8 General, Organic, and Biochemistry, 7e Bettelheim, Brown, and March © 2003 Thomson Learning, Inc. All rights reserved 8-1 8 Chapter 8 Acids and Bases © 2003 Thomson Learning, Inc. All rights reserved 8-2 8 Arrhenius Acids and Bases • In 1884, Svante Arrhenius proposed these definitions • acid: a substance that produces H3O+ ions aqueous solution • base: a substance that produces OH- ions in aqueous solution • this definition of an acid is a slight modification of the original Arrhenius definition, which was that an acid produces H+ in aqueous solution • today we know that H+ reacts immediately with a water molecule to give a hydronium ion + H ( aq) + H2 O( l) © 2003 Thomson Learning, Inc. All rights reserved + H3 O ( aq) Hydronium ion 8-3 8 Arrhenius Acids and Bases • when HCl, for example, dissolves in water, its reacts with water to give hydronium ion and chloride ion H2 O(l) + HCl(aq) H3 O+ (aq) + Cl- (aq) • we use curved arrows to show the change in position of electron pairs during this reaction : : © 2003 Thomson Learning, Inc. All rights reserved : : : : H O: + H Cl : H + H O H + :Cl: H 8-4 8 Arrhenius Acids and Bases • With bases, the situation is slightly different • many bases are metal hydroxides such as KOH, NaOH, Mg(OH)2, and Ca(OH)2 • these compounds are ionic solids and when they dissolve in water, their ions merely separate NaOH(s) H2 O + - Na (aq) + OH (aq) • other bases are not hydroxides; these bases produce OH- by reacting with water molecules NH3 ( aq) + H2 O(l) © 2003 Thomson Learning, Inc. All rights reserved NH4 + ( aq) + OH- (aq) 8-5 8 Arrhenius Acids and Bases • we use curved arrows to show the transfer of a proton from water to ammonia H + H N H + :O H H : : + HO H : © 2003 Thomson Learning, Inc. All rights reserved : H H N: H 8-6 8 Acid and Base Strength • Strong acid: one that reacts completely or almost completely with water to form H3O+ ions • Strong base: one that reacts completely or almost completely with water to form OH- ions • here are the six most common strong acids and the four most common strong bases Formula HCl HBr HI HNO3 H2 SO4 HClO4 © 2003 Thomson Learning, Inc. All rights reserved N ame Hydrochloric acid Hydrob romic acid Hydroiodic acid N itric acid Su lfu ric acid Perch loric acid Formula LiOH NaOH KOH Ba( OH) 2 N ame Lith iu m h yd roxide Sodiu m hydroxide Potass iu m h yd roxide Barium hydroxide 8-7 8 Acid and Base Strength • Weak acid: a substance that dissociates only partially in water to produce H3O+ ions • acetic acid, for example, is a weak acid; in water, only 4 out every 1000 molecules are converted to acetate ions CH3 COOH(aq) + H2 O( l) Acetic acid - CH3 COO ( aq) + H3O+ ( aq) Acetate ion • Weak base: a substance that dissociates only partially in water to produce OH- ions • ammonia, for example, is a weak base NH3 (aq) + H2 O( l) © 2003 Thomson Learning, Inc. All rights reserved NH4 + (aq) + OH-( aq) 8-8 8 Brønsted-Lowry Acids & Bases • • • • Acid: a proton donor Base: a proton acceptor Acid-base reaction: a proton transfer reaction Conjugate acid-base pair: any pair of molecules or ions that can be interconverted by transfer of a proton conju gate acid -base p air conju gate acid -base p air HCl(aq) Hyd rogen chloride (acid) © 2003 Thomson Learning, Inc. All rights reserved + H 2 O(l) Water (bas e) - Cl (aq) + Ch loride ion (conju gate b ase of HCl) + H3 O ( aq) Hyd ronium ion (con jugate acid of water) 8-9 8 