NAME _________________________________________ NOTES: UNIT 7 (1): PERIODIC TRENDS OF THE ELEMENTS I) Periodic Law: When the elements are arranged in order of increasing atomic number, there is a periodic repetition of their physical and chemical properties…establishing the concept of group chemistry (a.k.a. family chemistry) The question we should now ask is: How do we know about the atomic number? Well, it’s time for a story. HENRY MOSELEY’S BRILLANCE, THE WONDER OF RUTHERFORD’S CAVENDISH LABORATORY, AND LINKING THE ATOMIC NUMBER TO THE NUMBER OF PROTONS Henry Moseley is another one of those uber-bright folks, of whom you have never heard … But as with so many of these magnificent brains, there is quite a marvelous story to tell. All right, you must first understand the times, and what was, and was not, known. Around 1908, it is pretty well established that (there are): negative particles called electrons positive particles called alpha particles elements which chemically react similarly to their family members. ALSO…. Arrangement of the elements, on the still-developing periodic table in 1909 is by identifying the elements with a whole number (Hydrogen is 1; Helium is 2 and so forth). However, this whole number is just a placement tool, and has no real meaning or attachment to any physical characteristic of atoms or elements. Its use is to order the elements on the developing periodic table so that the elements line up correctly based upon similarities in chemical behavior (the use of the number aligns the elements in the correct families). Ernest Rutherford wins the Nobel Prize in Chemistry for his work on alpha particles, and the theory of half-life regarding radioactive isotopes. So, what are the problems? Well, as of 1908 no one knows about neutrons, protons, the nucleus, nuclear charge, electron configuration, or valence electrons. Additionally, chemists dislike using that “whole number” to organize the elements, but they have little choice. That whole number system works. Chemists and physicists are confused because the elements do not line up according to verified experimental measurements, like their relative atomic masses. Chemists and physicists cannot seem to get the relative atomic mass measurements completely correct. Based, upon the relative atomic mass, (not the chemistries) there are apparent problems with the periodic table positions of; argon to potassium, cobalt to nickel, and tellurium to iodine (Later on, this same problem is seen with thorium to protactinium.) In 1908, no one knows why. 488 Okay, celebrate the New Year and move onto 1909. Ernest Rutherford as the new director of the Cavendish Laboratories, and running high on his Nobel Prize in Chemistry, decides to attack the mystery of atomic structure. He designs his classic “gold-foil experiment”. He gets down and dirty with the gold-foil experiment (okay, he makes his students¸ Hans Geiger and Ernst Marsden get down and dirty….). But, Rutherford crunches the data. To quote Mel Brooks, “It’s good to be the king”. Loads of data are collected, and after the data are collected, it takes Rutherford about 2 years to crunch the data …. So, let a couple of New Year celebrations pass by. By 1911, Rutherford is pretty much convinced that there is a massive “nucleus” (whatever that is) at the heart of every atom. He also knows that the nucleus is positive in charge (because it deflected the positive alpha particles…whatever those are … he just knows their size and charge.) This positive nuclear charge of Rutherford’s nucleus is termed “Z”. Rutherford is clueless as to what makes up “Z”, but he hypothesizes that for atoms of the element gold, “Z” is approximately half the mass of a gold atom. (Spoiler Alert … If you think about it, protons and neutrons are often close to 1:1 ratio in non-radioactive isotopes, and they are almost the same in mass, so Rutherford’s guess at “Z” being about half the mass of the nucleus is pretty darn impressive … It turns out that “Z” is really the number of protons….but read on) Bohr gloms onto his teacher’s (yeah, Rutherford … again!) idea of the nucleus. Bohr begins to envision electrons around the nucleus (whatever that is…), since Rutherford showed that the positive charges and negative charges of the atom are not co-mingled but are separated from each other. Bohr does his bright-line emission thing for hydrogen atoms (only) … noting that the energies of the emitted wavelengths of electromagnetic energy are equal to wavelengths of visible light, which correlate to the quanta of energy absorbed and released by the electrons. It is now, 1913. (Bohr wins the Nobel Prize for Physics in 1922.) As Bohr releases his theory, Henry Moseley takes up this idea of absorbed and released energy. Using Bohr’s work (Moseley moves pretty darn fast, evidently…), he knows that x-rays are released when excited electrons, move from the second PEL (the L shell) down to the first PEL (the K shell). Moseley bombards atoms of 10 or so consecutive metal elements on the periodic table, with high-speed electrons, which displace the K-shell electrons of the bombarded atoms. (Some sources report that he bombards 12 consecutive sources … but you get the idea….) So, as the bombarded atoms get their “K” electrons knocked out, other electrons around the nucleus drop towards the nucleus filling the vacancy, and release characteristic x-rays. Moseley begins to notice that the wavelengths of the released x-rays become shorter (and thus more powerful, due to increased frequency) with increasing strength of the nuclear charge. Moseley accounts for this regular increase in x-ray emission, by suggesting that the larger the nuclear charge, the more tightly the inner K electrons are bound to it, thus releasing even more energy, as electrons fall into place. Translation: The bigger “Z”, the stronger the emitted energy. The released x-ray energy depends upon the size of the nuclear charge. 