Neutralization Titrations

widely used to determine the concentration of analytes

that are themselves acids or bases or are
convertible to such species by suitable treatment
water is the usual solvent ; readily available,
inexpensive , non-toxic, low temperature coefficient of
expansion
some analytes are not titratable in aqueous media ;
solubilities are too low ; strengths as acids or bases are
not sufficiently great to provide satisfactory end points
 Classification of Acid-Base Indicators
Acid-Base
1. Phthalein Indicators - are colorless in
Indicator moderately acidic solutions and exhibit a variety
of colors in alkaline media ; sparingly soluble in
water but readily dissolve in ethanol

is a chemical, Examples: Phenolphthalein ; Thymolphthalein

or mixture of 2. Sulfonphthalein Indicators - exhibit two

useful color-change ranges (one in somewhat
chemicals, acidic solutions and the other in neutral or
that changes moderately basic media
color over a Example: Phenol Red
known range 3. Azo Indicators - exhibit a color change from
of pH red to yellow with increasing basicity ; their
transition ranges are generally on the acidic side
of neutrality
Examples: Methyl Orange ; Methyl Red
 Some Important Acid/Base Indicators

Indicator Transition Color Change Indicator

Range, pH Type
Methyl Yellow 2.9 4.0 Red-Yellow 2
Methyl Orange 3.1 4.4 Red-Orange 2
Bromocresol Green 3.8 5.4 Yellow-Blue 1
Methyl Red 4.2 6.3 Red-Yellow 2
Bromocresol Purple 5.2 6.8 Yellow-Purple 1
Bromothymol Blue 6.2 7.6 Yellow-Blue 1
Phenol Red 6.8 8.4 Yellow-Red 1
Cresol Purple 7.6 9.2 Yellow-Purple 1
Phenolphthalein 8.3 10.0 Colorless-Red 1
Thymolphthalein 9.3 10.5 Colorless-Blue 1
Alizarin Yellow GG 10 - 12 Colorless-Yellow 2
 Neutralization Titrations

Titration Curves Titration of HCl with NaOH

plots of a concentration-
related variable as a
function of reagent
volume
judge feasibility of a titration
reaction
selection of indicator

plots of pH or pOH and

volume of titrant
 Standard Solutions of Acids

Acidic Characteristics / Properties

Titrants
1. HCl widely used for titration of bases
dilute solutions are stable indefinitely
do not cause troublesome precipitation reactions with
most cations
restandardization is never required
2. HClO4 solutions are also stable
useful for titrations where chloride ion interferes by
3. H2SO4 forming precipitates
restandardization is never required
4. HNO3 seldom encountered because of their oxidizing properties
 Standard Solutions of Bases

Basic Titrants Characteristics / Properties

1. NaOH none of these is obtainable in

primary-standard purity
2. KOH standardization is required after
3. Ba(OH)2 preparation
react rapidly with atmospheric CO2 to
produce corresponding CO32-
 Primary Standards for Acidic Titrants

Primary Standards h Characteristics

(Basic)
1. anhydrous 2 two end points are observed during
Na2CO3 the titration ( first at pH 8.3 ; second
at 3.8 )
sharper end point can be achieved by
boiling the solution briefly to
eliminate H2CO3 and CO2
2. TRIS / THAM 1 substantially greater equivalent weight
than sodium carbonate
Tris-(hydroxymethyl) aminomethane
3. Borax 2
4. HgO 2
 Primary Standards for Basic Titrants

Primary Standards h Characteristics

(Acidic)
1. KHP 1 ideal primary standard
non-hygroscopic crystalline solid with
high molar mass (204.2)
2. Benzoic Acid 1 its solubility in water is limited,
ordinarily dissolved in ethanol prior to
dilution with water and titration
blank test is required since
commercial alcohol is sometimes
slightly acidic
3. KH(IO3)2 1 excellent primary standard with a high
molecular mass per mole of protons
a strong acid that can be titrated using
virtually any indicator with a transition
range between pH 4 and 10
 Exercise 7

Calculate the average normal concentration of a

NaOH solution from the accompanying titration
data. In addition, calculate the standard deviation of
the data.
Weight of KHP taken Volume of NaOH Used
(g) (mL)
0.7644 34.56
0.5131 22.90
0.6985 31.70
0.7214 32.56
Molar Masses: KHP = 204.23 NaOH = 40.00
 Classification of Neutralization Titrations

I. Alkalimetric Method / Alkalimetry

Analyte/s Titrant

BASES STANDARD ACID

Organic or Inorganic

II. Acidimetric Method / Acidimetry

Analyte/s Titrant

ACIDS STANDARD BASE

Organic or Inorganic
Note: These methods employ one or a combination
of titration methods.
 Typical Applications

