Acids & Bases Edward Wen, PhD Learning Outcomes • Properties of acids and bases and definitions • pH scale and calculation of pH • Completing and balancing Neutralization reactions • Titration calculations for neutralization reactions • Defining Weak vs. Strong electrolytes (using the concept of equilibrium) • Buffers – recognition of a buffer system, how a buffer works 2 Types of Ionic Compounds • Acids = form H+ ions in water solution • Bases = combine with H+ ions in water solution increases the OH- concentration may either directly release OH- or pull H+ off H2O • Salts = Ionic compounds formed from Acid and Base. all strong electrolytes Cation: except H+ Anion: except OH3 Properties of Acids • Sour taste • react with “active” Metals i.e. Al, Zn, Fe, but NOT w/ Ag, Au Zn + 2 HCl ZnCl2 + H2 • react with Carbonates, producing CO2 marble, baking soda, limestone CaCO3 + 2 HCl CaCl2 + CO2 + H2O • change color of vegetable dyes blue litmus turns red • react with Bases to form ionic salts 4 Most food contains acids • Citric acid (HO2CCH(CO2H)COHCO2H): citrus fruits, tomato • Malic acid (HO2CCH2CHOHCO2H): green apple, tomato, grape • Ascorbic acid (aka Vitamin C) • Folic acid 5 Common Acids Chemical Name Formula Uses Strength Nitric Acid HNO3 explosive, fertilizer, dye, glue Strong explosive, fertilizer, dye, glue, batteries metal cleaning, food prep, ore refining, stomach acid fertilizer, plastics & rubber, food preservation plastics & rubber, food preservation, Vinegar Sulfuric Acid H2SO4 Strong Hydrochloric Acid HCl Phosphoric Acid H3PO4 Acetic Acid HC2H3O2 Hydrofluoric Acid HF metal cleaning, glass etching Weak Carbonic Acid H2CO3 soda water Weak Boric Acid H3BO3 eye wash Weak Strong Moderate Weak 6 Binary acids • (HmX): acid hydrogens attached to a nonmetal atom HCl, HF, HBr, HI H2S, H2Se Hydrofluoric acid 7 Oxyacids • acid hydrogens (H+) attached to an oxygen atom H2SO4, HNO3, H3PO4 HClO4 8 Carboxylic acids • Many exist in food like vinegar, tomato, citrus fruit • -COOH group HC2H3O2, H3C6H5O3 • only the first H in the formula is acidic the H is on the COOH 9 Properties of Bases • • • • also known as alkalis taste bitter solutions feel slippery change color of vegetable dyes different color than acid red litmus turns blue • react with acids to form ionic salts neutralization 10 Common Bases Chemical Name sodium hydroxide potassium hydroxide calcium hydroxide Aluminum hydroxide magnesium hydroxide ammonium hydroxide Formula NaOH Common Name lye, caustic soda KOH caustic potash Ca(OH)2 slaked lime NH4OH, {NH3(aq)} soap, plastic, petrol refining soap, cotton, electroplating Strength Strong Strong cement Strong Antacid Weak milk of magnesia antacid Weak ammonia water detergent, Windex fertilizer, explosives, fibers Weak Al(OH)3 Mg(OH)2 Common Uses 11 Structure of Bases • most ionic bases contain OH- ions Drano clog-remover: NaOH, Ca(OH)2 • some contain CO32- ion: it produces OH- with water Baking soda: CaCO3 Alka-Seltzer: NaHCO3 • molecular bases that react with H+ Windex: Ammonia (NH3) 12 Acid-Base Reactions (Neutralization, Double Displacement Reaction) • H+ (from the acid) + OH- (from the base) H2O it is often helpful to think of H2O as H-OH • Cation (from base) + Anion (from acid) Salt acid + base → salt + water HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l) 13 Acid Reactions. I. Reaction with Metals • Reaction