H

Unit 1 1s1
Hydrogen
 Hydrogen
•Natural State.

General Structure for the Chapters •Hydrogen Isotopes.

•Natural State. •Situation of hydrogen in the periodic

system. Atomic properties of H. The
•General Characteristics of the element: ions H+ and H-. Covalent compounds
electronic configuration; study of the
chemical bond posibilities. •Dihydrogen.
•Chemical Bond.
• Physical and Chemical Properties
•Physical and Chemical properties
(reactivity)
of dihydrogen.
•Production. •Dihydrogen production.
•Applications. •U s e s a n d applications of
dihydrogen.

•Classification of its compounds and •Binary hydrides: classification and

their properties. general properties.
•Hydrogen Bond.

•Study of the obtaining, properties and •Water as an example of covalent

applications of the most important hydride.
compounds of that element.
1
 Hydrogen Discovery
Diatomic hydrogen gas, H2, was formally first described by T.
Von Hohenheim (better known as Paracelsus, 1493-1541)
who artificially obtained it by mixing metals with strong acids.
Paracelsus was not aware that the flammable gas generated
in these chemical reactions was composed of a new
chemical element.

In 1766, Henry Cavendish was the first to recognize

gaseous hydrogen as a discrete substance, identifying the
gas produced in the metal-acid reaction as “inflammable
air" and discovering that combustion of gas generated
water.

In 1783, Antoine Lavoisier gave the element the name

of hydrogen (in French Hydrogène, from the Greek
ὕδωρ, ὕδᾰτος, "water" and γένος-ου, “creator") when
he verified (along with Laplace) the discovery of
Cavendish.
2
3
 Hydrogen: The simplest atom
H: 1s1
Properties (of Hydrogen):
• Boiling Point: -253 ºC
• It does not react with acidic aqueous
solutions.
• How are the compounds formed with
hydrogen and alkali metals?
Is it a metal or a nonmetal? 4
Atomic Properties
• Electronic configuration in the fundamental
state: 1s1
• It does not have any other electron other
than the valence electron, which is
neither shielded nor it shields any other.
• The next orbital in energy is the 2s, of
too high energy to intervene in the
formation of compounds

Location in the periodic table???

Grou 1: alkaline //// Group 17: halogens

5
 “Atomic” Properties

EI (kJ/mol) Electronegativity
H 1312 2,1
Li 520 1,0
Na 496 0,9

6
7
Conclusion: hydrogen is a unique element,
and that is why all (or the vast majority) of the
texts study it separately, in an isolated subject,
without including it in any family (group) of the
periodic table.
“Hydrogen; an exceptional element
... the physical and chemical properties of
hydrogen cannot be related to any of the
groups in the periodic table. Hydrogen is really
unique, and it is better to consider it
separately”
General Chemistry, R.H. Petrucci, F.G. Herring, J.D. Madura y C.
Bissonnette, 10ª Ed., Pearson Educación, 2011. 8
 Hydrogen: Natural State
• Hydrogen is the most
abundant element at the 7% 1%
Hidrógeno
universe, constituting the He
92% of the atoms number Resto

Stars: H2 y H 92%

Interestellar space: H

On Earth:
- “Free”, only traces in the low atmosphere (0.5 ppm, H2)
- When combined, it is very distributed:
a) H2O: 80% of our planet is covered by water.
b) Organic Compounds: such as carbohydrated and
proteins for the living matter. It is an essential element
for the living organisms.
c) Fossil fuels: hydrocarbons and natural gas.
9
When we talk about the hydrogen element,
what exactly are we referring to?

What is in a container that contains

hydrogen (under normal conditions and
room temperature)?

10
In the free state, under normal conditions, it is not in
its isolated atomic form but forming diatomic
molecules. The half-life of isolated atoms is very small
(~ 0.3 s) because the molecule has a very high
enthalpy of formation from them:
2 H(g) H2(g) ΔH = - 436 kJ/mol H2

The chemical bond in the H2 molecule

VBT MOT
H H linear
σ∗ combination of
atomic orbitals
E
s s 1sA 1sB (LCAO)
σ
H H
-Chemical Bond Order: 1

