Hydrogen

Hon’s 2nd Year 1st Semester

Chemistry of Elements (CHE-2131)

Aparna Sarker
Assistant Professor
Department of Chemistry
Jagannath University, Dhaka
1. First element in the periodic table with atomic mass 1 u and atomic number 1.

2. Hydrogen element that exists as a gas at room temperature.

3. It has smallest atom containing one proton at the nucleus and only one

electron revolving around the nucleus. But it’s isotopes are possible.

4. Pure hydrogen exists as gas, in which pairs of hydrogen atoms bonded

together to make molecule

In 1766, H. Cavendish isolated and identified the hydrogen

gas, and established conclusively that water was a compound

of 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”.
 Occurrence
1. Hydrogen is the most abundant element in the universe. It is believed that 90% of

the weight of the sun consists of hydrogen, so also other stars.

✓ Exists in combined form around 15.4% of the atoms in the earth’s crust and oceans

✓ 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%).

2. Water is the most abundant compound of hydrogen on the earth.

3. All organic compounds and natural organic substances contain hydrogen.

4. Hydrogen rarely occurs in the free state on the earth.

 Various forms of Hydrogen
Atomic and Physical Properties of Hydrogen

✓ Firstly despite its very simple electronic configuration (1s1) hydrogen can, paradoxically, exist in

over 50 different forms most of which have been well characterized. This multiplicity of forms

arises firstly from the existence of atomic, molecular and ionized species in the gas phase: H,

H2, H+, H- ;

✓ Secondly, from the existence of three isotopes: H(D) and iH(T), and correspondingly of D, D2,

HD, DT, etc.

✓ Finally, from the existence of nuclear spin isomers for the homonuclear diatomic species, i.e.

ortho- and para-dihydrogen, -dideuterium and -ditritium.

 Various forms of Hydrogen

Isotopes of hydrogen

Hydrogen as it occurs in nature is predominantly composed of atoms in which the nucleus is a

single proton. In addition, terrestrial hydrogen contains about 0.0156% of deuterium atoms in

which the nucleus also contains a neutron, and this is the reason for its variable atomic weight.

Addition of a second neutron induces instability and tritium is radioactive, emitting low-energy

p- particles with a halflife of 12.33 y.

In the molecular form, dihydrogen is a stable, colourless, odourless, tasteless gas with a very

low melting point and boiling point.

 Various forms of Hydrogen

Applications of Deuterium Applications of Tritium

Drugs Analytical chemistry
Nuclear weapons Controlled nuclear fusion
Contrast properties Tritium in hydrogen bomb secondaries
Tracing Boosting
NMR spectroscopy Neutron initiator
Nuclear reactors and Nuclear Power Plants Nuclear weapons
Self-powered lighting
Used as an oceanic transient tracer
 Various forms of Hydrogen

Reactive forms of hydrogen

✓ Nascent Hydrogen : Zn+H2SO4→ ZnSO4+2H

✓ Adsorbed Hydrogen: Absorbed on metals (Pb, Ni etc.) under certain conditions

✓ Active hydrogen: Produced by electric discharge.

✓ Ortho and Para hydrogen

✓ Ortho hydrogen molecules are those in which the spins of both the nuclei

are in the same direction.

✓ Molecules of hydrogen in which the spins of both the nuclei are in the

opposite direction are called para hydrogen.

✓ Ordinary dihydrogen is an equilibrium mixture of ortho and para hydrogen.

Physical properties of ortho hydrogen:-
✓ Ortho Hydrogen Shows parallel nuclear spin
✓ The Nuclear spin of ortho hydrogen = ½ + ½ = 1
✓ The Ortho form of hydrogen is stable at room temperature.
✓ The melting point of ortho hydrogen is 13.95 K.
✓ The boiling point of ortho hydrogen is 20.39 K.
✓ The magnetic moment of ortho hydrogen is twice that of a proton.

Physical properties of para hydrogen:-

✓ Para hydrogen shows antiparallel spin
✓ The nuclear spin of para hydrogen = ½ – ½ = 0
✓ Para form of hydrogen is more stable at a lower temperature.
✓ The melting point of para-hydrogen is 13.83 K.
✓ The boiling point of para-hydrogen is 20.39 K.
✓ The magnetic moment of para-hydrogen is zero as the spins neutralize each other.
✓ The vapour pressure of liquid para-hydrogen is higher than that of liquid ortho hydrogen.
✓ The internal molecular energy of para-hydrogen is lower than the ortho form of hydrogen.
Conversion of Para to Ortho hydrogen

