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Acids

and
Bases
Everyday Acids and Bases
Properties of Acids and Bases
Arrhenius Acid-base definition

• This is the earliest acid-base definition, which


classifies these substances in terms of their
behavior in water.
• An acid is a substance with H in its formula that
dissociates to yield H3O+.
• A base is a substance with OH in its formula that
dissociates to yield OH-.
• When an acid reacts with a base, they undergo
neutralization:
H+(aq) + OH-(aq) → H2O(l) DH°rxn = -55.9 kJ
Brønsted-Lowry Acid-Base
Definition
Lone pair
binds H+
• An acid is a proton donor, any species that
donates an H+ ion.
• An acid must contain H in its formula.
(acid, H+ donor) (base, H+ acceptor) • A base is a proton acceptor, any species
Lone pair that accepts H+ ion.
binds H+
• A base must contain a lone pair of
elecrtons to bond to H+.
• An acid-base reaction is a proton-transfer
process

(base, H+ acceptor) (acid, H+ donor)


The Lewis Acid-base Definition
• A Lewis base is any species that donates an electro pair to form a bond.
• A Lewis acid is any species hat accepts an electron pair to form a bond.

• The Lewis definition views an acid-base reaction as the donation and acceptance
of an electron pair to form a covalent bond.
Acids and Bases Theories
Strong and Weak Acids
• A strong acid dissociates completely into ions in water:
• HA(g or l) + H2O(l) → H3O+(aq) + A-(aq)
• A dilute solution of a strong acid contains no HA molecules.
• A weak acid dissociates slightly to form ions water.
• HA(aq) + H2O(l) H3O+(aq) + A-(aq)

• In A dilute solution of a weak acid, most HA molecules are


undissociated.
[H3O+][A-]
Kc = has a very small value.
[HA][H2O]
Figure 18.1A The extent of dissociation for strong acids.

Strong acid: HA(g or l) + H2O(l) → H3O+(aq) + A-(aq)

There are no HA molecules in solution.


Figure 18.1B The extent of dissociation for weak acids.

Weak acid: HA(aq) + H2O(l) H3O+(aq) + A-(aq)

Most HA molecules are undissociated.


Figure 18.2 Reaction of zinc with a strong acid (left) and a
weak acid (right).

Zinc reacts rapidly with


the strong acid, since
[H3O+] is much higher.

1 M HCl(aq) 1 M CH3COOH(aq)
The acid dissociation constant

HA(aq) + H2O(l) H3O+(aq) + A–(aq)

[H3O+][A–] [H3O+][A–]
Kc = Kc[H2O] = Ka =
[HA][H2O] [HA]

The value of Ka is an indication of acid strength.

Stronger acid higher [H3O+] larger Ka

Weaker acid lower % dissociation of HA smaller Ka


Acid dissociation constant
Values for some monoprotic
•k acids at 25o C
Classifying the relative
strengths of acids
• Strong acids include
• the hydrohalic acids (HCl, HBr, and HI) and
• oxoacids in which the number of O atoms exceeds the number of ionizable
protons by two or more (eg., HNO3, H2SO4, HClO4.)
• Weak acids include
• the hydrohalic acid HF,
• acids in which H is not bonded to O or to a halogen (eg., HCN),
• oxoacids in which the number of O atoms equals or exceeds the number of
ionizable protons by one (eg., HClO, HNO2), and
• carboxylic acids, which have the general formula RCOOH (eg., CH3COOH and
C6H5COOH.)
Classifying the Relative
Strengths of Bases
• Strong bases include
• water-soluble compounds containing O2- or OH- ions.
• The cations are usually those of the most active metals:
• M2O or MOH, where M = Group 1A(1) metal (Li, Na, K, Rb, Cs)
• MO or M(OH)2 where M = group 2A(2) metal (Ca, Sr, Ba).
• Weak bases include
• ammonia (NH3),
• amines, which have the general formula
• The common structural feature is an N atom with a lone electron pair.
Acid
Electronegativity
strength of Nonmetal
increases, so Hydrides
acidity increases

