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Inorganic Chemistry

 

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Inorganic Chemistry

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1H: protium 2H: D, deuterium, 16/100,000 3H: T, tritium, 1/1021

H-: two electrons are bound by just one proton D polarizable


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Inorganic Chemistry

Some of the processes that contribute to the biological hydrogen


cycle in a freshwater environment.
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Inorganic Chemistry

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Hydrogen may be found in a metallic state, such as the core of
Jupiter.
H²H Bond length: 74 pm
Electric discharge H2 DD H, H+, H2+, H3+ Y 

Bond enthalpy
homolytic dissociation H2(g) D H(g) + H(g) ¨H = 436 kJ/mol

heterolytic dissociation H2(g) D H+(g) + H-(g) ¨H = 1675 kJ/mol


Explosive reaction: 2 H2(g) + O2(g) D 2 H2O(g) ¨H = -242 kJ/mol
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Inorganic Chemistry

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1. 1$+!  :
 : individual, discrete molecules formed with
p-block elements. E
E--H bond: covalent bond Ex: CH4, NH3,
H 2O
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Inorganic Chemistry

2. |!
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 : ionic hydrides, formed with the most
electropositive elements. Ex: LiH, CaH2 containing H- ions.

3. 1!$  :
 : non-
non-stoichiometric, electrically conducting
solids with a metallic luster. Ex: NaBH4, LiAlH4
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Cu/ZnO
CH3OH(g) + H2O(g) CO2(g) + 3 H2(g) ¨H = 49 kJ/mol
Pd
CH3OH(g) + ½ O2(g) CO2(g) + 2 H2(g) ¨H = -155 kJ/mol

Reaction at temperature of 200-350 oC


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Inorganic Chemistry
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Inorganic Chemistry

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Inorganic Chemistry

H²H is the strongest single


homonuclear bond

D a compound to be exergonic and


stable with respect to its elements

D E²H should be stronger than H²



H

The weak bond formed by heavier


p-block elements
D poor overlap between the
relatively compact H 1s orbital and
the more diffuse s and p orbitals of
their atoms.
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Inorganic Chemistry

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Inorganic Chemistry

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ȕ decay (high-speed e-)

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Inorganic Chemistry

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2 Al + 2 OH- + 6 H2O D 2 Al(OH)4-(aq) + 3 H2(g)

Si + 2 OH- + H2O D SiO32-(aq) + 2 H2(g)

Zn + 2 H3O+ D Zn2+(aq) + H2(g) + 2 H2O

CaH2(s) + 2 H2O D Ca(OH)2(s) + 2 H2(g)


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Inorganic Chemistry

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CH4(g) + H2O(g) D CO(g) + 3 H2(g) ¨H = 206.2 kJ/mol

C(s) + H2O(g) D CO(g) + H2(g) ¨H = 131.4 kJ/mol


  

CO(g) + H2O(g) D CO2(g) + H2(g) ¨H = -41.2 kJ/mol

C(s) + 2 H2O(g) D CO2(g) + 2 H2(g) ¨H = 90.2 kJ/mol


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Inorganic Chemistry

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H2O(l) D H2(g) + ½ O2(g) E = -1.23 V, ¨G = 237 kJ/mol

An electrolysis cell for H2 production using Ni anodes and Fe cathodes


connected in series.
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Inorganic Chemistry

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Inorganic Chemistry

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Catalyst: Cu/ZnO/Al2O3
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Inorganic Chemistry

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425 oC
2 Cu(s) + 2 HCl(g) H2(g) + 2 CuCl(s)
electrolysis
4 CuCl(s) 2 Cu(s) + 2 CuCl2(s)
325 oC
2 CuCl2(s) + H2O Cu2OCl2(s) + 2 HCl(g)
550 oC
CH2OCl2(s) 2 CuCl(s) + ½ O2(g)

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Inorganic Chemistry

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Inorganic Chemistry

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Inorganic Chemistry
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Inorganic Chemistry
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Inorganic Chemistry

EXAMPLE 10.1 Determining which hydrogen atoms in a molecule


are the most acidic
Phosphorous acid, H3PO3, is a diprotic acid and is more helpfully
written as OP(H)(OH)2. Explain why the H atom bound to P is much
less protonic than the two H atoms bound to O ?

