Chemistry I

PD Dr. Christoph Wutz

christoph.wutz@chemie.uni-
christoph.wutz@chemie.uni-hamburg.de

http://www.chemie.uni-
http://www.chemie.uni-hamburg.de/tmc/wutz/
hamburg.de/tmc/wutz/

Page 1

Contents

1. Introduction
Books, Internet, History, Basic Concepts
2. General Chemistry
2.1 Atomic Structure
2.2 Periodic System
2.3 Chemical Bond, Molecules
3. Physical Chemistry
3.1 State of Matter, Phase
Transitions, Separation Proc.
3.2 Chemical Reaction
Thermodynamics, Kinetics
4. Inorganic Chemistry
4.1 Acids/Bases, pH-
pH-value
4.2 Salts, Solubility
4.3 Redox reactions
4.4 Electrochemistry

Page 2

1
 1. Introduction

classic basic advanced

€ 13.40 336 Pages; € 25.-
25.- 1397 Pages; € 53.-
53.-
ISBN: ISBN: 978-
978-0-19- 927789-6 ISBN: 978-
19-927789- 978-0-19-
19-927789-
927789-6
978-
978-0486656229

Page 3

On-
On-line

Introduction to Chemistry (Mark Bishop)

http://preparatorychemistry.com/

On-line textook (R. Dickerson; CalTech)

http://caltechbook.library.caltech.edu/178/

On-line lectures and notes (MIT):

http://ocw.mit.edu/courses/chemistry/

Test your knowledge on:

http://www.chemistry-drills.com/

Page 4

2
 History I:
Unintentional Chemistry
3000 BC.: Smelting of lead, copper and tin (bronze)
1. Roasting of metal ore at about 300°
300°C :

Malachite: CuCO3 CuO + CO2

2. Reduction at >1000°
>1000°C: 2 CuO + C 2 Cu + CO2
metal oxide + charcoal
→ metal + carbon dioxide

Page 5

History II:
Alchemy
Intentional, traditional, non-
non-scientific chemistry;
Protoscience:
Protoscience: Precursor of modern chemistry:
• Creation of the "philosopher's stone," (catalyst?)⇒
• Conversion of base metals into solver or gold
• Search for the universal solvent "alkahest"
Notion of Greece Buddhism China (Tao)
elements: Fire (hot) Fire Fire
Water (wet) Water Water
Earth (dry) Earth Earth
Air (cold) Wind
Spirit/Ether Space
Wood
Metal
Some Discoveries/Inventions:
Discoveries/Inventions:
•Sal ammoniac (NH4Cl), cinnabar (HgS
(HgS):
):
by Abu Musa Jabir ibn Hayyan,
Hayyan, Arabia 8. Jh.
Jh.
•Alcohol (ethanol C2H5OH), Italy ~1100 from wine
•Medicals; mercury, arsenic, antimony comp:
by Paracelsus, 16. Jh.
Jh.
•Phosphorous: Hennig Brand; Hamburg 1669
Discovery of Phosphor
•Porcelain: Johann Friedrich Böttger 1707/08 by Hennig Brand (1669)Page 6

3
 History III
Chemistry as Natural Science
After 17. Jh.:
Jh.:
Scientific chemistry:
Exemption from dogma and religion.
Rational conclusions
based of observation
and experiments.
Robert Boyle (1627-
(1627-1691)
Irish researcher
"The Sceptical Chymist"
Chymist" (1661)

Joseph Priestley Carl W. Scheele Antoine Lavoisier J. Gay-

Gay-Lussac Justus v. Liebig
(1733-
(1733-1804) (1742-
(1742-1786) (1743-
(1743-1794) (1778-
(1778-1850) (1803-
(1803-1873)
Engl. researcher Swed.
Swed. Pharm. French Chem. French Chem. German Chem.
Invent.: NH3, O2, Cl2, Ba, Mn; Oxidation Ideal gas law Chem.Analysis
N2O, CO, SO2 HCN, lactic acid
Page 7

Difference Chemistry-
Chemistry-Physics
Physics:
Physics: (Change of) State of Chemistry:
Chemistry: Change of Composi-
Composi-
Matter Example: tion of Matter
Iron: metallic, shiny, conductive, malleable.
Heating iron ⇒ melting Iron in humid air ⇒ gets rusty
cooling ⇒ solidification. Rust: red-
red-brown, non-
non-conductive
Properties unchanged. not moldable
Reversible change of state ⇒ Change of matter
Another example:
Platinum wire heating to red-
red-hot magnesium⇒
Heating magnesium⇒
Cooling: No change in prop. emission⇒
combustion with light emission⇒
Emission of light: physical proc. magnesium oxide (white powder)
⇒ change of matter
Last Example:
Heavy cooling of air ⇒ liquefaction Respired oxygen converts
Slow warming up (distillation) ⇒ carbohydrates into CO2+H2O.
Separation of oxygen and nitrogen Energy is released.
Properties unchanged. ⇒ Chemical process.
Liquefaction, evaporation, melting, Combustion, oxidation,
distillation: physical processes chem. synthesis: Chemical proc.Page 8

4
 Beginning and Resources of
Chemical Industry

before 1820: Production of:

• Soda (sodium carbonate) for processing of
glass, bleaching agents, detergents, etc.
• Synthetic fertilizers
• Dyes
Resources of chemical industry before 1870:
• Coal
• Minerals
• Plant products
• Animal products

Resources of chemical
industry after 1870 - ?
• Crude oil

Page 9

Chemical Hazards

21. Sept. 1921; BASF, Oppau,

Oppau, : Explosion of fertilizer plant:
561 Dead, 2000 Injured, 900 apartments destroyed, 100 m crater
2 NH4NO3 → 4 H2O + 2 N2 + O2 Page 10

5
 Benefit from Chemical Industry
Demographics
Population

Development of chemical industry • Synth. fertilizer

• Pesticides
• Medicals
• Hygiene items Page 11

Why bother with Chemistry?

Chemistry affects our life's:

Medicine
Carbohydrates,
Proteins, Glasses
Medical devices
Fats,
Vitamins, etc.

Toy Detergents
Sports
Soap
equip-
equip- Tooth paste
ment
Mobiles

Coal/Gas Dyes
Petrol Carpets
Batteries Furniture
Page 12

6
 Significance of Chemistry for the Living

from atom via molecules to organism

(>15 mio.!)
mio.!)

Ascorbic Acid

Chlorophyll

Page 13

Analytical/Synthetic Chemistry

Analytical chemistry: Synthetic Chemistry:

Understanding nature: Can we produce the same products
What is it made of? (or even better) in the lab?
What is in there?
and how much?

Wikipedia:
Science of matter and
changes it undergoes.

Page 14

7
 Basic Terms and Concepts
Measures and Units (SI
(SI))
Measure Symbol Unit Symbol
Length l Meter m
Mass m Gramm g
Volume V Liter L
Density ρ Gramm per cm3 g/cm3
Temperature T Kelvin K
Force F Newton N = kg·m/s2
Pressure p Pascal Pa = N/m2
Energy E Joule J = kg·m2/s2
Amount of substance n Mole mol
Molar Mass M Mass per Mole; M = m/n g/mol
Molar concentration c Mole per volume; c=n/V mol/l
Molar Enthalpy H Joule per Mol J/mol
Molar Entropy S J/mol·K

Page 15

General Structure of Matter

Substance Chemical Compound Atomic level

solid

Na+ Cl-
Salt
Sodium chloride
liquid

Hydrogen Oxygen
Water atom atom
Water molecules
gaseous

Air
Oxygen a. nitrogen
molecules (mixture) nitrogen atom Page 16

8
 Mixtures, Substances, Compounds,
Elements
separation by
physical methods
Mixture Substance e. g. water
e.g. distillation or pure
e. g. vodka filtration, extraction
water/alcohol are alcohol
either or

Chemical Decomposition Elements

compounds by chem. methods

composed of two or more different one type oft atom;

chemical elements (types of atoms) no decomposition
connected by chemical bonds by chem. methods
e. g. water H2O e. g. hydrogen (H)
two atoms of hydrogen (H) oxygen (O)
one atom of oxigen (O) iron (Fe)
Page 17

Symbols of Chemical Element

Symbols used for abbreviation of chemical

elements by Berzelius; today by IUPAC:
IUPAC:
One-
One- or two-
two-letters long, only first capitalized.
Mostly derived from Greek or Latin words.

H Hydrogen Na Sodium
He Helium Mg Magnesium
Li Lithium Al Aluminum
Be Beryllium Si Silicon
Jöns Jakob Berzelius
B Boron P Phosphorus Swedish chemist
C Carbon S Sulfur (1779-1848)
N Nitrogen Cl Chlorine
O Oxygen Ar Argon
F Fluorine K Potassium First 20 elements
Ne Neon Ca Calcium
Page 18

9
 Natural Abundance of Elements
Over 90% of the universe is hydrogen (H);
second most is helium (He).
Earth crust(0-40 km) Earth inner core
1% 1% 2%
2% 2%
3% 2%
3% 4%
5%
5%
Fe 7%
8%
Al
O 49%

Si Fe

26% 80%

O Si Al Fe Ca Na K Mg H Res. Fe Si Ni O S Res.

Common compounds: Earth inner core (3000 km)

SiO2, Silicates, Al- mainly composed of iron
Al-, iron oxides,
carbonates, sulfates, hydroxides (2900°
(2900°C, liquid). Fe/Ni-
Fe/Ni-convec-
convec-
tion at mantle ⇒magnetism Page 19

Change of Matter
by Chemical Reaction

Iron-
Iron-Sulfur-
Sulfur-
Iron Sulfur
Mixture: Fe + S

How can it be
separated?
(Fe) (S)

Iron-
Iron-sulfur-
sulfur-
compound
Iron sulfide (FeS
(FeS))
No physical
separation into
iron and sulfur
Chemical reaction possible

Page 20

10
 Chemical Reaction

A chemical reaction is a process that leads to the transformation

transformation
of one set of chemical substances (reactants; reagents)
to another (products).
Chemical equations used to graphically illustrate chemical reactions:
reactions:
Reactant 1 (+ reactant 2) product 1 + (product 2)
A chemical reaction alters the combination of atoms in substances,
substances,
the number of atoms of each elements remains constant.

"The mass of matter remains constant

during chemical reactions".
(Law of Conservation of Mass)

Antoine Lavoisier
fr. Chem. (1743-1794)
Page 21

Chemical Reaction
Example: Sodium Chloride
Example:
Sodium (Metal) Chlorine Salt (NaCl)

Chemical reactions involve a "rearrangement" of atoms.

New compounds are formed with different properties.
Which substance can react with which other substance
yielding which compound in which molar ratio?
Page 22

11
 Elemental Particles

Matter composed of atoms, composed of three elemental particles:

Proton (p+): "big", "heavy" (relatively!), positive

+ mass ~ 1 u

Neutron (n): "big", "heavy" (relatively!), neutral

0 mass ~ 1 u

- Electron (e-): tiny, lightweight, negative

mass ~ 1/1800 u
1,66⋅10-27 Kg
u extremely small unit: 1 u = 1,66⋅
Page 23

Radiation

Radiation is a process in which waves or particles travel through

a medium or space ⇒ Transport of energy or mass.
Dualism: Each radiation has wave and particle character.
Electromagnetic waves (light, micro-
micro-, radio-
radio-, x-
x-ray)
Energy ~ frequency ~1/wave length

Radioactive decay:
decay:
Atomic nucleus emits particle or wave
Name Character Mass Charge
α-radiation He nucleus: 4u +2
2 P+; 2 N
β-radiation Electron 1/1823 u -1
γ-radiation electromag.
electromag. - -
wave
Page 24

12
 2. General Chemistry
Atomic Structure: Early Atomic Models
Law of defined proportions = const. composition (J. Proust, 1794):
1794):
"A chemical compound always contains exactly the same propor-
propor-
tion of elements by mass". E. g. water: oxygen:hydrogen = 8:1

Stoichiometry
Law of multiple proportions (J. Dalton, 1803):
"The proportions of mass of two elements in different compounds
are rations of small whole numbers". E.g.:
100 g of carbon reacts with 133 g oxygen to carbon monoxide
100 g of carbon reacts with 266 g oxygen to carbon dioxide
266:133=2:1
Daltons Atomic Theory (180(1808):
8):
• Elements are made of tiny particles called atoms.
•The atoms of a given element are different from those of any other
other element;
they can be distinguished by their respective relative atomic weights.
•All atoms of a given element are identical.
•Atoms of one element can combine with others to form chemical compounds;
compounds;
a given compound always has the same relative numbers of types of atoms.
•Atoms cannot be created, divided into smaller particles, nor destroyed;
destroyed;
a chemical reaction simply changes the way atoms are grouped together.
together.
Page 25

Geiger-
Geiger-Marsden Gold Foil Experiment
Rutherford Model
1910: α-particles (positive
(positive He-
He-nuclei) directed onto very
thin gold foil: Very few particles deflected ⇒
1. Atoms are almost "empty"
2. Atomic mass concentrated in positive nucleus
3. Atomic volume represented by negative shell

Sir E. Rutherford
(Radium) New Zealand Chem.

ZnS Rutherford
Model
Page 26

13
 Rutherford Atomic Model

Atoms have a positive core (nucleus),

(nucleus),
surrounded by negative electron cloud (shell).
(shell).
Protons and neutrons located
Z=3
in nucleus (⇒(⇒nucleons).
nucleons).
Lithium
Neutrons: no charge,
Protons: charge = +1 ⇒
Number of protons = number of
(pos.) charges in nucleus
= Atomic number (Z) in
periodic system of elements (PSE)
The number of protons determines the element

Atomic diameter ~ 10-10 m, nucleus only 1/100000 of it:

Nucleus: tiny, "heavy", positive Shell: "bigger", light, negative
negative Page 27

Atomic Mass

Number of nucleons (protons + neutrons)= atomic mass (ma),

Mass of electrons can be neglected.

The number of protons determines, which element (type of atom)

(= atomic number Z)

The number of neutrons N plus protons Z determines,

which mass is has. (atomic mass ma = Z + N)

Example: Lithium
3 protons ⇒ atomic number Z = 3
4 neutrons ⇒ atomic mass = 7
Proton
Neutron
Electron
Page 28

14
 Molecular Mass

The mass of molecule mM of a chemical compound is the

sum of the atomic masses of the constituting elements

Example: Glucose C6H12O6

The empirical formula indicates the number of atoms

of each element in the molecule
mM = 6·
6·ma(C) + 12·
12·ma(H) + 6·
6·ma(O)

ma(C)
(C) = 12 u
ma(H)
(H) = 1 u
ma(O)
(O) = 16 u

mM (Glucose) = 6·
6·12u + 12·
12·1u + 6·
6·16u = 180 u
Page 29

Amount of Substance, Mole

The mass unit u measures extremely small quantities (single molecules):

molecules):
The Amount of Substance n (or Chemical Amount) with unit Mole is
a quantity that measures the size of an ensemble of elementary entities
entities
(atoms, molecules other particles) on lab-lab-scale.
The Amount of Substance is no mass, nor a number of entities
- it is, however, closely related to both:
The Amount
m of Substance n is the mass m of a portion related to the
n = Mass M of the substance. The Molar Mass M is a substance-
Molar substance-
M quantity with the unit [g/mol].
specific

Examples: Atomic/molecular mass Molar Mass M

Li = 7 u M(Li)
M(Li) = 7 g/mol
H2O = 18 u M(H2O) = 18 g/mol
H2 = 2 u M(H2) = 2 g/mol
C6H12O6 = 180 u M(C6H12O6) = 180 g/mol

One Mole Li weights 7 g, 1 Mole water ≈ 18 g; 2 Mol H2O ≈ 36 g.

