Arrhenius Definition

John W. Moore
Conrad L. Stanitski Arrhenius: any substance which ionizes in water to
Peter C. Jurs produce:
http://academic.cengage.com/chemistry/moore
• Protons is an Acid.
• Hydroxide ions is a Base.
Base

Chapter 15 Better version of the Arrhenius definition:

Acid: Hydronium ions (H3O+) in water are acidic.
Acids and Bases Base Hydroxide ions (OH-) in water are basic.
Base:

So, why
w is NH3(aq) basic?
Stephen C. Foster • Mississippi State University

Brønsted-Lowry Concept Brønsted-Lowry Concept

An alternative definition: Strong acids and bases almost completely ionize.
Brønsted-
Brønsted-Lowry Acid = Proton donor HNO3(aq) + H2O(ℓ) H3O+(aq) + NO3-(aq)
Brønsted-
Brønsted-Lowry Base = Proton acceptor Weak acids and bases do not fully ionize.
HF(aq) + H2O(ℓ) H3O+(aq) + F-(aq)
Works for non-aqueous solutions and explains why
NH3 is basic: H2O(ℓ) + NH3(aq) NH4+(aq) + OH-(aq)
Acid: Base: Acid: Base:
NH3(g) + H2O(ℓ) NH4+(aq) + OH-(aq) H+ donor H+ acceptor H+ donor H+ acceptor

Base: Acid:
H+ acceptor H+ donor
Note: the products are a new acid and base pair.

Water’s Role as Acid or Base Conjugate Acid-Base Pairs

Water acts as a base when an acid dissolves in water: Molecules or ions related by the loss/gain of one H+.
Conjugate Acid Conjugate Base
HBr(aq) + H2O(ℓ) H3O+(aq) + Br-(aq) H3 O + H2 O
acid base acid base
CH3COOH donate H+
CH3COO-
But water acts as an acid for some bases: NH4 + NH3
accept H+
H2SO4 HSO4-
H2O(ℓ) + NH3(aq) NH4+(aq) + OH-(aq) HSO4 - SO42-
acid base acid base
HCl Cl-

Water is amphiprotic - it can donate or accept a

NH4+ and NH2- are not conjugate, conversion
proton (act as acid or base).
requires 2 H+.

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Conjugate Acid-Base Pairs Relative Strength of Acids & Bases
Identify the base conjugate to HF(aq) and the acid Strong acids are better H+ donors than weak acids
conjugate to HCO3-(aq). Strong bases are better H+ acceptors than weak bases
• Stronger acids have weaker conjugate bases.
HF H+ + F- • Weaker acids have stronger conjugate bases.

Acid: Conjugate
H+ donor Base Strong acid + H2O H3O+ + conjugate base
Fully ionized, reverse reaction essentially does not occur.
HCO3- + H+ H2CO3 The conjugate base is weak.
Base: Conjugate
H+ acceptor Acid
Weak acid + H2O H3O+ + conjugate base
Weakly ionized, reverse reaction readily occurs.
( CO32- is the base conjugate to HCO3- ) The conjugate base is strong.

Relative Strength of Acids & Bases Relative Strength of Acids & Bases
Conjugate acid Conjugate base Problem
H2SO4 HSO4- extremely
strong
HBr Br- weak Is the following aqueous reaction Conj acid. Conj. base
HCl Cl- product or reactant favored? H2SO4 HSO4-
HNO3 NO3- HBr Br-
NH4+ + F-

Base strength increasing

NH3 + HF
Base strength increasing

H3O+ H2O
HCl Cl-
Acid strength increasing

Acid strength increasing

H2SO3 HSO3-
HSO4- SO42-
H3PO4 H2PO4-
HF is a stronger acid than NH4+. HF F-
HF F-
CH3COOH CH3COO-
(NH3 is a stronger base than F-)
H2S HS-
NH4+ NH3
H2PO4- HPO42- HF has greater tendency to
NH4+ NH3 ionize than NH4+.
HCO3- CO32- (NH3 more readily accepts H+ than F-)
H2O OH- OH- O2-
OH- O2- H2 H-
extremely H2 H-
Reactant Favored CH4 CH3-
strong
weak CH4 CH3-

