+ HOt cur Sosa ‘show that in a 0.1 M solution of Protons to water, F Acetic acid at 25°C only about 1% of the acetic acid molecules ionize by ‘Therefc ly of aity constant (K;)or px ep i isa weak etd Ase dal genoa ed prengt racer Acidity Constant, K, Teaction that occu; rs in an aqueou, for the a constant (ky Solution of acetic acid is an equilibrium, we can describe it with an K,, -14.0°1(CH,c0;] Sli ernconnecy (CH,CO,AY[H,O} solutions, the concentratior . m of water is essenti Ao sari : aii consian ire ‘cris essentially constant (~55.5M),so we can rewrite the expres @ new constant (K.) called the acidity constant: si H,0°] [(CH,CO;] K, = K,,[H,0) = [440°] (CH,Co;) LO = Te CORT acidity constant for acetic acid is 1.76 x 10°, write (aad J iressions for any weak acid dissolved in water. Using a generalized hypothetical acid ction in water is HA+H,O=H,0°+A~ R ssion for the acidity constant is {H,0"}+[A] THAT ‘concentrations of the products of the reaction are written in the numerator and the concentration of the jacid in the denominator, a large value of K, means the acid isa strong acid and a small value of K, means lis a weak acid. If the K, is greater than 10, the acid will be, for all. Practical purposes, completely dissociated in aC tions less than 0.01 M. 77 x 10. (a) What are the molar concentrations of the hydronium ion and formate +) in a 0.1M aqueous solution of formic acid? (b) What percentage of the formic acid is ionized? ity and pK, el usually express the acidity constant, K, as its negative logarithm, pK, pK, = -logk, to expressing the hydronium ion concentration as pH: pH = —log{H,0"] pK, = ~log(1.76x 10") = (4.75) =pX, and the strength of the Ls, Notice that there isan inverse relationship between the magnitude of the * The larger the value of the pX., the weaker is the acid. For example, acetic acid with pK, =4,75 isa weaker acid than trifluoros acetic acid with PK, =0(K, =) 5 id. (It is understood that a positive", MEK iy acid with pK, =—7 (K. wr stronger acid than trifluoroacetic aci than a negative pX,) ‘= 10°)i CH,CO,H < CF,CO,H < HCl pK,=0 pK, Table 3.1 lists pX, values for a selection of acids relative to water as the base. The values in the middle p4 the table are the most accurate becauise they can be measured in aqueous solution. Special methods myc, j.'*? ‘estimate the pK, values for the very strong acids atthe top of the table and for the very weak acids at the boy, PK, values for these very strong and weak acids are therefore approximate. All of the acids that we shay): this book will have strengths in between that of ethane (an extremely weak acid) and that of HSbF,(an asi strong that it is called a “superacid”). As you examine Table 3.1, take care not to lose sight of the vast range o, that it represents (a factor of 10°). = Table 3.1 Relative strength of selected acids and their conjugate bases oo ‘Approximate pk, Conjugate Base emcerst SbF, acid HSbF, Wana HI a H,SO, HsO, HBr a HCL a CBSO HH CHSO; (CH),0H (CH,),0 (CH),C=0H (CH),C-O CH,OH, CHLOH Be, H,0 : HNO, No; late! CF,CO; : EE FE CH,COn ison: oa S| CH,CO; | O HCO, b ee : CH,COHCOCH, Cation ee s a Hs 102 oe CHNH,’ 106 er BG, 187 on SACRO ee 16 CH,CH,O- (Continued) ee al3.1. Continued 61 The Stat of Bronsted Lowry Ais nd aes: and _, npure water at 25°C, the concentrations ; of hyai tion of water in pure water is 555M, we can cme nam and hy ‘an calculate the K, for water. k, = H,0° 10H] 'ydroxide ions are equal to 10M. Since the concentra- 107)(107 [H,0] 1) 10 pK, =15.7 practice Problem 3.8 | @an a has K, = 10”. What is its pk,? (b) Another acid (HB) has K, = 5; what is its pK,? (¢) Which is the Practice Problem 3.9 Show calculations proving that the pK, of the hydronium ion (H,O") is -1.74 as given in Table 3. 3.6C Predicting the Strength of Bases Inour discussion so far we have dealt only with the strengths of acids. Arising as a natural corollary to thisis a principle that allows us to estimate the strengths of bases. Simply stated, the principle is this: + The stronger the acid, the weaker will be its conjugate base. We can, therefore, relate the strength of a base to the pK, ofits conjugate acid. + The larger the pK, of the conjugate acid, the stronger is the base Consider the following as examples: cr CH,CO;- OH- Very weak base Weak base Strong base pK, of conjugate pK, of conjugate PK, of conjugate (HC) =-7 — acid (CHCO,H) =475 acid (H,0) = 15.7 We sce that the hydroxide ion isthe strongest inthis series of three bases because its conjugate acid, water, is the weak- ‘est acid. (We know that water is the weakest acid because it has the largest pK,.) ‘ ‘Amines are like ammonia in that they are weak bases. Dissolving ammonia in water brings about the following equilibrium:won wt AGH nal Dissolving methylamine in water causes the establishment of a similar equilibrium, Cai HS am cH + Q-H ce Conjugate Base Add cn eee Again we can relate the basicity of these substances to the strength of their conjugate acids, The Onjua, Gqrpomia is the ammonium ion, NH,.