Brønsted-Lowry Acids & Bases • Brønsted-Lowry definitions do not require water as a reactant con jugate acid-bas e pair con jugate acid-bas e pair CH3 COOH Acetic acid (acid) © 2003 Thomson Learning, Inc. All rights reserved + NH3 Ammonia (base) - + CH3 COO + NH4 Acetate Ammonium ion ion (con jugate base (conjugate acid acetic acid) of ammonia) 8-10 8 Brønsted-Lowry Acids & Bases • we can use curved arrows to show the transfer of a proton from acetic acid to ammonia : O: © 2003 Thomson Learning, Inc. All rights reserved : O: CH3 -C-O: + : : : : H CH3 -C-O H + :N H H Acetic acid Ammon ia (p roton donor) (proton acceptor) A cetate ion H + H N H H Ammon ium ion 8-11 8 Acid Strong HI Acid s HCl H2 SO4 HNO3 H3 O+ N ame of acid Hydroiodic acid Hydrochloric acid Su lfu ric acid N itric acid Hydron iu m ion HSO4 H3 PO4 CH3 COOH H2 CO3 H2 S - H2 PO4 + NH4 HCN C6 H5 OH HCO3 2- HPO4 Weak H2 O A cids C2 H5 OH © 2003 Thomson Learning, Inc. All rights reserved Conjugate Base I ClHSO4 NO3 H2 O N ame of ion Iod ide Chloride Hydrogen su lfate N itrate Water Weak Bases D ihydrogen p hosph ate Ammon ium ion Hydrocyanic acid Ph enol SO4 2 Su lfate H2 PO4 D ihydrogen p hosph ate CH3 COO Acetate HCO3 Bicarbonate HS Hydrogen su lfid e 2HPO4 Hydrogen ph os phate NH3 Ammon ia CN Cyan ide C6 H5 O Ph enoxide Bicarbonate ion CO3 Hydrogen su lfate ion Ph os phoric acid Acetic acid Carb on ic acid Hydrogen su lfid e 23- Hydrogen ph os phate ion PO4 OHWater C2 H5 O Eth anol Carb on ate Ph os phate Hydroxide Eth oxide S trong Bas es 8-12 8 Brønsted-Lowry Acids & Bases • Note the following about the conjugate acid-base pairs in the table 1. an acid can be positively charged, neutral, or negatively charged; examples of each type are H3O+, H2CO3, and H2PO42. a base can be negatively charged or neutral; examples are OH-, Cl-, and NH3 3. acids are classified a monoprotic, diprotic, or triprotic depending on the number of protons each may give up; examples are HCl, H2CO3, and H3PO4 © 2003 Thomson Learning, Inc. All rights reserved 8-13 8 Brønsted-Lowry Acids & Bases • carbonic acid, for example can give up one proton to become bicarbonate ion, and then the second proton to become carbonate ion + H2 CO3 + H2 O HCO3 + H3 O Carbonic Bicarbon ate acid ion - HCO3 + H2 O Bicarbonate ion 2- + CO3 + H3 O Carbonate ion 4. several molecules and ions appear in both the acid and conjugate base columns; that is, each can function as either an acid or a base © 2003 Thomson Learning, Inc. All rights reserved 8-14 8 Brønsted-Lowry Acids & Bases • the HCO3- ion, for example, can give up a proton to become CO32-, or it can accept a proton to become H2CO3 • a substance that can act as either an acid or a base is said to be amphiprotic • the most important amphiprotic substance in Table 8.2 is H2O; it can accept a proton to become H3O+, or lose a proton to become OH- 5. a substance cannot be a Brønsted-Lowry acid unless it contains a hydrogen atom, but not all hydrogen atoms in most compounds can be given up • acetic acid, for example, gives up only one proton © 2003 Thomson Learning, Inc. All rights reserved 8-15 8 Brønsted-Lowry Acids & Bases 6. there is an inverse relationship between the strength of an acid and the strength of its conjugate base • the stronger the acid, the weaker its conjugate base • HI, for example, is the strongest acid in Table 8.2, and its conjugate base, I-, is the weakest base in the table • CH3COOH (acetic