COURSE SYLLABUS

Inorganic chemistry 1 – Representative elements (3 credits)

Chapter I. Periodic law and periodic table (5 sessions)
Chapter II. Hydrogen, oxygen and water (5 sessions)
Chapter III. The group IA (1) elements (4 sessions)
Chapter IV. The group IIA (2) elements (4 sessions)
Chapter V. The group IIIA (13) elements (4 sessions)
Chapter VI. The group IVA (14) elements (3 sessions)
Chapter VII. The group VA (15) elements (6 sessions)
Chapter VIII. The group VIA (16) elements (6 sessions)
Chapter IX. The group VIIA (17) elements (7 sessions)
Chapter X. The group VIIIA (18) elements (1 sessions)

Chapter I. Periodic law and periodic table

CHAPTER II. HYDROGEN, OXYGEN, WATER, HYDROGEN

PEROXIDE
A. Hydrogen
2.1. Characteristics of atom and ion.
Electronic configuration of hydrogen 1s1. Three possible trends::
- It can lose an electron to give the proton H+. Superficially, this resembles to the
alkali metals which can lose an electron to give M+ (ns2np6)
Hg - 1e = Hg+ I = 13,6eV (1312 kJ/mol; 1eV = 23,06kcal, 1cal = 4,18j)
The ionization energy of alkali metals are listed in below table:
Atom Li Na K Rb Cs

I1 (eV) 5,39 5,14 4,34 4,18 3,89

The ionization energy of hydrogen is about 3 times higher than those of alkali, thus
the ability of giving 1e of hydrogen is much more difficult than those of alkali. The
hydrogen atom has a high ionization energy and in this it resembles the halogens
rather than the alkali metals.
Removal of the 1s electron leaves a bare proton which, having a radius of only
about 1.5 x 10-3 pm (1.5 x10-13cm), much smaller than those of alkali (normal atomic and
ionic sizes, r = 10-8cm).
Electron density = charge of ion / volume of ion
+
H has high electron density (about 5 times higher than alkali). So it is not a stable
chemical entity in the condensed phase or compounds in which the single proton is
present as a cation are not likely to form but many compounds of alkali elements are
essentially ionic and contain the singly charged ions. However, when bonded to other
species H+ is well known in solution and in solids, e.g. H3O+, NH4+, etc.
- It can gain an electron to give H- with the helium configuration ls2. Superficially, this
resembles to the halogens which can gain an electron to give an inert-gas configuration
ns2np6.
Hg + 1e = Hg- ΔH0 = - 72kj/mol or AH = - 0,72ev.
The electron affinitive of halogens are listed in below table:
Atom F Cl Br I At

Electron affinitive, eV - 3,58 - 3,81 - 3,56 - 3,29 - 3,29

AH is substantially smaller than the value for halogens (about 1/5 AX). Thus the
ability of gaining 1e of hydrogen is much more difficult than those of halogens.
The hydride ion (H-) has the same electron configuration as helium but is very
unstable because the single positive charge on the proton must now control the 2
electrons. The hydride ion is thus readily deformable and it only exit in crystals of
metallic hydrides like KH, CaH2. While the halide ions X- is quite stable, they can exit
singly in solution.
So the majority of hydrogen compounds contain hydrogen that has neither lost nor
gained an electron.
- Combining the electron to form covalent bond is the main trend of H: Most simple
hydrogen compounds are covalent as a result of the hydrogen atom sharing an electron
pair. Because the 1s level is singly occupied in the hydrogen atom, it also resembles in
many ways the halogens, which also require a single electron to complete the valence
shell.
In the periodic table, hydrogen can be placed in 2 first positions of column 1A and
column 7A
* Reasons for placing in column 1A (alkali column):
+ Suitable: like alkali, H have 1e at outermost of electron shell and can lose an electron
+ Unsuitable: The value of IH is about 3 time higher than alkalis, H+ is not a stable
chemical entity in the condensed phase unless associated with other atoms or molecules
while M+ can exit singly in both solution or solid states.
* Reasons for placing in column 7A (halogen column):
+ Suitable: The value of IH resembles the halogens, like halogens H can gain an electron
and ion H- can exit singly in metallic hydrides like halide salts.
+ Unsuitable: AH is about 1/5 Ahalogen. The halide ions X- is quite stable, they can can exit
singly in solution, while H- is unstable, it only exits in crystals of metallic hydrides.
a. Besides, hydrogen has an unique ability of creating hydrogen bonding (close
association with 2 other atoms in linear array). It can penetrate metals to form
nonstoichiometric metallic hydrides, though not unique to hydrogen, is one of its more
characteristic properties as is its ability to form nonlinear hydrogen bridge bonds in
many of its compounds. The reason for these is that hydrogen has no other electrons
in its .
H H H
B B and (CO)5Cr – H – Cr(CO)5
H H H
2.2. MOLECULAR STRUCTURE- ELECTRODE POTENTIAL
2.2.1. Molecular structure
The H–H bond energy is about 435 kJ/mol, the bond length of H-H is of 0,74Ao,
this magnitude of bond length indicate that valence radius of H atom of 0,37Ao.
Bond C-C N-N O-O F-F Cl-Cl

Bond energy, kJ/mol 347 169 140 159 242

Since H2 is formed from the overlapping of 2 sAO which have the lowest size and
small energy. So it is comparatively nonreactive at room temperature
Comments: ion H- has high heat of formation that can be balanced in reactions with
very high heat of formation and high heat of crystallization.This explains why H- can
only be found in hydrides of alkaline and alkaline earth metals.
H+ is characterized by a large heat of formation, larger than binding energy, so
bonds in which H is positively charged, are covalent. Even in H-F bond, the percent of
covalent bond is 54%. freeH+ is only formed when discharging H2.
2.2.2.Reduction potential
2H+ + 2e → H2↑ EO = 0,0V (pH < 7)
2H+ (10-7M) + 2e →H2↑ EO = - 0,414V (pH = 7)
2H2O + 2e → H2 + 2OH- EO = -0,828V (pH > 7)
2.3. OCCURRENCE AND ISOTOPES
2.3.1. Occurrence:
Hydrogen is the fuel for reactions of the Sun and other stars (fusion reactions)
 Hydrogen is the lightest and most abundant element in the universe. About 70%-
75% of the universe is composed of hydrogen by mass. All stars are essentially large
masses of hydrogen gas that produce enormous amounts of energy through the fusion of
hydrogen atoms at their dense cores. In smaller stars, hydrogen atoms collided and fused
to form helium and other light elements like nitrogen and carbon(essential for life). In
the larger stars, fusion produces the lighter and heavier elements like calcium, oxygen,
and silicon.
On Earth, hydrogen is mostly found in association with oxygen; its most abundant
form being water (H2O). Hydrogen is only .9% by mass and 15% by volume abundant on
the earth, despite water covering about 70% of the planet. Because hydrogen is so light,
there is only .5 ppm (parts per million) in the atmosphere, which is a good thing
considering it is EXTREMELY flammable.
2.3.2. Occurrence.
it has 3 isotopes and it is the only elements whose each isotopes is called differently:
1 2 3
1H (Protium H) 1 H (Deuterium D) 1 H (Tritium T)

99,984% 0,016% 10-4%

H and D are stable, T is radioactive. Their chemical properties are similar. The
difference is the rate of the reaction. D forms compounds similar to those of H, but with
different biochemical properties. exp H2O can be drunken but D2O can’t be.
2.4. Physical properties
-At room temperature, it is a colorless, odorless, tasteless gas. As the lightest gas, it
is easy to diffuse and therefore thermal conductive. it is used to cool down hot matter.
- H2 is stable, due to its small size, it is difficult to be polarized. Due to its small
mass, melting point (-259,1oC) and boiling point (-252,6oC) are very low.
- Hydrogen is slightly soluble in water and organic compound.
2.5. CHEMICAL PROPERTIES
2.5.1 Oxidization ability: when reacting with strong reducing agents such as alkaline
and alkaline earth metals with reduction potential less than -2,25(E H2/2H- )
Some metals Na, K, Ca, Ba…directly react with H2 gas:
2Na + H2 → 2 NaH (heated)
Mg + H2 → MgH2(heated)
2.5.2 Reducibility
- with non metals
with C: C + H2 CH4 (Ni, 500-1000oC)
2C + H2 C2H4 (Ni, 3000oC)
 with N2: N2 + 3H2 2NH3 (Fe, 450-500oC)
with O2: Oxygen starts to react with hydrogen at 300oC or when there exists a
catalyst. the reaction is extremely exothermic and can be explosive:
2H2 + O2 → 2H2O = -241,82kJ/mol
Mixture of 2 part of H and 1 part of O is an explosive mixture. However, at room
temperature, there is no reaction because the bonds in H2 O2 are stable.
with S:
when passing H2 through melted S, H2S is formed at T = 300oC.
H2 + S → H2 S = -20,08 kJ/mol
The reactions is a lot slower than that between H2 and O2
With halogens:
All halogen reacts with H2 to form HX.
with oxides of metals:
H2 can reduce oxides of some metals (based on ΔG: ΔGH2OK = -54,6 Kcal/mol.)
CuO +H2 → Cu + H2O
Fe2O3 + 3H2 → 2Fe + 3H2O (1)
PbO + H2 → Pb + H2O (2)

G , (1) = 3 G (H2O) - G (Fe3O4) = +57 kJ/mol

G , (2) = G (H2O) - G (PbO) = -40 kJ/mol

Hydrogen reduces PbO at 250 C; HgO at 100oC; CuO at 150oC; ZnO at 1000oC.
o

with H2SO4: H2 + H2SO4 → SO2 + 2H2O

2.5.3. Addition reaction
Hydrogen can be added to inorganic and organic compounds. Catalysts can be Ni
and other metals of group VIII such as Pt, Rh, Pd, Ru because they are able to absorb H2.
2.6. PREPARATION
2.6.1. Preparation
• In the lab
- Let Zn, Fe react with diluted HCl or H2SO4 in Kipps apparatus.
- dissolve Al, Zn, Sn in basic solutions:
2Al + 2OH- + 6H2O → 2[Al(OH)4]- + 3H2↑
Zn + 2OH- + 2H2O → [Zn(OH)4]2- + H2↑
2Sn + 4OH- + H2O → SnO22-+ SnO32- + 3H2↑
- Let alkaline metals react with water
 - Hydrolyze hydrides:
CaH2 + 2H2O → Ca(OH)2 + 2H2↑
• In industry
- Electrolyze NaOH hay KOH 25% with graphite electrodes. This is expensive
- Preparation from carbon at high temperature:.
C + H2 O CO + H2 (1000oC) = 130kJ
Pass the mixture (CO and H2) and excess water vapor through Fe2O3 catalyst at 500oC:
CO + H2O CO2 + H2 = -42kJ.
wash the mixture of CO2, H2 and CO with water at 25at, CO2 dissolves, leaving
hydrogen. Excess CO2, CO are cleaned with NaOH solution and and solution of Cu2CO3
in NH3:
CO2 + 2NaOH → Na2CO3 + H2O
Cu2CO3 + NH3 → [Cu(NH3)4]2+
[Cu(NH3)4]2+ + CO → [Cu(NH3)4(CO)]2
- From natural gases:
+ Heat the mixture of CH4 and water to 8000C, pass these mixture through Ni catalyst
H2O + CH4 → CO + 3H2
CO and H2 are processed as above.
+ un-completely heat O2: 2 CH4 + O2 → 2CO + 4H2
2.6.2. USES
- to fill gas balloons. - to prepare ammonium.
- to prepare HCl - to cool down matters. - H2 is the future fuel
2.7. ATOMIC HYDROGEN - NEWLY PREPARED HYDROGEN - ACTIVE
HYDROGEN
isolate H atoms is formed by discharging the air slightly: H2 → 2H
The process of combining H atoms is exothermic.
Reduction potentials are:
H+ + 1e → H EO = -2,10V (acid environment)
- O
H2O + 1e → H + OH E = -2,93 V (basic environment)
Isolate H can form hydrides with metals and non metals at room temperature, react
with oxides of many metals, push some metals (Cu, Ag, Pb) out of their salt solution, and
join some other reactions that Hydrogen molecule can not.
"Newly prepared" hydrogen is atomic hydrogen formed in chemical reactions or
electrolysis. These atoms haven’t combined to form H2↑. This atoms can reduce nitrogen
compounds to amine, Fe3+ to Fe2+, MnO4- to Mn2+, Cr2O72- to Cr3+.

exp: + H+ + H2 no reaction
when 1 piece of Zn is added to the solution, the color dissappears
Zn + 2H+ → Zn2+ + 2H
MnO4- + 3H+ + 5H → Mn2+ + 4H2O
"Active hydrogen" is atomic H formed from molecular hydrogen from discharging
2.8. HYDRIDES:
2.8.1. Ionic Hydrides
H is in H- state which has 2 e but only 1 proton. It forms hydrides solid compounds
with Li, Na, K, Rb, Cs, Ca, Ba,Sr, exp KH và BaH2
1/2H2(k) + e = H-(k) ΔH = 152kj/mol
Ionic hydrides are crystalline solids, similar to salts.
Due to Ionic bonding:
- hight melting and boiling points.
-electronic conductive when melted.
-Electrolysis of hydrides of alkaline metals, H2 is released at the positive electrode.
- thermally unstable. except for LiH, all ionic hydrides dissociates before being melted.
- soluble in melted halides of alkaline metals.
• Ionic hydrides are chemically active.
- Hydrolysis - Reducibility:
+ fully hydrolyzed in water to form hydroxide and hydrogen gas.
KH + H2O = KOH + H2
this is a redox reaction.
- Basicity:
Ionic hydrides act as bases when being hydrolyzed or when reacting with covalent
hydrides in ether to form complexes:
LiH + BH3 = Li [BH4]
bazơ Lewis axit Lewis Lithium borohydride
or KH + AlH3 = KAlH4 (potassium alanate)
2.8.2. Covalent hydrides - Hydrogen bonds
Covalent hydrides are hydrides of almost all non metals and semi metals, including
compounds of H with B, Al and elements of group 4,5,6,7
 • Characteristics:
- The covalent bonds are polar, with H is positive charged.
Depending on the electronegativity of other elements, the covalent level in the
bonds can be different:
HF 46% ion 54% covalence
HI 5% 95%
NH3 12% 88%
- most of them are volatile, some are gaseous, others are liquid at STD
- Chemical properties depend on the elements reacting with Hydrogen. Hydrides
dissolves in water to form an acid solution. HI is the strongest acid among ones that do
not contain oxygen.
• Changes in melting point and boiling point:
All hydrides have low boiling and melting points. Eg:
HF HCl HBr HI

Tnc(0C) -83 -144 -88 -50

Ts(0C) 19,5 -85 -67 -35

The melting and boiling point of the first hydride of a group is unexpectedly high.

.
H 2O

. .
H2Te
.
H2S
H2S
e
Down the group, the melting and boiling point increase.
EXP in group VI:
Hợp chất H 2O H 2S H2Se H2Te

Nđnc, oC 0 -85,6 -65,7 -51

Nđs, oC 100 -60,4 -41,4 -2

* Hydrogen bond: a weak type of force that forms a special type of dipole-dipole
attraction which occurs when a hydrogen atom bonded to a strongly electronegative
atom (H_X) exists in the vicinity of another electronegative atom with a lone pair of
electrons. Notation: X – H…Y.
 These bonds are generally stronger than ordinary dipole-dipole and dispersion
forces, but weaker than true covalent and ionic bonds.
When a hydrogen bond is formed, the X – H bond length increases (about 1%). The
H…Y distance is a lot longer than a normal H – Y bond, indicating this is a very weak
bond (Dissociation energy = 10-40 kj).
EXP: Bond lengths of normal covalent bonds:

O-H = 0,99 ; N-H =1,01 ; F-H = 0,92

Hydrogen bond lengths:

O-H…H : 2,7-2,8 O-H…N : 2,8-2,9

F-H…F : 2,6-2,7 N-H…O : 2,8-2,9

Hydrogen bond increase the boiling and melting points.
• Acid and base behavior of hydrides:
PKa of some hydrides are listed as belows:
Số oxi hoá -3 -2 -1
NH3 H2 O HF
pK 35 15,7 3,1
PH3 H2 S HCl
pK 27 7,2 -7,4
H2Se HBr
pK 3,7 -9,5
H2Te HI
pK 2,6 -10
In a periods, basicity decreases from left to right.
Down a group, the basicity increases.
The acidity depends on:
- The polarity of H-X the bond: the more polar it is, the easier H+ is detached.
The polarity depends on the electronegativity of X.
- The stability of H-X bond: the less stable it is, the better H+ is formed.
2.8.3. Hydrides of metals:
Self study.
2.8.4. Complex hydrides
Hydrides in which H- acts as a ligand, exp: Li[BH4]; Li[AlH4]. These are reducing
agents used in synthesizing organic compounds. They can reduce – COOH to – CH2OH,–
CONH2 to – CH2NH2.
Disadvantage of these compounds is that they are readily hydrolyzed by water, so
they are difficult to store.
2.8.5. Other hydrides
exp BeH2 and MgH2, they occurs in polymer styles, they can react with water. They
are intermediate states between ionic and covalent hydrides.
2.9. DEUTERIUM AND COMPOUNDS:
1. ND3 (Deuterated Ammonia)
- Mg3N2 + 6 H2O = Mg(OH)2 + NH3
Mg3N2 + 6 D2O = Mg(OD)2 + ND3
- NH3 + H2O = NH4+ + OH- ( weakly basic solution)
ND3 + H2O = ND4+ + OH- (weak basic solution)
2.NaOD
2Na + 2 H2O = 2NaOH + H2
2Na + 2 D2O = 2NaOD + D2
Preparation of D2 : analysis of H2O or D2O in acid or base solutions:
D2 O = D2 + O2
Other compounds such as D3PO4, D2SO4, DNO3, DClO4 are similar to those of H in
chemical properties, methods of preparation
exp: Al3+ + 3 OH- = Al(OH)3↓
Al3+ + 3 OD- = Al(OĐ)3↓
(NH4)2SO4 + 2 NaOH = Na2SO4 + 2NH3↑ + 2 H2O
(NH4)2SO4 + 2 NaOD = Na2SO4 + 2NĐ3↑ + 2 D2O

B. Oxygen – Ozone – Oxides – Peroxides – Superoxides

II.1. Oxygen
II.1.1.Atomic structure
Electron configuration: 1s2 2s2 2p4
Chemical trend: obtain or share electron to gain fill shell of noble gases.
+ add 2: O + 2e = O2- (in solution: O2_ + H2O = 2OH-, K=1022)
+ form two single valence bonds -O- or a double bond =O by sharing electrons: H-
O-H , O=C=O , (CH3)2O.
+ one single valence bond and gain one electron, e.g. OH-, C2H5O-.
+ create 3 single valence bonds, exp H3O+.
• Electron affinity, electronegativity, ionization energy:
O + 1e = O- A =-1,47eV (-142,3kJ/mol)
O- + 1e = O2- A = +8,3eV (795 kJ).
Total: O + 2e = O2- A = +6,83 eV (652,7 kJ/mol).
Electronegativity =3,5; I1=12,2ev
• Oxidation number: negative numbers in compounds, (except in compounds of
flouro F2O2, oxidation number is +1)

II.1.2.Molecular structure.
Because of 2 unpaired electron -> paramagnetic

Due to double bond: O=O distance (1,21 ) is smaller than O - O (1,48 ). Stable,
dissociaton energy is 496 kJ/mol.
II.1.3. Standard cell potential.
1. pH < 7
O2 + 4H+ + 4e = 2H2O Eo = +1,23V
O2 + 2H+ + 2e = H2O2 Eo = +0,682V
2. pH = 7:
O2 + 4H+ (10-7M) + 4e = 2H2O Eo = +0,815V
3. pH > 7
O2 + 2H2O + 4e =4OH- Eo = +0,401 V
O2 is easily reduced in acid environment, especially when catalyzed by transition
metals like Cu2+
II.1.4. Occurrence - Isotopes.
- occurrence: contains 20,93% (by volumes) of atmosphere ; found in compound
with all elements, except for He, Ne, Ar.
- isotopes: 15, 3 of them are stable 16O (99,759%); 17O (0,037%) và 18O (0,204%), 13
others have half life less than 3 minutes.
- allotropes: O2 and Ozon O3
II.1.5. Physical properties:
- Can be in gaseous, liquid, solid phases. paramagnetic.
- is gaseous at room temperature.
- part of O2 combine with each other to form O4 (ΔHform=0,13kcal/mol, very
small). 2 O2 are bound by unpaired electrons of opposite spin.
- liquid is a snow-like crystal with blue sky.
- Melting and boiling points are low = - 218,90C và - 1830C
- Solubility: slightly soluble in water, strongly soluble in some organic solvent
II.1.6. Chemical properties:
React directly with almost all elements at room and high temperature, except for
halogens, nobel gases, and nobel metals like Au, Ag, Pt where it acts as an oxidizer.
Oxi can be oxidized when reacting with F2 to form F2O .
1. React with elements:
• Reaction with metals (except Au, Ag, Pt)
- with Li, Na, K to form oxides, peroxides, superoxide when these metals are heated
in stream of gas.
4Li + O2 = 2Li2O
2Na + O2 = Na2O2
K + O2 = KO2
Oxide M2O (M: Na, K) can be only formed by heating peroxide with metals
Na2O2 + 2Na = 2Na2O
- with Ca, Mg to form CaO, MgO; with Ba tạo ra BaO2.
- with Al: At room temperature, Al reacts with oxygen to form a thin membrane of
oxide, protecting metals.
4Al + 3O2 = 2Al2O3
- with Cu to form Cu2O and CuO when letting Cu burn in oxi:
4Cu + O2 insufficient = 2Cu2O
2Cu + O2 excess = CuO
- with Fe: Fe burns in air to form Fe3O4
3Fe + 2O2 = Fe3O4, when completely burned, Fe2O3 is formed.
Fe which is not pure will be corroded to form Fe2O3.xH2O:
 4Fe + 3O2 + 2xH2O = 2Fe2O3 . xH2O
• Reaction with the non-metals.
- with B: to form B2O3 when B is heated in atmosphere or oxygen:
4B + 3O2 = 2B2O3
- with C, Si:
- with N2, P:
2. with S: S + O2 = SO2
2. Reaction with compounds:
Oxygen can oxidize a lot of compounds of inorganic and organic compounds. It
reacts
• with organic compound of H to form H2O
4NH3 + 5O2 = 4NO + 6H2O
• oxides of non metals in lower oxidation number to higher one:
2NO + O2 = 2NO2
2SO2 + O2 V 2O 5 2SO3
0
400 C
• hydroxide of metals with an oxidization of 2
4Fe(OH)2 + O2 + 2H2O = 4Fe(OH)3↓ (brown red)
In acid environment, can oxidize Fe2+ to Fe3+, iodide to iodine
4FeSO4 + O2 + 2H2SO4 = 2Fe2(SO4)3 + 2H2O
2KI + O2 + H2SO4 = K2SO4 + I2 + H2O
• oxidize organic compound
II.1.7. Preparation
1.Industry
• Hydrolysis of water (expensive)
• Periodically extract liquidized gas. (T0s O2 =-183, T0s N2 = -196)
2. In laboratory:
• Decomposition of oxides.
2Ag2O 4Ag + O2
2Pb3O4 6PbO + O2
• Decomposition of unstable salts rich in oygen
KNO3 KNO2 + O2
KClO3 KCl + O2 (main method)
 KMnO4 K2MnO4 +MnO2 + O2
• Reaction of H2SO4 concentrated with oxide or salt of metals at high
oxidization number.
2MnO + 2H2SO4 đ = 2MnSO4 + O2↑+ H2O (heat is needed)
2K2Cr2O7 + 10H2SO4 đ = 4KHSO4 + 2Cr(SO4)3 + 3O2↑+ 8H2O (heat is needed)
* Decomposition of hydrogen peroxide
2H2O2 = 2H2O + O2 (xt: Au, Ag, Pt)
More reactions: 2KMnO4+ 5H2O2 + 3H2SO4 = K2SO4 + 2MnSO4 + 5O2 + 8H2O
2Na2O2 + H2O = 4NaOH + O2↑
2BaO2 = 2BaO + O2 (heat is needed)
II.2. Oxide, peroxides
II.2.1.Oxides:
• Categories:
2 types: oxide forming salt and oxides which don’t form salt.
Oxides to form salt: acid oxide, base oxide and amphoteric oxide.
Typically:
Li Be B C N O F

Na Mg Al Si P S Cl

K Ca Ga Ge As Se Br

Rb Sr In Sn Sb Ie I

Cs Ba Tb Pb Bi Po Al

blues: amphoteric oxide, bottom left: base oxide, top right:acid oxide.
• Chemical properties:
* base oxide: soluble in water to form a alkaline environment:
O2_ + H2O = 2OH- K=1022
Na2O + H2O = Na2O
Insoluble oxides do not react with water.
React with acid oxides and acids
* Acid oxides: soluble in water to form: SO3 + H2O = H2SO4
react with acid oxide and base.
* amphoteric oxides: do not react with H2O, but dissolve in acids and bases,: Al2O3,
ZnO, Cr2O3
 Al2O3 + 6HCl + 9H2O = 2[Al(H2O)6] Cl3
Al2O3 + 6NaOH + 3H2O = Na3[Al(OH)6]
Note: for some metals, the higher the oxidation number, the stronger the acidity its
oxide is: CrO is a basic, Cr2O3 is amphoteric and CrO3 is acidic .
* Inert oxides: insoluble in water, acids and bases (still be active in redox reaction).
• Preparation
+ reaction of elements with O2
+ Heating hydroxide (insoluble bases/bases): M(OH)x, HnXOm
Cu(OH)2 (temp) CuO + H2O
HNO3 (temp) NO2 + O2 + H2O
2- 2- -
+ Composition of CO3 , SO4 , NO3 NThe stronger the acid is, the more difficult the
decomposition is
Carbonates dissociates, except for those of alkaline metals and salts of oxidation states of
3 which doesn’t occur. All sulphate, nitrate, oxalate dissociate except for those of alkaline
metals, exp: Ca(C2O4)2 → CaCO3 + CO; CaCO3 → CaO + CO2
+ oxidize oxides of low oxidation states to the higher ones
SO2 + O2 = SO3
+ Reduce oxides of high oxidation states to lower ones.
Fe2O3 + CO → Fe3O4 →FeO
+ Oxidize sulfide sals: FeS + O2 →Fe2O3 + SO2
II.2.2. Peroxide- superoxide - ozonide
In chemical processes, oxygen can share, gain or lose one electron to form O22-, O2-, O2+
1. Peroxides: oxides of O22-, alkaline metal, alkaline earths and some transition metals
create peroxide.
- Ion O22- is not paramagnetic, it reacts with water or dilute acid to form H2O2:
Na2O2 + 2H2O = H2O2 + 2NaOH
-Peroxides are strong oxidizers:
2KI + Na2O2 + 2H2SO4 = I2 + Na2SO4 + K2SO4 + 2H2O
- When reacting with stronger oxidizers, it acts as a reducing agent.
2KMnO4 + 5Na2O2 + 8H2SO4 = 5O2 + 5Na2SO4 + 2MnSO4 + K2SO4 + 8H2O
2. Superoxides: oxides containg O2-, Only alkaline metals form stable superoxides.
Alkaline metals and some transition metals form superoxides stable at solid solution.
- react with water to form H2O2 and O2:
4KO2 + 6H2O = 4KOH + 4H2O2 + O2
 -is a strong oxidizing agent.
3. Ozonide: contains O3-
II.2.3. Ozone
1. Molecular structure and half cell reduction potential
a)Molecular structures:

- dipole moment: 0,52D - OOO is 117o - R(O - O) =28 .

b) Standard reduction potential:
O3 + 2H+ + 2e = O2 + H2O E0 =2,07v O2 + 4H+ + 4e = 2H2O E0= 1,23v
O3 + 2H+(10-7) + 2e = O2 + H2O E0=1,65v O2 + 4H+(10-7) + 4e = 2H2O E0= 0,815v
O3 + H2O +2e = O2 + 2OH- E0 = 1,24v O2 + 2H2O +4e = 4OH- E0 = 0,41v
2. Physical properties:
- blue gaseous with special taste
- liquid is purple and solid is black
- high melting point (-192,70C) and boiling points (-111,90C) nđs (compare to O)
• 15 times more soluble in water than =O2 .
3. Chemical properties
- Pure ozone is relatively stable, if contaminated (or catalysts are present), it
dissociates without IR: 2 O3 D 3 O2
- Ozone is a stronger oxidizer than oxygen in all environment.
+ Oxidizes many metals (except Au, Pt and Ir) to form oxide, peroxides or
ozonides:
2Ag + O3 = Ag2O + O2
2Ag + O3 = Ag2O + O2
+ Oxidize Fe2+ to form Fe3+: 2Fe2+ + O3 + 2H+ = Fe3+ + O2↑+ H2O
Even when Fe2+ in stable complexes, (E0[Fe(CN)6]3+/[Fe(CN)6]4+=0,356v):
2[Fe(CN)6]4- + O3 + 2H2O = 2[Fe(CN)6]3- + O2 + 2OH-
+ oxidize sulfide to sulfate, H2S to H2SO4:
PbS + 4O3 = PbSO4 + 4O2
PbS + 4O3 = PbSO4 + 4O2
+ while O2 can oxidize I- only in acid environment, O3 can do it in base
environmental:
2KI + O3 + H2O = I2 + 2KOH + O2 EO (I2/I-) = 0,54 V
+ due to its strong ability to oxidize, ozone can kill bacterias in air and water.
 + Ozone reacts with many non saturated organic compounds to form ozonide,
which is unstable so it destroys rubber, so never use rubber tubes to transfer ozone,
alcohol burns when in touched with O3.
- When reacting with strong oxidizers like F2 (E0 F2/2F-) = 2,86), it acts as a
reducing reagent.
4. Ozonide
When obtaining 1 electron, ozone turns into ozonide O3- with 1 electron in MO
σ*. So it is strong oxidizer.
Ozonides of alkaline metals and ammonium ion has been extracted.
Structure of ozonide:
Ozone reacts with water to form O2 instead of H2O2:
4KO3 + 2H2O = 4KOH + 5O2↑
5. Preparation and uses of ozone:
a) Preparation:
• Discharge methods:
• Chemical methods:
- Slightly heat ammonium sulfate with concentrated HNO3:
(NH4)2S2O8 + 2HNO3 = H2S2O8 + 2NH4NO3
H2S2O8 + H2O = H2S2O5 + H2SO4
H2S2O5 + H2O = H2SO4 + H2O2
3H2O2 = 3H2O + O3
General: 3(NH4)2S2O8 + 6HNO3 = 6NH4NO3 + 6H2SO4 + O3↑
- reaction of H2SO4 with BaO2:
BaO2 + H2SO4 = BaSO4↓+ H2 O2
3H2O2 = 3H2O + O3↑
b)uses
Due to strong oxidizing ability, O3 can kill bacterias in air, it is used to clean
water. A small amount of O3 (<10-6 ) is good for health. Thanks to O3 layer, our life is
not threaten by UV rays because it is absorbed by O3 to form O2
C. Water –Hydrogen peroxide
III.1. Water
III.1.1. Electronic structure

O - H bond length is 0,99 , bonding energy: 376,5 kJ/mol, HOH angle is 105o.
H2O is bent, oxygen use sp3 hybrid orbitals to bond with 1s of hydrogen
 Question: Plot the energy diagram of H2O using MO theory. Give the electronic
structure.

