IC-chap 10

Shriver/ Atkins: Inorganic Chemistry
CHAPTER 10: Hydrogen

PART A: THE ESSENTIALS

10.1 The element
Lewis base: hydride ion, H-

Lewis acid: proton, H+
(a) The atom and its ions

Key points: The proton, H+, is always found in combination with a
Lewis base and is highly polarizing; the hydride ion, H-, is highly
polarizable.
1
H: protium 2
H: D, deuterium, 16/100,000 H: T, tritium, 1/1021
3
H-: two electrons are bound by just one proton  polarizable

Some of the processes that contribute to the biological hydrogen

cycle in a freshwater environment.
(b) Properties and reactions

Key points: Hydrogen has unique atomic properties that place it in
a special position in the periodic table. Dihydrogen is an inert
molecule and its reactions require a catalyst or initiation by
radicals.
Hydrogen may be found in a metallic state, such as the core of
Jupiter.
H—H Bond length: 74 pm
Electric discharge H2  H, H+, H2+, H3+ hydrogen plasma
Bond enthalpy
homolytic dissociation H2(g)  H(g) + H(g) ∆H = 436 kJ/mol
heterolytic dissociation H2(g)  H+(g) + H-(g) ∆H = 1675 kJ/mol

Explosive reaction: 2 H2(g) + O2(g)  2 H2O(g) ∆H = -242 kJ/mol
10.2 Simple compounds

(a) Classification of binary compounds
Key points: Compounds formed between hydrogen and other
elements vary in their nature ad stability. In combination with
metals, hydrogen is often regarded as a hydride; hydrogen
compounds with elements of similar electronegativity have low
polarity.
1. Molecular hydrides: individual, discrete molecules formed with
p-block elements. E-H bond: covalent bond Ex: CH4, NH3,
H2O
2. Saline hydrides: ionic hydrides, formed with the most

electropositive elements. Ex: LiH, CaH2 containing H- ions.
3. Metallic hydrides: non-stoichiometric, electrically conducting

solids with a metallic luster. Ex: NaBH4, LiAlH4
Shriver/ Atkins: Dihydrogen as a Fuel
Cu/ZnO
CH3OH(g) + H2O(g) CO2(g) + 3 H2(g) ∆H = 49 kJ/mol
Pd
CH3OH(g) + ½ O2(g) CO2(g) + 2 H2(g) ∆H = -155 kJ/mol
Reaction at temperature of 200-350 oC

(b) Thermodynamic consideration

Key points: In the s and p blocks, strengths of E-H bonds
decreases down each group. In the d block, strengths of E-H
bonds increase down each group.
H—H is the strongest single

homonuclear bond
 a compound to be exergonic and

stable with respect to its elements
 E—H should be stronger than H

—H
The weak bond formed by heavier

p-block elements
 poor overlap between the
relatively compact H 1s orbital and
the more diffuse s and p orbitals of
their atoms.
(c) Reactions of binary compounds

Key points: The reactions of binary compounds of hydrogen
fall into three classes depending on the polarity of the E—
H bond.
PART B: THE DETAIL

10.3 Nuclear properties
Key points: The three hydrogen isotopes H, D, T have large
differences in their atomic masses and different nuclear spins.
β decay (high-speed e-)
synthesis
Nuclear fusion
heated to > 100 MK
10.4 Production of dihydrogen

(a) Small-scale preparation
2 Al + 2 OH- + 6 H2O  2 Al(OH)4-(aq) + 3 H2(g)
Si + 2 OH- + H2O  SiO32-(aq) + 2 H2(g)
Zn + 2 H3O+  Zn2+(aq) + H2(g) + 2 H2O
CaH2(s) + 2 H2O  Ca(OH)2(s) + 2 H2(g)

