Acid-Base Chemistry

O Water
O pH
O eIinitions oI Acids and Bases
O $alts
O Acid-Base Character
O Acid-Base Titrations

ater
We typically talk about acid-base reactions in aqueous-phase environments -- that is, in the
presence oI water. The most Iundamental acid-base reaction is the dissociation oI water:
H
2
O H

OH
-

In this reaction, water breaks apart to Iorm a hydrogen ion (H

) and a hydroxide ion (OH

-
). In
pure water, we can deIine a special equilibrium constant (K
w
) as Iollows:
K
W
|H

||OH
-
| 1.00x10
-14

Where K
w
is the equilibrium constant Ior water at 25 C (unitless)
|H

| is the molar concentration oI hydrogen

|OH
-
| is the molar concentration oI hydroxide
An equilibrium constant less than one (1) suggests that the reaction preIers to stay on the side oI
the reactants -- in this case, water likes to stay as water. Because water hardly ionizes, it is a very
poor conductor oI electricity.
pH
What is oI interest in this reading, however, is the acid-base nature oI a substance like water.
Water actually behaves both like an acid and a base. The acidity or basicity oI a substance is
deIined most typically by the pH value, deIined as below:
pH -log|H

|
At equilibrium, the concentration oI H

is 1.00 10
-7
, so we can calculate the pH oI water at
equilibrium as:
pH -log|H

| -log|1.00 10
-7
| 7.00
$olutions with a pH oI seven (7) are said to be neutral, while those with pH values below seven
(7) are deIined as acidic and those above pH oI seven (7) as being basic.
pOH gives us another way to measure the acidity oI a solution. It is just the opposite oI pH. A
high pOH means the solution is acidic while a low pOH means the solution is basic.
pOH -log|OH
-
|
pH pOH 14.00 at 25C
efinitions of acids and bases
O Arrhenius
acid: generates |H

| in solution
base: generates |OH
-
| in solution
normal Arrhenius equation: acid base salt water
example: HCl(aq) NaOH(aq) NaCl(aq) H
2
O(l)
O Bronsted-Lowery:
acid: anything that donates a |H

| (proton donor)
base: anything that accepts a |H

| (proton acceptor)
normal Bronsted-Lowery equation: acid base acid base
example: HNO
2
(aq) H
2
O(aq) NO
2
-
(aq) H
3
O

(aq)
Each acid has a conjugate base and each base has a conjugate acid. These conjugate pairs
only diIIer by a proton. In this example: NO
2
-
is the conjugate base oI the acid HNO
2
and
H
3
O

is the conjugate acid oI the base H

2
O.
O Lewis:
acid: accepts an electron pair
base: donates an electron pair
The advantage oI this theory is that many more reactions can be considered acid-base
reactions because they do not have to occur in solution.
Salts
A salt is Iormed when an acid and a base are mixed and the acid releases H

ions while the base

releases OH
-
ions. This process is called hydrolysis. The pH oI the salt depends on the strengths
oI the original acids and bases:
Acid Base Salt pH
strong strong pH 7
weak strong pH ~ 7
strong weak pH 7
weak weak depends on which is stronger
These salts are acidic or basic due to their acidic or basic ions. When weak acids or weak bases
react with water, they make strong conjugate bases or conjugate acids, respectively, which
determines the pH oI the salt.
Acid-Base Character
For a molecule with a H-X bond to be an acid, the hydrogen must have a positive oxidation
number so it can ionize to Iorm a positive 1 ion. For instance, in sodium hydride (NaH) the
hydrogen has a -1 charge so it is not an acid but it is actually a base. Molecules like CH
4
with
nonpolar bonds also cannot be acids because the H does not ionize. Molecules with strong bonds
(large electronegativity diIIerences), are less likely to be strong acids because they do not ionize
very well. For a molecule with an X-O-H bond (also called an oxoacid) to be an acid, the
hydrogen must again ionize to Iorm H

. To be a base, the O-H must break oII to Iorm the

hydroxide ion (OH
-
). Both oI these happen when dealing with oxoacids.
Strong Acids: These acids completely ionize in solution so they are always represented in
chemical equations in their ionized Iorm. There are only seven (7) strong acids:
HCl, HBr, HI, H
2
$O
4
, HNO
3
, HClO
3
, HClO
4

To calculate a pH value, it is easiest to Iollow the standard "$tart, Change, Equilibrium" process.
Example Problem: etermine the pH oI a 0.25 M solution oI HBr.
Answer:

