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Exam Name 1) Which compound would be expected to show intense IR absorption at 3300 cm-1? A) butane B) CH3CH2C CH C)CH3C CCH3 D) but-1-ene 1) 2) Which compound would be expected to show intense IR absorption at 2820, 2710 and 1705 cm-1? A) CH3COCH2CH3 B) CH2 CHCOCH3 C) PhCOCH3 D) PhCHO 2) 3) Which compound would be expected to show intense IR absorption at 2250 cm-1? A) (CH3)2CHCN B) CH3CH2CH2CO2H C) CH3CH2CH2CONH2 D) (CH3)2CHCH2OH 3) 4) Which compound would be expected to show intense IR absorption at 1680 cm-1? 4) ESSAY. Write your answer in the space provided or on a separate sheet of paper. 5) Deduce a possible structure for the compound with the IR absorptions below. C3H3Br: 3300, 2900, 2100 cm-1 6) Deduce a possible structure for the compound with the IR absorptions below. C3H5N: 2950, 2250 cm-1 7) Deduce a possible structure for the compound with the IR absorptions below. C5H8O: 2950, 1750 cm-1 8) Deduce a possible structure for the compound with the IR absorptions below. C4H8O: 2950, 2820, 2715, 1715 cm-1 1

9) Deduce a possible structure for the compound with the IR absorptions below. C6H10: 3040, 2980, 1660 cm-1 10) How could IR spectroscopy be used to distinguish between the following pair of compounds? CH3OCH2CH3 and CH3CH2CH2OH 11) How could IR spectroscopy be used to distinguish between the following pair of compounds? HOCH2CH2CHO and CH3CH2CO2H 12) How could IR spectroscopy be used to distinguish between the following pair of compounds? CH3COCH CHCH2CH3 and CH3COCH2CH2CH CH2 13) How could IR spectroscopy be used to distinguish between the following pair of compounds? CH3CH2C CH and CH3C CCH3 14) Ethyne (HC CH) does not show IR absorption in the region 2000-2500 cm-1 because: A) C C stretches occur at about 1640 cm-1. B) there is a change in the dipole moment when the C C bond in ethyne stretches. C)there is no change in the dipole moment when the C C bond in ethyne stretches. D) C H stretches occur at lower energies. 14) ESSAY. Write your answer in the space provided or on a separate sheet of paper. 15) Describe the molecular ion region in the mass spectrum of CH3CH2Br. 16) 2-Methylhexane shows an intense peak in the mass spectrum at m/z = 43. Propose a likely structure for this fragment. 17) Which compound would show a larger than usual M+2 peak in the mass spectrum? A) CH3CH2SCH3 B) (CH3)2CHNH2 C) CH3(CH2)2CH3 D) CH3CH2CO2H 17) 18) Which compound would be expected to show intense IR absorption at 1715 cm-1? A) hex-1-yne B) (CH3)2CHCO2H C)(CH3)2CHNH2 D) 2-methylhexane 18) 19) Which compound would be expected to show intense IR absorption at 3363, 3185, 1660 cm-1? A) CH3CH2CH2OH B) but-1-ene C) CH3CH2CONH2 D) (CH3)2CHNH2 19) 2

20) Which compound would be expected to show intense IR absorption at 1746 cm-1? A) CH3CH2OCH2CH3 B) CH3CH2SCH3 C) CH3CO2CH2CH3 D) CH3CH2CN 20) 21) Absorption is the measurement of the amount of light absorbed by a compound as a function of the wavelength of light. 21) 22) An infrared wavelength of 4.48μm is equivalent to a wavenumber of cm-1. 22) 23) An infrared wavelength of 5.81μm is equivalent to a wavenumber of cm-1. 23) 24) Which has the higher speed in a vacuum, ultraviolet or infrared light? 24) 25) The wavelength and frequency of a given wave of electromagnetic radiation are proportional. 25) 26) The energy of a photon is proportional to its wavelength. 26) 27) The energy of a photon is proportional to its frequency. 27) 28) In what units are frequency values typically given? 28) 29) In an IR spectrometer, the uses prisms or diffraction gratings to allow only one frequency of light to enter the detector at a time. 29) 30) Which region of the electromagnetic spectrum, IR or UV, contains photons of the higher energy? 30) 31) Which region of the electromagnetic spectrum, radio or visible, is characterized by waves of shorter wavelength? 31) 32) Which region of the electromagnetic spectrum, IR or X-ray, is characterized by waves of lower frequency? 32) ESSAY. Write your answer in the space provided or on a separate sheet of paper. 33) Which has a lower characteristic stretching frequency, the C H or C D bond? Explain briefly. 34) Which has a lower characteristic stretching frequency, the C O bond or the C O bond? Explain briefly. 35) The region of the IR spectrum which contains the most complex vibrations (600-1400 cm-1) is called the region of the spectrum. 35) 3

