C« I Ni Ι Ce I Zit
mmâ
3
Hydrogen
3.1 Introduction
Hydrogen is the most abundant element in the
universe and is also common on earth, being the
third most abundant element (after oxygen and
silicon) on the surface of the globe. Hydrogen in
combined form accounts for about 15.4% of the
atoms in the earth's crust and oceans and is the
ninth element in order of abundance by weight
(0.9%). In the crustal rocks alone it is tenth
in order of abundance (0.15 wt%). The gradual
recognition of hydrogen as an element during the
sixteenth and seventeenth centuries forms part
of the obscure and tangled web of experiments
that were carried out as chemistry emerged
from alchemy to become a modern s c i e n c e /
Until almost the end of the eighteenth century
the element was inextricably entwined with the
concept of phlogiston and H. Cavendish, who is
generally regarded as having finally isolated and
identified the gas in 1766, and who established
conclusively that water was a compound of
1 J. W . MELLOR, A Comprehensive Treatise on Inorganic
and Theoretical Chemistry, Vol. 1, Chap. 3, Longmans,
Green & Co., London, 1922.
oxygen and hydrogen, actually communicated his
findings to the Royal Society in January 1784
in the following words: "There seems to be the
utmost reason to think that dephlogisticated air
is only water deprived of its phlogiston" and that
"water consists of dephlogisticated air united with
phlogiston".
The continued importance of hydrogen in
the development of experimental and theoretical
chemistry is further illustrated by some of the
dates listed in the Panel on the page opposite.
Hydrogen was recognized as the essential
element in acids by H. Davy after his work
on the hydrohalic acids, and theories of acids
and bases have played an important role ever
1} since. The electrolytic dissociation theory of
S. A. Arrhenius and W. Ostwald in the 1880s,
the introduction of the pH scale for hydrogen-
ion concentrations by S. P. L. S0rensen in 1909,
the theory of acid-base titrations and indicators,
and J. N. Br0nsted's fruitful concept of acids
and conjugate bases as proton donors and
acceptors (1923) are other land marks (see
p. 48). The discovery of ortho- and para-
hydrogen in 1924, closely followed by the
discovery of heavy hydrogen (deuterium) and
32
§3.1 Introduction 33

tritium in the 1930s, added a further range of
phenomena that could be studied by means of
this element (pp. 3 4 - 4 3 ) . In more recent times,
the technique of nmr spectroscopy, which was
first demonstrated in 1946 using the hydrogen
nucleus, has revolutionized the study of structural
chemistry and permitted previously unsuspected
phenomena such as fluxionality to be studied.
Simultaneously, the discovery of complex metal
hydrides such as L 1 A I H 4 has had a major
impact on synthetic chemistry and enabled new
classes of compound to be readily prepared
in high yield (p. 229). The most important
compound of hydrogen is, of course, water,

Hydrogen — Some Significant Dates

1671 R. Boyle showed that dilute sulfuric acid acting on iron gave a flammable gas; several other seventeenth-century
scientists made similar observations.
1766 H. Cavendish established the true properties of hydrogen by reacting several acids with iron, zinc and tin; he
showed that it was much lighter than air.
1781 H. Cavendish showed quantitatively that water was formed when hydrogen was exploded with oxygen, and that
water was therefore not an element as had previously been supposed.
1783 A. L. Lavoisier proposed the name "hydrogen" (Greek ύδωρ νεινομαι, water former).
1800 W. Nicholson and A. Carlisle decomposed water electrolytically into hydrogen and oxygen which were then
recombined by explosion to resynthesize water.
1810-15 Hydrogen recognized as the essential element in acids by H. Davy (contrary to Lavoisier who originally
considered oxygen to be essential — hence Greek όξνς νείνομαι, acid former).
1866 The remarkable solubility o f hydrogen in palladium discovered by T. Graham following the observation of
hydrogen diffusion through red-hot platinum and iron by H. St. C. De ville and L. Troost, 1863.
1878 Hydrogen detected spectroscopically in the sun's chromosphere (J. N. Lockyer).
1895 Hydrogen first liquefied in sufficient quantity to show a meniscus (J. Dewar) following earlier observations of
mists and droplets by others, 1 8 7 7 - 8 5 .
1909 The pH scale for hydrogen-ion concentration introduced by S. P. L. $0rensen.
191? H 3 discovered mass-spectrometrically by J. J. Thompson.
+

192Ô The concept of hydrogen bonding introduced by W. M. Latimer and W. H. Rodebush (and by
ML L. Huggins, 1921).
1923 J. N . Br0nsted defined an acid as a species that tended to lose a proton: A ^ *B+ H . +

1924 Ortko- and para-hydrogen discovered spectroscopically by R. Mecke and interpreted quantum-mechanically by
W. Heisenberg, 1927.
1 9 2 9 - 3 0 Concept of quantum-mechanical tunnelling in proton-transfer reactions introduced (without experimental
evidence) by several authors.
1931 First hydrido complex of a transition metal prepared by W. Hieber and F. Leutert.
1932 Deuterium discovered spectroscopically and enriched by gaseous diffusion of hydrogen and by electrolysis of
water (H. C. Urey, F. G. Brickwedde and G. M. Murphy).
1932 Acidity function H proposed by L. P. Hammett for assessing the strength o f very strong acids.
Q

1934 Tritium first made by deuteron bombardment of D 3 P O 4 and ( N D ) S 0 4 (i.e. D + D s * T + *H);

2 4 2 2

M. L. E. Oliphant, P. Harteck and E. Rutherford.

1939 Tritium found to be radioactive by L. W. Alvarez and R. Cornog after a prediction by T. W, Bonner in 1938.
1946 Proton nmr first detected in bulk matter by E. M. Purceil, H. C. Torrey and R. V. Pound; and by F. Bloch,
W. W. Hansen and M. E. Packard.
1947 L 1 A I H 4 first prepared and subsequently shown to be a versatile reducing agent; A. E. Finholt, A . C. Bond and
H. I. Schlesinger,
1950 Tritium first detected in atmospheric hydrogen (V. Faltings and P. Harteck) and later shown to be present in
rain water (W. F. Libby etal 1951).
y

1954 Detonation of the first hydrogen bomb on Bikini Atoll.

1960s "Superacids" ( 1 0 - 1 0 times stronger than sulfuric acid) studied systematically by G. A. Olah's group and by
7 1 9

R. J. Gillespie's group.
1966 The term "magic acid" coined in G. A. Olah's laboratory for the non-aqueous system HSO3F/SDF5.
1 9 7 6 - 7 9 Encapsulated H atom detected and located in octahedral polynuclear carbonyls such as [HRu6(CO)i8]~ and
[ H C o 6 ( C O ) i 5 ] ~ following A. Simon's characterization of interstitial H in H N b e l n -
1984 Stable transition-metal complexes of dihapto-dihydrogen (r/ -H2) discovered by G. Kubas.
2
34 Hydrogen Ch. 3

and a detailed discussion of this compound i.e. ortho- and /rara-dihydrogen, -dideuterium
is given on pp. 6 2 0 - 3 3 in the chapter on and -ditritium.^
oxygen. In fact, hydrogen forms more chemical
compounds than any other element, including
carbon, and a survey of its chemistry therefore 3.2.1 Isotopes of hydrogen
encompasses virtually the whole periodic table.
However, before embarking on such a review in Hydrogen as it occurs in nature is predominantly
Sections 3.4-3.7 it is convenient to summarize composed of atoms in which the nucleus is a
the atomic and physical properties of the various single proton. In addition, terrestrial hydrogen
forms of hydrogen (Section 3.2), to enumerate contains about 0.0156% of deuterium atoms
the various methods used for its preparation and in which the nucleus also contains a neutron,
industrial production, and to indicate some of its and this is the reason for its variable atomic
many applications and uses (Section 3.3). weight (p. 17). Addition of a second neutron
induces instability and tritium is radioactive,
emitting low-energy β~ particles with a half-
3.2 Atomic and Physical life of 12.33 y. Some characteristic properties
(2) of these 3 atoms are given in Table 3.1, and
Properties of Hydrogen
their implications for stable isotope studies,
Despite its very simple electronic configuration radioactive tracer studies, and nmr spectroscopy
1
( I s ) hydrogen can, paradoxically, exist in over are obvious.
50 different forms most of which have been well In the molecular form, dihydrogen is a
characterized. This multiplicity of forms arises stable, colourless, odourless, tasteless gas with
firstly from the existence of atomic, molecular a very low mp and bp. Data are in Table 3.2
and ionized species in the gas phase: H, H2, from which it is clear that the values for
+ + +
H , H " , H , H . . . , H + ; secondly, from the deuterium and tritium are substantially higher.
2 3 n

existence of three isotopes, jH, jH(D) and iH(T),

and correspondingly of D, D2, HD, DT, etc.; ' The term dihydrogen (like dinitrogen, dioxygen, etc.) is
used when it is necessary to refer unambiguously to the
and, finally, from the existence of nuclear spin molecule H2 (or N2, O2, etc.) rather than to the element as a
isomers for the homonuclear diatomic species, substance or to an atom of the element. Strictly, one should
use "diprotium" when referring specifically to the species
H2 and "dihydrogen" when referring to an undifferentiated
2
Κ . M . MACKAY, The element hydrogen, Comprehensive isotopic mixture such as would be obtained from materials
Inorganic Chemistry, Vol. 1, Chap. 1. Κ . M . MACKAY and having the natural isotopic abundances of Η and D; likewise
+
M . F. A. DOVE, Deuterium and tritium, ibid., Vol. 1, Chap. 3, "proton" only when referring specifically to H , but "hydron"
Pergamon Press, Oxford, 1973. when referring to an undifferentiated isotopic mixture.

Table 3.1 A t o m i c properties o f h y d r o g e n (protium), deuterium, and tritium

Property Η D Τ

Relative atomic mass 1.007 8 2 5 2.014102 3.016049

N u c l e a r spin quantum n u m b e r 1 1 1
1
( a )
Nuclear magnetic moment/(nuclear m a g n e t o n s ) 2.79270 0.857 38 2.978 8
N M R frequency (at 2 . 3 5 t e s l a ) / M H z 100.56 15.360 104.68
N M R relative sensitivity (constant field) 1.000 0.00964 1.21
2 8 2
N u c l e a r quadrupole m o m e n t / ( 1 0 ~ m ) 0 2.766 χ ΙΟ" 3
0
R a d i o a c t i v e stability Stable Stable β- ίι 12.33 y ( b )

(a) 2 7 - 1
N u c l e a r magneton μ Ν = eh/2m p = 5.0508 χ 1 0 ~ JT .
b )
^ £ m a x 18.6 keV; E mean 5.7 keV; range in air ~ 6 m m ; range in water ~ 6 μ π ι .
§3.2.2 Ortho- and pata-hydrogen 35

Table 3.2 Physical properties o f hydrogen, deuterium and tritium

Property ( a )
H 2
D 2 T 2

M P / K 13.957 18.73 20.62

B P / K 20.39 23.67 25.04

Heat of fusion/kJmol - 1
0.117 0.197 0.250
Heat of vaporization/kJmol - 1
0.904 1.226 1.393
Critical temperature/K 33.19 38.35 40.6 (calc)

Critical pressure/atm ( b )
12.98 16.43 18.1 (calc)

Heat of dissociation/kJmor 1
(at 2 9 8 . 2 K ) 435.88 443.35 446.9

Z e r o point energy/kJ m o l - 1
25.9 18.5 15.1
Internuclear distance/pm 74.14 74.14 (74.14)

(a)
D a t a refer to H of normal isotopic composition (i.e. containing 0.0156 atom % of deuterium,
2

predominantly as HD). All data refer to the mixture of ortho- and para-forms that are in equilibrium
at room temperature.
( b , 2
l a t m = 101.325 k N m - = 101.325 kPa.

For example, the mp of T is above the bp of 2 3.2.2 Ortho- and para-hydrogen

H . Other forms such as HD and DT tend to
2

have properties intermediate between those of All homonuclear diatomic molecules having
their components. Thus HD has mp 16.60 K, nuclides with non-zero spin are expected to
bp 22.13K, A / 7 f u s 0.159 k l m o l " , A// 1
v a p
show nuclear spin isomers. The effect was first
1
1.075kJmol" , T 35.91 K, P 14.64 atm and
c c
detected in dihydrogen where it is particularly
- 1
A / 7 d i s s o c 439.3 kJ m o l . The critical temperature
noticeable, and it has also been established for
, 4 I 5 , 7

T is the temperature above which a gas cannot D , T , N , N ,

2 2 2 0 , etc. When the two
2 2
c

be liquefied simply by application of pressure, nuclear spins are parallel {ortho-hydrogen) the
and the critical pressure P is the pressure resultant nuclear spin quantum number is 1 (i.e.
c
\ + ^) and the state is threefold degenerate (2S +
required for liquefaction at this point.
1). When the two proton spins are antiparallel,
Table 3.2 also indicates that the heat of dis­
however, the resultant nuclear spin is zero and
sociation of the hydrogen molecule is extremely
the state is non-degenerate. Conversion between
high, the H - H bond energy being larger than for the two states involves a forbidden triplet-singlet
almost all other single bonds. This contributes transition and is normally slow unless catalysed
to the relative unreactivity of hydrogen at room by interaction with solids or paramagnetic species
temperature. Significant thermal decomposition which either break the H - H bond, weaken it,
into hydrogen atoms occurs only above 2000 K: or allow magnetic perturbations. Typical catalysts
the percentage of atomic H is 0.081 at this tem­ are Pd, Pt, active F e 0 3 and NO. Para-hydrogen
2

perature, and this rises to 7.85% at 3000 Κ and (spins antiparallel) has the lower energy and this
95.5% at 5000 K. Atomic hydrogen can, how­ state is favoured at low temperatures. Above 0 Κ
ever, be conveniently prepared in low-pressure (100% para) the equilibrium concentration of
glow discharges, and the study of its reactions ortho-hydrogen gradually increases until, above
forms an important branch of chemical gas kinet­ room temperature, the statistically weighted
ics. The high heat of recombination of hydrogen proportion of 3 orthoA para is obtained, i.e.
atoms finds application in the atomic hydrogen 25% para. Typical equilibrium concentrations
torch — dihydrogen is dissociated in an arc and of para-hydrogen are 99.8% at 20 K, 65.4%
the atoms then recombine on the surface of a at 60 K, 38.5% at 100K, 25.7% at 210 K,
metal, generating temperatures in the region of and 2 5 . 1 % at 273 Κ (Fig. 3.1). It follows that,
4000 Κ which can be used to weld very high whereas essentially pure para-hydrogen can be
melting metals such as tantalum and tungsten. obtained, it is never possible to obtain a sample
containing more than 7 5 % of ortho-hydrogen.
Experimentally, the presence of both o-H and 2 p-H .2 Similar differences are found for the
p-H
2 is seen as an alternation in the intensities
of successive rotational lines in the fine structure
of the electronic band spectrum of H2. It also
explains the curious temperature dependence of
the heat capacity of hydrogen gas.
Similar principles apply to ortho- and para-
deuterium except that, as the nuclear spin
quantum number of the deuteron is 1 rather
than ~ as for the proton, the system is
described by Bose-Einstein statistics rather than
the more familiar Fermi-Dirac statistics. For
this reason, the stable low-temperature form is
ortho -deuterium and at high temperatures the
statistical weights are 6 ortho'3 para leading
to an upper equilibrium concentration of 33.3%
para-deuterium above about 190 Κ as shown in
Fig. 3.1. Tritium (spin resembles H rather
2
than D2.
Most physical properties are but little affected
by nuclear-spin isomerism though the thermal
conductivity of p-H is more than 50% greater
2
than that of 0-H2, and this forms a ready means of
analysing mixtures. The mp of p-H (containing
2
only 0.21% o-H ) is 0.15 Κ below that of
2
"normal" hydrogen (containing 7 5 % o-H ), and
2
by extrapolation the mp of (unobtainable) nure
0-U2 is calculated to be 0.24 Κ above that of
bps which occur at the following temperatures:
normal-H 20.39 K, o-H 20.45 K. For deuterium
2 2
the converse relation holds, o-D melting some
2
0.03 Κ below " n o r m a r - D (66.7% ortho) and
2
boiling some 0.04 Κ below. The effects for other
elements are even smaller.
3.2.3 Ionized forms of hydrogen
+
This section briefly considers the proton H ,
the hydride ion H~, the hydrogen molecule ion
+ +
H 2 , the triatomic 2-electron species H 3 and the
+ ( 3 , 4 )
recently established cluster species H „ , .
The hydrogen atom has a high ionization
_l
energy ( 1 3 1 2 k J m o l ) and in this it resembles
the halogens rather than the alkali metals.
Removal of the Is electron leaves a bare proton
which, having a radius of only about 1.5 χ
3
1 0 ~ p m , is not a stable chemical entity in the
condensed phase. However, when bonded to
other species it is well known in solution and in
3
N. J. KIRCHNER and M . T . BOWERS, J. Chem. Phvs. 86,
1 3 0 1 - 1 0 (1987).
4
M . OKUMURA, L . I. YEH and Y . T . LEE, J. Chem. Ph\s.
88, 7 9 - 9 1 (1988), and references cited therein.
§3.2.3 Ionized forms of hydrogen 37
+
solids, e.g. H 0 , N H 4 , etc. The proton affinity
3
+
(3.0160). The "observed" equilateral triangular 3-
of water and the enthalpy of solution of H+ in centre, 2-electron structure is more stable than the
water have been estimated by several authors and hypothetical linear structure, and the comparative
typical values that are currently accepted are: stability of the species is shown by the following
+ +
gas-phase enthalpies:
H (g) + H 0(g) 2 >H 0 (g);
3

