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Chapter 12: Principles of

Neutralization Titrations
By: Andie Aquilato

Solutions and
Indicators Used
Slides 2-6

Standard

Solutions: strong acids or


strong bases because they will react
completely

Acids: hydrochloric (HCl), perchloric (HClO4),


and sulfuric (H2SO4)

Bases: sodium hydroxide (NaOH), potassium


hydroxide (KOH)

Variables:

temperature, ionic strength of


medium and presence of organic
solvents or colloidal particles

Indicators
Acid/Base

Indicators: a weak organic acid or


weak organic base whose undissociated form
differs in color from its conjugate form (In
would be indicator)

HIn + H2O In- + H3O

or

(acid color) (base color)

In + H2O HIn+ + OH(base color) (acid color)

Ka = [H3O+][In-]
[HIn]

[H3O+] = Ka[HIn]
[In-]

Indicators (contd)

HIn pure acid color: [HIn]/[In-] 10


HIn pure base color: [HIn]/[In-] 0.1
~The ratios change from indicator to indicator~

Substitute the ratios into the rearranged Ka:


[H3O+] = 10Ka (acid color)
[H3O+] = 0.1Ka (base color)

pH range for indicator = pKa 1


acid color pH = -log(10Ka) = pKa + 1
base color pH = -log(0.1Ka) = pKa 1

Indicators (contd)
Commonly Used Indicators
Indicator

pH Range

Acid

Base

Thymol Blue

1.2-2.8

red

yellow

Thymol blue

8.0-9.6

yellow

blue

Methyl yellow

2.9-4.0

red

yellow

Methyl orange

3.1-4.4

red

orange

Bromcresol green

4.0-5.6

yellow

blue

Methyl red

4.4-6.2

red

yellow

Bromcresol purple

5.2-6.8

yellow

purple

Bromothymol Blue

6.2-7.8

yellow

blue

Phenol red

6.4-8.0

yellow

red

Cresol purple

7.6-9.2

yellow

purple

Phenolphthalein

8.0-10.0

colorless

red

Thymolphthalein

9.4-10.6

colorless

blue

Alizarin yellow GG

10.0-12.0

colorless

yellow

Calculating pH in
Titrations of Strong
Acids and Strong Bases
Slides 7-11

Titrating a Strong Acid with a


Strong Base calculating pH

Preequivalence: calculate the concentration of the


acid from is starting concentration and the amount
of base that has been added, the concentration of
the acid is equal to the concentration of the
hydroxide ion and you can calculate pH from the
concentration
Equivalence: the hydronium and hydroxide ions
are present in equal concentrations
Postequivalence: the concentration of the excess
base is calculated and the hydroxide ion
concentration is assumed to be equal to or a
multiple of the analytical concentration, the pH can
be calculated from the pOH

Calculating pH (contd) Ex.


Do the calculations needed to generate the hypothetical titration curve for the titration
of 50.00 mL of 0.0500 M HCl with 0.1000 M NaOH
Initial Point: the solution is 0.0500 M in H3O+, so pH = -log(.0500) = 1.30

Preequivalence Point (after addition of 10 mL reagent)


cHCl = mmol remaining (original mmol HCl mmol NaOH added)
total volume (mL)
= (50.0 mL x 0.0500 M) (10.00 mL x 0.1000 M)
50.0 mL + 10.00 mL
= 2.500 x 10 -2 M
pH = -log(2.500 x 10-2) = 1.602

Equivalence Point
[OH-] = [H3O+], pH = 7

Postequivalence Point (after addition of 25.10 mL reagent)


cHCl = mmol NaOH added original mmol HCl
total volume solution
= (21.10 mL x 0.1000 M) (50.00 mL x 0.0500 M)
50.0 mL + 25.10 mL
= 1.33 x 10-4 M
pOH = -log(1.33 x 10-4) = 3.88
pH = 14 pOH = 10.12

Other Things to Consider


Concentrations:

with a higher concentration


titrant (0.1 M NaOH versus 0.001 M NaOH),
the change in pH equivalence-point region is
large