In water molecule, O-H bond has great bonding energy, contains any anti-bonding
electrons mt water is thermally stable. It starts to dissociated at 1000oC, at 2000oC only
2% is dissociated..
The 2 paired electrons in hybrid orbitals, H2O have strong ability to give its pair
electrons to others.
III.1.2. Occurrence.
- water covers 3/4 of the surfaces the earth, and constitutes 70% the human body.
Animals and people can die if 10-20% of the water in their body is lost. Water is also an
important compound in industry.
- The purity of water from different sources is different. Rain water and snow is the
purest. River water, mineral water, ocean water, daily water, industry water are not very
pure. More than 97% of water in the earth is salty, the not salty salt (3%) is concentrated
in the 2 poles, of these around 1% is from salt, lake, underground water and snow.
Natural water is formed from combination of isotopes of oxide and hydrogen, the
most popular one is H2 O (99,73%).
- Water can be polluted due to many reasons such as wasted water trashed from
peopel, industry and agriculture. Before being discarded to the environment, water needs
to be analyzed. Lake contains a lot of organic waste that can kill animals.
III.1.3. Properties of water - Phase diagram
- At room temperature, water is a colorless, odorless, tasteless water. A thick water
is slightly blue.
- Only in gas phase, water occurs as single molecules. In liquid phase, water
molecules combined with each other to form a set of molecules. This is partly due to
dipole-dipole interaction, but more importantly the hydro bond between molecules.
The Hydrogen bonding is not very stable, molecules combined in one set can leave this
set and join another one. The least stable combination is (H2O)2. Therefore, water has
higher melting point and boiling point compared with other similar compounds.
 The structure of ice:( hydrogen bonds are shown as dotted lines)

(ice water) (liquid water)

3
The density of ice water is 0,92 g/cm , lighter than liquid water. This is due to the
empty spaces in ice water. In a ice crystal, each water molecule is surrounded by other
four water molecules to create a tetrahedral shape, in which each oxygen atom lies at the
center of a tetrahedral formed from 4 hydrogen atoms. The number of coordination of
oxygen reaches the maximum value, which is 4.
The density of water also change with temperature. This is because the water in
liquid phase combine to sets of big molecules by using hydrogen bonding. In water, 1
water molecule combines with 4 other water molecules to create a tetrahedral, so the ice
is fully packed and therefore not very dense. When melted, parts (15%) of hydrogen
bondings are broken, so they have chance to move closer to each other. Thus the melted
ice water is heavier than ice at O0C. However, if continued heating, the volume of water
increases, while the hydrogen bondings are broken, so the combination of molecules
decreases, and the density decreases.
 - Phase diagram of water:
It can be seen from that diagram that
When t0 > 0,010C and P>0,006 atm, water is in both liquid and gas phases.
When t0 < 0,010C and P<0,006: water is in solid and gas forms.
When pressure increases, the boiling point increases but the melting points decreases. At
high pressure (P>2115 at), melting point increase because the ice water occurs another
form.
Water has a high specific heat index, meaning it will take more heat to raise the
temperature and more time to cool the water down. This is helpful in regulating the earth
weather. The temperature of human body is 37oC. This is partly because water constitutes
70% of our body. The heat of vaporization of water is also very large (2260J/g), which is
also contributed to moderate the weather. If the heat of vaporization is small, then the
vaporizing and condensing of water will occur too fast, and this will affect the
environment.
III.1.4. Chemical properties
Water is active. In the reactions involved, it acts as acid, base, oxidizing agent and
reducing agent. The reactions are divided into 6 groups.
- The acidity is due to the strongly polar bond O-H, leaving a relative empty space
on the orbitals of H, and therefore it can gain one electron pair.
- The base behavior is due to the fact that the oxygen atom still has 2 pairs of non-
bonding electrons in the hybrid orbitals, which has strong tendency to give these electron
pairs.
- The ability to reduce is due to the low oxidation number of oxygen, (-2). It can be
oxidized to fomm O2:
O2 + 4H+ + 4e = 2H2O Eo = +1,23V
O2 + 4H+ (10-7M) + 4e = 2H2O Eo = +0,815V
 - The acidity is due to the high oxidation number of hydrogen in water (+1). water
can gain 1 electron to form H2: 2H2O + 2e = H2 + 2OH- EO = - 0,828V
• Water is a weak electrolyte, acid dissociation constant at 25oC is1,8.10-16.
• Hydration reaction: -definition - heat of hydration of salt.
Why are ions hydrated in water?: For electrolytes, hydration occurs due to interaction
between ions and the polar molecules (water) or by donor-accepter bond between the ion
and the water molecule with the lone paired electrons on O. For weak electrolytes or non
electrolytes that contain OH group, such as weak acid, alcohol, sugar, the hydration is
fast because of hydrogen bond between OH and H2O.
Because of being polarized, water can hydrate cations, reducing the density of charge,
making the cation more stable than in water.
- Hydration of cation:
nH2O + H+ = [H(H2O)n]+ (donor-accepter bond), n= 2→7, for simplicity useH3O
All metal ions are hydrated:
exp: 4H2O + Cu2+ = [Cu(H2O)4]2+
Besides, because of the ability to give the lone pair electrons, some water molecules
in the first hydration layer can form aqua complexes [M(H2O)x]n+ through direct metal-
oxygen bonds.
Al3+ + nH2O = [Al(H2O)n]3+ hay Al3+ + nH2O = Al3+.aq
Aqua complexes transition metals are usually colored: [Cu(H2O)6]2+ pale blue;
[Fe(H2O)6]3+ lime yellow; [Mn(H2O)6]2+ slight pink, [Ti(H2O)6]3+ red, [Ni(H2O)6]2+ pale
blue, [Cr(H2O)6]3+ blue, [Co(H2O)6]2+ pink.
- Hydration of anions through hydrogen bonding
OH- + nH2O = [OH(H2O)n]- (n=1, 2)
HO- + H2O = H – O…HOH (H3O2-).
Cl- + nH2O = Cl-.aq
- Hydrates: inorganic salts "containing water molecules combined in a definite ratio as
an integral part of the crystal" that are either bound to a metal center or that have
crystallized with the metal complex. Hydrates such as FeCl3.6H2O, MgCl2.6H2O,
FeSO4.7H2O, CuSO4.5H2O are in fact hydrate complexes, in which H2O can act as
ligands of the complex ions or the counterions.
- Hydrate melting and efflorescence: When exposed to air, some hydrates absorb
water to create a solution, which is called melting. On the other hand, some hydrates
loses water to form smooth powder, which is called efflorescence: VD. e.g
Na2SO4.10H2O easily lose their water of crystallization, efflorescing in air to a powder
of anhydrous Na2SO4
 The reason is the relationship between vapor pressure the air and the saturated
vapor pressure of hydrates over the saturated hydrate solution.
P (mmHg) hydrat Saturated water vapor pressure is 14mmHg at room temperature,
e solution CaCl2.6H2O melts because it absorbs water in air until
the vapor pressure of the solution created is equal the
CaCl2.6H2O 2,5 7,5 water vapor pressure in air. . Na2SO4.10 H2O has the
high vapor pressure, so it lose water, while CuSO4.5H2O
CuSO4.5H2O 5,1 16 is stable in air
Na2SO4.10 H2O 15,3 16,6

• Hydrolysis:
Hydrolysis is a reaction involving the breaking of a bond in a molecule using
water. In fact, it’s the interaction between the ions, acids, bases with H+ and OH- ions that
shift the equilibrium:
H2 O H+ + OH-
In many cases, hydrolysis is an acid-base reaction, in which water acts as an acid or base.
However, there are some reactions, in which the hydrolyses are redox reactions.
- Hydrolysis of AxBy (A: metals; B: non-metals, such as hydride, nitrite, phosphide,
carbide, sulfide) to form BHx and A(OH)y. These compounds are almost fully hydrolyzed.
Exp:
CaC2 + 2H2O = Ca(OH)2 + C2H2
Al2S3 + 6H2O = 2Al(OH)3 + 3H2S
Ca3P2 + 6H2O = 3Ca(OH)2 + 2PH3
2NaH + H2O = 2NaOH + H2
- Hydrolysis of AxBy (A and B are non metals), the products are acid and hydride of non
metals. These compounds are almost fully hydrolyzed:
NCl3 + 3H2O = 3HClO + 3NH3
PCl3 + 3H2O = H3PO3 + 3HCl
BCl3 + 3H2O = H3BO3 + 3HCl
- Salt hydrolysis results in acid, base or neutral environment: salts of strong acids and
bases: pH =7, strong acids and weak bases: pH<7, weak acid and strong base: pH>7. For
salts of weak acids and bases, the pH of the environment depends on the strength of acids
and bases. The weaker the acidic or basic environment is, the easier the salt is hydrolyzed
Na3CO3 + H2O NaOH + NaHCO3
3+
[Al(H2O)6] + H2O [Al(H2O)5(OH)]2+ + H3O+
(Similarly for salts of metals of high oxidation numbers :Sb3+, Bi3+, Fe3+, Cr3+ và
Cu2+, Zn2+)
CH3COONH4 is almost neutral because Ka = 1,8.10-5, Kb = 10-5
For salts of high oxidation states, redox reactions can occur:
Pb(SO4)2 + H2O = PbO2 + H2SO4
(CH3COO)4Pb + H2O = PbO2 + CH3COOH
• React with elements:
H2O can be oxidizing or reducing agent, so the products can be H2 or O2.
- Reaction with metals:
Alkaline metals, alkaline earth metals react strongly with water at room
temperature or low temperature.
Powder Al, Mg can continue to burn in water vapor at 100oC.
Metals such as Fe, Zn, Ni, Co, Mn, Cr react with water at high temperature (500oC).
The reactions are reversible.
- Reaction with halogens:
Fluorine can oxidize water at room temperature to form oxygen:
2F2 + 2H2O = 4HF + O2
For chlorine and bromine, the similar reaction is thermodynamically spontaneous, but the
activation energy is high, so the actual reactions are::
X2 + H2O = HX + HXO X = Cl, Br
For iodine: I2 + H2O = HI + HIO3
+ Reactions with P, C, Si and B.
10000C
C + H2 O CO + H2 ΔHo = 130kJ
Si + H2O = SiO2 + H2
• Reactions with some metal and nonmetal oxides.
• Reacts with organic compounds:
- Additive reaction to unsaturated compounds
- Hydrolysis of esters and amines.
Besides, water is also a catalyst or environment for a great amount of reactions. exp
NO can react with O2 to from NO2 and Fe reacts with Cl2 to form FeCl3 when H2O is
present.
III.1.5. Hard water - the hardness of water - Method to soften hard water.
1. Hard water
Hard water is water that has high mineral content Mg2+, Ca2+, Fe2+.
Effects:
 Prevents the lathering of soap, destroying the surfactant properties of the soap by
forming a solid precipitate (the soap scum).
Calcium and magnesium carbonates tend to precipitate out as adherent solids on the
surfaces of pipes and especially on the hot heat exchanger surfaces of boilers. The
resulting scale buildup can impede water flow in pipes.
2. Categories
The hardness of water is referred to by three types of measurements: grains per
gallon, milligrams per liter (mg/L), or parts per million (ppm).
- Temporary hardness is a type of water hardness caused by the presence of dissolved
bicarbonate minerals (calcium bicarbonate and magnesium bicarbonate).
- Permanent hardness is hardness (mineral content) that cannot be removed by boiling.
When this is the case, it is usually caused by the presence of calcium sulfate and/or
magnesium sulfates in the water, which do not precipitate out as the temperature
increases. Sr2+, Fe2+, Mn2+, Al3+, Fe3+ are also sources of hardness.
3. Methods of softening water
- Heating method
- Precipitating method: use calcium hydroxide or soda to precipitate hydro
carbonate salts of Ca, Mg, Fe
- Ion exchange: In this method "hardness" ions trade places with sodium and
chloride ions that are loosely bound to an ion-exchange resin or a zeolite (many zeolite
minerals occur in nature, but specialized ones are often made artificially.).
 - The illustration depicts a negatively-charged zeolite to which [positive] sodium
ions are attached. Calcium or magnesium ions in the water displace sodium ions,

which are released into the water. In a similar way, positively-charged zeolites bind
negatively-charged chloride ions (Cl–), which get displaced by bicarbonate ions in the
water. As the zeolites become converted to their Ca2+ and HCO3– forms they
gradually lose their effectiveness and must be regenerated. This is accomplished by
passing a concentrated brine solution though them, causing the above reaction to be
reversed.
III.2. HEAVY WATER
In heavy water, one or more hydrogen atoms are replaced by Deuterium: HDO
or D2O. The main component of heavy water in nature is HDO.
1- Preparation
Natural water contains D2O, so heavy water can be prepared by using
hydrolysis. Water is first hydrolysis, leaving a solution rich in D2O. Partition distillation
is used later to gain D2O with the efficiency of 99% (83 ml D2O obtained per 2250 liters
of water)
2- Physical and chemical properties .
- Physical properties: maximum density is reached at 16,6°C, melting point =3,82°C and
boiling point=101,42°C, auto-ionization constant at 25°C is [D+][OD-]=1,95.10-15,
density at 200C is 1,1086 (0,9982 for water). It slows down human reactivity because it
reduces the activation of enzymes. Almost all substances strongly soluble in water are
slightly soluble in hard water
- Chemical properties: many reactions of D2O are similar to those of H2O, but they are a
lot slower:
2Na + 2 D2O =2NaOD + D2
NaOD + DCl = NaCl + D2O
III.3. Hydrogen peroxide H2O2
1. Structure

d(O-H) = 0,95 ; d(O-O) = 1,48 ; OOH angle is 950, EO-O =

217,5 kJ/mol; EO-H = 376,5 kJ/mol
The O-O bond is single. EO-O < EO-H là because O-H is a polar covalent. Since the two O-
H bonds are not symmetric, the molecule is of a great dipole moment.
2. Physical properties
- similar to water in many points: pure H2O2 is colorless and viscous liquid. It is not
a popular solvent because it is a strong oxidizing reagents and are easily hydrolyzed. At
gas phase, there exists no combination of molecules, but at liquid and solid states, the
combination of molecules is better than in water.
- The boiling point is 152,10C and freezing point is -0,890C (measured at low
pressure to avoid decomposition, not very accurate).
- Dissolve in water to any ratio because it is strongly polar and can from hydrogen
bonds with water.
- can form peroxide hydrates: e.g K2CO3.3H2O2.
3. Chemical properties
• Stability:
Pure H2O2 is relatively stable. When contaminated or exposed to light, or affected
by temperature, it is ready to dissociate, especially in basic environment:
2H2O2 = 2H2O + O2 Ho = -98,74kJ/mol.
To decomposition a large amount of H2O2 , people heat it in basic environment or
with it with MnO2 which acts as a catalyst
To stabilize H2O2 solution, one can add phosphoric acid or sulfuric acid.
• Acidity:
H2O2 is a weak acid, but still stronger than water:
H2 O2 + H2 O H3O+ + HO Ka = 2.10-12
H2O2 + Ba(OH)2 = BaO2 + 2H2O
BaO2 + H2SO4 = BaSO4↓ + H2O2
• Oxidizing property:
H2O2. is represented by the strong oxidization ability. The reduction potential is
high in both acidic and basic environment.
H2O2 + 2H+ + 2e = 2H2O EO = +1,776V
H2O2 + 2e = 2OH- EO = 0,87V
It can oxidize I- to I2, sulfide to sulfate, and arsenite to arsenate
H2O2 + KI + H2SO4 = I2 + K2SO4 + 2H2O
H2O2 + 2KI = I2 + 2KOH
PbS + 4H2O2 = PbSO4 + 4H2O
H2O2 + H3AsO3 = H3AsO4 + H2O
H2O2 + KNO2 = KNO3 + H2O
• reduction ability: why?
O2 + 2H+ + 2e = H2O2 EO = 0,68V
 H2O2 acts as a reducing agent when reacting with strong oxidizers such as O3,
KMnO4, Cl2, hypochlorite.
2KMnO4 + 3H2SO4 + 5H2O2 = 2MnSO4 + K2SO4 + 5O2↑ + 8H2O
Cl2 + H2O2 = 2HCl + O2↑
H2O2 + NaClO = H2O + O2↑ + NaCl
Note: O2 in these reactions is from H2O2, meaning that O-O bond is not broken but
O - 2e = O2.
4. .use and Preparation
Preparation: - In the lab: Let Na2O2, BaO2 react with dilute H2SO4 solution (15-
18%) at low temperature: BaO2 + H2SO4 = BaSO4 + H2O2
- Manufacture: + Electrolysis of h H2SO4 50% solution at 5-10oC:
( + ): 2H2O-4e→4H+ +O2 (E=1,23v) (1) and 2SO42- -2e→ S2O82- (E=2,05v)(2)
( - ) : 2H+ +2e→ H2
(2) occurs first due to the overvoltage phenomenon. H2S2O8 formed reacts with water to
form H2O2: H2S2O8 + H2O → 2 H2SO4 + H2O2
The mixture is then filtered using vacuum filter to obtain H2O2.
• anthraquinone: use oxygen to oxidize anthraquinone. The product can be reduced by H2
khử to formed anthraquinone. This method is widely used because the reagents

hydrogen and oxygen are cheap.

Uses:
- H2O2 3% solution is used as an antiseptic compound. H2O2 30% can be used to bleach
paper , wool, rattan without damaging the materials. It can also be used to recover ancient
pictures drawn by while powder of 2PbCO3.Pb(OH)2
- H2O2 is also used as bubble generator in foam material industry
- It is also used as oxidizers
CHAPTER III. THE GROUP IA METAL – ALKALI METAL

3.1. General characteristics of alkali metal

Six elements of group IA of the periodic table system (periodic) Mendeleep as lithium
(Li), Sodium (Na), potassium (K), rubidium (Rb), Cesi (Cs) and Franci (Fr). The reason, they are
called metal alkaline (KLK), because our solution is alkaline. In particular, Franci is radioactive
elements.
Group 1 metals are called alkali metals. Alkali metals are abundant in minerals and sea
water. Especially the content of sodium, Na, in the Earth's crust is fourth after Al, Fe, and Ca.
Although the existence of sodium or potassium ions was recognized for many years, a number of
attempts to isolate the metals from aqueous solutions of their salts failed because of their high
reactivity with water. Potassium (1807) and subsequently sodium were isolated by the
electrolysis of molten salt of KOH or NaOH by H. Davy in the 19th century. Lithium Li was
discovered as a new element (1817), and Davy soon isolated it by molten salt electrolysis of
Li2O . Rubidium, Rb and Cesium, Cs, were discovered as new elements by spectroscopy in
1861. Francium, Fr, was discovered using a radiochemical technique in 193 low. 9. Its natural
abundance is very low.
Table 3.1. Some characteristics and physical properties of the elements of groups IA
As shown, melting-points, boiling points, and densities of alkali metals are low, and they are soft
metals. Since the outer shell contains only one s-electron, The large atomic radius ---> weak
lattice ---> large space in the unit cell ---> low specific weight, low melting temperature and low
boiling temperature, theionization energy is very low, and mono cations of alkali metals form
easily. Qualitative analysis of alkali metals is possible by means of flame reactions using
characteristic luminescence lines. Especially the orange D-line of sodium is used in the sodium
lamp. Alkali metals are oxidized by water evolving hydrogen gas due to their low reduction
potentials. Except lithium, the heavier alkali metals react violently with water, and sufficient
caution should be exercise in their handling.
In one period, the atomic radius of the alkali metal is largest. In contrast, when going
from top to bottom, atomic radius and ionic radius of the alkali metal increases with increasing
the nuclear charge.
In the periodic table, alkali metal has the lowest ionization energy. Because, in the shell
valence electrons of the alkali metal has one electron (ns1: where, n is the number of row) should
be joining a chemical reaction, easily giving away one electron to form ion M+ have sustainable
configuration of noble gases.
Number oxidation characteristics of alkali metal is +1. This may also explain why the
standard electrode potential alkali metals have very negative and alkali group metals have a
strong reducing properties in periodic table.
When you go from the top down, the ionization energy decreases. The second ionization energy
of alkali metal is great. Because ion M+ configuration of stable noble gas elements, making it
difficult to remove the second electron from the atom. Therefore, the second ionization energy is
much larger than the first ionization energy.
The alkali metal is formed mainly by ionic compounds with oxidation number is +1
unique characteristics. However, they also have the potential to create covalent linking of the
molecules Li2, Na2, K2, Rb2, Cs2 exist in a gaseous state. The binding energy of the molecules is
low and decreases from Li to Cs.
 Molecules Li2 Na2 K2 Rb2 Cs2
Bond energy, kJ.mol-1 108 73,2 49,8 47,3 43,5

Low energy of covalent links between the alkali metal atoms is consistent with low ionization
energy of them. The attraction between the electron nuclear charge of the alkali metal quite
weak, so the weaker force when receiving an electron from another atom. So metallic bonding in
alkali metal is weak. This made for melting, boiling them are low and declining from Li to Cs.
On the other hand, very soft alkali metal can be cut with a knife (where Li is the hardest metal).
Density of alkali metal is smaller than other metals. Li, Na and K are lighter than water. This is
explained by metallic bonding in alkali metal weak, empty space in the lattice structure of our
large volume makes the atom (or lattice) increased. Therefore, specific weight (mass/volume) of
them fell. When going from the top down, the density of alkali metal increases. Because, in the
direction of increasing nuclear charge, the atomic weight increases more rapidly. However, the
density of Na greater than K, because valence electrons fill sub-level of K 4s while still empty
sub-level 3d made atomic radius of the star K significantly increased with Na.
Alkali metal atoms and ions in the ground state (low energy) have no color. However,
when the molecule or compound of alkali metal into flames, the flame becomes colored. This is
explained as follows, when in flames the valence electron of atoms and ions of alkali metal
receive enough energy to jump on the excited stated with a higher energy level. Due to the
excited state is actually not durable, so in a very short time (about 10-8s) valence electrons will
return to the ground state having a lower energy level and releases energy in the form of
radiation in the visible light region.
Li - red, Na - yellow, K - purple, Rb - purple, pink Cs - blue
The alkali metals are mutually soluble and easy to form amalgams with mercury (alkali
metal/Hg). Mixtures between mercury amalgams and alkali metals with strong reducing
properties should be applied as a reducing agent.

3.2. The nature and composition of isotopes

In nature, Na and K are the two most common elements of alkali metal accounting
respectively 2.40 and 2.35% of the earth's crust. In addition, Li occupies prime 5.10-3%, Rb and
Cs accounted 8.10-3% accounted for 10-3%.
Due to the high activity, so naturally the alkali metal exist mainly in the form of M+ ions
in the mineral composition which is situated in the Earth's crust. In the lithosphere, the alkali
metals exist mainly in the form of orthoclase alumosilicate such as K2[Al2Si6O16], Anbit
Na2[Al2Si6O16]. But Li, Rb and Cs exist in the minerals and spodunmen lepidolit.
The alkali metals have odd numbers of nucleons, so the stable isotopes in their natural are
relatively low. Na and Cs have only one stable isotope; Li has two stable isotopes which is
accounted for 92.5% 7Li and 6Li accounting for 7.5%; K has three isotopes which are accounted
for 93.26% 39K, 41K and 40K followed by (0.01%) is unstable and weak radioactive β.
3.3. Chemical properties
Alkali metal is the active metal, because they have
- The electron configuration in the outermost layer ns1
- Low ionization energy
Due to the first ionization energy decreases from top to bottom in the group (from Li to Cs), so
alkali metal has unique chemical properties that are very strong reducing properties (the most
powerful in all the group metals) and increases from the top down. Therefore, alkali metal has
oxidation state +1 in chemical compounds.
3.3.1. Reaction with compounds
3.3.1.1. Reacts with water
Hydroxide and hydrogen gas that results from the reaction of water with alkali metal

When the reaction with water,

- Li reaction mellow, not explosive and does not constitute flame,
- Na melt into a well-rounded particles and running on the water, if large particles will explode
and create a fire. K caught fire immediately, and Rb and Cs explode.
Table 3.2. Characteristics of Atomic Energy of the IA group elements (eV/atom)

Based on the results in the table above we can see, Li is the metal most negative hydration
energy. This is explained by, Li+ ion has the smallest size in solution so it has very high
polarization. The result is a strong attraction of water molecules than the other alkali metal ions
so most negative energy carbohydrates. That is, the Li+ ion hydration is very convenient.
From the ΔH in the table above we can see, Li is the most active metal (most negative standard
electrode potential). However, the fact it does not react with water intensity. This is explained by
kinetic factors, because the breakdown of the crystal network Li difficult than the other alkali
metals for 2 reasons
- Li has no subclasses d, atomic radius Li small, Li-Li metal bonding in the crystal is the most
durable metal amongst alkali metals,
- Li has higher boiling and melting temperature as compared to the same group metals.
3.3.1.2. The reaction with acid
Alkali metals react violently with acid solution.
3.3.1.3. Dissolved in liquid ammonia
The alkali metals are soluble in liquid ammonia. Diluted solutions are green and electric
conductor, a solution with a higher concentration of red copper and metallic properties. In dilute
solutions alkali metals dissociate into ions and electrons by solvate of ammonia,

the electrons ammonia causes of this blue solution. By means of electron magnetic resonance
spectrum, determine the existence of free electrons in solution (solution paramagnetic
properties). However, the paramagnetic down to the concentration of the solution increases,
because the electron chemical ammonia can be combined together to create diamagnetic
compounds containing electron pairs

In liquid NH3 its reducibility is very good, They are applied in many inorganic chemistry and
organic chemistry.
The alkali metal can replace H in organic acid ions such as sodium salts make acetate, potassium
benzoate. Alkali metals also form covalent compounds such as methyl lithium (LiCH3), sodium
ethyl (NaC2H5). Compounds between alkali metals are formed when they interact with each
other.
The compounds are Na2K, Na2Cs2, K2Cs, K7Cs8, ...

3.3.2 Reaction with non-metallic elements

3.3.2.1 Reaction with air
When heat in air or in oxygen, Li forms Li2O, Na forms Na2O2 and others form MO2 (M: K, Cs,
Rb):

To interpret: a small cation is stabilized by a small anion (high charge density); a large cation is
stabilized by a large anion (low charge density).
The charge per unit of volume: O2- > O22- > O2-.
3.3.2.2 Reaction with hydrogen

M: alkaline metal; MH are ionic hydrides.

3.3.2.3 Reaction with halogens

X: F, Cl, Br, I; M+X- are ionic

3.3.2.4 Some other reactions

3.4 Preparation of alkali metals

Reduce M+ ions without the presence of water:

Na, K: are formed by electrolysis molten chlorides or hydroxides in the absence of oxygen.

Figure 3.1. Scheme for the electrolysis molten NaCl

Na: is produced by electrolysis a mixture of molten NaCl, NaF (25%) and KCl (12%), at
temperature 610-650oC.
Li: is produced by electrolysis a mixture of molten LiCl and KCl.
Rb and Cs are formed when Ca metal reacts with RbCl or CsCl at high temperature in vacuum.

Rb or Cs is vaporized.

3.5 Compound of alkali metals

3.5.1 Hydrides
The hydrides of alkaline metals are of salt type, in which M - H bonds are ionic
predominately. The ionic character increases from Li to Cs, because the ionization energy
decreases from Li to Cs. These include the cation M+ and hydride anion H- and NaCl-type
structure. Stability of the hydride increases from Li to Cs. When molten, the hydrides dissociate
while in gas phase they exist in MH molecules.
Features of alkaline metal hydrides: the melting point is relatively high, colorless, conduct
electricity which are consistent with the ionic character of the M-H bond. They are strong
reducing agents, the reaction with water liberating hydrogen gas:

3.5.2 Compounds with oxygen

3.5.2.1 Oxides and peroxides
a. Oxides (M2O)
Oxides of alkaline metals are all in cubic lattice. Their colors vary from white to orange.
Li2O Na2O K2 O Rb2O Cs2O
White White White Yellow Orange

Melting point, boiling point and stability decrease from Li2O to Cs2O.
They are basic oxides:

- They react with O2 at room temperature to form peroxides (except for Li2O)

- Preparation: heat peroxides, hydroxides, nitrate or nitrite with corresponding alkaline metals:

- Li2O is formed when heat hydroxide, nitrate or carbonate in hydrogen:

b. Peroxides M2O2 (O22-) and superoxides MO2 (O2-)

Peroxides and superoxides of alkaline metals are all solid with color ranging from white to
orange and red.
Na2O2 K2 O2 Rb2O2 Cs2O2 KO2 RbO2 CsO2
Yellow Yellow Yellow Yellow Yellow Orange Red

Stable to heat, absorb moisture strongly.

They are all strong oxidation. They react with water to form oxygen and hydroperoxide.
They are produced by heating alkaline metal in air or by the reaction of oxygen with solution of
the metal in ammonia.
Na2O2. Is the most important peroxide in application. It is used to supply oxygen in submarines,
diving suit; in bleaching.
mp 460oC; bp 660oC; dissociate at 600oC.
React intensely with water, release heat:

This reaction is to produce oxygen in laboratory.

