Acids and Bases http://www.unit5.org/chemistry/AcidBase.html Guiding Questions What is an acid? What makes acids dangerous? Is acid rain an issue for us? What does pH balanced mean? Table of Contents ‘Acids, Bases, and Salts’ Definitions pH Scale Acid Rain Common Acids Common Bases LeChatelier’s Principle Maintaining Blood pH Conjugate Acid-Base Pairs pKa Concentration vs. Strength pH Indicators Buffers Titration Swimming Pools Acids, Bases, and Salts You should be able to Understand the acid-base theories of Arrhenius, Brønsted-Lowry, and Lewis. Identify strong acids and bases and calculate their pH’s. Calculate the pH of a weak acid or base. Calculate the concentration of a strong or weak acid or base from its pH. Calculate the pH and ion concentration in a polyprotic acid. Predict the pH of a salt from its formula and then calculate the pH of the salt. Be familiar with titration curves and selection of an acid-base indicator. Lecture Outline – Acids and Bases Lecture Outline – Acids and Bases student notes outline textbook questions Lecture Outline – Acids and Bases textbook questions Keys text http://www.unit5.org/chemistry/AcidBase.html pH scale: measures acidity/basicity ACID BASE 10x10x 100x 10x 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 NEUTRAL Each step on pH scale represents a factor of 10. pH 5 vs. pH 6 pH 3 vs. pH 5 pH 8 vs. pH 13 (10X more acidic) (100X different) (100,000X different) pH scale: measures acidity/basicity Søren Sorensen (1868 - 1939) ACID BASE 10x10x 100x 10x 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 NEUTRAL Each step on pH scale represents a factor of 10. pH 5 vs. pH 6 pH 3 vs. pH 5 pH 8 vs. pH 13 (10X more acidic) (100X different) (100,000X different) Richter Scale - Earthquakes 7 6 5 . 4 3 2 1 pH = -log [H1+] Acid Base [H+] Acidic [H+] = [OH-] Neutral pH = 7 Basic [OH-] radius = 112.8 cm radius = 35.7 cm . radius = 11.3 cm radius = 3.6 cm radius = 1.1 cm radius = 0.1128 cm pH = 1 pH = 2 pH = 3 . pH = 4 5 6 Acids and Bases pH < 7 taste sour react w/bases proton (H1+) donor turn litmus red lots of H1+/H3O1+ react w/metals pH > 7 taste bitter react w/acids proton (H1+) acceptor turn litmus blue lots of OH1– don’t react w/metals Both are electrolytes. Acid vs. Base Different Alike pH < 7 Affects pH and litmus paper Topic sour taste react with metals Acid Different pH > 7 Topic Related to H+ (proton) concentration pH + pOH = 14 Base bitter taste does not react with metals Properties electrolytes electrolytes sour taste bitter taste turn litmus red turn litmus blue react with metals to form H2 gas slippery feel vinegar, milk, soda, apples, citrus fruits ammonia, lye, antacid, baking soda ChemASAP Copyright © 2007 Pearson Benjamin Cummings. All rights reserved. Common Acids and Bases Strong Acids (strong electrolytes) HCl HNO3 HClO4 H2SO4 hydrochloric acid nitric acid perchloric acid sulfuric acid Weak Acids (weak electrolytes) CH3COOH H2CO3 acetic acid carbonic Strong Bases (strong electrolytes) NaOH KOH Ca(OH)2 sodium hydroxide potassium hydroxide calcium hydroxide Weak Weak Base Base (weak (weak electrolyte) electrolyte) NH NH43OH ammonia NH3 + H2O NH4OH Kotz, Purcell, Chemistry & Chemical Reactivity 1991, page 145 Acid + Base Salt + Water • Orange juice + milk bad taste • Evergreen shrub + concrete dead bush • Under a pine tree + fertilizer white powder HCl + NaOH NaCl + HOH salt water Acid-Base Neutralization 1- 1+ + + H32O+ OH H2O- H2O H2O Water ion Hydronium Hydroxide Water ion Water Water Dorin, Demmin, Gabel, Chemistry The Study of Matter 3rd Edition, page 584 Acid-Base Neutralization 1- 1+ + + H3O+ OH- H2O H2O Hydronium ion Hydroxide ion Water Water Dorin, Demmin, Gabel, Chemistry The Study of Matter 3rd Edition, page 584 Acid Precipitation http://nadp.sws.uiuc.edu/amaps2/ Click Here Formation of Sulfuric Acid + + SO2(g) + H2O(l) H2SO3(aq) 2SO2(g) + O2(g) 2SO3(g) SO3(g) + H2O(l) H2SO4(aq) Sulfuric acid Catalyzed by atmospheric dust SO2(g) + H2O2(l) Kelter, Carr, Scott, Chemistry A World of Choices 1999, page 302 H2SO4(aq) Hydrogen ion concentration as pH from measurements made at the field laboratories during 2003 made at the Central Analytical Laboratory, 1999 The progressively darker red areas on the map indicate the lowest pH levels and areas most prone to problems from acid rain. National Atmospheric Deposition Program/National Trends Network http://nadp.sws.uiuc.edu Figure courtesy of the National Atmospheric Deposition Program, Champaign, Ill. Acid Rain Estimated sulfate ion deposition, 1999 Smoke stacks pollute SO2 into the atmosphere. This combines with water to form acid rain. SO4 Levels http://nadp.sws.uiuc.edu Coal Burning Power Plant Copyright © 2007 Pearson Benjamin Cummings. All rights reserved. Copyright © 2007 Pearson Benjamin Cummings. All rights reserved. CO2 (g) H2O (l) H2CO3 (aq) Carbon dioxide Water Carbonic acid Weak acid Copyright © 2007 Pearson Benjamin Cummings. All rights reserved. Carbon dioxide Water Carbonic Acid Carbon dioxide Water Carbonic Acid Copyright © 2007 Pearson Benjamin Cummings. All rights reserved. Common Acids Sulfuric Acid H2SO4 Battery acid Nitric Acid HNO3 Used to make fertilizers and explosives Phosphoric Acid H3PO4 Food flavoring Hydrochloric Acid HCl Stomach acid Acetic Acid Carbonic Acid CH3COOH H2CO3 Vinegar Carbonated water Common Acids Formula Name of Acid Name of Negative Ion of Salt HF HBr HI HCl HClO HClO2 HClO3 HClO4 H2S H2SO3 H2SO4 HNO2 HNO3 H2CO3 H3PO3 H3PO4 hydrofluoric hydrobromic hydroiodic hydrochloric hypochlorous chlorous chloric perchloric hydrosulfuric sulfurous sulfuric nitrous nitric carbonic phosphorous phosphoric fluoride bromide iodide chloride hypochlorite chlorite chlorate perchlorate sulfide sulfite sulfate nitrite nitrate carbonate phosphite phosphate Formation of Hydronium Ions 1+ 1+ 1+ + H+ H2O hydrogen ion (a proton) water H3O+ hydronium ion Sulfuric Acid, H2SO4 Sulfuric acid is the most commonly produced industrial chemical in the world. Uses: petroleum refining, metallurgy, manufacture of fertilizer, many industrial processes: metals, paper, paint, dyes, detergents Sulfuric acid is used in automobile batteries. H2SO4 “oil of vitriol” Nitric Acid, HNO3 Nitric acid stains proteins yellow (like your skin). Uses: make explosives, fertilizers, rubber, plastics, dyes, and pharmaceuticals. HNO3 “aqua fortis” Hydrochloric Acid, HCl The stomach produces HCl to aid in the digestion of food. Uses: For ‘pickling’ iron and