Acid-Base Equilibrium and Titration

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 1
 Aqueous Solution Equilibria
Electrolytes: Substances which form ion in
solution
Strong: Mostly in ionic form in solution
HCl, HNO3, NaOH, KOH
HCl + H2O H+(aq) + Cl-(aq)
Weak: Mostly not in ionic form in solution
H2CO3, acetic acid CH3COOH, NH3
NH3 + H2O NH4+(aq) + OH-(aq)

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 2
 A strong electrolyte is completely dissociated.
A weak electrolyte is partially dissociated.

Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

Introduction to Analytical Chemistry
10/9/2017 and Chemical Separation 3
 Arrhenius Theory (Nobel Prize 1894)

- Acid: any substance that ionizes in water

to give hydrogen ions (H+) that associate with
the solvent to increase H3O+ in solution.

- Base: ionizes in water to give hydroxyl

ions (OH-)

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 4
 Brnsted Lowry Theory
- Acid = proton donor
- Base = proton acceptor

acid base acid base

HCl + H2O H3O+ + Cl-
(strong) (weak)

H2CO3+ H2 O H3O+ + HCO3-

(weak) (strong)

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 5
 Brnsted Lowry Acid- Base Reactions
HA + H2O H3O+ + A-
acid1 base2 conj. acid2 conj. base1

base2 + proton conj. Acid2

acid1 conj. base1 + proton

Note: water can act as an acid or a base.

amphiprotic solvent
Introduction to Analytical Chemistry
10/9/2017 and Chemical Separation 6
 A Brnsted acid is a proton donor.
A Brnsted base is a proton acceptor.
acid = H+ + base
These are conjugate pairs.
There must be a proton acceptor before the acid releases its proton.

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 7
 Other amphiprotic solvents:
methanol, ethanol, glacial acetic acid
CH3OH CH3CH2OH CH3COOH
Some amphiprotic solutes:
HCO3- + H2O H3O+ + CO32-
HCO3- + H2O H2CO3 + OH-
HPO42- + H2O H3O+ + PO43-
HPO42- + H2O H2PO4- + OH-

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 8
 Amphiprotic solvent self-ionization
Autoprotolysis:
Generic: SH + SH SH2+ + S-
Water: H2O + H2O H3O+ + OH-
Methanol: CH3OH + CH3OH CH3OH2+ + CH3O-
Glacial acid acid:
CH3COOH + CH3COOH CH3COOH2+ + CH3COO-

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 9
 Acid-Base Equilibria in Water
Reaction: HOAc + HOH H3O+ + OAc-
Thermodynamic Equilibrium Constant
Thermodynamic acidity constant, Koa
Koa = a (H3 O +)
. a(OAc ) - /a (HOAc)
. a(H O)
2

Thermodynamic autoprotolysis or self-

ionization constant
H2O + H2O H3O+ + OH-
Koa = a(H O ) . a(OH )
3
+ - /a (HOH)
. a(HOH)

Koa = a (H3 O +)
. a(OH ) -

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 10
 Reaction: HOAc + HOH H3O+ + OAc-
Thermodynamic Equilibrium Constant
Thermodynamic acidity constant, Koa
Koa = a(H O ) . a(OAc )
3
+ - /a (HOAc)
. a(H O)
2

Molar equilibrium constants, Ka

Koa = Ka ((H O )(OAc ) /(HOAc))
3
+ -

Ka = [H3O+][OAc-]/[HOAc]

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 11
 The pH Scale
pH = -log a(H )
+ or pH -log[H+]
pAnything = - log Anything
pKw = -logKw at 25oC pKw = 14.00
Kw = [H+][OH-]
pKw = pH + pOH =14

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 12
 values
Fractions of Dissociating Species at Given pH
How much of each species?
Analytical concentration: C(H PO ) 3 4

C(H PO ) = [PO43-] + [HPO42-] + [H2PO4-] + [H3PO4]

3 4

0 = [H3PO4] /C(H PO ) , 1 = [H2PO4-] /C(H PO ) ,

3 4 3 4

2 = [H PO42-] /C(H PO ) , 3 = [PO43-] /C(H PO )

3 4 3 4

0 + 1 + 2 + 3 = 1
0 = [H+]3 / ([H+]3 + Ka1[H+]2 + Ka1Ka2[H+] + Ka1Ka2Ka3)
1 = Ka1[H+]2 / ([H+]3 + Ka1[H+]2 + Ka1Ka2[H+] + Ka1Ka2Ka3)
2= Ka1Ka2[H+] / ([H+]3 + Ka1[H+]2 + Ka1Ka2[H+] + Ka1Ka2Ka3)
3= Ka1Ka2K3 / ([H+]3 + Ka1[H+]2 + Ka1Ka2[H+] + Ka1Ka2Ka3)
Introduction to Analytical Chemistry
10/9/2017 and Chemical Separation 13
The common ion effect is the shift in equilibrium caused by the addition of a
compound having an ion in common with the dissolved substance.

