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All Textbook Solutions for Principles of Modern Chemistry

Quantum mechanics predicts that the energy of the ground state of the H atom is 13.6eV . Insight into the magnitude of this quantity is gained by considering several methods by which it can be measured. (a) Calculate the longest wavelength of light that will ionize H atoms in their ground state. (b) Assume the atom is ionized by collision with an electron that transfers all its kinetic energy to the atom in the ionization process. Calculate the speed of the electron before the collision. Express your answer in meters per second (ms1) and miles per hour (milesh1) . (c) Calculate the temperature required to ionize a H atom in its ground state by thermal excitation. (Hint: Recall the criterion for thermal excitation of an oscillator in Planck’s theory of blackbody radiation is that hvkBT .)29P Photoelectron spectroscopy studies of silicon atoms excited by X-rays with wavelength 9.8901010m show four peaks in which the electrons have speeds 2.097107ms1,2.093107ms1,2.014107ms1, and 1.971107ms1 . (Recall that 1J=1kgm2s2 .) (a) Calculate the ionization energy of the electrons in each peak. (b) Assign each peak to an orbital of the silicon atom.Photoelectron spectroscopy studies have determined the orbital energies for fluorine atoms to be 1s689eV2s34eV2p12eV Estimate the value of Zeff for F in each of these orbitals.32P For each of the following pairs of atoms or ions, state which you expect to have the larger radius. (a) Na or K (b) Cs or Cs+ (c) Rb+ or Kr (d) K or Ca (e) Cl or Ar For each of the following pairs of atoms or ions, state which you expect to have the larger radius. (a) Sm or Sm3+ (b) Mg or Ca (c) I orXe (d) Ge or As (e) Sr+ or Rb Predict the larger ion in each of the following pairs. Give reasons for your answers. (a) O,S2 (b) Co2+,Ti2+ (c) Mn2+,Mn4+ (d) Ca2+,Sr2+36P The first ionization energy of helium is 2370kJmol1 , the highest for any element. (a) Define ionization energy and discuss why for helium it should be so high. (b) Which element would you expect to have the highest second ionization energy? Why? (c) Suppose that you wished to ionize some helium by shining electromagnetic radiation on it. What is the maximum wavelength you could use?The energy needed to remove one electron from a gaseous potassium atom is only about two-thirds as much as that needed to remove one electron from a gaseous calcium atom, yet nearly three times as much energy as that needed to remove one electron from K+ as from Ca+ . What explanation can you give for this contrast? What do you expect to be the relation between the ionization energy of Ca+ and that of neutral K?Without consulting any tables, arrange the following substances in order and explain your choice of order: (a) Mg2+,Ar,Br,Ca2+ in order of increasing radius (b) Na, Na+ , O, Ne in order of increasing ionization energy (c) H, F, Al, O in order of increasing electronegativity Both the electron affinity and the ionization energy of chlorine are higher than the corresponding quantities for sulfur. Explain why in terms of the electronic structure of the atoms.The cesium atom has the lowest ionization energy, 375.7kJmol1 , of all the neutral atoms in the periodic table. What is the longest wavelength of light that could ionize a cesium atom? In which region of the electromagnetic spectrum does this light fall?Until recently, it was thought that Ca was unstable, and that the Ca atom therefore had a negative electron affinity. Some new experiments have now measured an electron affinity of +2.0kJmol1 for calcium. What is the longest wavelength of light that could remove an electron from Ca ? In which region of the electromagnetic spectrum does this light fall?In the hydrogen atom, the transition from the 2p state to the 1s state emits a photon with energy 16.21019J . In an iron atom, the same transition emits X-rays with wavelength 0.193 nm. Calculate the energy difference betweenthese two states in iron. Explain the difference in the 2p-1s energy level spacing in these two atoms.The energy needed to ionize an atom of element X when it is in its most stable state is 500kJmol1 . However, if an atom of X is in its lowest excited state, only 120kJmol1 is needed to ionize it. What is the wavelength of the radiation emitted when an atom of X undergoes a transition from the lowest excited state to the ground state?Suppose an atom in an excited state can return to the ground state in two steps. It first falls to an intermediate state, emitting radiation of wavelength 1 , and then to the ground state, emitting radiation of wavelength 2 . The same