3.1 THEORIES OF ACIDS AND BASES General Properties Acids Teste sour : ‘Change colour of wet . =. blue litmus paper to red . Sean 0-058 (oH<7) e React with metals a sAmsB RL — 7 “The pt values of some familiar ‘aqueous solutions. ARRHENIUS THEORY OF ACIDS AND Bases ¥ classifies these substances interms of theiy behavior in ware PSOE EESe “Arrhenius acid A supstance twat, when dissolved Asubstance that ,when Mm water, creases The concentration dissolved in water, increaser of hydeoxiae 16n,O8 Cag? ithe Arrhenius Acid Arrhenius Base NaOH HC\(ag) — H* (aq) + Cl"(aq) NaOH(aq) —+ Na* (aq) + OH™ (aq)LIMITATION OF ARRHEMIUS THEORY oF AUS AND BASES 4 only Considers acid-base reachons only inaqeous solutions: Naot cag) + Mag) ——? Nad ( tho awhenjus bate awhumut aid - it Vimits = -base to compounds that contain’ hydroxide ion eg: NH3 , Nato , Na.0 acids thai contain hydrogen ion eg (02, 503, 80,3.1 THEORIES OF ACIDS AND BASES Bronsted-Lowry Conjugate Acid-Base Pair ‘The Bronsted-Lowry concept provides broader definitions of acids and bases. Thus, further develop the Arrhenius theory. ‘An acid-base reaction invol @6B-e-.e Ho Na ‘ABronsted-Lowry together is compound thal as 08 both cated amphotere 3.1 THEORIES OF ACIDS AND BASES Bronsted-Lowry Conjugate Acid-Base Pair ‘Substances in the acid-base reaction that difer by the gain or loss of a proton, H°, are called a conjugate acid-base pair. HA(@g) + HO = faq) + HO*(ag) Bronsted Acid Bronsted Base Conjugate Base Conjugate Acid B:(aq) + HOM) = BH(aq) + ~—OH-(an) Bronsted Base Bronsted Acid Conjugate Acid Conjugate Base Note: Water can acts either as a base or as an acid 3.1 THEORIES OF ACIDS AND BASES Bronsted-Lowry Conjugate Acid-Base Pair Example: [Conedorh otowing ait-bar reactions. ently the ai, base, ‘sds conjugate pas 9:-8-08:-8 2) NH, (aq) + HCI (aq) = NA. (an) + C109) 3.1 THEORIES OF ACIDS AND BASES. Bronsted-Lowry Conjugate Acid-Base Pair Consider the following acé-base reactions. Identity the acid, base and ts conjugate ptr aa aca v b)NHy(aa) + ee Base ‘Acid Conjugate acid Conjugate base NlCheckpoint 1 Question | ‘nh the following eqn, idendty The acd base andity conjugate pair- a) COs” (aq) + 0H (aq) 0,” (aq)t Ho (2) acid base conjugate Conjugate A base aud 6) HOS cag) + HF taq) = Wal03 00a) + Fo tag) base acid conjugate conjugate a ye aud base CO tH MNO; aq) t WyL04 194) = MN 05" cag? +H S04 (aa) base acid Conjugate con) ugate el esl aud base 4) He P04 (aq) + OW” (aq) = B20 cag) + HP Og* cag) aud RS base, cunjUgre Conjugate ao oe” add base e) WOW (aq) * CN tag? = Tae (a4) + HUN (aq) aid § bare 3 Gonjugark Cnjugak La ww? hase aua xCheckpoint Question 2 Write the Gnjngade acd or Conjugate base for the folowing species bat i gust cor 4) (03° —>_ ho +) Ha Poy” —> hPow b tad mee is aadLEWIS THEORY OF Acips AND Bases Lewis acid Lewis Base - A specifies that aept etectvon = —- A speues that donate elecwon sepa frem anotner «peur pai © another spit “AN electron =acceptor + Pita thecon.-donoy- Example. BFa, (02 ,S0r, 50a Example mis ,Pds, CN7,OR™ Example: Electron transfer between boron trflouride and ammonia. RECOGNISINGr LEWIS ACIDS AnD Bases Lewis Acid Lewis Base A molecule with vacant Valence Possegs 4 non- bonding otbitals pair Clonepair) of decvory Ce-g- NH3, Pas) on, Capable of awepting an elechon por) —_- Negativery charged jong “A molewle with deocansed Th etechons (eg CW” ,OH) (eg. 6F3 has avacant 2p orbital thvolving two atoms with different “Pnions are better Lewis Uedvoneyativer involving otygen bar than neatral alomy (eg Mr, SO), S03) 4¥ mojeomles (ys ") ~ Generally ;the more Uechonegahve an atom, The less willy it fo be a lewis Bare (0 48)3.1 THEORIES OF ACIDS AND BASES ‘Summary + explained the acid. basedon electon Mansies reactions CHECKPOINT 2 dent the Lewis acids and Lewis bases in the folowing reactions: ye" > At nl Woe + aalgeed we ee (a) aad ad | Alok” Clewis Qewis aud) >) bates) at ya Jer tb) Co®* 4 6 NH; ——> [C0 (NN) ¢ J (Lewis (Lewis auds) bates) a3-2 STRENGTH OF Auvs AND pases The strength of an qed depends on how easily theproten W*, is lost or removed from an W— X bond Cbond srergh) in the acid species -the bond polarity belween Wand the atom fo which itis bonded Types of acids -Binay add, H- x (eg: HO, BBr) Payprohe aud, AmYOn (Ha 60y, W5Po4) - Oxoaud , WYOn leg: HNO3, Hclog) Orgame aud , R-coolt Ceq chy coon) Binary acid , + at going down a qrowp inthe periodic table, The sie af X increases make the Hx bonds get fonger andwearer, dns The strengin of the acids increase: | a 16 17 Relative aud siength WAP << WC

