TIFIFIFIFIIFAFIFIDIITIIIVITDIDIVIFIIIIIIIIIVGVG999 Chapter 2 IFanybody says he can think about quantum theory without ‘i getting giddy, it merely shows that he hasn't understood the Atomic Theory 3a Niels Bohr (1885-1962) Topics Covered: 2.1 Atomic Structure 2.1 Atomic Structure ‘2.2 The Periodic Table and Periodic Trends ELECTROMAGNETIC WAVES Electromagnetic waves are oscillations of an electromagnetic field that propagate through space at the speed of light, = 299.792. 458 ms = 3 x 10% ms (in vacuum) Light, X-rays, radio signals, etc., are all different forms of electromagnetic waves. Simple periodic waves are characterized by wavelength (A) or frequency (Vv). The wavelength refers to the distance between two closest equivalent points of the wave (Figure 2.1.1). Wavelengths are usually expressed in units of length (e.g. nanometers; 1 nm = 10° m). The frequency refers to the number of oscillation cycles chat occur at a fixed point in one second. The unit of frequency is s* or Hertz (abbreviated Hz).CHAPTER 2 ATOMIC THEORY 2-2 j____Wavelengh a arene Dtacon ‘A. Longer wavelength, lower frequency Wavelength ee bre Digcton 1. Shorter wavelength, higher frequency Figure 2.1.1 Characteristics of waves. A simple periodic wave propagating along an axis can be described by a sine function. A sine wave has alternating phases (denoted by + and -) above and be- low the axis. Another important characteristic of a wave is its amplitude (¥). The amplitude is the “height” of a wave (Figure 2.1.2). The square of the amplitude gives the wave's intensity. PIDIDIZIZIFZIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIGDITFFIIFIITFFIFTIVIITIIIIIVIIIFIVIITIIIGGIIFIGG9 CHAPTER 2 ATOMIC THEORY 23 ‘Wavelength, loner amplitude (ono {ieee Figure 2.1.2 Relationship between wave amplitude and light intensity, Frequency and wavelength of an electromagnetic wave are related to each other through the formula a where cis the speed of light. The longer the wavelength, the lower the frequency. The shorter the wavelength, the higher the frequency. If the wavelength is short, more waves pass by a fixed point in one second (higher frequency). If the wave- length is long, fewer waves pass by a fixed point in one second (lower frequency). Electromagnetic Spectrum The electromagnetic spectrum is the term used to describe the complete range of wavelengths (frequencies) of electromagnetic radiation. The wavelength (fre- quency) is the only characteristic that distinguishes one form of electromagnetic radiation from another, and the boundaries between different regions are arbitrary and somewhat fuzzy (Figure 2.1.3).CHAPTER 2» ATOMIC THEORY 24 Gammareys t Reco = le Ura 1 infrared vols Ht Wavelength (m) 10% 10" 1 TO" 10+ isle Spectrum 400 450 500550600 G50 -700750rm yiaveongh Wy [\_ {VP Lf Ay 4 * Figure 2.1.3 The electromagnetic spectrum. Most of the wavelengths in the electromagnetic spectrum are invisible to the human eye. In fact, our eyes are only able to detect electromagnetic radiation with wavelengths between 400-750 nm. This region is appropriately called the visible region or the visible spectrum. The wavelengths of light in the visible region correspond to a continuum of colours ranging from violet to red, in the order of the colours of the rainbow. DIVDIZFJIIIIFIIIIIIIFIIIIIIIIIIIIIIIIIIIIIIIIIIGDITDFIFIFIIIFIITDIFTIIFIIIIITIIITIFTIIIIIIIITIGGO99 CHAPTER 2 ATOMIC THEORY 25 Energy of Light A beam of light consists of a large number of tiny packets of energy called pho- tons. Each photon carries a fixed amount of energy that is related to the photon’s frequency V and wavelength d by the relations a be E=w=4 where h is a constant known as the Planck constant, bb = 6.6260696 x 10° J-s According to the above equation, the shorter the wavelength of light, the greater the energy possessed by its photons. Conversely, the longer the wavelengch, the lower the energy. Each photon of light can behave as a particle with a kinetic energy equal to E = by. When atoms and molecules interact with light, they can absorb and emit only whole photons, When a photon of frequency V is absorbed by a system (an atom or a molecule}, the energy of the system increases by E = hv. When a photon is ‘emitted, the system loses the energy E = bv. ‘The “take home” message of this section is that: (a) light is a stream of photons that can behave as waves or as particles; (b) energy of light can be absorbed or emitted only as small discrete portions (energies of individual photons); (c) the energy of each photon is determined by its frequency (or wavelength).CHAPTER 2» ATOMIC THEORY 26 EMISSION SPECTRUM OF ATOMIC HYDROGEN In the mid-19ch century, physicists discovered that when H, gasis placed in a tube and excited with a high-voltage electric discharge, H, molecules dissociate into excited H atoms and the atoms emit light with certain wavelengths (in nm): 410, 434, 486, 656, .... forming a series of spectral lines (Figure 2.1.4). This series of spectral lines is known today as the Balmer series, after the Swiss scientist Johann, Balmer who studied ic in the 1880s. Violet Blue-green High Votiage| 1 1 so | aes | 434 656 Wavelength (nm) Figure 2.1.4 Emission spectrum of hydrogen atoms. Several years after Balmer, Harvard University physicist Theodore Lyman discov- ‘ered that electrically excited hydrogen atoms emit nar only visible light, bur also ultraviolet light (ultraviolet light is outside of the visible spectrum, so it cannot be seen with the human eye). He detected discrete wavelengths at 97, 102, 122, nm, These