班 级：040911
指导教师：夏 平
教 师：吕春燕
1

2005 年 4 月
2

Central contents:
1. Know the general properties of elements of the nitrogen group and inert electron pair effect
2. Know the reactions of ammonia, understand the thermal decomposition trend of ammonium salts
3. Know the properties of nitrous acid and nitrites; understand the structure of nitric acid and nitrate radical; understand the thermal decomposition trend of nitrates
4. Know well the properties of phosphoric acid and phosphates
5. Know the properties of oxides of As, Sb, Bi and their hydrates; understand the properties of sulfides of As, Sb, Bi; know the trends of these compounds
6. Understand the properties of the salts of As, Sb, Bi
7. Understand the identification methods for NH
4
+ , NO
2
, NO
3
, PO
4
3 and Bi 3+
3

Section One The General Properties of Elements of the Nitrogen Group
1. Know the following:
1) Valence shell configuration ns
2 np
3
2) Nonmetal → metalloid → metal
3) Oxidation number: 0 、 +3 、 +5
4) Bonding character
2. Inert electron pair effect:
In the same group, the stability will increase from up to down when the elements have lower oxidation number; but the stability will decrease from up to down when the elements have higher oxidation number
4

Section Two Nitrogen and Its main Compounds
1.The properties of ammonia and ammonium salts
1) Physical properties of ammonia:
(1) Ammonia is a colorless gas with an exceedingly pungent ordor
(2) Readily soluble in the water, one volume H
2
O can dissolve seven hundred volumes NH
3
(15mol·L -1
)
(3) It condenses to a liquid at -33℃ at ambient pressure (25℃/9.9 atm)
(4) When liquid ammonia becomes gas, it will absorb a great deal of heat, so we can use it as a refrigeration reagent
(5) Liquid ammonia is in some ways similar to liquid water. Salts dissolve in ammonia to form conducting solutions, but solubilities are usually lower in ammonia than in water. Alkali metals dissolve in liquid ammonia, and the solution is called liquid ammonia solution
2) Chemical properties of ammonia:
(1)Addition reaction: H
+
, M n+
, molecules
NH
3
+ H
+
→ NH
4
+
4NH
3
+ Cu
2+
→ [Cu(NH
3
)
4
]
2+
2NH
3
+ Ag
+
→ [Ag(NH
3
)
2
]
+
8NH
3
+ CaCl
2
→CaCl
2
∙8NH
3
(2) Substitution reaction: One hydrogen atom is replaced: NaNH
2
; two hydrogen atoms are replaced: Ag
2
NH; three hydrogen atoms are replaced: Li
3
N
(3) Oxidation reaction: O
2
, M x
O y
, X
2
4NH
3
+ 3O
2
2N
2
↑ + 6H
2
O
4NH
3
+ 5O
2
 0    
4NO↑ + 6H
2
O
2NH
3
+3CuO 3Cu +N
2
↑ +3H
2
O
2NH
3
+ 3Cl
2
→ N
2
↑ + 6HCl
3) The properties of ammonium salts
Ions NH
4
+ r
+
/pm 143
K
+
133
Rb
+
148
Na
+
95
5

a) Ammonium salts of non-oxidative volatile acid
NH
NH
4
4
Cl
HCO
3
NH
3
↑ + HCl↑
NH
3
↑ + CO
2
↑ + H
2
O
NH
3
↑+ corresponding acid↑ b) Ammonium salts of non-oxidative involatile acid
(NH
4
)
3
PO
4
3NH
3
↑ + H
3
PO
4
NH
3
↑+acid or acid ammonium salt
(NH
4
)
2
SO
4
NH
3
↑ + NH
4
HSO
4 c) Ammonium salts of oxidative acid
N
2
O: laughing gas
(NH
4
)
2
Cr
2
O
7
N
2
↑ + Cr
2
O
3
+ 4H
2
O
N
2
↑+ H
2
O or N
2
O↑+ H
2
O
NH
4
NO
2
N
2
↑+ 2H
2
O
NH
4
NO
3
 210 0  
N
2
O↑+ 2H
2
O
2NH
4
NO
3
  0 C
2N
2
↑ + O
2
↑ + 4H
2
O d) Identification of NH
4
+
○,1 NH
4
+ + OH H
2
O +NH
3
↑
○,2NH
4
+ +Nessler’s reagent
red-brown↓
2.The properties of nitrous acid and nitrites:
1)HNO
2
is a weak acid, K a
θ =7.2×10 -4
2) The pure acid is unknown, even aqueous solutions of nitrous acid are unstable, decomposing when heated according to the reaction:
NO
2
-
+H
+ →HNO
2
→N
2
O
3
(blue)+H
2
O
NO↑+NO
2
↑
3) Most nitrites are soluble in water except AgNO
2
, and are poisonous and carcinogenic
4) Oxidizing-reducing properties
E
A
θ
: NO
3
-
0.94 HNO
2
0.996 NO
E
B
θ
: NO
3
-
0.01 NO
2
-
-0.46 NO
6

So in acid medium, we will mainly use HNO
2
as an oxidant, but in base medium, HNO
2
will be used as a reductant
NO
2
-
+Fe
2+
+2H
+ →NO↑+Fe 3+
+H
2
O
2NO
2
-
+2I
-
+4H
+ →2NO↑+I
2
+2H
2
O
5NO
2
-
+2MnO
4
-
+6H
+ →5NO
3
-
+2Mn
2+
+3H
2
O
3.The properties of nitric acid and nitrates
1) The structure of nitric acid
2) The structure of NO
3
-
3) The properties of HNO
3
○,1 Pure HNO
3
is a colorless liquid, can mix with water in any proportion
○,2HNO
3
is a strong monoacid and volatile
○,34HNO
3
  
4NO
2
↑ + O
2
↑ + 2H
2
O
○,4 HNO
3
is a strong oxidant
A) HNO
3
reacts with nonmetals
3C+4HNO
3
(dilute)→3CO
2
↑+2H
2
O+4NO↑
C+4HNO
3
(strong)→CO
2
↑+2H
2
O+4NO
2
↑
S→H
2
SO
4
, P→H
3
PO
4
, I
2
→HIO
3
B) HNO
3
reacts with metals; the products will be decided by the concentration of HNO
3
and the
7

strength of reductant
△ ,1 HNO
3
(strong) + metal → NO
2
Cu+4HNO
3
(strong)→Cu(NO
3
)
2
+2NO
2
↑+2H
2
O
Zn+4HNO
3
(strong)→Zn(NO
3
)
2
+2NO
2
↑+2H
2
O
△ ,2HNO
3
(dilute) + active metal → N
2
O
HNO
3
(dilute) + inactive metal → NO
3Cu+8HNO
3
(dilute)→3Cu(NO
3
)
2
+2NO↑+4H
2
O
4Zn+10HNO
3
(dilute)→4Zn(NO
3
)
2
+N
2
O↑+5H
2
O
△ ,3 HNO
3
(very dilute) + active metal → NH
3
H
 
NH
4
+
4Zn + 10HNO
3
(very dilute) →
4Zn(NO
3
)
2
+ NH
4
NO
3
+ 3H
2
O
○,5 Nitration
4) The properties of nitrates:
(1) Nitrates of active metals (>Mg) nitrites + O
2
↑
NaNO
3
NaNO
2
+ O
2
↑
(2) Nitrates of metals (Mg≥M≥Cu)
2Pb(NO
2Cu(NO
3
3
)
)
2
2
2PbO+ 4NO
2
↑ + O
2
↑
2CuO+ 4NO
2
↑ + O
2
↑ metallic oxide + NO
2
↑ + O
2
↑
(3) Nitrates of inactive metals (<Cu) metal + NO
2
↑ + O
2
↑
2AgNO
3
2Ag+ 2NO
2
↑ + O
2
↑
(4) Identification of NO
3
-
3Fe 2+ +NO
3
+4H + =3Fe 3+ +NO+ 2H
2
O
NO + FeSO
4
= [Fe(NO)]SO
4
8

