Acid-Base Titration

Acid-Base Titration:
Principles of Neutralization
Common Acids and Bases
Strong and Weak Acids & Bases
Table 4.2 Selected Acids and Bases
Acids Bases
Strong Strong
hydrochloric acid, HCl sodium hydroxide, NaOH

hydrobromic acid, HBr potassium hydroxide, KOH
hydroiodic acid, HI calcium hydroxide, Ca(OH)2
nitric acid, HNO3 strontium hydroxide, Sr(OH)2
sulfuric acid, H2SO4 barium hydroxide, Ba(OH)2
perchloric acid, HClO4
Weak Weak
hydrofluoric acid, HF ammonia, NH3
phosphoric acid, H3PO4
acetic acid, CH3COOH (or

HC2H3O2)
Dissociation of Strong Acids
Figure 18.1 The extent of dissociation for strong acids.
Strong acid: HA(g or l) + H2O(l) H2O+(aq) + A-(aq)

Dissociation of Weak Acids
Figure 18.2 The extent of dissociation for weak acids.
Weak acid: HA(aq) + H2O(l) H2O+(aq) + A-(aq)

Reactivity
Figure 18.3
with Metal
Reaction of zinc with a strong and a weak acid.
1M HCl(aq) 1M CH3COOH(aq)
Acid Dissociation Constant (Ka)
Strong acids dissociate completely into ions in water.
HA(g or l) + H2O(l) H3O+(aq) + A-(aq) Kc >> 1
Weak acids dissociate very slightly into ions in water.
HA(aq) + H2O(l) H3O+(aq) + A-(aq) Kc << 1
The Acid-Dissociation Constant
[H3O+][A-] stronger acid higher [H3O+]

Kc =
[H2O][HA] larger Ka
[H3O+][A-]
Kc[H2O] = Ka =
[HA] smaller Ka lower [H3O+]
weaker acid
Ka Values of Monoprotic Acids
ACID STRENGTH
Classifying Acid and Base Strength from the
Chemical Formula
PROBLEM: Classify each of the following compounds as a strong acid, weak acid,
strong base, or weak base.
(a) H2SeO4 (b) (CH3)2CHCOOH (c) KOH (d) (CH3)2CHNH2
PLAN: Pay attention to the text definitions of acids and bases. Look at O for acids
as well as the -COOH group; watch for amine groups and cations in bases.
SOLUTION: (a) Strong acid - H2SeO4 - the number of O atoms exceeds the
number of ionizable protons by 2.
(b) Weak acid - (CH3)2CHCOOH is an organic acid having a -COOH group.
(c) Strong base - KOH is a Group 1A(1) hydroxide.
(d) Weak base - (CH3)2CHNH2 has a lone pair of electrons on the N and is an
amine.
Autoionization of Water and the pH Scale
Autoionization of Water and the pH Scale
H2O(l) H2O(l)
H3O+(aq) OH-(aq)
Water Dissociation Constant (Kw)
H2O(l) + H2O(l) H3O+(aq) + OH-(aq)
[H3O+][OH-]
Kc =
[H2O]2
The Ion-Product Constant for Water
Kc[H2O]2 = Kw = [H3O+][OH-] = 1.0 x 10-14 at 250C
A change in [H3O+] causes an inverse change in [OH-].
In an acidic solution, [H3O+] > [OH-]

In a basic solution, [H3O+] < [OH-]
In a neutral solution, [H3O+] = [OH-]
Relationship between [H3O+] and [OH-]
The relationship between [H3O+] and [OH-] and the

relative acidity of solutions.
[H3O+] Divide into Kw [OH-]
[H3O+] > [OH-] [H3O+] = [OH-] [H3O+] < [OH-]
ACIDIC NEUTRAL BASIC

SOLUTION SOLUTION SOLUTION
Calculating [H3O+] and [OH-] in an Aqueous
Solution
SAMPLE PROBLEM
PROBLEM: A research chemist adds a measured amount of HCl gas to pure water
at 250C and obtains a solution with [H3O+] = 3.0x10-4M. Calculate
[OH-]. Is the solution neutral, acidic, or basic?
PLAN: Use the Kw at 250C and the [H3O+] to find the corresponding [OH-].
SOLUTION: Kw = 1.0x10-14 = [H3O+] [OH-] so
[OH-] = Kw/ [H3O+] = 1.0x10-14/3.0x10-4 = 3.3x10-11M
[H3O+] is > [OH-] and the solution is acidic.

The pH values of some familiar aqueous solutions
pH = -log [H3O+]
Relationship Between Ka and pKa
Table 18.3 The Relationship Between Ka and pKa
Acid Name (Formula) Ka at 250C pKa
Hydrogen sulfate ion (HSO4-) 1.02x10-2 1.991
7.1x10-4 3.15
Nitrous acid (HNO2)
Acetic acid (CH3COOH) 1.8x10-5 4.74
Hypobromous acid (HBrO) 2.3x10-9 8.64
Phenol (C6H5OH) 1.0x10-10 10.00

[H3O+], pH, [OH-], and pOH
Figure 18.6 The relations among [H3O+], pH, [OH-], and pOH.
Calculating [H3O+], pH, [OH-], and pOH
SAMPLE PROBLEM
PROBLEM: In an art restoration project, a conservator prepares copper-plate
etching solutions by diluting concentrated HNO3 to 2.0M, 0.30M, and
0.0063M HNO3. Calculate [H3O+], pH, [OH-], and pOH of the three
solutions at 250C.
PLAN: HNO3 is a strong acid so [H3O+] = [HNO3]. Use Kw to find the [OH-] and
then convert to pH and pOH.
SOLUTION: For 2.0M HNO3, [H3O+] = 2.0M and -log [H3O+] = -0.30 = pH
[OH-] = Kw/ [H3O+] = 1.0x10-14/2.0 = 5.0x10-15M; pOH = 14.30
For 0.3M HNO3, [H3O+] = 0.30M and -log [H3O+] = 0.52 = pH

