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Paula Yurkanis Bruice Students Solutions PDF
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Paula Yurkanis Bruice Students Solutions PDF
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to be accounted for. ‘The two oxygens in the molecular formula tells us that the compound is an ester because a broad singlet between 10 and 12 ppm that would indicate a carboxylic acid is not present, The remainder of the molecule contains two cutbons and five hydrogens. The two remaining signals, a triplet (1.4 ppm) that integrates to 3 protons and a quartet (4.4 ppm) that in- tegrates to 2 protons, are characteristic of an ethyl group. The three known segments can now be joined in ‘one of wo ways: ° | tL aun poe ( T OCHCH, CIACHY 0 SS ‘ethyl benzoate Ee ‘The choice hetween the two compounds can be made by looking at the chemical shift of the methylene protons. In the ethyl ester, the signal will be highly deshielded by the adjacent oxygen. In the phenyl es ter, the signal will be at ~2.1 ppm because the methylene protons would be next to the carbonyl group. Because the chemical shift of the methylene protons is 4.4 ppm benzoate. we know that the compound is ethyl CCopyrigt © 2014 Peason Edoction, Ine Spectroscopy Problems Because all three specira are given by ethylmethybenzenes. the low-frequency signals in both the 'H NMR, and "C NMR spectra can be ignored because they belong to the methyl and ethyl substituents, The key t0 determining which spectrum belongs to which ethylmethylbenzene can be found in the aromatic rexion of the 'H_ NMR and SC NMR spect c iw Jone l 7 a CHACHy, 4 The aromatic region of the "'C NMR spectrum of 4-ethylmethylbenzene will show Four signals because it has four different ring carbons, cH, = #1 le 8 oe CHSCHy The aromatic region of the '"C NMR spectrum of 3-ethylnethylbenzene will show six signals beeause it has six different ring carbons cH Hl 16 GQ #2 as #3 {cH.CH, a ighals because ‘The aromatic region of the '""C NMR spectrum of 2-cthylmethylbenzene will also show six it has six different ring carbons, We now know that spectrum (b) is the spectrum of 4-ethylmethylbenzene because its SC NMR spectrum hhas four signals and the other two compounds will show six signals To distinguish between 2-ethylmethylbenzene and 3-ethylmethylbenzene. we need to look at the spit patterns in the aromatic regions of the 'H NMR spectra, Analysis of the aromatic region fr spectrum (e) difficult because the signals are superimposed. Analysis of the aromatic region for spectrum (a) provides the needed information. A wiplet (7.2 ppm) that integrates to 1 proton is clearly present. This means that Copsright 2014 Beason Eaton, M. Spectroscopy Problems 45 spectrum (a) is 3-ethylmethylbenzene bec spectrum (¢) is 2-ethylmethylbenzene, ie 2-ethylmethylbenzene would not show a triplet. Therefore, R R oF + singket THD a NR S doublet 2H) } wiplet (Ui) f doublet 2H) spliting pattera for S-methylethyl benzene splitting patern for 2-merhylethyl benzene doublet 2H) ‘The final assignments ane: (a) $ethylmethylbenzene (b) 4-ethylmethylbenzene _(¢) 2-ethylmethylbenzene The simplicity of the NMR spectrum of a compound with 7 carbons and [4 hydrogens indicates that the compound must be symmetrical, From the molecular formula, we see that it has one degree of unsatura- tion. The absence of signals near 5 ppm rules out an alkene, Because the compound has an oxygen. the degree of unsaturation may be due to a carbonyl group. The doublet (1,1 ppm) that integrates to 12 protons and the septet (2.8 ppm) that integrates to 2 protons suggest the presence of 10 isopropyl groups If two isopropyl groups are subtracted from the molecular formula, we find that the remainder of the mol- ecule is composed of one earbon and one oxygen. Thus, the compound is the one shown here. voy ‘The molecular formula tells us that compound has one degree of unsaturation, The multiplet (5.2 ppm) that integrates to 1 proton is due to t vinylic proton (that is, itis attached to an sp” carbon). Thus, the degree of ‘unsaturation is duc to a carbon-carbon double bond. Because there is only one vinylie proton, we ean as- sume that the alkene is trisubstituted. ‘Three additional signals are present that each integrate to 3 protons, suggest ‘due to methyl groups. The alkene. therefore, iy 2-methyl-2-butene. all three signals are cH, N\ c / cH Notice that two of the three signals given by the methyl groups are singlets and one is a doublet. The methyl group that gives the doublet is bonded tothe carbon that is attached to the vinylic proton. The other two methyl groups are bonded to the other yp" eatbon. ©: Peaon Futon, he 36. Spectroscopy Problems at ~2120 em." indicates the presence of a carbon-carbon triple bond. The yydrogen bonded to an yp carbon. Thus. the A mediun-intensity absorp Shap absonption at 3300 em”! is due to the C—H steteh 01 compound is terminal alkyne. The intense and broad peak centered at 3300 em. ' isevidence of an OH group. ‘The NMR spectrum can be used to determine the co that integrates to 1 proton is due to the proton of the t jectivity between the groups, The sig minal alkyne, nal (2.5 ppm) The singlet (3.2 ppm) that integrates to 1 proton must be due to the proton of the OH group. The singlet (4.2 ppm} that integrates to 2 protons must be duc t0 an bonded carbon to the OH group. The compound is 2-propyn-I-ol ethylene group that connects the triply Ho CHO ‘This arrangement explains the absence of any splitting and the highly desbielded nature of the signal for the methylene group, The two singlets (4.9 and 5.1 ppm that each inte that the compound is an alkene. fate 10 | proton are viny ic protons, Therefore, we know ‘The singlet (2.8 ppm) that integrates to 3 protons is methyl ssoup. The deshieldi attached to an 9p" carbon, esulls from its being If we subtract the wo vinylic protons. the Wo 9p" carbons of the alkene, and the methyl group from the molecular formula, we are left with CHsCI. Thus, a catorometiy! group is the fourth substituent of the al ene and gives the singlet (4.9 ppm) that integrates te 2 protons. Its deshiclding is due 10 the proximity to the electronegative chlorine, Now we need to determine the substitution pattern of the alkene. The absence of splitting indicates that the {wo vinylic protons must be attached to the same carbon. If these protons were cis oF trans to one other they would give doublets with significant J values. Geminal protons attached to sp" carbons have very small J values. so splitting is typically not observed (sce Table 15.2 on page 676 of the text) ‘Thus. the compound is 3-choro-2-methyl-I-propene. 9 2084 Psa asain, 3. 3B Spectroscopy Problems 47 nal that intes The only the alcohol ates to | proton is the singlet at 2.2 ppm. This must be due to the OH group of ‘The signals centered around 7.3 ppm are those given by benzene-ring protons, Because they integrate to 5 protons, the benzene ring must be monosubstituted. “The two triplets (2.8 and 3.8 ppm) that cach integrate to 2 protons suggest two adjacent methylen Both signals are fairly deshielded, indicating an electronegative atom nearby. oups. ‘The fragments identified at this point are a monosubstituted benzene ring, an OH group, and two adjacent methylene groups, HO —CH,CI > Q Phere are no other signals in the NMR spect’um, so the compound must be the one shown here. on Se “The doublet (0.9 ppm) that integrates to 6 protons and the multiplet (1.8 ppm) that integrates to I proton suggest the presence of an isopropyl group. Because we are told thut the compound isan aleohol, the other signal that integrates te | proton (the triplet at 2.4 ppm) mast be due to the OH proton, The fact that the signal a triplet indicates that the OH group is probably attached to a methylene group. The signal for the methylene group must be the remaining signal at 3-4 ppm because it integrates (0 2 protons. The relatively high-frequency chemical shift confirms that the methylene group is attached to the oxygen. Putting together the isopropyl group and the methylene group that is attached to an OH group identifies the ‘compound as 2-methyl-I-propanol. ae ‘The protons that are responsible for the doublet (1.2 ppm) that integrates to 6 protons must be adjacent 10 ‘a carbon that is attached to only one proton. Because the spectrum does not have a signal that integrates to one proton, the compound must have two methyl groups in the same environment, and each must be adjacent to a carbon that is attached to one proton and those two single protons must also be in identical environments CConyrigi © 2014 Pearson Bdocatin, te: 48 40. 4. Spectroscopy Problems Because the compound must be symmetrical. the (wo oxygens in the compound must be due to two OH groups in identical environments. The hydrogens of the OH groups give a singlet (3.8 ppm) that integrates to 2 protons 4 on | en wu ‘The protons that give the triplet (2.6 ppm) must be bonded 10 a carbon that is adjacent t0 a total of two pro- tons, Because the triplet integrates to 2 protons, it mest be due to a methylene group that connects the two pieces H OHH OHH Seesessseeese cmc Pid d HORA —H a This structure is confirmed by the relatively high-trequency multiplet (4.2 ppm) that is given by the protons altached to the carbons that are attached to the OH groups. The signall for these protons is split by both the adjacent methyl group and the adjacent methylene group. ‘The absorption in the IR spectrum at ~1650 em! could he due to either a carbonyl group or an alkene. ity strength and breadth tells us that itis probably due to & carbonyl (C=O) group. The strong and broad absorption at 3300 cm! that contains wo broad peaks suggests Wo NH bonds: thus. an NH group ts present. When these two groups ate subtracted from the molecular formula, all that is left is CsHs ‘The triplet (~1.1 ppm) that integrates to 3 protons and the quartet (2.2 ppm) that integrates 10 2 protons indicate the presence of an ethyl group: this accounts for the CH fragment. Thus. all the fragments of the compound have been identified: C=O, NH;, and CH,CH>. The compound, therefore, is propanamide. ° A The presence of an amide explains the lower-than-normal frequency of the C=O stretch in the IR spec trum, The breadth of the NH stretches contirms that these are amide N—H stretches and not amine N—H stretches. The broad singlets (6.2 und 6.6 ppm) in the NMR spectrum are given by the protons. attached 10 the nitrogen, The protons resonate at different frequencies because the C-N bond has partial double bond character. which causes the protons to be in diferent environments NH, The singlet (2.3 ppm) in the first spectrum that integrates to 3 hydrogens must be due to an isolated methyl group. The triplet (1.1 ppm) that integrates to 3 protons and the quartet ( characteristic of an ethyl group. ppm) that integrates to 2 protons are CCopyeight © 218 Pearw Fito. In 2. Spectroscopy Problems 49 ‘The singlet (4.8 ppm) that integrates to 1 proton must be due to a single hydrogen attached to nitrogen. i it Hea eo 4 wn i Now that the three fragments have been identified, we know that the compound is ethylmethylamine. AWN \ H The second spectrum shows that a broad singlet (2.8 ppm) must be due to hydrogens that are attached t0 nitrogens, Because the signal integrates to 2 protons, we know that the compound is a primary amine, ‘The triplet (0.8 ppm) that integrates to 3 provons is due to a methyl group that is adjacent 10 a methylene ‘group. The triplet 2.7 ppm) that integrates to 2 protons must also be adjacent to a methylene group. The ‘multiplet (1.5 ppm) that integrates (0 2 protons is the methylene group that splits both the methyl and methylene groups. The two triplets and multiplet are characteristic of a propyl group.) Theretore. the compound is propykamine. ‘The relatively weak absorption in the IR spectrum ut ~1650 cm” "tells us itis probably due to a carbon carbon double bond. This is reinforced by the presence of absorptions at ~ 3080 em ', indicating CH shed to 9p? earbons, bond stretches of hydrogens atta “The shape of the two absorptions at ~3300 em”! suggests the presence of an NH, group of primary amine, (Compare these to the shape of the N—H stretches of an NH, group of an amide in Problem 39.) ‘The three signals in the NMR spectrum between 5.0 and 6.0 ppm that integrate as a group to 3 protons in- dicate that there are three vinylic protons. Therefore, we know that the alkene is monosubstituted, ‘The two remaining signals in the NMR spectrum are a doublet (3.3 ppm) and a singlet (1.3 ppm) that each integrate to 2 protons. Because splitting is 201 typically seen with protons attached to nitrogens, we can identity the singlet at 1.3 ppm as due to the two amine protons. The doublet must be due to a methylene ‘group that is attached to an sp" carbon and split by t vinylic proton that is attached to the same carbon. ‘The ‘compound, therefore, is allylamine. NH Now we can understand why the signal at 5.9 ppm is a multiplet, This vinylic proton is split by the methylene group and two unique vinylic protons, The signals for the other two vinylic protons are dou- blets because each is split by the single proton attached to the adjacent sp? carbon, Notice that the higher frequeney doublet has the larger J value, This is the signal for the proton that is trans to its coupled proton. (Copyright 92004 Peano Education, Ine 4 Spe roscopy Problems ‘The molecular formula tells us that the compound does not have any degrees of unsaturation, Therefore, the oxygen must be the oxygen of either an ether or an alcohol. Because there are no signals that int to one proton, we ean conclude that the compound isan eth The triplet (1.2 ppm) that integrates to 3 protons and the quartet (3.5 ppm) that integrates to 2 protons s gests the presence ofan ethyl group. The high-frequency chemical shift ofthe ethyls methylene group and the fact that it shows splitting only by the three protons of the methy! group indicate that the ethyl group is next 10 the oxygen, The two remaining signals are both triplets (3.4 and 3.5 ppm) and each int signals are due to wo adjacent methylene groups. Beeause both signals occur at high frequenci ‘must be attached to electron-withdrawing atoms. les 0 2 protons, Thus. the - both Because the molecular formula telly us that the compound contains a bromine. we ean conclude that the ‘compound is 2-bromoethyl ethy! ether. The IR spectrum shows a strong and broad absoxption at ~ 3300 em! aleohol. indicating that the compound is an tals in the NMR spectrum between 6 and 7 ppm indicate the presente of a benzene ring, Because these signals integrate to a total of 3 protons, the benzene ring must be Irisubstituted, Because the signal at 6.3 ppm is a doublet. it must be adjacent 10 one proton: and since the signal at 6.7 ppm is a triplet. it must be adjacent to two protons, Thus, the three benzene-ting protons must be adjacent to one other ‘The singlet at 8.7 ppm is the only signal in the spectrum that can be attributed to the proton of the OH. group, Because the signal i es to 2 protons. the compound must have two OH groups in the same environment, The singlet (2.0 ppm) that integrates to 3 protons incicates that the compound has i methyl group that is not adjacent to a carbon that is attached to any hydrogens, Therefore, we know that the three substituents that are attached to adjacent carbons on the benzene ring are {0 OH groups and a methyl group. Because the OH groups are in the same environment, the compound tmust be the one shown here cH Ho a SS Copyright 2014 son Elation In 4s. 47. Spectroscopy Problems SI We are told that the compound is an alcohol, Because the singlet (1.4 ppm) is the only signal tha to I proton, it must be the signal given by the OH group. integrates We know that a triplet that integrates to 3 protons and a quartet that integrates to 2 protons are characteris- tic of an ethyl group. In this ease, the triplet (9.8 ppm) integrates to 6 protons and the quartet integrates to 4 protons. Therefore, the compound must have (wo ethyl groups in identical environments. ‘The only other signal in the spectrum the singlet (1.2 ppm) that integrates to 3 protons. This signal must be due to a methyl group that is bonded to a carbon that is not attached to any hydrogens. an 4 a wa i Because the NMR spectrum does not show any additional Signals, the compound must be -methyl-3-pentanol on ALAN “Phe doublet (1.1 ppm) that integrates to 6 protons and the septet (3.8 ppm) that integrates to T proton sug gests an isopropyl group. The triplet (1.7 ppm) that integrates to 3 protons and the quartet (2.2 ppm) that integrates t0 2 protons suggests an ethyl group. When these two groups are subtracted from the molecu~ Jar formula, all that remains is COs, The observed splitting patterns tell us that the isopropyl and ethy! groups are isolated from one another. We can conclude then that the compound is an ester. There are 1wo possibilities: ° I oN oN cHCH “occ, 4, CHYCH™ ~0CH.CH: CH, cH isopropyl propanoate ethyl 2-methylpropanoate Because the highest-frequeney Signal (the septet) is given by the CH of the isopropyl group, we know the CH is attached to an oxygen. Therefore. we know that the compound that gives the NMR dat is iso propyl propanoate. “The multiplet (6.9-7.8 ppm) that integrates to 4 protons indicates a disubstituted benzene ring, Becuuse the signal isa multiplet, we know that the substituents are on either the I- and 2-positions or the I+ and 3-po- sitions. Uf the substituents swere on the [- and 4-positions, either one singlet (if the two substituents were identical) or two doublets (ifthe substituents were not identical) would be observed. “Three signals (1.4, 2.5. 28 ppm) each integrate to 2 protons. ‘The fact thatthe signals are two triplets and inultiplet suggests that the compound has three adjacent methylene groups. (The methylene groups on the ts would be tipets and the one in the middie woud bea multiplet.) A a CHACHACHy— RS CConytigt © 2014 Pearson Bat. Ie WB. 49, Spectroscopy Problems From the molecular formula, we know that the compound has ant oxygen. The triplet at 3.8 ppm indicates that that particular methylene group is next to the oxygen. The two fragments that we have identilied account for the entire molecular formula. Tha, the compound must have the structure shown here. The molecular formula indicates that the compound has one degree of unsaturation, The NMR spectrum docs not show any signals in the area expected for ¥ nylic protons, so the compound must be either a ke- tone ora cyclic ether. A eyclic ether would be expected to have protons on adjacent carbons. so the signals would show splitting. Because the two signals in the spectrum are both singlets, the compound must be a ketone. ‘The fact that the compound has 11 carbons and 22 hydrogens but g trum indicates that the compound must be symmetrical, only two singlets in the NMR spec We know that a rer/-butyl group givey a singlet that integrates to 9 protons. The symmetry of the molecule feuds us to conclude that the singlet that integrates to 18 protons is due to two sert-butyl groups, We can then assume that the singlet that integrates to 4 protons is due to two nonadjacent methylene groups. These fragments account for all atoms in the molecular formula, Therefore, the compound must be 2,2,4,4-tetramethyl-4-heptanone. 6 cu ck cue cuscen, cu, cn, 2.2.6.6-tetramethy|-+-heptanone The molecular formula has one degree of unsaturation, so it must have a carbon-carbon double bond. a cyclic structure. or a carbonyl group. ‘The signal (3.8 ppm) that integrates to 4 hydrogens suggests the presence of two methylene groups in iden tical environments because, other than the carbon in methane, a single carbon cannot be alached to four hydrogens. The chemical shift suggests that each methylene group must be attached fo un oxygen, Because there is only one oxygen in the compound, the two methylene groups must be attached to the same oxygen, ~CH,—0—CH,— (Copyright 204 Pearson Education, I Spectroscopy Problems 53 The signal (1.6 ppm) that integrates to 4 hydrogens also suggests the presence of two methylene groups in identical environments. The four methylene groups and the oxygen account for all the atoms in the mo- lecular formula, ‘Thus, the compound must be eyelic ether. ) 0" The fuct that the signal at the higher frequency is, structure. riplet and the other signal is a multiplet confirms this. ‘The doublet (7.3 ppm) that integrates to 4 protons and the doublet (7.7 ppm) that also integrates to 4 pro- tons are given by benzene-ring protons, Because a benzene ring does not have 8 protons, there must be two benzene rings in the compound. The doublets indicate that the benzene rings have substituents at the 1- and 4-positions and, because each doublet integrates to 4 protons, the two substituents on each of the benzene _ Rett ea ea tes 10 6 protons suggests the compound has two methyl groups in an es that each is attached to an electronegative The singlet (3.8 ppm) that integ. identical environment. The chemical shift of the singlet ind! atom, The molecular formula indicates that the electronegative atom is an oxygen. 2 — OCH: When the two disubstituted by Formula, all that remains is CO. TI enzene rings and the «wo CHO groups ae subtuicted from the molecular ai earbonyl group must connect the two benzene rings oO Hl cuo-{_)-€-€ oct Copyrigt 2014 Peano tation, Ine CHAPTER 1 Remembei Important Terms antibonding molecular orbital atomic number atomic orbital atomic weight aufbau principle mn energy bonding molecular o bond length carbanion carbocation condensed structure core electrons covalent bond degenerate orbitals dipole di He moment (y0) double bond electronegative electronegativity ing General Chemistry: Electronic Structure and Bonding 4 molecular orbital that results when Wo atomic orbitals with opposit interact. Electrons in an antibonding orbital decrease bond strength, phases al atom has. al number that tells us how many protons (or electrons) « neu aan orbital associated with an atom: the three-dimensional area around a nucleus where electrons are most likely to be found. the average miss of the atoms in the naturally occurring element 4 principle that states that ar electron will always go into the available orbital with the lowest energy, the amount of energy required to break st bond in a way that allows each of the atoms to retain one of the bonding electrons, or the amount of energy released when a bond is formed, a molecular orbital that results when two atomie orbitals with the same phase interact, Electrons in a bonding orbital increase bond stren; the internuclear dist ai species containing a positively charged earbon, aa structure that does not show some (or all) of the covalent bonds. electrons in filled shells, a bond created as result of sharing electrons, Is that have the sume energy tution of positive and negative charges. a measure of the separation of charge in a bond or in a molecule. 3 bond composed of a sigma bond and a pi bond. describes an element that readily aequires an electron, the tendeney of an atoni to pull electrons toward itselt 4 © 2014 Pear Edbcation. electrostatic attraction electrostatic potential map (potential map) equilibrium constant excited-state electronic formal charge free radical (radical) ground-state electronic configuration Heisenberg uncertainty hydride ion hydrogen ion (proton) ionic bond mnie compou ration energy isotopes Kekule structure Lewis structure lone-pair electrons (nonbonding el Chapter 1 55 aan attractive force between opposite ch ‘4 map that allows you to see how electrons are distributed ina molecule. the ratio of products to reactants at equilibrium the electronic configuration that results when an electron in the ground state has been moved to a higher-energy orbital the number of valence electrons ~ (the number of nonbonding number of bonding electrons) setrons + half the aa species with an unpaired electron. a description of which orbitals the electrons of an atom occupy when they are all in able energy orbitals. their lowest a «principle that states that both the precise location and the momentum of an atomic particle cannot be simultaneously determined. atrule that states that when there are degenerate orbitals, an electron will ovcupy an emply orbital before it will pair up with another electron. aun osbital formed by hybridizing (mixing) atomic orbitals. a negatively charged hydrogen (a hydrogen atom with an extra electron). « positively charged hydrogen (a hydrogen atom without its electron). a bond formed as a result of the attraction of opposite charges. 