CHAPTER 14 – ACID-BASE EQUILIBRIA

Last semester, we briefly introduced the concept of acid-base reactions

In this chapter, we are going to take a MUCH MORE in-depth look at acids, bases,
and the kinetics of these reactions

This topic is not just for show:

acid-base chemistry is an important aspect of chemistry

from INDUSTRIAL CHEMISTRY to ECOLOGY to BIOLOGY to BATTERIES to ...

14.1 – Brønsted-Lowry Acids and Bases

Acids and bases have been used and known for centuries, if not millennia.
However, what determines and defines an acid or a base has only been known for less than 150 years

Svante Arrhenius in the 1880’s gave an early description:

Acid: a substance that produces H+ ions when placed in an aqueous solution

Base: a substance that produces OH– ions when placed in an aqueous solution

Back in Section 7.2, you were told that:

acids were compounds that formed H+ ions when dissolved in water

bases were compounds that generated OH– when dissolved in water

These are called the Arrhenius definitions of an acid and a base,

and the compounds termed Arrhenius acids and Arrhenius bases

This is a general, but generally correct, definition of acids and bases...

Example:
We can extend it however by defining it via the H+, what we will refer to as a ‘PROTON’.

Remember: an H atom is exactly: a nucleus made up of 1 p+ only, with a single e– ‘orbiting’ around it...

If we lose an electron from the H atom to make an H+ cation,

all that remains is the nucleus with its 1 p+

Thus, we can reasonably refer to it as “a proton”...

Note: It isn’t that we are really trading free p+ around,

it’s just that the exchange between molecules is equivalent to the trading of an H+...

When an acid is dissolved in water, the H+ does not dissolve and float around like a Na+ ion

Instead, (and every time), the H+ becomes bound to water:

Brønsted and Lowry (in 1923) proposed a more inclusive definition of acids and bases based on the H+:

Brønsted-Lowry acid:

Brønsted-Lowry base:
 Simply, these two require each other! (Like how reduction and oxidation require each other...)

Acids can be many types of compounds:

neutral molecules:

cations:

anions:

The most common acids include the gases HCl, HBr, and the liquid H2SO4

These molecules will ‘donate’ a proton (H+) to water to form hydronium:

*Note:
Bases can also be of many types:

neutral molecules: ammonia (NH3), water (H2O), dimethylsulfide ((CH3)2S)

cations: rare, but some metal coordination complexes (e.g. [Fe(H2O)6]2+)

anions: bicarbonate (HCO3–), bisulfate (HSO4–), hydroxide (OH–)

The most well-known bases include OH-containing ionic compounds

e.g. KOH, Ca(OH)2

These compounds will react with acids to form water:

Acid-H + KOH → Acid– + K+ + H2O

When we think of reactions being reversible, we can think about an acid and a base in a reversible reaction:
When an acid donates its proton,

Examples: acid  proton + conjugate base

When a base accepts a proton,

Examples: base + proton  conjugate acid

In an acid-base reaction, an acid and a base exchange a proton
to become their conjugate base and conjugate acid, respectively

Example: HCl + NH3  Cl– + NH4+

Example: HNO3 + H2O  NO3– + H3O+

Skip to...
14.3 – Relative Strengths of Acids and Bases

Strong acids and strong bases essentially perform irreversible acid-base reactions with water:

Examples:

In contrast, weak acids and weak bases perform reversible acid-base reactions in water:

Examples:
Not all acids or bases are equal... I would imagine this shouldn’t come as a surprise...

We’ve discussed that H2O and HCl are both Brønsted-Lowry acids,

BUT while H2O is benign and harmless (at least to biology),

HCl is highly corrosive, nasty stuff!!

How ‘acidic’ an acid really is defined by how willingly it gives away the acidic proton...