steel. Pickling is the immersion of metals in acid solution to remove surface impurities. A dilute solution of HCl is called muriatic acid (available in many hardware stores). Muriatic acid is commonly used to adjust pH in swimming pools and in the cleaning of masonry. HCl(g) + H2O(l) hydrogen chloride water HCl(aq) hydrochloric acid Common Bases Name Formula Common Name Sodium hydroxide NaOH lye or caustic soda Potassium hydroxide KOH lye or caustic potash Magnesium hydroxide Mg(OH)2 milk of magnesia Calcium hydroxide Ca(OH) 2 slaked lime Ammonia water NH H 2O NH43.OH household ammonia NH41+ + OH1ammonium hydroxide Relative Strengths of Acids and Bases perchloric hydrogen chloride nitric sulfuric hydronium ion hydrogen sulfate ion phosphoric acetic carbonic hydrogen sulfide ammonium ion hydrogen carbonate ion water ammonia hydrogen Metcalfe, Williams, Catska, Modern Chemistry 1966, page 229 Formula HClO4 HCl HNO3 H2SO4 H3O+ HSO4H3PO4 HC2H3O2 H2CO3 H2S NH4+ HCO3H2O NH3 H2 acid Conjugate base Formula perchlorate ion chloride ion nitrate ion hydrogen sulfate ion water sulfate ion dihydrogen phosphate ion acetate ion hydrogen carbonate ion hydro sulfide ion ammonia carbonate ion hydroxide ion amide ion hydride ion conjugate base + H+ ClO4ClNO3HSO4H2O SO42H2PO4C2H3O2HCO3HSNH3 CO32OHNH2H- Decreasing Base Strength Decreasing Acid Strength Acid Binary Hydrogen Compounds of Nonmetals When Dissolved in Water (These compounds are commonly called acids.) The prefix hydro- is used to represent hydrogen, followed by the name of the nonmetal with its ending replaced by the suffix –ic and the word acid added. Examples: *HCl Hydrochloric acid HBr Hydrobromic acid *The name of this compound would be hydrogen chloride if it was NOT dissolved in water. Naming Simple Chemical Compounds Ionic (metal and nonmetal) Metal Forms only one positive ion Use the name of element Forms more than one positive ion Covalent (2 nonmetals) Nonmetal Single Negative Ion Use element Use the name name followed of the by a Roman element, but numeral to end with ide show the charge First nonmetal Second nonmetal Before element name use a prefix to match subscript Use a prefix before element name and end with ide Polyatomic Ion Use the name of polyatomic ion (ate or Ite) Naming Ternary Compounds from Oxyacids The following table lists the most common families of oxy acids. one more oxygen atom HClO4 perchloric acid most “common” HClO3 chloric acid H2SO4 sulfuric acid H3PO4 phosphoric acid HNO3 nitric acid one less oxygen HClO2 chlorous acid H2SO3 sulfurous acid H3PO3 phosphorous acid HNO2 nitrous acid two less oxygen HClO hypochlorous acid H3PO2 hypophosphorous acid (HNO)2 hyponitrous acid An acid with a name ending in A salt with a name ending in -ous forms -ite -ic forms -ate Hill, Petrucci, General Chemistry An Integrated Approach 1999, page 60 Oxyacids Oxysalts If you replace hydrogen with a metal, you have formed an oxysalt. A salt is a compound consisting of a metal and a non-metal. If the salt consists of a metal, a nonmetal, and oxygen it is called an oxysalt. NaClO4, sodium perchlorate, is an oxysalt. OXYACID OXYSALT HClO4 perchloric acid NaClO4 sodium perchlorate HClO3 chloric acid NaClO3 sodium chlorate HClO2 chlorous acid NaClO2 sodium chlorite HClO hypochlorous acid NaClO sodium hypochlorite ACID SALT per stem ic changes to per stem ate stem ic changes to stem ate stem ous changes to stem ite hyper stem ous changes to hypo stem ite HClO3 acid + Na1+ cation NaClO3 + H1+ salt Acid Definitions Lewis Acid Brønsted-Lowry Arrhenius acids Arrhenius Acids and Bases Acids release hydrogen ions in water. Bases release hydroxide ions in water. An acid is a substance that produces hydronium ions, H3O+, when dissolved in water. Brønsted-Lowry Definitions A Brønsted-Lowry acid is a proton donor; it donates a hydrogen ion, H+. A Brønsted-Lowry base is a proton acceptor; it accepts a hydrogen ion, H+. Lewis Definitions A Lewis acid is a substance than can accept (and share) an electron pair. A Lewis base is a substance than can donate (and share) an electron pair. Acid Definitions Lewis acids The Arrhenius model of acids and bases was broadened by the Brønsted-Lowry model. Brønsted-Lowry The Lewis acid-base model is the most general in scope. Arrhenius acids Ralph A. Burns, Fundamentals of Chemistry 1999, page 483 The Lewis definition of an acid includes any substance that is an electron pair acceptor; a Lewis base is any substance that can act as an electron pair donor. Acid Definitions Lewis acids The Arrhenius model of acids and bases was broadened by the Brønsted-Lowry model. Brønsted-Lowry The Lewis acid-base model is the most general in scope. Arrhenius acids Ralph A. Burns, Fundamentals of Chemistry 1999, page 483 The Lewis definition of an acid includes any substance that is an electron pair acceptor; a Lewis base is any substance that can act as an electron pair donor. Acid – Base Systems Type Acid Base Arrhenius H+ or H3O + producer OH - producer BrønstedLowry Lewis Proton (H +) donor Proton (H +) acceptor Electron-pair acceptor Electron-pair donor Arrhenius Acid Any substance that releases H+ ions as the only positive ion in the aqueous solution. 1- 1+ + + HCl H2O H3O+ Cl- hydrogen chloride (an Arrhenius acid) water hydronium ion chloride ion Definitions Arrhenius - In aqueous solution… • Acids form hydronium ions (H3O+) HCl + H2O H3O+ + Cl– H H Cl O H O H H – + Cl H acid Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem Definitions Arrhenius - In aqueous solution… • Bases form hydroxide ions (OH-) NH3 + H2O NH4 + + H H H N H O H – + O N H H OH H H base Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem H Arrhenius Bases and Their Properties According to the definition of Arrhenius a: Base - "a substance whose water solution yields... hydroxide ions (OH-) as the only negative ions." Are NaOH and NH3 considered to be Arrhenius bases? YES 1) Bases are electroytes Dissociation equation for NaOH NaOH(s) Na1+(aq) + OH1-(aq) Dissociation equation for NH3 NH3(g) + H2O(l) NH41+(aq) + OH1-(aq) 2) Bases cause indicators to turn a characteristic color 3) Bases neutralize acids NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l) 4) Water solutions of bases tasted bitter and feel slippery. Neutralization Neutralization is a chemical reaction between an acid and a base to produce a salt (an ionic compound) and water. NaOH(aq) + HCl(aq) base acid NaCl(aq) + H2O(l) salt water Some neutralization reactions: H2SO4(aq) + 2 NaOH(aq) sulfuric acid 2 HC2H3O2(aq) + acetic acid sodium hydroxide Ca(OH)2(aq) calcium hydroxide Na2SO4 + sodium sulfate 2 HOH water Ca(C2H3O2)2 + 2 HOH calcium acetate water Neutralization ACID + BASE SALT + WATER HCl + NaOH NaCl + H2O strong strong neutral HC2H3O2 + NaOH NaC2H3O2 + H2O weak strong basic • Salts can be neutral, acidic, or basic. • Neutralization does not mean pH = 7. Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem ACID + BASE SALT + WATER HCl + NaOH NaCl + H2O strong strong neutral HC2H3O2 + NaOH NaC2H3O2 + H2O weak strong basic • Salts can be neutral, acidic, or basic. • Neutralization does not mean pH = 7. Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem Salts NaCl Salts - Ionic compounds containing a positive ion other than the hydrogen ion andand a negative than salts the hydroxide ion. Formulas namesion of other common i.e., a metal and a non-metal SALT FORMULA Common Name Under what conditions do salts conduct current? sodium chloride NaCl(s) + H2O(l) sodium nitrate NaCl (table) salt Na1+(aq) + Cl1-(aq) NaNO3 Chile saltpeter sodium bicarbonate NaHCO3 baking soda potassium carbonate K2CO3 potash ammonium chloride NH4Cl sal ammoniac Salt Formation strong base strong acid NaOH HCl salt of a strong base and a strong acid NaCl NaOH + HCl NaCl + H2O strong base weak acid NaOH HC2H3O2 NaC2H3O2 salt of a strong base and a weak acid NaOH + HC2H3O2 NaC2H3O2 + H2O Note: that in each case H-OH (water) is formed Salt Formation weak base strong acid NH3 H2SO4 salt of a weak base and a strong acid (NH4) 2 SO4 H2SO4 NH4OH NH4OH + H2SO4 (NH4)2SO4 + H2O weak base weak acid NH3 HC2H3O2 NH4 C2H3O2 salt of a weak base and a weak acid NH4OH + HC2H3O2 NH4C2H3O2 + H2O Note: that in each case H-OH (water) is also formed weak base strong acid NH3 H2SO4 (NH4) 2 SO4 2 NH4OH ammonium ion + hydroxide ion salt of a weak base and a strong acid H2SO4 (NH4)2SO4 sulfuric acid ammonium sulfate + 2 HOH water sulfate ion 1- 1+ H2SO4 NH4OH 21+ 1- 1+ 2 NH4OH NH4+ NH4+ 1+ OHOH- + H2SO4 H2SO4 (NH4)2SO4 (NH4)2SO4 + 2 H 2O HOH HOH Reactions that produce salt acid + base salt + water H3PO4 + NH4OH (NH4)3PO4 + H2O phosphoric acid and ammonium hydroxide HNO3 nitric acid H2CO3 Mg(OH)2 magnesium hydroxide KOH yields ammonium phosphate and water Mg(NO3)2 magnesium nitrate K2CO3 carbonic acid potassium hydroxide potassium carbonate HC2H3O2 Al(OH)3 Al(C2H3O2)3 acetic acid aluminum hydroxide aluminum acetate HClO4 perchloric acid Ba(OH)2 barium hydroxide H2O Ba(ClO4)2 barium perchlorate H2O H2O H2O Brønsted-Lowry Acids and Bases Acid = any substance that donates a proton. Base = any substance that accepts a proton. d+ 1- 1+ d- + HCl H2O H3O+ Cl- (acid) (base) hydronium ion chloride ion Brønsted-Lowry Acids and Bases Acid = any substance that donates a proton. Base = any substance that accepts a proton. d+ 1- 1+ d- + HCl H2O H3O+ Cl- (acid) (base) hydronium ion chloride ion Brønsted-Lowry Acids and Bases d- 1- 1+ d+ + NH3 H2O (base) (acid) NH4+ ammonium ion OH- hydroxide ion Brønsted-Lowry Acids and Bases d- 1- 1+ d+ + NH3 H2O (base) (acid) NH4+ ammonium ion OH- hydroxide ion Brønsted-Lowry Acids and Bases d- 1- 1+ d+ + NH3 H2O (base) (acid) NH4+ ammonium ion OH- hydroxide ion Brønsted-Lowry Acids and Bases d- 1- 1+ d+ + NH3 H2O (base) (acid) NH4+ ammonium ion OH- hydroxide ion Definitions Brønsted-Lowry • Acids are proton (H+) donors. • Bases are proton (H+) acceptors. HCl + H2O acid – Cl + + H3O base conjugate base conjugate acid Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem Definitions H2O + HNO3 H3O+ + NO3– B A CA Base Acid O H O H N H O O Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem CB Definitions NH3 + H2O B A + NH4 CA Base + OH CB Acid H H N H Amphoteric H O H - can be an acid or a base. Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem Definitions Give the conjugate base for each of the following: - HF F H3PO4 H2PO4 + H3O H2O Polyprotic - an acid with more than one H+ Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem Definitions Give the conjugate acid for each of the following: Br - HBr HSO4 H2SO4 2CO3 HCO3 Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem Definitions Lewis • Acids are electron pair acceptors. • Bases are electron pair donors. Lewis base Lewis acid Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem Basic 7 Acid 14 Neutral pH Scale Acidic 0 Base Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 515 [H+] pH 10-14 14 10-13 13 10-12 12 10-11 11 10-10 10 10-9 9 10-8 8 10-7 7 10-6 6 10-5 5 10-4 4 10-3 3 10-2 2 10-1 1 100 0 1 M NaOH Ammonia (household cleaner) Blood Pure water Milk Vinegar Lemon juice Stomach acid 1 M HCl pH of Common Substances gastric juice 1.6 vinegar 2.8 carbonated beverage 3.0 0 1 2 acidic Timberlake, Chemistry 7th Edition, page 335 urine 6.0 4 5 bile 8.0 6 7 neutral [H+] = [OH-] 8 ammonia 11.0 bleach 12.0 seawater 8.5 9 1.0 M NaOH (lye) 14.0 milk of magnesia 10.5 detergents 8.0 - 9.0 milk 6.4 tomato 4.2 coffee 5.0 3 blood 7.4 potato 5.8 apple juice 3.8 lemon juice 2.2 drinking water 7.2 bread 5.5 orange 3.5 1.0 M HCl 0 water (pure) 7.0 soil 5.5 10 11 basic 12 13 14 pH of Common Substance More acidic More basic pH NaOH, 0.1 M Household bleach Household ammonia Lime water Milk of magnesia Borax Baking soda Egg white, seawater Human blood, tears Milk Saliva Rain Black coffee Banana Tomatoes Wine Cola, vinegar Lemon juice Gastric juice 14 13 12 11 10 9 8 7 76 5 4 3 2 1 0 [H1+] [OH1-] pOH 1 x 10-14 1 x 10-13 1 x 10-12 1 x 10-11 1 x 10-10 1 x 10-9 1 x 10-8 1 x 10-7 1 x 10-6 1 x 10-5 1 x 10-4 1 x 10-3 1 x 10-2 1 x 10-1 1 x 100 1 x 10-0 1 x 10-1 1 x 10-2 1 x 10-3 1 x 10-4 1 x 10-5 1 x 10-6 1 x 10-7 1 x 10-8 1 x 10-9 1 x 10-10 1 x 10-11 1 x 10-12 1 x 10-13 1 x 10-14 0 1 2 3 4 5 6 8 9 10 11 12 13 14 Acid – Base Concentrations concentration (moles/L) 10-1 pH = 3 pH = 11 OH- H3O+ pH = 7 10-7 H3O+ OH- OH- H3O+ 10-14 Timberlake, Chemistry 7th Edition, page 332 [H3O+] > [OH-] [H3O+] = [OH-] acidic solution neutral solution [H3O+] < [OH-] basic solution pH pH = -log [H1+] Kelter, Carr, Scott, Chemistry A World of Choices 1999, page 285 pH Calculations pH pH = -log[H3O+] [H3O+] [H3O+] = 10-pH [H3O+] [OH-] = 1 x10-14 pH + pOH = 14 pOH pOH = -log[OH-] [OH-] [OH-] = 10-pOH pH = - log [H+] Given: pH = 4.6 pH = - log [H+] choose proper equation 4.6 = - log [H+] substitute pH value in equation - 4.6 = 2nd log determine the [hydronium ion] - 4.6 = log [H+] log [H+] [H+] = 