489 By taking the square root of the x-ray frequency, Moseley finds that the increase in energy is constant from one element to the next. Moseley suggests that this regular increase from element to element is caused by something in the atom by stating that there is "a fundamental quantity which increases by regular steps as we pass from one element to the next." Further work showed that this “something” really was the positive charge in the nucleus. Moseley referred to this positive charge collectively as the atomic number. CLICK Rutherford’s “Z” and Moseley’s atomic number are now seen to be the same thing! By 1918, Rutherford (sweet glory …leave something for others to do!), suggests that there is a subatomic particle, equal to the magnitude of the electron’s charge, but positive and the particle is far greater in mass. He coins the term “proton”. He further suggests that the nuclear charge is an aggregation of protons. He proves the existence of protons, using a little trick with nitrogen gas … and by 1920; he is suggesting the existence of the neutron, to make up for the rest of the mass of an isotope. [Chadwick (another student of Rutherford’s), wins the 1935 Nobel Prize in Physics for his 1932 discovery of the neutron…proving Rutherford correct!] Understanding that Z and the atomic number are related, the position of the elements of the periodic table fall into line … in that the atomic number [the nuclear charge, a.k.a. the number of protons] IS PROVEN TO BE THE APPROPRIATE organizational schema for the elements. That silly “whole number” actually turns out to be all-important. By 1914, (when he was only 26 years of age!) Moseley’s work experimentally substantiates Rutherford’s goldfoil experiment, Bohr’s work on quantized electrons and quantum theory and Rutherford’s work on the proton. Is this guy good … or what? He is all set to walk away with the 1916 Nobel Prize in Physics by most estimates, but in 1914 WWI erupts. Moseley as with so many of Britain’s younger generation of men, volunteers for service. In August of 1915, during the Battle of Gallipoli, at the age of 27, he is shot dead. His death is seen as such a blow to scientific progress, that the British Government passes a law, forbidding its most promising scientific minds from serving in combat, ever again. It still holds to this day. In 1962, Niels Bohr said, "You see actually the Rutherford work [the nuclear atom] was not taken seriously. We cannot understand today, but it was not taken seriously at all. There was no mention of it any place. The great change came from Moseley." References Kean, S. (2011). The Disappearing Spoon. Little, Brown & Company http://hyperphysics.phy-astr.gsu.edu/hbase/quantum/xrayc.html http://www4.nau.edu/microanalysis/Microprobe/Xray-MoseleysLaw.html http://www.nobelprize.org/nobel_prizes/chemistry/laureates/1908/rutherford-bio.html http://www.nobelprize.org/nobel_prizes/physics/laureates/1935/chadwick-bio.html http://en.wikipedia.org/wiki/Henry_Moseley 490 Now, this current unit of study is all about the trends of the periodic table. And while we will speak frequently about those electrons …please be sure to understand that the Periodic Law (the organization based upon Moseley’s atomic number) is what leads us towards this luxury. These are the periodic trends we need to know ATOMIC & IONIC RADII FIRST IONIZATION ENERGY ELECTRONEGATIVITY these three trends help to account for a fourth trend METALLIC &/or NONMETALLIC ACTIVITY (Why are some elements more easily oxidized or reduced than others?) II) Reasons for the periodic trends really surround the ability of an atom’s nucleus * to attract its own valence electrons and/or the electrons of another atom. A) This ability comes down to a concept called Coulombic Forces of attraction and repulsion. 1) Essentially, August Coulomb established the idea that: * like charges repel each other and unlike charges attract each other. a) Thus electrons, which are negatively charged, repel each other but attract protons. Likewise, protons repel each other. There is a mathematical expression which relates the quantity of charge and the distance between the charges: F ∝ Q1Q2 r2 …. but for our work it is reasonable to summarize this by writing that: i) the closer oppositely charged species are, the stronger the coulombic force of attraction AND ii) the closer like charged species are, there is a stronger repulsive force. 