atom can also return to the ground state in one step, with the emission of radiation of wavelength . How are 1,2, and related? How are the frequencies of the three radiations related?For the Li atom, the energy difference between the ground state and the first excited state, in which the outermost electron is in a 2p orbital, is 2.961019J . In the Li2+ ion, the energy difference between the 2s and 2p levels is less than 0.00002 of this value. Explain this observation.How does the 3dxy orbital of an electron in O7+ resemble the 3dxy orbital of an electron in a hydrogen atom? How does it differ?The wave function of an electron in the lowest (that is, ground) state of the hydrogen atom is (r)=( 1 a 0 3 )1/2exp(r a 0 )ao=0.5291010m (a) What is the probability of finding the electron inside a sphere of volume 1.0pm2 , centered at the nucleus (1pm=1012m) ? (b) What is the probability of finding the electron in a volume of 1.0pm2 at a distance of 52.9 pm from the nucleus, in a fixed but arbitrary direction? (c) What is the probability of finding the electron in a spherical shell of 1.0 pm in thickness, at a distance of 52.9 pm from the nucleus?An atom of sodium has the electron configuration [Ne]6s1 . Explain how this is possible.(a) The nitrogen atom has one electron in each of the 2px , 2py , and 2pz orbitals. By using the form of the angular wave functions, show that the total electron density, 2(2px)+2(2py)+2(2pz) , is spherically symmetric (that is, it is independent of the angles and ). The neon atom, which has two electrons in each 2p orbital, is also spherically symmetric. (b) The same result as in part (a) applies to d orbitals, thus a filled or half-filled subshell of d orbitals is spherically symmetric. Identify the spherically symmetric atoms or ions among the following: F , Na, Si, S2,Ar+ , Ni, Cu, Mo, Rh, Sb, W, Au.Chromium(IV) oxide is used in making magnetic recording tapes because it is paramagnetic. It can be described as a solid made up of Cr4+ and O2 . Give the electron configuration of Cr4+ in CrO2 , and determine the number of unpaired electrons on each chromium ion.52AP Arrange the following seven atoms or ions in order of size, from smallest to largest: K,F+,Rb,Co25+,Br,F,Rb .Which is higher, the third ionization energy of lithium or the energy required to eject a 1s electron from a Li atom in a PES experiment? Explain.The outermost electron in an alkali-metal atom is sometimes described as resembling an electron in the corresponding state of a one-electron atom. Compare the first ionization energy of lithium with the binding energy of a 2s electron in a one-electron atom that has nuclear charge Zeff , and determine the value of Zeff that is necessary for the two energies to agree. Repeat the calculation for the 3s electron of sodium and the 4s electron of potassium.In two-photon ionization spectroscopy, the combined energies carried by two different photons are used to remove an electron from an atom or molecule. In such an experiment, a K atom in the gas phase is to be ionized by two different light beams, one of which has a 650-nm wavelength. What is the maximum wavelength for the second beam that will cause two-photon ionization?For the H atom, the transition from the 2p state to the 1s state is accompanied by the emission of a photon with an energy of 16.21019J . For an Fe atom, the same transition (2p to 1s) is accompanied by the emission of X-raysof 0.193-nm wavelengths. What is the energy difference between these states in iron? Comment on the reason for the variation (if any) in the 2p-1s energy-level spacing for these two atoms.(a) Give the complete electron configuration (1s22s22p) of aluminum in the ground state. (b) The wavelength of the radiation emitted when the outermost electron of aluminum falls from the 4s state to the ground state is about 395 nm. Calculate the energy separation (in joules) between these two states in the Al atom. (c) When the outermost electron in aluminum falls from the 3d state to the ground state, the radiation emitted has a wavelength of about 310 nm. Draw an energylevel diagram of the states and transitions discussed here and in (b). Calculate the separation (in joules) between the 3d and 4s states in aluminum. Indicate clearly which has higher energy.What experimental evidence does the periodic table provide that an electron in a 5s orbital is slightly more stable than an electron in a 4d orbital for the elements with 37 and 38 electrons?Determine the number of nodes along the internuclearaxis for each of the molecular orbitals for H2+ shown in Figure 6.5.Determine the number of nodes along the internuclearaxis and the number of nodal