DISCLAIMER: these notes are provided to assist you with mastering the course material but they are

e not intended as a replacement of the

lectures. Neither do they contain the comments and ancillary material of the lectures; they are just a set of points that you might bring to the
lectures to annotate instead of having to write everything down and/or they may assist you in organizing the material after the lectures, in
conjunction with your own notes.
Acid Base Equilibria
(Review from Chem122)
Classification and Definitions of Acids & Bases

- aqueous solutions involving H
+
(aq) and OH
-
(aq)
- Arrhenius : in water, acids increase [H
+
], bases increase [OH
-
]
- Acid: substance that releases H
+
when placed in water
- Base: substance that releases OH
-
when placed in water

Bronsted - Lowry Acids & Bases
- consider as proton-transfer reactions:

HCl(g) H (aq) + Cl (aq)
as HCl(g) + H O(l) H O (aq) + Cl (aq)
H O + -
2 3
+ -
2

- Bronsted - Lowry: acids are proton donors, bases are proton acceptors (this is the usual
treatment of acid and base reactions in aqueous solution)
- also applicable to non-aqueous reactions, eg. gas phase reaction:

..
..
..
..
-
+
+
+
:Cl H
N H
H
H
:Cl:
N
H
H
H
H
:


- another eg. (a Bronsted base)

NH (aq) + H O(l) NH (aq) + OH (aq)
3 2 4
+ -


- identify acid(s) and base(s); note formation of hydroxide (OH
-
), a strong base
- terminology:
- monoprotic acids: single proton donors, eg. HCl, HNO
3
, acetic acid
- polyprotic acids: donors of two or more protons, eg. H
2
SO
4
, H
3
PO
4
, carbonic acid
- likewise, mono- , polyprotic bases
- intermediate forms said to be amphiprotic (previously: amphoteric): capable of acting
as either acid (with another base) or base (with another acid), eg. HSO
4
-
, H
2
PO
4
-
,
HCO
3
-


Lewis Acids & Bases
- Lewis acid - an electron pair acceptor (eg. H
+
)
- Lewis base - an electron pair donor (eg. :NH
3
and H
2
O)

- more general as to what can be an acceptor
- eg. H
3
N: + BF
3
H
3
N-BF
3


- note absence of H
+
transfer and of water
- Lewis acids generally have vacant orbitals
2


Acids & Bases in Aqueous Solution: the Bronsted Lowry Scheme

Conjugate Acid - Base Pairs (extra)

NH (aq) + H O(l) NH (aq) + OH (aq)
3 2 4
+ -

base acid conjugate conjugate

acid base
add H
+
lose H
+

- these pairs of species related by presence or absence of a proton are conjugate acid-base pairs
- generalized: HA and A
-
or B: and BH
+

- can be neutral or charged
- warning: charge consistency!

- note that in egs. above water has acted as a base in the presence of an acid (eg. HCl, HNO
3
)
and as an acid in the presence of a base (eg. NH
3
), said to be amphiprotic (including
autoionization reaction)
- practice recognizing and writing conjugates

Conjugate Base: Species formed when an acid gives up a proton.

Acid proton Conjugate base
1. NH
4
+
---> H
+
NH
3

2. HSO
4
-
---> H
+
SO
4
2-

3. HCl ----> H
+
Cl
-

4. NH
3
----> H
+
NH
2
-

Note: the acid may be a cation, anion or a neutral species.

Conjugate acid: species formed when a base accepts a proton.

