cht oxy ha kh mnh, khi tng tc vi axit H2SO4
m c PbO2 gii phng O2, vi HCl gii phng Clo.
2PbO2 + 2H2SO4 = 2PbSO4 + 2H2O + O2
PbO2 + 2HCl = PbCl2 + 2H2O + Cl2
trong mi trng axit m c n oxy ha Mn(II) Mn(VII) v trong mi

trng kim mnh n oxy ha Cr(III) Cr(VI).
5PbO2 + 2MnSO4 + 6HNO3 = 2HMnO4 + 3Pb(NO3)2 + 2PbSO4 + 2H2O
3PbO2 + 2Cr(OH)3 + 10KOH 2K2CrO4 + 3K2[Pb(OH)4] + H2O
GeO2, SnO2 bn nn c iu ch bng cch t chy kim loi trong oxy

khng kh, ring PbO2 ch c th iu ch bng phng php gin tip.
V d: oxy ha mui ch II bng Clo, Br2 trong mi trng kim
Pb(CH3COO)2 + 2CaOCl2 + 2H2O = PbO2 + 2CaCl2 + 2CH3COOH
C QUI CH:
c qui ging nguyn t Gavani l phn ng oxy ha kh sinh ra dng

in mt chiu. Nhng khc ch sau khi phng in, c qui trng thi ban
u (tch in li).
c quy ch gm nhng cc l nhng tm li bng hp kim ch v

Antimoan (9%) pha ngoi c trt bt nho PbO, nhng tm cc dng ni lin
nhau t xen k vi nhng tm cc m cng ni lin nhau v nhng trong dung
dch H2SO4 38% do xy ra phn ng :
PbO + H2SO4 = PbSO4 +H2O
nn trn mt cc tm in cc c lp PbSO4 kh tan. Khi cho dng in 1 chiu

i qua c quy cc cc xy ra nhng phn ng sau:
186
cc m PbSO4 +2e + 2H+ = Pb + H2SO4
Pb2+ + 2e = Pb
cc dng PbSO4 -2e + SO42- +2H2O = PbO2 +2H2SO4
Pb2+ -2e = Pb4+
S chung khi tch in l:
2PbSO4 + 2H2O Pb + PbO2 + 2H2O2
Nh vy sau khi tch in, tm cc m ca c quy bin thnh tm Pb, tm cc

dng bin thnh tm PbO2 xp v nng ca H2SO4 tng ln.
Nu ni 2 cc ca c quy vi 1 dy dn th c dng in chy qua. Dng in

sinh ra c l nh nhng phn ng sau y xy ra cc cc .
cc m: Pb + SO42- = PbSO4 + 2e
(Pb = Pb2+ + 2e)
cc dng: PbO2 + H2SO4 + 2H+ + 2e = PbSO4 + 2H2O
(Pb4+ + 2e = Pb2+)
S ca phn ng chung l
Pb + PbO2 + H2SO4 phng in 2PbSO4 + H2O
Nh vy qu trnh phng in ngc vi qu trnh. Sau khi phng in,

hai tm cc m v dng u bin thnh nhng tm PhSO4 xp v nng
H2SO4 gim xung. V vy da vo nng ca axit H2SO4 (gim xung)
trong bnh c quy c th xc nh c trng thi tch in hay phng in ca
c quy. Sau khi c quy phng in ngi ta li tch in cho c quy.
Mi c quy ch trn y cho in th 2V mc ni tip 3 hay 6 c quy ta c cc

b c quy 6V - 12V theo mun.
X.3.2.2. Hydroxit M(OH)2 ca Ge, Sn, Pb
187
Cc Hydroxit M(OH)2 u l cc cht kt ta khng tan trong nc Ge(OH)2 c

mu da cam, Sn(OH)2, Pb(OH)2 c mu trng khi un nng chng d mt
nc to ra oxyt.
M(OH)2 MO + H2O
Cc M(OH)2 l cc hp cht lng tnh, t Ge Pb tnh baz tng, tnh axit

gim xung.
Chng c kh nng tan trong axit v baz mnh
M(OH)2 + 2HCl = MCl2 + H2O
M(OH)2 + 2KOH = K2[M(OH)4]
Do tnh baz tng t Ge(OH)2 Pb(OH)2, cc mui ca Ge b thy phn

hu nh hon ton, cc mui Pb2+ b thy phn rt t, cn mui Sn2+ mc
trung bnh.
Tt c cc mui ca Ge(II), Sn(II) l cc cht kh rt mnh trong khi

mui ca Pb(II) khng phi l cht kh.
V d: GeCl2 + Cl2 = GeCl4
SnCl2 + Cl2 = SnCl4
S th hin tnh kh cng th hin trong cc in cc sau y:
Ge2+ + 2H2O GeO2 + 4H+ + 2e E0 = 0,15V
Sn2+ Sn4+ + 2e E0 = 0,14V
Pb2+ + 2H2O PbO2 + 4H+ + 2e E0 = 1,46V
Cc Ge(OH)2, Sn(OH)2 c th kh c mui ca mt s kim loi n kim loi

t do
2Bi(NO3)3 + 3Na2[Sn(OH)4] + NaOH 2Bi + 3Na2[Sn(OH)6] + 6NaNO3
Cc Hydroxyt u c iu ch khi cho mui tc dng vi kim
188
M2+ + 2OH- = M(OH)2
X.3.2.3. Ch octhoplombat Pb2PbO4 hay Pb3O4
Ch OcthoPlumbat hay cn gi l minium l hp cht ca Ch c mc oxy

ha +2 v +4; l cht dng bt mu da cam, trong tinh th minium gm cc
bt din PbO6 lin kt vi nhau qua 2nguyn t oxy chung.
Khi tc dng vi dung dch long ca axit H2SO4 hay HNO3 n to nn

mui Pb(II) v PbO2
Pb3O4 + 4HNO3 = 2Pb(NO3)2 + PbO2 + 2H2O
Pb3O4 + H2SO4 = 2PbSO4 + PbO2 + 2H2O
Minium t tan trong nc v c, khi un nng n phn hy
Pb3O4 t0 3PbO + 1/2O

2
d dng b C, CO, H2 kh
0
Pb3O4 + 4CO t 3Pb + 4CO2
Trong mi trng axit n oxy ha c H2O2, mui Fe(II)
Pb3O4 + H2O2 + 3H2SO4 = 3PbSO4 + 4H2O + O2
Minium c dng sn xut thy tinh phal, men s l cht mu cho sn.
Minium c iu ch bng cch un nng PbO hay PbCO3 trong khng kh.
0
6PbO + O2 450 C 2Pb3O4
0
6PbCO3 + O2 300 C 2Pb3O4 + 6CO2
X.3.2.4. Sunfua ca Ge, Sn, Pb
Ngy nay ngi ta bit c tt c cc monoSulfua MS, iSulfua MS2

tr PbS2, chng l cc dng tinh th c mu khc nhau.
189
GeS SnS PbS GeS2 SnS2
nu nu en trng vng
Chng thc t khng tan trong nc v dung dch axit long, ring GeS2
hi tan trong nc v b nc thy phn chm
GeS2 + 2H2O GeO2 + 2H2S
chng tan trong axit HNO3, HCl m c
3PbS + 8HNO3 = 3PbSO4 + 8NO + 4H2O
3GeS2 + 4HNO3 = 3GeO2 + 6S + 4NO + 2H2O
SnS + 2HCl = SnCl2 + H2S
ring SnS2 c th tan trong dung dch kim
3SnS2 + 6KOH = 2K2SnS3 + K2[Sn(OH)6]
Cc Sulfua MS v MS2 khc vi nhau l khi tc dng vi dung dch

amni Sulfua cc MS khng tan cn li to ra mui ti.
V d: SnS2 + (NH4)2S (NH4)2SnS3
amni tiStanat.
Khc vi PbS, GeS v SnS b amni ply Sulfua oxy ha n iSulfua,

ri iSulfua tan trong amni Sulfua cho nn GeS, SnS tan c trong amni
ply Sulfua
SnS + (NH4)2S2 = SnS2 + (NH4)2S
SnS2 + (NH4)2S = (NH4)2SnS3
Da vo tnh cht ny ngi ta ch ha tch GeS, SnS ra khi PbS.
Cc mui ti khng bn d b axit phn hy.
(NH4)2MS3 + 2HCl H2MS3 + 2NH4Cl
190
(NH4)2SnS3 + 2HCl H2SnS3 + 2NH4Cl
Hydro Sulfua Stanat
H2SnS3 SnS2 + H2S
Cc MS v MS2 c th iu ch trc tip bng cch cho kim loi tc dng

vi S khi un nng hay cho kh H2S tc dng vi cc dung dch mui tng ng.
Sn + S SnS
Pb(NO3)2 + H2S PbS + 2HNO3
SnS2 c cng dng trong thc t, n c mu vng p nn c dng

m cc hnh trn g, trn giy c gi l vng gi, vng gi l cc vy mu
vng ng c iu ch bng cch un thic hn hng, lu hunh thng hoa v
NH4Cl.
X.3.2.5. ihalogenua ca Ge - Sn - Pb
Cc nguyn t Ge, Sn, Pb to nn iHalogenua vi tt c cc Halogen.

Chng l cc hp cht rn khng mu tr GeI2, SnBr2, PbI2 mu vng; SnI2 mu
.
Cc Halogenua khng phn hy khi bay hi. Sau y l nhit nng

chy, nhit si ca chng.
SnF2 SnCl2 SnBr2 SnI2 PbF2 PbCl2 PbBr2 PbI2
t0nc 210 247 232 320 822 501 370 412
t0s ---- 623 638 718 1290 954 914 872
Cc GeX2 v SnX2 d tan trong nc v thy phn mnh, cn ch

Halogenua t tan hn trong nc lnh nhng tan nhiu trong nc nng. tan
ca chng gim t PbCl2 PbI2. PbI2 khi un nng t mu vng chuyn sang
mu nu ri nu v khi ngui tr li mu vng. Cc GeX2 v SnX2 l cc
hp cht kh mnh, tt c cc MX2 u tc dng vi Halogenua kim loi kim
NX to nn phc cht kiu N2[MX4], N[MX3].
191
S to phc ny gii thch kh nng d ha tan ca iHalogenua trong

dung dch axit m c v mui ca chng.
V d: PbI2 + 2KI K2[PbI4]
PbCl2 + 2HCl H2[PbCl4]
GeCl2 c th iu ch
GeX4 Ge = 2GeX2
SnX2 c th iu ch t phn ng Sn tc dng vi axit
Sn + 2HCl SnCl2 + H2
PbX2 c th iu ch trc tip t cc nguyn t
Pb + Cl2 PbCl2
hoc bng phn ng trao i trong dung dch
Pb(NO3)2 + 2KCl PbCl2 + 2KNO3
Trong cc mui MX2 th mui Sn(II) c ng dng rng ri, dng lm

thuc th trong ha phn tch, lm cht kh trong ha hu c...
X.3.2.6. Tetra halogenua MX4 ca Ge - Sn - Pb
Ging Silic, cc tetra Halogenua ca Ge, Sn, Pb mc oxy ha +4 l

nhng hp cht cng ha tr, trong lin kt E-X c mt phn tnh cht kp.
Ngi ta bit c tt c cc Halogenua MX4 tr PbBr4, PbI4 c gii thch
l Br2, I2 khng c kh nng oxy ha Pb(II) thnh Pb(IV).
trng thi rn, tt c MX4 (tr SnCl4 v PbF4) u c mng li phn t

cho nn d bay hi. Ring SnF4 v PbF4 c mng li lp, cu to nn bi
nhng nhm bt din SnF6 hay PbF6 lin kt vi nhau qua nhng nguyn t F
chung, chng c nhit nng chy cao hn nhiu.
192
F F F
F F F F
Sn Sn Sn
F F F F
F F F
Nhit nng chy v nhit si ca cc tetra Halogenua MX4
GeF4 GeCl GeBr4 GeI4 SnF4 SnCl4 SnBr SnI4 PbF4 PbCl
4 4 4
t0nc -15 -30 26 144 200 -33 30 145 600 -15
t0s -37 80 186 377 ---- 113 203 344 ---- ----
V tnh cht l hc chng tng t nhng hp cht tng ng C v Si, t Ge

Pb bn nhit ca MX4 gim dn.
V mt ha hc cc MX4 kh hot ng, kh nng to phc cht kh mnh.
MF4 + 2HF H2[MF6]
MF4 + 2KF K2[MF6]
trong dung dch nc chng b thy phn tng nc cho n khi to nn axit.
193
CHNG IX. CC NGUYN T PHN NHM IIIA
Phn nhm IIIA gm cc nguyn t B, Al, Ga, In v Tl
c im ca nguyn t
Nng lng ion ha (kcal/ntg) Th

Nguy Cu hnh e in
Z I1 I2 I3 I4
n t nguyn t cc
(V)
B 5 [He] 2s2 2p1 191 580 870 5980 -
Al 13 [Ne] 3s2 3p1 138 434 655 2767 - 1.66
Ga 31 [Ar] 3d10 4s2 4p1 138 473 708 1480 - 0.53
In 49 [Kr] 4d10 5s2 5p1 133 435 646 1250 - 0.34
Tl 81 [Xe] 4f14 4d10 6s2 141 471 687 1170 + 0.72

6p1
(i vi Tl+ + e Tl E0 = - 0.336 V)
- Cu hnh electron ha tr ca cc nguyn t l ns2 np1. Cc nguyn t B

v Al ng ngay sau cc kim loi kim th nn lp electron st ngoi gm 2 v
8 electron tng ng. Cc nguyn t Ga, Ni v Tl ng sau dy nguyn t
chuyn tip nn lp electron st ngoi gm 18 electron. Vi cu hnh electron
nh vy nn cc nguyn t trong phn nhm IIA khng ging nhau nhiu nh
cc nguyn t kim loi kim v kim th.
- Nng lng ion ha th nht I1 ca B tng i ln, I2 v I3 cng ln

hn na. V th Nng lng cn thit to nn ion B3+ ln hn nhiu so vi
nng lng mng li ca cc hp cht ion hoc nng lng hydrat ha ca
chng trong dung dch. V th B khng d dng mt 3e to thnh ion B3+ m ch
c khuynh hng to lin kt cng ha tr m thi.
194
- Khuynh hng to ion M+3 tng ln r rt Al, trong khi B l nguyn t

khng kim loi th Al l kim loi hot ng.
- T Al n Ga tnh kim loi hi gim xung v Ga ng sau kim loi

chuyn tip nn chu s co rt d. T Ga n In tnh kim loi hi tng ln, nhng
t In n Tl tnh kim loi gim xung v Tl ng sau h Lantanoic nn chu s
co rt f.
- Trong cc hp cht, cc nguyn t phn nhm IIIA c mc oxy ha ch

yu l +3. Tuy nhin do I1 b hn tng I2 v I3 nn cc nguyn t Al, Ga, In, Tl
cn c mc oxy ha +1. bn ca mc oxy ha +1 tng ln t Al n Tl. Tl
th mc OXH +1 tri hn mc +3.
- B khng to nn cation trong dung dch nn th in cc ca n khng

xc nh c. Cc nguyn t cn li c th in cc b hn kim loi kim v
kim th.
- V nhiu mt th B ging nhiu vi Si IVA hn l ging vi Al v cc

nguyn t khc trong cng nhm.
XI.1. BO
XI.1.1. n cht
Tnh cht l ha
Bo tn ti di mt s dng th hnh: Bo tinh th v Bo v nh hnh.
Bo tinh th tinh khit khng mu, nhng thng c mu en xm v thng ln

tp cht borua cc kim loi. N c nh kim v b ngoi ging nh kim loi.
Bo v nh hnh cng nh Bo tinh th l nhng cht bn dn, dn in tng

theo nhit .
iu kin thng Bo rt tr v mt ha hc, n ch tng tc trc tip vi F,

khi un nng th n tng tc vi nhiu nguyn t.
- 7000C Bo chy trong khng kh phn ng tht nhiu nhit:
195
4B + 3 O2 2 B2O3 H = - 176 kcal/mol
- 12000C Bo tng tc vi N2 to thnh bo nitrua (BN) v 28000C vi

cacbon to thnh bo cacbua (B12C3)
- nhit thng Bo khng tan trong nc, nhng nhit cao n tng tc
vi hi nc to nn oxit v gii phng hydro:
2 B + 3 H2O B2O3 + 3 H2
- Bo cng khng tan trong dung dch HCl v HF, dng bt mn n tan chm
trong trong dung dch m c ca HNO3 , H2SO4 , H2O2 v mt s cht oxy
ha mnh khc bin thnh H3BO3.
B + 3 HNO3 H3BO3 + 3 NO2
- dng bt mn Bo c th tan trong dung dch kim c v un nng hoc kim

nng chy.
V d: 2 B + 2 NaOH + 2 H2O 2 NaBO2 + 2 H2
- Khi un nng trong kh quyn NH3 hoc NO, Bo cng to thnh BN:
2 B + 2 NH3 2 BN + 3 H2
5 B + 3 NO 3 BN + B2O3
Trng thi thin nhin v phng php iu ch
Bo l nguyn t tng i ph bin trong v qu t. Khong vt chnh

ca Bo l borat (Na2B4O7.10H2O).
iu ch Bo vi tinh khit cao, ngi ta dng Mg kh B2O3 nhit

cao
B2O3 + 3 Mg 2 B + 3 MgO
Hn hp sau phn ng c ra bng kim, HCl v HF. Ngoi ra c th

dng Na kh kali tetraborat nhit cao:
196
KBF4 + 3 Na B + KF + 3 NaF
XI.1.2. Cc hp cht quan trng
1, Boran
Trong thc t khng c nhng bo hydrua nh BH3, B2H4, B3H5... iu

ny l do trong cc hp cht B cha c bo ha v s phi tr v trng thi
lai ha sp2 ca B khng c lm bn thm nh lin kt khng nh ch nh
trong cc hp cht BF3, BCl3... S bo ha v s phi tr c th t c khi cc
phn t bo hydrua trn kt hp li vi nhau to thnh nhng phn t nh B 2H6,
B4H10... Cc bo hydrua ny gi chung l boran.
a. Cu to ca B2H6
Tng s electron trong phn t B2H6 l 12, khng to thnh 8 lin

kt cng ha tr bnh thng, mi lin kt do 1 cp electron m nhn. Ngi ta
ni rng diboran l hp cht thiu electron.
Phn t diboran gm 2 nhm t din lch BH4 ni vi nhau qua mt cnh

chung. Hai nguyn t B v 4 nguyn t H 2 u cng nm trn mt mt phng
cn 2 nguyn t H cu ni nm trn v di mt phng v i xng nhau.
Lin kt ca cc nguyn t H 2 u v nguyn t B l lin kt cng ha tr
bnh thng c to nn bi orbital lai ha sp3 ca B, trn mi orbital c 1
electron c thn xen ph vi orbital 1s ca H cng c 1 electron c thn. Lin
kt gia mi nguyn t H ca cu ni vi 2 nguyn t B (B H B) l kiu lin
kt c bit, ngha l y c 2 lin kt nhng ch c 1 cp electron.
Theo phng php MO th lin kt cng ha tr bnh thng l lin kt 2

tm, cn lin kt B H B l lin kt 3 tm. Trong phn t B2H6 c 2 lin kt 3
tm. Mi lin kt c hnh thnh nh s che ph ca 2 orbital lai ha sp 3 ca 2
nguyn t B, 1 orbital c electron c thn, cn 1 orbital khng cha electron
vi 1 orbital 1s ca nguyn t H cu ni c 1 electron c thn. Ba orbital t
hp thnh 3 orbital phn t: lin kt, khng lin kt vfa phn lin kt; cp
electron chung c phn b trn MO lin kt.
197
Sx
KLK sp3
sp3

1s Slk

Gin nng lng ca cc MO ca mt lin kt 3 tm trong B2H6
b. Tnh cht
iu kin thng B2H6 v B4H10 l cht kh; B5H9, B5H11 v B6H10 l

cht lng, cn li l cht rn c cc boran c mi kh chu v rt c.
Cc boran l hp cht km bn v hot ng v mt ha hc. Khi un

nng, chng phn hy thnh nguyn t. Tt c cc boran khi gp khng kh u
bc chy, phn ng pht nhiu nhit.
B2H6 + O2 B2O3 + H2O H = - 428 kcal
Cc sn phm chy to ra c khi lng b hn nn boran c dng lm

nhin liu tn la.
- Boran tng tc mnh vi halogen v b halogen thay th dn hydro:
B2H6 + Cl2 B2H5Cl + HCl
Khi d Cl2 th hydro c th b thay th hon ton:
B2H6 + Cl2 BCl3 + HCl
198
- Tt c cc boran u b nc v dung dch kim phn hy thnh axit boric hay

mui borat:
B2H6 + H2O H3BO3 + H2
- Diboran cn c th tng tc vi nhiu hp cht nh hydrua kim loi kim,

CO, NH3 ...
B2H6 + NaH NaBH4 (natri borohydrua)
Vi NH3 diboran to nn hp cht tinh th mu trng c thnh phn

B2H6.2NH3 . Dung dch ca hp cht ny trong NH3 lng dn in nn c l
cng thc phn t ca hp cht l: H2N(NH3 )2]+[BH4]-. Khi un nng n 200
0
C hp cht ny bin thnh borazol B3N3H6. l mt cht lng khng mu, c
khi lng phn t v cu to ging vi benzen, do c tnh cht ging vi
benzen nn ngi ta thng gi l benzen v c.
2, Oxit Boric
B2O3 c 2 dng th hnh: dng thy tinh v dng tinh th. B2O3 dng
thy tinh l cht dng khi rn, khng mu v gin. Khi un nng n tr nn
do ri to thnh khi nht, c th kp si v ha lng 6000C. B2O3 dng thy
tinh c cu to bi cc nhmBO3 ni vi nhau qua nguyn t O v sp xp
mt cch hn n. Dng tinh th c cu trc hon ton khc, gm nhng t din
lch BO4 ni vi nhau qua nhng nguyn t O. Trong 4 nguyn t O th c 1
nguyn t O chung cho 2 t din v 3 O cn li chung cho 3 t din.
- B2O3 rt bn vi nhit, n bt u si 18000C. Ngi ta a ra 2 cng

thc ca B2O3 l:
199
B O
O O O v B B
B O O
- Khi nung nng, than khng d dng kh c B2O3 thnh B
- B2O3 ht m rt nhanh v tan trong nc to thnh H3BO3
B2O3 + H2O H3BO3
3, Axit Boric
Axit boric l cht dng tinh th trong sut v c mu trng. N tan va

phi trong nc, qu trnh ha tan thu nhiu nhit. Do tan ca H3BO3 tng
nhanh theo nhit , ngi ta d dng kt tinh li H3BO3 dng rn.
Khi un nng H3BO3 (octhoboric) mt dn nc v 1000C to thnh axit

metaboric HBO2 v khi nhit cao hn na th bin thnh B2O3 .
t0 t0
H3BO3 H2O HBO2 H2O B2O3
- Tuy trong cng thc H3BO3 nhng axit octhoboric l axit mt nc v rt

yu, yu hn c axit H2CO3: H3BO3 + H2O [B(OH)4]- + H+
Ka = 10-9.
XI.2. NHM
XI.2.1 n cht
200
Tnh cht l hc
Nhm l kim loi mu trng bc, khi lu trong khng kh n tr nn

xm do to thnh mng oxit mng trn b mt.
- Nhm l kim loi dn in v dn nhit tt. B mt ca nhm trn v

bng c kh nng phn chiu tt nh sng nn ngi ta thng dng nhm
trng ln b mtca gng phn chiu trong cc knh vin vng.
- Nhm c kh nng to c nhiu hp kim vi cc kim loi khc, quan

trng nht l duyara (94% Al, 4% Cu, 2% Mg, Mn, Fe v Si). Duyara ngoi u
im l nh nh nhm cn c nhng tnh cht c l tt hn nhm.
Tnh cht ha hc
- Khc vi Bo, Al l kim loi hot ng (do bn knh nguyn t ln hn

hn Bo). iu kin thng Al b ph lp oxit Al2O3 rt mng (0,00001mm)v
bn lm cho Al tr nn km hot ng. Trong thc t n khng b g v bn vi
nc...
- Dy nhm hay l nhm dy khng chy khi c t nng mnh m

nng chy trong mng oxit to thnh nhng ti bn trong l nhm lng v bn
ngoi l oxit. L nhm mng khi t mnh s chy sng chi v pht nhiu
nhit.
4 Al + 3 O2 2 Al2O3 H = - 399 kcal/mol
Tm nhm khi c nhng trong dung dch mui thy ngn hoc thy
ngn kim loi th s b oxy ha n cng v khng c mng oxit bo v.
- Do i lc ln i vi oxi nn nhm l cht kh mnh, nhit cao n

d dng kh nhiu oxit kim loi n kim loi t do:
Al + Cr2O3 Al2O3 + 2 Cr
Trong thc t ngi ta dng phng php ny iu ch nhng kim loi

kh b kh v kh nng chy nh Fe, Cr, Mn, Ni, Ti, Zr, V...
201
-Al tuy c tng nng lng ion ha I1, I2 v I3 kh ln (1230 kcal/ntg)

nhng nh ion Al3+ c nng lng hydrat ha rt ln (1100 kcal/iong) nn Al
kim loi d dng chuyn thnh Al3+ trong dung dch
Al3+ (dd) + 3e Al (r) E0 = - 1,66V
Tuy c th in cc thp, v mt nguyn tc Al d dng y hydro ra khi