wavelengths are known today as the Lyman series. Often, one scientific discovery leads to another. The German physicist Friedrich Paschen soon discovered that electrically excited hydrogen atoms also emit infrared light. As in the case of visible and ulteaviolet light, only discrete wavelengths of infrared light are observed. The discrete wavelengths of infrared light emitted by hydrogen atoms are known today as the Paschen series. Although the observed wavelengths in the Balmer, Lyman, and Paschen series may appear random, they are all governed by one mathematical formula. This formula was devised in 1888 by Johannes Rydberg, Rydberg found that all wave- lengths of light emitted by excited H atoms could be exactly predicted by using, the following equation: DIVDIDIDZIFIIZIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIGDIFFTFFIVDIITIFIFITIFIIITIIIFIIITIFIIIFIIITVGG9 CHAPTER 2 ATOMIC THEORY 27 where mand m are integers (2 1, >) and Ry, = nowadays referred to as the Rydberg constant. 10973731.6 nr" isa constant, When 1 =1 and mt = 2, 3, .. the Rydberg formula gives all wavelengths of the Lyman series; for n = 2 and m= 3, 4,..., it gives the Balmer series; for m= 3 and m= 4, 5,..., the Paschen series, and so on. This was an exciting discovery, but it did not explain why hydrogen atoms emitted light only with certain wavelengths. The whole matter remained a mystery until 1913 when the Danish physicist Niels Bohr proposed a theory that explained the emission spectrum of H atoms and allowed Bohr to derive the Rydberg formula. THE BOHR MODEL OF THE HYDROGEN ATOM Based on data from the emission spectra, Bohr proposed that the electron in the hydrogen arom moves about the nucleus in a circular orbit, much like how planets orbit the sun. Bohr also postulated that only certain orbits are possible, so that the energy of the electron in each orbit is “quantized.” Bohr assigned each orbit (energy level) an integer index = 1, 2, 3, .., uch that the orbit with = 1 is the closest to the nucleus (see Figure 2.1.5). Under these assumptions, Bohr showed that when the electron is in the nth orbit, its energy is given by R ad E,= [As increases, the energy difference between the consecutive levels decreases.CHAPTER 2 ATOMIC THEORY 2-8 Excitation of a ground state electron ‘Transition rom a higher to a lower energy Figure 2.1.5 Bohr’s model of the hydrogen atom. Bohr thus explained hydrogen atom’s emission spectrum as follows. Normally, hydrogen’s electron occupies the orbit of lowest energy (rt = 1). This n = 1 state is known as the ground state. The electron can absorb energy of the electric discharge and go up to one of the higher energy levels (7), resulting in an excited state. The excited state is unstable, and when the electron returns to a lower energy level, the difference in energy is emitted in the form of light with wavelength 4 that exactly corresponds to the energy difference between the two levels involved, ie he z, rea oe = After division by be, the last equation results in the Rydberg formula. Since the sample contains many hydrogen atoms in different excited states, many discrete wavelengths of light are emitted simultaneously, giving rise to the unique emission ae As shown in Figure 2.1.5, the Lyman, Balmer, and Paschen emission series are due to transitions from a higher energy level labeled by m to a lower level labeled by nz 1,2, and n = 3, respectively. PIDIFDIDFIZIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIISIDFFFFFIAVIFDIAFDIIITIVIFIFIFIFIIIVIFIVIVIGIFIGIGSD CHAPTER 2 © ATOMIC THEORY 29 Although the Bohr model was successful in explaining the positions of the lines in the emission spectrum of hydrogen, it had serious drawbacks: + The Bohr model did not explain «When the H emission spectrum was how the electron can remain in the enlarged and scrutinized, it turned lowest-energy orbit (m= 1) without out that each line actually consist- ever falling on the nucleus. Nor did ed of two closely spaced lines (see it explain why only certain orbits Figure 2.1.6). This splitting did not are allowed. follow from Bohr's model. t 656.3 nm Figure 2.1.6 Fine splitting in the hydrogen atom emission spectrum. + The Bohr model did not work for atoms with more than one electron (e.g. He). ‘These and other deficiencies of the Bohr model meant that the concept of electrons circling the nucleus in fixed orbits was not the correct way to describe the atomic structure. The difficulties of the Bohr model were resolved by a new theory— quantum (or wave) mechanics, which emerged in the 1920s, THE QUANTUM-MECHANICAL MODEL Icrurns out that the correct theory of atoms, molecules, and solids requires treating electrons not as tiny point-like particle orbiting the nucleus but as waves. In order to understand the meaning and implications of this idea, we need to examine the bchavior of wave in greater detail Diffraction and Interference of Waves Consider a wave approaching a small slit in a barrier (here, “small” means that the wideh of the slit is comparable to the wavelength). As the wave passes through the slit, it expands to fill all space on the other side of the barrier. This phenomenon is called diffraction (Figure 2.1.7).CHAPTER 2 ATOMIC THEORY 2-10 Figure 2.1.7 Diffraction of waves. Waves also interact with each other via a process known as “interference.” This interaction occurs in two different ways. Constructive interference occurs when two interacting waves are “in phase” (the ‘maxima and minima are aligned). The result is a wave with an