Chapter 17 Acids and Bases

- we are all familiar with 'acids'

- depicted on television as burning liquids
- from foods (i.e. vinegar)
- taste "sour" or "tart'
- less familiar with 'bases'
- taste "bitter" - for example, beer or coffee

- several different definitions have been used for

the terms "acid" and "base" over the years
17.1 The Arrhenius Theory

Svante Arrhenius was interested in "electrolytes" and

"electrolysis" and he devised much of the early theory to
explain ions in solution

- according to Arrhenius, acids dissolve in water to give

protons while bases dissolve to give hydroxide ions and
these react to give water and a salt

- this reaction is called "neutralization":

acid + base → salt + water
for example,
hydrochloric acid yields a proton in solution
sodium hydroxide generates hydroxide ions

hence:
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O

in ionic form:
H+(aq) + Cl-(aq) + Na+(aq) + OH-(aq) → Na+(aq) + Cl-(aq) + H2O

or in "net" ionic form:

H+(aq) + OH-(aq) → H2O
- from the Arrhenius point of view, HCl is an acid because it
participates in a neutralization reaction that gives water
and a salt (in this case, "table salt") and NaOH is a base
because it also participates in a neutralization reaction

that is, the reason that we know that 'HCl' and 'NaOH'
are an acid and a base, respectively, is because they
give us water - hence, they must yield up a proton and a
hydroxide ion

this was a good "first step" but it was not sufficient

- for example, it does not explain "ammonia"
7.2 Bronsted-Lowry Theory

redefines acids and bases in terms of their ability to

donate or accept protons
an 'acid' is a 'proton donor'
a 'base' is a 'proton acceptor'

hence, anything that increases the proton content of a

solution is, by definition, an acid and anything that
decreases it - by accepting a proton - is a base

- explains ammonia which accepts protons

but this definition is also slightly flawed because bases
don't "accept" protons - they steal them!

- arrow pushing is how we show this:

Bronsted-Lowry gives us the concept of "conjugate acids
and bases"

NH4+(aq) + OH-(aq) → NH3 (aq) + H2O

acid base conj. conj.
base acid

NH4+/NH3 and OH-/H2O both form acid/base pairs and

the partner of an acid in such a pair is called "the
conjugate base" (and vice versa for a base)

Note: this all depends upon how the reaction is written!

also, most acid/base reactions are actually equilibria

for example, acetic acid

CH3COOH(aq) + H2O W CH3COO-(aq) + H3O+(aq)

acid base base acid

conjugates

we can write an equilibrium expression for this reaction

 Ka = [CH3COO-][H3O+] / [CH3COOH]

where [H2O] is treated as a constant and incorporated

into the value of Ka, the "acid ionization constant"

could equally well write an expression for Kb, the "base

ionization constant"

Bronsted-Lowry is better than Arrhenius at accounting

for substances that can both donate and accept protons
such as water. Such substances are called "amphiprotic"
17.3 The (Auto)Ionization of Water and pH

- water is one of many substances that are capable of

donating a proton to itself

that is, H2O + H2O W H3O+(aq) + OH-(aq)

acid base conj. conj.
acid base

this is more commonly written as,

H2O W H+(aq) + OH-(aq)
as an equilibrium, we can write the equilibrium constant
expression,

K = [H+(aq)][OH-(aq)] / [H2O]

but, since the concentration of water is a constant, this is

more commonly expressed as:

Kw = [H+][OH-]

simply put, the concentrations of [H+] and [OH-] in any

and all aqueous solutions are inversely related
furthermore,
Kw = 1.0 x 10-14 = [H+][OH-]

or, in pure water,

[H+] = [OH-] = (1.0 x 10-14)½ = 1.0 x 10-7

This is our definition of "neutral". In pure water with no

other species present, the concentrations of both H+(aq)
and OH-(aq) are the same.

Note: Kw is an "ion product" as it is only concerned with

the ionic components of the equilibrium.
Measuring the concentration of either the protons or
hydroxide ions in a solution results in a measurement of
the other.

We could use molarity and scientific notation to express

the concentration of protons and hydroxide ions (for
example, [H+] = 2.34 x10-5 M) but we more frequently
use a "p-function"

By definition, a p-function is the "negative log10" of the

quantity in question.
pH = -log [H+]
i.e. pH = -log (2.34 x10-5) = 4.631
note that p-functions are not restricted to simply
measuring pH

pOH = - log [OH-]

pKa = - log Ka
pKb = - log Kb
pO2 = - log [O2]
etcetera

The purpose of the p-functions is to change to a

logarithmic scale but not to change the answers.
Also, pH is not actually -log[H+] but rather it is the
negative logarithm of the hydrogen ion activity.