---

H30* (aq) + A’ (aq) ath tela * Cr 4 Astrong base dissociates completely with water. BOH (aq) > B* (aq) + OH (aq) eg: NaOH (aq) > Nat (aq) + OH: (aq) we “We BOH BOH OH Examples: _ Table 3.1: List of common strong acids and strong bases. Strong acids Ae HCI, hydrochloric acid LIOH, lithium hydroxide HBr, hydrobromic acid NaOH, sodium hydroxide HI, hydroiodic acid KOH, potassium hydroxide HNO,, nitric acid Ca(OH),, calcium hydroxide RIA narchlarin onic RalOH\. harinm hudrovide 3.2 STRENGTH OF ACIDS & BASES Weak Acids & Bases Weak acids and bases dissociate partially in water. + Reaction of weak acid with water; HA (aq) + H,0 (|) 7H;0* (aq) + A- (aq) aasocition dissociation eg: HF (aq) + HO (I) =) H,0* (aq) + F-(aq) + Reaction of weak base with water; :B (aq) + H,0 (1) = BH* (aq) + OH" (aq) eg: NH (aq) + HO (I) = NH," (aq) + OH" (aq) a>DISSOCIATION OF ACIDS AND BASES ANMDITS pssouATION constART Raid dissociahon Constan , ka The Strength of an acid depends on he degree of AiSOCIMAhon of the avidin water Consiacy the weak Asociation . WAtaqg) + Wao W30'taqrr A (aq) hevalue of add Aissocianon wnstant , ka can be expressed M -log vajue Where | Ka and pkq ar appncdole for meqsuring ‘me stiength of weak a cid \ Ka for drong aud © erhemuy large 3.2 STRENGTH OF ACIDS & BASES 3.2.2 Dissociation of Acids & Bases and Its Dissociation Constant Table 3.2:K, and pk, values for weak acids chloroacetic acid nitrous acid hydrofluoric acid cyanic acid formic acid barbituric acid acetic acid butanoic acid propanoic acid hypochlorous acid hydrogen cyanide *c. CICH,COOH HNO, HF HOCN HCOOH C,H,N,O, CH,COOH C3H,COOH C,H,COOH HOC! HCN +The larger the K,, the stronger the acid +The smaller the pi, the stronger the acid 2.85 3.15 6.8 x 104 3.5 x 104 1.8 x 104 9.8x 105 4.74 1.5.x 105 14x 105 7.52 6.2 x 10°79 “Write the K, and pK, values,Base Dissociation (onsiant, ky The sWenglh of an base depends onthe degree of dissociation of the base in water kb for shong base i exvemely large Thus, Kb 1s only apphcable for measuring the stvength of weak base Consider tne weak base dissociation = Bcaq) + W0(t) == BUT tag) + OW ca) The stvengihot abase canalso be measured ih terms of pho: pe logk & 3.2 STRENGTH OF ACIDS & BASES 3.2.2 Dissociation of Acids & Bases and Its Dissociation Constant + The larger the K,, , the stronger the base. + The smaller the pk, , the stronger the base Table 3.3: K, and pK, values for weak bases at 25 °C. butanamine C,HyNH, 3.23 methanamine CH,NH> 3.36 ammonia NH, 1.8x 105 hydrazine NoHy 1.7108 morphine Cy7HygNO3 6.13 hydroxylamine HONH, 6.6 x 109 pyridine CsHsN 4.7.x 109 aniline CyHsNH, 9.36 “Write the K, and pk, values.3.2 STRENGTH OF ACIDS & BASES lonic Product of Water Water is amphoteric: behaves either as an acid or as a base. ‘Water is a weak electrolyte and weakly ionized to give H'(aq) and OH(aq) ions. \ a Wp yan) H,0 (I) + H,0 (I) = H,0* (aq) + OH-(aq) Base Acid Conjugate Conjugate ad base We call the equilibrium constant the ion-product constant, Ky K,= [H,O° [OH] At 25°C, K,=1.0«10"* ‘As temperature increases, the value of K,, increases. 3.2 STRENGTH OF ACIDS & BASES lon-Product Constant of Water, K, + Autoionization of water proceeds only to a small extent. H,0 (1) +H,0 (I) = H,0*(aq) + OH-(aq) K,,= [Hj0°]OH-] = 1.0 x 10" at 25°C + In pure water, [H;0°] = [OH], then: [H,0']=[0H] = 10x10 =1.0%10 mol L* + Pure water is neutral because it contains equal concentrations of H,O* and OH" ions. + If there is addition of acid or base into water: > [H,0°] > [OH] ; acidic aqueous solutions. > [H,0"] < [OH] ; basic aqueous solutions. + There is an inverse relationship between [H,0*] and [OH] in aqueous solutions. + As the concentration of one increases, the other must decrease in order to keep K,, constant. 