27.2 – Effective Nuclear Charge Because electrons are – charged, they are attracted to nuclei (which are + charged)Many properties of atoms depend not only on their electron configurations, but also on how strongly their outer electrons are attracted to the nucleus.Coulomb’s law tells us the strength of this interaction depends on the signs and magnitude of their charges, as well as the distance between them.Thus, the force of the attraction between electron and nucleus depends on the:Net nuclear charge acting on the electronAverage distance between the nucleus and the electronThis force of attraction increases as the nuclear charge increase and decreases as the electron moves farther from the nucleus.
3In many-electron atoms, each electron is simultaneously attracted to the nucleus and repelled by other electrons.Generally, there are so many electron-electron repulsions that we cannot analyze the situation exactly.We CAN estimate the net attraction of each electron to the nucleus by looking at how the electron interacts with its average environmentEnvironment created by the nucleus and the other electrons in the atom.
4Effective Nuclear Charge By looking at the average situation, we treat each electron individually as if it were moving in a net electric field created by the nucleus and the electron density of other electrons.We view this net electric field as if it results from a single positive charge located at the nucleus.This charge is called the effective nuclear charge, Zeff
5The Zeff for an electron is less than the actual nuclear charge, because it takes the electron-electron repulsions into account.So if Z = actual nuclear chargeZeff < Z
6Finding ZeffA valence electron is attracted to the nucleus, but repelled by other electrons in the atom.In particular, the electron density that is due to the inner electrons are very effective at partially canceling the attraction of the valence electron to the nucleus.We say the inner electrons partially shield or screen the outer electrons from the attraction in the nucleus.We can write a relationship between the effective nuclear charge and the number of protons in the nucleus (Z)Zeff = Z – S
7Where S is a number called the screening constant S represents how much the inner electrons shield the valence electron from the nucleus.The value of S is usually close to the number of core electrons in an atom.Valence electrons don’t shield each other, only core electrons shield.
8Expected Zeff ValuesWhat would we expect the Zeff value for Sodium to be?[Ne]3s1So Z would be 11 (11 protons)We would expect S to be 10 (10 inner, or core, electrons)So the expected Zeff value would be +1.Is this what the Zeff actually is?NoBecause the 3s orbital has a very small change of being close to the nucleus (figure 6.18(c)), there is a change of the 3s electron will have a greater attraction than normal.
9Implications?This effective nuclear charge explains energy amounts for the different l values within the same energy level (same n)2s sublevel has greater probability to be closer to nucleus than the 2p.This leads to slightly greater attractive force between nucleus and 2sWhich leads to lower energy for 2s than for 2p.This rule applies to all of the energy differences between sublevels.
10Trends in Zeff for Valence Electrons The effective nuclear charge as we move across a row (period) increases.This is because the core electrons remain the same, but the total nuclear charge increases.In other words, Z increases, but S remains the same.Going down a column (family), the effective nuclear charge changes much less than moving across.The expected nuclear charge should stay the sameBut we actually experience a slight increase in effective nuclear charge as we move down a familyBut this slight increase is MUCH less than the increase in moving across a period.
117.3 – Sizes of Atoms and Ions An important property of atoms or ions is their sizeBut don’t think of an atom or ion as a hard, spherical objectRemember, there are no sharply defined boundaries at which electrons are, then aren’tBut, we can still define atom size in several ways, based upon the distance between individual atoms in different situations.
12Ways to Determine Radius Imagine a bunch of argon atoms at room temperatureWhen they collide, the ricochet apart like pool balls.This happens because the electron clouds of each atom can’t penetrate the other atomElectrons repelThe closest distance the nuclei get during such a collision determines the apparent radii of the argon atoms.We call this radius the nonbinding atomic radius
13Now imagine a chlorine molecule (Cl2) A chemical bond holds each chlorine atom to the otherThis attractive interaction brings the atoms closer than they would be in a nonbinding collision.This distance is called the bonding atomic radius, and is shorter than the nonbinding atomic radius.
