Acids & Bases

• Other acids, called polyprotic acids are capable

of donating two or more protons.

• Last semester, you were introduced to two defini-

tions of acids and bases: the Arrhenius and the
Bronsted–Lowry definition.
• Arrhenius acid: Any substance that when dis-
solved in water increases the concentration of hy-
drogen ions, H+.
• Arrhenius base: Any substance that increases the
concentration of hydroxide ions, OH-, when dis- POLYPROTIC ACIDS
solved in water. • At your desk show the dissociation
o A Brønsted–Lowry acid is a proton (H+) do- o H2SO3
nor. o H2SO3 ⇆ H+ + HSO3-
o A Brønsted–Lowry base is a proton acceptor. o Ka1 = 1.7 x 10−2
• At your desk show dissociation of HSO3−
ARRHENIUS THEORY o H2SO3- ⇆ H+ + SO32-
• Acid: Anything that produces hydrogen ions in a o Ka2 = 6.4 × 10−8
water solution. • Ka values for each successive step become
HCl → H+ + Cl− smaller.
• Base: Anything that produces hydroxide ions in a • Why??
water solution. o It’s more difficult to remove an H+ from a nega-
NaOH → Na+ + OH− tive species than from a neutral one.
• Monoprotic acids
Complete the following table: o HF, HCl, HNO3
# of elec- # of neu- # of pro- • Diprotic acids (polyprotic)
trons trons tons o H2SO4, H2CO3
H+ 0 0 1 • Triprotic acids (polyprotic)
o H3PO4
BRONSTED−LOWRY THEORY
• Expands the Arrhenius theory. Good theory, but BRØONSTED−-LOWRY ACIDS AND BASES
not big enough. Acids Bases
o Acid Proton donor • proton donors • proton acceptors
▪ adds H+ to solution. • donates H+ • accepts H+
o Base Proton acceptor
▪ removes H+ from solution.

THE BRONSTED-–LOWRY CONCEPT OF ACIDS & BASES

• Proton donors may be molecular compounds,
cations or anions.

HNO3(aq) + H2O(l) → NO3- (aq) + H3O+(aq)

NH4+ (aq) + H2O(l) → NH3 (aq) + H3O+(aq)
HCO3- (aq) + H2O (l) → CO32- (aq) + H3O+(aq)
• Proton acceptors may be molecular compounds,
cations or anions.
• Using the Bronsted definition, NH3 is a BASE in
water and water is itself an ACID.
Proton acceptor
NH3(aq) + H2O(l) → NH3+(aq) + OH- (aq)
Proton donor
What is the definition of a strong acid?
• A strong acid completely dissociates into its
ions.
HCl + H2O → H3O+ + Cl-
• A weak acid does not completely ionize in solu-
tion.
HC2H3O2 + H2O ⇆ H3O+ + C2H3O2-