3.2.2 Dissociation of Acids & Bases and Its Dissociation Constant Relationship between K,, K, and K, Boe(Sq) + H,0 (I) = H,0° (aq) +S-f8q) Ky AEG) +H.0 (\) = HtSq) + OH-(aq) _K, 1,0 (I) +H, (I) = Hs" (aq) + OH-(aq) Ky = [Hs0*][OH"] Ik, xk, ~ALIHs0°1, (HAIOH] «Ky = [HA] [A] Kyxk, =[HO-HOH]=Ky | A125°C, Ky=1x10-% CS es 10" ‘Acid conjugate base ‘any acid-base conjugate pair, ek 40% Tegardiess of the strength of Base conjugate ac the acid or base.3.2.2 Dissociation of Acids & Bases and Its Dissociation Constant Relationship between pK,, pK, and pK,, (K, x Ky= Ky) og -log K, + 4og K, = -logk, pK, + PK, = PKy clog=p pK, + pK, = -log 1x10 pK, + pK, = 14 3.2.2 Dissociation of Acids & Bases and Its Dissociation Constant Strength of acid-base members of conjugate pair. There is an inverse relationship between the strengths of the acid and base members of a conjugate pair. ‘The stronger the acid or base, the weaker its conjugate. SuieieSeeoe iacrestewe ‘ase strength ncroasesCHECKPOINT 4 Nitrite ions, NO," in nitrous acid HNO, produce a light blue solution in a cold condition. For the equilibrium that exists in an aqueous solution of nitrous acid, a) Write the equilibrium constant expression for this acid ) Using the following K,, values, indicate the correct order offase sat) No, 7 K,=4.0x 104 . HE Ki=72x104 aa HCN K=6.2x 10% 6 ©) Determine the equilibrium constant (base or acid dissociation constant) for the following reaction; 4) ka = tN to = Wyo. + wot kas Fyso" LENO] Lands} b) Stronger avd, wearer conignyalt \ac WR > WN 0 > WON © WE + Mo & F ttot Gg HNO) + Hau S NOQ? +t Wu! CeN + Wy = CN thot hye NO,” < WN be ky owCHECKPOINT 5 QuESTI 1 oP The dsepiiton of water, Ky sion an © 1,0 (1) +H,0 () = H,0" (aq) + OH (aq) ant ae the value of K, at higher temperature, (hint: larger or smaller than 1.0 x 10" mo L*) doy ry bw F wade J awhCHECKPOINT 5 QUESTION 2 ‘A esearch chemist adds a measured amount of HCI gas to pure water at 25°C and obtains a solution with [H,0"] = 3.0 x 104M. Calculate [OH]. Determine whether the solution formed is neutral, acidic, or basic. ra HO-40 2 Cl +Yyot Nh oF WW 5 yx yo Leso") Lor) se0xe® c Oita > loll 7 Lao) Yot | J AVL Col3.3 ACIDITY AND BASICITY MEASUREMENTS 33:1 pl and poll The concept of ph: the negative of the bare lo loganthm of he molar Hao! concenhati on, ph: -loglh3o'] The concept ot pol Ghegative ofthe bate to logarithms of the molar OH” cncermvahon Pure water at 25 ‘Cc: pls -leg LH30° T= log (oxte ") = 100 pot = ~tog Cow) = tog Croxto) = 1.0 Where Ph astc : ku > Tuyo Lond - box” kw 18 The i6n-product constant water3.3 ACIDITY AND BASICITY MEASUREMENT 3.3.1 pH and pOH PH values for different solutions: Solution pH Concentration of ions Acidic <7 [H30°] > [OH-] Neutral = [H,0°] = [0H-] Basic >7 [H,0°] < [OH-] —— Concentration of H* Concentration of O#”# —————> PSOE OS 6 7 GB) © pu sbysyabeg GS ———— jour > increasingly increasingly acidic basic 3.3 ACIDITY AND BASICITY MEASUREMENT 3.3.1 pH and pOH The Conversions involving H,0*, OH-, pH, and pOH 1x10" [OH] = ; = pease Ora [H,0"}= [OH] tH,0']=10| | pH=—toglH,0"] Oe pH=14—pOHCHECKPOINT 6 QUESTION 4 ‘The 1s in a certain household ammonia cleanir the concentration of Hons ang ts pH 'e concentration of OH: ion: solution is 0,0025 M. Calculate ae Colt] © -co0 M WH: -log TH, 0°) (iy6") dy bol? ji : be dy ok? m) Cot) > |i staal 0-0025M = 40x\07?™ [W30"] = 4-0x0"m CHECKPOINT 6 eee 2 collected in a certain region of the northeastem Unt Sates on a parieuar day was/62 Cau he pie 43h Cu got)? Th30"] ~4B2 = 740 = bso 2M3-3-2 pH of Strong Acids and Bases The concentahon of hydronium or hydride ih solution of strong aud or base is related to the stoichiometry of he acid or base Example Hclag) ts Hao lt) —— OF (ag) +130 tag) 1M Inn M Nag0q (aq) —> 2H30" (aq) + Sq lq) \rw, +4 im Na0ll (ag) —> ON" (aq) + Na*taq) im im \m BacwH) 2taq) —> 20H" (aq) + B47* cng) \m BIN \M wote That, the Strong acid and bases undeigo complete dilsectation when react with water.Example Calcujate the concembation s of hydronium ion ond fydroxide tons and the pl ef Solutions at 5° in: on a-0.15 M_ lnO3 | se \ b- 0-010M (aH), we 4) EVery mote ct _tino3/ comivibutes to one mae. of z0* n,0 The ltgo* cancendahon is 1S. Tre ON" Cenvembation W cbiained ffom-the eq yahon of Kw kw + [Hjo'] Con] Wad; 4 Hiro == Noy) + boxto . 0.05 x [oH] Haut Te Concentvathon of GH” in 015M Hox \66 1x07! Low] = voxe"4 2e-1ye"! 