491 B) Attractive Coulombic Forces: Effective Nuclear Charge (Major Reason #4) 1) Effective nuclear charge an example of an attractive coulombic force and is often described as the pull experienced by a valence electron, for a nucleus. It is the resultant force experienced by a valence electron, after the effect &/or number of shielding (inner) electrons between the valence electron and the nucleus has been taken into account. 2) The effective nuclear charge is related to the number of valence e- of an atom, and is increased / decreased by changes (or lack of changes), in a) shielding effect (an example of a repulsive coulombic forces, between like-charge e-) b) the position of the valence e- from the nucleus (due to the number of PEL and shielding effect). This position can affect the energy of the valence e- … The weaker the ENC, the greater the energy of the valence e-. and possibly, c) valence crowding when extra e- are gained (This could explain why nonmetal anions can be oxidized back to nonmetal atoms) What Happens: As a trend: it becomes more & more difficult to remove an e- (to be oxidized), thus gaining an e- becomes more probable It becomes easier and easier to lose an electron, (to become oxidized) We can infer then that gaining becomes more and more improbable 492 Explanation of Why the Trend Happens: Attractive coulombic forces (e.g. effective nuclear charge) for valence electrons becomes stronger and stronger and valence e- are bound more tightly to the nucleus and have less energy. This increase in attractive coulombic forces is due largely to the number of core electrons remaining the same, while nuclear charge increases. Any added electrons are valence e- and they do not shield each other well… Thus shielding is essentially constant, but nuclear charge increases, causing a resultant increase in the effective nuclear charge …thus indicating an increase in attractive coulombic forces. Not only are eadded to larger and larger PELs, but the number of PELs is also increasing. This causes a lessening of the attractive coulombic forces and valance e- are actually less tightly bound to the nucleus Evidence Used To Support What Happens: but: atomic radius and metallic activity decrease, 1st ionization energy, electronegativity, electron affinity and nonmetallic, activity (the tendency to become reduced) each increase atomic radius and metallic acitivity increase; and first ionization energy & electronegativity values decrease 493 Okay, let’s take a minute and dip stick for some understanding. Use the information on the previous 2 pages, dealing with “what happens”, “why it happens”, and “the evidence we use”. Answer these questions. 1) According to the information, as you move from element to element, left to right, across Period 3 are the valence electrons being held more tightly to the nucleus or less tightly? *more tightly 2) Keep comparing the elements from left to right along Period 3. Based upon your answer to #1, should it become easier or more difficult to remove one of those valence electrons? For instance, compare Na to Cl … is it easier or will it take more energy to remove a valence electron from Cl (as compared to Na)? *it will take more energy (more difficult to remove), due to the tighter hold 3) Based upon your reading and the interpretation of the information, should the first ionization energies increase, decrease or remain the same as you move from element to element, from left to right? *increase, since first ionization energy measures the removal of an e- 4) Now compare the quantum configurations of Na 1s2 2s2 2p6 3s1 & Rb 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 5s1 The valence electron of which atom experiences the weakest effective nuclear charge? * Rb 5) Keep comparing Na and Rb. Atoms of which element have valence electrons farthest away from the nucleus? *Rb 6) Keep comparing Na and Rb. According to the information, atoms of which element should lose an electron more easily? *Rb 494 III) In-depth look at attractive coulombic forces e.g. Effective Nuclear Charge (MR #4 …part 1) 1) The changes in the periodic table trends are due to either an increase or decrease in the effective nuclear charge (Zeff) (coulombic forces) for valence electrons a) Effective Nuclear Charge: the attraction an e- "feels" for a nucleus b) Effective Nuclear Charge decreases moving down a family, resulting in a more loosely attracted (held) electrons ...Thus, e- are more easily lost to other atoms c) Effective Nuclear Charge increases as you move across a period, resulting in a tighter hold a nucleus has on its electrons ... and even more e- tend to be gained.... .... reconnect this with the Pauli Exclusion Principle and why matter has volume. Dimension (volume) allows fermions like electrons to experience a greater level of effective nuclear charge by decreasing shielding effect .... d) The larger the effective nuclear charge (Zeff) the smaller the radius, because of the stronger hold on electrons e) The effective nuclear charge can be crudely approximated using: Zeff = total #protons – non-valence electrons (or shielding electrons) This method works effectively when comparing species