NEUTRALIZATION ANALYSIS

TITRATION CURVES
K
(A) + (R) (P)
analyte titrant product

Outline
NEUTRALIZATION
ANALYSIS

Introduction

Titrants

Titration curves Important points and regions:

2 points: before titration (at 0%) I. [A]
End point
detection at the end point (at 100 %) III. [A] = [R]
2 regions: before the end point (0.00..1 – 99.99…%) II. [A] + [P]
Applications after the end point (100.00..1 – ∞) IV. [P] + [R]
Titration curves:
1. Strong acid with strong base, Strong base with strong acid
2. Weak acid with strong base, Weak base with strong acid
3. Polyprotic acid with strong base
1
 TITRATION CURVES
1. Strong acid with strong base, Strong base with strong acid

Outline
NEUTRALIZATION
ANALYSIS
e.g. HCl + NaOH Cl– + Na+(H2O)
acid1 + base2 base1 + acid2
Introduction I. At the start: (very weak)

Titrants [H+] = [H3O+]=[HCl]0 [OH–] = [NaOH]0

pH = – lg [HCl]0 pOH = – lg [NaOH]0 pH = 14 – pOH
Titration curves
II. Before the end point:
End point [H+] = [H3O+]=[HCl]unreacted [OH–] = [NaOH]unreacted
detection pH = – lg [HCl]unreacted pOH = – lg [NaOH]unreacted
Applications
III. At the end point:
[H+] ≡ [OH–]
KW = 10–14 pH ≡ 7
IV. After the end point:
[OH–] = [NaOH]excess [H+] = [H3O+]=[HCl]excess
2
pOH = – lg [NaOH]excess pH = – lg [HCl]excess
 TITRATION CURVES
Titration curves:
1. Strong acid with strong base, Strong base with strong acid
2. Weak acid with strong base, Weak base with strong acid
3. Polyprotic acid with strong base

EFFECTS ON THE TITRATION CURVE:

1. Effect of the temperature:
Outline 25°C [H+]·[OH–] = Kw = 10–14 Neutr. point: pH = 7
NEUTRALIZATION
ANALYSIS 100°C [H+]·[OH–] = Kw = 10–12 Neutr. point: pH = 6
Introduction

Titrants

Titration curves 0 100

End point
detection

Applications
3
 EFFECTS ON THE TITRATION CURVE
2. Dependence on the initial concentrations (e.g. [HCl]):

[HCl]0 0% 50% 90% 99% 99.9% 100% 100.1% 101% 110%

↓
1N 0 0,3 1 2 3 7 11 12 13
0,1 N 1 1,3 2 3 4 7 10 11 12
0,01 N 2 2,3 3 4 5 7 9 10 11
0,001 N 3 3,3 4 5 6 7 8 9 10
Outline
pH change around the end point
NEUTRALIZATION
ANALYSIS
ΔpH
3 – 11
Introduction 4 – 10
5– 9
Titrants 6– 8

Titration curves

End point
detection

Applications
0 100 4
 EFFECTS ON THE TITRATION CURVE
3. Dependence on the acid strength (dissociation constants):

A. Weak acid with strong bases , 0 100

Outline e.g. 10–1 N CH3COOH is titrated with NaOH (Ka = 2x10–5)

NEUTRALIZATION % 0 50 90 99 99.9 100 100.1 101 110
ANALYSIS
Introduction pH 2.9 4.7 5.7 6.7 7.7 8.9 10 11 12

Titrants
B. Weak base with strong acid ΔpH pKInd ≈ 9 → PHENOLPHTALEIN
Titration curves
e.g. 10–1 N NH4OH is titrated with HCl (Kb = 2x10–5)
End point % 0 50 90 99 99.9 100 100.1 101 110
detection
pH 11.1 9.3 8.3 7.3 6.3 5.1 4 3 2
Applications
5
ΔpH pKInd ≈ 5 → METHYL RED
 TITRATION CURVES
II. Weak acid with strong base Weak base with strong acid
e.g. Titration of CH3COOH with NaOH , Titration of NH4OH with HCl:
I. At the start:
Weak acid pH Weak base
H  