• Acids such as HF, HCl, HNO3, and CH3CO2H

(acetic acid) are all capable of donating one pro-
ACID AND BASE STRENGTH
ton and so are called monoprotic acids. • Strong acids: dissociate completely in water.
 • Weak acids: partially dissociate in water (most
acids are weak).
• Strong bases: dissociate completely in water.
• Weak bases: partially dissociate in water.
STRONG & WEAK ACIDS / BASES
• HNO3, HCl, H2SO4 and HClO4 are classified as
strong acids.
• Strong Base: 100% dissociated in water.
NaOH(aq) → Na+(aq) + OH-(aq)
o Other common strong bases include
KOH and Ca(OH)2.
o CaO (lime) + H2O → Ca(OH)2 (slaked
lime)
• Weak base: less than 100% ionized in water.
o An example of a weak base is ammonia.
▪ NH3(aq) + H2O(l) ⇆ NH4+(aq) + OH-(aq)
• Weak acids are much less than 100% ionized in
water.
o Example: acetic acid = CH3CO2H
• This involves a competition for protons.
• Stronger acids lose protons easier.
• Stronger bases hold onto protons easier.
COMPARING STRENGTHS OF ACETIC AND HYDROCHLORIC ACID
• Write the reaction of hydrochloric acid with water.
o HCl + H2O → Cl− + H3O+
• Identify the stronger acid and the weaker acid.
o HCl (strong acid) + H2O → Cl− + H3O+
(weaker acid)
• An acid/base reaction normally goes in the direc-
tion of the weaker acid.
• Write the reaction of acetic acid with water.
o HC2H3O2 + H2O D C2H3O2− + H3O+
• Identify the stronger acid and the weaker acid.
o HC2H3O2 (weaker acid) + H2O D C2H3O2−
+ H3O+ (stronger acid)
Identify the Acid in the following
• HNO3(aq) + H2O(l) → NO3−(aq) + H3O+(aq)
o HNO3(aq)
• NH4+(aq) + H2O(l) ⇆ NH3(aq) + H3O+(aq)
o NH4+(aq)
• H2PO4−(aq) + H2O(l) ⇆ HPO42−(aq) +
H3O+(aq)
o H2PO4−(aq)
CONJUGATE ACID−BASE PAIRS
• You have an acid
• It donates an H+
• What is left over is its conjugate base
• Ergo
• HCl (acid)
• Donates H+
• Cl− (conjugate base)

RELATIVE STRENGTH OF ACIDS

Acid [HA] [H+] Type
HCl 0.10 0.10 Strong, 100% ionized
HOAc 0.10 0.0013 Weal, less than 100% ion-
ized • A conjugate acid–base pair consists of two spe-
cies that differ from each other by the presence of
one hydrogen ion.
• Every reaction between a Brønsted acid and a
Brønsted base involves two conjugate acid–base
pairs.

Identify the acid, base, and their conjugate pairs.

 • HClO and Cl−
• HF and F–
• HNO2 and NO2–
• H2CO3 and HCO3–
5. You have a 5.43 × 10−4 M solution of HNO3
at 25 °C. What is [OH−] in this solution?
• 1.84 × 10−11 M
• 5.43 × 10−4 M
• 5.43 × 10−10 M
• 3.67 × 10−8 M

Solution:
[H+][OH-] = 1.0 x 10 -14
[H+] [H+]

1.0 x 10 -14
5.43 10−4 M

= 1.84 × 10−11 M

AUTOIONIZATION OF WATER
• Write an equilibrium expression (Kw) for the fol-
lowing.
o 2H2O(l) ⇆ H3O+(aq) + OH−(aq)
Kw = [H3O+ ] [OH- ]
• To a very very small extent does water ionize to
conduct electricity.
• Let’s rewrite the Kw expression more quantita-
tively.
Kw = [H3O+] [OH−] = 1 × 10−14

SIGNIFICANCE
• Based on previous rules, H2O is left out of equa-
tion
• Kw is special symbol known as “autoionization
constant for water.”
• [H3O+] = [OH−] = 1 × 10−7
o Kw = 1.0 × 10−14 at 25°C

PH SCALE
• pH = – log [H+] • pOH = – log[OH–]
QUESTIONS: • acidic solution • basic solution
1. What is the conjugate base of the formic • [H+] > [OH–] • [OH–] > [H+]
acid HCO2H? • pH < 7 • pH > 7
• HCO2– Neutral solution
• HCO2H2+ [H+] = [OH–]
• CO3 2-
2. What is the conjugate acid of the ion PH AND POH
H2PO4–? • We need to measure and use acids and bases
• HPO4 2− over a very large concentration range.
• H3PO4 • pH and pOH are systems to keep track of these
• PO4 3− very large ranges.
3. What is the conjugate base of the ion o pH = −log[H3O+]
HCO3–? o pOH = −log[OH−]
• H3CO3+ o pH + pOH = 14
• HCO3–
• CO3 2− WATER & THE PH SCALE
4. Which of the following is NOT an • H2O can function as both an ACID and a BASE.
acid−base conjugate pair?
• In pure water there can be AUTOIONIZATION.
 1 × 10−3 3
1 × 10−4 4
1 × 10−12 12