We can describe the strength of an acid by the equilibrium of the acid-base reaction with water as a base:

HCl + H2O  H3O+ + Cl–

H2O + H2O  H3O+ + OH–

Some examples of strong acids and strong bases are given in Figure 14.6 (pg. 679).
These are compounds that essentially fully donate (acids) or accept (bases) protons,
such that there are very few reactant molecules left at equilibrium
By defining the extent of proton exchange with water,
this provides us with a quantifiable means to determine acidity:

The reaction of a Brønsted-Lowry acid with water is called acid ionization:

Generic Example:

Acid-ionization constant, Ka, and the base-ionization constant, Kb:

Ka is the equilibrium constant for the reaction of a given acid with water as a base:

For strong acids, where nearly complete dissociation occurs (i.e. very low [HA]),

Ka is going to be a very large number

For weaker acids, where there is a significant amount of [HA] remaining at equilibrium,
the value for Ka will be considerably smaller...

with weaker and weaker bases showing smaller and smaller Ka

Examples: HCl(aq) + H2O(l) 

H3O+(aq) + H2O(l) 
HF(aq) + H2O(l) 

H2PO4–(aq) + H2O(l) 

NH4+(aq) + H2O(l) 
H2O(l) + H2O(l) 
CH4 (aq) + H2O(l) 
The reaction of a Brønsted-Lowry base with water is called base ionization:

Examples:

Base-ionization constant, Kb:

Kb is the modified equilibrium constant for the reaction of a given base with water as an acid:

For strong bases, where nearly complete reaction occurs (i.e. very low [B]),

Kb is going to be a very large number

For weaker bases, where there is a significant amount of [B] remaining at equilibrium,

the value for Kb will be considerably smaller...

with weaker and weaker bases showing smaller and smaller Kb

Examples: OH–(aq) + H2O(l) 

NH3 (aq) + H2O(l) 

HPO42–(aq) + H2O(l) 

F–(aq) + H2O(l) 

H3O+(aq) + H2O(l) 
Ionization of Weak Acids and Weak Bases

Weak acids and weak bases are considered ‘weak’ because, unlike strong acids and strong bases,
they do not form H3O+ or OH– in a 1:1 ratio.

Instead, only partial ionization occurs and a standard equilibrium is achieved:

HC7H5O2 (aq) + H2O(l)  C7H5O2–(aq) + H3O+(aq)

benzoic acid benzoate anion

𝐾a =

From the equation and the Ka value,

We see the same with weak bases:

C6H5NH2 (aq) + H2O(l)  HC6H5NH2+(aq) + OH–(aq)

aniline anilinium
cation

𝐾b =

From the equation and the Kb value,

Example: At equilibrium, a “0.500 M” solution of formic acid (HCOOH) in water
contains 0.491 M formic acid with [H3O+] = [formate] = 9.40×10–3 M. What is
the Ka of this solution?

𝐾a =

Example: A “0.125 M” solution of the weak base trimethylamine ((CH3)3N) has an

equilibrium [OH–] of 2.82×10–3 M. What is the Kb of trimethylamine?

BUT:

SO:

𝐾b =
Back to 14.2 – pH and pOH

Water is goofy!
But this goofiness is one of its most important characteristics!

As we have seen in previous examples, water can be both an acid and a base:

water as an acid:

water as a base:

Since water can act as an acid and a base... then it can do so to itself!!

Such reactions are called autoionization reactions (meaning: self-ionizing)

As shown above, pure water undergoes autoionization to form hydronium and hydroxide ions

However, this only occurs a small fraction of the time...

Only ~4 molecules in every billion is ionized (two H3O+ and two OH–)

(From Chpt 15, would we be able to argue that K for this reaction is very large or very small?)
We can write the equilibrium constant, K, for this reaction as:

This special case of Kc is called the ion product constant of water and is represented by Kw

Thus:

At 25 °C, Kw = 1.0×10–14, so:

When the [H3O+] and [OH–] are equal, we consider the solution neutral

i.e. there is neither an excess of the acidic H3O+ or of the basic OH–

So: and

Therefore:
An important aspect of how we describe water and aqueous solutions is guided by
the [H3O+] and [OH–] of the particular solution

These values reflect the relative acidity or basicity of that solution:

acidic solutions:

If [H3O+] = 1.0×10–3 M, then:

basic solutions:

If [OH–] = 5.3×10–5 M, then:

Example: Potassium hydroxide was dissolved in water to give [H3O+] = 3.2×10–10 M.

