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Home , Inorganic chemistry

Selected Topics in General and Inorganic Table of topics:

1. Composition of the matter 2. Basic chemical laws and rules, formulae, equations 3. Structure of 4. of elements Lectures notes and interacve teaching by 5. Molecular structures & basic theories of chemical bonding 6. Principles of thermodynamics Jozef Noga 7. States of the matter at Faculty of Natural Sciences, 8. Introduction to 9. and bases Comenius University, Braslava 10. Introduction to 11. Elements and their basic compounds 12. Coordination chemistry 13. Organometallic compounds

Podmienky na absolvovanie predmetu (Grading policy): What is Chemistry? There will be two running written tests examinations An introduction to chemical science (maximum 20 points each) during the semester course. Final exam will consist of a 60-point test. Only those students will be admitted to final examination who achieve at least Chemistry is such a broad subject and one so full of 60 % of the points from tests and 60 % of laboratory work detail that it is easy for a newcomer to find it evaluation. For grade A, it is necessary to obtain at least 92 %, somewhat overwhelming, if not intimidating. The best for grade B at least 84 %, for grade C at least 76 %, for way around this is to look at Chemistry from a variety grade D at least 68 % and for grade E at least 60 % of of viewpoints: all points. Credits will not be assigned to a student, who will • How Chemistry relates to other sciences and to the world not earn at least 60% from running tests, or who will not earn in general at least 60% from laboratory work and to student, who will not • What are some of the fundamental concepts that extend earn at least 60 % from final exam. throughout Chemistry? • What are some of the major currents of modern-day Chemistry?

1 The scope of chemical science

Chemistry is too universal physics might be considered more dynamically-changing "fundamental" major focus: the structure and properties of substances on the changes that they undergo The real importance of Chemistry is that it serves as the interface to practically all of the other sciences

Chemist‘s view

Mainly theorecal to Mainly praccal

Why do parcular combinaons of What are the properes of a certain atoms hold together, but not compound? others?

How can I predict the shape of a How can I prepare a certain ? compound?

Why are some reacons slow, while Does a certain reacon proceed to others occur rapidly? compleon?

Is a certain reacon possible? How can I determine the Chemistry can be approached in different ways, each composion of an unknown yielding a different, valid, (and yet hopelessly incomplete) substance? view of the subject.

2 Chemistry is the study of substances; their properties, structure, and the changes they undergo. Macroscopic Microscopic Observation: Direct Indirect Realm: Macroscopic Microscopic

Stochiometric ratio, structures of solids, Composition formulae, mixtures ... , and atoms ... Thermal and other Changes stascs of energy energetic effects, (Energetics) distribuon equilibria Changes (dynamics) Reaction rates Mechanisms

Dynamics refers to the HISTORY details of that rearrangem- ents of atoms that occur Chemistry is a branch of science that has been around for a during , long time. In fact, chemistry is known to date back to as far as and that affect the rate the prehistoric times. Due to the amount of time chemistry at which change occurs. takes up on the timeline, the science is split into four general chronological categories. Energetics refers to the thermodynamics of che- The four categories are: mical change, relating to prehistoric times - beginning of the Christian era (black magic) the uptake or release of heat. beginning of the Christian era - end of 17th century () end of 17th century - mid 19th century (traditional chemistry)

mid 19th century - present (modern chemistry)

3 Milestones in the History of Chemistry Prehistoric Times – Beginning of the Christian Era ~300 BC - End of 17th Century (Alchemy) Fire – Smoke – Ceramics 300 BC-300 AD the Advent of the Alchemists ~3300 BC Bronze Age ( consisting primarily of attempt to transmute cheap metals to gold. The copper, with tin as the main additive) substance used for this conversion was called the Philosopher's Stone 1700 BC 6th Babylonian king Hammurabi’s reign – known metals were recorded and listed 13th-15th century intensive effort; in conjunction with heavenly bodies pope John XXII (1316-34) issued an edict against ~1300 BC Iron Age gold-making 430 BC Democritus proclaims the to be the Despite the alchemists' efforts, transmutation of cheap simplest unit of matter metals to gold never happened within this time period. 1493 – 1541 Paracelsus – (Philippus von Hohenheim) 300 BC Aristotle declares the existence of only four Modern , ; elements: fire, air, and earth Three principles: salt (solidity, inertness), properties: hot, cold, dry and wet (inflamability), (fluidity, heaviness, metallicity)

