4/27/2014

4/27/2014
CAC NHAN XET CHUNG
Ten goi chung: Cancogen (tc la chat co kha nang sinh quang), gom O,
S, Se, Te va Po.
Cau truc lp e ngoai cung: ns
2
np
4
.
Xu hng nhan them 2 e tao hp chat X
-2
, the hien tnh oxy hoa.
T O Te so lp e tang dan en hieu ng chan tang, hieu ng
xam nhap giam. T S tr i co cac AO d, f t do co kha nang tao
lien ket.
Tnh Ox giam nhng khong eu, Se va Te co tnh Ox giam ot ngot
rat nhieu.
T S tr i con co xu hng cho cac e hoa tr tao so Ox dng (+2, +4,
+6), the hien tnh kh.
4/27/2014
N CHAT
X O S Se Te Po
d (g/cm
3
) 1.27 2.06 4.80 6.24 9.30
r (A
o
) 0.66 1.04 1.14 1.12 -
F (EA, eV) 1.47 2.08 2.02 2.0 1.35
I
1
(eV) 13.62 10.36 9.75 9.01 8.43
t
nc
(
o
C) -218.61 -119.3 217 449.8 254
t
s
(
o
C) -182.87 444.6 634.8 990 962
DAT
(o am ien)
3.5 2.6 2.5 2.1 -
4/27/2014
ay xet chu yeu la Oxy va Lu huynh.
Oxy
Co 2 dang thu hnh la O
2
va O
3
.
Cong thc phan t cua O
2
:
2O [1s
2
2s
2
2p
4
] O
2
[(o
s
)
2
(o
s
*
)
2
(o
x
)
2
(t
y,z
)
4
(t
y
*
)
1
(t
z
*
)
1
]

Bac lien ket =2.
o dai lien ket:1.207A
o
(lien ket n O-O =1.48A
o
)
Ly tnh:
Ben nhiet (E
pl
=494 kJ/mol) do co lk oi. t
nc
, t
s
thap do ptl nho, gan nh
khong cc nen kem tan trong nc ( 0
0
C tan 5% v/v).
Thuan t do co e oc than.
4/27/2014
Hoa tnh:
Hoat tnh cao khi nhiet o cao hay co xuc tac. Tnh oxy hoa
manh (tao oxyt t He, Ne, Ar), so Ox = -2 (vi F co so OX +1, +2).
ieu che:
Trong cong nghiep chng cat phan oan khong kh long hay ien
phan nc.
Trong PTN: Nhiet phan cac muoi KClO3, KMnO4, Ca(ClO)2
KClO
3
(MnO
2
, t
o
) KCl + O
2
KNO
3
(t
o
) KNO
2
+ O
2

4/27/2014
Ozon
Lien ket CHT
O trung tam lai hoa sp
2
.
Cong thc e phan t: (o
s
)
2
(o
x
)
2
(t
y
)
2
(o
s
o
)
2

Ozon nghch t do khong co e oc than.
Kem ben hn oxy do ba lk ch = 1.5.
250
0
C t phan huy (cham), con ozon long va hon hp ozon
nong o cao (70%) b phan huy no.
O
3
O
2
+ O
Hoat tnh oxy hoa cao hn oxy (do tao O nguyen t)
Ag + O
3
Ag
2
O + O
2
116.5
o
1.26A
o
4/27/2014
ay xet chu yeu la Oxy va Lu huynh.
Lu huynh (S)
Bat au co cac AO 3d t do co kha nang tham gia tao lien ket.
S co kha nang tao mach zic-zac ong the.
Hoac tao vong kn (S
4
,
S
6
, S
8
).

Cac dang thu hnh khac nhau: S ta phng (S
o
), S n ta (S
|
), S
deo (S

), S vang da cam (S
6
), S o ta (S
2
). Ben va hay gap
ieu kien thng la S
o
(trong t nhien, mau vang chanh) va

S
|
.

108
o
2.05A
o
4/27/2014
t
nc
= 112.8
0
C. T 190 250
0
C co o nht cao nhat do S8 b pha
v tao day S, nen tang o nht, sau ay t>250
0
C th day S
b cat nho ra nen o nht giam.
t
s
= 444.6
0
C, don, cach nhiet, ien, khong tan trong H
2
O.
Trang thai lai hoa ben: sp3.

