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# Acids and Bases - the Three Definitions

1. Measurement of pH - the pH meter 2. Bronsted-Lowry definition of acids and bases - an acid is a proton donor - a base is a proton acceptor conjugate acid/conjugate base pairs - relationship of Ka of a conjugate acid and Kb of a conjugate base 3. Lewis definition of acids and bases - a base is an electron pair donor - an acid is an electron pair acceptor - some examples of Lewis acids and Lewis bases

Ionization Constants (1)

Ionization Constants (2) .

which is the strongest conjugate base? nitrous acid: oxalic acid (2): arsenic acid (2): carbonic acid (1): HNO2 / NO2HC2O4./ AsO43H2CO3 / HCO3- . (2) Find the values of pKa. (3) Which species is the strongest conjugate acid./ C2O42HAsO42.Exercise on Acid/Bases Strength For each conjugate acid/base pair. pKb. (1) Write the reactions defining Ka and Kb. and Kb.

acetate (pKb=9.25) hydrolyses to produce H3O+) 3. ammonium chloride (acidic (pH=5..25) hydrolyses to produce OH-) 2.(pKb2=6.79) hydrolyses to produce OH-) (you need to consider two conjugate acid/base pairs.10 M solution. 1. or neutral? Write the hydrolysis reaction (if any). sodium acetate (basic (pH=8.12). calcium chloride (neutral.12).88). HPO42. ammonium (pKa=9.) .Hydrolysis Reactions Which salts undergo hydrolysis? Is the resulting solution acidic. Calculate the pH of a 0. sodium monohydrogen phosphate (basic (pH=10. no hydrolysis) 4. basic.

1 .x = CH3COO.1) Approximation Method: Since Ka <<1.1 and x = [H+] = 0.75 x 10-6 .pH and % Dissociation of a Monoprotic Weak Acid What is the pH of 0.x = 1.75 * 10-5 = 1.+ x H+ x Ka = 1.0013 M x2 = 0. assume x<<0.10 M CH3COOH? CH3COOH 0.1 .1 * 1.75 x 10-5 (x << 0.75 x 10-5 (We let x = [H+]) Ka = [CH3COO-] [H+] [CH3COOH] = x2 0.

Calculating % Dissociation and the pH CH3COOH = CH3COO.3% .3 x 10-3 M pH = .88 % dissociation = 100 * [CH3COO-] [CH3COOH]init = x 0.1 = 1.+ H+ [H+] = 1.log10[H+] = 2.

Measurement of pH: the pH Meter pH varies linearly with output voltage and can be measured over the range pH 0 to pH 14 .

(aq) + H+ (aq) Ka = 6.6 x 10-4 pKa = 3.76 x 10-5 pKa = 4.(aq) + H+ (aq) Ka = 4.17 x 10-10 pKa = 9. the larger the Ka and the smaller the pKa: HNO2 (aq) = NO2.34 stronger CH3COOH (aq) = CH3COO.(aq) + H+ (aq) Ka = 1.Ka and Acid Strength The stronger the acid.75 HCN (aq) = CN.21 weaker .

Weak Acids stronger = = = = = = = weaker .

log10 (1. Kb is the equilibrium constant for this reaction.log10 Kb (definition) pKb = .in solution.8 x 10-5) = 4.(aq) [NH4+] [OH-] [NH4OH] Kb = = 1.76 x 10-5 pKb = .74 .Kb and pKb Arrhenius bases liberate OH. NH4OH (aq) = NH4+ (aq) + OH.

(aq) Kb = 1.(aq) + H2O (l) = HPO42.5 x 10-2 pKb = 1.74 Conclusion: phosphate anion is a stronger base than NH4OH. the larger the Kb and the smaller the pKb: stronger PO43.Kb and Base Strength The stronger the base.(aq) Kb = 4. weaker .8 x 10-5 pKb = 4.34 NH4OH (aq) = NH4+ (aq) + OH.(aq) + OH.

Kb's of weak bases Strength (Ranked) 3 7 6 1 5 2 4 .

Acids and Bases .Three Definitions Arrhenius Definition: Acids: increases [H+] in aqueous solution Bases: increases [OH-] in aqueous solution Bronsted-Lowry Definition: (based on proton transfer reactions) Acids: proton (H+) donor Bases: proton (H+) acceptor Lewis Definition: Acids: electron pair acceptor Bases: electron pair donor .

: O-H H water .. : I iodide H : N-H H ammonia . hydroxide .e..Some Lewis Acids and Bases Lewis bases are characterized by having an available lone pair.. electron pair acceptors Examples are: H+ Zn2+ metal cations Hg2+ Ag+ BF3 electron deficient compounds .. :.. 2:S : . :O-H.. sulfide Lewis acids are electron deficient .i.. Examples are: ..

Least general definition Arrhenius Bronsted-Lowry Most general definition Lewis Example: A strong acid reacts with a strong base: H+(aq) + :OH-(aq) = H2O(l) Electron pair acceptor electron pair donor .Lewis Acids/Bases .the Most General Definition The Lewis definition generalizes the acid/base concept: Every Arrhenius acid/base is also a Lewis acid/base. Every Bronsted acid/base is also a Lewis acid/base.

.......O : .O : .... .. + ..... . . . . [ O=N..and ClO2-). . : O-N= O ] . .O : H . . . ..... .. which compete for the acid The lone pairs donated by these bases are on oxygen atoms: . . : O-Cl= O ] . . .. O=Cl. ...The Lewis Acid-Base Reaction Lewis definition: Acid: electron pair acceptor Base: electron pair donor HNO2 + ClO2... .= HClO2 + NO2Bronsted-Lowry: acid1 base2 acid2 base1 The Lewis acid is H+ (the electron deficient species) There are 2 bases (NO2. ... + .. ... . . O=N... . . . . [ O=Cl. .O : H .

:O-H..Lewis Acids and Bases The acid/base concept is further generalized by the Lewis acid/base definition.an electron pair donor H+ Lewis acid + .. Lewis acid . = H-O H : F F-B F Lewis acid + H : N-H H Lewis base = F H F-B:N-H F H . The driving force is the donation of an electron pair to electron-deficient atom.. Lewis base .an electron pair acceptor Lewis base .

Complex Ions in Solution One example of Lewis acid-base neutralization involves the stepwise complexes formed between Hg(II) and I. There are four stepwise reactions. (red-brown ppt) . each of which is an acid/base neutralization by the Lewis definition: Hg2+(aq) + I-(aq) = HgI+(aq) HgI+(aq) + I-(aq) = HgI2(s) HgI2(s) + I-(aq) = HgI3-(aq) HgI3-(aq) + I-(aq) = HgI42-(aq) Identify the Lewis acid and Lewis base in each reaction.ion.

white precipitate .= Al(OH)4Identify the Lewis acid and Lewis base in each reaction. There are four stepwise reactions.ion.= Al(OH)3 (s) Al(OH)3 + :OH.= AlOH2+ AlOH2+ + :OH.Complex Ions and Solubility Stepwise Lewis acid/base complexes form between Al3+(aq) and OH. each of which is an acid/base neutralization by the Lewis definition: All Only the Al3+ + :OH. charged species are soluble in aqueous solution. uncharged Al(OH)3(s) forms a white precipitate.= Al(OH)2+ Al(OH)2+ + :OH.