-The pX, ofthe ammonium ion it 9.2. The conjugate acid of meqy CH,NH," ion. This ion, called the methylaminium ion, has pX, = 10.6. Since the conjugate acid of Methyi, ie thy ‘weaker acid than the conjugate acid of ammonia, we can conchide that methylamine is a stronger base ts Using the pX, values in Table 3.1 decide which is the Wesker H—O-H HC re stronger base, CH,OH or H,O. acid ff vr Answer pK,=-1.74 From Table 3.1, we find the pK, values of the conjugate Because water is the conjugate base of the Weaker i acids of water and methanol. is the stronger base. as HC. Wate base a H Practice Problem 3.10 a Using the pK, values of analogous compounds in Table 3.1 predict which would be the stronger base @ @ -6 or di) A 6 © @ A or Gil) JON NL Practice Problem 3.11 The pK, of the anilinium ion (CJH,NH,) is 4.63. On the basis of this fact, decide whether aniline (C11! stronger or weaker base than methylamine, 3.7 | HOW TO PREDICT THE OUTCOME OF ACID-BASE REACTIONS Table 3.1 gives the approximate pK, values for a range of representative a obably will \pounds, While you pro ai cxpocted to masnontes HUGE SPR SMAPSIRTIAG 9 Ita a good idea to begin to loam the gener! 01!"up. For example, ‘ proctic iven in Table irange PK, = 3-5). Ethy1 alcoho! 75,and, carey ive bi is Of ethyl alcohol (in the pat yi? 8¥°H aS an exn ‘ylie acids generally have pK, values near this ee P 8). and tHe OF Ah alcohol, and alcohols generally have pk, © on. (There are exceptions, of course, and we shall | are representative of their class #1) will react with aqueous NaOH in the following os acid (H,O) and weaker base (RCO,"): ‘OZ HS Nar Stronger acid PK,=35 ithe mixing of an aqueous solution of phenol, place because it would lead to the formation ofa weaker AGee Table 3.1), and NaOH. What acid-base acid (water) from the stronger acid (phenol), It would if any, would take place? also lead to the formation of a weaker base, C,H,ONa, from the stronger base, NaOH. the relative acidities of the reactant and of the acid that might be formed by @ proton transfer to the base (the ion). The following reaction would take Problem 3.12 7 he outcome of the following reaction. Water Solubility as the Result of Salt Formation ic acids containing fewer than five carbon atoms are soluble in water, many gh acai acid and other carbonic ee not appreciably soluble in water. Because oftheir aity, how ri acs oie cide dissolve in aqueous sodium hydroxide; they do 80 by reacting to form water- oluble carboxylicSoluble in water (due t0 its polarity ns 544) notable im Tiled with aqueous hydrochloric acid in the following way ‘We can also predict that an amine 23.4 cr R-NOH Cl + 0-H HOLH Cl RONH, * i h v be Weaker acd Weaker base pK,=9-10 Stronger: pK,=-L74 ‘While methylamine and most amines of low molecu Bre viubility, However, these water-insoluble weights such as aniline (CyH.NH.) have! Rey esicat ‘convert them into soluble salts: ily in hydrochloric acid because the aci & ‘Stronger base lar weight ae very soluble in water, amines with jp, imines dss | bs Lo SO CK — CH. NH Cr +:0—H CH—NH, + et cr CH; i i H arenas ‘Water-soluble salt 3.8 | RELATIONSHIPS BETWEEN STRUCT! URE AND ACIDITY i hich a proton can be separated f ‘The strength of a Bronsted-Lowry acid depends on the extent to w b ri ana ferred to es ‘Removing the proton involves breaking a bond to the proton, and it involves making the rad . base more electrically negative. ‘When we compare compounds in a single the dominating effect. * Bond strength to the proton decreases as we move down the column, increasing its acidity. column ofthe periodic table, the strength of the bond to the pn, This phenomenon is mainly due to decreasing effectiveness of orbital overlap between the hydrogen ls orbital an orbitals of successively larger elements in the column. The less effective the orbital overlap, the weaker iste b and the stronger is the acid..The aciities of the hydrogen halides furnish an example (Group 17). The sam acidities and basicities holds true in other columns of the periodic table, Consider, for example, the coluin hes ‘oxygen (Group 16): A PK, i 32 HF px ; ec 157 HO ¥ Group 17 and ~7 H— 1 uP Group16 79 ys |B ~9 HOBr ”~ F 39 Hse © ~10 HI Se (oe pon eee aaa fetagtd column in the periodic table due to decreasing bonds ity of the conjugate base. Tight in a given row of the periodic table due to increasingathe hydrogen halides with that the H—F HI. HBr. and HCI are strong aay ‘acidic than the other hy Fis the weakest andthe H S. their conjugate ‘cid and H—1 is the strongest. This follows ond is the weakest iS rogen halides fy bases (I', Br. C1’) are all weak bases. HF, however, Be eomespondingly more basic ng? o> OTders of magnitude (compare thal pie Sa ae TE ic th i iP pK, Species we commonly think of as basea nts Othe halide nions.The fluoride anion is still not nearly as ' bases, su uch ide anion, however. A comparison of the pK, lustrates this point ~H bond MMF (3.2) and H,0 (15.7) i the strongest bond is the © ‘strongest acid, 4s the hydroxi and H,0 is the weakest ‘acid; the weakest bond is the Se~H bond and ght when we compare fe compare compounds in a given row of the periodic table. ie Predominant factor becomes © atom in question affe 4 ton and it affects the relativ, ets aciain Er oce RPE rREeT ins cre Mn Duty of the anion (conjugate base) that forms when the proton is ost mpounds are all hydrides of first ror one, o™MPAT the acdities ofthe compounds CH,, NH,-H,0, and HE Beis riek (ee Tac 1, “ments, and electronegativity increases across a row of the periodic I$ Vary somewhat. bu the electronegativity of the atom bonded to the in two related ways. It affects the polarity of the ed on electronegativity and increasing pol o larization of the bonds to hydrogen, we see that almost no positive evident at the hydrogens of methane. Ver ty little positive charge is present at the hydrogens of ammonia. This ent with the weak clectronegativity of both carbon and nitrogen and hence with the behavior of methane and as exceedingly weak acids (pK, values of 48 and 38, respectively). Water shows significant positive charge at (PK, more than 20 units lower than ammonia), and hydrogen fluoride clearly has the highest amount of charge at its hydrogen (pK, of 3.2), resulting in strong acidity, H_Fis the strongest acid in this series, its conjugate base. the fluoride ion (F>), will be the weakest base. is the most electronegative atom and it accommodates the negative charge most readily: CM Big ines CH HN] Ogee: -methanide ion (CH;) is the least stable anion of the four, because carbon being the least electronegative ele- east able to accept the negative charge, The methanide ion, therefore. is the strongest base in this series. [The fon, a carbanion, and the amide ion (NH) are exceedingly strong bases because they are the conjugate ‘extremely weak acids.] fends in acidity within the periodic table are summarized in Fig. 3.2. The Effect of Hybridization ‘of ethyne are more acidic than those of ethene. which in turn are more acidic than those of ethat HH ‘ne er Ho Ethane PK,=80 \ eeai iodic trends in relative aci Seis aranateteacregerion ce We can explain this order of acidities on the basis of the hybridiza Electrons of 2s orbitals have lower energy than those of 2p orbitals b average, to be much closer to the nucleus than electrons in 2p orbitals. orbitals are spherical and centered on the nucleus; 2p orbitals have extended into space.) : ‘With hybrid orbitals, having more s character means that the electrons 0 in energy, and the anion will be more stable. ‘The sp orbitals of the C—H bonds of ethyne have 50% s character of one s orbital and one p orbital), those of the sp’ orbitals of ethene have 33 orbitals of ethane have only 25% s character. This means, in effect, that the ‘were more electronegative than the sp’carbon atoms of ethene and the ; Electronegativity measures an atom’s ability to hold bonding electrons close to the nucleus makes it more stable.) . The effect of hybridization on acidity can be seen in ethyne, ethene, and present on the hydrogens of ethyne (pK, = 25), but almost no positive char ethene and ethane (both having pK, values more than 20 units greater than effectively greater electronegativity of the sp orbitals in ethyne, which have m orbitals in ethene and ethane. [Also the negative charge resulting from ele« and ethene.] Now we can see how the order of relative acidities of ethyne, ethene, and ‘egativity of the carbon atom in each compound: Relative Acidity of the Hydrocarbons HC=CH >H,C=CH,>H,C—cH, Being the most electronegative, the sp-h extent, causing its hydrogens to be most 3 H,C— CH," > H,C=cH: Notice that the explanation given here involves acidities of HF, H,O,NH,,andCH,F 3,8 |, Relationships between Structure and 1 “jnductive Effects bon bond of ethane is completeh coups: CH\-CH, (the C-C bond ty nag eePOlar because at each end of the bond there are two equivalent Be as '8 non-polar), 1 gomdehowever: CH, > dijo® Polar). This is not the case with the carbon-carbon bond of ethyl 1 “ne end of the bond, the one nearer the fluorine son-crton bond Fsuts rom an intrinsic clectron arnt more negative than the other. This polarization of ‘the car- apie OUR PACE aN through the Bonds acting ability of the fluorine (because of its electronegativity) that of the molecule. Ch is i effects are electronic effects transmitted oan ie * Gonating or electron withdrawing. Inductive effect through bonds. The inductive effect of a group can be electron 's weaken as the dis 5 ft athe case of ethyl Nuoride, the positive char distance from the group increases. Hemet ibe forin is closer to CL. 8¢ that the fluorine imparts to Cl is greater than that imparted to C2 Inductive Effect (I Effect) of Groups Blectron donating groups show positive inductive effect (+1). For example, “ T>—D>—H —R>-0 —Se>—§ —C(CH,);>—CH(CH,),>—CH,—CH,> —CH, i —0>—C-0 Electron withdrawing groups show negative inductive effect (-1). For example, "—OR,>—NR, —F>—OR>—NR,>CR, a