ELECTRON CONFIGURATIONS Valence e-: Valence e- are the s and p e- just past the last noble gas.

. (Note: Sometimes d-orbital e- are also considered valence e-; it depends on the specific situation.) Valence e- = outer e- (on the atom surface); the valence e- determine the chemical reactions an atom undergoes Core e-: The e- that are not the valence e-; the noble gas electrons when using the shorthand notation; the core e- are not involved in common chemical reactions e- fill orbitals in a particular order: 1s22s22p63s23p64s23d104p65s24d105p66s24f145d106p67s25f14 the superscripts represent the number of electrons within that subshell Shorthand notation: place prior noble gas symbol in [ ]; this represents all electrons in the noble gas; e.g., Si = 1s22s22p63s23p2 or using the shorthand notation, Si = [Ne]3s23p2 where [Ne] = 1s22s22p6 Charged species add electrons (anions) or remove electrons (cations) from the last subshell Charged transition metals remove s-electrons first when ionizing, not the d-electrons! Hund's rule: The lowest energy e- configuration (called the ground state configuration), is the one with eunpaired and the spin maximized Exceptions: Common ones: Cr, Mo and Cu, Ag, Au because half-filled and filled subshells are more stable than partially filled subshells (some instructors except students to have the exceptions memorized) Determine number of unpaired electrons in both neutral and charged species ignore electrons in filled subshells and core electrons as these electrons are all paired Diamagnetic: All e- paired (e.g., Mg is diamagnetic) Paramagnetic: At least 1 e-unpaired (e.g., C is paramagnetic) Isoelectronic: same number of e- (e.g., N2 and CO are isoelectronic) Isovalent: same number of valence e- (e.g., Si and C, or P- and O are isovalent)

ORBITAL ENERGY DIAGRAM In 1e- systems, all subshells within one energy levels have the same energy. In multi-electron systems, e-e- interactions change the energies of subshells within one energy level
5s

4s
Energy

4p 3p 2p

4d +2 1 electron system = H, He +, Li no shielding and subshells within one energy level are at the same energy 3d

4f

4s

4p 3p 2p

4d 3d multi-electron system leads to shielding and the subshells in one energy level shift in energy relative to one another

2s

Energy

3s

3s 2s

1s

1s

Whichever subshell fills first will have a lower energy. (e.g., 2s is lower in energy than 2p) Orbital Box Diagram: (Note: The boxes have been placed in order of n value, not the order of filling!)
1s 2s 2p 3s 3p 3d
1s 2s

4s
2p

4p
3s 3p

4d
3d 4s

4f

Example: Draw an orbital box diagram for K:

BE ABLE TO WRITE ELECTRON CONFIGURATIONS BY USING THE PERIODIC TABLE.

s n 1 1s 2s 2 3s 3 4 4s 5 5s 6 6s 7 7s p
2p 1s

d
3d 4d 5d
As

3p 4p 5p 6p

f
4f 5f

Example: Write the electronic configuration of As (shown on Periodic Table above) in the ground state. Read the PT starting in the upper left corner left to right; when you get to the end of the PT on right side, go back all the way to the left side and go down 1 row; as you read across, each element box will represent 1e-; the electrons are written as superscripts; the subshells are shown in the PT above; the PT is organized by electron configuration such that all the subshells are grouped together. The first row: 1s2; go down 1 row and back to the left for the second row: 2s22p6; go down 1 row and back to the left for the third row: 3s23p6; finally go down 1 row and back to the left for the fourth row: 4s23d104p6. Electron configuration for As: 1s22s22p63s23p64s23d104p3; shorthand notation: [Ar]4s23d104p3

