9

Acid and Base Titrations - Equation Guide

Strong Acid + Strong Base:

Initial Region: pH = - log (nsa / Vsa) or pH = - log (Csa)
" n − nsb % #n − n &
Pre-Equivalence Region: pH = - log $ s a ' or pH = - log % sa sb
(
# Vs a + Vsb & $ Vtotal '
Equivalence: pH = 7
" n − ns a % #n − n sa &
Post-Equivalence Region: pH = 14 + log $ sb ' or pH€= 14 + log % sb
(
# Vsb + Vs a & $ Vtotal '

Strong Base + Strong Acid:

Initial Region: pH = 14 + log (nsb / Vsb) or pH = 14
€ + log (Csb)
" n − ns a % #n − n sa &
Pre-Equivalence Region: pH = 14 + log $ sb ' or pH = 14 + log % sb
(
# Vs a + Vsb & $ Vtotal '
Equivalence: pH = 7
" n − nsb % #n − n &
Post-Equivalence Region: pH = - log $ s a ' or pH = -€log % sa sb
(
# Vs a + Vsb & $ Vtotal '

Weak Acid + Strong Base:

n wa €
Initial Region: pH = - log K a * or pH = - log K a *Cwa
Vwa
" nsb %
Pre-Equivalence Region: pH = pKa + log $ '
# nwa − n sb & €
Half-Equivalence Region: pH = pKa
Kw n wa
Equivalence: pH = 14 + log * or pH= 14 + log K b *Ccb
K a ( Vwa + Vsb)
" n − nwa % #n − n wa &
Post-Equivalence Region: pH = 14 + log $ sb ' or pH = 14 + log % sb
(
# Vsb + Vwa & € $ Vtotal '

Weak Base + Strong Acid:

n wb €
Initial Region: pH = 14 + log Kb * or pH = 14 + log K b *Cwb
Vwb
#n − n sa &
wb
Pre-Equivalence Region: pH = 14 - pKb + log % (
$ n sa ' €

Half-Equivalence Region: pH = 14 - pKb

Kw
€ nwb
Equivalence: pH = - log * or pH= - log K a *Cca
K b ( Vwb + Vs a)
" n − nwb % #n − n &
Post-Equivalence Region: pH = - log $ s a ' or pH = - log % sa wb
(
# Vs a + Vwb & € $ Vtotal '

€
10
Acid and Base Titrations - Guide to Symbols

nsa = moles of strong acid

nsb = moles of strong base
nwa = moles of weak acid
nwb = moles of weak base
nca = moles of conjugate acid
ncb = moles of conjugate base

Vsa = volume of strong acid

Vsb = volume of strong base
Vwa = volume of weak acid
Vwb = volume of weak base
Vca = volume of conjugate acid
Vcb = volume of conjugate base

Csa = concentration of strong acid

Csb = concentration of strong base
Cwa = concentration of weak acid
Cwb = concentration of weak base
Cca = concentration of conjugate acid
Ccb = concentration of conjugate base

Ka = acid dissociation constant for a weak acid

pKa = - log Ka
Ka = 10-pKa

Kb = base dissociation constant for a weak base

pKb = - log Kb
Kb = 10-pKb

Kw = 10-14 = autoionization constant for water at 25 ˚C

Also, Kw = [H3O+]*[OH-] = Ka*Kb = 10-14

pH = - log [H3O+]

pOH = - log [OH-]

14 = pH + pOH = pKa + pKb

 11

Strong Acid + Strong Base Titration - Overview

14

12

10
post-equivalence (nsb > nsa)
8

equivalence (nsa = nsb), pH = 7

pH

initial (only nsa) pre-equivalence (nsa > nsb)

2

0
0 10 20 40 45 48 49 50 51 55 60 80 100
Volume (mL)

Initial: pH = - log [H3O+]

" nsa - nsb %
Pre-equivalence: pH = - log$ '
V
# sa + Vsb &
Equivalence: pH = 7 (neutral salt + water)
" nsb - nsa %
Post-equivalence:
€ pH = 14 + log$ '
# Vsb + Vsa &

€
12

Strong Base + Strong Acid Titration - Overview

initial (only nsb)

14

12

pre-equivalence (nsb > nsa)

10

equivalence (nsb = nsa), pH = 7

pH

4
post-equivalence (nsa > nsb)

0
0 10 20 40 49 50 51 60 80 100
Volume (mL)

Initial: pH = 14 + log [OH-]

" nsb - nsa %
Pre-equivalence: pH = 14 + log$ '
# Vsb + Vsa &
Equivalence: pH = 7 (neutral salt + water)
" nsa - nsb %
Post-equivalence: pH = - log$ '
€ V
# sa + Vsb &