QUESTIONS:
6. A solution that has a pH of 10.5 is
- BASIC
7. A solution that has a pH of 4.5 is
- ACIDIC
• Equilibrium constant for autoionization = Kw 8. The pH of a solution that has [H3O+] = 1.0
• Kw = [H3O+] [OH−] = 1.00 × 10−14 at 25°C × 10−8 M is
• In a neutral solution, [H3O+] = [OH-] - 8.00
• Both are equal to 1.00x10-7 M. 9. A solution has a pH of 4.50. The hydro-
• In an acidic solution, [H3O+] > [OH-] nium ion concentration is
• [H3O+] > 1.00x10-7 M and [OH-] < 1.00 ´ 10-7 M - 3.2 × 10−5 M
• In a basic solution, [H3O+] < [OH-] 10. A solution has a hydronium ion concen-
• [H3O+] < 1.00x10-7 M and [OH-] > 1.00 ´ 10-7 M tration of 3.2 × 10−5 M. The pOH is
- 9.50
THE PH SCALE Solution:
[H+][OH-] = 1.0 x 10 -14
[H+] [H+]

1.0 x 10 -14
3.2 x 10−5 M
= 3.125 x 10 -10
= - log (3.125 x 10 -10)
= 9.50

11. What are the pH and the ion concentra-

tions in a solution of 0.0015 M of NaOH?

• The pH of a solution is defined as the negative of

the base (10) logarithm (log) of the hydronium ion
concentration.
pH = - log[H3O+]
• In a similar way, we can define the pOH of a so- 12. A solution has [H3O+] = 1.0 × 10−8 M. The
lution as the negative of the base (10) logarithm hydroxide ion concentration is
of the hydroxide ion concentration. - 1.0 × 10−6 M
pOH = - log[OH-] 13. You have a 0.00100-M solution of NaOH at
pH + pOH = pKw = 14 25 °C. What is [H3O+] in this solution?
• The concentration of acid, [H3O+] is found by tak- - 1.00 × 10−11 M
ing the antilog of the solutions pH. 14. You add 0.535 g of NaOH to 100.0 mL of
[H3O+] = 10−pH water at 25 °C. What is [H3O+] in this so-
lution?
• In a similar way, [OH-] can be found from:
[OH-] 10−pOH - 7.48 × 10−14 M
15. You dilute 1.00 mL of 1.00 M HCl solution
• Once [H3O+] is known, [OH-] can be found from:
to 100.0 mL. What is [OH—] in this solu-
tion at 25 °C?
- 1.00 × 10−12 M

• And vice versa. ACID DISSOCIATION CONSTANT, Ka

• The strength of a weak acid can be expressed
with Ka
o HA (aq) + H2O(l) D H3O+(aq) + A− (aq)
• The strength of a weak acid is related to its equi-
HYDROGEN ION AND PH librium constant, Ka.
o Ka = [A−][H3O+] / [HA]
Hydrogen Ion Concentration pH
1 × 10−1 1 Ka AND Kb VALUES
1 × 10−2 2 • For weak acids and bases
 o Ka and Kb always have values that are
smaller than one.
o Acids with a larger Ka are stronger than ones
with a smaller Ka.
o Bases witha larger Kb are stronger than ones
with a smaller Kb.
• Most acids and bases are considered weak.

EQUILIBRIUM CONSTANTS FOR ACIDS & BASES

• Strong acids and bases almost completely ionize
in water (~100%):
Kstrong >> 1
(product favored)
• Weak acids and bases almost completely ionize
in water (<<100%):
Kweak << 1
(Reactant favored)
• The relative strength of an acid or base can also
be expressed quantitatively with an equilibrium
constant, often called an ionization constant. For
the general acid HA, we can write:

• The relative strength of an acid or base can also

be expressed quantitatively with an equilibrium
constant, often called an ionization constant. For
the general base B, we can write:
• [H+] and [OH–] depend on each other. Remem-
ber [H+] and [H3O+] are sometimes used inter-
changeably.
• [H3O+] × [OH–] = Kw
• Kw = 1.00 × 10–14 (at 25°C)
• For thought question you are asked to solve
• for a concentration based on this formula
o What are the concentrations of H3O+ and
OH− of the following?
▪ 1.2 M HBr
▪ 0.085 M Ca(OH)2
• The strongest acids are at the upper left. They
have the largest Ka values.
• Ka values become smaller on descending the
chart as the acid strength declines.
• The strongest bases are at the lower right. They
have the largest Kb values.
• Kb values become larger on descending the chart
as base strength increases.
• The weaker the acid, the stronger its conjugate
base: The smaller the value of Ka, the larger the
value of Kb.
• Aqueous acids that are stronger than H3O+ are
completely ionized.
• Their conjugate bases (such as NO3-) do not pro-
duce meaningful concentrations of OH- ions, their
Kb values are “very small.”
• Similar arguments follow for strong bases and
their conjugate acids.

IONIZATION CONSTANTS FOR ACIDS AND THEIR CONJUGATE BASES

 o Carbonic acid
• Logarithmic Scale of Relative Acid Strength, pKa o Formic acid
o Many chemists use a logarithmic scale to re- 18. What is the strongest base?
port and compare relative acid strengths. o CH3CO2- (acetate)
pKa = - log(Ka) o CO3 2- (carbonate)
o HS-
o NH3
19. A 0.10 M aqueous solution of K2CO3 will
• The lower the pKa, the stronger the acid. be.
- BASIC
20. A 0.10 M aqueous solution of NH4Br will
be.
- ACIDIC
21. A 0.10 M aqueous solution of FeCl3 will
be.
- ACIDIC
22. A 0.10 M aqueous solution of KNO3 will
be.
- NEUTRAL
RELATING THE IONIZATION CONSTANTS FOR AN ACID AND ITS 23. A 0.10 M aqueous solution of NaHPO4 will
CONJUGATE BASE be.
- BASIC

