Overview of Acid-Base Equilibria Questions -- KEY

The following questions are designed to give you an overview of the topics in Acids and Bases
and Equilibria in Acid-Base Solutions. Although not comprehensive, these few questions do a
good job of covering the majority of the concepts and calculations related to this subject area.
Please do your best to answer the questions completely. Keys will be posted.

Acid-Base Equilibria

1. a. A typical weak acid, HA, is prepared in such a way as to have an initial concentration
in water of 0.100 M. At equilibrium the solution has pH =2.87, what is K
a
for this acid?
The molarity of the conjugate base and the molarity of the hydronium ion are known since the
pH is given (pH = 2.87 gives [A
-
] = [H
+
] = 10
-pH
= 1.35x10
-3
M.
The reaction information is summarized as . . .

HA
(aq)
+ H
2
O
(l)
<===> H
3
O
+
(aq)
+ A
-
(aq)
initial 0.10 M ---- ~ 0 M 0 M
change - 1.35x10
-3
M ---- + 1.35x10
-3
M + 1.35x10
-3
M
equilibrium
0.10 - 1.35x10
-3

M
---- 1.35x10
-3
M 1.35x10
-3
M

As you can see, all the concentrations are known and it is a simple matter to solve for K
a
.
[ ][ ]
[ ]
( )( )
( )
5
3
3 3
3
10 8 . 1
10 35 . 1 10 . 0
10 35 . 1 10 35 . 1

+
=

= = x
x
x x
HA
A O H
K
a

As you can plainly see the reaction only proceeded to a small extent in the forward
direction in order to reach equilibrium . . . so this is a WEAK acid!

b. The conjugate base of the above acid exists as a sodium salt, NaA. What is K
b
for this
conjugate base.

Remember for conjugate acid base pairs (and only for pairs): K
w
= K
a
*K
b
So K
b
= K
w
/K
a
= (1.00x10
-14
)/( 1.8x10
-5
) = 5.6x10
-10

c. For a 0.100 M solution of the conjugate base in part b, what is the [OH
-
] at
equilibrium AND what is the pH?
NOTE: in this problem I referred to the base as B
-
. . . this is an inconsequential change.
This is a straightforward equilibrium problem. The changes in concentrations and the final
equilibrium concentrations will be expressed in terms of a single variable . . .

112

B
-
(aq)
+ H
2
O
(l)
<===> OH
-
(aq)
+ HB

(aq)
initial 0.10 M ---- ~ 0 M 0 M
change - x M ---- + x M + x M
equilibrium 0.10 - x M ---- x M x M

The variable expressions of the concentrations can be plugged into the equilibrium constant
expression and this expression can be solved. This should all look very familiar by now!
[ ][ ]
[ ]
( )( )
( )
10 . 0
10 6 . 5
10 . 0
2
10
x
x
x
x x
B
HB OH
K
b

= =

Giving x = [OH
-
] = [HB] = 7.5x10
-6
M and the following equilibrium conditions

B
-
(aq)
+ H
2
O
(l)
<===> OH
-
(aq)
+ HB
(aq)
equilibrium ~0.10 M ---- 7.5x10
-6
M 7.5x10
-6
M

And pOH = 5.12 along with pH = 14.00 - pOH = 8.88

d. For the same pair of weak acid and conjugate base in the questions above, what is the
pH of a buffer in which [HA] =[A
-
] =0.25 M?

For a buffer system,
[ ]
[ ] HA
A
pK pH
a

+ = log
with pK
a
= -logK
a
= 4.74 When [HA] = [A
-
], then pH = pK
a
= 4.74

e. For the same pair of weak acid and conjugate base to form a buffer with pH =5.00
when [HA] =0.25, what does [A
-
] have to be?

