MT S BI TP V HALOGEN

Bi 1: Cho mt l-ng dung dch cha 2,04 gam mui clorua ca

mt kim loi ha tr 2 khng i tc dng va ht vi mt l-ng
dung dch cha 1,613 gam mui axit ca axit sunfuhidric thy c
1,455gam kt ta to thnh. Vit ph-ng trnh phn ng xy ra v
gii thch ti sao phn ng xy ra -c.
+ t cng thc mui clorua l MCl
2
v mui sunfuhidro l R(HS)
x

.
* Nu phn ng to kt ta xy ra xMCl
2
+ R(HS)
x
xMS + +
RCl
x
+ xHCl
(cc mui clorua u tan tr ca Ag
+
, Pb
2+
nh-ng 2 ion ny cng
to + vi S
2
)
theo ph-ng trnh ta thy :
2,04 1, 455
71 32 M M
=
+ +
M = 65
Kt qu rt ph hp vi KL mol ca Zn. Tuy nhin bt hp l
ch :
- Khi thay tr s ca M vo t s :
( 71) 33
2, 04 1, 613
x M R x + +
= tnh -c R
= 74,53 li
khng tha mn mui no.
- Kt ta ZnS khng tn ti trong axit HCl cng v ph-ng
trnh phn ng.
* Vy khng to ra kt ta MS m to ra kt ta M(OH)
2
trong
dung dch n-c.
xMCl
2
+ 2R(HS)
x
+ 2x H
2
O xM(OH)
2
+ + 2x H
2
S | + 2RCl
x

.
Ta c :
2,04 1, 455
71 34 M M
=
+ +
M = 58 ng vi Ni
Thay tr s ca M vo t s
( 71) 33
2, 04 1, 613
x M R x + +
= tnh -c R = 18
ng vi NH
4
+

Vy NiCl
2
+ 2NH
4
HS + 2H
2
O Ni(OH)
2
+ + 2H
2
S | + 2NH
4
Cl
Bi 2 : Cht rn A l kim loi hoc l mt trong cc cht
MnO
2
, KMnO
4
, K
2
Cr
2
O
7
, CaOCl
2
, khi ho tan 15 gam A v dung dch
HCl th to ra 8,4 lt n cht kh B bay ra (ktc). Hy chng
minh rng B khng th l Cl
2

+ MnO
2
+ 4H
+
+ 2Cl
-
Mn
2+
+ Cl
2
| + 2H
2
O
2MnO
4
-
+ 16H
+
+ 10Cl
-
2Mn
2+
+ 5Cl
2
| + 8H
2
O
Cr
2
O
7
2-
+ 14H
+
+ 6Cl
-
2Cr
3+
+ 3Cl
2
| + 7H
2
O
OCl
2
2-
+ 2H
+
Cl
2
|+ H
2
O
Theo ph-ng trnh thu -c 8,4 lt Cl
2
(0.375 mol) th cn
0,125 s s mol A s 0,375
23,7g s m
A
s 47,6 gam. iu ny tri gi thit m
A
= 15. Vy B
khng th l Cl
2

Bi 3 : Vi phn ng

2MnO
4

+ 10X

+ 16H
+
2Mn
2+
+ 5X
2
+ 8H
2
O (X l
halogen)
a) Yu cu 1 : Trong phng th nghim Ho th-ng iu ch Cl
2

bng cch cho KMnO
4
tc dng vi dung dch HCl c. Nu thay
bng dung dch HCl 10
-4
M th c iu ch -c Cl
2
na khng ?
V sao ?
Cho E
0
(Cl
2
/2Cl

) = 1,359 V v E
0
(MnO
4

/Mn
2+
) =
1,51 V
+ - i vi HCl c : MnO
4

+ 8 H
+
+ 5e Mn
2+
+
4H
2
O
Th ca bn phn ng l :
-
4
2
0
8
MnO
4
0, 059
= E lg
5
. Mn
Mn
E
MnO H
+
+
+
(

