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HYDROGEN

Learning Outcomes

Describe different ways of producing hydrogen.

Use chemical reactions to demonstrate clear understanding of the

industrial production of hydrogen.

Use chemical equations to illustrate the chemical properties of

hydrogen.

Illustrate and differentiate between ionic, covalent and interstitial

hydrides.

Explain the conditions required to produce atomic hydrogen and the

bare proton, indicating their uses and importance industrially.

Position in the Periodic Table

Hydrogen is the first element in the periodic table and is represented by

the symbol H.

Hydrogen, contains only one proton and one electron, and it is the
simplest element.

It is usually placed in Period 1 and Group 1 of the periodic table.

The proton is the center, or nucleus, of the hydrogen atom, and the
electron travels around the nucleus.

Pure hydrogen exists as hydrogen gas, in which pairs of hydrogen

atoms bond together to make molecules.

Hydrogen- continued

Hydrogen Production Processes

Steam Methane Reforming
Electrolysis
Thermochemical
Laboratory Preparation of H2 Gas

In the laboratory, H2 gas can be prepared by the action of dilute acids on

many metals.

A convenient reaction is that between zinc and dilute HCl:

Zn(s) + 2HCl(aq)

ZnCl2(aq) + H2(g)

Steam Methane Reforming (SMR)

Most common method of producing commercial bulk hydrogen.

Most common method of producing hydrogen used in the industrial

synthesis of ammonia.

It is the least expensive method.

High temperature process (700 1100 C).

Nickel based catalyst (Ni)

At 700 1100 C and in the presence of a nickel based catalyst (Ni),

steam reacts with methane to yield carbon monoxide and hydrogen.
CH4 + H2O CO + 3H2

Additional hydrogen can be recovered by a lower-temperature gas-shift

reaction with the carbon monoxide produced. The reaction is summarized
by:
CO + H2O CO2 + H2

Purification of Hydrogen

Carbon dioxide and other impurities are removed from the gas
stream, leaving essentially pure hydrogen.

Endothermic reaction (Heat must be added to the reactants for the

reaction to occur.)
Schematic of the Steam Methane Reforming Process
H2O

Water
Methane
Ethanol
Methanol

10%
CO

REFORMER

2,000ppm
CO

WATER GAS SHIFT

REACTOR

<100ppm
CO

REMOVAL OF CO
AND CO2

H2

FUEL CELL
STACK

O2

The Separation of CO2 from H2 Gas

The CO2 can be separated from H2 gas in several ways:
The products are cooled below the condensation temperature of
CO2 (-78C) which is much higher than that of H2 (-253C).
Passage of the gas mixture through a solution of K2CO3. CO2 is an
acid oxide. One mole of CO2 reacts with an excess of carbonate
ion and water to give two moles of the hydrogen carbonate ion:
CO2 + CO32- + H2O

2HCO3-1

When the reaction is complete, the KHCO3 solution can be removed

and heated to regenerate the K2CO3, while the pure CO2 gas can be
collected and pressurized:

K2CO3(aq) + CO2(g) + H2O(l) 2KHCO3(aq)

The Separation of CO2 from H2 Gas - contd

For most purposes the purity of H2 obtained from thermochemical

processes is satisfactory.

Very pure H2 gas is generated by an electrochemical route, the

electrolysis of NaOH or KOH solution.

The reaction produces O2 gas at the anode and the H2 gas at the
cathode:

Cathode: 2H2O(l) + 2e-

Anode: 3H2O(l)

2HO-(aq) + H2(g)
2H3O+(aq) + O2(g) + 2e-

Electrolysis
Electrolysis is the technical name for using electricity to split water into
its constituent elements, hydrogen and oxygen.
The splitting of water is accomplished by passing a DC electric current
through water.
The electricity enters the water at the cathode, a negatively charged
terminal, passes through the water and exits via the anode, the
positively charged terminal.

The hydrogen is collected at the cathode and the oxygen is collected

at the anode. Electrolysis produces very pure hydrogen for use in the
electronics, pharmaceutical and food industries.

Electrolysis- continued
Electrolysis: Splitting water with electricity to produce H2 and O2

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Theoretical Enthalpy Cycle for the Formation of Water

The Chemical Reactions of H2

The Reaction of H2 with halogens decreases down the group.