ACID-BASE PROPERTIES OF SALTS

• Anions that are conjugate bases of strong acids

o (for example, Cl- or NO3-).
NO3− (aq) + H2O(l) → No Reaction
• These species are such weak bases that they
have no effect on solution pH.
• Anions such as CO3- that are the conjugate ba-
ses of weak acids will raise the pH of a solution.
CO3 2−(aq) + H2O(l) → HCO3−(aq) + OH−(aq)
• Hydroxide ions are produced via “Hydrolysis”.
A partially deprotonated anion (such as HCO3-)
is amphiprotic. Its behavior will depend on the
QUESTIONS”: other species in the reaction.
16. Place the following acids in order of in- • Alkali metal and alkaline earth cations have no
creasing acid strength. measurable effect on solution pH.
a) Anilinium ion, C5H6N+, pKa = 4.60 Na+(aq) + H2O(l) → No Reaction
b) Benzilic acid, pKa = 3.09 • Since these cations are conjugate acids of strong
c) Chloroacetic acid, pKa = 2.98 bases, hydrolysis does not occur.
d) Dibromophenol, pKa = 8.06 • Basic cations are conjugate bases of acidic cati-
- d, a, b, c ons such as [Al(H2O)6]3+.
17. What is the strongest acid? • Acidic cations fall into two categories:
o H3PO4 a. metal cations with 2+ and 3+ charges and;
o Boric acid
 b. ammonium ions (and their organic deriva-
tives).
• All metal cations are hydrated in water, forming
ions such as [M(H2O)6]n+.
ACID− BASE PROPERTIES OF SALTS SUMMARY
• Anions that are conjugate bases of strong acids
are such weak bases that they have no effect on
solution ph.
• There are numerous basic anions. All are the con-
jugate bases of weak acids.
• The acid−base behavior of anions of polyprotic
acids depends on the extent of deprotonation. A
solution may be acidic or basic depending on the
relative strength of the anion as an acid or base.
• Alkali metal and alkaline earth cations have no
measurable effect on solution pH.
• Basic cations are conjugate bases of acidic cati-
ons such as [Al(H2O)6]3+.
• Acidic cations fall into two categories:
o Metal cations with 2+ and 3+ charges
o Ammonium ions (and its organic derivatives)
o All metal cations are hydrated in water, form-
ing ions such as [M(H2O)6]n+
PREDICTING THE DIRECTION OF ACID –BASE REACTIONS
• According to the Brønsted–Lowry theory, all
acid–base reactions can be written as equilibria
involving the acid and base and their conjugates.
• All proton transfer reactions proceed from the
stronger acid and base to the weaker acid and
base.
QUESTIONS:
24. Knowing that HF is a stronger acid than
CH3CO2H, determine, if possible, in which
direction the following equilibrium lies.
HF (aq) + CH3CO2–aq) ⇄ F—(aq) +
CH3CO2H (aq)
o equilibrium lies to the left.
o equilibrium lies to the right.
o equilibrium is perfectly balanced between
left and right.
o cannot be determined.
25. Knowing that H2S is a stronger acid than
HCN, determine, if possible, in which di-
rection the following equilibrium lies.
HCN (aq) + HS—(aq) ⇄ CN—(aq) +
H2S(aq)
o equilibrium lies to the left.
o equilibrium lies to the right.
o equilibrium is perfectly balanced between
left and right.
o cannot be determined.
26. For the reaction below, decide whether
the equilibrium lies predominantly to the
right or to the left.
HCl(aq) + CO3 2−(aq) ⇄ Cl−(aq) + HCO3
(aq)
o Right
o Left
27. For the reaction below, decide whether
the equilibrium lies predominantly to the
right or to the left.
HCO3–(aq) + NH3(aq) ⇄ CO3 2− (aq) +
NH4+(aq)
o Right
o Left
28. For the reaction below, decide whether
the equilibrium lies predominantly to the
right or to the left.
NH4+(aq) + F−(aq) ⇄ NH3(aq) + HF(aq)
o Right
o Left
TYPES ACIDS–BASE REACTIONS
STRONG ACID (HCL) + STRONG BASE (NAOH)
HCl(aq) + NaOH(aq) D H3O+(aq) + NaCl(aq)
o Net ionic equation
H3O+ (aq) + OH−(aq) D 2H2O(l)
o Mixing equal molar quantities of a strong acid
and strong base produces a neutral solution.
WEAK ACID (HCN) + STRONG BASE (NAOH)
HCN(aq) + OH−(aq) D CN−(aq) + H2O(l)
o Mixing equal amounts (moles) of a strong
base and a weak acid produces a salt whose
anion is the conjugate base of the weak acid.
The solution is basic, with the pH depending
on Kb for the anion.
STRONG ACID (HCL) + WEAK BASE (NH3)
H3O+(aq) + NH3(aq) D H2O(l) + NH4+(aq)
o Mixing equal amounts (moles) of a weak base
and a strong acid produces a conjugate acid
of the weak base. The solution is basic, with
the pH depending on Ka for the acid.
 there is not enough information given to
WEAK ACID (CH3CO2H) + WEAK BASE (NH3) tell for sure.
CH3CO2H(aq) + (NH3) D CH3CO2−(aq) + NH4+(aq) CH3CO2H(aq) + NH3(aq) → ?
o Mixing equal amounts (moles) of a weak acid o Acidic
and a weak base produces a salt whose cat- o Neutral
ion is the conjugate acid of the weak base o Basic
and whose anion is the conjugate base of the o Cannot be determined from information
weak acid. given.
o The solution pH depends on the relative Ka 33. The following reactants are mixed in equal
and Kb values. molar portions. Predict if the resulting solu-
tion will be acidic, basic, neutral, or if there is
not enough information given to tell for sure.
CHARACTERISTICS OF ACID−BASE REACTIONS HCl(aq) + Ca(OH)2(aq) → ?
o Acidic
o Neutral
o Basic
o Cannot be determined from information
given.