Page 30

15
 Avogadro´
Avogadro´s Number
Illustration of the Mole
An amount of substance n = 1 mol contains always
the same number of particles: Avogadro´
Avogadro´s Number NA:
1 mol ≈ NA = 6·
6·1023 particles
1 mol lithium ≈ 6·1023 Li atoms
1 mol hydrogen ≈ 6·1023 H2 molecules = 12·
12·1023 H atoms
1 mol helium ≈ 6·10 He atoms
23

Representation: 1 particles ⇒ 1023 particles

1 mol lithium 1 mol hydrogen
6·1023 atoms 6·1023 molecules 1 mol water
(7 g) (2 g) 6·1023 molecules
(2+16 = 18 g)

4 mol carbon
1 mol carbon 4·6·1023 atoms
6·1023 atoms (48 g)
(12 g) Page 31

Calculating with the Amount of Substance

The mass m [g] and the amount of substance n [mol)]

can be converted by the molar mass M [g/mol]:
m
M=
n
m
m = M ⋅n n=
Examples: M
What is the mass of 0,2 mol glucose?
m = 180 g / mol ⋅ 0,2mol = 36 g
What is 5,85 g Sodium chloride (NaCl) in Mol?
mA(Na) (Cl) = 35,5 u ⇒ MNaCl= 58,5 g/mol
(Na) = 23 u; mA(Cl)
5,85 g
n= = 0,1mol
58,5 g / mol
Page 32

16
 Illustration of
Stoichiometry and Molar Mass

2 H2 + O2 2 H2O oxygen atom (O):

8 P+;8 N⇒ma=16 u
hydrogen atom (H):
1P+⇒ ma = 1u
2 diatomic 1 diatomic 2 water molecules
hydrogen molecules oxygen molecules
mH2O = 16+2=18u
A water molecule (H2O) consists of 2 hydrogen and 1 oxygen atoms.
The reactants must contain twice as much H atoms as O atoms.
Both elements are diatomic molecules.
Molar Masses: M(H2)=2 g/mol; M(O2)=32 g/mol; M(H2O)=18 g/mol
Hydrogen + Oxygen = Water
(2⋅2u = 4u )
2 molecules (2⋅ (2⋅16u=32u) 2 molecule (2⋅
1 molecule (2⋅ (2⋅18u=36 u)
2000 molecules 1000 molecules 2000 molecules
(2⋅6 ⋅1023
2 mol (2⋅ (6⋅1023
1 mol (6⋅ (2⋅6⋅1023 molecules)
2 mol (2⋅
molecules) molecules)
4g + 32 g = 36 g
Conservation of mass! Page 33

Molar Volume of Gases

6⋅1023 particles,
1 Mole of any gas contains always 6⋅
either atoms (noble gases, e. g. He),
or diatomic molecules (other gaseous elements: H2, N2, O2, F2, Cl2)
or compound molecules (e. g. CO2).

1 Mole of ideal gas has a volume of V = 22,4 L under STP.

Molar volume of gases: Vm = 22,4 L/mol :

Example:
Example: A volumeV of 1,12 L of gas contains
V of=substance n [mol]?
which amount
m
n
V 1,12 L V
n =⋅ n =
V =V n == 0,05mol
m V 22,4 L mol Vm
m

Page 34

17
 Concentration - Molarity
Many chemical reactions in solvent (e. g. water)
How many reactant particles are in the solution?
n
The molar concentration c defined as amount of a consti-
consti- c=
tuent n divided by the volume of mixture (or solvent*) V
*Dissolving a substance in a solvent does not change the
V
volume significantly. The density is increased.
Examples:
Examples: 2mol
2 Mole of a substance are dissolved c = = 4mol / L
in 500 mL solvent. c = ? 0,5 L
Which amount of substance has to be dissolved in 200 ml,
yielding a solution ? n = c ⋅V = 0,5mol / L ⋅ 0,2L = 0,1mol
2 Mole have to be dissolved in n 2mol
how much solvent, so that c = 0,1 mol/L? V = = = 20 L
c 0,1mol / L
1,8 g glucose in 100 ml water; c = ?.
m 1,8 g 0,01mol
n= = = 0,01mol = 10− 2 mol c= = 0,1mol / L
M 180 g / mol 0,1L Page 35

Isotopes

Isotopes are variants of atoms of a particular chemical element,

differing in the numbers of neutrons and in the atomic mass.
They contain the same number of protons,
but a different number of neutrons.
Examples:
Examples: 2
1 Deuterium: 1 H
Hydrogen: 1 H
12 13
Carbon: 6 C ~99% nat. abundance; C ~1%
6
14
Traces of 6 C ; instable ⇒ radioactive
(Radiocarbon dating)
235
Uranium: 92 U fissile; 238U non fissile, both radioactive
radioactive
92
Isotopes have identical chemical properties (bonding),
but different physical properties (mass)
Page 36

18
 Non-
Non-whole Number Masses

The atomic masses of many elements in the PSE are,

non-
non-whole numbers, since they consist of mixtures of isotope.

Example:
Example: Chlorine, average atomic mass = 35,45 u
consists of:
Calculation:
- 35Cl: 75.7%
- 37Cl: 24.2% 0,757 ⋅ 35 + 0,24 ⋅ 37 = 35,45

Elements that form only one stable type of atom (isotop

(isotop))
are named pure elements.
elements.

Example: 19Fluorine
Example:

Page 37

Ions
Atoms contain as many electrons in the shell as protons
in the nucleus and are consequently neutral.
Ions are atoms or molecules in which the number of electrons
is not equal to the total number of protons,
giving it a net positive or negative electrical charge.

Ions have completely different properties than the resp. atoms !

Examples: Na → Na+ + e- Positive ions = cations,,
cations
Cl + e → Cl
- -
Negative ions = anions.
anions.
Cations derived from metal name (sodium (cat)ion
(cat)ion,, silver (cat)ion
(cat)ion))
or have the suffix –ium (NH4+ = ammonium ion)
Anions from non-
non-metal atoms have the suffix –ide (chloride)
in compounds with oxygen –ate (SO42-=sulfate) or –ite (SO32-=sulfite)
Ions can carry multiple charges: Examples: Al3+, O2-
Examples:
Page 38

19
 Review of Rutherford Model
Rutherford´
Rutherford´s model makes no statement about the electron-
electron-structure of
the atom or the energy of the electrons in the shell; it does not
not explain
the differences in chemical behavior of the elements .

Experiment:
Experiment: Hydrogen absorbs specific
colors = wave length from the spectrum of
visible light
H2 Prism
Absorption spectrum of hydrogen
Vice versa, thermally activated hydrogen emits
light of exactly the same wave lengths.

H2
Emissions spectrum of hydrogen

Why specific wave length = energies?

Page 39

Discrete Energy Levels

of Electrons
Electrons can occupy diffe-
diffe-
rent well-
well-defined (=discrete)
energy levels in the shell.
Transition between level
by absorption or release
of energy
(net energy conservation)
Excitation: By additional energy
(heat, photon, electricity) the Excitation of atom by light
electron can be moved to
higher level (outer orbit).
If photon energy too high
⇒ ionization
Deactivation of excited
electrons under emission of
electromagnetic wave and
return to lower level
(inner orbit).
Deactivation by emission of light Page 40

20
 Bohr Model

Electrons travel around nucleus in circular orbits

(shells) associated with definite energy levels
n=1
with the principle quantum number n.
n=2
The orbit radius r and the electron energy
Nucl n=3 increases as n2.
The shells are filled with electrons
from inside (lowest energy level)
Shell n elec-
elec- to outside.
trons
Each shell can carry a certain
K 1 2
number of electrons:
L 2 8
M 3 18 2 ·n 2
In the heaviest atoms
N 4 32
7 shells are occupied.
Only the electrons of the outermost (valence-
(valence-) shell Niels Bohr, Dan. phys.
Atomic model 1913
can participate in formation of chemical bonds. Nobel prize 1922 Page 41

Electron Configuration
Element Z n=1 n=2 n=3 n=4
max. 2 max. 8 max 8+10
H 1 1
He 2 2
Li 3 2 1
Be 4 2 2
F 9 2 7
Ne 10 2 8
Na 11 2 8 1
Mg 12 2 8 2
Cl 17 2 8 7
Ar 18 2 8 8
Complete (closed) shells The number of valence electrons
Valence electrons determines chemical properties!
Page 42

21
 Atomic Emission Spectrometry
Flame Photometry
Each element has its unique electron configuration
and hence characteristic electron transitions and corresponding
lines in the emission spectrum ⇒ atomic emission spectrometry.
spectrometry.
Slit
Sample

Eye Prism Optic

Light
source
Magnesium
Silicon

Sodium
Copper
Even without spectrometer some elements Na Li Cu
can be distinguished by the color of the flame: Page 43

Periodic Table (System) of Elements

Prediction of Elements by Mendeleev

Ga

Dimitri Mendeleev
Periodic table
(1869)
Properties of Gallium (Ga)
Prediction Reality
Atomic mass ~ 68 69,72
Density ~ 5,9 g/cm3 5,91 g/cm3
Melting Temp. ~ 30°C 29,8°C
Oxide X2O3 Ga2O3
Chloride XCl3 GaCl3
Page 44

22
 Periodic Table of Elements

Elements listed with increasing value of atomic number

= no. Protons in nucleus = no. electrons in shell. Page 45

Structure of Periodic Table

Main group number Main groups

Main groups = number of
valence electrons
I. Groups VIII.
1. II. III. IV. V. VI. VII.
2. Auxiliary groups
3.
Periods 4.
5.
6. La
7. Ac

Lanthanids
Actinids
Page 46

23
 Metals,
Metals, Metaloids (Semimetals)
Semimetals),
Non-
Non-metals

•isolators
(exept carbon
as graphite)
•gaseous or
low melting
•brittle solids

•conductive
•solid
(except mercury)
some high melting
•malleable, ductile
Metallic character of elements in the periodic table
decreases from bottom left to top right.
> 80% of the elements are metals.
Page 47

Main Group Elements

I. Alkali metals:
metals: silver, low melting, soft
Highly reactive,
reactive, natural abundance
only in compounds,
compounds, not elemental.
II. Alkali earth metals:
metals: like alkali, but less
reactive (stable in air).
Auxilliary Groups

III. Boron group:

VII. Halogens:
Halogens: all nonmetals
F/Cl
F/Cl gas, Br liquid, I solid
reactive; form salts with I and II
VIII. noble (inert) gases:
gases:
extremely low reactivity
→ elemental state: as traces in air
group: B hard metalloid,
Al→Tl soft metals. Al-
Al→ Al-compounds
highly abundant in Earth´
Earth´s crust.
IV. Carbon group:
group: C nonmetal, Si,Ge meta-
meta-
loids;
loids; Sn,
Sn, Pb met.; different properties.
Si high abundance (quartz); C→natural
compounds; Pb high density.
V. Nitrogen group:
group: N=non-
N=non-metall (gaseous)
P/As met. and nonmet.
nonmet. allotropes,
Sb/Bi=met.;
Sb/Bi=met.; N main ingredient air 78%
VI. Chalcogens:
Chalcogens: O gaseous, nonmetal,vital
in water; 21% of air). S yellow solid
Se, Te, Po metalloid/metal allotropes
Page 48

24
 Orbitals
Flaw of Bohr´
Bohr´s model: A circulating charged particle emits radiation
→ energy loss; and: experiments indicate electron has wave character.
character.
⇒ Orbital model: Atomic orbitals are (energy) states
or wave forms of electrons in the atom (quantum mechanics)
The probability of finding an electron in a certain
volume of space is the electron density.
s-, p-
p-, d-
d-, and f-
f-orbitals exist:
s-orbitals are spherical.
The K-K-shell (n=1; 2 e-) has only 1s-
1s-orb.
In the 2. shell (L-- shell, max. 8 e-)
(L
2s-orbital (max. 2e-), afterwards
at first the 2s-
the p-
p-orbitals are occupied.
p-orbitals dumbbell shaped.
There are three: px, py, pz
having the same energy state.
Each contains max. 2 e-
Every next shell ⇒ new type of orbital
(more complex shape). s, p, d hist., no meaning Page 49

Energy Levels of Orbitals

Main energy levels ("shells"): 1, 2, 3, 4, 5, 6

Within each shell the energy level s- s- < p-
p- < d-
d-orbital.
Electrons fill low energy orbitals before they fill higher energy
energy ones.
3. and 4. main energy level overlap ⇒
4s-
4s-orbitals are filled before the 3d-
3d-orbitals
(see PSE: After K, Ca (s-(s -block), introduction of transition metals with
valence electrons in d-d- orbitals. Afterwards Ga,Ge,As etc. (p-
(p-block)

Page 50

25
 Quantum Numbers

Quantum numbers describe the energy of electrons in atoms.

Name Symbol Orbital meaning Range Value
of Values Example
Principal (prim.) q.n.
q.n. n shell (main n≥1 n = 1,2,3,...
1,2,3,...
energy level)
Azimuthal q.n.
q.n. l subshell: s ⇒ 0 0 ≤ l ≥ n-1 for n = 3:
subshell:
(angular momentum) (orbital) p ⇒ 1 l = 0,1,2
d⇒2 (s,p,d)
s,p,d)
Magnetic q.n.
q.n. ml orientation of -l ≤ ml ≥ +l for l = 1 (p-
(p-Orb.)
(Projection of subshell shape ml = -1,0,+1
angular momentum)
px,py,pz
Spin q.n.
q.n. ms Spin of electron ½ : clockwise
-½: counter-
counter-clockwise

Page 51

Fitting Electrons into Orbitals

Pauli Principle/Hund
Principle/Hund´´s rule
Pauli principle: Two electrons my not occupy same quantum state⇒ state⇒
Each orbital occupied by max. two electrons with different spin ↑↓.
↑↓.
Hund´
Hund´s rule: When several orbitals of equal energy are available,
electrons enter singly with parallel spins (minimizes repulsion).
repulsion).

Examples:
Phosphorus 15P Sulfur 16S

n=3, l=1, ml=+1 "electrons-

"electrons-in-
in-boxes"
Page 52

26
 "Full" Outer Valence Shell
Noble Gas Configuration

The number of valence electrons (VE) in the outer shell

determines the chemical behavior.
"Full", closed-
closed-shell configuration have a favorable low energy.
Elements with a closed-
closed-shell (no valence electrons)
(18. group or VIII. main group: He, Ne, Ar,
Ar, etc.) show very
little tendency to participate in chemical reactions
Since they are all gases they are called noble (or inert) gases.
gases.
Electron configurations with a closed-
closed-shell are called
noble gas configuration.
Atoms of other elements can reach lower energy states
by undergoing chemical reactions. By loss or gain of electrons
they can reach a noble gas electron configuration.
configuration.
Page 53

Noble Gas Configuration/Octet Rule

Examples
Octet rule (of thumb): Atoms tend to combine in a way that they
each have eight electrons in their valence shells, giving them
the same electronic configuration as a noble gas
(applicable to the main-
main-group elements, except helium).
Examples:
Noble gas: 10Ne
1s2 2s2 2p6

-e- Na+ Atoms that lose electrons

11Na
have less negative charges
1s2 2s2 2p6 3s1 1s2 2s2 2p6 in shell than positive protons
+e- in the core and become
9F F- positive cations.
cations.
1s2 2s2 2p5 1s2 2s2 2p6
Atoms that gain electrons
become negative anions.
anions.
Page 54

27
 More Examples for
Noble Gas Configuration

Potassium (19K, alkali) looses 1 e-, becomes K+ cation,

with the same electron configuration like Argon 18Ar.
Its chemical and physical properties are of cause
completely different (different number of protons).
The same electron configuration achieves chlorine
(17Cl, halogen) by gaining 1e- becoming Cl- (chloride ion).

In a similar manner calcium (20Ca, alkali earth metal)

can lose two e- ⇒Ca2+, or 16S + 2 e- → S2-
both ions have the same electron configuration as 18Ar

By loss or gain of electrons particles reach the favorable,

low energy closed-
closed-shell (noble gas configuration).