6A(16) 7A(17)
• For nonmetal hydrides (E-H), acid
H 2O HF
strength depends on:
• The electronegativity of the central
decreases, so acidity

nonmetal (E), and


• The strength of the E-H bond.
Bond strength

H 2S HCl
• Across a period, acid strength increases.
increases

• Electronegativity increases across a period,


H2Se HBr so the acidity of E-H increases.
• Down a group, acid strength increases.
• The length of the E-H bond increases down
H2Te HI a group and its bond strength therefore
decreases.
Acid Strength of Oxoacids
• All oxoacids have the acidic H bonded to
an O atom.
• Acid strength of oxoacids depends on:
• The electronegativity of the central
nonmetal (E), and
• The number of O atoms around E.
• For oxoacids with the same number of
O atoms, acid strength increases as the
electronegativity of E increases.
• For oxoacids with different numbers of
O atoms, acid strength increases with
the number of O atoms.
Hydrated Metal Ions
• Some hydrated metal ions are able to transfer an H+ to H2O. These metal ions will form acidic
solutions.
• Consider a metal ion in solution, Mn+.
Mn+(aq) + H2O(l) → M(H2O)xn+(aq)
• If Mn+ is small and highly charged, it will withdraw enough e- density from the O-H bonds of
the bound H2O molecules to release H+.
M(H2O)xn+(aq) + H2O(l) M(H2O)x-1OH(n-1)+(aq) + H3O+(aq)
Autoionization of water

• Water dissociates very slightly into ions in an equilibrium process known as


autoionization or self-ionization.
• 2H2O (l) H3O+ (aq) + OH- (aq)
The Ion-Product Constant for
Water (kw)
2H2O (l) H3O+ (aq) + OH- (aq)
[H3O+][OH-]
Kc =
[H2O]2

Kc[H2O]2 = Kw = [H3O+][OH-] = 1.0x10-14 (at 25°C)

In pure water,
[H3O+] = [OH-] = = 1.0x10-7 (at 25°C)

Both ions are present in all aqueous systems.


• A change in [H3O+] causes an inverse change in [OH-], and vice versa.

Higher [H3O+] lower [OH-]


Higher [OH-] lower [H3O+]
• We can define the terms “acidic” and “basic” in terms of the relative
concentrations of H3O+ and OH- ions:

In an acidic solution, [H3O+] > [OH–]


In a neutral solution, [H3O+] = [OH–]
In a basic solution, [H3O+] < [OH–]
The relationship between [H3O+] and
[OH-] and the relative acidity of
solutions.
Sample Problem 18.2 Calculating [H3O+] or [OH–] in an Aqueous Solution

PROBLEM: A research chemist adds a measured amount of HCl gas to pure water at
25°C and obtains a solution with [H3O+] = 3.0x10–4 M. Calculate [OH–].
Is the solution neutral, acidic, or basic?

PLAN: We use the known value of Kw at 25°C (1.0x10–14) and the given [H3O+] to solve
for [OH–]. We can then compare [H3O+] with [OH–] to determine whether the
solution is acidic, basic, or neutral.

SOLUTION:

Kw = 1.0 x 10–14 = [H3O+] [OH–] so

Kw 1.0 x 10–14
[OH–] = = = 3.3x10–11 M
[H3O+] 3.0 x 10–4

[H3O+] is > [OH–] and the solution is acidic.


Problem set
• Calculate [H3O+] in a solution that is at 25˚C and has
[OH-] = 6.7x10-2 M. is the solution neutral, acidic or basic?
Copyright  The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

The ph scale

pH = -log[H3O+]
The pH The pH of a solution indicates its relative acidity:
values of
some familiar
aqueous In an acidic solution, pH < 7.00
solutions. In a neutral solution, pH = 7.00
In a basic solution, pH > 7.00

The higher the pH, the lower the [H3O+] and the
less acidic the solution.
pH, pOH, and pKw
Kw = [H3O+][OH–] = 1.0x10–14 at 25°C

pH = –log[H3O+]
pKw = pH + pOH = 14.00 at 25°C
pOH = –log[OH–]

pH + pOH = pKw for any aqueous solution at any temperature.