+ - 1
-AH -VlOkJmor 1
H + H + H+ = H 3 ; -AH 855.9 kJ m o l
+ +
H (g) • H 0 (aq);
3 H + H+ = H
2 3
+
; -AH 423.8klmol" 1

1
-AH - 1090 kJ m o l " H + H 2
+
= H 3
+
; -AH 600.2 kJ m o l - 1

It follows that the heat of solution of +

- 1
The H ion is the simplest possible example of a
3
the oxonium ion in water is ^ 3 8 0 k J m o l ,
three-centre two-electron bond (see discussion of
intermediate between the values calculated for
1 + 1
bonding in boranes on p. 157) and is also a model
Na+ (405 kJ m o l " ) and K (325 kJ m o l " ) . 2
for the dihapto bonding mode of the ligand rç -H 2
Reactions involving proton transfer will be
(pp. 4 4 - 7 ) :
considered in more detail in Section 3.5.
]
The hydrogen atom, like the alkali metals (ns ) + H
2 5
H
and halogens (ns np ), has an affinity for the
H
electron and heat is evolved in the following or
process: H
L
H
1
H(g) + e " • H " ( g ) ; -AH cak = 72kJmol" +
A series of ions H „ with η-odd up to 15
This is larger than the corresponding value for and Η-even up to 10 have recently been observed
_ 1
Li ( 5 7 k J m o l ) but substantially smaller than mass-spectrometrically and characterized for the
(3,4)
the value for F (333 kJ m o l ) . The hydride - 1
first t i m e . The odd-numbered species are
ion H~ has the same electron configuration as much more stable than the even-numbered
helium but is much less stable because the single members, as shown in the subjoined table which
positive charge on the proton must now control gives the relative intensities, / , as a function of η
the 2 electrons. The hydride ion is thus readily +
(in H „ ) obtained in a particular experiment with
deformable and this constitutes a characteristic a high-pressure ion source, relative to H + : . 3
( 3 )

feature of its structural chemistry (see p. 66).

+
The species H + and H 2 are important as
3 η 1 2 3 4 5 6
model systems for chemical bonding theory. The 10 / 4
160 50 10000 4.2 4200 210
hydrogen molecule ion H + comprises 2 protons2 η 7 8 9 10 11
and 1 electron and is extremely unstable even 10 / 4
3200 7.4 2600 18 34
in a low-pressure gas discharge system; the
energy of dissociation and the internuclear The structures of H 5 + , H 7 and Hq+ are +

distance (with the corresponding values for H 2 related to that of H with H molecules added 3
+
2

in parentheses) are: perpendicularly at the corners, whereas those of

+

A// 255(436) kJ m o l ; - 1 H +, H
4 and H + feature an added Η atom at the
6 8
d i s s o c

first corner. Typical structures are shown below.

r ( H - H ) 106(74.2) pm
The structures of higher members of the series,
The triatomic hydrogen molecule ion H was 3
+
with η > 10 are unknown but may involve further
first detected by J. J. Thomson in gas discharges loosely bonded H molecules above and below 2

+
and later fully characterized by mass spectrome­ the H plane. Enthalpies of dissociation are
3

+ 1
try; its relative atomic mass, 3.0235, clearly dis­ AH° (H
m H + + H ) 2 8 k J m o l " and
5 3 2

tinguishes it from HD (3.0219) and from tritium AH° (H

300
+
H + H ) 13kJmor .
7 5
+
2
1 ( 4 )
38 Hydrogen Ch. 3

on an industrial scale when integrated with the

chloralkali industry (p. 798). Other bulk pro­
cesses involve the (endothermic) reaction of
steam on hydrocarbons or coke:

1100°C
CH + H 0
4 2 > CO + 3 H 2

1000° c
C + H 0 2 > CO + H 2 (water gas)

In both processes the CO can be converted to

C 0 by passing the gases and steam over an iron
2

oxide or cobalt oxide catalyst at 400°C, thereby

generating more hydrogen:
3.3 Preparation, Production and
(56) 400° C
Uses CO + H 0 2 >C0 + H 2 2
catalyst

3.3.1 Hydrogen This is the so-called water-gas shift reac­

- 1
tion (—AG° 19.9 kJ m o l ) and it can also be
29S

Hydrogen can be prepared by the reaction effected by low-temperature homogeneous cata­

of water or dilute acids on electropositive lysts in aqueous acid solutions. The extent of (7)

metals such as the alkali metals, alkaline earth subsequent purification of the hydrogen depends
metals, the metals of Groups 3, 4 and the on the use to which it will be put.
lanthanoids. The reaction can be explosively
The industrial production of hydrogen is con­
violent. Convenient laboratory methods employ
sidered in more detail in the Panel. The largest
sodium amalgam or calcium with water, or
single use of hydrogen is in ammonia synthe­
zinc with hydrochloric acid. The reaction of
sis (p. 421) but other major applications are in
aluminium or ferrosilicon with aqueous sodium
the catalytic hydrogénation of unsaturated liquid
hydroxide has also been used. For small-scale
vegetable oils to solid, edible fats (margarine),
preparations the hydrolysis of metal hydrides is
and in the manufacture of bulk organic chemicals,
convenient, and this generates twice the amount
particularly methanol (by the "oxo" or hydro-
of hydrogen as contained in the hydride, e.g.:
formylation process):

CaH + 2 H 0
2 2 • Ca(OH) + 2 H 2 2 cobalt
CO + 2 H 2 > MeOH
catalyst
Electrolysis of acidified water using platinum
electrodes is a convenient source of hydrogen Direct reaction of hydrogen with chlorine is
(and oxygen) and, on a larger scale, very a major source of hydrogen chloride (p. 811),
pure hydrogen (>99.95%) can be obtained from and a smaller, though still substantial use is in
the electrolysis of warm aqueous solutions of the manufacture of metal hydrides and complex
barium hydroxide between nickel electrodes. The metal hydrides (p. 64). Hydrogen is used in
method is expensive but becomes economical metallurgy to reduce oxides to metals (e.g. Mo,
W) and to produce a reducing atmosphere. Direct
5
T . A . C z u p p o n , S . A . K n e z a n d D . S. N e w s o m e , H y d r o ­ reduction of iron ores in steelmaking is also now
g e n , i n Kirk-Othmer Encyclopedia of Chemical Technology, becoming technically and economically feasible.
4th edn., V o l . 13, W i l e y , N e w York, 1995, pp. 838-94.
6
P. H a u s s i n g e r R. L o h m u l l e r and A. M. W a t s o n , Hy­
d r o g e n , in Ullmann's Encyclopedia of Industrial Chemistry, 7
C.-H. Cheng and R. E i s e n b e r g , ./. Am. Chem. Soc. 100,
5rtTedn., V o l . A13, V C H , Weinheim. 1989, pp. 297-442. 5969-70 (1978).
§3.3.2 Deuterium 39

Industrial Production of Hydrogen

Many reactions are available for the preparation of hydrogen and the one chosen depends on the amount needed, the
purity required, and the availability of raw materials. Most (^-97%) of the hydrogen produced in industry is consumed in
integrated plants on site (e.g. ammonia synthesis, petrochemical works, etc.). Even so, vast amounts of the gas are produced
for the general market, e.g. ~ 6 . 5 χ 1 0 m or 5.4 million tonnes yearly in the U S A alone. Small generators may have a
î 0 3

capacity of 1 0 0 - 4 0 0 0 m h , medium-sized plants 4 0 0 0 - 1 0 0 0 0 m h " , and large plants can produce l f Z - l u m h .

3 - 1 3 1 5 3 _ 1

The dominant large-scale process in integrated plants is the catalytic steam - hydrocarbon reforming process using natural
gas or oil-refinery feedstock. After desulfurization (to protect catalysts) the feedstock is mixed with process steam and
passed over a nickel-based catalyst at 7 0 0 - 1000°C to convert it irreversibly to CO and H2, e.g.

900 C
4>

C Hg + 3 H 0
3 2 • 3CO + 7 H 2

catalyst

Two reversible reactions also occur to give an equilibrium mixture o f Ha, CO, COa and H2O:
CO -f H2O ^ = = ± CO2 «f H2

The mixture i s cooled to ~ 3 5 0 ° C before entering a high-temperature shift converter where the major portion of the C O is
catalytically and exothermically converted to CO2 and hydrogen by reaction with H2O. The issuing gas is further cooled
to 200° before entering the low-temperature shift converter which reduces the CO content to 0.2 vol%. The product is
further cooled and CO2 absorbed in a liquid contacter. Further removal of residual CO and CO2 can be effected by
methanation at 350°C to a maximum of lOppm. Provided that the feedstock contains no nitrogen the product purity is
about 98%. Alternatively the low-temperature shift process and methanation stage can be replaced by a single pressure-
swing absorption (PSA) system in which the hydrogen is purified by molecular sieves. The sieves are regenerated by
adiabatic depressurizatton at ambient temperature (hence the name) and the product has a purity of >99.9%.
At present about 77% o f the industrial hydrogen produced is from petrochemicals, 18% from coal, 4 % by electrolysis of
aqueous solutions and at most 1% from other sources. Thus, hydrogen is produced as a byproduct of the brine electrolysis
process for the manufacture of chlorine and sodium hydroxide (p. 798). The ratio o f H2:Oa:NaOH is, of course, fixed
by stoichiometry and this is an economic determinant since bulk transport of the byproduct hydrogen is expensive. To
illustrate the scale of the problem: the total world chlorine production capacity is about 38 million tonnes per year which
corresponds to 1 0 5 0 0 0 tonnes of hydrogen (1.3 χ 1 0 m ) . Plants designed specifically for the electrolytic manufacture
I 0 3

of hydrogen as the main product, use steel cells and aqueous potassium hydroxide as electrolyte. H i e cells may be operated
at atmospheric pressure (Knowles cells) or at 30 atm (Lonza cells).
When relatively small amounts of hydrogen are required, perhaps in remote locations such as weather stations, then
small transportable generators can be used which can produce l - 1 7 m h ~ . During production a 1:1 molar mixture of
3 l

methanol and water is vaporized and passed over a "base-metal chromite** type catalyst at 400°C where it is cracked into
hydrogen and carbon monoxide; subsequently steam reacts with the carbon monoxide to produce the dioxide and more
hydrogen:
400° c
MeOH >α> + 2 Η 2

catalyst
CO + H2O ^C0 + H
2 2

All the gases are then passed through a diffuser separator comprising a large number of small-diameter thin-walled tubes
of palladium-silver alloy tightly packed in a stainless steel case. The solubility of hydrogen in palladium is well known
(p. 1150) and the alloy with silver is used to prolong the life of the diffuser by avoiding troublesome changes in dimensions
during the passage of hydrogen. Trie hydrogen which emerges is cool, pure, dry and ready for use via a metering device.

Another medium-scale use is in oxyhydrogen and fuel cells if the notional "hydrogen economy"
torches and atomic hydrogen torches for welding (see Panel on p. 40) is ever developed.
and cutting. Liquid hydrogen is used in bubble
chambers for studying high-energy particles and
3.3.2 Deuterium
as a rocket fuel (with oxygen) in the space
programme. Hydrogen gas is potentially a large- Deuterium is invariably prepared from heavy
scale fuel for use in internal combustion engines water, D 0 , which is itself now manufactured
2
40 Hydrogen Ch. 3

The Hydrogen Economy ~ (6g H)

The growing recognition during the past decades that world reserves of coal and oil are finite and that nuclear power
cannot supply all our energy requirements, particularly for small mobile units such as cars, has prompted an active search
for alternatives. One solution which has many attractive features is the "hydrogen economy*' whereby energy is transported
and stored in the form of liquid or gaseous hydrogen. Enthusiasts point out that such a major change in the source of
energy, though apparently dramatic, is not unprecedented and has in fact occurred twice during the past 100 y. In 1880
wood was overtaken by coal as the main world supplier of energy and now it accounts for only about 2% of the total.
Likewise in 1960 coal was itself overtaken by oil and now accounts for only 15% of the total. (Note, however, that this
does not imply a decrease in the total amount of coal used: in 1930 this was 14.5 χ 1 0 barrels per day of oil equivalent 6

and was 75% of the then total energy supply whereas in 1975 coal had increased in absolute terms by 11% to 16.2 χ 1 0 6

b/d oe, but this was only 18% of the total energy supply which had itself increased 4,6-fold in the interim.) Another
change may well be in the offing since nuclear power, which was effectively non-existent as an industrial source of
energy in 1950, now accounts for 16% of the world supply of electricity; it has already overtaken coal as a source of
energy and may well overtake oil during the next century. ITie aim o f the "hydrogen economy" is to transmit this energy,
not as electric power but in the form of hydrogen; this overcomes the great problem of electricity — that it cannot be
stored — and also reduces the costs of power transmission.
The technology already exists for producing hydrogen electrically and storing it in bulk. For example huge quantities
of liquid hydrogen are routinely stored in vacuum insulated cryogenic tanks for the U S space programme, one such
tank alone holding over 3400 m ( 9 0 0 0 0 0 US gallons). Liquid hydrogen can be transported by road or by rail tankers
3

of 75.7 m capacity ( 2 0 0 0 0 US gallons). Underground storage of the type currently used for hydrogen — natural gas
3

mixtures and transmission through large pipes is also feasible, and pipelines carrying hydrogen up to 80 km in the USA
and South Africa and 2 0 0 k m in Europe have been in operation for many years. Smaller storage units based on metal
alloy systems have also been suggested, e.g. LaNis can absorb up to 7 moles of Η atoms per mole of LaNi5 at room
temperature and 2.5 atm, the density o f contained hydrogen being twice that in the liquid element itself, Other systems
include M g - M g H , M g N i ~ M g N i H 4 , T t - T i H and TiFe-TiFeHi^s*
2 2 2 2

