1. Chapter 18 The d-block elements(Ⅱ)
§18.1 The elements of copper family
§18.2 The elements of zinc family

2. §18.1 The elements of copper family
18.1.1
The elemental substances
of copper family
18.1.2
The compounds of copper
The copper ions in aqueous
solution and the related reactions

3. 18.1.1 The elemental substances of copper family
1.Existence
Elemental substance：Cu, Ag, Au
Mineral: malachite：Cu2(OH)2CO3 (孔雀石)
argentite：Ag2S (辉银矿）
calaverite：AuTe2 (碲金矿)
2.Physical properties
•Color：Cu(violet red), Ag(white), Au(yellow)
•m.p and b.p are lower than that of other transition
metals
•Good conductor of heat and electricity, the order is
Ag>Cu>Au
•Good ductibility

4. Au and Ag can’t react with oxygen，but the reaction
3.Chemical properties
• reacts with oxygen Δ
2Cu + O2 ⎯⎯ 2CuO(black)→ Δ
2Cu + O 2 + H 2 O + CO 2 ⎯⎯→
Cu 2 (OH) 2 CO3 (green)
碱式碳酸铜
basic cupric carbonate
Au and Ag can’t react with oxygen，but the reaction
can occur in the presence of precipitating agent or
coordinating ligand

5. 2Ag+ 2H2S + O2 ⎯ 2Ag2S + 2H2 O⎯→ M = Cu, Ag,Au O2
4M + O 2 + 2H 2 O + 8CN ⎯ 4[M(CN) 2 ] + 4OH⎯→ − − −
4Cu + O 2 + 2H 2 O + 8NH 3 ⎯⎯→
4[Cu(NH 3 ) 2 ] (无色) + 4OH + − O2
colorless 2+
[Cu(NH 3 ) 4 ] (蓝) blue
Aqueous ammonia can’t be shipped in copper
containers.
2Ag+ 2H2S + O2 ⎯ 2Ag2S + 2H2 O⎯→
Silver turnS black after sever years.

6. Ag + Cl 2 ⎯ proceed slowly at r.t.⎯→
• Reacts with X2
r. t.
Cu + Cl2 ⎯⎯→ √
Ag + Cl 2 ⎯ proceed slowly at r.t.⎯→
Au + Cl 2 ⎯⎯→ proceed only at high temp.
Chemical reactivity order ：Cu>Ag>Au
• reacts with acids
①Cu, Ag, Au can’t displace +H
ions in dilute acid
(poor reduction ability)；

7. ②Forming precipitates or complexes can strengthen
reduction ability of the elemental substances；
2Ag + H 2S ⎯ Ag2S(s) + H 2 (g)⎯→
2Ag + 2H + 4I ⎯ 2AgI + H 2 (g)⎯→ + − - 2
2Cu + 2H + 4CS(NH2 ) 2 ⎯ 2Cu[CS(NH ) ] + H 2 (g)⎯→
thiourea 硫脲 + +
2 2 2
HCl
4M + O 2 + 2H 2 O + 8CN → 4[M(CN) 2 ] + 4OH − − −
M = Cu, Ag, Au

8. ③ Cu,Ag and Au are soluble in oxidizing acids
conc.)
Cu + 4HNO3 (浓) ⎯ Cu(NO3 )2 + 2NO2 + 2H2O⎯→
conc.)
Ag + 2HNO3 (浓) ⎯ AgNO3 + NO 2 + H 2 O⎯→
Cu + 2H 2SO 4 (浓) ⎯ CuSO 4 + SO 2 + 2H 2 O⎯→conc.)
conc.)
2Ag + 2H 2SO 4 (浓) ⎯ Ag 2SO 4 (s) + SO 2 + 2H 2 O⎯→
Au + 4HCl(conc.) + HNO3(conc.) → H[AuCl4] + NO(g) + 2H2O

9. The compounds of copper
18.1.2
The compounds of copper
1.The compounds of copper
Cu(I):
Compounds of Cu(I) are white or colorless,
no d-d transition
10,d
Cu(II):
Compounds of Cu(II) have colors,
d-d transition
9,d
Cu(III):
8,d
K3CuF6(light green), strong oxidizing agent
d-d transition