€
 13

Weak Acid + Strong Base Titration - Overview

14

12 post-equivalence
(nsb > nwa)
10

equivalence
8 (nwa = nsb)
pH > 7
pH

6
pKa pre-equivalence
(nwa > nsb)
4

2
half-equivalence
initial (only nwa)
0
0 5 10 15 20 25 30 35
Volume (mL)

Initial: pH = - log K aCa

" nsb %
Pre-equivalence: pH = pK a + log$ '
# nwa - nsb &
€ " K w %" nwa %
Equivalence: pH = 14 + log $ '$ '
K
# a &# waV + Vsb &
€ " nsb - nwa %
Post-equivalence: pH = 14 + log$ '
V
# sb + V wa &
€

€
14

Weak Base + Strong Acid Titration - Overview

10

7 pre-equivalence
initial (only nwb) (nwb > nsa)
6
pH

4
equivalence
14 - pKb half-equivalence (nwb = nsa)
3
pH < 7
2
post-equivalence
1 (nsa > nwb)
0
0 5 10 15 20 25 30 35 40
Volume (mL)

Initial: pH = 14 + log K bCb

" nwb - nsa %
Pre-equivalence: pH = 14 - pK b + log$ '
# nsa &
€ " K w %" nwb %
Equivalence: pH = - log $ '$ '
# K b &# Vwb + Vsa &
€ " nsa - nwb %
Post-equivalence: pH = - log$ '
# Vsa + Vwb &
€

€
 15
CH 223 Guide to Acid and Base Titrations
Acid and base titrations can be a challenging concept for students to conquer in CH 223. This handout
will help prepare you for the types of problems associated with titrations.

A titration is an experimental procedure whereby a solution (usually either acidic or basic) is added
dropwise to a second solution (usually either acidic or basic.) One solution will be acidic while the other will
be basic. The solution that is added dropwise is called the titrant. Titrations are often graphed using pH as the
y-axis and Volume of Titrant (mL) as the x-axis. Sometimes a second y-axis is used to plot the first
derivative; we shall explore this concept in the labs during CH 223.

pH is defined as the negative log of the hydronium concentration, i.e. pH = - log [H3O+]. All of the
calculations given below reflect this basic idea. Values of pH less than seven indicate acidic conditions, while
pH values greater than seven indicate basic conditions; a pH reading of 7 is neutral (neither acidic nor basic).
Weak acids, weak bases, strong acids and strong bases require different formulas to find the concentration of
[H3O+]; hence, there are different mathematical approaches to titrations depending on the substituents being
titrated. We shall concern ourselves only with monoprotic acids and bases - those that have only one
equivalent of H3O+ or OH- to offer.

We will study four monoprotic titration combinations:

• Strong acid titrated with strong base: the pH is initially acidic but becomes more basic as
the strong base titrant is added
• Strong base titrated with strong acid: the pH is initially basic but becomes more acidic as
the strong acid titrant is added
• Weak acid titrated with strong base: the pH is initially somewhat acidic but becomes
more basic as the strong base titrant is added
• Weak base titrated with strong acid: the pH is initially somewhat basic but becomes more
acidic as the strong acid titrant is added

Weak acid + weak base titration combinations require an intensive analysis of Ka and Kb constants and
are of limited versatility; hence, we will cover only the first four types of titrations.

Before you begin calculations for any titration in CH 223, do the following:

1) Determine if solution to be titrated contains an acid or a base, and determine if it is strong or weak.
2) Determine if the titrant is an acid or base and if it is weak or strong
3) If the solution contains a weak acid, find the Ka; if a weak base, find Kb .
4) Refer to the appropriate section:

• Strong Acid (solution) titrated with a Strong Base: Section One

• Strong Base (solution) titrated with a Strong Acid: Section Two
• Weak Acid (solution) titrated with a Strong Base: Section Three
• Weak Base (solution) titrated with a Strong Acid: Section Four

Note: Weak acids with weak bases and weak bases with weak acids will not be covered in CH 223
Polyprotic acid and base titrations will not be mathematically covered in CH 223
Redox titrations will be covered in the subsequent electrochemistry chapter.
Additional information on pH calculations can be found in the Web-only handout "A Closer Look at
Titrations" available on the CH 223 website
16
Section One: Strong Acid + Strong Base (SA + SB) Titration
Equivalence Point pH = 7 neutral

Before you begin:

Strong acids titrated with strong bases will neutralize each other at the equivalence point. Therefore,
you should expect to see a neutral pH when the quantity of acid equals the quantity of base added.