-Magnetic Properties: diamagnetic

11
 p+n
nE Hydrogen Isotopes
1 2 3
1H 1H 1H

Name protium deuterium tritium

Symbol H D T T ⇒t1/2= 12 años
Nucleus 1p+0n 1p+1n 1p+2n
composition
Mass (uma) 1.0078 2.0141 3.0161
Abundance(%) 99.985 0.015 10−15

12
http://www.ciaaw.org/pubs/Periodic_Table_Isotopes.pdf
13
Isotopes in
Chemistry

14
 Study of the hydrogen bonding
possibilities.
Electronic configuration of the fundamental state :
1s1 ⇒ A hydrogen atom can stabilise through
three different ways:

•Lossing of 1 e- → H+ (proton) Cationic Ionic Chemistry

•Gainning of 1 e- → H- (hydride ion) Anion Ionic Chemistry

•Sharing of 1 e- → H–E Covalent Chemistry

•Others (metallic hydrides...)

15
H+ Formation ⇒ Ionic compounds with H+ cation

H(g) → H+(g) + 1e- ΔHEI = 1311 kJ.mol-1

ΔH o (kJ)
f
218 1311
1/2 H2(g) H(g) H+(g) 1529 Very high value

M(s) M(g) M+(g)

Li 162 520 682

Affordable values

Cs 79 375 454

16
There is no cationic chemistry in
hydrogen ⇒ There are no stable
compounds (under normal
conditions) in which hydrogen is as
an H+ cation.

In aqueous solution: not free, associated

to water molecules Hydronium ion

H+(g) + H2O(l) → H3O+(aq)

o
ΔH = -1120 kJ 17
 -
H Formation (Hydride ion)
H(g) + 1e- → H-(g) ΔHAE = -73 kJ.mol-1
ΔH o (kJ)
f
1/2 H2(g) 218 H(g) -72 H- (g) 146

1/2 X2(g) X(g) X-(g)

F 79,4 -332,6 -253,2

I 75,6 -295,5 -219,9

The electro-affinity of H is much lower than that of any halogen (the Z effec on
that second electron is very low and the repulsions between the two electrons
in an orbital as small as 1s are much greater than in the case of np orbitals of
halogens).
By gaining 1 e- the H- ion is formed in salts when it faces slightly
polarizing cations, such as alkaline and alkaline earth. 18
 Ionic hydrides
(contain the H- anion)

This anion can only be considered

to exist in its combinations with
the alkaline and alkaline earth
elements (the most electropositive
metals)
(except Be and Mg)
19
 Covalent Bond Formation H-E
This is the most abundant chemistry
for hydrogen: H2; H2O; CH4 (all organic
compounds);H2SO4; HX...
It forms compounds of this type with most of the elements of
the periodic system, except with the most electropositive and
with some transition metals.

• The formed bonds (H-E) are very strong due to the high
electron density of its small valence orbital.
• When bonding atoms of elements of electronegativity
different (E) from its own, the bond has a more or less
polar character (δ+/δ ), in one sense or another.
20
 Covalent Bond Formation H-E
As a function of the electronegativity of
the element E:
• χΗ ≈ χΕ: Η atom is almost neutral (apolar bond)
i.e. CH4 (hydrocarbons), PH3
• χΗ < χΕ: Ηδ+ →Ε δ )

) E= F, O, N, Cl, Br, S
) ) Βδ Ηδ+ Ε δ , hydrogen bond

21
22
23
 Hydrogen Properties

Physical Properties

Molar Mass Boiling Point Bond energy

(g.mol-1) (ºC) (kJmol-1)

H2 2.02 -253 436

•Hydrogen under normal conditions

is a colorless and odorless gas with
a very low boiling point. It is
practically insoluble in water.
•It is the lightest gas that exists.

Química General”. P.W. Atkins; Ed. Omega, Barcelona 1992.

24
Hydrogen Reactivity (dihydrogen)
• Hydrogen is not very reactive in n.c. (much less
than halogens or alkali metals for example), mainly
for kinetic reasons, because of their high binding
energy (436 kJ / mol)*
• Its most outstanding chemical property is its (soft)
reducing character
Molecular hydrogen is activated (becomes more
reactive) on the surface of some metals (Ni, Pd, Pt)
or by the formation of a metal complex.
*For fundamentally kinetic causes, although also partly
thermodynamic: remember that only when the binding energies of
the products are similar to those of the reagents, or greater,
spontaneous reactions are likely to occur.
25
In chemistry, the reactivity of a chemical
species is its ability (impetus) to react in the
presence of other chemicals. One can
distinguish between thermodynamic
reactivity and kinetic reactivity.

