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The Advanced Placement Examination in Chemistry

Part II - Free Response Questions & Answers 1970 to 2005


F .F. With this as the basis. ... non-linear structure. In CH2F2 the C-F and C-H bonds are polar and the molecule is not symmetrical. Answer: The correct structure is NNO. give an example of a (b) For a metal M. 16. the molecules is polar and would show a dipole moment.London forces + dipole-dipole interactions NH3 .. . . . N-O bond dipole. 1974 D The possible structures for the compound dinitrogen oxide are NNO and NON.. Nonexistence of NF5 because of no low energy d orbital for N. For each of the two shapes. Answer: B 120_ A B B trigonal planar B A B B trigonal pyramid Example: trigonal planar.Bonding and Molecular Structure 1973 D Discuss briefly the relationship between the dipole moment of a molecule and the polar character of the bonds within it. The molecular structure is always based on the positions of the atoms. therefore it is a trigonal pyramid rather than a tetrahedron. .. . trigonal pyramid.F . .F... 28..e. .. . Answer: . . . ... therefore.. . On the basis of structural and bonding considerations. 1975 D Suppose that a molecule has the formula AB3. the molecule is non-polar and would not show a dipole moment. and 14 are obtained in the mass spectrometer. molecular dipole moment. Sketch (a) Bond polarity and molecular polarity (dipole and name two different shapes that this molecule may moment) have..... Spectral Data (mass of molecular fragments): 44 = NNO 28 = NN 14 = N 30 = NO 16 = O A fragment of 28 couldn’t be made if the structure was NON. Answer: In order to have a dipole moment (i. but the molecule is symmetrical. OR The NH3 molecule has four pairs of electrons: three bonding pairs and one non-bonding pair. 30. ionization energy and electrode .. . BF3. 1978 D State precisely what is meant by each of the following four terms.F N . F . F . NH3 For BF3. one in which the vector sum of the bond dipoles ≠ 0). Write the electrondot formulas for these molecules. . P . .weak London dispersion (van der Waals) forces H2S . interpret the shape in the context of a modern bonding theory. compressing the bonding pairs to an angle of 107º. . . account for the fact that NF3 and PF5 are stable molecules but NF5 does not exist. Then distinguish clearly between each of the two terms in part (a) and between each of the two terms in part (b). account for the difference between the dipole moments of CH2F2 and CF4. . Describe the sp3 bonding for NF3 and the sp3d for PF5.London + dipole + hydrogen bonding page 2 known molecule that has that shape. the arrangement that will minimize the repulsions is a flat (planar) arrangement with the electron pairs furthest apart at 120º angles.F. By experimentation it has been found that the molecule of dinitrogen oxide has a non-zero dipole moment and that ions of mass 44. N-N=O. . . 1976 D NF3 and PF5 are stable molecules. . Answer: CH4 . For one of the molecules you have named.e. The best arrangement for four electron pairs is a tetrahedral structure (109. the boron atom is surrounded by three pairs of electrons.5º) with the lone (non-bonding) electron pair at the apex requiring more space than the bonding pairs. . In CF4 the C-F bonds are polar. . Which of the structures is supported by these data? Show how the data are consistent with this structure. non-symmetrical. 1974 D The boiling points of the following compounds increase in the order in which they are listed below: CH4 < H2S < NH3 Discuss the theoretical considerations involved and use them to account for this order. to be a polar molecule) a molecule must have polar bonds and must have a molecular geometry which is not symmetrical (i.. using chemical equations or examples where helpful. therefore.

1-propanol can interact with water by both Draw Lewis structures for CO2.(ºC) in water Butane CH3CH2CH2CH3 0 insoluble : : : 2: O :S O : Trigonal pyramidal or dis: : : : :O : torted tetrahedral ion : . their boiling points and solubilities in water are listed Explain how you arrived at your predictions. Data on (c) Predict the molecular shapes for the three species. Distinction (normally included within the definitions). 1-propanol molecules show these two H types of attraction. (b) Both chloroethane and acetone are polar. acetone forms hydrogen bonds to water much more effectively than chloroethane does. 1-propanol is polar and can form hydrogen 1979 D bonds. including resonance structures where appropriate. SO3 and SO32. Thus. 1-propanol can also :O: undergo hydrogen bonding. Answer: (a) Bond polarity . However. H2. Answer: (a) Butane is nonpolar. : : O :C O : Linear or straight m : : : olecule (d) Acetone molecules are attracted to each other by : : van der Waals attraction and dipole-dipole H : : Bent or angular molecule S : attraction.related to energy associated with oxidation or reduction or associated with a tendency to gain or lose electrons. This distinguishing : : feature results in the higher boiling point of 1S Triangular planar molecule : : : : propanol.result of the separation of the centers of positive and negative charges in an entire molecule (The dipole moment is a measure). chloroethane.1 additional point] Electrode potential . Butane predict the shape of each species. (b) water solubilities of chloroethane and acetone. or from bonding of atoms with different electronegativities. CO2. thus a higher boiling point for chloroethane. A quantity measured relative to the hydrogen electrode or related to the energy changes in an electrochemical cell. can interact with water by neither means. (b) Ionization energy . chloroethane is polar. (c) water solubilities of butane and 1-propanol. O :O : : : 1982 D (a) Draw the Lewis electron-dot structures for CO32-. Chloroethane page 3 CH3CH2Cl O || Acetone 12 56 CH3C C CH3 insoluble completely miscible completely miscible 1-Propanol CH3CH2CH2OH 97 On the basis of dipole moments (molecular polarities) and/or hydrogen bonding.resulting from unequal sharing of electrons between bonding atoms. in the table below. Distinction (normally included within the definitions). Intermolecular forces of attraction in liquid chloroethane are larger due to dipole-dipole attraction. resulting in greater solubility of acetone in water. approximately the same molecular weights. or the result of the non-zero vector sum of bond dipoles and lone-pair electrons.Bonding and Molecular Structure potential. Answer: Boiling Solubility (a) Compound Formula Pt. (d) boiling points of acetone and 1-propanol.and dipole-dipole forces and hydrogen bonds. explain in a qualitative way the differences in the (a) boiling points of butane and chloroethane. However. 1Answer: propanol is much more soluble. acetone. 1979 D (b) Which of the three species has the shortest C-O Butane. and CO.. Molecular polarity . (c) Butane is non-polar and cannot form hydrogen required to remove an electron from an atom [if atom is described as gaseous or isolated . and 1-propanol all have bond length? Explain the reason for your answer.