Page 55

Chemical Bonds + Molecules

Types of Bonds
When atoms of different elements form chemical compounds,
their chemical and physical properties change significantly.
Example: Sodium (metal)
Chlorine Salt (NaCl)

Three types of chemical bond

nonmetal-
nonmetal- metal with non-
non- metal with
nonmetal metal (often) metal
Covalent bond Ionic bond metallic bond coordinate
bond

molecules salts metals (alloys) metal complexes

e. g. H2O e.g. Na+Cl- e. g. bronze Page 56

28
 Metallic Bonding

Metallic bonding: Electrostatic attractive force between positively

positively
charged cations (nucleus + inner e-), which form a 3D lattice and
negative, delocalized, shared valence electrons (" ("electron sea").
The free mobility of the valence
electrons causes electrical con-
con-
ductivity of metals.

Metal bonding exists between

atoms of a pure metal,
as well as in blends of two
or more metals (alloys).

Common alloys: bronze = copper/tin; brass= copper/zinc

Rose gold=gold/copper; white gold=Au-
gold=Au-Ag/Ni/Pd
Amalgam: mercury/silver
Page 57

Ionic Bond
Ionization
When atoms lose or gain electrons, ions are formed:
cations. Na -
Ions with positive charge are called cations. e- Na+
They have lost electrons.

In return, anions have gained electrons

-
to fill their valence shell.
Cl + e Cl-
They are negatively charged.
The atomic number (number of protons
in nucleus) does not change.
The mass does not change significantly.
Whether an atom tends to lose or gain one or more electrons
depends on the related change of its energy level.
The system as a whole strives to achieve the lowest energy state.
state.
Metals tend to lose electrons –
nonmetals tend to gain electrons.
Page 58

29
 Ionization Energy

Ionization I energy required Within a period the number of protons

to remove an electron increases binding electrons stronger ⇒
from an atom. Ionization energy increases.
Full and semi-filled shells are
⇒ cation favorable.
1,6·10-19 J)
(Unit: eV = 1,6· Within a group,
group, resp.
Ionization from period to period,
period,
Element 2s 2p
energy the outer electron are shielded

eV]]
Ionization energy [[eV
Li agaist the nuclear charge
Be by the inner electrons
⇒ I.-
I.-Energy decreases.
decreases.
B

Ne

atomic number → Page 59

Electron Affinity

The electron affinity EA is the counter part of the ionization energy.

energy.
Amount of energy released when an electron is added to an atom
⇒ negative anion.
anion.

Electron affinities (eV

(eV))
Positive values:
System would go to higher
energy state ⇒ gain of electrons
not possible.
Negative EA-
EA-values:
Energy is released.
Halogens and chalcogens
have high electron affinities
⇒Large amounts of energy is
released, if they gain electrons.
Page 60

30
 Electronegativity (EN)

Electronegativity (EN) describes the tendency of an atom (or a func-

func-
tional group) to attract electrons (or electron density) towards itself.
I II III IV V VI VII VIII
H He EN increases from
2,20 bottom left to
Li Be B C N O F Ne top right in the PSE
0,97 1,47 2,01 2,50 3,07 3,50 4,10 Alkali (I. MG) and alkali
Na Mg Al Si P S Cl Ar earth metals (II. HG)
1,01 1,23 1,47 1,74 2,06 2,44 2,83 electropositive. ⇒
Ionic bonds with
K Ca Ga Ge As Se Br Kr halogens (VII. MG) and
0,91 1,04 1,82 2,02 2,20 2,48 2,74 chalcogens (VI. HG)
Rb Sr In Sn Sb Te I Xe For organic chem.:
0,89 0,99 1,49 1,72 1,82 2,01 2,21 Hal/O >> C > H

Larger difference in EN ⇒ more polar bond; ∆EN>1,5 ⇒ ionic

Compounds of alkali-
alkali-/alkali earth metals and chalcogens
resp. halogens are ionic as a rule of thumb. Page 61

Atomic and Ionic Radius

Gain or loss of electrons alters the radius of the particle.

The radii of atoms and their respective ions are significantly different.
(⇒ cation) decreases the radius,
Loss of electrons (⇒
since the residual electrons are attracted more by the nuclear charge.
charge.
(⇒ anion) increases the radius, since the electron
Gain of electrons (⇒
shell becomes wider by the additional negative charge.
Li+ F-
Examples:

Na+ Mg2+ Cl-

K+ Ca2+ Br-
Br-

I-

Page 62

31
 Salts, Ionic Lattice
Salts are solids, that consist of ions (ionic bond).
Cations (+) and anions (-(-) are attracted by electrostatic
forces.
forces. The ions are positioned in a three-
three-dimensional crystal lattice
with regular long-
long-range order.
Such ionic crystals have high melting temperatures, are hard + brittle.
brittle.

Example: NaCl crystal (excerpt)

Each ion is surrounded by six counter
ions in octahedral geometry

With consi-
deration of
the ionic
radius.
Page 63

Chemical Formulas of Salts

The ionic crystal lattice is a continuous structure with no overall

overall charge
(electrical neutral). Positive charges of cations are compensated by
negative charges of anions ⇒ defined molar ratio (stoichiometry)
of cations and anions.
anions.
Since cations and anions can carry different amounts of charge,
their ratio can differ from 1:1.
x resp. y = 1
General composition of a salt: {x⋅An+ y⋅Bm-} = AxBy omitted
Ionic notation Empirical formula
(displays charges) (only molar ratio)

Examples: Elements Ions with Formula Name

in compound closed-
closed-shell of salt
Na Br Na+ Br- NaBr {Na+Br-} sodium bromide
Combination of
ions in com-
com- K S K+ S2- K2S {2K+S2-} potassium sulfide
pound so that Ca O Ca2+ O2- CaO {Ca2+O2-} Calcium oxide
charges are Ba Cl Ba2+ Cl- BaCl2 {Ba2+2Cl-} Barium chloride
compensated
Al F Al3+ F- AlF3 {Al3+3F-} Aluminum fluoride
Al O Al3+ O2- Al2O3 {2Al3+3O2-}Aluminum oxide
Page 64

32
 Covalent Bond

Atoms with low EN differences can form shared pair of electrons

The electron shells (or orbitals) overlap ⇒ covalent bond.
bond.
⇒ molecules

+ + + +

+ +
H-atoms H2-molecule
Examples:
Examples: Compound Emp. formula Structural formula
Hydrogen H2 H:H H-H

: :
Hydrogen fluoride HF H-F : H-F *
O ::

: :
O
Water H2O H H H H
* H forms exclusively covalent bonds, because no free H+ (proton=elemental part.)
Valence electrons not involved in covalent bonds
form free (or lone) electron pairs.
pairs.
Octet rule (of thumb): Atoms tend to combine in a why that they each
have 8 electrons (4 electron pairs) in their valence shell Page 65

Bond Character

The presented types of bonds are only models.

Real bonds can be intermediates; bond character
varies continuously throughout the PSE.
Examples:
Compounds of chlorine with elements of the 3. period:

Ionic bond Covalent bond

Compounds of sodium with elements of the 3. period:

Metallic bond Ionic bond

Elements of the 3. period

Metallic bond Covalent bond

Page 66

33
 Chemical Compounds
Molecules, Molecular Mass
A molecule is an electrically neutral group of at least two atom
(of same or different element) held together by covalent chemical
chemical bonds

All gaseous elements*

elements* form diatomic molecules:
H2, N2, O2, F2, Cl2
*besides noble gases
The nonmetals bromine (liquid) and iodine (solid) too: Br2, I2
The molar mass of a molecule is the sum of the molar masses of
the constituting atoms.
Examples:
Examples:Formula Molar mass of atom Molar mass [g/mol]
HCl H=1,00 Cl=35,45
Cl=35,45 1,00 + 35,45 = 36,45

CH4 H=1,00 C=12,01 12,01 + (4·

(4·1,00)=16,01
H2SO4 S=32,07 O=16,00 (2·
(2·1)+32,07+(4
1)+32,07+(4··16)=98,07
Page 67

Stoichiometric Valency
The valency is a measure of the number of bonds formed
by a given element. It depends on the number of valence
electrons.
Rules: • H has always valence number 1
• Alkali metals (I. MG.) have always valence number 1
• Alkali earth metals (II. MG) always 2
• Elements of III. MG have valency 3
• Halogens (VII. MG: F, Cl,Cl, Br, I) are always single valent
• O very often valency 2
• Other elements different valency (MG. elements max. 4)
• Products of lower case indices and valency in binary
compounds constant (last example)

Examples:
Examples: H2O: 2-
2-valent oxygen binds two single valent H
NaCl: Both single valent ⇒ combine 1:1
MgCl2: 2-
2-valent Mg binds 2 single valent Cl
Al2O3: 2·Al (3-
(3-valent): 2·3 = 6; 3·O (2-
(2-valent): 3·
3·2 = 6
Page 68

34
 Chemical/Structural Formulas of Molecules
Single/Double/Triple Bonds
Chemical (empirical) formula:
formula: Simplest whole number ratio
of atoms of each element present in a compound.
Structural formula:
formula: Graphical representation of molecular structure,
showing how the atoms are arranged.
= Valence structure = LEWIS formula
All valence electrons (bonding and lone electron pairs) represented.
represented.
Hydrogen
More examples: Ammonia H N H sulfide S H
NH3 H2S H
H
Some compounds (in particular of C, N, and O) contain
double or triple bonds:
Examples: Oxygen O O Carbon dioxide O C O
Nitrogen N N
Check valency and octet rule!
Page 69

Polyatomic Compound Ions

Ions can also be formed from groups of joined atoms: Compound ions
ions
Most common compound ions:

Ammonium ion NH4+ Hydroxide ion OH- Nitrate ion NO3-

H
+ O - O
H N H - N
O H
H O

Sulfate ion SO42- Carbonate ion CO32- Hydrogen carbonate

ion HCO32-
O - O O O O H
O O C C
S - - -
- O O
O
Page 70

35
 Chemical Models
Mesomeric Resonance

"This is no carbonate ion !"

It is a (crude!) model
of a carbonate ion.
Experiments indicate:
All O-
O-atoms same charge;
all bonds identical;
all bond angles identical.
Christopher Ingold (1933): Mesomerism =
Representation of delocalized electrons
Rene Margritte:
Margritte:
"This is no apple" by different contributing structures.

Page 71

Double Bond Rule

(empirical)
empirical)

Elements of the second period (C, N, O) often form double bonds.

The analogous elements of the 3. period (and higher), however,
form in analogous compounds form preferably single bonds.

Main group: → IV. V. VI.

2. Period:
(CO2) (N2) (O2)

3. Period:
(S8)
(SiO2) (P4)

Page 72

36
 Bond Theory
Orbital Hybridization (sp3)
Carbon essential element in organic compounds; forms covalent bonds.
bonds.
C has 4 electrons in valence shell: configuration 2s2 2p2 (ground state)
1 lone electron pair (s2) and 2 p-
p-electron could form only 2 bonds.
Prediction: CH2 But: Carbon is 4-4-valent! Example.: CH4 ?!
Explanation: The valence electrons are rearranged in a way,
that 4 electrons can form bonds.
The s-
s-orbital and the three p-
p-orbitals are mixed to form
four sp3-hybrid orbitals of identical energy.

Hybridization is not a physical fact -,

it's only an model to explain experimental observations!
(e. g. molecule geometry) ! Page 73

sp3-Hybrid Orbitals

Geometry of hybrid orbitals

+
p s hybrid orbital

The 4 sp3 hybrid orbitals

arranged in space with a
maximum separation:
tetrahedral

Page 74

37
 Single Bonds
Two hydrogen atoms form a single bond (σ -bond)
by head-
head-on overlapping between the atom orbitals.

Highest electron density between the two nuclei.

σ-bond is symmetrical with respect to rotation about bond axis.

Other orbitals
can also form
σ-bonds:

Page 75

Single Bonds in Hydrocarbons

C-H-bonds and C-
C-C single bonds are σ-bonds.
Four σ-bonds ⇒ complies with octet rule.
Example:
Methane
4 C-
C-H-
σ-bonds

Example:
Ethane
3 C-
C-H-
1 C-
C-C-
σ-bonds

Free rotation about σ-bonds

Page 76

38
 sp2-Hybridisation
Example: Boron

Boron (ground state): hybridization:

1s2 2s2 2p1 One s-
s- and two p-p-
E orbitals mix to form
E
tree sp2 hybrids of
2p 2sp2 equivalent energy
2s each occupied
by one electron
1s 1s

Trigonal-
Trigonal-planar F Boron trifluoride
geometry of (BF3) does not
F B comply with
three sp2-hybrid
orbitals in space. F octet rule
⇒ electron gap
⇒ Lewis acid
Page 77

sp2-Hybridisation of Carbon

E carbon The 2s-

2s-orbital and the two 2p-
2p-orbitals mix
to form three sp2-hybrid orbitals.
2p The third p-
p-orbital unaffected.
unaffected.
2sp2 Each occupied with single electron.

1s
In an ethene molecule three sp2-hybrid
electrons form three σ-bonds:
Two with the H-atoms and one with
the other C-
C-atom (trigonal
(trigonal--planar).
planar).
The fourth electrons occupy the
remaining, unhybridized pz-orbitals,
sidewise overlapping above and
beneath the plane to form a π-bond.
bond.
H H
C-C-σ-bond and π-bond
C C
sp2-hybrid
orbitals of carbon together form double bond.
and bonds formed in ethene. H H
Page 78

39
 sp-
sp-Hybridization

Which elements can mix one s-

s- and one p-
p- orbital to two sp hybrids
to form two σ-bonds and how are they arranged in space?

Beryllium (II. main group) can form two sp-

sp-hybrid orbitals,
which can form two σ-bonds (linear, 180°
180°) e. g.: H-
H-Be-
Be-H

The two sp-

sp-hybrids of each C-
C-atom
form two σ-bonds (C-
(C-C and C- C-H).
The two remaining p-p-orbitals
overlap crossbred sidewise
C-C π-bonds.
to form two C- bonds.

H One C-C σ-bondH and

two π-bonds together form a
triple bond:
sp-hybrid orbitals of carbon
and bonds formed in ethyne. H C C H
Page 79

Polar Covalent Bonds

Dipolar Molecules
A polar bond is a covalent bond between two atoms
with different electronegativities ∆EN>0.
EN>0.
The electron density of the bonding electron pair is higher
in the vicinity of the atom with the higher electronegativity.
Partial charges and a permanent dipole are formed.
δ+ δ-
H Cl H Cl
EN: 2,2 2,8
Dipolar momentum

δ- _
EN (O): 3,5 O δ+
δ- δ-
O O
EN (H): 2,2 H H C
+ δ+
δ+
Water molecule angled ⇒ Carbon dioxide: linear
partial charges asymmetrical partial charges symmetrical
⇒ dipole molecule ⇒ no dipolar molecule
⇒strong intermolecular forces ⇒weak intermolecular forces
⇒ liquid (high boiling temp.) ⇒ gas (low boiling temp.) Page 80

40
 Cleavage of Covalent Bonds
Before new bonds can be formed in a chemical reaction,
existing bonds must be cleaved by high temp. or energetic radiation.
radiation.
Distinction between:
Homolysis: Cleavage of non-
non-polar covalent bond into two radicals:
Radicals are atoms or molecules with a non-
non-shared electron.
They are very energetic, have high reactivity and short lifetime.
lifetime.
UV, heat Initiation of chlorine/
Example: Cl Cl Cl⋅ + ⋅Cl hydrogen gas explosion
Cl⋅

Heterolysis:
Heterolysis: Cleavage of a polar covalent bond into cation + anion:

H H O⊕ H
O H Cl + Cl
H δ- δ+ H
+
Proton (H ) transfer
Page 81

2.3.4 Intermolecular (physical) Forces

Different attractive interactions can occur between

molecules, distinguished by strength and origin:

• Hydrogen- (bridge)-bonds: ≈ 10kJ/mol; by polar H

Hydrogen-(bridge)-
strengh

Dipole-dipole interactions: ≈ 5kJ/mol by dipoles

• Dipole-
• Van-der-Waals interactions: ≈ 1kJ/mol by all atoms
Van-der-

In contrast to intramolecular chemical (primary) bonds inside molecules,

these intermolecular forces between molecules are physical
(secondary) bonds.
At the boiling temperature the kinetic energy of the molecules
exceeds the attractive forces.