14Space-Filling ModelsSpace-filling atomic models, like the one below are based on the non-binding radii (also called the van der Waals radii) and binding radiiNon-binding radii used to determine size of each sphereBinding atomic radius used to determine how deep each sphere penetrates the other
15Chemists use different methods to measure the distance separating nuclei in molecules. In the I2 moleculeThe distance separating the nuclei is found to be 2.66Å (1 Å = m)We find the bonding atomic radius to be ½ the bond distance, so 1.33Å.Generally, the bonding atomic radius is ½ the nonbinding radius
16Where Can We Find Nonbinding Radii? pg. 266Figure 7.6Where Can We Find Nonbinding Radii?
17Periodic Trends in Atomic Radii Within each column (family) atomic radius tends to increase as you go down the column.This is primarily because of the increase in the principal quantum numberElectrons have a greater probability of being farther from the nucleus.Within each row (period), atomic radius tends to decrease from left to rightThis is primarily because of the increase in the Zeff, which draws valence electrons closer to the nucleusCausing atomic radius to decrease
18Periodic Trends in Ionic Radii The radii of ions are based upon the distances between ions in ionic compounds.Like the size of an atom, the size of an ion depends on its nuclear charge, on the # of electrons it has, and on the orbitals in which the valence electrons are found.
19CationThe formation of a cation empties the larger occupied orbitals in an atom, and also decrease the number of electron-electron repulsions.Cations will be smaller than their parent atoms
20AnionsThe formation of an anion begins to fill the larger occupied orbitals in an atom, and also increases the number of electron-electron repulsions.Anions will be larger than their parent atoms
21Similar ChargesFor ions with the same charge size increases as we go down in a column of the periodic table
23Isoelectric IonsAn isoelectric series is a group of ions that have the same number of electronsO2-, F-, Na+, Mg2+, and Al3+ all have 10 electronsIn any isoelectric series, we can list the members in order of increasing atomic number (nuclear charge)Because the number of electrons remains the same, the radius of the ions decrease with increasing atomic number, as the electrons are more strongly attracted to the nucleus
247.4 – Ionization EnergyThe ease with which electrons are removed from an atom or ion has a major effect on chemical behavior.The ionization energy of an atom or ion is the minimum energy required to remove an electron from the ground state of the gaseous atom or ion.
25The first ionization energy, or I1, is the energy needed to remove the first electron from a neutral atomNa(g) Na+(g) + e-The second ionization energy, or I2, is the minimum energy needed to remove the second electron from an ion that has already lost one electronNa+(g) Na2+(g) + e-The greater the ionization energy, the more difficult it is to remove an electron.
26Variations in Successive Ionization Energies As successive electrons are removed from an atom, the ionization energy increases for that ion.I1 < I2 < I3 and so onThis is because it is harder to pull an electron away from a more positive and positive ion.
27There is a sudden increase in ionization energy when an inner shell electron is removed. Silicon[Ne]3s23p2I1 = 786 kJ kJ/molI4 = 4360 kJ/molI5 = 16,100 kJ/molThis is because the 2p electrons are closer to the nucleus than the four 3rd shell electrons, and thus the 2p electrons experience a greater Zeff.
28Every element shows a large increase in ionization energy when electrons are removed from its noble-gas core.This lends support to the idea that only the outermost electrons (beyond the noble-gas core) are involved in bonding.The inner electrons are too tightly bound to the nucleus to be lost or even shared with another atom.
29Periodic Trends in the First Ionization Energies Within each row (period), I1 will generally increase with increasing atomic number.So alkali metals show the lowest, and noble gases show the highest.Within each column (group, the ionization energy generally decreases with increasing atomic energy.Helium has higher ionization energy than xenon.
30The representative elements show a larger range of values of I1 than transition-metals do. Generally, transition metals increase slowly as we proceed from left to right in a period.The f-block metals only show a very small increase in ionization energies.
32In general Smaller atoms have higher ionization energies. Because the same factors that effect atomic size also influence ionization energies.The energies needed to remove an electron from the outermost shell depends on both the effective nuclear charge and the distance from the nucleus.As Zeff increases, ionization energies increase.
33There are occasional irregularities within a given row. Explained by energy levelsHigher energy level generally = lower ionization energies.
