8
氢 Hydrogen
碱金属 The Alkali Metal
碱土金属 The Alkaline Earth Metals
89% in universe
d (H2) / d (H2O) ca,1/10
密度 d,0.089 g/L
H2 from?
? (a) CH4(g) + H2O(g) → CO(g) +3H2(g)
– Ni catalyst (synthesis gas合成气 )
? (b) CO(g) + H2O(g) → CO 2(g) + H2(g)
Fe/Cu catalyst
? C(s) + H2O(g) → CO(g) +3H2(g) (水煤气 )
? 2H2O(l) → 2H 2(g) + O2(g) (光解?)
(电解 )
? Zn(s) + 2HCl(aq) → ZnCl 2(aq) + H2(g)
(实验室 )
天
然
气
煤
Application of H2
? Haber process to ammonia (1.5× 108 Kg / y)
? 2H2(g) + CO(g) → CH 3OH(l)
? Cu2+(aq) + H2(g) → Cu(s) + 2H +(aq) (冶金 )
? H2 + …C=C… → …C -C… ( 氢化 )
燃料
人造黄油
冶金
肥料
原料
Vegetable oil to fat
植物油 氢化到 脂肪
火箭燃料
NaH(s) + H2O(l) → NaOH(aq) + H 2(g)
(a) Li
(b) Na
(c) K
(d) Rb,Cs
Li – Cs,Ba = Fe bcc
Ca,Sr ccp
Be,Mg hcp
体心立方
面心立方
立方密堆
六方密堆
Melting points
A Na-K alloy is a liquid at RT
? The first ionization energies,low
– Their compounds are ionic
? Ionization energies,low
– Excellent reducing agents
? The standard potentials,strongly negative
– They can even reduce the hydrogen in H2O
6Li(s) + N2(g) → 2Li 3N(s)
过氧化物
超氧化物
2M(s) + 2H2O(l) → 2MOH(aq) + H 2(g)
Li Na K
Na dissolved in liquid
NH3,
Higher Na 浓度,
bronze
Lower,ink-blue
Li2O Na2O2 KO2
1,Positive Cap
2,Seal (密封 )
3,PTC Device
4,Electrode Jell Roll
5,Electrolyte (LixCoyO2)
电解液
Lithium Cell
Li2CO3 an effective treatment for manic-depressive disorder
(狂燥 -郁闷 紊乱 )
Ca + H2O The 1st and 2nd 电离能
Be shows a hint of nonmetallic character,but the
other elements are all typical metals,The vigor of
reaction (反应活性 ) with water and oxygen increase
down the group,
两性的
Be compounds are very
TOXIC,
Highly polarizing
Small size
Moderately covalent
Tetrahedral BeX4
? MgO (mp2800° C),耐火、导热、绝缘
? Mg(OH)2,抗胃酸、泻药
? MgSO4,常用泻药 (Epsom salts)
叶绿素 a,b
(Mg 的最重要化合物 )
? CaO(s) + SiO2(s) = CaSiO3(l)
(炼铁时造渣,50 kg / Ton Fe)
? Ca5(PO4)3OH (s) + 4H3O+(aq) (牙齿腐蚀 )
= 5Ca2+(aq) + 3HPO4-(aq) + 5H2O(l)
Ca5(PO4)3OH (s) + F-(aq) (氟化 )
= Ca5(PO4)3F (s) + OH-(aq)
(1kg Ca / adult human body,mostly in bone)
ds 区元素
s区 ds区
最外层 ns1?2 ns1?2
次外层 (n?1)s2 or (n?1)s2(n?1)p6
(n?1)s2(n?1)p6 (n?1)d10
价层 ns1?2 (n?1)d10 ns1?2
离子的 2e构型 or 18e构型
电子构型 8e构型
s区与 ds区金属的电子构型的异同
同周期中 s区与 ds区元素
Z?(ds) > Z?(s),r(ds) < r(s)
① 金属活泼性 s区 > ds区
（ d电子屏蔽作用弱）
② 化合物中共价成分 ds区 > s区
③ 氧化态 Cu2+,Au3+
(与族数不一致 )
重要的铜矿,Cu(I)FeS2,CuCO3.Cu(OH)2,Cu(I)2S
黄铜矿,孔雀石,辉铜矿
铜的冶炼
? 选矿：浮选 (sulfide ores are wetted by oil)
? 冶炼,
pyrometallurgical (火法冶金 )
2CuFeS2(s) + 3O2(g) → 2CuS(s) + 2 SO2(g)
CuS(s) + O2(g) → Cu(l) + SO2(g) (+ CaO → CaSO 3)
(blister copper,泡铜 )
hydrometallurgical (湿法冶金 )
阳极,Cu(粗 ) – 2e = Cu2+ (阳极泥含,Pt,Ag,Au)
阴极,Cu2+ + 2e = Cu (99.95%)
工业炼铜
Cu,Ag,Au
立方密堆积 (ccp)
面心立方 (fcc)
Cu的性质
? Alloys,Cu-Zn,Cu-Sn,Cu-Ni 等；
? Activity of Cu,electrochemical series?