CALCULATIONS WITH EQUILIBRIUM CONSTANTS

• Using RICE Table again

QUESTIONS:
29. The following reactants are mixed in equal
molar portions. Predict if the resulting so-
lution will be acidic, basic, neutral, or if
there is not enough information given to
tell for sure.
HCl(aq) + NaOH(aq) → ?
o Acidic
o Neutral
o Basic
o Cannot be determined from information
given.
30. The following reactants are mixed in equal
molar portions. Predict if the resulting so-
lution will be acidic, basic, neutral, or if
there is not enough information given to
tell for sure.
HF(aq) + KOH(aq) → ?
o Acidic
o Neutral
o Basic
o Cannot be determined from information
given.
31. The following reactants are mixed in equal
molar portions. Predict if the resulting so-
lution will be acidic, basic, neutral, or if
there is not enough information given to
tell for sure.
H2SO4(aq) + KOH(aq) → ?
o Acidic
o Neutral
o Basic
o Cannot be determined from information
given.
32. The following reactants are mixed in equal
molar portions. Predict if the resulting so-
lution will be acidic, basic, neutral, or if
CALCULATIONS WITH EQUILIBRIUM CONSTANTS Calculate the hydronium ion concentration and pH of the
1. Determining K from Initial Concentrations and solution that results when 22.0 mL of 0.15 M acetic acid,
pH CH3CO2H, is mixed with 22.0 mL of 0.15 M NaOH.

Solution: From the volume and concentration of each

solution, the moles of acid and base can be calculated.
Knowing the moles after the reaction and the equilibrium
constants, the concentration of H3O+ and pH can be
calculated.

All of the acetic acid is converted to acetate ion.

• In general, the approximation that

initial is valid whenever [HA]initial is greater than

or equal to 100 x Ka.
• If this is not the case, the quadratic equation must
by used.

METHOD OF APPROXIMATIONS
• FOR WEAK ACIDS AND BASES, WE CAN AP- QUESTIONS:
PROXIMATE IONIZATIONS. 34. A 0.040-M solution of an acid, HA, has a
• This way we can avoid using the quadratic equa- pH of 3.02 at 25 °C. What is Ka for this
tion. We must check the validity of the assump- acid?
tion. o 2.3 × 10−5
o 5.7 × 10−4
o 2.4 × 10−2
THE RULE GOES o 4.3 × 10−10
• Simplifying assumptions that produce an x value 35. What is [H3O+] in a 0.10-M solution of HCN
of less than 5% of the initial concentration of a re- at 25 °C? (Ka for HCN = 4.0 × 10−10)
actant are acceptable because the produce neg- o 1.6 × 10−9 M
ligible errors in the value of x. o 6.3 × 10−6 M
o 2.0 × 10−5 M
2. Determining pH after an acid/base reaction: o 4.0 × 10−11 M
 36. What is [OH—] in a 0.050-M solution of b. What is the equilibrium concentration of the
NH3 at 25 °C? (Kb for NH3 = 1.8 × 10−5) sulfite ion, SO3 2− in the 0.45 M solution of
o 4.2 × 10−3 M H2SO3?
o 9.5 × 10−4 M
o 6.9 × 10−12 M
o 0.22 M
37. What are the pH and ion concentrations in • Since 100 x Ka is not << 0.45M, the quadratic
a solution of 0.10-M sodium formate, Na- equation must be used.
CHO2?
Kb for the formate ion HCO2− is 5.6 × 10−11.
POLYPROTIC ACIDS
pH [Na+] [CHO2-] [OH-]
• pH of many polyprotic depend primarily on the
1 5.63 0.10 0.10 2.4 x 10 -6 first ionization step, the hydronium ion produced
2 8.37 0.10 0.10 2.4 x 10 -6 in the second step can be ignored.
3 8.22 0.050 0.050 1.7 x 10 -6
4 5.63 0.10 0.10 4.2 x 10 -9
38. If you have a 0.15-M solution of Na2CO3,
what will be the concentrations of H3O+
and OH− and what will be the pH of the so-
lution? Kb for CO3 2− is 2.1× 10−4.
[H3O+] [OH-] Ph
1 5.61 x 10 -3 1.78 x 10 -12 5.61
2 1.78 x 10 -12 5.61 x 10 -3 11.75
3 5.61 x 10 -3 1.78 x 10 -12 11.75
4 1.78 x 10 -12 5.61 x 10 -3 5.61
39. You mix 15.0 mL of 0.400-M HCl with 15.0
mL of 0.400-M NH3. What is the pH of the
resulting solution?
o less than 7
o equal to 7
o greater than 7
40. You mix 25 mL of 0.15-M H3PO4 with 25 2. Sulfurous acid, H2SO3, is a weak acid capable of
mL of 0.45-M NaOH. What is the pH of the providing two H+ ions.
resulting solution? a. What is the pH of a 0.45 M solution of
o less than 7 H2SO3?
o equal to 7 b. What is the equilibrium concentration of the
o greater than 7 sulfite ion, SO3 2− in the 0.45 M solution of
41. You mix 0.40 g of NaOH (molar mass = 40 H2SO3?
g/mol) with 100 mL of 0.10 M acetic acid.
What is the pH of the resulting solution?
o less than 7
o equal to 7
o greater than 7