• By heating it above 800 °C

• By passing through electric discharge tube

• By treatment of catalyst
Preparation
✓ In the laboratory it is made by the action of an acid on zinc or other metals
2H3O++ Zn → Zn2+ + H2 + 2H2O
✓ Commercially hydrogen is produced by the water gas process
C + H2O→CO + H2
✓ The purest form of hydrogen is obtained by electrolysis of water
2H2O→2H2 + O2 — 135 Kcal
Physical properties:
• Lightest gas because of its low density, it is used instead of helium to fill balloons for meteorology.
• Colorless, odorless gas slightly soluble in water.
• Combustible.
• Very low m. p. and b. p. indicating small intermolecular attraction in gaseous hydrogen molecule.
• Inversion temperature of 195K indicates that when hydrogen gas is cooled to below 195 K, release of
pressure produces cooling and liquefaction. Above 195 K, release of pressure produces warming.
• Hydrogen diffuses faster than any other gas because of the lowest molecular mass than all gases.
 Chemical Properties of Hydrogen
✓ Hydrogen forms diatomic molecules H2,and the two atoms are joined by a very strong covalent bond (bond
energy 435.9kJ mol-1).
✓ Hydrogen is not very reactive under normal conditions.
✓ The chemical properties of hydrogen require the breaking up of the bond in H2 molecule that requires
435.9kJ mol-1, hence there is a high activation energy to such reactions.
✓ Consequently many reactions are slow, or require high temperatures, or catalysts (often transition metals).
Many important reactions of hydrogen involve heterogeneous catalysis, where the catalyst first reacts with
H2 and either breaks or weakens the H-H bond, and thus lowers the activation energy. Examples include:
• The Haber process for the manufacture of NH3 from N2 and H2 using a catalyst of activated Fe at 380-450°C
and 200 atmospheres pressure.
:

• The hydrogenation of a variety of unsaturated organic compounds, (including the hardening of oils), using
finely divided Ni, Pd or Pt as catalysts.
• The production of methanol by reducing CO with H2 over a Cu/Zn catalyst at 300°C.
 Chemical Properties of Hydrogen

1. Reaction with nitrogen: 5. Reaction with halogens:

200atm
N2(g)+3H2(g) ⇌2NH3(g) H2(g)+X2(g)→2HX
450-500 °C, Fe X=F, Cl, Br, I

2. Reaction with unsaturated hydrocarbon: 6. Reaction with Lithium:

Pt
CH3CH2CH=CH2 + H2 → CH3CH2CH2CH3 2Li(s) + H2(g) → 2LiH(s)

3. Reaction with carbon-monoxide: 7. Reaction with metal oxide:

Co
CO(g) + 2H2(g) → CH3OH(g) WO3(s) + 3H2(g) → W(s) + 3H2O(g)

4. Production of water:

2H2+O2 →2H2O, ∆H=-484 kJ

 Bonding of Hydrogen
The chemistry of hydrogen depends mainly on the three electronic processes
(1) loss of a valence electron to give H+,
(2) acquisition of an electron to give H-, and
(3) formation of a single covalent bond, as in CH4

However, hydrogen has additional unique bonding features. The nature of the proton and the complete absence of
any shielding of the nuclear charge by electron shells allow other forms of chemical activity.
1. The formation of numerous compounds, often nonstoichiometric, with metallic elements. These compounds
are generally called hydrides but cannot be regarded as simple saline hydrides. LaH2.87, ZrH1.9
2. The formation of hydrogen bridge bonds in electron-deficient compounds and transition metal complexes.

3. The hydrogen bond dominates the chemistry of water, aqueous solutions, hydroxylic solvents, and OH-
containing species and have importance in biological systems, since they are responsible for the linking of
polypeptide chains in proteins and the base pairs of nucleic acids
 Hydrides

Binary compounds of hydrogen with another element is generally known as hydrides.

Types
✓ Ionic Hydrides / Saline hydride/Salt like hydrides >> NaH, CaH2
✓ Covalent hydrides / Molecular hydrides >> NH3, H2S
✓ Metallic hydrides / Transition metal hydrides/ Interstitial hydrides >> HMn(CO)5 , ZrH1.9
 Hydrides
p block
s block
1 2 Intermediate hydrides 13 14 15 16 17 18
d block
3 4 5 6 7 8 9 10 11 12

Intermediate Covalent
Ionic Metallic hydrides
hydrides hydrides
hydrides
f block
 Saline hydride
The saline hydrides are insoluble in common nonaqueous solvents but they do dissolve in molten alkali
halides. Electrolysis of these molten-salt solutions produces hydrogen gas at the anode (the site of
oxidation):
2H-(melt) → H2 (g) + 2e-
This reaction provides chemical evidence for the existence of H- ions.
The reaction of saline hydrides with water, as in
NaH(s) + H2O(l) → NaOH(aq) + H2 (g) is dangerously vigorous.
Alkali metal hydrides are convenient reagents for making other hydride compounds because they are
direct providers of H- ions for the following synthetically useful reactions:
1. Metathesis with a halide, such as the reaction of finely divided lithium hydride with silicon
tetrachloride in dry diethyl ether (et):
4LiH(s) + SiCl4 (et) → 4 LiCl(s) + SiH4 (g)
2. Addition to a Lewis acid, for example reaction with a trialkylboron compound yields a hydride complex
that is a useful reducing agent and source of hydride ions in organic solvents:
NaH(s) + B(C2H5) 3 (et) → Na[HB(C2H5)3 ](et)
where ‘et’ denotes solution in diethyl ether
3. Reaction with a proton source, to produce H2 :
NaH(s) + CH3OH(et) → NaOCH3 (s)+H2 (g)
 Molecular hydrides
Molecular hydrides are formed with p-block elements and Be.
Types:
Electron-precise: in which all valence electrons of the central atom are engaged in bonds.
e.g. CH4 ,silane(SiH4) , and germane(GeH4)
Electron-rich: In which there are more electron pairs on the central atom than are needed for bond formation
(that is, there are lone pairs on the central atom). Electron-rich compounds are formed by the elements in
Groups 15 to 17. e.g. H2O, NH3, HX.
Electron-deficient: in which there are too few electrons to be able to write a Lewis structure for the molecule.
Electron-deficient hydrogen compounds are common for boron and aluminium. e.g. Diborane (B2H6)
 Hydrides