2.51x10-5 M multiply both sides by -1 take antilog of both sides Recall, [H+] = [H3O+] 10x antilog You can check your answer by working backwards. pH = - log [H+] pH = - log [2.51x10-5 M] pH = 4.6 Acid Dissociation monoprotic e.g. HCl, HNO3 HA(aq) 0.03 M H1+(aq) + A1-(aq) 0.03 M 0.03 M pH = ? pH = - log [H+] pH = - log [0.03M] pH = 1.52 diprotic e.g. H2SO4 H2A(aq) 0.3 M 2 H1+(aq) + A2-(aq) 0.6 M 0.3 M pH = - log [H+] pH = - log [0.6M] pH = 0.22 polyprotic e.g. H3PO4 H3PO4(aq) ?M 3 H1+(aq) + PO43-(aq) xM Given: pH = 2.1 find [H3PO4] assume 100% dissociation Given: pH = 2.1 3 H1+(aq) + PO43-(aq) 0.00794 M H3PO4(aq) XM find [H3PO4] assume 100% dissociation Step 1) Write the dissociation of phosphoric acid Step 2) Calculate the [H+] concentration pH = - log [H+] [H+] = 10-pH 2.1 = - log [H+] [H+] = 10-2.1 - 2.1 = log [H+] [H+] = 0.00794 M 2nd 7.94 x10-3 M log - 2.1 = 2nd log log [H+] [H+] = 7.94 x10-3 M Step 3) Calculate [H3PO4] concentration Note: coefficients (1:3) for (H3PO4 : H+) 7.94 x10-3 M = 0.00265 M H PO 3 4 3 How many grams of magnesium hydroxide are needed to add to 500 mL of H2O to yield a pH of 10.0? Step 1) Write out the dissociation of magnesium hydroxide Mg(OH)2(aq) -4 M 0.5 5 x10-5 Step 2) Calculate the pOH Step 3) Calculate the [OH1-] Mg2+(aq) + 2 OH1-(aq) 1 x10-4 M Mg2+ OH1Mg(OH)2 pH + pOH = 14 10.0 + pOH = 14 pOH = 4.0 pOH = - log [OH1-] [OH1-] = 10-OH [OH1-] = 1 x10-4 M Step 4) Solve for moles of Mg(OH)2 x mol mol 5 x10 -5 M 0.5 L L Step 5) Solve for grams of Mg(OH)2 M x g Mg(OH)2 = 2.5 x 10-5 mol Mg(OH)2 x = 2.5 x 10-5 mol Mg(OH)2 58 g Mg(OH)2 = 0.00145 g Mg(OH)2 1 mol Mg(OH)2 I WISH I HAD SWEAT GLANDS. Equilibrium • LeChatelier’s Principle CO2 + CaO CaCO3 “chicken breath” “food” “egg shell” As temperature increases, chickens “pant” more. This stresses the system and shifts the equilibrium to the This makes the egg shells THIN and fragile. LEFT I wish I had sweat glands. In a chicken… CaO + CO2 In summer, [ CO2 ] in a chicken’s blood -- shift CaCO3 (eggshells) due to panting. ; eggshells are thinner How could we increase eggshell thickness in summer? [ CO2 ] , shift -- give chickens carbonated water [ CaO ] , shift -- put CaO additives in chicken feed -- air condition the chicken house TOO much $$$ -- pump CO2 gas into the chicken house would kill all the chickens! LeChatelier’s Principle N2 + 3 H2 2 NH3 + heat Raising the temperature… Increasing the pressure… Decreasing the concentration of NH3… Dorin, Demmin, Gabel, Chemistry The Study of Matter 3rd Edition, page 532 …favors the endothermic reaction (the reverse reaction) in which the rise in temperature is counteracted by the absorption of heat. …favors the forward reaction in which 4 mol of gas molecules is converted to 2 mol. …favors the forward reaction in order to replace the NH3 that has been removed. Animation by Raymond Chang All rights reserved Equilibrium Expression Haber Process N2 + 3 H2 products K eq reactants Dorin, Demmin, Gabel, Chemistry The Study of Matter 3rd Edition, page 532 2 NH3 + heat NH3 K eq 3 N2 H2 2 reversible reaction: Reactant Product Reactant and P R Product Acid dissociation is a reversible reaction. H2SO4 equilibrium: 2 H1+ + SO42– Rate at which Rate at which R P P R = looks like nothing is happening, however… system is dynamic, NOT static Le Chatelier’s principle Le Chatelier’s principle: When a system at equilibrium is disturbed, it shifts to a new equilibrium that counteracts the disturbance. N2(g) + 3 H2(g) Disturbance 2 NH3(g) Equilibrium Shift Add more N2………………….. “ “ H2………………….. “ “ NH3………………… Remove NH3………………….. Add a catalyst………………… Increase pressure……………. Fritz Haber no shift Light-Darkening Eyeglasses AgCl + energy (clear) Go outside… Ago + Clo (dark) Sunlight more intense than inside light; “energy” shift to a new equilibrium: GLASSES DARKEN Then go inside… “energy” shift to a new equilibrium: GLASSES LIGHTEN Sensitive Sunglasses Oxidation-reduction reactions are the basis for many interesting and useful applications of technology. One such application is photochromic glass, which is used for the lenses in light sensitive glasses. Lenses manufactured by the Corning Glass Company can change from transmitting 85% of light to only transmitting 22% of light when exposed to bright sunlight. Photochromic glass is composed of linked tetrahedrons of silicon and oxygen atoms jumbled together in a disorderly array, with crystals of silver chloride caught in between the silica tetrahedrons. When the glass is clear, the visible light passes right through the molecules. The glass absorbs ultraviolet light, however, and this energy triggers an oxidation-reduction reaction between Ag+ and Cl-: Ag+ + Cl- --> Ag0 + Cl0 To prevent the reaction from reversing itself immediately, a few ions of Cu+ are incorporated into the silver chloride crystal. These Cu+ ions react with the newly formed chlorine atoms: Cu+ + Cl0 --> Cu2+ + ClThe silver atoms move to the surface of the crystal and form small colloidal clusters of silver metal. This metallic silver absorbs visible light, making the lens appear dark (colored). As the glass s removed from the light, the Cu2+ ions slowly move to the surface of the crystal where they interact with the silver metal: Cu2+ + Ag0 --> Cu+ + Ag+ The glass clears as the silver ions rejoin chloride ions in the crystals. Maintaining Blood pH Carbon dioxide is exhaled Acid entering the blood stream HCO31- + H+ H2CO3 H2O + CO2 Bicarbonate ion circulates in the blood stream where it is in equilibrium with H+ and OH-. In the lungs, bicarbonate ions combine with a hydrogen ion and lose a water molecule to form carbon dioxide, which is exhaled. Kelter, Carr, Scott, Chemistry A World of Choices 1999, page 291 Alkalosis If our breathing becomes too fast (hyperventilation)… Carbon dioxide is removed from the blood too quickly. This accelerates the rate of degradation of carbonic acid into carbon dioxide and water. The lower level of carbonic acid encourages the combination of hydrogen ions and bicarbonate ions to make more carbonic acid. The final result is a fall in blood H1+ levels that raises blood pH which can result in over-excitability or death. Kelter, Carr, Scott, Chemistry A World of Choices 1999, page 291 Acidosis If breathing becomes too slow (hypoventilation)… …free up acid, pH of blood drops, with associated health risks such as depression of the central nervous system or death. The normal pH of blood is between 7.2 – 7.4. This