what London) forces. will be formed? Explain in terms of the electronic configurations given in HF has a higher melting point because part (a).C has two bonding pairs and no lone pairs . if any.CO2 is nonpolar and must be linear. but Ar atom is smaller and has a greater nuclear charge. and the ionic forces are (kJ/mol) stronger than van der Waals forces and hydrogen Q 496 4568 6920 bonds. I2. (d) Formula is QCl. explain why the bonds in these substances. (c) CO32. C3H8 -190 I3) for magnesium and argon are as follows: HF -92 I1 I2 I3 CsI 621 (kJ/mol) LiF 870 Mg 735 1443 7730 SiC >2.C has three bonding pairs and no lone pair. (c) Only MgCl2 forms. strong covalent bonds. Removal of third electron from Mg atom is from n = 2 level and electrons in this level experience strong nuclear attraction. discuss Ar.Bonding and Molecular Structure :O : C : :O : : : O =C =O : : :C O: : :O : :O : O: : :O : C : :O: : :O : : :O : : :O : C : :O 2 2 6 1 page 4 : C O: : C O: (b) CO has the shortest bond because there is a triple bond.or .000 (a) Discuss how the trend in the melting points of the Ar 1525 2665 3945 substances tabulated above can be explained in (a) Give the electronic configurations of Mg and Ar. C bonding is sp hybrid . OR because there is the greatest number of electrons between C and O in CO. (d) Element Q has the following first three ionization CsI and LiF have still higher melting points energies: because ionic lattice forces must be overcome to I1 I2 I3 break up the crystals. Thus.or . ionization energies for Mg are less than those for Ar. 1985 D Substance Melting Point. and ionization energies for Ar atoms are high. ºC 1982 D H2 -259 The values of the first three ionization energies (I1. values of the first and second ionization energies of Mg are significantly lower than the values for (b) For any pairs of substances that have the same kind(s) of attractive forces and/or bonds. intermolecular hydrogen bonding is important. Ar.trigonal planar (planar and triangular). CO2 linear. Answer: (a) Mg: 1s 2s 2p 3s Ar: 1s2 2s22p6 3s23p6 (b) Valence electrons for Mg and Ar are in the same principal energy level. Mg atoms readily lose 2 valence electrons each. Very high second ionization energy indicates that there is only one valence electron. . Electron affinity for Ar is low. compounds. Two atoms determine a straight line. C bonding is sp2 hybrid . (c) If a sample of Ar in one container and a sample of Answer: Mg in another container are each heated and (a) H2 and C3H8 have low melting points because the forces involved were the weak van der Waals (or chlorine is passed into each container. What is the formula for the most likely compound SiC is an example of a macromolecular substance of element Q with chlorine? Explain the choice of where each atom is held to its neighbors by very formula on the basis of the ionization energies.or . whereas the third ionization energy of Mg is the factors that cause variations in the strengths of much larger than the third ionization energy of the forces and/or bonds. terms of the types of attractive forces and/or (b) In terms of these configurations. CO linear. Ionization energy for third electron very high.