Carboxylic Acids and Amines Carboxylic Acids and Amines

Organic acids The carboxylic acid H is acidic (will ionize). All other
protons are non acidic:
Contain the carboxylic acid functional group:
O O
CH3 – C + H2O CH3 – C + H3O +
OH O-

• O is very electronegative.
• O withdraws e- from the O–H bond (weakens O-H).
• Makes it easier for H+ to leave.
• Once formed, the anion is stabilized by resonance:
O O-
CH3 – C CH3 – C
O- O

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Carboxylic Acids and Amines Autoionization of Water
.. .. .. Two water molecules can react to form ions.
Amine group: R–NH2 , R–NHR or R–NR2
Autoionization occurs:
• R = any hydrocarbon.
H2O(ℓ) + H2O(ℓ) H3O+(aq) + OH-(aq)
• Lone-pair on N accepts a proton (like NH3).
Base Acid Acid Base

Heavily reactant favored.

Only a very small fraction is ionized:
Kw = [ H3O+ ] [ OH- ] [H2O]2 is
ionization omitted…
constant for = (1.0 x 10-7)(1.0 x 10-7)
water
= 1.0 x 10-14 (at 25°C)

Ionization Constant for Water Autoionization of Water

Kw, like all equilibrium constants, is T-dependent. H3O+ and OH- are present in all aqueous solutions.
T = 25°C (77°F) is usually used as the standard T. Neutral solution.
solution.
Pure water (@ 25°C): [H3O+] = 10-7 M = [OH-]

T (°C) Kw Acidic solution

10 0.29 x 10-14 If acid is added to water:
15 0.45 x 10-14 • [ H3O+ ] is increased, disturbing the equilibrium:
20 0.68 x 10-14
2 H2O H3O+ + OH-
25 1.01 x 10-14
30 1.47 x 10-14 • Equilibrium shifts to remove [H3O+] (and [OH-]).
50 5.48 x 10-14 • Equilibrium is reestablished: [ H3O+ ] > 10-7 M > [OH-]
• [ H3O+ ][OH-] = Kw = 1.0 x 10-14 at 25°C.

Autoionization of Water Autoionization of Water

Basic solution.
solution.
If base is added to water.
• Equilibrium shifts to remove [ OH- ] (and [H3O+]).
• New equilibrium: [H3O+] < 10-7 M < [OH-].
• [ H3O+ ][OH-] = Kw = 1.0 x 10-14 at 25°C.
Example
Calculate the hydronium and hydroxide ion
concentrations at 25°C in a 6.0 M aqueous sodium
hydroxide solution.
Kw = [H3O+][OH-] = 1.0 x 10-14
NaOH (aq) is strong (100% ionized) so [OH-] = 6.0 M.
[H3O+](6.0) = 1.0 x 10-14
[H3O+] = 1.7 x 10-15 M [ OH- ] = 6.0 M

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The pH scale The pH scale
Acid concentration can vary over a very large range.
Examples
A logarithmic scale is more convenient:
log10 (1 x 10-x) = -x
Lemon juice: [H3O+] = 1 x 10-2 M
pH = −log10[H3 O+]
pH = −(−2.0) = 2.0
At 25°C a neutral aqueous solution has:
pH = −log10[1.0 x 10-7] = −(−7.00) = 7.00 weak acid: [H3O+] = 2.4 x 10-5 M
pH = −(−4.62) = 4.62
Acidic solutions: pH < 7.00 (lower pH = more acidic).
2 sig. digits - digits after the decimal point
Basic solutions: pH > 7.00 (higher pH = more basic). are significant: “-4” is the power of 10 for
the number (0.24 x 10-4).