Determine the following quantities:

Vsa = volume of strong acid initially present
nsa = moles of strong acid (= Csa * Vsa)
Csb = concentration of strong base
Vsb = volume of strong base to reach equivalence point (= nsa / Csb)

Analysis Section:

There are four regions in SA + SB titrations that require specific approaches to calculate the pH:

• Initial Region: pH = - log (nsa / Vsa)

The pH will reflect the strong acid only - no strong base has been added.

" n − nsb %
• Pre-Equivalence Region: pH = - log $ s a '
# Vs a + Vsb &
The pH will reflect the remaining acid in solution after some neutralization with strong base.
nsa > nsb in this region.

• Equivalence: pH = 7
nsa = nsb, so water and a neutral salt will be produced at this point.

" n − ns a %
• Post-Equivalence Region: pH = 14 + log $ sb '
# Vs a + Vsb &
The pH will reflect the excess base remaining after neutralizing the strong acid.
nsb > nsa in this region.

Example: Titrate 50.0 mL of 0.200 M HNO3 with 0.100 M NaOH. Determine the pH after 0.00, 10.0,
100. and 150. mL of NaOH has been added.

HNO3 is a strong acid, NaOH is a strong base; the equivalence point pH = 7

Vsa = 50.0 mL = 0.0500 L
nsa = 0.200 M * 0.0500 L = 0.0100 mol
Csb = 0.100 M
Vsb = 0.0100 mol / 0.100 M = 0.100 L = 100. mL NaOH to the equivalence point

At 0.00 mL: Initial point: pH = - log (nsa / Vsa ) = - log (0.0100 mol / 0.0500 L) = 0.70

The pH reflects only the strong acid; no strong base has been added at this point.
 17

" n − ns b %
At 10.0 mL: Pre-equivalence point: pH = - log $ sa '
# Vsa + Vs b &

At 10.0 mL, Vsb = 0.0100 L, and nsb = 0.0100 L * 0.100 M = 0.00100 mol

" n − ns b %
pH = - log $ sa ' = - log " 0.0100 − 0.00100 $ = 0.82
# Vsa + Vs b & # 0.0500 + 0.0100 %

Note: 10.0 mL < 100. mL (equivalence point), so this point is in the pre-equivalence region

At 100. mL: Equivalence point, pH = 7

At 100.0 mL, nsb = 0.100 L * 0.100 M = 0.0100 mol = nsa
Equal molar quantities of acid and base have been added; therefore,
HNO3 + NaOH --> H2O + NaNO3
NaNO3 is a neutral salt, and the pH of water is 7; therefore, the equivalence pH is 7.

" n − nsa %
At 150. mL: Post-equivalence point: pH = 14 + log $ s b '
# Vsa + Vs b &

At 150.0 mL, nsb = 0.150 L * 0.100 M = 0.0150 mol, which is larger than nsa. This point lies in the post-
equivalence region, so:

" n − nsa %
pH = 14 + log $ s b ' = 14 + log " 0.0150 − 0.0100 $ = 12.40
# Vsa + Vs b & # 0.150 + 0.0500 %

The titration graph for a strong acid + strong base would look like this:

Notice the sharp slope around the equivalence point region - this is indicative of strong acid + strong base
titrations. Note that the equivalence point pH is 7.0 - this is also what we would expect for this type of titration.
Knowing how to predict the type of titration from a graph can be of considerable assistance to you in CH 223.
18
Section Two: Strong Base + Strong Acid (SB + SA) Titration
Equivalence Point pH = 7 neutral

Analysis of this type of titration is very similar to the analysis for a Strong Acid + Strong Base (Section 1,
above) except that the strong base will be dominant initially, followed by a slow erosion with a strong acid.
Notice the subtle changes to the equations in this section when compared to section 1; you should see a pattern
developing which can help you in your calculations.

Before you begin:

As in section 1, strong bases titrated with strong acids will neutralize each other at the equivalence point.
Therefore, you should expect to see a neutral pH when the quantity of base equals the quantity of acid added.

Determine the following quantities:

Vsb = volume of strong base initially present
nsb = moles of strong base (= Csb * Vsb)
Csa = concentration of strong acid
Vsa = volume of strong acid to reach equivalence point (= nsb / Csa)

Analysis Section:

There are four regions in SB + SA titrations that require specific approaches to calculate the pH:

• Initial Region: pH = 14 + log (nsb / Vsb)

The pH will reflect the strong base only - no strong acid has been added.
Note the presence of "14" in the equation; this is due to the fact that:

pOH = - log (nsb / Vsb)

and

14 = pH + pOH

Combining these equations and solving for pH gives pH = 14 + log (nsb / Vsb).