That is, pH = -log(άH+)

The "activity" is the amount of a substance that is

actually available to react - which is not necessarily
equal to the amount present. This is a subtle point and
not one that we will pursue further in this course.
Note:

Kw = [H+][OH-] = 1.0 x10-14

pKw = pH + pOH = 14

- as pH decreases, pOH increases

and vice versa
Acid Strength
- the strength of an acid is not necessarily correlated with
its concentration
- that is, a dilute solution of a strong acid might be
more reactive than a concentrated solution of a
dilute acid

- acid strength is a measure of how freely an acid will

donate it proton
- for example, perchloric acid (HClO4) is a strong
acid because it will readily give up its proton to any
other base - hence, the perchlorate ion (ClO4-) is a
lousy base
- the stronger the acid, the weaker the conjugate base
- that is, a strong acid will lose its proton to any other
base and is incapable of stealing the proton back

- the strongest acid in water is the hydronium ion (H3O+)

- strong acids, when dissolved in water, will donate their

proton to water
i.e. HCl + H2O → Cl- + H3O+
HClO4 + H2O → ClO4- + H3O+
HNO3 + H2O → NO3- + H3O+
- but any acid (or base) can only donate to their
concentration

- that is, if the concentration of hydrochloric acid in

an aqueous solution is 0.010 M, then the maximum
concentration of H+ is 0.010 M.
(and it can only react with 0.010 M of
anything else!)

- hence, a dilute solution of a strong acid is not

particularly reactive but a concentrated solution is!
17.4 Strong Acids and Strong Bases

- a strong acid or a strong base will completely

dissociate in aqueous solution - giving the concentration
of H+ and OH- directly

- generally, can ignore the contribution of water as it will

be very small compared to the contribution from the
strong acid or base - except when the concentration of
the strong acid or base is close to or less than 1 x10-7 M
- hence, calculating the pH, the pOH, or the pCl for the
dissolution of 0.23M HCl is aqueous solution is
straightforward:

0.23M HCl → 0.23M H+ + 0.23M Cl-

pH = -log(0.23) = 0.638

since, [H+] = [Cl-], pCl = pH = 0.638

pOH = 14 - pH = 14 - 0.638 = 13.362

Table 17-2 has the common "Strong acids and Bases"
"Are you wondering ….."
These are sections of the book that seem a little tangental at times.
However, the ones on pgs. 676 and 682 are important.

pg. 676 How to calculate [H3O+] in an extremely dilute

solution of a strong acid.

Example: What is the pH of a solution of 1.0 x10-8 HCl?

If we assume [H+]total = 1.0 x10-8, then the answer would

be pH = -log (1.0 x 10-8) = 8
- but clearly, an acid should have a pH more acidic
than neutral
- must take auto-ionization of water into account

H2O + H2O W H3O+ + OH-

HCl + H2O W H3O+ + Cl-

[H3O+]total = 1.0 x10-8 + x (from water)

- hence, Kw = [H3O+][OH-] = 1.0 x10-14

(x + 1.0 x10-8)(x) = 1.0 x10-14

x2 + 1.0 x10-8x - 1.0 x10-14 = 0

solving the quadratic equation gives,

x = -(1.0 x10-8) ± [(1.0 x10-8)2 - 4(1)(1.0 x10-14)]½

2(1)

= -1.0 x10-8 ± 2.0024 x10-7

2
Î x = 9.512 x10-8

and [H3O+]total = 1.0 x10-8 + x

= 1.0 x10-8 + 9.952 x10-8
= 1.0512 x10-7 Î pH = 6.978
17.5 Weak acids and Weak bases

- the difference between a "strong acid" and a "weak

acid" is that a weak acid is only partially dissociated

- some of the "parent" acid will be present in solution

along with the conjugate base
i.e.
strong acid: HClO4 + H2O W H3O+ + ClO4- Keq > 106

weak acid: CH3COOH + H2O W CH3COO- + H3O+

Keq = 1.8 x10-5
- the size of the equilibrium constants tell us that in the
strong acid, the concentrations of H3O+ and ClO4- are
very large compared to the concentration of HClO4
whereas in the weak acid, the concentrations of H3O+
and CH3COO- are small compared to CH3COOH.