Reactivity is a somewhat vague concept in

chemistry.
Wikipedia:
https://es.wikipedia.org/wiki/Reactividad
https://en.wikipedia.org/wiki/Reactivity_(chemistry)
Acceso el 21/02/2017

The reactive concept is a relative

one 26
Reactividad del hidrógeno (dihidrógeno)

HX#(HF,#HCl,…)#

X2#
O2# H2O#
H2#
M# N2#

MHn# C# NH3#

CH4#

31
 Hydrogen reactivity (dihydrogen)
Most important reactions for dihydrogen

Against very electronegative elements

H2 + F2 → 2 HF 3 H2 + N2 → 2 NH3*

H2 + ½ O2 → H2O H2 + Br2 → 2 HBr*

H2 + Cl2 → 2 HCl H2 + I2 → 2 HI*

It acts as a (soft) reductant!

*very slow in the absence of catalyst and at ambient P and T

Other nonmetals give even slower and more difficult reactions (for
example, the reaction with carbon to produce methane) 32
When we mix hydrogen and oxygen under normal
conditions, will they react?

33
 H2(g) + O2(g) → ?
What products can we get?
ΔGº298 K K298 K
(kJ/mol H2O)

H2(g) + ½ O2(g) → H2O(l) −238 1038

H2(g) + O2(g) → H2O2(l) −120 1019

34
 Thermodynamic Study
A mixture of hydrogen and oxygen, will it give a spontaneous
reaction?

¿ΔGs/r?
ΔGs = ΔHs - TΔSs
The variation of free energy of a reaction (of
a system) is related to changes
"in the strength of the bonds" and in the
degree of order of the system.
35
 Calculation of the enthalpy of
reaction from the binding energies
ΔHr = Σ ΔH(bond break) + ΣΔH(bond formation)

≈ Σ Ee(reactants) - Σ Ee(products)

We calculate the "heat of reaction" by

making an energy balance with the bonds
that are broken and those that are formed
in the course of the reaction.

Slide 36 of 48 General Chemistry: Chapter 10 Copyright © 2011 Pearson Canada Inc.

36
 Estimation of the ΔHr of a reaction from
tabulated values ​of average bond energies.
Hess cycle

H2(g) + ½ O2(g) → H2O(l)

ΔH condensación =
Ee H-H ½Ee O=O -ΔHvap

- 2 Ee O-H
2 H(g) + O(g) H2O(g)
- 2 Ee O-H
ΔHr ≈ Σ Ee(reactants) - Σ Ee(products)=
= EeH-H + ½ EeO=O - ΔHvap - 2 EeO-H
37
The enthalpy of vaporization is the amount
of heat that must be absorbed for a certain
amount of liquid to vaporize at constant
temperature.
Química General, R.H. Petrucci, W.S. Harwood y F.G. Herring; 8ª ed., Pearson Educación,
S.A., Madrid, 2003. Pág. 482.

ΔH condensación = -ΔHvap

38
Estimation of the ΔHr of a reaction from tabulated values ​of
average bond energies. Hess cycle

H2(g) + ½ O2(g) → H2O(l)

Ee H-H ½Ee O=O ΔH condensación =
-ΔHvap

2 H(g) + O(g) H2O(g)

- 2 Ee O-H

ΔHr ≈ Σ Ee(reactants) - Σ Ee(products)=

= EeH-H + ½ EeO=O - ΔHvap - 2 EeO-H=
= 436 + 249 – 44 – 928 = – 287 kJ/mol H2O
(Very) Exothermic Reaction 39
 H2(g) + ½ O2(g) → H2O(l)

ΔHr ≈ Σ Ee(reactants) - Σ Ee(producos)=

= EeH-H + ½ EeO=O - ΔHvap - 2 EeO-H= – 287 kJ/mol

ΔSr = ΣS(products) - ΣS(reactants) =

= 70 – (131 + 205/2) = – 163 J/mol H2O.K

ΔGs = ΔHs – TΔSs= -287- (298×-0,163) = -238

KJ/mol H2O
40
Estimation of the ΔHr of a reaction from tabulated
values ​of enthalpies of formation