(b) Production from fossil sources

Key points: Most H2 from industry is produced by high-
temperature reaction of H2O with CH4 or a similar reaction
with coke.
CH4(g) + H2O(g)  CO(g) + 3 H2(g) ∆H = 206.2 kJ/mol
C(s) + H2O(g)  CO(g) + H2(g) ∆H = 131.4 kJ/mol at 1000 oC
CO(g) + H2O(g)  CO2(g) + H2(g) ∆H = -41.2 kJ/mol
C(s) + 2 H2O(g)  CO2(g) + 2 H2(g) ∆H = 90.2 kJ/mol

(c) Production from renewable sources

Key points: Production of H2 by electrolysis of water is costly
and viable only in areas where electricity is cheap or if it is
a byproduct of an economically important process.
H2O(l)  H2(g) + ½ O2(g) E = -1.23 V, ∆G = 237 kJ/mol
An electrolysis cell for H2 production using Ni anodes and Fe cathodes

connected in series.
10.5 Reactions of dihydrogen

Key points:
Molecular hydrogen is activated by homolytic or heterolytic

dissociation on a metal or metal oxide surface or by
coordination to a d-block metal.
Reactions of hydrogen with O2 and halogens involve a

radical chain mechanism.
(a) Homolytic dissociation
(b) Heterolytic dissociation
CO(g) + 2 H2(g)  CH3OH(g)
Catalyst: Cu/ZnO/Al2O3
(c) Radical chain reactions

Initiation, by heat or light
Br2  Br• + Br•
Propagation
Br• + H2  HBr + H•
H• + Br2  HBr + Br•
Termination
H• + H•  H2
Br• + Br•  Br2
H• + Br•  HBr
2 H2(g) + O2(g)  2 H2O(g) ∆H = -242 kJ/mol

Shriver/ Atkins: BOX 10.3 Hydrogen from Solar Energy
425 oC
2 Cu(s) + 2 HCl(g) H2(g) + 2 CuCl(s)
electrolysis
4 CuCl(s) 2 Cu(s) + 2 CuCl2(s)
325 oC
2 CuCl2(s) + H2O Cu2OCl2(s) + 2 HCl(g)
550 oC
CH2OCl2(s) 2 CuCl(s) + ½ O2(g)
Dye-Sensitized Solar Cells (DSSCs)
(photosensitiser)
Dye-Sensitized Solar Cell (DSSCs)

10.6 Compounds of hydrogen

(a) Molecular hydrides
(i) Nomenclature and classification
Key points: Molecular compounds of hydrogen are classified
as electron-rich, electron-precise, or electron-deficient.
Electron-precise: all valence electrons of the central atom

are engaged in bonds. (CH4, CH3CH3, SiH4, GeH4)
Electron-rich: there are more electron pairs on the central

atom than are needed for bond formation. (lone pairs on
the central atom; NH3, H2O, H2S)
Electron-deficient: there are too few

electrons to be able to write a Lewis
structure for the molecule. (B2H6
3-center, 2-eletron bonds)
(ii) Reactions of molecular hydrides
Homolytic dissociation occurs for the hydrogen compounds
of some p-block elements
R3SnH + R’X  R’H + R3SnX RF < RCl < RBr < RI

(R3Sn• & H•)
Thermal decomposition
250-300 oC
AsH3(g) As(s) + 3/2 H2 ∆H = - 66.4 kJ/mol
Others 2200 oC
H2O(g) ½ O2(g) + H2 ∆H = 242 kJ/mol
4 H2O
AlH4- + 4 RCHO  Al(OCH2R)4-
Al(OH)4- + 4 RCH2OH
EXAMPLE 10.1 Determining which hydrogen atoms in a molecule

are the most acidic
Phosphorous acid, H3PO3, is a diprotic acid and is more helpfully
written as OP(H)(OH)2. Explain why the H atom bound to P is much
less protonic than the two H atoms bound to O ?
Ans: P-H bond enthalpy: 321 kJ/mol

O-H bond enthalpy: 464 kJ/mol
but O in more electronegative than P  O-H is more protonic

(iii) Hydrogen bonding
Key points: Compounds and functionalities containing H
atoms attached to electronegative elements with at least
one lone pair often associate through hydrogen bonds.
An E-H is highly polar: -E—H+ •••• -E—H+ •••• -E—H+

hydrogen bond
b.p. /m.p. ↑  H bond ↑
Figure 10.6 Normal boiling points of p-block binary hydrogen compounds.