Vi cac nguyen to co o am ien nho hn (DAT cua S la
2.6) no the hien tnh Ox.
S + H
2
H
2
S , AH
0
298
= -22 kJ/mol
4/27/2014

Trong phan ng vi halogen va Oxy th S the hien tnh kh:
S + O
2
SO
2
, AH
0
298
= -297 kJ/mol
S + KClO
3
SO
2
+ KCl
Hay S + HNO
3
() H
2
SO
4
+ NO
2
(S S
+6
)
Khi nung nong S tan trong nuc soi hay kiem soi, no t Ox-Kh.
S + NaOH (nc) Na
2
S + Na
2
SO
3
+ H
2
O
4/27/2014
Se, Te, Po
Se, Te giong S ca ve phng dien cau tao phan t, thu hnh
va tnh chat ly hoa.

Trong day
S Se Te Po

Tnh kh tang, tnh Ox giam.

Cac nguyen to nay hiem, t gap trong quang oc lap (thng
i kem quang S).
4/27/2014
CAC HP CHAT
CAC HP CHAT CO SO Ox AM
HP CHAT CUA OXY
Gom oxide va peroxide.
Phan t O
2
co F =0.8 eV va I =12.2 eV nen no co kha nang tao
nen cac ion phan t O
2
-2
, O
2
-1
, O
2
+1
bang cach cho hay nhan e
(trong bang sau).

Cac hp chat peroxide O
2
-2
, O
2
-1
co ac iem chung ve cau tao la
cac day oxy (cau oxy O O ).
VD: Na
2
O
2
Na O O Na
4/27/2014
Phan t ion
O
2
-2
O
2
-1

O
2


O
2
+1

Cau tao
Bac lien ket 1 1.5 2 2.5
d
O-O
(A
o
) 1.48 1.26 1.207 1.12
E
O-O
(kJ/mol) 210 328 493 641
Loai O
2
-1
goi la peroxide bac cao, do O
2
ket hp trc tiep vi cac loai kiem
manh :
K + O
2
(to) KO
2
No thuan t, co mau (do co e oc than) va co tnh Ox manh.
4/27/2014
H
2
0
2
Tnh acid rat yeu: H
2
O
2
H
+
+ H
2
O
-
Va co tnh Ox va co tnh Kh, tnh Ox ac trng hn.
O
2
-
+ 2e 2O
-2
: Tnh Ox.
O
2
-
- 2e O
2
: Tnh Kh.
VD:
4H
2
O
2
+ PbS PbSO
4
+ 4H
2
O
KMnO
4
+ H
2
O
2
+ H
2
SO
4
MnSO
4
+ O
2
+
K
2
SO
4
+ H
2
O
4/27/2014
HP CHAT CUA LU HUYNH
S(-2) va S(-1) the hien trong cac hp chat sulfua (sulfide) va polysulfua (tng
t oxide va peroxide).
Cac sulfur rat giong vi cac oxide ve moi mat: Thanh phan, cau tao, tnh
chatVD:
Vi Na (base): Na
2
O, NaOH, Na
2
S, NaSH.
Vi Al (lng tnh): Al
2
O
3
, Al(OH)
3
, Al
2
S
3
, Al(SH)
3
Vi P (acid): P
2
O
5
, H
3
PO
4
, P
2
S
5
, H
3
PS
4


H
2
S:
Goc (HSH)=92
o
, t
nc
=-85.6
0
C, t
s
=-60.75
0
C. Kem ben hn H
2
O, rat oc (khong
kem HCN).
4/27/2014
Tnh chat ac trng cua H
2
S: Kh.
FeCl
3
+ H
2
S FeCl
2
+ HCl +S
Khi b Ox S
-2
co the S
+6
, va de dang S
0
.
Kha nang tao mach ong the cua S:
Na
2
S + (n-1)S Na
2
S
n
(n = 2 9)
Tang ham lng S, mau cac sulfur thay oi t vang (S
2
-2
)
sang o (S
9
-2
), cau tao mach bieu dien nh sau:
-2
4/27/2014
CAC HP CHAT CUA Se, Te, Po

Cac hp chat cua Se, Te, Po co tnh base, tang len t Se en Po.
Tnh kh tang t Se en Po.
Khuynh hng tao thanh cac hp chat co lk kim loai tang len trong
day O S Se Te.
Oxyt Sulfua ____________Selenua Telurua
So lk kim loai t Nhieu chat la ban dan
Cac chat ban dan cua Selenua va Telurua: ZnX, HgX, CdX.
4/27/2014
CAC HP CHAT CO SO Ox DNG

T S tr i co kha nang tao X (+1 en +6) ma ac trng nhat la
+4 va +6. Trang thai + the hien ien hnh trong cac hp chat vi
halogen va oxy.

