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The atom and isotopes
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CHEM 18 MODULE 1: ELECTRONIC STRUCTURE OF THE ATOM AND ATOMIC PROPERTIESIons Ions are charged substances that have formed through the gain or loss of electrons. Cations form from the loss of electrons and have a positive charge while anions form through the gain of electrons and have a negative charge. Cation Formation Cations are the positive ions formed by the loss of one or more electrons. The most commonly formed cations of the representative elements are those that involve the loss of all of the valence electrons. Consider the alkali metal sodium (Na) . It has one valence electron in the n=3 energy level. Upon losing that electron, the sodiu ion now has an octet of electrons from the second energy level and a charge of 1+ . The electron arrangement of the sodium ion is now the same as that of the noble gas neon. Consider a similar process with magnesium and aluminum. In this case, the magnesium atom loses its two valence electrons in order to achieve the same arrangement as the noble gas neon and a charge of 2+ . The aluminum atom loses its three valence electrons to have the same electron arrangement as neon and a charge of 3+ . For representative elements under typical conditions, three electrons is usually the maximum number that will be los. Representative elements will not lose electrons beyond their valence because they would have to "break" the octet of the previous energy level which provides stability to the ion. Anions Anions are the negative ions formed from the gain of one or more electrons. When nonmetal atoms gain elections, they often do so until their outermost principal energy level achieves an octet. For fluorine, which has an electron arrangement of (2, 7), it only needs to gain one electron to have the same electron arrangement as neon. Forming an octet (eight electrons in the outer shell) provides stability to the atom. Fluorine will gain one electron and have a charge of 1− . The electron arrangement of the fluoride ion (2, 8) will also change to reflect the gain of an electron. Oxygen has an electron arrangement of (2, 6) and needs to gain two electrons to fill the n=2 energy level and achieve an octet of electrons in the outermost shell. The oxide ion will have a charge of 2− as a result of gaining two electrons. Under typical conditions, three electrons is the maximum that will be gained in the formation of anions. Subatomic Particles in an Ion Since ions form from the gain or loss of electrons, we can also look at the number of subatomic particles (protons, neutrons, and electrons) found in an ion. Remember that the number of protons determines the identity of the element and will not change in a chemical process. Example 2.5.1 How many protons, neutrons, and electrons in a single oxide (O2−) ion? Solution Oxygen has the atomic number 8 so both the atom and the ion will have 8 protons. The average atomic mass of oxygen is 16. Therefore, there will be 8 neutrons (atomic mass−atomic number=neutrons) . A neutral oxygen atom would have 8 electrons. However, the anion has gained two electrons so O2− has 10 electrons. We can also use information about the subatomic particles to determine the identity of an ion. Example 2.5.2 An ion with a 2+ charge has 18 electrons. Determine the identity of the ion. Solution If an ion has a 2+ charge then it must have lost electrons to form the cation. If the ion has 18 electrons and the atom lost 2 to form the ion, then the neutral atom contained 20 electrons. Since it was neutral, it must also have had 20 protons. Therefore the element is calcium. Polyatomic Ions A polyatomic ion is an ion composed of two or more atoms that have a charge as a group (poly = many). The ammonium ion (see figure below) consists of one nitrogen atom and four hydrogen atoms. Together, they comprise a single ion with a 1+ charge and a formula of NH+4 . The hydroxide ion (see figure below) contains one hydrogen atom and one oxygen atom with an overall charge of 1− . The carbonate ion (see figure below) consists of one carbon atom and three oxygen atoms and carries an overall charge of 2− . The formula of the carbonate ion is CO2−3 . The atoms of a polyatomic ion are tightly bonded together and so the entire ion behaves as a single unit. The figures below show several examples. Soult Screenshot 2-2-1.png Figure 2.5.1 : The ammonium ion (NH+4) is a nitrogen atom (blue) bonded to four hydrogen atoms (white). Soult Screenshot 2-2-2.png Figure 2.5.2 : The hydroxide ion (OH−) is an oxygen atom (red) bonded to a hydrogen atom. Soult Screenshot 2-2-3.png Figure 2.5.3 : The carbonate ion (CO2−3) is a carbon atom (black) bonded to three oxygen atoms. The table below lists a number of polyatomic ions by name and by structure. The heading for each column indicates the charge on the polyatomic ions in that group. Note that the vast majority of the ions listed are anions - there are very few polyatomic cations. 