of a period For groups, the calculation is more complicated, using Coulomb’s Law. e.g.) Calculate and compare the effective nuclear charges of a sodium atom and a chlorine atom. Sodium has an electron configuration of [Ne] 3s1 and Chlorine has an electron configuration of [Ne] 3s2 2p5 Na: * Zeff = total #protons – non-valence electrons = 11 10 * Zeff = +1 Cl: * Zeff = total #protons – non-valence electrons = 17 12 [the 2p electrons are not shielding] * Zeff = +5 495 3) Effective Nuclear Charge and Family Trends: Consider a single family. As one moves from top to bottom the number of principal energy levels increases in the atoms of each element. The hold of the nucleus for the valence electrons lessens with each successive principal energy level Diagram of the PEL for Every Family of Elements nucleus ee- eeeeea) Because Effective Nuclear Charge (attractive coulombic forces) weaken as we go down a family …. * valence electrons are more loosely bound to the nucleus, and have greater energy, requiring a lesser ionization energy 3) To a lesser issue, there is something called Shielding Effect. Shielding Effect: The result of inner e- "blocking" the positive nucleus from the valence edue to interference and mutual repulsion (Shielding Effect is an application of repulsive coulombic forces). (MR #4 …part 2) Recall Hund’s Rule and that a) increasing shielding effect destabilizes the valence level by increasing electron energy b) decreasing shielding effect creates more stable electron configuration, because electrons are at lower energy. (MR #2, and 4 combined!!!) 496 4) Effective Nuclear Charge and Period Trends 1 Analysis of the PEL of Period 2 Elements: Groups 1 – 16 2 13 14 15 16 a) Notice that the “space” in which electrons are to be configured does not increase in terms of the number of principal energy levels. This is a key point to note. What is the consequence in terms of shielding effect, of keeping the number of inner electrons constant, across Period 2? * Shielding Effect changes as the number of inner electrons changes. Since the number of inner electrons is relatively constant across a period, like Period 2, the shielding effect is constant, or relatively unchanging. In fact, as one moves from left to right along a period of the table, an extra proton and an extra electron are added. Creating an increase in effective nuclear charge Summary for Periodic Trends The trends occur due to a strengthening / weakening in coulombic forces Group Trends: These are most easily explained by a lessening of attractive coulombic forces, caused by consistent increases in the size & number of PELs (affecting radius). Since Coulomb’s law states that attraction decreases as distance INcreases, the valence e- of higher atomic number atoms of a GROUP, to be at higher energies…thus requiring a lesser first ionization energy… having a lower electronegativity…and larger radius. These statements best explain the lessening of ionization energy, electron affinity, & electronegativity, yet increases in radius, and metallic activity. Period Trends: These are most easily explained by a strengthening of (increase in) effective nuclear charge, and thus an increase in attractive coulombic forces. The number of PEL is a constant across a period. This means that the number of core electrons remains the same, while absolute nuclear charge increases. Any added electrons are valence e- and they do not shield each other well … Thus shielding is essentially constant, but the absolute nuclear charge increases, resulting in an increase in the effective nuclear charge. This primary idea of increasing ENC, explains increases in ionization energy, electron affinity, electronegativity & nonmetallic activity BUT decreases in radius 497 III) A Short History: Working to understand the periodic trends and the work of Dimitri Mendeleev Antoine Laurent Lavoisier divided the few elements known in the 1700’s into four classes. In the early 1800's Dobereiner, noted that similar elements often had relative atomic masses and created triads. Dobereiner’s triads were followed by Cannizaro who determined relative atomic masses for the 60 or so recognized elements in the 1860s. Then Newlands arranged a table with the elements given a serial number in order of their relative atomic masses, beginning with hydrogen. This made evident that "the eighth element, starting from a given one, is a kind of repetition of the first", which Newlands called the Law of Octaves. This is the first hint (although incomplete) of what is now known as the Periodic Law. However, the Periodic Law would not make complete sense until Moseley’s work of 1913. By 1869, both Julius Lothar Meyer and Dimitri Mendeleev (Mendeleyev) constructed periodic tables independently. The periodicity of physical properties impressed Meyer, while Mendeleev was more interested in the chemical properties. As Mendeleev constructed his version of the periodic table, he "left blanks" between elements, he found chemically related, but not so closely as to go next to each other. He believed that unknown elements, would "bridge" these gaps. Mendeleev published his periodic table in 1869 and predicted the