At low temperature:

React with CO, CO2, and solution of CO2 in water:

Na2O2 is a strong oxidation compound:

KO2.
Absorb moisture strongly; mp 440oC.
Easily react with water, carbon dioxide to form oxygen:

The mixture of Na2O2 and KO2 (ratio 1:2 in mole) to use in diving suit and in submarine.
In vacuum, it dissociates forming K2O2 and K2O:

It is a strong oxidation compound:

KO2 is prepared by the reaction of KNO3 with K metal or by heating K metal in a silver cup.
c. Ozonite MO3 (O3-)
So far has only KO3, CsO3 and NH4O3 been known.
MO3 is strong oxidation substance. It reacts with water to form oxygen. At room temperature it
dissociates into superoxide and oxygen.
Preparation:

3.5.2.2 Hydroxide
Hydroxides of alkaline metals are white solid. Low melting point. Form transparent, highly
mobile liquid when melt.
LiOH NaOH KOH RbOH CsOH
Mp, oC 450 328 360 301 271

In the molten state, they corrode glass, ceramic and the Pt (in the presence of air), so need to use
the tools of iron, nickel or silver to smelt the MOH.
MOH is stable to heat, when heated to high temperatures, the MOH evaporation without
dehydration (loss of water at 500oC except LiOH create Li2O).
The MOH strongly hygroscopic, the air is flowing washes and then dissolved into solution.
Therefore, MOH is used in the desiccator, dry organic bases.
MOH are easily soluble in water, release heat (except LiOH). They are also easily dissolve in
ethanol, ether.
The MOH is strongest base, they interact easily with acid oxides and acid. Their solution also
interacts with the metal hydroxide that is amphoteric such as Al2O3, ZnO,... and nonmetals such
as Si, P, halogen ...
The MOH is prepared by electrolysis of solution of alkali metal chloride or alkali metal reacts
with water.
*Sodium hydroxide NaOH
NaOH is very important, especially in the manufacturing industry. Sodium hydroxide is used in
the production of cellulose from wood, soap, paper and rayon, and oil mining, pharmaceutical
preparations and dyes, ...and is very commonly used in laboratories.
NaOH is a white solid, absorb moisture strongly.
NaOH is a strong base:
NaOH + H+ → Na+ + H2O
2NaOH + CO2 → Na2CO3+ H2O
NaOH + CO2 → NaHCO3
2Al + 2NaOH + 2H2O → 2NaAlO2 + 3H2
React with some nonmetal elements:
Si + 2NaOH + H2O → Na2SiO3 + 2H2
2C + 6NaOH → 2Na + 2Na2CO3 + 3H2
4P + 3NaOH + 3H2O → 3NaH2PO2 + PH3
Cl2 + 2NaOH → NaClO + NaCl + H2O
React with ceramic and glass:
SiO2 + 2NaOH → Na2SiO3 + H2O

React with some salt to form hydroxides which are insoluble in water and to form weak bases:
NH4Cl + NaOH → NaCl + NH3 + H2O
CH3NH3Cl + NaOH → NaCl + CH3NH2 + H2O
* Production of NaOH in industry:
Method 1: Reaction of Ca(OH)2 with dilute solution of Na2CO3:
Ca(OH)2 + Na2CO3 → 2NaOH + CaCO3↓
This method is often used to recover NaOH in paper production
Method 2: electrolysis of saturated solution of NaCl:
NaCl → Na+ + Cl-
H2O ↔ H+ + OH-
Anôt (+): 2Cl- - 2e- → Cl2
Catôt (-): 2H+ + 2e- → H2

To avoid explosive reaction between H2 and Cl2; and Cl2 not to come into contact with
NaOH solution, a porous membrane is used between two electrodes. Porous membrane
allows fluid permeable but prevents air bubbles passing.
 Figure 3.2. Electrolysis tank with semi-permeable membrane

3.5.3 Salts of alkali metals

The alkali metal salts are colorless except salts such as anion KMnO4 colored purple by ion
MnO4-.
Almost all alkaline metal salts are solvable, except some lithium salts. They form non hydrate
crystals except for some of lithium and sodium such as LiCl.H2O, LiNO3.H2O, NaCl.2H2O…
They have high melting point and boiling point and conduct electricity when molten.
3.5.3.1. Halogenides of alkaline metals
- Colorless crystals.
- Ionic compounds except for LiI
Table 3.3. Lattice energy and enthalpy of dissolution of halogenides of alkali metals
Ion Lattice energy, kJ.mol-1 Energy of dissolution, kJ.mol-1

F- Cl- Br- I- F- Cl- Br- I-

Li+ 1008 828 790 732 +4,18 -37,63 -50,20 -62,76

Na + 903 769 736 690 0 +4,18 +4,18 +8,36
K+ 803 698 673 631 -16,73 +16,73 +20,92 +20,92
Rb+ 769 677 648 615 -25,10 +16,73 +25,10 +29,28
Cs+ 715 640 640 585 -37,65 +20,92 +29,28 +37,65
High melting point and boiling point; decrease from Li+ to Cs+ and from F- to I-.
Table 3.4. Melting point (left) and boiling point (right) of halogenides of alkali metals

They are all easy to dissolve in water (except for LiF) and their solubility increase rather rapidly
at high temperature.
* Sodium chloride. Is the most important salt amongst halogenides of alkaline metals.
- Ionic compound, face centered cubic lattice.
- Exist in sea water (3% in weight), in salt lakes, …
- Dissolve in water, its solubility changes little when temperature changes while the solubility of
KCl change much when temperature changes. This property is used to separate the two salts.
- NaCl is used to produce Na, Cl2, HCl, NaOH and other compounds of sodium.
* Javel water NaCl+NaClO
Contain ions Cl-, ClO-; chlorine smell; has base properties.
- Javel water is a high oxidation substance. The reason is it react with CO2 to form oxygen atom.
Therefore it is used to erase color.

NaClO is decomposed by heating:

Javel water is prepared by the reaction of Cl2 with alkaline solution:

In industry, it is produced by electrolysis of dilute NaCl solution without membrane.

3.5.3.2 Carbonate of alkaline metals

Two types: hydrocarbonate MHCO3 and carbonate M2CO3.
They are all very soluble (except for Li2CO3 and NaHCO3). They are hydrolyzed:
MHCO3 is decomposed when heat:

M2CO3 is very stable to heat, they melt without dissociation. Below are their melting points:
CHAPTER 4. GROUP IIA METALS

4.1 Introduction
The Group 2 or alkaline earth metals exemplify and continue the trends in properties
noted for the alkali metals. No new principles are involved, but the ideas developed in the
preceding chapter gain emphasis and clarity by their further application and extension. Indeed,
there is an impressively close parallelism between the two groups as will become increasingly
clear throughout the chapter. The discovery of beryllium in 1798 followed an unusual train of
events. The mineralogist R.-J. Hauy had observed the remarkable similarity in external
crystalline structure, hardness and density of a beryl from Limoges and an emerald from Peru,
and suggested to L.-N. Vauquelin that he should analyse them to see if they were chemically
identical? As a result, Vauquelin showed that both minerals contained not only alumina and
silica as had previously been known, but also a new earth, beryllia, which closely resembled
alumina but gave no alums, apparently did not dissolve in an excess of KOH (perhaps because it
had been fused?) and had a sweet rather than an astringent taste. Caution : beryllium compounds
are now known to be extremely toxic, especially as dusts or smokes; it seems likely that this
toxicity results from the ability of Be2+ to displace Mg2+ from Mg-activated enzymes due to its
stronger coordinating ability. Both beryl and emerald were found to be essentially Be3A12Si6O18,
the only difference between them being that emerald also contains 2% Cr, the source of its green
colour. The combining weight of Be was 4.7 but the similarity (diagonal relation) between Be
and A1 led to considerable confusion concerning the valency and atomic weight of Be (2 x 4.7 or
3 x 4.7); this was not resolved until Mendeleev 70 year later stated that there was no room for a
tervalent element of atomic weight 14 near nitrogen in his periodic table, but that a divalent
element of atomic weight 9 would fit snugly between Li and B. Beryllium metal was first
prepared by F. Wohler in 1828 (the year he carried out his celebrated synthesis of urea from
NH4CNO); he suggested the name by allusion to the mineral. The metal was independently
isolated in the same year by A.-B. Bussy using the same method - reduction of BeC12 with
metallic K. The first electrolytic preparation was by P. Lebeau in 1898 and the first commercial
process (electrolysis of a fused mixture of BeF2 and BaF2) was devised by A. Stock and H.
Goldschmidt in 1932. The close parallel with the development of Li technology (pp. 68-70) is
notable.

4.2 The Elements

4.2.1 Terrestrial abundance and distribution
Beryllium, like its neighbours Li and B, is relatively unabundant in the earth’s crust; it occurs to
the extent of about 2 ppm and is thus similar to Sn (2.1 ppm), Eu (2.1 ppm) and As(1.8
ppm). However, its occurrence as surface deposits of beryl in pegmatite rocks (which are
the last portions of granite domes to crystallize makes it readily accessible. Crystals as large
as 1 m on edge and weighing up to 60 tonnes have been reported. World reserves in
commercial deposits are about 4 million tonnes of contained Be and mined production in
1985-86 was USA 223, USSR 76 and Brazil 37 tonnes of contained Be, which together
accounted for 98% of world production. The cost of Be metal was $690/kg in 1987. By contrast,
world supplies of magnesium are virtually limitless: it occurs to the extent of 0.13% in sea
water, and electrolytic extraction at the present annual rate, if continued for a million years,
would only reduce this to 0.12%.

4.2.2 Production and uses of the metals

Beryllium is extracted from beryl by roasting the mineral with Na2SiF6 at 700-750oC, leaching
the soluble fluoride with water and then precipitating Be(OH)2 at about pH 12. The metal is
usually prepared by reduction of BeF2 with Mg at about 1300°C or by electrolysis of fused
mixtures of BeC12 and alkali metal chlorides. It is one of the lightest metals known and has one
of the highest mps of the light metals. Its modulus of elasticity is one-third greater than that of
steel. The largest use of Be is in high-strength alloys of Cu and Ni. Magnesium is produced on a
large scale (400000 tonnes in 1985) either by electrolysis or silicothermal reduction. The major
producers are the USA (43%), the former Soviet Union (26%), and Norway (17%). The
electrolytic process uses either fused anhydrous MgCl2 at 750°C or partly hydrated MgC12 from
sea water at a slightly lower temperature. The silicothermal process uses calcined dolomite and
ferrosilicon alloy under reduced pressure at 1150°C:
2(MgO.CaO) + FeSi → 2Mg + Ca2SiO4 + Fe
Magnesium is industry's lightest constructional metal, having a density less than two-thirds that
of Al.
The other alkaline earth metals Ca, Sr and Ba are produced on a much smaller scale than Mg.
Calcium is produced by electrolysis of fused CaC12 (obtained either as a byproduct of the Solvay
process or by the action of HCl or CaCO3). It is less reactive than Sr or Ba, forming a protective
oxide-nitride coating in air which enables it to be machined in a lathe or handled by other
standard metallurgical techniques. Calcium metal is used mainly as an alloying agent to
strengthen Al bearings, to control graphitic C in cast-iron and to remove Bi from Pb. Chemically
it is used as a scavenger in the steel industry (0, S and P), as a getter for oxygen and nitrogen, to
remove N2 from argon and as a reducing agent in the production of other metals such as Cr, Zr,
Th and U. Calcium also reacts directly with H2 to give CaH2, which is a useful source of H2.

4.2.3 Properties of the elements

Table 5.1 lists some of the atomic properties of the Group 2 elements. Comparison with the data
for Group 1 elements shows the substantial increase in the ionization energies; this is related to
their smaller size and higher nuclear charge, and is particularly notable for Be. Indeed, the “ionic
radius” of Be is purely a notional figure since no compounds are known in which uncoordinated
Be has a 2+ charge. In aqueous solutions the reduction potential of Be is much less than that of
its congeners, again indicating its lower electropositivity. By contrast, Ca, Sr, Ba and Ra have
reduction potentials which are almost identical with those of the heavier alkali metals; Mg
occupies an intermediate position.
Be and Mg are silvery white metals whereas Ca, Sr and Ba are pale yellow (as are the divalent
rare earth metals Eu and Yb) although the colour is less intense than for Cs (p. 74). All the
alkaline earth metals are lustrous and relatively soft, and their physical properties (Table 5.2),
when compared with those of Group 1 metals, show that they have a substantially higher mp, bp,
density and enthalpies of fusion and vaporization. This can be understood in terms of the size
factor mentioned in the preceding paragraph and the fact that 2 valency electrons per atom are
now available for bonding. Again, Be is notable in melting more than 1100" above Li and being
nearly 3.5 times as dense; its enthalpy of fusion is more than 5 times that of Li. Beryllium
resembles Al in being stable in moist air due to the formation of a protective oxide layer, and
highly polished specimens retain their shine indefinitely. Magnesium also resists oxidation but
the heavier metals tarnish readily. Beryllium, like Mg and the high-temperature form of Ca
(>450"C), crystallizes in the hcp arrangement, and this confers a marked anisotropy on its
properties; Sr is fcc, Ba and Ra are bcc like the alkali metals.

4.2.4 Chemical reactivity and trends

Beryllium metal is relatively unreactive at room temperature, particularly in its massive form. It
does not react with water or steam even at red heat and does not oxidize in air below 600°C,
though powdered Be burns brilliantly on ignition to give BeO and Be3N2. The halogens (X2)
react above about 600°C to give BeX2 but the chalcogens (S, Se, Te) require even higher
temperatures to form BeS, etc. Ammonia reacts above 1200°C to give Be3N2 and carbon forms
Be2C at 1700°C. In contrast with the other Group 2 metals, Be does not react directly with
hydrogen, and BeH2 must be prepared indirectly. Cold, concentrated HNO3 passivates Be but the
metal dissolves readily in dilute aqueous acids (HCl, H2SO4, HNO3) with evolution of hydrogen.
Beryllium is sharply distinguished from the other alkaline earth metals in reacting with aqueous
alkalis (NaOH, KOH) with evolution of hydrogen. It also dissolves rapidly in aqueous NH4HF2
(as does Be(OH)2), a reaction of some technological importance in the preparation of anhydrous
BeF2 and purified Be:
2NH4HF2(aq) + Be(s) → (NH4)2BeF4 + H2 (g)
(NH4)2BeF4(s) → BeF2(s) + 2NH4F (subl)
Magnesium is more electropositive than the amphoteric Be and reacts more readily with most of
the non-metals. It ignites with the halogens, particularly when they are moist, to give MgX2, and
burns with dazzling brilliance in air to give MgO and Mg3N2. It also reacts directly with the other
elements in Groups 15 and 16 (and Group 14) when heated and even forms MgH2 with hydrogen
at 570oC and 200atm. Steam produces MgO (or Mg(OH)2) plus H2, and ammonia reacts at
elevated temperature to give Mg3N2. Methanol reacts at 200o to give Mg(OMe)2 and ethanol
(when activated by a trace of iodine) reacts similarly at room temperature. Alkyl and aryl halides
react with Mg to give Grignard reagents RMgX. The heavier alkaline earth metals Ca, Sr, Ba
(and Ra) react even more readily with nonmetals, and again the direct formation of nitrides M3N2
is notable. Other products are similar though the hydrides are more stable and the carbides less
stable than for Be and Mg. There is also a tendency, previously noted for the alkali metals, to
form peroxides MO2 of increasing stability in addition to the normal oxides MO. Calcium, Sr and
Ba dissolve in liquid NH3 to give deep blue-black solutions from which lustrous, coppery,
ammoniates M(NH3)6 can be recovered on evaporation; these ammoniates gradually decompose
to the corresponding amides, especially in the presence of catalysts:

4.3 Compounds
4.3.1 Introduction
The predominant divalence of the Group 2 metals can be interpreted in terms of their electronic
configuration, ionization energies, and size (see Table 5.1). Further ionization to give simple
salts of stoichiometry MX3 is precluded by the magnitude of the energies involved, the third
stage ionization being 14849 kJ.mol-1 for Be, 7733 kJ.mol-1 for Mg and 4912 kJ.mol-1 for Ca;
even for Ra the estimated value of 3281 kJ.mol-1 involves far more energy than could be
recovered by additional bonding even if this were predominantly covalent. Reasons for the
absence of univalent compounds MX are less obvious. The first-stage ionization energies for Ca,
Sr, Ba and Ra are similar to that of Li though the larger size of the hypothetical univalent Group
2 ions, when compared to Li, would reduce the lattice energy somewhat (p. 82). By making
plausible assumptions about the ionic radius and structure we can estimate the approximate
enthalpy of formation of such compounds and they are predicted to be stable with respect to the
constituent elements; their non-existence is related to the much higher enthalpy of formation of
the conventional compounds MX2, which leads to rapid and complete disproportionation. For
example, the standard enthalpy of formation of hypothetical crystalline MgCl, assuming the
NaCl structure, is -125 kJ.mol-1, which is substantially greater than for many known stable
compounds and essentially the same as the experimentally observed value for AgCl: ∆H: = - 127
kJ.mol-1. However, the corresponding (experimental) value for ∆H; (MgC12) is -642 kJ.mol-1,
whence an enthalpy of disproportionation of - 196 kJ.mol-1 :

4.3.2 Hydrides and halides

The shapes of the monomeric molecules of the Group 2 halides (gas phase or matrix isolation)
pose some interesting problems for those who are content with simple theories of bonding and
molecular geometry. Thus, as expected on the basis of either sp hybridization or the VSEPR
model, the dihalides of Be and Mg and the heavier halides of Ca and Sr are essentially linear.
However, the other dihalides are appreciably bent, e.g. CaF2 - 145o, SrF2 - 120o, BaF2 - 108o;
SrC12 - 130o, BaC12 - 115o; BaBr2 – 115o; BaI2 - 105o. The uncertainties on these bond angles
are often quite large (±10o) and the molecules are rather flexible, but there seems little doubt that
the equilibrium geometry is substantially non-linear. This has been interpreted in terms of sd
(rather than sp) hybridization or by a suitable ad hoc modification of the VSEPR theory.
The crystal structures of the halides of the heavier Group 2 elements also show some
interesting trends (Table 5.3). For the fluorides, increasing size of the metal enables its
coordination number to increase from 4 (Be) to 6 (Mg) and 8 (Ca, Sr, Ba). CaF2 (fluorite) is a
standard crystal structure type and its cubic unit cell is illustrated in Fig. 3.2. The other halides
(CI, Br, I) show an increasing trend away from three-dimensional structures, the Be halides
forming chains and the others tending towards layer lattice structures such as CdC12, CdI2 and
PbI2. SrI2 is unique in this group in having sevenfold coordination (Fig. 3.3);
Table 4.3 Crystal structures of alkaline earth halines
 Figure 3.2 Unit cell of CaF2 showing eightfold (cubic) coordination of Ca by 8F
and fourfold (tetrahedral) coordination of F by 4Ca. The structure can be thought of as an
fcc array of Ca in which all the tetrahedral interstices are occupied by F.

Figure 4.3 Structure of SrI2 showing sevenfold coordination of Sr by I. The

planes 1 and 2 are almost parallel (4.5o) and the planes la2a2d and lb2b2c1c are at an
angle of 12o to each other.
CaF2 is a white, high-melting (1418°C) solid whose low solubility in water permits quantitative
analytical precipitation. The other fluorides (except BeF2) are also high melting and rather
insoluble. By contrast, the chlorides tend to be deliquescent and to have much lower mps (715-
960o); they readily form numerous hydrates and are soluble in alcohols. MgC12 is one of the
most important salts of Mg industrially and its concentration in sea water is exceeded only by
NaC1. CaC12 is also of great importance, as noted earlier.
The bromides and iodides continue the trends to lower mps and higher solubilities in water and
their ready solubility in alcohols, ethers, etc., is also notable; indeed, MgBr2 forms numerous
crystalline solvates such as MgBr2.6ROH (R = Me, Et, Pr), MgBr2.6Me2CO, MgBr2.3Et2O, in
addition to numerous ammines MgBr2.nNH3 (n = 2-6).
The ability of Group 2 cations to form coordination complexes is clearly greater than that of
Group 1 cations.
Alkaline earth salts MHX, where M = Ca, Sr or Ba and X = C1, Br or I can be prepared by
fusing the hydride MH2 with the appropriate halide MX2 or by heating M+MX2 in an atmosphere
of H2 at 900o. These hydride halides appear to have the PbClF layer lattice structure though the H
atoms were not directly located. The analogous compounds of Mg have proved more elusive and
the preceding preparative routes merely yield physical mixtures. However, MgClH and MgBrH
can be prepared as solvated dimers by the reaction of specially activated MgH2 with MgX2 in thf:

The chloride can be crystallized but the bromide disproportionates. On the basis of mol wt and
infrared spectroscopic evidence the proposed structure is:

4.3.3 Oxides and hydroxides

The oxides MO are best obtained by calcining the carbonates; dehydration of the hydroxides at
red heat offers an alternative route. BeO (like the other Be chalcogenides) has the wurtzite
structure and is an excellent refractory, combining a high mp (2507°C) with negligible vapour
pressure below this temperature; it has good chemical stability and a very high thermal
conductivity which is greater than that of any other non-metal and even exceeds that of some
metals. The other oxides in the group all have the NaCl structure and this structure is also
adopted by the chalcogenides (except MgTe which has the wurtzite structure). Lattice energies
and mps are again very high: MgO mp 2832o, CaO 2627o, SrO 2665o, BaO 1913°C (all ca. 30o).
The compounds are comparatively unreactive in bulk but their reactivity increases markedly with
decrease in particle size and increase in atomic weight. Notable reactions (which reverse those
used to prepare the oxides) are with CO2 and with H2O. MgO is extensively used as a refractory:
like BeO it is unusual in being both an excellent thermal conductor and a good electrical
insulator, thus finding widespread use as the insulating radiator in domestic heating ranges and
similar appliances. CaO (lime) is produced on an enormous scale in many countries and, indeed,
is one of the half-dozen largest tonnage industrial chemicals to be manufactured.
In addition to the oxides MO, peroxides MO2 are known for the heavier alkaline earth
metals and there is some evidence for yellow superoxides M(O2)2 of Ca, Sr and Ba; impure
ozonides Ca(O3)2 and Ba(O3)2 have also been reported. As with the alkali metals, stability
increases with electropositive character and size: no peroxide of Be is known; anhydrous MgO2
can only be made in liquid NH3 solution, aqueous reactions leading to various peroxide hydrates;
CaO2 can be obtained by dehydrating CaO2.8H2O but not by direct oxidation, whereas SrO2 can
be synthesized directly at high oxygen pressures and BaO2 forms readily in air at 500o Reactions
with aqueous reagents are as expected, and the compounds can be used as oxidizing agents and
bleaches:
MgO2 has the pyrite structure and the Ca, Sr and Ba analogues have the CaC2 structure
The hydroxides of Group 2 elements show a smooth gradation in properties, with steadily
increasing basicity, solubility, and heats of formation from the corresponding oxide. Be(OH)2 is
amphoteric and Mg(OH)2 is a mild base which, as an aqueous suspension (milk of magnesia), is
widely used as a digestive antacid. Note that, though mild, Mg(OH)2 will neutralize 1.37 times as
much acid as NaOH, weight for weight, and 2.85 times as much as NaHCO3. Ca(OH)2 and
Sr(OH)2 are moderately strong to strong bases and Ba(OH)2 approaches the alkali hydroxides in
strength.
Beryllium salts rapidly hydrolyse in water to give a series of hydroxo complexes of
undetermined structure; the equilibria depend sensitively on initial concentration, pH,
temperature, etc., and precipitation begins when the ratio OH-/Be2+(aq) > 1. Addition of further
alkali redissolves the precipitate and the properties of the resultant solution are consistent (at
least qualitatively) with the presence of isopolyanions of the type [(HO)2(Be(p-OH)2],Be(OH)2
Further addition of alkali progressively depolymerizes this chain anion by hydroxyl addition
until ultimately the mononuclear beryllate anion [Be(OH)4]2- is formed. The analogy with
Zn(OH)2 and Al(OH)3 is clear.
The solubility of Be(OH)2 in water is only -3 x 10-4 gl-1 at room temperature, compared
with 3 x 10-2 g l-1 for Mg(OH)2 and 1.3 gl-1 for Ca(OH)2. Strontium and barium hydroxides have
even greater solubilities.
The crystal structures of M(OH)2 also follow group trends. Be(OH)2 crystallizes with 4-
coordinate Be in the Zn(OH)2 structure which can be considered as a diamond or cristobalite
(SiO2) lattice distorted by H bonding. Mg(OH)2 (brucite) and Ca(OH)2 have 6-coordinate cations
in a CdI2 layer lattice structure with OH bonds perpendicular to the layers and strong O-H...O
bonding between them. Strontium is too large for the CdI2 structure and Sr(OH)2 features 7-
coordinate Sr (3 + 4), the structure being built up of edge-sharing monocapped trigonal prisms
with no H bonds. (The monohydrate has bicapped trigonal prismatic coordination about Sr.) The
structure of Ba(OH)2 is complex and has not yet been fully determined.

4.3.4 Oxoacid salts and coordination complexes

The chemical trends and geochemical significance of the oxoacid salts of the alkaline earth
metals have already been mentioned and the immense industrial importance of the carbonates
and sulfates in particular can hardly be over emphasized. A speciality use can also be noted:
mother-of-pearl (nacre) is a material composed of thin plates of chalk (in the form of aragonite)
stuck together with a protein glue. It is irridescent and highly decorative when polished and,
despite being 95% chalk, is very strong. Calcium sulfate usually occurs as the dihydrate
(gypsum) though anhydrite (CaSO4) is also mined. Alabaster is a compact, massive, finegrained
form of CaSO4.2H2O resembling marble. When gypsum is calcined at 150-165°C it looses
approximately three-quarters of its water of crystallization to give the hemihydrate CaSO4.1H2O,
also known as plaster of Paris because it was originally obtained from gypsum quarried at
Montmartre. Heating at higher temperatures yields various anhydrous forms:

Magnesium forms few halide complexes of the type MX42-, though [NEt4]2[MgC14] has been
reported; examples of MXn(n-2)- for the heavier alkaline earths are lacking, though hydrates and
other solvates are well known. The first examples of monomeric six-coordinate (octahedral)
complexes of strontium salts have recently been characterized, viz. trans-[SrI2(hmpa)4] and cis-
[Sr(NCS)2(hmpa)4] where hmpa is (Me2N)3PO; they were made as colourless crystals by
refluxing a mixture of NH4I (or NH4SCN) with metallic Sr and hmpa in toluene for 1 hour.

4.3.5 Organometallic compounds

Compounds containing M-C bonds are well established for Be and Mg but, as with the
alkali metals, reactivity within the group increases with increasing electropositivity, and
relatively few organometallic compounds of Ca, Sr or Ba have been isolated.
Magnesium dialkyls and diaryls, though well established, have been relatively little studied by
comparison with the vast amount of work which has been published on the Grignard reagents
RMgX. The dialkyls (and diaryls) can be conveniently made by the reaction of LiR (LiAr) on
Grignard reagents, or by the reaction of HgR2 (HgAr2) on Mg metal (sometimes in the presence
of ether). On an industrial scale, alkenes can be reacted at 100o under pressure with MgH2 or
with Mg in the presence of H2:

A suitable laboratory method is to shift the Schlenk equilibrium in a Grignard solution by adding
dioxan to precipitate the complex MgX2.diox; this enables MgR2 to be isolated by careful
removal of solvent under reduced pressure:
CHAPTER 5. THE GROUP IIIA ELEMENTS (ALUMINUM, GALLIUM, INDIUM,
THALIUM)

5.1 Introduction
Aluminium derives its name from alum, the double sulfate KAl(SO4)2.12H2O, which was
used medicinally as an astringent in ancient Greece and Rome (Latin alumen, bitter salt).
Humphry Davy was unable to isolate the metal but proposed the name “alumium” and then
“aluminum”; this was soon modified to aluminium and this form is used throughout the world
except in North America where the ACS decided in 1925 to adopt “aluminum” in its
publications. The impure metal was first isolated by the Danish scientist H. C. Oersted using the
reaction of dilute potassium amalgam on AlC13. This method was improved in 1827 by H.
Wohler who used metallic potas- sium, but the first commercially successful process was devised
by H. St.-C. Deville in 1854 using sodium. In the same year both he and R. W. Bunsen
independently obtained metallic aluminium by electrolysis of fused NaAlCl4. So precious was
the metal at this time that it was exhibited next to the crown jewels at the Paris Exposition of
1855 and the Emperor Louis Napoleon III used A1 cutlery on state occasions. The dramatic
thousand-fold drop in price which occurred before the end of the century (Table 7.1) was due
first to the advent of cheap electric power follow-ing the development of the dynamo by W. von
Siemens in the 1870s, and secondly to the independent development in 1886 of the electrolysis
of alumina dissolved in cryolite (Na3AlF6) by P. L. T. HCroult in France and C. M. Hall in the
USA; both men were 22 years old at the time. World production rose quickly and in 1893
exceeded 1000 tonnes pa for the first time.

5.2 The Elements

5.2.1 Terrestrial abundance and distribution
Aluminium is the most abundant metal in the earth’s crust (8.3% by weight); it is exceeded in
abundance only by 0 (45.5%) and Si (25.7%), and is approached only by Fe (6.2%) and Ca
(4.6%). Aluminium is a major constituent of many common igneous minerals including feldspars
and micas. These, in turn, weather in temperate climates to give clay minerals such as kaolinite
[Al2(OH)4Si2O5], montmorillonite and vermiculite. It also occurs in many well-known though
rarer minerals such as cryolite (Na3AlF6), spinel (MgAl2O4), garnet [Ca3Al2(SiO4)3], beryl
(Be3Al2Si6O18), and turquoise [Al2(OH)3PO4H2O/Cu]. Corundum (Al2O3) is one of the hardest
substances known and is therefore used as an abrasive; many gemstones are impure forms of
Al2O3, e.g. ruby (Cr), sapphire (Co), oriental emerald, etc. Commercially, the most important
mineral is bauxite AlOx(OH)3-x, (0 < x < 1); this occurs in a wide belt in tropical and subtropical
regions as a result of the leaching out of both silica and various metals from aluminosilicate.

5.2.2 Preparation and uses of the metals

The huge difference in scale between the production of A1 metal, on the one hand, and the other
elements in the group is clear from the preceding section. The tremendous growth of the Al
industry compared with all other non-ferrous metals is indicated in Table 7.3 and A1 production
is now exceeded only by that of iron and steel.
Production of A1 metal involves two stages: (a) the extraction, purification and dehydration of
bauxite, and (b) the electrolysis of Al2O3 dissolved in molten cryolite Na3AlF6. Bauxite is now
almost universally treated by the Bayer process; this involves dissolution in aqueous NaOH,
separation from insoluble impurities (red muds), partial precipitation of the trihydrate and
calcining at 1200o. Bauxites approximating to the "monohydrate" AlOOH require higher
concentrations of NaOH (200-300 g l-1) and higher temperatures and pressures (200-250oC, 35
atm) than do bauxites approximating to Al(OH)3 (100-150 gl-1 NaOH, 120-140°C). Electrolysis
is carried out at 940-980°C in a carbon-lined steel cell (cathode) with carbon anodes. Originally
Al2O3 was dissolved in molten cryolite (HCroult-Hall process) but cryolite is a rather rare
mineral and production from the mines in Greenland provide only about 30000 tonnes pa, quite
insufficient for world needs. Synthetic cryolite is therefore manufactured in lead-clad vessels by
the reaction of HF on sodium aluminate (from the Bayer process):

No further cryolite is actually needed once the smelting process is in operation because it is
produced in the reduction cells by neutralizing the Na2O brought into the cell as an impurity in
the alumina using AlF3:

Gallium metal is now obtained as a byproduct of the A1 industry. The Bayer process for
obtaining alumina from bauxite gradually enriches the alkaline solutions from an initial weight
ratio GdA1 of about 1/5000 to about 1/300; electrolysis of these extracts with an Hg electrode
gives further concentration, and the solution of sodium gallate is then electrolysed with a
stainless steel cathode to give Ga metal. Ultra high-purity Ga for semiconductor uses is obtained
by further chemical treatment with acids and O2 at high temperatures followed by crystallization
and zone refining.
Indium, like Ga, is normally recovered by electrolysis after prior concentration in
processes leading primarily to other elements (Pb/Zn). It is a soft, silvery metal with a brilliant
lustre and (like Sn) it gives out a high-pitched “cry” when bent. Formerly it was much used to
protect bearings against wear and corrosion but the pattern of use has been changing in recent
years and now its most important applications are in low-melting alloys and in electronic
devices. Thus meltable safety devices, heat regulators, and sprinklers use alloys of In with Bi,
Cd, Pb and Sn (mp 50-100°C) and In-rich solders are valuable in sealing metal-nonmetal joints
in high vacuum apparatus. Indium is of particular importance in the manufacture of p-n-p
transistor junctions in Ge (p. 369) and to solder semiconductor leads at low temperature; the
softness of the metal also minimizes stress in the Ge during subsequent cooling. So-called III-V
semiconductors like InAs and InSb are used in low-temperature transistors, thermistors and
optical devices (photoconductors), and InP is used for high-temperature transistors.
Technical grade Tl is purified from other fluedust elements (Ni; Zn, Cd; In; Ge, Pb; As;
Se, Te) by dissolving it in warm dilute acid, then precipitating the insoluble PbSO4 and adding
HCl to precipitate TlCl. Further purification is effected by electrolysing Tl2SO4 in dilute H2SO4
with short Pt wire electrodes, followed by fusion of the deposited Tl metal at 350-400°C under
an atmosphere of H2.