1 compound composed of a positive ion and a negative ion, the energy required to remove an electron from an atom. atoms with the same umber of protons but x different number of neutrons. st model that represents the bonds between atoms as lines. a model that represents the bonds between electrons as dots. oms as lines or dots and the lone-pair valence electrons not used in bonding. Congsight 020-4 Pearson Esco, I 36 Chapter! mass number molecular orbital molecular orbital (MO) theory node nonbonding electrons nonpolar covalent bond octet rule orbital orbital hybridization organic compound Pauli exclusion principle pi (a7) bond polar covalent bond potential map (electrostatic potential proton (hydrogen ion) quantum mechanies radical (free rad sigma (7) bond single bond tetrahedral bond angle the number of protons plus the number of neutrons in an atom. aan orbital associated with a molecule that results from the combination of atomic orbitals aa theory that describes a mocel in which the clectrons occupy orbitals as they do in ‘atoms but the orbitals extend over the entire molecule. jon within an orbital where there is zero probability of finding an electron, valence e eetrons not used in bonding. a bond formed between two atoms that share the bonding electrons equally. a rule that states that an atom will give up. accept, or share electrons in order to achieve a filled outer shell (or an outer shell that contains eight electrons) and no electrons of higher energy. Because a filled second shell contains this is known as the octet rule the volume of space around the nucleus where an electron is most likely to be found. mixing of atomic orbitals, 4 compound that contains carbon 4 principle that states that no more than two electrons can occupy an orbital and that the two electrons must have opposite spin. a bond formed as a result of side-to-side overlap of p orbitals, a bond formed between two atoms that do not share the bonding electrons equally a map that allows you to see how electrons are distributed in a molecule. a positively charged hydrogen ion. the use of mathematical equations to describe the behavior of electrons in atoms or molecules. 4a species with an unpaired electron. i bond with a symmetrical distribution of electrons about the internuclear axis «single pair of electrons shared between two atoms the bond angle (109.5%) formed by an sp" hybridized central atom, tetrahedral carbon trigonal planar carbon triple bond valence electron valence-shell electron-pai repulsion (VSEPR) model wave equation wave functions Chapter | 37 an sp° hybridized carbon; a carbon that forms covalent bonds using four sp* hybrid orbitals, aan sp? hybridized carbon. ‘composed of a sigma bond and two pi bonds, an electron in an outermost shell a model for the prediction of molecular geometry based on the minimization of electron repulsion between regions of electron density (that is, between bonds and nonbonding electrons) around an atom, «an equation that describes the behavior of each electron in an atom or a molecule. a series of solutions to a wave equation, Copyright © 201 Pearson Education, tn 58. i Chapter 1 Solutions to Problems ‘The atomic number = the number of protons The mass number = the number of protons + the number of neutrons. All isotopes have the same atomic number: in the case of oxygen it is 8, Therefore: ‘The isotope of oxygen with a mass number of 16 hay 8 protons and 8 neutrons ‘The isotope of oxygen with amass number of 17 has 8 protons and 9 neutrons, The isotope of oxygen with a mass number of 18 has 8 protons and 10 neutrons. (percentage of naturally occurring SCI x atomie mass of Cl) + (percentage of naturally occurring YEUX atomie mass of "CD (1577 x 34.969) + (.2823 x 36.966) (26496 + 8.957) = 35.453 All four atoms have (Wo core electrons (in their filled shell); the valence electrons are in the outer shell Notice that because the four atoms in the question are in the Sime row of the periodic table. they have the ‘same number of core electrons. a3 bo © 6 ded Use the authau principle (electrons go into available orbitals with the lowest energy) and the Paul exclusion principle (no more than two electrons are in each atomic orbital). The order in which the orbitals are filled is: ly <2y < 2p < 39 < p< M< dy < 4p < dd < 58 < Sp nerate The question can be answered if you remember that there are one » atomic orbital and three des atomic orbitals in each shell. To write the electronic configurations for Br and I. you need to remem ber that there are five degenerate d atomic orbitals in the third and fourth shell CLs 262 2ph 392 3p* Br 1s? 2s? 2p 30° 3p aall ay 11s 2s? 2p 3s ph Bala b, They each have seven electrons in their outer shell (two are in an s orbital and five are in p orbitals) ‘Thus. they each have seven valence electrons. Notice that because they all are in the same column of the periodic table. they all have the same number of valence electrons, ‘The atomic numbers can be found in the periodic table on the last page of the text, Notice that elements in the same column of the periodic table have the same number of valence electrons and their valence elec~ irons are in similar orbitals a, carbon (atomic number = 6; 2 silicon (atomic number = 14: 10 core, 4 valent ore, 4 valence): 1 Is 2° sn (atomic number = 8: 2 core, 6 valence): Ly? 2s? 2p’ sulfur (atomic number = 16: 10 core. 6 valencey: Ly? 2s? 2p" 39° 3p" Copyright 612014 Posen Eaeton o: 0. 12. Chapter! 59 c. nitrogen (atomic number = 7; 2 core, 5 valence): Is? 2s? 2p! phosphorus (atomic number = 15: 10 core, 5 valence): 1s? 2s? 2p" 39? 3p 28 Oph 397 s° Oph 3s? 3p 4s? ‘a, Potassium is in the first coh the b. tho nn of the periodic table; therefore, like lithium and sodium that are also in c electron, iL column, potassium has one valers cupies a 4s orbital ‘The polarity of « bond can be determined by the difference in the electronegativities (given in Table 1.3 on page 11 of the text) of the atoms sharing the bonding electrons. The greater the difference in electronega- tivity the more polar the bond. . CI—CH, b. HOH H-P a. ClCH, KCI has the most polar bond because negativity. The electronegativity differe two bonded atoms have the greatest differences in electro- ces in the four listed compounds are as follows: KCL 3.0 08 = 22 LiBr 28 = 1.0 = 18 Nal 25-09 = 1.6 Ch 30-30=0 Cl, has the teust polar bond because the two chlorine atoms share the bonding electrons equally. Solved in the text. ‘To answer this question, compare the electrone, using Table 1.3 on page 11 of the text ities of the two atoms sharing the bonding electrons = 38 & 8 & 8 HOH bP Br HC Nip a nc—c1 a ab be 8 3 3- HOT EXCL ge Ic bh. 1LN—O1 (Notice that if the atoms being compared are in the same row of the periodic table, the atom farther to the right is the more electronegative; if the atoms being compared ate in the same column, the one closer to the top of the column is the more electronegative } Solved in the text The dipole moment is the magnitude of the charge times the distance between the charges. Because fluorine is more electronegative than Cl, the charge or H and F in HPF is larger than the charge on H and Clin HCI The larger charge on F compared to the charge on Cl is more than enough to make up for the fact that H—F isa shorter bond than HCl. a. LiH and HP are polar (they have a red endl and a blue end). b. A potential map marks the edges of the molecule’s electron cloud. The electron cloud is largest around the H in LiH, because that H has more electrons around it than the Hs in the ether molecules. €. Because the hydrogen of HF is blue, we know that this compound has the most positively charged hydrogen and, therefore, it will be most apt to attract a negatively changed species. Copgsight® 2018 Peanon Bustin, In oo M4. 16. Chapter | By answering this question you will see that « formal charge is a book-keeping device. It does nor necessarily tell you which atom has the greatest electron density oF is the most electron deticient. aL oxygen b. oxygen (itis the more red) ec. oxygen d. hydrogen (itis the deepest blue) Notice that in hydroxide ion, the atom with the formal negative charge is the atom with the greater electron density. In the hydronium ion, however, the atom with the formal positive charge is not the most electron- deficient atom. formal charge = number of valence electrons — (number of lone-pair electrons + half the number of bonding electrons) In all four structures. every H is singly bonded and thus has a format charge = 1 ~ (0 + 1) = 0 Similarly. all CH, carbon atoms have four bonds and a formal charge = 4 — (0 + 4) = 0. The formal charges on the remaining atoms follow: ci a. CHy oew b. Wen © Cnn H. iH H ci nn formal chargeon formal chargeon formal charge on N formal charge on 6-243)=4 A-Q43)=-1 S-FA=F | NS-(F4)=+1 B:3- (+4) =-1 The bond between two atoms can be shown by a pair of dots or by a fine. so there are two ways each of the answers can be written © & Net or or or or Copyright © 2014 Pearson Bd, he 18. 1, 20. ih Chapter 61 Because the compounds are neutral, « halogen will have three lone pairs, an oxygen will have two, a nitrogen will have one, and carbon or a hydrogen will have no lone pairs. cH b. CHANHCH; a CH,CH,CH,CI b. cH,CocHct ‘a, the (green) chlorine atom b. the (red) oxygen atoms CHACHC CHCHCNCH,CH, Hy the (blue) nitrogen atoms the (black) carbon atoms and (gray) hydrogen atoms i wacom HC —C—B: | I ee 4 H i ge H-C——c——C~c CCH | 1 ele ee " Copyright © 2014 Peanon Eduction, Ie 62 22. 24. Chapter 1 oO OO .Com auball larger than the ball larger than the bull that represents all that represents 2s orbital a 3s orbital He; has three electrons, Using Figure 1.4-on page 25 of the text. two electrony would be in a bonding molecular orbital and one electron would be in an antibonding motecular orbital. Because there are mo electrons in the bonding molecular orbital than in the antibonding molecular orbital. Hes exists a, 7 This involves out-of-phase overlap of atomic orbitals (the overlapping orbitals have different col- ors), leading to an antibonding molecular orbital. Because this example involves the side-to-side overlap of p orbitals, this results in a 77* antizonding molecular orbital This involves in-phase overlap of atomic orbitals (the overlapping orbitals have the same color). leading to a bonding molecular orbital. Because this example involves the side-to-side overlap of p orbitals, this results in a 7 bonding molecular orbital ¢. o® This involves out-of-phase overlap of atomic orbitals (the overlapping orbitals have different col- os), leading to an antibonding molecular orbital. Because this example involves the end-on over- Lap of atomic orbitals. this results in a 0° antibonding molecular orbital do This involves in-phase overlap of atomic orbitals (the overlapping orbitals have the same color. Jeading to a bonding molecular orbital, Because this example involves the end-on overlap of atomic orbitals, this results in a or bonding molecular orbital ‘The carbon-carbon bonds form ay a result of sp'—sp" overlap. ‘The carbon-hydrogen bonds form as a result of sp'—» overlap. ‘The electron density of the large lobe of an sp* orbital iy greater than the electron density of a lobe of a p orbital. Therefore, the overlap of an s orbital with an sp° orbital forms a stronger bond than the overlap oF aan y orbital with a p orbital Solved in the text a. One s orbital and three p orbitals form four 9° orbitals b, One s orbital and two p orbitals form three sp" orbitals One s orbital and one p orbital form two sp orbitals a(1), Solved in the text (1). Solved in the text (2). ‘The carbon forms four bonds, and each chlorine forms one bond. “c b2). The earbon uses sp" orbitals 10 form the bonds with the chlorine atoms, so the bond angles are all 109°. Copyright ©2014 Pearson Eaton, Ie Chapter! 63 3). The first attempt at drawing a Lewis structure shown below shows that carbon does not have a complete octet and does not form the needed number of bonds. Using one of oxygen’s lone pairs to pat a double bond between the carbon and oxygen solves both problems. (3). The sp" hybridized CH, carbon has 109.5° bond angles and the yp* hybridized CH=O carbon has 120° bond angle: ‘j no ype HA Pe" on wostel ff 4). In onder to fil their octets and form the required number of bonds, carbon and nitrogen must form «triple bone. Hc (4). Because the carbon is yp hybridized, the bond angle is 180°. 10 a 120 b. 120° ¢. Because the carbon is sp" hybridized and it hay a lone pair, you can predict that the bond angle is similar to that in NH, (107.3°), ‘The nitrogen atom hus the greatest electron density The hydrogens are the bluest atoms. Therefore, they have the least electron density. In other words, they have the most positive (least negative) electrostatic potential. Water is the most polar—it has a deep red area and the most intense blue area. Methane is the least pokar—it is all nearly the same color (green) with no red or blue areas, Solved in the text Electrons in atomic orbitals farther from the nucleus form longer bonds; they also form weaker bonds due to less electron density in the region of orbital overlap, Theretore: a, relative lengths of the bond in the halogens are: Bry > Cls relative strengths of the bonds are: Cl > Bry b, relative lengths: CH, —Br > CH, —Cl > CH, — relative strengths: CH;—F > CH;—Cl > CH,— Br Copyright © 2614 Peano Faction. ne 64 Chapter 1 —t 2 C¢-cl 3 Hcl —cl 2 C=C 3. HOP 35. a longer: 1. b. stronger: 1. carbon in CCl; iy bonded to four atoms. so it uses four yp" orbitals F Each carbon-chlorine bond is formed by the overlap of an sp* orbital of carbon with an sp! orbital of chlorine. Because the four sp" orbitals of carbon orient themselves to get as far away from each other as possible, the bond angles are all 109.5. bond angles = 109.5° b. CO, ‘The carbon in COs is bonded to two atoms. soi uses 140 9p orbitals, Each carbon-oxygen bond isa double bond. One of the bonds of each double bend is formed by the overlap of an sp orbital of carbon with an sp? orbital of oxygen The second bond af he double bond is formed asa result of side-to-side overlap ofa p orbital of carbon with p orbital of oxygen. Because curbon's two sp orbitals orient themselves to get as far away from each other as possible, the bond angle in COs is 180°, 0 ° bond angle = 180 «. HCOOH ‘The double-bonded carbon and the double-bonded oxygen in HCOOH cach uses sp" orbitals: thus. the bonds around the double-bonded carbon are all 120°, The single-bonled oxygen forms bonds using yp" orbitals, whereas each hydrogen uses an s orbital The predicted C—-O—H bond angle is based on an sp* oxygen that has a reduced bond angle due to the two lone pairs. The bond angle is predicted to be similar to that in HO (104.5°) the o bond is formed by sp?—sp? overlap the bond is formed by p—p overlap, ys overlap / C104 alloter bond angles are 120 HOH a, wap? overlap dN, ‘The viple bond consists of one o bond and two = bonds. Bach nitrogen has wo sp orbitals; one is used to form the o bond, and the other contains the lone pair. Each nitrogen has wo p orbitals that are used to form the two 7 bonds. A bond angle iy the angle formed by three atoms. Therefore. there are no bond angles in this two-atom containing compound. the o bond is formed by yp—yp overlap ‘each bond is formed by p—p overlap -_ | Copsrigh #2014 Psaron idan. be 9. 40. Chapter 165 Each sp* orbital of boron overlaps an sp* orbital of fluorine. The three sp” orbitals orient themselves to. get as far away from each other as possible, resulting in bond angles of 120°. Solved in the text We know that the « bond is stronger than the a bond, because the or bond in ethane has a bond dissociation energy of 90.2 keal/mol, whereas the bond dissociation energy of the double bond (a + 7) in ethene is 174.5 kcal/mol, which is less than twice as strong. Because the or bond is stronger, we know that it has more effective orbital-orbital overlap. Because electrons in an y orbital are closer an average to the nucleus than those in a p orbital, the greater the » character in the interacting orbitals, the stronger (and shorter) will be the bond. Therefore, the carbon- carbon @ bond formed by sp?-—sp? overlap is stronger (and shorter), because an sp? orbital has 33.3% » character, whereas an sp" orbital has 25% s character. OOO ¢. the nitrogen and chlorine atoms Copyeigh © 214 Pearson Ed 66 a. 4B. 4 45. 46. 4. 50. Chapter | ‘The bond angle depends on the central atom. a, sp’ nitrogen with no Tone pair: 109.5° —e_sp* carbon with no fone pair: 109.5" b, sp nitrogen with a lone pair: 107.3° sp? carbon with no lone pair 109.5° ‘The one with the greater electronegativity will decrease the electron flow toward the F. giving the com- pound a smaller dipole moment. Since CH,F has a smaller dipole moment than CDsP. we know that hy- drogen is more electronegative than deuterium. ‘The electrostatic potential map of ammonia is not symmetrical in the distribution of the charge—the ni- trogen is more electron rich and therefore more red than the three hydrogens, Therefore, its shape. which indicates charge distribution, is not symmetrical, ‘The electrostatic potential map of the ammonium ions symmetrical in the distribution of the charge, so its shape is symmetrical. Its symmetry results from the fact that nitrogen forms a bond with each of the four hhydrogens and the four bonds point to the comers of a regular tetrahedron, The nitrogen in the ammonium ion has significantly lower electron density than the nitrogen in ammonia since the lone pair has formed bond to hydrogen a, €, gyand have a dipole moment of zero because they are symmetrical molecules, ci—Be—cl B a. CHCHy b. CHP If the central atom is sp" hybridized. the bond angle will depend on the number of lone paity it has none = 109.5%: one = 107.¥':two = 1045° a. sph 107.3 ce. sph 109.5° sp’. 7.3" b. sp, 120° £ sp 120° eeeteseaee esp! 1073 9p. 180" de pF, 120° he sp’, 109.5% a CHCH,CH, ob CHYCH=CH, CHC ‘The hybridization of the central atom determines the bond angle. If the hybridization iy yp’. the number of Jone pairs on the central atom determines the bond angle. a. 109.5° b. 104.5" 107.3" a. 1073 © 104.5° is the correct prediction based on the bond angle in water. However. the bond angle is actually somewhat larger (108.2°) because the bond opens up to minimize the interaction between the electron cloud of the relatively bulky CH) group. Copscght ©2014 Pearson Faeation las Me Wf cet et Chapter | 67 3s He iy 3. 4 19228 2p 32 te el a ae2e ce seacee 2 ap 30 3% b. &. a. b. sreater the electronegativity between the two bonded atoms. the more polar the bond. (See Table 1.3 on page 11.) cr c-cl > H-O > C-N > wt l CHCH=CHs oe it cHCCHS c-o c—Br HoN crH ae H a cng H ap sf CHACH.OH CHCH=NCHy ” sp i f CHOCHCHy Copysigtt 2014 Pearson Education, le 59. Chapter t a 120° a HC Br be HCL formal charge = 109.5" 180° a. 109.5° HONE fe HyC—On a ibe fiCtty NH number of vatlence electrons = (number of lone-puir electrons + half the number of bonding electrons) In all four compounds. H has a single bond and is neutral and each C has four bonds and is neutral. Thus, the indicated formal charge is for O or N. H I a Hoe gon H formal charge 6-4 +2)=0 ‘The open arrow in sph ap? 1 cHncH ow ah 2. cHCCH.OH wi dp ”, eeHe WO? sp’ For 1.2, and 3: For 4 and 5: For 6: H 4 H b. oo H HCO aw é NH ah 4 hon formal charge formal charg formal charge 6-24 a4 6-H D> = 243-0 led bonds in e: ‘h compound, the str ‘ures points to the shorter of the two ind 3. CHNHCHSCHN sp sp sp wp 4 » | 4 Scone Sc* a Wore ee 4 Be—~CH.CHSCHy sp) sp sp (ct yp triple bond is shorter than a double bond, which is shorter than a single bond. ‘The greater the y character inthe hybrid orbital. the shorter is the bond formed using that orbital. because an s orbita. is closer than a p orbital to the nucleus, Therefore, the bond formed by a hydrogen and an sp carbon is shorter than the bond formed by a hydrogen and an sp" carbon, whieh is shorter than the bond formed by a hydrogen and an sp* carbon, (See Table 1.7 on page +4 of the text.) Cl forms a bond using a 3yp* orbital and Br forms a bond using a 4yp" orbital, There- fore, the C—CI bond is shorter Cops © 2004 Paar don Chapter 1 69 Cr 4 . nn # Me ween iN re ee .¢ hon ad “The thre carbons are all sp* hybridized, WAyy All the bond angles are 109.5°. ws" uw 5 wR S e WO Nemc 1" ee W\ woo ” ‘The four carbons are all sp? hybridized All the bond angles are 120°. 2. 63. 4 Towest dipole moment 64. 65. cmh=CH chy Copysiht © 2014 Pessow Elution, Ie 70 66. 67. 0. 70. Chapter 1 In an alkene, six atoms are in the same plane: the two sp? carbons and the two atoms that are bonded to each ofthe to sp? carbons. The other atoms inthe molecule will not be inthe same plane with these six atoms, 28s If you put stars next to the six atoms that lie in a plane in each molecule, you will be able to see more clearly whether the indicated atoms lie in the same plane. cHy orbital of C, whereas the CCl bond in CHy=CHC1 is formed by the overlap of an sp" orbital of C1 with an sp" orbital of C. (The more the s character, the shorter und stronger the bond.) CHC; has the larger dipole moment because the three chlorines are withdrawing electrons in the same gen- eral direction, whereas in CH3C1, two chlorines are withdrawing electrons in the same general direction. ‘The dipole moment is 2.95 D because the two Cls are withdrawing electrons in the same general direction so their electron withdrawing effect is additive Copyright® 2044 Poor doch Chapter 1 a 71, The bond angles at the triple-bonded carbons, when the bonding orbitals overlap maximally, are 180°. A 180° angle cannot fit into the ring structure. Therefore. the overlap between the yp orbital and the adjacent sp" orbital becomes distorted from the ideal end-on overlap. This poor overlap causes the compound 10 be unstable, (Compare the structure shown here with Figure 3.8 on page 125 of the text.) " iy Oe cf : 72. 73. 4 bo HOCoN=N: a NENG: " Ia H-G=N ceonteibutors these are resonance contributors Copysigt 02914 Pear Fat n 2 Chapter 1 Chapter 1 Practice Test Angwer the following: a Which bond has a greater dipole moment, « carbon-oxygen bond or a earbon-fluorine bond? b. If Hed has three electrons in its molecular orbitals, how many electrons are in an antibonding molecu- lar orbital? ¢. Which is the longer bond, « carbon-hydrogen bond in ethene or a curbon-hydrogen bond in ethane? @. Which is le in ammonia? xz the bond angle in water or the bond 2 e. Which is stronger. a sigma bond or a pi bond? What is the hybridization of the carbon atom in each of the following compounds? *CH, CH; -*CHy Draw the Lewis structure for HCO, Circle the compounds below that have a dipole moment = 0. CHCl CHCH, CHCL-HC=0 CCI, ss. HO or *NHy? Which compound has greater bond a Draw the structure For each of the following: a, methyl carbocation b. ahydride ion a bromine radical dan alkane with only prima carbons Draw the structure of compound that contains five carbons, two of which are y which are sp" hybridized. ybridized and three of ‘What is the hybridization of each of the indicated atoms? CC ££ 8 (if CHCSNCH, CHACCH) 0. Hy \ a, What orbitals do carbon’s electrons occupy before promotion? 1b. What orbitals do carbon’s electrons occupy atter promotion and before hybridization? Copyright © 204 Peuron Edt 10, i 2 Chapter! 73 Answer the followin; a, What is the HC —0 bond angle in CH/OH? 1b. What is the H—Be—H bond angle in BeH;? €. What is the H—B—H bond angle in BH,? dd. What is the C O—H bond angle in CHOH? ndicate the hybridization of the atom to which the arrow is poi Foreach of the following compounds. i HCOH HE=N- CiHOCHy CHK KOR KX XR Indicate whether each of the following statements is true oF false. A pi bond is stronger than a sigma bond. T b. A triple bond is shorter than a double bond. T F ‘The oxygen-hydrogen bondy in water a’e formed by the overlap of an spF orbital of oxygen with an y orbital of hydrogen, T F dA double bond iy suomger thar a singke bom i F fe. A tetrahedral carbon has bond angles of 107.5°. T F | ANSWERS TO ALL THE PRACTICE TESTS CAN BE FOUND AT THE END OF | ‘THE SOLUTIONS MANUAL. J 63014 Pear Econ I CHAPTER 2 Acids and Bases: Central to Understanding Org: Important Terms (Bronsted acid) acid-base reaction acid dissociation constant acidity hase (Bransted base) basicity Bronsted acid Bronsted base buffer solution delocalized electrons, equilibrium constant Henderson—Hasselbaleh, equation ductive el withdrawal Lewis acid Lewis base pH PA, proton proton transfer reaction resonance resonance contributors, resonance hybrid aaypecies that donates a proton sion in which an acid donates a proton to a bave. a measure of the degree to which an acid dissociates measure of how easily @ compound gives up a proton at species that aveepts @ proton a measure of the tendency of a compound to share its electrons with a proton, a species that donates a proton 1 species that accepts a protor solution of a weak acid and ils conjugate base the species formed when a base accepts a proton the species formed when an acid loses a proton, electrons that are shared by three or more atoms (that is. do not belong to a single atom nor are they shared in a bond between two atoms). the ratio of products to reactants at equilibrium, pK, = pH + log(HA)/(A the pull of electrons through sigma bonds by an atom or by a group of atom, at species that uccepts an elect-on pair: species that donates an electron pair th 1 scale used to describe the acidity of a solution (pH = log H* a measure of the tendency of a compound to lose a proton (pK, = “log K,. where K, is the acid dissociation constant) 4 positively charged hydrogen ion, reaction in whieh a proton is transferred from an acid to a Base. having delocalized electrons, Structures with localized elections that together approximate the true structure of a compound with delocalized electrons, the actual structure of a compound with delocalized electrons. WW Chapter2— 75 Solutions to Probler 1. COs and CCL, are not aeids because neither has a proton that it can lose, 2 a HCl + NHy SE Ch + TNK, b. HO + °NH; S== HO™ + NHy 3. The conjugate acid is obtained by adding an H’ to the species. a () ‘NH, @) HCL 3) HO) HO ‘The conjugate base is obtained by removing an H trom the species. b. UD) NH) 2) Br (3) NO} (4) HO” 4. a, The lower the p&;, the stronger the acid, so the compound with pX, = 5.2 is the stronger acid, b. The greater the dissociation constant, the stronger the acid, so the compound with a dissociation 3.4 X 10's the stronger avd. cconstan S.