The advantages claimed for hydrogen as an automobile fuel are the greater energy release per unit weight of fuel
and the absence of polluting emissions such as CO, C 0 , NO*, S 0 , hydrocarbons, aldehydes and lead compounds.
2 2

The product of combustion is water with only traces of nitrogen oxides. Several conventional internal-combustion petrol
engines have already been simply and effectively modified to run on hydrogen. Fuel cells for the regeneration of electric
power have also been successfully operated commercially with a conversion efficiency of 70%, and test cells at higher
pressures have achieved 85% efficiency.
Non-electrolytic sources of hydrogen have also been studied. The chemical problem is how to transfer the correct amount
of free energy to a water molecule in order to decompose it. In the last few years about 1 0 0 0 0 such thermochemical
water-splitting cycles have been identified, most of them with the help of computers, though it is significant that the most
promising ones were discovered first by the intuition of chemists.
The stage is thus set, and further work to establish safe and economically viable sources of hydrogen for general energy
usage seems destined to flourish as an active area of research for some while.

on the multitonne scale by the electrolytic The equilibrium constant for the exchange
enrichment of normal w a t e r / The enrich­ 12, l 3 ) reaction
ment is expressed as a separation factor between
the gaseous and liquid phases: H 0 + HD
2 HDO + H 2

s = (H/D) /(H/D)! g
is about 3 at room temperature and this would
lead to a value of s = 3 if this were the only
effect. However, the choice of the metal used for
8D. P. GREGORY, The hydrogen economy, Chap. 23 in
Chemistry in the Environment, Readings from Scientific the electrodes can also affect the various elec­
American, 1973, pp. 2 1 9 - 2 7 . trode processes, and this increases the separation
9 L. B. M C G O W N and J. O ' M . BOCKRIS, How to Obtain still further. Using alkaline solutions s values in
Abundant Clean Energy, Plenum, New York, 1980, 275 pp.
L. O. WILLIAMS, Hydrogen Power, Pergamon Press, Oxford,
1980, 158 pp. 1 2 G . VASARU, D . U R S U , A. MIHÂILÂ and P . SZENT-GYORGYI,
1 0C. J. WINTER and J. NITSCH (eds.), Hydrogen as an Energy Deuterium and Heavy Water, Elsevier, Amsterdam, 1975,
Carrier, Springer Verlag, Berlin, 1988, 377 pp. 404 pp.
1 1B . BOGDANOVIC, Angew. Chem. Int. Edn. Engl. 24, H . K. RAE (ed.), Separation of Hydrogen
1 3 Isotopes, ACS
2 6 2 - 7 3 (1985). Symposium Series No. 68, 1978, 184 pp.
§3.3.3
the range 5 - 7 . 6 are obtained for many metals, ris­
ing to 13.9 for platinum cathodes and even higher
for gold. By operating a large number of cells in
cascade, and burning the evolved H2/D2 mixture
to replenish the electrolyte of earlier cells in the
sequence, any desired degree of enrichment can
ultimately be attained. Thus, starting with normal
water (0.0156% of hydrogen as deuterium) and
a separation factor of 5, the deuterium content
rises to 10% after the original volume has been
reduced by a factor of 2400. Reduction by 66 000
is required for 90% deuterium and by 130000 for
99% deuterium. If, however, the separation factor
is 10, then 9 9 % deuterium can be obtained by a
volume reduction on electrolysis of 22 000. Prior
enrichment of the electrolyte to 15% deuterium
can be achieved by a chemical exchange between
H2S and H2O after which a fortyfold volume
reduction produces heavy water with 9 9 % deu­
terium content. Other enrichment processes are
now rarely used but include fractional distillation
1 8
of water (which also enriches 0 ) , thermal diffu­
sion of gaseous hydrogen, and diffusion of H2/D2
through palladium metal.
Many methods have been used to determine
the deuterium content of hydrogen gas or
water. For H2/D2 mixtures mass spectroscopy
and thermal conductivity can be used together
with gas chromatography (alumina activated with
manganese chloride at 77 K). For heavy water
the deuterium content can be determined by
density measurements, refractive index change,
or infrared spectroscopy.
The main uses of deuterium are in tracer
studies to follow reaction paths and in kinetic
studies to determine isotope effects. A (14)
good discussion with appropriate references is
in Comprehensive Inorganic Chemistry, Vol. 1,
pp. 9 9 - 1 1 6 . The use of deuterated solvents
is widespread in proton nmr studies to avoid
interference from solvent hydrogen atoms, and
deuteriated compounds are also valuable in
structural studies involving neutron diffraction
techniques.
1 4
L . MELANDER and W. H . SAUNDERS, Reaction Rates
Isotopic Molecules, Wiley, N e w York, 1980, 331 pp.
Tritium 41
3.3.3 Tritium w
Tritium differs from the other two isotopes
of hydrogen in being radioactive and this
immediately indicates its potential uses and its
method of detection. Tritium occurs naturally to
1 8
the extent of about 1 atom per 1 0 hydrogen
atoms as a result of nuclear reactions induced by
cosmic rays in the upper atmosphere:
1 4 l 3 , 2
N + n = H + c
^ N + } H = ?H + fragments
2 2
H + H = ÎH+{H
The concentration of tritium increased by over a
hundredfold when thermonuclear weapon testing
began on Bikini Atoll in March 1954 but has now
subsided as a result of the ban on atmospheric
weapon testing and the natural radioactivity of
the isotope ( n 12.33 y).
Numerous reactions are available for the artifi­
cial production of tritium and it is now made on
a large scale by neutron irradiation of enriched
6
L i in a nuclear reactor:
*Li + ^η = He + ]H 4
2
The lithium is in the form of an alloy with mag­
nesium or aluminium which retains much of the
tritium until it is released by treatment with acid.
Alternatively the tritium can be produced by neu­
tron irradiation of enriched LiF at 450° in a vac­
uum and then recovered from the gaseous prod­
ucts by diffusion through a palladium barrier. As
a result of the massive production of tritium for
thermonuclear devices and research into energy
production by fusion reactions, tritium is avail­
able cheaply on the megacurie scale for peaceful
purposes.^ The most convenient way of storing
the gas is to react it with finely divided uranium
15
E . A. EVANS, Tritium and its Compounds, 2nd edn., But-
terworths, London, 1974, 840 pp. E . A. EVANS, D. C. WAR-
RELL, J. A. ELVÏDGE and J. R . JONES, Handbook of Tritium
NMR Spectroscopy and Applications, Wiley, Chichester,
1985, 249 pp.
of f See also p. 18 for the influence on the atomic weight of
commercially available lithium in some countries.
42 Hydrogen
to give U T 3 from which it can be released by
heating above 400°C.
Besides being one of the least expensive radio­
isotopes, tritium has certain unique advantages
1 4
as a tracer. Like C it is a pure low-energy β~
emitter with no associated y-rays. The radiation
is stopped by ~ 6 m m of air or —όμιτι of mate­
- 3
rial of density 1 g e m (e.g. water). As the range
is inversely proportional to the density, this is
reduced to only ~ 1 μ m in photographic emul­
- 3
sion (p ~ 3 . 5 g c m ) thus making tritium ideal
for high-resolution autoradiography. Moreover,
tritium has a high specific activity. The weight
of tritium equal to an activity of 1 Ci is 0.103 mg
and 1 mmol T2 has an activity of 58.25 Ci. [Note:
, 0
1 Ci (curie) = 3.7 χ 1 0 B q (becquerel); 1 Bq =
- 1
1 s . ] Tritium is one of the least toxic of radio­
isotopes and shielding is unnecessary; however,
precautions must be taken against ingestion, and
no work should be carried out without appropriate
statutory authorization and adequate radiochemi­
cal facilities.
Tritium has been used extensively in hydrolog-
ical studies to follow the movement of ground
waters and to determine the age of various bod­
ies of water. It has also been used to study
the adsorption of hydrogen and the hydrogéna­
tion of ethylene on a nickel catalyst and to
study the absorption of hydrogen in metals. Auto­
radiography has been used extensively to study
the distribution of tritium in multiphase alloys,
though care must be taken to correct for the pho­
tographic darkening caused by emanated tritium
gas. Increasing use is also being made of tritium
as a tracer for hydrogen in the study of reaction
mechanisms and kinetics and in work on homo­
geneous catalysis.
The production of tritium-labelled organic com­
pounds was enormously facilitated by Κ. E. Wilz-
bach's discovery in 1956 that tritium could be
introduced merely by storing a compound under
tritium gas for a few days or weeks: the β~
radiation induces exchange reactions between the
hydrogen atoms in the compound and the tritium
gas. The excess of gas is recovered for further
use and the tritiated compound is purified chro-
matographically. Another widely used method of
Ch. 3
general applicability is catalytic exchange in solu­
tion using either a tritiated solution or tritium gas.
This is valuable for the routine production of tri­
tium compounds in high radiochemical yield and
- 1
at high specific activity ( > 5 0 mCi m m o l ) . For
example, although ammonium ions exchange rel­
atively slowly with D2O, tritium exchange equi­
libria are established virtually instantaneously: tri­
tiated ammonium salts can therefore be readily
prepared by dissolving the salt in tritiated water
and then removing the water by evaporation:
(NH ) S0 + HTO (NH T) S0 + H 0 , etc.
4 2 4 3 2 4 2
For exchange of non-labile organic hydrogen
atoms, acid-base catalysis (or some other cat­
alytic hydrogen-transfer agent such as palladium
or platinum) is required. The method routinely
gives tritiated products having a specific activity
almost 1000 times that obtained by the Wilzbach
method; shorter times are required ( 2 - 1 2 h ) and
subsequent purification is easier.
When specifically labelled compounds are
required, direct chemical synthesis may be
necessary. The standard techniques of preparative
chemistry are used, suitably modified for small-
scale work with radioactive materials. The
starting material is tritium gas which can be
obtained at greater than 9 8 % isotopic abundance.
Tritiated water can be made either by catalytic
oxidation over palladium or by reduction of a
metal oxide:
Pd
2T + 0
2 2 • 2T 0 2
T + CuO
2 > T 0 + Cu
2
Note, however, that pure tritiated water is
virtually never used since 1 ml would contain
2650 Ci; it is self-luminescent, irradiates itself
at the rate of 6 χ 1 0 e V m l s 17
(MO - 1 - 1 9
- 1
rad d a y ) , undergoes rapid self-radiolysis,
and also causes considerable radiation damage
to dissolved species. In chemical syntheses
or exchange reactions tritiated water of 1%
- 1
tritium abundance (580 mCi m m o l ) is usually
sufficient to produce compounds having a specific
- 1
activity of at least lOOmCi m m o l . Other useful
§3.4 Chemical properties and trends 43

synthetic reagents are NaT, L1AIH3T, N a B H T ,
NaBT4, B 2 T 6 and tritiated Grignard reagents.
Typical preparations are as follows:
LiH + T
L1BH4 + T
4LiT + AlBr
B H + T
2 6
3NaBT + 4 B F . O E t
4 3
3 T 0 ( g ) + P(CN)
2 3
3 This reaction can be used as a sensitive
test for the presence of hydrogen. At higher
temperatures hydrogen reacts vigorously, even
explosively, with many metals and non-metals to
350°C give the corresponding hydrides. Activation can
• LiT + HT
2
also be induced photolytically, by heterogeneous
200°C catalysts (Raney nickel, Pd, Pt, etc.), or by
• L1BH3T + HT
2
means of homogeneous hydrogénation catalysts.
ether Industrially important processes include the
3 • L1AIT4 + 3LiBr hydrogénation of many organic compounds and
the use of cobalt compounds as catalysts in
2 B2H5T + H T the hydroformylation of olefins to aldehydes
and alcohols at high temperatures and pressures
2 • 2 B T + 3NaBF
2 6 4
(p. 1140):
• 3TCN + T P 0 3 3
R C H = C H + H + CO — + RCH2CH2CHO
2 2

700°C RCH CH CHO + H

2 2 2 • RCH CH CH OH
2 2 2
2AgCl + T 2 • 2TC1 + 2Ag
uv An even more effective homogeneous hydrogéna­
tion catalyst is the complex [RhCl(PPh ) ] which 3 3

Br + T
2 2 • 2TBr permits rapid reduction of alkenes, alkynes and
P(red) + 1 + HTO > TI + HI + . · . other unsaturated compounds in benzene solution
2
at 25°C and 1 atm pressure (p. 1134). The Haber
NH + T 3 2 • N H T + TH
2
process, which uses iron metal catalysts for the
direct synthesis of ammonia from nitrogen and
Mg N + 6T 0 3 2 2 2 N T + 3Mg(OT)
3 2
hydrogen at high temperatures and pressures, is
χ heat a further example (p. 421).
M + -T 2 • MT,
The hydrogen atom has a unique electronic
1
configuration I s : accordingly it can gain an
The preparation and use of L i E t B T and L1AIT4 3 electron to give H~ with the helium configuration
- 1
at maximum specific activity (57.5 Ci m m o l ) 2
I s or it can lose an electron to give the
(16)
has also been described. +
proton H (p. 36). There are thus superficial
resemblances both to the halogens which can
gain an electron to give an inert-gas configuration
3.4 Chemical Properties and 2 6
ns np , and to the alkali metals which can
Trends +
lose an electron to give M (ns np ). 2 6
However,
because hydrogen has no other electrons in its
Hydrogen is a colourless, tasteless, odourless gas structure there are sufficient differences from
which has only low solubility in liquid solvents. each of these two groups to justify placing
It is comparatively unreactive at room temper­ hydrogen outside either. For example, the proton
ature though it combines with fluorine even in 3
is so small (r M . 5 χ 1 0 ~ p m compared with
the dark and readily reduces aqueous solutions normal atomic and ionic sizes of ~ 5 0 - 2 2 0 p m )
of palladium(II) chloride: that it cannot exist in condensed systems unless
associated with other atoms or molecules. The
PdCl (aq) + H
2 2 > Pd(s) + 2HCl(aq) transfer of protons between chemical species
constitutes the basis of acid-base phenomena
1 6
H. A N D R E S , H. MORIMOTO and P. G. WILLIAMS, J. Chem. (see Section 3.5). The hydrogen atom is also
Soc, Chem. Commun., 6 2 7 - 8 ( 1 9 9 0 ) . frequently found in close association with 2
44 Hydrogen Ch. 3

other atoms in linear array; this particularly Table 3.3 Stereochemistry o f h y d r o g e n

important type of interaction is called hydrogen CN Examples
bonding (see Section 3.6). Again, the ability
1 HC1, H S , P H , N H , B H ~ , etc.; [ H M n ( C O ) ] ,
2 3 4 + 4 5
to penetrate metals to form nonstoichiometric
[H Fe(CO) ], [H Ta(C H ) ], [H Cr(dmpe) ],
2 4 3 5 5 2 4 2

metallic hydrides, though not unique to hydrogen, [CoH ] ", [H W(PR ) ], [{H Re(PR ) } Ag]+,
5 4 6 3 3 7 3 2 2

is one of its more characteristic properties [H Re(PR )]", [ReH ] "

8 3 9 2

as is its ability to form nonlinear hydrogen 2 B H , [Me NAlH ] , [H BHCu(PMePh ) ],

