Survey
* Your assessment is very important for improving the workof artificial intelligence, which forms the content of this project
* Your assessment is very important for improving the workof artificial intelligence, which forms the content of this project
Chapter 14 Acids and Bases Properties of Acids and Bases • Acids – Give foods a tart or sour taste • What acidic foods might you eat? – Aqueous solutions of acids are electrolytes • Conduct Electricity – Some are strong electrolytes (strong acids) – Some are weak electrolytes (weak acids) • Cause indicator dyes to change colors • Many metals react with acids producing hydrogen gas • React with compounds containing hydroxide ions to form water and a salt Properties of Acids and Bases • Bases – Have bitter taste, and slippery feel – Aqueous solutions of bases are also electrolytes • Conduct Electricity – Some are strong electrolytes (strong bases) – Some are weak electrolytes (weak bases) • Cause indicator dyes to change colors • Water and salt are formed when a base that contains hydroxide ions react with an acid Arrhenious Acids and Bases • Acids are hydrogen-containing compounds that ionize to yield hydrogen ions (H+) in aqueous solution • Bases are compounds that ionize to yield hydroxide ions (OH-) in aqueous solution Arrhenious Acids • Can be monoprotic, diprotic, or triprotic – Monoportic: HNO3 → H+ + NO3• Ionization yields one hydrogen ion – Diprotic: H2SO4 → 2H+ + SO42• Complete ionization yields 2 hydrogen ions – Triprotic: H3PO4 → 3H+ + PO43• Complete ionization yields 3 hydrogen ions • Not all the hydrogens in an acid may be released as hydrogen ions • Not all hydrogen containing compounds are acids – Only hydrogens joined to very electronegative elements, and thus have very polar bonds, are ionizable in water H O H C C O- H Ethanoic Acid H+ Nonionizable Hydrogen Ionizable Hydrogen Arrhenious Bases • NaOH → Na+(aq) + OH-(aq) • KOH → K+(aq) + OH-(aq) – Bases formed with group one metals are very soluble and caustic – Can be made by reacting group one metals with water • Na + H2O → Na+(aq) + OH-(aq) H2 (g) • Bases of group 2 metals are very weak resulting low solubility – Examples are Ca(OH)2 and Mg(OH)2 Bronsted-Lowry Acids and Bases • Arrhenious definition of acids and bases is not very comprehensive and does not explain why certain substances have basic or acidic properties – Ammonia (NH3) is a base, but there is no hydroxide (OH-) in the compound to ionize • The Bronsted-Lowry theory defines an acid as a hydrogen-ion donor, and a base as a hydrogen-ion acceptor – Why ammonia is a base NH3(aq) + H2O(l) → NH4+(aq) + OH-(aq) Hydrogen ion aceptor, BronstedLowry Base Hydrogen ion donar, BronstedLowry Acid Makes the solution basic Conjugate Acids and Bases conjugate acid-base pair NH4+(aq) + OH-(aq) NH3(aq) + H2O(l) Base Conjugate Acid Acid Conjugate Base conjugate acid-base pair • • • A conjugant acid is the particle formed when a base gains a hydrogen ion A conjugant base is the particle that remains when an acid has donated a hydrogen ion A conjugate acid-base pair consists of two substances related by the loss or gain of a single hydrogen ion conjugate acid-base pair HCl(aq) + H2O(l) Acid Base H3O+(aq) + Cl-(aq) Conjugate Acid conjugate acid-base pair Conjugate Base Conjugate Acids and Bases conjugate