Since Kw is a constant, the values of pH, pOH, [H3O+], and [OH–] are
interrelated:
• If [H3O+] increases, [OH–] decreases (and vice versa).
• If pH increases, pOH decreases (and vice versa).
Sample Problem 18.3 Calculating [H3O+], pH, [OH-], and pOH for
Strong Acids and Bases
PROBLEM: Calculate [H3O+], pH, [OH–], and pOH for each solution at
25°C:
(a) 0.30 M HNO3, used for etching copper metal; and
(b) 0.0042 M Ca(OH)2, used in leather tanning to remove hair from hides.

PLAN:
HNO3 is a strong acid; so it dissociates completely, and [H3O+] = [HNO3]init.
Likewise, Ca(OH)2 is a strong base that dissociates completely, and
[OH–] = 2[Ca(OH)2]init.
We use the given concentrations and the value of Kw at 25°C to find [OH–]
and [H3O+]. We can then calculate pH and pOH.
Sample Problem 18.3

SOLUTION:
(a) Calculating the values for 0.30 M HNO3:
[H3O+] = 0.30 M pH = –log[H3O+] = -log(0.30) = 0.52
K 1.0 x 10 –14
[OH–] = w = = 3.3 x 10-14 M
[H3O+] 0.30
pOH = –log[OH–] = –log(3.3 x 10–14) = 13.48
(b) Calculating the values for 0.0042 M Ca(OH)2:
Ca(OH)2 is a strong electrolyte: Ca(OH)2(aq) → Ca2+(aq) + 2 OH–(aq)
[OH–] = 2 (0.0042 M) = 0.0084 M
pOH = –log[OH–] = -log 0.0084 = 2.08
K 1.0 x 10 -14
+
[H3O ] = w = = 1.2 x 10–12 M
[OH–] 0.0084
pH = –log[H3O+] = –log(1.2 x 10–12) = 11.92
Methods for measuring the pH of
an aqueous solution.
Copyright  The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

pH paper

pH meter
Problem Set
• A solution of NaOH has a pH of 9.52. What is its pOH, [H3O+], and [OH-] at 25˚C?
Brønsted-Lowry Acid-Base
Definition
An acid is a proton donor, any species that donates an
H+ ion.
• An acid must contain H in its formula.

A base is a proton acceptor, any species that accepts


an H+ ion.
• A base must contain a lone pair of electrons to bond
to H+.

An acid-base reaction is a proton-transfer process.


Figure 18.7 Dissolving of an acid or base in water as a Brønsted-
Lowry acid-base reaction.
Lone pair Copyright  The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

binds H+

(acid, H+ donor) (base, H+ acceptor)


Lone pair
binds H+

(base, H+ acceptor) (acid, H+ donor)


Conjugate Acid-Base Pairs
In the forward reaction:
NH3 accepts a H+ to form NH4+.

H2S + NH3 HS– + NH4+

H2S donates an H+ to form HS-.


In the reverse reaction:
NH4+ donates a H+ to form NH3.

H2S + NH3 HS– + NH4+

HS– accepts an H+ to form H2S.


Conjugate Acid-Base Pairs
H2S + NH3 HS– + NH4+
H2S and HS– are a conjugate acid-base pair:
HS– is the conjugate base of the acid H2S.
NH3 and NH4+ are a conjugate acid-base pair:
NH4+ is the conjugate acid of the base NH3.
A Brønsted-Lowry acid-base reaction occurs when an acid and a
base react to form their conjugate base and conjugate acid,
respectively.

acid1 + base2 base1 + acid2


Table 18.4 The Conjugate Pairs in some Acid-Base Reactions
Conjugate Pair

Acid + Base Base + Acid

Conjugate Pair

Reaction 1 HF + H2O F– + H3O+

Reaction 2 HCOOH + CN– HCOO– + HCN

Reaction 3 NH4+ + CO32– NH3 + HCO3–

Reaction 4 H2PO4– + OH– HPO42– + H2O

Reaction 5 H2SO4 + N2H5+ HSO4– + N2H62+

Reaction 6 HPO42– + SO32– PO43– + HSO3–


Sample Problem 18.4 Identifying Conjugate Acid-Base Pairs

PROBLEM: The following reactions are important environmental


processes. Identify the conjugate acid-base pairs.
(a) H2PO4–(aq) + CO32– (aq) HPO42-–(aq) + HCO3–(aq)
(b) H2O(l) + SO32–(aq) OH–(aq) + HSO3–(aq)