Elemental Analysis

several important Element Converted to

elements that occur in N NH3
organic and biological
systems S SO2
non-metallic (e.g. C CO2
carbon, chlorine, bromine,
fluorine and few other less Cl / Br HCl / HBr
common species F SiF4
pretreatment converts the P H3PO4
element to an inorganic
acid or base that is then
titrated
 Typical Applications

Kjeldahl Method

most common method for suitable factor for protein

determining organic content computation: 6.25
nitrogen which is based for meats ; 6.38 for dairy
on a neutralization products ; 5.70 for cereals
titration
the standard means for steps followed in the
determining the protein analysis: decomposition,
content of grains, meats distillation and titration
and other biological
materials
 Exercise 8
The ammonia produced Analysis of a Cereal Sample
in a Kjeldahl Sample
decomposition of a 0.760- Analyte
g sample was collected in Indicator
50.00-mL of 0.1005-M
Titrant/s
HCl. Titration of the
excess acid required 2.44- Method
mL of 0.01168-M NaOH. Given
Express the results of this Answer/s
analysis in terms of
percent: Molar Masses:
a. nitrogen HCl 36.46
b. cereal protein NaOH 40.00
N 14.0067
 Exercise 8
A Kjeldahl analysis was Analysis of Impure Biguanide
Sample
performed upon a
Analyte
0.0550-g sample of
Indicator
impure biguanide,
Titrant/s
C2H7N5. The liberated
Method
ammonia, collected in
Given
40-mL of 4% boric acid,
Answer/s
was titrated with 19.51-
mL of 0.1060-M HCl. Molar Masses:
Calculate the C2H7N5 101.1
percentage of biguanide HCl 36.46
in the sample.
 Determination of Inorganic Substances

numerous inorganic species can be determined by

titration with strong acids or bases
ammonium salts are conveniently determined by
conversion to ammonia with strong base followed by
distillation ; the ammonia collected and titrated as in
the Kjeldahl method
method described for ammonium salts can be
extended to the determination of inorganic nitrate or
nitrite ; are first reduced to ammonium ion by
Devardas alloy or Arnds alloy
 Determination of Inorganic Substances

qualitative and quantitative determination of the

constituents in a solution containing NaOH, Na2CO3
and NaHCO3, either alone or admixed
no more than two of these constituents can exist in an
appreciable amount in any solution because reaction
will eliminate the third
analysis of such mixture requires two titrations: one
with an alkaline-range indicator (e.g. Pp) and the other
with an acid-range indicator (e.g. MO)
 Carbonate and Carbonate Mixtures

Qualitative Quantitative
Determination Determination

composition of the once the composition

solution can then be of the solution has
deduced from the been established, the
relative volumes of volume data can be
acid needed to titrate used to determine the
equal volumes of the concentration of each
sample component in the
sample
Titration Curves : Double Indicator Titration
 Double Indicator Titration: One Sample

Composition Volume Relationship Volume Expression

Pure NaOH mL Pp mL Pp
mL MO = 0.00 mL
Pure Na2CO3 mL Pp = mL MO (mL Pp + mL MO) or

2(mL Pp) or 2(mL MO)

Pure NaHCO3 mL Pp = 0.00 mL mL MO
mL MO
Mixture : mL Pp > mL MO (mL Pp - mL MO)
NaOH & Na2CO3 2(mL MO)
Mixture : mL Pp < mL MO 2(mL Pp)
Na2CO3 & NaHCO3 (mL MO - mL Pp)
 Double Indicator Titration: Two Samples

Composition Volume Volume Expression

Relationship
Pure NaOH mL Pp = mL MO mL Pp or mL MO
Pure Na2CO3 mL Pp = (mL MO) 2(mL Pp) or mL MO
Pure NaHCO3 mL Pp = 0.00 mL mL MO
mL MO
Mixture : mL Pp > (mL MO) mL MO - [2(mL MO-mL Pp)]
NaOH & Na2CO3 2(mL MO mL Pp)
Mixture : mL Pp < (mL MO) 2(mL Pp)
Na2CO3 & NaHCO3 mL MO - [2(mL Pp)]
 Exercise 9
A series of solutions containing NaOH, Na2CO3 and NaHCO3, alone or
in compatible combination, was titrated with 0.1202-M HCl. The
volumes of acid needed to titrate 25.00-mL portions of each solution
to a (1) phenolphthalein and (2) bromocresol green endpoint are given
in the table that follows. Use this information to deduce the
composition of the solutions. In addition, calculate the number of
milligrams of each solute per milliliter of solution.
Solution mL Pp mL BCG
1 29.64 36.42
2 0.00 33.33
3 22.42 22.44
4 15.67 42.13
5 16.12 32.23
 Exercise 9
Five samples, each weighing 5.041-g, containing NaOH, Na2CO3 and
NaHCO3, alone or in some combination, along with inert material was
analyzed. When each sample was titrated with 0.1533-N HCl, the
following end points were observed.
Solution Pp Titration (mL) MO Titration (mL)
A 37.48 18.74
B 20.67 20.67
C 15.41 0.00
D 12.06 33.90
E 0.00 31.49
Use this information to deduce the composition of the samples. In
addition, calculate the percentage of each solute in the above listed
samples.
 Modified Double Indicator Titration

