http://www.chem.wisc.edu/areas/clc (Resource page) Prepared by Dr. Tony Jacob
Nuggets: Chapter 6: Electron Configurations; Orbital Energy Diagram; Orbital Box Diagram; Core vs. Valence Electrons; Charged Elements; Charged Transition Metals; Shorthand Notation; Isoelectronic; Isovalent; #Unpaired Electrons; Hunds Rule; Half-filled/Filled Subshells; Exceptions; Chapter 7: Effective Nuclear Charge; Shielding; PT Trends: Ionization Energy, Electron Affinity, Atomic Radii, Ionic Radii
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 - are outermost e - (those 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: 1s 2 2s 2 2p 6 3s 2 3p 6 4s 2 3d 10 4p 6 5s 2 4d 10 5p 6 6s 2 4f 14 5d 10 6p 6 7s 2 5f 14
the superscripts represent the number of electrons within the subshell Shorthand notation: place prior noble gas symbol in [ ]; this represents all electrons in the noble gas; e.g., Si = 1s 2 2s 2 2p 6 3s 2 3p 2 or using the shorthand notation, Si = [Ne]3s 2 3p 2 where [Ne] = 1s 2 2s 2 2p 6
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 e -
unpaired as long as possible and the electron 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 expect 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; has 2 unpaired electrons) Isoelectronic: same number of e - (e.g., N 2 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 1s 2s 3s 4s 2p 3p 4p 3d 4d 4f E n e r g y 1 electron system = H, He , Li no shielding and subshells within one energy level are at the same energy + + 2
1s 2s 3s 4s 2p 3p 4p 3d 4d 5s E n e r g ymulti-electron system leads to shielding and the subshells in one energy level shift in energy relative to one another
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 4s 3d 4p 4d 4f
Example: Draw an orbital box diagram for K: 1s 2s 3s 4s 2p 3p 3d
BE ABLE TO WRITE ELECTRON CONFIGURATIONS BY USING THE PERIODIC TABLE. 1 2 3 4 5 6 7 p d s f 2s 3s 4s 5s 6s 7s 2p 3p 4p 5p 6p 3d 5d 4d 4f 5f 1s 1s n As
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: 1s 2 ; go down 1 row and back to the left for the second row: 2s 2 2p 6 ; go down 1 row and back to the left for the third row: 3s 2 3p 6 ; finally go down 1 row and back to the left for the fourth row: 4s 2 3d 10 4p 6 . Electron configuration for As: 1s 2 2s 2 2p 6 3s 2 3p 6 4s 2 3d 10 4p 3 ; shorthand notation: [Ar]4s 2 3d 10 4p 3
CHAPTER 7 EFFECTIVE NUCLEAR CHARGE: Z eff (sometimes written as Z * ): The nuclear charge the electron experiences is different than the number of protons in the nucleus. Z eff takes into account the shielding from other electrons (which lowers Z eff ) and the penetration of the electron (which raises Z eff ); Z eff = Z S where S is a screening constant; the number of core electrons ! S Z eff ! " move left to right across a period (e.g., Z eff (Be) > Z eff (Li)) Z eff ! Z S where Z = atomic number and S = #core e - ; for Li: Z eff = 3 - 2 = +1 while for Be: Z eff = 4 - 2 = +2 Z eff ! " move down a column (e.g., Z eff (Na) > Z eff (Li)); core electrons are less effective at screening as you move down a column; using Z eff = Z S you would expect the following " Li: Z eff = 3 - 2 = +1; Na: Z eff = 11 - 10 = +1; the Z eff should be the same; however the actual Z eff values are " Li: Z eff = +1.28; Na: Z eff = +2.50 Z eff :
Shielding: Shielding or screening occurs when inner core electrons (i.e., 1s 2 2s 2 2p 6 for Na) shield or screen the interaction between the electrons in the outer shells (3s 1 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 ! " E subshell # (more stable) Slaters rule for Z eff : Use Z eff = Z S where S is the screening constant. (most instructors skip Slaters Rule) Z = atomic number (from periodic table); S = screening constant and is calculated following the steps below. Calculate S: 1. Write the electron configuration in the order with increasing n-value and grouping s and p electrons. (1s) (2s, 2p) (3s, 3p) (3d) (4s, 4p) (4d) (4f) (5s, 5p) the electrons in each parentheses are called groups and note this is not the necessarily the order of filling. 2. Any electrons to the right of the electron of interest (based on the order in step 1) are assumed to not screen that electron and are not added in to the S value " ignore; S = 0 3. Any electron in the same group " S = 0.35 4. If electron of interest is a s- or p-electron: one less than the n value of the electron of interest " S = 0.85 two less than the n value of the electron of interest " S = 1.00 5. If electron of interest is a d or f electron: all electrons to the left of the electron of interest " S = 1.00 Slaters rule Example: What is Z eff for a 5p electron in I? Z = 53; electron configuration: 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 6 4d 10 5s 2 5p 5 " (1s) 2 (2s, 2p) 8 (3s, 3p) 8 (3d) 10 (4s, 4p) 8 (4d) 10 (4f) 0 (5s, 5p) 7 ; Calculate S: 0 electrons to the right of a 5p electron " S = 0 6 electrons in the same group " S = 0.35 x 6 = 2.10 18 electrons with n value one less than the n value of the electron of interest " S = 0.85 x 18 = 15.30 28 electrons with n value two less than the n value of the electron of interest " S = 1.0 x 28 = 28.00 S = 0 + 2.10 + 15.30 + 28.00 = 45.4; Z eff = 53 45.4 = 7.6