planes for each of the molecular orbitals for H2+ shown in Figure 6.5.Sketch the shape of each of the molecular orbitals for H2+ shown in Figure 6.5 in a plane perpendicular to the internuclear axis located at the midpoint between the two nuclei. Repeat the sketches for a plane perpendicular to the internuclear axis located at a point one quarter of the distance between the two nuclei.Sketch the shape of each of the molecular orbitals for H2+ shown in Figure 6.5 in a plane perpendicular to the internuclear axis located at the midpoint between the two nuclei. Repeat the sketches for a plane perpendicular to the internuclear axis located at a point one quarter of the distance between the two nuclei.Compare the electron density in the 1g and 1u* molecular orbitals for H2+ shown in Figure 6.5 with the classical model for bonding for H2+ summarized in Figure 3.22b. Which of these molecular orbitals describes the bond in H2+ ?Explain why 1g is the ground state for H2+ . By combining your answer with the answer to Problem 5, what conclusions can you draw about the molecular orbital description of the bond in H2+ ?7P Predict the ground electronic state of the He22+ ion. What is the bond order? Will it be stable in the ground state?9P 10P Without consulting tables of data, predict which species has the greater bond length, H2 or He2+ .Without consulting tables of data, predict which species has the greater bond length, He2+ or H2 .Without consulting tables of data, on the same graph sketch the effective potential energy curves for H2 and He2+ .Without consulting tables of data, on the same graph sketch the effective potential energy curves for He2+ and H2 .Suppose we supply enough energy to H2 to remove one of its electrons. Is the bond energy of the resulting ion larger or smaller than that of H2 ? Is the bond length of the resulting ion larger or smaller than that of H2 ?Suppose we supply enough energy to He2+ to remove its most weakly bound electron. Is the bond energy of the resulting ion larger or smaller than that of He2+ ? Is the bond length of the resulting ion larger or smaller than that of He2 ?17P When one electron is added to an oxygen molecule, a superoxide ion (O2) is formed. The addition of two electrons gives a peroxide ion (O22) . Removal of an electron from O2 leads to O2+ . (a) Construct the correlation diagram for O2 . (b) Give the valence electron configuration for each of the following species: O2+,O2,O2,O22 . (c) Give the bond order of each species. (d) Predict which species are paramagnetic. (e) Predict the order of increasing bond dissociation energy among the species.Predict the valence electron configuration and the total bond order for the molecule S2 , which forms in the gas phase when sulfur is heated to a high temperature. Will S2 be paramagnetic or diamagnetic?Predict the valence electron configuration and the total bond order for the molecule I2 . Will I2 be paramagnetic or diamagnetic?21P For each of the following valence electron configurations of a homonuclear diatomic molecule or molecular ion, identify the element X, Q, or Z and determine the total bond order. (a) X2:( g2s)2(u* 2s)2( g2 p z )2( u2p)4(g* 2p)2 (b) Q2:( g2s)2(u* 2s)2( u2p)3 (c) Z22+:( g2s)2(u* 2s)2( g2 p z )2( u2p)4(g* 2p)2 For each of the electron configurations in Problem 21, determine whether the molecule or molecular ion is paramagnetic or diamagnetic.For each of the electron configurations in Problem 22, determine whether the molecule or molecular ion is paramagnetic or diamagnetic.Following the pattern of Figure 6.21, work out the correlation diagram for the CN molecule, showing the relative energy levels of the atoms and the bonding and anti-bonding orbitals of the molecule. Indicate the occupation of the MOs with arrows. State the order of the bond and comment on the magnetic properties of CN.Following the pattern of Figure 6.21, work out the correlation diagram for the BeN molecule, showing the relative energy levels of the atoms and the bonding and antibonding orbitals of the molecule. Indicate the occupation of the MOs with arrows. State the order of the bond and comment on the magnetic properties of BeN.The bond length of the transient diatomic molecule CF is 1.291 Å; that of the molecular ion CF+ is 1.173 Å. Explain why the CF bond shortens with the loss of an electron. Refer to the proper MO correlation diagram.The compound nitrogen oxide (NO) forms when the nitrogen and oxygen in air are heated. Predict whether the nitrosyl ion (NO+) will have a shorter or a longer bond than the NO molecule. Will NO+ be paramagnetic like NO or diamagnetic?What would be the electron configuration for a HeH