CHAPTER 7 EFFECTIVE NUCLEAR CHARGE: Zeff (sometimes written as Z*): The nuclear charge the electron experiences is different than the number of protons in the nucleus. Zeff takes into account the shielding from other electrons (which lowers Zeff) and the penetration of the electron (which raises Zeff); Zeff = Z S where S is a screening constant; the number of core electrons S Zeff move left to right across a period (e.g., Zeff (Be) > Zeff (Li))
Zeff Z S where Z = atomic number and S = #core e-; for Li: Zeff = 3 - 2 = +1 while for Be: Zeff = 4 - 2 = +2

Zeff move down a column (e.g., Zeff (Na) > Zeff (Li)); core electrons are less effective at screening as you move down a column; using Zeff = Z S you would expect the following Li: Zeff = 3 - 2 = +1;
Na: Zeff = 11 - 10 = +1; the Zeff should be the same; however the actual Zeff values are Li: Zeff = +1.28; Na: Zeff = +2.50

Zeff: Shielding: Shielding or screening occurs when inner core electrons (i.e., 1s22s22p6 for Na) shield or screen the interaction between the electrons in the outer shells (3s1 for Na) and the nuclear charge Penetration: How close an e- is to the nucleus; average penetration: s > p > d > f in the same energy level n (i.e., 4s penetrates more than 4p); Penetration Esubshell (more stable)

PERIODIC TABLE TRENDS Atomic Radii: Size of the atoms; up/down columns: n size; left/right in a row: Zeff size
increasing

Increases down and to the left on Periodic Table. First Ionization Energy: The energy required to remove the first electron from a gaseous atom. Removing the 1st e- (1st ionization energy) Removing the 2nd e- (2nd ionization energy) Removing the 3rd e- (3rd ionization energy) Removing the 4th e- (4th ionization energy)
increasing

X(g) X+(g) + eX+(g) X+2(g) + eX+2(g) X+3(g) + eX+3(g) X+4(g) + e-

IE1 IE2 IE3 IE4

Generally increases up and right on Periodic Table; values are always positive (endothermic); as atom gets smaller, IE; up/down columns: n IE; left/right in row: Zeff IE Exceptions: Be family higher than B family (B has a higher energy 2p electron); N family higher than O family because of electron-electron repulsions in O family IE1 < IE2 < IE3 (no exceptions); IE1, IE2, etc. = always endothermic IE1 use X and trend; IE2 use X+ and trend; IE3 use X+2 and trend Electron Affinity: The energy change associated with the addition of an electron to a neutral gaseous atom to form a negatively charged gaseous atom. Adding an e- to a neutral atom Adding a 2nd e- to a negative atom
more negative

X(g) + e- X-(g) X-(g) + e- X-2(g)

EA1 < 0 (-; exothermic) EA2 > 0 (+; endothermic)

Generally more negative up and to the right on the Periodic Table (more negative is more favorable). Negative value energy given off. Trend has exceptions. (Some instructors expect
students to know the EA exceptions; check with your instructor.)

EA1 < 0 (-) exothermic; EA2 > 0 (+) endothermic because adding an e- to a negative species; Period 3 > Period 2 because strong e-e- repulsions in Period 2; EAAl > EAB, EASi > EAC, EAS > EAO, EACl > EAF; > = more negative Be, Mg (filling higher energy subshell); N atom (half-filled subshell so high e-e- repulsions), and noble gases (filling higher energy subshell) have EA 0 Cl has the highest EA (most negative) value of any element O-2 is not favored to form (EA1 + EA2 for O > 0 (zero)) but is found in many compounds because of the cation-anion stabilization (e.g., Na+O-2Na+)

Ionic Radii: anions are larger than cations; cations have larger Zeff while anions have smaller Zeff