( (


Thay nng cc cht = 1 (ktc) = 298
0
K th E = E
0

v E
4
2
0
MnO
Mn

+
= 1,51 > E
2
0
2
Cl
Cl

= 1,359 nn phn ng t xy
ra
- Khi nng H
+
= 10
-4
M . Tnh t-ng t cho
E
4
2
0
MnO
Mn

+
= 1,51 +
8
4
0,059
lg 10
5

(

= 1,132 < 1,359 khng c
phn ng v
khng c Cl
2
|
b) Yu cu 2 : Mt dung dch cha Cl

nng 10
-2
M v Br

nng
2.10
-2
M -c oxiha bng KMnO
4
. Hy tnh pH ca dung dch sao
cho ch oxiha hon ton Br

m khng oxiha Cl

. Cho E
0
MnO4
-
/Mn
2+
=
1,50V ; E
0
Br2/2Br
-
=1,10V; E
0
Cl2/2Cl
-
= 1,36V.
Coi nng cc cht cn li = 1 v p sut cc kh =1.
+ iu kin MnO
4

oxiha -c X

l E
4
2
MnO
Mn

+
> E
2
2
X
X

Theo gi thit : E(Br
2
/2Br

) = 1,10 -
0, 059
2
lg[Br

]
2
= 1,2 V
E(Cl
2
/2Cl

) = 1,36 -
0, 059
2
lg[Cl

]
2
=
1,478 V
E(MnO
4

/Mn
2+
) = 1,5 +
0, 059
5
lg [H
+
]
8
= 1,5 -
0,0944 pH
ch oxiha hon ton Br

m khng oxiha Cl

th :
1,2 < 1,5 - 0,0944 pH < 1,478 0,233
< pH < 3,178
Bi 4 : . Tm cu hnh electron ca nguyn t Clo cc
trng thi kch thch.Trong cc trng thi nguyn t Clo
ng vi cc s oxiha no ? Dn chng mt s hp cht chng
minh.



F


F


+ Trng thi kch thch th 1 :
17
Cl [
10
Ar] |+ +| | |
|
Trng thi kch thch th 2 :
17
Cl [
10
Ar] |+ | | |
| |
Trng thi kch thch th 3 :
17
Cl [
10
Ar] | | | |
| | |
ng vi cc s oxiho +3 ; +5 ; +7. Mt s hp cht : HClO
2

(axit clor) ,
HClO
3
(axit cloric) , HClO
4
(axit pecloric)
Bi 5 : . Cho phn t: ClF
3
hy: - Vit cng thc cu to;
Cho bit kiu lai ho trong phn t; M t hnh dng phn t.
Cho: ( phn cc) ca phn t l O,55 D ; gc lin kt FClF
= 87
0

+ + Cu to ClF
3
: Nguyn t Clo lai ho sp
3
d.
+ Hnh dng phn t: L-ng chp tam gic hoc ch T
Ba obitan lai ha sp
3
d -c s dng to lin kt vi
obitan p ca ba nguyn t F, cn li hai obitan lai ha
(trn mi obitan c mt cp e t do)
Bi 6 : . phn ly nhit (tnh theo %) 1000 K ca cc
halogen:
F
2
Cl
2
Br
2
I
2

% 4,3 0,035 0,23 2,8
Hy nu quy lut chung ca s bin thin phn ly nhit,
gii thch s bt th-ng v phn ly nhit t F
2
n Cl
2