BGI PCH —As— City> —So—cH, 3 A ee ci CH, |, een + JR It =0— >—sR,>—SeR,>—TeR, s ’ —SiR,>—GeR, _ —OR,>—OR i 7 ae. jH>—CH=Ni _ —SR,>—SR : 7c =Nn>—CH = NH, > —CH,—NH, —NH,>—NH, —CH=0>—CH =NH>—CH=CH, —ocH,>—s—CH,>—Se—CH, _ =C=CH> CH=CH, in —F>—CI>—Br>—I ‘ >—CH=CH, —CH=0>—CH,-0— iv +<\ ‘CH =O>—CH,—O—CH, unsaturated and conjugated systems by the orbitals to generate centres of hhenomena is known as mesomeric (M) or resonance (R) effect. redistributions take place in _high-and Jow-electron densities. This p! ap Mesomeric Effect (M) Groups mesomeric effect (+M). for example, donating groups show positive— CH, LR =No > ——Ny —O>=0=R>= 07 CH, R a . CH, =NH,>—NH—C—CH, ~$>—S—CH,>-S. es cH, 9 ; —o-—C—CH, =~ i-cH, Berd, &: F CCL NG > -0- Res ~~ %o | —O—CH,>—S—CH,>— —CHy —O>—NnH,>-oH © ee H \ —F>—Cl>—Br>—I Electron withdrawing groups show negative mesomeric effect. For example, —CH=0 >—CH =NH,>—CH=CH, —CH=S >—CH =O —C=N >-C=CH —C=N —CH,>C=N 3.9 | ENERGY CHANGES ‘Chemical energy is a form of potential energy. It exists because attractive and repulsive electrical forces exist betye, different pieces of the molecules. Nuclei attract electrons, nuclei repel each other, and electrons repel each othe; Itis usually impractical (and often impossible) to describe the absolute amount of potential energy contained a substance. Thus we usually think in terms of its relative potential energy. We say that one system has more or, potential energy than another. a BE Another term that chemists frequently use in this context is the term stability or relative stability. The relay stability of a system is inversely related to its relative potential energy. * The more potential energy an object has, the less stable itis. Consider, as an example, the relative potential energy and the relative stability of snow when it lies high on a mo, tainside and when it lies serenely in the valley below. Because of the attractive force of gravity, the snow high on mountain has greater potential energy and is much less stable than the snow in the valley. This greater potential ener of the snow on the mountainside can become converted into the enormous kinetic energy of an avalanche. By contrast the snow in the valley, with its lower potential energy and with its greater stability, is incapable of releasing such enesa, 3.9A Potential Energy and Covalent Bonds Atoms and molecules possess potential energy—often called chemical energy—that can be released as heat when heat results from a change from potential they react. Because heat is associated with molecular motion, this release of energy to kinetic energy. From the standpoint of covalent bonds, the state of the atoms are not bon ‘A convenient way to represent the relative ies, or heat contents, . (Enthalpy comes from en +B.10 | The Relationshi “ onship between the Equilibrium Constant andthe Standard Fre Energy Changes 46 om ‘ AG =27kI mob! HoH | ; CHCOR cHycHon 4.3 (2) Free-energy changes that accompany ionization ic acid an ative potential BUTS rcen stor and hydrogen ray a of acetic acid and ethanol. (b) Relative po! and products in a chemical change is called the enthalpy change and is symbolized by AH. [The 4 (delta) in ‘aquantity usually means the difference, or change, in the quantity. The superscript” indicates that the measure- emis made under standard conditions} ‘convention. the sign of AH” for exothermic reactions (those evolving heat) is negative. Endothermic reactions + (pose that absorb eat) have a positive AH. The heat of reaction, 4/7" measures the change in enthalpy of the atoms the reactants as they are converted to products. For an exothermic reaction, the atoms have a smaller enthalpy as prods than they do as reactants. For endothermic reactions, the reverse stu. THE STANDARD FREE-ENERGY CHANGE, AG° “animportant relationship exists between the equilibrium constant (K,,) and the standard free-energy change (AG?) fora reaction. AG? =-RT Ink, ‘ehere Ris the gas constant and equals 8.314 J K” mol” and Tis the absolute temperature in kelvins (K), This equation tells us the following « For a reaction to favor the formation of products when equilibrium is reached it must have a negative value for AG? Free energy must be lost as the reactants become products: that is. the reaction must go down an energy hil. is more negative than 13 kJ mot” the For such a reaction the equilibrium constant will be greater than one, If G° ining that more than 99% of the librium constant will be large enough for the reaction to go to completion, mea eactants will be converted to products when equilibrium is reached. «+ For reactions with a positive AG”, the formation of products at equilibrium is ‘stant for these reactions will be less than one. The free-energy change (AG°) has two components, the enthalpy change (AH) and the entropy change (AS"). The telationship between these three thermodynamic quantities is AG" = AH? -TAS* unfavorable, The equilibrium con- 3.10 | THE RELATIONSHIP BETWEEN THE EQUILIBRIUM CONSTANT AND | . We