[OH-] = Kw/ [H3O+] = 1.0x10-14/0.30 = 3.3x10-14M; pOH = 13.48
For 0.0063M HNO3, [H3O+] = 0.0063M and -log [H3O+] = 2.20 = pH

[OH-] = Kw/ [H3O+] = 1.0x10-14/6.3x10-3 = 1.6x10-12M; pOH = 11.80
Measuring pH
Figure 18.7 Methods for measuring the pH of an aqueous solution
pH (indicator) paper
pH meter
Bronsted-(Lowry) Concept
Figure 18.8 Proton transfer as the essential feature of a Brønsted-
Lowry acid-base reaction.
Lone pair
binds H+
+ +
HCl H2O Cl- H3O+

(acid, H+ donor) (base, H+ acceptor)
Lone pair
binds H+
+ +
NH3 H2O NH4+ OH-

(base, H+ acceptor) (acid, H+ donor)
Brønsted-Lowry Acid-Base Definition
An acid is a proton donor, any species which donates a H+.
A base is a proton acceptor, any species which accepts a H+.
An acid-base reaction can now be viewed from the

standpoint of the reactants AND the products.
An acid reactant will produce a base product and the two will
constitute an acid-base conjugate pair.
Conjugate Pairs in Some Acid-Base Reactions
Table 18.4 The Conjugate Pairs in Some Acid-Base Reactions

Conjugate Pair
Acid + Base Base + Acid
Conjugate Pair
Reaction 1 HF + H2O F- + H3O+
Reaction 2 HCOOH + CN- HCOO- + HCN
Reaction 3 NH4+ + CO32- NH3 + HCO3-
Reaction 4 H2PO4- + OH- HPO42- + H2O
Reaction 5 H2SO4 + N2H5+ HSO4- + N2H62+
Reaction 6 HPO42- + SO32- PO43- + HSO3-

Identifying Conjugate Acid-Base Pairs
PROBLEM: The following reactions are important environmental processes.

Identify the conjugate acid-base pairs.
(a) H2PO4-(aq) + CO32-(aq) ⇌ HPO42-(aq) + HCO3-(aq)
(b) H2O(l) + SO32-(aq) ⇌ OH-(aq) + HSO3-(aq)
PLAN: Identify proton donors (acids) and proton acceptors (bases).

conjugate pair conjugate pair2
1
SOLUTION: (a) H2PO4-(aq) + CO32-(aq) ⇌ HPO42-(aq) + HCO3-(aq)

proton proton proton proton
donor acceptor acceptor donor
conjugate pair1 conjugate pair2
(b) H2O(l) + SO32-(aq) ⇌ OH-(aq) + HSO3-(aq)

proton proton proton proton
donor acceptor acceptor donor
Predicting the Net Direction of an Acid-Base Reaction
PROBLEM: Predict the net direction and whether Ka is greater or less than 1 for
each of the following reactions (assume equal initial concentrations of
all species):
(a) H2PO4-(aq) + NH3(aq) ⇌ HPO42-(aq) + NH4+(aq)
(b) H2O(l) + HS-(aq) ⇌ OH-(aq) + H2S(aq)
PLAN: Identify the conjugate acid-base pairs and then consult Figure 18.10
(button) to determine the relative strength of each. The stronger the
species, the more preponderant its conjugate.
SOLUTION: (a) H2PO4-(aq) + NH3(aq) ⇌ HPO42-(aq) + NH4+(aq)

stronger acid stronger base weaker base weaker acid
Net direction is to the right with Kc > 1.
(b) H2O(l) + HS-(aq) ⇌ OH-(aq) + H2S(aq)
weaker acid weaker base stronger base stronger acid
Net direction is to the left with Kc < 1.
Strengths of conjugate acid-base pairs
Strengths of
conjugate acid-base
pairs
Finding the Ka of a Weak Acid from the pH of Its Solution
PROBLEM: Phenylacetic acid (C6H5CH2COOH, simplified here as HPAc) builds

up in the blood of persons with phenylketonuria, an inherited disorder
that, if untreated, causes mental retardation and death. A study of the
acid shows that the pH of 0.13M HPAc is 2.62. What is the Ka of
phenylacetic acid?
PLAN: Write out the dissociation equation. Use pH and solution concentration to find
the Ka.
Assumptions: With a pH of 2.62, the [H3O+]HPAc >> [H3O+]water.

[PAc-] ≈ [H3O+]; since HPAc is weak, [HPAc]initial ≈ [HPAc]initial -
[HPAc]dissociation
SOLUTION: HPAc(aq) + H2O(l) ⇌ H3O+(aq) + PAc-(aq)
Ka = [H3O+][PAc-]
[HPAc]
Finding the Ka of a Weak Acid from the pH of Its Solution
Concentration(M) HPAc(aq) + H2O(l) ⇌ H3O+(aq) + PAc-(aq)
Initial 0.12 - 1x10-7 0

