Acid/base properties Definitions › Polyprotic Acids › Amphoteric › Anhydrides › Arrhenius › Bronsted-Lowry › Lewis › Neutralization › Sulfides › Carbonates Acid-Base Reactions pH/pOH Scale Acid/base strength › Factor affecting › K a, K b , K w › Percent ionization Vocabulary Acids/Bases & Salts › Determine acidity › Calculations Common Ion Effect Buffers › Henderson-Hasselbalch Titration › Indicators › 4 types of curves Sour taste React with active metals to produce hydrogen gas Change the color of acid-base indicators React with bases to produce salt and water Conduct an electric current (electrolytes) Turn litmus paper red Sulfuric Acid › Car batteries; production of metals, paints, dyes, detergents Nitric Acid › Explosives, pharmaceuticals, rubber, plastics, dyes Phosphoric acid › Soda, fertilizers, animal feed, detergents Hydrochloric Acid › Stomach acid, cleaning metals, found in hardware stores (muriatic acid) Acetic Acid › Vinegar, food supplements, fungicide Citric Acid › Fruit juices Binary acids › Contain only two different elements › Name as “hydro - ic acid” › Example: HCl (hydrochloric acid) Oxyacids › Acid consisting of hydrogen and a polyatomic anion that contains oxygen (oxyanion) › To name, drop ending of polyatomic ion and ad “- ic acid” › Example: HNO3 (nitric acid) Taste bitter Feel slippery Change the color of acid-base indicators React with bases to produce salt and water Conduct an electric current (electrolytes) Turn litmus paper blue Ammonium hydroxide › Household cleaners, window cleaner Ammonia › (Gas) inhalant to revive unconscious person Sodium bicarbonate (baking soda) › Acid neutralizers in acid spills › Antacids for upset stomachs Sodium hydroxide › Drain cleaner (drano), oven cleaner, production of soap Magnesium hydroxide › Antacids, milk of magnesia, laxatives Acid › Substance that ionizes in water and produces H+ ions › Example: HCl H+ + Cl Base › Substance that ionizes in water and produces OH- ions › Example: NaOH Na+ + OH- Acid › Substance that is capable of donating a proton (H+ ion) Base › Substance that is capable of accepting a proton (H+ ion) HC2H3O2 + H2O ↔ C2H3O2- + H3O+ Acids: HC2H3O2 and H3O+ Bases: H2O and C2H3O2NH3 + H2O ↔ NH4+ + OHAcids: H2O and NH4+ Bases: NH3 and OHNotice that water can act as an acid or a base Conjugate Pair – a BL acid/base pair(one with H+ and one without H+) › Examples: HC2H3O2 and C2H3O2 H3O+ and H2O H2O and OH NH4+ and NH3 The more easily a substance gives up a proton, the less easily the conjugate base accepts a proton (and vice versa) › The stronger the acid, the weaker the conjugate base › The stronger the base, the weaker the conjugate acid Neutralization › Salt + water Sulfides › Salt + sulfide gas Carbonates › Salt + CO2 + H2O Solution of an acid and solution of a base are mixed Products have no characteristics of either the acid or the base Acid + Base (metal hydroxide) salt + water › Salt comes from cation of base and anion of acid HY + XOH XY + H2O HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l) Acid reacts with a sulfide Gaseous product (H2S) has a foul odor (rotten eggs) Acid + metal sulfide salt + hydrogen sulfide › Salt comes from cation of sulfide and anion of acid HY + XS XY + H2S HCl(aq) + Na2S(aq) NaCl(aq) + H2S(g) Carbonates and bicarbonates react with acids HY + XHCO3 XY + H2CO3 H2CO3 is not stable so breaks into H2O and CO2 Then HY + XHCO3 XY + H2O + CO2 HCl(aq) + NaHCO3(aq) NaCl(aq) + H2CO3 (aq) HCl(aq) + NaHCO3(aq) NaCl(aq) + H2O(l) + CO2(g) pH