10. The compounds of copper
18.1.2
The compounds of copper
1.The compounds of copper
Cu(I):
Compounds of Cu(I) are white or colorless,
no d-d transition
10,d
Cu(II):
Compounds of Cu(II) have colors,
d-d transition
9,d
Cu(III):
8,d
K3CuF6(light green), strong oxidizing agent
d-d transition

11. The important compounds of copper：+2 +2 +2 +2 +1
oxidation
state
compound
氧化铜
CuO
硫酸铜
5HCuSO4· 2O
硝酸铜
Cu(NO3)2·
3H2O
Blue crystal
氯化铜
CuCl2·2H2O
氯化亚铜
CuCl
Color state
Brownish
black crystal
6.32~6.43
Blue crystal
Green crystal
White tetrahedron
crystal
3.53~3.68 -
density(g/cm 2 )
m,p, /℃
heated
situation
2.29
2.05
2.50
1148
1000℃时分
解为，加热时
能被 H2、CO
还原为 Cu2O
或 Cu
260℃以上变
为无水白色
CuSO4 粉末，
653℃以上分
解为 CuO 和
SO3
114．5℃熔
化，强热时分
解为碱式盐。
后变为。用和
乙醇溶液浸
湿的纸，干后
可自燃
137.8(0℃)在
湿空气中易
潮解，能溶于 乙醇
在 140~150℃
时在干燥的
HCl 气流中
加热可得无
水 CuCl2，呈
黄褐色，比重
为 3.05
77.0，能溶于
乙醚和丙醇
中，易溶于甲
醇和乙醇中
425℃熔化约 1000
℃沸腾
solubilty
(g/100gH2O)
(anhydrous
salt)
几乎不溶于
水(2.3× -3 -3
10 %)，易溶
于氨水
20.7，无水
CuSO4 易吸 水
1.5（25℃），难溶
于水。在空气中吸
湿后变绿，溶于氨 水

12. extremely unstable in solution
(1) Conpounds of Cu(I)
(i)
+:Cu
extremely unstable in solution
+2Cu
2++CuCu
， K
6=1.0×10
(ii) solid Cu(I) compounds show higher thermal
stability than that of solid Cu(II) ones
1100°C →
2CuO(s)
Cu2O(s, dull-red) + ½ O2
1800°C
2Cu(s) + ½ O2
1990 °C
CuCl 2 (s) ⎯ ⎯ ⎯ → CuCl(s) + Cl 2⎯ 2

13. (iii) Cu(I) compounds show low solubility in H2O
with an order for solubility below:
CuCl＞CuBr＞CuI＞CuSCN＞CuCN＞Cu2S
(iv) Cu(I) compounds react with O2：
200°C
2Cu 2 O + O 2 ⎯⎯ ⎯ → 4CuO⎯
(used to remove the trace of oxygen from) nitrogen
(v)is a soft acid, can form complexes with the
following ligands with stability in an order below: + Cu
-＜Br-＜I-＜SCN-＜NHCl
＜S2O33
2-＜CS(NH
)22
-＜CN
K f small
large

14. Cu(NH ) Cu(NH ) 0.161V Cu+ 0.52V Cu 0.447V [CuCl2] 0.232V Cu [CuCl2
(vi) The coordination number of Cu(I) in the
corresponding complexes is normally 2, sometimes 3 or 4.
(vii) Cu(I) complexes are not easy to be disproportionated
0.161V Cu+ 0.52V Cu
2+Cu -
2+Cu
0.447V [CuCl2] 0.232V Cu Δ
HCl) → CuCl2 ( dust-yellow土黄色）
Cu + 2+ Cu +
-(conc.4Cl -
dilution
[CuCl2 -]
CuCl( s, white) +
-Cl
0.013V
-0.128V Cu
Cu(NH ) 2+
3 4 +
3 2
Cu(NH )

15. Cu 2 O + H 2 SO 4 ⎯ CuSO 4 + Cu + H 2 O⎯→
(viii) solid Cu(I) compounds are not easy to be
disproportionated 沉淀物不易歧化
0.561V CuCl 0.117V Cu
2+Cu
0.161V Cu+ 0.52V Cu
2+Cu
c.f.:
Θ(right)＞EΘ(left)，solution：E
In an aqueous
+ disproportionatesCu
+2Cu
2++CuCu
， K
6=1.0×10
Cu 2 O + H 2 SO 4 ⎯ CuSO 4 + Cu + H 2 O⎯→
Cu 2 O + 2HCl ⎯ 2CuCl(s) + H 2 O⎯→