34Electron Configuration of Ions When electrons are removed from an atom to form a cation, they always come from the orbitals of the highest energy level first.Iron exampleFe Fe2+[Ar]3d64s2 [Ar]3d6If we removed a 3rd electron, it would now be removed from the 3rd energy level, now that the 4th is empty.
357.5 – Electron AffinitiesThe first ionization energy of an atom measures the energy change associated with the removal of an electron from the atom to form a positively charged ion.Cl(g) Cl+(g) + e- ΔE = 1251 kJ/molThe positive ΔE tells us energy must be put into the atom to remove the electron.
36Most atoms can gain electrons to form negatively charged ions. This energy change that occurs when an electron is added to a gaseous atom is called the electron affinityMeasures the attraction, or affinity, of the atom for the added electron.For most atoms, energy is released when an electron is added.
38Ionization Energy ≠ Electron Affinity Ionization energy measures the ease with which an atom LOSES an electronElectron affinity measures the ease with which an atom GAINS an electron
39The greater the attraction between a given atom and an added electron, the more negative the atom’s electron affinity.For some elements (like the noble gases), the electron affinity has a positive value.Means the anion is higher in energy than the separated atom and electronMeans we must add energy to it to add an electron
41Trends in Electron Affinity The halogens will have the highest electron affinityGaining an electron gives them a noble-gas configurationThe electron affinities of the noble-gases, Be, and Mg are positiveAny more electrons and we’d have to start filling up in a currently-empty higher-energy subshellInteresting notes(N, P, As, Sb)The added electron gets put into an orbital that is already occupied (p subshell), leading to increased electron-electron repulsion
42As we move down a group electron affinity doesn’t change greatly. Although the electrons would be more spaced out (less electron-electron repulsion) the distance to the nucleus is greater (lower electron-nucleus attraction).
437.6 – Metals, Nonmetals and Metalloids The elements can be broadly grouped into the categories of metals, nonmetals and metalloids.
45Most elements are metals, found in the left and middle portion of the periodic table. Nonmetals are found at the top right cornerMetalloids are between the metals and nonmetals
46Metals Most have a shiny luster Conduct heat and electricity Malleable All (except mercury) are solid at room temperatureLow ionization energiesTend to form cations relatively easilyCharacterized as an “oxidizer” because they tend to lose electrons during chemical reactions.
47Metals and OthersCompounds of metals with nonmetals tend to be ionic substancesOftentimes produce oxides, a group metal ions where a metal bonds with an oxygenNiO, Na2OMost metal oxides are basicWhen they dissolve in water, they react to form metal hydroxidesThe metal hydroxides are basicThe basicity of metal oxides are due to the oxide ion.
48Nonmetals Nonmetals vary greatly in appearance Not lustrous Generally poor conductors of heat and electricityMelting points tend to be lower than those of metalsSeven nonmetals exist as diatomic moleculesH2, N2, O2, F2, Cl2, Br2, I2Nonmetals can be solids, liquids or gases at room temperature
49Chemical ReactionsBecause of their electron affinities, nonmetals tend to gain electrons when they react with metals.Compounds made entirely of nonmetals are molecular substances.Most nonmetal oxides are acidicWhen they dissolve in water they will react to form acids
50Metalloids B, Si, Ge, As, Sb, Te, At are the metalloids Have properties somewhere between metals and nonmetalsSilicon looks like a metal, but is brittle and is a poor conductor of heat and electricity than most metals.Compounds of metalloids have characteristics of the compounds of metals or nonmetals, depending on the compound.