K a C acid H    K a CH 3 COOH OH   
K b C base OH  

K b NH 4 OH

II. Before the end point:

Buffer (acid / salt) pH Buffer (base / salt)
Outline H   K

a
C acid
C salt
CH COOH
H   KCH
 a

COO 
3
3

OH   K

b
C base
C salt
OH   K NH OH
 b

NH 
4
4


NEUTRALIZATION
ANALYSIS III. At the end point:
Introduction
Hydrolysing salt (Brönsted base) pH Hydrolysing salt (Brönsted acid)
Titrants OH    Kw
C salt H  
 Kw
Kb
C salt
Ka

Titration curves OH  


K b Csalt OH  


K b CH3 COO  H  

K a C salt H  


K a NH 4


End point
detection IV. After the end point:
Excess of strong base pH Excess of strong acid
Applications
[OH–] = Cexcess base [OH–] = [NaOH]excess [H+] = Cexcess acid [H+] = [HClexcess 6
 TITRATION CURVES
III. Polyprotic acid with strong base
e.g. Titration of H3PO4 with NaOH

1. H3PO4 + OH– H2PO4– + H2O Ka1 = 7x10–3

2. H2PO4– + OH– HPO42– + H2O Ka2 = 6x10–8
3. HPO42– + OH– PO43– + H2O Ka3 = 10–12

Outline
NEUTRALIZATION
ANALYSIS
Introduction

Titrants

Titration curves

End point
detection

Applications
7
 ACID / BASE INDICATORS
1. Azo-compounds
Genearal structure:
INDICATOR R1 R2 R3 ∆pH Acidic Basic
color color
METHYL- -N(CH3)2 H SO3Na 3.1 – 4.4 red orange
ORANGE
METHYL -N(CH3)2 COOH H 4.4 – 6.2 red yellow
-RED
p-ETHOXY- -OC2H5 NH2 NH2 3.5 – 5.5 red yellow
CHRISOIDINE
TROPAEOLIN -SO3Na OH OH 11.1 – yellow orange
0 12.7!

Outline
NEUTRALIZATION
ANALYSIS
Mechanism:
Introduction

Titrants

Titration curves

End p. detection
- chemical
- instrumental
Yellow Yellow Red
Applications (basic) (intermediate) (acidic) 8
(aromatic) (protonated) (quinoid)
 ACID / BASE INDICATORS
2. PHTHALEIN-derivatives
General structure:
INDICATOR R R1 R2 R3 ∆pH Acidic Basic
color color
PHTALEINS COOH basic colorless colored
PHENOLPHTHALEIN COOH H H H 8.2 – colorless red
10.0
THYMOLPHTHALEIN COOH CH(CH3)2 H CH3 8.3 – colorless blue
10.5

SULFON- SO3H basic / colored colored

PHTHALEINS acidic
PHENOL RED SO3H H H H 6.4 – yellow red
8.0
THYMOL BLUE SO3H CH(CH3)2 H CH3 a)1.2 – red yellow