The presence of a common ion suppresses the ionization

of a weak acid or a weak base.

Consider mixture of CH3COONa (strong electrolyte) and CH3COOH (weak acid).

CH3COONa (s) Na+ (aq) + CH3COO- (aq)

common
CH3COOH (aq) H+ (aq) + CH3COO- (aq) ion

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 14
 Consider mixture of salt NaA and weak acid HA.

NaA (s) Na+ (aq) + A- (aq)

[H+][A-]
Ka =
HA (aq) H+ (aq) + A- (aq) [HA]

Ka [HA]
[H+] =
[A-] Henderson-Hasselbalch equation
[HA]
-log [H+] = -log Ka - log
[A-]
[conjugate base]
pH = pKa + log
[A-] [acid]
-log [H+] = -log Ka + log
[HA]
[A-]
pH = pKa + log pKa = -log Ka
[HA]

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 15
 What is the pH of a solution containing 0.30 M HCOOH and 0.52 M HCOOK?

Mixture of weak acid and conjugate base!

HCOOH (aq) H+ (aq) + HCOO- (aq)

Initial (M) 0.30 0.00 0.52

Change (M) -x +x +x

Equilibrium (M) 0.30 - x x 0.52 + x

[HCOO-]
Common ion effect pH = pKa + log
[HCOOH]
0.30 x 0.30
[0.52]
0.52 + x 0.52 pH = 3.77 + log = 4.01
[0.30]

HCOOH pKa = 3.77

Introduction to Analytical Chemistry
10/9/2017 and Chemical Separation 16
A buffer solution is a solution of:
1. A weak acid or a weak base and
2. The salt of the weak acid or weak base
Both must be present!

A buffer solution has the ability to resist changes in pH upon the addition of
small amounts of either acid or base.

Consider an equal molar mixture of CH3COOH and CH3COONa

Add strong acid

H+ (aq) + CH3COO- (aq) CH3COOH (aq)
Add strong base
OH- (aq) + CH3COOH (aq) CH3COO- (aq) + H2O (l)

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 17
 HCl H+ + Cl-

HCl + CH3COO- CH3COOH + Cl-

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 18
 Which of the following are buffer systems? (a) KF/HF
(b) KBr/HBr, (c) Na2CO3/NaHCO3

(a) KF is a weak acid and F- is its conjugate base

buffer solution

(b) HBr is a strong acid

not a buffer solution

(c) CO32- is a weak base and HCO3- is it conjugate acid

buffer solution

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 19
 Calculate the pH of the 0.30 M NH3/0.36 M NH4Cl buffer system. What is the
pH after the addition of 20.0 mL of 0.050 M NaOH to 80.0 mL of the buffer
solution?

NH4+ (aq) H+ (aq) + NH3 (aq)

[NH3] [0.30]
pH = pKa + log pKa = 9.25 pH = 9.25 + log = 9.17
[NH4 +] [0.36]

start (moles) 0.029 0.001 0.024

NH4+ (aq) + OH- (aq) H2O (l) + NH3 (aq)

end (moles) 0.028 0.0 0.025

final volume = 80.0 mL + 20.0 mL = 100 mL

0.028 0.025 [0.25]

+]
[NH4 = [NH3] = pH = 9.25 + log = 9.20
0.10 0.10 [0.28]
Introduction to Analytical Chemistry
10/9/2017 and Chemical Separation 20
 Chemistry In Action: Maintaining the pH of Blood

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 21
 Introduction to Analytical Chemistry
10/9/2017 and Chemical Separation 22
 Acid-base titration is a process for calculating the
concentration of a known volume of acid or
base.
Usually, we are interested in how much acid or
base is present in a sample
However, by analyzing a titration curve, we can
also determine pK values for multiple acid/base
components in the sample

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 23
 Equivalence point the point at which the reaction is complete

Indicator substance that changes color at (or near) the

equivalence point

Slowly add base

to unknown acid
UNTIL

The indicator
changes color
(pink)

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 24
 Titration of strong acid-
strong base:
there are three regions
of the titration curve:
before, after, and at
the equivalence point.
The equivalence point
in this situation will
be pH=7 because H+
from a strong acid
reacts
stoichiometrically
with OH-.
Introduction to Analytical Chemistry
10/9/2017 and Chemical Separation 25
Strong Acid-Strong Base Titrations
100% ionization!
NaOH (aq) + HCl (aq) H2O (l) + NaCl (aq)
No equilibrium
OH- (aq) + H+ (aq) H2O (l)