History of Chemistry ~1700 – ~1850 (Traditional Chemistry) 16th century Alchemists not only wanted to convert metals to Johann Joachim Becher – 1667 phlogiston theory gold, but they also wanted to find a chemical postulated a fire-like element called phlogiston, concoction that would enable people to live longer and cure all ailments. This elixir of life contained within combustible bodies, that is released during combustion (rusting). never happened either. 1774 Joseph Priestly heated calx of mercury, collect- th 17 century – 1661 Robert Boyle ed the colorless and burned different substances in this gas (discovery of oxygen) hypothesis that matter consisted of atoms and clusters of atoms in – oxygen (1778); (1783) motion and that every phenomenon disproved the phlogiston theory; list of elements was the result of collisions of particles law of mass conservation - Father of Modern Chemistry in motion John Dalton – 1803 Atomic Theory which states sometimes called that all matter is composed of atoms, which are small founder of modern chemistry and indivisible

4 History of Chemistry ~1850 - present (Modern Chemistry) 2009, IBM Imaging a real in Switzerland 1854 Heinrich Geissler creates the first vacuum tube. molecule!

1879 William Crookes – plasma - ZnS fluorescence  cathode AFM: rays atomic force microscopy

1885 Eugen Goldstein - positive particles - protons atoms-thin metallic probe is drawn ever-so-slightly 1895 Wilhelm Roentgen accidentally discovered X-rays above the surface of an 1896 Henri Becquerel - fluorescence of pitchblend – natural immobilized pentacene radioactivity – Nobel Prize in Physics1903 molecule cooled to nearly with Marie Skłodowska-Curie and Pierre Curie absolute zero.

1897 J.J. Thomson – discovery of the

Currents of modern Chemistry Synthesis is both one of the oldest areas of chemistry and one of the most actively pursued: few of the areas that have emerged as being especially important in modern chemistry major threads

Synthesis Separation science thread: something acting as the New-moleculecontinuous link orsynthesis theme of a - Identification and assay Chemistswhole are always challenged to come up Materials, polymers, and with molecules and containing novel features Theoretical and computational such as new shapes or chemistry unusual types of bonds.

5 Materials, polymers, refers to a of largely- automated techniques for generating tiny quantities of huge numbers of different attempts to molecules ("libraries") and relate the physical properties then picking out those having certain desired properties. and performance of engineering Although it is a major drug materials to their underlying discovery technique, it also has many other applications. with the aim - synthetic methods of developing improved that focus on reducing or eliminating materials for various the use or release of toxic or non- biodegradable chemicals or applications. byproducts.

Polymer chemistry Organic developing polymeric number of potential ("plastic") advantages over materials for conventional metalloid- industrial uses. based devices. Connecting individual Nanodevice chemistry polymer molecules by constructing molecular- cross-links (red) scale assemblies for ordinary polyethylene is a fairly soft increases the specific tasks such as material with a low , but strength of the computing, producing the cross-linked form is more rigid and material. resistant to heat. motions, etc.

6 , nanotubes and nanowires, Biosensors and biochips graphene Fullerenes were first identified in 1985 as products of experiments in which graphite was vaporized using a laser

R. F. Curl, Jr., R. E. Smalley, and H. W. Kroto shared the 1996 the surfaces of metals and semiconductors research is expected to lead to new "decorated" with biopolymers can serve as materials, lubricants, coatings, catalysts, electro- extremely sensitive detectors of biological optical devices, and medical applications substances and infectious agents

Biochemistry and Molecular biology Drug design looks at interactions between enzymes and possible inhibitors

Computer- modeling is an essential tool in this ranging from the fundamental chemistry of gene express- work and enzyme-substrate interactions to drug design

7 Proteomics Chemical genomics

This huge field focuses on the relations between structure explores the and function of proteins chain of events there are about 400,000 in which different kinds in humans. signaling molecules Proteomics is related to genetics in that the DNA regulate gene sequences in genes get decoded into proteins expression which eventually define and regulate a particular organism.