Section Three Main Compounds of Phosphorus
1. Oxyacids of phosphorus
Oxidation number Chemical formal Name
+5
+3
H
3
PO
4
H
3
PO
3
Phosphoric acid
Phosphorous acid
+1 H
3
PO
2
Hypophosphorous acid
H
3
PO
4
-H
2
O→HPO
3
metaphosphoric acid
2H
3
PO
4
-H
2
O→H
4
P
2
O
7
diphosphoric acid
3H
3
PO
4
-2H
2
O→H
5
P
3
O
10
triphosphoric acid
3H
3
PO
4
-3H
2
O→(HPO
3
)
3
trimetaphosphoric acid
4H
3
PO
4
-4H
2
O→(HPO
3
)
4
tetrametaphosphoric acid
Condensation degree of phosphoric acid ↑ acidity↑
2. The properties of H
3
PO
4
3. Preparation of H
3
PO
4
Ca
3
(PO
4
)
2
+H
2
SO
4
→2H
3
PO
4
+ CaSO
4
P
2
O
5
+ 3H
2
O→ 2H
3
PO
4
4. The properties of phosphates
1) Solubility
2) Hydrolysis
PO
4
3-
+ H
2
O ↔ HPO
4
2-
+OH
-
HPO
4
2 + H
2
O ↔ H
2
PO
4
+OH -
HPO
4
2 ↔ PO
4
3 +H +
H
2
PO
4
-
+ H
2
O ↔ H
3
PO
4
+OH
-
H
2
PO
4
-
↔ HPO
4
2-
+ H
+
5. Identification of PO
4
3:
PO
4
3-
+12MoO
4
2-
+24H
+
+3NH
4
+
→
(NH
4
)
3
PO
4
∙12MoO
3
∙6H
2
O↓(yellow)+6H
2
O
Ca
3
(PO
4
)
2
+ 2H
2
SO
4
+ 4H
2
O →2(CaSO
4
·2H
2
O) + Ca(H
2
PO
4
)
2
Ca
3
(PO
4
)
2
+4H
3
PO
4
→3Ca(H
2
PO
4
)
2
9

Section Four Main Compounds of arsenic, stibium and bismuth
1. Oxides of arsenic, stibium and bismuth
+3 As
2
O
3
Sb
2
O
3
Bi
2
O
3
white white black
+5 As
2
O
5
Sb
2
O
5
Bi
2
O
5
white red red-brown
Preparation:
○,14M + 3O
2
→ 2M
2
O
3
○,2HNO
3
+M→HMO
3
→M
2
O
5
Bi(OH)
3
+Cl
2
+3NaOH=NaBiO
3
+2NaCl+3H
2
O
NaBiO
3
Bi
2
O
5
2. Hydrates of their oxides
Acidity↑
+3
+5
H
3
AsO
3
H
3
AsO
4
M 3+ +3OH -

M(OH)
3
≡H
3
MO
3

3H + +MO
3
3-
Add H
+ : equilibrium ← form M 3+
Add H
+ : equilibrium → form MO
3
3-
3. Oxidizing-reducing properties
φ ø
(H
3
AsO
4
/H
3
AsO
3
)=0.581V, φ ø
(NaBiO
3
/Bi
3+
)=1.8V
Sb(OH)
3
H
3
SbO
4 basicity↑
Oxidation number
+5
+3
Bi(OH)
3
NaBiO
3
Oxidation state
As→Bi
Oxidizing properties↑
Reducing properties↓
10

pH<0.5 φ ø
(H
3
AsO
4
/H
3
AsO
3
)>φ ø
I
2
/I
pH>1.0 φ ø
(H
3
AsO
4
/H
3
AsO
3
)<φ ø
I
2
/I
-
H
3
AsO
4
+2I +2H +
H
+
H
3
AsO
3
+I
2
+H
2
O
OH -
2Mn
2+
+NaBiO
3
+14H
+
=2MnO
4
-
+5Bi
3+
+5Na
+
+7H
2
O
4. Salts of arsenic, stibium and bismuth
1) Hydrolysis of chlorides
AsCl
3
+3H
2
O=H
3
AsO
3
+3HCl
SbCl
3
+ H
2
O=SbOCl↓+2HCl
BiCl
3
+ H
2
O=BiOCl↓+2HCl
Sb(NO
3
)
3
, Sb(SO
4
)
3
2) Sulfides
○,1Type and color
Oxidation number
Ⅲ
Color
Ⅴ
Color
As
2
S
3 yellow
As
2
S
5 yellow
○,2Solubility
Substance
Sb
2
S
3 orange red
Sb
2
S
5 orange red
Sulfide H
As
As
2
2
S
S
3
5
2
O Dilute HCl Strong HCl
–
–
Sb
2
S
3
–
Sb
2
S
5
–
–
–
–
–
–
–
Dissolve
Dissolve
NaOH
Na
2
S or
(NH
4
)
2
S
Dissolve Dissolve
Dissolve Dissolve
Dissolve Dissolve
Dissolve Dissolve
Bi
2
S
3 black
11

Bi
2
S
3
– –
Dissolve
Acidic/neutral sulfide + basic sulfide → sulfoacid salt
Acidic/neutral sulfide + base → oxysalt + sulfoacid salt
As
2
S
3
+ 3Na
2
S →2Na
3
AsS
3
As
2
S
3
+6OH
→AsO
3
3-
+AsS
3
3-
+3H
2
O
As
2
S
5
+ 3Na
2
S →2Na
3
AsS
4
4As
2
S
5
+24OH
→3AsO
4
3-
+5AsS
4
3-
+12H
2
O
– –
12

Central Contents:
1. Know the general properties of group Ⅵ
2. Understand the structure of ozone and formation of π bond
3. Understand the structure and properties of H
2
O
2
4. Know well the properties of H
2
S, M x
S y
5. Understand the properties of the oxyacids of sulfur (H
2
SO
4
, H
2
S
2
O
3
, H
2
S
2
O
7
, H
2
S
2
O
8
) and their salts
6. Know how to identify S
2-
, SO
3
2-
, S
2
O
3
2-
and SO
4
2-
Section One General Properties
Element
Oxygen
(O)
8
Sulfur
(S)
16
Selenium
(Se)
34
Tellurium
(Te)
52
Polonium
(Po)
84 Atomic number
Valence shell electron configuration
Atomic radius/pm
2s
2
2p
66
4
3s
2
3p
4
4s
2
4p
4
5s
2
5p
4
6s
2
6p
4
153
Oxidation number -1,-2,0
140
-
104
-2,0,
+4,+6
184
29
117
-2,0,+2,
+4,+6
198
42
137
-2,0,+2,
+4,+6
221
56
-
-
67
Ionic radius/pm
M
6+
M
2-
First ionization energy
I
1
/kJ∙mol -1
Electronic affinity
E
A1
/kJ∙mol -1
Electronegativity
1314
-141
3.5
1000
-200.4
2.5
941
-195
2.4
869
-190.2
2.1
812
-173.7
2.0
13

Oxidation number
-2
-1
Type of compounds Examples
Normal oxides, oxyacids, oxysalts Na
2
O, CaO, H
2
O
Peroxides Na
2
O
2
, BaO
2
, H
2
O
2
-1/2 Hyperoxides KO
2
-1/3
0
Ozonides
O
2
, O
3
For the following oxides, determine the type:
PbO
2
, BaO
2
, SnO
2
, Na
2
O, KO
2
, Na
2
O
2
The properties of peroxides and hyperoxides:
1. React with water or acid:
Na
2
O
2
+ 2H
2
O = 2NaOH + H
2
O
2
Na
2
O
2
+ H
2
SO
4
= Na
2
SO
4
+ H
2
O
2
2KO
2
+ 2H
2
O = 2KOH + H
2
O
2
+ O
2
↑
2KO
2
+ H
2
SO
4
= K
2
SO
4
+ H
2
O
2
+ O
2
↑
2. React with carbon dioxide
2Na
2
O
2
+ 2CO
2
= 2Na
2
CO
3
+ O
2
↑
2BaO
2
+ 2CO
2
= 2BaCO
3
+ O
2
↑
4KO
2
+ 2CO
2
= 2K
2
CO
3
+ 3O
2
↑
1. Ozone :O
3
1) Formation: bond
2) Structure
Section Two Oxygen, and hydrogen peroxide
2. H
2
O
2
(hydrogen peroxide):
1) Structure
2) Properties
KO
3
○,1Pure hydrogen peroxide is a colorless liquid; hydrogen peroxide molecules will associate if they exist in liquid state or solid state because of hydrogen bonds; hydrogen peroxide can dissolve in water in any proportion
14