1− 2− 3− 1+ Table 2.5.1 : Common Polyatomic Ions acetate, CH3COO− carbonate, CO2−3 arsenate, AsO3−3 ammonium, NH+4 bromate, BrO−3 chromate, CrO2−4 phosphite, PO3−3 chlorate, ClO−3 dichromate, Cr2O2−7 phosphate, PO3−4 chlorite, ClO−2 hydrogen phosphate, HPO2−4 cyanide, CN− oxalate, C2O2−4 dihydrogen phosphate, H2PO−4 peroxide, O2−2 hydrogen carbonate, HCO−3 silicate, SiO2−3 hydrogen sulfate, HSO−4 sulfate, SO2−4 hydrogen sulfide, HS− sulfite, SO2−3 hydroxide, OH− hypochlorite, ClO− nitrate, NO−3 nitrite, NO−2 perchlorate, ClO−4 permanganate, MnO−4 The vast majority of polyatomic ions are anions, many of which end in -ate or -ite. Notice that in some cases such as nitrate (NO−3) and nitrite (NO−2) , there are multiple anions that consist of the same two elements. In these cases, the difference between the ions is the number of oxygen atoms present, while the overall charge is the same. As a class, these are called oxyanions. When there are two oxyanions for a particular element, the one with the greater number of oxygen atoms gets the -ate suffix, while the one with the fewer number of oxygen atoms gets the -ite suffix. The four oxyanions of chlorine are shown below, which also includes the use of the prefixes hypo- and per-. ClO− , hypochlorite ClO−2 , chlorite ClO−3 , chlorate ClO−4 , perchlorate Not your usual ion Soult Screenshot 2-2-4.png "Drink you milk. It's good for your bones." We're told this from early childhood, and with good reason. Milk contains a good supply of calcium, part of the structure of bone. However, there are two other ionic components of hydroxyapatite, the mineral component. Phosphate ion and hydroxide ion make up the remainder of the inorganic material in bone. News You Can Use Bone is a very complex structure. It is composed of protein (mainly collagen), hydroxyapatite (a calcium-phosphate-hydroxide mixture), some other minerals, and contains 10 - 20% water. The calcium/phosphate ratios are not stoichiometric, but vary somewhat from one portion of bone to the next. Bones are very strong but will break under enough stress. Regular exercise and proper nutrition help to increase bone strength. Watch a video about bone structure at http://www.youtube.com/watch?v=d9owEvYdouk Nitrate is an anion with a complex bonding structure. Major sources for this ion in drinking water are runoff from fertilizer, septic tank leakage, sewage, and natural deposits. High concentrations of nitrates represent a significant health hazard, especially to infants. The nitrate in the body is converted to nitrite, which then binds to hemoglobin. This binding decreases the ability of hemoglobin to transport oxygen, thus depriving the cells of the O2 needed for proper functioning. Cyanide production is widespread throughout nature. Forest fires will produce significant amounts of cyanide. Many plants contain cyanide, and it is produced by a number of bacteria, algae, and fungi. Cyanide is used industrially in metal finishing, iron and steel mills, and in organic synthesis processes. This material is also an important component for the refining of precious metals. Formation of a complex between cyanide and gold allows extraction of this metal from a mixture.Covalent Molecules and Compounds Just as an atom is the simplest unit that has the fundamental chemical properties of an element, a molecule is the simplest unit that has the fundamental chemical properties of a covalent compound. Some pure elements exist as covalent molecules. Hydrogen, nitrogen, oxygen, and the halogens occur naturally as the diatomic (“two atoms”) molecules H2, N2, O2, F2, Cl2, Br2, and I2 (part (a) in Figure 3.1.1). Similarly, a few pure elements exist as polyatomic (“many atoms”) molecules, such as elemental phosphorus and sulfur, which occur as P4 and S8 (part (b) in Figure 3.1.1). Each covalent compound is represented by a molecular formula, which gives the atomic symbol for each component element, in a prescribed order, accompanied by a subscript indicating the number of atoms of that element in the molecule. The subscript is written only if the number of atoms is greater than 1. For example, water, with two hydrogen atoms and one oxygen atom per molecule, is written as H2O. Similarly, carbon dioxide, which contains one carbon atom and two oxygen atoms in each molecule, is written as CO2. Covalent compounds that predominantly contain carbon and hydrogen are called organic compounds. The convention for representing the formulas of organic compounds is to write carbon first, followed by hydrogen and then any other elements in alphabetical order (e.g., CH4O is methyl alcohol, a fuel). Compounds that consist primarily of elements