—_ Because we know that Ky = Ko, [HO] K, 53 x 10° K, = ABA st6 x 10" (H,0 6 Its K, value is 151 10, I iy a weaker acid than vit 6.8 * 10 ‘in the Problem-Solving Strate: C whose K, value was determined to be 1 oa HO + WT = HO b. HCO + HY == HCO) EHO + CO. = HCO, = HAO + CO 8. If the pH iy <7, the body fluid is acidie: if the pH is >7, the body fluid is basic. 9. Remember tha a proon wil be pike upby an atom tat has one WF or ane pas, Nati that wo Sayers hae Tone pin pate To see which one gts the proton, ee Table 2.1 on page OD of he x ° ‘OH é é a CCHS: CHLCHOH—-«& cTSON a cancH, ec Son 10. In each of the following reactions, the position of equilibrium is established by analyzing the relative strengths of the acids on either side of the reaction—the equilibrium favors reaetion of the stronger acid 10 form the weaker acid (see Section 2.5), (Nove that HCI is a stronger acid than H,O': see Appendis 1 in the text) Iethe lone p: nol shown: a. CHOHasan avid: CHO + NH; == CH,O + NHy CHOH asabase: CHJOH + HCL = ernoH rch H Copyright © 2014 Pears Buti, I M. M4, Chapter 2 Ifthe lone pairs are not shown: a. CH3OHasan acid: CH;OH + NH; == CHO” + NH, CHOHasabae: CHO + HCL = CHRON + Cr i bo NH wana) NH FIMO” EN + COM Nee ee ee Che lone pairs are shown: a. CHOHasunacid: CHQH + NH CHOH asa base: CHGH + HE bh. NH ay an acid: NH, + CHOr Ng as a base: Ny + HBr: a. ~40 b= 15 «<5 a ~10 a CH,COO- is the stronger base, Because CH;COOH is the weaker acid. it has the stronger conjugate base b. “NH is the stronger base. Because NH is the Weaker acid, it has the stronger conjugate base, 10 is the stronger base, Because H,O" is the weaker acid, it has the stronger conjugate base. The conjugate acids of the given bases have the following relative strengths: © t CHO, > CH OH > CHYNHy > CHOH > CHNH: ‘The bases. therefore. have the following relative sirength conjugate base - sinee the weakest acid has the strongest ¢ t CHWNH > CHAO” > CHWNH: > CHyT SO- > CH\OH Methanol is the acid because it has a pA, value of ~ 15, whereas methylamine is a much weaker aeid with a PK, value of about 40, Copyright © 2014 Pearson Eat Chapter? 77 15. Notice that in each cave, the equilibrium favors reaction of the stronger acid to form the weaker acid. a CHOH + HO CHO” + LO pK, = 155 pk, =157 (CH OH HOge | CHOW 10} 7 9 0 ix cny ‘on + HO PR, =48 9 fa Ko te to CHy ‘OH cHy Son 6 CHNH, + HO cH + pk, =40 CURNH) + HOT SS CNH; + 0 pK, =10.7 bo HCL + HO HOt + oc DK, =-17 NH, + = TNH, + HO pK, = 15.7 pk, = 94 16, Because a strong acid is more likely to lose a proton than a weak acid, the equilibrium will fuvor loss of a proton from the strong acid and formation of the weak acid ec Che st HOS pk,=25 b. HOSCH + “NH, WeSC pky=25 ok, © Np would be a better base because when it removes a proton, the equilibrium favors the produets When HO” removes a proton, the equilibrium favors the re 17, Each of the following bases will remove a proton from acetic because each of these bases will form an acid that is a weaker id in a reaction that favors products, id than acetic acid. HO" CHWNH, = HC=C The other three choices will Form an acid that isa stronger acid than acetic acid, Copy 204 Pearson cation. Ine 78 19. 20, mM Chapter? pK = p&, (reactant acid) ~ p&, (product acid) Fora the reactant acid is HCI and the product acid is HO" For b the reactant avid is CH;COOH and the produet acid iy HO™ For € the reactant acid is HO and the produet acid is CHNHs For d the reactant acid is CHyNHs und the product acid is Hs0° a pKy = -7 - (-17) = -53 G PKy = 15.7 - (10.7) = 5.0 Ky = 20 10° Kg, = 1.0% 105 be pKa = 48 ~ (-1.7) = 68 pKa = 00.7 = (=1.7} = 124 Ky = 32x10 Ky = xo Recall that the weakest avid has the strongest conjugate base. CHy > NH) > HO” > Aeuin, recall that the weukest acid ha the strongest conjugate base, CCH: = C= CH > HOS The protonated Ketone is the stronger acid becuuse its hydrogen is attached to an 97" 0x we than the sp’ oxygen to Which the hydrogen in the protonated alcohol is attached. more electrones’ ak CH 6 CHCH: = HI + CHCHs BOH.C=CH, + HCSC =e CH=CH + HOCH C CHCH. + HYC=CH T= CH CH: + HC =CH; be Only A. because only A hay a reactant that isa stranger acid than the acid that is formed in the product The smaller the ion, the stronger itis as at hase eee ce Be b. HS . CH,SH tivity in determin stability. Therefore. even SH isa stron- The size of an ont is more important than its electron tive than sulfur, HLS is a stronger acid than HyO and C nis more electron ger acid than CHOH. Because the sulfur atom is larger. the electrons in its cong Which stabilizes it, The more stable the base, the stronger its conjugate acid, we buse are spread out over a greater volume. “The stronger avid will have its proton attached to the more el swative atom (if the atoms are about the same size) ar to the larger atom (if the atoms are not the same size). a. HBr be CIACHCHOH, eG. CHACHICHLOH— d.CHACHSCH,SII Remember that the stronger the acid. the weaker (or more stable) ity conjugate base. ‘a. Because Hl is the strongest acid. 1” is the most suble (weakest) base bb. Because HF is the weakest acid, Fis the Teast table (strongest) base Copyright 2 2014 Pear Education tn 2. 28. 30. 2 3B. Chapter? 79 pate acids, recall Compare the acid strengths of the conju a, HO because H,O isa weaker acid than H,0" b. NH; because "NH, is a weaker acid than H,O! €. CHO" because CH,OH is a weaker acid than CHyCOOH. 4. CHO™ because CH,OH is a weaker acid than CH,SH. ial a weuker acid has a stronger conjugate base, a. CHOCHCHOH because its conjugate base hay its negative charge stabilized by electron withdrawal by the CH,O group. b. CHCHACHZOHy because oxygen is more electronegative than nitrogen, © CHCHLOCHCHLOH because the electron-withdrawing oxygen is closer to the OH group. f dd. CHACHACOH because the electron-withdrawing C=O is closer to the OH group. CH:CHCH.OH > CHCHCHLON > CHLCHLCHLOH > CH/CHCH.OM cc cl a ‘The first listed compound is the most acidic because it has two electron-withdrawing substituent that will stabilize its conjugate base The second listed compound is a stronger acid than the third listed compound because the chlorine in the second compound is closer to the O— H bond. The compound on the far right does not have a substituent that withdraws electrons inductively, so itis the least acidic of the four compounds, ‘The weaker acid has a stron ° ° wer conjugate base. oO I ii I & cHeHCO” b, caneHCHACOe ad. CHCCHCH;O Br a Solved in the text ‘a, Because the atom (P) to which each of the OH groups is attached is also atached to two eleetrone tive oxygens, Is) b. The middle OH group is the weakest of the remaining acidic groups. It is an alcohol (pK, and the atom (C) to which it is attached is not attached to any strongly electronegative atoms. (The protonated amino group has a pX, value of ~ 10.) When a sulfonic acid loses a proton, the electrons left behind are shared by three oxygens. In contrast, when a carboxylic acid loses a proton, the electrons left behind are shared by only «wo oxygens. The sulfo- nate ion, therefore, is more stable than the carboxylate ion cc carboxylate ion Copyright 9 14 Peaon dasa, In 80. 35. Chapter 2 ‘The more stable the base. the stronger is its conjugate acid. Thu. the sulfonic acid is a stronger acid than the carboxylic acid. Os I Remember, the smaller the pX,. the stronger the acid, a CHC=NH b. CHyCHy f . FXCCOH d.an sp’ oxygen “on ©. H CH CH, CHOCH; pa=-7.3 PRE 30 fe CH;C=NH > NHCH, > CH3CHyNHy cH pK. =10.1 p= pk,= 110 If the solution is more acidic than the compound’s pK, value, the compound will be in ity seidie form (with, ity proton) If the solution is more basic than the compound's pX, value, the compound will be in its basic form (with- ‘out its proton) a. CH,COO™ c HO e NHy g ON b. CH.CHNH, Br HOS pH 104 (As long as the pH is greater than the pX, value of the compound. at least 50% of the compound will be in ity basic form.) as 1 neutral b. 1. charged 1 neutral 2. neutral 2. charged 2 neutral 3. charged 3. charged 3. neutral 4. charged 4, charged 4, neuteal 5. charged 5. neutral 5. neutral 6. charged 6. neutral 6. neutral Copyright 9) 2014 Pear Educa, bs 39. 40. al. a © Chapter2 81 ‘The “NH, group withdraws electrons, which inereases the acidity of the COOH group. Both the COOH group and the “NH, group will be in their acidic forms, because the solution is more acidie than both of their pK, values. The COOH group will be in its basic form because the solution is more basic than its pK, value. ‘The “NH; group will be in its acidic Form because the solution is more acidic than its pK, value ° i c cucu 0) ONE, Both the COOH group and the “NH; group will be in their basic forms because the solution is more basic than both of their pX;, values, ° I ow cuca ~o- NHy No, alanine can never be without a charge. To be without a charge would require a group with a pK, Value of 9.69 10 lose a proton before a group with a pK, value of 2.34, This clearly cannot happen. A weak acid cannot have a stronger tendercy to love a proton than a stronger acid has, AN the pH becomes more basic than 2.34, the COOH group will become more negatively charged As the pH becomes more acidic than 9.69, the “NHj group will become more positively charge: ‘Therefore, the amount of negative change will be the same as the amount of positive charge at the pH that is equidistant from the two pk, vals. 2.34 + 9.69 5 = 6.002 10.4 (to log units more basic than the pk) 2.7 (one log unit more acidic than the pk) 64 (two log units more acidic than the P&,) 7.3 (when the plH is equal to the pk) 5.6 (one log unit more basic than the pk.) 1. pH = 4.9 When the pH = pX, half the compound will be in its acidic form (with its proton) and half will be in its basic form (without its proton), 2 pH = 10.7 1. pH > 6.9 Because the basic form is the form in which the compound is charged, the pH needs to be more than two units more basic than the pA, value pH < 8.7 Because the avidie form is the form in which the compound is charged. the pH needs to be more than two units more acidic than the px, value. Copyright © 2014 Peon Paci, bs 46. 47. 48. Chapter 2 a. Solved in the text b. For the carboxylic acid to dissolve in water, it must be charged (in ity basie form), so the pH will have to be greater than 6.8, For the amine to dissolve in ether, it will have to be neutral (in its basic form). so the pH will have to be greater than 12.7 to have essentially all of iin the neutral form, Therefore, the pH of the water layer must be greater than 12.7, ¢. To dissolve in ether, the carboxylic acid will have to be neutral, so the pH will have to be less than 2.8 to have essentially all the carboxylic acid in the acidic (neutral) form. To dissolve in water, the amine will have to be charged. so the pH will have to be less than 8.7 to have essentially all the amine in the acidic form, Therefore, the pH of the water kayer must be less than 2.8, a, The hasie form of the buffer removes a proton from the solution. cH,CoO- + HY CH,COOH b. ‘The acidic form of the buffer donates a proton in order to remove an hydroxide from the solution, CH.COOH + HO. CH.COD- + HO Solved in the text a ZC + CHOH === Zac; oe we Br—FeBry CI AICh, ab, ¢, and hare Bronsied aeids (provon-donating acids). Therefore they rect with HO” by givi dye. fyand g are Lewis acids, They react with HO” by accepting a pair of electrons from it aiprotun tit a CHOH + HOT === CHO™ + H,0 b. NH, + HOT — Mm, + HO CHS, + HOO === CHAN, + 10 BR + HOM HO-BF, CH + HO cH oH Feb, + HO” HOW Febry AIC + HOT HO—AIcl, . CH,COOH + HOT === — CH,COO™ + HO a. CCICH;OH > CHCICH;OH > CH,CICH.OH b. The greater the number of electron-withdrawing chlorine atoms equidistant from the OH group. the Stronger the acid. (Notice that the larger the K,, the stronger the avid) The stro hase has the weuker conjugate weil 1 HO” b. CHSNH « CHO a Cl fe CHYCOO™ —f CH,CHBrCOO™ Copyright 02014 Pear btn. Ine 49. Si. 4. Chapter2 83 “oN co é a NH, 4 ow oo b. HO! + Febry 1,0 Feber; aN “an é é HH” SOH Ho SOH + WY a, CHsCHsCHCOOH > CH;CHCH3COOH > CICHsCHyCH{COOH > CHyCH;CH;COOH & & b, An electron-withdrawing substituent makes the carboxylic acid more acidic, because it stabilizes its conjugate base by decreasing the electron density around the oxygen atom, (Remember that the larger the K,, the stronger the acid.) ‘The closer the electron-withdrawing chloro substituent is to the acidic proton, the more it can decrease the electron density around the oxygen atom, so the more it stabilizes the conjugate base and increases the avidity ofits conjugate ac it St a co au, an, A HOCH.CHLNHy —-b. “OCHSCHLNH, ive than N. which is more electronegative than C. Theretore, the alcohol is more dic than the amine, which is more acidic than the alkane. Sis larger than O. so CH\CH,SH is more acidic than CH\CH,OH. CHCH:SH > CH\CHJOH > CHC! > CHC Hy If the solution iy more acidic than the p&, of the compound, the compound will be in its acidic Form (with the proton), If the solution is more ba the proton). je than the pX, of the compound, the compound will be in its basic form (without CHCOOH —b, atpH=3 CH\CH,NH, =e. atpH=3 CRC a tpl alpH=6 — CH;COO™ atpH=6 CHACHSNHy atpH=6 — CRCHOH atpH= 10, CH;COO™ atpH=10. CH,CH,NH, alpH=10) CE.CHOH alpH= 14 CHy “00 atpH=14 CH,CHNHy atpH=l4 CECH LO" Copyright 2004 Pearson Eakin, Ie 56. 58. 60, 61. 2. Chapter 2 In all four reactions, the products are favored at equilibrium, (Recall that the equilibrium favors formation of the weaker acid.) a, CH\COOH + CH,O™ CH,COO” + CH,OH b, CHCHJOH +°N CH\CHJO- + NHy ¢ CH\COOH + CH\NHy CH,COO” + CHANHy {1 q 4 a. CHCHLON + HEL cHcHoH, + cI &. HCSCCH.OH > CHY=CHCHOH > CHCHCHOH b. These three compounds differ only inthe group that is attached to CH:OH. The more electronegative the group attached to CHJOH, the stronger the because inductive electron withdrawal stabilizes the conjugate base. and the more stable the base, the stronger its conjugate acid. An sp carbon is more clecttonegative than an sp? carbon, which is more eletronegative than an sp" carbon, In each compound. the nitrogen atom is the most apt to be protonated because itis the stronger base. cH cts a cen —cHsy & cyt —oH > c—CHOH on oN NH ‘The log of 10-* = —4. the log of 10°* = —5, the log of 10° = —6, and so on. Because the pK, = log K,.the pK, of an acid with a K, of 10-4is =(=4) = 4 An acid with a K, of 4.0 X 10 isa stronger acid than one with a K, of 0 x 104 Therefore. the px, can be estimated as being between 3 and 4 a. 1. between Sand 4) beoL pk = 34 2. between ~2 and ~1 2 3. between 10 and I 3 4. between 9 and 10 4. 5. between 3 and 4 5 © ‘The direction of the dipole will be toward the more electronegative of the two atoms that are sharing the bonding electrons. a CH —C=CH ob. CH CH The hy ywen bonded to the oxygen is the most acidic hydrogen in Tenormin, A and C because, in each case, the acid is stronger than the acid (H;O) that will be formed as a product ‘The reaction with the more Favorable equilibrium constant will be the one with the smallest difterence between the pK, value of the reactant acid and the pX, value of the product acid, because pK, = pK, (reactant acid) ~ pK, (product acid) and the smaller the pA the larger the Ky a. 1. CH,CH,OH has a pk, value = 15.9 CHOW has a pX, value NH, has a pX, value = 9.4 35 Copyright © 2014 Peano Eaton. Ine Chapter? 85 PK, (reactant acid) ~ pi, (product acid) 15.9 ~ 94 = 65: Ky = 3.2 107 = 155-98 79x 107 Thus. the reaction of CH;OH with NH; has the more favorable equilibrium constant. 2. CHCH.OH haya pX, value = 15.9 *NH, has a pK, value = 9.4 CHNH, has a pX, value = 10.7 PKoy = pK, (reactant acid) — pk, (product acid) 5.9 — 9.4 = 65: Ky = 3.2 x 107 ISS ~ 10,7 = 5.2: Ky = 6.3 x 10% ‘Thus. the reaction of CH,CH,OH with CHNH; has the more favorable equil um constant, Because the reaction of CH\CH,OH with CH,NH) has the smallest difference between the pA, values of the reactant and product acid it hay most favorable equilibrium constant. 63. IV the reaction is producing protons. the basic form of the bu‘fer will pick up the protons. At the pH at which the reaction is carried out (pH = 10,5), a protonated methylamine/methylamine bulfer with a PK, = 10.7 will have a larger percentage of the butfer in the needed basic form than will a protonated cthylamine/ethylamine buffer with a p&, of 11.0. 64a. CHCOOH because an sp? carbon iy more electronegative than an sp" carbon because an oxygen can withdraw electrons inductively because an sp carbon is more electronegative than an sp” carbon because an sp" nitrogen is more electronegative than an sp* nitrogen a. 65. a, The first pX, is lower than the pK, of acetic acid because citrie acid has additional oxygen-containing groups that withdraw electrons inductively and thereby stabilize the conjugate base. The third pA; is greater than the pX, of acetic acid because loss of the third proton puts a third negative Charge on the molecule. Increasing the number of charges on a species destablizes it (H"] [HO] ~ THO] Since [H"] = [H”), both must be 1x 10-7 M (Lx 107) x 107) 66. 555 K,= 180 x 10% pk, = ~log 180 10-1 pK, = 15.7 Copyright © 204 Pearson Facation. be 86 Chapter The answer can also be obtained in the following way [Ho HO] Ka (Ho! 17] (HO take the log of both sides log K, + log[H.0 } multiply both sides by 1 Jog K, — log[ HO] = [H0] = pH + poH [HO] = 14 14 + log] H,0! = log(H'] + log! HO] -} ~ log( HO ater, and uncharged compounds will dissolve in ether. The acide 67. Charged compounds will dissolve in w und the busie Forms are charged. The acidie forms of forms of carboxylic acids und aleohols are neutr amines are charged. and the basie forms are neutral coon “NH on Bia 1 CJ we NU 9.95 pK, = 10.66 Feiner WaterapH=20 ther layer wld ether ‘add HOt pH ist pH of HO to besween 7 and 8 fates eter layer wae yar ether ayer NH coo | OH cl A a oh aad HO with pl water yer ether hiper o a A = 1) CCopyigbt 2004 Peano Elston Chapter? 87 68. Foradiscussion of how to do problems such ay Problems 68-70, see Special Topic [(pH, pk, and Butters). [HA] pk = pH Tog The above equation, called the Henderson-Hasselbalch equation, shows that 1. When the value of the pH is equal to the value of the pX,, the concentration of buffer in the acidic form [HA] equals the concentration of butfer in the basie form [A 2. When the solution is more acide than the value of the p&, more butler species are in the acidic form than in the basic form, 3. When the solution is more basic than the value ofthe PX, more bur species are in the basi form than in the acidic form, Because the pH of the blood (~7.3) iy greater than the pk, value of the butfer (6.1), more buffer species are in the basic form than in the acidic form. Therefore, the buffer is better at neutralizing excess acid fei amount in the acidic form fraction present in the acidic form = = amount in the acidic form ++ amount in the basic form (Hal [HAT + [A] 69. Because there are two unknowns, we must define one in terms of the other By using the definition of the acid dissociation constant, we can define [A] in terms of [HA]. [H" ] and K,, So we have only one unknown, (HLA) [HA] pc] = MAHA 161 = a Substituting the definition of [A] into the equation for the fraction present in the acidic form gives: __ [HA] (HA) 1 [a] [HA] + [A] , KLHA) K "] + K, (Wal + ep ae ‘Therefore, the pereentage that is present in the acidic form is given by [Ho] cat,
7.
4.
8,
A solution with a pH = 2 is more acidic than a solution with a pH
A solution with a pH = 12 is more basic than a solution with a pH
Determining the pH of a Solution
To determine the pH of a solution, the concentration of hydrogen ion [H” ) in the solution must be determined.
a1
Copyeigh ©2014 Peason Eduction. te 92 Special Topie 1
Strong Acids
A strong acid is one that dissociates completely in solution. Strong acids have pk, values <1
Becauye a strong acid dissociates completely the concentration of hydrogen ions is the same as the concentration
of the acid: 1,0 M HC! solution contains [.0 M [H*]:a 13 M HCI solution contains 1.5 MH, Therefore, to
determine the pH of a strong acid, the [H*) value does not have to be calculated: it is the same as the molarity of
the strong acid
Solution Tal pH
LOMHCI 10M 0
1.0.x 107 MHCI 10x107M 20
64 x 104 MHCI 64x10%M 32
Strong Bases
Siro
wases are compounds such as NaOH or KOH that dissociate completely in water.
Because they dissociate completely. the [ HO” ] is the same as the molarity of the strong base
pOH describes the basicity of a solution. The smaller the pOH. the more basic the solution: just like the smaller the
pH the more acidic the solution
pOH = —log [HO]
[HOT | and [ H” | are related by the ionization consiant for water (K.)
Ky = [H*}[HO-]
pH + pOH = 14
Solution [HO™| poH pH
10M NaOH Lom 0 140-0 = 140
10x10“ MNaOH 10x 104M 40 140-40 = 100
78107 MNaOH 78x 107M Ld 0-11 = 129
Weak Acids
A weak avid does not dissociate completely in solution. Therefore, [H” ] must be calculated before the pH ean be
determined,
Acetic acid (CH\COOH) is an example of a weak acid. It hay an avid dissociation constant of 1.74 < 10 *
(pK, = 4.76). The pH of a 1.00 M solution of acetic acid can be calculated as follows:
CH,COOH == HY + CH,COO™
(LH JICH,COO"|
ICH,COOH}
Copyright 2014 Pearson Bdation, Ine Special Topic 93.
Each molecule of acetic acid that dissociates forms one proton and one acetate ion, Therefore, the concentration of
protons in solution equals the concentration of acetate ions. Fach has a concentration that can be represented by x
‘The concentration of acetic avd, therefore, isthe concentration we started with minus x.
(oa)
1.00= x
174 x 10%
‘The denominator (1,00 — x) can be simplified to 1.00 because 1.00 is much greater than x. (When we actually
calculate the value of x, we see that itis 0.004. And 1,00 ~ 0.004 = 1.00.)
1.74 x 10 = 3
1.00
x= 417 x 10%
pH = log 4.17 x 10
pH = 238
Formic acid (HCOOH) has a pK, value of 3.75. The pH of a 1.50 M solution of formic acid can be calculated as
follows:
HCOOH === H' + HCOO™
[H"}IHCOO}
{HCOOH |
A compound with a pk, = 3.75 has an acid dissociation constant of 1.78% 10
178 x 10% oe = in
x7 = 150(1,78 x 10)
v= 267 x 10%
1.63 x 107
log (1.63 x 10)
pH = 1.79
Weak Bases
When a weak base is dissolved in water, it accepts a proton from water, ereating hydroxide ion.
Determining the concentration of hydroxide allows the pOH to be determined, and this in turn allows the pH t0 be
determined.
Copycigh 2014 Peason Euaton. 94 Special Topic 1
‘The pH of a 1.20 M solution of sodium acetate can be calcu ated as follows
CH\COO” +H,0 === CH,COOH + HO”
Ky _ [HO [CH,COOH)
Ky ICH,COO"|
Loo x 10" _ wou
17x10 120—%
5.75 x 10°"
120
6.86 x 10"
62 * 10"
1HO-]
log 2.62 x 105
pH = 14.00-4.58,
pH = 9.42
Notice that by setting up the equation equal to K,,/K,, we can avoid the introduction of a new term (Kj). because
K./K, = Ky
Buffer Solutions
A butter solution is a solution that maintains nearly constant pH in spite of the addition of small amounts of H” ot
HO. That is because a bufter solution contains both a weak acid and its conjugate base, The weak acid ean donate
4 proton to any HO” added to the solution, and the conjugate base can accept any H~ that is added to the solution,
so the adulition of small amounts of HO or H” does not signiticantly change the pH of the solution.
A buffer can maintain nearly constant pH in a range of one pH unit on either side of the pK, of the conjugate acid
For example. an acetic acid/sodium acetate mixture can be used as a buffer in the pH range 3.76-5.76 because
acetic acid has a pX, = 4.76: methylammonium ion/methylamine can be used as a buffer in the pH range 9.7-11.7
because the methylimmonium ion has a px, = 10.7.
‘The pH of a buffer solution can be determined from the Henderson-Hasselblch equation. This equation comes
directly from the expression defining the acid dissociation constant. Its derivation is found on page 74 of the text.