- why does this happen? the covalent bond between the

proton and the acetate ion is much stronger than the one
holding the proton to the perchlorate ion

Note: even the strongest covalent bond will eventually

break, so even methane (CH4) is an acid - just a very,
very weak acid!
- to talk about weak acids, we use pKa's as a method of
presenting the acid equilibrium constant
working through questions follows the same steps that
we used in solving other equilibrium problems:

example: determine the Ka of a weak acid if the total

concentration of acid is 0.300 M and the pH is 2.46

step 1) write out equilibrium

HA W H+ + A-

step 2) write out equilibrium constant expression

Ka = [H+][A-] / [HA]
step 3) ICE table
HA W H+ + A-
initial 0.300 M 0.0 M 0.0 M
change -x +x +x
equilibrium 0.300 - x x x

but, in this case, we know "x" because we know the final

pH - hence, x = [H+] = 10-2.46 = 3.467 x10-3 M

hence, [H+] = [A-] = 0.003467 M; [HA] = 0.2965 M

Ka = (0.003467)(0.003467)/(0.2965) = 4.054 x10-5

Example:
What is the pH of a 1.0 M solution of a weak acid (Ka =
4.054 x10-5)?

step 1) equation: HA W H+ + A-

step 2) equilibrium: Ka = [H+][A-] / [HA]

step 3) ICE: HA W H+ + A-
initial 1.0 0.0 0.0
change -x +x +x
equilibrium 1.0 - x x x
step 4) Ka = (x)(x) / (1.0 - x) = 4.054 x10-5

step 5) x2 = 4.054 x10-5(1.0 - x)

= 4.05 x10-5 - 4.054 x10-5x

x2 + 4.054 x10-5x - 4.054 x10-5 = 0

step 6)
x = -(4.054 x10-5) ± [(4.054 x10-5)2 - 4(1)(4.054x10-5)]½
2(1)
x = -4.054 x10-5 ± 1.2734 x10-2 Î x = 0.00635
2
step 7) [H+] = x = 0.00635
pH = -log(0.00635) = 2.197

step 8) can't really check the pH but we can check the

equilibrium:
Ka = (0.00635)2 /(1 - 0.00635) = 4.058 x10-5

Also, does a pH of 2.197 sound reasonable? Yes. In the

last problem, an acid concentration of 0.300 M resulted
in a pH of 2.46. It makes sense that an increase in the
acid concentration should result in a decrease in pH (an
increase in the number of H+ ions in solution).
Example:
A solution of vinegar is typically about 3% acetic acid in
water, which corresponds to about 0.500 M. At this
concentration, with Ka = 1.8 x10-5, what is the pH of
vinegar?

step 1)
What about weak bases?
Example:
What is the pH of a 2.3 x102 M solution of Ammonia
(Kb = 1.8 x10-5)?
step 1)
book advocates using a simplifying assumption - that the
amount of dissociation is small compared to the overall
concentration of acid

in acetic acid example, we had

Ka = (x)(x) / (0.500 - x) = 1.8 x10-5

but if x << 0.500 then (0.500 - x) ≈ 0.500 and the equation

would be:
x2 / 0.500 = 1.8 x10-5
x2 = 0.90 x10-5 Î x = 0.003 M
this is reasonably close to the value that we got using
the quadratic, 2.99 x10-3 M, and certainly within rounding
errors
- hence, we could have saved some time this way

however, consider the example of a weak base such as

ammonia
Kb = (x)(x) / (0.023 - x) = 1.8 x10-5
after simplifying,
x2 / 0.023 = 1.8 x10-5
x2 = 4.14 x10-5 Î x = 6.434 x10-4
compared to 6.345 x10-4
- while this is close, they are not exactly the same and
could lead to errors.

Simplification does not always work. It is necessary to

know the long route, no matter what.

As an approach, you can always try the short route first

but if x is more than 5% of the concentration, then do the
quadratic.