○,2 Instability: 2H
2
O
2
=2H
2
O+O
2
E
A
θ
O
2
0.695 H
2
O
2
1.76 H
2
O
E
B
θ
O
2
-0.076 HO
2
+0.867 OH -
E
θ right
>E
θ left
→Disproportionation reaction
Factors that affect decomposition of H
2
O
2
:
△ ,1 Light or heat
△ ,2 Acid or base (In basic medium, the disproportionation reaction will be fast)
△ ,3 Impurity: some ions of heavy metals: Mn
2+
, Fe
3+
, Cr
3+
, Cu
2+
or their compounds will accelerate decomposition
○,3 Oxidizing /reducing properties
△ ,1 Oxidizing properties
H
2
O
2
+ 2I
-
+ 2H
+
= I
2
+ 2H
2
O
PbS + 4 H
2
O
2
= PbSO
4
+ 4H
2
O
2Cr(OH)
4
-
+3H
2
O
2
+2OH
-
=2CrO
4
2-
+8H
2
O
△ ,2 Reducing properties
2MnO
4
-
+5H
2
O
2
+6H
+
=2Mn
2+
+5O
2
↑+8H
2
O
Cl
2
+ H
2
O
2
= 2HCl + O
2
5H
2
O
2
+ 2HIO
3
= I
2
+ 5O
2
↑ + 6H
2
O
5H
2
O
2
+ I
2
= 2HIO
3
+ 4H
2
O
○,4 Weak acid
Section Three Sulfur and main compounds of sulfur
Oxidation number
-2
-1
0
Type of compounds Examples
Sulfides, sulfoacids and the salts Na
2
S, As
2
S
3
, Na
2
SnS
3
Polysulfide Na
2
S
2
Simple substance S
8
15

+2
+2.5
+4
+6
Thiosulfuric acid
Tetrathionic acid
Sulfurous acid
Disulfuric acid, sulfuric acid
+6
1. Hydrogen sulfide
Persulfuric acid
1) Colorless gas, stinky poisonous gas
CH
3
CSNH
2
+2H
2
O=CH
3
COO
-
+NH
4
+
+H
2
S↑
CH
3
CSNH
2
+2OH
-
=CH
3
COO
-
+NH
4
+
+S
2-
2) Weak acid
3) Reducing properties
2H
2
S + O
2
= 2S↓ + 2H
2
O
2H
2
S + 3O
2
= 2SO
2
↑ + 2H
2
O
2Fe 3+ + H
2
S = 2Fe 2+ + S↓ + 2H +
H
2
S + I
2
= 2HI + S↓
H
2
S + Cl
2
+ 4H
2
O = H
2
SO
4
+ 8HCl
5H
2
S+8MnO
4
-
+24H
+
=8Mn
2+
+ 5H
2
SO
4
+12 H
2
O
2. Sulfides
1) Solubility:
○,1 Acid salt: dissolve
○,2 Normal salt
2) Hydrolysis:
○,1 S 2: S 2 + H
2
O ↔ HS + OH -
○,2 Al
2
S
3
, Cr
2
S
3
(Complete hydrolysis)
Al
2
S
3
+ 6H
2
O = 2Al(OH)
3
↓ + 3H
2
S↑
Cr
2
S
3
+ 6H
2
O = 2Cr(OH)
3
↓ + 3H
2
S↑
Dissolve Insoluble, but dissolve in following solutions
Na
2
S
2
O
3
Na
2
S
4
O
6
Na
2
SO
3
, SO
2
SO
3
, Na
2
S
2
O
7
H
2
S
2
O
8
Hydrolysis
16

Dilute
HCl
Strong HCl
ⅠA
NH
4
+
ⅡA *
ZnS
MnS
FeS
CoS
*
NiS
*
PbS
CdS
SnS
SnS
2
Sb
2
S
3
Sb
2
S
5
K sp
θ
Note
3) Reducing properties
Bi
2
S
3
>10
-24
10
-25
~10
-30
ⅡA *
: Sparingly soluble
3. Polysulfides
1) Preparation:
Na
2
S + (x-1)S = Na
2
S x
S
2-
+ (x-1)S = S x
2-
(x:2~6)
x↑ color↑ yellow → orangish yellow→ red
2) Properties
○,1 Instability: S
2
2-
+ 2H
+
= H
2
S
2
→ H
2
S+S↓
HNO3
Ag
2
S
CuS
Cu
2
S
As
2
S
3
As
2
S
5
CoS
NiS
10
-30
~10
-50
Aqua regia
HgS
Hg
2
S
<10
-50
○,2 Oxidizing/reducing properties
Oxidizing properties:
SnCl
2
S 2 SnS↓ S
2
2

SnS
3
2-
Reducing properties
4FeS
2
(pyrite) + 11O
2
= 2Fe
2
O
3
+ 8SO
2
2) Application
3)
Section Five Oxyacids and Oxysalts of Sulfur
1. Sulfurous acid and sulfites
Al
2
S
3
Cr
2
S
3
17

1) Sulfurous acid
○,1 Instability: H
2
SO
3
= H
2
O + SO
2
○,2 Acidity: K
1
θ =1.3×10 -2
, K
2
θ =6.2×10 -8
○,3 Oxidizing/reducing properties
E
A
θ
: SO
4
2-
0.158 H
2
SO
3
0.449 S
E
B
θ
: SO
4
2-
-0.936 SO
3
2-
-0.59 S
Reducing properties:
△ ,1In acidic medium:
I
2
+ SO
3
2-
+ H
2
O = SO
4
2-
+ 2I
-
+ 2H
+
5SO
3
2-
+2MnO
4
-
+6H
+
=2Mn
2+
+5SO
4
2-
+ 3H
2
O
2H
2
SO
3
+ O
2
= 2H
2
SO
4
△ ,2In basic medium:
SO
3
2-
+ I
2
+ 2OH
-
= SO
4
2-
+2I
-
+ H
2
O
Oxidizing properties:
H
2
SO
3
+ 2H
2
S = 3S↓ + 3H
2
O
2) Sulfites
○,1 Solubility: Acid salts and some normal salts (K + , Na + , NH
4
+ ) will be readily soluble, others will be insoluble
CaSO
3
+ SO
2
+ H
2
O = Ca(HSO
3
)
2
○,2 Thermal stability
4Na
2
SO
3
 3 Na
2
SO
4
+ Na
2
S
○,3 Reducing properties
2Na
2
SO
3
+ O
2
→ 2Na
2
SO
4
○,4 Identification of SO
3
2-
SO
3
2 + 2H + = H
2
SO
3
→ SO
2
↑+ H
2
O
The test paper of fuchsine: red → colorless
2. Sulfuric acid and sulfates
18

1) Sulfuric acid:
Structure
Properties:
Physical properties
Chemical properties
○,1 Strong acid: H
2
SO
4
→ H
+
+ HSO
4
-
HSO
4
↔ H +
+ SO
4
2-
K
2
θ
=1.0×10
-2
○,2 Thermal stability
H
2
SO
4
SO
3
+ H
2
O
○,3 Oxidizing properties:
△ ,1Sparse sulfuric acid: H +
△ ,2 Concentrated sulfuric acid:
◇
,
1
Reacts with many metals and nonmetals:
Cu+2H
2
SO
4
(strong)=CuSO
4
+SO
2
↑+2H
2
O
C+2H
2
SO
4
(strong)=CO
2
↑+SO
2
↑+2H
2
O
S+2H
2
SO
4
(strong)=3SO
2
↑+2H
2
O
◇ ,
2
Reacts with active metals:
Zn+2H
2
SO
4
(strong)=ZnSO
4
+SO
2
↑+2H
2
O
3Zn+4H
2
SO
4
(strong)=3ZnSO
4
+S+4H
2
O
4Zn+5H
2
SO
4
(strong)=4ZnSO
4
+ H
2
S↑+4H
2
O
◇ ,
3
Passivation: Fe, Al, Cr
○,4 Water absorption: strong, H
2
SO
4
can dissolve in water in any proportion
19