other than carbon and hydrogen are called inorganic compounds; they include both covalent and ionic compounds. In inorganic compounds, the component elements are listed beginning with the one farthest to the left in the periodic table, as in CO2 or SF6. Those in the same group are listed beginning with the lower element and working up, as in ClF. By convention, however, when an inorganic compound contains both hydrogen and an element from groups 13–15, hydrogen is usually listed last in the formula. Examples are ammonia (NH3) and silane (SiH4). Compounds such as water, whose compositions were established long before this convention was adopted, are always written with hydrogen first: Water is always written as H2O, not OH2. The conventions for inorganic acids, such as hydrochloric acid (HCl) and sulfuric acid (H2SO4), are described elswhere. Note! For organic compounds: write C first, then H, and then the other elements in alphabetical order. For molecular inorganic compounds: start with the element at far left in the periodic table; list elements in same group beginning with the lower element and working up. Write the molecular formula of each compound. a. The phosphorus-sulfur compound that is responsible for the ignition of so-called strike anywhere matches has 4 phosphorus atoms and 3 sulfur atoms per molecule. b. Ethyl alcohol, the alcohol of alcoholic beverages, has 1 oxygen atom, 2 carbon atoms, and 6 hydrogen atoms per molecule. c. Freon-11, once widely used in automobile air conditioners and implicated in damage to the ozone layer, has 1 carbon atom, 3 chlorine atoms, and 1 fluorine atom per molecule. Solution: a. • A The molecule has 4 phosphorus atoms and 3 sulfur atoms. Because the compound does not contain mostly carbon and hydrogen, it is inorganic. • B Phosphorus is in group 15, and sulfur is in group 16. Because phosphorus is to the left of sulfur, it is written first. • C Writing the number of each kind of atom as a right-hand subscript gives P4S3 as the molecular formula. b. • A Ethyl alcohol contains predominantly carbon and hydrogen, so it is an organic compound. • B The formula for an organic compound is written with the number of carbon atoms first, the number of hydrogen atoms next, and the other atoms in alphabetical order: CHO. • C Adding subscripts gives the molecular formula C2H6O. c. • A Freon-11 contains carbon, chlorine, and fluorine. It can be viewed as either an inorganic compound or an organic compound (in which fluorine has replaced hydrogen). The formula for Freon-11 can therefore be written using either of the two conventions. • B According to the convention for inorganic compounds, carbon is written first because it is farther left in the periodic table. Fluorine and chlorine are in the same group, so they are listed beginning with the lower element and working up: CClF. Adding subscripts gives the molecular formula CCl3F. • C We obtain the same formula for Freon-11 using the convention for organic compounds. The number of carbon atoms is written first, followed by the number of hydrogen atoms (zero) and then the other elements in alphabetical order, also giving CCl3F. Write the molecular formula for each compound. a. Nitrous oxide, also called “laughing gas,” has 2 nitrogen atoms and 1 oxygen atom per molecule. Nitrous oxide is used as a mild anesthetic for minor surgery and as the propellant in cans of whipped cream. b. Sucrose, also known as cane sugar, has 12 carbon atoms, 11 oxygen atoms, and 22 hydrogen atoms. c. Sulfur hexafluoride, a gas used to pressurize “unpressurized” tennis balls and as a coolant in nuclear reactors, has 6 fluorine atoms and 1 sulfur atom per molecule. Answer: a. N2O b. C12H22O11 c. SF6. Ionic Compounds The substances described in the preceding discussion are composed of molecules that are electrically neutral; that is, the number of positively-charged protons in the nucleus is equal to the number of negatively-charged electrons. In contrast, ions are atoms or assemblies of atoms that have a net electrical charge. Ions that contain fewer electrons than protons have a net positive charge and are called cations. Conversely, ions that contain more electrons than protons have a net negative charge and are called anions. Ionic compounds contain both cations and anions in a ratio that results in no net electrical charge. Note! Ionic compounds contain both cations and anions in a ratio that results in zero electrical charge.An ionic compound that contains only two elements, one present as a cation and one as an anion, is called a binary ionic compound. One example is MgCl2, a coagulant used in the preparation of tofu from soybeans. For binary ionic compounds, the subscripts in the empirical formula can also be obtained by crossing charges: use the absolute value of the charge on one ion as the subscript for the other ion. This