In a buffer system,
[ ]
[ ] HA
A
pK pH
a

+ = log
with pK
a
= -logK
a
= 4.74 and [HA] = 0.25 M
Then for pH = 5.00, we find
5.00 - 4.74 = log[A
-
]- log[0.25] which then solves to -0.342 = log [A
-
] so . . .
[A
-
] = 0.45
5
M
This makes good sense, b/c for pH > pK
a
, [A
-
] should be > [HA]

113
f. When 4.00 L of the buffer in part e (the pH =5.00 buffer) has 0.100 mole of HCl
(g)

added, what is the new pH? HINT: should it be higher or lower than 5.00? Why?
The simplest solution is,
[ ]
[ ]
93 . 4
100 . 0 25 . 0 * 4
100 . 0 45 . 0 * 4
log 74 . 4
5
=
+

+ = pH
Note: moles of A
-
were used instead of [A
-
] and moles of HA instead of [HA]. This is perfectly
acceptable since both species exist in the same 4.00 L volume. Also note that the answer
makes good sense b/c an addition of acid should decrease the pH

g. When 0.100 mole of HCl
(g)
is added to 4.0 L of pure water (pH =7.00), what is the
new pH? What are [H
+
] and [OH
-
] and pOH? How does the pH change of the water
compare to that of the above buffer?

The added HCl creates a [H
+
] =0.100 mole/4.0 L =0.025 M
This gives: pH =1.60, pOH =12.40, and [OH
-
] =4.0x10
-13
M (check [H
+
][OH
-
] =K
w
) OK
Note: water is not a good buffer!!

2. a. 0.100 M NaOH
(aq)
is used to titrate 25.00 mL of 0.200 M HCl
(aq)
. Calculate the pH
during this titration at the following volumes of added NaOH: 0.00 mL, 25.00 mL, 49.00
mL, the equivalence point, 51.00 mL, and 60.00 mL.

The balanced reaction: HCl
(aq)
+ NaOH
(aq)
NaCl
(aq)
+ H
2
O
(l)

Note: M =mole per liter may also be mmole per mL . . . which for problems like this one can save a great deal of effort

initial mmole HCl =(0.200 mmole/mL)(25.00 mL) =5.00 mmole HCl
mmole NaOH added =(0.100 mmole/mL)(volume added in mL) =3
rd
column

mL NaOH need to reach equiv. pt. =5.00 mmole needed / 0.100 M =50.0 mL NaOH soln
NOTE: at the equivalence point only NaCl is present in the solution and pH =7.00

mmole excess H
+
=mmole initial HCl mmole added NaOH =4
th
column
mmole excess OH
-
=mmole added NaOH mmole initial HCl =5
th
column
[H
+
] =mmole excess H
+
/ total volume =6
th
column before equiv. pt.
[OH
-
] =mmole excess H
+
/ total volume =6
th
column after equiv. pt.
pH =-log [H
+
], note after the equivlance pt. I used pH =14.00 - pOH

mL
NaOH
mmole H+
initial
mmole
OH- added
mmole H+
excess
mmole OH-
excess
[H+], M pH
0.00 5.00 0.00 5.00 - 2.00E-01 0.70
25.00 5.00 2.50 2.50 - 5.00E-02 1.30
49.00 5.00 4.90 0.10 - 1.35E-03 2.87
50.00 5.00 5.00 0.00 0.00 1.00E-07 7.00
[OH-], M
51.00 5.00 5.10 - 0.10 1.32E-03 11.12
60.00 5.00 6.00 - 1.00 1.18E-02 12.07
Note: see sketch of titration curve below . . . due to limitations of Excel, the shape to the curve is a little odd
114

titration curve of HCl with NaOH
0.00
2.00
4.00
6.00
8.00
10.00
12.00
14.00
0.00 20.00 40.00 60.00
mL 0.100 M NaOH
p
H


b. 0.100 M NaOH
(aq)
is used to titrate 25.00 mL of 0.200 M acetic acid
(aq)
.
[for acetic acid, K
a
=1.8 x 10
-5
] Calculate the pH during this titration at the following
volumes of added NaOH: 0.00 mL, 25.00 mL, 49.00 mL, the equivalence point, 51.00
mL, and 60.00 mL.

