Descriptive Chemistry of the Elements

HYDROGEN

© Ch111.20 / 211 2018-19

 HYDROGEN The Element

Hydrogen is the most abundant element in the universe and the tenth
most abundant by mass on Earth, where it is found in the oceans,
minerals, and in all forms of life.

The partial depletion of elemental hydrogen from Earth reflects its

volatility during formation of the planet.

The stable form of elemental hydrogen under normal conditions is

dihydrogen , H2 , which occurs at trace levels in the Earth’s lower
atmosphere (0.5 ppm) and is essentially the only component of the
extremely thin outer atmosphere.

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 HYDROGEN The Element

It is produced naturally, as a product of fermentation and as a

by-product of ammonia biosynthesis.

Dihydrogen has many uses. It is often cited as the ‘fuel of the

future’ on account of its availability from fully renewable
resources (water and sunlight) and its clean and highly
exothermic reaction with O2 .

The volatility and low energy density of H2 pose challenges for

its direct use as a fuel for vehicles, but it can be used to
produce energy-dense hydrocarbon fuels and is an essential
raw material for the industrial production of ammonia.

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HYDROGEN The Element

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HYDROGEN The Element

The hydrogen atom, with ground-state configuration 1s1 , has

only one electron so it might be thought that the element’s
chemical properties will be limited, but this is far from the
case.

Hydrogen has richly varied chemical properties and forms

compounds with nearly every other element. It ranges in
character from being a strong Lewis base (the hydride ion, H
−
) to being a strong Lewis acid (as the hydrogen cation, H+,
the proton;

H atoms can form bonds to more than one other atom

simultaneously. The ‘hydrogen bond’ formed when an H atom
bridges two electronegative atoms is fundamental to life: it is
because of hydrogen bonding that water occurs as a liquid
rather than a gas, and proteins and nucleic acids fold into the
complex, highly organized three-dimensional structures that
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determine their functions.
HYDROGEN The Element

There are three isotopes of hydrogen: hydrogen itself (1H),

deuterium (D, 2H), and tritium (T, 3H); tritium is radioactive.
The lightest isotope, 1H (very occasionally called protium), is
by far the most abundant. Deuterium has variable natural
abundance with an average value of about 16 atoms in 100
000. Tritium occurs to the extent of only 1 in 1021

The different names and symbols for the three isotopes

reflect the significant differences in their masses and the
chemical properties that stem from mass, such as the rates
of diffusion and bond cleavage reactions.

The nuclear spin of 1H (I = 1/2) is exploited in NMR

spectroscopy for identifying hydrogen-containing molecules
and determining their structures.
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HYDROGEN The Element

The free hydrogen cation (H+ , the proton) has a very high
charge-to-radius ratio and it is not surprising to find that it
is a very strong Lewis acid.

In the gas phase it readily attaches to other molecules and

atoms; it even attaches to He to form HeH+ . In the
condensed phase, H+ is always found in combination with a
Lewis base, and its ability to transfer between Lewis bases
gives it the special role in chemistry.

The molecular cations H2+ and H3+ have only a transitory

existence in the gas phase and are unknown in solution. In
contrast to H+ , which is highly polarizing, the hydride ion,
H− , is highly polarizable because two electrons are bound
by just one proton. © Ch 47 2017_18 RMF
HYDROGEN Properties and reactions

Hydrogen’s unique properties distinguish it from all other

elements in the periodic table.

It is often placed at the head of Group 1 because like the

alkali metals it has only one electron in its valence shell.
That position, however, does not truly reflect the chemical or
physical properties of the element.

In particular, its ionization energy is far higher than the other

Group 1 elements, so hydrogen is not a metal, although it is
predicted to exist naturally in a metallic state where
extreme pressures exist, such as the core of Jupiter.

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HYDROGEN Properties and reactions

In some versions of the periodic table hydrogen is placed at

the head of Group 17 because, like the halogens, it requires
only one electron to complete its valence shell.

But the electron affinity of hydrogen is far lower than any of

the elements of Group 17 and the discrete hydride ion, H− , is
encountered only in certain compounds.