The pOH scale pH Calculations

Base concentrations: Given two aqueous solutions (25°C).
pOH = −log10 [OH-] Solution A: [OH-] = 4.3 x 10-4 M,
Solution B: [H3O+] = 7.5 x 10-9 M.
A neutral solution (25°C) has: Which has the higher pH? Which is more acidic?
pOH = −log10[1.0 x 10-7] = −(−7.00) = 7.00
Solution A: pOH = −log[ OH-] = 3.37
Since Kw = [ H3O+ ][ OH- ] = 1.0 x 10-14
pH + pOH = pKw = 14.00
−log(KW)= −log[H3O+] + (−log[OH-]) = −log(1.0 x 10-14)
pH = 10.63
pKw = pH + pOH = 14.00
Solution B: pH = −log[ H3O+] = 8.12
(Valid in all aq. solns. at 25°C: acidic, neutral or basic) A has higher pH, B is more acidic

Measuring pH Ionization Constants of Acids and Bases

H3O+ concentrations can be measured with an: When an acid ionizes in water:
Electronic pH meter:
meter
HA(aq) + H2O(ℓ) H3O+(aq) + A-(aq)
• fast and accurate.
• preferred method.
The acid ionization constant is used to report the
degree of ionization:
[A-][H3O+] (Water omitted, as usual)
Acid-base Indicator: Ka =
[HA]
• substance changes color over a small pH range.
• may have multiple colors (e.g. bromthymol blue).
• one “color” may be colorless (e.g. phenolphthalein).
Strong acids have large Ka values.
• cheap and convenient. Weak acid have small Ka values.

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Base Ionization Constants Values of Acid and Base Ionization Constants

For a base in water: See Table 15.2: ionization constants for common
acids and their conjugate bases.
B(aq) + H2O(ℓ) BH+(aq) + OH-(aq)
Strong acid Ka are hard to measure.
The base ionization constant,
constant Kb, is: • They are very large, ≈100% ionized.
[BH+][OH-] • Assume they are fully ionized.
Kb = [B] • Larger Ka = stronger acid.
If the base is an anion:
A-(aq) + H2O(ℓ) HA(aq) + OH-(aq) Strong base Kb are hard to measure…
• Larger Kb = stronger base.
[HA][OH-]
Kb = [A-]

Ka Values for Polyprotic Acids Ka Values for Polyprotic Acids

Some acids can donate more than one H+: Phosphoric acid (H3PO4) has three acidic protons:
Formula Name Acidic H’s
H2 S Hydrosulfuric Acid 2 H3PO4(aq) + H2O(ℓ) H3O+(aq) + H2PO4- (aq)

H+ harder to remove
H3PO4 Phosphoric Acid 3 Ka = 7.5 x 10-3
H2CO3 Carbonic Acid 2
HOOC-COOH Oxalic acid 2 H2PO4-(aq) + H2O(ℓ) H3O+(aq) + HPO42- (aq)
C3H5(COOH)3 Citric acid 3 Ka = 6.2 x 10-8

Each H+ ionization has a different Ka. HPO42-(aq) + H2O(ℓ) H3O+(aq) + PO43- (aq)
• The 1st proton is easiest to remove.
Ka = 3.6 x 10-13
• The 2nd is harder, etc.

Molecular Structure and Acid Strength Strength of Oxoacids

What makes a strong acid? H-O-Z
• A weak H–A bond, so H+ can be easily removed!
Acid Bonding ENZ Ka
hypochlorous acid HClO H-O-Cl 3.0 4 x 10-8
Consider the binary acids HF, HCl, HBr, HI.
hypobromous acid HBrO H-O-Br 2.8 3 x 10-9
smaller bond energy

HX Bond Energy (kJ) Ka

larger acid strength

hypoiodous acid HIO H-O-I 2.5 2 x 10-11

HF weak acid 566 7 x 10-4
strong acids

HCl 431 1 x 107

HBr 366 1 x 108 Weaker H-O bond … Stronger acid.
HI 299 1 x 1010 If Z is electronegative it will pull e- to it: H–O–Z
Larger ENZ = weaker bond (stronger acid).