5.2.3 Properties of the elements

The atomic properties of the Group 13 elements (including boron) are compared in Table 7.4. All
have odd atomic numbers and correspondingly few stable isotopes. The varying precision of
atomic weights has been discussed. The electronic configuration is ns2np1 in each case but the
underlying core varies considerably: for B and Al it is the preceding noble gas core, for Ga and
In it is noble gas plus d10, and for Tl noble gas plus 4f145d10. This variation has a substantial
influence on the trends in chemical properties of the group and is also reflected in the ionization
energies of the elements. Thus, as shown in Fig. 4.1, the expected decrease from B to A1 is not
followed by a further decrease to Ga because of the "d-block contraction" in atomic size and the
higher effective nuclear charge for this element which stems from the fact that the 10 added d
electrons do not completely shield the extra 10 positive charges on the nucleus. Similarly, the
decrease between Ga and In is reversed for T1 as a result of the further influence of the f block or
lanthanide contraction. It is notable that these irregularities for the Group 13 elements do not
occur for the Group 3 elements Sc, Y and La, which show a steady decrease in ionization energy
from B and Al, all 5 elements having the same type of underlying core (noble gas). This has a
decisive influence on the comparative chemistry of the two subgroups.
Table 5.1. Atomic properties of Group 13 elements

Boron is a covalently bonded, refractory, nonmetallic insulator of great hardness and is thus not
directly comparable in its physical properties with Al, Ga, In and T1, which are all low melting,
rather soft metals having a very low electrical resistivity (Table 4.5). The heats of fusion and
vaporization of the metals are also much lower than those of boron and tend to decrease with
increasing atomic number. In all these properties the metals resemble the neighbouring metals
Zn, Cd, Hg; Sn, Pb, etc., and it is probable that in each case the properties are related to the
rather small number of electrons available for metallic bonding. Some have seen this as a
manifestation of the “inert-pair effect” (see p. 226). The interatomic distances in these elements
are also somewhat longer than expected from general trends.

Figure 5.1 Trends in successive ionization energies IM(I), IM(II), and IM(III), and their sum Σ for
elements in Groups 3 and 13.

The crystal structure of A1 is fcc, typical of many metals, each A1 being surrounded by 12
nearest neighbours at 286pm. Thallium also has a typical metallic structure (hcp) with 12 nearest
neighbours at 340pm. Indium has an unusual structure which is slightly distorted from a regular
close-packed arrangement: the structure is facecentred tetragonal and each In has 4 neighbours at
324pm and 8 at the slightly greater distance of 336pm Gallium has a unique orthorhombic
(pseudotetragonal) structure in which each Ga has 1 very close neighbour at 244pm and 6 further
neighbours, 2 each at 270, 273 and 279pm. The structure is very similar to that of iodine and the
appearance of pseudo-molecules Ga2 may result from partial pair-wise interaction on
neighbouring atoms of the single p electron outside the [Ar]3d104s2 core which immediately
follows the first transition series. As such it can be compared with Hg which also has a very low
mp and completes the [Xe]4f145d106s2 “pseudo-noble-gas” configuration following the
lanthanide elements. Note that all interatomic contacts in metallic Ga are less than those in Al,
again emphasizing the presence of a “d- block contraction”. Gallium is also unusual in
contracting on melting, the volume of the liquid phase being 3.4% less than that of the solid; the
same phenomenon occurs with the next element in the periodic table Ge, and also with Sb and
Bi, in addition to the well-known example of H2O. In each case, a structural feature in the solid
is broken down to permit more efficient packing of atoms in the liquid state.
Table 5.5 Physical properties of Group 13 elements

The standard electrode potentials of the heavier Group 13 elements reflect the decreasing
stability of the f3 oxidation state in aqueous solution and the tendency, particularly of Tl, to form
compounds in the +I oxidation state (p. 226). The trend to increasing electropositivity of the
group oxidation state which was noted for Groups 1 and 2 does not occur with Group 13 but is
found, as expected, in Group 3 (Fig. 4.2). Similarly, the steady decrease in electronegativity in
the series B > A1 > Sc > Y > La > Ac is reversed in Group 13 and there is a steady increase in
electronegativity from Al to Tl.

5.2.4 Chemical reactivity and trends

The Group 13 metals differ sharply from the non-metallic element boron both in their greater
chemical reactivity at moderate temperatures and in their well-defined cationic chemistry for
aqueous solutions. The absence of a range of volatile hydrides and other cluster compounds
analogous to the boranes and carboranes is also notable. Aluminium combines with most non-
metallic elements when heated to give compounds such as AlN, Al2S3, AlX3, etc. It also forms
intermetallic compounds with elements from all groups of the periodic table that contain metals.
Because of its great affinity for oxygen it is used as a reducing agent to obtain Cr, Mn, V, etc., by
means of the thermite process of J. W. Goldschmidt. Finely powdered A1 metal explodes on
contact with liquid O2, but for normal samples of the metal a coherent protective oxide film
prevents appreciable reaction with oxygen, water or dilute acids; amalgamation with Hg or
contact with solutions of salts of certain electropositive metals destroys the film and permits
further reaction. Aluminium is also readily soluble in hot concentrated hydrochloric acid and in
aqueous NaOH or KOH at room temperature with liberation of H2. This latter reaction is
sometimes written as

though it is likely that the species in solution is the hydrated tetrahydroxoaluminate anion
[Al(OH)4]-(aq) or [Al(H2O)2(OH)4]-.

Figure 5.2 Trends in standard electrode potential Eo and electronegativity χ for elements in
Groups 3 and 13.
Al(OH)3 is amphoteric, forming both salts and aluminates (Greek amphoteros, in both ways).
Thus the freshly precipitated hydroxide is readily soluble in both acid and alkali:

In these reactions the coordination number of A1 has been assumed to be 6 throughout though
direct evidence on this point is rarely available. Amphoterism is also exhibited in anhydrous
reactions, e.g.:
Aluminium compounds of weak acids are extensively hydrolysed to [Al(H2O)3(OH)3] and the
corresponding hydride, e.g. Al2S3 → 3H2S, AlN → NH3, and Al4C3 → 3CH4. Similarly, the
cyanide, acetate and carbonate are unstable in aqueous solution. Hydrolysis of the halides and
other salts such as the nitrate and sulfate is incomplete but aqueous solutions are acidic due to the
ability of the hydrated cation [Al(H2O)6]3+ to act as proton donor giving [Al(H2O)5 (OH)]2+, [Al(
H2O)4 (OH)2]+, etc. If the pH is gradually increased this deprotonation of the mononuclear
species is accompanied by aggregation via OH bridges to give species such as

and then to precipitation of the hydrous oxide. This is of particular use in water clarification
since the precipitating hydroxide nucleates on fine suspended particles which are thereby thrown
out of suspension. Still further increase in pH leads to redissolution as an aluminate (Fig. 4.3).
Similar behaviour is shown by BeII, ZnII, GaIII, SnII, PbII etc. A detailed quantitative theory of
amphoterism is difficult to construct but it is known that amphoteric behaviour occurs when (a)
the cation is weakly basic, (b) its hydroxide is moderately insoluble, and (c) the hydrated species
can also act as proton donors.
Anhydrous Al salts cannot be prepared by heating the corresponding hydrate for reasons closely
related to the amphoterism and hydrolysis of such compounds. For example, AlCl3.6H2O is, in
reality, [Al(H2O)6]Cl3 and the strength of the Al-O interaction precludes the formation of Al-Cl
bonds:
Figure 5.3 Schematic representation of the variation of concentration of an A1 salt as a function
of pH.
The amphoteric behaviour of GaIII salts parallels that of AlIII; indeed, Ga2O3 is slightly more
acidic than Al2O3 and solutions of gallates tend to be more stable than aluminates. Consistent
with this, pK, for the equilibrium

is 4.95 for A1 and 2.60 for Ga. Indium is more basic than Ga and is only weakly amphoteric. The
metal does not dissolve in aqueous alkali whereas Ga does. This alternation in the sequence of
basicity can be related to the electronic and size factors. Thallium behaves as a moderately strong
base but is not strictly comparable with other members of the group because it normally exists as
TlI in aqueoussolution. Thus, Tl metal tarnishes readily and reacts with steam or moist air to give
TlOH. The electrode potential data in Table 7.5 show that TlI is much more stable than TlIII in
aqueoussolution and indicate that TlIII compounds can act as strong oxidizing agents.
Compounds of TlI have many similarities to those of the alkali metals: TlOH is very soluble and
is a strong base; Tl2CO3 is also soluble and resembles the corresponding Na and K compounds;
TlI forms colourless, well crystallized salts of many oxoacids, and these tend to be anhydrous
like those of the similarly sized Rb and Cs; TlI salts of weak acids have a basic reaction in
aqueous solution as a result of hydrolysis; TlI forms polysulfides (e.g. Tl2S5) and polyiodides,
etc. In other respects TlI resembles the more highly polarizing ion Ag+,e.g. in the colour and
insolubility of its chromate, sulfide, arsenate and halides (except F), though it does not form
ammine complexes in aqueous solution and its azide is not explosive.
The stability of the + 1 oxidation state in Group 13 increases in the sequence A1 < Ga < In < T1,
and numerous examples of MI compounds will be found in the following sections. The
occurrence of an oxidation state which is 2 less than the group valency is sometimes referred to
as the "inert-pair effect" but it is important to recognize that this is a description not an
explanation. The phenomenon is quite general among the heavier elements of the p block (i.e. the
post-transition elements in Groups 13-16). For example, Sn and Pb commonly occur in both the
+2 and +4 oxidation states; P, As, Sb and Bi in the +3 and +5; S, Se, Te and Po in the +2, +4, and
+6 states. The term "inert-pair effect" is somewhat misleading since it implies that the energy
required to involve the ns2 electrons in bonding increases in the sequence A1 < Ga < In < T1.
Reference to Table 4.4 shows that this is not so (the sequence is, in fact, In < A1 < T1 < Ga).
The explanation lies rather in the decrease in bond energy with increase in size from A1 to T1 so
that the energy required to involve the s electrons in bonding is not compensated by the energy
released in forming the 2 additional bonds. The argument is difficult to quantify since the
requisite energy terms are not known. Thus it is unrealistic to use the simple ionic bond model to
calculate the heat of formation of MX3 because compounds like TlC13 are not ionic, i.e. [Tl3+(Cl-
)3] - the energy for the ionization of M(g) to M3+(g) is greater than 5000 kJ mol-1 for each
element and substantial covalent interaction between M3+ and X- would also be expected. In the
absence of semi-empirical bond energy data or ab initio MO calculations it is only possible to
note that the higher oxidation state becomes progressively less stable with respect to the lower
oxidation state as atomic number increases within the group. This is seen, for example, by
comparing the standard electrode potentials in aqueous solution for MIII and MI in Table 4.5.
Similarly, from the somewhat fragmentary data available, it appears that the enthalpy of
formation of the anhydrous halides remains approximately constant for MX but diminishes
irregularly from Al to Tl for MX3 (X = C1, Br, I). The overall result depends not only on the
simple Born-Haber terms but also on a combination of several other factors including changes in
structure and bond type, covalency effects, enthalpies of hydration, entropy effects, etc., and a
quantitative rationalization of all the data has not yet been achieved.
Group 13 metals furnish a good example of the general rule that an element is more
electropositive in its lower than in its higher oxidation state: the lower oxide and hydroxide are
more basic and the higher oxide and hydroxide more acidic. The reasons for this behaviour are
similar to those already discussed when comparing Group 2 with Group 1 and turn on the
relative magnitude of ionization energies, cationic size, hydration enthalpy and entropy, etc.
Again, the higher the charge on an aquo cation [M(H2O)x]n+ the more readily will it act as a
proton donor. Other group trends will emerge in subsequent sections. However, it is worth noting
here an important vestigial structural relation of these elements to the icosahedral units in
elementary boron. Thus, the structures of both B-rhombohedral boron and the cubic alloy phase
Al5CuLi3 can be constructed from 60-vertex truncated icosahedra, although linked in very
different ways in the 3-dimensional crystalline lattice. Likewise, Ga12 icosahedra have been
found in intermetallic phases such as RbGa7, CsGa7, Li2Ga7, K3Gal3 and Na22Ga39. This has led
to the proposal that the Group 13 elements should be given the collective epithet of 'icosagens'.

5.3 Compounds
5.3.1 Hydrides and related complexes
The extensive covalent cluster chemistry of the boron hydrides finds no parallel with the heavier
elements of Group 13. AlH3 is a colourless, involatile solid which is extensively polymerized via
Al-H-A1 bonds; it is thermally unstable above 150-200o, is a strong reducing agent and reacts
violently with water and other protic reagents to liberate H2. Several crystalline and amorphous
modifications have been described and the structure of α-AlH3 has been determined by X-ray
and neutron diffraction: each A1 is octahedrally surrounded by 6 H atoms at 172pm and the Al-
H-Al angle is 141o. The participation of each Al in 6 bridges, and the equivalence of all AI-H
distances suggests that 3-centre 2-electron bonding occurs as in the boranes. The closest Al - A1
distance is 324 pm, which is appreciably shorter than in metallic Al (340pm), but there is no
direct metal-metal bonding and the density of AlH3 (1.477g.cm-3) is markedly less than that for
Al (2.699gcm-3); this is because in Al metal all 12 nearest neighbours are at 340pm whereas in
AlH3 there are 6 Al at 324 and 6 at 445pm.
AlH3 is best prepared by the reaction of ethereal solutions of LiAlH4 and AlC13 under
very carefully controlled conditions:

The LiCl is removed and the filtrate, if left at this stage, soon deposits an intractable etherate of
variable composition. To avoid this, the solution is worked up with an excess of LiAlH4 and
some added LiBH4 in the presence of a large excess of benzene under reflux at 76-79°C. Crystals
of α-AlH3 soon form. Slight variations in the conditions lead to other crystalline modifications of
unsolvated AlH3,6 of which have been identified. AlH3 readily forms adducts with strong Lewis
bases but these are more conveniently prepared by reactions of the type

[AlH3(NMe3)] has a tetrahedral structure and can take up a further mole of ligand to give
[AlH3(NMe3)2]; this was the first compound in which Al was shown to adopt a 5-coordinate
trigonal bipyramidal structure. Such complexes are now of interest since their thermal
decomposition can be used to prepare ultra-thin carbon-free A1 films by chemical vapour
deposition on GaAs semiconductor devices.

5.3.2 Halides and halide complexes

Several important points emerge in considering the wide range of Group 13 metal halides and
their complexes. Monohalides are known for all 4 metals with each halogen though for Al they
occur only as short-lived diatomic species in the gas phase or as cryogenically isolated solids.
This may seem paradoxical, since the bond dissociation energies for Al-X are substantially
greater than for the corresponding monohalides of the other elements and fall in the range 655 kJ
mol-1 (AlF) to 365 kJ mol-' (AlI). The corresponding values for the gaseous TlX decrease from
460 to 270 kJ mol-1 yet it is these latter compounds that form stable crystalline solids. In fact, the
instability of AlX in the condensed phase at normal temperatures is due not to the weakness of
the Al-X bond but to the ready disproportionation of these compounds into the even more stable
AlX3:

The reverse reaction to give the gaseous species AlX(g) at high temperature accounts for the
enhanced volatility of AlF3 when heated in the presence of A1 metal, and the ready volatilization
of Al metal in the presence of AlC13. Using calculations the standard heats of formation of the
crystalline monohalides AlX and their heats of disproportionation have been estimated as:

Aluminium trihalides
AlF3 is made by treating Al2O3 with HF gas at 700o and the other trihalides are made by the
direct exothermic combination of the elements.
AlF3 differs from the other trihalides of Al in being involatile and insoluble, and in having a
much greater heat of formation (Table 4.6). These differences probably stem from differences in
coordination number (6 for AlF3; change from 6 to 4 at mp for AlC13; 4 for AlBr3 and AlI3) and
from the subtle interplay of a variety of other factors mentioned below, rather than from any
discontinuous change in bond type between the fluoride and the other halides. Similar
differences dictated by change in coordination number are noted for many other metal halides,
e.g. SnF4, BiF3 and BiX3, etc., and even more dramatically for some oxides such as CO2 and
SiO2. In AlF3 each Al is surrounded by a distorted octahedron of 6 F atoms and the 1:3
stoichiometry is achieved by the comer sharing of each F between 2 octahedra. The structure is
thus related to the ReO3 structure but is somewhat distorted from ideal symmetry for reasons
which are not understood. Maybe the detailed crystal structure data are wrong. The relatively
"open" lattice of AlF3 provides sites for water molecules and permits the formation of a range of
nonstoichiometric hydrates. In addition, well-defined hydrates AlF3.nH2O (n = 1, 3, 9) are
known but, curiously, no hexahydrate corresponding to the familiar [Al(H2O)6]Cl3. In the gas
phase at 1000°C the AlF3 molecule has trigonal planar symmetry (D3h) with Al-F 163.0 pm
which is considerably shorter than in the solid phase 170-190pm (for 6- coordinate Al).
Table 4.6. Properties of crystalline AlX3

The structure of AlCl3 is similarly revealing. The crystalline solid has a layer lattice with
6-coordinate Al but at the mp 192.4o the structure changes to a 4-coordinate molecular dimer
Al2Cl6; as a result there is a dramatic increase in volume (by 85%) and an even more dramatic
drop in electrical conductivity almost to zero. The mp therefore represents a substantial change
in the nature of the bonding. The covalently bonded molecular dimers are also the main species
in the gas phase at low temperatures (150-200o) but at higher temperature there is an increasing
tendency to dissociate into trigonal planar AlCl3 molecules isostructural with BX3.
By contrast, Al2Br6 and Al2I6 form dimeric molecular units in the crystalline phase as well as in
the liquid and gaseous states and fusion is not attended by such extensive changes in properties.
In the gas phase ∆Hdissoc = 59 kJmol-1 for AlBr3 and 50 kJmol-1 for AlI3. In all these dimeric
species, as in the analogous dimers Ga2Cl6, Ga2Br6, Ga2I6 and In2I6, the M-X, distance is 10-
20pm shorter than the M-X, distance; the external angle XtMXt is in the range 110- 1250 whereas
the internal angle XµMXµ is in the range 79-102o.

Trihalides of gallium, indium and thallium

These compounds have been mentioned several times in the preceding sections. As with AlX, the
trifluorides are involatile and have much higher mps and heats of formation than the other
trihalide; e.g. GaF3 melts above 1000o, sublimes at -950o and has the 6- coordinate FeF3-type
structure, whereas GaCl3 melts at 77.8o, boils at 201.2o, and has the 4-coordinate molecular
structure Ga2Cl6. GaF3 and InF3 are best prepared by thermal decomposition of (NH4)3MF6:

The volatile trihalides MX3 form several ranges of addition compounds MX3L, MX3L2, MX3L3,
and these have been extensively studied because of the insight they provide on the relative
influence of the underlying d10 electron configuration on the structure and stability of the
complexes. With halide ions X- as ligands the stoichiometry depends sensitively on crystal lattice
effects or on the nature of the solvent and the relative concentration of the species in solution.
Thus X-ray studies have established the tetrahedral ions [GaX4]-, [InCl4]-, etc., and these persist
in ethereal solution, though in aqueous solution [InCl4]- loses its Td symmetry due to
coordination of further molecules of H2O. [NEt4]2[InCl5] is remarkable in featuring a square-
pyramidal ion of C4v symmetry (Fig. 4.8) and was one of the first recorded examples of this
geometry in nontransition element chemistry (1969), cf SbPh5 and the hydrido aluminate species.
The structure is apparently favoured by electrostatic packing considerations though it also
persists in nonaqueous solution, possibly due to the formation of a pseudo-octahedral solvate
[InCl5S]2-. It will be noted that [InCl5]2- is not isostructural with the isoelectronic species SnCls-
and SbCls which have the more common D3h symmetry. Substituted 5-coordinate
chloroderivatives of InIII and TlIII often have geometries intermediate between square pyramidal
and trigonal bipyramidal.

Figure 4.7 Trends in the standard enthalpies of formation ∆H; for Groups 3 and 13 trihalides as
illustrated by data for MF3 and MBr3.

Lower halides of gallium, indium and thallium

Table 4.7 Some properties of TlX

5.3.3 Oxides and hydroxides

The structural relations between the many crystalline forms of aluminium oxide and hydroxide
are exceedingly complex but they are of exceptional scientific interest and immense
technological importance. The principal structural types are listed in Table 4.8 and many
intermediate and related structures are also known. Al2O3 occurs as the mineral corundum.
Table 4.8 The main structural types of aluminium oxides and hydroxides
 Figure 4.11 Schematic representation of the structure of (α-Al2O3. (a) pattern of
occupancy by Al (●) of the octahedral sites between hcp layers of oxide ion (○), and (b) stacking
sequence of successive planes of Al atoms viewed in the direction of the arrow in (a).
CHAPTER 6. METALS OF GROUP IVA
6.1. General characteristics
Group IV A contains: carbon (C), silicon (S), germanium (Ge), tin (Sn) and lead (pb).
Table 5.1 Some general characteristics of group IV A.

C Si Ge Sn Pb
Atomic nunmber 6 14 32 50 82
Electron congifuration 2s22p2 3s23p2 4s24p2 5s25p2 6s26p2
Atomic radius R (A0) 0,77 1,17 1,22 1,40 1,75
4+ 0
Radius of ion R (A ) 0,2 0,39 0,44 0,67 0,76
Ionization energyI1(eV) 11,26 8,15 7,88 7,33 7,42
Comments:
- the number of valence electrons = the number of valence orbitals
- The Group 14 elements tend to adopt oxidation states of +4 and, for the heavier elements, +2
due to the inert pair effect.
- Members of this group conform well to general periodic trends. The atomic radii increase
down the group, and ionization energies decrease. Metallic properties increase down the
group. Carbon is a non-metal, silicon and germanium are metalloids, and tin and lead are poor
metals (they conduct heat and electricity less effectively than other metals such as copper).
6.2. Occurrence:
- These metals are not abundant. Of the earth crust, Ge constitutes 2.10-4 %, Sn constitutes 6.10-4
%, Pb constitutes 1.10-4 %
- Minerals of Ge contain germanite (7CuS.FeS.GeS2), canfieldite (4Ag2S.(Sn,Ge)S2)
Sn can be found in cassiterite(SnO2),Pbcan be found ingalen(PbS) and cerussite(PbCO3).
- 1 liter of ocean water contains 6.10-5 mg Ge, 3.10-3 Sn and 1.10-5 Pb.
6.3 Physical properties
Ge, Sn and Pb are metals. Their physical properties are listed in the table following:

Ge Sn Pb
Melting point (0C) 936 232 827
Boiling point 2700 2270 1737
Density 5,35 7,30 11,34
Electrode potential(V) ~0 -0,136 -0,126
Conductivity(Hg=1) 0,001 8,3 4,6
Hardness(diamond=10) 6 1,5 1,5
- Germanium is gray-white in color and forms crystal structures.
- Tin is a soft, malleable metal with a low melting point. It has two solid-state allotropes at
regular temperatures and pressures, denoted α and β. At higher temperatures (above 13°C), tin
exists as white tin, or β-tin, and is often used in alloys. At lower temperatures, tin can transform
into gray tin, (α-tin); it loses its metallic properties and turns powdery.
- Lead, (also known as plumbate), is similar to tin in that it is a soft, malleable metal with a low
melting point.Lead is toxic to humans, especially children. Even low levels of exposure can
cause nervous system damage and can prevent proper production of hemoglobin (the molecule in
red blood cells responsible for carrying oxygen through the body)

6.4. Chemical properties:

From Ge to Pb, metallic properties increase. The tendency of the elements to form compounds in
which their oxidation states are +2 also increases down the group. Ge (IV) compounds are
common. Sn(II) and Sn(IV) compounds are both popular but Sn (IV) compounds are more
stable. Ge(II) and Sn(II) compounds are strong reducing agents, especially in basic
environments. Pb(IV) compounds are strong oxidizers, especially in acid environment and they
show almost no oxidizing behavior in basic environment.
At STP, Ge and Si don’t react with oxygen, Pb is oxidized by oxygen to form a blue-grey
oxide layer on the surface, preventing Pb from being continuously oxidized. When heated, Sn is
oxidized. Ge is oxidized at 7000C.

Ge do not react directly with H2, but H2 can be dissolved in hot, melted Ge at T> 1000 0C. Sn
reacts with H2 when SnH4 catalyst is present. Pb react directly with H2 at T> 8000C.

All 3 metals react with halogens and some nonmetals.

Ge and Sn do not react with water, even water vapor. Pb reacts slowly with water when O2 is
present (slowly detaches the oxide layer and continue to reacts)

Reduction potential of Ge is almost 0, so it only dissolve in concentrated H2SO4 and HNO3

solution.

GeO2.xH2O can be written as H2GeO3 .

Reduction potential of Sn and Pb are less than 0 so they are soluble in acids. Sn is soluble in
HCl, especially when heated.

Sn is soluble in concentrated H2SO4 and HNO3:

Pb reacts with diluted HCl and H2SO4 (C<80%) only at the surface, because PbCl2 and PbSO4
are formed. More concentrated solution dissolves these salts, so Pb is dissolved in concentrated
HCl and H2SO4:

Pb reacts with HNO3 at any concentration. Pb can also react with acetic acid and some other
organic compounds when O2 is present:

Ge does not react with basic environment. Sn and Pb react when heated to form stanite and
plombit.

Ge only dissolves in concetrated basic environment when H2O2 is present.

6.5. Preparation
See text book.
6.6. Oxide and hydroxides of metals of group IV A.
6.6.1. Oxide MO
Monoxides are solid: GeO and Sn O are black, PbO has 2 allotropes, PbO α is red and PbO β is
yellow.

MOs are amphoteric:

when heated in air, MO is converted to oxides with higher oxidization numbers:

MO is reduced by H2, C, Co when heated (except GeO):

GeO is prepared by heating Ge with GeO2 at 8000C.

SnO is prepared by stealing water from Sn(OH)2:

or by heating till melted the mixture of SnCl2.2H2O and Na2CO3.10H2O or from decomposition
of Sn(II) oxalate when air is present.

Pb is prepared by decomposition of hydroxide, carbonate and nitrate compounds:

or decomposition of Pb(II) oxalate at 300 0C.

6.6.2 Hydroxides M(OH)2

M(OH)2 are gel precipitates which are slightly soluble in water. Ge(OH)2 is orange, Sn(OH)2 and
Pb(OH)2 are white.
When heated, all dissociate to MO:
They are amphoteric. The basicity increases from Ge(OH)2 to Pb(OH)2:

[M(OH)4]2 are strongly hydrolyzed so they are only stable in excess basic solution.
The ability to be hydrolyzed decrease from Ge2+ salt to Sn2+ and Pb2+ salt, consistent with the
decrease in basicity from Ge(OH)2 to Pb(OH)2
All salts of Ge2+ and Sn2+ are strong reducing agents, salts of Pb2+ show no reducibility.

M(OH)2 are prepared by letting M2+ react with basic environment.

or

6.6.3. Oxide MO2

All are solid. GeO2 and SnO2 are white, PbO2 is brown-black.
GeO2 and SnO2 are thermally stable. When heated they turn glassy. PbO2 lose O2 gradually when
heated to become oxides with lower oxidization numbers.

black brown yellow-red red yellow

MO2 are not very chemically active. GeO2 is slightly soluble in water, SnO2 and PbO2 are
insoluble. They are amphoteric but they dissolve in basic better than acid solutions. When
dissolve in basic environment, they form [M(OH)6]2-.

when melted with bases or corresponding oxides, they form MO32-and MO42-:

MO is easily reduced by C, CO, H2, Mg, Al to M.

The oxidizing properties are not representative for GeO2 and SnO2, but they are representative of
PbO2.
PbO2 reacts with concentrated H2SO4 to liberate O2, with HCl to librate Cl2.
In concentrated acid environment, PbO2 oxidizes Mn(II) to Mn(IV):

In strong base environment, PbO2 oxidizes Cr(III) to Cr(IV):

Preparations:
GeO2:

SnO2:

PbO2:

6.6.4.Hydroxide of M(IV):
Hydroxide of M(IV) do not exist in M(OH)4 but in MO2.xH2O with composition changing. They
are gel precipitate soluble in water. GeO2.xH2O and SnO2.xH2O are white, PbO2.xH2O is brown.
Hydroxide of M(IV) are amphoteric, but it is easier for them to dissolve in basic than acid
environment. When dissolved in basic environment, they form:

From GeO2.xH2O to PbO2.xH2O, the acidity reduces, the basicity increases.