Henderson-Hasselbalch equation
[Ha]
ay
pk, = pH + log
Copyright 92014 Peano blwation Ine Special Topic! 95
The pH of an acetic acid/sodium acetate buffer solution (pK, of acetic acid = 4.76) that is 1.00 M in a
and 0,50 M in sodium acetate is calculated as follows:
etic acid
[ua]
= pH + log
‘a = ol om
1.00
4.16 = pH + tog
050
4.76 = pH + log2
4.76 = pH + 0.30
pH = 4.46
Remember from Section 2.10 that compounds exist primarily in their acidic forms in solutions that are more acidic
than their pX, values and primarily in their basic forms in solutions that are more basic than theit pK, values.
Therefore. it could have been predicted that the above solution will have a pH less than the pX, of ae
because there is more conjugate acid than conjugate base in the solution,
ie acid,
‘There are three way
ys a buffer solution can be prepared:
1. Weak Acid and Weak Base
A buffer solution can be prepared by mixing a solution of a weak acid with a solution oF its conjugate base.
‘The pH of a formic acid/sodium formate buffer (pK, of formic acid = 3.75) solution prepared by mixing 25 ml. of
0.10 M formic acid and 15 mi. of 0.20 M sodium formate is calculated as tollows
‘The equation below shows that the number of millimoles (mmol) of each of the buffer components can be
determined by multiplying the number of milliliters (mL) by the molarity (MD.
noles __millimoles
M = molarity =
milliliters
Theretiore
25mL x 010M =
15imL x 0.20M = 3.0 mmol sodium formate
5 mmol formic acid
Notice that in the following equation we use mmol for (HA ] and [A] rather than molarity (mmol/mL) because
both the acid and the conjugate base are in the same solution so they have the same volume. Therefore, volumes
will cancel in the equation.
IAI
Di .
ia]
pH + log
25
415 = pH + loss
2.75 = pH + log 083
3.15 = pH - 0.08
pH = 3.83
i could hive been predicted that the above solution would have a pH greater than the pX, of Formic acid, because
there is more conjugate baye than conjuigate acid in the solution:
CCongrght © 2914 Pearson Faation Ine 96 Special Topie t
Weak Acid and Strong Bast
A buffer solution can be prepared by mixing a solution of a weak acid with a strong base such ay NaOH. The
NaOH reacts completely with the weak acid, thereby creating the conjugate base needed for the buffer solution.
For example, if 20 mmol of a weak acid and $ mmol of a strong base are added to a solution. the 5 mmol of strong
base will react with 5 mmol of weak acid. 1 ‘mmol of weuk base and leaving behind 15 mmol of weak acid
“The pH of « solution prepared by mixing 10 mL. of a 2.0 M solution of a weak acid with a pX, of 5.86 with 5.0 mL
of a 1.0 M solution of sodium hydroxide can be calculated as follows
When the 20 mmol of HA and the 5.0 mmol of HO” are mixed. the 5.0 mmol of strong base will react with
5.0 mmol of HA. with the result that 5.0 mmol of AV will be formed and 15 mmol (20 mmol ~ 5.0 mmol) of HA.
will be left unreacted.
1OmL x 20M = 20mmol HA |= ——> 15mmol HA
5.0mL x 10M = 5.0 mmol HO” ——+ 5.0 mmol A
[Ha
pk, = pH + log
:
5.6 = Hh + gS
pH + log3
pH + 0.48
5.38
3, Weak Base and Strong Acid
‘A butfer solution can be prepared by mixing a solution of a weak base with a strong acid such as HCI. The strong
acid will react completely with the weak base. thereby forming the conjugate acid needed for the buffer solution.
‘The pH of an ethylammonium ion/ethylamine bulfer (pK, of CH\CHsNH; = 11.0) prepared by mixing 30 mL. of
0.20 Methylamine with 40 mL of 0.10 M HC! can be calculated as follows:
30m x 0.20M = 6.0mmol RNH, ———= 2.0 mmol RNH»
dom x 0.10M = A0mmnal #” ——= Lommel RS,
Notice that 4.0 mmol H> reacts with 4.0 mmol RNH), forming 4.0 mmol RNH;, leaving behind 2.0 mmol RN}
. [HAL
pk, = pil + top
110 = pH + tog 22
20
11.0 = pH + loz 2.0
11.0 = pH + 030
pH = 10.7
Copysight © 2014 Pearson Eaton. Ie Special Topic 97
Fraction Present in the Acidic or the Basie Form
A common question asked is what fraction of a butler will be in a particular form at a given pH: either what fra
tion will be in the acidic form or what fraction will be in the basic form. This is an easy question to answer if you
remember the following formulas that are derived at the end of this section:
fraction present in the acidic form = —!41__
K+")
K,
fraction present in the basie form = 2
K+ 1H")
What traction of an acetic acid/sodium acetate buffer (pK, of acetic acid = 4.76; K, — 1.74 % 10°) is present in
the acide form at pH = 5.20: [H"} = 6.31 x 10°"?
url 631 x 10°
KO +H") (78x 10) + (631 x 10%)
631 x 10°
CTA x 10) + (6.31 x 10)
631 x 10° 631
aa oe BT
0.26
‘What fraction of a formic acid/sodium formate buffer (pK, of formic aci 3.75; K, = 1.78 X 10) is present
| = 1.26 x 1047
1.78 x 104
8 x 104) + (1.26 x 10)
118x104 _ 178
3.04 x 10 3.04
0.586
= 059
The Formulas describing the fraction present in the acidic or basic form are obtained from the definition of the acid
dissociation constant
_ LH" IA]
[Ha]
To derive the equation for the fraction present in the acidic form, we need to define [A] in terms of [HA], so we
will have only one unknown in the equation
K, [ua]
1H")
Ay
(Copycat © 2014 Peanon Education, I 98 Special Topic I
tract in the acidic form = [HA] [Ha] 1
raction present in the acidic form = —l#A]__ __ [HA] _ =
ALOT aay, SEAT 1 &
{H*] iH")
K+ In)
“To derive the equation for the fraction present in the basic Form, we need to define [HA in terms of [A]. s0 we
«can get rid of the [HA] term.
LAT
{Ha]
[aay = HAT
fraction present im the basic form = A |__ =
THA} IAT ayy UAT
+ (A)
Preparing Buffer Solutions
The type of calculations just shown can be used to determine how to make a buifer solution.
For example, how can 100 mL of a 1,00 M buffer solution with a pH = 4.24 be prepared if you have available to
you 1.50 M solutions of acetic acid (pK, = 4.76: K, = 1.74 < 10), sodium acetate, HCI, and NaOH?
First. we need to determine what fraction of the buffer will be present in each form at pH = 4.24:
[H’] = 5.75 X 10 5, We will start by calculating the fraction of the buifer present in the acide form,
iH’) 5.15 x 1
K+ (HT | (74 x 10%) +
5.15 x10)
7.49 x 10
= 077
Ita 1.00 M buffer solution is desired, the buffer must be 0.77 M in acetic acid and 0.23 M in sodium acetate
014 Peron Edi, te Special Topic 99
‘There are three ways to make sueh a buffer solution:
1. By mixing the appropriate amounts of acetic acid and sodium acetate in water, and adding water
to obtain a final volume of 100 mL.
The amount of a
ic acid needed: [CH,COOH] = 0.77 M
mmol _ x mmol
mL 100mL
x = 77mmol
M=
= 077M
Therefore, we need to have 77 mmol of scetic acid in the final solution,
To obtain 77 mmol of acetic acid from a 1.50 M solution of acetic acid:
TIimmel _ sp
ym
y = 51.3mL
Notice that the formula M = mmol/mL was used twice. The first time it was used to determine
the number of mmol of acetic acid that is needed in the final solution. The second time it was used
to determine how that number of mmel can be obtained from an acetic acid solution of a known
concentration,
The amount of sodium acetate needed: [CH;COO™| = 0.23M
xmmol _
100mL
x = 23mmol
0.23
To obtain 23 mmol of Sodium acetate from a 1.50 M solution of sodium acetate
2m! _ 5p ng
ym
y = 15.3 ml
The desired butler solution ean be prepared using: 51.3 mL 1.50 M acetie acid
15.3 mL 1.50 M sodium acetate
33.4 mL H,0
100.0 mL
Copyright © 2014 Pearson Flt ne 100
. By mixing the appropriate amounts of acetic acid and so
. By mixing the appropr
Special Topic |
ium hydroxide, and adding water to
obtain a final volume of 100 mL.
Soxtiuim hydroxide is used to convert some of the acetic acid into sodium acetate, This meuns that acetic
aeid will be the source of both acetic acid and sodium acetate
‘The coneentrations needed are: [CH;COOH] = 1.00 M
NaOH ] = 023M
The amount of acetic acid needed: [CH\COOH) = 1.00M
x mmol
TOO mL
x = 100 mmol
= 100M
To obtain 100 mmol of acetic acid front 1.50 M solution of acetic acia:
100 mmol
yb
y= 66.7 mL
=1,50M
The amount of sodium hydroxide needed: [NaOH] = 0.23M
xnmol
100mL,
023M
x=23mmol
‘To obtain 23 mmol of sodium hydroxide from a 1.50 M solution of NaOH:
23mmol
ym
= 150M
3m
‘The desired bulter solution can be prepared using: 66.7 mL. 1.50 M avetie acid
15.3 mL 150M NaOH
18.0 mL H,0
100.0 ml
ite amounts of sodium acetate and hydrochloric acid, and adding water
to obt 1 volume of 100 mL
a
Hydrochloric acid is used to convert some of the sodium a
te into acetic acid,
This means that sodium acetate will be the source of both acetic acid and sodium ac
The concentrations needed are: (CH\COONa] = 1.00 M.
HCI] = 077M
Copyright © 2014 Pearn Futon Ie Special Topic 101
“The amount of sodium acetate needed: [CHyCOONa} = 1.00 M
x mmol
= 100M
100 mL.
x =100 mmol
To obtain 100 mmol of sodium acetate from a 1.50 M solution of sodium acetate:
100 mmol
100 mmol _ 150M
yk
y= 06.7 mL.
‘The amount of hydrochloric acid needed:
[HCI] = 0.77 M
immo ees
100 mL.
x = 77 mmol
To obtain 77 mmol of hydrochloric acid from a 1.50 M solution of HCL
TI mmol
ym
y
150M
S13mL
100 mL. of a 1.00 M acetic acid/acetate buffer cannot be made from these reagents, because the volumes.
needed (66.7 mL + 51.3 mL) add up to more than 100 mL. To make this buffer using sodium acetate and
hydrochloric acid, you would need to use a more concentrated solution (> 1.50 M) of sodium acetate or a
‘more concentrated solution (> 1.50 M) of HCI.
Copyeight © 2914 Pearson Education, Ine 102 Special Topic 1
Problems on pH, pX.. and Buffers
1. Calculate the pH of each of the following solutions:
1x 10° M HCI
b. 0.60 M HCI
e140 x 102M HCI
d. 1 10M KOH
3.70 x 10M NaOH
311.20 M solution of an acid with a pk, = 4.23
g. 1.60 x 107 M sodium acetate (pK; of acetic acid = 4.76)
2. Calculate the pH of each of the following buffer solutions:
‘A buffer prepared by mixing 20 mL of 0.10 M formic acid and [5 mL. of 0.50 M sodium formate
(pK, of formic acid = 3.75),
A buffer prepared by mixing 10 mL of 0.50 M aniline and 15 mL of 0.10 M HCI
(pK, of the anitinium ion = 4.60).
©. A butfer prepared by mixing 15 mL of 1.00 M acetic acid and 10 mL of 0.50 M NaOH
(pK, of acetic acid = 4.76).
3. What fraction of a carboxylic acid with pk, = 5.23 would be ionized at pH = 4.987
4. What would be the concentration of formic acid and sedium formate in a 1.00 M butler solution with a
pH = 3.12 (pK, of formic acid = 3.75)?
You have found a bottle labeled 1,00 M RCOOH. You want to determine what carboxylic acid it is, so you
decide to determine its pK, value, How would you do this?
6. a, How would you prepare 100 mL ofa buffer solution that is 0.30 M in acetic acid and 0.20 M in sodium
acetate using a 1.00 M acetic acid solution and a 2.00 M sodium acetate solution?
ter or less than 4,76?
b. The pK, of acetic acid is 4.76. Would the pH of the above solution be
7. You have 100 ml. of a 1.50 M acetic acid/sodium acetate buffer solution that has a pH = 4.90, How could
‘you change the pH of the solution to 4.50?
8. You have 100 mL of a 1,00 M solution of an acid with a px, = 5.62 to which you add 10 mL of 1.00 M
sodium hydroxide. What fraction of the acid will be in the acidic form’? How much more sodium hydroxide
will you need to add in order to have 40% of the acid in its acidic form (that is, with its proton)?
Copyright © 2014 Pearon Education, be Special Topic 1 103
Describe three ways to prepare a 1.00 M acetie acid/sodium acetate bulfer solution with a pH = 4.00,
You have available to you 1.50 M solutions of acetic acid, sodium acetate, sodium hydroxide, and hydro:
chloric acid, How would you make 50 mL of each of the buffers described in the preceding problem?
How would you make a 1.0 M butter solution with a pH = 3.302
You are planning to carry out a reaction that will produce protons. In order for the reaction to take place at
constant pH, it will be carried in a solution bullered at pH = 4.2, Would it be better to use a formic acid
formate buffer or an acetic acid/acetate butler?
2014 Peano Faeaton ne 10 Special Topic 1
Solutions to Problems on pH, pX,, and Buffers
Secret caeecttremceaee erate
=
= =log 0.60
= 0.22
= -log (140 x 10)
= 185
4d. pOH = og (1 x 10)
pOH = 3
pH= 14 -3=11
fe. pOH = —log (3.70 x 10)
POH = 3.43
pH = 10.57
pK, = 4.23. K, = 5.89 x 105
HWA)
[ual
589 x 105 = *
1.20
x= 7.07 x 10%
y= 841 x 10%
pH = 208
Ky THOMA) ig = 1 = 174 x 0)
K [Ad
ho x 10"
174 x 107
PAREN Ue
= 9.20 x 10°?
v= 303x 10°
Bas
Copyright © 2014 Pearson Feat, In Special Topic 105
a. formie avid: 20 mL. * 0.10M
sodium formate: 15 mL 0.50 M
2.0 mmol
7.5 mmol
_
Ag
pH + top 22
75
3.15 = pH + log 0.27
pl + (0.57)
pH = 4.32
b. aniline: 10 mL x 050M = 5.0 mmol —> 3.5 mmol aniline (RNH,) .
HCE 15 mL. X 010M = 1.5 mmol —* 1.5 mmol anilinium hydrochloride (RNH)
[na]
pK,
4.60
4.60
4.60
pH
= pH + log 0.43
pH + (037)
497
ce. acetic acid: [S mL 100M = 15 mmol —> 10 mmol acetic acid
NuOH: 10 mL x 0.50M = 5.0mmol —> 5.0: mmol sodium acetate
+ tog HA]
IAT
4.76
10
PL + los
4.76
4.76
pH
pH + log 2
pH + 0.30
46
3. ‘The ionized form is the basic form. Therefore, we need to use the equation that allows us to calculate the
Fraction present in the basie form,
K, 5.89 x 10° 5.89 x 10°
K+ THT] G89 x 10) + (1047 x 10%) 16.36 x 10
fraction of buffer in the basic form: =
= 0.36
Copyright © 2014 Pearson Edin, be 106 Special Topic 1
x10t
14 (759% 10
4. fraction of buffer in the basic form =
IH") 1178 x 10
L78 x 107
9.37 10%
= 019
sodium formate, = 0.19 M.
[tormie acid) = 0.81 M
From the Henderson-Hasselbaleh equation, we see that the pH of the solution is the sume as the px, of
the species in the acidic form when the concentration of the species in the acidic form is the same as the
concentration of the species in the basie form,
pk
when [HA]
pK
‘Thus. in order to have a solution in which the pH will be the same as the p&;, the number of mmol of acid
rust equal the number of mmol of conjugate base
Preparing a sohution of» mmol of RCOOH and 1/2. mmol NaOH will give a solution in which
FRCOOH? = [RCOO
For example: 20 mL. of 1.00 M RCOOH = 20 mmol
10 mL of 1.00 M NaOH = 10 mmol
This will give a solution that contains 10 mmol RCOOH and 10 mmol RCOO
‘The pH of this solution is the pX, of RCOOH.
6 mmol _ 9 39 y4 mmol _ 999 \4
100 mi 100 mL.
4 = 30 mmolofaceticaeid x = mmol of sodiumavetate
30 mmol 20 mmol
Smet 00M Ammo! 300M
yml. yk.
y = 30mL of 1,00 M acetic acid J = 10 mL. of 2.00 M acetic acid
‘The butter solution could be prepared by mixing: 30 mL. of 1,00 M acetic aeiel
10 mL of 2.00 M sodium acetate
60) mL of water
100 mi.
1b, Because the concentration of butler in the acidic form (0.30 M) is greater than the concentration of
butfer in the basic form (0.20 M). the pH of the solution will be less than 4.76.
© 2014 Pearson Fain, In Special Topic L107
Original solution
K
fraction of buffer in the basic form = ———*—— = ——— pany
K, +1] (74x 10) + (1.26 x 10)
174 x 10%
© 3.00 x 10%
= 058
0.58 x 1.50 M = 087M
IA] = 087M
[HA] = 063M
Desired solution
K 174 x 10%
fraction of buffer in the basic form
AFF” Gdex 0) + Ibe
174 x 10%
4.90 x 107
0.35 x 150M=
=
[Ha] = 097M
“The original solution contains 87 mmol of A (100 mL. x 0.87 M).
‘The desired solution with a pH = 4.50 must contain 53 mmol of A”,
‘Therefore, 34 mmol of A’ (87 ~ 53 = 34) must be converted to HA.
‘This can be done by adding 34 mmol of HCI +0 the original solution.
If you have a 1.00 M HCI solution, you will need to add 34 mL. to the original solution in order to change its
pH from 4.90 10 4.50.
34 mmol
xm
x= Mol
00 M.
+ it will be more dilute
Note that after adding HCI to the original solution, it will no Jonger be a 1.50 M butle
(150 mmol/134 mL. = 1.12 M).
‘The change in the concentration of the buffer solution will be less if'a more concentrated solution of HCL is
used 1o change the pH. For example, if you have a 2,00 M HCI solution:
34mmol _ 599M
xml
x= 1TmL
Copycih ©2014 Pearson Education, In 108 Special Topic 1
You will need to add 17 mL. to the original solution, and the concentration of the butler will be
1.28 M (150 mmol/117 mL = 1.28 M).
8. acid: 100 mL. x 1.00M
NaOH: 10 mL. 1.00 M
‘Therefore, 90% is in the acidic form,
100 mmol HA. —> 90 mmol HA.
10mmol HO") —> 10. mmol
For 40% to be in the acidie form, you need
40 mmol HA
60 mmol A”
You need to have 60 mmol rather than 10 mmol in the basie form. To get the additional SO mmol in the basic
orm, you would need to add 50 mL. of 1.0 M NaOH.
9. fraction of butler ws 174 x10
inthe basic form 4 [HT] (74 x 10) + (1.00 x 10 (LTH x 10°) + (10.00 x 10°
_ La x 10%
174x107
= 015
[A] = 015M
[Ha] = 085M
a. [acetic acid] = 0.85 M b. [acetic acid] = 1.00M_ —e. [xodium acetate) = 1.00 M
[ sodium acetate] = 0.15 M [NaOH] = 0.15 M [HCI] = 0.85 M
mmol
Wa = 085M
& So mL.
X = 42.5 mmol of acetic acid
425
mmol _ 59 Mt
ym.
y = 283mLof 150M acetic ucid
0.15M
7.5 mmol of sodium acetate
150M
y= 5.0 mL of 1.50 M sodium acetate
28.3 mL of 1.50 M acetic acid
O mL of 1.50 M sodium acetate
16.7 mL. of HO
50.0 mL.
Copyright 2014 Pearson Education, be Special Topic |
be Emme! 9 Mt
50 mL.
x = SO mmol of avetie seid
SOmmol _ | 59 y4
ymk.
33.3 mL of 1.50M aceticacid
xmmol
50 mL
015M
7.5 mmol of NaQH
= 150M
= 5.0 mL of 1.50 M NaOH
33.3 mL of 1.50 M acetic acid
5.0 mL of 1.50 M NaOH
of HO
50.0 mL,
100M
50 mmol of sodium acetate
50
ym
150M
33.3 mL of 1.50 M sodium acetate
xmmol
50.ml.
0.85 M
= 42.5 mmol of HCL
LSM
28.3 mL of 1.5 MHCI
We cannot make the required butter with these solutions, because 33.3 mL + 28.3 mL > 50 mL,
(Copysight © 2014 Pearson Eduction, In
109 Ho
ML.
Special Topic 1
Because formic acid has a pk, — 3.75. a formic acid/formate butfer ean be a buffer at pH = 3.30, sinee this,
pH is within one pH unit of the pk, value.
78 x 104
(178 10-41) + 5.01 x 104)
fraction of butler in the basie form Ky |]
Las x 10+
679x107
= 0.6
The solution must have [ formic acid } = 0.74 M and / sodium formate” = 0.26 M.
The reaction to be carried out will Ke protons that will react with the basic form of the buffer in order
tw Keep the pH constant
ne
Therefore. the better bulfer would be the one that has the larger percentage of the butler in the basie form,
The pX, of formic acid is 3.74. Because the pH of the solution (4.2) is more basic than the p&, value of the
compound. formic acid will exist primarily in its basic form,
The pk, of acetic acid is 4.76, Because the pH of the solutions is more aidie than the p&, value of the
‘compound. acetic acid will exist primarily in its avidie form,
‘Therefore. the formate bulfer iy preferred, because it bus u greater perentage of the butler in the basic form,
Copseigh © 2014 Paso Elation, I An Introduction to Organic Compound:
Nomenclature, Physical Properties, and Representation of Structure
mportant Terms
alcohol
alkane
alkyl halide
alkyl substituent
amine
angle strain
anti conf
bond
boat conformer
boiling point
chair conformer
cis fused
cis isomer
(for a eyelie compound)
n name
conformation
conformational analysis
a compound with an OH group in place of one of the hydro
(ROH)
wens of an alkane
a hydrocarbon that contains only single bonds.
a compound with halogen in place of one of the hydrogens of an alkane.
‘a substituent formed by removing a hydrogen from an alkane,
a compound in which one or more of the hydrogens of NHy are replaced by an
alkyl substituent (RNHs, RSNH, RsN)
the strain introduced into a molecule as & result of its bond angles being distorted
rom their ideal values,
the staggered conformer in which the largest substituents bonded to the two
carbons are opposite each other, It is the most stable of the st
ered contormers,
a bond of the chair conformer of eyelohexane that points directly up or directly
down,
a conformer of cyclohexane that roughly resembles a boat
the temperature at which the vapor pressure of a liquid equals the atmospheric
pressure.
air, I is the most stable
a conformer of cyclohexane that roughly res
conformer of cyclohexane.
two rings fused together in such a way thet if the second ring were considered to
be two substituents of the first ring, the two substituents would be on the same side
of the first ring
the isomer with two substituents on the same side of the ring,
see the definition of “cis isomer” and “trans isomer.
non-systematie nomenclature:
the three-dimensional shape of a molecule at a given instant
the investigation of various conformers of a molecule and their relative stabilities.
ut
Copyright © 2014 Pearson Baveaton. 112 Chapter 3
conformers
constitutional isomers
(structural isomers)
cyeloalkane
1,3-diaxial interaction
dipole-dipole interaction
eclipsed conformer
equatorial bond
ether
flagpole hydrogens
functional geoup
gauche conformer
half-chair conformer
homologue
homologous series
hydrocarbon
hydrogen bond
different conformations of a molecule,
molecules that have the same molecular formula but differ in the way the atoms
wre connected,
aan alkat
e with its carbon chain arranged in a closed ring.
the interaction between an axial substituent and one of the other two axial substitu-
cents on the same side of a eyclohexane ring.
an interaction between the dipole of one molecule and the dipole of another.
a conformer in which the bonds on adjacent carbons are parallel to each other
when viewed looking down the carbon-carbon bond
a bond of the chair conformer of eyctohexane that juts out from the ring but does
‘not point directly up or directly down,
«at compound in which an oxyzen is bonded to two alkyl substituents (ROR).
the two hydrogens in the beat conformer of cyclohexane that are at the 1- and
4-positions of the ring,
the center of reactivity of a molecule.
a staggered conformer in which the largest substituents bonded to the two carbons
are gatiche to each other: that is, their bonds have a dihedral angle of approxi-
mately 60°.
key
TAY The substituents are gauche to each other.
oy
the interaction between two atoms or groups that ure
luche to each other,
cis-trans (or £.Z) isomers.
the least stable conformer of cyclohexane.
