ORGANIC ACIDS AND BASES Prepared by Maria Nora 8. del Rosario ACIDS AND BASES Same common household acids (left) and bases (right) Solution pH NaOH, 0.1m ~~~ Household bleach Houssholc ammania Milk of magnesia — Cola, vinegar Lemon juice — Gastric Juice -Arrhenius Concept ‘Acids * substances that ionizes in water solution to produce Hi... or HO e.g, HCl, H350,/ HsPO, HOAC, H,CO, strong weak He: —— HO" +: hydrogen chortle 10: tor é HG HT é cae ag + eng Sar acatic acd Monoprotic/monobasic acids, e.g. HCl, HNO, Diprotic/dibasic acids, e.g. H280,, HCO, Arrhenius Concept Bases « substances that ionizes in water solution to produce OF eg) e.g., NaOH, Mg(OH)},, Al(OH)5 H,0 NaOH > Nat.) + OH js) Manohydroxic / mono-acidic bases, e.g, NaOH, NH Dihydroxic / diacidic bases, e.g, Mg(OH), The M*"(OH), type where M is a metal of very low conductivityBronsted-Lowry Concept Acids ® proton donors & Contain H attached to arather electronegative atom, e.g., HO, ROH, NH,, RNH, Bases ® proton acceptors > Must have an unshared pair of e's with which it can attract and hold a proton, e.g., OH", H,0, NH,, NH, CH,O-, CH,GH, CH,OCH,, CH,;, CN:, CH,NH, Brénsted-Lowry Concept a@ & J = & A proton-transfer reaction. When s proton is transferred from HCI to water, HCI acts as the Brénsted-Lowry acid and HO acts as the Bronsted- Lowry base. A gas-phase acid-base reaction. The HCliy escaping from concentrated hydrochloric acid and the NH,,., escaping from aqueous ammonia combine to form a white fog of NH,Cl,Br6énsted-Lowry Concept CH;OH + HO’ CHO + FLO am acid: CHOH + H,0* — CH,OH + 0 a base a a o I CL HO- c + Ho cHy OL * CHT eam an-aciel 9 one + oF Ss + HO CHy “OH a ~ base HN, + HOW CH,NH + HO an acd CHNH; + HOt == CHAN, + H0 a base Lewis Concept Examples: 1 Atoms or molecules that have an incomplete - octet, e.¢., BF,, AICI, ed 2. Cations, e.g., Be, Mg‘, Al’? ecu nony Agi + 2NH, > AgiNH,),t ee AP + 6H,O > Al(H,0),% ® Must be electron deficient; it must havean empty orbital capable of receiving the &- pair of the base 3. Compounds that have a central atom capable of expanding its valence shell, & Sif, + 2F > Sif? SnCl, + 2Cr > Snci? 4 Compounds that have an acidic site because of one or more multiple bonds between atoms of dissimilar electronegativities, €.g., co, + OH > HCO, 5. Carbonium ionsLewis Concept Bases * electron-pair donors ® Must have an electron pair capable for sharing. ‘the curved arrovs indlcates enere the pair of electrons. Starts trom and where fends up = a cca” + cHcH, <= ci-ardtcn, 1 & du, aluminum wrichloride dimothyl othor ahowisacd a Lows base HO H HOH ash + ae —= ae 4 borane: ammenis a lewis acid a Lowts base EXERCISES 1. Determine the Bronsted-Lowry acid, predict the product, and write the equation invalve in the following solutions (a) (©}}OH in NaQH (b) H550, in HNO, (c) HCI in CH,NH5 2. Identify the Lewis acid and complete the following equation: CsH, + SO, > CH3Br + FeBrs >Strength of Acids and Bases From Arrhenius concept: % The strength of an acid is defined in terms of the concentration of H*j,,) that is present ina water solution of a given concentration of acid, and the strength of a base depends upon the relative concentration of OH in an aqueous solution of the base. tii These three solutions contain the acid- base indicator brothymal blue. (a) The NaCl salution is neutral (pH = 7.0}; (b) the NH,CI solution is acidic {pH = 3.5); (c} the NaClO solution is ‘basic (pH = 9.5). Strength of Acids and Bases » Strong acids / bases are strong electrolytes virtually 100% ionized in water solution to produce solutions with relatively high concentration