Experiment 3

ACID – BASE TITRATION

Objectives
Upon the completion of the experiment, the student should be able to:
1. define the basic principles and techniques involved in the preparation,
standardization, and of comparison of solutions, and analysis of unknown samples
for acid-base titrations;
2. define the principles and proper techniques involved in using double indicator
titrations for analysis of samples;
3. determine quantitively the components of a carbonate mixture in the original
sample; and
4. calculate the percent of the components of a carbonate minute in the original
sample; and
5. perform acid-base titration properly in determining the purity of a sample.

Introduction

There are many types of volumetric analyses in the study of analytical chemistry. One
of the most common and easiest methods is titration. In determining the exact concentration
of a solution, a procedure called a titration is commonly used. Titration is a process in which
a solution containing a known amount of a substance can react with a second solution
containing an unknown concentration of another substance that will react with the first
substance in a known and reproducible manner. The substances can react until there is some
indication that equivalent amounts of the substances have reacted. Titrations are based on a
reaction between the analyte and the titrant. Volumetric titrations includes measuring the
volume of a solution of known concentration that is needed to react completely with the
analyte, gravimetric titrations includes having the mass of the reagent be measured instead
of its volume, coulometric titrations includes having the “reagent” a constant direct electrical
current of known magnitude that consume the analyte, other titration method includes:
redox titrations, amperometric titrations, and spectrophotometric titrations. The completed
reaction of a titration is usually indicated by a color change or a pH measurement.
Acid-base titrations are chemical reaction that is involved between acids and bases
are called as neutralization reactions, from which the product is a salt, and a by-product of
water. The water is produced by combining the hydrogen (hydronium) ions present in the
acid, to the hydroxide ions present in the base. By knowing the concentration of an acid using
a standardized basic solution is called as alkalimetry or acidimetry. An acid-base
neutralization reaction will yield salt and water. Acid-base reactions do not show visible
physical changes when products are formed (i.e. do not form solids nor vapors, nor show
changes in temperature) and thus the equivalence point is difficult to determine. In this
regard, aside from the acid and base, another important component of an acid-base titration
is an acid-base indicator, which is a weak organic acid or base whose undissociated form
differs in color from its conjugate form. The acid-base indicator changes its color upon
adding a very slight excess of the titrant. In an acid-base titration, the neutralization reaction
between the acid and base can be measured with either a color indicator or a pH meter. An
indicator’s entire color transition must lie within the sharp transition in pH occurring near
the equivalence point.
Acid + Base  Salt + Water

A titration can be performed with almost any chemical reaction for which the
balanced chemical equation is known. A titration can be performed with almost any chemical
reaction for which the balanced chemical equation is known. All acid-base titration reactions,
as all acid-base reactions, are simply exchanges of protons, as in the case of

HCl + NaOH NaCl + H2O,

although the reaction would be correctly written as

H3O+ + OH- H2O

In acid-base titration, the neutralization point occurs at a pH of 7.0. Since indicators react
with the solution being measured, they should be used in moderation—only a few drops if
possible. The point at which the titrant fully neutralizes all the titer, leaving neutral water, is
called the “equivalence point.” This is when the titrant has "used up" all the titer. The acid
and base have fully canceled each other out. The product of the equivalence point volume
(Veq) and the concentration of the titrant (CT) will give the moles of titrant reacting with the
analyte.
Moles titrant = Veq x CT

The moles of analyte can then be calculated by applying stoichiometry of the titration
reaction

During the process, two important stages known as endpoint and equivalence point
are reached. An equivalence point in a titration refers to a point in which the added titrant is
chemically equivalent to the analyte in the sample. Endpoint, on the other hand, is a point
where the indicator changes its color. The main difference between equivalence and
endpoint is that the equivalence point is a point where the chemical reaction comes to an
end while the endpoint is the point where the color change occurs in a system. The
equivalence point of a titration cannot be determined experimentally. Although, the
endpoint is normally regarded as the equivalence point, they are not the same, but since
there is only a slight difference between an equivalent point and an end point, it can be
considered the same for laboratory purposes. The difference in volume or mass between the
equivalence point and the end point is the titration error. Indicators are often added to the
analyte solution to produce an observable physical change (signaling the end point) at or
near the equivalence point. The titration error is given as:

Et =VepVeq

Where Vep is the actual volume of reagent required to reach the end point and Veq is the
theoretical volume necessary to reach the equivalence point. The titration error can be
estimated with a blank titration, in which the same procedure is done but without the
analyte.