The magnitude of such forces is determined by the 1989 D number of electrons in the atom. Larger radii -> smaller attraction and lower . Lattice energy (VSEPR) model to explain the geometry of each 1 of these molecules. thus the molecule is polar. and CsI? Explain bonds.) increase from F2 to I2. and in which the dipoles cancel. while CO2 (maximize bond angles). (c) What is the expected trend in the melting points of (c) SiO2 is a covalent network solid. Larger radii of ions as CF4 XeF4 ClF3 listed. Copper chloride is a rigid ionic solid with (b) Using bonding principles. OR C3H8 is weakly the molecules above and identify the shape of polar and H2 is nonpolar. CO2 is composed of discrete. NaCl. melting points) decrease. ClF3 = 3 bonding pairs and 2 lone pairs give Answer: trigonal bipyramid with one pairs in equatorial (a) Xe and Ne are monatomic elements held together positions 120º apart. even though Si and XeF4 = 4 bonding pairs and 2 lone pairs give C are in the same chemical family. + − Answer: U is proportional to r + r . (Size of the Li to Cs. individual copper(II) ions. (a) : : :F: : : : : 1988 D :F: F : F : : : : : F :C : F : : : : : : Cl : : : Using principles of chemical bonding and/or : : : : : F : : Xe : : : :F: intermolecular forces. dipoles caused by polarization of electron clouds. but solid copper chloride is not. While in BF3 there is no lone pair on the central As molecules increase in size (F2 to I2). There are strong the compounds LiF. but those of BF3 are of Xe atom not. As cations increase in size (Li to Cs).Bonding and Molecular Structure page 5 (b) C3H8 and H2: There are more interactions per (a) Draw a Lewis electron-dot structure for each of molecule in C3H8 than in H2. The dipoles don’t (b) Halogen molecules are held in place by dispersion (van der Waals) forces: bonds due to temporary cancel. (b) The electrical conductivity of copper metal is (a) Using bonding principles. simultaneously to volatilize SiO2. In contrast. thus the molecule is the attractive forces (and melting points) increase. nonpolar. bands). each. explain each of the following. LiF and CsI: The smaller ions in LiF result in a (b) Use the valence shell electron-pair repulsion higher lattice energy than CsI has. nonpolar CO2 molecules so Answer: that the only forces holding the molecules (a) Alkali metals have metallic bonds: cations in a sea of electrons. regular tetrahedron to minimize repulsion (c) SiO2 melts at a very high temperature. many of which must be broken this trend using bonding principles. account for the based on mobile valence electrons (partially filled decrease in the melting points of the alkali metals. tetrahedral square planar T-shaped (b) Solid copper is an excellent conductor of (b) CF4 = 4 bonding pairs around C at corners of electricity. the larger atom so the molecule has a trigonal planar shape electron clouds are more readily polarized. account for the the valence electrons of copper localized in decrease in the melting points of the halogens. octahedral shape with lone pairs on opposite sides (d) Molecules of NF3 are polar. F : F :F: : : : : : : (a) Xenon has a higher boiling point than neon has. the melting points of the halogens atom was accepted but mass was not. A Xe atom has The melting points of the alkali metals decrease from more electrons than a neon atom has. by London dispersion (van der Waals) forces. together are the weak London dispersion (van der charge density decreases and attractive forces (and Waals) forces. (c) Melting point order: LiF > NaCl > KBr > CsI 1989 D Compounds are ionic. KBr. is a gas at room temperature. (d) In NF3 a lone pair of electrons on the central atom results in a pyramidal shape.

28 1. (a) MgCl2 and SiCl4 (c) F2 and Br2 (b) MgCl2 and MgF2 (d) F2 and N2 Answer: (a) MgCl2 is IONIC while SiCl4 is COVALENT. whereas I2(s) has a Molten State (ohm-1) solubility of only 0. (b) The H-N-H bond angle is 107. Triple bonds are stronger and therefore shorter than single bonds.5º. are right angles to the I-I-I. MgCl2 714 > 20 Answer: SiCl4 -70 0 MgF2 1261 > 20 (a) K conducts because of its metallic bonding .Bonding and Molecular Structure melting points. 1990 D (Required) Use simple structure and bonding models to account for each of the following. the 3 lone pairs on the 1992 D central atom are arranged as a triangle in a plane Explain each of the following in terms of atomic and molecular structures and/or intermolecular forces. (c) The bonding in SO3 can be described as a combination of 3 resonance forms of 1 double and 2 single bonds. Experimental data provide the basis for interpreting (b) SbCl3 has measurable dipole moment.ion is linear. whereas 1991 D solid KNO3 does not. (a) The bond length between the two carbon atoms is shorter in C2H4 than in C2H6. The electrostatic. (c) The bond length in Br2 is larger than in F2 because the Br atom is bigger (more shells) than the F atom. SbCl5 does not. in NH3. Answer: (a) C2H4 has a multiple bond. (d) The I3.or – . Molten MgCl2 contains mobile ions that conduct electricity whereas molten SiCl4 is molecular.03 gram per 100 grams of BeCl2 405 0. The actual structure is intermediate among the 3 resonance forms. Bonding pairs are forced together because repulsion between lone pair and bonding pairs is greater than between bonding pairs. whereas differences in properties of substances. To minimize repulsion. not ionic. shorter than single bonds. (c) The bond lengths in SO3 are all identical and are shorter than a sulfur-oxygen single bond. :O : : S : : O: : : : : :O : : :O : : :S : : : : O: :O: : :O : : S : : :: : O : :O : page 6 TABLE 2 Substance Bond Length (angstroms) F2 Br2 N2 1. C2H6 has a single bond. whereas Melting Electrical that of CBr4 is 190ºC.ions and the smaller interionic distances in MgF2 cause stronger forces and higher melting point. TABLE 1 (c) The normal boiling point of CCl4 is 77ºC. (a) Solid K conducts an electric current. interionic forces in magnesium chloride are much stronger then the intermolecular (dispersion) forces in SiCl4 and lead to a higher melting point for MgCl2.09 Account for the differences in properties given in Tables 1 and 2 above in terms of the differences in structure and bonding in each of the following pairs. and has no conductivity.axis. (d) The bond length in N2 is less than in F2 because the N≡ N bond is triple and the F-F is single. (b) MgF2 has a higher melting point than MgCl2 because the smaller F. (d) The central I atom has 3 lone pairs and 2 bonding : : : : : I:I : I: : : : pairs around it. shorter) than an S-O single bond. having 3 bonds that are equal and stronger (therefore. Compound Point (ºC) Conductivity of (d) NaI(s) is very soluble in water. Multiple bonds are stronger and.42 2.086 water. therefore. (b) NH3 has 3 bonding pairs of electrons and 1 lone pair.