Winkler Method

mixtures of carbonate & presence of the sparingly

hydrogen carbonate ions soluble barium carbonate
and carbonate & does not interfere as long
hydroxide ions as the concentration of
barium ion is greater than
greatly improved by 0.1-M
taking advantage of the presence of solid barium
limited solubility of carbonate does not
barium carbonate in hamper end-point
neutral and basic medium detection
 Exercise 10
A 1.217-g sample of commercial KOH contaminated by
K2CO3 was dissolved in water, and the resulting solution
was diluted to 500.0-mL. A 50.00-mL aliquot of this
solution was treated with 40.00-mL of 0.05304-N HCl and
boiled to remove CO2. The excess acid consumed 4.74-mL
of 0.04983-N NaOH (phenolphthalein indicator). An
excess of neutral BaCl2 was added to another 50.00-mL
aliquot to precipitate the carbonate as BaCO3. The solution
was then titrated with 28.56-mL of the acid to a
phenolphthalein end point. Calculate the percentage of
KOH, K2CO3, and H2O in the sample, assuming that these
are the only compounds present.

Molar Masses : KOH = 56.11 ; K2CO3 = 138.21 ; H2O = 18.015

 Exercise 10

A 0.5000-g sample containing NaHCO3, Na2CO3, and H2O

was dissolved and diluted to 250.0-mL. A 25.00-mL aliquot
was the boiled with 50.00-mL of 0.01255-M HCl. After
cooling, the excess acid in the solution required 2.34-mL of
0.01063-M NaOH when titrated to a phenolphthalein end
point. A second 25.00-mL aliquot was then treated with an
excess of BaCl2 and 25.00-mL of the base; precipitation of
all the carbonate resulted, and 7.63-mL of the HCl were
required to titrate the excess base. Calculate the
composition of the mixture.
Molar Masses :
NaHCO3 = 84.01 ; Na2CO3 = 105.99 ; H2O = 18.015
Determination of Organic Functional Groups

Amine Groups Ester Groups

many amines that are are commonly

too weak to be titrated determined by
as bases in water are saponification with a
readily titrated in non- measured quantity of
aqueous solvents, such standard base ; excess
as anhydrous acetic base is then titrated
acid, which enhance with standard acid
their basicity
Determination of Organic Functional Groups

Hydroxyl Groups Carbonyl Groups

can be determined by can be determined with

esterification with a solution of
various carboxylic acid hydroxylamine
anhydrides or chlorides hydrochloride
(e.g. acetic anhydride
the reaction produces
and phthalic anhydride)
an oxime and the
liberated hydrochloric
acid is titrated
Determination of Organic Functional Groups

Carboxylic and Sulfonic Acid Groups

two most common equivalent weights serve

structures that impart as an aid in qualitative
acidity to organic identification of organic
compounds acids
neutralization titrations
are often employed to
determine the
equivalent weight of
purified organic acids
 Determination of Salts

total salt content of a standard acid or base

solution can be solutions can also be
accurately and readily prepared with ion-
determined by an acid- exchange resins
base titration
salt is converted to an
equivalent amount of an
acid or base by passage
through a column
packed with an ion-
exchange resin
 Exercise 11

A 0.8160-g sample containing dimethylphthalate

and unreactive species was saponified by refluxing
with 50.00-mL of 0.1031-M NaOH. After the
reaction was complete, the excess NaOH was back-
titrated with 24.27-mL of 0.1644-M HCl. Calculate
the percentage of dimethylphthalate in the sample.
Molar Masses:
C6H4(COOCH3)2 = 194.19 NaOH = 40.00 HCl = 36.46
 Exercise 11

A 50.00-mL sample containing methylethyl ketone

and unreactive species was treated with an excess of
hydroxylamine hydrochloride H2NOH . HCl. After
oxime formation was complete, the liberated HCl was
titrated with 19.15-mL of 0.01123M NaOH. Calculate
the number of milligrams of CH3COC2H5 per liter of
sample.
Molar Masses:
CH3COC2H5 = 71.11 NaOH = 40.00
 Exercise 12

The Merck Index indicates that 10-mg of guanidine,

CH5N3, may be administered for each kilogram of body
weight in the treatment of myasthenia gravis. The
nitrogen in a 4-tablet sample that weighed a total of
7.50-g was converted to ammonia by a Kjeldahl
digestion, followed by distillation into 100.0-mL of
0.1750-M HCl. The analysis was completed by titrating
the excess acid with 11.37-ml of 0.1080-M NaOH. How
many of these tablets represent a proper dose for a 48
kilogram patient. Molar Mass : CH5N3 = 59.08