acid-base pair HCl(aq) + H2O(l) Acid Base H3O+(aq) + Cl-(aq) Conjugate Acid Conjugate Base conjugate acid-base pair • A water molecule that gains a hydrogen ion becomes a positively charged hydronium ion H3O+ – In above equation, what is the hydrogen ion donor (acid) and which is the hydrogen ion acceptor (base) • Notice, water can both accept and donate a hydrogen ion and thus act as an acid and a base – A substance that can act as both an acid and a base is said to be amphoteric • Amino Acids as an example Lewis Acids and Bases • Acids accept a pair of electrons during a reaction while a base donates a pair of electrons – Lewis acid – a substance that can accept a pair of electrons to form a covalent bond – Lewis base – a substance that can donate a pair of electrons to form a covalent bond NH3 + BF3 → NH3BF3 Identify the Lewis Acid and the Lewis Base in the above equation Acid-Base Definitions Review Type Acid Base Arrhenius H+ producer OH- producer Bronsted-Lowry H+ donor H+ acceptor Lewis electron-pair acceptor electron-pair donor Hydrogen Ions and Acidity • Occasionally collusions between water molecules cause them to react forming hydroxide ions and hydronium ions – The reaction in which water molecules produce ions is called the self ionization of water H2O(l) H2O (l) + H2O (l) H+(aq) + OH-(aq) H3O+(aq) + OH-(aq) • In aqueous solution, hydrogen ions H+ are always joined to a water molecule as hydronium ions • In pure (neutral) water, the self-ionization of water results in 1 x 10-7 M of H+ ions and 1 x 10-7 M of OH- ions – Any aqueous solution in which H+ and OH- ions are equal is described as a neutral solution Ion Product Constant for Water • For aqueous solutions, the product of the hydrogen-ion concentration and the hydroxide-ion concentration equals 1.0x10-14 Kw = [H+][OH-] = 1.0x10-14 M • • The product of the concentrations of the hydrogen ions and hydroxide ions in water is called the ion-product constant Aqueous acids and bases sift the ratio of hydrogen ions to hydroxide ions in solution causing it to become either acidic or basic – In a basic solution aka alkaline solution, the hydroxide ion (OH-) is greater than 1x10-7 M and the hydrogen ion (H+) is less 1x10-7 M – In a acidic solution, the hydrogen ion (H+) is greater than 1x10-7 M and the hydroxide ion (OH-) is less 1x10-7 M • Regardless of the acidity or alkalinity of the solution, the product of the Molarity (M) concentration of H+ and OH- always equals 1x10-14 at 25ºC – If the hydrogen ion H+ concentration in a soft drink is 1 x 10-5 M, what is the concentration of the hydroxide ion OH-? – Is the solution basic, neutral, or acidic? The pH Concept • Expressing hydrogen-ion concentrations in molarity is cumbersome – Soren Sorensen suggested that the hydrogen ion concentration be expressed as the negative log of the hydrogen-ion concentration giving us much smaller numbers to work with pH = -log[H+] • The pH of a solution is the negative logarithm of the hydrogen ion concentration • A neutral solution H+ = 1x10-7 has a pH = -log[1x10-7]= 7 • A solution in which the [H+] is greater than 1x10-7 M and has a pH less than 7.0 is acidic • The pH of pure water or a neutral solution has a pH of 7 • A solution with a pH greater than 7 is basic and has a [H+] concentration of less than 1x10-7 M – You can