have seen that AH is associated with changes in bonding that occur in a reaction. If, collectively stronger bonds Ti formedin the products than existed in the starting materials, then AH" will be negative (Le. the reaction is exovher- ‘mie)-Mithe reverse is true, then AH° will be positive (the reaction is endothermic). A negative value for AH”, therefore, wl contribute to making AG” negative and will consequently favor the formation of products. For the ionization of Tiss the less positive or more negative the value of 4/1”, the stronger the acid willbe Mestropy changes have to do with changes inthe relative onder ofa sysiem, The more random a system is, the Ba carrery. Therefore, positive entropy change (+85°) it always associated with a change from a more ypten to ess ordered one-A negative enopy change (-AS") accompanies the reverse process Inthe equa- eee the entropy change (multiplied by 7) preceded by a negative signthis means that @ postiveall contribution 0G" and is energetically, xtropy change rom reo orden) makers mee ren... Fora, ee ae oducts equals the number of motccuj ‘many reactions in which the umber of moles ogy shang? Bena THe or, (€.g.. when two molecules react to produce {WO Wen if AS° is small) the value of Af" i hgh temperatres where he ter Tas become te vei is large and negative (ifthe reaction wether or not the formation protic wl al. HtaH ispostive (ithe reaction"! then the formation of products will be : ie Practice Problem 3.13 ‘As®, to be positive, negative, Or approximately rey, ‘ ‘State whether you would expect the entropy change, the following reactions. (Assume the reactions take place in the a ae me a, () AsB—cC () A+B—C+D ae Asn —c | eee eee 1am sein ac required to prod (a) What is the val for a reaction where K,,= 1? (The change in roduce a 10-f) inthe equiltriom ee eae for rfl term to remember.) (b) Assuming that the entropy change for hs negligible (or zero), what change in AH? is required to produce @ 3.11 | THE ACIDITY OF CARBOXYLIC ACIDS VERSUS ALCOHOLS acids However, carborylic acids are much more acidic than the corres, the range of3-5;alcohols have pK as in the range of 15-18, Cony. proportions but with very different acidities acetic acid andi Ie ny 10-fold increase in the equilibrium consign Both carboxylic acids and alcohols are weak alcohols. Unsubstituted carboxylic acids have pK, in examples two compounds of about the same molecular ‘Acetic acid pK, = 475 ‘AG?=27ks mot? 4G?= 908 kJ mol (AG? values are for OH proton ionization.) Using the pK, for acetic acid (4.75), one can calculate that the free-energy change (AG*) for ionization of the cat proton of acetic acid is +27 KJ mol’, a moderately endergonic (unfavorable) process, since the AG* value is po Using the pK, of ethanol (16), one can calculate that the corresponding free-energy change for ionization « is +90.8 kJ mol, much more endergonic (and hence even less favorable) process hydroxyl proton of ethanol calculations reflect the fact that ethanol is much less acidic than acetic acid. Figure 3.3 depicts the magnitude of hex energy changes in a relative sense. How do we explain the much greater acidity of carboxylic acids than alcohols? Consider first the structurel that occur if both acetic acid and ethanol act as acids by donating a proton to water. ‘Acetic acid acting as an acid eer: c. + ee HOF Hes iar He Oo ‘Acetic acid Water Acetateion Hy dronium ion Ethanol acting asan acid cnn ek = HCHO + H-OF Ethoxidelon — Hydronium ion What we need to focus on is the relative stability eh aR : Re is is smaller free-energy, njugate bases derived from a carboxylic acid and ® ‘Tui is becauteie 3 tion Of a carboxylic acid (c.g., acetic acid) as comps"""3:1 | The Acidity of Carbone Acids versus Alohols EI sethanol) has been attribur, . Stabilization of the ne Greater s feation cr catct Stabilization of the we ‘ative charge in the carboxylate ion as com c Of harge (as depicted by nea eeevtate tom appears to arise from two factors: (a) Resonance . ~ sec. Although both effects manus stustutes for the carboxylate jon), and (b) Inductive ito which effect is more important 88 We cha, SOnFIbution to the greater acidity of carboxylic acids, the shall see, has ‘Not been resolved. _ The Resonance Effect ted to great rs the greater acidity of ¢. . “arboxylic acids This explanation invokes a pind Actes Was attributed primarily to resonance stabilization of the car pe especially when the molecule on eg esonance theory that states that molecules and ions are stabilized ce structures of equal stabilin,), "a" P€ TePresented by two or more equivalent resonance structures nce structures can be writ stabilization ofthe anion te yea eO* Sli acid and two for its anion (Fig. 34), and it can be assumed separation of opposite charges cece esau the resonance structures forthe anion afe equivalent and es that have separated cheroos ne it them. Separation of opposite charges requires energy, and reso- i stbnon tS sc escapes a creas = Sarboxylic acid (relative