have sp2 hybridization requires a large amount of energy to destabilize it NO2 will dimerize. These stronger forces occur because CBr4 is larger and/or has more electrons than CCl4.. being polar. in CaO these are +2 and .Bonding and Molecular Structure “sea” of mobile electrons (or free electrons). whereas I2 is non-polar (or covalent). Account for this difference. combined with the larger charges. (b) Lattice energy can be represented by Coulomb’s Q 1Q 2 (c) (d) law: lattice energy = k r . but not as easily as its first 4s electron. : -2 respectively.460 kilojoules per mole. while in K2O they are +1 and -2.or . Account for this difference. (Like dissolves like accepted if polarity of water is clearly indicated. where Q1 and Q2 are the charges on the has a trigonal pyramidal structure . KNO3 does not conduct because it is ionically bonded and has immobile ions (or immobile electrons). on N calcium has paired 4s electrons which require NO2+ . Ca+ has a remaining 4s1 electron that will pair readily with another.3 charge centers around N.< NO2 < NO2+ thus accounts for the larger lattice energy.a clear diagram illustrating any of the above. because it contains an odd and create a K2+ ion. Answer: (a) (b) page 7 1994 D Use principles of atomic structure and/or chemical bonding to answer each of the following. (a) The radius of the Ca atom is 0. which has a much smaller size because the (-)/(+) charge ratio is less than 1 causing a contraction of the electron shell.140 (c) Explain the difference between Ca and K in regard to (i) their first ionization energies. electron.or (ii) a K+ ion has a stable [Ar] electron core and NO2/NO2.or . Ca = [Ar] 4s2 electrons on N (i) Potassium has a single 4s electron that is easily NO2 .099 nanometer. NO2. (c) Select one of the species and give the hybridization of the nitrogen atom in it. lone pair of (c) Electron arrangements: K = [Ar] 4s1. N N : : :: : : : :: : : : The r (the distance between ions) is slightly O : :O O: :O : : O :N O: : : : : smaller in CaO. (b) List the species in order of increasing bond angle. (d) The first ionization energy of Mg is 738 kilojoules per mole and that of Al is 578 kilojoules per mole. (d) NaI has greater aqueous solubility than I2 because NaI is ionic (or polar). (b) SbCl3 has a measurable dipole moment because it has a lone pair of electrons which causes a dipole .3 charge centers around N. (b) The lattice energy of CaO(s) is -3. In a calcium ion these electrons are absent and the highest energy electrons are 3p. NO2+ is linear. Justify your answer. NO2. the radius of the Ca2+ ion is 0.its dipoles do not cancel . (ii) their second ionization energies. (a) Draw the Lewis electron-dot structure for each of the three species. whereas. the lattice energy for K2O(s) is -2. electron that is more easily removed than a core forming N2O4.) 1992 D NO2 NO2NO2+ Nitrogen is the central atom in each of the species given above. . Account for this difference. (c) CBr4 boils at a higher temperature than CCl4 because it has stronger intermolecular forces (or van der Waal or dispersion). single electron removed to produce an [Ar] core. (d) Identify the only one of the species that dimerizes and explain what causes it to do so. interacts with the ions of NaI but not with I2.050 Ca 590 1. has sp hybridization .or .197 nanometer. Ionization Energy (kJ/mol) First Second K 419 3.2 charge centers on N greater energy to remove one. Water. Answer: (a) The valence electrons in a calcium atom are the 4s2.240 kilojoules per mole.

As Point (ºC) Room Temp. (c) Halides of cobalt(II) are colored. Water ++ ++ ++ (1) (2) Solution Solid Key: - - ++ Not Tested ++ Good conductor + Poor conductor . (d) Liquid (concentrated) sulfuric acid and sulfuric acid solution. is a covalently bonded molecule that does not ionize 2 2 1 Mg = [Ne] 3s . conduct the charge. These conduction electrons are free to travel throughout the metal crystal (c) Fused sucrose does not contain any ions to carry an electrical charge whereas the ions in silver The results of the tests are summarized in the nitrate are now free to move in the liquid and following data table. it is added to water. (b) Solid silver nitrate and solid sodium metal. Answer: 1995 D Explain the following in terms of the electronic structure and bonding of the compounds considered. Mobil electrons are furnished when electrons in filled molecular orbitals are excited into empty ones. to move and conduct an electric current.Bonding and Molecular Structure page 8 (d) Electron arrangements. Silver nitrate has an ionic 3p electron from the aluminum than to remove bond between the silver cation and the nitrate one electron from a paired 3s orbital in anion that is hydrated in water producing a magnesium. appreciable amounts of ions Liquid ++ ++ + are present as the molecular H2SO4 is dissociated (fused) into hydrogen and sulfate ions. (a) Liquid oxygen is attracted to a strong magnet. Empty Source of molecular orbitals are close in energy to filled Direct Current molecular orbitals. a metal crystal. (a) Sucrose. Answer: (a) N2 O2 . AgNO3 Sucrose Na H2SO4 (98%) (d) Concentrated sulfuric acid has very little water to Melting 212º 185º 99º Liquid at hydrolyze its ions and is only slightly ionized. Al = [Ne] 3s . (b) Silver nitrate has covalent bonds in the nitrate 1995 D (Required) anion and an ionic bond between the cation and The conductivity of several substances was tested anion but in the solid state these ions are not free using the apparatus represented by the diagram below. In sodium. Include the Lewis (electron-dot) structures in your explanation. the conductivity increases when a small amount of arsenic is incorporated (doped) into the crystal. however. 3p in water and. does not produce a It is easier to remove a shielded. unpaired conducting solution. whereas the CO2 molecule has no dipole moment. (a) Sucrose solution and silver nitrate solution. composed of all non-metals. whereas liquid nitrogen is not. (c) Liquid (fused) sucrose and liquid (fused) silver nitrate. therefore. it has a large number of closely spaced molecular orbitals that form a virtual continuum of levels called bands. whereas halides of zinc(II) are colorless. (b) The SO2 molecule has a dipole moment. conducting ionic solution.Nonconductor (1) Dissolves. account for the differences in conductivity between the two samples in each of the following pairs. single. (d) A crystal of high purity silicon is a poor conductor of electricity. accompanied by evolution of flammable gas (2) Conduction increases as the acid is added slowly and carefully to water Using models of chemical bonding and atomic or molecular structure.