16. (viiii) Cu(I) complexes can adsorb CO and olefins：
- + CO-[CuCl2][CuCl2(CO)]
-[CuCl2]
+ C2H4
[CuCl2(C2H4
-)]
[Cu(NH3)2 + CO +]
[Cu(NH3)2
+(CO)]
[Cu(NH2CH2CH2OH)2 + C2H4 +]
[Cu(NH2CH2CH2OH)2(C2H4
+)]
Can be used to separate olefin from petroleum gas
用于石油气中分离出烯烃。

17. Cu 2 O + 2HCl ⎯ 2CuCl(s) + H 2 O⎯→
In a word, the stability of Cu(I) increases in the
presence of ligands and precipitating agent
Cu 2 O + 2HCl ⎯ 2CuCl(s) + H 2 O⎯→
VCu
CuI V Cu -
VCu
CuCl2 Cu
0.232V
VCu
CuCl Cu
0.117V
VCu(NH3)4
VCu(NH3)2 Cu

18. Cu 2 (OH) 2 CO 3 ⎯⎯ → 2CuO + CO 2 + H 2 O⎯
(2) Cu(Ⅱ) compounds
(i) Preparation and properties of CuO
Cu 2 (OH) 2 CO 3 ⎯⎯ → 2CuO + CO 2 + H 2 O⎯
200℃
entropy production 熵增
CuO + 2HNO 3 ⎯ Cu(NO 3 ) 2 + H 2 O⎯→
CuO + H 2SO 4 ⎯ CuSO 4 + H 2 O⎯→
CuO + 2HCl ⎯ CuCl 2 + H 2 O⎯→

19. Cu + 2OH → Cu(OH)2 (s) ⎯⎯⎯→CuO(s)+ H2O
(ii) properties of Cu(OH)2 and oxidizing ability of Cu(II)
Cu + 2OH → Cu(OH)2 (s) ⎯⎯⎯→CuO(s)+ H2O 2+ -
80~90℃
light blue浅蓝
Cu(OH) 2 +2OH (excess，浓) ⎯⎯ [Cu(OH) 4 ]→ − 2− Δ△
2[Cu(OH)4 ] + C6 H12O6 ⎯⎯→ 2−
Cu 2O(s,红) + C6 H12O7 + 2H 2O + 4OH −
Testing diabetes(糖尿病）：Red means disease
blue is not

20. + 4CN ⎯⎯ 2CuCN(s,white) + (CN) 2→ -CN− 2Cu2+
+ 4I ⎯⎯ 2CuI(s,white) + I 2→ −
2Cu -I -
CuI
2(clolorless) 2+
+ 4CN ⎯⎯ 2CuCN(s,white) + (CN) 2→
-CN−
[Cu(CN) 2 ] -
2Cu

21. (iii) structure and properties of CuSO4·5H2O
CuSO4 ⋅ 5H 2 O ⎯⎯ → CuSO4 ⋅ 3H 2 O ⎯⎯ →⎯⎯
102°C
113°C
CuSO4 ⋅ H 2 O ⎯⎯ → CuSO4⎯
258°C

22. (iv) hydrolysis of [Cu(H2O)6
2+]
2+2Cu
+2H2O
[Cu2(OH)2
2+ +]
+2H
K =
－10.610
(weak acid)
(v) identification of
2+：Cu
neutral
Cu2[Fe(CN)6] (s, red-brown红棕色
or tartish
2Cu2+ + [Fe(CN)6]4-
yellow prussiate of potash

23. (vi) The complexes of Cu(II):
its cordination number often is 4.
Cu(Ⅱ) complexes are less stable than Cu(I) ones
[CuCl4[CuCl2
lgK f
2+−2-Cu + 4Cl (浓) ⎯⎯ CuCl 4 (yellow)→
2-] -]
H2O 2+ 6
Cu(H2 O)
NH3 (适量)
NH3 (过量) 2+ 2+
3 4 Cu
Cu 2 (OH)2 SO4 (s)
Cu(NH )
pale blue浅蓝
Dark blue深蓝 4- 7 4- 7
P2 O (适量)
P2 O (过量) 2+ 6−
7 2 Cu
Cu 2 P2 O 7 (s)
Cu(P2 O )
blue蓝
pale blue浅蓝