of H"jsq OF H39°/ OH tag) Weak acids / bases are weak electrolytes incompletely ionized in water solution to produce solutions of relatively low concentration of H¥ aq) OF H,0*/ OH faq) H,0 " F HCl > Hig + Choa) 100% ionized H,0 HOAC > Htiag) + OAC iq) 19 ionizedStrength of Acids and Bases = For weak electrolytes, a dynamic equilibrium exist. © Acid/Base strength is measured by the acid (or base) dissociation constant. HA + 4,0 =5 H,0' + A~ = — HOTT _ gy x, - HHOTUAT a Tay 7 Kel 0 ca [HO] - Beeqaitorars = Ka = [HAC HOAC = Hy + OAC hoa) er Prot RSneDE. Where Ka = acid dissociation constant Gy kb [NH,J}0#) 2 en . NH] NH, _NHs%ay * OF om) Where Kb = base dissociation constant Strength of Acids and Bases |the Henderson-Hasselbalch equation | pH = —log[H,07) —log K, » Ka (Kb) gives a qualitative idea of the strength of the electrolyte The larger the Ka (Kb), the stronger the acid (base). ‘ pKa (pKb) relates to a pawer of 10 and negative value. Hence, the smaller the pKa (pKb}, the stronger the acid (base). ‘very strong acids moderately strong acids weak acids extremely weak acidsStrength of Acids and Bases Ka Ka Hclo, > 10° H-C=C-H 10% CH,COOH = 1.8 x 10° NH; 10°35 {o)-OH 108 HjC=CH, = 1042 HOH 10“ HAC-CH, = <10* CH,CH,OH 108 The organic classes of compounds by decreasing acid strength: RCOOH > ()-OH > HOH > ROH > HC=CH > NH, > RH s Strength of Acids and Bases From Brénsted-Lowry Concept: The reaction of an acid and a base always leads to the formation of a new acid and a new base. The reaction is actually a competition between the 2 existing bases for a proton. The strength of an acid is determined by its tendency te donate protons; the strength of a base is dependent upon its tendency to accept protons. The stronger the acid, the more readily it donates a proton; the stronger the base, the more readily it accepts a proton. @g,Na'cH,coo + HCl HOAc + Natch stronger stronger = weaker = weaker base acid acid baseStrength of Acids and Bases Conjugate pair = An acid-base pair related through the loss or gain of a proton. eg. HOAc + H,0 > H,O* + OAc acid, base, acid, —_ base, Conjugate acid-base pairs HOAc-Oac” H,0*-H,0 HEE Birk Hr anacid a base anacid NH, + HO: = + HO abase an acid an acid a base Strength of Acids and Bases + A strong acid with a great tendency to lose protons is necessarily conjugate to s weak base with 3 small tendency to gain and hold protons, Hence, the stronger the acid, the weaker is its conjugate base [ Ng (eq) + HzO(t) ss NH," (ag) + OH™aq) Base Acid Conn gate Conjugate * ina given reaction, the position of equilibrium favors the formation of the weaker acid and the weaker base. RCSCH + HO = hydroxide anion weaker base = Rt acetylice anion + Ro = weaker acid amide ion acetylide fon: weaker base [Rrenger acid] weaker acid]Strength of Acids and Bases NH3 NHa* Hydrogen ion transfer. A HO molecule acts as a proton donor (acid), and NH; as ¢ proton acceptor (base). Only a fraction of the NH reacts with H)0; NH isa weak electrolyte. Strength of Acids and Bases “The weaker the base, the stronger is its conjugate acid. “#Stable bases are weak bases. “The more stable the base, the stronger is its conjugate acid. i + NH; = c. cHy ~o7 stranger base weaker base = CH;CH,O- weaker base stronger baseStrength of Acids and Bases + The relative base strength of the conjugate bases is just the reverse. In order of decreasing base strength: R'>"NH, > HCEC > RO" > HO" > (2)-0" > RCOO™ 5 [acidic form basic form RCOOH == RCOO- + Ht RNB; RNH, + Ht Strength of Acids and Bases Felatve acd strengths Faia cy cy, pees felative base strengths