PERIODIC TABLE TRENDS Atomic Radii: Size of the atoms; up/down columns: n! " size!; left/right in a row: Z eff # " size! i ncreas i ng 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 - (1 st ionization energy) X(g) $ X + (g) + e - IE 1 Removing the 2nd e - (2 nd ionization energy) X + (g) $ X +2 (g) + e - IE 2 Removing the 3rd e - (3 rd ionization energy) X +2 (g) $ X +3 (g) + e - IE 3 Removing the 4th e - (4 th ionization energy) X +3 (g) $ X +4 (g) + e - IE 4 i ncreas i ng 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: Z eff ! " 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 IE 1 < IE 2 < IE 3 (no exceptions); IE 1 , IE 2 , etc. = always endothermic IE 1 use X and trend; IE 2 use X + and trend; IE 3 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 X(g) + e - $ X - (g) EA 1 < 0 (-; exothermic) Adding a 2nd e - to a negative atom X - (g) + e - $ X -2 (g) EA 2 > 0 (+; endothermic) more ne gat i ve 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.) EA 1 < 0 (-) exothermic; EA 2 > 0 (+) endothermic because adding an e - to a negative species; Period 3 > Period 2 because strong e - e - repulsions in Period 2; EA Al > EA B , EA Si > EA C , EA S > EA O , EA Cl > EA F ; > = 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 (EA 1 + EA 2 for O > 0 (zero)) but is found in many compounds because of the cation-anion stabilization (e.g., Na + O -2 Na + ) Ionic Radii: anions are larger than cations; cations have larger Z eff while anions have smaller Z eff
Some Chemical Reactions by Group (not all instructors cover these reactions) Group IA 2M(s) + H 2 (g) $ 2MH(s) (H = H - = hydride) 2M(s) + S(s) $ M 2 S(s) 2M(s) + 2H 2 O(l) $ 2MOH(aq) + H 2 (g) Some reactions with O 2 yield: oxdes (O -2 ; common); peroxides (O 2 -2 ); and superoxides (O 2 - ) Group IIA M(s) + 2H 2 O(l) $ M(OH) 2 (aq) + H 2 (g) M(s) + X 2 $ MX 2 (s) (X = F, Cl, Br, I) 2M(s) + O 2 (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 O 2 and O 3
1. a. What is a possible set of the four quantum numbers (n, l, m l , m s ) for the highest energy e - in radium (Ra)? b. What is a possible set of the four quantum numbers (n, l, m l , m s ) 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 e. Te
5. Which of the following is the correct electron configuration for strontium? a. [Kr]3s 2 b. [Kr]4s 2 c. [Kr]5s 2 d. [Kr]4d 2 e. [Kr]4f 2
6. For a non-hydrogen atom, which orbital is lowest in energy? a. 2s b. 4f c. 4d d. 2p 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. N - d. 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 K 2 O? a. LiF b. Na 2 S c. S 2 O d. MgBr 2 e. H 2 O
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 e. Na II. Which of the following atoms has the lowest second ionization energy? a. Mg b. Na c. Sr d. Li e. Rb
15. Which material would most likely be the most dense? a. beryllium(s) b. lithium(s) c. boron(s) d. need additional info
16. Write the reaction for the 4 th ionization energy reaction for beryllium.
17. Predict which atom would make the most sense in having the following ionization energies: IE 1 = ~580kJ/mol IE 2 = ~1800kJ/mol IE 3 = ~2700kJ/mol IE 4 = ~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 e. Zn
19. Which atom or ion is largest? a. N -3 b. P -3 c. As -3 d. Se -2 e. Kr
20. Determine the energy for each reaction below using the data given. (Not all instructors do this type of question.) I. Br - (g) + F(g) $ Br(g) + F - (g) IE 1 for F = 1681kJ/mol IE 2 for F = 3374kJ/mol IE 3 for F = 6050kJ/mol EA 1 for F = -328kJ/mol
IE 1 for Br = 1140kJ/mol IE 2 for Br = 2104kJ/mol IE 3 for Br = 3500kJ/mol EA 1 for Br = -343kJ/mol II. O(g) + Mg(g) $ O(g) -2 + Mg(g) +2
IE 1 for O = 1314kJ/mol IE 2 for O = 3388kJ/mol IE 3 for O = 5300kJ/mol EA 1 for O = -141kJ/mol EA 2 for O = 844kJ/mol IE 1 for Mg = 738kJ/mol IE 2 for Mg = 1451kJ/mol IE 3 for Mg = 7732kJ/mol EA 1 for Mg = 0kJ/mol
21. (Skip this problem if your instructor did not cover Slaters rule.) a. What is Z eff for a 3p electron in Cl? b. What is Z eff for a 3p electron in Al? c. What is Z eff for a 3s electron in Na?