. This results in a net dipole in the molecule. While there is a dipole in the carbon-oxygen bond.. . oxygen sets of d orbitals. If the amount of arsenic is kept small then these ions don’t interact. . (c) The N-O bonds in the NO2. (b) Molecules of AsF3 are polar. The extra electrons from the arsenic 1997 D (Required) occupy orbitals in a narrow band of energies that Consider the molecules PF3 and PF5. . Paramagnetism is associated with unpaired electrons. Answer: (a) hydrogen bonding (dipole-dipole attraction) is much larger in HF than in HCl. (c) The N-O bonds in the nitrite ion are stabilized by resonance and are of equal length.. In zinc ions. .. and yz). includes empty d orbitals that can be used to (d) Arsenic atoms have one more valence electron expand its valence shell.. (d) For sulfur. the fluorides SF2. 2 2 2 differently (the x -y and z more than the xy. There is an energy difference between the (d) There are only four orbitals in the valence shell of oxygen. It has 2 paired d electrons and 3 unpaired electrons. As a result. (c) A cobalt(II) ion has the electron configuration of [Ar] 3d7.. . whereas they are unequal in HNO2. This structure decreases the amount of energy required to excite an electron into the lowest-energy empty band in the silicon and increases the number of electrons that have enough energy to cross this gap. (b) :O: . sets of d orbitals is comparable to the energy of which it gets when it forms OF2.Bonding and Molecular Structure σ π σ 2p* 2p* 2p 2p 2s * 2s page 9 a a _ a _ a _ a _ a _ a _ a _ a _ a _ a E π σ σ a _ lie between the filled and empty bands of the silicon. lattice points in the silicon crystal.. According to crystal field theory. HF (normal boiling point = 20ºC) is a liquid. whereas for oxygen only OF2 is known to exist. and SF6 are known to exist.. but in HNO2. one s and three p’s. since that effect is stronger than diamagnetism.ion are equal in length.. − – metal electrons affects the metal d orbitals × [: O :: N : O :] [: O : N :: O :] . repulsion between the chloride lone pairs and the . S :O: :O: . Any substance that has both paired and unpaired electrons will exhibit paramagnetism. xz. resonance is no longer possible. The AsF5 molecule has a highly symmetrical trigonal bipyramidal shape with no lone electron pairs. as the chloride ion approaches the cobalt(II) ion. whereas HCl (normal boiling point = -114ºC) is a gas.. (a) At ordinary conditions.. Molecular Orbital Energy Level Diagrams Paramagnetism causes a substance to be attracted into the inducing magnetic field. 1996 D Explain each of the following observations in terms of the electronic structure and/or bonding of the compounds involved. as in oxygen but diamagnetism (repelled from the inducing magnetic field) is associated with paired electrons as in nitrogen.. whereas molecules of AsF5 are nonpolar. . . The valence visible light. the 180º bond angle cancels the dipole moment in the molecule. The energy difference between can hold no more than eight valence electrons. . :O = C = O: There is a dipole moment between the oxygen and the sulfur in sulfur dioxide and a bond angle of 119º. (b) AsF3 forms a pyramidal shaped molecule with a lone pair of electrons creating an asymmetrical region opposite the three highly electron-affinitive fluorine in the base.. with a hydrogen attached to an oxygen. S :O: . . .. SF4. Sulfur has 10 valence than silicon atoms and can lose an electron to + electrons in forming SF4 and 12 valence electrons form As ions which can occupy some of the to form SF6 (sp3d2 hybrid orbitals). all the d orbitals are orbitals of sulfur are in the n = 3 shell and paired and all the orbitals are degenerate.