To reflect its unique characteristics, we place H in its own

special position at the head of the entire table.

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HYDROGEN Properties and reactions

H2 has so few electrons, the intermolecular forces

between H2 molecules are weak, and at 1 atm the
gas condenses to a liquid only when cooled to 20 K.

If an electric discharge is passed through H2 gas at

low pressure, the molecules dissociate, ionize, and
recombine, forming a plasma containing, in addition
to H2 spectroscopically observable
amounts of H, H+ , H2+ , and H3+

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HYDROGEN Properties and reactions

The H2 molecule has a high bond enthalpy (436 kJ mol−1 ) and a

short bond length (74 pm).

The high bond strength results in H2 being quite an inert molecule,

and reactions of H2 do not occur readily unless a special activation
pathway has been provided. In the gas phase it is much more
difficult to dissociate H2 heterolytically than homolytically,
because the former incurs a large additional energy cost to
separate the opposite charges.

Heterolytic cleavage is therefore assisted by reagents that form

strong bonds to H+ and H − : Both homolytic and heterolytic
dissociation are catalysed by molecules or active surfaces

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HYDROGEN Properties and reactions

In the gas phase, the explosive reaction of H2 with O2 ,

proceeds by a complex radical chain mechanism.

Hydrogen is an excellent fuel for large rockets on account of

its high specific enthalpy (the standard enthalpy of
combustion divided
by the mass), which is approximately three times that of a
typical hydrocarbon.

H2 can also react reversibly without cleavage to form

dihydrogen d-metal complexes

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HYDROGEN Simple compounds

The nature of the bonding in binary compounds of

hydrogen, i.e. with other elements E (EHn ), is largely
rationalized by noting that an H atom has a high
ionization energy (1310 kJ mol−1 ) and a low but positive
electron affinity (77 kJ mol−1 ).
Although binary hydrogen compounds are often known
as ‘hydrides’ (we will use this term throughout this
chapter), very few actually contain a discrete H− anion.

The (Pauling) electronegativity of hydrogen is

intermediate in value, so it is normally assigned the
oxidation number –1 when in combination with metals
(as in NaH and AlH3 ) and +1 when in combination with
nonmetals (as in H2O and HCl).

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HYDROGEN Classification of binary compounds

The binary compounds of hydrogen fall into

three classes, although there is a range of
structural types and some elements form
compounds with hydrogen that do not fall
strictly into any one category:

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HYDROGEN Classification of binary compounds

The binary compounds of hydrogen fall into three classes,:

Molecular hydrides exist as individual, discrete molecules;

they are usually formed with p-block elements of similar or
higher electronegativity than H. Their E–H bonds are best
regarded as covalent.

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HYDROGEN Classification of binary compounds

The binary compounds of hydrogen fall into three classes:

Saline hydrides , also known as ionic

hydrides , are formed with the most
electropositive
elements. Saline hydrides, such as LiH
and CaH2 , are nonvolatile,
electrically nonconducting,
crystalline solids, although only
those in Group 1 and the
heavier elements of Group 2
should be regarded as hydride
‘salts’ containing discrete H−
ions.
LiH
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HYDROGEN Classification of binary compounds

The binary compounds of hydrogen fall into three classes:

Metallic hydrides are nonstoichiometric,

electrically conducting solids with a
metallic lustre.

Metallic hydrides are formed with many d- and f-block elements. The H
atoms are often regarded as occupying interstitial sites within the metal
structure although this occupation rarely occurs without expansion or
phase change and frequently leads to loss of ductility and a tendency to
fracture—a process known as embrittlement

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HYDROGEN Classification of binary compounds

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HYDROGEN Thermodynamic considerations

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HYDROGEN Thermodynamic considerations

The standard Gibbs energies of formation of the hydrogen compounds

of s- and p-block elements reveal a regular variation in stability .
With the possible exception of BeH2 (for which good data are not
available), all the s-block hydrides are exergonic (ΔfG < < 0) and
therefore thermodynamically stable with respect to their elements at
room temperature. No hydride of Group 13 is exergonic at room
temperature.