What is the [OH–] in the basic solution?
Example: Suppose we add acid to pure water and the resulting [H3O+] = 1.7×10–4 M.
What is the [OH–] in the acidic solution?

We are rarely going to see (or even be capable of) [H3O+] and [OH–] above 1.0 M, so...

Since Kw = 1.0×10–14, we can treat the [H3O+] and [OH–] as being in a range of
1.0×10–14 M to 1.0 M

BUT, this is a BIG range... the concentration of both ions spans a range of 1014!!

Chemists then, came up with a way to simplify (shorten) these values, but still get the point across:
use a logarithmic scale: p-function
The most widely used p-function is ‘pH’

pH =

Similarly, pOH =

Since, at 25 °C: Kw = [H3O+][OH–] = 1.0×10–14

In a neutral solution, [H3O+] = [OH–],

We can confirm this by going back to the [H3O+] and [OH–] in pure water at 25 °C:

From this information, we can say that at 25 °C:

acidic solutions:

basic solutions:

Summarized in Figure 14.2 (pg. 675)

Roberts: The Box!!

Example: What is the pH of a solution of household (10%) vinegar with a hydronium
concentration of 5.44×10–3 M?

What is the concentration of hydroxide in this solution?

Check:

Since Kw is dependent on T, we find that the [H3O+] and [OH–] at neutral will vary depending on T

Example: At 50 °C, Kw = 5.48×10–14. What is the pH and pOH of a neutral solution?

Is this reaction EXOTHERMIC or ENDOTHERMIC?

Back to...
14.2 (cont’d)

For a strong acid, the acid completely dissociates to become H3O+:

HCl + H2O → Cl– + H3O+

This means that the [HCl]i = [H3O+]eq

So, for a “ 0.100 M “ solution of HCl:

Similarly, for a strong base, the base reacts to completely form OH–:

NaOH → Na+ + OH–

Thus, for a “ 0.0025 M “ solution of NaOH:

For the above 0.100 M HCl solution, the pH =

In contrast, acetic acid (HC2H3O2) is NOT a strong acid:

For a 0.100 M solution of HC2H3O2, pH =

Since, [H3O+] = 10–pH, then [H3O+] =

And again, for the above 0.0025 M NaOH solution, the pOH =

For the weak base, ammonia (NH3): 0.0025 M NH3 has a pOH of
Example: A solution of a weak acid (HA) has some pH. What is the Ka of HA?
HA(aq) + H2O(l)  A–(aq) + H3O+(aq)
Example: What is the pH of a 0.0369 M solution of acetic acid? Ka = 1.8×10–5
HC2H3O2(aq) + H2O(l)  C2H3O2–(aq) + H3O+(aq)

𝐾a =

So:

pH =
Example: A 0.0555 M solution of the weak base, butylsulfide (CH3CH2CH2CH2S–),
has a pH of 11.74. What is the Kb of butylsulfide?
CH3CH2CH2CH2S–(aq) + H2O(l)  CH3CH2CH2CH2SH(aq) + OH–(aq)

BUT:

𝐾b =
Percent ionization is a simple method for determining acidity:

Example: A 0.573 M solution of acetic acid in water yields [H3O+] = 3.22×10–3 M;

what is the % ionization of acetic acid?

% 𝑖𝑜𝑛𝑖𝑧𝑎𝑡𝑖𝑜𝑛 =

Example: A 0.0256 M solution of ammonia in water has a pH of 10.83;

what is the % ionization of acetic acid?

% 𝑖𝑜𝑛𝑖𝑧𝑎𝑡𝑖𝑜𝑛 =
Mixture of a strong acid with a weak acid:

Suppose we make a solution of 0.100 M HCl with 0.100 M HC2H3O2, what is the final pH?

Notice that:

The [H3O+] derives from three sources: HCl, HC2H3O2, and H2O

However, HCl being a strong acid converts completely to H3O+,

Thus, 0.100 M HCl yields 0.100 M H3O+

Since we know the [HC2H3O2]i and the “starting concentration” of H3O+ from HCl,

we can determine the [HC2H3O2]eq and [C2H3O2–]eq

𝐾a =
 So: In the presence of a strong acid,

the contribution of H3O+ to the solution by the weak acid is negligible compared to

the H3O+ generated by the strong acid

When mixing two weak acids, this gets more complicated...