properties of the missing elements. Chemists began to appreciate it when the discovery of elements predicted by the table took place. http://periodictable.com/pages/AAE_History.html Mendeleev’s work allowed him to make predictions for undiscovered elements such as germanium, gallium, scandium, rhenium and even technetium (which really exists only due to radioactive decay)! Additionally, Mendeleev was able to correct several elements’ values for relative atomic mass. For example, the original atomic mass for indium was 76, due to the assumption that indium oxide had the formula of InO. This atomic mass placed indium, which has metallic properties, among the nonmetals. Mendeleev assumed the atomic mass was incorrect and proposed that the formula for the oxide was really In2O3. Based upon this correct formula, indium has an atomic mass of approximately 113, placing the element among the metals. He repeated this system of correction for beryllium and uranium. Zumdahl 3rd edition p 307 and Contemporary Chemistry 1981 p131 Mendeleev's Genius Studied Properties Predicted Values for Ekasilicon Atomic Mass (1871) 72 Experimentally Determined Properties of Germanium (1886) *72.32 Density 5.5 g/cm3 5.47 g/cm3 Specific Heat 0.31 J/(gK) 0.32 J/(gK) Melting Point very high 960C Oxide Formula (oxidation #) XO2 GeO2 Oxide Density 4.7 g/cm3 4.70 g/cm3 Chloride Formula (oxidation #) XCl4 (X = +4 oxidation state) Specific Gravity 5.5 GeCl4 (Ge = +4 oxidation state) 5.47 NB: While your teacher waxes nostalgically regarding Dimitri Mendeleev’s genius ... it is fair to note that he pulled some really odd ideas out of that magnificent brain as well. For instance, (rather inexplicitly), he put hydrogen in a group (family) with copper, silver and mercury!!! http://web.lemoyne.edu/~giunta/EA/MENDELEEVann.HTML Additionally, Dimitri Mendeleev never accepted the concept of … the electron! This giant gaff should tell you that those years were chaotic, and illustrate, just how important both a community of thinkers, & the freedom to think, really are. Check out: http://www.wimp.com/thegenius/ 498 The values for the First Ionization Energy, Electronegativity and Atomic Radius are listed for most elements on Table S . IV) Electronegativity: a unit-less value which implies the tendency of an atom to *attract the electrons of a different atom (Major Reason #4 …part 3) to which it is bonded. The scale runs from 0.7 to 4.0 Trends to Know: __Ionization Energy __Electronegativity __Atomic Radius __Ionic Radius __Metallic & Nonmetallic Activity. http://employees.csbsju.edu/hjakubowski/classes/ch111/olsg-ch111/chembond/2atomspolarcoval.gif A) As you move left to right across a period electronegativity values * tend to increase As you move down a group electronegativity values * tend to decrease (just like ionization energies) 1) The Pauling Scale is a scale of 0.7 to not likely to attract an e- 3.98 (most texts round that to 4.0, which was the original upper value) very likely to attract the e- in a bond 2) evaluates the tendency of one atom to attract the bonding electron(s) of a different atom in a bond. 3) In an ionic bond, one species pretty much dominates the other, rather completely, by gaining the electron fully, while the other species loses that same electron, fully. This creates fully realized + and – charged species 4) In a covalent bond, the species are so close in this attractive ability, that no one species can completely dominate & thus gain the bonding electrons. Rather, there’s an accommodation or a compromise reached between the attractive and repulsive forces, creating a sharing of the bonding electron. This has a tremendous consequence: This sharing creates partial + and - oxidation states which lack the magnitude of a full positive or negative charge. This partial charge is symbolized by a charge and the small case form of the Greek letter, delta (± ) 499 Atoms with larger electronegativity values tend to acquire the electrons of a bond, and the atom becomes partially negative in oxidation state. No difference in the ability to gain δ+ A : 3.0 A 3.0 δ: X 3.5 A 3.0 δA : 3.0 Bonding e- are more attracted to the more electronegative atom. δ+ X 2.2 Electronegativity Values NA 2.1 1 2 13 14 15 16 17 18 1.0 1.6 2.0 2.6 3.0 3.5 4.0 NA 0.9 0.8 Why would “not applicable” be used to represent the electronegativity for the noble gases? 0.8 0.8 0.7 B) Given the following bonded atoms, and the above electronegative values, assign partial charges to each atom of the molecule. .. H:F: . . .. :O:F .. H:N:H . . . . F H .. .. :O:: C::O: 500 1) a large electronegativity value, such as fluorine’s * 4.0 indicates that the nuclei of atoms of fluorine have a * strong tendency / ability to attract electrons of (a) bond(s) 2) a small electronegativity value, such as cesium’s 0.7 indicates the the cesium nuclei * have relatively no ability to attract electrons of bonds ....thus atoms of Cs, will inevitably lose all control over the bonding electron V) First Ionization Energy: The number of kJ required to remove 1 mol of the most loosely held electrons from 1 mol of atoms in the gaseous phase. Trends to Know: __Ionization Energy __Electronegativity __Atomic Radius __Ionic Radius __Metallic & Nonmetallic Activity. http://sun.menloschool.org/~dspence/chemistry/atomic/ionization.html A) As you move from left to right across a period of elements, the first ionization energy tends to * increase / become larger 1) This means that as you go across a period, it requires more and more * energy to * remove / lose * oxidation The process of * reduction the most loosely held electron. Thus the process of becomes more and more difficult and less likely to occur. is therefore more likely as you move right. 