nc nhng do mng oxit bn bo v nn Al khng tc dng vi H2O, khng tc
dng vi dung dch long ca axit H3PO4 v CH3COOH. Al ch d dng tan
trong dung dch long ca axit HCl v H2SO4 :
Phn ng chung ca Al khi tan trong dung dch axit l:
2 Al + 6 H3O+ + 6 H2O 2[Al(H2O)6]3+ + 3 H2
Trong axit HNO3 v H2SO4 m c ngui th Al b th ng ha.
- Tng t Be, Al tan trong dung dch kim mnh gii phng H2 :
2 Al + 2 OH- + 6 H2O 2[Al(OH)4]- + 3 H2
Trng thi thin nhin v phng php iu ch
- Al l mt trong nhng nguyn t ph bin nht. Phn ln Al tp trung

vo alumosilicat: octhoclaz (K2O.Al2O3.6SiO2), caolinit (Al2O3.SiO2.2H2O )...
Hai khong vt quan trng ca Al trong cng nghip l boxit (Al 2O3 .nH2O) v
cryolit.
- Gia TK 19, phng php sn xut Al ch yu l dng kim loi kim

kh mui AlCl3 hoc natri tetracloroaluminat NaAlCl4 trng thi nng chy.
Do gi thnh ca Al rt cao.
AlCl3 + 3 Na Al + NaCl
NaACl4 + Na Al + NaCl
- Cui TK 19, Al mi c sn xut quy m cng nghip bng phng

php in phn hn hp Al2O3 (6 8%) v Na3AlF6 (92 94%) nng chy.
202
+ Qung boxit cha nhiu tp cht, tinh ch ngi ta un nng bt

boxit trong dung dch NaOH 40% 1500C di p sut 5 6 atm. Khi :
Al2O3 + 2 NaOH + 3 H2O 2 Na[Al(OH)4]
Lc ly dung dch v pha long th Al(OH)3 s kt ta lng xung
Na[Al(OH)4] Al(OH)3 + NaOH
Lc ly kt ta v nung nhit cao ta c Al2O3 tinh khit.
+ Cryolit trong t nhin kh him nn ngi ta thng iu ch bng cch

ha tan Al(OH)3 v Na2CO3 trong dung dch HF:
2 Al(OH)3 + 12 HF + 3 Na2CO3 2 Na3[AlF6] + 9 H2O + 3 CO2
C ch qu trnh in phn Al2O3 trong cryolit n nay vn cha xc nh

dt khot. Ngi ta cho rng: cryolit l hn hp ca AlF3 v NaF, khi in phn
th ch c NaF b in phn to Na v F2. Na sinh ra s tc dng vi Al2O3 to
thnh Al kim loi v mui NaF, cn F2 s y oxy trong Al2O3 to thnh AlF3.
V th nng cryolit trong bnh in phn khng thay i.
XI.2.2. Mt s hp cht quan trng
1. Nhm hydrua
- Nhm hydrua l hp cht polyme (AlH3)n. N l cht rn v nh hnh,

mu trng, khng bay hi v phn hy nhit trn 105 0C v to thnh
nguyn t.
Tng t bo hydrua, nhm hydrua l hp cht thiu electron. N c cu

trc lp, mi nguyn t Al c bao quanh bi 6 nguyn t H theo kiu bt
din. Mi nguyn t Al ni vi 3 nguyn t Al bn cnh bng nhng lin kt 3
tm qua mt nguyn t H nh lin kt 3 tm trong diboran.
- Nhm hydrua l hp cht rt nhy i vi O2 v H2O, n bc chy trong

khng kh. Khi tan trong dung dch ete n d dng kt hp vi hydrua kim loi
kim tho thnh hydroxyaluminat:
203
n LiH + (AlH3)n n Li[AlH4]
Li[AlH4] l cht kh mnh, n thng c dng trong cc phn ng tng hp

hu c.
H H
H H H
Al Al
H H H
H H H H
Al Al
H H H H
H H H
Al Al
H H H
H H
Cu trc ca (AlH3)n
- nhit thp, nhm hydrua d dng kt hp vi nhng cht cho electron

nh NH3, MNH2, M2NH, M3N (M l kim loi kim), N(CH3)3:
(AlH3)n + n NH3 n AlH3.NH3
2. Nhm oxit (Al2O3 )
Nhm oxit
- nhit thng corundum rt tr v mt ha hc, khng tan trong nc, axit

v kim. Nhng 10000C n tng tc mnh vi hydroxit, cacbonat,
hydrosunfat v disunfat kim loi kim trng thi nng chy:
204
Al2O3 + Na2CO3 NaAlO2 + CO2
Al2O3 + K2S2O7 Al2(SO4)3 + K2SO4
- nhit cao Al2O3 tng tc vi mt s oxit kim loi to nn nhng sn

phm c tnh cht ging nh ngc chng hn: spinen MgO.Al2O3, alexandrit
BeO.Al2O3
- Trong thc t Al2O3 c dng lm vt liu chu la, sn xut Al...
- Trong cng nghip Al2O3 c iu ch bng cch nung Al(OH)3 nhit

1200 1400 0C
Al(OH)3 Al2O3 + H2O
3. Nhm hydroxit (Al(OH)3 )
Nhm hydroxit c to nn khi hydroxit kim loi kim tc dng vi

mui nhm, l kt ta nhy trng, thc t khng tan trong nc. Bng
phng php thc nghim (nhiu x tia X), ngi ta nhn thy rng n khng c
cu trc tinh th. lu n mt nc dn, sy kh ri nung n khi lng
khng i to thnh oxit Al2O3. Nh vy kt ta nhy trng ca hydroxit nhm
thc cht l Al2O3 .nH2O.
O O
O O O
O O O
O O O O
O O O O
O O O
O O O
O O
205
Cu trc ca lp hydragilit
- Al(OH)3 c to ra khi cho kh CO2 sc qua dung dch NaAlO2, tinh

th ny chnh l tinh th hydroxit nhm trong t nhin l gipxit (hydragilit).
Hydragilit gm nhng tinh th n t v cu trc lp. Mi lp gm 2 mt ng
cc nhm OH v nhng nguyn t Al nm gia 2 lp . Mi nguyn t Al
c 6 nhm OH bao quanh.
Hydragilit bn nhit di 1500C , n c trong thnhnnnn ca nhiu

loi boxit.
- Nhm hydroxit l cht lng tnh in hnh, khi mi kt ta n d dng

tan trong axit v kim:
Al(OH)3 + 3 H3O+ [Al(H2O)6]3+
Al(OH)3 + OH- + 2H2O [Al(OH)4(H2O)2]-
Anion [Al(OH)4(H2O)2]- thng vit gn di dng [Al(OH)4]- gi l ion

aluminat. Mui khan thu c khi lm bay hi dung dch natri aluminat l
NaAlO2. Mui ny bi thy phn rt mnh, trong dung dch long s b thy phn
hon ton. V th khi sc kh CO2 vo dung dch NaAlO2 th s thu c
Al(OH)3 .
4. Nhm halogennua
Cc hp cht nhm halogenua khc nhau nhiu v cu to cng nh tnh

cht. Nhm florua c cu trc ion, nhm bromua v iodua mi trng thi u
gm nhng phn t Al2Br2 v Al2I2, nhm clorua trng thi rn c kin trc
ion, nhng trng thi kh v trng thi tan gm nhng phn t Al2Cl6.
206
a. Nhm florua
- Nhm florua l cht dng tinh th, c mu trng, nng chy 1290 0C.
- N rt tr v mt ha hc, khng tan trong nc, axit v baz.
- N ch d dng kt hp vi florua kim loi to thnh cc

floroaluminat kim loi c cng thc chung l M[AlF4], M2[AlF5], M3[AlF6]
trong M l kim loi kim. Quan trng nht l cryolit
Na3[AlF6].
- Nhm florua c iu ch bng cch cho Al hay Al2O3 tng tc vi

kh HF
Al + HF AlF3 + H2
Al2O3 + HF AlF3 + H2O
b. Nhm clorua
- Nhm clorua l cht rn dng tinh th mu trng, n thng ng mu

vng v cha tp cht FeCl3 . Nhm clorua trng thi kh cng nh trng thi
tan dng dime Al2Cl6.
Cl
Cl 2,12 A0
Cl
2,06 A0
0
Al 80 C Al
Cl Cl
Cl
Cu trc phn t Al2Al6
207
Mi mt lin kt Al Cl Al khng cn phi m t nh lin kt 3 tm

nh trong diboran m c th coi l mt lin kt cng ha tr bnh thng v mt
lin kt cho nhn m Cl l nguyn t cho.
- Phn t Al2Cl6 ny phn ly hon ton thnh nguyn t 8000C
- Nhm clorua bc khi kh mnh trong khng kh v n ht m mnh ri

thy phn gii phng HCl, v th cn bo qun nhm clorua trong l kn. N ha
tan mnh trong nc ng thi ta nhit mnh, dung dch c mi trng axit.
AlCl3 + H2O Al(OH)3 + HCl
- AlCl3 kt hp d dng vi clorua kim loi kim to thnh cloroaluminat

c cng thc chung l
M[AlCl4], M2[AlCl5], M3[AlCl6] trong M l kim loi kim.
- Mui khan d dng kt hp vi NH3 , H2O , PCl5 v mt s hp cht

hu c. V vy n c dng rng ri trong tn hp hu c.
- Di tc dng ca kh O2 kh, mui khan b phn hy gii phng Cl2
Al2Cl6 + O2 Al2O3 + Cl2
- 10000C n tng tc vi Al kim loi to thnh mui Al c mc oxi

ha thp hn:
Al2Cl6 + Al AlCl
Nhm clorua khan c th iu ch bng cch cho kh Cl2 tng tc vi

bt Al 500 5500C hoc vi hn hp Al2O3 v than 10000C :
Cl2 + Al2O3 + C AlCl3 + CO
5. Nhm sunfat v phn nhm
- Nhm sunfat Al2(SO4)3 khan l cht bt mu trng, n phn hy nhit

trn 7700C. T dung dch nc n kt tinh dng hydrat Al2(SO4)3.18H2O.
208
- Nhm sunfat c th kt hp vi sunfat kim loi kim to thnh mui kp

M2SO4.Al2(SO4)3.24H2O thng gi l phn nhm. Phn l mt loi mui c
cng thc chung M2SO4.E2(SO4)3.24H2O trong M (K, Na, Rb, Cs, NH4...), E
(Al, Cr, Fe, Ga, In, Tl, Co). Chng ng hnh vi nhau v to nn nhng tinh th
bt din. c s dng nhiu hn ht l phn nhmkali
K2SO4.Al2(SO4)3.24H2O, phn crom kali K2SO4.Cr2(SO4)3.24H2O v phn st
amoni (NH4)2SO4.Fe2(SO4)3.24H2O.
- Nhm sunfat v phn nhm kali c nhng cng dng ch yu ging

nhau trong cng nghip giy, nhum, thuc da v lm trong nc. Nhng cng
dng ny xut pht t ch mui nhm thy phn kh mnh trong nc to thnh
hydroxit nhm. Khi nhum vi, hydroxit nhm b vi hp th v gi cht trn
si s kt hp vi phm nhum to thnh mu bn, nn n c gi l cht cn
mu. Tc dng lm trong nc l do hydroxxit nhm hp th cht l lng v vi
khun trong nc lm cho chng cng lng xung di. Trong cng nghip
giy, nhm sunfat hay phn nhm c cho vo bt giy cng vi mui n.
Nhm clorua to nn do phn ng trao i, b thy phn mnh hn to thnh
hydroxit. Hydroxit ny s kt dnh nhng si xenluloza vi nhau lm cho giy
khng b nhe mc khi vit.
- Phn nhm kali c iu ch bng cch cho kt tinh t hn hp dung

dch Al2(SO4)3 v K2SO4 cng nng .
XI.3. GALI, INI V TALI
XI.3.1. n cht
Tnh cht vt l
- trng thi t do Ga, In l nhng kim loi c mu trng bc, Tl c mu

xm xanh. Tt c u c nhit nng chy thp.
- Ga v In u c tnh cht phn chiu tt nh sng nn c dng

trng gng, c bit l In l kim loi khng th thiu c trong lnh vc sn
xut knh thin vn chnh xc.
209
- Cng nh Al, cc kim loi Ga, In v Tl d to nn hp kim vi cc kim

loi khc. V d: hp kim gm 18,1% In, 41% Bi, 22,1% Pb, 10,5% Sn v 8,2%
Cd nng chy 47 0C c dng b xng trong nhng trng hp phc tp
Tnh cht ha hc
- Ging vi Al, cc kim loi Ga, In bn trong khng kh v c mt lp oxit

bn bo v cn Tl b oxi ha chm.
- Khi un nng, Ga, In v nht l Tl tng tc mnh lit vi O2 v S
- Vi Cl2 v Br2 chng tng tc mnh lit nhit thng, i vi I2

th cn phi un nng.
- Ga v In tan d dng trong dung dch HCl v H2SO4 nhng Tl tng tc

chm v trn b mt to thnh lp mui kh tan bo v. Ngc li trong HNO3
th Ga phn ng rt chm trong khi Tl phn ng rt mnh.
- Ging vi Al, Ga cng tan trong dung dch kim to mui galat
Ga + OH- + H2O [Ga(OH)4]- + H2
Nu khng c cht oxi ha th In v Tl khng tan trong kim. Ga c th

tan r rt trong dung dch NH3 .
Trong thin nhin cc nguyn t Ga, In v Tl u t ph bin v rt phn

tn, chng khng c nhng khong vt ring m thng di dng tp cht
trong mt s qung ca cc kim loi Al, Zn, Fe v Cu. Nguyn liu chnh sn
xut Ga l qung boxit, In l sunfua ca cc kim loi Zn, Pb v Cu cn Tl l
qung pyrit FeS2.
Qu trnh iu ch kh phc tp. Sau nhiu ln ch ha qung v tinh ch,

ngi ta tch ra c oxit hoc clorua ri in phn dung dch mui clorua hoc
dng kh H2 kh oxit ca chng.
XI.3.2. Hp cht
210
XI.3.2.1. Cc hp cht c mc oxy ha +3
1. Oxit (E2O3)
- Cc oxit E2O3 u l cht rn, Ga2O3 mu trng, In2O3 mu vng cn

Tl2O3 mu hung. Ph hp vi gi tr sinh nhit:
Oxit Al2O3 Ga2O3 In2O3 Tl2O3
H (Kcal/mol) - 399 - 285 - 222 - 120
Ga2O3 nng chy 1740 0C khng phn hy, In2O3 nng chy 850 0C v
chuyn thnh In3O4 cn Tl2O3 bt u mt oxy 100 0C v bin thnh Tl2O. V
vy khi t nng trong khng kh Tl to nn hn hp Tl2O3 v Tl2O.
- Tt c cc E2O3 u khng tan trong nc, dung dch kim v dung dch
axit tr Tl2O3 tan c trong axit
- Tr Tl2O3, tt c cc oxit E2O3 cn li u c th iu ch bng cch t

chy kim loi trong khng kh. Ngoi ra c 3 oxit u c th iu ch bng cch
nhit phn hydroxit hay mui nitrat:
4Ga(NO3)3 2Ga2O3 + 12NO2 + 3O2
2. Hydroxit E(OH)3
- Cc hydroxit ny l kt ta nhy, thc t khng tan trong nc v c

thnh phn khng xc nh. Gali hydroxit c mu trng tn ti 2 dng
Ga(OH)3 v GaOOH, indi hydroxit ch c mt dng In(OH)3 c mu trng v
tali hydroxit c mu hung tn ti 2 dng Tl(OH)3 v TlOOH. Khi un nng
h, huyn ph Tl(OH)3 chuyn thnh TlOOH v khi un si chuyn thnh Tl2O3.
- Cc hydroxit tan d dng trong dung dch axit to thnh mui:
In(OH)3 + 3 H3O+ [In(H2O)6]3+
- Tr Tl(OH)3, chng cng tan trong dung dch kim ging nh nhm
hydroxit to thnh mui hydroxygalat v hydroxyindat c thnh phn v tnh
cht tng t aluminat:
211
In(OH)3 + OH- [In(OH)4]-
- Ring Ga(OH)3 cn tan c trong dung dch NH3 m c, iu ny

chng t tnh axit ca Ga(OH)3 mnh hn nhm hydroxit.
- Tt c cc E(OH)3 u c iu ch bng cch cho mui E(III) tc

dng vi dung dch kim
3. Mui E(III)
- a s mui ca axit mnh d tan trong nc nhng b thy phn kh

mnh ging nh mui nhm lm cho dung dch c mt trng axit. Trong
nhng mui tan ca axit yu, nhiu mui b thy phn hon ton.
- Cc halogen EX3 ni chung ging mui AlCl3. Chng tng i d nng

chy, d tan trong nc v mt s dung mi hu c. Ging vi AlCl3, cc mui
khan GaCl3 v InCl3 cng bc khi mnh trong khng kh. Chng d dng kt
hp vi MX to thnh nhng phc cht kiu M3[EX6] v M[EX4] vi M l
kim loi kim.
V d: GaCl3 + 3 KCl K3[GaCl6]
XI.3.2.2. Cc hp cht ca Tl c mc oxy ha +1
Ion Tl+ c bn knh 1,44 A0, tng ng vi bn knh ca cc ion K+, Rb+, Ag+
nn hp cht ca chng ging vi nhiu hp cht kim loi kim v bc.
1. Tl2O
- L cht b mu en, nng chy 3000C thnh cht lng mu vng tng
tc mnh vi thy tinh. N ht m v tan d dng trong nc to Tl (I) hydroxit:
Tl2O + H2O TlOH
- N cng tan d dng trong ru v axit. Khi un nng trong O2 hay

trong khng kh n bin thnh Tl2O3:
Tl2O + O2 Tl2O3
- N d b hydro hay CO kh n kim loi.

212
2. TlOH
- L cht dng tinh th mu vng, khng bn v mt nc 1000C to

thnh Tl2O. N hp th kh CO2 v tan trong nc thnh dung dch kim mnh.
Dung dch ca n cng hp th kh CO2, tc dng vi thy tinh v s. Tuy nhin
TlOH l baz yu hn KOH.
- TlOH c th iu ch bng cch ha tan Tl2O vo nc hoc cho mui

Tl2SO4 tc dng vi Ba(OH)2
Tl2SO4 + Ba(OH)2 Tl(OH) + BaSO4
3. Mui Tl(I)
- Tng t mui kim, cc mui Tl(I) l hp cht ion. Dung dch mui
Tl(I) rt c, ch mt lng nh cng lm rng tc.
- Tng t mui bc, TlF d tan nhng TlCl, TlBr v TlI tng i t tan.
213
CHNG XII. CC NGUYN T NHM IIA
(KIM LOI KIM TH)
Cc kim loi kim th thuc nhm IIA ca BHTTH. Chng bao gm cc

nguyn t Be, Mg, Ca, Sr, Ba, Ra. Chng c gi l kim loi kim th v mt
mt cc oxit CaO, BaO, SrO tan c trong nc cho dung dch kim mnh v
mt khc cc oxyt c tan b v bn nhit cao ngha l c nhng tnh
cht m cc nh gi kim thut ngy xa gi l th (t). Sau y l mt s c
im ca cc nguyn t kim loi kim th:
Be Mg Ca Sr Ba Ra
S th t 4 12 20 38 56 88
Cu hnh electron 2s2 3s2 4s2 5s2 6s2 7s2
Bn knh ngt (A0) 1,13 1,6 1,97 2,15 2,21 2,35
Bn knh ion M2+ (A0) 0,34 0,74 1,04 1,2 1,33 1,14
I1 Kcal/ntg) 214,9 176,3 140,9 131,3 120,2 121,7
I2 Kcal/ntg) 419,9 346,6 273,8 254,3 230,7 234,9
Th in cc (V) -1,85 -2,37 -2,87 -2,89 -2,9 -2,92
- Do c 2 electron ha tr ns2 ngoi cu hnh bn ca kh tr, cc nguyn

t kim loi kim th d dng mt 2 electron to thnh ion M2+, chng l kim loi
hot ng v hot tnh tng dn t Be Ra. So vi cc nguyn t kim loi
kim cng chu k th kim loi kim th t hot ng hn v c in tch ht nhn
ln hn v bn knh nguyn t nh hn.
- Vic I2 ln hn nhiu so vi I1 cho thy dng nh cc kim loi kim

th d to nn M+. Nhng trn thc t, nhiu phn ng c thc hin trong
dung dch nn nng lng hydrat ha cao ca M2+ b p cho nng lng ion
ha cao nn nguyn t kim loi kim th d mt 2 electron ha tr to ra M2+.
214
- Trong cc hp cht, cc kim loi kim th ch c mc oxy ha +2. Be

to nn ch yu nhng hp cht lin kt cng ha tr, cc nguyn t cn li ch
yu to hp cht ion.
XII.1 N CHT
XII.1.1.TNH CHT L HC
Cc kim loi kim th c mu trng bc hoc xm nht trong khng kh

Be, Mg vn gi c nh kim cn cc kim loi khc mt mu nh kim nhanh
chng. Nhit nng chy, nhit si ca kim loi kim th ln hn kim loi
kim.
Tr Be v Mg, cc kim loi kim th t do v cc hp cht d bay hi ca

chng khi cho vo ngn la khng mu lm cho ngn la c mu c trng: Ca,
da cam; Sr, son; Ba, mu lc hi vng. Trong ha hc phn tch ngi ta
da vo mu c trng ny nhn bit cc kim loi .
Mt s hng s vt l quan trng ca kim loi kim th
Be Mg Ca Sr Ba Ra
T trng (g/cm3) 1,85 1,74 1,6 2,6 3,75 5
t0nc (0C) 1285 651 851 770 710 960
t0s (0C) 2970 1107 1482 1880 1640 1140
dn in ring (, 1,7.10
-1
28.104 25.104 23.104 3.104 4 -
cm )
XII.1.2. TNH CHT HA HC
Cc kim loi kim th l nhng kim loi hot ng ng sau kim loi
kim. Trong cc phn ng chng th hin tnh kh v tnh kh tng ln dn t
Be Ra.
215
1, Tc dng vi hydro
Khi un nng cc kim loi Ca, Sr v Ba tc dng d dng vi H2 to ra

hydrua ion MH2. Chng hn hydrua canxi c to ra 150 0C:
Ca + H2 CaH2
Cc hydrua ion ca kim loi kim th bn hn hydrua ion kim loi kim.
2, Tc dng vi oxi
Be, Mg chy trong khng kh to ra BeO v MgO
2Mg + O2 2MgO + 292KCal
Ca, Sr, Ba nhanh chng b oxy ha trong khng kh to ra lp oxit mu

vng nht. Khi c xt Ba c th bc chy. Mg khi chy cn pht ra nh sng
pht ra nh sng chi v giu tia t ngoi nn c dng lm pho sng.
3, Tc dng vi cc cht khc
Khi un nng kim loi kim th tc dng mnh vi halogen, S, P, N2, C,