molecular ion? What bond order would you predict? How stable should such a species be?The molecular ion HeH+ has an equilibrium bond length of 0.774 Å. Draw an electron correlation diagram for this ion, indicating the occupied MOs. Is HeH+ paramagnetic? When HeH+ dissociates, is a lower energy state reached by forming He+H+ or He++H ?31P Predict the ground state electronic configuration of HeBe. What is the bond order?The bond dissociation energies for the species NO, CF , and CF+ are ordered as CF+NOCF . Use MO theory to explain this ordering.The ionization energy of CO is greater than that of NO. Explain this difference based on the electron configurations of these two molecules.Photoelectron spectra were acquired from a sample of gaseous N2 using He(I) light with energy 21.22 eV as the ionization source. Photoelectrons were detected with kinetic energy values 5.63 eV and also with 4.53 eV. Calculate the ionization energy for each group of electrons. Identify the MOs that were most likely the sources of these two groups of electrons.Photoelectron spectra were acquired from a sample of gaseous O2 using X-ray radiation with wavelength 0.99 nm and energy 1253.6 eV. The spectrum contained a large peak for photoelectrons with speed of 1.57107ms1 . Calculate the ionization energy of these electrons. Identify the orbital from which they were most likely emitted.37P From the n=0 peaks in the photoelectron spectrum for O2 shown in the figure in Connections box, prepare a quantitative energy level diagram for the molecular orbitals of O2 .The photoelectron spectrum of HBr has two main groups of peaks. The first has ionization energy 11.88 eV. The next peak has ionization energy 15.2 eV, and it is followed by a long progression of peaks with higher ionization energies. Identify the molecular orbitals corresponding to these two groups of peaks.The photoelectron spectrum of CO has four major peaks with ionization energies of 14.5, 17.2, 20.1, and 38.3 eV. Assign these peaks of molecular orbitals of CO, and prepare a quantitative energy level correlation diagram for CO. The ionization energy of carbon atoms is 11.26 eV, and the ionization energy of oxygen atoms is 13.62 eV.Write simple valence bond wave functions for the diatomic molecules Li2 and C2 . State the bond order predicted by the simple VB model and compare with the LCAO predictions in Table 6.3.Write simple valence bond wave functions for the diatomic molecules B2 and O2 . State the bond order predicted by the simple VB model and compare with the LCAO predictions in Table 6.3.Both the simple VB model and the LCAO method predict that the bond order of Be2 is 0. Explain how each arrives at that conclusion.Both the simple VB model and the LCAO method predict that the bond order of Ne2 is 0. Explain how each arrives at that conclusion.Write simple valence bond wave functions for formation of bonds between B atoms and H atoms. What BH compound does the VB model predict? What geometry does it predict for the molecules?Write simple valence bond wave functions for formation of bonds between C and H atoms. What CH compound does the VB model predict? What geometry does it predict for the molecules?Write simple valence bond wave functions for the bonds in NH3 . What geometry does the VB model predict for NH3 ?Write simple valence bond wave functions for the bonds in H2O . What geometry does the VB model predict for H2O ?Formulate a localized bond picture for the amide ion (NH2) . What hybridization do you expect the central nitrogen atom to have, and what geometry do you predict for the molecular ion?Formulate a localized bond picture for the hydronium ion (H3O+) . What hybridization do you expect the central oxygen atom to have, and what geometry do you predict for the molecular ion?51P Draw a Lewis electron dot diagram for each of the following molecules and ions. Formulate the hybridization for the central atom in each case and give the molecular geometry. (a) BF3 (b) BH4 (c) PH3 (d) CS2 (e) CH3+Describe the hybrid orbitals on the chlorine atom in the ClO3+ and ClO2+ molecular ions. Sketch the expected geometries of these ions.Describe the hybrid orbitals on the chlorine atom in the ClO4 and ClO3 molecular ions. Sketch the expected geometries of these ions.The sodium salt of the unfamiliar orthonitrate ion (NO43) has been prepared. What hybridization is expected on the nitrogen atom at the center of this ion? Predict the geometry of the NO43 ion.Describe the hybrid orbitals used by the carbon atom in NCCl . Predict the geometry of the molecule.Describe the bonding in the bent molecule NF2 . Predict its energy level diagram and electron configuration.Describe