acid) is a stronger acid that H2CO3 (carbonic acid); conversely, CH3COO- (acetate ion) is a weaker base that HCO3- (bicarbonate ion) © 2003 Thomson Learning, Inc. All rights reserved 8-16 8 Acid-Base Equilibria • we know that HCl is a strong acid, which means that the position of this equilibrium lies very far to the right Cl- + H3 O+ HCl + H2O • in contrast, acetic acid is a weak acid, and the position of its equilibrium lies very far to the left CH3 COO- + H3 O+ Acetate ion CH3 COOH + H2 O Acetic acid • but what if the base is not water? How can we determine which are the major species present? CH3 COOH Acetic acid (acid) © 2003 Thomson Learning, Inc. All rights reserved + NH3 Ammonia (b ase) ? - CH3 COO + + NH4 Acetate ion Ammon ium ion (conju gate b ase (con jugate acid of N H 3 of CH 3COOH 8-17 8 Acid-Base Equilibria • To predict the position of an acid-base equilibrium such as this, we do the following • identify the two acids in the equilibrium; one on the left and one on the right • using the information in Table 8.2, determine which is the stronger acid and which is the weaker acid • also determine which is the stronger base and which is the weaker base; remember that the stronger acid gives the weaker conjugate base, and the weaker acid gives the stronger conjugate base • the stronger acid reacts with the stronger base to give the weaker acid and weaker base; equilibrium lies on the side of the weaker acid and weaker base © 2003 Thomson Learning, Inc. All rights reserved 8-18 8 Acid-Base Equilibria • identify the two acids and bases, and their relative strengths CH3 COOH + NH3 A cetic acid Ammonia (stron ger acid) (s tronger base) ? - CH3 COO + NH4 + A cetate ion Ammonium ion (w eak er b ase) (w eaker acid) • the position of this equilibrium lies to the right CH3 COOH + NH3 Acetic acid Ammonia (s tronger acid) (stronger bas e) © 2003 Thomson Learning, Inc. All rights reserved - CH3 COO + NH4 + Acetate ion Ammonium ion (weaker base) (weaker acid) 8-19 8 Acid-Base Equilibria • Example: predict the position of equilibrium in this acid-base reaction - H2 CO3 + OH © 2003 Thomson Learning, Inc. All rights reserved ? - HCO3 + H2 O 8-20 8 Acid-Base Equilibria • Example: predict the position of equilibrium in this acid-base reaction ? - H2 CO3 + OH - HCO3 + H2 O • Solution: the position of this equilibrium lies to the right H2 CO3 + OH - S tronger Stron ger acid bas e © 2003 Thomson Learning, Inc. All rights reserved HCO3 - Weaker base + H2 O Weak er acid 8-21 8 Acid Ionization Constants • when a weak acid, HA, dissolves in water HA + H2 O - + A + H3 O • the equilibrium constant, Keq, for this ionization is K eq = [A-] [H3 O+ ] [HA][ H2 O] • because water is the solvent and its concentration changes very little when we add HA to it, we treat [H2O] as a constant equal to 1000 g/L or 55.5 mol/L • we combine the two constants to give a new constant, which we call an acid ionization constant, Ka Ka = Ke q [H 2 O] = © 2003 Thomson Learning, Inc. All rights reserved [ A- ][ H3 O+ ] [HA] 8-22 8 Acid Ionization Constants • Ka for acetic acid, for example is 1.8 x 10-5 • because the acid ionization constants for weak acids are numbers with negative exponents, we commonly express acid strengths as pKa where pKa = -log Ka • the value of pKa for acetic acid is 4.75 • values of Ka and pKa for some weak acids are given in Table 8.3 • as you study the entries in this table, note the inverse