Page 82

41
 Hydrogen Bonds
Hydrogen bond = attractive interaction of a hydrogen atom with an
electronegative atom (N, O, F, ...) that comes from another molecule
or chemical group. The hydrogen must be covalently bonded to
another electronegative atom to create the bond.
These phys. bonds can occur between molecules (intermolecular),
or within different parts of a larger single molecule (intramolecular
(intramolecular).
).
This type of bond occurs in both inorganic molecules such as water
water
and organic molecules such as proteins, cellulose or DNA
molecule molar mass boiling temp.
CH4 16 g/mol -161 °C
NH3 17 g/mol -33 °C
H2O 18 g/mol 100 °C
Boiling temperature is increased
by hydrogen bonds
Hydrogen (bridge)
bonds in water
Page 83

Dipole-
Dipole-Dipole Interactions
Dipole–
Dipole–dipole interactions = electrostatic interactions of permanent
dipoles in molecules (asymmetrical polar bonds; e. g. H2O, HCl, HF).
Attractive force between positive part of molecule and negative
part of neighbored molecule
Polar atomic group without hydrogen:
e. g. carbonyl group (org. chem.)

δ+ C δ-
O

asym.⇒ dipole
asym. sym.⇒ no dipole
sym.⇒
Melting temperature 17 °C -76 °C
Boiling temperature 44 °C -10 °C

Phase transition temperatures increases by dipolar interactions.

Page 84

42
 London Dispersion Forces
(Van-
Van-der-
der-Waals Interactions)
Interactions)
London dispersion forces (LDF)
also called Van-
Van-der-
der-Waals forces
in the strict sense are weak
intermolecular interactions
arising from induced instantaneous
polarization by random fluctuation of
the electron density.

The LDF between molecules increases with surface:

Example:

n-pentane 2-methyl butane 2,2-dimethyl propane

old name: pentane old name: iso-pentane old name: neo-pentane

boiling T: 36°C 28°C 9,4°C

Page 85

Chemical Bonds and Physical Bonds

Summary

Bond type positive charge negative charge

Energy (kJ/mol)
Ionic bond Cations anions
Lattice enthalpy
chemical

≈1000
metallic bond Cations delocalized electrons
(electron sea)
Covalent bond Nucleus Electron shell
≈ 300 per bond
Hydrogen bond H atom (polar bond to Electronegative atom
≈ 20 kJ/mol electronegative atom, N, O,) with lone-
lone-pair (O, Cl)
Cl)
physical

Dipole-
Dipole-dipole
dipole permanently positively permanently positive-
positive-
≈ 5 kJ/mol polarized atom in mol. ly polarized atom
Van-
Van-der-
der-Waals-
Waals- instantaneously positively instantaneously posi-
posi-
bond ≈ 1 kJ/mol polarized atom tively polarized atom
Page 86

43
 Polar/non-
Polar/non-polar Solvents
hydrophilic/lipophilic
Several types of chemical reactions occur in solution, if a suitable
suitable
solvent for the reactants can be found. The solubility depends onon
polarity of solvent and solute. The number, potency and arrangement
arrangement
of polar bonds in the molecule influences the polarity of the solvent:
solvent:

Benzene Ether Ester Alcohol Water

Polarity Polar solutes or atomic groups
are water soluble = hydrophilic
Fats are non-
non-polar and not
Hydrophilicity water soluble (hydrophobic
(hydrophobic))
Non-
Non-polar compounds
Hydrophobicity = Lipophilicity are lipophilic.

(Na+Cl-) or polar compounds (methanol) exhibit good solubility

Ionic (Na
in water. Non-
Non-polar compounds (fat, oil, grease) are soluble in non-
non-polar
solvents (white spirit, ether, chloroform, etc.)

Page 87

3. Physical Chemistry

Topics:
• State of matter/phase transitions
• Phase diagrams
• Homogeneous/heterogeneous systems
• Separation processes
• Thermodynamics
• Kinetics
• Chemical equilibrium

Page 88

44
 State of Matter
Phase Transitions; Separation

Sublimation

Melting Evaporation

solid liquid gaseous Temp.

Solidification Condensation

Resublimation
A phase is a region of space (in a thermodynamic system) throughout
which all physical properties of a material are essentially uniform.
uniform.
States of matter are phases. The change of the state of matter is is a
phase transition.
The state of matter of a material or compound depends on
temperature T and pressure p ⇒ p-t-phase diagram
Page 89

Phase Diagram

Position of
pressure p

melting curve,
curve,
boiling curve and
sublimation curve
liquid substance-
substance-specific.
solid Triple point:
solid, liquid, and
gaseous phase
Normal coexist.
pressure
Example:
Example: Solid
gaseous compound at nor-
nor-
Triple point mal conditions
annealed until it
Ambient Tm Tb Temperature T melts (Tm) and
temp. evaporates (Tb)

Page 90

45
 Liquefaction of Gases

Pressure p Gas can be

liquefied by
cooling or
solid compression
liquid

Normal
pressure

gaseous

Ambient Temperature T
temp.

Page 91

Phase Diagram of Water

Pressure p [hPa]

Anomaly:
Anomaly:
Liquid water has a
higher density than
ice.
Water (Negative slope of
Ice melting curve)
Skating:
Skating:
At const. low tempera-
tempera-
ture (~ -5°C) pressure
1013 is increased
⇒ ice melts
Water vapor
Pressure cooker:
Higher pressure ⇒
0 100 Temperature T [°C] higher boiling temp.
⇒ faster cooking

Page 92

46
 Multi Phase Systems
heterogeneous Systems
heterogeneous Systems:
Systems: Two or more components (= phases).
Physical (and chemical) properties change instantaneously
at phase boundaries.
boundaries.
Differentiation by combination of states of matter (Example)
(1) solid/solid Mixture (Granite = feldspar + quartz+ mica)
(2) solid/liquid Suspension (Blood = blood cells in blood plasma)
(3) liquid/liquid Emulsion (Milk = fat droplets in water)
(4) solid/gaseous Smoke; foam (cigarette smoke, Styrofoam)
(5) liquid/gaseous Fog; foam (Fog, whipped cream)
= Aerosols
Heterogeneous mixtures can of be separated into homogeneous
(uniform) components by physical operations like filtration,
centrifugation, decantation, etc.

Page 93

Homogeneous Systems

In homogeneous systems the properties are uniform throughout the

whole sample; no phase boundaries.
Homogeneous systems can be pure substances or multi component
systems (=solutions).
Different types of solutions:
(1) solid/solid (metal alloys, z. B. bronze)
(2) solid/liquid (sugar dissolved in water)
(3) liquid/liquid (alcohol + water)
(4) solid/gaseous (solution of hydrogen in platinum)
(5) liquid/gaseous (air dissolved in water)
(6) gaseous/gaseous (air)

Homogeneous mixtures can also be separated into their components

by physical operations, e. g.:
• Distillation: Separation by different boiling points; (distilling)
(distilling)
• Extraction: Separation by different solubility's; (coffee cooking)
cooking)

Page 94

47
 Distillation

Thermal separation process: Mixture is separated into components by

the differences in their boiling temperatures.
Mixture (2) is annealed (1); More volatile component (lower Tb) evapo-
evapo-
rates. Thermometer (4) indicates temperature of vapor (3)
= boiling temperature.
In condenser (here Liebig cooler) (5)
with cooling water plugs (6;7)
the more volatile component
condenses and drops into receiving
flask (8).
Volume extension during
evaporation ⇒ pressure equalization (9).
High boiling compounds bp.>200
bp.>200°°C:
low pressure (vacuum) distillation.
⇒ Lower boiling temperatures.
Examples:
Examples: Essential Oils, pure alcohol,
sea water ⇒ freshwater
Page 95

The Chemical Reaction

A chemical reaction is a process that leads to the transformation

of one set of chemical substances to another. Existing bonds between
the atoms of the reactants (=reagents) are partly broken, new bonds
bonds
are formed

Reaction equation: Reactant 1 (+ react. 2) product 1 + (product 2)

The connections among the atoms are altered, the number of atoms
of the respective element remains constant.

During a chemical reaction the total

mass of matter remains constant.
Law of conservation of mass

Antoine Lavoisier
fr. Chem. (1743-1794)
Page 96

48
 Chemical Thermodynamics
Chemical Kinetics
The electronic structure of the reactants (valency, polarity, etc.)
etc.)
indicate which chemical reactions are possible in general,
but do they really take place and under which conditions?
Sometimes side reactions can occur. Which product is formed?
Whether a chemical reaction takes place, to which extent and how
fast is determined by the chem. thermodynamics and kinetics. kinetics.

Chem. thermodynamics:
thermodynamics:
Under which conditions does a reaction occur spontaneously ?
Is heat released or consumed?
Chem. reactions always involve conversion of energy.
Whether a reaction occurs or not is related to the available
chemical energy stored in the reactants and products.
Reaction kinetics:
kinetics: Study of rate of chemical reactions:
How much product is formed in time under given experimental
conditions (e. g. concentration).
Page 97

Reaction Enthalpy
Exothermal/Endothermal Reaction
Reaction enthalpy (∆HR) (= reaction heat) = how much heat
is released or consumed during reaction.
Enthalpy negative ∆HR<0 ⇒ heat released = exothermal
EnthaIpy pos. (∆(∆HR>0) ⇒ heating necessary = endothermal.
endothermal.
products II
endothermal
enthalpy

∆HR<0 ∆HR>0 ∆HR

exothermal reactants reaction
endothermal
exothermal
products I
Chemical energy is stored in chemical compounds.
If the products (I) have lower energy state than reactants ⇒
exothermal, energy released. (heat, light, bang)
If products (II) have higher energy content, reaction is endothermal,
endothermal,
feed of energy required (heat, electricity).
Page 98

49
 Example for
Exothermal/Endothermal Reaction

Example:

Hydrogen-
Hydrogen-oxygen reaction
2 H2 + O2 2 H2O
Electrolysis

Oxyhydrogen reaction

H2-O2-reaction ∆HR = - 286 kJ/mol (released; heat, light, bang)

During electrolysis of water ∆HR = 286 kJ/mol
(consumed; electrical power)

Page 99

Enthalpy of Formation
Calculation of Standard Enthalpy of Reaction
The chemical internal energy = enthalpy H of a system cannot
be measured directly. Change in enthalpy ∆H more useful quantity.
By definition all elements have an enthalpy of zero.
(25°C, 1 bar): H0
funct. of T und p ⇒ Standard cond. (25°
Enthalpies are funct.
Molar Enthalpy of Formation of a compound ∆Hf = amount of heat
released or consumed during its formation from the elements.

Example:
Example: Molar standard enthalpy of formation of water:
H2 + ½ O2 → H2O (l) ∆HR = -286 kJ/mol
∆Hf = 0 0 -286 kJ/mol
The reaction enthalpy can be calculated from the enthalpies of forma
forma--
tion of involved compounds:
∆HR0 = ∑∆H0f ( products
) − ∑∆H0f (reactants)
Example:
Example: Combustion of ethene:
C2H4 + 3 O2 → 2 CO2 + 2 H2O (g) ∆HR = -1322,9 kJ/mol
∆Hf0 = 52,3 0 2·
2·(-393,5) 2·
2·(-241,8) kJ/mol
Page 100

50
 Hess Law

Hess: the enthalpy change for a reaction carried out in a series of steps
is equal to the sum of the enthalpy changes for the individual steps
steps

Example: ∆Hf CO not directly measurable, because CO2 is formed too.

Example:
∆Hf (CO)= -110,5 kJ/mol (calculated)
(

rea re
ctio ac ∆HR = -283
n
tio
∆Hf (CO2)= -393,5 kJ/mol
n kJ/mol
(measured)

∆Hf (CO) = ∆Hf (CO2) - ∆HR (CO→

(CO→ CO2)

Page 101

Hess Law
and Biological Processes

Photosynthesis

Combustion

Respiration
(Glycolysis,
Glycolysis, Citrate cycle,
cycle, ...)

Page 102

51
 Entropy

Another thermodynamic property of matter is the entropy:

entropy: Interpretation
as molecular disorder or statistical number of possible arrangements.
arrangements.
Ssolid < Sliquid < Sgas

solid liquid gas

Spure substance< Smixture

pure subst. mixture

Page 103

Change of Entropy

In closed thermodynamic systems, the entropy remains

constant for completely reversible processes.
For irreversible processes the entropy increases.
Examples for irreversible processes
with increase of entropy:
Heat exchange: 60 °C
50
40 20 °C
30
40
Diffusion:

Reaction entropy: ∆S R0 = ∑ ∆S 0 ( produkte) − ∑ ∆S 0 ( Edukte)

Page 104

52
 Gibbs (Free) Energy

The reactions enthalpy indicates, if process is exo-

exo- or endothermal,
but not, if reaction occurs spontaneously. Endothermal spontaneous
spontaneous
reactions can occur, which consume heat from the environment,
which is cooled.
Driving force for a reaction is the Gibbs (Free) Energy ∆G.
Gibbs-Helmholtz equation: ∆G = ∆H -T·∆S
Gibbs-
Reactions occur spontaneously, if ∆G < 0 (exergonic
(exergonic reaction).
If ∆G > 0 ⇒ endergonic reaction, absorbs energy from surrounding.

„somebody has
to lift the ball“
ball“

Page 105

Activation Energy
Catalysis
The activation energy is the minimum energy required to start a chemi-
chemi-
cal reaction („
(„igniting spark“
spark“) (cleavage of existing bonds), even for
exothermal reactions in which the released heat exceeds the activation
activation
energy by far.
A catalyst (chem. compound
added in small amounts
to reaction)
Activation energy •lowers activation energy,
energy

with catalyst •increases reaction rate

reactants •doesn't influence equilibrium
reaction
•is not consumed by reaction

H-H
H⋅⋅⋅H
⋅⋅⋅H reactant
reaction
enthalpy
∆HR < O Platinum
products ⇒ exothermal
Page 106

53
 Kinetics

Reaction kinetics: Speed of chemical reactions.

Reaction rate defined as change of concentration with time
d [ A] d [ B] d [ P]
For a reaction: A + B → P: r=− =− =
dt dt dt
i.e.: increase of concentration of product P
resp. decrease of reactant A or B with time.
Monitoring progress of reaction by
• change of color
• spectroscopic
• conductometric
• calorimetric (heat measurement)

reduction of methylene
blue by glucose Page 107

Rate Law
Reaction Order
The reaction rate depends on the concentration of the involved
compounds ⇒ rate law:
law: d [ A]
r=− = k (T ) ⋅ [ A] ⋅ [ B]
a b
For A + B → P: dt

The order of reaction is defined as the sum of all the exponents

of the reactants involved in the rate equation.
k is the rate constant, which is temperature dependent as a rule.

reaction order rate law

A→P 1. order -d[A]/dt = k·[A]
[A]
A+B→P 2. order -d[A]/dt = k·[A]·
[A]·[B]
[B]

Page 108

54
 Chemical Equilibrium
Reversible/Irreversible Reaction

In general, a chemical reaction can be reversed:

The products can react with each other to form the original reactants.
reactants.
Such a reaction is called a reversible reaction.