method is shown schematically as follows: Crossing charges. One method for obtaining subscripts in the empirical formula is by crossing charges. When crossing charges, it is sometimes necessary to reduce the subscripts to their simplest ratio to write the empirical formula. Consider, for example, the compound formed by Mg2+ and O2−. Using the absolute values of the charges on the ions as subscripts gives the formula Mg2O2:Polyatomic Ions Polyatomic ions are groups of atoms that bear net electrical charges, although the atoms in a polyatomic ion are held together by the same covalent bonds that hold atoms together in molecules. Just as there are many more kinds of molecules than simple elements, there are many more kinds of polyatomic ions than monatomic ions. Two examples of polyatomic cations are the ammonium (NH4+) and the methylammonium (CH3NH3+) ions. P. The method used to predict the empirical formulas for ionic compounds that contain monatomic ions can also be used for compounds that contain polyatomic ions. The overall charge on the cations must balance the overall charge on the anions in the formula unit. Thus, K+ and NO3− ions combine in a 1:1 ratio to form KNO3 (potassium nitrate or saltpeter), a major ingredient in black gunpowder. Similarly, Ca2+ and SO42− form CaSO4 (calcium sulfate), which combines with varying amounts of water to form gypsum and plaster of Paris. The polyatomic ions NH4+ and NO3− form NH4NO3 (ammonium nitrate), a widely used fertilizer and, in the wrong hands, an explosive. One example of a compound in which the ions have charges of different magnitudes is calcium phosphate, which is composed of Ca2+ and PO43− ions; it is a major component of bones. The compound is electrically neutral because the ions combine in a ratio of three Ca2+ ions [3(+2) = +6] for every two ions [2(−3) = −6], giving an empirical formula of Ca3(PO4)2; the parentheses around PO4 in the empirical formula indicate that it is a polyatomic ion. Writing the formula for calcium phosphate as Ca3P2O8 gives the correct number of each atom in the formula unit, but it obscures the fact that the compound contains readily identifiable PO43− ions.Summary • There are two fundamentally different kinds of chemical bonds (covalent and ionic) that cause substances to have very different properties. • The composition of a compound is represented by an empirical or molecular formula, each consisting of at least one formula unit.Contributors The atoms in chemical compounds are held together by attractive electrostatic interactions known as chemical bonds. Ionic compounds contain positively and negatively charged ions in a ratio that results in an overall charge of zero. The ions are held together in a regular spatial arrangement by electrostatic forces. Most covalent compounds consist of molecules, groups of atoms in which one or more pairs of electrons are shared by at least two atoms to form a covalent bond. The atoms in molecules are held together by the electrostatic attraction between the positively charged nuclei of the bonded atoms and the negatively charged electrons shared by the nuclei. The molecular formula of a covalent compound gives the types and numbers of atoms present. Compounds that contain predominantly carbon and hydrogen are called organic compounds, whereas compounds that consist primarily of elements other than carbon and hydrogen are inorganic compounds. Diatomic molecules contain two atoms, and polyatomic molecules contain more than two. A structural formula indicates the composition and approximate structure and shape of a molecule. Single bonds, double bonds, and triple bonds are covalent bonds in which one, two, and three pairs of electrons, respectively, are shared between two bonded atoms. Atoms or groups of atoms that possess a net electrical charge are called ions; they can have either a positive charge (cations) or a negative charge (anions). Ions can consist of one atom (monatomic ions) or several (polyatomic ions). The charges on monatomic ions of most main group elements can be predicted from the location of the element in the periodic table. Ionic compounds usually form hard crystalline solids with high melting points. Covalent molecular compounds, in contrast, consist of discrete molecules held together by weak intermolecular forces and can be gases, liquids, or solids at room temperature and pressure. An empirical formula gives the relative numbers of atoms of the elements in a compound, reduced to the lowest whole numbers. The formula unit is the absolute grouping represented by the empirical formula of a compound, either ionic or covalent. Empirical formulas are particularly useful for describing the composition of ionic compounds, which do not contain readily identifiable molecules. Some ionic compounds occur as hydrates, which contain specific ratios