Change -x - +x +x
Equilibrium 0.12-x - x +(<1x10-7) x
[H3O+] = 10-pH = 2.4x10-3 M which is >> 10-7 (the [H3O+] from water)
x ≈ 2.4x10-3 M ≈ [H3O+] ≈ [PAc-] [HPAc]equilibrium = 0.12-x ≈ 0.12 M
(2.4x10-3) (2.4x10-3)
So Ka = = 4.8 x 10-5
0.12
1x10-7M
Be sure to check for % error. [H3O+]from water; x100 = 4x10-3 %
2.4x10-3M
[HPAc]dissn; 2.4x10-3M
x100 = 2.0 %
0.12M
Determining Concentrations from Ka and Initial [HA]
PROBLEM: Propanoic acid (CH3CH2COOH, which we simplify and HPr) is an

organic acid whose salts are used to retard mold growth in foods.
What is the [H3O+] of 0.10M HPr (Ka = 1.3x10-5)?
PLAN: Write out the dissociation equation and expression; make whatever
assumptions about concentration which are necessary; substitute.
Assumptions: For HPr(aq) + H2O(l) ⇌ H3O+(aq) + Pr-(aq)
x = [HPr]diss = [H3O+]from HPr= [Pr-] Ka = [H3O+][Pr-]
SOLUTION: [HPr]
Concentration(M) HPr(aq) + H2O(l) ⇌ H3O+(aq) + Pr-(aq)

Initial 0.10 - 0 0
Change -x - +x +x
Equilibrium 0.10-x - x x
Since Ka is small, we will assume that x << 0.10

Determining Concentrations from Ka and Initial [HA]
continued
[H3O+][Pr-] (x)(x)
1.3x10-5 = =
[HPr] 0.10
= 1.1x10-3 M = [H3O+]
Check: [HPr]diss = 1.1x10-3M/0.10 M x 100 = 1.1%

Polyprotic Acids, Ka
ACID STRENGTH
Amines,Weak Bases, Kb
[BH+][OH-]
Kb =
[B]
BASE STRENGTH
Amine and Water
Figure 18.11 Abstraction of a proton from water by methylamine.
Lone pair
binds H+
CH3NH2 H2O
methylamine
CH3NH3+ OH-
methylammonium ion
Acidity trend
Figure 18.12 The effect of atomic and molecular properties on
nonmetal hydride acidity.
6A(16) 7A(17) Electronegativity increases,

acidity increases
H2O HF
Bond strength decreases,
acidity increases
H2S HCl
H2Se HBr
H2Te HI
Oxoacids
Figure 18.13 The relative strengths of oxoacids.
H O I > H O Br > H O Cl
+ − + − + −
H O Cl << H O Cl O
+ −
+ −
O
Hydrated Metal Ions, Ka
Table 18.7 Ka Values of Some Hydrated Metal Ions at 250C
Free Ion Hydrated Ion Ka

Fe3+ Fe(H2O)63+(aq) 6 x 10-3
Sn2+ Sn(H2O)62+(aq) 4 x 10-4
Cr3+ Cr(H2O)63+(aq) 1 x 10-4
ACID STRENGTH
Al3+ Al(H2O)63+(aq) 1 x 10-5
Cu2+ Cu(H2O)62+(aq) 3 x 10-8
Pb2+ Pb(H2O)62+(aq) 3 x 10-8
Zn2+ Zn(H2O)62+(aq) 1 x 10-9
Co2+ Co(H2O)62+(aq) 2 x 10-10
Ni2+ Ni(H2O)62+(aq) 1 x 10-10
Hydrated Al3+ ion, acidity
Figure 18.13 The acidic behavior of the hydrated Al3+ ion.
Electron density drawn Nearby H2O acts

toward Al3+ as base
H2O H3O+
Al(H2O)63+ Al(H2O)5OH2+
Behavior of Salts in H2O
Lewis Acids
Molecules as Lewis Acids
An acid is an electron-pair acceptor.
A base is an electron-pair donor.
F F
H
H
B + N
B N
F HH F
F F HH
acid base adduct
M(H2O)42+(aq)
M2+
H2O(l) adduct
Chlorophyll
Figure 18.15
The Mg2+ ion as a Lewis acid in the

chlorophyll molecule.
Buffer
Figure 19.1
The effect of addition of acid or base to …
acid added base added
Figure 19.2 an unbuffered solution
acid added base added
or a buffered solution
Ionic Equilibrium
Table 19.1
The Effect of Added Acetate Ion on the Dissociation of Acetic Acid
[CH3COOH]initial [CH3COO-]added % Dissociation* pH
0.10 0.00 1.3 2.89
0.10 0.050 0.036 4.44
0.10 0.10 0.018 4.74
0.10 0.15 0.012 4.92
[CH3COOH]dissoc
* % Dissociation = x 100
[CH3COOH]initial
How buffer Works
Buffer after addition of H3O+ Buffer with equal Buffer after addition of OH-
concentrations of conjugate
base and acid
H3O+ OH-
H2O + CH3COOH H3O+ + CH3COO- CH3COOH + OH- H2O + CH3COO-

Calculating the Effect of Added H3O+
or OH- on Buffer pH
PROBLEM: Calculate the pH:
(a) of a buffer solution consisting of 0.50M CH3COOH and 0.50M CH3COONa
(b) after adding 0.020mol of solid NaOH to 1.0L of the buffer solution in part (a)
(c) after adding 0.020mol of HCl to 1.0L of the buffer solution in part (a)
Ka of CH3COOH = 1.8x10-5. (Assume the additions cause negligible volume changes.
PLAN: We know Ka and can find initial concentrations of conjugate acid and base. Make
assumptions about the amount of acid dissociating relative to its initial concentration.
Proceed step-wise through changes in the system.
SOLUTION: (a)
Concentration (M) CH3COOH(aq) + H2O(l) ⇌ CH3COO-(aq) + H3O+(aq)
Initial 0.50 - 0.50 0

Change -x - +x +x
Equilibrium 0.50-x - 0.50 +x x
or OH- on Buffer pH
continued (2 of 4)
[H3O+] = x [CH3COOH]equil ≈ 0.50M [CH3COO-]initial ≈ 0.50M