" n − ns a %
• Pre-Equivalence Region: pH = 14 + log $ sb '
# Vsb + Vs a &

The pH will reflect the remaining base in solution after some neutralization with strong acid.
nsb > nsa in this region.

• Equivalence: pH = 7
nsb = nsa, so water and a neutral salt will be produced at this point.

" n − nsb %
• Post-Equivalence Region: pH = - log $ s a '
# Vs a + Vsb &

The pH will reflect the excess acid remaining after neutralizing the strong base.
nsa > nsb in this region.
 19

Example: Titrate 100. mL of 0.500 M NaOH with 1.00 M HCl. Determine the pH after 0.00, 25.0,
50.0 and 80.0 mL of NaOH has been added.

NaOH is a strong base, HCl is a strong acid; the equivalence point pH = 7

Vsb = 100. mL = 0.100 L
nsb = 0.500 M * 0.100 L = 0.0500 mol
Csa = 1.00 M
Vsa = 0.0500 mol / 1.00 M = 0.0500 L = 50.0 mL HCl to the equivalence point

At 0.00 mL: Initial point: pH = 14 + log (nsb / Vsb ) = 14 + log (0.0500 mol / 0.100 L) = 13.70

The pH reflects only the strong base; no strong acid has been added at this point.

" n − nsa %
At 25.0 mL: Pre-equivalence point: pH = 14 + log $ s b '
# Vs b + Vsa &

At 25.0 mL, Vsa = 0.0250 L, and nsa = 0.0250 L * 1.00 M = 0.0250 mol

" n − nsa %
pH = 14 + log $ s b ' = 14 + log " 0.0500 − 0.0250 $ = 13.30
# Vs b + Vsa & # 0.100 + 0.0250 %

Note: 25.0 mL < 50.0 mL (equivalence point), so this point is in the pre-equivalence region
Notice how there is little pH change upon adding this much acid. Strong base + strong acid pH curves
change slowly until the equivalence point is reached, then the change becomes quite noticeable.

At 50.0 mL: Equivalence point, pH = 7

At 50.0 mL, nsa = 0.0500 L * 1.00 M = 0.0500 mol = nsb
Equal molar quantities of base and acid have been added; therefore,
NaOH + HCl --> H2O + NaCl
NaCl is a neutral salt, and the pH of water is 7; therefore, the equivalence pH is 7.

" n − ns b %
At 80.0 mL: Post-equivalence point: pH = - log $ sa '
# Vsa + Vs b &

At 80.0 mL, nsa = 0.0800 L * 1.00 M = 0.0800 mol, which is larger than nsb. This point lies in the post-
equivalence region, so:

" n − ns b %
pH = - log $ sa ' = - log " 0.0800 − 0.0500 $ = 0.78
# Vsa + Vs b & # 0.0800 + 0.100 %

Notice how the pH changed rapidly between 25.0 mL of acid added (still quite basic) and 80.0 mL of
acid added (where the pH is quite acidic). As the concentration of strong acids and bases increases, the titration
curves will show a steeper equivalence point.
20

The titration graph for a strong base + strong acid would look like this:

As in section 1, notice the sharp slope around the equivalence point region - this is indicative of strong base +
strong acid titrations. Note that the equivalence point pH is 7.0 - this is also what we would expect for this type
of titration. At first, the NaOH dominated the titration, and the graph pH was quite basic. At the conclusion of
the titration, HCl dominated and overcame the NaOH present in solution, and the pH became quite acidic.
Remembering simple facts can aid your analysis of titrations in CH 223.
 21
Section Three: Weak Acid + Strong Base (WA + SB) Titration
Equivalence Point pH > 7 basic

Weak acids and weak bases have incomplete ionization in solution, which is in marked contrast to their
strong acid and strong base counterparts. For example, if we have a solution of 1.00 M HCl in water,

HCl(aq) -> H+(aq) + Cl-(aq)

we would have 100% of the HCl(aq) converted to H+(aq) and Cl-(aq); no HCl would remain in solution.
If we had a solution of 1.00 M HC2H3O2 in water,

HC2H3O2(aq) <=> H+(aq) + C2H3O2-(aq)

we would have roughly 99% of the HC2H3O2 still present in solution; less than 1% of the HC2H3O2(aq) would
ionize into H+(aq) and C2H3O2-(aq). Weak acids and weak bases do not ionize completely in solution. Recall that
if HC2H3O2 is our weak acid, C2H3O2-(aq) will be the conjugate base in this system. Strong acids and bases do
not have effective conjugate acids or bases.
To account for the discrepancy in ionization behavior, we will use the acid equilibrium constant, Ka,
and the base equilibrium constant, Kb, in our calculations. Recall that Ka and Kb are related to Kw, the
autoionization of water constant, by the following expression:

Kw = Ka * Kb

To speed our calculations when the weak acid or weak base is present in excess, we can use the
Henderson-Hasselbalch equation. We will use a slightly modified form in this section, but the generic
equation is:

pH = pKa + log
[Conj. base ]
[acid ]

where pH = pH of system
pKa = -log Ka = - log (acid dissociation constant for weak acid in buffer)
[Conj. base] = concentration or moles of base in solution
[acid] = concentration or moles of weak acid in solution

The Henderson-Hasselbalch equation tells us that when the moles of the strong base added equal one-
half the moles of weak acid initially present (i.e. 1/2 nwa = nsb), a special condition occurs; this point is called the
half-equivalence point, and pH = pKa here. Therefore, we need to add an additional region to our calculations,
the half-equivalence region.

Before you begin: Determine the following quantities:

Vwa = volume of weak acid initially present
nwa = moles of weak acid (= Cwa * Vwa)
Ka = acid dissociation constant for the weak acid
pKa = - log Ka (this is a just a unitless number)
Csb = concentration of strong base
Vsb = volume of strong base to reach equivalence point (= nwa / Csb)
Also remember that at room temperature, Kw = 10-14
22
Analysis Section: There are five regions in WA + SB titrations in which to calculate the pH:

n wa
• Initial Region: pH = - log K a *
Vwa

The pH will reflect the weak acid only - no strong base has been added. Recall that for weak acids,

[H3O+] = K a * Cwa

and Cwa = nwa / Vwa, just as pH = - log [H3O+].

" nsb %
• Pre-Equivalence Region: pH = pKa + log $ '
# nwa − n sb &

Because nwa > nsb in this region, the pH will be affected by two factors: 1) the remaining weak acid in the
solution, and 2) the conjugate base present upon addition of strong base. For weak acids HA reacting with
strong base NaOH,

HA + NaOH -> HOH + Na+ + A-

The species A- is the conjugate base of the weak acid HA, and it will react with water to re-form the weak acid:

A- + H2O <=> HA + OH-

The generation of OH- from the conjugate base will affect pH.
Fortunately, the weak acid / conjugate base system can be treated like a buffer; hence, the usefulness of
the Henderson-Hasselbalch equation. Recall that the Henderson-Hasselbalch equation is

pH = pKa + log
[Conj. base ]
[acid ]

[Conj. base] and [acid] can be re-written as nsb and (nwa - nsb), respectively*, or

ns b
pH = pKa + log
nwa − ns b

* Why? OK, here goes: for every mole of conjugate base created, an equal number of moles of strong base
must be added, so [Conj. base] = nsb. Also, the moles of weak acid present in solution will depend on how
many moles of strong base have been added, so [acid] = (nwa - nsb).
Note that there is no volume dependence in the pre-equivalence region; you need not calculate total
volume, etc. in this region if using the Henderson-Hasselbalch equation.

• Half-Equivalence Region: pH = pKa

At half-equivalence, 1/2 nwa = nsb, and the log term in the pre-equivalence equation goes to zero (log 1 =
0). Note that you can predict the pH of any weak acid system at half-equivalence by calculating the pKa!
 23
Kw n wa
• Equivalence: pH = 14 + log *
K a ( Vwa + Vsb)

At the equivalence point, nwa = nsb, and the only factor affecting pH is the conjugate base (see discussion
on pre-equivalence, above.) To find [OH-] for a weak base, use:

n cb
[OH-] = K b * C cb = K b *
Vcb

For every mole of weak acid, an equal number of moles of conjugate base are created; hence, ncb = nwa.
The term Vcb must take into account the total volume present in solution, hence, Vcb = Vwa + Vsb.
Kb can be rewritten as Kw / Ka.
Converting [OH-] to pH provides the necessary equation

Kw nwa
pH = 14 + log *
K a ( Vwa + Vs b )

Note that in titrations of weak acids with strong bases, the equivalence point pH will be affected by the
pH of the conjugate base only; no weak acid remains in solution. Therefore, expect basic pH values at the
equivalence point in weak acid + strong base titrations.

" n − nwa %
• Post-Equivalence Region: pH = 14 + log $ sb '
# Vsb + Vwa &

The pH will reflect the excess strong base remaining after neutralizing the weak acid. (nsb > nwa)
Note that the contribution of the conjugate base will have no appreciable effect on the pH assuming
even a small portion of strong base is present in solution; therefore, it is omitted from the calculation.

Example: Titrate 50.0 mL of 0.100 M HC2H3O2 (Ka = 1.80*10-5) with 0.100 M NaOH. Determine the pH
after 0.00, 10.0, 25.0, 40.0, 50.0 and 60.0 mL of NaOH has been added.

