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Chapter 2 Atoms, Elements, Orbitals, and Electron Configurations 2.1 Atomic Theory • The last chapter dealt with chemistry on a large-scale or macroscopic level. • Now we need to look at matter on a sub-microscopic, or atomic level. Questions about the fundamental nature of matter can be traced as far back as the Greek philosophers. • Aristotle believed that matter could be divided indefinitely. • Democritus argued that there was a limit. John Dalton proposed atomic theory in 1808. − The work atom literally means "uncuttable." − All matter is composed of atoms. − The atoms of a given element differ from the atoms of all other elements. Chemical compounds consist of atoms combined in specific ratios. Law of Definite Proportions – atoms combine in whole number ratios to form compounds. Water is always H2O, not H2.1O or HO2 Law of Multiple Proportions – The same kinds of atoms can combine in more than one proportion. If you change the ratio, you change the compound. H2O is water but H2O2 is hydrogen peroxide Chemical reactions change the way that atoms are combined in compounds. The atoms themselves are unchanged. 2H2 + O2 2H2O Chapter 2 Page 1 of 19 The Make-up of an Atom Atoms are composed of tiny subatomic particles. (There are many more particles (e.g., ferions, bosons, etc. that have been identified, but these three still provide the core that is needed to understand most chemical properties and transitions.) The three fundamental subatomic particles are: 1. Protons – positively charged subatomic particles 2. Neutrons – electrically neutral subatomic particles 3. Electrons – negatively charged subatomic particles. Characteristics of Particles Particle Mass (g) Mass (amu)* -24 Proton (p) 1.67262 x 10 1.007276 amu -24 Neutron (n) 1.67493 x 10 1.008665 amu -28 Electron (e ) 9.10933 x 10 0.000549 amu -24 0.00091 x 10 *amu = atomic mass units to be explained later Charge +1 0 -1 Electrons are so much lighter that protons and neutrons that their mass is usually ignored when computing the mass of an atom. Atoms are extremely tiny. Atomic diameters range from: Hydrogen at 7.4 x 10-11 m to Cesium at 5.24 x 10-10 m Atomic mass values range from: Hydrogen at 1.67 x 10-24 g to Uranium at 3.95 x 10-22 g By comparison, a penny weighs 2.5 g Chapter 2 Page 2 of 19 What is an amu? The masses of subatomic particles are so small that they are hard to work with. • A relative scale was devised. • Since carbon is one of the most abundant elements and it is the basis for all living matter, the relative scale was based on carbon, C. • Carbon-12 (aka C-12), which has 6 protons and 6 neutrons in its nucleus, is the standard and is arbitrarily assigned the mass of 12amu. • All other element's masses are defined relative to C-12. 1 amu = 1.6605 x 10-24g (1/12 the mass of one C-12 atom) Problem: What is the mass, in grams, of a copper atom weighing 62.95 amu? 62.95 amu 1.6605 x10−24 g x = 1.045285 x10− 22 g ⇒ 1.045 x10− 22 g amu Problem: How many atoms are in 0.500g of sodium, Na, if each atom of sodium weights 23 amu? 0.500 g − x 1 amu 1 Na atom x = 1.309 x 10 22 ⇒ −24 1.6605 x 10 g 23.0 amu 1.31 x10 22 Na atoms − Problem: What is the mass in grams of 2.4x1013 helium atoms, each having a mass of 4.0 amu?? − 2.4 x1013 atoms 4.0 amu 1.6605 x 10 −24 g x x = 1.6 x 10 −10 g atom amu Chapter 2 Page 3 of 19 Arrangement of Subatomic Particles The arrangement of the particles is not random. − Nucleus- a dense core within the atom that contains the protons and neutrons (and therefore almost all of the mass). − Surrounding space – is mostly empty and contains the electrons. − If an atom was the size of a large domed stadium, the nucleus would only occupy a volume the size of a pea!!! Structure of the Atom • The structure of the atom is determined by interplay of different forces. • Opposite electrical charges attract each other. • Like charges repel each other. • The positively charged protons attract the negatively charged