It has a violent reaction with F2 to give HF:

H2(g) + F2(g)

The reaction of H2 with N2 is very slow in the absence of a catalyst:

3H2(g) + N2(g)

2NH3(g)

At high temperatures many metal oxides are reduced by H 2 to the

metallic element:
CuO(s) + H2(g)

2HF(g)

Cu(s) + H2O(g)

In the presence of a catalyst ( Pd or Pt) H2 reduces carbon-carbon

double and triple bonds to single bonds:
H2C=CH2(g) + H2(g)

H3C-CH3(g)

Properties of hydrogen
H2 is a colourless odourless gas.
H2 is sparingly soluble in water and the solubility is not much affected
by change of temperature.
H forms compounds with a large number of elements.
Chemically, hydrogen reacts with most elements.
H2 liquefies at -253 C and solidifies at -259 C.

Chemical Properties of hydrogen - continued

In the presence of a catalyst H2 reduces carbon-carbon double and

triple bonds to single bonds:

Hydrides

Binary compounds of hydrogen are given the generic name of hydrides.

Hydrogen which forms binary compounds with most elements has an EN

only slightly above the median value of all the elements in the periodic
table.

H element thus behaves as a weakly electronegative non-metal, forming

ionic compounds with very

electropositive metals

and covalent

compounds with non-metals.

The theoretical enthalpy change in the formation of HCl from H2 and Cl2
is as follows:

Cl2(g) +121 kJ.mol -1 Cl(g) + e--369 kJ.mol Cl-(g)

-1

H2(g) +218 kJ.mol -1 H(g) +

-1
e- -69 kJ.mol

H-(g)

H overall = -248 kJ.mol -1

H overall = +149 kJ.mol -1

Hydrides contd
The H-H bond is much stronger than the Cl-Cl bond.
There is a much lower electron affinity of hydrogen than chlorine.
The anion formation for the hydride ion is significantly positive whereas for
chloride is very negative.
Based on the above information only a cation with a very low ionization
energy (such as those of alkali metals) will enable the net enthalpy
change for the hydride formation to be negative.
The hydride ion is a strong reducing agent which reduces water to H 2 gas:
CaH2(s) + H2O(l)

Ca(OH)2(s) + H2(g)

Covalent Hydrides

Hydrogen forms compounds containing covalent bonds with all the nonmetals (except noble gases) and with very weakly electropositive metals
such as gallium and tin.

There are three subcategories of covalent hydrides:

Those in which the H atom is nearly neutral.

Those in which the hydrogen atom is substantially positive.

Those in which the hydrogen atom is slightly negative, including the

electron-deficient boron compounds.

For the first category, because of their low polarity, the sole
intermolecular force between neighbouring hydride molecules is
dispersion force.

Covalent Hydrides - contd

These covalent hydrides are gases with low boiling points.

Typical examples of these hydrides are hydrogen selenide(H 2Se) and

phosphine (PH3) with the boiling points of -60 C and -90 C respectively.

The largest group of near-neutral covalent hydrides contains carbon

the hydrocarbons.

They comprise of alkanes, alkenes, alkynes and the aromatic

hydrocarbons.

All the hydrocarbons are thermodynamically unstable toward oxidation,

e.g. CH4(g) + 2O2(g)

CO2(g) + 2H2O(g)

Covalent Hydrides - contd

Ammonia,
fluoride

water
belong

and
to

hydrogen

the

second

category of covalent hydrides.

These compounds contain positively

charged hydrogen atoms.

They differ from the other covalent

hydrides due to their abnormally high
melting and boiling points.

The positively charged hydrogen in

these compounds is attracted by an
electron pair on another atom to form
hydrogen bond.

Covalent Hydrides - contd

The third category of hydrides in which hydrogen is slightly negative

includes diboranes (B2H6), silane (SiH4), germane (GeH4) and stannane
or tin(IV)hydride (SnH4).

These monomeric hydrides react violently with O2 e.g.:

SnO4(g) +O2(g)

A partially negative hydrogen (a hydridic hydrogen) is much more

SnO2(g) + 2H2O(l)

reactive than a partially positive hydrogen atom.

Metallic (d-Block) Hydrides

Some transition metals form metallic hydrides.

These compounds are often non-stoichiometric, for example, the

highest hydrogen-titanium ratio has been found in a compound with the
formula TiH1.9.

The nature of these compounds is complex.