However, if one weak acid has a Ka more than 100× the other AND

the concentrations are equal (or there is more of the “better” weak acid),

then the same ASSUMPTION can be made: the weaker acid does not contribute significantly
14.4 – Hydrolysis of Salts

Acids: H3O+(l) + H2O(l)  H3O+(aq) + H2O(l) Ka = ~1 (100)

HF(aq) + H2O(l)  H3O+(aq) + F–(aq) Ka = 6.6×10–4
H2PO4–(aq) + H2O(l)  H3O+(aq) + HPO42–(aq) Ka = 6.3×10–8
NH4+(aq) + H2O(l)  H3O+(aq) + NH3 (aq) Ka = 5.6×10–10
H2O(l) + H2O(l)  H3O+(aq) + OH–(aq) Ka = ~10–14

Bases: OH–(aq) + H2O(l)  OH–(aq) + H2O(l) Kb = ~1 (100)

NH3 (aq) + H2O(l)  OH–(aq) + NH4+(aq) Kb = 1.8×10–5
HPO42–(aq) + H2O(l)  OH–(aq) + H2PO4–(aq) Kb = 1.6×10–7
F–(aq) + H2O(l)  OH–(aq) + HF(aq) Kb = 1.5×10–11
H2O(l) + H2O(l)  OH–(aq) + OH–(aq) Kb = ~10–14

Note that in the above examples, from most-to-least basic, we get:

basicity (most-to-least):

This is opposite to what we see for the acidity of their conjugate acids:

acidity (most-to-least):

If we take any pair of conjugate acid/conjugate base, we notice something particular:

HA(aq) + H2O(l)  A–(aq) + H3O+(aq) ... with some associated value for Ka

A–(aq) + H2O(l)  HA(aq) + OH–(aq) ... with some associated value for Kb

Adding together:
 [H3 O+ ][A− ] [HA][OH− ]
Further, since: 𝐾a = and 𝐾b =
[HA] [A− ]

So:

Example: We can see this is true with HF/F–:

Example: The Ka of benzoic acid is determined to be 6.4×10–5; what is the Kb of its
conjugate base, benzoate?

Because of this relationship of Ka and Kb to a constant,

this has significant implications about the strength of the conjugate pair:

When Ka is large,

When Kb is large,

Examples: NH3 has a Kb = 1.8×10–5

H3O+ has a Ka ~1

Figure 14.8 (pg. 682) shows the relationships between conjugate pairs and their acid and base strengths
Ionic salts are really just the products of an acid-base reaction:

Example: NH3 (aq) + HCl(aq)  NH4Cl(aq) = NH4+(aq) + Cl–(aq)

When dissolving the salt made from a weak base and strong acid,
we can understand the effect on the acidity of the solution:

Example:

BUT, what if we don’t know the Ka of this “conjugate acid”?

 Example: What is the pH of a solution of 0.754 M NH4Cl? (Solving using assumptions...)

Salts of Weak Acids and Strong Bases

HCH3CO2 (aq) + NaOH(aq)  NaCH3CO2 (aq) + H2O(l)

When dissolving a salt made from a weak acid and a strong base,
we can understand the effect on the basicity of the solution:

Example: NaCH3CO2 (aq) = CH3CO2–(aq) + Na+(aq)

 Again, we don’t know the Kb of CH3CO2–,

Example: What is the pH of a solution of 0.0345 M NaCH3CO2? (This time, no assumptions...)

CH3CO2–(aq) + H2O(l)  HCH3CO2 (aq) + OH–(aq)

Equilibrium in a Solution of Weak Acid and a Weak Base

The solution is determined by the Ka of acid and Kb of base

Example: If we dissolve ammonium fluoride in water, will the solution be basic or acidic?
NH4F(s)  NH4+(aq) + F–(aq)

Example: If we dissolve anilinium acetate, C6H5NH3CH3CO2, in water,

will the solution be basic or acidic?
C6H5NH3CH3CO2 (s)  C6H5NH3+(aq) + CH3CO2–(aq)
14.5 – Polyprotic Acids (and Bases)

So far, we have talked about Brønsted-Lowry acids donating a single H+,

but there are many acids that can donate more than one H+...
(Technically, every H in a compound can be acidic... some are just much more acidic than others.)