24. 2. The compounds of Ag and Au
Some familiar compounds of Ag and Au
AgNO3
Colorless
Burgundy dust rhombus crystal
AgO
Ag2SO4
AuCl3
Deep red water
imbibition solid
Color state
White crystal -2
density(g/cm )
7.52
4.355
208.5 ，强热时
分解，混有机
物时见光变 黑
5.40
660 ， 1085 ℃
时分解为
Ag， SO 2 和 O2
2.44
m.p. /℃
300 ℃以上即
分解为 Ag 和 O2
Change with
heated
196
溶于少量水中呈
0.75(18 ℃ ) ，
红棕色，在大量水
1.4 （ 100 ℃），
中呈红黄色，易溶
易溶于 NH 3
于醇、醚中，在酸
水，不溶于醇
性溶液中稳定，中
类，较易溶于
性溶液中则析出
浓 H 2 SO 4 中 Au
0.002~0.005
(20 ℃)，微溶
于水，呈碱
性，易溶于
HNO 3 和 NH 3 水 中
2.22(20 ℃)，
水溶液呈中
性，易溶于甘
油，可溶于乙
醇，几乎不溶
于浓 HNO 3
solubility
(g/100gH 2 O)

25. Oxidation number +1：Ag2O， AgNO3， Ag2SO4
Oxidation number +2： AgO，AgF2
Strong
oxidant
Oxidation number +3： Ag2O3
(1)The features of the compounds of Ag(I)：
(i) Most compounds are insoluble
soluble：AgNO3, AgF, AgClO4
insoluble：AgCl, AgBr, AgI, AgCN, AgSCN,
Ag2S, Ag2CO3, Ag2CrO4。

26. (ii) Poor thermal stability 440° → 2Ag + 2NO + OC
300° → 2Ag + 1 O C
⎯Ag 2O ⎯⎯ ⎯2 2
(iii) Sensitivity to light 1
AgI: manual rainhν
⎯→ Ag + X 2 (X = Cl, Br, I)AgX ⎯
AgBr: photo2
(iv) Colors: mechanism of color here: charge-transfer
AgCl AgBr AgI Ag2O Ag2CrO4 Ag2S
white pale yellow yellow brown
brick red
black 白
浅黄 黄 褐 砖红 黑

27. Ag 2 O + 4NH 3 + H 2 O ⎯ 2Ag(NH ) + 2OH⎯→
4. Chemical reactions of Ag(I) ion
① 2Ag + 2OH ⎯⎯ Ag 2 O(s,brown) + H 2 O→ + -
②2Ag + 2NH 3 (trace) + H 2 O ⎯⎯→ Ag 2 O(s) + 2NH + + 4
Ag 2 O + 4NH 3 + H 2 O ⎯ 2Ag(NH ) + 2OH⎯→ +
3 2 -
Silver mirror reaction (银镜反应)：
2Ag(NH ) + HCHO + 3OH ⎯⎯→ +
3 2 -
HCOO + 2Ag ↓ +4NH3 + 2H2O -
2Ag(NH ) + C 6 H12 O 6 + 2OH ⎯⎯→ +
3 2 -
C 6 H12 O 7 + 2Ag ↓ +4NH 3 + H 2 O

28. Ag 2 CrO 4 + 4NH 3 ⎯ 2Ag(NH ) + CrO⎯→
⎯→③ 4Ag + Cr2 O + H 2 O ⎯ 2Ag 2 CrO 4 (s) + 2H + 2- 7 +
Ag 2 CrO 4 + 4NH 3 ⎯ 2Ag(NH ) + CrO⎯→ +
3 2 2- 4
2Ag + S2 O (little) ⎯⎯ Ag 2S2 O3 (s,white)→ ④ + 2- 3
H 2O
⎯⎯⎯ Ag 2S(s,black)→
Ag + 2S2 O (excess) ⎯⎯ [Ag(S2 O3 ) 2 ]→ + 2+ 3 3-