the bonding in the bent molecule OF2 . Predict its energy level diagram and electron configuration.The azide ion (N3) is a weakly bound molecular ion. Formulate its MO structure for localized s bonds and delocalized bonds. Do you expect N3 and N3+ to be bound as well? Which of the three species do you expect to be paramagnetic?Formulate the MO structure of (NO2+) for localized bonds and de-localized bonds. Is it linear or nonlinear? Do you expect it to be paramagnetic? Repeat the analysis for NO2 and for NO2 .Discuss the nature of the bonding in the nitrite ion (NO2) . Draw the possible Lewis resonance diagrams for this ion. Use the VSEPR theory to determine the steric number, the hybridization of the central nitrogen atom, and the geometry of the ion. Show how the use of resonance structures can be avoided by introducing a de-localized MO. What bond order does the MO model predict for the NO bonds in the nitrite ion?Discuss the nature of the bonding in the nitrate ion (NO3) . Draw the possible Lewis resonance diagrams for this ion. Use the VSEPR theory to determine the steric number, the hybridization of the central N atom, and the geometry of the ion. Show how the use of resonance structures can be avoided by introducing a de-localized MO. What bond order is predicted by the MO model for the NO bonds in the nitrate ion?The pyridine molecule (C5H5N) is obtained by replacing one CH group in benzene with a nitrogen atom. Because nitrogen is more electronegative than the CH group, orbitals with electron density on nitrogen are lower in energy. How do you expect the MOs and energy levels of pyridine to differ from those of benzene?For each of the following molecules, construct the MOs from the 2pz atomic orbitals perpendicular to the plane of the carbon atoms. (a) Cyclobutadiene HC (b) Allyl radical Indicate which, if any, of these orbitals have identical energies from symmetry considerations. Show the number of electrons occupying each MO in the ground state, and indicate whether either or both of the molecules are paramagnetic. Assume that the C atoms in the allyl radical are all sp2 hybridized.(a) Sketch the occupied MOs of the valence shell for the N2 molecule. Label the orbitals as or orbitals, and specify which are bonding and which are antibonding. (b) If one electron is removed from the highest occupied orbital of N2 , will the equilibrium NN distance become longer or shorter? Explain briefly.Calcium carbide (CaC2) is an intermediate in the manufacturing of acetylene (C2H2) . It is the calcium salt of the carbide (also called acetylide) ion (C22) . What is the electron configuration of this molecular ion? What is its bond order?The B2 molecule is paramagnetic; show how this indicates that the energy ordering of the orbitals in this molecule is given by Figure 6.18a rather than 6.18b.The Be2 molecule has been detected experimentally. It has a bond length of 2.45 Å and a bond dissociation energy of 9.46kJmol1 . Write the ground-state electron configuration of Be2 and predict its bond order using the theory developed in the text. Compare the experimental bonding data on Be2 with those recorded for B2,C2,N2, and O2 in Table 6.3. Is the prediction that stems from the simple theory significantly incorrect?69AP The molecular ion HeH+ has an equilibrium bond length of 0.774 Å. Draw an electron correlation diagram for this molecule, indicating the occupied MOs. If the lowest energy MO has the form C11sH+C21sH , do you expect C2 to be larger or smaller than C1 ?The MO of the ground state of a heteronuclear diatomicmoleculeAB is mol=CAA+CBB If a bonding electron spends 90% of its time in an orbital A on atom A and 10% of its time in B on atom B, what are the values of CA and CB ? (Neglect the overlap of the two orbitals.)The stable molecular ion H3+ is triangular, with HH distances of 0.87 Å. Sketch the molecule and indicate the region of greatest electron density of the lowest energy MO.According to recent spectroscopic results, nitramide is a nonplanar molecule. It was previously thought to be planar. (a) Predict the bond order of the NN bond in the nonplanarstructure. (b) If the molecule really were planar after all, what would be the bond order of the NN bond?trans-tetrazene (N4H4) consists of a chain of four nitrogen atoms with each of the two end atoms bonded to two hydrogen atoms. Use the concepts of steric number and hybridization to predict the overall geometry of the molecule. Give the expected structure of cis-tetrazene.1P Is it possible for a motor fuel to have a negative octane rating? Explain.A gaseous alkane is burned completely in oxygen. The volume of the carbon dioxide that forms