scale: measures concentration of hydrogen ions in solution pH = -log[H+] therefore [H+] = 10-pH Example: What is the pH of a solution with a [H+] of 1.4×10-5? pH = -log[1.4×10-5] = 4.9 Acids: pH < 7 Neutral: pH = 7 Bases: pH > 7 Increasing [H+] means decreasing pH Increasing pH means decreasing [H+] pOH scale: measures concentration of hydroxide ions in solution pOH = -log[OH-] therefore [OH-] = 10-pOH Example: What is the [OH-] of a solution with a pOH of 6.2? [OH-] = 10-6.2 = 6.3×10-7 pH + pOH = 14 An acid has a pH of 4, what is the pOH? 4 + pOH = 14 pOH = 10 pH meter › Electrodes measure [H+] Acid-base indicators › Change color in presence of acid or base (or certain pH ranges) › Litmus paper, phenolphthalein, cabbage juice, methyl orange, thymol blue… Completely ionize in solution (strong electrolytes) Strong Acids Strong Bases HCl Group 1 metals + OH HBr (LiOH, NaOH, KOH,…) HI HClO3 Heavy group 2 metals + OH HClO4 Ca(OH)2, Sr(OH)2, Ba(OH)2 HNO3 H2SO4 If acid/base is not on this list, it is a weak acid/base Do not completely ionize in water (weak electrolytes) Common weak acids: › HF, acids with -COOH group Common weak bases: › NH3 1. Electronegativity of element bonded to H › Binary acids › More electronegative bond = stronger acid › Example: HCl stronger than HBr 2. Bond Strength › Stronger bonds do not allow hydrogen to dissociate as easily › Reason why HF is not a strong acid (F is most electronegative, but H-F bond is strongest bond) 3. Stability of Conjugate base › More stable the conjugate base, the stronger the acid 4. For polyatomic ions, the more electronegative the nonmetal, the stronger the acid (when comparing acids with same number of O atoms) › Example: HClO3 is stronger than HBrO3 5. For polyatomic ions, when nonmetal is the same, the more O atoms, the stronger the acid › Example: HClO3 is stronger than HClO2 Tells us what percent of an acid (or base) is ionized in water › Helps determine the strength of an acid (or base) Percent Ionization = [H+] at equilibrium Initial Acid Concentration ×100 A 0.035 M solution of HNO2 contains 3.7×10-3 M H+(aq). Calculate the percent ionization. = 3.7×10-3 M 0.035 M = 11% This means that 11% of the acid will dissociate in water. HA(aq) + H2O(l) H+(aq) + A-(aq) acid water proton conjugate base Strong acids dissociate completely The dissociation is not reversible The acid is the only significant source of H+ ions, so pH can be calculated directly from the [H+] › Example: A 0.20 M solution of HNO3 has an [H+] of 0.20 M › pH = -log[H+] Strong bases dissociate completely The dissociation is not reversible The base is the only significant source of OH- ions, so pOH can be calculated directly from the [OH-] › Example: A 0.30 M solution of NaOH has a [OH-] of 0.30 M › pOH = -log[OH-] Do not dissociate completely Reversible reactions Need to use equilibrium to solve for [H+] K= [Products] [Reactants] HA(aq) + H2O(l) H+(aq) + A-(aq) acid water proton conjugate base Write the equilibrium expression for the acid dissociation constant, Ka. [ H ][ A ] Ka [ HA] B(aq) + H2O(l) ↔ BH+(aq) + OH-(aq) base water conjugate hydroxide acid ion Write the equilibrium expression for the base dissociation constant, Kb. [ BH ][OH ] Kb [ B] The greater the Ka, the stronger the acid The smaller the Ka, the weaker the acid The greater the Kb, the stronger the base The smaller the Kb, the weaker the base What is the pH of a 0.50 M solution of acetic acid, HC2H3O2, Ka = 1.8 x 10-5 ? HC2H3O2 C2H3O2- + H+ Step #1: Write the dissociation