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HYDROGEN Thermodynamic considerations

In all the other groups of the p block, the simple hydrogen compounds
of the first members of the groups (CH4 , NH3 , H2O, and HF) are
exergonic but the analogous compounds of their congeners become
progressively less stable down the group, a trend that is illustrated by
decreasing E–H bond energies . The heavier hydrides
become more stable on going from Group 14 across to the halogens.
For example, SnH4 is highly endergonic (Δ f G < > 0) whereas HI is
barely so.

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HYDROGEN Thermodynamic considerations

These thermodynamic trends can be traced to the variation in

atomic properties. The H–H bond is the strongest single
homonuclear bond known (apart from D–D or T–T bonds) and in
order for a compound to be exergonic and stable with respect
to its elements, it needs to have E–H bonds that are even
stronger than H–H. For molecular hydrides of the p-block
elements, bonding is strongest with the Period 2 elements and
becomes progressively weaker down each group.

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HYDROGEN Thermodynamic considerations

The weak bonds formed by the heavier p-block elements are

due to the poor overlap between the relatively compact H1s
orbital and the more diffuse s and p orbitals of their atoms.
Although d-block elements do not form binary molecular
compounds, many complexes contain one or more hydride
ligands. Metal–hydrogen bond strengths in the d block increase
down a group because the 3d orbitals are too contracted to
overlap well with the H1s orbital and better overlap is afforded
by 4d and 5d orbitals

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HYDROGEN Reactions of binary copounds

The reactions of binary compounds of hydrogen fall into three

classes depending on the polarity of the E–H bond

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HYDROGEN Reactions of binary compounds

The reactions of binary compounds of hydrogen fall into three

classes depending on the polarity of the E–H bond

In compounds where E and H have similar electronegativities, cleavage of

the E–H bond tends to be homolytic, producing, initially, an H atom and a
radical, each of which can go on to combine with other available radicals:

Common
examples of
homonuclear
cleavage include
the thermolysis
and combustion
of
hydrocarbons. © Ch 47 2017_18 RMF
HYDROGEN Reactions of binary copounds

The reactions of binary compounds of hydrogen fall into three

classes depending on the polarity of the E–H bond

In compounds where E is more electronegative than

H, heterolytic cleavage occurs, releasing a proton:

The compound behaves as a Bronsted acid and is

able to transfer H+ to a base. In such compounds
the H atom is termed protonic .

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HYDROGEN Reactions of binary copounds

The reactions of binary compounds of hydrogen fall into three

classes depending on the polarity of the E–H bond

Heterolytic bond cleavage also occurs in

compounds where E is less electronegative than H,
including saline hydrides:

In this case the H atom is hydridic and an H −

ion is transferred to a Lewis acid, such as a
boron-containing reagent

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HYDROGEN Thermodynamic considerations

The reducing agents NaBH4 and LiAlH4 used in organic synthesis are
examples of hydride-transfer reagents. By analogy with Bronsted
acidity, which measures the ability of a species to donate a proton, a
hydridicity scale can be compiled that compares the abilities of species to
donate a hydride.

The scale may be based on calculations performed for species in the gas
phase or experimental data for hydride transfer equilibria in a suitable
solvent. Through its ability to exist in both protonic (H + ) and hydridic (H− )
states, a bound hydrogen atom can act as a two-electron redox agent.

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HYDROGEN Nuclear Properties

The three hydrogen isotopes H, D, and T have large

differences in their atomic masses and different nuclear
spins, which give rise to easily observed changes in IR,
Raman, and NMR spectra of molecules containing these
isotopes.

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HYDROGEN Nuclear Properties

Neither 1 H nor 2H (deuterium, D) is

radioactive, but 3H (tritium, T) decays by the
loss of a β particle to yield a rare, but stable,
isotope of helium:

The half-life for this decay is 12.4 years.