501 B) As you move down a family (or group) of elements, the first ionization energy tends to * decrease 1) This means that as you go down a group, it requires * less energy * remove (to lose) the most loosely held electron. Thus the process of * oxidation (ionization) becomes * easier (quicker, more likely) The process of * reduction (gaining an e-) down a group. C) to is therefore, less likely farther e.g. 496 kJ + 1 mole Na0 1 mole Na1+ + 1 mole e1251 kJ + 1 mole Cl0 1 mole Cl1+ + 1 mole e- (a larger value suggests that this oxidation is much less likely to occur relative to sodium's) First Ionization Values Visualized 2372 1312 520 900 801 1086 1402 1314 1681 2081 496 419 403 376 393 502 1) A large value such as helium’s 2,372 kJ/mol means * It requires a relatively large amount of energy to remove the valence electron(s) of 1 mol of helium atoms. Due to such large energy requirements, this oxidation will probably not occur naturally, on Earth. 2) A small value such as potassium’s 419 kJ/mol means * relatively little energy is needed to have the most loosely held electrons removed. Thus, potassium atoms are more likely than helium to be oxidized. 3) these values help to compare atoms as to which is more likely to be * oxidized if reacted chemically. VI) Covalent (Atomic) Radius: Often defined as ½ the distance between two nuclei of bonded atoms of the same element. X X A) The radius of an atom can change, depending upon the atom(s) to which it is bonded. Thus this is a rather highly generalized trend due to differences in measurement. 1) Trend from left to right across a period: *decrease in atomic radius Trends to Know: __Ionization Energy __Electronegativity __Atomic Radius __Ionic Radius __Metallic & Nonmetallic Activity. Thus: valence electrons are * attracted to their own nucleus more strongly ______________. Thus the chance for becoming * oxidized and the chance for becoming * reduced decreases increases. 2) Trend from top to bottom down a family: * increase in the size of the atomic radius due to an increasing number of PEL’s 3) It is important to grasp the trend in atomic radius, for it can be applied to trends in ionic radius. a) For instance …. K0 has a larger atomic radius than Na0, thus K+ while smaller than K0, the K+ is larger than Na+ … Thus if we know the atomic radius trend, the ionic radius trend (when comparing) will hold. 503 Trends in Atomic Radii as well as Changes in Ionic Radii http://cwx.prenhall.com/bookbind/pubbooks/hillchem3/medialib/media_portfolio/08.html Key Atom Ion 1 2 13 14 15 16 17 VII) Ionic Radius: *Generally refers to the size of an ion A) When a metal atom is oxidized and becomes a cation, the ionic radius of the cation is *smaller Na0 than the atomic radius of the original metal atom 1) so the cation has a *smaller radius Na+1 than the metal atom 2–8–1 2-8 B) When a nonmetal atom is reduced and becomes an anion, the ionic radius of the anion is * larger than the atomic radius of the original nonmetal atom Cl0 1) the anion has a * greater radius Cl-1 than the nonmetal atom 2–8–7 2-8–8 due to increased electron /electron repulsion in the valence level. There is an increase in the repulsive forces (due to the extra e-) as the (-) electrons interact, resulting in an increase in radius. You see, greater distance between e- helps to reduce the effect of those repulsive forces. 504 VIII) Metallic Activity: * The tendency of an atom to be oxidized (lose electrons) in a chemical reaction A) Study Period 2 of the Periodic Table: _______________________________________ B) Study Group 14 of the Periodic Table: ________________________________________ C) High metallic activity is linked to the nucleus’ inability to attract effectively its own valence eTrends to Know: __Ionization Energy __Electronegativity __Atomic Radius __Ionic Radius __Metallic & Nonmetallic Activity. Thus atoms with a high metallic activity tend to * lose electrons or high metallic activity is associated with atoms that are easily * oxidized This poor attraction links up with: Lower first ionization energy Lower electronegativity Larger atomic radius Losers of electrons IX) NONmetallic Activity: * The tendency to gain electrons (become reduced) A) High NONmetallic activity is linked to the nucleus’ tremendous ability to hold onto its own electrons and attract electrons from other atoms. Thus atoms with a high NONmetallic activity tend to *gain electrons or high NONmetallic acitivity is associated with atoms that are easily * reduced This strong attraction links up with: GREATER first ionization energy GREATER electronegativity Smaller atomic radius The following