Reversible reaction: A+B C+D

Forward and reversed reaction occur simultaneously so that
a dynamic equilibrium is formed, in which A and B react continuously
to C und D, while C and D form A and B again. Once the equilibrium
equilibrium
is reached, the net concentrations remain constant.

A reaction without reversed reaction is called irreversible.

irreversible.
It occurs until A and/or B are consumed completely or, if C and/or
and/or D
are removed from the reaction site.
Irreversible reaction: A + B C+D

Page 109

Law of Mass Action

The equilibrium state of a chemical reaction can be described

quantitatively by the Law of Mass Action (Guldberg/Waage 1865).
k← c(C ) ⋅ c( D)
A+B C+D Equilibrium constant kc = =
k→ c( A) ⋅ c( B )
Concentrations are multiplied! By convention product ⇒ numerator

[C ]c ⋅ [ D]d
in general: aA + bB ⇔ cC + dD kc =
[ A]a ⋅ [ B]b
Almost complete
reaction:
A+ B → C + D kc>>1 ; z.B. 1012
Equivalent
equilibrium:
A+ B C + D kc=1
Barely occurring
reaction:
A+ B ←C + D kc<<1 ; z.B. 10-12
Application of • Solubility of salts
Law of Mass Action: • Autoprotolysis of water Page 110

55
 Le Chatelier´
Chatelier´s Principle

Change of concentration:
concentration:
Changing the concentration of an
ingredient (C) will shift the equilibrium
A+ B C+D
A+ B ← C+ D
to the side that would reduce the change.
By the reversed reaction C and D are
consumed partly, while the concentration
of A and B is increased until kC reached.A+ B
[C ] ⋅ [ D ]
C+ D

kc =
[ A] ⋅ [ B ]
A+ B C + D + Energy
Change of temperature.:
temperature.:
Exothermal reaction has energy (heat) as product. Cooling removes
removes
heat and the equilibrium is shifted to the product side.
Endothermal reactions are enhanced by feeding energy.
Change of pressure/volume:
pressure/volume: In reactions with volume decrease (com-
(com-
pression)
pression) increasing pressure shifts the equilibrium to product side.
Example:
Example: N2 + 3 H2 2 NH3 A + B + P /V C+D
Page 111

4. Inorganic Chemistry
4.1 Acids – Bases
Historically, acids are compounds, which taste sour (vinegar,
lemon). Those compounds
change the color of
certain vegetal ingre-
ingre-
dients to red (red
cabbage; litmus).
(R. Boyle, 1663)
acidic red cabbage extr.
extr. alkaline
Substances, which taste and feel soapy, were called alkalis
(arab.:Plant ash←Potassium hydroxide). Lye = corrosive alkaline
substance. Later such chemicals were called bases,
bases, since
they are (together with an acid) the base for formation of salts.
salts.
Bases can change the color of certain plant ingredients, too.
Lavoisier (~1770) assumed, that acids contain oxygen, because
non-
non-metal oxide (e. g. CO2) together with water form acids.
Observation:
Observation: (Hydrochloric) acid dissolves lime (CaCO3) and zinc
involving gas development. It does not react with copper. Page 112

56
 Acid Rain

The source of acid rain are the The produced acids are harmful for
oxides of carbon, nitrogen and plants, waters, and buildings:
sulfur, which are formed by the
combustion of fossil fuels
(coal, mineral oil, natural gas)
They react with water molecules
to produce acids.
Carbon dioxide:
• CO2 + H2O → H2CO3
Nitroxides:
Nitroxides:
• 2 NO2 + H2O → HNO2 + HNO3
Sulfur oxides:
1908 1968
• SO2 + H2O → H2SO3 limestone sculptures in industr. area
• SO3 + H2O → H2SO4
CaCO3+2H2SO4→CO2+H2O+Ca2++SO42-
solid gaseous soluble
Page 113

Acid-
Acid-Base Theory by Brø
Brønsted
Comprehensive acid-
acid-base theory by Brø
Brønsted (1923):
Acids: Proton donators; compounds or specimens,
that release protons.
Bases:Proton acceptors; compounds or specimens,
that absorbs (gains) protons.
Advantage: Definition is Joh.
Joh. N. Brø
Brønsted
dan.
dan. Chem.
Chem.
• independent of water as solvent
• not restricted to liquid phase ⇒ HCl (g) + NaOH (s) →
• more bases, e. g. ammonia (NH3) Na+Cl –(s) + H2O (l)
Bases must have a lone In water Brø
Brønsted
pair to receive a proton acids produce
hydronium ions:
ions:

O A- + H O⊕H
H-A +
H H H
Page 114

57
 Dissociation Equilibrium
Conjugate Acid/Base
If an acid HA reacts with a base B, a proton is transferred from
the acid to the base (protolysis
(protolysis).
).
conjugate
acid base acid base

In the reversed reaction, a proton is transferred from HB+ to A-

i. e., HB+ acts as acid, A- as base.
In such a dissociation equilibrium two sets of
acid-
acid-base pairs occur: S1/B1 and S2/B2.
A- is called conjugate base to HA
and HB+ conjugate acid to B.
Acid and bases can be neutral molecules or ions.
Example: Acetic acid + ammonia → ammonium-
Example: ammonium- + acetate ion
Page 115

Ampholyte

An ampholyte molecule (or ion) can either donate or accept

a proton, thus acting either as an acid or a base.

Example:
Water reacts toward nitric acid H2O + HNO3 → H3O+ + NO3-
as a base: It receives a proton and
becomes a hydronium ion.
Towards the base ammonia
water reacts as an acid, however,
releasing a proton and becoming H2O + NH3 → OH- + NH4+
a hydroxide ion.

More ampholytes:
HCO3- (Hydrogen carbonate ion), HSO4- (Hydrogen sulfate ion)
Acid/base designates a chemical behavior towards a reaction partner,
rather than a class of substance.
Names (e .g. nitric acid) are historical regarding reaction with water.
Page 116

58
 Acid-
Acid-Base Theory by Lewis

1927; G.N. Lewis: Even more general def. for acids and bases:
(independent of protons or hydroxide ions)

Lewis-
Lewis-acid: Specimen, with empty outer orbital, ready to receive
electron pair; has electron pair gap (does not comply with octet
octet rule!)

Lewis-
Lewis-acid: Electron pair acceptor

Lewis-
Lewis-base has a free electron pair, which can add to a Lewis acid
to form a new electron pair bond.
Lewis-
Lewis-base: Electron pair donator
Example: Brö
Brönstedt-
nstedt-
acid
New bond by overlap
of empty boron orbital
with occupied nitrogen
orbital Lewis acid Lewis base Lewis acid-
acid-base aduct
Page 117

General Structure of Acids

What is the general structure of a Brø

Brønsted acid?
Brø
Brønsted acids contain polar bonded hydrogen.
Which elements form polar bonds with H ?
Non-
Non-metals (electronegative!) form polar bonds with H.

Example:
Example: Hydrogen chloride H Cl other halogens analogous

Elements with lower electronegativity (S,N,P,C) can increase

polarity by additional bonds to oxygen atoms:
Examples: Nitric acid Sulfuric acid Citric acid
O O
H H
O O O
N S
O H
O
Page 118

59
 Strong/Weak Acids/Bases

Acids and bases are graded strong or weak regarding their

tendency to release resp. receive protons.
The more polar the hydrogen is bonded, the greater the
tendency for dissociation = protolysis,
protolysis, the stronger the acid.
Examples: Sulfuric acid Sulfurous acid Hydrogen
O O sulfide
H is H is H
O O stronger O stronger
S acid S acid
H than: H than: S
H
O O
Strong acids (HCl, H2SO4, HNO3, H3PO4, HClO4)
completely: HA + H2O→H3O+ + A-
dissociate in water almost completely:

Strong acids have weak conjugate bases;

strong bases have weak conjugate acids.
Page 119

Polyacids

Some acids can release more than one proton via different
protolysis steps. The second step is hampered compared to the first.
Example:
Example: two-
two-proton acid carbonic acid (H2CO3).
conjugate acid-base-pairs
H2CO3 + H2O step
HCO3– + H3O+ 1. Stufe H2CO3 / HCO3– und H3O+ / H2O
HCO3– + H2O CO32–+ H3O+ step
2. Stufe HCO3– / CO32– und H3O+ / H2O

Intermediate (e. g. hydrogen carbonate ion) = ampholyte !

More
poly-
poly- Oxalic acid H2C2O4
acids:
Sulfuric acid H2SO4

Phosphoric acid
H3PO4
Page 120

60
 Concentrate/Dilute Strong Acids
Molarity

Mixing of pure, concentrate acid with water ⇒ dilute acid.

acid.
Warning: During dilution of concentrate acids (in particular sulfuric acid)
acid)
with water large amounts of heat are released;, rapid evaporation
evaporation of
water; uncontrolled spray of acidic liquid
Rule:
Rule: Add acid slowly to water – never add water to conc. acid!

Concentration c (= Molarity M (outdated but still common)) of acid/base

= Number of Mole dissolved acid/base in 1 L.
M > 1 mol/L ⇒ conc. acid; M < 1 mol/L ⇒ dilute acid
Example: conc. (69%mass) nitric acid has density ρ=1,41 g/cm3
Example:
L⇔1410g; 69%⇔
1 L⇔ 69%⇔973g pure HNO3; molar mass=63 g/mol;
n=m/M = 973g/63g/mol=15,4 mol ⇒conc. nitric acid = 15,4 M HNO3
How much conc. acid for 100 ml of 0,1 M (dilute) HNO3 ?
n = V·c = 0,01 mol HNO3
1000ml x
= ⇒ x = 0,65ml ⇔ 0,92g
15,4mol 0,01mol
Page 121

Strong Acids

acid: Made from sulfur trioxide (SO3) + H2O→H2SO4

Sulfuric acid:
100%: ρ=1,8 g/cm3; 1800g/98g/mol = 18 mol/L = 18 M H2SO4
additional phys. solution of SO3 ⇒ Oleum (hygroscopic)
Hydrochloric acid = aqueous solution of hydrochloric gas (HCl)
(HCl)(g)
(g);
max. 40 % ⇒13 mol/L hydrochloric acid
Complete dissociation: HCl + H2O → H3O+ + Cl-
> 36% = fuming acid. ⇐ HCl gas evaporates
Nitric acid = HNO3 ; concentrate = fuming 90% HNO3
⇒ free NO2 (brown toxic gas);
dissolves silver, but not gold (aqua fortis)
fortis)
Nitrating acid:
acid: Mixture of nitric + sulfuric acid for nitration
of compounds; e g. toluene ⇒ trinitrotoluene (TNT)

Aqua Regia = HCl/HNO3 (3:1) dissolves gold

Page 122

61
 Common Acids
and their Conjugate Bases
Hydrochloric acid HCl(aq)
(aq) Chloride ion Cl-
Hydrofluoric acid HF Fluoride ion F-
Sulfuric acid H2SO4 Hydrogen sulfate HSO4- Sulfate SO42-
Sulfurous acid H2SO3 Hydrogen sulfite HSO3- Sulfite SO32-
Nitric acid HNO3 Nitrate ion NO3-
Nitrous acid HNO2 Nitrite ion NO2-
Phosphoric H3PO4 Dihydrogen phosphate H2PO4- Phosphate PO43-
acid Hydrogen phosphate HPO42-
Carbonic acid H2CO3 Hydrogen carbonate HCO3- Carbonate CO32-
Perchloric acid HClO4 Perchlorate ion ClO4-
Hydrogen cyanide HCN Cyanide ion CN-
Acetic acid CH3COOH Acetate ion CH3COO-

Ampholytes
Page 123

Common Bases/Alkalis

Caustic soda = alkaline solution of sodium hydroxide

(NaOH) in water; max. 1200 g = 30 mol/L
exothermal process!
Production: Electrolysis of alkali chlorides
(see: Industrial Chemistry)
Chemistry)
Potash lye = alkaline solution of potassium hydroxide
(KOH) in water; exothermal process!

Ammonia water = Ammonium hydroxide = Sal ammoniac

← NH + + OH-
Ammonia (gas) dissolved in water: NH3 + H2O → 4

Page 124

62
 Carbonic Acid

Gaseous carbon dioxide

(CO2)(g) (CO2)(aq).
soluble in water:
partly reacts to carbonic acid: CO2 (aq
(aq))+ H2O H2CO3
Carbonic acid is a weak
acid, dissociates only partly H2CO3 + H2O HCO3- + H3O+
forming hydrogen carbonate
ions (Ampholyt).

In a second protolysis step

carbonate ions can be produced: HCO3- + H2O CO32- + H3O+

In carbonated water all species coexist in a chemical equilibrium

equilibrium
in different concentrations. Addition of lemon (acid, H3O+) shifts all
equilibriums to the left ⇒ more CO2 gas escapes.
Page 125

Autoprotolysis of Waters

Salt solution are electrical conductive, since they contain ions.

ions.
Application of voltage ⇒ ions are moved: Cat+→ cathode (neg. pole)
: An- → anode (pos. pole)
Pure, distilled water is conductive too,
because water always contains ions due to autoprotolysis:
autoprotolysis:

H2O + H2O [H3O]+ + [OH]-

Water acts as acid and as base,

hydronium ions and hydroxide ions are produced
in small concentrations.
Page 126

63
 Ion(ic)
Ion(ic) Product of Water

Law of mass action Derivation of ion product of water

for autoprotolysis from law of mass action

The ion product of aqueous solutions is always 10-14 mol²

mol²/L²
/L²
By addition of hydronium
H2O + H2O [H3O]+ + [OH]-
ion (from acid)
acid) shifts the
equilibrium, H3O+ and OH-
equilibrium,
react until KW =10-14 again. H O + H2O
again. 2
[H3O]+ +[OH]-
Now, [H3O+]>10-7 and
Now,
H2O + H2O [H3O]+ + [OH]-
[OH-]< 10-7
[OH- Page 127

The pH Value

The concentration of hydronium ions is a measure for

acidic or alkaline character of a solution.
Representation as decimal number confusing
in powers of 10 inconvenient, therefore definition:
The pH value is the negative decimal logarithm of the
hydronium ion concentration. (p
(potentia hydrogenii)
ydrogenii)
pH = − lg[c( H 3O + )]
c(H3O+) mol/L decimal c(H3O+) mol/L power pH value solution
1 100 0 very acidic
0.0001 10-4 4 moderate acidic
0.0000001 10-7 7 neutral
0.0000000001 10-10 10 moderate alkaline
0.00000000000001 10-14 14 very alkaline
Page 128

64
 Relationship between Hydronium and
Hydroxide Ion Concentration

In neutral water is: c(H3O+) = c(OH-) = 10-7 mol/L

For every solution is: c(H3O+) · c(OH-) = 10-14 mol²
mol²/L²
/L²
Note: concentrations are multiplied!
Analogous to pH a pOH value can be defined:
The pOH value is the negative decimal logarithm of the
hydroxide ion concentration.
pOH = − log[c (OH − )]
c(H3O+)·c(OH-)=10-14 mol/L logarithm ⇒ pH + pOH = 14
Examples: pH pOH solution
2 12 acidic
7 7 neutral
11 3 alkaline
Page 129

pH calculation
(strong acid or strong base)
base)

Example:
Example:
n =0,1mol of strong acid (HA) added to V=10 L water.
water. pH = ?
HA + H2O→H3O+ + A- (1 mol acid produces 1 mol hydronium)
hydronium)
c( H 3O + ) = nHA / V = 0,1mol / 10L = 0,01mol / L = 10−2 mol / L
pH = − log[c( H 3O + )] = − log10 −2 = 2

Example:
Example:
0,01 mol of strong base added to 100 L of water.
water. pH = ?
c(OH − ) = nB / V = 0,01mol / 100L = 0,0001mol / L = 10−4 mol / L
pOH = − log[c(OH − )] = − log 10 −4 = 4
pH = 14 − pOH = 14 − 4 = 10
Page 130

65
 pH Values of Common Solutions

Substance pH-Wert Art Substance pH-Wert Art

Battery acid -0,5 Acidic
Saliva 6,5 – 7,4 Acidic to
Gastric acid 2,0
Lemon juice 2,4 Blood 7,34 – 7,45 Alkaline
Coke 2-3 Sea water (today) 8,05
2,7 Sea water 8,16
Vinegar 2,9 (pre-industrial)
Orange/apple juice 3,5 Intestine 8,3
Soap 9,0 – 10,0
Wine 4,0
Sour milk 4,5 Sal ammoniac 11,5
Beer 4,5 – 5,0 Bleaching agent 12,5
Acid rain <5,0 Concrete 12,6
Coffee 5,0
Caustic Soda 13,5
Tee 5,5
Rain 5,6
Mineral water 6,0
Milk 6,5
Distilled water 7,0 Neutral
Page 131

pH Indicator

A pH indicator is a halochromic compound added in small amounts

to a solution to visualized acidity resp. basicity by color.
Indicators are colored compounds, which undergo acid- acid-base-
base-
reactions ⇒ chemical structure and color is changed.
Indicator enable a rough determination of the pH value:
Examples: Litmus

Chemical structure of the

indicator methyl orange Page 132

66
 pH Test Strip/pH Meter

pH Test strips contain a mixture In a pH-

pH-Meter electrochemical
of different indicators. determination of H3O+ ion
Comparison of color with concentration and calculated
reference scale ⇒ pH value. pH value displayed.

