Hydrogen and its compound

1. Discuss the implications of the position of hydrogen in the

periodic table.

2. Discuss the the ortho and para forms of hydrogen.

3. Discuss the industrial preparation of hydrogen, the existence of

its various atomic and molecular forms and its potential as an
alternative fuel.

4. Describe the anomalous properties of water, the various

structures with which it is associated and the formation of
hydrogen bonds using hydridic compounds.

5. Describe the occurrence, properties and uses of some hydrides of

selected main group metallic and non-metallic elements.
Hydrogen
 H2(g) → 2H(g); ΔH = + 436 kJ/mol (high activation energy – relative
unreactivity of hydrogen at rt)
 3 isotopes - 1H (protium H), 2H (deuterium D), 3H (tritium T)
 Melting and boiling points of D2O higher than that of H2O
 Density of D2O also higher than that of H2O
 The implications of H2 in the periodic table (see slide on reactivity)

Nuclear Spin Isomerism –

 ortho-H2 : () parallel nuclear spins, S = 1, 2S+1 = 3 three fold
degenerate- hence triplet.

 para-H2 : () anti-parallel spins, S= 0, 2S + 1 = 1

non-degenerate-hence called singlet.

 Conversion b/w two states is slow unless catalysed

 para-H2 has lower energy so is favoured at low T.
 At rt ratio of ortho:para is 3:1
Hydrogen - Preparation of molecular hydrogen H 2

 Laboratory:
1) electrolysis of water
2H2O(l) →2H2(g) + O2(g) ΔH  = +572kJ
2) action of dilute H+ on active metals such as Zn or Fe
Zn(s) + 2H+(aq) → H2(g) + Zn2+ (aq)
3) Also hydrolysis of metal hydrides:
MH(s) + H2O(l) → H2(g) + MOH(aq)

 Industrial: steam hydrocarbon reforming -

CH4 + H2O  CO + 3H2 (1000C, Ni catalyst)
Mixture of CO and H2 is called ‘synthesis gas or syngas”

Water-gas shift reaction can increase the proportion of H2

CO + H2O  CO2 + H2 (400 iron chromate catalyst)
Hydrogen
Uses of H2
 N2 + 3H2 →2NH3 (Haber Process)
 CO + 2H2 →CH3OH (Syn of methanol)
 C=C + H2 →C-C (catalytic hydrogenation of
unsaturated vegetable oils to solid edible fats)

.
HYDROGEN as a FUEL –
“The Hydrogen Economy”

In the hydrogen economy, hydrogen fuel cells would replace internal

combustion engines in vehicles, and hydrogen would replace gasoline.
Energy is transported or stored in the form of solid, liquid or gaseous
hydrogen

 ADVANTAGES:
-greater energy release per unit weight of fuel
 Heat liberated when H2 burns is more than twice that of gasoline, oil or
natural gas on a mass basis
2H2(g) + O2(g) → 2H2O(l) ΔH  = -242 kJ (ie. 121 kJ/g)

-absence of polluting emissions CO, CO2, SO2 product of combustion is H2O

+ small amts of nitrogen oxides
-source of hydrogen is inexhaustible with no ecological upheaval
see 2H2O(l) →2H2(g) + O2(g)
-other by product of H2 production by electrolysis is O2 which has numerous
applications

LIMITATIONS AND HOW TO OVERCOME LIMITATIONS:

 Major Limitations to Hydrogen
Economy: Steps to Overcome them
Production
Not Economically Viable:2H2O(l) →2H2(g) + O2(g)
Electrolysis is not thermodynamically favourable and
thermolysis requires too much energy !
T = 2,500°C
Proposals to overcome this limitation:
1. Zn + H2O (l) → ZnO + H2(g) T = 350°C.Zn is obtained from
ZnO (mined) using solar energy!
2. Conversion of solar radiation to electricity in photovoltaic cells
followed by electrolysis of water in a separate cell.
3. MOST RECENT DEVELOPMENT: Microbial Fuel Cell (action of
bacteria on any biodegradable, dissolved, organic matter -
human, agricultural or industrial wastewater quadruple hydrogen
production!
 Major Limitations to Hydrogen
Economy: Steps to Overcome them
Storage
Two possible ways of storing H2 are in cryogenic systems as
a liquid or in pressurized cylinders as a gas.
This is limited for some practical applications especially
transportation.
For transportation use, on−board storage of hydrogen is a
more difficult challenge.

