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The Periodic Table of the Elements 1869~Dmitri Mendeleev 1944~Glenn Seaborg History of the Periodic Table • By 1860, more than 60 elements had been discovered. • Different chemists used different atomic masses for the same elements, resulting in different compositions being proposed for the SAME compounds. How could one chemist understand the results of another? • In September 1860, the 1st International Congress of Chemists was held to address these issues. They agreed on standard values for atomic masses. Mendeleev’s Periodic Table • When the Russian chemist Dmitri Mendeleev heard about the Congress, he decided to include the new values for atomic masses in a textbook he was writing. • His idea was to organize the elements by their chemical and physical PROPERTIES as well as their atomic masses. • Chemical properties included their “combining capacity” with other elements, especially with oxygen and chlorine. Physical properties included melting and boiling points. Mendeleev’s Periodic Table • Mendeleev noticed that when the elements were organized by increasing atomic mass, certain similarities in their chemical properties occurred at regular intervals. Such repeating patterns are referred to as PERIODIC. • Mendeleev created a table in which elements with similar properties were grouped together—the first Periodic Table of the Elements. Predictions for Undiscovered Elements • Mendeleev’s procedure left several empty spaces in his table. In 1871, he predicted the existence and properties of three of these elements. • By 1886, these three elements—Gallium, Germanium, and Scandium—had been Predicting Properties • Mendeleev used the average of properties of elements just above and below an unknown element to predict its properties. • Germanium was unknown, but the density of silicon is 2.3 g/cm3 and tin’s density is 7.3 g/cm3. • What would you estimate germanium’s density to be? When germanium was discovered in 1886, its density was found to be 5.3 g/cm3, about 10% different than the prediction of 4.8 g/cm3! Predicting Properties • Formulas for chemical compounds can also be predicted. We know that carbon and oxygen form carbon dioxide (CO2). What formula would you predict for a compound of carbon and sulfur? Since oxygen and sulfur are in the same group (16), we can predict that the compound would be carbon disulfide (CS2). Your turn! 1. Krypton (Kr) wasn’t known in Mendeleev’s time. Given that the boiling point of argon (Ar) is -186°C and of xenon (Xe) is -108°C, estimate the boiling point of Kr. 2. The melting points of potassium and cesium (Cs) are 337 K and 302 K respectively. (a) Estimate the melting point of rubidium (Rb). (b) Do you expect the melting point of sodium to be higher or lower than that of rubidium? Explain the evidence you used for your prediction. Solutions 1. The estimated BP of krypton would be halfway between that of argon and xenon, or -147°C. (The actual value is -153°C.) 2. (a) The estimated MP of rubidium would be 320 K. (Actual is 312 K.) (b) I would predict the MP of sodium to be higher than that of rubidium as MP decreases as you go down the group, and sodium is higher than rubidium in the group. Mendeleev’s Principle of Chemical Periodicity • Mendeleev’s successful predictions persuaded most chemists to accept his periodic table; however, not all elements could be arranged in order of ATOMIC MASS. • In 1911(40 years later) Henry Moseley’s work on atomic spectra led to the discovery that the elements fit the pattern of increasing ATOMIC NUMBER better than atomic mass. The Periodic Law • The Periodic Law today is known as: The physical and chemical properties of the elements are periodic functions of their atomic numbers. In other words, when the elements are arranged in order of increasing atomic number, elements with similar properties appear at regular intervals. Periodic Variation in Properties • Horizontal rows are called PERIODS • Vertical columns are called GROUPS or FAMILIES. The elements in each group have similar properties. ALKALI METALS—1st column; highly reactive— form ECl chlorides and E2O oxides ALKALINE EARTH—2nd column TRANSITION METALS—3rd through 12th column HALOGEN—17th column (2nd from right); readily form 1- anions NOBLE GASES—18th column (far right column); very unreactive Valence Electrons • VALENCE ELECTRONS are those electrons of an atom which are in outer shells and are available to form chemical bonds. • For a main group element, a valence electron can only be in the outermost electron shell. • In a transition metal, a valence electron can also be in an inner shell. Valence Electrons for Main Period Groups • For Groups 1, 2, 13 through 18, it is easy to identify the number of valence electrons for each group. Valence Electrons for Transition Metals • A valence electron for a transition metal is defined as an electron that resides outside a noble-gas core, which can be in an inner or outer shell. • The energies of electrons in the d sublevels are comparable to the s sublevel of the next highest main level (3d and 4s, 4d and 5s), so an element’s possible valence electrons are any outside the noble gas core. Also, the further right in each series, the lower the energy of an electron in a d subshell and the less such an electron has the properties of a valence electron. • So, the number of valence electrons for transition metals is hard to predict! Metals, Metalloids, Nonmetals Metals Metalloids Nonmetals Types of Elements • As you can see, the Periodic Table is broadly divided into two main types of elements, METALS and NONMETALS with a few metalloids in between. • Where are metals located on the periodic table? • Where are nonmetals located? Properties of Metals, Non-metals, and Metalloids • Metals have LUSTER (are shiny), are MALLEABLE (capable of being shaped or stretched without shattering), and conduct ELECTRICITY well. • Nonmetals are usually DULL in appearance, are BRITTLE, and NONCONDUCTING. • Metalloids have intermediate properties of both metals and nonmetals. Silicon and germanium are examples and are used extensively in computers. What determines properties? • Mostly it is the number and arrangement of the atom’s electrons. • Also, metal atoms lose electrons more readily than nonmetal atoms do. • Stronger attractions among the atoms of metals going from left to right in the Periodic Table means their boiling points increase. What do you notice now about the abrupt change in BP and MP for Period 2 and 3 elements? Metals are dark blue, metalloids are lavender, and non-metals are aqua. Atomic Bonding • Most elements do not exist in their ‘pure’ form but combine with other elements to form substances with properties different from the elements themselves. • A compound is a substance that consists of two or more elements that are chemically combined in specific proportions. • Compounds are formed when atoms combine with others by gaining, losing, or sharing electrons, a process called chemical bonding. Types of Chemical Bonds • Ionic bonds form between positive and negative ions. An ion is an atom that has an electrical charge through transferral (loss or gain) of electrons. Types of Chemical Bonds • Covalent bonds form when atoms share electrons. A molecule is the smallest part of a covalent compound that has the properties of that compound. Water and many atmospheric gases such as carbon dioxide are molecules with covalent bonds. Types of Chemical Bonds • Metallic bonds form by sharing a sea of "free" electrons among a lattice of positively charged ions. Properties of Bonds • Ionic compounds are rigid solids with high melting and boiling points. When solid, they are poor conductors of electricity, but when melted are good conductors. Most are Groups 1 and 2 reacting with Groups 16 and 17. • Covalent compounds have low melting and boiling points and have poor electrical conductivity even when melted. • Metallic compounds are malleable (easily shaped), ductile (easily drawn into wires), and are excellent electrical conductors. PBS Learning Media Ionic bonding Covalent bonding Trends in the Periodic Table Electronegativity Electronegativity Trend in Atomic Radius • As you go from left to right across a period, the atomic radius (distance from nucleus to outermost electron) tends to decrease. As the positive charge in the nucleus increases, the electrostatic attraction on the electrons also increases, pulling them inward. Remember that as you go across a period, you stay at the same energy level. • The atomic radius usually increases while going down a group due to the addition of a new energy level (shell)—the outermost electrons are farther from the nucleus. Metallic Character Reactivity • Character = how much like a metal it behaves; reactivity = how easily it loses (or gains) electrons to form chemical bonds • As you go across a period from left to right, the nuclear charge increases while the number of energy levels stays the same, so there is a stronger and stronger attraction for the electrons. It becomes more and more difficult to lose electrons, so the reactivity of metals decreases as you go from left to right across the periodic table. Metallic Character Reactivity • As you go down a group, the nuclear charge increases but so does the number of shielding electrons. This means we have more and more energy levels and the electrons are further and further away from the nucleus, and it is easier for those electrons to come off. • So going down a group means a metal’s reactivity INCREASES. Ionization Energy The energy needed to remove one • or more electrons from a neutral atom to form a positively charged ion is a physical property that influences the chemical behavior of the atom. The first ionization energy of an element is the energy needed to remove the outermost, or highest energy, electron from a neutral atom in the gas phase. Ionization Energy • Ionization energy tends to increase across a period because the greater number of protons (higher nuclear charge) attracts the orbiting electrons more strongly, thereby increasing the energy required to remove one of the electrons. • Down a group, the ionization energy will likely decrease since the valence electrons are farther away from the nucleus and experience a weaker attraction to the nucleus' positive charge. Second, Third, etc. Ionization Energies • It will ALWAYS take more energy to remove a second electron from an ion than it does to remove the first (outermost) electron from a neutral atom. Similarly for third, fourth, etc. e• Can it take so much energy to that removing an electron is unlikely? Consider this: First, Second, Third, and Fourth Ionization Energies of Sodium, Magnesium, and Aluminum (kJ/mol) Electron Affinity • If ionization energy measures the tendency of a neutral atom to RESIST the loss of an electron, electron affinity measures the tendency of a neutral atom to GAIN an electron. • It requires energy to remove an electron, but energy is given off when an electron is gained (except for Be, N, and noble gases which are very stable and require energy to accept another electron!). • Electron affinities are generally smaller than ionization energies for reasons we’ll skip for now. Electron Affinity Trends • Going across the Periodic Table from left to right, electron affinities of the main group elements tend to INCREASE. • Going down a group, electron affinities tend to DECREASE (increase bottom to top). • The trends are the same as ionization energies. Electronegativity The tendency of an atom to attract pairs of electrons towards itself for bonding. An atom's electronegativity is affected by both its atomic number and the distance that its valence electrons reside from the charged nucleus. Electronegativity and Bonding • The difference in electronegativity between two elements determines the type of bonding that occurs between the elements. • If the difference is large, the bond will be IONIC. • If the difference is small, the bond will be COVALENT. Electronegativity • Moving left to right across a period, electronegativity increases due to the stronger attraction for electrons as the nuclear charge increases. • Moving down a group, electronegativity decreases due to the longer distance between the nucleus and the valence electron shell, reducing the attraction for electrons. Melting and Boiling Point Trends Down a Group What is the trend in BP? In MP? Why do you suppose is the cause for these trends? Melting and Boiling Point Trends Across Periods 2 and 3 Quick check Discuss these with a partner and answer: 1. Identify which trend in the diagram below describes atomic radius: a) b) Increases Increases Increases Increases c) Increases Increases Quick check 2. Identify which trends below in the diagram identifies ionization energy, electron affinity, and electronegativity: Increases Increases Increases Increases Increases Increases • Why don’t boiling point and melting point follow a simple trend across a period? • The answer lies in the type of BONDS that elements form with other elements to make chemical compounds. • One of the trends you did note was an element’s METALLIC CHARACTER REACTIVITY. While we will learn about a metal’s reactivity later, now is a good time to learn about METALS, METALLOIDS and NON-METALS.