+ Qui lut: nhn chung t F n I phn li nhit tng do: bn
knh nguyn t tng, di lin kt tng, nng l-ng lin kt
gim.
* Gii thch s bt th-ng: - Flo trong phn t ch c lin kt
n (khng c obitan d).
- Clo ngoi lin kt cn c lin kt t gia cc obitan d cn
trng v cp e ch-a lin kt.
Bi 7 : . Cho cc tr s gc lin kt: 100,3
0
; 97,8
0
;
101,5
0
; 102
0
v cc gc lin kt IPI ; FPF; ClPCl ; BrPBr . Hy
gn tr s cho mi gc lin kt v gii thch.
+ Cc gc lin kt: IPI (102
0
) > BrPBr (101,5
0
) > ClPCl (100,3
0
) >
FPF(97,8
0
)
- Trong cc phn t , ng-yn t P u lai ha sp
3
v u cn
1 cp e ch-a chia.
- m in ca phi t cng tng th cp e lin kt cng
lch v pha phi t (cng xa P) lc y gia cc cp e
lin kt cng gim gc lin kt gim.
Bi 8 : . a) Ti sao trong cc phn t H
2
O,NH
3
cc gc lin
kt HOH(104,29
0
) v HNH (107
0
) li nh hn gc t din
(109
0
,28) ?
b) Xt 2 phn t H
2
O v H
2
S ti sao gc HSH(92
0
15) li nh hn
HOH(104
0
29)
c) Xt 2 phn t H
2
O v F
2
O ti sao gc FOF(103
0
15) li nh hn
HOH(104
0
29)
+ a) Trong cc phn t trn, nguyn t trung tm trng thi
lai ho sp
3
c cc cp e ch-a lin kt y mnh hn cp e
lin kt.
b) Khi m in ca nguyn t trung tm gim (hoc khi
m in ca phi t tng)th cc cp in t ca lin kt b
y nhiu v pha cc nguyn t lin kt nn chng ch cn mt
khong khng gian nh chung quanh nguyn t trung tm. m
in ca S < O nn gc HSH < gc HOH.
c) m in ca F > H nn FOF < HOH
Bi 9 : . Cho cc phn t: Cl
2
O ; O
3
; SO
2
; NO
2
; CO
2
v cc
tr s gc lin kt: 120
0
; 111
0
; 132
0
; 116,5
0
; 180
0
. Hy
ghi gi tr gc lin kt trn cho ph hp vi cc
phn t t-ng ng v gii thch (ngn gn)
+ m in ca nguyn t trung tm cng mnh ko cc cp e
dng chung v trung tm tng lc y gia cc cp e tng
gc lin kt.
* m in ca obitan lai ha sp > sp
2
> sp
3
.
Cc phn t: O
3
: (116,5
0
); SO
2
: (120
0
); NO
2
: (132
0
) ; c
lai ho sp
2
nn gc lin kt nh hn CO
2
: lai ho sp v ln
hn Cl
2
O: lai ho sp
3
.
* Mt e, ln ca obitan ch-a tham gia lin kt lm tng
lc y khp gc lm gim gc lin kt.
- NO
2
c gc lin kt ln nht v obitan ch-a tham gia lin
kt ch c 1e nn lc y khp gc km hn so vi O
3
v SO
2
u
c obitan ch-a tham gia lin kt cha cp e.
- SO
2
c cu trc phn t dng gc rt ging O
3
nh-ng c gc
lin kt ln hn mt cht v ngoi nguyn t trung tm S c bn
knh ln hn nguyn t trung tm O, cn tn ti mt phn lin
kt t kiu p d to bi obitan p cha cp e t do ca phi t
O vi obitan d cn trng ca S.
- Phn t CO
2
: lai ho sp nn gc lin kt ~ 180
0