pH is maintained by the bicarbonate ion and other buffers. Kelter, Carr, Scott, Chemistry A World of Choices 1999, page 291 Acids: Concentration vs. Strength WEAK STRONG CONCENTRATED H+ A- H+ A- H+ A- H+ A- HA A- H+ A- H+ A- H+ A- H+ A H+ A- HA H+ A- H+ A- H+ AA- H+ A- H+ A- H+ A- H+ A- H+ H+ A - H + A - H + A - HA H + A A- H+ A- H+ A- H+ A- H+ A– H+ A- H+ A- H+ A- H+ A- H+ A- H+ A- H+ A- H+ A- H+ AHA A- H+ A- H+ A- H+ A- H+ HA HA H+ A- HA HA HA HA HA HA HA H+ A- HA HA HA HA HA HA H+ A- HA HA HA HA HA H+ A- HA H+ A- HA HA HA HA HA HA HA H+ A- HA H+ A- HA HA HA HA HA HA H+ A- HA HA HA H+ AHA HA HA HA HA HA HA DILUTE H+ A- H+ A- HA A- H+ A- H+ A– H+ A- H+ A- H+ A- H+ HA H+ A- HA H+ HA A- HA HA HA H+ A - HA HA HA HA H+A– A- Dissociate nearly 100% HA H1+ + A- + A- H+ HA HA HA H+A– HA STRONG ACIDS HA WEAK ACIDS Dissociate very little HA H1+ Comparison of Strong and Weak Acids Type of acid, HA Reversibility of reaction Ka value Ions existing when acid, HA, dissociates in H2O Strong Not reversible Ka value very large H+ and A-, only. No HA present. Weak reversible Ka is small H+, A-, and HA HA(aq) + H2O(l) H3O+(aq) + A-(aq) The equilibrium expression for the reaction is Ka = [H3O+] [A-] [HA] Note: H3O+ = H+ Strong vs. Weak Acid Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 508 Concentrated vs. Dilute 0.3 M HCl 10.0 M CH3COOH Dilute, strong acid Concentrated, weak acid 2.0 M HCl Concentrated, strong acid OR Dilute, strong, acid 12.0 M HCl Concentrated, strong acid Naming Acids Anion Acid _________ ide (chloride, Cl1-) add H+ _________ ate (chlorate, ClO3-) (perchlorate, ClO4-) add H+ _________ite (chlorite, ClO2-) (hypochlorite, ClO-) add H+ ions ions ions Hydro____ ic acid (hydrochloric acid, HCl) _________ic acid (chloric acid, HClO3) (perchloric acid, HClO4) ______ous acid (chlorous acid, HClO2) (hypochlorous acid, HClO) 7A HF No acid or base properties Weak base --- Weak acid SiH4 PH3 H2S HCl No acid or base properties Weak base Weak acid Strong acid Increasing acid Strength Increasing base Strength Brown, LeMay, Bursten, Chemistry 2000, page 625 Increasing acid Strength Period 3 6A H2O 4A CH4 Increasing base Strength Period 2 Group 5A NH3 Equilibrium and pH Calculations Weak acid Strong acid H3O+ + A- HA + H2O HA + H2O H3O+ + A- acid-dissociation constant calculations Ka = [A-] [H3O+] [HA] [HA] = [H3O+] [H3O+] + antilog(-pH) 7 [OH-] -log [H3O+] = pH 0 1 x 10-14 = [OH-] 14 Tocci, Viehland, Holt Chemistry Visualizing Matter 1996, page 525 1 x 10-14 [H3O+] = - Strengths of Conjugate Acid-Base Pairs Acid strength increases strong HCl H2SO4 medium weak very weak HNO3 H3O+ HSO4- H3PO4 HC2H3O2 H2CO3 H2S H2PO4- NH4+ HCO3- HPO42- H2O Cl- HSO4- negligible NO3 H2O SO42- H2PO4- very weak C2H3O2- HCO3- HS- HPO42- weak Base strength increases NH3 medium CO32- PO43- OH- strong Conjugate Acid Strength Relative acid strength Relative conjugate base strength Very strong Very weak Strong HA H+ + A- Weak [H+] [A-] pKa = [HA] Weak Strong Very weak Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 508 Very strong Solutions of Acids and Bases: The Leveling Effect • No acid stronger than H3O+ and no base stronger than OH– can exist in aqueous solution, leading to the phenomenon known as the leveling effect. • Any species that is a stronger acid than the conjugate acid of water (H3O+) is leveled to the strength of H3O+ in aqueous solution because H3O+ is the strongest acid that can exist in equilibrium with water. • In aqueous solution, any base stronger than OH– is leveled to the strength of OH– because OH– is the strongest base that can exist in equilibrium with water • Any substance whose anion is the conjugate base of a compound that is a weaker acid than water is a strong base that reacts quantitatively with water to form hydroxide ion Weak Acids (pKa) Weak Acids – dissociate incompletely (~20%) Strong Acids – dissociate completely (~100%) A(g) + 2 B(g) 3 C(g) + D(g) Equilibrium constant (Keq) = Keq = [Products] [Reactants] [C ]3 [D] [ A][B ]2 LeChatelier’s Principle (lu-SHAT-el-YAY’s) H+(aq) + C2H3O21-(aq) HC2H3O2(aq) 1 Equilibrium constant Keq = [H ][C2H3O2 ] [HC2H3O2 ] = Ka = Acid dissociation constant Ka = 1.8 x 10-5 @ 25 oC for acetic acid 1 [H ][C2H3O2 ] Ka = [HC2H3O2 ] 1 1.8 x 10-5 [H ][C2H3O2 ] = [HC2H3O2 ] Ionization Constants for Acids Ka HCl H+ + Cl1- very large HNO3 H+ + NO31- very large H2SO4 H+ + HSO41- HC2H3O2 H2S large H+ + C2H3O21- 1.8 x 10-5 H+ 9.5 x 10-8 + HS1- Ionization of Acids Acid Hydrochloric Ionization Equation HCl Sulfuric H2SO4 Acetic HC2H3O2 Ionization Constant, pKa H1+ + Cl1H1+ + HSO41H1+ + C2H3O21- very large large 1.8 x 10-5 Formula Name Value of Ka* HSO4HClO2 HC2H2ClO2 HF HNO2 HC2H3O2 HOCl HCN NH4+ HOC6H5 hydrogen sulfate ion chlorous acid monochloracetic acid hydrofluoric acid nitrous acid acetic acid hypochlorous acid hydrocyanic acid ammonium ion phenol 1.2 x 10-2 1.2 x 10-2 1.35 x 10-3 7.2 x 10-4 4.0 x 10-4 1.8 x 10-5 3.5 x 10-8 6.2 x 10-10 5.6 x 10-10 1.6 x 10-10 *The units of Ka are mol/L but are customarily omitted. Increasing acid strength Values of Ka for Some Common Monoprotic Acids Sample 1) One gram of concentrated sulfuric acid (H2SO4) is diluted to a 1.0 dm3 volume with water. What is the molar concentration of the hydrogen ion in this solution? What is the pH? Solution) First determine the number of moles of H2SO4 x mol H2SO4 = 1 g H2SO4 H2SO4 H+ + HSO41- 1 mol H2SO4 98 g H2SO4 & = 0.010 mol H2SO4 HSO41- H+ + SO42- OVERALL: H2SO4 0.010 M 2 H+ + SO42- in dilute solutions...occurs ~100% 0.020 M pH = - log [H+] substitute into equation pH = - log [0.020 M] pH = 1.69 A volume of 5.71 cm3 of pure acetic acid, HC2H3O2, is diluted with water at 25 oC to form a solution with a volume of 1.0 dm3. What is the molar concentration of the hydrogen ion, H+, in this solution? (The density of pure acetic acid is 1.05 g/cm3.) Step 1) Find the mass of the acid Mass of acid = density of acid x volume of acid = 1.05 g/cm3 x 5.71 cm3 = 6.00 g Step 2) Find the number of moles of acid. (From the formula of acetic acid, you can calculate that the molar mass of acetic acid is 60 g / mol). 