Note: quadratic formula always works but is slower.

simplification doesn't always work but is fast.
Percent Ionization

- the percent ionization gives the proportion of ionized

molecules (or dissociated molecules)

% ionization = molarity of H+ from HA x 100%

molarity of HA

- strong acids - percent ionization is virtually 100%

- weak acids - percent ionization is less than 100%
but it changes with concentration
- the more dilute the acid, the greater the % ionization
i.e. for acetic acid
% ionization is 0.6% at 0.500 M
% ionization is 4% at 0.010 M
% ionization is 100% at 0.0000010 M

- this gives us a clue as to what sort of answer to expect

as the more dilute the acid, the closer the concentration
of H+ will be to the concentration of the acid
that is, [H+] goes to [HA] as the acid gets more dilute
Were you wondering ….. on page 682
- math is obtuse and it is not something that we are
going to deal with overtly at this point, however, it is a
reminder that water is a good acid and a good base
under dilute conditions

- also, the iterative process is a stepwise approach used

in a lot of computer programming

- we will need to consider this when we talk about ions

as acids and bases, and more importantly, the titration of
weak acids and bases - but we will find a mathematically
less obtuse answer!
17.6 Polyprotic Acids

- most of the acids that we have dealt with so far are

"mono-protic" - they only give up a single proton upon
dissociation (and the bases only accept a single proton)

- some acids are "polyprotic" as are some bases:

polyprotic acids: H3PO4, H2SO4, H2SO3, H2CO3

also the organic acids: oxalic, maleic, succinic

polyprotic bases: diaminoethane, morphine, DNA, RNA

- as examples, we will deal with two that are of equal
importance to industry - phosphoric acid and sulfuric acid

Phosphoric acid, H3PO4, has three acid equilibria:

1) H3PO4 W H+ + H2PO4-
Ka1 = [H+][H2PO4-] / [H3PO4] = 7.1 x10-3
2) H2PO4- W H+ + HPO42-
Ka2 = [H+][HPO42-] / [H2PO4-] = 6.3 x10-8
3) HPO42- W H+ + PO43-
Ka3 = [H+][PO43-] / [HPO42-] = 4.2 x10-13
as you might expect, Ka1 > Ka2 > Ka3
- it gets harder to remove the positively charged
proton as the species gets more negatively charged

One way to illustrate what is going on is with a

"speciation curve" - a plot of pH versus concentration:
Working questions with polyprotic acids means that we
have to take each deprotonation into account.

Example,
What is the pH of a 0.10M solution of phosphoric acid?
- need to do this step-wise
first reaction:
step 1) H3PO4 W H+ + H2PO4-

step 2) Ka = [H+][H2PO4-] / [H3PO4] = 7.1 x10-3

step 3) ICE table
H3PO4 W H+ + H2PO4-
initial 0.10 M 0.0 0.0
change -x x x
equilibrium 0.10 - x x x

step 4) Ka = x2 /(0.10 - x) = 7.1 x10-3

check simplification: x2 / 0.10 = 7.1 x10-3

x = (7.1 x10-3 x 0.10)½
= 0.026 M
which is not small compared to 0.10 M
step 5) go the quadratic route
x2 = 7.1 x10-3(0.10 - x)
x2 + 7.1 x10-3x - 7.1 x10-4 = 0

step 6) x = -(0.0071) ± [(0.0071)2 - 4(1)(-7.1 x10-4)]½

x = -0.0071 ± 0.05376 Î x = 0.02333
2

step 7) [H+] = [H2PO4-] = 0.02333M; [H3PO4] = 0.07667M

step 8) check the equilibrium - it works

but what about the second step? does the second
deprotonation now contribute?

step 1) write out equation: H2PO4- W H+ + HPO42-

step 2) Ka = [H+][HPO42-] / [H2PO4-] = 6.3 x10-8

Note that we already have [H+] = 0.02333 M and [HPO4-] =

0.02333 M from the first equilibrium. This means that we
are not starting from "scratch" here and the ICE table
must reflect this.
step 3) ICE table
H2PO4- W H+ + HPO42-
initial 0.02333M 0.02333M 0.0M
change -x +x +x
equlibrium 0.02333 - x 0.02333 + x x

step 4) re-write Ka
Ka = (0.02333 + x)(x) / (0.02333 - x) = 6.3 x10-8

if we assume that 'x' is small compared to 0.02333,

then we get: (0.02333)(x) / (0.02333) ≈ 6.3 x10-8
or: x = 6.3 x10-8 M
In this instance, the simplification works as 6.3 x10-8 M is
very much smaller than 0.02333 M. Hence,