[H3O+][CH3COO-] [CH3COOH]
Ka = [H3O+] = x = Ka = 1.8x10-5M
[CH3COOH] [CH3 COO-]
Check the assumption: 1.8x10-5/0.50 X 100 = 3.6x10-3 %
(b) 0.020 mol

[OH-]added = = 0.020M NaOH
1.0L soln
Concentration (M) CH3COOH(aq) + OH-(aq) ⇌ CH3COO-(aq) + H2O (l)
Before addition 0.50 - 0.50 -

Addition - 0.020 - -
After addition 0.48 0 0.52 -
or OH- on Buffer pH
continued (3 of 4)
Set up a reaction table with the new values.
Initial 0.48 - 0.52 0

Change -x - +x +x
Equilibrium 0.48 -x - 0.52 +x x
0.48
[H3O+] = 1.8x10-5 = 1.7x10-5 pH = 4.77
0.52
0.020 mol
(c) [H3O+]added = = 0.020M H3O+
1.0L soln
Concentration (M) CH3COO-(aq) + H3O+(aq) ⇌ CH3COOH(aq) + H2O (l)
Before addition 0.50 - 0.50 -

Addition - 0.020 - -
After addition 0.48 0 0.52 -
or OH- on Buffer pH
continued (4 of 4)
Set up a reaction table with the new values.
Initial 0.52 - 0.48 0

Change -x - +x +x
Equilibrium 0.52 -x - 0.48 +x x
0.52
[H3O+] = 1.8x10-5 = 2.0x10-5 pH = 4.70
0.48
The Henderson-Hasselbalch Equation
The Henderson-Hasselbalch Equation
HA + H2O H3O+ + A-
Ka = [H3O+] [A-]
[HA]
Ka [HA]
[H3O+] =
[A-]
[A-]
- log[H3O+] = - log Ka + log
[HA]
[base]
pH = pKa + log
[acid]
Buffer Capacity and Buffer Range
Buffer Capacity and Buffer Range
Buffer capacity is the ability to resist pH change.
The more concentrated the components of a buffer, the greater

the buffer capacity.
The pH of a buffer is distinct from its buffer capacity.
A buffer has the highest capacity when the component

concentrations are equal.
Buffer range is the pH range over which the buffer acts effectively.
Buffers have a usable range within ± 1 pH unit of the pKa of

its acid component.
The relation between buffer capacity and pH change.
Preparing a Buffer
STEPS:
1. Choose the conjugate acid-base pair.
2. Calculate the ratio of buffer component

concentrations.
3. Determine the buffer concentration.
4. Mix the solution and adjust the pH.

Preparing a Buffer
PROBLEM: An environmental chemist needs a carbonate buffer of pH 10.00 to
study the effects of the acid rain on limsetone-rich soils. How many
grams of Na2CO3 must she add to 1.5L of freshly prepared 0.20M
NaHCO3 to make the buffer? Ka of HCO3- is 4.7x10-11.
PLAN: We know the Ka and the conjugate acid-base pair. Convert pH to [H3O+],
find the number of moles of carbonate and convert to mass.
SOLUTION:
[CO32-][H3O+]
HCO3-(aq) + H2O(l) ⇌ CO32-(aq) + H3O+(aq) Ka =
[HCO3-]
[CO32-](1.0x10-10)
pH = 10.00; [H3O+] = 1.0x10-10 4.7x10-11 = [CO32-] = 0.094M
0.20
moles of Na2CO3 = (1.5L)(0.094 mol/L) = 0.14

105.99g
0.14 moles = 15 g Na2CO3
mol
Preparing a Buffer
Volume = 100.0 mL Concentration = 0.10 M phosphate pH = 7.0

Weak acid: NaH2PO4 (119.98 g/mol) Conjugate base: Na2HPO4 (141.96 g/mol)
51
Preparing a Buffer
53
Acid-Base Indicators
Colors and approximate pH range of some common acid-
Figure 19.5
base indicators.
pH
The color change of the indicator bromthymol blue.
basic
acidic change occurs

over ~2pH units
An acid-base titration.
Start of titration Point of Slight excess of

Excess of acid neutralization base
Endpoint
REMEMBER: A significant or remarkable change in
some property of the solution happens at the equivalence
point.
• The end point is chosen so that it coincides or occurs as

close as possible to the equivalence point.
Graphic Endpoint
Specific Compound Formers
Colored Titrants/Analytes
Nonspecific, Equilibrium-dependent
Compounds
Titration Curve
• Plot of some property of the titration mixture that

changes as the reaction progresses
• For acid-base reactions, the titration reaction is

monitored by measuring the pH of the mixture as
increasing volumes of the titrant are added
General Shapes of a Titration Curve
The intersection of the two

line segments indicates the
position of the end point.
2 straight line
segments with
different slopes
Line Segment Curve

Sigmoidal curve or S curve:

consists of 2 lines that are parallel to one another
Titration Curve of 25.00 mL of 0.120 M HCl with 0.100 M NaOH
14.000
12.000
10.000
8.000
pH
6.000
4.000
2.000
0.000
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00 65.00
Volume (mL) Titrant
Sigmoidal curve or S curve:

consists of 2 lines that are parallel to one another
14.000
12.000
10.000 pH break or pH transition

8.000
pH break range:
pH
6.000
A sudden change in the pH of
the solution causes the slope of
4.000
the line to change
2.000
0.000
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00 65.00
Volume (mL) Titrant
Stoichiometric Relationship Between
the Analyte and the Titrant
• The number of inflection points (or steep portions) of the
titration curve is an indication of the stoichiometric ratio
between the analyte and the titrant.
14.000
12.000
10.000
Inflection points
8.000
pH
6.000
4.000 Inflection point