H2(g) + ½ O2(g) → H2O(l)

∆H° = ∑νp∆Hf°(products) - ∑νr∆Hf°(reactants)

ΔHr = -286 – [0 + 0] = -286 kJ/mol of H2O

41
 Conclusions of the enthalpy study

•This is an exothermic reaction, and therefore

probably spontaneous at room temperature1.
•Exothermic reactions are exothermic because
stronger bonds are formed than those that break (in
this case the O-H bonds are very strong).
•The reaction occurs because dioxygen is a strong
oxidant (a chemical species very eager for electrons),
which reacts with many substances (reductants, even
if they are mild like H2), in what we will call a redox
reaction.
1…only when the binding energies of the products are similar to
those of the reactants, or higher, are spontaneous reactions likely
to occur. (Rayner, 2ª Ed., pág. 118)
42
• The reaction rate at 298 K is negligible. For the
reaction to proceed appreciably, we must raise the
temperature or use a catalyst (or start it, for
example by means of an electric spark).

43
Knowing more… Hydrogen explodes in contact with air?

Hydrogen and air explode when

the mixture contains 4 to 75%
hydrogen. The flame burns
quietly until the mixture enters
this range. Ted Lister, “Experimentos de química
clásica”, Ed. Síntesis (2002), pág. 141

Explosion of a balloon filled with

hydrogen and oxygen when a candle
approaches it.
The Hindenburg, moments after it Brown, LeMay y Bursten, “Química, la ciencia central”, 9ª.
burned down at the mooring base at edición, Pearson Educación, 2004.
Lakehurst Aircraft Station, New Jersey,
on May 6, 1937. It was completely
destroyed in less than 40 seconds.

Fuente: wikipedia: http://es.wikipedia.org/wiki/

Dirigible_Hindenburg

44
Reactividad del hidrógeno (dihidrógeno)

HX#(HF,#HCl,…)#

X2#
O2# H2O#
H2#
M# N2#

MHn# C# NH3#

CH4#

45
 Hydrogen reactivity (dihydrogen)
Most important reactions for dihydrogen

Against very electropositives elements:

(Alkali, Ca, Sr and Ba)

Δ# M+H3#
M##+#H2###→###
M2+(H3)2#

It acts as a (soft) oxidant!

46
Metales más reductores que el H2
H2(g) + 2 e−→ 2H−(“ac”) - 2,25 V
47
 Hydrogen reactivity (dihydrogen)
Against some transition metals:
a) Stoichiometric combinations:
Δ (MH , MH ,…MH )
M + H2 → 2 3 n

Constant ratios and simple and complete numbers

b) Non-stoichiometric combinations:
there is an interaction with the metal that may or may not lead to the
total breaking of the bond (in this case the link is weakened) (M8H1,6).

Schematic representation of the interaction of an H2 molecule with the surface of a metal for
adsorbed hydrogen atoms. It is the basis of the catalytic effect of these metals in some
hydrogen reactions (for example to form NH3).
Adaptado de Housecroft C.E., Sharpe A.G., “Química Inorgánica” 2º Ed.; Pearson Educación, 2006
48
 Hydrogen reactivity (dihydrogen)
Frente a compuestos: H2 always acts as reductant
!Óxidos metálicos:

Δ
MO(s) + H2(g) → M(s) + H2O(g)
Δ
MOx + H2 → MOy + H2O (y<x)

!Double and triple bonds:

Hydrogenation reactions:

Oil refining

General Chemistry: Chapter 22 Copyright © 2011 Pearson Canada Inc. 49

 H• Radicals in chain reactions
Many gas phase reactions are chain reactions. The intermediaries of a
chain reaction are called chain propagators. In radical chain reactions,
chain propagators are radicals (species with a missing electron "very
reactive").