Tritium’s abundance of 1 in 1021 hydrogen
atoms in surface water reflects a steady state
between its production by bombardment of
cosmic rays on the upper atmosphere and its
loss by radioactive decay. Tritium can be
synthesized by neutron bombardment of 6Li or
7
Li:

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HYDROGEN Nuclear Properties

Continuous production of tritium from lithium is a key step in the

projected future generation of energy from nuclear fusion rather
than nuclear fission. In a fusion reactor, tritium and deuterium are
heated to over 100 MK to give a plasma in which the nuclei react
to produce 4He and a neutron:

The neutron is used to bombard a lithium blanket that has been

enriched in 6Li to generate further tritium. This process carries
far fewer environmental risks than fission of 235U and is
essentially renewable: of the two primary fuels required,
deuterium is readily available from water and lithium is also
widely distributed

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HYDROGEN Production of dihydrogen

Hydrogen is important both as a raw material for the

chemical industry and, increasingly, as a fuel. Although it is
not present in significant quantities in the Earth’s
atmosphere or in underground gas deposits, there is a high
biological turnover, because various microorganisms use
H+ as an oxidant or H2 as a fuel.

Industrially, most H2 is produced from natural gas by using

steam reforming (in the US, about 95 per cent is produced
in this way).

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HYDROGEN Production of dihydrogen

Increasingly, H2 is being produced by

other methods, notably coal gasification (ideally this
would be
with carbon dioxide capture, and thermally assisted
electrolysis. In 2012, world production of H2 exceeded
65 Mt.
Most H2 is used close to its site of production, for the
synthesis
of ammonia (the Haber process), hydrogenation of
unsaturated
fats, hydrocracking of crude oil, and large-scale
manufacture
of organic chemicals.

In the future, H2 may be produced from

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entirely renewable sources such as water, capturing
HYDROGEN Production of dihydrogen – Small scale produtcion

In the laboratory, H2 is easily produced by

a) the reactions of electropositive elements with aqueous
acid or alkali,
b) or by hydrolysis of saline hydrides.
c) by electrolysis.

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HYDROGEN Production of dihydrogen – from fossil sources

Most H2 for industry is produced by

high-temperature reaction of H2O
with CH4 or a similar reaction with
coke.
The main commercial process for the production of
H2 is currently hydrocarbon (steam) reforming, the
catalysed reaction of H2O (as steam) with
hydrocarbons (typically methane) from natural gas)
at high temperatures:

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HYDROGEN Production of dihydrogen – from fossil sources

coal or coke is used in a coal

gasification
which occurs at 1000oC, is

The mixture of CO and H2 is known as water gas and further

reaction with water (the water gas shift reaction) produces
more H2 :

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HYDROGEN Production of dihydrogen – from fossil sources

Overall, the combination of coal

gasification (and hydrocarbon reforming)
with the water gas shift reaction results in
production of CO2 and H2 :

By implementing a system for capturing CO2 from

the mixture
it is possible to use fossil fuels and minimize
release of the greenhouse gas CO2 into the
atmosphere. However, this process is not a
renewable route for H2 production as it is based on
the use of fossil fuels.

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HYDROGEN Production of dihydrogen – from renewable sources

Production of H2 by electrolysis of water is costly and viable

only in areas where electricity is cheap, or if it is a by-
product of an economically important process.
Environmental pressures are driving technologies to
produce H2 more efficiently from surplus or renewable
energy, including solar and biological sources

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HYDROGEN Production of Hydrogen

An industrial
electrolysis cell
for H2 production
using Ni
anodes and Fe
cathodes
connected in
series.

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HYDROGEN Production of Hydrogen

Electrolysis is used to produce H2 that is free

from contaminants:

To drive this reaction, a large overpotential is required to offset the

sluggish electrode kinetics, particularly for the production of O2 . The
best catalysts are based on platinum, but this is too expensive to
justify its use in large-scale plants. As a consequence, electrolysis of
water is economical and environmentally benign only if the electrical
power stems from cheap, renewable resources or if it is surplus to
demand.

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HYDROGEN Production of Hydrogen

The most important electrolytic H2 production

method
is the chloralkali process, in which H2 is
produced
as a by-product of NaOH manufacture. In this
process the other gaseous product is Cl2 ,
which requires a lower overpotential than O2.

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HYDROGEN Production of Hydrogen

Hydrogen can be produced by fermentation,

using anaerobic bacteria that use cultivated
biomass or biological waste as their energy
source. Biological production could take
place in ‘hydrogen farms’ by nurturing
photosynthetic microorganisms that have been
modified to produce H2 as well as organic
molecules.