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. 1s 2 2s 2 2p 6 3s 2 3p 2 b. 1s 2 2s 2 2p 6 3s 2 3p 5 c. 1s 2 2s 2 2p 6 3s 2 3p 6 4s 2 3d 6
d. 1s 2 2s 2 2p 6 3s 2 3p 6 4s 2 3d 10 4p 6 e. 1s 2 2s 2 2p 6 3s 2 3p 6 4s 2 3d 10 4p 2 f. 1s 2 2s 2 2p 6 3s 2 3p 6 4s 2 3d 10 4p 6 5s 2 4d 10 5p 3
g. 1s 2 2s 2 2p 6 3s 2 3p 6 h. 1s 2 2s 2 2p 6 3s 1 i. 1s 2 2s 2 2p 6 3s 2 3p 6 j. 1s 2 2s 2 2p 6 3s 2 3p 6 4s 1 3d 10 k. 1s 2 2s 2 2p 6 3s 2 3p 6 4s 1 3d 5
3. a. 3s 2 3p 3 b. 1s 2 2s 2 2p 6 4. e 5. c 6. a 7. a. 1s 2 2s 2 2p 6 3s 2 3p 6 4s 2 3d 5 b. 5 c. 4 d. Co +3 or any cation with 24 electrons 8. b {Mn: [Ar]4s 2 3d 5 ; Mn +2 : [Ar]3d 5 since s electrons are removed 1 st } 9. Ti +2 {Ti: [Ar]4s 2 3d 2 ; Ti +2 : [Ar]3d 2 since s electrons are removed 1 st } 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 IE 2 : 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 IE 2 } II. c {compare +1 ions because it is IE 2 : 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 IE 2 } 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 {Since the IE 4 is so large as compared to the other IE, the removal of the 4 th electron probably breaks a noble gas configuration. Only Al breaks a noble gas configuration during IE 4 : Al +3 $ Al +4 + e - } 18. c {reaction is EA 1 ; Cl has highest EA 1 of any element (memorized)} 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) - : EA 1 for F; Br - (g) $ Br(g) : -EA 1 for Br; %H rxn = EA 1 (F) + (-EA 1 (Br)) = -328 + (-(-343)) = 15kJ/mol II. 2892kJ/mol {O(g) $ O(g) -2 : EA 1 + EA 2 for O: O(g) + e - $ O - (g) and O - (g) + e - $ O -2 (g); -141 + (844) = 703kJ/mol; Mg(g) $ Mg(g) +2 : IE 1 + IE 2 for Mg; Mg(g) $ Mg + (g) + e - and Mg + (g) $ Mg +2 (g) + e - ; 738 + 1451 = 2189kJ/mol; %H rxn = [EA 1 (O) + EA 2 (O)] + [IE 1 (Mg) + IE 2 (Mg)] = 703 + 2189 = 2892kJ/mol} 21. a. Z eff = 7.9 {Z = 17; electron configuration: 1s 2 2s 2 2p 6 3s 2 3p 5 " (1s) 2 (2s, 2p) 8 (3s, 3p) 7 ; Calculate S: 0 electrons to the right of a 3p electron " S = 0 6 electrons in the same group " S = 0.35 x 6 = 2.10 8 electrons with n value one less than the n value of the electron of interest " S = 0.85 x 8 = 6.80 2 electrons with n value two less than the n value of the electron of interest " S = 1.0 x 2 = 2.00 S = 0 + 2.10 + 6.80 + 2.00 = 10.90; Z eff = 17 10.9 = 7.9} b. Z eff = 3.5 {Z = 13; electron configuration: 1s 2 2s 2 2p 6 3s 2 3p 1 " (1s) 2 (2s, 2p) 8 (3s, 3p) 3 ; Calculate S: 0 electrons to the right of a 3p electron " S = 0 2 electrons in the same group " S = 0.35 x 2 = 0.70 8 electrons with n value one less than the n value of the electron of interest " S = 0.85 x 8 = 6.80 2 electrons with n value two less than the n value of the electron of interest " S = 1.0 x 2 = 2.00 S = 0 + 0.70 + 6.80 + 2.00 = 9.50; Z eff = 13 9.50 = 3.5} c. Z eff = 2.2 {Z = 11; electron configuration: 1s 2 2s 2 2p 6 3s 1 " (1s) 2 (2s, 2p) 8 (3s, 3p) 1 ; Calculate S: 0 electrons to the right of a 3s electron " S = 0 0 electrons in the same group " S = 0.35 x 0 = 0.0 8 electrons with n value one less than the n value of the electron of interest " S = 0.85 x 8 = 6.80 2 electrons with n value two less than the n value of the electron of interest " S = 1.0 x 2 = 2.00 S = 0 + 0.0 + 6.80 + 2.00 = 8.80; Z eff = 11 8.80 = 2.2} (Note how the Z eff is decreasing across the period; as the Z eff decreases the radii increase)
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