1 mol HC 2H3O 2 = 0.10 mol acetic acid (in 1 L) x mol acetic acid = 6.00 g HC2H3O2 60 g HC H O 2 3 2 Molarity: M = mol / L Substitute into equation M = 0.10 mol / 1 L M = 0.1 molar HC2H3O2 Step 3) Find the [H+] Ka = HC2H3O2 Step 3) Find the 0.1 M [H+] weak acid H+ + C2H3O21- 0.1? M Ka = 1.8 x 10-5 @ 25 oC for acetic acid 1 [H ][C2H3O2 ] Ka = [HC2H3O2 ] 1 1.8 x 10-5 [H ][C2H3O2 ] = [HC2H3O2 ] How do the concentrations of H+ and C2H3O21- compare? [x][x] [HC2H3O2 ] Substitute into equation: 1.8 x 10-5 1.8 x 10 -5 x2 [0.10 M] pH = - log[H+] x2 = 1.8 x 10-6 M x = 1.3 x 10-3 molar pH = - log [1.3 x10-3 M] = [H+] pH = 2.9 H+ Concentrations …Strong vs. Weak Acid Moles of Acid used to make 1 L of solution H+ pH 0.010 mol H2SO4 0.0200 M 1.7 Strong acid 0.100 mol HC2H3O2 0.0013 M 2.9 Weak acid Note: although the sulfuric acid is 10x less concentrated than the acetic acid... …it produces > 10x more H+ pH = - log[H+] Practice Problems: 1a) What is the molar hydrogen ion concentration in a 2.00 dm3 solution of hydrogen chloride in which 3.65 g of HCl is dissolved? 1b) pH 2a) What is the molar concentration of hydrogen ions in a solution containing 3.20 g of HNO3 in 250 cm3 of solution? 2b) pH 3a) An acetic acid solution is 0.25 M. What is its molar concentration of hydrogen ions? 3b) pH 4) A solution of acetic acid contains 12.0 g of HC2H3O2 in 500 cm3 of solution. What is the molar concentration of hydrogen ions? 1a) 0.0500 M 1b) pH = 1.3 2a) 0.203 M 2b) pH = 0.7 3a) 2.1 x 10-3 M 3b) pH = 2.7 4) 2.7 x 10-3 M Weak Acids Cyanic acid is a weak monoprotic acid. If the initial concentration of cyanic + is 4.8 x 10-3 M, acid is 0.150 M and the equilibrium concentrationHof3O H3+O(aq) calculate Ka for cyanic acid. 4.8 x 10-3 M 0.150 M Ka = + CN1-(aq) H+(aq) HCN(aq) [Products] [Reactants] Ka = 4.8 x 10-3 M [H3O+] [CN1-] [HCN] [4.8 x 10-3 M][4.8 [CNx1-10 ] -3 M] Ka = [0.150 M] Ka = 1.54 x 10-4 How is [H3O+] determined? Measure pH of solution and work backwards Acid Dissociation + H 1- HCl Cl Acid Conjugate base Conjugate pair Kelter, Carr, Scott, Chemistry A World of Choices 1999, page 280 Conjugate Acid-Base Pairs conjugates HCl + base acid H 2O H3O+ + acid Clbase conjugates HCl acid + H 2O H3O+ base CA + ClCB Conjugate Acid-Base Pairs conjugates acid NH3 + H2O base base NH41+ + OH- acid conjugates NH3 base + H2O acid NH41+ CA + OHCB Water is Amphoteric Amphoteric or Amphiprotic substances: Substances which can act as either proton donors (acids) or proton acceptors (bases) depending on what substances are present. HCl + acid NH3 base + H2O H3O+ base CA H2O acid NH41+ CA + ClCB + OHCB Amphoteric A substance that can act as either an acid or a base. 11+ + H3O+ hydronium ion + HSO4hydrogen sulfate ion 1- H2O water H2SO4 sulfuric acid 2- 1- + HSO4hydrogen sulfate ion OHhydroxide ion + SO42- H2O sulfate ion water Amphoteric A substance that can act as either an acid or a base. 11+ + H3O+ hydronium ion + HSO4hydrogen sulfate ion (HSO4- as a base) H2SO4 sulfuric acid H2O water Amphoteric A substance that can act as either an acid or a base. 1- 21- + + HSO4- OH- SO42- H2O hydrogen sulfate ion hydroxide ion sulfate ion water (HSO4- as an acid) Conjugate Acid-Base Pairs conjugates base2 HC2H3O2 + H2O acid2 H3O1+ + acid1 C2H3O2OHbase1 conjugates HC2H3O2 + H2O acid base H3O1+ CA + C2H3O2OHCB The reaction proceeds in the direction such that the stronger acid donates its proton to the stronger base. Litmus Paper Copyright © 2007 Pearson Benjamin Cummings. All rights reserved. pH Paper pH 0 1 2 3 4 5 6 pH 7 8 9 10 11 12 13 Copyright © 2007 Pearson Benjamin Cummings. All rights reserved. Desired Features of Sensors pH paper 1904 pH 0 1 2 3 4 5 pH 7 8 9 10 11 12 6 13 Detection limit Low deflection High sensitivity High selectivity Wide dynamic range Simple to use Cost-effective Range and Color Changes of Some Common Acid-Base Indicators pH Scale 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Indicators Methyl orange Methyl red Bromthymol blue Neutral red Phenolphthalein 3.1 – 4.4 red red 4.4 yellow yellow 6.2 6.2 red colorless 6.8 yellow 7.6 8.0 8.0 blue yellow 10.0 red Bromthymol blue indicator would be used in titrating a strong acid with a strong base. Phenolpthalein indicator would be used in titrating a weak acid with a strong base. Methyl orange indicator would be used in titrating a strong acid with a weak base. colorless beyond 13.0 pH Copyright © 2007 Pearson Benjamin Cummings. All rights reserved. INDICATOR COLORS IN TITRATION Indicator Acid color Transition color Base color STRONG ACID – STRONG BASE Litmus 2 pH Bromthymol blue 3 4 5 6 7 8 9 10 11 12 INDICATOR COLORS IN TITRATION Indicator Acid color Transition color Base color WEAK ACID – STRONG BASE Phenolphthalein 2 pH Phenol red 3 4 5 6 7 8 9 10 11 12 INDICATOR COLORS IN TITRATION Indicator Acid color Transition color Base color STRONG ACID – WEAK BASE Methyl orange 2 pH Bromphenol blue 3 4 5 6 7 8 9 10 11 12 Indicator 1 2 Orange IV 4 5 6 Colorless Phenolphthalein Methyl Red 3 Red Orange Peach Orange 7 8 9 10 11 12 Pink Yellow Yellow Red Common pH Indicators Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 520 Edible Acid-Base Indicators COLOR CHANGES AS A FUNCTION OF pH INDICATOR pH 2 3 4 5 6 7 8 9 10 11 12 RED APPLE SKIN BEETS BLUEBERRIES RED CABBAGE * CHERRIES GRAPE JUICE RED ONION YELLOW ONION PEACH SKIN PEAR SKIN PLUM SKIN RADISH SKIN RHUBARB SKIN TOMATO TURNIP SKIN *YELLOW at pH 12 and above Red Cabbage Indicator Copyright © 2007 Pearson Benjamin Cummings. All rights reserved. H+ Phenolphthalein Indicator Colorless = Acidic pH Pink = Basic pH -O O C C OH HO C O- O (Colorless acid form, HIn) C OH O- O (Pink base form, In-) Preparation of an Ester Acetylsalicylic Acid (Aspirin) OBJECTIVE: Aspirin Synthesis To become familiar with the techniques and principle of esterification. DISCUSSION: Aspirin is a drug widely used as an antipyretic agent (to reduce fever), as an analgesic agent (to reduce pain), and/or as an anti-inflammatory agent (to reduce redness, heat or swelling in tissues). Chemically, aspirin is an ester. Esters are the products of reaction of acids with alcohols, as shown in the following equation using type formulas: O O R – C – OH + ACID R’ – OH R – C – O – R’ ALCOHOL ESTER + H2O WATER The symbol R refers to the hydrocarbon portion (radical) of the molecules aside from the O functional group. In an organic acid, R – C – OH, the functional group is the carboxyl O group (-COOH) or –C-OH. The type of formula for an alcohol is R-OH, where the functional group is the hydroxyl group (-OH). The symbol R’ indicates that the two R-groups in the ester formula need not be the same. It has been shown by radioactive tracer methods that in the mechanism of the esterification reaction, the –OH group is split from the acid and the –H from the alcohol. Aspirin