2.000
0.000
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00 65.00
Volume (mL) Titrant
Stoichiometric mole ratio (SMR) between

the analyte and the titrant is 1:1
Diequivalent Base titrated with a Strong Acid
Inflection points
Four Stages of the Titration Curve
Strong Acid-Strong Base Reaction
14.000
Before
12.000
Equivalence
Point Stage 25.00 mL of 0.120 M HCl
10.000 0 < VT < VEP

After Equivalence
8.000
point stage VT > VEP
pH
6.000
Initial stage
Equivalence point
4.000 stage VEP
2.000
0.000
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00
Volume (mL) NaOH
Four Stages of a Titration Reaction
Stage 1: Initial Stage (VT = 0)
Stage 2: Before The Equivalence Point Stage

(0 < VT < VEP)
Stage 3: During The Equivalence Point Stage

(VT = VEP )
Stage 4: After The Equivalence Point Stage

(VT  VEP )
At this stage, only the analyte is present.
The pH of the titration mixture: depends on the analyte.

At this stage, only the analyte is present.
• The pH of the solution depends on the nature of the analyte
If the analyte is acidic, the pHSOLUTION is less than 7

If the analyte is basic, the pHSOLUTION is greater than 7
• GUIDE QUESTIONS:
Is the analyte acidic or basic? Weak or strong?
Stage 2: Before The Equivalence Point Stage

(0 < VT < VEP)
The titrant is the limiting reactant; the analyte is present in excess.

The amount of the product depends on the amount of the titrant.
The pH of the titration mixture: depends on the analyte and

product.
Stage 2: : Before The Equivalence Point
Stage (0 < VT < VEP)
At this stage, the titrant is the limiting reagent while the

analyte is present in excess.
▪ The amount of the product formed depends on the amount of the

titrant
▪ The pH of the solution depends on the nature of the product and

analyte present
▪ GUIDE QUESTIONS:
What is the nature of the product and reactant?
Stage 3: During The Equivalence Point Stage
(VT = VEP )
A stoichiometric amount of the titrant has been added to the

solution.
The reaction is considered to be complete.
Only the product is present.
The pH of the titration mixture: depends on the product.


(VT  VEP )
The analyte is completely consumed; the titrant in present in excess.

The amount of product depends on the amount of analyte
The pH of the titration mixture: depends on the product and titrant.

(VT  VEP)
At this stage, the analyte is the limiting reactant

while the titrant is present in excess.
The amount of product depends on the amount of analyte
The pH of the solution depends on the nature of the product

and the excess or unreacted titrant.
GUIDE QUESTIONS:
What is the nature of the product and titrant?
Various information that can be obtained from the
titration curve
Consider the following titration

data: Volume of analyte solution:
Concentration
25.00 mL Initial concentration of of the titrant is
Analyte: 0.120 M Concentration of 0.100 M
the titrant: 0.100 M
25.00 mL of the
analyte with an initial
concentration of
0.120 M
Nature of the reacting species
Strong Acid (Analyte) - Strong Base (Titrant)
14.000
12.000
25.00 mL of 0.120 M HCl
10.000
8.000
pH
6.000
4.000
2.000
0.000
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00
Volume (mL) NaOH
Strong Base (Analyte) - Strong Acid (Titrant)
Strong Base - Strong Acid Reaction
14.000
12.000
25.00 mL of 0.120 M NaOH
10.000
8.000
pH
6.000
4.000
2.000
0.000
0.00 10.00 20.00 30.00 40.00 50.00 60.00
Volume (mL) of 0.100 M HCl
Superimposed Titration Curves
Strong Acid (A)-Strong Base (T) and Strong Base (A) -Strong Acid (T)
14.000
12.000
10.000
8.000
6.000
4.000
2.000
0.000
0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00
Vol ume ( mL) T

Weak Acid (Analyte) - Strong Base (Titrant)
Titration of 25.00 mL of 0.120 M Acetic acid with 0.100 M NaOH
14.000
12.000
10.000
8.000
pH
6.000
4.000
2.000
0.000
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00 65.00
Volume (mL) Titrant
Weak Base (Analyte) - Strong Acid (Titrant)
Titration of 25.00 mL of 0.120 M NH3 with 0.100 M HCl
12.000
10.000
8.000
pH
6.000
4.000
2.000
0.000
0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00
Volume (mL) T
Relationship between the pH break and the equilibrium
constant of the reaction
• The height of the pH break (distance between the two
parallel regions) is directly proportional to the KRXN
14.000
12.000
25.00 mL of 0.120 M HCl
10.000
8.000
pH break
pH
6.000
4.000
2.000
0.000
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00
Volume (mL) NaOH
• Factors that affect the shape of the titration curve for acid-base
reactions: Limited to Reactions whose stoichiometric mole ratio
(SMR) between the analyte and the titrant is 1:1
Comparison Between the Titration Curves of a Strong
Acid vs a Weak Acid
Titration Curves of 25.00 mL of 0.120 M Strong Acid and Weak Acid
14.000
12.000
Unchanged
10.000
pH > 7
8.000
pH = 7
pH
6.000
4.000
2.000
0.000
0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00
Volume (mL) T
Comparison Between the Titration Curves of a Strong
Acid vs a Weak Acid
Titration Curves of 25.00 mL of 0.120 M Strong Acid and Weak Acid
14.000
12.000
10.000
Height of the pH break (WA) is
shorter compared with the
8.000
Height of the pH break (SA)
pH
6.000
4.000
2.000
0.000
0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00
Volume (mL) T
KRXN for the strong acid (SA)-strong base (SB)
The KRXN for the strong acid (SA)-strong base reaction is

H+(aq) + OH−(aq) ⎯→ H2O(l)
1 1
KRXN = =
[H+ ][OH− ] KW
The KRXN for the weak acid (WA)-strong base reaction.
HA(aq) + OH−(aq) ⎯→ H2O(l) + A−(aq)