29. H 2SO 4 + Ag 2S(s,black ) Identification of S2O3 ion：2-
Ag2S2O3(s,white)+ H 2 O
H 2SO 4 + Ag 2S(s,black )

30. 5. Important reactions of
+Ag
NH3
HCl
Br AgBr(s) - +
3 2 +
Ag(NH ) Ag
AgCl 3− 3
S2 O
HNO 3 − - 2-
CN AgI(s) I Ag(S O ) 3−2 3 2 - I −
AgI2
S Ag(CN) −
Ag2S(s)2
-10(AgCl)=1.8×10
Ksp
K f ( Ag(NH ) ) = 1.67×10
3−13
K f ( Ag(S2 O 3 ) 2 ) = 2.9×10 +
3 2 7
Ksp (AgBr)=5.3×10-13
Ksp (AgI)=8.3×10-17
K f ( Ag(CN) ) = 2.48×10 − 2 20
Ksp (Ag2S)=6.3×10-50

31. AgI(s, yellow) ⎯→Ag + HCl ⎯ AgCl(s) + H ⎯→AgCl + 2NH3 ⎯ Ag(NH ) + Cl
6. Identification of
+ ionAg
HCl
Ag ⎯⎯ → AgCl(s,)⎯ +
AgCl(s,white)
HNO3
NH3
+⎯⎯⎯→ Ag(NH3 ) 2 -I
AgI(s, yellow)
⎯→Ag + HCl ⎯ AgCl(s) + H + +
⎯→AgCl + 2NH3 ⎯ Ag(NH ) + Cl +
3 2 −
⎯→Ag(NH ) + 2H + Cl ⎯ AgCl(s) + 2NH +
3 2 + − + 4
⎯→Ag(NH ) + I ⎯ AgI(s) + 2NH3 +
3 2 −

32. ? You know E 2 why can not oxidize to I2 when is added to
Ө(I /I-)=0.535V，EӨ(Ag+/Ag)=0.799V，
E 2
why
+Ag
can not oxidize -I
to I2 when -I
is added to
+ solution?Ag

33. §18.2 The elements of zinc family
The elemental substances
of zinc family
The compounds of zinc family
The zinc family ions in aqueous
solution and the related reactions

34. 18.2.1 The elemental substances of zinc family
Mineral: Blende(闪锌矿):ZnS; Cinnabar(辰砂) (HgS)
1. Physical properties：
•Low m.p：
Zn：419℃，Cd：321℃，Hg：-39℃
mercury is the only liquid metal at room temperature
•Forming alloys
Brass(黄铜)：Cu-Zn
Amalgam(汞齐)：Na-Hg, Au-Hg, Ag-Hg
mainly used for the extraction of noble metals
and as reductant for organic synthesis

35. • Reacts with O2：(stable in dry air)
10ns2(n-1)d
2. Chemical properties:
• Reacts with O2：(stable in dry air)
Moist atmosphere：
4Zn + 2O 2 + CO 2 + 3H 2 O ⎯⎯→
ZnCO3 ⋅ 3Zn(OH)2
碱式碳酸锌
Heated：
2Zn + O2 ⎯⎯ 2ZnO(s,white)→
stability decreases 稳 定 性 下 降
2Cd + O2 ⎯⎯ 2CdO(s,reddish brown)→
360℃ 2HgO(s,red, yellow)
470℃
2Hg + O2

36. • Reacts with S
ZnS( white白)
CdS( yellow黄)
M+S MS
HgS( red红，vermilion朱砂)
(black黑，cinnabar辰砂)

37. • Reacts with acids • Zinc reacts with→ M+
+(diluted)2H 2+ M
+ H2 (M = Zn, Cd)
Hg + 2H2SO4(conc.) → HgSO4 + SO2 + 2H2O
Hg + 4HNO3(conc.) → Hg(NO3) + 2NO2 + 2H2O
3Hg + 4HNO3(diluted, excess) → Hg(NO3) + 2NO + 4H2O
cold
6Hg (excess) + 8HNO3(diluted) → 3Hg2(NO3)2 + 2NO + 4H2O
• Zinc reacts with
-，NHOH 3
Zn + 2OH + 2H 2 O ⎯ Zn(OH) + H 2⎯→ − 2- 4
Zn + 4NH 3 + 2H 2 O ⎯ Zn(NH ) + H 2 + 2OH⎯→ 2+
3 4 −

38. 18.2.2 The compounds of Zinc family
The oxidation number of Zn and Cd: normally +2, their
properties are similar;
while oxidation number of Hg: +2, +1, many propertis
differing from those of Zn and Cd compounds .
1. Compounds of Zn and Cd
and(1) Hydrolysis of
H+[Zn(H2O)6][Zn(OH)(H2O)5]
2+Zn
2+Cd
K =
H+[Cd(H2O)6][Cd(OH)(H2O)5]
－9.0
K = 10
－9.6610