of loosely bound water molecules called waters of hydration.Structure of an ion and compare it to the atomScience Exam Parts of the Atom: The atom consists of a nucleus at its center, containing protons (positively charged) and neutrons (neutral), while electrons (negatively charged) orbit in electron shells around the nucleus. Atomic Number: The atomic number of an element is the number of protons in its nucleus. It defines the element and determines its place on the periodic table. Properties of Metals: Metals have properties like conductivity, malleability (can be flattened into sheets), and ductility (can be drawn into wires). Elements, Compounds, and Mixtures: Elements consist of only one type of atom. Compounds are made of two or more different elements chemically bonded. Mixtures are combinations of substances that are physically mixed but not chemically bonded. Homogeneous and Heterogeneous Mixtures: Homogeneous mixtures have a uniform composition (e.g., saltwater), while heterogeneous mixtures have different phases (e.g., oil and water). Changes of State: Changes like melting, evaporation, and condensation are examples of physical changes of state. Chemical and Physical Properties: Chemical properties describe how a substance can change to form a new substance, while physical properties are characteristics like color, texture, and state (solid, liquid, gas). Physical and Chemical Change: A physical change involves the appearance or state of matter, but the substance remains the same. A chemical change involves the formation of new substances. Chemical Equations: Chemical reactions can be represented with chemical equations that show reactants (what you start with) and products (what is formed). Chemical Formulas: Chemical formulas represent the composition of compounds. For example, NaHCO3 is sodium bicarbonate, consisting of one sodium (Na), one hydrogen (H), one carbon (C), and three oxygen (O) atoms. Energy: Types of Energy: Energy can be kinetic (related to motion), potential (stored energy), thermal (heat energy), electrical, chemical, and more. Units of Energy: Common units of energy include joules (J) and calories (cal). Law of Conservation of Energy: Energy cannot be created or destroyed, only transferred or transformed from one form to another. Energy Transfer and Transformation: Energy moves from one object to another, changing forms along the way. Useful and Waste Energy: Useful energy is what can be harnessed and used for a specific purpose. Waste energy is energy that is not used and is often lost. Energy Flow Diagrams: These diagrams show how energy is transferred or transformed within a system. Energy Efficiency: Efficiency is a measure of how much useful energy is obtained from a system. It can be calculated using the equation: Efficiency = (Useful Energy Output / Total Energy Input) x 100%. Fossil Fuels and Renewable Energy: Fossil fuels, like coal, oil, and natural gas, are non-renewable sources of energy. Renewable energy sources include solar, wind, and hydroelectric power. Variables: Independent Variable: The variable that is manipulated or changed in an experiment. Dependent Variable: The variable that is measured or observed and is affected by changes in the independent variable. Controlled Variables: Factors that are kept constant to ensure a fair and accurate experiment.Short Quiz in Science 9 explain how the Quantum Mechanical Model of the atom describes the energies and positions of the electronsUnderstanding Quantum Theory of Electrons in Atoms The goal of this section is to understand the electron orbitals (location of electrons in atoms), their different energies, and other properties. The use of quantum theory provides the best understanding to these topics. This knowledge is a precursor to chemical bonding. As was described previously, electrons in atoms can exist only on discrete energy levels but not between them. It is said that the energy of an electron in an atom is quantized, that is, it can be equal only to certain specific values and can jump from one energy level to another but not transition smoothly or stay between these levels. The energy levels are labeled with an n value, where n = 1, 2, 3, …. Generally speaking, the energy of an electron in an atom is greater for greater values of n. This number, n, is referred to as the principal quantum number. The principal quantum number defines the location of the energy level. It is essentially the same concept as the n in the Bohr atom description. Another name for the principal quantum number is the shell number. The shells of an atom can be thought of concentric circles radiating out from the nucleus. The electrons that belong to a specific shell are most likely to be found within the corresponding circular area. The further we proceed from the nucleus, the higher the shell number, and