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Applied Chemistery-I Session 2009-10 , UET Lahore Period Classification of elements on the basis of structure of atoms The periodiс table of the chemical elements (also Mendeleev's table, periodic table of the elements or just periodic table) is a tabular display of the chemical elements. Although precursors to this table exist, its invention is generally credited to Russian chemist Dmitri Mendeleev in 1869, who intended the table to illustrate recurring ("periodic") trends in the properties of the elements. The layout of the table has been refined and extended over time, as new elements have been discovered, and new theoretical models have been developed to explain chemical behavior. The periodic table is now ubiquitous within the academic discipline of chemistry, providing an extremely useful framework to classify, systematize, and compare all of the many different forms of chemical behavior. The table has found wide application in chemistry, physics, biology, and engineering, especially chemical engineering. The current standard table contains 117 elements as of July 2009 (elements 1–116 and element 118). Structure of the periodic table Group 1 # Period 1 1 H 3 2 Li 11 N 3 a 4 5 6 7 2 3 5 6 7 8 9 10 11 12 13 14 15 16 17 18 8 O 9 F 2 He 10 Ne 13 14 15 16 Al Si P S 17 Cl 18 Ar 27 28 29 30 31 32 33 34 Co Ni Cu Zn Ga Ge As Se 35 Br 36 Kr 45 46 47 48 49 50 51 52 Rh Pd Ag Cd In Sn Sb Te 53 54 I Xe 4 Be 12 M g 5 B 25 19 20 21 22 23 24 26 M K Ca Sc Ti V Cr Fe n 37 42 38 39 40 41 43 44 R M Sr Y Zr Nb Tc Ru b o 55 56 * 72 73 74 75 76 Cs Ba Hf Ta W Re Os 77 78 79 80 81 Ir Pt Au Hg Tl 11 10 10 10 10 10 10 11 11 112 87 88 ** 3 4 5 6 7 8 9 0 1 Uu Fr Ra Uu Rf Db Sg Bh Hs Mt Ds Rg b t 57 La 89 ** Actinoids A c * Lanthanoids 1 4 58 59 60 61 62 63 64 Ce Pr Nd Pm Sm Eu Gd 95 96 90 91 92 93 94 A C Th Pa U Np Pu m m 6 C 7 N 82 83 84 Pb Bi Po 85 At (117 114 115 116 ) Uu Uu Uu (Uus q p h ) 65 66 67 68 69 70 71 Tb Dy Ho Er Tm Yb Lu 97 98 99 100 101 102 103 Bk Cf Es Fm Md No Lr Hasan Qayyum Chohan , Reg. No. 2009-CH-204 Chemical Engineering UET Lahore 86 Rn 118 Uu o Applied Chemistery-I Session 2009-10 , UET Lahore This common arrangement of the periodic table separates the lanthanoids and actinoids from other elements. The wide periodic table incorporates the f-block. The extended periodic table adds the 8th and 9th periods, incorporating the f-block and adding the theoretical g-block. Element categories in the periodic table Metals Alkali metals Nonmetals Inner transition Alkaline Transition Other Metalloids Other Noble Unknown elements earth Halogens elements metals nonmetals gases metals Lanthanoids Actinoids Borders show natural occurrence Atomic number colors show state at standard temperature and pressure (0 °C and 1 atm) Solids Liquids Gases Unknown Primordial From decay Synthetic (Undiscovered) Other alternative periodic tables exist:Some versions of the table show a dark stair-step line along the metalloids. Metals are to the left of the line and non-metals to the right. The layout of the periodic table demonstrates recurring ("periodic") chemical properties. Elements are listed in order of increasing atomic number (i.e., the number of protons in the atomic nucleus). Rows are arranged so that elements with similar properties fall into the same columns (groups or families). According to quantum mechanical theories of electron configuration within atoms, each row (period) in the table corresponded to the filling of a quantum shell of electrons. There are progressively longer periods further down the table, grouping the elements into s-, p-, d- and f-blocks to reflect their electron configuration.In printed tables, each element is usually listed with its element symbol and atomic number; many versions of the table also list the element's atomic mass and other information, such as its abbreviated electron configuration, electronegativity and most common valence numbers.As of 2006, the table contains 117 chemical elements whose discoveries have been confirmed. Ninety-four are found naturally on Earth, and the rest are synthetic elements that have been produced artificially in particle accelerators. Elements 43 (technetium), 61 (promethium) and all elements greater than 83 (bismuth), beginning with 84 (polonium) have no stable isotopes. The atomic mass of each of these element's isotope having the longest half-life is typically reported on periodic tables with