This process involves an analyte of unknown concentration, and a titrant, that usually
has a known concentration. Dilution is the process of decreasing the concentration of a solute
in a solution, usually simply by mixing with more solvent like adding more water to a
solution. To dilute a solution means to add more solvent without the addition of more solute.
One of the best working formulas for this is the dilution equation, which is;
C1V1 = C2V2
wherein C1 is the molarity of the titrant, V1 the volume of the titrant that is used to complete
the reaction, V2 the volume of the analyte which has an unknown concentration, and C2,
which is what is usually the unknown.
Using the dilution equation, measurements needed to dilute solutions can be made. The
following experiment requires 500 mL of 0.05 M HCl solution. The equation can be used to
compute the amount of 1.0 M HCl needed to prepare the required solution.
C2 ∙ V2 0.05 M ∗ 0.5 L
V1 = =
C1 1.0 M
V1 = 0.025 L or 25 mL
Implying that 25 mL 1.0 M HCl is needed to prepare 500 mL of 0.05 M HCl solution.
Dilution factor refers to the ratio of the volume of the initial (concentrated) solution
to the volume of the final (dilute) solution. The formula for the dilution factor can also be
derived from the dilution equation.
V2
Dilution factor =
V1
Given a dilution ratio of 1:25, the volume of original sample needed for each of the certain
sizes of volumetric flask can be calculated using the formula for dilution factor.
Table 3.1. Amount of original sample needed for varying volumetric flasks.
Volumetric flask size (mL) Amount of Original Sample Needed
50 mL
50 mL V1 = = 2 mL
25

100 mL
100 mL V1 = = 4 mL
25

250 mL
250 mL V1 = = 10 mL
25

In titration there are different methods, and this experiment is focused on acid-base
reactions. The reaction involves mainly a base and an acid, from which either one has a
known concentration. Certain procedures must be followed in the process of acid-base
titrations, such as standardization of the acid/base solution. The method of determining the
exact concentration of standard solutions is referred to as standardization. The method
makes use of a solid pure substance, a primary standard to determine the exact
concentration of a secondary standard solution.

NaOH is an inexpensive, highly soluble, and relatively easy to use base, so it's often
the go-to chemical for simple titrations; however, it is far from perfect. Solid NaOH absorbs
water from the air, so accurately weighing a sample during the preparation of a solution is
impossible and a solution of NaOH tends to absorb atmospheric carbon dioxide, which is
weakly acidic. Standardization is typically carried out by titrating the NaOH solution with a
primary standard, an ultra-pure, easily soluble acid such as potassium hydrogen phthalate
(KHP). A primary standard is a reference chemical used to measure an unknown
concentration of another known chemical. It can be used directly when performing titrations
or used to calibrate standard solutions. Primary standards exhibit distinctive characteristics
that ideally suit them for making accurate and reliable assessments of concentration without
the need for specialized equipment. These characteristics include high purity, low reactivity
with the air or surrounding environment, low hygroscopicity, large molar mass and a
predictable reactivity. Unlike NaOH, KHP can be used to prepare a solution whose
concentration is known with a high degree of precision. The only way to accurately assess
the molar concentration of a previously prepared NaOH solution, is to titrate it with a
solution such as KHP. Once the NaOH solution has been standardized and its concentration
is well-known, it can be used to titrate other acid solutions such as HCl. The reaction of KHP
titrated with standardized NaOH solution is
KHC8H4O4 + NaOH → NaKC8H4O4 + H2O
This experiment includes diluting solid NaOH pellets in distilled water to prepare 500 mL of
0.05 M NaOH solution and the mass of NaOH pellets needed is 1 g.
0.05 mol NaOH 40 g NaOH 0.5 L
mass of NaOH pellets needed = ( )( )( )
L mol NaOH 1
mass of NaOH pellets needed = 1 g
Double titration is a method of determining the amount of substance present in the
form of a solution along with another solution. It can be used in the case of a mixture of bases
involving NaOH, Na2CO3 or NaHCO3. These bases are titrated against strong acids with
proper indicators. Generally, a single indicator is not enough, so two indicators are used.
Qualitative and quantitative determinations of the constituents in a solution containing
Na2CO3, NaHCO3 and NaOH alone or in a mixture provide an interesting example for
neutralization titrations. Mixing of NaOH with NaHCO3 results in the formation of Na2CO3
until one or the other (or both) of the original reactants is used up.