HC2H3O2 is a weak acid, NaOH is a strong base; the equivalence point should be basic
Vwa = 50.0 mL = 0.0500 L
nwa = 0.100 M * 0.0500 L = 0.00500 mol
Csb = 0.100 M
Vsb = 0.00500 mol / 0.100 M = 0.0500 L = 50.0 mL NaOH to the equivalence point
The half-equivalence point will be reached at (50.0 mL / 2) or 25.0 mL NaOH
pKa = - log Ka = - log (1.80*10-5) = 4.74

At 0.00 mL: Initial point:

nwa 0.00500
pH = - log K a * = - log 1.8 *10−5 * = 2.87
Vwa 0.0500

The pH reflects only the weak acid; no strong base has been added at this point.
Note how the initial pH of a weak acid is considerably more basic than the initial pH of a strong acid;
this is due to the incomplete ionization of the weak acid (and the resulting dependency on Ka.)
24

At 10.0 mL: Pre-equivalence point:

ns b 0.00100
pH = pKa + log = 4.74 + log = 4.14
nwa − ns b 0.00500 − 0.00100

At 10.0 mL, Vsb = 0.0100 L, and nsb = 0.0100 L * 0.100 M = 0.00100 mol
Note: 10.0 mL < 50.0 mL (equivalence point), so this point is in the pre-equivalence region

At 25.0 mL: Half-equivalence point: pH = pKa = 4.74

This is a simple calculation but one which gives tremendous insight into the system being studied.

At 40.0 mL: Pre-equivalence point:

ns b 0.00400
pH = pKa + log = 4.74 + log = 5.34
nwa − ns b 0.00500 − 0.00400

At 40.0 mL, Vsb = 0.0400 L, and nsb = 0.0400 L * 0.100 M = 0.00400 mol
Note: 40.0 mL < 50.0 mL (equivalence point), so this point is in the pre-equivalence region

At 50.0 mL: Equivalence point:

Kw nwa 10 −1 4 0.00500
pH = 14 + log * = 14 + log −5 * = 8.72
K a ( Vwa + Vs b ) 1.80 *10 (0.0500 + 0.0500)

Note that this equation looks somewhat nasty, but really it's just a good old "plug and chug" equation.
Notice how the equivalence pH is basic as predicted.

At 60.0 mL: Post-equivalence point:

" n − n wa %
pH = 14 + log $ s b ' = 14 + log " 0.00600 − 0.00500 $ = 11.96
# Vs b + Vwa & # 0.0600 + 0.0500 %

At 60.0 mL, nsb = 0.0600 L * 0.100 M = 0.00600 mol, which is larger than nwa. This point lies in the
post-equivalence region.
The titration graph for a weak acid + strong base would look like the diagram below:

Note that the equivalence point is basic in a weak acid + strong base titration, a result of the conjugate base of
the weak acid. Also note how the slope around the equivalence point is not as steep as it was when strong acids
and bases were mixed together.
 25
Section Four: Weak Base + Strong Acid (WB + SA) Titration
Equivalence Point pH < 7 acidic

As discussed in section three (WA + SB), weak acids and bases do not ionize completely in solution.
For example, if we had a solution of 1.00 M NH3 (ammonia, a weak base) in water,

NH3(aq) + H2O(l) <=> NH4+(aq) + OH-(aq)

we would have roughly 99% of the ammonia still present in solution; less than 1% of the NH3(aq) would ionize
with water into NH4+(aq) and OH-(aq). Recall that NH4+(aq) will be the conjugate acid in this system. This lack of
complete ionization forces a dependency upon the base equilibrium constant, Kb, in our calculations.
As before, to speed our calculations when the weak base is present in excess, we can use the
Henderson-Hasselbalch equation. We will use a slightly modified form for this section. The half-
equivalence point will also be of use to use just as it was in the WA + SB titration.