are additional ideas regarding atomic radius to help clarify, and to consider. Essentially, the following is the "fine print", dealing with; dioxygen, dinitrogen, the noble gases Atomic Radius Calculations for Metals and Som Non-metals Like Oxygen and Nitrogen etc… The atomic radius is half the distance apart of two atoms of the element in its normal state. The atomic radius of a metal depends on its co-ordination numbers, or number of nearest neighbors. For a non-metal the atomic radius is half the distance between a pair of bonded atoms of the element. Molecules such as oxygen and nitrogen are multiply bonded so the atomic radii of these elements are calculated from molecules such as hydrogen peroxide (HOOH) and hydrazine (H2NNH2) which contain only single bonds. Gases like neon, which are atomic rather than molecular and are not known to form compounds, are more of a problem. Their radii are calculated from the structures the elements adopt at (near) absolute zero. See the next page, for more on the noble gases. http://www.chemsoc.org/viselements/pages/radii.html 505 Atomic Radius Determination For The Noble Gases For our current work on “trends” in atomic radius, it seems like you have to ignore the noble gas at the end of each period. Because neon and argon don't form bonds, you can only measure their van der Waals radius - a case where the atom is pretty well "un-squashed". All the other atoms are being measured where their atomic radius is being lessened by strong attractions. You aren't comparing like with like if you include the noble gases. http://www.chemguide.co.uk/atoms/properties/atradius.html http://www.chemguide.co.uk/atoms/properties/at Additionally, atomic radii are called covalent radii when referring to non-metallic elements and are called metallic radii when referring to metals. Technically, the atomic radius is one half of the equilibrium inter-nuclear distance between two adjacent atoms (which may either bonded covalently or present in a closely packed crystal lattice) of an element. A covalent radius is one-half the distance between nuclei of two of the same atoms that are bonded to each other. Covalent radii for elements whose atoms cannot bond to each another can be estimated by combining radii of those that do with the distances between unlike atoms in various molecules. A metallic radius is one-half of the closest inter-nuclear distance in a metallic crystal. http://en.wikipedia.org/wiki/Atomic_radius REMEMBER / RECALL / DON'T FORGET / HOLD ONTO THE IDEA Effective Nuclear Charge decreases as you move down a family, bc of more PEL and more shielding thus causing the electrons to be held more loosely Effective Nuclear Charge increases as you move across a period, bc of a buildup of opposite charges attracting in a limited space, thus causing the electrons to be held more tightly to the nucleus, and thus "shrinking" the size of the atom, despite more subatomic particles. 506 DIRECTIONS: Use your reference tables and answer each question by selecting the most correct response to each. 1) Think: Periods run horizontally The elements in Period 3 all contain the same number of: 1) 2) 3) 4) protons neutrons valence electrons occupied principal energy levels 2) Think: What do you know about nonmetals? What information does Table S give you? Compared to atoms of metals, atoms of nonmetals generally: 1) 2) 3) 4) have higher electronegativity values have lower first ionization energies conduct electrical currents more readily lose electrons more readily 3) Compared to an atom of potassium, an atom of calcium has a 1) 2) 3) 4) larger radius and a less active metal larger radius and a more active metal smaller radius and less active metal smaller radius and more active metal 4) Think: Hey use Table S and look up values!!! In Period 2 of the Periodic Table, which Group contains the element with the highest first ionization energy? 1) alkali metals 2) alkaline-earth metals 3) halogens 4) noble gases 5) As the atoms of the elements in Group1 of the Periodic Table are considered from top to bottom, the number of valence electrons in the atoms of each successive element 1) decreases 2) increases 3) remains the same 6) Elements in the Periodic Table are arranged according to their 1) atomic number 2) atomic mass 3) relative activity 4) relative size 7) Think: What term is used to describe the “attraction for electrons”? Now look up Table S. Which of the following elements has the strongest attraction for electrons? 1) boron 2) aluminum 3) oxygen 4) sulfur 507 8) Think: What is meant by “nuclear charge”? What occurs as the atomic number of the elements in Period 2 increases? 1) The nuclear charge of each successive atom decreases, and the covalent radius decreases 2) The nuclear charge of each successive atom decreases, and the covalent radius increases 3) The nuclear charge of each successive atom increases, and the covalent radius decreases 4) The nuclear charge of each successive atom increases, and the covalent radius increases 9) An element has a first ionization energy of 1314 kJ, and an electronegativity of 3.5. It is classified as a 1) metal 2) nonmetal 3) metalloid 4) halogen 10) The properties of carbon are expected to be most similar to those of 1) boron 2) aluminum 3) silicon 4) phosphorus 11) At which location in the Periodic Table would the most active metallic element be found? 