Base Proton Conjugate acid
OH
-
H
+
HOH
PO
4
3-
H
+
HPO
4
2-

HOH H
+
H
3
O
+

NH
3
H
+
NH
4
+

CH
3
OH

H
+
CH
3
OH
2
+


Practice :
For each of the following identify the acid, base and conjugate base and acid.
1. HCl + OH
-
----> HOH + Cl
-


2. HSO
4
-
+ HOH ----> H
3
O
+
+ SO
4
2-

3. CN
-
+ HOH <----> HCN + OH
-


4. HSO
4
-
+ H
3
O
+
<----> H
2
O + H
2
SO
4

3


Conjugate Acid - Base Strengths (a survey)
- The strength of an acid depends on the degree of ionization.
- define strong acids: [H
3
O
+
] ~ initial concentration of acid
Strong acid: nearly complete ionization. The conjugate base has little attraction for the proton.
This means that the conjugate base is very weak.
HCl(aq) + H
2
O(l) H
3
O
+
(aq) + Cl
-
(aq)
stronger acid stronger base weaker acid weaker base
than H
3
O
+
than Cl
-
than HCl than H
2
O

- whereas weak acids: [H
3
O
+
] << initial concentration of acid. Relative little ionization.
The conjugate base must be relatively strong because it has a strong attraction for H
+
.

CH
3
CO
2
H(aq) + H
2
O(l) H
3
O
+
(aq) + CH
3
CO
2
-
(aq)
weaker acid weaker base stronger acid stronger base
than H
3
O
+
than CH
3
CO
2
-
than CH
3
CO
2
H than H
2
O

- conversely, strong base: [OH
-
] ~ initial concentration of base
- eg. O
2-
(aq) + H
2
O(l) 2 OH
-
(aq)
- and weak base: [OH
-
] << initial concentration of base
- eg. ammonia, above, or CO
3
2-
(aq) + H
2
O(l) HCO
3
-
(aq) + OH
-
(aq)

Strong acid has a weak conjugate base.
Weak acids have a strong conjugate base.
Strong bases must have a weak conjugate acid.
Weak bases must have a strong conjugate acid.

Remember seven strong acids are aqueous solutions of the following:
HCl, HBr, HI, HClO
4
, HNO
3
, H
2
SO
4
, HClO
3
.
Note : All acids that are not strong ( above list ) are weak

most common strong bases, metal hydroxides, eg. NaOH, KOH, Ca(OH)
2
; fully
dissociated
some bases stronger than OH
-
, dissolve to form OH
-
(eg. O
2-
, H
-
, N
3-
)

The degree of ionization depends on the following:
a. Relative bond strength. Which depends to some extend on the charge density of the
anion, X
-
.
b. Bond polarity: difference in electronegativity of H and X. The greater the bond
polarity the stronger the acid.
c. Stability of the conjugate base (the anion). The stability of a charged species increases
as the charge is dispersed over a larger volume. Thus, the lower the charge density the greater
the stability of the anion and the stronger the acid.







4


Examples: Arrange the following in order of increasing strength.
1). Consider the binary halide acids: HF, HCl, HBr and HI.
a. Based on bond strength (increasing charge density of the anion)
HF HCl HBr HI
-------------->
decreasing bond strength and increasing acid strength.
b. Based on stability of the anion: Charge density of the anion.
HF HCl HBr HI
-------------->
increasing stability of the anion and increasing acid strength.
2). Strength as an acid: HClO
2
, HClO
4
, HClO
3
, HClO. .
ANS: HClO, HClO
2
, HClO
3
, HClO
4
. Strongest acids since ClO
3
is the most electronegative.
3). Strength as an acid: CH
3
COOH, CF
3
COOH, CH
2
FCOOH, CHF
2
COOH.
ANS: CH
3
COOH, CH
2
FCOOH, CHF
2
COOH, CF
3
COOH.
4). Strength as a base: KOH NaOH CsOH LiOH
ANS: LiOH NaOH KOH CsOH
Conjugate Acid-Base Pairs Arranged by Strength
The stronger the acid, the weaker the conjugate base. The stronger the base, the weaker the conjugateacid.
ACID BASE
Strength of
Acid
Name Formula Formula Name Strength of Base


STRONG
ACIDS
perchloric acid HClO
4
ClO
4

perchlorate ion Neutral Anion
sulfuric acid H
2
SO
4
HSO
4

hydrogensulfate ion Moderately Strong
Acid!
hydroiodic acid HI I

iodide ion
Neutral
Anions
hydrobromic acid HBr Br

bromide ion
hydrochloric acid HCl Cl

chloride ion
nitric acid HNO
3
NO
3

nitrate ion
Strong Acid hydronium ion H
3
O
+
H
2
O water Neutral
Moderately
Strong Acid!
hydrogensulfate ion HSO
4

SO
4
2
sulfate ion Neutral Anion!