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Strength of Oxoacids Problem Solving Using Ka and Kb
Example: Ka from pH
H-O-Z with Z = group of atoms.
Lactic acid is monoprotic. The pH of a 0.100 M
Acid Bonding Ka solution was 2.43 at 25°C. Determine Ka for this acid.
perchloric acid HClO4 H-O-ClO3 1 x 108
chloric acid HClO3 H-O-ClO2 1 x 103 Using the pH information:
chlorous acid HClO2 H-O-ClO 1 x 10-2 - log [H3O+] = 2.43 [H3O+] = 10-2.43 = 0.0037 M
hypochlorous acid HClO H-O-Cl 4 x 10-8
These hydronium ions are produced by:
Stronger acid = weaker H-O bond. HA(aq) + H2O(ℓ) H3O+(aq) + A-(aq)
If Z is:
and from the autoionization of water:
More e- withdrawing = weaker bond = stronger acid.
More O atoms = more e- withdrawing. H2O(ℓ) + H2O(ℓ) H3O+(aq) + OH-(aq)

Problem Solving Using Ka and Kb Problem Solving Using Ka and Kb

Example: pH from Ka
HA(aq) + H2O(ℓ) H3O+(aq) + A-(aq)
Determine the pH of a 0.100 M propanoic acid
[ ]initial 0.100 1.0 x 10-7 0
(water autoionization) solution at 25°C. Ka = 1.4 x 10-5. What % of acid is
ionized?
[ ]change -0.0037 +0.0037 +0.0037

[ ]equil 0.100 – 0.0037 0.0037* 0.0037

C2H5COOH + H2O(ℓ) H3O+(aq) + C2H5COO-(aq)
*Ignore the water contribution because it is so small.

+ -
Or HA + H2O H3O+ + A-
Ka = [H3O ][A ]
[HA] + -
Ka = [H3O ][A ] = 1.4 x 10-5
[HA]
= (0.0037)(0.0037) = 1.4 x 10-4
(0.100 – 0.0037)

Problem Solving Using Ka and Kb Problem Solving Using Ka and Kb

Determine the pH of 0.001 M propanoic acid soln. at 25°C. Ka = 1.4 x10-5. What %
of acid is ionized?
x2
1.4 x 10-5 ≈
HA(aq) + H2O(ℓ) H3 O+(aq) + A-(aq) 0.100
[ ]initial 0.100 0* 0
[ ]change -x +x +x x = (1.4 x 10-5 )(0.100) = 0.00118 M
[ ]equil 0.100 – x x* x
*Ignore the water contribution (x << 0.100 M; the approximation is good)

[H3O+][A-] x2 2
Ka= 1.4 x 10-5 = = ≈ x pH = -log(0.00118) = 2.93
[HA] (0.100 – x) 0.100
x
x << 0.1 (Ka is very small)
%-ionized = ( 0.100 )100% = 1.18 %

6
Problem Solving Using Ka and Kb Problem Solving Using Ka and Kb
Determine [OH-]
and pH of a 0.060 M dimethylamine
solution at 25°C. Kb = 5.9 x 10-4. x = (5.9 x 10-4 )(0.060) = 0.0059 M = [OH-]
(CH3)2NH + H2O(ℓ) (CH3)2NH2+(aq) + OH-(aq)
pOH = 2.23 pH = 14.00 – 2.23 = 11.77
B(aq) + H2O(l) BH+(aq) + OH-(aq)
[ ]initial 0.060 0 0*
x ≈ [B]/10, the approximation of x << [B] is marginal…
[ ]change -x +x +x
[ ]equilib 0.060 – x x x*
*Ignore water.
+ -
Kb = 5.9 x 10-4 = [BH ][OH ]
[B]
x2 x2
= ≈
(0.060 – x) 0.060