atoms.doesn’t exist. explain your prediction. is not very soluble in water.06× 1014 s–1) 1998 D = 4. 1999 B Answer the following questions regarding light and its interactions with molecules. (b) A certain line in the spectrum of atomic hydrogen (c) On the basis of bonding principles.06 × 1014 waves/sec 3 form the dsp orbitals and is large enough to (ii) ∆E = ν accommodate 5 fluorine atoms around it. (i) Calculate the frequency. atom from the sixth energy level (n = 6) to the In each case. the electron must release basis of its increased water solubility.02× 10–19 J Answer each of the following using appropriate (iii) (4.178× 10–18 ( OR 1 1 ) J = 4. (a) The longest wavelength of light with enough energy to break the Cl–Cl boned in Cl2(g) is 495 nm. arsenic can hybridize to = 6.63× 10–34 joule. in s–1. = (6. (iii) Account for the observation that the amount of energy associated with the same electronic transition (n = 6 to n = 2) in the He+ ion is greater than that associated with the corre(b) polar.s)(6.Bonding and Molecular Structure page 10 (a) Draw the Lewis electron-dot structures for PF3 (ii) Calculate the energy. = 241. of the light. in nm. justify your choice.does exist.02× 10–19 J)(6. predict is associated with the electronic transition of the H whether each of the following compounds exists. each.870 J = 242 kJ (c) Dimethyl ether. of a photon of the and PF5 and predict the molecular geometry of light.178∞1018 J = –6. PF5 = trigonal bipyramid (ii) Calculate the wavelength. net dipole moment toward the nonsponding transition in the H atom.00 ×10 m / s = ? accommodate 5 fluorine atoms around it. ν = c = 3. 2. Answer: (a) PF3 = tripod (pyramid). Justify your answer. In each case. The n = 6 state is at a higher that is much more soluble in water and explain the energy than n = 2.84× 10–19 J OR ∆E = –2. Explain.445× 10–19 J 2 HH 2 | | H O C |C H – – – –| (c) The O-H bond in ethyl alcohol is very polar and will allow the molecule to be attracted to and dissolve in the polar water. H3C-O-CH3. 495 ×109 m (ii) AsF5 . Answer (c) (i) NF5 .84× 10–19 J 2 – 2 62 . in J. (iii) Calculate the minimum energy. second energy level (n = 2).02× 1023 mol–1) = chemical principles. Draw a structural isomer of dimethyl ether (b) (i) emits energy. (b) Is the PF3 molecule polar. in kJ mol–1. symmetrical position of the fluorines. nitrogen can’t hybridize to 8 form the dsp3 orbitals and is also too small to (a) (i) c = λν . H H E6 = 2. (i) NF5 (i) Indicate whether the H atom emits energy or (ii) AsF5 whether it absorbs energy during the transition. of the radiation associated with the spectral line.05× 10–20 J 2 6 ∆E = E6 – E2 = 4. or is it nonpolar? of the Cl–Cl bond.178∞1018 J Answer (ii) E2 = = –5. energy go to the lower state. and ions.

Se (atomic number 34).g.. (ii) Account for the fact at the carbon-oxygen bond length in CO32– is greater than the car. (a) Samples of natural selenium contain six stable isotopes.Answer: cal and are about 1 1/3 bond) found in a carbonate (a) all the isotopes have 34 protons but a different number of neutrons in the nucleus. Indicate the number of unpaired electrons in (b) Consider the molecules CF4 and SF4..(b) Write the complete electron configuration (e. the fact that the CF4 molecule is nonpolar. it has a stronger hold on the electron. explain (i) Draw the complete Lewis electron-dot strucwhat these isotopes have in common. F it releases more energy. explain why the first ture for each molecule. This requires more energy for the F electron to move to higher energy levels and when • S • the electron moves from higher to lower energies. they differ. In terms of atomic structure.84 ×10 J = . and whereas the SF4 molecule is polar. the polar C-F bonds are cancelled out by the equiangular pull of the 4 OR bonds. (d) Selenium reacts with fluorine to form SeF4. CO32–. therefore. account for (i) less than that of bromine (atomic number 35).30 × 10 sec •• •• •• •• •• •• •• •• page 11 λ= hc E 4. the carbonate ion.00 ×1017 nm/sec) bipyramidal structure. state. Indicate similar resonance structures for the carbonate ion. the ground-state atom. there are two other the complete Lewis electron-dot structure for SeF4 •• •• O C O •• •• and sketch the molecular structure.. •• •• F •• •• •• F C F •• •• •• F •• •• •• F •• F •• F •• S •• •• F •• . CO2.ν = = E h 6.(c) In terms of atomic structure. and selenium. etc. With an expanded octet and trigonal (6. + has a nuclear charge of 2+ vs H with (iii) the He F a 1+. F 1999 D Answer the following questions using principles of 2000 D chemical bonding and molecular structure.84 × 10−19 J electrons at the center of the bipyramid.) for a selenium atom in the ground bon-oxygen bond length in CO2. and explain your reasoning. (i) Draw the complete Lewis electron-dot struc. (ii) the pi O=C double bond in CO2 is shorter than a single O-C resonance sigma-bond (all are identi.11×10−7 m 14 −1 ν 7. 1s2 2s2.626 ×10-34 J ⋅ sec −19 (b) (i) (ii) in the tetrahedral CF4.00 ×10−18 m/sec λ= = = 4. and justify your answer. ion. this gives = 411 nm a “seasaw” shape to the molecule and an uneven pull to the polar S-F bonds. SF4 has a pair of unbonded λ= = 4. whether the molecule is polar or nonpolar.Bonding and Molecular Structure =7.30× 1014 sec–1 c 3. Answer the following questions about the element (a) Consider the carbon dioxide molecule. ionization energy of selenium is (ii) In terms of molecular geometry. Draw •• •• :••: O O::C :: O (a) (i) ••::••: •• : . and how ture for each species.626 × 10−34 J ⋅ sec)(3. (ii) greater than that of tellurium (atomic number Answer 52).

