* Acid-Base ( | * C { £ ® C OH + Hye == CHAOH, + @ Bromsted-Lowry Acids & Bases @ Lewis Acids & Bases @ Acid-Base Equilibrium @ How t Rank Acids & Bases Qcording tm Their Strength @ Equitibriam Constant Caveutations @ Typicad Acid-Base Exam Questions @ pKa Table & How te Use Tt Code: ATIEEOcid- Base Equitibrium “ Dissociation of a generic acid can be represented by the following equation HA =—= H®+ A® Reconding te the Brénsted-Lowry definition, conjugate the is @ donor of H® while the base base is an acceptor of H® in the solution Examples: oO oe © CHC?) GNHy === CHC? | + NH SN 2uS = S08 ‘ ~ Cacia base) conjugate) — coniuy bose atid, IMPORTANT: Once the acid toses the » ib becomes a conjugate base Cikewize, When the base accepts the proton from the olution, it becomes the conjugate acid. H-O,.40 “Aom + sf 4 HNO LC eto OTR So 207s J vee base acid: conjugote conjugate we wea STRONG ACIDS vs WEAK ACIDS ‘Strong acids dissociate warty Quantitavely while weak acids dissociate partially. We describe the oni tent of this “dissociation with the Ka & oka. values a cts © 2.» LomeoSItH] CH Co == CHece tH ‘om on oe TOR COOH] aes 5 Ka. of CH3COOH = 18x40” => acetic acid only dissociates partially, => Qcebic acid is of weak acid. High Ka = strong acid & Low Ka= weak acid Raw Ko values are hard. to operate => we use pKa values instead By definition, pka= — tog Ko. - pka. Of CHACOOH = 4.45 Low pka.= sbong acid & High pka= weak acid Ashiasis Tyg Sov Code’ ATIEEHO-H 48.9 Hy ®o-4 hoe Hee a weNN 8°) ppc a8 . 7 oH -48 O-H H eo Aged ES ®0-H HS-H 20 | Hyc-c ae i aXe 2 H-r -4.0 Rh eg Proc? 4.2 Ig. net os ordre 6.2 H-Be -4.0 SO-H 4 _H e “4.0 wa ae | earch, oss Seam «hom H H-F 3.2 ° a ZR we Fyc-C% -0.25 aw 19-20 |R R H-cN 9.2 *o-H RS 22-25 Osx -2.4 ARR ee OK" HH j H-O,, Ree Bet CHa-O-H 15.5 SH H-O7"$Q 2.0 eH Koy 7° eobok “4 RO 2.2 H-O 24 - HOH [foSpe0 22 | ProorH 10-0 Jo RA oss H-07 12.3) | Ss-H 100 |g Q oR LH ° — Nob he Ris HON ~A.8 Phos 0 HH -\ Ke q NH 52 [ecg cy |" ea) H-07F$0 65 1 ‘e -N>- 40.5 R-G-H 45-©O H-H as R y H MsO-H -2.6 |. | UH ° 4H K=C0 40-50 i a Aa Ax, 5 \ TsO-H 2.8 Hyc7 CHa, Ph-N-H 4.6 —CSCH 23-20 e 4 TEO-H | -44.0 4 Hal-C 82 cx 45 oH H-CEN-H -12 Hx@_H H ay 9.2 dgC-H 25 How to find the K of a XN N=C-CHH 25 | HA+ & <= e+ He Ko. CHEP- pka CHA) =10F HOO-H 44.9 OuN-CH2-H 44 K Molenaicildrig Siydrogens are hightighted . Code: ATIEEAcid - Base. Equilibriam Summary. Type 4: Ocicity HOA —— He+ AP librium ® determined by the stobihty of the eo Conjugate base a Type 2: basic Neo t B+ Ho == BH Equilibrium is determined oy the auailability of the aiebbon pair on base B+ Factors Affecting Stability of AP Dt mgjor resonance condibutors Cmore = more stable) Z e ~E vw Ae Ke NO reSonance 2 resonance structures ° = ou ica sbonger acid than ~~ou pka= 495 pka=10 @ Size of an atom with the © charge Coigger = More stable) é nd S is in 3 period while O's in the 2 ~S& w rE >sis0 "rarger Gon =? Ns 5 2 stronger acid than “oy pKa=10 pka= le @B) Electronegativi an odom with the © charge larger = more. gee f 8 8 stable.) “~8 vs Ry a5 BO + Blechronegartvity. =? on iS @ sbenger acid than —~nuie Pka=10 pka=3e A Inductve effect of neighboring Elecon- Withdrawing, Grcueps o Oo r on a CHa C_ ve (FECH-CL pko= 2,60 ‘OH “5 ‘OH pka= 4.30 XN Electron -Withdrowing Group Code: ATIEEe Hybridizetion of an atom wth the © charge (sp >sp*> sp CHa cae? vs CHs-CH,— ay $ sp 39° <— Hybridization =? CHa CSC-H iS more acidic than CHa-CH2—CHs pka: 2s pka= 55 These factors are, listed in order of their appoximate importance , so poag. > analyse ypu compounds in rae 23a ® St oe ‘the ‘rst erence , then stop there Factors Affecting Electron Availability of Bs As we are, essentially, looking edt the reversed equilibrium » the factors are also reversed: ® Resonancely conjugated Zs are less basic $ uF 8 #— — loca lized x AH ays) is less basic than (a * conjugated @ Electrons on smaller atoms are more basic Nu, is