equation What is the pH of a 0.50 M solution of acetic acid, HC2H3O2, Ka = 1.8 x 10-5 ? Step #2: ICE I C E HC2H3O2 C2H3O2- + H+ 0.50 -x 0.50 - x 0 0 +x +x x x What is the pH of a 0.50 M solution of acetic acid, HC2H3O2, Ka = 1.8 x 10-5 ? Step #3: Set up the equilibrium expression 2 ( x)(x) x 1.8 x10 (0.50 x) (0.50) 5 3 x 3.0 x10 If percent ionization is less than 5%, you can ignore using the quadratic. What is the pH of a 0.50 M solution of acetic acid, HC2H3O2, Ka = 1.8 x 10-5 ? Step #5: Solve for pH 3 pH log(3.0 x10 ) 2.52 You can use the Kb expression to solve for pOH using the same method! A student prepared a 0.10 M solution of formic acid (HCOOH) and measured its pH. The pH at 25°C was found to be 2.38. Calculate the Ka for formic acid at this temperature. Step #1: Solve for [H+] from pH [H+] = 10-2.38 = 4.2×10-3 M A student prepared a 0.10 M solution of formic acid (HCOOH) and measured its pH. The pH at 25°C was found to be 2.38. Calculate the Ka for formic acid at this temperature. Step #2: Set up ICE table HCOOH(aq) HCOO- + I C E 0.10 0 H+ 0 4.2×10-3 A student prepared a 0.10 M solution of formic acid (HCOOH) and measured its pH. The pH at 25°C was found to be 2.38. Calculate the Ka for formic acid at this temperature. Step #3: Use stoichiometry to complete table HCOOH(aq) HCOO- + H+ I C 0.10 0 0 4.2×10-3 4.2×10-3 4.2×10-3 E 0.0096 4.2×10-3 4.2×10-3 A student prepared a 0.10 M solution of formic acid (HCOOH) and measured its pH. The pH at 25°C was found to be 2.38. Calculate the Ka for formic acid at this temperature. Step #4: Solve for Ka using equilibrium expression Ka = 1.8×10-4 The larger the value of Ka, the stronger the acid According to Bronsted Lowry, H2O can act as either an acid or a base Auto-ionization: One water molecule can donate a proton to another water molecule › Extremely rapid reaction and no molecule remains ionized for long › At room temperature 1 out of every 109 molecule are ionized at a given instant › Water is a nonelectrolyte and consists almost entirely of H2O molecules H2O(l) + H2O(l) ↔ H3O+ + OH- H2O(l) + H2O(l) ↔ H3O+ + OH- Auto-ionization of water is an equilibrium process (use Kw - ion product constant) Kw = [H3O+][OH-] Also written as Kw = [H+][OH-] At 25°C, Kw =1.4×10-14 1.4×10-14 = [H+][OH-] In basic solutions, [OH-] > [H+] In acidic solutions, [H+] > [OH-] In neutral solutions, [H+] = [OH-] 1.4×10-14 = [H+][OH-] If the concentration of one ion is known, you can solve for the concentration of the other ion Example: Calculate the concentration of H+ in a solution in which the concentration of OH- is 0.010M. 1.4×10-14 = [H+][0.010] [H+] = 1.0×10-12 M Acid or base dissociation constants are sometimes expressed as pKa and Kb. › pKa = –logKa › pKb = -logKb pKw = 14 = pKa+ pKb Acids with more than one ionizable H+ ion H2SO3(aq) ↔ H+(aq) + HSO3-(aq) HSO3-(aq) ↔ H+(aq) + SO3-2(aq) Ka1 = 1.7×10-2 Ka2 = 6.4×10-8 The acid-dissociation constants are Ka1, Ka2, etc… The first proton is most easily removed › As protons are removed, it becomes more and more difficult to remove protons › Ka1>Ka2>Ka3…. To calculate the overall K for the reaction, treat it as a multi-step equilibrium H2SO3(aq) ↔ H+(aq) + HSO3-(aq) HSO3-(aq) ↔ H+(aq) + SO3-2(aq) Ka1 = 1.7×10-2 Ka2 = 6.4×10-8 Overall reaction… H2SO3(aq) ↔ 2H+(aq) + SO3-2(aq) Ka = (1.7×10-2)(6.4×10-8) = 1.1×10-9 Ka = Ka1 × Ka2 Strong acids (ex H2SO4) completely ionize with the first step › pH can be calculated by treating the acid as if it were a monoprotic acid (one ionizable