1. NaOH+ NaHCO3→ Na2CO3 + H2O

Considering a mixture of NaOH and Na2CO3, the reaction between HCl and Na2CO3 takes
place in two stages:

2. HCl + Na2CO3- → NaHCO3 + H2

3. HCl + NaHCO3- → NaCl + CO2 + H2O

While that between HCl and NaOH completes in only one step:

4. HCl + NaOH- → NaCl+ H2O

Solution mixture of reaction (1) at the equivalence point is alkaline, that of reaction (2)
is acidic and that of reaction (3) is neutral. Thus, the whole titration should have three breaks
in the pH curve, corresponding to the above three stages. Reactions (1) and (3) can be
indicated by phenolphthalein and that of reaction (2) can be indicated by methyl orange.

Analysis of such mixtures requires the use of two indicators in their titrations with
standard acid solutions. An indicator with a transition range in the pH range of 8 to 10, such
as phenolphthalein, is used for detecting the first end point; an acid range indicator such as
bromocresol green is used for the second end point. Titration can be done using one sample,
using both indicators by successive addition of acid solution after each color change or using
two samples containing the with HCl until phenolphthalein endpoint while the total basic
strength of the mixture is determined by titration with the same standard acid until the
methyl orange endpoint same amount of mixture solution and applying two indicators
separately. The composition of the solution can be obtained using the volumes of acid used
for reaching each end point. Once the composition is known, the data can then be used to
determine the concentration of each components in the sample. In the quantitative analysis
of the components, the carbonate present in the sample will be precipitated with BaCl2,
leaving the NaOH component in the solution to be titrated.
The titrant reacts with the analyte and forms an insoluble substance. The titration is
continued till the last drop of the analyte is consumed. When the titrant is excess it reacts
with the indicator and signals to terminate the titration process. A typical precipitation
reaction occurs when an aqueous solution of barium chloride is mixed with one containing
sodium sulfate. To know if the precipitation is complete, there should be no more solid that
appears to be forming as the barium chloride is being added. The equation for the
precipitation reaction between BaCl2 and Na2CO3 is
BaCl2 + Na2CO3 → BaCO3 + 2NaCl

Table 3.2. Qualitative analysis of carbonate mixtures using volumes at end points.
Volume relationship of standard acid used to reach end points*
Component present
NaOH Vph = Vmo
Na2CO3 Vph = ½ Vmo
NaHCO3 Vph = 0; Vmo >0
NaOH, Na2CO3 Vph > ½ Vmo
Na2CO3, NaHCO3 Vph < ½ Vmo
*Vph = volume of acid needed to reach end point using phenolphthalein
Vmo = volume of acid needed to reach end point using methyl orange
The following equations will be used for the calculation of needed data

Σ|xi − x̅|
average deviation = d̅ =
n

mass of solute
Normality =
equivalent mass ∙ volume of solution
molar mass
equivalent mass =
n
mass of KHC8 H4 O4
Purity of KHP % = ∙ 100
mass of KHP sample
Vph = Vblank – Vsample