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); H = + 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.

Hydrogen - Preparation of molecular hydrogen H

Laboratory: 1) electrolysis of water 2H2O(l) 2H2(g) + O2(g) H = +572kJ 2) action of dilute H+ on active metals such as Zn, Cu 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 (1000C, 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) H = -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 = 2,500C Proposals to overcome this limitation:
1. 2. 3.

Zn + H2O (l) ZnO + H2(g) T = 350C.Zn is obtained from ZnO (mined) using solar energy! Conversion of solar radiation to electricity in photovoltaic cells followed by electrolysis of water in a separate cell. 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, onboard storage of hydrogen is a more difficult challenge. Proposals to overcome this limitation 1. threedimensional 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

2M(s) + H2 2MH(s) 300 -700C where M = Li-Cs and Ca-Ba

These are white, crystalline stoichiometric hydrides with considerable ionic character (increases down the group). They contain M+ and 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
1.

These include: Neutral hydrides like XH4 cmpds of grp 14 such as CH4, SiH4 and all hydrocarbons Basic hydrides like the XH3 cmpds of group 15 NH3 and PH3, AsH3, SbH3, BiH3 Weakly acidic or amphoteric XH2 cmpds fo grp 16 such as H2O and H2S Strongly acidic hydrides like HX cmpds of grp 17 such as HI, HCl, HBr Hydridic complexes of hydrogen such as LiAlH4 and NaBH4 Numerous covalent hydrides of boron (borane B2H6, tetraborane B4H10, pentaborane B5H11

2.

3.

4.

5.

6.

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-HY
Electronegative element Electronegative 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.
There are small spaces (interstices) which contain water molecules that disturb the network this makes water slightly denser than ice.

c.

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.