hydrogen) If Ka values differ by a factor of 103 or more, acids can be treated as monoprotic Monoprotic acid = 1 ionizable H+ Diprotic acid = 2 ionizable H + Triprotic acid = 3 ionizable H + Etc… Substances that can act as either acids or bases › Example: H2O Can give up H+ to become OH Can receive H + to become H3O + › Example: H2PO4 Can give up H + to become HPO4-2 Can receive H + to become H3PO4 Acid Anhydride: combines with water to form an acid › CO2 + H2O H2CO3 › SO3 + H2O H + + HSO4 Base Anhydride: combines with water to form a base › CaO + H2O Ca(OH)2 › Na2O + H2O 2Na+ + 2OH- #1 If a salt is composed of the conjugates of a strong acid and strong base, the solution will be neutral. #2 If a salt is composed of the conjugates of a weak base and a strong acid, its solution will be acidic. #3 If a salt is composed of the conjugates of a strong base and a weak acid, its solution will be basic. #4 If a salt is composed of the conjugates of a weak base and a weak acid, the pH of its solution will depend on the relative strengths of the conjugate acid and base of the specific ions in the salt. If a salt is composed of the conjugates of a strong acid and strong base, the solution will be neutral. HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l) The Na+ and Cl- ions do not further ionize in water If a salt is composed of the conjugates of a strong acid and weak base, the solution will be acidic. HCl(aq) + NH3(aq) NH4Cl(s) The NH4Cl ionizes in water to produce some H+ ions (the Cl - ions do not react in water) NH4Cl(s) NH4+(aq) + Cl-(aq) NH4+ + H2O NH3+ + H+ Solution Is acidic If a salt is composed of the conjugates of a weak acid and strong base, the solution will be basic. NaOH(aq) + HC2H3O2(aq) NaC2H3O2(s) + H2O(l) The NaC2H3O2 ionizes in water NaC2H3O2(s) Na+(aq) + C2H3O2-(aq) The Na+ ions do not react at all, but the C2H3O2ions react to produce OH- in solution C2H3O2-(aq) + H2O HC2H3O2 + OH- Solution Is basic If a salt is composed of the conjugates of a weak acid and weak base, the pH of the solution will depend on the relative strengths of the conjugate acid and base of the specific ions in the salt. › The ion with the larger equilibrium constant (Ka or Kb) will have the greater influence on pH) Hydrolysis › When the ions react with water to produce hydrogen or hydroxide ions in solution Example: Strong Acid/Weak Base Example: Strong Acid/Strong Base Solve similar to weak acid/weak base problems Solve for Ka or Kb depending on if the salt makes an acidic (Ka) or basic (Kb) solution › Use the ion of the strong acid or strong base for equilibrium equation What is the pH of a 0.10 M solution of acetic acid, NaC2H3O2. The Ka of HC2H3O2 is 1.8 x 10-5 . C2H3O2- + H2O HC2H3O2 + OH Step #1: We will use Kb because the solution will be basic. First find the Kb for HC2H3O2. What is the pH of a 0.10 M solution of acetic acid, NaC2H3O2. The Ka of HC2H3O2 is 1.8 x 10-5 . C2H3O2- + H2O HC2H3O2 + OHKw = K aKb 1.0 × 10-14 = (1.8x10-5)(Kb) Kb = 5.6 × 10-10 Step #2: Write the equilibrium expression. C2H3O2- + H2O HC2H3O2 + OH- Kb = [HC2H3O2][OH-] [C2H3O2-] What is the pH of a 0.10 M solution of acetic acid, NaC2H3O2. The Ka of HC2H3O2 is 1.8 x 10-5 . Step #3: ICE I C E C2H3O20.10 -x 0.10 - x HC2H3O2 OH- 0 0 +x +x x x Step #4: Solve for OH-. C2H3O2- + H2O HC2H3O2 + OH- 5.6×10-10 = [x][x] [0.10-x] = [x][x] [0.10] = 7.5×10-6 Step #4: Solve for OH-. C2H3O2- + H2O HC2H3O2 + OH- x = 7.5×10-6 = [OH-] Step #5: Solve for pH. [OH-] = 7.5×10-6 pOH = -log[OH-] = -log[7.5×10-6] pOH = 5.1 14 = pH + pOH 14 = pH + 5.1 pH = 8.9 Use LeChatlier’s Principle to determine how the addition of a substance will affect the equilibrium HC2H3O2 C2H3O2 - + H+ The addition of the acetate ion (adding soluble salt) causes the equilibrium to shift to the LEFT The hydrogen concentration will DECREASE The acetic acid ionizes less with the addition of the acetate ion than it would alone in solution A solution with a very stable pH › You can add an acid or base to a buffer solution without it greatly affecting the pH of the solution Consists a weak acid-base conjugate pair › Usually a weak acid or base with the salt of that acid or base › Resists changes in addition of strong acid or base Example: blood (pH of 7.4) Buffer Capacity – the amount of acid or base the buffer can neutralize before the pH begins to change to an appreciable degree pH Range (of a buffer) – the range over which the buffer acts effectively [ A ] [base] pKa log pH pKa log [acid] [ HA] [ BH ] [acid] pKb log pOH pKb log [base] [ B] Reminder: pKa = –logKa and pKb = -logKb Given on AP Cheat Sheet! What is the pH of a buffer solution with concentrations of 0.20M HC2H3O2 and 0.50 M C2H3O2-? The acid dissociation constant for HC2H3O2 is 1.8×10-5. [ A ] [base] pKa log pH pKa log [acid] [ HA] pH = -log(1.8×10-5) + log(0.50/0.20) pH = 4.7 + 0.4 = 5.1 What is the pH of a buffer solution with concentrations of 0.20M HC2H3O2 and 0.20 M C2H3O2-? The acid dissociation constant for HC2H3O2 is 1.8×10-5. [ A ] [base] pKa log pH pKa log [acid] [ HA] pH = -log(1.8×10-5) + log(0.20/0.20) pH = 4.7 + 0 = 4.7 When concentrations of acid and conjugate base are the same, pH = pKa (and pOH = pKb) When you want to prepare a buffer with a desired pH, choose an acid with a pKa close to the desired pH. The salt will contain the anion of the acid, and the cation of a strong base (NaOH, KOH) Weak Acid Formula of the acid Hydrofluoric HF Formic HCOOH Benzoic C6H5COOH Acetic Carbonic Propanoic Hydrocyanic CH3COOH H2CO3 HC3H5O2 HCN Example of a salt of the weak acid KF – Potassium fluoride KHCOO – Potassium formate NaC6H5COO – Sodium benzoate NaH3COO – Sodium acetate NaHCO3 - Sodium bicarbonate NaC3H5O2 - Sodium propanoate KCN - potassium cyanide The salt will contain the cation of the base, and the anion of a strong acid (HCl, HNO3) Formula of the base Example of a salt of the weak acid NH3 NH4Cl - ammonium chloride Methylamine CH3NH2 CH3NH3Cl – methylammonium chloride Ethylamine C2H5NH2 C2H5NH3NO3 - ethylammonium nitrate Aniline C6H5NH2 C6H5NH3Cl – aniline hydrochloride Base Ammonia Pyridine C5H5N C5H5NHCl – pyridine hydrochloride Example of a buffer of HC2H3O2 with NaC2H3O2 HC2H3O2 ↔ C2H3O2- + H+ When adding a strong acid to a buffer solution, the base acts to neutralize the acid (ex: add HCl) NaC2H3O2 + HCl ↔ HC2H3O2 + NaCl Na+ + C2H3O2- + H+ + Cl- ↔ HC2H3O2 + Na+ + Cl- When adding a strong base to a buffer solution, the acid acts to neutralize the base (ex: add KOH) HC2H3O2 + KOH ↔ KC2H3O2 + H2O HC2H3O2 + K+ + OH- ↔ K+ + C2H3O2- + H2O What is the pH of a buffer solution with concentrations of 0.20M HC2H3O2 and 0.50 M C2H3O2- after the addition of 0.10 M KOH? The acid dissociation constant for HC2H3O2 is 1.8×10-5. The strong base is neutralized by the acid: HC2H3O2 + KOH C2H3O2 - + H+ 0.20 - 0.10 0.10 0.10 - 0.10 0 0.50 + 0.10 0.60 New conc. for acid and salt What is the pH of a buffer solution with concentrations of 0.20M HC2H3O2 and 0.50 M C2H3O2- after the addition of 0.10 M KOH? The acid dissociation