amplitude that is the sum of the amplitudes of the two waves. Destructive interference occurs when two interacting waves are in opposite phases, (maxima of one wave are aligned with minima of the other). The result is a wave with zero amplitude—in other words, the two waves cancel each other. - appr = NM ® MAP fy i Figure 2.1.8 Constructive and destructive interference, 933333133333333333333333333333333333333333333DTTFFTFFIFIFVIFTFAVIFAFIAGIFIFIVITFIFIIIITIIIIIFIFIIIGIGVG CHAPTER 2 ATOMIC THEORY 211 The Two-Slit Experiment Consider a beam of light approaching a screen with two closely spaced slits, (Figure 2.1.9). After passing through the slits, secondary light waves propagate all directions from each slit (diffraction) and produce an “interference pattern” — an alternation of bright and dark bands, which are the results of constructive and destructive interference, respectively. Ze Waves in phase: bright banal Waves out of phace: arktend rasta wee Side View Front view of film vontwees ay Figure 2.1.9 The two-slit experiment. Ifthe beam of light is replaced with a stream of particles, the two-slit experiment produces only two bright bands but no interference pattern. Therefore, the dou- bble-slit experiment can be used to distinguish particles from waves. De Broglie Waves and Particle-Wave Duality In 1924, the French physicist Louis de Broglie put forward a radical hypothesis that, since light waves can behave as particles, then perhaps particles shouldJ ) CHAPTER 2 ATOMIC THEORY 2-12 behave like waves. In particular, he suggested that electrons might exhibit wave~ like behavior in addition to their well-known particle-like properties. After careful analysis, De Broglie proposed an equation relating mass (7) and velocity (v) of a particle to its wavelength: ate Because the Planck constant b is very small, both the mass and the velocity must also be very small in order for the wavelength to be measureable. This means that wave-like behavior ean in practice be observed only for microscopic particles such as electrons. De Broglie’s idea received its experimental confirmation in 1927, when Davison and Germer observed that a beam of electrons reflected from a crystal produced an interference pattern identical to that previously observed for X-rays (a form of electromagnetic radiation). Reflection and diffraction of waves by a crystal lattice is physically similar to the process of passing through a double slit. Later, scientists also carried out the actual two-slit experiment with an electron beam and also observed a tell-tale interference pattern (Figure 2.1.10). Bight bands eee yas Interference pattern Particle beam Election source Expected behavior for particles ‘Actual electron behavior Figure 2.1.10 Particle vs. wave behavior. 99292323239 3233232323333333333833333339 33333313133DIVTIFTFIIVIFTITIITFIIFVIFTVIFIVIIIIIIIFIFIIFG9899 CHAPTER 2 ATOMIC THEORY 213 Electrons as Standing Waves Quantum mechanics, also known as wave mechanics, treats electrons in an atom as waves. Recall that a wave is a disturbance that travels through space and time, usually accompanied by a transfer of energy. There are two types of waves: travelling and standing. A travelling wave is a disturbance in which every point undergoes oscillatory motion with the same amplitude (e.g., water ripples). A standing wave is a disturbance where different points oscillate with different amplitudes, and some points may not oscillate at all (e.g.,a guitar string). The points of a standing wave that are never displaced are called nodes. Standing, ‘waves can only oscillate at certain discrete frequencies. The greater the number of nodes, the higher the energy of the wave (Figure 2.1.11)CHAPTER 2 ATOMIC THEORY 214 tof Principal quantum nodes number, 2 3 1 2 ° 1 Fred end Feed ond © Wavetunction (#) describes the wave Figure 2.1.11 Wavefunctions of an electron confined in one dimension. It turns out that electrons in atoms and molecules behave like standing waves, similar to what is shown in Figure 2.1.11. The figure is a simplification in that it depicts standing waves in one dimension, whereas electrons in atoms are standing waves in 3D. Wavefunctions and the Schrédinger Equation ‘The de Broglie waves of individual electrons are mathematically described by electronic wavefunctions, . In 1926, Austrian physicist Erwin Schrodinger de- veloped a differential equation that allows one to calculate the shape of electronic wavefunctions and their associated energies. This equation is now known as the BPI DIFZIIFIZIZIIFIZIIIIIZIIIIIZIIIIIZIIZIIIIIIIIII2II33993DIFIFIFFAVIFDIADIAIDITDITDIDITIIIIFIVITIIISIIIVGIR99 CHAPTER 2 ATOMIC THEORY 2.15 Schrdinger equation. For example, the shape of the standing waves depicted in Figure 2.1.11 can be obtained by solving the Schrodinger equation EB), subject to the boundary condition ¥(0) = ¥(L) = 0, where 0 and L are the x-coor- dinates of the confining walls. In this equation, the unknowns are the wavefunction, Yl) and the corresponding energy E. In the process of solving this equation one obtains not one but infinitely many wavefunctions (x) and energy levels Fall of which exactly agree with experiment. By setting up and solving his equation for a hydrogen atom (an electron moving in 3D the presence of a proton), Schrddinger was able to derive the Rydberg formula for emission lines of the H atom without making the arbitrary assumprions thar Bohr had to make. This was a triumph that earned Schrodinger a Nobel Prize for Physies in 1933. Orbitals Schridinger’s equation