Scribd
Upload
67 views

Chapter 10

Hydrogen and its compounds are discussed, including isotopes of hydrogen, dihydrogen, and hydrogen bonding. There are four major classes of binary hydrides: metallic, saline, molecular, and covalent hydrides with extended structures. Hydrogen is used as a feedstock for methanol and ammonia production, and plays a role in metal production and water of crystallization in crystals.

Uploaded by

Harris Ali
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
67 views

Chapter 10

Hydrogen and its compounds are discussed, including isotopes of hydrogen, dihydrogen, and hydrogen bonding. There are four major classes of binary hydrides: metallic, saline, molecular, and covalent hydrides with extended structures. Hydrogen is used as a feedstock for methanol and ammonia production, and plays a role in metal production and water of crystallization in crystals.

Uploaded by

Harris Ali
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 13

Chapter 10

Hydrogen

Hydrogen and hydride ions


Isotopes of hydrogen
Dihydrogen
Polar and non-polar E-H bonds
Hydrogen Bonding
Classes of binary hydrides

Major Uses of Hydrogen

Feedstock
for CH3OH

-C-C- NH3 for


hydrogenation of fertilizers
unsaturated fats
and oils
H2

Metal
Fuel
Production

1
Water of crystallization
• Solids that consist of molecules of a compound along with
water molecules are named hydrates.

• Contain water bound to cations to anions or other electron


rich atoms via hydrogen bonds.
– [M(OH2)6]n+ etc.

• Water of crystallization found in some crystals and hydrated


metal halides e.g. CuSO4.5H2O

• CoCl2(H2O)6 has a coordination sphere around the metal as


trans-[CoCl2(H2O)4] and two equivalents of water of
crystallization that are not bound to Co.

Hydrated Protons

H(g)  H+(g) + e- Ionization Energy 1312 kJ mol-1


[H3O]+ is the hydrated proton or oxonium ion
• DhydHo(H+, g) = 1091 kJ mol-1

[H5O2]+

2
Hydride Ion
H(g) + e-  H-(g) DEAH(298K) = -73 kJ mol-1
In the solid state, all alkali metal hydrides crystallize with the
NaCl structure type.
•From the crystal structure, the radius of H- can be estimated
by: internuclear distance = rcation + ranion

Isotopes of Hydrogen

Three common isotopes: protium, deuterium, and tritium

3
Kinetic Isotope Effect

The zero point energy


(corresponding to the
lowest vibrational state)
of a CD bond is lower
than that of a CH bond
and this results in the
bond dissociation
enthalpy, D, of the CD
bond being greater than
that of the CH bond.

Selected properties of H2O and D2O (‘heavy water’).

Why is the boiling point of D2O greater than that of H2O?

What about tritium? Where does it come from?

4
Dihydrogen

Selected physical properties of H2.

Dihydrogen production

Zn(s) + 2HCl(aq)  ZnCl2(aq) + H2(g)


2Al(s) + 2NaOH(aq) + 6 H2O(l)  2Na[Al(OH)4](aq) + 3 H2(g)
CaH2(s) + 2H2O(l)  Ca(OH)2(aq) + 2H2(g)

Cu/ZnO catalyst
CO + 2H2 CH3OH Haber Process
~550 K, 50 bar

Reagents above are known as synthesis gas. and the


mixture is manufactured by the water-gas shift reaction.
Ni catalyst
CH4 + H2O CO + 3H2
~1200 K

iron oxide catalyst


CO + H2O CO2 + H2
~700 K

hydrogen economy – formation of H2 from H2O requires a large energy input

5
Hydrogen Economy

Photocatalyst

[Ru(bpy)3]3 (bpy = 2,2'-bipyridine)

6
Reactivity

Interaction of an H2 molecule with a metal


surface to give adsorbed hydrogen atoms

Polar and non-polar bonds

The direction of the dipole


moment in a polar EH bond
depends upon the relative
electronegativity values.
• The direction in which the
arrow points ( to ) is
defined by SI convention.

The difference in electronegativity values between E and H means the bond may be:
•Non-polar, or polar in either of the senses given the diagram above.
•When E is a p-block element, B-H, C-H, Si-H bonds are essentially non-polar
•When E is a metal (electropositive) H carries a partial negative charge.
•When E is N, O, or F the H atom carries a partial positive charge

7
Hydrogen bonding

Hydrogen bonding in formic acid

monomer

solid state

dimer

8
Trends in (a) melting and (b) boiling points for some p-block hydrides, EHn.

DvapH (measured at the boiling Trouton’s Rule


point of the liquid) for some p-
block hydrides, EHn.
An interesting and useful approximation:
• The ratio of the heat of vaporization and the
boiling point is (approximately) constant
DvapS = DvapH/bp ~ 88 J K-1 mol-1

• Boiling point of cyclohexane is 69°C.


Therefore,
DvapH = (69 + 273)(88) ~ 30 kJ/mol
which is within 2-3% of the experimental value

• Works well for unassociated liquids and gives


useful information about degree of association.

9
Solid state structure of HF [HF2] ion

stabilization in the solid state of [H5O2] and


[H7O3] by hydrogen bonding to crown ethers

Hydrogen-bonded chains in the solid-


state structure of Me2NNO2

10
Dihydrogen Bond

Hydrogen bonding in biological systems

11
Binary Hydrides

Four major classes: metallic, saline


(salt like), molecular, covalent (with
extended structures)

Molecular hydrido complexes

[CoH5]4 [FeH6]4

[ReH9]2 [Pt2H9]5

12
Polymeric Hydrides

polymeric chain structure of BeH2

13

You might also like