Acids and Bases Acid-Base chemistry important in our everyday lives acidity of our blood is carefully controlled making sulfuric acid is an important industry sulfuric acid is needed to make fertilizers, polymers, steel, etc. environmental impact of acid rain

Acids and Bases Properties of acids taste sour e.g. vinegar, citric acid in soda and candies react with many metals (to form the metal ion and hydrogen gas 2H+ + Zn --> H2 + Zn+2 react with carbonates (to form CO2) 2H+ + CaCO3 --> Ca+2 + H2O + CO2

Acids and Bases Properties of bases bitter taste slippery feel

Acids and Bases Definitions of Acids Arrhenius - an acid produces H+ in aqueous solutions Bronsted-Lowry - an acid is an H+ donor Lewis - e- pair acceptor

Acids and Bases Definitions of Bases Arrhenius - a base produces hydroxide ions in solution Bronsted-Lowry - a base is an H+ acceptor Lewis - a base is an e- pair donor

Acids and Bases Acid-Base Definitions Arrhenius definition is limited to aqueous solutions, and only allows for one kind of base, those with hydroxide ions. Bronsted-Lowry is a more general definitions, water can now act as a base. Lewis - the most general definition

Acids and Bases Terms to know: proton - H+ ion hydronium ion - H3O+; results from water reacting with H+ H2O + H+ --> H3O+ conjugate base - whatever is left from an acid after a proton has been donated conjugate acid - whatever has been formed when a proton has been accepted by a base

Acids and Bases Acid Dissociation Constant an equilibrium constant for the ionization or dissociation of an acid Ka for HA(aq) + H2O(l) <==> H3O+(aq) + A-(aq) Ka = [H3O+][A-] / [HA] which is equivalent to Ka = [H+][A-] / [HA] remember, pure liquids, like water, are not included in the equilibrium expression

Acids and Bases Acid Strength defined by the equilibrium position of the dissociation reaction Strong Acid - equilibrium lies far to the right, i.e. the acid is 100% ionized the conjugate base of a strong acid is a much weaker base than water, i.e. the conjugate base will not accept the H+ the stronger the acid the weaker the conjugate base

Acids and Bases Weak acid not 100% ionized equilibrium lies to the left very little HA is ionized the conjugate base of a weak acid is a stronger base than water, the conjugate base is more likely to accept an H+ than water the weaker the acid, the stronger the conjugate base

Acids and Bases The Six Strong Acids HCl H2SO4 HNO3 HBr HI HClO4

Acids and Bases Oxyacids Organic acids Most acids are oxyacids The acidic proton is attached to an oxygen atom Organic acids Generally weak acids Contain the -COOH (carboxyl) group ex: CH3COOH - acetic acid

Acids and Bases Water The most common amphoteric substance water can act as both an acid and a base water can autoionize: H2O + H2O <==> H3O+ + OH- one water molecule acts as an acid (H+ donor), the other acts as an acid (an H+ acceptor) Kw = [H3O+][OH-] = 1.00 x 10-14 @ 25oC dissociation or ion product constant for water

Acids and Bases Kw In any aqueous solution at 25oC, the product of [H+] and [OH-] will be 1.0 x 10-14 So if you know the [H+], you can figure out the [OH-] and vice versa If [H+] = [OH-], the solution is neutral If [H+] > [OH-], the solution is acidic If [H+] < [OH-], the solution is basic

Acids and Bases pH scale Because the [H+] in any solution is generally quite small, it is easier to use the pH scale to represent a solution’s acidity. pH comes from the Danish…potenz or strength of the H+ ion pH = - log[H+] pOH = - log [OH-]

Acids and Bases pH is a log scale when the pH changes by one, the [H+] concentration changes by a power of 10. A solution with a pH of 3 has 10 times more H+ than a solution with a pH of 4, and 100 times more H+ than a solution with a pH of 5. As pH decreases, the [H+] increases. Rule for significant figures for logarithms - the number of places after the decimal point is equal to the number of significant figures in the original number pH = - log 1.0 x 10-9 M (2 significant figures in 1.0 x 10-9) pH = 9.00 ( 2 places after the decimal point for significant figures)

Acids and Bases Acid-Base Equilibria…or doing acid-base problems the aqueous solutions contain many components you must be able to determine which components are most significant and which can be ignored you must be able to determine which reaction is most important of all the possible reactions