therefore. references to both substances. Account for each of the following observations about your answer must include references to both pairs of substances. (a) Even though NH3 and CH4 have similar molecular masses. 2002 D Required Use the principles of atomic structure and/or chemical 2001 D bonding to explain each of the following. · · Se ·· ·· · F · ·F · · · · · · Se · ·F· ·F· · · · · ·· ·· required to overcome this higher IMF in NH3 and. . 4s [↑↓ 4p [↑↓ ] ][↓ ][↑ ] Hund’s rule indicates that each of the orbitals will (b) Both ethane’s and hexane’s IMF consist mainly of weak London dispersion forces. (a) Be has 1 more electron in the 2s orbital than Li. paired 4p orbital. use appropriate substances. proton to “pull in” the 2s orbital. F The larger ionic charge creates a stronger F Coulombic attraction between the anion and (d) see-saw shape cation in MgO and a higher temperature is Because F is very electronegative and the required to overcome it and melt it. In each part. F (b) At 25°C and 1. your answer must include (a) The atomic radius of Li is larger than that of Be. (a) NH3 exhibits hydrogen bonding (H attached to (b) the second ionization energy (IE ) removes the 2 nitrogen. greater than it is in C2H6. The greater be filled with a single electron before it gets number of electrons in hexane (50 vs. in ethane to condense. ethane (C2H6) is a gas and (d) The boiling point of Cl is lower than the boiling 2 hexane (C6H14) is a liquid. (d) Magnesium oxide is a Mg2+O2– ionic compound while sodium fluoride is a Na+F– ionic compound. The IE2 in potassium is removing a very than CH4 which doesn’t exhibit H-bonding. leaving a noble gas between molecules which creates a larger IMF kernel. has a higher boiling point. point of Br2. molecule is asymmetric with respect to the fluorines. the single paired 4p electrons has 1 elecat 25oC but for ethane. principles of chemical bonding and/or intermolecular forces. the removal of 1 electron still leaves a (c) Si forms strong network covalent bonds (4 per atom) to create a high melting solid. More energy is which requires a great deal more energy.852°C) than NaF (993°C). Cl–Cl) do makes it easier to remove a electron (lower not form strong IMF.Bonding and Molecular Structure (b) 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p4 page 12 2 unpaired electrons.410°C) Answer: than Cl2 (-101°C). (d) MgO melts at a much higher temperature not in another larger orbital. making it smaller Answer: than Li. (b) The second ionization energy of K is greater than the second ionization energy of Ca. the fewer electrons make a tron easily removed to create the 3 unpaired 4p smaller IMF and that is not strong enough to cause orbitals which is energetically favorable. Be also has 1 more (2. weak London dispersion forces). this molecule is polar. only stable 3p orbital electron in its noble gas kernel. The non(ii) the shielding effect is stronger in Te and polar molecules of Cl2 (covalent bond. only weak London ionization energy). attracted to N in adjacent molecule) second 4s orbital in calcium. NH3 has a much higher normal boiling (c) The carbon-to-carbon bond energy in C2H4 is point (-33°C) than CH4 (-164°C).0 atm. In each part. dispersion forces and that makes it easy to melt at F a low temperature. ethane’s 18) paired. enough to make it a liquid (c) (i) in Se. In your answers. creates a greater IMF. (c) Si melts at a much higher temperature (1. bromine.

therefore a higher boiling point than (b) (i) propane. larger molar mass means a slower molecule. H—C—C≡ C—H (a) At 25˚ C and 1 atm. propanone. whereas and the total number of pi (π) bonds in the the shape of BF4– ion is tetrahedral. which is stronger than the carbon-to-carbon Answer: H O H single bond in C2H6. (a) (i) H–C–C–C–H page 13 H H more electrons mean greater vander Waals attractions in Br2. explain why they do not have the same value for their standard O – C–H heat of vaporization. indicated by the arrow in the structure above. In each part. 32 electrons. ∆H˚vap. H (i) indicate the hybridization of the carbon atom (b) The melting point of NaF is 993˚ C. H–C–C–C–H (ii) predict the approximate carbon-to-carbon-toH H carbon bond angle. (You must include H–C – C–H specific information about both compounds in H H each pair.0 32.0 47. molecule . molar mass = 44 Cl2. molar mass = 58 2003 D (repeated in organic) Compound Compound Name Formula Propane Propanone 1-propanol CH3CH2CH3 CH3COCH3 CH3CH2CH2OH ∆H˚vap (kJ mol-1) higher # electrons means larger van der Waal forces. answer the following questions about organic compounds.Bonding and Molecular Structure (c) the carbon-to-carbon bond in C2H4 is a double bond. (d) Cl2 has 34 electrons and Br2 has 70 electrons. H (b) For each pair of compounds below. F2 is a gas whereas I2 is a | solid. 2 pi (ii) Propanone and 1-propanol (c) Draw the complete structural formula for an 2004 D isomer of the molecule you drew in.3 Using the information in the table above.) (d) (i) sp (i) Propane and propanone H–C=C–O–C–H H H H H H H H–C – C – O-H C H H O – C – C–H C H H H (ii) 6 sigma. each of the following observations. Use appropriate chemical principles to account for (d) Given the structural formula for propyne below. more energy to overcome them when (ii) 120˚ it boils and. your H response must include specific information about both | ↓ substances. 26 electrons. H H H H H H H–C=C–C–O–H H–C=C–C–H HO H H H HO–C=C–C–H H H 19. the oxygen creates a polar molecule and dipol–dipole interactions (ii) 1-propanol has an –OH which creates a site for hydrogen bonding with other –OH on adjacent molecules increasing intermolecular forces that must be overcome in order to vaporize the liquid. whereas the melting point of CsCl is 645˚. part (a) (i). (a) For propanone. (ii) indicate the total number of sigma (σ) bands (c) The shape of ICl4– ion is square planar. H H (i) draw the complete structural formula (showing (c) H H O all atoms and bonds).