Proposals to overcome this limitation

1. three−dimensional solids with open structures in which
H2 or atoms can be adsorbed on internal surfaces.
2. pores in carbon nanotubes.
3. interstitial hydrides.
Reactivity of hydrogen
3 Electronic Processes Govern the Chemistry of Hydrogen

1. Loss of electron to form H+ (similar to alkali metals)

 H(g) →H+(g) + e-Ei = +1312 kJ/mol (acidic H compounds eg???)

2. Gain an electron to form H- (similar to halogens)

 H(g) + e- →H-(g) Eea = -73 kJ/mol (hydridic H compounds eg.???)

3. Formation of an electron-pair bond in covalent cmpds (H·)

 CH4, NH3, H2O, HF (neutral H compounds)

Discuss the implications of the position of H in the periodic table.

Unique bonding features –

 H-bridged bonds in electron deficient cmpds such as B2H6 (diborane)
(see structure and explain bonding in diborane, do on the board)
 Formation of hydrogen bonds
Hydrides – while all H containing cmpds are termed hydrides not all such
compounds display “hydridic” character. (hydridic: react as or contain H-)
Objective 5

Hydrogen combines with many elements to form binary

hydrides – (contain H and one other element)

 Hydrogen gains an electron to form ionic hydrides containing H-

(s-block elements except Be and Mg) called saline hydrides.

 Hydrogen shares electrons in the covalent hydrides (p-block

elements)

 Hydrogen is involved in metallic bonding in the interstitial or

metallic hydrides (transition metals)
 Saline (salt-like) hydrides

These are white, crystalline stoichiometric

 2M(s) + H2  2MH(s) hydrides with considerable ionic character
300 -700C (increases down the group). They contain M+ and
where M = Li-Cs and Ca-Ba H- ions. LiH to CsH have NaCl (rock salt)
structure while CaH2 to BaH2 have PbCl2 structure.

 They are very reactive, reactivity increases down the grp

 They react with water to form the metal hydroxide and H2
MH(s) + H2O(l) →H2(g) + MOH(aq)

(H- is a powerful base hence saline hydrides are very

good reducing agents or H transfer agents )
 Covalent hydrides

 These include:
1. Neutral hydrides like XH4 cmpds of grp 14 such as CH4, SiH4
and all hydrocarbons

2. Basic hydrides like the XH3 cmpds of group 15 NH3 and PH3,
AsH3, SbH3, BiH3

3. Weakly acidic or amphoteric XH2 cmpds fo grp 16 such as H2O

and H2S

4. Strongly acidic hydrides like HX cmpds of grp 17 such as HI,

HCl, HBr

5. Hydridic complexes of hydrogen such as LiAlH4 and NaBH4

6. Numerous covalent hydrides of boron (borane B2H6,
tetraborane B4H10, pentaborane B5H11
 Hydrogen Bonds

 A H-bond is an attractive interaction

between a hydrogen atom bonded to a
very electronegative atom (O, N, F, Cl)
and an unshared electron pair on
another electronegative atom.

X-H··Y

Electronegative
Electronegative element
element
Hydrogen bond
 Hydrogen Bonds

Consider the boiling

points of group 14
hydrides

Consider the bp of group

15, 16 and 17 hydrides

Explain!
 Importance of H-bonds seen
in :
Structure and properties of water and ice
Double helix structure of DNA
Crucial three dimensional shape of large
proteins and enzymes
Life as we know it could not exist
without H-bonds
Hydrogen Bonds in DNA
 Structure of water and ice

Over 9 known modifications to the structure of ice.

Most of the ice in the biosphere exist as the hexagonal form.
Key features: water molecules arrange in hexagonal rings with O atoms at the
vertices and the sides formed by H-bonds. The results in an open framework
and makes ice less dense than water (see structure of water on next slide).
Structure of water and ice

The structure of water is similar to

that of ice and differs in the
following ways:
a. The H-bonds are dynamic,
breaking and reforming.
b. The H-bonded network does not
extend over long distances
without breaks.
c. There are small spaces
(interstices) which contain water
molecules that disturb the
network – this makes water
slightly denser than ice.
 Anomalous properties of water
 High surface tension.
 Capillary action.
 High boiling point and latent heat
of vaporization .
 High freezing and melting points.
 Water expands on freezing.