1) in Group 1 at the top 2) in Group 1 at the bottom 3) in Group 17 at the top 4) in Group 17 at the bottom 12) Think: Chlorine is a nonmetal. What occurs when an atom of chlorine forms a chloride ion? 1) 2) 3) 4) The chlorine atom gains an electron, and its radius becomes smaller The chlorine atom gains an electron, and its radius becomes larger The chlorine atom loses an electron, and its radius becomes smaller The chlorine atom loses an electron, and its radius becomes larger 13) Think: What is true about a Period of the PT? As the elements in Period 2 of the Periodic Table are considered in succession from left to right, there is a decrease in atomic radius with increasing atomic number. This may be explained, in part, due to the fact that the number of protons, 1) 2) 3) 4) increases, increases, decreases, decreases, and the number of and the number of and the number of and the number of shells of electrons remains the same shells of electrons increases shells of electrons remains the same shells of electrons increases 508 14) The strength of an atom's attraction for the electrons in a chemical bond is the atom's 1) electronegativity 2) ionization energy 3) heat of reaction 4) heat of formation 15) Germanium is classified as a 1) metal 2) metalloid 3) nonmetal 4) noble gas 16) This equation represents the formation of a 1) fluoride ion, which is smaller in radius than a fluorine atom 2) fluoride ion, which is larger in radius than a fluorine atom 3) fluorine atom, which is the same in radius as a fluoride ion 4) fluorine atom, which is larger in radius than a fluoride ion 17) When a lithium atom forms a Li+ ion, the lithium atom 1) gains a proton 2) gains an electron 3) loses a proton 4) loses an electron 18) Electronegativity is a measure of an atom's ability to 1) 2) 3) 4) attract the electrons in the bond between the atom and another atom repel the electrons in the bond between the atom and another atom attract the protons of another atom repel the protons of another atom 19) Think: What type of elements are “brittle”? Which element is brittle in the solid phase and is a poor conductor of heat and electricity? 1) calcium 2) sulfur 3) strontium 4) copper 20) How does the size of a barium ion compare to the size of a barium atom? 1) 2) 3) 4) The ion is smaller because it has fewer electrons The ion is smaller because it has more electrons The ion is larger because it has fewer electrons The ion is smaller because it has more electrons 509 21) Which of the following groups in the Periodic Table contain elements so highly reactive they are never found in the free state? 1) 1 and 2 2) 1 and 11 3) 2 and 15 4) 11 and 15 22) Think: What class of elements have high electronegativity values? Which element at STP is a poor conductor of electricity and has a relatively high electronegativity? 1) Cu 2) S 3) Mg 4) Fe 23) Think: What terms of periodic trends is associated most closely with the ability to “attract electrons”? Which element is lowest? Which of these elements in Period 3 has the least tendency to attract electrons? 1) Mg 2) Al 3) S 4) Cl 24) In which area of the Periodic Table are the elements with the strongest nonmetallic properties located? 1) lower left 2) upper left 3) lower right 4) upper right 25) Think: What measurement is associated with the loss of electrons? Look up information on Table S. Which of these metals loses electrons most readily? 1) calcium 2) magnesium 3) potassium 4) sodium 26) Bullet at least 4 reasons a student might use to explain why atoms of fluorine are reduced more readily than atoms of bromine. (That is, provide 4 reasons why fluorine is a more active nonmetal than bromine) 510 27) Bullet at least 4 reasons a student might use to explain why atoms of potassium are oxidized more easily than atoms of calcium. 28) Bullet at least 4 reasons a student can use to explain why atoms of potassium are oxidized more easily than atoms of sodium Answers: 1 -25 1) 4 2) 1 3) 3 4) 4 5) 3 Members of the same family based upon their common number of val. e- 6) 1 7) 3 8) 3 10) 3 It is in the same family (has the same # val. e-) 13) 1 14) 1 15) 2 17) 4 18) 1 11) 2 12) 2 9) 2 16) 2 19) 2 Did you note that 3 of them are metals and only 1 is a nonmetal? Think … this matters… 20) 1 Ba is a metal and metals lose electrons. 21) 1 22) 2 It’s asking about nonmetals. Did you note that three of the choices are metals and only one is a nonmetal? 23) 1 24) 4 Excluding the noble gases, O,F,Cl are the big nonmetal hitters. 25) 3 It has the lowest first ionization energy 26) Here are a few ideas: atoms of fluorine have a stronger effective nuclear charge than atoms of bromine atoms of fluorine have a greater first ionization energy atoms of fluorine have a greater electronegativity atoms of BROMINE have more principal energy levels, (a larger atomic radius) thus a weaker hold on valence electrons (atoms of BROMINE have a weaker effective nuclear charge) Variations of the above apply to 27 and 28 511