CHAPTER #2 HYDROGEN

POSITION OF HYDROGEN IN THE PERIODIC TABLE:

Elements are arranged in the periodic table according to their electronic configuration and properties.
Hydrogen partially resemble with group IA (Alkali metals), group IVA (Carbon family) and group VIIA
(Halogens) but does not resemble completely with any one of the group.
HYDROGEN AND GROUP IA (ALKALI METALS):
RESEMBLANCE:
1. Hydrogen and alkali metals possess one electron in the s-orbital of the valence shell.
1
H= 1s1
3
Li= 1s2, 2s1
2. Both are monovalent.
3. Both are electropositive and form positive ions like H+ and Na+.
4. Both react with electronegative elements and form electrolytes.
H2 + Cl2 → 2H+Cl-
2Na + Cl2 → 2Na+Cl-
5. Both are reducing agents.
DIFFERENCES:
1. Hydrogen is a gas and alkali metals are solids.
2. Hydrogen makes covalent bond while alkali metals form ionic bond
3. Nature of oxides are different. For example Na2O is basic and H2O is neutral.
4. Hydrogen can make negative ions but alkali metals cannot.

HYDROGEN AND GROUP VIIA (HALOGENS):

RESEMBLANCE:
1. Both of them are non-metals and bad conductors of heat and electricity.
2. Both are diatomic molecule like H2, F2.
3. Both react with metals, hydrogen form hydrides and halogens form halides. For example: Na+H- sodium
hydride, Na+Cl- sodium chloride
4. Both of them form negative ions by gaining one electron from electropositive metals.
H + e- → H-
F + e- → F -
DIFFERENCES:
1. Electron affinity of hydrogen is much less than halogens.
2. H- Ion is unstable while halogens form stable negative ions.
3. Nature of oxides are different. For example Cl2O7 is acidic and H2O is neutral.
4. Hydrogen is a reducing agent whereas halogens are oxidizing agents.
HYDROGEN AND GROUP IVA CARBON FAMILY):
RESEMBLANCE:
1. The valence shell of hydrogen and elements of group IVA are half filled.
2. Ionization potential and electron affinity values are similar.
3. Hydrogen and group IV A elements are non-metals.

DIFFERENCES:
1. Hydrogen is a gas while members of group IVA are solids.
2. Hydrogen is monovalent, while members of group IVA are tetravalent
3. Hydrogen’s valence shell consist of only s orbital and group IV A members consist of s and p orbital.

INDUSTRIAL PREPARATION OF HYDROGEN GAS:

1. By electrolysis of water:
When electricity is passed through water containing small quantity of electrolyte (an acid, base or salt), water
decomposes into hydrogen and oxygen gases. Hydrogen collects at cathode and oxygen collects at anode. The
gases produced are in the purest form.
2H2O → 2H2 + O2
2. By steam and hydrocarbon process:
A mixture of hydrogen and carbon monoxide commonly known as water gas is formed when a mixture of
steam and natural gas is passed over nickel catalyst at 900oC.
CH4 + H2O → 3H2 + CO
3. By the action of steam on coal:
Water gas is formed when steam is passed over red hot coke at about 1000oC.
C + H2O → H2 + CO
4. Steam methanol process:
A mixture of steam and vapours of methanol when heated at 250oC produces a mixture of H2 and CO2. H2 is
separated by dissolving CO2 in water under high pressure.
CH3OH + H2O → 3H2 + CO2
5. Thermal decomposition of hydrocarbons:
Methane when heated in the absence of oxygen is decomposed into its elements.
CH4 → 2H2 + C
6. Thermal decomposition of ammonia:
In this process ammonia is decomposed by heating it at 1000oC by passing it over an active catalyst. The
mixture of nitrogen and hydrogen is cooled up to -196oC, nitrogen liquefies and hydrogen is separated.
2NH3 → N2 + 3H2
METHODS OF SEPERATION OF HYDROGEN FROM WATER GAS:
1. First method (Bosch process):
By heating water gas with more steam at 500oC in the presence of catalyst (iron oxide or cobalt oxide). Carbon
monoxide is oxidized into carbon dioxide and separated by dissolving in water under high pressure leaving
behind free hydrogen gas.
CO + H2 + H2O → CO2 + 2H2

2. Second method:
By cooling water gas at -200oC with the help of liquid air. Carbon monoxide liquefies and free hydrogen gas is
separated. Traces of carbon monoxide are further removed by passing contaminated hydrogen through NaOH
solution, which absorbs carbon monoxide to form sodium formate.
CO + NaOH → HCOONa

ATOMIC HYDROGEN:
“The product obtained as a result of dissociation of molecular hydrogen is called atomic hydrogen”. It is in
atomic state. Atomic hydrogen has very short life and combine quickly together or with other atoms to form
molecules.

PREPARATION OF ATOMIC HYDROGEN:

1. First method:
Atomic hydrogen is prepared by thermal decomposition of ordinary hydrogen.
H2 → 2H ΔH= +104kcal/mol
2. Second method:
Atomic hydrogen is formed by electrical dissociation of ordinary hydrogen under reduced pressure.
H2 → 2H
PROPERTIES OF ATOMIC HYDROGEN:
1. It has very short life and quickly combines to form H2 molecules.
2. Atomic hydrogen is a strong reducing agent and reacts with metals and non-metals at ordinary temperature.