? Oxidation number,+1 (高温固相 ),+2 (aq),+3
2Cu+ = Cu2+ + Cu ?o = 0.521-0.153 = 0.368V
lgK = n?o/0.0592 = 6.276
要在水溶液中使 Cu2+→Cu +，降低 Cu+的浓度！
CuI(s),CuCl(s),Cu2O(s); [Cu(CN)2]-
Sulfate solution,[Cu(H2O)6]2+,pale blue
Solid CuSO4.5H2O,[Cu(H2O)4]2+,deeper blue
Copper corrodes (侵蚀 ) in
air to form a pale green
layer of basic copper
carbonate,
2Cu(s) + H2O(l) + O2(g) +
CO2(g) → Cu2(OH)2CO3(s)
+1.69 V
高温超导体
CuCO3 + Y2O3 + BaCO3 → YBa 2Cu3O6.5-7 (123)
铜蓝蛋白
(Role of Ceruloplasmin in Cellular Iron
Uptake,Chinmay K,Mukhopadhyay,Zouhair
K,Attieh,and Paul L,Fox Science 1998
January 30; 279,714-717,)
Ag的性质
? Ag + H+(aq) → H 2 ×
? Ag+ → Ag 2+ + Ag ×
? Oxidation number,+1,almost all Ag cpds
? 重要的盐,AgNO3
(除 AgNO3,AgF外,难溶 )
Au的性质
? Au,惰性，天然存在形式
? Alloys,pure Au,24-carat; Au-Ag alloys
? 高延展性,1g Au → 1m 2 → 2km
? Too noble to react
Au+(aq) + e- → Au(s) Eo = +1.69V
Au3+(aq) + 3e- → Au(s) Eo = +1.40V
NO3-(aq)+4H+(aq)+3e→NO(g)+2H 2O(l) Eo=+0.96V
Au(s) + 6H+(aq) + 3NO3-(aq) + 4Cl-(aq) →
[AuCl4]-(aq) + 3NO2(g)+3H2O(l)
4Au + 8NaCN + O2 + 2H2O = 4Na[Au(CN)2] + 4NaOH
2Na[Au(CN)2] + Zn = 2NaCN + Zn(CN)2 + Au (s)
8-carat,14-carat,white gold,18-carat,24-carat
(white gold – 6 parts Au and 18 parts of Ag)
俄国大教堂顶
The thin gold leaf coating
protects the structure
beneath from corrosion,
hcp
Zn的性质
? ZnS in sphalerite(闪锌矿 ),天然存在形式,常与铅伴生,
The ore is concentrated by forth flotation (浮选 ),and
the metal is extracted by roasting and then smelting
with coke,
2ZnS(s) + 3 O2(g) → 2ZnO(s) + 2SO 2(g)
ZnO(s) + C(s) → Zn(l) + CO(g)
? Zn 的金属活泼性, Zn(s)+2HCl(aq) → ZnCl 2(aq)+H2(g)
? 电镀在铁表面，与铜相似,Zn形成硬的 Zn2(OH)2CO3
? Zn的两性,Zn(s)+2OH-(aq)+2H2O(l)
→[Zn(OH) 4]2-(aq)+H2(g)
? Zn(OH)2的两性
ZnCl42- Zn(CN)42- ZnS
Cd的性质
? Cd,is obtained in a similar manner with Zn,
? Zn and Cd are silvery reactive metals,
Cd,more metallic,has a more basic oxide