[ A− ] 1 Ka
KRXN = −
= =
[HA ][OH ] K b KW
Effect of Ka of the weak acids on the titration curve
As the Ka decreases (the relative strength of the weak acid
decreases) the height of the pH break decreases.
Titration of 2 Weak Acids
14.000
12.000
10.000
8.000
pH
6.000
4.000
2.000
0.000
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00 65.00
Volume (mL) Titrant
Effect of Concentration of the Analyte and Titrant
Figure A: Titration of 25.00 mL of 0.120 M HCl with 0.100 M NaOH
Figure B: Titration of 25.00 mL of 0.0120 M HCl with 0.0100 M NaOH
Effect of Concn on the Titration Curve
14.000
A
12.000
The overall effect on
B
the titration curve:
10.000
The titration curve of

8.000
solution B is shorter
pH
6.000 than that of the

titration curve of the
4.000
B more concentrated
A
2.000 solution A.
0.000
0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00
Volume (mL) T
Guide to Titration Curve Problems
Step 1. Calculate the initial amount (mmol) of the

strong acid and the strong base.
Step 2. Identify the excess and the limiting reactants.
Step 3. Determine the amount (mmole) of the excess

reactant that will remain in the solution.
Step 4. Calculate the concentration of the excess

reactant and related this to the pH of the solution .
Titration of SA vs SB
HCl (aq) + NaOH (aq) ⟶ H2O (l) + NaCl (aq)
H+(aq) + OH-(aq) ⟶ H2O (l)
• Titration of 25 mL of 0.100 M HCl with 0.100 M NaOH. Let us show calculation of

pH at VNaOH (mL) = 0.00, 5.00, 10.0, 25.0, 30.0 and 35.0.
Titration of 25.0 mL of .100 M HCl with 0.100 NaOH
1. Before titration: pH=?

MHCl=0.100M | VHCl=25.0 mL | VNaOH = 0.00 mL
87
2. Before Equivalence Point: pH=?

MHCl=0.100M * VHCl=25.0 mL | MNaOH = 0.100 M * VNaOH = 5.00 mL

Concentration (M)
0.100 0.100
Volume (mL) 25.0 5.00
Available (mmol) 2.50 0.500
Reacted (mmol) Produced
0.500 0.500 0.500
Excess (mmol) 2.00 0.00
88


Concentration (M)
0.100 0.100
Volume (mL) 25.0 10.0
1.00 1.00 1.00
89
3. At the Equivalence Point: pH=?


Concentration (M)
0.100 0.100
Volume (mL) 25.0 25.00
2.50 2.50 2.500
90
4. After the Equivalence Point: pH=?


Concentration (M)
0.100 0.100
Volume (mL) 25.0 30.0
2.50 2.50 2.50
91


Concentration (M)
0.100 0.100
Volume (mL) 25.0 35.0
2.50 2.50 2.50
92
Titration of WA vs SB
CH3COOH (aq) + NaOH (aq) ⟶ CH3COONa (aq) + H2O (l)
CH3COOH (aq) + OH- (aq) ⟶ CH3COO- (aq) + H2O (l)
• Titration of 25 mL of 0.100 M HAc (Ka=1.8x10-5) with 0.100 M NaOH. Let us

show calculation of pH at VNaOH (mL) = 0.00, 5.00, 10.0, 25.0, 30.0 and 35.0.
Titration of 25.0 mL of .100 M HAc with 0.100 NaOH

MHAc=0.100M | VHAc=25.0 mL | VNaOH = 0.00 mL
HAc (aq) + H2O (l) ⇌ Ac- (aq) + H3O+ (aq) Ka=1.8 x10-5
Initial 0.100 0 0
Change -x +x +x
Equilibrium 0.100 - x x x
94

MHAc=0.100M * VHAc=25.0 mL | MNaOH = 0.100 M * VNaOH = 5.00 mL
HAc (aq) + NaOH (aq) ⟶ NaAc (aq) + H2O (l)

Concentration (M) 0.100 0.100
Volume (mL) 25.0 5.00
mmol Available 2.50 0.500
mmol Reacted 0.500 0.500 0.500 Produced
mmol Excess 2.00 0.00
95
2. Before Equivalence Point: pH=? VNaOH = 5.00 mL

Initial 0
Change
Equilibrium
96

Using HHE
97


Volume (mL) 25.0 10.0
mmol Reacted 1. 00 1.00 1.00 Produced
98

Initial 0
Change
Equilibrium
99

Using HHE
100


Volume (mL) 25.0 25.0
101
3. At the Equivalence Point: pH=? VNaOH = 25.0 mL
Ac- (aq) + H2O (l) ⇌ HAc (aq) + OH- (aq) Kb=?

Initial 0 0
Change
Equilibrium
102


Volume (mL) 25.0 30.0
103


Volume (mL) 25.0 35.0
104
Titration of WB vs SA
HCl (aq) + NH3 (aq) ⟶ NH4Cl (aq) H+ (aq) + NH3 (aq) ⟶ NH4+ (aq)
NH4+ (aq) + H2O (l) ⇌ NH3 (aq) + H+ (aq)
• Titration of 25 mL of 0.100 M NH3 (Kb=1.8x10-5) with 0.100 M HCl. Let us show

calculation of pH at VHCl (mL) = 0.00, 5.00, 10.0, 25.0, 30.0 and 35.0.
Titration of 25.0 mL of .100 M NH3 with 0.100 HCl

MNH3=0.100M | VNH3 =25.0 mL | VHCl = 0.00 mL
NH3 (aq) + H2O (l) ⇌ NH4+ (aq) + OH- (aq) Kb=1.8 x10-5
Initial 0.100 0 0
Change -x +x +x
Equilibrium 0.100 - x x x
106

MNH3=0.100M * VNH3=25.0 mL | MHCl = 0.100 M * VHCl = 5.00 mL
NH3 (aq) + HCl (aq) ⟶ NH4+ (aq) + Cl- (aq)

Volume (mL) 25.0 5.00
107
2. Before Equivalence Point: pH=? VHCl = 5.00 mL

Initial 0
Change
Equilibrium
108

Using HHE
109


Volume (mL) 25.0 10.0
mmol Reacted 1. 00 1.00 1.00 Produced
110

Initial 0
Change
Equilibrium
111

Using HHE
112


Volume (mL) 25.0 25.0
113
3. At the Equivalence Point: pH=? VHCl = 25.0 mL
NH4+ (aq) + H2O (l) ⇌ NH3 (aq) + H3O+ (aq) Ka=?