Some Chemical Reactions by Group (not all instructors cover these reactions) Group IA 2M(s) + H2(g) 2MH(s) (H = H- = hydride) 2M(s) + S(s) M2S(s) 2M(s) + 2H2O(l) 2MOH(aq) + H2(g) Some reactions with O2 yield: oxdes (O-2; common); peroxides (O2-2); and superoxides (O2-) Group IIA M(s) + 2H2O(l) M(OH)2(aq) + H2(g) M(s) + X2 MX2(s) (X = F, Cl, Br, I) 2M(s) + O2(g) 2MO(s) Metals low IE tend to form cations; Nonmetals high EA tend to form anions Allotropes: an element can take on several naturally occurring forms (e.g., C: diamond, graphite, Buckyballs) Oxygen can be found as O2 and O3 1. a. What is a possible set of the four quantum numbers (n, l, ml, ms) for the highest energy e- in radium (Ra)? b. What is a possible set of the four quantum numbers (n, l, ml, ms) for the highest energy e- in cesium (Cs)? 2. Write the ground state electron configuration without abbreviations for each atom or ion. a. Si b. Cl c. Fe d. Kr e. Ge f. Sb g. K+ h. Si+3 i. S-2 j. Cu k. Cr 3. a. What are the valence electrons for P? b. What are the core electrons for Cl? 4. Which of the following atoms has the largest number of valence electrons? a. P b. Al c. Sr d. Sb 5. Which of the following is the correct electron configuration for strontium? a. [Kr]3s2 b. [Kr]4s2 c. [Kr]5s2 d. [Kr]4d2 6. For a non-hydrogen atom, which orbital is lowest in energy? a. 2s b. 4f c. 4d d. 2p e. Te e. [Kr]4f2 e. 3d

7. a. Write the electron configuration for Mn. Do not use abbreviations. b. How many unpaired electrons does Mn have? c. How many unpaired electrons does Mn+3 have? d. List one cation that is isoelectronic with Fe+2? (There are many possible answers here.) 8. Which atom or ion has the most unpaired electrons in the ground state? a. Si b. Mn+2 c. Nd. Pb+2

e. P

9. Which atom or ion does not have zero unpaired electrons in the ground state? Na+, He, P-3, Ti+2 10. The second ionization energy for any element is a. always about the same as the first ionization energy. b. larger or smaller than the first ionization energy depending on the element. c. always smaller than the first ionization energy. d. predicted using Hund's Rule. e. always larger than the first ionization energy.

11. Which compound would be expected to possess the most similar chemical properties to K2O? a. LiF b. Na2S c. S2O d. MgBr2 e. H2O 12. In each set, select those elements/ions/compounds which are isoelectronic? a. Cl-, Ar, F-, Br-, Ca+1 b. CN-, Si, S-2, Mg-2, Ca+2 13. On the basis of periodic trends rank the elements Al, Rb, and Ca in order of their increasing atomic radii. a. Rb < Ca < Al b. Ca < Rb < Al c. Al < Ca < Rb d. Rb < Al < Ca e. Al < Rb < Ca 14. I. Which of the following elements will have the highest second ionization energy? a. Be b. Li c. K d. Mg II. Which of the following atoms has the lowest second ionization energy? a. Mg b. Na c. Sr d. Li 15. Which material would most likely be the most dense? a. beryllium(s) b. lithium(s) c. boron(s) d. need additional info e. Na e. Rb

16. Write the reaction for the 4th ionization energy reaction for beryllium. 17. Predict which atom would make the most sense in having the following ionization energies: IE1 = ~580kJ/mol IE2 = ~1800kJ/mol IE3 = ~2700kJ/mol IE4 = ~11,600kJ/mol a. Li b. Mg c. C d. Al e. none of the above 18. Which of the following will release the most energy in the process: E + e- E-? a. I b. B c. Cl d. Cs 19. Which atom or ion is largest? a. N-3 b. P-3 c. As-3 d. Se-2

e. Zn

e. Kr

20. Determine the energy for each reaction below using the data given. (Not all instructors do this type of question.) IE1 for F = 1681kJ/mol IE1 for Br = 1140kJ/mol I. Br-(g) + F(g) Br(g) + F-(g)
IE2 for F = 3374kJ/mol IE3 for F = 6050kJ/mol EA1 for F = -328kJ/mol IE2 for Br = 2104kJ/mol IE3 for Br = 3500kJ/mol EA1 for Br = -343kJ/mol

