Hydrogen - Brief Notes
Hydrogen - Brief Notes
COMPOUNDS
By
Nitin Verma
General Points About Hydrogen:
• It’s the most abundant element in the universe.
• Due to its extremely small size (~1.5 × 10–15 m), H+ does not exist in the free state.
• H has 3 isotopes: protium (1H1), deuterium (1H2 or D) and tritium (1H3 or T).
• 1H
3 is radioactive; it emits low-energy 𝛽– particles (electrons) and has a half-life (t½) of
12.33 years.
• The order of melting and boiling points, density, enthalpies of fusion and vaporization,
and bond energy:
H<D<T (due to increase in mass)
• The isotopes of H have similar chemical properties due to similar electronic configuration
and different physical properties due to different masses.
Ortho and Para Hydrogen:
The two nuclei spin in the same The two nuclei spin in the opposite
direction directions
2) Zn + 2NaOH → Na2ZnO2 + H2
4) High purity (> 99.95%) H2: By electrolysis of aqueous Ba(OH)2 using Ni electrodes.
1270 K, Ni
Example: CH4 (g) + H2O (g) CO (g) + 3H2 (g)
• The mixture of CO and H2 is called water gas or “synthesis gas” or “syngas” since it is
used in making methanol and many hydrocarbons.
cobalt catalyst
CO (g) + 2H2 (g) CH3OH (l)
9) Lane’s process:
3Fe + 4H2O → Fe3O4 + 4H2
Fe3O4 + 4CO → 3Fe + 4CO2
Preparation of Hydrogen (H2):
10) Bosch process:
• By passing steam over red-hot coke at high temperature.
C + H2O ⟶ CO + H2
• It is difficult to separate hydrogen from water gas. Hence, to increase the production of
hydrogen, the water gas is mixed with steam in the presence of iron chromate as a
catalyst.
(CO + H2) + H2O ⟶ CO2 + 2H2
Reactions and Uses of Hydrogen (H2):
Reactions:
• Less reactive due to high bond energy of H–H bond.
• Hydroformylation of olefins (alkenes) yields aldehydes which further undergo reduction
to give alcohols.
H2 + CO + RCH=CH2 → RCH2CH2CHO
H2 + RCH2CH2CHO → RCH2CH2CH2OH
Uses:
• Atomic H and oxy-hydrogen torches used in cutting and welding metals.
• As a rocket fuel.
Hydrides:
Types:
1) Ionic / saline / salt-like
2) Metallic / non-stoichiometric / interstitial
3) Covalent / molecular
Ionic or Saline Hydrides:
• Formed by s-block elements.
• Exceptions: LiH, BeH2, and MgH2 have covalent character.
• BeH2 and MgH2 are polymeric.
• Crystalline, non-volatile and non-conducting in solid state.
• Liberate H2 gas at anode on electrolysis, which confirms the existence of H– ion.
2H– (melt) → H2 (g) + 2e–
• LiH is used in making other hydrides as it does not react with O2 or Cl2:
8LiH + Al2Cl6 → 2LiAlH4 + 6LiCl
2LiH + B2H6 → 2LiBH4
Covalent or Molecular Hydrides:
• Formed by p-block elements.
• They are of 3 types: electron-deficient, electron-precise, and electron-rich hydrides.
Electron-deficient hydrides:
• Formed by group 13 elements.
• Act as Lewis acids (electron acceptors).
• Example: Diborane (B2H6).
Electron-precise hydrides:
• Formed by group 14 elements.
• Have 8 valence electrons and tetrahedral geometry.
• Example: CH4.
Covalent or Molecular Hydrides:
Electron-rich hydrides:
• Formed by group 15–17 elements.
• Have excess electrons as lone pairs.
• Act as Lewis bases (electron donors).
• Example: NH3, H2O and HF.
Metallic or Non-stoichiometric (or Interstitial)
Hydrides:
• Formed by many d- and f-block elements.