relationship between values of Ka and pKa • the weaker the acid, the smaller its Ka, but the larger its pK © 2003 Thomson Learning, a Inc. All rights reserved 8-23 8 Acid Name Ka pKa H3 PO4 Phosph oric acid 7.5 x 10-3 2.12 HCOOH Formic acid 1.8 x 10-4 3.75 CH3 CH( OH)COOH Lactic acid 8.4 x 10-4 3.08 CH3 COOH Acetic acid 1.8 x 10-5 4.75 H2 CO3 Carbonic acid 4.3 x 10-7 6.37 Dih yd rogen ph osp hate ion 6.2 x 10-8 7.21 H2 PO4 - Boric acid 7.3 x 10-1 0 9.14 Ammonium ion 5.6 x 10-1 0 9.25 HCN Hydrocyanic acid 4.9 x 10-1 0 9.31 C6 H5 OH Phenol 1.3 x 10-1 0 9.89 H3 BO3 NH4 + HCO3 - Bicarb on ate ion 5.6 x 10-1 1 10.25 HPO 2- Hydrogen phosp hate ion 2.2 x 10-1 3 12.66 © 2003 Thomson Learning, Inc. 4 All rights reserved 8-24 8 Properties of Acids & Bases • Neutralization • acids and bases react with each other in a process called neutralization; these reactions are discussed in Section 8.10 • Reaction with metals • strong acids react with certain metals (called active metals) to produce a salt and hydrogen gas, H2 + Mg(s) 2HCl(aq) Magnes ium Hydrochloric acid MgCl2 (aq) + H2 (g) Magnesium Hydrogen chloride • reaction of a strong acid with a metal is a redox reaction; the metal is oxidized to a metal ion and H+ is reduced to H2 © 2003 Thomson Learning, Inc. All rights reserved 8-25 8 Properties of Acids & Bases • Reaction with metal hydroxides • reaction of an acid with a metal hydroxide gives a salt plus water HCl(aq) + KOH( aq) KCl(aq) + H2 O Potass ium Hydrochloric Potassiu m Water chloride acid h yd roxide • the reaction is more accurately written as + + H3 O + Cl + K + OH + 2 H2 O + Cl + K • omitting spectator ions gives this net ionic equation + H3 O + OH © 2003 Thomson Learning, Inc. All rights reserved 2 H2 O 8-26 8 Properties of Acids & Bases • Reaction with metal oxides • strong acids react with metal oxides to give water plus a salt + 2 H3 O (aq) + CaO( s) 2+ 3 H2 O(l) + Ca ( aq) Calciu m oxide © 2003 Thomson Learning, Inc. All rights reserved 8-27 8 Properties of Acids & Bases • Reaction with carbonates and bicarbonates • strong acids react with carbonates to give carbonic acid, which rapidly decomposes to CO2 and H2O + 22 H3 O (aq) + CO3 (aq) H2 CO3 (aq) 2 H3 O+ (aq) + CO3 2 -(aq) H2 CO3 (aq) + 2 H2 O(l) CO2 (g) + H2 O( l) CO2 (g) + 3 H2 O(l) • strong acids react similarly with bicarbonates + H3 O ( aq) + HCO3 ( aq) H2 CO3 (aq) © 2003 Thomson Learning, Inc. + All rights reserved H3 O ( aq) + HCO3 ( aq) H2 CO3 (aq) + H2 O( l) CO2 (g) + H2 O( l) CO2 (g) + 2 H2 O(l) 8-28 8 Properties of Acids & Bases • Reaction with ammonia and amines • any acid stronger than NH4+ is strong enough to react with NH3 to give a salt • in the following reaction, the salt formed is ammonium chloride, which is shown as it would be ionized in aqueous solution HCl( aq) + NH3 (aq) + - NH4 ( aq) + Cl (aq) • in Ch 16 we study amines, compounds in which one or more hydrogens of NH3 are replaced by carbon groups HCl(aq) + CH3 NH2 (aq) Methylamin e © 2003 Thomson Learning, Inc. All rights reserved + CH3 NH3 (aq) + Cl ( aq) Methylammon ium ion 8-29 8 Self-Ionization of Water • pure water contains a very small number of H3O+ ions and OH- ions formed by proton transfer from one water molecule to another H2 O + H2 O A cid Base - OH + + H3 O Conjugate Conjugate base of H2 O acid of H 2 O • the equilibrium expression for this reaction is K eq = [H3 O+ ] [HO-] [H2 O] 2 • we can treat [H2O] as a constant = 55.5 