with many metals: Al, Zn, Fe, Mg but not all!! Not for Cu, Au, Ag, etc. • Producing a Salt and hydrogen gas H2 3 H2SO4(aq) + 2 Al(s) → Al2(SO4)3(aq) + 3 H2(g) 14 Acid Reactions. II Reaction with Metal Oxides • when acids react with metal oxides, they produce a salt and water 3 H2SO4 + Al2O3 → Al2(SO4)3 + 3 H2O 15 Acid Reactions. III Gas-evolving Reaction with Salts • when acids react with metal carbonate, bicarbonate, sulfide, sulfite, and bisulfite, gas will be produced along with other products 2 HNO3 + FeCO3 → Fe(NO3)2 + CO2 + H2O HCl + NaHCO3 → NaCl + CO2 + H2O ZnS + 2 HBr → ZnBr2 + H2S CaSO3 + 2 HI → CaI2 + SO2 + H2O H2SO4 + 2 NH4HSO3 → (NH4)2SO4 + 2SO2 + 2H2O 16 Base Reactions • Neutralization of acids • Reaction with Nonmetal oxides, CO2 2 NaOH + CO2 → Na2CO3 + H2O • Strong bases will react with Al metal to form sodium aluminate and hydrogen gas Example: Dissolving recycled aluminum can with NaOH solution 2 NaOH + 2 Al + 6 H2O → 2 NaAl(OH)4 + 3 H2 17 Relative Strength of Acids Acid Strong Acid Conjugate Base Hydroiodic acid HI I- Hydrobromic acid HBr Br- Hydrochloric Acid HCl Cl- Sulfuric Acid H2SO4 HSO4- Nitric Acid HNO3 NO3- Hydronium ion H3O+ H2O Phosphoric Acid H3PO4 H2PO4- Hydrofluoric Acid HF F- Acetic Acid HC2H3O2 C2H3O2- Carbonic Acid H2CO3 HCO3- Ammonium ion NH4+ NH3 18 Strong Acids • The stronger the acid, the more willing it is to donate H+ Stomach acid HCl H+ + Cl- use water as the standard base • Strong acids donate practically all their H+ 100% ionized in water • [H3O+] = [strong acid] [ ] = molarity 19 Strong Acids Examples: • Binary Acid: HCl, HBr, HI • Oxyacid: HNO3, H2SO4, HClO4, HClO3 • Example: HNO3 = H+ + NO3H2SO4 = 2H+ + SO42- 20 Weak Acids • Weak acids donate a small fraction of their H+ Vinegar HC2H3O2 H+ + C2H3O2- most of the weak acid molecules do not donate H+ to water • [H3O+] << [weak acid] 21 Weak Acids Examples: • Binary Acid: HF, H2S, H2Se • Oxyacid: HNO2, H2SO3, H3PO4, HClO • Most carboxylic acids, such as acetic acid 22 Strong Bases • The stronger the base, the more willing it is to accept H+ DranoTM use water as the standard acid NaOH Na+ + OH- • Strong bases: practically all molecules are dissociated into OH– or accept H+ 1 mol NaOH = 1 mol OH 1 mol Ca(OH)2 = 2 mol OH- • [OH–] = [strong base] x (# OH) 23 Weak Bases • Definition: a small fraction of molecules accept H+ WindexTM NH3 + H2O NH4+ + OH- most of the weak base molecules do not take H+ from water • [HO–] << [weak base] 24 Autoionization of Water • Water: extremely Weak electrolyte therefore there must be a few ions present • about 2 out of every 1 billion water molecules form Ions: Autoionization H2O + H2O H3O+ + OH– H2O H+ + OH– • ALL aqueous solutions contain both H+ and OH– the concentration of H+ and OH– are equal in water @ 25°C: [H+] = [OH–] = 10-7M 25 Ion Product of Water • [H+] x [OH–] = constant: Ion Product of water, Kw • At 25°C, [H+] x [OH–] = 1 x 10-14 = Kw • as [H+] increases, [OH–] must decrease so the product stays constant 14 110 [H ] [OH ] 14 110 [OH ] [H ] 26 Acidic and Basic Solutions • Neutral solutions have equal [H+] and [OH–] [H+] = [OH–] = 1 x 10-7 M • Acidic solutions : [H+] > [OH–] [H+] > 1 x 10-7 M [OH–] < 1 x 10-7 M • Basic solutions: [OH–] > [H+] [H+] < 1 x 10-7 M [OH–] > 1 x 10-7 M 27 Practice - Determine the [H+] concentration and whether the solution is acidic, basic or neutral for the