36) In order for a vibration mode to be observable in the IR, the vibration must change the of the molecule. 36) 37) What effect does conjugation typically have on the frequency at which absorption by C C occurs? A) Conjugation decreases the frequency at which absorption occurs. B) Conjugation increases the frequency at which absorption occurs. C) Conjugation does not affect the frequency at which absorption occurs. 37) ESSAY. Write your answer in the space provided or on a separate sheet of paper. 38) Describe the fate of a molecule from introduction to detection in a mass spectrometer. 39) When a high energy electron impacts molecule M in the ionization chamber, what type of species is initially produced? A) cation B) radical C) radical cation D) radical anion E) anion 39) 40) In a mass spectrum, the peak of greatest abundance is referred to as the. 40) 41) What spectroscopic technique can be used to determine the molecular formula of a compound? 41) ESSAY. Write your answer in the space provided or on a separate sheet of paper. 42) The natural abundances of chlorine's two major isotopes are 35Cl (75.5%) and 37Cl (24.5%). If the mass spectrum of chlorobenzene contains a peak at m/z 114 with an abundance of 15.0%, calculate the % abundance of the peak at m/z 112. 43) An molecular ion peak usually indicates the presence of an odd number of nitrogen atoms in the molecule. A) intense B) odd C) absent D) even 43) 44) The mass spectrum of alcohols often fail to exhibit detectable M peaks but instead show relatively large peaks. A) M-17 B) M+2 C) M+1 D) M-18 E) M-16 44) 4

45) How could IR spectroscopy be used to distinguish between the following pair of compounds? 45) CH2 CHCH2CH(CH3)2 and CH3CH2CH2CH(CH3)2 46) How could IR spectroscopy be used to distinguish between the following pair of compounds? 46) (CH3)3N and CH3NHCH2CH3 47) Sodium borohydride can be used to reduce cyclohexanone to cyclohexanol. How could one use IR to determine if all starting material had been consumed? 47) 48) Which compound would be expected to show intense IR absorption at 3367, 3282 cm-1? A) but-1-ene B) CH3OCH2CH3 C) PhCO2H D) PhCH2NH2 48) 49) Which compound would be expected to show intense IR absorption at 1640 cm-1? A) CH3CH2CH2OH B) 2-methylheptane C) CH3CH2COCH3 D) hex-1-ene 49) 50) The two most abundant isotopes of boron are 10B and 11B, with 11B being about 4 times more abundant. In the mass spectrum of trimethylborate [(CH3O)3B],. A) the peak at m/z 103 has an intensity which is 1/4 the intensity of the peak at m/z 104 B) the peaks at m/z 103 and m/z 104 have equivalent intensities C)the peak at m/z 103 has an intensity which is 4 times that of the m/z 104 peak D) none of the above 50) 51) Absorption of what type of electromagnetic radiation results in ionization? A) microwaves B) X-rays C) infrared light D) radio waves E) ultraviolet light 51) 52) Absorption of what type of electromagnetic radiation results in electronic transitions? A) ultraviolet light B) microwaves C) radio waves D) X-rays E) infrared light 52) 5

53) Absorption of what type of electromagnetic radiation results in transitions among allowed rotational motions? A) radio waves B) infrared light C) ultraviolet light D) X-rays E) microwaves 53) 54) Absorption of what type of electromagnetic radiation results in transitions among allowed vibrational motions? A) infrared light B) X-rays C) radio waves D) ultraviolet light E) microwaves 54) 55) Absorption of what type of electromagnetic radiation results in transitions among allowed nuclear magnetic spin states? A) ultraviolet light B) radio waves C) infrared light D) X-rays E) microwaves 55) 56) At approximately what wavenumber does one expect to find the carbon-carbon triple bond stretch in the IR spectrum of an alkyne? 56) 57) Which of the following fragment peaks would not be present in the mass spectrum of n-hexane? A) 71 B) 29 C)57 D) 43 E) 87 57) 58) A compound (C5H8O) shows IR absorptions at 3600 and 3300 cm-1. Its 1H NMRspectrum contained singlets at δ 1.5, 2.2, and 2.9 (broad) (ppm) in a ratio of 6:1:1. Name this compound. 58) 59) Provide an equation which relates the energy of a photon to its wavelength. 59) 60) The frequency of the stretching vibration of a bond in IR spectroscopy depends on what two quantities? A) the electronegativity of the atoms and the nuclear charges of the atoms B) the masses of the atoms and the stiffness of the bond C) the stiffness of the bond and the electronegativity of the atoms D) the electronegativity of the atoms and the masses of the atoms E) the nuclear charges of the atoms and the atomic radii 60) 6