is central to chemistry because its solution gives energy levels of electrons and electronic wavefunctions. Wavefunctions of individual elec- trons are called orbitals. Iris very important to realize that, according to quantum mechanics, electrons in an atom do not “orbit” the nucleus as was assumed in the Bohr model. The planetary model of the atom, however appealing, is simply at clash with reality. ‘The shape of an atomic orbital describes the spatial distribution of probabilities of finding the electron near various points of space. The greater the value of the square of the orbital at a particular point, (x,y,z), the greater the probability of finding the electron near that point. Quantum Numbers To characterize the state of an electron in a hydrogen atom, four quantum num- hers are used: 1, 1, m, andl an, "The first three of these are called achiral quantum numbers. They arise in the process of solving the Schrédinger equation for the H atom and are also used to label the orbitals themselves, The fourth quantum number (11,) describes an intrinsic property of each electron called spin.CHAPTER 2 ATOMIC THEORY 2-16 Principal Quanturn Number, 1 = 1,2, ‘The principal quantum number determines the energy and size of an orbital. [t can assume only positive integer values. As increases, so do the size and the energy of the orbital. Orbitals with the same 1 are said to form a shell. The principal quantum number also gives the total number of nodes for the orbital according, to the relation: number of nodes = - 1 Azimuthal Quantum Number, |= 0,1, 2, +005 0-1 Also known as the orbital angular momentum quantum number, | describes the shape of an orbital and the angular momentum of an electron in that orbital. Only specific values of [are allowed, and these values range from 0 to 7 — 1. For instance, if = 4, then can be 0, 1, 2, or 3. More / values and hence more shapes are possible for higher 1 values. Orbitals with particular numbers » and I are collectively referred to as a sublevel. “The I values of 0, 1,2, and 3 represent shapes that are respectively known as charp, principal, diffuse, and fine, These names come from atomic spectroscopy. Table 2.1.1 provides a summary of the possible I values at various principal quantum numbers (1) and also introduces the shorthand spdf notation for the » and [ valves. TABLE 2.1.1 QUANTUM NUMBERS 7 AND / a 1 -spdf DESIGNATION nanr-aneeieninne: Selienieasianne Tammie) 2 4d 1 4p 0 4s 3 2 30, 1 0 1 0 oO 3p 35 2p 25 1s FIVPIDIZFDIZIFZIFZIFIIIIIIIIIIIFIIIIIIIIIIIIIIIIIVISDIFIFDFFIFFIFFIFIIAFIFTIIIIIVAIIIITIIIITITIIFIIIIIGGS CHAPTER 2 ATOMIC THEORY 217 Magnetic Quantum: Number, mt,= 0, 1,42, .0 #1 ‘The magnetic quantum number describes the orientation of an orbital with a given / relative to the xyz axes. Possible values for m, are integers ranging from =I, through zero, to 4. For instance, the 2p sublevel includes three orbitals that differ by their magnetic quantum numbers m1, = =1, 0, and 1. If = 0, then only m,=(0is possible. This is why there is only one s orbital for each r. If =1, then m, = =1, 0, +1. This is why there are three p-orbitals for each f= 2, then m,=~2,-1, 0, +1,42. This is why there are five d-orbitals for each n. Each unique combination of 1, [, and mis significant because it represents an orbital. In a hydrogen atom, all orbitals with the same have the same energy. Orbitals chat have che same energy are said to be degenerate, Table 2.1.2 provides, a summary of the possible ff, and m, values up to m= 4, as well as the number of atomic orbitals and maximum possible number of electrons. TABLE 2.1.2 SUMMARY OF QUANTUM NUMBERS n, /, AND m, AND MAXIMUM NUMBER OF ELECTRONS IN ATOMIC ORBITALS NO. n I spd TOTAL MAX m, ORBITALS IN (SHELL) (SUBLEVEL) DESIGNATION SUBLEVEL ORBITALS ELECTRONS pos ey eo REERENEL 4 3 ar 7 z 4d 5 16 32 1 4p 3 0 4s i 3 2 3d | 2.0.1.2 5 1 3p. =1.0,1 3 9 18 0 35 0 1 2 1 2 7 2p 10,1 3 7 : oO 25 oO 1 1 o Is ° 1 1 2CHAPTER 2 ATOMIC THEORY 2-18 Spin Quantum Number, m, = £112 The fourth quantum number is associated with an intrinsic angular momentum of each electron called spine. The spin isa vector that, loosely speaking, can have only two orientations with respect to an identified direction: up (when mt, = +1/2) or down (when m, =-1/2). Figure 2.1.12 shows schematically the two possible spin states: “spin up” and “spin down.” Because of spin, every electron has a magnetic moment that is manifested in how the electron interacts with a magnetic field. cp ¥ Spin up Spin down Figure 2.1.12 Direction of magnetic field generated by electron spin Pauli Exclusion Principle According to the Pauli exclusion principle, formulated by Austrian physicist Wolfgang Pauli, no two electrons in an atom can have the same four quantum numbers. Put differently, each and every electron in an atom has a unique set of four quantum numbers. Since each orbital can hold two electrons, is it possible for two electrons in the same orbital to have the same spin? If two electrons are in the same orbital, they must have the same set of », /, and 7, numbers. If they also have the same spin, the Pauli exclusion principle would be violated. Therefore, if two electrons are in the same orbital, they must have opposite spins (different m, values). The state in which two electrons occupying the same orbitals have parallel spins is quan- tum-mechanically “forbidden.” In diagrams, electron spins are usually represented by arrows pointing up or down, as shown in the Figure 2.1.13. JIDIIDIIVZIIIIIIIIIIIIIQIIIIIIIIIIIIIIIIIIIIIVISDIFIFFFIFVIFFIFVVFVVFVVTVVVIVVVIIIIIVIVIVGIGSS CHAPTER 2 ATOMIC THEORY 2-19 Electrons with Electrons with paralle! ‘opposite spins Figure 2.1.13. Representation of electron spins in orbitals. Summary The four quantum numbers are independent of each other, but assume only specific values. The allowed values are: + 121,23... + m= 0,41, 42, 0H © 120,1,2,.0401 som, 41/2 Example 2.1.1. Quantum Number Validity (In-Class Exercise) Which of the following sets of quantum numbers, in the order of nl, m, and m, are possible? In the valid sets, identify the orbital (2) 3, 1,0, +12 (1, 1,0, -172 (c) 2,0, 0, +12 (a) 4,3, 2, -12 THE SHAPES OF ATOMIC ORBITALS In quantum mechanics, one-electron wavefunctions (orbitals) are used to describe the energy and the likelihood of finding the electrons near various points in space. Although we sometimes use the one-dimensional wavefunction x) for illustrative purposes, it is important to realize that the actual wavefunction of the electron is in 3D, ¥{x,y,2). An orbital is nota “balloon” or “container” in which the electron “lives,” nor is it a trajectory of the electron. Rather, an orbital isa function whose square describes how likely the electron is to be found near various points in space.CHAPTER 2 ATOMIC THEORY 2-20 ‘The probability of finding an electron at various points can be visualized by plot- ting the electron density, which is given by the square of the orbital. -W'(|Elocton probability centy ‘Wavetunction Figure 2.1.14 Wavefunetion and electron density plots in one dimension. In Figure 2.1.14, only one subscript (71) was used to label the wavefunction. How- ever, in order to visualize orbitals in 3D, it is necessary to specify two additional quantum numbers, ! and m,, Thus, an orbital is generally specified as a At principal quantum number of 1 = 1, only ! = 0 and m, = 0 values are allowed. ‘This combination of m = 1, = 0, and m, = 0 gives rise to only one orbital (1s), denoted as ¥,, of Yyy9- The Is wavefunction has the shape of a sphere centered at the nucleus. The shape of the Is orbital can be represented in various ways shown in Figure 2.1.15. Because the 1s orbital is spherically symmetric, its shape can be completely described using only one coordinate, the radial distance r from the nucleus. Note also that the 1s orbital has no nodes. 93333333333333333333333333333333333333333333DFFITFFTIIFIFIVIFDIDIITFIFIVIIIIIIIIFIIFIIFIIIIGGS CHAPTER 2 ATOMIC THEORY 22d @) vis ©) wy x x wave function ‘ection pobabity density Oe © w, Ieosutace probabity density map Figure 2.1.15 Various representations of the 1s orbital, ‘The square of an orbital gives the electron density as a function of distance from the nucleus (Figure 2.1.15c). To better visualize the electron density in 3D, a probability density map may be used (Figure 2.1.15d). The greater the density of the dots in a particular region of such a map, the greater the probability of finding the electron there. n=2 For the principal quantum number » = 2, two types of orbitals, 2s and 2p, are possible. The respective combinations of quantum numbers (nl, for these two orbital types are (2, 0, 0) and (2, 1, [-1, 0, or +1)). In general, orbitals become larger as m increases, so the orbitals for m = 2 are larger than for 1 = 1. Like the 1s orbital, the 2s orbital (wavefunction ¥,, or ¥,,) is also spherically symmetric, But unlike the nodeless 1s orbital, the 2s orbital has a node. Posi:ive and negative lobes are usually shown by different colours.(CHAPTER 2 » ATOMIC THEORY 2-22 Figure 2.1.16 shows: a. The ¥4,, wavefunction (i.e, 2s orbital) itself bb. The spherical shape of the orbital ©. The square of the orbital d. The probability density map @ Vo () Wy ‘wavefunction clectron probability density (o) (a) Isosurace probabiliy density map Figure 2.1.16 Various representations of the 2s orbital. In the case of 2p orbitals, three different m, numbers (-1, 0, +1) are possible. Therefore, there are three 2p orbitals. These orbitals are designated as 2p,, 2p,, and 2p,. They are stretched along the x, y, and z axes and hence are perpendicular to each other. All three 2p orbitals are degenerate (i.e., have the same energy). They collectively (but not respectively) correspond to the wavefunctions “5 Yo» and ¥,,,- Each of the 2p orbitals has one node (see Figure 2.1.17). 33133 IIII33I3I33I133333333333333333333333333333DFFIFIFFIIFIIFITVIIIIFIFIIIFIFIIVIVIIIIFIIIIFIFIGGO9 CHAPTER 2 ATOMIC THEORY 2-23 m , ¥, wave function ‘Schematic representations ofthe three 2p orbitals ~ oe lectron probability density probabilly density map Figure 2.1.17 Various representations of the 2p orbitals. Example 2.1.2. Nodal Planes in 2p Orbitals Where are the nodes in each of the 2p orbitals, and on which Cartesian planes are the nodes found? n=3 For the principal quantum number » = 3, the possible orbital types are 3s, 3p, and 3d. The 3s and 3p orbitals have shapes similar to those of the 2s and the 2p orbitals, respectively, but have more nodes. The orbitals for 1 = 3 are larger than those for n= 2. ‘The ive possible 3d orbitals are shown in Figure 2.1.18, Four of these orbitals have four equal lobes—two positive and two negative. The fifth 3d orbital is different from the rest in that it has two lobes stretched along the z axis and a thick ring.CHAPTER 2 » ATOMIC THEORY 2-28 suse x yi Looking down axis y Zz yin 3d, x x Looking down Lookina down zaxis yas Figure 2.1.18 The five 3¢ orbitals. a Example 2.1.3. Wavetunctions for n= 3 Orbitals ‘Write the wavefunction symbols for n= 3 using the ,,, nomenclature and the ap- propriate n, |, and my, values. Indicate which symbols correspond to the 3s, 3p, and 3d orbitals. 313II1IIIII3IIIIGIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIDITDITFIFITIFIFAVIFTITIIIVDITITIIIIIFIIITIIIIFFIIGS CHAPTER 2 ATOMIC THEORY 2.25 The Relative Energies of the Atomic Orbitals Orbital energy levels are quantized, meaning that only certain energy values are allowed. In the case of the hydrogen atom, orbital energies depend only on the principal quantum number, . That is, the 1 = 1 orbital has the lowest energy, the r= 2 orbitals (2s and 2p) have a higher energy, the m = 3 orbitals (3s, 3p, and 3d) are yet higher in energy, and so forth However, in many-electron atoms, orbitals with the same m but different / quan- tum numbers have different energies. For a given 1, the s orbital has the lowest energy, followed by pd, and f. This happens because s, p, d,etc., orbitals have different shapes, so electrons in those orbitals interact with each other and with the nucleus differently. The order of the sublevel energies has important consequences. According to the Aufbau principle (Aufbau is German for “building up”), electrons occupy (fill) orbieals in the order of increasing energy. The energies of vacant orbicals increase in the order shown on the right-hand side of Figure 2.1.19. As ns np ad at gt iii sq OO000 aT Sera oO 5p OOO 40000000 ASA det 830 aq DOOo0o ee Ts ao ”900 sooooo ete et SS ee fhao *o0H ae & 2| 3 aso ooo sa Figure 2.1.19 Relative energies of vacant atomic orbitals.CHAPTER 2 ATOMIC THEORY 2-26 ‘The relative energies of atomic orbitals shown in Figure 2.1.19 are #ot fixed and may change as the orbitals get filled. In particular, ifthe 3d sublevel is occupied by at least one electron, it becomes lower in energy than the 4s sublevel. Moreover, after the switch has occurred, the 4s electrons do not relocate to the now-lower 3d orbitals but stay where they are, in the 4s sublevel. The switch from the order 4s < 3d to 3d < 4s occurs in all species (atoms and ions) starting with Z = 21 (scandium) and to the end of the periodic table. Similarly, the Ss sublevel drops below the 4d sublevel starting with Z = 39 (yttrium). Such effects play a decisive role in determining the ground-state electron configurations of transition metal atoms and ions. ELECTRON CONFIGURATIONS In the ground state of an atom the electrons distribute themselves among the orbitals in such a way as to minimize the total energy, while obeying the Pauli exclusion rule. Using this principle and knowing the relative energies of the o- bitals, one can write down the ground-state electron configuration for an atom, There are two common ways of writing electron configurations. Full Electron Configuration {A full electron configuration shows the number of electrons (indicated by a super- script) for each sublevel. For example, the electron configuration for the H atom in its ground state is written as 1s', since there is only one electron and it resides in the Is sublevel. (If the electron is in an excited state, electron configurations such as 2s* and 3p! are possible.) For the N atom, which has seven electrons, the ground-state electron configuration is 1s'2s*2p'. Example 2.1.4. Full Electron Configurations (In-Class Exercise) Write ground-state electron configurations for O and Br. Abbreviated Electron Configuration Abbreviated electron configurations show noble-gas atom electron configurations as “cores” in square brackets, followed by the full specification of the remaining electrons (see Table 2.1.3). PIPPI VIIIFIIFIFIIIFIIFIIIIIIIIIIIIIIIIIIIIIIIIIIIIGDIFFFTFIIIFAITIFIITIVIFIIIIIIIFIFIIFIFIITIGO999 CHAPTER 2 ATOMIC THEORY 227 TABLE 2.1.3 ABBREVIATED ELECTRON CONFIGURATIONS. ELEMENT CONFIGURATION __ CONFIGURATION Sayan Sedeeerd) [Sa Tiree Sicon SiGe secten) —[1eas7aFap wr Pasun KD) [19252853945 wis can ca eects) —[wavasarares wis Fi GT ero) [1525 aa ASUS iss ie, 6Seeorrs) —_[ waravaravararapaaves | wads cas, 5 GS aecvon) —isasaravaraeuraraassr6s [ales Example 2.1.5. Abbreviated Electron Configurations (In-Class Exercise) Write abbreviated ground-state electron configurations for cobalt, barium, and tel- lurium: Valence and Core Electrons For main-geoup elements, valence electrons are those with the highest principal quantum number, 2. The remaining electrons of the lower-lying shells are referred to as core. Valence electrons participate in the formation of chemical bonds with other atoms, whereas core electrons usually do not participate in such reactions. For transition metals, the determination of the valence electrons is more complex because some or all of the d-electrons of the second-to-last shell can behave as valence electrons. Identification of valence electrons in transition elements is beyond the scope of this course. Example 2.1.6. Identify Valence and Core Electrons (In-Class Exercise) Write the electron configurations for the O and Al atoms, and identify the core and valence electrons in each of them,CHAPTER 2 ATOMIC THEORY 2-28 Cations, Anions, and Isoelectronic Species ‘When cations (positively charged ions) are formed from atoms, electrons are first removed from the highest-occupied sublevel. Consider the formation of Na* and Ca: Na (1s'2s*2p*3st) — Na! ( pte Ca (1s*2s*2p*3s*3p*4s*) > Ca?" (1s*2s*2p°3s*3p*) + 2e~ ‘When anions (negatively charged ions) are formed from atoms, electrons are added to the lowest available sublevel. Consider the formation of N* and Cl: N (1s*2s*2p*) + 3e° + N* (1s*2s2p*) Cl (1s2284 3s3p') + © 9 Ch (18282p'3S3p%) Example 2.1.7. Isoelectronic Species (In-Class Exercise) Write the ground-state electron configurations for O°, F-, Na’, and Mg’. How do these electron contigurations compare with Ne? All five species have exactly the same electron configuration and therefore form an isoelectronic species. Isoelectronic species have the same number of electrons in the same orbitals. Electron Configurations of Transition Metal Cations According to Figure 2.1.19, the empty 4s level has a slightly lower energy than the empty 3d. However, when both the 4s and 3d levels each contain at least one electron, the order is reversed and the 3d level “sinks” below 4s. This effect has very important consequences for the chemistry of transition metals. In transition metals, the outermost s and d sublevels both contain at least one electron, so their energy ordering is 3d < 4s. Therefore, when a transition-metal atom is ionized, electrons are removed first from the highest-energy 4s orbital and only then from 3d. 92I2IIIIIIZIIIZIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIGDIFFIFFFIFIFFIITFIOTDADTIIIIFIVTIIIIIVIFIFIIFIIIIO99 CHAPTER 2 ATOMIC THEORY 2.29 For example: V: [Ar] 3d! 4° Ve [Ar] 3d 4st Vis [Ar] 3a A useful mnemonic that may help you remember the above rule is, for 3¢-tran- sition metals, the 4s electrons are first in, first out. Example 2.1.8, Electron Configurations of lons (In-Class Exercise) Write the ground-state electron configurations for V+, Ga, Mn®. ORBITAL DIAGRAMS Although convenient, electron configurations do not tell us how the electrons are distributed within the sublevels. Orbital diagrams, which employ lines or boxes to represent the individual orbitals, are used to show this information. In 1925, German physicist and mathematician Friedrich Hund established a gen= eral principle governing the arrangement of electrons in atomic sublevels. This principle is known as Hund’s rule: Electrons fill orbitals of equal energy singly, with parallel spins, and start pairing up only after all these orbitals are balf-filled. In other words, electrons do not pair up until they have to. For example, the 2p sublevel fills with electrons as shown in Figure 2.1.20. Electronsiin singly occupied itals in a degenerate set have parallel spins and, when paired, have opposite spins. Nitrogen, therefore, has its theee 2p electrons in three separate orbitals, and all three electrons have the same spin, c os ee Figure 2.1.20 Ground-state filling of 2p orbitals.CHAPTER 2 ATOMIC THEORY 2-30 Similarly, V, Mn, and Fe have respective d orbital configurations of 3a°, 3d, and 3d and these are filled as shown in Figure 2.1.21. ee Litit Ske aa Figure 2.1.21 Ground-state filling of 3d orbitals in V, Mn, and Fe. ‘The orbital diagrams above only show the last sublevel filled. Itis also possible, of course, to draw orbital diagrams for all filled sublevels. Example 2.1.9. Drawing Orbital Diagrams (In-Class Exercise) Draw ground-state orbital diagrams for the valence levels of As and Br, showing all orbitals and electrons. Which element has the greater number of unpaired electrons? Exceptions: Cr and Cu ‘The ground-state (lowest-energy) electron configuration of the chromium atom is [Ar] 3d'4s!, not [Ar] 3d°4s?, as one may expect (see Figure 2.1.22). The reason for this cannot be explained in terms of orbital energies alone because the total electronic energy of an atom is NOT the sum of the energies of electrons in the occupied orbitals. JIDIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIISITITFFIFIIFTFITVDIFIFITVDITSIIIIIIIIIIITIIIITIIFI9999 CHAPTER 2 ATOMIC THEORY 231 Chromium i ees 30° Actual Figure 2.1.22 Expected and actual ground-state electron configurations of the Cr atom. ‘The ground-state (lowest-energy) electron configuration of the copper atom is [Ar] 3d!4s!, not [Ar] 34°4s" (sce Figure 2.1.23). Copper Figure 2.1.23 Expected and actual ground-state electron configurations of the Cu atom Cr and Cu are the only two atoms of the first transition-metal row that exhibit such behaviour. A useful method for remembering the ground-state electron con- figurations of chromium and copper is to think of half-filled and completely filled d-sublevels as especially stable. Then one can say that atoms such as Cr and Ci “rush” to attain these electron arrangements by having one of the 4s electrons transferred to 3d sublevel.CHAPTER 2 ATOMIC THEORY 2-32 Practice Problems 1. How are the energy, wavelength, and frequency of electromagnetic radiation related? 2. Using the Bohr model, explain the origin of the Balmer, Lyman, and Paschen emission series. 3. Why is the one-dimensional wave shown by ,(x) in Figure 2.1.11 higher in energy than ¥, (x)? 4. Whatare the Pauli exclusion principle, the Aufbau principle, and Hund’ rule? 5. Explain, in the context of quantum mechanics, what a node is. How many nodes are present in each of the orbitals of principal quantum numbers 1, 2, 3,4, and 5? Draw a 3s orbital and identify the radial nodes. 6. In quantum mechanies, whatis the definition of an orbital? Why are multiple colours often used to draw orbitals of = 2 and higher? 7. Why do 2p orbitals have three magnetic quantum numbers? Are 2p orbitals, of different magnetic quantum numbers degenerate? 8. Which of the following sets of quantum numbers (n, l,m 7) are valid? OF the valid numbers, identify the orbital. a. 2,1,0,-12 b. 3,0,0, +172 12,3412 @. 4,3,1,-12 e. 4,3,2,-12 9. Which combination of fp and my, is not posible for an electron in an atom? a. 2,1,-1,-12 b. 2,0,1,412 cc. 1,0,0, 41/2 IIVPIFGIDZIIIIJIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIISFITFFIFAIITFFIFIFIFAIIIIITIIITIFIIIFIIFSIITIIIIIO99 CHAPTER 2 ATOMIC THEORY 2-33 d. 3,2,2,-12 ec. 3,2,-2, 41/2 10. Which of the following are the possible values for the magnetic quantum, number, m1, of a 3p electron? a. -1,0,41 b. 42,41, 0,-1,-2 ce. 0,41, 42 $142,538 fe. Oonly 11, Which of the following combinations of 7, and m, quantum numbers does not describe an electron in the ground state of a carbon atom? a 1410 b 210 « 20,0 d& 21-1 & 1,00 12, Write the electronic configurations (in full and abbreviated forms) for O, Ca, Ni, Cr, and Cu in their ground state. 13. Define the following terms: valence electron, core electrons, ground state, excited state. 14, Which one of the following has the largest number of unpaired electrons in its ground state? a. Zn a. Cu Ee iGs je Mg om. Gur bP e Te h. Fe k. Fe . ove i Ma LG 15, Which one ofthe following has the electronic configuration 1s°2s'2pX3s'3p'3d* in the ground state? a. Mn b. Cr Fe d. Mn eveCHAPTER 2 ATOMIC THEORY 2:34 16. Which of the following statements is/are correct for selenium (Se) in the ground state? a. Ithas two unpaired electrons. b. ‘The highest-energy electron is in a Sp orbital c. The highest-energy electron could have a value of m, d._Itis isoelectronic with Br. 17. Which of the following species is/are isoelectronic with Ar? a. Kr b. Ca 6 d. Cr e. AP 18. In which of the following goups are all three species isoelectronic with each other? a. Cs‘, Ba®*, Te b. S*, An, Ca¥ c. O*7, F,Mg* 19. Which of the following are d-block elements? a Sn b. Ag © Sr d. Rn e Ar PIDVDIFVIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIGDITFFFFFIFIFFIFIIIIITIFIIITIFIIITIFSIIITIIIGGGS CHAPTER 2 ATOMIC THEORY 2:35 2.2 The Periodic Table and Periodic Trends INTRODUCTION In this topic, the arrangement of elements in the periodic table is examined, along, with four important periodic properties: atomic size, ionization energy, electron affinity, and electronegativity. ‘THE FIRST PERIODIC TABLE The fist periodic table of the elements was drafted in 1869 by the Russian chemist Dmitri Mendeleev, who is aptly called the “father ofthe periodic table.” Mendeleev based his arrangement of the elements on observed physical properties such as density and reactivity. His organization and attention to detail were exceptional Using his table, he predicted not only the existence of gallium (Ga) before its discovery in 1875, but also the density of this element within 1% accuracy. ‘The term “periodic” is a reference to the Periodic Lavy, proposed independently by Mendeleev and German chemist Lothar Meyer in 1869: When the elements are arranged in order of increasing atomic mass, cer- tain sets of properties recur periodically. ‘THE MODERN PERIODIC TABLE In the modern periodic table, the elements are arranged by their atomic number Zina series of rows (periods) of variable length. The atomic number is shown, above the symbol of the element, its atomic mass is below. If the atomic mass is shown in parentheses, it means the mass number of the most stable artificial isotope of the element. The table arrangement places similar elements in vertical groups (see Figure 2.2.1).CHAPTER 2 ATOMIC THEORY 2:36 Note: To accurately retlect the spd bods, this vorsion ofthe parade table chows He ‘over in Group 2 beside H. Future versions ‘ofthe periodic table wll show He back at pberolemerte the top of Group 18 ‘block elements eee ia &x |e | Fe | Go| Hi | Cu | 2 | Ga | Ge As | Se | 8 | Ke Ea Mo | Te | Ru | Bh $n Sb Te | | xe, = fu) Ho| [Pe BL Fe,| At | ee naa Pe ae &, Bt | Bs | By | Uo] it |Uia| Uap van ™ |w so. Pa Pt Los 7h] Pa] 6 | Np) Bu] Am] Gm) k| Gt] eS) Fim) Naa) No | br Figure 2.2.1 The periodic table showing the spdf blocks. SIVIVIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIGDIDIFIFIIFIFFITFAITIIIFIFIFIITTITIFIIIIIIFIVIGIGGS CHAPTER 2 ATOMIC THEORY 2-37 THE MAIN GROUP ELEMENTS The spdf blocks in the periodic table are defined by the orbitals that are occupied by valence electrons. The s-block and p-block elements are called the main group elements. The row in which a main group element is placed is given by the prin- cipal quantum number of its valence shell. BLOCK (GROUPS 1 AND 2) ‘The s-block elements have either one valence clectron (Group 1: alkali metals) or two valence electrons (Group 2: alkaline earth metals). Note that all elements in the same group have an identical valence electron configuration. Group 1 - elements have an 1s’ valence configuration, while Group 2 elements have an st valence configuration. p-BLOCK (GROUPS 13 TO 18) ‘The presence of the valence electrons in p orbitals defines this section of the pe- riodic table. The p-block elements are those from Group 13 to Group 18 and the elements in their respective groups are collectively known as: + The triels (Group 13): 3 valence + The halogens (Group 17; from the electrons. Greek word balas meaning “salt forming”): 7 valence electrons. + The tetrels (Group 14): 4 valence electrons. + The noble gases (Group 18): 8 valence electrons. Their name is derived from the fact that these ‘elements appeared completely unre- aetive and do not make compounds + The chaleogens (Group 16; from the (now known to be untrue). Greek word chaleos meaning “ore forming”): 6 valence electrons. + The pnictogens (Group 155 from the Greek word pnictos meaning “to choke”): 5 valence electrons. Asummary ofthe valence-shell configurations of the s-block and p-block elements is shown in Table 2,