following All [H+] compared to 1 x 10-7 M • [OH–] = 3.50 x 10-8 M • [NaOH] = 0.000250 M • [HCl] = 0.50 M 28 Practice - Determine the [H+] concentration and whether the solution is acidic, basic or neutral for the following • [OH–] = 3.50 x 10-8 M [H+] -14 1 x 10 -7 M = = 2.86 x 10 3.50 x 10-8 [H+] >[OH-], therefore acidic • NaOH = 0.000250 M [H+] -14 1 x 10 = = 4.00 x 10-11 M [H+] < [OH-], therefore basic 0.000250 • [HCl] = 0.50 M [H+] = 0.50 M [H+] > 1.0 x 10-7 M therefore acidic Acidic/Basic: [H+] vs. [OH-] [H+] 100 10-1 + H OH- Acid 10-3 10-5 + H OH- [OH-]10-14 10-13 10-11 10-9 10-7 10-9 Base 10-11 H+ + H 10-13 10-14 H+ OH OH OH 10-7 10-5 10-3 10-1 100 even though it may look like it, neither H+ of OH- will ever be 0 the sizes of the H+ and OH- are not to scale because the divisions are powers of 10 rather than units 30 pH • The measure of the acidity/basicity of a solution • pH = -log[H+], [H+] = 10-pH exponent on 10 with a positive sign pHwater = -log[10-7] = 7 need to know the [H+] concentration to find pH • pH < 7 : Acidic; • pH = 7 : Neutral pH > 7 : Basic 31 pH scale • pH↓, Acidity↑ • pH↑, basicity↑ 1 pH unit corresponds to a factor of 10 difference in acidity • normal range 0 to 14 pH 0 is [H+] = 1 M, pH 14 is [OH–] = 1 M 32 pH measurement pH can be measured by pH meter: • The change in [H+] affects the voltage of a standard cell 33 pH of Common Substances Substance pH 1.0 M HCl 0.0 0.1 M HCl 1.0 stomach acid 1.0 to 3.0 lemons 2.2 to 2.4 soft drinks 2.0 to 4.0 plums 2.8 to 3.0 apples 2.9 to 3.3 cherries 3.2 to 4.0 unpolluted rainwater 5.6 human blood 7.3 to 7.4 egg whites 7.6 to 8.0 milk of magnesia (sat’d Mg(OH)2) 10.5 household ammonia 10.5 to 11.5 1.0 M NaOH 14 34 Example - Calculate the pH of the following strong acid or base solutions • 0.0020 M HCl • 0.010 M NaOH 35 Example - Calculate the pH of the following strong acid or base solutions • 0.0020 M HCl HCl as strong acid, so [H+] = 0.0020 M pH = - log (2.0 x 10-3) = 2.7 • 0.010 M NaOH NaOH as strong base, so [OH-] = 0.010 M [H+] = 1 x 10-14= 1 x 10-12 M 1 x 10-2 pH = - log (1.0 x 10-12) = 12 36 pH in everyday life Stomach acid Vinegar Pure water Windex pH 0 1 [H+] 100 10-1 + H OH- Acid 3 10-3 5 7 9 10-5 10-7 10-9 + H OH- [OH-]10-14 10-13 10-11 10-9 + H Base 11 13 10-11 OH 10-5 14 10-13 10-14 H+ H+ OH 10-7 Drano OH 10-3 10-1 100 37 Example - Calculate the concentration of [H+] for a solution with pH 3.7 [H+] = 10-pH [H+] = 10-3.7 = 2 x 10-4 M = 0.0002 M 38 Find concentration of Acid or Base? Titration • Purpose: using Reaction Stoichiometry to determine the Concentration of an unknown solution • Titrant (solution of known concentration) added from a Buret • Indicators: chemicals added to help determine when a reaction is complete • the Endpoint of the titration occurs when the reaction is complete 39 Titration: Color change w/ Indicator 40 Titration Start: The base solution as titrant in the buret. Titrating: As the Base is added to the Acid, H+ + OH– HOH. But still excess Acid present so the color does not change. Endpoint: just enough Base to neutralize all the acid. The indicator changes color. 