• The metals of group 7, 8 and 9 do not form hydrides (called hydride gap).
• In group 6, only Cr forms CrH.
• Poor conductors of heat and electricity compared to their parent metals.
• Non-stoichiometric, deficient in hydrogen.
• Do not obey the law of constant composition.
• Have different lattice from that of the parent metal (other than the hydrides of Ni, Pd, Ce
and Ac).
Examples: LaH2.87, VH0.56, etc.
Water:
• Due to H-bonding:
• water has high values of freezing point, boiling point, heat of vaporisation and heat
of fusion.
• water dissolves many substances.
• the density of ice is less than that of water.
• ice floats on water.
• At 1 atm pressure, ice crystallises in the hexagonal form, but at very low temperatures it
condenses to cubic form.
• Water has maximum density at 4 °C.
Structure of ice:
Ca3P2 + H2O →
P4O10 + H2O →
SiCl4 + H2O →
AlN + H2O →
Cl2O7 + H2O →
Hydrates:
a) Coordinated water e.g., [Cr(H2O)6]Cl3
• Hard water is unsuitable for laundry and harmful for boilers due to scale deposition.
• Hardness of water is of 2 types: temporary hardness and permanent hardness.
Temporary Hardness:
• Due to the presence of Ca(HCO3)2 and Mg(HCO3)2.
• Called “temporary” hardness because it can be removed by boiling.
2) Calgon’s method:
• Sodium hexametaphosphate, Na6P6O18, (called calgon) is added to hard water.
Permanent Hardness:
M2+ + [Na4P6O18]2– → [Na2MP6O18]2– + 2Na+
3) Ion-exchange method:
• Hydrated NaAlSiO4 (called zeolite or permutit or NaZ) is added in hard water.
2NaZ (s) + M2+ (aq) → MZ2 ↓ + 2Na+ (aq)
[M = Mg, Ca]
• First, hard water is passed through cation-exchange resins (sulfonic acids), which are
converted to RNa on reaction with NaCl.
2RNa (s) + M2+ (aq) → R2M (s) + 2Na+ (aq) [M2+ = Ca2+, Mg2+ ]
• The exhausted cation and anion exchange resins are regenerated by reaction with dilute acid
and alkali solutions, respectively.
Degree of Hardness:
• It is expressed as equivalents of CaCO3 in ppm or mg L–1.
Question:
100 mL of hard water contains 0.02 g of CaCO3. Calculate the degree of hardness of water in
ppm of CaCO3.
(200)
Question:
1 L of hard water contains 0.012 g of MgSO4. Calculate the degree of hardness of water.
(10)
Question:
100 mL of hard water contains 0.19 g of MgCl2 and 0.024 g of MgSO4. Calculate the degree
of hardness of water.
(2200)
Question:
1 L sample of hard water is found to contain 11.1 mg of CaCl2 and 24 mg of MgSO4.
Calculate the degree of hardness of water in ppm of CaCO3.
(30)
Hydrogen Peroxide (H2O2):
Preparation:
1) BaO2.8H2O + H2SO4 → BaSO4 ↓ + H2O2 + 8H2O
Electrolysis Hydrolysis
2) 2HSO4 – H2S2O8 2HSO4– + 2H+ + H2O2
Uses:
• As a hair bleach, mild disinfectant, and antiseptic (as perhydrol).
• In making sodium perborate and percarbonate (used in high quality detergents).
Concentration of H2O2:
Volume strength: x-volume H2O2 means 1 L of H2O2 solution gives x L of O2 gas at STP on
complete decomposition.
%Strength: 0.303x %
x
Molarity: M
11.2
x
Normality: N
5.6
Question:
Calculate the strength in g/L, %strength, molarity, and normality of 30-volume H2O2
solution.
ents
(2019 Main, 12 Jan II)
7. The correct statements among (a) to (d) are: 14. The correct statements among (a) to (d) regar
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