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Chemistry 1311

Problem Set 1

1. Calculate the ratio of the energies of the n=3 to n=1 transitions of the hydrogen atom and the Li2+ ion. The energy of a transition is given by E = -13.6Z2 eV (1/nf2-1/ni2). Since both n values for the transitions in question are the same the ratio of the energies is determined only by the ratio of the Z2 values or (1)2/(3)2 = 1/9. Thus the energy of the n=3 to n=1 transition in Li2+ ion is 9 times greater than that for H atom. 2. How many orbitals can have the designations: 5p; 3dxz; 4d; n=5, mo=3? The point here is how many 5p orbitals are there? (3) How many 3dxz orbitals? (1) How many 4d orbitals? (5) How many orbitals with n=5, mo=3? (Ordinarily one would not ask this particular question, but as written the correct answer is 2, since one of the 5f and one of the 5g orbitals will have mo=3 3. How many electrons in a given can have the set of quantum numbers, n=3, o=2? An o value defines a subshell, in this case the 3d subshell. Since there are five d orbitals, each of which can hold two electrons, so that a total of ten electrons can have this set of quantum numbers. 4. Calculate the ratio of the ionization energies for each of the following species to that of the hydrogen atom using the Bohr model: He+, Fe25+. Note how the value depends upon Z2. This problem basically involves the same concepts as problem 1. The ionization energy of any one-electron species is the same as a transition of an electron from n=1 to n=infinity or E = 13.6Z2. Thus the ratio of the ionization energies of any pair of oneelectron species is simply given by the ratio of the squares of their nuclear charges. H to He1+ = (1)2/(2)2 = 1/4; H to Fe25+ = (1)2/(26)2 = 1/676. Although there is no such thing as a Fe25+ ion the calculated ionization energy approximates what is required to ionize an electron from the 1s orbital of an iron atom or more normal +2 or +3 ion. Certain types of spectroscopy involve irradiation of a sample with high energy radiation that ionizes a core electron. Photons emitted as a 2s or 2 p electron drops to fill the 1s vacancy are detected. 5. What is meant by the statement that "a 4s electron is more penetrating than a 3d electron." This simply refers to the difference in radial distribution for the 3d and 4s orbitals. The 4s orbital has a significant portion of its electron density near the nucleus, which thus is "penetrating" the core electron density (the electrons in levels of lower principal quantum number). An alternative way to view this is that the core electrons screen (shield) electrons in the 3d level more than those in the 4s level.

6. Write the electron configurations of S1+, O1-, Fe. Indicate the number of unpaired electrons for each species. S1+ [Ne] 3s2 3px13py13pz1 (3 unpaired electrons) O1- [He] 2s2 2p5 (one unpaired electron) Fe [Ar] 4s2 3d23d13d13d13d1 (4 unpaired electrons) 7. Give an example of an excited state for C and Na. Any arrangement of electrons other than that of the ground state constitutes an excited state. For carbon this may take the form 2s12p4, 2s22p13s1, or even 2s22px2 or 2p2 configuration with nonparallel spins. Similar considerations apply to the Na atom. 8. Use Excel or another spreadsheet or plotting program to generate plots of the radial density (surface density) function 4r2R2 for the 2s orbital for the hydrogen atom and the Li2+ ion. Beyond the obvious that the two curves have the same shape and each displays the single radial node that is expected from the 2-Zr/ao term in the wave function, the effect of the higher nuclear charge of the Li2+ ion is responsible for the constriction of the electron density in this ion compared to the hydrogen atom. The reduction in size and the increase in electron density of the Li2+ orbital are apparent in the smaller r and higher value of the surface density. Note that there will be n-o-1 radial nodes for any orbital.
16

14

12

Hydrogen Lithium 2+

10

0 0 1 2 3 r 4 5 6

9. Calculate the energy required to remove an electron from the n=4 level of the He+ ion. The energy of any transition in a one-electron species is given by E = -13.6Z2 eV (1/nf21/ni2). Since nf is infinity for ionization, then the energy is E = 13.6]22/42 = 3.4 eV. The value is positive since energy must be added to the system to achieve ionization. 10. Describe the trends of the following properties on going from left to right, and from top to bottom, in the periodic table: a. electronegativity; b. atomic radius; c. covalentbond energy; d. common oxidation numbers. In what blocks of the periodic table (if any) do you find anomalous counter trends and account for the anomaly.