Before you begin:

Determine the following quantities:

Vwb = volume of weak base initially present
nwb = moles of weak base (= Cwb * Vwb)
Kb = base dissociation constant for the weak base
pKb = - log Kb (this is a just a unitless number)
Csa = concentration of strong acid
Vsa = volume of strong acid to reach equivalence point (= nwb / Csa)
Also remember that at room temperature, Kw = 10-14

Analysis Section:

There are five regions in WB + SA titrations that require specific approaches to calculate the pH:

n wb
• Initial Region: pH = 14 + log Kb *
Vwb

The pH will reflect the weak base only - no strong acid has been added. Recall that for weak bases,

[OH-] = K b * C wb

and Cwb = nwb / Vwb. Recall that pOH = - log [OH-] and that pH + pOH = 14; therefore,

n wb
pH = 14 + log K b *
Vwb
26
• Pre-Equivalence Region: This region uses a modified version of the Henderson-Hasselbalch equation to
calculate pH:

#n − n &
pH = 14 - pKb + log % wb sa
(
$ n sa '

Because nwb > nsa in this region, the pH will be affected by two factors: 1) the remaining weak base in
€ addition of strong acid. For a weak base A- reacting with
the solution, and 2) the conjugate acid present upon
strong acid HCl,

A- + HCl -> HA + Cl-

The species HA is the conjugate acid of the weak base A-, and it will react with water to re-form the weak acid:

HA + H2O <=> A- + H3O+

The generation of H3O+ from the conjugate acid will affect pH.
As in the weak acid / strong base scenario, the weak base / conjugate acid system can be treated like a
buffer; hence, the usefulness of the Henderson-Hasselbalch equation. Recall that the Henderson-Hasselbalch
equation is

pH = pKa + log
[Conj. base ]
[acid ]

We will modify the Henderson-Hasselbalch equation to our weakly basic system. [Conj. base] and [acid] can
be re-written as (nwb - nsa) and nsa, respectively*, and since pKa + pKb = 14, we can re-write our equation as

#n − n &
pH = 14 - pKb + log % wb sa (
$ nsa '

* Why? OK, here goes: for every mole of conjugate acid created, an equal number of moles of strong acid
must be added, so [acid] = nsa. Also, the moles of weak base present in solution will depend on how many
€ base] is (n - n ).
moles of strong acid have been added, therefore [Conj. wb sa
Note that there is no volume dependence in the pre-equivalence region; you need not calculate total
volume, etc. in this region if using the Henderson-Hasselbalch equation.

• Half-Equivalence Region: pH = 14 - pKb

At half-equivalence, 1/2 nwb = nsa, and the log term in the pre-equivalence equation goes to zero (log 1 =
0). Note that you can predict the pOH of any weak base system at half-equivalence by calculating the pKb!
Converting to pH requires a simple but necessary calculation.

Kw nwb
• Equivalence: pH = - log *
K b ( Vwb + Vs a)
 27
At the equivalence point, nwb = nsa, and the only factor affecting pH is the conjugate acid (see discussion
on pre-equivalence, above.) To find [H3O+] for a weak acid:

nca
[H3O+] = K a * Cca = K a *
Vca

For every mole of weak base, an equal number of moles of conjugate acid are created; hence, nca = nwb.
The term Vca must take into account the total volume present in solution, hence, Vca = Vwb + Vsa.
Ka can be rewritten as Kw / Kb.
Converting [H3O+] to pH provides the necessary equation

Kw nwb
pH = - log *
K b ( Vwb + Vsa )

Note that in titrations of weak bases with strong acids, the equivalence point pH will be affected by the
pH of the conjugate acid only; no weak base or strong acid remains in solution. Therefore, expect acidic pH
values at the equivalence point in weak base + strong acid titrations.

" n − nwb %
• Post-Equivalence Region: pH = - log $ s a '
# Vs a + Vwb &

The pH will reflect the excess strong acid remaining after neutralizing the weak base.
nsa > nwb in this region.
Note that the contribution of the conjugate acid will have no appreciable effect on the pH assuming even
a small portion of strong acid is present in solution; therefore, it is omitted from the calculation.

Example: Titrate 100. mL of 0.0500 M NH3 (Kb = 1.80*10-5) with 0.100 M HCl. Determine the pH after
0.00, 10.0, 25.0, 50.0 and 60.0 mL of HCl has been added.

NH3 is a weak base, HCl is a strong acid; the equivalence point should be acidic
Vwb = 100. mL = 0.100 L
nwb = 0.0500 M * 0.100 L = 0.00500 mol
Csa = 0.100 M
Vsa = 0.00500 mol / 0.100 M = 0.0500 L = 50.0 mL HCl to the equivalence point
The half-equivalence point will be reached at (50.0 mL / 2) or 25.0 mL HCl
pKb = - log Kb = - log (1.80*10-5) = 4.74

At 0.00 mL: Initial point:

n wb 0.00500
pH = 14 + log Kb * = 14 + log 1.8 *10−5 * = 10.98
Vwb 0.100

The pH reflects only the weak base; no strong acid has been added at this point.
Note how the initial pH of a weak base is considerably more acidic than the initial pH of a strong base;
this is due to the incomplete ionization of the weak base (and the resulting dependency on Kb.)
28
At 10.0 mL: Pre-equivalence point:

#n − n & 0.00500 − 0.00100

pH = 14 - pKb + log % wb sa ( = 14 - 4.74 + log = 9.86
$ nsa ' 0.00100

At 10.0 mL, Vsa = 0.0100 L, and nsa = 0.0100 L * 0.100 M = 0.00100 mol
Note: 10.0 mL < 50.0 mL (equivalence point), so this
€ point is in the pre-equivalence region
€
At 25.0 mL: Half-equivalence point: pH = 14 - pKb = 14 - 4.74 = 9.26

This is a simple calculation (yeah!) but one which gives tremendous insight into the system being
studied.

At 50.0 mL: Equivalence point:

Kw nwb 10 −1 4 0.00500
pH = - log * = - log −5 * = 5.37
K b ( Vwb + Vsa ) 1.80 *10 (0.0500 + 0.100)

Note that this equation looks somewhat nasty, but really it's just a good old "plug and chug" equation.
All of the values have been calculated, and the application will become easier with time.
Notice how the equivalence point pH is acidic as predicted.

At 60.0 mL: Post-equivalence point:

" n − nwb %
pH = - log $ sa ' = - log " 0.00600 − 0.00500 $ = 2.20
# Vsa + Vwb & # 0.0600 + 0.100 %

At 60.0 mL, nsa = 0.0600 L * 0.100 M = 0.00600 mol, which is larger than nwb. This point lies in the
post-equivalence region.

The titration graph for a weak base + strong acid would look like this:

Note that the equivalence point is acidic in a weak base + strong acid titration, a result of the conjugate acid of
the weak base. Also note how the slope around the equivalence point is not as steep as it was when strong acids
and bases were mixed together.
 29
Exercises: Complete these problems using the worksheet on the next page. Also, construct a graph of pH
versus Volume of Titrant for each problem.

1. You wish to titrate 50.0 mL of a 0.100 M HCl solution with 0.100 M NaOH. Calculate the pH after the
addition of 0.00 mL, 10.0 mL, 20.0 mL, 40.0 mL, 45.0 mL, 48.0 mL, 49.0 mL, 50.0 mL, 51.0 mL, 55.0 mL,
60.0 mL, 80.0 mL and 100.0 mL. Plot the results of your calculations as pH versus mL of NaOH added.

2. You wish to titrate 50.0 mL of a 0.100 M NaOH solution with 0.100 M HCl. Calculate the pH after the
addition of 0.00 mL, 10.0 mL, 20.0 mL, 40.0 mL, 49.0 mL, 50.0 mL, 51.0 mL, 60.0 mL, 80.0 mL, 90.0 mL
and 100.0 mL. Plot the results of your calculations as pH versus mL of HCl added.

3. A 25.0 mL solution of 0.100 M lactic acid (HC3H5O3, pKa = 3.85) is titrated with 0.100 M NaOH. Calculate
the pH after the addition of 0.00 mL, 4.00 mL, 8.00 mL, 12.5 mL, 20.0 mL, 24.0 mL, 24.5 mL, 25.0 mL,
26.0 mL, 28.0 mL and 30.0 mL of NaOH. Plot the results of your calculations as pH versus mL of NaOH
added.

4. A student titrates 25.0 mL of 0.100 M pyridine (Kb = 1.7*10-9) with 0.100 M HCl. Calculate the pH after
the addition of 0.00 mL, 4.00 mL, 8.00 mL, 12.5 mL, 20.0 mL, 24.0 mL, 24.5 mL, 25.0 mL, 26.0 mL, 28.0
mL, 30.0 mL and 35.0 mL of HCl. Plot the results of your calculations as pH versus mL of HCl added.
30
 31
CH 223 Titration Calculations Answer Sheet Name: ______________________

Provide answers to the questions (found on the previous page) using the sheet below. Report all pH values to
the hundredths place. Circle the equivalence point and the half-equivalence point volume (if appropriate)
on the handout below. In addition, computer generated graphs (using Excel, etc.) of the titrations and all
necessary calculations must be included to receive full credit; staple additional pages to the back of this
handout.

Question #1 Question #2 Question #3 Question #4

Volume NaOH pH Volume HCl pH Volume NaOH pH Volume HCl pH

0.00 0.00 0.00 0.00

10.0 10.0 4.00 4.00

20.0 20.0 8.00 8.00

40.0 40.0 12.5 12.5

45.0 49.0 20.0 20.0

48.0 50.0 24.0 24.0

49.0 51.0 24.5 24.5

50.0 60.0 25.0 25.0

51.0 80.0 26.0 26.0

55.0 90.0 28.0 28.0

60.0 100.0 30.0 30.0

80.0 35.0

100.0
32