△ ,1 If we mix H
2
SO
4
and H
2
O, we get a lot of heat
△ ,2 H
2
SO
4
is a kind of dryer: Cl
2
, CO
2
△ ,3 H
2
SO
4
can be used as dehydrater in organic reactions
2) Sulfates
○,1 Solubility: Acid salts and the great number of normal salts will be readily soluble, few will be insoluble just like BaSO
4
, PbSO
4
and Ag
2
SO
4
○,2 When soluble salts precipitate out of solution, the salts will contain crystal water (crystalline hydrate):
CuSO
4
∙5H
2
O: bluestone
FeSO
4
∙7H
2
O: copperas
○,3 Thermal stability is determined by the charge, radius and ionic electron configuration of corresponding cation (ionic polarization)
△ ,1 Cation electron configuration: 8
K
2
SO
4
, Na
2
SO
4
, BaSO
4
: stable
△ ,2 Cation electron configuration: 18, 18+2, 9~17
CuSO
4
, Ag
2
SO
4
, PbSO
4
, Fe
2
(SO
4
)
3
: unstable
3. Disulfuric acid and pyrosulfates
1) Disulfuric acid: H
2
S
2
O
7
If we cool oleum, we can get disulfuric acid
SO
3
+ H
2
SO
4
= H
2
S
2
O
7
(colorless)
-H
2
O
2H
2
SO
4
H
2
S
2
O
7
H
2
S
2
O
7
+ H
2
O → 2H
2
SO
4
2) Pyrosulfates
○,1 Preparation: 2KHSO
4
K
2
S
2
O
7
+ H
2
O
○,2 K
2
S
2
O
7
K
2
SO
4
+ SO
3
○,3 Al
2
O
3
+3K
2
S
2
O
7
Al
2
(SO
4
)
3
+3 K
2
SO
4
20

Cr
2
O
3
+3K
2
S
2
O
7
Cr
2
(SO
4
)
3
+3 K
2
SO
4
4. Thiosulfuric acid and thiosulfates
1) Thiosulfuric acid: Thermal instability: H
2
S
2
O
3
→SO
2
↑+S↓+H
2
O
2) Thiosulfates:
Na
2
S
2
O
3
∙5H
2
O: sodium thiosulfate, hypo
○,1Preparation: Na
2
SO
3
+ S Na
2
S
2
O
3
○,2 S
2
O
3
2-
is stable in neutral or basic medium, if we add acid to solution, the following reaction will occur:
S
2
O
3
2-
+ 2H
+
=H
2
S
2
O
3
→SO
2
↑+S↓+H
2
O
○,3 Reducing properties
S
2
O
3
2-
+ I
2
= S
4
O
6
2-
+ 2I
-
S
2
O
3
2-
+4Cl
2
+5H
2
O=2SO
4
2-
+8Cl
-
+10H
+
○,4AgCl+2S
2
O
3
2-
=[Ag(S
2
O
3
)
2
]
3-
+Cl
-
AgBr+2S
2
O
3
2-
=[Ag(S
2
O
3
)
2
]
3-
+Br
-
○,5Identification
Add acid: S
2
O
3
2-
+ 2H
+ →SO
2
↑+S↓+H
2
O
Add AgNO
3
: 2Ag
+
+S
2
O
3
2→Ag
2
S
2
O
3
↓
Ag
2
S
2
O
3
+H
2
O→Ag
2
S↓+H
2
SO
4
White-yellow-orange-brown-black
5. Persulfuric acid and persulfates
1) Persulfuric acid
○,1Structure
○,2Preparation: electrolyze NH
4
HSO
4
Anode: 2SO
4
2-
- 2e = S
2
O
8
2-
Cathode: 2H
+
+ 2e = H
2
2HSO
4
electroly
S
2
O
8
2sis
+ H
2
2) Persulfates
21

(NH
4
)
2
S
2
O
8
+2KHSO
4
=K
2
S
2
O
8
+2NH
4
HSO
4
K
2
S
2
O
8
+ H
2
O 2KHSO
4
+ H
2
O
2
Oxidizing properties:
S
2
O
8
2-
+ 2e = 2SO
4
2-
E
θ
=1.96v
H
+
2Mn
2+
+5S
2
O
8
2-
+8H
2
O 2MnO
4
-
+10SO
4
2-
+16H
+
2I
-
+ S
2
O
8
2-
Ag +
I
2
+ 2SO
4
2-
Thermal instability:
2K
2
S
2
O
8

2K
2
SO
4
+ O
2
↑+2SO
3
↑
Central Contents:
1. Know preparation methods and general properties of halogens
2.Understand the reducing properties, acidity, stability and trends of halogen acids
3. Understand the properties of halides (bond type and solubility) and their trends
4. Understand oxyacids and oxysalts of chlorine and their trends
5. Know the disproportionation law of X
2
, XO
-
in basic medium
6. Know the ionization of hydrates (R-O-H rule)
7. Know how to identify of Cl
-
, Br
-
and I
-
Section One General Properties of Halogens
Halogens: Fluorine, chlorine, bromine, iodine, astatine
1.Natural occurring forms
1) F : CaF
2
(fluorite),Na
3
AlF
6
(cryolite)
2) Cl, Br, I: Exist in seawater (inorganic salt: Na, K, Ca, Mg)
3) At: Unstable (radioactive)
2. General properties
1) Valence shell configuration:ns
2 np
5
22

2) Oxidation number:
F: 0, -1
Cl, Br, I: -1, 0, +1, +3, +5, +7
3) Comparing with other families, halogens are most active non-metals, and they have highest electronegative and first ionization energy
Element F Cl Br I
Atomic number 9 17 35 53
Atomic radius/pm 64 99 114 133
I
1
/kJ•mol -1
χ p
1681
E
A1
/kJ•mol -1
-327.9 -349 -324.7 -295.1
4.0
1251
3.0
1140
2.8
1008
2.5
Section Two Elementary Substance of Halogens
1. Physical properties
1) The elements all form diatomic molecules, and when they exist in the solid state, they are molecular crystals
2) They have low melting and boiling points, but the melting and boiling points of the elements increase with increased atomic number. Fluorine and chlorine are gases, bromine is a liquid, and iodine is a solid
3) The halogen molecules are all colored. This is due to the absorption of visible light. The excitation energies follow the same trend as the ionization energies; excitation of the larger iodine atom requires less energy. Gaseous molecules of F
2
absorb violet light (high energy) and therefore appear yellow, whereas gaseous molecules of I
2
absorb yellow light (lower energy) and appear violet
Substance
State
F
2
Gas
Cl
2
Gas
Br
2
Liquid
I
2
Solid
Color Pale yellow Olivine Red-brown Purple-black
Color Light be absorbed
23

Olivine
Yellow
Orange
Red
Mauve
Color
Violet
Wavelength
400-450nm
Blue 450-480nm
Greenish blue 480-490nm
Blue-green 490-500nm
Green 500-560nm
Violet
Blue
Olivine 560-580nm
Yellow 580-600nm
Greenish blue Orange
Blue-green Red
600-650nm
650-750nm
E=hν=hc/λ E↑ λ↓
4) Solubility
○,1Cl
2
, Br
2
, I
2
have low solubility in water
○,2They are already soluble in some organic solvent like CCl
4
, CS
2
, ethyl ether and benzene
○,3 I
2
is quite soluble in solution of KI, HI or other iodides: I
2
+I
-
I
3
-
5) Toxic
6) Dissociation energy Cl
2
→Br
2
→ I
2
↓
2. Chemical properties
1) Oxidizing properties F
2
→ I
2
↓
○,1E θ
(F
2
/F
-
) >E
θ
(Cl
2
/Cl
-
) >E
θ
(Br
2
/Br
-
) >E
θ
(I
2
/I
-
)
○,2Fluorine is the most reactive of all the elements in the periodic table. It reacts with all the other elements except the lighter noble gases (He, Ne, Ar). Reactions with many elements are vigorous, and often explosive. The reactivity of the other halogens decreases in the order Cl>Br>I.
2) Reactions of the halogens with water
○,1 Fluorine is such a strong oxidizing agent that it oxidizes water to oxygen. The large negative free energy change indicates a strongly exothermic and spontaneous reaction: 2F
2
+2H
2
O
24