constant for HC2H3O2 is 1.8×10-5. HC2H3O2 + KOH C2H3O2 - + H+ [ A ] pH pKa log [ HA] pH = -log(1.8×10-5) + log(0.60/0.10) pH = 4.7 + 0.8 = 5.5 What is the pH of a buffer solution with concentrations of 0.20M HC2H3O2 and 0.50 M C2H3O2- after the addition of 0.05 M HBr? The acid dissociation constant for HC2H3O2 is 1.8×10-5. The strong acid is neutralized by the base: C2H3O2 - + HBr HC2H3O2 + Br- 0.50 - 0.05 0.45 0.05 - 0.05 0 0.20 + 0.05 0.25 New conc. for acid and salt What is the pH of a buffer solution with concentrations of 0.20M HC2H3O2 and 0.50 M C2H3O2- after the addition of 0.10 M KOH? The acid dissociation constant for HC2H3O2 is 1.8×10-5. HC2H3O2 + KOH C2H3O2 - + H+ [ A ] pH pKa log [ HA] pH = -log(1.8×10-5) + log(0.45/0.25) pH = 4.7 + 0.3 = 5.0 A base of known concentration is slowly added to an acid of unknown concentration (or vice versa) to reach neutralization Indicators are added to the solution that change color to signal the equivalence point › Equivalence point – point at which stoichiometrically equivalent quantities of acid and base have been brought together - neutralization Titration Curve graph of the pH as acid or base is added to the solution Indicators are added to the solution that change color to signal the equivalence point › Equivalence point – point at which stoichiometrically equivalent quantities of acid and base have been brought together – neutralization Different indicators change at different pH levels Indicator Low pH color Gentian violet (Methyl violet 10B) yellow 0.0–2.0 blue-violet Leucomalachite green (first transition) Leucomalachite green (second transition) yellow green 0.0–2.0 11.6–14 green colorless Thymol blue (first transition) red 1.2–2.8 yellow Thymol blue (second transition) yellow 8.0–9.6 blue Methyl yellow Bromophenol blue Congo red Methyl orange Bromocresol green Methyl red Methyl red Azolitmin Bromocresol purple Bromothymol blue Phenol red Neutral red Naphtholphthalein Cresol Red Phenolphthalein Thymolphthalein Alizarine Yellow R Litmus red yellow blue-violet red yellow red red red yellow yellow yellow red colorless to reddish yellow colorless colorless yellow red Transition pH range High pH color 2.9–4.0 3.0–4.6 3.0–5.0 3.1–4.4 3.8–5.4 4.4–6.2 4.5–5.2 4.5–8.3 5.2–6.8 6.0–7.6 6.8–8.4 6.8–8.0 7.3–8.7 7.2–8.8 8.3–10.0 9.3–10.5 10.2–12.0 4.5-8.3 yellow purple red orange blue yellow green blue purple blue red yellow greenish to blue reddish-purple fuchsia blue red blue 1. Strong acid-strong base titration 2. Weak acid-strong base titration 3. Strong acid-weak base titration 4. Polyprotic acid-strong base titration 13 12 11 10 9 pH 8 7 Endpoint is at pH 7 A solution that is 0.10 M HCl is titrated with 0.10 M NaOH 6 5 4 3 2 1 0.00 5.00 10.00 15.00 20.00 25.00 milliliters NaOH (0.10 M) 30.00 35.00 40.00 45.00 13 12 11 10 9 pH 8 Endpoint is above pH 7 7 6 A solution that is 0.10 M CH3COOH is titrated with 0.10 M NaOH 5 4 3 2 1 0.00 5.00 10.00 15.00 20.00 25.00 milliliters NaOH (0.10 M) 30.00 35.00 40.00 45.00 13 12 11 10 9 pH 8 7 6 5 Endpoint is below pH 7 A solution that is 0.10 M HCl is titrated with 0.10 M NH3 4 3 2 1 0.00 5.00 10.00 15.00 20.00 25.00 milliliters NH3 (0.10 M) 30.00 35.00 40.00 45.00 The titration curve will have as many bumps as there are hydrogen ions to give up This curve has 2 bumps so it represents a diprotic acid Remember M1V1 = M2V2 When finding the concentration or volume at which an acid and base neutralize each other, we use the same calculation MaVa = MbVb (a = acid and b=base)