Figure 10.8 Base pairing in DNA.

Cytosine recognizes guanine through
the formation of three hydrogen bonds.
Figure 10.7 The structure of ice.

The structure shows all possible
atom positions, but only half are
actually occupied.
Cl-H-Cl: linear but not symmetrical

F-H-F : not linear but symmetrical
Figure 10.9 The variation of the potential energy with the position of the proton
between two atoms in a hydrogen bond.
Figure 10.11 The orientation of lone pairs as indicated by VSEPR theory

compared with the orientation of HF in the gas-phase H-bonded complex.
Figure 10.12 The cages of water molecules in clathrate hydrates; in this case
Xe4(CCl4)8(H2O)68.
Shriver/ Atkins: Inorganic Chemistry Methane clathrate hydrate
Ionic compound
(b) Saline hydrides
Electrolysis of molten-salt
solution
2 H- (melt)  H2(g) + 2 e-
Reaction with water (dangerous!!)

NaH(s) + H2O  NaOH(aq) + H2(g)
1. Metathesis: 4 LiH(s) + SiCl4  4 LiCl(s) + SiH4(g)
2. Addition to a Lewis acid:

NaH(s) + B(C2H5)3  Na[HB(C2H5)3]
3. Reaction with a proton source:

NaH(s) + CH3OH  NaOCH3(s) + H2(g)
Shriver/ Atkins: BOX 10.4 H2 Storage Materials
3 bar H2, 210 oC

Li3N(s) + H2(g) Li2NH(s) + LiH(s) ∆H = 148 kJ/mol
vacuum, > 320 oC at 298 K
3 bar H2, 255 oC

Li2NH(s) + H2(g) LiNH2(s) + LiH(s) ∆H = 45 kJ/mol
vacuum, < 200 oC
at 298 K
Figure B10.4 Structure relationship between Li2NH and LiNH2

(C) Metallic hydrides

Key points: No stable binary metal hydrides are known for
the metals in Groups 7 to 9; metallic hydrides have
metallic conductivity and in many the hydrogen is very
mobile.
Most metal hydrides:
- metallic luster, electrically conducting, less dense than the
parent metal, brittle
- variable composition (ZrH1.3 ~ ZrH1.75)
- CeH2-x is a metallic conductor, CeH3 is an insulator
Ni, Pt – hydrogenation catalysts.

Pd – at moderate pressure  PdHx, X<1
Pd absorbs up to 900 times its own volume of H2, which is given

off again on heating.
LaNi5  LaNi5H6: greater density of hydrogen than H2(liq)
Figure 10.14 Schematic diagram of a hydrogen

Figure 10.13 Hydrides formed by d- and f-block elements. The formulae are
limiting stoichiometries based on the structure type.
EXAMPLE 10.2 Correlating the classification and properties of

hydrogen compounds
Classify the compounds PH3, CsH and B2H6 and discuss their
probable physical properties. For the molecular compounds specify
their subclassification (electron-deficient, electron-precise or
electron-rich).
Ans: Cs: group 1  saline hydride  insulator & rock-salt structure
P, B: p-block  molecules  low molar masses &
high volatilities
PH3: lone pair  electron-rich
B2H6: electron-deficient
(C) Hydrido and dihydrogen complexes

Key points: A large number of d-block metals complexes are
known in which the dihydrogen molecule or hydride anion
are ligands.
Zn/NH3
Rh (aq)
3+
[RhH(NH3)5]2+
NaBH4
[FeI2(CO)4] [Fe(H)2(CO)4]
10.7 General methods for synthesis
1. Direct combination (hydrogenolysis)
2 E + H2(g)  2 EH
2. Protonation of a Brønsted basic anion:
E- + H2O  EH + OH-
3. Reaction of an ionic hydride or hydride donor with a halide