equals twice the volume of the alkane burned (the volumes are measured at the same temperature and pressure). Name the alkane and write a balanced equation for its combustion.A gaseous alkyne is burned completely in oxygen. The volume of the water vapor that forms equals the volume of the alkyne burned (the volumes are measured at the same temperature and pressure). Name the alkyne and write a balanced equation for its combustion.Write a chemical equation involving structural formulas for the catalytic cracking of decane into an alkane and an alkene that contain equal numbers of carbon atoms. Assume that both products have straight chains of carbon atoms. Draw and name one other isomer of the alkene.6P 7P 8P 9P 10P 11P 12P 13P State the hybridization of each of the carbon atoms in the hydrocarbon structures in Problem 12.15P 16P 17P In a recent year, the United States produced 6.26109kg 1,2-dichloroethane and 3.73109kg vinyl chloride. Assuming that all significant quantities of vinyl chloride were produced from 1,2-dichloroethane, what fraction of the 1,2-dichloroethane production went into making vinyl chloride? What mass of hydrogen chloride was generated as a by-product?19P 20P 21P 22P 23P 24P 25P 26P Acetic acid can be made by the oxidation of acetaldehyde (CH3CHO). Molecules of acetaldehyde have a CH3 group, an oxygen atom, and a hydrogen atom attached to a carbon atom. Draw the Lewis diagram for this molecule, give the hybridization of each carbon atom, and describe the orbitals and the number of electrons that occupy each one. Draw the three-dimensional structure of the molecule, showing all angles.Acrylic fibers are polymers made from a starting material called acrylonitrile, H2C(CH)CN. In acrylonitrile, aCN group replaces a hydrogen atom on ethene. Draw the Lewis diagram for this molecule, give the hybridization of each carbon atom, and describe the orbitals and the number of electrons that occupy each one. Draw the three-dimensional structure of the molecule, showing all angles.Compare the bonding in formic acid (HCOOH) with that in its conjugate base formate ion (HCOO). Each molecule has a central carbon atom bonded to the two oxygen atoms and to a hydrogen atom. Draw Lewis diagrams, determine the steric numbers and hybridization of the central carbon atom, and give the molecular geometries. How do the orbitals differ in formic acid and the formate molecular ion? The bond lengths of the CO bonds in HCOOH are 1.23 (for the bond to the lone oxygen) and 1.36 (for the bond to the oxygen with a hydrogen atom attached). In what range of lengths do you predict the CO bond length in the formate ion to lie?30P 31P 32P 33P 34P 35P Describe the changes in hydrocarbon structure and functional groups that are needed to make testosterone from cortisone (see Fig. 7.39).trans-Cyclodecene boils at 193C, but cis-cyclodecene boils at 195.6C. Write structural formulas for these two compounds.38AP 39AP Consider the following proposed structures for benzene, each of which is consistent with the molecular formula C6H6. (iv) CH3CCCCCH3 (v) CH2=CHCCH=CH2 When benzene reacts with chlorine to give C6H5Cl, only one isomer of that compound forms. Which of the five proposed structures for benzene are consistent with this observation? When C6H5Cl reacts further with chlorine to give C6H4Cl2, exactly three isomers of the latter compound form. Which of the five proposed structures for benzene are consistent with this observation?41AP 42AP 43AP 44AP 45AP The steroid stanolone is an androgenic steroid (a steroid that develops or maintains certain male sexual characteristics). It is derived from testosterone by adding a molecule of hydrogen across the C=C bond in testosterone. Using Figure 7.39c as a guide, draw the molecular structure of stanolone. What is the molecular formula of stanolone?The structure of the molecule cyclohexene is Does the absorption of ultraviolet light by cyclohexene occur at longer or at shorter wavelengths than the absorption by benzene? Explain.48CP 1P 2P 3P 4P 5P 6P 7P 8P 9P 10P 11P 12P 13P 14P 15P 16P 17P 18P 19P 20P 21P 22P 23P 24P 25P 26P 27P 28P 29P 30P 31P 32P 33P 34P 35P 36P 37P 38P 39P 40P 41P 42P 43P 44P 45P 46P 47AP 48AP 49AP 50AP 51AP 52AP 53AP 54AP 55AP 56AP 57AP 58AP 59AP 60AP 61AP 62AP 63AP 64AP 65AP 66AP 67AP 68AP 69AP 70AP 71AP 72AP 73AP 74CP 75CP 76CP 1P 2P 3P 4P 5P 6P 7P 8P 9P 10P 11P 12P 13P 14P 15P 16P 17P 18P 19P 20P 21P 22P 23P 24P 25P 26P 27P 28P 29P 30P 31P 32P 33P 34P 35P 36P 37P 38P 39P 40P 41P 42P 43P 44P 45P 46P 47P 48P 49P 50P 51P 52P 53P 54P 55P 56P 57P 58P 59P 60P 61AP 62AP 63AP 64AP 65AP 66AP 67AP 68AP 69AP 70AP

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