Outline 2.8
b)8.0 –
9.6
yellow blue

NEUTRALIZATION
ANALYSIS
Mechanism: Thymol blue
Introduction

Titrants

Titration curves

End p. detection
- chemical
- instrumental
Colorless Colorless Purple
Applications (acidic) (intermediate) (basic) 9
 INSTRUMENTAL DETECTION
(Summary)
The titration process is followed by electrochemical,
photometric or other sensing devices.
Outline
Method Sensing device Type of titration
POTENTIOMETRY Different types of Neutralization titr.
INSTRUMENTAL Complexometric titr.
DETECTION (Potential vs %) electrodes Precipitation titr.
Redox titr.
AMPEROMETRY Pt electrode Redox titr.
Advantages
(Current vs %) (dead stop…)
Types
CONDUCTOMETRY Conductivity cell Neutralization titr.
Potentiometric (Conductivity vs %) Precipitation titr.
end point
detection PHOTOMETRY Spectrophotometer Complexometric
(A = ε · c · l vs %) titr.
Conductometric
end point ENTALPHYMETRY Thermistor Neutralization titr.
detection Complexometric titr.
(Q = f (c, ΔH) vs % Precipitation titr.
Redox titr.
10
 POTENTIOMETRY
Electrode potential developed
between:
Indicator electrode Reference electrode
 Potential (Eind) varies  Known, constant potential (Eref)
Outline  Depends on  Independent
the analyte concentration of the analyte concentration
Common reference electrodes:
INSTRUMENTAL Solid metal / its „unsoluble” salt / saturated conc. of anion
DETECTION
e.g. Ag / AgCl / KCl
Hg / Hg2Cl2 / KCl
Hg / Hg2SO4 / K2SO4
Advantages
0.059
E  E0 
Nernst equation: n
lg c
Types
Glass electrode Neutralization titration: E = E0 + 0.059 lg [H+]
Potentiometric
end point Metal
Complexometric titration: E = E0 + 0.059 lg [Mn+]
detection electrode n
Conductometric Ion-selective Precipitation titration:
end point electrode E = E0 + 0.059 lg [X−]
detection
Nobel metal Redox titration: E = E0 + 0.059lg [ox]
electrode n [red] 11
 POTENTIOMETRY
Neutralization analysis External
Indicator electrode: reference electrode Glass electrode

GLASS ELECTRODE
Outline
INSTRUMENTAL H+ conc. to be determined
DETECTION

Electrochemical cell for measurement of pH:

Advantages
External reference || H+ conc. |pH-sensitive | Internal | Internal reference
Types electrode || to be | glass- | buffer sol. | electrode
Potentiometric (Hg/Hg2Cl2/KCl) ||determined | membrane | (KCl) (pH = 7) | (Ag/AgCl/KCl)
end point
detection ███████████
External Dry glass Internal
Conductometric hydrated hydrated
end point
detection
gel layer gel layer

12
 POTENTIOMETRY
Glass electrode
Composition of glass:
E.g. 22 % Na2O, 6 % CaO, 72 % SiO2.
Na+ mobile membrane solution
H+
Outline Ion-exchange reaction:
Na++
H
Na+
between H++
Na
H+ in the solution and
INSTRUMENTAL
DETECTION Na+ in the glass:
K
H+ + Na+Gl−  Na+ + H+Gl– K = LARGE!
Advantages
solution glass solution glass
Types Combination glass electrode:
Potentiometric
end point
detection

Conductometric
end point
detection

13
 POTENTIOMETRY
Titration curve

Potentiometric titration curve: Titration curve

Outline Measuring the potential of a suitable
indicator electrode (pH) as a function
INSTRUMENTAL of volume titrant.
DETECTION

1st derivative
Advantages
Determination of the end point:
from the derivatives
Types

Potentiometric
end point
detection 2nd derivative

Conductometric
end point
detection

14
 CONDUCTOMETRIC
TITRATION CURVES
I. Titration of strong acid (a) with strong base e.g. HCl with NaOH
(b) with weak base e.g. HCl with NH4OH
Outline
INSTRUMENTAL
DETECTION

Advantages %
II. Titration of weak acid (c) with strong base e.g. CH3COOH with NaOH
Types
(d) with weak base e.g. CH3COOH with NH4OH
Potentiometric
end point
detection

Conductometric
end point
detection

% 15
 APPLICATIONS
TITRATIONS

 Direct  Back (indirect):

Outline Analyte
Titrant in excess
to measure
NEUTRALIZATION to calculate
ANALYSIS I. Determination of strong acids / bases:
Equivalence point: pH = 7
e.g. NaOH
Introduction