Si.
Khi kim loi kim th chy trong khng kh, ngoi oxyt MO cn c nitrua
M3N2
3Mg + N2 Mg3N2
Cc nitrua c pht hin do phn ng vi nc cho NH3
Mg3N2 + 6H2O 3Mg(OH)2 + 3NH3
Li dng kh nng d phn ng d phn ng vi O2, N2 ngi ta dng Ca

vo vic loi O2, N2 ra khi cc kh tr.
Khi tc dng vi C, Be to ra Be2C gii phng CH4 khi thy phn, cn

cc kim loi kim th khc to ra cacbua MC2 gii phng C2H2 khi b thy phn.
2Be + C Be2C
216
Ca + C CaC2
Be2C + 4H2O 2Be(OH)2 + CH4
CaC2 + 2H2O C2H2 + Ca(OH)2
Khi tc dng vi Si tt c cc kim loi kim u to ra cc Silixua M2Si
2Ca + Si Ca2Si Silixua Canxi
Do i lc mnh vi oxy cc kim loi kim th khi un nng c th kh

nhiu oxyt bn nh B2O3, CO2, SiO2, TiO2, Al2O3, Cr2O3...
2Mg + CO2 2MgO + C
2Be + TiO2 2BeO + Ti
C th in cc b tng ng vi kim loi kim, cc kim loi kim th

d dng tc dng vi H2O gii phng H2 v cng d vi axit. Thc t Be khng
tan v Be(OH)2 khng tan trong nc, Mg khng tc dng vi nc lnh, tc
dng chm trong nc nng.
Ca + H2O Ca(OH)2
Ring Be do c hydroxit Be(OH)2 lng tnh nn tan c trong dung

dch kim mnh hay kim nng chy to ra mui berilat v gii phng H2.
Be + 2NaOH + 2H2O Na2[Be(OH)4] + H2
Be + 2NaOH(nc) Na2BeO2 + H2
Cng nh kim loi kim, cc kim loi Ca, Sr, Be c th tan trong NH3
lng cho dung dch mu xanh lam thm. V bn cht v tnh cht ha hc ca
dung dch mu xanh lam ny ging dung dch kim trong NH3 lng, nhng khc
ch sau khi NH3 bay hi th dung dch kim loi kim cho kim loi kim cn
kim loi kim th li tinh th vng ng nh c thnh phn khng i l
M(NH3)6 (M = kim loi kim th), khi un nng c mt xc tc ta thu c
amiua
217
Ca(NH3)6 Ca(NH2)2 + 4NH3 + H2
Canxi hexaamin Canxi amiua
XII.2. CC HP CHT CA KIM LOI KIM TH
XII.2.1. Oxyt
c im chung
Cc oxit MO l cht bt hoc cc mu trng, khi nu chy trong l in

ngui, chng s dng tinh th. BeO c mng li tinh th lc phng, cc
oxit khc c mng li lp phng. V c nng lng mng li rt ln nn cc
oxit MO rt kh nng chy v rt bn nhit, chng c th bay hi m khng b
phn hy.
BeO MgO CaO SrO BaO
Nng lng mng li Kcal/ptg - 938 841 792 756
t0nc (0C) 2252 2800 2570 2460 1925
t0s (0C) 4200 3100 3600 2500 2000
V vy cc oxit MO dng lm vt liu chu la.
Tnh cht ha hc
- BeO khng tan trong nc, MgO tan chm v rt t; cc oxyt Ca, Sr, Ba tan d
dng v phn ng ta nhiu nhit.
MO + H2O M(OH)2
- Cc oxit CaO, SrO, BaO u ht m mnh v c kh nng hp th kh CO2
BaO + CO2 BaCO3
218
- MO l cc oxit baz c th tan trong dung dch axit to ra mui
MO + HCl MCl2 + H2O
ring BeO kh tan trong axit d tan trong dung dch kim to ra mui berilat
BeO + 2NaOH Na2BeO2 + H2O
BeO + 2HCl + 3H2O [Be(OH)2]Cl2
- nhit cao, cc MO c th b kim loi kim, Al, Si kh n kim loi.
ng dng
Trong thc t BeO dng lm cht xc tc, chn nung, cng nghip thy
tinh. MgO lm gch chu la, iu ch Mg kim loi ximng magi. CaO (vi
sng) dng lm vt liu xy dng, iu ch CaC2...
iu ch
Nguyn tc chung ca phng php iu ch oxit MO l nhit phn mui

cacbonat, nitrat hoc hydroxit ca kim loi kim th
CaCO3 CaO + CO2
XII.2.2 Peoxyt
Tng t kim loi kim, cc cation kim loi kim th c bn knh ln

cng c kh nng lm bn mt s anion ln nh peoxyt, supeoxit. Be khng
to nn peoxyt; Mg ch to nn peoxyt dng hydrat c ln peoxyt MgO2; cn
Ca, Sr v Ba to nn cc peoxyt MO2 l cht bt mu trng kh tan trong nc
khi un nng MO2 to ta MO v O2
MO2 MO + 1/2O2
- Cc MO2 u l cht oxy ha mnh, nhng khi tc dng vi cht oxy ha

mnh hn chng l cht kh.
MO2 c iu ch khi cho H2O2 tc dng vi dung dch hydroxit tng ng:
219
Ca(OH)2 + H2O2 + 6H2O CaO2.8H2O
CaO2.8H2O CaO2 + 8H2O
Ring BaO2, SrO2 c th iu ch bng cch cho oxyt kt hp trc tip vi oxyt
2BaO + O2 2BaO2
Peoxit quan trng nht l BaO2 l mt cht bt mu trng nng chy

450 C, phn hy 6000C, kt hp 4000C:
0
2BaO2 2BaO + O2
BaO2 kh tan trong nc, ru, te nhng d tan trong dung dch axit long gii
phng H2O2
BaO2 + HCl BaCl2 + H2O2
BaO2 + H2SO4 BaSO4 + H2O2
khi un nng BaO2 tng tc vi H2, S, C, NH3
BaO2 + H2 Ba(OH)2
BaO2 + S 2BaO + SO2
vi axit HCl c, gii phng kh Cl2
4HCl + BaO2 BaCl2 + Cl2 + H2O
BaO2 c th kh kim loi qu, nng thnh kim loi t do
HgCl2 + BaO2 Hg + BaCl2 + O2
XII.2.3. Hydroxyt M(OH)2
Cc Hydroxyt M(OH)2 khan u dng bt mu trng. Be(OH)2,

Mg(OH)2 rt kh tan, Ca(OH)2 tan tt trong nc. M(OH)2 khng bn nhit khi
un nng, mt nc to ra oxyt bn nhit tng ln t Be Ba
M(OH)2 MO + H2O
220
Cc M(OH)2 bao gm hon ton cc ion kim loi M2+ v ion OH-, trong
dung dch chng l nhng baz tnh, baz tng ln t Be(OH)2 Ba(OH)2.
Be(OH)2 l mt baz rt yu, Mg(OH)2 yu, Ca(OH)2, Sr(OH)2, Ba(OH)2 l
nhng baz mnh. Cc M(OH)2 c kh nng hp th CO2, d tan trong axit to
ra mui.
Ba(OH)2 + CO2 BaCO3 + H2O
Ba(OH)2 + HCl BaCl2 + H2O
ring Be(OH)2 cn c kh nng tan trong dung dch kim hay dung dch
cacbonat kim loi kim m c.
Be(OH)2 + 2NaOH Na2[Be(OH)4]
iu ch Be(OH)2, Mg(OH)2 cho dung dch kim tc dng vi dung dch mui
MgCl2 + 2NaOH Mg(OH)2 + 2NaCl
BeCl2 + 2NH3 + 2H2O Be(OH)2 + 2NH4Cl
Ss(OH)2, Ca(OH)2, Ba(OH)2: c iu ch bng cch cho oxit + H2O
BaO + H2O Ba(OH)2
XII.2.4. Mui ca kim loi kim th
Cc mui kim loi kim th dng tinh th v trong dung dch ch gm

cc ion, khng mu. Cc mui halogenua, axetat, xyanua, sulfua, tioxyanat u
d tan, mui florua kh tan, tr BeF2 d tan. Mui BeSO4 v MgSO4 tan, CaSO4,
SrSO4, BaSO4 khng tan; cc mui crmmat CrO4-, oxalat C2O42-, phtphat,
cacbonat u t tan.
1. Halogenua kim loi kim th
MX2 c nhit nng chy, nhit si kh cao, mt s phn hy trc

khi si. Halogen quan trng ca Be v Mg l BeCl2 v MgCl2 tan tt trong nc,
mui khan tan tt trong (nc) ru BeCl2 l hp cht plyme c cu trc mch
di
221
Cl
Cl Cl
Cl Cl
Be Be Be Be Be
Cl Cl
Cl Cl
Cl
Be Be
Trong nhng mt Cl vung gc vi nhau. Mi nguyn t Be

ni
vi hai nguyn t Cl bng lin kt cng ha tr bnh thng v ni vi hai

nguyn t cho khc bng hai lin kt cho nhn (phi tr)
iu ch BeCl2 bng cch cho kh Cl2 kh i qua hn hp BeO, C un nng

9000C
Cl2 + BeO + C = BeCl2 + CO
MgCl2 c iu ch tch ra t nc bin, MgCl2 khan c th iu ch

bng cch cho Cl2 tc dng trc tip vi Mg
Cl2 + Mg MgCl2
dung dch MgCl2 30% trn vi bt MgO nung to thnh khi nho ng cng
sau vi gi gi l ximng magi. Trong ch yu to nn hp cht cao phn t
c cu trc mch di.
Cl-Mg-O-Mg-...........O-Mg-OH
Cc Clorua kim loi kim th khc c iu ch nh sau:
MCO3 + 2HCl MCl2 + H2O + CO2

222
Mun c CaCl2 khan nung nng CaCl2.6H2O 2600C, CaCl2 khan l mt cht
ht m, cht lm kh kh. Hp cht cha NH3 khng nn dng CaCl2 ht m v
CaCl2 + 2NH4OH 2NH4Cl + Ca(OH)2
Dung dch CaCl2 dng tri mt ng cho khi bi, trong phng th nghim
BaCl2 dng pht hin ion SO42-.
2. Mui sulfat kim loi kim th
Cc mui sulfat MSO4 l nhng cht rn dng tinh th. BeSO4 v

MgSO4 tan rt nhiu trong nc cn cc sulfat khc t tan trong nc, nht l
BaSO4.
Mui sulfat thng ngm 2 phn t nc MSO4.2H2O cc mui Sulfat

quan trng l CaSO4, BaSO4, MgSO4.
iu ch thch cao 2CaSO4.H2O ngi ta tin hnh nung CaSO4.2H2O

160 - 1700C:
2CaSO4.2H2O 2CaSO4.H2O + H2O
Bt CaOS4.H2O nho vi nc c khi nho, sau vi gi ng cng li

thnh thch cao. Dng thch cao lm cht kt dnh trong xy dng, nn tng,
b bt, ph gia cho ximng.
BaSO4 km tan nht, c dng xc nh nh tnh Ba2+, v nh lng

SO42-. N l cht cn quang chp Rnghen a dng. MgSO4.7H2O tan tt
trong nc dng lm cht nhun trng.
3. Mui cacbonat ca cc kim loi kim th
MCO3 l cc cht rn dng tinh th. Tr BeCO3 cc cacbonat khc u

t tan trong nc cho nn chng tn ti t do trong thin nhin.
Khc M2CO3 (M = kim loi kim), cc MCO3 u khng bn vi nhit,

bn nhit tng ln t Be Ba.
223
Cc MCO3 tan c trong nc c cha kh CO2, BeCO3, MgCO3 tan khi

c d kh CO2, nh chuyn thnh mui HCO3-
MCO3 + H2O + CO2 M(HCO3)2
Khc vi hydrocacbonat kim loi kim MHCO3, cc M(HCO3)2 khng

tch ra trng thi t do m ch tn ti trong dung dch. Khi un nng dung dch
cc M(HCO3)2 mt nc, CO2 to ra MCO3
M(HCO3)2 MCO3 + H2O + CO2
Cc Cabonat quan trng l CaCO3
CaCO3 khi kt tinh t dung dch nng c dng nhng tinh th t phng,
ngui chuyn dn sang dng mt thoi.
- CaCO3 rt t tan trong nc, 1 lt nc c 0,014g CaCO3 ha tan nn d kt ta

trong dung dch NH4Cl hay c mt kh CO2
CaCO3 + 2NH4Cl CaCl2 + 2NH3 + CO2 + H2O
CaCO3 + CO2 + H2O Ca(HCO3)2
y l phn ng n mn vi trong thin nhin v do phn ng trong

nc sng thng c mt lng Ca(HCO3)2. Khi un nng Ca(HCO3)2 phn hy
Ca(HCO3)2 CaCO3 + H2O + CO2
Phn ng ny gii thch s to thnh cc thch nh trong cc hang ng

vi, hay s to thnh cn trong cc m un nc v ni hi.
- CaCO3 phn hy 9000C
CaCO3 CaO + CO2
- nhit cao n tc dng vi cc oxit nh SiO2, Al2O3, NO2 vi kh NH3
CaCO3 + SiO2 CaSiO3 + CO2
CaCO3 + 2NH3 Ca(CN)2 + 3H2O
224
XII.3. NC CNG
Nc trong thin nhin c cha mt lng ln mui tan ca Ca2+, Mg2+

gi l nc cng. cng ca nc c biu th bng s mili ng lng
gam ca ion Ca2+ v Mg2+ c trong mt lt nc. cng ca nc c th dao
ng trong mt gii hn tng i rng.
Nng (Ca2+ + Mg2+) (mE/l) Loi nc
<4 mm
48 Nc cng tm thi
8 12 Nc cng
> 12 Nc rt cng
Ngi ta phn bit lm hai loi cng
- cng tm thi hay cng cacbonat: do mui Ca(HCO3)2, Mg(HCO3)2

gy ra.
- cng vnh cu: do cc mui clorua, sulfat Mg, Ca gy ra.
Tng s cng tm thi v cng vnh cu gi l cng chung.
Nu dng nc cng cho vo cc ni hi th trn thnh ni s to nn mt

lp cn bm rt cht, lp cn ny lm gim truyn nhit ca thnh ni do
lm tng s hao ph nhin liu. Mt khc v truyn nhit km nn lp cn ny
lm cho thnh ni b nung nng ln rt mnh v c th lm n ni hi. Ngoi ra
git bng nc cng s tn nhiu x phng, lu sch.
2RCOONa + Mg2+(Ca2+) (RCOO)2Mg + 2Na2+
V vy phi lm mm nc ngha l lm gim nng Ca2+, Mg2+.
Ph cng tm thi: V cc bicacbonat d b nhit phn nn c th kh nc

cng tm thi bng cch un nng.
Ca(HCO3)2 CaCO3 + CO2 + H2O

225
Nhng thng kh cng tm thi bng cch thm Ca(OH)2, lng Ca(OH)2
thm vo c tnh ton t lng bicacbonat c trong dung dch
Ca(HCO3)2 + Ca(OH)2 CaCO3 + 2H2O
Kh nc cng vnh cu bng cch thm Na2CO3, Na3PO4 vo nc
CaCl2 + Na2CO3 CaCO3 + 2NaCl
3CaCl2 + 2Na3PO4 Ca3(PO4)2 + 6NaCl
Trong thc t thng lm mm nc cng bng phng php trao i

cation. Phng phng php ny li dng kh nng c th trao i cation ca
mt s hp cht cao phn t thin nhin v nhn to gi l ionit.
Nhng cht c kh nng trao i cation gi l cationit, nhng cht c kh

nng trao i anion gi l anionit.
Mt cationit thng dng lm mm nc gi l Zeolit c thnh phn l

Na2Al2SiO8.xH2O, ion Na+ c trong mng li tinh th ca Zeolit c mt kh
nng di chuyn nht nh. Khi di nc cng qua cc ht Zeolit, mt s ion Na+
i vo nc nhng ch cho cc ion Ca2+, Mg2+ v Fe2+ trong nc i vo
Zeolit qu trnh trao i cation xy ra nh sau:
Na2Al2SiO8.xH2O + CaCl2 CaAl2Si2O8.xH2O + 2NaCl
ti sinh li Zeolit s dng ngi ta cho dung dch NaCl bo ha i

qua Zeolit.
CaAl2Si2O8.xH2O + 2NaCl Na2Al2Si2O8.xH2O + CaCl2
Nh vy qu trnh lm mm nc bng Zeolit ch tiu tn NaCl r tin.
Mun loi tr c cation Ca2+ v anion ngi ta cho nc cng ln lt i qua 2

ct, mt ct ng cationit, mt ct ng anionit.
Nha y l nhng hp cht cao phn t hu c c cha nhm axit, c cng

thc chung l RCOOH (R- gc hu c phc tp) qua ct ny cc cation trong
nc b gi li trong nc sinh ra axit.
226
2RCOOH + CaCl2 Ca(RCOO)2 + 2HCl
Nha anionit l cc hp cht cao phn t hu c cha nhm baz c cng thc
chung l RNH3OH, qua ct ny cc ion m b gi li
RNH3OH + HCl RNH3Cl + H2O
Nhng nha ny sau khi c s dng c th c ti sinh bng cch cho ngm
trong dung dch axit, kim.
Ca(RCOO)2 + H2SO4 CaSO4 + 2RCOOH
RNH3Cl + NaOH RNH3OH + NaCl
XII.4. TRNG THI T NHIN - IU CH
Ngi ta thng gp cc kim loi ny dng nc bin, mui khong,

lmit CaCO3.MgCO3 , Cacnalit MgCl2.KCl.6H2O.
Nguyn tc chung iu ch kim loi kim th cng nh kim loi kim

l in phn mui nng chy. Ngoi ra c th dng cc cht kh kh cc
oxyt. hoc mui ca chng thnh kim loi.
Be c iu ch bng cch in phn hn hp BeCl2 v NaCl nng chy

vi m cc bng Hg trong kh quyn Ar.
Rai l cht phng x hot ng mnh, sn phm phn hy ht nhn ca 238U.
Mg c iu ch bng cch in phn nng chy mui MgCl2. MgCl2

c tch t nc bin:
- Nung lmit 9000C:
CaCO3.MgCO3 CaO + MgO + 2CO2
sau ngm hn hp oxit trong nc bin ta thu c Mg(OH)2.
CaO + H2O Ca(OH)2
227
Ca(OH)2 + Mg2+ Mg(OH)2 + Ca2+
t Mg(OH)2, MgO MgCl2 sau in phn nng chy
MgCl2 Mg + Cl2
c th kh qung lmit bng silixua st 1500 0C
CaCO3.MgCO3 + FeSi Mg + CO2 + Silicat Fe v Ca
iu ch Ca bng cch in phn nng chy hay kh bng Na
CaCl2 + 2Na 2NaCl + Ca
Trong luyn kim Mg iu ch kim loi sch, kh oxyt kim loi, hp

kim Al-Mg tr khng tc dng vi kim, v c HF, khng b r.
Hp kim 2% Mn, 98% Mg khng tc dng vi nc, hp cht CaCO3, bt

nh, Ca(OH)2 baz r tin, CaO dng cho thy tinh, ximng, s...
228
CHNG XIII. CC NGUYN T PHN NHM IA
Nhm ny bao gm cc nguyn t: Li, Na, K, Rb, Cs v Fr. S d gi l

kim loi kim v hydroxit ca chng l cht kim mnh.
Mt s c im ca kim loi kim
Nguyn t Li Na K Rb Cs Fr
S th t 3 11 19 37 55 87
Electron ha tr 2s1 3s1 4s1 5s1 6s1 7s1
Bn knh kl ca ngt 1,55 1,89 2,36 2,48 2,68 2,8

()
Bn knh ion X+ () 0,68 0,98 1,33 1,49 1,65 1,75
NL ion ha X0 X+ 5,39 5,14 4,34 4,17 3,89 3,98

(eV)
Th in cc (V) -3,02 -2,71 -2,92 -2,99 -3,02
- Do c mt electron ha tr ns1 bn ngoi cu hnh bn ca kh tr nn

cc nguyn t kim loi kim d dng mt electron ha tr to thnh M+. V
th, kim loi kim l nhng kim loi in hnh nht. Mc oxy ha c trng ca
chng l +1.
- Kim loi kim phn ln to hp cht lin kt ion. Tuy nhin chng cng
c th to nn lin kt cng ha tr trong cc phn t : Li2, Na2, K2, Rb2, Cs2
nhng nng lng lin kt kh b. Do tc dng phn cc khng ng k ca cc
ion (in tch nh, tnh bn ca cu trc electron, kch thc ion M+ ln) nn s
to phc ca K+, Rb+, Cs+, v Fr+ khng c trng, i vi chng ngay c cc
hydrat tinh th cng hu nh cha bit.
- Trong cc kim loi kim Liti chim mt v tr c bit so vi cc kim

loi kim khc. V d: Liti c th in cc m hn cc kim loi kim khc.
229
XIII.1. N CHT
Cc kim loi kim u c cu trc tinh th lp phng tm khi. y l

nguyn nhn c bn tnh cht l hc ca chng bin thin kh u n t trn
xun trong nhm, nh khi lng ring tng dn, nhit nng chy, si gim
dn
Cc kim loi kim l cht rn, mu trng bc, tr cesi c mu vng.

Chng c khi lng ring nh: liti, natri v kali nh hn nc, mm, c th ct
chng d dng bng dao, ko; nhit nng chy thp do lin kt trong tinh th
yu; dn in cao do vng ha tr ch b chim mt na
Cc kim loi kim tan trong thy ngn ngay nhit thng to thnh
cc hp kim gi l hn hng. Hn hng natri thng c dng lm cht kh
m du
Khi t cc kim loi kim hay cc hp cht ca chng trn ngn la c

mu c trng: liti c mu son, natri c mu vng, kali mu tm, rubi mu tm
hng, cesi mu xanh da tri. C th da vo cc mu ny nhn bit chng
Cc kim loi kim hot ng ha hc nht trong tt c cc kim loi. Kh

nng ny lin quan ch yu n nng lng mng li kim loi v nng lng
ion ha I1 nh ca chng. Chng th hin tnh kh mnh v tng dn u n t
trn xung trong nhm, tr mt s trng hp i vi liti
iu kin thng trong khng kh cc kim loi b oxi ha: liti b oxi ha
chm, natri b oxi ha nhanh, phn ng tng ln kali, cn rubidi v cesi t bc
chy trong khng kh. V l do trn, nn cc kim loi kim phi c bo qun
trong kh quyn tr (agon). Mt lng nh natri, kali c th bo qun trong du
ha
khi t chy trong khng kh, liti to thnh oxit Li2O v nitrua Li3N, natri
to thnh peoxit Na2O2, kali, rubidi v cesi sinh ra supeoxit MO2. iu ny
chng t rng bn nhit ca MO2 v M2O2 ca cc kim loi kim theo cc
phn ng
2MO2 (r) M2O2 (r) + O2 (k)
230
2M2O2 2 M2O (r) + O2 (k)
Tng ln khi bn knh ca ion tng
Ch liti tc dng trc tip vi nito v cacbon to thnh nitrua Li3N v

cacbua Li3C2. phn ng vi nito xy ra ngay nhit thng. Nguyn nhn
chnh ca s khc bit ny ca liti so vi cc kim loi kim khc l do bn knh
ion Li+ nh hn nhiu so vi cc ion M+ ca cc kim loi kim khc, nn to ra
cc hp cht Li3N v Li2C2 c nng lng mng li rt ln thun li cho phn
ng to thnh chng. iu ny c th thy r qua gi tr nhit to thnh chun
H 298,s
0
:
Hp cht Li3N Na3N K3N Rb3N Cs3N
H 298,s
0
, kJ/mol -318 -151 +84 +180 +314
Khi un nng cc kim loi kim vi hidro to thnh cc hidrua ion MH

trong hidro mang in tch m H-
Th kh chun ca cp M+/M ca cc kim loi kim rt m v cc

hidroxit MOH d tan trong nc, nn cc kim loi y d dng khi hidro khi
nc
2M + 2 HOH MOH + H2
Nu dng mt mu nh kim loi kim tc dng vi nc ta thy liti phn

ng m du, natri phn ng nhanh, kali phn ng mnh km theo ngn la, cn
rubidi v cesi n khi tip xc vi nc
Liti c th kh chun b nht so vi cc kim loi kim khc do bn knh

ion Li nh nht, nn kh nng ha ca ion Li+ ln nht. Nu ch da vo th
+
kh th liti phi phn ng vi nc mnh nht, cn rubidi v cesi phn ng

tng t kali. y phi ch n khi lng ring v nhit nng chy ca
chng. Khi cho kim loi kim tc dng vi nc th rubidi v cesi chm trong
nc, cn cc kim loi khc ni ln trn mt nc, nhng liti c khi lng
ring nh nht, ni ln trn mt nc nhiu nht, nn din tch tip xc phn
ng vi nc l t nht. Ngoi ra liti c nhit nng chy cao nht nn nhit
231
lng ta ra do phn ng khng lm nng chy liti, trong khi cc kim loi
kim khc b nng chy khi phn ng vi nc. Mt cht th lng bao gi
cng d phn ng hn th rn
Di tc dng ca nh sng, cc kim loi kim phng ra cc e ha tr. Li

dng tnh cht ny ngi ta dng cesi v rubidi ch to t bo quang in
Do hot ng ha hc mnh ca kim loi kim, nn trong thin nhin ch

gp chng dng hp cht. Natri v kali thuc s cc nguyn t ph bin.
Nhng hp cht thin nhin cha natri, kali l natri clorua c trong nc bin,
cng nh to thnh nhng va ln nhiu ni trn tri t, KCl (xinvin),
NaCl.KCl (xinvinit), KCl.MgCl2.6H2O (cacnalit), Na2CO3 ( trona), KNO3 (dim
tiu)... Liti, rubidi v cesi l nhng nguyn t him, khong vt chnh ca chng
l aluminosilicat,
Liti v natri c iu ch bng phng php in phn clorua nng

chy: i vi liti dng hn hp LiCl v KCl khong 4500C, cn natri dng hn
hp NaCl, BaCl2 v CaCl2 khong 6000C
Kali, rubidi v cesi d bay hi nhn c bng tc dng ca natri, canxi

hoc canxi cacbua CaC2 vi cc clorua nng chy ca chng p sut thp
Cc kim loi kim, nht l natri, sau l kali, liti v cc hp cht ca

chng c s dng rng ri. Hp cht c natri v kali rt cn cho c th ngi.
Natri trong c th dng mui tan ch yu l clorua, photphat v hidrocacbonat.
p sut thm thu ca huyt tng mu c duy tr mc cn thit trc ht
l do natri clorua. Ion kali ng vai tr quan trng trong mt s qu trnh sinh l
v sinh ha
XIII.2. HP CHT
Liti oxit Li2O c th iu ch bng tc dng trc tip cc n cht, cn

cc oxit ca cc kim loi kim khc M2O ch c to thnh bng phng php
gin tip. V d:
Na2O2 + 2 Na 2 Na2O
KO2 + 3 K 2K2O
232
Liti oxit phn ng chm vi nc, cn cc M2O khc phn ng rt mnh

vi nc v ta nhiu nhit:
M2O + H2O 2 MOH
Cc hidroxit MOH l nhng cht rn mu trng, nng chy nhit

tng i thp, ht m mnh, chy ra trong khng kh m, hp th kh
cacbonic thnh cacbonat, tan trong ru v nc, ha tan ca liti hidroxit nh
hn so vi cc hidroxit kim loi kim khc
Hidroxit kim loi kim l nhng bazo mnh nht trong s cc bazo
bit. Chng n mn mnh vi, da, giy v cc cht hu c khc. Natri hidroxit
cn c gi l kim n da l xut pht t tnh cht ny. Khi un cao hn nhit
nng chy, liti hidroxit mt nc to thnh oxit Li2O, cn cc hidro MOH
khc ch bay hi khng b phn hy. trng thi nng chy cc hidroxit MOH
n mn thy tinh, s v khi c mt oxi khng kh n mn c platin. Do khi
thc hin phn ng trng thi nng chy c mt kim phi dng dng c bng
st, niken hoc bc
Hidroxit c s dng rng ri nht l NaOH. Mt lng ln n c

dng lm sch cc sn phm ch bin du m, trong cng nghip x phng,
giy, dt, sn xut si nhn to
Phng php ch yu iu ch natri hidroxit l in phn dung dch nc

ca natri clorua c mng ngn:
2NaCl + 2HOH 2NaOH + Cl2 + H2
i khi cn dng phn ng gia dung dch natri cacbonat v vi ti:
Na2CO3 + Ca(OH)2 CaCO3 + 2NaOH
Kali hidroxit c s dng t hn v gi cao. Phng php iu ch tng

t nh natri hidroxit:
Nh ni trn, tr liti, cc kim loi kim khc phn ng vi oxi to ra

peoxit, supeoxit. Chng u l cc cht rn, ht m mnh, chy ra trong khng
kh, phn ng mnh vi nc gii phng kh oxi. V d:
233
Na2O2 + 2HOH H2O2 + 2NaOH
Hidro peoxit to thnh khng bn trong mi trng kim:
2H2O2 2H2O + O2
Do trong phng th nghim, ngi ta thng dng Na2O2 cho tc dng

vi nc iu ch oxi
Cc peoxit, supeoxit cng gii phng oxi khi tc dng vi kh cacbonic, v d:
2Na2O2 + 2CO2 2Na2CO3 + O2
Phn ng ny thng c dng ti sinh oxi nhng ni c lp
C gi tr nht trong cc peoxit, supeoxit l natri peoxit. N c iu ch

bng cch un nng chy natri trong dng khng kh loi sch kh cacbonic
v hi m:
2Na + O2 Na2O2 ; H0298 = -504,6 kJ
Sn phm thu c c mu vng nht do ln natri supeoxit NaO2. Natri

peoxit l cht oxi ha mnh, nhiu cht hu c bc chy khi tip xc vi n.
Natri peoxit c dng ty trng vi, len, la...
Hu ht cc mui ca kim loi kim d tan trong nc. S mui t tan

trong nc ca liti nhiu hn, v d LiF, Li2CO3 , Li3PO4
Ngi ta thy rng nhng mui ca kim loi kim vi anion ha tr mt kch
thc b c tan tng theo kch thc ca ion M+. V d tan tng theo chiu
LiF NaF KF RbF CsF
Ngc li cc mui ca chng vi anion ln ha tr mt li c ha tan

gim theo kch thc ca ion M+. V d ha tan gim theo chiu
NaClO4 - KclO4 RbClO4 CsClO4
234
CHNG XIV. PHC CHT
XIV.1. NH NGHA
XIV.1.1. Phc cht
Phc cht hay cn gi l hp cht phi tr l hp cht ha hc m phn t

ca n cha ion phc. Trong ion phc tn ti mt nguyn t hay ion trung tm
gi l nhn trung tm, thng l kim loi chuyn tip, bao quanh n l cc
nguyn t, phn t hay ion lin kt vi n gi l cc phi t. S cc phi t ny
vt qu s cn thit ng vi ha tr c in ca nhn trung tm trong cc hp
cht thng thng:
V d phn t phc cht K3[Co(NO2)6] cha ion phc cht [Co(NO2)6]3-.