parentheses. Isotopes of elements 43, 61, 93 (neptunium) and 94 (plutonium), first discovered synthetically, have since been discovered in trace amounts on Earth as products of natural radioactive decay processes.The primary determinant of an element's chemical properties is its electron configuration, particularly the valence shell electrons. For instance, any atoms with four valence electrons occupying p orbitals will exhibit some similarity. The type of orbital in which the atom's outermost electrons reside determines the "block" to which it belongs. The number of valence shell electrons determines the family, or group, to which the element belongs.The total number of electron shells an atom has determines the period to which it belongs. Each shell is divided into different subshells, which as atomic number increases are filled in roughly this order (the Aufbau principle): Subshell: S G F D P Period 2 1 1s 2 2s 2p Hasan Qayyum Chohan , Reg. No. 2009-CH-204 Chemical Engineering UET Lahore Applied Chemistery-I Session 2009-10 , UET Lahore 3 3s 3p 4 4s 3d 4p 5 5s 4d 5p 6 6s 4f 5d 6p 7 7s 5f 6d 7p 8 8s 5g 6f 7d 8p Hence the structure of the table. Since the outermost electrons determine chemical properties, those with the same number of valence electrons are grouped together. Progressing through a group from lightest element to heaviest element, the outer-shell electrons (those most readily accessible for participation in chemical reactions) are all in the same type of orbital, with a similar shape, but with increasingly higher energy and average distance from the nucleus. For instance, the outer-shell (or "valence") electrons of the first group, headed by hydrogen, all have one electron in an s orbital. In hydrogen, that s orbital is in the lowest possible energy state of any atom, the first-shell orbital (and represented by hydrogen's position in the first period of the table). In francium, the heaviest element of the group, the outer-shell electron is in the seventh-shell orbital, significantly further out on average from the nucleus than those electrons filling all the shells below it in energy. As another example, both carbon and lead have four electrons in their outer shell orbitals. Note that as atomic number (i.e., charge on the atomic nucleus) increases, this leads to greater spinorbit coupling between the nucleus and the electrons, reducing the validity of the quantum mechanical orbital approximation model, which considers each atomic orbital as a separate entity. The elements ununbium, ununtrium, ununquadium, etc. are elements that have been discovered, but so far have not received a trivial name yet. There is a system for naming them temporarily. Classification Groups Main article: Group (periodic table) A group or family is a vertical column in the periodic table. Groups are considered the most important method of classifying the elements. In some groups, the elements have very similar properties and exhibit a clear trend in properties down the group. These groups tend to be given trivial (unsystematic) names, e.g., the alkali metals, alkaline earth metals, halogens, pnictogens, chalcogens, and noble gases. Some other groups in the periodic table display fewer similarities and/or vertical trends (for example Group 14), and these have no trivial names and are referred to simply by their group numbers Periods Main article: Period (periodic table) A period is a horizontal row in the periodic table. Although groups are the most common way of classifying elements, there are some regions of the periodic table where the horizontal trends and similarities in properties are more significant than vertical group trends. This can be true in the d-block (or "transition metals"), and especially for the f-block, where the lanthanoids and actinoids form two substantial horizontal series of elements. Blocks Main article: Periodic table block 3 Hasan Qayyum Chohan , Reg. No. 2009-CH-204 Chemical Engineering UET Lahore Applied Chemistery-I Session 2009-10 , UET Lahore Because of the importance of the outermost shell, the different regions of the periodic table are sometimes referred to as periodic table blocks, named according to the subshell in which the "last" electron resides. The s-block comprises the first two groups (alkali metals and alkaline earth metals) as well as hydrogen and helium. The p-block comprises the last six groups (groups 13 through 18) and contains, among others, all of the semimetals. The