4HF+O
2
ΔG = -795 kJ·mol -1
The oxidation of water by chlorine is thermodynamically possible, but since the energy of activation is high, this reaction almost never occurs. In fact, another reaction occurs
○,2Disproportionation reaction
X
2
+H
2
O H
+
+ X
-
+ HXO
Substance Cl
2
K
θ 4.2×10 -4
Br
2
7.2×10
-9
I
2
2.0×10
-13
Section Three Hydrogen Halides
1. Physical properties
1) Hydrogen halides are colorless gases with penetrating odor; gaseous HF is very toxic
2) They will combine with the water in air to form acid vapor
3) Hydrogen halides are soluble in water
4) Melting and boiling points:
HCl→HBr→HI ↑ HF is abnormal
2. Chemical properties
1) Acidity
Substance HF HCl HBr HI
Melting point/ ℃ -83.1 -114.8 -88.5 -50.8
Boiling point/ ℃ 19.54 -84.9 -67 -35.38
Substance HF HCl HBr HI
K a

6.3×10 -4
1.74×10
8
1.5×10
10
3.5×10
11
2) Reducing properties: F
→Cl →Br →I ↑
3) Thermal stability
25

Substance HF HCl HBr HI
D
θ (HX,g)/kJ·mol -1
568.6 431.8 365.7 298.7
 f
H m

/kJ·mol -1
-271.1 -92.3 -36.4 +26.5
4) Preparation of hydrogen halides
HF: CaF
2
+H
2
SO
4
(strong)→CaSO
4
+2HF↑
HCl:NaCl+H
2
SO
4
(strong)→NaHSO
4
+HCl↑
HBr: PBr
3
+3H
2
O→H
3
PO
3
+3HBr↑ or 3Br
2
+2P+6H
2
O →2H
3
PO
3
+6HBr↑
HI: PBr
3
+3H
2
O→H
3
PO
3
+3HBr↑ or 3I
2
+2P+6H
2
O →2H
3
PO
3
+6HI↑
5) SiO
2
+ 4HF→ SiF
4
↑ + 2H
2
O
CaSiO
3
+6HF→SiF
4
↑+CaF
2
+3H
2
O
Section Four Halides
1. Properties and bond type
1) Bond type
○,1 Same period ○,2Same family
NaF MgF
2
AlF
3
SiF
4
PF
5
SF
6
Ionic type Covalent type
NF
3
PF
3
AsF
3
SbF
3
BiF
3
Covalent type Transition Ionic type
3 Same metal, different halogens eru ○,4Same metal, different oxidation number
AlF
3
AlCl
3
AlBr
3
AlI
3
Ionic type Covalent type
2) Properties
○,1 Solubility
SnCl
2
,PbCl
Ionic type
2
SnCl
4
, PbCl
4
Covalent type
26

△ ,1Most fluorides are insoluble. A few are soluble: AgF, PbF
2
, Hg
2
F
2
, fluoride of IA family
(except Li)
△ ,2Most halides (chlorine, bromine and iodine) are soluble. A few are insoluble: AgX, PbX
2
,
Hg
2
X
2
, CuX
○,2Hydrolysis properties
△ ,1 Halides of active metals do not hydrolyze, but F
-
hydrolyzes
△ ,2 Halides of middle active metals hydrolyze by step, for example: AlCl
3
, FeCl
3
, MgCl
2
△ ,2Halides of nonmetals hydrolyze completely, for example: SiF
4
, PCl
3
, PCl
5
, BCl
3
, BF
3
(except
CCl
4
, SF
6
)
△ ,3 Some halides hydrolyze to form a precipitate or basic salt
SbCl
3
+H
2
O → SbOCl↓ + 2HCl
BiCl
3
+H
2
O → BiOCl↓ + 2HCl
SnCl
2
+H
2
O → Sn(HO)Cl↓ + HCl
Section Five Oxyacids
1. Type
Chlorine, bromine and iodine form four series with formulae: HXO, HXO
2
, HXO
3
, and HXO
4
, in which the oxidation states of the halogens are Ⅰ , Ⅲ , Ⅴ , Ⅶ respectively
HXO
Hypohalous acid
HXO
2
Halous acid
HXO
3
Halic acid
HXO
4
Perhalic acid
Chlorous Bromous Iodous Hypochlorous Hypobromous Chloric bromic iodic Perchloric perbromic periodic acid acid acid acid acid acid acid acid acid acid acid
2. Chlorous acid and hypochlorites
1) Chlorous acid
○,1Preparation
27

Cl
2
2Cl
+ H
2
2
O
+ 2HgO + H
2
HClO + HCl
O 2HClO + HgO·HgCl
2
↓
○,2Properties
△ ,1 Weak acid, K a
θ =4.0×10 -8
△ ,2 Instability
2HClO
 
2HCl +O
2
3HClO HClO
3
+ 2HCl
△ ,3 Oxidizing properties
Page 318-319
( E

A
, E

B
)
: Elemental standard electrode potential diagrams
◇ ,
1
When HClO is an oxidant, the reductive product is Cl
-
◇ ,
2
E

A
( HClO / Cl

)

E
B

( ClO

/ Cl

)
◇
,
3
In acid medium, HClO + Cl
→Cl
2
2) Hypochlorites
○,1Preparation
Cl
2
+2NaOH NaClO+NaCl +H
2
O
Cl
2
+Na
2
CO
2Cl
3
2
+3Ca(OH)
NaClO+NaCl +CO
2
2
Ca(ClO)
2
+CaCl
2
·Ca(OH)
2
·H
2
O+H
2
O
○,2Properties
△ ,1 Oxidizing properties blue
Cr
3
 OH

  
Cr ( OH )
3

violet greyish -
OH green

  
Cr ( OH bright -
)
4

ClO green

  
CrO 4
2 yellow

2Cr 3+ +3ClO + 10OH →2CrO
4
2+3Cl +5H
2
O
△ ,2 Thermal stability
28

3KClO  KClO
3
+ 2KCl
3. Chloric acid and chlorates
1) Chloric acid
○,1Preparation
3HClO HClO
3
+ 2HCl
Ba(ClO
3
)
2
+H
2
SO
4
→2HClO
3
+BaSO
4
○,2Properties
△ ,1Strong acid
△ ,2Instability, when its content>40%:
3HClO
3
→2O
2
↑+Cl
2
↑+HClO
4
+H
2
O
△ ,3Oxidizing properties: strong oxidant
2HClO
3
+I
2
→2HIO
3
+Cl
2
↑
(5Cl
2
+I
2
+6H
2
O→2IO
3
-
+10Cl
-
+12H
+
)
2) Chlorates
○,1Preparation
△ ,13KClO

KClO
3
+ 2KCl
△ ,23Cl
2
+6KOH

KClO
3
+5KCl+3H
2
O
△ ,3Industrial method: electrolysis
2NaCl+2H
2
O
   is 
Cl
2
↑+H
2
↑+2NaOH
3Cl
2
+6NaOH NaClO
3
+5NaCl+3H
2
↑
NaClO
3
+KCl
  
KClO
3
+NaCl
○,2Properties
△ ,1 Thermal stability: KClO
3
>HClO
3
2KClO
3
 
3O
2
↑ + 2KCl
29

4KClO
3
3KClO
△ ,2 Oxidizing properties
4
↑ + KCl
◇ ,
1
The solid of KClO
3
is a strong oxidant, when mixed with S, P, C in given proportion, if the mixture is stroked, explosion will happen.
◇ ,
2
In the solution of water, KClO
3
has oxidation ability after acidification
ClO
3
-
+6I
-
+6H
+ →3I
2
+Cl
-
+3H
2
O
ClO
3
-
+Cl
-
+H
+ →Cl
2
+ H
2
O
BrO
3
-
+Br
-
+H
+ →Br
2
+ H
2
O
IO
3
-
+I
-
+H
+ →I
2
+ H
2
O
4. Perchloric acid and perchlorates
1) Perchloric acid
○,1Preparation:
KClO
4
+H
2
SO
4
  
HClO
4
+KHSO
4
NaClO
3
+H
2
O
    
NaClO
4
+H
2
↑
NaClO
4
+HCl→HClO
4
+NaCl
○,2HClO
4
2) Perchlorates
2Cl
2
↑+7O
2
↑+2H
Thermal stability: KClO
4
> KClO
3
2
O
O
A
D
HClO HClO
2
HClO
3
HClO
4
Weak acid Middle strong acid Strong acid Strongest acid
T
Acidity increases
S
Thermal stability increases (TSI)
Oxidizing ability decreases (OAD)
I
MClO MClO
2
MClO
3
MClO
4
30

