SSCC 1703

INORGANIC CHEMISTRY

HYDROGEN
Hydrogen
 Hydrogen
3rd most abundance element on the surface of the
earth
• In the form of H2O, and organic substances
• Essential element in animal and plant
• Element in the sun, many stars and variety of
nebulae
• Produced from hydrocarbon or water
• Combustion of H for fuel convert back to H2O
Meaning of Hydrogen
HYDRO = water, GENES=form
Hydrogen = forming water
 Hydrogen
Discovery:
• Henry Cavendish > A. Lavoisier
Physical Properties:
• e- configuration - 1s1
• AMU = 1.0079
• m.p = -259.1oC b.p = -252.720 °C
• Density = 0.08988 g L-1 (gaseous phase)
= 70.8 gL-1 (liquid)
= 70.6 gL-1 (solid)
• Colorless gas, does not smell and tasteless
• Does not dissolve in water (only 2% v/v , 0 °C)
 Ortho Para Hydrogen
• The proton, which forms the nucleus of protium, has spin I
= 1/2 (measured in units of h/2p)

• In the H2 molecule, the two nuclei can have their spins

– parallel (ortho hydrogen)
– antiparallel (para hydrogen)
to each other

ORTHO PARA
 Ortho Para Hydrogen
• Transitions between the ortho and para states are
theoretically forbidden, but in practice they occur very
slowly

• At the temperature of liquid air (~ 80 K) the molecules

are in their lowest rotational energy state and para
hydrogen is the form thermodynamically favored.

• At higher temperatures increasing amounts of ortho

hydrogen are present in the equilibrium mixture to the
limiting……
At 20°C : ratio 3 ortho : 1 para
 Ortho Para Hydrogen

Ortho hydrogen Para hydrogen

At room 75% 25%

temp.
stability more stable less stable

•Different physical properties

•Similar chemical properties.
 Isotopes of hydrogen
%
Isotope Symbol AMU
Abundance
Hydrogen/ 1H 1.008 99.04
Protium
Deuterium 2H (D) 2.0150 0.0156
Tritium# 3H (T) 3.0178 10-17
#Tritiumis radioactive (t1/2 = 12.26 years) decay
into 3He with b- radiation

3 H à He + b-
3
 Position of Hydrogen
in the Periodic Table
• lightest element known having atomic number 1.
• Dihydrogen
• The position of hydrogen is anomalous in periodic table

Alkali metals Halogens

• In modern periodic table it is located in first group.

 Resemblance with
Alkali Metals
1. Electronic configuration
1
1 H = 1s
2 2 6 1
11 Na = 1s , 2s , 2p , 3s
2 2 6 2 6 1
19 K = 1s , 2s , 2p , 3s , 3p , 4s

2. Electropositive character
H+, Na+, K+ etc.

3. Oxidation state: +1
 Resemblance with
Halogens
1. Electronic configuration:
Both contain one electron less than the nearest noble gas
configuration
1 H = 1s1
(near to 2He )
9 F = 1s2
, 2s2
, 2p 5
(near to 8 Ne )
17 Cl = 1s 2
, 2s 2
, 2p 6
, 3s2
, 3p5
(near to 18 Ar )
2. Non-metallic character:
Typical non-metals.

3. Atomicity:
Diatomic molecules.
 Resemblance with
Halogens
4. Formation of similar types of compounds:
i. Halides: CCl4, SiCl4, GeCl4
ii. Hydrides: CH4, SiH4, GeH4

5. Oxidation state: –1
+1 -1 +1 -1
Na H Na Cl
 Preparation of
Hydrogen
In laboratory

i) Reaction of metal ( Zn, Fe, Cu) with diluted acids

Zn(s) + 2HCl(aq) à ZnCl2(aq) + H2(g)

Hydrogen is collected by replacement of water

ii) Electrolysis of Water (adding a small amount of H+)

Cathode : 2H2O(l) + 2e- à H2(g) + 2OH-(aq)
Anode : 2H2O(l) à O2(g) + 4H+(ak) + 4e
 Preparation of
In industry
Hydrogen
By ‘STEAM REFORMING PROCESS’ using hydrocarbon
or coal 1

H2O (steam)
CH4 CO + H2
900oC, Ni
(Syn gas or water gas)

2
H2O (steam)
CO2 + H2
400oC, Cu/Fe
3
K2CO3
H2O H2
4 D
KHCO3
15
 Preparation of
Hydrogen
In industry
By ‘STEAM REFORMING PROCESS’ using hydrocarbon
or coal

What is the major advantage of producing H2 using this

method?