PLAN: To find the conjugate pairs, we find the species that donated
an H+ (acid) and the species that accepted it (base). The acid
donates an H+ to become its conjugate base, and the base
accepts an H+ to become its conjugate acid.

SOLUTION:

(a) H2PO4–(aq) + CO32–(aq) HPO42–(aq) + HCO3–(aq)


acid1 base2 base1 acid2
The conjugate acid-base pairs are H2PO4–/HPO42– and CO32–/HCO3–.
Sample Problem 18.4

(b) H2O(l) + SO32–(aq) OH–(aq) + HSO3–(aq)


acid1 base2 base1 acid2

The conjugate acid-base pairs are H2O/OH– and SO32–/HSO3–.


Net Direction of Reaction

The net direction of an acid-base reaction depends on


the relative strength of the acids and bases involved.

A reaction will favor the formation of the weaker acid


and base.
H2S + NH3 HS– + NH4+

stronger acid weaker base


stronger base weaker acid

This reaction favors the formation of the products.


Strengths of conjugate
Copyright  The McGraw-Hill Companies, Inc. Permission required for reproduction or display. acid-base pairs.

The stronger the acid


is, the weaker its
conjugate base.
When an acid reacts
with a base that is
farther down the list,
the reaction proceeds
to the right (Kc > 1).
Sample Problem 18.5 Predicting the Net Direction of an Acid-Base
Reaction
PROBLEM: Predict the net direction and whether Kc is greater or less than 1 for each of the
following reactions (assume equal initial concentrations of all species):

(a) H2PO4–(aq) + NH3(aq) HPO42–(aq) + NH4+(aq)


(b) H2O(l) + HS–(aq) OH–(aq) + H2S(aq)

PLAN: We identify the conjugate acid-base pairs and consult figure 18.8 to see which acid and
base are stronger. The reaction favors the formation of the weaker acid and base.

SOLUTION:
(a) H2PO4–(aq) + NH3(aq) HPO42–(aq) + NH4+(aq)
stronger acid stronger base weaker base weaker acid

The net direction for this reaction is to the right, so Kc > 1.


(b) H2O(l) + HS–(aq) OH–(aq) + H2S(aq)
weaker acid weaker base stronger base stronger acid

The net direction for this reaction is to the left, so Kc < 1.


Problem Set

Identify the Conjugate acid-base pairs of the following reaction. Identify the
direction of the reaction and if K is greater than 1 or les than.
a. CH3COOH (aq) + H2O (l) CH3COO- (aq) + H3O+ (aq)
b. H2O (l) + F -(aq) OH- (aq) + HF (aq)
Solving Problems Involving
Weak-Acid equilibria

• Write a balanced equation.


• Write an expression for Ka
• Define x as the change in concentration that occurs during the reaction.
• Construct a reaction table in terms of x.
• Make assumptions that simplify the calculation.
• Substitute values into the Ka expression and solve for x.
• Check that the assumptions are justified.
Solving Problems Involving
Weak-Acid equilibria
• The Notation system
• Molar concentrations are indicated by [ ].
• A bracketed formula with no subscript indicates an equilibrium concentration.
• The Assumptions
• [H3O+] from the autoionization of H2O is negligible.
• A weak acid has a small Ka and is dissociation is negligible.
• [HA] = [HA]init -[HA]dissoc = [HA]init
Sample Problem 18.7 Finding Ka of a Weak Acid from the Solution pH

PROBLEM: Phenylacetic acid (C6H5CH2COOH, simplified here as HPAc) builds up in the blood
of persons with phenylketonuria, an inherited disorder that, if untreated, causes
mental retardation and death. A study of the acid shows that the pH of 0.12 M
HPAc is 2.62. What is the Ka of phenylacetic acid?