‘a member of a homologous series.
satan
lene group,
‘of compounds in which each member differs from the next by’ one methy
a compound that contains only carbon and hydrogen.
an unusually strong dipole-cipole attraction (5 keal/mol) between a hydrogen
bonded to O. N, or F and the lone pair of a different O. N. or F.
Copyright © 2014 Pearson Eaton tne hyperconjugation
nduced dipole-induced
dipole interaction
IUPAC nomenclature
n
melting poi
methylene group
‘Newman projection
packing
parent hydrocarbon
perspective formula
polarizability
primary alcohol
primary alky! halide
primary amine
primary carbon
primary hydrogen
quaternary ammonium
salt
ring-flip (chair-chair
interconversion)
sawhorse projection
secondary alcohol
secondary alkyl h
secondary amine
secondary carbon
ndary hydrogen
Chapter} 113
delocalization of electrons by the overlap of a or orbital with an empty orbital,
an interaction between a temporary dipole in one molecule and the dipole that the
temporary dipole induces in another molecule.
systematic nomenelature.
the temperature at which a solid becomes a liquid,
a CH, group.
‘a way to represent the three-dimensional spatial relationships of a
down the length of a particular carbon-carbon bond.
oms by looking
a property that determines how well individual! molecules fit into a crystal lattice.
the longest continuous earbon chain in a molecule: if the molecule has a functional
‘group. itis the longest continuous carbon chain that contains the functional group.
1 way to represent the three-dimensional spatial relationships of atoms u
adjacent solid fines, one solid wedge, and one hatched wedge.
the ease with which an electron cloud of an atom can be distorted.
aan aleohol in which the OH
oup is bonded to a primary carbon,
dan alkyl halide im whieh the bl
1s bonded toa primary carbon,
4m amine with one alkyl group bonded to the nitrogen.
4 carbon bonded to enly one other carbon.
athydrogen bonded to a primary carbon
a nite
yen compound with four alkyl groups bonded to the nitrogen, plus an
accompanying anion,
the conversion of a chair conformer of cyclohexane into the other chair conformer,
Bonds that are axiel in one chair conformer are equatorial in the other chair
conformer
‘way to represent the three-dimensional spatial relationships of atoms by looking
at the carbon-carbon bond from an oblique angle,
aan alcohol in which the OH group is bonded to a secondary carbon,
aan alkyl halide in which the halogen is bonded to a secondary carbon,
aan amine with ovo alkyl groups bonded to the nitrogen.
a carbon bonded to two other carbons
a hydrogen bonded to a secondary carbon.
Copysight ©2014 Peano Eduction, Ie TL Chapter 3
skeletal structure
skew-boat conformer
solubility
solvation
staggered conformer
steric hindrance
steric strain
straight-chain alkane
Structural isomers
‘constitutional isomers)
symmetrical ether
systematic nomenclature
tertiary alcohol
te
ary alkyl halide
tertiary amine
tertiary carbon
to
iary hydrogen
ns-fused
trans isomer
(for a cyclic compound)
twist-boat conformer
unsymmetrical ether
van der Waals fores
4 structure that shows the carbon-carbon bonds as Tines and does not show the
carbon-hydrogen bonds,
‘ong of the conformers af a eyelohesane ring
the extent to which a compound dissolves in a solvent,
the interaction between a solvent and another molecule (or ion}
a conformer in which the bonds on one carbon biseet the bond angles on the adja
‘hy
ain
hindrance due to groups occupying a volume of space
the repulsion between the e eetron cloud of an atom or group of atoms and the
electron cloud of another atom or group of atoms,
aan alkane in which the carbons form a continuous chain with no branches,
molecules that have the same molecular formula but differ in the way the atoms
are connected,
ian ether with two identical alkyl substituents bonded to the oxygen.
a system of nomenclature based on rules such ats TUPAC nomenclature,
an alcohol in which the OH group is bonded to « tertiary carbon,
aan alkyl halide in whict the Falogen is bonded to a tertiary carbon,
aan amine with three alky! groups bonded to the nitrogen.
carbon bonded to three other carbons,
ahydros
sn bonded to a tertiary carbon,
wether in such a way that if the second
be two substituenty of the first ring, the two substituents would he on opposite
Sides of the first ring.
Wg Were considered {0
the isomer with two substituents on opposite sides of the ring.
one of the conformers of a eyelohexane ri
aan ether with two different alkyl substituents bonded 10 the oxyzen.
induced dipole-induced dipole interactions
Copygbt © 2014 Peano flation In: Chapter} 115.
Solutions to Problems
1. a G)Hyy) I'there are 17 carbons, then there are 36 hydrogens.
5
7.
Db. CyHy 3 If there are 74 hydrogens, then there are 36 carbons.
CHSCHLCHACHE,CHACHCH CH, CHYCHCHLC HCH,
octane Cy isooctane
a. propyl alcohol by butyl methyl ether ¢.propylamine
cHNHCH CH, bs
cHy
2-methylbutane 2.2-dimethylpropane
Notice that each carbon forms four bonds, and each hydrogen and bromine forms one bond.
on
CH,CH CHyCHBr CHCHCHCH, conesch CHCCHy
| |
Br Hy Br
n-butyl bromide sec-butyl bromide isobutyl bromide tert-butyl bromide
or
butyl bromide
‘Dibromomethane does not have constitutional isomers” proves that carbon is tetrahedral
if carbon were flat, rather than being tetrahedral, dibromomethane would have constitutional isomers
because the two structures shown below would be different since the bromines would be 90° apart in one
compound and 180° apart in the other compound. Only because carbon is tetrahedral are the two structures
identical
m
ney u
be
an
a. cucuott e ancien fe cnent
ci bu bi
cn
b cucnencnsr a cHton f CHKCHCH.CHACHCHLCHCHBr
an buen
Copyright 9 2044 Peanon Eduction, be 116 Chapter 3
8. a. ethyl methylether ——e,sec-butylamine €. isobutyl bromide
b, methyl propylether butyl alcohol or n-butylaleohol—f sec-butyl chloride
CHy CH, CH
9 a. Solvedindhe tet cu diene—bicncn,
dich
cn
CHy CHy
i I
CH,CHCHSCHCHCH:CHLCHy,
I
chy
i
oo
cy
HCH f
HyCHCHCHsCHSCH,
I
CHCCH,
|
chy
Hh CH
|
10. a #1 CHSCHSCHSCHSCH,CHACH CH, #10. CH\CHCH—CHCH.CHH,
octane 3.4-dimethy hexane
cu on
HsCHsCHSCHy #1 CHC CHCHCHy
#2 CHCHCHS
CH cH
2-methy heptane -trimethy pentane
cus
#3 CHACHSCHCH CHSCH-CH, #2 crngensci,
al
Hs
3-methylhneptane
#4 CH,CHSCHCHCHSCHSCH;
I
ox
-bmethyheptane 2.3.3:41imethypemane
Cis cH cll, chk
#5 cncencn.cu.c, fe center,
an
2.2 meth hexane 2.3b4rimethypentne
Copyright © 2014 Peuson Easton os
#6 CHCHSCCHSCH.CH,
I
cH
3.3-dimethylhexane
#7 CH CHy
I I
CHACH—CHCHSCHSCHy
2.3-dimethythexane
on
CH,CHCHSCHCH:CHs
2.4-dimethylhexane
cHy
I
_ gh
#9 CH,CHCH.CHSCHCHy
2.5-dimethylhexane
b. The syst
Chapter3 117
CH CH
#15
Hy
tetramethylbutane
CH CHACHCH.CHLCH
#16
CHACHy
3-ethythexane
cH
#7 cHcH.cHCHEH,
éineny
3-ethyl-2-methylpentane
#18 °CHSCHy
CHACH,
3-ethyl-3-methylpentane
natic name is under each structure,
c. Only #1 (octane or n-octane) and #2 (isonctane) have com
on names.
#247, #8, #9, $12. #13, #14, #7
co #38, #10, #1)
f AS HII HI #15
a, 2.2.4-trimethylhexane f. S-ethyl-4.4-dimethyloctane
b. 2.2-dimethylbutane g 33-diethyIhexane
€. methyl-4-propytheptane bh, 4(1-methylethy! octane
4d. 2.2,S-trimethylhexane i, 2.5-dimethylheptane
fe. 3.3diethyl-+-methyl-5-propyloctane
cH, an os
|
a. CH,CHSCHSCHCHy—b. CHSCCHs CHCHCHSCHs —d. CHCHCHSCHs
|
CH
pentane .2-dimethytpropane 2-methylbutane 2-methylbutane
1B.
CConyight ©2014 Pearson Bd. 1s
14.
16.
17.
18,
Chapter 3
a
e ‘OH
be
GH CCH,
CH,CHCHCHCH ,CH,CH, b.
i
CHSCH,
L-ethy!-2-methyleyelopentane
ethyleyelobutane
-ethyl-1.2-dimethylcyclohexane
3.6-dimethyldecane
lopropyliiesane
sce-butyl chloride
2-chlorobutane
secondary
yelohexy! bromide
bromocyclonexane
secondary
Copssaht
os
CHLECHSCHCHICH,
CH, CH,
xa
£Lethy[-3-(2-methylpropyleyelohexane
(I-mnethylethy nonane
hh. 1-(L-methy ethy1)-4-11-methylproply ieyelohexane
i. heptane
J. Pbromohesane
€. isohexyl chloride
{-chloro-+-methytpentane
primary
4. isopropyl Muoride
2-fluoropropane
secondary
2114 Paro shin. I 19,
20,
2.
2.
Note that the name of a CH;CI
sustituent is “chloromethyl,
because a Clis in place of one of
the Hs of a methyl substituent
chloromethyleyclohexane
ech
a An
2 a
J-chloro-2-methyleyclohexane
| -chloro-3-methyleyclohexane
Chapter3 119
b Cl CHy
LY
|-chloro- I-methyleyclohexane
cHy
1. methoxyethane 4, |-isopropoxy-3-methylbutane
2. ethoxyethane 5. I-propoxybutane
4-methoxyoctane 6, 2-isopropoxyhexane
b. No
fe. 1 ethyl methyl ether 4, isopentyl isopropyl ether
2. diethyl ether 5. butyl propyl ether
3. -nocommon name 6. no common name
cHOH CH\CHCH;CHOH
common = methyl aleahol common = butyl alcohol or n-butyl alcohol
systematic = methanol systematic = I-butanol
CH,CH.OH (CH\CH,CHCH,CHLOH
common = ethyl alcohol ‘common = pentyl aleohol or n-penty! alcohol
systematic = ethanol
systematic = [-pentanol
CH\CH.CH.OH CH,CH)CHCH,CH,CH,OH
common = propyl alcohol or n-propyl alcotol common = hexyl alcohol or n-hexyl aleohol
systematic = I-propanol systematic = I-hexanol
a, [-pentanol ¢.S-methyl-3-hexanol
primary secondary
b, S-chloro-2-methy d.T-methyl-3,5-octanediol (Notice that because there
tertiary
are two OH groups, the suffix is “dio.”)
both alcohol groups are secondary
Copytigh © 2014 Pearson Education, te mM.
26.
2.
28.
Chapter 3
Se
a
chy cH
| I
CHCCH:CH:CH, CHCH.CCH.CH,
| 1
on on
2-methyl-2-pentanol — 3-methyl-3-pentanol
a, 4-chloro-3-ethyleyclohexanol
secondary
b._ 7.8dimethy!-3-nonanol
secondary
a, tertiary alkyl halide —b. tertiary alcohol
a. hexylamine
I-hexanamine
primary
1b. see-butylisobutylamine
\N-isohutyl-2-butanamine
secondary
¢. diethylmethylamine
N-ethy|-N-methylethanamine
tertiary
a CHyCHSCH.NHCH,CHCHs
|
cH
b. CH)CI:NHCHCH,
6. CHACHCH:CH:CH:CHLNI
I
cH,
a, 6-methyl-I-heptanamine
isooetylamine
primary
b. cyclohexanamine
ee
cyclohexylan
primary
on
Se
I
CHC—CHCH,
I
OH CH
2.3-dimethyl-2-butanol
. I-bromo-5.5-dimethy!
second:
heptanol
4d. 4-methyleyctohexanol
secondary
¢. primary amine
._butylpropylamine
N-propyl--butan
secondary
fe. diethylpropylamine
N,N-diethyl-I-propanamine
tertiary
£Neethyl-3-methyleyclopentanamine
no common name
secondary
ad. cHACHCHNCHCHCH,
Hy
fe. CH\CHSCHCHSCHy
I
N.
aN
ct “oH
S—vew.cns
I
cH
¢.4-methyl-N-propyl-1-pentanamine
isohexylpropylamine
secondary
d. 2.5-dimethyleyctohexanamine
‘no common name
primary
Copyright © 2014 Peusontavetion Ine 2».
33.
MM
Chapter3 121
‘The bond angle is predicted to be similar to the bond angle in water (104.5°)..
The bond angle is predicted to be similar to the bond angle in ammonia (107.3°).
‘The bond angle is predicted to be similarto the bond angle in water (104.5°).
The bond angle is predicted to be similar to the bond angle in the ammonium ion (109.5°).
Fe
To be a liquid at room temperature, the compound must have a boiling point that is greater than room
temperature.
pentane or 2-methylbutane
a 1. 4vand 5
1.2.4, 5, and 6
ich water molecule has two hydrogens that can form hydrogen bonds, whereas each alcohol mole-
cule has only one hydrogen that can forma hydrogen bond. Therefore, there are more hydrogen bonds
between water molecules than between alcohol molecules.
O-H--:G-H O—CHy
| | |
" u H
aaa:
H
b. Bach water molecule has two hydrogens that
an form hydrogen bonds and two lone pairs that can
accept hydrogen bonds, so both hydrogens of a water molecule can engage in hydrogen bonding, In
contrast. ammonia has three hydrogens that can form hydrogen bonds but only one lone pair that can
accept hydrogen bonds, so only one hydrogen of an ammonia molecule can engage in hydrogen bond-
ing, so it will have a lower boiling point than water.
€. Bach water molecule has two hydrogens that can form hydrogen bonds und two lone pairs that ean
accept hydrogen bonds, so both lone pairs of a water molecule can engage in hydrogen bonding. In
contrast, HF has three lone pairs that can accept hydrogen bonds but only one hydrogen that can form a
hydrogen bond, so only one lone pair of a HF molecule can engage in hydrogen bonding, so it will have
4 lower boiling point than water,
4d, HF and ammonia can each form only one hydrogen bond, but HF has a higher boiling point because
the hydrogen bond formed by HF is stronger since fluorine is more electronegative than nitrogen
Copyright © 2014 Pearson Boston, Ie Chapter 3
PARA AR LAA
i a ae
: my NNO AR OA
oH 0 °
b. HOCH;CH,CH,OH > CH,CHSCH,OH > CH,CH,CHJCH,OH > CH,CH,CH.CH:
Because cyclohexane is a nonpolar compound, it will have the lowest solubility in the most polar solvent,
Which, of the solvents given, is ethanol
CHjCH2CH3CH3CH{OH CH,CH,06
1-pentanol ‘diethyl eth
2CHy — CHsCHj0H = CHyCHyCH)CHCH CH,
ethanol hexane
Start with the least stable conformer and then obtain the others by keeping the front carbon constant and
rotating the back carbon clockwise.
sao vee
a. deat, dns "hye wets
Sdn Yt We yguscs
HW e u W
‘ 6
Hs _ cus
HCH aa
4 4 HCH:
. cmt
H Hq iy H oH
cH.cH, cllen, 4
E F
Potential
nergy
0 0 0 180 240 wo we
Degrewsof Rotation 4.
ai.
42.
4
Chapter3. 123
‘The Newman projection shows rotation about the
OH
4
a Te ~ ethyl-2-pentanol
1b, The Newmian projection shows rotation about the C-2—C-3 bond.
2-methy!-2-pentanamine
‘To draw the most stable conformer: put the gest group on the front earbon opposite the largest group on
the back carbon
a CHy be CHSCHy Ge CHyCHy
noon H HW " u
YIy y
u oH Ho CHy CHy ‘CHy
CHscHh och, Ga.ci,
. 360°
340 =
a. iso * ba ty
180° ~ 40° = 140°
You can get the total strain ‘of eycloheptane by subtracting the strainless heat of formation from the
atctual heat of Formation
The
The actual heut of formation of
trainless” heat of Formation of eycloheptane is 7 (—4.92) = ~34.4 keal/mol.
-yeloheptane is ~28,2 keal /mol (trom Table 3.8 on page 127 of the text).
2 keal /mol,
Therefore, the total strain energy of eycloheptane is ~28.2 — (~34.4) =
Hexethal would be expected to be the more effective sed
henethal has a hexyl group in place of the ethyl group of barbital. Being less polar, hexethal will be better
able 0 penetrate the nonpolar membrane of the eel
ve because it is less polar than barbital since
acl a bo a
‘Two 13-diaxial (gauche) interactions cause the chair conformer of fuorocyelohexane to be 0.25 keal/mol
less stable when the fluoro substituent is in the axial position than when it is in the equatorial position.
The gauche conformer of |-fuoropropane his one gauche interaction (see Figure 3.15 on page 131 of the
text), Therefore, the gauche conformer is (0125/2) = 0.13 keal/mol less stable than the anti conformer
that has no gauche interactions
Copysighh © 2014 Pear uct, I 124
45.
46.
47.
48.
49.
Chapter 3
[equatorial conformer] _ 5.4
[axial conformer | 1
[equatorial conta
al conformer] +
mer]
% of equatorial conformer x 100
[equator xia conformer |
4 sa
= 5 x 100 = x 100 = 84%
Fa ay * 100 = GX 100 = 8
If both substituents point downward or both point upward. it isa cis isomer
Ione substituent points upward and the other downward, itis a trans isomer
a cis b. cis cis dans.
Both srans-1 4-dimethyleyclohexane and cis-L-rert-butyl-3-methyleyclohexune have a conformer with two
substituents in the equatorial position and a conformer with two substituents in the axial position
civ-|-tert-Buty!-3-methyleyelohexane will | of the diequatorial-substituted
conformer because the bulky tert-butyl substituent will have & greater preference for the equatorial posi-
tion than will a less bulky methyl substituent, since the larger substituent will have greater destabiliz
1.3-diaxial interactions when itis in an axial positior
her percents
a HH. b. FHC:
La —L-chy
Hs
trans-1-Eihyl-2-methyleyclohexane ix more stable beeause both substituents can be in equatorial
positions.
a. one equatorial and one axial in each one equatorial and one axial in each
. both equatorial in one and both awial in the other €. ane equatorial and one axial in each
¢. both equatorial in one and both axial in the other f& both equatorial in one and both awial in the other
a, and) b, Solved in the text
cHy chs H
i H HW oe a
iC Y
cur DN 7 WPAN ea,
4H H H 4
d. There will be equal amounts of the two conformers at equilibrium because they have the same
stability—each one has one methyl group on an equatorial bond and one methyl group on an axial
bond.
a. One chair conformer of rrans-1_4-dimethyleyclohexane has both substituents in equatorial positions,
so it does not have any 1.3-diavial interactions, The other chair conformer hats both substituents in
axial positions. When a substituent is in an axial position, it experiences two 1.3-diaxial interactions,
so this chair conformer hay a total of four 1.3-diaxial interactions.
Copyright © 2014 Pearson keaton, ln Chapter 3125
Because the 1.3-diavial interaction between a methyl group and a hydrogen causes a strain energy of
0.9 keal/mol, the chair conformer with both substituents in a
less stable than the chair conformer with both substituents in equatorial po
oer By ates
b, Each of the chair conformers of ef
positions is 4 x 0.9
3.6 keal/mol
A
°CHy
a1. 3-diaxial
1 .4-dimethyleyclohexane has one substituent in an equatorial
position and one in an axial position. Therefore, the two conformers are equally stable,
52. Both condensed and skeletal structures are shown,
oy
a. CHCHSCHOCCH
TK
1b. CHCHCH;CH;CH;CH.OH
I
Hy
AWA
¢. CHSCHsCHNHy
1
chs
oe
4 cHycricnycier
CHy
cH
cueny
« cnc,
CH,CH.CH.CH.CHCH
NN
HCH
|
f CHCHN
|
CHCHy
aa
.
Congright ©2614 Peann Edoaton, I 126 Chapter 3
J. CH.CH.CHY
|
CHCH,
I
~ ~N
oe ee
we ~N S
® ou
h, eee ees Hs, KK. CHyCF:CHCHCH)CH:CH.CHy,
re
(CH,CHCH,,
i. ie 1 CHyCH)CH;CHCH)CH)CH,CH)CH,,
bene
Ae a
L
oe
: on De
53, >No > - > NO
| a x
|
NN >
hydiogen ands dipole-dipole
ker ipoteipole tracts
iments than
mpage Bose
negative thin
Copyright ©1204 Pearon Educabon 56.
57.
Chapter3 127
2.6-trimethytheptane 7. dethoxyheptane
romo-2-methyloctane 8, 1.3-dimethoxypropane
S-methyl-3-hexanol 9, NW-dimethyleyelohexanamine
dicthylpentane 10, 3-ethyleyclohexanol
5-bromo-N-ethyl-[-pentanamine HL. L-bromo-4-m
6. 2.3.S-trimethythexane
b.
NN
7 Sg ey
A J
Hy Gh os .
2 HCHCH:CH, 6. CH,CHCHCHCHCH wf a
br cry i
on
8 POON
snd D are cis isomers, (In C both substituents are downward pointing: in D both substituents are upward
pointing.)
abs 24 ob LO 2S oe 34
The
interactions will not be as Lary
between two CH, groups,
ist conformer (A) is the most stable because the three substituents are more spread out, so its gauche
the Clin A is between a CHy and an H. whereas the Clin B and C is
oH cH
a be CHYC—CCHy & CHREHCHCHCH,
Lt I
CH) CH CH CH
Copyright ©2014 Pearson Fastin, Ine 128
59.
60.
61.
62.
caper
b. 2ebyobae -hrom-2 methane
Wey tuananine bh. tg penn
a. ettospropne L_omoetopenane
fe. 2-methylpentane Ge cyclohexanol
a. -bromhecane aero aeatersurfce ———g_Praoentne homing ager nd move
we potwite
pentyl chloride (greater surface area than h._ butyl alcohol (forms hydrogen bonds)
the branched compound) K.octane (sce Table 3.1)
e. hunol ever cao) J. open el rms stoner hydrogen
4. I-hexanot (forms hydrogen bonds) bonds)
tpl ts yaogen bony iyaosen bos nd sects aie)
a CHy CHy H
Soa aod
OP PM oe Pen,
Hoon i
b. the one on he ight would predominate atc ease it i me sble ing bath met
pear neq sions
:
cH a
Sho"
4 CHy
Sob
io
. There would be equal amounts of each one at equilibrium, because they have the same stability since
each conformer hats one methyl group in an equatterial position and one methyl group in an axial position,
Ansaid is more soluble in water. It has 3 fluoro substituent that ean form a hydrogen bond with water
Hydrogen bonding increases its solubility in water,
GH CHy CH
CHy CHy Hy
H—Q)—-H—Q>-H—O:
Copyright © 2014 Peary Fadaton, 65.
66.
7.
68.
Chapter3 129
‘The student named only one compound correctly.
a, 2-bromo-3-pentanol & correct
b. d-ethyl-2,2-dimethythepiane h, 2,5-dimethytheptane
¢. 3-methyleyelohexanol i, S-bromo-2-pentanol
dd, 2,2-dimethyleyclohexanol -ethyl-2-methyloctane
e methylpropy! jnonane k. 2.3.3-trimethyloctane
f.I-bromo-3-methylbutane 1. NNSetrimethyl-3-hexanamine
All three compounds are diaxial-substituted cyclohexanes. B has the highest energy. Only B has
1.3-diawial interaction between CH; and Cl. which will be greater than a 1,3-diaxial interaction between
CH and H or between Cl and H
The only one is 2,2.3-trimethylbutane.
CH CHy
i
CH,C—CHCH,
I
Hy
ioe
essseecemecreseserea
pees
a _
First draw the structure, so you know what groups to put on the bonds in the Newman projections.
es
CH=CH CH) —CHy CH CH
CHy
Hs
a CHCH,
Hi H
H "
CHACHy
most stable least stable
Rotation can occur about all the C—C bonds. There are six carbon-carbon bonds in the compound, so
there are five other carbon-carbon bonds. in addition to the C\—C; bond, about which rotation can occur,
CCopysght ©2914 Pearson ducati, Ie 130
69.