mol/L © 2003 Thomson Learning, Inc. All rights reserved 8-30 8 Self-Ionization of Water • combining these constants gives a new constant called the ion product of water, Kw • in pure water, the value of Kw is 1.0 x 10-14 + - Kw = Ke q [H 2O]2 = [ H3 O ][OH ] Kw = 1.0 x 10-14 • in pure water, H3O+ and OH- are formed in equal amounts (remember the balanced equation for the selfionization of water) • this means that in pure water + [ H3 O ] = 1.0 x 10-7 mol/L - -7 [ OH ] = 1.0 x 10 mol/L © 2003 Thomson Learning, Inc. All rights reserved in pure w ater 8-31 8 Self-Ionization of Water • the equation for the ionization of water applies not only to pure water but also to any aqueous solution • the product of [H3O+] and [OH-] in any aqueous solution is equal to 1.0 x 10-14 • for example, if we add 0.010 mole of HCl to 1 liter of pure water, it reacts completely with water to give 0.010 mole of H3O+ • in this solution, [H3O+] is 0.010 or 1.0 x 10-2 • this means that the concentration of hydroxide ion is - [OH ] = © 2003 Thomson Learning, Inc. All rights reserved 1.0 x 10-14 -1 2 = 1.0 x 10 1.0 x 10-2 8-32 8 pH and pOH • because hydronium ion concentrations for most solutions are numbers with negative exponents, we commonly express these concentrations as pH, where pH = -log [H3O+] • we can now state the definitions of acidic and basic solutions in terms of pH • acidic solution: one whose pH is less than 7.0 • basic solution: one whose pH is greater than 7.0 • neutral solution: one whose pH is equal to 7.0 © 2003 Thomson Learning, Inc. All rights reserved 8-33 8 pH and pOH • just as pH is a convenient way to designate the concentration of H3O+, pOH is a convenient way to designate the concentration of OHpOH = -log[OH-] • the ion product of water, Kw, is 1.0 x 10-14 + - -14 Kw = [H3 O ][ OH ] = 1.0 x 10 • taking the logarithm of this equation gives pH + pOH = 14 • thus, if we know the pH of an aqueous solution, we can easily calculate its pOH © 2003 Thomson Learning, Inc. All rights reserved 8-34 8 pH and pOH • pH of some common materials Material pH Material pH Battery acid 0.5 Gastric juice 1.0-3.0 Lemon juice 2.2-2.4 Vin egar 2.4-3.4 Tomato juice 4.0-4.4 Carb on ated beverages 4.0-5.0 Black coffee 5.0-5.1 Saliva Pu re w ater Blood Bile Pan creatic flu id Seaw ater Soap Urine Rain (unp ollu ted) 5.5-7.5 6.2 Milk of magnesia Househ old ammon ia 10.5 11.7 Milk 6.3-6.6 Lye (1.0 M N aOH) 14.0 © 2003 Thomson Learning, Inc. All rights reserved 6.5-7.5 7.0 7.35-7.45 6.8-7.0 7.8-8.0 8.0-9.0 8.0-10.0 8-35 8 pH of Salt Solutions • When some salts dissolve in pure water, there is no change in pH from that of pure water • Many salts, however, are acidic or basic and cause a change the pH when they dissolve • We are concerned in this section with basic salts and acidic salts © 2003 Thomson Learning, Inc. All rights reserved 8-36 8 pH of Salt Solutions • Basic salt: the salt of a strong base and a weak acid; when dissolved in water, it raises the pH • as an example of a basic salt is sodium acetate • when this salt dissolves in water, it ionizes; Na+ ions do not react with water, but CH3COO- ions do + CH3 COOH2 O A cetate ion Water (w eak er b ase (w eaker base) CH3 COOH + OHAcetic acid Hyd roxide ion (s tronger acid) (stronger bas e) • the position of equilibrium lies to the left • nevertheless, there are enough OH- ions present in 0.10 M sodium acetate to raise the pH to 8.88 © 2003 Thomson