tothe acid itself) lowers the free energy of the Be 2 Positive free-energy change required for the ionbation me Hint: Any factor that makes the free-encn, he axed seronger je free-energy change for the ionization of an acid less positive (or more nega- Acetate ion > HO = on + HO eae = O: ee ‘Small resonance stabilization (The structures Larger resonance stabilization are not equivalent and the lower structure. (The structures are equivalent and there Stites (resin eeu nd te Figure 3.4 Resonance structures of carboxylic acid and carboxylate ion. resonance structures are possible for an alcohol or its anion: CH—CH,-G—-H +H,0 = CH,—cH, +H,O No resonance stabilization No resonance stabilization delocalizafion is always a stabilizing factor, and because of charge stabilization, the energy difference ‘of a carboxylate ion from a carboxylic acid is less than the energy difference for formation of an alkox- om an alcohol. Since the energy difference for ionization of a carboxylic acid is less than for an alcohol, the acid is a stronger acid. } The Inductive Effect how the negative charge in a carboxylate ion can be delocalized over two oxygen atoms by Freese is clcctronegatvity of these oxygen atoms further helps to stabilize the charge, by whats called ‘clectron-withdrawing effect. Consider the following two compounds:H CH-CH-O<4 Ethanol (weaker acid) Jectronegativity of the oxye egret A mpinahe corresponding postion of iT of ace a large posi soup i highly polarize arbon ato of He Bee ie, Eine hyesoxyl group attache ie carton ot earactng inductive effet ORBLE i proson ofthe alcool. Tis preater poi) tfc make the carboxylic acd prown mers. proton separates MOT” To " fhoton ofthe carboxyic acid helps explain W19 Bas relates to the rela Of the conjugate, re hare : the acetate ion iS forms from acetic acid, and ‘ O° er oy CH.—CH:< 0” i . 5 Ethoxide anion Accieipae Stronger base “ 5 better than ethoxide.The negative charge inthe scet The ability of acetate to stabilize the Soa to ethoxide, where the negative charge is localized oy" Se vee aan terete Shape is what makes acetate a weaker base than ethoxide ‘conjugate acid stronger than ethanol). Onitson and he : — inantly due to the ability of its conus, eae Jey acidity of a carboxylic acid is predominantly bs @ Sea wai EAE ie ‘charge better than an alkoxide ion, the conjugate base of an alcohg Pradie Pte. CTCSC—~CCCT ‘Draw contributing resonance structures and a hybrid resonance structure that explain two related facts: The ch ‘oxygen bond distances in the acetate ion are the same, and the oxygens of the acetate ion bear equal nem, charges. ¥ 3.11C Inductive Effects of Other Groups The acid-strengthening effect of other electron-attracting groups (other than the carbonyl group) can be sho comparing the acidities of acetic acid and chloroacetic acid: 9 os Bee cH Yocn Ycu* Yo YAH; NH Weaker Weaker eee ‘Stronger, ‘base en PK ro NANT to a triply bonded carbon) have yx pK, = 38 : hed Most terminal alkynes (alkynes with a proton alli vain the same way that cthyn 4," Bes ahanstote al dearth Foduoaemee aT Ss, Ye des reaction is Jiguid, R—Cm=CH + NH, ee i Wen ‘Stronger base acid pK, 225 a? pK,=38 «_cctyons because, being somewhat less polar than ware, Heveareiptios eo solvents for oF as Miso offers the advantage of using RO ions (ce rt an organic compounds Using ae tases than hydroxide ions because alcohols are yey toms) as nes Alkoridfonsate Son of sod sthoxide (CH,CH,ONa) in ethyl alcohol by 94 meat sarcememnacee oro aay cing bane theyre ion react realy with ethyl alcohol He ee, CH,CH,A cucu02n soa Weaker ‘Stronger acid Stronger ie =16 base PRI rom Nad ‘The sert-butoxide ion, (CH,),CO”, in ter-butyl alcohol, (CH) alcohol, and it can be prepared in a similar way _serbutyl Fi ea, (CHC (cH) CO7H + SH © Stronger acid Stronger ‘Weaker Weaker rae pase base acid PK,=18 (trom NaH) pK, =35 yllithium (RLi) has covalent character, itis polarized so asm carbon negative: R Li. Allyllithium reagents react as though they contain alkanide (R-) ions and, being ths jugate bases of alkanes alkanide ions are the strongest bases that we shall encounter. Ethyllithium (CH ti ‘example, acts 2s though it contains an ethanide (CH,CH,®) carbanion. It reacts with ethyne in the following n—c=c2H” + ScH,CH, "5 H—-C=C: + CH,CH, Stronger acid Stronger Weaker Weaker pK, =25 base base id (om CH,CHL) ay Although the carbon-tithium bond of an al Alkyllithiums can be easily prepared by allowing an alkyl bromide to react with lithium metal in an ether solen' as diethyl ether). Practice Problem 3.18 Wie exuatons forthe iba ato that would eo we eh of he following compouns priate pK, values (Table 3.1), in sree, the weaker acid and weaker base, by using “i ee, ble acid-base reaction would occur, you should indicate this)B.S | Acid. Base Reactions and the Synthesis of Deuterium: and Tum Labeled Compounds is dto CHOW. aH, is added to ethyllithium in hexane is added to HO. (b) NaNH, is added to CH,CH,OH. (@) NH,Clis added to sodium amide in