Let's have a look at the example of a (simplified) mechanism of such a

reaction, the reaction of hydrogen with chlorine

Initiator can be a photon, a

Cl2 → 2 Cl• Iniciation spark, heating, etc
Cl•(g) + H2→ HCl + H•
Propagation (Chain Reaction)
H• + Cl2 → HCl + Cl•

H• + Cl• → HCl termination step (Low probability)

These reactions, depending on the conditions (temperature, pressure ...)

can be explosive (thermal explosion).
50
 H2 Production
- water
Natural Sources:
- hydrocarbons

H+ (o H3O+) reduction in water or acids: H+ + e- → ½ H2

At the laboratory
Strong acid with diluted metal:
Zn(s) + 2H3O+(ac) → H2(g) + Zn2+(ac) +2H2O(l)

Zn(s) + 2HCl(ac) → H2(g) + Zn2+(ac)+ 2Cl-(ac)

Metal + Base: Al(s) + 3 OH-(ac) + H2O→ H2(g) + [Al(OH)4]- (ac)

Metal G1/G2 in water: Na(s) + 2H2O(ac) → H2(g) + NaOH(ac)
51
52
 H2 Production
In the industry
a) “Water Gas” Process

Ni, 800°C
CH4(g) + H2O(g) CO(g) + 3 H2(g)
ΔH= 230 kJ ΔS > 0
Fe2O3/Cr2O3
CO(g) + H2O(g) 400°C CO2(g) + H2(g)

ΔH= -40 kJ ΔS = 0
*Química General, R.H. Petrucci, W.S. Harwood y F.G. Herring; 8ª ed., Pearson Educación, S.A., Madrid, 2003. Pág. 656
53
 Ni, 800°C
CH4(g) + H2O(g) CO(g) + 3 H2(g)
Fe2O3/Cr2O3
CO(g) + H2O(g) 400°C
CO2(g) + H2(g)

K2CO3(ac) + CO2(g) + H2O(l) → 2 KHCO3(ac)

54
 H2 Production
In the industry
b) Electrolysis of water (of a solution of sodium
hydroxide or potassium hydroxide, to make it conductive):
more expensive, but high purity hydrogen is obtained
H+ + e- → ½ H2 (E = -0,414V a pH= 7)
problem: Electric energy price
Cátodo: 2 H+(ac) [H3O+] + 2e- → H2(g) + 2 H2O(l) E1o = 0,0 V (pH = 0)
2 H2O(l) + 2 e- → H2(g) + 2 OH-(ac) E1o = - 0,8 V (pH = 14)

Ánodo: 2 H2O(l) → O2(g) + 4 H+(ac) + 4 e- E2o = - 1,23 V (pH = 0)

4 OH-(ac) → O2(g) + 2 H2O(l) + 4 e- E2o = - 0,40 V (pH = 14)

2 H2O(l) → O2(g/ac) + 2 H2(g/ac) ET(pila) = - 1,23 V (at any pH)

55
c) As a by-product in obtaining chlorine

Electrolysis of aqueous NaCl solutions

Electrolysis
NaCl(ac) Cl2 (g) + H2(g) + NaOH (ac)

56
 Applications
H2O M

M+ ProducciÛn
Metal
O2 de metal
Production
As fuel
H2
C=C N2

-C-C- NH3 General Chemistry, R.H. Petrucci, F.G. Herring, J.D. Madura y C. Bissonnette, 10ª
Ed., Pearson Education, 2011

Margarina
Margarine Fertilizantes
Fertilizers
HNO3

As fuel:
H2 + ½ O2 → H2O ΔH = -286 kJ

57
How wonderful would be if…!

58
Learn more… Hydrogen as fuel

The space shuttle's cylindrical

tanks store 11458,000 L of
liquid hydrogen and 542,000 of
liquid oxygen, which run out in
a few first minutes of flight!

By NASA; edited by jjron (tilt corrected) - http://spaceflight.nasa.gov/gallery/images/shuttle/sts-120/html/sts120-

s-028.html, Public Domain, https://commons.wikimedia.org/w/index.php?curid=16141567
59
Most relevant
H-compounds:

Hydrides
Water

60
Binary Hydrides: Clasification and general properties

(ionic) (covalent)

Definition: Binary hydrogen compounds: EHn

Nomenclatura: “ide” to the most electronegative element: NaH; HCl.
Common names: H2O; NH3 etc.
Clasification: based on the most prevalent chemical bond type 61
Classification of hydrides according to the type of bond

Ionic Hydrides (saline): those that show properties of salts.

Metal hydrides: show characteristic properties of metals

Covalent hydrides: those whose properties agree with

those derived from a covalent bond metal.