? Toxic
? Oxidation number,Zn(II),Cd(II)
+2 in all their compounds
Hg的性质
? HgS in cinnabar (辰砂 )，天然存在形式, It is separated
from cinnabar by froth floation and then roasting,
HgS(s) + O2(g) → Hg(g) + SO2(g)
The volatile (挥发性 ) metal is distilled off and
condensed,
? Hg is unique in being the only metallic element that is
liquid at room temperature,室温液态！
? Hg + H+(aq) → H 2 × 但
Hg + H+ +NO3- → Hg 2+ + NO + H2O (Hg过量时,Hg22+)
? Oxidation number,+1 in Hg22+,+2。 与 +1 价 Ag一样，
Hg(I)也倾向于形成难溶盐。
Hg及其化合物的毒性
? Hg化合物，特别是有机化合物 剧毒 ！
(1952年在日本 Minimata，因含 Hg化合物
工业废水泄漏进浅海造成 52人死亡。在
海水中,Hg被变成 CH3HgSCH3,被鱼吸
收，而鱼是当地居民的主要食物。 )
? Hg蒸气是阴毒，因其效应是累积的。经
常暴露于低水平的 Hg蒸气下会使 Hg在体
内积累。其效应包括 记忆丧失 。
Summary
? Metals in Group 11 (铜族 ) and 12 (锌族 )
are easily reduced from their compounds
and have low reactivity as a result of poor
shielding by the d-electrons,
? Copper is extracted from its ores by either
pyrometallurgical (火法冶金 ) or
hydrometallurgical ( 湿法冶金 ) processes,
氢 Hydrogen
碱金属 The Alkali Metal
碱土金属 The Alkaline Earth Metals
89% in universe
d (H2) / d (H2O) ca,1/10
密度 d,0.089 g/L
H2 from?
? (a) CH4(g) + H2O(g) → CO(g) +3H2(g)
– Ni catalyst (synthesis gas合成气 )
? (b) CO(g) + H2O(g) → CO 2(g) + H2(g)
Fe/Cu catalyst
? C(s) + H2O(g) → CO(g) +3H2(g) (水煤气 )
? 2H2O(l) → 2H 2(g) + O2(g) (光解?)
(电解 )
? Zn(s) + 2HCl(aq) → ZnCl 2(aq) + H2(g)
(实验室 )
天
然
气
煤
Application of H2
? Haber process to ammonia (1.5× 108 Kg / y)
? 2H2(g) + CO(g) → CH 3OH(l)
? Cu2+(aq) + H2(g) → Cu(s) + 2H +(aq) (冶金 )
? H2 + …C=C… → …C -C… ( 氢化 )
燃料
人造黄油
冶金
肥料
原料
Vegetable oil to fat
植物油 氢化到 脂肪
火箭燃料
NaH(s) + H2O(l) → NaOH(aq) + H 2(g)
(a) Li
(b) Na
(c) K
(d) Rb,Cs
Li – Cs,Ba = Fe bcc
Ca,Sr ccp
Be,Mg hcp
体心立方
面心立方
立方密堆
六方密堆
Melting points
A Na-K alloy is a liquid at RT
? The first ionization energies,low
– Their compounds are ionic