Problem Solving Using Ka and Kb Relationship between Ka and Kb values

Check the exact solution. For an acid-base conjugate pair: HA and A-
x2
5.90 x 10-4 = [H3O+][A-] [HA][OH-]
0.060 – x Ka x Kb = = [H3O+][OH-] = Kw
[HA] [A-]
x2 = (5.90 x 10-4)(0.060 – x)

x2 + 5.90 x 10-4 x – 3.54 x 10-5 = 0 Phenol, C6H5OH, is a weak acid, Ka = 1.3 x 10-10 at
Quadratic solution: x = 0.0057 M 25°C. Calculate Kb for the phenolate ion C6H5O-.
pOH = 2.25 pH = 11.75 Ka x Kb = 1.0 x 10-14
The approximate method gave pOH = 2.23 1.0 x 10-14
Kb = = 7.7 x 10-5
In general, approx. method is “good” if x < [ ]/20 1.3 x 10-10

Acid Base Reactions of Salts Salts of Strong Bases and Strong Acids
Salt = ionic compound formed in acid + base reaction.
H3O+(aq) + OH-(aq) H2O(ℓ) + H2O(ℓ)
HX(aq) + MOH(aq) MX(aq) + H2O(ℓ)
acid base salt Acid Base Base Acid

Strong acid + strong base:

base
HCl(aq) + NaOH(aq)
H3O+(aq) + Cl-(aq) + Na+(aq) + OH-(aq)
Na+(aq) + Cl-(aq) + 2 H2O(ℓ)
Net ionic equation: H3O+(aq) + OH-(aq)
• Na+ and Cl- are spectators – appear as reactants
NaCl(aq) + H2O(ℓ)
and products.
• Net products are water: weak acid and weak base.
• Final solution has pH = 7.
Strong acid + strong base → salt and water.
2 H2O(ℓ) Equal moles generate a neutral solution.

7
Salts of Strong Bases and Weak Acids Salts of Strong Bases and Weak Acids
Weak acid + strong base is more complex. CH3COOH(aq) + OH-(aq) CH3COO-(aq) + H2O(ℓ)
CH3COOH(aq) + NaOH(aq)
Acid Base Base Acid
CH3COONa(aq) + H2O(ℓ)

Weak acids partially ionize in solution. Acetate ions form:

• Do not dissociate the acid on the reactant side. • acetate is a weak base (much stronger than water).
• solution is basic (pH > 7.0).
CH3COOH(aq) + Na+(aq) + OH-(aq)
Na+(aq) + CH3COO-(aq) + H2O CH3COO-(aq) + H2O(ℓ) CH3COOH(aq) + OH-(aq)

Net ionic: CH3COOH(aq) + OH-(aq) A hydrolysis reaction – water is broken apart.

CH3COO- + H2O(ℓ)

Salts of Strong Bases and Weak Acids pH of a Salt Solution

For a weak acid + strong base, pH depends on Kb. What is the pH of a 1.50 M Na2CO3(aq)? Kb = 2.1 x 10-4

Larger Kb = stronger base

CO32-(aq) + H2O(ℓ) HCO3-(aq) + OH-(aq)
Example What is the pH of 1.50 M Na2CO3(aq)? [ ]initial 1.50 0 0
Kb (CO32-) = 2.1 x 10-4. [ ]change -x +x +x
[ ]equil 1.50 - x x x
Na+ is the conjugate acid of NaOH (strong base). - - x2 x2
• It remains 100% ionized. Kb = 2.1 x 10-4 = [HCO3 ][OH ] = ≈
2-
[CO3 ] (1.50 – x) 1.50
• Na+ has no effect on pH.
CO32- is the conjugate base of HCO3- (weak acid). x = 1.77 x 10-2 pOH = −log(1.77 x 10-2) = 1.75
• Hydrolysis: CO32- + H2O → HCO3- and OH-
pH = 14.00 - 1.75 = 12.25
• Changes the pH.