so the higher the energy level (Figure 9.4.1). The positively charged protons in the nucleus stabilize the electronic orbitals by electrostatic attraction between the positive charges of the protons and the negative charges of the electrons. So the further away the electron is from the nucleus, the greater the energy it has. This quantum mechanical model for where electrons reside in an atom can be used to look at electronic transitions, the events when an electron moves from one energy level to another. If the transition is to a higher energy level, energy is absorbed, and the energy change has a positive value. To obtain the amount of energy necessary for the transition to a higher energy level, a photon is absorbed by the atom. A transition to a lower energy level involves a release of energy, and the energy change is negative. This process is accompanied by emission of a photon by the atom. The following equation summarizes these relationships and is based on the hydrogen atom: The values nf and ni are the final and initial energy states of the electron. The principal quantum number is one of three quantum numbers used to characterize an orbital. An atomic orbital, which is distinct from an orbit, is a general region in an atom within which an electron is most probable to reside. The quantum mechanical model specifies the probability of finding an electron in the three-dimensional space around the nucleus and is based on solutions of the Schrödinger equation. In addition, the principal quantum number defines the energy of an electron in a hydrogen or hydrogen-like atom or an ion (an atom or an ion with only one electron) and the general region in which discrete energy levels of electrons in a multi-electron atoms and ions are located. Another quantum number is l, the angular momentum quantum number. It is an integer that defines the shape of the orbital, and takes on the values, l = 0, 1, 2, …, n – 1. This means that an orbital with n = 1 can have only one value of l, l = 0, whereas n = 2 permits l = 0 and l = 1, and so on. The principal quantum number defines the general size and energy of the orbital. The l value specifies the shape of the orbital. Orbitals with the same value of l form a subshell. In addition, the greater the angular momentum quantum number, the greater is the angular momentum of an electron at this orbital. Orbitals with l = 0 are called s orbitals (or the s subshells). The value l = 1 corresponds to the p orbitals. For a given n, p orbitals constitute a p subshell (e.g., 3p if n = 3). The orbitals with l = 2 are called the d orbitals, followed by the f-, g-, and h-orbitals for l = 3, 4, 5, and there are higher values we will not consider. There are certain distances from the nucleus at which the probability density of finding an electron located at a particular orbital is zero. In other words, the value of the wavefunction ψ is zero at this distance for this orbital. Such a value of radius r is called a radial node. The number of radial nodes in an orbital is n – l – 1. Consider the examples in Figure 9.4.2. The orbitals depicted are of the s type, thus l = 0 for all of them. It can be seen from the graphs of the probability densities that there are 1 – 0 – 1 = 0 places where the density is zero (nodes) for 1s (n = 1), 2 – 0 – 1 = 1 node for 2s, and 3 – 0 – 1 = 2 nodes for the 3s orbitals. The s subshell electron density distribution is spherical and the p subshell has a dumbbell shape. The d and f orbitals are more complex. These shapes represent the three-dimensional regions within which the electron is likely to be found. Principal quantum number (n) & Orbital angular momentum (l): The Orbital Subshell: https://youtu.be/ms7WR149fAY If an electron has an angular momentum (l ≠ 0), then this vector can point in different directions. In addition, the z component of the angular momentum can have more than one value. This means that if a magnetic field is applied in the z direction, orbitals with different values of the z component of the angular momentum will have different energies resulting from interacting with the field. The magnetic quantum number, called ml, specifies the z component of the angular momentum for a particular orbital. For example, for an s orbital, l = 0, and the only value of ml is zero. For p orbitals, l = 1, and ml can be equal to –1, 0, or +1. Generally speaking, ml can be equal to –l, –(l – 1), …, –1, 0, +1, …, (l – 1), l. The total number of possible orbitals with the same value of l (a subshell) is 2l + 1. Thus, there is one s-orbital for ml = 0, there are three p-orbitals for ml = 1, five d-orbitals for ml = 2, seven f-orbitals for ml = 3, and so forth. The principal quantum number defines the general value of the electronic energy. The angular momentum quantum number determines the shape of the orbital. And the magnetic quantum