Central contents:
1. General properties of carbon family and boron family
2. Properties of carbonic acid and carbonates, silicic acid and silicates
3. Properties of oxides of tin (Sn) and lead (Pb), properties of their hydrates; the trends of these compounds
4. Reducing properties of Sn (Ⅱ) and oxidizing properties of Pb (Ⅳ)
5. Properties and structure of diborane
6. Properties of boric acid and borates
7. Properties of AlCl
3
, Al
2
O
3
and Al(OH)
3
; structure of AlCl
3
8. Concept of vitriol and diagonal rule
9. Know how to identify Al
3+
, Sn
2+
and Pb
2+
Section One General Properties of Carbon Family
1. Nonmetal
→ metalloid
→ metal
2. Valence shell configuration: ns
2 np
2
3. Oxidation number
4. Type of crystal lattice
Section Two Main compounds of Carbon
Carbonic acid and carbonates
1. Properties of carbonic acid
1) Binary weak acid
2) Instability: H
2
CO
3
= CO
2
↑+H
2
O
2. Properties of carbonates
1) Solubility: most acid carbonates are soluble; most normal carbonates are insoluble except sodium carbonate, potassium carbonate and ammonium carbonate
△ ,1 Insoluble carbonates Solubility:
31

Acid carbonate > normal carbonate
For example: S
CaCO3
< S
Ca(HCO3)2
CaCO
3
+ H
2
O + CO
2
→Ca(HCO
3
)
2
△ ,2 Soluble carbonates Solubility:
Acid carbonates < normal carbonates
For example: S
Na2CO3
> S
NaHCO3
2) Hydrolysis
△ ,1 Normal carbonates
CO
3
2-
+ H
2
O HCO
3
-
+ OH
-
HCO
3
-
+ H
2
O H
2
CO
3
+ OH
-
△ ,2 Acid carbonates
3) M n+
+ CO
3
2-
HCO
3
-
+ H
2
O H
2
CO
3
+ OH
-
HCO
3
-
CO
3
2-
+ H
+
△ ,1S hydrate
< S carbonate
→ hydrate
For example: Fe
3+
, Al
3+
, Cr
3+
2Fe
3+
+CO
3
2-
+3H
2
O→2Fe(OH)
3
↓+3CO
2
↑
2Al
3+
+CO
3
2-
+3H
2
O→2Al(OH)
3
↓+3CO
2
↑
△ ,2S hydrate
≈S carbonate
→ basic carbonate
For example: Bi
3+
, Cu
2+
, Mg
2+
, Pb
2+
2Cu
2+
+2CO
3
2-
+H
2
O→Cu
2
(OH)
2
CO
3
↓+CO
2
↑
△ ,3S hydrate
>S carbonate
→ carbonate
For example: Ca
2+
, Sr
2+
, Mn
2+
, Ba
2+
Ca
2+
+ CO
3
2-
→ CaCO
3
↓
4) Thermal stability of carbonates
Cation: polarization↑ thermal stability↓
△ ,1 M n+
: 8 electron configuration
32

Sample
(Same charge)
Decomposition temperature/K
MgCO
M 2+
675
3
CaCO
3
1087
SrCO
r↑ polarization↓ thermal stability↑
3
1371
BaCO
3
1550
△ ,2 Same electron configuration, M n+ :
n↑ r↓ polarization↑ thermal stability↓, for example: Na
2
CO
3
is more stable than MgCO
3
, acid carbonates will be decomposed easily (H
+
r↓ polarization↑)
△ ,3 M n+ : 18, 18+2, 9~17 electron configuration, just like Fe 2+ , Cd 2+ , Pb 2+ etc. their carbonates are instability
Stability: Normal carbonates > acid carbonates > carbonic acid
5) 2H
+
+ CO
3
2-
=H
2
CO
3
→CO
2
↑+H
2
O
CaCO
3
+2H
+
=Ca
2+
+CO
2
↑+H
2
O
Section Three Silicon and Its Main Compounds
1. Silicic acid: xSiO
2
·yH
2
O x y Chemical formula Name
1
1
1
2
H
2
SiO
3
H
4
SiO
4
MetaSilicic acid silicic acid
2 1
2 3
H
H
2
6
Si
Si
2
2
O
O
5
7
3 2 H
4
Si
3
O
8
SiO
2
+ 4HF → SiF
4
+ 2H
2
O
SiO
2
+ 2NaOH  Na
2
SiO
3
+ H
2
O
SiO
2
+ Na
2
CO
3
 Na
2
SiO
3
+ CO
2
↑
Properties:
Dimetasilicic acid
Disilicic acid
Trimetasilicic acid
○,1Binary weak acid:
K
1
θ =2.5×10 -10
; K
2
θ =1.6×10 -12
○,2SiO
3
2 + 2H + → H
2
SiO
3
↓
33

Na
2
SiO
3
+2HCl→H
2
SiO
3
↓+2NaCl
SiO
3
2-
+2NH
4
+
+2H
2
O→H
2
SiO
3
↓+2NH
3
·H
2
O
2. Silicates
1) Preparation
SiO
2
+ 2NaOH  Na
2
SiO
3
+ H
2
O
SiO
2
+ Na
2
CO
3
 Na
2
SiO
3
+ CO
2
↑
2) Solubility: most of silicates are insoluble except M
2
SiO
3
(M: alkali metals)
3) Hydrolysis:
SiO
3
2 + H
2
O → HSiO
3
+ OH -
HSiO
3
+ H
2
O → HSiO
3
+ OH -
3)
4)
Different silicates of heavy metals have different color (p375)
Section Four Main Compounds of Tin and Lead
1. Properties of oxides and hydrates
1) Acid-base properties and trends
Acidity
Sn(OH)
2
SnO
Sn(OH)
4
SnO
2
Acidity
PbO
Pb(OH)
2
Pb(OH)
4
PbO
2
Basicity
2) React with acid or base
Pb
3
O
4
+4HNO
3
→2Pb(NO
3
)
2
+PbO
2
+2H
2
O
M(OH)
2
+ 2H
+
→ M
2+
+ 2H
2
O
M(OH)
4
+ 4H
+
→ M
4+
+ 4H
2
O
M(OH)
2
+ 2OH
-
→M(OH)
4
2-
Basicity
34

M(OH)
4
+ 2OH →M(OH)
6
2-
2) α-stannic acid and β-stannic acid
α-stannic acid: H
2
SnO
3
Sn
4+
+4OH
-
=Sn(OH)
4
↓

H
2
SnO
3
SnO
2
+NaOH→Na
2
SnO
3
H
 
H
2
SnO
3
β-stannic acid: H
2
SnO
3
3Sn+4HNO
3
+H
2
O→3H
2
SnO
3
+4NO
2. Salts of tin and lead
E
A
θ
/V
Sn
4+
0.154 Sn
2+
-0.136 Sn
PbO
2
1.46 Pb
2+
-0.126 Pb
E
B
θ
/V
[Sn(OH)
6
]
2-
-0.93[Sn(OH)
4
]
2-
-0.136Sn
PbO
2
0.28 PbO -0.580 Pb
1) Reducing properties of Sn (Ⅱ)
3[Sn(OH)
4
] 2+6OH +2Bi 3+ =2Bi↓+3[Sn(OH)
6
] 2 (Identification method for Bi 3+ )
SnCl
2
+ 2HgCl
2
= SnCl
4
+ Hg
2
Cl
2
↓
SnCl
2
+ Hg
2
Cl
2
= SnCl
4
+ 2Hg↓
Bi:black Hg
2
Cl
2
:white Hg:black
(Identification method for Hg
2+
and Sn
2+
)
2)Oxidizing properties of Pb(Ⅳ): PbO
2
PbO
2
+4HCl(strong) →PbCl
2
+Cl
2
↑+2H
2
O
PbCl
2
+2HCl(strong) →[PbCl
4
]
2-
+2H
+
5PbO
2
+2Mn 2+ +4H + →2MnO
4
+5Pb 2+ +2H
2
O
E
θ
(O
2
/H
2
O)>E
θ
(Sn 4+ /Sn 2+ )>E
θ
(Sn 2+ /Sn)
2Sn
2+
+ O
2
+ 4H
+
→ 2Sn
4+
+ 2H
2
O
Sn
4+
+ Sn → 2Sn
2+
3) Hydrolysis
SnCl
2
+ H
2
O → Sn(OH)Cl↓ + HCl
35

