Chemistry: A Molecular Approach, 2nd Ed.

Nivaldo Tro

Chapter 15
Acids and
Bases

Roy Kennedy
Massachusetts Bay Community College
Wellesley Hills, MA
Copyright  2011 Pearson Education, Inc.

Stomach Acid & Heartburn
• The cells that line your stomach produce
hydrochloric acid
 to kill unwanted bacteria
 to help break down food
 to activate enzymes that break down food
• If the stomach acid backs up into your
esophagus, it irritates those tissues, resulting in
heartburn
 acid reflux

Tro, Chemistry: A Molecular Approach, 2/e 2 Copyright  2011 Pearson Education, Inc.

Curing Heartburn

• Mild cases of heartburn can be cured by
neutralizing the acid in the esophagus
 swallowing saliva, which contains bicarbonate
ion
 taking antacids that contain hydroxide ions
and/or carbonate ions

Tro, Chemistry: A Molecular Approach, 2/e 3 Copyright  2011 Pearson Education, Inc.

GERD
• Chronic heartburn is a problem for some people
• GERD (gastroesophageal reflux disease) is chronic
leaking of stomach acid into the esophagus
• In people with GERD, the muscles separating the
stomach from the esophagus do not close tightly,
allowing stomach acid to leak into the esophagus
• Physicians diagnose GERD by attaching a pH
sensor to the esophagus to measure the acidity
levels of the fluids over time

Tro, Chemistry: A Molecular Approach, 2/e 4 Copyright  2011 Pearson Education, Inc.

chalk. Fe. Al.e. producing CO2  marble. Properties of Acids • Sour taste • React with “active” metals  i. Zn. baking soda. Chemistry: A Molecular Approach. or Au 2 Al + 6 HCl AlCl3 + 3 H2  corrosive • React with carbonates.. limestone CaCO3 + 2 HCl CaCl2 + CO2 + H2O • Change color of vegetable dyes  blue litmus turns red • React with bases to form ionic salts Tro. . Inc. 2/e 5 Copyright  2011 Pearson Education. but not Cu. Ag.

Common Acids Tro. Inc. Chemistry: A Molecular Approach. 2/e 6 Copyright  2011 Pearson Education. .

Inc. HF Tro. . 2/e 7 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach. Structures of Acids • Binary acids have acid hydrogens attached to a nonmetal atom  HCl.

HNO3 Tro. Inc. Structure of Acids • Oxy acids have acid hydrogens attached to an oxygen atom  H2SO4. Chemistry: A Molecular Approach. 2/e 8 Copyright  2011 Pearson Education. .

. 2/e 9 Copyright  2011 Pearson Education. Structure of Acids • Carboxylic acids have COOH group  HC2H3O2. H3C6H5O7 • Only the first H in the formula is acidic  the H is on the COOH Tro. Chemistry: A Molecular Approach. Inc.

. 2/e 10 Copyright  2011 Pearson Education. Inc. Properties of Bases • Also known as alkalis • Taste bitter  alkaloids = plant product that is alkaline  often poisonous • Solutions feel slippery • Change color of vegetable dyes  different color than acid  red litmus turns blue • React with acids to form ionic salts  neutralization Tro. Chemistry: A Molecular Approach.

Inc. Common Bases Tro. . Chemistry: A Molecular Approach. 2/e 11 Copyright  2011 Pearson Education.

. 2/e 12 Copyright  2011 Pearson Education. Inc. Chemistry: A Molecular Approach. Structure of Bases • Most ionic bases contain OH− ions  NaOH. Ca(OH)2 • Some contain CO32− ions  CaCO3 NaHCO3 • Molecular bases contain structures that react with H+  mostly amine groups Tro.

Inc. blue in base • Phenolphthalein  found in laxatives  red in base. Chemistry: A Molecular Approach. 2/e 13 Copyright  2011 Pearson Education. colorless in acid Tro. . Indicators • Chemicals that change color depending on the solution’s acidity or basicity • Many vegetable dyes are indicators  anthocyanins • Litmus  from Spanish moss  red in acid.

ionizable H written in front HC2H3O2(aq) → H+(aq) + C2H3O2−(aq) Tro. by the water HCl(aq) → H+(aq) + Cl−(aq)  in formula. 2/e 14 Copyright  2011 Pearson Education. or ionized. Inc. Chemistry: A Molecular Approach. Arrhenius Theory • Bases dissociate in water to produce OH− ions and cations  ionic substances dissociate in water NaOH(aq) → Na+(aq) + OH−(aq) • Acids ionize in water to produce H+ ions and anions  because molecular acids are not made of ions. they cannot dissociate  they must be pulled apart. .

NaOH dissociates in water. producing H+ and Cl– ions producing Na+ and OH– ions Tro. 2/e 15 Copyright  2011 Pearson Education. . Inc. Arrhenius Theory HCl ionizes in water. Chemistry: A Molecular Approach.

Inc. Chemistry: A Molecular Approach. . Hydronium Ion • The H+ ions produced by the acid are so reactive they cannot exist in water  H+ ions are protons!! • Instead. mainly hydronium ion. H(H2O)n+ Tro. H3O+ H+ + H2O  H3O+  there are also minor amounts of H+ with multiple water molecules. 2/e 16 Copyright  2011 Pearson Education. they react with water molecules to produce complex ions.

2/e 17 Copyright  2011 Pearson Education. Inc. Chemistry: A Molecular Approach. . Arrhenius Acid–Base Reactions • The H+ from the acid combines with the OH− from the base to make a molecule of H2O  it is often helpful to think of H2O as H-OH • The cation from the base combines with the anion from the acid to make a salt acid + base → salt + water HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l) Tro.

Inc. 2/e 18 Copyright  2011 Pearson Education. dissolve in water to form acidic solutions – even though they do not contain H+ ions • Does not explain acid–base reactions that take place outside aqueous solution Tro. . Chemistry: A Molecular Approach. Problems with Arrhenius Theory • Does not explain why molecular substances. such as NH3. such as CO2. dissolve in water to form basic solutions – even though they do not contain OH– ions • Does not explain how some ionic compounds. such as Na2CO3 or Na2O. dissolve in water to form basic solutions – even though they do not contain OH – ions • Does not explain why molecular substances.

• Any reaction that involves H+ being transferred from one molecule to another is an acid–base reaction  regardless of whether it occurs in aqueous solution. Another Definition: Brønsted-Lowry Acid-Base Theory • Brønsted and Lowry redefined acids and bases based on what happens in a reaction. Chemistry: A Molecular Approach. but many more do as well Tro. or if there is OH− present • All reactions that fit the Arrhenius definition also fit the Brønsted-Lowry definition. . 2/e 19 Copyright  2011 Pearson Education. Inc.

Inc. the acid molecule gives an H+ to the base molecule H–A + :B:A– + H–B+ Tro. Brønsted-Lowry Theory • In a Brønsted-Lowry acid–base reaction. . 2/e 20 Copyright  2011 Pearson Education. an H+ is transferred • The acid is an H donor • The base is an H acceptor  base structure must contain an atom with an unshared pair of electrons • In a Brønsted-Lowry acid-base reaction. Chemistry: A Molecular Approach.

Chemistry: A Molecular Approach. the HCl is the acid because HCl transfers an H+ to H2O. 2/e 21 Copyright  2011 Pearson Education. forming H3O+ ions  water acts as base. . Brønsted-Lowry Acids • Brønsted-Lowry acids are H+ donors  any material that has H can potentially be a Brønsted-Lowry acid  because of the molecular structure. accepting H + HCl(aq) + H2O(l) → Cl–(aq) + H3O+(aq) acid base Tro. Inc. often one H in the molecule is easier to transfer than others • When HCl dissolves in water.

the NH3(aq) is the base because NH3 accepts an H+ from H2O. forming OH–(aq)  water acts as acid. Inc. Chemistry: A Molecular Approach. Brønsted-Lowry Bases • Brønsted-Lowry bases are H+ acceptors  any material that has atoms with lone pairs can potentially be a Brønsted-Lowry base  because of the molecular structure. donating H+ NH3(aq) + H2O(l)  NH4+(aq) + OH–(aq) base acid Tro. often one atom in the molecule is more willing to accept H + transfer than others • When NH3 dissolves in water. . 2/e 22 Copyright  2011 Pearson Education.

. Chemistry: A Molecular Approach. 2/e 23 Copyright  2011 Pearson Education. You need to be able to recognize when an atom in a molecule has lone pair electrons and when it doesn’t! Tro. A Warning! • Because chemists know common bonding patterns. Inc. we often do not draw lone pair electrons on our structures.

Chemistry: A Molecular Approach. 2/e 24 Copyright  2011 Pearson Education. Practice – Draw structures of the following that include lone pairs of electrons HClO HCO3− Tro. Inc. .

Inc. Amphoteric Substances • Amphoteric substances can act as either an acid or a base  because they have both a transferable H and an atom with lone pair electrons • Water acts as base. 2/e 25 Copyright  2011 Pearson Education. donating H+ to NH3 NH3(aq) + H2O(l)  NH4+(aq) + OH–(aq) Tro. Chemistry: A Molecular Approach. . accepting H+ from HCl HCl(aq) + H2O(l) → Cl–(aq) + H3O+(aq) • Water acts as acid.

Brønsted-Lowry Acid-Base Reactions • One of the advantages of Brønsted-Lowry theory is that it allows reactions to be reversible H–A + :B  :A– + H–B+ • The original base has an extra H+ after the reaction. 2/e 26 Copyright  2011 Pearson Education. Inc. so it will act as an acid in the reverse process • And the original acid has a lone pair of electrons after the reaction – so it will act as a base in the reverse process :A– + H–B+  H–A + :B Tro. Chemistry: A Molecular Approach. .

Inc. and the original acid becomes its conjugate base Tro. Conjugate Pairs • In a Brønsted-Lowry acid–base reaction. 2/e 27 Copyright  2011 Pearson Education. . Chemistry: A Molecular Approach. and the original acid becomes a base in the reverse process • Each reactant and the product it becomes is called a conjugate pair • The original base becomes its conjugate acid. the original base becomes an acid in the reverse reaction.

Chemistry: A Molecular Approach. Brønsted-Lowry Acid–Base Reactions H–A + :B  :A– + H–B+ acid base conjugate conjugate base acid HCHO2 + H2O  CHO2– + H3O+ acid base conjugate conjugate base acid H2O + NH3  HO– + NH4+ acid base conjugate conjugate base acid Tro. Inc. . 2/e 28 Copyright  2011 Pearson Education.

. Chemistry: A Molecular Approach. 2/e 29 Copyright  2011 Pearson Education. Inc. Conjugate Pairs In the reaction H2O + NH3  HO– + NH4+ H2O and HO– constitute an acid/conjugate base pair NH3 and NH4+ constitute a base/conjugate acid pair Tro.

. Practice – Write the formula for the conjugate acid of the following H2O H3O+ NH3 NH4+ CO32− HCO3− H2PO41− H3PO4 Tro. Inc. 2/e 30 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach.

2/e 31 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach. it cannot be an acid H2PO41− H2PO41− HPO42− Tro. Inc. . Practice – Write the formula for the conjugate base of the following H2O HO− NH3 NH2− CO32− because CO32− does not have an H.

Example 15. . it accepts an H+ so H2O must be the base and H3O+ its conjugate acid H2SO4 + H2O  HSO4– + H3O+ acid base conjugate conjugate base acid Tro. it loses an H+ so H2SO4 must be the acid and HSO4 its conjugate base When the H2O becomes H3O+. Inc.1a: Identify the Brønsted-Lowry acids and bases. 2/e 32 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach. and their conjugates. in the reaction H2SO4 + H2O  HSO4– + H3O+ When the H2SO4 becomes HSO4.

Chemistry: A Molecular Approach.1b: Identify the Brønsted-Lowry acids and bases and their conjugates in the reaction HCO3– + H2O  H2CO3 + HO– When the HCO3 becomes H2CO3. Inc. Example 15. 2/e 33 Copyright  2011 Pearson Education. . it donats an H+ so H2O must be the acid and OH its conjugate base HCO3– + H2O  H2CO3 + HO– base acid conjugate conjugate acid base Tro. it accepts an H+ so HCO3 must be the base and H2CO3 its conjugate acid When the H2O becomes OH.

2/e 34 Copyright  2011 Pearson Education. Inc. conjugate acid. Chemistry: A Molecular Approach. and conjugate base in the following reaction HSO4−(aq) + HCO3−(aq)  SO42−(aq) + H2CO3(aq) Acid Base Conjugate Conjugate Base Acid Tro. . base. Practice – Identify the Brønsted-Lowry acid.

. base acid HSO4− HSO4− + H2O  SO42− + H3O+ Acid Base Conj. 2/e 35 Copyright  2011 Pearson Education. Conj. base acid Tro. Practice—Write the equations for the following reacting with water and acting as a monoprotic acid & label the conjugate acid and base HBr HBr + H2O  Br− + H3O+ Acid Base Conj. Conj. Chemistry: A Molecular Approach. Inc.

Inc. acid base Tro. Chemistry: A Molecular Approach. . acid base CO32− + H2O  HCO3− + OH− CO32− Base Acid Conj. Conj. Conj. Practice—Write the equations for the following reacting with water and acting as a monoprotic-accepting base and label the conjugate acid and base I− I− + H2O  HI + OH− Base Acid Conj. 2/e 36 Copyright  2011 Pearson Education.

Comparing Arrhenius Theory and Brønsted-Lowry Theory • Arrhenius theory • Brønsted–Lowry theory HCl(aq)  H+ HCl(aq) + H2O(l)  Cl− (aq) + Cl−(aq) (aq) + H3O+(aq) HF(aq)  H+(aq) HF(aq) + H2O(l)  F− + F−(aq) (aq) + H3O+(aq) NaOH(aq)  Na+ (aq) + OH−(aq) NaOH(aq)  Na+ (aq) + OH−(aq) NH4OH(aq)  NH4+ NH3(aq) + H2O(l)  NH4+ (aq) + OH−(aq) (aq) + OH−(aq) Tro. 2/e 37 Copyright  2011 Pearson Education. Inc. . Chemistry: A Molecular Approach.

Chemistry: A Molecular Approach. Inc. Arrow Conventions • Chemists commonly use two kinds of arrows in reactions to indicate the degree of completion of the reactions • A single arrow indicates all the reactant molecules are converted to product molecules at the end • A double arrow indicates the reaction stops when only some of the reactant molecules have been converted into products  in these notes Tro. . 2/e 38 Copyright  2011 Pearson Education.

either through dissociation or reaction with water. Chemistry: A Molecular Approach. → • A strong base is a strong electrolyte practically all the base molecules form OH– ions. . 2/e 39 Copyright  2011 Pearson Education.  • A weak base is a weak electrolyte  only a small percentage of the base molecules form OH– ions. Strong or Weak • A strong acid is a strong electrolyte  practically all the acid molecules ionize. → • A weak acid is a weak electrolyte  only a small percentage of the molecules ionize. either through dissociation or reaction with water.  Tro. Inc.

.10 M H3O+ Tro. Inc. Chemistry: A Molecular Approach.10 M HCl = 0. Strong Acids • The stronger the acid. 2/e 40 Copyright  2011 Pearson Education. the more willing it is to donate H HCl  H+ + Cl−  we use water as the standard HCl + H2O  H3O+ + Cl− base to donate H to • Strong acids donate practically all their H’s  100% ionized in water  strong electrolyte • [H3O+] = [strong acid]  [X] means the molarity of X 0.

Weak Acids • Weak acids donate a small HF  H+ + F− fraction of their H’s HF + H2O  H3O+ + F−  most of the weak acid molecules do not donate H to water  much less than 1% ionized in water • [H3O+] << [weak acid] 0. . Inc. 2/e 41 Copyright  2011 Pearson Education.10 M HF ≠ 0. Chemistry: A Molecular Approach.10 M H3O+ Tro.

Inc. . 2/e 42 Copyright  2011 Pearson Education. Strong & Weak Acids Tro. Chemistry: A Molecular Approach.

Chemistry: A Molecular Approach.Tro. Inc. . 2/e Copyright  2011 Pearson Education.

. the stronger the acid or base • The position of equilibrium depends on the strength of attraction between the base form and the H+  stronger attraction means stronger base or weaker acid Tro. Chemistry: A Molecular Approach. acid or base strength is measured by determining the equilibrium constant of a substance’s reaction with water HAcid + H2O  Acid− + H3O+ Base: + H2O  HBase+ + OH− • The farther the equilibrium position lies toward the products. Inc. Strengths of Acids & Bases • Commonly. 2/e 44 Copyright  2011 Pearson Education.

neutral stronger acid than anion  H3O+ > H2O > OH−. NH4+ > NH3 > NH2−  trend in base strength opposite Tro. . the weaker the conjugate base is at accepting H • Higher oxidation number = stronger oxyacid  H2SO4 > H2SO3. 2/e 45 Copyright  2011 Pearson Education. HNO3 > HNO2 • Cation stronger acid than neutral molecule. Chemistry: A Molecular Approach. Inc. General Trends in Acidity • The stronger an acid is at donating H.

Ka • Acid strength measured by the size of the equilibrium constant when reacts with H2O HAcid + H2O  Acid− + H3O+ • The equilibrium constant for this reaction is called the acid ionization constant. Inc. Chemistry: A Molecular Approach. . Ka  larger Ka = stronger acid         Ka   Tro. Acid Ionization Constant. 2/e 46 Copyright  2011 Pearson Education.

Inc. 2/e 47 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach. .Tro.

Chemistry: A Molecular Approach. 2/e 48 Copyright  2011 Pearson Education. . Autoionization of Water • Water is actually an extremely weak electrolyte  therefore there must be a few ions present • About 2 out of every 1 billion water molecules form ions through a process called autoionization H2O  H+ + OH– H2O + H2O  H3O+ + OH– • All aqueous solutions contain both H3O+ and OH–  the concentration of H3O+ and OH– are equal in water  [H3O+] = [OH–] = 10−7M @ 25 °C Tro. Inc.

2/e 49 Copyright  2011 Pearson Education. you can calculate the other • As [H3O+] increases the [OH–] must decrease so the product stays constant  inversely proportional Tro. . Inc. Ion Product of Water • The product of the H3O+ and OH– concentrations is always the same number • The number is called the Ion Product of Water and has the symbol Kw  aka the Dissociation Constant of Water • [H3O+] x [OH–] = Kw = 1.00 x 10−14 @ 25 °C  if you measure one of the concentrations. Chemistry: A Molecular Approach.

00 x 10−7. Inc.00 x 10−7 Tro. .00 x 10−7 • Basic solutions have a larger [OH–] than [H3O+]  [H3O+] < 1.00 x 10−7 • Acidic solutions have a larger [H3O+] than [OH–]  [H3O+] > 1.00 x 10−7. Chemistry: A Molecular Approach. [OH–] > 1. Acidic and Basic Solutions • All aqueous solutions contain both H3O+ and OH– ions • Neutral solutions have equal [H3O+] and [OH–]  [H3O+] = [OH–] = 1. 2/e 50 Copyright  2011 Pearson Education. [OH–] < 1.

. 2/e 51 Copyright  2011 Pearson Education. Practice – Complete the table [H+] vs. Inc. Chemistry: A Molecular Approach. [OH−] [H+] 100 10−1 10−3 10−5 10−7 10−9 10−11 10−13 10−14 H+ H + + H H H + + OH − OH − OH − OH − OH − [OH−] Tro.

Inc. Practice – Complete the table [H+] vs. neither H+ nor OH− will ever be 0 The sizes of the H+ and OH− are not to scale because the divisions are powers of 10 rather than units Tro. . [OH−] Acid Base [H+] 100 10−1 10−3 10−5 10−7 10−9 10−11 10−13 10−14 H+ H + H H H + + + OH OH − − OH− OH − OH − [OH−]10−14 10−13 10−11 10−9 10−7 10−5 10−3 10−1 100 Even though it may look like it. 2/e 52 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach.

basic. Chemistry: A Molecular Approach. Example 15.2b: Calculate the [OH] at 25 °C when the [H3O+] = 1. 2/e 53 Copyright  2011 Pearson Education. and determine if the solution is acidic.5 x 10−9 M.5 x 10−9 M Find: [OH] Conceptual Plan: [H3O+] [OH] Relationships: Solution: Check: the units are correct. . the fact that the [H3O+] < [OH] means the solution is basic Tro. or neutral Given: [H3O+] = 1. Inc.

. Practice – Determine the [H3O+] when the [OH−] = 2. Inc.5 x 10−9 M Tro. 2/e 54 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach.

Inc. .5 x 10−9 M Find: [H3O+] Conceptual Plan: [OH] [H3O+] Relationships: Solution: Check: the units are correct. the fact that the [H3O+] > [OH] means the solution is acidic Tro. Practice – Determine the [H3O+] when the [OH−] = 2. 2/e 55 Copyright  2011 Pearson Education.5 x 10−9 M Given: [OH] = 2. Chemistry: A Molecular Approach.

. 2/e 56 Copyright  2011 Pearson Education. Inc. Measuring Acidity: pH • The acidity or basicity of a solution is often expressed as pH • pH = −log[H3O+]  exponent on 10 with a positive sign  pHwater = −log[10−7] = 7  need to know the [H3O+] concentration to find pH • pH < 7 is acidic. pH > 7 is basic. Chemistry: A Molecular Approach. pH = 7 is neutral • [H3O+] = 10−pH Tro.

Figs. .30303… = 6. • Because the part of the scientific notation number that determines the significant figures is the decimal part. Chemistry: A Molecular Approach. the sig figs are the digits after the decimal point in the log log(2.30 Tro.30303..0 x 106) = 6. Inc. 2/e 57 Copyright  2011 Pearson Education.0) = 6 + 0. Sig. & Logs • When you take the log of a number written in scientific notation. the digit(s) before the decimal point come from the exponent on 10. and the digits after the decimal point come from the decimal part of the number log(2.0 x 106) = log(106) + log(2..

2/e 58 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach. Inc. What Does the pH Number Imply? • The lower the pH. the higher the pH. . the more acidic the solution. the more basic the solution  1 pH unit corresponds to a factor of 10 difference in acidity • Normal range of pH is 0 to 14  pH 0 is [H3O+] = 1 M. pH 14 is [OH–] = 1 M  pH can be negative (very acidic) or larger than 14 (very alkaline) Tro.

Chemistry: A Molecular Approach. . 2/e 59 Copyright  2011 Pearson Education.3b: Calculate the pH at 25 °C when the [OH] = 1. the fact that the pH > 7 means the solution is basic Tro. or neutral Given: [OH] = 1.3 x 10−2 M Find: pH Conceptual Plan: [OH] [H3O+] pH Relationships: Solution: Check: pH is unitless. basic. Inc. Example 15. and determine if the solution is acidic.3 x 10−2 M.

Chemistry: A Molecular Approach. Inc. Practice – Determine the pH @ 25 ºC of a solution that has [OH−] = 2. 2/e 60 Copyright  2011 Pearson Education. .5 x 10−9 M Tro.

Inc. 2/e 61 Copyright  2011 Pearson Education. .5 x 10−9 M Given: [OH] = 2. Practice – Determine the pH @ 25 ºC of a solution that has [OH−] = 2. Chemistry: A Molecular Approach. the fact that the pH < 7 means the solution is acidic Tro.5 x 10−9 M Find: pH Conceptual Plan: [OH] [H3O+] pH Relationships: Solution: Check: pH is unitless.

.40 Tro. 2/e 62 Copyright  2011 Pearson Education. Practice – Determine the [OH−] of a solution with a pH of 5. Chemistry: A Molecular Approach. Inc.

.40 Find: [OH−]. M Conceptual Plan: pH [H3O+] [OH] Relationships: Solution: Check: because the pH < 7.40 Given: pH = 5. [OH−] should be less than 1 x 10−7. Chemistry: A Molecular Approach. Practice – Determine the [OH−] of a solution with a pH of 5. 2/e 63 Copyright  2011 Pearson Education. and it is Tro. Inc.

0 Tro. Inc. pOH • Another way of expressing the acidity/basicity of a solution is pOH • pOH = −log[OH]. Chemistry: A Molecular Approach. 2/e 64 Copyright  2011 Pearson Education. pOH = 7 is neutral • pH + pOH = 14. pOH > 7 is acidic. . [OH] = 10−pOH  pOHwater = −log[10−7] = 7  need to know the [OH] concentration to find pOH • pOH < 7 is basic.

pH and pOH
Practice – Complete the table

pH
[H+] 100 10−1 10−3 10−5 10−7 10−9 10−11 10−13 10−14
H+
H +

H H
H
+
+ +
OH OH − −
OH − OH − OH −
[OH−]10−14 10−13 10−11 10−9 10−7 10−5 10−3 10−1 100

pOH

Tro, Chemistry: A Molecular Approach, 2/e 65 Copyright  2011 Pearson Education, Inc.

pH and pOH
Practice – Complete the table
Acid Base
pH 0 1 3 5 7 9 11 13 14
[H+] 100 10−1 10−3 10−5 10−7 10−9 10−11 10−13 10−14
H+
H +

H H
H
+
+ +
OH OH − −
OH − OH − OH −
[OH−]10−14 10−13 10−11 10−9 10−7 10−5 10−3 10−1 100
pOH 14 13 11 9 7 5 3 1 0

Tro, Chemistry: A Molecular Approach, 2/e 66 Copyright  2011 Pearson Education, Inc.

Relationship between pH and pOH
• pH + pOH = 14.00
at 25 °C
you can use pOH to find pH of a solution

[H3O         
  
  
 
       
    
 
   
   
    
      
    

Tro, Chemistry: A Molecular Approach, 2/e 67 Copyright  2011 Pearson Education, Inc.

Example: Calculate the pH at 25 °C when the [OH]
= 1.3 x 10−2 M, and determine if the solution is acidic,
basic, or neutral
Given: [OH] = 1.3 x 10−2 M
Find: pH
Conceptual
Plan: [OH] pOH pH

Relationships:
Solution:

Check: pH is unitless; the fact that the pH > 7 means
the solution is basic
Tro, Chemistry: A Molecular Approach, 2/e 68 Copyright  2011 Pearson Education, Inc.

. 2/e 69 Copyright  2011 Pearson Education. Practice – Determine the pOH @ 25 ºC of a solution that has [H3O+] = 2. Inc. Chemistry: A Molecular Approach.5 x 10−9 M Tro.

Inc.5 x 10−9 M Find: pOH Conceptual Plan: [H3O+] pH pOH Relationships: Solution: Check: pH is unitless.5 x 10−9 M Given: [H3O+] = 2. the fact that the pH < 7 means the solution is acidic Tro. . Chemistry: A Molecular Approach. 2/e 70 Copyright  2011 Pearson Education. Practice – Determine the pOH @ 25 ºC of a solution that has [H3O+] = 2.

the smaller the pKb  larger Kb = smaller pKb Tro. . Inc. Kb = 10−pKb • The stronger the acid. Ka = 10−pKa • pKb = −log(Kb). 2/e 71 Copyright  2011 Pearson Education. pK • A way of expressing the strength of an acid or base is pK • pKa = −log(Ka). Chemistry: A Molecular Approach. the smaller the pKa  larger Ka = smaller pKa because it is the –log • The stronger the base.

Chemistry: A Molecular Approach. 2/e 72 Copyright  2011 Pearson Education. generally < 1 x 10−4 M Tro. Inc. [H3O+] and [OH−] in a Strong Acid or Strong Base Solution • There are two sources of H3O+ in an aqueous solution of a strong acid – the acid and the water • There are two sources of OH− in an aqueous solution of a strong acid – the base and the water • For a strong acid or base. the contribution of the water to the total [H3O+] or [OH−] is negligible  the [H3O+]acid shifts the Kw equilibrium so far that [H3O+]water is too small to be significant except in very dilute solutions. .

30 Tro. Finding pH of a Strong Acid or Strong Base Solution • For a monoprotic strong acid [H3O+] = [HAcid]  for polyprotic acids.20 M and pH = 13. .10 M and pH = 1. Inc.10 M HCl has [H3O+] = 0. 2/e 73 Copyright  2011 Pearson Education. only one lone pair accepts an H. [OH−] = (number OH−)x[Base]  for molecular bases with multiple lone pairs available.00 • For a strong ionic base. the other ionizations can generally be ignored for H2SO4. the other reactions can generally be ignored  0.10 M Ca(OH)2 has [OH−] = 0. the second ionization cannot be ignored  0. Chemistry: A Molecular Approach.

Chemistry: A Molecular Approach. Inc. finding the [H3O+] is complicated by the fact that the acid only undergoes partial ionization • Calculating the [H3O+] requires solving an equilibrium problem for the reaction that defines the acidity of the acid HAcid + H2O  Acid + H3O+ Tro. Finding the pH of a Weak Acid • There are also two sources of H3O+ in an aqueous solution of a weak acid – the acid and the water • However. . 2/e 74 Copyright  2011 Pearson Education.

Chemistry: A Molecular Approach.6: Find the pH of 0.200 M HNO2(aq) solution @ 25 °C write the reaction for HNO2 + H2O  NO2 + H3O+ the acid with water construct an ICE [HNO2] [NO2−] [H3O+] table for the reaction initial 0. Example 15. and the reaction is proceeding forward Tro. Qc = 0. Inc.200 0 ≈0 enter the initial change concentrations – equilibrium assuming the [H3O+] from water is ≈ 0 because no products initially. . 2/e 75 Copyright  2011 Pearson Education.

.200 0 0 terms of x change x +x +x sum the columns to equilibrium 0. 2/e 76 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach.6: Find the pH of 0.200 M HNO2(aq) solution @ 25 °C represent the [HNO2] [NO2−] [H3O+] change in the concentrations in initial 0.200 x x x find the equilibrium concentrations in HNO2 + H2O(l)  NO2−(aq) + H3O+(aq) terms of x substitute into the equilibrium constant expression Tro. Example 15. Inc.

200 0 ≈0 because Ka is very small. . Example 15. Chemistry: A Molecular Approach.200 M HNO2(aq) solution @ 25 °C Ka for HNO2 = 4.200 x x [HNO2]init and solve for x Tro. Inc.6 x 10−4 determine the value [HNO2] [NO2−] [H3O+] of Ka from Table 15. approximate change −x +x +x the [HNO2]eq = 0.5 initial 0. 2/e 77 Copyright  2011 Pearson Education.200x equilibrium 0.6: Find the pH of 0.

6 x 10−3 the approximation is valid Tro.200 x x x = 9. Chemistry: A Molecular Approach. Example 15.200 M HNO2(aq) solution @ 25 °C Ka for HNO2 = 4. 2/e 78 Copyright  2011 Pearson Education.6: Find the pH of 0.200 0 ≈0 x < 5% of [HNO2]init change −x +x +x equilibrium 0.6 x 10−4 check if the [HNO2] [NO2−] [H3O+] approximation is valid by seeing if initial 0. . Inc.

0096 x = 9.0096 x 0.200−x x 0.6 x 10−3 Tro. Example 15. Chemistry: A Molecular Approach. Inc.190 0.200 M HNO2(aq) solution @ 25 °C Ka for HNO2 = 4.6 x 10−4 substitute x into [HNO2] [NO2−] [H3O+] the equilibrium concentration initial 0.200 0 ≈0 definitions and change −x +x +x solve equilibrium 0. . 2/e 79 Copyright  2011 Pearson Education.6: Find the pH of 0.

6 x 10−4 substitute [H3O+] [HNO2] [NO2−] [H3O+] into the formula for pH and solve initial 0.0096 Tro.0096 0.200 0 ≈0 change −x +x +x equilibrium 0.200 M HNO2(aq) solution @ 25 °C Ka for HNO2 = 4.190 0. Inc. Chemistry: A Molecular Approach. .6: Find the pH of 0. Example 15. 2/e 80 Copyright  2011 Pearson Education.

Inc.0096 0.200 0 ≈0 into the equilibrium change −x +x +x constant expression and comparing the equilibrium 0.6: Find the pH of 0.200 M HNO2(aq) solution @ 25 °C Ka for HNO2 = 4.190 0.0096 calculated Ka to the given Ka though not exact.6 x 10−4 check by substituting [HNO2] [NO2−] [H3O+] the equilibrium concentrations back initial 0. the answer is reasonably close Tro. Chemistry: A Molecular Approach. Example 15. 2/e 81 Copyright  2011 Pearson Education. .

. Inc. 2/e 82 Copyright  2011 Pearson Education. HC6H4NO2? (Ka = 1. Practice – What is the pH of a 0.4 x 10−5 @ 25 °C) Tro.012 M solution of nicotinic acid. Chemistry: A Molecular Approach.

Inc. .012 M solution of nicotinic acid. 2/e 83 Copyright  2011 Pearson Education. HC6H4NO2? write the reaction HC6H4NO2 + H2O  C6H4NO2 + H3O+ for the acid with water [HA] [A−] [H3O+] construct an ICE table for the initial 0.012 0 ≈0 reaction change enter the initial equilibrium concentrations – assuming the [H3O+] from water is ≈ 0 Tro. Practice – What is the pH of a 0. Chemistry: A Molecular Approach.

Practice – What is the pH of a 0. Inc.012 M solution of nicotinic acid.012 0 0 sum the columns x +x change +x to find the equilibrium equilibrium 0. Chemistry: A Molecular Approach.012 x x x concentrations in terms of x substitute into the equilibrium constant expression Tro. HC6H4NO2? represent the HC6H4NO2 + H2O  C6H4NO2 + H3O+ change in the concentrations in [HA] [A−] [H3O+] terms of x initial 0. 2/e 84 Copyright  2011 Pearson Education. .

.012 0 ≈0 the [HA]eq = [HA]init change −x +x +x and solve for x equilibrium 0. Practice – What is the pH of a 0. approximate initial 0.012 M solution of nicotinic acid. Inc. HC6H4NO2? Ka = 1. Chemistry: A Molecular Approach.4 x 10−5 @ 25 °C determine the HC6H4NO2 + H2O  C6H4NO2 + H3O+ value of Ka [HA] [A−] [H3O+] because Ka is very small.012x x x Tro. 2/e Copyright  2011 Pearson Education.012 0.

HC6H4NO2? Ka = 1. Inc.012 M solution of nicotinic acid.012 x x x = 4.4 x 10−5 @ 25 °C Ka for HC6H4NO2 = 1.4 x 10−5 check if the [HA] [A−] [H3O+] approximation is valid by seeing if initial 0. Chemistry: A Molecular Approach. . 2/e 86 Copyright  2011 Pearson Education.1 x 10−4 the approximation is valid Tro. Practice – What is the pH of a 0.012 0 ≈0 x < 5% of change −x +x +x [HC6H4NO2]init equilibrium 0.

1 x 10−4 Tro. HC6H4NO2? Ka = 1.012−x x x x = 4.4 x 10−5 @ 25 °C substitute x into the [HA] [A−] [H3O+] equilibrium concentration initial 0. 2/e 87 Copyright  2011 Pearson Education. . Inc.012 0 ≈0 definitions and change −x +x +x solve equilibrium 0. Chemistry: A Molecular Approach. Practice – What is the pH of a 0.012 M solution of nicotinic acid.

2/e 88 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach.4 x 10−5 @ 25 °C substitute [H3O+] [HA] [A−] [H3O+] into the formula for pH and solve initial 0. .012 0.00041 Tro. Practice – What is the pH of a 0.012 M solution of nicotinic acid. HC6H4NO2? Ka = 1. Inc.012 0 ≈0 change −x +x +x equilibrium 0.00041 0.

00041 calculated Ka to the given Ka the values match Tro.012 M solution of nicotinic acid.4 x 10−5 @ 25 °C check by substituting [HA] [A−] [H3O+] the equilibrium concentrations back initial 0.00041 0. Chemistry: A Molecular Approach. .012 0 ≈0 into the equilibrium change −x +x +x constant expression and comparing the equilibrium 0.012 0. HC6H4NO2? Ka = 1. 2/e 89 Copyright  2011 Pearson Education. Inc. Practice – What is the pH of a 0.

Chemistry: A Molecular Approach. Inc.7: Find the pH of 0. 2/e 90 Copyright  2011 Pearson Education.100 0 ≈0 reaction change enter the initial equilibrium concentrations – assuming the [H3O+] from water is ≈ 0 Tro. . Example 15.100 M HClO2(aq) solution @ 25 °C write the reaction for the acid with HClO2 + H2O  ClO2 + H3O+ water [HClO2] [ClO2−] [H3O+] construct an ICE table for the initial 0.

Example 15.7: Find the pH of 0.100 M
HClO2(aq) solution @ 25 °C
represent the [HClO2] [ClO2−] [H3O+]
change in the
concentrations in initial 0.100 0 ≈0
terms of x change −x +x +x
sum the columns equilibrium 0.100−x x x
to find the
equilibrium
concentrations in
terms of x
substitute into the
equilibrium
constant
expression
Tro, Chemistry: A Molecular Approach, 2/e 91 Copyright  2011 Pearson Education, Inc.

Example 15.7: Find the pH of 0.100 M
HClO2(aq) solution @ 25 °C
determine the value Ka for HClO2 = 1.1 x 10−2
of Ka from Table 15.5
[HClO2] [ClO2−] [H3O+]
because Ka is very
initial 0.100 0 ≈0
small, approximate
the [HClO2]eq = change −x +x +x
[HClO2]init and solve equilibrium 0.100−x x x
for x

Tro, Chemistry: A Molecular Approach, 2/e 92 Copyright  2011 Pearson Education, Inc.

Example 15.7: Find the pH of 0.100 M
HClO2(aq) solution @ 25 °C
Ka for HClO2 = 1.1 x 10−2
check if the [HClO2] [ClO2−] [H3O+]
approximation is
valid by seeing if x initial 0.100 0 ≈0
< 5% of [HNO2]init change −x +x +x
equilibrium 0.100−x x x

x = 3.3 x 10−2

the approximation is invalid
Tro, Chemistry: A Molecular Approach, 2/e 93 Copyright  2011 Pearson Education, Inc.

Example 15.7: Find the pH of 0.100 M
HClO2(aq) solution @ 25 °C
Ka for HClO2 = 1.1 x 10−2
if the
approximation is
invalid, solve for x
using the quadratic
formula

Tro, Chemistry: A Molecular Approach, 2/e 94 Copyright  2011 Pearson Education, Inc.

028 Tro.100 0 ≈0 definitions and change −x +x +x solve equilibrium 0. Example 15.1 x 10−2 substitute x into [HClO2] [ClO2−] [H3O+] the equilibrium concentration initial 0. 2/e 95 Copyright  2011 Pearson Education.028 x 0. Chemistry: A Molecular Approach.072 0. Inc.028 x x = 0. .100 M HClO2(aq) solution @ 25 °C Ka for HClO2 = 1.100−x 0.7: Find the pH of 0.

072 0. 2/e 96 Copyright  2011 Pearson Education.028 Tro.028 0. Chemistry: A Molecular Approach. Inc. Example 15.100 M HClO2(aq) solution @ 25 °C Ka for HClO2 = 1.100 0 ≈0 change −x +x +x equilibrium 0.1 x 10−2 substitute [H3O+] [HClO2] [ClO2−] [H3O+] into the formula for pH and solve initial 0. .7: Find the pH of 0.

Inc. 2/e 97 Copyright  2011 Pearson Education.100 0 ≈0 constant expression and comparing the change −x +x +x calculated Ka to the equilibrium 0.1 x 10−2 the equilibrium concentrations back [HClO2] [ClO2-] [H3O+] into the equilibrium initial 0.7: Find the pH of 0.100 M HClO2(aq) solution @ 25°C check by substituting Ka for HClO2 = 1. .028 given Ka the answer matches Tro. Chemistry: A Molecular Approach.072 0. Example 15.028 0.

Example 15. Inc.8: What is the Ka of a weak acid if a 0. 2/e 98 Copyright  2011 Pearson Education.6E-05 reaction enter the initial concentrations and [H3O+]equil Tro. .100 M solution has a pH of 4.100 0 ≈0 construct an ICE change table for the equilibrium 5.25? use the pH to find the equilibrium [H3O+] HA + H2O  A + H3O+ write the reaction [HA] [A−] [H3O+] for the acid with water initial 0. Chemistry: A Molecular Approach.

6E-05 Ka expression and compute Ka Tro. change −5.25? fill in the rest of the HA + H2O  A + H3O+ table using the [H3O+] as a guide [HA] [A−] [H3O+] if the difference is initial 0. . 2/e 99 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach.8: What is the Ka of a weak acid if a 0.100 0 0 insignificant.6E-05 [HA]equil = [HA]initial 0.6E-05 5.6E-05 +5.100  equilibrium 0.6E-05 substitute into the 5.100 5.100 M solution has a pH of 4. Example 15. Inc.6E-05 +5.

. 2/e 100 Copyright  2011 Pearson Education.40? Tro.012 M solution of nicotinic acid has a pH of 3. Practice – What is the Ka of nicotinic acid. Inc. HC6H4NO2. Chemistry: A Molecular Approach. if a 0.

Chemistry: A Molecular Approach.0E-04 concentrations and [H3O+]equil Tro.012 M solution of nicotinic acid has a pH of 3. . Practice – What is the Ka of nicotinic acid. if a 0. HC6H4NO2. 2/e 101 Copyright  2011 Pearson Education.012 0 ≈0 table for the reaction change enter the initial equilibrium 4. Inc.40? use the pH to find the equilibrium [H3O+] HA + H2O  A + H3O+ write the reaction for the acid with water [HA] [A−] [H3O+] construct an ICE initial 0.

Practice – What is the Ka of nicotinic acid.012 Ka expression and compute Ka Tro. −4.0E-04 4. .012 M solution of nicotinic acid has a pH of 3.0E-04 0.0E-04 [HA]equil = [HA]initial change 0.40? fill in the rest of the HA + H2O  A + H3O+ table using the [H3O+] as a guide [HA] [A−] [H3O+] if the difference is initial 0.0E-04 +4. Chemistry: A Molecular Approach.012  4. HC6H4NO2. Inc.0E-04 +4.0E-04 substitute into the equilibrium 4.012 0 0 insignificant. 2/e 102 Copyright  2011 Pearson Education. if a 0.

2 H = diprotic. 3 H = triprotic  HCl = monoprotic. Chemistry: A Molecular Approach. H2SO4 = diprotic. Polyprotic Acids • Acid molecules often have more than one ionizable H – these are called polyprotic acids  the ionizable H’s may have different acid strengths or be equal  1 H = monoprotic. Inc. H3PO4 = triprotic • Polyprotic acids ionize in steps  each ionizable H is removed sequentially • Removing of the first H automatically makes removal of the second H harder  H2SO4 is a stronger acid than HSO4 Tro. . 2/e 103 Copyright  2011 Pearson Education.

. 2/e 104 Copyright  2011 Pearson Education. Inc. Chemistry: A Molecular Approach. the stronger the acid • Because [ionized acid]equil = [H3O+]equil Tro. Percent Ionization • Another way to measure the strength of an acid is to determine the percentage of acid molecules that ionize when dissolved in water – this is called the percent ionization  the higher the percent ionization.

Inc. Chemistry: A Molecular Approach. 2/e 105 Copyright  2011 Pearson Education.5 0 ≈≈00 enter the Initial change x +x +x Concentrations equilibrium 2.5 M HNO2 solution? write the reaction for HNO2 + H2O  NO2 + H3O+ the acid with water construct an ICE [HNO2] [NO2−] [H3O+] table for the reaction initial 2. Example 15.5  x x x define the change in concentration in terms of x sum the columns to define the equilibrium concentrations Tro.9: What is the percent ionization of a 2. .

Example 15. Inc.5 [HNO2] [NO2−] [H3O+] because Ka is very initial 2. approximate the [HNO2]eq = change −x +x +x [HNO2]init and solve equilibrium 2. .5−x ≈2.5 x x for x Tro.6 x 10−4 of Ka from Table 15. 2/e 106 Copyright  2011 Pearson Education.5 0 ≈0 small.9: What is the percent ionization of a 2. Chemistry: A Molecular Approach.5 M HNO2 solution? determine the value Ka for HNO2 = 4.

Inc.5 x 0. .9: What is the percent ionization of a 2.034 x 0. Chemistry: A Molecular Approach.034 x = 3.4 x 10−2 Tro.5 M HNO2 solution? HNO2 + H2O  NO2 + H3O+ substitute x into [HNO2] [NO2−] [H3O+] the equilibrium concentration initial 2.5 0 ≈0 definitions and change −x +x +x solve equilibrium 2. Example 15. 2/e 107 Copyright  2011 Pearson Education.5 x 2.

Inc.034 because the percent ionization is < 5%.5 0. . the “x is small” approximation is valid Tro.034 0. Example 15. Chemistry: A Molecular Approach. 2/e 108 Copyright  2011 Pearson Education.9: What is the percent ionization of a 2.5 0 ≈0 change −x +x +x equilibrium 2.5 M HNO2 solution? HNO2 + H2O  NO2 + H3O+ apply the definition [HNO2] [NO2−] [H3O+] and compute the percent ionization initial 2.

Chemistry: A Molecular Approach. .4 x 10−5 @ 25 °C) Tro.012 M solution of nicotinic acid. 2/e 109 Copyright  2011 Pearson Education. Practice – What is the percent ionization of a 0. HC 6H4NO2? (Ka = 1. Inc.

Practice – What is the percent ionization of a 0.012 0 ≈0 enter the initial change concentrations – equilibrium assuming the [H3O+] from water is ≈ 0 Tro. 2/e 110 Copyright  2011 Pearson Education. Inc. . HC 6H4NO2? write the reaction for HC6H4NO2 + H2O  C6H4NO2 + H3O+ the acid with water construct an ICE [HA] [A−] [H3O+] table for the reaction initial 0. Chemistry: A Molecular Approach.012 M solution of nicotinic acid.

HC 6H4NO2? represent the HC6H4NO2 + H2O  C6H4NO2 + H3O+ change in the concentrations in [HA] [A−] [H3O+] terms of x initial 0. 2/e 111 Copyright  2011 Pearson Education.012 x x x concentrations in terms of x substitute into the equilibrium constant expression Tro. Inc. Chemistry: A Molecular Approach.012 M solution of nicotinic acid. Practice – What is the percent ionization of a 0.012 0 0 sum the columns change x +x +x to find the equilibrium equilibrium 0. .

012 M solution of nicotinic acid. Practice – What is the percent ionization of a 0.4 x 10−5 HC6H4NO2 + H2O  C6H4NO2 + H3O+ determine the value of Ka [HA] [A−] [H3O+] because Ka is very initial 0. 2/e 112 Copyright  2011 Pearson Education.012 0 ≈0 small. .012 0.012x x x Tro. HC6H4NO2? Ka = 1. approximate change −x +x +x the [HA]eq = [HA]init and solve for x equilibrium 0. Inc. Chemistry: A Molecular Approach.

1 x 10−4 Tro. Chemistry: A Molecular Approach. HC6H4NO2? substitute x into [HA] [A−] [H3O+] the equilibrium concentration initial 0.012−x x x x = 4.012 M solution of nicotinic acid. Inc. . 2/e 113 Copyright  2011 Pearson Education. Practice – What is the percent ionization of a 0.012 0 ≈0 definitions and change −x +x +x solve equilibrium 0.

the “x is small” approximation is valid Tro. Practice – What is the percent ionization of a 0. Inc. 2/e 114 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach. .012 M solution of nicotinic acid.012 0 ≈0 change −x +x +x because the equilibrium 0.1E-04 4.012 4.1E-04 percent ionization is < 5%. HC 6H4NO2? apply the definition [HA] [A−] [H3O+] and compute the percent ionization initial 0.

2/e 115 Copyright  2011 Pearson Education. Inc. . Relationship Between [H3O+]equilibrium & [HA]initial • Increasing the initial concentration of acid results in increased [H3O+] at equilibrium • Increasing the initial concentration of acid results in decreased percent ionization • This means that the increase in [H3O+] concentration is slower than the increase in acid concentration Tro. Chemistry: A Molecular Approach.

Why doesn’t the increase in H3O+ keep up with the increase in HA? • The reaction for ionization of a weak acid is HA(aq) + H2O(l)  A−(aq) + H3O+(aq) • According to Le Châtelier’s Principle. 2/e 116 Copyright  2011 Pearson Education. Inc. Chemistry: A Molecular Approach. . the equilibrium should shift to the right to increase the total number of dissolved particles  we can reduce the (aq) concentrations by using a more dilute initial acid concentration • The result will be a larger [H3O+] in the dilute solution compared to the initial acid concentration • This will result in a larger percent ionization Tro. if we reduce the concentrations of all the (aq) components.

the complete ionization of the strong acid provides more than enough [H3O+] to shift the weak acid equilibrium to the left so far that the weak acid’s added [H3O+] is negligible • For mixtures of weak acids. and their concentrations are similar Tro. you can ignore the contribution of the weaker acid to the [H3O+]equil • For a mixture of a strong acid with a weak acid. Inc. Chemistry: A Molecular Approach. generally only need to consider the stronger for the same reasons  as long as one is significantly stronger than the other. . Finding the pH of Mixtures of Acids • Generally. 2/e 117 Copyright  2011 Pearson Education.

0 x 10−14 sufficiently different.100 M HClO2(aq) write the reactions for HF + H2O  F + H3O+ Ka = 3.5 x 10−4 the acids with water and determine their Kas HClO + H2O  ClO + H3O+ Ka = 2. Inc. Chemistry: A Molecular Approach.9 x 10−8 if the Kas are H2O + H2O  OH + H3O+ Kw = 1.10: Find the pH of a mixture of 0. 2/e 118 Copyright  2011 Pearson Education. use the strongest acid to construct an ICE [HF] [F−] [H3O+] table for the reaction initial 0. .150 M HF(aq) solution and 0.150 0 ≈0 enter the initial concentrations – change assuming the [H3O+] from water is ≈ 0 equilibrium Tro. Example 15.

150 0 0 term of x change x +x +x sum the columns to find the equilibrium equilibrium 0. Chemistry: A Molecular Approach.150 x x x concentrations in terms of x substitute into the equilibrium constant expression Tro.10: Find the pH of a mixture of 0.150 M HF(aq) solution and 0.100 M HClO2(aq) represent the [HF] [F-] [H3O+] change in the concentrations in initial 0. Inc.Example 15. 2/e 119 Copyright  2011 Pearson Education. .

approximate the [HF]eq = [HF]init initial 0. . Inc.150 0 ≈0 and solve for x change −x +x +x equilibrium 0.150 0.100 M HClO2(aq) Ka for HF = 3.5 x 10−4 because Ka is very [HF] [F-] [H3O+] small.Example 15.10: Find the pH of a mixture of 0. 2/e 120 Copyright  2011 Pearson Education.150 x x x Tro.150 M HF(aq) solution and 0. Chemistry: A Molecular Approach.

2/e 121 Copyright  2011 Pearson Education. .Example 15.150 0 ≈0 x < 5% of [HF]init change −x +x +x equilibrium 0.100 M HClO2(aq) Ka for HF = 3.150 M HF(aq) solution and 0.5 x 10−4 check if the [HF] [F-] [H3O+] approximation is valid by seeing if initial 0. Chemistry: A Molecular Approach.2 x 10−3 the approximation is valid Tro. Inc.10: Find the pH of a mixture of 0.150 x x x = 7.

150-x x 0. . Chemistry: A Molecular Approach.150 0 ≈0 definitions and change −x +x +x solve equilibrium 0.Example 15.143 0. Inc.0072 x 0.100 M HClO2(aq) Ka for HF = 3.150 M HF(aq) solution and 0.2 x 10−3 Tro.0072 x = 7. 2/e 122 Copyright  2011 Pearson Education.10: Find the pH of a mixture of 0.5 x 10−4 substitute x into [HF] [F-] [H3O+] the equilibrium concentration initial 0.

143 0. Inc.100 M HClO2(aq) Ka for HF = 3.5 x 10−4 substitute [H3O+] [HF] [F-] [H3O+] into the formula for pH and solve initial 0.10: Find the pH of a mixture of 0.150 0 ≈0 change −x +x +x equilibrium 0.0072 0. .0072 Tro. 2/e 123 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach.Example 15.150 M HF(aq) solution and 0.

Example 15. 2/e 124 Copyright  2011 Pearson Education.5 x 10−4 check by substituting [HF] [F-] [H3O+] the equilibrium concentrations back initial 0.150 0 ≈0 into the equilibrium change −x +x +x constant expression and comparing the equilibrium 0. Inc.100 M HClO2(aq) Ka for HF = 3. the answer is reasonably close Tro.0072 0.10: Find the pH of a mixture of 0. . Chemistry: A Molecular Approach.0072 calculated Ka to the given Ka though not exact.150 M HF(aq) solution and 0.143 0.

.045 M HCl and 0.15 M HF Tro. Chemistry: A Molecular Approach. Practice – Determine the pH @ 25 ºC of a solution that is a mixture of 0. Inc. 2/e 125 Copyright  2011 Pearson Education.

Inc.5 x 10−2 M. the fact that the pH < 7 means the solution is acidic Tro.15 M Find: pH Conceptual Because HCl is a strong acid and HF is a weak acid. 2/e 126 Copyright  2011 Pearson Education. [HF] = 0. Plan: [H3O+] = [HCl] [HCl] [H3O+] pH Relationships: Solution: Check: pH is unitless.045 M HCl and 0. . Practice – Determine the pH @ 25 ºC of a solution that is a mixture of 0.15 M HF Given: [HCl] = 4. Chemistry: A Molecular Approach.

Chemistry: A Molecular Approach. Strong Bases • The stronger the base. the more willing it is to accept H NaOH  Na+ + OH−  use water as the standard acid • For ionic bases. Inc. . practically all units are dissociated into OH– or accept H’s  strong electrolyte  multi-OH strong bases completely dissociated • [HO–] = [strong base] x (# OH) Tro. 2/e 127 Copyright  2011 Pearson Education.

0030 M Check: pH is unitless. the fact that the pH > 7 means the solution is basic Tro.0015 M Sr(OH)2 solution and determine if the solution is acidic. Example 15. 2/e 128 Copyright  2011 Pearson Education.11: Calculate the pH at 25 °C of a 0. Chemistry: A Molecular Approach. or neutral Given: [Sr(OH)2] = 1. Inc. basic.0015) = 0.5 x 10−3 M Find: pH Conceptual [Sr(OH)2] [OH] [H3O+] pH Plan: [OH]=2[Sr(OH)2] Relationships: Solution: [OH] = 2(0. .

.0020 M HCl [H3O+] = [HCl] = 2.0 x 10−3) = 2. Chemistry: A Molecular Approach. Practice – Calculate the pH of the following strong acid or base solutions 0.52 pH = 14.52 pH = 11.48 Tro.0015 M Ca(OH)2 [OH−] = 2 x [Ca(OH)2] = 3. 2/e 130 Copyright  2011 Pearson Education.00 − pOH = 14.0 x 10−3 M pOH = −log(3.70 0.0 x 10−3) = 2.00 − 2.0 x 10−3 M pH = −log(2. Inc.

Chemistry: A Molecular Approach. Weak Bases • In weak bases. only a small fraction of molecules accept H’s  weak electrolyte NH3 + H2O  NH4+ + OH−  most of the weak base molecules do not take H from water  much less than 1% ionization in water • [HO–] << [weak base] • Finding the pH of a weak base solution is similar to finding the pH of a weak acid Tro. 2/e 131 Copyright  2011 Pearson Education. . Inc.

Kb • Base strength measured by the size of the equilibrium constant when react with H2O :Base + H2O  OH− + H:Base+ • The equilibrium constant is called the base ionization constant. 2/e 132 Copyright  2011 Pearson Education. Kb  larger Kb = stronger base Tro. . Chemistry: A Molecular Approach. Inc. Base Ionization Constant.

. 2/e 133 Copyright  2011 Pearson Education.Tro. Inc. Chemistry: A Molecular Approach.

. Structure of Amines Tro. Inc. Chemistry: A Molecular Approach. 2/e 134 Copyright  2011 Pearson Education.

2/e 135 Copyright  2011 Pearson Education. Example 15. Chemistry: A Molecular Approach. Inc.12:Find the pH of 0.100 0 ≈0 table for the change reaction equilibrium enter the initial concentrations – assuming the because no products initially. . [OH] from water and the reaction is proceeding forward is ≈ 0 Tro. Qc = 0.100 M NH 3(aq) write the reaction NH3 + H2O  NH4+ + OH for the base with water [NH3] [NH4+] [OH] construct an ICE initial 0.

Example 15.100 0 0 terms of x change x +x +x sum the columns to equilibrium 0. Inc. .100 x x x find the equilibrium concentrations in terms of x substitute into the equilibrium constant expression Tro.12: Find the pH of 0. Chemistry: A Molecular Approach.100 M NH 3(aq) represent the [NH3] [NH4+] [OH] change in the concentrations in initial 0. 2/e 136 Copyright  2011 Pearson Education.

76 x 10−5 of Kb from Table 15.100 M NH 3(aq) determine the value Kb for NH3 = 1. Inc.8 [NH3] [NH4+] [OH] because Kb is very initial 0.100 0 ≈0 small. Chemistry: A Molecular Approach. . Example 15. 2/e 137 Copyright  2011 Pearson Education.12: Find the pH of 0. approximate change −x +x +x the [NH3]eq = [NH3]init and solve for x 0.100 x x Tro.100x equilibrium 0.

2/e 138 Copyright  2011 Pearson Education.76 x 10−5 check if the [NH3] [NH4+] [OH] approximation is valid by seeing if initial 0.33 x 10−3 the approximation is valid Tro. . Example 15. Chemistry: A Molecular Approach.100 M NH 3(aq) Kb for NH3 = 1. Inc.100 x x x = 1.12: Find the pH of 0.100 0 ≈0 x < 5% of [NH3]init change −x +x +x equilibrium 0.

12: Find the pH of 0.76 x 10−5 substitute x into [NH3] [NH4+] [OH] the equilibrium concentration initial 0. Inc.33E-3 x = 1.33E-3 x x 1. .100 0 ≈0 definitions and change -x +x +x solve equilibrium 0. Example 15.099x 1. Chemistry: A Molecular Approach. 2/e 139 Copyright  2011 Pearson Education.100 0.33 x 10−3 Tro.100 M NH 3(aq) Kb for NH3 = 1.

100 M NH 3(aq) Kb for NH3 = 1. .12: Find the pH of 0. Chemistry: A Molecular Approach.76 x 10−5 use the [OH−] to [NH3] [NH4+] [OH] find the [H3O+] using Kw initial 0.33E−3 for pH and solve Tro.099 1. Example 15.33E−3 1. Inc. 2/e 140 Copyright  2011 Pearson Education.100 0 ≈0 substitute [H3O+] change −x +x +x into the formula equilibrium 0.

100 M NH 3(aq) Kb for NH3 = 1. Inc.76 x 10−5 check by substituting the [NH3] [NH4+] [OH] equilibrium concentrations back initial 0.33E−3 calculated Kb to the given Kb though not exact.099 1.33E−3 1. . 2/e 142 Copyright  2011 Pearson Education. Example 15. the answer is reasonably close Tro.100 0 ≈0 into the equilibrium change −x +x +x constant expression and comparing the equilibrium 0.12: Find the pH of 0. Chemistry: A Molecular Approach.

2/e 143 Copyright  2011 Pearson Education. Kb = 1. Chemistry: A Molecular Approach. . Inc.6 x 10−6 Tro.0015 M morphine solution. Practice – Find the pH of a 0.

Practice – Find the pH of a 0.0015 M morphine solution

write the reaction
for the base with B + H2O  BH+ + OH
water [B] [BH+] [OH]
construct an ICE initial 0.0015 0 ≈0
table for the
reaction change
enter the initial equilibrium
concentrations –
assuming the
because no products initially, Qc = 0,
[OH] from water
is ≈ 0 and the reaction is proceeding forward

Tro, Chemistry: A Molecular Approach, 2/e 144 Copyright  2011 Pearson Education, Inc.

Practice – Find the pH of a 0.0015 M morphine solution

represent the B + H2O  BH+ + OH
change in the
concentrations in [B] [BH+] [OH]
terms of x
initial 0.0015 0 0
sum the columns
to find the change x +x +x
equilibrium equilibrium 0.0015 x x x
concentrations in
terms of x
substitute into
the equilibrium
constant
expression
Tro, Chemistry: A Molecular Approach, 2/e 145 Copyright  2011 Pearson Education, Inc.

Practice – Find the pH of a 0.0015 M morphine solution

determine the Kb for morphine = 1.6 x 10−6
value of Kb
[B] [BH+] [OH]
because Kb is very initial 0.0015 0 ≈0
small, approximate
the [B]eq = [B]init change −x +x +x
and solve for x equilibrium 0.0015
0.0015 x x x

Tro, Chemistry: A Molecular Approach, 2/e 146 Copyright  2011 Pearson Education, Inc.

Practice – Find the pH of a 0.0015 M morphine solution
Kb for morphine = 1.6 x 10−6
check if the [B] [BH+] [OH]
approximation is
valid by seeing if initial 0.0015 0 ≈0
x < 5% of [B]init change −x +x +x
equilibrium 0.0015 x x
x = 4.9 x 10−5

the approximation is valid
Tro, Chemistry: A Molecular Approach, 2/e 147 Copyright  2011 Pearson Education, Inc.

0015 0 ≈≈ 00 definitions and change −x +x +x +x solve equilibrium 0.9 x 10−5 Tro.9E−5 x = 4. Chemistry: A Molecular Approach. 2/e 148 Copyright  2011 Pearson Education.9E−5 x 4.6 x 10−6 substitute x into [B] [BH++] [OH [OH]] the equilibrium concentration initial 0. Inc.0015 M morphine solution Kb for morphine = 1. Practice – Find the pH of a 0.0015 x 0. .0015x 4.

2/e 149 Copyright  2011 Pearson Education.0015 4. Chemistry: A Molecular Approach. Practice – Find the pH of a 0.9E−5 4. .9E−5 for pH and solve Tro.0015 0 ≈0 change −x +x +x substitute [H3O+] into the formula equilibrium 0. Inc.0015 M morphine solution Kb for morphine = 1.6 x 10−6 use the [OH−] to [B] [BH+] [OH] find the [H3O+] using Kw initial 0.

0015 4.6 x 10−6 check by substituting the [B] [BH+] [OH] equilibrium concentrations back initial 0. . Inc.0015 M morphine solution Kb for morphine = 1.9E−5 calculated Kb to the given Kb the answer matches the given Kb Tro.9E−5 4.0015 0 ≈0 into the equilibrium change −x +x +x constant expression and comparing the equilibrium 0. Chemistry: A Molecular Approach. 2/e 151 Copyright  2011 Pearson Education. Practice – Find the pH of a 0.

2/e 152 Copyright  2011 Pearson Education. Inc. Acid–Base Properties of Salts • Salts are water-soluble ionic compounds • Salts that contain the cation of a strong base and an anion that is the conjugate base of a weak acid are basic  NaHCO3 solutions are basic  Na+ is the cation of the strong base NaOH  HCO3− is the conjugate base of the weak acid H 2CO3 • Salts that contain cations that are the conjugate acid of a weak base and an anion of a strong acid are acidic  NH4Cl solutions are acidic  NH4+ is the conjugate acid of the weak base NH 3  Cl− is the anion of the strong acid HCl Tro. Chemistry: A Molecular Approach. .

the weaker the conjugate base is • An anion that is the conjugate base of a strong acid is pH neutral Cl−(aq) + H2O(l)  HCl(aq) + OH−(aq) • An anion that is the conjugate base of a weak acid is basic F−(aq) + H2O(l)  HF(aq) + OH−(aq) Tro. Chemistry: A Molecular Approach. . 2/e 153 Copyright  2011 Pearson Education. Anions as Weak Bases • Every anion can be thought of as the conjugate base of an acid • Therefore. Inc. every anion can potentially be a base  A−(aq) + H2O(l)  HA(aq) + OH−(aq) • The stronger the acid is.

Example 15.13: Use the table to determine
if the given anion is basic or neutral

a) NO3−
the conjugate base of
a strong acid,
therefore neutral
b) NO2−
the conjugate base of
a weak acid, therefore
basic

Tro, Chemistry: A Molecular Approach, 2/e 154 Copyright  2011 Pearson Education, Inc.

Relationship between Ka of an Acid and
Kb of Its Conjugate Base

• Many reference books only give tables of Ka
values because Kb values can be found from them
when you add
equations, you
multiply the K’s

Tro, Chemistry: A Molecular Approach, 2/e 155 Copyright  2011 Pearson Education, Inc.

Na+ is the cation
of a strong base – Example 15.14: Find the pH of
pH neutral. The 0.100 M NaCHO2(aq) solution
CHO2− is the
anion of a weak
acid – pH basic CHO2− + H2O  HCHO2 + OH
write the reaction [CHO2−] [HCHO2] [OH]
for the anion with initial 0.100 0 ≈0
water
change
construct an ICE
table for the equilibrium
reaction
enter the initial
concentrations –
assuming the
[OH] from water
is ≈ 0
Copyright  2011 Pearson Education, Inc.

Example 15.14: Find the pH of 0.100
M NaCHO2(aq) solution
represent the
change in the [CHO2−] [HCHO2] [OH]
concentrations in
terms of x initial 0.100 0 ≈0
sum the columns to change x +x +x
find the equilibrium
concentrations in equilibrium 0.100 x x x
terms of x

Calculate the value
of Kb from the value
of Ka of the weak
acid from Table 15.5
substitute into the
equilibrium constant
expression
Tro, Chemistry: A Molecular Approach, 2/e 157 Copyright  2011 Pearson Education, Inc.

approximate the [CHO2−]eq = initial 0.6 x 10−11 because Kb is very [CHO2−] [HCHO2] [OH] small. .100 0 ≈0 [CHO2−]init and solve change −x +x +x for x equilibrium 0.100 M NaCHO2(aq) Kb for CHO2− = 5. Chemistry: A Molecular Approach.14: Find the pH of 0. 2/e 158 Copyright  2011 Pearson Education.100 0. Example 15.100x x x Tro. Inc.

. 2/e 159 Copyright  2011 Pearson Education.14: Find the pH of 0.100 x x x = 2.100 M NaCHO2(aq) Kb for CHO2− = 5.100 0 ≈0 x < 5% of change −x +x +x [CHO2−]init equilibrium 0. Chemistry: A Molecular Approach.4 x 10−6 the approximation is valid Tro. Inc. Example 15.6 x 10−11 check if the [CHO2−] [HCHO2] [OH] approximation is valid by seeing if initial 0.

Inc.100 M NaCHO2(aq) Kb for CHO2− = 5. .100−x x 2.14: Find the pH of 0. Example 15.100 0.4E-6 x = 2.6 x 10−11 substitute x into [CHO2−] [HCHO2] [OH] the equilibrium concentration initial 0.4 x 10−6 Tro. Chemistry: A Molecular Approach.4E-6 x 2. 2/e 160 Copyright  2011 Pearson Education.100 0 ≈0 definitions and change −x +x +x solve equilibrium 0.

100 M NaCHO2(aq) Kb for CHO2− = 5.4E-6 for pH and solve Tro. 2/e 161 Copyright  2011 Pearson Education.100 2.4E-6 2. Chemistry: A Molecular Approach. Inc.100 0 ≈0 substitute [H3O+] change −x +x +x into the formula equilibrium 0.6 x 10−11 use the [OH−] to find the [H3O+] [CHO2−] [HCHO2] [OH] using Kw initial 0.14: Find the pH of 0. Example 15. .

the answer is reasonably close Tro.100 0 ≈0 back into the equilibrium change −x +x +x constant equilibrium 0. 2/e 163 Copyright  2011 Pearson Education.100 2. Chemistry: A Molecular Approach.4E−6 2. Example 15.4E−6 expression and comparing the calculated Kb to the given Kb though not exact. Inc.6 x 10−11 substituting the [CHO2−] [HCHO2] [OH] equilibrium concentrations initial 0.14: Find the pH of 0.100 M NaCHO2(aq) check by Kb for CHO2− = 5. .

Practice – If a 0. Chemistry: A Molecular Approach.45. what is the Ka of HA? Tro. 2/e 164 Copyright  2011 Pearson Education. Inc. .15 M NaA solution has a pOH of 5.

what is the Ka of HA? Because pOH is < 7. Inc. of 5.45.0015 M NaA solution has a pOH pOH neutral. the solutinon is basic. A is basic.Na+ is the cation of a strong base – If a 0.100 0 ≈0 water change construct an ICE table for the equilibrium reaction enter the initial concentrations – assuming the [OH] from water is ≈ 0 165 Copyright  2011 Pearson Education. − A − + H 2O  HA + OH  write the reaction [A−] [HA] [OH] for the anion with initial 0. .

15 M NaA solution has a pOH of 5. 2/e 166 Copyright  2011 Pearson Education. .6E-6 Tro.6E−6 equilibrium 0. Inc.6E−6 +3.6E-6 3.15 3. Practice – If a 0.45. Chemistry: A Molecular Approach. what is the Ka of HA? use the pOH to [A−] [HA] [OH] find the [OH−] initial 0.6E−6 +3.15 0 ≈0 use [OH−] to fill in other items change −3.

6E−6 equilibrium 0. 2/e 167 Copyright  2011 Pearson Education. what is the Ka of HA? calculate the [A−] [HA] [OH] value of Kb of A− initial 0.15 M NaA solution has a pOH of 5.6E-6 3. Practice – If a 0. Inc.6E−6 +3.6E−6 +3.45. . Chemistry: A Molecular Approach.15 0 ≈0 change −3.6E-6 Tro.15 3.

what is the Ka of HA? use Kb of A− to [A−] [HA] [OH] find Ka of HA initial 0.6E-6 3.6E−6 +3. Chemistry: A Molecular Approach.15 3.15 0 ≈0 change −3. .6E-6  K b     Tro.15 M NaA solution has a pOH of 5. Inc.6E−6 equilibrium 0. Practice – If a 0.45. 2/e 168 Copyright  2011 Pearson Education.6E−6 +3.

some cations can potentially be acidic  MH+(aq) + H2O(l)  MOH(aq) + H3O+(aq) • The stronger the base is. the weaker the conjugate acid is  a cation that is the counter-ion of a strong base is pH neutral  a cation that is the conjugate acid of a weak base is acidic NH4+(aq) + H2O(l)  NH3(aq) + H3O+(aq)  because NH3 is a weak base. Inc. 2/e 169 Copyright  2011 Pearson Education. . the position of this equilibrium favors the right Tro. Chemistry: A Molecular Approach. Polyatomic Cations as Weak Acids • Some cations can be thought of as the conjugate acid of a weak base  others are the counter-ions of a strong base • Therefore.

Inc. . Metal Cations as Weak Acids • Cations of small. highly charged metals are weakly acidic  alkali metal cations and alkali earth metal cations are pH neutral  cations are hydrated Al(H2O)63+(aq) + H2O(l)  Al(H2O)5(OH)2+ (aq) + H3O+(aq) Tro. 2/e 170 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach.

therefore acidic Tro. therefore neutral a) Cr3+ a highly charged metal ion. Inc. Example 15. therefore acidic b) Ca2+ the counter-ion of the strong base Ca(OH)2. . Chemistry: A Molecular Approach.15: Determine if the given cation Is acidic or neutral a) C5N5NH2+ the conjugate acid of the weak base pyridine. 2/e 171 Copyright  2011 Pearson Education.

Basic. it will form a neutral solution  NaCl Ca(NO3)2 KBr • If the salt cation is the counter-ion of a strong base and the anion is the conjugate base of a weak acid. . Classifying Salt Solutions as Acidic. 2/e 172 Copyright  2011 Pearson Education. or Neutral • If the salt cation is the counter-ion of a strong base and the anion is the conjugate base of a strong acid. Inc. it will form a basic solution  NaF Ca(C2H3O2)2 KNO2 Tro. Chemistry: A Molecular Approach.

Classifying Salt Solutions as Acidic. Chemistry: A Molecular Approach. Inc. or Neutral • If the salt cation is the conjugate acid of a weak base and the anion is the conjugate base of a strong acid. . it will form an acidic solution  NH4Cl • If the salt cation is a highly charged metal ion and the anion is the conjugate base of a strong acid. Basic. 2/e 173 Copyright  2011 Pearson Education. it will form an acidic solution  Al(NO3)3 Tro.

Ka of NH4+ is larger than Kb of the F−. Basic. therefore the solution will be acidic Tro. Classifying Salt Solutions as Acidic. . 2/e 174 Copyright  2011 Pearson Education. Inc. the pH of the solution depends on the relative strengths of the acid and base  NH4F because HF is a stronger acid than NH4+. Chemistry: A Molecular Approach. or Neutral • If the salt cation is the conjugate acid of a weak base and the anion is the conjugate base of a weak acid.

Inc. pH neutral Cl− is the conjugate base of a strong acid. Example 15. basic. Chemistry: A Molecular Approach. .16: Determine whether a solution of the following salts is acidic. or neutral a) SrCl2 Sr2+ is the counter-ion of a strong base. pH neutral solution will be acidic b) CH3NH3NO3 CH3NH3+ is the conjugate acid of a weak base. acidic NO3− is the conjugate base of a strong acid. 2/e 175 Copyright  2011 Pearson Education. highly charged metal ion. pH neutral solution will be pH neutral b) AlBr3 Al3+ is a small. weak acid Cl− is the conjugate base of a strong acid. pH neutral solution will be acidic Tro.

basic. .16: Determine whether a solution of the following salts is acidic. solution will be acidic Tro. Chemistry: A Molecular Approach. or neutral d) NaCHO2 Na+ is the counter-ion of a strong base. basic Ka(NH4+) > Kb(F−). basic solution will be basic d) NH4F NH4+ is the conjugate acid of a weak base. Example 15. 2/e 176 Copyright  2011 Pearson Education. Inc. pH neutral CHO2− is the conjugate base of a weak acid. acidic F− is the conjugate base of a weak acid.

or neutral K+ is the counter-ion of a strong base. pH neutral the solution is pH basic • Ba(HCO3)2 CH NH + isis the HCO the conjugate conjugate of of aa weak weak acid. Practice – Determine whether a solution of the following salts is acidic. . pH neutral • KNO3 NO − is the counter-ion of a strong acid. 2/e 177 Copyright  2011 Pearson Education. pH neutral 3 the Co3+solution is pH is a highly neutralcation. Chemistry: A Molecular Approach. Inc.pH pHbasic − 3 3 3 acidic the solution is pH acidic • CH3NH3−NO3 NO3 is the counter-ion of a strong acid. pH acidic charged • CoCl3 Cl− is the counter-ion of a strong acid. base. basic. pH neutral Tro. pH neutral the 2+ solution is pH acidic Ba is the counter-ion of a strong base.

each H has a separate Ka • Ka1 > Ka2 > Ka3 • Generally. . Ionization in Polyprotic Acids • Because polyprotic acids ionize in steps. the difference in Ka values is great enough so that the second ionization does not happen to a large enough extent to affect the pH  most pH problems just do first ionization  except H2SO4  use [H2SO4] as the [H3O+] for the second ionization • [A2−] = Ka2 as long as the second ionization is negligible Tro. Chemistry: A Molecular Approach. 2/e 178 Copyright  2011 Pearson Education. Inc.

. Chemistry: A Molecular Approach. 2/e 179 Copyright  2011 Pearson Education. Inc.Tro.

Ka2 = 5.12 M solution of carbonic acid. H2CO3? (Ka1 = 4. Inc. Chemistry: A Molecular Approach. . Practice – What is the pH of a 0.6 x 10−11) Tro.3 x 10−7. 2/e 180 Copyright  2011 Pearson Education.

Inc.12 M solution of carbonic acid. . H2CO3? H2CO3 + H2O  HCO3 + H3O+ write the reactions for the acid with HCO3− + H2O  CO32− + H3O+ water one H at a time [HA] [A−] [H3O+] construct an ICE table for the initial 0. 2/e 181 Copyright  2011 Pearson Education.12 0 ≈0 reaction change enter the initial equilibrium concentrations – assuming the second ionization is negligible Tro. Practice – What is the pH of a 0. Chemistry: A Molecular Approach.

2/e 182 Copyright  2011 Pearson Education. . Inc. Practice – What is the pH of a 0. H2CO3? represent the H2CO3 + H2O  HCO3 + H3O+ change in the concentrations in [HA] [A−] [H3O+] terms of x initial 0.12 M solution of carbonic acid.12 0 0 sum the columns x +x change +x to find the equilibrium equilibrium 0. Chemistry: A Molecular Approach.12 x x x concentrations in terms of x substitute into the equilibrium constant expression Tro.

Inc. . Ka2 = 5.3 x 10−7.012 x x Tro.12 x 0. approximate initial 0. 2/e 183 Copyright  2011 Pearson Education.12 M solution of carbonic acid. H2CO3? determine the Ka1 = 4.12 0 ≈0 the [HA]eq = [HA]init change −x +x +x and solve for x equilibrium 0.6 x 10−11 value of Ka1 [HA] [A−] [H3O+] because Ka1 is very small. Practice – What is the pH of a 0. Chemistry: A Molecular Approach.

27 x 10−4 the approximation is valid Tro. .12 M solution of carbonic acid.12 0 ≈0 x < 5% of change −x +x +x [H2CO3]init equilibrium 0.12 x x x = 2.3 x 10−7 check if the [HA] [A−] [H3O+] approximation is valid by seeing if initial 0. H2CO3? Ka1 for H2CO3 = 4. Inc. 2/e 184 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach. Practice – What is the pH of a 0.

12 0 ≈0 definitions and change −x +x +x solve equilibrium 0.12−x x x x = 2. Chemistry: A Molecular Approach. Practice – What is the pH of a 0.3 x 10−4 Tro. . 2/e 185 Copyright  2011 Pearson Education. H2CO3? substitute x into the [HA] [A−] [H3O+] equilibrium concentration initial 0.12 M solution of carbonic acid. Inc.

H2CO3? substitute [H3O+] [HA] [A−] [H3O+] into the formula for pH and solve initial 0.00023 Tro. .12 M solution of carbonic acid. Practice – What is the pH of a 0. Inc.12 0.00023 0. 2/e 186 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach.12 0 ≈0 change −x +x +x equilibrium 0.

00023 0.12 M solution of carbonic acid.12 0 ≈0 constant expression change −x +x +x and comparing the calculated Ka to the equilibrium 0. 2/e 187 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach. . Practice – What is the pH of a 0. Inc. H2CO3? check by substituting Ka1 for H2CO3 = 4.00023 given Ka the values match within sig figs Tro.3 x 10−7 the equilibrium [HA] [A−] [H3O+] concentrations back into the equilibrium initial 0.12 0.

12 M solution of carbonic acid.3 x 10−7. Practice – What is the [CO32−] in a 0. Inc. Ka2 = 5. H2CO3? (Ka1 = 4. . 2/e 188 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach.6 x 10−11) Tro.

. Inc.00023 0 0.12 M solution of carbonic acid. Chemistry: A Molecular Approach.00023 enter the initial change concentrations for equilibrium the second ionization using the equilibrium concentrations from first ionization Tro. Practice – What is the [CO32−] in a 0. H2CO3? write the reactions for the acid with H2CO3 + H2O  HCO3 + H3O+ water one H at a HCO3− + H2O  CO32− + H3O+ time construct an ICE [HCO3−] [CO32−] [H3O+] table for the reaction initial 0. 2/e 189 Copyright  2011 Pearson Education.

3E−4 x x 2.3E−4 +x concentrations in terms of x substitute into the equilibrium constant expression Tro.00023 0 0. H2CO3? represent the HCO3− + H2O  CO32− + H3O+ change in the concentrations in [HCO3−] [CO32−] [H3O+] terms of x initial 0. 2/e 190 Copyright  2011 Pearson Education.12 M solution of carbonic acid. Practice – What is the [CO32−] in a 0. .00023 sum the columns change x +x +x to find the equilibrium equilibrium 2. Chemistry: A Molecular Approach. Inc.

approximate change −x +x +x the [HA]eq = [HA]init. Therefore [CO32−] = Ka2 Tro.3E−4 −x +x and solve for x using this approximation.3 x 10−7.00023 0 0. equilibrium 2. Inc.00023 small.3E−4 xx 2. H2CO3? determine the Ka1 = 4. Practice – What is the [CO32−] in a 0. . [H3O+]eq = [H3O+]init.6 x 10−11 value of Ka2 [HCO3−] [CO32−] [H3O+] because Ka2 is very initial 0. it is seen that x = Ka2.12 M solution of carbonic acid. 2/e 191 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach. Ka2 = 5.

Chemistry: A Molecular Approach. use the given [H2SO4] = [HSO4−]initial = [H3O+]initial Tro.2 x 10−2 • For most sulfuric acid solutions. Inc. the second ionization is significant and must be accounted for • Because the first ionization is complete. 2/e 192 Copyright  2011 Pearson Education. . Ionization in H2SO4 • The ionization constants for H2SO4 are H2SO4 + H2O  HSO4 + H3O+ strong HSO4 + H2O  SO42 + H3O+ Ka2 = 1.

2/e 193 Copyright  2011 Pearson Education.0100 0 0.18: Find the pH of 0. Example 15. Chemistry: A Molecular Approach. .0100 reaction change enter the initial concentrations – equilibrium assuming the [HSO4−] and [H3O+] is ≈ [H2SO4] Tro. Inc.0100 M H2SO4(aq) solution @ 25 °C write the reactions H2SO4 + H2O  HSO4 + H3O+ for the acid with water HSO4 + H2O  SO42 + H3O+ construct an ICE table for the [HSO4 ] [SO42 ] [H3O+] second ionization initial 0.

Inc.0100 0 0. .0100 M H2SO4(aq) solution @ 25 °C represent the [HSO4 ] [SO42 ] [H3O+] change in the concentrations in initial 0. Example 15.0100 x 0.0100 −x −x equilibrium concentrations in terms of x substitute into the equilibrium constant expression Tro.18: Find the pH of 0. 2/e 194 Copyright  2011 Pearson Education.0100 terms of x change −x +x +x sum the columns to find the equilibrium 0. Chemistry: A Molecular Approach.

18: Find the pH of 0. Chemistry: A Molecular Approach.0100 M H2SO4(aq) solution @ 25 °C Ka for HSO4− = 0.012 expand and solve for x using the quadratic formula Tro. Inc. 2/e 195 Copyright  2011 Pearson Education. Example 15. .

0100 0.0045 Tro.0145−x x = 0.012 substitute x into [HSO4 ] [SO42 ] [H3O+] the equilibrium initial 0. Chemistry: A Molecular Approach.0100 0.0055−x 0. Inc.0045 x 0. Example 15.0100 M H2SO4(aq) solution @ 25 °C Ka for HSO4− = 0. .18: Find the pH of 0.0100 0 0.0100 concentration definitions and change −x +x +x solve equilibrium 0. 2/e 196 Copyright  2011 Pearson Education.

Inc.0100 0 0.012 substitute [H3O+] [HSO4 ] [SO42 ] [H3O+] into the formula initial 0.0100 for pH and solve change −x +x +x equilibrium 0.0100 M H2SO4(aq) solution @ 25 °C Ka for HSO4− = 0.0055 0. Chemistry: A Molecular Approach. Example 15. .0145 Tro.0045 0. 2/e 197 Copyright  2011 Pearson Education.18: Find the pH of 0.

18: Find the pH of 0. 2/e 198 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach. Inc.0045 0.012 check by [HSO4 ] [SO42 ] [H3O+] substituting the initial 0.0145 constant expression and comparing the calculated Ka to the given Ka the answer matches Tro. .0100 M H2SO4(aq) solution @ 25 °C Ka for HSO4− = 0.0100 equilibrium concentrations back change −x +x +x into the equilibrium equilibrium 0. Example 15.0055 0.0100 0 0.

. 2/e 199 Copyright  2011 Pearson Education. Strengths of Binary Acids • The more + H─X − polarized the bond. Chemistry: A Molecular Approach. Inc. the weaker the acid • Binary acid strength increases to the right across a period  acidity: H─C < H─N < H─O < H─F • Binary acid strength increases down the column  acidity: H─F < H─Cl < H─Br < H─I Tro. the more acidic the bond • The stronger the H─X bond.

Chemistry: A Molecular Approach. . Relationship between Bond Strength and Acidity Bond Energy Type of Acid Acid kJ/mol HF 565 weak HCl 431 strong HBr 364 strong Tro. Inc. 2/e 200 Copyright  2011 Pearson Education.

Chemistry: A Molecular Approach. H–O–Y • The more electronegative the Y atom. the stronger the oxyacid  H2CO3 > H3BO3  acidity of oxyacids increases to the right across a period  opposite trend of binary acids • The more oxygens attached to Y. the stronger the oxyacid  HClO > HIO  acidity of oxyacids decreases down a group  same trend as binary acids  helps weakens the H–O bond • The larger the oxidation number of the central atom. 2/e 201 Copyright  2011 Pearson Education. Strengths of Oxyacids. . the stronger the oxyacid  further weakens and polarizes the H–O bond  HClO3 > HClO2 Tro. Inc.

0 x 10−9 H─O─I 2. Relationship Between Electronegativity and Acidity Acid Electronegativity Ka H─O─Y of Y H─O─Cl 3.5 2. 2/e 202 Copyright  2011 Pearson Education. Inc.8 2.3 x 10−11 Tro.0 2. Chemistry: A Molecular Approach. .9 x 10−8 H─O─Br 2.

Chemistry: A Molecular Approach. . Inc. 2/e 203 Copyright  2011 Pearson Education. Relationship Between Number of Oxygens on the Central Atom and Acidity Tro.

Practice – Order the Following • By Acidity (Least to Most) H3PO4 HNO3H3PO3 H3AsO3 • By Acidity (Least to Most) HCl HBr H2S HS− • By Basicity (Least to Most) CO32− NO3− HCO3− BO33− Tro. 2/e 204 Copyright  2011 Pearson Education. . Chemistry: A Molecular Approach. Inc.

2/e 205 Copyright  2011 Pearson Education. . Chemistry: A Molecular Approach. Practice – Order the Following • By Acidity (Least to Most) H3PO4 HNO3H3PO3 H3AsO3 H3AsO3 < H3PO3 < H3PO4 < HNO3 • By Acidity (Least to Most) HCl HBr H2S HS− HS− < H2S < HCl < HBr • By Basicity (Least to Most) CO32− NO3− HCO3− BO33− NO3− < HCO3− < CO32− < BO33− Tro. Inc.

. therefore electrophile Tro. 2/e 206 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach. Inc. Lewis Acid–Base Theory • Lewis Acid–Base theory focuses on transferring an electron pair  lone pair  bond  bond  lone pair • Does NOT require H atoms • The electron donor is called the Lewis Base  electron rich. therefore nucleophile • The electron acceptor is called the Lewis Acid  electron deficient.

the less willing it is to be a Lewis Base  O: < S: Tro. Inc. the more electronegative an atom. Chemistry: A Molecular Approach. Lewis Bases • Lewis Base has electrons it is willing to give away to or share with another atom • Lewis Base must have lone pair of electrons on it that it can donate • Anions are better Lewis Bases than neutral atoms or molecules  N: < N:− • Generally. . 2/e 207 Copyright  2011 Pearson Education.

Lewis Acids • Electron deficient. highly charged metal cations have empty orbitals they can use to accept electrons • Atoms that are attached to highly electronegative atoms and have multiple bonds can be Lewis Acids Tro. either from  being attached to electronegative atom(s)  not having an octet • Must have empty orbital willing to accept the electron pair • H+ has empty 1s orbital • B in BF3 has empty 2p orbital and an incomplete octet • Many small. . 2/e 208 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach. Inc.

2/e 209 Copyright  2011 Pearson Education. . Inc. Chemistry: A Molecular Approach. Lewis Acid–Base Reactions • The base donates a pair of electrons to the acid • Generally results in a covalent bond forming H3N: + BF3  H3N─BF3 • The product that forms is called an adduct • Arrhenius and Brønsted-Lowry acid–base reactions are also Lewis Tro.

Examples of Lewis Acid–Base Reactions Tro. 2/e 210 Copyright  2011 Pearson Education. . Inc. Chemistry: A Molecular Approach.

2/e 211 Copyright  2011 Pearson Education. Examples of Lewis Acid–Base Reactions Ag+(aq) + 2 :NH3(aq)  Ag(NH3)2+(aq) Lewis Lewis Adduct Acid Base Tro. Inc. Chemistry: A Molecular Approach. .

. Practice – Identify the Lewis Acid and Lewis Base in Each Reaction Lewis Base Lewis Acid Lewis Lewis Base Acid Tro. Inc. 2/e 212 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach.

. Fuel Consumption • Over 85% of the energy use in the United States comes from the combustion of fossil fuels  oil. coal • Combustion of fossil fuels produces CO2 CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(g) • Natural fossil fuels also contain small amounts of S that burn to produce SO2(g) S(s) + O2(g) → SO2(g) • The high temperatures of combustion allow N2(g) in the air to combine with O2(g) to form oxides of nitrogen N2(g) + 2 O2(g) → 2 NO2(g) Tro. U. Inc. natural gas.S. 2/e 213 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach.

What Is Acid Rain? • Natural rain water has a pH of 5.6 is called acid rain • Acid rain is linked to damage in ecosystems and structures Tro. . Inc. Chemistry: A Molecular Approach.6  naturally slightly acidic due mainly to CO2 • Rain water with a pH lower than 5. 2/e 214 Copyright  2011 Pearson Education.

SO2. NO2 • Nonmetal oxides are acidic CO2(g) + H2O(l)  H2CO3(aq) 2 SO2(g) + O2(g) + 2 H2O(l)  2 H2SO4(aq) 4 NO2(g) + O2(g) + 2 H2O(l)  4 HNO3(aq) • Processes that produce nonmetal oxide gases as waste increase the acidity of the rain  natural – volcanoes and some bacterial action  man-made – combustion of fuel Tro. Chemistry: A Molecular Approach. 2/e 215 Copyright  2011 Pearson Education. . Inc. What Causes Acid Rain? • Many natural and pollutant gases dissolved in the air are nonmetal oxides  CO2.

Chemistry: A Molecular Approach. 2/e 216 Copyright  2011 Pearson Education. pH of Rain in Different Regions Tro. Inc. .

Inc. even though it has very low sulfur emissions. Weather Patterns • The prevailing winds in the United States travel west to east • Weather patterns may cause rain to be acidic in regions other than where the nonmetal oxide is produced • Much of the northeast United States has rain of very low pH. due in part to the general weather patterns Tro. . 2/e 217 Copyright  2011 Pearson Education. Chemistry: A Molecular Approach.

Inc. Chemistry: A Molecular Approach. . Sources of SO2 from Utilities Tro. 2/e 218 Copyright  2011 Pearson Education.

and other metallic structures • Acid rain damages buildings and other structures made of limestone or cement • Acidifying lakes affects aquatic life • Soil acidity causes more dissolving of minerals and leaching more minerals from soil  making it difficult for trees Tro. . 2/e 219 Copyright  2011 Pearson Education. Damage from Acid Rain • Acids react with metals. Inc. cars. and materials that contain carbonates • Acid rain damages bridges. Chemistry: A Molecular Approach.

Damage from Acid Rain Tro. Inc. Chemistry: A Molecular Approach. . 2/e 220 Copyright  2011 Pearson Education.

Chemistry: A Molecular Approach. Inc. 2/e 221 Copyright  2011 Pearson Education. . Acid Rain Legislation • 1990 Clean Air Act attacks acid rain  forces utilities to reduce SO2 • Result is acid rain in the Northeast stabilized and beginning to be reduced Tro.