0.45 The pl of HNO; -tog. {i130") >= tog Lot5) can b) calculate the Concentrations ot hydronium ion and hydroxide ions ond the pit of Golurhons at 25°C in Caco. oa Oneal Ca(08), 6) —— ** (aq t208" tag) Every molt of (doll), that dissolves yrerds two motes of on” Qa" {ok Therefore, 0-(10M Cath8)e contains 2x 0.010M__0H~| «0-020 MOR”: The W130" concentration obtained from: ko = £3 0°JLON [oxio™ ~ CHy0"J ¥0-020 CW}. s-oxw-8 pl coon > -10y [50°F = -loghs-oxto""7 +23-3-3 plof Weak Acids and Bases Example: CHa (COON (aq) Ho (2) == C3600" aq) + N30" tag? IM. <<)M <<{M WN3 (aq) + Ho () = OW cag) + Nat cag) \m <<\M <<1M Wote that, weak acids and bases undergo mcomplete dissociation when react with water: Amethods (40 deteymine TMg0*] or Low") 1) ACE table: solve using qua dranc ean i NVE MS ed i) orfeenat Ve _sing Simpified empEnxomple -Calcuiaton ef pt ot weak aud Nitvonic acl, Ce Handa sa form of Vitamin B3 which 16 an efserkat human hutvient nm fhe pH of 010M nicotinic auid Yotuton ttn of WG ano, i raxto? © Write the acid dissociaton equahon and tabulate the Ice table Nicotinic dissociates by donating @ pweton 12 water HCeHaNOg a4) + Hole) == N30 faq) + CeHyNOs” (aq) | oJ} Elan Q ic a - AK th € OV" i ta © write ka expression and subshtute equilibrium concenvaton Values ihto the expression ka = Tec Hew ICH30") ba eyo > [Ta p? | THC hyn.) [o1-4] @ Nise the quadrane equahon to solve x -due to sman_extent of difsociation of weak add ; the value of x will be significantly less than 00M , so the x in tHe dtnominatyr canbe ignored 40. Con u Ow -x F010 han ®|axq Lt 2 TN6D 12 x10M ary @ Carnrate the pH value pis-tog LH30") >-tog Chaxto-*) «2.9Ritevnative method (simpiifying method) Weak acid dissoci hon: HAtag) Holt) == M20 * caq) + Av cag) (Cem Ciba + GaAs due fo small_ extent of weak aud jomahay , ka_=_Cio*1 in" =r cn XC Tua] (a) Kaw? H2VCCx ka) where x - LH30"] c | THy30') - [cex ka) base Ajssouaboy = Brag) + H20(t) == BHT tag) +4 0NCaq) Weak \ iG - > iz -H el +H seu c cre x + Ko = Le* fot] - ani) due toimau extent of weak bave Cwe) ect) ioniahon Cure Monona al- (coheed where x- CoH J © poh - = Jog Con’) pues po delCHECKPOINT 7 ( monoprotic, K, =3.30 x 10-4 at 25 °C. MM : 180.16 g mot pet Calculate the pH of the solution obtained by dissolving a 0.325 g tablet of aspirin, CgH,O, (acetylsalicylic acid) in 0.500 L of water. The acid is net ta mer B0r0 Sad 3 Sq} (qHaby ‘16g mol” 0;S001. 1 S001 of water = baOxw Sol + 8-61X10 > y C caoaaeae Hro()—= 180 Sq) +callaOqta) 4M AG " = na due bsmall extent vonca' (-n) of aud, 1 -can nen beygnord qd a Cc ka_ = [x2 c ka xt =? a . 350X104 x 6K oxo? Tv0') - Lea wm > ~lng J 09x10" )CHECKPOINT 8 Morphine, CHyNOs. isa naturally aloo (akaloi) which "administe pee to relieve Coleulate Solution of morphine at (ac. tC wt aro Cri Hhanos (9) + rot) = CaNgngb (aq) Ca ) Cc cl L c he i +H AH Elemis ed = De Hm Kb = Ces tandgt*] Cow) = O10) due tosmatertent {Crthanos) (c-a) of weak bare ,xignored a Yomabon x ic kio| = |_at qc kb xc =| 23 ee CoxKb) = s} Co.0015m x1-¢x10°99 = boas yjo4 Tot] = oqsxw tm pO = tog (r995xi0 Im) 2 3-46 > 400 poll epi > 1400 pi si4-o0 -poW = 14-00 - 0p pv +03.3.4 Degree of Dissociation Ostwaid diluhon law Thedegvee of disgodabon yanes with concentvahor Howevey, the dliscudhor Constant remain unchanged Percent. sonizahion =lonized aud concenvation at equilibrium a 100%, Invhal cnanwanon ot oud For 4 monopwhc aud HA, percent lonizahion - Ht) x 1002 Cand. = inihal ancentahon CuajoExample -calcuiation of percent ionilahion of acd Aweak acid has a pkq of 4289 Mf the solution pH « 3.2. Determine the percent ioniZation of the acid © convert pka tka -pk -4.289 - ka toll. = 51axio"® @©_the pl gives CH '] {and tne tad) CH'D= oP! 20°87. Gav gto © _ Determine the concenhation of the_weak acid ka > (cwtatwd) /cwnd srgnio® + L6-31x 10%) (6.g1xt0% )] fad CHAI. 1146xIo mM © _petermine percent_jonizahon AW ¢ 00 6.a1slo y 100 = 812 Craq ri4gex®Checkpoi™ 4 Question} A 0.005 M_ weak acid has solution pi 3-3 - Calunlate degree of dissociation =p Inds? 38 raat. = [p93 Mote 4? Tn) UiWAle , =_b¢dxjo M 6-0u5M = ale iG Question 2 A Solution of acehc acid ,Ka =) 11X10 has a ph of 2616. Gkulate its percent toni2aron _ pit Nan ean tard : 2-816 433 x0 3M ka: [utl tad 4A] Leraxte = 033x103) 133 x03) (any Hh oto. a ee (had > yh3-4 SALT HYDROLYSIS Neutra) salt: Basic save thong aud F weal Strong base aud + Strang base “acide Sant Stvong aud t weak audt weak weak base. hare ‘The acid-base properties of ions and. saits “When a Salt dissowes in water, one or both of its tons may read with water and affect the pit of salution These saits are said to have hydrolyzed inwater Salt hydrdysts i$aveachon between a satt and water + ilher hydrontum tons ov hydride ions are spit out of the wate macuteral_ Sait A satt that consisis of the Conjugate base anion) of a Strong aid and the Conjugate acd (cation) of a Strong