PLAN: We start with the balanced dissociation equation and write the expression for Ka.
We assume that [H3O+] from H2O is negligible and use the given pH to find [H3O+],
which equals [PAc–] and [HPAc]dissoc. We assume that [HPAc] ≈ [HPAc]init because
HPAc is a weak acid.

SOLUTION: HPAc(aq) + H2O(l) H3O+(aq) + PAc–(aq)

Ka = [H3O+][PAc–]
[HPAc]
Sample Problem 18.7

Concentration (M) HPAc(aq) + H2O(l) H3O+(aq) + PAc–(aq)

Initial 0.12 - 0 0
Change –x - +x +x
Equilibrium 0.12 – xx - x x
[H3O+] = antilog -pH = 2.4 x 10–3 M which is >> 10–7 (the [H3O+] from
water)
x ≈ 2.4 x 10–3 M ≈ [H3O+] ≈ [PAc–] [HPAc] = 0.12 - x ≈ 0.12 M
(2.4 x 10–3) (2.4 x 10–3)
So Ka = = 4.8 x 10–5
0.12
Checking the assumptions by finding the percent error in concentration:
1 x 10–7 M
+
[H3O ]from H2O = x 100 = 4 x 10–3 % (< 5%; assumption is justified).
2.4 x 10–3 M
–3
[HPAc]dissoc = 2.4 x 10 M x 100 = 2.0 % (< 5%; assumption is justified).
0.12 M
Sample Problem 18.8 Determining Concentration from Ka and
Initial [HA]

PROBLEM: Propanoic acid (CH3CH2COOH, which we simplify as HPr) is a carboxylic acid


whose salts are used to retard mold growth in foods. What is the [H3O+] of 0.10
M HPr (Ka = 1.3x10−5)?

PLAN: We write a balanced equation and the expression for Ka. We know [HPr]init but
not [HPr] (i.e., the concentration at equilibrium). We define x as [HPr]dissoc and
set up a reaction table. We assume that, since HPr has a small Ka value, it
dissociates very little and therefore [HPr] ≈ [HPr]init.

SOLUTION: HPr(aq) + H2O(l) H3O+(aq) + Pr−(aq)

Ka = [H3O+][Pr−]
[HPr]
Sample Problem 18.8

Concentration (M) HPr(aq) + H2O(l) H3O+(aq) + Pr–(aq)


Initial 0.10 - 0 0
Change -x - +x +x
Equilibrium 0.10 - x - x x

Since Ka is small, we will assume that x << 0.10 and [HPr] ≈ 0.10 M.
[H3O+][Pr–] x2
Ka = 1.3x10–5 = ≈
[HPr] 0.10
x ≈ √(0.10)(1.3 x 10–5) = 1.1 x 10–3 M = [H3O+]

1.1 x 10–3 M
Check: [HPr]diss = x 100 = 1.1% (< 5%; assumption is justified.)
0.10 M
Problem Set
• The conjugate acid of ammonia is NH4+, a weak acid if a 0.2M NH4Cl
solution has a pH of 5.0, what is the Ka of NH4+?
Concentration and extent of
dissociation
[HA]dissoc
Percent HA dissociated = x 100
[HA]init

As the initial acid concentration decreases, the percent dissociation of the


acid increases.

HA(aq) + H2O(l) H3O+(aq) + A–(aq)

A decrease in [HA]init means a


decrease in [HA]dissoc = [H3O+] = [A–],
causing a shift toward the products.

The fraction of ions present increases, even though the actual [HA]dissoc decreases.
WEAK BASES
A Brønsted-Lowry base is a species that accepts an H+.
For a weak base that dissolves in water:

B(aq) + H2O(l) BH+(aq) + OH–(aq)

The base-dissociation or base-ionization constant is


given by:
[BH+][OH–]
Kb =
[B]

Note that no base actually dissociates in solution, but ions are


produced when the base reacts with H2O.
Figure 18.9 Abstraction of a proton from water by the base methylamine.