✓ Homolytic dissociation of an E-H bond to produce a radical E· and hydrogen atom H occurs most
readily for the hydrides of the heavy p-block elements.
H2O(g) → 1/2 O2 (g)+H2 (g)
✓ Hydrogen attached to an electronegative element has protic character and the compound is typically a
Brønsted acid.
H3PO4 → HPO4-+H+
✓ Hydrogen attached to an electropositive element can be transferred to an acceptor as a hydride ion.
4H2O
AlH4-+4RCHO→ Al(OCH2R)4- → Al(OH)4- +4RCH2OH
 Metallic hydrides

✓ Many of the d- and f-block elements react with H2 to produce metallic hydrides.
✓ No stable binary metal hydrides are known for the metals in Groups 7 to 9

✓ Have a metallic luster

✓ Have metallic conductivity and in many the hydrogen is very mobile
✓ They are less dense than the parent metal and are brittle.

Types:
• Stoichiometric >> Re2H8(PR3)4, HMn(CO)5
• Nonstoichiometric >> LaH2.87, TiH1.7
 Hydrides
p block
s block
1 2 Intermediate hydrides 13 14 15 16 17 18
d block
3 4 5 6 7 8 9 10 11 12

Intermediate Covalent
Ionic Metallic hydrides
hydrides hydrides
hydrides
f block
Uses of Hydride
✓ They are used as reducing agents in many chemical industries. e.g. LiAlH4
✓ Hydrides are highly significant in battery storage technologies such as nickel
hydride batteries.
✓ They are used as drying agents. e.g. CaH2
✓ They are used as strong bases in organic synthesis. e.g. NaH
✓ Metal hydrides are also used for their heat storage, hydrogen storage and
compressors capabilities. e.g. LaNi5H6
 Heavy Water
Water which is composed of deuterium oxide (D2O) molecules, is called heavy water.
In 1933, Urey showed that D2O is present in ordinary water to the extent of I part in 6,000 parts.
Water actually contains three types of molecules—HOH, HOD and DOD (ignoring tritium, T).
Preparation
1. Electrolysis of water containing alkali between nickel electrodes gives D2O.
H2O Molecules undergo electrolysis at a faster rate than D2O molecules:
2 H2O → 2H2 + O2 fast
2 D2O →2D2 + O2 Slow
After prolonged electrolysis the residual liquid remaining in the electrolytic cell on distillation becomes enriched in D2O,
Pure D2O can be isolated in small amount on repeated processing.

2. Exchange equilibrium process in which commercial hydrogen gas mixed with steam is passed over a catalyst to give
D2O. The process is less costly and is applied in atomic energy work in commercial hydrogen is exchanged with steam:
D2 +H2O → H2 + D2O
On condensing the steam to water it becomes enriched with D2O. This water is then decomposed by the electrolytic
process. The whole process is repeated until nearly pure D2O (heavy water) is obtained.
Properties :
Exchange Reaction of Heavy Water
➢ Hydrogen in any compound is exchanged with D:
NH4CI + 2 D2O → ND4Cl + 2 H2O
2CH3COOH + D2O → 2CH3COOD + H2O2

➢ Pure compounds of D can be prepared by reactions similar to that of water. Thus,

CaC2 + D2O → CaO + C2D2 (deuteroacetylene)

➢ Tracer experiments : D2O, is 10% heavier than H2O >> readily be distinguished by mass
spectrograph or by weight >> act as "tracer" in finding the path of chemical reaction and in
physical changes such as digestion and metabolism in the body.
Example: tracer experiment with D2O, is the reaction between Zn and HCl solution in water :
H2O
Zn + 2HCl → ZnCl2 + 2H2
D2O
Zn + 2DCl → ZnCl2 + 2D2
Whether all the H2 comes from HCI or also from H2O has been solved by tracing the reaction
with D2O. It has been found that H2 comes from both HCI and H2O
Uses of Heavy Water
• Heavy water is largely used to slow down fast neutrons in nuclear
reactors and is one of the well-known moderators for atomic
reactors.
• In preparation of heavy hydrogen
• In tracer studies
Thank you