CHAPTER 7: GROUP VA ELEMENTS
VII.1. Characteristics:
Table 7.1. Characteristics of elements of group VA.
N0 Properties N P As Sb Bi

1 Atomic number 7 15 33 51 83

2 Electron configuration 2s22p5 3s23p3 4s24p3 5s25p3 6s26p3

3 Atomic radius, 0,71 1,30 1,48 1,61 1,82

Ionic radius
4 1,48 1,86 1,92 2,08 2,13
X3-,

5 ionic radius X5+ , 0,15 0,35 0,47 0,62 0,74

6 Ionization enegy I1, eV 14,53 10,48 9,81 8,64 7,29

7. Electronegativity 3,0 2,1 2,0 1,9 1,9

8. Electron affinity, eV 0,05 0,77 - 72 70,7

Comments:
• Due to the electron configuration of ns2np3, the elements have the tendency to use
3 unpaired electrons to form 3 covalent bonds, in which they are of -3 or +3 oxidization
states. 2 other electrons can form donor acceptor bond with elements of higher
electronegativity, so they usually have an oxidization state of +5. Only N can gain 3 e to
form have an oxidization number of -3
• Except for N, all elements have empty d orbitals that can create two other covalent
bonds.
• The properties change gradually form N đến Bi: N and P are non metal, As and
At are both metal and non metal, Bi is metal.
VII.2. NITROGEN
VII.2.1. Occurrence and isotopes
1. Occurrence:
Nitrogen constitute 0,03% of the number of the atoms of the earth crust. It
constitute 78% of volume of air. Minerals of N contain (NaNO3). It is also found in
protein of living things.
2. Isotopes: 14N (99,635%) and 15N (0,365%) are stable
VII.2.2. Physical properties.
 N is a colorless, odorless, tasteless gas
It is difficult to liquefy (boiling point = -195,8oC) and solidify (MP = -210oC)
Difficult to dissolve in water and organic solvents.
VII.2.3. Structures:
Electron affinity:

2 atoms are bonded by a triple bond (1 σ and 2 π)

VII.2.4. Chemical properties:
Due to the stable triple bond, (dissociation energy = 940kJ/mol), it is super stable,
(even at 3000oC, only 0,1% of molecules dissociate to atoms), and therefore is weakly
active. At room temperature, nitrogen is chemically inert. At high temperature, especially
with the help of a catalyst, it is more active.
1. Reacts with metals:
At normal temperature, N2 reacts with lithium:
6 Li + N2 = 2Li3N
The reaction is faster at 500oC.
With Na, K, Rb, N2 forms M3N when slightly discharged
With Mg, Ca, Ba, Sr: M3N2 is formed powder metals are heated in nitrogen air Mg
(780 - 800oC); Ca (500 - 600oC); Sr (500 - 500oC) và Ba (560 - 600oC);
3Mg + N2 = Mg3N2
with Al: AlN is formed when Al reacts with N2 at 1050 - 1200oC.
2Al + N2 = 2AlN.
2. Reacts with non metal elements:
- with Hydrogen to form NH3, (preparation of NH3 in industry):
3N2 + 3H2 2NH3
Reaction occurs at 450 - 500oC, Fe (activated by Al2O, K2O and water) is used as
a catalyst.
- with oxygen to form NO: N2 + O2 = 2NO
(occurring at 2000oC or in discharge)
VII.2.5.Preparation and uses:
1. Preparation:
- In industry: partially distill liquid air
- In laboratory: decomposition of NH4NO2 at high temperature:
NH4NO2 = N2+ 2H2O
 NH4NO2 can be replaced by NH4Cl and NaNO2.
or : (NH4)2Cr2O7 → Cr2O3 + N2 + H2O
or CuO + NH3 → Cu + N2 + H2O
Pure N2 can be obtained by electrolysis of NaN3: 2NaN3 → 2Na + 3N2
2. Uses: Self study
VII.2.6. Nitrides:
1. Categories
Base on the nature of the bonds, the nitrides are dived in to ionic nitrides, covalent
nitrides and nitride of transition metals.
2. Chemical properties:
Properties of nitrides change periodically. In small periods, there is changes from
basic to acid nitrides:
Elemetns Na Mg Al Si P S Cl

Nitride Na3N Mg3N2 AlN Si3N4 P 3N 5 S 4N 4 Cl3N

Nature Base amphoteric Acid

Nitrides of s elements are active. They are easily hydrolyzed:

Na3N + 3H2O = 3NaOH + NH3 ↑
Mg3N2 + 6H2O = 3Mg(OH)2 + 2NH3↑
AlN are amphoteric compound which can be hydrolyzed in both acid and base
environment:
AlN + 3H2O = Al (OH)3 + NH3
AlN + 4HCl = AlCl3 + NH4Cl
AlN + NaOH + H2O = NaAlO2 + NH3
NCl3 is a liquid. It is explosive and an acid:
NCl3 + 3H2O = 3HClO = NH3
Covalent nitrides such as Si3N4 and BN are solid polymers with high temperatures
(1900oC and 3000oC respectively) and are chemically stable. They are semiconductors.
Nitrides of transition metals are solids, which are super hard, flashy and electronic
conductive. They are chemically and thermally stable: they are not hydrolyzed by acids,
not be oxidized in air.
VII.3. AMMONIA AND AMMONIUM
VII.3.1. Ammonia
 1. Structure:

2. Physical properties
Ammonia is a colorless gas with a characteristic
pungent smell. Boiling point is - 33,35oC and
melting point is - 77,75oC.
Due to the polarity of the molecule and ability to form hydrogen bond, it is strongly
dissolve in water.
3. Chemicial properties
NH3 are chemically active.
• Addition reactions:
- with water: when dissolved in water, NH3 combine with H+ to form NH4+, giving a
weak base solution.
NH3 + H2O NH4+ + OH- Kb = 1,8.10-5
- Combine with acids to form ammonium salts:
2NH3 + H2SO4 = (NH4)2SO4
NH3(g) + HCl(g) = MH4Cl (white smoke).
- Combine with other salts to form salts:: CuSO4.4NH3, CaCl2.8NH3, AlCl3.6NH3…
• Reaction with oxidizers (tính khử)
- NH3 burns in oxygen giving yellow flame:
4NH3 + 3O2 = 2N2 + 6H2O
When Pt - Rh catalyst is used, NO is formed:
4NH3 + 5O2 = 4NO + 6H2O (T=800 oC)
- Halogens oxidize strongly NH3 gas or aqua NH3.
exp1. : 2NH3 + 3Cl2 = N2 + 6HCl
HCl reacts with NH3 to form NH4Cl.
If excess Cl2 is present: 2NH3 + 6Cl2 = 2NCl3 + 6HCl
exp: 5MH3 + 3I2 = 3NH4I + NH3 . NI3 ↓(black) (dry and explosive when touched)
- NH3 reduces some melted metal oxides: 3PbO + 2NH3 = 3Pb + N2 + 3H2O
• Replacement reaction: at high temperature, H atoms in ammonium can be
replaced by active metals to form compounds containing NH2-, NH2-, N3-
• Decomposition
2NH3 N2 + 3H2
at P = 1atm, NH3 fully dissociates at 500oC.
 • Ability to form complexes:
Due to the lone pair electrons, NH3 can form complexes with many metals
containing empty d orbital:
exp: Ag+ + 2NH3 = [Ag(NH3)2]+ K = 10-7,23
Compounds slightly soluble in water can be dissolved in NH3 solution because of
the ability to form complexes:
exp: Zn(OH)2 + 4NH3 = [Zn(NH3)]2+ + 2OH-
AgCl + 2NH3 = [Ag(NH3)]+ + Cl-
4. Preparation and uses:
• Self study
VII.3.2. Ammonium
1. Structure:

2. Chemical properties
- Hydrolysis: Soluble ammonium salts are readily hydrolyzed to form a weak acid
environment:
NH4+ + H2O NH3 + H3O+ Ka = 10-4,75
- Thermal decomposition: all ammonium is unstable to heat. They dissociate to
form NH3 and the corresponding acids and subsequent products depending on the
properties of acids.
(NH4)2SO4 = NH3 + H2SO4 → SO2 + N2 + H2O
(NH4)3PO4= NH3 + H3PO4
3.Uses: self study
VII.4. Hydrazine N2H4
VII.4.1. Structure

VII.4.2. Physical properties

It is a colorless liquid, miscible with water and with a range of organic solvents, and
is corrosive and toxic, its vapor forms explosive mixtures with air.
 Liquid hydrazine dissolves alkaline metals to form a blue solution and liberate H2:
2N2H4 + 2Na = 2NaN2H3 + H2↑
VII.4.3. Chemical properties
1. Combination reaction
- Hydrazine can combine H+ of water, acting as a weak base (weaker than NH3):
N2 H4 + H2 O N2H5+ + OH- K1 = 8,5.10-7
N2 H5 + + H2 O N2H62+ + OH- K2 = 8,9.10-16
N2H5+ is relatively stable in water, N2H62+ is hydrolyzed:
N2H62+ + H2O N2H5+ + H3O+ với k = 11
-Hydrazine can combine with proton of acid to form 2 salts: [N2H5]Cl or N2H4. HCl
and [N2H6]2SO4 or N2H4. H2SO4…
- Like water and ammonia, N2H4 can combine with some salts to form salts such as:
CrCl2.2N2H4 , Co(ClO4)3.3N2H4.
2. Strong reducibility:
Hydrazine and its derivatives are less stable than those of NH3 and NH4+. Unlike
H2O2, N2H4 is a strong reducing agent.
Acid environment: N2↑ + 5H+ + 4e = N2H4.H+ EO = - 0,23 V
Basic environment: N2↑+ 4H2O + 4e = N2H4+ 4OH- EO = -1,16V
Hydrazine can burn in air : N2H4(I) + O2(K) = N2(K) + 2H2O (I) (ΔH= -705
kJ/mol).
In solution, it can reduce halogens, ion MnO4-, Fe3+, IO3- and metal ions to metals
(Ag, Au, Pt, Hg), forming N2:
N2H4 + Cl2 = N2 + 4HCl
5N2H4 + 4 KMnO4 + 6H2SO4 = 5N2↑+4MnSO4 + 2K2SO4 + 16H2O
5N2H4 + 4IO3- + 4H+ = 5N2 + 2I2 + 12H2O
N2H4 + 4AgNO3 = 4Ag + N2↑ + 4HNO3
3. Oxidization ability
When reacting with stronger reducing agents such as Zn, Sn, Sn2+, hydrazine can be
reduced to NH3 (NH4+):
acid environment: N2H4. H+ + 3H+ + 2e = 2NH4+ EO = 1,27V
base environment: N2H4 + 2H2O + 2e = 2NH3 + 2OH- EO= 0,10V
reactions: N2H4 + Zn + 4HCl = 2NH4Cl + ZnCl2
N2H4 + SnCl2 + 4HCl = 2NH4Cl + SnCl4
4. Ability to form complexes:
 Co2+ + 2N2H4 = [Co (N2H4)2]2+ Kkb = 10-3,34
Zn2+ + 2N2H4 = [Zn(N2H4)2]2+ Kkb = 10-3,70
VII.4.4. Preparation and uses:
Self study
VII.5. Hydroxylamine NH2OH

VII.5.1. Structure:
VII.5.2. Physical properties:
The pure material is a white, unstable crystalline, hygroscopic compound. However,
hydroxylamine is almost always provided and used as an aqueous solution.
It is soluble in water in any ration. It is easily dissolved in water but insoluble in
benzene
VII.5.3. Chemical properties: unstable, gradually dissociate at room temperature
to form NH3, N2, H2O and N2O
1. Combination reaction
- When dissolved in water, NH2OH combine with water to form NH2OH. It is a
weaker base than NH3 and N2H4.
NH2OH + H2O [NH3OH]+ + OH- Kb = 8,9.10-9
- reacts with acid:
NH2OH + HCl → NH3OHCl
- Like NH3 and H2O, it can form combination products with metal salts: MgCl2.
2NH2OH, ZnCl2. 2NH2OH.
2. Reacts with oxidizers:
The ability to oxidize others decreases from H2O2 to NH2OH to N2H4
H2O + 2e = 2NH2OH + OH- EO = -3,04V
N2↑ + 2H2O + 4H+ + 2e = 2NH2OH.H+ EO = - 1,87V
In basic environment, NH2OH is a strong reducing agent but weaker than hydrazine.
It reduces salts of Ag, Au, Hg to metals (not Pt), reduces nitric acid, hypochlorite, iodide,
to form NO, N2O, N2:
 NH2OH + HNO3 = 2NO + 2H2O
2NH2OH + I2 + 2 KOH = N2 + 2KI + 4H2O
3. Reacts with reducing agents:
In acid environment, NH2OH acts as an oxidizer:
NH2OH.H+ + 2H+ + 2e = NH3 + + H2O EO = 1,35V
NH2OH + H2O + 2e = NH3 + 2OH- EO = 0,42V
Hiđroxylamin oxi hóa được Fe(OH)2 to Fe(OH)3, oxidize Fe(II) to Fe(III):
NH2OH + 2Fe(OH)2 + H2O = Fe(OH)3 + NH3
2NH2OH + 4FeSO4 + 3H2SO4 = 2Fe2(SO4)3 + (NH4)2SO4 + 2H2O
Besides:
3NH2OH = NH3 + N2 + 3H2O
4. Ability to create complexes:
Ag+ + 2NH2OH = [Ag(NH2OH)2]+ Kkb = 10-4,9
Ni2+ + 6NH2OH = [Ni(NH2OH)6] Kkb = 10-18,6
VII.5.4. Preparation
VII.6. OXIDES OF NITROGEN:
Stable oxides are N2O, NO, N2O3, NO2, N2O4, N2O5
VII.6.2. Nitrous oxide N2O
1. Structure
2. Physical properties: Dinitrogen monoxide has a faint, sweet odor. boiling point
is - 89oC ad melting point is -91oC.
3. Chemical properties
At STD, N2O is stable and therefore inactive. When heated to 500oC, it dissociates
to elements:
2N2O = 2N2 + O2 = -163kJ
So when heated it can react with any compound which can react with oxygen.
Glowing C, P, and other compounds can continuously burn in N2O.
Mixture of N2O with H2 or NH3 will explode if heated.
N2 O + H2 = N2 + H2 O ΔΗ= -323 kJ
3N2O + 2NH3 = 4N2 + 3H2O ΔΗ = -753 kJ
N2O + S = N2 + SO2
4. Preparation: self study
 VII.6.2. Nitrogen monoxide NO
1. Structure: (textbook)
2. Physical properties
NO is a colorless, toxic gas, with melting point of -163oC and BP of-150oC.
3. Chemical properties
NO is active, easy to be oxidized and reduced
- Reacts with reducing agents
2NO + 2H2S = N2 +2S + H2O
2NO + SO2 = N2 + SO3
NO + Cu N2 + CuO
- reacts with oxidizers :
2NO + O2 = 2NO2 (indication of NO)
2NO + Cl2 = 2NOCl
NOCl + H2O → HNO3 + HCl
Strong oxidizers KMnO4, HClO, CrO3, K2Cr2O7 oxidize NO to HNO3:
6KMnO4 + 10NO + 9H2SO4 = 10HNO3 + 3K2SO4 +6MnSO4 + 4H2O
3HClO + 2NO + H2O = 2HNO3 + 3HCl
3CrO3 + 3NO + 3H2SO4 = Cr2(SO4)3 + Cr(NO3)3 + 2H2O
- NO react with salts of metals:
FeSO4 + NO = [Fe(NO)]SO4, (dark brown) when heated, NO is formed
4. Preparation
textbook
VII.5.3. Nitrogen dioxide
1. Structure: textbook
2. Physical properties
NO2 is a brown gas, with melting point of =-11oC and BP of -1oC. NO2 is toxic
3. Chemical properties:
• Coexistence of NO2 and N2O4
2NO2 N2O4 ΔΗ = -61,5 kJ
colorless red-brown
At the normal boiling point of -1oC, the mixture contains 16% nitrogen dioxide, but the
proportion of nitrogen dioxide rises to 99% at 135oC
 • at : Decomposition 1500C nitrogen dioxide dissociates, at it fully dissociates
NO2 → NO + O2
• Reactions with oxidizing and reducing agents:
NO2 acts as both reducing and oxidizing reagents.
NO2 - 1e = NO2+ ΔΗ = 9,8eV,
NO2 + 1e = NO2- ΔΗ = 1,62eV
- Reacts with reducing reagents to form NO:
Cl2 + 2NO2 = 2NOCl
7H2 + 2NO2 = NH3 + 4H2O
2Cu + NO2 = Cu2O + NO
CO + NO2 = CO2 + NO
SO2 + NO2 = SO3 + NO
- Reacts with strong oxidizers to form NO3-
O3 + 2NO2 = N2O5 + O2
H2O2 + NO2 = 2HNO3
2KI + H2O + NO2 = 2KOH + I2 + NO↑
5 NO2 + MnO4- + H2O = Mn2+ + 5 NO3- + 2H+
Properties of diluted N2O4: N2O4 can interact with some alkaline metals,
chlorides, chlorites. In this case, it is considered as salt of NO3- (NO+NO3-)
M + N2O4 = M(NO3)x + NO (M: alkaline metals, Ag, Cu, Pb)
KCl + N2O4 =KNO3 + NOCl
NaClO3+ N2O4 = NaNO3 + NO2 + ClO2
4. Preparation:
VII.6. Nitrous acid and sodium nitrite
VI.6.2. Nitrous acid HNO2
1. Structure:

2.Chemical properties
 • Decomposition
HNO2 is unstable so it is chemically active. In gas phase, there is the equilibrium:
2 HNO2 ↔ NO + NO2 + H2O
In aqua solution, it is quickly dissociated, especially when heated:
3HNO2 = HNO3 + 2NO + H2O
• Oxidization : In acid environment, HNO2 is a relatively strong acid.
HNO2 + H+ + 1e = NO↑ + H2O EO = 0,98V
2HNO2 + 4H+ + 4e = N2O↑+ 3H2O EO = 1,29 V
2HNO2 + 6H+ + 6e = N2↑ + 4H2O EO = 1,44 V
It can oxidize HI to I2, SO2 to H2SO4, Fe2+ to Fe3+:
2KI + 2HNO2 + H2SO4 + I2 + 2NO + 2H2O
2HI + 2HNO2 = 2NO + I2 + 2H2O
H2S + 2HNO2 = 2NO + S + 2H2O
• Reducibility: When reacting with stronger oxidizer, HNO2 is oxidized to HNO3:
NO3- + 3H+ + 2e = NHO2 + H2O EO = 0,94V
exP: NaClO + HNO2 = NaCl + HNO3
H2O2 + HNO2 = HNO3 + H2O
MnO2 + HNO2 + H2SO4 = MnSO4 + HNO3 + H2O
3.Preparation: acidify nitrite solutions
Ba(NO2)2 + H2SO4 = BaSO4 + 2 HNO2
VII.6.2. Nitrites
1. Structure:

2. Chemical properties
• Thermal stability: Nitrite ion is more stable than HNO2. Nitrites of alkaline metas
are stable with heat, they only dissociates at T > 500oC. Nitrites of other metals are less
stable, e.g AgNO2 (dissociates at 140oC) and Hg(NO2)2(at 75oC):
AgNO2 = Ag + NO2
• soluble in water and strongly hydrolyzed
• Reacts with reducing and oxidizing reagents:
In acid environment, its oxidizing and reducing behaviors are similar to HNO2.
 In basic environment: NO2- + H2O + e = NO ↑ + 2OH- EO = -0,46V
2NO2- + 4H2O + 6e = N2 ↑+ 8OH- EO = +0,41V
NO3- + H2O + 2e = NO2- + 2OH- EO = +0,01V
• Ability to form complexes:
As a ligand, ion NO2- forms many types of complexes:
Ag+ + 2NO2- = [Ag(NO2)2]- K = 10-2,83
Hg2+ + 4NO2- = [Hg(NO2)4]2- K = 10-13,54
There also exist M – ONO and M – NO2.
VII.7. NITRIC ACID AND NITRATE
VII.7.1. Nitric acid HNO3
1. Structure: linear, N is sp3 hybrized.
2. Physical properties
- Colorless liquid, which dissolves in water to any ratio, produces visible smoke.
Melting point = -41oC and boiling point is -86oC. D = 1,52g/ml, at -43,30 it turns into a
clear crystalline solid.
- Unstable, easy to dissociate if exposed to light and heated:
4HNO3 = 4NO2 + O2 + 2H2O
brown-red NO2 is soluble in HNO3 so if left unattended in air, HNO3 gradually
turns to yellow.
Unstability of HNO3 maybe due to small size of N atom which results in astrong
repulsive forces between O atoms
-liquid HNO3 is a good ionization solvate, self ionization of pure HNO3 can occur:
2HNO3 = NO2+ + NO3- + H2O Ionization constant is = 0,2601 at -100 C
When dissolved in HClO4 or H2SO4, HNO3 acts as an base:
HNO3 + HClO4 NO2++ 2ClO4-+ H3O+
4HNO3 + 2H2SO4 4NO2+ + 2HSO4- +
3. Chemical properties
• Acidity
- In water and weaker acid solvates, HNO3 acts as an acid.
HNO3 + H2O = NO3- + H3O+
Chemically, HNO3 is a strong acid, it reacts with base oxide, base, salts to form
nitrates
- HNO3 solution with concentration less than 2M reacts with metals to liberate H2
nhờ tính oxi hóa của H3O+ : Mg + 2HNO3 = Mg(NO3)2 + H2↑
 Fe + 2HNO3 = Fe(NO3)2 + H2↑
• Strong oxidization ability:
-When reacting with strong reducing agents, HNO3 is reduced to some products:
NO3- + 2H+ + 1e = NO2 + H2O EO = 0,80V

NO3- + 3H+ + 2e = HNO2 + H2O EO = 0,94V

NO3- + 4H+ + 3e = NO + 2H2O EO = 0,96V

2NO3- + 10H+ + 8e = N2O + 5H2O EO = 1,15V

2NO3- + 12H+ + 10e = N2 + 6H2O Eo = 1,24 V

NO3- + 8H+ + 6e = NH3OH+ + 2H2O EO = 0,73 V

NO3- + 10H+ + 8e = NH4++ 3H2O EO = 0,88V

What is the main product depends on several factors: concentration of acid,

temperature and nature of reducing agents.
+ Reacts with metals.
HNO3 reacts with almost all metals, except Au, Pt, Rh, Ta, Ir.
Al, Fe, Cr, Ni, Co does not react with concentrated acid (d ≥ 1,45 g/cm3,
corresponding to 80%) due to the acid layers formed.
Metals with a negative reduction potential will reduce HNO3 to lower oxidization
numbers:: N2O, N2, NH3OH+ , NH4+.
Zn usually forms N2O but when reacting with diluted HNO3 it forms NH4+ or
NH3OH+:
4Zn + 10HNO3 = 4Zn(NO3)2 = 4Zn (NO3)2 + N2O + 5H2O
4Zn + 10HNO3 = 4Zn(NO3)2 + NH4NO3 + 3H2O
Other metals reduce concentrated HNO3 to NO2 and diluted HNO3(3 - 6M) to NO:
Cu + 4HNO3con = Cu(NO3)2 + 2NO2 + 2H2O
3Cu + 8HNO3 dil = 3Cu(NO3)2 + 2NO + 4H2O
Fe reacts with diluted HNO3 (d = 1,034 - 1,115 g/cm3 or 1M - 3M) to form
Fe(NO3)2 và NH4+.
4Fe + 10HNO3 loãng = 4Fe(NO3)2 + NH4NO3 + 3H2 O
With solution with d> 1,115 g/cm3 , Fe (NO3)3 and NO are formed
For Sn, the reactions are more complicate:
4Sn + 10 HNO3 loãng = 4 Sn(NO3)2 + NH4NO3 + 3 H2O
Some other oxides of N are formed and the processes are slow.
 Sn + 4 HNO3 con = H2SnO3 (axit α stanic hay SnO2.x H2O)+ 4NO2 + H2O
+Reacts with non metal elements: Many non metal elements react with concentrated
HNO3 to form NO2 and diluted HNO3 to form NO, the non-metal elements are oxidized
to acid oxides:
S + 2HNO3 dilute = H2SO4 + 2NO
S + 6HNO3 con = H2SO4 + 6NO2 + H2O
C + 4HNO3 con = CO2 + 4NO2 + 2H2O
P + 5HNO3 = H3PO4 + 5NO2 + H2O
reacts with As to form H3AsO4, I2 to form HIO3.
+ Reacts with compounds: Nitric acid oxidizes many compounds:
Oxidizes Fe2+ to Fe3+ , NO is formed. If excess Fe2+ is present, NO combines with
Fe2+ to form a brown and unstable complexe:
6FeSO4 + 3H2SO4 + 2HNO3 = 3Fe2(SO4)3 + 2NO + 4H2O
FeSO4 + NO = [Fe(NO)]SO4
Oxidizes SO32- or SO2 to form sulfuric acid or sulfates:
Na2SO3 + 2HNO3 = 2NaNO3 + 2NO2 + H2O
SO2 + 2HNO3 = H2SO4 + 2NO2
Cold, concentrated HNO3 oxidizes H2S to S. Hot, concentrated HNO3 oxidizes H2S
to H2SO4.
Oxidizes HNO2 to NO2
HNO3 + HNO2 = 2NO2 + H2O
Concentrated HNO3 oxidizes HCl to from Cl2 and NOCl. Diluted HNO3 can not
oxidize HI to I2 :
HNO3 + 3HCl = NOCl + Cl2 + 2H2O
NOCl is unstable: 2NOCl = 2NO + Cl2
The mixture of 1V concentrated HNO3 and 3V concentrated HCl is called Aqua
regia or nitro-hydrochloric acid. It is a highly corrosive mixture of acids, a fuming yellow
or red. It was named so because it can dissolve the noble metals, gold and platinum. The
reactions involving are:
HNO3 + 3HCl = NOCl + 2Cl + 2H2O; NOCl = NO + Cl;
For Au: Au + 3Cl + HCl = H [AuCl4]
Au + HNO3 + 4HCl = H[AuCl4] + NO + 2H2O
For Pt: 3Pt + 4HNO3 + 12HCl = 3PtCl4 + 4NO + 8H2O;
PtCl4 + 2HCl = H2[PtCl6]
 Latimer diagram of nitrogen:

VII.7.2. Preparation and uses:

VII.7.3. Nitrates
1. Structure:

2. Chemical properties:
• Decomposition (NĐV) of nitrites of metals before Mg, and from Mg to Cu, metals
which is less reactive than Cu
• Oxidization ability:
- In acid environment, the oxidation behavior of nitrites (especially in solid forms) is
similar to that of nitric acid.
3Cu + 2KNO3 + 8HCl = 3CuCl2 + 2KCl + 2NO↑ + 4H2O
2KNO3 + 6FeSO4 + 4H2SO4 = 3Fe2(SO4)3 + K2SO4 + 2NO↑ + 4H2O
- In neutral environment, ion NO3- represents almost no oxidization ability, in basic
environment, it can be reduced to NH3 by Al, Zn:
4Zn +NO3- + 7OH- + 6H2O = 4 [Zn(OH)4]2- + NH3
8Al + 3NO3- + 5OH- + 18H2O = 8[Al(OH)4]2- + 3NH3
• Ability to form complexes:
self study
3. Potassium nitrate KNO3:
Is used to produce gunpowder, a mixture of 75% KNO3 + 10%S + 15% C:
2 KNO3 + S + 3 C = K2S + 3 CO2 + N2
4. Preparation and uses: self study
 VII.9. PHOSPHOROUS
Phosphor (3s23p33d0) is different form N in that it contains AO3d that can be
hybridized (hybrid orbitals which can be formed are sp3, sp3d và sp3d2). The sp3 Hybrid
orbitals corresponding with the coordination number of 4 is the most popular.. Different
from N, the maximum coordination number of P is 6, corresponding to sp3d2 hybrid
states.
VII.9.1. Occurrence and isotopes
1. Occurrence:
2. Isotopes:
Phosphor has only one stable isotope, which is 31P. Other radioactive isotopes have
been synthesized.
VII.9.2. Physical properties - Allotropes:
Elemental phosphorus can exist in several allotropes; the most common of which
are white and red solids. Solid violet and black allotropes are also known. Gaseous
phosphorus exists as diphosphorus and atomic phosphorus.
1. White Phosphorous:
- White phosphorus is a translucent waxy solid that quickly becomes yellow when
exposed to light. For this reason it is also called yellow phosphorus. It glows greenish in
the dark (when exposed to oxygen), is highly flammable and pyrophoric (self-igniting)
upon contact with air as well as toxic (causing severe liver damage on ingestion and
phossy jaw from chronic ingestion or inhalation).
- White phosphorus, or yellow phosphorus, or simply tetraphosphorus (P4) exists as
molecules made up of four atoms in a tetrahedral structure. Gaseous and yellow arsenic
and antimony and solid arsenic phosphide (AsP3) each have a similar tetrahedral
structure. The tetrahedral arrangement results in ring strain and instability. The molecule
is described as consisting of six single P–P bonds. Two different crystalline forms are
known. The α form, which is stable under standard conditions, has a body-centered cubic
crystal structure. It transforms reversibly into the β form at 195.2 K. The β form is
believed to have a hexagonal crystal structure
2. Red phosphorous
3. Black phosphorous
- is the thermodynamically stable form of phosphorus at room temperature and
pressure. It is obtained by heating white phosphorus under high pressures (12,000
atmospheres). In appearance, properties and structure it is very like graphite, being black
and flaky, a conductor of electricity, and having puckered sheets of linked atoms.
 VII.9.3. Physical properties
Despite of the lower electronegativity, P is more active than N. This is because in
N2 , the N-N bond is triple (bonding energy is 936 kJ/mol). In P4, P - P bond is single,
(bonding energy is 220 kJ/mol). Different from N, P atom can be excited so that it has 5
unpaired electrons than can form 5 covalent bond. Beside, P has empty d orbitals that can
form high valences. These compounds are stabilized by π bond of p -> d donor-accepter
bond.
Almost all compounds of P are covalent.
The difference in structures of 3 allotropes of P results in the difference in chemical
properties: white P is the most active, black P is the least active.
Exp: white P burns in air at 40oC, red P burn at T > 250oC and P burns at T >
400oC.
At normal temperature: white P is oxidized gradually by oxygen, so it need to stored
in water.
P can act as an oxidizer or reducing agent.
• Reacts with non-metal elements:
- When burning in excess O2, P forms P4O10 and in insufficient O2 , it forms P4O6
and P4O10. White smoke observed is due to P4O10, which combine with water to form
HPO3. White P is oxidized at normal temperature, giving a pale blue light which is
visible in dark.
- Reacts with halogens to form PX3 and PX5. Reacts with Iodine to form PI3 (white
P and crystalline Iodine must be used)
- Reacts with S to form P2S3 and P2S5 (similar to reactions with oxygen).
• Reacts with metals: P can reacts with many metals to form phosphide, but not
easily.
These phosphide is hydrolyzed by water to form PH3.
• Reacts with compounds:
- White P can reduce metal ions (Au, Ag, Cu, Pb) to free metals:
P + 5AgNO3 + 4H2O = 5Ag + H3PO4 + 5HNO3
2P + 5CuSO4 + 8H2O = 5Cu + 2H3PO4 + 5H2SO4
CuSO4 is used to heal the burnt caused by P or clean excess P in lab instrument.
- At high temperature (8000C), red P can react with water to form H3PO4 (Catalyst
Pt or Cu is needed): 2P + 8H2O = 2H3PO4 + 5H2
- Red P can burn when colliding with strong oxidizers such as KClO3, KNO3,
K2Cr2O7. It can react with hot and concentrated HNO3 and H2SO4 to form H3PO4
 - When reacting with concentrated bases, white P are prone to autoxidation
reduction reactions:
P4 + 3KOH + 3H2O = PH3 + 3KH2PO2
2P4 + 3Ba(OH)2 + 6H2O = 2PH3 + 3Ba(H2PO2)2
VII.10. PHOSPHINE AND DIPHOSPHANE
VII.10.1. Phosphine PH3
1. Structure:
2. Physical properties: Phosphine is a colorless, highly poisonous gas. The boiling
temperature is - 87,40C and melting point is- 1330C. It is slightly soluble in water due to
the weakly polar P - H bond.
3. Chemical properties: The most noticeable property of PH3 is the reducibility.
- It does not react with water, but only interact with H+ of strongest acids HClO4,
HX (X = Cl, Br, I) to form PH4+, which is similar to NH4+
PH3 + HClO4 = PH4ClO4
- Burns strongly in air, especially at night or early birth time when there is high
water vapor, giving blue flame
PH3 + 2 O2 = H3PO4
Reacts with halogens to form PX5 : PH3 + 4Cl2 = PCl5 + 3HCl
It can reduce silver and copper ions to metals:
6AgNO3 + PH3 + 3H2O = 6Ag + 6HNO3 + H3PO3
4. Preparation: text book
VII.10.2. Diphosphane P2H4 (Self study)
VII.11. OXIDES OF PHOSPHOROUS (text book)
VII.11.1. Phosphorus trioxide P4O6
1. Structure:
2. Physical properties
3. Chemical properties
• Acidity: P4O6 is hydrolyzed in water to form phosphorous (Phosphoric(III) ) acid
H3PO3: P4O6 + 6 H2O = 4 H3PO3
In hot water, P4O6 , a mixture of P, PH3 and H3PO4 is formed
P4O6 also reacts with HCl to form H3PO3: P4O6 + 6 HCl = 2 H3PO3 + 2 PCl3
and reacts with bases: P4O6 + 8NaOH = 4Na2[HPO3] + 2H2O
• to oxidized is it C,o60 50 at but stable is 6O4P temperature, room at Reducibility:
10:O4 P form 10 O4 P = 2 O2 + 6 O4 P
It reacts strongly with chlorine and bromine to form POX3, and with iodine to form P2I4.
• Decomposition: when left in a closed container at 200 - 2500C for several days,
P4O6 dissociates into red P and (PO2)n: nP4O6 = 3(PO2)n + nP
(PO2)n is an intermediate oxide which slowly reacts with water to form H3PO3 and
H3PO4.
4. Preparation:
P4O6 is prepared by slowly oxidize white P at low temperature and with insufficient
amount of air
VII.11.2. Phosphorus pentoxide P4O10
1. Structure
2. Physical properties:
3. Chemical properties
P4O10 absorb water strongly so it is used to dry gases. It can steal water of organic
compounds and oxyacids (HNO3, H2SO4, HClO4):
4HNO3 + P4O10 = 4HPO3 + 2N2O5
When reacting with cold water, it forms HPO3
P4O10 + 2H2O = 4HPO3
and when reacting with excess hot water, it forms H3PO4
P4O10 + 6H2O = 4H3PO4
VII.12. OXYACID OF PHOSPHOROUS (textbook)
VII.12.1. Electronic structures:
P forms many oxyacids, including H3PO2, HPO2, H4P2O5, H3PO3, H4P2O6, HPO3,
H4P2O7, H5P8O10, H3PO5 và H4P2O5. The most important are H3PO2, H3PO3 and H3PO4.
VII. 12.2 Hypophosphorous acid: H3PO2
1- Physical properties
2- Chemical properties
• Acidity
H3PO2 is a strong mono-proton acid, even though it contains 3 H atoms. It is
hydrolyzed in water as follows:
H3PO4 + H2O = H3O+ + H2PO2- Ka =5.9.10-2
Its salts, hypophosphites are soluble
• Reducibility
H3PO2 and hypophosphites are strong reducing agents, however, the reactions
involved are usually slow. Reduction potentials are presented below:
 pH < 7: H3PO3 + 2H+ + 2e = H3PO2 + H2O Eo = -0.50V
H3PO4 + 4H+ + 4e = H3PO2 + 2 H2O Eo = -0.94V
pH > 7: HPO32- + 2H2O + 2e = H2PO2- + 3OH- Eo = -1.57V
PO33- + 4H2O + 4e = H2PO2- + 6OH - Eo = -1.35V
It reacts with halogens to form phosphoric acid:
H3PO2 + 2Cl2 + 2H2O = H3PO4 + 4HCl
It can reduce metal ions such as those of Au, Ag, Pd and heavy metals like Ni, Cu,
Hg, Bi to free metals:
H3PO2 + 2CuSO4 + 2H2O = 2Cu + 2H2SO4 + H3PO4
NaH2PO2 + NiCl2 + H2O = Ni + NaH2PO3 + 2HCl
• Oxidization ability
When reacting with stronger reducing reagents, H3PO2 acts as an oxidizing reagent:
pH < 7: H3PO2 + H+ + 1e = P↓+ 2H2O EO = - 0,51 V
H3PO2 + H+ + 4e = PH3↑+ H2O EO = -0,08V
pH > 7 H2PO2- + 1e = P↓ + 2OH- EO = -2,05V
H2PO2- + 3H2O + 4e = PH3↑ + 5OH Eo= -1,18 V
In fact, H3PO2 is reduced by Zn in H2SO4 to phosphine:
2Zn + H3PO2 + 2H2SO4 = 2ZnSO4 + PH3↑ + 2H2O
VII.12.3. Phosphorous acid H3PO3
1. Physical properties
2. Chemical properties
• Stability: at 200 oC it is dissociated as follows: 4 H3PO3 = 3 H3PO4 + PH3
• Acidity: H3PO3 is a medium diprotic acid:
H3PO3 H2PO3- + H+ K1 = 10-2
H2PO3- HPO32- + H+ K2 = 3.10-7
It salts are called phosphites, which are colorless and hard to dissolve.
• Reducibility; H3PO3 is a strong reducing reagents, however, the reactions involved
are slow and complicate. Half cell potentials are:
H3PO4 + 2H + 2e = H3PO3 + H2O Eo = -0,276V
PO43- + 2H2O + 2e = HPO32- + 3OH- EO = -1,12V
H3PO3 can reduce halogens, ions of non reactive metals to turn itself to phosphoric acid:
H3PO3 + H2O + Cl2 = H3PO4 + 2 HCl
HgCl2 + H3PO3 + H2O = H3PO4 + Hg + 2HCl
 • Ability to oxidize: It is a weak oxidizer, however, it can be reduced by Zn in
H2SO4 (newly prepared H) to phosphine:
3Zn + H3PO3 + 3H2SO4 = 3ZnSO4 + PH3↑+ 3H2O
3. Preparation
H3PO3 can be prepared by letting P4O6 react with water or hydrolyzing PCl3
PCl3 + 3H2O = H3PO3 + 3HCl
VII.12.4. Phosphoric acid H3PO4
1. Physical properties;
2. Chemical properties:
- H3PO4 is a medium triprotic acid (K1 = 7,6.10-3; K2 = 6,2.10-8; K3 = 4,4.10-13). It
forms 3 salts: dihydrogen phosphates containing H2PO4-, hydrogen phosphate containing
HPO42- and phosphate containing chứa PO33-.
- Different from hypophosphorous acid and phosphorous acid, phosphoric acid
shows no reducibility. The explanation is that in the series PH4+ - H2PO2- - HPO3- - PO43- ,
the number of π bonds increases mt the stability of the ions increases and the reducibility
decreases. Another reason is that PO43- contain no P-H bond.
- Different form nitric acid, phosphoric acid is stable and show no ability to oxidize
others at temperature lower than 350 - 4000C. At higher temperature, it is a weak oxidizer
and can react with metals.
- Stability: stable, when heated to 260oC, it loses water to form glassy H4P2O7 a
tetraprotic acid which is stronger H3PO4 (when cooled, H4P2O7 converts to H3PO4), if
continuously heated to 300 độ, H4P2O7 changes to glassy HPO3. To distinguish H3PO4
and H4P2O7 (and HPO3), AgNO3 is used. (Ag3PO4 is yellow, Ag4P2O7 and AgPO3 are
white).
3. Preparation
Let P4O10 react water or hydrolyze PCl5 or let P react with HNO3.
4. Uses:
5. Phosphates, Fertilizers.
VII.13. PHOSPHOROUS HALIDES (text book)
VII.13.1. Phosphorous trichloride PCl3:
VII.13.2. Phosphorous pentachloride PCl5
VII.14. ASENIC, ANTIMONY VÀ BISMUTH (SGK)
VII.14.1.General descriptions
VII.14.2. Elements
VII.14. 3. Hydrides of As, Sb and Bi
 1. Electronic structures:
As, Sb and Bi forms hydrides of EH3 form with electronic structures similar to
NH3, in which the center atom is sp3 hybridized.
Some common characteristics of EH3 are presented in this table.
No Substances NH3 PH3 AsH3 SbH3
1 HEH angle 107o 93,5o 92o 91o
1 Tmelting, oC -78 -133 -116 -88
2 Tboiling, oC -33 -88 -62 -18
3 Binding energy, kJ/mol 380 323 281 256

4 Bond length, 1,01 1,42 1,52 1,70

6 Dipole moment 1,47 0,58 0,22 0,12

7 Heat of formation ΔH298, kJ/mol -26,19 -9,6 +67 +147

In series AsH3- SbH3- BiH3 the stability of the bond decreases due to the increase in
the size of valence electron clouds from As to Sb to Bi, and the decrease in the electron
density
The ability to form sp3 hybrid orbital decreases down the group, the angle in the
series AsH3- SbH3- BiH3 decrease and asymptotically reaches 90o.
The decrease in dipole moment value is due to the decrease in ability to form sp3
hybrid orbital and the decrease in the polarizability of E – H bond.
2- Physical properties
At normal temperature, AsH3 (Arsine), SbH3(Stibine) và BiH3(Bismuthine) are
poisonous gases.
3- Physical properties
• Basicity: From N to Bi, the contribution of s orbital to sp3 hybrid orbitals
decreases, therefore the ability to give the lone pair electrons decreases in the series
NH3 - PH3 - AsH3 - SbH3. If NH4+ is totally stable, AsH4+ is detected from IR spectrum.
SbH4+ and BiH4+ are not seen.
• Reducibility: The reducibility increases from NH3 to SbH3. PH3, AsH3 and SbH3
are strong reducing agents, they are ready to burn in air, able to reduce ions of Au, Cu
to the free metals:
AsH3 + 6AgNO3 + 3H2O = H3AsO3 + 6Ag + 6HNO3
CHAPTER 8: GROUP VIA ELEMENTS
8.1. CHARACTERISTICS OF VIA ELEMENTS
Table 6.1. Some characteristics of VIA elements:
No Properties O S Se Te Po

1 Atomic number 8 16 34 52 84

2. Electron configuration 2s22p4 3s3p4 4s24p4 5s25p4 6s26p4

3. 0,66 1,04 1,17 1,37 -

Atomic radius,

4. 1,40 1,84 1,98 3,21 -

Ion radius of X2-,

5. Electronegativity 3,5 2,6 2,5 2,1 2,0

6. Ionization energy I1, eV 13,62 10,36 9,75 9,01 8,43

7 Melting point, oC -218 119,3 217,6 450 252

8. Boiling point, oC -183 444,6 685 990 962

9. Bonding energy X2, kJ/mol 494 322 267 226 -

10. Electron affinity, eV 1,47 2,07 - - -

Properties of electrons of the outermost shell :

All elements have electron configuration of ns2np4 so they are typical non metals,
except Te. They have tendency to obtain 2e to form X2- or to share 2e with others to
create 2 covalent bonds. Their oxidization states are +2 in compounds with more
electronegative elements and -2 in compounds with less electronegative elements. Except
for O, all elements can have oxidization number of +4 or +6.
Except for O, other elements have empty AOd that can be hybridized with other
AOs and AOp to form compound of high coordination number. Se and especially S can
use empty AOd to form π bond of p mt d.
States: at STP, oxygen is gaseous, the others are solid.
Changes in ionization energy, radius, electronegativity from O to are gradual and
consistent with normal laws. The sudden change in electron affinity between O and S can
be explained in a similar way as with F and Cl
8.2. SULFUR
8.2.1. Electronic structure and reduction potential.
1. Characteristics:
S are chemically different from O because:
 - S electron affinity is lower than that of O, almost all compounds of S are covalent,
not ionic. The stability of bonds between S and O with other elements are different, and
especially hydrogen bond stability in S is very low. EXP in H2S, there is almost no
hydrogen bond.
- S can form π bond of p mt d but is not able to form π bond of p - p type. EXP in ion
sulfate, the S – O bond is shorted due to π bond of p mt d type.
- Valence of S is not only 2, but can be 4 or 6 because of the involvement of orbital
d that can be hybridized.
- S has a tendency to form polysulfur compounds because dissociation energy of S-
S (322kj/mol) is greater than that of O-O (210kj/mol). EXP S t
2. Latimer diagram of S (page 236)
• In acid environment
• In base environment
8.2.2. Occurrence and isotopes
1. Occurrence
relatively popular and one the earliest non metals to be known. constitutes 0,03% of
atoms of the earth shell, forms compounds with almost all elements.
In nature, S can exist freely, concentrated in S mine. A part portion of S lies in
compounds such as FeS2, FeCuS2, PbS, ZnS, and some minerals like CaSO4.2H2O,
BaSO4, SrSO4 and in protein.
2. Isotopes
S has 4 natural and 3 radioactive isotopes. 4 stable isotopes are 32S (95,1%), 33S
(0,74%), 34S(4,2%) và 36S (0,016%).
8.2.3. Physical properties.
S can form allotropes which are rings of varying size and chains. The compounds
are stable because S is sp3 hybridized, the bond S - S is covalent (d 2,05 ), and the
angle SSS = 1070. The most stable is S8 ring with the structure shown in the figure below.
Beside, there exist cyclic S6, S4 rings and other open rings Sn

The most stable allotrope is orthorhombic sulfur (Sα) and it occurs naturally as large
yellow crystals in volcanic areas. At 367.2K, Sα transforms reversibly into monoclinic
sulfur (Sβ). Both Sα and Sβ forms contain S8 rings; the density of Sα is 2.07g.cm-3,
compared with 1.94 g cm-3 for S in which the packing of the rings is less efficient.
β
 Properties of the two allotropes:
Properties Orthorhombic Monoclinic

Color yellow slightly yellow

Tmelting (oC) 112,8 119,2

Density (g/cm3) 2,06 1,96

Stable temperature normal temperature above 95,5 oC

Sá Sâ ÄHo= 0,401kj/mol

Both Sα and Sβ are insoluble in water, slightly soluble in alcohol, ether, strongly
soluble in petroleum, benzene and especially in CS2. In these solvent, Sα dissolves better
than Sβ
Phase diagram of S (hình 82 trang 219):
8.2.4. Chemical properties
Because of S8 structure, S is not very active at normal temperature. When heated, S
is relatively active. reacting with almost all elements except inert gases, Nitrogen, iodine,
gold, Pd, Os.
Due to some intermediate oxidization numbers, S can act as both oxidizing and
reducing agents.
1. Oxidization: S +2e = S-2
Reacts with nonmetals:
• With: when heated to 3000C, S reacts with H2 to form H2S:
H2 + S = H2 S H0 = 20,08kJ
This reaction is less violent compared to that between H and O
• With elements of group IV: C, Si.
When passing vapor of S through hot carbon, carbon disulfide is formed:
C + 2S = CS2
When heated amorphous Si with excess S, SiS2 is formed.
• With elements of group V(P): S reacts with white P at1000C and red P at 3500C to
form some sulfide salts such as P2S3 and P2S5.
2P + 3S = P2S3
2P + 5S = P2S5
Reacts with metals: S reacts with metals to form sulfides, for alkaline, alkaline earth
metals, Ag, Hg, reactions occur at normal temperature. for other metals, heat is needed.
 • group I.
- Alkaline metals form M2S, M2S2 and other polysulfides. M2S is formed at normal
temperature: 2Na + S = Na2 S
- Cu forms Cu2S.
- Ag forms Ag2S when Cu powder is heat with S.
• group II.
- Alkaline earth metals form MS.
- Zn, Cd, Hg form ZnS, CdS, HgS. Reaction between Hg and S is ready at normal T
Hg + S = HgS
• group III: when heated, the mixture of Al powder with S powder forms Al2S3. The
salt is hydrolyzed fully to form Al(OH)3 and H2 S.
• Group VI: Chromium reacts with S at high temperature to form Cr2S3. Like Al2S3,
the salt is also hydrolyzed.
• group VII: Mn reacts with S to form MnS.
• group VIII: Fe reacts with S when heated to form FeS: Fe + S = FeS
2. Reduction ability: S + 4e =S+4 hoặc S + 6e = S+6
Reacts with nonmetals:
• group VI (O2): S burns in air, giving the pale blue flame.
S + O2 = SO2 ΔH0 = 297kJ
• group VII
Fluorine reacts with S at normal temp to form SF6.
Chlorine, bromine reacts with S melted to form S2 Cl2, S2Br2. For Chlorine SCl4,
SxCl2 (x = 2 100) can be formed
Reacts with acids
S reacts with hot and concentrated H2SO4 solution to form SO2 and with hot,
concentrated HNO3 solution to form H2SO4.
S + 2H2SO4 = 3SO2 + 2H2O
S + 6HNO3 = H2SO4 + 6NO2↑+ 2H2O
Reacts with other strong oxidizers: KNO3, KClO 3, K2Cr2O7,...
to
3S + 2 KClO3 = 2 KCl + 3SO2
Black explosive mixture is a mixture of 68% KNO3, 15% S và 17% C, almost
corresponding to 2KNO3 + 3C + S. The explosion occurs as follows:
2KNO3 + 3C + S = N2↑ + 3CO2 ↑ + K2S Q = - 707kJ.
2KNO3 + 2S = K2SO4 + SO2↑ + N2↑
 4KNO3 + 5C = 2 K2CO3 + 3CO2↑ + 2N2
S burns when exposed to peroxide of alkaline metals.
2S + Na2O2 = Na2O + SO2
Heating K2Cr2O7 with S:o
t
K2Cr2O7 + S = K2SO4 + Cr2O3
3. Self oxidation reduction:
S is not soluble in water but soluble in alkaline solution or melted hydroxides of alkaline
metals.
3S + 6 NaOH = 2Na2S + Na2SO3 + 3 H2O
if excess S is present: Na2SO3+ S = Na2S2O3
Na2S + 4S = Na2S5
8.2.5. Preparation and uses of S
Preparation: Extracted from S mine by liquefying S under ground before pumping it up
to the ground and finally distilled in special equipment. Also extracted by heating FeS2 at
temperature above 600
FeS2 = FeS + S
uses: S is used in preparation of H2SO4 and và để lưu hoá cao su. In industry, it is used as
the first reagent to produce CS2 and dye substance. Can also be used as antibacterica in
agriculture.
8.3. HYDROSUlFIDE H2S
8.3.1. Electronic structure:
Molecules H 2O H 2S Molecules H 2O H 2S

Bonding angle 1050 92,20 dien moi constant 80 9

bond length Melting point 0 -85,6

0,99 1,33

dipole moment 1,84 D 1,02D Boiling point 100 -60,4

bonding energy 463 347

8.3.2. Physical properties

States: at STD, H2 S is a colorless gas with special smell of destroyed egg. tmelting = -
85,6 C, tboiling = -60,75 oC.
o

Solubility: slightly soluble in water because of low polarity and weak ability to form
hydrogen bond. more soluble in organic compounds. at liquid state, it auto ionizes but
with smaller dissociation constant: H2S + H2S ↔ HS- + H3S+ K = [H3S+].[HS-] = 3.10-33
 Toxicity: H2S is toxic because it can form precipitate with Fe(II) in hemoglobin
(FeS↓ black), turning blood into black and making it lose the ability to transfer oxygen.
Only 0,1% H2S in air can cause serious contamination.
8.3.3. Chemical properties
1. Stability: Unstable to temperature, start to dissociate at 400 oC and fully dissociate at
1700 oC.
H2 S ↔ S + H2
2. Weak acidity
In aqua solution, hydrogen sulfide is a weak di-acid
H2 S + H2 O H3O+ + HS- K1 = 1.10-7
HS- + H2O H3O+ + S2- K2 = 1.10-14
H2S forms 2 types of salts: Hydrosulfide containing HS- and sulfide containing S2-. K2 is
super small so S2- can only exist in very basic environment of [OH- ] > 8M. (Carbonic
acid has K1 = 4,5.10-7, K2 = 4,8.10-11, so it can not push H2S from sulfide salts)
H2S acts as an acid when reacting with strong base. It reacts with salts to form
slightly soluble salts:
H2S + Pb (CH3COO)2 = PbS ↓ + 2CH3COOH
Reaction with FeCl2 is reversible:
H2S + FeCl2 = FeS ↓ + 2HCl
3. Strong reducibility
From Latimer diagram:

Acidic environment: = + 0,14V;

In basic environment: ; -0,68V

Reacts with oxidizers to form S, SO2, H2SO4 depending on the conditions, but in many
cases S is formed.
• with halogen:
• with compound
- Reduce HNO2 (or NaNO2 in acid environment) to form S và NO.
- In acidic environment, H2S turns purple KMnO4 to colorless, turns yellow-orange
K2Cr2O7 to blue (Cr3+). Both cases form S.
- Reduce Fe(III) to Fe(II), HNO3 to NO2, solution of SO2 to S.
• with oxygen: H2S burns in oxygen giving light blue flame, with excess oxygen, SO2
is formed. with insufficient oxygen, S is form:
H2S solution left exposed to air is not clear. based on this reaction, S can be extracted
form industry waste.
• with halogens
- H2S gas reduces halogens to form HX and S:
H2S + X2 = S + 2HX (X = Cl, Br, I).
- H2S solution is oxidized by Cl2, Br2 to H2SO4, by I2 to S:
4Cl2 + H2S + 4H2O = H2SO4 + 8HCl
4Br2 + H2S + 4H2O = H2SO4 + 8HBr
• with compounds
- reduces HNO2 (NaNO2 in acid environment), Eo (HNO2, H+/NO) = 0,98v
2HNO2 + H2S = 2NO + S + 2H2O
2NaNO2 + H2S + 2HCl = 2NaCl + 2NO + S + 2H2O [
- In acid environment, H2S turn purple KMnO4 to colorless, turn yellow orange K2Cr2O7
to blue (Cr3+). In both cases, S is formed:
2KMnO4 + 5H2S + 3H2SO4 + K2SO4 + 2MnSO4 + 5S↓ + 8H2O
K2Cr2O7 + 3H2S + 4H2SO4 = K2SO4 + Cr2(SO4)3 + 3S ↓+ 7H2O
- reduces Fe(III) to Fe(II), concentrated HNO3 to NO2, SO2 to S:
2FeCl3 + H2S = 2FeCl2 + S ↓ + 2H2O
2HNO3 + H2S = 2NO2 + S+ 2 H2O
8HNO3 + H2S = 8NO2 + H2SO4 + 4H2O
SO2 + 2H2S = 3S ↓ + H2O
8.3.4. Preparation of H2S
In manufacture: byproducts of the process of oil extraction.
In laboratory: produced in Kipp’s appratus:
FeS + 2H2SO4= FeSO4 + H2S
8.3.5. Sulfide salts:
1. Clasical
• Bases on the nature of bond, sulfide salts can be divide into:
- Ionic sulfides: sulfides of alkaline, alkaline earth metals, Al, and some other metals.
These are fully hydrolyzed to form an basic environment
S2- + H2O HS- + OH-
- covalent sulfide: Almost are slightly soluble in water.
• Based on the solubility, sulfides can be divided into:
- Sulfide soluble in water and hydrolyzed to form basic environment: sulfide of alkaline
metals, alkaline earth metals: Na2S, K2S, BaS. Sulfides of Cr, Al, Fe (Cr2S3, Al2S3, Fe2S3)
are insoluble in water but fully hydrolyzed:
Cr2S3 + H2O D H2S + Cr(OH)3
- Sulfide insoluble in water by soluble in diluted acidic solution: include sulfides of great
solubility product constant. MnS pink (T = 2,5.10-10), FeS black (T= 910-18), ZnS white
(T =1,610-21), CoS black (T= 4.10-21)...
- Sulfides insoluble in water and dilute acid solutions: CdS yellow (T = 7,9.10-29), HgS
red (T = 1,6.10-52), SnS (T = 1.10-25), PbS black (T = 2,5.10-27), CuS black
2. Preparation of sulfides: 4 methods
• Direct to reaction of metals with S:
Zn + S = ZnS

• Sulfides of alkaline and alkaline earth metals can be prepared by using C to

reduce sulfate at high temperature:
600 - 8000C
BaSO4 + 4C BaS + 4CO
0
1000 C
Na2SO4 + 4C Na2S + 4CO

• readily soluble sulfides can be prepared by passing H2S through alkaline solution:
H2S + 2NaOH = Na2S + 2H2O
• Difficultly soluble can be prepared by letting solution of H2S or(NH4)2S react
with salt solution:
(NH4)2S + Pb (NO3)2 = PbS↓ + 2NH4NO3
H2S + Cu(NO3)2 = CuS ↓+ 2HNO3
8.4. SULFUR DIOXIDE
8.4.1. Structures:

OSO is V shape, with an O-S-O bond angle of 119,5o and S-O bond length of
1,43Ao
S is sp2 hybridized, it uses 1 sp2 AO filled with 1e to form σ bond with one O atom
and 1AO filled with 2e to form donor accepter bond with the empty AO bond of O.
S still have 1AO pz not hybridized, this is used to form π bond with 1 O (non
located bond)
 S still have one 1AO with lone pair electrons so it can acts as a reducing agent. The
shortening of S-O bond is due to the fact that S uses 1 empty AO dz2 or dx2-y2 to overlap
with AO p 2e of O to form one more π bond.
8.4.2. Physical properties
• States: at normal temperature, SO2 is a colorless, dense, toxic gas and acid "taste".
(Tboiling = -10oC, Tmelting = -75oC).
• Solubility: SO2 is strongly soluble in water because it is strongly polar. (µ =
1,59D).
8.4.3. Chemical properties
1. Acidity.
SO2 is strongly soluble in water to form SO2. n H2O, giving a weak acid
environment:
SO2 + nH2O SO2. nH2O H3O+ + HSO3-+ (n-2) H2O
SO2 + 2 H2O HSO3- + H3O+ K1 = 1,7.10-2
HSO3- + H2O SO32- + H3O+ K2 = 6,2.10-8
In SO2 solution, H2SO3 does not exist, but we can detect both sulfite and
hydrosulfite, so H2SO3 is a diprotic acid.
It reacts with bases, oxide bases, salts of weaker acids
BaO + SO2 = BaSO3
2. Strong reducibility.
Solution of SO2 in water is a relatively strong reducing agent, reductions potentials
are:
SO42- + 2e + 4H+ = H2SO3 + H2O EO = +0,17V
SO42- + 2e + H2O = SO32- + 2OH- EO = -0,93V
The reducibility is better in basic environment rather than in acidic environment.
This is due to the S-H bonds presenting in basic environment.
Strong oxidizers HNO3, KMnO4, K2Cr2O7, FeCl3, halogens... oxidize SO2,
hydrosulfite and sulfite to sulfate:
2FeCl3 + SO2 + 2H2O = 2FeCl2 + 2HCl + H2SO4
2HNO3 + SO2 = H2SO4 + 2NO2
Cl2 + SO2 + 2H2O = H2SO4 + 2HCl
Br2 + SO2 + 2H2O = H2SO4 + 2HBr
5SO2+ 2KMnO4 + 2H2O = K2SO4 + 2MnSO4 + 2H2SO4
K2Cr2O7 + 3SO2 + 2H2SO4 = Cr2(SO4)3 + K2SO4 + 2H2O
 Oxygen reacts with SO2 to form SO3 with Pt catalyst at 400oC. Now, catalyst V2O5
is used, and reaction is carried out at 500oC. The efficiency can be as high as 98%.
2SO2 + 5000C O2 2SO3 ΔH0 = -96,23 kJ/mol
H2 O2 reacts with SO2 to form H2SO4 when heated
H2O2 + SO2 = H2SO4
3. Oxidation ability: when reacting with stronger reducing agents, SO2 acts as an
oxidizer, the products is mainly S
SO2 + 4H+ +4e = S + 2H2O Eo = 0,5v
SO32- + 3H2O + 4e = S + 6OH- Eo = -0,66v
• H2S reduces SO2 to S.
2H2S + 2SO2 + 3S + 2H2O

5000C
2H2 + SO2 S + 2H2O
(Pt)

8000C
2C + SO2 S + 2CO
5000C
CO + SO2 S + CO2
boxit

• H2, C, CO reduces SO2 to S at different temperature and with different catalysts.