Salts of Weak Bases and Strong Acids pH of a Salt Solution

Similar arguments. Find the pH of 0.132 M NH4Br(aq). Is this solution
NH3(aq) + HCl(aq) NH4+(aq) + Cl-(aq) acidic, basic or neutral? Ka(NH4+) = 5.6 x 10-10.
The solution contains NH4+ ions and Br- ions.
NH3(aq) + H3O+(aq) + Cl-(aq)
• NH4+ is the conjugate acid of NH3 (a weak base).
NH4+(aq) + Cl-(aq) + H2O(ℓ)
+
 NH4+ + H2O NH3 + H3O+
Net ionic: NH3(aq) + H3O (aq) NH4+(aq) + H2O(ℓ)
 Acidic solution!
An equimolar reaction produces an acidic solution:
NH4+(aq) + H2O(ℓ) NH3(aq) + H3O+(aq) • Br- is the conjugate base of HBr (a strong acid).
The final pH depends on Ka:  Br- ions stay fully ionized.

Larger Ka = more acidic  Does not change the pH.

8
pH of a Salt Solution Salts of Weak Bases and Weak Acids
pH of 0.132 M NH4Br? Acidic, basic or neutral? Ka(NH4+) = 5.6 x 10-10. The most difficult. Consider qualitative results. e.g.
NH4F(aq) + H2O(ℓ) ?
NH4+(aq) + H2O(ℓ) NH3(aq) + H3O+(aq)
[ ]initial 0.132 0 0 NH4+(aq) + H2O(ℓ) NH3(aq) + H3O+(aq)
[ ]change -x +x +x
[ ]equil 0.132 - x x x F-(aq) + H2O(ℓ) HF(aq) + OH-(aq)

+ x2 x2
Ka = 5.6 x 10-10 = [NH3][H+3O ] = ≈ Ka(NH4+) = 5.6 x 10-10 ; Kb(F-) = 1.4 x 10-11
[NH4 ] (0.132 – x) 0.132
Ka (weak acid) > Kb (weak base)
x = 8.57 x 10-6 pH = −log(8.57 x 10-6) = 5.07 The ammonium reaction is more favorable.

Acidic! The solution will be acidic!

Acids, Bases and Salts Lewis Acids and Bases

The most general acid-base definition:
Strong acid + strong base → salt solution, pH = 7

A Lewis acid accepts a pair of e- to form a bond.

Strong acid + weak base → salt solution, pH < 7
A Lewis base donates a pair of e- to form a bond.

Weak acid + strong base → salt solution, pH > 7

A + A B
..
B

Acid Base Coordinate

e- pair donor
Weak acid + weak base → salt solution, pH = ? e- pair acceptor covalent bond

Need K’s “strongest wins” bond a shared e- pair, with both e-

Coordinate covalent bond:
donated by the same atom.

Lewis Acids and Bases Positive Metal Ions as Lewis Acids

Examples: H H Metal ions can act as Lewis acids. They have:
• Missing e-.
H + O H O H
• Empty valence orbitals.
Lewis acid Lewis base H • Metal ion + Lewis base → complex ion
H+ + H2O H3O+
Ag+ (aq) + 2 :NH3 (aq) [H3N:Ag:NH3]+ (aq)
F H F H
F B N H Hydroxide ions are Lewis bases. δ- δ+
F B + N H
:O–H -
: :

• O is e- rich (has large electronegativity):

F H F H • Can easily donate an e- pair to a bond.
Lewis acid Lewis base

9
Positive Metal Ions as Lewis Acids Neutral Molecules as Lewis Acids
Many metal hydroxides are amphoteric – they react Non-metal oxides act as Lewis acids.
with acids and bases. • O attracts e- from any multiple bond.
• Leaves the other non-metal e- deficient.
Aluminum hydroxide can act as a Lewis acid: δ+ δ+
S S δ- δ+ δ-
Al(OH)3(s) + OH-(aq) [Al(OH)4 ]-(aq) O=C=O
δ- O O δ- δ- O O δ-

or as a Brønsted-Lowry base: • Susceptible to attack by Lewis base:

- -
Al(OH)3(s) + 3 H3O+(aq) Al3+(aq) + 6 H2O(ℓ) H O H O
C=O
O=C=O O

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