Acids and Bases Ex: Calculate the pH of 1.0 M HCl First: Determine the major species HCl is a strong acid, 100% ionized Major species then will be H+, Cl- and H2O Since this is an acidic solution with “lots” of H+, the [OH-] will be insignificant. What about H2O <==> H+ + OH- ? Will any H+ come from this reaction? Le Chatelier’s principle tells us that the reverse reaction will be favored because of the high concentration of H+ from the HCl, so we can ignore this reaction as a source of H+. Thus the pH = - log (1.0) = 0.00

Acids and Bases pH of Weak Acid Solutions Calculate the pH of 1.0 M HF Determine the major species: HF (because it is a weak acid, very little of it ionizes), and H2O Which of these major species will provide the H+ ions? Consider the Ka and Kw

Acids and Bases HF <==> H+ + F- Ka = 7.2 x 10-4 H2O <==> H+ + OH- Kw = 1.0 x 10-14 Because the Ka of HF is greater than the Kw, HF is a stronger acid than H2O, and will be the primary contributor of H+ in solution. Use the Ka for HF to determine the [H+] at equilibrium, and then determine the pH.

Acids and Bases Simplifying acid-base equilibrium calculations If Ka is small, then “x” is small relative to the original concentrations. 1.00 - x becomes essentially 1.00 in these calculations Is this a valid assumption? Please check at the end! Compare x to [HAo], if x < 5% of [HAo], then the assumption is valid

Acids and Bases The pH of a mixture of weak acids Calculate the pH of a solution that contains 1.00 M HCN (Ka = 6.2 x 10-10), and 5.00 M HNO2 (Ka = 4.0 x 10-4). Determine the major species: HCN, HNO2, and H2O Compare Ka’s and Kw. The Ka for HNO2 is larger than Kw and the Ka for HCN HNO2 <==> H+ + NO2- is the reaction of interest.

Acids and Bases % dissociation or % ionization gives us an idea of the amount of weak acid that has dissociated % dissociation = ([H+] /[HAo]) x 100 For a weak acid, the % ionization increases as the concentration gets more dilute.

Acids and Bases Bases Strong Bases 100% ionized Group I hydroxides (e.g. NaOH, KOH, etc) heavy Group II hydroxides (Ca(OH)2, Ba(OH)2, Sr(OH)2) A base does not have to contain OH- ion to be a base

Acids and Bases Bases Ammonia: NH3 + H2O <==> NH4+ + OH- The [OH-] increases due to the reaction of ammonia with water, so ammonia is a base, specifically, a Bronsted-Lowry base, because it is a proton acceptor. Many bases are like ammonia with a lone pair of electrons on the nitrogen that can accept H+. Consider these bases as substituted ammonia molecules e.g. CH3NH2, (CH3)2NH, (CH3)3N, C2H5NH2

Acids and Bases General reaction between a base and water B + H2O <==> BH+ + OH- Kb = [BH+][OH-]/[B] In equilibrium problems involving weak bases, if Kb < Kw, then the base will be the primary source of OH-.

Acids and Bases Polyprotic Acids (many proton acids) Some acids can donate more than one H+ e.g. H2SO4 and H3PO4 Polyprotic acids lose 1 H+ at a time. H2SO4--> H+ + HSO4- Ka1 >> 0 HSO4- <==> H+ + SO4-2 Ka2 = 1.2 x 10-2 The decreasing Ka as protons are lost indicate it is less favorable (as the negative charge on the acid increases) to lose the second (or third) proton

Acids and Bases Acid-Base Properties of Salts Salt = an ionic compound salts dissolve in water to form ions sometimes these ions can react with water to form weak acids or weak bases

Acids and Bases Neutral Salts When these salts dissolve in water, the pH does not change. There is no reaction of the ions from the salt with water. The anion and cation are derived from a strong acid and a strong base, respectively.

Acids and Bases Ex. NaCl is a neutral salt. Na+, the cation, can be considered as coming from NaOH, a strong base. Cl-, , the anion, can be considered as coming from HCl, a strong acid. Remember the conjugates of strong acids and strong bases are very weak, weaker than water, and so are unlikely to react with water to reform the acid or base.

Acids and Bases Na+ + H2O cannot form NaOH + H+…strong bases do not re-form in solution. Cl- + H2O cannot HCl + OH- …strong acids do not re-form in solution.