Learning, Inc. All rights reserved 8-37 8 pH of Salt Solutions • Acidic salt: the salt of a strong acid and a weak base; when dissolved in water, it lowers the pH • an example of an acidic salt is ammonium chloride • chloride ion does not react with water, but the ammonium ion does + + + + H2 O NH3 H3 O NH4 Water A mmonia Hydron ium ion A mmonium ion (w eak er acid) (w eaker bas e) (s tronger b ase) (s tronger acid • although the position of this equilibrium lies to the left, there are enough H3O+ ions present to make the solution acidic © 2003 Thomson Learning, Inc. All rights reserved 8-38 8 Acid-Base Titrations • Titration: an analytical procedure in which a solute in a solution of known concentration reacts with a known stoichiometry with a substance whose concentration is to be determined • in this chapter, we are concerned with titrations in which we use an acid (or base) of known concentration to determine the concentration of a base (or acid) in another solution © 2003 Thomson Learning, Inc. All rights reserved 8-39 8 Acid-Base Titrations • An acid-base titration must meet these requirement 1. we must know the equation for the reaction so that we can determine the stoichiometric ratio of reactants to use in our calculations 2. the reaction must be rapid and complete 3. there must be a clear-cut change in a measurable property at the end point (when the reagents have combined exactly) 4. we must have accurate measurements of the amount of each reactant © 2003 Thomson Learning, Inc. All rights reserved 8-40 8 Acid-Base Titrations • As an example, let us use 0.108 M H2SO4 to determine the concentration of a NaOH solution • requirement 1: we know the balanced equation H2 SO4 (aq) + 2NaOH(aq) (concentration (concentration known) not known) Na2 SO4 (aq) + 2H2 O( l) • requirement 2: the reaction between H3O+ and OH- is rapid and complete • requirement 3: we can use either an acid-base indicator or a pH meter to observe the sudden change in pH that occurs at the end point of the titration • requirement 4: we use volumetric glassware © 2003 Thomson Learning, Inc. All rights reserved 8-41 8 Acid-Base Titrations • experimental measurements V olu me of 0.108 M H 2 SO 4 Volume of N aOH Trial I Trial II 25.0 mL 25.0 mL 33.48 mL 33.46 mL Trial III 25.0 mL 33.50 mL average = 33.48 mL • doing the calculations 2 mol NaOH mol NaOH 0 .1 0 8 mol H 2 SO4 0 .0 2 5 0 L H2 SO4 = x x L N aOH 1 L H2 SO4 0 .0 3 3 4 8 L NaOH 1 mol H2 SO4 = © 2003 Thomson Learning, Inc. All rights reserved 0 .1 6 1 mol NaOH = 0 .1 6 1 M L NaOH 8-42 8 pH Buffers • pH buffer: a solution that resists change in pH when limited amounts of acid or base are added to it • a pH buffer as an acid or base “shock absorber” • a pH buffer is common called simply a buffer • the most common buffers consist of approximately equal molar amounts of a weak acid and a salt of the weak acid; that is, approximately equal molar amounts of a weak acid and a salt of its conjugate base • for example, if we dissolve 1.0 mole of acetic acid and 1.0 mole of its conjugate base (in the form of sodium acetate) in water, we have an acetate buffer © 2003 Thomson Learning, Inc. All rights reserved 8-43 8 pH Buffers Ad ded as CH 3COO -Na+ Ad ded as CH 3COOH CH3 COOH + H2 O - + CH3 COO + H3 O • How an acetate buffer resists changes in pH • if we add a strong acid, such as HCl, added H3O+ ions react with acetate ions and are removed from solution + CH3 