39. (2). Hydroxides of Zn and Cd
• Zn(OH)2 can react with both
-OH
and +H - -
OH (excess) 2+
2-Zn(OH) 2 (s,白)Zn
Zn(OH) 4 + H
H+398K
ZnO(s)
398K
Zn(OH) 2 (white）⎯⎯⎯ ZnO(white） H 2 O→+
OH (right)
ZnO can dissolve in both acid and base
• Cd(OH)2 can react only with +H - OH
523K CdO(s) 2+
Cd(OH) 2 + Cd H
523K
Cd(OH) 2 (white）⎯⎯⎯ CdO(white） H 2 O→+

40. + H 2S + 2NH 3 ⎯ ZnS(s) + 2NH⎯→ Zn
(3). Sulfides of Zn and Cd + −1
Zn + H 2S ⎯⎯⎯⎯⎯⎯ ZnS(s, white) + 2H→ 2+
c (H ) < 0.3mol⋅L + 2+
+ H 2S + 2NH 3 ⎯ ZnS(s) + 2NH⎯→ + 4 Zn
Cd + H 2S 2+
CdS(s,yellow)
++2H
insoluble in diluted acid; 2+
a characteristic reaction to identify Cd
ZnSO 4 (aq) + BaS(aq) ⎯⎯ ZnS ⋅ BaSO 4 (s,white)→
lithopone锌钡白(立德粉)

41. (3). Complexes of Zn and Cd
2+, Cd2+ can react with X-，NH ，CN- to formZn 3
2+, [Cd(NH ) ]2+, [Zn(CN) ]2-,complexes [Zn(NH3)4]3 44
2-, [CdCl ]2- et al[Cd(CN)4]4
Features: coordination number 4，stable，
tetrahedral configuration，normally corless.
2+ are more stable than those of Zn2+Complexes of Cd
when ligands are the same
----ClBrIE.g.:F
2+Zn
lgK f1
0.73
0.43
-0.60
<-1
2+Cd
lgK f1
0.46
1.95
1.75
2.10

42. Identification of ion (basic condition) 1 2 二苯硫腙
2+Zn
ion (basic condition) 1 2
二苯硫腙
pink (in water): upper layer
(CCl4溶液)
brown (in CCl4): lower layer
green

43. Hg2Cl2：calomel(甘汞),Cl − Hg − Hg − Cl
2. Compounds of mercury
(1). Compounds of Hg(I)
Hg2Cl2：calomel(甘汞),Cl − Hg − Hg − Cl
Linear covalent molecule with a sweet taste,
insoluble in water and non-toxic
Hg 2(NO3)2: ionic compound and soluble in water.

44. HgCl2：mercury chloride (升汞), Cl
(2).Compounds of Hg(II)
229pm
229pm
HgCl2：mercury chloride (升汞), Cl Hg Cl
Linear covalent molecule, sublimation, soluble to
a small extent in water, toxic
HgBr2, HgI2: Same situation as HgCl2
HgF2: ionic comp.
Hg(NO3)2: ionic compound and soluble in water, toxic.
HgO: ionic compound and soluble in water, it
decomposes into Hg and O2 at 400 ℃.

45. (3) The important reactions of mercury
(i). Reacts with
-OH
ion
1OH400°C
⎯⎯⎯→ HgO(s,yellow) ⎯⎯⎯⎯ Hg(s) + O 2→ 2
-OH
⎯⎯ Hg 2 O(s,brown) ⎯⎯ HgO(s) + Hg→→ − 2+ Hg 2+ 2 Hg
(ii). Reacts with
2-S
ion
Hg + S ⎯⎯ HgS(s,black)→ 2+ 2−
Hg + S ⎯⎯ HgS + Hg→ 2+ 2 2-
3Hg + 2NO + 2S ⎯⎯ Hg(NO3 )2 ⋅ 2HgS (s,yellow)→ 2+ - 3 2−
Hg(NO3 )2 ⋅ 2HgS + S ⎯⎯ 3HgS(s,black) + 2NO→ 2- - 3