What about the biggest drawback?

 Preparation of
In industry
Hydrogen
By ‘STEAM REFORMING PROCESS’ using hydrocarbon
or coal

What is the major advantage of producing H2 using this

method?
Cheap.

What about the biggest drawback?

Major by products: CO, CO2 and greenhouse gases.
 Preparation of
Hydrogen: Industrial
1. Steam Reforming

Ni
CH4(g) + H2O(g) CO(g) + 3H2(g)
900oC
2. Water Gas Shift

Cu
CO(g) + H2O(g) CO2(g) + H2(g)
400oC
3. CO2(g) + H2O + K2CO3 à 2KHCO3

4. 2KHCO3 è K2CO3 + H2O + CO2

D
3 molecules of H2 are obtained from step #1 and 1 molecule from step
#2. Step #3 and step #4 show how the feedstock are generated back
to go through step #1 and #2 again. (so that it will be continuous)
 Major Uses of Hydrogen
(Industrial Processes)
1. Production of NH3 ( Haber Process ), fertilizers, plastics

Fe
3H2(g) + N2(g) 2NH3(g) - Haber Process
400-500oC

2. Methanol Production (Feed stock)- Steam reforming

Cr
2H2(g) + CO(g) CH3OH(l)
300oC, 300 atm

3. Production of margarine -Hydrogenation of unsaturated oil

H2

C=C Ni C- C
 Major Uses of Hydrogen
(Industrial Processes)

4. Production of Metals – Reduction process

H2(g) + MO (s) à Pb(s) + H2O(l)

(M= Pb, Ni, Co, Mn)

5. As Fuel.
 Chemistry & Special
Properties of Hydrogen

When undergoing chemical reaction, atomic H can

i. Lose electron à H+ (proton, hydrogen ion)
ii. Gain electron à H- (hydride)
iii. Share a pair of electron with other atom à covalent bond
 Chemistry & Special
Properties of Hydrogen
Reaction of Hydrogen
1. Combustion
2H2(g) + O2(g) à 2H2O DH = - 572 kJ
release high energy è use in wielding, fuel, bomb
2. Reducing agent
Reduce oxide of weak electropositive metals
H2(g) + MnO2(s) à MnO(s) + H2O(l)
H2(g) + PbO (s) à Pb(s) + H2O(l)
(M= Pb, Ni, Co, Mn)
 Chemistry & Special
Properties of Hydrogen
Cont: Reaction of Hydrogen
3. React with other more electronegative elements
H2(g) + X2(g) à 2HX
4 React with more electropositive elements à forming
hydride
H2(g) + Na(s) à NaH
5. Homolytic dissociation
H2 à 2 H (atomic)
takes place at high temperature with the help of Pt or Ni
catalyst. Use for hydrogenation of alkenes,
reduction of aldehyde à alcohol
 Chemistry & Special
Properties of Hydrogen

Cont: Reaction of Hydrogen

6. Heterolytic dissociation- induced by metal oxide (ZnO/Al2O3)
as catalyst.
7. Radical Chain Reaction – induced by heat or light
 Special Properties
of Hydrogen
Due to small size
1. Hydrogen tends to form covalent bond with other
element except those of very electropositive metals
2. Shorter and strong covalent bond

Element Bond energy/kJ mol-1 Bond length/nm

H-X C-X H-X C-X
H 440 0.07
C 410 350 0.11 0.15
Cl 430 340 0.13 0.18
Br 370 280 0.14 0.19
O 460 360 0.095 0.14
N 390 300 0.10 0.15
 Special Properties
of Hydrogen
3. Show anomaly:
– Form interstitial hydrides with transition metals,
lanthanide and actinide
e.g. LaH 2.87, TiH 1.7