70.
db
Chapter 3
4d. Three of the carbon-carbon bonds have staggered conformers that are equally stable because each is
bonded to a carbon with three identical substituents,
(CHyCH,CH3CH,CH2Br
cHoHeRCHCH,
he
cmcr.crcnsct,
th
om,
crncHenscnte
ony
“HCH
oi
CCH
CHHy
Br
i
CIRCHEHCH
ch
Hy
I
HCH
Hy
e
!
CH= CH—CH)—CH)— CH CHy
SI
cHy
a, I-bromopentane
b. pentyl bromide
a, 2-bromopentane
b. no common name
a. 3-bromopentane
b. no common name
a. -bromo-3-methylbutane
b. isopenty! bromide
a. I-bromo-2-methylbutane
b. no common name
a, 2-bromo-2-methytbutane
b. tert-pentyl bromide
a. 2-bromo-3.methylbutane
b. no common name
a. [-bromo-2.2-dimethylpropane
1b, no common name. but in older
literature the common name
neopenty| bromide is used.
‘our isomers are primary alkyl halides.
4. Three isomers are secondary alk! halides,
One isomer i. tertiary alky! halide,
a. butane
b. L-propanol
. S-propyldecane
4d. 4:propylt-non
fe. 2methyls
nol
a cn
Lochs
7
sc
more stable
I-methylethyl octane
ime
primary alkyl halide
secondary alkyl halide
secondary alkyl halide
primary alkyl halide
primary alkyl halide
tertiary alkyl halide
secondary alkyl halide
primary alky! halide
6-chloro-4-ethy|-3-methyloctane
{methoxy 5-methyl-propythexane
1-6-(2-methylpropy! jdecane
i. fen 4-decunamine
Hs CHLCH)
2014 Pearson Education, Is
| -methyl-2-(2-methylpropyl cyclohexane HICH,
~—CHCH ys
more stable’
CH:CHy
CHACH,
cqually stable
® CHC,
ae 7
ichy.ct
(CHy;CHCH:CHy
7 pic (cH cre ee
more stable CH2CHy
72, Alcohols with low molecular weights are mote water soluble than alcohols with high molecular weights
because. as a result of having fewer carbons, they have a smaller nonpolar component that has to be dragged
into water.
73. a
12
keal/mol
” hae 20" 300"
Diihodral Angle
b, a © 1245.2 = 64keal/mol — d. 12 + 9.3 = 10.5 kcal/mol
a
Copyright ©:214 Pearson acai, te 132
16.
7.
Chapter 3
‘The most stable isomer is the one that has a conformer with both substituents in equatorial positions. Using
the Following structu that has both substituents in axial positions,
“That will be the isomer that has both groupy in equatorial positions
a
a Thecis isomer ofa | asubtuted compou isthe most stab
isomer, It has a conformer with both
b. The trans isomer of a 14-disubstituted compound is the most stable isomer. It has a conformer with
both substituents in axial positions, so its other conformer has both groups in equatorial positions,
¢. The trans isomer of a 1.2-disubstituted compound is the most stable isomer. It has a conformer with
both substituents in axial positions, so its other conformer has both groups in equatorial positions.
Six ethers have the molecular formula ~ CHO.
caocnicrscrsct emeucnscty cnerocnen.en,
OA a
(tae 2-etonybt Leon
ms wechuy et cig aye
my
I
cnn eotocts cancncrsocrs
devin by on
Porn a pa
Zthowpranie ———athory-2aneinppane——_Fansthon-2ti poe
eit hopropt treet ett Ta et eth
‘The most stable conformer has two CHs groups in equatorial positions and one in an axial position,
(The other conformer would have two CH groups in axial positions and one in an equatorial position.
chy
a, N-methyl-6-methyl-3-heptanamine d. 2.3-dimethylpentane
b, 3-cthyl-2.5-dimethytheptane fe. S:butyl-3,4-dimethylnonane
.1.2-dichloro-3-methylpentane f S-butyl-3,3.9-trimethylundecane (undecane
is an 11 carbon stra
wrbon
chain hydro
Table 3.1 on page 91 of the texd.
Congright © 2014 Pearson tauetion tne 78.
1”.
80.
81.
82.
Chapter} 133
One chair conformer of trany-1,2-dimethyleyclohexane has both substituents in equatorial positions, so it
does not have any 1.3-diaxial interactions. However, the figure on top of page 134 of the text shows that the
two methyl substituents are gauche (0 one another (as they would be in gauche butane: see Figure 3.15 on
page 131), giving ita strain energy of 0.87 kcal/mol
fa gauche
The other chair conformer of frans-1,2-dimethyleyclohexane has both substituents in axial positions
When a substituent isin an axial position, it experiences two 1,3-diaxial interactions. This chair conformer,
therefore. has a total of four 1.3-diaxial interactions. Each diaxial interaction is between a CH, and an HH
so each results in a strain energy of 0.87 kcal/mol. Therefore, this chair conformer has a strain energy of
3.48 keal/mol (4 x 0.87 = 3.48),
a, S-methyl-3-hexanol fe. .5-hexanediol
b. _I-bromo-2-propyleyelopentane f. 6-bromo-2-hexanol
c. 2amethyl-3-pentanol g. d-ethy!-3-methyleyclohexanol
d,_5-bromo-2-methyloctane bh. 4-bromo-I-ethyl-2-methyleyclohexane
a, [-Hexanol has a higher boiling point than 3-hexanol because the alkyl group in I-hexanol can better
engage in van der Waals interactions, because the OH group of 3-hexaniol makes it more difficult for its
six carbons to lie close to the six carbons of another molecule of 3-hexanol
The floppy ethyl groups in diethyl ether make it difficult for the water molecules to approach the oxygen
in order to engage in hydrogen bonding. Therefore, itis less soluble in water than is tetrahydrofuran in
which the alkyl groups are pinned back ina ring
One of the chair conformers of cis-1,3-dimethyleyclohexane has both substituents in equatorial positions,
so there are no unfavorable 1,3-diaxial interactions, The other chair conformer has three 1,3-diaxial inter
actions, two between a CH, and an H and one between two CH; group:
‘We know that a 1.3-diaxial interaction between a CH) and an H is 0.87 keal /mol, Subtracting 1.7, for
the two interactions between a CHy and an H, from 5.4 (the energy difference between the two conformers)
results in a value of 3.7 keal/mol for the 1,3-diaxial interaction between the two CH, groups.
Hoo CHy
Lions
Lg
QT
cy
Copyeight ©2014 Pearson Edocation, IM
85.
Chapter 3
Because bromine has a larger diameter than chlorine, one would expect bromine to have a greater prefer-
tence for the equatorial position as would be indicated by a larger AG°, However. Table 3.9 on page 131 of
the text indicates that it has a smaller AG®, indicating that it has less preference for the equatorial position
than chlorine has. The C—Br bond is longer than the C—CI bond, which causes bromine to be farther
away than chlorine from the other axial substituents, Apparently, the longer bond more than offsets the
diameter.
a. T-bromo-6-ethyl--decanol
b, S-chloro-3-ethyl-2.7-dimethylnonane
AG 2.61 kcal/mol
AG = -ATIN Ky
2.61 keal/mol = -1.986 x 10'* keal/mol K x 298 K * In Ky
2.61 keal mol = 0.5918 keal/mol In Key
441
equatorial
oo
e both axial
percentage of molecule both 2
oth equatorial 82.3
‘with both groups in = te x 100 = = x 100 = 98.8%,
een both equatorial + both axial B34
equatorial positions
The conformer on the left has two 1,3-diaxial interactions between a CHy and an H (2. 0.87 keal/mol)
for total strain energy of 1.7 keal mol.
Hoot
Jat
Zz oe ai
1
cH
CHe CH
‘The conformer on the right has three 1.3-diaxial interactions, two between a CHy and an H (1.7 keal/mol)
and one between two CH groups (3.7 keal /mol: see Problem 82) fora total strain energy of 5.4 keal /mol
‘Therefore. the conformer on the left will predominate at equilibrium.
Copsrght © 2014 Pearson taeston Chapter3 135
Name the following compounds,
oH
a, the most stable of all the conformers
the least stable of all the conformers,
iche conformer
‘What are the common and systematic names of the following compounds?
HCHCH, b. CH,CHCH,CH;CH.OH eat
| i EX
a cH \A sor
Label the three compounds in each set in order from highest boiling to lowest boiling,
a. CHYCHCHCHyCHSBr CHACH CH Br CHCHSCHCHBe
b. CH,CHSCH.CHCHy CHACH;CHSCHLOH— CHYCHSCH,CH,CI
Gy CH
I
€ CHE—CCH, CHYCHCHSCHCH{CHACH:CHy CH{CHCHCH,CH:CH.CH,
I
Chis CH cH
Name each of the following compounds:
& CHRCHCHCHREHCH:CH, ©
CH On
I
b. CH;CHLCHOCH.CH, @. CHLCHCHCHCHCH.CI
a
“HSCH.CHy CH.CHy
Copysighe 92914 Persin Bain, fe 136
6.
ra
10,
u.
12,
Chapter 3
Draw the other chair conformer for the following compound:
ae
Which is more stable, cis-t-isopropyl-3-methyleycloexane or trans |-isopropyl-3-methyleyclohesane?
Which of the following has:
a, the higher boiling point: diethyl ether or butyl alcohol?
b. the greater solubility in water: I-butanol or I-pentanol?
¢. the higher boiling point: hexane or iyohexane?
4d. the higher boiling point: pentylamine or ethylmethylamine?
€. the greater solubility in water: ethyl alcohol or ethy! chloride?
What are the common and systematic names of the following
a. CHACHCHCHBr b. CH CHCH.CHOH © CHACHCHSCH.NHs
Hy Cy cH
sompounds?
Draw the more stable conformer of:
aL cis-L-see-bulyl-4-isopropyleyelohexane
Db. srans-1-see-butyl-+-isopropyleyelohexane
syans-t-see-butyl-3-isopropyleyelohexane
Draw the structure for each of the Following:
aa secondary alkyl bromide that has three carbons
b. a secondary amine that has three carbons
‘¢.amalkane with no secondary hydrogens
4. a constitutional isomer of butane
€. three compounds with molecular formula C,H,O-
Name the following compounds:
ee Cx
b. cryeuctt CHaCHSCH3CHBr & 1CHCH,OCH,CH.
i
LL ft
ch OH
Copyright © 2014 Peano Eaton In Isomers: The Arrang
chiral
chiral probe
chromatography
cis isomer
cis-trans isomers
configuration
configurational isomers
constitutional isomers
(structural isomers)
dextrorotatory
dias
enantiomerically pure
enantiomeric excess
(optical purity)
enantiomers
erythro enantiomers
nent of Atoms in Space
a molecule or objec: that contains an element (a plane oF x point) of symmetry: an
achiral molecule is superimposable on its mirror image.
results when a compound containing an sp* hybridized nitrog
rapidly invents
in with a lone pair
an atom that is bonded to four different substituents,
«chiral molecule has & nonsuperimposable mirror image:
something capable of distinguishing between enantiomers.
separation technique in which the mixture to be separated is dissolved in a solvent
and the solution is pussed through a column packed with an adsorhent stationary
phase:
the isomer with substituents on the same side of a cyclic structure, or the isomer
with the hydrogens on the same side of a double bond.
isomers that result fiom not being able to rotate about a carbon-carbon double bond,
the three-dimensional structure of a chiral compound. The configuration at a
specific atom is designated by R or S,
stereoisomers that cannot interconvert unless a covalent bond is broken. Cis-t
isomers and isomers with ayymmetric ce
are configurational isomers,
molecules that have the same molecular formula but differ in the way the atoms
are connected
the enantiomer that rotates the plane of polarization of pla
clockwise dircetion (+).
ne-polarized lis
hin a
stereoisomers that are not enantiomers.
‘only one enantiomer is present in an enantiomerically pure sample,
how much
of one enantiomer is present in a mixture ofa pa
expressed as a percent
nonsuperimposable mirror-image molecules,
the pair of enantiomers with similar groups on the same side (in the ease of stereo-
isomers with adjacent asymmetric centers) when drawn in a Fischer projection.
137
Conysght ©2914 Pearson Boat, 138 Chapter 4
Fischer projection
levorotatory
‘meso compound
observed rotation
optically active
optically inactive
perspective formula
plane-polarized light
plane of symmetry
polarimeter
polarized light
racemic mixture
(racemic modification,
racemate)
R configuration
resolution of a racemi
mixture
the spatial arr poups bonded to an ayy
ric center, The asymmetric center is the point of intersection of two perpendicular
lines: the horizontal lines represent bonds that project out of the plane of the paper
toward the viewer, and the vertical lines represent bonds that projeet ack from the
plane oF the paper away from the viewer.
nonidentical compounds with the same molecular formu
the enantiomer that rotates the plane of polarization of pline-polarized fight in a
counterclockwise direction (=),
a compound that possesses asymmetric centers and a pling of symmetry: itis aehi-
ral, because it has «t pkine of symmetry.
the amount of rotation observed in at pokarimeter,
rotates the plane of polarization of phine- polarized light,
does not rotate the plane of polarization of plane-polarized light.
how much excess of one enantiomer is present in a misture oF a pair of enantionters,
a method of representing the spatial arrangement of groups bonded to an asym-
metric center, Two adjacent bonds are drawn in the plane of the paper: a solid
wedge depicts a bond that projects out of the plane of the paper toward the viewer.
aind a hatched weuge depicts a bond that projects back from the paper away from
the viewer
that oscillates in a single plane,
nary plane that biseetsa molecule into pieces that are a pair of mirror in
aan instrument that measures the rotation of the pkine af polarization of plane-
polarized light
light that oscillates in only one plane.
4a migture of equal amounts of a pair of enantiomers,
aifter assigning relative priorities to the four groups bonded to an usymmetrie center,
if he lowest-priority group is on a vertical axis in a Fischer projection (or pointing
away from the viewer in a perspective Formula). an arrow drawn from the highest-
priority group to the next highest-priority group an then (0 the nest highest priority
group goes in a clockwise direction.
mig mixture into the individual
separation of a ra antiomers,
CConpsight 9 2014 Peurwn Fae S configuration
specific rotation
stereocenter
(stereogenic center)
trans isomer
Chapter4 139
after assigning relatve priorities to the four groups bonded to an ayymmetrie
ter. if the lowest-priority group is on a vertical axis in a Fischer projection (or
pointing away from the viewer in a perspective formula), an arrow drawn from
the highest-priority group to the next highest-priority group and then to the next
highest priority group goes in a counterclockwise direction,
the amount of rotation that will be observed for a compound with a concentration
zziven in grams per 100 mL. of solution (or g/mL i iis a pure liquid) in a sample
tube 1.0 dm tong,
aan atom at which the interchange of two groups produces a sterevisomer
isomers that differ in the way the atoms are arranged in space,
the pair of enantiomers with similar groups on opposite sides (in the case of Stereo
isomers with adjacent asymmetric centers) when drawn in a Fischer projection.
the isomer with substituents on the opposite sides of a eyelie structure, or the isomer
‘with the hydrogens on the opposite sides of a double bond,
Copyciht ©2014 Pearson Education te 130 Chapter 4
Solutions to Problems
1 CHCH:CHLOH CIneHOH —CHCHAOCH,
bu
b. ‘There re seven cottons! omer th mole fomula C,H
i
cHencincHon cHeHcHOH — CHEOK —_CHLCHEALCH,
bn, yon
CHHCH,OCH,CH CHOCHCHCHy CHLOCHICH,
cH
- CHy cH,
Z
CHC, cHCH,
3 a Land
ee H 3.
\ Vd
c cad
y oN
Hl Wo “cu.ci.cH,
cis trans cis trans
4. BS Oy
4 NS
os cn
§. CHyCH;CHCH=CH, = CH;C=CHCH, ~—CHCH;C=C1
6. Only Chas. dipole moment of zero. because the bond dipoles cancel since they are in opposite directions.
HA
exe
oy OM
7. a,b, ¢, f. and h are chiral.
de. and g are each superimposable on its mirror image. These, therefore. are achiral.
8. a.e,and f have asymmetric centers.
Copyrigt 2014 Pearson Edocaion ba 10.
ML
12.
Chapters 14
Solved in the text
a, €,and f, because in ofder 0 be able 10 exist as. pair of enantiomers, the compound must have an asym~
mttic center except in the ease of certain compounds with unusual structures; see Problem 86)
a It has one asymmetric center
b._ Ithas three stereocenters.
Draw the first enantiomer with the groups in any order you want. Then draw the second enantiomer by
drawing the mirror image of the first enantiomer. Your answer might not look exactly ike the ones shown
below because the first enantiomer can be drawn with the four groups on any of the four bonds. The next
fone is the mirror image of the first one
ak CHy ie 2 ie a CH:CH,Ch
I I
“ c ., co
Bro M"CHOH —- HOCHS"/ > Br crycHy W'CHy cHe7 ~CHCHy
u H H H
3 a m
7 co
acHycu® W'CH. CHE SCHICHY
h i
bea cin 2 cnene cucu!
we—f—n ne e—fon
Giron Gihon cH.cl,
Roh cy
Ho + " wf on
CHecHy CEH:
Solved in the text
o 6 © SO
Qo oO o
@
SO 40 So
forms 2 bonds to attached to attached only
C, so considered TC forms 3bondsio tw Hy
ached C. so considered
1020s to be attached
was
© 3014 Parson Eston, Ine 142
18.
Chapter 4
a. Solved in the text
bok
c. Todetermine the configuration, first aud the fourth bond to the asymmetric center, Remember that it
cannot be drawn between the wo solid bonds. (It can be dranvn on either side of the solid wedge.)
LNA
tui Sow
&
s bok ce
as
The easiest way to determine whether (wo compounds are identical or enantiomers is to determine their
configurations: If both ase R (or both are $), they are identical. Ione is ® and the other is S, they are
enantiomers,
idenvical enantiomers. entmfiomens. enantiomers
a a b. br
c co
cnet VN cHer \"H
eH, ‘cite
2. Sohed inthe ext b. coo
wen
cHcH,
a. levonotatory——b. dexttorotutory
i ‘observed rotation (a
speeitic rotation = ——S NSE
eoncentration (g/L m
2) < length (dm)
+138 +13.
lal =
—_ +168
4g in 100 mL. x 2am
a -24 boo
a. OUtisara
emie mixture.)
b, S06 of the mixture is excess (++-mandelic acid,
optical parity = 0.50 = —_Sesetved specitie rotation _
specific rotation of the pure enantiomer
observed spe
+158
fa rotation
observed specific rotation = +79
50% of the mixture is excess (—)-mandelie acid
observed specific tation = ~79 (For the calculation, sce part b.)
Copyesht 0) 2014 Pear Fon Chapterd 143
24. a. From the data given, you cannot determine the configuration of naproxen.
b. 97% of the commercial preparation is (+)-naproxen; 3% is a racemic mixture, Therefore, the
commercial preparation forms 98.5% (+ )-naproxen and 1.5% (= )-naproxen.
25, Solved in the text.
26. Asa result of the double bond, the compourd has a cis isomer and a trans isomer. Because the compound
also has an asymmetric center, the cis isomer can exist as @ pair of enantiomers and the trans isomer can
exist aa pair of enantiomers,
HCH,
Ec
Br VCH
Tees
J =
W chy cH H
trans enantiomers
27. a. This statement is correct, Although there are many examples where there would be fewer than 2"
stereoisomers (for example, trans-2-butene has two stereocentery but only two stereoisomers, there are
zo situations where there will be more than 2" stereoisomers)
This statement is not correct. For example, the compound in Problem 26 has one asymmetric center
(therefore, 2" = 2). but the compound has four stereoisomers.
28, a. enantiomers
identical compounds (Therefore, they are not stereoisomers.)
¢. diastereomers
29. a. Find the sp' carbons that are bonded (o four different substituents: these are the asymmettie centers.
Cholesterol has eight asymmetric centers. They are indicated by arrows.
Pe ee.
ci Y
xX — CHy
le
NS
. aa
HO’ S
b. 2° = 256
Only the stereoisomer shown above is found in nature,
Copyrigtn 214 Pes Education. Ie 144 Chapter 4
30. Your perspective formulas may not look exactly like the ones drawn here because you can draw the first
one with the groups attached (0 any bonds you want, Just make certain that the second one is a mirror
¢ of the first one.
ima
Leucine hay one asymmetric center, so it will have two stereoisomers,
ce he we fet nen
ccHyscuci, ¥ Py SHMCHD: Coen on.
b. Isoleucine has two asymmetric centers, so it has four stereoisomers, Again your perspective formu-
las may not look exactly like the ones drawn here. To make sure you have all four, determine the
configuration of each of the asymmetric centers. You should have R\R. 5.5. R.S, and $.R. Notice that
the asymmetric centers in the mirror image have the opposite configurations.
“o0c 4 " coo" coo- coo"
\ Se od
Nene th CSC :
wee Zo Ninn or HY NG ns
Wf oncn, cna, aa RA
ss kok
cnet, cnc
~OOC \ H H, coo” coo” Ccoo™
cet, Wetec . .
wo a wine awn s
HaN* CHICHy, *NHy CHy HOS H CH, R
RS
CHLCH, CHSCHy
31. Band D have no symmetric centers.
Aand C each have one asymmetric center.
a CK
(Ff
A c
E has two asymmetric centers
(Copyright 204 Pear Education, I Chapterd 145
: CH, Hy
avs Yc
W CIRCHCH, —CHACIRCH: 1H eee eee
Ros kos CHCHACH; —— CHCHCHs
ony cH
HW 4
0H Wee u-as cin ek
> 4 vn eee H——OHR
ccc, cHcHCH, er
i CHCHCH, —— CHLCHLCH,
b. CHy CHy
uf—Brs Hk
& 4 Bo u 4 H—-4H
Awe AL far
sk Rs . one
Bl Br cl cy
AAL ee u Ls
Ses ROR n—ton HH
a Hos Ho
CHACHy
cH cHy
© HAC, H HL CH) cl HR Hcl S
‘ —e=c 7 Soo }
cr < wo Ql ci}—-us Hale
Wf cue cach, YY
Rs RS CHCHy
Hc, cus
Nie a Nn
cl CHCH, © CH;CH,
sos RR
da
CHACHiBr
oo
crc SH
‘Br
5
CHACHBr m CH.CH,Br
br—}—u HBr
cu. cHACH,
s R
Gopyeigh 2014 Pearson tsa, te Lo
BB.
Chapter 4
LCL
: \ 48
an cu
cis-2-methyleyelohesanol
fo t
a a
I-ehloro-L-methyleyelooctane —cis-F-elloro-S-methyleyelonetane —srwns-L-cbloro-S-methyleyelooetane
There is more than one diastereomer for ay b, and d: ¢ has only one diastereomer
To draw a diastereomer of a, by or d. switch any one pair of substituents bonded to one of the ayymmetric
pair can be switched. your diastereomer may not be the one drawn here. unless
centers. Because any on
you happened to switch the same pair that is switched here.
a cH eC
H——oH
W
HOH
cH
ba u a
sel
wee
cHH, Hs
A = identical B= enantiomer C= diastereomer—D = identical
B.D. and F because each has two asymmetric centers and the same four groups bonded to each of the
asymmetric centers.