517.7 – Group Trends for the Active Metals We’re going to look at the chemistry of the alkali metals (1A)and the alkaline earth metals (2A)
52Group 1A: The Alkali Metals Soft metallic solidsSilvery metallic luster and high thermal and electrical conducivenessNamed from the Arabic word meaning “ashes”Originally isolated from wood ashes by early chemistsLow densities and melting pointsMelting points decrease as we move down the groupDensities increase as we move down the group
53Since they have the lowest I1 values, they can have electrons very easily removed Very reactiveSo reactive, they exist in nature only as compounds.Combine directly with most nonmetals
54React vigorously with water, producing H2 gas and a solution of an alkali metal hydroxide M stands for any alkali metal2M(s) 2H2O(l) 2MOH(aq) + H2(g)This reaction is very exothermicOften enough energy is released to ignite the H2This reaction is more violet with lower alkali metals, since they more easily lose their electron, and are more reactive
55Other reactionsWhen oxygen reacts with metals, metal oxides (containing O2- ion) are formed4Li(s) + O2 2Li2OWhen dissolved in water, Li2O and other soluble metal oxides react with water to form OH- ions from the reaction of O2- with H2O
56Other alkali metals all react with oxygen to form metal peroxides, which contain the O22- ion 2Na(s) + O2(g) Na2O2(s)K, Rb, Cs also form compounds that contain the O2- ion, called superoxide ion.K(s) + O2(g) KO2(s)
57Generally Generally we only worry about the oxide formation Don’t worry about the peroxides or superoxides
58Flame TestsAlthough alkali metal ions are colorless, each emits a color when put into a flame.The ions are reduced to gaseous metal atoms, then the flame exists the valence electrons.As the valence electrons fall back, they emit light.
59Reaction ExampleWrite a balanced equation for the reaction of cesium metal with water.
60Group 2A: The Alkaline Earth Metals Like alkali metals, all solid at room temperature and have typical metallic propertiesTend to be harder, more dense and have higher melting points than the alkali metalsI1 is low, but higher than the alkali metals, so less reactive.
61Reactions Be doesn’t react with water Mg won’t react with liquid water, but will react with steamMg(s) + H2O(g) MgO(s) + H2(g)Ca, Sr, Ba and Ra will react with water (but slower than the alkali metals)Ca(s) + 2H2O(l) Ca(OH)2(aq) + H2(g)In general, tends to lose their two outer s electrons to form 2+ cations.
62Burning!Like the alkali metals, the heavier alkaline earth metals give off colors when strongly heated
637.8 – Group Trends for Selected Nonmetals HydrogenBecause it has a 1s1 electron, usually positioned with the alkali metalsBut H really doesn’t belong in any groupNot an alkali metal, because it’s usually a colorless diatomic gasThough under extreme pressure, hydrogen can be metallicLike found at the core of Jupiter or Saturn
64Reactions between hydrogen and nonmetals tend to be VERY exothermic Because there is no nuclear shielding of its sole electron, the ionization energy for H is quite highActually closer to the ionization energies for nonmetals such as O or ClLess likely to lose an electron than the alkali metalsTends to share its electrons and form molecular compoundsReactions between hydrogen and nonmetals tend to be VERY exothermicReacts with metals to form solid metal hydridesContains the hydride ion, H-This property of hydrogen gaining electrons makes it more like a halogen than an alkali metalBut hydrogen can lose its electron to form a cationH+(aq) ion is relatively common, but we’ll study it later
65Group 6A: The Oxygen Group Going down 6A, we change from nonmetallic to metallic elementsOxygen, sulfur and selenium are nonmetalsTellurium is a metalloidPolonium is a metalAll except oxygen are solids at room temperature
66Oxygen 2 common forms of oxygen O2 and O3 O2 commonly referred to as just “oxygen”O3 referred to as “ozone.”O2 is more stableThese two forms are examples of allotropesAn allotrope are different forms of the same element in the same state
67Sulfur Most stable of the sulfur allotropes is S8 Even though solid sulfur contains S8, we usually write it as S(s) to simplify stoichiometric coefficients.Like oxygen, tends to gain electrons to form sulfides, which form the S2- ionMost sulfur in nature is actually in the form of metallic sulfides.Though less likely to form sulfides than oxygen is to form oxides.
68Group 7A: The HalogensAstatine is usually left out of this group, because it’s unstable and many of its properties not yet well known.Typical nonmetalsMelting and boiling points increase with increasing atomic numberF and Cl are gasses, Br is a liquid, and I is a solidAll are diatomic
69Chemical Properties Highly negative electron affinities Tend to gain electrons from other atoms to form halide ions, X-X being used to represent any of the halogensF and Cl more reactive than Br and I