also calculate pOH which is the negative logarithm of hydroxide ion concentration pOH = -log[OH-] Work some pH problems (pH of 1 x10-5 M H+?) Relationship between pH and pOH pH + pOH = 14 pH = 14 – pOH pOH = 14 - pH pH and significant figures • Hydrogen ion concentrations should always be reported to two significant figures • pH and pOH calculations should always be reported to two decimal places – Rules are due to the sensitivity of pH meters Acid-Base Indicators Dyes • An indicator (HIn) is an acid or base that undergoes dissociation in a known pH range – An indicator is a valuable tool for measuring pH because its acid form and base form have different colors in solution HIn (aq) Acid Form H+ OH- H+ (aq) + In- (aq) Base Form – The acid form of the indicator dominates the disassociation equilibrium at low pH – The basic form of the indicator dominates the disassociation equilibrium at high pH – Color change of an indicator occurs in a narrow pH range ≈ 2 pH units – Thus it takes many indicators to span the entire pH spectrum • Indicator dyes have limitations Acid-Base Indicators pH Meter • Makes rapid, accurate pH measurements • Can record pH continuously over time when performing a reactions • Measures pH to two decimal places • Color and cloudiness of solution does not interfere with reading • Are many different types specialized for different jobs were pH measurements are required http://www.vittbi.com/photogallery/biotech/PH-Meter.jpg http://personals.galaxyinternet.net/tunga/Meter.jpg Strengths of Acids and Bases Strong and Weak Acids and Bases • Acids are classified as strong or weak depending on the degree to which they ionize in water – A strong acid have an equilibrium that lies far to the right (almost all the original HA ionizes) – Weak acids have an equilibrium that lies far the left (ionize only slightly in aqueous solution) – What are some example of strong acids and weak acids HCl(q) + H2O(l) CH3COOH(aq) + H2O(l) H3O+(aq) + Cl-(aq) 100% ionized H3O+(aq) + CH3COO-(aq) <1% ionized pH of 0.10 M Solutions of Common Acids and Bases • • • • • • • • • • • • • • • • • • • • • • • • Compound HCl (hydrochloric acid) H2SO4 (sulfuric acid) NaHSO4 (sodium hydrogen sulfate) H2SO3 (sulfurous acid) H3PO4 (phosphoric acid) HF (hydrofluoric acid) CH3CO2H (acetic acid) H2CO3 (carbonic acid) H2S (hydrogen sulfide) NaH2PO4 (sodium dihydrogen phosphate) NH4Cl (ammonium chloride) HCN (hydrocyanic acid) Na2SO4 (sodium sulfate) NaCl (sodium chloride) NaCH3CO2 (sodium acetate) NaHCO3 (sodium bicarbonate) Na2HPO4 (sodium hydrogen phosphate) Na2SO3 (sodium sulfite) NaCN (sodium cyanide) NH3 (aqueous ammonia) Na2CO3 (sodium carbonate) Na3PO4 (sodium phosphate) NaOH (sodium hydroxide, lye) pH 1.1 1.2 1.4 1.5 1.5 2.1 2.9 3.8 (saturated solution) 4.1 4.4 4.6 5.1 6.1 6.4 8.4 8.4 9.3 9.8 11.0 11.1 11.6 12.0 13.0 http://www.cartage.org.lb/en/themes/sciences/chemistry/Inorganicchemistry/AcidsBases/Common/Common.htm Acid Disassociation Constant • The equilibrium constant for weak acids (HA) can be written as: Acid Conjugate base H3O+(aq) + A-(aq) HA(aq) + H2O(l) Keq = [H3O+] [A-] [HA] [H2O] • For dilute solutions, the concentration of water is a constant, and can be combined with Keq to give the acid dissociation constant (Ka) Keq X H2O = Ka= [H3O+] [A-] [HA] • Ka reflects the fraction