these reactions are used to produce S from SO2 in industry
• At high temperature, some metals Mg, K, Fe reduces SO2 to metal oxides, S or
sulfides or thiosulfates:
2Mg + SO2 = 2MgO + S
this is used to collect S in industry waste
Mg + SO2 = MgO3 + Mg2S2O3
K + 3SO2 = K2SO3 + K2S2O3
3Fe + SO2 = 2FeO + FeS
8.4.4. Preparation of SO2
• In industry: SO2 is prepared by burning S in oxygen or oxygen in air, or burning
sulfide minerals:
to
4FeS2 + 11O2o = 2Fe2O2 + 8SO2
t
2ZnS + 3O2 = 2ZnO + 2SO2
• In laboratory
- let H2SO4 react with sulfite or crystal hydrosulfite:
 K2SO3 + 2H2SO4 = 2KHSO4 + SO2↑ + H2O
NaHSO3 + H2SO4 = NaHSO4 + SO2↑ + H2O
- heat solution of SO2
SO2. x H2O H3O+ + HSO3- + (x-2) H2O exothermic reaction
8.4.5. Sulfites:
1. Electronic structures
2. Strong reducibility
Because S still has one hybrid AO with lone pair electrons, it can give this pair to become
the stable tetrahedral shape like HSO4- or SO42-
SO42- + 2e + H2O = SO32- + 2OH- EO = -0,93 V
- sulfites are more stable than hydro sulfites, sulfites of alkaline metals dissociate at 600
o
C: 4 K2SO3 = 3K2SO4 + K2S
- hydrosulfites of alkaline metals lose water gradually at room temperature to form
disulfites: 2KHSO3 = K2S2O5 + H2O
- All are strong reducing reagents, they are gradually oxidized by oxygen dissolved in
water: 2K2SO3 + O2 = 2 K2SO4
if leaf unattended in air, sulfites and hydrosulfites turn to sulfates
Strong oxidizers (KMnO4…) oxidize SO32- to SO42-:
Cl2 + Na2SO3 + H2O = Na2SO4 + 2HCl
KMnO4 oxidizes SO32- in all environment:
2KMnO4 + 5K2SO3 + 3H2SO4 = 2MnSO4 + 6K2SO4+ 3H2O
2KMnO4 + 3K2SO3 + H2O = 2MnO2 ↓+ 3K2SO4 + 2KOH
2KMnO4+ K2SO3 + 2KOH = 2K2MnO4 + H2O
8.5. SULFIDE TRIOXIDE SO3
8.5.1. Structures:
The molecule is trigonal planar shape, OSO angle is 120o, S-O bond length is là
1,43 , dipole moment is 0.
S is sp2 hybridized. It uses 2 hybrid AOs with 2e to form
donor acceptor bonds with 2 O, 1 hybrid AO with 1e to form σ
with the other O. S uses the un-hybridized AO to form π bond
with the third O. Because all 3 O atoms are the same, the bonds
are not located. Due to the shortening of S-O bond, SO3 still has 1
π bond formed by overlapping of an empty AO d of S and AO p of O.
The bond order is: 1/3 (8-0)/2 = 4/3
 8.5.2. Physical properties
S which is sp2 hybridized is not stable, it has the tendency to turn in to sp3 hybrid.
At high temperature, SO3 is a gas (tboiling = 44,8oC), when cooled, it changes to
liquid form containing cyclic (SO3)3, when cooled to 16,8 oC, the liquid changes to a clear
solid like ice water, which is SO3- γ still containing cyclic trimers. Under 16,8 oC, SO3- γ
becomes white crystals of SO3- β
8.5.3. Chemical properties
1. Acidity.
SO3 is an acidic oxide, it reacts strongly with water to form H2SO4, the reaction is
exothermic so one has to gradually add SO3 into water to avoid explosion. SO3 left
untended in air can become smoke.
SO3 + H2O = H2SO4 ΔHO = -89,12kJ
H2SO4 can lose water for P2O5 to form SO3. SO3 reacts with concentrated H2SO4
solution to form polysulfuric acid (oleum) H2Sn+1O3n+4.
Due to high water affinity, SO3 can steal water from many organic compounds such
as Cellulose, sugar, turning them to C.
SO3 also reacts with bases, basic oxide to form sulfates:
BaO + SO3 = BaSO4
SO3 can combine with water, HF, HCl, NH3
SO3 + HX = HSO3X halogenosulfuric acid ( X=F, Cl)
SO3 + NH3 = H3SO3N
2. Strong oxidization ability
reacts with halides of metals and non metals to liberate halogens.
8.5.3. Preparation of SO3
- Industry: oxidize SO2 in air at 500 oC and catalyst V2O5:
SO2 + O2 = SO3
- In laboratory: small amount of SO3 is prepared by distilling oleum
8.6. SULFURIC ACID AND SULFATES
8.6.1. Sulfuric acid.
1. Structure:
 dS = O = 1,45 and dS - OH = 1,53
3
S is sp hybridized so it is stable. In H2SO4, S uses all valence orbitals to form
bonds, sot H2SO4 and sulfates are stable.
2. Physical properties:
- H2SO4 is a colorless, odorless, heavy and viscous liquid, d =1,84g/cm3
- concentrated H2SO4 solution can absorb water vapor at any concentration
because the vapor pressure over the surface is super small. It is therefore used to dry
reagents. Note: do not use H2SO4 to dry H2 because it is partly reduced by H2 (use P2O5).
H2SO4 concentrated + H2 = SO2 + H2O
H2SO4 can also steal water from many organic compounds:cellulose, sugar, turing them
into carbon.
- Infinitively soluble in water and the reaction is strongly exothermic, therefore
when diluting H2SO4, H2SO4 must be added slowly to water, not the reverse process and
the mixture should be stirred continuously.
- At STD, it is nonvolatile, when heated, the dilute solution is volatile and stops
when the temperature reaches 337 oC and the concentration reaches 98,5%. If continue
heating the solution with concentration greater than 98,5%, SO3 evaporates and the
boiling point increases until it reaches 337 oC. 337 oC is considered as the boiling point of
H2SO4, the condensing temperature is 10,40C. High boiling temperature allows H2SO4 to
push easily volatile acids out of their salt solutions.
- H2SO4 100% is not electrically conductive, but its dilute solution, especially ones
30% is electronically conductive.
- pure H2SO4 can dissolve SO3 in any ratio to form oleum
- pure H2SO4 is ionization solvent, it also self-ionizes:
H2SO4 + H2SO4 = H3SO4+ + HSO4-
In H2SO4 may acids act as bases:
H2SO4 + CH3COOH = HSO4- + CH3COOH2+
3. Chemical properties of diluted H2SO4:
A typical strong acid:
H2SO4 = H+ + HSO4-
HSO4- H+ + SO42- Ka = 10-2
Dissolve many metals to liberate H2 due to the oxidation ability of H3O+
Fe + H2SO4 = FeSO4 + H2↑
Dissolve Cu when oxygen is presented:
 2Cu + 2H2SO4 + O2 = 2CuSO4 + 2H2O
4. Chemical properties of concentrated H2SO4 solution.
• Strong acidity: reacts with bases, basic oxides, salts. Used to prepare easily
volatile acids.
NaCl + H2SO4 = NaHSO4 + HCl ↑
KF + H2SO4 = NaHSO4 + HF ↑
• Strong oxidization ability.
Reacts with reducing reagents to form many products, mainly SO2, S and H2S.
- Reacts with metals: reacts with almost all metals to form SO2 and metal ions of
high oxidization numbers, for metals with strong reducibility such as Zn, Mg, S can be
formed:
Zn + 2H2SO4 = ZnSO4 + SO2↑ + 2H2O
3Zn + 4 H2SO4 = 3ZnSO4 + S↓ + 4H2O
But Al, Fe, Cr do not react with cold concentrated H2SO4 solution because the reaction
forms an oxide layer on the surface of the metals which is insoluble in water
- With non metals: C, S, P, As reacts with hot and concentrated H2SO4 to form SO2
and oxides of highest oxidization states of non metals.
C + 2H2SO4 = 2SO2 + CO2 + H2O
S + 2H2SO4 = 2SO2 + 2H2O
4P + 8H2SO4 = 4H3PO4 + 7SO2↑ + S + 2H2O
4As + 6H2SO4 = As4O6 + 6SO2↑ + 6H2O
- With compounds: concentrated H2SO4 oxidizes many compounds::
2HBr + H2SO4 = SO2 + Br2 + H2O
8HI + H2SO4 = H2S + 4I2 + 4H2O
• Can steal water from crystals of hydrates:
H2SO4 đ
CuSO4 . 5H2O CuSO4 + 5H2O
and some other organic and inorganic compounds:
H2SO4 đ 2HClO4 H2SO4 đ Cl2O7 + H2O
2HMnO4 H2SO4 đ Mn2O7 + H2O
(C6H10O5)n 6nC +5nH2O
8.6.2. Sulfates and hydrosulfates:
1. Structure:
SO42-: is tetrahedral shape, d S-O = 1,49Ao, S is sp3 hybridized, 4 hybrid AOs form
4 σ bond with 4 O atoms, therefore both ion SO42- and HSO4- are stable. The shortening
in S-O bond is due to π bond formed by overlapping between AO 2p of O and empty AO
d of S. these bonds are not located.
2. Solubility
Almost all sulfates are easily soluble in water and easy to be crystalized in hydrates:
Na2SO4.10H2O; CuSO4.5H2O, MgSO4.xH2O (x= 1-12); MnSO4.4H2O, MSO4.7 H2O (M:
Mg, Mn, Fe, Co, Ni, Zn) because of great heat of hydration. Some insoluble salts can only
formed in solid forms: Ba, Ca, Sr, Pb
Sulfates are often double salts:
M2SO4. MSO4 . 6H2O (MI là K+, Na+, NH4+, Rb+; MII là Be2+, Mg2+, Fe2+, Zn2+)
M2SO4. M2(SO4)3 . 24H2O hay MI MIII (SO4)2. 12H2O
(MI là Na+, K+, NH4+, Rb+, Cs+, Tl+; MIII là Al3+, Fe3+, Cr3+, Ti3+)
alum: K2SO4. Al2(SO4)3. 24 H2O (can replace K = Li, Na, NH4)
Mohr’s salt: (NH4)2SO4. FeSO4. 6H2O
3. Decomposition by heat
Hydrosulfates of alkaline metals are extracted in crystal forms. Other are only found
in solutions. Hydrosulfates of alkaline metals are ready to dissociate to sulfate, SO3 and
water.
NaHSO4 = Na2SO4 + SO3 + H2O
Sulfate of alkaline metals, Ca, Ba is not thermally dissociative. Others dissociate to
form SO3 and the corresponding basic oxides. If continuously heated, SO3 dissociates to
SO2 and O2, oxides of metals after Cu dissociates ot metals.
2CuSO4.5H2O = 2CuO.SO3 + 10H2O (653 - 6700C)
The thermally stability increase with electron density and polarizability.
Salt T0C start dissociating ToC best dissociated Products

FeSO4 167 480 Fe2O3.2 SO2

Fe2O3. 2SO3 492 560 Fe2O3

Al2(SO4)3 590 639 Al2O3

PbSO4 307 705 6PbO. 5SO3

CuSO4 653 670 2CuO. SO3

MnSO4 699 790 Mn3O4

NiSO4 702 760 NiO

CoSO4 720 770 CoO

 MgSO4 890 972 MgO

Ag2SO4 917 925 Ag

CaSO4 1200 CaO

4. Ability to form complexes:

5. Preparation of sulfates.
8.7. OTHE OXYACID OF S
8.7.1. Thiosulfuric acid and thosulfate

H- O S H- O O
or
S S

H- O O H- S O

1. Acid H2S2O3
- structure:
-Properties:
H2 S2O3 is unstable, ready to dissociate at normal temperature, stable at -780C
H2 S2O3 = H2O + S + SO2
due to the un-stability, acid dissociation constant can not be determined. it is
assumed to be a strong acid cause it is not hydrolyzed like Na2S2O3
2. Sodium thiosulfate
• Structure:

Ion S2O32- is tetrahedral shape similar to SO42-, d S - S = 1,99 and d S - O = 1,48

. In S2O32- there exist weak π S - S bond and strong π S - O bond, S2O32- is less stable
than SO42-.
In S2O32-, in addition to an S atom of +6 oxidization number, there is another S with
-2 oxidization number, so it can be oxidized to form sulfuric acid or sulfates.
• Stability: Ion S2O32 is more stable than H2S2O3, in solution it slowly dissociate
under effects of acids:
S2O32- + 2H+ = SO2 + S + H2O
• Reduction potentials:
pH<7: 2SO42- + 10H+ + 8e = S2O32- + 5H2O EO = 0,29V
 pH>7: 2SO42- + 5H2O + 8e = S2O32- + 10OH- EO = 0,76V
The reducibility is better in basic environment.
• Strong Reducibility (Na2S2O3 is Na2SO3.S)
is oxidized by Cl2, HClO, KMnO4, Br2, I2 to form sulfuric acid or sulfates:
4Cl2 + Na2S2O3 + 5H2O = Na2SO4 + H2SO4 + 8HCl
Cl2 + Na2S2O3 + H2O (hơi ẩm) = Na2SO4 + S + 2HCl
This reaction is used to discard Cl2 left after beaching.
Na2S2O3 + Br2 (saturated) + H2O (wet vapor) = Na2SO4 + S + 2HBr
Na2S2O3 + HClO → Na2SO4 + S + HCl
5Na2S2O3 + 8KMnO4 + 7H2SO4 → 5Na2SO4 + 8MnSO4 + 4K2SO4 + 7H2O

Iodine titration: I2 + 2Na2S2O3 = Na2S4O6+ 2NaI

S4O62- + 2e = 2S2O32- EO = 0,09V
• Ability to form complexes:
S2O32- can dissolve slightly soluble slats by forming complexes:
AgBr + 2S2O32- = [Ag(S2O3)2]- + Br-
Na2S2O3 is use in film industry to get rid of excess AgBr
• Preparation of Na2S2O3
8.7.2. Peroxymonosulfuric, Peroxydisulfuric acids and correponding salts
1. Acids:
a. Structures
b. Properties.
- both are colorless crystals and can absorb water very well. Like sulfuric acid, they
react strongly with H2O, sugar, cellulose.
- In aqua solution, and dilute sulfuric acid, they are hydrolyzed to form H2O2.
H2SO5 + H2O = H2SO4 + H2O2
H2S2O8 + 2H2O = 2H2SO4 + H2O2
-are strong oxidizers, H2SO5 is stronger oxidizer than H2S2O8:
S2O82- + 2e = 2SO42- EO = 2,0V
H2SO5 + 2KI = K2SO4 + I2 + H2O (fast)
H2S2O8 2KI + H2O = K2SO4 + I2 + H2SO4 (slow)
2. Salts:
 - Peroxysulfates are less stable than peroxydisulfates which can be extracted in
solid form.
- Are strong oxidizing agents: S2O82- + 2e = 2SO42- E0 = 2,01v
Can oxidize Mn2+ to Mn7+, Cr3+ to Cr+6.
2MnSO4 + 5 (NH4)2S2O8 + 8H2O = 2HMnO4 + 5(NH4)2SO4 + 7H2SO4
Cr2(SO4)3 + 3 (NH4)2S2O8 + 7H2O = H2Cr2O7 + 3(NH4)2SO4 + 6H2SO4
In the lab, K2S2O8 and (NH4)2S2O8 are used as oxidizers.
3. (NH4)2S2O8
are white crystals, soluble in water where it is hydrolyzed slowly at normal
temperature and fast at high temperature. in water:
(NH4)2S2O8 + 2H2O = 2NH4HSO4 + H2O2
8.8. Se - Te - Po
8.8.1. Occurrence
Se, Te are available in crust of the earth (10-5 và 10-7%) with other metals Cu, Pb,
Hg, Ag, Au. Their minerals are usually mixed with those of S. Po is radioactive
8.8.2. Physical properties
Se grey Te crystal Po

Tmelting (0C) 217,6 450 252

Tboiling (0C) 688 990 962

band gap (ev) 1,8 0,35 metals

E0 (X +2e = X2-)ev

8.8.3. Chemical properties

- Po is the strongest metals. O, S are non electronic conductive, Se, Te are
semiconductors and Po are electronic conductive
- Like S, Se and Te react with many metals to form selenides and tellurides
- Se reacts with H2 at high T, while Te does not. Se and Te react with F2 at normal
T, with O2 when heated
- Se does not react with H2O but Te reacts to form H2
- Se, Te do not react with acid, but Po does:
Po + 2HCl = PoCl2 + H2
- with concentrated H2SO4 and HNO3, Se and Te react similarly to S, Po reacts
similarly to a metals: Po + 8HNO3 = Po(NO3)4 + 4NO2 + 4H2O
- Like S, Se and Te are soluble in alkaline solutions:
 3E + 6KOH = K2EO3 + 2K2E + 3H2O
8.8.4. Compound with hydrogen:
Properties of H2E
No Properties H 2O H 2S H2Se H2Te

HEH angle 104,50 92,20 910 900

0,96 1,33 1,46 1,69

E - H bond length,

Bonding energy E - H, kJ 463 347 276 238

-285,8 -21 33 99,7

, kJ/mol

Melting point, oC 0 -85,6 -65,7 -51

Boiling point, oC 100 -60,4 -41,4 -2

Acid dissociation constant Ka 1,8.10-16 1..10-7 1,7.10-4 1.10-3

reducible potential 1,23V 0,14 -0,4 -0,51

- H2Te and H2Se are more soluble in water than H2S, the solutions are weakly acidic.
- The reducibility increase from H2O to H2Te
8.8.5. Oxides of Se, Te, Po.
1. Dioxides EO2: SeO2 - TeO2 - PoO2
• EO2 are polymers because the hybrid sp2 states are representative with Se, Te, Po.
• The acidity increase from SeO2 to TeO2 to PoO2 because the stability of S - O
bond decreases from SeO2 to PoO2.
SeO2 is readily soluble in water to form acid.
SeO2 + H2O = H2SeO3
TeO2 is almost insoluble in water but soluble in basic solution:
TeO2 + 2KOH = K2TeO3
PoO2 is only soluble in melted KOH:
PoO2 + 2KOHmelted = K2PoO3
2. Trioxide EO3
CHAPTER 9: GROUP VIIA ELEMENTS (HALOGENS)
9.1. CHARACTERISTICS AND GENERAL TRENDS OF HALOGENS
Group VIIA includes F, Cl, Br, I, At, of which At is radioactive. All elements of
the periodic tables create halides, except He, Ne, Ar.
Table: Characteristic of halogens:
N0 Tính chất F Cl Br I At

1 S ốth ứtự 9 17 35 53 85

2 Cấu hình electron 2s22p5 3s23p5 4s24p5 5s25p5 6s26p5

3 Bán kính nguyên t ử( ) 0,64 0,99 1,14 1,33 1,40

4 Năng lượng ion hóa I1, eV 17,42 13,01 11,84 10,45 9,5

5 Ái lực electron, eV 3,58 3,81 3,56 3,29 3,29

6 Đ ộâm điện 3,98 3,16 2,96 2,66 2,20

7 Trạng thái oxi hóa -1 -1 -1 -1 -1

+2,+4,+6,
+1,+3,+5,+7 +1,+3,+5 +1,+3,+5,+7

- The properties of halogens change gradually down the group, however there is a big
difference in electron affinity between F and Cl. This is because F doesn’t contain AO d.
- Halogens have the tendency to obtain one electron to form X- or share one electron
with others to form a covalent bond. They are typical non metals.
Except for F not containing orbital d, other elements have empty orbital d that can
form electron donor accepter bond with other atoms with the lone paired electrons.
- Oxidization states: The oxidization number of halogens in compounds is -1. Except
for F, all halogens have oxidization states ranging from +1 đến +7 in their compounds
with more electronegative elements such as F, O, N. However compounds of high
oxidization numbers are less stable than halides. F is also the strongest oxidizing
element.
- Atomic radius increases with Z because of the increase in the numbers of electrons
shells.
- Electron affinity: Even though F is more electronegative, but its electron affinity is
less than F. This is due to the small size of F and therefore a large electron density,
making obtaining electrons less favorable. Down the group, electron affinity decreases
 - Ionization energy: decreases down the group because the radius increases and the
electronegative decreases. High ionization energy of F explain why it doesn’t have
positive oxidation numbers.
- From F to I, the coordination numbers increase. This is due to the involvement of the
d orbitals in types of hybrid orbitals. Another reason is the increase in radius from F to I.
9.2. HALOGENS
9.2.1. Occurrence and isotopes
• Occurrence
Halogen are chemically active, therefore they are usually found in compounds.
- Fluorine: popular, can be found in some minerals such as fluorite (CaF2), cryolite
(Na3AlF6), fluorapatite Ca5(PO4)3F or (3Ca3(PO4)2Ca(F,Cl)2) found in teeth enamel
- Chlorine: found in NaCl (ocean water, salt mine), sylvinite NaCl.KCl, carnallite
KCl. MgCl2.6H2O, NaCl in blood and HCl in gastric acid in stomach.
- Bromine and Iodine: somewhat popular. Bromine goes with minerals of K of Cl in
salt lakes, mainlands, and sea salt. I is available in salt seeds and thyroid hormone. Sea
salt and oil drilling water are two main source to extract these 2 elements.
• Isotopes:
- F has 5 isotopes 17F, 18F, 19F, 20F and 21F but only 19F is stable.
- Cl has 8 isotopes: 32Cl, 33Cl, 34Cl, 35Cl, 36Cl, 37Cl, 38Cl and 39Cl, of them 2 are
stable: 35Cl(75,53%) and 37Cl (24,47%)
- Br has 16 isotopes, of which only 2 are stable: 79Br(50,56%) and 82Br(49,44%).
- I has 21 isotopes but only one is stable 27I (100%).
- At is radioactive
9.2.2. Halogens X2
Table: Characteristics of halogens:
No Compounds F2 Cl2 Br2 I2 At2

1 Melting point, 0C -219,6 -101,9 -7,3 113,6 -

2 Boiling point, 0C -187,9 -34,4 58,2 184,5 -

3 Dissociation energy, kJ/mol 159 242 192 150 117

4 Bond length, 1,42 1,99 2,28 2,67 -

5 Heat of hydration X-,kJ/mol -506 -376 -343 -297 -

6 Reduction potential X2, 2X- 2,87 1,36 1,07 0,54 -

 7 Decomposition temperature 450 800 600 400 -

Comments:
• Electronic structures:
• Boiling points and melting points
Halogens interact with each other through van der Waals, mainly through diffusion
forces. From F2 to I2, r increases mt the ability to be polarized increases so diffusion force
increases from F2 to I2. Besides, mass increases from F2 to I2, this is also another reason.
• Change in bonding energy:
2 halogen atoms are linked by a σ bond. In Cl2, Br2 and I2, in addition to σ, there is a
π formed by overlapping between orbital p containing lone paired e of the halogen này
and an empty d orbital of the other. Fluorine doesn’t have orbital d, so it can not form π
bond, so dissociation energy of F2 is smaller than Cl2. From Cl2 to I2, bonding energy
decreases when bond length increases.
V.2.3. Physical properties:
-Appearance: At STD, F2, Cl2 are gases, Br2 is a liquid and I2 is solid. All taste
terribly and toxic
- Color: Table: Absorption wavelengths and colors of halogens.
Halogen F2 Cl2 Br2 I2

ëmax, nm absorb 285 330 420 520

Color pale yollow pale green red-bround violet-black

The colors of halogens are due to the absorption of UV light to transfer from π* to
σ*. From F2 đến I2, difference in energy between these 2 levels decreases, wavelength
increases and the color is darker.
- Solubility:
As non polar covalent compounds, halogens are slightly soluble in water. When
cooled from water, it forms crystals of hydrate X2.8H2O in which halogens occupy empty
spaces formed between water molecules due to hydrogen bonds.
Halogens are strongly soluble in organic solvent such as benzene, carbon disulfide,
alcohol, ether.
-Some properties of Iodine:
Sublimation: when a solid changes directly the gas phase without passing the liquid
state when changing temperature. For I, vapor pressure over the surface of I crystal is
greater than atmosphere pressure, so it is ready to sublime.
 I2 is strongly soluble in solution containing I- to form I-3 complexes which is brown,
iodine turn starch to blue because I2 occupy the space inside the starch helix. When
heated, the helix is stretches, releasing I2.
9.2.4. Chemical properties:
Halogens are strong oxidizers. The oxidation ability decreases down the group,
consistent with the decrease in reduction potential and electron affinity.
Down the group, the reducing ability increases. F2 can not act as reducing agent.
F has lower electron affinity than F, but it is still more reactive. This is due to the small
binding energy of F. In solution, F is also a stronger oxidizer, cause the X2→2X- depends
also on heat of hydration, which is large for F due to its small radius. Beside, all chemical
bonds of fluorine compounds are usually stable.
1. React with hydrogen
Reagent Products Ho298, ht Conditions Characterization

F2 HF -288,6 Darkness,-2520C Endothermic

Cl2 HCl -92,3 light, slightly heat explosivable

Br2 HBr -35,98 200-3000C, Pt catalyst non explosivable

I2 HI +25,9 4000C, Pt catalyst reversed, endothermic

2. React with other non metals:

X2 react with almost all non metals, F2 does not react with N2 and He, Ar, only reacts
with O2 in liquid air. Cl2, Br2 does not react directly with C, N, O, noble gases (Br’s
reactions are less violent), iodine doesn’t react directly with B, C, N, O , S, inert gases.
Group Elements F2 Cl2 Br2 I2

III B BF3 (l) BCl3 (l) BBr3 (l) -

C CF4 - - -
IV
Si SiF4 (k) SiCl4 (l) SiBr4 (l) SiI4 (r)

N2 - - - -
V PI3 (P white,I2
P PF3, PF5 PCl3(l), PCl5(r) PBr3(1),PBr5(r)
crystal)

O2 F 2O 2 - - -
VI
S SF6 S2Cl2(l) S2Br2(l) -

VII F2 - ClF, ClF3 BrF, BrF3, BrF5 IF5, IF7

 ClF (250oC)
Cl2 - HBrO3 HIO3
ClF3 (280oC)

Br2 BrF, BrF3, BrF5 HBrO3 - -

I2 IF5, HIO3 - -

3. React with metals

Halogens can react with almost all metals to form products in which metals are of
high oxidization states (except I2), for I2 all reaction need to be done a high temperature.
Group Elements F2 Cl2 Br2 I2

IA M MF MCl MBr

I Cu CuF2 CuCl2, CuCl

IB Ag AgF AgCl

IIA M MF2 MCl2 MBr2 MI2

II Zn ZnF2 ZnCl2 ZnBr2 ZnI2

IIB
Hg HgF2 HgCl2 HgBr2 HgI2(red), Hg2I2 (blue)

III IIIA Al AlF3 AlCl3 AlBr3 AlI3 (to, H2O cat)

Sn SnF4 SnCl4 SnBr4 SnI4

IV IVA
Pb PbF2 PbCl2 PbBr2 PbI2

VI VIB Cr CrF3 CrCl3

VII VIIB Mn MnF2 MnCl2 MnBr2 MnI2`

VIII VIIIB Fe FeF3 FeCl3 FeBr2, ít FeBr3 FeI2

Note: Cu, Ni, Mg are not corrosive in F2 gas because the formed compounds are stable
and cover the surface of the metals.
4. Reacts with hydride:
CH4: Cl2 and Br2 (gas) react with CH4 when expose to light: X2 + CH4 = C + HX
For NH3:
- Florine: 6F2 + 3NH3 = N2 + NF3 + 9HF
- Chlorine, bromine: 3Cl2 + 2NH3 = N2 + 6HCl
and: NH3 + HCl = NH4Cl (white smoke)
- Iodine: 5NH3 + 3I2 = 3NH4I + NH3 . NI3↓ (brown).
H2 O
- F2: reacts violently with water to form O2 (products can also be O3 and H2O2)
2F2 + 2H2O = 4HF + O2
3F2 + 3H2O = 6HF + O3
F2 + 2H2O = 2HF + H2O2
- Cl2, Br2: oxidization of water to form O2 is spontaneous, but requires high activation
energy, so the reactions are: X2 + H2O D HX + HXO (K = 4,2.10-4 for Cl and 7,2.10-9
for I2)
Chlorine water is used to bleach because HClO is a very strong oxidizer, but it is not used to
bleach wool cause it also oxidizes -NH groups in petit.
- I2 : I2 + 2H2O = H3O+ + I- + HIO K = 2,1.10-13
The equilibrium constant is to small, it can be considered that I2 does not react with water
that way, but this way:
I2 + H2O D HI + HIO3
• H2S:
- Cl2 : 4Cl2 + H2S + 4H2O = 8HCl + H2SO4
- Br2: Br2 + H2S = 2HBr + S
and 4Br2 + H2S + 4H2O = 8HBr + H2SO4
- I2 : I2 + H2S = 2HI + S
• Hydride ions: KH + Cl2 = KCl + HCl
5. Reaction with basic solution
- F2 :
2F2 + 2NaOHdilute 2% = OF2 + 2NaF + H2O
2F2 + 4NaOHconcentrated = O2 + 4NaF + 2H2O
- Cl2:
Cl2 + NaOHdil = tNaCl
0 + NaClO + H2O
3Cl2 + 6NaOHcon = 5NaCl + NaClO3 + 3H2O
- Bromine and Iodine:
3X2 + 6NaOH = 5NaX + NaXO3 + 3H2O (X = Br, I)
BrO and IO are not stable in basic environment, they are easily converted into BrO3- và
- -

IO3- 3XO- = 2X- + XO3- (X = Br, I)

Similar reactions occur for hydroxide solution of other alkaline and alkaline earth
metals:
 2Cl2 + 2Ca(OH)2 = CaCl2 + Ca(OCl)2 + 2H2O
6Cl2 + 6Ca(OH)2 = 5CaCl2 + Ca(ClO3)2 + 6H2O
6. Exchange reaction:
- F2 :
F2 + 2KCl(t.t) = Cl2 + 2KF
4F2 + 2KBr(t.t) = 2BrF3 + 2KF
6F2 + 2KI = 2IF5 + 2KF
- Cl2, Br2:
Cl2 + 2NaBr = Br2 + 2NaCl
Br2 + 2KI = I2 + 2KBr
I2 + KI = KI3
7. Reacts with compounds of metals
Aqua solution of chlorine, bromine oxidize Fe(II) to Fe(III), K4[Fe(CN)6] to
K3[Fe(CN)6], Sn(II) to Sn(IV):
FeCl2 + Cl2 = FeCl3
K4[Fe(CN)6] + Cl2 = KCl + K3[Fe(CN)6]
Iodine water oxidizes Sn(II) to Sn(IV):
Sn2+ + I2 = Sn4+ + 2I-
8. Reacts with strong oxidizers
Beside oxidization, Br2 and I2 can act as reducing reagents when reacting with stronger
oxidizers: 5Cl2 + Br2 + 6H2O = 10HCl + 2HBrO3
I2 + AgNO3 = AgI + INO3
3INO3 = I2 + I(NO3)3
9.2.2. Preparation
General principle: oxidize halides (X-) by strong oxidizer or electrical current.
• Fluorine: due to its strong oxidizer, the only method is to electrolyze the mixture
of KF + 3HF (the melting point is 660C)
• Chlorine:
- in laboratories: chlorine is prepared by heating the mixture of concentrated HCl
with strong oxidizer like MnO2, CaOCl2, KMnO4, K2Cr2O7, PbO2, HNO3.
VD: heating the mixture of MnO2 and concentrated HCl, MnCl3 is form and dissociated
to MnCl2 and Cl2.
2MnO2 + 8HCl = 2MnCl3 + Cl2↑ + 4H2O
2MnCl3 = 2MnCl2 + Cl2↑
 The mixture of sodium chlorine and MnO2 + 3H2SO4 can also be used:
2NaCl + MnO2 + 3H2SO4 = 2NaHSO4 + MnSO4 + Cl2↑ + 2H2O.
Other reactions:
2HCl + CaOCl2 = CaCl2 + Cl2 + H2O
3HCl + HNO3 = NOCl + Cl2 + 2H2O
- Manufacturing: chlorine is prepared by oxidizing HCl by oxygen in the air at 400 -
o
450 C, with the catalyst of CuCl2:
4HCl + O2 = 2H2O + Cl2
or electrolyzing saturated NaCl solution:
2NaCl + 2H2O = 2NaOH + Cl2↑ + H2↑
or electrolyzing concentrated HCl solution:
• Bromine and iodine:
Bromine and iodine can be prepared by using Cl2 to oxidize bromide and iodide
salts available in ocean water (Br) or seaweeds oil drilling water (I)
Cl2 + 2NaBr = 2NaCl + Br2
distill the mixture and at the same time, use air to blow bromine into soda solution until it
is saturated.
2Br2 + 3Na2CO3 = 5NaBr + NaBrO3 + 3CO2.
finally acidify by sulfuric acid:
5NaBr + NaBrO3 + 3H2SO4 = 3Br2 + 3H2O + 3Na2SO4.
9.3. HIĐRO Halides
9.3.1. Some characteristics:
Table: Some characteristics:
N0 Properties HF HCl HBr HI