WEAK ACIDS

Acid strength
INCREASES as
you go UP the
column.
hydrofluoric acid HF F

fluoride ion
WEAK BASES

Base strength
INCREASES as you
go DOWN the
column.
nitrous acid HNO
2
NO
2

nitrite ion
acetic acid HC
2
H
3
O
2
C
2
H
3
O
2

acetate ion
carbonic acid H
2
CO
3
HCO
3

hydrogencarbonate
ion
hydrosulfuric acid H
2
S HS

hydrogensulfide ion
ammonium ion NH
4
+
NH
3
ammonia
hydrocyanic acid HCN CN

cyanide ion
Basic Anion! hydrogencarbonate
ion
HCO
3

CO
3
2
carbonate ion
Weak Acid methylammonium ion CH
3
NH
3
+
CH
3
NH
2
methylamine
Neutral Water H
2
O OH

hydroxide ion Strong Base
Basic Molecule ammonia NH
3
NH
2

amide ion
STRONG
BASES
Neutral
Molecules
hydrogen H
2
H

hydride ion
methane CH
4
CH
3

methide ion
Strong Base! hydroxide ion OH

O
2

oxide ion
5


The Hydronium Ion & Autoionization of Water

- autoionization:
H O(l) H (aq) + OH (aq)
K =
[H ][OH ]
H O]
2
+ -
+ -
2

[


- very little dissociation, [H
2
O]

K
w
= [H
+
][OH
-
]
K
w
= ion-product constant
K
w
= 1 x 10
-14
at 25C (Table 10.1)

- in neutral solution: [H
+
] = [OH
-
] = 1 x 10
-7
M
- note: K
w
a constant, regardless of whether solution neutral

The Proton in H
2
O
- H
+
unlikely; more likely is H
3
O
+
, hydronium ion or higher order H
5
O
2
+
or H
9
O
4
+

- equation above is more likely:

H O(l) + H O(l) H O (aq) + OH (aq)
2 2 3
+ -


- H
+
(aq) and H
3
O
+
(aq) used interchangably in terminology; K
w
unaffected

Water and the Acid Base Level
- water Ionization Constant, K
w

- in pure water, K
w
= 1 x 10
-14
= [H
3
O
+
][OH
-
]; and [H
3
O
+
] = [OH
-
] = 1 x 10
-7
M (at 25
o
C)
- this is a neutral solution
- disturb this equilibrium by adding acid or base, K
w
= 1 x 10
-14
= [H
3
O
+
][OH
-
], but [H
3
O
+
] =
[OH
-
]
- in acidic solution, [H
3
O
+
] > 1 x 10
-7
M
- in basic solution, [OH
-
] > 1 x 10
-7
M


Example problems.
1. Calculate the [H
+
] and [OH
-
] in a 0.200M HClO
4
(aq) solution.
First get the chemistry right (GCR). What is HClO
4
(aq)?
ANS: A strong acid so it will ionize completely.
HClO
4
(aq) ---> H
+
(aq) + ClO
4
-
(aq)
Initial 0.200 0 0
Complete Rxn.-0.200 +0.200 +0.200
End 0 0.200 0.200

Solve for [OH
-
] using K
w
= [H
3
O
+
][OH
-
] = 1.00 x 10
-14
.
ANS: [H
+
] = 0.200M and [OH
-
] = 5.00 x 10
-14


6


3. Calculate the [H
+
] and [OH
-
] in a 0.0400M Ba(OH)
2
(aq) solution.
First get the chemistry right (GCR). What is Ba(OH)
2
(aq)?
A strong base which will dissociate completely.

Ba(OH)
2
(aq) ---> Ba
2+
(aq) + 2 OH
-
(aq)
Initial 0.0400 0 0
Complete Rxn -0.0400 +0.0400 +0.0800
End 0 +0.0400 +0.0800

[OH
-
] = 0.0800 M and use K
w
= [H
3
O
+
][OH
-
] = 1.00 x 10
-14
.
ANS: [H
+
] = 1.3 x 10
-13
M.