2 6 2 2 3 3 2 3

bridge bonds in many of its compounds. These [m^-Ir(B H )(CO)(PPh ) ], 5 8 3 2

properties will be further discussed during the [(CO) WHW(CO) ]-, 5 5

general classification of the hydrides of the [(C Me5)Ir(M -H) Ir(C Me5)
5 2 3 5

elements in section 3.7. The most important 3 [ c W B H ( / x - H ) ] - , [(M -H)Rh (C H ) ],

6 6 3 3 3 5 5 4

compound of hydrogen is, of course, water and a [(/z -H) Co (C H ) ]

3 4 4 5 5 4

detailed discussion of this compound is given on 4 [( M 4 -H)Ru (CO) H] - 8 2 1 2

pp. 6 2 0 - 3 3 in the chapter on oxygen. 5 £ - M g N i H ( d ) (1 "covalent" N i - D 1 4 9 p m plus

2 4 4

4 "ionic" M g - D 230 p m )
6 [HNb I ], [HRu (CO) ]", [HCo (CO) r,
6 n 6 1 8 6 1 5

[ ( - H ) N i ( C O ) ] - , [(M6-H)Ni (CO) ] -
3.4.1 The coordination chemistry of M 6 2 1 2 2 1 2 1 2 2 1 3

hydrogen

Perhaps the most exciting recent development in

the chemistry of hydrogen is the discovery that,
in transition metal polyhydrides, the molecule H2
can act as a dihapto ligand, y/ -H2 (see below).2

Even the H atom itself can form compounds in

which its coordination number (CN) is not just 1
(as expected) but also 2, 3, 4, 5 or even 6. A rich
and unexpectedly varied coordination chemistry
is thus emerging. We shall deal with the H atom
first and then with the H2 molecule.
By far the most common CN of hydrogen is 1,
as in HC1, H S , PH3, CH4 and most other covalent
2

hydrides and organic compounds. Bridging modes

in which the H atom has a higher CN are shown
schematically in the next column — in these struc­
tures M is typically a transition metal but, partic­
The crucial experiment suggesting that the
ularly in the β2-ιηοά& and to some extent in the
H2 molecule might act as a dihapto ligand
^3-mode, one or more of the M can represent a
to transition metals was the dramatic obser­
main-group element such as B, Al; C, Si; Ν etc.
v a t i o n ™ that toluene solutions of the deep
Typical examples are in Table 3 . 3 . Fuller ( 1 7 - 1 9 )
purple coordinatively unsaturated 16-electron
discussion and references, when appropriate, will
complexes [ M o ( C O ) ( P C y ) ] and [W(CO) - 3 3 2 3

be found in later chapters dealing with the indi­

(PCy )2] (where Cy = cyclohexyl) react read­
3

vidual elements concerned.

ily and cleanly with H2 (1 atm) at low
temperatures to precipitate yellow crystals of
17 D. S. MOORE and S. D. ROBINSON, Chem. Soc. Revs. 1 2 , [ M ( C O ) H ( P C y ) ] in 8 5 - 9 5 % yield. The
3 2 3 2

415-52 (1983).
1 8 A . DEDIEU (ed.). Transition Metal Hydrides, V C H , Berlin,
1991, 4 1 6 pp. 2 0 G . J. KUBAS, J. Chem. Soc, Chem. Commun., 6 1 - 2
(1980).
1 9 T. P . FEHLNER, Polyhedron, 9, 1 9 5 5 - 6 3 (1990).
§3.4.1 The coordination chemistry of hydrogen 45

H2 could be quantitatively removed at room substitution reaction. Examples are:

temperature either by partial evacuation or by
[W(CO) (PP4) ] + 3 2 H 2 — •
sparging the solution with argon. Definitive con­
firmation that the complexes did indeed contain [W(CO)3(^ -H )(PP4)2] 2 2

?7 -H2 came from X-ray and neutron diffraction

2

studies on the bis(tri /-propylphosphine) analogue [FeClH(R PCH CH PR2)2] + H + NaBPh*

2 2 2 2

at —100°, which revealed the side-on coordina­ • [FeH(rç -H )(R2PCH2CH PR2)2] 2 2 2 +

tion of H2 as shown in Fig. 3 . 2 . During the (21)

past decade many other such compounds have + BPÎ14- -h NaCl

been prepared and studied in great detail, and the i r a ^ - [ I r H ( H 0 ) ( P P h ) 2 ( B q ) ] -f H
2 3 + 2 •
field has been well r e v i e w e d . ( 2 2 _ 2 4 )

rm,25-[IrH(r? -H )(PPh ) (Bq)] 2 2 3 2 +

hv
[Cr(CO) ] -f H — • [Cr(CO) (rç -H )] + CO
6 2 5 2 2

hq. X e

hv
Co(CO) (NO) + H 3 2 — •
hq. X e
[Co(CO) (rç -H )(NO)] + CO 2 2 2

The second general method involves the protona­

tion of a polyhydrido complex using a strong acid
such as H B F . E t 2 0 . Typical examples involving
4

Figure 3.2 T h e geometry o f mer-trans-[W(CO)^- d , d , d or d metal centres are:

2 4 6 8

(rç -H )(PPr3) ] f r o m X - r a y a n d n e u ­
2 2 2

tron diffraction data: r ( H - H ) 8 4 p m (d ) 2 [MoH (dppe) ] + 2 H 4 2 +

[MoH (*? -H2)(dppe) ] 2+

( c o m p a r e d w i t h 7 4 . 1 4 p m for free H ) , 2
4 2 2
r ( W - H ) 175 p m . Infrared vibration s p e c ­
troscopy gives υ ( Η - Η ) 2 6 9 0 c m " c o m ­ 1
H+
pared w i t h 4 1 5 9 c m (Raman) for free d ) 4 [IrH (PCy ) ] 5 3 2

H . 2 NEt 3

[IrH (^ -H2)2(PCy )2]

2 2 3 +

There are two general routes to η -H2

complexes. The first involves direct addition (d ) 6 [RuH (dppe) ] + H 2 2 + •
of molecular H2 either to an unoccupied [RuH(^ -H2)(dppe) ] 2 2 +

coordination site in a 16-electron complex (as

above) or by displacement of a ligand such as (d ) 8 [RhH{P(CH CH PPh ) }] + H 2 2 2 3 + •
CO, Cl, H2O in the coordination sphere of an [Rh(r -H ){P(CH CH PPh2) }] ?2 2 2 2 3 +

18-electron complex; in this latter case ultraviolet

irradiation may be required to assist in the There is even a rare example involving a d°
polyhydride: (25)

2 1 G . J. K U B A S , R . R . RYAN, Β . I. SWANSON, P . I. VERGA- H (-80°)+

MINI and H . J. WASSERMAN, J. Am. Chem. Soc. 1 0 6 , 4 5 2 - 4

(1984).
(d°) [ReH (PCy ) ] 7 3 2

NEt 3

2 2 G . J. K U B A S , Acc. Chem. Res. 2 1 , 1 2 0 - 8 ( 1 9 8 8 ) .

2 3 R . H . CRABTREE and D . G . HAMILTON, Adv. Organomet. [ReH - ( / -H ),(PCy )2] 8 2 x y 2 2 3 +

Chem. 28, 299-338 ( 1 9 8 8 ) ; R . H . CRABTREE, Acc. Chem.

Res. 2 3 , 9 5 - 1 0 1 (1990).
2 4 A . G . GINZBURG and A. A. BAGATURANTS, Organomet. 2 5 X. L. R. FONTAINE, Ε. H. FOWLES and B. L. SHAW, J.
Chem. in USSR 2 , 1 1 1 - 2 6 ( 1 9 8 9 ) . Chem. Soc, Chem. Commun., 4 8 2 - 3 ( 1 9 8 8 ) .
46 Hydrogen Ch. 3

If deuterio acids are used then T? -HD complexes 2

are formed; these are particularly useful in estab­

lishing the retention of substantive H - H bonding
in the coordinated ligand by observation of a
1:1:1 triplet in the proton nmr spectrum (the pro­
ton signal being split by coupling to deuterium
with nuclear spin 7 = 1).
The stability of η -ΙΪ2 complexes varies con­ 2

siderably, from those which can be observed only

in low-temperature matrix-isolation experiments
to those which are moderately robust even at
room temperature and above. Stability depends (a) (b)

on the electron configuration of the metal centre, Figure 3.3 Schematic representation o f the t w o
the electronic and steric nature of the co-ligands, c o m p o n e n t s o f the i 7 - H - m e t a l bond:
2 2

the overall charge on the complex, the state of (a) donation from the filled (hatched)
aggregation and, of course, the temperature. Most σ - Η b o n d i n g orbital into a vacant hybrid
2

orbital o n M ; (b) π - b a c k d o n a t i o n from a

?? -H2 complexes involve transition metals in
2
filled d orbital (or hybrid) o n M into the
Groups 6 - 8 , in oxidation states having a formal vacant σ* antibonding orbital o f H . 2

d electron configuration. No rç -H2 complexes

6 2

are yet known for transition metals in Groups 3 or

4 of the periodic table, although examples involv­
ing Group 5 metals have recently been reported,
e.g. the d species 4 [Υ(η -0 Η )(0Ο) (η -Η )]
and [ N b ( ^ - C 5 H ) ( C O ) 3 ( r ? - H 2 ) ] .
5 Within a
given Group, the first and second members
more readily form η Ή2 complexes while the 2 donation from an occupied d orbital on the
third member tends to form polyhydrido species,
e.g. [Fe(H) (rç -H2)(PEtPh )3] and [Ru(H) (rç -
2 2
H ) ( P P h ) ] but [Os(H) (P(o-tol) ) ].
2 3 3 Stability
4 3
is also enhanced by an overall cationic charge on
the complex (remember protonation as a route
to rç -H2 complexes). In such cases, however,
2 being donated from the H2 ligand is in the
stability of the resulting compound depends on
the presence of a non-coordinating anion such as
B F ~ , otherwise there is a risk of decomposi­
4 bond; and (b) the H2 antibonding orbital involved
tion by displacement of the more weakly coordi­
nating (rç -H ). Neutral complexes are also well
2 2
known, but no examples of anionic rç -H2 com­
plexes have been reported.
M. T . HAWARD, M. W . GEORGE,
2 6
M. POLIAKOFF, J. Chem. Soc,
(1990).
2 7 M. T. HAWARD, M. W. GEORGE, P . HAMLEY and M. POLI­
AKOFF, J. Chem. Soc, Chem. Commun., 1 1 0 1 - 3 (1991).
R . H . CRABTREE and D . G . HAMILTON, J. Am. Chem.
2 8
1 0 8 3 1 2 4 - 5 (1986).
Most of the observed facts can be understood
in terms of a bonding scheme which envisages
5 5 5 3 2 2 (26) donation of electron density from the σ bond
2 (27) of H2 into a vacant hybrid orbital on the
metal, plus a certain amount of synergic back
metal into the σ* antibonding orbital of H2 (see
2 2 2 Fig. 3.3). This is reminiscent of the bonding in
3 (28) the well known metal-alkene complexes (to be
discussed in more detail on p. 931) but with two
significant differences: (a) the electron density
single-bond σ orbital whereas for alkenes such as
H 2 C = C H 2 it is in the π component of the double
in accepting back-donated electron density has
σ* symmetry rather than π* as in alkenes. It
2 is clear from this description that an overall
positive charge on the metal centre encourages
H \
forward donation to form the 3-centre >—M
H'
S . M. HOWDLE and
bond, but diminishes the extent of back donation.
Chem. Commun., 9 1 3 - 5
By contrast, an overall negative charge might
be expected to enhance back donation into
the σ* antibonding orbital and thus promote
Soc.
rupture of the H2 single bond, with concommitant
formation of two new hydrido M - H bonds.
§3.4.1 The coordination chemistry of hydrogen 47

The bonding scheme is also consistent with the studies (32)

have revealed one Η· · H contact of
observed lengthening of the H - H distance to 137.7(7) pm whereas all other H - H distances
about 8 4 - 9 0 pm in the η -ΙΪ2 complexes (as
2
in the complex are greater than 174 pm. (This
compared with 74 pm in free molecular H2), distance of 137.7 pm is seen to be intermediate
and with the lowering of the v(H-H) vibration between values of ca. 80 pm typical of η -Η2 2

1
frequency from 4159 c m " in free H2 to values complexes and values greater than ca. 160 pm
- 1
typically in the range 2 6 5 0 - 3 2 5 0 c m in the which are found in classical hydrido complexes.)
complexes. Likewise, some trihydrogen complexes, such as
There is evidently a very fine balance between 5
[Ir(rç -C H )H3(PMe3)], 5have nmr behaviour
5
(33)

2
the two options {M(j7 -H )} and {M(H)2}; indeed,
2 which suggests the presence of a bent (or possibly
examples of an equilibrium between the two 3
triangular) η -11 ligand which is bonded "side- 3
(27,29,30)
forms have recently been d i s c o v e r e d : on" rather like an allylic group (pp. 9 3 3 - 5 ) .
1
The possibility of rç -^ "end-on" coordination
-78° to + 2 5 °
has also been mooted. For example, deposition
of Pd atoms onto a krypton matrix doped with
[Nb(^-C H )(CO)3(H) ] 5 5 2
H at 12 Κ apparently yields both Pd(r/ -H ) and 1
2 2

-85° to -65° 2
Pd(rç -H2) species, whereas with a Xe/H2 matrix
2 +
[Re(CO)(r/ -H2)(H)2(PMe Ph)3] ν 2
only Pd(rç -H ) was o b t a i n e d .2
Again, the (34)
2

[Re(CO)(H) (PMe Ph) ] 4 2 3

+
complex [ R e C l ( H 2 ) ( P M e P h 2 ) 4 ] appears to feature
an asymmetrically-bonded H2 ligand which may
hexane/r.t. ι 5)
2
[Ru(^ -H2)(^-0 CCF3)(PCy ) ] , well be (η -Η )Ρ 2
2 3 2

Nearly one hundred η -ΙΪ2 complexes have so 2

[Ru(H) (r; -0 CCF3)(PCy3)2]

2
2
2
far been prepared and the crystal and molec­
ular structure of about half a dozen have
the η -Η2 form (27) 2
In the niobium s y s t e m
been determined by X-ray/neutron diffraction.
is marginally the more stable, with AH =
- 1 (29)
Some are dinuclear, such as the homobimetallic
2.0 kJ m o l , whereas in the rhenium s y s t e m , 2
[(P-N)(i -H )Ru(M-Cl)2(M-H)Ru(H)(PPh )2]
? 2 3
(36)

it is the tetrahydrido form which is the

- 1
and the heterobimetallic [ ( P P h 3 ) 2 H R e ( μ - H ) ( μ -
more stable, with — AG208 = 2.5 kJ m o l and 2
Cl) (M-CO)Ru(^ -H )(PPh )2] .
2 2 3
+ (37)