d-block comprises groups 3 through 12 and contains all of the transition metals. The f-block, usually offset below the rest of the periodic table, comprises the rare earth metals. Other The chemical elements are also grouped together in other ways. Some of these groupings are often illustrated on the periodic table, such as transition metals, poor metals, and metalloids. Other informal groupings exist, such as the platinum group and the noble metals. Periodicity of chemical properties The main value of the periodic table is the ability to predict the chemical properties of an element based on its location on the table. It should be noted that the properties vary differently when moving vertically along the columns of the table than when moving horizontally along the rows. Periodic trends of groups Modern quantum mechanical theories of atomic structure explain group trends by proposing that elements within the same group have the same electron configurations in their valence shell, which is the most important factor in accounting for their similar properties. Elements in the same group also show patterns in their atomic radius, ionization energy, and electronegativity. From top to bottom in a group, the atomic radii of the elements increase. Since there are more filled energy levels, valence electrons are found farther from the nucleus. From the top, each successive element has a lower ionization energy because it is easier to remove an electron since the atoms are less tightly bound. Similarly, a group will also see a top to bottom decrease in electronegativity due to an increasing distance between valence electrons and the nucleus. Periodic trends of periods Periodic trend for ionization energy. Each period begins at a minimum for the alkali metals, and ends at a maximum for the noble gases. Elements in the same period show trends in atomic radius, ionization energy, electron affinity, and electronegativity. Moving left to right across a period, atomic radius usually decreases. This occurs because each successive element has an added proton and electron which causes the electron to be drawn closer to the nucleus. This decrease in atomic radius also causes the ionization energy to increase when moving from left to right across a period. The more tightly bound an element is, the more energy is required to remove an electron. Similarly, electronegativity will increase in the same manner as ionization energy because of the amount of pull that is exerted on the electrons by the nucleus. Electron affinity also shows a slight trend across a period. Metals (left side of a period) 4 Hasan Qayyum Chohan , Reg. No. 2009-CH-204 Chemical Engineering UET Lahore Applied Chemistery-I Session 2009-10 , UET Lahore generally have a lower electron affinity than nonmetals (right side of a period) with the exception of the noble gases. History Main article: History of the periodic table In 1789, Antoine Lavoisier published a list of 33 chemical elements. Although Lavoisier grouped the elements into gases, metals, non-metals, and earths, chemists spent the following century searching for a more precise classification scheme. In 1829, Johann Wolfgang Döbereiner observed that many of the elements could be grouped into triads (groups of three) based on their chemical properties. Lithium, sodium, and potassium, for example, were grouped together as being soft, reactive metals. Döbereiner also observed that, when arranged by atomic weight, the second member of each triad was roughly the average of the first and the third. This became known as the Law of triads.[citation needed] German chemist Leopold Gmelin worked with this system, and by 1843 he had identified ten triads, three groups of four, and one group of five. Jean Baptiste Dumas published work in 1857 describing relationships between various groups of metals. Although various chemists were able to identify relationships between small groups of elements, they had yet to build one scheme that encompassed them all. German chemist August Kekulé had observed in 1858 that carbon has a tendency to bond with other elements in a ratio of one to four. Methane, for example, has one carbon atom and four hydrogen atoms. This concept eventually became known as valency. In 1864, fellow German chemist Julius Lothar Meyer published a table of the 49 known elements arranged by valency. The table revealed that elements with similar properties often shared the same valency. English