– Hydrogen will participate in three-center bonds, forming

bridging hydrogen bonding
e.g. boron hydride

H H H

B B
H H H
 Special Properties
of Hydrogen
- Form unusual attractive force called ‘hydrogen bonding’
- When coupled to a highly electronegative atom (F, O or N)
eg : water

d+ H Hd+
d-O
H
d+ d-
d+ H H O
H
d-O

d+ H d-
O
H
Structure of ice, hexagonal structure
 Special Properties
of Hydrogen
Detection of Hydrogen Bond:
Abnormal melting and
boiling points

Hydride of N (HN3), O (H2O) and F

(HF) do not follow the order of
increasing boiling point with
increasing molecular weight

More energy/heat is required

to break down the hydrogen
bond between the molecules
à higher melting/boiling point
 Problem
• Is there Hydrogen bond in the following
molecules:
CH3COOH
NaH
HCl
H2SO4
 Effect of Hydrogen
Bond
• Unexpectedly high molecular weights of
hydrogen-containing species are often due to
hydrogen bonding. For example, many
carboxylic acids are dimeric both in
hydrocarbon solvents and in the vapor state:

O H O
R C C R
O H O
 Effect of Hydrogen
Bond
• Solubility
Occur when the molecule of the solvent bonded to the solute
through hydrogen bond.
e.g.
H2O – polar molecule having partial charge d+(H) and d-(O).

Any ionic or polar molecules will attract terminal d+(H) and

d-(O) from water and form hydrogen bonding à dissolve
e.g. ethanol , CH3CH2OH (polar) dissolve in water

Any non polar molecule (eg: chloromethane, CH3CH2Cl)

insoluble (does not dissolve) in water
 Effect of Hydrogen
Bond
• Density of the solid is less than in liquid
due to its larger volume as crystallization takes
place.
e.g.
ice (solid H2O) floats in water (liquid H2O)
due to its open crystal structure having larger
volume
Density of water: 1.0 g/cm3
Density of ice : 0.9167 g/cm³ .
 Compound of
Hydrogen - HYDRIDES
Compounds of hydrogen are classify as
– Ionic Hydride (H-) – Saline Hydride
– Covalent hydride (H•, or H+)
– Nonstoichiometric hydrides (interstitial
compounds)

H may be bound in its compounds essentially as (or

serve, on reaction, as a source of) H-, H•, or H+,
respectively
 Classification of the
binary hydrogen (H-X)
compounds
 Ionic Hydride
(Saline Hydride)
• Compound of H bonded to highly electropositive
elements
• Hydride of alkali metal (LiH, NaH, KH, RbH and
CsH)
• Hydrides of alkali earth metal (CaH2, SrH2, BaH2)
• The hydride of heavier metals contains metal cations
Mn+ and H- ion.
• Hydrides of Be and Mg (Group II) an Li(Group I)
have more covalent character due to the small size
and high charge density of the ions
 Cont: Ionic Hydrides
• The saline hydrides are ionic substances, as
shown by the facts that
ü They conduct electricity when molten, and
ü When dissolved and electrolyzed in molten halides, the
saline hydrides evolve H2 at the anode (positive electrode),
where oxidation of H- takes place. This proved that H is in
the form of anionic H-
Reaction of ionic hydrides
• Quite reactive with water and air to give base with evolve H2
MH(s) + H2O(l) à H2(g) + MOH(aq)
• Powerful reducing or hydrogen-transfer agents
NaH + ROH à NaOR + H2
4NaH + TiCl4 à Ti + 4NaCl + 2H2
 Covalent Hydride
(molecule)
• Compounds of H with non metal element on the
right hand side of The periodic table
The covalent hydrides include
• Neutral, binary XH4 compounds of Group IVA(14)
e.g: CH4.
• Somewhat basic, binary XH3 compounds of Group VA(15).
E.g. NH3, and PH3,
• Weakly acidic or Amphoteric, binary XH2 compounds of
Group VIA(16),
E.g:, H2S and H2O.
• Strongly acidic, binary HX compounds of Group VIIA(17).
E.g.: HCl and HI.
 Covalent Hydride
• Numerous covalent hydrides of boron
e.g. BnH2n

• Hydridic, complex compounds of hydrogen

e.g.: LiAlH4 and NaBH4,
Al - H and B - H bonds in these
substances are essentially covalent in nature.
 Water (Covalent Hydride)
• The most abundant and important substance in
earth

• Show anomalous behaviour because of

HYDROGEN BONDING even in vapour phase.