The balanced reaction: HOAc
(aq)
+ NaOH
(aq)
NaOAc
(aq)
+ H
2
O
(l)

Notes: OAc
-
represents the acetate ion and HOAc represents acetic acid
M =mole per liter may also be mmole per mL . . . which for problems like this one can save a great deal of effort

initial mmole HOAc =(0.200 mmole/mL)(25.00 mL) =5.00 mmole HOAc
mmole NaOH added =(0.100 mmole/mL)(volume added in mL) =3
rd
column

mL NaOH need to reach equiv. pt. =5.00 mmole needed / 0.100 M =50.0 mL NaOH soln

pH at 0.00 mL is found using an ICE table for 0.20 M acetic acid [K
a
=1.8x10
-5
]
[H
+
] =square root of K
a
*0.20 =1.9x10
-3
M, pH =-log[H
+
] =2.72

mL
NaOH
mmole
HOAc
initial
mmole
OH-
added
mmole
HOAc
excess
mmole
OAc-
formed
[H+], M pH
0.00 5.00 0.00 5.00 - 1.90E-03 2.72
25.00 5.00 2.50 2.50 2.50 1.82E-05 4.74
49.00 5.00 4.90 0.10 4.90 1.35E-03 6.43
[OH-], M
50.00 5.00 5.00 0.00 5.00 6.11E-06 8.79
51.00 5.00 5.10 -
5.00 1.32E-03
11.12
60.00 5.00 6.00 -
5.00 1.18E-02
12.07
115
at 25.00 mL pH =pKa because [HOAc] =[OAc
-
] since one half of the acid has been converted
into the conjugate base and

pH =pK
a
+log [base]/[acid], where base means the basic buffer species and acid is the acidic
buffer species

at 49.00 mL added NaOH the remaining HOAc =0.100 mmole and the OAc
-
=4.90 mmole
since
pH =pK
a
+log [base]/[acid] we find pH =4.74 +log (4.90/0.10) =6.43
Note that we can still use this equation even though we are outside of the buffer range because
our assumptions about the mmole of basic and acidic buffer species are valid

At the equivalence pt. we need to solve an ICE table for the acetate ion with K
b
=5.6x10
-10
since
K
b
=K
w
/K
a
we find [OH-] =square root of 5.6x10
-10
*(5.00 mmole/75.00 mL) =6.1x10
-6
M
Using what should now be standard practice we find pH =14.00 pOH =8.79

Beyond the equivalence point the pH is controlled by the excess NaOH added and the
calculations are the same as found in part (a) at 51.00 and 60.00 mL added NaOH.

Note: see sketch of titration curve below . . . due to limitations of Excel, the shape to the curve is a little odd, adding more data
point could improve the shape.

titration of HOAc with NaOH
0.00
2.00
4.00
6.00
8.00
10.00
12.00
14.00
0.00 10.00 20.00 30.00 40.00 50.00 60.00
mL 0.100 M NaOH
p
H




116
c. Make rough sketches of the above titrations. Note any significant differences and/or
similarities. [ex. look at initial pH, pH at equiv. pt., vol. of NaOH at equiv. pt., etc.]

See (a) and (b) above
similarities: since the stoichiometry of both titrations are 1:1 and the concentration and volumes
used are the same, the equivalence point volume of NaOH is the same. Also, since the
concentration of NaOH and volumes are the same, the pH beyond the equivalence pt. is
the same for both curves
differences: HCl is a strong acid and acetic acid is a weak acid, therefore, the pH of the HCl
curve is lower at the start of the titration. Also, the acetic acid titration curve passes
through a buffer region [centered on pH =pK
a
at the equivalence point]

d. Explain how you might select an indicator for the above titrations? HINT: pK
In
.