62
 Ionic Hydrides (saline) (MH, MH2)
(M = alkaline, alkaline earth except Be and Mg: only
the most electropositive metals!)
•They contain “the H– ion”

•Direct synthesis: 500-700 ºC

M + ½ H2 Δ → MH ΔHf < 0

•Non-volatile crystalline solids

They are
•High conductivity in fluid phase considered
fundamentally
•Crystallize in ionic networks: ionic compounds
Alkaline (NaCl, cubic lattice)
CaH2, SrH2, BaH2 (PbCl2, Hexagonal close packed)

63
 Ionic Hydrides: Chemical properties
•Reactivity: They are very reactive. They are used as
strong reducing agents, as indicated by the potential value
of the H2/H- semipar:

Eo (½H2/H-) = - 2,25 V
Their reactivity increases in the group with the atomic weight.
(alkaline hydrides more active than alkaline earth hydrides)
Down the group:
- The difference in electronegativity increases (X-H), so H-
becomes very reactive.
- The differences in size between X and H increases.
(Crystalline packings are less stable ! more reactive)

64
 Ionic Hydrides: Chemical properties
•Reactivity: They are very reactive. They are used as
strong reducing agents, as indicated by the potential value
of the H2/H- semipar:

Eo (½H2/H-) = - 2,25 V
2 MH(s) + O2(g) → M2O(s) + H2O(g) / 2 MOH

NaH(s) + H2O(l) → NaOH(ac) + H2(g)

CaH2(s) + 2 H2O(l) → Ca(OH)2(s) + 2 H2(g)
These two reactions could actually be considered both redox and
acid-base reactions (hydride can be considered a very strong
base).
MH + H+ → M+ + H2(g) H- + H2O → H2 + OH-
65
CaH2(g) + H2O(g) → Ca(OH)2(s) + 2 H2(g)

Calcium Hydride

General Chemistry: Chapter 22 Copyright © 2011 Pearson Canada Inc.

66
 Hydrolysis
Name given to acid-base reactions in which ions
act as acids or as bases
Química General, R.H. Petrucci, F.G. Herring, J.D. Madura y
C. Bissonnette, 10ª Ed., Pearson Educación, 2011.

Reaction of a substance with water or its

ions. (NaH(s) + H2O(l) → NaOH(ac) + H2(g))
K. W. Whitten, R. E. Davis y M. L. Peck, Química General,
Ed. McGraw-Hill. 5ª ed (1998)

67
 Ionic metal hydrides play a very important role
in organic chemistry. For example, CaH2 is used
to remove water from organic solvents because
it reacts easily with water.…
…Lithium hydride (LiH) is used to obtain lithium
aluminum hydride (LiAlH4) which is a powerful
reducing agent used in organic chemistry .

Química General, R.H. Petrucci, F.G. Herring, J.D. Madura y C. Bissonnette,

10ª Ed., Pearson Educación, 2011.

68
 Covalent hydrides
• They are those formed between hydrogen and nonmetals (except
noble gases).
• Most molecular or covalent hydrides are volatile and have simple
structures that meet the VSEPR (Valence shell electron pair
repulsion) theory
a) With elements of analog electronegativity. Molecular species.
Gases(CH4; SiH4 ; PH3) (Low intermolecular forces)

b) With high electronegativity elements: Hδ+. Associated molecules by

hydrogen bond: gases or liquids (HF; H2O; NH3);

a) With low electronegativity elements: Hδ-. Polymers: BeH2

69
 Covalent hydrides
Obtention
Direct synthesis (S, N2, O2, X2):
½ Cl2(g) + ½ H2(g) ! HCl(g)
N2(g) + 3H2(g) → 2 NH3(g) (Δ, P, cat)

Properties (acid-base, redox)

Variables:
•HX: strong acid
•H2O: amphoteric species
•NH3: weak base 70
 Metallic Hydrides or Interstitial
• They are so named because they are conductors of electricity.
• They originate with elements of the transition metals.
• They are obtained by direct synthesis, with heating.
• Many times they have a variable composition (they are non-stoichiometric:
TiH1.9).
• Hydrogen atoms occupy holes in the metal lattice.
• They release hydrogen (as H2) when heated or treated with an acid.
• The nature of the bond between M and H is not clearly established.

Química General”. P.W. Atkins; Ed. Omega, Barcelona 1992.