-AH = 4 . 6 k J m o l " . 1

2
The coordination chemistry of hydrogen is still
In a sense the formation of rç -H2 complexes
being intensively studied and new developments
can be thought of as an intermediate stage in
are continually being reported.
the oxidative addition of H2 to form two M - H
bonds and, as such, the complexes might serve
3 2
L . BRAMMER, J. A . K . HOWARD, O . JOHNSON, T . F . KOET-
as a model for this process and for catalytic
31 )
ZLE, J. L. SPENCER and A . M. STRINGER, J. Chem. Soc,
hydrogénation reactions by metal h y d r i d e s / Chem. Commun., 2 4 1 - 3 ( 1 9 9 1 ) .
2
Indeed, intermediate cases between τ? -Η2 and 3 3
D. M. HEINEKEY, N. G . PAYNE and G . K. SCHULTE, J. Am.
(σ-Η) coordination are occasionally observed, as
2
Chem. Soc. 1 1 0 , 2 3 0 3 - 5 (1988).
3 4
G . A . OZIN and J. GARCIA-PRIETO, J. Am. Chem. Soc 1 0 8 ,
in [ReH7(P(/?-tol)3)2], where neutron-diffraction
3 0 9 9 - 1 0 0 (1986).
3 5
F . A . COTTON and R. L . LUCK, Inorg. Chem. 3 0 , 7 6 7 - 7 4
2 9
X.-L. Luo and R. H. CRABTREE, J. Chem. Soc, Chem. (1991).
3 6
Commun., 1 8 9 - 9 0 (1990). C . HAMPTON, W. R. CULLEN and B . R. JAMES, J. Am.
3 0
T. ANLIGUIE and B . CHAUDRET, J. Chem. Soc, Chem. Chem. Soc 1 1 0 , 6 9 1 8 - 9 ( 1 9 8 8 ) . In this compound, P - N is
Commun., 1 5 5 - 7 ( 1 9 8 9 ) . a complex substituted ferrocene ligand. See also A . M. JOSHI
3 1
C . BIANCHINI, C . MEALLI, A . MELI, M . PERUZZINI and and B . R. JAMES, J. Chem. Soc, Chem. Commun., 1 7 8 5 - 6
F. ZANOBINI, J. Am. Chem. Soc. 110, 8 7 2 5 - 6 (1988). (1989).
3 7
See also L . D . FIELD, Α . V . GEORGE, Ë . Y . MALOUF and M . CAZANOUE, Ζ. H E , D. NEILBECKER and R. MATHIEU, J.
D . J. YOUNG, Chem. Soc, Chem. Commun., 9 3 1 - 3 ( 1 9 9 0 ) . Chem. Soc, Chem. Commun., 3 0 7 - 9 ( 1 9 9 1 ) .
48 Hydrogen Ch. 3
(38)
3.5 Protonic acids and bases [ F e ( H 0 ) 6 ] . The hydrogen-ion concentration is
2

usually expressed as pH (see Panel). In dilute

Many compounds that contain hydrogen can solution the concentration of water molecules
donate protons to a solvent such as water and is constant at 25°C ( 5 5 . 3 4 5 m o l l ) , and the -1

so behave as acids. Water itself undergoes ionic dissociation of the acid is often rewritten as
dissociation to a small extent by means of
autoprotolysis; the process is usually represented H A ^ H +
+ A";
formally by the equilibrium + 1
K = [ H ] [ A " ] / [ H A ] moll""
a

H 0 + H 0
2 2 H 0 + + OH~
3

The acid constant K a can also be expressed by

though it should be remembered that both the relation
ions are further solvated and that the time a
proton spends in close association with any pK a = - log AT . e Hence, as K a = 55.345 Κ
one water molecule is probably only about
13
10~ s. (See also pp. 6 3 0 - 2 for structural studies pKa =pK- 1.734
+ 1
on [ Η ( Ο Η ) ] η = 1-6.) Depending on what
2 π

aspect of the process is being emphasized, the Further, as the free energy of dissociation is given
+
species H 3 0 ( a q ) can be called an oxonium by
ion, a hydrogen ion, or simply a solvated
(hydrated) proton. The equilibrium constant for AG° = -RTXnK = -23026RT\ogK,
autoprotolysis is
the standard free energy of dissociation is
2
K = [H 0+][OH-]/[H 0]
x 3 2

Δ^ 9 8 . ΐ 5 = 5.708ptf
and, since the concentration of water is essen­
tially constant, the ionic product of water can be = 5.708(pJf + 1 . 7 3 4 ) k J m o r
e
1

written as
2 2
Textbooks of analytical chemistry should be
K = [Η 0 ][ΟΗ ] m o l r + _
w 3
consulted for further details concerning the
The value of K depends on the temperature,
w
ionization of weak acids and bases and the theory
being 0.69 χ 1 0 - m o l r atO°C, 1.00 χ 1 0 ~
1 4 2 2 14
of indicators, buffer solutions, and acid-alkali
039 40
at 25°C and 47.6 χ 1 0 ^ at 100°C. It follows 14
titrations. "
that the hydrogen-ion concentration in pure water Various trends have long been noted in the
7
at 25°C is 1 0 ~ m o l l . Acids increase this _ 1
acid strengths of many binary hydrides and
(38)
concentration by means of the reaction oxoacids. Values for some simple hydrides
are given in Table 3.4 from which it is clear
HA 4- H 0 2 H 0 + + A";
3
that acid strength increases with atomic number
= [H3O+HA-] both in any one horizontal period and in any
[HA][H 0] 2

3 9

It is to be understood that all the species are in A. I. VOGEL, Quantitative Chemical Analysis, 5th edn.,
Sections 2 . 1 2 - 2 . 2 7 , pp. 3 1 - 6 0 . Longman, London, 1989.
aqueous solution and the symbol HA implies only 4 0
A. HULANICKI, Reactions of Acids and Bases in Analytical
that the (aquatéd) species can act as a proton Chemistry, Ellis Horwood (Wiley), Chichester, 1987, 308 pp.
donor: it can be a neutral species (e.g. H S ) , 2
4 1
D . ROSENTHAL and P. ZUMAN, Acid-base equilibria,
an anion (e.g. Η Ρ θ 4 ~ ) or a cation such as
2
buffers and titrations in water, Chap. 18 in I. M. KOLTHOFF
and P. J. ELVING (eds.), Treatise on Analytical Chemistry, 2nd
edn., Vol. 2, Part 1, 1979, pp. 1 5 7 - 2 3 6 . Succeeding chapters
3 8
R . P . BELL, The Proton in Chemistry, 2nd edn. Chapman (pp. 2 3 7 - 4 4 0 ) deal with acid-base equilibria and titrations
& Hall, London, 1973, 223 pp. in non-aqueous solvents.
§3.5 Protonic acids and bases 49

The Concept of pH -
Hie now niaversally used measure of the hydiogen-ton cxHicjentnitton was Imoêmé k S 9 0 ¥ ^ à » ^ ^
S. Ε Lv Sffcensen during Ms wot* at te Carlsberg Breweries {Biochem, Ζ 21,131,1909):

The symbol pH derives from the French /wiswnr^ d'hydrogène,referringto the e x r x ^ t or "power of ten" a^d to

whl h i ^ ^ have a lower pH. For example, a stiongidàof c o n « p a f | g | i

pH 3, whereas a strong alkali of the same cojicentraOon has pH 11 since [H3O+J = 10~ /[OIT] m\ 14

Untaunately, it is tar simpler 10 define pH thantomeasure it, despite the commercial j

pugg***toéo mis, Most instruments use an electrochemical cell such as
glass eleetrodeftest solution|3.5 m KCl(aq)(Hg Cl2|Hg 2 ;/
Assuming thai me glass electrode shows an idea! hydrogen electrode response, the einf of th^cel! i ^ ^ p @ p # | o n m e
magnitude of the liquid junction potential E and me activity coefficients y of me ionjb species;, - : ; ί φ φ <
s , > H ?

fréter -V . · .\>
t ^.«, ' ^ r : A f v ^ - - * '* * V ^ ; > v / ' ; | | ^ # ^ ^ # : ' : / .
For to reason the pH ^ " '
simple furidamental significance. It Is defined by the equation

pH(X)s*pH(S)-f ^^falo^
whcrt pH(S)u the assigned pH of a standard buffer solution such as those supplied wi&ph meÉets,
Only in the case of dilute aqueous solutions (<&1 rnoir ) which are neither strongly acid or aUbn1ne(2 < p H < 12)
1

'\ \ ^ ' [ Τ :. \ '

4 pue*) * - fagOTty* ± om /

.«*β» ? * î %&,mm® ionic activity coefficient of a typical uni-univalent electrolyte, is #ve» fey /'$ ν - p> :

In this expression / is the ionic strength of the solution and Λ is a ten^)erature*dependent constant (OJlli mol"? at
25°C; 0.50!^ mori at 15°C). It is clearly unwise to associate a pH meter reading too closely with pH unless under very
controlled conditions, and still less sensible to relate the reading to the actual hydrogen-ion conœntrarion in solution.
For tether discussion of pH measurements, see Pure AppL Chem. 57, 531 -42 (1985): Definition of pH Scales, Standard
Reference Values, Measurement of pH and Related Terminology. Also CaE News, Oct 20, 1997, p. 6.

Table 3.4 A p p r o x i m a t e v a l u e s o f pK a for s i m p l e periodic table could be ascribed to the increasing

hydrides electronegativity of the elements which would
CH 4 46 NH^ 35 OH 2 16 FH 3 favour release of the proton, but this is clearly
PH 3 27 SH2 7 C1H -7 not the dominant effect within any one group
SeH 2 4 BrH -9 since the trend there is in precisely the opposite
TeH 2 3 IH -10
direction. Within a group it is the diminution
in bond strength with increasing atomic number
that prevails, and entropies of solvation are
vertical group. Several attempts have been made also important. It should, perhaps, also be
to interpret these trends, at least qualitatively, emphasized that thermodynamic computations
but the situation is complex. The trend to do not "explain" the observed acid strengths;
increasing acidity from left to right in the they merely allocate the overall values of AG,
50 Hydrogen Ch. 3

AH and AS to various notional subprocesses „ [Η+][ΗΡ0 -] 4

2
ο „ _ !
such as bond dissociation energies, ionization K 2 = 6 3 1 X 1 0 m 0 1 1 ;
= [Η Ρ0 -]2 4

energies, electron affinities, heats and entropies

ρΚ 2 = 7.20
of hydration, etc., which themselves have
empirically observed values that are difficult to 2
Η Ρ 0 " = = = Η+ + Ρ 0
4 4
3
";
compute ab initio. 3
[Η+][Ρ0 -] 4
Regularities in the observed strengths of Κ 3 = = 4.22 χ Ι Ο " mol Γ ; 1 3 1

oxoacids have been formulated in terms of two [ΗΡ0 -] 4

rules by L. Pauling and others: ρΚ 3 = 12.37

(i) for polybasic mononuclear oxoacids,

Qualitatively, a reduction in pK for each succes­ a

successive acid dissociation constants

sive stage of ionization is to be expected since the
diminish approximately in the ratios
5 10
proton must separate from an anion of increas­
1:10- :ΚΓ :...; ingly negative charge, though the approximately
(ii) the value of the first ionization constant constant reduction factor of 10 is more difficult 5

for acids of formula X O ( O H ) „ depends m

to rationalize quantitatively.
sensitively on m but is approximately inde­ Acids which illustrate the second rule are sum­
pendent of η and X for constant m, being marized in Table 3.5. The qualitative explanation
8 2 3
< 1 ( T for m = 0, ~ 1 0 " for m = 1, M O for this regularity is that, with increasing numbers
8
for m = 2, and > 1 0 for m = 3. of oxygen atoms the single negative charge on the
anion can be spread more widely, thereby reduc­
Thus to illustrate the first rule:
ing the electrostatic energy attracting the proton
and facilitating the ionization. On this basis one
Η Ρ0 ^=^Η++Η Ρθ4;
3 4 2
might expect an even more dramatic effect if the
[H+][H P0 -] 2 4
- 3 1
anion were monoatomic (e.g. S , S e , Te ~) 2 - 2 - 2

= 7.11 χ Ί Ο moll"" ;
[H3PO4] since the attraction of these dianions for protons
will be very strong and the acid dissociation con­
pK } =2.15
stant of S H " , SeH~ and TeH~ correspondingly
Η ΡΟ,'4
2 ^= Η +
+ ΗΡ0 -; 4
2
small; this is indeed observed and the ratio of

Table 3.5 Values o f pK a for s o m e m o n o n u c l e a r o x o a c i d s X O ( O H ) m n (pK % S-5n)

a

X(OH)„ XO(OH)„ X0 (OH)„

2 X0 (OH)„ 3

(very w e a k ) (weak) (strong) (very strong)

Cl(OH) 7.2 NO(OH) 3.3 N0 (OH)

2 -1.4 C10 (OH) 3 (-10)
Br(OH) 8.7 CIO(OH) 2.0 C10 (OH) 2 -1 Mn0 (OH) 3 —
I(OH) 10.0 CO(OH) 2
3.9 ( a )
I0 (OH)
2 0.8
B(OH) 3
9.2 SO(OH) 2
1.9 S0 (OH)
2 2 <0
As(OH) 3
9.2 SeO(OH) 2 2.6 Se0 (OH) 2 2 <0
Sb(OH) 3
11.0 TeO(OH) 2 2.7
Si(OH) 4
10.0 PO(OH) 3 2.1
Ge(OH) 4
8.6 AsO(OH) 3 2.3
Te(OH) 6
8.8 IO(OH) 5
1.6
HPO(OH) 2 1.8 (b)

( b )
H PO(OH)
2 2.0
(a)
Corrected for the fact that only 0.4% of dissolved C 0 is in the form of H C 0 ; the conventional value is pK 6.5. 2 2 3 a

(b)
N o t e that the value of pK for hypophosphorous acid H Pt> is consistent with its (correct) formulation as HPO(OH) rather
a 3 3 2

than as P(OH) , which would be expected to have pK > 8. Similarly for H P 0 , which is H PO(OH) rather than HP(OH) .
3 a 3 2 2 2
§3.5 Protonic acids and bases 51

Table 3.6 First and s e c o n d ionization constants or hydroxobridged polynuclear species that
for H S , H S e and H T e
2 2 2
eventually precipitate as hydrous oxides (see
p*i pK 2
ApK discussion of the chemistry of many elements in
later chapters). A useful summary is in Fig. 3.4.
H S 2 7 14 1
H Se 4 12 8
By contrast, extensive studies of the pK values a
2

H Te 2 3 11 8 of hydrated metal ions in solution has generated

a wealth of numerical data but no generalizations
such as those just discussed for the hydrides
(42)
the first and second dissociation constants is M O 8
and oxoacids of the non-metals. Typical pK Q

rather than 1 0 (Table 3.6). 5

values fall in the range 3 - 1 4 and, as expected,
The results for dinuclear and polynuclear there is a general tendency for protolysis to be
oxoacids are also consistent with this interpre­ greater (pK values to be lower) the higher the
a

tation. Thus for phosphoric acid, H4P2O7, the cationic charge. For example, aqueous solutions
successive pK values are 1.5, 2.4, 6.6 and 9.2;
a
of iron(III) salts are more acidic than solutions
the ~ 10-fold decrease between pATi and pK 2
of the corresponding iron(II) salts. However, it
(instead of a decrease of 10 ) is related to the 5
is difficult to discern any regularities in pK for a

fact that ionization occurs from two different series of cations of the same ionic charge, and it
P O 4 units. The third stage ionization, however, is clear that specific "chemical" effects must also
5
is M O less than the first stage and the differ­ be considered.
ence between the mean of the first two and the Br0nsted acidity is not confined to dilute
5
last two ionization constants is ~ 5 χ 1 0 . aqueous solutions and the ideas developed in the
Another phenomenon that is closely associated preceding pages can be extended to proton donors
(43,44)
with acid-base equilibria is the so-called hydrol­ in nonaqueous s o l u t i o n s . In organic solvents
ysis of metal cations in aqueous solution, which and anhydrous protonic liquids the concepts
is probably better considered as the protolysis of of hydrogen-ion concentration and pH, if not
hydrated cations, e.g.: actually meaningless, are certainly operationally
inapplicable and acidity must be defined on some
"hydrolysis": other scale. The one most frequently used is
Fe 3 +
+ H 0 ===== [ F e ( O H ) ] 2+
+ H + the Hammett acidity function Ho which enables
2

various acids to be compared in a given solvent

protolysis: and a given acid to be compared in various
[Fe(H 0) ] ++H 0==== 3 solvents. For the equilibrium between a base
2 6 2

and its conjugate acid (frequently a coloured

2 +
[Fe(H 0) (OH)] 2 5 + H3O+; pK 3.05 a indicator)

[ F e ( H 0 ) ( O H ) ] + + H 0 =====
2 5
2
2 Β + H+ ===== BH+
+
[Fe(H 0) (OH) ]+ + H 0 ;
2 4 2 3 pK 3.26 a the acidity function is defined as

It is these reactions that impart the characteristic Ho = pK BH+ - log{[BH+]/[B]}

yellow to reddish-brown coloration of the
In very dilute solutions
hydroxoaquo species to aqueous solutions of
iron(III) salts, whereas the undissociated ion K +
BH = [B][H+]/[BH+]
3 +
[ F e ( H 0 ) 6 ] is pale mauve, as seen in crystals
2

of iron(III) alum { [ F e ( H 0 ) ] [ K ( H 0 ) ] ( S 0 ) } 2 6 2 6 4 2
4 2
L . G . SILLÉN, Q. Rev. (London) 1 3 , 1 4 6 - 6 8 ( 1 9 6 9 ) ; Pure

and iron(III) nitrate { [ F e ( H 0 ) ] ( N 0 ) . 3 H 0 } . Appl. Chem. 1 7 , 5 5 - 7 8 ( 1 9 6 8 ) .