Initial 0 0
Change
Equilibrium
114


Volume (mL) 25.0 30.0
115


Volume (mL) 25.0 35.0
116
Acid-Base Titration:
Principles of Neutralization
with Sir Adolf

Let’s try this . . .
1. Calculate the pH of a 25.00 mL of 0.120 M HCl.
2. Complete the tables representing the titration of 25.00 mL of

0.120 M HCl with 0.100 M NaOH.
Let’s try this…
continuation of #2
119
Let’s try this …
3. Calculate the pH of the mixture resulting from the reaction
between 25.00 mL of 0.140 M HCl and 25.00 mL of 0.180 M
NaOH.
120
4. How may mL of 0.1400 M HNO3 are needed to reach the
equivalence point 25.00 mL of 0.1200 M Ba(OH)2?
121
5. Calculate the pH of a 25.00 mL solution of 0.120 M
CH3COOH (Ka= 1.75 x 10-5)
122
6. Complete the tables representing the titration of 25.00 mL of 0.120 M CH3COOH
(Ka= 1.75 x 10-5) with 0.100 M NaOH.
123
continuation of #6
124
7. Calculate the pH of a 25.00 mL of 0.120 M NH3 (Kb=
1.76 x10-5)
125
8. Complete the tables representing the titration of 25.00 mL
of 0.120 M NH3 (Kb= 1.76 x10-5) with 0.100 M HCl.
126
continuation of #8
127
9. Consider the acid dissociation constant of CH3COOH at 250C as 1.75
x10-5 and the base dissociation constant of NH3 at 250C as 1.76 x10-5.
Calculate the pH of the following mixtures:
a) 50.00 mL of 0.140 M CH3COOH and 25.00 mL of 0.120 M NaOH
b) 25.00mL of 0.0860 M CH3COOH and 30.00 mL of 0.120 M NaOH
c) 50.00 mL of 0.110 M NH3 and 30.00 mL of 0.120 M HCl
d) 30.00 mL of 0.0920 M NH3 and 20.00 mL of 0.140 M HCl
128
Polyfunctional Acids and Bases
Polyfunctional Acids
• With this acid, as with other polyprotic acids, Ka₁＞Ka₂＞Ka₃.

Polyfunctional Bases
Describing polyfunctional Base
• The overall basic dissociation reaction of sodium
carbonate is described by the equations
• Solving the several simultaneous equations that are

involved can be difficult and time consuming.
Fortunately, simplifying assumptions can be invoked
when the successive equilibrium constants for the
acid (or base) differ by a factor of about 10³ (or
more).
Finding the pH of Solutions of Amphiprotic Salts
• The solution could be acidic because of
or basic because of
• Whether a solution of NaHA is acidic or basic

depends on the relative magnitude of the equilibrium
constants for these processes:
Finding the pH of Solutions of Amphiprotic Salts
• As we derive, solution of these equations yields an

approximate value of [H₃O⁺] that is given by the
equation
• Frequently, the ratio cNaHA/Ka₁ is much larger than

unity in the denominator of Equation above and
Ka₂cNaHA is considerably greater than Kw in the
numerator.
• Calculate the hydronium ion concentration of a 0.100

M NaHCO₃ solution.We first examine the
assumptions leading to Equation 8-4. The
dissociation constants for H₂CO₃ are Ka₁= 1.5×10⁻⁴
and Ka₂=4.69×10⁻¹¹. Clearly, cNaHA/ Ka₁ in the
denominator is much larger than unity; in addition,
Ka₂cNaHA has a value of 4.69×10¯¹², which is
substantially greater than Kw . Thus, Equation 8-4
applies and
Titration curve of Polyprotic Acids
Titration of 20.00 mL
of 0.1000 M H2A with
0.1000 M NaOH. For
H2A, Ka1=1.00 x 10-3,
and Ka2=1.00 x10-7. The
method of pH calculation
is shown for several
points and regions on the
titration curve.
• ratio Ka1/Ka2 is
somewhat greater than
103
Constructing Titration Curves for Polyfunctional Acids
Curves for the titration of

polyprotic acids. A
0.1000 M NaOH solution
is used to titrate 25.00 mL
of 0.1000 M H3PO4
(curve A), 0.1000 M
oxalic acid (curve B), and
0.1000 M H2SO4 (curve
C).
Drawing Titration Curves for Polyfunctional Bases
Curve for the

titration of 25.00
mL of 0.1000 M
Na2CO3 with
0.1000 M HCl.
Titration curves of Polyfunctional acids and Bases
In general, the titration of acids or

bases that have two reactive
groups yields individual end
points that are of practical value
only when the ratio between the
two dissociation constants is at
least 104. If the ratio is much
smaller than this 104, the pH
change at the first equivalence
point will prove less satisfactory
for an analysis.
Titration of Zwitterion
• The internal proton transfer from the carboxyl

group to the amine group of an amino acid is
very favorable in aqueous solution so that
amino acids exist as zwitterions as shown
below for glycine.
• The conjugate acid of the zwitterion can be treated
as a polyprotic acid.
• The zwitterion can act as an acid because of the

second proton transfer or as a base because of
• The pH at which no net migration occurs is

called the isoelectric point; this point is an
important physical constant for characterizing
amino acids. The isoelectric point is readily
related to the ionization constants for the
species. Thus, for glycine,
• At the isoelectric point,

