Acids and Bases Chapter 15 Acids in Industry Sulfuric acid, H2SO4, is the chemical manufactured in greatest quantity in the U.S. Eighty billion pounds of sulfuric acid are used each year to manufacture: -fertilizers -pharmaceuticals -detergents -storage batteries -plastics -metals -petroleum Properties of Acids Acids: • taste sour (citrus fruits & vinegar) • affect indicators (e.g. turn blue litmus red) • produce H+ ions in aqueous solution • corrosive to metals • pH < 7 Classifying Acids Organic acids contain a carboxyl group or -COOH -- HC2H3O2 & citric acid. Inorganic acids -- HCl, H2SO4, HNO3. Oxyacids -- acid proton attached to oxygen -- H3PO4. Monoprotic -- HCl & HC2H3O2 Diprotic -- H2SO4 Triprotic -- H3PO4 Properties of Bases Bases: • taste bitter • feel slippery • affect indicators (e.g. turn red litmus blue) • produce OH- ions in aqueous solution • pH > 7 • caustic Models of Acids and Bases Arrhenius Concept: Acids produce H+ in solution, bases produce OH ion. Brønsted-Lowry: Acids are proton (H+) donors, bases are proton (H+) acceptors. HCl + H2O Cl + H3O+ acid base Bronsted-Lowry Model The Bronsted-Lowry Model is not limited to aqueous solutions like the Arrhenius Model. NH3(g) + HCl(g) ----> NH4Cl(s) This is an acid-base reaction according to Bronsted-Lowry, but not according to Arrhenius! Hydronium Ion Hydronium (H3O+) ion is a hydrated proton -H+ . H2O. The H+ ion is simply a proton. It has a very high charge density, so it is strongly attracted to the very electronegative oxygen of the polar water molecule. Conjugate Acid/Base Pairs HA(aq) + H2O(l) H3O+(aq) + A(aq) conj acid 1 conj base 2 conj acid 2 conj base 1 conjugate base: everything that remains of the acid molecule after a proton is lost. conjugate acid: formed when the proton is transferred to the base. Which is the stronger base--H2O or A-? Conjugate Acid-Base Pairs Conjugate Acid Substance Conjugate Base OHHOH H3O+ NH4+ NH3 NH2- H2SO4 HSO4- SO42- H3PO4 H2PO4- HPO42- H2PO41 - HPO4 2- PO43- Conjugate Acid-Base Pairs Which of the following represent conjugate acid-base pairs? a) HF, F- e) OH-, HNO3 b) NH4+, NH3 f) H2O, H3O+ c) HCl, H2O g) H2SO4, SO42- d) HC2H3O2, C2H3O2- h) HClO4, ClO4- Conjugate Bases Write the conjugate base for each of the following: a) HClO4 ClO4- b) H3PO4 H2PO4- c) CH3NH3+ CH3NH2 Acid Strength Strong Acid: - Its equilibrium position lies far to the right. (HNO3) - Yields a weak conjugate base. (NO3) Acid Strength (continued) Weak Acid: - Its equilibrium lies far to the left. (HC2H3O2) - Yields a much stronger (water is relatively strong) conjugate base than water. (C2H3O2-) 14_1577 H+ - H+ A A H+ AH+ A(a) AH+ H+ H+ A- H+ HB A- HB H+ HB HB H+ H+ H+ HB HB A- AA- A- H+ HB A- HB HB B- HB HB (b) A strong acid is nearly 100 % ionized, while a weak acid is only slightly ionized. 14_322 Before dissociation HA After dissociation, at equilibrium H+ A– (a) HA HA H+ A– (b) Diagram a represents a strong acid, while b represents a weak acid which remains mostly in the molecular form. 14_323 Relative acid strength Very strong Relative conjugate base strength Very weak Strong Weak Weak Strong Very weak Very strong The relationship of acid strength and conjugate base strength for acid-base reactions. Bases Bases are often called alkalis because they often contain alkali or alkaline earth metals. “Strong” and “weak” are used in the same sense for bases as for acids. strong = complete dissociation (hydroxide ion supplied to solution) NaOH(s) Na+(aq) + OH(aq) Bases (continued) weak = very little dissociation (or reaction with water) NH3(aq) + HOH(l) NH4+(aq) + OH(aq) Water as an Acid and a Base Water is amphoteric (it can behave either as an acid or a base). H2O + H2O <---> H3O+ + OH acid 1 base 2 conj acid 2 conj base 1 Kw = 1 1014 M2 at 25°C Kw = [H+][OH-] Only about two molecules in a billion ionize!! Ion product Constant, Kw Kw is called the ion-product constant or dissociation constant. neutral solution [H+] = [OH-] = 1.0 x 10 -7 M acidic solution [H+] > [OH-] [H+] > 1.0 x 10-7 M basic solution [H+] < [OH-] [H+] < 1.0 x 10-7 M No matter what the concentration of H+ or OH- in an aqueous solution, the product, Kw, will remain the same. [H+] & [OH-] Calculations Calculate the [H+] for a 1.0 x 10-5 M OH-. Kw = [H+][OH-] [H+] = Kw/[OH-] [H+] = 1.0 x 10-14 M2/1.0 x 10-5 M [H+] = 1.0 x 10-9 M [H+] & [OH-] Calculations Continued Calculate the [OH-] for a 10.0 M H+. Kw = [H+][OH-] [OH-] = Kw/[H+] [OH-] = 1.0 x 10-14 M2/10.0 M [OH-] = 1.0 x 10-15 M [H+] & [OH-] Calculations Calculate the [H+] for a 2.0 x 10-2 M OH-. Kw = [H+][OH-] [H+] = Kw/[OH-] [H+] = 1.0 x 10-14 M2/2.0 x 10-2 M [H+] = 5.0 x 10-13 M The pH Scale pH = log[H+] pH in water usually ranges from 0 to 14. Kw = 1.0 1014 M2 = [H+] [OH] pKw = 14.00 = pH + pOH As pH rises, pOH falls (sum = 14.00). Figure 15.5: Indicator paper being used to measure the pH of a solution Figure 15.4: A pH meter pOH = 14 1x 10-14 pOH = 7 1 x 10-7 pOH = 0 1 x 100 OH - OH- + O H3 H3O+ OH H3O+ 1 x 100 pH = 0 1 x 10-7 pH = 7 1 x 10-14 pH = 14 Logarithms -log 1.00 x 10-7 = 7.000 7.000 characteristic mantissa The number of significant digits in 1.00 x 10-7 is three, therefore, the log has three decimal places. The mantissa represents the log of 1.00 and the characteristic represents the exponent 7. 14_324 [H+] pH 10–14 14 –13 10 Basic 13 10–12 12 –11 10 1 M NaOH 11 Ammonia (Household cleaner) 10–10 10 10–9 9 10–8 8 Neutral 10–7 7 10–6 6 10–5 5 10–4 4 10–3 3 10–2 2 10–1 1 1 0 Acidic Blood Pure water Milk Vinegar Lemon juice Stomach acid 1 M HCl pH scale and pH values for common substances. A pH of 1 is 100 times more acidic than a pH of 3. pH & Significant Figures log # Significant Figures -------> # decimal places <------inv log pH = - log [H+] [H+] = inv log (-pH) [H+] = 1.0 x 10-5 M pH = 5.00 pH Calculations Calculate the pH value for the following solution at 25 oC. [H+] = 1.0 x 10-9 M pH = - log [H+] pH = - log [1.0 x 10-9] pH = 9.00 pH Calculations Calculate the pH for the following solution at 25 oC. [OH-] = 1.0 x 10-6M pH + pOH = 14.00 pOH = - log [OH-] pH = 14.00 - pOH pOH = - log [1.0 x 10-6] pH = 14.00 - 6.00 pOH = 6.00 pH = 8.00 pH Calculations What is the pOH, [H+], & [OH-] for human blood with a pH of 7.41? pH + pOH = 14.00 pOH = 14.00 - pH pOH = 14.00 - 7.41 pOH = 6.59 pH Calculations Continued What is the pOH, [H+], & [OH-] for human blood with a pH of 7.41? pH = - log [H+] [H+] = antilog (-pH) [H+] = antilog (-7.41) [H+] = 3.9 x 10-8 M Note: The number of significant figures in the antilog is equal to the number of decimal places in the pH. pH Calculations Continued What is the pOH, [H+], & [OH-] for human blood with a pH of 7.41? pOH = - log [OH-] [OH-] = antilog (-pOH) [OH-] = antilog (-6.59) [OH-] = 2.6 x 10-7 M Note: The number of significant figures in the antilog is equal to the number of decimal places in the pOH. pH of Strong Acid Solutions Calculate the pH of a 0.10 M HNO3 solution. Major species are: H+, NO3-, and H2O Sources of H+ are from HNO3 and H2O -amount from water is insignificant. [H+] = 0.10 M Note: The number of significant figures in the [H+] is the same as the decimal places in the pH. pH = - log [H+] pH = - log [0.10] pH = 1.00 A Buffered Solution . . . resists change in its pH when either H+ or OH are added. 1.0 L of 0.50 M HC2H3O2 + 0.50 M Na C2H3O2 pH = 4.74 Adding 0.010 mol solid NaOH raises the pH of the solution to 4.76, a very minor change. Preparation of Buffered Solutions Buffered solution can be made from: 1. a weak acid and its salt (e.g. HC2H3O2 & NaC2H3O2). 2. a weak base and its salt (e.g. NH3 & NH4Cl). Other examples of buffered pairs are: H2CO3 & NaHCO3 H3PO4 & NaH2PO4 NaH2PO4 & Na2HPO4 Na2HPO4 & Na3PO4 Characteristics of a Buffer 1. The solution contains a weak acid HA and its conjugate base A-. 2. The buffer resists changes in pH by reacting with any added H+ or OH- so that these ions do not accumulate. 3. Any added H+ reacts with the base A-. 4. Any added OH- reacts with the weak acid HA. Buffered Solutions Used when need to maintain a certain pH in the system. Blood Buffers work by reacting with added H+1 or OH-1 ions so they do not accumulate and change the pH. Buffers will only work as long as there is sufficient weak acid and conjugate base molecules present. Buffering Mechanism HC2H3O2(aq) <---> H+(aq) + C2H3O2-(aq) The buffering materials dissolved in the solution prevent added H+ or OH- from building up in solution. Buffering Capacity . . . represents the amount of H+ or OH the buffer can absorb without a significant change in pH.