? Ionization energies,low
– Excellent reducing agents
? The standard potentials,strongly negative
– They can even reduce the hydrogen in H2O
6Li(s) + N2(g) → 2Li 3N(s)
过氧化物
超氧化物
2M(s) + 2H2O(l) → 2MOH(aq) + H 2(g)
Li Na K
Na dissolved in liquid
NH3,
Higher Na 浓度,
bronze
Lower,ink-blue
Li2O Na2O2 KO2
1,Positive Cap
2,Seal (密封 )
3,PTC Device
4,Electrode Jell Roll
5,Electrolyte (LixCoyO2)
电解液
Lithium Cell
Li2CO3 an effective treatment for manic-depressive disorder
(狂燥 -郁闷 紊乱 )
Ca + H2O The 1st and 2nd 电离能
Be shows a hint of nonmetallic character,but the
other elements are all typical metals,The vigor of
reaction (反应活性 ) with water and oxygen increase
down the group,
两性的
Be compounds are very
TOXIC,
Highly polarizing
Small size
Moderately covalent
Tetrahedral BeX4
? MgO (mp2800° C),耐火、导热、绝缘
? Mg(OH)2,抗胃酸、泻药
? MgSO4,常用泻药 (Epsom salts)
叶绿素 a,b
(Mg 的最重要化合物 )
? CaO(s) + SiO2(s) = CaSiO3(l)
(炼铁时造渣,50 kg / Ton Fe)
? Ca5(PO4)3OH (s) + 4H3O+(aq) (牙齿腐蚀 )
= 5Ca2+(aq) + 3HPO4-(aq) + 5H2O(l)
Ca5(PO4)3OH (s) + F-(aq) (氟化 )
= Ca5(PO4)3F (s) + OH-(aq)
(1kg Ca / adult human body,mostly in bone)
ds 区元素
s区 ds区
最外层 ns1?2 ns1?2
次外层 (n?1)s2 or (n?1)s2(n?1)p6
(n?1)s2(n?1)p6 (n?1)d10
价层 ns1?2 (n?1)d10 ns1?2
离子的 2e构型 or 18e构型
电子构型 8e构型
s区与 ds区金属的电子构型的异同
同周期中 s区与 ds区元素
Z?(ds) > Z?(s),r(ds) < r(s)
① 金属活泼性 s区 > ds区
（ d电子屏蔽作用弱）
② 化合物中共价成分 ds区 > s区
③ 氧化态 Cu2+,Au3+
(与族数不一致 )
重要的铜矿,Cu(I)FeS2,CuCO3.Cu(OH)2,Cu(I)2S
黄铜矿,孔雀石,辉铜矿
铜的冶炼
? 选矿：浮选 (sulfide ores are wetted by oil)
? 冶炼,
pyrometallurgical (火法冶金 )
2CuFeS2(s) + 3O2(g) → 2CuS(s) + 2 SO2(g)
CuS(s) + O2(g) → Cu(l) + SO2(g) (+ CaO → CaSO 3)
(blister copper,泡铜 )
hydrometallurgical (湿法冶金 )
阳极,Cu(粗 ) – 2e = Cu2+ (阳极泥含,Pt,Ag,Au)
阴极,Cu2+ + 2e = Cu (99.95%)
工业炼铜
Cu,Ag,Au
立方密堆积 (ccp)
面心立方 (fcc)
Cu的性质
? Alloys,Cu-Zn,Cu-Sn,Cu-Ni 等；
? Activity of Cu,electrochemical series?