• Stable towards thermal decomposition due to high

O-H bond energy (460 kJ mol-1)

• Lewis structure:
 Water
Important reactions:
• Self ionization
H2O + H2O H3O+ + OH-
Kw = [H3O+] [OH-] = 1.0 x 10-14
• Element:
ü Electropositive: liberate H2 from cold, hot and vapor H2O
ü Halogen: hydrolyzed to HX or HOX (in cold)
ü metallic oxides: soluble basic oxides when dissolve in water à
basic hydroxides (hydrolysis of O2-)
O2- + H2O à 2OH-
CaO, BaO, Na2O à Ca(OH)2, Ba(OH)2, NaOH
ü Nonmetallic oxides when dissolve in water: à acidic solution
SO2, NO2, P4O10, CO2 à H2SO3, HNO2, H2PO3, H2CO3:
 Water
• Amphoteric in nature:
ü Proton donor: H2O + NH3 à NH4+ + OH-
ü Proton acceptor: H2O + HCl à H3O+ + Cl-
• Salt hydrolysis:
ü Ion of weak acids (CO32-, PO43-, acetate, oxalate)
CH3COO- + H2O à CH3COOH + OH- (basic
solution)
ü Ion of weak bases (Fe3+, Ti4+, Cu2+, Cr3+)
Fe3+ + H2O à Fe(OH)2+ + H+ (acidic
solution)
 Solid Water = ICE
• Structure
Open structure which O form puckered 6- membered rings and
arrangement of atom having 4-coordinated oxygen atom (sp3) with 2
H atom at 0.101 nm and 2 other at 0.174 nm, O-O distance 0.276 nm –
resulted distorted tetrahedral arrangement
o
o 0.174 nm
o o o
o •
0.101 nm
o o
• •
o • o
• o
Atom H
o Atom O
Hexagonal sturcture
Density of the solid is less than in liquid due to its larger volume as crystallization
takes place
Structure
of
Ice

Oxygen

Hydrogen
 Hydroxonium ion (H3O+)
– Proved hydrogen presents as H+ (proton)
– H+ is stabilized in the presence of solvent
having lone pair electron such as H2O à H3O+ is
generated

H •• H + ••
H
O•
•
H+
H
O
H
= H3O+
 Hydroxonium ion (H3O+)
• Found in acids : binary (H-X) or oxoacid (HO -
X)
d+ +
H d- d+ d- H
O H X H
H H
O + X-
d+

• Polarizability of H2O molecule depends on the

strength electronegativity of X in H-X.
• The more electronegative the X, the more H2O
can be easily protonated à or the more acidic the
H-X
 Hydroxonium ion (H3O+)
• Reaction of H3O+
Acid react with base
2H3O+ + CO32- à 3H2O + CO2
H3O+ + OH- à 2H2O
2H3O+ + S2- à 2H2O + H2S
Change litmus paper from blue à red
Thimol blue: yellow
Methyl orange : red
 Interstitial Hydride
(metallic)
• Compound of H with transition metals forming
non stoichiometric compound
• The bonding is considered metallic
• Hydrogen reacts with many transition metals or
their alloys on heating to give exceedingly
complicated substances
• They are black or grayish-black,
nonstoichoimetric solids
e.g. : LaH2.87, YbH2.55, TiH1 7, and ZrH19
 Interstitial Hydride
• Due to smaller size of H, hydrogen atoms can be
adsorbed and are located in regular interstices
between the metal atoms, and these substances
are therefore sometimes termed the interstitial
hydrides.

• The element palladium (and to a lesser extent Pt)

can absorb very large volumes of hydrogen, and
thus can be used to store hydrogen (Hydrogen
storage).
Learnt so far?

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TUTORIALS 1 & 2

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