Use the Henderson-Hasselbalch equation to understand that we want to choose an indicator that
will change color over a pH range of about 2 pH units [for the same reason that buffers
are effective over about a 2 pH unit range]. Then select an acid-base indicator with a pKa
that falls on the steep part of the titration curve . . . ideally pKa of the indicator will
perfectly match the pH at the equivalence point. When this is not true, there can be a
difference between the added titrant volume at which the color change of the indicator is
observed (known as the end-point) vs. the volume at which the equivalence point is
reached. Our goal is to choose an indicator that will minimize this end-point error.

See the table or figure of indicators in your text:

For the HCl titration we might use chlorphenol red pKa ~6, bromthymol blue pKa ~6.8, or
phenol red pKa ~7.2 . . . but since the equivalence pt. region is VERY steep for a strong
acid-strong base titration, we can even get away with using phenolphthalein pKa ~8.8
and only have a small end-pt error

For the HOAc titration we will want to avoid the chlorphenol red, bromthymol blue, and phenol
red options listed above. Sticking with phenolphthalein for this titration is an excellent
idea [phenolphthalein is a very common choice of indicator for a weak acid-strong base
titration indicator since the pH at the equivalence point will be controlled by a weak base
in these tirations the equivalence point pH will be >7 but also <11]

Note, that for the next curve [weak base-strong acid titration] we will select an indicator that
changes color at a pH <7 but >3 since a weak acid will be present at the equivalence
point.

e. Based on what you have learned from the above, make a sketch of the titration curve
of 25.00 mL 0.200 M ammonia [K
b
=1.8 x 10
-5
] with 0.100 M HCl. You neednt make
calculations, but do understand how you would do so if asked.

See the next page: no calcs. discussed, but a table of values is included.

117
mL HCl mmole
NH3
initial
mmole
H+
added
mmole
NH3
excess
mmole
NH4+
formed
[OH-], M pH
0.00 5.00 0.00 5.00 - 1.90E-03 11.28
25.00 5.00 2.50 2.50 2.50 5.50E-10 9.26
49.00 5.00 4.90 0.10 4.90 1.35E-03 7.57
[H+], M
50.00 5.00 5.00 0.00 5.00 6.11E-06 5.21
51.00 5.00 5.10 - 5.00 1.32E-03 2.88
60.00 5.00 6.00 - 5.00 1.18E-02 1.93

Note: see sketch of titration curve below . . . due to limitations of Excel, the shape to the curve is a little odd, adding more data
point could improve the shape.

titration of NH3 with HCl
0.00
2.00
4.00
6.00
8.00
10.00
12.00
0.00 10.00 20.00 30.00 40.00 50.00 60.00
mL 0.100 M HCl
p
H



3. Calculate the pH of the following two solutions: (i) 0.100 M H
3
PO
4
and (ii) 0.100 M
Na
3
PO
4
. Also, find the concentrations of the following species in each of the two
solutions: H
3
PO
4
, H
2
PO
4
-
, HPO
4
-2
, and PO
4
-3
. HINT: make sure you choose the
correct equilibrium constants at the correct times.

For H
3
PO
4
Acidic
species
Relationship Basic
Conjugate
For Na
3
PO
4
K
a1
= 6.9 x 10
-3
H
3
PO
4
K
w
=K
a1
*K
b3
H
2
PO
4
1-
K
b3
= 6.9 x 10
-3
K
a2
=6.2 x 10
-8
H
2
PO
4
1-
K
w
=K
a2
*K
b2
HPO
4
2-
K
b2
=6.2 x 10
-8
K
a3
=4.5 x 10
-13
HPO
4
2-
K
w
=K
a3
*K
b1
PO
4
3-
K
b1
=4.5 x 10
-
13
Note: the best acid has the least good conjugate base