of an acid in the ionized form and thus is sometimes referred to as the ionization constant • Weak acids have small Ka values, while stronger acids have larger Ka values; why? Base Disassociation Constant • The equilibrium constant for weak Bases (B) can be written as: base Conjugate acid BH+(aq) + HO-(aq) B(aq) + H2O(l) Keq = [BH+] [HO-] [B] [H2O] • For dilute solutions, the concentration of water is a constant, and can be combined with Keq to give the base dissociation constant (Kb) Keq X H2O = Kb= [BH+] [OH-] [B] • Kb is the ratio of the concentration of the conjugate acid times the concentration of the hydroxide ion to the concentration of the base • The magnitue of Kb indicates the ability of a weak base to compete with the very strong base OH- for hydrogen ions • The smaller the Kb the weaker the base Relationship Between Ka and Kb 𝑯+ [𝑨− ] 𝑯𝑨 [𝑶𝑯− ] + − 𝑲𝒂 × 𝑲𝒃 = × = 𝑯 𝑶𝑯 = 𝑲𝒘 = 𝟏. 𝟎 × 𝟏𝟎−𝟏𝟒 − [𝑯𝑨] [𝑨 ] • Allow you to calculate Kb from Ka or Ka from Kb Concentration and Strength • Remember, the word strong and weak acids and bases refers to the number particles of the acid or base that completely dissociate into their respective ions in solution • Concentration and dilute refer to how many moles of an acid or base is diluted in a constant volume of solution • Even though an acid may be “weak”, if it is highly concentrated, it will result in much lower pH of the solution it is dissolved in than a dilute solution of the same weak acid Various Ways to Describe Acid Strength Property 𝐾𝑎 Value Position of the dissociation (ionization) equilibrium Strength of conjugate base compared with that of water Strong Acid Weak Acid 𝐾𝑎 is large 𝐾𝑎 is small 𝐻+ ≈ [𝐻𝐴]0 𝐻 + ≪ [𝐻𝐴]0 𝐴− much weaker base than 𝐻2 𝑂 𝐴− much stronger base than 𝐻2 𝑂 Practice Problems 𝑲𝒂 Values HF 7.2 × 10−4 𝐻𝑁𝑂2 4.0 × 10−4 HCN 6.2 × 10−10 • Relative base strength – Using the table above and your knowledge of strong acids, arrange the following species according to their strength as bases: – 𝐻2 𝑂, 𝐹 − , 𝐶𝑙 − , 𝑁𝑂2− , 𝐶𝑁 − Practice Problems • Calculating [𝐻+ ] or 𝑂𝐻− – Calculate [𝐻 + ] or 𝑂𝐻 − as required for each of the following solutions at 25°C, and state whether the solution is neutral, acidic, or basic a) 1.0 × 10−5 𝑀 𝑂𝐻 − b) 1.0 × 10−7 𝑀 𝑂𝐻 − c) 10.0 M 𝑀 𝐻 + Practice Problems • Calculating pH and pOH – Calculate the pH and pOH for each of the following solutions at 25°C. a) 1.0 × 10−3 𝑀 𝑂𝐻 − b) 1.0 𝑀 𝐻 + Practice Problems • Calculating pH – The pH of a sample of human blood was measured to be 7.41 at 25°C. Calculate pOH, [H+], and [OH-] for the sample. Practice Problems • pH of Strong Acids – Calculate the pH of 0.10 M HNO3. – Calculate the pH of 1.0 × 10−10 M HCl. Calculating the pH of Weak Acid Solutions 1. List the major species in the solution 2. Choose the species that can produce H+, and write balanced equations for the reactions producing H+ 3. Using the values of the equilibrium constants for the reaction you have written, decide which equilibrium will dominate in producing H+ 4. Write the equilibrium expression for the dominant equilibrium 5. List the initial concentrations of the species participating in the dominant equilibrium 6. Define the change needed to achieve equilibrium; that is define x 7. Write the equilibrium concentration in terms of x 8. Substitute the equilibrium