[H+] = 0.02333 + 6.3 x10-8 ≈ 0.02333 M

and pH = -log(0.02333) = 1.632

Note that since Ka3 is even smaller, it would make a very

small contribution to [H+] - one that we can safely ignore.
Example:
What is the pH of a 0.10M solution of sulfuric acid?
- for sulfuric acid, the first deprotonation proceeds
100% as it is a "strong acid" and hence, we don't have to
calculate this as the concentration of protons will equal
the concentration of the acid. That is,
H2SO4 → H+ + HSO4-
0.10M 0.10M

Note that these are the initial concentrations for these

species in the second deprotonation, so once again, for
the second deprotonation we are not starting from
'scratch'.
the second deprotonation:
step 1) HSO4- W H+ + SO42-

step 2) Ka = [H+][SO42-] / [HSO4-] = 0.013

step 3) ICE table:

HSO4- W H+ + SO42-
initial 0.10 0.10 0.0
change -x x x
equilibrium 0.10 - x 0.10 + x x

step 4) Ka = (0.10 + x)(x) / (0.10 - x) = 0.013

step 5)
x2 + 0.10x = 0.013(0.10 - x) = 0.0013 - 0.013x
x2 + 0.113x - 0.0013 = 0

step 6) x = -(0.113) ± [(0.113)2 - 4(1)(-0.0013)]½

2(1)
= (-0.113 ± 0.134)/2
Î x = 0.0105 or x = -0.1235

step 7) [H+]e = 0.10 + x = 0.10 + 0.0105 = 0.1105M

pH = -log(0.1105) = 0.957
less than 1, as expected, because 0.10M H+ = pH 1
17.7 Ions as Acids and Bases
- ionic species that are components of acid/base
equilibria will change the pH of a solution when dissolved

- further, "the product of the ionization constant of an

acid and its conjugate base equals the ion product of
water"
- that is, Ka x Kb = Kw

for example, NaF in water gives F- which binds H+

because it is the conjugate base of a weak acid
F- + H+ W HF Ka-1 = [HF]/[H+][F-]
Hydrolysis
- dissolving NaCl in water gives Na+(aq) and Cl-(aq) but no
change in pH as Cl- is a weak base and doesn't pull
protons from water and Na+ is a weak acid
- dissolving NH4Cl in water gives NH4+(aq) and Cl-(aq)
which undergoes a change in pH due to the hydrolysis of
the ammonium ion
NH4+ + H2O W NH3 + H3O+

- the ionic component of a weak acid or base, when

added to water as a salt, will result in the breaking up of
water molecules and a shift in the pH from neutrality
Example:
What is the pH of a 0.10M solution of NaF?

step 1) F- + H2O W HF + OH-

step 2) Kb = [HF][OH-] / [F-] = Kw/Ka = 1.52 x10-11

step 3) ICE: F- W HF + OH-

initial 0.10M 0.0 0.0
change -x x x
equilibrium 0.10 - x x x
step 4) Kb = (x)(x) / (0.10 - x) = 1.52 x10-11

step 5) in this case, it is safe to assume that 'x' is

going to be very much less than 0.10, hence,

x2 / 0.10 = 1.52 x10-11

x = [(1.52 x10-11)(0.10)]½
= 1.23 x10-6

step 7) [OH-]e = x = 1.26 x10-6 Î pOH = 5.909

Î pH = 14 -5.909 = 8.09
- the fluoride ion shifts the pH from neutral to basic
17.8 Molecular Structure and Acid-Base Behaviour

- this section deals with questions around why some

acids are strong and some are weak - and the simple
answer is the strength of the bond holding the proton

- however, general trends are:

acidity increases going down a group
HF Ka = 6.6 x10-4
HCl Ka = 1.3 x106
HBr Ka = ≈108
HI Ka = ≈109
oxoacids - acidity increases with the number of oxygens
KHClO2 < KHClO3 < KHClO4
- decreases for different central atoms as one
goes down a group
KHClO4 > KHBrO4 > KHIO4

strength of organic acids

- the length of the organic chain has little effect
- presence of an electron withdrawing group has a
major effect on Ka

strength of amine bases - leave for organic chemistry

17.9 Lewis Acids and Bases
- this is the most useful and general definition of acids
and bases
- it encompasses all of the other definitions and then
some

- a "Lewis acid" is an electron pair acceptor

- a "Lewis base" is an electron pair donor

i.e. H+ accepts a pair of electrons from OH-

O2 donates a pair of electrons to the iron in
hemoglobin