118
(i) First phosphoric acid, 0.100 M
H
3
PO
4(aq)
+ H
2
O
(l)
<===> H
3
O
+
(aq)
+ H
2
PO
4
1-
(aq)
initial 0.10 M ---- ~ 0 M 0 M
change - x M ---- + x M + x M
equilibrium 0.10 - x M ---- x M x M


[ ][ ]
[ ] ( )
3
- 1
4 2 3
1
10 6 . 6
10 . 0
] ][ [ PO H

+
=

= = x
x
x x
HA
O H
K
a

Since this K
a
is reasonably large we cannot simplify by the assumption that x is small . . . oh well
at least this is not on an exam! So we solve the quadratic equation and take the one root
that is reasonable giving x =[H
3
O
+
] =2.3 x 10
-2
M =[H
2
PO
4
1-
] and pH =1.64
and [H
3
PO
4
] =0.077 M
Note: this is 23% ionization so we certainly cannot avoid the quadratic!

Next we carry through these findings into the second equilibria . . .
H
2
PO
4
1-
(aq)
+ H
2
O
(l)
<===> H
3
O
+
(aq)
+ HPO
4
2-
(aq)
initial 2.3 x 10
-2
M ---- 2.3 x 10
-2
M 0 M
change -y M ---- + y M +y M
equilibrium 2.3 x 10
-2
- y M ---- 2.3 x 10
-2
+ y M y M


[ ][ ]
[ ]
8
2
2
- 1
4 2
- 2
4 3
2
10 2 . 6
] 10 3 . 2 [
] ][ 10 3 . 2 [
PO H
HPO

+
=

+
= = x
y x
y y x O H
K
a

This time we can assume that y is small because this K
a
is small! When we do this we find that
y = [HPO
4
2-
] =K
a2
=6.2 x 10
-8
M and our assumption is valid and the pH =1.64 is still correct

Next we carry through findings from steps one and two into the third equilibria . . .
HPO
4
1-
(aq)
+ H
2
O
(l)
<===> H
3
O
+
(aq)
+ PO
4
3-
(aq)
initial 6.2 x 10
-8
M ---- 2.3 x 10
-2
M 0 M
change -z M ---- + z M +z M
equilibrium 6.2 x 10
-8
-z M ---- 2.3 x 10
-2
+ z M z M


[ ][ ]
[ ]
13
8
2
- 2
4
- 3
4 3
3
10 8 . 4
] 10 2 . 6 [
] ][ 10 3 . 2 [
HPO
PO

+
=

+
= = x
z x
z z x O H
K
a


We can now VERY safely assume that z is small. This yields z =[PO
4
3-
] =1.3 x 10
-18
M and the
pH still is 1.64 !!!!!
119
(ii) For Na
3
PO
4
0.100 M we have a very similar process starting with the phosphate and working
through the steps in the order K
b1
, then K
b2
, then K
b3
we will find . . .. .

from the first equilibrium
PO
4
3-
(aq)
+ H
2
O
(l)
<===> OH
-
(aq)
+ HPO
4
2-
(aq)

solving the quadratic once again!!!!

[OH
-
] =[HPO
4
2-
] =x = 0.037 M
[PO
4
3-
] =0.100 x =0.063 M
btw, this yields pOH =1.43 giving pH =12.57

from the second base ionization step we find
HPO
4
2-
(aq)
+ H
2
O
(l)
<===> OH
-
(aq)
+ H
2
PO
4
1-
(aq)

[H
2
PO
4
-
] = y =1.6x10
-7
M =K
b2
which is such a small change as to not alter the results found above and pH =12.57 is still valid!

from the third base ionization step we find
H
2
PO
4
1-
(aq)
+ H
2
O
(l)
<===> OH
-
(aq)
+ H
3
PO
4(aq)

[H
3
PO
4
] =z =6.5 x 10
-18
M
which is once again such a tiny change that our prior assumptions are all OK and pH =12.57 still
120