Ion phc thng c vit trong du ngoc mc vung. Ha tr thng thng
ca coban l hai v ba, nhng trong ion phc ny nhn trung tm Co 3+ lin kt
c ti 6 phi t NO2-
Ion phc c th cha mt nhn trung tm gi l ion phc mt nhn, nu

n cha nhiu hn mt nhn trung tm gi l ion phc nhiu nhn. V d, ion
phc [Co2(NH3)8(OH)2]4+ cha hai nhn trung tm Co3+
Ion phc c th l anion hoc cation (nh hai v d trn xt)
Ion phc cn c tn l cu ni ca phc cht, v ngoi ion phc trong

phn t phc cht cn c cc ion nm ngoi ion phc cht gi l cu ngoi ca
phc cht. V d 3 ion K+ l cu ngoi ca phc cht K3[Co(NO2)6]
Cng tn ti cc phc cht khng c cu ngoi, v d [Co(NH3)3Cl3]
Mt s phn t phc cht cha nhiu hn mt ion phc chng hanh

[Pt(NH3)4][PtCl4] cha hai ion phc [Pt(NH3)4]2+ v [PtCl4]2-
XIV. 1.2. S phi tr ca nhn trung tm
235
S phi tr ca nhn trung tm l s lin kt ca nhn trung tm vi cc

phi t trong ion phc kho st. V d, s phi tr ca nhn trung tm Co3+ trong
cc phc cht xt trn u bng 6
a s nhn trung tm c s phi tr bin i ph thuc vo bn cht ca

phi t, cng thng ph thuc c vo nng , nhit v cu ngoi. V d,
cc nhn trung tm Cu2+, Ni2+, Zn2+ thng c s phi tr bin i, chng hn
Ni2+ c s phi tr bng 6 trong ion phc [Ni(NH3)6]2+, nhng c s phi tr 4
trong ion phc [Ni(CN)4]2- . Mt s nhn trung tm c s phi tr khng i nh
Co3+, Cr3+, Rh3+ , Ir3+, Pt4+, Ir4+. Chng u c s phi tr bng 6
Hin cha c l thuyt no tin on c chnh xc s phi tr ca nhn

trung tm, s phi tr thng gp nht l 6 v 4
XIV.1.3. Dung lng phi tr ca phi t
Dung lng phi tr ca phi t l s lin kt ca mt phi t lin kt

vi nhn trung tm. V d NH3, OH-, Cl-, NO2-, CN-, trong cc phc cht xt
trn u c dung lng phi tr bng mt. Phi t c dung lng phi tr bng
mt gi l phi t n cng. Nhiu phi t c dung lng phi tr ln hn mt
gi l phi t a cng. V d etilendiamin H2N CH2 CH2 NH2, ion oxalat
C2O42- c dung lng phi tr bng hai
Mi phn t etilendiamin v ion oxalat u c hai nguyn t lin kt c

vi nhn trung tm, ngha l gp i so vi cc phi t n cng
Khi phi t a cng lin kt vi nhn trung tm s to thnh vng v phc

cht cha phi t a cng gi l phc cht vng cng. V d cc ion phc vng
cng trn, hai phi t etilendiamin v ion oxalat u to thnh vng nm cnh
Trong ha hc hu c chng ta bit vng nm cnh khng cha lin

kt bi v vng su cnh cha lin kt kp l cc vng bn. Vng bn cnh t
bn v vng ba cnh rt khng bn
XIV.2. THUYT LIN KT HA TR GII THCH LIN KT HA

HC TRONG ION PHC
236
gii thch lin kt ha hc trong ion phc cht hin nay ngi ta dng
3 thuyt: thuyt lin kt ha tr, thuyt trng tinh th v thuyt obitan phn t
Thuyt lin kt ha tr c cc nh ha hc phc cht dng rng ri

trong khong thi gian t nm 1935 n nm 1950. Nhng hin nay trc
nhng thuyt mi v lin kt trong phc cht, thuyt ny hu nh mt gi tr.
Mc du bit nhng thiu st r rng ca thuyt ny, nhiu nh ha hc vn
cn thy n n gin v mt nh tnh, thun tin gii thch v so snh cc kt
qu nghin cu ca mnh
Thuyt trng tinh th dng so snh tnh cht ca cc phc cht rt c

kt qu. N coi lin kt gia nhn trung tm v cc phi tr v lin kt in ha
tr, trong khi thuyt lin kt ha tr tha nhn lin kt ny l cng ha tr
Thuyt obitan phn t kho st trng thi ca e trong phn t ging nh

thuyt obitan phn t xt trng thi ca e trong nguyn t. Thuyt ny ngy cng
c cc nh ha hc ch . Tuy nhin do tnh phc tp ca h nhiu e, nhiu
tm, nn vic p dng thuyt obitan phn t cho phc cht cn hn ch
Trong cc ti liu chng ta cn gp thuyt trng phi t. l thuyt

nghin cu lin kt ha hc trong phc cht trn c s phi hp hai thuyt
trng tinh th v obitan phn t. Trong gio trnh ny s khng trnh by thuyt
ny v c s ca n nm trong thuyt trng tinh th v thuyt obitan phn t
Tt c cc thuyt u xut pht t vic nghin cu phc cht ca cc kim

loi chuyn tip, c bit cc kim loi chuyn tip d, v phc cht l loi hp
cht rt c trng ca chng v c nghin cu k lng hn c
Thuyt lin kt ha tr l thuyt u tin da trn c s c hc lng t

nghin cu lin kt ha hc trong phc cht. Theo thuyt ny lin kt to thnh
trong ion phc l lin kt cho nhn. Phi t l cht cho cp e, cn nhn trung
tm dng cc obitan lai ha nhn cc cp e ny. Lin kt cho nhn l lin
kt cng ha tr v mi lin kt cho nhn ng vi mt v tr phi tr. V d, s
to thnh ion phc [CoF6]3- t ion Co3+ v su phi t F-. Mi phi t F- a ra
mt cp e ha tr lin kt vi nhn trung tm Co3+. Su cp e ca su ion F- s
chim su obitan lai ha sp3d2 ca Co3+. Su obitan ny c nng lng bng
237
nhau, hng ti 6 nh ca hnh tm mt. Cc obitan ha tr ca ion Co 3+ l

3d64s04p04d0. Su cp e ca 6 ion F- chim 6 obitan lai ha sp3d2 ca nhn trung
tm c to thnh t mt obitan 4s, 3 obitan 4p, v hai obitan 4dz2, 4dx2-y2
Phc cht ny to thnh c s tham gia ca cc obitan d ha tr bn ngoi

ca Co3+ (4d) nn c tn l phc cht obitan ngoi. N cn c gi l phc
cht spin cha ghp cp hoc phc cht spin t do hoc phc cht spin cao,
ngha l trong phc cht ny vn gi c s e cha ghp cp ca nhn trung
tm trng thi t do. Do ion phc [CoF6]3- cha e c thn, nn phc cht
cha n c tnh cht thun t
S to thnh ion phc [Co(NH3)6]3+ hi khc so vi s to thnh ion

[CoF6]3-
y c s lai ha d2sp3 ca cc obitan ha tr ca Co3+, ngha l s

dng cc obitan ha tr d bn trong ca nhn trung tm (3d). S lai ha ny c
c khi to ion phc do 4 e c thn 3d6 ca Co3+ phi ghp cp gii phng
ra hai obitan trng nhn cc cp ca cc phi t. Loi phc cht ny cha t
hoc khng cha cc e c thn so vi nhn trung tm trng thi t do, nn c
tn l phc cht spin ghp cp, phc cht spin thp hoc phc cht obitan trong.
Ion [Co(NH3)6]3+ khng cha e c thn, nn phc cht cha n l nghch t
Nguyn nhn to thnh hai loi phc cht trn thuyt lin kt ha tr
khng gii thch c
Ngoi s to lin kt bng cc obitan lai ha, thuyt lin kt ha tr cn

gii thch c s to lin kt gia nhn trung tm v cc phi t. Khi to lin
kt cho nhn, nhn trung tm ch dng hai obitan d z v d x y bn cnh cc
2 2 2
obitan s v p, cn ba obitan dxy, dxz v dyz y cc e hay c mt phn cc e

khng c kh nng tham gia lin kt , nhng c th to thnh lin kt , nu
phi t c obitan tng ng
Thuyt lin kt ha tr gii thch nh tnh n gin s to thnh cc phc

cht bng lin kt cho nhn. Da vo thuyt ny c th gii thch c phc cht
obitan ngoi t bn hn phc cht obitan trong, nn kh nng phn ng ca phc
238
cht obitan ngoi ln hn so vi phc cht obitan trong, c th gii thch c

tnh cht thun t v nghch t ca phc cht
Tuy nhin cn nhiu tnh cht ca phc cht khng gii thch c bng
thuyt ny, nh tnh cht t chi tit, v d, tnh d hng t, cng hng t,
khng gii thch c s bt i xng v cu to ca ion phc m th nghim
quan st thy, khng gii thch c tnh cht quang hc ca phc cht
XIV.3. THUYT TRNG TINH TH
Thuyt trng tinh th gi thit rng lin kt cho nhn gia nhn trung
tm v cc phi t l in ha tr. y l thuyt c pht trin trn c s thuyt
tnh in n gin ca Kossel nm 1916. Nm 1930 hai nh vt l hc l Bethe
v van vleck dng thuyt ny gii thch tnh cht t v mu ca cc mui
tinh th, nn c tn gi l thuyt trng tinh th. Nm 1951 mt s nh ha hc
dng thuyt trng tinh th gii thch ph ca cc phc cht. V thuyt
ny p dng c kt qu, nn chng bao lu c dng rng ri nghin cu
phc cht
Thuyt trng tinh th da vo cc gi thuyt c bn sau:
- Phc cht tn ti c v bn nh vo lc tnh in gia nhn trung tm

v cc phi t
- Nhn trung tm c kho st trn c s cu hnh e ca n, c th l xt

s bin thin nng lng ca 5 obitan d ha tr ca nhn trung tm di tc dng
in trng khng i ca cc phi t l ion m hay phn t lng cc. Cc
phi t c coi l cc in tch im khng c cu trc
- Phc cht c m t bng cc nh lut ca c hc lng t
Ngoi ra cn gi thit rng phc cht c tnh cht i xng xc nh
Cc gi thit th hai v th ba l hon ton mi so vi thuyt tnh in n gin
XIV.4. THUYT OBITAN PHN T GII THCH S TO THNH

LIN KT HA HC TRONG ION PHC
239
Khc vi thuyt trng tinh th, thuyt obitan phn t ch c n cu

hnh e ca phi t. C s ca thuyt ny dng cho phc cht ging nh cho cc
phn t n gin. Ngi ta thng dng phng php gn ng gi l phng
php obitan phn t - t hp tuyn tnh cc obitan nguyn t. N da vo mt s
gi thit gn ng sau. Ch cc e ha tr tham gia to thnh lin kt ha hc, cc
e lp bn trong nh ch gn ht nhn ca cc nguyn t ring bit. Cc obitan
phn t c to thnh bng t hp tuyn tnh cc obitan tham gia lin kt
Xt v d s to thnh ion phc tm mt AL6x+. Nhn trung tm c chn

obitan ha tr tham gia to thnh cc obitan phn t
XIV.5. HNG S IN LI V HNG S BN CA ION PHC
Khi tan trong nc phn t phc cht in li hon ton thnh ion cu
ngoi v ion cu ni (ion phc). Sau ion phc in li yu tng nc ra cc phi
t . i lng c trng cho s in li ca ion phc l hng s in li
240
CHNG XV
TNH CHT CHUNG CA CC KIM LOI CHUYN TIP d
XV.1. C IM CU HNH ELECTRON HA TR CA CC

NGUYN T
Cc nguyn t chuyn tip d gm 4 dy thuc cc chu k 4, 5, 6 v 7
Nguyn t ca cc nguyn t d c c im cu hnh e ha tr nh sau:
- Chng u c hai hoc him hn 1 lp ngoi cng, tr mt trng hp

ca palidi Pd (Z =46) vi cu hnh e ha tr 4d105s0, ngha l n chu k 5
nhng lp e ngoi cng khng c e
- Nng lng ca cc e hai phn lp ngoi cng l (n-1)dxns1-2 gn

nhau, nn ni chung cc e hai phn lp ny u l cc e ha tr
- T tri sang phi trong mt dy ni chung nng lng cc e ns v (n-

1)d u gim v hiu nng lng Ens E(n-1)d tng, nn cc e (n-1)d bn trong tr
nn cng kh tham gia lin kt ha hc cng vi cc e ns
- T trn xung trong mt nhm B ni chung nng lng cc e ns bin

i t, nhng hiu nng lng Ens E(n-1)d gim, nn cc e (n-1)d bn trong tr
nn cng d tham gia lin kt cng vi cc e ns
- Phn lp e bo ha (n-1)d10 v na bo ha (n-1)d5 l cc phn lp bn,

nn mt s trng hp ta thy cc e hai phn lp ny tham gia lin kt ha
hc cng vi cc e ns hn ch hn so vi cc e cc phn lp (n-1)d x khc
XV.2. TNH CHT CHUNG CA CC NGUYN T d
- Chng u l cc kim loi v s e lp ngoi cng t hn 3. T tri sang

phi trong mt dy v t trn xung di trong mt nhm B ni chung tnh cht
kim loi gim dn
241
- Cc nguyn t d th hin nhiu s oxi ha khc nhau, v ngoi cc e ha

tr ns, chng cn c cc e ha tr (n-1)d
- S oxi ha ln nht ca cc nguyn t bng tng s e ns v (n-1)d v

bng s th t nhm cha chng tr cc nguyn t cc nhm IB, IIB v a s
nguyn t cc nhm III B, VIII B
- T tri sang phi trong mt dy bn ca s oxi ha ln nht (bng

tng s e ns v (n-1)d) ca cc nguyn t ni chung gim dn, v hiu nng
lng Ens E(n-1)d tng dn lm cho cc e (n-1)d tr nn cng kh tham gia lin
kt cng vi cc e ns. V d, cc nguyn t cc nhm IV B v V B u cc
dy c s oxi ha ln nht tng ng l +IV v +V bn, trong khi cc nguyn
t cui dy khng pht hin thy s oxi ha ln nht bng tng s e ns v
(n-1)d
- T trn xung di trong nhm B ni chung bn ca s oxi ha ln

nht tng dn, do hiu nng lng Ens E(n-1)d gim dn. bn ca cc s oxi
ha khc nhau lin quan n tnh cht oxi ha kh ca cc hp cht. V d
mangan c s oxi ha ln nht +VII t bn, nhng s oxi ha +II bn trong mi
trng axit, nn hp cht Mn(VII) c tnh oxi ha mnh, d b kh thnh Mn 2+
trong mi trng axit, trong khi hp cht Mn2+ c tnh kh yu trong mi
trng axit
- Cc nguyn t d v c bit cc ion kim loi d c in tch thp d to

phc cht, v cc e ha tr d thun li cho vic to thnh lin kt ha hc trong
phc cht
- Phc cht to thnh bi ion trung tm l nguyn t d dy th hai v ba

thng l phc cht spin thp hoc bn hn phc cht tng ng to thnh bi
ion dy th nht, v cc obitan ha tr 5d (dy ba) v 4d (dy hai), tri trong
khng gian ln hn obitan 3d (dy mt), nn cc cp e trn cc obitan y
nhau km so vi trn obitan 3d lm nng lng cp i e p nh hn. Cng c
th do th tch cc obitan 5d v 4d ln hn 3d m tng tc vi cc phi t
mnh hn lm cho gi tr thng s tch trong phc cht ln hn
242
- a s cc nguyn t d c kh nng to thnh cc hp cht thun t, v

phn lp e (n-1)d c s e cha bo ha, nhiu trng hp vn gi c s e c
thn khi to hp cht
- Nhit nng chy ca cc kim loi nhm II B thp nht trong dy, cn
ca mangan thp hn cc kim loi trc v sau n trong cng dy. iu ny c
lin quan ch yu n cc phn lp e bn bo ha s e (n -1)d10 v na bo ha
3d5
- Nhit nng chy ca cc kim loi chuyn tip ni chung ln hn so

vi cc kim loi khng chuyn tip, v cc kim loi chuyn tip c s obitan
tham gia lin kt kim loi nhiu hn
243
CHNG XVI. CC NGUYN T PHN NHM IB
(Cu, Ag, Au)
Cu Ag Au
in t ha tr 3d10 4s1 4d10 5s1 5d10 6s1
Bn knh kim loi (A0) 1,28 1,44 1,44
Bn knh ion M+ (A0) 0,98 1,13 1,37
Nng lng ion ha I1 (Ev) 7,72 7,57 9,22
i lc in t (eV) 1,2 1,3 2,3
- Nng lng ion ha ca cc kim loi phn nhm IB ln hn nhiu so vi

ca kim loi phn nhm IA do chu nh hng ca s co d v s tng in tch
ht nhn. Do chng l cc kim loi km hot ng, hot ng gim t Cu
n Ag v Au.
- Mc d cu hnh (n -1)d bo ha 10 in t nhng v va mi hon

thnh nn cha n nh (tr Ag), do mt s in t vn tham gia to lin kt.
- Cu: mc oxy ha thng gp l +1, +2, s oxy ha +2 bn hn. Ag: s

oxy ha bn nht +1, bn ca s oxy ha +1 ca Ag c gii thch l do cu
hnh 4d10 c hnh thnh t nguyn t Pd nn kh bn vng. Au: S oxy ha
bn nht l +3
- Cc hp cht ca cc kim loi phn nhm IB thng to lin kt c tnh

cng ha tr nhiu hn do s phn cc ha ion.
XVI.1. N CHT
Tnh cht vt l
Cu: mu , Ag: trng bc, Au: vng c cu trc mng tinh th lp

phng mt tm cht ch nn c khi lng ring ln. Nhit nng chy
244
tng i cao. Chng do, mm, d ko di v dt mng. C tnh dn in v

dn nhit tt hn cc kim loi khc.
Tnh cht ha hc
- L nhng kim loi km hot ng, hot tnh ha hc gim dn trong dy

Cu - Ag - Au.
- Ch c Cu phn ng trc tip vi oxy v cng b oxy ha chm nhit

cao. Khi lu trong khng kh Cu b ph mt lp (CuOH)2CO3 cacbonat
baz ng (tanh ng). Ag v Au khng b oxy ha ngay c khi nung nng. Nu
trong khng kh c H2S th khi lu Ag s b xm v:
2Ag + 2H2S + O2 2Ag2S + 2H2O
- Chng ng sau hydro trong dy in th ( E0 Cu2+/Cu = 0,34V; E0

Ag+/Ag = 0,79V; E0 Au3+/Au = 1,42V) nn khng phn ng vi cc axit khng
c tnh oxy ha. Cu v Ag tan trong HNO3 v H2SO4 c nng, cn Au ch tan
trong nc cng thy v dung dch HCl bo ha Cl2. Trong cc phn ng
Au tan c l nh to thnh anion phc cloro
Au + HNO3 + 4HCl = H[AuCl4] + NO + H2O
Au + Cl2 + HCl = H[AuCl4]
- Cu kim loi c th tan c trong cc axit khng tnh oxy ha nu c

mt ca oxy.
Cu + 2HCl + 1/2O2 = CuCl2 + H2O
2Cu + O2 + H2SO4 = 2CuSO4 + 2H2O
- Au3+, Cu2+ to phc bn vi OH-, NH2... nn n tan c trong cc dung

dch xyanua NH4OH khi c mt oxy.
4Au + O2 + 8NaCN + 2H2O = 4Na[Au(CN)4] + 2NaOH
Phn ng c s dng tch Au ra khi qung c hm lng vng thp

v khng th tch bng phng php trng lc.
245
- Au, Cu d to hp kim vi nhau v hp kim vi nhiu kim loi khc.
Trng thi t nhin - iu ch
Hm lng trong v tri t: Cu: 4,7.10-3%; Ag: 10-5%; Au: 5.10-8%. C 3

nguyn t tn ti c trng thi t do di dng kim loi t sinh. Tuy nhin
phn ln ng nm di dng qung sunfua: khong ch yu chancopyrit
CuFeS2, cuprit Cu2O, Kovelin CuS. Ag t gp di dng t sinh, ch yu tn ti
di dng Ag2S ln trong qung sunfua ca cc kim loi khc.
- ng c th c iu ch bng phng php nhit nhit luyn hoc

thy luyn. Phng php nhit luyn t chancopirit.
2CuFeS2 + 5O2 + 2SiO2 = 2Cu + 2FeSiO3 + 4SO2
Cu nng chy nm di cn st nm trong x ni trn. Phng php

thy luyn da trn s ha tan chn lc cc khong ca Cu trong H2SO4 long
hay trong NH3... tch ng ra di dng mui, sau t dung dch mui thu
c ngi ta iu ch Cu bng phng php in phn.
- Au c iu ch t cc loi qung t sinh bng phng php trng lc.