Cac hp chat X(+4)
Lu huynh SO
2
, H
2
SO
3
, SO
3
-2
.
SO
2
cau tao giong O
3
, la chat kh
co t
nc
=-75
0
C, t
s
=-10
0
C.

119.5
o
1.43A
o
4/27/2014
SO
2
ben nhiet (AH
0
tt
=-296.9 kJ/mol) la do trang thai lai hoa sp
2
cua
S c on nh nh s xuat hien cua lk t khong nh cho
(bac lk = 1.5).
Do cap e t do ma SO
2
co cac phan ng:
+ Cong (khong thay oi so Ox).
+ Oxy hoa (nhan them e).
+Kh (cho i 1 cap e): Kha nang ac trng hn.
VD:
SO
2
+ H
2
O H
2
SO
3

SO
2
+ 2CO (500
0
C) 2CO
2
+S
SO
2
+ O
2
(t
o
, xt) SO
3

4/27/2014
SO
3
co dang khoi thap trong o S trang thai sp
3
, con d 1 cap
e.




SO
3
co kha nang cho phan ng cong.
Oxy hoa: H
2
SO
3
+ H
2
S H
2
O

+ S
Kh (ac trng hn)
Na
2
SO
3
+ Cl
2
+ H
2
O Na
2
SO
4
+HCl
-2
4/27/2014
Cac hp chat X(+6)
Lu huynh SO
3
, H
2
SO
4
, SO
4
-2
, SO
2
X
2

S lai hoa sp
2
, bac lien ket =1.5.
AH
0
tt
=-395 kJ/mol.
Do trang thai sp
3
nen SO
3
de
polymer hoa tao thanh mach vong (SO
3
)
3

(trime) hay mach h zic-zac (SO
3
)

(long va ran).

120
o
1.43A
o
4/27/2014
(SO
3
)
3
16.80C hoa ran thanh dang -SO
3
de bay hi, boc khoi,
tan de.
-SO
3
e lau bien thanh o-SO
3
giong amiang [(SO
3
)

], khong co
t
nc
xac nh, kho tan.
Oleum: Acid polysulfuric H
2
SO
4
.xSO
3
.
x=3 H
2
S
3
O
10


4/27/2014
SO
3
+ H
2
O H
2
SO
4
, AH
0
298
= -89 kJ/mol
SO
3
SO
2
+ O
2
(t 400-1000
0
C)
Tnh Ox rat manh.
SO
3
+ KI K
2
SO
3
+ I
2

Nhiet hoa tan acid sulfuric:
H
2
SO
4
+ nH
2
O H
2
SO
4
.nH
2
O, AH
0
ht
=-79.4kJ/mol
H
2
SO
4
nguyen chat khong the hien tnh acid, khi pha loang la acid
manh. Phan ly 2 bac (k
1
=, k
2
=2.10
-2
), nen ieu kien thng
ch tao muoi sulfate acid, khi co nhiet o co the tao sulfate trung
tnh.

4/27/2014
Acid H
2
SO
4
ac nong co tnh Ox manh
H
2
SO
4
() + Cu (t
o
) CuSO
4
+ SO
2
| + H
2
O
H
2
SO
4
ac nguoi thu ong hoa Fe, Al, Cr.

Mot so acid va muoi khac cua S.
Acid polythionic H
2
S
x
O
6
(x= 3-6), thu c khi cho
H
2
S suc qua dung dch
SO
2
va ch ton tai trong
dung dch.
4/27/2014
Acid thiosulfuric H
2
S
2
O
3
, trong phan t 1 S(+4), 1S(0), khong ben, de
b phan huy.
Na
2
S
2
O
3
+H
2
SO
4
H
2
S
2
O
3
+Na
2
SO
4

H
2
S
2
O
3
H
2
O + SO
2|
+ S+
Co tnh kh do S
0
gay ra.

Na
2
S
2
O
3
co kha nang hoa tan AgCl, AgBr, AgI tao nen cac phc tan.
AgBr + Na
2
S
2
O
3
Na
3
[Ag(S
2
O
3
)
2
] +NaBr
4/27/2014
Cac hp chat cua Se, Te, Po.

Giong nh lu huynh.
SeO
2
H
2
SeO
3
(anhydric selenous() acid)
SeO
3
H
2
SeO
4
(anhydric selenic acid)
TeO
2
H
2
TeO
3
(anhydric telurous() acid)
TeO
3
H
2
TeO
4
(anhydric telunic acid)
Day SeO
2
TeO
2
PoO
2
co tnh acid giam, tnh base tang. Tnh Ox
ac trng hn tnh kh.