46. Hg + Hg = Hg K = 80 0.9083V Hg2 0.7955V Hg HgS -0.758V Hg2S -0.598V Hg2+
0.7955V Hg
Hg22+ no disproportionation, different from Cu+
Hg + Hg = Hg 2+ 2+ 2
K = 80
HgS V
Hg2S V Hg
ion can not disproportionate, while it can
when forming solid or complexes (except Hg2Cl2)
+So,Hg
• dissolution of HgS
HgS： Ksp
-52=1.6×10
⎯→3HgS + 2HNO HCl ⎯ 3H 2 [HgCl 4 ]
+ 2NO + 3S + 4H 2 O
HgS + S 2-
2-⎯ HgS2⎯→

47. Hg(SCN) (aq, colorless)
(iii) Reacts with HNO3：
HgO + 2HNO3Hg(NO3 ) 2 + H 2 O
Hg + 4HNO3 (浓)
Hg(NO3 ) 2 + 2NO2 + 2H 2 O
Hg + Hg(NO3 ) 2
Hg 2 (NO3 ) 2
(iv) Reacts with
-SCN ： 2+
+ 2SCN - Hg
Hg(SCN) 2 (s)
Hg(SCN) 2 + 2SCN -
Hg(SCN) (aq, colorless) 2- 4

48. HgCl 2 + 4NH 3 ⎯ Hg(NH )⎯→ + 2Cl → HgCl2 + 2NH3 [ Hg (NH3)2Cl2]
(v). Reacts with NH3
HgCl2 + 2NH3
NH2 HgCl(s)+ NH + Cl + 4 -
氨基氯化汞
NH4Cl →
HgCl2 + 2NH3
[ Hg (NH3)2Cl2]
NH4Cl
[Hg(NH3) 2 Cl 2] + 2NH 3
[Hg(NH3 ) 4 ]Cl2
Hg(NH3)4 can form only in NH3.H2O in the
presence of excess NH4Cl 2+
NH4Cl
HgCl 2 + 4NH 3 ⎯ Hg(NH )⎯→ 2+
3 4
+ 2Cl −

49. HgO ⋅ NH 2 HgNO3 (s,white ) + 3NH
Hg + NO + 4NH 3 + H 2 O ⎯⎯→ 2+ - 3
HgO ⋅ NH 2 HgNO3 (s,white ) + 3NH + 4
Addition of NH4 is favorable for straight-forward reaction +
HgO ⋅ NH2 HgNO3 + 3NH + 4NH3 ⎯⎯→ + 4 2+
3 4
+ NO + H 2O - 3
2Hg(NH )
2Hg + NO + 4NH3 + H2O ⎯⎯→ 2+ 2 - 3
HgO ⋅ NH2 HgNO3 (s,white ) + 2Hg + 3NH + 4
Hg2Cl2 + 2NH3 → NH2HgCl(s)+ Hg(l)+ NH4Cl

50. (vi). Reacts with ions Hg + 2I - HgI2 + 2I )HgI2 (s, golden red金红色） 2-2+ -
)HgI2 (s, golden red金红色） 2-
)HgI4 (aq, colorless
HgI4
2-:
Nessler reagent，usable to identify NH4 + Hg
NH + 2[HgI4 ] + 4OH + 4 2- - O
NH2 I(s, reddish brown) Hg
+ 7I + 3H 2O -
Hg + 2I 2+ 2
HgI2 + Hg - )
Hg 2 I 2 (s, grass green) - I
HgI + Hg 2- 4

51. (vii). Identification of ion
2+Hg
ion
2Hg + Sn + 8Cl ⎯⎯ Hg 2Cl2 (s,white) + SnCl→ 2+ 2+ - 2- 6
Hg 2Cl2 (s) + Sn + 4Cl ⎯⎯ 2Hg(l,black) + [SnCl6 ]→ 2+ - 2-
In reverse, HgCl2 can be used to identify
2+Sn
(4) Complexes of Hg 汞的配合物
[Hg(SCN)4
2-,]
[Hg(NH3)4
2+,]
[HgI4
2-,]
[HgCl4
2- etc]
characters: coordination number often is 4, diamagnetic Θ≈ Θ Θ
Kf3 Θ
Kf1
Kf2 >>
and Kf4
K f1
K f2
K f3
K f4
[HgCl4
2-]
6.7410
6.4810
0.8510
1.0010