can be made as follows: C – OH CH3 – C – OH + Acetic acid HO – C – OH CH3 – C – O– + Salicylic acid Aspirin (containing an -OH group) (acetylsalicylic acid, an ester) H2O The use of acetic anhydride instead of acetic acid, however, is a better preparative method, because the anhydride with the water to form acetic acid tends to drive the reaction to the right as shown below. An acid catalyst also is used to speed up the reaction. CH3 O C C CH3 C – OH O O Acetic anhydride + HO – C – OH CH3 – C – O– Salicylic acid Aspirin (138.12 g/mol) (180.15 g/mol) + CH3 – C – OH Acetic acid How to read a buret volume 23 24.55 mL? 23.45 mL (not 24.55 mL) 24 Titration standard solution Titration • Analytical method in which a standard solution is used to determine the concentration of an unknown solution. unknown solution Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem Titration Equivalence point (endpoint) • Point at which equal amounts of H3O+ and OH- have been added. • Determined by… • indicator color change • dramatic change in pH Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem Titration + O moles H3 = moles MVn = MVn M: Molarity V: volume n: # of H+ ions in the acid or OH- ions in the base Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem OH Titration 42.5 mL of 1.3M KOH are required to neutralize 50.0 mL of H2SO4. Find the molarity of H2SO4. H3O+ OH- M=? M = 1.3M V = 50.0 mL n=2 V = 42.5 mL n=1 MV# = MV# M(50.0mL)(2) =(1.3M)(42.5mL)(1) M = 0.55M H2SO4 Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem Acid-Base Titration Data Table 0.10 M HCl Base (mL) Calibration Curve 0.00 mL 1.00 mL 2.00 mL 4.00 mL 9.00 mL 17.00 mL 27.00 mL 48.00 mL ? M NaOH 1.00 mL 1.00 mL 2.00 mL 5.00 mL 8.00 mL 10.0 mL 15.0 mL Acid (mL) 1) 2) 3) Solution Solution of of NaOH NaOH Create calibration curve of six data points Using [HCl], determine concentration of NH3 Determine vinegar concentration using [NaOH] determined earlier in lab Solution of HCl 5 mL Titration Curve Titration indicator -changes color to indicate pH change e.g. phenolpthalein is colorless in acid and pink in basic solution endpoint pink equivalence point pH 7 Pirate…”Walk the plank” once in water, shark eats and water changes to pink color base Calibration Curve endpoint Base (mL) pink pH 7 equivalence point Acid (mL) Pirate…”Walk the plank” once in water, shark eats and water changes to pink color base indicator - changes color to indicate pH change e.g. phenolphthalein is colorless in acid and pink in basic solution Calibration Curve endpoint Base (mL) pink pH 7 equivalence point Acid (mL) Pirate…”Walk the plank” once in water, shark eats and water changes to pink color base indicator - changes color to indicate pH change e.g. phenolphthalein is colorless in acid and pink in basic solution Titration Curve Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 527 Acid-Base Titrations Titration of a Strong Acid With a Strong Base 14.0 12.0 Solution of NaOH 10.0 OHNa+ Na+ pH - OH- OH Na+ Na+ OH- 8.0 equivalence point 6.0 4.0 Solution of HCl H+ Cl- 2.0 Cl H+ H+ Cl- H+ Cl- 0.0 0.0 10.0 20.0 30.0 40.0 Volume of 0.100 M NaOH added (mL) Additional Adding additional NaOH NaOH from isNaOH added. the buret is added. pH to increases hydrochloric pH rises and as acid theninlevels the flask, off as the NaOH a strong equivalence is acid. addedInbeyond point the beginning is the approached. equivalence the pH increases point. very slowly. Titration Data pH 0.00 10.00 20.00 22.00 24.00 25.00 26.00 28.00 30.00 40.00 50.00 1.00 1.37 1.95 2.19 2.70 7.00 11.30 11.75 11.96 12.36 12.52 Solution of NaOH Na+ OH- OHNa+ Na+ OH- Solution of HCl H+ Cl- 25 mL 14.0 12.0 10.0 8.0 equivalence point 6.0 4.0 2.0 OHNa+ Titration of a Strong Acid With a Strong Base pH NaOH added (mL) 0.0 0.0 10.0 20.0 30.0 40.0 Volume of 0.100 M NaOH added (mL) ClH+ H+ Yellow Blue Cl- H+ Cl- Bromthymol blue is best indicator: pH change 6.0 - 7.6 Titration of a Strong Acid With a Strong Base (20.00 mL of 0.500 M HCl by 0.500 M NaOH) 14.0 12.0 Color change alizarin yellow R 10.0 Color change phenolpthalein pH 8.0 Color change bromthymol blue equivalence point 6.0 Color change bromphenol blue 4.0 Color change methyl violet 2.0 0.0 0.0 10.0 20.0 30.0 Volume of 0.500 M NaOH added (mL) Hill, Petrucci, General Chemistry An Integrated Approach 2nd Edition, page 680 Titration of a Weak Acid With a Strong Base Titration of a Weak Acid With a Strong Base Titration Data 14.0 NaOH added (mL) 12.0 10.0 pH equivalence point 8.0 6.0 4.0 2.0 0.0 0.0 10.0 20.0 30.0 Volume of 0.100 M NaOH added (mL) 40.0 0.00 5.00 10.00 12.50 15.00 20.00 24.00 25.00 26.00 30.00 40.00 pH 2.89 4.14 4.57 4.74 4.92 5.35 6.12 8.72 11.30 11.96 12.36 Phenolphthalein is best indicator: pH change 8.0 - 9.6 Titration of a Weak Base With a Strong Acid Titration of a Weak Base With a Strong Acid Titration Data 14.0 HCl added (mL) pH 0.00 10.00 20.00 30.00 40.00 45.00 47.00 48.00 49.00 50.00 51.00 11.24 9.91 9.47 8.93 8.61 8.30 7.92 7.70 7.47 5.85 3.34 12.0 pH 10.0 8.0 6.0 equivalence point 4.0 2.0 0.0 0.0 10.0 20.0 30.0 40.0 Volume of 0.100 M HCl added (mL) 50.0 7. What is the pH of a solution made by dissolving 2.5 g NaOH in 400 mL water? Determine number of moles of NaOH 1 mol NaOH x mol NaOH = 2.5 g NaOH 0.0625 mol NaOH 40 g NaOH Calculate the molarity of the solution M mol L 0.0625 mol NaOH 0.4 L [Recall 1000 mL = 1 L] MNaOH = 0.15625 molar NaOH 0.15625 molar Na1+ + 0.15625 molar pOH = -log [OH-] OH10.15625 molar or kW = [H+] [OH-] pOH = -log [0.15625 M] 1 x 10-14 = [H+] [0.15625 M] pOH = 0.8 [H+] = 6.4 x 10-14 M pOH + pH = 14 pH = -log [H+] 0.8 + pH = 14 pH = 13.2 pH = -log [6.4 x 10-14 M] What volume of 0.5 M HCl is required to titrate 100 mL of 3.0 M Ca(OH)2? 2 HCl x mL 0.5 M + "6.0 M" Ca(OH)2 100 mL 3.0 M CaCl2 M1V1 = M2V2 (0.5 M) (x mL) = (3.0 M) (100 mL) + 2 HOH M1V1 = M2V2 (0.5 M) (x mL) = (6.0 M) (100 mL) x = 600 mL of 0.5 M HCl mol M L HCl 0.3 mol x = 1200 mL of 0.5 M HCl HCl molHCl = M x L Ca(OH)2 mol Ca(OH)2 = M x L mol = (0.5 M)(0.6 L) mol = (3.0 M)(0.1 L) mol = 0.3 mol HCl mol = 0.3 mol Ca(OH)2 H1+ + 0.3 mol Cl1- Ca(OH)2 0.3 mol 0.3 mol [H+] = [OH-] Ca2+ + 2OH1- 0.3 mol 0.6 mol 6. 10.0 grams vinegar titrated with 65.40 mL of 0.150 M NaOH (acetic acid + water) moles HC2H3O2 = A) moles NaOH mol M L NaOH molNaOH = M x L therefore, you have ... 