electrons. - This keeps them in the area around the nucleus. • Electron repel electrons – So they stay far away from each other. - This accounts for the large space they occupy. • Protons and neutrons in the nucleus are held together by the nuclear strong force . - This takes a lot of energy. Chapter 2 Page 4 of 19 2.2 Elements and Atomic Number • Atomic Number ( Z ) is the number of protons in atoms of a given element. – All atoms of a particular element have the same number of protons in the nucleus. – They will all have the same number of electrons , since the atom is neutral. – They may have different numbers of neutrons . - If so they are isotopes of each other. • Mass Number (A) is the sum of the protons plus neutrons in an atom. 2.3 Isotopes and Atomic Weight Isotopes Definition: Atoms (of the same element) with identical atomic numbers but different mass numbers. Representation: Mass number → AX Atomic number → Z ← Element symbol Z = atomic number = # of protons A = Z(# of protons) + N (# of neutrons) There are three isotopes of hydrogen: − 1 1 H protium 2 1 H deuterium or D Chapter 2 Page 5 of 19 3 1 H tritium or T Most isotopes do not have specific names the way those of hydrogen do. Isotopes are usually referred to by their mass number. For example: 235 92 U is referred to as uranium-235 or U-235. Problem: Which element has atomic number 17? (ANS: Cl) Problem: How many protons, neutron, and electrons are in the isotope with Z=13 and A=27? What is the element? a) # p = Z = 13 # e = Z = 13 (since it is neutral) # n = A – Z = 27 – 13 = 14 b) Element # 13 = Al Problem: How many neutrons are in U-238? (ANS: n=238-92=146) Problem: Complete each of the following isotope symbols: 11 5 ? = 11 5 B 56 ? Fe = 56 26 Fe Atomic Weight Naturally occurring elements are mixtures of isotopes. Atomic Mass values (aka atomic weights) listed for elements are the weighted average mass of an element’s atoms. • The individual masses of the naturally occurring isotopes and the percentage ( as a fractional abundance) of each must be known. Atomic weight = Σ[(isotope abundance) × (isotope mass)] The Greek symbol Σ indicates sum of terms Chapter 2 Page 6 of 19 Problem: Copper consists of only two isotopes with masses and abundances of 62.95 (70.5%) and 64.96 (??%). Calculate the atomic mass of Cu to the correct number of significant figures from the data. [ANS: see periodic chart. (63.5)] All percentages must add up to 100% so the other is 100-70.5=29.5% Cu (62.95*0.705) + (64.96*0.295) = 44.380 + 19.163 = 63.543 ⇒ 63.5 amu/atom 2.4 The Periodic Table History of The Periodic Table • Only 10 elements have been known since the beginning of recorded history. (Sb, C, Cu, Au, Fe, Pb, Hg, Ag, S, Sn) • By the American Revolution, 24 elements had been identified. • In the late 1700s and early 1800s, as more elements were discovered, chemists began to look for similarities among elements. • Dmitri Mendeleev organized elements by mass, then into columns based on chemical behavior. • Holes in the table predicted the discovery of new elements. Mendeleev’s 1871 Periodic Table There are over 110 elements currently identified. Chapter 2 Page 7 of 19 This is the periodic table in the front of your book. (Show on overhead.) This is the most current one that you can always download. I like the format better. Most Current Periodic Table from webelements.com This is the one we will be using in class. It has the format of webelements but the same atomic weights as your textbook. Chapter 2 Page 8 of 19 Using The Periodic Table Each box in the periodic Table gives us specific information about that element. − − Columns are called Groups of Families (elements in the same group exhibit similar chemical behavior) − Main Groups - The two groups on the far left ( 1 - 2 ) and the six on the far right ( 13 - 18 ). (These are often designated with an A.) − Transition Metal Groups - Elements in groups ( 3 – 12 ). − Inner Transition Metals— The 14 elements following lanthanum are the lanthanides , and the 14 elements following actinium are the actinides . − Rows are called Periods (Tell why) An example of a periodic property A graph of atomic radius versus atomic number shows a periodic riseand-fall pattern. The maxima occur for group 1A , elements, and the minima occur for group 7A elements. Problem: Identify the group 5 element in period 4 (ANS: V) Chapter 2 Page 9 of 19 2.5 Characteristics of Different Groups Periodic Table Groupings Handout Group I (1A) – Alkali Metals − Shiny, soft metals with low melting points. − Not found in nature as the free element (very reactive) − Form alkaline solutions in water Group 2 (2A) – Alkaline Earth Metals − Lusterous, silvery metals Show sodium and potassium in water movie. Reaction is: 2Na + 2H2O H2 + 2NaOH + heat (requires Quicktime) − Reactive (but less so than Group 1) − Not found in nature as the free element − Form alkaline solutions in water Group 17 (7A) - Halogens − Colorless and corrosive nonmetals − Only found in nature combined with metals (e.g. NaCl) − All except astatine (At) are diatomic They exist as pairs as pure elements; i.e. F2, Cl2, Br2, I2. (Note: 3 additional elements are diatomic: H2, N2, O2. Group 18 (8A) – Noble Gases − Colorless gases − Very unreactive (previously known as inert gases) (Groups 3-12) Transition Elements & (no group number) Lanthanide/Actinides Series − Transition elements are common − Lanthanides and Actinides are not common Chapter 2 Page 10 of 19 Zigzag Line The periodic table can be grouped into 3 categories: Metals, nonmetals, and metalloids (semimetals). Metals − Left side of the periodic table − Most elements are metals − They do not combine with each other; they combine with nonmetals − solid (except Hg) Nonmetals − Right side of periodic table (Far right column referred to as the noble gases[very non-reactive]; next group referred to as the halogens[very reactive]) − Seven are diatomic (come in pairs in nature) H2, N2, O2, F2, Cl2, Br2, I2 (Emphasize that they are only diatomic when they are the free element, not when they are combined with other elements.) − can be solids, liquids, or gasses Metalloids − Share some characteristics with both metals and non-metals. − Are near the zigzag line from Boron to Astatine (Metals to the left of the line, nonmetals to the right) Textbooks differ; Semimetals are B, Si, Ge, As, Sb, Te, (Sometimes astatine (At) and/or polonium (Po). We will consider all elements touching the line (except Al) as a semimetal. Chapter 2 Page 11 of 19 2.6 Electronic Structure of Atoms The properties of the elements are determined by the arrangement of electrons in their atoms. This arrangement is understood using the quantum mechanical model developed by Erwin Schrödinger. – (According to this theory), atoms are not completely free to move around the atom. • Each electron is restricted to specific probability regions that are known as orbitals. – The energy associated with each orbital is different • The energy that electrons can have is quantized (can only have discreet values) e.g., stairs are quantized, a ramp is not. – Electrons have both properties. particle - like and wave - like – The behavior of electrons can be described using an equation called a wave function. • The wave function also provide each electron with an “address” within an atom consisting of a shell, subshell, and orbital. Shells, Subshells, and Orbitals Orbitals are grouped into shells and subshells. Shells (aka Primary Quantum Number, n) Electrons are grouped in layers or shells around the nucleus. • The farther out from the nucleus, - the larger the shell - the more electrons it can hold, and - the higher the energy level of the electrons. Chapter 2 Page 12 of 19 Shell Numbering: • Shells are numbered with integers starting with 1. • A shell can have as many subshells as the shell value. Subshells Subshells “Numbering”: Subshells are lettered in order s, p, d, f Therefore: - Shell n=1 has 1 subshell (only an s subshell) - Shell n=2 has 2 subshells (s and p subshells) - Shell n=3 has 3 subshells (s, p, and d subshells) - Shell n=4 has 4 subshells (s, p, d and f subshells) Leave room for 3 more rows! Orbitals Each subshell contains a grouping of orbitals. s subshells can have 1 orbital d subshells can have 5 orbitals p subshells can have 3 orbitals f subshells can have 7 orbitals Each orbital can hold 2 electrons of opposite spin. Chapter 2 Page 13 of 19 Orbital Summary Problem: What is the maximum # of e- that can occupy the following subshells? The number does not affect the # of 3p? (6) 2s? (2) 2p? (6) e- a subshell can hold! Problem: What is the maximum # of electrons that can occupy the third shell? 3s(2) + 3p(6) + 3d(10) = 18 Problem: How many electrons are present in an atom in which the 1s, 2s, and 2p subsells are filled? Name the element. 1s(2) + 2s(2) + 2p(6) =10 e- ∴element = Ne Orbital Shapes Since orbitals are “probability regions”, they have shapes. s orbitals are spheres. p orbitals are dumbbells. 1 lobe 2 lobes Chapter 2 Page 14 of 19 The shapes of d (4 lobes per orbital) and f orbitals (8 lobes per orbital) are more complex. The shapes of f subshells are very complex. Usually 8 lobes Usually 4 lobes 2.7–2.8 Electronic Configurations and the Periodic Table The exact arrangement of electrons in an atom’s shells and subshells is the atom’s electron configuration. It can be predicted by applying 3 rules. The 3 Principles for Order of Filling Energy Levels • Rule 1: Always fill the lowest levels first. (Aufbau Principle) energy - This is complicated by “crossover” of energies above the 3p sublevel. - The energy diagram can be used to predict the order of filling, but there are easier ways! • Rule 2:Each orbital can hold a maximum of 2 electrons of opposite spin. (Pauli Exclusion Principle) • Rule 3: If you have orbitals of the same energy ( degenerate ), you fill 1 in each orbital before you double up. All unpaired e- all have the same spin. (Hund’s Rule) Chapter 2 Page 15 of 19 The periodic table provides a method for remembering the order of orbital filling. It can be divided into “blocks” elements according to the last subshell filled. Atomic Electron Configurations A summary of the orbital location of each electron is written as, for example: Mg 1s2 2s2 2p6 3s2 etc. Shell # Subshell Type The number of electrons in the subshell Chapter 2 Page 16 of 19 Problem: Determine the electron configuration and orbital box diagram for: V 1s2 2s2 2p6 3s2 3p6 4s2 3d3 OR [Ar] 4s2 3d3 often re-written with the OR [Ar] 3d3 4s2 This can be called valence___electrons last (outer shell) shortcut notation or a noble gas notation. Have class try: W [Xe] 6s2 4f14 5d4 ⇒ [Xe] 4f14 5d4 6s2 An alternate trick that can be used to determine the order or sublevel filling is: Chapter 2 Page 17 of 19 Problem: Determine the electron configuration for the following elements. Also show the orbital diagram for each. Determine the number of unpaired electrons. Al 1s22s22p63s23p1 ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ . 1s 2s 2p 3s V ONE UNPAIRED ELECTRON 1s22s22p63s23p64s23d3 ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑ ↑_ __ __ 1s 2s 2p 3s 3p 4s 3d THREE UNPAIRED ELECTRONS Problem: Determine the noble gas electron configuration for the following elements. Se 1s22s22p63s23p64s23d104p4 [Ar] 4s23d104p4 Sn 1s22s22p63s23p64s23d104p65s24d105p2 [Kr] 5s24d105p2 Bi 1s22s22p63s23p64s23d104p65s24d105p66s24f145d106p3 [Xe] 6s24f145d106p3 Chapter 2 Page 18 of 19 2.9 Electron Dot Symbols Since valence electrons are so important in the behavior of atoms, it is useful to be able to show them with the chemical symbol. Electron-dot symbol—An atomic symbol with dots placed around it to indicate the number of valence electrons. These are cartoons and do not imply actual shapes. Draw out row 1 on the board. Problem: Write the electron dot symbol for element X in group 5 (5A). Problem: Write the electron dot symbol for lead. Problem: Write the electron dot symbol for strontium. Chapter 2 Page 19 of 19