base. Na cl Nat isthe Cony C1 isthe ony base & 0,0 Grong aad- gad of Nadl a thong base - The anions oF strong audare vey The cation of @ song base WAK Conjugate base iS very Weak Conjugate aud: Heo t = Sal} dissociation Nad) —— Nat (aq) + cag) 0K & i. Naliaq)—> Wa" (ag) +4 CI (aq) Hy droty sic hone Therefore, yitttl a heutvaltolution Aude Salt W salt that consists of the conjugate base (anion) of ashong aud and the conjugale aud Cahon) Of @ weak base ity cl Na tis the Conj- aad a Whe con) base st of Nis, qweak base ha 4 strong aud The ations of @ weak bate are Sheng and hydielyzed inwater {Lo Galt, drssociation Ny Clg) ——> Nita (aq) +O” cag? Hydhotysis Wa Nag) +H 0(0) = 03 (09) 9 Ws 0" cad The Solution will be adic, becawe Ne’ will reat wih lao & predue bot.Basic Salt A sot that consists of The conjugate base of a weak avd and tne conugate add ot a Strong base yields a banc Solution (A300 Na JA aS CH3C0O" is the. Cony Na’ \sthe cory aud _ of: base of Chyc00H, 4 Naot, a srohg bate weak acid The anions of 4 weak acid are strong and hycholyzed Inw ater. Wt: Satt_ dissodaton CH; (00Na os) =, CH3(00" ay) 4 Na? aq) By drotystt Hy (00'cag) 4 Wa.0(L) == CH,L00H faq) +40 N° (04) Thesoluhion with be basic, because CH 6607 will reacl with 20 to produce Ol” —ALSatt ot Weak Aud and Weak Base Hf a. Satt consist of the cony bate of 2 weak acd and the conj acid of 4 weak base, both fons hydrolyze iN waher ~The type ot Sart formed deponds onthestength of dud and base used Niky Cn) 2 4 Nat isthe Cw" it The cory bare con) acid of 9 of a weak aud, HOW weak bast, Wis The plat Mesoiudon will depend onthe verati\e Wiha" Coq) 4He0 (0) = NM 3taq) +H30* taqr shength ail _o baw Aydohys CN (aq) + Hho (C= BON tag) + ON aqEXAMPLE: Predict whether the following solutions will be acidic, basic or neutral. Write the equation of salt dissociation and hydrolysis a. NHGl b. KNO, NaNO, Hints: First break up the salt into its cation and anion components and then examine the possible reaction of each ion with water. CHECKPOINT 10 a we = A soon: OX oi ween > Gijon = fe mea wisoaenon = Wed » howe — “a0 yd wh ») (SetesetoR) FOC) > Kian) © NOL (a0) EE : We 110 sonra _yaow a o [sitaroen) — w,00) >on) + OND HOHE Nove Hon WRF ea+ tvoa varus tn wpe ‘Suggest the appropriate acid and base for the formation of the following salts. Write equations for the reaction of any ion with water. a. Potassium perchlorate, KCIO, b. Sodium benzoate, C,HsCOONa 4. Satl_nydrolysis RUS oS st sh an is pace a Z Y kd04 faq) —? _k* faq) 1 ClO4 cag) art i fn QutaL oO al io dN sao hoe WON4 (aq) 2 Cutis Oo (au) and ‘an) Ces Coo” €420 > Cet(o0 Niu prot" acEXAMPLE 1: Calculation of pH of basic salt solution Calculate the pH of a 0.10 M solution of NaOCl. Given, K, of HOC! is 3.0 « 10%, Ky = 1.0 * 10-4 SOLUTION: ‘Step 1: Write the salt dissociation equation. (Saitaissseiationl] © NaOCI (aq) — Nav(aq) + OCI (aq) ‘Step 2: Choose the strong conjugate ion to further react with water. Write the hydrolysis equation “+ (Beare oct (aq) + H,0 (1) + HOC! (aq) + (OH-Kaq) Step 3: Calculate K, trom given K, value If OH- yields in hydrolysis HOcI|[oH stor i MHOCILOH] 4, Ky 1.010 [ocr] + K, 30x107 =3.3x107 EXAMPLE 1: Calculation of pH of basic salt solution SOLUTION (cont.): ‘Step 4: Calculate the pH value using ICE table or simplifying method. OCI (aq) +H,0 (I) = HOC! + OH Initial 0.10 - - - Change +x +x Equilibrium 0.7 x x [HOCT] = [OH] = x [HOCI[OH] _(x)(x) pOH = -IoglOH'] = = 33107 [ocr] ~0.10-x 0.107 99*10 pOH = -log(1.810*) 2? =(0.10)(3.3x107)=3.3x10* POH = 3.74 x = V3.3x10° =1.8x104M Pee eoee pH=14.00-3.74 pH=10.26 = 10 EXAMPLE 2: Calculation of pH of acidic salt solution Calculate the pH of 0.10 M ammonium nitrate, NH,NO, solution. The K, for ammonia is 1.8 x 10-° at 25°C. SOLUTION: Step 1: Write the salt dissociation equation. Salt dissociation NH,NO, (aq) -> NH,*(aq) + NO, (aq) Step 2: Choose the strong conjugate ion to further react with water. Write the hydrolysis equation. Hydrolysis NH," (aq) + H,0()) = NH,(aq) {H,O%aq) = ‘Step 3: Calculate K, from given K, value if H,0* yields in hydrolysis. K,=Ky = 1x10" = 5.56 x 101" K, 18x 105 Step 4: Calculate the pH value using ICE table or simplifying method. [H,O°] = [5.56 x (10° x 0.1)} = 2.36 x 10° M pH log (2.36 x 10°) = 5.6CHECKPOINT 11 QUESTION 1 Calculate the pH of 0.5 M CH,COOK solution. Determine whether the solution is acidic, basic or neutral. Given, K, for CHjCOOH = 1.76 x 10-5CHECKPOINT 11 QUESTION 2 Calculate the pH of a 0.69 M solution of NH,CI. Given, K,, for NH, = 1.8 x 10°, C x \3.5 Aad- BASE TiTRANON Awo iwoicAToRS 3.5 ACID-BASE TITRATIONS CURVE AND INDICATORS. 