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 26
 - Write balanced chemical equation between
titrant and analyte

- Calculate composition and pH after each

addition of titrant

- Construct a graph of pH versus titrant

added
Introduction to Analytical Chemistry
10/9/2017 and Chemical Separation 27
 - Consider titration of base with acid

H+ + OH- H2O

K = 1/Kw = 1/10-14 = 1014

- Equilibrium constant = 1014

- Reaction goes to completion

H+ + OH- H2O

At equivalence point

moles of titrant = moles of analyte

(V titrant)(M titrant) = (V analyte)(M analyte

Introduction to Analytical Chemistry
10/9/2017 and Chemical Separation 28
 Consider 50.00 mL of 0.100 M NaOH with 0.100 M HCl

- Three regions of titration curve exists

- Before the equivalence point where pH is determined by

excess OH- in the solution

- At the equivalence point where pH is determined by

dissociation of water (H+ OH-)

- After the equivalence point where pH is determined by

excess H+ in the solution
Introduction to Analytical Chemistry
10/9/2017 and Chemical Separation 29
 First calculate the volume of HCl needed to
reach the equivalence point

(V HCl)(0.100 M) = (50.00 mL)(0.100 M)

Volume HCl = 50.00 mL

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 30
 Before the equivalence point

Initial amount of analyte (NaOH)

= 50.00 mL x 0.100 M = 5.00 mmol

After adding 1.00 mL of HCl

mmol H+ added = mmol OH- consumed
mmol H+ = (1.00 mL)(0.100 M) = 0.100 mmol
mmol OH- remaining = 5.00 0.100 = 4.90 mmol

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 31
 Before the equivalence point

Total volume = 50.00 mL + 1.00 mL = 51.00 mL

[OH-] = 4.90 mmol/51.00 mL = 0.0961 M

pOH = - log(0.0961) = 1.017

pH = 14.000 - 1.017 = 12.983

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 32
 - Repeat calculations for all volumes added

- Increments can be large initally but must be reduced just

before
and just after the equivalence point (around 50.00 mL in this
case)

- Sudden change in pH occurs near the equivalence point

- Greatest slope at the equivalence point

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 33
 At the equivalence point

- pH is determined by the dissociation of water

H2O H+ + OH-

Kw = x2 = 1.0 x 10-14

x = 1.0 x 10-7

pH = 7.00 (at 25 oC)

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 34
 After the equivalence point

- Excess H+ is present

After adding 51.00 mL of HCl

Excess HCl present = 51.00 50.00 = 1.00 mL

Excess H+ = (1.00 mL)(0.100 M) = 0.100 mmol

Total volume of solution = 50.00 + 51.00 = 101.00 mL

[H+] = 0.100 mmol/101.00 mL = 9.90 x 10-4 M
pH = -log(9.90 x 10-4) = 3.004
Introduction to Analytical Chemistry
10/9/2017 and Chemical Separation 35
 Equivalence point
(maximum slope or point of inflection)
pH

50.00

Volume
Introduction of HCl
to Analytical added
Chemistry (mL)
10/9/2017 and Chemical Separation 36
Weak Acid-Strong Base Titrations

CH3COOH (aq) + NaOH (aq) CH3COONa (aq) + H2O (l)

CH3COOH (aq) + OH- (aq) CH3COO- (aq) + H2O (l)

At equivalence point (pH > 7):

CH3COO- (aq) + H2O (l) OH- (aq) + CH3COOH (aq)

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 37
 Consider 50.00 mL 0f 0.0100 M acetic acid with 0.100 M
NaOH

pKa of acetic acid = 4.76

HC2H3O2 + OH- C2H3O2- + H2O

For the reverse reaction

Kb = Kw/Ka = 5.8 x 10-10

Equilibrium constant = 1/Kb = 1.7 x 109

So large that we can assume the reaction goes to completion

Introduction to Analytical Chemistry
10/9/2017 and Chemical Separation 38
 Determine volume of base at equivalence point

mmol HC2H3O2 mmol OH-

(V NaOH)(0.100 M) = (50.00 mL)(0.0100 M)

Volume NaOH = 5.00 mL

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 39
 Four types of calculations to be considered

Before OH- is added

- pH is determined by equilibrium of weak

acid

HA H+ + A-

[x 2 ] [x 2 ]
Ka = =
[F - x] [0.0100 - x]
[x 2 ]
=
[0.0100 - x]
Introduction to Analytical Chemistry and
10/9/2017 Chemical Separation 40
 Before equivalence point