POLYPROTIC ACIDS & BASES

• Because polyprotic acids are capable of donating
more than one proton they present us with addi-
tional challenges when predicting the pH of their
solutions.
• For many inorganic polyprotic acids, the ioniza-
tion constant for each successive loss of a proton
is about 104 to 106 smaller than the previous
step.
• This implies that the pH of many inorganic poly- MOLECULAR STRUCTURE, BONDING, & ACID–BASE BEHAVIOR
protic acids depends primarily on the hydronium
ion generated in the first ionization step.
• The hydronium ion produced in the second step
can be neglected.
1. Sulfurous acid, H2SO3, is a weak acid capable of
providing two H+ ions.
a. What is the pH of a 0.45 M solution of
H2SO3?
 • Halide Acid Strengths
o Experiments show that the acid strength in-
creases in the order:
HF << HCl < HBr < HI.
o Stronger acids result when the H-X bond is
readily broken (as signaled by a smaller, pos-
itive value of DH for bond dissociation) and a
more negative value for the electron at-
tachment enthalpy of X.
Carboxylic Acids as Brønsted Acids
MOLECULAR STRUCTURE AND ACID STRENGTH
• Strength is dependent on how easily H+ is lost or
removed.
For an acid of the formula H−X
• As you go down a group on the P.T. , the size of
X increases, and H−X bond strength decreases,
acidity strength increases.
• As electronegativity of X increases bond polarity
increases and acid strength increases. WHY ARE CARBOXYLIC ACIDS BRØNSTED ACIDS?
• For oxyacids, acid strength increases with # of ox- • The carboxylate anion is stabilized by resonance.
ygen atoms.
• In polyprotic acids, acid strength decreases with
more negative anionic charge.

OXOACIDS
• contain oxygen
• contain at least one other element
• has at least one hydrogen atom bound to oxygen
• forms an ion by the loss of one or more Protons WHY ARE CARBOXYLIC ACIDS BRONSTED ACIDS?
• The acidity of carboxylic acids is enhanced if elec-
tronegative substituents replace the hydrogen at-
oms in the alkyl (–CH3 or –C2H5) groups.
• Compare, for example, the pKa values of a series
of acetic acids in which hydrogen is replaced se-
quentially by the more electronegative element
• Comparing Oxoacids: HNO2 and HNO3
chlorine.
o In all the series of related oxoacid com-
pounds, the acid strength increases as the
number of oxygen atoms bonded to the cen-
tral element increases.
o Thus, nitric acid (HNO3) is a stronger acid
than nitrous acid (HNO2).

ACID STRENGTH TRENDS

• Strength increases as the # of Oxygen atoms
bonded to the central atom increases
• HNO3 > HNO2
• HOCl < HOClO< HOClO2 < HOClO3
• Formal charge and Resonance also play a part
(first semester)

WHY ARE CARBOXYLIC ACIDS BRØNSTED ACIDS?

