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Chapter 16: Acids and Bases, A Molecular Look. Chemistry: The Molecular Nature of Matter, 6E Jespersen/Brady/Hyslop. Arrhenius Acids and Bases. Acid produces H 3 O + in water Base gives OH – Acid-base neutralization Acid and base combine to produce water and a salt.

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chapter 16 acids and bases a molecular look

Chapter 16: Acids and Bases, A Molecular Look

Chemistry: The Molecular Nature of Matter, 6E


arrhenius acids and bases
Arrhenius Acids and Bases

Acid produces H3O+ in water

Basegives OH–

Acid-base neutralization

    • Acid and base combine to produce water and a salt.

e.g. HCl(aq)+ NaOH(aq) H2O + NaCl(aq)

H3O+(aq) + Cl–(aq) + Na+(aq) + OH–(aq) 2H2O + Cl–(aq) + Na+(aq)

  • Many reactions resemble this without forming H3O+ or OH– in solution
gas phase acid base
Gas Phase Acid-Base
  • Not covered by Arrhenius definition

e.g. NH3(g) + HCl(g) NH4Cl(s)

br nsted lowry definition
Brønsted-Lowry Definition
  • Acid = proton donor
  • Base = proton acceptor
  • Allows for gas phase acid-base reactions

e.g. HCl + H2O  H3O+ + Cl–

    • HCl = acid
      • Donates H+
    • Water = base
      • Accepts H+
conjugate acid base pair
Conjugate Acid-Base Pair
  • Species that differ by H+

e.g. HCl + H2O  H3O+ + Cl–

  • HCl = acid
  • Water = base
  • H3O+
    • Conjugate acid of H2O
  • Cl–
    • Conjugate base of HCl
formic acid is bronsted acid
Formic Acid is Bronsted Acid
  • Formic acid (HCHO2) is a weak acid
  • Must consider equilibrium
    • HCHO2(aq) + H2O CHO2–(aq) + H3O+(aq)
  • Focus on forward reaction
formate ion is bronsted base
Formate Ion is Bronsted Base
  • Now consider reverse reaction
  • Hydronium ion transfers H+ to CHO2–
learning check1
Learning Check
  • Write a reaction that shows that HCO3– is a Brønsted acidwhen reacted with OH–
  • HCO3–(aq)+ OH–(aq)
  • Write a reaction that shows that HCO3– is a Brønsted basewhen reacted with H3O+(aq)
  • HCO3–(aq) + H3O+(aq)

H2O + CO32–(aq)

H2CO3(aq) + H2O

your turn
Your Turn!

In the following reaction, identify the acid/base conjugate pairs.

(CH3)2NH + H2SO4 → (CH3)2NH+ + HSO4–

A. (CH3)2NH / H2SO4 (CH3)2NH+ / HSO4–

B. (CH3)2NH / (CH3)2NH+ H2SO4 / HSO4–

C. H2SO4 / HSO4– (CH3)2NH+ / (CH3)2NH

D. H2SO4 / (CH3)2NH (CH3)2NH+ / HSO4–

amphoteric substances
Amphoteric Substances
  • Can act as either acid or base
    • Can be either molecules or ions

e.g. Hydrogen carbonate ion:

    • Acid

HCO3–(aq) + OH–(aq) CO32–(aq) + H2O

    • Base

HCO3–(aq) + H3O+(aq)  H2CO3(aq) + H2O

[Amphiprotic substances can donate or accept a proton. This is a subtle but important difference from the word amphoteric]

your turn1
Your Turn!

Which of the following can act as an amphoteric substance?


B. HCl

C. NO2–

D. HPO42–

strengths of acids and bases
Strengths of Acids and Bases

Strength of Acid

  • Measure of its ability to transfer H+
  • Strongacids
    • React completely with water e.g.HCl and HNO3
  • Weak acids
    • Less than completely ionized e.g.CH3COOH and CHOOH

Strength of Baseclassified in similar fashion:

  • Strong bases
    • React completely with water e.g.Oxide ion (O2–) and OH–
  • Weak bases
    • Undergo incomplete reactions

e.g.NH3 and NRH2 (NH2CH3, methylamine)

reactions of strong acids and bases
Reactions of Strong Acids and Bases

In water

  • Strongest acid= hydronium ion, H3O+
    • If more powerful H+ donor added to H2O
    • Reacts with H2O to produce H3O+


  • Strongest baseis hydroxide ion (OH–)
    • More powerful H+ acceptors
    • React with H2O to produce OH–
position of acid base equilibrium
Position of Acid-Base Equilibrium
  • Acetic acid (HC2H3O2) is weak acid
    • Ionizes only slightly in water

HC2H3O2(aq) + H2O H3O+(aq) + C2H3O2–(aq)

weaker acidweaker basestronger acidstronger base

  • Hydronium ion
    • Better H+ donor than acetic acid
    • Stronger acid
  • Acetate ion
    • Better H+ acceptor than water
    • Stronger base
  • Position of equilibrium favors weakeracid and base
your turn2
Your Turn!

In the reaction:

HCl + H2O → H3O+ + Cl–

which species is the weakest base ?

A. HCl

B. H2O

C. H3O+

D. Cl–

in general
In General
  • Stronger acids and bases tend to react with each other to produce their weaker conjugates
    • Stronger Brønsted acid has weaker conjugate base
    • Weaker Brønsted acid has stronger conjugate base
  • Can be applied to binary acids (acids made from hydrogen and one other element)
learning check2
Learning Check

Identify the preferred direction of the following reactions:

H3O+(aq)+ CO32–(aq) HCO3–(aq)+ H2O

Cl–(aq)+ HCN(aq) HCl(aq)+ CN–(aq)

trends in binary acid strength
Trends in Binary Acid Strength

Binary Acids = HnX

X = Cl, Br, P, As, S, Se, etc.

  • Acid strength increases from left to right within same period (across row)
    • Acid strength increases as electronegativity of Xincreases

e.g. HCl is stronger acid than H2S which is stronger acid than PH3

    • or PH3 < H2S < HCl
trends in binary acid strength1
Trends in Binary Acid Strength

Binary Acids = HnX

X = Cl, Br, P, As, S, Se, etc.

2. Acid strength increase from top to bottom within group

  • Acid strength increases as size of Xand bond length increases

e.g. HCl is weaker acid than HBr which is weaker acid than HI

  • or HCl < HBr < HI
learning check3
Learning Check
  • Which is stronger?
  • H2S or H2O
  • CH4 or NH3
  • HF or HI
  • H2S
  • NH3
  • HI
trends in oxoacid strength
Trends in Oxoacid Strength

Oxoacids (HnX Om)

    • Acids of H, O, and one other element
    • HClO, HIO4, H2SO3, H2SO4, etc.
  • Acids with same number of oxygen atoms and differing X
    • Acid strength increasesfrom

bottom to top within group

      • HIO4 < HBrO4 < HClO4
    • Acid strength increases from left to right within period as the electronegativity of the central atom increases H3PO4 < H2SO4 < HClO4
trends in oxoacid strength1
Trends in Oxoacid Strength

Oxoacids (HnXOm)

  • For same X
    • Acid strength increases with number of oxygen atoms
      • H2SO3 < H2SO4
      • More oxygens, remove more electron density from central atom, weakening O—H bond make H more acidic
learning check4
Learning Check

Which is the stronger acid in each pair?

  • H2SO4 or H3PO4
  • HNO3 or H3PO3
  • H2SO4 or H2SO3
  • HNO3 or HNO2





your turn3
Your Turn!

Which corresponds to the correct order of acidity from weakest to strongest acid ?

A. HBrO3, HBrO, HBrO2

B. HBrO, HBrO2, HBrO3

C. HBrO, HBrO3, HBrO2

D. HBrO3, HBrO2, HBrO

alternate definition of acid strength
Alternate Definition of Acid Strength
  • Acid strength can be analyzed in terms of basicity of anion formed during ionization
  • Basicity
    • Willingness of anion to accept H+ from H3O+
  • Consider HClO3 and HClO4:
comparing basicity
Comparing Basicity
  • Lone oxygens carry most of the negative charge
    • ClO4– has 4 O atoms, so each has –¼ charge
    • ClO3– has 3 O atoms, so each has –1/3 charge
  • ClO4–weaker base than ClO3–
    • Thus conjugate acid, HClO4, is stronger acid
  • HClO4 stronger acid as more fully ionized
learning check5
Learning Check
  • Arrange the following in order of increasing acid strength:
  • HBr, AsH3, H2Se
    • AsH3 < H2Se < HBr
  • H2SeO4, H2SO4, H2TeO4
    • H2TeO4 < H2SeO4 < H2SO4
  • HBrO3, HBrO, HBrO4, HBrO2
    • HBrO < HBrO2 < HBrO3 < HBrO4
strength of organic acids
Strength of Organic Acids
  • Organic acid —COOH
  • Presence of electronegative atoms (halide, nitrogen or other oxygen) near —COOH group
    • Withdraws electron density from O—H bond
    • Makes organic acid, stronger acids

e.g.CH3CO2H < CH2ClCO2H < CHCl2CO2H < CCl3CO2H

your turn4
Your Turn!

Which of the following is the strongest organic acid?






lewis definition of acid and base
Lewis Definition of Acid and Base
  • Broadest definition of species that can be classified as either acid or base
  • Definitions based on electron pairs
  • Lewis acid
    • Any ionic or molecular species that can acceptpair of electrons
    • Formation of coordinate covalent bond
  • Lewis base
    • Any ionic or molecular species that can donatepair of electrons
    • Formation of coordinate covalent bond
lewis neutralization
Lewis Neutralization
  • Formation of coordinate covalent bond between electron pair donor and electron pair acceptor
  • NH3BF3 = addition compound
    • Made by joining two smaller molecules

Addition Compound

lewis acid base reaction
Lewis Acid-Base Reaction
  • Electrons in coordinate covalent bond come from O in hydroxide ion
lewis acids
Lewis Acids:
  • Molecules or ions with incomplete valence shells

e.g. BF3 or H+

  • Molecules or ions with complete valence shells, but with multiple bonds that can be shifted to make room for more electrons

e.g. CO2

  • Molecules or ions that have central atoms that can expand their octets
    • Capable of holding additional electrons
    • Usually, atoms of elements in Period 3 and below

e.g. SO2

lewis bases
Lewis Bases:
  • Molecules or ions that have unshared electron pairs and that have complete shells
    • e.g. O2– or NH3

Lewis Definition is Most General

    • All Brønsted acids and bases are Lewis acids and bases
    • All Arrhenius acids and bases are Brønsted acids and bases
h transfer from lewis perspective
H+ Transfer from Lewis Perspective

e.g.H2O—H+ + NH3 H2O + H+—NH3

learning check6
Learning Check

Identify the Lewis acid and base in the following:

  • NH3 + H+NH4+


  • F– + BF3BF4–


  • SeO3 + O2–SeO42–


your turn5
Your Turn!

Which of the following species can act as a Lewis base ?

A. Cl–

B. Fe2+

C. NO2–

D. O2–

acid base properties of elements and their oxides
Acid-Base Properties of Elements and Their Oxides

Nonmetal oxides

  • React with H2O to form acids
  • Upper right hand corner of periodic table
  • Acidic Anhydrides
  • Neutralize bases
  • Aqueous solutions redto litmus
  • SO3(g) + H2O  H2SO4(aq)
  • N2O5(g) + H2O  2HNO3(aq)
  • CO2(g) + H2O  H2CO3(aq)
acid base properties of elements and their oxides1
Acid-Base Properties of Elements and Their Oxides

Metal oxides

  • React with H2O to form hydroxide (Base)
  • Group 1A and 2A metals (left hand side of periodic table)
  • BasicAnydrides
  • Neutralize acids
  • Aqueous solutions blue to litmus
  • Na2O(s) + H2O  2NaOH(aq)
  • CaO(s) + H2O  Ca(OH)2(aq)
metal oxides m x o y
Metal Oxides MxOy
  • Solids at room temperature
  • Many insoluble in H2O
  • Why?
    • Too tightly bound in crystal
    • Can't remove H+ from H2O
    • Do dissolve in solution of strong acid
    • Now H+ free, can bind to O2– and remove from crystal

Fe2O3(s) + 6H+(aq) 2Fe3+(aq) + 3H2O

your turn6
Your Turn!

What is the acid formed by P2O3 when it reacts with water ?

A. H2PO4

B. H2PO2

C. H3PO4

D. H3PO3

  • P2O3 + 3H2O → 2H3PO3
metal ions in solution once anion is removed
Metal Ions in Solution (Once Anion is Removed)
  • Exist with sphere of water molecules with their negative poles directed toward Mn+
  • Mn+(aq) + mH2O M(H2O)mn+(aq)

Lewis AcidLewis Basehydrated metal ion = addition compound

    • n= charge on metal ion = 1, 2, or 3 depending on metal atom
    • For now assume m = 1 (monohydrate)
hydrated metal ions weak br nsted acids
Hydrated Metal Ions = Weak Brønsted Acids

M(H2O)n+(aq) + H2OM(OH)n+(aq) + H3O+(aq)

your turn7
Your Turn!

The following reactions:

Al(OH)3 + 3H+ → Al3+ + H2O

Al(OH)3 + OH– → Al(OH)4–

illustrate the concept of

A. neutralization

B. amphoteric property of Al(OH)3

C. oxidation of Al

D. reduction of OH–

hydrated metal ions can act as weak acids
Hydrated Metal Ions Can Act as Weak Acids
  • Electron deficiency of metal cations causes them to induce electron density towards metal from water of hydration
  • Higher charge density = more acidic metal
  • Acidity increases left to right across period
  • Acidity decreases top to bottom down group
acidity of hydrated metal ions
Acidity of Hydrated Metal Ions
  • Degree to which M(H2O)mn+ produces acidic solutions depends on
    • Charge on cation
    • Cation's size

1. As charge increases on Mn+, acidity increases

    • Increases metal ion’s ability to draw electron density to itself and away from O—H bond
acidity of hydrated metal ions1
Acidity of Hydrated Metal Ions

2. As size of cation decreases, acidity increases

  • Smaller, more concentrated charge
  • Means greater pull of electron density from O—H bond
  • Net result
    • Very small, highly charged cations are very acidic

[Al(H2O)6]3+(aq) + H2O [Al(H2O)5(OH)]2+(aq) + H3O+(aq)

your turn8
Your Turn!

In the following list of pairs of ions, which is the more acidic ?

Fe2+ or Fe3+; Cu2+ or Cu+; Co2+ or Co3+

A. Fe3+, Cu+, Co2+

B. Fe2+, Cu2+, Co3+

C. Fe3+, Cu2+, Co3+

D. Fe2+, Cu2+, Co2+

trends in acidity of m n
Trends in Acidity of Mn+
  • Acidity increases up group (column) as cation size decreases
  • Acidity increases across period (row) as cation size decreases


Moderately weak

Other Alkaline earth metals (Ba2+, Ca2+ Sr2+, Mg2+)

Very Weak

Transition metal ions, Al3(often +3, +4 charges)

Quite acidic

learning check7
Learning Check
  • Identify each of the following as acidic or basic and give their reaction with water:
  • P2O5

P2O5(s) + 3H2O2H3PO4(aq)

2H3PO4(aq) 2H+(aq) + 2H2PO4–(aq)

  • MnO2

MnO2(s) + 2H2OMn2+(aq) + 4OH–(aq)



ceramic materials
Ceramic Materials
  • Date back to prehistoric times
    • Pottery as far back as 13,000 years old
  • Today found in brick, cement, and glass
    • Porcelain dinnerware, tiles, sinks, toilets, artistic pottery and figurines
    • Composed of Silicates — compounds containing anions composed of silicon and oxygen
  • Advanced ceramic materials
    • Made in chemistry laboratories
    • High-tech applications
    • Found in cell phones and diesel engines
traditional ceramic synthesis
Traditional Ceramic Synthesis
  • Pulverize components of ceramic into fine powders
  • Mix with
    • Water and pour into mold or
    • Binder and press into desired shape
  • Heat in kiln, tC > 1000 ˚C
    • Sintering – particles fuse together to form ceramic
  • Problems:
    • Hard to form uniform, very small particles
    • Ceramics formed often have small crackswhich decreases their strength
    • Composition not easily reproducible
sol gel process
Sol-Gel Process
  • Synthesis of ceramics that avoid problems of particle size and uniformity
  • Based on acid–base reactions
  • Starting materials are
    • Metal salts or
    • Compounds where metal or metalloid (e.g., Si) is bonded to some number of alkoxide groups
sol gel process1
Sol-Gel Process
  • Metal alkoxide salts generally soluble in alcohols
  • Alcohols are very weak acids
    • Essentially no tendency to lose H+
  • Alkoxide ions very strong bases
    • React with water to form alcohol and OH–
    • C2H5O– + H2O  C2H5OH + OH–
  • Basis of sol-gel process


your turn9
Your Turn!

Which of the following is an example of an alkoxide ion ?




D. OH–

sol gel process2
Sol-Gel Process
  • Gradually add water to alcohol solution of alkoxide salts
  • Alkoxide ions gradually replaced by OH– ions

Hydrolysis reaction

Zr(C2H5O)4 + H2O  Zr(C2H5O)3OH + C2H5OH

  • When two Zr(C2H5O)3OH encounter each other, they undergo an acid-base reaction and lose H2O
sol gel process3
Sol-Gel Process
  • As more H2O is added:
    • More alkoxide ions converted to alcohols
    • Form more oxide linkages bridging Zr ions
    • Result is very fine particles of metal oxides with residual OH ions suspended in alcohol (gel-like)
  • Sol-gel used in various ways
    • Dip coated on surface yields thin film ceramics
    • Cast into mold produces semisolid gelatin-like material = wet gel
      • Dry wet gel by evaporation gives porous gel = xerogel
      • Heating xerogel yields dense ceramic or glass with uniform structure
sol gel process4
Sol-Gel Process
  • Sol-gel used in various ways
    • Remove solvent from wet gel at temperature above critical temperature of solvent yields very porous and extremely low density solid = aerogel
    • Adjust viscosity of gel suspension and spinning yields ceramic fibers
    • Precipitation of sol-gels yields ultrafine and uniform ceramic powders

TiN coating

Ceramic heat tiles