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HYDROGEN Reactions of dihydrogen

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 H2 with O2 and halogens

involve a radical chain mechanism.

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HYDROGEN Reactions of dihydrogen

Although H2 is quite an inert molecule, it reacts very rapidly

under special conditions. Conditions for activating H2 include:

Homolytic dissociation into H atoms, induced by adsorption at

certain metal surfaces:

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HYDROGEN Reactions of dihydrogen

Heterolytic dissociation into H+ and H−

ions induced by adsorption on a
heteroatom surface, such as a metal
oxide:

or reaction with a molecule that can provide both

Bronsted base and hydride acceptor.

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HYDROGEN Reactions of dihydrogen - homolytic dissociation

High temperatures are required to dissociate H2 into

atoms.

An important example of homolytic dissociation at normal

temperatures is the reaction of H2 at finely divided Pt or
Ni metal
This reaction, in which H2 is dissociatively
chemisorbed as H atoms, is used to catalyse
a) the hydrogenation of alkenes and
b) the reduction of aldehydes to alcohols.

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HYDROGEN Reactions of dihydrogen –homolytic dissociation

Another example of homolytic cleavage involves

the initial
coordination of molecular H2 as an η2-H2 species in
discrete
metal complexes.

Dihydrogen complexes provide examples of species

intermediate between molecular H2 and a dihydrido
complex.

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HYDROGEN Reactions of dihydrogen- heterolytic dissociation

Heterolytic dissociation of H2 depends upon a metal

ion (for
hydride coordination) and a Bronsted base being in
Reaction
closeof H 2 with a ZnO surface appears to produce a
proximity.
Zn(II)-bound hydride and an O-bound proton.

This reaction is involved in the production of methanol by catalytic

hydrogenation of carbon monoxide over Cu/ZnO/Al2O3 :

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HYDROGEN Reactions of dihydrogen – radical chain reactions

Radical chain mechanisms account for the thermally

or photochemically initiated reactions between H2
and the halogens in which atoms are generated that
act as radical chain carriers in
the propagation reaction. Chain termination occurs
when the
radicals recombine:

The highly exothermic reaction of H2 with O2 also

occurs by
a radical chain mechanism. Certain mixtures explode
violently © Ch 47 2017_18 RMF
HYDROGEN Compounds of hydrogen

Hydrogen forms compounds with most of the elements. These

compounds are classified into:
a) molecular hydrides,
b) Saline hydrides (salts of the hydride anion),
c) metallic hydrides (interstitial compounds of d-block elements),
d) discrete complexes of d-block elements in which hydride or
dihydrogen are ligands.

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HYDROGEN Compounds of hydrogen – molecular hydrides

 Molecular hydrides are formed with p-block

elements and Be.

 The bonding is covalent but variations in bond

polarity (depending on the electronegativity of the
atoms to which hydrogen is attached) result in a
range of reaction types in which hydrogen is
formally transferred as H+ , H− , or H.

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HYDROGEN Compounds of hydrogen – nomenclature

The systematic names of the molecular hydrogen

compounds
are formed from the name of the element and the
suffi x ‘-ane’,
as in phosphane for PH3 .

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HYDROGEN Compounds of hydrogen – molecular hydrides

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HYDROGEN Compounds of hydrogen – molecular hydrides

Molecular compounds of hydrogen are divided further

into three sub-categories:

 Electron-precise , in which all valence electrons of the

central atom are engaged in bonds. SiH4, CH4

 Electron-rich , in which there are more electron pairs

on the central atom than are needed for bond
formation (that is, there are lone pairs on the central
atom) NH3, H2O

 Electron-deficient , in which there are too few electrons

available to fill the bonding and nonbonding orbitals.
HYDROGEN Reactions of molecular hydrides

Homolytic dissociation of an E–H bond to

produce a radical, E°E, and hydrogen atom,
H, occurs most readily for the hydrides of
the heavy p-block elements.

Hydrogen attached to an electronegative

element
has protic character and the compound is
typically a Bronsted acid.