By adding OH- a buffer solution of HA and

A- is formed

After adding 0.100 mL OH-

HA + OH- A- + H2O
Initial mmol 0.500 0.0100
0
Final mmol 0.490 0
0.0100

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 41
 Before equivalence point
[A - ]
pH = pK a + log
[HA]

[A - ]
pH = pK a + log
[HA]
[0.0100]
pH = 4.76 + log = 3.07
[0.490]

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 42
 Before equivalence point

If volume of OH- added is half the volume

at equivalence point
HA = A- = 0.250 mmol

[0.250]
pH = 4.76 + log
[0.250]

pH = pKa = 4.76

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 43
 At equivalence point

Volume of OH- = 5.00 mL

mmol OH- = (5.00 mL)(0.100 M) = 0.500

mmol

HA is used up and [HA] = 0

mmol A- = 0.500 mmol

Kb = Kw/Ka = 5.8 x 10-10

x = [OH-] = 2.3 x 10-6

pOH = 5.64
pH = 14.00 5.64 = 8.36

pH is not 7.00 but greater than 7.00

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 44
 At equivalence point

Only A- is present in solution

A- + H2O HA + OH-

[A-] = (0.500 mmol)/(50.00 mL + 5.00 mL) =

0.00909 M

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 45
 At equivalence point

[x 2 ]
Kb =
[F - x]

Kb = Kw/Ka = 5.8 x 10-10

x = [OH-] = 2.3 x 10-6

pOH = 5.64
pH = 14.00 5.64 = 8.36

pH is not 7.00 but greater than 7.00

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 46
 After equivalence point

- Strong base (OH-) being added to weak base (A-)

- pH is determined by the excess [OH-] (approximation)

- After adding 5.10 mL OH-

[OH-] = (0.10 mL)(0.100 M)/(50.00 mL + 5.10 mL)

= 1.81 x 10-4

pH = 14.00 pOH = 14.00 3.74 = 10.26

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 47
Strong Acid-Weak Base Titrations

HCl (aq) + NH3 (aq) NH4Cl (aq)

H+ (aq) + NH3 (aq) NH4Cl (aq)

At equivalence point (pH < 7):

NH4+ (aq) + H2O (l) NH3 (aq) + H+ (aq)

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 48
 Cara menghitung pH titrasi
untuk titrasi asam lemah - basa kuat

Spesi yang
terdapat
Persamaan HA + OH - A- + H2O
pada larutan

HA H3O++ A- Ka = [H3O ][A ]

+ -
HA + H2O
T=0 asam [HA]
terionisasi [H3 O +] = Ka.[HA] [H3 O +]= [A-]

T<1 HA dan A-
Ka =
[H3O+][A-] [A-]
buffer [HA] pH = pKa + log
[HA]
[HA][OH -]
T=1 A- A- + H2O HA + OH -
Kb =
[A-]
Garam [OH-] = Kb.[A-] [HA] = [OH -]
terhidrolisis

T>1 OH- [OH-] = kelebihan titran

Introduction to Analytical Chemistry and
10/9/2017 Chemical Separation 49
 Cara menghitung pH titrasi
untuk titrasi basa lemah - asam kuat

Spesi yang
terdapat Persamaan B + H3O+ HB+ + H2O
pada larutan
[HB+][OH -]
B B + H 2O HB+ + OH - Kb =
T=0 Basa [B]
[OH-] = Kb.[A-]
terionisasi [HB] = [OH -]

T<1 B dan HB+ [HB+][OH -] [HB+]

buffer
Kb = pOH = pKb + log
[B] [B]
T=1 HB+ HB+ + H2O H3O++ B Ka =
[H3O+][B]
[HB+]
Garam
[H3O+] = Ka.[HB+] [H3O+] = [B]
terhidrolisis

T>1 H3O+ [H3O+] = kelebihan titran

Introduction to Analytical Chemistry
10/9/2017 and Chemical Separation 50
 Acid-Base Indicators
HIn (aq) H+ (aq) + In- (aq)
[HIn]
10 Color of acid (HIn) predominates
[In-]

[HIn]
10 Color of conjugate base (In-) predominates
[In-]

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 51
 The titration curve of a strong acid with a strong base.

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 52
 Which indicator(s) would you use for a titration of HNO2 with KOH ?

Weak acid titrated with strong base.

At equivalence point, will have conjugate base of weak acid.

At equivalence point, pH > 7

Use cresol red or phenolphthalein

Introduction to Analytical Chemistry

10/9/2017 and Chemical Separation 53
 Introduction to Analytical Chemistry
10/9/2017 and Chemical Separation 54
 Introduction to Analytical Chemistry
10/9/2017 and Chemical Separation 55