The pH Scale
- [H
+
] in many aqueous solutions of interest is often quite small, expressed in terms of pH:

pH = - log [H
+
]

- neutral solution: [H
+
] = 1 x 10
-7
M, pH = 7.0
- pH decreases as [H
+
] increases

recall, [H
+
] and [OH
-
] related by K
w

The General Math with the pX.
1. pX = - log [X] and the [X] = 10
-pX
.
2. Other common pX terms.
pH = - log [H
3
O
+
] pOH = - log [OH
-
] pK = - log K
eq


Example : What is the [H
3
O
+
] in a solution with pH = 12.30?
pH = - log [H
3
O
+
] = 12.30
[H
3
O
+
] = 10
-pH
= 10
-12.30
= 5.0 x 10
-13

Relationship between pH and pOH.
[H
3
O
+
][OH
-
] = 1.00 x 10
-14
now obtain logs of both sides
log [H
3
O
+
] + log[OH
-
] = -14 and change the sign
- log [H
3
O
+
] - log[OH
-
] = 14 and use pH and pOH definitions
pH + pOH = 14 Learn

Example problems.
1. Calculate the [H
3
O
+
], [OH
-
], pH and pOH for a 0.0350 M NaOH(aq) solution.
ANS: [OH
-
] = 0.0350M, pOH = 1.46 pH = 12.54, [H
3
O
+
] = 2.86 x 10
-13


Measuring pH
- pH meter
- estimates using colour changes of acid - base indicators,
- equilibrium: HIn + H
2
O H
3
O
+
+ In
-
, and two forms of indicator have different
colours (note: this is also an acid-base equilibrium)

7


Acid & Base Strength (Weak Acids & Bases)

- weak acid, partial dissociation:
-
HA(aq) + H
2
O(l) H
+
(aq) + A
-
(aq)

- equilibrium constant = acid-dissociation constant
K =
[H ][A ]
HA
a
+ -
[ ]

- the larger K
a
, the stronger the acid (note: K
a
s of weak acids always < 1 (strong acids, K
a
>>
1)
- can be neutral molecules (eg. formic acid, HF, HCN and others), cations (eg. ammonium,
NH
4
+
) or anions (eg. H
2
PO
4
-
)
-
- similarly for weak bases:

B(aq) + H
2
O(l) BH
+
(aq) + OH
-
(aq)

K =
[BH ][OH ]
B
b
+
[ ]

- the larger K
b
, the stronger the base (note: K
b
s of weak bases always < 1 (strong bases, K
b
>>
1)
- can be neutral molecules (eg. CH
3
NH
2
) or anions (eg. CN
-
)

Connection Between K
a
and K
b
for a Conjugate Pair
- use NH
4
+
/NH
3
conjugate pair as eg.

NH
4
+
(aq) NH
3
(aq) + H
+
(aq)
NH
3
(aq) + H
2
O(l) NH
4
+
(aq) + OH
-
(aq)

K =
[NH ][H ]
[NH ]
; K =
[NH ][OH ]
[NH ]
a
3
+
4
+
b
4
+ -
3

- add the above two equilibria, net is:

H O(l) H (aq) + OH (aq)
2
+ -


- two equilibria are consecutive reactions leading to the overall above, equm constant for
equlibria thus added is product of individual equm constants

K x K =
[NH ][H ]
[NH ]

[NH ][OH ]
[NH ]
= [H ][OH ] = K
a b
3
+
4
+
4
+ -
3
+ -
w
|
\

|
.
|
|
\

|
.
|


- this result is general: for a conjugate pair
K
a
x K
b
= K
w

8


Weak Acid & Base Equilibria on the pH-Scale
- rather than using K
a
and K
b
, express these on the logarithmic pH-scale:
- define: pK
a
= - log K
a
(lower, stronger acid) and pK
b
= - log K
b
(lower, stronger
base)
- from: K
a
x K
b
= K
w
; hence: pK
a
+ pK
b
= 14 (at 25
o
C)