Titanium hydride is believed to consist of (Ti4+)(H-)1.9(e-)2.1.

It is the free electrons that account for the metallic lustre and high
electrical conductivity of these compounds.

The density of the metal hydride is often less than that of the pure
metal because of structural changes in the metallic crystal lattice.

These compounds are usually brittle.

Metallic (d-Block) Hydrides - contd

The electrical conductivity of the metallic hydrides is generally lower

than that of the parent metal.

Most metallic hydrides can be prepared by warming the metal with

hydrogen under high pressure.

At high temperatures, the hydrogen is released as H 2 gas.

A major use of a metal hydride is in the nickel metal hydride batteries

that are used in portable computers, cordless vacuum cleaners, cellular
phones and many other cordless electrical devices.

A metal hydride battery is made up of a metal alloy that reversibly

absorbs and releases hydrogen at ambient temperatures.

Metallic (d-Block) Hydrides - contd

These hydrogen-absorbing alloys combine metal A, whose hydride

formation is exothermic with another metal B, whose hydride formation is
endothermic.

The alloys exist as four possible ratios; namely, AB (e.g. TiFe), AB 2 (e.g.
ZnMn2), AB5 (e.g. LaNi5) and A2B (e.g. Mg2Ni).

Metal combinations should give an essentially energy-neutral hydride

formation.

Combinations such as TiNi2 and LaNi5 are best suitable for the function.

Metallic (d-Block) Hydrides - contd

Ni(II) hydroxide is oxidized to Ni(III)oxide hydroxide at the anode in the

cell.

Water is reduced to hydrogen atoms at the cathode which are then

absorbed into the metal alloy:

Anodic reaction: Ni(OH)2(s) + HO-(aq)

Cathodic reaction: [Ni-alloy]- + H2O(l) + e-

NiO(OH)(s) + H2O(l) + e[Ni-alloy]H + HO-(aq)

Water and Hydrogen Bonding

Water is supposed to be a gas at the

common range of temperatures when
compared to the other hydrides of
chalcogens (Group VI elements).

Hydrogen bonding results in a very

rare property of water.

If H2O molecules were not bound to

one another by hydrogen bonds, the
H2Os liquid range would be between
-90 C and -100 C.

Water and Hydrogen Bonding - contd

The liquid phase of water is denser than the
solid phase - the rare property of water.
For most substances the molecules are
closely packed in the solid phase than in the
liquid phase resulting in higher density of
solids than liquids.

A solid is therefore expected to settle at the bottom as it starts to

crystallise from the liquid phase.

In subzero temperatures, a layer of ice forms over the surface keeping the
water beneath in the liquid phase in dams, rivers, lakes or oceans.

The open structure of ice due to the network of H-bonds causes this
abnormality of ice.

Water and Hydrogen Bonding - contd

On the melting of ice some of the hydrogen bonds are broken and the
open structure collapses.

This change increases the liquids density.

The density reaches a maximum at 4 C.

Above 4 C the increase in density due to the collapsing of the

hydrogen-bonded clusters of water molecules is overtaken by the
decrease in density due to the increasing molecular motion resulting
from the rise in temperature.

Water and Hydrogen Bonding - contd

Phase diagram can also be used to study the

unusual behaviour of water.

A phase diagram shows a thermodynamically

stable phase of an element or compound with
respect to pressure and temperature.

Diagram A is an idealised phase diagram.

The regions between the solid lines represent the

phase that is thermodynamically stable under
those particular combinations of pressure and
temperature.

At 100 kPa the standard melting and boiling

points can be determined by considering phase
changes.

Water and Hydrogen Bonding - contd

A horizontal dashed line is projected from the point

of standard pressure.

The temperature at which the dashed line crosses

the solid-liquid boundary is the melting point.

The temperature at which the dashed line crosses

the liquid-gas line is the boiling point.

For almost all substances, the solid-liquid line has

a positive slope.

This trend means that application of a sufficiently

high pressure to the liquid phase will cause the
substance to solidify.

Water and Hydrogen Bonding - contd

Phase

diagram

illustrates

the

abnormal

behaviour of water based on the density of ice

being lower than that of liquid water.

Le Chteliers principle indicates that the denser

phase is favoured by increasing pressure.

Application of pressure to the less dense solid

phase of water causes it to melt to the denser
liquid phase.

END OF LECTURE