(metathesis)
EH + EX  E+X- + EH
NaCl(s) + H2SO4(l)  NaHSO4(s) + HCl(g)
LiAlH (s) + SiCl (l)  LiAlCl (s) + SiH (l)

EXAMPLE 10.3 Using hydrogen compounds in synthesis

Suggest a procedure for synthesizing lithium
tetraethoxyaluminate, Li[Al(OEt)4], from LiAlH4 and reagents
and solvents of your choice.
Ans: AlH4-  H- donor: strong Brønsted base than EtO-
LiAlH4 + 4 C2H5OH  Li[Al(OEt)4] + 4 H2

EXERCISE
10.2
10.3
10.7
10.8
10.10
10.14
10.20

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Shriver/ Atkins: Inorganic Chemistry

CHAPTER 10: Hydrogen

PART A: THE ESSENTIALS

Lewis base: hydride ion, H-

(a) The atom and its ions

H-: two electrons are bound by just one proton  polarizable

Some of the processes that contribute to the biological hydrogen

(b) Properties and reactions

heterolytic dissociation H2(g)  H+(g) + H-(g) ∆H = 1675 kJ/mol

10.2 Simple compounds

2. Saline hydrides: ionic hydrides, formed with the most

3. Metallic hydrides: non-stoichiometric, electrically conducting

Reaction at temperature of 200-350 oC

(b) Thermodynamic consideration

H—H is the strongest single

 a compound to be exergonic and

 E—H should be stronger than H

The weak bond formed by heavier

(c) Reactions of binary compounds

PART B: THE DETAIL

10.4 Production of dihydrogen

2 Al + 2 OH- + 6 H2O  2 Al(OH)4-(aq) + 3 H2(g)

Si + 2 OH- + H2O  SiO32-(aq) + 2 H2(g)

Zn + 2 H3O+  Zn2+(aq) + H2(g) + 2 H2O

CaH2(s) + 2 H2O  Ca(OH)2(s) + 2 H2(g)

(b) Production from fossil sources

C(s) + H2O(g)  CO(g) + H2(g) ∆H = 131.4 kJ/mol at 1000 oC

CO(g) + H2O(g)  CO2(g) + H2(g) ∆H = -41.2 kJ/mol

C(s) + 2 H2O(g)  CO2(g) + 2 H2(g) ∆H = 90.2 kJ/mol

(c) Production from renewable sources

An electrolysis cell for H2 production using Ni anodes and Fe cathodes

10.5 Reactions of dihydrogen

Molecular hydrogen is activated by homolytic or heterolytic

Reactions of hydrogen with O2 and halogens involve a

(a) Homolytic dissociation

(b) Heterolytic dissociation

CO(g) + 2 H2(g)  CH3OH(g)

(c) Radical chain reactions

Br2  Br• + Br•

H• + Br2  HBr + Br•

Br• + Br•  Br2

2 H2(g) + O2(g)  2 H2O(g) ∆H = -242 kJ/mol

Dye-Sensitized Solar Cell (DSSCs)

10.6 Compounds of hydrogen

Electron-precise: all valence electrons of the central atom

Electron-rich: there are more electron pairs on the central

Electron-deficient: there are too few

R3SnH + R’X  R’H + R3SnX RF < RCl < RBr < RI

EXAMPLE 10.1 Determining which hydrogen atoms in a molecule

Ans: P-H bond enthalpy: 321 kJ/mol

but O in more electronegative than P  O-H is more protonic

An E-H is highly polar: -E—H+ •••• -E—H+ •••• -E—H+

b.p. /m.p. ↑  H bond ↑

Figure 10.6 Normal boiling points of p-block binary hydrogen compounds.

Figure 10.8 Base pairing in DNA.

Figure 10.7 The structure of ice.

Cl-H-Cl: linear but not symmetrical

Figure 10.11 The orientation of lone pairs as indicated by VSEPR theory

(b) Saline hydrides

Reaction with water (dangerous!!)

1. Metathesis: 4 LiH(s) + SiCl4  4 LiCl(s) + SiH4(g)

2. Addition to a Lewis acid:

3. Reaction with a proton source: