Class03 ChemistryG12 Notes and Homework
Class03 ChemistryG12 Notes and Homework
OLYMPIADSCHOOL
Chapter3 Atoms,ElectronsandPeriodicTrends
Rutherford performed several calculations that led him to an inescapable conclusion: the atom is made up mainly of empty space, with a small massive region of space small, concentrated charge at the centre. The charge on the central region was determined to be positive, and was named the atomic nucleus. B ii d d h i l Because Rutherfords atomic model, showed electrons in motion around an atomic nucleus, chemists often call this the nuclear model of the atom. Also referred to as a planetary model because the electrons resemble the planets in motion around a central body.
According to these assu p o s, a e ec o in motion cco d g o ese assumptions, an electron o o around a central body must continuously give off radiation. One should be able to observe a continuous spectrum (a rainbow) of light energy as the electron rainbow ) gives off its radiation. Because the electron should also lose energy as a result of this radiation, the radius of its orbit should continuously decrease in size until it spirals into the nucleus. nucleus This predicted annihilation of the atom would occur in a fraction of a second. However, atoms were not seen to destabilize as predicted by this model. Nineteenth-century physics could not explain why Rutherfords model corresponded to a stable atom.
On what basis could Bohr make these claims? I 1900 a physicist named M Pl In 1900, h i i t d Max Planck proposed an k d idea that was so revolutionary that he himself was g p p gg unwilling to accept its implications. Planck suggested that matter, at the atomic level, can absorb or emit only discrete quantities of energy. E h of th Each f these specific quantities i called a quantum of ifi titi is ll d t f energy. In other words, Planck said that the energy of an atom is quantized. Something that is quantized can exist q g q only in certain discrete amounts. It is not continuous. In this sense, the rungs of a ladder are quantized, while the smooth slope of a ramp is not. Unlike ladders and not ramps, however, a quantum is an extremely small packet of energy. Although Planck said that the energy of matter is quantized, he continued to describe energy quantized as travelling in the form of waves. He was unwilling to consider that energy might have particle-like properties.
In 1905, however, Albert Einstein was prepared to make just such an assertion Light according to Einstein, is also assertion. Light, Einstein quantized. It occurs as quanta of electromagnetic energy that have particle-like properties. These particle-like packets of energy were l t called photons. I Einsteins view, li ht ( d later ll d h t In Ei t i i light (and, by extension, all electromagnetic energy) travels in the form of photons of energy. Light is emitted as photons of energy, and light is absorbed as photons of energy. The energy that is associated with the coloured lines in this spectrum corresponds to the change in energy of an electron as it moves to higher or lower energy levels.
For example, when a hydrogen atom is exposed to electrical current, c rrent or to another form of electromagnetic energ its energy, electron absorbs photons of energy. The atom is now said to be in an excited state. Another common way for atoms to become excited is through atomic collisions. For example, when two hydrogen atoms collide, some of the kinetic energy from one atom is transferred to the other atom. gy The electron of the second hydrogen atom absorbs this energy and is excited to a higher energy level. y g When the electron of a hydrogen atom that has been excited to the third energy level falls to the second energy level, it emits light of certain energy. Specifically, a e ect o t at makes a t a s t o from t e t d Spec ca y, an electron that a es transition o the third energy level to the second energy level emits a photon of red light with a wavelength of 656 nm. Because line spectra result when atoms in an excited state emit photons as they fall to a lower energy level, these spectra are also called emission spectra.
The figure shows the energy transitions that are responsible for the coloured lines in hydrogens emission spectrum. N designates the allowed energy levels for the hydrogen atom: n = 1 n = 2 and so on This symbol, n 1, 2, on. symbol n, represents a positive integer (such as 1, 2, or 3), and is called a quantum number.
Another kind of spectrum that is related to an atoms emission spectrum is an absorption spectrum. This kind of spectrum results when electrons of atoms absorb photons of certain wavelengths, and so are excited from lower energy levels to higher energy levels. The figure shows the absorption spectrum for hydrogen As you can see hydrogen. see, discrete, dark lines appear in the precise locations (wavelengths) as those of the coloured lines in hydrogens emission spectrum.
There was a problem with Bohrs model, however. It successfully explained only one-electron systems. Th t is, it worked fi f h d That i k d fine for hydrogen and f i d for ions with only one ith l electron, such as He+, Li2+, and Be3+. Bohr s unable however, Bohrs model was unable, however to explain the emission spectra produced by atoms with two or more electrons. Either Bohrs model was a coincidence, or it was an oversimplification in need of modification. Further investigation was in order.
The quantum mechanical model of the atom: This model describes atoms as having certain allowed quantities of energy because of the wave-like properties of their electrons. Th b f h lik i f h i l The figure depicts the volume surrounding the nucleus of the atom as being indistinct or cloud-like because of a scientific principle called the uncertainty principle. The German physicist Werner Heisenberg p p g proposed the uncertainty p y principle in 1927. p
Using mathematics, Heisenberg showed that it is impossible to know both the position and the momentum of an object beyond a certain measure of precision. (An objects momentum is a precision object s property given by its mass multiplied by its velocity.)
According to this principle, if you can know an electrons precise position and path around the nucleus, as you would by defining its orbit, you cannot know with certainty its velocity. Similarly, if you know its precise velocity, y cannot know with certainty its y y p y you y position. Based on the uncertainty principle, Bohrs atomic model is flawed because you cannot assign fixed paths (orbits) to the motion of electrons.
Clearly however electrons exist And they must exist Clearly, however, exist. somewhere. To describe where that somewhere is, scientists used statistics. You cannot talk about electrons in terms of certainties, b t you can t lk about them in t t i ti but talk b t th i terms of probabilities. f b biliti Schrdinger used a type of equation called a wave equation to define the probability of finding an atoms electrons at a atom s particular point within the atom. There are many solutions to this wave equation, and each solution represents a particular wave function.
Each wave function gives information about an electrons energy and location within an atom Chemists call these wave atom. functions ORBITALS. In further studies of chemistry and physics, you will learn that the wave functions that are solutions to the Schrdinger equation have no direct, physical meaning. They are just mathematical ideas. However, the square of a wave function does have a physical meaning. It is a quantity that describes the probability that an electron is at a particular p p point within the atom at a particular p time. The square of each wave function (orbital) can be used to plot three-dimensional probability distribution graphs for that orbital. These plots help chemists visualize the space in which electrons are most likely to be found around atoms. These plots are also referred to as electron probability density graphs graphs. Note: Although orbitals are wave functions without associated physical characteristics like shape and size, chemists often use the term orbitals when the mean three dimensional probabilit hen they three-dimensional probability distribution graphs.
We will discuss the size and shapes of orbitals. However, what is really meant is their associated probability distribution graph, which is calculated using the square of the wave function. E h orbital h it own associated energy, and each Each bit l has its i t d d h represents information about where, inside the atom, the electrons would spend most of their time. Scientists cannot determine the actual paths of the moving electrons. However, orbitals indicate where there is a high probability of fi di electrons. b bilit f finding l t
The next figure represents the probability of finding an electron at any point in space when the electron is at the lowest energy level (n = 1) of a hydrogen atom. Where the density of the dots is greater, there is a higher probability of finding the electron This graph is fuzzy looking electron. fuzzy-looking because the probability of finding the electron anywhere in the n = 1 energy level of a hydrogen atom is never zero. Farther from the nucleus, the probability becomes very small, but it will still never reach zero. Therefore, because the shape of the n = 1 orbital for hydrogen represents the level of probability of finding an electron, and since the probability never reaches zero, you have to select a cut-off level of probability. cut off probability A level of probability is usually expressed as a percentage. Therefore, the contour line in B defines an area that represents 95 percent of the probability graph This two dimensional shape graph. two-dimensional is given three dimensions in C. What this means is that, at any time, there is a 95 percent y p chance of finding the electron within the volume defined by the spherical contour.
The First Quantum Number: Describing Orbital Energy Level and Size
The principal quantum number (n) is a positive whole number that specifies the energy level of an atomic orbital and its relative size. The value of n therefore may be 1 2 3 and so on A n, therefore, 1, 2, 3, on. higher value for n indicates a higher energy level. A higher n value also means that the size of the energy level is larger, with a higher probability of finding an electron farther from the nucleus. The greatest number of electrons that is possible in any energy level is 2n2.
Noticethatthe numberofpossiblevaluesforlinagivenenergylevel isthesameasthe valueofn.Inotherwords,ifn=2,thenthereare onlytwopossiblesublevels (twotypesoforbitalshapes)atthis only two possible sublevels (two types of orbital shapes) at this energylevel. Eachvalueforlisgivenaletter:s,p,d,orf. g , p, , Thel=0orbitalhastheletters;Thel=1orbitalhastheletterp;Thel =2orbitalhastheletterd;Thel=3orbitalhastheletterf. Theorderofthe"shells"is Some Poor Dumb Fool,OR Silly Professors Dance Funny. Afterthe F subshell ,justfollow F in alphabeticalorder. alphabetical order Toidentifyanenergysublevel(typeoforbital),youcombinethe value ofnwiththeletteroftheorbitalshape. p Forexample,thesublevelwith n=3andl=0iscalledthe3ssublevel. Thesublevelwithn=2andl=1 isthe2psublevel.
Orbital S
Value l=0,m=0
NumberofValuesfor m 1
l=1,m=1,0,+1
l=2,m=2,1,0,+1,+2
l=3,m=3,2,1,0,+1,+2,+3
l=4,m=4,3,2,1,0,+1,+2, 9 +3,+4
Wherethequantumnumber isthesubshell,themagnetic number ml representsthenumberofpossiblevaluesforavailable energylevelsofthatsubshell asshowninthetable. l l f h b h ll h h bl Noticethatforanygivenvalueofl,thereare(2l+1)valuesforml. Thetotalnumberoforbitals f Th t t l b f bit l foranyenergylevelnisgivenbyn. l l i i b Forexample,ifn=2,ithasatotalof4orbitals (ansorbital andthree porbitals). p orbitals)
Shapes of Orbitals
An orbital is associated with a size, a three-dimensional shape, and an orientation around the nucleus. T Together, the size, shape, and position of an orbital th th i h d iti f bit l represent the probability of finding a specific electron around the nucleus of an atom atom. The figure shows the probability shapes associated with the s, p, and d orbitals. (The f orbitals have bee o e a d o b a s ( e o b a s a e been omitted ed due to their complexity.)
Atoms with two or more electrons have orbitals with shapes that are similar to those of hydrogen. However, the interactions among the additional electrons result in orbitals with th same value of n, b t diff ith the l f but different energies. t i For example, the figure shows an energy level diagram for the lithium atom, which has three electrons. You can see that the 2s orbital has a lower energy than the 2p orbitals orbitals. Similarly, the 3p orbitals are lower in energy than the 3d orbitals. Notice, however, that all the orbitals within a sublevel have the same energy. For example, example the three p orbitals in the 3p sublevel have the same energy
Since low energy usually means stability, it is reasonable that the most stable energy state (ground state) for any atom is one in which its electrons are in the lowest possible energy level level. As you know, this is the 1s orbital (n = 1). However, the electrons of most atoms are not packed into this orbital. In fact, p , experimental evidence shows that only two atoms have all their electrons in the 1s orbital: hydrogen and helium. T explain h To l i how and why thi i th case, we must consider d h this is the t id another property of the electron.
The spin quantum number (ms) specifies the direction in which the electron is spinning. This quantum number has only two possible values: +1/2 or -1/2. ibl l 1/2 1/2 In 1925, an Austrian physicist, Wolfgang Pauli, proposed that only two electrons of opposite spin could occupy an orbital This orbital. proposal became known as the Pauli exclusion principle. What the exclusion principle does is place a limit on the total number of electrons that may occupy any orbital. is only, That is, an orbital may have a maximum of two electrons only each of which must have the opposite spin direction of the other. It may also have only one electron of either spin direction. An y y p orbital may also have no electrons at all.
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Consider the significance of lithiums quantum numbers. The first two electrons occupy the 1s orbital, and have the same sets of quantum numbers as heliums two electrons helium s electrons. According to the Pauli exclusion principle, the 1s orbital (n = 1) is now full because it contains the maximum number of electrons: two. For lithiums third electron, n cannot equal 1. Therefore, the next principal energy l t i i l level f th electron i n = 2 If n = 2 l l for the l t is 2. 2, may have a value of 0 or 1. Remember that an atoms ground state represents its lowest energy state. p gy
Because an orbital with l = 0 (an s orbital) has a lower energy than an orbital with l = 1 (a p orbital), you would expect a hi h probability of finding lithiums third electron high b bili f fi di li hi hi d l in the s orbital given by n = 2, l = 0. In fact, experimental evidence supports this expectation expectation. You know that if l = 0, ml has only one possible value: 0. Finally, by convention, ms is +1/2.
It is possible to distinguish atoms by writing sets of quantum numbers for each of their electrons. However electrons However, writing quantum numbers for an atom such as uranium, which has 92 electrons, would be tedious. Fortunately, chemists have developed a shortcut to represent the number and orbital arrangements of electrons in each atom You will see the close connections atom. to the periodic table, and you will find out why orbital energies differ (for example, why a 2s orbital is lower in energy than a 2p orbital).
PLEASE keep the following in mind: According to quantum mechanics: Electrons do not occupy orbitals. N d orbitals bit l Nor do bit l contain electrons. El t t i l t Electrons d not fill do t orbitals one at a time. Nor do electrons have properties that designate individual electrons as first, second, third, fourth, etc. g , , , , Orbitals do not really have substance or shapes. Orbitals are mathematical equations that can be used to calculate probability densities for electrons electrons. The shapes, and the impression of substance, result from the contour lines used to set a limit on the extent of those probabilities. It takes time and experience for people to think about and talk about atoms in completely quantum mechanical terms. terms It is much simpler to think about orbitals as if they have substance. occupying filling You will read about electrons occupying and filling orbitals, but this terminology is not scientifically correct, its just easier to understand the concepts.
The figure shows the total number of orbitals in which electrons are written in electron configurations. A atoms electron configuration i a shorthand notation th t An t l t fi ti is h th d t ti that shows the number and arrangement of electrons in its orbitals. Because the value of n ranges to infinity, there are an infinite g y, number of electron configurations that are possible for each atom. F each atom, all b t one of these represent the atom in an For h t ll but f th t th t i excited state. However, an atoms chemical properties are mainly associated with its g y ground state electron configuration. g That is what we will address. For example, the ground state electron configuration for a hydrogen atom is 1s (pronounced one ess one) The superscript 1 indicates that only one one one ). electron is in the s orbital. g g The ground state electron configuration for a helium atom is 1s (pronounced one ess two), where the superscript 2 indicates that there are two electrons in the s orbital. For a lithium atom it is 1s 2s Again the superscript numbers atom, 2s. Again, indicate the number of electrons in each of the orbitals.
In learning this, it is helpful to start with the f f first element in the periodic table (hydrogen), and build up the electronic structure of its atom by adding an electron to its lowest available energy level. You move on to the next element (helium) by adding a proton (and several neutrons) to the nucleus, and by adding an electron to the appropriate orbital orbital. This imaginary process of building up the ground state electronic structure for each atom, in order of atomic number, is called the aufbau principle. (Aufbau comes from a German word that means to build up.)
2) The n value of the highest occupied energy level is the period number For example, atoms of elements that have number. example electrons with n = 3 appear in period 3. Atoms of elements that have electrons with n = 6 appear in p pp period 6. 3) The square of the n value (n) equals the total number of orbitals in that energy level. Furthermore, since each orbital may h have a maximum of t i f two electrons, th maximum number l t the i b of electrons in any principle energy level is 2n. For example, with n = 2, there a e four orbitals: one 2s orbital a d three 2p , e e are ou o b a s o e s o b a and ee p orbitals. Squaring the n value gives 2 = 4. The total number of electrons in this energy level is eight, given by 2n.
Notice that there are eight elements in period 2. This is no coincidence. Compare this result with the next period. Does the pattern hold? For period 3 elements, n = 3. The number of orbitals is n = 9. , y The number of electrons is 2n = 18. However, there are only eight elements in period 3. Why? The 4s orbital has a lower energy than the 3d orbitals, and thus fills first. The fill fi t Th 3d orbitals fill after th 4 orbitals. Th f bit l ft the 4s bit l Therefore, there th are 18 elements in period 4. Recall that the 4f orbitals do not fill until after the 6s orbital fills.
The p block includes elements of groups 13 (IIIA) through 18 (VIIIA). Electron configurations of the p block atoms take the general f l form ns2npa, where a represents a value ranging f h t l i from 1 to 6. Because the three p orbitals can hold a maximum of six electrons, the p block elements span six groups. Unique among the p block elements are the atoms of group 18 (VIIIA) elements: the noble gases, renowned for their chemical y g general form stability. Their electron configuration takes the g ns2np6, representing a ground state outer energy level with fully occupied s and p orbitals. The stability of this configuration is a key factor th t d i k f t that drives the formation of chemical b d th f ti f h i l bonds.
The d block includes all the transition elements. In general, atoms of d block elements have filled ns orbitals, as well as filled or partially filled d orbitals orbitals. Generally, the ns orbitals fill before the (n - 1)d orbitals. However, there are exceptions (such as chromium and copper) because these two sublevels are very close in energy, especially at higher values of n. Because the five d orbitals can hold a maximum of ten electrons, the d block spans ten groups. The f block includes all the inner transition elements. Atoms of f block l bl k elements have filled s orbitals i th outer energy levels, t h fill d bit l in the t l l as well as filled or partially filled 4f and 5f orbitals. In general, the notation. for the orbital filling sequence is ns, followed by (n - 2)f, followed by (n - 1)d, followed by (for period 6 elements) np. However, there are many exceptions that make it difficult to predict electron configurations Because there are seven f configurations. orbitals, with a maximum of fourteen electrons, the f block spans fourteen groups. The d and f blocks are not as critical at THIS time as the s and p blocks.
Homework
Homework