3.5 ACID-BASE TITRATIONS CURVE AND INDICATORS. SE TITRATIONS CURVE AND Volumetric Analysis (Tiration) 3.5 ACID-BASE TITRATIONS CURVE AND INDICATORS 3.8 ACID-BASE TITRATIONS CURVE AND INDICATORS hraton Curve “tration Curve Tory 7 ("I ‘Te intl pt wv (Ww 35 ACID.SASE TITRATIONS CURVE AND INDICATORS acip. ASE TITRATIONS CURVE AND INDICATORS caer nsseet mae =a Ge + Fra goneral at base react: eHA+bMOH-cH,0+ ama (cid) (Base) (Water) (Sat) 3.5 ACID-BASE TITRATIONS CURVE AND INDICATORS. Calculation of Acid-Base Reaction 3.5 ACID-BASE TITRATIONS CURVE AND site mgt coment eoaeut xc aot stn ws (coh Seles Gos Gee eect ‘re O40) a oe mee ane “4 (orto, eaacipeaiaa er pore fore puo 10x 0 pis ag (1.0 107m)3.8 ACID-BASE TITRATIONS CURVE AND INDICATORS. Calculation of pH in strong acid-strong base titration EXAMPLE 1 Ip - Hol (an) + NaOH (aq) + NaCl (ag) +H.0 (a3) ‘To each equivalent et (0.02501 of HCI 0.100 + ecu hr et 00 eH at ore we Nit L=2503 10° ma ACh : y= BHELOHT font = VK xT 3.5 ACID-BASE TITRAHONS CURVE AND INDICATORS alulation of BH i wgak bag, ron acd ration vA K HI (oa) + Ne) NHCH fag) seve yas tH." (9) + H0 1) © NH on) 1,009) ‘Atequvalence point (oH <7) \_4y 0 HAs = BH +a B+ HO w BH +0H BH + Oe 8 + HL0" Int pH Ole vex 8) a rm — 1 frame [aeons [0 | meen wore Woy = SBE ye He [aed mate ExT ETS ‘eiiysceinwts: | p0H= og) f= toato7 Vose* View ‘ Peres ZO pi ation COC Poretoesit 3.5 ACID-BASE TITRATIONS CURVE AND INDICATORS. Calculation of pH at equivalence point SOLUTION: ey” The etn of econ Hag) + HCI (ag) > NH,CI aa) Atsaualonze pot he amour me NH, ae eqs the amour ot michele cnc Fm te aan seo ne can tare Reticle ence wih fer pa ae tammy hone. Sos 2.5 ACID-BASE TITRATIONS CURVE AND INDICATOR? mole, ERIE = can Mecatt 3.5 ACID-BASE TITRATIONS CURVE AND INDICATORS Calculation of pH at equivalence point SOLUTION: ‘Step 3: Caleta ne po a ska farmed at equivalence pont SOLUTION ‘The neon equation or this eason NHCI(aq) > Na" Caq) (Ct 1 waa and i cs a act be ‘shan ie Cr nt oppearesin ais equim senna Troy Socata NH) +40 # Nisan) +140") 0.0500 Mot NHC! = 0.05000 Ne NH (aq) + HO NHulagh + HsO%aa) nti 0.0500 0.000 0.000 change * * “Thus, the pte gen by Equioium (Mj (0500-2) x 0 data ane @ maletable - mealt @ hy dayne akCHECKPOINT 12 25,0 mL of 0.100 M NaOH react with 25.0 mL of 0.100 M CH,COOH in a titration. Calculate the pH of solution at the equivalence point. Ke for ‘CH,COOH is 1.8 105. ca) mot fae Naoh 4 Ch cool > Cy @oNa + tho mothefore 25X10 a5xio? 9 ©) motatded |-2isxto*) |-asxto? +2 ue nyarsty® c ° 0 abo? Mi “om ds-omt 50m) ™ 0-05 M salt cooNa <== CH3,@0° 4 not wad ‘on) base (M4, 0 lr Hao] | ct a ceol] +qH7 onc table 4 (00 hao ma CH; wou oH” | 0-05 oO c| |W 44 +1 ©1 [pas it A metad pa xb 2 kw ci mph & (0-08 a)CHECKPOINT 13 NO3C5-A) 3:21 10" bm | alg Ie ct an we td 004 JNO 6-1OVA IM Seateiat te pt at tn equvatnce pont) Given K or CH.NH, is 4.4 10 ‘V2.1 trol 30° = modo” oa hy kia wo) v=20mh Ymor =2.3x(0" md M =0-15M Mayo .4. CSN, t Ano, —> cha N¥anu, mevy O ma tavte = Cha nia r Anos J __ ia NN3NIS bine 2-3 x10 AdAW o batty 23x10? 2-97 10° 42-3x10"? mat hval © ° 2.3xi07* volume 2ome 22 4mb Adame m o0oS4M © sav__drssouah on Ug hlgnd2 cg ———>_CHg WIT ng) 7 e 0." coop Gath Wane a) t hydiolye, V hyautyse Hydislyss: Chants" +80 —> Chyna + tgot ®m fable CA3NIgt 4 Iho — yw 4 Ayot 10-054 - ° s bax kb> lo cl |-n An | FAL | kas eye -¢ & 9 0-H n a fragt, = 9 2aqxW3.5 ACID-BASE TITRATIONS CURVE AND INDICATORS 353. pH Indicator + knack net whose from oa + Many dee change ct depending on HSE “fk aca shows eae age 9 tne of tant a be + Anindcator can therfore be used te dternine tei he i ‘aton iat pat enivalence point oH CHECKPOINT 14 QUESTION 1 Graph below shows 7 ore aan 3.8 ACID-BASE TITRATIONS CURVE AND INDICATORS 353. pH indicator ‘Mesh seen ont ‘ya 3228 anes fea oyetow ose loutstoved rer ule toeen 5268 Yetow wpupe ean tow treat a7a3 Festoabe 7088 oto prerpnaten 200 terest ‘Aan yetow mox20 ‘eli ted ‘anyon mua tow tab CHECKPOINT 14 ‘question 2 ‘Graph below shows the reaction between NaOH and CH,COOM. Choose ‘ne sutabandetor hat can be used in ts tran, CHECKPOINT 14 Se es & QUESTION 3 Graph below shows the reaction between NH, and H,SO,. Choose