- Phn t Cl
2
O: lai ho sp
3
: gc lin kt ~111
0

Bi 10 : . Cho 3 phn t SCl
2
, F
2
O, Cl
2
O vi cc tr s gc
o -c bng 111
0
, 103
0
, 105
0
. Hi l nhng gc no? Gii
thch.
+ Cc phn t trn u thuc loi AX
2
E
2
vi lai ha sp
3
v cu
trc hnh ch V.
* Nguyn t trung tm c m in ln hn s ht cp e
lin kt v pha mnh dn ti s tng lc y gia cc cp e
ny v gc lin kt tng. S khc nhau v gc lin kt trong
phn t SCl
2
v OCl
2
-c gii thch bng s khc nhau v
m in ca nguyn t trung tm, v _
O
> _
S
nn ClOCl > ClSCl
* Ng-c li, phi t c m in ln hn s ht cp e
lin kt lm cho n xa nguyn t trung tm hn, lc y gim
gc lin kt gim. V _
F
> _
Cl
nn FOF < ClOCl .
* Do bn knh nguyn t S > O nn cp e lin kt xa
nguyn t trung tm hn
lc y yu hn gc lin kt nh hn ClSCl <FOF
Vy ClSCl = 103
0
; FOF = 105
0
; ClOCl = 111
0
.
Bi 11 : . Gii thch ti sao CCl
4
l hp cht tr, khng b
thu phn trong H
2
O, cn SiCl
4
li b thu phn rt mnh trong
H
2
O. Vit ph-ng trnh phn ng.
+ Phn t CCl
4
y electron nn c tnh trung ha v tr.
SiCl
4
cn obitan d trng ca Si c th nhn thm electron nn
c tnh axit, ng thi d b thy phn: SiCl
4
+ 2H
2
O
SiO
2
+ 4HCl
SiCl
4
+ 4NaOH SiO
2
+ 4NaCl + 2H
2
O
Bi 12 : . Hp cht A c tng s electron trong phn t =
100. A -c to thnh t 2 phi
kim thuc cc chu k nh v thuc 2 nhm khc nhau. Xc
nh cng thc phn t ca A, bit rng tng s nguyn t cc
nguyn t trong A l 6. M t cu to phn t A (hnh dng,
kiu lin kt).
+ Gi 2 phi kim trong A l X v Y A c dng XY
5
hoc X
2
Y
4

(khng l X
3
Y
3
v s
cng phn nhm).
in tch ht nhn trung bnh ca X,Y = 7 16
6
100
, = phi kim
duy nht thuc
chu k nh c s Z > 16,7 l Clo (Z = 17) thuc phn nhm
VIIA.
a) Nu A l XY
5
ta c 17 + 5Y = 100 Y = 16,6 (loi)
X + 517 = 100 X = 15 ~
Photpho (Z = 15)
Cng thc phn t l PCl
5
.
b) Nu A l X
2
Y
4
ta c 2 17 + 4Y = 100 Y = 16,5 (loi)
2X + 4 17 = 100 X =
16 ~ L-u hunh (Z = 16)
Do hp cht S
2
Cl
4
khng c trong thc t
(do kh nng to lin kt) nn cng thc
phn t ng ca A l PCl
5
.
PCl
5
c cu trc l-ng chp tam gic.
Nguyn t P tm ca tam gic u y
l-ng thp v c lai ho sp
3
d.
Lin kt gia P v Cl l lin kt cng
ho tr gia cc
obitan lai ho sp
3
d ca pht pho vi
obitan p ca nguyn t Cl (lin kt o)
Bi 13 : . Axit Flohydric l mt axit yu nht trong cc
axit HX nh-ng li to -c mui axit cn cc axit khc th
khng c kh nng ny ?
P
Cl
Cl
Cl
Cl
Cl
+ Mt phn v nng l-ng lin kt H F rt ln, mt phn v
khi tan trong n-c ion F
-


t-ng tc vi phn t HF to ra ion
phc HF
2
-
. Do 1 phn phn t HF lin kt to ra HF
2
-
nn hm
l-ng t-ng i ca ion H
3
O
+
khng ln HF c tnh axit yu.
ng thi dung dch HF c cc ion dng HF
2
-
, H
2
F
3
-
, H
3
F4
-
khi
trung ha to ra cc mui axit nh- KHF
2
, KH
2
F
3
-