number specifies orientation of the orbital in space, as can be seen in Figure 9.4.3. Figure 9.4.4 illustrates the energy levels for various orbitals. The number before the orbital name (such as 2s, 3p, and so forth) stands for the principal quantum number, n. The letter in the orbital name defines the subshell with a specific angular momentum quantum number l = 0 for s orbitals, 1 for p orbitals, 2 for d orbitals. Finally, there are more than one possible orbitals for l ≥ 1, each corresponding to a specific value of ml. In the case of a hydrogen atom or a one-electron ion (such as He+, Li2+, and so on), energies of all the orbitals with the same n are the same. This is called a degeneracy, and the energy levels for the same principal quantum number, n, are called degenerate energy levels. However, in atoms with more than one electron, this degeneracy is eliminated by the electron–electron interactions, and orbitals that belong to different subshells have different energies. Orbitals within the same subshell (for example ns, np, nd, nf, such as 2p, 3s) are still degenerate and have the same energy. While the three quantum numbers discussed in the previous paragraphs work well for describing electron orbitals, some experiments showed that they were not sufficient to explain all observed results. It was demonstrated in the 1920s that when hydrogen-line spectra are examined at extremely high resolution, some lines are actually not single peaks but, rather, pairs of closely spaced lines. This is the so-called fine structure of the spectrum, and it implies that there are additional small differences in energies of electrons even when they are located in the same orbital. These observations led Samuel Goudsmit and George Uhlenbeck to propose that electrons have a fourth quantum number. They called this the spin quantum number, or ms. The other three quantum numbers, n, l, and ml, are properties of specific atomic orbitals that also define in what part of the space an electron is most likely to be located. Orbitals are a result of solving the Schrödinger equation for electrons in atoms. The electron spin is a different kind of property. It is a completely quantum phenomenon with no analogues in the classical realm. In addition, it cannot be derived from solving the Schrödinger equation and is not related to the normal spatial coordinates (such as the Cartesian x, y, and z). Electron spin describes an intrinsic electron “rotation” or “spinning.” Each electron acts as a tiny magnet or a tiny rotating object with an angular momentum, even though this rotation cannot be observed in terms of the spatial coordinates. The magnitude of the overall electron spin can only have one value, and an electron can only “spin” in one of two quantized states. One is termed the α state, with the z component of the spin being in the positive direction of the z axis. This corresponds to the spin quantum number ms=12. The other is called the β state, with the z component of the spin being negative and ms=−12. Any electron, regardless of the atomic orbital it is located in, can only have one of those two values of the spin quantum number. The energies of electrons having ms=−12 and ms=12 are different if an external magnetic field is applied. Figure 9.4.5 illustrates this phenomenon. An electron acts like a tiny magnet. Its moment is directed up (in the positive direction of the z axis) for the 12 spin quantum number and down (in the negative z direction) for the spin quantum number of −12. A magnet has a lower energy if its magnetic moment is aligned with the external magnetic field (the left electron) and a higher energy for the magnetic moment being opposite to the applied field. This is why an electron with ms=12 has a slightly lower energy in an external field in the positive z direction, and an electron with ms=−12 has a slightly higher energy in the same field. This is true even for an electron occupying the same orbital in an atom. A spectral line corresponding to a transition for electrons from the same orbital but with different spin quantum numbers has two possible values of energy; thus, the line in the spectrum will show a fine structure splitting. The Pauli Exclusion Principle An electron in an atom is completely described by four quantum numbers: n, l, ml, and ms. The first three quantum numbers define the orbital and the fourth quantum number describes the intrinsic electron property called spin. An Austrian physicist Wolfgang Pauli formulated a general principle that gives the last piece of information that we need to understand the general behavior of electrons in atoms. The Pauli exclusion principle can be formulated as follows: No two electrons in the same atom can have exactly the same set of all the four quantum numbers. What this means is that electrons can share the same orbital (the