61) In IR spectroscopy, the C O bond has a frequency than the C N bond because. A) lower, an O atom has more mass than an N atom B) higher, an O atom has an even number of neutrons C)higher, an O atom has more electronegativity than an N atom D) higher, an O atom has more mass than an N atom E) lower, an O atom has more electronegativity than an N atom 61) 62) A nonlinear molecule with n atoms generally has fundamental vibrational modes. A) 2n B) 2n - 2 C)3n - 6 D) 3n - 3 E) 3n 62) 63) The IR spectrum of a sample contains absorptions at 3050, 2950, and 1620 cm-1. To what class of organic compound does this sample most likely belong? A) alkyne B) ester C) alkene D) alcohol E) alkane 63) ESSAY. Write your answer in the space provided or on a separate sheet of paper. 64) How does the O-H stretch in the IR spectrum of a carboxylic acid differ from the O-H stretch of an alcohol? 65) When a compound contains a sulfur atom, its mass spectrum contains a larger than usual peak. A) M+2 B) M-1 C)M-2 D) M E) M+1 65) 66) Arrange the following regions of the electromagnetic spectrum in order of increasing energy: microwave, UV, visible, and IR. 66) 67) Arrange the following regions of the electromagnetic spectrum in order of increasing wavelength: X ray, radio, UV, and IR. 67) 68) What wavenumber corresponds to the wavelength of 4 μm? 68) 69) Rank the following bonds in order of increasing stretching frequency (cm-1) in IR spectroscopy: C H, C C, C O, and C=O. 69) 70) Rank the following bonds in order of increasing stretching frequency (cm-1) in IR spectroscopy: O H, C N, C N, and C=O. 70) 71) Which of the following most closely matches the C C stretching frequency? A) 3000 B) 3300 C) 2200 D) 1200 E) 1700 71) 7

72) Which of the following has a C H stretch that occurs at the highest stretching frequency? A) hex-1-ene B) hexane C)(E)-hex-2-ene D) hex-2-yne E) hex-1-yne 72) 73) Which of the following compounds has the lowest carbonyl stretching frequency? 73) 74) What m/z characterizes a strong peak in the mass spectrum of cyclopentanol? A) 84 B) 86 C)68 D) 85 E) 70 74) 75) The presence of which element is indicated by a peak at m/z 127 and a characteristic 127-unit gap in the mass spectrum? A) Cl B) I C)S D) Br E) N 75) 76) What wavelength in mm is equivalent to a wavenumber of 1750 cm-1? 76) 77) Which of the following molecules would be expected to have its C=C stretching frequency at the highest wavenumber: benzene, 1,3-pentadiene, or 1-pentene? 77) 78) Which of the following would not have a C-H stretch at about 3050 cm-1? A) 2-pentene B) 2-methyl-2-pentene C) 2,3-dimethyl-2-pentene D) 1-pentene E) 2,4-dimethyl-2-pentene 78) 79) Which of the following stretches tends to be the least intense? A) C-H B) C=C C)C=O D) O-H (carboxylic acid) E) O-H (alcohol) 79) 8

80) Which of the following compounds would contain characteristic IR stretches at 3300 and 2200 cm-1? A) CH3CH=CHCH2OH B) (CH3)2CHCN C) CH3C CCH2CH3 D) CH3CH2CH2C CH E) CH3CH2CHO 80) 81) Which of the following does not have a broad absorption with one or more spikes that is centered about 3300 cm-1 in the IR? A) (CH2=CHCH2)2NH B) (CH3CH2CH2)3N C) CH3CH2CH2NH2 D) (CH3)3CNH2 E) (CH3CH2CH2)2NH 81) 82) In addition to a carbonyl stretch, which of the following molecules exhibits two characteristic stretches at 2700 and 2800 cm-1? A) CH3CH2CH2COCl B) CH3CH2CO2CH3 C) CH3CH2CH2CO2H D) CH3CH2CH2CHO E) (CH3CH2)2CO 82) 83) Which of the following molecules would have the highest frequency carbonyl stretch? A) (CH3CH2)2CO B) CH3CH2CH2CO2H C) CH3CH2CH2CHO D) CH3CH2CH2CONH2 E) CH3CH2CO2CH3 83) 84) Which of the following bonds, C N, C N, or C N, has an IR stretch around 1600 cm-1? 84) 85) Arrange the following IR bond stretches in order of increasing wavenumber: C O, C C, O-H, and C C. 85) 9

