Fundamentals of Chemistry Lesson 1 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Prof. Roberto Paolesse Dept. of Chemical Science and Technologies University of Rome "Tor Vergata" Via della Ricerca Scientifica 00133 Rome, Italy Phone: 39.06.72594752 Fax: 39.06.72594328 e-mail: roberto.paolesse@uniroma2.it 2 Textbook: Raymond Chang: General Chemistry: the essential concepts 6th edition ; ISBN 0071313680 McGraw-Hill Ed. 3 The Study of Chemistry Macroscopic Microscopic 4 The scientific method is a systematic approach to research A hypothesis is a tentative explanation for a set of observations tested modified 5 A law is a concise statement of a relationship between phenomena that is always the same under the same conditions. Force = mass x acceleration A theory is a unifying principle that explains a body of facts and/or those laws that are based on them. Atomic Theory 6 Chemistry is the study of matter and the changes it undergoes Matter is anything that occupies space and has mass. A substance is a form of matter that has a definite composition and distinct properties. liquid nitrogen gold ingots silicon crystals 7 A mixture is a combination of two or more substances in which the substances retain their distinct identities. 1. Homogenous mixture – composition of the mixture is the same throughout. soft drink, milk, solder 2. Heterogeneous mixture – composition is not uniform throughout. cement, iron filings in sand 8 Physical means can be used to separate a mixture into its pure components. magnet distillation 9 An element is a substance that cannot be separated into simpler substances by chemical means. • 117 elements have been identified • 82 elements occur naturally on Earth gold, aluminum, lead, oxygen, carbon, sulfur • 35 elements have been created by scientists technetium, americium, seaborgium 10 11 A compound is a substance composed of atoms of two or more elements chemically united in fixed proportions. Compounds can only be separated into their pure components (elements) by chemical means. lithium fluoride quartz dry ice – carbon dioxide 12 Classifications of Matter 13 Dalton s Atomic Theory (1808) 1. Elements are composed of extremely small particles called atoms. 2. All atoms of a given element are identical, having the same size, mass and chemical properties. The atoms of one element are different from the atoms of all other elements. 3. Compounds are composed of atoms of more than one element. In any compound, the ratio of the numbers of atoms of any two of the elements present is either an integer or a simple fraction. 4. A chemical reaction involves only the separation, combination, or rearrangement of atoms; it does not result in their creation or destruction. 14 16 X + 8Y 8 X2Y Law of Conservation of Mass 15 Cathode Ray Tube J.J. Thomson, measured mass/charge of e(1906 Nobel Prize in Physics) 16 Cathode Ray Tube 17 Millikan s Experiment Measured mass of e(1923 Nobel Prize in Physics) e- charge = -1.60 x 10-19 C Thomson s charge/mass of e- = -1.76 x 108 C/g e- mass = 9.10 x 10-28 g18 Types of Radioactivity (uranium compound) 19 Thomson s Model 20 Rutherford s Experiment (1908 Nobel Prize in Chemistry) α particle velocity ~ 1.4 x 107 m/s (~5% speed of light) 1. atoms positive charge is concentrated in the nucleus 2. proton (p) has opposite (+) charge of electron (-) 3. mass of p is 1840 x mass of e- (1.67 x 10-24 g) 21 Rutherford s Model of the Atom atomic radius ~ 100 pm = 1 x 10-10 m nuclear radius ~ 5 x 10-3 pm = 5 x 10-15 m If the atom is the Houston Astrodome, then the nucleus is a marble on the 50yard line. 22 Chadwick s Experiment (1932) (1935 Noble Prize in Physics) H atoms - 1 p; He atoms - 2 p mass He/mass H should = 2 measured mass He/mass H = 4 α + 9Be 1n + 12C + energy neutron (n) is neutral (charge = 0) n mass ~ p mass = 1.67 x 10-24 g 23 mass p ≈ mass n ≈ 1840 x mass e24 Properties of Waves Wavelength (λ) is the distance between identical points on successive waves. Amplitude is the vertical distance from the midline of a wave to the peak or trough. Frequency (ν) is the number of waves that pass through a particular point in 1 second (Hz = 1 cycle/s). The speed (u) of the wave = λ x ν 25 Maxwell (1873), proposed that visible light consists of electromagnetic waves. Electromagnetic radiation is the emission and transmission of energy in the form of electromagnetic waves. Speed of light (c) in vacuum = 3.00 x 108 m/s All electromagnetic radiation λ x ν = c 26 27 Mystery #1, Heated Solids Problem Solved by Planck in 1900 When solids are heated, they emit electromagnetic radiation over a wide range of wavelengths. Radiant energy emitted by an object at a certain temperature depends on its wavelength. Energy (light) is emitted or absorbed in discrete units (quantum). E = h x ν