A-has two asymmetric centers but it does not have a sereoisomer that is meso compound, heeause it does
not have the same four groups bonded t0 each of the asymmetric centers,
C and Edo not have & stereoisomer that is a meso compound. because they do not have asymmetrie
centers
Solved in the text
a CHCH, CHLCH, chyBe Chiste
co or HCH, CH}
WL CHyBr
cu, CHACHs CHC,
kg s R 5
Conse» 24 Porn cain. Is b. CHC, CHLCH.CL
|
© or u—pecHy
oh
sere)
eee cH cucu,
® g
CH
Chapter 147
CH,CHCH,OH No stereoisomers. because the compound does not have an asymmetric center
cH cron CH.OH
|
o a
HY ~CH,OH
i cu.cn, cnc
s k s
Hy
fe. CHjCHZCCH CH, No stereoisomers, because the compound does not have an asymmetric center.
|
a
cn cH,
taco ay HOL- RR Hons
me abr ts ot . e
ee Gon fH Sn a
" ‘ CHy Hy
ks kos
chy cit
ro
Wonca pee ee
S
Ho! cH ston s H—p-err
sos Be
cH, cry
cnc,
nas
cucH: ct
ae uae
ween or
of crc cnc,
sR
a meso compound a meso compound
cic, cH,
HW euch, n—t-cis ote e
Cl ce
S Hg 1k
cHcns ca, “Cl Gg eae)
7 an cHichy cH.cn,
CCoysright ©2014 Peano dbcain, Ine U8 Chapter 4
h
cl
a
cH cH cH
AA was wfas atwe
2 meosompound ot tn
a oa a oa H—-ck c——n s u—y—cr
RR ss meso compound
{ith a plane of
symmetry
cH cu
a 4 a oa Hop=c ss cl—f-n ke
ee ee iy HW "
sR Ros Hc & Cis
CHYCHSCHs
or
cH cH
ao Gl nas c—-He
AARK AAN a
cs kor clin s Hc
CincrecHs —CHLCHLCHS
Oo CLL tse
af Ya of oor ‘< meesompoun
\/ a meso compound.
ci or cl
Br
Br
Br
I pal
cl a ‘Br Bi
1
Br
‘This compound does not have any asymmetric
centers, so it has only cis-trans isomers,
ar
cr
Copyrigt © 2014 Pearson Zdoean a: Chapter4 149
40. and 41, How to draw perspective formulas for compounds that have two asymmetric centers is described on
page 175 of the ext
eae cul
n—b-on wo—f-n
nea cen
caer, cnc
(283R-1 3aiehtore2-pentanal —2RAS}-1 ach? penal
cnet cnet
n—ton won
u H+ ch
cucu, cicth
(2839-1 3chlow2-pemanal ORAM Sichlor-2pentnol
b. cL CHC)
Hp
a NUH
cnet, Yon
28.48) 1eticlone- pent!” QR 38}-1chloo2 penal
ccs cue
coer ae
wee 1"
Ho cH.cHs ‘ou
(25.381 Seichlow2:pemtanol Jihlow-2-pentanl
42. Ro BR
wo) (
ection
NOs
43. Your answer might be correet yet not look like the answers shown here. If you ean get the answer shown
here by interchanging two pairs of groups bonded to an ayymmettic center on the structure you drew, then
{Your answer is correct. If you get the answer shown here by interchanging one pair of groups bonded to an
symmetric center, then your angwer is not correct
a a b. Br Hu
( Nee CH:CHs
swe V4 aS
HocHscihy Yytcu, r jr
Copyeit © 2014 Pearson Fuca, te 130
46.
47.
a
Chapter +
H a.
Suse: t
cI Bro
Cs CHSCH,
a. 3-chloro-4-methythexane €. (1R3S)-3-bromocyelopentanol
Db. (25.35}-2-bromo-3-chloropentane 4. (2R.3R)-2.3-diehoropentane
‘The carbon of the COO group is C-1. The first structure is 28.35. Therefore, naturally occurring threonine,
with a configuration of 25.32. is the mirror image of the first structure, Thus. the second structure is
reoni
naturally occurr
a, Solved in the text
b. cH:
| HO, a
Nee
ee
WB
| Clige crn
cn
a. Solved inthe text
boc on cl
oot
cM SSX ON
WO cn.cn
on
Start by naming the first stercosiomer, Finding that A iy 2R.32 allows you to answer both questions
a Ais erythrose, 1b. p-Threose hay the opposite configuration at C-2 and the same
oO 20 configuration at C-3, Therefore, C is p-threose,
“c
u—*-on
u—Lon
CHLOH
Solved in the text
We sce that the (28)-alkyl halide reacty with HO” to form the (R)-alcohol, We are told that the product (the
(R)-alcohol is {~). We ean, therefore, conclude that the (+ }-tleohol has the § configuration.
(+)-Limonene has the R configuration, soit isthe stereoisomer found in oranges. 53.
4.
Chapter4 151
Compound A has (wo stereoisomers, because it hay an asymmetric center (at N),
Compound B does not have stereoisomers, because it does not have an asymmetric center
Compound C has an asymmetric center at N but, because of the lone pair, the two enantiomers rapidly
interconvert, so it exists as a single compound.
chy oy
CHCH=CHCH:CHy— CHy=CHCHSCH;CH, — CH\C=CHCHy CH,CHCH= CH,
2 sterenisomers no stereoivomers no stereoisomers ho stereoisomers
sand tans}
ve aa a
1 A LN
CHCHC=CH, cll, cHechy HC Sons
no stereodsomens osteresisomers ao sereosomens 3 serensomers
[Cis is. a meso compound. |
cus [rans iva pte of enantio
no stereoisomers no seroisomers
r laa
2 » \ <)
\ { /
\ om S Xv
my Gt ea Gs
vs 7 cH, cus
c © 4 + Br we H
Choy + weFS or .
_ crcnch, WN * 17 Scuncact,
Pee eeechs Hc 1 CHACHCH, CHCHCH,
on cn | {
cng cin,
s k s k
: lan
* <> q
4% 4 é
Gace cy eae cl
au meso compound
da. CHy CHy CH
wert
utn on n—ton w—few
Hao on wtea
cy cn ci cn
r\
Br Sect Br a
<0 tC)
cis and trans,
aX
CHy
aX
chy YC CH,
Copytight © 2014 Pearson Elacation. Ine 182 Chapter 4
chy
on, mo le
\ a JNA
c= omc ‘ar
a - A
W uc OH :
sean
h crycaecHcts No isomers are possible for this compound, because it does not have an
by asymmetric center
i, i |
cr Br Br = cr “Br BY ch
br bs
ci
cis and trans only (no asymmetric centers)
55. Only the fourth one (CHFBrC1) has an atom with four different atoms attached to a carbon, so itis the
‘only one that has an asymmetric center.
36. a 2 chloro-2-pentanol
.2.5-pentanetriol
58, a, diastereomers (one asymmetric center has the same configuration in both compounds and the other has
the opposite configuration in both compounds)
enantiomers (they are mirror images)
constitutional isomers,
diastereomers (the configuration of two asymmetric centers is the same and the con
asymmetric center is different)
diastereomers
identical
es
=
ration of one
CCopysght ©2014 Pearson Eaton 39.
61.
62.
63.
Chaper4 1
diastereomers (cis-trans isomers are diastereomers because they sre stereoisomers that are not
enantiomers)
1h, identical (if you flip one over. you can see that they are superimposable)
Only the compound on the far right is optically active, because it is the only one that has one or more
asymmetric centers,
a. Because there are two ayymmetric centers, there are four possible stereoisomers.
b Q
4
© Noe NHCHS
\
re
Ho
1) Caw
ry s
(2RAS.68)-4-chloro-6-methyl-2-octanol b. (R)-3-bromo
Compounds a. de. fh. i and j have a stereoisomer that is achiral
Compounds a. d, fi and j have two asymmetric centers bonded (o identical substituents, Thus, there are
three stereoisomers, one of which is an achiral meso compound.
Compounds € and h do not have any asymmetric centers: they have eis and trans stereosiomers. so each is
achiral and, therefore, each has an achiral stewoisomer
Compounds b and g each have two asymmetric centers bonded to different substituents. Thus, there are
four stereoisomers, all of which are chiral
Compound e does not have any asymmetric centers: itis, therefore, achiral but it does not have any
stereoivomers
a, One asymmetric center bas the same configuration in both compounds and the other asymmetric center
has the opposite configuration in both, so the compounds are diastereomers.
1b, Both asymmetric centers in one compound have the opposite configuration in the other, so the com-
pounds are enantiomers.
€. They are identical because if one is flipped over, it will superimpose on the other
4d. They are constitutional isomers because the atoms are hooked up differently: one compound is
|-chloro-2-methyleyclopentane and the other is [-chloro-3-methyleyelopentane.
W
2CH,COOH
Ho™ VCOOK
" cu.coon
(Seite acid
b, The reaction is catalyzed by an enzyme. Only one stereoisomer is typically formed in an
enzyme-citalyzed reaction because an enzyme has a chiral binding site that allows reagents to be
delivered to only one side oF the functional group of the reactant
‘c. The product of the reaction will be achiral because if it does not have a '4C label, the two CH;COOH
soups will be identical. so it will not have an asymmetric center
Copyeih © 2008 Pearson Esko, In 66.
67.
68.
0.
70.
Chapter 4
a, identical e. constitutional isomers
b, identical f diastereomers
enantiomers constitutional isomers
d._ constitutional isomers h, enantiomers
sia
*87
optical purity 0.16 = 16% excess R enantiomer
100% ~ 16% = 84% is uracen
Renantiomer = 1/2 (84%) + 16%
mixture
42% + 16% = 58%
R bs eA A
ON
te
od a bck
“we
s CHyCHs HCHs
® 5
Fisher projections show the molecule with eclipsed bonds.
Therefore, to anywer parts € and f. first rotate the Newman
projection so itis eclipsed. Then turn the Newman projection
Butackamol has four asymmetric centers: three of them are carbons and one is a nitrogen.
2) on
(Fearn
inal
L - KHL
~
‘The only way that R and S are related to (+) and (—) is that if one configuration (s
cone is (—)
Ry is (+) the other
Because some compounds with the & configuration are (+) and some are (—). there iy no way to determine
‘whether a particular & enantiomer is (+) or (—) witrout putting the compound in a polarimeter or finding
‘out whether someone else has previously determined how the compound rotates the plane of polarization
of plane-polarized light.
Copyright 8 2014 Pearson Eaton. n.
2.
Chaprer4d 155
First convert the staggered Newman projection to an eclipsed Newman projection, which ean then be
converted (0 a Pischer projection since thal too is eclipsed (see page 188 of the text). Then name the
Fischer projection
a, Since one is R and the other is S. they are enantiomers
ae on
u-®—ony
Ln
H Hy CHCH,
1
on HyC CH;
"Ne CH,
AS ”
i in
bb, Since one is R.R and the other is $,S, they are enantiomers:
Hy eon CHy
hy ‘ n—®—crscny
OAK Buy bran
WO CCH, dhicns
a Br a
cuscHy cic, CHCHy
" oy ccHy
a ~ Be Ste
Woon a Gi,
be H a
a The compound has four stereoisomers.
cH.on con cron cuy0n
H on H—}-oH fon HO —H
n—-on Mo algo oat
n—} on H—f-on Ho—j—H H—}—on
Cixon cron cron CHL0H
1b. The first nwo stereoisomers are optically inaetive because they are meso compounds. (They each have
plane of symmetry.)
a. ‘CH.CH2Br Bb. BCHy, OH ce. HAC CH CHy
necnert pec er"
mm 7 N
V"H ) 'Scu=o nO) (be
{_ CH2CH2CH) o )
aK n ak k s
Copyright © 200 Penn Fastin, Ine 156 Chapter 4
74. acand b.
cH, chy
jeinen
[ eases
cthyleyelobutane 1 1-dimathyleyctobutane
nc Yen, uch vcr ne Nc,
civ 2alimethyleyeluutane tas. 2atimethsleyeloburane
ells cy
iz |
7A y
Hy nyc
cis Aalimethyleyelobutane ———tray-1.3-timethyleyelobutane
Le ethyteyclobutane
1 L-aimethyleyelobutane
1.2-dimethyleyelobutane
| 3-dimethyicyelobutane
2. the three isomers of 1.2-dimethyleyclobutane
the two isomers of | 3-dimeihyleyelobucane
cis- and rrany-1.2-dimethyleyelobutane
cis- and trany-1 3dimethyl
sclobutane
4. the bvo trans stereoisomers of 1.2-dimethyleyclobutane
all the isomers except the two trans stereoisomers of 1.2-dimethyleyelobutane
6. cis-1.2-dimethyleyetobutane
(Note: civ-1.3-dimethyley
asymmetrie centers.)
obutane is no
meso compound because it does not have any
7. the two trany stereoisomers al clobutane
2-aimethyley
8. civ-1.3-dimethyleyclobutane and trans-1.3-dimethyle
cis-|.2aimethyleyclobutane and
clobutane
her of the enantiomers of srany-L.2-dimethyleyelobutane
Coppi ©2014 Pour Fl 75.
16.
7.
78.
Chapter4 157
observed specific rotation = —PPSF¥Ed Tokton
concentration x length
6.52"
—_057" ___agy
0.187 g/100 ml. x Tdm
observed specific rotation
seve specie Tone __5 409)
Specific rotation of the pure enantiomer
‘% optical purity
eof the (+)-isomer=
% of the (~)-isomer =}
astercomers (the configur
both
identical (by rotating one compound. you can see that
€. constitutional isomers
4. diastereomers. (the configuration of all the stereoisomers is not the same in both and not opposite in
both)
aoe br _ or
H a ‘
‘
jon of all the symmetric centers is not the same in both and not opposite
is superimposable on the other)
Br “Br Br Br
CHACH.CHy
cHy e CHCHy CHLCH,
clin He chy
Ha HS 4 Cl
CHACHy H chy H
© oY
/
~f
Cis cH
In the wansition state for amine inversion, the nitrogen atom is sp" hybridized, which means it has bond
angles of 120°, A nitrogen atom in a three-membered ring cannot achieve a 120° bond angle. so the
amine inversion that would interconvert the enantiomers cannot occur. Therefore, the enantiomers
separated,
“The fact that the optical purity is 72% means that there is 72% enantiomeric excess of the S isomer and 28%
racemic mixture. Therefore. the actual amount of the $ isomer in the sample is 72% + 1/2(28%) = 86%.
‘The amount of the R isomer in the sample is 1/2(28%) = 14% (or 100% ~ 86% = 14%),
A= adiastereomer C= adiastereomer adiastereomer
B= adiastereomer = adiastereomer
Copycat © 204 Pear Fakcation, fe 158 Chapters
soa
a cl
cf a
I f
ot Yonel
ac
cel
cr a
boca
ca
ca oa
/
Coa cl
a
ca
(
aoa
aL, I f i
aoa
This is & pair of enantiomers
cr cy because they are
nonsuperimposable
aa
cl
LZ
oo)
PN L
mS Oy
areas
This is the most stable isomer becwuse. since the
chloro substituents are all trans to each other. they
can all be in the more stable equatorial position,
(Recall that there is less sterie strain when a sub-
stituent is in the equatorial position.)
83, Yes. as long as the Fischer projection is drawn with the #1 carbon at the top of the chain of earbons..
Re
mA ou
‘CH,
of
oH
« ke
SS
Br
Copyright 2014 Posen Education. I Chapter4 159
85. The trans compound exits as a pair of enantiemers,
"CICHy)s ich
As a result of ring-flip. each enantiomer has two chair
is the one with the larger wroup (the sert-butyl group)
conformers. In each
the equatorial position
.e. the more stable conformer
8 HW
cy ae chy
LET H es CHy _
React, (cine
W CecHns (Hyco in
noe stable snore stable
86. a. The compounds do not have any asymmetric
b. 1. his not chiral
2, Its chiral, Because of its unusual geometry its chiral molecule, even though it does not have
any asymmetric centers, because it cannot be superimposed on its mirror image. This will be
easier to understand if you build models.
ners
H
o
images av sperimposthle
4 a 4
Nc c c
?
Hac Neu, HC
ot superimposable
87. The compound is not optically active because it has a point of symmetry.
A point of symmetry is « point, and if a line is drawn to this point from an atom or group and then extended
‘an equial distance beyond the point, the line would touch an identical atom or grouy
point of symmetry
‘cr
Copprght © 2014 Pearson Bacon, Ie 160 Chapter +
Chapter 4 Practice Tes
1, Ate the following pairs of compounds identieal or a pair of enantiomess?
cH: cH
CH CH} —CH.OH and Woy be am ew.
| We WH oF Scucny
Hh cHLOH o W
2 100 mL. of a solution containing 0.80 g of a compound rotates the plane of polarized light —4.8° in a
polarimeter with a 2-dm sample tube, What is the specific rotation of the compound?
3. Which are meso compounds?
cn, cH, cHy cH, cH,
Hcl oH cl Br aon a aH
HW cao Ho Br a) co we
HCH, HCH cul Hy cHy
4. Draw all the constitutional isomers with molecular formula CHCl
Draw all the possible stereoisomers for each of the following compounds that has them,
a a d. CHCH,CHCHCH,CI
Hom on bh
b. CHLCHCHCHCH, ©
br
c. CHACHYCHCH CH, £ Wo )—cH,
a
6. Which of the following three perspective formulas arz the same as the Fischer projection shown here?
coon
ho——H
Hon
on
Ho, tH H Ho, Lon
H Con HO: . H 7 pH
HooC ‘cH, Hood ci HOOK ony
Coppi 2014 Pear Chapters 161
7. (R)-(=)-2-methyl-I-butanol can be oxidized to ( +-)-2-methylbutanoie acid without breaking any of the
bonds to the asymmetric center, What is the configuration of (~)-2-methylbutanoie acid?
HOH cooH
“ “
our Nfl oH “hon
(8 ))-2-methyl- -butanol }-2-methylbutanoie acid
8 (~)-Cholesterol has a specific rotation of ~32, What would be the observed specific rotation of a solution
that contains 25% (+)-cholesterol and 75% (—)-cholesteral””
9, Which of the following have the R configuration?
4 ony cHCHBr ow
br on br Hl
cinbe cH on CHCHICH:
uc cy nor ey
ca Vn Scmcn, CHO" cHc, Ch cH city
bro " u
10, Answer the following:
Are the following compounds identical or a pair of enantiomers?
H
concn} eon
CHy cH
HOH
CHXCHs
Put the remaining groups on the structure so it represents (R)-2-butanol.
2 Put the remaining groups on the Fischer projection so it represents the Newman projection shown,
chy cHy
HO H {
u “cl
CHSCHy CHICH,
Copyright ©2014 Peuson Eduction, te 162
AL
Chapter 4
, Draw a diastereomer for each of the Following:
CHy
H OH
Hy
Indicate whether each of the following statements is true or false:
fa, Diastereomers have the same melting points.
b. 3-Chloro-2.3-dimethylpentane has two ayymmetric centers. T
¢. Meso compounds do not rotate the plane of polarization of
plane-polarized light 7
d, 2.3-Dichloropentane has a stereoisomer that is a meso compound, 7
€. All chiral compounds with the R configuration are dextrorotatory, T
centers can have a maximum
fA compound with three asymmet
of nine stereoisomers 7
Which of the following have cis-trans isomers?
2-bromo-3-hexene 2-methyl-2-hexene
Lepentene s-methy
Copyright ©2014 Pearson Edution CHAPTERS
Alkenes: Structure, Nomenclature, and an Introduction to Reaeti
Important Terms
active site
acyclic
alkene
allyl group
allylic carbon
allylic hydrogen
Arrhenius
quati
talyst
degree of unsatui
clectrophile
electrophilic additi
reaction
ndergonic
ndothermie reaction
enthalpy
+ Thermodynamics and Kinetics
I the bond-maki
catalyzed reaction occur,
the pocket of an enzyme whei
and bond-breaking steps of un
reaction in which atoms or groups are added to the rea
hydrocarbon that contains a double bond.
CH)= CHCH)—
an sp" carbon adjaceat to a vinyl carbon
a hydrogen bonded to an allylic carbon.
an equation that relates the rate constant of reaction tothe energy of activation
and to the temperature at which the reaction i caried out (& = Ae #1”)
‘species that increases the rate at which a reaction occurs without being consumed
in the reaction.
the isomer with the Fydrogens on the same side of the double bond.
the sum of the number of a bonds and rings in a hydrocarbon,
the isomer with the high-priority groups on opposite sides of the double bond,
an electron-del
‘ent atom or molecule.
aan addition reaction in which the first species that adds to the reactant isan
electrophile.
a reaction with a positive AG": it consumes more energy than it releases
reaction with a positive AH"
the heat given off (if AA’ < 0) or the heat absorbed (if AAP > 0) during the
course of a reaction.
a measure of the freedom of motion in a system,
4 protein that is a biological catalyst
avreaction with a negative AG*; it releases more energy than it consumes.
163
Copyright © 214 Pearson Edun, lot Chapters
exothermic react
experimental et
activation
(E, = MH + RT)
first-order rate €
ergy of
tant
first-order reaction
(unimolecular react
free energy of a
(AG)
functional group
geometric isomers
(cis-trans stereoisomers)
Gibbs free
energy change (AG°)
intermediate
Kinetics
Kinetic stability
Le Chatetier's principle
mechanism of the reaction
molecular
recognition
nucleophile
pheromone
rate constant
rate-determining step
rate-limiting step
sureaction with a negative MIP.
measure of the approximate energy bartier to a reaction.
(cis approximate because it does not contain an entropy eomponent.)
the rate constant ofa firstorder reaction
reaction whose rate is dependent on the concer
ration of one reactant
the true energy barrier to a reaction
the center of reac
ity of a moleet
trany (or E.Z) isomers.
the difference between the free energy content of the products and the free energ
content of the reactants at equilibrium under standard conditions (1M. 25 °C. 1 atm).
species formed during 4 rexetion that is not the final product of the reaction,
the field of chemistry that deals with the ratey of chemical reactions
Kinetic stability is indicated by AG?. If AG is large. the compound is kinetically
stable tis not very reactive), [F AG? iy small, the compound is kinetically unstable
(is very reactive),
«principle states that if un equilibrium is disturbed. the components of the equilib-
rium will adjust in a way that will offyet the disturbanee.
aa description of the step-by-step process by which reaetanty are changed into
products,
the ability of one molecule to recognize another as «result of intermolecular
interactions,
aan electron-tich atom oF molecule.
‘a chemical Substance used for the purpose of communication,
the proportionality constant in the rate equation that quantifies the rate of a
reaction,
the step in a reaetion that has the transition state with the highest energy,
‘Copy © 24 Peston Fst. reaction coordinate
diagram
saturated hydrocarbon
second-order rate constant
second-order reaction
solvati
substrate
thermodynamic stability
thermodynamics
trans isomer
unsaturated hydrocarbon
vinyl group
vinylic carbon
vinylic hydrogen
Zisomer
ChapterS 165
1 diagram that describes the energy changes that take place during the course of a
reaction,
a hydrocarbon that is completely saturated with hydrogen (contains no double or
Lriple bonds),
the rate constant of a second-order reaction
a reaction whose r:
the square of the concentration of a single reactant
is dependent on the concentration of wo reactants. or on
the interaction between a solvent and another molecule (or ion),
the reactant of an enzyme-catalyzed reaction,
thermodynamic stability is indicated by AG. If AG? is negative, the products are
more stable than the reactants. If AG? is positive, the reactants are more stable
than the products.
the field of chemistry that describes the properties of a system at equilibrium.
the isomer with the hydrogens on opposite sides of the double bond.
the energy maximum in a reaction step on a reaction coordinate diagram. In the
transition state, bonds in the reactant that will break are partially broken and bonds
in the product that will form are partially formed,
au hydrocarbon that contains one or more double or triple bonds,
CH=CH
carbon that is doubly bonded (0 another carbon.
avhydrogen bonded fo a vinylie carbon,
the isomer with the high-priority groups on the same side of the double bond. 10,
Chapter 5
Problems
a Clb Ce Clg
as ba etl @3s eB
a, degree of unsaturation = 1b, degree of unsaturation = 2. degree of unsaturation =
cHCH= cH HOSCCH.CH,
cH
A CH= CHCH=CH;
CHy=C=CHCH,
A hydrocarbon with no rings and no double bonds would have molecular Formula ot CyyHy3- CayHsy hats
26 fewer hydrogens. Therefore, B-carotene hay a total of 13 rings and double bonds. Since we know that it
has two rings, it has 11 double bonds,
a. Ithas two vinylic hydrogens.
b. Ithas four allylic hydrogens.
c CHy
CH,OCH=CHy
CHy
cH
I
b. CHC =CCH.CH.CH.Br dd. CH) =CHCHOH
|
Cis
a. 4-methyl-2-pentene
b, 2-chloro-3.4-dimethyl-3-herene
¢. [-bromocyclopentene
d.[-bromo-4-methyl-3-hexene
fimethylcyclohexene
F-outoxy-I-propene
1-promo-2-methyl-1.3-pentadiene
8.8-dimethy!-
FERS
‘nonene
as bo 4 a6
a. -1 > —Br > -OH > -CHy
b. -OH > -CH.CI > -CH
Hy) > —CH.CH.OH
‘The high-priority groups are on same side of the double bond, so ta thas the Z configuration,
Copysight ©2014 Pearson dueton ne Chapters 167
un.
z
cHy
|
cH.cl Hy CHCH,
a ee
\ a
‘CHCH, cH: CHC
‘ I
cuy
z
cH
a
N
ecHiys
Roa NA ©
Ake
i eK
- OOH
a
Copyright 02014 Pearson Eduction, ke 168 Chapter 5
13. a. (£)-Xheptene —b. (Z)-3.d-dimethyl2-pentene—@.(Z}-1-chloro-3.
14. oy
CHCH,
“CHACHCHSCH,
\
cHy
A-hexadione — (Z)-2-methyl-2.4-hesai
b.