Most of the examples we have looked at so far are examples of monoprotic acids:
acids that can donate a single H+ (mono-: one, proto: proton)

Examples: HCl: HCl(aq) + H2O(l)  Cl–(aq) + H3O+(aq)

HCH3CO2: HCH3CO2 (aq) + H2O(l)  CH3CO2–(aq) + H3O+(aq)
HNO3: HNO3 (aq) + H2O(l)  NO3–(aq) + H3O+(aq)

In each of the above cases, a single proton is donated to a base (H2O) to yield H3O+
Note: acetic acid (HCH3CO2) is considered monoprotic
because the other three H’s are incredibly weak acids (Ka < 10–30 !!!)

Other acids can donate multiple H+s:

Acids that can donate two H+ are called diprotic acids (di-: two, proto: proton)

Examples:

It is important to observe that ionization occurs in a stepwise fashion:

One H+ is donated first, with an associated Ka1,

THEN the second H+ is donated, with its own Ka2

The 2nd H+ is always less acidic than the first (i.e. Ka2 < Ka1),

Also, because an H+ is donated,

Example: Carbonic acid (H2CO3):
1st ionization:

2nd ionization:
Example: What are the [H3O+], [HCO3–], and [CO32–] in a solution with
an initial [H2CO3] = 0.033 M?
Triprotic acids, while uncommon, do occur... (tri-: three, proto: proton)

The ‘flagship’ example of a triprotic acid is phosphoric acid (H3PO4):

H3PO4: 1st ionization:

2nd ionization:

3rd ionization:

As with acids, there are polyprotic bases:

Example:
14.6 – Buffers

Acetic acid (HCH3CO2) has a Ka = 1.8×10–5, which defines it as a:

When 1.00 M HCH3CO2 is added to pure water,

only a small amount of CH3CO2– and H3O+ is produced

In fact, at equilibrium, the [CH3CO2–] = [H3O+] = 4.19×10–3 M

Which means only about 0.419% of the acid actually donated a H+...
However, the solution now has a pH = 2.38, so the solution is:

Similarly, acetate (CH3CO2–), the conjugate base of acetic acid, has a 𝐾b =

When 1.00 M CH3CO2– is added to pure water,

only a small amount of HCH3CO2 and OH– is produced

In fact, at equilibrium, the [HCH3CO2] = [OH–] = 2.38×10–5 M

Which means only about 0.00238% of the base actually accepted a H+...
However, the solution now has a pH = 9.38, so the solution is:

NOTE: In neither case will the [HCH3CO2] and [CH3CO2–] be equal... ever!!

Acetic acid only produces a small amount of acetate,

then the reaction is at equilibrium and IS DONE!
Acetate only produces an even smaller amount of acetic acid,
then the reaction is at equilibrium and IS DONE!
So then, what happens if we intentionally make a solution with both 1.00 M HCH3CO2 AND
1.00 M CH3CO2–?

As it turns out, very interesting things!!

Example: So: 1.00 M HCH3CO2 and 1.00 M CH3CO2–...What is the pH of this solution?
HCH3CO2 (aq) + H2O(l)  C2H3O2–(aq) + H3O+(aq) Ka = 1.8×10–5

So: A 1.00 M HCH3CO2 solution gives a pH = 2.38, and a 1.00 M CH3CO2– gives a pH = 9.38
But a solution of 1.00 M HCH3CO2 and 1.00 M CH3CO2– gives a pH = 4.75

Ka of HCH3CO2 =

Kb of CH3CO2– =
But, things get even more interesting...

Consider 0.100 M HCl... Because HCl is a strong acid, the [H3O+]eq = [HCl]i

So: pH =

Let’s consider adding 0.100 M HCl to our mixed solution above... What is the pH now?

Example:

This shows us that, instead of HCl reacting with the water to generate H3O+,
the HCl reacted with acetate (C2H3O2–) to give acetic acid (HC2H3O2)...