1 Bonding energy, kJ/mol 565 431 364 297

2 0,92 1,27 1,41 1,60

Bond length,

3 Dipole moment ,D 1,98 1,07 0,79 0,38

4 Melting point, oC -83 -114,2 -88 -50

5 Boiling point, oC +19,5 -84,9 -66,7 -35,8

6 Solubility S (g/100gH2O) ∞ 78 210 234

 • Electronic structure: text book
• Bond length: decrease down the group. This is because down the group, the radius
increases, the difference in energy and spatial structure of 2p orbitals of halogens with
AO1s of H increases, the overlapping between them is weaker, bond length increases so
bonding energy decreases
• Dipole moment: decreases down the group due to the decrease in electronegativity
of halogens. Because 4e in non bonding MO nx and ny H - X bonds are polar
9.3.2. Physical properties:
States: all hydrogen halides are gases at normal condition.
Melting and boiling points:
Melting and boiling points are low and decrease from HF to HCl, but increases from
HCl to HI. This is because the interaction between these polar molecules are Van de
waals forces which increase from Cl to I due to the increase in R of halogens, and
therefore the increase in diffusion forces, and the increase in molar mass. The melting
and boiling points of HF are high because of the hydrogen bonding that can combine 2-6
molecules of HF molecules can combine to to form poly-molecules: nHF→(HF)n, at
temperature above 90oC HF is a fully mono-molecule. Also for this reason, liquid HF is a
good solvent to ionize. Pure HF liquid can auto-ionize as:
HF + HF = H2F+ + F- K = 10-10
liquid HF is a super strong acid. Such strong acids as HNO3 are still bases in liquid HF:
HNO3 + 2HF = H2NO3+ + HF2-
Solubility:
Strongly soluble in water because all H - X bonds are polar. The dissolution is
exothermic because of the large heat of hydration of X- and H+. Constant boiling mixtures
can be formed: HCl 20,2% (toboiling=110oC), HBr 47,5% (toboiling=126oC), HI 57%
(toboiling=127oC).
Toxicity: H - X smells shocking, HF is toxic.
9.3.3. Chemical properties
• Stability:
at high temperature, HX dissociates and the efficiency increases down the group:
2HF F2 + H2
2 HCl H2 + Cl2 0,014%
2 HBr H2 + Br2 0,5%
2 HI H 2 + I2 33%
 • Acidity
- Acid dissociation constants:
Acid HF HCl HBr HI
Ka 7,8.10-4 1,5.107 1,2.109 4,6.1010
Ka increases from HF to HI because bonding energy decreases due to increase in
halogen radius mt the ability to dissociate to H+ increases => the acidity increases. HF is
weaker acid because of the reaction of F- and HF.
aqua HF is a weak acid:
HF + H2O H3 O+ + F- Ka = 4.10-4
HF +F- HF2- K=5
-hydrohalic acids are strong acids which react with metals, bases, basic oxide, salts, and
with metal compounds of low oxidization numbers of metals.
Fe + HCl = FeCl2 + H2
Note
HX + KOH = KX + H2O ( X=Cl, Br, I)
2HF + NaOH = NaHF2 + H2O (Na[H2F3], Na[H3F4], Na[H4F5]
and HF is the only acid that reacts with SiO2
SiO2 + 4HF = SìF4 + 2 H2O
SiF4 + HF = H2SiF6
• Reduction ability
Due to the decrease in H-X bonding energy and the electronegativity down the
group,the reduction ability of hydrohalic increases from HF to HI:
HF does have any reduction ability.
HCl acts as a reducing reagent only when reacting with strong oxidizers like
KMnO4, MnO2, PbO2, K2Cr2O7, HNO3…
HBr and HI are strong reducing agents. Concentrated sulfuric acid is reduced by
HBr to SO2 and by HI to H2S:
2HBr + H2SO4 = Br2 + SO2 + 2H2O
8HI + H2SO4 = 4I2 + H2S + 4H2O
HCl + HNO3 = no reaction
HBr + HNO3 concentrated= Br2 + NO2 + H2O
HI + HNO3 concentrated= I2 + NO2 + H2O
KI + FeCl3 = I2 + FeCl2 + KClS
Solutions of HBr, HI turn to yellow brown if exposed to air cause oxygen oxidizes these
solutions to free halogens. HCl reacts with O2 only in gas phase and when heated with
presence of CuCl2 : 4HI + O2 = 2H2O + 2I2
To purify contaminated HBr, HI, one can extract halogens using organic solvents or
reducing agents like H2S, H2SO3…
9.3.4. Preparation of H-X
1. HF:
The only method in manufacture and in laboratory is to let fluoride (usually CaF2)
react with concentrated H2SO4 at 250oC:

CaF2solid +H2SO4concetrated CaSO4 + 2HF

2. HCl
normal T
- Laboratory:
NaCl(t.t) + 4000C H2SO4concentrated = NaHSO4 + HCl↑
NaHSO4 + NaCl Na2SO4 + HCl↑
0
t - Manufacture:
H2 + Cl2 2HCl
3. HBr and HI:
-hydrolysis of bromides and iodides of phosphor.
PX3 + 3H2O = H3PO3 + 3 HX (X: Br, I)
In fact, one can let Br2 or I2 react directly with P and H2O.
9.3.5. Uses of hydrogen halides
- HF: used in etching glass, cleaning sand on surface of metals, organic synthesis,
preparation of fluoride and, cryolite.
- HCl: used in preparation of vinyl chloride in polymer industry, fluorides in industry,
ammonium chloride, medicine and dye solution.
V.3.6. Halides: compounds of halogens with other elements
- divided into 2 groups: ionic halides and covalent halides.
- Ionic halides include halides of alkaline metals except Li, alkaline earth metals except
Be and transition metals, lanthanide , actinides.
- Covalent halides include halides of non metals, amphoteric metals, or metals with high
oxidization numbers.
1. Solubility
-Ionic halides: soluble except these of Ag+, Cu+, Hg+(Hg2Cl2), Pb2+. fluoride are insoluble
in general. VD CaF2 is insoluble but CaCl2, CaBr2, CaI2 are soluble so Ca2+ is an
indicator of F-. AgF is soluble while other silver halides are unsoluble so Ag+ is an
indicator of halides (except F-) .
- Covalent halides are easy to evaporate, soluble in non-polar solvent, easy to hydrolyzed
, not electrical conductive when melted and easy to be polymerized: exp (BeCl2)2,
(AlCl3)2
2.Reduction ability
Self study
3. Ability to form complexes
Halides can form complexes with metal ions. Most important are complexes of
fluoride and chloride, formed when halides of metals or non metals (acid) interact with
halide ions (base):
AlF3 + 3F- = AlF6-
FeF3 + 3F- = FeF6-
BF3 + F- = BF4-
PF5 + F_ = PF6-
The stability of the complexes follows the trend: F- > Cl- > Br- > I- with some
exceptions.
9.4.OXIDES AND OXYAXID OF HALOGEN
Oxi
F Cl Br I
state
+7 Cl2O7 HClO4
+6 Cl2O3, Cl2O6 BrO3
+5 HClO3 HBrO3 I2 O 5 HIO3
+4 ClO2 BrO2
+3 Cl2O3 HClO2
+2
+1 HFO Cl2O HClO Br2O HBrO HIO
-1 F2On(n=1-4)
9.4.1. Oxides of halogens: Chlorine forms Cl2O, Cl2O3, ClO2, Cl2O6, Cl2O7, of
which only Cl2O7 is stable at normal condition
*Cl2O (Dichlorine monoxide): - orange gas at STP, smell like chlorine.
- not stable, ready to dissociate to Cl2 and O2 so reacts violently with many elements.
Soluble in water to form a yellow orange solution containing ClO-.
- preparation: Let newly prepared HgO react with chlorine gas:
2 Cl2 + 2 HgO = HgO.HgCl2 + Cl2O
*ClO2: - yellow-blue gas at STP, unstable, needs to be prepared where and when it will
be used, strong oxidizer:
Cl2O + 4H+ + 5e = Cl- + 2 H2O E0 = 1,5v
- strongly soluble in water and can form stable hydrate at temperature below 180C
- dilute solution is stable in dark, when exposed to light, it gradually dissociates to HCl
and HClO3
2Cl2O + 2KOH = KClO2 + KClO3 + H2O
*Cl2O7: colorless and viscous liquid at STP. Dissociates at1200C. It is the weakest
oxidizer among all oxides of chlorines, can form an explosion mixture with Iodine.
Infinitively soluble in CCl4 but slowly soluble in water:
Cl2O7 + H2O = 2 HClO4
Prepared by using P4O10 to absorb water of HClO4
9.4.2. OXYAXIDs of halogen
1. Hypohalous acid HXO and hypohalite (X = F, Cl, Br , I)
• Hypohalous acid HXO (X = F, Cl, Br , I)
- Structure:
with X = Cl, Br, I: O - X bond is stable by π acceptor-donor bond.
- Stability:
+ HFO is strong acid which is different from others, can be extracted into free form, can
dissociate to HF and O2 at STP
2 HFO + H2O =HF + H2O2
+ Other acids can only exist in dilute solution and the immediately dissociate to HX and O2
- Acidity:
All Hypohalous acid are weak acid: HXO + H2O = H3O+ + XO-
Acids HClO HBrO HIO
Ka 2,3.10-8 2,2.10-9 2,3.10-11
Explain: From HClO to HIO, stability of HO bonds increase because the stability of
O - X bonds decreases, reducing the ability to dissociate to H+. HIO dissociates like a
base with Kb = 3,10-10
In basic environment, ClO- dissociates slowly at room temperature, fast at T above 75oC:
 room T: Cl2 + 2KOH = KCl + KClO + H2O (1)
When heated: 3Cl2 + 6KOH = 5KCl + KClO3 + 3 H2O (2)
- Oxidization and reduction ability: (Latimer diagram).
Hypohalous acids are strong oxidizing agents. The oxidization decreases from Cl to
I, as illustrated by their reduction potential in acid environments.
HClO + H+ + 2e = Cl- + H2O Eo = 1,50V
HBrO + H+ + 2e = Br- + H2O Eo = 1,34V
HIO + H+ +2e = I- + H2O Eo = 0,99V
2HClO + 2H+ + 2e = Cl2 + 2H2O Eo = 1,63v
2HBrO + 2H+ + 2e = Br2 + 2H2O Eo = 1,59v
2HIO + 2H+ + 2e = I2 + 2H2O Eo = 1,45v
O2 + 4H+ + 4e = 2 H2O E0 = 1,23v
In acid solutions, HClO can oxidize Fe2+ to Fe3+, Cl- to Cl2, I- to I2:
HClO +2Fe2+ + H+ = 2Fe3+ + Cl- + H2O
HClO + Cl- + H+ = Cl2 + H2O
HClO +2I- + H+ = I2 + Cl- + H2O
- Preparation of HXO: (Hoàng Nhâm -267)
HClO: 2 NaClO + H2SO4 = Na2SO4 + 2 HClO
Cl2 + H2O ↔ HCl + HClO
let the mixture run through HgO: HCl + HgO = HgO.HgCl2 and finally let chlorine gas
pass by Cl2 + H2O + HgO = HClO + Hg2Cl2↓yellow

• hypohalite: XO- (X = Cl, Br, I)

- Stability:
Ion XO- is more stable than the corresponding HXO, the stability decreases from ClO- to
IO-. These salts are known to exist only in solutions, except for salts of K, Na, Ca and
ClO- can be extracted in solid forms. tách ra được ở trạng thái rắn.
In basic environment, XO- dissociates as follows:

3XO- 2X- + XO
The dissociation ability increases from ClO- to IO- due to the decrease in bond
stability. Ion ClO- dissociates slow at normal T but fast at 75oC. Ion BrO- dissociates
slowly at 0oC but fast at normal T; ion IO- dissociates in all temperature so I2 reacts with
alkaline solution following the reaction:
3I2 + 6KOH = 5KI + KIO3 + 3H2O
-Oxidization:
In basic environment, XO- are strong oxidizers:
Cặp oxi hóa - khử X = Cl X = Br X=I

XO-/X2 0,40V 0,45V 0,45V

XO-/X- 0,88V 0,76V 0,49V

ClO- can oxidize H2O2 to O2, Mn2+ to MnO42-, Cr3+ to, NH3 to N2:
H2O2 + ClO- = O2 + Cl- + H2O
2Mn2+ + 2ClO- + 4OH- = 2MnO42- + 2Cl- + 2H2O
2Cr3+ + 3ClO- + 10OH- = 2CrO42- + 3Cl- + 5H2O
2NH3 + 3ClO- = N2 + 3Cl- + 3H2O
• Javel water and bleach powder: (HHVC ở trường PTHT, 70-73).
Javen water: aqueous solution of NaCl, NaClO, H2O (Can replace Na = K)
- Preparation:
+ In laboratory PTN, Javel water is prepared by by passing chlorine gas through a
solution of NaOH or KOH at normal temperature: Cl2 + 2NaOH = NaCl + NaClO +
H2 O
+ In manufacture, Javel water is prepared by electrolyzing diluted table salt solution (15 -
20%) with no boundary membrane:
2NaCl + H2O = 2NaOH + Cl2 + H2
2NaOH + Cl2 = NaCl + NaClO + H2O
- Properties: + unstable with heat
KClO KCl + KClO3
KClO3 KClO4 + KCl
KClO4 KCl + O2
+ are strong oxidizers in any environment. The bleaching ability is due to ion ClO- with
high oxidizing ability. It can bleach wool but also destroy wool:
NaOCl + PbS = PbSO4 + NaCl
NaOCl + H2O2 = NaCl + O2 + H2O
NaOCl + HCl concentrated = NaCl + Cl2 + H2O
Bleach powder (chlorine powder): CaOCl2, a yellow white solid with strong smell of
Cl2 it is a bleach powder with composition of: (3Ca(ClO)2. 2Ca(OH)2.. H2O +
CaCl2.Ca(OH)2.H2O
- Preparation: Passing Cl2 through concentrated solution of Ca(OH)2 at 300C:
Cl2 + Ca(OH)2 = Ca(OCl)2 + H2O + CaCl2
- Properties:
+ undergoes rapid decomposition: when exposed to light, 2CaOCl2 =2CaCl2 + O2
+ is a strong oxidizer in any environment, therefore used in killing bacteria, paper, wool
industry. Also used in preparation of Cl2 and O2
CaOCl2 + 2HCl = CaCl2 + Cl2 +H2O
2CaOCl2 = 2CaCl2 +O2
2. Halous acid and halite salt
• Chlorous acid
+ Acidity: HClO2 is a medium acid, dissociating in water as follows: :
HClO2 H+ + ClO2- Ka = 1,1.10-2
+ Stability: HClO2 is unstable, only exist in solutions and quickly dissociate due to
the reaction:
4HClO2 = 2ClO2 + HClO3 + HCl + H2O
+ Oxidizing ability: HClO2 is a strong oxidizer as indicated by high reduction
potentials:
HClO2 + 2H+ + 2e = HClO + H2O E0 = 1,64V
2HClO2 + 6H+ + 6e = Cl2 + 4H2O E0 = 1,63V
HClO2 +3H+ + 4e = Cl- + 2H2O E0 = 1,56V
+ Preparation of HClO2:
H2SO4 + Ba(ClO2)2 suspension = 2HClO2 + BaSO4↓
• chlorite salt
+ Structure:
Cl - O bond is 1,64A, shorter than length of the single bond (1,73 A).
+ Stability:
Ion ClO2- is more stable than HClO2 because in ClO2-, electron intensity is higher
in oxygen atoms, enabling formation of π bond of p→ d donor-acepter .
+ Oxidization ability: In alkaline solution, ion ClO2- is a strong oxidizer:
ClO2- + H2O + 2e = ClO- + 2OH- E0 = 0,66V
ClO2- + 2H2O + 4e = Cl- + 4OH- E0 = 0,77V
0,33 0,77
From Latimer diagram : ClO3- ClO2- Cl-
in alkaline environment, ClO2- dissociates when heated:
3ClO2- = Cl- + 2ClO3-
 In fact, when heated NaClO2 dissociates into chloride and chlorate.
3NaClO2 = NaCl + 2NaClO3
+ Preparation:
2ClO2 + Na2O2 = 2NaClO2 + O2
ClO2 + BaO2 = BaClO2 + O2
3. Halic acid and halate salt
• Halic acid HXO3 ( X = Cl, Br, I)
+ Acidity:
In water, they are strong acids, with acid force decrease from Cl to I. Acid
dissociation constants are Ka =101, 2.10-1, 1,7.10-1
+ Stability: increases from HClO3 to HIO3.
HClO3 and HBrO3 only found in solution. At concentration above 50%, HClO3 and
HBrO3 dissociate as follows:
3HClO3 = HClO4 + 2ClO2 + H2O
4HBrO3 = 2Br2 + 5O2 + 2H2O
HIO3 can occur as a colorless crystal, it is easy to dissolve in water and easy to absorb
water in air.
+Oxidization ability:
Are strong oxidizers as indicated by the following reduction potentials:
Cặp oxi hoá - khử X = Cl X = Br X=I

X 3 -, H + / X 2 1,47V 1,52V 1,20V

X 3 -, H + / X - 1,45V 1,45V 1,08V

They react with S, P, As, SO2. Paper, cotton ball burn immediately after exposed to
HClO3 40% solution.
+ Preparation: let halate salts react with concentrated H2SO4 solution:
Ba(ClO3)2 + H2SO4 = 2HClO3 + BaSO4↓
NaIO3 + H2SO4 = HIO3 + NaHSO4
HIO3 can be prepared by reaction of I2 with concentrated HNO3 solution:
3I2 + 10HNO3 = 6HIO3 + 10NO + 2H2O
I2 + 5Cl2 + 6H2O = 2HIO3 + 10HCl
• Halate salts:
+ Structure: chóp tam giác đều, halogen atoms are X sp3 hybridized
+ Stability:
 More stable than the corresponding acids because they are ionic compounds.
+ Oxidizing ability:
In neutral environment, the halates are weaker oxidizer than in acid environment
X = Cl X = Br X=I

XO3-+ 3H2O + 6e = X- + 6OH- 0,63V 0,61V 026V

2XO3- + 6H2O + 10e = X2 + 12OH- 0,49V 0,50V 0,21V

At solid states, all halates are strong oxidizers and the oxidization ability decreases
from chlorate to iodate: P, S, C can form an explosion mixture with halates:
2KClO3 + 3S = 2KCl + 3SO2 (heat is needed)
2KClO3 + 3C = 2KCl + 3CO2 (heat is needed)
When heated, all halates dissociate to librate O2:
900C
2NH4ClO3 N2 + Cl2 + O2 + 4H2O
Potassium chlorate (KClO3)
- Preparation: + Electrolyze KCl 20% at 70oC
Cl2 + KOH =KCl + KClO + H2O
KClO = KCl + KClO3
then precipitate KClO3 out of solution.
+ Passing Cl2 water through hot calcium hydroxide solution
6Cl2 + 6Ca(OH)2 = Ca(ClO)3 + 5CaCl2 + 6 H2O
sau đó Ca(ClO)3 + 2KCl = CaCl2 + 2 KClO3
based on solubility at 0oC KCl CaCl2 CaClO3 KClO3
g/100gH2O 27,6 59,5 177 5,3
we can precipitate KClO3 out of the solution as above.
- Properties: +colorless crystal, slightly soluble in cold water, strongly soluble in hot
water, melting point is 356oC (150 to 300 oC)
+ is a stable compound but easy to dissociate when heated.
KClO3 = KClO4 +KCl (356 to 400 oC)
KClO4 = KCl + O2 (550 to 620 oC)
when catalyzed by MnO2 KClO3 = KCl + O2 (150 to 300 oC)
+ is a strong oxidizer, forms a self burning mixture with P
10KClO3 + 12 Pred = 10KOH + 3P4O10
(mixture includes KClO3, sugar, S, Al powder is an explosive mixture).
- Uses: Potassium chlorate was one key ingredient in early firearms percussion caps,
when mixed with a suitable fuel, it may form an explosive material, a so-called Sprengel
explosive. Another application of potassium chlorate is as the oxidizer in a smoke
composition such as used in, e.g., smoke grenades
4. Perhalic acid and perhalic salts
Among perhalic acids, most popular are perchloric and periodic acids; and most
valuable are HClO4 and KClO4
• Perchloric acid
- Structure:
Cl is sp3 hybridized. Cl-O bond length is much shorter than the single bond,
indicating that the ability to form π bond (p → d) is stronger than ClO3-.
- Tính chất:
+ is a colorless liquid, smokes in air, Tboiling=130oC, tmelting=-112độ
+ unstable, and most stable in oxyacid of chlorine, but more stable in water due to
hydrogen bond. HClO4 = H2O + Cl2O7
+ is the strongest acid among all acids, Ka=108. In H2SO4, HNO3, CH3COOH, HClO4
solvent, it is still an acid.
+ is a strong oxidizer in solid form, in dilute solution, it is stable and have almost no
oxidization ability, does not react with strong reducers such as HI, H2S, SO2, H atom.
ClO4- + H2O +2e = ClO3- + 2OH- E0 = 0,36V
2ClO4- + 16H+ + 14e = Cl2↑ + 8H2O E0 = 1,39V
ClO4- + 4H2O +8e ⇌ Cl- +8OH- E0 = 0,56V
- Uses: use in analytical chemistry to blow a easy vaporizing acid out of its solution.
• Chlorate salt:
- Structure:
Ion ClO4- shape is tetrahedral, similar to SiO44-, PO33-, và SO42-. It is the most stable
compound of choline that contains oxygen.
- Properties:
When heated, it dissociates to chloride and oxygen. In solution, it doesn’t have
oxidization ability. The solid form can act as an oxidizing reagent, especially when
heated.
- Preparation:
KClO4 + H2SO4concentrated = KHSO4 + HClO4
CHAPTER X: GROUP VIIIA ELEMENTS (NOBLE GASES)
I. Characteristics of elements of group VIIIA
Noble gases, or inert gases include: He, Ne, Ar, Kr, Xe, Rn. He, Ne are light
gases, Ar, Kr, Xe are heavy gases and Rn is an radioactive element.
N0 Characteristic He Ne Ar Kr Xe Rn

2 Electron configuration 1s2 2s22p6 3s23p6 4s24p6 5s25p6 6s26p6

3 1,22 1,60 1,92 1,98 2,18 2,20

Atomic radius

4 Ionization energy I1, eV 24,58 21,56 15,76 13,99 12,13 10,75

- The outer shells include 8e except for He , all electrons are paired. These
configurations are stable, so elements of group VIIIA, especially light gases, are
relatively inert or non active.
- The atomic radius increases with Z, so the inertia decreases.
- Ionization energy is high, and decreasing with Z because all electrons of the
outside shell are paired, and the radius increases with Z.
II. Occurrence and isotopes
- Occur in nature in the forms of free elements with a small compound, total noble gas
constitutes less than 1% of the atmosphere.
- He has 2 isotopes 23He and 24He (≈ 100%), Ne has 3 isotopes 1020Ne, 1021Ne, 1022Ne, Ar
has 3 isotopes, Kr has 6 isotopes in which 3684Kr makes up 56,9%, Xe has 9 isotopes, of
which the most dominant are 54132Xe (26,89%), 54129Xe (26,44%).
* Method for extraction of noble gases:
- He is extracted by fractional distillation from natural gas, which contain up to 70%
helium.
- Neon, argon, krypton, and xenon are obtained from air using the methods of
liquefaction of gases, to convert elements to a liquid state, and fractional distillation, to
separate mixtures into component parts.
III. Physical and chemical properties
1. Physical properties:
Molecules He Ne Ar Kr Xe

Composition in dry air,

5,2.10-4 1,8.10-3 0,93 1,1.10-4 8,7.10-6
%V

Ts (0C) -269 -246 -106 -153 -109

 Tnc (0C) -270 -249 -189 -157 -12

S (200C,ml/l H2O) 9,7 26 56 110 242

- Nobel gases occur in monoatomic substances which are colorless, odorless,

tasteless, except for Kr, which is blue..In discharge tubes, these gases give specific
colors: He is yellow, Ne is red, Ar is blue, Kr is purple and Xe is pale blue. .
- The interaction between monatomic gases are weak so noble gases have low
melting and boiling point. Down the group, atomic radius and interatomic forces
INCREASE resulting in an INCREASED melting point, boiling point, enthalpy of
vaporization, and solubility.
- The inert gases are soluble in water and their solubility increases down the group.
The gases are more soluble in organic solvents such as alcohol, ether, benzene. Can be
readily absorbed by carbon. In solid state, He crystal is similar to H2 while Ne, Ar, Xe, Kr
crystals are face center cubic.
2. Chemical properties
- Inert gases used to be though as fully inert. Now, one knows that except for He,
Ne, Ar which are inert, Xe, Kr, Rn are reducing agents. Due to the fact that I1 of Xe is
1169kj/mol and of O2 is 1084kj/mol, and their radiuses are about the same, (around 4 ),
N. Barlett think that Xe should react with PtF6 like O2. He mix xenon and PtF6 at
temperature and obtain an orange crystal, with component of Xe+[PtF6]-+. Xe+[PtF6]-
sublimates in air, and dissociate in water to form Xe, O2, HF và PtO2.
O2 + PtF6 = Ο2+[PtF6]-
Xe + PtF6 = Xe+[PtF6]-
Noble gases can no gain electrons so they can not act as oxidizers.
- Now a day, many compounds of Kr, Xe and Rn are synthesized and their
properties are studied. The oxidization states of +1, +2, +4, +6, +8 have been known.
Since Rn is a radioactive element, their compounds have not been studied a lot.
Substances that can create compounds with noble gases are F2, O2, Cl2. In fact, studied
compounds are essentially ones formed from Xe with F and O. Kr can create some
compounds but they are unstable.
3. Uses
- He is the one with lowest boiling point. Many experiments require low
temperature and therefore are carried in liquid Helium.
- He is the lightest and non-flammable, so it is uses as gases to fill a gas balloon.
Helium and Argon are used to shield welding arcs and the surrounding base metal from
the atmosphere. Neon tubings are used in advertising and elaborate decorations. Xenon
has various applications in incandescent lighting, x-ray development, plasma display
panels (PDPs), and more. Incandescent lighting uses xenon because less energy can be
used to obtain the same light output as a normal incandescent lamp.

MO antibonding
MO non bonding
2
5p 2p 2p
MO bonding

IV. Some compounds of Xe

1. Xenon difluoride
a. Structure
XeF2 are linear. Orbital 5p of Xe with 2e overlaps with 2AOp containing one
unpaired electron of 2 F atoms, creating 3MO as described in the diagram.

Since their is no anti bonding electron, XeF2 are relatively stable, d (Xe - F) = 2,0
b. Physical properties
At STD, XeF2 is a colorless crystal. melting point = 140oC.
XeF2 is slightly soluble in water
c. Chemical properties
- Ready to dissociate: 2XeF2 = Xe + XeF4
- Soluble in water and be hydrolyzed. The process is quick in basic, but slow in acidic
and neutral environment:
XeF2 + 2H2O = 2Xe + 4HF + O2
- Strong oxidization.:
In aqua solution, XeF2 is a strong oxidizer than can oxidize I- to I2, Co2+ to Co3+… exp:
KIO3 + XeF2 + 3H2O = KH4IO6 + Xe + 2HF
2KI + XeF2 = Xe + I2 + 2KF
When reacting with H2 or NH3 , it form Xe:
H2 + XeF2 Xe + 2HF
8NH3 + 3XeF2 = 3Xe + 6N2 + NH4F
- Combination reaction
XeF2 can create valence compounds when reacting with fluoride:
XeF2 + 2SbF5 = Xe[SbF6]2 (yellow)
XeF2 + 2TaF5 = Xe[TaF6]2
These are diamagnetic compounds with such a structure:
F5SbF — Xe — FSbF5
2. Xenon tetra fluoride (XeF4).
- XeF4 is of square planar. Hybrid orbitals sp3d2 is used. Any F - Xe - F can be described
as 3 center bond like in the case of XeF2.
- at STD, it is a colorless solid, melting at 1140C without dissociating clearly:
3XeF4 = 2XeF6 + Xe
- Chemical properties: + also a strong oxidizer, reacts with H2, Hg, I- to form Xe
XeX4 + 2H2 = Xe + 4HF
+ Dissolves in water and hydrolyzes:
6XeX4 + 12H2O =2XeO3 + 4Xe + 3O2 + 24HF
3. Xenon hexafluoride XeF6
- Structure: XeF6 have octahedral shape, with center Xe atom in hybrid states sp3d2f. In
XeF6, any linear F-Xe-F is also described as a 3 center bond as in the case of XeF2.
- At STD, it is a colorless and stable solid.
- Chemical properties: XeF6 is strongly reactive.
+ Reacts violently with H2O, SiO2
XeF6 + 3H2O = XeO3 + 6HF
2XeF6 + SiO2 = 2XeOF4 + SiF4
XeOF4 + 5H2O = Xe(OH)6 + 4HF
+ is an oxidizer which can oxidize I- to I2
+ Due to the lone pair electrons, XeF6 can combine with some compounds such as: SbF5,
BF3, VF5: XeF6 + SbF5 = XeF6. SbF5
4. Xenon trioxide XeO3
- At STD, it is a white crystal, which is unstable and flammable.
- is an oxidizer: XeO3 + 6KI + 6HCl = Xe + 3I2 + 6KCl + 3H2O
- when reacting with strong oxidizers, it acts as a reducing reagent.
XeO3 + 4NaOH + O3 =Na4XeO6 + O2 + 2H2O
-Reacts with strong base: XeO3 + NaOH = NaHXeO4
5. Xenon tetroxide XeO4

XeO4 shape is tetrahedral, with Xe at the center, bond length Xe – O is 1,6 . XeO4 can
be prepare by letting concentrated H2SO4 react with Ba2XeO6 at normal temperature.
Ba2XeO6 + 2H2SO4 = 2BaSO4 + XeO4 + 2H2O
The existence of compounds of Kr, Xe, Rn with different oxidation numbers,
especially ones of oxidization number of 8 such as XeO4, H4XeO6 allows people to group
them into group VIIIA.
6. H4XeO6:
- Only found in solution, can not be extracted
- Solution of H4XeO6 is a strong oxidizer, it can oxidize Cr3+ to Cr2O72-, ClO-3 to ClO4-,
Mn2+ to MnO4-, Br- to BrO3-...