chemist John Newlands published a series of papers in 1864 and 1865 that described his attempt at classifying the elements: When listed in order of increasing atomic weight, similar physical and chemical properties recurred at intervals of eight, which he likened to the octaves of music. This law of octaves, however, was ridiculed by his contemporaries. Portrait of Dmitri Mendeleev Russian chemistry professor Dmitri Ivanovich Mendeleev and Julius Lothar Meyer independently published their periodic tables in 1869 and 1870, respectively. They both constructed their tables in a similar manner: by listing the elements in a row or column in order of atomic weight and starting a new row or column when the characteristics of the elements began to repeat. The success of Mendeleev's table came from two decisions he made: The first was to leave gaps in the table when it seemed that the corresponding element had not yet been discovered. Mendeleev was not the first chemist to do so, but he went a step further by using the trends in his periodic table to predict the properties of those missing elements, such as gallium and germanium. The second decision was to occasionally ignore the order suggested by the atomic weights and switch adjacent elements, such as cobalt and nickel, to better classify them into chemical families. With the development of theories of atomic structure, it became apparent that Mendeleev had inadvertently listed the elements in order of increasing atomic number. 5 Hasan Qayyum Chohan , Reg. No. 2009-CH-204 Chemical Engineering UET Lahore Applied Chemistery-I Session 2009-10 , UET Lahore With the development of modern quantum mechanical theories of electron configurations within atoms, it became apparent that each row (or period) in the table corresponded to the filling of a quantum shell of electrons. In Mendeleev's original table, each period was the same length. However, because larger atoms have more electron sub-shells, modern tables have progressively longer periods further down the table. In the years that followed after Mendeleev published his periodic table, the gaps he left were filled as chemists discovered more chemical elements. The last naturally-occurring element to be discovered was Francium (referred to by Mendeleev as eka-caesium) in 1939. The periodic table has also grown with the addition of synthetic and transuranic elements. The first transuranic element to be discovered was neptunium, which was formed by bombarding uranium with neutrons in a cyclotron in 1939. Quantum number Quantum numbers describe values of conserved quantities in the dynamics of the quantum system. Perhaps the most peculiar aspect of quantum mechanics is the quantization of observable quantities. This is distinguished from classical mechanics where the values can range continuously. They often describe specifically the energies of electrons in atoms, but other possibilities include angular momentum, spin etc. Since any quantum system can have one or more quantum numbers, it is a rigorous job to list all possible quantum numbers How many quantum numbers? The question of how many quantum numbers are needed to describe any given system has no universal answer, although for each system one must find the answer for a full analysis of the system. The dynamics of any quantum system are described by a quantum Hamiltonian, H. There is one quantum number of the system corresponding to the energy, i.e., the eigenvalue of the Hamiltonian. There is also one quantum number for each operator O that commutes with the Hamiltonian (i.e. satisfies the relation OH = HO). These are all the quantum numbers that the system can have. Note that the operators O defining the quantum numbers should be independent of each other. Often there is more than one way to choose a set of independent operators. Consequently, in different situations different sets of quantum numbers may be used for the description of the same system. These are conventionally known as The principal quantum number (n = 1, 2, 3, 4 ...) denotes the eigenvalue of H with the J2 part removed. This number therefore has a dependence only on the distance between the electron and the nucleus (ie, the radial coordinate, r). The average distance increases with n, and hence quantum states with different principal quantum numbers are said to belong to different shells. The azimuthal quantum number (l = 0, 1 ... n−1) (also known as the angular quantum number or orbital quantum number) gives the orbital angular momentum through the relation . In chemistry, this quantum number is very important, since it specifies the shape of an atomic orbital and strongly influences chemical bonds and bond angles. In some contexts, l=0 is called an s orbital, l=1, a p orbital, l=2, a d orbital and l=3, an f orbital. The magnetic quantum number (ml = −l, −l+1 ... 