Ans: P-H bond enthalpy: 321 kJ/mol


O-H bond enthalpy: 464 kJ/mol

but O in more electronegative than P D O-


 is more protonic
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Inorganic Chemistry
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Inorganic Chemistry

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Figure 10.6 Normal boiling points of p-


p-block binary hydrogen compounds.
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Inorganic Chemistry

Figure 10
10..8 Base pairing in DNADNA..
Cytosine recognizes guanine through
the formation of three hydrogen bonds
bonds..

Figure 10
10..7 The structure of ice
ice..
The structure shows all possible
atom positions, but only half are
actually occupied
occupied..
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Inorganic Chemistry

Cl-
Cl-H-Cl: linear but not symmetrical
F-H-F : not linear but symmetrical

Figure 10.9 The variation of the potential energy with the position of the proton
between two atoms in a hydrogen bond.
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Inorganic Chemistry

Figure 10.11 The orientation of lone pairs as indicated by VSEPR theory


compared with the orientation of HF in the gas-
gas-phase H-
H-bonded complex.
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Inorganic Chemistry

Figure 10.12 The cages of water molecules in clathrate hydrates; in this case
Xe4(CCl4)8(H2O)68.
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Inorganic Chemistry 1 !
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Inorganic Chemistry

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3 bar H2, 210 oC


Li3N(s) + H2(g) Li2NH(s) + LiH(s) ¨H = 148 kJ/mol
vacuum, > 320 oC at 298 K

3 bar H2, 255 oC


Li2NH(s) + H2(g) LiNH2(s) + LiH(s) ¨H = 45 kJ/mol
vacuum, < 200 oC at 298 K

Figure B10.4 Structure relationship between Li2NH and LiNH2


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Inorganic Chemistry

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Most metal hydrides:
- metallic luster, electrically conducting, less dense than the
parent metal, brittle
- variable composition (ZrH1.3 ~ ZrH1.75)
- CeH2-x is a metallic conductor, CeH3 is an insulator

Ni, Pt ± hydrogenation catalysts.


Pd ± at moderate pressure D PdHx, X<1
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Inorganic Chemistry

Pd absorbs up to 900 times its own volume of H2, which is given


off again on heating.

LaNi5 D LaNi5H6: greater density of hydrogen than H2(liq)

Figure 10.14 Schematic diagram of a hydrogen


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Inorganic Chemistry

Figure 10.13 Hydrides formed by d- and f-block elements. The formulae are
limiting stoichiometries based on the structure type.
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Inorganic Chemistry

EXAMPLE 10.2 Correlating the classification and properties of


hydrogen compounds

Classify the compounds PH3, CsH and B2H6 and discuss their
probable physical properties. For the molecular compounds specify
their subclassification (electron-deficient, electron-precise or
electron-rich).
Ans: Cs: group 1 D saline hydride D insulator & rock-salt structure
P, B: p-block D molecules D low molar masses &
high volatilities
PH3: lone pair D electron-rich
B2H6: electron-deficient
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Inorganic Chemistry

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Inorganic Chemistry
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Inorganic Chemistry

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Inorganic Chemistry

EXAMPLE 10.3 Using hydrogen compounds in synthesis


Suggest a procedure for synthesizing lithium
tetraethoxyaluminate, Li[Al(OEt)4], from LiAlH4 and reagents
and solvents of your choice.

Ans: AlH4- D H- donor: strong Brønsted base than EtO-

LiAlH4 + 4 C2H5OH D Li[Al(OEt)4] + 4 H2


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Inorganic Chemistry

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