Separation methods: Identification tools:

8 Nature of the material world

Theoretical and Matter (Substance) (Physical) Field

^ Internally discretized, Continuous internal particles with non-zero rest structure, H Ψ = E Ψ mass

What is a substance composed of? Measures of the changes in material objects (as related to Chemistry) Elementary particles Mass (SI: kg) Energy (SI: J) A quantitative measure ... leptons quarks ... A measure of inertia of a body, (resistance to the motion of diverse forms of the composite particles changes); motion; can be transferred to other objects; converted atoms neutron, proton (baryons) rest mass velocity A. Einstein (1905) Molecules – entities composed of atoms light v. entity – discrete unit with a defined unique structure and properties, able of an The Law of Conservation of Mass and Energy independent existence Σ m = const. Σ E = const. ... associates, crystals ... – condensed systems M. V. Lomonosov 1758

Chemistry A. L. Lavoisier 1774-7 M. V. Lomonosov 1760

9 Atom (in a „nutshell“) Atomic mass: ~ 10-27 - 10-25 kg N u c l e u s surrounded by: not practical → relative atomic mass Ar Protons (+) nucleons electrons (-) Unified atomic mass unit (or constant): Neutrons (0) 1 12 -27 Z – proton number A = Z+N mu= 12 m( 6 C) = 1,660565.10 kg N – neutron number A 23 A ( A E ) = m( A E )/m A – nucleon number Z E 11 Na r Z Z u Nuclide: atomic species characterized by a specific constitution of its nucleus. more  weighted avarage Isotopes: same Z, different A 58 Approval by: IUPAC napr. 54 Fe , 56 Fe , 57 Fe , Fe 26 26 26 26 International Union of Pure and Applied Chemistry Isobars: different elements, equal „A“

Molecules – entities composed of atoms, with Molar mass: M(A) = m(A)/n(A) unambiguous structure and unique properties

Molar volume (Vm): Relative molecular mass Mr Avogadro‘s law – for an ideal gas M = m(X Y ) /m = a A (X) + b A (Y) - equal volumes of all , at the same r a b u r r temperature and pressure, have the same Molar fraction (n) (SI): mol - number of NA entities number of molecules

12 equal n(A)  equal volume NA Avogadro‘s constant = number of atoms in 12g C 3 -1 standard: (T=273.1 K; p=101.32 kPa; Vm =22.41 dm mol ) 23 -1 NA = 6,022140.10 mol otherwise: Vm = V/n

Amedeo Avogadro, 1776-1856, Italian

10 Physical properties of materials Classification of material systems Extensive Intensive depend on the amount do not depend on the Homogeneous Heterogeneous of a substance amount of a substance uniform intensive two or more phases properties throughout mass, volume, density, colour, its volume total energy content, boiling point, total electric resistance electric conductivity, A Phase boundaries total content of a given concentration, ... element, ... Used to characterize the colloids: no clear phase bondaries, substance intesive properties vary within the volume Dichotomy – a unique classification is not always possible e. g. pressure – both dependent and independent

Pure substances– Chemical individuals Pure substances

Unique physical and chemical properties Chemical elements Compounds Melting point (temperture), boiling p., spectral properties, ... heteroatomic isoatomic composition composition Production: from mixtures by separation methods same proton number Isomers – different alotropic modification Destilation, crystalization, liquid extraction, modifications with

... O: O2, O3 equal composition. C: grafite, diamant, Are they really pure? fulleren, amorfous , Different molecular structures (locations of ... pure For analysis Chemically pure C-nanotubes, graphene, ... atoms in space) Extra chemically pure substances Gr. allos , different tropos kind special – 99,999 % Si - number of 9s Jöns Jakob Berzelius 1779-1848, Swedish

11 Changes in the substances Chemical formulae Chemical change - reaction

Stochiometric (empirical, summary) Macroscopically: Microscopically: H2PO3 process of creation reorganisation of atoms in the space of new compounds Molecular H4P2O6 A + B → C + D (OH) OP-PO (OH) O Rational 2 2 reactants products A + B → C + D Structural chemical equilibrium

Chemical equations, mass balance, charge balance

Empirical laws Empirical laws Law of constant composition Law of multiple proportions (Law of definite proportions) (John Dalton – 1803) (Joseph Luis Proust – 1799, Francúz) (John Dalton – 1803, Angličan) If two elements form more than one compound between A always contains exactly the same them, then the ratios of the masses of the second proportion of elements by mass, irrespective of the way of element which combine with a fixed mass of the first preparation element will be ratios of small whole numbers. H2 + Cl2 → 2 HCl H:Cl = 2.76%:97.24% 3 H O + PCl → 3 HCl +H PO 2 3 3 3 Mn = 1 MnO, MnO2 daltonides bertholides – non-stochiometric O(MnO): O(MnO2)= 1:2 Claude Louis Berthollet 1748-1822 Francúz

12 Empirical laws Law of combining volumes (Joseph Luis Gay-Lussac – 1808, Francúz)

The ratio between the volumes of the reactant gases and the products can be expressed in simple whole numbers.

H2 + Cl2 → 2 HCl 1 l 1 l 2 l

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