same set of the quantum numbers n, l, and ml), but only if their spin quantum numbers ms have different values. Since the spin quantum number can only have two values (±12), no more than two electrons can occupy the same orbital (and if two electrons are located in the same orbital, they must have opposite spins). Therefore, any atomic orbital can be populated by only zero, one, or two electrons. The properties and meaning of the quantum numbers of electrons in atoms are brieflyWhat do an ancient Greek philosopher and a 19th century Quaker have in common with Nobel Prize-winning scientists? Although they are separated over 2,400 years of history, each of them contributed to answering the eternal question: what is stuff made of? It was around 440 BCE that Democritus first proposed that everything in the world was made up of tiny particles surrounded by empty space. And he even speculated that they vary in size and shape depending on the substance they compose. He called these particles "atomos," Greek for indivisible. His ideas were opposed by the more popular philosophers of his day. Aristotle, for instance, disagreed completely, stating instead that matter was made of four elements: earth, wind, water and fire, and most later scientists followed suit. Atoms would remain all but forgotten until 1808, when a Quaker teacher named John Dalton sought to challenge Aristotelian theory. Whereas Democritus's atomism had been purely theoretical, Dalton showed that common substances always broke down into the same elements in the same proportions. He concluded that the various compounds were combinations of atoms of different elements, each of a particular size and mass that could neither be created nor destroyed. Though he received many honors for his work, as a Quaker, Dalton lived modestly until the end of his days. Atomic theory was now accepted by the scientific community, but the next major advancement would not come until nearly a century later with the physicist J.J. Thompson's 1897 discovery of the electron. In what we might call the chocolate chip cookie model of the atom, he showed atoms as uniformly packed spheres of positive matter filled with negatively charged electrons. Thompson won a Nobel Prize in 1906 for his electron discovery, but his model of the atom didn't stick around long. This was because he happened to have some pretty smart students, including a certain Ernest Rutherford, who would become known as the father of the nuclear age. While studying the effects of X-rays on gases, Rutherford decided to investigate atoms more closely by shooting small, positively charged alpha particles at a sheet of gold foil. Under Thompson's model, the atom's thinly dispersed positive charge would not be enough to deflect the particles in any one place. The effect would have been like a bunch of tennis balls punching through a thin paper screen. But while most of the particles did pass through, some bounced right back, suggesting that the foil was more like a thick net with a very large mesh. Rutherford concluded that atoms consisted largely of empty space with just a few electrons, while most of the mass was concentrated in the center, which he termed the nucleus. The alpha particles passed through the gaps but bounced back from the dense, positively charged nucleus. But the atomic theory wasn't complete just yet. In 1913, another of Thompson's students by the name of Niels Bohr expanded on Rutherford's nuclear model. Drawing on earlier work by Max Planck and Albert Einstein he stipulated that electrons orbit the nucleus at fixed energies and distances, able to jump from one level to another, but not to exist in the space between. Bohr's planetary model took center stage, but soon, it too encountered some complications. Experiments had shown that rather than simply being discrete particles, electrons simultaneously behaved like waves, not being confined to a particular point in space. And in formulating his famous uncertainty principle, Werner Heisenberg showed it was impossible to determine both the exact position and speed of electrons as they moved around an atom. The idea that electrons cannot be pinpointed but exist within a range of possible locations gave rise to the current quantum model of the atom, a fascinating theory with a whole new set of complexities whose implications have yet to be fully grasped. Even though our understanding of atoms keeps changing, the basic fact of atoms remains, so let's celebrate the triumph of atomic theory with some fireworks. As electrons circling an atom shift between energy levels, they absorb or release energy in the form of specific wavelengths of light, resulting in all the marvelous colors we see. And we can imagine Democritus watching from somewhere, satisfied that over two millennia later, he turned out to have been right all along.