concentrations into the equilibrium expression 9. Solve for x the “easy” way, that is, by assuming that [𝐻𝐴]0 − 𝑥 ≈ [𝐻𝐴]0 10.Use the 5% rule to verify whether the approximation is valid – 𝑥 [𝐻𝐴] × 100 ≤ 5% 11.Calculate [H+] and pH Practice Problem • Calculating the pH of a weak acid 1. Calculate the pH of 0.100 M solution of hypochlorous acid. (𝐾𝑎 = 3.5 × 10−8 𝑀) Practice Problems • The pH of week acid mixtures 1. Calculate the pH of a solution that contains 1.00 M HCN (𝐾𝑎 = 6.2 × 10−10 ) and 5.00 M HNO2 (𝐾𝑎 = 4.0 × 10−4 ). Also calculate the concentration of the cyanide ion in this solution at equilibrium. Calculating Dissociation Constants • Disassociation constants are calculated from experimental data • To find the Ka of weak acid or the Kb of a weak base, substitute the measured concentrations of all the substances present at equilibrium into the expression for Ka or Kb • A 0.1000M solution of ethanoic acid is only partially ionized and has a pH of 2.87. What is the acid dissociation constant (Ka) of ethanoic acid? Percent Dissociation • The percent dissociation of a weak acid is 𝑚𝑜𝑙 𝑎𝑚𝑜𝑢𝑛𝑡 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑒𝑑 ( ) 𝐿 𝑃𝑒𝑟𝑐𝑒𝑛𝑡 𝐷𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛 = × 100% 𝑚𝑜𝑙 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 ( ) 𝐿 1. Calculate the percent dissociation of acetic acid (𝐾𝑎 = 1.8 × 10−5 ) in each of the following solutions. a) b) – 1.00 M 𝐻𝐶2 𝐻3 𝑂2 0.100 M 𝐻𝐶2 𝐻3 𝑂2 For solutions of any weak acid HA, [𝐻 + ] decreases as [𝐻𝐴]0 decreases, but the percent dissociation increases as [𝐻𝐴]0 decreases Practice Problems • Calculating Ka from percent dissociation 1. Lactic acid (HC3H5O3 2. ) is a waste product that accumulates in muscle tissue during exertion, leading to pain and feeling of fatigue. In a 0.100 M aqueous solution, lactic acid is 3.7% dissociated. Calculate the value of Ka for this acid. Practice Problem • The pH of strong bases 1. Calculate the pH of 5.0 × 10−2 𝑀 NaOH solution. Practice Problem • pH of a weak base 1. Calculate the pH for a 15.0 M solution of NH3 (𝐾𝑏 = 1.8 × 10−5 ) 2. Calculate the pH of a 1.0 M solution of methylamine 𝐶𝐻3 𝑁𝐻2 𝐾𝑏 = 4.38 × 10−4 Polyprotic Acids • Polyprotic Acids are Acids that can furnish more than one proton • Example is the triprodic acid phosphoric acid 𝐻3 𝑃𝑂4 𝑎𝑞 ↔ 𝐻 + 𝑎𝑞 + 𝐻2 𝑃𝑂4− 𝐾𝑎1 = 7.5 × 10−3 𝐻2 𝑃𝑂4− 𝑎𝑞 ↔ 𝐻 + 𝑎𝑞 + 𝐻𝑃𝑂42− 𝐾𝑎2 = 6.2 × 10−8 𝐻𝑃𝑂42− 𝑎𝑞 ↔ 𝐻 + 𝑎𝑞 + 𝐻2 𝑃𝑂43− 𝐾𝑎3 = 4.8 × 10−13 – For a typical weak polyprotic acid 𝐾𝑎1 ≫ 𝐾𝑎2 ≫ 𝐾𝑎3 • Means that only the first dissociation step makes an important contribution to [H+] Practice Problem • Calculate the pH of a 5.0 M H3PO4 solution and the equilibrium concentrations of the species 𝐻3 𝑃𝑂4 , 𝐻2 𝑃𝑂4− , 𝐻𝑃𝑂42− , 𝑎𝑛𝑑 𝑃𝑂43− Sulfuric Acid • Sulfuric Acid is unique in the common acids since it is a strong acid in its first dissociation step and a weak acid in its second step: 𝐻2 𝑆𝑂4 𝑎𝑞 → 𝐻 + + 𝐻𝑆𝑂4− 𝑎𝑞 𝐾𝑎 𝑖𝑠 𝑣𝑒𝑟𝑦 𝑙𝑎𝑟𝑔𝑒 𝐻𝑆𝑂4− 𝑎𝑞 → 𝐻 + + 𝑆𝑂42− 𝑎𝑞 𝐾𝑎2 = 1.2 × 10−2 1. Calculate the pH of a 1.0 M sulfuric acid solution 2. Calculate the pH of a 0.0100 M sulfuric acid solution Acid-Base Properties of Salts • A salt is an ionic compound – In dilute solutions, it is assumed that salts break up into their respective ions • Sometimes, the ions can behave as acids or bases Acid-Base Properties of Various Types of Salts