41 Calculations in Titration • At the Endpoint of the titration, acid base neutralization reaction is complete. The mole ratio between acid and base in the reaction mixture is the same as in the balanced equation. • Given the concentration of titrant, the mole of titrant can be calculated as: mole = Molarity x Volume (L) • Then the mole of the other reactant can be calculated from the mole of titrant and the mole ratio in the equation (review stoichiometry: mole-to-mole). • Finally, the molarity of other reactant can be determined. Example: Acid-Base Titration Example: • The titration of 10.00 mL of HCl solution of unknown concentration requires 12.51 mL of 0.100 M Ba(OH)2 solution to reach the endpoint. What is the concentration of the unknown HCl solution? 44 Example: The titration of 10.00 mL of HCl solution of unknown concentration requires 12.54 mL of 0.100 M Ba(OH)2 solution to reach the end point. What is the concentration of the unknown HCl solution? Information Given: 10.00 mL HCl 12.54 mL 0.100 M Ba(OH)2 Find: M HCl • First, write balanced equation: 2 HCl(aq) + Ba(OH)2(aq) → BaCl2 (aq) + 2H2O(l) 2 mole HCl = 1 mole Ba(OH)2 0.100 M Ba(OH)2 0.100 mol Ba(OH)2 1 L sol’n moles solute M olarity liters solution 45 Example: The titration of 10.00 mL of HCl solution of unknown concentration requires 12.51 mL of 0.100 M Ba(OH)2 solution to reach the end point. What is the concentration of the unknown HCl solution? Information Given: 10.00 mL HCl 12.51 mL Ba(OH)2 Find: M HCl CF: 2 mol HCl = 1 mol Ba(OH)2 0.100 mol Ba(OH)2 = 1 L M = mol/L • Write a Solution Map: mL Ba(OH)2 L Ba(OH)2 0.001 L 1 mL mL HCl 0.001 L 1 mL mol Ba(OH)2 0.100 mol Ba O H 2 1 L Ba OH 2 L HCl mol HCl 2 mol HCl 1 mol Ba(OH) 2 moles HC l M olarity liters HC l 46 Example: The titration of 10.00 mL of HCl solution of unknown concentration requires 12.51 mL of 0.100 M Ba(OH)2 solution to reach the end point. What is the concentration of the unknown HCl solution? Information Given: 10.00 mL HCl 12.51 mL Ba(OH)2 Find: M HCl CF: 2 mol HCl = 1 mol Ba(OH)2 0.100 mol Ba(OH)2 = 1 L M = mol/L SM: mL Ba(OH)2 → L Ba(OH)2 → mol Ba(OH)2 → mol HCl; mL HCl → L HCl & mol M = 2.50 x 10-3 mol HCl 47 Example: The titration of 10.00 mL of HCl solution of unknown concentration requires 12.51 mL of 0.100 M Ba(OH)2 solution to reach the end point. What is the concentration of the unknown HCl solution? Information Given: 10.00 mL HCl 12.51 mL Ba(OH)2 Find: M HCl CF: 2 mol HCl = 1 mol Ba(OH)2 0.100 mol Ba(OH)2 = 1 L M = mol/L SM: mL Ba(OH)2 → L Ba(OH)2 → mol Ba(OH)2 → mol HCl; mL HCl → L HCl & mol M 0.001 L 1 0.00 mL H Cl 0 . 01000 L H Cl 1 mL -3 2.50 x 10 moles HCl Molarity 0.250 M 0.01000 L HCl 48 How does pH change? Initial pH 1 L Pure water 1 L 0.14 M K2HPO4 + 0.10 M KH2PO4 pH after pH after adding 1 mL adding 1 mL 1 M HCl 1 M NaOH 4.00 10.00 7.00 6.99 7.01 7.00 49 Buffers • Definition: solutions that resist changing pH when small amounts of acid or base are added • The mixture of 0.14 M K2HPO4 + 0.10 M KH2PO4 solution has much smaller pH change when strong acid or base is added, thus is called Buffer. • Ingredient: mixing together a weak acid and its conjugate base or weak base and it conjugate acid Online demo: https://www.youtube.com/watch?v=P-R-Cqvb5yo • Human body fluid as buffer: H2CO3/HCO350 Buffer Composition: • a weak acid + its salt; example: HC2H3O2 / NaC2H3O2, HF/KF When acid is added: C2H3O2- + H+ HC2H3O2 When base is added: OH- + HC2H3O2 C2H3O2- + H2O • OR, a weak base + its salt example: NH3 / NH4Cl 51 Acetic Acid/Acetate Buffer 52 Treasure Hunt: Which two can combine into a Buffer? HCl NH4+ C2H3O2ClHCO3CO32HC2H3O2 NH3 H2CO3 53