Glas electrode

Page 133

Neutralization

Combination of an acidic solution with a certain with a certain

c(H3O+) with an identical volume of an alkaline solution with
the same c(OH-) produces a neutral solution (pH=7).
The underlying reaction is a neutralization.
neutralization.
H3O+ + OH- H2O + H2O
If identical amounts of substance (equimolar
(equimolar amounts)
of H3O+ and OH- are combined, they react in a neutralization
reaction to neutral water.
Attributes of a neutralization:
• represents an acid- base-reaction, proton transfer H3O+ to OH-.
acid-base-
• exothermal reaction; reaction heat is released!
• used in quantitative analysis for determination
of unknown c(H3O+) or c(OH-): Acid-
Acid-base titration (later)

Page 134

67
 Calculation of Neutralization Reaction

In a submarine 180 L acid are leaked out of the battery cells

with pH = 1. How much sodium hydroxide solution of c = 2 mol/L
is necessary for a complete neutralization (pH = 7) ?

Neutralization means:
amount of substance of acid (H3O+)
is equal to amount of base (OH-)
nA = nB
cA⋅VA = cB⋅VB cA = 10-pH = 0,1 mol/L
VB = cA⋅VA/cB

0 ,1mol/L ⋅180 L
VB = = 9L
2mol/L

Page 135

Formation of Salt by Neutralization

In addition to H3O+ and OH- -ions acidic and alkaline solutions

both contain counter ions (electric neutrality).
They can be product of a previous acid-
acid-base-
base-reaction
from production of the acidic solution:
Example: HCl (g) + H2O (l) → Cl- (aq)
aq) + H3O+ (aq)
aq)

or they result from the dissolution of a compound in water:

H O (l)
Example: NaOH (s) 2 → Na+ (aq)
aq) + OH- (aq)
aq)
Total reaction of the neutralization:
Cl-(aq)
(aq) + H3O+(aq) + Na+(aq) aq) → Na+(aq)
(aq) + OH-(aq) (aq) + Cl-(aq)
(aq) + 2H2O

If the water is evaporated NaCl (table salt) is remaining.

Acid + Base → Salt (+ Water)
Page 136

68
 Quantitative Analysis
Titration
Determination of the concentration of an unknown solution by defined
defined
addition of another solution (standard solution with known conc.)
conc.)
until equivalence point is reached, visualized by indicator.
Standard solution

At equivalence point:
nknown = nunknown
cknown·Vknown.= cunknown.·Vunknown
Reaction has to be:
cknown·Vadded • complete
cunknown= V • known stoichiometry
Burette

receiving • fast
• End point detectable
Suitable reactions:
• Neutralization
• Redox reaction
unknown • (Complexation)
solution Page 137

Acid-
Acid-Base-
Base-Titration
(Principle)
Acidic solution, c(H3O+) = ?
Measuring a certain volume
of acid VA; Drop wise addition
of sodium hydroxide solution
with known concentration cB
until pH=7 (neutralization);
Measuring the consumption
of basic solution VB.
At equivalence point:
n A ⋅ ( z A ) = nB
with number of acid protons zA
with n = c ⋅V
VB
c A ⋅ VA ⋅ ( z A ) = cB ⋅VB c A = cB ⋅
VA ⋅ ( z A ) Page 138

69
 Quantitative Acid-
Acid-Base-
Base-Reaction
(Strong Acid/Base)
If a certain amount of base is added to an existing acidic solution,
solution,
the acid is neutralized partly.
What is the concentration of the remaining acid ?;
Which pH-
pH-value is reached ?
In the existing acid with a volume VA and a concentration
cA the amount of H3O+ is: n + = c A ⋅ VA ⋅ z A
0 ( H 3O )

The addition of base produces a certain amount of OH- ions:

n(OH − ) = cB ⋅VB

Part of the H3O+ is neutralized; the remaining amout is:

c A ⋅VA ⋅ z A − cB ⋅VB
n( H O + ) = n0 ( H O + ) − n(OH − ) with the conc.: c( H 3O + ) =
3 3 VS + VB
Volumes have to be added
For identical conc. cA=cB und zA=1, simple equation:
c ⋅ (VA − VB )
c( H O + ) =
3
V A + VB Page 139

Titration Curve
(Strong Acid/Strong Base)
Titration of 20 ml 0.1 molar HCl
with 0.1 M NaOH (c (cA=cB , zA=1) Equivalence point
0,1 ⋅ (20 − VB ) nA = nB
c( H O + ) =
3
20 + VB
Addition VB c(H3O+) mol/L pH value Neutral point
NaOH [ml] c(OH-) mol/L pH = 7
0 0,1 1
5 0,06 1,22
10 0,033 1,47
15 0,014 1,84
19 0,0025 2,6
19,9 2,5·10-4
2,5· 3,6
19,99 2,5·10-5
2,5· 4,6
20 10-7 7* * Ion product of water relevant
21 0,0025 11,4 0,1 ⋅ (VB − 20)
30 0,02 12,3 c(OH − ) =
40 12,5 20 + VB
Page 140

70
 Acidity Constant;
pKA Value
In addition to very strong acids, which dissociate completely,
weaker acids exist, which dissociate only partly.
Their equilibrium reaction in water is described by
the law of mass action.
HA + H2O → H3O+ + A-

c( H 3O + ) ⋅ c( A− ) since c(H2O)≈ c( H 3O + ) ⋅ c( A− )
K= KA =
c( HA) ⋅ c( H 2O ) const. ⇒ c( HA)
The acidity constant KS is a measure for the strength of the acid

Often, the negative decimal logarithm pKA is represented:

pK A = − log K A Analogous KB and pKB for bases
Important note: pH describes individual solution property
In contrast to: pKA describes compound property! Page 141

pKA Table

conjugated conjugated
acid Name pKA acid Name pKA
very strong

base base
HClO4 Perchloric acid ClO4- -9 H2S Hydrogen sulfide HS- 7,06
weak

HCl Hydrochloric acid Cl- -6

H2PO4- Dihydrogenphosph. HPO42- 7,21
H2SO4 Sulfuric acid HSO4- -3
HClO Hypochloric acid ClO- 7,25
H3O+ Hydronium ion H2O -1,74
NH4+ Ammonium ion NH3 9,21
moderate

HNO3 Nitric acid NO3- -1,32

HClO3 Chloric acid ClO3- 0 HCO3- Hydrogencarbonate CO32- 10,4

HSO4- Hydrogen sulfate SO42- 1,93 H2O2 Hydrogen peroxide HO2- 11,62
strong

H3PO4 Phosphoric acid H2PO4- 1,96 HPO42- Hydrogenphosphate PO43- 12,32

HF Hydrofluoric acid F- 3,14 Hydrogensulfid-
HS- S2- 12,9
strong

CH3COO ion
H
Acetic acid CH3COO- 4,75 H2O water OH- 15,74
weak

(H2CO3) Carbonic acid HCO3- 6,46 OH- hydroxide-ion O2- 24

For conjugated acid-

acid-base pairs is: pK A + pK B = 14

Page 142

71
 Degree of Protolysis
(Degree of Dissociation)

Degree of protolysis α = Fraction of dissociated acid in equilibrium.

α= concentration of dissociated acid c( HA)0 − c( HA)

total concentration of acid =
c( HA)0

Degree of protolysis depends on KA value (resp. pKA)

and on initial concentration of acid c0:

Ostwald Law of Dilution: α = K A c0

Stronger acid or
lower concentration
⇒ more dissociation
(=protolysis
(=protolysis))

Page 143

pH Calculation II
(Weak Acid)

c( H 3O + ) ⋅ c( A− ) since c(H3O)+=c(A-)
KA = and weak acid ⇒
c( HA) c(HA) ≈ c(HA)0
little dissociation: c(HA)

c ( H 3O + ) 2
KA = ⇒ c( H 3O + ) = K A ⋅ c( HA) 0
c( HA) 0

logarithm ⇒ pH = 1
2 [ pK A − log c( HA) 0 ]
Example:
0,1 mol acetic acid (pK
(pKA = 4,75) in 1 L water:
pH = 1
2 [4,75 − log 0,1] = 1
2 ( 4,75 + 1) = 2,875

Page 144

72
 Buffer Solutions

Buffer solutions contain a weak acid and its conjugate weak

base together.
Buffers stabilize the pH value against external acid/base attack.
attack.
Only minor changes of pH by addition of acid or base.

c( H 3O + ) ⋅ c( A− ) + c( HA)
KA = ⇒ c ( H 3O ) = K A ⋅
c( HA) c ( A− )
c( A− )
take logarithm ⇒ pH = pK A + log
c( HA)
Henderson-
Henderson-Hasselbalch equation:
Calculation of pH of buffer solution

For pH < pKA, more acid than conjugate base;

for pH > pKA, more conjugate base than acid.
Page 145

Buffer Effect

Buffer solution neutralizes added

strong acid or base partly, by
shifting the equilibrium.
Most effective buffer,
if c(HA):c(A-) = 1:1
(so that pH = pKA)
(H3O+) is converted
Strong acid (H
into weak acid

H3O+ + A- → HA + H2O
Buffering of base analogous
Excess of acid or base by
a factor of 10 alters
the pH value only by 1!
Molar fraction of base Page 146

73
 Titration Curve
Weak Acid/Strong Base
Example: Neutral point:pH = 7<Equivalence pH=8,72
20 ml 0.1 molar acetic acid
(pKA=4,75); 0.1 M NaOH added
Initially:
pH = 1 2 [4,75 − log 0,1] = 2,875
By addition of NaOH solution:
X
HAc + OH- → Ac- + H2O X
−
HAc/Ac-- pH = 4,75 + log c( Ac )
HAc/Ac Buffer
Buffer: c( HAc) region
Addition NaOH [ml] pH-
pH-Wert
0 2,875
5 4,27
10 4,75
19 6
19,86 7 Equivalence p.: all HAc neutralized;
20 8,72 only 0,05 mol/L Ac- (pKB = 9,25)
>25 as for HCl/NaOH pH = 14 − 1 2 [9,25 − log 0,05] = 8,72
Page 147

Titration Curve of Phosphoric Acid

Phosphoric acid dissociates in three steps:

H3PO4 + H2O → H2PO4– + H3O+ pKS1 = 2,0

H2PO4– + H2O → HPO42– + H3O+ pKS2 = 7,2

HPO42– + H2O → PO43– + H3O+ pKS3 = 12,3

value Titration curve 10 mL 0.1 M H3PO4 PO43–

E
(not complete)
E
HPO42–

E
H2PO4–

H3PO4
(0,1 M)
Page 148

74
 4.2 Salts, Solubility
The Crystalline State
Microscopic characteristics of the crystalline state is:
• 3D regular spatial arrangement (crystal lattice)
• of ions (salts), atoms (metals), or molecules
• with high symmetry and long range order.
order.
Macroscopic crystals: flat surfaces, high symmetry.
Examples:

Quartz
CaF2 (SiO2)
Such single crystals are transparent, but refractive.
Polycrystalline material (µ
(µm size crystals) are opaque. Page 149

Crystal Lattice

Different types of atomic crystal lattices exist, which are represented

represented
in the external shape of the macroscopic crystal: Cubic, tetragonal,
tetragonal,
hexagonal, monoclinic, triclinic. Dense sphere packing is sought ⇒
highest lattice energy; arrangement of counter ions electric neutral.
neutral.
Crystal type depends on ratio of ion radii r(cation):r((anion).
r(cation):r((anion).
CsCl-type: Cs+:Cl- > 0,7 ⇒
CsCl- NaCl-type: Na+:Cl- <0,7 ⇒
NaCl-
cubic body-
body-centered lattice; cubic face-
face-centered.
Each Cs+ surrounded by 8 Cl- Each Na+ surrounded by 6 Cl-
(and vice-
vice-versa).
Na+
Cl-

In ZnS-
ZnS-(Zincblende)-
(Zincblende)-type:
type:
Zn2+:S2-<0,4 ⇒ coordination number 4. Page 150

75
 Amorphous State

The amorphous state is formed by the same molecular entities

as the crystal lattice (ions, molecules), but without long
range order.
order. Also denoted as glassy state.
state.
Amorphous solids have bent fracture surfaces.
Examples:
Examples: Glasses and sediments like flint stone, opal and
Malachite = (Cu(OH)2·CuCO3)
Anisotropy is the proper-
proper-
ty of being directionally
dependent.
E. g. refractive index

Crystals are anisotropic;

Amorphous bodies
are isotropic.

Page 151

Salts

Salts are ionic solids, in which the cations (+) and anions (- (-) are
arranged regularly in a 3D crystal lattice.
lattice.
Due to the strong electrostatic attractions between oppositely char char--
ged ions (lattice energy) salts have high melting points (NaCl 800° 800°C).
Salt crystals are electrically neutral, i. e. the charges of cations
cations and
anions are balanced = no net charge.
mAn + + nB m − → Am Bn
In salts of main group elements (I, II, VI, VII) the monoatomic ions
comply with the octet rule ⇒ defined stoichiometry: (NaCl, MgCl2, Na2S)
Salts of auxiliary group elements (transition metals) often have
variable valancy:
valancy: FeCl2 = {Fe2+2Cl-} = iron(II)
iron(II)-chloride
FeCl3 = {Fe3+3Cl-} = iron(III)
iron(III)-chloride
Cu2O = {2Cu+O2-} = copper(I)
copper(I)-oxide
CuO = {Cu2+O2-} = copper(II)
copper(II)-oxide
Salts can also be composed of polyatomic ions:
Ammonium- NH4+, Carbonate-
Ammonium- Carbonate- CO32-, Sulfate-
Sulfate- SO42-, Phosphate-
Phosphate- PO43-
Dichromate- 2- -
Dichromate- Cr2O7 , Permanganate-
Permanganate- MnO4 .
Composition of the salt with according to charge balance; e. g.:
KMnO4={K+MnO4-}, K2Cr2O7={2K+Cr2O72-}; (NH4)2CO3={2NH4+CO32Page -}
152

76
 Salts and Minerals
(Trivial names)
A mineral is a naturally occurring solid chemical NaCl=table salt=
substance formed through biogeochemical pro- pro- rocksalt=halite
rocksalt=halite
cesses,
cesses, having characteristic composition,
composition,
highly ordered atomic structure,
structure, and specific
physical properties
Common minerals:
Sandstone = sedimented quartz grains (SiO2)
Chalk = calcium carbonate (CaCO3)⇒
Lime stone = Calcium carbonate, too (CaCO3), ⇒
Marble = Calcium carbonate, too (CaCO3)
Gypsum = Calcium sulfate (CaSO4)
Sulfidic minerals:
minerals: Silicates:
Silicates: Si-
Si-Oxides with Al, Fe, Mg, Na, K, ions.
Zincblende (ZnS),
ZnS), Most rock-
rock-forming minerals
Pyrite (FeS2),
Galena (PbS Other important minerals
(PbS))
Bauxite: mainly Al(OH)3
Oxides: Corundum (Al2O3); Chile niter: NaNO3
Oxides:
Iron oxides: Hematite (Fe2O3),
Magnetite (Fe3O4), W üstite (FeO)
FeO)
Page 153

Lime Cycle

Page 154

77
 Solvation of Salts
Hydrate Shell
Ion crystals can be dissolved preferably in the polar solvent water.
water.
At surface water molecules are attracted by the ions; ions are dis-
dis-
solved. They are surrounded by a hydrate shell.
shell. (hydration)

Solvation of NaCl in water:

hydrated ions

crystal

Page 155

Solubility Product

The solubility of a certain ionic compound in the respective solvent

solvent is
limited. The solubility of salts quantified by the solubility product.
product.
Heterogeneous equilibrium between saturated solution of the salt
and solid, sedimented salt: A+ B − → A + + B −
(s) ( aq ) ( aq )

+ −
Solubility product: K Sp = c ( A ) ⋅ c( B )

Form of solubility product depends on stoichiometry:

2+ − 2+ −
Example: A 2 B ( s ) → A ( aq ) + 2 B ( aq ) e. g. CaCl2

KSp = c( A2+ ) ⋅ c 2 ( B − ) and for Al2O3 ?