Choosing

an indicator: you need to choose


an indicator that has a color change in the
same range as your equivalence point

Titrating a Strong Base with a


Strong Acid calculating pH

Preequivalence: calculate the concentration of the base


from is starting concentration and the amount of acid that
has been added, the concentration of the base is equal to
the concentration of the hydronium ion and you can
calculate pOH from the concentration, and then the pH
Equivalence: the hydronium and hydroxide ions are
present in equal concentrations, so the pH is 7
Postequivalence: the concentration of the excess acid is
calculated and the hydronium ion concentration is the
same as the concentration of the acid, and the pH can be
calculated

Buffer Solutions
Slides 12-19

Calculating pH of Buffer
Solutions

A buffer is a mixture of a weak acid and its conjugate base or a


weak base and its conjugate acid that resists change in pH
HA + H2O H3O+ + AKa = [H3O+][A-]
[HA]
A- + H2O OH- + HA
Kb = [OH-][HA]
[A-]

Mass-Balance Equation for [HA]: [HA]=cHA [H3O+] + [OH-]

Mass-Balance Equation for [A-]: [A-] = cNaA + [H3O+] [OH-]

Calculating pH of Buffer
Solutions (contd)
[HA] cHA
[A-] cNaA

We can eliminate the rest of the mass-balance equations


because of the inverse relationship between the hydronium and
the hydroxide ion, as well as because the difference in
concentration is so small relative to the concentrations of the
acid and conjugate base

If we substitute the concentration equations for [HA] & [A -] into


the dissociation constant expression, we get
[H3O+] = Ka cHA
cNaA

The hydronium ion concentration is dependent only on the ratio of


the molar concentrations of the weak acid and its conjugate base,
and is independent of dilution because the molar concentrations
change proportionately

Buffer Formed From a Weak


Acid and its Conjugate Base
What is the pH of a solution that is 0.400 M in formic acid and 1.00
M in sodium formate?
HCOOH + H2O H3O+ + HCOOKa = 1.80 x 10-4
HCOO- + H2O HCOOH + OHKb = Kw/Ka = 5.56 x 10-11

[HCOO-] cHCOO- = 1.00 M


[HCOOH] cHCOOH = 0.400 M
[H3O+] = (1.80 x 10-4) (0.400) = 7.20 x 10-5
(1.00)
pH = -log(7.20 x 10-5) = 4.14

Buffer Formed From a Weak


Base and its Conjugate Acid
Calculate the pH of a solution that is 0.200 M in NH 3 and 0.300 M in
NH4Cl.
NH4+ + H2O NH3 + H3O+
Ka = 5.70 x 10-10
NH3 + H2O NH4+ + OHKb = Kw/Ka = 1.75 x 10-5

[NH4+] cNH4Cl = 0.300 M


[NH3] cNH3 = 0.200 M
[H3O+] = (5.70 x 10-10) (0.300) = 8.55 x 10-10
(0.200)
pH = -log(8.55 x 10-10) = 9.07

Properties of Buffers

Dilution: the pH of a buffer solution is essentially


independent of dilution until the concentrations of
the species are decreased to the point so that we
cannot assume that the differences between the
hydronium and hydroxide ion concentrations is
negligible when calculating the concentration of the
species
Added Acids and Bases: buffers are resistant to pH
change after addition of small amounts of strong
acids or bases

Buffer Capacity (the number of moles of strong


acid or strong base that causes one liter of the buffer to
change pH by one unit)
Calculate the pH change that takes place when a 100 mL portion of 0.0500 M NaOH is
added to a 400 mL buffer consisting of 0.2 M NH3 and 0.3 M NH4Cl (see example for Buffers
Formed from a Weak Base and its Conjugate Acid)
An addition of a base converts NH4+ to NH3: NH4+ + OH- NH3 + H2O
The concentration of the NH3 and NH4Cl change:
cNH3 = original mol base + mol base added
total volume
cNH3 = (400 x 0.200) + (100 x 0.300) = 0.170 M
500
cNH4Cl = original mol acid mol base added
total volume
cNH3 = (400 x 0.300) + (100 x 0.300) = 0.230 M
500
[H3O+] = (5.70 x 10-10) (0.230) =7.71 x 10-10
(0.170)
pH = -log(7.71 x 10-10) = 9.11
pH = 9.11 9.07 = 0.04

Preparing Buffers

In principle the calculations work, but there are


uncertainties in numerical values of dissociation
constants & simplifications used in calculations
How to Prepare/Get:

Making up a solution of approximately the desired pH and


then adjust by adding acid or conjugate base until the
required pH is indicated by a pH meter
Empirically derived recipes are available in chemical
handbooks and reference works
Biological supply houses

Calculating pH in Weak
Acid (or Base) Titrations
Slides 20-24

Steps
1.