Ngi ta cng dng phng php thy luyn chuyn Au v dng phc xyanua,
sau in phn hiu dng kim loi hot ng hn y n ra khi mui.
2Na2[Au(CN)2] + Zn = Na2[Zn(CH)4] + 2Au
XVI.2. CC HP CHT C MC OXI HA +1
c tnh chung
- S oxy ha +1 bn i vi Ag cn i vi Cu n ch c lm n nh
trong nhng hp cht c tch s tan rt nh v cc phc cht bn vng hoc
nhng iu kin hon ton kh. Hin tng ny c gii thch l do ion Cu2+
c nng lng hydrat ha ln hn nhiu so vi Cu2+ do khi mt nc Cu2+ tr
nn bn vng hn nhiu. Cc hp cht Cu(+1) thng th hin tnh kh d b
oxy ha ln Cu(+2) hoc b d phn. Cc hp cht ca Ag(+1) c tnh oxy ha
v b kh v Ag kim loi.
Cu+ = Cu + Cu2+
246
- Trong cc hp cht Ag(+1), Cu(+1) cc ion Ag+ v Cu2+ c cu hnh d10

nn cc hp cht ca chng thng khng mu (tr khi anion c mu hoc do
ph chuyn v in tch).
- Ag(+1) c s phi tr 2 hoc 4 vi cu trc mch thng hng hoc t

din, cn Cu(+1) lun c s phi tr 4, cc hp cht ca Cu(I) u c xy
dng nn t cc t din CuX4.
- Vi cc cu hnh 18e cc ion Ag+, Cu+ c kh nng phn cc ln, cc

hp cht ca chng c c tnh cng ha tr cao nn a s hp cht t tan trong
nc.
Cc hp cht
- Cc hydroxit AgOH, CuOH rt km bn chng b phn hy ngay khi

va c iu ch to thnh oxyt t tan MOH M2O + H2O
Cu2O: mu , Ag2O: mu nu en
- Cc halogenua v cc gi halogenua: MX, MCN, MSCN u t tan, cc

sunfua t tan
Trong cng mt dy hp cht tan ca mui gim dn khi bn knh

anion cng tng.
TAgI < TAgBr < TAgCl; TCuI < TCuBr < TCuCl
Cc hp cht ny thng c iu ch bng phn ng trong dung dch

gia cc mui Ag(+1) tan , mui Cu(+2) tan vi dung dch cha anion tng
ng.
AgNO3 + NaCl = AgCl + NaNO3
i vi cc hp cht ca Cu (+1) do s to thnh mui t tan lm n

nh s oxy ha +1.
2Cu2+ + 4I- = 2CuI2
2CuI2 2CuI + I2
247
2Cu2+ + 4CN- = 2Cu(CN)2
2Cu(CN)2 2CuCN + (CN)2
- Cc mui vi oxy axit ca Ag+ tng i bn vng, cc mui d tan ca

Ag(+) l AgNO3, AgClO, AgCH3COO, mui vi cc oxy axit khc t tan. Mui
vi oxy axit ca Cu(+1) rt km bn, trong dung dch nc n phn hy ngay
khi va ha tan.
- Cc mui ca Ag(+1) v Cu(+1) u km bn, chng b phn hy di

tc dng ca nhit hoc nh sng.
2AgX 2Ag + X2
CuCl CuCl2 + Cu
Phc cht ca Ag(+1) v Cu(+1)
Ag(+1) v Cu(+1) to c phc cation v phc anion vi nhiu phi t v

c v hu c. Phc aqu ca Ag(+1) bn trong dung dch nc, cn phc aqu
ca Cu(+1) km bn b ph hy ngay trong dung dch nc v phc aqu km
bn nn cc hp cht thng dng tinh th khan. Phc amin bn hn do
nhiu hp cht t tan ca Ag(+1) v Cu(+1) tan c trong dung dch NH3.
CuCl + 2NH3 = [Cu(NH3)2]Cl
Ag2O + 4NH3 + H2O = 2[Ag(NH3)2]OH
- Phc anion phong ph hn: [Ag(S2O3)2]3-, [AgCl4]3-, [Ag(CN)2]-,

[Cu(CN)4]3-, [Cu(Hal)2]-, phc bn nht vi cc phi t v c l phc
[Ag(S2O3)2]3-, [Cu(CN)4]3-, cc phc khc km bn hn ch to thnh khi rt d
phi t v b ph hy khi pha long.
- V s hnh thnh phc anion vi CN-, X- nn cc mui AgX, AgCN,

CuX, CuCN t tan trong nc li tan c trong thuc th d.
Ag+ + KI = AgI
AgI + KI = K[AgI2]
248
CuCl + HCl = H[CuCl2]
XVI.3.CC HP CHT C MC OXI HA +II
- S oxy ha +2 ch c trng vi Cu.
- i vi Ag cc hp cht s oxy ha +2 c tnh oxy ha rt mnh nn

n oxy ha ngay nc v quay tr v s oxy ha +1. E0Ag2+Ag+ = 2,0V
- Au gn nh khng c s oxy ha +2.
- S phi tr cc i ca Cu (+2) l 6 vi hnh bt din lch. Do cu hnh

in t d9 nn 2 phi t nm trn trc z b y ra xa v trong trng hp gii
hn n s b y tht xa v cu hnh bt din chuyn thnh cu hnh vung
phng.
- Vi cu hnh in t d9 s phi tr 4 c trng hn l s phi tr 6.
- Trong mi trng c H2O cc hp cht Cu(+2) bn vng hn hp cht

cng kiu ca Cu(+1).
Khi ha tan trong nc hoc trong axit s to thnh phc aqu

[Cu(H2O)6]2+ c mu xanh da tri. Phc aqu ca Cu(+2) bn nn cc mui
ng thng kt tinh di dng cc tinh th hydrat khi iu ch t dung dch
nc. Cc mui Cu(2+) d tan, tr CuS, CuCO3, CuC2O4. Khi tan cc mui
ng b thy phn mt phn pH thch hp c th to thnh cc mui baz t
tan (v d: CuCl2.3Cu(OH)2, CuSO4.2Cu(OH)2, Cu(NO3)2.3Cu(OH)2...).
- Cu to nhiu phc cation v anion, phc cation ngoi phc aqu cn

bit [Cu(NH3)4]2+.
Cu(OH)2(r) + 4NH3(dd) + H2O = [Cu(NH3)4(H2O)2](OH)2
Phc anion kh phong ph: phc vi cc phi t v c c bit l:

[Cu(CN)4]2-, [CuX4]2- v c phc vi cc phi t SO42-, CO32-...
Cc hp cht Cu(+2) c nhiu ng dng trong thc t, quan trng nht l

CuSO4.5H2O. Nhiu hp cht ca Cu c dng lm bt mu, lm cht dit
nm mc cho cy ci.
249
XVI.4. CC HP CHT C MC OXI HA +III
- S oxy ha +3 c trng i vi Au. Hp cht c ng dng nhiu

nht l H[AuCl4].H2O nhn c khi ha tan Au trong nc cng thy; AuCl3
to thnh khi Clo ha Au; khi cho kim tc dng vi dung dch AuCl 3 hoc
HAuCl4 s to thnh kt ta hydroxyt vng. Kt ta ny khi sy kh s to thnh
AuOOH v khi un nng lu n 140 - 1500C s chuyn thnh Au2O3, nhit
cao hn n s b phn hy thnh Au v O2.
- Au lng tnh d tan trong kim v axit
NaOH + Au(OH)3 = Na[Au(OH)4]
Au(OH)3 + 4HNO3 = H[Au(NO3)4] + 3H2O
- Au(+3) to phc vi nhiu phi t: [AuX4]-, [Au(CN)4]-, [Au(SO4)2]-...

Tnh axit ca Au(OH) th hin r rng nn phc anion ca n kh bn (v du:
[AuCl4]- c hng s bn 2.1021) iu ch c dng axit hoc dng mui,
chng thng d tan trong nc.
Cc hp cht Au(+3) c tnh cht oxy ha.
V d:
HAuCl4 + 3FeSO4 = Au + Fe2(SO4)3 + FeCl3 + HCl
Phn ng ny c s dng trong phn tch tch Au ra khi nguyn t

khc.
250
CHNG XVII. CC NGUYN T PHN NHM IIB
(Zn, Cd, Hg)
Zn Cd Hg
Cu hnh in t ha tr 3d10 4s2 4d10 5s2 5d10 6s2
Bn knh kim loi (A0) 1,39 1,56 1,60
Bn knh ion E2+ (A0) 0,83 0,99 1,12
Nng lng ion ha I1 (eV) 9,39 8,99 10,44
- C 3 nguyn t u c cu hnh in t ha tr hon ton tng t vi

phn lp v (n - 1)d10 bo ha v hon ton bn vng (v c hon thnh
t cc nguyn t phn nhm IB). Chnh v l do cc nguyn t ny x s
dng nh chng ch c 2 in t ha tr thuc phn lp ns v tnh cht ca cc
n cht v hp cht c nhiu nt ging vi cc nguyn t phn nhm IIA tng
ng: chng cng c s oxy ha +2 bn vng v l s oxy ha duy nht ca Zn,
Cd, cc ion Zn2+, Mg2+ cng khng mu...
- S khc nhau gia 2 phn nhm ch yu c gy ra bi in tch ht

nhn ln hn v bn knh nh hn. Lin kt trong cc hp cht ca Cd, Zn, Hg
c nhiu tnh cht cng ha tr hn, kh nng to phc mnh hn (nht l phc
vi cc phi t c kh nng nhn ).
- Ring thy ngn do cp in t 6s2 c tnh bn c bit nn to thnh

cc hp cht c cha ion Hg22+. Ion ny c to thnh nh lin kt gia cp
in t 6s2 ca nguyn t thy ngn vi orbital 6s trng ca ion Hg2+.
Hg + Hg2+ Hg22+
- Trong cc hp cht cc nguyn t thng c cc s phi tr sau:
Zn: 4 Cd: 6 Hg: 2, 4, 6
251
XVII.1. N CHT
Tnh cht vt l
- Zn, Cd, Hg l nhng kim loi c mu trng bc, t khi nh hn so vi

kim loi tng ng nhm IB v chng kt tinh c cu lc lng c bin dng
c c nh. Do cp in t 6s2 c bn ln nn trng thi n cht ca
thy ngn tn ti c lin kt kim loi v lin kt Vanderwaal gia cc phn t
Hg, do thy ngn c nhit nng chy thp hn hn.
Zn Cd Hg
t0nc (0C) 419 321 -39
t0s (0C) 907 767 357
- p sut hi trn b mt ca Hg rt ln nn n bay hi ngay c nhit

thng, hi Hg rt c nn cn phi y kn l ng Hg v ni thong kh.
- D to hp kim vi nhau v vi cc kim loi khc. Hp kim ca Hg

c gi l hn hng, khi to hn hng cc kim loi tr nn hot ng hn
nhiu. c bit Hg to hn hng c vi cc kim loi kim v NH4, chnh v vy
Hg c dng lm in cc trong qua trnh in phn iu ch NaOH c nng
cao v tinh khit.
Tnh cht ho hc
- Hot tnh ha hc gim dn theo dy Zn, Cd, Hg.
- Zn, Cd ng trc hydro trong dy in th cn thy ngn ng sau

hydro.
E0Zn2+/Zn = - 0,76V; E0Cd2+/Cd = -0,403V; E0Hg2+/Hg = 0,83V
- Zn c tnh cht lng tnh, tan c trong axit v kim
Zn + 2H3O+ + 2H2O = H2 + [Zn(H2O)4] 2-
Zn + 2H2O + 2OH- = H2 + [Zn(OH)4] 2-
252
- Cd hu nh khng tan trong kim, tan trong axit cng km hn so vi

Zn. Hg ch tan trong cc axit c tnh cht oxy ha, nu d axit s to thnh hp
cht Hg(2+) cn nu thiu s to thnh hp cht Hg22+.
Hg + 4HNO3(c, d) = Hg(NO3)2 + NO2 + H2O
6Hg + 8HNO3(long, thiu) = 3Hg2(NO3)2 + 2NO + 4H2O
- C 3 nguyn t phn ng mnh vi nhiu khng kim loi hot ng khi

un nng. c bit Hg phn ng vi S v I2 ngay nhit thng do HgS v
HgI2 rt bn. Cn phn ng vi oxy xy ra chm nhit thng, xy ra kh
nhanh khi nhit khong 300 - 3500C nhng trn 4000C s xy ra theo chiu
nghch.
Hg + O2 HgO
- Khong quan trng: ZnS (sphalerit), Xinoba HgS, Grinockit CdS, chng
thng tn ti trong cc khong a kim. Ring thy ngn cn tn ti trng thi
n cht. Zn, Cd, Hg v cc hp cht ca n u c.
- Zn thng c iu ch bng phng php nhit luyn
2ZnS + 3O2 = 2ZnO + 2SO2
ZnO + C = Zn + CO
Zn thot ra dng hi v c ngng t li.
- T cc qung ngho ngi ta c th iu ch bng phng php thy

luyn, chuyn n thnh ZnSO4 sau in phn.
- Cd c iu ch ch yu bng phng php thy luyn chuyn

thnh CdSO4 sau thu c Cd bng cch in phn hoc dng Zn kh.
- Ngi ta iu ch Hg bng cch t chy Xinova.HgS
HgS + O2 = Hg + SO2
253
Hg c lm sch bng cch ra vi dung dch HNO3 20%. Hg tinh khit

hn c iu ch bng cch ct trong chn khng hoc in phn.
- Zn c s dng m cc vt liu bng st, dng iu ch cc hp

kim, lm in cc trong k ngh pin... Cd c dng trong hp kim ca ng
lm tng bn ca chng lm cc thanh iu chnh trong k ngh in t. Hg
c dng lm in cc m trong k ngh iu ch NaOH, lm xc tc cho
nhiu phn ng hu c.
XVII.2. CC HP CHT C MC OXI HA +II
MO v M(OH)2 c tnh cht lng tnh, tnh axit v baz tng i yu.
Tnh baz tng chm t hp cht ca Zn (+2) sang hp cht ca Cd (+2) v
gim t Cd (+2) sang Hg (+2).
ZnO CdO HgO ZnS CdS HgS Zn(OH) Cd(OH) HgI2

2 2
trng en trng vng en trng trng
- Ring Hg(OH)2 khng c bit v n phn hy ngay khi va to thnh
Hg(NO3)2 + 2KOH = HgO + 2KNO3 + H2O
- Zn(OH)2 c tnh lng tnh in hnh cn Cd(OH)2 tnh lng tnh th

hin km. Zn(OH)2 tan d dng trong axit v kim, Cd(OH)2 tan trong axit
nhng ch tan trong kim m c.
- Cc mui ca Zn2+, Cd2+, Hg2+ hu ht d tan, tr mui ccbonat, oxalat,

photphat, sunfat v HgI2. Do cc ion b hydrat ha mnh nn thng iu ch
c cc mui hydrat: Zn(NO3)2.6H2O, Zn(B2O3)2.6H2O, Cd(NO3)2.4H2O,
Hg(NO3)2.2H2O... Cc mui tan b thy phn mt phn khi ha tan. S thy
phn tng t mui Zn(+2) n Hg(+2).
- Zn(+2), Cd(+2), Hg(+2) to phc vi nhiu phi t, v d: phc

halogeno [EX4]2-, phc amin [E(NH3)4]2+, [E(NH3)6]2+, [E(CN)4]2-.
254
bn ca phc cht tng dn t Zn2+ n Hg2+ nu cng phi t. bn

ca phc cht cng tng nu cc phi t c kh nng nhn tng dn.
V d:
Phc [ZnCl4]2- [CdCl4]2- [HgCl4]2- [ZnI4]2 [CdI4]2- [HgI4]2-
PKbn -1,52 1,7 15,22 -0,5 5,55 29,83
Chnh v vy cc phc vi phi t I-, CN- bn hn v c bit bn cc

phc ca Hg2+.
Do kh nng to phc vi NH3, I-, CN-... nn nhiu hp cht khng tan

trong nc ca Zn2+, Hg2+, Cd2+ li tan c trong cc thuc th c cha cc
phi t .
HgI2 + I- [HgI4]2-
Zn(OH)2 + 4NH3 [Zn(NH3)6](OH)2
c bit HgS do tch s tan qu nh hu nh khng tan trong bt c dung

mi no, n ch b ph hy bi nc cng thy do phn ng oxy ha kh.
3HgS + 6HCl + HNO3 = 3HgCl4 + 2NO + 3S + 4H2O
- Cc hp cht Zn(+2), Cd(+2) hu nh khng th hin tnh oxy ha hoc

kh cn cc hp cht Hg(+2) th hin tnh oxy ha.
HgCl2 + SO2 + H2O = Hg + H2SO4 + HCl
2HgCl2 + SnCl2 = Hg2Cl2 + SnCl4
Cc hp cht Hg22+
c bit mt s dn xut chung ca Hg22+, a s kh tan trong nc (v

d: Hg2O (en); Hg2Cl2 (trng), cc Hg2I2 (vng lc)), ch c mui Hg2(NO3)2 d
tan.
- Cc hp cht ca Hg22+ km bn, chng d b d phn khi un nng:
Hg2I2 = HgI2 + Hg
255
- Nhiu khi s phn hy xy ra rt nhanh v khng cho php iu ch

c cc dn xut bng phn ng trao i:
Hg22+ + S2- = Hg2S
Hg2S HgS + Hg
Hg22+ + CN- = Hg2(CN)2
Hg2(CN)2 Hg(CN)2 + Hg
dn xut bn nht ca Hg22+ l Hg2Cl2 v Hg2SO4, tuy nhin chng cng b phn
hy khi un nng hoc chiu sng mnh
XVII.3. HP CHT THY NGN C S OXI HA +I
Hp cht Hg (I) thng dng l Hg2(NO3)2. l cht tinh th mu trng,

d tan trong nc phn li thnh ion Hg22+:
Hg2(NO3)2 Hg22+ + 2NO3-
Thy ngn (I) nitrat c iu ch bng phn ng gia axit nitric long v
thy ngn d:
6Hg + 8 HNO3 3Hg2(NO3)2 + 2NO + 4H2O
N l hp cht u thng dng iu ch cc hp cht khc ca Hg (I).

V d:
Hg2(NO3)2 + 2NaCl Hg2Cl2 (trng) + 2 NaNO3
Khi tc dng dung dch Hg2(NO3)2 vi kim mnh khng thu c

hidroxit Hg2(OH)2 m c kt ta en Hg2O:
Hg2(NO3)2 + 2NaOH Hg2O + 2 NaNO3 + H2O
Tuy nhin Hg2O phn hy dn thnh cc kt ta HgO vng v Hg en:
Hg2O HgO + Hg
256
Phn ng tng ln mnh khi c mt kim d, un nng hoc chiu sng

mnh
Phn ng gia Hg22+ v S2- hoc CN- cng khng thu c mui Hg (I)
tng ng m c mui Hg (II) v Hg;
Hg22+ + S2- HgS (en) + Hg
Hg22+ + 2CN- Hg(CN)2 + Hg
Hg(CN)2 + 2CN-(d) [Hg(CN)4]2-
C th gii thch s xy ra cc phn ng da vo cn bng sau:
Hg22+ Hg2+ + Hg ;
[ Hg 2 ]
K = 6.10-3
[ Hg 22 ]
Hng s cn bng K < 1, ngha l iu kin chun phn ng theo chiu

nghch, do ta c th iu ch hp cht Hg22+ bng phn ng nghch. Tuy
nhin v cc phn ng trn to ra HgS rt t tan v Hg(CN)2 in li rt yu lm
nng Hg2+ gim mnh v cn bng chuyn dch theo chiu thun
Cc hp cht Hg(I) va th hin tnh cht oxi ha va th hin tnh cht kh. V
d:
Hg2Cl2 + SnCl2 2Hg + SnCl4
Hg2Cl2 + Cl2 2HgCl2
257
CHNG XVIII. CC NGUYN T PHN NHM IIIB
(Sc, Y, La, Ac)
- Trong bng cho thy tnh cht ca nguyn t cc nguyn t phn nhm
IIIA v IIIB
B Al Sc Y La Ac Ga In Tl
CH e ha tr ns2 np1 (n - 1)d1 ns2 ns2 np1
RM (A0) 0,91 1,43 1,64 1,81 1,87 2,03 1,39 1,66 1,71
RM3+ (A0) 0,21 0,57 0,83 0,97 1,04 1,11 0,62 0,92 1,05
I1 (eV) 8,29 5,98 6,56 6,22 5,58 5,1 5,99 5,78 6,11
- Mc d cu hnh in t ca cc nguyn t phn nhm IIIA v IIIB

khng ging nhau nhng s in t trn phn lp (n - 1)d ca cc nguyn t
phn nhm IIIB mi ch c 1 electron, do n nh hng cha nhiu n tnh
cht ca nguyn t. Chnh v vy nn nhiu tnh cht thay i kh u n t cc
nguyn t chu k 2, 3 ca nhm IIIA qua cc nguyn t thuc phn nhm IIIB
ca cc chu k 4, 5, 6. Nhiu khi s thay i cn u n hn s thay i
trong bn thn phn nhm IIIA v cc nguyn t Ga, In, Tl ng ngay sau 10
nguyn t d v chu nh hng ca s "co d" nhiu hn.
- Trong thc t nhn vo gi tr ca nng lng ion ha chng ta thy r

rng tnh kim loi tng kh u n trong phn nhm IIIB. Sc c tnh cht rt
ging Al, l mt kim loi lng tnh.
- Cu hnh (n - 1)d1 cha bn vng in t d ny rt d tham gia lin kt

hoc mt i v cc nguyn t hu nh ch th hin s oxy ha +3. Cc ion E3+
cng c cu hnh 8 in t bn vng nn tnh cht ca cc hp cht ca chng
ging vi cc hp cht ca kim loi s v p.
XVIII.1. SCANDI, YTRI, LANTAN V ACTINI
258
Tnh cht ha hc
- Scani, ytri, lantan v catini l nhng nguyn t d u cc dy nguyn t

chuyn tip d, nguyn t ca chng u c 3 e ha tr (n-1)d1ns2. S oxi ha c
trng ca chng trong cc hp cht l +III
- trng thi n cht Sc, Y, La l cc kim loi rt hot ng, ch km

cc kim loi kim v kim th. Hot tnh tng dn t Sc n La.
E0Sc3+/Sc = -2,08V E0La3+/La = -2,52V
- Trong khng kh Sc, Y khng b bin i cn La b ph mt lp mng

hydroxyt.
- To hp kim vi nhiu kim loi khi nu chy.
Th kh chun ca cp M3+/M rt m, nn chng d tan trong cc axit. V

d:
2La + 3H2SO4 (long) La2(SO4)3 + 3H2
- Sc khng phn ng vi nc cn La phn ng vi nc gii phng ra

hydro.
2La + 6H2O = 2La(OH)3 + 3H2
Cc oxit M2O3 c to thnh bng phn ng trc tip cc kim loi vi

oxi hoc bng cch nhit phn mui nitrat, cacbonat hay oxalat. V d:
4La(NO3)3 2La2O3 + 12NO2 + 3O2
Cc oxit l nhng cht rn, mu trng, kh nng chy, thc t khng tan
trong nc, nhng d kt hp vi nc to thnh hidroxit t tan. V d:
La2O3 + 3H2O 2La(OH)3
Kh nng phn ng vi nc ca cc oxit tng dn t trn xung trong

nhm
259
Theo chiu Sc(OH)3 - Y(OH)3 - La(OH)3 - Ac(OH)3 tan trong nc

v tnh tnh cht bazo tng dn. Scandi hidroxit c tnh cht lng tnh yu, cn
lantan hidroxit l bazo kh mnh. Tt c hidroxit u d tan trong cc axit,
scandi tan c trong kim:
Sc(OH)3 + 3HNO3 Sc(NO3)3 + 3 H2O
Sc(OH)3 + 3NaOH Na3[Sc(OH)6]
Cc ion M3+ khng mu, cc mui thng dng cha M3+ ha tan trong
nc l nitrat, clorua, axetat; cn florua, cacbonat, photphat, oxalat tan t trong
nc
Tng ng vi tnh cht bazo tng dn ca cc hidroxit theo Sc(OH)3

Ac(OH)3, s thy phn ca cc mui gim dn theo chiu trn
- Trong t nhin cc nguyn t phn nhm IIIB khng tn ti di dng

cc khong ring m phn tn trong cc kim loi qung khc. Chnh v vy
chng l nhng nguyn t kh iu ch, ngun nguyn liu l cc phn thu c
khi ch ha cc hp cht ca cc nguyn t khc.
- iu ch cc kim loi ngi ta chuyn Sc, Y, La v dng oxyt hoc

clorua sau dng Ca kh hoc em in phn cc mui nng chy.
XVIII.2. H LANTAN
H lantan cn c tn gi l cc lantanoit. Tn gi ny c lin quan cht

ch vi tn nguyn t lantan, v tnh cht ca chng rt ging vi tnh cht ca
lantan. H lantan gm 14 nguyn t: Ceri, Prazeodim, Neodim, Prometi, Samari,
Eropi, Galodini, Tecbi, Dyprozi, Honmi, Ecbi, Tuli, Ytecbi, Lutexi
Cc nguyn t h lantan thuc dy th nht cc nguyn t chuyn tip f