If product of ion concentration < KSp ⇒ unsaturated solution;

If product of ion concentration > as KSp ions crystallize as salt.

The solubility product is temperature dependent.

(like all equilibrium constants) Page 156

78
 Solubility Products
Poor Solubility Salts

Low solubility: KSp < 10-4 mol2/L2

Compound KSp Compound KSp
Hints:
Hints:
Halogenides Sulfates
• alkali metal salts
AgCl 10-10 mol2/l2 CaSO4 2·10-5 mol2/l2
have good solubility
AgBr 5·10-13 mol2/l2 BaSO4 1·10-9 mol2/l2
• alkali earth salts
AgI 8·10-17 mol2/l2 PbSO4 1·10-8 mol2/l2
Sulfides
have lower solubility
Carbonates
HgS 10-54 mol2/l2
• Heavy metal salts
CaCO3 5·10-9 mol2/l2
10-36 mol2/l2
(Ag, Pb,
Pb, Ba,
Ba, Cd)
Cd)
BaCO3 2·10-9 mol2/l2 CuS
Hydroxides CdS 10-28 mol2/l2
poorly soluble
Mg(OH)2 10-11 mol3/l3 PbS 10-28 mol2/l2
• Sulfides (S2-) are
Al(OH)3 10-33 mol4/l4 ZnS 10-22 mol2/l2
poorly soluble
Fe(OH)2 10-15 mol3/l3 NiS 10-21 mol2/l2
Fe(OH)3 10-38 mol4/l4 MnS 10-15 mol2/l2
Cr(OH)3 10-30 mol4/l4 Ag2S 10-50 mol3/l3
Page 157

Precipitation Reactions

Silver nitrate (AgNO3) is the best soluble silver salt.

What happens, if a sodium chloride solution is added
to a saturated solution of silver nitrate?
Ag (+aq ) + NO3−( aq ) + Na(+aq ) + Cl(−aq ) → ?

The solubility product of silver chloride (10-10) is exceeded

and the salt AgCl precipitates.
{
Ag (+aq ) + NO3−( aq ) + Na(+aq ) + Cl(−aq ) → Na(+aq ) + NO3−( aq ) + Ag + Cl − ↓ }
Page 158

79
 The Solubility

Due to the different unit dimension KSp values are hard to compare.
Therefore, definition of the solubility S of a salt:
For A+ B − ( s ) → A+ ( aq ) + B − ( aq ) S = c( A+ ) = c( B − ) = K Sp

Example: AgCL)=10-10 mol2/L2

Example: KSp (AgCL)=10 LAgCl = 10 −10 = 10 −5 mol / L
c( Ag + ) = c(Cl − ) = c( AgCl ) = 10 −5 mol / L
m = M ⋅ n = 143,5 g / mol ⋅10 −5 mol = 1,435mg
For the general case of a salt AxBy:

c( A y + ) c( B x − ) x + y K Sp
S= = =
x y xx ⋅ y y

Page 159

Temperature Dependence
of the Solubility

The dissociation of ions from the crystal is a highly endothermic

endothermic
(energy consuming) process .
In contrast, energy is released when the ion is solvated.

Lattice energy
Solvation
- Solvation energy
= Solution energy
Energy

Solution energy > 0 ⇒ endothermic

endothermic process solution
Solution energy < 0 ⇒
exothermic
exothermic process.

Most solution processes are endothermic

⇒ improved solubility at higher temperatures.
←
A+ B − ( s ) + Energie → A+ ( aq ) + B − ( aq ) Page 160

80
 Common-
Common-Ion Effect

The common-
common-ion effect is the decrease of the solubility of one salt,
when another salt, which has an ion in common with it, is also present. present.
For example, the solubility of silver chloride,
chloride, AgCl,
AgCl, is lowered when
sodium chloride, a source of the common ion chloride, is added.
c( Ag + ) = c(Cl − ) = 10 −5 mol / L
Example:
Example: An amount of NaCl-
NaCl-solution is added to a saturated AgCl- AgCl-
- - 3
solution, so that c(Cl )=10 mol/L.
mol/L. The solubility product of AgCl is
exceeded; AgCl has to precipitate until: K Sp = c( Ag + ) ⋅ c(Cl − ) = 10−10 mol / L

The solubility product remains constant!

The concentration of silver ions K Sp 10 −10

c(Ag+) ≠ c(Cl-) is then: c( Ag + ) = = = 10 −7 mol / L
c(Cl − ) 10 −3

Page 161

4.3 Redox Reactions

Basics, Definitions
Redox reactions are essential for chemical energy
storage and conversion: Fuel-
cell
Both in Battery
technology:
and
in nature: Combustion
Photosynthesis
alcoholic fermentation

Page 162

81
 Origin of the Terms
Oxidation/Reduction
Originally the term oxidation
oxidation described the reaction
of organic materials or metals with atmospheric oxygen;
i. e. the combustion of
wood, oil, wax or coal or the rust of iron
4 Fe + 3 O2
→ 2 Fe2O3

C + O2 → CO2
Reduction was the recovery of (precious) metals
from their respective salts e. g.: 2 HgO → 2 Hg + O2

Since there are many similar processes, which don't involve oxygen,
oxygen,
the term oxidation nowadays is used in a more general concept.
Page 163

Today's Definition of
Oxidation/Reduction
Oxidation is the loss of electrons by an atom, ion or molecule
⇒ increase of oxidation number (state)
Oxidation = Electron donation
A transfer of electrons changes material properties substantially:
substantially:
E.g.: Copper (red shiny metal) is transformed into Cu2+ ions.
Cu2+-Ions form together with anions salts or are solvated.
Solvated Cu2+ ions have a hydrate sheath and blue color.
This process
is reversible

Reduction is the gain of electrons by an atom, ion or molecule

⇒ decrease of oxidation number (state)
Reduction = Electron acceptance:
Page 164

82
 Redox Reaction
Thermite Reaction
Iron oxide powder mixed with aluminum powder.
Reaction initiated with sparkler or blowpipe (activation energy!).
energy!).
Exothermic
reaction!
Energy released
as heat and light.

Thermite
process used for
How can you prove that the welding rails
produced metal is iron,
not aluminum?
Page 165

Redox Reactions
Examples
No free electrons exist! Oxidation and reduction coexistent!
Redox reaction = Electron transfer:
Depending on the reactants several electrons can be transferred
In redox reactions the gain of electrons in the reduction must be
be
identical to the loss of electrons in the oxidation.
Electrons never show up in the total equation!
Example: Zinc + sulfur: Oxidation: Zn → Zn2+ + 2e-
Reduction: S + 2 e-→ S2-
Redox reaction: Zn + S → Zn2+ + S2- = ZnS
A redox reaction can formally be subdivided into oxidation and
reduction. The two parts reaction never occur separately!
Conservation of mass and charge: On both sides of reaction arror
same number of the atoms of each element and same total charge.
Note: Do not subtract electrons Zn - 2e- → Zn2+
No half molecules : ½ Cl 2 Page 166

83
 Balancing of Redox Equations
Aluminum reacted with bromine
yielding aluminum bromide:
Interim eq.: Al + Br2 → AlBr3
Bromine diatomic,
Aluminum ion 3 valent,
Bromide 1 valent

0 + III
3+
Oxidation ⇒ oxidation number increases! Al → Al + 3e −
0 −I
Reduction ⇒ oxidation number decreases! Br 2 + 2 e − → 2 Br −

Lost = gained electrons: Ox (·

(·2); Red (·3)
2 Al → 2 Al 3 + + 6 e − Total equation by
3 Br 2 + 6 e − → 6 Br − addition of partial
reaction equations;
2 Al + 3 Br2 → 2 Al 3 + + 6 Br − = 2 AlBr3 e- eliminated!
Page 167

More Redox Reactions

Reduction of iron-
iron-(II)-
(II)-oxide to iron:
Redox : 2 FeO + C → CO2 + 2 Fe
Oxidation : C + 2 O2- → CO2 + 4 e-
Reduction: 2 Fe + 4 e → 2 Fe
2+ -

Redox reaction without oxygen:

Redox: 2 Na + Cl2 → 2 NaCl
Oxidation: 2·(Na → Na+ + e-)
Reduction: Cl2 + 2 e- → 2 Cl-
Redox reaction with complex stoichiometry:
Redox: 16 Al + 3 S8→8 Al2S3={2Al3+3S2-}
Oxidation: 16·(Al → Al3+ + 3 e-)
Reduction: 3·(S8+16 e-→8S2-)
The stoichiometric factors result from combination
of the partial reaction steps.
Na (I. mg) looses 1 e-,
Cl (VII. mg) gains 1 e-,
to obey octet rule.
Chlorine diatomic gas.
Al (III. mg) looses 3 e-,
S (VI. mg) gains 2 e-,
to obey octet rule.
sulfur as S8 ring.
Page 168

84
 Oxyhydrogen Reaction

Many redox reaction are exothermic, i. e. release of energy.

Another reaction this kind the oxyhydrogen reaction (hydrogen test)
test)
Biggest hydrogen-
hydrogen-oxygen reaction
of all times?

Zeppelin "Hindenburg"
2 H2 + O2 → 2 H2O + energy Lakehurst 1937

Oxidation: H2 → 2 H+ + 2 e- H (I. mg) losses 1 e-,

O (VI. mg) gains 2 e-,
Reduction:O2 + 4 e- → 2 O2- ⇒ noble gas configuration.
configuration.
Redox: 2 H2 + O2 → (4H+ + 2O2-)→ 2H2O Both diatomic gases!
Page 169

Oxidizer/Reducer

Compounds which are able to oxidize other species (eliminate electrons)

electrons)
are called oxidizers (oxidants, oxidizing agents) = electron acceptors
The oxidizer itself is being reduced!
Common oxidizers:
• Oxygen O2 + 4 e-→ 2 O2-
• Chlorine Cl2 + 2 e-→ 2 Cl-
z.B.: MnO4- (Permanganate), Cr2O72- (Dichromate)
• Oxoanions z.B.:
z.B. ClO4- (Perchlorate)
• Anions of halogen oxoacids, z.B.
• Noble metal ions, e. g. Ag + e-→ Ag
+

Compounds which are able to reduce other species (donate electrons)

electrons)
are called reducers (reductants, reducing agents) = electron donators
The reducer itself is being oxidized!
Common reducers:
• Hydrogen H2 → 2 H+ + 2 e-
• Zn, Fe, Mg Zn → Zn2+ + 2e-
• Carbon
Page 170

85
 Oxidation Numbers/State

How do you know, its a redox reaction

and which species gains or looses how many electrons?
Redox reaction ⇒ change of oxidation numbers
Oxidation number = hypothetical charge an atom would have
if all bonds to atoms of different elements were 100% ionic.
Rules (order of priority) agreed-
agreed-upon for determ.
determ. Examples:
of oxidation state (roman numeral superscript): 0 0 0 0
1. Free elements always have oxidation number 0 H 2, Cl2, Na, Al
+I +II -II
2. Monoatomic ions: OxNo = charge Na+, Ca2+, S2-

3. H OxNo = +I ; O OxNo = -II

-I +I -I
(exception: Hydrides MeHx; H2O2)
-IV+I +IV-
+IV-II
4. In molecules ΣOxNo=0
OxNo=0 ; CH4, CO2
in molecular ions ΣOxNo=
OxNo= charge +VII-
+VII-II, +VI-
+VI-II
MnO4-, SO42-
Page 171

Oxidation Numbers
of Selected Compounds
Compounds of chlorine with various oxidation numbers:
OxNo -I 0 +I +IV +V +VII
Formula Cl- Cl2 ClO- ClO2 ClO3- ClO4-
HClO HClO3 HClO4
Name Chloride Chlori Hypochlorite Chloro-
Chloro- Chlorate Perchlorate
ne hypochloric acid dioxide Chloric acid Perchloric acid

Compounds of sulfur with various oxidation numbers:

OxNo -II 0 +III +IV +VI
Formula S2-/H2S S8 S2O42- SO2/SO32-/ SO3/SO42-/
H2SO3 H2SO4
Name Sulfide/Hydro Sulfur Dithionite Sulfur dioxide S.trioxide/Sulfate
S.trioxide/Sulfate
gen sulfide sulfurous ac. sulfuric acid
Compounds and oxidation numbers of manganese:
OxNo +II +IV +VI +VII
Formula Mn2+ MnO2 MnO42- MnO4-
Name Manganese Manganese Manganate Permanganate
(II) ion dioxide (blue) (violet)
Page 172

86
 Redox Reactions and pH-
pH-Value

In some redox reactions (often in aqueous solution)

H3O+ resp. OH- ions for the charge compensation
under consideration of the acidic or alkaline/basic environment

E.g.:
E.g.: Permanganate reduced to manganese(II)
manganese(II) in acidic environment
+VII +II
For compensation fo charges (left -6;
MnO4- + 5 e- → Mn2+
right +2) 8 H3O+ are introduced
(acidic environment).
MnO4 + 5 e + 8 H3O → Mn + 12 H2O Together with 4 O
- - + 2+ 2-

(formally) they form 12 H2O

E.g.:
E.g.: Hydrogen peroxide is oxidized to oxygen in alkaline.
alkaline.
-I 0
H2O2 → O2 + 2 e- +2 H+ Note: There are
no free protons!
H2O2 + 2 OH- → O2 + 2 e- +2 H2O

Both examples only partial reaction equations!