71
Metallic hydrides
Absorb large amount of
H2, which can be
released at will

H2 storage

They are used in modern nickel

metal hydride batteries (NiMH)

72
Water

73
 Water as example of covalent hydride

H2O(gas):
• Discrete molecules
• Angular geometry. 104,5º
• AB2E2; hybridizationn sp3
• Dipole moment. µ = 1,84 D
H2O(sólida):
• Strong association by hydrogen
bond
• Tetracoordinated Oxygen
• Bond angle109,5º
• Open structure
• “Low” density
•O-H distance increases to 1 Å El agua

74
 Comparison of boiling points of some hydrides of the elements of groups 14 - 17
Petrucci, General Chemistry: Chapter 12 Copyright © 2011 Pearson Canada Inc.

It is generally expected that the melting and boiling points of

members of a series of related molecular compounds increase
with increasing molecular size, owing to an increase in
intermolecular dispersion forces
75
 Comparison of boiling points of some hydrides of the elements of groups 14 - 17
Petrucci, General Chemistry: Chapter 12 Copyright © 2011 Pearson Canada Inc.

A hydrogen bond is formed between an H atom attached to an

electronegative atom and an electronegative atom that has an
unshared pair of electrons.
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 Liquid water as solvent
It is a widely used solvent for many reasons,
including:
• It is very cheap
• It is a harmless sustance
• It dissolves a large number of substances (specially
polar compounds)
• It is able to dissolve ionic species:
ΔHº(hidr), ε = 80 ; µ = 1,84 D.
• wide range in liquid state.
• It dissociates many substances (electrolytes) into
ions producing conductive solutions (of the electric
current).

77
 Liquid water as solvent

Most important reactions

- Acid-base processes
NaOH (aq) + HCl (aq) → NaCl (aq) + H2O

- Redox processes
4 HNO3 (c) + Pb → Pb(NO3)2 + 2 NO2 + 2 H2O

- Dissolution (precipitation)
AgNO3 (aq) + NaCl (aq) → AgCl ↓ + NaNO3 (aq)

78
Liquid water as a solvent for ionic
compounds

79
¿Son solubles en agua los siguientes hidruros
(todos gases en c.n.): CH4; NH3; H2S; HCl?
 Water: chemical properties

Acid-Base character. Amphoterism

H2O(l) + H2O(l) H3O+(aq) + OH-(aq)

Kw = 10-14

AH(aq) + H2O(l) A-(aq) + H3O+ (aq)

B(aq) + H2O(l) BH+(aq) + OH-(aq)

81
 Water: chemical properties
Water redox behaviour
As oxydant, it reduces to hydrogen:
2 H2O + 2 e- → 2 OH- + H2

As reductant, it oxydizes to oxygen:

2 H2O → 4 H+ + O2 + 4 e-

•It is a weak reducing agent

a neutral
•It is a weak oxidizing agent pH

The pH of the reaction will be very important in

the redox behavior of the water.
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 Redox behavior of water: E-pH diagrams Redox stability
diagram of water

H+ + e- ½ H2 Eo = 0,00 V (pH=0) (1)

H 2O + e - ½ H2 + OH- Eo = -0,826 V (pH=14) (1’)
O2 + 4 H+ + 4 e- 2 H 2O Eo = 1,23 V (pH=0) (2)
O2 + 2 H2O + 4 e- 4 OH- Eo = 0,404 V (pH=14) (2’)
E (V)
(3)
1,23
(2) (4)
(2’)
Thermodynamc
0,00 0,404
Stability region
-0,5
(1) Kinetic stability region
(1)

-0,826
(2)
•It is a weak reducing agent
14 (1’)
0 7
pH •It is a weak oxidant agent
Diagram E-pH (Pourbaix diagram) 83
Learn more ... Water as a crystallization solvent
Crystallisation solvent
When crystals of a compound are formed in a solvent, they may contain
crystallization solvent; If the solvent is water, the compound is a hydrate.
The formula of the solvated compound shows the molar ratio in which the
crystallization solvent is present, for example CuSO4 · 5H2O, copper (II)
sulfate pentahydrate or copper (II) sulfate-water (1/5).

Clathrates (from latin word clathratus “enclosed behind bars”)

Substance in which molecules or atoms are trapped inside the cavities of
the crystalline framework (crystalline network) of other molecules. They
usually form when atoms or molecules of a solute are trapped in the
crystalline network of the liquid solvent when it solidifies.

84
CH4