Titrants

Titration curves

End point
Vphen. OH−  H2O
detection
Vmeth.r.
Applications

16
 APPLICATIONS
II. Determination of weak acids :
Equivalence point: pH > 7 (phenolphtalein indicator)
weak bases :
Equivalence point: pH < 7 (methyl red indicator)
II. (a) Determination of weak acids : Ka ≥ 10–5. (10–7 - 10–4)
Outline  Direct: e.g.  carboxylic acids of low carbon atoms
e.g. CH3COOH
NEUTRALIZATION
 fatty acids (e.g. fat, wax, oil)
ANALYSIS  Back : if the weak acid is volatile
e.g.  CO2 (as carbonate or hydrogencarbonate)
Introduction bubble-free
distillation
Titrants CO2 known amount of Ba(OH)2
Distillation apparatus 
Titration curves
(Maros- Schulek) back titration of excess Ba(OH)2
End point with standard HCl
Application of CO2 determination:
detection
 Determination of organic materials
Applications  Determination of CO2, HCO3– , CO32–
content of natural waters
 Nonaqueous solvents: Ka < 10–7
17
> 10–12
 APPLICATIONS
II. (b) Determination of weak bases : Kb ≥ 10–5 (10–7 - 10–4)
 Direct:  e.g. NH4OH
strong base (NaOH)
 Back:  NH4+ -salt NH3
boiling
Outline
distillation into known excess of acid
Kjeldahl method: 
NEUTRALIZATION NH3 back titration of excess acid (HCl)
ANALYSIS known HCl with basic titrant (NaOH)
Application of NH3 determination:
Introduction  N-containing organic compounds (e.g. amino acids, proteins,…)
Decomposition (mineralization) with cc. H2SO4, 300 °C
Titrants
+ catalyst: Se, or Cu2+
Titration curves Ox. number: – 3  (NH4)2SO4
(e.g.. – NH2, –N(CH3)2, =NH, –N<)
End point
detection Ox. number: + 3, +1  HNO3 (+5)
(e.g.,azo- (-N=N-), nitro-, nitrozo comp.) Reduction
Applications with Zn, Na2S2O4,..
NH4+
 Nonaqueous solvents: Kb < 10–7
18
> 10–12
 APPLICATIONS
III. Determination of salts:
(a) Neutral salts: NOT MEASURABLE!
(b) Salt hydrolyzing to acid: Brönsted acid (strong acid + weak base)
MA + H2O  MOH + A– + H+
Outline if pK > 7! can be TITRATED
with base
E.g. Aniline · HCl; Benzidine ·H2SO4; Papaverine · HCl…
(c) Salt hydrolyzing to base: Brönsted base (strong base + weak acid)
NEUTRALIZATION
ANALYSIS MA + H2O  HA + M+ + OH–
if pK > 7 can be TITRATED
with acid
E.g. Na2B4O7 (B4O7 +7 H2O  4H3BO3 + 2OH ) methyl red
2– –
Introduction
E.g. Na2CO3 (CO32– + H2O  HCO3– + OH–) phenolpht.
Titrants
(CO32– +2 H2O  H2CO3 +2 OH–) methyl red
NaHCO (HCO3 + H2O  H2O + CO2 +OH ) methyl red
Titration curves – –
3
End point Na2CO3 NaHCO3
detection

Applications

HCO3−  H2CO3
CO32− HCO3− H2CO3
Vphen Vphen = 0
Vmeth.r. 19
Vmeth.r.
 APPLICATIONS
(d) Specific determinations:
NaOH – Na2CO3 NaHCO3 – Na2CO3
in the presence of each other in the presence of each other

Outline
NEUTRALIZATION
ANALYSIS OH−, CO32− HCO3− H2CO3 CO32− HCO3− HCO3−  H2CO3
Vphen Vphen
Vmeth.r. Vmeth.r.
Introduction Warder’s method :
one sample :
Warder’s method :
Titrants A. OH– + H+  H2O phenolpht.
CO32– + H+  HCO3–. two samples :
Titration curves
B. HCO3– + H+  H2CO3 methyl red A. CO32– + H+  HCO3–
End point two samples : phenolpht.
detection B. OH− + H+  H2O B. HCO. – + H+  H CO
CO32– +2H+  H2CO3 methyl red 3 2 3
Applications CO3 2− +2H+  H2CO3
Winkler’s method :
methyl red
A. + BaCl2
CO32– +Ba2+ BaCO3
20
OH– + H+  H2O phenolpht.