a. electronegativity. Electronegativity increase going from left to right in a period (row) and from top to bottom in any family (column) of the periodic table. The former effect is a result of generally increasing electron affinities and ionization energies on going from left to right. The latter effect is a result of generally decreasing electron affinities and ionization energies on going down a family. There are no anomalies in electronegativities. b. atomic radius. Atomic radii decrease on going from left to right in a period and increase on going from top to bottom in a family. The former effect is a result of steadily increasing a steadily increasing effective nuclear charge, which constricts the electron density and results in a smaller atom. The latter effect is a result of the increase in principle quantum level for each period and the greater distance through which the effective nuclear charge must operate. There are no particular anomalies in atomic radii. c. covalent bond energies. Covalent bond energies are largely restricted to bonds between elements in the p-block and hydrogen. First one must differentiate between homonuclear and heteronuclear bonds and for simplicity let us only consider single bonds. In general both homonuclear and heteronuclear cases bond energies decrease as one goes down a family because the atomic sizes are increasing and orbitals are becoming larger and more diffuse (lower electron density). Therefore the distances between nuclei are greater and bond energies are lower. In general, the trend in homonuclear bond energies is an increase on going from left to right, except in the second period where they decrease. The general effect is smaller orbital, therefore greater overlap, which leads to a stronger bond. The reason for the anomaly in the second period is the increase in electron-electron repulsion due to lone pairs. For heteronuclear bonds, the trend is generally increasing bond energy with increasing difference in electronegativity in a period because of the contribution of ionic bonding (recall the original method of computing electronegativity). This means that C-F and SiF are stronger than O-F and S-F, respectively. Energies decrease generally on going to heavier members of a family, except between the second and third row fluorides where lone pair repulsions result in weaker bonds for the former, because of the increasing sizes of the atoms even though the electronegativity differences are obviously greater. d. oxidation state. Here one needs to differentiate between positive and negative oxidation states and to decide what is meant by normal. But in general the common oxidation states of the s- and p-block elements will result in either a rare gas configuration (octet) or filled subshell configuration. Transition metal ions represent a special case. Normal positive oxidation states for the s-block and transition metal elements might be considered to be those commonly found in hydrated ions, which usually result from ionization of the s electrons, and sometimes an additional d electron for the transition elements. However, once manganese is reached, all of the +3 ions except for iron are so highly oxidizing that their hydrated forms are not stable. The high oxidizing potential of the +3 ions results from the increase in effective nuclear charge. The reason that hydrated iron(III) is stable is a result of the special stability associated with a half-filled shell. Positive oxidation states in the p block elements vary

considerably but there is a rational pattern for groups 13-15 where they equal either the number of p electrons or the number of p+s electrons. This means that the oxidation states of group 13 are +1 and +3, group 14 are +2 and +4, and for group 15, +3 and +5. The situation is a bit different for groups 16 and 17 where the same pattern does not hold. For group 16 there are three oxidation states +2, +4 and +6 and for group 17 four, +1, +3 + 5 and +7. However, what is true for all p-block elements is that the stable positive oxidation states are those that do not result in any unpaired spins, since this would normally lead to formation of a sigma bond between two such moieties. Negative oxidation states, which exist only for the p-block elements, result from addition of sufficient electrons to generate filled valence shells (rare gas configurations). Thus for group 14, -4 (few examples here), group 15, -3, group 16, -2 and group 17, -1. Obviously all electrons are paired in these forms. 11. Within each of the following groups arrange the species in order of increasing radius and in order of increasing ionization energy: O2-, F-, Na+, Mg2+ Li, C, F, Ne. Explain the reason for the order of each series. radius: O2-> F->Na+>Mg2+ The order in this isoelectronic group of ions is a result of the increasing effective nuclear charge binding the valence electrons as one progresses through the series. ionization energy: O2-< F-<Na+<Mg2+ The order is again the result of increasing effective nuclear charge which binds the electrons more strongly on going from the more negative to the more positive ion. radius: Li> C> F> Ne These are not isoelectronic, but the decrease in size is a result of a steadily increasing effective nuclear charge which results in constriction of the electron density and therefore size of the atom. The situation with F and Ne is a bit confusing because some tables, including table 17.11 in Oxtoby suggest that Ne is larger than F. However, the problem here is one of method of determination. If radii are computed then the radius of Ne is found to be less than that of F. There are extensive data and an outstanding discussion of atomic sizes in WebElements, one of the weblinks provided. ionization energy: Li< C< F< Ne As in the first series the trend in ionization energy must always be opposite the trend in size. 12. Draw sketches of the dxz and pz orbitals on a labeled Cartesian coordinate system. Indicate the phase (sign of the wave function) in each portion of the orbital.

z x

z x

The shaded portion of each orbital corresponds to the positive sign (phase). Note that the d orbital has a center of symmetry whereas the p orbital does not.