Acids and Bases • From the Latin word conjugare,

Some Definitions meaning “to

• Arrhenius join together.”
Acid: Substance that, when • Reactions between acids and bases
dissolved in always
water, increases the concentration of yield their conjugate bases and acids.
hydrogen ions. Acid and Base Strength
Base: Substance that, when • Strong acids are
dissolved in completely dissociated in
water, increases the concentration of water.
hydroxide ions. Their conjugate bases are
Some Definitions quite weak.
• Brønsted–Lowry • Weak acids only
Acid: Proton donor dissociate partially in
Base: Proton acceptor water.
A Brønsted–Lowry acid… Their conjugate bases are
…must have a removable (acidic) weak bases.
proton. Acid and Base Strength
A Brønsted–Lowry base… • Substances with
…must have a pair of nonbonding negligible acidity do not
electrons. dissociate in water.
If it can be either… Their conjugate bases are
exceedingly strong.
...it is amphiprotic.
HCO3 Acid and Base Strength
In any acid-base reaction, the
− equilibrium will favor the reaction that
HSO4 moves the proton to the stronger base.
− HCl(aq) + H2O(l)  H3O+(aq) +
H2O Cl−(aq)
What Happens When an Acid H2O is a much stronger base than Cl−,
Dissolves in Water? so the
• Water acts as a equilibrium lies so far to the right K is
Brønsted–Lowry base not
and abstracts a proton measured (K>>1).
(H+) from the acid. Acid and Base Strength
• As a result, the Acetate is a stronger base than H2O,
conjugate base of the so the
acid and a hydronium equilibrium favors the left side (K<1).
ion are formed. C2H3O2(aq) + H2O(l) H3O+(aq) +
Conjugate Acids and Bases: C2H3O2
−(aq)
Autoionization of Water so its pH is >7.
• As we have seen, water is pH
amphoteric. These are
• In pure water, a few molecules the pH
act as values for
several
bases and a few act as acids. common
• This is referred to as substances.
autoionization. Other “p” Scales
H2O(l) + H2O(l) H3O+(aq) + OH−(aq) • The “p” in pH tells us to take the
Ion-Product Constant negative log of the quantity (in this
• The equilibrium expression for case,
this hydrogen ions).
process is • Some similar examples are
Kc = [H3O+] [OH−] pOH −log [OH−]
• This special equilibrium constant is pKw −log Kw
referred to as the ion-product constant Watch This!
for water, Kw. Because
• At 25°C, Kw = 1.0  10−14 [H3O+] [OH−] = Kw = 1.0  10−14,
pH we know that
pH is defined as the negative base-10 −log [H3O+] + −log [OH−] = −log Kw
logarithm of the hydronium ion = 14.00
concentration. or, in other words,
pH = −log [H3O+] pH + pOH = pKw = 14.00
pH How Do We Measure pH?
• In pure water, • For less accurate
Kw = [H3O+] [OH−] = 1.0  10−14 measurements, one
• Because in pure water [H3O+] = can use
 Litmus paper
[OH−], • “Red” paper turns
[H3O+] = (1.0  10−14)1/2 = 1.0  10−7 blue above ~pH = 8
pH • “Blue” paper turns
red below ~pH = 5
• Therefore, in pure water, An indicator
pH = −log (1.0  10−7) = 7.00 How Do We Measure pH?
• An acid has a higher [H3O+] than For more accurate
pure water, measurements, one
so its pH is <7 uses a pH meter,
• A base has a lower [H3O+] than pure which measures the
water, voltage in the
solution. • The pH of a 0.10 M solution of
Strong Acids formic acid,
• You will recall that the seven strong HCOOH, at 25°C is 2.38. Calculate
acids are Ka for
HCl, HBr, HI, HNO3, H2SO4, HClO3, formic acid at this temperature.
and • We know that
HClO4. [H3O+] [COO−]
• These are, by definition, strong Ka = [HCOOH]
electrolytes Calculating Ka from the pH
and exist totally as ions in aqueous • The pH of a 0.10 M solution of
solution. formic acid,
• For the monoprotic strong acids, HCOOH, at 25°C is 2.38. Calculate
[H3O+] = [acid]. Ka for
Strong Bases formic acid at this temperature.
• Strong bases are the soluble • To calculate Ka, we need the
hydroxides, equilibrium
which are the alkali metal and heavier concentrations of all three things.
alkaline earth metal hydroxides (Ca2+, • We can find [H3O+], which is the
Sr2+, same as
and Ba2+). [HCOO−], from the pH.
• Again, these substances dissociate Calculating Ka from the pH
completely in aqueous solution. pH = −log [H3O+]
Dissociation Constants 2.38 = −log [H3O+]
• For a generalized acid −2.38 = log [H3O+]
dissociation, 10−2.38 = 10log [H3O+] = [H3O+]
the equilibrium expression would 4.2  10−3 = [H3O+] = [HCOO−]
be Calculating Ka from pH
• This equilibrium constant is Now we can set up a table…
[HCOOH], M [H3O+], M [HCOO−], M
called the Initially 0.10 0 0
acid-dissociation constant, Ka. Change −4.2  10-3 +4.2  10-3 +4.2  10−3
[H3O+] [A−] At
Equilibrium
Kc = [HA]
0.10 − 4.2  10−3
HA(aq) + H2O(l) A−(aq) + H3O+(aq) = 0.0958 = 0.10
Dissociation Constants 4.2  10−3 4.2  10−3
The greater the value of Ka, the Calculating Ka from pH
stronger [4.2  10−3] [4.2  10−3]
the acid. [0.10]
Calculating Ka from the pH Ka =
= 1.8  10−4 We are assuming that x will be very small
compared to 0.30 and can, therefore, be
Calculating Percent ignored.
Ionization Calculating pH from Ka
• Percent Ionization =  100 Now,
• In this example (x)2
[H3O+]eq = 4.2  10−3 M 1.8  10 (0.30) −5 =
[HCOOH]initial = 0.10 M (1.8  10−5) (0.30) = x2
[H3O+]eq 5.4  10−6 = x2
[HA]initial 2.3  10−3 = x
Calculating Percent Calculating pH from Ka
Ionization pH = −log [H3O+]
Percent Ionization =  100 pH = −log (2.3  10−3)
pH = 2.64
4.2  10−3
0.10 Polyprotic Acids
• Have more than one acidic proton.
= 4.2% • If the difference between the Ka for
Calculating pH from Ka the first
Calculate the pH of a 0.30 M dissociation and subsequent Ka values
solution of acetic is
acid, HC2H3O2, at 25°C. 103 or more, the pH generally depends
HC2H3O2(aq) + H2O(l) H3O+(aq) + only
C2H3O2 on the first dissociation.
−(aq) Weak Bases
Ka for acetic acid at 25°C is 1.8
Bases react with water to produce
 10−5. hydroxide ion.
Calculating pH from Ka Weak Bases
The equilibrium constant expression
is The equilibrium constant expression
[H3O+] [C2H3O2 for
−]
[HC2H3O2] this reaction is
Ka = [HB] [OH−]
Calculating pH from Ka Kb = [B−]
We next set up a table… where Kb is the base-dissociation
[C2H3O2], M [H3O+], M [C2H3O2 constant.
−], M
Initially 0.30 0 0 Weak Bases
Change −x +x +x
At Equilibrium 0.30 − x  0.30 x x
Kb can be used to find [OH−] and, • Anions are bases.
through it, pH. • As such, they can react with
pH of Basic Solutions water in a
What is the pH of a 0.15 M solution hydrolysis reaction to form OH−
of NH3?
[NH4
and the
+] [OH−] conjugate acid:
[NH3] X−(aq) + H2O(l) HX(aq) + OH−(aq)
Kb = = 1.8  10−5 Reactions of Cations with
NH3(aq) + H2O(l) NH4 Water
+(aq) + OH−(aq) • Cations with acidic protons
pH of Basic Solutions (like NH4
Tabulate the data. +) will lower the pH