COO + H3 O CH3 COOH + H2 O • if we add a strong base, such as NaOH, added OH- ions react with acetic acid and are removed from solution CH3 COOH + OH © 2003 Thomson Learning, Inc. All rights reserved CH3 COO + H2 O 8-44 8 pH Buffers • The effect of a buffer can be quite dramatic • consider a phosphate buffer prepared by dissolving 0.10 mole of NaH2PO4 (a weak acid) and 0.10 mole of Na2HPO4 (the salt of its conjugate base) in enough water to make 1 liter of solution pH w ater 7.0 0.10 M ph os phate bu ffer 7.21 © 2003 Thomson Learning, Inc. All rights reserved pH after addition of 0.010 mole HCl pH after addition of 0.010 mole N aOH 2.0 7.12 12.0 7.30 8-45 8 pH Buffers • Buffer pH • if we mix equal molar amounts of a weak acid and a salt of its conjugate base, the pH of the solution will be equal to the pKa of the weak acid • if we want a buffer of pH 9.14, for example, we can mix equal molar amounts of boric acid (H3BO3), pKa 9.14, and sodium dihydrogen borate (NaH2BO3), the salt of its conjugate base © 2003 Thomson Learning, Inc. All rights reserved 8-46 8 pH Buffers • Buffer capacity depends both its pH and its concentration pH Con centration © 2003 Thomson Learning, Inc. All rights reserved The clos er the p H of the b uffer is to the pKa of th e w eak acid, th e greater th e buffer capacity The greater the con centration of the w eak acid and its con jugate b ase, the greater the bu ffer capacity 8-47 8 Blood Buffers • The average pH of human blood is 7.4 • any change larger than 0.10 pH unit in either direction can cause illness • To maintain this pH, the body uses three buffer systems • carbonate buffer: H2CO3 and its conjugate base, HCO3• phosphate buffer: H2PO4- and its conjugate base, HPO42• proteins: discussed in Chapter 21 © 2003 Thomson Learning, Inc. All rights reserved 8-48 8 Henderson-Hasselbalch Eg. • Henderson-Hasselbalch equation: a mathematical relationship between • pH, • pKa of the weak acid, HA • concentrations HA, and its conjugate base, A• It is derived in the following way + A + H3 O HA + H2 O Ka = [ A- ][ H3 O+ ] [HA] • taking the logarithm of this equation gives [A ] + © 2003 Thomson Learning, Inc. log K a = log [ H3 O ] + log All rights reserved [ HA] 8-49 8 Henderson-Hasselbalch Eg. • multiplying through by -1 gives - [A ] + -log Ka = -log [H3 O ] - log [HA] • -log Ka is by definition pKa, and -log [H3O+] is by definition pH; making these substitutions gives [A ] pKa = pH - log [HA] • rearranging terms gives - pH = pKa + log © 2003 Thomson Learning, Inc. All rights reserved [A ] [HA] Henderson-Hasselbalch Equation 8-50 8 Henderson-Hasselbalch Eg. • Example: what is the pH of a phosphate buffer solution containing 1.0 mole of NaH2PO4 and 0.50 mole of Na2HPO4 dissolved in enough water to make 1.0 liter of solution © 2003 Thomson Learning, Inc. All rights reserved 8-51 8 Henderson-Hasselbalch Eg. • Example: what is the pH of a phosphate buffer solution containing 1.0 mole of NaH2PO4 and 0.50 mole of Na2HPO4 in enough water to make one liter of solution • Solution • the equilibrium we are dealing with and its pKa are H2 PO4 - + H2 O 1.0 mol/L HPO4 2 - + H3 O+ 0.50 mol/L pKa = 7.21 • substituting these values in the H-H equation gives pH = 7.21 + log 0.50 1.0 © 2003 Thomson Learning, Inc. All rights reserved = 7.21 - 0.30 = 6.91 8-52 8 Chapter 8 Acids and Bases End Chapter 8 © 2003 Thomson Learning, Inc. All rights reserved 8-53
© Copyright 2025 Paperzz