2.

3.

4.

At the beginning: pH is calculated from the concentration


of that solute and its dissociation constant
After various increments of titrant has been added: pH is
calculated by the analytical concentrations of the
conjugate base or acid and the residual concentrations of
the weak acid or base
At the equivalence point: the pH is calculated from the
concentration of the conjugate of the weak acid or base ~
a salt
Beyond the equivalence point: pH is determined by the
concentration of the excess titrant

Example Calculation
Determine the pH for the titration of 50.00 mL of 0.1000 M acetic acid after adding
0.00, 5.00, 50.00, and 50.01 mL of 0.100 M sodium hydroxide
HOAc + H2O H3O+ + OAcOAc- + H2O HOAc + OHKa = 1.75 x 10 -5

Starting Point:
[H3O+] = 1.32 x 10-3
pH = -log(1.32 x 10-3) = 2.88

After Titrant Has Been Added (5.00 mL NaOH):


*the buffer solution now has NaOAc & HOAc*
cHOAc = mol original acid mol base added
total volume
cHOAc = (50.00 x 0.100) (5.00 x 0.100) = 0.075
60.0
cNaOAc = mol base added
total volume
cNaOAc = (5.00 x 0.100) = 0.008333
60.0
*we can then substitute these concentrations into the dissociation-constant expression for acetic acid*
Ka = [H3O+][OAc-]
[HOAc]
Ka = 1.75 x 10-5 = [H3O+][0.008333]
[0.075]
[H3O+] = 1.58 x 10-4
pH = -log(1.58 x 10-4) = 3.80

Example Calculation (contd)

Equivalence Point (50.00 mL NaOH):


*all the acetic acid has been converted to sodium acetate*
[NaOAc]= 0.0500 M
*we can substitute this in to the base-dissociation constant for OAc -*
Kb = [OH-][HOAc] = Kw
[OAc-]
Ka
[HOAc] = [OH-]

[OH-]2 = 1.00 x 10-14


0.0500 1.75 x 10-5
[OH-] = 5.34 x 10-6
pH = 14.00 (-log(5.34 x 10-6))
pH = 8.73
Beyond the Equivalence Point (50.01 mL NaOH):
*the excess base and acetate ion are sources of the hydroxide ion, but the acetate ion
concentration is so small it is negligible*
[OH-] = cNaOH = mol base added original mol acid
total volume
[OH-] = (50.01 x 0.100) (50.00 x 0.100)
100.01
[OH ] = 1.00 x 10-5
pH = 14.00 (-log(1.00 x 10-5))
pH = 9.00

The Effect of Variables

The Effect of Concentration: the change in pH in the


equivalence-point region becomes smaller with
lower analyte and reagent concentrations

The Effect of Reaction Completeness: pH change in


the equivalence-point region becomes smaller as
the acid become weaker (the reaction between the
acid and the base becomes less complete)

Choosing an Indicator: the color change must occur


in the equivalence-point region

How do Buffer Solutions


Change as a Function of
pH?
Slides 25-27

Alpha Values

Def.: the relative equilibrium concentration of the


weak acid/base and its conjugate base/acid (titrating
with HOAc with NaOH):
*at any point in a titration, cT = cHOAc + cNaOAc*
0 = [HOAc]
cT
1 = [OAc-]
cT
*alpha values are unitless and are equal to one*
0 + 1 = 1

Derivation of Alpha Values


*alpha values depend only on [H3O+] and Ka, not cT*
*mass-balance requires that cT = [HOAc] + [OAc-]*
For 0, we rearrange the dissociation-constant expression to:

[OAc-] = Ka[HOAc]
[H3O+]
*substitute mass-balance into the dissociation-constant expression*
0 = [HOAc] = [ H3O+ ]
cT
[H3O+] + Ka
For 1, we rearrange the dissociation-constant expression to:
[HOAc] = [H3O+] [OAc-]
Ka
*substitute mass-balance into the dissociation-constant expression*
1 = [OAc-] = _____Ka________
cT
[H3O+] + Ka