This should not be surprising since acetate (Kb = 5.6×10–10) is a better base
than water (Kb = 10–14)
This is a handy property!!!
What you have seen is the power of a buffer...

Buffer: a solution of a weak acid and its conjugate base (or weak base and conjugate acid)
in equal (or near equal) proportions

Buffer solutions contain both an acid that is better than water and a base that is better than water
This mixture of acid and base then protects the pH by absorbing acids and bases that may be added,
preventing large changes in the [H3O+] and [OH–]
Henderson-Hasselbach Equation

[A− ][H3 O+ ]
For any given acid: 𝐾a =
[HA]

Rearranging:

So, the pH of a buffered solution is determined by pKa (–log Ka)

and the ratio of acid and conjugate base

When there is equal amounts of acid and conjugate base, the pH = pKa
When there is more acid present than conjugate base,

When there is more conjugate base present than acid,

Example: What is the pH of acetic acid/acetate buffer containing equal amounts of acetic acid and
acetate ion?
Ka = 1.8×10–5

Example: What is the pH of acetate buffer containing 0.025 M acetic acid and
0.100 M acetate?

Example: What is the pH of an ammonia buffer containing 0.0667 M NH3 and 0.183 M NH4+?
Kb of ammonia = 1.8×10–5
From the original example of the acetate buffer: 0.025
M acetic acid and 0.025 M acetate,
we saw that addition of 0.00100 M HCl changed the pH from 4.74 to 4.71...
about a 0.63% decrease

If we add 0.00100 M HCl to a different acetate buffer solution:

0.045 M acetic acid and 0.0050 M acetate,
we find that the pH changes from 3.79 to 3.69... about a 2.7% decrease
This is quite a bit larger than in the first case

Note: while the total concentration of acetic acid and acetate in both buffer solutions is the same:
(0.025 M + 0.025 M) = (0.045 M + 0.0050 M) = 0.050 M
the buffer with equal concentrations did a better job of protecting the pH than the buffer with less base

So: the buffering effect is not permanent:

In the above buffer, if we add more and more HCl,

we find that the [H3O+] (and pH) will eventually shift:
5

HCl (M) [H3O+] (M) pH

0.000 1.8×10–8 4.7 4

0.001 2.0×10–8 4.7

0.005 2.7×10–8 4.6 3
pH

0.010 4.2×10–7 4.4

0.015 7.1×10–7 4.1 2

0.020 1.6×10–7 3.8

0.022 2.6×10–6 3.6 1

0.024 5.6×10–6 3.3

0.025 9.4×10–6 3.0 0
0 0.005 0.01 0.015 0.02 0.025 0.03
0.026 1.6×10–6 2.8
HCl added (M)
0.028 3.3×10–6 2.5
0.030 5.2×10–6 2.3
The absolute amount of buffer molecules matters as well...

In our example acetate buffer: 1.00

M acetic acid and 1.00 M acetate,
we saw that addition of 0.100 M HCl changed the pH from 4.74 to 4.66... about a 1.7%
decrease

0.200 M acetic acid and 0.200 M acetate,

If we decrease the concentrations to:
addition of 0.100 M HCl changes the pH from 4.74 to 4.44... about a 6.3% decrease

If we further decrease the concentrations to: 0.100

M acetic acid and 0.100 M acetate,
addition of 0.100 M HCl changes the pH from 4.74 to 2.88... about a 39% decrease

This is a much larger change in pH for the same amount of acid...

When the pH of a buffer is at its pKa, the buffer is at its maximum buffering ability

For most buffers, once the pH has shifted ±1 pH unit, the buffer has lost most of its buffering ability

When plugged into the Henderson-Hasselbalch equation: pH = pKa ± 1

Buffer Capacity is the range across which a buffer can mute or protect the change in pH (or pOH)

Within the buffer range, the buffer can ‘absorb’ acid and base with the pH changing only very little...

Outside of this range, the buffer is unable to ‘protect’ the solution from dramatic changes in pH
 Selection of a Good Buffer:

1.

2.

14.7 – Acid-Base Titrations

Covered by the DEMO!