0.00981 mol HC2H3O2 mol = (0.150 M)(0.0654 L) mol = 0.00981 mol NaOH 60 g HC3H2O2 0.59 g HC2H3O2 1 mol HC3H2O2 B) x g HC2H3O2 = 0.00981 mol HC2H3O2 C) part % = x 100% whole 0.59 g acetic acid % = x 100% 10.0 g vinegar % = 5.9 % acetic acid Commercial vinegar is sold as 3 - 5 % acetic acid Carboxylic Acid HC2H3O2 H = acetic acid O H C C 1O H H H+ CH3COOH R - COOH carboxylic acid C2H4O2 O H O H C O H H C H H Lactic Acid OH H3C C CO2H H Lactic acid C3H6O3 Titration ? 1.0 M HCl titrate with ? M NaOH 2.00 mL 1.00 mL M1 V1 = M2 V2 (1.0 M)(1.00 mL) = (x M)(2.00 mL) X = 0.5 M NaOH 1+ 2.0 M H 1.0 M H2SO4 1.00 mL titrate with ? M NaOH 2.00 mL M1 V1 = M2 V2 (1.0 M)(1.00 mL) = (x M)(2.00 mL) X = 0.5 M NaOH HCl Hydrochloric acid stomach acid, pickling metal H2SO4 Sulfuric acid battery acid, # 1 selling chemical H3PO4 Phosphoric acid food flavoring HNO3 Nitric acid fertilizer, explosives CH3COOH Acetic acid vinegar HF Hydrofluoric acid etch glass NaOH Ca(OH)2 NH4OH sodium hydroxide calcium hydroxide ammonium hydroxide Soren Sorenson developed pH scale 7 neutral pH scale 0 [H+] = [OH-] acid 14 base (alkalinity) Arnold Beckman invented the pH meter pH = -log [H+] pOH = -log [OH-] pH + pOH = 14 kW = [H+] [OH-] kw = 1 x 10-14 H+ + H2O proton H3O+ hydronium ion Concentrated vs. Dilute Concentration: Molarity molality mol M= L mol m = kg H2SO4 2 H1+ 3M “6 M” + SO42- Normality Strong / Weak Acid Strong HA H+ + A- (~100% dissociation) Weak HA H+ + A- (~20% dissociation) H2A 2 H+ [Product] Ka = [Reactant] + Ka = A- [H+]2 [A-] [H2A] acid dissociation constant Ka 0.8 0.0021 H3PO4 HF 3H+ + PO43H + + F- Acid + Base Salt + Water How would you make calcium sulfate in the lab? H2?SO4 + Ca(OH) ? 2 BASE ACID Sour taste, litmus CaSO4 + 2 H2O red bitter taste, litmus blue Arrhenius – H+ as only ion in water Arrhenius – OH- as only ion in water Brønsted-Lowry – proton donor Brønsted-Lowry – proton acceptor Indicators colorless weak acid phenolphthalein yellow strong acid bromthymol blue universal indicator & blue strong base R O Y G B I V pH 4 litmus paper pink strong base pH paper 7 12 Buffers - salts of weak acids and weak bases that maintain a pH e.g. Aspirin (acetyl salicylic acid) vs. Bufferin low pH upsets stomach LeChatelier’s Principle - acidosis & alkalosis (bicarbonate ion acts as buffer) - darkening glasses - egg shells thinner in summer (warm) Acid – Base Concentrations concentration (moles/L) 10-1 pH = 3 pH = 11 OH- H3O+ pH = 7 10-7 H3O+ OH- OH- H3O+ 10-14 Timberlake, Chemistry 7th Edition, page 332 [H3O+] > [OH-] [H3O+] = [OH-] acidic solution neutral solution [H3O+] < [OH-] basic solution Amino Acids – Functional Groups Amine Base Pair Carboxylic Acid R- COOH NH21lose H+ NH21- H+ NH3 amine ammonia NH41+ ammonium ion 1+ : 1- N N N H H : : H H H H H H H Amino Acids – Functional Groups Amine NH21- Base Pair Carboxylic Acid R- COOH + d+ H H+ O2- d http://fig.cox.miami.edu/~cmallery/150/chemistry/sf3x17b.jpg Water – Amphiprotic lose H+ OH1- H+ hydroxide H2O H3O1+ water hydronium ion : N H H : : N H 1+ H 1- N H H H H H Water – Also Amphiprotic Amphiprotic – Act as an acid (proton donor) or base (proton acceptor) OH1hydroxide lose H+ H+ H2O H3O1+ water hydronium ion + d+ H H+ O2- d Amino Acids – Functional Groups Amphiprotic – Act as an acid (proton donor) or base (proton acceptor) OH1hydroxide lose H+ H+ H2O H3O1+ water hydronium ion + d+ H H+ O2- d http://fig.cox.miami.edu/~cmallery/150/chemistry/sf3x17b.jpg Range and Color Changes of Some Common Acid-Base Indicators pH Scale 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Indicators Methyl orange Methyl red Bromthymol blue 3.1 – 4.4 red red 4.4 yellow Neutral red red Phenolphthalein colorless yellow 6.2 6.2 6.8 yellow 7.6 blue 8.0 8.0 yellow 10.0 red colorless beyond 13.0 Range and Color Changes of Some Common Acid-Base Indicators pH Scale 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Indicators Methyl orange Methyl red Bromthymol blue 3.1 – 4.4 red red 4.4 yellow Neutral red red Phenolphthalein colorless yellow 6.2 6.2 6.8 yellow 7.6 blue 8.0 8.0 yellow 10.0 red colorless beyond 13.0 pH Paper pH Paper pH 0 1 2 3 4 5 pH 7 8 9 10 11 12 6 pH 0 1 2 3 4 5 13 pH 7 8 9 10 11 12 13 6 pH Paper 6 pH Paper pH 0 1 2 3 4 5 pH 7 8 9 10 11 12 6 pH 0 1 2 3 4 5 13 pH 7 8 9 10 11 12 13 Neutralization of Bug Bites Wasp - stings with base Red Ant - bites with acid (neutralize with lemon juice or vinegar) (neutralize with baking soda) Strength Strong Acid/Base • 100% ionized in water • strong electrolyte HCl HNO3 H2SO4 HBr HI HClO4 - + NaOH KOH Ca(OH)2 Ba(OH)2 Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem Strength Weak Acid/Base • does not ionize completely • weak electrolyte HF CH3COOH H3PO4 H2CO3 HCN - + NH3 Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem Ionization of Water H 2O + H 2 O Kw = + [H3O ][OH ] H3 + O + = 1.0 Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem OH -14 10 Why is pure water pH = 7? 1 in 500,000,000 water molecules will autoionize. H2O + H2O H3O+ + OH1 This yields a hydronium ion concentration of 1 x 10-7 M H3O+ per liter of solution pH = -log[H3O+] pH = -log[1 x 10-7] or pH = 7 H H O 1- H O H H H H H 1+ O H O O O H O H H H H H O H H Ionization of Water Find the hydroxide ion concentration of 3.0 10-2 M HCl. [H3O+][OH-] = 1.0 10-14 [3.0 10-2][OH-] = 1.0 10-14 [OH-] = 3.3 10-13 M Acidic or basic? Acidic Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem pH Scale 14 0 7 INCREASING ACIDITY pH = NEUTRAL INCREASING BASICITY + -log[H3O ] pouvoir hydrogène (Fr.) “hydrogen power” Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem pH Scale pH = + -log[H3O ] pOH = -log[OH ] pH + pOH = 14 Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem pH Scale What is the pH of 0.050 M HNO3? pH = -log[H3O+] pH = -log[0.050] pH = 1.3 Acidic or basic? Acidic Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem pH Scale What is the molarity of HBr in a solution that has a pOH of 9.6? pH + pOH = 14 pH = -log[H3O+] pH + 9.6 = 14 4.4 = -log[H3O+] pH = 4.4 -4.4 = log[H3O+] Acidic [H3O+] = 4.0 10-5 M HBr Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem Resources - Acids and Bases Objectives Episode 16 – The Proton in Chemistry Worksheet - vocabulary Video (VHS) - future of the past Worksheet - pH and pOH calculations Outline - Worksheet - practice problems (key) Worksheet - Textbook - text ?'s chemical equilibrium Worksheet - Worksheet - weak acid, pKa Worksheet - Article - aspirin Worksheet - Lab - synthesis of aspirin Worksheet - aqueous acids and bases titration Lab - titration Textbook - questions Outline (general)