HBr (aq) H

(aq) Br
-
(aq)
$tart: .25 M

0 M

0 M
Change: -.25

.25

.25
Equilibrium: 0

.25

.25

pH -log|H

| -log(.25) 0.60

eak Acids: These are the most common type oI acids. They Iollow the equation:
HA(aq) H

(aq) A
-
(aq)
The equilibrium constant Ior the dissociation oI an acid is known as K
a
. The larger the value oI
K
a
, the stronger the acid.
K
a

|H

||A
-
|

|HA|
Example Problem: etermine the pH oI 0.30 M acetic acid (HC
2
H
3
O
2
) with the K
a
oI 1.8x10
-5
.
Answer:
Write an equilibrium equation Ior the acid:
HC
2
H
3
O
2
H

C
2
H
3
O
2
-

Write the equilibrium expression and the K
a
value:
K
a

|H

||C
2
H
3
O
2
-
|

|HC
2
H
3
O
2
|
1.8x10
-5


"$tart, Change, Equilibrium":

HC
2
H
3
O
2
H

C
2
H
3
O
2
-

$tart: 0.30 M

0 M

0 M

Change: -x

x

x

Equilibrium: 0.30 - x

x

x


$ubstitute the variables (disregard the "-x" because it is so small compared to the 0.30)
and solve Ior |H

|:

K
a
1.8x10
-5

(x)(x)

(.30 - x)

x
2


.30


x |H

| 2.3x10
-3


pH -log|H

| 2.64

Strong Bases: Like strong acids, these bases completely ionize in solution and are always
represented in their ionized Iorm in chemical equations. There are only eight (8) strong bases:
LiOH, NaOH, KOH, RbOH, CsOH, Ca(OH)
2
, $r(OH)
2
, Ba(OH)
2

Example Problem: etermine the pH oI a 0.010 M solution oI Ba(OH)
2
.
Answer:

Ba(OH)
2
(aq) Ba
2
(aq) 2OH
-
(aq)
$tart: .010 M

0 M

0 M
Change: -.010

.010

.010
Equilibrium: 0

.010

.010
pOH -log|OH
-
| -log(.010) 1.70

pH 14.00 - 1.70 12.30

eak Bases: These Iollow the equation:
Weak Base H
2
O conjugate acid OH
-

example: NH
3
H
2
O NH
4

OH
-

K
b
is the base-dissociation constant:
K
b

|conjugate acid||OH
-
|

|weak base||H
2
O|
example: K
b

|NH
4

||OH
-
|

|NH
3
|H
2
O|
K
a
x K
b
K
w
1.00x10
-14

To calculate the pH oI a weak base, we must Iollow a very similar "$tart, Change, Equilibrium"
process as we did with the weak acid, however we must add a Iew steps.
Example Problem: etermine the pH oI 0.15 M ammonia (NH
3
) with a K
b
1.8x10
-5
.
Answer:
Write the equilibrium equation Ior the base:
NH
3
H
2
O NH
4

OH
-

Write the equilibrium expression and the K
b
value:
K
b

|NH
4

||OH
2
-
|

|NH
3
||H
2
O|
1.8x10
-5


"$tart, Change, Equilibrium":

NH
3
H
2
O NH
4

OH
-

$tart: 0.15 M

--

0 M

0 M

Change: -x

--

x

x

Equilibrium: 0.15 - x

--

x

x


$ubstitute the variables (disregard the "-x" because it is so small compared to the 0.15)
and solve Ior |OH
-
|:

K
b
1.8x10
-5

(x)(x)

(.15 - x)

x
2


.15


x |OH
-
| 1.6x10
-3
M

pOH -log|OH
-
| 2.80

pH 14.00 - 2.80 - 11.20

When dealing with weak acids and weak bases, you also might have to deal with the "common
ion eIIect". This is when you add a salt to a weak acid or base that contains one oI the ions
present in the acid or base. To be able to use the same process to solve Ior pH when this occurs,
all you need to change are your "start" numbers. Add the molarity oI the ion, which comes Irom
the salt, and then solve the K
a
or K
b
equation as you did earlier.
Example Problem: Find the pH oI a solution Iormed by dissolving 0.100 mol oI HC
2
H
3
O
2
with a
K
a
oI 1.8x10
-8
and 0.200 mol oI NaC
2
H
3
O
2
in a total volume oI 1.00 L.
Answer:

HC
2
H
3
O
2
(aq) H

(aq)
C
2
H
3
O
2
-
(aq)
$tart: .10 M

0 M

.20 M
Change: -x

x

x
Equilibrium: .10 - x

x

.20 x
K
a
1.8x10
-8

(x)(.20 x)

(.10 - x)

(x)(.20)

(.10)

x H
+
] -9.0x10
-9


pH -log(9.0x10
-9
) 8.05

Acid-Base Titrations
An acid-base titration is when you add a base to an acid until the equivalence point is reached
which is where the number oI moles oI acid equals the number oI moles oI base. For the titration
oI a strong base and a strong acid, this equivalence point is reached when the pH oI the solution
is seven (7) as seen on the Iollowing titration curve:

For the titration oI a strong base with a weak acid, the equivalence point is reached when the pH
is greater than seven (7). The halI equivalence point is when halI oI the total amount oI base
needed to neutralize the acid has been added. It is at this point where the pH pK
a
oI the weak
acid.

In an acid-base titration, the base will react with the weak acid and Iorm a solution that contains
the weak acid and its conjugate base until the acid is completely gone. To solve these types oI
problems, we will use the K
a
value oI the weak acid and the molarities in a similar way as we
have beIore. BeIore demonstrating this way, let us Iirst examine a short cut, called the
Henderson-Hasselbalch Equation. This can only be used when you have some acid and some
conjugate base in your solution. II you only have acid, then you must do a pure K
a
problem and
iI you only have base (like when the titration is complete) then you must do a K
b
problem.
pH pK
a
log
-ase]

acid]
Where:
pH is the log oI the molar concentration oI the hydrogen
pK
a
is the equilibrium dissociation constant Ior an acid
|base| is the molar concentration oI a basic solution
|acid| is the molar concentration oI an acidic solution
Example Problem: 25.0 mL oI 0.400 M KOH is added to 100. mL oI 0.150 M benzoic acid,
HC
7
H
5
O
2
(K
a
6.3x10
-5
). etermine the pH oI the solution.
Answer:
etermine where in the titration we are:
0.400 M x 0.025 L 0.0100 mol KOH added
0.150 M x 0.100 L 0.0150 mol HC
7
H
5
O
2
originally
because only 0.100 mol oI base has been added, that means the thitration is not
complete; this means there are two ways to solve this problem: the normal way
and the way using the Henderson-Hasselbalch Equation.
Normal way:

HC
7
H
5
O
2
OH
-

C
7
H
5
O
2
-
H
2
O
beIore reaction: 0.015 mol

0.0100 mol

0 mol

--
change: -0.0100

-0.0100

0.0100

--

aIter reaction: 0.0050

0

0.0100

--

K
a

|H

||C
7
H
5
O
2
-
|

|HC
7
H
5
O
2
|
6.3x10
-5

(x)(0.0100)

0.0050

x |H

| 3.2x10
-5
M
pH -log(3.2x10
-5
) 4.49
Henderson-Hasselbalch Way:
|HC
7
H
5
O
2
|
0.0050 mol

0.125 L
0.040 M

|C
7
H
5
O
2
-
|
0.0100 mol

0.125 L
0.0800 M

pH pK
a
log
|base|

|acid|

pH -log(6.3x10
-5
) log
0.0800

0.0400
4.20 0.30 4.50

This equation is used Irequently when trying to Iind the pH oI buIIer solutions. A buIIer solution
is one that resists changes in pH upon the addition oI small amounts oI an acid or a base. They
are made up oI a conjugate acid-base pair such as HC
2
H
3
O
2
/C
2
H
3
O
2
-
or NH
4

/NH
3
. They work
because the acidic species neutralize the OH
-
ions while the basic species neutralize the H

ions.
The buIIer capacity is the amount oI acid or base the buIIer can neutralize beIore the pH begins
to change to a signiIicant degree. This depends on the amount oI acid or base in the buIIer. High
buIIering capacities come Irom solutions with high concentrations oI the acid and the base and
where these concentrations are similar in value.
ractice weak acid problem:
C
6
H
5
COONa is a salt oI a weak acid C
6
H
5
COOH. A 0.10 M solution oI C
6
H
5
COONa has a pH
oI 8.60.
1. Calculate |OH
-
| oI C
6
H
5
COONa
2. Calculate K
b
Ior: C
6
H
5
COO
-
H
2
O ---~ C
6
H
5
COOH OH
-

3. Calculate K
a
Ior C
6
H
5
COOH
$ee the weak acid solution.
Practice titration problem:
20.00 mL oI 0.160 M HC
2
H
3
O
2
(K
a
1.8x10
-5
) is titrated with 0.200 M NaOH.
1. What is the pH oI the solution beIore the titration begins?
2. What is the pH aIter 8.00 mL oI NaOH has been added?
3. What is the pH at the equivalence point?
4. What is the pH aIter 20.00 mL oI NaOH has been added?