Bi 14 : . Bo v Nhm l hai nguyn t k nhau phn nhm
IIIA. ti sao c phn t Al
2
Cl
6
nh-ng khng c phn t B
2
Cl
6
?
+ c -c c cu bn vng hn
trng thi
khng n-c, AlCl
3
c khuynh h-ng
dime ho.
Do hiu ng lp th m phn t
BCl
3
khng c
khuynh h-ng ny.V kch th-c ca nguyn t
B qu nh nn s c mt ca 4 nguyn t Clo c th tch
t-ng i ln, quanh n s gy ra t-ng tc y nhau ln
lm cho phn t khng bn vng.
Bi 15 : Nng l-ng lin kt ca BF
3
= 646 kJ/mol cn ca
NF
3
ch = 280 kJ/mol. Gii thch s khc bit v nng l-ng
lin kt ny.
+ NF
3
c N lai ha sp
3
(dng thp),cn BF
3
c B lai ha sp
2
trong c mt phn lin kt t cho to bi xen ph AO p ch-a
lin kt ca F vi AO p cn trng ca B lin kt BF bn hn
nn nng l-ng lin kt ca BF
3
ln hn so vi ca NF
3
.
Bi 16 : im si ca NF
3
= 129
0
C cn ca NH
3
= 33
0
C.
Amoniac tc dng nh- mt baz Lewis cn NF
3
th khng. Momen
l-ng cc ca NH
3
= 1,46D ln hn nhiu so vi momen l-ng cc
ca NF
3
= 0,24D mc d m in ca F ln hn nhiu so vi
H. Hy gii thch.
+ - m in ln ca F lm gim mt e trn N v gim
tnh baz ca N
trong NF
3.
- NH
3
c t
0
si > t
0
si ca NF
3
do NH
3
c lin kt H lin phn
t.
- Trong NF
3
i e khng lin kt to momen l-ng cc theo
chiu ng-c li vi chiu momen l-ng cc chung ca cc lin
kt NF (do m in ca F > N)
cc momen l-ng cc trit tiu nhau nn nh ~ 0.Cn
trong NH
3
momen l-ng cc ca i e khng lin kt cng h-ng
vi momen l-ng cc chung ca cc lin kt NH (do m in
ca N > H).
Bi 17 : Ti sao c cc phn t BF
3
, BCl
3
, BBr
3
nh-ng khng
c phn t BH
3
?
+ S c mt ca lin kt t trong cc phn t BF
3
, BCl
3
lm
cho cc lp v ho tr ca nguyn t B ln nguyn t halogen
t quy tc bt t(bn vng). Khng c -c lin kt t BH
3
,
quanh B ch c 6e lp v ngoi cng nn phn t BH
3
khng
bn vng v c khuynh h-ng dime ho c cu trc bn vng.(
Cl
Cl
Cl
Cl
Cl
Cl
Al Al
S c mt 2 lin kt 3 tm xut hin s xen ph ca 2 obital
lai ha sp
2
ca nguyn t B v obital 1s ca H lm cho cc
nguyn t B u bo ho phi tr v c c cu bn vng)
Bi 18 : Nhm clorua khi ho tan vo mt s dung mi hoc
khi bay hi nhit khng qu cao th tn ti dng ime
(Al
2
Cl
6
). nhit cao (700
0
C) ime b phn li thnh monome
(AlCl
3
). Vit cng thc cu to Lewis ca phn t ime v
monome; Cho bit kiu lai ho ca nguyn t nhm, kiu lin
kt trong mi phn t ; M t cu trc hnh hc ca cc phn
t .
+ * Nhm c 2 s phi tr c tr-ng l 4 v 6. Ph hp vi quy
tc bt t, cu to Lewis ca phn t i me v monome:
Monome
ime ;






* Kiu lai ho ca nguyn t nhm : Trong AlCl
3
l sp
2
v Al c 3
cp electron ho tr;
Trong Al
2
Cl
6

l sp
3
v Al c 4 cp electron ho tr.
AlCl
3
c 3 lin kt cng ho tr c cc gia nguyn t Al
vi 3 nguyn t Cl.
Al
2
Cl
6
: Mi nguyn t Al to 3 lin kt cng ho tr vi 3
nguyn t Cl v 1 lin kt cho nhn vi 1
nguyn t Cl (Al: nhn; Cl: cho).
Trong 6 nguyn t Cl c 2 nguyn t Cl c
2 lin kt, 1 lin kt cng ho tr thng
th-ng v lin kt cho nhn.
* Cu trc hnh hc:
Phn t AlCl
3
: nguyn t Al lai ho kiu
sp
2
nn phn t c cu trc tam gic phng, u, nguyn t Al
tm cn 3 nguyn t Cl 3 nh ca tam
gic.
Phn t Al
2
Cl
6
: cu trc 2 t din ghp
vi nhau. Mi nguyn t Al l tm ca mt
t din, mi nguyn t Cl l nh ca t
din. C 2 nguyn t Cl l nh chung ca 2
t din. (-~ Al; O ~ Cl)