SmONgeSt S.CH.CH > HyC=CH > NU > HC=C > HO > raEXERCISES 1. Identify the canjugate base of the ff. compounds. a, b. (s)-cooH = 0H 2. Given the following pairs of compounds, predict if any reaction will take place and give the products a.CH,COOK + HOH b.CH,COOH + CH,CH, c.H-CSC-H + NaNH, ©. (CHg)sCOH d. CHjNH, Structural Effects “To be acidic in the Arrhenius or Brénsted- Lowry sense, a molecule must contain H. “PAppreciable acidity is generally shown by compounds in which H is attached to a rather electronegative atom (e.g., N, O, X, 3). } The bond holding the hydrogen is polar and the relatively positive H can separate as the positive ion. > From another viewpoint, an electronegative element can better accommodate the pair of electron left behind.Structural Effects Acidity is HA = A + Ht anion proton CH,CH;OH — CH,CH,O” + BY ethanol > The more stable the anion, A’, the more acidic is HA. > Acidity depends on how much A‘ readily accommodates the negative charge of e’s left behind. " The ability to accommodate the ‘pair seems to depend upon several factors (1) the atom’s electronegativity, and (2)its size. Structural Effects Acid strength: Binary acids, HX, where X is a nonmetal chy Nis 4,0 HF In polar solvents, (or H-CH,) (or H-NH,) (or H-OH) Hel | || acidity increases due as to inc. size (or —___ > © polarizability} of X HI In non-polar solvents, Acidity increases due to increasing acidity decreases due electronegativity (or en) of X to dec. enofX + The strength of an acid is often @ combination of all three factors: (1) polarity of the H-* bond, (2) the strength of the H-X bond, and (3) the stability of the conjugate base, X-Structural Effects relative electronegativities: C < N< O< E lrelative stabilities: “CH, < "NH, < HO- < F- most stable relative acidities: CH, < NH, = H,O < HF strongest acid pea3 RoI) pheda Structural Effects relative electronegativities: oF > Cl > Br > I nod ] electronegative relative stabilities: Be Ch a Bes i relative acidities: HF < HCl < HBr < HIStructural Effects The pKa Values of Some Simple Acids CHa NHa HF pk, = 50 pKa = 36 px, = 3.2 HC! pk, = -7 HBr pk, = 9 HI pk, = -10 Structural Effects “ To be basic in either the Brénsted-Lowry or the Lewis sense, a molecule must have e-pair available for sharing. ® The availability of these unshared e's is determined largely by the atom that holds them: its electronegativity, its size, its charge. ® The better an atom accommodates the e"pair, the less available the pair is for sharing.Structural Effects Basicity is He + ‘Bo == H:Bt ‘NH; —= H—NH, base donates a share in a pair of electrons > The more available the nonbonding e’pair of B, the more basic. & The more the cation, HB*, is stabilized, the more basic is B. } Basicity depends on the ability of HB* to accommodate the (+) charge. Structural Effects Base strength: Brénsted-Lowry bases 1. For monoatomic anions of elements of the 2" pd.: NB > 02>F CH, > NH, > OH: > F | Base strength decreases NH, > 4,0 HE ck | decreasing (-) charge onthe ion Basicity Br & decreases F w/ increasing en 2. For monoatomic anions of similar charge Base strength decreases with increasing sizeThe pa Values of the Conjugate acids of the Leaving Groups of Carbonyl Compounds Ccarbonyt Leaving Conjugate nt ot cane ame eee ke Own i i we o Wa = Ak Aa Jo x i ae ae nr “9 a OR! one ROE ~1s ln “On Oo 13.7 less 7H, NH ae on rod Hy 0 i. . Go Structural Effects relative basicities of the leaving groups Ro cle cn on onEXERCISES 1. Arrange the ff. compounds in each set in order of increasing basicity. 