? Oxidation number,+1 (高温固相 ),+2 (aq),+3
2Cu+ = Cu2+ + Cu ?o = 0.521-0.153 = 0.368V
lgK = n?o/0.0592 = 6.276
要在水溶液中使 Cu2+→Cu +，降低 Cu+的浓度！
CuI(s),CuCl(s),Cu2O(s); [Cu(CN)2]-
Sulfate solution,[Cu(H2O)6]2+,pale blue
Solid CuSO4.5H2O,[Cu(H2O)4]2+,deeper blue
Copper corrodes (侵蚀 ) in
air to form a pale green
layer of basic copper
carbonate,
2Cu(s) + H2O(l) + O2(g) +
CO2(g) → Cu2(OH)2CO3(s)
+1.69 V
高温超导体
CuCO3 + Y2O3 + BaCO3 → YBa 2Cu3O6.5-7 (123)
铜蓝蛋白
(Role of Ceruloplasmin in Cellular Iron
Uptake,Chinmay K,Mukhopadhyay,Zouhair
K,Attieh,and Paul L,Fox Science 1998
January 30; 279,714-717,)
Ag的性质
? Ag + H+(aq) → H 2 ×
? Ag+ → Ag 2+ + Ag ×
? Oxidation number,+1,almost all Ag cpds
? 重要的盐,AgNO3
(除 AgNO3,AgF外,难溶 )
Au的性质
? Au,惰性，天然存在形式
? Alloys,pure Au,24-carat; Au-Ag alloys
? 高延展性,1g Au → 1m 2 → 2km
? Too noble to react
Au+(aq) + e- → Au(s) Eo = +1.69V
Au3+(aq) + 3e- → Au(s) Eo = +1.40V
NO3-(aq)+4H+(aq)+3e→NO(g)+2H 2O(l) Eo=+0.96V
Au(s) + 6H+(aq) + 3NO3-(aq) + 4Cl-(aq) →
[AuCl4]-(aq) + 3NO2(g)+3H2O(l)
4Au + 8NaCN + O2 + 2H2O = 4Na[Au(CN)2] + 4NaOH
2Na[Au(CN)2] + Zn = 2NaCN + Zn(CN)2 + Au (s)
8-carat,14-carat,white gold,18-carat,24-carat
(white gold – 6 parts Au and 18 parts of Ag)
俄国大教堂顶
The thin gold leaf coating
protects the structure
beneath from corrosion,
hcp
Zn的性质
? ZnS in sphalerite(闪锌矿 ),天然存在形式,常与铅伴生,
The ore is concentrated by forth flotation (浮选 ),and
the metal is extracted by roasting and then smelting
with coke,
2ZnS(s) + 3 O2(g) → 2ZnO(s) + 2SO 2(g)
ZnO(s) + C(s) → Zn(l) + CO(g)
? Zn 的金属活泼性, Zn(s)+2HCl(aq) → ZnCl 2(aq)+H2(g)
? 电镀在铁表面，与铜相似,Zn形成硬的 Zn2(OH)2CO3
? Zn的两性,Zn(s)+2OH-(aq)+2H2O(l)
→[Zn(OH) 4]2-(aq)+H2(g)
? Zn(OH)2的两性
ZnCl42- Zn(CN)42- ZnS
Cd的性质
? Cd,is obtained in a similar manner with Zn,
? Zn and Cd are silvery reactive metals,
Cd,more metallic,has a more basic oxide
? Toxic
? Oxidation number,Zn(II),Cd(II)
+2 in all their compounds
Hg的性质
? HgS in cinnabar (辰砂 )，天然存在形式, It is separated
from cinnabar by froth floation and then roasting,
HgS(s) + O2(g) → Hg(g) + SO2(g)
The volatile (挥发性 ) metal is distilled off and
condensed,
? Hg is unique in being the only metallic element that is
liquid at room temperature,室温液态！
? Hg + H+(aq) → H 2 × 但
Hg + H+ +NO3- → Hg 2+ + NO + H2O (Hg过量时,Hg22+)
? Oxidation number,+1 in Hg22+,+2。 与 +1 价 Ag一样，
Hg(I)也倾向于形成难溶盐。
Hg及其化合物的毒性
? Hg化合物，特别是有机化合物 剧毒 ！
(1952年在日本 Minimata，因含 Hg化合物
工业废水泄漏进浅海造成 52人死亡。在
海水中,Hg被变成 CH3HgSCH3,被鱼吸
收，而鱼是当地居民的主要食物。 )
? Hg蒸气是阴毒，因其效应是累积的。经
常暴露于低水平的 Hg蒸气下会使 Hg在体
内积累。其效应包括 记忆丧失 。
Summary
? Metals in Group 11 (铜族 ) and 12 (锌族 )
are easily reduced from their compounds
and have low reactivity as a result of poor
shielding by the d-electrons,
? Copper is extracted from its ores by either
pyrometallurgical (火法冶金 ) or
hydrometallurgical ( 湿法冶金 ) processes,