(chu k 6), s in e vo nguyn t ang c thc hin phn lp 4f. Nh vy
v nguyn t ca chng ch khc nhau v s e 4f, ngha l lp e th ba k t
ngoi vo nhn, tr galodini v lutexi c s chuyn mt e t 4f ra 5d. y l
nguyn nhn c bn quyt nh s ging nhau v tnh cht ca cc lantanoit, v
260
cc e lp th ba rt kh tham gia lin kt cng vi cc e lp ngoi. Chnh do

s ging nhau ny m trong thin nhin chng thng i km vi nhau trong cc
qung v vic tch chng di dng tinh khit rt kh khn, lm tng gi thnh
v hn ch ng dng ca chng. Trong cc qung lantanoit cng thng c cha
scandi, ytri, lantan, v th lantanoit cng vi ba nguyn t ny thng c gi
l cc nguyn t t him
Tuy nhin khi i t u dy n cui dy trong h cng c s bin thin

no v tnh cht do s tng in tch ht nhn v s e. Li dng s khc nhau
ny tch ring cc nguyn t t him ra khi nhau
Ngun ch yu iu ch cc latanoit l qung monaxit, l ct mu

nu sm c thnh phn bin i. N gm ch yu l lantanoit orthophotphat,
nhng c th cha n 30% thori. Lantan, ceri, prazeodim v neodim thng
chim ti 90% hm lng tng cng cc lantanoit trong cc khong, phn cn
li l ytri v cc nguyn t nng hn
Cc lantanoit c tch ra khi a s cc nguyn t khc bng cch kt

ta florua hoc oxalat t dung dch nitrat. S tch ring cc nguyn t c thc
hin bng phng php trao i ion
Tt c cc lantanoit u l kim loi mu trng bc, kh nng chy. Hot

ng ha hc ca chng ch thua kim loi kim v kim th. T tri sang phi
ni chung tnh kim loi gim dn, tuy s bin thin ny rt chm
Trong khng kh cc kim loi lantanoit b m nhanh chng, khi t chy

to ra oxit M2O3, tr CeO2. Chng cng d dng phn ng vi cc phi kim khc
khi nng. Vi hidro chng ch bt u phn ng 300 4000C to thnh cc
hidrua MH2 v MH3. Phn ln cc hidrua ny c tnh cht ca hidrua ion
Cc hp cht ca lantanoit c c tnh ion gn ging cc hp cht ca cc

kim loi kim th. Cc oxit M2O3 l nhng cht rn kh nng chy, trong khng
kh chng hp th kh CO2 v hi nc chuyn thnh cacbonat v hidroxit
Cc hidroxit M(OH)3 hu nh khng tan trong nc v c to thnh

bng cc phn ng trao i. Do bn knh ion M3+ gim dn t tri sang phi
261
trong h nn ni chung theo chiu t Ce(OH)3 n Lu(OH)3 ha tan, tnh cht

bazo v bn nhit gim dn
Ceri to thnh oxit rt bn CeO2. l cht rn mu vng sng, c to

thnh khi un ceri hay cc hp cht ca n trong khng kh. Hidroxit tng ng
ca n l Ce(OH)4, l cht kt ta keo mu vng c to thnh bng phn
ng trao i. N c tnh cht lng tnh yu. Hp cht Ce (IV) l cht oxi ha
mnh trong mi trng axit, tri li hp cht Ce (III) trong mi trng kim d
b oxi ha thnh Ce (IV) ngay c bng oxi khng kh
Nhiu lantanoit v hp cht ca chng c ng dng trong cc lnh vc

khoa hc v k thut khc nhau. Trong luyn kim, chng c dng ch yu
di dng mismetal (hp kim ca cc lantanoit vi hm lng chnh l ceri v
lantan). Cht lng ca thp khng g, thp ct gt nhanh, thp chu nng v
gang s tng ln khi cha mt lng nh kim loi t him. Hp kim niken-
crom c thm 0,35 % mismetal s c thi gian s dng tng gp mi ln
10000C. Vic thm lantanoit vo hp kim nhm v magie s lm tng bn
ca n nhit cao
Cc kim loi t him cn c s dng trong k thut chn khng v

chng c kh nng kt hp nhiu cht kh
XVIII. H ACTINI
H actini cn c tn gi l cc actinoit. Tn gi ny lin quan n tn

nguyn t actini ng ngay trc h trong bng tun hon, v chng c nhiu
tnh cht tng t actini. H actini gm 14 nguyn t: Thori, Protactini, Uran,
Neptuni, Plutoni, Amerixi, Curi, Beckeli, Califoni, Ensteni, Fecmi, Mendelevi,
Nobeli, Lorenxi
Ging nh trong trng hp lantanoit, cc nguyn t actinoit cc e ang

in vo phn lp 5f, lp th ba k t ngoi vo. Ni chung cu to ca hai lp
e ngoi cng cc nguyn t ca chng ging nhau, nn tnh cht ha hc ca
chng gn ging nhau.
Tt c cc actinoit u c tnh phng x. Trong thin nhin gp cc qung

thori, protactini v uran v cc ng v ca chng c chu k bn r ln. Cng
262
gp mt lng nh neptuni trong thin nhin. Cc nguyn t cn li c iu

ch nhn to
Thori trong v tri t khong 10-3 %. Khong vt ca n lun i cng

vi cc nguyn t t him, uran v mt s kim loi khc. Khong vt quan
trng nht ca thori cho cng nghip l monoaxit
trng thi n cht, thori l kim loi do, kh nng chy, mu trng
bc. S oxi ha c trng nht l + IV, oxit quan trng l ThO2
Thori c s dng trong k thut ht nhn. Di tc dng ca noowtron,

thori thin nhin chuyn thnh uran, c dng cho nhin liu ht nhn. Thori
cn c dng lm cu t hp kim ha
Tnh cht quan trng nht ca uran l ht nhn ca n c kh nng v ra

khi hp th notron, khi mt lng ln nng lng ta ra. Tnh cht ny c
s dng trong l phn ng ht nhn, lm ngun nng lng cng nh c s hot
ng ca bom nguyn t
Uran to c kh nhiu hp cht. Hp cht c trng nht cha uran s

oxi ha VI. V d UO3 , H2UO4, H2U2O7
Cc actinoit u to c hidroxit M(OH)3 c tnh cht bazo v mui ca

chng c ha tan tng t cc mui tng t ca lantanoit
XVIII.4. MT S HP CHT
Cc hp cht c mc oxy ha +III
- Sc(OH)3 c tnh cht lng tnh tng t Al(OH)3:
Sc(OH)3 tan c trong axit v tan c khi cho phn ng vi dung dch
m c hay khi nng chy
Na3[Sc(OH)6] Sc(OH)3 ScCl3
Nu trong kim nng chy n s to thnh dng meta scandinat NaScO2.
263
- Cc mui M(NO3)3, M2(SO4)3, MCl3 d tan trong nc, cc mui

M2(CO3)3, MF3, M2(C2O4)3 t tan. Khi tan trong nc cc M3+ b hydrat ha v
to thnh cc phc aqu [Sc(H2O)6]5+, [Y(H2O)9]3+, [La(H2O)9)3+.
- Khi c mt cc mui ca kim loi kim cc mui E(+5) thng to

thnh cc mui phc:
MIn[MXn+3] (n = 1, 2, 3)
MI3[ML3] (L = SO42-, CO42-, C2O42-)
MI[ML2] (L = SO42-, CrO42-)
MI4[M(NO3)5]
Cc phc ny km bn, ch tn ti trong dung dch c nng phi t rt

d hoc kt tinh trng thi rn, khi ha tan trong nc chng b ph hy v
phn ly hon ton. Chng ging mui kp hn l phc cht. Phc bn nht trong
s l [ScF5]3-.
264
CHNG XIX. CC NGUYN T PHN NHM IVB
(Ti, Zr, Hf, Ku)
Ti Zr Hf
in tch ht nhn 22 40 72
in t ha tr 3d2 4s2 4d2 5s2 5d2 6s2
Bn knh kim loi (A0) 1,46 1,6 1,59
Bn knh quy c ca ion E4+ 0,64 0,82 0,82
Nng lng ion ha I1 (eV) 6,82 6,84 7,5
- Th ion ha tng dn, tnh kim loi gim dn. Trong dy Ti, Zr, Hf th
bn knh nguyn t v bn knh ion ca Zr v Hf rt gn nhau nn tnh cht
ging nhau hn so vi Ti.
- Cc nguyn t u c s oxy ha +4 bn. Ring Ti thuc dy 3d nn cn

c cc s oxy ha +2 v +3, tuy nhin cc s oxy ha ny km bn.
- Lin kt trong cc hp cht M (+4) ch yu c tnh cht cng ha tr, cc

ion n gin E4+ khng tn ti.
- Cc hp cht Ti (+2), Ti (+3) c nhiu tnh cht ion hn nn cc ion

Ti2+, Ti3+ c th tn ti trong dung dch di dng cc ion solvat ha.
- Khong c bn ca Ti: TiO2 (di dng khong Rutin, brukit, anata):

Ilmenit FeTiO3; peropkit CaTiO3.
- Zr c trong khong badelit ZrO2, khong Zircon ZrSiO4. Hafni thng

lun lun i km vi Zr trong cc khong ca Zr (thng c t 0,5 n 4% hm
lng ca Zr).
XIX.1. N CHT
265
- Titan l kim loi trng bc, c nhit nng chy cao (t0nc = 16680C)
nh hn so vi nhiu kim loi (d = 4,5 g/cm3 trong khi t khi ca st l d =
7,9 g/cm3) nhng c tnh bn c bit tng i vi s n mn.
- Khng b r ngoi khng kh do to thnh lp mng oxyt TiO2 che ch.

Tuy nhin khi t nng n phn ng vi nhiu phi kim (Halogen, cacbon,
nit...) to thnh cc hp cht ca Ti (+4) v cc hp cht kiu kim loi, cc
dung dch rn.
Ti + Cl2 TiCl4
- Titan c th oxy ha kh thp hn nhiu so vi hydro
E0Ti2+/Ti = -1,63V E0Ti3+/Ti = -1,26V
nhng n ch tan c trong HCl c, nng, ch khng tan trong cc axit long
2Ti + 6H3O+ + 3H2O = 2[Ti(H2O)6]3+ + 3H2
- Trong cc axit c tnh oxy ha nh HNO3, H2SO4 nhit thp n b

th ng. Nhng d tan trong HF hoc trong hn hp HNO3 + HF, nc cng
thy, H2SO4 c nng.
Ti + 6HF = H2[TiF3] + 2H2
3Ti + 4HNO3 + 18HF = 3H3[TiF6] + 4NO + 8H2O
- Titan bn vi cc dung dch clorua, sunfat, nc bin...
iu ch
- Chuyn TiO2 thnh TiCl4 bng phn ng:
TiO2 + 2C + 2Cl2 TiCl4 + 2CO
T TiCl4 iu ch titan kim loi bng cch kh vi Hg hoc Na
TiCl4 + 4Na 4NaCl + Ti
Zr v Hf c tnh cht rt ging nhau v c nhiu nt ging titan.
266
Zr v Hf kim loi cng c tnh cht chng n mn cao khng tan trong
axit v kim long.
Trong cng nghip titan, ziriconi v hafini c iu ch bng cch dng

magie hay natri kh tetraclorua nhit cao trong kh quyn tr. V d t
qung titan trc tin thng chuyn thnh dioxxit TiO2 sau thnh tetraclorua
TiCl4 v cui cng thnh titan:
TiO2 + 2Cl2 + 2C TiCl4 + 2CO ( t0 = 8000C)
TiCl4 + 2Mg Ti + 2MgCl2 ( t0 = 8000C, mi trng Ar)
ng dng ca titan v ziriconi l trong luyn kim ch to cc hp kim nh,

bn vi cc tc dng ha hc v mi trng n mn, nht l nc bin. V d
hp kim titan nhm vanadi nh, bn, dng cho ngnh hng khng v tr.
Ferotitan dng trong luyn thp c bit. Ziriconi dng tch oxi, nito, lu
hunh trong sn xut thp. N cng l cu t hp kim ha mt s loi thp thit
gip, thp khng g v thp chu nhit
ng dng ca hafini cn rt hn ch, n c dng ch yu cng vi ziriconi

trong k thut ht nhn
XIX.2. HP CHT
1, Mt s hp cht ca Titan
Cc hp cht kim loi v hp cht kiu kim loi
Titan to thnh hyrua khi phn ng vi hyr. Hyrua ca n c tnh

cht trung gian gia cc hyrua kiu mui vi cc dung dch rn, thnh phn gn
tng ng vi cng thc TiH2. Khi phn hy n s to thnh kim loi dng
bt.
Titan to thnh dung dch rn vi C, O, N, Si ...
V d :TiO, TiN, c cu trc NaCl c s dng lm vt liu cho cc l phn

ng
267
Khi cho Titan phn ng vi oxy n cng to thnh cc dung dch rn kim
loi v cc hp cht kim loi
Ti + O2 TiO Ti5O Ti3O Ti2O3 TiO2
Khi hm lng oxy tng ln t l gia lin kt kim loi v lin kt cng
ha tr gim dn v cui cng s to thnh TiO2 vi lin kt cng ha tr.
Cc hp cht Ti(+4)
TiO2 l cht rn mu trng, khng tan trong nc, khng tan trong axit
long v kim long. Khi un nng lu n tan chm trong axit. Khi un vi
kim nng chy n cng tan. Axit tng ng l axit titanic c thnh phn khng
xc nh TiO2.xH2O. Dng mi iu ch d tan trong axit v kim (dng ) cn
nu lu n chuyn sang dng kh tan trong c axit v kim. Hin tng ny
gn lin vi s chuyn dng cu trc plyme vi cc cu ni OH trong dng
sang cu trc polyme vi cu ni O trong dng .
- Khi ha tan TiO2 hoc axit ngi ta thng dng HF hoc H2SO4 m
c.
Khi tan trong cc axit, Ti to thnh cc mui titanyl TiO+2
Ti + H2SO4 + H2O TiOSO4 + H2
Cc titanyl cng c to thnh khi thy phn khng hon ton cc hp

cht bc 2 ca Ti(+4).
Khi nu chy vi kim, ty thuc vo lng MOH s to thnh MI2TiO3,

MI4TiO4, MIITiO3, MII2TiO4.
Cc titanat kim loi kim d tan trong nc, khi tan s b thy phn hon
ton.
- Cc halogenua titan (TiX4): tr TiF4 c mt phn lin kt ion nn c cu

trc mch to thnh t cc bt din TiF6. Cc halogenua cn li c mng li
tinh th phn t vi cc phn t t din TiX4.
268
Phn t c lm bn do lin kt ca cp in t ca X vi vn o d
trng ca nguyn t Titan.
Quan trng nht l TiCl4 l mt cht lng (t0nc = -230C) rt ht nc, bc

khi mnh trong khng kh m to thnh axit titanc.
- Ph hp vi tnh axit, phc anion c trng cho Ti(+4). Quan trng nht
l cc phc halogeno [TiX6]2-, [Ti(SO4)3]2-, [TiO(C2O4)2]2- trong [TiF6]2- l
phc bn nht, chnh s hnh thnh phc cht ny l nguyn nhn lm cho cc
hp cht kh tan ca titan tr nn d tan khi c mt ca HF. Ti(+4) cn to
phc peroxyt c mu da cam khi c mt ca H2O2
TiOSO4 + H2O2 + H2SO4 = H2[TiO (H2O2)(SO4)2]
Phn ng ng ny thng c s dng phn tch Ti(+4) c nng

nh bng phng php o quang.
Cc hp cht Ti(+3), Ti(+2)
Cc hp cht Ti(+3) c to thnh khi kh cc hp cht Ti(+4) trong

dung dch axit bng cc kim loi hot ng.
2TiOCl2 + Zn + HCl 2TiCl3 + ZnCl2 + H2O
Trong dung dch nc, ion Ti3+ tn ti di dng phc aqu [Ti(H2O)6]3+
c mu tm. Cc phc cht ca Ti(+3) cng thng c mu tm.
- Cc hp cht Ti2O3, TI(OH)3 l cc cht rn khng tan trong nc v c

bn cht baz. Cc mui TiCl3, Ti2(SO4)3 tan trong nc, cc mui u c tnh
kh, chng b oxy ha t t trong khng kh.
2TiCl3 + 2HCl + 1/2O2 2TiCl4 + H2O
Cc hp cht Ti(+2) c to thnh khi kh mnh cc hp cht Ti(+4)

chng c tnh kh rt mnh, b oxy ha ngay c bng nc.
Ti(OH)2 + H2O = Ti(OH)3 + H2
2, Mt s hp cht ca Zr v Hf
269
Cc hp cht ca Zr v Hf s oxy ha +3 rt km bn v cn t c
nghin cu.
Cc hp cht Zr(+4), Hf(+4) bn, chng cng to thnh cc oxyt EO2,

Halogenua EX4 cc phc halogenua, to thnh cc ion EO2+. Tnh baz ca
ZrO2 cao hn ca TiO2. Trong cc hp cht Zr v Hf thng c s phi tr 7 v
8.
V d: ZrOCl2.8H2O, HfOCl2.8H2O; ZrF73-, HfF73-, ZrF84-.... Cc hp cht

c s dng nhiu nht l EO2 v EO.
Cc MO2 khng tan trong nc v cc axit long, phn ng rt chm vi

axit HF si v H2SO4 c nng:
ZrO2 + 4NaOH Na4ZrO4 + 2H2O
HfF4 khng tan trong nc, ZrF4 tan t v b thy phn, cc tetrahalogenua
khc b thy phn mnh trong dung dch to ra cc hp cht c thnh phn khc
nhau ty thuc vo nng v nhit . Sn phm ca s thy phn l kt ta
trng hidrat oxit xMO2.yH2O. Sn phm trung gian ca s thy phn thng
cha cc gc titanyl (TiO2+), ziriconyl (ZrO2+) v (HfO2+):
M4+ + H2O MO2+ + 2H+
Qu trnh hp th kh hidro ca titan, ziriconi v hafini l thun nghch

ph thuc p sut ca hidro v nhit , khi to thnh hidrua kim loi v cc
dung dch rn. Hidrua bn nht ca chng l MH2. Chng tng t kim loi
nhng khc kim loi l gin. S c mt ca hidrua trong kim loi lm chng tr
nn gin
Titan, ziriconi v hafini phn ng mnh vi nito nhit cao to thnh

cc dung dch rn v nitrua, ch yu l MN. Cc nitrua l cht tng t kim loi,
chng kh nng chy v rt rn. TiN rn gn bng kim cng. Cc nitrua dn
in, kh tr v phng din ha hc
nhit cao cc kim loi nhm IVB phn ng vi cacbon to thnh

cacbua MC. l nhng cht tng t kim loi, rt rn, kh nng chy, dn
in, d to vi kim loi v cacbua khc thnh hp kim rt rn v kh nng
270
chy. Cc MO kh tr nhit thng, nhit cao chng c tnh cht gn

kim loi tng ng, nh phn ng vi halogen, oxi, lu hunh, nito, axit to
thnh cc sn phm ging nh khi kim loi tc dng
ZrC c rn cao c dng lm vt liu mi mn v dao ct thy tinh

hay kim cng
Titan, ziriconi v hafini cng to vi photpho, silic v bo nhng hp cht tng

t cacbua
271
CHNG XX. CC NGUYN T PHN NHM VB
(V, Nb, Ta)
V Nb Ta
Cu hnh electron ha tr 3d3 4s2 4d4 4s1 5d3 6s2
Bn knh nguyn t (A0) 1,34 1,45 1,46
Bn knh ion quy c M+5 (A0) 0,4 0,66 0,66
Nng lng ion ha I1 (eV) 6,74 6,88 7,89
- Do lp ngoi cng c cha t 1 n 2 electron, mt khc do phn lp (n

- 1)d c cha electron nn cc nguyn t V, Nb v Ta c tnh cht c tnh kim
loi tri hn hn so vi cc nguyn t tng ng phn nhm VA. T V n
Ta hot tnh ha hc gim dn.
- Do nh hng ca s co d v co f nn Nb v Ta c bn knh rt gn nhau

v tnh cht ca chng rt ging nhau.
- S oxy ha bn nht l +5 v bn ca s oxy ha ny tng t V n

Nb, Ta.
- Cc hp cht ca V(+2) c tnh baz nn tn ti cation V2+. Cc hp

cht s oxy ha cao c bn cht lng tnh nhng khng to thnh cc cation
n gin M+5, M+4 m to thnh cc anion phc tp MO43-, MO3- hoc cc cation
MO2+, MO2+.
XX.1. N CHT
Tnh cht
- V, Nb, Ta l cc kim loi mu trng bc, c bn c hc cao, khi kim

loi c ln tp cht chng tr nn dn do to thnh hp cht thnh phn thay i.
272
- nhit thng chng khng phn ng vi nhiu cht (oxy, nc,

dung dch mui...).
- Khi un nng chng phn ng vi oxy (to thnh M2O3), vi cc

halogen (to VF5, VCl4, VBr3, VI3), vi S, H2, C... Khi dng bt chng phn
ng c vi hi nc nhit cao gii phng ra hydro. Vanadi c kh nng
phn ng mnh hn so vi Nb v Ta. V d: ngay nhit thng V ha
tan trong HF (to VF3), khi un nng tan trong HNO3 (to VO2NO3), trong nc
cng thy (to VO2Cl), trong H2SO4 c (to VOSO4).
- Nb v Ta phn ng vi HF rt chm v ch tan trong hn hp HF +

HNO3
3M + 5HNO3 + 21HF 3H2[MF7] + 5NO + 10H2O
- Khi c mt cht oxy ha V, Nb v Ta tan trong kim nng chy.
4M + 5O2 + 12KOH 4K3MO4 + 6H2O
Chng l cc nguyn t phn tn, tn ti ch yu trong cc khong ca

F, Al, Ti, Pb... di dng tp cht. V phn tn nn cc hp cht ca V, Nb, Ta
kh iu ch v c gi thnh cao mc d hm lng ca Vanadi trong v tri t
cao hn hm lng ca nhiu nguyn t.
Khong mt na lng V iu ch c l i t qung st c cha

Vanadi. X thu c sau khi luyn thp c cha vanadi dng FeVO4 c
ch ha chuyn thnh vanadat.
4FeVO4 + 4NaCl + O2 4NaVO3 + 2Fe2O3 + 2Cl2
Ch ha dung dch vanadat bng axit s thu c V2O5. Thu c vanadi

kim loi bng cch kh oxyt vi hydro hoc kh VCl3 nng chy bng Mg.
Nb v Ta cng c iu ch bng cch chuyn chng (t b thi ca

cng nghip ch ha cc kim loi chnh) v dng oxyt M2O5 hoc mui phc
K2[MF7] sau kh hoc in phn nng chy cc mui .
273
Hm lng Nb v Ta trong cc qung rt nh nn thu c sn phm

tinh khit phi ch ha kh phc tp v thng phi chit bng cc dung mi
hu c.
XX.2. HP CHT
Hp cht kiu kim loi - Hp cht kim loi
- Khi cho V, Nb, Ta phn ng vi cc khng kim loi (O, N, C, H...)

thng ban u bao gi cng to thnh cc dung dch rn sau mi dn to
thnh hp cht c thnh phn tng i xc nh c cu trc tinh th. V d:
MH, MN, MC, MB, MB2...
- Nitrua, ccbua v cc hp cht ca V, Nb, Ta vi cc khng kim loi

km hot ng khc thng l cc hp cht c tnh chng n mn cao.
- V, Nb, Ta to hp kim vi nhiu kim loi, cc hp kim ny thng c

nhiu tnh cht vt l qu (v d: V lm tng bn mi mn ca thp, Nb cho
thp tnh chng r v tnh bn nhit).
Hp cht E(+2)
- Cc hp cht V(+2) rt km bn chng thng c to thnh khi dng

hydro mi sinh kh cc tp cht V(+3), VO, V(OH)2 l cc hp cht baz,
chng d tan trong axit to mui, trong dung dch nc cc mui ny tn ti
dng cation phc aqu [V(H2O)6]2+ vi cu hnh in t d3 ca ion trung tm
nn c mu tm. Cc mui hydrat ca V(+2) cng c mu ny. Cc hp cht
V(+2) c tnh kh mnh, chng b oxy ha bi nc gii phng ra hydro.
- Nb(+2), Ta(+2) ch tn ti dng cc phc Laste.
Cc hp cht E(+3)
- Hp cht V(+3) to thnh khi kh cc hp cht V(+4) hoc V(+5) bng

dng in.
274
- V2O3, V(OH)3 c tnh cht lng tnh nhng tnh baz tri hn. Khi ha
tan trong axit chng to phc aqu [V(H2O)6]3+ mu xanh l cy hoc
[V(H2O)4Cl2]+, VO+.
- Tnh axit th hin kh nng to thnh cc phc anion: [VX5]3-,