one ‘suitable indicator that can be used inthis titration,3.6 BUFFER sotution 3-61 Types of Buffer “ R buffer solution 15 asotubion. of weak coqugat® acid-base pair: + Both components (1) and (2) must be present ©) @ weak acid or a weal base and Q) its sale Ty pes of buffer + AeidtGosbuiten “mixture of WemRiaca otis cenjugatembatts CCHy coo ana cy (00) >. Basie buffer : mixture of weak bate with il enugate add CRs and Niyt) 3.6 BUFFER SOLUTIONS. fics [A bufer system can be: represented as. sal-acid lor conjugate base-acis - Example: CH,COONaICH,COOH CH,COO/CH,COOH AA buffer system can be represented as salt-basic or conjugate acid-base. Example: NH.CUNH,Applications of Bufter Inthe body Routter Of Carbome acid CH2 3) and hydrogen carbonate CH(O;”) ; keep the pit of the blood steam at a neutal +4 as any deviahon fom the human bueed (Cp Of 135 7-45) can hove exvemely lyruphve etteds, +The buffers within tne human body isthe haemoglobin compter, which binds excess protons CH tions) muses tleate during exeraie 0 thal tne body conuse Me oxygen Commeraal products - Shampoo contains buffers of citric aad and sodium hydioride ,whrth work te balance out the natural alkalinity of soap Baby lotion js buffered fo slightly audic pH of 6, which inhibits the growth of baderia and cther pathogens CHECKPOINT 15 QUESTION 1 Choose the mixture that yields a buffer solution when equal volumes and concentration of the two solutions are mixed, aud AGicllana Nact ‘and NaCiO, axe Seo onan A HE tMrg = Fo tngot ZA Naf 2 Nat +F7 fect lowearg Jaret iNHow Actinic BUFFER woRKS Ho (2) + WR (aq) == A (aq) +30 tag) Buffers work by applying Le thatener's Punuple weak aud equilibrium Radic buffer solutions Contain significant. amounts of The weak aud molecules, NA These molecules neutralise the added base ol Coy KA ¢aq? +N (aq) —— > Baa) + tho (d The buffer solution also contains ognificant amounts of the conjugate anioy , A" - These ions combine woth added acid, z0*caq) to praduce more Na Re caqy + 36" cag? ——* PAtaq> + haotey pee thet 2.6 BUFFER SOLUTIONS c-aud ae How DOES BUFFER wars“ cok hoot Tne bufler components (cH COOH and ne 1 ove able 40 Consume small amounts cf added OW” ex Ag0* by a shift_in equilibrium positon CHAO cag + Hao 1) = CH: cag) +80 (aq) Gdded ol ve oct wrth added yO" reads wi Us lool ;cau ting a shift foThengnt CHyUpo~, causing shift tb the lett Added bace,oW” chy cooH cag) +08" Can) —> CHZCO0™Caq) + Hrort) Added aug,laO" CHa WO cag) +420" can) —% CH, C008 caqy +Mr0ll)CHECKPOINT 16 Given is the hydrolysis equation for CH,NH, 7 +O” CH,NY, (aq) + H,0 (I) = CH.NH," (aq) + OH (aq) Cor, seen now no eh ccs oan sat anodgdt (OR ated ta soluion ao : (- Rdded ‘gnt- haded base, ol SNM) Cag) + OW” —> CHanly Magradsotl) 1G ashett tote ol noc \ ov (lh | aa ory? Cigna’ toh Chan, rHs0 A canary Gait t toms (AtCOMMON (oN EFFtCT SWAT In Gn done equilibHiuM couied by ‘Me addion ot ASelute Common yon) that fakes part (nthe equilibuum, ¥ fhe presence of a common son suppresses jrtops ‘the ionyaton ofa weak aud or weak base galt ak X consider mixiire of CH CON Céfreng elecholyte) and CH3L00H (weak aud) - Ciycoona cs) — NOt cag) tli CoO Ka) common CH, coo (aq) — Ht (oy) +4 CHa) ———- Fov examplty Acetic add in wat dijsoiates shghhy produce some acetate ion : CW COOH cag) = + “Rao te) = CH3 COO" (aq) +N30* faq) acetic te + aaa 'f Nauscoo ts Odded, ir powder b The addihon of C300” Cine common @ Source of CH3@0~- ion and the yon) reduces (Surpresses) he 4, equilibrium Shifts fothe lel: Ch 30" A\(souahon of tne aud: iW common te bot coluhons.3.6 BUFFER SOLUTIONS 36 ofa Buffer Solution “Tara ave wo mead used a atm he pH ter ston 1 Equitoum Approgch se us ICE table ~The equation atows us o qc culate hop ofa bur souton trom be il eonenirns of bre component ng a he = 3.6 BUFFER SOLUTIONS 383 pl of Butter Solution Honderson-Hasselbalch equation “Tris equations gore egestas as = 0K, eo ooo) ‘me expressions ae fous 3.6 BUFFER SOLUTIONS. 363 pH Butfer Solution (xyo.stex) (20319 (.090-x) (0.000) (o0aoft 8.10) =15x10* 19x10" leatho"T= 5104) 3.6 BUFFER SOLUTIONS 383 plot a Butfer Solution Henderson Hasselbach equation Hata) +.0 0) 4,000) +08) 3.6 BUFFER SOLUTIONS 353 pH ofa Butfor Solution EXAMPLE 1: Calculation of pH of an acide butter solution ‘Conse but sohiton cortaring aets acd, CHCOOH, ad som ‘setae N2CH,COO: Ie butler ston INBCH,COO) = 0.11 M and {CH.COOHH = 0.09 (alate the po rs sun. Kyler CH,COOH = 1X" ‘SOLUTION: >: come er,c00H ta) «14019 600-5) + HO ‘at oo ano Gane - oe Exum 0000 ome <1an00° 2.6 BUFFER SOLUTIONS road Soe oy? cncdbniad +00" OED") + Hor) 353. pl ofa Butter Solution Henderson. a 3.6 BUFFER SOLUTIONS. 