more basic than Ps (Nis smaller than P) @ Atoms with lower electronegativity. are more wasic e CHg-NH is more basic than CHa-o 40 as ~ Elecbronegarts ay AD Trductive effect of neighboring EWGs decreases the basici 2 F-CH, is less basic than CH, |B Higher hybridizations make Z's more available , thus increasing basicity CHar CHa NH iS more basic than Clg Cnt e Sp <— Hybridization © Slectrons should be sterically. accessible “AH, is more basic than Ara Ash Tyggy Sd R Code: ATIEE@ Consider the reaction you have, e.g ° °O CHs-c? + «CHO CHa-C% + CHOH ‘OH ‘o® (D) Taentify the avid & the base for the reagents and their conjugates: ° ° CHs-C? + CHO CHa-C% + CHAOH ‘OH oe acid base conjugate conjugate bal aot @ Cotions: Compare the bases => equitibrium shifts inwards the weaker base ° © e ° CHS us CHa Co CH a I Oo a oS Crore stable cue te the resonance stabilization = equilibrium is shifted towards the CHsCCO® species Option 2: Compare the acids => equitibrium shifts towards the weaker acid oO CHsc% us. CHAOH “OH pko= 4.35 pka= 15.5 weaker acid => equitibrium shifts towards CH3CH. canes £ C ccd eliminating ang peso or uncertainty, Ashiasis Tyg Sov Code’ ATIEEHow to Cateulate the Equitibriam Constant” Consider the following reaction: eo CHy-C + CH,OH NGe o CHs-c% + CHa ‘OH acid, base Conjugate Conjugate cos aed The equitibriam constant for this reaction can be defined as: LProducts] _ [cHacoo ][ cHa0] Ke [Reagents] [ cHyccou][ CHac®] While we dort know the concentrations of the nents in this reaction, we know the tabulated pka values of the acids in this reaction: pka CCHSCH)= 18.5 & pKa CCHyCOCH = 4.95 Since the pka= -togka , we can cosify caleutate the Kas. How does that help? 9 By ‘definition e e Ka CCHsOH)= Leos] = BAoKto” [chsoH] [uP] cHscoc?] “ Ko. CCHaCOCH) = Teneo] = 48x40 Using simple mathematical manipulations, we can show the fretowing: ke [c,cod JL CH30H] = [creed JLH® __[chsox] ~ KaCcHscooH) [chgcoon][ cHsc®] [chscooH] = [cHs0P][H®]_ KaCcscw)_/ Ws bt KaCcHsCooH) 4 Ka CCH3OH) 4 Cc rey aworable towards ue Products. Code: ATIEEHow to Use the pKa Table to Choose the Acid or Bash” EXAMPLE 4 Which of the fottouing bases can quantitatively Ce eee 5 © ° © O ewe AY se HO A 2 N ee N-H He & Cc D e pka= 45 To solve this question, we need to consider the following equitibrium: Oo i Yl {pes + Baoe —~ Cr + Conj, Acid, ous = <3 S Keto 5. 45> pko= 415 re) ee O pka= 4. 1 oN H HOH ° Kat! 5-15, 1? —___ - \ CHO ae a CHAOH pka= 16.5 oo AX Ag plore? 0 ©. 5 ' \wi7 S yard BSS ig CHa CH CZ pka=495 ‘oe “OH AA-45 409) K=10 =40 H,O H30® pkas-49 Since this question has a qyontitodve aspect to ib, youl need to use the pka values “for the Conjugate acids Of each of the bases in question. (Set up the stem far your acid-base equilibrium @ wrte the cogjugate ovis for your bares (B) Find the pKa values of those conjugate acids pkacc.8)- placa) @) Careutote the K values by using K=O) equation B Compare your K values & the K value in the question Ashiasis Tyg Sov Code’ ATIEEHou to Use the pKa Table to Choose the Acid or Bast EXAMPLE 2 Which of the following acids can prtcnate pyridine with K>40° 9 we H,80y Chee HNs = CH30H HO CO A & c D € § “To solve this question, we need to consider the Plowing equilibrium : 3s O + Add ——— = a + Conjugate Bove 5 N N | H pka= 5.2 works! H,S0y kam -S Ke 4082 Lo? = S.2-4A5, O48 CHACOOH pka= 4.55 K= 10 40 6.2-49 _ Os HNa pka= 44+ K=10 40 CHEOH pas 15.5 K=408771S Se yt S.2-159_ 10.5 H,O pka= 154 K=410) 40 An this question we already have a set of acids fir our ts, SO we need te compare their pka voluts with the pka of conjugate asia. formed. by the base in question. (A) Set up the stem fir your acid-base equilibriam @ wrte the comjugate acids fir your base @® Fina the pKa values of the acids in question pkacc.8)- pkaca) @ Coseutote the K vadues by using Ke40 equation ® Compare your K values te the K value in the question Ashiasis Tyg Sov Code’ ATIEEHow to Use the pKa Table to Choose the Acid or Base EXAMPLE 3 3 K>I0 Which base can be used to deprotonate the most acidic proton in Salicytic acid , but eave the second most acidic proton untouched 9. ke keio® © List ° O i possible 1 y—pkaz 3.0 Sw Awd CHa-C. 6g @ | bases . eu CPNO a OH a a c OH pKas 13.8 g Licyeic NH, CH3OH & “Ns Ok D E F Since the acid is given to us with the corresy ing pKa values, weit need to unite the structures of the conjugate acids "made by cur bases: 52-80_ 2.2 almost = 40°" “Works Ky=10 P A j —_—~ I pka=5.2 | S, S, ABB = N Ne Kye 40 Fe ah? H B83 8s Ky= 10° “= 40 Anr >» Ank ses |” 8 T Pp Kon Be 9242 4 2= 10 = 40) Pe ° { Ke ASPB sot 4 CHK —_— CHA pka= 4.45 ° Ky 1077-8 Moe? ee NA, — NHy pka=4.2 A. e Ky 1077 * = 405° CHOH = CHAOH, pas -2 oe K, 407 BB _ 108 i x Ky= 10 F 2 pot —— Ka= 40.8 aDenost e“~_ © en 43. “38 oS oO” on PF Kan 10 PF. yo? Goer Ashiasis Tyg Sov Code’ ATIEERelationship between the pH & pka™ definition, pH = - tog [H°] *woncentration i Q RB What is pH § ak discribes Houo basic’ or of H® in the Acidic the aqueous sotution is Sotution H is oni ficable to aqueous solutions & is meaninggess i ic sotvents. Concierge Seene acid dciatin equations tT oT) ° HJLA H-A === H°+ 0° & ite dissociation constant on we can mathematicaly express the pH via pka: _ [HIP] ° [A®] Ko Tae) > gba tag lHt] + bg -Fas oY Ce] “leg liPl = = beg ka. + bog tual pH pk An important conctusion comes fiom the H-H Equation: if Ca®J=CHAl, then ape s How is this usefid This means that if’ pHpKa, you have more of CA], o in other words, the acid is depotonated. casity determine Wf a certain group is ionized on this principle, we can Coue a given pH value oc oO range. not in an aqueous sotution at Example: ° ° ° °o Bo pkag 2.98 Noy oon Cre . i fers OOM, OC OL A ‘OH ‘OH ~ Of OH" pKa, = 18.82 O1238456934 04 24 PH scale tee saeuces ‘ acidic i Using the pka values for ic Avil, We can concude that at pH< 2.93 the decid is 1 Qt “pH behween 2.99 to 13.82 only the carboxytic acid is deprtei ruohite fully deprotonated acid onty evict at pH 18.82, Ashiasis Tyg Sov Code’ ATIEEMore Examples of the pH- pka Qnadysis' Example 4: Aspartic acid is a non-essential ol-amino acid fund in many mammalian . What chacge ae any) does the aspartic acid have “in physiological: conditions CPi a4) a of pKa +99 at pH= 7.4 Et Ba 1.44) H> pKa, (3.40) HO NHS“ pKa.= 9.90 Cthe - Ru, ) Phe Cea (4.90) Pee . P fen sain re v ays protonated ok PH=7.4 aspartic acid will book Like this: ° °, © . & > therefore , its total WHF “SS Example 2: Ok whot pH succinic acid is fuuly Prtonated in an aqueous soution ? 9 ( Ka,= 4.2 Since the Cowest pKa is 4.2, need WoAL 0H P P yee pka,=S.6 tre pH of your sodution tp be <4.2 t howe © the succinte acid to stay filly protonated. succinic acic Example 8: Qk which pH the amino acid gPycine has the overatl change = p © HN-CH,- & os Phan 2.34 pka=0.65 8g pe SO os © 8 SN ° @ oe the 73g MENTOR HAN-CH,- CO at © eons, the pH when its a5 o Perfectey neutral is 4 fer 6232565 total charge Ashiasis Tyg Sov Code ATIEELewis Acids & Bases “ Lewis acid-base theory is abt about electrons Lewis Acid = electon acceptor Lewis Base = electron donor Typical Examples Typical Examples of | QU Lewis acids have an Foie Guide f ¥P Lewis Bases incomptete valence electon z shell, while all Lewis bases BH, NH howe a spare electron pair BF, HO: that can be used for Alcs PPh, i FeBrs CHaOH ae K Lewis acid-base reaction is typically called 2 complexation & the product of such @ reaction is catted Lewis Complex: ¢ Pn em a HB NPL ph ———>_ H-E-Bo Ph” “Lewis complex i pa Compleiaion PNG Lewis Lewis H asia base 2 KX woos oe + mel ae §-ah ew Lewis Complex Lewis Lewis a base acid The complexation equifibrium constants axe often Large, however, we will fypicatty ony see Lewis acids as sts in WFC reactions & wont be fPeusingy on qhantitative aspects of thaw elaine. Ashiasis Tyg Sov Code’ ATIEE