An Introduction
by Anthony Carpi, Ph.D.
For thousands oI years people have known that vinegar, lemon juice and many other Ioods taste
sour. However, it was not until a Iew hundred years ago that it was discovered why these things
taste sour - because they are all acids. The term acid, in Iact, comes Irom the Latin term acere,
which means "sour". While there are many slightly diIIerent deIinitions oI acids and bases, in
this lesson we will introduce the Iundamentals oI acid/base chemistry.
In the seventeenth century, the Irish writer and amateur chemist Robert Boyle Iirst labeled
substances as either acids or bases (he called bases alkalies) according to the Iollowing
characteristics:
Acids taste sour, are corrosive to metals, change litmus (a dye extracted Irom lichens) red, and
become less acidic when mixed with bases.
Bases Ieel slippery, change litmus blue, and become less basic when mixed with acids.
While Boyle and others tried to explain why acids and bases behave the way they do, the Iirst
reasonable deIinition oI acids and bases would not be proposed until 200 years later.
In the late 1800s, the $wedish scientist $vante Arrhenius proposed that water can dissolve many
compounds by separating them into their individual ions. Arrhenius suggested that acids are
compounds that contain hydrogen and can dissolve in water to release hydrogen ions into
solution. For example, hydrochloric acid (HCl) dissolves in water as Iollows:
PCl
P2C

P
+
(f) + Cl

(f)
Arrhenius deIined bases as substances that dissolve in water to release hydroxide ions (OH-) into
solution. For example, a typical base according to the Arrhenius deIinition is sodium hydroxide
(NaOH):
naCP
P2C
na
+
(f) + CP

(f)
The Arrhenius deIinition oI acids and bases explains a number oI things. Arrhenius's theory
explains why all acids have similar properties to each other (and, conversely, why all bases are
similar): because all acids release H

into solution (and all bases release OH

-
). The Arrhenius
deIinition also explains Boyle's observation that acids and bases counteract each other. This idea,
that a base can make an acid weaker, and vice versa, is called neutralization.
Neutralization
As you can see Irom the equations, acids release H

into solution and bases release OH

-
. II we
were to mix an acid and base together, the H

ion would combine with the OH

-
ion to make the
molecule H
2
O, or plain water:
P
+
(f) + CP

(f)

P
2
C
The neutralization reaction oI an acid with a base will always produce water and a salt, as shown
below:
n

8ase

Water

Sa|t
PCl + naCP

P
2
C + naCl
P8r + kCP

P
2
C + k8r
Though Arrhenius helped explain the Iundamentals oI acid/base chemistry, unIortunately his
theories have limits. For example, the Arrhenius deIinition does not explain why some
substances, such as common baking soda (NaHCO
3
), can act like a base even though they do not
contain hydroxide ions.
In 1923, the anish scientist Johannes Bronsted and the Englishman Thomas Lowry published
independent yet similar papers that reIined Arrhenius' theory. In Bronsted's words, "... acids and
bases are substances that are capable oI splitting oII or taking up hydrogen ions, respectively."
The Bronsted-Lowry deIinition broadened the Arrhenius concept oI acids and bases.
The Bronsted-Lowry deIinition oI acids is very similar to the Arrhenius deIinition, any substance
that can donate a hydrogen ion is an acid (under the Bronsted deIinition, acids are oIten reIerred
to as proton donors because an H

ion, hydrogen minus its electron, is simply a proton).