4) Solubility: Most salts of tin (Ⅱ) are soluble; most salts of lead (Ⅱ) are insoluble, but Pb(NO
3
)
2 and Pb(Ac)
2
are soluble, PbCl
2
can dissolve in hot water and PbSO
4
can dissolve in the solution of
NH
4
Ac
2Pb
2+
+2CO
3
2-
+H
2
O→[Pb(OH)]
2
CO
3
↓+CO
2
Pb
2+
+ CrO
4
2-
→ PbCrO
4
↓
Pb
2+
+ 2I
-
→ PbI
2
↓
PbI
2
+ 2I
-
→ [PbI
4
]
2-
3. Sulfides of tin and lead
Solvent
SnS
HCl


×
HNO
3


×
Na
2
S
×
Na
2
S
2

×
PbS
SnS
2
×
 ×
SnS
2
+ Na
2
S → Na
2
SnS
3
Na
2
SnS
3
+2H
+ →H
2
SnS
3
→SnS
2
↓+H
2
S↑
SnS + S
2
2-
→ SnS
3
2-
H
 
SnS
2
↓+H
2
S↑
3PbS+8HNO
3
→3Pb(NO
3
)
2
+3S↓+2NO↑+4H
2
O
PbS+4HCl(strong)→H
2
[PbCl
4
]+H
2
S↑
Acidic/amphoteric sulfide + Na
2
S/ (NH
4
)
2
S → salt of sulfoacid
H
 
sulfoacid → sulfide+H
2
S↑
1. Nonmetal → metal
Section Five General Properties of Boron Family
2. Valence shell configuration: ns
2 np
1
3. Oxidation number
B Al Ga In Tl
0, +3 0, +1, +3
Section Six Main Compounds of Boron
1. Hydrides of boron: B n
H n+4
, B n
H n+6
B
2
H
6
(diborane) :
36

1) Preparation
○,1 2BCl
3
+ 6H
2
→ B
2
H
6
+ 6HCl
○,24BCl
3
+3Li(AlH
4
)→2B
2
H
6
+3AlCl
3
+3LiCl
2) Structure
3) Properties:
B
2
H
6
(g)+3O
2
(g)→B
2
O
3
(s)+3H
2
O (g)
B
2
H
6
(g)+6H
2
O(l)→2H
3
BO
3
(aq)+6H
2
↑
B
2
H
6
+ 2CO → 2[H
3
B←CO]
B
2
H
6
+ 2NH
3
→ 2[H
3
B←NH
3
]
2. Oxyacids of boron
HBO
2
H
3
BO
3
xB
2
O
3
·H
2
O
1) H
3
BO
3
169
0 
HBO
2
300 0 
B
2
O
3
2) Structure of H
3
BO
3
3) Properties of boric acid
○,1 Boric acid is a monobasic acid and is quite weak, K a
θ
= 5.8×10
-10
○,2 H
3
BO
3
+3CH
3
OH→B(OCH
3
)
3
+3H
2
O
H
3
BO
3
+3C
2
H
5
OH→B(OC
2
H
5
)
3
+3H
2
O
37

3. Borates
H
3
BO
3
+NaOH
 
NaBO
2
+2H
2
O

9 .
6
4H
3
BO
3
+2NaOH
Na
2
B
4
O
7
·10H
2
O borax
Na
2
B
4
O
7
+7H
2
O
Chemical formula: Na
2
B
4
O
5
(OH)
4
·8H
2
O
Na
2
B
4
O
5
(OH)
4
·8H
2
O
 
400 0 
Na
2
B
4
O
7
878 0 
Na
2
B
4
O
7
(vitreous body)
B
4
O
7
2-
+7H
2
O 4 H
3
BO
3
+ 2OH
-
Na
2
B
4
O
7
+H
2
SO
4
+5H
2
O→4H
3
BO
3
+Na
2
SO
4
Na
2
B
4
O
7
+CoO→2NaBO
2
·Co(BO
2
)
2
blue
Na
2
B
4
O
7
+MnO→2NaBO
2
·Mn(BO
2
)
2
green
4. Halides of boron
1) Preparation
B
2
O
3
+3CaF
2
+H
2
SO
4
B
2
O
3
+3C+3Cl
2
2BF
3
+3CaSO
4
+3H
2
O

0 
2BCl
3
+3CO
2) Properties:
BF
3
BCl
3
BBr
3
Gas Liquid
Hydrolysis: BX
3
+3H
2
O→H
3
BO
3
+3HX
Liquid
BF
3
+HF → H[BF
4
]
Section Seve Main Compounds of Aluminum
1. Al
2
O
3
and Al(OH)
3
1) Al
2
O
3
preparation
α- Al
2
O
3
: 4Al+3O
2
2Al
2
O
3
γ- Al
2
O
3
: Al(OH)
3
500 0 
Al
2
O
3
+H
2
O
2) Al(OH)
3
preparation
Al
3+
+3NH
3
·H
2
O→Al(OH)
3
↓+3NH
4
+
BI
3
Solid
38

Al(OH)
3
+3HNO
3
→Al(NO
3
)
3
+3H
2
O
Al(OH)
3
+OH
→Al(OH)
4
-
Al(OH)
3
+2NaOH(s)

2NaAlO
2
+2H
2
O
2. AlCl
3
1) Structure
2) Properties
AlCl
3
·6H
2
O Al(OH)
3
↓+3HCl+3H
2
O
3) Preparation: 2Al + 3Cl
2
→ 2AlCl
3
4) Al
2
S
3
+6H
2
O→2Al(OH)
3
↓+3H
2
S↑
2Al
3+
+3CO
3
2-
+3H
2
O→2Al(OH)
3
↓+3CO
2
↑
3. Vitriol: M
Ⅰ
M
Ⅲ
(SO
4
)
2
·12H
2
O
For example: KAl(SO
4
)
2
·12H
2
O
KCr(SO
4
)
2
·12H
2
O r
M(Ⅰ)
>100pm: Na
+
,K
+
,Rb
+
,Tl
+
,NH
4
+ r
M(Ⅲ)
:50-70pm: Al 3+ ,Fe 3+ ,Cr 3+ ,Co 3+
4. Diagonal rule
Li Be B C N
Na Mg Al Si
Element
React with KOH
Oxyacids Acidity
B
KBO
2
+H
2
K
θ ≈10 -10
Si
H
2
SiO
3
+H
2
K
θ ≈10 -10
39

Stability
Oxysalts of heavy metals
Stable
Insoluble
(color)
Halides Hydrolysis (HBO
2
)
Si+ 2OH
-
+ H
2
O → SiO
3
2-
+ 2H
2
↑
Stable
Insoluble (color)
Hydrolysis (H
2
SiO
3
)
2B + 2OH
-
+ 2H
2
O BO
2
-
+ 3H
2
↑
1. Structure
1) HNO
3
, O
3
:∏
3
4
, NO
3
:∏
4
6
B
2
H
6
:3c-2e; Al
2
Cl
6
:3c-4e
2) (p-d)π bond: H x
RO y
(y>x)
H
2
SiO
3
, H
3
PO
4
, H
2
SO
4
, HClO
3
, HClO
4
3) Double bond:
H x
RO y
: H
2
CO
3
, HNO
2
4) Single bond: H- O- X
2. Properties of some elements
1) Metallic, nonmetallic
○,1Same period, from left to right, metallic↓, nonmetallic↑
○,2 Same Group: from up to down, metallic↑, nonmetallic↓
2) Inert electron pair effect
3) Diagonal rule
4) Properties of F
2
, Cl
2
, Br
2
, I
2
5) Properties of other simple substances
(1) Main group metals (S area):
○,1ⅠA,ⅡA: Strong reducing properties
○,2 React with acids: most of them can replace hydrogen atom and give out hydrogen gas
40