• If we substitute Kw/[H₃O⁺] for [OH¯] and

rearrange, we get
• The isoelectric point for glycine occurs at a pH

of 6.0. That is,
Indicate whether an aqueous solution of the
following compounds is acidic, neutral, or basic.
Explain your answer.
a) NH4OAc b) Na2C2O4
Ka = 5.70 × 10–10 Ka2 = 5.42 × 10–5
Ka = 1.75 × 10–5
Suggest an indicator that would give an end point for the
titration of the first proton and second proton in H3AsO4.
Assume that the CNa2HAsO4= 0.033 M at the equivalence
point . Also, Ka1 = 5.3 × 10–3 Ka2 = 1.1 × 10–7 and Ka3 = 3.2
× 10–12
Indicators
Calculate the pH of a solution that is 0.0400 M in H3PO4.
Calculate the pH of a solution that contains the following
analytical concentrations: 0.0500 M in H3PO4 and 0.0200 M in
NaH2PO4.
Let’s try this…
Describe the composition of the ff titration curves

Acid-Base Titration

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Acid-Base Titration

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Acid-Base Titration:

hydrochloric acid, HCl sodium hydroxide, NaOH

acetic acid, CH3COOH (or

Strong acid: HA(g or l) + H2O(l) H2O+(aq) + A-(aq)

Weak acid: HA(aq) + H2O(l) H2O+(aq) + A-(aq)

HA(g or l) + H2O(l) H3O+(aq) + A-(aq) Kc >> 1

Weak acids dissociate very slightly into ions in water.

HA(aq) + H2O(l) H3O+(aq) + A-(aq) Kc << 1

The Acid-Dissociation Constant

[H3O+][A-] stronger acid higher [H3O+]

(c) Strong base - KOH is a Group 1A(1) hydroxide.

H2O(l) + H2O(l) H3O+(aq) + OH-(aq)

The Ion-Product Constant for Water

Kc[H2O]2 = Kw = [H3O+][OH-] = 1.0 x 10-14 at 250C

A change in [H3O+] causes an inverse change in [OH-].

In an acidic solution, [H3O+] > [OH-]

The relationship between [H3O+] and [OH-] and the

[H3O+] Divide into Kw [OH-]

[H3O+] > [OH-] [H3O+] = [OH-] [H3O+] < [OH-]

ACIDIC NEUTRAL BASIC

SOLUTION: Kw = 1.0x10-14 = [H3O+] [OH-] so

[OH-] = Kw/ [H3O+] = 1.0x10-14/3.0x10-4 = 3.3x10-11M

[H3O+] is > [OH-] and the solution is acidic.

Acid Name (Formula) Ka at 250C pKa

Hydrogen sulfate ion (HSO4-) 1.02x10-2 1.991

Acetic acid (CH3COOH) 1.8x10-5 4.74

Hypobromous acid (HBrO) 2.3x10-9 8.64

Phenol (C6H5OH) 1.0x10-10 10.00

For 0.3M HNO3, [H3O+] = 0.30M and -log [H3O+] = 0.52 = pH

For 0.0063M HNO3, [H3O+] = 0.0063M and -log [H3O+] = 2.20 = pH

HCl H2O Cl- H3O+

NH3 H2O NH4+ OH-

An acid is a proton donor, any species which donates a H+.

A base is a proton acceptor, any species which accepts a H+.

An acid-base reaction can now be viewed from the

Table 18.4 The Conjugate Pairs in Some Acid-Base Reactions

Acid + Base Base + Acid

Reaction 1 HF + H2O F- + H3O+

Reaction 2 HCOOH + CN- HCOO- + HCN

Reaction 3 NH4+ + CO32- NH3 + HCO3-

Reaction 4 H2PO4- + OH- HPO42- + H2O

Reaction 5 H2SO4 + N2H5+ HSO4- + N2H62+

Reaction 6 HPO42- + SO32- PO43- + HSO3-

PROBLEM: The following reactions are important environmental processes.

(b) H2O(l) + SO32-(aq) ⇌ OH-(aq) + HSO3-(aq)

PLAN: Identify proton donors (acids) and proton acceptors (bases).

SOLUTION: (a) H2PO4-(aq) + CO32-(aq) ⇌ HPO42-(aq) + HCO3-(aq)

conjugate pair1 conjugate pair2

(b) H2O(l) + SO32-(aq) ⇌ OH-(aq) + HSO3-(aq)

(b) H2O(l) + HS-(aq) ⇌ OH-(aq) + H2S(aq)

SOLUTION: (a) H2PO4-(aq) + NH3(aq) ⇌ HPO42-(aq) + NH4+(aq)

PROBLEM: Phenylacetic acid (C6H5CH2COOH, simplified here as HPAc) builds

Assumptions: With a pH of 2.62, the [H3O+]HPAc >> [H3O+]water.

SOLUTION: HPAc(aq) + H2O(l) ⇌ H3O+(aq) + PAc-(aq)

Concentration(M) HPAc(aq) + H2O(l) ⇌ H3O+(aq) + PAc-(aq)

Initial 0.12 - 1x10-7 0

PROBLEM: Propanoic acid (CH3CH2COOH, which we simplify and HPr) is an

Concentration(M) HPr(aq) + H2O(l) ⇌ H3O+(aq) + Pr-(aq)