• There is a large class of organic acids, all like
acetic acid (CH3CO2H) have the carboxylic acid
group, -CO2H
• They are collectively called carboxylic acids.
• Trichloroacetic acid is a much stronger acid ow-
ing to the high electronegativity of Cl.
• Cl withdraws electrons from the rest of the mole-
cule.
• This makes the O—H bond highly polar. The H of
O—H is very positive.
THE LEWIS CONCEPT OF ACIDS & BASES
• The concept of acid–base behavior advanced by
Brønsted and Lowry in the 1920’s works well for
reactions involving proton transfer.
• However, a more general acid– base concept,
was developed by Gilbert N. Lewis in the 1930’s.
• A Lewis acid is a substance that can accept a
pair of electrons from another atom to form a new
bond.
• A Lewis base is a substance that can donate a LEWIS ACID-BASE REACTIONS
pair of electrons to another atom to form a new
bond.
• Lewis acid
o Is a substance that can accept a pair of elec-
trons from another atom to form a new bond
• Lewis base
o Is a substance that can donate a pair of elec-
trons to another atom to form a new bond

REACTION OF A LEWIS ACID & LEWIS BASE

• New bond formed using electron pair from the
Lewis base. • Metal cations often act as Lewis acids because of
• Coordinate covalent bond open d−orbitals.
• Notice geometry change on reaction.

• The formation of a hydronium ion is an example

of a Lewis acid / base reaction

• The H+ is an electron pair acceptor.

• Water, with its lone pairs, is a Lewis acid donor.

Lewis acid
a substance that accepts
an electron pair.

• Aqueous solutions of Fe3+, Al3+, Cu2+, Pb2+,

etc. are acidic through hydrolysis.
Lewis
base
a substance that donates
an electron pair

LEWIS ACIDS & BASES

• The combination of metal ions (Lewis acids) with
• Lewis bases such as H2O and NH3 leads toCoor-
dinate Complex ions.
MOLECULAR LEWIS ACIDS
• Because oxygen is more electronegative than C,
the C-O bonding electrons in CO2 are polarized
away from carbon and toward oxygen.
 THE LEWIS CONCEPT OF ACIDS & BASES

• The product is often called an acid–base ad-

• This causes the carbon atom to be slightly posi-
tive, and it is this atom that the negatively charged
Lewis base OHcan attack to give, ultimately, the
bicarbonate ion.
• Ammonia is the parent compound of an enor-
mous number of compounds that behave as
Lewis and Brønsted bases. These molecules all
have an electronegative N atom with a partial
negative charge surrounded by three bonds and
a lone pair of electrons.
duct. In Section 8.3, this type of chemical bond
was called a coordinate covalent bond.
• Lewis acid−base reactions are very common. In
general, they involve Lewis acids that are cations
or neutral molecules with an available, empty va-
lence orbital and bases that are anions or neutral
molecules with a lone electron pair.
LEWIS ACID–BASE INTERACTIONS IN BIOLOGY
• The heme group in he-
moglobin can interact
with O2 and CO.
• The Fe ion in hemoglo-
bin is a Lewis acid
• O2 and CO can act as
Lewis Bases

QUESTIONS:
42. Which of the compounds or ions below is
a Lewis acid?
• This partially negative N atom can extract a pro- o NH2(CH3)
ton from water. o Ag+ in Ag(NH3)2+
o :C ≡ O: in Ni(CO)4
LEWIS ACIDS & BASES
• Many complex ions containing water underg
• HYDROLYSIS to give acidic solutions.

CATIONIC LEWIS ACIDS

• Form coordinate covalent bonds
• Called complex ions
• Coordination complexes
• Fe+3 + 6[:C≡N:] → [Fe(C≡N:)6]3−

AMPHOTERISM
• Defined—Can act as an acid or a base

Product called an acid base adduct

A + B: → B→A (adduct)