II. O(g) + Mg(g) O(g)-2 + Mg(g)+2

IE1 for O = 1314kJ/mol IE2 for O = 3388kJ/mol IE3 for O = 5300kJ/mol EA1 for O = -141kJ/mol EA2 for O = 844kJ/mol

IE1 for Mg = 738kJ/mol IE2 for Mg = 1451kJ/mol IE3 for Mg = 7732kJ/mol EA1 for Mg = 0kJ/mol

ANSWERS 1. a. (7, 0, 0, +1/2) or (7, 0, 0, -1/2) b. (6, 0, 0, +1/2) or (6, 0, 0, -1/2) 2. a. 1s22s22p63s23p2 b. 1s22s22p63s23p5 c. 1s22s22p63s23p64s23d6 d. 1s22s22p63s23p64s23d104p6 e. 1s22s22p63s23p64s23d104p2 f. 1s22s22p63s23p64s23d104p65s24d105p3 g. 1s22s22p63s23p6 h. 1s22s22p63s1 i. 1s22s22p63s23p6 j. 1s22s22p63s23p64s13d10 k. 1s22s22p63s23p64s13d5 3. a. 3s23p3 b. 1s22s22p6 4. e 5. c 6. a 7. a. 1s22s22p63s23p64s23d5 b. 5 c. 4 d. Co+3 or any cation with 24 electrons 8. b {Mn: [Ar]4s23d5; Mn+2: [Ar]3d5 since s electrons are removed 1st} 9. Ti+2 {Ti: [Ar]4s23d2; Ti+2: [Ar]3d2 since s electrons are removed 1st} 10. e 11. b {elements in the same family have similar chemical properties} 12. a. Cl-, Ar b. CN-, Si, Mg-2 13. c 14. I. b {compare +1 ions because it is IE2: Be+(3e-), Li+(2e-), K+(18e-), Mg+(11e-), Na+(10e-) by placing them on the PT (e.g.,
Na+ would be placed on Ne on the PT); then whichever is highest and to the right will have highest IE2} II. c {compare +1 ions because it is IE2: Mg+(11e-), Na+(10e-), Sr+(37e-), Li+(2e-), Rb+(36e-) by placing them on the PT (e.g., Rb+ would be placed on Kr on the PT); then whichever is lowest and to the left will have lowest IE2} 15. c {D = m/V; B would be the smallest in size and has the greatest mass so would be the most dense} 16. Be+3(g) Be+4(g) + 1e-

17. d

18. 19. c {greater the negative charge, nearly always the larger it is; given three -3 anions, the largest is the one furthest down the PT} 20. I. 15kJ/mol {F(g) F(g)- : EA1 for F; Br-(g) Br(g) : -EA1 for Br; Hrxn = EA1(F) + (-EA1(Br)) = -328 + (-(-343)) =
15kJ/mol

{Since the IE4 is so large as compared to the other IE, the removal of the 4th electron probably breaks a noble gas configuration. Only Al breaks a noble gas configuration during IE4: Al+3 Al+4 + e-} c {reaction is EA1; Cl has highest EA1 of any element (memorized)}

II. 2892kJ/mol {O(g) O(g)-2 : EA1 + EA2 for O: O(g) + e- O-(g) and O-(g) + e- O-2(g); -141 + (844) = 703kJ/mol;
Mg(g) Mg(g)+2 : IE1 + IE2 for Mg; Mg(g) Mg+(g) + e- and Mg+(g) Mg+2(g) + e-; 738 + 1451 = 2189kJ/mol; Hrxn = [EA1(O) + EA2(O)] + [IE1(Mg) + IE2(Mg)] = 703 + 2189 = 2892kJ/mol}