2 6 3 3 2
4 3
C. H. ROCHESTER, Acidity Functions, Academic Press,
Such reactions may proceed to the stage
London, 1 9 7 0 , 3 0 0 pp.
where the diminished charge on the hydrated 4 4
G . A. OLAH, G . K . S . PRAKASH and J. SOMMER, Super­
cation permits the formation of oxobridged, acids, Wiley, New York, 1 9 8 5 , 3 7 1 pp.
 Figure 3.4 Plot o f effective i o n i c radii versus o x i d a t i o n state for various e l e m e n t s .

so that in water H$ becomes the same as pH. 3.6 The Hydrogen Bond* » 457
Some values for typical anhydrous acids are in
Table 3.7 and these are discussed in more detail The properties of many substances suggest that,
in appropriate sections of later chapters. in addition to the "normal" chemical bonding
between the atoms and ions, there exists some
T a b l e 3.7 H a m m e t t acidity functions for s o m e a n h y ­ further interaction involving a hydrogen atom
drous acids placed between two or more other groups
Acid -Ho Acid -H 0
of atoms. Such interaction is called hydrogen
H S 0 F + SbF
3 15-27 5 HF -11 bonding and, though normally weak ( 1 0 - 6 0 kJ
HF + S b F (1M) 20.4
5 H3PO4 5.0 per mol of Η-bonded H), it frequently has a
HS0 F 3 15.0 H S 0 ( 6 3 % in H 0 )
2 4 24.9 decisive influence on the structure and properties
H2SO4 12.0 HCQ H 2.2
2
of the substance. A hydrogen bond can be said to
exist between 2 atoms A and Β when these atoms
It will be noted that addition of SbFs to HF con­ approach more closely than would otherwise
siderably enhances its acidity and the same effect be expected in the absence of the hydrogen
can be achieved by other fluoride acceptors such atom and when, as a result, the system has
as B F and TaF :
3 5
a lower total energy. The bond is represented

2HF + MF„ ===== H F + + M F „ f 2 +

4 5 G . C . PIMENTEL and A . L . MCCLELLAN, The Hydrogen
Bond, W . H . Freeman, San Francisco, 1 9 6 0 , 4 7 5 pp.
The enhancement of the acidity of H S O 3 F by 4 6W . C. HAMILTON and J. A . IBERS, Hydrogen Bonding in
the addition of S b F is more complex and the
5 Solids, W . A . Benjamin, New York, 1 9 6 8 , 2 8 4 pp.
equilibria involved are discussed on p. 570. 4 7 J. EMSLEY, Chem. Soc. Revs. 9 , 9 1 - 1 2 4 ( 1 9 8 0 ) .
§3.6.1 Hydrogen bonds: influence on properties 53

F i g u r e 3.5 S o m e e x a m p l e s o f branched H b o n d s : (a) the bifurcated b o n d i n l , 3 - d i o x a n o l - 5 ( 4 9 ) ; and trifurcated

b o n d s in ( b ) A ^ , ^ V - b i s ( 2 - h y d r o x y e t h y l ) g l y c i n e (50) a n d ( c ) the nitrilotriacetate dianion. ( 5 , )

as A - H · · · Β and usually occurs when A is It will be convenient first to indicate the range
sufficiently electronegative to enhance the acidic of phenomena which are influenced by H bonding
nature of Η (proton donor) and where the and then to discuss more specifically the nature
acceptor Β has a region of high electron density of the bond itself according to current theories.
(such as a lone pair of electrons) which can The experimental evidence suggests that strong
interact strongly with the acidic hydrogen. In fact, H bonds can be formed when A is F, Ο or N;
the Η bond in A - H · · Β can be either linear as weaker Η bonds are sometimes formed when
in schematic structure (1) or significantly non­ A is C or a second row element, P, S, CI or
linear as in structures ( l b ) and (lc). Η-bonds can even Br, I. Strong Η bonds are favoured when
also join three adjacent atoms (bifurcated) as in the atom Β is F, Ο or Ν ; the other halogens
structure (2) or even four atoms (trifurcated) as Cl, Br, I are less effective unless negatively
in structure (3). charged and the atoms C, S and Ρ can also
sometimes act as Β in weak Η bonds. Recent
examples of C - H - · · Ν and C - H - · · C bonds are
in bis(phenylsulfonyl)trimethylbutylamine ( 4 ) (52)

Η · · Β
Η ' and the carbanion of [l.l]ferrocenophane ( 5 ) . (53)

(la) (lb) (le)

(pH4 · · · f|!H · · · (psH 4

NMei
A — Η - H ; - B 2 \ X is the S-bonded
Γ ϊ Γ
X ŒH CH(MeKH
2 2 2 P h S 0 2 g r o u P
" B 2

C5H4 · · *CH · · · C5H4

(4)
(2) (3) (5)

Thus, in a recent survey of 1509 N - H - · 0 = C

hydrogen bonds in organic carbonyls or carb- 3.6.1 Influence on properties
oxylates, nearly 80% (1199) were unbranched,
some 20% (304) were bifurcated, but only 0.4% It is well known that the mps and bps of N H 3 ,
(6) were trifurcated. Some examples are in
(48)
H 0 and H F are anomalously high when com­
2

Fig. 3.5. pared with the mps and bps of the hydrides of
other elements in Groups 15, 16 and 17, and the

4 8 R . TAYLOR, O . KENNARD and W . VERICHEL, J. Am. Chem.

Soc. 106, 2 4 4 - 8 ( 1 9 8 4 ) . 5 1 S . H . WHITLOW, Acta Crystallogr. B28, 1 9 1 4 - 9 ( 1 9 7 2 ) .
4 9 J. L . ALONSO and Ε. B . WILSON, J. Am. Chem. Soc. 102, 5 2 R. L . HARLOW, C . LI and M. P . SAMMES, J. Chem. Soc,
1248-51 (1980). Chem. Commun., 8 1 8 - 9 (1984).
5 0 V . CODY, J. HAZEL and D . LANGS, Acta Crvstallogr. B33, 5 3 P . AHLBERG and O . DAVIDSSON, J. Chem. Soc, Chem.
905-7 (1977). Commun., 6 2 3 - 4 (1987).
 54 Hydrogen Ch. 3

same effect is noted for the heats of vaporization, free-energy change on passing from the solid to
as shown in Fig. 3.6. The explanation normally the liquid phase:
given is that there is some residual interaction (H
bonding) between the molecules of N H , H2O 3
AG m = AH -T AS =0;
m m m

and HF which is absent for methane, and either hence T m = AH /ASm m

absent or much weaker for heavier hydrides. This

argument is probably correct in outline but is
deceptively oversimplified since it depends on the
assumption that only some of the H bonds in solid
HF (for example) are broken during the melting
process and that others are broken on vaporiza­
tion, though not all, since HF is known to be
substantially polymerized even in the gas phase.
The mp is the temperature at which there is zero
It can be seen that a high mp implies either a high
enthalpy of melting, or a low entropy of melting,
or both. Similar arguments apply to vaporization
and the bp, and indicate the difficulties in quan­
tifying the discussion.
Other properties that are influenced by H
bonding are solubility and miscibility, heats
of mixing, phase-partitioning properties, the

F i g u r e 3.6 Plots s h o w i n g the h i g h v a l u e s o f m p , b p and heat o f vaporization o f N H , H 0 and H F w h e n c o m p a r e d

3 2

with other hydrides. N o t e a l s o that the m p o f C H ( - 1 8 2 . 5 ° C ) is slightly h i g h e r than that o f S i H

4 4

(-185°C).
§3.6.1 Hydrogen bonds: influence on properties 55

existence of azeotropes, and the sensitivity of mainly in the range 5 0 - 7 5 o h m c m m o l .

- 1 2 - 1

chromatographic separation. Liquid crystals (or (To convert to mobility, t ; c m s V , divide

2 _ 1 _ 1

mesophases) which can be regarded as "partly by 9 6 4 8 5 C m o l . ) It is also notable that the

- 1

melted" solids also frequently involve molecules dielectric constant is not linearly related to
that have Η-bonded groups (e.g. cholestérols, molecular dipole moments for Η-bonded liquids
polypeptides, etc.). Again, H bonding frequently being much higher due to the orientating effect
results in liquids having a higher density and of the H bonds: large domains are able to
lower molar volume than would otherwise have
align in an applied electric field so that the
been expected, and viscosity is also affected (e.g.
molecular dipoles reinforce one another rather
glycerol, anhydrous H2SO4, H3PO4, etc.).
than cancelling each other due to random thermal
Electrical properties of liquids and solids are
motion. Some examples are given in Fig. 3.7,
sometimes crucially influenced by H bonding.
which also illustrates the substantial influence
The ionic mobility and conductance of ^ 0 +
of temperature on the dielectric constant of H-
and OH~ in aqueous solutions are substantially
bonded liquids presumably due to the progressive
greater than those of other univalent ions
due to a proton-switch mechanism in the H- thermal dissociation of the H bonds. Even
bonded associated solvent, water. For example, more dramatic are the properties of ferroelectric
at 25°C the conductance of H 0 and OH~
3 +
crystals where there is a stable permanent electric
are 350 and 192 o h m c m m o l , whereas for
- 1 2 - 1
polarization (see Fig. 3.8). Hydrogen bonding
other (viscosity-controlled) ions the values fall is one of the important ordering mechanisms

F i g u r e 3.7 Dielectric constant o f s e l e c t e d liquids.

responsible for this phenomenon as discussed in
more detail in the Panel o p p o s i t e . (54,55)
Intimate information about the nature of the
H bond has come from vibrational spectroscopy
(infrared and Raman), proton nmr spectroscopy,
and diffraction techniques (X-ray and neutron). In
vibrational spectroscopy the presence of a hydro­
gen bond A - H · Β is manifest by the following
effects:
(i) the A - H stretching frequency y shifts to
lower wave numbers;
(ii) the breadth and intensity of y ( A - H )
increase markedly, often more than
tenfold;
(iii) the bending mode <5(A-H) shifts to higher
wave numbers;
(iv) new stretching and bending modes of the
Η bond itself sometimes appear at very
low wave numbers ( 2 0 - 2 0 0 c m ) .
C. KITTELL, Introduction to Solid State Physics,
5 4
Chap. 13, pp. 3 9 9 - 4 3 1 . Wiley, New York, 1976.
5 5H.-G. UNRUH, Ferroelectrics in Ullmann's Encyclopedia
of Industrial Chemistry, Vol. A10, VCH, Weinheim, 1987,
pp. 3 0 9 - 2 1 , and references cited therein.
Most of these effects correlate roughly with
the strength of the Η bond and are particularly
noticeable when the bond is strong. For example,
for isolated non-H-bonded hydrogen groups,
y ( O - H ) normally occurs near 3 5 0 0 - 3 6 0 0 c m
_1
and is less than 10 c m - 1 broad whereas in the
presence of O - H · · · Ο bonding y t i s y m drops
an
to M 7 0 0 - 2 0 0 0 c m , is several hundred c m
- 1 - 1
broad, and much more intense. A similar effect
of Δ ν - 1 5 0 0 - 2 0 0 0 c m is noted on F - H · · F
- 1
formation and smaller shifts have been found for
N - H · · · F (Αν < 1 0 0 0 c m " ) , N - H · Ο (Ay <
1
4 0 0 c m " ) , O - H - N (Ay < 1 0 0 c m " ) , etc. A
1 1
full discussion of these effects, including the
influence of solvent, concentration, temperature
and pressure, is given in ref. 45. Suffice it to note
that the magnitude of the effect is much greater
than expected on a simple electrostatic theory of
hydrogen bonding, and this implies appreciable
- 1
electron derealization (covalency) particularly
for the stronger Η bonds.
5th edn., Proton nmr spectroscopy has also proved
valuable in studying Η-bonded systems. As
might be expected, substantial chemical shifts
are observed and information can be obtained
§3.6.1 Hydrogen bonds: influence on properties 57
58 Hydrogen Ch. 3
•liiiiiiiiiiii^^
Hie closely related phenomenon of annferroelectric behaviour is also kaown, M which there h an ordered, self-
cancelling arrangement of permanent electric dipole moments below a certain transition temperature; H bonding is again
implicated in the ordering mechanism for several aminonium salts of this type, e.g. (Νί^Η^Κ^ 148 Κ, (ΝΗ^^ΡΟ*
242 K. (NH4)H As0 216K, (NHOD^AsC^ 304 & and (NRihHjIQ* 254 Κ, As with ferroelectrics, antiferroe^n^ can
2 4

also arise by a displacive mechanism in perovskite-type structures, and epical examples, w u t thek transition tempera­
tures, are: ' ' ': .- - " '>· ; '^''\·-.
1 : ! '' ^ '^^^Χ'Κ^'
< Ίτ^--ν ,, - / ; ' . ί > ^ *
; >

FhZr0 506Κ, PbHfOa 488 Κ, NaNbOs 793,911Κ WOa 1010 Κ.