[NH3], M [NH4 of a solution.

+], M [OH−], M • Most metal cations that are
Initially 0.15 0 0 hydrated in solution also
At Equilibrium 0.15 - x  0.15 x x lower the pH of the solution.
pH of Basic Solutions Reactions of Cations with Water
• Attraction between nonbonding
(1.8  10−5) (0.15) = x2 electrons on oxygen and the
2.7  10−6 = x2 metal causes a shift of the
1.6  10−3 = x2 electron density in water.
(x)2 • This makes the O-H bond more
1.8  10 (0.15) −5 = polar and the water more acidic.
pH of Basic Solutions • Greater charge and smaller size
Therefore, make a cation more acidic.
[OH−] = 1.6  10−3 M Effect of Cations and Anions
pOH = −log (1.6  10−3) 1. An anion that is the
pOH = 2.80 conjugate base of a strong
pH = 14.00 − 2.80 acid will not affect the pH.
pH = 11.20 2. An anion that is the
conjugate base of a weak
Ka and Kb acid will increase the pH.
Ka and Kb are related in this way: 3. A cation that is the
Ka  Kb = Kw conjugate acid of a weak
Therefore, if you know one of them, base will decrease the pH.
you can Effect of Cations and Anions
calculate the other. 4. Cations of the strong
Arrhenius bases will not
Reactions of Anions with affect the pH.
Water 5. Other metal ions will
cause a decrease in pH. • Atoms with an empty valence orbital
6. When a solution contains can be Lewis
both the conjugate base
acids.
of a weak acid and the
conjugate acid of a weak Lewis Bases
base, the affect on pH • Lewis bases are defined as electron-
depends on the Ka and Kb pair donors.
values. • Anything that could be a Brønsted–
Factors Affecting Acid Strength Lowry base is
• The more polar the H-X bond and/or a Lewis base.
the weaker • Lewis bases can interact with things
the H-X bond, the more acidic the other than
compound. protons, however.
• Acidity increases from left to right
across a row and
from top to bottom down a group.
Factors Affecting Acid Strength
In oxyacids, in which
an OH is bonded to
another atom, Y, the
more
electronegative Y is,
the more acidic the
acid.
Factors Affecting Acid
Strength
For a series of oxyacids, acidity
increases
with the number of oxygens.
Factors Affecting Acid
Strength
Resonance in the conjugate bases of
carboxylic acids stabilizes the base
and
makes the conjugate acid more acidic.
Lewis Acids
• Lewis acids are defined as electron-
pair
acceptors.