Type of Salt Examples Comment pH of Solution Cation is from strong base; anion is from strong acid NaCl, KNO3, NaCl, NaNO3 Neither acts as an acid or a base Netural Cation is from strong base; anion is from weak acid NaC2H3O2, KCN, NaF Anion acts as a base; cation has no effect on pH Basic Cation is conjugate acid of weak base; anion is from strong acid NH4Cl, NH4NO3 Cation acts as acid; anion has no effect on pH Acidic Cation is conjugate acid of weak base; anion is conjugate base of weak acid NH4C2H3O2, NH4CN Cation acts as an acid; anion acts as a base Acidic if 𝐾𝑎 > 𝐾𝑏 , basic if 𝐾𝑎 < 𝐾𝑏 , neutral if 𝐾𝑎 = 𝐾𝑏 Cation is highly charged metal ion; anion is from strong acid Al(NO3)3, FeCl3 Hydrated cation acts as an acid; anion has no effect on pH Acidic Practice Problem • Salts as a weak base – Calculate the pH of a 0.30 M NaF solution. The Ka value for HF is 7.2 × 10−4 . Practice Problem • Salts as weak acids – Calculate the pH of a 0.10 M NH4Cl solution. The Kb value for NH3 is 1.8 × 10−5 . – Calculate the pH of a 0.010 M AlCl3 solution. −5 The Ka value for 𝐴𝑙(𝐻2 𝑂)3+ is 1.4 × 10 6 2+ + (𝑎𝑞) 𝐴𝑙(𝐻2 𝑂)3+ (𝑎𝑞) ↔ 𝐴𝑙(𝑂𝐻)(𝐻 𝑂) 𝑎𝑞 + 𝐻 2 6 5 Practice Problem • The Acid-Base Properties of Salts – Predict whether an aqueous solution of each of the following salts will be acidic, basic, or neutral a) 𝑁𝐻4 𝐶2 𝐻3 𝑂2 b) 𝑁𝐻4 𝐶𝑁 c) 𝐴𝑙2 (𝑆𝑂4 )3 • • • • 𝑁𝐻4+ , 𝐾𝑎 = 5.6 × 10−10 𝐶2 𝐻3 𝑂2− , 𝐾𝑎 = 5.6 × 10−10 𝐶𝑁 − , 𝐾𝑏 = 1.6 × 10−5 𝑆𝑂42− , 𝐾𝑏 = 8.3 × 10−13 The affection of structure on Acid-Base Properties • The two main factors that determine whether a molecule containing a X—H bond will behave as a Bronsted-Lowry acid are the bond strength and polarity – C—H bonds are do not produce acidic solutions since a C—H bond is strong an nonpolar – The H—Cl bond, however, is stronger than the C—H bond, but it also much more polar and readily dissociates in water Bond Strengths and Acid Strengths for Hydrogen Halides H—X Bond Bond Strength (kJ/mol) Acid Strength in water H—F 565 Weak H—Cl 427 Strong H—Br 363 Strong H—I 295 Strong Most Polar H—F Bond Polarity > H—Cl > Least Polar HBr > H--I Oxyacids Oxyacid 𝐻𝐶𝑙𝑂4 𝐻𝐶𝑙𝑂3 Ka Value Structure Large O H O Cl O O ~1 H O Cl 𝐻𝐶𝑙𝑂2 1.2 × 10−2 H O Cl O 𝐻𝐶𝑙𝑂 3.5 × 10−8 H O Cl • Oxyacids characteristically contain the grouping (H—O—X) – Acid strengths increases with increasing oxygen • Due to very electronegative oxygen atoms are able to draw electrons away form the chlorine atom and O—H bond making it weaker and more polar Oxyacids Comparison of electronegativity of X and Ka Values for a series of oxyacids Acid X Electronegativity of X Ka for Acid HOCl Cl 3.0 4 × 10−8 HOBr Br 2.8 2 × 10−9 HOI I 2.5 2 × 10−11 HOCH3 CH3 2.3 (for Carbon in CH3) ~10 × 10−15 • The more electronegative X is, the stronger the acid is Acids of Highly Charged Metal Ions • The acidity of water molecules attached to the metal ion is increased by the attraction of electrons to the positive metal ion: H Al3+ O H Acid Base Properties of Oxides • A compound containing the H—O—X group will produce an acidic solution in water the O—X bond is strong and covalent 𝑆𝑂3 (𝑔) + 𝐻2 𝑂(𝑙) → 𝐻2 𝑆𝑂4 𝑎𝑞 𝐶𝑂2 𝑔 + 𝐻2 𝑂(𝑙) → 𝐻2 𝐶𝑂3 (𝑎𝑞) 2 𝑁𝑂2 𝑔 + 𝐻2 𝑂(𝑙) → 2𝐻𝑁𝑂3 (𝑎𝑞) • If the O—X bond is ionic, the compound will produce a basic solution in water 𝐶𝑎𝑂 𝑠 + 𝐻2 𝑂(𝑙) → 𝐶𝑎(𝑂𝐻)2 (𝑎𝑞) 𝐾2 𝑂(𝑠) + 𝐻2 𝑂(𝑙) → 2𝐾𝑂𝐻(𝑎𝑞)