Hydrogen attached to an electropositive

element can be transferred to an acceptor
as a hydride ion.

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HYDROGEN Reactions of molecular hydrides

Homolytic dissociation occurs readily for the

hydrogen
compounds of some p-block elements, especially
the heavier elements. For example, the use of a
radical initiator greatly facilitates the reaction of
trialkylstannanes, R3SnH, with haloalkanes, RX,
as a result of the formation of R3Sn. radicals:

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HYDROGEN Reactions of molecular hydrides

Thermal decomposition reactions of molecular

hydrides yielding H2 and the element occur by
homolytic dissociation.

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HYDROGEN Compounds of hydrogen – molecular hydrides

compounds reacting by proton donation are said to show protic

behavior - in other words, they are Bronsted acids. acid
strength increases from left to right across a period in the p
block (in the order of increasing electron affinity) and down a
group (in the order of decreasing bond energy).

One striking example of this trend is the increase in acidity

from CH4 to HF
and then from HF to HI. Binary hydrogen compounds of
elements
on the right of the periodic table typically undergo these
reactions.

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HYDROGEN Compounds of hydrogen – molecular hydrides

Molecules in which hydrogen is bound to a more

electropositive element can act as hydride-ion donors.
Important examples are the complex hydrido anions such as
BH4 − and AlH4 − which are used to hydrogenate compounds
containing a multiple bond. Other examples include
numerous compounds of d-block elements, including many
catalysts.

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HYDROGEN Hydrogen bonding

Compounds and functionalities containing H atoms

attached to electronegative elements with at least one
lone pair often associate through hydrogen bonds

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HYDROGEN Hydrogen bonding

Evidence for hydrogen bonding is provided by the trends in

normal boiling points, which are unusually high for the
strongly hydrogen-bonded molecules: water, ammonia, and
hydrogen fluoride. The relatively low boiling points of PH3 ,
H2S, HCl, and the heavier p-block molecular hydrides
indicate that these molecules do not form strong hydrogen
bonds.

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HYDROGEN Hydrogen bonding

Although hydrogen bonds are usually much weaker

than conventional bonds their collective action is
responsible for stabilizing complex structures such
as the open network structure of ice

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HYDROGEN Hydrogen bonding

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HYDROGEN saline hydrides

 Hydrogen compounds of the most electropositive

metals may be regarded as ionic hydrides;

 They liberate H2 in contact with Bronsted acids and

transfer H− to electrophiles.

 As direct hydride donors they react with halide

compounds to form anionic hydride complexes.

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HYDROGEN saline hydrides

The saline hydrides are ionic solids containing

discrete H− ions
and are analogous to corresponding halide salts.

The ionic radius of H− varies from 126 pm in LiH to

154 pm in CsH.

This wide variability reflects the poor control that

the single
charge of the proton has on its two surrounding
electrons and
the resulting high compressibility and polarizability
of H−.

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HYDROGEN saline hydrides

Hydrides of Group 1 and 2 elements, with the

exception of Be, are ionic compounds. All Group 1
hydrides adopt the rock-salt structure.

With the exception of MgH2 which has the rutile

structure, the Group 2 hydrides adopt the fluorite
structure at high temperature and the related PbCl2
structure at low temperature.

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HYDROGEN saline hydrides - reactions

the reaction of saline hydrides reacts with water

vigorously.

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HYDROGEN saline hydrides

Alkali metal hydrides are convenient reagents for making

other hydride compounds because they are direct providers
of H− ions for the following synthetically useful reactions:

 Metathesis with a halide

 Addition to a Lewis acid

 Reaction with a proton source

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HYDROGEN saline hydrides

The absence of convenient solvents limits the use of

saline hydrides as reagents, but this problem is partially
overcome by the availability of commercial dispersions
of finely divided NaH in oil.

Even more finely divided and reactive alkali metal

hydrides can be prepared from the metal alkyl and
hydrogen

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HYDROGEN saline hydrides

Saline hydrides are pyrophoric; indeed, finely divided

sodium hydride can ignite simply if it is left exposed to humid
air.