Acids and Bases Basic Salts The anion from this salt will react with water to form a weak acid and OH-. The anion must have come from a weak acid originally. Ex: NaCH3COO. The Na+ comes from a strong base, NaOH. CH3COO- comes from a weak acid, CH3COOH. Na+ + H2O cannot form NaOH + H+ CH3COO- + H2O <==> CH3COOH + OH-

Acids and Bases Acidic Salts The cation from an acidic salt will react with water to form a weak base and H+. The cation must have come from a weak base. Ex: NH4Cl. The NH4+ comes from a weak base, and will react with water to re-form the weak base and H+ (H3O+). The Cl- comes from a strong acid, and cannot react with water to re-form HCl. NH4+ + H2O <==> NH3 + H3O+

Acids and Bases How do we know the Kb for the conjugate base of a weak acid? How do we know the Ka for the conjugate acid of a weak base? CH3COOH + H2O <==> CH3COO- + OH- Ka = 1.8 x 10-5 CH3COO- + H2O <==> CH3COOH + OH- Kb = [CH3COOH][OH-]/[CH3COO-] = ? Ka. Kb = Kw

Acids and Bases Salts that are derived from both a weak acid and a weak base We can predict whether the solution will be acidic or basic based on the Ka of the acidic ion and the Kb of the basic ion. Ka > Kb pH < 7, acidic solution Kb > Ka pH > 7, basic solution Kb = Ka pH = 7, neutral solution

Acids and Bases The effect of structure on acid-base properties Any molecule containing hydrogen could theoretically act as an acid. However, most of these molecules don’t. Organic molecules with lots of C-H bonds are not acidic because the C-H is both strong, and relatively nonpolar, so there is no tendency to lose H+ However, while the H-Cl bond is stronger than the C-H bond, the H-Cl bond is very polar, and there is a strong tendency to lose H+.

Acids and Bases Two Factors that determine the acidity of a molecule containing X-H strength of the X-H bond polarity of the X-H bond Consider polarity of the X-H bond H-F > H-Cl > HBr > HI in terms of polarity H-F > H-Cl > H-Br > HI in terms of bond strength HF is a weak acid, HCl, HBr, and HI are strong acids even though the H-F bond is very polar, the H-F bond is very strong, so HF is a weak acid

Acids and Bases Oxyacids contains the grouping H-O-X HClO4 Ka >>> 0 HClO3 Ka = 1 HClO2 Ka = 1.2 x 10-2 HClO Ka = 3.5 x 10-8 As the number of oxygen atoms increase, the acid strength increases

Acids and Bases Oxygen is very electrognegative. With increasing number of oxygen atoms, the oxygen atom draw more and more of the electron density towards themselves, thus polarizing and weakening the O-H bond,

Acids and Bases This behavior also occurs with hydrated metal ions. Al+3 is strongly attracted to water, weakening the O-H bond. The greater the charge on the metal ion, the stronger the acidity.

Acids and Bases The greater the electronegativity of X in the H-O-X grouping, the stronger the acid. X is able to withdraw electron density from the H-O bond, thus weakening and polarizing the H-O bond, resulting in a stronger acid

Acids and Bases Comparison of Electronegativity of X and Ka

Acids and Bases Acid-Base Properties of Oxides An H-O-X grouping in a molecule may result in a molecule that behaves as a base or an acid. The nature of the O-X bond will determine the acidic or basic behavior of the molecule

Acids and Bases If X is very electronegative, the O - X bond will be covalent (not as polar because of similar E.N.’s), and strong. The O - X bond will remain intact in water, while the polar and weak H - O bond will break, resulting in acidic behavior. e.g. HClO2 or H2SO4 If X is not very electronegative, the O - X bond will be ionic, and can be broken in water, resulting in basic behavior. e.g. NaOH or KOH

Acids and Bases Basically… Nonmetal oxides will form acids in water SO2 + H2O <==> H2SO3 CO2 + H2O <==> H2CO3 Metal oxides will form bases in water Na2O + H2O --> 2 NaOH CaO + H2O --> Ca(OH)2 (the oxide ion has a high affinity for protons and reacts with water to form hydroxide ions)

Acids and Bases Lewis acids and bases are electron pair acceptors and electron pair donors, respectively A very general model for acids-base reactions…see Lewis structures for explanations...