\ fo"
CH.CHy H H
2.4-heptadiene (QE4Z)2.4-heptadiene
H
\
H
HAC
/
CHACHy H u
HZABL2A-heptadiene (22.42)-24-hepradione
nH CHy
()-13-pentadione
and € have only two stereoisomers beeause. in each case, there are Ovo ide
‘one of the sp? carbons, so only one of the double bonds can have either the £'or the 7 configuration,
al substituents bonded to
16, a. AICI; isthe electrophile and NH; is the nucleophile
b. The H™ of HBr is the electrophile and HO” is the nucleophile
17. nucleophiles: Hee | CH Og cH,
electrophiles: CH CHCH
CCopgrght © 2044 Pessoa Fluent Chapter S169
I
cue +
i
cH.
Drawing the arrows incorrectly leads to a bromine with an incomplete octet and a positive
charge as well ay an oxygen with 10 valence electrons and 2~ charge,
CH,
CH
Drawing the arrows incorrectly leads to an oxygen with an incomplete octet and a 2+ charge.
2. This one cannot be drawn because the arrow is supposed to show where the electrons move to, but
there are no electrons on the H to go anywhere.
‘The product cannot be drawn because the destination of the electrons in the breaking bond is
not clear
4. This one cannot be drawn because the arrow is supposed to show where the electrons move to, but
there are no electrons on the C to go anywhere.
ae :
ic] + Ho ae + HO
a CH on 1 cH SoH °
H
nucleophile eleetrophile
Br
b. we
on
nucleophile eleetrophite
+ HO
electrophile nucleophile
Copyrigin 2 2014 Pearson Ldn, fe 170
20.
Chapter 5
‘The labels are under the structures in Problem 19,
ise the equilibrium constants for all the monosubstituted eyelohesanes in Table 3.9 on page 131
reater than 1. all of the equilibria have negative AG* values
a Bee
of the text
(Recall that AG? = —RT In Kay)
b.rert-butyleyclohenane
ert-butyleyclohexane, because it is the largest substituent
RT W Koy
Is
= 1,986 10 keal/mol KX 298 KX In ES (recall that = °C + 273)
0,59. Tn 18 eal / mol
= =0.59 2.89 keal /mol
AG = =1.7keal/mol
a. Solved in the text
b. RT In Key
L986 10° X 298 % In Ky
356
k= 38
K Lisopropyleyclohexane |,, a5.
‘~~ Tisopropyleyetohexane |.) 1
6 of equatorial isoproayleyelohewane} gars
of equi __[nomeovteseloherinelowsiel _. gy
isopropyleyelohexane ~ [isopropyleyelohesane) gua + [isopropyleyeloenane
x 10K)
S41
= 100
36. ate
= 97%
c. Ibopropyleyclohexane has a greater pereentage ofthe conformer with the substituent in the equatorial
position because the isopropyl substituent is larger than the fluoro substituent, The larger the sub-
Situent, the less stable is the conformer in which the substituent is in the axial position because of the
1.3-diasial interactions,
iticant in reactions in which the number of reactant molecules and the number of product
molecules are not the same,
LA+B==C
2 A+B C
AS is more si
b, None of the four reactions has a positive AS
In order to have a positive AS°. the products must have greater freedom of motion than the reactants
(In other words. there should be more molecules of products than molecules of reactant.)
CCopsright © 2014 Peano falstion tne 25,
26.
27.
ChapterS 171
ad AG = AW - TAs AG? = -RTINKy
(recall that 7 = °C + 273) AG? = —(1.986 * 10-1)(303) In Ky,
AG? = =12 = (273 + 30)(.01) 15 = —0.60 In Ky
AG? = =12 = 3 = -15 “AY
Y
ee
cH,
¢
24. sensey, NHs isa good nucleophile, so this is an $
HW SCH,
He 7 HECHS The product has the inverted configuration compared to that of the reactant
cHy 5
en Loren anyon L/h
irbon from the top oF the
b. (CH
Once the tertiary carbocation forms, methanol can attack the sp"
bottom of the planar carbocation,
Copyrigtt ©2014 Peason Eston, Ie 294
2.
Chapter 9
LAN
S,2 ives back-side attack only.
Ss
* SyI gives ba
‘OCH, ‘ocH,
C
OC,
‘The fate ofan St reaction snot alfested by insreang the eancentation of the mleopil. wheres the
rate of an Sy2 reaction is increased when the concentration of the nucleophile is increased. Therefore. we
first have (0 determine whether the reactions are Sy! or Sy2 reactions.
oct
k-side and front-side attack,
A isan Sy2 reaction because the conliguration of the product is inverted compared with that of
the reactant.
B i
Cis an Sx1 reaction because the reactant is a tertiary alkyl halide.
Sx2 reaction because the reactant is a primary alkyl halide,
Because they are S,2 reactions. the rate of A and B will inerease if the concentration of the nucleophile is
increased,
Because it is an Sx reaction, the rate of C will not chan
increased,
we if the concentration of the nucleophile is
on will be faster
Because both reactants in the rate-limiting step are neutral, the react
solvent is increased.
Fthe polarity of the
a, Increasing the polarity will decrease the rate of the reaction because the concentration of charge on the
reactants is greater (the reactants are charged) than the concentration of change on the transition state
b. Increasing the polarity will decrease the rate of the reaction because the concentration of charge on the
reactants is greater (the reactants are charged) then the concentration of charge on the transition state.
- Increasing the polarity will increase the rate of the reaction because the concentration of charge on the
reactants iy less (the reactants are not charged) than the concentration of charge on the
a. CHsBr + HO" - CHOW + Br
HO” isa better nucleophile than HO.
bo CHL + HO] + CHOH + I
1 isa better leaving group than Cl
¢. CHyBr + NHy CHNH, + Be
NH, isa better nucleophile than H,O.
a. CHyBr + HOT —PMSO, CHLOH + Br
Unlike ethyl alcohol, DMSO will not stabilize the nucleophile (and therefore decrease the rate of the
reaction) by hydrogen bonding,
HOH CH ANH, + Br
CHyBr + NH,
A more polar solvent is able to stabilize the transition state, (EtOH is ethanol.)
Copsright © 2014 Peason Flat, In 3B.
Solved in the text
Acetate ion will be a better nucleophile in dimethyl sulfoxide because dimethyl sulfoxide will not stabili
the negatively charged nucleophile by ion-dipole interactions, whereas methanol will stabilize it by ior
dipole interactions,
Only an Syl reaction will give the product with retention of configuration. Because the Sy1 reaction is
favored by a polar solvent, a greater percentage of the reaction will take place by an Sy! pathway in 50%
water/50% ethanol, the more polar of the two solvents
a HOTS because it forms a six-membered ring, whereas the other compound
would form a seven-membered ring. A seven-membered ri
more strained than a six-membered ring, so the six-membered ring
is formed more easily. (See Table 3.8 on page 127 of the text)
b WO LALA, because it forms a five-membered ring, whereas the other compound
‘would form a four-membered ring, A four-membered ring is more
strained than a five-membered ring. so the five-membered ring is
formed more easily.
ed ring, whereas the other
Jat-membered
so the seven-
& HOLA ALAA, because it forms a seven-membe
© compound would form an eight-membered ring. An
s more strained than a seven-membered Fi
membered ring is formed more easily: also, the Br and OH in the
compound that leads to the eight-membered ring are less likely t0
be in the proper position relative to one another for reaction because
there are more bonds around which rotation to an unfavorable con-
formation can occur, (See page 434 of the text.)
a. When hydride ion removes a proton fron the OH group, the alkoxide ion cannot react in an intramo
Jecular reaction with the alky! chloride to form an epoxide, because it cannot reuch the back side of the
carbon attached to the chlorine, Thus, the major product will result from aa intermolecular re
\
»
b. Hydride ion removes a proton from the OH group more rapidly than it attacks the alkyl chloride, Once
the alkoxide ion is formed, it attacks the back side of the alkyl chloride, forming an epoxide.
Copgnigin #14 Pers Edo, I 296 Chapter9
Hydride ion removes a proton from the OH
carbon attached to the bromine, forming at si
group. and the alkoxide fon attacks the back side of the
membered ring ether
a :
BrcH.CH,cH,CHCH,oH "Br HCH CHSCH CHG
4. Hydlride ion removes a proton from the OH group, and the alkoxide ion attacks the back side of the
carbon attached to the chlorine, forming an epoxide.
cH, cH, Hs
" 4
pe cHeHc—cHy tt
CHICKS Gy
After the halohydrin is formed, hydride jon removes a proton from the OH
forms an epoxide.
roup and the alkoxide jon
CH,CH.CHsCH=CHs
i
Se oncncncn enc) > cence ate
ou o
’
CHACH.CH
3H. Instead of attacking the back side of the carbon (0 the right of the sul
side of the carbon to the left of the sulfur.
Nitty
. N
am rs
YN NNO
Ca o|
Lo
HY
HO OH
a. © CHCHCHSCH, ©. CHCH.CHOCH,
b. CH\CHsCH.NHy d. CH\CH,CH,SH © CHyCH:CH:NH;CH;
(Notice that the produet in part ¢ is not protonated because its pX, is ~ —7: the product in “E" is proton-
ated because its p&, is ~ 11. In part & CH,NH(CH;CH-CH, jy and CH,N(CH3CH.CH,); ean also be formed.
depending on the concentration of I-bromopropane: see Problem 15 on page 415 of the text.)
Copysight © 2014 Peron Faleton. 37.
40.
a
Chapter 9 297
Ithe atoms are in the same horizontal row ef the periodic table, the stronger base is the better nucleophile.
If the atoms are in the same column, the larger atom is the better nucleophile in the protic polar solvent
because the solvent will form stronger hydrogen bonds with the smaller atom,
a. HO HS
b. NH, a. HS” fs Be
The weaker base is the better leaving group.
a, 1,0 c. HLS et
b. 1,0 a Hs f Br
a, HO CH NH; e. CH.CH.S & CEN
°
b. CHO a HS CH CO he CHACHC
Jn parte, a tertiary amine and a quaternary ammonium ion can also form unless a large excess of CHsNHs
is used. (See Problem 15 on page 415 of the text.)
‘a, The rate will be increased nine-fold.
b. ‘The reaction will be slower because of tie more polar solvent
¢. The reaction will be slower because it will be an Sy? reaction with a poor nucleophile.
4. The reaction will be slower because the leaving group will be poorer
fe. The reaction will be slower because there will be more sterie hindrance.
a, The reaction will be slower hecause the leaving group will be poorer.
b. The reaction will be slower because it will be an Sx2 reaction with a poor nucleophile.
Oo
(A large excess of methylamine will have to be used in the second step in order to minimize the
formation of a tertiary amine and a quartemary ammonium ion.)
¢. Half of the cyclohexene is converted to bromocyclohexane, and half iy converted to an alkoxide ion,
‘The ether is formed from the reaction of bromocyclohexane with the alkoxide ion,
OQ” cr"
- - OO
Son o
LJ Or
Cong © 2914 Pearson Eston, I 298 Chapter 9
oa CHCHSS ce NH, > 10
i
b ( )-o ato Be > cr
43, The pk, would increase (it would be a weaker acid) because of a decreased tendeney to form a charged
species in less polar solvent, (See Problem 29.)
ones ay, an, cn
CHCCH, |
a
b. The products are obtained as a result of the nucleophiles reseting with the carbocation, 2-Bromo-
2-methylpropane and 2-chloro-2-methylpropane form the same carbocation, so boti alkyl halides form
the same products
43. a. The Sy2 reuetion takes place with inversion of configuration
CHCHCH GcHscH,
{ Ho i
Be WZ >ocns
‘Hs Hs
(R}-2-bromopentane (S)-2-mnethoxypentane
cHy City
br H MnO octy
CHCH.CH: CHCHCHs
CHCH, HCH, CHCH,
I HOH |
po ne act
be CH CHCHLCH,~ \°CHy CHCHCH CH, VCH, © CHE 7 CHACHACHACH,
Br OCH; cH
{R)-3-bromo-3-methytheptane (Ry-Femethoxy-3-meliytheptane —_(5)-3-methoyy-3-methytheptane
HCH, CHCHy CHCA,
e——a anon eno Hy + cry 0c
JCHACHSCHy CHCHCHCH, LCHyCH.CHy
Copyright ©2014 Pearson Fadaton Chapter9 299
_
c CHAOCH;CH,
\=/
a crscrcnc HCHOCH,
cro
fe. CHLCH=CHCH,Br = CH,CH=CHCH,OCH,
11,08
f CHCH=CHCH Br "+ CH.CH=CHCHOCH, +
46. a
Br Meson OCHSCH,
‘rewtesned
CHB CH ch
—o- OF o&
+ Br :
encom cnenon|
ore ° ci:
“och CH,
tote an
a ae
Br
cnernont ‘cusctton
‘ ,
NZ “Yow
OCH.CHs OcH.CH:
Thiscompounl is a agmatiie Thi conpount fas asym
ene, oats Rud esr ath the Ra 8
Sfremonet il eet, Seuomers il tain
47. Methoxide ion will be a better nucleophile in DMSO. because DMSO cannot stabilize the anion by hydro
gen bonding.
Boa oe “The nucleophile isles sterically
_ = _ + Cr hindered
CCongtght © 2014 Peason Education. ne 300 Chapter 9
Ho The eleetron-withdrawing oxygen
ro OTOH + CF increases the elecirophilicity of the
ee
Og ano
carbon that the nucleophile attacks,
b.
al Steric strain is decreased when the
alkyl halide diysoeiates to form the
a carbocation because the hybridiza.
~ L
“ ae tion of the carbon changes from
a TA sp to ap allowing th bond ag
“ between the bulky groups to increase
from 109.5" 120" Therefore the
fers forme more ply
@. (CH yCBr
Because the reactants are neutral.
the
the reaction will be faster
more polar solvent.
9. cr NN
SY
a ow SNS cac
&
7 an eee
os |
50, a. CHO « & \-o
Br
4. ie)
cag
si. on on
\ IX
wl Vf wf
— NM Ory
ye
a LN
we
Kd
N
NHy |
0.
oe Ns )
Neer
TI
On OH
Copysight © 2014 Peano Eaton Ine Chapter9 301
52, The slow step of the solvolysis reuetion is formation of the carbocation. Because the products of the slow
Step are charged, they will be better stabilized by formic acid than by acetic acid, because formic acid has
«greater dielectric constant, Because the products are more stabilized. the transition state leading to them
will also be more stabilized, so the reaction will be faster in the solvent with the greater dielectric constant
‘Therefore, the second reaction is faster
a this is an Sy1 reaction because acetate ion is a relatively poor nucleophile and the
alkyl halide is tertiary.
53. a. We can predict t
CHy Hy
i
|
CHACCH=CHCI CHCH CH; += CHjC=CHCHCH.CH,
el 6 et
I
cuco
Hy
+ CH\C=CHCHCHCHy
occHy
I
oO
mn predict that this is an Sy reaction because acetate ion is relatively poor nucleophile
cH cH cn,
4-4-6.
fo
Congright 012014 Pearn Baan, Ie s7.
Chapter 9
CH CH CH Br + Ht CHCHCHIC SCH oe CHCHLCHSCHSCH
°
1
b. CHACH,CH,Br CHCHCH GE CHACHICHLCCH
1 Ree
6. CHACHCH:Br + “> CHACH CHC =CH Site tos io” °
CH.CH.CH,CH.CH
d. CHACHCH.Br + CH,CH,CH,C = CHCHCH CH=CH
CHACHACHS
‘The equilbrium contstant is given by the relative stabilities of the produets and reactants, Therefore. any
Factor that stabilizes the products will increase the equilibrium constant
produ
[reactants]
K
eater
Ethanol will stabilize the charged products more than will diethyl ether because ethanol has a g
dielectric constant, Therefore, the equilibrium will lie 9 (Qoward products) in ethanol
is less sterivally
a, The reaetion with quinuelidine had the la
hindered as a result of the substituents an the nitrogen being pulled back into 3 ring structure.
fer rate constant because quinuclidin
b, The reaction with quinuctidine had the larger rate constant for the same reason given in para
Isopropyl iodide has the larger difference in rate constants and therefore the ka
ratio because, since itis more sterically hindered than m
in the amount of serie hindrance in the nucleophile
Bet Kesnaciie/ Kristy ine
Wl iodide. itis more affected by differences
Because methanol is a poor nucleophile. the reaction will Luke plice predominately via an Syl pathway:
The bromine that will depart is the one that Formis & secondary benzylic cation and not the one tht would
have to form a secondary carbocation. The nucleophile can approach from the top oF the bottom of the pla
nar carbocation,
OCH; och,
co, Oa,
i Chapter9 303
‘The number of atoms in the ring is given by n. Three- and four-membered rings are strained, so they are
harder to make than five- and six-membered rings. The three-membered ring is formed faster than the
four-membered ring because the compound leading to the three-membered ring has one less ¢
single bond that can rotate to give a conformer in whieh the reacting groups are positioned too far from one
another For reaction,
conformer in which the reacting groups are positioned too far from one another for reaction (compared to
the compound that form the four-membered ring), the five-membered ring is formed faster because it is
relatively strain free. So lack of strain more than makes up for the lower probability of hav
groups in the proper position for reaction,
‘The rate of the ring-forming reaction gets slower as the size of the ring being formed gets larger, because
the reactant has more bonds that can rotate (o give conformers in which the reacting groups are positioned
too far from one another for reaction
Because all the reactions are Sy? reactions, the configuration of the asymmetric center attached to the Br in
the reactant will be inverted in the product.
CHACH,
a. CHO, H
pee ee oe 7
one CH
CCH, CHCA R45)
bo cho
CHC CCH) oF
We NG HCH
CHCHy CMs RAR)
cH,
HCH
HW H——ocn
ScHicHy °F s
No HO} CHy
CH say
CULCHy
cue
ana He _ ole
eer
a Noes ctu
CHO KCl: sas)
CHACHs
Copycight © 2014 Peano Esco, te 304 Chapter 9
60, a -LCH,CHLC=CCH.CH, 2. CH\CH,CH,OCH,
be CH CHC + CH.CH,CH.CH;Br or CH,CH,CH,CH,C=
+ CHCHBr
6 CHYCHO” + CH,CHCH,CH\Br or CHCHCHSCH.O + CH,CHBr
Hy chy
ol. os
Fc, — =
o :
. cu
CHOW : Ba
n+ ocn, “CH GH \_} 6cn,
HH
62, Tetrahydrofuran ean solvate a charge better than diethyl ether ean, because the floppy ethyl substituents
of diethy! ether provide sterie hindrance, maki
approach the positive charge that is to be solvated,
electrons of the oxygen to
y+ kt SSS CHCH + Kcr
6. CHC!
+ KCK precipitates out
in acetone, which drives
the reaction to the right
os
Chel —
|
ny
Br
Br
AN
*LAR A,
‘OCH, S07 S01
un HBS
b. Two products are obtained because methanol can add to the top or the bottom of the planar double bond
One bromine is etiminated with the help of one of oxygen’s lone pairs. forming a carbocation where
the positive charge is shared by a carbon and an oxygen. The oxygen cannot help the oth
dissociate,
Copyright © 2014 Peurwont ation. 67.
Chapter9 305
A Diels-Alder reaction between hexachlorocyclopentadiene and 1.4-dichlorocyclopentene forms
chlordane.
a
cl
cl
‘cl
a
1 is a good nucleophite in a polar solvent such as methanol, so it reacts rapidly with methyl bromide, caus:
ing the concentration of Lt decrease rapidly.
seni A cai
Lens 5 i
1 isa good leaving group so methyl iodide undergoes an Sy2 reaction with methanol.
Methanol is a poor nucleophile, so the Sy2 reaction is slow. Therefore. iodide ion returns slowly to its
original concentration.
cong «cH croc, +
ae
Iwill not undergo an $y2 reaction, because of steric hindrance to back-side altack
Tt will not undergo an Syl reaction, because the carbocation that would be formed is unstable, since the
ring structure prevents it trom achieving the 120° bond angles required for an sp? carbon,
57.
‘The equation needed to calculate K., from the change in free energy is given in Sect
In Kay =
Ink = 2D eal mol!) 2.7
BRS 0.001986 keal mol 'K'X303K 0.60
In Ky = 36.1
Ku = 48 x10"
As expected. this highly exergonic reaction has at very karge equilibrium constant
CConyrght © 2014 Pearson Eaton a: 306
Chapter 9
Chapter 9 Practice Test
Which of the following is more reactive in an Sx 1 reaction?
a © S-cuencny or &-
Br br
HACHCH,
re Br
i
b. CH\CH=CCH, or CHCH=CHCHCHs
Which of the followi
cH Hci
is more reactive in an S.2 reaction?
|
a. CHSCHCHBr or CH.CH;CHBr
Draw the product(s) of the following reactions. showing the stereoisomers that are formed:
ee
Ch
cH,
» CS cwenen,
Br
cH,
3 al ee
HCH
cH,
| cist
© cen kT
caon
fe. CH,CH=CHCH.Br .
Copyright 912014 Pearson Eduction a 4.
Chapier9 307
Indicate whether each of the following statements is true or false:
a, Increasing the concentration of the nucleophile favors an Sy1 reaction over
aan Sy2 reaction, T F
b. Ethyl iodide is more reactive than ethyl chloride in an Sy? reaction, T F
¢. Inan Syt reaction, the product with the retained configuration is obtained
in greater yield. 7 Fi
4. ‘The rate of a substitution reaction in which none of the reactants is charged
will increase if the polarity of the solvent i increased. T F
fe. An Sy? react
n is a two-step reaction, y F
f. The pX, of a carboxylic acid is greater in water than itis in a mixture of
dioxane and water. v F
4
2 4-Bromo-I-butanol will form a eyelie ether faster than will 3-bromo-T-propanol
Answer the following
a, Which ia stronger base, CH\O" or CHS”?
b. Which is a better nucleophile in an aqueous solution, CHO™ or CHS”?
For each of the following pairs of Sx? reactions, indicate the one that occurs with the greater rate constant
that is, occurs faster}:
a CHCHCIC] + HO- or CHACHCH) + HO
&
b. CHCHCHCL + HO- or CHYCHSCHSE + HO
6. CHCHYCH:Br + HO" or CH\CHSCHaBr + 1,0
d. CH.CHCH, or CHYCHCH, CHO”
I ‘cHon
br Br
@. BICH,CH)CH;CH)NHCH; or BrCH,CH,CH)NHCH,
Circle the aprotie solvents
a, dimethyl sulfoxide b. diethyl! ether ¢. ethanol hexane
How would inereasing the polarity of the solvent alfeet the following?
athe rate of the $x2 reaction of methylamine with 2-bromobutane
b. the rate of the Sx! reaction of methylamine with 2-bromo-2-methylbutane
6. the rate of the $,2 reaction of methoxide ion with 2-bromobutane
d. the pX, of acetic acid
the pk, of phenol
CCongright © 2014 Peano Basen, le anti
anti-periplanar
dehydrohalogenation
deuterium kinetic
isotope effect
regiosel
sawhorse projection
syn elimination
syn-periplanar
target molecule
Williamson ether
synthesis
Zaitsey’s rule
aan elimination reaction in which the substituents being eliminated are removed.
trom opposite sides of the molecule,
substituents are attached (© parallel bonds on apposite sides of a molecule,
elimination of a proton and a halide ion,
ratio of the rate constant obtsined for the reaction of a compound containin;
hydrogen and the rate constant obtained For the reaction of an analogous compound
in which one or more of the hydrogens have been replaced by deuterium,
‘a reaetion that removes atoms or groups from the reactant to form a1 7 bond.
aan elimination reaction where the groups being eliminated are bonuled to adjacent
carbons,
4 unimolecular elimination reaction
a bimolecular elimination reaction
the preferential formation of « constitutional isomer,
‘4 way (o represent the three-cimensional spatial relationships of atoms by looking.
at the carbon-carbon bond from an oblique angle,
aan elimination reaction in which substituents being eliminated are removed from
the same side of the molecule
substituents are attached to parallel bonds on the same side of a molecule,
the desired end product ofa synthesis
formation of an ether from the reaction of an alkoxide ion with an alkyl halide,
the cule that states that the more stuble alkene product of an elimination reaction is
obtained by removing a proton from the B-carbon that is bonded 10 the Fewest
hydrogens.
308,
Copyright 2014 Pearson acon Chapter 10 309
chy cH, cH
La cHERCHCH, wh eMC=CHE, — & CCLLCH=CH,
ony
a aia The alkene (2-butene) that is formed is more stable than the alkene
(C-butene) that is formed from the other alkyl halide.
Br
b on Br’ isa better leaving group (weaker base) than Cl
‘The alkene (2-methyl-2-pentene) that is formed is more stable than
be
eX the alkene -methyl-2-pemene) tha is formed fom te oer aly
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