Page 173

Redox Titration
Example: Permanganometry
Redox reactions can be used in quantitative analysis (titration) for
determination of an unknown concentration of a solution,
if the equivalence point is detectable, e. g. change of color
Permanganometry:
Permanganometry: Titration of a solution of an oxidizable compound
(e. g. Fe2+) with potassium permanganate solution (KMnO4; violet);
The Fe2+ are oxidized by the drop wise added MnO4- ions gradually
yielding Fe3+ ions. At the same time the violet MnO4- ions are reduced
to colorless Mn2+ ions ⇒ decolorization of the added permanganate
permanganate
solution as long as Fe2+ ions are present.
After equivalency (Fe2+ ions consumed) no reaction of added MnO4-
ions⇒ violet coloring of the iron ion solution.
ions⇒

From volume and concentration of consumed permanganate solution

the concentration of Fe2+ solution can be calculated.
Account for stoichiometry! 1 mol MnO4- oxidizes 5 mol Fe2+. Page 174

87
 Chromatometry, Iodometry
Two other analytic methods like permanganometry (titrations)
but with different stoichiometry:
Chromatometry (dichromate titration):
titration):
Cr2O7 + 6 Fe + 14 H3O+ → 6 Fe3+ + 2 Cr3+ + 21 H2O
2- 2+

Dichromate
Iodometry:
Iodometry: determination of concentration by means of redox system
2 I- ⇒ I2 + 2 e-: Elemental iodine forms with starch solution a
deep blue complex.
complex.
Reversed titration method:
Example: determination c(Cu2+):
Example:
- Measure off defined volume (e. g. 20 ml)
- Add excess of KI solution ⇒ 2 Cu2+ + 2I- → 2 Cu+ + I2
- 2 mol Cu2+ produce 1 mol I2, which dyes the solution blue
- Determination of the molar of produced iodine by redox
titration with reductant solution of known concentration.
- I2+2S2O32- → 2I-+S4O62- (2 mol thiosulfate reduces 1 mol iodine)
- From vol. and conc. of used S2O32- ⇒n(I2)⇒n(Cu2+)⇒c(Cu c(Cu2+) Page 175

Noble/Base Metals

Why does iron rust, but gold does not? Does aluminum oxidize?
What is the difference between noble and base metals?
In general all metals can react by loosing electrons,
forming metal kations, i. e. they oxidize. But:
The various metals have a different oxidizability:
Noble metals:
metals: resistant to oxidation, low reactivity, occur in
elemental form. Gold, platinum, silver, (copper)
Base metals:
metals: readily oxidizable, reactive, occur in compounds
all main-
main-group metals:
(Alkali, alkaline earth H
metals, aluminum)
Transition metals: Li Be B
Iron, Zinc, etc. Na Mg Al
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In
Cs Ba La * Hf Ta W Re Os Ir Pt Au Hg Tl
Page 176

88
 Chemical Reactivity
(Oxidizability) of Alkali Metals
Alkali metals have highest reactivity.
Storage in inert media (ether) or
paraffin oil. Otherwise intense
reactions, like

4 Na + O2 → 2 Na2O

Sodium under paraffin oil

Water not feasible as storage medium,
since sodium (like all alkali metals) reacts with water.
2 Na + 2 H 2O → 2 Na(+aq ) + 2OH (−aq ) + H 2 ↑

Sodium hydroxide is produced

and hydrogen, which is inflamed.
The sodium melts (Tm=98°
=98°C)
due to reaction heat
Page 177

Redox Reactions
of Noble and Base Metals

Cu2+ Zn2+

Zn+2 HCl → Cu+2HCl →

Zn + Cu2+→Zn2++Cu
Zn2++2Cl-+H2↑
Why?
Why?

Page 178

89
 Table of Noble/Base Metals

Gold The oxidizability of metals, i. e. their tendency

Platinum to loose electrons, can be compared by direct
noble

Palladium reaction with each other ⇒ ranking

Mercury
Examples: Ag + Au+ → Ag 2++ Au
+ +
Silver Cu + 2 Ag → Cu + 2 Ag
Copper Ni + Cu2+→ Ni2++Cu
Lead decreasing oxidizability Fe + Ni2+ → Fe2+ + Ni
Zn + Fe2+→ Zn2+ + Fe
increasing reducing reaction
Tin
Nickel but: Cu + Zn2+ →
Cobalt
Cadmium Driving force for the oxidation of base metals
Iron by noble metal kations is: ∆G<O
reactive

Chromium
Zinc How can the tendency of electron
Aluminum attraction or repulsion be quantified?
Magnesium
Sodium How can the energy released in redox
Calcium reactions be utilized?
Potassium
Lithium
Page 179

Conversion of Energy

Chemical energy Heat z.B.: C + O2 → CO2

z.B.:
Oder: Zn + Cu2+→Zn2++Cu
Electric motor
Electric energy Mechanical energy
Dynamo

Battery
Chemical energy Electrical energy

Spatial separation of oxidation (Zn → Zn2++ 2e-) and

(Cu2++ 2e- → Cu) reaction. Instead of direct transfer from
reduction (Cu
oxidation to reduction site. electrons have to flow through conductor.
conductor.
Accumulator
Chemical energy Electrical energy
Page 180

90
 4.4 Electrochemistry:
Redox Potential; Galvanic (Voltaic) Cell
Between a metal bar (electrode) and the surrounding metal ion solution
solution
(electrolyte) charges are exchanged by chemical reactions building
building up a
difference in the chemical potential. More noble metals have a lower
lower
tendency to loose electrons. If two such half-
half-cell are connected by a
conductor the potential difference ∆E can be measure as voltage.
voltage.

∆E=1,1 V
Half-cells

less more
noble noble
⊕ ⊕ ⊕
⊕ ⊕ ⊕
⊕ ⊕
⊕ ⊕
Page 181

Table of Standard Electrode Potenials

Strength oxidizing/reducing agents

depends on change of Gibbs free ener-ener- Ox. ne Red. ∆E0

gy ∆G during electron loss or gain: Fluor (F) F2 + 2e- ↔ 2F- +2,87 V

Gold (Au) Au+ + e- ↔ Au +1,69 V
Each redox system (electrode/
Platinum (Pt) Pt2+ + 2e- ↔ Pt +1,20 V
electrolyte ⇒ redox potential;
potential;
increasing reducing activity

Chlorine (Cl) Cl2 + 2e- ↔ 2Cl- +1,31 V

listed in Table of Standard Electrode
oxygen (O2) O2+4H+ + 4e- ↔2 H2O +0,85 V
Potential.
Potential.
increasing oxidation activity

Silver (Ag) Ag+ + e- ↔ Ag +0,80 V

Isolated potential (half-
(half-cell)= not Sulfur (S) S + 2e- ↔ S2- +0,48 V
obtained emp. ⇒ only galvanic cell Copper (Cu) Cu2+ + 2e- ↔ Cu +0,35 V
potial between pairs of electrodes ∆E. hydrogen (H2) 2H+ + 2e- ↔ H2 0
E0 Hydrogen Electrode defined 0 Lead (Pb) Pb2+ + 2e- ↔ Pb -0,13 V
Stronger oxidizers (Ox) Tin (Sn) Sn2+ + 2e- ↔ Sn -0,14 V
⇒ positive potential ∆E0 Nickel (Ni) Ni2+ + 2e- ↔ Ni -0,23 V
Stronger reduction agents (Red) Cadmium (Cd) Cd2+ + 2e- ↔ Cd -0,40 V
⇒ negative potential ∆E0 Iron (Fe) Fe2+ + 2e- ↔ Fe -0,41 V
Stand.cond.(25°
(25°C,1013 hPa,1 mol/L).
mol/L). Zinc (Zn) Zn2+ + 2e- ↔ Zn -0,76 V

∆ R G 0 = − ne ⋅ F ⋅ ∆ E 0 Faraday-
Faraday-Konst.
Konst. F Aluminum (Al) Al3+ + 3e- ↔ Al -1,66 V
Magnesium (Mg) Mg2+ + 2e- ↔ Mg -1,66 V
Base metals oxidized by acid (H+⇒H2 Sodium (Al) Na +
+ 1e- ↔ Na -2,71 V
noble metals and copper are not. Lithium (Li) Li+ + 1e- ↔ Li -3,02 V Page 182

91
 Standard Hydrogen Electrode (SHE)

Determination of standard electrode potentials in comparison

to Standard Hydrogen Electrode (set to ∆E0=0 V)

∆E0=0 Volt
Salt bridge

Page 183

Galvanic Cell / Voltaic Element

Electromotive Force (EMF)
Combination of two halb-
halb-cells is a Galvanic Cell
∆E0= ∆E0 (cathode) -∆E0 (Anode) = EMF (Electromotive Force)

Daniell cell

Anode cathode
0.35-(-0.76)V

metallic
copper
Zink electrode precipitated
dissolved

Page 184

92
 Nernst Equation
Concentration Dependence of Electrode Potential
The potential of a real electrode depends on the standard potential
potential of the
redox system (electrode/electrolyte) an on the conditions (concentration,
(concentration,
pressure, temperature).
Under standard condition (c = 1mol/L solution,1013 hPa,
hPa, 25°
25°C)
the standard potential E0 is listed in the table.
For higher or lower concentration of the electrolyte the electrode
electrode potential
of the half-
half-cell E can be calculated by the Nernst equation:

0,059 Nernst
E = E0 + ⋅ log c( Me n + ) equation
n
Example:
Example: What is the potential of a copper electrode
in a Cu2+-ion solution of c = 0,1 mol/L? Walter Hermann Nernst

0,059 0,059
E = 0,35 + ⋅ log 10 −1 = 0,35 + ⋅ (−1) = 0,3205V
2 2
Page 185

Corrosion,
Corrosion, Passivation

Corrosion:
Corrosion: Disintegration of an engineered material
due to chemical reaction with its surrounding (oxygen, acid)
2 Me + O2 + 2 H 2O → 2 Me 2+ + 4OH −
2 Me + 2 H 3O + → 2 Me 2+ + 2 H 2O + H 2 ↑
Basic metals oxidized by atmospheric oxygen ⇒ few nm oxide layer.
Formation of hard, non-
non-reactive surface film inhibits further corrosion
Ti),⇒ Passivation)
(e.g. Al2O3 on Al, ZnO on Zn, TiO2 on Ti),⇒ Passivation)
Iron, however, forms a porous oxide layer (rust). oxygen can penetrate
penetrate
rust layer until complete corrosion (Fe2O3, Fe3O4) (Pitting
(Pitting).
).
In hot-
hot-dip galvanizing process iron or steel are coated with a zinc layer
layer
by passing metal through molten zinc bath (460°
(460°C). Exposed to atmo-
atmo-
sphere, zinc reacts with O2 to form ZnO and further
with CO2 to ZnCO3, a dull grey, fairly strong material
protecting the iron below against further corrosion
(passivation). If the coating is damaged, zinc works
as a galvanic anode so that iron is not oxidized.
Page 186

93
 Galvanic Corrosion
Galvanic (Sacrificial)
Sacrificial) Anode
Galvanic Corrosion:
Corrosion:
Short-
Short-circuited galvanic element;
Direct connection with a more noble
metal enhances oxidation (corrosion)
of the more basic metal, since electrons
are deflected. Contact between gold and Hg,Ag,Sn
amalgam fillings should be avoided,
otherwise mercury and tin are dissolved.
Galvanic anode:
anode: Basic metal
(Zn, Mg, Al, alloy) in direct contact
protects metal (Fe) from corrosion;
itself being dissolved (sacrificed)
In ships, pipes, etc.
Iron nail in saline with indicator
(with Fe3+ green dye):
Galvanic corrosion (contact with nobler
Cu) enhances iron dissolution,
Galvanic anode from Zn stops
corrosion. Zn2+(aq) colorless Fe/Cu Fe Fe/Zn
Page 187

Batteries:
Batteries:
Zinc-
Zinc-Carbon Battery (Dry Cell)
Cell)
Anode (Minus pole, Zinc case):
Zn → Zn2+ + 2e-
Cathode (Plus pole, carbon rod):
+IV +III
MnO2+ H++ 1e- → MnO(OH)
MnO(OH)
Manganese dioxide → Manganoxid-
Manganoxid-
hydroxid electrolyte Manganese
dioxide
Regeneration of H+ from the paste
Cathode
Ammonium chloride electrolyte:
NH4+ → NH3+ H+
Zinc ions bind produced ammonia
Graphite

as complex:
Zn2++ 2NH3 → [Zn(NH3)2]2+
rod

This complex forms with the chloride

ions (ammonium chloride) a salt
[Zn(NH3)2]2+ + 2Cl- →[Zn(NH3)2]Cl2(s) zinc case
anode
Total reaction:
reaction:
Zn + 2MnO +2NH4Cl → 2MnO(OH) + [Zn(NH3)2]Cl2
2MnO2 +2NH all solid!
Page 188

94
 Lead-
Lead-Acid Battery

Lead Lead electr.

electr. DISCHARGING
electrode Lead
(minus pole) dioxide
coating
(plus pole)

dissociated sulfuric acid

The chemical reactions are (charged to discharged):
Minus pol:
Plus pol:
0 +IV discharge+II = comproportionation

charging = disproportionation
For car: 12 Volt
stacking!
Page 189

Fuel Cell

Idea:
Idea: 1838 Christian Schö
Schönbein; since 1950 in space technology.
Electrodes separated by
membrane or electrolyte.
electrolyte. Theor. max.1,23 V: pract. 0,5-1 V ⇒ Stacking
Anode flushed with fuel
(H2, methane,
methane, ethanol,
ethanol,
glucose solution),
solution), DC
cathode with oxidizing
agent (O2, H2O2).
Electrodes made of
carbon nano tubes air
with Pt-
Pt- or Pd-
Pd-coating
as catalyst.
catalyst.

Typs:
Alkaline Fuel Cell
H2/ O2/OH- (100kW)
Direct Methanol Fuel Cell Membrane Cathode
MeOH/Luft/Polymer/H+ (500 kW)
Page 190

95
 Electrolysis

Processes in voltaic cells can be Voltaic cell

reversible: Applying DC-
DC-voltage at spontaneous
electrodes leads to electrolysis:
electrolysis:
Elements in the electolyte are separated Electrolysis
by enforced redox reaction.
reaction. non-
non-spontaneous

Ion migration due to electrostatic attraction:

attraction:
Positive Cations (Cu2+)→minus pole (cathode
(cathode))
Negative Anions (Cl-) → plus pole (anode
(anode))
Cathode: Cu2+ + 2 e– → Cu Reduction
Anode: 2 Cl– → Cl2 + 2 e–
Oxidation
Note:
Note: Polarity of cathode/anode reversed with
→ minus pole
element: Plus ←
respect to voltaic element:

Electrolysis of cop- Oxidation always at the anode!

anode!
per chloride solution
Page 191

Electrolysis of Water

Hoffman
faucet faucet
electrolysis
apparatus
oxygen hydrogen

acidic alkaline

2 H2O→ 1O2 + 4 H+ + 4 e- 4 H2O + 4 e- → 2 H2 + 4 OH-

anode platinum electrode (cathode)
cathode)

15 Volt DC !
Page 192

96
 Electrolytic Copper Purification

Crude copper anode

(99,5% pure) dissolved
Anode Cathode
at 0.2-0.3 V at anode.
Highly pure copper Crude copper Pure copper
(99,95%) precipitated
at cathode.
Impurities of base
metals (Fe, Zn) remain
in solution (as ions); Copper sulfate sol.
noble metal particles
are deposited on the
ground (anode sludge).
Anode sludge

Page 193

Aluminum Production
Hall-
Hall-Heroult Process
Aluminum ore (bauxite) heated in
conc. NaOH sol. 200°200°C (Bayer proc.).
Aluminum hydroxide ⇒ sol. Aluminate
Al(OH)3 + NaOH
Na+ + [Al(OH)4]-
Filtering of solid impurities;
Neutralisation → pure Al(OH)3 precip.;
precip.;
(1000°C) ⇒ Alumina.
Calcination (1000°
2 Al(OH)3
Al2O3 + 3 H2O

Alumina dissolved in molten cryolite

(Na3AlF6) at 1000°
1000°C in a ceramic vat;
electro-
electro-chem.
chem. reduction to Aluminum
5 Volt DC, some 100,000 A current!
Anodes of fused coke are consumed
by oxidation:

2Al2O3 + 3C → 4Al + 3CO2;

∆H = + 0,835 MegaJ/mol
MegaJ/mol Al
Extreme energy consumption!
Page 194

97