The Bronsted deIinition oI bases is, however, quite diIIerent Irom the Arrhenius deIinition. The
Bronsted base is deIined as any substance that can accept a hydrogen ion. In essence, a base is
the opposite oI an acid. NaOH and KOH, as we saw above, would still be considered bases
because they can accept an H

Irom an acid to Iorm water. However, the Bronsted-Lowry

deIinition also explains why substances that do not contain OH
-
can act like bases. Baking soda
(NaHCO
3
), Ior example, acts like a base by accepting a hydrogen ion Irom an acid as illustrated
below:
n

8ase

Sa|t
PCl + naPCC
3


P
2
CC
3
+ naCl
In this example, the carbonic acid Iormed (H
2
CO
3
) undergoes rapid decomposition to water and
gaseous carbon dioxide, and so the solution bubbles as CO
2
gas is released.
\
Under the Bronsted-Lowry deIinition, both acids and bases are related to the concentration oI
hydrogen ions present. Acids increase the concentration oI hydrogen ions, while bases decrease
the concentration oI hydrogen ions (by accepting them). The acidity or basicity oI something,
thereIore, can be measured by its hydrogen ion concentration.
In 1909, the anish biochemist $ren $rensen invented the pH scale Ior measuring acidity.
The pH scale is described by the Iormula:
|og
+
noLe concenLraLlon ls commonly abbrevlaLed by uslng square brackeLs
Lhus P
+
hydrogen lon concenLraLlon When measurlng pP P
+
ls ln
unlLs of moles of P
+
per llLer of soluLlon

For example, a solution with |H

| 1 x 10
-7
moles/liter has a pH equal to 7 (a simpler way to
think about pH is that it equals the exponent on the H

concentration, ignoring the minus sign).

The pH scale ranges Irom 0 to 14. $ubstances with a pH between 0 and less than 7 are acids (pH
and |H

| are inversely related - lower pH means higher |H

|). $ubstances with a pH greater than

7 and up to 14 are bases (higher pH means lower |H

|). Right in the middle, at pH 7, are

neutral substances, Ior example, pure water. The relationship between |H

| and pH is shown in
the table below alongside some common examples oI acids and bases in everyday liIe.

+
am|e
Aclds
1 x 10
0
0 PCl
1 x 10
1
1 SLomach acld
1 x 10
2
2 Lemon [ulce
1 x 10
3
3 vlnegar
1 x 10
4
4 Soda
1 x 10
3
3 8alnwaLer
1 x 10
6
6 Mllk
neuLral 1 x 10
7
7 ure waLer
8ases
1 x 10
8
8 Lgg whlLes
1 x 10
9
9 8aklng soda
1 x 10
10
10 1ums

anLacld
1 x 10
11
11 Ammonla
1 x 10
12
12 Mlneral llme Ca(CP)
2

1 x 10
13
13 urano

1 x 10
14
14 naCP
Related Modules




Le Chatelier's Principle states: "When a stress is applied to a chemical system at equilibrium, the
equilibrium concentrations
ill shift in a direction that reduces the effect of the stress.
The stress that ill be applied in our investigation ill be either:
the addition of more reactant or product to the equilibrium mixture, increasing their concentration.
the addition of a species that chemically reacts ith either a reactant or product in the equilibrium
mixture, loering their
concentration.
The systems ill involve equilibriums that you may have already studied: eak acid and base, (Ka and
Kb), solubility, (Ksp),
and complex ion formation, (Kf). Although no calculations ill be done, you should be able to recognize
the type of
equilibrium under investigation.
The folloing is an example of an equilibrium system similar to the five you ill investigate. The first step
in the process is
to establish the equilibrium given the alloed reagents. The equilibrium concentrations are shifted (to the
left or right) by
applying a stress to the equilibrium system by adding one of the given reagents. Changes in the
appearance of the system are
recorded. Finally, a net-ionic equation is ritten to understand the chemistry behind the change in
equilibrium
concentrations.
An


An example equilibrium
Consider the folloing equilibrium beteen aluminum ions and ammonia:
Al3+(aq) + 3 NH3(aq) + 3 H2O(aq) Al(OH)3(s) + 3 NH4
+(aq)
Reagents
To establish equilibrium: aluminum nitrate, 0.1 M ammonia, 0.1 M
To shift equilibrium concentrations: hydrochloric acid, 1 M
1. Al(OH)3(s) might be produced by:
"Adding aluminum nitrate ith ammonia
a) Observation:
"When the to clear and colorless solutions ere mixed, a hite precipitate formed.
b) Net-ionic equation:
"Al3+(aq) + 3 NH3(aq) + 3 H2O(l) Al(OH)3(s) + 3 NH4
+(aq)
2. The equilibrium concentrations can be shifted 019by adding:
"HCl
a) Observation:
"The precipitate dissolved.
b) Net-ionic equation:
"Al3+(aq) + 3 H2O(l) < Al(OH)3(s) + 3 H+(aq)