Planck s constant (h) h = 6.63 x 10-34 J•s 28 Mystery #2, Photoelectric Effect Solved by Einstein in 1905 Light has both: 1. wave nature 2. particle nature hν KE e- Photon is a particle of light hν = KE + W KE = hν - W where W is the work function and depends how strongly electrons are held in the metal 29 Line Emission Spectrum of Hydrogen Atoms 30 Il modello di Bohr Bohr s Model of the Atom (1913) 1. e- can only have specific (quantized) energy values 2. light is emitted as emoves from one energy level to a lower energy level En = -RH ( 1 n2 ) n (principal quantum number) = 1,2,3,… RH (Rydberg constant) = 2.18 x 10-18J 32 E = hν E = hν 37 Ephoton = ΔE = Ef - Ei ni = 3 ni = 3 ni = 2 nf = 2 1 Ef = -RH ( 2 nf 1 Ei = -RH ( 2 ni 1 ΔE = RH( 2 ni ) ) 1 n2f nnf f==11 38 ) 40 Why is e- energy quantized? De Broglie (1924) reasoned that e- is both particle and wave. 2πr = nλ h λ = mu u = velocity of em = mass of e42 43 44 Schrodinger Wave Equation In 1926 Schrodinger wrote an equation that described both the particle and wave nature of the eWave function (ψ) describes: 1 . energy of e- with a given ψ 2 . probability of finding e- in a volume of space Schrodinger s equation can only be solved exactly for the hydrogen atom. Must approximate its solution for multi-electron systems. 45 46 Schrodinger Wave Equation ψ is a function of four numbers called quantum numbers (n, l, ml, ms) principal quantum number n n = 1, 2, 3, 4, …. distance of e- from the nucleus n=1 n=2 n=3 47 Where 90% of the e- density is found for the 1s orbital 48 Schrodinger Wave Equation quantum numbers: (n, l, ml, ms) angular momentum quantum number l for a given value of n, l = 0, 1, 2, 3, … n-1 n = 1, l = 0 n = 2, l = 0 or 1 n = 3, l = 0, 1, or 2 l=0 l=1 l=2 l=3 s orbital p orbital d orbital f orbital Shape of the volume of space that the e- occupies 49 l = 0 (s orbitals) l = 1 (p orbitals) 50 l = 2 (d orbitals) 51 Schrodinger Wave Equation quantum numbers: (n, l, ml, ms) magnetic quantum number ml for a given value of l ml = -l, …., 0, …. +l if l = 1 (p orbital), ml = -1, 0, or 1 if l = 2 (d orbital), ml = -2, -1, 0, 1, or 2 orientation of the orbital in space 52 ml = -1, 0, or 1 3 orientations is space 53 ml = -2, -1, 0, 1, or 2 5 orientations is space 54 Schrodinger Wave Equation (n, l, ml, ms) spin quantum number ms ms = +½ or -½ ms = +½ ms = -½ 55 Schrodinger Wave Equation quantum numbers: (n, l, ml, ms) Existence (and energy) of electron in atom is described by its unique wave function ψ. Pauli exclusion principle - no two electrons in an atom can have the same four quantum numbers. Each seat is uniquely identified (E, R12, S8) Each seat can hold only one individual at a time 56 57 58 Schrodinger Wave Equation quantum numbers: (n, l, ml, ms) Shell – electrons with the same value of n Subshell – electrons with the same values of n and l Orbital – electrons with the same values of n, l, and ml How many electrons can an orbital hold? If n, l, and ml are fixed, then ms = ½ or - ½ ψ = (n, l, ml, ½) or ψ = (n, l, ml, -½) An orbital can hold 2 electrons 59 How many 2p orbitals are there in an atom? n=2 2p If l = 1, then ml = -1, 0, or +1 3 orbitals l=1 How many electrons can be placed in the 3d subshell? n=3 3d l=2 If l = 2, then ml = -2, -1, 0, +1, or +2 5 orbitals which can hold a total of 10 e60 Energy of orbitals in a single electron atom Energy only depends on principal quantum number n n=3 n=2 En = -RH ( 1 n2 ) n=1 61 Energy of orbitals in a multi-electron atom Energy depends on n and l n=3 l = 2 n=3 l = 0 n=2 l = 0 n=3 l = 1 n=2 l = 1 n=1 l = 0 62 63 Fill up electrons in lowest energy orbitals (Aufbau principle) ?? B 1s22s22p1 B 5 electrons Be 1s22s2 Be 4 electrons Li 1s22s1 Li 3 electrons H 1 electron He 2 electrons He 1s2 H 1s1 64 The most stable arrangement of electrons in subshells is the one with the greatest number of parallel spins (Hund s rule). 65 Order of orbitals (filling) in multi-electron atom 1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s 66 Electron configuration is how the electrons are distributed among the various atomic orbitals in an atom. number of electrons in the orbital or subshell 1s1 principal quantum number n angular momentum quantum number l Orbital diagram H 1s1 67 What is the electron configuration of Mg? Mg 12 electrons 1s < 2s < 2p < 3s < 3p < 4s 1s22s22p63s2 2 + 2 + 6 + 2 = 12 electrons Abbreviated as [Ne]3s2 [Ne] 1s22s22p6 What are the possible quantum numbers for the last (outermost) electron in Cl? Cl 17 electrons 1s22s22p63s23p5 1s < 2s < 2p < 3s < 3p < 4s 2 + 2 + 6 + 2 + 5 = 17 electrons Last electron added to 3p orbital n=3 l=1 ml = -1, 0, or +1 ms = ½ or -½ 68 69 70 71 72 73 Outermost subshell being filled with electrons 74 75 Paramagnetic unpaired electrons 2p Diamagnetic all electrons paired 2p 76