[V(SO4)2]-, [V(CN)5]3-...
- Cc hp cht ca Nb v Ta s oxy ha +3 l cc Claste.
Cc hp cht E(+4)
- S oxy ha +4 bn nht i vi vanai, do cc s oxy ha thp d b

oxy ha thnh V(+4) cn cc hp cht V(+5) cng d b kh thnh V(+4).
Vanai c s phi tr trong cc hp cht V(+4)
- Cc hp cht bc 2 khng c trng lm (ch bit VO2, VF4 v Vcl4).
- Oxyt v hydroxyt (VO(OH)2) khng tan trong nc nhng d tan trong

dung dch kim to hypo vanadat MI2V4O9.7H2O. Trong kim nng chy to
meta v nadat M2IVO3, M2IV2O5.
VO2 tan trong axit to thnh cc dn xut ca phc aqu ca ion vanadyl
2+
VO c mu xanh da tri nht.
VO2 + 2H+ + 4H2O = [VO(H2O)5]2+
- Ion VO2+ thng c gi nguyn trong cc phn ng ha hc do kh

bn nh lin kt gia nguyn t oxy vi vn o d cn trng ca vanadi (V =
0)2+ . Chnh v l do phc cht ca V(+4) chnh l phc ca VO2+ (v d cc
phc: [VO(SO4)4]2-, [VO(SCN)4]2-, VOCl2, VOSO4, VO(OH)2... Cc ha cht
ca VO2+ b thy phn trong nc.
- Cc hp cht VO(+4), Ta(+4) l cc Laste.
Cc hp cht E(+5)
- C 3 nguyn t u to oxyt E2O3 khng tan trong nc. V2O5 ca tnh

cht lng tnh tan c c trong axit v kim Nb2O5, Ta2O5 c tnh axit hn
nn thc t khng tan trong axit m ch tan trong kim nng chy.
275
Khi tan trong kim oxyt vanadi s to thnh cc vanadat. l cc hp

cht c cu trc polyme thnh phn ca hp cht trong dung dch thay i ty
thuc vo nng ca vanadat v pH dung dch. Nhn chung th nng
vanadat tng s to iu kin cho s hnh thnh cc polyvanadat. Khi tng mi
trng kim s to iu kin cho s ph hy cc phc a nhn v chuyn thnh
phc 1 nhn (orto vanadat VO43-).
S thay i thnh phn phc km theo s thay i mu (VO43- hu nh

khng mu cn V2O5.xH2O c mu da cam). Ch c orto vanadat ca cc kim
loi kim d tan cn cc vanadat ca kim loi khc u kh tan.
- Khi ha tan V2O5 trong axit s to thnh ion VO2+ hoc VO3+. Nh vy
khi thay i pH trong dung dch ca cc hp cht V(+5) s xy ra s chuyn
bin nh sau:
VO2+ HVO3 VO3- 4VO42- VO43-
Tng pH
Vanadi cng to cc phc cht hoc cc hp cht trong ion VO2+ hoc
VO3+ ng vai tr ion trung tm. V d: VOHal3, [VOF4]-, [VOF5]2-, [VO2F3]2-,
[VF6]-...
Trong cc hp cht Nb(+5) v Ta(+5) c s phi tr 6, 7, 8 chng to

thnh cc hp cht EHal5, EOHal3 d b thy phn. Cc phc vi phi t l oxy
km c trng cho Nb(+5) v Ta(+5), chng thng to phc vi phi t l
halogen (vd: [EOF5], [EF5]-, [EF7]2-, [EOF5], [EF8]3-...
NG DNG
V, Nb, Ta v cc hp kim ca n l nhng vt liu quan trng ca k

thut hin i do c nhit nng chy cao, bn chng n mn ln, h s dn
n nhit nh.
Cc hp cht ca vanadi c s dng lm cht xc tc cho nhiu qu

trnh ha hc.
276
CHNG XXI. CC NGUYN T PHN NHM VIB
(Cr, Mo, W)
Phn nhm VIB bao gm cc nguyn t Cr, Mo, W l nhng nguyn t d.
Mt s c im ca cc nguyn t
Cr Mo W
S th t 24 42 74
KLNT 52,01 95,95 183,92
Cu hnh electron 3d5 4s1 4d5 4s1 5d5 5s1
Bn knh ngt kim loi A0 1,27 1,39 1,4
Bn knh quy c ca ion M6+ 0,35 0,65 0,65
NL ion ha X0 X+ (eV) 6,764 7,1 7,98
- Trong dy Cr - Mo - W th ion ha tng, ngha l cc lp v electron b

co li, c bit mnh khi chuyn t Mo W. Do s co Lantanit nn W c bn
knh ion v bn kinh nguyn t gn vi Mo. V vy tnh cht ca Mo v W gn
nhau hn so vi Cr.
- Mc oxy ha bn ca Crm l III v VI, ca Mo l V v VI.
- Cng nh cc nguyn t d khc, Cr, Mo, W lng tnh. c trng i

vi chng l cc phc cht cation v anion. Khi mc oxy ha tng th bn ca
cc phc cht anion tng, cn ca cc phc cation gim.
XXI.1. N CHT
iu kin thng cc kim loi Cr, Mo, W cu to t cc tinh th lp phng

tm khi, c mu trng nh xm, nhit nng chy cao. Tnh cht c hc ca
277
chng ph thuc vo tinh khit ca kim loi. Cc tp cht cacbon, nito, oxi,
hidro bin i mnh tnh cht c hc ca chng. V d, crom tinh khit c tnh
do, nhng thng ln tp cht nn gin
Cc kim loi ca nhm ny c hot ng ha hc km v gim dn t trn

xung trong nhm
- Trong dy Cr, Mo, W hot tnh ha hc ca cc kim loi gim r rt:
V d: Cr, ha tan c trong dung dch axit HCl v H2SO4 long cho kh H2 .
Cr + 2HCl CrCl2 + H2
trong khi W ch ha tan trong hn hp HF v HNO3 m c nng:
W + HNO3 + HF H [WF6]
- nhit cao Cr cn tc dng vi hi nc to ra oxit Crm v H2
2Cr + 3H2O Cr2O3 + 3H2
Cr b th ng ha trong axit HNO3 m c ngui v axit H2SO4 m

c ngui.
Do to thnh cc phc cht anion XO42- m Mo, W cn tc dng c vi

kim khi nng chy c mt cht oxy ha.
X + 3NaNO3 + 2NaOH Na2XO4 + 3NaNO2 + H2O
Khi un nng v c bit trng thi nghin nh Cr, Mo v W kh d b

nhiu kim oxy ha.
V d: Cr + Cl2 CrCl3
4Cr + O2 2Cr2O3
2Mo + 3O2 2Mo2O3
278
V d b th ng ha nn Crm c dng rng ri iu ch thp

khng r, Mo c dng ch to cc my mc ha hc, W c dng trong
cng nghip k thut in.
Crm tng i tinh khit c iu ch theo phng php nhit kim

loi.
Cr2O3 + 2Al Al2O3 + 2Cr
Cn Mo v W bng cch dng H2 kh oxyt ca chng.
XXI.2. CC HP CHT
1. Cc hp cht Cr (II), Mo (II), W (II)
i vi Crm II v c bit vi Mo II, W II ngi ta ch bit c mt s

hp cht sau:
CrO mu en, Cr(OH)2 mu vng, CrS en, CrCl2 khng mu...
Cc hp cht ha tr II ca Crm thc t ch th hin tnh baz.
V d: CrO, Cr(OH)2 ch tc dng vi axit
CrO + 2H3O+ + 3H2O [Cr(H2O)6]2+
Cc phc aqu [Cr(H2O)6]2+ c mu xanh bin, cc mui Hydrat ca

Cr(II) cng c mu . V d: CrSO4.7H2O, CrSO4.4H2O.
Phc cht Hexa-aqu [Cr(H2O)6]2+ c cu to bt din. Do d dng to

phc aqu ca ion Cr2+ nn dung dch mui Cr2+ l dung dch ca mui phc
aqu. Chng d b oxy ha bi oxy khng kh.
4[Cr(H2O)6]2+ + O2 + 4H+ 4[Cr(H2O)6]3+ + 2H2O
Nu khng c cht oxy ha th chng b nc phn hy dn.
2CrCl2 + 2H2O 2Cr(OH)Cl2 + H2
2. Cc hp cht Cr (III), Mo(III), W(III)
279
S phi tr ca Cr(III) l 6 ng vi trng thi lai ha sp3 d2

3d 3p 3p
- Cr2O3 l mt cht bt mu lc sm, cn trng thi tinh th c mu

en v nh kim, Cr2O3 kh nng chy (t0nc = 22650C) tr v mt ha hc khng
tan trong nc, axit, kim. Bn cht lng tnh ca n th hin khi nu chy vi
cc hp cht tng ng. V d:
2KOH + Cr2O3 2KCrO2 + H2O
K2S2O7 + Cr2O3 Cr2(SO4)3 + 3K2SO4
- Cr(OH)3 c mu xanh thm, kt ta t dung dch c thnh phn thay i

Cr2O3.xH2O l mt plyme.
H - O Cr .... Cr OH Cr OH Cr OH
H-O OH OH OH
Khi yn Cr2O3.xH2O mt dn nc to ra Cr(OH)3 v mt hot tnh.

Cr(OH)3 va c iu ch (Cr2O3.xH2O) tan nhiu khi c mt axit v kim:
Cr(OH)3 + 3H3O+ [Cr(H2O)6]3+
Cr(OH)3 + 3OH- [Cr(OH)6]3-
Ta c th biu din qu trnh iu ch Cr(OH)3 v chuyn n thnh cc

phc cht anion v cation bng phng trnh tng cng sau y:
Cc phc cht [Cr(H2O)6)3+ c mu tm xanh, mt s hydrat tinh th ca

Cr(III) cng c mu , chng hn: Cr2(SO4)3.18H2O, Cr(NO3)3.9H2O...
Ty thuc vo iu kin nhit , nng , axit m thnh phn ca cc

phc cht aqu, cation thay i, ko theo s bin i mu ca chng t tm sang
lc. [Cr(H2O)6]3+ [Cr(H2O)4Cl2]+
(tm xanh) (lc sm)

280
Trong dung dch cc hp cht Cr(III) t nhiu u b thy phn. C th

xem s hnh thnh phc cht Hydroxo penta aqu [Cr(OH)(H2O)5]2+ l giai on
u ca qu trnh thy phn cc Halogenua, Sulfat, Nitrat Crm (III).
[Cr(H2O)6]3+ + H2O [Cr(OH)(H2O)5]2+ + H3O+
S thy phn lm cho CrCl3, Cr2(SO4)3 mu tm s tr thnh mu lc.

Cr2S3 mu en b thy phn to ra Hydroxit plyme
Cr2S3 + 6H2O 2Cr(OH)3 + 3H2S
Ngoi cc phc cht aqu cn c phc [Cr(NH3)6]3+ phc ny bn trng

thi rn trong dung dch n b phn hy dn.
[Cr(NH3)6]Cl3 + 6H2O Cr(OH)3 + 3NH4Cl + 3NH4OH
V vy iu ch phc amiatcat ngi ta iu ch trong NH3 lng.
Sau y l mt s phn ng to thnh phc anion ca Crm III
3KOH + Cr(OH)3 K3[Cr(OH)6] (mu lc)
3KCl + CrCl3 K3[CrCl6] (mu )
3KCN + Cr(CN)3 K3[Cr(CN)6] (mu vng)
Cr2(SO4)3 + H2SO4 2H3[Cr(SO4)3] (mu lc)
Cc hp cht Cr (VI), Mo (VI), W (VI)
Trong dy dn xut cng kiu ca Cr(VI), Mo(VI), W (VI) bn tng

ln. i vi Cr(VI) ch c oxit CrO3 v cc xhalogenua CrO2F2, CrO2Cl2 l
bn. i vi Mo(VI) v W (VI) ngoi nhng hp cht trn ra cn c MF6 (cng
nh WCl6, WBr6) cc Sulfua MS3 , cc oxhalohenua XOHal4 cng l cc hp
cht c trng. Cc Halogenua MX6, oxhalogenua MOX4, MO2X2 v oxit MO3
l nhng hp cht axit ng vi chng l cc phc cht anion. Trong s cc phc
cht Cr(VI) in hnh l CrO42-, CrO3X- i vi Mo v W ngoi cc phc kiu
trn cn c MF82-, MS42-, MO3N3- bn.
281
Bn cht axit ca MF6 th hin khi tc dng vi cc florua baz.
2KF + MF6 K2[MF8]
c trng i vi Cr l cc oxhalogenua CrO2F2 v CrO2Cl2 (Crmyl Clorua) l

cht lng mu nu (t0nc = -96,50C, t0s = 1170C) c to thnh khi cho CrO3
tc dng vi HCl kh.
CrO3 + 2HCl CrO2Cl2 + H2O
Cc hp cht MO2X2 thy phn thun nghch
MO2Cl2 + H2O H2MO4 + HCl
Cn bng ca CrO2Cl2 chuyn dch v bn phi, MoO2Cl2 v WO2Cl2 b

thy phn vi mc t hn iu ny chng t du hiu axit yu i trong dy
CrO2X2, MoO2X2, WO2X2.
ng vi Oxhalogenua ta c cc mui vi kim loi kim M nh sau:
M[CrO3X], M2[MO2F4], M3[MO3F3
Cc tri oxyt l cc cht tinh th CrO3 mu sm, MoO3 mu lc, WO3 mu

vng. Khi t nng CrO3 nng chy 1900C d b phn hy
2CrO3 Cr2O3 + 3/2O2
MoO3 c t0nc = 7910C, WO3 c t0nc = 14730C nng chy th thng hoa khng b
phn hy.
CrO3 l cht oxy ha mnh, n phn ng n vi nhiu cht kh, c
2CrO3 + 12HCl 2CrCl3 + 3Cl2 + 6H2O
khc vi MoO3, WO3 khng tan, CrO3 tan trong nc to ra axit
CrO3 + H2O H2CrO4 axit Crmic
bn cht axit ca MoO3 v WO3 th hin khi tan trong kim.
2KOH + MoO3 K2MoO4 + H2O

282
2KOH + WO3 K2WO4 + H2O
H2CrO4 khng tch c trng thi t do, dung dch n l axit Crmic c
mnh trung bnh H2MoO4 v H2WO4 l nhng cht bt khng tan c mu trng
v vng, khi un nng chng d mt nc to ra axit.
H2MoO4 MoO3 + H2O
Trong dy H2CrO4, H2MoO4, H2WO4 mnh axit gim dn, du hiu

baz tng ln, v d: H2MoO4 v H2WO4 d tc dng vi axit
MO2(OH)2 + 2HCl MO2Cl2 + 2H2O
Tan c trong nc ch c cc cromat, molipdat, wonframat ca kim loi

kim v Mg. Cc dn xut ca CrO42- c mu vng, cc dn xut ca MoO42- v
WO42- khng mu.
i vi Cr (VI) v c bit l Mo (VI), W (VI) ngi ta bit c

nhiu dn xut ca cc phc cht anion plyme. V d: K2Cr2O7 icrmat,
K2Cr3O10 Tricrmat, K2Cr4O13 Tetracrmat, cng thc chung ca ply crmat l
K2[CrO4(CrO3)n-1]. Cc axit ng vi ply crmat, ply Molipdat, ply Vnfram
khng iu ch c trng thi t do.
Cc ply Crmat c iu ch khi cho Crmat tc dng vi axit
2K2CrO4 + H2SO4 K2Cr2O7 + K2SO4 + H2O
3K2Cr2O7 + H2SO4 2K2Cr3O10 + K2SO4 + H2O
Khi lm lnh v axit ha tip tc dung dch bng axit Sulfuric th nhng
tinh th anhydrit Crmic sm s tch ra.
K2CrO4 + H2SO4 CrO3 + K2SO4 + H2O
Cn nu cho kim tc dng ln cc dung dch ply crmat th qu trnh

xy ra theo hng ngc li cui cng thu c crmat.
C th biu din qu trnh chuyn ha tng h crmat v icrmat bng

phng trnh thun nghch nh sau:
283
2CrO42- + 2H3O+ Cr2O72- + 3H2O
Ngoi cc oxCrmat cn c peoxCrmat [Cr2O12]2- mu xanh
2-
O O O O
O Cr O O Cr O
O O O O
Kali poexo Crmat c iu ch bng cch rt cn thn dung dch H2O2

30% vo dung dch K2Cr2O7 00C
K2Cr2O7 + 5H2O2 K2[Cr2O2(O2)5] + 5H2O
i vi Mo (VI) v W (VI) cn bit c cc dn xut ca cc phc cht

kiu [MS4]2- [MOS3]2-, [MO2X2]2-, [MO3S]2- chng c iu ch bng cch cho
Hydro Sulfua H2S tc dng vi dung dch Mlipat v Vnfram
K2MO4 + H2S K2[MS4] + 4H2O
Cc hp cht ca Crm (VI) l cc cht oxy ha mnh
K2Cr2O7 + 3(NH4)2S + H2O 2Cr(OH)3 + 3S + 6NH3 + 2KOH
trong mi trng kim
K2Cr2O7 + 3(NH4)2S + 4KOH + H2O 2K3[Cr(OH)6] + 3S +

6H3N
Cc Crmat c hot tnh oxy ha ln nht trong mi trng axit. Tnh oxy
ha ca cc hp cht Mo (VI) v W (VI) ch th hin khi gp cht kh mnh
nh H nguyn t.
Trong s cc dn xut ca Crm v cc nguyn t tng t n ch yu ch

c cc hp cht ca Crm l c ng dng, v d: Cr2O3 dng iu ch sn mu,
284
lm xc tc, CrO3 dng iu ch Crm v m Crm cc chi tit my. Cc hp

cht khc ca Crm dng trong phn tch ha hc.
285
CHNG XXII. CC NGUYN T PHN NHM VIIB
(Mn, Tc, Re)
Mangan (Mn), Tecnexi (Tc), Rni (Re) l nhng nguyn t hon ton
tng t nhau v cu to electron, cu hnh electron ha tr l: (n - 1)d5 ns2.
Mt s d kin nguyn t
Nguyn t Mn Tc Re
S th t 25 43 75
Cu hnh electron 3d5 4s2 4d5 5s2 5d5 6s2
RNT (A0) 1,3 1,36 1,37
- Khc vi cc nguyn t p, Mn, Tc, Re to nn cc lin kt ha hc nh

cc electron cc phn lp bn ngoi 3d, 4s, 4p. Cc trng thi lai ha in hnh
nht l sp3d2, sp3.
- S oxy ha c trng ca Mn l +2, +4 v +7. Ngoi ra c nhng hp

cht Mn vi mc oxy ha +3 v +6.
- Tc v Re c bn knh nguyn t gn nhau cho nn v tnh cht gn nhau

nhiu hn so vi Mn.
XXII.1. N CHT
Tnh cht vt l
Do cc nguyn t Mn v ca nhng nguyn t tng t n c nhiu

obitan ha tr t do nn di dng n cht chng l nhng kim loi in hnh:
Mn, Re mu trng bc cn Tc mu nh.
286
Trng thi thin nhin
Khong vt ch yu ca Mn l pyrzylit MnO2. Re khng to thnh

khong c lp m l nguyn t phn tn. S tn ti Tc equa Mangan c
.I Meneleep tin on nm 1871. Tecnxi l nguyn t u tin c iu ch
bng con ng nhn to. Ngy nay ngi ta tm c 19 ng v ca Tc,
ng v bn l 99Tc (T1/2: 2,5.105 nm). S tng hp Tc xy ra trong cc v sao
c bit l mt tri. Trong v tri t c mt lng khng ln Tc. Ngi ta
cho rng n c to thnh do cc bc x ca v tr tc dng ln khong vt ca
Mo, Nb, Ru cng nh s phn r t pht ca ht nhn Uran.
Ngi ta iu ch Mn bng s in phn dung dch MnSO4
MnSO4 + H2O Mn + 1/2O2 + H2SO4
hay bng phng php nhit Silic
MnO2 + Si Mn + SiO2
Ngi ta iu ch Re bng cch t nng NH4RO4 trong dng H2
2NH4RO4 + 4H2 2Re + N2 + H2O
Ngun iu ch Tc l sn phm phn chia Uran
Tnh cht ha hc
Hot tnh ha hc gim xung t Mn Tc. Mn ng trc H cn Re v

Tc ng sau trong dy in th nn Mn ha tan c trong dung dch axit HCl
v H2SO4 long
Mn + 2HCl MnCl2 + H2
Mn + H2SO4 MnSO4 + H2
cn RE v Tc ch tc dng vi axit HNO3
3Tc + 7HNO3 3HTcO4 + 7NO + 2H2O
do hot tnh ha hc cao nn Mn d dng b oxy khng kh oxy ha

287
2Mn + O2 2MnO
tc dng vi cc kim khc khi un nng
Mn + Cl2 MnCl2
Rc, Tc tham gia tng tc vi kim nhit cao hn
XXII.2. CC HP CHT
Cc hp cht Mn (II), Re (II), Tc (II)
Cc hp cht bc hai ca Mangan ha tr II l cc cht tinh th. S phi tr

ca Mn (II) trong cc tinh th thng bng VI. Mt s dng th hnh v d MnO,
MnS c cu trc kiu NaCl, cn MnF2 c cu trc kiu Rutin. a s cc hp
cht Mn (II) d tan trong nc, t tan l MnO, MnS, MnF2, Mn(OH)2, MnCO3 v
Mn3(PO4)2. Khi tan trong nc cc mui Mn (II) phn ly to phc cht aqu
kiu [Mn(H2O)6]2+ lm cho dung dch c mu hng.
MnSO4 + 6H2O [Mn(H2O) 6]SO4
Ngoi nhm H2O ra cc anion thnh phn cng ng vai tr phi t.
MnO, Mn(OH)2 MnO: mu xanh xm t0nc = 17800C c thnh phn thay i

(MnO MnO1,5) v c tnh bn dn, ngi ta iu ch bng cch t nng
MnO2 trong kh quyn H2 hay nhit phn MnCO3
MnO2 + H2 MnO + H2O
MnCO3 MnO + CO2
Mn(OH)2 mu trng iu ch theo phn ng trao i
MnSO4 + 2KOH Mn(OH)2 + K2SO4
hay thy phn cc phc anion ca Mn (II)
[Mn(NH3)6]Cl2 + 6H2O Mn(OH)2 + 2NH4Cl + 4NH4OH
MnO v Mn(OH)2 d tan trong axit
288
MnO + 2H3O+ + 3H2O [Mn(H2O)6]3+
MnO + 2HNO3 + 5H2O [Mn(H2O)6](NO3)2
cn vi kim chng ch tc dng khi un nng kh mnh v lu
Mn(OH)2 + 4OH- [Mn(OH)6]4-
s to phc anion cn c
4KCN + Mn(CN)2 K4[Mn(CN)6]
4KF + MnF2 K4[MnF6]
2KCl + MnCl2 K2[MnCl4]
Khi tc dng vi cc cht oxy ha cc dn xut Mn (II) th hin tnh kh,

v d: trong mi trng kim Mn(OH)2 d b O2 khng kh oxy ha
6Mn(OH)2 + O2 2Mn2MnO4 + 6H2O
Trong mi trng kim mnh s oxy ha km theo s to thnh

oxmanganat VI
3MnSO4 + 5PbO2 + 6HNO3 2HMnO4 + 3Pb(NO3)2 + 2PbSO4 +

2H2O
Cc hp cht Tc (II), Re (II) khng c trng
Cc hp cht Mn (IV), Tc (IV), Re (IV)
i vi Mn (IV) hp cht bn l oxit MnO2 v Hydroxyt Mn(OH)4 cc

dn xut phc Manganat IV kiu [MnF6]2- v [MnCl6]2- bn, trong khi MnF4,
MnCl4 li d b phn hy. S phi tr cao nht ca Mn (IV) l 6 tng ng vi
s tham gia to thnh lin kt ca cc obitan sp3d2.
Oxit MnO2 v hydroxit Mn(OH)4
289
MnO2 mu en, Mn(OH)4 mu nu sm l nhng hp cht lng tnh

khng tan trong nc khi tc dng vi axit HNO3 v H2SO4 c chng to thnh
nhng hp cht khng bn
MnO2 + 2H2SO4 Mn(SO4)2 + 2H2O
(en)
Khi cho nng chy vi kim chng to thnh cc ox manganat IV c

thnh phn M2MnO3, M4MnO4 v c gi l cc manganit (M: kim loi kim)
2KOH + MnO2 K2MnO3 + H2O
Cc hp cht Mn (IV) l cc cht oxy ha mnh
MnO2 + HCl MnCl2 + H2O + Cl2
cn khi tc dng vi cc cht oxy ha mnh hn th Mn (IV) b oxy ha to ra

Mn (VI) v Mn (VII).
3MnO2 + KClO3 + 6KOH 3K2MnO4 + KCl + 3H2O
2MnO2 + 3PbO2 + 6HNO3 2HMnO4 + 3Pb(NO3)2 + 2H2O
i vi Tc v Re ngi ta bit c cc dn xut kiu MO2, MX4, cc dn

xut ca Tc (IV) v Re (IV) tng i bn hn cc hp cht cng loi ca Mn
(IV) v Re (IV).
Cc hp cht Mn (VI), Tc (VI), Re (VI)
Trng thi oxy ha VI i vi Mn v cc nguyn t tng t n khng

bn. Trng thi oxy ha VI ca Mn c n nh phn no trong phc cht
anion MnO42-, i vi Tc v Re cng bit c nhng phc cht nh vy, cc
dn xut MnO42-, TcO42-, ReO42- ch tn ti trong dung dch nc c d kim,
trong trng hp ngc li chng b phn hy.
3K2MO4 + 2H2O 2KMO4 + MO2 + 4KOH
cc dn xut Hydro d dng b phn hy ngay khi va iu ch
290
K2MnO4 + H2SO4 H2MnO4 + K2SO4
3H2MnO4 2HMNO4 + MnO2 + 2H2O
Cc Halogen, oxyt v ox Halogenua l nhng hp cht axit d dng b nc

thy phn
3TcF6 + 12H2O 2HTcO4 + Tc(OH)4 + 18HF
3ReOF4 + 9H2O 2HReO4 + Re(OH)4 + 12HF
Cc hp cht Mn (VI) l nhng cht oxy ha mnh. Tuy vy khi tc dng vi

cht oxy ha mnh hn chng b oxy ha
2K2MnO4 + Cl2 2KMnO4 + 2KCl
Ngc li Tc (VI) v Re (VI) l nhng cht kh d b ngay c oxy khng kh

oxy ha
4K2MnO4 + O2 + 2H2O 4KMO4 + 4KOH
Cc hp cht Mn (VII), Te (VII), Re (VII)
Trong dy hp cht mc oxy ha VII tnh bn tng ln t Mn Re. Mn