Such fires are difficult to extinguish because even carbon

dioxide is reduced when it comes into contact with hot metal
hydrides (water, of course, forms even more flammable hydrogen);
they may, however, be blanketed with an inert solid, such
as sand.

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HYDROGEN The Element

In addition to the use of calcium dihydride in portable H2

generators, magnesium dihydride MgH2 is under
investigation
as a hydrogen storage medium for transport purposes,
where lightness is important .

The amount of H atoms in a given volume of MgH2 is

about 50 per cent higher than in the same volume of
liquid H2.

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HYDROGEN Metallic hydrides

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.

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HYDROGEN Metallic hydrides

Many of the d- and f-block elements react with H2 to

produce
metallic hydrides.

Most of these compounds (and the hydrides of alloys)

have a metallic lustre and are electrically conducting
(hence their name).

They are less dense than the parent metal and are brittle
—a property that poses challenges for the construction of
pipes carrying H2.

Most metallic hydrides have variable composition (they

are nonstoichiometric).
For example, at 550˚C zirconium hydride exists over a
composition range from ZrH 1.30 to ZrH 1.75; it has a
fluorite structure with ©
a Ch
variable
47 2017_18number
RMF of anion sites
HYDROGEN Metallic hydrides

The variable stoichiometry and metallic conductivity

of these hydrides can be understood in terms of a
model in which the band of delocalized orbitals
responsible for the conductivity accommodates the
electrons supplied by arriving H atoms. In this model,
the H atoms as well as the metal atoms take up
equilibrium positions in the electron sea.

© Ch 47 2017_18 RMF
HYDROGEN Metallic hydrides

The Group 10 metals, especially Ni and Pt, are often used as

hydrogenation catalysts in which surface hydride formation is
thought to be involved.

However, somewhat surprisingly, at moderate pressures only

Pd forms a stable bulk phase; its composition is PdHx, with
x<1. Nickel forms hydride phases at very high pressures but Pt
does not form any at all.

Apparently, the Pt–H bond enthalpy is sufficiently great to

disrupt the H–H bond but not strong enough to offset
the loss of Pt–Pt bonding, which would occur upon formation
of a bulk platinum hydride.
© Ch 47 2017_18 RMF
HYDROGEN hydrido and dihydrogen complexes of d metals

A large number of d-block metals

complexes are known in which the
dihydrogen molecule or hydride
anion are ligands.

These complexes play important

roles in catalysis and hydrogen
activation.

© Ch 47 2017_18 RMF
© Ch 47 2017_18 RMF
HYDROGEN Methods for synthesis of binary compounds of H

There are three common methods for synthesizing

binary hydrogen compounds:

 Direct combination of the elements (hydrogenolysis)

 Protonation of a Bronsted basic anion:

 Reaction of an ionic hydride or hydride donor (MH) with a

halide (metathesis):

© Ch 47 2017_18 RMF
END

© Ch 47 2017_18 RMF
HYDROGEN Assignment 1

Name and classify the following hydrogen

compounds: (a) BaH2, (b) SiH4, (c) NH3, (d)
AsH3, (e) PdH0.9, (f) HI.

© Ch 47 2017_18 RMF
HYDROGEN Assignment 2

Which hydrogen bond would you expect to

be stronger, S-H…O or O-H…S? Why?

© Ch 47 2017_18 RMF
HYDROGEN Assignment 3

Identify the reaction that is most likely to give the

highest proportion of HD and give your reasoning: (a)
H2 + D2 equilibrated over a platinum surface, (b) D2O +
NaH, (c) electrolysis of HDO.

© Ch 47 2017_18 RMF
HYDROGEN Assignment 4

Identify the compound in the following list that is most

likely to undergo radical reactions with alkyl halides,
and describe the reason for your choice: H2O, NH3,
(CH3)3SiH, (CH3)3SnH.

© Ch 47 2017_18 RMF
HYDROGEN Assignment 5

 Write balanced chemical equations for three major

industrial preparations of hydrogen gas. Propose two
different reactions that would be convenient for the
preparation of hydrogen in the laboratory.

© Ch 47 2017_18 RMF