Copyright  The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Lone pair of N pair


binds H+
Table 18.6 Kb Values for Some Molecular (Amine) Bases at 25°C
Sample Problem 18.11 Determining pH from Kb and Initial [B]

PROBLEM: Dimethylamine, (CH3)2NH, a key intermediate in detergent manufacture, has a Kb


of 5.9x10–4. What is the pH of 1.5 M (CH3)2NH?

PLAN: We start with the balanced equation for the reaction of the amine with H2O,
remembering that it is a weak base. We then write the expression for Kb, set up a
reaction table and solve for [OH–]. From [OH–] we can calculate [H3O+] and pH.
We make similar assumptions to those made for weak acids. Since Kb >> Kw, the
[OH–] from H2O is negligible. Since Kb is small, we can assume that the amount
of amine reacting is also small, so [(CH3)2NH] ≈ [(CH3)2NH]init.

SOLUTION: (CH3)2NH(aq) + H2O(l) (CH3)2NH2+(aq) + OH–(aq)

[(CH3)2NH2+][OH–]
Kb =
[(CH3)2NH]
Sample Problem 18.11

Concentration (M) (CH3)2NH(aq) + H2O(l) (CH3)2NH2+(aq) + OH–(aq)


Initial 1.5 - 0 0
Change -x - +x +x
Equilibrium 1.5 - x - x x

Since Kb is small, x << 1.5 and 1.5 – x ≈ 1.5


[(CH3)2NH2+][OH–] x 2
Kb = = 5.9 x 10–4 ≈
[(CH3)2NH] 1.5

x = [OH–] = 3.0 x 10–2 M

Check assumption:
3.0 x 10–2 M x 100 = 2.0% (< 5%; assumption is justified).
1.5 M
Sample Problem 18.11

K 1.0x10 –14
w –13 M
[H3O+] = = = 3.3 x 10
[OH–] 3.0x10–2

pH = –log (3.3 x 10–13) = 12.48


Problem Set
• Pyridine (C5H5N, see margin) serves as a solvent and base in organic syntheses. It
has a pKb of 8.77. What is the pH of 0.10 M pyridine?
Ka and Kb for a Conjugate Acid-Base Pair

HA + H2O H3O+ + A-
A- + H2O HA + OH–
2H2O H3O+ + OH–

Kc for the overall equation = K1 x K2, so

[H3O+][A–] x [HA][OH–] = [H O+][OH–]


3
[HA] –
[A ]
Ka x Kb = Kw

This relationship is true for any conjugate acid-base pair.


Sample Problem 18.12 Determining the pH of a Solution of A-

PROBLEM: Sodium acetate (CH3COONa, or NaAc for this problem) has applications in
photographic development and textile dyeing. What is the pH of 0.25 M
NaAc at 25ºC? Ka of acetic acid (HAc) is 1.8 x 10–5.

PLAN: Sodium salts are soluble in water and acetate is the anion of HAc so it acts
as a weak base. We write the base dissociation equation and the
expression for Kb, and solve for [OH-]. We recall that any soluble ionic salt
dissociates completely in solution, so [Ac–]init = 0.25 M.

SOLUTION: Ac–(aq) + H2O(l) HAc(aq) + OH–(aq)

[HAc][OH–]
Kb =
[Ac–]
Sample Problem 18.12

Concentration (M) Ac–(aq) + H2O(l) HAc(aq) + OH–(aq)


Initial 0.25 - 0 0
Change -x - +x +x
Equilibrium 0.25 - x - x x

Kw 1.0x10–14 –10 M
Kb of Ac- = = = 5.6x10
Ka 1.8x10–5

[HAc][OH–] x2
Kb = 5.6x10-10 = ≈ so x = [OH–] = 1.2x10–5 M

[Ac ] 0.25

Checking the assumption:

1.2x10–5 x 100 = 4.8x10-3% (< 5%; assumption is justified)


0.25
Sample Problem 18.12

K 1.0x10 –14
w –10 M
[H3O+] = = = 8.3x10
[OH–] 1.2x10–5

pH = – log (8.3x10–10) = 9.08