3.63 pH of a Buffer Solution EXAMPLE 2: Calculation of pH of a basic buffer solution Calculate the pH ofa ber soliton consis of 0.30 M NH, and 0:38 M NHC butler Baty’ 408" syetom (pK Woe 7 WHY thy S INH (aa) Hf) 1030) pH = (144.75) + og, 92CHECKPOINT 17 QUESTION 1 Alton prepa by mixing 50 mL of 0.19 M NeOC! an £00 mL of 020 M solution, Ko HOGI, Caleuate the pH of is a Th NqoG —> sat bm) ~ 0-05 ch oo} Yew =leg (2 2x10 %) 4) o by [SP3.6 BUFFER SOLUTIONS 363 pH of aBuffor Solution Bufer soliton can also be prepared by using Henderson Hasselbach ‘eon + Determine the dosed pt + Choose ne conjugate scldtase pal. ~The BK, of te weak aed component shoul be close tothe desired ma + Caleta the ratio ofbller component concentrations oncom (SE 3.6 BUFFER SOLUTIONS 363 pH of A Buffer Solution EXAMPLE 4: [An ervirnmental chat nec a caanate bur of pH 10.00 to sy the ‘ects of ha ald anon imestone-ich sls Getermane the mass of Ns, ir gyams (CO,", con} base) must she ado 1.5 Lo esl prepared 0.20 NCO ody, ca opr omake Pe ber ee GOy et HO SOLUTION: pit ph og SOE} mat coe1 peed [95x02 M) mol COs) smal 000.14 mot 0.14 metNe,C0,x 105909 NesCO, Tiel N9,CO,| 15 9N2,CO, 3.6 BUFFER SOLUTIONS 3.63. pH of a Buffor Solution EXAMPLE 3: ‘Suggest one ofthe following acids shouldbe used to prepare a buter with 2 pHotas A HOGHLOCOOM, K, = 1010-3 8 OHH(COOH), K,= 29% 10-4 LCOOH.K, = 18x10-5 4.) CxHs0.CO0H,K, = 4.03 10-6 SOLUTION ‘The best choice Is acetic acid because its PK; les closest othe desired pH,pe CHECKPOINT 18 oe QUESTION 1 ao on The pH of blood is 7.38 It is maintained in part by the/buffer system composed of carbonic acd (H,CO.) and the bicarbonate (hydrogen carbonate, HCO;) ion. Calculate the rato of [bcarbonatey/[carbonie acid at this pH. 1, of carbonic acid = 42 x 107 Gg Ph > 2:35, pl = pas tag Wak aud TAS = lug 42x11) tly bae aud V4S_= 6:37.68 | + leg bole aud G78 2) =| tes | oe ood Lae = Gq laud3.6 BUFFER SOLUTIONS 3.6.4 Effectiveness of a Buffer + Buffer solutions work most efficiently when the ratio of [A-] to [HA] is close to 1. + pH = pK, ; when [HA] = [A] + A buffer is most effective (most resistant to pH changes) when the concentrations of acid and conjugate base are high. * pK, of the weak acid mostly determines where, on the pH scale, a buffer can work best. bh] *+ As long as the ratio of jjjq) in a buffer solution is from 1 to 10 the buffer will maintain pH effectively: 104 > pH= pK, #1 > Lowest pH for effective buffer ; pH = pK, > Highest pH for effective buffer ; pH = pK, + 1 3.6 BUFFER SOLUTIONS 3.6.4 Effectiveness of a Buffer + Buffer capacity, the amount of acid or base that the buffer can react with before showing’ significant pH change. It depends on the amount of conjugate acid or base in the solution. > increases with increasing absolute concentrations of the buffer components. > Initially in a buffer solution there is 0.10 mol CH;COO-. If 0.10 mol HCI is added, this will react completely with the 0.10 mol CH,COO- to give 0.10 mol CH,COOH > Addition of ~0.10 mol HCI exhausts the capacity of the buffer.CHECKPOINT 19 \ ow QUESTION 1 ‘A buffer solution consists of carbonate (CO,#) and hydrogen carbonate (HCO,") conjugate acid-base pair. Choose the following buffers that can neutralise the greatest amount of added hydrochloric acid 1 Lof0.9MCO;*and 0.1 M HCO,” : B.1 Lof0.1 MGO." and 0.9 M HCO,” ow WEALOfOSMCO;~ and OSM HOOP) D.1 Lof 0.1 MCO,* and 0.1 M HCO, 1 i _ CHECKPOINT 20 « pe clo) QUESTION 1 Pyridine, C,HeNy acts as a weak base with a K, of 1.52 x 10°. In a preparation ofits butfer solution, 0.15 mol of coge 18 added into 1.5 L of 0.125 M pyridine soluton. z a conps of 2 a) Calculate the pH of the prepared solution, b) Write an appropriate equation to show the effect on the equilibrium if 0.15 mol of HBr is added into that solution, ©) Determine whether the pH is raised, lowered or maintained in (b). State paginel 7 p len d Lae ay ye ~ Gla + leg OTUs o1m A = 5+ oe coy? 5 f + CaP [Ane] ties [ib Var AA v) od a it manta y) added ard 05 MC Hosts Winted coneSUMMARY: Calculation of pH STRONG ACID or STRONG BASE WEAK ACID or WEAK BASE TITRATION BUFFER HENDERSON- HASSELBALCH EQUATION ae t