○,3 React with bases: most of them don’t react with bases, rare amphoteric elements can react with strong bases to form oxyacids and give out hydrogen gas, just like Al, Be, Ge, Sn etc.
○,4React with water: Alkali metals are so active that they can react with water to form bases and give out hydrogen gas
(2) Main group nonmetals (P area)
○,1 Most of these nonmetals have oxidizing properties and reducing properties
○,2 Most of these nonmetals don’t react with water under the normal temperature except halogens, but red-hot carbon can react with water steam
○,3Simple substances of iodine, sulfur, phosphorus, carbon and boron can be oxidized by strong
HNO
3
and strong H
2
SO
4
to form oxyacids, others do not react with acids
○,4Parts of nonmetals react with thick alkali:
◇ ,
1
Disproportionation reaction:
X
2
+2OH
→X -
+XO
-
+H
2
O
3X
2
+6OH - 5X +XO
3
+3H
2
O
3S+6OH 2S 2+SO
3
2+3H
2
O
4P+3OH
-
+3H
2
O 3H
2
PO
2
-
+PH
3
↑
◇ ,
2
Displacement reactions: Si, B
Si +2OH
-
+ H
2
O→SiO
3
2-
+2H
2
↑
2B+2OH
-
+2H
2
O 2BO
2
-
+3H
2
↑
○,5React with H
2
O
F
2
: displacement reaction
Cl
2
, Br
2
, I
2
: disproportionation reactions
3. Hydrides
ⅣA ⅤA ⅥA ⅦA
CH
4
NH
3
H
2
O HF
41

SiH
4
PH
3
H
2
S HCl
GeH
4
AsH
3
H
2
Se HBr
SnH
4
SbH
3
H
2
Te HI
○,1 Melting point and boiling point increase from up to down, but HF, H
2
O and NH
3
are abnormal
○,2 Thermal stability
Substance NH
3
H
2
O HF
Temperature/℃ 300 1200
3000
Decomposition 97% 0.02% -
Same period: thermal stability increases from left to right
Substance HF HCl HBr HI
Decomposition - 3273 1868 1073 temperature/ K
Same group: thermal stability decreases from up to down
○,3 Reducing properties:
Same period: Reducing properties decrease from left to right
Same group: Reducing properties increase from up to down
Reducing properties: HF< HCl< HBr< HI (HF and HCl don’t react with strong H
2
SO
4
, but HBr and HI react with strong H
2
SO
4
: SO
2
+ Br
2
; I
2
+ H
2
S)
○,4Acidic/basic properties of aqueous solution:
Same period: from left to right, acidity↑; NH
3
, H
2
O, HF
Same group: from up to down, acidity↑;
Acids H
2
S H
2
Se H
2
Te HF HCl, HBr, HI
K
θ
10 -7 10 -6 10 -4 Weak acid Strong acid, acidity↑
4. Halides
1) Same period: From left to right, ionic → covalence
2) Same group: From up to down, the trend of forming ionic compounds increases
3) Different oxidation numbers of same metal, generally, higher oxidation number compounds are covalence while lower oxidation number compounds are ionic
42

4) Different halides of same metal of same oxidation number, F→Cl→Br→I, ionic → covalence
5) Hydrolysis
5. Sulfides
Soluble Dilute
HCl
Strong
HCl
Solve in following solution
HNO
3
Aqua regia
PbS Ag
2
S
ⅠA ZnS
CdS CuS
MnS
SnS Cu
2
S HgS
NH
4
+ FeS
SnS
2
As
2
S
3
ⅡA*
CoS*
NiS*
Sb
2
S
3
As
2
S
5
Hg
2
S
Sb
2
S
5
CoS
Bi
2
S
3
NiS
K sp
θ
>10 -24 10 -25 ~10 -30 10 -30 ~10 -50 <10 -50
H
2
S
2
→ H
2
S↑ + S↓
SnS + S
2
2-
→ SnS
3
2-
4FeS
2
+11O
2
→2Fe
2
O
3
+SO
2
6. Oxides
1) Classification
Na
2
S
( NH
4
)
2
S
Na
2
S
2
Hydrolysis
SnS
As
As
Sb
Sb
2
2
2
2
S
S
S
S
2
3
5
3
5
SnS
Al
2
S
3
Cr
2
S
3
Oxidation number
-2
Type of compounds Examples
Normal oxides, oxyacids, oxysalts Na
2
O, CaO, H
2
O
-1
-1/2
-1/3
0
Peroxides
Hyperoxides
Ozonides
O
2
, O
3
Na
2
O
2
, BaO
2
, H
2
O
2
KO
2
KO
3
Properties:
A: Acidity oxides, SO
2
, NO
2
;
B: Alkaline oxides, Na
2
O, CaO;
C: Amphoteric oxides, BeO, Al
2
O
3
, As
2
O
3
;
43

D: Inert oxides, CO, NO
Bond type: ionic and covalent
7. Hydrates
1) R-O-H model
2) Ionic potential (Φ) Φ=z/r (P 295)
Φ
1/2
<7 7~10 >10
Properties Base Amphoteric Acid
Zn(OH)
2
: Φ 1/2 =5.2
3) The strength of oxyacids:
(1)Polyacids: K
1
θ
: K
2
θ
: K
3
θ ≈1:10 -5
:10
-10
(2) H n
RO m
[RO m-n
(OH) n
]: H
3
PO
4
: PO(OH)
3
; H
2
SO
4
: SO
2
(OH)
2
; HNO3: NO
2
(OH)
2
m-n K
1
θ
Strength of acids Examples
0 <10
-8
Weak acid HClO, H
3
BO
3
, H
3
AsO
3
1 10 -2 ~10 -4 Middle strong H
3
PO
4
, HNO
2
, H
2
SO
3
2
≈10 3
Strong H
2
SO
4
, HClO
3
, HNO
3
3
≈10 8
Very strong HClO
4
4) Thermal stability
5) Reducing/oxidizing properties
6) Classification
(1) Reducing/oxidizing properties
○,1Oxidizing acid: HClO, HClO
3
,, HClO
4
, strong H
2
SO
4
, H
2
S
2
O
8
, HNO
3
, H
3
AsO
4
○,2Reducing acid: H
3
AsO
3
, H
2
S
2
O
3
, H
2
S
○,3 H
2
SO
3
, HNO
2
○,4 H
3
PO
4
, H
2
SiO
3
, H
3
BO
3
(2) Solubility
○,1 Insoluble: H
2
SiO
3
, H
2
SnO
3
○,2 Sparsely soluble: H
3
BO
3
44

○,3 Soluble: sulfuric acid, nitric acid, phosphoric acid etc.
8. Oxysalts
1) Solubility
2) Hydrolysis
3) Carbonates
4) Thermal stability
○,1Same metal: if the oxyacid is more stable, the oxysalt will be more stable
○,2Normal salt > acid salt > acid
○,3Same acid radical: alkali metals >alkaline-earth metals > transition metals > ammonium
Na
2
CO
3
1800℃
CaCO
910℃
3
ZnCO
350℃
3
(NH
4
58℃
)
2
CO
3
○,4 K
2
SO
4
> K
2
SO
3
;
KClO
4
>KClO
3
>KClO
2
>KClO
○,5 CO
3
2-
, NO
3
-
, NH
4
+
5) Reducing/oxidizing properties
9. Important oxidizing agents and reducing agents oxidizing agents
ClO
ClO
3
X
2
（ H
+ ）
ClO +Cl +H +
（
H
+ ）
ClO
3
+Cl +H + products
X
-
Cl
-
Cl
2
Cl -
Cl
2
Oxidizing agents
NO
2
（ H
+ ） NO
HNO
3
NO
2
,NO,N
2
O,NH
4
+
H
3
AsO
4
NaBiO
3
（ H
+ ）
PbO
2
（
H
+ ） products
H
3
AsO
Bi
Pb
3+
2+
3 reducing agents
X
-
H
2
O
2
S
2
2-
SO
3
2-
S
2
O
3
2-
H
H
2
2
O
O
2
2
（
（
H +
OH -
）
）
H
2
O
OH
-
MnO
4
（
Cr
2
O
7
H
2-
+ ） Mn
Cr
2-
3+
H
3
AsO
SnCl
2
3 products
X
2
O
2
SO
2
SO
4
2-
SO
4
2-
I
2
: S
4
O
6
2-
H
3
AsO
4
SnCl
4
45

S
2
2-
SO
3
2-
H
2
SO
4
（ strong ）
S
2
O
8
2-
S
2-
S
SO
2
,S,H
2
S
SO
4
2-
10. Identification
11. Local name/popular name
（ H + ）
HgCl
2
Hg
2
Cl
2
Fe
3+
Bi
3+ （ OH
）
Hg
2
Cl
2
Hg
Fe
2+
Bi （ black ）
Sn(OH)
4
2-
Fe
2+
Cr(OH)
4
-
Sn(OH)
6
2-
Fe
3+
CrO
4
2-
S
2-
NO
2
-
S,SO
2
,SO
4
2-
NO
3
-
46