3

Ferroelectrics have many practical applications: they can he nsed as inhsiamte ceraj^ capacitors because of their large
capacitance, and their dectro-optical characteristics enable them go modulate and deflect laser beams. Ine temperatnre
dependence of spontaneous polarization in<htces a s i n ^
detection. Many applications depend on me lad mat all ferroelectrics aie also pkzoeiectrics. ftc^le<aricity is the property
of acquiring (or altering) an electric polarization Ρ under external mechanical stress, or conversely, te prt^erty of c h a n g e
size (or shape) when subjected to an external electric field E. Inns ferroelectrics have been used as transducers to convert
mechanical pulses into electrical ones and vice versa, and and extensive application in ultrasonic generators, mksophoiies,
and gramophone pickups; they can also be used as fre<|uency controllers, electric titers* modulating devices, frequency
muldpliers, and as switches, counters and omer bistable elements in computer circuits. A further ingeneous application §S^A £•
in delay lines by means of which an electric signal Is transformed into an acoustic signal which passes
down the piezoelectric rod at the velocity of sound unfit at ttië other end, ϋ is reconverted into a (delayed) electric, signal.
It should be noted that, whereas ferroelectrics are necessarily piezoelecnm the converse need not apply. The necessary
condition for a crystal to be riezoele<^ is that M Of me 32 point groups, 20
qualify for piezoelectricity on mis criterion; bot fœ Émockc&te behaviour a further criterion is required (the possession
of a single non-eqpnvalent direction) and only 10 space groups meet mis additional tequir^^
that is pkioetoric but not ferroeie<^ since Êà;p$M^
quartz for oscillator stabilization has permitted ^ffry^^pBMWil. <Hf^yMwiw^y accurate clocks (1 in I0 ) and has also made
8

rxmib^^

llllllllle

concerning Η-bond dissociation, proton exchange there is a magnetic anisotropy effect due to B;
times, and other relaxation processes. The this will be positive (upfield shift) if the principal
chemical shift always occurs to low field and symmetry axis of Β is towards the Η bond, but
some typical values are tabulated below for the the effect is presumably small since the overall
shifts which occur between the gas and liquid shift is always downfield.
phases or on dilution in an inert solvent: Ultraviolet and visible spectra are also
influenced by Η bonding, but the effects are more
Compound CH 4 C H
2 6 CHC1 3 HCN NH 3 PH 3
difficult to quantify and have been rather less
<5ppm 0 0 0.30 1.65 1.05 0.78 used than ir and nmr. It has been found that the
Compound H 0
2 H S
2 HF HC1 H B r HI η -> 7Γ* transition of the base Β always moves to
<5ppm 4.58 1.50 6.65 2.05 1.78 2 . 5 5 high frequency (blue shift) on Η-bond formation,
the magnitude of Av being ~ 3 0 0 - 4 0 0 0 c m - 1

The low-field shift is generally interpreted, for bands in the region 15 0 0 0 - 3 5 000 c m . By - 1

at least qualitatively, in terms of a decrease contrast π -> π* transitions on the base Β usually
in diamagnetic shielding of the proton: the move to lower frequencies (red shift) and shifts
formation of A - H · Β tends to draw Η are in the range —500 to —2300 c m for bands
- 1

towards Β and to repel the bonding electrons in the region 30 0 0 0 - 4 7 000 c m " . Detailed
1

in A - H towards A thus reducing the electron interpretations of these data are somewhat
density about Η and reducing the shielding. The complex and obscure, but it will be noted that the
strong electric field due to Β also inhibits the shifts are approximately of the same magnitude
diamagnetic circulation within the Η atom and as the enthalpy of formation of many Η bonds
this further reduces the shielding. In addition, (83.59 c m per atom = 1 k J m o l ) .
- 1 - 1
§3.6.2 Hydrogen bonds: influence on structure 59

H H H

Ov
I Ov ,0
Ov

0 0 Ο 0 ο
I Ι

H
1
Η
I
Η Η
I
Ι Η
I

C c

O - H Ο 265 pm
in both cases -Cv
Ο c ο

I I
Η Η

α - f o r m : layer structure with easy cleavage (H b o n d s remain intact)

Η — O ^ ^O—Η—Ο ^O—H—O^ —

/ c - c x / C - c x / C - c x

—Ο Ο—Η—Ο Ο—Η—Ο Ο—Η

β-form : long chains giving crystals that cleave into laths parallel to the chain

F i g u r e 3.9 S c h e m a t i c representation o f the t w o f o r m s o f o x a l i c acid, (-C0 H) .2 2

3 . 6 . 2 Influence cn structure (56 57)

with F - H - F distance 249 pm and the angle
HFH 120.Γ. Likewise, the crystal structure
The crystal structure of many compounds is of N H 4 H F 2 is completely determined by Η
dominated by the effect of Η bonds, and bonds, each nitrogen atom being surrounded by
numerous examples will emerge in ensuing 8 fluorines, 4 in tetrahedral array at 280 pm due
chapters. Ice (p. 624) is perhaps the classic to the formation of N - H · F bonds, and 4
example, but the layer lattice structure of B ( O H ) further away at about 310 pm; the two sets of
3

(p. 203) and the striking difference between the
a- and β-forms of oxalic and other dicarboxylic
acids is notable (Fig. 3.9). The more subtle
distortions that lead to ferroelectric phenomena
in K H 2 P O 4 and other crystals have already
been noted (p. 57). Hydrogen bonds between
fluorine atoms result in the formation of infinite
zigzag chains in crystalline hydrogen fluoride
5 6
L. PAULING, The Nature of the Chemical Bond, 3rd edn.,
Chap. 12, Cornell University Press, Ithaca, 1960.
5 7
A. F. WELLS, Structural Inorganic Chemistry,
Clarendon Press, Oxford, 1984, 1382 pp.
fluorine atoms are themselves bonded pairwise
at 232 pm by F - H - F interactions. Ammonium
azide N H 4 N 3 has the same structure as N H 4 H F 2 ,
with N - H · · Ν 298 pm. Hydrogen bonding also
leads N H F to crystallize with a structure
4
different from that of the other ammonium (and
alkali) halides: N H 4 C I , N H B r and N H I each 4 4
have a low-temperature CsCl-type structure and a
high-temperature NaCl-type structure, but N H 4 F
adopts the wurtzite (ZnS) structure in which each
NH +
group is surrounded tetrahedrally by 4 F
4
to which it is bonded by 4 N - H · · F bonds
5th edn.,
at 271pm. This is very similar to the structure
60 Hydrogen Ch. 3
( 4 6 5 7 )
Table 3.8 L e n g t h o f typical H b o n d s '

Bond Length/pm E/pm ( a )

Examples

F- H- F 227 (270) NaHF , KHF 2 2

F- H. • F 245-249 (270) KH4F5, H F

0 - -H •F 265-287 (275) CuF .2H 0, FeSiF .6H 02 2 6 2

0 - -H •Cl 295-310 (320) HCI.H2O, ( N H O H ) C l , C u C l . 2 H 0 3 2 2

0 - -H • B r 320-340 (335) NaBr.2H 0, HBr.4H 0 2 2

0 - -H-- 0 240-263 (280) Ni dimethylglyoxime, K H maleate, H C r 0 2

Na H(C0 ) .2H 0 3 3 2 2

0 -H •0 248-290 (280) K H P 0 , N H H P 0 , K H A s 0 , AlOOH,

2 4 4 2 4 2 4

c * - H I 0 , n u m e r o u s hydrated metal sulfates

3

and nitrates
Ο -H •S 310-340 (325) MgS 0 .6H 0 2 3 2

Ο -H •· Ν 268-279 (290) N H .4MeOH, N H . H 0

2 4 2 4 2

N--H •·F 262-296 (285) NH F, N H F , (N H )SiF

4 2 6 2 2 6 6

N--H α 300-320 (330) Me NHCl, Me NH Cl, (NH OH)Cl

3 2 2 3

N-- H I 346 (365) Me NHI3

N--H • 0 281-304 (290) H S 0 N H , (NH ) S0 , NH OOCH, CO(NH )

3 2 4 2 4 4 2 2

N-- H •s 323, 329 (335) N H (HS)

2 5

N-- H •· Ν 294-315 (300) N H N , N C N C ( N H ) (i.e. d i c y a n d i a m i d e )

4 3 2 2

P - Η- • · I 424 (405) PH I 4

( a )
E = sum of van der Waals' radii (in pm) of A and Β (ignoring Η which has a value of ~ 120 pm) and
using the values F 135, Cl 180, Br 195, I 215; Ο 140, S 185; Ν 150, Ρ 190.

of ordinary ice. Typical values of A - H · · · Β into larger structural units. These may be:
distances found in crystals are given in Table 3.8. 3
finite groups: H F " ; [ 0 C O - H - · O C 0 ] ~ 2 2 2
The precise position of the Η atom in
in N a H ( C 0 ) 2 . 2 H 2 0 dimers of carboxylic
3 3
crystalline compounds containing Η bonds has
acids, etc.;
excited considerable experimental and theoret­
infinite chains: HF, HCN, H C 0 " , H S 0 " , 3 4

ical interest. In situations where a symmet­

etc.;
ric Η bond is possible in principle, it is fre­ infinite layers: N H F , B(OH) , B 0 ( O H ) , 2 6 2 3 3 3 3

quently difficult to decide whether the proton H S 0 , etc.; 2 4

is vibrating with a large amplitude about a sin­ three-dimensional nets: NH4F, H2O, H2O2,
gle potential minimum or whether it is vibrating Te(OH) , H2PO4- in K H P 0 , etc. 6 2 4

with a smaller amplitude but is also statistically

disordered between two close sites, the potential
energy barrier between the two sites being
(46,47)
small. It now seems well established that
the F - H - F bond is symmetrical in NaHF2 and
KHF2, and that the O - H - O bond is symmetrical
in HCrC>2. Other examples are the intra-molecular
Η bonds in potassium hydrogen maleate,
+
K [ d 5 - C H = C H C ( 0 ) 0 - H - O C ( 0 ) ] - and its
monochloro derivative: Numerous other exam­
ples of Η bonding will be found in later chapters.
In summary, we can see that Η bonding influ­
ences crystal structure by linking atoms or groups
Η bonding also vitally influences the conforma­
tion and detailed structure of the polypeptide
chains of protein molecules and the comple­
mentary intertwined polynucleotide chains which
(56,58)
form the double helix in nucleic a c i d s . Thus,
proteins are built up from polypeptide chains of
the type shown at the top of the next column.
These chains are coiled in a precise way
which is determined to a large extent by
N - H · Ο hydrogen bonds of length 279 ±
5 8
G . A . JEFFREY and W . SAENGER, Hydrogen Bonding in
Biological Structures, Springer Verlag, Berlin, 1991, 567 pp.
§3.6.3 Strength of hydrogen bonds and theoretical description 61

of developments of fundamental importance in

biochemistry. (58)

3.6.3 Strength of hydrogen bonds and

theoretical description (59)

Measurement of the properties of H-bonded

systems over a range of temperatures leads
to experimental values of AG, AH and
12 pm depending on the amino-acid residue AS for Η-bond formation, and these data
involved. Each amide group is attached by such have been supplemented in recent years
a hydrogen bond to the third amide group by increasingly reliable ab initio quantum-
from it in both directions along the chain, mechanical calculations. Some typical values(60)

resulting in an α-helix of pitch (total rise of for the enthalpy of dissociation of Η-bonded pairs
helix per turn) of about 538 pm, corresponding in the gas phase are in Table 3.9.
to 3.60 amino-acid residues per turn. These The uncertainty in these values varies
helical chains can, in turn, become stretched and between ± 1 and ± 6 k J m o l . In general, Η - 1

form hydrogen bonds with neighbouring chains bonds of energy < 2 5 k J m o l are classified as _ 1

to generate either parallel-chain pleated sheets weak; those in the range 2 5 - 4 0 kJ m o l " are 1

(repeat distances 650 pm) or antiparallel-chain medium; and those having AH > 4 0 k J m o l - 1

pleated sheets (700 pm). are strong. Until recently, it was thought
Nucleic acids, which control the synthesis of that the strongest H bond was that in
proteins in the cells of living organisms and the hydrogendifluoride ion [ F - H - F ] ; this is -

which transfer heredity information via genes, are difficult to determine experimentally and values
also dominated by H bonding. Their structure in the range 1 5 0 - 2 5 0 kJ m o l have been - 1

involves two polynucleotide chains intertwined reported. A recent theoretically computed value is
to form a double helix. The complimentariness 1 6 9 k J m o l which agrees well with the value of
- 1

in the structure of the two chains is ascribed to 163 ± 4 k J m o l from ion cyclotron resonance
- 1

the formation of H bonds between the pyrimidine studies/ In fact, it now seems that the H
61}

residue (thymine or cytosine) in one chain and the bond between formic acid and the fluoride ion,
purine residue (adenine or guanine) in the other
as illustrated in Fig. 3.10. Whilst there is still 5 9 A . C. LEGON and D . J. MILLEN, Chem. Soc. Revs. 21,
some uncertainty as to the precise configuration 71-8 (1992).
P. A . KOLLMAN, Chap. 3 in H . F . SCHAEFFER (ed.),
of the N - H · Ο and N - H · · · Ν hydrogen bonds 6 0

Applications of Electronic Structure Theory, Plenum Press,

in particular cases, the extraordinary fruitfulness New York, 1 9 7 7 .
of these basic ideas has led to a profusion 6 1 J. EMSLEY, Polyhedron 4, 4 8 9 - 9 0 (1985).

Table 3.9 Enthalpy of dissociation of Η-bonded pairs in the gas phase,

A// 2 9 8 (A-H...B)/kJmor 1

Weak Medium Strong

HSH-- SH 2 7 FH- · F H 29 HOH- · -Cr 55

NCH- · NCH 16 C1H- • O M e 2 30 HCONH - · OCHNH2 2 59
H NH-
2 ••NH 3 17 FH- · • O H
2 38 HCOOH OCHOH 59
MeOH • OHMe 19 HOH- - F - 98
HOH- · •OH 2 22 H OH+ - · OH
2 2 151
FH- - F - 169
HC0 H- 2 F" -200
62 Hydrogen Ch. 3