- Table of Ka and Kb values







Equilibrium Calculations for Weak Acids & Bases
- two types:
- calculate K
a
or K
b
from initial concentration(s) and measured pH
- calculate equilibrium concentrations and pH from initial concentrations and known K
a
or
K
b

- four steps:
- write the ionization equilibrium equation
- write the equilibrium expression
- construct a table( ICE box , initial, change equilibrium concentrations for all species)
- solve for unknown (may or may not be quadratic)

Calculating K
a
or K
b
from Measured pH
- using a known solution:
- 0.10 mol propanoic acid made up to 1.0 L in H
2
O; measured pH = 2.94
1. write ionization equilibrium:
C
3
H
5
O
2
H

(aq) H
+
(aq) + C
3
H
5
O
2
-
(aq)

2. write equilibrium expression:
K =
[H ][C H O
[HC H O
= ?
a
+
3 5 2
-
3 5 2
]
]

3. construct table as in equilibrium chapter : 2.94 = - log [H
+
]; hence, [H
+
] = 1.15 x 10
-3
M
(assume noneof this comes from water ionization)

C
3
H
5
O
2
H

(aq) H
+
(aq) + C
3
H
5
O
2
-
(aq)
Initial 0.10 M 0 0
Change - x M (= - 1.15 x 10
-3
) + x M (1.15 x
10
-3
)
+ x M (1.15 x
10
-3
)
Equilibrium (0.10 - 1.15 x 10
-3
) ~ 0.10
M
1.15 x 10
-3
M 1.15 x 10
-3
M

4. substitute equilibrium concentrations in expression
( )
K =
[H ][C H O
[C H O H
=
1.15 x 10
= 1.32 x 10 ; pK = 4.88
a
+
3 5 2
-
3 5 2
-3
-5
a
]
] .
2
010

9



Calculating Equilibrium Concentrations and pH for Solutions of Weak Acids

- using K
a
and a known solution, 4 steps; use 0.30 M acetic acid as example

1. write ionization equilibrium:
C
2
H
3
O
2
H(aq) H
+
(aq) + C
2
H
3
O
2
-
(aq)

2. write equilibrium expression:
K =
[H ][C H O
[C H O H
= 1.8 x 10
a
+
2 3 2
-
2 3 2
-5
]
]


3. construct table as in equilibrium chapter:

C
2
H
3
O
2
H(aq) H
+
(aq) + C
2
H
3
O
2
-
(aq)
initial 0.30 M 0 0
change - x M + x M + x M
equilibrium (0.30 - x) M x M x M


4. substitute equm concns in expression
K =
[H ][C H O
[C H O H
=
(x)(x)
0.30 - x
= 1.8 x 10
a
+
2 3 2
-
2 3 2
-5
]
]


- quadratic in x , avoid as long as (0.30 - x) ~ 0.30; start by assuming this, then:

K
a
= x
2
/0.30 = 1.8 x 10
-5
[H
+
] = x = 2.3 x 10
-3
M
pH = - log(2.3 x 10
-3
) = 2.64

- now check assumption, also calculate % ionization of acetic acid:
% ionization = (0.0023/0.30)100 = 0.77%

- as long as < 5%, assumption OK (alternatively, OK if [HA]
o
> 100K
a
); if not, solve
quadratic

- compare with strong acid (eg. HCl, same amount): pH = - log(0.30) = 0.52
- results of above calculations also show that [H
+
] much lower than [HA] added - properties
reflect this, eg. conductivity

- another example, if stronger acid (formic acid, K
a
= 1.8 x 10
-4
) and lower initial acid
concentration (1 mM) given, hence must solve quadratic

similarly for calculating equilibrium concentrations and pH for an aqueous solution of a weak
base, eg. pyridine and ammonia