Bi 19 : Phn t HF v phn t H
2
O c momen l-ng cc, phn
t khi gn bng nhau (HF =1,91 D, H
2
O = 1,84 D, M
HF
= 20,
2
H O
M = 18); nh-ng nhit nng chy ca hiroflorua l 83
0
C
thp hn nhiu so vi nhit nng chy ca n-c l 0
0
C,
hy gii thch v sao?

Cl
Cl
Cl
Al
Al
Cl
Cl
Cl
Al
Cl
Cl Cl
120
0
120
0
120
0
O
O
O
O
O
O
Cl
Cl
Cl
Al
M = 20
= 1,91
Debye
M = 18
= 1,84
Debye

+* Phn t H-F ; Phn t
H-O-H



c th to lin kt hiro - H
.
F - c th to
lin kt hiro - H
.
O -
* Nhit nng chy ca cc cht rn vi cc mng l-i
phn t (nt l-i l cc phn t) ph thuc vo cc yu t:
- Khi l-ng phn t cng ln th nhit nng chy cng
cao.
- Lc ht gia cc phn t cng mnh th nhit nng chy
cng cao. Lc ht
gia cc phn t gm: lc lin kt hiro, lc lin kt van
der Waals .
*Nhn xt: HF v H
2
O c mo men l-ng cc xp x nhau, phn
t khi gn bng nhau v u c lin kt hiro kh bn, ng
l hai cht rn phi c nhit nng chy xp x nhau, HF
c nhit nng chy phi cao hn ca n-c (v HF mo men
l-ng cc ln hn, phn t khi ln hn, lin kt hiro bn
hn). Tuy nhin, thc t cho thy T
nc
(H
2
O) = 0
0
C > T
nc
(HF) =
83
0
C.
* Gii thch:
Mi phn t H-F ch to -c 2 lin kt hiro vi 2 phn t
HF khc hai bn
H-F

H-F

H-F. Trong HF rn cc phn t H-F lin kt vi nhau

nh lin kt hiro to thnh chui mt chiu, gia cc
chui lin kt vi nhau bng lc van der Waals yu. V vy
khi un nng n nhit khng cao lm th lc van der Waals
gia cc chui b ph v, ng thi mt phn lin kt hiro
cng b ph v nn xy ra hin t-ng nng chy.
Mi phn t H-O-H c th to -c 4 lin kt hiro vi 4
phn t H
2
O khc nm 4 nh ca t din. Trong n-c
mi phn t H
2
O lin kt vi 4 phn t H
2
O khc to thnh mng
l-i khng gian 3 chiu. Mun lm nng chy n-c cn phi
ph v mng l-i khng gian 3 chiu vi s l-ng lin kt
hiro nhiu hn so vi HF rn do i hi nhit cao
hn.
Bi 20 : Phn ng S
2
O
8
2-
+ 2 I
-

2 SO
4
2-
+ I
2
(1)
-c kho st bng thc nghim nh- sau: Trn dung dch KI
vi dung dch h tinh bt, dung dch S
2
O
3
2-
; sau thm dung
dch S
2
O
8
2-
vo dung dch trn. Cc dung dch u c nng
ban u thch hp.
Vit cc ph-ng trnh phn ng xy ra; ti sao dung dch t
khng mu chuyn sang mu xanh lam?
+ Cc ph-ng trnh phn ng xy ra:
S
2
O
2
8

+ 2 I
-
2
SO
2
4

+ I
2
(1)
I
2
gii phng ra b S
2
O
2
3

kh ngay
2 S
2
O
2
3

+ I
2

S
4
O
2
6

+ 2 I

(2)
Khi ht S
2
O
2
3

th mt t I
2
gii phng ra t (1) tc dng
vi dung dch h tinh bt lm cho dung dch xut hin mu
xanh lam.