F i g u r e 3.10 Structural details o f the bridging units b e t w e e n pairs o f b a s e s in separate strands o f the d o u b l e helix
o f D N A : (a) the t h y m i n e - a d e n i n e pair (b) the c y t o s i n e - g u a n i n e pair.
§3.6.3 Strength of hydrogen bonds and theoretical description
[HCC^H- · F ], is some 3 0 k J m o l stronger 1
than that calculated on the same basis for
H F 2 -.(62)
Early discussions on the nature of the hydrogen
bond tended to adopt an electrostatic approach
in order to avoid the implication of a covalency
greater than one for hydrogen. Indeed, such
calculations can reproduce the experimental H-
bond energies and dipole moments, but this is
not a particularly severe test because of the
parametric freedom in positioning the charges.
However, the purely electrostatic theory is unable
to account for the substantial increase in intensity
of the stretching vibration v ( A - H ) on H bonding
or for the lowered intensity of the bending
mode <5(A-H). More seriously, such a theory
does not account for the absence of correlation
between Η-bond strength and dipole moment of
the base, and it leaves the frequency shifts in
the electronic transitions unexplained. Nonlinear
A - H - · Β bonds would also be unexpected,
though numerous examples of angles in the range
(46)
150-180° are k n o w n .
Valence-bond descriptions envisage up to five
contributions to the total bond wave function,
but these are now considered to be merely
computational devices for approximating to the
true wave function. Perturbation theory has also
been employed and apportions the resultant
bond energy between (1) the electrostatic energy
of interaction between the fixed nuclei and
the electron distribution of the component
molecules, (2) Pauli exchange repulsion energy
between electrons of like spin, (3) polarization
energy resulting from the attraction between the
polarizable charge cloud of one molecule and
the permanent multipoles of the other molecule,
(4) quantum-mechanical charge-transfer energy,
and (5) dispersion energy, resulting from second-
order induced dipole-induced dipole attraction.
The results suggest that electrostatic effects
predominate, particularly for weak bonds, but
that covalency effects increase in importance as
the strength of the bond increases. It is also
6 2
J. EMSLEY, O . P . A . HOYTE and R . E . OVERILL, J.
Soc, Chem. Commun., 2 2 5 ( 1 9 7 7 ) .
63
possible to apportion the energy obtained from
(63)
ab initio SCF-MO calculations in this w a y .
For example, in one particular calculation
for the water dimer HOH- · OH2, the five
energy terms enumerated above were calculated
tO be: £ l e c stat ~~ 26.5,
e £p uli +
a 18, iipolar ~ 2,
1
E h tr — 7.5, f d i s p O k J m o l " . There was also a
C
coupling interaction E \ — 0.5, making in all a
m x
total attractive force Δ £ = ^ d i m e r ~ ^ m o n o m e r s =
0
- 1
—18.5 kJ m o l . To calculate the enthalpy change
Δ/Υ298 as listed on p. 6 1 , it is also necessary to
consider the work of expansion and the various
spectroscopic degrees of freedom:
Δ//298 = £ o + A ( P V ) + A £ t r a n s + AE Vlb + Δ£ Γ Ο Ι
Such calculations can also give an indication of
the influence of Η-bond formation on the detailed
electron distribution within the interacting
components. There is general agreement that in
the system X - A - H - B - Y as compared with
the isolated species Χ Α Η and BY, there is a
net gain of electron density by X, A and Β and
a net loss of electrons by Η and Y. There is
also a small transfer of electronic charge (~0.05
(45)
electrons) from BY to Χ Α Η in moderately strong
1
Η bonds ( 2 0 - 4 0 kJ m o l " ) . In virtually all neutral
dimers, the increase in the A - H bond length on
Η-bond formation is quite small ( < 5 pm), the
one exception so far studied theoretically being
C1H- · NH3, where the proton position in the H
bond is half-way between completely transferred
to NH3 and completely fixed on HC1.
It follows from the preceding discussion that
the unbranched H bond can be regarded as a
3-centre 4-electron bond A - H · · Β in which
the 2 pairs of electrons involved are the bond
pair in A - H and the lone pair on B. The
degree of charge separation on bond formation
will depend on the nature of the proton-donor
group AH and the Lewis base B. The relation
between this 3-centre bond formalism and the
3-centre bond descriptions frequently used for
boranes, polyhalides and compounds of xenon
is particularly instructive and is elaborated in
Chem. 6 3
H . UMEYAMA and K . MOROKUMA, J. Am. Chem. Soc. 99,
1 3 1 6 - 3 2 (1977).
64
Figure 3.11 S c h e m a t i c representation o f the energy l e v e l s in various t y p e s o f 3-centre b o n d . T h e B - H - B ("elec­
tron deficient") b o n d is non-linear, the ("electron e x c e s s " ) F - X e - F b o n d is linear, and the A - H
h y d r o g e n b o n d can b e either linear or non-linear d e p e n d i n g o n the c o m p o u n d .
Fig. 3.11. Numerous examples are also known
in which hydrogen acts as a bridge between
metallic elements in binary and more complex
hydrides, and some of these will be mentioned in
the following section which considers the general
question of the hydrides of the elements.
3.7 Hydrides of the
Elements* " * 64 6
Hydrogen combines with many elements to
form binary hydrides MH* (or M H „ ) . All the m
main-group elements except the noble gases and
perhaps indium and thallium form hydrides, as
do all the lanthanoids and actinoids that have
been studied. Hydrides are also formed by the
more electropositive transition elements, notably
Se, Y, La, Ac; Ti, Zr, Hf; and to a lesser
6 4Κ . M . MACKAY, Hydrogen Compounds of the Metallic
Elements^ E. and F. N. Spon, London, 1966, 168 pp.;
Hydrides, Comprehensive Inorganic Chemistry, Vol. 1,
Chap. 2, Pergamon Press, Oxford, 1973.
6 5E. WIBERG and E. AMBERGER, Hydrides of the Elements
of Main Groups I-IV, Elsevier, Amsterdam, 1971, 785 pp.
6 6 W . M . MUELLER, J. P. BLACKLEDGE and G . G . LIBOWITZ
(eds.), Metal Hydrides, Academic Press, New York, 1968,
791 pp.
Hydrogen Ch. 3
•Β
extent V, Nb, Ta; Cr; Cu; and Zn. Hydrides of
other transition elements are either non-existent
or poorly characterized, with the spectacular
exception of palladium which has been more
studied than any other metal hydride s y s t e m . (67)
The situation is summarized in Fig. 3.12; this
indicates the idealized formulae of the known
hydrides though many of the d-block and f-block
elements form phases of variable compositions.
It has been customary to group the binary
hydrides of the elements into various classes
according to the presumed nature of their
bonding: ionic, metallic, covalent, polymeric, and
"intermediate" or "borderline". However, this is
unsatisfactory because the nature of the bonding
is but poorly understood in many cases and
the classification obscures the important point
that there is an almost continuous gradation
in properties — and bond types(?) — between
members of the various classes. It is also
somewhat misleading in implying that the various
bond types are mutually exclusive whereas it
seems likely that more than one type of bonding
is present in many cases. The situation is not
unique to hydrides but is also well known for
F. A. LEWIS, The Palladium-Hydrogen
6 7 System, Academic
Press, London, 1967, 178 pp.
§3.7 Hydrides of the elements
He
Figure 3.12 T h e hydrides o f the e l e m e n t s .
binary halides, oxides, sulfides, etc.: this serves
to remind us that the various bond models
represent grossly oversimplified limiting cases
and that in most actual systems the position
is more complex. For example, oxides might
be classed as ionic (MgO), metallic (TiO,
ReO^), covalent (CO2), polymeric (S1O2), or
as intermediate between these various classes,
though any adequate bonding theory would
recognize the arbitrary nature of these distinctions
which merely emphasize particular features of
the overall assembly of molecular orbitals and
electron populations.
The metals in Groups 1 and 2 of the periodic
table react directly with hydrogen to form
white, crystalline, stoichiometric hydrides of
formula MX and MX2 respectively. The salt-like
character of these compounds was recognized by
G. N. Lewis in 1916 and he suggested that they
contained the hydride ion H~. Shortly thereafter
65
(1920) K. Moers showed that electrolysis of
molten LiH (mp 692°C) gave the appropriate
amount of hydrogen at the anode; the other
hydrides tended to decompose before they could
be melted. As expected, the ionic-bond model is
most satisfactory for the later (larger) members of
each group, and the tendency towards covalency
becomes more marked for the smaller elements
LiH, M g H , and particularly B e H , which is best
2 2
described in terms of polymeric covalent bridge
bonds. X-ray and neutron diffraction studies
show that the alkali metal hydrides adopt the
cubic NaCl structure (p. 242) whereas MgH2
has the tetragonal T1O2 (rutile type) structure
(p. 961) and C a H , S r H and B a H adopt the
2 2 2
orthorhombic PbCh-type structure (p. 382). The
implied radius of the hydride ion H~ ( I s ) varies
2
considerably with the nature of the metal because
of the ready deformability of the pair of electrons
surrounding a single proton. Typical values are
66
given below and these can be compared with
r ( F " ) - 133 pm and r ( C l " ) - 184 pm.
Free H"
Compound M g H 2 LiH NaH KH RbH CsH (calculated)
r(H"Vpm 130 137 146 152 154 152 208
The closest M - M approach in these compounds
is often less than for the metal itself: this should
occasion no surprise since this is a common fea­
ture of many compounds in which there is sub­
stantial separation of charge. For example, the
shortest C a - C a interatomic distance is 393 pm in
calcium metal, 360 pm in CaH2, 380 pm in CaF2,
and only 340 pm in CaO (why?).
The thermal stability of the alkali metal
hydrides decreases from lithium to caesium, the
temperature at which the reversible dissociation
pressure of hydrogen reaches lOmmHg being
- 5 5 0 ° C for LiH, - 2 1 0 ° C for NaH and KH, and
~170°C for RbH and CsH. The corresponding
figures for the alkaline earth metal hydrides are
C a H 885°C, S r H 585°C and B a H 230°C,
2 2 2
though for MgH2 it is only 85°C. Chemical
reactivity depends markedly on both the purity
and the state of subdivision but increases from
lithium to caesium and from calcium to barium
with CaH2 being rather less reactive than LiH.
The reaction of water with these latter two
compounds forms a convenient portable source
of hydrogen, but with NaH the reaction is more
violent than with sodium itself. RbH and CsH
actually ignite spontaneously in dry air.
Turning next to Group 3, Fig. 3.12 indicates
that hydrides of limiting stoichiometry MH2 are
also formed by Se, Y, La, Ac and by most
of the lanthanoids and actinoids. In the special
11 7
case of E u H (Eu 4f ) and Y b H ( Y b 4 f ) the
2 2
n 14
hydrides are isostructural with CaH2 and the ionic
bonding model gives a reasonable description
of the observed properties; however, YbH2 can
absorb more hydrogen up to about YbH2.5. The
other hydrides adopt the fluorite (CaF2) crystal
structure (p. 118) and the supernumerary valence
electron is delocalized, thereby conferring
considerable metallic conductivity. For example,
LaH2 is a dark-coloured, brittle compound with
- 1 - 1
a conductivity of about 10 o h m c m ( ~ 1 % of
Hydrogen Ch. 3
that of La metal). Further uptake of hydrogen
progressively diminishes this conductivity to
1 - 1 - 1
< 10" o h m c m for the cubic phase L a H 3
1
(cf. - 3 χ l O ^ o h m ^ c n r for Y b H ) . The 2
other Group 3 elements and the lanthanoids and
actinoids are similar.
There is a lively controversy concerning the
interpretation of these and other properties, and
cogent arguments have been advanced both for
the presence of hydride ions H~ and for the
+
presence of protons H in the d-block and
(64,66)
f-block hydride p h a s e s . These difficulties
emphasize again the problems attending any
classification based on presumed bond type, and
a phenomenological approach which describes
the observed properties is a sounder initial basis
for discussion. Thus the predominantly ionic
nature of a phase cannot safely be inferred either
from crystal structure or from calculated lattice
energies since many metallic alloys adopt the
NaCl-type or CsCl-type structures (e.g. LaBi, β-
brass) and enthalpy calculations are notoriously
insensitive to bond type.
The hydrides of limiting composition MH3
have complex structures and there is evidence
that the third hydrogen is sometimes less strongly
bound in the crystal. For the earlier (larger)
lanthanoids La, Ce, Pr and Nd, hydrogen enters
octahedral sites and L n H has the cubic Li Bi 3 3
(57)
structure. For Y and the smaller lanthanoids
Sm, Gd, Tb, Dy, Ho, Er, Tm and Lu, as
well as for the actinoids Np, Pu and Am, the
hexagonal H0H3 structure is adopted. This is a
rather complex structure based on an extended
(68)
unit cell containing 6 Ho and 18 H a t o m s .
The idealized structure has hep Ho atoms with
12 tetrahedrally coordinated H atoms and 6
octahedrally coordinated H atoms; however, to
make room for the bulky Ho atoms, close pairs
of tetrahedral H atoms are slightly displaced and
there is a more substantial movement of the
"octahedral" H atoms towards the planes of the
Ho atoms so that 2 of the H atoms are actually in
the Ho planes and are trigonal 3-coordinate. The
6 8
M . M A N S M A N N and W . E . WALLACE J. de Physique 25,
4 5 4 - 9 (1964).
§3.7 Hydrides of the elements
hydrogen atoms are thus of three types having
respectively 14, 11, and 9 H neighbours for the
distorted trigonal, octahedral and tetrahedral sites.
Each H atom has 3 Ho neighbours at either 210
or 217 or 2 2 4 - 2 9 9 pm respectively, and each Ho
has 11 hydrogen neighbours, 9 at 2 1 0 - 2 2 9 pm
and 2 somewhat further away at 248 pm. The 3-
coordinate hydrogen is most unusual, the only
other hydride in which it occurs being the
complex cubic phase TI14H15.
Uranium forms two hydrides of stoichiometric
composition UH3. The normal β-form has a
complex cubic structure and is the only one
formed when the preparation is carried out
above 200°C. Below this temperature increasing
amounts of the slightly denser cubic α-form
occur and this can be transformed to the β-
phase by warming to 250°C. Both phases have
ferromagnetic and metallic properties. Uranium
hydride is commonly used as a starting material
for the preparation of uranium compounds as it is
finely powdered and extremely reactive. It is also
used for purifying and regenerating hydrogen (or
deuterium) gas.
The hydrides of Ti, Zr and Hf are characterized
by considerable variability in composition and
structure. When pure, the limiting phases MH2
form massive, metallic crystals of fluorite
structure (TiH ) or body-centred tetragonal
2
structure (ZrH , HfH , T h H ) , but there are
2 2 2
also several hydrogen-deficient phases of variable
composition and complex structure in which
several M - H distances o c c u r . ( 5 7 , 6 4
' 6 6 )
These
phases (and others based on Y, Ce and Nb)
have been extensively investigated in recent
years because of their potential applications as
moderators, reflectors, or shield components for
high-temperature, mobile nuclear reactors.
Other hydrides with interstitial or metallic
properties are formed by V, Nb and Ta; they
are, however, very much less stable than the
compounds we have been considering and have
extensive ranges of composition. Chromium also
forms a hydride, CrH, though this must be
prepared electrolytically rather than by direct
reaction of the metal with hydrogen. It has the
anti-NiAs structure (p. 555). Most other elements
67
in this area of the periodic table have little or no
affinity for hydrogen and this has given rise to the
phrase "hydrogen gap". The notable exception
is the palladium-hydrogen system which is
discussed on p. 1150.
The hydrides of the later main-group elements
present few problems of classification and are
best discussed during the detailed treatment of the
individual elements. Many of these hydrides are
covalent, molecular species, though association
via H bonding sometimes occurs, as already
noted (p. 53). Catenation flourishes in Group 14
and the complexities of the boron hydrides
merit special attention (p. 151). The hydrides of
aluminium, gallium, zinc (and beryllium) tend
to be more extensively associated via M - H - M
bonds, but their characterization and detailed
structural elucidation has proved extremely
difficult.
Two further important groups of hydride
compounds should be mentioned and will receive
detailed attention in later chapters. One is the
group of complex metal hydrides of which
notable examples are L1BH4, NaBH4, L1AIH4,
(69)
A1(BH4) , etc. 3 The other is the growing
number of compounds in which the hydrogen
atom is a monodentate or bidentate (bridging)
( 7 0 _ 7 3 )
ligand to a transition e l e m e n t : these date
from the early 1930s when W. Hieber discovered
[Fe(CO) H ] and [Co(CO) H] and now cover
4 2 4
an astonishing variety of structural types. The
modest steric requirements of the H atom enable
2-
complexes such as [ R e H g ] to be synthesized,
and bridged complexes such as the linear
[ C r ( C O ) H ] - and bent [ W ( C O ) H ( N O ) ] , are
2 10 2 9
2
known. For rç -H complexes see pp. 4 4 - 7 .
2
The role of hydrido complexes in homogeneous
catalysis is also exciting considerable attention.
6 9
A. HAJOS, Complex Hydrides, Elsevier, Amsterdam, 1 9 7 9 ,
398 pp.
7 0
J. C. GREEN and M . L . H . GREEN, Comprehensive Inor­
ganic Chemistry, Vol. 4 , Chap. 4 8 , Pergamon Press, Oxford,
1973.
7 1
H . D . KAESZ and R . B . SAILLANT, Chem. Rev. 72, 231 - 81
(1972).
7 2
A. P. HUMPHRIES and H . D . KAESZ, Progr. Inorg. Chem.
25, 145-222 (1979).
7 3
G . L . GEOFFROY, Progr. Inorg. Chem. 2 7 , 1 2 3 - 5 1 ( 1 9 8 0 ) .