10


There are few common weak bases:
Best known examples are ammonia and organic derivatives of ammonia where one, two or three
of the N-H bonds have been replaced by a N-C bond. The organic derivatives of ammonia are
called amines. a. An unusual derivative is H
2
NOH (hydroxylamine).
b. Methylamine is CH
3
NH
2

c. Dimethylamine is (CH
3
)
2
NH
d. Trimethylamine is (CH
3
)
3
N
- same rules of thumb for when quadratic must be solved
- note that calculations first furnish [OH
-
] and then pOH; convert latter to pH

Acid-Base Properties of Salt Solutions: Hydrolysis

- strong electrolytes, dissolve readily, but many have anions and/or cations that react with
water, i.e.- undergo hydrolysis
- eg. anions from weak acids produce OH
-
:

A
-
(aq) + H
2
O(l) HA(aq) + OH
-
(aq)
- for sodium acetate (NaCH
3
COO); pH of 8.9 calculated for 100 mM solution
- cations such as ammonia derivatives dissociate in water to give acidic solutions:

NH
4
+
(aq) NH
3
(aq) + H
+
(aq)

- eg. exercise: pH of 0.50 M aqueous ammonium chloride?

1. write ionization equilibrium (see above):

2. write equilibrium expression:
10.2) (Table 10 x 5.6 =
] [NH
] ][NH [H
= K
10 -
+
4
3
+
a


3. construct table as in equilibrium chapter:

NH
4
+
(aq) NH
3
(aq) + H
+
(aq)
Initial 0.50 M 0 0
Change - x M + x M + x M
Equilibrium (0.50 - x) M x M x M

4. substitute equm concns in expression
K =
[H ][C H O
[C H O H
=
(x)(x)
0.50 - x
= 5.6 x 10
a
+
2 3 2
-
2 3 2
-10
]
]

- quadratic in x , avoid as long as (0.50 - x) ~ 0.50; start by assuming this, then:

K
a
= x
2
/0.50 = 5.6 x 10
-10
[H
+
] = x = 1.7 x 10
-5
M
pH = - log(1.7 x 10
-5
) = 4.8
- now check assumption, also calculate % ionization of ammonium cation:
% ionization = (1.7 x 10
-5
/0.50)100 = 0.0034%
11



Sample calculations.
1. Calculate the pH, [OH
-
] and % ionization for a 1.00M solution of methylamine if K
b
= 4.4
x 10
-4
. CH
3
NH
2
+ HOH <--> CH
3
NH
3
+
+ OH
-
Set up ICE
K
b
= [CH
3
NH
3
+
][OH
-
]/[CH
3
NH
2
] = x
2
/(1.00 - x) = 4.4 x 10
-4
. Assume x is small compared to
1.00.
ANS: [CH
3
NH
3
+
] = [OH
-
] = 0.021. pH = 12.32 and 2.1% ionized.
Check: 0.021 is 2.1% of 1.00 so our assumption is justified. Note this is the same as the %
ionization.

2. An aqueous solution of ammonia is found to be 7.5% ionized. What is the initial
concentration of ammonia if K
b
= 1.8 x 10
-5
? DO
ANS: Let x = initial concentration of ammonia.
% ionization = [ionized]/[initial] x 100 so that
7.5 = [ionized]/[x] x 100 and then [ionized] = 0.075x.

NH
3
+ HOH <--> NH
4
+
+ OH
-
Set up ICE
I x -- 0 0
C -0.075x -- +0.075x +0.075x
E 0.925x 0.075x 0.075x

K
b
= [NH
4
+
][OH
-
]/[NH
3
] = (0.075x)
2
/(0.925x) = 1.8 x 10
-5

x = 3.0 x 10
-3
= [NH
3
] initially.
Notice that in this case if we had been ask to calculate the initial concentration of ammonia
given the pH we would not have been able to use the simplifying assumption because the
solution is 7.5% ionized. Even though the K
b
is small the initial concentration is also very small
so we would need to use the quadratic.