(VII) ch bit c oxyt Mn2O7 v ox florua MnO3F cn i vi Re (VII) iu
ch c cc hp cht dy ReF7, ReOF5, ReO2F3, Re2O7.
Mn2O7: Anhydrit Permanganic: l mt cht lng nhn, mu en xanh,

khng bn. Ngi ta iu ch n bng cch tc dng H2SO4 c ln Manganat
VII.
2KMnO4 + H2SO4 Mn2O7 + K2SO4 + H2O
Nu khng dng bin php c bit Mn2O7 s phn hy n
2Mn2O7 4MnO2 + 3O2
Mn2O7 v MnO3F l nhng cht oxy ha rt mnh nht l mi trng axit. Cc

cht hu c bng chy khi tip xc.
291
Tc2O7, Re2O7 l nhng cht tinh th mu vng bn, c th iu ch chng bng

cch oxy ha trc tip cc n cht hoc t nng HTcO4, HReO4. Cc
Halogenua, ox Halogenua, oxit ca Mn, Te, Re VII l cc hp cht axit in
hnh. Chng tc dng mnh vi nc.
M2O7 + H2O 2HMO4
MO3F + H2O HMO4 + HF
Trong dung dch nc HXO4 l nhng cht axit mnh v c gi l axit per
manganic HMnO4, HTcO4, HReO4 mnh ca axit phn no b gim xung.
Phn ln cc dn xut MnO4-, TcO4-, ReO4- d tan trong nc. Tng i kh
tan l cc mui ca K+, Rb+, Cs+. Ion MnO4-: tm , TcO4-: hng, ReO4-: khng
mu.
MnO4- l cht oxy ha, sn phm kh permangant ph thuc vo mi trng.
2MnO4- + 5SO32- + 6H+ 2Mn2+ + 5SO42- + 3H2O
2MnO4- + 3SO32- + 6H2O 2MnO2 + 3SO42- + 2OH-
2MnO4- + SO32- + 6OH- 2MnO42- + SO42- + 2H2O
Khi t nng KMnO4 b phn hy.
2KMnO4 K2MnO4 + MnO2 + O2
Trong nhng dn xut ca nguyn t Mn th MnO2 c ng dng ln nht, l

sn phm iu ch tt c cc dn xut khc ca Mn
292
CHNG XXIII. CC NGUYN T PHN NHM VIIIB
Phn nhm VIIIB gm c 3 b ba nguyn t d.
B 1 Fe Co Ni
Cu hnh electron ha tr 3d64s2 3d74s2 3d84s2
Bn knh nguyn t (A0) 1,26 1,25 1,34
B 2 Ru Rh Pd
Bn knh nguyn t (A0) 1,34 1,34 1,37
B 3 Os Ir Pt
Bn knh nguyn t (A0) 1,35 1,38 1,38
a s cc nguyn t phn nhm ny c 2 electron lp electron ngoi

cng, tt c chng l kim loi. Trong cc nguyn t ny cc orbital ln lt c
in thm electron th 2, iu ny lm cho cc nguyn t ng cnh nhau trong
1 chu k c tnh cht ging nhau.
Vic so snh tnh cht l ha hc ca cc nguyn t nhm VIIIB chng

t rng Fe - Co - Ni nm trong chu k ln u tin rt ging nhau, trong khi
chng khc xa vi cc nguyn t vi hai b ba cn li. Do ngi ta thng
tch chng ra thnh h st. Su nguyn t cn li ca nhm VIII c gi chung
l cc kim loi h Platin.
XXIII.1. CC NGUYN T H ST
293
XXIII.1.1. n cht st
St l mt kim loi mu trng nh kim l kim loi ph bin nht trn qu

t sau nhm, n chim 4% khi lng v tri t ngi ta gp st di dng
cc qung: qung st t Fe3O4, qung st Fe2O3, qung st nu 2Fe2O3.3H2O,
xyderit FeCO3, pyrit FeS2. St trng thi t do ch c trong cc thin thch.
Tnh cht ha hc
Trong khng kh m Fe b r nhanh ngha l b ph mt lp st oxit hydrat

mu nu xp nn khng bo v c st khi b oxy ha tip tc khi d oxy.
2Fe + 3/2O2 + 4H2O Fe2O3.nH2O
khi thiu oxy
3Fe + nH2O + 2O2 Fe3O4.nH2O
St d dng tc dng vi cc kim khc nh X2, S khi c un nng:
2Fe + 3Cl2 2FeCl3
St ha tan trong axit HCl c nng bt k
Fe + 2HCl FeCl2 + H2
S ha tan xy ra tng t trong axit H2SO4 long
Fe + H2SO4 FeSO4 + H2
Trong dung dch H2SO4 m c Fe b oxy ha ln Fe (III)
2Fe + 6H2SO4 Fe2(SO4)3 + 3SO2 + 6H2O
Fe th ng trong axit H2SO4 m c ngui. Trong dung dch axit HNO3 long
v nng va phi Fe b ha tan.
Fe + 4HNO3 Fe(NO3)3 + NO + 2H2O
Khi nng HNO3 ln s ha tan tr nn chm li v Fe tr nn th ng
294
XXIII.1.2. Hp cht ca Fe
1. Cc hp cht Fe(II)
- Mui Fe(II) c to thnh bng cch cho tc dng trc tip Fe vi acid.
Cc hp cht Fe (II) c s phi tr 6. V d: [Fe(H2O)6]2+, [Fe(OH)6]4-
,[Fe(CN)6]4- ngi ta cng thy c cc phc cht t din ca kiu [FeCl4]2-,
[Fe(SCN)4]2-. Cc phc anion cng nh phc cht cation u c trng vi
Fe(II).
V d : FeO (en), Fe(OH) 2 (lc nht), FeS (en), FeCO3 (trng) u d tan
trong cc acid long to thnh phc cht aqu.
FeO + 2H3O+ + 3H2O [Fe(H2O)6]3+
FeCO3 + 2H3O+ + 3H2O [Fe(H2O)6]2+ + CO2
Ion [Fe(H2O)]2+ c mu lc nht, cng l mu c trng cho cc hydrat tinh

th ca Fe(II): FeCl2.6H2O, Fe(NO3)2.6H2O, FeSO4.7H2O,.....khi c mt hi m
FeS, FeCO3 b oxy khng kh oxy ha dn dn
4FeS + O2 + 10H2O 4Fe(OH)3 + 4H2S
S oxy ha xy ra d dng trong mt kim Fe(OH)2 ngay khi va iu ch

chuyn sang Fe(OH)3
4Fe(OH)2 + O2 + 2H2O 4Fe(OH)3
Trong s cc phc cation ca Fe(II) ngi ta cng bit c phc amin

[Fe(NH2)6]2+ ch bn trng thi rn, trong dung dch nc d b ph hy
[Fe(NH3)6]Cl2 + 6H2O Fe(OH)2 + 2NH4Cl + 4NH4OH
Phn ln dn xut phc anion ca Fe(II) t bn v ging mui kp thuc

loi ny c: M2[FeCl4], M2[Fe(SCN)4], (NH4)2SO4.FeSO4.6H2O (mui Mo). Ch
c Fe(II) phc cht xyanua [Fe(CN)6]4- l bn v d iu ch
Fe(CN)2 + 4KCN K4[Fe(CN)6]
295
dung dch ny khi tng tc vi mui Fe(III) to phc mu xanh Beclin, c

dng lm phn ng nh tnh i vi ion Fe3+
3K4[Fe(CN)6] + 4FeCl3 Fe4[Fe(CN)6]3 + 12KCl
2. Cc hp cht ca Fe (III)
Cc hp cht ca Fe(III) s phi tr bng 6. Chng hn: FeCl3 l cht tinh

th c mu nu sm nh lc, trong dung dch b thy phn n mui baz
FeCl3 + 6H2O [Fe(H2O)6]Cl3
[Fe(H2O)6]3+ + H2O [Fe(H2O)5OH]2+ + H3O+
- Oxit Fe2O3 c mu t thm n tm en, c 3 dng th hnh , , ,

c iu ch bng cch loi nc Fe(OH)3
2Fe(OH)3 Fe2O3 + 3H2O
Fe2O3, Fe(OH)3 tan c trong axit to thnh phc cht aqu khng mu, t
nhng dung dch s tch ra cc Hydrat tinh th FeCl3.6H2O, Fe(NO3)3.6H2O,
Fe2(SO4)3.18H2O...
Mu ca cc hp cht Fe (III) cn ph thuc vo bn cht anion.
V d: FeCl3 (nu sm), Fe(SCN)3 ( mu), Fe(NO3)3.6H2O tm nht.
- Fe(OH)3 va mi iu ch d tan trong kim c to thnh hexahydroxo

ferat kiu M3[Fe(OH)6]:
Fe(OH)3 + 3KOH K3[Fe(OH)6]
Khi nu chy Fe2O3 hay Fe(OH)3 vi kim hay xa s to thnh ox

metaferat kiu MFeO2 gi l ferit.
Na2CO3 + Fe2O3 2NaFeO2 + CO2
- Trong s cc phc cht anion th [Fe(SCN)6]3-, [Fe(CN)6]3- l phc bn.

Phc ny c iu ch nh sau:
296
2K4[Fe(CN)6] + Cl2 2K3[Fe(CN)6] + 2KCl
K3[Fe(SCN)6] mui mu mu; K3[Fe(CN)6] l thuc th nhn bit

ion Fe2+
3Fe2+ + 2[Fe(CN)6]3- = Fe3[Fe(CN)6]2
xanh tuabin (xanh m)
3. Cc hp cht Fe (VI)
- Nu ta un v bo thp hoc Fe2O3 vi KNO3 v KOH th to thnh hn

hp nng chy trong c cha kali ferat K2FeO4 l mui ca axit feric
H2FeO4.
Fe2O3 + 4KOH + 3KNO3 2K2FeO4 + 3KNO2 + 2H2O
Khi ha tan trong nc ta thu c dung dch mu tm , khi cho tc

dng vi dung dch BaCl2 ta thu c Bari ferat BaFeO4 kt ta khng tan trong
nc.
BaCl2 + K2FeO4 BaFeO4 + 2KCl
Tt c cc ferat u l cht oxy ha rt mnh, mnh hn c KMnO4,

chng khng bn d b phn hy
2K2FeO4 + 2NH3 2KFeO2 + N2 + 2KOH + 2H2O
2K2FeO4 2KFeO2 + K2O + 3/2O2
axit feric H2FeO4 anhydrit ca n FeO3 khng iu ch c trng thi t do
4. Cc hp cht Fe (0)
- Fe c kh nng to thnh cc hp cht nh c tng tc cho nhn. V d:

khi un bt Fe nng trong dng kh CO 150 - 2000C v p sut gn 100atm th
Fe Penta Cacbonyl Fe(CO)5 s c to thnh
Fe + 5CO Fe(CO)5
297
Fe(CO)5 l mt cht lng mu vng d bay hi t0nc = -200C, t0s = 1030C tan trong
Benzen v te nhng khng tan trong nc, phn t c cu hnh khi kp tam
gic ng vi s lai ha sp3d
3d 4s 4p
Khi un nng th Cacbonyl b ph hy nn chng c dng iu ch

kim loi tinh khit nht. Khi Cacbonyl ca cc kim loi b oxy ha kh chng
vn gi mt phn hay ton b cc nhm phi tr CO.
Trong NH3 lng Fe(CO)5 tc dng vi Na.
Fe(CO)5 + 2Na Na2[Fe(CO)4] + CO
trong dung dch ru n tc dng vi kim
Fe(CO)5 + 4KOH K2[Fe(CO)4] + K2CO3 + 2H2O
Cc hp cht kiu M2[Fe(CO)4] l nhng mui chng d dng b thy

phn thnh Cacbonyl Hydrua H2[Fe(CO)4] l hp cht c tnh cht ca axit.
2KOH + H2[Fe(CO)4] = K2[Fe(CO)4] + 2H2O
Khi oxy ha thn trng Fe(CO)5 bng Halogen, th mt nhm CO c

thay th bng 2 nguyn t Halogen.
Fe(CO)5 + I2 [Fe(CO)4]I2 + CO
5. Hp kim ca Fe
Cng nghip luyn kim ngy nay ch to c rt nhiu hp kim ca

Fe c thnh phn khc nhau. Ty theo thnh phn ngi ta chia nhng hp kim
ny ra lm 3 loi: St non, gang v thp. St non l Fe gn nguyn cht nht. C
ba th hp kim ny u c tnh cht ha hc gn ging nhau nhng li c tnh
cht vt l v c hc rt khc nhau.
298
- Gang:
Gang l hp kim ca Fe c cha t 2 6% C ngoi ra trong gang cn c

mt s nguyn t khc nh: Si (1 - 4%), Mn (0,5 - 3%), P (0,1 - 2%), S (0,1 -
1%)... Ty thnh phn v cch luyn, ngi ta chia ra gang xm, gang trng v
gang c bit.
+ Gang xm: Ch to nhit cao cha nhiu C (3,5 - 6%) v Si (1,5 -

4%) khi c ha rn chm, C tch ra v kt tinh di dng than ch lm cho
hp kim c mu xm. Loi gang ny cng v gin khng ko si v dt mng
c. N c th c d dng v trng thi lng rt linh ng v khi ha rn th
tch ca n tng t t.
Ngi ta dng gang xm c nhiu vt dng khc nhau: l, ct, cc

ng dn nhit, ph tng my mc.
+ Gang trng: Ch to nhit thp hn, cha t Cacbon t do hn

gang xm 2 - 3% v rt t Si, khi lm lnh nhanh nhng tinh th Cacbua Fe Fe 3C
(xementit) c hnh thnh v lm cho gang c mu trng. Gang trng rt cng
v rt gin khng dng c khun c. Ngi ta dng gang trng luyn
thp.
+ Gang c bit: C cha mt t l thch hp ca nhiu nguyn t khc

nhau: Mn, Cr, Si, W... Gang c bit dng trn thm vo gang thng
luyn nhng kim loi thp qu.
- Thp
L hp kim ca Fe vi Cacbon v mt s nguyn t khc trong lng C

chim t 0,01 - 2%. Thp chia ra lm 2 loi chnh:
+ Thp thng: Cha t Cacbon, Si v Mn hn gang, P v S c rt t trong loi

thp ny. Tnh cht c hc ca loi thp ny ph thuc vo lng Cacbon c
trong thp v nhit khi ch ha. Thp mm dng iu ch cc b phn
my mc, cc ng, bulng, inh...
299
+ Thp c bit: c nhiu nguyn t khc nh Mn, Si, Cr, Ni, W... nhng
nguyn t ny gi l nhng nguyn t kt hp. S c mt ca nhng nguyn t
kt hp ny lm thay i cn bn tnh cht ca thp.
V d: thm Si lm tng tnh n hi, dng lm l xo, dp xe...
Thm Mn: s lm tng tnh nht, sc chu ma st v va chm dng lm my

nghin , ng ray ch r hay cong.
Thm W lm tng tnh cng; v d: Thp cha 18%W, 4%Cr, 1%V gi l thp
gi rt cng dng ch li ct, mi khoan. Thp cha Cr, Ni rt do, bn, chu
nng v khng b oxy ha. Thp cha 36%Ni, 0,5%Mn, 0,5%C c h s dn n
b c dng to ra cc dng c o lng chnh xc.
XXIII.1.3. Coban
Co t ph bin trong t nhin, hm lng trong v tri t khong 0,004%

(KL) Cban thng gp hn c l trong hp cht vi Asen di dng khong
xmantit CoAs2, Cobatin CoAs.
Co l kim loi ng nh, rn, c t tnh ging st. iu kin thng n

khng tc dng vi cc kim loi in hnh nh O2, S, Cl2... nhng khi un
nng chng phn ng mnh lit, Co tan trong axit long kh hn Fe.
Co to thnh CoO v Co2O3, chng ng vi cc hydroxyt Co(OH)2 v

Co(OH)3, ng vi cc cht ny l hai loi mui Co (II) v Co(III), trong
Co(II) bn hn. Mui Co (II) trng thi khan thng c mu xanh cn dung
dch nc v hydrat tinh th ca n c mu hng. V d: CoCl2.6H2O l tinh th
mu hng.
Co(OH)2: c iu ch khi cho kim tc dng vi dung dch mui.
CoCl2 + 2NaOH Co(OH)2 + 2NaCl
Hp cht Coban (II) b oxy ha kh hn nhiu so vi hp cht Fe(III), Co(OH)2

b oxy ha trong khng kh chm hn Fe(OH)2
4Co(OH)2 + O2 + 2H2O 4Co(OH)3
300
hng en
Tuy vy khi c mt cht oxy ha mnh nh NaClO th s oxy ha Co(OH)2 xy

ra nhanh.
2Co(OH)2 + NaClO + H2O 2Co(OH)3 + NaCl
Khi cho axit c cha oxy tc dng vi Co(OH)3 th khng to ra mui Co (III)
m to ra Co (II) v oxy. V d:
4Co(OH)3 + 4H2SO4 4CoSO4 + 10H2O + O2
Co (III) Hydroxit + axit HCl to ra Cl2 v CoCl2
2Co(OH)3 + 6HCl 2CoCl2 + Cl2 + 6H2O
Nh vy hp cht Co (III) t bn hn so vi hp cht Fe (III) v th hin kh

nng oxy ha mnh hn.
Cc mui n gin ca Co3+ rt t, hu nh ch c mui Co2(SO4)3.8H2O, c

iu ch bng cch oxyha anod mui CoSO4, nhng mui ny cng khng bn,
trong nc b phn hy gii phng O2.
Kh nng to thnh phc ca Co (III) rt c trng, phc ca Co (II) t bn. S

phi tr ca phc Co (III) l 6.
V d: [Co(NH3)6]Cl3, K3[Co(NO2)6]...
XXIII.1.4. Niken (Ni)
Tng t nh Cban, Niken gp trong thin nhin ch yu di dng hp

cht vi As hoc S. V d: khong Cufeniken NiAs, gecofit NiAsS; Ni chim
khong 0,01%.
Niken l kim loi c mu trng bc, nh vng nht rt cng, d nh

bng, b nam chm ht. N c bn cao vi s n mn, bn ha do kh
nng th ng ca n.
Hp cht ca Niken rt ging hp cht ca Cban.
301
Niken to ra 2 oxit l NiO v Ni2O3 v 2 hydroxit tng ng Ni(OH)2, Ni(OH)3.

Tuy nhin ta ch bit mt loi mui Niken trong n c mc oxy ha +2.
Ni(OH)2: Kt ta di dng mu lc sng
NiCl2 + 2NaOH Ni(OH)2 + 2NaCl
khi un nng Ni(OH)2 NiO + H2O
lc xm
Ni(OH)2 khng b oxy khng kh oxy ha iu ny chng t rng hp

cht Ni (II) kh b oxy ha hn so vi Fe (II) v Co (II).
Mui Niken phn ln c mu lc, v d: NiSO4.7H2O l nhng tinh th

mu xanh ngc lc bo rt p.
Ni(OH)3 c mu nu en v c to thnh khi kim tc dng vi mui

Niken c cht oxy ha mnh.
Mui ca Ni3+ khng tn ti.
Cc mui Ni (II) to thnh nhiu mui phc, c s phi tr 6;

[Ni(H2O)6]F2, [Ni(NH3)6]Cl2...
Trong cc hp cht ca Niken (III) th oxit Ni2O3 c dng to acqui

kim Cadimi - Niken hoc St - Niken.
c qui kim Cadimi - Niken (k hiu CN) v St Niken (k hiu SN) rt

ging nhau. S khc nhau c bn gia chng l vt liu lm tm in cc m:
trong c qui CN n l Cd, cn trong cqui SN l Fe. c qui CN c ng dng
rng ri nht.
c qui kim c sn xut ch yu l cc c qui c cc in cc tm

mng - tm phng c l. Cht hot ng trong cc bn dng l Ni 2O3.H2O hoc
NiOOH. Ngoi ra trong cn c Grafit n c thm vo lm tng dn
in, cht hot ng trong bn m ca cqui CN l hn hp Cd xp vi bt Fe,
cn ca SN l bt Fe, dung dch KOH c cha mt lng nh LiOH dng lm
cht in ly.
302
Ta xt cc qu trnh xy ra khi cqui phng in.
Cc (-): qu trnh oxy ha: Cd - 2e + 2OH- Cd(OH)2
Cc (+): qu trnh kh: 2NiOOH + 2H2O + 2e 2Ni(OH)2 + 2OH-
Khi mch ngoi xy ra s chuyn electron t in cc Cd n in

cc Ni. in cc Cd l anot v tch in m, cn in cc Niken l Catot v tch
in dng, phn ng xy ra khi pin lm vic c vit nh sau:
2NiOOH + 2H2O + Cd = 2Ni(OH)2 + Cd(OH)2
Sc in ng ca cqui Cd - Ni tch in l 1,4V. Khi c qui tch in

cc qu trnh in ha trn cc in cc ca n xy ra ngc li. Trn in cc
Cd xy ra s kh kim loi:
Cd(OH)2 + 2e Cd + 2OH-
Trn in cc Niken xy ra s oxy ha Niken Hydroxyt
2Ni(OH)2 + 2OH- - 2e = 2NiOOH + 2H2O
Phn ng khi tch in ngc vi phn ng xy ra khi phng in
2Ni(OH)2 + Cd(OH)2 = 2NiOOH + 2H2O + Cd
303

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Bi ging: Ha V C Khoa Cng ngh Ha v Mi trng

CHNG I: MT S KIN THC C BN V PHN NG HA HC

I.1. IU KIN XY RA PHN NG HA HC

Mt phn ng ha hc ch c th xy ra nu c hai iu kin sau:

- iu kin nhit ng: th ng p ca qu trnh phn ng phi gim

- iu kin ng hc: tc phn ng phi ln

Nhng s liu tnh ton G ca cc phn ng ha hc c tng i trong

- tng nng (hoc tng p sut nu l cht kh)

- dng dung mi thch hp

Cgr + O2(k) CO2(k)

C G0298 = - 394,38kj/mol <<0, ngha l nhit 298K phn ng l thun li

T nhng iu kin trnh by trn ta thy rng c th d on c

I.2. MI LIN H GIA G CA PHN NG HA HC V CC I

I.2.1. Cng thc tng qut cho mi phn ng

G ca mi phn ng c th c tnh bng cc cng thc sau:

G = G2,,s - G1,s (I.2)

Trong : G: s bin thin th ng p ca phn ng, J

H: entanpi ca phn ng, J

S: s bin thin entropi ca phn ng, JK-1

G2,,s : tng cc th ng p to thnh ca cc sn phm phn ng, J

G1,s : tng cc th ng p to thnh ca cc cht tham gia phn ng, J

Trong : K- l hng s cn bng ca phn ng

R: hng s kh l tng, R = 8,314J.K-1mol-1

I.2.2. Cng thc tng qut cho mi phn ng iu kin chun

iu kin chun s bin thin th ng p chun G0 ca mi phn ng

G0 = G2,,s0 - G1,s0 (I.5)

Nu phn ng l thun nghch th:

Hng s cn bng Kp ca phn ng lin h vi cc hng s cn bng Kc,

P: p sut chung ca h phn ng khi cn bng, atm

ni tng s mol kh c mt trong h phn ng khi cn bng

n- hiu s s mol kh hai v v s mol kh v mt ca phng trnh phn

Hai hng s Kp, Kc ch ph thuc vo nhit

I.2.3. Cng thc tnh G cho phn ng oxi ha - kh xy ra trong dung

i vi cc phn ng oxi ha - kh trong dung dch nc, ngi ta

Nu phn ng iu kin chun th:

F-hng s Faraday, F 96500 C/mol

0 = 0ox - 0kh - 0ox - th kh chun ca cp oxi ha kh c dng oxi ha

=ox - kh , ca mt cp oxi ha kh lin h vi 0 ca n bng cng thc

Nu cp oxi ha kh ny lin h vi nhau bng phng trnh:

Nhn xt: th kh ca mt cp oxi ha kh cng ln th tnh oxi ha ca

I.3.MI LIN H GIA CC I LNG NHIT NG CA PHN

1, Cng thc ca G ph thuc vo nhit :

2, Cng thc hng s cn bng K ph thuc vo nhit :

3, S ph thuc ca entanpi phn ng vo nhit :

4, S ph thuc ca S phn ng vo nhit :

Thng thng ta c cc gi tr GT1, KPT1, HT1, ST1 nhit T1 = 298K v

1.4. MI LIN H GIA CHIU PHN NG V NNG LNG LIN

Phn ng ha hc xy ra l do s ph v lin kt trong cc cht tham gia

1.4.1. S lin h gia H ca phn ng v nng lng lin kt

thy r mi lin h ny ta xt v d sau:

2HaNa ECl-Cl -2UNaCl

H = 2Ha Na + ECl-Cl + 2INa + 2ACl 2UNaCl

Phn ng ny cho thy H lin h vi entanpi nguyn t ha kim loi natri

I.4.2. S lin h gia S ca phn ng v nng lng lin kt

Ta bit S ca phn ng c tnh theo cng thc:

Trong S2 tng entropi ca cc sn phm phn ng, JK-1;

S1 tng entropi ca cc cht tham gia phn ng, JK-1

V entropi l i lng c trng cho hn n ca cc cht nn lin kt trong

Skhi >> Slng > Srn

Chng hn S0H2O(k) = 188,72 J.K-1.mol-1; S0H2O(l) = 69,94 JK-1.mol-1v S0H2O(r) =

T ta c th d on c s bin thin entropi (S) ca cc phn ng. Nhn

I.5. THUYT AXIT BAZO

Trong ti liu ny chng ta dng thuyt axit bazo ca Bronsted:

- Axit l tiu phn (phn t, ion) c kh nng cho proton