0 ... l−1, l) is the eigenvalue, This is the projection of the orbital angular momentum along a specified axis. . Results from spectroscopy indicated that up to two electrons can occupy a single orbital. However two electrons can never have the same exact quantum state nor the same set of quantum numbers according 6 Hasan Qayyum Chohan , Reg. No. 2009-CH-204 Chemical Engineering UET Lahore Applied Chemistery-I Session 2009-10 , UET Lahore to Hund's Rules, which addresses the Pauli exclusion principle. A fourth quantum number with two possible values was added as an ad hoc assumption to resolve the conflict; this supposition could later be explained in detail by relativistic quantum mechanics and from the results of the renowned Stern-Gerlach experiment. The spin projection quantum number (ms = −1/2 or +1/2), is the intrinsic angular momentum of the electron. This is the projection of the spin s=1/2 along the specified axis. To summarize, the quantum state of an electron is determined by its quantum numbers: name symbol orbital meaning principal quantum number shell azimuthal quantum number (angular momentum) subshell (s orbital is listed as 0, p orbital as 1 etc.) magnetic quantum number, (projection of angular momentum) energy shift (orientation of the subshell's shape) spin projection quantum number spin of the electron (-1/2 = counterclockwise, 1/2 = clockwise) range of values value example for : for : for an electron, either: Example: The quantum numbers used to refer to the outermost valence electron of the Carbon (C) atom, which is located in the 2p atomic orbital, are; n = 2 (group 2), l = 1 or 0, ml = 1, or 0, or −1, ms = −1/2 or 1/2. 7 Hasan Qayyum Chohan , Reg. No. 2009-CH-204 Chemical Engineering UET Lahore Applied Chemistery-I Session 2009-10 , UET Lahore Note that molecular orbitals require totally different quantum numbers, because the Hamiltonian and its symmetries are quite different. Quantum numbers with spin-orbit interaction For more details on this topic, see Clebsch-Gordan coefficients. When one takes the spin-orbit interaction into consideration, l, m and s no longer commute with the Hamiltonian, and their value therefore changes over time. Thus another set of quantum numbers should be used. This set includes The total angular momentum quantum number (j = 1/2,3/2 ... n−1/2) gives the total angular momentum through the relation . The projection of the total angular momentum along a specified axis (mj = -j,-j+1... j), which is analogous to m, and satisfies mj = ml + ms. Parity. This is the eigenvalue under reflection, and is positive (i.e. +1) for states which came from even l and negative (i.e. -1) for states which came from odd l. The former is also known as even parity and the latter as odd parity For example, consider the following eight states, defined by their quantum numbers: 1. 2. 3. 4. 5. 6. 7. 8. n = 2, l = 1, ml = 1, ms = +1/2 n = 2, l = 1, ml = 1, ms = -1/2 n = 2, l = 1, ml = 0, ms = +1/2 n = 2, l = 1, ml = 0, ms = -1/2 n = 2, l = 1, ml = -1, ms = +1/2 n = 2, l = 1, ml = -1, ms = -1/2 n = 2, l = 0, ml = 0, ms = +1/2 n = 2, l = 0, ml = 0, ms = -1/2 The quantum states in the system can be described as linear combination of these eight states. However, in the presence of spin-orbit interaction, if one wants to describe the same system by eight states which are eigenvectors of the Hamiltonian (i.e. each represents a state which does not mix with others over time), we should consider the following eight states: 8 j = 3/2, mj = 3/2, odd parity (coming from state (1) above) j = 3/2, mj = 1/2, odd parity (coming from states (2) and (3) above) j = 3/2, mj = -1/2, odd parity (coming from states (4) and (5) above) j = 3/2, mj = -3/2, odd parity (coming from state (6)) j = 1/2, mj = 1/2, odd parity (coming from states (2) and (3) above) j = 1/2, mj = -1/2, odd parity (coming from states (4) and (5) above) j = 1/2, mj = 1/2, even parity (coming from state (7) above) j = 1/2, mj = -1/2, even parity (coming from state (8) above) Hasan Qayyum Chohan , Reg. No. 2009-CH-204 Chemical Engineering UET Lahore