Polyprotic Acids & Bases

- more than one H
+
can dissociate, eg. (all aq)

H
2
SO
3
H
+
+ HSO
3
-
; K
a1
= 1.7 x 10
-2
; pK
a1
= 1.8
HSO
3
-
H
+
+ SO
3
-2
; K
a2
= 6.4 x 10
-8
; pK
a2
= 7.2
- similarly phosphoric acid: K
a1
= 7.5 x 10
-3
; K
a2
= 6.2 x 10
-8
; K
a3
= 3.6 x 10
-13
(pK
a
s 2.1,
7.2, 12.4, respectively)

- note: second dissociation much weaker (more difficult to remove second positive charge
from a molecule already negative), typically 10
4
10
6
times weaker (4 6 log units, i.e.-
pH/pK units)
- in determining solution pH of a polyprotic acid (fully protonated form) or its full
conjugate base (fully deprotonated), it is the first equilibrium which dominates
- eg. the K
b1
process for Na
2
CO
3
(the CO
3
2-
to HCO
3
-
step), this generalization falls down
when the two pKs are 3 or less units apart



12


Common Ion Effect
- eg. salt of conjugate base added to soln of weak acid decreases [H
+
], i.e.- increases pH
- eg.
C H O H(aq) H (aq) + C H O (aq)
2 3 2
+
2 3 2
-

- generate common ion from acid - base reaction: dissociation of weak electrolyte decreases
due to addition of strong electrolyte that has an ion in common (Le Chatelier; we will see this
later in the shape of titration curves before the equivalence point; presence of acetate, above,
acts to suppress further dissociation of acid)

- Example: calculate pH of 2.67 for 0.25 M acetic acid, pH of 4.35 of same in presence of 0.10
M sodium acetate

- for a weak base, common ion lowers pH, eg.
NH (aq) + H O(l) NH (aq) + OH (aq)
3 2 4
+ -

Buffer Solutions

- mixture of weak acid - base conjugate pairs

- resists change in pH due to added H
+
or OH
-
(will see later with titration curves)


-
Example: compare addition of strong acid to water with addition to acetate buffer
-
1.0 mL of 1.0 M HCl added to 1.0 L water or to 1.0 L of acetic acid/sodium acetate
buffer in which [CH
3
CO
2
H] = 0.70 M, [CH
3
CO
2
-
] = 0.60 M. Calculate pHs
-
calculate pH of HCl in water = 3.0; pH of buffer 4.68, same with added HCl
-
this is the buffering effect

-
analogous example: 0.50 L of a buffer composed of 0.50 M formic acid and 0.70 M sodium
formate; pH before and after adding 10.0 mL of 1.0 M HCl? (formic acid K
a
= 1.8 x 10
-4
)










13


General Expressions for Buffer Solutions


(aq.) A + (aq.) H HA(aq.)
- +


[HA(aq.)]
(aq.)]
-
(aq.)][A [H

a
K
+
=


aq.)] (
-
[A
HA(aq.)] [
a
K = (aq.)] [H
+


- take (-logarithm) of each side to get:

key equation: Henderson Hasselbalch

- NB: at [base] = [acid], pH = pK
a
, hence the importance and utility of pK
a
s

- best buffering at pH near pK
a
of conjugate pair, ie.- capacity to "mop up" added acid or
base best


- capacity also increased by concentration of conjugate pair
- important properties of a buffer are its pH and capacity

- quantitative aspects:
- use of the equation to calculate pH
- use of the equation to prepare buffers of known pH

- note: from the equation it is the mole ratio of the conjugate pair that is important, not their
absolute concentrations; hence, pH of a buffer does not change with dilution (but capacity
does)


- could equally use K
a
or K
b
for these buffering equilibria but since Henderson Hasselbalch
equation is defined in terms of pK
a
it is convenient and simpler to treat all of these acid base
equilibria as acid dissociations



[HA]
]
A
-
[
log + pK
a
= pH


14


Acid - Base Titration Curves (to be covered in Chem 123)

- pH as a function of added strong base or acid, not just at the equivalence point
- especially when a weak acid or base titrated with a strong base or acid, respectively


Strong Acid - Strong Base Titrations
- HCl and NaOH
- rapid change through equivalence point for small additions of base
- excess ion dictates solution pH
- eg. 100.0 mL of 0.10 M HCl + 0.10 M NaOH, stages of titration