This creates a greater solute-solvent attraction and greater solubility.: . . making it harder to melt. . is very soluble in water. . (ii) What is the hybridization of the valence orbitals of P in PF5? CF4 (iii) What is the geometric shape formed by the atoms in SF4? (c) Two Lewis structures can be drawn for the OPF3 molecule. (a) In the boxes provided. The I2 molecule has 106 electrons to the 18 of the F2 and.: . water.: . answer the following questions about the chemical bonding particular molecule indicated. therefore. Answer: (a) F2 is a smaller & lighter molecule than I2. . . is only moderately soluble in water. :O : . P F F . . . exhibits a greater vander Waal attraction. on average is faster than I2. :. (c) The ICl4– ion contains the sp3d2 hybridization due to the expanded octet around the central iodine. The chlorides are equatorially bonded in a square around the iodine with the extra pairs of electrons along the axis. :O : . (b) each ion in NaF has a smaller size than the corresponding ion in CsCl. :F . NH3. . as shown below. SF4 PF5 page 14 2005 D Required 6. at the same temperature F2. (d) ammonia is a more polar molecule than phospine and can make hydrogen bonds with the solvent. :F P F . draw the complete Lewis (i) What is the F-C-F bond angle in CF4? structure (electron-dot diagram) for each of the three molecules represented below.: . PH3. :F . . The BF4– ion has sp3 hybridization which characteristically has the tetrahedral shape. whereas phosphine. Answer the following questions that relate to (b) On the basis of the Lewis structures drawn above.Bonding and Molecular Structure (d) Ammonia. . Structure 1Structure 2 (i) How many sigma bonds and how many pi bonds are in structure 1? (ii) Which one of the two structures best repre- . This smaller size creates a larger charge density and greater ion Coulombic attraction in the NaF. .

Bonding and Molecular Structure page 15 sents a molecule of OPF3? Justify your anpoints of the substances. . phosphorus is 0 (5 valence electrons – 5 (i) Identify the element. n = 2. Justify your answer. phosphorus is +1 (5 valence electrons – 4 (a) (i) assigned electrons) force NH3 NF3 According to the electroneutrality rule. .) of the valence electrons in the atom. for its electrons than the other two. whereas the boiling point of NF3(l) is 144 K. (c) As shown in the table below. the better Lewis structure is the one with the smallest separation of formal charge.. bonding and/or intermolecular forces to respond to each of the following. (ii) Which isotope is more abundant? Justify your In structure 2. trons). The valence electrons – 6 assigned electrons).: . . 1 pi (ii) Explain the reasons for the trend in the first (ii) structure 1. whereas the charged chlorine atom has the greatest attraction melting point of NaCl(s) is 801˚C.Answer: trons). In structure 1. ionization energy. the first ionization Answer: energies of Si.. P.93 amu and the orine is 0 (7 valence electrons – 7 assigned elecmass of the other isotope is 64. London dispersion polar attraction hydrogen bonding ionic attraction + + + + + - (ii) the ability of ammonia to create intermolecular hydrogen bonds. leads to higher amount of energy to separate the molecules by boiling them. The opposite is (ii) Account for the difference in the melting . This means (i) Identify the type of bonding in each substance.. P 1012 (b) (i) 109.g. n = 3. . :F: :F: Element First Ionization Energy :F : :F ::F : . (kJ mol-1) : F P F: .. etc.5˚ Cl 1251 (ii) sp3d (i) For each of the three elements. and Cl show a trend.. Your responses must include specific information about all substances referred to in each (b) question. assigned electrons). . Si > P > Cl and points of the substances.. (a) At a pressure of 1 atm. . each flumass of one of the isotopes is 62. n = 3 (ii) Account for the difference in the boiling (ii) in terms of atomic radius. This smaller size creates a larger charge density and greater ion Coulombic attraction in the NaCl. each fluorine is 0 (7 valence electrons – 7 assigned elec. that it takes more energy to remove an electron from chlorine that the other two. P.93 amu. (i) Identify the intermolecular forces(s) in each substance. Cl. n =1. : F: Si 786 : F: : F .. nuclear charge Cl > P > Si. swer in terms of formal charge. oxygen has a formal charge of 0 (6 (d) A certain element has two stable isotopes. (a) : F C F: ... . :F. . (c) (i) 4 sigma. . identify the (iii) see-saw quantum level (e. . (c) (i) Si.... making it harder to melt.. .. the boiling point of NH3(l) is 240 K.e. 2005 D Use principles of atomic structure. the smaller and higher (b) The melting point of KCl(s) is 776˚C.. ... . i. (i) both compounds have ionic bonding (ii) the sodium ion in NaCl is a smaller size than the corresponding potassium ion in KCl. valence electrons – 7 assigned electrons). structure 1. S : . oxygen has a formal charge of –1 (6 answer.. n = 3.

the isotope that is closer to the atom mass of the element is more abundant of the two (63.93. then the atomic mass of the element must be between 62. page 16 (ii) 62. 64. since the atomic mass of an element is the weighted average of its natural isotopes.94.93 and 64.546 = 1.384) .94 – 63. (d) (i) copper.Bonding and Molecular Structure true for silicon and it should have the smallest value.93 = 0.546 – 62.616.