liqui (0) NaOH is added to (CH,),COH. id ammonia wunds in which deuter earns ase deuterium or writium atoms have replaced one oF more hydrogen om, of =e entiying particular hydrogen atoms, Deuterium (CH) and tritium (1H) Ir 2 and 3 atomic mass units (amu), respectively. ‘chemical aa deuterium and tritium atoms in a molecule tre an much the same way that ordi- en atoms behave. The extra mass and additional neutrons associated with a deuterium or tritium atom ‘its position in a molecule casy to locate by certain spectroscopic methods. Tritium is also radioactive, which ‘easy to locate. (The extra mass associated with these labeled atoms may also cause compounds contain- mor tritium atoms to react more slowly than compounds with ordinary hydrogen atoms. This. effect, called effect.” has been useful in studying the mechanisms of many reactions) "way to introduce a deuterium or tritium atom into a specific location in a molecule is through the aci takes place when a very strong base is treated with D,O or T,O (water that has deuterium or hnydrogens). For example, treating a solution containing (CH,),CHLi (isopronyllithium) with D,O results tion of propane labeled with deuterium at the central atom: “ CH, cH, l yexane cHCH Li + 0,0 “2S crdH-p + 0D pee, 2-Deuterio- ¢hium ropane (Stronger (Stronger Qweaker (Weaker base) acid) acid) base) you have available propyne, a solution of Then adding T,O (a much stronger acid than NH,) to the “amide in liquid ammonia, and T;O, show how you solution will produce CH,C = CT: the tritium-labeled compound CH,C=CT. cucecr +1,0 “2, cHc=cr+oT Stronger Stronger Weaker Weaker base acid acid base propyne to sodium amide in liquid ammonia. ing acid-base reaction will take place: BCH + NH, PSP™, CHYC=C: + NH, Stronger Weaker Weaker base base acid Problem 3.19 the following acid-base reactions: ie e %) The solution obtained in (a) +D,0 > (a) CH,CH,OH+ Nal pean (f) CH\CH,CH,Li+ D,O jg CH + NaH aac _Lit D,O—Fexane olution obtained in (d) +1,0 >317 1 Steric “ o-n + Nalco, — {9} + NaH 5 Answer 1. co, 2.€O, 3. CO, 4. Hy nH, Ro CH, cn, Xo, % om the carbon atom of the phenyl ring and nitro; present in 2 and 6 positions, this coplan ice, Next, consider compounds (P) and (Q) gen of amino moiety lie in the same plane, When the sub- ‘arity is inhibited and the lone pair of nitrogen is not involved in (P) (Q) id (P) due to steric hindrance across nitrogen, bond rotation across C1 and nitrogen will be hindered pair of electrons on nitrogen is configured perpendicular to ring thereafter. will not be involved in fe with the phenyl ring. As a result, the compound (P) is more basic than compound (Q), because the lone ogen is not involved in resonance in (P). stabilities in the following pair of carbocations Answer v Y Carbocation (B) is more stable than (A) because struc- ture of (B) is resonance stabilized. Resonance is not pos- sible in cation (A) because of steric inhibition, (A) (B)have been widely used for in Merpret ful in inferring the following STPretyibstituted aniline isa stronger base than aniline NH, NI © or OcH, grease in the bond angle of H-N-H leads to increase in steric hindrance; therefore, the conjugate acid of the 3 aniline is unstable. This hinders the protonation of at tol aa 4 n protonation of amino group, Thus, ortho effect of aniline is also pown as steric inhibition of protonation (SIP), However, the ort ine will not operate when tl ' rated BEE ). However, the ortho effect of aniline will not operate when thé ee) ‘Compare acid strength of the following sets of compounds: Answer L COH CO.H CO.H lo” CL ° a i = effect effect effect 0-Toluidine Conjugate acid (unstable) cH, (A) (B) (c) ry a > B oe 2 COW CO.H CO.H Yor leas : Och, Ortho —Leffect +M effect effec! of -OCH, of OCH, ‘OCH, OCH, Bethe Ca “ ®) © ieee 3. COM con CoH oie NO ve eae esac) Compare base strength ofthe following setsof compounds: 2 NH. NH, NH, NH, 1 NH, NH, NH, Om CL OQ ‘ cH, a No, ® © : CH, a) © : cH, (A) (B) ©ny ons fa ; No, “7 lo ‘NO, mNitrotoluene — p-Nitrotoluene 7 oy ) a ‘Carhanton Carbanion Carhanlon nivel by — sable by sailed =RofNO, Clveffet = RofNO, =1ofNO, of NOjonly = FAENO, (Vis makionu) (Trion) follows the order is the following set of nitrophenols AxCoB On on HI on 5, oO" ON. NO, No, ©) « “ I pcssgn will be: F>E>D>B>C>oA er (B) is less acidic than the para isomer (D) due to intramolecular hydrogen bonding. ring has substituent groups showing +R and ~ effects. Consider.for example, the followingcompounds. siiiteaaadiiaiaatanameailil cH, cu; CH; ocH, Fi i ‘OCH, fi CH, - “ my © & ‘The anion ‘The anion ‘The anion destabilized by stabilized by destabilized by : Reffect of OCH, —Leffect of OCH, +R effect of OCH, ‘and stabilized tnd stabilized by by -Leffect of OCH, “Teffect of OCH, (Ais maximo) (Leffeet is minimum) strength follows the order: B > A> C. the following compounds: oH H HH och, o. ‘OCH, HM, ®) © 7S) strength follows the order: B > A> C‘Three (-I) effects pK 475 a a | effect of the substituent a1 a aybridized PK, Values