Weak Acid - Strong Base Titrations
- eg. acetic acid plus NaOH,
- four regions of interest:
1. pH before the titration begins, the weak acid solution itself (pH = 2.87 for 0.10 M
acetic acid)
2. pH at the mid-point of the titration, the pK
a
(for acetic acid, 4.74); near mid-point,
shallow slope, i.e.- relatively insensitive to added strong acid or strong base =
buffering region
3. pH at the equivalence point; here basic due to hydrolysis of conjugate base of weak
acid
4. pH when base added beyond the equivalence point

- steps in calculations:
- stoichiometric calculation to give concentrations of conjugate pair
- equilibrium calculation, usually with Henderson - Hasselbalch equn before the
equivalence point
- as acid becomes weaker, the equivalence point region of the titration curve is less easy to
discern

Weak Base - Strong Acid Titrations
- eg. ammonia plus HCl; acidic end-point, hence, methyl red appropriate indicator











15


1.

A 30.00 millilitre sample of a weak monoprotic acid was titrated with a standardized solution of NaOH. A pH meter
was used to measure the pH after each increment of NaOH was added, and the curve above was constructed.
(a) Explain how this curve could be used to determine the molarity of the acid.
(b) Explain how this curve could be used to determine the dissociation constant K
a
of the weak monoprotic acid.
(d) Sketch the titration curve that would result if the weak monoprotic acid were replaced by a strong monoprotic
acid, such as HCl of the same molarity. Identify differences between this titration curve and the curve shown
above.

2.
In an experiment to determine the molecular weight and the ionization constant for ascorbic acid (vitamin C), a
student dissolved 1.3717 grams of the acid in water to make 50.00 millilitres of solution. The entire solution was
titrated with a 0.2211 molar NaOH solution. The pH was monitored throughout the titration. The equivalence point
was reached when 35.23 millilitres of the base has been added. Under the conditions of this experiment, ascorbic
acid acts as a monoprotic acid that can be represented as HA.
(a) From the information above, calculate the molecular weight of ascorbic acid.
(b) When 20.00 millilitres of NaOH had been added during the titration, the pH of the solution was 4.23. Calculate
the acid ionization constant for ascorbic acid.
(c) Calculate the equilibrium constant for the reaction of the ascorbate ion, A

, with water.
(d) Calculate the pH of the solution at the equivalence point of the titration.

3.
The acid ionization constant, K
a
, for propanoic acid, C
2
H
5
COOH, is 1.310
5
.
(a) Calculate the hydrogen ion concentration, [H
+
], in a 0.20molar solution of propanoic acid.
(b) Calculate the percentage of propanoic acid molecules that are ionized in the solution in (a).
(c) What is the ratio of the concentration of propanoate ion, C
2
H
5
COO

, to that of propanoic acid in a buffer

solution with a pH of 5.20?
(d) In a 100.milliliter sample of a different buffer solution, the propanoic acid concentration is 0.35molar and
the sodium propanoate concentration is 0.50molar. To this buffer solution, 0.0040 mole of solid NaOH is
added. Calculate the pH of the resulting solution.

Weak Diprotic Acid - Strong Base Titrations
- eg. oxalic acid, first equivalence point not easily discerned from graph
- eg. carbonic acid (dissolve CO
2
in water),
- neutralization stages:
H CO OH HCO H O
2 3
-
3
-
2
+ +

3 3
-
2
2
-
HCO
+
-
OH

CO
+ H O

- here, first ionization practically complete before second starts (pK
a
's 6.4 and 10.3)
X
X
X
X
X
X
X
X
0
2
4
6
8
10
12
0 5 10 15 20 25 30
pH
millilitres of NaOH
16


- titration curve shows discrete waves (as long as pK
a
's not closer than about 3 pH units)
- other polyprotic acids: H
2
SO
4
, H
3
PO
4
, amino acids H
3
N
+
CHRCO
2
H , proteins and
nucleic acids (polymers)