Acid and Base Strength. Weak Acid-Base Equilibrium. Acid and Base Strength 1.
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1 Weak Acid-Base Equilibrium Acid and Base Strength A molecule with negligible acidity contains hydrogen but does not demonstrate any acidic behavior in water. Its conjugate base is extremely strong. Possibly explained by Lewis theory. No measurable H +. Acid and Base Strength 1. A strong acid completely transfers its protons to water leaving no undissociated (ionized) molecules. Its conjugate base is extremely weak. Easily explained by Arrhenius Concentration of H + is defined stoichometrically by initial acid concentration 2. Acid and Base Strength A weak acid only partially dissociates in aqueous solution and therefore exists in the solution as a mixture of the acid and its conjugate base. Its conjugate base is fairly strong. Explained by Arrhenius but better explained by BL. Concentration of H + must be determined applying equilibrium calculations. Dissociation Constants For a generalized acid dissociation, HA(aq) + H 2 O(l) the equilibrium expression would be K c = [H 3 O + ] [A ] [HA] A (aq) + H 3 O + (aq) This equilibrium constant is called the acid-dissociation constant, K a. 1
2 Weak Acid-Base Equilibrium For the weak acid acetic acid, the equilibrium exists as: CH 3 CO 2 H + H 2 O CH 3 CO 2- + H 3 O + Therefore, we can define K as K = [CH 3 CO 2- ] [H 3 O + ] / [CH 3 CO 2 H] = K a Where: K a = acid dissociation constant for Acetic Acid The acid-dissociation constant (K a ) describes the ratio of H + and acid anion to acid molecules for weak acid dissociation using the Law of Mass Action. Using what we now know about equilibrium, we can calculate the concentrations of dissociated ions and undissociated acid molecules at equilibrium, thereby allowing us to find K a for any acid. (AP equation Sheet) The ph of a.1 M solution of formic acid, HCOOH, at 25 C is Calculate K a for formic acid at this temperature. The ph of a.1 M solution of formic acid, HCOOH, at 25 C is Calculate K a for formic acid at this temperature. We know that K a = [H 3 O + ] [HCOO ] [HCOOH] To calculate K a, we need the equilibrium concentrations of all three things. We can find [H 3 O + ], which is the same as [HCOO ], from the ph. ph = log [H 3 O + ] 2.38 = log [H 3 O + ] 2.38 = log [H 3 O + ] = 1 log [H3O+] = [H 3 O + ] = [H 3 O + ] = [HCOO ].1 2
3 =.958 = K a = [ ] [ ] [.1] = Two things to note: A. We neglected the [H + ] due to the autoionization of water in aqueous solutions only one source of H + is dominant. Even weak acids have a much higher H + concentration than water B. Given the number of significant figures, [RCO 2 H] o [RCO 2 Weak acids usually have very little dissociation (K<<1). We will learn to make this assumption as long as we do not affect the H + concentration by more than 5% 1. Niacin, one of the B vitamins, has the following molecular structure: A.2 M solution of niacin has a ph of 3.26, What is the K a for Niacin? 3
4 Dissociation Constants The greater the value of K a, the stronger the acid. The magnitude of K a describes the weak acid strength, just as K eq described the magnitude of a reaction. The larger the value of K a, the greater the dissociation, the further to the right the equilibrium is shifted, meaning the greater the acid strength. Examine the Acetic acid equilibrium again. CH 3 CO 2 H + H 2 O CH 3 CO 2- + H 3 O + A 1 B 1 B 2 A 2 Look Up K a values for both acids We know that K<<1; so, the equilibrium favors the reactants. But what does that say about the rest of the species in equilibrium? Because H 3 O + is a stronger B-L acid than acetic the reaction lies to the left. This brings us to an important observation: In every acid-base reaction, equilibrium favors the transfer of the proton from the stronger acid to the stronger base to firm the weaker acid and the weaker base. 2. Write the dissociation (ionization) reaction for each of the following and determine if the equilibrium will lie to the right or the left using what you know about acid strengths. Then label as acid/base or conjugate acid/base. a. NH 3 + H 2 O b.hso CO 3 2- c. PO H 2 O Percent Ionization Another measure of acid strength, besides Ka, is the acid percent ionization (dissociation) The percent dissociation of an acid,or base, is the percent of initial concentration that is dissociated in a weak acid-base solution. As the weak acid/base concentration increases, the percent ionization decreases 4
5 Calculating Percent Ionization =.958 = [H Percent ionization = 3 O + ] eq [HA] 1 initial From our earlier example, [H 3 O + ] eq = M [HCOOH] initial =.1 M Percent ionization =.1 1 = 4.2% Weak Bases Bases react with water to produce hydroxide ion. 212 Pearson Education, Inc. Weak Bases The equilibrium constant expression for this reaction is K b = [HB] [OH ] [B ] 3. For base reactions, K b can be determined following the same equilibrium guidelines. Calculate the K b for a.5 M CO 3 2- solution having a ph of where K b is the base-dissociation constant. 212 Pearson Education, Inc. (AP equation Sheet) The relationship between K a and K b conj. is described by the ion-product constant of water (K w ) 4. Calculate K b for the fluoride ion, using Appendix D. K b for F - is not given, but its conjugate acid is. K a x K b conj. = K w The product of the aciddissociation constant and basedissociation constant for the conjugate acid-base pair equals the ion-product constant of water 5
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