 Reaction with non-metals form different products

P +3H → PH3
O2 + 2H → H2O2
Cl2 + 2H → 2HCl
 Reaction with metals form hydrides
Ca + 2H → CaH2
2Na + 2H → 2NaH
 It reduces oxides into metals
CuO + 2H → Cu + H2O
HgO + 2H → Hg + H2O
USES OF ATOMIC HYDROGEN:
Atomic hydrogen is used to produce atomic hydrogen torch to attain a temperature 4000-5000oC, which is used
for welding aluminium alloys, high chromium and nickel steel products. Heat is produced by combination of
hydrogen atoms.
H + H → H2 ΔH= -104kcal/mol

NASCENT HYDROGEN:
Atomic hydrogen produced during a chemical reaction is called nascent hydrogen.
Zn + 2HCl → ZnCl2 + 2[H]
BINARY COMPOUNDS OF HYDROGEN:
Hydrogen combines with other elements and forms binary compounds which are called hydrides. There are six
types of hydrides.

1. IONIC HYDRIDES (SALT LIKE HYDRIDES):

Ionic hydrides are formed by the metals of group IA (alkali metals) and group IIA (alkaline earth metals)
except Be and Mg. Metals form positive ions by losing one valence electron and hydrogen form negative ion
by gaining that electron. They have general formula (M+H-) in case of group IA and (M+2H2(-1)) in case of
group IIA. Therefore they are known as the ionic hydrides. They possess salt like characteristics so they are
called salt like or saline hydrides OR true hydrides.

Preparation:
They are prepared by passing hydrogen gas over hot alkali metals or alkaline earth metals.
2Na + H2 ___heat__ 2NaH
o
200 C Sodium hydride

Ca + H2 ___heat_____ CaH2
200 º C Calcium hydride
Properties:
1. They are colourless, salt like solids with high melting points.
2. They possess ionic bonds
3. They are insoluble in organic solvent but soluble in water. They react with water and produce hydrogen gas.
Na+ H- + H2O → NaOH + H2
CaH2 + 2H2O → Ca(OH)2 + 2H2
4. They produce hydrogen gas on reaction with acids and alcohols.
NaH + HCl → NaCl + H2
Hydrochloric acid
NaH + C2H5OH → C2H5ONa + H2
Ethyl alcohol
2. COVALENT HYDRIDES:
Elements from group III A to VII A form binary compounds with hydrogen , they contain covalent bond so
they are called covalent hydrides.

Preparation:

(i) By direct union of free elements:

H2 +Cl2 → 2HCl
2H2 + O2 → 2H2O
H2 + S → H2S

(ii) By the hydrolysis of the compound:

CaC2 + 2H2O → Ca(OH)2 + C2H2
Al4C3 + 6H2O→ 2Al2O3 + 3CH4
Mg3N2 + 6H2O→ 3Mg(OH)2 + 2NH3
Ca3P2 + 6H2O → 3Ca(OH)2 + 2PH3
PCl3 + 3H2O → H3PO3 + 3HCl
Properties:
1. They are colourless gases or volatile liquids having low boiling points.
2. Hydrides of group IIIA and group IVA are neutral, hydrides of group VA are basic, while hydrides of group
VIA and VIIA are acidic.

3. COMPLEX HYDRIDES:
Hydrides of group IIIA elements combine with hydrides of alkali metals and form complex compounds, which
contain all three types of chemical bonds. These compounds are called complex hydrides. Their general
formula is ABH4 where A+ is alkali metal ion B3+ is ion of group IIIA elements.

Preparation:
They are formed by the action of alkali metal hydrides on hydrides of group IIIA elements or trihalides.
LiH + AlH3 → LiAlH4
NaH + BH3 → NaBH4
4NaH + BF3 → NaBH4 + 3NaF

Properties:
1. They are salt like solids stable up to 300oC.
2. They have tetrahedral structure.
3. They are soluble in water.
4. They react with water to produce hydrogen.
NaAlH4 + 4H2O → Al(OH)3 + NaOH + 4H2

4. METALLIC HYDRIDES:
The binary compounds of hydrogen with transition metals are called metallic hydrides.

Preparation:
In metallic hydrides, hydrogen is absorbed in metals and occupy interstitial spaces (empty space between metal
atoms) in crystal lattice of metal. No chemical bond is present in these hydrides. They are also called
interstitial hydrides.

Properties:
On heating these hydrides release hydrogen in atomic state that’s why platinum and nickel are used as a
catalyst in hydrogenation reaction.

5. POLYMERIC HYDRIDES:
First two members of group II A i.e. Be and Mg form BeH2 and MgH2. Large number of molecules of these
hydrides join and form polymer so they are called polymeric hydrides.

Properties:
Their properties are intermediate between ionic hydrides and covalent hydrides.

n
6. BORDER LINE HYDRIDES:
These hydrides are formed by metals of group I B, II B and few metals of group III A such as indium and
thallium. For example, CuH2, ZnH2 and TlH2.

Properties:
Their properties are intermediate between metallic hydrides and covalent hydrides.

ISOTOPES:
“Elements which have same atomic number but different mass number are called isotopes”
OR
“Elements which have same number of protons but different number of neutrons”

ISOTOPES OF HYDROGEN:

1. Protium ( 1H1):
Free hydrogen contains 99.98% protium. It is known as ordinary hydrogen.
Number of protons = 1
Number of electrons = 1
Number of neutrons = 0
Atomic number = 1
Mass number = 1

2. Deuterium (1H2 or D):

It is called “Heavy hydrogen”. Free hydrogen contains 0.0156% deuterium.
Number of protons = 1
Number of electrons = 1
Number of neutrons = 1
Atomic number = 1
Mass number = 2

3. Tritium (1H3 or T):

Free hydrogen contains about 4×10-15 tritium. It is radioactive form of hydrogen with half life of 12.5 years.
Number of protons = 1
Number of electrons = 1
Number of neutrons = 2
Atomic number = 1
Mass number = 3