is reflected in the Pair on 5p? hybricizey Protonating 41 effect increases sith length alkyl chain an. base strength.of inductive effect an Base Strength ‘Comment Nu, Lone pair of electrons on nitrogen Increases in aniline is delocalized, 17 Delocalization of negative charge and base strength Base Strength Increases3.18 | Ortho and Pi otfects AE tule and base strength Lone pair is not delocalized in (b) because it violates Bred’ rule Base Strength Decreases Mpa a 1 ~M™ basic strength Base Strength ‘Comment Increases Lone pair of electrons is not delocalized in (b) {due to SIR and so it s more basic. ‘Comment. Base Strength ‘Bese strength deceascs dus. rine elies aerts Conpeund he 20 ay ee 9 1 I we COW CL 2a i cou 42 25 i CHy COH 43 =25 i CH- COH 45 “17 27 S CH; ‘NH, 51 et i 52 H 29 Me cHo-{ in, 53 32 or =NHCH, CH, 3S 3.2 34 34 38 3910,3 10.5 10.6 16 16.0 36 418 | Ortho ond Pars Effects Ey ee 8bah Acids and Bases the conjugate base of each of the followin RWO te 1 acids? =CH ©) CHON (hiro Dases you gave as answe decreasing basicity 8 (0 Problem 3.20 in FC CHINE, (e) CHC, NEW? decreasing acidity. and Bases the Lewis acid and Lewis base in each of the = ¢ ;—O + AICI, — CH,CH,—c1—al— cy, I . a { (CH,— OH + BF, —> CH,—. aa a HOF cH ite each of the following reactions using curved arrows and show all nonbonding electron pairs: i) CH,OH + HI > CH,+ OH," +1 Strength and Equilibria methyl alcohol is treated with NaH, the product is ia" eras not Na’-CH,OH (and H,). why this is so. {reaction will take place if ethyl alcohol is added to tion of HC = C:"Na’ in liquid ammonia? -K, of formic acid (HCO,H) is 1.77 x 10. What is PK,? 7 is the K, of an acid whose pK, = 13 feview Problems [ETI Thal 329 Ac cil HA has pK, = 20, acd HB has a pK = 10. (4) Which ig a” Wh cid (0) Willan acid-base reaction with an equilibrium ying {abe iebt take place if Na’A”is added 10 H Xplain your answer 3.8 0 , " equation, uging the curved-arrow notation, for Ne acid-base reaction that will take place when each OF the following are mixed, If no appreciable acid-base {Giction takes place, because the equilibrium is unfavora- bile, you should so indicate, (9) Aqueous NaOH and CH,CH,CO,HL (0) Aqueous NaOH and CH,SO\H (©) CH,CHLONa in ethyl alcohol and ethyne (@) CH,CH,Li in hexane and ethyne (©) CH\CH,Li in hexane and ethyl alcohol Starting with appropriate unlabeled organic compounds, show syntheses of each ofthe following: (@) GH,—c=c—T @) CD cH, (©) CH,CH,CH,OD 3.32. (a) Arrange the following compounds in order of decreas- ing acidity and explain your answer: CH,CH,NH,, (CH,CH,OH, and CH,CH,CH,. () Arrange the conjugate bases of the acids given in part (©) in order of increasing basicity and explain this answer. 3.33 Arrange the following compounds in order of decreasing acidity: (a) CH,CH =CH,,CH,CH,CH,,CH,C=CH (®) CH,CH,CH,OH, CH,CH,CO,H, CH,CHCICO,H (©) CH,CH,OH, CH,CH,O+H,+, CH,OCH, 3.34. Arrange the following in order of increasing basicity: (a) CH,NH,, CH,NH,",CH,NH™ (b) CH,O", CH,NH’, CH,CH,” (©) CH\CH = Cit, CH,CH,CH,, CH,C=C 3.31 General Problems 3.35. Whereas H,PO, is a triprotic acid, HPO, is a diprotic acid. Draw structures for these two acids that account for this difference in behavior. 3.36 Supply the curved arrows necessary for the following. reaction, ) H-e + RTS aaa .O—CH, 1Q—CH, eHe acta | name square acta both protons on a , dianion obtained ait." the carbon-carbon joni! the above sequence of reac, for A through E. mtr te the reaction sequence, shoy, ponding electron pairs and using cor "show electron pair movements, plete and balance each of the eq choosing among ethanol, hexane, an, te which (there may be more than 9 ‘solvents for each of these reaction’, si limitations that come from co; 2 Sato OH (Iv) ‘« (b) I> 11> II>1V (@) 1V>Ul>1>1 that has the indicated hydrogen ant respect to increasing acid (b) (1) < (im) <(l!) (@) (a) (V)>()>(1) (b) (1) > A) > AV) > (1) (© (N)>(v)>()>() a) GY) > GID) > G1) > (D 10. What is the most acidic of the hydrogens on propyl acetoacetate? (CH,—CO—CH,—CO,—CH, —CH, —CH; v w xan @Vv ow @x WY 14. Which of the following compounds has the most acidic echydrogens? @ oO : l ) i cucu, CHO, © o @ i ° 0 oleae CH cucu, 42. Which hydrogen in the following molecule would you expect tobe the most acidic (i... most easily removed as H")? i, iH, » es » ff oe NH, oe cc Ce Ne - ‘OH H Ht jer 43, Most acidic phenol derivative HH 1H @ ()13 15. Te com ang lowing species is ———.0.NH, OH, NH (@) NH; > OH->NH,> 1.0 (@) OH>NH;>H0>NH, (©) NH,>H,0>NH;> OH (@ 1,0 >NH, > OH> NH; 16. The compound having most basic ritrogen is “2-0-0 roan Ou ‘Tata number of moles of NAHCO, consume, y reaction wil be (x).S0 the value ofx will ne Matrix Match Type a (a) CH,COOH () 5.69 (©) (CH),N'CH,COOH (427 (© (CH).N'(CH),COOH @ 183 @ 0,C-CH,-COOH (8) 4.80 2 ‘Coumat int Colum i fo s-nsioo (Pp) NH, —O—H + Nao. “ ) eo @Co, ? Optom — Boo O)f otra — ir 1.) 6. (d) 7-© 40) 5. (b) % (0) 10. (b)12. (b) 13. (a) 14, (c) 15. (a) Type " ;c-9(q); d(p) +(q);c—+(s); d(p)