3.F,HO",HjN,H3C b. HF, HO, NHS RCH,OH > R,CHOH > R,COH + R releases e's, destabilizes anion and thus, decreases acidity. CH,OH CH,CH,OH methanol ethanol Pi s 15, Electronic Effects o o 1 wt or }cH; “OH H™ “OH = Trend in Acidity ateticacid) formic acid PK, = 4.76 pK,= 3.75 For the carboxylic acids 1. ee > HCOOH > CH,COOH 3.75 472 pks values: 2. Oo -o > S 2 H,Electronic Effects Acid Strength ies ‘oF e'w/drawing substituents ereleasing disperses the (-) charge substituents > stabilizes the anion intensifies the(-) charge > increases acidity. > destabilizes the anion > decreases acidity. a o 6 a o I I 1 I oe Zon, ae Zon aon Hy “OH = ICH “OH BICHy “OH = GCHY “OH = FCHY “OH BK, = 476 y= 3.15 Bk, 286 y= 281 Py = 2.66 Electronic Effects Inductive Effect ™ Trend in Acidity 3. CHyCH,CHCICOOH > CH5CHCICH,COOH > CICH,CH,CH,COOH 2.84 4.06 452 | pkavslues Inductive effect decreases with distance. 0 o o i I 1 é é (CH.CH,CH,CH” “OH CH,CH.CHCHS” “OH CHCHCH,CHS” “OH CH,CH.CH.CHy” ~OH BK,= 2.97 pK, = 461 k= 458 bk, = 471 EXERCISE: Which compound in the pair is the stronger acid? 2-chloroethanol, ethanolElectronic Effects pKa Values of Some Aliphatic Carboxylic Acids. pKa values HCOOH 3.75 CH3COOK 472 CH,CH,COOH 487 (CH),CHCOOH 4.34 (CH,);CCOOH 5.03 pKa values CICH,COOH 2.86 CLCHCOOH 1.26 CL,CCOOH 0.64 pKa values CH,OCH,COOH 355 N=CCH,COOH 2.46 O,NCH,COOH 1.70 Electronic Effects Inductive Effect pa CHSNH; Nis = Trends in Basicity eee aaa ® For the aliphatic amines (H,C),N-H > H,C-NH, > NH, R releases es R releases es makes unshared epair stabilizes ion more available increases basicityElectronic Inductive Effect Effects = Trends in Basicity > For the aromatic amines Electronic Base Strength Effects NH, (oy ew + Ht Electron-releasing group pushes electron towards N > makes e-pair more available for sharing with an acid. +NH. oa ow Electron-releasing group disperses the positive charge > stabilizes the cation > increases basicity.Electronic Effects Base Strength NH, em. «J G Electron-w/drawing group helps pull e away from N > makes e-pair less available for sharing. (ey G Electran-w/drawing group intensifies the (+) charge > destabilizes the cation > decreases basicity. Electron Resonance Effect = Trend in Acidity Examples: > For the organic acids: &: RCOOH > CC H_ H(or R) ic Effects 2 > HOH > ROHElectronic Effects Resonance Effect The acidity of a carboxylic acid is due to the powerful resonance stabilization of its anion. PP Ro — ‘Gn relatively stable *+Resonance contributors of a carboxylate ion are exactly equivalent structures. Hence, the anian is resonance stabilized. Electronic Effects Resonance Effect fSSmeGa cr i cHeH, cae Ost pi, = 4.76Electronic Effects Free eneroy Electronic Effects : piesa bilized anion phenol 7205 O= Ox om phenol ceneninel Phe 10 BK, = 16 she ‘sElectronic Effects The resonance forms show that groups which withdraws e- when placed at o- and p- positions should make the phenol more acidic. OH gt er oH O,NYA-NO eNO, o Oy 0, “Yo, 0, K+ —___ oO Solubility class AL Soluble in both 5% NaOH & 5% NaHCO, Solubility class AZ Soluble in 59% NaOH but Insol. in 596 NaHCO3 Electronic Effects “ The ability of aldehydes and ketones to undergo tautomerism exhibits the acidic properties of the a- hydrogens. & The high acidity of the a-hydrogen of aldehydes and ketones is due to the ability of the carbonyl group to help accommodate the negative charge of the resulting anion. ° ° | RCH-C—-R == R-CH—C-R t $s oma] baselElectronic Effects 2 rb cucn, — n_-¢ocnen, te d K an enolate ion Electronic Effects Resonance Effect “Only aldehydes and ketones with a-hydrogen exhibit reactions due to acidity of a-H Aldehydes & Ketones Aldehydes & Ketones with oH with no aH P CHy CH;CH, HG H3 H o ° CCH, CH OF cyclohexanoneElectronic Effects Resonance Effect q 7 RCH—C—R eal keto tautomer enol tautomer [Base- & Acid-catalyzed Enolization acid- Bia aeons “#Benzoic acid with ortho- substituents tend to release a H* ion much more easily than with meta- or para- substituents. Steric Effects = Trend in basicity For the amines (H,C),N: < (H,C),NH “ The presence of three methyl groups in trimethylamine makes the lone pairs of N less available for protonation.Steric Effects » For the aromatic amines — Br ~~ i Orn < er )-NH, + Substituents, whether ereleasing ore w/drawing, weaken basicity of aniline when they are o- to the amino group. Hybridization changes Example: ™ Trend in acidity for the hydracarbons: HCSCH > H,C=CH, > HC-CH3 Follow trend in electronegativity of the different hybrid ¢ Csp > Csp? > Csp? H attached to triply bonded C shows appreciable acidity * sp orbital has the most s character > pair of e's is closest to the nucleus & is held most tightly > most electronegative > can best accommodate (-} charge R-C=C" is the most stable anion IHC=CH = -H;C=CH; — CH;CHs ethyne ethene ethane pKa= 25 pK, = 44 pK, =50Intramolecular H-bonding O-H...0 Acidity: (un < O -O-N*=0 “+The ortho isomer is less acidic due to intramolecular H-bonding. eS Acids J Bg | Structures, Names, and pKa Values of Some Simple Dicarboxylic Acids ee —— mee volo cone ols ei sedge iain stew selon iad an ee Ce oe oes aeEXERCISE Explain why the Ka’s of the acidic hydrogens of low-MW dicarboxylic acids, HOOC(CH,),COOH differ such that Ka, > Kay, but for dicarboxylic acids of high-MW Ka, = Ka. pKa values of benzoic acids Substituent Ortho- CH,0- 4.09 CH,- 3.91 H- 4.20 cl- 2.92 O,N- 2.17 Meta- 4,10 4,27 3.82 3.49 Para- 4.47 4.37 3.98 3.42pKb values of anilines Substituent Ortho- Meta- Para- H- 9.4 Br- 11.47 10.42 10.14 cl- 11.35 10.48 10.02 N=c- 13.05 11.25 12.26 CH;0- 9,48 9.77 8.66 CH;- 9.56 9.28 8.90 O,N- 14.26 11.53 13.00 CF3- 10.80 11.25 pKa values of phenols Substituent = Ortho- Meta- Para- H- 10.00 Br- 8.42 8.87 9.26 cl- 8.48 9.02 9.38 N=c- 7.95 CH,0- 9.98 9.65 10.21 CH,- 10.29 10.09 10.26 O,N- 7.22 8.39 7.15Approximate pKa Values a protonated akcohol ‘OH 1 oes Ro “OH a protonated catborylle add +H," protonated water pKa Values ‘OH CHOH CH.CH.OH é “HL = ie cHy “OH protonated methanol protonated athanal protonated acetic acid pK, = 2! 2d Pi, = “6. CHNH, CH,CH:NH; protonated methylamine protonated ethylamine | = 1047 pK= 110 CH.OH ‘CH.NH, methanol methylamine pk, = 15.5 pk, =40 ‘CH,OH, CHSNE; protonated methanol protonated methylamine. pk,=-25Reactions Due to Acidity and Basicity Reactions used to determine solubility of organic compounds in acids & bases °O a NaOH — RC + HO ON 0 oO # s RC NaHCO, —* RG + H,O + CO, \ ‘ OH ONa* A stronger acid can displace a weaker acid from its salt. Reactions Due to Acidity and Basicity ONa* + H,O O-H NaOH | ONat + %H, Na R-OH + Na R-ONe* + 4 Ho.) To differentiate phenol from cyclohexanol, use 5% NeOH OH HReactions Due to Acidity and Basicity R-CEC-H + Na + R-CECNa* + 4Hy,) R-CEC-H + Ag(NH,),NO; > R-C=C-Ag +NH,NO; Se pea ‘Reaction used as 2 quali test for acer H R-NH, + HCl + R-NH,*Cl EXERCISES Arrange the compounds in order of decreasing acidity. a. 2,4,6-trinitrophenol, p-nitrophenol, phenol, p-methyl phenol b. methyl alcohol, ethyl alcohol, isopropyl alcohol, t-butyl alccholEXERCISES Arrange the compounds in order of decreasing basicity. a. NHg, aniline, aminocyclohexane b. CH3CH,NH, HO-CH,CH3NH3, HOCH, CH,CH,NH, c. aniline, p-methoxyaniline, p-cyanoaniline