86) Which of the following structures is consistent with the IR spectra shown below? 86) A) B) C) D) E) 87) One of the following functional groups, sometimes shows a single weak to medium IR adsorption peak in the 2100 to 2250 cm-1 range. Depending on the structure of the compound this peak is sometimes not present, making it easy to misinterpret the spectrum. Which functional group is it? A) Alkene B) Alcohol C) Alkyne D) Carboxylic acid E) Carbonyl 87) 10

88) Which of the following structures is consistent with the IR spectra shown below? 88) A) B) C) D) E) 11

89) Which of the following structures is consistent with the mass spectrum shown below? 89) A) B) C) D) E) 12

90) What are the predicted m/z values (masses )and relative heights of all the molecular ions of 1-bromoethane that would appear on a mass spectrum (excluding peaks produced by 13C and 2H)? A) M+ peak at m/z = 79 and an M+1 peak at 81 The M+1 peak is approximately the same height as the M+ peak. B) M+ peak at m/z = 108 and an M+2 peak at m/z = 110 The M+2 peak is approximately the same height as the M+ peak. C)M+ peak at m/z = 108 and an M+2 peak at m/z = 110 M+2 peak is approximately 1/2 the height of the M+ peak. D) M+ peak at m/z =108 and an M+1 peak at m/z =110 The M+1 peak is approximately 1/2 the height of the M+ peak. E) M+ peak at m/z = 79 and an M+1 peak at 81 The M+1 peak is approximately 1/2 the height of the M+ peak. 90) 13

Answer Key Testname: SPEC_ALL 1) B 2) D 3) A 4) Compound C 5) HC CCH2Br 6) CH3CH2CN 7) cyclopentanone 8) CH3CH2CH2CHO 9) cyclohexene 10) O-H stretch at 3300 cm-1 11) A carboxylic acid will have a very broad O-H absorption near 3000 cm-1; an aldehyde has characteristic C-H stretches at 2820 and 2720 cm-1. 12) C O absorption in conjugated carbonyl appears at lower wavenumber 13) Terminal alkyne stretch at 3300 cm-1, lower intensity C C absorption in internal alkyne 14) C 15) The natural abundance of the isotopes 79Br and 81Br are about the same; therefore, there will be peaks of equal intensity at m/z 108 and 110. 16) (CH3)2CH+ 17) A 18) B 19) C 20) C 21) spectroscopy 22) 2230 23) 1720 24) They have the same speed. 25) inversely 26) inversely 27) directly 28) Hertz or cycles/sec or sec-1 29) monochromator 30) UV 31) visible 32) IR 33) C D; heavier atoms vibrate more slowly 34) Stronger bonds are generally stiffer, thus requiring more force to stretch or compress them. The C O bond is the weaker of the two and hence has the lower stretching frequency. 35) fingerprint 36) dipole moment 37) A 38) Upon introduction, sample molecules are ionized by an electron beam passing through a vacuum chamber. The resulting radical cation and fragment cations are accelerated into the flight tube of the magnet by a negatively charged plate. In the flight tube, the path of the ions is bent by the existing magnetic field. For a given magnetic field strength, only one m/z will be bent in such a way that its path matches the curvature of the tube and reaches the detector. The entire m/z range is scanned by varying the strength of the magnetic field. 39) C 40) base peak 41) high resolution mass spectrometry 14

Answer Key Testname: SPEC_ALL 42) 46.2% 43) B 44) D 45) C C stretch around 1640 cm-1; vinylic C H stretch above 3000 cm-1 46) N-H absorption near 3300 cm-1 47) Presence of C O stretch would indicate incomplete reaction. 48) D 49) D 50) A 51) B 52) A 53) E 54) A 55) B 56) 2100-2200 cm-1 57) E 58) 2-methylbut-3-yn-2-ol 59) E = (hc)/λ 60) B 61) A 62) C 63) C 64) Because of the unusually strong hydrogen bonding in carboxylic acids, the broad O-H stretch is shifted to about 3000 cm-1 centered on top of the usual C-H absorption. This broad O-H absorption gives a characteristic overinflated shape to the peaks in the C-H region. 65) A 66) microwave < IR < visible < UV 67) X ray < UV < IR < radio 68) 2500 cm-1 69) C O < C=O < C C < C H 70) C N < C=O < C N < O H 71) C 72) E 73) 74) C 75) B 76) 5.71 mm 77) 1-pentene 78) C 79) B 80) D 15

Answer Key Testname: SPEC_ALL 81) B 82) D 83) E 84) C N 85) C O < C C < C C < O H 86) B 87) C 88) C 89) A 90) B 16