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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
Page 3
On-
On-line
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 :
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)
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
Resources of chemical
industry after 1870 - ?
• Crude oil
Page 9
Chemical Hazards
5
Benefit from Chemical Industry
Demographics
Population
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
Ascorbic Acid
Chlorophyll
Page 13
Analytical/Synthetic Chemistry
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
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
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.
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
Antoine Lavoisier
fr. Chem. (1743-1794)
Page 21
Chemical Reaction
Example: Sodium Chloride
Example:
Sodium (Metal) Chlorine Salt (NaCl)
11
Elemental Particles
Radiation
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
Atomic Mass
Example: Lithium
3 protons ⇒ atomic number Z = 3
4 neutrons ⇒ atomic mass = 7
Proton
Neutron
Electron
Page 28
14
Molecular Mass
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
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
4 mol carbon
1 mol carbon 4·6·1023 atoms
6·1023 atoms (48 g)
(12 g) Page 31
16
Illustration of
Stoichiometry and Molar Mass
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).
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
18
Non-
Non-whole Number Masses
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
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.
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
20
Bohr Model
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
Sodium
Copper
Even without spectrometer some elements Na Li Cu
can be distinguished by the color of the flame: Page 43
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
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
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
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
Page 50
25
Quantum Numbers
Page 51
Examples:
Phosphorus 15P Sulfur 16S
26
"Full" Outer Valence Shell
Noble Gas Configuration
27
More Examples for
Noble Gas Configuration
Page 55
28
Metallic Bonding
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.
29
Ionization Energy
eV]]
Ionization energy [[eV
Li agaist the nuclear charge
Be by the inner electrons
⇒ I.-
I.-Energy decreases.
decreases.
B
Ne
Electron Affinity
30
Electronegativity (EN)
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.
With consi-
deration of
the ionic
radius.
Page 63
32
Covalent Bond
+ + + +
+ +
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
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
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
Ions can also be formed from groups of joined atoms: Compound ions
ions
Most common compound ions:
35
Chemical Models
Mesomeric Resonance
Page 71
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.
sp3-Hybrid Orbitals
+
p s hybrid orbital
Page 74
37
Single Bonds
Two hydrogen atoms form a single bond (σ -bond)
by head-
head-on overlapping between the atom orbitals.
Other orbitals
can also form
σ-bonds:
Page 75
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
38
sp2-Hybridisation
Example: Boron
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
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
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
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
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.
≈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:
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
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
Normal
pressure
gaseous
Ambient Temperature T
temp.
Page 91
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
Page 94
47
Distillation
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
49
Example for
Exothermal/Endothermal Reaction
Example:
Hydrogen-
Hydrogen-oxygen reaction
2 H2 + O2 2 H2O
Electrolysis
Oxyhydrogen reaction
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
rea re
ctio ac ∆HR = -283
n
tio
∆Hf (CO2)= -393,5 kJ/mol
n kJ/mol
(measured)
Page 101
Hess Law
and Biological Processes
Photosynthesis
Combustion
Respiration
(Glycolysis,
Glycolysis, Citrate cycle,
cycle, ...)
Page 102
51
Entropy
Change of Entropy
52
Gibbs (Free) Energy
„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
H-H
H⋅⋅⋅H
⋅⋅⋅H reactant
reaction
enthalpy
∆HR < O Platinum
products ⇒ exothermal
Page 106
53
Kinetics
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
Page 108
54
Chemical Equilibrium
Reversible/Irreversible Reaction
Page 109
[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
Ampholyte
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
Example:
Example: Hydrogen chloride H Cl other halogens analogous
59
Strong/Weak Acids/Bases
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
More
poly-
poly- Oxalic acid H2C2O4
acids:
Sulfuric acid H2SO4
Phosphoric acid
H3PO4
Page 120
60
Concentrate/Dilute Strong Acids
Molarity
Strong Acids
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
Page 124
62
Carbonic Acid
Autoprotolysis of Waters
63
Ion(ic)
Ion(ic) Product of Water
The pH Value
64
Relationship between Hydronium and
Hydroxide Ion Concentration
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
pH Indicator
66
pH Test Strip/pH Meter
Glas electrode
Page 133
Neutralization
Page 134
67
Calculation of Neutralization Reaction
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
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 )
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
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
HSO4- Hydrogen sulfate SO42- 1,93 H2O2 Hydrogen peroxide HO2- 11,62
strong
CH3COO ion
H
Acetic acid CH3COO- 4,75 H2O water OH- 15,74
weak
Page 142
71
Degree of Protolysis
(Degree of Dissociation)
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
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
Buffer Effect
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
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
In ZnS-
ZnS-(Zincblende)-
(Zincblende)-type:
type:
Zn2+:S2-<0,4 ⇒ coordination number 4. Page 150
75
Amorphous State
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)
hydrated ions
crystal
Page 155
Solubility Product
+ −
Solubility product: K Sp = c ( A ) ⋅ c( B )
78
Solubility Products
Poor Solubility Salts
Precipitation Reactions
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
c( A y + ) c( B x − ) x + y K Sp
S= = =
x y xx ⋅ y y
Page 159
Temperature Dependence
of the Solubility
Lattice energy
Solvation
- Solvation energy
= Solution energy
Energy
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
Page 161
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
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 −
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+ -
84
Oxyhydrogen Reaction
Zeppelin "Hindenburg"
2 H2 + O2 → 2 H2O + energy Lakehurst 1937
Oxidizer/Reducer
85
Oxidation Numbers/State
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
86
Redox Reactions and pH-
pH-Value
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-
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
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⇒
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
Redox Reactions
of Noble and Base Metals
Cu2+ Zn2+
Page 178
89
Table of Noble/Base Metals
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
Battery
Chemical energy Electrical energy
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
∆ 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)
∆E0=0 Volt
Salt bridge
Page 183
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
94
Lead-
Lead-Acid Battery
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
Electrolysis of Water
Hoffman
faucet faucet
electrolysis
apparatus
oxygen hydrogen
acidic alkaline
15 Volt DC !
Page 192
96
Electrolytic Copper Purification
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
97